MOSER HANS (CH)
BRUNNER HANS-GEORG (CH)
PISSIOTAS GEORG (DE)
MOSER HANS (CH)
BRUNNER HANS GEORG (CH)
| EP0238711A1 | 1987-09-30 | |||
| EP0304920A2 | 1989-03-01 | |||
| EP0273417A1 | 1988-07-06 |
CHEMICAL ABSTRACTS, vol. 86, no. 5, 31 January 1977, Columbus, Ohio, US; abstract no. 29859y, page 375; column L;
CHEMICAL ABSTRACTS, vol. 120, no. 1, 3 January 1994, Columbus, Ohio, US; abstract no. 2802h, page 333; column R;
| 1. | A thiadiazabicyclodecane of formula I wherein Z is oxygen or sulfur; R is CrC6alkyl, C3C6cycloalkyl, CrC6haloalkyl, C3C6alkenyl, C3C6alkynyl, C3C6haloalkenyl, C3C6haloalkynyl, phenyl that is unsubstituted or substituted by CrC alkyl, C1C4alkoxy, C1C4haloalkyl or by halogen, or is benzyl that is unsubstituted or substituted by CrC4alkyl, C1C4alkoxy, C1C4haloalkyl or by halogen, it being possible for the unsubstituted or substituted phenyl and benzyl groups each to occur only once; W is a group of formula W: to W10 Rlt R^, R^, R^, R27, R30, R33, R37, R38 and R41 are each independently of the others hydrogen or halogen; R2 is cyano, nitro, halogen, CrC4alkyl, CrC4haloalkoxy or C1C4haloalkyl; A is hydrogen, cyano, nitro, COR3, X3R4, COR , N(R13)SO2R14, — Aj is cyano or COR16; R3 is halogen, X4R5, amino, CrC4alkylamino, diC1C4alkylamino, C2C4haloalkyl amino, diC2C4haloalkylamino, diCrC4alkoxyalkyl amino, C3 or C4alkenylamino, diallylamino, Npyrrolidino, Npiperidino, Nmorpholino, Nthiomo holino, Npiperazino, ON=C(CH3)CH3 or OCH2CH2ON=C(CH3)CH3; R4, R42 and R43 are hydrogen, CrC10alkyl, C1C4alkoxyC1C4alkyl, CrC4alkylthio CrC4alkyl, diC^alkylaminoC^alkyl, CrC8haloalkyl, C2C8alkenyl, C2C8haloalkenyl, C3C8alkynyl, C3Cτcycloalkyl, oxetan3yl, haloC3CτCyclo alkyl, CrC8alkylcarbonyl, allylcarbonyl, C3C7cycloalkylcarbonyl, benzoyl that is unsubstituted or is substituted at the phenyl ring by up to three identical or different substituents selected from halogen, CιC4alkyl, C C4haloalkyl, Ci haloalkoxy and CrC4alkoxy; C1C4alkyl substituted by cyano, nitro, carboxy, CrC8alkylthio Cj.C8alkoxycarbonyl, phenyl, halophenyl, CrC4alkylphenyl, Cx alkoxyphenyl, Cι.C4haloalkylphenyl, CrC4haloalkoxyphenyl, CjCgalkoxycarbonyl, C1C4alkoxyC1C8alkoxycarbonyl, C3C8alkenyloxycarbonyl, C3C8alkynyloxy carbonyl, C Cgalkylthiocarbonyl, C3C8alkenylthiocarbonyl, C3C8alkynylthio carbonyl, carbamoyl, CrC4alkylaminocarbonyl, diCj alkylaminocarbonyl; phenylaminocarbonyl that is unsubstituted or substituted at the phenyl by up to three identical or different substituents selected from halogen, C1C alkyl, CrC4halo alkyl, CrC4haloalkoxy and CrC4alkoxy or by one substituent selected from cyano and nitro; dioxolan2yl that is unsubstituted or substituted by one or two C1C alkyl radicals; or dioxanyl that is unsubstituted or substituted by one or two CrC4alkyl radicals; R5 is hydrogen, CrC10alkyl, C1C4alkoxyC1C4alkyl, C2C8haloalkyl, C1C10alkylthioC1C4alkyl, diC1C4alkylaminoC1C4alkyl, cyanoCrC8alkyl, C3C8alkenyl, C3C8haloalkenyl, C3C8alkynyl, C3C7cycloalkyl, oxetan3yl, C3C7cycloalkylC1C4alkyl, haloC3Cτcycloalkyl, or is benzyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C1C4alkyl, CrC4haloalkyl, C1C4haloalkoxy and CrC4alkoxy; an alkali metal, alkaline earth metal or ammonium ion; or is a group — [CHR6(CH2) JCOORo ; R20 and R21 are each independently of the other hydrogen, C1C alkyl or fluorine; R6, R26, R28, R32, R34, R39, R40. R46» R47» R49» Rso and R51 are each independently of the others hydrogen or C C4alkyl; R7 and R^ are each independently of the other hydrogen, CrC6alkyl, C3C8alkenyl, C3C8alkynyl, CrC8alkoxyC2C8alkyl, C1C8alkylthioC1C8alkyl or C3C7cyclo alkyl; R8 is hydrogen or CrC4alkyl; R^ and R45 are each independently of the other hydrogen, CrC4alkyl, CrC4haloalkyl or C1C4alkoxyC1C4alkyl; Rg and R10 are each independently of the other CrC4alkyl, C2C4haloalkyl or C2C8alkoxyalkyl; or R9 and R10 together are an ethano, a propano or a cyclohexanel,2diyl bridge, it being possible for those groups to be either unsubstituted or substituted by one or two radicals from the group Cj alkyl, Ci haloalkyl and Cx hydroxyalkyl; Rn is hydrogen, C1C5alkyl or C3C7alkenyl; R12 is CiCβalkyl; R13 is hydrogen, CiCsalkyl, benzyl, CrC4haloalkyl, C3C8alkenyl or C3C8alkynyl; R14 is CrC6alkyl, CrC5haloalkyl or di alkylamino; R15 is hydrogen, fluorine, chlorine, bromine, CrC4alkyl or trifluoromethyl; R16 is chlorine, X5R17, amino, C alkylamino, diC1C4alkylamino, C2C4haloalkyl amino, diC2C4haloalkylamino, CiQalkoxyalkylamino, diCrC4alkoxyalkyl amino, C3C4alkenylamino, diallylamino, Npyrrolidino, Npiperidino, Nmorpholino, Nthiomorpholino, Npiperazino, or is a group ON=C(CH3)CH3, OCH2CH2ON=C(CH3)CH3 or N(OR46)R< R17 is hydrogen, C1C10alkyl, C1C4alkoxyC1C4alkyl, C C8haloalkyl, C1C10alkyl thioCrC4alkyl, diC1C4alkylaminoC1C4alkyl, cyano Csalkyl, C3C8alkenyl, C3C8haloalkenyl, C3C8alkynyl, C3C7cycloalkyl, C3C7cycloalkylC1C4alkyl, haloC3C7cycloalkyl, or is benzyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, CrC4alkyl, haloalkyl, CrC4haloalkoxy and C1C4alkoxy; an alkali metal, alkaline earth metal or ammonium ion, or is a group [CHR47(CH2)m]COOR 8 or [CHR49(CH2)tSi(R18)3]; m is 0, 1, 2, 3 or 4; t is 0, 1, 2, 3 or 4; R18 is CrC4alkyl; R19 is hydrogen, C C6alkyl, C2C4alkenyl or C2C6alkynyl; halosubstituted CrC6alkyl, C2C4alkenyl or C3C6alkynyl; CrC4alkoxyCrC4alkyl, CrC4alkoxy C1C2alkoxyC1C2alkyl, lphenylpropen3yl, cyano or C3C6cycloalkyl substituted CrC6aIkyl; carboxyCrC4alkyl, C1C6alkoxycarbonylC1C alkyl, C2C6haloalkoxycarbonylC1C4alkyl, C1C4alkoxyC1C2alkoxycarbonyl Cx alkyl, C1C6alkoxycarbonylC1C2alkoxycarbonylC1C4alkyl, C3C6cyclo alkylC1C2alkoxycarbonylC1C4alkyl, C1C5alkylaminocarbonylC1C4alkyl, diC1C4alkylaminoC1C4alkyl, diC1C5alkylaminocarbonylC1C4alkyl, C3C6cycloalkyl, CjC^^alkylthioCi^alkyl, benzyl or halosubstituted benzyl, CrC4alkylsulfonyl, C3C6alkenyloxyC1C4alkyl, CrC4alkoxycarbonyl, CrC8alkylcarbonyl, cιc4a"kylCOO <^0 , C C.al ylCOO < % Cr C4alkylthiocarbonylC1C4alkyl, or is a group [CHR^CH^ COXeCHR^CH^COOR^ ; R25> R29» R3i» R35 an< R36 are eacn independently of the others hydrogen, CrC4alkyl, CjCghaloalkyl, C3C8alkenyl, C3C8haloalkenyl, C3C8alkynyl, CrC4alkoxy CrC8alkyl, cyanoC1C4alkyl, CjCgalkoxycarbonylCj alkyl, C3C7cycloalkyl, C3C7cycloalkylC1C4alkyl, benzyl, Ci alkyl substituted by Nmorpholino, Nthiomorpholino or by Npiperazino, diC1C4alkylaminoC1C4alkyl, C1C alkylaminocarbonylC1C alkyl, diC1C4alkylaminocarbonylC1C4alkyl, C1C4alkoxycarbonyl or CrC4alkylcarbonyl; Xlt X2, X3, X4, X5 and X6 are each independently of the others oxygen or sulfur; and nlt n2, n3, n4 and n5 are each independently of the others 0, 1, 2, 3 or 4; or a salt, complex or stereoisomer thereof. |
| 2. | A compound according to claim 1, wherein Z is oxygen. |
| 3. | A compound according to claim 1 of formula la wherein Z, A, R, Rlt R2 and n2 are as defined in claim 1. |
| 4. | A compound according to claim 3, wherein A is X3R , COR8, COR3 ORg OR10 CCN , CR44 or N(R13)SO2R14. NOR42 NOR43 . |
| 5. | A compound according to claim 4, wherein X3 is sulfur and R4 is CrC4alkyl substituted by Cj alkoxycarbonyl. |
| 6. | A compound according to claim 3, wherein Rj and R2 are halogen. |
| 7. | A compound according to claim 6, wherein Rj is fluorine and R2 is chlorine. |
| 8. | A compound according to claim 1 of formula lb wherein Z, R, R19, R22, Xlf R^, Hi and n2 are as defined in claim 1. |
| 9. | A compound according to claim 8, wherein R19 is CrC4alkyl, C3 or C4alkenyl, C3 or C4haloalkenyl, C3C6alkynyl, C1C4alkoxyC1C4alkyl, cyanoCj alkyl, C1C6alkoxycarbonylC1C4alkyl, C3C6cycloalkyl, C3C6cycloalkylCrC4alkyl, benzyl, diC1C alkylamino CrC4alkyl, C1C4alkylaminocarbonylC1C4alkyl, diC1C4alkylaminocarbonyl C1C4alkyl, CrC alkoxycarbonyl or CrC4alkylcarbonyl. |
| 10. | A compound according to claim 9, wherein Z is oxygen; R19 is Cx alkyl, CjCsalkoxycarbonylC or C2alkyl or C3 or C alkynyl; R^ is hydrogen or fluorine; R50 is hydrogen; and n2 is 0 or 1. |
| 11. | A compound according to claim 1, wherein nx is 0 or 1. |
| 12. | A compound according to claim 11, wherein nx is 0. |
| 13. | A compound according to claim 1 selected from the group 10(4chloro2fluoro5isopropoxycarbonylphenylimino)9thial,7diazabicyclo[3.5.0] decan8one; and 10(4chloro2fluoro5methoxycarbonylphenylimino)9thial,7diazabicyclo[3.5.0] decan8one. |
| 14. | A process for the preparation of a compound of formula I wherein Z, W, R and nj are as defined for formula I in claim 1, which comprises converting an isothiocyanate of formula π S=C=NW (H), wherein W is as defined for formula I in claim 1, with a compound of formula III wherein R and are as defined, into a compound of formula IV which is then reacted, where appropriate in the presence of a base, with a compound of formula N CZC12 (N), wherein Z is oxygen or sulfur. |
| 15. | A compound of formula VI wherein R is C1C6haloalkyl, C3C6haloalkenyl or C3C6haloalkynyl; and nx is 1, 2, 3 or 4. |
| 16. | A compound of formula HI wherein R is C3C6cycloalkyl, Ci haloalkyl, C3C6alkenyl, C3C6alkynyl, C3C6haloalkenyl or C3C6haloalkynyl; and nx is 1, 2, 3 or 4. |
| 17. | A compound of formula IV S wherein R is C3C6cycloalkyl, CrC6haloalkyl, C3C6alkenyl, C3C6alkynyl, C3C6haloalkenyl or C3C6haloalkynyl; ti is 1, 2, 3 or 4; and W is as defined for formula I. |
| 18. | A herbicidal composition which comprises a compound of formula I or a salt thereof according to claim 1. |
| 19. | A composition according to claim 18, which comprises from 0.1 to 95 percent by weight of active ingredient of formula I according to claim 1. |
| 20. | A method of controlling undesired plant growth, which comprises treating the crop plants to be protected against weeds and/or the weeds and grasses with a compound of formula I according to claim 1 or with a composition comprising that compound according to claim 18. |
| 21. | A method according to claim 20, which comprises applying a compound of formula I in an amount of from 0.001 to 2 kg per hectare. |
| 22. | A method according to claim 20 for the selective pre or postemergence control of weeds and grasses in crops of useful plants. |
| 23. | The use of a composition according to claim 18 for the selective pre or post emergence control of weeds and grasses in crops of useful plants. |
The present invention relates to novel, herbicidally active thiadiazabicyclodecanes, to processes for the preparation thereof, to compositions comprising those compounds as active ingredients, and to the use thereof in controlling weeds, especially selectively in crops of useful plants, such as cereals, maize, soybeans, rape, rice and cotton.
Thiadiazabicyclo derivatives having herbicidal activity are already known. Such compounds are disclosed, for example, in EP-A-0 238711, EP-A-0 304920, US-A-4 885023, US-A-4684397, US-A-4 801 408 and JP-A-05 213970.
Novel thiadiazabicyclodecanes having selective herbicidal activity have now been found.
The thiadiazabicyclodecanes according to the invention correspond to formula I
wherein
Z is oxygen or sulfur;
R is C r C 6 alkyl, C 3 -C 6 cycloalkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl,
C 3 -C 6 haloalkenyl, C 3 -C 6 haloalkynyl, phenyl that is unsubstituted or substituted by C r C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or by halogen, or is benzyl that is unsubst¬ ituted or substituted by C r C 4 alkyl, C r C 4 alkoxy, C r C 4 haloalkyl or by halogen, it being possible for the unsubstituted or substituted phenyl and benzyl groups each to
occur only once; W is a group of formula W j to W 10
R lt R 2 , R 23 , R 24 . R 27 « R 30 » R 33 > R 37 » R 38 and R 41 are each independently of the others hydrogen or halogen; R 2 is cyano, nitro, halogen, C r C 4 alkyl, C r C 4 haloalkoxy or Cj- haloalkyl;
A is hydrogen, cyano, nitro, -COR 3 , -X 3 R , _< jr "CN » -COR 8 , "" C~R 4 ,
N-OR 42 N-OR 43
- X 4 - [CHR„(CH 2 ) 2- 3 Si(R 12 )3 , -N(R 13 )-SO R 14 ,
A : is cyano or -COR 16 ;
R 3 is halogen, -X 4 -R 5 , amino, C r C 4 alkylamino, di-C r C 4 alkylamino, C 2 -C 4 haloalkyl- amino, di-C 2 -C 4 haloalkylamino, Cx- alkoxyalkylamino, di-C 1 -C 4 alkoxyalkyl- amino, C 3 - or C 4 -alkenylamino, diallylamino, -N-pyrrolidino, -N-piperidino, -N-morpholino, -N-thiomorpholino, -N-piperazino, -O-N=C(CH 3 )-CH 3 or -O-CH 2 -CH 2 -O-N=C(CH 3 )-CH 3 ;
R 4 , R 42 and R 43 are hydrogen, Cj-Cjoalkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkylthio- C r C 4 alkyl, di-C 1 -C 4 alkylamino-C 1 -C 4 alkyl, C r C 8 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 - haloalkenyl, C 3 -C 8 alkynyl, C 3 -C 7 cycloalkyl, oxetan-3-yl, halo-C 3 -C 7 cycloalkyl, C r C 8 alkylcarbonyl, allylcarbonyl, C 3 -C 7 cycloalkylcarbonyl, benzoyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, - alkyl, Cj- haloalkyl, - haloalkoxy and C 1 -C 4 alkoxy; C r C 4 alkyl substituted by cyano, nitro, carboxy, C^Csalkylthio- Ci-Cgalkoxycarbonyl, phenyl, halophenyl, Cx- alkylphenyl, Cx- alkoxyphenyl, C r C 4 haloalkylphenyl, C r C 4 haloalkoxyphenyl, Cj- alkoxycarbonyl, C r C 4 - alkoxy-Ci-Cβalkoxycarbonyl, C 3 -C 8 alkenyloxycarbonyl, C 3 -C 8 alkynyloxycarbonyl, C r C 8 alkylthiocarbonyl, C 3 -C 8 alkenylthiocarbonyl, C 3 -C 8 alkynylthiocarbonyl, carb- amoyl, Cx-Qalkylaminocarbonyl, di-C r C 4 alkylaminocarbonyl; phenylaminocarb- onyl that is unsubstituted or substituted at the phenyl by up to three identical or different substituents selected from halogen, C r C 4 alkyl, Cj- haloalkyl, C r C 4 - haloalkoxy and Cp alkoxy or by one substituent selected from cyano and nitro; dioxolan-2-yl that is unsubstituted or substituted by one or two C r C 4 alkyl radicals; or dioxanyl that is unsubstituted or substituted by one or two C r C 4 alkyl radicals;
R 5 is hydrogen, C 1 -C 10 alkyl, Cj- alkoxy-C alkyl, C 2 -C 8 haloalkyl, C r C 10 alkyl- thio-C r C 4 alkyl, di-C 1 -C 4 alkylamino-C 1 -C 4 alkyl, cyano-C r C 8 alkyl, C 3 -C 8 alkenyl,
C 3 -C 8 haloalkenyl, C 3 -C 8 alkynyl, C 3 -C 7 cycloalkyl, oxetan-3-yl, C 3 -C 7 cycloalkyl- C C 4 alkyl, halo-C 3 -C 7 cycloalkyl, or is benzyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C r C 4 alkyl, C r C 4 haloalkyl, C C 4 haloalkoxy and C r C 4 alkoxy; an alkali metal, alkaline earth metal or ammonium ion; or a group — [CHR 6 (CH 2 ) ,]-COOR 7
R 2 o and R 21 are eacn independently of the other hydrogen, C r C 4 alkyl or fluorine;
R 6 , R 26 , R 28 , 32 > R 34 > R 3 9> R 40 > R 46 > R 4 7> R 9 » R 5 0 anci 51 are each independently of the others hydrogen or C r C 4 alkyl;
R 7 and R 48 are each independently of the other hydrogen, C r C 6 alkyl, C 3 -C 8 alkenyl,
C 3 -C 8 alkynyl, C r C 8 alkoxy-C 2 -C 8 alkyl, C r C 8 alkylthio-C r C 8 alkyl or C 3 -C 7 cyclo- alkyl;
R 8 is hydrogen or C r C 4 alkyl;
R 44 and R 45 are each independently of the other hydrogen, C r C 4 alkyl, C 1 -C 4 haloalkyl or C r C 4 alkoxy-C r C 4 alkyl;
R 9 and R 10 are each independently of the other C 2 -C 4 haloalkyl or C 2 -C 8 - alkoxyalkyl; or
R 9 and R 10 together are an ethano, a propano or a cyclohexane-l,2-diyl bridge, it being possible for those groups to be either unsubstituted or substituted by one or two radicals from the group C r C 4 alkyl, C C 4 haloalkyl and C r C 4 hydroxyalkyl;
Rπ s hydrogen, C 1 -C 5 alkyl or C 3 -C 7 alkenyl; R 12 s C r C 8 alkyl;
R 13 s hydrogen, C r C 5 alkyl, benzyl, C r C 4 haloalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl; R 14 s C C 6 alkyl, C j -Cshaloalkyl or di-C 1 -C 4 alkylamino; R 15 s hydrogen, fluorine, chlorine, bromine, C r C 4 alkyl or trifluoromethyl; R 16 s chlorine, -X 5 -R 17 , amino, C r C 4 alkylamino, di-C r C alkylamino, C 2 -C 4 haloalkyl- amino, di-C 2 -C 4 haloalkylamino, C r C alkoxyalkylamino, di-C r C 4 alkoxyalkyl- amino, C 3 -C 4 alkenylamino, diallyla ino, -N-pyrrolidino, -N-piperidino, -N-morpholino, -N-thiomorpholino, -N-piperazino, or is a group -O-N=C(CH 3 )-CH 3 , -O-CH 2 -CH 2 -O-N=C(CH 3 )-CH 3 or -N(OR 46 )-R 6 ;
R 17 is hydrogen, C r C 10 alkyl, C r C 4 alkoxy-C r C 4 alkyl, C 2 -C 8 haloalkyl, C r C 1() alkyl- thio-C r C 4 alkyl, di-C 1 -C 4 alkylamino-C 1 -C 4 alkyl, cyano-C r C alkyl, C 3 -C 8 alkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 alkynyl, C 3 -C 7 cycloalkyl, C 3 -C 7 cycloalkyl-C r C 4 alkyl, halo-C3-C 7 cycloalkyl, or is benzyl that is unsubstituted or substituted at the phenyl ring by up to three identical or different substituents selected from halogen, C r C 4 -
alkyl, C r C haloaIkyl, C 1 -C 4 haloalkoxy and C r C 4 alkoxy; an alkali metal, alkaline earth metal or ammonium ion, or a group -[CHR 7 -(CH 2 ) m |-COOR 48 or -[CHR 49 -(CH 2 ) t -Si(R 18 ) 3 l; m is O, 1, 2, 3 or 4; t is 0, 1, 2, 3 or 4;
R 18 is C r C 4 alkyl;
R 19 is hydrogen, C r C 6 alkyl, C 2 -C 4 alkenyl or C 2 -C 6 alkynyl; halo-substituted C j -Cg- alkyl, C 2 -C 4 alkenyl or C 3 -C 6 alkynyl; C r C 4 alkoxy-C ] -C 4 alkyl, C ] -C 4 alkoxy-C ] -C 2 - alkoxy-C C 2 alkyl, l-phenylpropen-3-yl, cyano- or C 3 -C 6 cycloalkyl-substituted C j -C 6 alkyl; carboxy-C ] -C 4 alkyl, C C 6 alkoxycarbonyl-C C 4 alkyl, C^Cghalo- alkoxycarbonyl-C j -Q^alkyl, C ] -C 4 alkoxy-C 1 -C 2 alkoxycarbonyl-C 1 -C 4 alkyl, C C 6 - alkoxycarbonyl-C 1 -C 2 alkoxycarbonyl-C r C 4 alkyl, C 3 -C 6 cycloalkyl-C r C 2 alkoxy- carbonyl-C]-C 4 alkyl, Cι-C 5 alkylaminocarbonyl-C r C 4 alkyl, C r C 4 alkyl, di-Cι-C 5 alkylaminocarbonyl-C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C j -C 4 alkyl- thio-C j -C alkyl, benzyl or halo-substituted benzyl, C 1 -C alkylsulfonyl, C 3 -C 6 alken- yloxy-C 1 -C 4 alkyl, Cj- alkoxycarbonyl, - alkylcarbonyl,
C r C 4 alkyl-COO ___ "θ ? C r C 4 alkyl-COO > s
C 1 -C 4 alkylthiocarbonyl-C 1 -C 4 alkyl, or a group -[CHR 47 -(CH 2 ) m ]COX 6 -CHR 47 -(CH 2 ) m -COOR 48 ;
R 25 > R 2 9» R 3 i> 35 an d 36 are eacn independently of the others hydrogen, C r C 4 alkyl, C r C 6 haloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 alkynyl, C r C 4 alkoxy- C r C 8 alkyl, cyano-C r C 4 alkyl, C r C 8 alkoxycarbonyl-Cj-C 4 alkyl, C 3 -C 7 cycloalkyl, C 3 -C 7 cycloalkyl-C 1 -C 4 alkyl, benzyl, C]-C 4 alkyl substituted by -N-morpholino, -N-thiomorpholino or by -N-piperazino, di-C r C 4 alkylamino-C r C 4 alkyl, C r C 4 - alkylaminocarbonyl-C 1 -C 4 alkyl, di-CrC 4 alkylaminocarbonyl-C]-C 4 alkyl, C C 4 - alkoxycarbonyl or - alkylcarbonyl;
Xj, X 2 , X 3 , X 4 , X 5 and X 6 are each independently of the others oxygen or sulfur; and nj, n 2 , n 3 , n 4 and n 5 are each independently of the others 0, 1, 2, 3 or 4; and the salts, complexes and stereoisomers thereof.
In the above definitions, halogen is to be understood as being fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
Suitable alkyl groups are straight-chained or branched alkyl groups, for example methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, ten-butyl, and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl and decyl radicals.
Suitable as haloalkyl are alkyl groups mono- or poly-substituted, especially mono- to tri- substituted, by halogen, halogen being individually bromine or iodine and especially fluorine or chlorine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloro- ethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl; preferably difluorochloromethyl, trifluoromethyl, dichlorofluoro- methyl and trichloromethyl.
Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy, ethoxy and isopropoxy.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-tri- fluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-tri- chloroethoxy; preferably difluoromethoxy, trifluoromethoxy and 2-chloroethoxy.
Alkylthio is, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio or isomeric pentylthio, preferably methylthio and ethylthio.
Alkenyl is to be understood as being straight-chained or branched alkenyl, such as vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-l-yl, pentenyl, 2-hexenyl or 3-heptenyl; the same applies also to the alkenyl moiety of alkenyloxy, alkenylthio and alkenylamino groups. Preference is given to alkenyl radicals having a chain length of from 2 to 4 carbon atoms.
The alkynyl radicals in the definitions of the substituents may be straight-chained or branched, such as ethynyl, propargyl, 3-butynyl, 1 -methylpropargyl, 1 -pentynyl or 2-hexynyl; the same applies also to the alkynyl moiety of alkynyloxy and alkynylthio groups. Preference is given to ethynyl, propargyl and 1 -methylpropargyl.
Cycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl or cycloheptyl, but preferably cyclopropyl, cyclopentyl and cyclohexyl.
Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl,
isopropoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl and ethoxy- carbonyl.
Alkoxyalkyl is, for example, methoxymethyl, ethoxymethyl, propoxymethyl, methoxy- ethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl or propoxypropyl.
Alkylthioalkyl is, for example, methylthiomethyl, ethylthiomethyl, methylthioethyl, ethyl- thioethyl or isopropylthioethyl.
Alkylamino is, for example, methylamino, ethylamino and isomeric propyl- and butyl- amino.
Cyanoalkyl is, for example, cyanomethyl, cyanoethyl or cyanopropyl.
Halocycloalkyl is, for example, 2,2-dichlorocyclopropyl or pentachlorocyclohexyl.
Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl or butyl- sulfonyl, preferably methyl- and ethyl-sulfonyl.
Phenyl, also as part of a substituent such as phenoxy, phenylthio, phenoxycarbonyl, phenylaminocarbonyl, benzyl or benzoyl, may generally be unsubstituted or substituted. In the latter case, the substituents may be in the ortho-, meta- and/or para-position. Preferred substituent positions are the ortho- and para-positions to the ring-linkage position. Preferred substituents are halogen atoms.
The substituents in combined definitions, such as alkoxyalkoxycarbonylalkyl, alkylthio- alkoxycarbonyl, haloalkoxycarbonylalkyl, alkoxyalkoxyalkyl, cycloalkylalkyl, cycloalkyl- alkoxycarbonylalkyl and alkoxyalkylamino, may have the same definitions as those above.
The salts of compounds of formula I having acidic hydrogen, especially of derivatives having carboxylic acid groups (A= -C(O)-X 4 R 5 wherein X 4 is oxygen and R 5 is hydrogen), are, for example, alkali metal salts, such as sodium and potassium salts; alkaline earth metal salts, such as calcium and magnesium salts; ammonium salts, i.e. unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, such as tri- ethylammonium and methylammonium salts; or salts with other organic bases.
Examples of amines suitable for salt formation are primary, secondary and tertiary aliphatic and aromatic amines, such as methylamine, ethylamine, n-propylamine, iso- propylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octyl- amine, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butyl- amine, di-n-amylamine, di-isoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethylethanolamine, N-ethyl- propanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2-amine, propylenediamine, diethanolamine, trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tri- n-butylamine, tri-isobutylamine, tri-sec-butylamine, tri-n-amylamine; heterocyclic amines, such as pyridine, quinoline, isoquinoline, morpholine, thiomorpholine, N-methylmorpho- line, N-methyl-thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, such as anilines, methoxyanilines, ethoxyanilines, o,m,p- toluidines, phenylenediamines, benzidines, naphthylamines and o,m,p-chloroanilines.
The fact that at least one asymmetric carbon atom may be present in compounds of formula I, for example in ester and ether derivatives having substituted aliphatic and ali- cyclic groups, means that the compounds may occur both in the form of optically active individual isomers and in the form of racemic mixtures. In the present invention, compounds of formula I are to be understood as being both the pure optical antipodes and the racemates. If an aliphatic C=C or C=N double bond is present, geometric isomerism may also occur.
Preference is given to compounds of formula I wherein Z is oxygen.
Preference is likewise given to compounds of formula la
wherein Z, A, R, R l R 2 and nj are as defined for formula I.
Of those compounds, special preference is given to those wherein A is -X 3 R 4 , -COR 8 , -COR 3> or -N(R 13 )-SO 2 -R 14 , wherein X 3 is especially
sulfur and R 4 is C 1 -C 4 a]kyl substituted by Ci- alkoxycarbonyl.
In especially preferred compounds of formula la, Rj and R 2 are halogen; Rj is especially fluorine and R 2 is especially chlorine.
The preferred compounds likewise include those of formula lb
wherein Z, R, R 19 , R 22 , X lt R 50 , nj and n 2 are as defined for formula I.
Of those compounds, special preference is given to those wherein R 19 is C r C 4 alkyl, C 3 - or C 4 -alkenyl, C 3 - or C 4 -haloalkenyl, C 3 -C 6 alkynyl, -Q- alkoxy-C 1 -C 4 alkyl, cyano-C r C 4 alkyl, C 1 -C 6 alkoxycarbonyl-C 1 -C 4 alkyl, C 3 -C 6 - cycloalkyl, C 3 -C 6 cycloalkyl-C r C 4 alkyl, benzyl, di-C 1 -C 4 alkylamino-C 1 -C 4 alkyl, C 1 -C 4 alkylaminocarbonyl-C 1 -C 4 alkyl, di-C 1 -C 4 alkylaminocarbonyl-C 1 -C 4 alkyl,
Cj- alkoxycarbonyl or C C 4 alkylcarbonyl.
Of those compounds very special preference is given to those wherein
Z is oxygen;
R 19 is C r C 3 alkyl, Cx-Csalko ycarbonyl-C or -C 2 -alkyl or C 3 - or C 4 -alkynyl;
R^ is hydrogen or fluorine;
R 50 is hydrogen; and n 2 is 0 or 1.
Especially significant are compounds of formula I wherein nj is 0 or 1.
Of those, compounds of formula I wherein n x is 0 are of very special significance.
Very especially preferred individual compounds within the scope of formula I that may be mentioned are:
10-(4-cWoro-2-fluoro-5-isopropoxycarbonyl-phenylimino)-9- thia-l,7-diazabicyclo[3.5.0]- decan-8-one; and
10-(4-chloro-2-fluoro-5-methoxycarbonyl-phenylimino)-9-th ia-l,7-diazabicyclo[3.5.0]- decan-8-one.
The process according to the invention for the preparation of compounds of formula I
wherein Z, W, R and nj are as defined for formula I, is carried out analogously to known processes and comprises converting an isothiocyanate of formula π
S=C=N-W (II),
wherein W is as defined for formula I, with a compound of formula III
11 -
wherein R and n x are as defined, into a compound of formula IN
which is then reacted, where appropriate in the presence of a base, with a compound of formula V
CZC1 2 (V)
wherein Z is oxygen or sulfur.
The reaction of an isothiocyanate of formula π with a compound of formula HI is advant¬ ageously carried out in an inert organic solvent at temperatures of from -5°C to the boiling temperature of the solvent, especially from 0 to +50°C, preferably at room temperature. Examples of suitable solvents for that reaction are toluene, xylenes, ethyl acetate and acetonitrile.
The reaction of a compound of formula IN with a compound of formula N is advantage¬ ously carried out in an inert organic solvent at low temperatures, preferably at from 0 to +50°C, especially at from 0 to +15°C. Examples of bases suitable for that reaction are pyridine, triethylamine and Ν,Ν-dimethylaniline. Suitable solvents are, for example, 1,2-dichloroethane, dichloromethane and toluene.
The starting compounds of formula m wherein R is alkyl and nj is as defined for formula I that are required for the preparation process according to the invention are either
known or can be prepared analogously to processes known from the literature. The prepar¬ ation of such compounds from 1,5-dibromopentanes and hydrazine is described, for example, in "Archiv der Pharmazie" 295 (7), 526 (1962) and J. Org. Chem. 46, 442 (1981).
Compounds of formula ϋla (dihydrobromide)
wherein R and n t are as defined for formula I, can be prepared in accordance with Reaction scheme 1.
Reaction scheme 1 :
p-to]yl
VI Vlb
Br-[C 5 -(n
VII
HBr
Ilia (dihydrobromide)
In Reaction scheme 1, formulae VI, Via and Vlb are each an unbranched aliphatic pentane chain having a hydroxy group (VI) or an R 0 SO 2 O group (Vlb) or bromine (Via) bonded to each of its terminal carbon atoms C_ and C 5 . The radical R can be linked 0, 1 , 2, 3 or 4 times to all of the 5 carbon atoms of the n-pentane chain, where appropriate also geminally.
The intermediates of formulae III and IV wherein R is C 3 -C 6 cyc oalkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkenyl, or C 3 -C 6 haloalkynyl, and of formula VI
wherein R is C r C 6 haloalkyl, C 3 -C 6 haloalkenyl or C 3 -C 6 haloalkynyl, and λ is 1, 2, 3 or 4 are novel and have been developed especially for the synthesis of the compounds of formula I. The present invention therefore relates also thereto.
The isothiocyanates of formula π are known or can be prepared analogously to known processes. Such compounds are described, for example, in EP-A-0304920, EP-A-0238 711, EP-A-0409 025, EP-A-0 373461, EP-A-0 311 135 and DE-OS-3 724098.
For the use of the compounds of formula I according to the invention or compositions comprising them there are suitable any of the methods of application customary in agricul¬ ture, such as preemergence application, postemergence application and seed dressing, as well as various methods and techniques, such as the controlled release of active ingredient In that method the compound is applied in solution to mineral granule carriers or polymer¬ ised granules (urea/formaldehyde) and dried. Where appropriate, it is also possible to apply a coating (coated granules) which allows the active ingredient to be released in metered amounts over a specific period.
The compounds of formula I can be used in unmodified form, i.e. as obtained during synthesis, but are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules and microcapsules. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circum¬ stances.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, where appropriate, one or more solid or liquid adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the adjuvants, e.g. solvents or solid carriers. Surface-active compounds (surfactants) may additionally be used in the preparation of the formulations.
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, such as mixtures of alkylbenzenes, e.g. xylene mixtures or alkylated
naphthalenes; aliphatic and cycloaliphatic hydrocarbons such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols, such as ethanol, propanol or butanol; glycols and their ethers and esters, such as propylene glycol or dipropylene glycol ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils and their esters, such as rape oil, castor oil or soybean oil; and optionally also silicone oils.
The solid carriers used e.g. for dusts and dispersible powders are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable non-sorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, such as especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants having good emulsify¬ ing, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil; mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfon- ates. The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C 8 -C 22 alkyl radical, which also includes the alkyl moiety of acyl radicals, for example the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the
salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benz- imidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo- aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, it being possible for said derivatives to contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkyl¬ phenols.
Further suitable non-ionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit
Representative examples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy- polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C 8 -C 22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethyl- ammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in formulation technology, which can also be used in the compositions according to the invention, are described inter alia in the following
publications:
- "Mc Cutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp., Glen Rock, New Jersey, 1988.
- M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-m, Chemical Publishing Co., New York, 1980-1981.
- Dr. Helmut Stache "Tensid-Taschenbuch" (Surfactant Handbook), Carl Hanser Verlag, Munich/Vienna 1981.
The herbicidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula 1, 1 to 99 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant
Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further ingredients such as stabilisers, e.g. vegetable oils and epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
Preferred formulations have especially the following composition (throughout, percent¬ ages are by weight)
Emulsifiable concentrates: active ingredient: 1 to 90%, preferably 5 to 50% surfactant: 5 to 30%, preferably 10 to 20% liquid carrier: 15 to 94%, preferably 70 to 85%
Dusts: active ingredient: 0.1 to 50%, preferably 0.1 to 1% 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%
surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders: active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 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 compounds of formula I are generally used successfully at rates of application of from 0.001 to 2 kg/ha, especially from 0.005 to 1 kg ha. The concentration required to achieve the desired effect can be determined by experiment It is dependent upon the type of action, the stage of development of the crop plant and of the weed, and also upon the application (place, time, method) and, in dependence on those parameters, can vary within wide limits.
When used at relatively low rates of application, the compounds of formula I are distinguished by growth-inhibiting and herbicidal properties that make them outstandingly suitable for use in crops of useful plants, especially in cereals, maize, rape, soybeans, rice and cotton.
Crops are also to be understood as being those which have been rendered tolerant to herbicides or classes of herbicide by conventional methods of breeding or by genetic techniques.
The Examples that follow further illustrate, but do not limit, the invention.
Preparation examples:
Example PI: Preparation of 3-trifluoromethyl-1.5-pentanediol (intermediate)
CH 2 -CH 2 OH
F 3 C — CH
X CH 2 - CH 2 OH
Under a pressure of 150 mm Hg, 136.3 g of 3-trifluoromethylglutaric acid diethyl ester in 1400 ml of ethanol at 150°C are hydrogenated with hydrogen in the presence of 136.0 g of copper chromite catalyst. When a stoichiometric amount of hydrogen has been absorbed, the catalyst is filtered off and the solution is concentrated in vacuo. The residue is distilled in vacuo to yield 76.9 g of the desired product having a boiling point of 132-135°C/- 24 mm Hg.
Example P2: Preparation of l,5-bismethanesulfonyloxy-3-trifluoromethylpentane (intermediate)
CH 2 -CH 2 OSO 2 -CH 3 F3C — CH
S CH 2 - CH 2 OSO 2 -CH 3
With stirring at 0°C, 63 ml of methylsulfonyl chloride in 40 ml of toluene are added drop- wise to a solution of 69.3 g of 3-trifluoromethyl-l,5-pentanediol and 140 ml of triethyl¬ amine in 150 ml of toluene. After 12 hours' stirring at room temperature, the solid portions are filtered off and the toluene solution is concentrated in vacuo to give in almost quantitative yield l,5-bismethanesulfonyloxy-3-trifluoromethylpentane; m.p. 40-45°C.
Example P3: Preparation of 1.2-dicarboxylic acid di-tert-butyl-5-trifluoromethyl-l,2- diazacvcloheptane (intermediate)
At 0-5°C, under a nitrogen atmosphere, a solution of 3.5 g of hydrazine-N,N' -dicarboxylic
acid di-tert-butyl ester in 50 ml of dimethylformamide is added dropwise to a suspension of 1.2 g of sodium hydride in 60 ml of dimethylformamide. After one hour, 5.1 g of l,5-bismethanesulfonyloxy-3-trifluoromethylpentane are added thereto at room temper¬ ature. The reaction mixture is then stirred for 16 hours at that temperature, then poured onto ice-water and filtered to yield 4.4 g of the desired 1,2-dicarboxylic acid di-tert-butyl- 5-trifluoromethyl-l,2-diazacycloheptane having a melting point of 98-100°C.
Example P4: Preparation of 5-trifluoromethyl-l,2-diazacvcloheptane dihvdrobromide (intermediate)
With stirring at room temperature, 6 ml of 33 % hydrobromic acid in glacial acetic acid are added dropwise to a solution of 4.3 g of 1,2-dicarboxylic acid di-tert-butyl-5-trifluoro- methyl-l,2-diazacycloheptane in 120 ml of diethyl ether. After 1/2 hour the salt precipi¬ tates partially in the form of a white crystalline compound. After the addition of a further 120 ml of diethyl ether the product precipitates completely. The crystalline precipitate is filtered off and the desired product is obtained in a yield of 2.0 g. The very hygroscopic product is dried over phosphorus pentoxide and immediately reacted further.
Example P5: Preparation of l-r2-chloro-4-fluoro-5-(l-(5-trifluoromethyl)-hexahydro- diazepinyl-thiocarbonylaminol-benzoic acid methyl ester (intermediate)
With stirring at 0-5°C, a solution of 2.2 g of l-(2-chloro-4-fluoro-5-isothiocyanatobenzoic acid methyl ester in 90 ml of ethylene chloride is added dropwise to a solution of 3.0 g of 5-trifluoromethyl-l,2-diazacycloheptane dihydrobromide in 100 ml of ethanol and 2.7 ml of triethylamine. After three hours' stirring at room temperature, the reaction mixture is taken up in 100 ml of water and 250 ml of ethyl acetate. The organic phase is separated
off, dried over sodium sulfate and concentrated in vacuo to yield 3.7 g of the desired inter¬ mediate; m.p. 103°C.
Example P6: Preparation of 10-r4-chloro-2-fluoro-5-methoxycarbonyl-phenylimino1-9- thia-4-trifluoromethyl- 1 ,7-diazabicvclor5.3.01decan-8-one
With stirring at 0-5°C, a solution of 3.7 g of l-[2-chloro-4-fluoro-5-(l-(5-trifluoro- methyl)-hexahydrodiazepinyl-thiocarbonylamino]-benzoic acid methyl ester in 100 ml of toluene is added dropwise to a solution of 50 ml of toluene and 7 ml of a 20 % solution of phosgene in toluene. The reaction mixture is then stirred for 12 hours at room temperature and then poured onto ice-water. The organic phase is separated off, dried over sodium sulfate and concentrated in vacuo to yield 2.5 g of the desired product having a m.p. of 75°C.
The compounds of formula I listed in the following Tables 1 to 16 are prepared in an analogous manner.
Table 1: Compounds of formula Ic:
Comp.
No. R x R 2 phys. data
no 0 1.6069
nj, 9 1.5548
Comp.
No. R_ R 2 phys. data
CH,
/
1.020 F Cl -COOCH(CH 3 )-CH 2 -S-CH
\
CH,
1.021 F Cl -COOCH(CH 3 )-CH 2 -S-C 4 H 9 1.022 F Cl -COOCH(CH 3 )-CH 2 -S-C 5 H n
CH,
1.023 F Cl -COOCH(CH 3 )-CH 2 -N
\
CH,
1.033 F Cl
Comp.
No. R t R 2 phys. data
1.034 F Cl —CON
1.035 F Cl -CON S
1.047 F Cl
Comp.
No. Rj R 2 phys. data
1.048 F Cl -COOCH 2 —
1.049 F Cl -COOCH A
CH
1.050 F Cl -COOCH 2
1.051 F Cl
Comp.
No. R x R 2 phys. data
CH,
Comp.
No. ^ R 2 phys. data
Comp.
No. R t R 2 phys. data
29-
Comp.
No. R ! R 2 phys. data
Comp.
No. R t R 2 phys. data
1.127 F Cl -ST COO-CH 2 -CH 2 -Cl
1.128 F Cl S- - COOCsHπ
1.129 F Cl -S^T^ - COOCH 2 -CH 2 -O-CH 3
1.130 F Cl -S-y^r COOCH(CH 3 )-CH 2 -S-CH 3
CH 3
/
1.131 F Cl -ST COOCH(CH 3 )-N
CH 3
1.132 F Cl -S zsr COO
■
1.134 F Cl -S- z ^- COO-CH 2 -CH 2 -CH=CH 2
1.135 F Cl S-^ COO-CH 2 -C=CH 2
Cl
1.136 F Cl -S- ^- COO-CH 2 -C≡CH
1.137 F Cl -S-ry COOH
1.138 F Cl -S- z ^- CONH 2
1.139 F Cl -S-Z5T C0NH - CH 3
1.140 F Cl -S zs - COOC 2 H 5
CH 3
phys. data
nj 8 1.6049
Comp.
No. R λ R 2 A phys. data
Comp.
No. R ! R 2 phys. data
Comp.
No. R x R 2 phys. data
1.194 H Cl -S- -COOC 2 H 5
F
1.197 H Cl -S- zs -COOH
1.201 H Cl -S-7^-COOC 2 H s
CH-CH 3
I
CH 3
1.202 H Cl -NH-SO 2 -C 2 H 5
1.203 H Cl -NH-SO 2 -CH 2 -Cl
1.204 F CN -COOH
Comp.
No. R ! R 2 phys. data
Comp.
No. Ri R 2 phys. data
resin
-37-
Table 2: Compounds of formula Id:
Comp.
No. R 2 R 2 phys. data
m.p.75°C
nj 8 1.5572
Comp.
No. R γ R 2 phys. data
Comp.
No. R j R 2 phys. data
2.045 F Cl -COO-CH-C≡CH
CH 3
2.046 F Cl -COO — /
Comp.
No. R j R 2 phys. data
2.048 F Cl -COOCH 2 — /
2.049 F Cl -COOCH A N
CH,
2.050 F Cl -COOCHj - O
2.051 F Cl
2.052 F Cl -COOCH 2
2.053 F Cl -COSCH 3
2.054 F Cl -COSC 2 H 5
2.055 F Cl -COSC 3 H 7
2.056 F Cl -COS-CH 2 -CH=CH 2
2.057 F Cl -COS-CH 2 -COOCH 3
2.058 F Cl -COS-CH 2 -COOC 2 H 5
2.059 F Cl -COS-CH 2 -COOC 5 H π
2.060 F Cl — COS-CH-COOCH 3
CH 3
2.061 F Cl -COS-CH-COOC 2 H 5
CH 3
Comp.
No. R t R 2 phys. data
Comp.
No. R x R 2 phys. data
resm
CH
2.087 F Cl -O-CH 2 -COOC 2 H 5
2.088 F Cl -O-CH-COOC 2 H 5
CH 3
2.089 F Cl O-CH 2 -CH 2 -O-CH 3
2.090 F Cl -O-CH-CH 2 -S-CH 3
CH 3
2.091 F Cl -O-CH-CH 2 -S-C 2 H 5
CH 3
2.092 F Cl -O-CH-CH 2 -S-C 3 H 7
CH 3
2.093 F Cl -O-CH 2 -CH 2 -Cl
2.094 F Cl -O-CH 2 -CN
2.095 F Cl -O-CH-CN
CH
Comp.
No. R x R 2 phys. data
nj 8 1.5719
44
Comp.
No. Rj R 2 phys. data
2.116 F Cl -C-CH 3
II N-O-CH 3
2.117 F Cl -C-CH 3
II N-O-CH 2 -C≡CH
2.118 F Cl -C-CH 2 -O-CH 3
II N-O-CH 3
2.123 F Cl -S-y^- COOCH 3
2.125 F Cl -S-7^- COOC 3 H 7
CH 3 /
2.126 F Cl -S-^- COOCH CH 3
Comp.
No. R t R 2 phys. data
m.p. 95°C (decomp.)
Comp.
No. R r R 2 phys. data
m.p. 190°C resin
Comp.
No. R x R 2 phys. data
Comp.
No. R x R 2 phys. data
Comp.
No. R j R 2 phys. data
2.194 H Cl -S-7^-COOC 2 H 5
F
2.197 H Cl -S- 7 -COOH
2.201 H Cl -S^T^-COOCzHg
CH-CH 3
I
CH 3
2.202 H Cl -NH-SO 2 -C 2 H 5
2.203 H Cl -NH-SO 2 -CH 2 -Cl
2.204 F CN -COOH
Comp.
No. R x R 2 phys. data
Comp.
No. R x R 2 A phys. data
n^ 8 1.5826
Table 3: Compounds of formula le:
Comp.
No. R t R 2 phys. data
Comp.
No. R x R 2 phys. data
3.033 F Cl -CON \
Comp.
No. R j R 2 phys. data
CH,
3.047 F Cl -COO - O
Comp.
No. R x R 2 phys. data
Comp.
No. Rj R 2 phys. data
3.079 F Cl -OCH 2 CH=CH 2
3.080 F Cl — OCH 2 -C=CH 2
Cl
3.081 F Cl -OCH 2 CH=CHCl
3.082 F Cl -OCH 2 C=CH
57
Comp.
No. R j R 2 phys. data
Comp.
No. R j R 2 phys. data
3.101 F Cl -S-CH 2 -C=CH 2
I Cl
3.113 F Cl -C-CN
II N-O-CH 3
3.114 F Cl -C-CN
II N-O-CH 2 -COOCH 3
3.115 F Cl -C-CN
II N-O-CH 2 -C≡CH
Comp.
No. R ! R 2 phys. data
Comp.
No. Ri R 2 A phys. data
3.134 F Cl -S ^- COO-CH 2 -CH 2 -CH=CH 2
3.135 F Cl -S- ^- COO-CH 2 -C=CH 2
Cl
3.136 F Cl -S7 COO-CH 2 -C≡CH
3.137 F Cl -ST^-COOH
3.138 F Cl -S- z ^-CONH 2
3.139 F Cl -S- z ^-CONH-CH 3
3.141 F Cl -S- ZS -COOC 2 H 5
C 2 H 5
phys. data
Comp.
No. R x R 2 phys. data
Comp.
No. Rj R 2 A phys. data
N-OCH 3
3.191 H Cl -ST^- COOH
CH 3
/
3.192 H Cl -S- 7 vCOO-CH
\
CH 3
phys. data
Comp.
No. R j R 2 A phys. data
Comp.
No. R j R 2 phys. data
Table 4: Compounds of formula If:
phys. data
resin
n^ 1.5879
Comp.
No. Ri R 2 phys. data
4.14 F Cl -S-^-CCK ^Hs
CF 3
4.15 H Cl -S-CH 2 -COOCH 3
4.16 F Cl ~°— <^°
4.17 H Cl -o— ζ ) o
4.18 F Cl -c-o-< o
4.19 H Cl -c-o-e^o
Table 5: Compounds of formula Ig
Comp.
No. Ri R 2 phys. data
Comp.
No. Ri R 2 phys. data
5.14 F Cl -S- ^-COO βs
CF 3
5.15 H Cl -S-CH 2 -COOCH 3
5.16 F Cl -o-/\>
5.17 H Cl -o— ζ ) o
5.18 F Cl _c-o-^o o
5.19 H Cl -C-O-C D
Table 6: Compounds of formula Ih
Comp.
No. Xι R 19 n 2 phys. data
0 1 0 0 1
/ CH,
6.06 O - CH 0
\
CH,
/ CH,
6.07 O - CH
0 1 0 1 1 0 1 0
Comp.
No. X j R 19 n 2 phys. data
0 0 0
0
0 0 0 0 0 0 0
0
0
0 0
0 0
Comp.
No. Xi R 19 n 2 phys. data
Comp.
No. Xι R 19 n 2 phys. data
Comp.
No. Xi R 19 n 2 phys. data
6.66 S -CH 0 _>
6.69 -CH ι 2 -CH 2 -N N-CH, 0
Comp. No. Xι R 19 "2 phys. data
Comp.
No. X ! R 19 n 2 phys. data
6.104 S F-CH 2 -CH 2 -O-C-CH- 0
O CH 3
6.105 S 0
6.106 S CF 3 -CH 2 -O-C(O)-CH(CH 3 )- 0
6.107 S CH 3 O - CH 2 CH 2 -O-C(O)-CH 2 - 0
6.108 S C 2 H 5 -O-CH 2 -CH 2 -O-C-CH 2 - 0
O
6.109 S C 3 H 7 -O-CH 2 -CH 2 -O-C-CH 2 - 0
O
6.110 S C 2 H 5 -O- $C-CH-O-C ϊ-CH- 0
CH 3 CH 3
6.114 S 0
6.115 S CH 3 -S-CH 2 -CH 2 - 0
Comp. No. Xi R 19 n 2 phys. data
0
0
0 0
Comp.
No. X : R 19 n 2 phys. data
CH,
6.127 S H^,— S-C CH— O -c II
0
O II CH-
I
CH 3
CH,
Table 7: Compounds of formula Ii
Comp. No. R R 23 phys. data
7.08 -CH H
H,
7.09 -CF 3 F 7.10 -CF 3 H
Table 8: Compounds of formula Ii
Comp. No. R R24 R 25 R 26 phys. data
,
/ CH,
8.06 H -CH -CH,
Comp. No. R R^ R ' 25 R 26 phys. data
8.12 -CF 3 F -CH 2 -C≡CH H
8.13 -CF 3 F -CH 2 -C≡CH -CH 3
Table 9: Compounds of formula Be
Comp. No. R R 38 R39/R4O phys. data
84-
Table 10: Compounds of formula π
Comp. No. R i R 32 phys. data
- 85
Table 11: Compounds of formula Im
Comp.
No. R R 27 R 29 R^ phys. data
11.01 H H H H
11.02 H F H H
11.03 H F -CH 3 H
11.04 -CH 3 F -CH 3 H
11.05 -CH 3 F -CH 2 -C≡CH H
11.06 H F -CH 2 -C≡CH H
CH 3
11.07 -CH F -CH 2 -C≡CH H
CH 3
11.O8 -CF 3 F -CH 2 -C≡CH H
11.09 -CF 3 F -CH 2 -C≡CH -CH 3
11.10 H H -CH 2 -C≡CH -CH 3
11.11 H F -CH 2 -C≡CH -CH 3
86
Table 12: Compounds of formula In
Comp. No. R R 37 R 36 phys. data
-87
Table 13: Compounds of formula lo
Comp. No. R R v-3„3 R ■ 3'4 R 35 phys. data
Table 14: Compounds of formula Ip
Comp. No. R R 30 R 31 phys. data
H H -CH 3
CH 3 -CH CH 3
-CH 2 -C≡CH -O-CH 2 -C≡CH
-O-CH 2 -C≡CH
Table 15: Compounds of formula Ig
Comp.
No. X j R 19 n 2 phys. data
0 1 0 0 1
0
0 1 0 1 1 0 1 0 0 0
Comp.
No. Xj R 19 "2 phys. data
15.18 S -C 3 H 7 (n)
CH 3
15.19 S -Cl 0
< ^CH 3
15.20 S -C 4 H<,(n) 0
15.21 S -C 4 H 9 (s) 0
15.22 S -C 4 H 9 (i) 0
15.23 S -C 4 H 9 (t) 0
15.24 S -CH 2 -CH=CH 2 0
15.25 S -CH 2 -CH=CH-CH 3 0
15.26 S -CH 2 -C=CH 2 0
CH 3
15.27 S -CH 2 -C≡CH 0
15.28 S -CH 2 -C≡C-CH 3 0
15.29 S -CH-C≡CH 0
CH 3
15.30 S -CH 2 -C=CHC1 0
I Cl
15.31 S -CH 2 -C=CH 2 0
Cl
15.32 S -CH 2 -CH=CHC1 0
15.33 S -CH 2 -CH=C-CH 3 0
Cl
15.34 S -CH 2 -CH=CH-Br 0
15.35 S -CH 2 -C=CH-Br 0
Br
15.36 S -CH 2 -C=CH 2 0
Br
Comp.
No. Xi R 19 n 2 phys. data
CH,
Comp.
No. Xi R 19 «2 phys. data
Comp.
No. X j R 19 n 2 phys. data
15.69 S -CH 2 -CH 2 -N / ~ Λ N- ■ CH 3 0
15.71 S -CH-C-NH-CH 3 0
I II
CH 3 O
15.74 S FCH 2 - 0 15.75 S F 2 CH- 0 15.76 S FCH 2 -CH 2 - 0 15.77 S CF 3 -CH 2 - 0 15.78 S FCH 2 -CH 2 -CH 2 - 0 15.79 S C1-CH 2 - 0
Comp.
No. Xι R 19 n 2 phys. data
,
Comp.
No. X R 19 n 2 phys. data
Comp.
No. X ! R 19 n 2 phys. data
Comp.
No. X ! R 19 «2 phys. data
o o
II II
15.127 S H- — s-c — CH— o— c 0
I I
CH 3 CH-
CH,
CH,
Table 16: Compounds of formula Ir
Comp.
No. Xi R 19 n 2 phys. data
0 1 0 0 1
0
0 1 0 1 1 0 1
Comp.
No. Xi R 19 n 2 phys. data
Br
Comp.
No. X! R 19 n 2 phys. data
16.52 S -CH-COOCH 3 0
CH 3
16.53 S -CH-COOC 2 H 5 0
CH 3
Comp.
No. Xι R 19 n 2 phys. data
16.55 S -CH-COOC 3 H 7 (n) 0
CH 3
16.56 S -CH-COOC 4 H 9 (n) 0
CH 3
16.57 S 0
16.58 S -CH-COOC 4 H 9 (i) 0
CH 3
16.59 S -CΑ-COOC 4 E 9 (t) 0
CH 3
16.60 S -CH-COOC 5 H n 0
CH 3
16.61 S -CH-COOCH 3 0
C 2 H 5
Comp.
No. Xi R 19 n 2 phys. data
16.69 S 0
16.71 -CH-C-NH-CH 3 0
I II 3
CH 3 O
Comp.
No. Xi R 19 «2 phys. data
16.101 S F-CH 2 -CH 2 -CH 2 -O-C-CH 2 - 0
O
16.102 S F 5 C 2 -CH 2 -O-C(O)-CH 2 - 0
16.103 S Cl-CH 2 -CH 2 -O-C-CH- 0
O CH 3
Comp.
No. Xi R 19 n 2 phys. data
16.104 S F-CH 2 -CH 2 -O-C-CH- 0
O CH 3
16.105 S F-CH 2 -CH 2 -CH 2 -O-C-CH- 0
O CH 3
16.106 S CF 3 -CH 2 -O-C(O)-CH(CH 3 )- 0
16.107 S CH 3 -O-CH 2 -CH 2 -O-C(O)-CH 2 - 0
16.108 S C 2 H 5 -O-CH 2 -CH 2 -O-C-CH 2 - 0
O
16.109 S C 3 H r O-CH 2 -CH 2 -O-C-CH 2 - 0
O
16.110 S C 2 H 5 -O- ϊC-CH-O-C ϊ-CH- 0
CH 3 CH 3
16.114 S 0
16.115 S CH 3 -S-CH 2 -CH 2 - 0
Comp.
No. X ! R 19 n 2 phys. data
Comp.
No. Xi R 19 n 2 phys. data
o o
16.127 HC — S-C — C
CH,
Formulation examples for compounds of formula I (throughout, percentages are b y weight)
FI. Emulsifiable concentrates a) b) c) d)
a compound of Tables 1-16 5% 10% 25% 50% calcium dodecylbenzene- 6% 8% 6% 8% sulfonate castor oil polyglycol ether 4 % - 4 % 4 %
(36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide) cyclohexanone - - 10% 20% aromatic hydrocarbon mixture 85% 78% 55% 16%
C 9 -C 12
Emulsions of any desired concentration can be produced from such concentrates by dilution with water.
F2. Solutions a) b) c) d)
a compound of Tables 1-16 5 % 10 % 50 % 90 % dipropylene glycol methyl ether - 20 % 20 % polyethylene glycol mol. wL 400 20 % 10 %
N-methyl-2-pyrrolidone - - 30 % 10 % aromatic hydrocarbon mixture 75 % 60 % C 9 -C 12
These solutions are suitable for application in the form of micro-drops.
F3. Wettable powders a) b) c) d)
a compound of Tables 1-16 5 % 25 % 50 % 80 % sodium lignosulfonate 4 % - 3 % - sodium lauryl sulfate 2 % 3 % - 4 % sodium diisobutylnaphthalene - 6 % 5 % 6 %
sulfonate octylphenol polyglycol ether - 1 % 2 % -
(7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3 % 5 % 10 % kaolin 88 % 62 % 35 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
F4. Coated granules a) b) c )
a compound of Tables 1-16 0 .1 % 5 % 15 % highly dispersed silicic acid 0 .9 % 2 % 2 % inorganic carrier 99 .0 % 93 % 83 %
(diameter 0.1 - 1 mm) such as CaCO 3 or SiO 2
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
F5. Coated granules a) b) c)
a compound of Tables 1-16 polyethylene glycol mol. wL 200 highly dispersed silicic acid inorganic carrier (diameter 0.1 - 1 mm) such as CaCO 3 or SiO 2
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder granules a) b) c) d)
a compound of Tables 1-16 sodium lignosulfonate carboxymethylcellulose kaolin
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c )
a compound of Tables 1-16 0 .1 % 1 % 5 % talcum 39 . 9 % 49 % 35 % kaolin 60 . 0 % 50 % 60 %
Ready-for-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
a compound of Tables 1-16 ethylene glycol nonylphenol polyglycol ether
(15 mol of ethylene oxide) sodium lignosulfonate carboxymethylcellulose
37% aqueous formaldehyde solution silicone oil emulsion 0 .8 % 0 .8 % 0 .8 % 0 .8 % water 87 % 79 % 62 % 38 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
Biological Examples:
Example Bl: Preemergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in plastic pots containing standard soil and, immediately after sowing, are sprayed with an aqueous suspension of the test compounds, prepared from a 25 % wettable powder formulation (Formulation example F3 b)), corresponding to a rate of application of 2 kg of active ingredient/hectare (5001 of water/ha). The test plants are then cultivated in a greenhouse under optimum conditions. After 3 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of 1 to 4 (especially 1 to 3) indicate good to very good herbicidal action.
Test plants: Avena, Lolium, Setaria, Sinapis, Solanum, Stellaria.
The compounds of Tables 1 to 16 exhibit pronounced herbicidal action in this test
Examples of the good herbicidal action are listed in Table Bl.
Table Bl: Preemer ence action
The same results are obtained when the compounds of formula I are formulated in accordance with Examples FI, F2 and F4 to F8.
Example B2: Post-emergence herbicidal action (contact herbicide) Monocotyledonous and dicotyledonous test plants are raised in a greenhouse in plastic pots containing standard soil and in the 4- to 6-leaf stage are sprayed with an aqueous suspension of the test compounds of formula I, prepared from a 25 % wettable powder
- Ill -
formulation (Formulation example F3 b)), corresponding to a rate of application of 2 kg of active ingredient hectare (5001 of water/ha). The test plants are then grown on in the greenhouse under optimum conditions. After about 18 days the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of 1 to 4 (especially 1 to 3) indicate good to very good herbicidal action.
Test plants: Avena, Lolium, Setaria, Sinapis, Solanum, Stellaria
The compounds of formula I according to the examples in Tables 1 to 16 exhibit good herbicidal action in this test also.
Examples of the good herbicidal activity of compounds of formula I are shown in Table B2.
Table B2: Post-emer ence action
The same results are obtained when the compounds of formula I are formulated in accordance with Examples FI, F2 and F4 to F8.