Benzoxaborole compounds

Abstract

The present invention relates to the use of the compounds of formula (I) ##STR00001##
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.

Claims

1. A method for controlling unwanted vegetation, wherein the unwanted vegetation, their seed, and/or their habitat is treated with a herbicidally effective amount of the compound of formula I ##STR00010## wherein X is O, NR.sup.7, S, SO, or SO.sub.2; Y is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, and C.sub.3-C.sub.6-alkynyl wherein the radicals are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C(═O)O(C.sub.1-C.sub.6-alkyl) and phenyl which is unsubstituted or substituted by halogen, C.sub.1-C.sub.6-alkyl, or C.sub.1-C.sub.6-haloalkyl; 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, and (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, wherein the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; 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; 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, and (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, wherein the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.6 is H; 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, and C.sub.3-C.sub.6-alkynyl; or an agriculturally suitable salt or N-oxide thereof.

2. The method of claim 1, wherein X is O.

3. The method of claim 1, wherein Y is C.sub.1-C.sub.6-alkyl which is unsubstituted.

4. The method of claim 1, wherein Y is —CH.sub.2-.

5. The method of claim 1, wherein Y is C.sub.1-C.sub.6-alkyl which is substituted by 1 or 2 identical or different substituents selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C(═O)O(C.sub.1-C.sub.6-alkyl) and phenyl.

6. The method of claim 5, wherein Y is —CH.sub.2— which is substituted by 1 or 2 identical or different substituents selected from the group consisting of CH.sub.3, CH.sub.2CH.sub.3, C(═O)(OCH.sub.3), OCH.sub.3 and unsubstituted phenyl.

7. The method of 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.

8. The method of claim 7, wherein R.sup.1 and R.sup.2 are both H.

9. The method of 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.

10. The method of claim 9, wherein R.sup.3 is H.

11. The method of 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.

12. The method of claim 11, wherein R.sup.5 is selected from the group consisting of H, Cl, and F.

13. A compound of the formula (I) as defined in claim 1 ##STR00011## wherein X is O, NR.sup.7, S, SO, or SO.sub.2.sup.−; Y is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl, and C.sub.3-C.sub.6-alkynyl wherein the radicals are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C(═O)O(C.sub.1-C.sub.6-alkyl) and phenyl which is unsubstituted or substituted by halogen, C.sub.1-C.sub.6-alkyl, or C.sub.1-C.sub.6-haloalkyl; 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, and (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, wherein the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; 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; 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, and (C.sub.1-C.sub.6-alkoxy)-C.sub.3-C.sub.6-alkynyl, wherein the aliphatic parts of the aforementioned radicals are unsubstituted, partly or completely halogenated; R.sup.6 is H; 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, and C.sub.3-C.sub.6-alkynyl; with the proviso that if R.sup.1 and R.sup.2 are H R.sup.4 is not H, Cl and F; and if R.sup.1 or R.sup.2 is CH.sub.3 R.sup.4 is not H.

14. An agrochemical composition comprising a herbicidal active amount of at least one compound as claimed in claim 13 and at least one inert liquid and/or solid carrier and, if appropriate, at least one surface-active substances.

15. The method of claim 1, wherein R.sup.4 is selected from the group consisting of H, Cl, and F.

16. The method of claim 1, wherein R.sup.4 is selected from the group consisting of Cl and F.

Description

A. PREPARATION EXAMPLES

Example 1: Methyl 2-[(5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-yl)oxy]-2-methoxy-acetate (see table below)

(1) ##STR00007##

(2) 0.17 g (1.0 mmol) 5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-ol (CAS 1629140-80-2) was dissolved in 8 ml dimethylformamide and 0.41 g (3.0 mmol) K2CO3 and 0.22 g (1.2 mmol) 2-bromo-2-methoxyaceticacidmethylester were added. After stirring at room temperature for 24 h water was added and the mixture was extracted with dichloromethane. After evaporation of the solvents the residue was chromatographed with dichloromethane/methanol resulting in 30 mg of methyl 2-[(5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-yl)oxy]-2-methoxy-acetate as a colorless oil.

(3) 1H-NMR (d6-DMSO): 3.5 (s, 3H); 3.8 (s, 3H); 4.9 (s, 2H); 5.7 (s, 1H); 7.4 (d, 1H); 7.6 (d, 1H); 9.3 (s, 1H)

Example 2: Methyl 2-[(5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-yl)oxy]-2-phenyl-acetate (see table below)

(4) ##STR00008##

(5) 0.17 g (1.0 mmol) 5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-ol (CAS 1629140-80-2) was dissolved in 8 ml dimethylformamide and 0.41 g (3.0 mmol) K2CO3 and 0.28 g (1.2 mmol) 2-bromo-2-phenylaceticacidmethylester were added. After stirring at room temperature for 24 h water was added and the mixture was extracted with ethylacetate. After evaporation of the solvents the residue was chromatographed with dichloromethane/methanol resulting in 117 mg of methyl 2-[(5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-yl)oxy]-2-phenyl-acetate as a colorless oil. 1H-NMR (d6-DMSO): 3.7 (s, 3H); 4.9 (s, 2H); 6.0 (s, 1H); 7.3-7.6 (m, 5H); 9.3 (s, 1H)

Example 3: 2-[(5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-yl)oxy]-2-phenyl-acetatic acid (see table below)

(6) ##STR00009##

(7) 0.055 g (0.17 mmol) methyl 2-[(5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-yl)oxy]-2-phenyl-acetate was dissolved in 1 ml isopropanol and 0.35 ml (0.35 mmol) 1M aqueous LiOH-solution was added. After stirring at room temperature for 2 h the solvents were evaporated, water was added and extracted with dichloromethane. The aqueous phase was acidified with 2N Hcl and the precipitate filtrated, resulting in 29 mg of 2-[(5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-yl)oxy]-2-phenyl-acetatic acid as colorless solid.

(8) 1H-NMR (d6-DMSO): 4.9 (s, 2H); 5.8 (s, 1H); 7.4-7.6 (m, 5H); 9.3 (s, 1H); 13.3 (br, 1H)

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

(10) TABLE-US-00005 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 X Y CAS nunnber I-1 H H H H H H O —CH.sub.2—  947164-82-1 I-2 H H H H H CH.sub.2 O —C(CH.sub.3).sub.2— 1268390-39-1 CH.sub.3 I-3 H H H H H CH.sub.3 O —CH.sub.2— 1268390-35-7 I-4 H H H H H H O —C(CH.sub.3).sub.2— 1296850-35-5 I-5 H H H F H CH.sub.3 O —CH.sub.2— 1803546-90-8 I-6 H H H F H H O —CH.sub.2— 0.941 I-7 H H H Cl H CH.sub.3 O —CH.sub.2— 1803547-27-4 I-8 H H H Cl H H O —CH.sub.2— 0.956 I-9 H H H Cl Cl CH.sub.3 O —CH.sub.2— 1.061 I-10 H H H F H CH.sub.3 O —CH(C═O)(OCH.sub.3)— 1803546-93-1 I-11 H H H F H CH.sub.3 O —CH(OCH.sub.3)— 3.5 (s, 3H); 3.8 (s, 3H); 4.9 (s, 2H); 5.7 (s, 1H); 7.4 (d, 1H); 7.6 (d, 1H); 9.3 (s, 1H) I-12 H H H F H CH.sub.3 O —CH(CH.sub.3).sub.2— 0.898 I-13 H H H F H CH.sub.3 O —CH(CH.sub.2CH.sub.3)— 1803546-86-2 I-14 H H H F H CH.sub.3 O —CHPh— 3.7 (s, 3H); 4.9 (s, 2H); 6.0 (s, 1H); 7.3-7.6 (m, 5H); 9.3 (s, 1H) I-15 H H H Cl Cl H O —CH.sub.2— 0.98 I-16 H H H F H H O —CHPh— 4.9 (s, 2H); 5.8 (s, 1H); 7.4-7.6 (m, 5H); 9.3 (s, 1H); 13.3 (br, 1H) I-17 H H H H H CH.sub.3 NH —CH.sub.2— 0.703 I-18 CH.sub.3 H H H H H O —CH.sub.2— 0.723 I-19 H H H H H CH.sub.3 NCH.sub.3 —CH.sub.2— 0.785 I-20 CH.sub.3 H H H H CH.sub.3 O —CH.sub.2— 0.858 I-21 H H H F H H O —(CH.sub.2).sub.2— 0.748 I-22 H H H F H H S —CH.sub.2— 0.931 I-23 H H F F H H O —CH.sub.2— 0.861 I-24 H H H F F H O —CH.sub.2— 0.852 I-25 H H H F H H O —(CH.sub.2).sub.3— 0.779 I-26 H H H H H CH.sub.2 O —CHF— 0.919 CH.sub.3 I-27 CH.sub.3 H H F H CH.sub.3 O —CH.sub.2— 0.908 I-28 H H H F H CH.sub.3 S —CH.sub.2— 0.955 I-29 H H H F F CH.sub.3 O —CH.sub.2— 0.893 I-30 H H H F F H O —CHCH.sub.3— 0.894 I-31 H H F F H CH.sub.3 O —CH.sub.2— 0.891 I-32 H H Cl F H H O —CH.sub.2— 0.903 I-33 H H F F F H O —CH.sub.2— 0.875 I-34 H H H F H CH.sub.2 O —CHF— 0.963 CH.sub.3 I-35 H H H F F CH.sub.3 O —CHCH.sub.3— 0.955 I-36 CH.sub.3 H F F H CH.sub.3 O —CH.sub.2— 0.96 I-37 H H H F H H SO.sub.2 —CH.sub.2— 0.755 I-38 H H Cl F H CH.sub.3 O —CH.sub.2— 1.078 I-39 H H F F F CH.sub.3 O —CH.sub.2— 0.97 I-40 H H H F H CH.sub.2 O —(CH.sub.2).sub.3— 1.007 CH.sub.3 I-41 CH.sub.2 H F F H CH.sub.3 O —CH.sub.2— 1.019 CH.sub.3 I-42 H H H F H CH.sub.3 SO.sub.2 —CH.sub.2— 0.809

B USE EXAMPLES

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

(12) 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.

(13) 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.

(14) 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.

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

(16) 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.

(17) 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.

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

(19) TABLE-US-00006 Bayer code Scientific name ABUTH Abutilon theophrasti ALOMY Alopecurus myosuroides AMARE Amaranthus retroflexus AVEFA Avena fatua ECHCG Echinocloa crus-galli SETVI Setaria viridis

(20) 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 1-10 below.

Example 1

(21) At an application rate of 2 kg/ha, the compound I-1 applied by the post-emergence method, showed 100%, 90%, 100%, 90% and 100% herbicidal activity against Echinocloa crus-galli, Abutilon theophrasti, Amaranthus retroflexus, Avena fatua and Setaria viridis respectively.

Example 2

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

Example 3

(23) At an application rate of 2 kg/ha, the compound I-3 applied by the post-emergence method, showed 98%, 100%, 100% 90% and 100% herbicidal activity against Echinocloa crus-galli, Abutilon theophrasti, Amaranthus retroflexus, Avena fatua and Setaria viridis respectively.

Example 4

(24) At an application rate of 2 kg/ha, the compound I-5 applied by the post-emergence method, showed 98%, 98%, 100%, 100%, 98% and 98% herbicidal activity against Echinocloa crus-galli, Alopecurus myosuroides, Abutilon theophrasti, Amaranthus retroflexus, Avena fatua and Setaria viridis respectively.

Example 5

(25) At an application rate of 2 kg/ha, the compound I-6 applied by the post-emergence method, showed 98%, 90%, 100%, 100%, 98% and 100% herbicidal activity against Echinocloa crus-galli, Alopecurus myosuroides, Abutilon theophrasti, Amaranthus retroflexus, Avena fatua and Setaria viridis respectively.

Example 6

(26) At an application rate of 2 kg/ha, the compound 1-7 applied by the post-emergence method, showed 100%, 95%, 100%, 100%, 98% and 100% herbicidal activity against Echinocloa crus-galli, Alopecurus myosuroides, Abutilon theophrasti, Amaranthus retroflexus, Avena fatua and Setaria viridis respectively.

Example 7

(27) At an application rate of 2 kg/ha, the compound 1-8 applied by the post-emergence method, showed 100%, 98%, 100%, 100%, 98% and 95% herbicidal activity against Echinocloa crus-galli, Alopecurus myosuroides, Abutilon theophrasti, Amaranthus retroflexus, Avena fatua and Setaria viridis respectively.

Example 8

(28) At an application rate of 2 kg/ha, the compound 1-10 applied by the post-emergence method, showed 90% and 95% herbicidal activity against Amaranthus retroflexus and Setaria viridis respectively.

Example 9

(29) At an application rate of 2 kg/ha, the compound 1-15 applied by the post-emergence method, showed 85%, 100% and 90% herbicidal activity against Echinocloa crus-galli, Amaranthus retroflexus and Setaria viridis respectively.

Example 10

(30) At an application rate of 2 kg/ha, the compound 1-4 applied by the post-emergence method, showed 85% herbicidal activity against Echinocloa crus-galli and Abutilon theophrasti.

Example 11

(31) At an application rate of 2 kg/ha, the compound 1-39 applied by the post-emergence method, showed 100% herbicidal activity against Amaranthus retroflexus and Setaria viridis.

Example 12

(32) At an application rate of 2 kg/ha, the compound 1-25 applied by the post-emergence method, showed 95% herbicidal activity against Amaranthus retroflexus and Setaria viridis.

Example 13

(33) At an application rate of 2 kg/ha, the compound 1-28 applied by the post-emergence method, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Setaria viridis.

Example 14

(34) At an application rate of 2 kg/ha, the compound 1-42 applied by the post-emergence method, showed 100% herbicidal activity against Abutilon theophrasti and Amaranthus retroflexus.

Example 15

(35) At an application rate of 2 kg/ha, the compound 1-33 applied by the post-emergence method, showed 98%, 100% and 98% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Setaria viridis respectively.

Example 16

(36) At an application rate of 2 kg/ha, the compound 1-22 applied by the post-emergence method, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Setaria viridis.

Example 17

(37) At an application rate of 2 kg/ha, the compound 1-37 applied by the post-emergence method, showed 100% herbicidal activity against Amaranthus retroflexus.

Example 18

(38) At an application rate of 2 kg/ha, the compound 1-29 applied by the post-emergence method, showed 95%, 100% and 100% herbicidal activity against Echinocloa crus-galli, Amaranthus retroflexus, Setaria viridis respectively.

Example 19

(39) At an application rate of 2 kg/ha, the compound 1-26 applied by the post-emergence method, showed 90%, 100% and 85% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Setaria viridis respectively.

Example 20

(40) At an application rate of 2 kg/ha, the compound 1-35 applied by the post-emergence method, showed 100%, 100% and 98% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Setaria viridis respectively.

Example 21

(41) At an application rate of 2 kg/ha, the compound 1-24 applied by the post-emergence method, showed 100%, 100% and 95% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Setaria viridis respectively.

Example 22

(42) At an application rate of 2 kg/ha, the compound 1-30 applied by the post-emergence method, showed 85%, 95% and 100% herbicidal activity against Alopecurus myosuroides, Abutilon theophrasti and Amaranthus retroflexus respectively.