SULFONAMIDE-HETEROCYCLIC HERBICIDAL COMPOUNDS

Title:

SULFONAMIDE-HETEROCYCLIC HERBICIDAL COMPOUNDS

Document Type and Number:

WIPO Patent Application WO/2015/004282

Kind Code:

Abstract:

The present invention relates sulfonanilide derivatives of the formula (I) wherein A, W, X, Z, m, n, p, R, R1, R2, R5, R6, R11 and R12 are as defined in the specification. Furthermore, the present invention relates to herbicidal compositions comprising these compounds and to methods of using these compounds to control plant growth.

Inventors:

WHITTINGHAM WILLIAM GUY (GB)
MITCHELL GLYNN (GB)
INGRAM KATHARINE MARY (GB)
DALENCON ANNE JACQUELINE (GB)
THOMPSON ALISON JANE (GB)
ARMSTRONG SARAH (GB)
DE FRAINE PAUL JOHN (GB)

Application Number:

PCT/EP2014/064983

Publication Date:

January 15, 2015

Filing Date:

July 11, 2014

Export Citation:

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Assignee:

SYNGENTA LTD (GB)

International Classes:

C07D401/06; A01N43/40; A01N43/52; A01N43/56; A01N43/78; A01N43/80; C07D409/04; C07D413/04; C07D417/04

Domestic Patent References:

WO2004070050A2	2004-08-19
WO2006010643A1	2006-02-02
WO2002016318A1	2002-02-28
WO2005054179A2	2005-06-16
WO2013061973A1	2013-05-02

Foreign References:

EP2420493A1

2012-02-22

Other References:

DOMINIQUE LESUISSE ET AL: "Discovery of the first non-ATP competitive IGF-1R kinase inhibitors: Advantages in comparison with competitive inhibitors", BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, vol. 21, no. 8, 1 April 2011 (2011-04-01), pages 2224 - 2228, XP055140461, ISSN: 0960-894X, DOI: 10.1016/j.bmcl.2011.03.003
DATABASE REGISTRY [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 5 December 2011 (2011-12-05), "Methanesulfonamide, N-[4-[4-(1,1-dimethylethyl)phenyl]-5,5-dimethyl-2,4-dioxo-1-imidazolidinyl]methyl]-2-pyridinyl]-", XP002729828, Database accession no. 1348826-57-2

Attorney, Agent or Firm:

SYNGENTA INTERNATIONAL AG (Schwarzwaldallee 215, Basel, CH)

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Claims:

CLAIMS

1 . A herbicidal compound of formula (I):

wherein:

A is a 5- or 6-membered heteroaromatic ring containing 1 , 2, 3, or 4 heteroatoms selected from oxygen, sulphur and nitrogen, with the proviso that A is not

m is an integer selected from 0, 1 or 2; n is an integer selected from 0, 1 , 2 or 3; p is an integer selected from 0, 1 , 2, or 3; with the proviso that 0 < n + p < 3; W is oxygen or sulphur; X is oxygen, sulphur, SO, S0₂ or CR³R⁴; Z is oxygen, sulphur, CR⁸R⁹ or NR ⁰; R is Ci-₆alkyl or d-₆haloalkyl;

R is H, Ci-₄alkyl, C₃.₅alkenyl, propargyl, d. 4haloalkoxyCi-₂alkyl, cyanoCi_₂alkyl, d.

4alkoxycarbonylCi-₂alkyl, arylCi_₂alkyl optionally substituted by 1 -3 groups R²⁰, heteroarylCi_₂alkyl optionally substituted by 1 -3 groups R²⁰, arylthioCi_₂alkyl optionally substituted by 1 -3 groups R²⁰, arylCi-₂alkoxyCi-₂alkyl optionally substituted by 1 -3 groups R²⁰, arylCi.₂alkylthioCi-₂alkyl optionally substituted by 1 -3 groups R²⁰, arylcarbonylCi_₂alkyl optionally substituted by 1 -3 groups R²⁰, rylcarbonyloxyCi_₂alkyl optionally substituted by 1 -3 groups R²⁰, aryloxycarbonyloxyCi_₂alkyl optionally substituted by 1 -3 groups R²⁰, Ci_₈alkylcarbonyl, C₂-₅alkenylcarbonyl, Ci_ ₄haloalkylcarbonyl, Ci-₄alkoxyCi-₂alkylcarbonyl, C₃.₆cycloalkylcarbonyl, Ci.₄alkoxycarbonylCi_ ₂alkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R²⁰, aryloxyd-₂alkylcarbonyl optionally substituted by 1-3 groups R²⁰, Ci_i₀alkoxycarbonyl, Ci_₄haloalkoxycarbonyl, C₃.

5alkenyloxycarbonyl, propargyloxycarbonyl, Ci.₄alkoxyCi.₂alkoxycarbonyl, Ci_₄alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R²⁰, arylCi_₂alkoxycarbonyl optionally substituted by 1-3 groups R²⁰, aminocarbonyl, Ci.₄alkylaminocarbonyl, di(Ci.₄alkyl)aminocarbonyl, Ci_₆alkylsulphonyl, Ci_₆haloalkylsulphonyl or arylsulphonyl optionally substituted by 1-3 groups R²⁰, and each R²⁰ is, independently, halogen, C₁_₄alkyl, C-|.₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci_ ₂alkoxyCi_₂alkoxy, hydroxy, phenyl or phenoxy;

R² is halogen, nitrile, C₁_₄alkyl, C-|.₄haloalkyl, C₃.₆cycloalkyl, C₂.₄alkenyl, C₂.₄alkynyl, Ci_₄alkoxy, Ci_ ₄haloalkoxy, Ci_₂alkoxyCi_₂alkoxy, hydroxy, Ci_₄alkylcarbonyl, Ci_₄alkylsulphonyl, or phenyl or two R² groups together form -OCH₂0- or -OCH₂CH₂0-;

R³ and R⁴ are, independently, H, C₁_₄alkyl, C-|.₄haloalkyl, Ci_₄alkoxycarbonyl, or aryl optionally substituted by 1-3 groups R²³ or R³ and R⁴ together form a C₂.₅alkylene chain or an oxo group or R³ together with one of R⁵, R⁸ or R forms a bond or R³ and R⁸ together form a C₂.₅alkylene chain and each R²³ is, independently, halogen, C₁_₄alkyl, C-|.₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci_

2alkoxyCi_₂alkoxy, hydroxy, phenyl or phenoxy;

R⁵ and R⁶ are, independently, H, Ci_₅alkyl, Ci_₄haloalkyl, C₃.₆cycloalkyl optionally substituted with 1- 3 groups selected from halogen, d_₄alkyl or phenyl, Ci_₄alkoxyCi_₄alkyl, d- ₄alkoxycarbonylaminoCi_₄alkyl, Ci_₄alkylcarbonyloxyCi_₂alkyl, arylCi_₂alkyl optionally substituted by 1-3 groups R² , aryloxyCi_₂alkyl optionally substituted by 1-3 groups R² , arylCi_₂alkoxyCi_₂alkyl optionally substituted by 1-3 groups R² , C₂.₄alkenyl, hydroxy, Ci_₄alkoxy, Ci_₄alkylthio, d- ₄alkylcarbonyloxy, aryl optionally substituted by 1-3 groups R² , aryloxy optionally substituted by 1-3 groups R² , arylthio optionally substituted by 1-3 groups R² , heteroaryl optionally substituted by 1- 3 groups R² or R⁵ and R⁶ together form an oxo group or a C₂.₆alkylene chain optionally containing an oxygen or sulphur atom and optionally substituted by 1-3 groups selected from halogen or d- ₂alkyl or R⁵ together with together with one of R³, R⁸ or R forms a bond or R⁵ and R together form a C₂-salkylene chain and each R² is, independently, halogen, cyano, d_₄alkyl, d_₄haloalkyl, Ci_₄alkoxy, Ci.₄haloalkoxy, Ci.₂alkoxyCi.₂alkoxy, hydroxy, phenyl or phenoxy or two R² groups together form OCH₂0 or OCH₂CH₂0;

R⁸ and R⁹ are, independently, H, halogen, cyano, d_₄alkyl, d_₄haloalkyl, d-salkenyl, d-salkynyl, Ci_₄alkoxy, d_₄alkylthio, Ci_₄alkoxycarbonyl, aryl optionally substituted by 1-3 groups R²⁴, aryloxy optionally substituted by 1-3 groups R²⁴ or arylthio optionally substituted by 1-3 groups R²⁴ or R⁸ and R⁹ together form a d-salkylene chain or an oxo group or R⁸ together with one of R³ or R⁵ forms a bond or R⁸ and R³ together form a d-salkylene chain and each R²⁴ is, independently, halogen, cyano, d_₄alkyl, C-|.₄haloalkyl, Ci.₄alkoxy, d_₄haloalkoxy, Ci.₂alkoxyCi.₂alkoxy, hydroxy, phenyl or phenoxy;

R ⁰ is H, d_₄alkyl, d-salkenyl, aryl optionally substituted by 1-3 groups R²², arylCi_₂alkyl optionally substituted by 1-3 groups R²², heteroaryl optionally substituted by 1-3 groups R²², d_₄alkylcarbonyl, Ci-₄alkoxycarbonyl, Ci_₄haloalkoxycarbonyl, Ci-₄alkoxyCi-₂alkoxycarbonyl, C₃.₅alkenyloxycarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R²², arylCi_₂alkoxycarbonyl optionally substituted by 1-3 groups R²², aminocarbonyl, Ci.₄alkylanriinocarbonyl, di(Ci.₄alkyl)aminocarbonyl, Ci_₆alkylsulphonyl or d-₆haloalkylsulphonyl and each R²² is, independently, halogen, nitro, cyano, Ci-₄alkyl, Ci_₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy, Ci-₂alkoxyCi-₂alkoxy, hydroxy, Ci_₄alkylthio, Ci_

₄haloalkylthio, Ci_₄alkylsulphonyl, Ci_₄alkoxycarbonyl, phenyl or phenoxy;

R and R ² are, independently, H, halogen, hydroxy, C₁_₄alkyl, C-|.₄haloalkyl, Ci_₄alkoxy, carboxy, Ci_₄alkoxycarbonyl or R and R ² together form an oxo group or R together with one of R³ or R⁵ forms a bond or R and R⁵ together form a C₂-₅alkylene chain. 2. The compound of claim 1 , wherein A is a 5-membered heteroaromatic ring containing 1 to 4

heteroatoms selected from oxygen, sulphur and nitrogen.

3. The compound of claim 2, wherein A is a pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, 1 ,2,3-triazole, 1 ,2,4-triazole, 1 ,2,3-oxadiazole, 1 ,2,5-oxadiazole, 1 ,2,3-thiadiazole, 1 ,2,5-thiadiazole or tetrazole ring. 4. The compound of claim 3, wherein A is a thiophene, pyrazole, thiazole, 1 ,2,4-triazole or tetrazole ring.

5. The compound of claim 1 , wherein A is a 6-membered heteroaromatic ring containing 1 to 3

nitrogen atoms.

6. The compound of claim 5, wherein A is a pyridine, pyridazine, pyrimidine, pyrazine, 1 ,2,3-triazine or 1 ,2,4-triazine ring.

7. The compound of claim 6, wherein A is a pyridazine, pyrimidine or pyrazine ring.

8. The compound of any one of the preceding claims, wherein W is oxygen.

9. The compound of any one of the preceding claims, wherein X is oxygen or CR³R⁴.

10. The compound of any one of the preceding claims, wherein Z is oxygen, CR⁸R⁹ or NR ⁰; 11. The compound of any one of the preceding claims, wherein m is 0 or 1.

12. The compound of claim 11 , wherein m is 0.

13. The compound of any one of the preceding claims, wherein n is 0, 1 or 2 and p is 0, 1 or 2 with the proviso that 1 < n + p < 2.

14. The compound of any one of the preceding claims, wherein R is Ci-C₆ alkyl.

The compound of any one of claims 1 to 13, wherein R is Ci_₄haloalkyl.

16. The compound of claim 15, wherein R is trifluoromethyl.

17. The compound of any one of the preceding claims, wherein R is H, Ci.₄alkoxyCi.₂alkyl, d. ₄alkoxyCi-₂alkoxyCi-₂alkyl, Ci-₄haloalkoxyCi-₂alkyl, arylCi_₂alkyl optionally substituted by 1-3 groups R²⁰, arylCi.₂alkoxyCi-₂alkyl optionally substituted by 1-3 groups R

arylcarbonyloxyCi-₂alkyl optionally substituted by 1-3 groups R²⁰,

Ci_₈alkylcarbonyl, Ci_₄haloalkylcarbonyl, Ci_i₀alkoxycarbonyl, Ci_ 4haloalkoxycarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R²⁰, arylCi_₂alkoxycarbonyl optionally substituted by 1-3 groups R²⁰, Ci_₆alkylsulphonyl or Ci-₆haloalkylsulphonyl, and each R²⁰ is, independently, halogen, C₁_₄alkyl, C-|.₄haloalkyl, d-₄alkoxy or Ci-₄haloalkoxy

18. The compound of claim 17, wherein R is H, Ci_₅alkylcarbonyl, Ci_₄haloalkylcarbonyl, Ci_

5alkoxycarbonyl, Ci_₄haloalkoxycarbonyl or Ci_₄haloalkylsulphonyl.

19. The compound of claim 18, wherein R is H, Ci_₅alkylcarbonyl or Ci_₅alkoxycarbonyl.

20. The compound of any one of the preceding claims, wherein R² is halogen, C₁_₄alkyl, C-|.₄haloalkyl, Ci_₄alkoxy or Ci_₄alkylsulphonyl.

21. The compound of claim 20, wherein R² is halogen or methyl. 22. The compound of any one of the preceding claims,wherein R³ and R⁴ are, independently, H,

halogen or C₁_₄alkyl.

23. The compound of claim 22, wherein R³ and R⁴ are, independently, H or methyl.

24. The compound of any one of the preceding claims, wherein R⁵ and R⁶ are, independently, H, d.

5alkyl, Ci_₄haloalkyl, C₃.₆cycloalkyl, Ci_₄alkoxyCi_₄alkyl, arylCi_₂alkyl optionally substituted by 1-3 groups R² , C₂-₄alkenyl, Ci_₄alkoxy, Ci_₄alkylthio, aryl optionally substituted by 1-3 groups R² , aryloxy optionally substituted by 1-3 groups R² , arylthio optionally substituted by 1-3 groups R² , heteroaryl optionally substituted by 1-3 groups R² or R⁵ and R⁶ together form a C₂-₅alkylene chain optionally containing an oxygen atom, and each R² is, independently, halogen, cyano, C₁_₄alkyl, Ci-₄haloalkyl, Ci_₄alkoxy or Ci_₄haloalkoxy. 25. The compound of claim 24, wherein R⁵ and R⁶ are, independently, H, d_₄alkyl, C-|.₃haloalkyl, cyclopropyl, Ci_₃alkoxy, Ci_₃alkylthio, aryl optionally substituted by 1-3 groups R² , aryloxy optionally substituted by 1-3 groups R² , arylthio optionally substituted by 1-3 groups R² , heteroaryl optionally substituted by 1-3 groups R² or R⁵ and R⁶ together form a C₃.₅alkylene chain, and each R² is, independently, halogen, cyano, d_₄alkyl, C-|.₄haloalkyl, Ci_₄alkoxy or Ci_₄haloalkoxy. 26. The compound of claim 25, wherein R⁵ and R⁶ are, independently, H, Ci_₃alkyl, trifluoromethyl, cyclopropyl, Ci_₃alkoxy, aryl optionally substituted by 1-2 groups R² or R⁵ and R⁶ together form a C₃.₅alkylene chain, and each R² is, independently, halogen, methyl or methoxy.

27. The compound of any one of the preceding claims, wherein R⁸ and R⁹ are, independently, H, halogen, d_₄alkyl, C-|.₄haloalkyl, Ci_₄alkoxy, Ci_₄alkylthio, aryl optionally substituted by 1-3 groups R²⁴, aryloxy optionally substituted by 1-3 groups R²⁴ or arylthio optionally substituted by 1-3 groups

R²⁴ and each R²⁴ is, independently, halogen, cyano, C-^alkyl, Ci_₄haloalkyl, Ci_₄alkoxy or Ci_ ₄haloalkoxy.

28. The compound of claim 27,wherein R⁸ and R⁹ are, independently, H, halogen, C₁_₄alkyl, C-|.

4haloalkyl, Ci_₄alkoxy, Ci_₄alkylthio, aryl optionally substituted by 1-2 groups R²⁴, and each R²⁴ is, independently, halogen, methyl or methoxy.

29. The compound of claim 28, wherein R⁸ and R⁹ are, independently, H, halogen, d-₃alkyl, Ci_₃alkoxy or Ci-₃alkylthio.

30. The compound of any one of the preceding claims, wherein R ⁰ is H, C₁_₄alkyl, aryl optionally

substituted by 1-3 groups R²², heteroaryl optionally substituted by 1-3 groups R²², Ci_₄alkylcarbonyl, Ci-₄alkoxycarbonyl, Ci_₄alkylsulphonyl or Ci_₄haloalkylsulphonyl and each R²² is, independently, halogen, cyano, C₁_₄alkyl, C-|.₄haloalkyl, Ci_₄alkoxy, Ci_₄haloalkoxy or Ci_₄alkylsulphonyl.

31. The compound of claim 30, wherein R ⁰ is H, Ci_₃alkyl or aryl optionally substituted by 1-3 groups R²², and each R²² is, independently, halogen, methyl or methoxy.

32. The compound of any one of the preceding claims, wherein R and R ² are, independently, H, hydroxy, C₁_₄alkyl, C-|.₄alkoxy, carboxy, Ci_₄alkoxycarbonyl or R and R ² together form an oxo group.

33. The compound of claim 32, wherein R and R ² are each H.

34. A herbicidal composition comprising a compound of formula (I) as defined in any one of claims 1 to

33 together with at least one agriculturally acceptable adjuvant or diluent.

35. A composition according to claim 34 which comprises a further herbicide in addition to the

compound of formula (I).

36. A composition according to claim 34 or 35 which comprises a safener.

37. Use of a compound of formula (I) as defined in any one of claims 1 to 33 or a composition as

defined in any one of claims 34 to 36 as a herbicide.

38. A method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a compound of formula (I) as defined in any one of claims 1 to 33 or a composition as claimed in any one of claims

34 to 36.

Description:

SULFONAMIDE-HETEROCYCLIC HERBICIDAL COMPOUNDS The present invention relates to herbicidal sulfonanilide derivatives.

Some haloalkylsulfonanilide derivatives are known to have herbicidal activities - see EP 2 420 493 and EP 2 336 104.

The object of the present invention is to provide new herbicides, which are highly effective against various weeds at low doses.

Accordingly, the present invention provides a compound of formula (I) or an agrochemically acceptable salt thereof:

wherein:

A is a 5- or 6-membered heteroaromatic ring containing 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulphur and nitrogen, with the proviso that A is not

m is an integer selected from 0, 1 or 2; n is an integer selected from 0, 1 , 2 or 3; p is an integer selected from 0, 1 , 2 or 3; with the proviso that 0 < n + p < 3; W is oxygen or sulphur; X is oxygen, sulphur, SO, S0 ₂ or CR ³R ⁴;

Z is oxygen, sulphur, CR ⁸R ⁹ or NR ⁰;

R is Ci- ₆alkyl or d- ₆haloalkyl; R is H, Ci- ₄alkyl, C ₃. ₅alkenyl, propargyl, Ci_ ₄haloalkoxyCi. ₂alkyl, cyanoCi_ ₂alkyl, Ci_

4alkoxycarbonylCi. ₂alkyl, arylCi_ ₂alkyl optionally substituted by 1-3 groups R ²⁰, heteroarylCi_ ₂alkyl optionally substituted by 1-3 groups R ²⁰, arylthioCi_ ₂alkyl optionally substituted by 1-3 groups R ²⁰, arylCi_ ₂alkoxyCi_ ₂alkyl optionally substituted by 1-3 groups R ²⁰, arylCi_ ₂alkylthioCi_ ₂alkyl optionally substituted by 1-3 groups R ²⁰, arylcarbonylCi_ ₂alkyl optionally substituted by 1-3 groups R ²⁰, d. ₄alkylcarbonyloxyCi_ ₂alkyl, arylcarbonyloxyCi_ ₂alkyl optionally substituted by 1-3 groups R ²⁰, Ci_

4alkoxycarbonyloxyCi_ ₂alkyl, aryloxycarbonyloxyCi_ ₂alkyl optionally substituted by 1-3 groups R ²⁰, Ci_ ₈alkylcarbonyl, C ₂. ₅alkenylcarbonyl, Ci_ ₄haloalkylcarbonyl, Ci_ ₄alkoxyCi_ ₂alkylcarbonyl, C ₃.

6cycloalkylcarbonyl, Ci_ ₄alkoxycarbonylCi_ ₂alkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R ²⁰, aryloxyCi- ₂alkylcarbonyl optionally substituted by 1-3 groups R ²⁰, Ci_i ₀alkoxycarbonyl, Ci_

4haloalkoxycarbonyl, C ₃. ₅alkenyloxycarbonyl, propargyloxycarbonyl, Ci_ ₄alkoxyCi_ ₂alkoxycarbonyl, Ci_ ₄alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R ²⁰, arylCi_ ₂alkoxycarbonyl optionally substituted by 1-3 groups R ²⁰, aminocarbonyl, Ci. ₄alkylaminocarbonyl, di(Ci_

4alkyl)aminocarbonyl, Ci_ ₆alkylsulphonyl, Ci_ ₆haloalkylsulphonyl or arylsulphonyl optionally substituted by 1-3 groups R ²⁰, and each R ²⁰ is, independently, halogen, C ₁_ ₄alkyl, C-|. ₄haloalkyl, Ci_ ₄alkoxy, Ci_

4haloalkoxy, Ci_ ₂alkoxyCi_ ₂alkoxy, hydroxy, phenyl or phenoxy;

R ² is halogen, nitrile, C ₁_ ₄alkyl, C-|. ₄haloalkyl, C ₃. ₆cycloalkyl, C ₂. ₄alkenyl, C ₂. ₄alkynyl, Ci_ ₄alkoxy, Ci_ ₄haloalkoxy, Ci_ ₂alkoxyCi_ ₂alkoxy, hydroxy, Ci_ ₄alkylcarbonyl, Ci_ ₄alkylsulphonyl or phenyl or two R ² groups together form -OCH ₂0- or -OCH ₂CH ₂0-;

R ³ and R ⁴ are, independently, H, C ₁_ ₄alkyl, C-|. ₄haloalkyl, Ci_ ₄alkoxycarbonyl or aryl optionally substituted by 1-3 groups R ²³ or R ³ and R ⁴ together form a C ₂. ₅alkylene chain or an oxo group or R ³ together with one of R ⁵, R ⁸ or R forms a bond or R ³ and R ⁸ together form a C ₂. ₅alkylene chain and each R ²³ is, independently, halogen, C ₁_ ₄alkyl, C-|. ₄haloalkyl, Ci_ ₄alkoxy, Ci_ ₄haloalkoxy, Ci_ ₂alkoxyCi_ ₂alkoxy, hydroxy, phenyl or phenoxy;

R ⁵ and R ⁶ are, independently, H, Ci_ ₅alkyl, Ci_ ₄haloalkyl, C ₃. ₆cycloalkyl optionally substituted with 1-3 groups selected from halogen, d_ ₄alkyl or phenyl, Ci_ ₄alkoxyCi_ ₄alkyl, Ci_ ₄alkoxycarbonylaminoCi. ₄alkyl, Ci_ ₄alkylcarbonyloxyCi_ ₂alkyl, arylCi_ ₂alkyl optionally substituted by 1-3 groups R ² , aryloxyCi_ ₂alkyl optionally substituted by 1-3 groups R ² , arylCi_ ₂alkoxyCi_ ₂alkyl optionally substituted by 1-3 groups R ² , C ₂. ₄alkenyl, hydroxy, Ci_ ₄alkoxy, Ci_ ₄alkylthio, Ci_ ₄alkylcarbonyloxy, aryl optionally substituted by 1-3 groups R ² , aryloxy optionally substituted by 1-3 groups R ² , arylthio optionally substituted by 1-3 groups R ² , heteroaryl optionally substituted by 1-3 groups R ² or R ⁵ and R ⁶ together form an oxo group or a C ₂. ₆alkylene chain optionally containing an oxygen or sulphur atom and optionally substituted by 1-3 groups selected from halogen or Ci_ ₂alkyl or R ⁵ together with together with one of R ³, R ⁸ or R forms a bond or R ⁵ and R together form a C ₂. ₅alkylene chain and each R ² is, independently, halogen, cyano, d_ ₄alkyl, Ci- ₄haloalkyl, Ci_ ₄alkoxy, Ci_ ₄haloalkoxy, Ci_ ₂alkoxyCi_ ₂alkoxy, hydroxy, phenyl or phenoxy or two R ² groups together form OCH ₂0 or OCH ₂CH ₂0;

R ⁸ and R ⁹ are, independently, H, halogen, cyano, d_ ₄alkyl, C-|. ₄haloalkyl, C ₂. ₅alkenyl, C ₂. ₅alkynyl, Ci- ₄alkoxy, Ci_ ₄alkylthio, Ci_ ₄alkoxycarbonyl, aryl optionally substituted by 1-3 groups R ²⁴, aryloxy optionally substituted by 1-3 groups R ²⁴ or arylthio optionally substituted by 1-3 groups R ²⁴ or R ⁸ and R ⁹ together form a C ₂- ₅alkylene chain or an oxo group or R ⁸ together with one of R ³ or R ⁵ forms a bond or R ⁸ and R ³ together form a C ₂- ₅alkylene chain and each R ²⁴ is, independently, halogen, cyano, C ₁_ ₄alkyl, C-|. ₄haloalkyl, d- ₄alkoxy, Ci_ ₄haloalkoxy, hydroxy, phenyl or phenoxy;

R ⁰ is H, Ci- ₄alkyl, C ₂- ₅alkenyl, aryl optionally substituted by 1-3 groups R ²², arylCi_ ₂alkyl optionally substituted by 1-3 groups R ²², heteroaryl optionally substituted by 1-3 groups R ²², Ci_ ₄alkylcarbonyl, Ci_ ₄alkoxycarbonyl, Ci_ ₄haloalkoxycarbonyl, Ci. ₄alkoxyCi. ₂alkoxycarbonyl, C ₃. ₅alkenyloxycarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R ²², arylCi_ ₂alkoxycarbonyl optionally substituted by 1-3 groups R ²², aminocarbonyl, Ci_ ₄alkylaminocarbonyl, di(Ci_ ₄alkyl)aminocarbonyl, Ci_ ₆alkylsulphonyl or Ci_ ₆haloalkylsulphonyl and each R ²² is, independently, halogen, nitro, cyano, Ci_ ₄alkyl, Ci_ ₄haloalkyl, Ci_ ₄alkoxy, Ci_ ₄haloalkoxy, Ci_ ₂alkoxyCi_ ₂alkoxy, hydroxy, Ci_ ₄alkylthio, Ci_ ₄haloalkylthio, Ci_ ₄alkylsulphonyl, Ci_ ₄alkoxycarbonyl, phenyl or phenoxy;

R and R ² are, independently, H, halogen, hydroxy, d_ ₄alkyl, C-|. ₄haloalkyl, Ci_ ₄alkoxy, carboxy, Ci_ ₄alkoxycarbonyl or R and R ² together form an oxo group or R together with one of R ³ or R ⁵ forms a bond or R and R ⁵ together form a C ₂. ₅alkylene chain.

In particularly preferred embodiments of the invention, the preferred groups for A, W, X, Z, m, n, p, R, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁸, R ⁹, R ⁰, R ¹¹, R ², R ²⁰, R ² , R ²² and R ²⁴, in any combination thereof, are as set out below.

In one embodiment, A is a 5-membered heteroaromatic ring containing 1 to 4 heteroatoms selected from oxygen, sulphur and nitrogen, with the proviso that A is not

Preferably, the 5-membered ring is a pyrrole, furan, thiophene (other than the thiophene above), pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, 1 ,2,3-triazole, 1 ,2,4-triazole, 1 ,2,3- oxadiazole, 1 ,2,5-oxadiazole, 1 ,2,3-thiadiazole, 1 ,2,5-thiadiazole or tetrazole ring. More preferably, the 5-membered ring is a thiophene (other than the thiophene above), pyrazole, thiazole, 1 ,2,4-triazole or tetrazole ring. Most preferably, the 5-membered ring is a thiophene ring (other than the thiophene above).

In another embodiment, A is a 6-membered heteroaromatic ring containing 1 to 3 nitrogen atoms. Preferably, the 6-membered ring is a pyridine, pyridazine, pyrimidine, pyrazine, 1 ,2,3-triazine or 1 ,2,4- triazine ring. More preferably, the 6-membered ring is a pyridazine, pyrimidine or pyrazine ring. Most preferably, the 6-membered ring is a pyrimidine ring.

Preferably, W is oxygen. Preferably, X is oxygen or CR ³R ⁴. Preferably, Z is oxygen, CR ⁸R ⁹ or NR ⁰.

Preferably, m is 0 or 1. Most preferably, m is 0.

Preferably, n is 0, 1 or 2 and p is 0, 1 or 2 with the proviso that 1 < n + p < 2. In one embodiment, R is Ci-C ₆ alkyl.

In another embodiment, R is d- ₄haloalkyl. More preferably, R is trifluoromethyl.

Preferably, R is H,

arylCi- ₂alkyl optionally substituted by 1-3 groups R ²⁰, arylCi- ₂alkoxyCi- ₂alkyl optionally substituted by 1-3 groups R ²⁰, C-i^alkylcarbonyloxyC-i^alkyl, arylcarbonyloxyCi_ ₂alkyl optionally substituted by 1-3 groups R ²⁰, Ci- ₄alkoxycarbonyloxyCi- ₂alkyl, Ci_ ₈alkylcarbonyl, Ci_ ₄haloalkylcarbonyl,

Ci-i ₀alkoxycarbonyl, Ci_ ₄haloalkoxycarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R ²⁰, arylCi_ ₂alkoxycarbonyl optionally substituted by 1-3 groups R ²⁰, Ci_ ₆alkylsulphonyl or Ci_ ₆haloalkylsulphonyl, and each R ²⁰ is, independently, halogen, C ₁_ ₄alkyl, C-|. ₄haloalkyl, Ci_ ₄alkoxy or Ci_ ₄haloalkoxy. More preferably, R is H, Ci_ ₅alkylcarbonyl, Ci_ ₄haloalkylcarbonyl, Ci_ ₅alkoxycarbonyl, Ci_ ₄haloalkoxycarbonyl or Ci_ ₄haloalkylsulphonyl. Most preferably, R is H, d- ₅alkylcarbonyl or Ci_ ₅alkoxycarbonyl.

Preferably, R ² is halogen, C ₁_ ₄alkyl, C-|. ₄haloalkyl, Ci_ ₄alkoxy or Ci_ ₄alkylsulphonyl. Most preferably, R ² is halogen or methyl.

Preferably, R ³ and R ⁴ are, independently, H, halogen or C ₁_ ₄alkyl. Most preferably, R ³ and R ⁴ are, independently, H or methyl.

Preferably, R ⁵ and R ⁶ are, independently, H, Ci_ ₅alkyl, Ci_ ₄haloalkyl, C ₃. ₆cycloalkyl, Ci. ₄alkoxyCi_ ₄alkyl, arylCi_ ₂alkyl optionally substituted by 1-3 groups R ² , C ₂- ₄alkenyl, Ci_ ₄alkoxy, Ci_ ₄alkylthio, aryl optionally substituted by 1-3 groups R ² , aryloxy optionally substituted by 1-3 groups R ² , arylthio optionally substituted by 1-3 groups R ² , heteroaryl optionally substituted by 1-3 groups R ² or R ⁵ and R ⁶ together form a C ₂- ₅alkylene chain optionally containing an oxygen atom, and each R ² is, independently, halogen, cyano, C ₁_ ₄alkyl, C-|. ₄haloalkyl, Ci_ ₄alkoxy or Ci. ₄haloalkoxy. More preferably, R ⁵ and R ⁶ are, independently, H, d_ ₄alkyl, C-|. ₃haloalkyl, cyclopropyl, Ci_ ₃alkoxy, Ci_ ₃alkylthio, aryl optionally substituted by 1-3 groups R ² , aryloxy optionally substituted by 1-3 groups R ² , arylthio optionally substituted by 1-3 groups R ² , heteroaryl optionally substituted by 1-3 groups R ² or R ⁵ and R ⁶ together form a C ₃. ₅alkylene chain, and each R ² is, independently, halogen, cyano, d_ ₄alkyl, C-|. ₄haloalkyl, Ci_ ₄alkoxy or d- ₄haloalkoxy Most preferably, R ⁵ and R ⁶ are, independently, H, Ci_ ₃alkyl, trifluoromethyl, cyclopropyl, Ci_ ₃alkoxy, aryl optionally substituted by 1-2 groups R ² or R ⁵ and R ⁶ together form a C ₃. ₅alkylene chain, and each R ² is, independently, halogen, methyl or methoxy.

Preferably, R ⁸ and R ⁹ are, independently, H, halogen, d_ ₄alkyl, d. ₄haloalkyl, Ci_ ₄alkoxy, d- ₄alkylthio, aryl optionally substituted by 1-3 groups R ²⁴, aryloxy optionally substituted by 1-3 groups R ²⁴ or arylthio optionally substituted by 1-3 groups R ²⁴, and each R ²⁴ is, independently, halogen, cyano, d_ ₄alkyl, d- ₄haloalkyl, Ci_ ₄alkoxy or d. ₄haloalkoxy. More preferably, R ⁸ and R ⁹ are, independently, H, halogen, Ci- ₄alkyl, Ci_ ₄haloalkyl, d- ₄alkoxy, Ci_ ₄alkylthio, aryl optionally substituted by 1-2 groups R , and each R ²⁴ is, independently, halogen, methyl or methoxy. Most preferably, R ⁸ and R ⁹ are, independently, H, halogen, Ci_ ₃alkyl, Ci_ ₃alkoxy or Ci_ ₃alkylthio.

Preferably, R ⁰ is H, C ₁_ ₄alkyl, aryl optionally substituted by 1-3 groups R ²², heteroaryl optionally substituted by 1-3 groups R ²², Ci_ ₄alkylcarbonyl, Ci_ ₄alkoxycarbonyl, Ci_ ₄alkylsulphonyl or Ci_

4haloalkylsulphonyl, and each R ²² is, independently, halogen, cyano, C ₁_ ₄alkyl, C-|. ₄haloalkyl, Ci_ ₄alkoxy, Ci_ ₄haloalkoxy or Ci_ ₄alkylsulphonyl. Most preferably, R ⁰ is H, Ci_ ₃alkyl or aryl optionally substituted by 1-3 groups R ²², and each R ²² is, independently, halogen, methyl or methoxy.

Preferably, R and R ² are, independently, H, hydroxy, C ₁_ ₄alkyl, C-|. ₄alkoxy, carboxy, Ci_

4alkoxycarbonyl or R and R ² together form an oxo group. Most preferably, R and R ² are each H.

The compounds described below are illustrative of compounds of the invention. In the tables the different values of rin A are as follows:

A1 A2 A3 A4 A5 A6

A7 A8 A9 A10 A1 1 A12

A13 A14 A15 A16 A17 A18

A19 A20 A21 A22 A23 A24

A25 A26 A27 A28 A29 A30

A31 A32 A33 A34 A35 A36

A37 A38 A39 A40 A41 A42

A43 A44 A45 A46 A47 A48

A49 A50 A51 A52 A53 A54

A55 A56 A57 A58 A59 A60

A61 A62 A63 A64 A65

Table 1 below provides 801 compounds designated compounds 1-1 to 1-801 respectively, of formula (I), wherein ring A is A1.

TABLE 1

Cpd

No R R ¹ W (CR ¹¹R ¹²) _n X (CR ⁵R ⁶) _P Z

1 Me H 0 CH ₂ CH ₂ CH ₂

2 Me COEt 0 CH ₂ CH ₂ CH ₂

3 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂

4 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂

5 CF ₃ H 0 CH ₂ CH ₂ CH ₂

6 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂

7 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂

8 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂

9 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂

10 Me H 0 CH ₂ CHMe CH ₂

11 Me COEt 0 CH ₂ CHMe CH ₂

12 Me C0 ₂Et 0 CH ₂ CHMe CH ₂

13 Me S0 ₂Me 0 CH ₂ CHMe CH ₂

14 CF ₃ H 0 CH ₂ CHMe CH ₂

15 CF ₃ COEt 0 CH ₂ CHMe CH ₂

16 CF ₃ C0 ₂Et 0 CH ₂ CHMe CH ₂ CF ₃ S0 ₂CF ₃ 0 CH ₂ CHMe CH ₂

CF ₃ S0 ₂Me 0 CH ₂ CHMe CH ₂

Me H 0 CH ₂ CMe ₂ CH ₂

Me COEt 0 CH ₂ CMe ₂ CH ₂

Me C0 ₂Et 0 CH ₂ CMe ₂ CH ₂

Me S0 ₂Me 0 CH ₂ CMe ₂ CH ₂

CF ₃ H 0 CH ₂ CMe ₂ CH ₂

CF ₃ COEt 0 CH ₂ CMe ₂ CH ₂

CF ₃ C0 ₂Et 0 CH ₂ CMe ₂ CH ₂

CF ₃ S0 ₂CF ₃ 0 CH ₂ CMe ₂ CH ₂

CF ₃ S0 ₂Me 0 CH ₂ CMe ₂ CH ₂

Me H 0 CH ₂ CHPh CH ₂

Me COEt 0 CH ₂ CHPh CH ₂

Me C0 ₂Et 0 CH ₂ CHPh CH ₂

Me S0 ₂Me 0 CH ₂ CHPh CH ₂

CF ₃ H 0 CH ₂ CHPh CH ₂

CF ₃ COEt 0 CH ₂ CHPh CH ₂

CF ₃ C0 ₂Et 0 CH ₂ CHPh CH ₂

CF ₃ S0 ₂CF ₃ 0 CH ₂ CHPh CH ₂

CF ₃ S0 ₂Me 0 CH ₂ CHPh CH ₂

Me H 0 CHMe CH ₂ CH ₂

Me COEt 0 CHMe CH ₂ CH ₂

Me C0 ₂Et 0 CHMe CH ₂ CH ₂

Me S0 ₂Me 0 CHMe CH ₂ CH ₂

CF ₃ H 0 CHMe CH ₂ CH ₂

CF ₃ COEt 0 CHMe CH ₂ CH ₂

CF ₃ C0 ₂Et 0 CHMe CH ₂ CH ₂

CF ₃ S0 ₂CF ₃ 0 CHMe CH ₂ CH ₂

CF ₃ S0 ₂Me 0 CHMe CH ₂ CH ₂

Me H 0 CMe ₂ CH ₂ CH ₂

Me COEt 0 CMe ₂ CH ₂ CH ₂

Me C0 ₂Et 0 CMe ₂ CH ₂ CH ₂

Me S0 ₂Me 0 CMe ₂ CH ₂ CH ₂

CF ₃ H 0 CMe ₂ CH ₂ CH ₂

CF ₃ COEt 0 CMe ₂ CH ₂ CH ₂ CF ₃ C0 ₂Et 0 CMe ₂ CH ₂ CH ₂

CF ₃ S0 ₂CF ₃ 0 CMe ₂ CH ₂ CH ₂

CF ₃ S0 ₂Me 0 CMe ₂ CH ₂ CH ₂

Me H 0 CH ₂ CH ₂ CH ₂ CH ₂

Me COEt 0 CH ₂ CH ₂ CH ₂ CH ₂

Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CH ₂

Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CH ₂

CF ₃ H 0 CH ₂ CH ₂ CH ₂ CH ₂

CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ CH ₂

CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CH ₂

CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ CH ₂

CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CH ₂

Me H 0 CH ₂ CH ₂ CHMe CH ₂

Me COEt 0 CH ₂ CH ₂ CHMe CH ₂

Me C0 ₂Et 0 CH ₂ CH ₂ CHMe CH ₂

Me S0 ₂Me 0 CH ₂ CH ₂ CHMe CH ₂

CF ₃ H 0 CH ₂ CH ₂ CHMe CH ₂

CF ₃ COEt 0 CH ₂ CH ₂ CHMe CH ₂

CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CHMe CH ₂

CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CHMe CH ₂

CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CHMe CH ₂

Me H 0 CH ₂ CH ₂ CMe ₂ CH ₂

Me COEt 0 CH ₂ CH ₂ CMe ₂ CH ₂

Me C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ CH ₂

Me S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ CH ₂

CF ₃ H 0 CH ₂ CH ₂ CMe ₂ CH ₂

CF ₃ COEt 0 CH ₂ CH ₂ CMe ₂ CH ₂

CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ CH ₂

CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CMe ₂ CH ₂

CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ CH ₂

Me H 0 CH ₂ CH ₂ C(Me)(Et) CH ₂

Me COEt 0 CH ₂ CH ₂ C(Me)(Et) CH ₂

Me C0 ₂Et 0 CH ₂ CH ₂ C(Me)(Et) CH ₂

Me S0 ₂Me 0 CH ₂ CH ₂ C(Me)(Et) CH ₂

CF ₃ H 0 CH ₂ CH ₂ C(Me)(Et) CH ₂ 87 CF ₃ COEt 0 CH ₂ CH ₂ C(Me)(Et) CH ₂

88 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ C(Me)(Et) CH ₂

89 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ C(Me)(Et) CH ₂

90 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ C(Me)(Et) CH ₂

91 Me H 0 CH ₂ CH ₂ CH ₂ CHSMe

92 Me COEt 0 CH ₂ CH ₂ CH ₂ CHSMe

93 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CHSMe

94 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CHSMe

95 CF ₃ H 0 CH ₂ CH ₂ CH ₂ CHSMe

96 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ CHSMe

97 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CHSMe

98 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ CHSMe

99 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CHSMe

100 Me H 0 CHMe CH ₂ CH ₂ CH ₂

101 Me COEt 0 CHMe CH ₂ CH ₂ CH ₂

102 Me C0 ₂Et 0 CHMe CH ₂ CH ₂ CH ₂

103 Me S0 ₂Me 0 CHMe CH ₂ CH ₂ CH ₂

104 CF ₃ H 0 CHMe CH ₂ CH ₂ CH ₂

105 CF ₃ COEt 0 CHMe CH ₂ CH ₂ CH ₂

106 CF ₃ C0 ₂Et 0 CHMe CH ₂ CH ₂ CH ₂

107 CF ₃ S0 ₂CF ₃ 0 CHMe CH ₂ CH ₂ CH ₂

108 CF ₃ S0 ₂Me 0 CHMe CH ₂ CH ₂ CH ₂

109 Me H 0 CHMe CH ₂ CMe ₂ CH ₂

110 Me COEt 0 CHMe CH ₂ CMe ₂ CH ₂

111 Me C0 ₂Et 0 CHMe CH ₂ CMe ₂ CH ₂

112 Me S0 ₂Me 0 CHMe CH ₂ CMe ₂ CH ₂

113 CF ₃ H 0 CHMe CH ₂ CMe ₂ CH ₂

114 CF ₃ COEt 0 CHMe CH ₂ CMe ₂ CH ₂

115 CF ₃ C0 ₂Et 0 CHMe CH ₂ CMe ₂ CH ₂

116 CF ₃ S0 ₂CF ₃ 0 CHMe CH ₂ CMe ₂ CH ₂

117 CF ₃ S0 ₂Me 0 CHMe CH ₂ CMe ₂ CH ₂

118 Me H 0 CMe ₂ CH ₂ CH ₂ CH ₂

119 Me COEt 0 CMe ₂ CH ₂ CH ₂ CH ₂

120 Me C0 ₂Et 0 CMe ₂ CH ₂ CH ₂ CH ₂

121 Me S0 ₂Me 0 CMe ₂ CH ₂ CH ₂ CH ₂ 122 CF ₃ H 0 CMe ₂ CH ₂ CH ₂ CH ₂

123 CF ₃ COEt 0 CMe ₂ CH ₂ CH ₂ CH ₂

124 CF ₃ C0 ₂Et 0 CMe ₂ CH ₂ CH ₂ CH ₂

125 CF ₃ S0 ₂CF ₃ 0 CMe ₂ CH ₂ CH ₂ CH ₂

126 CF ₃ S0 ₂Me 0 CMe ₂ CH ₂ CH ₂ CH ₂

127 Me H 0 CMe ₂ CH ₂ CHMe CH ₂

128 Me COEt 0 CMe ₂ CH ₂ CHMe CH ₂

129 Me C0 ₂Et 0 CMe ₂ CH ₂ CHMe CH ₂

130 Me S0 ₂Me 0 CMe ₂ CH ₂ CHMe CH ₂

131 CF ₃ H 0 CMe ₂ CH ₂ CHMe CH ₂

132 CF ₃ COEt 0 CMe ₂ CH ₂ CHMe CH ₂

133 CF ₃ C0 ₂Et 0 CMe ₂ CH ₂ CHMe CH ₂

134 CF ₃ S0 ₂CF ₃ 0 CMe ₂ CH ₂ CHMe CH ₂

135 CF ₃ S0 ₂Me 0 CMe ₂ CH ₂ CHMe CH ₂

136 Me H 0 CH ₂ CH ₂ CHEt CH ₂

137 Me COEt 0 CH ₂ CH ₂ CHEt CH ₂

138 Me C0 ₂Et 0 CH ₂ CH ₂ CHEt CH ₂

139 Me S0 ₂Me 0 CH ₂ CH ₂ CHEt CH ₂

140 CF ₃ H 0 CH ₂ CH ₂ CHEt CH ₂

141 CF ₃ COEt 0 CH ₂ CH ₂ CHEt CH ₂

142 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CHEt CH ₂

143 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CHEt CH ₂

144 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CHEt CH ₂

145 Me H 0 CH ₂ CH ₂ CH ⁿPr CH ₂

146 Me COEt 0 CH ₂ CH ₂ CH ⁿPr CH ₂

147 Me C0 ₂Et 0 CH ₂ CH ₂ CH ⁿPr CH ₂

148 Me S0 ₂Me 0 CH ₂ CH ₂ CH ⁿPr CH ₂

149 CF ₃ H 0 CH ₂ CH ₂ CH ⁿPr CH ₂

150 CF ₃ COEt 0 CH ₂ CH ₂ CH ⁿPr CH ₂

151 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ⁿPr CH ₂

152 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ⁿPr CH ₂

153 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ⁿPr CH ₂

154 Me H 0 CH ₂ CH ₂ CH ^cPr CH ₂

155 Me COEt 0 CH ₂ CH ₂ CH ^cPr CH ₂

156 Me C0 ₂Et 0 CH ₂ CH ₂ CH ^cPr CH ₂ 157 Me S0 ₂Me 0 CH ₂ CH ₂ CH ^cPr CH ₂

158 CF ₃ H 0 CH ₂ CH ₂ CH ^cPr CH ₂

159 CF ₃ COEt 0 CH ₂ CH ₂ CH ^cPr CH ₂

160 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ^cPr CH ₂

161 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ^cPr CH ₂

162 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ^cPr CH ₂

163 Me H 0 CH ₂ CH ₂ C(CH ₂) ₄ CH ₂

164 Me COEt 0 CH ₂ CH ₂ C(CH ₂) ₄ CH ₂

165 Me C0 ₂Et 0 CH ₂ CH ₂ C(CH ₂) ₄ CH ₂

166 Me S0 ₂Me 0 CH ₂ CH ₂ C(CH ₂) ₄ CH ₂

167 CF ₃ H 0 CH ₂ CH ₂ C(CH ₂) ₄ CH ₂

168 CF ₃ COEt 0 CH ₂ CH ₂ C(CH ₂) ₄ CH ₂

169 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ C(CH ₂) ₄ CH ₂

170 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ C(CH ₂) ₄ CH ₂

171 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ C(CH ₂) ₄ CH ₂

172 Me H 0 CHMe CH ₂ CHMe CH ₂

173 Me COEt 0 CHMe CH ₂ CHMe CH ₂

174 Me C0 ₂Et 0 CHMe CH ₂ CHMe CH ₂

175 Me S0 ₂Me 0 CHMe CH ₂ CHMe CH ₂

176 CF ₃ H 0 CHMe CH ₂ CHMe CH ₂

177 CF ₃ COEt 0 CHMe CH ₂ CHMe CH ₂

178 CF ₃ C0 ₂Et 0 CHMe CH ₂ CHMe CH ₂

179 CF ₃ S0 ₂CF ₃ 0 CHMe CH ₂ CHMe CH ₂

180 CF ₃ S0 ₂Me 0 CHMe CH ₂ CHMe CH ₂

181 Me H 0 CH ₂ CHMe CH ₂ CH ₂

182 Me COEt 0 CH ₂ CHMe CH ₂ CH ₂

183 Me C0 ₂Et 0 CH ₂ CHMe CH ₂ CH ₂

184 Me S0 ₂Me 0 CH ₂ CHMe CH ₂ CH ₂

185 CF ₃ H 0 CH ₂ CHMe CH ₂ CH ₂

186 CF ₃ COEt 0 CH ₂ CHMe CH ₂ CH ₂

187 CF ₃ C0 ₂Et 0 CH ₂ CHMe CH ₂ CH ₂

188 CF ₃ S0 ₂CF ₃ 0 CH ₂ CHMe CH ₂ CH ₂

189 CF ₃ S0 ₂Me 0 CH ₂ CHMe CH ₂ CH ₂

190 Me H 0 CH ₂ CHEt CH ₂ CH ₂

191 Me COEt 0 CH ₂ CHEt CH ₂ CH ₂ 192 Me C0 ₂Et 0 CH ₂ CHEt CH ₂ CH ₂

193 Me S0 ₂Me 0 CH ₂ CHEt CH ₂ CH ₂

194 CF ₃ H 0 CH ₂ CHEt CH ₂ CH ₂

195 CF ₃ COEt 0 CH ₂ CHEt CH ₂ CH ₂

196 CF ₃ C0 ₂Et 0 CH ₂ CHEt CH ₂ CH ₂

197 CF ₃ S0 ₂CF ₃ 0 CH ₂ CHEt CH ₂ CH ₂

198 CF ₃ S0 ₂Me 0 CH ₂ CHEt CH ₂ CH ₂

199 Me H 0 CH ₂ CMe ₂ CH ₂ CH ₂

200 Me COEt 0 CH ₂ CMe ₂ CH ₂ CH ₂

201 Me C0 ₂Et 0 CH ₂ CMe ₂ CH ₂ CH ₂

202 Me S0 ₂Me 0 CH ₂ CMe ₂ CH ₂ CH ₂

203 CF ₃ H 0 CH ₂ CMe ₂ CH ₂ CH ₂

204 CF ₃ COEt 0 CH ₂ CMe ₂ CH ₂ CH ₂

205 CF ₃ C0 ₂Et 0 CH ₂ CMe ₂ CH ₂ CH ₂

206 CF ₃ S0 ₂CF ₃ 0 CH ₂ CMe ₂ CH ₂ CH ₂

207 CF ₃ S0 ₂Me 0 CH ₂ CMe ₂ CH ₂ CH ₂

208 Me H 0 CH ₂ CMe ₂ CH ₂ CHMe

209 Me COEt 0 CH ₂ CMe ₂ CH ₂ CHMe

210 Me C0 ₂Et 0 CH ₂ CMe ₂ CH ₂ CHMe

211 Me S0 ₂Me 0 CH ₂ CMe ₂ CH ₂ CHMe

212 CF ₃ H 0 CH ₂ CMe ₂ CH ₂ CHMe

213 CF ₃ COEt 0 CH ₂ CMe ₂ CH ₂ CHMe

214 CF ₃ C0 ₂Et 0 CH ₂ CMe ₂ CH ₂ CHMe

215 CF ₃ S0 ₂CF ₃ 0 CH ₂ CMe ₂ CH ₂ CHMe

216 CF ₃ S0 ₂Me 0 CH ₂ CMe ₂ CH ₂ CHMe

217 Me H 0 CH ₂ CH ₂ CH ₂ CHMe

218 Me COEt 0 CH ₂ CH ₂ CH ₂ CHMe

219 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CHMe

220 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CHMe

221 CF ₃ H 0 CH ₂ CH ₂ CH ₂ CHMe

222 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ CHMe

223 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CHMe

224 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ CHMe

225 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CHMe

226 Me H 0 CH ₂ CH ₂ CH ₂ CMe ₂ 227 Me COEt 0 CH ₂ CH ₂ CH ₂ CMe ₂

228 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CMe ₂

229 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CMe ₂

230 CF ₃ H 0 CH ₂ CH ₂ CH ₂ CMe ₂

231 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ CMe ₂

232 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CMe ₂

233 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ CMe ₂

234 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CMe ₂

235 Me H 0 CH ₂ CHMe CH ₂ CMe ₂

236 Me COEt 0 CH ₂ CHMe CH ₂ CMe ₂

237 Me C0 ₂Et 0 CH ₂ CHMe CH ₂ CMe ₂

238 Me S0 ₂Me 0 CH ₂ CHMe CH ₂ CMe ₂

239 CF ₃ H 0 CH ₂ CHMe CH ₂ CMe ₂

240 CF ₃ COEt 0 CH ₂ CHMe CH ₂ CMe ₂

241 CF ₃ C0 ₂Et 0 CH ₂ CHMe CH ₂ CMe ₂

242 CF ₃ S0 ₂CF ₃ 0 CH ₂ CHMe CH ₂ CMe ₂

243 CF ₃ S0 ₂Me 0 CH ₂ CHMe CH ₂ CMe ₂

244 Me H 0 CH ₂ CH ₂ CH ₂ CHEt

245 Me COEt 0 CH ₂ CH ₂ CH ₂ CHEt

246 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CHEt

247 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CHEt

248 CF ₃ H 0 CH ₂ CH ₂ CH ₂ CHEt

249 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ CHEt

250 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CHEt

251 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ CHEt

252 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CHEt

253 Me H 0 CH ₂ CH ₂ CHPh CH ₂

254 Me COEt 0 CH ₂ CH ₂ CHPh CH ₂

255 Me C0 ₂Et 0 CH ₂ CH ₂ CHPh CH ₂

256 Me S0 ₂Me 0 CH ₂ CH ₂ CHPh CH ₂

257 CF ₃ H 0 CH ₂ CH ₂ CHPh CH ₂

258 CF ₃ COEt 0 CH ₂ CH ₂ CHPh CH ₂

259 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CHPh CH ₂

260 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CHPh CH ₂

261 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CHPh CH ₂ 262 Me H 0 CH ₂ CH ₂ CH ₂ CHPh

263 Me COEt 0 CH ₂ CH ₂ CH ₂ CHPh

264 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CHPh

265 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CHPh

266 CF ₃ H 0 CH ₂ CH ₂ CH ₂ CHPh

267 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ CHPh

268 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ CHPh

269 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ CHPh

270 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ CHPh

271 Me H 0 CH ₂CH ₂ CH ₂ CH ₂ CH ₂

272 Me COEt 0 CH ₂CH ₂ CH ₂ CH ₂ CH ₂

273 Me C0 ₂Et 0 CH ₂CH ₂ CH ₂ CH ₂ CH ₂

274 Me S0 ₂Me 0 CH ₂CH ₂ CH ₂ CH ₂ CH ₂

275 CF ₃ H 0 CH ₂CH ₂ CH ₂ CH ₂ CH ₂

276 CF ₃ COEt 0 CH ₂CH ₂ CH ₂ CH ₂ CH ₂

277 CF ₃ C0 ₂Et 0 CH ₂CH ₂ CH ₂ CH ₂ CH ₂

278 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ CH ₂ CH ₂ CH ₂

279 CF ₃ S0 ₂Me 0 CH ₂CH ₂ CH ₂ CH ₂ CH ₂

280 Me H 0 CH ₂CH ₂ CH ₂ CHMe CH ₂

281 Me COEt 0 CH ₂CH ₂ CH ₂ CHMe CH ₂

282 Me C0 ₂Et 0 CH ₂CH ₂ CH ₂ CHMe CH ₂

283 Me S0 ₂Me 0 CH ₂CH ₂ CH ₂ CHMe CH ₂

284 CF ₃ H 0 CH ₂CH ₂ CH ₂ CHMe CH ₂

285 CF ₃ COEt 0 CH ₂CH ₂ CH ₂ CHMe CH ₂

286 CF ₃ C0 ₂Et 0 CH ₂CH ₂ CH ₂ CHMe CH ₂

287 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ CH ₂ CHMe CH ₂

288 CF ₃ S0 ₂Me 0 CH ₂CH ₂ CH ₂ CHMe CH ₂

289 Me H 0 CH ₂CH ₂ CHMe CH ₂ CH ₂

290 Me COEt 0 CH ₂CH ₂ CHMe CH ₂ CH ₂

291 Me C0 ₂Et 0 CH ₂CH ₂ CHMe CH ₂ CH ₂

292 Me S0 ₂Me 0 CH ₂CH ₂ CHMe CH ₂ CH ₂

293 CF ₃ H 0 CH ₂CH ₂ CHMe CH ₂ CH ₂

294 CF ₃ COEt 0 CH ₂CH ₂ CHMe CH ₂ CH ₂

295 CF ₃ C0 ₂Et 0 CH ₂CH ₂ CHMe CH ₂ CH ₂

296 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ CHMe CH ₂ CH ₂ 297 CF ₃ S0 ₂Me 0 CH ₂CH ₂ CHMe CH ₂ CH ₂

298 Me H 0 CH ₂CH ₂ CMe ₂ CH ₂ CH ₂

299 Me COEt 0 CH ₂CH ₂ CMe ₂ CH ₂ CH ₂

300 Me C0 ₂Et 0 CH ₂CH ₂ CMe ₂ CH ₂ CH ₂

301 Me S0 ₂Me 0 CH ₂CH ₂ CMe ₂ CH ₂ CH ₂

302 CF ₃ H 0 CH ₂CH ₂ CMe ₂ CH ₂ CH ₂

303 CF ₃ COEt 0 CH ₂CH ₂ CMe ₂ CH ₂ CH ₂

304 CF ₃ C0 ₂Et 0 CH ₂CH ₂ CMe ₂ CH ₂ CH ₂

305 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ CMe ₂ CH ₂ CH ₂

306 CF ₃ S0 ₂Me 0 CH ₂CH ₂ CMe ₂ CH ₂ CH ₂

307 Me H 0 CH ₂ CH ₂ N(2,6-dichlorophenyl)

308 Me COEt 0 CH ₂ CH ₂ N(2,6-dichlorophenyl)

309 Me C0 ₂Et 0 CH ₂ CH ₂ N(2,6-dichlorophenyl)

310 Me S0 ₂Me 0 CH ₂ CH ₂ N(2,6-dichlorophenyl)

311 CF ₃ H 0 CH ₂ CH ₂ N(2,6-dichlorophenyl)

312 CF ₃ COEt 0 CH ₂ CH ₂ N(2,6-dichlorophenyl)

313 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ N(2,6-dichlorophenyl)

314 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ N(2,6-dichlorophenyl)

315 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ N(2,6-dichlorophenyl)

316 Me H 0 CH ₂ CH ₂ CH ₂ NH

317 Me COEt 0 CH ₂ CH ₂ CH ₂ NH

318 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ NH

319 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ NH

320 CF ₃ H 0 CH ₂ CH ₂ CH ₂ NH

321 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ NH

322 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ NH

323 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ NH

324 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ NH

325 Me H 0 CH ₂ CH ₂ CH ₂ NMe

326 Me COEt 0 CH ₂ CH ₂ CH ₂ NMe

327 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ NMe

328 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ NMe

329 CF ₃ H 0 CH ₂ CH ₂ CH ₂ NMe

330 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ NMe

331 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ NMe 332 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ NMe

333 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ NMe

334 Me H 0 CH ₂ CH ₂ CH ₂ NC0 ₂Et

335 Me COEt 0 CH ₂ CH ₂ CH ₂ NC0 ₂Et

336 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ NC0 ₂Et

337 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ NC0 ₂Et

338 CF ₃ H 0 CH ₂ CH ₂ CH ₂ NC0 ₂Et

339 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ NC0 ₂Et

340 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ NC0 ₂Et

341 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ NC0 ₂Et

342 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ NC0 ₂Et

343 Me H 0 CH ₂ CH ₂ CMe ₂ NH

344 Me COEt 0 CH ₂ CH ₂ CMe ₂ NH

345 Me C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ NH

346 Me S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ NH

347 CF ₃ H 0 CH ₂ CH ₂ CMe ₂ NH

348 CF ₃ COEt 0 CH ₂ CH ₂ CMe ₂ NH

349 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ NH

350 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CMe ₂ NH

351 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ NH

352 Me H 0 CH ₂ CH ₂ CMe ₂ NMe

353 Me COEt 0 CH ₂ CH ₂ CMe ₂ NMe

354 Me C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ NMe

355 Me S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ NMe

356 CF ₃ H 0 CH ₂ CH ₂ CMe ₂ NMe

357 CF ₃ COEt 0 CH ₂ CH ₂ CMe ₂ NMe

358 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ NMe

359 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CMe ₂ NMe

360 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ NMe

361 Me H 0 CH ₂ CH ₂ CMe ₂ NC0 ₂Et

362 Me COEt 0 CH ₂ CH ₂ CMe ₂ NC0 ₂Et

363 Me C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ NC0 ₂Et

364 Me S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ NC0 ₂Et

365 CF ₃ H 0 CH ₂ CH ₂ CMe ₂ NC0 ₂Et

366 CF ₃ COEt 0 CH ₂ CH ₂ CMe ₂ NC0 ₂Et 367 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ NC0 ₂Et

368 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CMe ₂ NC0 ₂Et

369 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ NC0 ₂Et

370 Me H 0 CH ₂CH ₂ CH ₂ CH ₂ NH

371 Me COEt 0 CH ₂CH ₂ CH ₂ CH ₂ NH

372 Me C0 ₂Et 0 CH ₂CH ₂ CH ₂ CH ₂ NH

373 Me S0 ₂Me 0 CH ₂CH ₂ CH ₂ CH ₂ NH

374 CF ₃ H 0 CH ₂CH ₂ CH ₂ CH ₂ NH

375 CF ₃ COEt 0 CH ₂CH ₂ CH ₂ CH ₂ NH

376 CF ₃ C0 ₂Et 0 CH ₂CH ₂ CH ₂ CH ₂ NH

377 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ CH ₂ CH ₂ NH

378 CF ₃ S0 ₂Me 0 CH ₂CH ₂ CH ₂ CH ₂ NH

379 Me H 0 CH ₂ 0 CH ₂ NMe

380 Me COEt 0 CH ₂ 0 CH ₂ NMe

381 Me C0 ₂Et 0 CH ₂ 0 CH ₂ NMe

382 Me S0 ₂Me 0 CH ₂ 0 CH ₂ NMe

383 CF ₃ H 0 CH ₂ 0 CH ₂ NMe

384 CF ₃ COEt 0 CH ₂ 0 CH ₂ NMe

385 CF ₃ C0 ₂Et 0 CH ₂ 0 CH ₂ NMe

386 CF ₃ S0 ₂CF ₃ 0 CH ₂ 0 CH ₂ NMe

387 CF ₃ S0 ₂Me 0 CH ₂ 0 CH ₂ NMe

388 Me H 0 CH ₂ CH ₂ 0

389 Me COEt 0 CH ₂ CH ₂ 0

390 Me C0 ₂Et 0 CH ₂ CH ₂ 0

391 Me S0 ₂Me 0 CH ₂ CH ₂ 0

392 CF ₃ H 0 CH ₂ CH ₂ 0

393 CF ₃ COEt 0 CH ₂ CH ₂ 0

394 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ 0

395 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ 0

396 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ 0

397 Me H 0 CH ₂ CMe ₂ 0

398 Me COEt 0 CH ₂ CMe ₂ 0

399 Me C0 ₂Et 0 CH ₂ CMe ₂ 0

400 Me S0 ₂Me 0 CH ₂ CMe ₂ 0

401 CF ₃ H 0 CH ₂ CMe ₂ 0 402 CF ₃ COEt 0 CH ₂ CMe ₂ 0

403 CF ₃ C0 ₂Et 0 CH ₂ CMe ₂ 0

404 CF ₃ S0 ₂CF ₃ 0 CH ₂ CMe ₂ 0

405 CF ₃ S0 ₂Me 0 CH ₂ CMe ₂ 0

406 Me H 0 CH ₂ C(Me)( ^cPr) 0

407 Me COEt 0 CH ₂ C(Me)( ^cPr) 0

408 Me C0 ₂Et 0 CH ₂ C(Me)( ^cPr) 0

409 Me S0 ₂Me 0 CH ₂ C(Me)( ^cPr) 0

410 CF ₃ H 0 CH ₂ C(Me)( ^cPr) 0

411 CF ₃ COEt 0 CH ₂ C(Me)( ^cPr) 0

412 CF ₃ C0 ₂Et 0 CH ₂ C(Me)( ^cPr) 0

413 CF ₃ S0 ₂CF ₃ 0 CH ₂ C(Me)( ^cPr) 0

414 CF ₃ S0 ₂Me 0 CH ₂ C(Me)( ^cPr) 0

415 Me H 0 CH ₂ C(Me)( CF ₃) 0

416 Me COEt 0 CH ₂ C(Me)( CF ₃) 0

417 Me C0 ₂Et 0 CH ₂ C(Me)( CF ₃) 0

418 Me S0 ₂Me 0 CH ₂ C(Me)( CF ₃) 0

419 CF ₃ H 0 CH ₂ C(Me)( CF ₃) 0

420 CF ₃ COEt 0 CH ₂ C(Me)( CF ₃) 0

421 CF ₃ C0 ₂Et 0 CH ₂ C(Me)( CF ₃) 0

422 CF ₃ S0 ₂CF ₃ 0 CH ₂ C(Me)( CF ₃) 0

423 CF ₃ S0 ₂Me 0 CH ₂ C(Me)( CF ₃) 0

C(Me)(2-

424 Me H 0 CH ₂ fluorophenyl) 0

C(Me)(2-

425 Me COEt 0 CH ₂ fluorophenyl) 0

C(Me)(2-

426 Me C0 ₂Et 0 CH ₂ fluorophenyl) 0

C(Me)(2-

427 Me S0 ₂Me 0 CH ₂ fluorophenyl) 0

C(Me)(2-

428 CF ₃ H 0 CH ₂ fluorophenyl) 0

C(Me)(2-

429 CF ₃ COEt 0 CH ₂ fluorophenyl) 0

C(Me)(2-

430 CF ₃ C0 ₂Et 0 CH ₂ fluorophenyl) 0

C(Me)(2-

431 CF ₃ S0 ₂CF ₃ 0 CH ₂ fluorophenyl) 0

C(Me)(2-

432 CF ₃ S0 ₂Me 0 CH ₂ fluorophenyl) 0

433 Me H 0 CMe ₂ CH ₂ 0

434 Me COEt 0 CMe ₂ CH ₂ 0

435 Me C0 ₂Et 0 CMe ₂ CH ₂ 0 436 Me S0 ₂Me 0 CMe ₂ CH ₂ 0

437 CF ₃ H 0 CMe ₂ CH ₂ 0

438 CF ₃ COEt 0 CMe ₂ CH ₂ 0

439 CF ₃ C0 ₂Et 0 CMe ₂ CH ₂ 0

440 CF ₃ S0 ₂CF ₃ 0 CMe ₂ CH ₂ 0

441 CF ₃ S0 ₂Me 0 CMe ₂ CH ₂ 0

442 Me H 0 CH ₂ CH ₂ CH ₂ 0

443 Me COEt 0 CH ₂ CH ₂ CH ₂ 0

444 Me C0 ₂Et 0 CH ₂ CH ₂ CH ₂ 0

445 Me S0 ₂Me 0 CH ₂ CH ₂ CH ₂ 0

446 CF ₃ H 0 CH ₂ CH ₂ CH ₂ 0

447 CF ₃ COEt 0 CH ₂ CH ₂ CH ₂ 0

448 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ₂ 0

449 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ₂ 0

450 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ₂ 0

451 Me H 0 CH ₂ CH ₂ CHMe 0

452 Me COEt 0 CH ₂ CH ₂ CHMe 0

453 Me C0 ₂Et 0 CH ₂ CH ₂ CHMe 0

454 Me S0 ₂Me 0 CH ₂ CH ₂ CHMe 0

455 CF ₃ H 0 CH ₂ CH ₂ CHMe 0

456 CF ₃ COEt 0 CH ₂ CH ₂ CHMe 0

457 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CHMe 0

458 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CHMe 0

459 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CHMe 0

460 Me H 0 CH ₂ CH ₂ CHEt 0

461 Me COEt 0 CH ₂ CH ₂ CHEt 0

462 Me C0 ₂Et 0 CH ₂ CH ₂ CHEt 0

463 Me S0 ₂Me 0 CH ₂ CH ₂ CHEt 0

464 CF ₃ H 0 CH ₂ CH ₂ CHEt 0

465 CF ₃ COEt 0 CH ₂ CH ₂ CHEt 0

466 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CHEt 0

467 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CHEt 0

468 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CHEt 0

469 Me H 0 CH ₂ CH ₂ CH ⁿPr 0

470 Me COEt 0 CH ₂ CH ₂ CH ⁿPr 0 471 Me C0 ₂Et 0 CH ₂ CH ₂ CH ⁿPr 0

472 Me S0 ₂Me 0 CH ₂ CH ₂ CH ⁿPr 0

473 CF ₃ H 0 CH ₂ CH ₂ CH ⁿPr 0

474 CF ₃ COEt 0 CH ₂ CH ₂ CH ⁿPr 0

475 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH ⁿPr 0

476 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH ⁿPr 0

477 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH ⁿPr 0

478 Me H 0 CH ₂ CH ₂ CMe ₂ 0

479 Me COEt 0 CH ₂ CH ₂ CMe ₂ 0

480 Me C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ 0

481 Me S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ 0

482 CF ₃ H 0 CH ₂ CH ₂ CMe ₂ 0

483 CF ₃ COEt 0 CH ₂ CH ₂ CMe ₂ 0

484 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CMe ₂ 0

485 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CMe ₂ 0

486 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CMe ₂ 0

487 Me H 0 CH ₂ CH ₂ C(Me)( CF ₃) 0

488 Me COEt 0 CH ₂ CH ₂ C(Me)( CF ₃) 0

489 Me C0 ₂Et 0 CH ₂ CH ₂ C(Me)( CF ₃) 0

490 Me S0 ₂Me 0 CH ₂ CH ₂ C(Me)( CF ₃) 0

491 CF ₃ H 0 CH ₂ CH ₂ C(Me)( CF ₃) 0

492 CF ₃ COEt 0 CH ₂ CH ₂ C(Me)( CF ₃) 0

493 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ C(Me)( CF ₃) 0

494 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ C(Me)( CF ₃) 0

495 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ C(Me)( CF ₃) 0

496 Me H 0 CH ₂ CH ₂ C(Et)( CF ₃) 0

497 Me COEt 0 CH ₂ CH ₂ C(Et)( CF ₃) 0

498 Me C0 ₂Et 0 CH ₂ CH ₂ C(Et)( CF ₃) 0

499 Me S0 ₂Me 0 CH ₂ CH ₂ C(Et)( CF ₃) 0

500 CF ₃ H 0 CH ₂ CH ₂ C(Et)( CF ₃) 0

501 CF ₃ COEt 0 CH ₂ CH ₂ C(Et)( CF ₃) 0

502 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ C(Et)( CF ₃) 0

503 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ C(Et)( CF ₃) 0

504 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ C(Et)( CF ₃) 0

505 Me H 0 CH ₂ CH ₂ CEt ₂ 0 506 Me COEt 0 CH ₂ CH ₂ CEt ₂ 0

507 Me C0 ₂Et 0 CH ₂ CH ₂ CEt ₂ 0

508 Me S0 ₂Me 0 CH ₂ CH ₂ CEt ₂ 0

509 CF ₃ H 0 CH ₂ CH ₂ CEt ₂ 0

510 CF ₃ COEt 0 CH ₂ CH ₂ CEt ₂ 0

511 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CEt ₂ 0

512 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CEt ₂ 0

513 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CEt ₂ 0

514 Me H 0 CH ₂ CH ₂ C( ^cPr)(Me) 0

515 Me COEt 0 CH ₂ CH ₂ C( ^cPr)(Me) 0

516 Me C0 ₂Et 0 CH ₂ CH ₂ C( ^cPr)(Me) 0

517 Me S0 ₂Me 0 CH ₂ CH ₂ C( ^cPr)(Me) 0

518 CF ₃ H 0 CH ₂ CH ₂ C( ^cPr)(Me) 0

519 CF ₃ COEt 0 CH ₂ CH ₂ C( ^cPr)(Me) 0

520 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ C( ^cPr)(Me) 0

521 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ C( ^cPr)(Me) 0

522 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ C( ^cPr)(Me) 0

523 Me H 0 CH ₂ CH ₂ C(CH ₂) ₄ 0

524 Me COEt 0 CH ₂ CH ₂ C(CH ₂) ₄ 0

525 Me C0 ₂Et 0 CH ₂ CH ₂ C(CH ₂) ₄ 0

526 Me S0 ₂Me 0 CH ₂ CH ₂ C(CH ₂) ₄ 0

527 CF ₃ H 0 CH ₂ CH ₂ C(CH ₂) ₄ 0

528 CF ₃ COEt 0 CH ₂ CH ₂ C(CH ₂) ₄ 0

529 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ C(CH ₂) ₄ 0

530 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ C(CH ₂) ₄ 0

531 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ C(CH ₂) ₄ 0

532 Me H 0 CH ₂ CH ₂ CH(2-fluorophenyl) 0

533 Me COEt 0 CH ₂ CH ₂ CH(2-fluorophenyl) 0

534 Me C0 ₂Et 0 CH ₂ CH ₂ CH(2-fluorophenyl) 0

535 Me S0 ₂Me 0 CH ₂ CH ₂ CH(2-fluorophenyl) 0

536 CF ₃ H 0 CH ₂ CH ₂ CH(2-fluorophenyl) 0

537 CF ₃ COEt 0 CH ₂ CH ₂ CH(2-fluorophenyl) 0

538 CF ₃ C0 ₂Et 0 CH ₂ CH ₂ CH(2-fluorophenyl) 0

539 CF ₃ S0 ₂CF ₃ 0 CH ₂ CH ₂ CH(2-fluorophenyl) 0

540 CF ₃ S0 ₂Me 0 CH ₂ CH ₂ CH(2-fluorophenyl) 0 541 Me H 0 CH ₂ CHMe CH ₂ 0

542 Me COEt 0 CH ₂ CHMe CH ₂ 0

543 Me C0 ₂Et 0 CH ₂ CHMe CH ₂ 0

544 Me S0 ₂Me 0 CH ₂ CHMe CH ₂ 0

545 CF ₃ H 0 CH ₂ CHMe CH ₂ 0

546 CF ₃ COEt 0 CH ₂ CHMe CH ₂ 0

547 CF ₃ C0 ₂Et 0 CH ₂ CHMe CH ₂ 0

548 CF ₃ S0 ₂CF ₃ 0 CH ₂ CHMe CH ₂ 0

549 CF ₃ S0 ₂Me 0 CH ₂ CHMe CH ₂ 0

550 Me H 0 CH ₂ CMe ₂ CH ₂ 0

551 Me COEt 0 CH ₂ CMe ₂ CH ₂ 0

552 Me C0 ₂Et 0 CH ₂ CMe ₂ CH ₂ 0

553 Me S0 ₂Me 0 CH ₂ CMe ₂ CH ₂ 0

554 CF ₃ H 0 CH ₂ CMe ₂ CH ₂ 0

555 CF ₃ COEt 0 CH ₂ CMe ₂ CH ₂ 0

556 CF ₃ C0 ₂Et 0 CH ₂ CMe ₂ CH ₂ 0

557 CF ₃ S0 ₂CF ₃ 0 CH ₂ CMe ₂ CH ₂ 0

558 CF ₃ S0 ₂Me 0 CH ₂ CMe ₂ CH ₂ 0

559 Me H 0 CHMe CH ₂ CH ₂ 0

560 Me COEt 0 CHMe CH ₂ CH ₂ 0

561 Me C0 ₂Et 0 CHMe CH ₂ CH ₂ 0

562 Me S0 ₂Me 0 CHMe CH ₂ CH ₂ 0

563 CF ₃ H 0 CHMe CH ₂ CH ₂ 0

564 CF ₃ COEt 0 CHMe CH ₂ CH ₂ 0

565 CF ₃ C0 ₂Et 0 CHMe CH ₂ CH ₂ 0

566 CF ₃ S0 ₂CF ₃ 0 CHMe CH ₂ CH ₂ 0

567 CF ₃ S0 ₂Me 0 CHMe CH ₂ CH ₂ 0

568 Me H 0 CMe ₂ CH ₂ CH ₂ 0

569 Me COEt 0 CMe ₂ CH ₂ CH ₂ 0

570 Me C0 ₂Et 0 CMe ₂ CH ₂ CH ₂ 0

571 Me S0 ₂Me 0 CMe ₂ CH ₂ CH ₂ 0

572 CF ₃ H 0 CMe ₂ CH ₂ CH ₂ 0

573 CF ₃ COEt 0 CMe ₂ CH ₂ CH ₂ 0

574 CF ₃ C0 ₂Et 0 CMe ₂ CH ₂ CH ₂ 0

575 CF ₃ S0 ₂CF ₃ 0 CMe ₂ CH ₂ CH ₂ 0 576 CF ₃ S0 ₂Me 0 CMe ₂ CH ₂ CH ₂ 0

577 Me H 0 CH ₂CH ₂ CH ₂ CH ₂ 0

578 Me COEt 0 CH ₂CH ₂ CH ₂ CH ₂ 0

579 Me C0 ₂Et 0 CH ₂CH ₂ CH ₂ CH ₂ 0

580 Me S0 ₂Me 0 CH ₂CH ₂ CH ₂ CH ₂ 0

581 CF ₃ H 0 CH ₂CH ₂ CH ₂ CH ₂ 0

582 CF ₃ COEt 0 CH ₂CH ₂ CH ₂ CH ₂ 0

583 CF ₃ C0 ₂Et 0 CH ₂CH ₂ CH ₂ CH ₂ 0

584 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ CH ₂ CH ₂ 0

585 CF ₃ S0 ₂Me 0 CH ₂CH ₂ CH ₂ CH ₂ 0

586 Me H 0 CH ₂CH ₂ CHMe CH ₂ 0

587 Me COEt 0 CH ₂CH ₂ CHMe CH ₂ 0

588 Me C0 ₂Et 0 CH ₂CH ₂ CHMe CH ₂ 0

589 Me S0 ₂Me 0 CH ₂CH ₂ CHMe CH ₂ 0

590 CF ₃ H 0 CH ₂CH ₂ CHMe CH ₂ 0

591 CF ₃ COEt 0 CH ₂CH ₂ CHMe CH ₂ 0

592 CF ₃ C0 ₂Et 0 CH ₂CH ₂ CHMe CH ₂ 0

593 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ CHMe CH ₂ 0

594 CF ₃ S0 ₂Me 0 CH ₂CH ₂ CHMe CH ₂ 0

595 Me H 0 CH ₂CH ₂ CMe ₂ CH ₂ 0

596 Me COEt 0 CH ₂CH ₂ CMe ₂ CH ₂ 0

597 Me C0 ₂Et 0 CH ₂CH ₂ CMe ₂ CH ₂ 0

598 Me S0 ₂Me 0 CH ₂CH ₂ CMe ₂ CH ₂ 0

599 CF ₃ H 0 CH ₂CH ₂ CMe ₂ CH ₂ 0

600 CF ₃ COEt 0 CH ₂CH ₂ CMe ₂ CH ₂ 0

601 CF ₃ C0 ₂Et 0 CH ₂CH ₂ CMe ₂ CH ₂ 0

602 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ CMe ₂ CH ₂ 0

603 CF ₃ S0 ₂Me 0 CH ₂CH ₂ CMe ₂ CH ₂ 0

604 Me H 0 CH ₂ 0 CH ₂ CH ₂

605 Me COEt 0 CH ₂ 0 CH ₂ CH ₂

606 Me C0 ₂Et 0 CH ₂ 0 CH ₂ CH ₂

607 Me S0 ₂Me 0 CH ₂ 0 CH ₂ CH ₂

608 CF ₃ H 0 CH ₂ 0 CH ₂ CH ₂

609 CF ₃ COEt 0 CH ₂ 0 CH ₂ CH ₂

610 CF ₃ C0 ₂Et 0 CH ₂ 0 CH ₂ CH ₂ 611 CF ₃ S0 ₂CF ₃ 0 CH ₂ 0 CH ₂ CH ₂

612 CF ₃ S0 ₂Me 0 CH ₂ 0 CH ₂ CH ₂

613 Me H 0 CH ₂ 0 CHMe CH ₂

614 Me COEt 0 CH ₂ 0 CHMe CH ₂

615 Me C0 ₂Et 0 CH ₂ 0 CHMe CH ₂

616 Me S0 ₂Me 0 CH ₂ 0 CHMe CH ₂

617 CF ₃ H 0 CH ₂ 0 CHMe CH ₂

618 CF ₃ COEt 0 CH ₂ 0 CHMe CH ₂

619 CF ₃ C0 ₂Et 0 CH ₂ 0 CHMe CH ₂

620 CF ₃ S0 ₂CF ₃ 0 CH ₂ 0 CHMe CH ₂

621 CF ₃ S0 ₂Me 0 CH ₂ 0 CHMe CH ₂

622 Me H 0 CH ₂ 0 CMe ₂ CH ₂

623 Me COEt 0 CH ₂ 0 CMe ₂ CH ₂

624 Me C0 ₂Et 0 CH ₂ 0 CMe ₂ CH ₂

625 Me S0 ₂Me 0 CH ₂ 0 CMe ₂ CH ₂

626 CF ₃ H 0 CH ₂ 0 CMe ₂ CH ₂

627 CF ₃ COEt 0 CH ₂ 0 CMe ₂ CH ₂

628 CF ₃ C0 ₂Et 0 CH ₂ 0 CMe ₂ CH ₂

629 CF ₃ S0 ₂CF ₃ 0 CH ₂ 0 CMe ₂ CH ₂

630 CF ₃ S0 ₂Me 0 CH ₂ 0 CMe ₂ CH ₂

631 Me H 0 CH ₂ 0 C(Me)( CF ₃) CH ₂

632 Me COEt 0 CH ₂ 0 C(Me)( CF ₃) CH ₂

633 Me C0 ₂Et 0 CH ₂ 0 C(Me)( CF ₃) CH ₂

634 Me S0 ₂Me 0 CH ₂ 0 C(Me)( CF ₃) CH ₂

635 CF ₃ H 0 CH ₂ 0 C(Me)( CF ₃) CH ₂

636 CF ₃ COEt 0 CH ₂ 0 C(Me)( CF ₃) CH ₂

637 CF ₃ C0 ₂Et 0 CH ₂ 0 C(Me)( CF ₃) CH ₂

638 CF ₃ S0 ₂CF ₃ 0 CH ₂ 0 C(Me)( CF ₃) CH ₂

639 CF ₃ S0 ₂Me 0 CH ₂ 0 C(Me)( CF ₃) CH ₂

640 Me H 0 CH ₂ 0 C(CH ₂) ₃ CH ₂

641 Me COEt 0 CH ₂ 0 C(CH ₂) ₃ CH ₂

642 Me C0 ₂Et 0 CH ₂ 0 C(CH ₂) ₃ CH ₂

643 Me S0 ₂Me 0 CH ₂ 0 C(CH ₂) ₃ CH ₂

644 CF ₃ H 0 CH ₂ 0 C(CH ₂) ₃ CH ₂

645 CF ₃ COEt 0 CH ₂ 0 C(CH ₂) ₃ CH ₂ 646 CF ₃ C0 ₂Et 0 CH ₂ 0 C(CH ₂) ₃ CH ₂

647 CF ₃ S0 ₂CF ₃ 0 CH ₂ 0 C(CH ₂) ₃ CH ₂

648 CF ₃ S0 ₂Me 0 CH ₂ 0 C(CH ₂) ₃ CH ₂

649 Me H 0 CH ₂ 0 C(CH ₂) ₄ CH ₂

650 Me COEt 0 CH ₂ 0 C(CH ₂) ₄ CH ₂

651 Me C0 ₂Et 0 CH ₂ 0 C(CH ₂) ₄ CH ₂

652 Me S0 ₂Me 0 CH ₂ 0 C(CH ₂) ₄ CH ₂

653 CF ₃ H 0 CH ₂ 0 C(CH ₂) ₄ CH ₂

654 CF ₃ COEt 0 CH ₂ 0 C(CH ₂) ₄ CH ₂

655 CF ₃ C0 ₂Et 0 CH ₂ 0 C(CH ₂) ₄ CH ₂

656 CF ₃ S0 ₂CF ₃ 0 CH ₂ 0 C(CH ₂) ₄ CH ₂

657 CF ₃ S0 ₂Me 0 CH ₂ 0 C(CH ₂) ₄ CH ₂

658 Me H 0 CHMe 0 CH ₂ CH ₂

659 Me COEt 0 CHMe 0 CH ₂ CH ₂

660 Me C0 ₂Et 0 CHMe 0 CH ₂ CH ₂

661 Me S0 ₂Me 0 CHMe 0 CH ₂ CH ₂

662 CF ₃ H 0 CHMe 0 CH ₂ CH ₂

663 CF ₃ COEt 0 CHMe 0 CH ₂ CH ₂

664 CF ₃ C0 ₂Et 0 CHMe 0 CH ₂ CH ₂

665 CF ₃ S0 ₂CF ₃ 0 CHMe 0 CH ₂ CH ₂

666 CF ₃ S0 ₂Me 0 CHMe 0 CH ₂ CH ₂

667 Me H 0 CHMe 0 CMe ₂ CH ₂

668 Me COEt 0 CHMe 0 CMe ₂ CH ₂

669 Me C0 ₂Et 0 CHMe 0 CMe ₂ CH ₂

670 Me S0 ₂Me 0 CHMe 0 CMe ₂ CH ₂

671 CF ₃ H 0 CHMe 0 CMe ₂ CH ₂

672 CF ₃ COEt 0 CHMe 0 CMe ₂ CH ₂

673 CF ₃ C0 ₂Et 0 CHMe 0 CMe ₂ CH ₂

674 CF ₃ S0 ₂CF ₃ 0 CHMe 0 CMe ₂ CH ₂

675 CF ₃ S0 ₂Me 0 CHMe 0 CMe ₂ CH ₂

676 Me H 0 CH ₂CH ₂ 0 CH ₂

677 Me COEt 0 CH ₂CH ₂ 0 CH ₂

678 Me C0 ₂Et 0 CH ₂CH ₂ 0 CH ₂

679 Me S0 ₂Me 0 CH ₂CH ₂ 0 CH ₂

680 CF ₃ H 0 CH ₂CH ₂ 0 CH ₂ 681 CF ₃ COEt 0 CH ₂CH ₂ 0 CH ₂

682 CF ₃ C0 ₂Et 0 CH ₂CH ₂ 0 CH ₂

683 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ 0 CH ₂

684 CF ₃ S0 ₂Me 0 CH ₂CH ₂ 0 CH ₂

685 Me H 0 CH ₂CHMe 0 CH ₂

686 Me COEt 0 CH ₂CHMe 0 CH ₂

687 Me C0 ₂Et 0 CH ₂CHMe 0 CH ₂

688 Me S0 ₂Me 0 CH ₂CHMe 0 CH ₂

689 CF ₃ H 0 CH ₂CHMe 0 CH ₂

690 CF ₃ COEt 0 CH ₂CHMe 0 CH ₂

691 CF ₃ C0 ₂Et 0 CH ₂CHMe 0 CH ₂

692 CF ₃ S0 ₂CF ₃ 0 CH ₂CHMe 0 CH ₂

693 CF ₃ S0 ₂Me 0 CH ₂CHMe 0 CH ₂

694 Me H 0 CH ₂CHEt 0 CH ₂

695 Me COEt 0 CH ₂CHEt 0 CH ₂

696 Me C0 ₂Et 0 CH ₂CHEt 0 CH ₂

697 Me S0 ₂Me 0 CH ₂CHEt 0 CH ₂

698 CF ₃ H 0 CH ₂CHEt 0 CH ₂

699 CF ₃ COEt 0 CH ₂CHEt 0 CH ₂

700 CF ₃ C0 ₂Et 0 CH ₂CHEt 0 CH ₂

701 CF ₃ S0 ₂CF ₃ 0 CH ₂CHEt 0 CH ₂

702 CF ₃ S0 ₂Me 0 CH ₂CHEt 0 CH ₂

703 Me H 0 CH ₂CMe ₂ 0 CH ₂

704 Me COEt 0 CH ₂CMe ₂ 0 CH ₂

705 Me C0 ₂Et 0 CH ₂CMe ₂ 0 CH ₂

706 Me S0 ₂Me 0 CH ₂CMe ₂ 0 CH ₂

707 CF ₃ H 0 CH ₂CMe ₂ 0 CH ₂

708 CF ₃ COEt 0 CH ₂CMe ₂ 0 CH ₂

709 CF ₃ C0 ₂Et 0 CH ₂CMe ₂ 0 CH ₂

710 CF ₃ S0 ₂CF ₃ 0 CH ₂CMe ₂ 0 CH ₂

711 CF ₃ S0 ₂Me 0 CH ₂CMe ₂ 0 CH ₂

712 Me H 0 CHMeCH ₂ 0 CH ₂

713 Me COEt 0 CHMeCH ₂ 0 CH ₂

714 Me C0 ₂Et 0 CHMeCH ₂ 0 CH ₂

715 Me S0 ₂Me 0 CHMeCH ₂ 0 CH ₂ 716 CF ₃ H 0 CHMeCH ₂ 0 CH ₂

717 CF ₃ COEt 0 CHMeCH ₂ 0 CH ₂

718 CF ₃ C0 ₂Et 0 CHMeCH ₂ 0 CH ₂

719 CF ₃ S0 ₂CF ₃ 0 CHMeCH ₂ 0 CH ₂

720 CF ₃ S0 ₂Me 0 CHMeCH ₂ 0 CH ₂

721 Me H 0 CH ₂CH ₂ 0 CHMe

722 Me COEt 0 CH ₂CH ₂ 0 CHMe

723 Me C0 ₂Et 0 CH ₂CH ₂ 0 CHMe

724 Me S0 ₂Me 0 CH ₂CH ₂ 0 CHMe

725 CF ₃ H 0 CH ₂CH ₂ 0 CHMe

726 CF ₃ COEt 0 CH ₂CH ₂ 0 CHMe

727 CF ₃ C0 ₂Et 0 CH ₂CH ₂ 0 CHMe

728 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ 0 CHMe

729 CF ₃ S0 ₂Me 0 CH ₂CH ₂ 0 CHMe

730 Me H 0 CH ₂CH ₂ 0 CMe ₂

731 Me COEt 0 CH ₂CH ₂ 0 CMe ₂

732 Me C0 ₂Et 0 CH ₂CH ₂ 0 CMe ₂

733 Me S0 ₂Me 0 CH ₂CH ₂ 0 CMe ₂

734 CF ₃ H 0 CH ₂CH ₂ 0 CMe ₂

735 CF ₃ COEt 0 CH ₂CH ₂ 0 CMe ₂

736 CF ₃ C0 ₂Et 0 CH ₂CH ₂ 0 CMe ₂

737 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ 0 CMe ₂

738 CF ₃ S0 ₂Me 0 CH ₂CH ₂ 0 CMe ₂

739 Me H 0 CH ₂CH ₂ 0 CHPh

740 Me COEt 0 CH ₂CH ₂ 0 CHPh

741 Me C0 ₂Et 0 CH ₂CH ₂ 0 CHPh

742 Me S0 ₂Me 0 CH ₂CH ₂ 0 CHPh

743 CF ₃ H 0 CH ₂CH ₂ 0 CHPh

744 CF ₃ COEt 0 CH ₂CH ₂ 0 CHPh

745 CF ₃ C0 ₂Et 0 CH ₂CH ₂ 0 CHPh

746 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ 0 CHPh

747 CF ₃ S0 ₂Me 0 CH ₂CH ₂ 0 CHPh

748 Me H 0 CH ₂CH ₂ s CH ₂

749 Me COEt 0 CH ₂CH ₂ s CH ₂

750 Me C0 ₂Et 0 CH ₂CH ₂ s CH ₂ 751 Me S0 ₂Me 0 CH ₂CH ₂ s CH ₂

752 CF ₃ H 0 CH ₂CH ₂ s CH ₂

753 CF ₃ COEt 0 CH ₂CH ₂ s CH ₂

754 CF ₃ C0 ₂Et 0 CH ₂CH ₂ s CH ₂

755 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ s CH ₂

756 CF ₃ S0 ₂Me 0 CH ₂CH ₂ s CH ₂

757 Me H 0 CH ₂CH ₂ 0 CH ₂ CH ₂

758 Me COEt 0 CH ₂CH ₂ 0 CH ₂ CH ₂

759 Me C0 ₂Et 0 CH ₂CH ₂ 0 CH ₂ CH ₂

760 Me S0 ₂Me 0 CH ₂CH ₂ 0 CH ₂ CH ₂

761 CF ₃ H 0 CH ₂CH ₂ 0 CH ₂ CH ₂

762 CF ₃ COEt 0 CH ₂CH ₂ 0 CH ₂ CH ₂

763 CF ₃ C0 ₂Et 0 CH ₂CH ₂ 0 CH ₂ CH ₂

764 CF ₃ S0 ₂CF ₃ 0 CH ₂CH ₂ 0 CH ₂ CH ₂

765 CF ₃ S0 ₂Me 0 CH ₂CH ₂ 0 CH ₂ CH ₂

766 Me H 0 0 CMe ₂ CH ₂

767 Me COEt 0 0 CMe ₂ CH ₂

768 Me C0 ₂Et 0 0 CMe ₂ CH ₂

769 Me S0 ₂Me 0 0 CMe ₂ CH ₂

770 CF ₃ H 0 0 CMe ₂ CH ₂

771 CF ₃ COEt 0 0 CMe ₂ CH ₂

772 CF ₃ C0 ₂Et 0 0 CMe ₂ CH ₂

773 CF ₃ S0 ₂CF ₃ 0 0 CMe ₂ CH ₂

774 CF ₃ S0 ₂Me 0 0 CMe ₂ CH ₂

775 Me H 0 0 CH ₂CH ₂ CH ₂

776 Me COEt 0 0 CH ₂CH ₂ CH ₂

777 Me C0 ₂Et 0 0 CH ₂CH ₂ CH ₂

778 Me S0 ₂Me 0 0 CH ₂CH ₂ CH ₂

779 CF ₃ H 0 0 CH ₂CH ₂ CH ₂

780 CF ₃ COEt 0 0 CH ₂CH ₂ CH ₂

781 CF ₃ C0 ₂Et 0 0 CH ₂CH ₂ CH ₂

782 CF ₃ S0 ₂CF ₃ 0 0 CH ₂CH ₂ CH ₂

783 CF ₃ S0 ₂Me 0 0 CH ₂CH ₂ CH ₂

784 Me H 0 0 CH ₂CHEt 0

785 Me COEt 0 0 CH ₂CHEt 0 786 Me C0 ₂Et 0 0 CH ₂CHEt 0

787 Me S0 ₂Me 0 0 CH ₂CHEt 0

788 CF ₃ H 0 0 CH ₂CHEt 0

789 CF ₃ COEt 0 0 CH ₂CHEt 0

790 CF ₃ C0 ₂Et 0 0 CH ₂CHEt 0

791 CF ₃ S0 ₂CF ₃ 0 0 CH ₂CHEt 0

792 CF ₃ S0 ₂Me 0 0 CH ₂CHEt 0

793 Me H 0 0 CH ₂CH ₂CMe ₂ CH ₂

794 Me COEt 0 0 CH ₂CH ₂CMe ₂ CH ₂

795 Me C0 ₂Et 0 0 CH ₂CH ₂CMe ₂ CH ₂

796 Me S0 ₂Me 0 0 CH ₂CH ₂CMe ₂ CH ₂

797 CF ₃ H 0 0 CH ₂CH ₂CMe ₂ CH ₂

798 CF ₃ COEt 0 0 CH ₂CH ₂CMe ₂ CH ₂

799 CF ₃ C0 ₂Et 0 0 CH ₂CH ₂CMe ₂ CH ₂

800 CF ₃ S0 ₂CF ₃ 0 0 CH ₂CH ₂CMe ₂ CH ₂

801 CF ₃ S0 ₂Me 0 0 CH ₂CH ₂CMe ₂ CH ₂

801 compounds are described, designated compounds 2-1 to 2-801 respectively, of formula (I) wherein ring A is A2, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 3-1 to 3-801 respectively, of formula (I) wherein ring A is A3, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 4-1 to 4-801 respectively, of formula (I) wherein ring A is A4, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 5-1 to 5-801 respectively, of formula (I) wherein ring A is A5, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 6-1 to 6-801 respectively, of formula (I) wherein ring A is A6, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 7-1 to 7-801 respectively, of formula (I) wherein ring A is A7, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 8-1 to 8-801 respectively, of formula (I) wherein ring A is A8, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 9-1 to 9-801 respectively, of formula (I) wherein ring A is A9, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. compounds are described, designated compounds 10-1 to 10-801 respectively, of formula (I) wherein ring Ais A10, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 11-1 to 11-801 respectively, of formula (I) wherein ring Ais A11, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 12-1 to 12-801 respectively, of formula (I) wherein ring Ais A12, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 13-1 to 13-801 respectively, of formula (I) wherein ring Ais A13, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 14-1 to 14-801 respectively, of formula (I) wherein ring Ais A14, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 15-1 to 15-801 respectively, of formula (I) wherein ring Ais A15, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 16-1 to 16-801 respectively, of formula (I) wherein ring Ais A16, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 17-1 to 17-801 respectively, of formula (I) wherein ring Ais A17, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 18-1 to 18-801 respectively, of formula (I) wherein ring Ais A18, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 19-1 to 19-801 respectively, of formula (I) wherein ring Ais A19, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 20-1 to 20-801 respectively, of formula (I) wherein ring Ais A20, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 21-1 to 21-801 respectively, of formula (I) wherein ring Ais A21, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 22-1 to 22-801 respectively, of formula (I) wherein ring Ais A22, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 23-1 to 23-801 respectively, of formula (I) wherein ring Ais A23, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 24-1 to 24-801 respectively, of formula (I) wherein ring Ais A24, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 25-1 to 25-801 respectively, of formula (I) wherein ring Ais A25, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 26-1 to 26-801 respectively, of formula (I) wherein ring Ais A26, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 27-1 to 27-801 respectively, of formula (I) wherein ring Ais A27, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 28-1 to 28-801 respectively, of formula (I) wherein ring Ais A28, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 29-1 to 29-801 respectively, of formula (I) wherein ring Ais A29, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 30-1 to 30-801 respectively, of formula (I) wherein ring Ais A30, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 31-1 to 31-801 respectively, of formula (I) wherein ring Ais A31, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 32-1 to 32-801 respectively, of formula (I) wherein ring Ais A32, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 33-1 to 33-801 respectively, of formula (I) wherein ring Ais A33, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 34-1 to 34-801 respectively, of formula (I) wherein ring Ais A34, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 35-1 to 35-801 respectively, of formula (I) wherein ring Ais A35, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 36-1 to 36-801 respectively, of formula (I) wherein ring Ais A36, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 37-1 to 37-801 respectively, of formula (I) wherein ring Ais A37, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 38-1 to 38-801 respectively, of formula (I) wherein ring Ais A38, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 39-1 to 39-801 respectively, of formula (I) wherein ring Ais A39, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 40-1 to 40-801 respectively, of formula (I) wherein ring Ais A40, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 41-1 to 41-801 respectively, of formula (I) wherein ring Ais A41, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. compounds are described, designated compounds 42-1 to 42-801 respectively, of formula (I) wherein ring Ais A42, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 43-1 to 43-801 respectively, of formula (I) wherein ring Ais A43, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 44-1 to 44-801 respectively, of formula (I) wherein ring Ais A44, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 45-1 to 45-801 respectively, of formula (I) wherein ring Ais A45, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 46-1 to 46-801 respectively, of formula (I) wherein ring Ais A46, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 47-1 to 47-801 respectively, of formula (I) wherein ring Ais A47, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 48-1 to 48-801 respectively, of formula (I) wherein ring Ais A48, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 49-1 to 49-801 respectively, of formula (I) wherein ring Ais A49, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 50-1 to 50-801 respectively, of formula (I) wherein ring Ais A50, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 51-1 to 51-801 respectively, of formula (I) wherein ring Ais A51, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 52-1 to 52-801 respectively, of formula (I) wherein ring Ais A52, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 53-1 to 53-801 respectively, of formula (I) wherein ring Ais A53, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 54-1 to 54-801 respectively, of formula (I) wherein ring Ais A54, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 55-1 to 55-801 respectively, of formula (I) wherein ring Ais A55, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 56-1 to 56-801 respectively, of formula (I) wherein ring Ais A56, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 57-1 to 57-801 respectively, of formula (I) wherein ring Ais A57, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. compounds are described, designated compounds 58-1 to 58-801 respectively, of formula (I) wherein ring A is A58, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 59-1 to 59-801 respectively, of formula (I) wherein ring A is A59, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 60-1 to 60-801 respectively, of formula (I) wherein ring A is A60, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 61-1 to 61-801 respectively, of formula (I) wherein ring A is A61 , and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 62-1 to 62-801 respectively, of formula (I) wherein ring A is A62, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1. 801 compounds are described, designated compounds 63-1 to 63-801 respectively, of formula (I) wherein ring A is A63, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 64-1 to 64-801 respectively, of formula (I) wherein ring A is A64, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

801 compounds are described, designated compounds 65-1 to 65-801 respectively, of formula (I) wherein ring A is A65, and the values of R, R , W, (CR R ²) _n, X, (CR ⁵R ⁶) _P and Z are as defined in Table 1.

The herbicidal compounds of formula (I) may exist as different geometric isomers, or in different tautomeric forms. This invention covers all such isomers and tautomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds.

The herbicidal compounds of this invention may contain an asymmetric carbon atom and some of the compounds of this invention may contain one or more asymmetric centers and may thus give rise to optical isomers and diastereomers. While shown without respect to stereochemistry, the present invention includes such optical isomers and diastereomers; as well as the racemic mixture and resolved, enantiomerically pure R and S stereoisomers; as well as other mixtures of the R and S stereoisomers and agrochemically acceptable salts thereof. It is recognized that one optical isomer, including diastereomer and enantiomer, or stereoisomer may have favorable properties over the other. Thus when disclosing and claiming the invention, when one racemic mixture is disclosed, it is clearly contemplated that both optical isomers, including diastereomers and enantiomers, or stereoisomers substantially free of the other are disclosed and claimed as well.

Hydroxy or hydroxyl, as used herein, refers to the group -OH. Cyano, or nitrile, as used herein, refers to the group -CN.

Nitro, as used herein, refers to the group -N0 ₂.

Oxo, as used herein, refers to the group =0.

Carboxy, as used herein, refers to the group -C(0)OH. Alkyl, as used herein, refers to an aliphatic hydrocarbon chain and includes straight and branched chains e. g. of 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, and isohexyl.

Alkenyl, as used herein, refers to an aliphatic hydrocarbon chain having at least one double bond, and preferably one double bond, and includes straight and branched chains e. g. of 2 to 6 carbon atoms such as ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), isopropenyl, but-1-enyl, but-2-enyl, but-3-enyl, 2- methypropenyl.

Alkynyl, as used herein, refers to an aliphatic hydrocarbon chain having at least one triple bond, and preferably one triple bond, and includes straight and branched chains e. g. of 2 to 6 carbon atoms such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl) but-1-ynyl, but-2-ynyl and but-3-ynyl.

Alkylene, as used herein, means a branched or linear divalent hydrocarbon radical. Examples of alkylene are methylene, 1 , 1-ethylene, 1 ,2-ethylene, 1 ,1-propylene, 1 ,2-propylene, 1 ,3-propylene and 2,2- propylene etc.

Cycloalkyl, as used herein, refers to a cyclic, saturated hydrocarbon group having from 3 to 6 ring carbon atoms. Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Alkylthio, as used herein, refers to the group -SR, wherein R is alkyl as defined above. Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tert-butylthio, and the like.

Cyanoalkyl, as used herein, refers to an alkyl group substituted with one or more cyano groups.

Alkoxy, as used herein, refers to the group -OR, wherein R is alkyl as defined above. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentoxy, isopentoxy, neo-pentoxy, n-hexyloxy, and isohexyloxy.

Alkoxyalkyl, as used herein, refers to the group -ROR, wherein each R is independently alkyl group as defined herein.

Alkoxyalkoxy, as used herein, refers to the group -OROR, wherein each R is independently alkyl as defined herein.

Alkoxyalkoxyalkyl, as used herein, refers to the group -ROROR, wherein each R is independently alkyl as defined herein.

Alkylthioalkyl, as used herein, refers to the group -RSR, wherein each R is independently alkyl as defined herein.

Halogen, halide and halo refer to iodine, bromine, chlorine and fluorine.

Haloalkyl, as used herein, refers to an alkyl group as defined herein wherein at least one hydrogen atom has been replaced with a halogen atom as defined above. Examples of haloalkyl groups include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and trifluoromethyl. Haloalkylthio, as used herein, refers to the group -SR, wherein R is haloalkyl as defined herein.

Haloalkoxy, as used herein, refers to the group -OR, wherein R is haloalkyl as defined herein.

Haloalkoxyalkyl, as used herein, refers to the group -ROR', wherein R is alkyl as defined herein and R' is haloalkyl as defined herein. Alkylcarbonyl, as used herein, refers to the group -C(0)R, wherein R is alkyl as defined herein.

Examples of alkylcarbonyl groups include ethanoyl, propanoyl, n-butanoyl, etc.

Alkenylcarbonyl, as used herein, refers to the group -C(0)R, wherein R is alkenyl as defined herein.

Cycloalkylcarbonyl, as used herein, refers to the group -C(0)R, wherein R is cycloalkyl as defined herein.

Haloalkylcarbonyl, as used herein, refers to the group -C(0)R, wherein R is haloalkyl as defined herein.

Alkoxycarbonyl, as used herein, refers to the group -C(0)OR, wherein R is alkyl as defined herein.

Alkenyloxycarbonyl, as used herein, refers to the group -C(0)OR, wherein R is alkenyl as defined herein.

Propargyloxycarbonyl, as used herein, refers to the group -C(0)OCH ₂C≡CH.

Haloalkoxycarbonyl, as used herein, refers to the group -C(0)OR, wherein R is haloalkyl as defined herein.

Alkylcarbonylalkyl, as used herein, refers to the group -RC(0)R, wherein each R is independently alkyl as defined herein.

Alkoxycarbonylalkyl, as used herein, refers to the group -RC(0)OR, wherein each R is independently alkyl as defined herein.

Alkoxyalkylcarbonyl, as used herein, refers to the group -C(0)ROR, wherein each R is independently alkyl as defined herein. Alkoxyalkoxycarbonyl, as used herein, refers to the group -C(0)OROR, wherein each R is independently alkyl as defined herein.

Alkoxycarbonylalkylcarbonyl, as used herein, refers to the group -C(0)RC(0)OR, wherein each R is independently alkyl as defined herein.

Aminocarbonyl, as used herein, refers to the group -C(0)NH ₂. Alkylaminocarbonyl, as used herein, refers to the group -C(0)NHR, wherein R is alkyl as defined herein. Dialkylaminocarbonyl, as used herein, refers to the group -C(0)NRR, wherein each R is independently alkyl as defined herein.

Alkylthiocarbonyl, as used herein, refers to the group -C(0)SR, wherein R is alkyl as defined herein. Alkoxycarbonylaminoalkyl, as used herein, refers to the group -RNHC(0)OR, wherein each R is independently alkyl as defined herein.

Alkylcarbonyloxy, as used herein, refers to the group -OC(0)R, wherein R is alkyl as defined herein.

Alkylcarbonyloxyalkyl, as used herein, refers to the group -ROC(0)R, wherein each R is independently alkyl as defined herein.

Alkoxycarbonyloxyalkyl, as used herein, refers to the group -ROC(0)OR, wherein each R is independently alkyl as defined herein.

Alkylsulfonyl, as used herein, refers to the group -S(0) ₂R, wherein R is alkyl as defined herein.

Haloalkylsulphonyl, as used herein, refers to the group -S(0) ₂R, wherein R is haloalkyl as defined herein.

AlkylsulphonylalkyI, as used herein, refers to the group -RS(0) ₂R, wherein each R is independently alkyl as defined herein.

Aryl, as used herein, refers to an unsaturated aromatic carbocyclic group of from 6 to 10 carbon atoms having a single ring (e. g., phenyl) or multiple condensed (fused) rings, at least one of which is aromatic (e.g., indanyl, naphthyl). Preferred aryl groups include phenyl, naphthyl and the like. Most preferably, an aryl group is a phenyl group.

Aryloxy, as used herein, refers to the group -OAr, wherein Ar is aryl as defined herein. Preferred aryloxy groups include phenoxy, naphthyloxy and the like.

Arylalkyl, as used herein, refers to the group -RAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein. Preferred arylalkyl groups include phenylmethyl (benzyl).

Aryloxyalkyl, as used herein, refers to the group -ROAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.

Arylthio, as used herein, refers to the group -SAr, wherein Ar is aryl as defined herein.

Arylthioalkyl, as used herein, refers to the group -RSAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.

Arylalkylthioalkyl, as used herein, refers to the group -RSRAr, wherein each R is independently alkyl as defined herein and Ar is aryl as defined herein. Arylalkoxyalkyl, as used herein, refers to the group -RORAr, wherein each R is independently alkyl as defined herein and Ar is aryl as defined herein.

Arylcarbonyl, as used herein, refers to the group -C(0)Ar, wherein Ar is aryl as defined herein.

Arylcarbonylalkyl, as used herein, refers to the group -RC(0)Ar, wherein R is alkyl as defined herein and Ar is aryl as defined herein.

Aryloxycarbonyl, as used herein, refers to the group -C(0)OAr, wherein Ar is aryl as defined herein.

Aryloxyalkylcarbonyl, as used herein, refers to the group -C(0)ROAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.

Arylalkoxycarbonyl, as used herein, refers to the group -C(0)ORAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein.

Arylcarbonyloxyalkyl, as used herein, refers to the group -ROC(0)Ar, wherein R is alkyl as defined herein and Ar is aryl as defined herein.

Aryloxycarbonyloxyalkyl, as used herein, refers to the group -ROC(0)OAr, wherein R is alkyl as defined herein and Ar is aryl as defined herein. Arylsulphonyl as used herein refers to the group -S(0) ₂Ar, wherein Ar is aryl as defined herein.

Heteroaryl/heteroaromatic ring, as used herein, refers to a ring system containing 5 to 10 ring atoms, 1 to 4 ring heteroatoms and consisting either of a single aromatic ring or of two or more fused rings, at least one of which is aromatic. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be independently chosen from nitrogen, oxygen and sulfur. When a ring system contains a sulphur atom, the sulphur atom may be present in any one of its oxidation states e.g. -S-, -S(=0)- or -S(=0) ₂-. Examples of such groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl. Examples of bicyclic groups are benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl and pyrazolo[1 ,5- a] pyrimidinyl.

Heteroarylalkyl, as used herein, refers to the group -RHet, wherein R is alkyl as defined herein and Het is heteroaryl as defined herein.

Optionally substituted' as used herein means the group referred to can be substituted at one or more positions by any one or any combination of the radicals listed thereafter. For most groups, one or more hydrogen atoms are replaced by the radicals listed thereafter. For halogenated groups, for example, haloalkyl groups, one or more halogen atoms are replaced by the radicals listed thereafter.

Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula N ⁺(R ²⁹R ³⁰R ³ R ³²) wherein R ²⁹, R ³⁰, R ³ and R ³² are independently selected from hydrogen, Ci-C ₆ alkyl and Ci-C ₆ hydroxyalkyl. Salts of the compounds of formula (I) can be prepared by treatment of compounds of formula (I) with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine. Amine salts are often preferred forms of the compounds of formula (I) because they are water-soluble and lend themselves to the preparation of desirable aqueous based herbicidal compositions.

Acceptable salts can be formed from organic and inorganic acids, for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids when a compound of this invention contains a basic moiety.

The sulphonanilide derivatives of the present invention may be made as the skilled person will appreciate by applying and/or adapting, as appropriate, the methods described in the prior art (see for example, EP2336104 and WO 2010/119906).

In addition, general methods for the production of compounds of formula (I) are described below. Unless otherwise stated in the text, the substituents R, R , R ², R ⁵, R ⁶, R , R ², m, n, p, A, W, X and Z are as defined hereinbefore. The abbreviations LG and LG' as used herein refer to any suitable leaving group, and includes halogen and sulphonate groups. The abbreviation R' as used herein refers to an alkyl group, typically a methyl or ethyl group.

The starting materials used for the preparation of the compounds of the invention may be purchased from usual commercial suppliers or may be prepared by known methods. The starting materials as well as the intermediates may be purified before use in the next step by state of the art methodologies such as chromatography, crystallization, distillation and filtration.

Compounds of formula (I) in which R is H may be prepared from compounds of formula (A) and compounds of formula (B) as shown in reaction scheme 1.

Reaction scheme 1

w (B) (I)

For example, A compound of formula (A) may be heated with a compound of formula (B) in the presence of a catalyst, for example an acid, such as para-toluene sulphonic acid, in a suitable solvent, for example toluene or chlorobenzene. The process may conveniently be carried out using microwave heating or conventional heating in an apparatus for the removal of water, for example a Dean-Stark trap. Compounds of formula (B) are commercially available or can be made by standard methods well known in the chemical literature.

Compounds of formula (A) may be prepared from compounds of formula (C) as shown in reaction scheme 2.

Reaction scheme 2

For example, a compound of formula (C) may be treated with a reducing agent such as lithium aluminium hydride in a suitable solvent such as tetrahydrofuran.

Compounds of formula (C) may be prepared from compounds of formula (D) as shown in reaction scheme 3.

Reaction scheme 3

For example, a compound of formula (D) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.

Compounds of formula (D) are commercially available or can be made by standard methods well known in the chemical literature.

Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (E) as shown in reaction scheme 4.

Reaction scheme 4

(E) (I)

For example, a compound of formula (E) in which LG' is a halogen, for example a chlorine atom, may be treated with a sulphonamide RS0 ₂NH ₂ in the presence of a base, for example an inorganic base such as caesium carbonate or sodium hydride, in a suitable solvent such as dioxane. Optionally the reaction may be performed in the presence of a suitable catalyst, for example a metal catalyst such as a palladium dibenzylidene acetone complex, and optionally a ligand, for example a phosphine ligand such as XantPhos.

Compounds of formula (E) may be prepared from compounds of formula (F) and compounds of formula (B) as shown in reaction scheme 5.

Reaction scheme 5

' (B) (E)

For example, a compound of formula (F) in which LG and LG' are halogens, for example chlorine atoms, may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as sodium hydride, in a suitable solvent, for example tetrahydrofuran.

Compounds of formula (F) are commercially available or can be made by standard methods well known in the chemical literature. For example, compounds of formula (F) may be prepared from compounds of formula (G) as shown in reaction scheme 6. Reaction scheme 6

(G) (F)

For example, a compound of formula (G) may be treated with a halogenating agent, for example /V-bromosuccinimide, in a suitable solvent, for example carbon tetrachloride, optionally in the presence of a reaction initiator, for example a radical initiator such as azobisisobutyronitrile or irradiation with UV or visible light.

Alternatively, compounds of formula (F) may be prepared from compounds of formula (H) as shown in reaction scheme 7.

Reaction scheme 7

(H) (F)

For example, a compound of formula (H) may be treated with a halogenating agent, for example, thionyl chloride, in a suitable solvent, for example dichloromethane.

Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (J) as shown in reaction scheme 8.

Reaction scheme 8

For example, a compound of formula (J) may be treated with a carbonylating agent such as triphosgene, in the presence of a base, for example an organic base such as 2-tert-butyl-1 , 1 ,3,3- tetramethylguanidine (Barton's base), in a suitable solvent, for example dichloromethane.

Compounds of formula (J) may be prepared from aldehydes of formula (K) and amines of formula (L) as shown in reaction scheme 9.

Reaction scheme 9

For example, a compound of formula (J) may be formed by the reaction of an aldehyde of formula (K) with an amine of formula (L) in the presence of a reducing agent, for example a hydride reducing agent such as sodium borohydride, in a suitable solvent, for example an alcohol such as ethanol.

Amines of formula (L) are commercially available or can be made by standard methods well known in the chemical literature.

Aldehydes of formula (K) may be prepared from compounds of formula (M), as shown in reaction scheme 10.

Reaction scheme 10

(K)

For example, an aldehyde of formula (M) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.

Aldehydes of formula (M) are commercially available or can be made by standard methods well known in the chemical literature.

Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (N) as shown in reaction scheme 11.

Reaction scheme 11

(N)

For example, a compound of formula (N) in which LG is a halogen atom, for example a chlorine atom, may be treated with a base, for example an inorganic base such as sodium hydride, in a suitable solvent, such as dimethylformamide.

Compounds of formula (N) may be made from amines of formula (O) and acylating agents of compound (P), as shown in reaction scheme 12.

Reaction scheme 12

(P)

(N)

For example, an amine of formula (O) may be reacted with an acylating agent of formula (P) in which LG and LG' are halogen atom, for example chlorine atoms, in the presence of a suitable base, for example an organic base such as pyridine, in a suitable solvent, for example dichloromethane. Compounds of formula (P) are commercially available or can be made by standard methods well known in the chemical literature.

Amines of formula (O) may be prepared from nitriles of formula (P) as shown in reaction scheme

13.

Reaction scheme 13

For example, a nitrile of formula (Q) may be treated with a reducing agent, for example a hydride reducing agent such as lithium aluminium hydride, in a suitable solvent, for example tetrahydrofuran.

Nitriles of formula (Q) may be prepared from compounds of formula (R), as shown in reaction scheme 14.

Reaction scheme 14

(R)

(Q)

For example, a nitrile of formula (R) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.

Compounds of formula (R) are commercially available or can be made by standard methods well known in the chemical literature.

Compounds of formula (I) in which R is H may alternatively be prepared from compounds of formula (S) as shown in reaction scheme 15

Reaction scheme 15

(S) (I)

For example, a compound of formula (S) may be treated with a sulphonylating reagent, for example a sulphonic anhydride such as trifluoromethanesulphonic anhydride or a sulphonyl halide such as methanesulphonyl chloride, in the presence of a base, for example an organic base such as triethylamine, in a suitable solvent, for example dichloromethane.

Compounds of formula (S) may be prepared from compounds of formula (T) as shown in reaction scheme 16.

Reaction scheme 16

For example, a compound of formula (T) may be treated with a reducing agent, for example a dissolving metal such as iron and ammonium chloride, in a suitable solvent, for example a mixture of water and ethanol.

Compounds of formula (T) may be made from compounds of formula (U) and compounds of formula (B), as shown in reaction scheme 17.

Reaction scheme 17

For example, a compound of formula (U) in which LG is a halogen, for example a bromine atom, may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as sodium hydride or caesium carbonate, in a suitable solvent, for example dimethylformamide.

Compounds of formula (U) are commercially available or can be made by standard methods well known in the chemical literature.

Compounds of formula (I) in which R is not H may be prepared from compounds of formula (I) in which R is H as shown in reaction scheme 18.

Reaction scheme 18

For example, a compound of formula (I) in which R is H may be treated with a base, for example an inorganic base such as sodium hydride or an organic base such as triethylamine, and an electrophilic reagent LG-R , in a suitable solvent, for example dichloromethane.

One skilled in the art will realise that it is often possible to alter the order in which the

transformations described above are conducted, or to combine them in alternative ways to prepare a wide range of compounds of formula (I). Multiple steps may also be combined in a single reaction. All such variations are contemplated within the scope of the invention. The skilled man will also be aware that some reagents will be incompatible with certain values or combinations of the substituents R, R , R ², R ⁵, R ⁶, R , R ², m, n, p, A, W, X and Z as defined herein, and any additional steps, such as protection and/or deprotection steps, which are necessary to achieve the desired transformation will be clear to the skilled man.

The compounds of formula (I) according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. Therefore, the invention also relates to a herbicidal composition which comprises a herbicidally effective amount of a compound of formula (I) in addition to formulation adjuvants. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo- emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. Such formulations can either be used directly or they are diluted prior to use. The dilutions can be made, for example, with water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Ν,Ν-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethyl- hexanol, ethylene carbonate, 1 ,1 , 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N- methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for diluting the concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001. (c) & (d).

A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface- active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium

dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di- alkylphosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981.

Further adjuvants that can usually be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralizing or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilizers.

The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhone-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C ₈-C ₂₂ fatty acids, especially the methyl derivatives of Ci ₂-Ci ₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS- 112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.

The application and action of the oil additives can be further improved by combination with surface- active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non- ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C ₁₂-C ₂₂ fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of the surface-active substances in relation to the total additive is generally from 1 to 30 % by weight. Examples of oil additives consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).

If desired, it is also possible for the mentioned surface-active substances to be used in the formulations on their own, that is to say, without oil additives.

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture may contribute to an additional enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80 % by weight of the total weight. Oil additives that are present in admixture with solvents are described, for example, in US-A-4,834,908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).

In addition to the oil additives listed above, for the purpose of enhancing the action of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray mixture as action-enhancing agent.

The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula (I) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The rates of application of compounds of formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the grass or weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula (I) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.

Preferred formulations have especially the following compositions (% = percent by weight): Emulsifiable concentrates:

active ingredient: 1 to 95 %, preferably 60 to 90 %

surface-active agent: 1 to 30 %, preferably 5 to 20 %

liquid carrier: 1 to 80 %, preferably 1 to 35 % Dusts:

active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %

solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates:

active ingredient: 5 to 75 %, preferably 10 to 50 %

water: 94 to 24 %, preferably 88 to 30 %

surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powders:

active ingredient: 0.5 to 90 %, preferably 1 to 80 %

surface-active agent: 0.5 to 20 %, preferably 1 to 15 %

solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules:

active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %

solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The following Examples further illustrate, but do not limit, the invention.

Formulation Examples for herbicides of formula (I) (% = % by weight)

F1. Emulsifiable concentrates a) b) c) d) active ingredient 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % - 4 % 4 %

(36 mol of ethylene oxide)

octylphenol polyglycol ether - 4 % - 2 %

(7-8 mol of ethylene oxide)

NMP - - 10 % 20 % arom. hydrocarbon mixture 85 % 78 % 55 % 16 % Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.

F2. Solutions a) b) c) d)

active ingredient 5% 10% 50% 90%

1-methoxy-3-(3-methoxy- propoxy)-propane - 20 % 20 %

polyethylene glycol MW 400 20 % 10%

NMP - - 30% 10%

arom. hydrocarbon mixture 75% 60%

The solutions are suitable for use in the form of microdrops.

F3. Wettable powders a) b) c) d)

active ingredient 5% 25% 50% 80%

sodium lignosulfonate 4 % - 3 %

sodium lauryl sulfate 2 % 3 % - 4 %

sodium diisobutylnaphthalene- sulfonate - 6 % 5 % 6 %

octylphenol polyglycol ether - 1 % 2 %

(7-8 mol of ethylene oxide)

highly dispersed silicic acid 1 % 3% 5% 10%

kaolin 88% 62% 35%

The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated qranules a) b) c)

active ingredient 0.1 % 5% 15%

highly dispersed silicic acid 0.9 % 2 % 2 %

inorganic carrier 99.0 % 93 % 83 %

(diameter 0.1 -1 mm)

e.g. CaC0 ₃ or Si0 ₂ The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.

F5. Coated qranules a) b) c)

active ingredient 0.1 % 5 % 15 %

polyethylene glycol MW 200 1.0 % 2 % 3 %

highly dispersed silicic acid 0.9 % 1 % 2 %

inorganic carrier 98.0 % 92 % 80 %

(diameter 0.1 - 1 mm)

e.g. CaC0 ₃ or Si0 ₂

The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

F6. Extruder qranules a) b) c) d)

active ingredient 0.1 % 3 % 5 % 15 %

sodium lignosulfonate 1.5 % 2 % 3 % 4 %

carboxymethylcellulose 1.4 % 2 % 2 % 2 %

kaolin 97.0 % 93 % 90 % 79 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

F7. Dusts a) b) c)

active ingredient 0.1 % 1 % 5 %

talcum 39.9 % 49 % 35 %

kaolin 60.0 % 50 % 60 %

Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d)

active ingredient 3 % 10 % 25 % 50 %

ethylene glycol 5 % 5 % 5 % 5 %

nonylphenol polyglycol ether - 1 % 2 % -

(15 mol of ethylene oxide)

sodium lignosulfonate 3 % 3 % 4 % 5 % carboxymethylcellulose 1 % 1 % 1 % 1 %

37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 %

solution

silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 %

water 87 % 79 % 62 % 38 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension

concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

The invention also provides a method of controlling plants which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I).

The invention also provides a method of inhibiting plant growth which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (I).

The invention also provides a method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful crop plants, a compound or a composition of the invention.

The invention also provides a method of selectively controlling grasses and/or weeds in crops of useful plants which comprises applying to the useful plants or locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (I).

The term "herbicide" as used herein means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on the growth of plants. Controlling or modifying effects include all deviation from natural development, for example: killing, retardation, leaf burn, albinism, dwarfing and the like. The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. The term "locus" is intended to include soil, seeds, and seedlings, as well as established vegetation and includes not only areas where weeds may already be growing, but also areas where weeds have yet to emerge, and also to areas under cultivation with respect to crops of useful plants. "Areas under cultivation" include land on which the crop plants are already growing and land intended for cultivation with such crop plants. The term "weeds" as used herein means any undesired plant, and thus includes not only agronomically important weeds as described below, but also volunteer crop plants.

The compounds of the invention can be applied before or after planting of the crops, before weeds emerge (pre-emergence application) or after weeds emerge (post-emergence application), and are particularly effective when applied pre-emergence.

Crops of useful plants in which the composition according to the invention can be used include, but are not limited to, perennial crops, such as citrus fruit, grapevines, nuts, oil palms, olives, pome fruit, stone fruit and rubber, and annual arable crops, such as cereals, for example barley and wheat, cotton, oilseed rape, maize, rice, soy beans, sugar beet, sugar cane, sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, maize, rice and soy beans.

The grasses and weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eriochloa, Lolium, Monochoria, Panicum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Euphorbia, Galium, Ipomoea, Kochia, Nasturtium, Polygonum, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. auxins or ALS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®, respectively.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesize such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and

Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavor). Any method of application to weeds/crop of useful plant, or locus thereof, which is routinely used in agriculture may be used, for example application by spray or broadcast method typically after suitable dilution of a compound of formula (I) (whether said compound is formulated and/or in combination with one or more further active ingredients and/or safeners, as described herein).

The compounds of formula (I) according to the invention can also be used in combination with other active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators. Such mixtures, and the use of such mixtures to control weeds and/or undesired plant growth, form yet further aspects of the invention. For the avoidance of doubt, mixtures of invention also include mixtures of two or more different compounds of formula (I). In particular, the present invention also relates to a composition of the invention which comprises at least one further herbicide in addition to the compound of formula (I).

When a compound of formula (I) is combined with at least one additional herbicide, the following mixtures of the compound of formula (I) are preferred: compound of formula (I) + acetochlor, compound of formula (I) + acifluorfen, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + aclonifen, compound of formula (I) + acrolein, compound of formula (I) + alachlor, compound of formula (I) + alloxydim, compound of formula (I) + allyl alcohol, compound of formula (I) + ametryn, compound of formula (I) + amicarbazone, compound of formula (I) + amidosulfuron, compound of formula (I) + aminocyclopyrachlor, compound of formula (I) + aminopyralid, compound of formula (I) + amitrole, compound of formula (I) + ammonium sulfamate, compound of formula (I) + anilofos, compound of formula (I) + asulam, compound of formula (I) + atrazine, compound of formula (I) + aviglycine, compound of formula (I) + azafenidin, compound of formula (I) + azimsulfuron, compound of formula (I) + BCPC, compound of formula (I) + beflubutamid, compound of formula (I) + benazolin, compound of formula (I) + bencarbazone, compound of formula (I) + benfluralin, compound of formula (I) + benfuresate, compound of formula (I) + bensulfuron, compound of formula (I) + bensulfuron-methyl, compound of formula (I) + bensulide, compound of formula (I) + bentazone, compound of formula (I) + benzfendizone, compound of formula (I) + benzobicyclon, compound of formula (I) + benzofenap, compound of formula (I) + bicyclopyrone, compound of formula (I) + bifenox, compound of formula (I) + bilanafos, compound of formula (I) + bispyribac, compound of formula (I) + bispyribac-sodium, compound of formula (I) + borax, compound of formula (I) + bromacil, compound of formula (I) + bromobutide, compound of formula (I) + bromophenoxim, compound of formula (I) + bromoxynil, compound of formula (I) + butachlor, compound of formula (I) + butafenacil, compound of formula (I) + butamifos, compound of formula (I) + butralin, compound of formula (I) + butroxydim, compound of formula (I) + butylate, compound of formula (I) + cacodylic acid, compound of formula (I) + calcium chlorate, compound of formula (I) + cafenstrole, compound of formula (I) + carbetamide, compound of formula (I) + carfentrazone, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + CDEA, compound of formula (I) + CEPC, compound of formula (I) + chlorflurenol, compound of formula (I) + chlorflurenol-methyl, compound of formula (I) + chloridazon, compound of formula (I) + chlorimuron, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + chloroacetic acid, compound of formula (I) + chlorotoluron, compound of formula (I) + chlorpropham, compound of formula (I) + chlorsulfuron, compound of formula (I) + chlorthal, compound of formula (I) + chlorthal-dimethyl, compound of formula (I) + cinidon-ethyl, compound of formula (I) + cinmethylin, compound of formula (I) + cinosulfuron, compound of formula (I) + cisanilide, compound of formula (I) + clethodim, compound of formula (I) + clodinafop, compound of formula (I) + clodinafop-propargyl, compound of formula (I) + clomazone, compound of formula (I) + clomeprop, compound of formula (I) + clopyralid, compound of formula (I) + cloransulam, compound of formula (I) + cloransulam-methyl, compound of formula (I) + CMA, compound of formula (I) + 4-CPB, compound of formula (I) + CPMF, compound of formula (I) + 4-CPP, compound of formula (I) + CPPC, compound of formula (I) + cresol, compound of formula (I) + cumyluron, compound of formula (I) + cyanamide, compound of formula (I) + cyanazine, compound of formula (I) + cycloate, compound of formula (I) + cyclosulfamuron, compound of formula (I) + cycloxydim, compound of formula (I) + cyhalofop, compound of formula (I) + cyhalofop-butyl, compound of formula (I) + 2,4-D, compound of formula (I) + 3,4-DA, compound of formula (I) + daimuron, compound of formula (I) + dalapon, compound of formula (I) + dazomet, compound of formula (I) + 2,4-DB, compound of formula (I) + 3,4-DB, compound of formula (I) + 2,4-DEB, compound of formula (I) + desmedipham, formula (I) + desmetryn, compound of formula (I) + dicamba, compound of formula (I) + dichlobenil, compound of formula (I) + ortho-dichlorobenzene, compound of formula (I) + para-dichlorobenzene, compound of formula (I) + dichlorprop, compound of formula (I) + dichlorprop-P, compound of formula (I) + diclofop, compound of formula (I) + diclofop-m ethyl, compound of formula (I) + diclosulam, compound of formula (I) + difenzoquat, compound of formula (I) + difenzoquat metilsulfate, compound of formula (I) + diflufenican, compound of formula (I) + diflufenzopyr, compound of formula (I) + dimefuron, compound of formula (I) + dimepiperate, compound of formula (I) + dimethachlor, compound of formula (I) + dimethametryn, compound of formula (I) + dimethenamid, compound of formula (I) + dimethenamid-P, compound of formula (I) + dimethipin, compound of formula (I) + dimethylarsinic acid, compound of formula (I) + dinitramine, compound of formula (I) + dinoterb, compound of formula (I) + diphenamid, formula (I) + dipropetryn, compound of formula (I) + diquat, compound of formula (I) + diquat dibromide, compound of formula (I) + dithiopyr, compound of formula (I) + diuron, compound of formula (I) + DNOC, compound of formula (I) + 3,4-DP, compound of formula (I) + DSMA, compound of formula (I) + EBEP, compound of formula (I) + endothal, compound of formula (I) + EPTC, compound of formula (I) + esprocarb, compound of formula (I) + ethalfluralin, compound of formula (I) + ethametsulfuron, compound of formula (I) + ethametsulfuron-methyl, compound of formula (I) + ethephon, compound of formula (I) + ethofumesate, compound of formula (I) + ethoxyfen, compound of formula (I) + ethoxysulfuron, compound of formula (I) + etobenzanid, compound of formula (I) + fenoxaprop, compound of formula (I) + fenoxaprop-P, compound of formula (I) + fenoxaprop-ethyl, compound of formula (I) + fenoxaprop-P-ethyl, compound of formula (I) + fenoxasulfone, compound of formula (I) + fentrazamide, compound of formula (I) + ferrous sulfate, compound of formula (I) + flamprop- M, compound of formula (I) + flazasulfuron, compound of formula (I) + florasulam, compound of formula (I) + fluazifop, compound of formula (I) + fluazifop-butyl, compound of formula (I) + fluazifop-P, compound of formula (I) + fluazifop-P-butyl, formula (I) + fluazolate, compound of formula (I) + flucarbazone, compound of formula (I) + flucarbazone-sodium, compound of formula (I) + flucetosulfuron, compound of formula (I) + fluchloralin, compound of formula (I) + flufenacet, compound of formula (I) + flufenpyr, compound of formula (I) + flufenpyr-ethyl, compound of formula (I) + flumetralin, compound of formula (I) + flumetsulam, compound of formula (I) + flumiclorac, compound of formula (I) + flumiclorac-pentyl, compound of formula (I) + flumioxazin, compound of formula (I) + flumipropin, compound of formula (I) + fluometuron, compound of formula (I) + fluoroglycofen, compound of formula (I) + f I uoroglycof en-ethyl, formula (I) + fluoxaprop, compound of formula (I) + flupoxam, compound of formula (I) + flupropacil, compound of formula (I) + flupropanate, compound of formula (I) + flupyrsulfuron, compound of formula (I) + flupyrsulfuron-methyl-sodium, compound of formula (I) + flurenol, compound of formula (I) + fluridone, compound of formula (I) + flurochloridone, compound of formula (I) + fluroxypyr, compound of formula (I) + flurtamone, compound of formula (I) + fluthiacet, compound of formula (I) + fluthiacet-methyl, compound of formula (I) + fomesafen, compound of formula (I) + foramsulfuron, compound of formula (I) + fosamine, compound of formula (I) + glufosinate, compound of formula (I) + glufosinate-ammonium, compound of formula (I) + glyphosate, compound of formula (I) + halauxifen, compound of formula (I) + haloauxifen- methyl, compound of formula (I) + halosulfuron, compound of formula (I) + halosulfuron-methyl, compound of formula (I) + haloxyfop, compound of formula (I) + haloxyfop-P, compound of formula (I) + HC-252, compound of formula (I) + hexazinone, compound of formula (I) + imazamethabenz, compound of formula (I) + imazamethabenz-methyl, compound of formula (I) + imazamox, compound of formula (I) + imazapic, compound of formula (I) + imazapyr, compound of formula (I) + imazaquin, compound of formula (I) + imazethapyr, compound of formula (I) + imazosulfuron, compound of formula (I) + indanofan, compound of formula (I) and indaziflam, compound of formula (I) + iodomethane, compound of formula (I) + iodosulfuron, compound of formula (I) + iodosulfuron-methyl-sodium, compound of formula (I) + iofensulfuron, compound of formula (I) + ioxynil, compound of formula (I) and ipfencarbazone, compound of formula (I) + isoproturon, compound of formula (I) + isouron, compound of formula (I) + isoxaben, compound of formula (I) + isoxachlortole, compound of formula (I) + isoxaflutole, formula (I) + isoxapyrifop, compound of formula (I) + karbutilate, compound of formula (I) + lactofen, compound of formula (I) + lenacil, compound of formula (I) + linuron, compound of formula (I) + MAA, compound of formula (I) + MAMA, compound of formula (I) + MCPA, compound of formula (I) + MCPA-thioethyl, compound of formula (I) + MCPB, compound of formula (I) + mecoprop, compound of formula (I) + mecoprop-P, compound of formula (I) + mefenacet, compound of formula (I) + mefluidide, compound of formula (I) + mesosulfuron, compound of formula (I) + mesosulfuron-methyl, compound of formula (I) + mesotrione, compound of formula (I) + metam, compound of formula (I) + metamifop, compound of formula (I) + metamitron, compound of formula (I) + metazachlor, compound of formula (I) and metazosulfuron, compound of formula (I) + methabenzthiazuron, compound of formula (I) + methazole, compound of formula (I) + methiozolin, compound of formula (I) + methylarsonic acid, compound of formula (I) + methyldymron, compound of formula (I) + methyl isothiocyanate, compound of formula (I) +

metobenzuron, compound of formula (I) + metobromuron, compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + metosulam, compound of formula (I) + metoxuron, compound of formula (I) + metribuzin, compound of formula (I) + metsulfuron, compound of formula (I) + metsulfuron-methyl, compound of formula (I) + MK-616, compound of formula (I) + molinate, compound of formula (I) + monolinuron, a compound of formula (I) +monosulfuron, compound of formula (I) + monosulfuron-ester, compound of formula (I) + MSMA, compound of formula (I) + naproanilide, compound of formula (I) + napropamide, compound of formula (I) + naptalam, compound of formula (I) + NDA-402989, compound of formula (I) + neburon, compound of formula (I) + nicosulfuron, compound of formula (I) + nipyraclofen, compound of formula (I) + n-methyl glyphosate, compound of formula (I) + nonanoic acid, compound of formula (I) + norflurazon, compound of formula (I) + oleic acid (fatty acids), compound of formula (I) + orbencarb, compound of formula (I) + orthosulfamuron, compound of formula (I) + oryzalin, compound of formula (I) + oxadiargyl, compound of formula (I) + oxadiazon, compound of formula (I) + oxasulfuron, compound of formula (I) + oxaziclomefone, compound of formula (I) + oxyfluorfen, compound of formula (I) + paraquat, compound of formula (I) + paraquat dichloride, compound of formula (I) + pebulate, compound of formula (I) + pendimethalin, compound of formula (I) + penoxsulam, compound of formula (I) + pentachlorophenol, compound of formula (I) + pentanochlor, compound of formula (I) + pentoxazone, compound of formula (I) + pethoxamid, compound of formula (I) + petroleum oils, compound of formula (I) + phenmedipham, compound of formula (I) + phenmedipham- ethyl, compound of formula (I) + picloram, compound of formula (I) + picolinafen, compound of formula (I) + pinoxaden, compound of formula (I) + piperophos, compound of formula (I) + potassium arsenite, compound of formula (I) + potassium azide, compound of formula (I) + pretilachlor, compound of formula (I) + primisulfuron, compound of formula (I) + primisulfuron-methyl, compound of formula (I) + prodiamine, compound of formula (I) + profluazol, compound of formula (I) + profoxydim, compound of formula (I) + prohexadione-calcium, compound of formula (I) + prometon, compound of formula (I) + prometryn, compound of formula (I) + propachlor, compound of formula (I) + propanil, compound of formula (I) + propaquizafop, compound of formula (I) + propazine, compound of formula (I) + propham, compound of formula (I) + propisochlor, compound of formula (I) + propoxycarbazone, compound of formula (I) + propoxycarbazone-sodium, compound of formula (I) + propyzamide, compound of formula (I) + prosulfocarb, compound of formula (I) + prosulfuron, compound of formula (I) + pyraclonil, compound of formula (I) + pyraflufen, compound of formula (I) + pyraflufen-ethyl, compound of formula (I) + pyrasulfotole, compound of formula (I) + pyrazolynate, compound of formula (I) + pyrazosulfuron, compound of formula (I) + pyrazosulfuron-ethyl, compound of formula (I) + pyrazoxyfen, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyributicarb, compound of formula (I) + pyridafol, compound of formula (I) + pyridate, compound of formula (I) + pyriftalid, compound of formula (I) + pyriminobac, compound of formula (I) + pyriminobac-methyl, compound of formula (I) + pyrimisulfan, compound of formula (I) + pyrithiobac, compound of formula (I) + pyrithiobac-sodium, compound of formula (I) + pyroxasulfone, compound of formula (I) + pyroxulam, compound of formula (I) + quinclorac, compound of formula (I) + quinmerac, compound of formula (I) + quinoclamine, compound of formula (I) + quizalofop, compound of formula (I) + quizalofop-P, compound of formula (I) + quizalofop-ethyl, compound of formula (I) + quizalofop-P-ethyl, compound of formula (I) + rimsulfuron, compound of formula (I) + saflufenacil, compound of formula (I) + sethoxydim, compound of formula (I) + siduron, compound of formula (I) + simazine, compound of formula (I) + simetryn, compound of formula (I) + SMA, compound of formula (I) + sodium arsenite, compound of formula (I) + sodium azide, compound of formula (I) + sodium chlorate, compound of formula (I) + sulcotrione, compound of formula (I) + sulfentrazone, compound of formula (I) + sulfometuron, compound of formula (I) + sulfometuron-methyl, compound of formula (I) + sulfosate, compound of formula (I) + sulfosulfuron, compound of formula (I) + sulfuric acid, compound of formula (I) + tar oils, compound of formula (I) + 2,3,6-TBA, compound of formula (I) + TCA, compound of formula (I) + TCA-sodium, compound of formula (I) + tebutam, compound of formula (I) + tebuthiuron, compound of formula (I) + tefuryltrione, compound of formula (I) + tembotrione, compound of formula (I) + tepraloxydim, compound of formula (I) + terbacil, compound of formula (I) + terbumeton, compound of formula (I) + terbuthylazine, compound of formula (I) + terbutryn, compound of formula (I) + thenylchlor, compound of formula (I) + thiazafluron, compound of formula (I) + thiazopyr, compound of formula (I) + thifensulfuron, compound of formula (I) + thiencarbazone, compound of formula (I) + thifensulfuron-methyl, compound of formula (I) + thiobencarb, compound of formula (I) + tiocarbazil, compound of formula (I) + topramezone, compound of formula (I) + tralkoxydim, a compound of formula (I) and triafamone, compound of formula (I) + tri-allate, compound of formula (I) + triasulfuron, compound of formula (I) + triaziflam, compound of formula (I) + tribenuron, compound of formula (I) + tribenuron-methyl, compound of formula (I) + tricamba, compound of formula (I) + triclopyr, compound of formula (I) + trietazine, compound of formula (I) + trifloxysulfuron, compound of formula (I) +

trifloxysulfuron-sodium, compound of formula (I) + trifluralin, compound of formula (I) + triflusulfuron, compound of formula (I) + triflusulfuron-methyl, compound of formula (I) + trifop, compound of formula (I) + trifop-methyl, compound of formula (I) + trihydroxytriazine, compound of formula (I) + trinexapac-ethyl, compound of formula (I) + tritosulfuron, compound of formula (I) + [3-[2-chloro-4-fluoro-5-(1-methyl-6- trifluoromethyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester (CAS RN 353292-31-6), compound of formula (I) + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione and the compound of formula (I) + VX-573.

In particular, the following mixtures are important:

Mixtures of a compound of the formula (I) with a triazine (e.g. compound of formula (I) + ametryn, compound of formula (I) + atrazine, compound of formula (I) + cyanazine, compound of formula (I) + dimethametryn, compound of formula (I) + metribuzin, compound of formula (I) + prometon, compound of formula (I) + prometryn, compound of formula (I) + propazine, compound of formula (I) + simazine, compound of formula (I) + simetryn, compound of formula (I) + terbumeton, compound of formula (I) + terbuthylazine, compound of formula (I) + terbutryn, compound of formula (I) + trietazine).

Mixtures of a compound of formula (I) with an HPPD inhibitor (e.g. compound of formula (I) + isoxaflutole, compound of formula (I) + mesotrione, compound of formula (I) + pyrasulfotole, compound of formula (I) + sulcotrione, compound of formula (I) + tembotrione, compound of formula (I) + topramezone, compound of formula (I) + bicyclopyrone, compound of formula (I) + benzobicyclon or compound of formula (I) + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxa linyl]carbonyl]1 ,3- cyclohexanedione (CAS RN 1342891-70-6)).

Mixtures of a compound of formula (I) with an auxin (e.g. compound of formula (I) + dicamba, compound of formula (I) + 2,4-D, compound of formula (I) + 2,4-DB, compound of formula (I) + MCPA, compound of formula (I) + fluroxypyr, compound of formula (I) + picloram, compound of formula (I) + triclopyr, compound of formula (I) + quinclorac, compound of formula (I) + clopyralid, compound of formula (I) + aminopyralid, compound of formula (I) + aminocyclopyrachlor, compound of formula (I) + halauxifen, compound of formula (I) + halauxifen-methyl). Mixtures of a compound of formula (I) with a VLCFA inhibitor (e.g. compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + acetochlor, compound of formula (I) + dimethenamid-P, compound of formula (I) + pyroxasulfone, compound of formula (I) + dimethachlor, compound of formula (I) + flufenacet, compound of formula (I) + metazachlor, compound of formula (I) + napropamide, compound of formula (I) + pretilachlor). Mixtures of a compound of formula (I) with a triazolinone (e.g. compound of formula (I) + amicarbazone).

Mixtures of a compound of formula (I) with an ALS inhibitor (e.g. compound of formula (I) + chlorsulfuron, compound of formula (I) + cinosulfuron, compound of formula (I) + cloransulam, compound of formula (I) + ethametsulfuron, compound of formula (I) + flazasulfuron, compound of formula (I) + foramsulfuron, compound of formula (I) + flumetsulam, compound of formula (I) + imazamethabenz, compound of formula (I) + imazamox, compound of formula (I) + imazapic, compound of formula (I) + imazapyr, compound of formula (I) + imazethapyr, compound of formula (I) + iodosulfuron, compound of formula (I) + iofensulfuron, compound of formula (I) + metsulfuron, compound of formula (I) + nicosulfuron, compound of formula (I) + oxasulfuron, compound of formula (I) + primisulfuron, compound of formula (I) + prosulfuron, compound of formula (I) + pyrithiobac, compound of formula (I) + pyroxsulam, compound of formula (I) + rimsulfuron, compound of formula (I) + sulfosulfuron, compound of formula (I) +

thifensulfuron, compound of formula (I) + triasulfuron, compound of formula (I) + tribenuron, compound of formula (I) + trifloxysulfuron, compound of formula (I) + thiencarbazone, compound of formula (I) + tritosulfuron, compound of formula (I) + bispyribac-sodium, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) +flucarbazone-sodium, compound of formula (I) +bensulfuron-methyl, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + sulfometuron-methyl, compound of formula (I) + diclosulam, compound of formula (I) + florasulam, compound of formula (I) + penoxsulam).

Mixtures of a compound of formula (I) with a PPO inhibitor (e.g. compound of formula (I) + fomesafen, compound of formula (I) + flumioxazin, compound of formula (I) + sulfentrazone, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + lactofen, compound of formula (I) + oxyfluorfen, compound of formula (I) + oxadiazon, compound of formula (I) + butafenacil, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoro- methyl-2,4-dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester).

Mixtures of a compound of formula (I) with and ACCase inhibitor (i.e. compound of formula (I) + clodinafop, compound of formula (I) + fluazifop, compound of formula (I) + fenoxaprop, compound of formula (I) + clethodim, compound of formula (I) + quizalofop, compound of formula (I) + haloxyfop, compound of formula (I) + pinoxaden, compound of formula (I) + cycloxydim, compound of formula (I) + sethoxydim).

In addition, the following mixtures are also preferred: compound of formula (I) + glyphosate, compound of formula (I) + glufosinate, compound of formula (I) + paraquat, compound of formula (I) + diquat, compound of formula (I) + pendimethalin, compound of formula (I) + trifluralin, compound of formula (I) + metamitron, compound of formula (I) + clomazone, compound of formula (I) + prodiamine, compound of formula (I) + saflufenacil, compound of formula (I) + prosulfocarb, compound of formula (I) + diflufenican, compound of formula (I) + isoxaben, compound of formula (I) + beflubutamide, compound of formula (I) + flurtamone, compound of formula (I) + benfluralin, compound of formula (I) + chlorotoluron, compound of formula (I) +linuron, compound of formula (I) + isoproturon, compound of formula (I) + triallate, compound of formula (I) + hexazinone, compound of formula (I) + diuron, compound of formula (I) + propanil, compound of formula (I) + indaziflam.

Thus, in particular, the following mixtures are preferred: compound of formula (I) + ametryn, compound of formula (I) + atrazine, compound of formula (I) + cyanazine, compound of formula (I) + dimethametryn, compound of formula (I) + metribuzin, compound of formula (I) + prometon, compound of formula (I) + prometryn, compound of formula (I) + propazine, compound of formula (I) + simazine, compound of formula (I) + simetryn, compound of formula (I) + terbumeton, compound of formula (I) + terbuthylazine, compound of formula (I) + terbutryn, compound of formula (I) + trietazine, compound of formula (I) + isoxaflutole, compound of formula (I) + mesotrione, compound of formula (I) + pyrasulfotole, compound of formula (I) + sulcotrione, compound of formula (I) + tembotrione, compound of formula (I) + topramezone, compound of formula (I) + bicyclopyrone, compound of formula (I ) + benzobicyclon compound of formula (I) + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione (CAS RN 1342891-70-6), compound of formula (I) + dicamba, compound of formula (I) + 2,4-D, compound of formula (I) + 2,4-DB, compound of formula (I) + MCPA, compound of formula (I) + fluroxypyr, compound of formula (I) + picloram, compound of formula (I) + triclopyr, compound of formula (I) + quinclorac, compound of formula (I) + clopyralid, compound of formula (I) + aminopyralid, compound of formula (I) + aminocyclopyrachlor, compound of formula (I) + halauxifen, compound of formula (I) + halauxifen-methyl, compound of formula (I) + metolachlor, compound of formula (I) + S-metolachlor, compound of formula (I) + acetochlor, compound of formula (I) + dimethenamid-P, compound of formula (I) + pyroxasulfone, compound of formula (I) + dimethachlor, compound of formula (I) + flufenacet, compound of formula (I) + metazachlor, compound of formula (I) + napropamide, compound of formula (I) + pretilachlor, compound of formula (I) + amicarbazone, compound of formula (I) + chlorsulfuron, compound of formula (I) + cinosulfuron, compound of formula (I) + cloransulam, compound of formula (I) + ethametsulfuron, compound of formula (I) + flazasulfuron, compound of formula (I) + foramsulfuron, compound of formula (I) + flumetsulam, compound of formula (I) + imazamethabenz, compound of formula (I) + imazamox, compound of formula (I) + imazapic, compound of formula (I) + imazapyr, compound of formula (I) + imazethapyr, compound of formula (I) + iodosulfuron, compound of formula (I) + iofensulfuron, compound of formula (I) + metsulfuron, compound of formula (I) + nicosulfuron, compound of formula (I) + oxasulfuron, compound of formula (I) + primisulfuron, compound of formula (I) + prosulfuron, compound of formula (I) + pyrithiobac, compound of formula (I) + pyroxsulam, compound of formula (I) + rimsulfuron, compound of formula (I) + sulfosulfuron, compound of formula (I) + thifensulfuron, compound of formula (I) + triasulfuron, compound of formula (I) + tribenuron, compound of formula (I) + trifloxysulfuron, compound of formula (I) + thiencarbazone, compound of formula (I) + tritosulfuron, compound of formula (I) + bispyribac-sodium, compound of formula (I) + pyribenzoxim, compound of formula (I) + pyriftalid, compound of formula (I) +flucarbazone- sodium, compound of formula (I) +bensulfuron-methyl, compound of formula (I) + chlorimuron-ethyl, compound of formula (I) + sulfometuron-methyl, compound of formula (I) + diclosulam, compound of formula (I) + florasulam, compound of formula (I) + penoxsulam, compound of formula (I) + fomesafen, compound of formula (I) + flumioxazin, compound of formula (I) + sulfentrazone, compound of formula (I) + acifluorfen-sodium, compound of formula (I) + lactofen, compound of formula (I) + oxyfluorfen, compound of formula (I) + oxadiazon, compound of formula (I) + butafenacil, compound of formula (I) + carfentrazone-ethyl, compound of formula (I) + [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4- dioxo-1 ,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester, compound of formula (I) + clodinafop, compound of formula (I) + fluazifop, compound of formula (I) + fenoxaprop, compound of formula (I) + clethodim, compound of formula (I) + quizalofop, compound of formula (I) + haloxyfop, compound of formula (I) + pinoxaden, compound of formula (I) + cycloxydim, compound of formula (I) + sethoxydim, compound of formula (I) + glyphosate, compound of formula (I) + glufosinate, compound of formula (I) + paraquat, compound of formula (I) + diquat, compound of formula (I) + pendimethalin, compound of formula (I) + trifluralin, compound of formula (I) + metamitron, compound of formula (I) + clomazone, compound of formula (I) + prodiamine, compound of formula (I) + saflufenacil, compound of formula (I) + prosulfocarb, compound of formula (I) + diflufenican, compound of formula (I) + isoxaben, compound of formula (I) + beflubutamide, compound of formula (I) + flurtamone, compound of formula (I) + benfluralin, compound of formula (I) + chlorotoluron, compound of formula (I) +linuron, compound of formula (I) + isoproturon, compound of formula (I) + triallate, compound of formula (I) + hexazinone, compound of formula (I) + diuron, compound of formula (I) + propanil, compound of formula (I) + indaziflam.

The following mixtures are particularly preferred: compound of formula (I) + atrazine, compound of formula (I) + terbuthylazine, compound of formula (I) + isoxaflutole, compound of formula (I) + mesotrione, compound of formula (I) + S-metolachlor, compound of formula (I) + acetochlor, compound of formula (I) + pyroxasulfone, compound of formula (I) + dimethachlor, compound of formula (I) + flufenacet, compound of formula (I) + nicosulfuron, compound of formula (I) + fomesafen, compound of formula (I) + glyphosate, compound of formula (I) + glufosinate, compound of formula (I) + paraquat, compound of formula (I) + saflufenacil, compound of formula (I) + prosulfocarb.

For the avoidance of doubt, the present invention also includes three-way mixtures of a compound of formula (I), a herbicide as defined above and a further herbicide. In particular, the following three-way mixtures are preferred: compound of formula (I) + atrazine + mesotrione, compound of formula (I) + atrazine + S-metolachlor, compound of formula (I) + S-metolachlor + mesotrione, compound of formula (I) + glyphosate + mesotrione, compound of formula (I) + glufosinate + mesotrione, compound of formula (I) + atrazine + isoxaflutole, compound of formula (I) + S-metolachlor + isoxaflutole, compound of formula (I) + glyphosate + isoxaflutole, compound of formula (I) + glufosinate + isoxaflutole, compound of formula (I) + glyphosate + fomesafen.

In addition, the present invention also includes four-way mixtures of a compound of formula (I), a herbicide as defined above and two further herbicides. In particular, the following four-way mixtures is preferred: the compound of formula (I) + atrazine + mesotrione + S-metolachlor. The mixing partners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. The reference to acifluorfen-sodium also applies to acifluorfen, the reference to dimethenamid also applies to dimethenamid-P, the reference to glufosinate-ammonium also applies to glufosinate, the reference to bensulfuron-methyl also applies to bensulfuron, the reference to cloransulam-methyl also applies to cloransulam, the reference to flamprop- M also applies to flamprop, and the reference to pyrithiobac-sodium also applies to pyrithiobac, etc.

The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 to

1000: 1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) with the mixing partner). The mixtures according to the invention can also be used in combination with further active ingredients, e.g. further herbicides and/or insecticides and/or acaricides and/or nematocides and/or molluscicides and/or fungicides and/or plant growth regulators. Such mixtures, and the use of such mixtures to control weeds and/or undesired plant growth, form yet further aspects of the invention. For the avoidance of doubt, mixtures of invention also include mixtures of two or more different compounds of formula (I).

The compounds of formula (I) according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of a compound of formula (I) according to the invention with one or more further active ingredients, in particular with one or more further herbicides, can also be used in combination with one or more safeners. The term "safener" as used herein means a chemical that when used in combination with a herbicide reduces the undesirable effects of the herbicide on non-target organisms, for example, a safener protects crops from injury by herbicides but does not prevent the herbicide from killing the weeds. Where a compound of formula (I) is combined with a safener, the following combinations of the compound of formula (I) and the safener are particularly preferred.

Compound of formula (I) + AD 67 (MON 4660), compound of formula (I) + benoxacor, compound of formula (I) + cloquintocet-mexyl, compound of formula (I) + cyometrinil and a compound of formula (I) + the corresponding (Z) isomer of cyometrinil, compound of formula (I) + cyprosulfamide (CAS RN 221667- 31-8), compound of formula (I) + dichlormid, compound of formula (I) and dicyclonon, compound of formula (I) and dietholate, compound of formula (I) + fenchlorazole-ethyl, compound of formula (I) + fenclorim, compound of formula (I) + flurazole, compound of formula (I) + fluxofenim, compound of formula (I) + furilazole and a compound of formula (I) + the corresponding R isomer or furilazome, compound of formula (I) + isoxad if en-ethyl, compound of formula (I) + mefenpyr-diethyl, compound of formula (I) and mephenate, compound of formula (I) + oxabetrinil, compound of formula (I) + naphthalic anhydride (CAS RN 81-84-5), compound of formula (I) and TI-35, compound of formula (I) + N-isopropyl- 4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4) and a compound of formula (I) + N- (2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulf onamide.

In particular, the following compound/safener combinations are preferred: compound of formula (I) + cloquintocet-mexyl, compound of formula (I) + cyprosulfamide, compound of formula (I) + N-(2- methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfona mide, compound of formula (I) + isoxad if en-ethyl, compound of formula (I) + benoxacor, compound of formula (I) + dichlormid and the compound of formula (I) + fluxofenim .

The safeners of the compound of formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. The reference to cloquintocet-mexyl also applies to cloquintocet and to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO02/34048 and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.

Preferably the mixing ratio of compound of formula (I) to safener is from 100: 1 to 1 :10, especially from 20: 1 to 1 : 1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (I) and any further active ingredient, in particular a further herbicide, with the safener). It is possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied simultaneously. For example, the safener, a compound of formula (I) and one or more additional herbicide(s), if any, might be applied to the locus pre-emergence or might be applied to the crop post-emergence. It is also possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied sequentially. For example, the safener might be applied before sowing the seeds as a seed treatment and a compound of formula (I) and one or more additional herbicides, if any, might be applied to the locus pre-emergence or might be applied to the crop post-emergence.

For the avoidance of doubt, where a literary reference, patent application, or patent, is cited within the text of this application, the entire text of said citation is herein incorporated by reference.

Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention.

EXAMPLES Example 1 : Synthesis of A -{2-methyl-4-[(2-oxo-1 -piperidyl)-methyl]-pyrazol-3-yl}- methanesulfonamide (Compound 15-55)

Step 1.1 Synthesis of ethyl 5-(methanesulfonamido)-1-methyl-pyrazole-4-carboxylate

Triethylamine (0.49 ml, 3.5 mmol) was added to a stirred solution of ethyl 5-amino-1-methyl-pyrazole-4- carboxylate (0.50 g, 3.0 mmol) in dichloromethane (30 ml) at 0°C. After 5 minutes methanesulfonyl chloride (0.23 ml, 3.0 mmol) was added dropwise. The resulting mixture was allowed to warm to room temperature over 18 hours and then partitioned between 1 M hydrochloric acid and dichloromethane. The phases were separated and the aqueous extracted with further dichloromethane. The combined organic phases were passed through a PhaseSep® cartridge and concentrated under reduced pressure to leave ethyl 5-(methanesulfonamido)-1-methyl-pyrazole-4-carboxylate, which was used without further purification.

Characterising data for the compound are as follows: H NMR (400 MHz, CDCI ₃) δ 7.97 (s, 1 H), 4.34 (t, 2H), 3.92 (s, 3H), 3.51 (s, 3H) and 1.36 (t, 3H) ppm.

Other compounds made using this general method are listed in Table 2 below.

TABLE 2 Compounds made according to the general method described in Step 1.1.

Step 1.2 Synthesis of A/-[4-(hvdroxymethvn-2-methyl-pyrazol-3-yll-methanesulfonami de

A solution of ethyl 5-(methanesulfonamido)-1 -methyl-pyrazole-4-carboxylate (0.55 g, 2.2 mmol) in tetrahydrofuran (6.7 ml) was added to a stirred suspension of lithium aluminium hydride (1 M solution in tetrahydrofuran; 5.6 ml, 5.6 mmol) at -20°C. The resulting mixture was allowed to warm to room temperature, stirred for 1 hour, then water added. The mixture was adjusted to pH 4 and extracted twice with ether. The aqueous phase was then further acidified to pH 1 and extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate and concentrated under reduced pressure to provide A/-[4-(hydroxymethyl)-2-methyl-pyrazol-3-yl]-methanesulfonam ide (0.121 g, 27%). Characterising data for the compound are as follows: H NMR (400 MHz, d6-DMSO) δ 7.02 (s, 1 H), 4.09 (s, 2 H) and 3.46 (s, 6 H) ppm.

Other compounds made using this general method are listed in Table 3 below.

TABLE 3 Compounds made according to the general method described in Step 1.2.

Step 1.3 Synthesis of A/-{2-methyl-4-[(2-oxo-1-piperidvn-methyll-pyrazol-3-yl)-met hanesulfonamide (Compound 15-55)

A mixture of A/-[4-(hydroxymethyl)-2-methyl-pyrazol-3-yl]-methanesulfonam ide (0.121 g, 0.590 mmol), 4- methylbenzenesulfonic acid hydrate (0.1 12 g, 0.590 mmol), piperidin-2-one (0.058 g, 0.590 mmol) and toluene (2.95 ml) was heated at 140°C under microwave irradiation for 30 minutes. The mixture was allowed to cool, water and ethyl acetate added and the phases separated. The aqueous phase was acidified with dilute hydrochloric acid and extracted with ethyl acetate. The combined organic phases were dried over magnesium sulphate and concentrated under reduced pressure. The residue was purified by reverse phase preparative HPLC, using FractionLynx (X Bridge column, ammonium acetate buffer) to give A/-{2-methyl-4-[(2-oxo-1-piperidyl)-methyl]-pyrazol-3-yl}-me thanesulfonamide (43 mg, 25%).

Characterising data for the compound are as follows: ¹ H NMR (400 MHz, CDCI ₃) δ 9.17 (br s, 1 H), 7.36 (s, 1 H), 4.13 (s, 2H), 3.67 (s, 3H), 3.13 (m, 2H), 2.99 (s, 3H), 2.17 (t, 2H) and 1.64 (m, 4H) ppm. compounds made using this general method are listed in Table 4 below.

TABLE 4 Compounds made according to the general method described in Step 1.3.

Characteristic data is melting point (°C) or ¹H nmr data (400 MHz, CDCI ₃ unless otherwise stated) δΗ ppm.

Example 2: Synthesis of A -{4-[(4-methyl-2-oxo-1 -piperidyl)-methyl]-pyrimidin-5-yl}- methanesulfonamide (Compound 60-64) Step 2.1 Synthesis of 5-bromo-4-bromomethylpyrimidine

/V-Bromosuccinimide (5.96 g, 31.8 mmol) and azobisisobutyronitrile (0.50 g, 2.9 mmol) were added to a solution of 5-bromo-4-methyl-pyrimidine (5 g, 29 mmol) in carbon tetrachloride (72 ml). The resulting mixture was heated at reflux for 16 hours, then allowed to cool and filtered. The solid was washed with dichloromethane and the filtrate concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography (gradient elution: 5 - 100% ethyl acetate in /so-hexane) to provide 5- bromo-4-bromomethylpyrimidine (4.22 g, 58%). Characterising data for the compound are as follows: ¹ H NMR (400 MHz, CDCI ₃) δ 9.10 (s, 1 H), 8.84 (s, 1 H) and 4.57 (s, 2H) ppm.

Other compounds made using this general method are listed in Table 5 below.

TABLE 5 Compounds made according to the general method described in Step 2.1.

Name Structure Ή nmr data (400 MHz, CDCI ₃) δ _Η ppm

5-Bromomethyl-4- 8.95 (s, 1 H), 8.77 (s, 1 H), 4.53 (s,

chloropyrimidine 2H) Step 2.2 Synthesis of 1-[(5-bromopyrimidin-4-yl)-methyll-4-methyl-piperidin-2-one

Sodium hydride (0.543 g, 13.6 mmol) was added to a stirred solution of 4-methylpiperidin-2-one (1.23 g, 10.9 mmol) in tetrahydrofuran (27 ml) at 0°C. After 1 hour a solution of 5-bromo-4-(bromomethyl)- pyrimidine (4.22 g, 9.04 mmol) in tetrahydrofuran (13 ml) was added and the mixture stirred for 15 minutes at 0°C then allowed to slowly warm to ambient temperature over 20 hours. Dilute hydrochloric acid and ethyl acetate were added and the phases separated. The aqueous phase was extracted with ethyl acetate and the combined organic phases were washed with brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure to leave a residue that was purified by silica gel chromatography (gradient elution: 25 - 100% ethyl acetate in /so-hexane) to provide 1-[(5-bromopyrimidin-4-yl)-methyl]-4-methyl-piperidin-2-one (1 .08 g, 42%).

Characterising data for the compound are as follows: ¹ H NMR (400 MHz, CDCI ₃) δ 9.00 (s, 1 H), 8.71 (s, 1 H), 4.73 (ABq, 2H), 3.49 (m, 1 H), 3.40 (m, 1 H), 2.59 (m, 1 H), 2.1 1 (m, 2H), 1.90 (m, 1 H), 1.60 (m, 1 H) and 1 .09 (d, 3H) ppm.

Other compounds made using this general method are listed in Table 6 below.

TABLE 6 Compounds made according to the general method described in Step 2.2.

Name Structure Ή nmr data (400 MHz, CDCI ₃) δ _Η ppm

4-[(5- 9.05 (s, 1 H), 8.77 (s, 1 H), 4.79 (s,

Br O

Bromopyrimidin- 2H), 4.30 (s, 2H), 4.00 (t, 2H), 3.55

4-yl)-methyl]- (t, 2H)

morpholin-3-one

1- 1(4- 8.90 (s, 1 H), 8.59 (s, 1 H), 4.70

Chloropyrimidin- (ABq, 2H), 3.40 (m, 2H), 2.60 (br d,

5-yl)-methyl]-4- 1 H), 2.04 (m, 3H), 1.56 (m, 1 H), methyl-piperidin- 1.08 (d, 3H)

2- one ⁰^ ⁰k

Step 2.3 Synthesis of /V-{4-[(4-methyl-2-oxo-1-piperidvn-methyll-pyrimidin-5-yl)-m eth

(Compound 60-64)

A mixture of 1-[(5-bromopyrimidin-4-yl)-methyl]-4-methyl-piperidin-2-one (0.5 g, 1.76 mmol),

methanesulfonamide (0.184 g, 1 .94 mmol), caesium carbonate (1.72 g, 5.28 mmol), XantPhos (0.157 g, 0.264 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.083 g, 0.088 mmol) and 1 ,4-dioxane (8.8 ml) was at 140°C under microwave irradiation for 2 hours. The reaction mixture was allowed to cool, then dilute hydrochloric acid added and the mixture extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure to provide a residue that was purified by silica gel chromatography (gradient elution: 30 - 100% ethyl acetate in /so-hexane) to provide A/-{4-[(4-methyl-2-oxo-1-piperidyl)-methyl]- pyrimidin-5-yl}-methanesulfonamide (280 mg, 53%).

Characterising data for the compound are as follows: melting point 117-121 °C; H NMR (400MHz, CDCI ₃) 5 = 10.40 (br s, 1 H), 8.96 (s, 1 H), 8.89 (s, 1 H), 4.72 (d, 1 H), 4.58 (d, 1 H), 3.66 (ddd, 1 H), 3.52 (dt, 1 H), 3.15 (s, 3H), 2.61 - 2.50 (m, 1 H), 2.06 - 1.86 (m, 3H), 1.52 - 1.39 (m, 1 H) and 1.01 (d, 3H) ppm.

Other compounds made using this general method are listed in Table 7 below.

TABLE 7 Compounds made according to the general method described in Step 2.3.

Characteristic data is melting point (°C) or ¹H nmr data (400 MHz, CDCI ₃ unless otherwise stated) δΗ ppm. -

(m, (m,

3.38

Example 3: Synthesis of A -{4-[(4-methyl-2-oxo-1 -piperidyl)-methyl]-pyrimidin-5-yl}-A - methylsulfonyl-propanamide (Compound 60-65)

Sodium hydride (0.032 g, 0.80 mmol) was added to a stirred solution of A/-[4-[(4-methyl-2-oxo-1- piperidyl)-methyl]-pyrimidin-5-yl]-methanesulfonamide (0.08 g, 0.27 mmol) in tetrahydrofuran (2.7 ml) at 0°C. The resulting mixture was stirred for 30 min then propanoyl chloride (0.070 ml, 0.80 mmol) was added. The reaction mixture was allowed to warm to ambient temperature and stirred for 3.5 hours. Water, followed by dilute hydrochloric acid, was added and the resulting mixture extracted with ethyl acetate. The combined organic extracts were washed with aqueous sodium hydroxide and brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography (gradient elution: 25 - 100% ethyl acetate in /so-hexane) to provide A/-{4-[(4-methyl-2-oxo-1-piperidyl)-methyl]-pyrimidin-5-yl}- A/-methylsulfonyl-propanamide (77 mg, 81 %). Characterising data for the compound are as follows: melting point 187-190°C; ^"Ή NMR (400MHz, CDCI ₃) 5 = 9.14 (d, 1 H), 8.52 (d, 1 H), 5.17 (dd, 1 H), 3.96 (dd, 1 H), 3.91 - 3.74 (m, 1 H), 3.57 (s, 3H), 3.55 - 3.48 (m, 1 H), 2.64 - 2.43 (m, 2H), 2.19 - 1.91 (m, 4H), 1.73 - 1.52 (m, 1 H), 1.16 (t, 3H), 1.04 (d, 3H) ppm. Example 4: Synthesis of 1,1 ,1 -trifluoro-A -{3-[(2-oxo-1 -piperidyl)-methyl]-2-pyridyl}- methanesulfonamide (Compound 55-59)

Step 4.1 Synthesis of 1 ,1 , 1-trifluoro-A/-[3-(hvdroxymethyl)-2-pyridyll-methanesulfonam ide

Triethylamine (4.67 ml, 33.5 mmol) was added to a stirred solution of (2-amino-3-pyridyl)-methanol (3.33 g, 26.8 mmol) in dichloromethane (233 ml) at 0°C. After 5 minutes a solution of trifluoromethanesulfonic anhydride (5.76 ml, 33.5 mmol) in dichloromethane (6.7 ml) was added dropwise. The resulting mixture was stirred for 30 minutes, and then partitioned between water and dichloromethane. The phases were separated and the aqueous extracted with further dichloromethane. The combined organic phases were dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography (gradient elution: 5 - 100% ethyl acetate in /so-hexane) to provide 1 , 1 ,1-trifluoro-A/-[3-(hydroxymethyl)-2-pyridyl]-methanesulfona mide (2.37 g, 34%) as an orange solid.

Characterising data for the compound are as follows: H NMR (400 MHz, CDCI ₃) δ 12.45 (br s, 1 H), 8.01 (d, 1 H), 7.73 (d, 1 H), 7.02 (t, 1 H), 4.70 (s, 2H) and 2.88 (br s, 1 H) ppm.

Step 4.2 Synthesis of A/-[3-(chloromethyl)-2-pyridyll-1 ,1 , 1-trifluoro-methanesulfonamide

Thionyl chloride (0.57 ml, 7.8 mmol) was added to a solution of 1 ,1 , 1-trifluoro-A/-[3-(hydroxymethyl)-2- pyridyl]-methanesulfonamide (1 .00 g, 3.90 mmol) in chloroform (19.5 ml). The resulting mixture was stirred at 50°C for 2 hours, allowed to cool and concentrated under reduced pressure to provide N-[3- (chloromethyl)-2-pyridyl]-1 , 1 ,1-trifluoro-methanesulfonamide (1.07 g, 100%) as a brown oil that was used without further purification.

Characterising data for the compound are as follows: H NMR (400 MHz, CDCI ₃) δ 12.50 (br s, 1 H), 8.12 (d, 1 H), 7.81 (d, 1 H), 7.04 (t, 1 H) and 4.64 (s, 2H) ppm. Step 4.3 Synthesis of 1 , 1 , 1-trifluoro-A/-{3-[(2-oxo-1-piperidyl)-methyll-2-pyridyl)-me thanesulfonamide (Compound 55-59)

Sodium hydride (0.463 g, 11.6 mmol) was added to a stirred solution of piperidin-2-one (0.383 g, 3.86 mmol) in tetrahydrofuran (19 ml) at 0°C under nitrogen. After stirring for 30 minutes a solution of N-[3- (chloromethyl)-2-pyridyl]-1 , 1 ,1-trifluoromethanesulfonamide (1.06 g, 3.86 mmol) in tetrahydrofuran (9.6 ml) was added and the resulting mixture was stirred at ambient temperature for 115 hours. Saturated aqueous ammonium chloride was added and the mixture extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure. The residue was purified by reverse phase preparative HPLC, using FractionLynx (X Bridge column, ammonium acetate buffer) to give 1 ,1 , 1 -trifluoro-/V-{3-[(2- oxo-1-piperidyl)-methyl]-2-pyridyl}-methanesulfonamide (50 mg, 11 %) as a white solid.

Characterising data for the compound are as follows: ¹ H NMR (400MHz, CDCI ₃) 5 = 12.46 (br s, 1 H), 8.02 (d, 1 H), 7.66-7.58 (m, 1 H), 6.95 (t, 1 H), 4.52 (s, 2H), 3.54 - 3.44 (m, 2H), 2.47-2.36 (m, 2H) and 1.89 - 1.76 (m, 4H) ppm. Other compounds made using this general method are listed in Table 8 below.

TABLE 8 Compounds made according to the general method described in Step 4.3.

Example 5: Synthesis of 1,1,1 -trifluoro-A -[3-{[6-(2-fluorophenyl)-2-oxo-1,3-oxazinan-3-yl]-methyl}- 2-pyridyl]-methanesulfonamide (Compound 55-536)

Step 5.1 Synthesis of 1 ,1 , 1-trifluoro-A/-(3-formyl-2-pyridyl)-methanesulfonamide

A solution of trifluoromethanesulfonic anhydride (1 .5 ml, 8.9 mmol) in dichloromethane (20 ml) was added dropwise to a stirred solution of 2-aminopyridine-3-carbaldehyde (1.0 g, 8.2 mmol) and diisopropylethyl amine (1 .57 ml, 9.0 mmol) in dichloromethane (50 ml) at 0°C. The resulting mixture was stirred for 2 hours at 0°C, then allowed to warm to ambient temperature and stirred for a further 1 hour. Water was added and the solid removed by filtration. The filtrate was extracted with dichloromethane and the combined organic extracts evaporated under reduced pressure to leave a sticky solid which was triturated with dichloromethane to provide a solid that was removed by filtration. The solids were combined to provide 1 , 1 , 1-trifluoro-A/-(3-formyl-2-pyridyl)-methanesulfonamide (0.87 g, 42%).

Characterising data for the compound are as follows: ¹ H NMR (400MHz, d6-DMSO) δ = 10.2 (s, 1 H), 8.49 (d, 1 H), 8.45 (d, 1 H) and 7.39 (t, 1 H) ppm.

Other compounds made using this general method are listed in Table 9 below.

TABLE 9 Compounds made according to the general method described in Step 5.1.

Step 5.2 Synthesis of 1 ,1 , 1 rifluoro-/V-{3-[|[3-(2-fluorophenvn-3-hvdroxy-propyll-amino) -methyll-2- pyridvD-methanesulfonamide

A solution of 3-amino-1-(2-fluorophenyl)-propan-1-ol (prepared as described in Example 6.3; 146 mg, 0.87 mmol) in ethanol (2 ml) was added slowly to a stirred solution of 1 , 1 ,1-trifluoro-A/-(3-formyl-2-pyridyl)- methanesulfonamide (200 mg, 0.79 mmol) in ethanol (3 ml). A few activated molecular sieves were added, the mixture stirred at ambient temperature for 17 hours and then filtered. The filtrate was cooled to 0°C and sodium borohydride (33 mg, 0.87 mmol) added portionwise. The resulting mixture was stirred for 3 hours at ambient temperature, then methanol (3 ml) added and stirring continued for a further hour. Water and ethyl acetate were added, the phases separated and the aqueous extracted with ethyl acetate. The combined organic phases were dried over anhydrous magnesium sulphate, filtered and evaporated under reduced pressure to provide 1 ,1 ,1-trifluoro-A/-{3-[{[3-(2-fluorophenyl)-3-hydroxy- propyl]-amino}-methyl]-2-pyridyl}-methanesulfonamide (445 mg) as a brown gum which was used without further purification.

Other compounds made using this general method are listed in Table 10 below.

TABLE 10 Compounds made according to the general method described in Step 5.2. Name Structure Characteristic Data

1 , 1 , 1-Trifluoro-/V- Used without characterisation

{3-[{[3-(2- fluorophenyl)-3- ¥

hydroxy-propyl]- amino}methyl]-4- pyridyl}- methanesulfona

mide

Step 5.3 Synthesis of 1 , 1 ,1-trifluoro-A/-[3-|[6-(2-fluorophenyl)-2-oxo-1 ,3-oxazinan-3-yll-methyl)-2- pyridyll-methanesulfonamide (Compound 55-536)

2-ieri-Butyl-1 , 1 ,3,3-tetramethylguanidine (0.75 ml, 3.18 mmol), followed by triphosgene (156 mg, 0.53 mmol), was added to a stirred solution of 1 , 1 ,1-trifluoro-A/-{3-[{[3-(2-fluorophenyl)-3-hydroxy-propyl]- amino}-methyl]-2-pyridyl}-methanesulfonamide (215 mg, 0.53 mmol) in dichloromethane (5 ml) at 0°C. The resulting mixture was allowed to warm to ambient temperature, stirred for 17 hours, and then poured into iced dilute hydrochloric acid. The resulting mixture was extracted with dichloromethane and the combined organic extracts dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure to provide a brown gum which was purified by reverse phase preparative HPLC, using FractionLynx (X Bridge column, ammonium acetate buffer) to provide 1 , 1 ,1-trifluoro-A/-[3-{[6-(2- fluorophenyl)-2-oxo-1 ,3-oxazinan-3-yl]-methyl}-2-pyridyl]-methanesulfonamide as a brown solid. Characterising data for the compound are as follows: ¹ H NMR (400MHz, d6-DMSO) δ = 13.45 (br s, 1 H), 8.00 (t, 2H), 7.49 (d, 1 H), 7.38 (m, 1 H), 7.19 (m, 3H), 5.67 (m, 1 H), 4.37 (ABq, 2H), 3.58 (m, 1 H), 3.28 (m, 1 H) and 2.19 (m, 2H) ppm.

Other compounds made using this general method are listed in Table 11 below.

TABLE 11 Compounds made according to the general method described in Step 5.3.

Compound Structure Ή nmr data (400 MHz, d6-DMSO)

Number δ _Η ppm 53-536 8.20 (m, 2H), 7.59 (d, 1 H), 7.44 (m,

1 H), 7.38 (m, 1 H), 7.20 (m, 2H), 5.60 (t, 1 H), 4.30 (ABq, 2H), 3.60 (m, 1 H), 3.27 (m, 1 H) and 2.16 (m, 2H)

Example 6: Synthesis of starting materials

Example 6.1 Synthesis of 5-chloro-4-(chloromethvn-1-methyl-3-(trifluoromethvn-pyrazol e

Thionyl chloride (1.0 ml, 14.0 mmol) was added dropwise to a solution of [5-chloro-1-methyl-3- (trifluoromethyl)-pyrazol-4-yl]-methanol (2.50 g, 11.7 mmol) in dichloromethane (58 ml). The resulting mixture was stirred at room temperature for 30 minutes, then concentrated under reduced pressure to provide 5-chloro-4-(chloromethyl)-1-methyl-3-(trifluoromethyl)-pyraz ole (2.66 g, 98%).

Characterising data for the compound are as follows: H NMR (400MHz, CDCI ₃) δ = 4.53 (s, 2H) and 3.90 (s, 3H) ppm.

Example 6.2 Synthesis of ethyl 4-(trifluoromethylsulfonylamino)-thiazole-5-carboxylate

A mixture of ethyl 4-chlorothiazole-5-carboxylate (0.5 g, 2.6 mmol), trifluoromethanesulfonamide (0.43 g 2.9 mmol), caesium carbonate (2.6 g, 7.8 mmol), XantPhos (0.23 g, 0.39 mmol),

tris(dibenzylideneacetone)dipalladium(0) (0.12 g, 0.13 mmol) and 1 ,4-dioxane (13 ml) was heated at 140°C under microwave irradiation for 1 hour. The reaction mixture was allowed to cool, dilute hydrochloric acid added and the mixture extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure to provide a residue that was purified by silica gel chromatography to provide ethyl 4- (trifluoromethylsulfonylamino)-thiazole-5-carboxylate (270 mg, 34%).

Characterising data for the compound are as follows: H NMR (400MHz, CDCI ₃) δ = 9.34 (br s, 1 H), 8.84 (s, 1 H), 4.41 (q, 2H) and 1.39 (t, 3H) ppm.

Example 6.3 Synthesis of 3-amino-1-(2-fluorophenyl)-propan-1-ol

A solution of 3-(2-fluorophenyl)-3-oxo-propanenitrile (5.5 g, 36.8 mmol) in tetrahydrofuran (120 ml) was added dropwise to a stirred solution of lithium aluminium hydride (1 M in tetrahydrofuran; 135 ml, 135 mmol) in tetrahydrofuran (120 ml) at 0°C. The reaction mixture was then allowed to warm to ambient temperature and stirred for 20 hours. It was cooled to 0°C, further lithium aluminium hydride (1 M in tetrahydrofuran; 40 ml, 40 mmol) added and the mixture allowed to warm to ambient temperature and stirred for 4 hours. Water (6.8 ml) was added, the resulting mixture stirred for 30 minutes, then sodium hydroxide (15% aqueous solution; 13.8 ml) and water (20.4 ml) added and stirring continued for a further 30 minutes. The mixture was filtered and the filtrate extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulphate, filtered and evaporated under reduced pressure to provide 3-amino-1-(2-fluorophenyl)-propan-1-ol (4.19 g, 73%) as a brown gum that was used without further purification.

Characterising data for the compound are as follows: H NMR (400MHz, CDCI ₃) δ = 7.49 (t, 1 H), 7.22 (m, 1 H), 7.16 (t, 1 H), 7.07 (dd, 1 H), 4.92 (t, 1 H), 2.63 (t, 2H) and 1 .62 (q, 2H) ppm.

Example 6.4 Synthesis of 1-[(3-chloro-4-pyridyl)-methyll-4-methyl-piperidin-2-one

A mixture of (3-chloro-4-pyridyl)-methanol (0.97 g, 6.8 mmol), 4-methylpiperidin-2-one (1.5 g, 14 mmol), 4-methylbenzenesulfonic acid hydrate (1.3 g, 6.8 mmol) and chlorobenzene (38 ml) were heated at reflux using a Dean Stark trap for 17 hours, then allowed to cool and concentrated under reduced pressure. The residue was purified by reverse phase preparative HPLC, using FractionLynx (X Bridge column, ammonium acetate buffer) to provide 1-[(3-chloro-4-pyridyl)-methyl]-4-methyl-piperidin-2-one (0.33 g, 20%) as a brown oil.

Characterising data for the compound are as follows: H NMR (400MHz, CDCI ₃) δ = 8.69 (s, 1 H), 8.53 (d, 1 H), 7.34 (d, 1 H), 4.77 (ABq, 2H), 3.46 - 3.27 (m, 2H), 2.71 - 2.62 (m, 1 H), 2.21 - 1.92 (m, 3H), 1.65-1.51 (m, 1 H), 1 .09 (d, 3H) ppm.

Example 7: Pre-emergence biological efficacy

Seeds of Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Solanum nigrum (SOLNI), Amaranthus retroflexus (AMARE) and Ipomoea hederaceae (IPOHE) were sown in standard soil in pots. After cultivation for one day under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give a final dose of 500 or 1000 g/ha of test compound.

The test plants were then grown under controlled conditions in the glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant). Results are shown below in Table 12.

TABLE 12 Percentage damage caused to weed species by compounds of the invention when applied pre-emergence.

Species

Rate

Cpd No

(g/ha)

ZEAMX SETFA ALOMY ECHCG LOLPE SOLNI AMARE IPOHE ABUTH

9-59 1 ,000 80 70 90 60 60 70

15-55 1 ,000 0 30 10 20 30 10

15-64 1 ,000 0 0 0 0 0 0

16-68 1 ,000 0 0 0 0 0 0

24-64 1 ,000 0 0 0 0 0 0

37-68 1 ,000 0 0 0 0 0 0

53-536 500 0 0 0 0 0 0

54-68 900 20 70 20 50 60 20

55-59 1 ,000 80 50 90 40 40 20

55-536 1 ,000 50 20 20 30 0 0 59-64 1 ,000 0 0 0 0 0 0

60-64 1 ,000 0 0 0 0 0 0

60-65* 1 ,000 10 20 10 10 30 40

60-68 1 ,000 60 70 90 60 80 60

60-676 1 ,000 0 0 0 0 0 0

60-680 1 ,000 0 50 30 40 60 30

61-64 1 ,000 0 0 0 0 0 0

61-68 1 ,000 0 20 10 0 0 10

* Test evaluated 9 days after treatment

Example 8: Post-emergence biological efficacy

Seeds of Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Solanum nigrum (SOLNI), Amaranthus retroflexus (AMARE) and Ipomoea hederaceae (IPOHE) were sown in standard soil in pots. After cultivation for 8 days under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS RN 9005-64-5) to give a final dose of 500 or 1000 g/ha of test compound.

The test plants were then grown on under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days the test was evaluated (100 = total damage to plant; 0 = no damage to plant). Results are shown below in Table 13.

TABLE 13 Percentage damage caused to weed species by compounds of the invention when applied post-emergence

Species

Rate

Cpd No

(g/ha)

ZEAMX SETFA ALOMY ECHCG LOLPE SOLNI AMARE IPOHE ABUTH

9-59 1 ,000 70 70 80 70 50 80

15-55 1 ,000 0 0 0 0 0 0

15-64 1 ,000 0 0 0 0 0 0

16-68 1 ,000 20 0 0 0 0 20

24-64 1 ,000 0 0 0 0 0 0 37-68 1,000 20 0 0 0 0 10

53-536 500 0 0 10 10 0 20

54-68 900 20 50 50 30 10 40

55-59 1,000 70 40 70 40 20 80

55-536 1,000 10 10 40 50 0 50

59-64 1,000 20 10 0 10 10 10

60-65* 1,000 10 0 0 0 10 10

60-64 1,000 40 10 0 0 0 40

60-68 1,000 40 60 80 30 30 70

60-676 1,000 20 0 0 0 0 0

60-680 1,000 30 40 40 40 60 60

61-64 1,000 0 0 0 0 0 0

61-68 1,000 10 20 10 0 0 20

* Test evaluated 9 days after treatment

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