HERBICIDAL HALOALKYLSULPHONAMIDE COMPOUNDS

The present invention relates to certain haloalkylsulphonamide derivatives, to processes for their preparation, herbicidal compositions comprising them, and their use in controlling plants or inhibiting plant growth.

Herbicidal haloalkylsulphonamide derivatives of the formula (i)

are taught in WO 2010/026989. Similar compounds are taught in WO 2010/119906.

However, new haloalkylsulphonamide derivatives with an improved efficacy and/or spectrum of activity and/or improved crop tolerance with respect to the known derivatives have now been identified.

Accordingly, in a first aspect, the invention provides compounds of the formula (I)

(I)

wherein

A is selected from CH=CH, CR ³ =CH, CH=CR ³ , CR ³ =CR ³ and S; W is selected from oxygen and sulphur;

X is selected from H, cyano, nitro, NR ⁹ R ¹⁰ , C ₁ _ ₄ alkyl, C ₃ . ₆ cycloalkyl, aryl optionally substituted by 1-3 groups R ²⁵ , d- ₈ alkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R ²⁵ , d. ₄ alkoxycarbonyl, Ci_ ₄ alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R ²⁵ , aminocarbonyl, Ci_ ₄ alkylaminocarbonyl, di(Ci_ ₄ alkyl)aminocarbonyl, Ci_ ₆ alkylsulphonyl and arylsulphonyl optionally substituted by 1-3 groups R ²⁵ , and each R ²⁵ is, independently, selected - - from halogen, C ₁ _ ₄ alkyl, C-|. ₄ haloalkyl, Ci_ ₄ alkoxy, Ci_ ₄ haloalkoxy, hydroxy, phenyl and phenoxy; m is 0, 1 or 2; n is 1 , 2, 3 or 4; p is 0, 1 , 2 or 3; with the proviso that 2 < n + p < 4;

R is Ci- ₆ haloalkyl;

R is selected from H, Ci_ ₄ alkyl, C ₃ . ₅ alkenyl, propargyl, Ci. ₄ alkoxyCi. ₂ alkyl, Ci_ ₄ alkoxyCi_ ₂ alkoxyCi- ₂ alkyl, Ci. ₄ haloalkoxyCi. ₂ alkyl, C ₁ _ ₄ alkylthioC ₁ _ ₂ alkyl, cyanoCi_ ₂ alkyl, Ci_

4alkylcarbonylCi_ ₂ alkyl, Ci. ₄ alkoxycarbonylCi. ₂ alkyl, Ci. ₄ alkylsulphonylCi. ₂ alkyl, arylCi_ ₂ alkyl optionally substituted by 1-3 groups R ²⁰ , heteroarylCi_ ₂ alkyl optionally substituted by 1-3 groups R ²⁰ , arylthioCi- ₂ alkyl optionally substituted by 1-3 groups R ²⁰ , optionally substituted by 1-3 groups R ²⁰ , optionally substituted by 1-3 groups R ²⁰ , arylcarbonylCi_ ₂ alkyl optionally substituted by 1-3 groups R ²⁰ , Ci. ₄ alkylcarbonyloxyCi. ₂ alkyl, arylcarbonyloxyCi- ₂ alkyl optionally substituted by 1-3 groups R ²⁰ , Ci. ₄ alkoxycarbonyloxyCi. ₂ alkyl, aryloxycarbonyloxyCi_ ₂ alkyl optionally substituted by 1-3 groups R ²⁰ ,Ci_ ₈ alkylcarbonyl, C ₂ - ₅ alkenylcarbonyl, Ci_ ₄ haloalkylcarbonyl, Ci. ₄ alkoxyCi. ₂ alkylcarbonyl, C ₃ . ₆ cycloalkylcarbonyl, d- ₄ alkoxycarbonylCi_ ₂ alkylcarbonyl, arylcarbonyl optionally substituted by 1-3 groups R ²⁰ , aryloxyCi_ ₂ alkylcarbonyl optionally substituted by 1-3 groups R ²⁰ , Ci_i ₀ alkoxycarbonyl; d- ₄ haloalkoxycarbonyl, C ₃ . ₅ alkenyloxycarbonyl, propargyloxycarbonyl, Ci_ ₄ alkoxyCi_

₂ alkoxycarbonyl, Ci_ ₄ alkylthiocarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R ²⁰ , arylCi_ ₂ alkoxycarbonyl optionally substituted by 1-3 groups R ²⁰ , aminocarbonyl, d- ₄ alkylaminocarbonyl, di(Ci_ ₄ alkyl)aminocarbonyl, Ci_ ₆ alkylsulphonyl, Ci_ ₆ haloalkylsulphonyl and arylsulphonyl optionally substituted by 1-3 groups R ²⁰ , and each R ²⁰ is, independently, selected from halogen, Ci_ ₄ alkyl, Ci_ ₄ haloalkyl, Ci_ ₄ alkoxy, Ci_ ₄ haloalkoxy, hydroxy, phenyl and phenoxy; each R ² is, independently, selected from halogen, nitrile, Ci_ ₄ alkyl, Ci_ ₄ haloalkyl, C ₃ . ₆ cycloalkyl, C ₂ - ₄ alkenyl, C ₂ - ₄ alkynyl, Ci_ ₄ alkoxy, Ci_ ₄ haloalkoxy, hydroxy, Ci_

4alkylcarbonyl, Ci_ ₄ alkylsulphonyl and phenyl, or two R ² groups together form -OCH ₂ 0- or - OCH ₂ CH ₂ O-; each R ³ is, independently, selected from halogen, nitrile, Ci_ ₄ alkyl, Ci_ ₄ haloalkyl, C ₃ . ₆ cycloalkyl, C ₂ - ₄ alkenyl, C ₂ - ₄ alkynyl, Ci_ ₄ alkoxy, Ci_ ₄ haloalkoxy, hydroxy, d- ₄ alkylcarbonyl, Ci. ₄ alkylsulphonyl and phenyl, or two R ³ groups together form -OCH ₂ 0- or - OCH ₂ CH ₂ O-; - - each R ⁵ and R ⁶ are, independently, selected from H, halogen, cyano, hydroxy, C ₁ _ ₄ alkyl, d_ ₄ haloalkyl, C ₃ . ₆ cycloalkyl, C ₂ - ₅ alkenyl, C ₂ - ₅ alkynyl, Ci_ ₄ alkoxy, Ci_ ₄ alkylthio, d- ₄ alkoxycarbonyl, aryl optionally substituted by 1-3 groups R ²⁴ , aryloxy optionally substituted by 1- 3 groups R ²⁴ and arylthio optionally substituted by 1-3 groups R ²⁴ or R ⁵ and R ⁶ on the same carbon atom together form a C ₂ - ₅ alkylene chain optionally containing an oxygen atom, or R ⁵ and R ⁶ on different carbon atoms together form a Ci_ ₄ alkylene chain, or R ⁵ and R ⁰ together form a Ci- ₃ alkylene chain and each R ²⁴ is, independently, selected from halogen, cyano, Ci_ ₄ alkyl, d- ₄ haloalkyl, Ci_ ₄ alkoxy, Ci_ ₄ haloalkoxy, hydroxy, phenyl and phenoxy; each R ⁷ and R ⁸ are, independently, selected from H, Ci_ ₅ alkyl, Ci_ ₄ haloalkyl, C ₃ . ₆ cycloalkyl optionally substituted with 1-3 groups selected from halogen, Ci_ ₄ alkyl or phenyl, Ci_ ₄ alkoxyCi_ ₄ alkyl, Ci. ₄ alkoxycarbonylaminoCi_ ₄ alkyl, Ci. ₄ alkylcarbonyloxyCi. ₂ alkyl, arylCi_ ₂ alkyl optionally substituted by 1-3 groups R ² , aryloxyCi_ ₂ alkyl optionally substituted by 1-3 groups R ² , aryld- ₂ alkoxyCi_ ₂ alkyl optionally substituted by 1-3 groups R ² ,C ₂ . ₄ alkenyl, hydroxyl, Ci_ ₄ alkoxy, d- ₄ alkylthio, Ci_ ₄ alkylcarbonyloxy, 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 and heteroaryl optionally substituted by 1-3 groups R ² , or R ⁷ and R ⁸ on the same carbon atom together form a C ₂ . ₆ alkylene chain optionally containing an oxygen or sulphur atom and optionally substituted by 1-3 groups selected from halogen, Ci_ ₂ alkyl and an oxo group, or R ⁷ and R ⁸ on different carbon atoms together form a Ci_ ₄ alkylene chain, or R ⁸ and R ⁰ together form a Ci_ ₃ alkylene chain and each R ² is, independently, selected from halogen, cyano, Ci_ ₄ alkyl, Ci_ ₄ haloalkyl, Ci_ ₄ alkoxy, d- ₄ haloalkoxy, Ci. ₂ alkoxyCi. ₂ alkoxy, hydroxy, phenyl and phenoxy or two R ² groups together form -OCH ₂ 0- or -OCH ₂ CH ₂ 0-;

R ⁹ is selected from H, d_ ₆ alkyl, Ci_ ₆ haloalkyl, C ₃ - ₆ cycloalkyld. ₂ alkyl, d ecycloalkyl, aryl optionally substituted by 1-3 groups R ²² , arylCi_ ₂ alkyl optionally substituted by 1-3 groups R ²² and heteroaryl optionally substituted by 1-3 groups R ²² and each R ²² is, independently, selected from halogen, nitro, cyano, d_ ₄ alkyl, d_ ₄ haloalkyl, d_ ₄ alkoxy, Ci_ ₄ haloalkoxy, Ci. ₂ alkoxyCi. ₂ alkoxy, hydroxy, d- ₄ alkylthio, Ci. ₄ haloalkylthio, Ci. ₄ alkylsulphonyl, d_ ₄ alkoxycarbonyl, phenyl and phenoxy;

R ⁰ is selected from H, d_ ₆ alkyl, d_ ₄ alkylcarbonyl, Ci_ ₄ alkoxycarbonyl, Ci. ₄ haloalkoxycarbonyl, Ci. ₄ alkoxyCi. ₂ alkoxycarbonyl, d-salkenyloxycarbonyl, aryloxycarbonyl optionally substituted by 1- 3 groups R ²³ , arylCi_ ₂ alkoxycarbonyl optionally substituted by 1-3 groups R ²³ , aminocarbonyl, d- ₄ alkylaminocarbonyl, di(Ci. ₄ alkyl)aminocarbonyl, -C(=S)NH ₂ , -C(=NH)NH ₂ , d. ₆ alkylsulphonyl, d- ₆ haloalkylsulphonyl and arylsulphonyl optionally substituted by 1-3 groups R ²³ or R ⁰ together with one R ⁵ or R ⁸ form a d_ ₃ alkylene chain, and each R ²³ is, independently, selected from halogen, nitro, cyano, d_ ₄ alkyl, d_ ₄ haloalkyl, Ci_ ₄ alkoxy, Ci. ₄ haloalkoxy, Ci. ₂ alkoxyCi. ₂ alkoxy, hydroxy, d_ ₄ alkylthio, Ci_ ₄ haloalkylthio, Ci. ₄ alkylsulphonyl, Ci. ₄ alkoxycarbonyl, phenyl and phenoxy; or an N-oxide or salt form thereof. - -

In particularly preferred embodiments of the invention, the preferred groups for A, W, X, m, n, p, R , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ⁰ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ in any combination thereof, are as set out below:

Preferably, A is selected from CH=CH and CR ³ =CH. Most preferably, A is CH=CH.

Preferably, W is oxygen.

Preferably, X is NR ⁹ R ¹⁰ .

Preferably, m is 0 or 1.

Most preferably, m is 0. Preferably, n is 2, 3 or 4.

Preferably, p is 0.

Preferably, R is d- ₂ haloalkyl.

More preferably, R is trifluoromethyl.

Preferably, R is selected from H, d- ₄ haloalkoxyCi- ₂ alkyl, arylCi_ ₂ alkyl optionally substituted by 1-3 groups R ²⁰ , arylCi- ₂ alkoxyCi- ₂ alkyl optionally substituted by 1-3 groups R ²⁰ , C-i^alkylcarbonyloxyC-i^alkyl, arylcarbonyloxyCi_ ₂ alkyl optionally substituted by 1-3 groups R ²⁰ , Ci_ ₈ alkylcarbonyl, d- ₄ haloalkylcarbonyl, Ci_i ₀ alkoxycarbonyl; Ci_ ₄ haloalkoxycarbonyl, d- ₄ alkoxyCi- ₂ alkoxycarbonyl, aryloxycarbonyl optionally substituted by 1-3 groups R ²⁰ , arylCi. ₂ alkoxycarbonyl optionally substituted by 1-3 groups R ²⁰ , d. ₆ alkylsulphonyl and d- ₆ haloalkylsulphonyl.

More preferably, R is selected from H, d. ₅ alkylcarbonyl, d. ₄ haloalkylcarbonyl, d- ₅ alkoxycarbonyl, Ci. ₄ haloalkoxycarbonyl and Ci. ₄ haloalkylsulphonyl.

Most preferably, R is selected from H, d. ₅ alkylcarbonyl and d. ₅ alkoxycarbonyl. Preferably, R ² is selected from halogen, C ₁ _ ₄ alkyl, C-|. ₄ haloalkyl, Ci. ₄ alkoxy and d-

₄ alkylsulphonyl.

Most preferably, R ² is selected from halogen and methyl.

Preferably, R ³ is selected from halogen, C ₁ _ ₄ alkyl, C-|. ₄ haloalkyl, d_ ₄ alkoxy and d- ₄ alkylsulphonyl. Most preferably, R ³ is selected from halogen and methyl. - -

Preferably, R ⁵ and R ⁶ are, independently, selected from H, halogen, C ₁ _ ₄ alkyl, Ci_ ₄ haloalkyl, Ci_ ₄ alkoxy, Ci_ ₄ alkylthio, aryl optionally substituted by 1-3 groups R ²⁴ , aryloxy optionally substituted by 1-3 groups R ²⁴ and arylthio optionally substituted by 1-3 groups R ²⁴ .

More preferably, R ⁵ and R ⁶ are, independently, selected from H, halogen, Ci_ ₄ alkyl, d. ₄ haloalkyl, Ci_ ₄ alkoxy, Ci_ ₄ alkylthio and aryl optionally substituted by 1-2 groups R ²⁴ .

Most preferably, R ⁵ and R ⁶ are, independently, selected from H, halogen, Ci_ ₃ alkyl, d. ₃ alkoxy and Ci_ ₃ alkylthio.

Preferably, R ⁷ and R ⁸ are, independently, selected from H, Ci_ ₅ alkyl, Ci_ ₄ haloalkyl, C ₃ . ₆ cycloalkyl, Ci_ ₄ alkoxyCi_ ₄ alkyl, arylCi_ ₂ alkyl optionally substituted by 1-3 groups R ² , C ₂ - ₄ alkenyl, Ci_ ₄ alkoxy, Ci_ ₄ alkylthio, 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 and heteroaryl optionally substituted by 1-3 groups R ² , or R ⁷ and R ⁸ on the same carbon atom together form a C ₂ - ₅ alkylene chain optionally containing an oxygen atom, or R ⁷ and R ⁸ on adjacent carbon atoms together form a Ci_ ₄ alkylene chain. More preferably, R ⁷ and R ⁸ are, independently, selected from H, Ci_ ₄ alkyl, Ci_ ₃ haloalkyl, cyclopropyl, Ci- ₂ alkoxyCi- ₂ alkyl,Ci- ₃ alkoxy, Ci_ ₃ alkylthio, 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 and heteroaryl optionally substituted by 1-3 groups R ² , or R ⁷ and R ⁸ on the same carbon atom together form a C ₃ . ₅ alkylene chain optionally containing an oxygen atom, or R ⁷ and R ⁸ on adjacent carbon atoms together form a Ci_ ₄ alkylene chain.

Most preferably, R ⁷ and R ⁸ are, independently, selected from H, Ci_ ₃ alkyl, trifluoromethyl, cyclopropyl, methoxymethyl, Ci_ ₃ alkoxy and aryl optionally substituted by 1-2 groups R ² , or R ⁷ and R ⁸ together form a C ₃ . ₅ alkylene chain optionally containing an oxygen atom, or R ⁷ and R ⁸ on adjacent carbon atoms together form a -CH ₂ - group. Preferably, R ⁹ is selected from H, Ci_ ₄ alkyl and aryl optionally substituted by 1-3 groups

R ²² .

Preferably, R ⁰ is selected from H, Ci_ ₄ alkyl, Ci_ ₄ alkylcarbonyl, Ci_ ₄ alkoxycarbonyl, aminocarbonyl, Ci_ ₄ alkylaminocarbonyl, di(Ci_ ₄ alkyl)aminocarbonyl, -C(=S)NH ₂ , -C(=NH)NH ₂ and arylsulphonyl optionally substituted by 1-3 groups R ²³ . More preferably, R ⁰ is selected from H and Ci_ ₄ alkyl.

Preferably, R ²⁰ is selected from halogen, Ci_ ₄ alkyl, Ci_ ₄ haloalkyl, Ci_ ₄ alkoxy and Ci_ ₄ haloalkoxy.

Preferably, R ² is selected from halogen, cyano, Ci_ ₄ alkyl, Ci_ ₄ haloalkyl, Ci_ ₄ alkoxy and d. ₄ haloalkoxy. Most preferably, R is selected from halogen, methyl and methoxy.

Preferably, R ²² is selected from halogen, d- ₂ alkyl, Ci_ ₂ haloalkyl, Ci_ ₂ alkoxy and d.

2haloalkoxy.

Preferably, R ²³ is, independently, selected from halogen, Ci_ ₂ alkyl, Ci_ ₂ haloalkyl, Ci_ ₂ alkoxy and Ci_ ₂ haloalkoxy.

Preferably, R ²⁴ is selected from halogen, cyano, C ₁ _ ₄ alkyl, C-|. ₄ haloalkyl, Ci_ ₄ alkoxy and d. 4haloalkoxy.

More preferably, R ²⁴ is selected from halogen, methyl and methoxy.

Table 1 below provides 282 compounds, designated compounds 1-1 to 1-282 respectively, of formula (la), wherein R is H and A is CH=CH.

(la) TABLE 1

- -

- -

- -

- -

- -

282 compounds are described, designated compounds 2-1 to 2-282 respectively, of formula (la), wherein R is H, m is 0, A is CF=CH and the values of R ⁷ , R ⁸ , R ⁷ , R ⁸ and X are as defined in Table 1. 282 compounds are described, designated compounds 3-1 to 3-282 respectively, of formula (la), wherein R is H, A is S and the values of R ⁷ , R ⁸ , R ⁷ , R ⁸ and X are as defined in Table 1.

282 compounds are described, designated compounds 4-1 to 4-282 respectively, of formula (la), wherein R is C0 ₂ Et, A is CH=CH and the values of R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 1.

282 compounds are described, designated compounds 5-1 to 5-282 respectively, of formula (la), wherein R is C0 ₂ Et, A is CF=CH and the values of R ⁷ , R ⁸ , R ⁷ , R ⁸ and X are as defined in Table 1.

282 compounds are described, designated compounds 6-1 to 6-282 respectively, of formula (la), wherein R is C0 ₂ Et, A is S and the values of R ⁷ , R ⁸ , R ⁷ , R ⁸ and X are as defined in Table 1.

Table 2 below provides 52 compounds, designated compounds 7-1 to 7-52 respectively, of formula (lb), wherein R is H and A is CH=CH. - -

(lb) TABLE 2

- -

52 compounds are described, designated compounds 8-1 to 8-52 respectively, of formula (lb), wherein R is H, A is CF=CH and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 2. 52 compounds are described, designated compounds 9-1 to 9-52 respectively, of formula

(lb), wherein R is H, A is S and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 2.

52 compounds are described, designated compounds 10-1 to 10-52 respectively, of formula (lb), wherein R is C0 ₂ Et, A is CH=CH and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 2. 52 compounds are described, designated compounds 11-1 to 11-52 respectively, of formula (lb), wherein R is C0 ₂ Et, A is CF=CH and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 2.

52 compounds are described, designated compounds 12-1 to 12-52 respectively, of formula (lb), wherein R is C0 ₂ Et, A is S and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 2.

Table 3 below provides 442 compounds, designated compounds 13-1 to 13-442 respectively, of formula (lc), wherein R is H and A is CH=CH.

(Ic) TABLE 3

- -

- -

- -

- -

- -

- -

- -

- -

442 compounds are described, designated compounds 14-1 to 14-442 respectively, of formula (lc), wherein R is H, A is CF=CH and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 3. 442 compounds are described, designated compounds 15-1 to 15-442 respectively, of formula (lc), wherein R is H, A is S and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 3.

442 compounds are described, designated compounds 16-1 to 16-442 respectively, of formula (lc), wherein R is C0 ₂ Et, A is CH=CH and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 3.

442 compounds are described, designated compounds 17-1 to 17-442 respectively, of formula (lc), wherein R is C0 ₂ Et, A is CF=CH and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 3.

442 compounds are described, designated compounds 18-1 to 18-442 respectively, of formula (lc), wherein R is C0 ₂ Et, A is S and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 3. - -

Table 4 below provides 115 compounds, designated compounds 19-1 to 19-115 respectively, of formula (Id), wherein R is H and A is CH=CH.

TABLE 4

- -

- -

1 15 compounds are described, designated compounds 20-1 to 20-1 15 respectively, of formula (Id), wherein R is H, A is CF=CH and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 4.

1 15 compounds are described, designated compounds 21-1 to 21-1 15 respectively, of formula (Id), wherein R is H, A is S and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 4.

1 15 compounds are described, designated compounds 22-1 to 22-1 15 respectively, of formula (Id), wherein R is C0 ₂ Et, A is CH=CH and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 4.

1 15 compounds are described, designated compounds 23-1 to 23-1 15 respectively, of formula (Id), wherein R is C0 ₂ Et, A is CF=CH and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 4.

1 15 compounds are described, designated compounds 24-1 to 24-1 15 respectively, of formula (Id), wherein R is C0 ₂ Et, A is S and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 4.

Table 5 below provides 124 compounds, designated compounds 25-1 to 25-124 respectively, of formula (le), wherein R is H and A is CH=CH. - -

(le) TABLE 5

- -

- -

124 compounds are described, designated compounds 26-1 to 26-124 respectively, of formula (le), wherein R is H, A is CF=CH and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 5.

124 compounds are described, designated compounds 27-1 to 27-124 respectively, of formula (le), wherein R is H, A is S and the values of R ⁵ , R ⁶ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 5.

124 compounds are described, designated compounds 28-1 to 28-124 respectively, of formula (le), wherein R is C0 ₂ Et, A is CH=CH and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 5.

124 compounds are described, designated compounds 29-1 to 29-124 respectively, of formula (le), wherein R is C0 ₂ Et, A is CF=CH and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 5.

124 compounds are described, designated compounds 30-1 to 30-124 respectively, of formula (le), wherein R is C0 ₂ Et, A is S and the values of R ⁵ , R ⁶ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and X are as defined in Table 5.

Table 6 below provides 276 compounds, designated compounds 31-1 to 31-276 respectively, of formula (If), wherein R is H and A is CH=CH. - -

TABLE 6 - -

- -

- -

- -

- -

276 compounds are described, designated compounds 32-1 to 32-276 respectively, of formula (If), wherein R is H, A is CF=CH and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" , R ^{7 '} , R ^8" and X are as defined in Table 6. 276 compounds are described, designated compounds 33-1 to 33-276 respectively, of formula (If), wherein R is H, A is S and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" , R ^{7 "'} , R ^8" and X are as defined in Table 6.

276 compounds are described, designated compounds 34-1 to 34-276 respectively, of formula (If), wherein R is C0 ₂ Et, A is CH=CH and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" , R ^{7 "'} , R ^8" and X are as defined in Table 6.

276 compounds are described, designated compounds 35-1 to 35-276 respectively, of formula (If), wherein R is C0 ₂ Et, A is CF=CH and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" , R ^{7 "'} , R ^8" and X are as defined in Table 6.

276 compounds are described, designated compounds 36-1 to 36-276 respectively, of formula (If), wherein R is C0 ₂ Et, A is S and the values of R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" , R ^{7 "'} , R ^8" and X are as defined in Table 6.

Table 7 below provides 143 compounds, designated compounds 37-1 to 37-143 respectively, of formula (Ig), wherein R is H and A is CH=CH.

(ig)

TABLE 7

Cpd

R ⁷ R ⁸ R ^7' R ^8' R ^7" R ^8" X R ⁵ R ⁶ No

1 H H H H H H NH ₂ H H

2 Me H H H H H NH ₂ H H

3 H H Me H H H NH ₂ H H

4 H H H H Me H NH ₂ H H

5 H H H H Et H NH ₂ H H

6 H H H H 'Pr H NH ₂ H H

7 H H H H ⁿ Pr H NH ₂ H H

8 H H H H ^c Pr H NH ₂ H H - -

- -

143 compounds are described, designated compounds 38-1 to 38-143 respectively, of formula (Ig), wherein R is H, A is CF=CH and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 7. 143 compounds are described, designated compounds 39-1 to 39-143 respectively, of formula (Ig), wherein R is H, A is S and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 7.

143 compounds are described, designated compounds 40-1 to 40-143 respectively, of formula (Ig), wherein R is C0 ₂ Et, A is CH=CH and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 7.

143 compounds are described, designated compounds 41-1 to 41-143 respectively, of formula (Ig), wherein R is C0 ₂ Et, A is CF=CH and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 7.

143 compounds are described, designated compounds 42-1 to 42-143 respectively, of formula (Ig), wherein R is C0 ₂ Et, A is S and the values of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' , R ^7" , R ^8" and X are as defined in Table 7.

Table 8 below provides 31 compounds, designated compounds 43-1 to 43-31 respectively, of formula (Ih), wherein R is H and A is CH=CH. - -

TABLE 8

31 compounds are described, designated compounds 44-1 to 44-31 respectively, of formula (Ih), wherein R is H, A is CF=CH and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 8.

31 compounds are described, designated compounds 45-1 to 45-31 respectively, of formula (Ih), wherein R is H, A is S and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 8. - -

31 compounds are described, designated compounds 46-1 to 46-31 respectively, of formula (Ih), wherein R is C0 ₂ Et, A is CH=CH and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 8.

31 compounds are described, designated compounds 47-1 to 47-31 respectively, of formula (Ih), wherein R is C0 ₂ Et, A is CF=CH and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 8.

31 compounds are described, designated compounds 48-1 to 48-31 respectively, of formula (Ih), wherein R is C0 ₂ Et, A is S and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ⁷ , R ⁸ , R ^7' , R ^8' and X are as defined in Table 8. Table 9 below provides 142 compounds, designated compounds 49-1 to 49-142 respectively, of formula (li), wherein R is H and A is CH=CH.

(li)

TABLE 9

- -

- -

- -

142 compounds are described, designated compounds 50-1 to 50-142 respectively, of formula (li), wherein R is H, A is CF=CH and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ^5" , R ^6" , R ⁷ , R ⁸ and X are as defined in Table 9. 142 compounds are described, designated compounds 51-1 to 51-142 respectively, of formula (li), wherein R is H, A is S and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ^5" , R ^6" , R ⁷ , R ⁸ and X are as defined in Table 9.

142 compounds are described, designated compounds 52-1 to 52-142 respectively, of formula (li), wherein R is C0 ₂ Et, A is CH=CH and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ^5" , R ^6" , R ⁷ , R ⁸ and X are as defined in Table 9.

142 compounds are described, designated compounds 53-1 to 53-142 respectively, of formula (li), wherein R is C0 ₂ Et, A is CF=CH and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ^5" , R ^6" , R ⁷ , R ⁸ and X are as defined in Table 9.

142 compounds are described, designated compounds 54-1 to 54-142 respectively, of formula (li), wherein R is C0 ₂ Et, A is S and the values of R ⁵ , R ⁶ , R ^5' , R ⁶ , R ^5" , R ^6" , R ⁷ , R ⁸ and X are as defined in Table 9.

The 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 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 all such optical isomers and diastereomers as well as the racemic and resolved, enantiomerically pure R and S stereoisomers and other mixtures of the R and S stereoisomers and agrochemically acceptable salts thereof. It is recognized that certain optical isomers, or diastereomers may have favorable properties over the other. Thus when disclosing and claiming the invention, when a racemic mixture is disclosed, it is clearly contemplated that both optical isomers, including diastereomers substantially free of the other are disclosed and claimed as well.

Alkyl, as used herein, means an aliphatic hydrocarbon chain and includes straight and branched chains e. g. of 1 to 8 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. - -

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

Cycloalkylalkyl, as used herein, means a radical -R-cycloalkyl, wherein R is alkyl as defined above.

Alkenyl, as used herein, means 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 8 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, means 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 8 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 linear saturated divalent hydrocarbon radical of one to six carbon atoms or a branched saturated divalent hydrocarbon radical of three to six carbon atoms, e.g. methylene, ethylene, propylene, 2-methylpropylene and the like.

Alkoxy, as used herein, means a radical -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, means a radical -ROR, wherein each R is, independently, an alkyl group as defined above.

Alkoxyalkoxy, as used herein, means a radical -OROR, wherein each R is, independently, alkyl as defined above.

Alkoxyalkoxyalkyl, as used herein, means a radical -ROROR, wherein each R is, independently, alkyl as defined above.

Cyanoalkyl, as used herein, means an alkyl group as defined above substituted with one or more cyano groups.

Alkylthio, as used herein, means a radical -SR, wherein R is alkyl as defined above.

Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tert-butylthio, and the like.

Alkylthioalkyl, as used herein, means a radical -RSR, wherein each R is, independently, alkyl as defined above.

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

Haloalkyi, as used herein, means an alkyl group as defined above wherein at least one hydrogen atom has been replaced with a halogen atom as defined above. Examples of haloalkyi groups include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and trifluoromethyl. Preferred haloalkyi groups are fluoroalkyi groups {i.e. haloalkyi groups, containing fluorine as the only halogen). More highly preferred haloalkyi groups are perfluoroalkyi groups, i.e. alkyl groups wherein all the hydrogen atoms are replaced with fluorine atoms.

Haloalkoxy, as used herein, means a radical -OR, wherein R is haloalkyi as defined above.

Haloalkoxyalkyl, as used herein, means a radical -ROR', wherein R is alkyl as defined above and R' is haloalkyi as defined above.

Haloalkylthio, as used herein, means a radical -SR, wherein R is haloalkyi as defined above.

Alkylcarbonyl, as used herein, means a radical -C(0)R, wherein R is alkyl as defined above. Alkenylcarbonyl, as used herein, means a radical -C(0)R, wherein R is alkenyl as defined above.

Cycloalkylcarbonyl, as used herein, means a radical -C(0)R, wherein R is cycloalkyl as defined above.

Alkoxycarbonyl, as used herein, means a radical -C(0)OR, wherein R is alkyl as defined above.

Alkoxyalkoxycarbonyl, as used herein, means a radical -C(0)OROR, wherein each R is, independently, alkyl as defined above.

Alkenyloxycarbonyl, as used herein, means a radical -C(0)OR, wherein R is alkenyl as defined above. Propargyloxycarbonyl, as used herein, means a radical -C(0)OR, wherein R is propargyl.

Alkylcarbonylalkyl, as used herein, means a radical -RC(0)R, wherein each R is, independently, alkyl as defined above.

Alkoxycarbonylalkyl, as used herein, means a radical -RC(0)OR, wherein each R is, independently, alkyl as defined above. Alkoxyalkylcarbonyl, as used herein, means a radical -C(0)ROR, wherein each R is, independently, alkyl as defined above. - -

Alkoxycarbonylalkylcarbonyl, as used herein, means a radical -C(0)RC(0)OR, wherein each R is, independently, alkyl as defined above.

Alkylthiocarbonyl, as used herein, means a radical -C(0)SR, wherein R is alkyl as defined above. Haloalkylcarbonyl, as used herein means a radical -C(0)R, wherein R is haloalkyi as defined above.

Haloalkoxycarbonyl, as used herein, means a radical -C(0)OR, wherein R is haloalkyi as defined above.

Alkylcarbonyloxy, as used herein, means a radical -OC(0)R, wherein R is an alkyl group as defined above.

Alkylcarbonyloxyalkyl, as used herein, means a radical -ROC(0)R, wherein each R is, independently, alkyl as defined above.

Alkoxycarbonyloxyalkyl, as used herein, means a radical -ROC(0)OR, wherein each R is, independently, alkyl as defined above. Alkylsulphonyl, as used herein, means a radical -S(0) ₂ R, wherein R is alkyl as defined above.

Haloalkylsulphonyl, as used herein, means a radical -S(0) ₂ R, wherein R is haloalkyi as defined above.

Alkylsulphonylalkyl, as used herein, means a radical -RS(0) ₂ R, wherein each R is, independently, alkyl as defined above.

Hydroxy or hydroxyl, as used herein, means the group -OH.

Nitro, as used herein, means the group -N0 ₂ .

Cyano, or nitrile, as used herein, means the group -CN.

Oxo, as used herein, means the group =0. Aryl, as used herein, means 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, means a radical -O-Aryl, wherein Aryl is as defined above.

Preferred aryloxy groups include phenoxy, naphthyloxy and the like.

Arylalkyl, as used herein, means a radical -R-Aryl, wherin R is alkyl as defined above. - -

Arylalkoxyalkyl, as used herein, means a radical -ROR-Aryl, wherein each R is, independently, alkyl as defined above.

Aryloxyalkyl, as used herein, means a radical -RO-Aryl, wherein R is alkyl as defined above. Arylthio, as used herein, means a radical -S-Aryl.

Arylthioalkyl, as used herein, means a radical -RS-Aryl, wherein R is alkyl as defined above.

Arylalkylthioalkyl, as used herein, means a radical -RSR-Aryl, wherein each R is, independently, alkyl as defined above. Arylcarbonyl, as used herein, means a radical -C(0)-Aryl.

Arylcarbonylalkyl, as used herein, means a radical -RC(0)-Aryl, wherein R is alkyl as defined above.

Aryloxycarbonyl, as used herein, means a radical -C(0)0-Aryl.

Arylalkoxycarbonyl, as used herein, means a radical -C(0)OR-Aryl, wherein R is alkyl as defined above.

Aryloxyalkylcarbonyl, as used herein, means a radical -C(0)RO-Aryl, wherein R is alkyl as defined above.

Arylcarbonyloxyalkyl, as used herein, means a radical -ROC(0)-Aryl, wherein R is alkyl as defined above. Aryloxycarbonyloxyalkyl, as used herein, means a radical -ROC(0)OAryl, wherein R is alkyl as defined above.

Arylsulphonyl, as used herein, means a radical -S(0) ₂ Aryl.

Heteroaryl, as used herein, means 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. 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, means a radical -R-Het, wherein R is alkyl as defined above and Het is heteroaryl as defined above.

Heterocyclyl, as used herein, means a non-aromatic ring system containing 3 to 10 ring atoms, at least one ring heteroatom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur. Examples of such groups include pyrrolidinyl, imidazolinyl, pyrazolidinyl, piperidyl, piperazinyl, quinuclidinyl, morpholinyl, tetrahydrofuranyl, together with unsaturated or partially unsaturated analogues such as 4,5,6,7- tetrahydro-benzothiophenyl, chromen-4-onyl, 9H-fluorenyl, 3,4-dihydro-2H-benzo-1 ,4-dioxepinyl, 2,3-dihydro-benzofuranyl, piperidinyl, 1 ,3-dioxolanyl, 1 ,3-dioxanyl and 4,5-dihydro-isoxazolyl.

Aminocarbonyl, as used herein, means a radical -C(0)NH ₂ .

Alkylaminocarbonyl, as used herein, means a radical -C(0)NRH, wherein R is alkyl as defined above.

Dialkylaminocarbonyl, as used herein, means a radical -C(0)NRR, wherein each R is, independently, alkyl as defined above.

Alkoxycarbonylaminoalkyl, as used herein, means a radical -RNHC(0)OR, wherein each R is, independently, alkyl as defined above.

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 ²⁹ R ³⁰ R 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 also 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.

Compounds of the invention may be prepared by techniques known to the person skilled in the art of organic chemistry. 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 ⁷ , R ⁸ , R ⁹ , R ⁰ , m, n, p, A, W and X 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

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 (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 trifluoromethanesulphonyl 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

For example, a compound of formula (E) in which LG' is a halogen, for example a bromim atom, may be treated with a sulphonamide RS0 ₂ NH 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

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.

Compounds of formula (G) are commercially available or can be made by standard methods well known in the chemical literature. Alternatively, compounds of formula (F) may be prepared from compounds of formula (H) as shown in reaction scheme 7.

Reaction scheme 7 - -

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 (H) 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 (J) and compounds of formula (B) as shown in reaction scheme 8

Reaction scheme 8

(B) (I) For example, a compound of formula (J) in which LG is a halogen, for example a chlorine atom, may be reacted with a compound of formula (B) in the presence of a base, for example an inorganic base such as potassium t-butoxide, in a suitable solvent, for example tetrahydrofuran.

Compounds of formula (J) may be prepared from compounds of formula (A) as shown in reaction scheme 9. Reaction scheme 9

For example, a compound of formula (A) 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 (K) as shown in reaction scheme 10

Reaction scheme 10

(K) (I)

For example, a compound of formula (K) may be treated with an amine derivative H ₂ NX or its salt, for example a substituted hydrazine hydrochloride, in the presence of a base, for example a mild base such as sodium acetate, in a suitable solvent, for example methanol.

Compounds of formula (K) may be prepared from compounds of formula (J) and compounds of formula (L) as shown in reaction scheme 1 1.

Reaction scheme 1 1

(L) (K)

For example, a compound of formula (J) in which LG is a halogen, for example a chlorine atom, may be reacted with a compound of formula (L) in the presence of a base, for example an inorganic base such as potassium t-butoxide, in a suitable solvent, for example tetrahydrofuran. Alternatively, compounds of formula (K) may be prepared from compounds of formula (M) as shown in reaction scheme 12.

Reaction scheme 12

- -

For example, a compound of formula (M) may be reacted with an aldehyde, for example aqueous formaldehyde, in the presence of an acid, for example an organic acid such as para- toluene sulphonic acid, in a suitable solvent, for example dioxane.

Compounds of formula (M) in which R is H and p = 0 may be prepared from compounds of formula (N) in as shown in reaction scheme 13

Reaction scheme 13

(N) (I)

For example, a compound of formula (N) may be treated with a base, for example a strong base such as sodium hexamethyldisilazide, and a nitrosylating agent, for example isopentyl nitrite, in a suitable solvent, for example tetrahydrofuran.

Compounds of formula (N) may be prepared by methods known in the literature, for example as described in WO2010/026989 and WO2015/004282.

Compounds of formula (I) in which R is H may be prepared from compounds of formula (O) as shown in reaction scheme 14 Reaction scheme 14

(I)

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

Compounds of formula (O) may be prepared from compounds of formula (P) as shown in reaction scheme 15.

Reaction scheme 15 - -

(P) (O)

For example, a compound of formula (P) 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 (P) may be made from compounds of formula (Q) and compounds of formula (B), as shown in reaction scheme 16.

Reaction scheme 16

( ^Q ) (B) (P)

For example, a compound of formula (Q) 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 (Q) are commercially available or can be made by standard methods well known in the chemical literature. Compounds of formula (B) may be made from compounds of formula (L) as shown in reaction scheme 17

Reaction scheme 17

- -

For example, a compound of formula (L) may be treated with an amine derivative H ₂ NX or its salt, for example a hydrazine hydrochloride salt, in the presence of a base, for example a mild base such as sodium acetate, in a suitable solvent, for example methanol.

Compounds of formula (L) are commercially available or can be made by standard methods well known in the chemical literature. For example, compounds of formula (L) may be prepared from compounds of formula (R) as shown in reaction scheme 18.

Reaction scheme 18

For example, a compound (R) may be treated with an oxidising agent, for example a hypervalent iodine compound such as the Dess-Martin periodinane, in a suitable solvent, for example dichloromethane.

Compounds of formula (R) may be prepared from compounds of formula (S) as shown reaction scheme 19.

Reaction scheme 19

(S) (R)

For example, a compound of formula (S) may be reacted with a base, for example an inorganic base such as potassium carbonate, in a suitable solvent, for example an alcoholic solvent such as methanol.

Compounds of formula (S) may be prepared from compounds of formula (T), as shown in reaction scheme 20.

Reaction scheme 20 - -

For example, a compound of formula (T) in which LG is a bromine atom may be reacted with a suitable nucleophile, for example potassium acetate, optionally in the presence of an additive such as 18-crown-6, in a suitable solvent, for example acetonitrile. Compounds of formula (T) may be prepared from compounds of formula (U), as shown in reaction scheme 21.

Reaction scheme 21

For example, a compound of formula (U) may be treated with a halogenation reagent, for example a brominating reagent such as phenyltrimethylammonium tribromide, optionally in the presence of a base, for example an organic base such as triethylamine, and a suitable additive, for example a silylating agent such as trimethylsilyl trifluoromethanesulphonate, in a suitable solvent, for example dichloromethane.

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

Alternatively compounds of formula (R) may be prepared from compounds of formula (V), as shown in reaction scheme 2.

Reaction scheme 22 - -

For example, a compound of formula (V) may be reacted with a Lewis acid, for example, boron tribromide, in a suitable solvent, for example dichloromethane.

Compounds of formula (V) may be prepared from compounds of formula (W), as shown in reaction scheme 23.

Reaction scheme 23

(W) (V)

For example, a compound of formula (W) may be treated with a reducing agent, for example a metal hydride reducing agent such sodium borohydride, optionally in the presence of an additive, for example a metal salt such as cobalt chloride, in a suitable solvent, for example tetrahydrofuran.

Compounds of formula (W) in which p = 0 can be prepared from compounds of formula (X), as shown in reaction scheme 24.

Reaction scheme 24

- -

For example, a compound of formula (X) may be heated with a suitable additive, for example a metal salt such as lithium chloride, in a suitable solvent, for example dimethyl sulphoxide.

Compounds of formula (X) may be prepared from compounds of formula (Y) and compounds of formula (Z), as shown in reaction scheme 25.

Reaction scheme 25

(Y) (Z) (X)

For example, a mixture of a compound of formula (Y) and a compound of formula (Z) maybe treated with a base, for example a strong base such as lithium hexamethyldisilazide, in a suitable solvent, such as tetrahydrofuran.

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

Compounds of formula (Z) may be prepared from compounds of formula (AA) and compounds of formula (BB), as shown in reaction scheme 26.

Reaction scheme 26

(AA) (BB) (Z)

For example, a mixture of a compound of formula (AA) and a compound of formula (BB) may be treated with a base, for example an organic base such as piperidine, optionally in the presence of a suitable solvent, for example tetrahydrofuran. Compounds of formula (AA) and compounds of formula (BB) are commercially available or can be made by standard methods well known in the chemical literature.

Alternatively, compounds of formula (L) in which p = 0 may be prepared from compounds of formula (CC), as shown in reaction scheme 27.

Reaction scheme 27 - -

For example, a compound of formula (CC) may be heated in the presence of a catalyst, for example an acid, such as para-toluene sulphonic acid, in a suitable solvent, for example dioxane.

Compounds of formula (CC) may be prepared from compounds of formula (DD), as shown in reaction scheme 28.

Reaction scheme 28

(DD) (CC)

For example, a compound of formula (DD) may be heated with morpholine.

Compounds of formula (DD) may be prepared from compounds of formula (U), as shown in reaction scheme 29.

Reaction scheme 29

(U) (DD)

For example, a compound of formula (U) may be treated with a chlorinating reagent, for example phosphorus pentachloride, in a suitable solvent, for example chloroform.

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 30.

Reaction scheme 30 - -

(I) e>

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.

Alternatively, a compound of formula (I) in which R is not H may be prepared from compounds of formula (EE) as shown in reaction scheme 31.

Reaction scheme 31

(EE) (I)

For example, a compound of formula (EE) may be treated with a sulphonylating reagent, for example a sulphonyl halide such as trifluoromethanesulphonyl chloride, in the presence of a base, for example an inorganic base such as sodium hydride, in a suitable solvent, for example dimethoxyethane.

Compounds of formula (EE) may be prepared from compounds of formula (O), as shown in reaction scheme 32. Reaction scheme 32

(O) (EE)

For example, a compound of formula (O) may be treated with a base, for example an inorganic base such as sodium bicarbonate or an organic base such as triethylamine, and an - - electrophilic reagent LG-R , for example a chloroformate, in a suitable solvent, for example acetonitrile.

Compounds of formula (I) in which m is not 0 may be prepared from compounds of formula (I), as shown in reaction scheme 33.

Reaction scheme 33

For example, a compound of formula (I) in which R is H may be treated with a suitable electrophilic reagent, for example a halogenating agent such as N-bromosuccinimide, optionally in the presence of an additive, such as a radical initiator such as AIBN, in a suitable solvent, for example carbon tetrachloride.

Compounds of formula (I) in which R ⁹ or R ⁰ is not H may be prepared from compounds of formula (I) in which R ⁹ or R ⁰ is H and an electrophilic reagent (FF) as shown in reaction scheme 34

Reaction scheme 34

For example, a compound of formula (I) in which R ⁰ is not H may be treated with an electrophilic reagent (FF) in the presence of a base, for example a strong base such as potassium t-butoxide, in a suitable solvent, for example tetrahydrofuran.

Electrophilic reagents (FF) are commercially available or can be made by procedures well known in the literature.

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 ⁷ , R ⁸ , m, n, p, A, W and X 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 compounds according to the invention are generally formulated in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. 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 and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, 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. 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 can 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. 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 formulations 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, N,N- dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, 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, 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, tetrahydro- furfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2- pyrrolidone and the like.

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.

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 dodecyl- benzenesulfonate; 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 be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.

The formulations according to the invention can 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 mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a 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, 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. Preferred oil additives comprise alkyl esters of C ₈ -C ₂ 2 fatty acids, especially the methyl derivatives of d ₂ - C-I8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 ^th Edition, Southern Illinois University, 2010. The formulations generally comprise from 0.1 to 99 % by weight, especially from 0.1 to

95 % by weight, of the compound 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 may preferably be formulated as concentrates, the end user will normally employ dilute formulations. The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha. Preferred formulations can have the following compositions (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.

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

Powders for drv seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % - -

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

The combination 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.

I Coated qranules I I - -

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

Suspension concentrate

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable concentrate for seed treatment

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension - -

28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose. 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) or a composition according to the invention.

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) or a composition according to the invention.

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 plants or to the locus of said useful plants, a compound of formula (I) or a composition according to 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) or a composition according to the invention.

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 "locus" as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.

The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.

The term "plant propagation material" denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants. - -

Crops of useful plants in which the compounds and composition according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.

Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour). Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors. An example of a crop that has been rendered tolerant to

imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer 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 Round upReady®, Herculex I® and LibertyLink®.

Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.

An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant - - can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

Compounds and compositions of the invention can typically be used to control a wide variety of monocotyledonous and dicotyledonous weed species. Examples of monocotyledonous species that can typically be controlled include Alopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloa crus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poa annua, Setaria viridis, Setaria faberi and Sorghum bicolor. Examples of dicotyledonous species that can be controlled include Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochia scoparia, Polygonum convolvulus,

Sida spinosa, Sinapis arvensis, Solanum nigrum, Stellaria media, Veronica persica and Xanthium strumarium.

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 to the weeds.

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).

Compounds of formula I can be used in combination with one or more other herbicides to provide various herbicidal mixtures. Specific examples of such mixtures include (wherein Ί" represents a compound of formula I):- 1 + acetochlor, I + acifluorfen, I + acifluorfen-sodium, I + aclonifen, I + acrolein, I + alachlor, I + alloxydim, I + allyl alcohol, I + ametryn, I +

amicarbazone, I + amidosulfuron, I + aminocyclopyrachlor, I + aminopyralid, I + amitrole, I + ammonium sulfamate, I + anilofos, I + asulam, I + atrazine, I + aviglycine, I + azafenidin, I + azimsulfuron, I + BCPC, I + beflubutamid, I + benazolin, I + bencarbazone, I + benfluralin, I + benfuresate, I + bensulfuron, I + bensulfuron-methyl, I + bensulide, I + bentazone, I + benzfendizone, I + benzobicyclon, I + benzofenap, I + bicyclopyrone, I + bifenox, I + bilanafos, I + bispyribac, I + bispyribac-sodium, I + borax, I + bromacil, I + bromobutide, I +

bromophenoxim, I + bromoxynil, I + butachlor, I + butafenacil, I + butamifos, I + butralin, I + - - butroxydim, I + butylate, I + cacodylic acid, I + calcium chlorate, I + cafenstrole, 1 + carbetamide, I + carfentrazone, I + carfentrazone-ethyl, I + CDEA, I + CEPC, I + chlorflurenol, I + chlorflurenol-methyl, I + chloridazon, I + chlorimuron, I + chlorimuron-ethyl, I + chloroacetic acid, I + chlorotoluron, I + chlorpropham, I + chlorsulfuron, I + chlorthal, I + chlorthal-dimethyl, I + cinidon-ethyl, I + cinmethylin, I + cinosulfuron, I + cisanilide, I + clethodim, I + clodinafop, I + clodinafop-propargyl, I + clomazone, I + clomeprop, I + clopyralid, I + cloransulam, I + cloransulam-methyl, I + CMA, I + 4-CPB, I + CPMF, I + 4-CPP, I + CPPC, I + cresol, I + cumyluron, I + cyanamide, I + cyanazine, I + cycloate, I + cyclosulfamuron, I + cycloxydim, I + cyhalofop, I + cyhalofop-butyl, I + 2,4-D, I + 3,4-DA, I + daimuron, I + dalapon, I + dazomet, I + 2,4-DB, I + 3,4-DB, I + 2,4-DEB, I + desmedipham, I + desmetryn, I + dicamba, l + dichlobenil, I + ortho-dichlorobenzene, I + para-dichlorobenzene, I + dichlorprop, I + dichlorprop-P, I + diclofop, I + diclofop-methyl, I + diclosulam, I + difenzoquat, I + difenzoquat metilsulfate, I + diflufenican, I + diflufenzopyr, I + dimefuron, I + dimepiperate, I +

dimethachlor, I + dimethametryn, I + dimethenamid, I + dimethenamid-P, I + dimethipin, I + dimethylarsinic acid, I + dinitramine, I + dinoterb, I + diphenamid, I + dipropetryn, I + diquat, I + diquat dibromide, I + dithiopyr, I + diuron, I + DNOC, I + 3,4-DP, I + DSMA, I + EBEP, I + endothal, I + EPTC, I + esprocarb, I + ethalfluralin, I + ethametsulfuron, I + ethametsulfuron- methyl, I + ethephon, I + ethofumesate, I + ethoxyfen, I + ethoxysulfuron, I + etobenzanid, I + fenoxaprop, I + fenoxaprop-P, I + fenoxaprop-ethyl, I + fenoxaprop-P-ethyl, I + fentrazamide, I + ferrous sulfate, I + flamprop-M, I + flazasulfuron, I + florasulam, I + fluazifop, I + fluazifop- butyl, I + fluazifop-P, I + fluazifop-P-butyl, I + fluazolate, I + flucarbazone, I + flucarbazone- sodium, I + flucetosulfuron, I + fluchloralin, I + flufenacet, I + flufenpyr, I + flufenpyr-ethyl, I + flumetralin, I + flumetsulam, I + flumiclorac, I + flumiclorac-pentyl, I + flumioxazin, I + flumipropin, I + fluometuron, I + fluoroglycofen, I + f I uoroglycof en-ethyl, I + fluoxaprop, I + flupoxam, I + flupropacil, I + flupropanate, I + flupyrsulfuron, I + flupyrsulfuron-methyl-sodium, I + flurenol, I + fluridone, I + flurochloridone, I + fluroxypyr, I + flurtamone, I + fluthiacet, I + fluthiacet-methyl, I + fomesafen, I + foramsulfuron, I + fosamine, I + glufosinate, I + glufosinate-ammonium, I + glyphosate, I + halauxifen, I + halauxifen-methyl, I + halosulfuron, I + halosulfuron-methyl, I + haloxyfop, I + haloxyfop-P, I + HC-252, I + hexazinone, I + imazamethabenz, I + imazamethabenz-methyl, I + imazamox, I + imazapic, I + imazapyr, I + imazaquin, I + imazethapyr, I + imazosulfuron, I + indanofan, I and indaziflam, I +

iodomethane, I + iodosulfuron, I + iodosulfuron-methyl-sodium, I + ioxynil, I + ipfencarbazone, I + isoproturon, I + isouron, I + isoxaben, I + isoxachlortole, I + isoxaflutole, I + isoxapyrifop, I + karbutilate, I + lactofen, I + lenacil, I + linuron, I + MAA, I + MAMA, I + MCPA, I + MCPA- thioethyl, I + MCPB, I + mecoprop, I + mecoprop-P, I + mefenacet, I + mefluidide, I + mesosulfuron, I + mesosulfuron-methyl, I + mesotrione, I + metam, I + metamifop, I + metamitron, I + metazachlor, I + metazosulfuron, I + methabenzthiazuron, I + methazole, I + methiozolin, I + methylarsonic acid, I + methyldymron, I + methyl isothiocyanate, l + metobenzuron, I + metobromuron, I + metolachlor, I + S-metolachlor, I + metosulam, I + metoxuron, I + metribuzin, I + metsulfuron, I + metsulfuron-methyl, I + MK-616, I + molinate, I + monolinuron, I + monosulfuron, I + monosulfuron-ester I + MSMA, I + naproanilide, I + - - napropamide, I + naptalam, I + NDA-402989, I + neburon, I + nicosulfuron, I + nipyraclofen, I + n-methyl glyphosate, I + nonanoic acid, I + norflurazon, I + oleic acid (fatty acids), I + orbencarb, I + orthosulfamuron, I + oryzalin, I + oxadiargyl, I + oxadiazon, I + oxasulfuron, I + oxaziclomefone, I + oxyfluorfen, I + paraquat, I + paraquat dichloride, I + pebulate, l + pendimethalin, I + penoxsulam, I + pentachlorophenol, I + pentanochlor, I + pentoxazone, I + pethoxamid, I + petrolium oils, I + phenmedipham, I + phenmedipham-ethyl, I + picloram, I + picolinafen, I + pinoxaden, I + piperophos, I + potassium arsenite, I + potassium azide, I + pretilachlor, I + primisulfuron, I + primisulfuron-methyl, I + prodiamine, I + profluazol, I + profoxydim, I + prohexadione-calcium, I + prometon, I + prometryn, I + propachlor, I + propanil, I + propaquizafop, I + propazine, I + propham, I + propisochlor, I + propoxycarbazone, l + propoxycarbazone-sodium, I + propyzamide, I + prosulfocarb, I + prosulfuron, I + pyraclonil, I + pyraflufen, I + pyraflufen-ethyl, I + pyrasulfotole, I + pyrazolynate, I + pyrazosulfuron, I + pyrazosulfuron-ethyl, I + pyrazoxyfen, I + pyribenzoxim, I + pyributicarb, I + pyridafol, I + pyridate, I + pyriftalid, I + pyriminobac, I + pyriminobac-methyl, I + pyrimisulfan, I + pyrithiobac, I + pyrithiobac-sodium, I + pyroxasulfone, I + pyroxulam, I + quinclorac, I + quinmerac, I + quinoclamine, I + quizalofop, I + quizalofop-P, I + quizalofop-ethyl, I + quizalofop-P-ethyl, I + rimsulfuron, I + saflufenacil, I + sethoxydim, I + siduron, I + simazine, I + simetryn, I + SMA, I + sodium arsenite, I + sodium azide, I + sodium chlorate, I + sulcotrione, I + sulfentrazone, I + sulfometuron, I + sulfometuron-methyl, I + sulfosate, I + sulfosulfuron, I + sulfuric acid, I + tar oils, I + 2,3,6-TBA, I + TCA, I + TCA-sodium, I + tebutam, I + tebuthiuron, I + tefuryltrione, I + tembotrione, I + tepraloxydim, I + terbacil, I + terbumeton, I + terbuthylazine, I + terbutryn, I + thenylchlor, I + thiazafluron, I + thiazopyr, I + thifensulfuron, I + thiencarbazone, I + thifensulfuron-methyl, I + thiobencarb, I + tiocarbazil, I + topramezone, I + tralkoxydim, I + triafamone I + tri-allate, I + triasulfuron, I + triaziflam, I + tribenuron, I + tribenuron-methyl, I + tricamba, I + triclopyr, I + trietazine, I + trifloxysulfuron, I + trifloxysulfuron-sodium, I + trifluralin, I + triflusulfuron, I + triflusulfuron-methyl, I + trifop, I + trifop-methyl, I +

trihydroxytriazine, I + trinexapac-ethyl, I + tritosulfuron, 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), I + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl-1 ,3-cyclohexanedione, I + 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methoxyphenyl)-5-fluoropyridine-2-carboxylate and I + VX-573.

In particular, the following mixtures are important:

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

Mixtures of a compound of formula (I) with an HPPD inhibitor (e.g. I + isoxaflutole, I + mesotrione, I + pyrasulfotole, I + sulcotrione, I + tembotrione, I + topramezone, I + bicyclopyrone, I + benzobicyclon or I + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione (CAS RN 1342891-70-6)). Mixtures of a compound of formula (I) with an auxin (e.g. I + dicamba, I + 2,4-D, I + 2,4- DB, I + MCPA, I + fluroxypyr, I + picloram, I + triclopyr, I + quinclorac, I + clopyralid, I + aminopyralid, I + aminocyclopyrachlor, I + halauxifen, I + halauxifen-methyl).

Mixtures of a compound of formula (I) with a VLCFA inhibitor (e.g. I + metolachlor, I + S- metolachlor, I + acetochlor, I + dimethenamid-P, I + pyroxasulfone, I + dimethachlor, I + flufenacet, I + metazachlor, I + napropamide, I + pretilachlor).

Mixtures of a compound of formula (I) with a triazolinone (e.g. I + amicarbazone).

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

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

Mixtures of a compound of formula (I) with a PPO inhibitor (e.g. I + fomesafen, I + flumioxazin, I + sulfentrazone, I + acifluorfen-sodium, I + lactofen, I + oxyfluorfen, I + oxadiazon, I + butafenacil, I + carfentrazone-ethyl, 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).

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

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

Thus, in particular, the following mixtures are preferred: I + ametryn, I + atrazine, I + cyanazine, I + dimethametryn, I + metribuzin, I + prometon, I + prometryn, I + propazine, I + simazine, I + simetryn, I + terbumeton, I + terbuthylazine, I + terbutryn, I + trietazine, I + isoxaflutole, I + mesotrione, I + pyrasulfotole, I + sulcotrione, I + tembotrione, I + topramezone, I + bicyclopyrone, I + benzobicyclon, I + 2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2- quinoxalinyl]carbonyl]1 ,3-cyclohexanedione (CAS RN 1342891-70-6), I + dicamba, I + 2,4-D, I + 2,4-DB, I + MCPA, I + fluroxypyr, I + picloram, I + triclopyr, I + quinclorac, I + clopyralid, I + aminopyralid, I + aminocyclopyrachlor, I + halauxifen, I + halauxifen-methyl, I + metolachlor, I + S-metolachlor, I + acetochlor, I + dimethenamid-P, I + pyroxasulfone, I + dimethachlor, I + flufenacet, I + metazachlor, I + napropamide, I + pretilachlor, I + amicarbazone, I + chlorsulfuron, I + cinosulfuron, I + cloransulam, I + ethametsulfuron, I + flazasulfuron, I + foramsulfuron, I + flumetsulam, I + imazamethabenz, I + imazamox, I + imazapic, I + imazapyr, I + imazethapyr, I + iodosulfuron, I + iofensulfuron, I + metsulfuron, I + nicosulfuron, I + oxasulfuron, I + primisulfuron, I + prosulfuron, I + pyrithiobac, I + pyroxsulam, I + rimsulfuron, I + sulfosulfuron, I +

thifensulfuron, I + triasulfuron, I + tribenuron, I + trifloxysulfuron, I + thiencarbazone, I + tritosulfuron, I + bispyribac-sodium, I + pyribenzoxim, I + pyriftalid, I +flucarbazone-sodium, I +bensulfuron-methyl, I + chlorimuron-ethyl, I + sulfometuron-methyl, I + diclosulam, I + florasulam, I + penoxsulam, I + fomesafen, I + flumioxazin, I + sulfentrazone, I + acifluorfen- sodium, I + lactofen, I + oxyfluorfen, I + oxadiazon, I + butafenacil, I + carfentrazone-ethyl, 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, I + clodinafop, I + fluazifop, I + fenoxaprop, I + clethodim, I + quizalofop, I + haloxyfop, I + pinoxaden, I + cycloxydim, I + sethoxydim, I + glyphosate, I + glufosinate, I + paraquat, I + diquat, I + pendimethalin, I + trifluralin, I + metamitron, I + clomazone, I + prodiamine, I + saflufenacil, I + prosulfocarb, I + diflufenican, I + isoxaben, I + beflubutamide, I + flurtamone, I + benfluralin, I + chlorotoluron, I +linuron, I + isoproturon, I + triallate, I + hexazinone, I + diuron, I + propanil, I + indaziflam.

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

For the avoidance of doubt, the present invention also includes three-way mixtures of a compound of formula (1 ), a herbicide as defined above and a further herbicide. In particular, the following three-way mixtures are preferred: I + atrazine + mesotrione, I + atrazine + S- metolachlor, I + S-metolachlor + mesotrione, I + glyphosate + mesotrione, I + glufosinate + mesotrione, I + atrazine + isoxaflutole, I + S-metolachlor + isoxaflutole, I + glyphosate + isoxaflutole, I + glufosinate + isoxaflutole, 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 mixture is preferred: 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. For example, 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).

Compounds of formula (I) may also be combined with herbicide safeners. As

combinations with safeners, are preferred, for example, (wherein Ί" represents a compound of formula (I)) I + AD-67, I + benoxacor, I + cloquintocet-mexyl, I + cyomerinil, I + dichlormid, I + dicyclonone, I + cyprosulfamide, I + diethorate, I + DKA-24, I + dymron, I + fenclorazole ethyl, I + fenclorim, I + HEXIM, I + flurazole, I + fluxofenim, I + furilazole, I + isoxadifen, I + isoxadifen ethyl, I + MCPA, I + mecoprop, I + mefenpyr, I + mefenpyr ethyl, I + mefenpyr diethyl, I + mephenate, I + MG-191 , I + NA (naphthalic anhydride), I + OM (octamethylene diamine), I + oxabetrinil, I + PPG-1292, I + R-29148, I + N-(2-methoxybenzoyl)-4-

[(methylaminocarbonyl)amino]benzenesulfonamide and the like are mentioned. These components can be used alone or by mixing 2 or more types, and the ratio when they are mixed can also be freely selected.

In particular, the following compound/safener combinations are preferred: I + cloquintocet- mexyl, I + cyprosulfamide, I + N-(2-methoxybenzoyl)-4-

[(methylaminocarbonyl)amino]benzenesulfonamide, I + isoxad if en-ethyl, I + benoxacor, I + dichlormid and 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. For example, 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.

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.

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.

Examples

Example 1 Preparation of 1,1 ,1 -trifluoro-A -(2-{[(£)-9-oxo-10-(phenylhydrazono)-8- azaspiro[4.5]decan-8-yl]methyl}phenyl)methanesulfonamide and 1,1 ,1 -trifluoro-A/-(2-{[(Z)- 9-oxo-10-(phenylhydrazono)-8-azaspiro[4.5]decan-8- yl]methyl}phenyl)methanesulfonamide (Compound 13-302)

Step 1.1 Synthesis of 2-cvano-2-cvclopentylidene-acetic acid

Piperidine (0.18 g, 2.12 mmol) was added to a stirred mixture of ethyl 2-cyanoacetate (6g, 53 mmol) and cyclopentanone (4.4 g, 53 mmol) at room temperature and stirring continued for 2 hours. The reaction mixture was diluted with water (100 ml) and extracted with ethyl acetate (3 x 100 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 2-cyano-2-cyclopentylidene-acetic acid (8.27 g, 87%). H NMR (400 MHz, CDCI ₃ ) δ 4.27 (m, 2H), 3.0 (t, 2H), 2.81 (t, 2H), 1.9-1.7 (m, 4H), 1.34 (t, 3H) ppm.

Step 1.2 Synthesis of 2-cvano-2-[1-(2-hvdroxy-1-methoxy-2-oxo-ethyl)cvclopentyllac etic acid

Ethyl-2-methoxyacetate (2.9 g, 24.5 mmol) was slowly added to a stirred solution of lithium hexamethyldisilazide (1 M in THF; 30 ml, 30 mmol) in tetrahydrofuran (40 ml) at -78 °C. After stirring for 40 minutes at -78 °C a solution of 2-cyano-2-cyclopentylidene-acetic acid (4 g, 22 mmol) in tetrahydrofuran (20 ml) was added. The resulting mixture was stirred for 1 hour at -78 °C, allowed to warm to room temperature over 30 minutes, stirred for 2 hours, then water (60 ml) added. The mixture was extracted with ethyl acetate (3 x 150 ml) and the combined organic extracts washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was then purified by silica gel chromatography to provide 2-cyano-2-[1- (2-hydroxy-1-methoxy-2-oxo-ethyl)cyclopentyl]acetic acid (5.4 g, 90 %). H NMR (400 MHz, CDCI ₃ ) δ 4.28 (m, 4H), 3.93 (m, 2H), 3.34 (s, 3H), 2.17-1.36 (m, 8H), 1.37- 1.33 (m, 6H) ppm.

Step 1.3 Synthesis of 2-[1-(cyanomethyl)cvclopentyll-2-methoxy-acetic acid

A solution of lithium chloride (2.49 g, 58.8 mmol) in water (35 ml) was added to a stirred solution of 2-cyano-2-[1-(2-hydroxy-1-methoxy-2-oxo-ethyl)cyclopentyl] acetic acid (7 g, 24 mmol) in dimethyl sulfoxide (70 ml) at room temperature. The resulting mixture was heated at 1 10 °C for 45 hours, then allowed to cool to room temperature, water added and extracted with ethyl acetate (3 x 100 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 2-[1-(cyanomethyl)cyclopentyl]-2-methoxy-acetic acid (4.6 g, 87%). H NMR (400 MHz, CDCI ₃ ) δ 4.26 (m, 2H), 3.69 (s, 1 H), 3.38 (s, 3H), 2.69-2.45 (m, 2H), 1.89- 1.69 (m, 2H), 1.70-1.64 (m, 5H), 1.63 (m, 1 H), 1.33 (t, 3H) ppm.

Step 1 .4 Synthesis of 10-methoxy-8-azaspiro[4.5ldecan-9-one - -

A solution of cobalt (II) chloride hexahydrate (2.56 g, 19.8 mmol) in water (44.5 ml) was added to a solution of 2-[1-(cyanomethyl)cyclopentyl]-2-methoxy-acetic acid (4.45 g, 19.8 mmol) in tetrahydrofuran (89 ml). Sodium borohydride (3.81 g, 98.8 mmol) was added portionwise over 15 minutes to this stirred mixture at room temperature and stirring continued for 18. The resulting mixture was diluted with 20% isopropyl alcohol in chloroform (40 ml) and filtered through a bed of Celite®. The filtrate was washed with water (30 ml), dried over sodium sulfate and concentrated under reduced pressure to provide 10-methoxy-8-azaspiro[4.5]decan-9-one (3.2 g, 88%). H NMR (400 MHz, CDCI ₃ ) 5 6.01 (s, 1 H), 3.59 (s, 3H), 3.39-3.28 (m, 2H), 3.24 (s, 1 H), 2.04 - 1.69 (m, 1 H), 1.78 (m, 1 H), 1.66 (m, 4H), 1 .56-1.36 (m, 4H) ppm.

Step 1 .5 Synthesis of 10-hydroxy-8-azaspiro[4.5ldecan-9-one

Boron tribromide (1 M solution in dichloromethane; 1.06 ml, 1.06 mmol) was added dropwise to a stirred solution of 10-methoxy-8-azaspiro[4.5]decan-9-one (150 mg, 0.81 mmol) in

dichloromethane (6 ml) maintaining the temperature below -70 °C. The mixture was stirred for 30 minutes, allowed to warm to room temperature and stirred for 2 hours. Aqueous sodium bicarbonate solution was added until the mixture reached pH 7 and the mixture extracted with dichloromethane (3 x 30 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to provide 10-hydroxy-8- azaspiro[4.5]decan-9-one (130 mg, 97 %), which was used without further purification. H NMR (400 MHz, CDCI ₃ ) δ 5.85 (br s, 1 H), 3.95 (s, 1 H), 3.39-3.26 (m, 2H), 2.01-1.86 (m, 1 H), 1.85-1.70 (m, 1 H), 1.74-1.54 (m, 6H), 1.71-1.34 (m, 2H) ppm.

Step 1.6 Synthesis of 8-azaspiro[4.5ldecane-9, 10-dione - -

Dess-Martin periodinane (0.39 g, 0.92 mmol) was added to a stirred solution of 10-hydroxy-8- azaspiro[4.5]decan-9-one (130 mg, 0.76 mmol) in dichloromethane (2.6 ml) under nitrogen and the resulting mixture stirred for 2 hours at room temperature. Dichloromethane (50 ml) was added, followed by 2% aqueous sodium thiosulfate (5 ml) and saturated aqueous sodium bicarbonate (15 ml). The organic layer was separated, dried over sodium sulfate and concentrated under reduced pressure to provide 8-azaspiro[4.5]decane-9, 10-dione (125 mg, 97 %), which was used without further purification. H NMR (400 MHz, CDCI ₃ ) δ 8.06 (s, 1 H), 3.50-3.42 (m, 2H), 2.12-2.04 (m, 4H), 1.73-1.68 (m, 4H), 1.52-1.48 (m, 2H) ppm.

Step 1 .7 Synthesis of 10-methoxyimino-8-azaspiro[4.5ldecan-9-one

Sodium acetate (59 mg, 0.71 mmol) and O-methoxylamine hydrochloride (59 mg, 0.71 mmol) were added to a stirred solution of 8-azaspiro[4.5]decane-9, 10-dione (100 mg, 0.59 mmol) in methanol (1 ml) at room temperature. The resulting mixture was heated at reflux for 2 hours, allowed to cool to room temperature and concentrated under reduced pressure. Water was added to the residue and the resulting mixture extracted with ethyl acetate (3 x 30 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 10-methoxyimino-8-azaspiro[4.5]decan-9-one (62 mg, 53 %). H NMR (400 MHz, CDCI ₃ ) δ 7.80 (s, 1 H), 4.06 (s, 3H), 3.34-3.25 (m, 2H), 2.31-2.26 (m, 2H), 1.88-1.84 (m, 2H), 1.77-1.72 (m, 2H), 1.65-1.62 (m, 2H), 1.58-1.43 (m, 2H) ppm.

Step 1.8 Synthesis of 1 ,1 , 1-trifluoro-A/-{2-[(10-methoxyimino-9-oxo-8-azaspiro[4.5ldec an-8- vDmethyllphenvDmethanesulfonamide - -

Potassium tertiary butoxide (1 M in tetrahydrofuran; 0.64 ml, 0.64 mmol) was added to a stirred solution of 10-methoxyimino-8-azaspiro[4.5]decan-9-one (50 mg, 0.25 mmol) in tetrahydrofuran (1 ml) at room temperature and stirring continued for 15 minutes. A/-[2-(Chloromethyl)phenyl]- 1 , 1 , 1-trifluoro-methanesulfonamide (77 mg, 28 mmol) was added and the resulting mixture stirred for 3 hours. Saturated aqueous ammonium chloride was added and the mixture extracted with ethyl acetate (3 x 30 ml ). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 1 ,1 ,1-trifluoro-A/-{2-[(10-methoxyimino-9-oxo-8- azaspiro[4.5]decan-8-yl)methyl]phenyl}methanesulfonamide (35 mg, 32 %).

Melting point 213-215 °C; H NMR (400 MHz, CDCI ₃ ) δ 1 1 .12 (s, 1 H), 7.60 (d, 1 H), 7.39 (m, 1 H), 7.32 (m, 1 H), 7.24 (m, 1 H), 4.56 (s, 2H), 4.08 (s, 3H), 3.57 (m, 2H), 2.27 (m, 2H), 1.85 (m, 2H), 1 .75 (m, 2H), 1.66 (m, 2H), 1 .41 (m, 2H) ppm. Step 1 .9 Synthesis of A/-{2-[(9, 10-dioxo-8-azaspiro[4.5ldecan-8-yl)methyllphenyl)-1 , 1 , 1-trifluoro- methanesulfonamide

p-Toluenesulfonic acid monohydrate (8.7 g, 46 mmol), formalin (37% aq.; 18 ml, 230 mmol) and water (1 1 ml) were added to a stirred solution of 1 ,1 ,1-trifluoro-A/-{2-[(10-methoxyimino-9-oxo-8- azaspiro[4.5]decan-8-yl)methyl]phenyl}methanesulfonamide (10 g, 23.07 mmol) in dioxane (100 ml) at room temperature. The resulting mixture was heated at 100 °C for 30 minutes, allowed to cool and concentrated under reduced pressure. Water was added and the resulting mixture extracted with ethyl acetate (3 x 300 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide A/-{2-[(9, 10-dioxo-8- azaspiro[4.5]decan-8-yl)methyl]phenyl}-1 , 1 ,1-trifluoro-methanesulfonamide (6.23 g, 67 %). H NMR (400 MHz, CDCI ₃ ) δ 10.71 (s, 1 H), 7.60 (d, 1 H), 7.43 (t, 1 H), 7.35-7.28 (m, 2H), 4.58 (s, 2H), 3.75 (t, 2H), 2.14-2.05 (m, 4H), 1.72-1.48 (m, 6H) ppm. Step 1 .10 Synthesis of 1 , 1 , 1-trifluoro-A/-(2-{[(E)-9-oxo-10-(phenylhydrazono)-8- azaspiro[4.51decan-8-yllmethyl)phenyl)methanesulfonamide and 1 ,1 , 1-trifluoro-A/-(2-{[(Z)-9-oxo- 10-(phenylhvdrazono)-8-azaspiro[4.5ldecan-8-vnmethyl)phenyl) methanesulfonamide (Compound 13-302)

Sodium acetate (165 mg, 1 .97 mmol) and phenylhydrazine hydrochloride (175 mg, 1 .18 mmol) were added to a stirred solution of A/-{2-[(9, 10-dioxo-8-azaspiro[4.5]decan-8-yl)methyl]phenyl}- 1 , 1 , 1-trifluoro-methanesulfonamide (400 mg, 0.98 mmol) in methanol (4 ml) at room

temperature. The resulting mixture was heated at reflux for 2 hours, allowed to cool to room temperature and concentrated under reduced pressure. Water was added to the residue and the resulting mixture extracted with ethyl acetate (3 x 80 ml). The combined organic extracts were washed with water, dried over sodium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 1 ,1 ,1-trifluoro-A/-(2-{[(E)-9- oxo-10-(phenylhydrazono)-8-azaspiro[4.5]decan-8-yl]methyl}ph enyl)methanesulfonamide (197 mg, 40%) and 1 ,1 ,1-trifluoro-A/-(2-{[(Z)-9-oxo-10-(phenylhydrazono)-8-azaspi ro[4.5]decan-8- yl]methyl}phenyl)methanesulfonamide (250 mg, 51 %).

E isomer:

Melting point 139-141 °C; H NMR (400 MHz, d6-DMSO) δ 13.05 (s, 1 H), 7.26-7.35 (m, 5H), 7.14 (m, 3H), 6.86 (m, 1 H), 4.72 (s, 2H), 3.33 (m, 2H), 2.05 (m, 2H), 1 .90 (m, 2H), 1.78 (m, 2H), 1.69 (m, 2H), 1.56 (m, 2H) ppm.

Z isomer:

Melting point 145-147 °C; H NMR (400 MHz, d6-DMSO) δ 8.47 (s, 1 H), 7.35 (m, 4H), 7.30 (m, 4H), 6.91 (m, 1 H), 4.67 (s, 2H), 3.35-3.45 (m, 2H), 2.20 (m, 2H), 1 .95 (m, 2H), 1.80 (m, 4H), 1.59 (m, 2H) ppm.

Example 2 Preparation of 1,1,1-trifluoro-A -(2-{[(1S,2 ?,6S,Z)-6-isopropyl-2-methyl-4-oxo-5- (phenylhydrazono)-3-azabicyclo[4.1.0]heptan-3-yl]methyl}phen yl)methanesulfonamide (Compound 13-308)

Step 2.1 Synthesis of (1 2 5S)-5-isopropyl-2-methyl-bicyclo[3.1.0lhexan-3-one E-oxime - -

A solution of sodium hydroxide (2.40 g, 60.0 mmol) in water (45 ml) was added slowly to a stirred solution of (1 R,2R,5S)-5-isopropyl-2-methyl-bicyclo[3.1.0]hexan-3-one (5 ml, 30 mmol) and hydroxylamine hydrochloride (2.09 g, 30.0 mmol) in ethanol (15 ml) and water (15 ml) at 0 °C under nitrogen, maintaining the temperature below 30 °C. The resulting mixture was stirred at room temperature for 24 hours and then extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide (1 R,2R,5S)-5-isopropyl-2-methyl-bicyclo[3.1.0]hexan-3-one E-oxime (2.93 g, 58%). H NMR (400 MHz, CDCI ₃ ) 5 7.71 (br s, 1 H), 2.71 (d, 1 H), 2.68-2.59 (dq, 1 H), 2.40 (td, 1 H), 1.36 (quintet, 1 H), 1.16 (d, 3H), 1.01-0.91 (m, 7H), 0.55 (ddd, 1 H), 0.04 (dd, 1 H) ppm.

Step 2.2 Synthesis of (1 S,2 6S)-6-isopropyl-2-methyl-3-azabicyclo[4.1.0lheptan-4-one

A solution of sodium hydroxide (2.77 g, 69.4 mmol) in water (17 ml) was added slowly to a stirred solution of (1 R,2R,5S)-5-isopropyl-2-methyl-bicyclo[3.1.0]hexan-3-one E-oxime (2.90 g, 17.3 mmol) in acetone (52 ml). A solution of 4-methylbenzenesulfonyl chloride (5.95 g, 31 .2 mmol) in acetone (52 ml) was added and the resulting mixture stirred at room temperature for 24 hours.

Hydrochloric acid was added to bring the mixture to neutral pH and it was then extracted with dichloromethane. The combined organic extracts were dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide (1 S,2R,6S)-6-isopropyl-2-methyl-3-azabicyclo[4.1 .0]heptan-4-one

(2.43 g, 88%). H NMR (400 MHz, CDCI ₃ ) δ 3.76-3.68 (m, 1 H), 2.49 (br d, 2H), 2.20 (br s, 1 H), 1 .33 (d, 3H), 1.17-1.06 (m, 1 H), 0.99 (d, 3H), 0.95 (d, 3H), 0.91-0.78 (m, 1 H), 0.60 (t, 1 H), 0.50 (dd, 1 H) ppm. Step 2.3 Synthesis of 1 , 1 , 1 -trifluoro-A/-(2-{[(1 S,2 6S)-6-isopropyl-2-methyl-4-oxo-3- azabicyclo[4.1.01heptan-3-yllmethyl)phenyl)methanesulfonamid e

Potassium tertiary butoxide (1 M in tetrahydrofuran; 30.2 ml, 30.2 mmol) was added to a stirred solution of provide (1 S,2R,6S)-6-isopropyl-2-methyl-3-azabicyclo[4.1 .0]heptan-4-one (2.42 g, 14.5 mmol) in tetrahydrofuran (30 ml) at room temperature and stirring continued for 15 minutes. A solution of A/-[2-(chloromethyl)phenyl]-1 , 1 ,1 -trifluoro-methanesulfonamide (3.31 g, 12.1 mmol) in tetrahydrofuran (18 ml) was added and the resulting mixture stirred for 16 hours. Hydrochloric acid was added and the mixture extracted with ethyl acetate. The combined organic extracts were washed with water, dried over magnesium sulfate and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 1 , 1 ,1- trifluoro-A/-(2-{[(1 S,2R,6S)-6-isopropyl-2-methyl-4-oxo-3-azabicyclo[4.1.0]hepta n-3- yl]methyl}phenyl)methanesulfonamide (3.91 g, 80 %). H NMR (400 MHz, CDCI ₃ ) 5 1 1 .64 (br s, 1 H), 7.61 (dd, 1 H), 7.37 (t, 1 H), 7.27 (dd, 1 H), 7.23- 7.16 (m, 1 H), 4.65 (d, 1 H), 4.17 (d, 1 H), 3.90 (dd, 1 H), 2.63 (dd, 1 H), 2.52-2.44 (m, 1 H), 1.31 (d, 3H), 1.16-1.04 (m, 1 H), 1.02-0.88 (m, 7H), 0.32 (ddd, 1 H), 0.13 (t, 1 H) ppm.

Step 2.4 Synthesis of 1 , 1 , 1 -trifluoro-A/-(2-{[(1 S,2 6S,Z)-5-hvdroxyimino-6-isopropyl-2-methyl-4- oxo-3-azabicyclo[4.1 .01heptan-3-yllmethyl)phenyl)methanesulfonamide

Sodium hexamethyldisilazide (1 M in tetrahydrofuran; 7.4 ml, 7.4 mmol) was added to a stirred solution of 1 , 1 , 1 -trifluoro-A/-(2-{[(1 S,2R,6S)-6-isopropyl-2-methyl-4-oxo-3- azabicyclo[4.1.0]heptan-3-yl]methyl}phenyl)methanesulfonamid e (0.86 g, 2.1 mmol) in tetrahydrofuran (10.6 ml). The resulting mixture was stirred at room temperature for 30 minutes, then isopentyl nitrite (0.43 ml, 3.2 mmol) was added and stirring continued. Further sodium hexamethyldisilazide (1 M in tetrahydrofuran; 3.7 ml, 3.7 mmol) and isopentyl nitrite (0.43 ml, 3.2 mmol) were added and stirring continued for 17 hours. Hydrochloric acid was added and the mixture extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulphate, filtered and concentrated under reduced pressure to leave a - - residue which was purified by silica gel chromatography to provide 1,1,1-trifluoro-A/-(2- {[(1S,2R,6S,Z)-5-hydroxyimino-6-isopropyl-2-methyl-4-oxo-3-a zabicyclo[4.1.0]heptan-3- yl]methyl}phenyl)methanesulfonamide (0.29 g, 31%). H NMR(400 MHz, CDCI ₃ )513.26 (br s, 1H), 10.00 (brs, 1H),7.59 (d, 1H),7.42 (dt, 1H),7.32- 7.24 (m, 2H), 4.81 (d, 1H), 4.13 (d, 1H), 4.08-4.01 (m, 1H), 2.19 (m, 1H), 1.41-1.35 (m, 4H), 1.01 (d, 3H), 0.96-0.90 (m, 1H), 0.89 (d, 3H), 0.42 (t, 1H) ppm.

Step 2.5 Synthesis of 1,1,1 -trifluoro-A/-(2-{[(1S,2 6S)-6-isopropyl-2-methyl-4,5-dioxo-3- azabicvclo[4.1.01heptan-3-yllmethyl)phenyl)methanesulfonamid e

p-Toluenesulfonic acid monohydrate (0.19 g, 0.50 mmol), formalin (37% aq.; 0.37 ml, 5.0 mmol) and water (0.25 ml) were added to a stirred solution of 1,1,1-trifluoro-A/-(2-{[(1S,2R,6S,Z)-5- hyd roxyi mi no-6-isopropyl-2-m ethyl-4-oxo-3-azabicyclo[4.1.0] heptan-3- yl]methyl}phenyl)methanesulfonamide (0.215 g, 0.496 mmol) in tetrahydrofuran (2.2 ml) at room temperature. The resulting mixture was heated at 100 °C for 90 minutes in a microwave reactor, then allowed to cool. Water was added and the resulting mixture extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatog raphy to provide 1,1,1 -trif I uoro-A/-(2-{[( 1 S,2R, 6S)-6-isopropyl-2-m ethyl-4 ,5-d ioxo-3- azabicyclo[4.1.0]heptan-3-yl]methyl}phenyl)methanesulfonamid e (147 mg, 71 %). H NMR (400 MHz, CDCI ₃ ) δ 7.58 (d, 1H), 7.43-7.24 (m, 3H), 4.81 (d, 1H), 4.18-4.05 (m, 2H), 1.92 (heptet, 1H), 1.76 (ddd, 1H), 1.44 (d, 3H), 1.19 (dd, 1H), 1.05-0.94 (m, 7H) ppm.

Step 2.6 Synthesis of 1,1,1-trifluoro-A/-(2-{[(1S,2 6S,Z)-6-isopropyl-2-methyl-4-oxo-5-

(phenylhvdrazono)-3-azabicvclo[4.1.0lheptan-3-yllmethyl)p henyl)methanesulfonamide

(Compound 13-308)

Phenylhydrazine (0.01 ml, 0.1 mmol) was added to a stirred solution of 1,1,1-trifluoro-A/-(2- {[(1S,2R,6S)-6-isopropyl-2-methyl-4,5-dioxo-3-azabicyclo[4.1 .0]heptan-3- - - yl]methyl}phenyl)methanesulfonamide (34 mg, 0.08 mmol) in ethanol (1.2 ml) at room temperature. The resulting mixture was heated at reflux for 17 hours, then further

phenylhydrazine (0.01 ml, 0.1 mmol) added and the mixture heated at reflux for a further 24 hours. Additional phenylhydrazine (0.01 ml, 0.1 mmol) was added, the mixture heated at reflux for 4 hours, then allowed to cool to room temperature. Hydrochloric acid was added and the resulting mixture extracted with ethyl acetate. The combined organic extracts were washed with water, dried over magnesium sulfate, filtered and concentrated under reduced pressure to leave a residue which was purified by silica gel chromatography to provide 1 , 1 , 1 -trif I uoro-/V-(2- {[(1 S,2R,6S,Z)-6-isopropyl-2-methyl-4-oxo-5-(phenylhydrazono)-3- azabicyclo[4.1.0]heptan-3- yl]methyl}phenyl)methanesulfonamide (34 mg, 82%). H NMR (400 MHz, d6-DMSO) δ 12.01 (s, 1 H), 1 1.02 (br s, 1 H), 7.63 (d, 1 H), 7.41-7.36 (m, 1 H), 7.32-7.27 (m, 3H), 7.24-7.14 (m, 3H), 6.90 (t, 1 H), 4.53-4.43 (m, 2H), 3.99-3.93 (m, 1 H), 2.26 (br s, 1 H), 1 .31 (ddd, 1 H), 1.21 (d, 3H), 1.10 (d, 3H), 0.95 (d, 3H), 0.93-0.85 (m, 1 H), 0.52 (t, 1 H) ppm. Example 3 Preparation of ethyl A -(2-{[(1 S,2 ?,6S,Z)-6-isopropyl-2-methyl-4-oxo-5- (phenylhydrazono)-3-azabicyclo[4.1.0]heptan-3-yl]methyl}phen yl)-A - (trifluoromethylsulfonyl)carbamate (Compound 16-308) and ethyl A -[2-({(1 S,2 ?,6S,Z)-5- [ethoxycarbonyl(phenyl)hydrazono]-6-isopropyl-2-methyl-4-oxo -3-azabicyclo[4.1.0]heptan- 3-yl}methyl)phenyl]-A -(trifluoromethylsulfonyl)carbamate (Compound 16-440)

Sodium hydrogen carbonate (12 mg, 0.14 mmol) and ethyl chloroformate (0.013 ml, 0.14 mmol) were added to a stirred solution of 1 ,1 ,1-trifluoro-A/-(2-{[(1 S,2R,6S,Z)-6-isopropyl-2-methyl-4-oxo- 5-(phenylhydrazono)-3-azabicyclo[4.1.0]heptan-3-yl]methyl}ph enyl)methanesulfonamide (35 mg, 0.069 mmol) in acetonitrile (1.5 ml) and the mixture was heated at reflux for 4 hours, then allowed to cool to room temperature. Water and hydrochloric acid were added and the resulting mixture extracted with ethyl acetate. The combined organic extracts were washed with aqueous sodium - - hydroxide and brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography to provide ethyl Λ/-(2- {[(1 S,2R,6S,Z)-6-isopropyl-2-methyl-4-oxo-5-(phenylhydrazono)-3- azabicyclo[4.1.0]heptan-3- yl]methyl}phenyl)-A/-(trifluoromethylsulfonyl)carbamate (33 mg, 83%) and ethyl N-[2- ({(1 S,2R,6S,Z)-5-[ethoxycarbonyl(phenyl)hydrazono]-6-isopropyl-2 -methyl-4-oxo-3- azabicyclo[4.1.0]heptan-3-yl}methyl)phenyl]-A/-(trifluoromet hylsulfonyl)carbamate (3 mg, 7%).

Ethyl A/-(2-{[(1 S,2R,6S,Z)-6-isopropyl-2-methyl-4-oxo-5-(phenylhydrazono)-3- azabicyclo[4.1.0]heptan-3-yl]methyl}phenyl)-A/-(trifluoromet hylsulfonyl)carbamate: H NMR (400 MHz, CDCI ₃ ) δ 12.39 (d, 1 H), 7.50-7.46 (m, 1 H), 7.40-7.33 (m, 2H), 7.29-7.24 (m, 2H), 7.24-7.18 (m, 1 H), 7.18-7.13 (m, 2H), 6.87 (dt, 1 H), 5.24 (d, 0.5H), 5.04 (d, 0.5H), 4.43-4.27 (m, 2.5H), 4.10 (d, 0.5H), 3.75-3.69 (m, 0.5H), 3.67-3.62 (m, 0.5H), 2.44-2.21 (m, 1 H), 1.36-1.29 (m, 4H), 1.29-1.20 (m, 3H), 1.17-1.12 (m, 3H), 0.98 (d, 3H), 0.96-0.91 (m, 1 H), 0.91-0.82 (m, 1 H) ppm.

Ethyl A/-[2-({(1 S,2R,6S,Z)-5-[ethoxycarbonyl(phenyl)hydrazono]-6-isopropyl-2 -methyl-4-oxo-3- azabicyclo[4.1.0]heptan-3-yl}methyl)phenyl]-A/-(trifluoromet hylsulfonyl)carbamate: H NMR (400 MHz, CDCI ₃ ) δ 7.52-7.32 (m, 7H), 7.24-7.12 (m, 2H), 4.74 (d, 0.5H), 4.56 (q, 1 H), 4.39-4.15 (m, 4.5H), 3.71-3.61 (m, 1 H), 2.32-2.10 (m, 1 H), 1.47-1.41 (m, 1 H), 1.41-1.36 (m, 1.5H), 1.35-1.21 (m, 7.5H), 1.05-0.98 (m, 7H), 0.95-0.82 (m, 1 H) ppm.

Compounds made using the general methods described are listed in Table 10 below.

TABLE 10 Compounds made according to the general methods described.

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

Compound Structure Characteristic Data

Number

1-181 (Z 1 1.55 (s, 1 H), 7.62 (d, 1 H), 7.40 (m, 1 H), isomer)

7.31-7.22 (m, 4H), 7.18-7.10 (m, 2H), 6.91 (s, 1 H), 4.44 (s, 2H), 3.37 (s, 2H), 1.28 (s, 6H)

- -

2H),

3H), 1H), 1H)

H), (s, - -

Example 4 - Herbicidal action

EXAMPLE 4a Pre-emergence biological efficacy Seeds of Zea mays (ZEAMX), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Lolium perenne (LOLPE), Amaranthus retroflexus (AMARE) and Abutilon theophrasti (ABUTH) 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 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 1 1.

TABLE 11 Percentage damage caused to weed species by compounds of the invention when applied pre-emergence.

EXAMPLE 4b Post-emergence biological efficacy

Seeds of Zea mays (ZEAMX), Setaria faberi (SETFA), Echinochloa crus-galli (ECHCG), Lolium perenne (LOLPE), Amaranthus retroflexus (AMARE) and Abutilon theophrasti (ABUTH) 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 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 12.

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

I Cpd No I Species I - -

ZEAMX SETFA ECHCG LOLPE AMARE ABUTH

-181 (Z) 70 70 50 60 50 40-181 (£) 70 80 70 60 60 40

13-295 70 70 50 50 70 60-302(£) 80 70 70 70 80 80 -302(Z) 70 70 80 70 70 80 -308(Z) 60 70 60 60 80 80

13-346 70 60 70 40 70 70

13-390 50 60 70 40 80 70 -308(Z) 50 70 70 40 80 80

16-346 40 70 60 60 80 70