Diaminotriazine derivatives as herbicides

Abstract

The present invention relates to diaminotriazine compounds of the formula (I) and to their use as herbicides. The present invention also relates to agrochemical compositions for crop protection and to a method for controlling unwanted vegetation. ##STR00001## wherein q is 0, 1, 2 or 3 R.sup.a is selected from the group consisting of C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-haloalkylthio, (C.sub.1-C.sub.6-haloalkyl)sulfinyl, (C.sub.1-C.sub.6-haloalkyl)-carbonyl, etc.; R.sup.b is selected from the group consisting of halogen, OH, CN, amino, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, etc.; R.sup.1 is selected from the group consisting of H, OH, S(O).sub.2NH.sub.2, CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, etc.; R.sup.2 is selected from the group consisting of H, OH, S(O).sub.2NH.sub.2, CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, etc.; R.sup.3 is selected from the group consisting of H, halogen, OH, CN, C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, etc.; R.sup.4 is H, halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; R.sup.5 is selected from the group consisting of halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, etc.; or R.sup.4 and R.sup.5 together with the carbon atom to which they are attached form a moiety selected from the group consisting of carbonyl, C.sub.3-C.sub.6-cycloalkan-1,1-diyl, ipso-C.sub.3-C.sub.6-cycloalkendiyl, three- to six-membered saturated or partially unsaturated ipso-heterocyclodiyl; including their agriculturally acceptable salts.

Claims

1. A diaminotriazine compound of formula (I) ##STR00024## wherein q is 0, 1, or 2; R.sup.a is selected from the group consisting of C3-C6-cycloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, and (C3-C6-cycloalkyl)-C.sub.1-C.sub.4-alkoxy; R.sup.b is selected from the group consisting of halogen; R.sup.1 is selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)carbonyl, and (C.sub.1-C.sub.6-alkoxy)carbonyl; R.sup.2 is selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)carbonyl, and (C.sub.1-C.sub.6-alkoxy)carbonyl; R.sup.3 is selected from the group consisting of H, fluorine, chlorine, C.sub.1-C.sub.4-alkyl, and C.sub.1-C.sub.4-alkoxy; R.sup.4 is selected from the group consisting of H, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, and C.sub.1-C.sub.6-haloalkoxy; R.sup.5 is selected from the group consisting of CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkenyl and C1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, where the aliphatic and cycloaliphatic parts of the 7 aforementioned radicals are unsubstituted, partly or completely halogenated; or R.sup.4 and R.sup.5 together with the carbon atom to which they are attached may form a moiety selected from the group consisting of carbonyl, C.sub.3-C.sub.6-cycloalkan-1,1-diyl, ipso-C.sub.3-C.sub.6-cycloalkendiyl, three- to six-membered saturated or partially unsaturated ipso-heterocyclodiyl, where the carbocycle and the heterocycle are unsubstituted, partly or completely halogenated or carry from 1 to 6 C.sub.1-C.sub.6-alkyl groups, and the moiety >CCR.sup.XR.sup.Y, where R.sup.x and R.sup.y are hydrogen, C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-haloalkyl; including their agriculturally acceptable salts.

2. The compound of claim 1, wherein R.sup.b is fluorine.

3. The compound of claim 1, wherein the moiety ##STR00025## is represented by the moiety ##STR00026## wherein R.sup.a is as defined in claim 1 and wherein R.sup.b1, R.sup.b2 and R.sup.b3 are identical or different and are hydrogen or have one of the meanings of R.sup.b defined in claim 1.

4. The compound of claim 3, wherein R.sup.b1, R.sup.b2 and R.sup.b3 are selected from the group consisting of hydrogen and fluorine.

5. The compound of claim 1, wherein the moiety ##STR00027## is selected from the group consisting of 2-fluoro-6-(cyclopropyloxy)phenyl, 2-fluoro-6-(cyclobutyloxy)phenyl, 2-fluoro-6-(cyclopentyloxy)phenyl, 2-fluoro-6-(cyclohexyloxy) phenyl, 2-fluoro-6-[(cyclopropyl)methyloxy]phenyl, 2-fluoro-6-[(cyclobutyl)methyloxy]phenyl, 2-fluoro-6-[(cyclopentyl)methyloxy]phenyl, 2-fluoro-6-[(cyclohexyl)methyloxy]phenyl, 2-fluoro-6-prop-2-enoxyphenyl, 2-fluoro-6-prop-2-ynoxyphenyl, 2,3-difluoro-6-(cyclopropyloxy)phenyl, 2,3-difluoro-6-(cyclobutyloxy)phenyl, 2,3-difluoro-6-(cyclopentyloxy)phenyl, 2,3-difluoro-6-(cyclohexyloxy)phenyl, 2,3-difluoro-6-[(cyclopropyl)methyloxy]phenyl, 2,3-difluoro-6-[(cyclobutyl)methyloxy]phenyl, 2,3-difluoro-6-[(cyclopentyl)methyloxy]phenyl, 2,3-difluoro-6-[(cyclohexyl)methyloxy]phenyl, 2,3-difluoro-6-prop-2-enoxyphenyl, 2,3-difluoro-6-prop-2-ynoxyphenyl, 2,4-difluoro-6-(cyclopropyloxy) phenyl, 2,4-difluoro-6-(cyclobutyloxy)phenyl, 2,4-difluoro-6-(cyclopentyloxy)phenyl, 2,4-difluoro-6-(cyclohexyloxy)phenyl, 2,4-difluoro-6-[(cyclopropyl)methyloxy]phenyl, 2,4-difluoro-6-[(cyclobutyl)methyloxy]phenyl, 2,4-difluoro-6-[(cyclopentyl)methyloxy]phenyl, 2,4-difluoro-6-[(cyclohexyl)methyloxy]phenyl, 2,4-difluoro-6-prop-2-enoxyphenyl, 2,4-difluoro-6-prop-2-ynoxyphenyl, 2,5-difluoro-6-(cyclopropyloxy)phenyl, 2,5-difluoro-6-(cyclobutyloxy)phenyl, 2,5-difluoro-6-(cyclopentyloxy)phenyl, 2,5-difluoro-6-(cyclohexyloxy)phenyl, 2,5-difluoro-6-[(cyclopropyl)methyloxy]phenyl, 2,5-difluoro-6-[(cyclobutyl)methyloxy]phenyl, 2,5-difluoro-6-[(cyclopentyl)methyloxy]phenyl, 2,5-difluoro-6-[(cyclohexyl)methyloxy]phenyl, 2,5-difluoro-6-prop-2-enoxyphenyl, 2,5-difluoro-6-prop-2-ynoxyphenyl, 2,3,5-trifluoro-6-(cyclopropyloxy)phenyl, 2,3,5-trifluoro-6-(cyclobutyloxy)phenyl, 2,3,5-trifluoro-6-(cyclopentyloxy)phenyl, 2,3,5-trifluoro-6-(cyclohexyloxy)phenyl, 2,3,5-trifluoro-6-[(cyclopropyl)methyloxy]phenyl, 2,3,5-trifluoro-6-[(cyclobutyl)methyloxy]phenyl, 2,3,5-trifluoro-6-[(cyclopentyl) methyloxy]phenyl, 2,3,5-trifluoro-6-[(cyclohexyl)methyloxy]phenyl, 2,3,5-trifluoro-6-prop-2-enoxyphenyl, 2,3,5-trifluoro-6-prop-2-ynoxyphenyl, 2,4,5-trifluoro-6-(cyclopropyloxy)phenyl, 2,4,5-trifluoro-6-(cyclobutyloxy)phenyl, 2,4,5-trifluoro-6-(cyclopentyloxy)phenyl, 2,4,5-trifluoro-6-(cyclohexyloxy)phenyl, 2,4,5-trifluoro-6-[(cyclopropyl)methyloxy]phenyl, 2,4,5-trifluoro-6-[(cyclobutyl)methyloxy]phenyl, 2,4,5-trifluoro-6-[(cyclopentyl)methyloxy]phenyl, 2,4,5-trifluoro-6-[(cyclohexyl)methyloxy]phenyl, 2,4,5-trifluoro-6-prop-2-enoxyphenyl, 2,4,5-trifluoro-6-prop-2-ynoxyphenyl, 2,3,4-trifluoro-6-(cyclopropyloxy)phenyl, 2,3,4-trifluoro-6-(cyclobutyloxy)phenyl, 2,3,4-trifluoro-6-(cyclopentyloxy)phenyl, 2,3,4-trifluoro-6-(cyclohexyloxy)phenyl, 2,3,4-trifluoro-6-[(cyclopropyl)methyloxy]phenyl, 2,3,4-trifluoro-6-[(cyclobutyl)methyloxy]phenyl, 2,3,4-trifluoro-6-[(cyclopentyl)methyloxy]phenyl, 2,3,4-trifluoro-6-[(cyclohexyl)methyloxy]phenyl, 2,3,4-trifluoro-6-prop-2-enoxyphenyl, and 2,3,4-trifluoro-6-prop-2-ynoxyphenyl.

6. The compound of claim 1, wherein R.sup.1 is H, C.sub.1-C.sub.4-alkyl, or (C.sub.1-C.sub.4-alkyl)carbonyl.

7. The compound of claim 6, wherein R.sup.1 is H.

8. The compound of claim 1, wherein R.sup.2 is H, C.sub.1-C.sub.4-alkyl, or (C.sub.1-C.sub.4-alkyl)carbonyl.

9. The compound of claim 8, wherein R.sup.2 is H.

10. The compound of claim 1, wherein R.sup.4 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.6-haloalkoxy.

11. The compound of claim 1, wherein R.sup.5 is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, and C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl.

12. The compound of claim 1, wherein R.sup.4 and R.sup.5 together with the carbon atom to which they are attached form a moiety selected from the group consisting of C.sub.3-C.sub.6-cycloalkan-1,1-diyl, ipso-C.sub.3-C.sub.6-cycloalkendiyl and three- to six-membered saturated or partially unsaturated ipso-heterocyclodiyl.

13. The compound of claim 1, wherein the combination of R.sup.3, R.sup.4, and R.sup.5 are as given in the following table, where a merged column for R.sup.4 and R.sup.5 indicates that R.sup.4 and R.sup.5 together with the carbon atom to which they are attached correspond to the specified group: TABLE-US-00010 # R.sup.3 R.sup.4 R.sup.5 3 F H CH.sub.3 4 F CH.sub.3 CH.sub.3 6 F H C.sub.2H.sub.5 8 F CH.sub.3 C.sub.2H.sub.5 11 F C.sub.2H.sub.5 C.sub.2H.sub.5 18 F CH.sub.3 CH(CH.sub.3).sub.2 24 F CH.sub.3 CH.sub.2CH.sub.2CH.sub.3 30 F CH.sub.3 C(CH.sub.3).sub.3 36 F CH.sub.3 Cyclopropyl 37 H CH.sub.3 CF.sub.3 42 F CH.sub.2CH.sub.2 43 Cl CH.sub.2CH.sub.2 47 F CH.sub.2CH.sub.2CH.sub.2 48 Cl CH.sub.2CH.sub.2CH.sub.2 52 F CH.sub.2CH.sub.2CH.sub.2CH.sub.2 53 Cl CH.sub.2CH.sub.2CH.sub.2CH.sub.2 57 F CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2 58 Cl CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2.

14. An agrochemical composition comprising a herbicidal active amount of at least one compound as claimed in claim 1 and at least one inert liquid and/or solid carrier and, if appropriate, at least one surface-active substances.

15. A method of controlling undesired vegetation, which comprises allowing a herbicidally active amount of at least one compound as claimed in claim 1 to act on plants, their environment or on seed.

16. A method for the desiccation and/or defoliation of plants comprising allowing a composition comprising a compound of claim 1 to act on plants, their environment or on seed.

Description

A PREPARATION EXAMPLES

Example 1

N2-[2-(Cyclopentoxy)-6-Fluoro-Phenyl]-6-(1-Fluoro-1-Methyl-Ethyl)-1,3,5-Triazine-2,4-Diamine

(1) ##STR00022##

Step 1:1-(Cyclopentoxy)-3-Fluoro-2-Nitro-Benzene

(2) A suspension of cyclopentanol (1.62 g, 18.8 mmol), 1,3-difluoro-2-nitro-benzene (1.5 g, 9.42 mmol) and Cs.sub.2CO.sub.3 (6.14 g, 18.8 mmol) in DMF (30 mL) was heated at 100 C. over night. The resulting mixture was diluted with water and EtOAc and afterwards the phases were separated. The water phase was further extracted with EtOAc (2) and the organic phases were combined, dried over anhydrous Na.sub.2SO.sub.4 and the solvent was removed. Purification by column chromatography (gradient: 100% CH to 4:1 CH: EtOAc) afforded the desired compound (900 mg, 4 mmol, 42%).

(3) .sup.1H NMR (CDCl.sub.3, 400 MHz): =7.32 (m, 1H), 6.79 (d, 1H, J=8.7 Hz), 6.74 (dt, 1H, J=8.7, 0.9 Hz), 4.85 (q, 1H, J=4.0 Hz), 1.85 (m, 4H), 1.75 (m, 2H), 1.59 (m, 2H).

Step 2: 2-(Cyclopentoxy)-6-Fluoro-Aniline

(4) Powdered Pd/C (10%, 300 mg) was added to a solution of 1-(cyclopentoxy)-3-fluoro-2-nitro-benzene (900 mg, 4 mmol) in methanol (100 mL) and the resulting mixture was stirred under H.sub.2 pressure for 2 h at ambient temperature. The mixture was filtered through Celite while being rinsed with methanol. The combined solutions were evaporated to give the crude title compound (730 mg, 3.74 mmol, 94%), which was used in the next step without further purification.

(5) .sup.1H NMR (CDCl.sub.3, 400 MHz): =6.61 (m, 3H), 4.78 (m, 1H), 3.69 (brs, 2H, NH.sub.2), 1.89 (m, 4H), 1.80 (m, 2H), 1.63 (m, 2H).

Step 3:1-Carbamimidoyl-3-[2-(Cyclopentoxy)-6-Fluoro-Phenyl]Guanidine

(6) Aq. HCl (38% w/w, 1 mL) was added, with stirring, to a solution of 2-(cyclopentoxy)-6-fluoro-aniline (0.73 g, 3.74 mmol) and 2-cyanoguanidine (0.38 g, 4.5 mmol) in acetonitrile (50 mL). The mixture was heated under microwave radiation (140 C., 15 bar) for 45 min. After cooling to ambient temperature aq. NaOH (2 mol/L) was added until a pH of 12 was reached. Ethyl acetate was added to the mixture and the phases were separated. The organic phase was dried over anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure. The resulting crude product (0.88 g, 3.16 mol, 84%) was used without further purification in the next step.

(7) MS (ESI) m/z=279.4 [M+H.sup.+].

Step 4: N2-[2-(Cyclopentoxy)-6-Fluoro-Phenyl]-6-(1-Fluoro-1-Methyl-Ethyl)-1,3,5-Triazine-2,4-Diamine

(8) 2-Fluoro-2-methyl-propanoyl chloride (0.39 g, 3.13 mmol) was slowly added, with stirring, to a solution of 1-carbamimidoyl-3-[2-(cyclopentoxy)-6-fluoro-phenyl]guanidine (0.88 g, 3.15 mmol) and triethylamine (1.3 mL, 9.45 mmol) in THF (30 mL). The resulting mixture was heated at 60 C. for 6 hours. The reaction mixture was cooled to ambient temperature, diluted with water and ethyl acetate, and the phases were separated. After washing the aqueous phase with EtOAc the combined organic phases were washed with brine, dried over anhydreous Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. Column chromatography of the resulting crude product (gradient: 100% CH to 1:1 CH: EtOAc) afforded the desired product (120 mg, 0.34 mmol, 11%).

(9) .sup.1H NMR (CDCl.sub.3, 400 MHz): =7.13 (m, 1H), 6.72 (m, 2H), 6.60 (brs, 1H, NH), 5.42 (brs, 2H, NH.sub.2), 4.76 (sept, 1H, J=3.0 Hz), 1.84 (m, 4H), 1.69 (m, 2H), 1.67 (s, 3H), 1.62 (s, 3H), 1.58 (m, 2H).

(10) The HPLC-MS data for the compound prepared according to Example 1 are given in the following table C. Also included in table C are the data for compounds of Examples 2 and 3 which have been prepared by analogy to the procedures described above for Example 1 and are depicted as formula (I) below.

(11) ##STR00023##

(12) TABLE-US-00008 TABLE C RT MS .sup.1) No. R.sup.a R.sup.3 R.sup.4 R.sup.5 [min] [m/z] 1 cyclopentyloxy F CH.sub.3 CH.sub.3 0.980 349.9 2 (cyclopropyl)methyloxy F CH.sub.3 CH.sub.3 0.927 335.8 3 cyclohexyloxy F CH.sub.3 CH.sub.3 1.032 363.8 .sup.1) Mass Spectrum M.sup.+ or [M + H].sup.+ [m/z]

B USE EXAMPLES

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

(14) 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.

(15) 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.

(16) For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 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.

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

(18) 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.

(19) 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.

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

(21) TABLE-US-00009 Bayer code Scientific name ABUTH Abutilon theophrasti AMARE Amaranthus retroflexus APESV Apera spica-venti

(22) Example 1 applied by pre-emergence method at an application rate of 0.250 kg/ha, showed very good herbicidal activity against AMARE and good herbicidal activity against APESV.

(23) Example 2 applied by pre-emergence method at an application rate of 0.250 kg/ha, showed very good herbicidal activity against ABUTH, AMARE and APESV.