Benzoxaborole compounds

Abstract

The present invention relates to the use of the compound of formula (I), wherein the variables are defined according to the description, for controlling unwanted vegetation. Further the invention relates to novel compounds of the formula (I),compositions comprising them a method for controlling unwanted vegetation which comprises allowing a herbicidal effective amount of at least one azine of the formula (I) to act on plants, their seed and/or their habitat. ##STR00001##

Claims

1. A method of controlling unwanted vegetation, comprising allowing a herbicidally effective amount of a compound of formula (I) or of an agriculturally suitable salt or N-oxide thereof: ##STR00019## wherein A is a fused saturated or unsaturated, 4- to 7-membered carbocycle or a fused saturated or unsaturated, 4- to 7-membered heterocycle having 1, 2 or 3 heteroatoms or heteroatom moieties, selected from O, S, SO, SO.sub.2, N or NR.sup.7 as ring members, R.sup.1 is selected from the group consisting of H and C.sub.1-C.sub.6-alkyl; R.sup.2 is selected from the group consisting of H and C.sub.1-C.sub.6-alkyl; R.sup.3 is selected from the group consisting of H, halogen, OH, CN, amino, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, where the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.4 is selected from the group consisting of H, halogen, OH, CN, amino, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, where the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.5 is selected from the group consisting of H, halogen, OH, CN, amino, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, where the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.6 is selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, phenyl, phenyl-C.sub.1-C.sub.6-alkyl, where the aliphatic and phenyl parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.7 is selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl; to act on plants, their seed and/or their habitat.

2. The method according to claim 1, wherein A is a fused saturated 5- or 6-membered heterocycle having one or two O atoms as ring member.

3. The method according to claim 1, wherein A is a fused unsaturated 5- or 6-membered heterocycle having one or two O atoms as ring member.

4. The method according to claim 1, wherein A is a fused saturated 5- or 6-membered carbocycle.

5. The method according to claim 1, wherein A is a fused unsaturated 5- or 6-membered carbocycle.

6. The method according to claim 1, wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of H and C.sub.1-C.sub.4-alkyl.

7. The method according to claim 1, wherein R.sup.3 is selected from the group consisting of H, halogen, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-haloalkyl.

8. The method according to claim 1, wherein R.sup.4 is selected from the group consisting of H, halogen, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-haloalkyl.

9. The method according to claim 1, wherein R.sup.5 is selected from the group consisting of H, halogen, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-haloalkyl.

10. The method according to claim 1, wherein R.sup.6 is selected from the group consisting of H and C.sub.1-C.sub.6-alkyl.

11. The method according to claim 1, wherein R.sup.6 is H or CH.sub.3 and R.sup.4 is selected from the group consisting of halogen, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-haloalkyl.

12. The method according to claim 1, wherein when A is cyclohexane, and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each H then R.sup.6 is not H or CH.sub.3.

13. An agrochemical composition comprising a herbicidal active amount of a compound of formula (I) or of an agriculturally suitable salt or N-oxide thereof: ##STR00020## wherein A is a fused saturated or unsaturated, 4- to 7-membered carbocycle or a fused saturated or unsaturated, 4- to 7-membered heterocycle having 1, 2 or 3 heteroatoms or heteroatom moieties, selected from O, S, SO, SO.sub.2, N or NR.sup.7 as ring members, R.sup.1 is selected from the group consisting of H and C.sub.1-C.sub.6-alkyl; R.sup.2 is selected from the group consisting of H and C.sub.1-C.sub.6-alkyl; R.sup.3 is selected from the group consisting of H, halogen, OH, CN, amino, NO.sub.2, C.sub.1-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkoxy, (C1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, where the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.4 is selected from the group consisting of H, halogen, OH, CN, amino, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.1-C6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1C-.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, where the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.5 is selected from the group consisting of H, halogen, OH, CN, amino, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-.sub.6-alkynyloxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkenyl, (C1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, where the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.6 is selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, phenyl, phenyl-C.sub.1-C.sub.6-alkyl, where the aliphatic and phenyl parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.7 is selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl; and at least one inert liquid and/or solid carrier.

14. The method according to claim 6, wherein each of R.sup.1 and R.sup.2 are H.

15. The method according to claim 7, wherein R.sup.3 is selected from the group consisting of H, Cl, and F.

16. The method according to claim 8 wherein R.sup.4 is selected from the group consisting of H, CF.sub.3, CH.sub.3, Cl and F.

17. The method according to claim 9, wherein, R.sup.5 is selected from the group consisting of H, Cl, and F.

18. The method according to claim 1, wherein R.sup.6 is selected from the group consisting of H, CH.sub.3, and CH.sub.2CH.sub.3.

19. The method according to claim 11, wherein R.sup.6 is Cl or F.

20. The method of claim 13 further comprising at least one surface-active substance.

Description

A. PREPARATION EXAMPLES

1. ethyl 4-bromo-5-formyl-1,3-benzodioxole-2-carboxylate

(1) ##STR00010##

(2) A mixture of 2-bromo-3,4-dihydroxy-benzaldehyde (CAS 4815-97-8) (1.6 g, 7.4 mmol), 2,2-dibromoaceticacid ethyl ester (3.6 g, 14.8 mmol), K.sub.2CO.sub.3 (2 g, 14.8 mmol) in DMF (20 mL) was heated to 100 C. for 2 h. The reaction was quenched by the addition of H.sub.2O, extracted with EtOAc and the combined organic phase were washed with brine. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and concentrated. The residue was purified by the column to give ethyl 4-bromo-5-formyl-1,3-benzodioxole-2-carboxylate (1 g, 45%) as a yellow solid.

(3) .sup.1H NMR: CDCl.sub.3 400 MHz 10.16 (d, J=1.51 Hz, 1H) 7.61 (dd, J=8.28, 1.76 Hz, 1H) 6.93 (d, J=8.16 Hz, 1H) 6.47 (s, 1H) 4.30-4.40 (m, 2H) 1.32-1.39 (m, 3H)

2. ethyl-4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5-formyl-1,3-benzodioxole-2-carboxylate

(4) ##STR00011##

(5) A mixture of ethyl 4-bromo-5-formyl-1,3-benzodioxole-2-carboxylate (2.7 g, 9 mmol), 2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5,5-dimethyl-1,3,2-dioxaborinane (3.4 g, 13.5 mmol), KOAc (2.6 g, 27 mmol) and Pd(dppf)Cl.sub.2 (270 mg) in Dioxane (30 mL) was heated to 80 C. for 2 h under N.sub.2. The reaction was quenched by the addition of H.sub.2O, extracted with EtOAc and the combined organic phase were washed with brine. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and concentrated. The residue was purified by the column to give ethyl 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5-formyl-1,3-benzodioxole-2-carboxylate (1.8 g, 66%) as a yellow solid.

(6) .sup.1H NMR: CDCl.sub.3 400 MHz 9.85 (s, 1H) 7.43 (d, J=7.91 Hz, 1H) 6.95 (d, J=8.03 Hz, 1H) 6.37 (s, 1H) 4.32 (q, J=6.99 Hz, 2H) 3.46-3.53 (m, 4H) 1.28-1.36 (m, 3H) 1.13 (s, 6H)

3. ethyl 1-hydroxy-3H-[1,3]dioxolo[4,5-g][2,1]benzoxaborole-7-carboxylate

(7) ##STR00012##

(8) NaBH.sub.4 (20 mg, 0.54 mmol) was added to the solution of ethyl 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5-formyl-1,3-benzodioxole-2-carboxylate (360 mg, 1.08 mmol) in MeOH (10 mL) in portions at 0 C. under N.sub.2. Then the mixture was stirred for 30 min. The reaction was quenched by the addition of H.sub.2O and adjust to pH=1 with HCl (6N), extracted with EtOAc and the combined organic phase were washed with brine. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and concentrated. The residue was triturated with MTBE to give ethyl 1-hydroxy-3H-[1,3]dioxolo[4,5][2,1]benzoxaborole-7-carboxylate (200 mg, 60%) as a yellow solid.

(9) .sup.1H NMR: DMSO 400 MHz 9.23 (s, 1H) 7.12 (d, J=7.91 Hz, 1H) 6.89 (d, J=7.91 Hz, 1H) 6.66 (s, 1H) 4.93 (s, 2H) 4.24 (q, J=7.07 Hz, 2H) 1.24 (t, J=7.09 Hz, 3H)

4.1-hydroxy-3H-[1,3]dioxolo[4,5-g][2,1]benzoxaborole-7-carboxylic acid

(10) ##STR00013##

(11) LiOH (96 mg, 4 mmol) was added to the solution of ethyl 1-hydroxy-3H-[1,3]dioxolo[4,5-g][2,1]benzoxaborole-7-carboxylate (500 mg, 2 mmol) in THF (6 mL)/H.sub.2O (2 mL) in portions at 20 C. under N.sub.2. Then the mixture was stirred for 2 h. The reaction was quenched by the addition of H.sub.2O, extracted with EtOAc. The aqueous phase was adjusted to pH=1 with HCl (6N), extracted with EtOAc and the combined organic phases were washed with brine, dried and concentrated. The residue was triturated with MTBE to give 1-hydroxy-3H-[1,3]dioxolo[4,5-g][2,1]benzoxaborole-7-carboxylic acid (200 mg, 40%) as a yellow solid.

(12) .sup.1H NMR: DMSO 400 MHz 9.22 (s, 1H) 7.09 (d, J=7.72 Hz, 1H) 6.87 (d, J=7.94 Hz, 1H) 6.54 (s, 1H) 4.93 (s, 2H).

5. methyl 5-formyl-4-hydroxy-2,3-dihydrobenzofuran-2-carboxylate

(13) ##STR00014##

(14) To the mixture of methyl 4-hydroxy-2,3-dihydrobenzofuran-2-carboxylate (CAS 403619-67-0) (1.94 g, 10 mmol), para-formaldehyde (660 mg, 22 mmol) and MgCl2 (1.9 g, 20 mmol) in THF (50 mL) was added Et.sub.3N (2.02 g, 20 mmol) drop-wise at 20 C. under N.sub.2. Then the mixture was stirred for 3 h at 85 C. The reaction was quenched by the addition of H.sub.2O, extracted with EtOAc and the combined organic phase were washed with brine. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered and concentrated. The residue was purified by the column to give methyl 5-formyl-4-hydroxy-2,3-dihydrobenzofuran-2-carboxylate (1 g, 50%) as a yellow solid.

(15) .sup.1H NMR: CDCl.sub.3 400 MHz 11.45 (s, 1H) 9.66-9.74 (m, 1H) 7.40 (d, J=8.41 Hz, 1H) 6.59 (d, J=8.41 Hz, 1H) 5.35 (dd, J=10.73, 6.59 Hz, 1H) 3.76-3.86 (m, 3H) 3.54 (dd, J=16.06, 10.79 Hz, 1H) 3.35 (dd, J=16.00, 6.46 Hz, 1H)

6. methyl 7-chloro-5-formyl-4-hydroxy-2,3-dihydrobenzofuran-2-carboxylate

(16) ##STR00015##

(17) To a solution of methyl 5-formyl-4-hydroxy-2,3-dihydrobenzofuran-2-carboxylate (13.6 g, 60 mmol), MeOH (7.7 g, 24 mmol) in DCM (140 mL) was added sulfurylchloride (32.5 g, 24 mmol) at 0 C. dropwise. The mixture was stirred at 0 C. for 16 h. The reaction was quenched with H.sub.2O and extracted with EtOAc. The combined organics were washed with brine. Dried and concentrated. The crude product was triturated with MTBE to give methyl 7-chloro-5-formyl-4-hydroxy-2,3-dihydrobenzofuran-2-carboxylate (6.4 g, 41%) as a yellow solid.

(18) .sup.1H NMR: CDCl.sub.3 400 MHz 9.65-9.71 (m, 1H) 7.42 (s, 1H) 5.43 (dd, J=10.69, 6.50 Hz, 1H) 3.82-3.89 (m, 3H) 3.61 (dd, J=16.10, 10.80 Hz, 1H) 3.37-3.49 (m, 1H)

7. methyl-7-chloro-5-formyl-4-(trifluoromethylsulfonyloxy)-2,3-dihydrobenzofuran-2-carboxylate

(19) ##STR00016##

(20) To a solution of methyl 7-chloro-5-formyl-4-hydroxy-2,3-dihydrobenzofuran-2-carboxylate (6.4 g, 25 mmol) and Et.sub.3N (10.1 g, 100 mmol) in DCM (70 mL) was added trifluoromethane sulfonic acid anhydride (10.6 g, 37.5 mmol) at 0 C. dropwise. The mixture was stirred at 0 C. for 2 h. The reaction was quenched with H.sub.2O and extracted with EtOAc. The combined organics were washed with brine, dried and concentrated. The crude was purified by column (PE:EtOAc=100:120:1) to give methyl 7-chloro-5-formyl-4-(trifluoromethylsulfonyloxy)-2,3-dihydrobenzofuran-2-carboxylate (5 g, 52%) as a yellow solid.

(21) .sup.1H NMR: CDCl.sub.3 400 MHz 10.04 (s, 1H) 7.90 (s, 1H) 5.49 (dd, J=10.58, 6.17 Hz, 1H) 3.87 (s, 3H) 3.79-3.85 (m, 1H) 3.62-3.71 (m, 1H)

8. methyl-7-chloro-4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5-formyl-2,3-dihydrobenzofuran-2-carboxylate

(22) ##STR00017##

(23) The mixture of methyl 7-chloro-5-formyl-4-(trifluoromethylsulfonyloxy)-2,3-dihydrobenzofuran-2-carboxylate (6 g, 15.46 mmol), 2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5,5-dimethyl-1,3,2-dioxaborinane (10.48 g, 46.38 mmol), KOAc (9.1 g, 92.76 mmol) and Pd(dppf)Cl.sub.2 in Dioxane (60 mL) was stirred at 90 C. for 1 h. The reaction was quenched with H.sub.2O and extracted with EtOAc. The combined organics were washed with brine, dried and concentrated. The crude was purified by column (PE:EtOAc=50:110:1) to give methyl 7-chloro-4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5-formyl-2,3-dihydrobenzofuran-2-carboxylate (4 g, 74%) as a yellow solid.

(24) .sup.1H NMR: CDCl.sub.3 400 MHz 10.04 (s, 1H) 7.74 (s, 1H) 5.36 (dd, J=10.80, 6.84 Hz, 1H) 3.83 (s, 3H) 3.80 (s, 4H) 3.70-3.78 (m, 1H) 3.51-3.58 (m, 1H) 1.11 (br s, 1H) 1.09 (s, 5H)

9. methyl-5-chloro-1-hydroxy-3-methyl-7,8-dihydro-3H-furo[2,3-g][2,1]benzoxaborole-7-carboxylate

(25) ##STR00018##

(26) To a solution of methyl 7-chloro-4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-5-formyl-2,3-dihydrobenzofuran-2-carboxylate (5 g, 14.2 mmol) and in THF (60 mL) was added methyl magnesium bromide (9.5 mL, 28.4 mmol, 3M) at 0 C. dropwise under N.sub.2. The mixture was stirred at 20 C. for 16 h. To the reaction was added HCl (4 mL, 6N). The reaction was quenched with H.sub.2O and extracted with EtOAc. The combined organics were washed with brine, dried and concentrated. The crude was purified by prep-HPLC (TFA, CH.sub.3CNH.sub.2O) to give methyl 5-chloro-1-hydroxy-3-methyl-7,8-dihydro-3H-furo[2,3-g][2,1]benzoxaborole-7-carboxylate (409 mg, 10%) as a yellow solid.

(27) .sup.1H NMR: CDCl.sub.3 400 MHz 7.09 (s, 1H) 5.35 (dd, J=10.58, 6.39 Hz, 1H) 5.25 (qd, J=6.54, 2.43 Hz, 1H) 3.82 (d, J=1.32 Hz, 3H) 3.70-3.79 (m, 1H) 3.53-3.61 (m, 1H) 1.48 (dd, J=6.50, 2.09 Hz, 3H)

(28) The compounds 2 to 3 listed below in Table 3 have been prepared by analogy to the example 1 mentioned above.

(29) TABLE-US-00005 MS m/z (M + 1)/ MS-retention time/ .sup.1H-NMR(DMSO)/ Compound R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 ACO.sub.2R.sup.6 CAS number 2 H H H H H H OCH(CO.sub.2R.sup.6)O 223 3 H H H H H CH.sub.2CH.sub.3 OCH(CO.sub.2R.sup.6)O 251 4 H H H H H CH.sub.3 OCH(CO.sub.2R.sup.6)O 237 5 H H H H H CH.sub.3 OCH(CO.sub.2R.sup.6)CH.sub.2 235 6 H H H H H H OCH(CO.sub.2R.sup.6)CH.sub.2 221 7 H H H Cl H CH.sub.3 OCH(CO.sub.2R.sup.6)CH.sub.2 269 Enantiomer 1 8 H H H Cl H CH.sub.3 OCH(CO.sub.2R.sup.6)CH.sub.2 269 Enantiomer 2 9 CH.sub.3 H H Cl H CH.sub.3 OCH(CO.sub.2R.sup.6)CH.sub.2 283 10 H H H F H CH.sub.3 OC(CO.sub.2R.sup.6)CH 251 11 H H H F H H OC(CO.sub.2R.sup.6)CH 237 12 H H H F H CH.sub.3 OCH(CO.sub.2R.sup.6)CH.sub.2 253 13 H H H F H H OCH(CO.sub.2R.sup.6)CH.sub.2 239 14 H H H H H CH.sub.3 CH.sub.2CH(CO.sub.2R.sup.6)CH.sub.2 233 15 H H H H H CH.sub.2CH.sub.3 OCH(CO.sub.2R.sup.6)CH.sub.2O 265 16 H H H H H CH.sub.2CH.sub.3 OCH.sub.2CH(CO.sub.2R.sup.6)O 265 17 H H H H H CH.sub.3 CH.sub.2CH(CO.sub.2R.sup.6)O 235 18 H H H H H H CH.sub.2CH(CO.sub.2R.sup.6)O 221 19 H H H CF.sub.3 H CH.sub.3 CH.sub.2CH(CO.sub.2R.sup.6)CH.sub.2 301 20 H H H H H CH.sub.3 CH.sub.2CH(CO.sub.2R.sup.6)CH.sub.2CH.sub.2 247 21 H H H H H H CH.sub.2CH(CO.sub.2R.sup.6)CH.sub.2CH.sub.2 233 22 H H H CF.sub.3 H H CH.sub.2CH(CO.sub.2R.sup.6)CH.sub.2 287 23 H H H H H CH.sub.3 SCH(CO.sub.2R.sup.6)CH.sub.2 251 24 H H H H H H SCH(CO.sub.2R.sup.6)CH.sub.2 237 25 H H H H H CH.sub.2CH.sub.3 OCH(CO.sub.2R.sup.6)CH.sub.2 249 26 H H H H H CH.sub.2CCH OCH(CO.sub.2R.sup.6)CH.sub.2 259 27 H H H H H CH.sub.2CF.sub.3 OCH(CO.sub.2R.sup.6)CH.sub.2 303 28 H H H H H CH.sub.2CH.sub.2OCH.sub.3 OCH(CO.sub.2R.sup.6)CH.sub.2 279 29 H H H H H CH.sub.3 OC(CH.sub.3)(CO.sub.2R.sup.6)CH.sub.2 249 30 H H H H H C.sub.6H.sub.5 OCH(CO.sub.2R.sup.6)CH.sub.2 297

B USE EXAMPLES

(30) The herbicidal activity of the azines of formula (I) was demonstrated by the following greenhouse experiments:

(31) The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

(32) For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients.

(33) For the post-emergence treatment, the test plants were first grown to a height of 3 to 8 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.

(34) Depending on the species, the plants were kept at 10-25 C. or 20-35 C., respectively.

(35) The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

(36) Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A moderate herbicidal activity is given at values of at least 60, a good herbicidal activity is given at values of at least 70, and a very good herbicidal activity is given at values of at least 85.

(37) The plants used in the greenhouse experiments were of the following species:

(38) TABLE-US-00006 Bayer code Scientific name ABUTH Abutilon theophrasti ALOMY Alopecurus myosuroides AMARE Amaranthus retroflexus AVEFA Avena fatua ECHCG Echinocloa crus-galli POLCO Polygonum convolvulus SEBEX Sesbania exaltata SETVI Setaria viridis SETFA Setaria faberi

(39) The results of the herbicidal activity of compounds I against various weed species and certain monocot crop plants at different application rates are summarized in Examples 1-9 below.

Example 1

(40) At an application rate of 2 kg/ha, the compound 2 applied by the post-emergence method, showed 100%, 90% and 80% herbicidal activity against Amaranthus retroflexus, Abutilon theophrasti and Setaria viridis respectively.

Example 2

(41) At an application rate of 2 kg/ha, the compound 3 applied by the post-emergence method, showed 100% and 100% herbicidal activity against Amaranthus retroflexus and Setaria viridis respectively.

Example 3

(42) At an application rate of 2 kg/ha, the compound 4 applied by the post-emergence method, showed 100% and 100% herbicidal activity against Amaranthus retroflexus and Abutilon theophrasti respectively.

Example 4

(43) At an application rate of 2 kg/ha, the compound 5 applied by the post-emergence method, showed 100%, 100 and 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria viridis respectively and by the pre-emergence method, showed 95%, 80 and 85% herbicidal activity against Amaranthus retroflexus, Abutilon theophrasti and Setaria faberi respectively.

Example 5

(44) At an application rate of 2 kg/ha, the compound 6 applied by the post-emergence method, showed 100%, 100% and 98% herbicidal activity against Amaranthus retroflexus, Abutilon theophrasti and Alopecurus myosuroides respectively and by the pre-emergence method, showed 80% herbicidal activity against Amaranthus retroflexus.

Example 6

(45) At an application rate of 2 kg/ha, the compound 7 applied by the post-emergence method, showed 100%, 100% and 100% herbicidal activity against Amaranthus retroflexus, Abutilon theophrasti and Avena fatua respectively.

Example 7

(46) At an application rate of 2 kg/ha, the compound 8 applied by the post-emergence method, showed 100%, 100% and 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria viridis respectively and by the pre-emergence method, showed 80% herbicidal activity against Setaria faberi.

Example 8

(47) At an application rate of 2 kg/ha, the compound 9 applied by the post-emergence method, showed 100%, 100% and 98% herbicidal activity against Amaranthus retroflexus, Abutilon theophrasti and Avena fatua respectively.

Example 9

(48) At an application rate of 0.25 kg/ha, the compound 12 applied by the post-emergence method, showed 100%, 95% and 100% herbicidal activity against Sesbania exaltata, Polygonum convolvulus and Amaranthus retroflexus respectively.

Example 10

(49) At an application rate of 0.25 kg/ha, the compound 13 applied by the post-emergence method, showed 100%, 85% and 100% herbicidal activity against Sesbania exaltata, Polygonum convolvulus and Amaranthus retroflexus respectively.

Example 11

(50) At an application rate of 0.25 kg/ha, the compound 14 applied by the post-emergence method, showed 100% herbicidal activity against Abutilon theophrasti, Sesbania exaltata and Amaranthus retroflexus.

Example 12

(51) At an application rate of 2 kg/ha, the compound 15 applied by the post-emergence method, showed 90% herbicidal activity against Abutilon theophrasti and Amaranthus retroflexus.

Example 13

(52) At an application rate of 2 kg/ha, the compound 16 applied by the post-emergence method, showed 100% herbicidal activity against Amaranthus retroflexus.

Example 14

(53) At an application rate of 2 kg/ha, the compound 17 applied by the post-emergence method, showed 100% herbicidal activity against Amaranthus retroflexus.

Example 15

(54) At an application rate of 1 kg/ha, the compound 18 applied by the post-emergence method, showed 100% and 90% herbicidal activity against Amaranthus retroflexus and Setaria viridis respectively.

Example 16

(55) At an application rate of 1 kg/ha, the compound 19 applied by the post-emergence method, showed 100%, 100% and 90% herbicidal activity against Amaranthus retroflexus, Abutilon theophrasti and Setaria viridis respectively.

Example 17

(56) At an application rate of 1 kg/ha, the compound 20 applied by the post-emergence method, showed 100% herbicidal activity against Amaranthus retroflexus, Abutilon theophrasti and Setaria viridis.

Example 18

(57) At an application rate of 1 kg/ha, the compound 21 applied by the post-emergence method, showed 100%, 80% and 80% herbicidal activity against Amaranthus retroflexus, Setaria viridis and Alopecurus myosuroides respectively.

Example 19

(58) At an application rate of 1 kg/ha, the compound 22 applied by the post-emergence method, showed 100%, 100% and 95% herbicidal activity against Amaranthus retroflexus, Abutilon theophrasti and Alopecurus myosuroides respectively.