DIAMINOTRIAZINE COMPOUNDS

Abstract

The present invention relates to diaminotriazine compounds and to their use as herbicides. It also relates to agrochemical compositions for crop protection and to a method for controlling unwanted vegetation.

##STR00001##

Claims

1. A diaminotriazine compound of formula (I) ##STR00080## wherein q is 0, 1, 2 or 3 Q is a O, S(O).sub.m, CR.sup.q1R.sup.q2 NR.sup.q3, C(O), S(O).sub.mNR.sup.q3 or, wherein m is 0, 1 or 2; R.sup.q1, R.sup.q2 are hydrogen, halogen, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-halogenalkyl; R.sup.q3 is H, CN, C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, where the aliphatic parts of the radicals are unsubstituted, partly or completely halogenated; R.sup.a is selected from the group consisting of hydrogen, 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, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, C.sub.1-C.sub.6-alkylthio, (C.sub.1-C.sub.6-alkyl)sulfinyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6 alkyl)amino, di(C.sub.1-C.sub.6-alkyl)amino, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)-carbonyl, (C.sub.1-C.sub.6-alkyl)-carbonyloxy, where the aliphatic and cycloaliphatic parts of the radicals are unsubstituted, partly or completely halogenated; 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, 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.2-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkylthio, (C.sub.1-C.sub.6-aklyl)sulfinyl, (C.sub.1-C.sub.6 alkyl)sulfonyl, (C.sub.1-C.sub.6-alkyl)amino, di(C.sub.1-C.sub.6-alkyl)amino, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)-carbonyl, (C.sub.1-C.sub.6-alkyl)-carbonyloxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkoxy, where the aliphatic and cycloaliphatic parts of the radicals are unsubstituted, partly or completely halogenated and where the cycloaliphatic parts of the last 4 mentioned radicals may carry 1, 2, 3, 4, 5 or 6 methyl groups, for q=2 or 3 it being possible that R.sup.b are identical or different; 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.1-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.3-C.sub.6-cycloalkyl)-carbonyl, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl and (C.sub.1-C.sub.6-alkoxy)sulfonyl, where the aliphatic and cycloaliphatic parts of the radicals are unsubstituted, partly or completely halogenated, phenyl, phenyl-C.sub.1-C.sub.6-alkyl, phenylsulfonyl, phenylaminosulfonyl, phenylaminocarbonyl, phenyl(C.sub.1-C.sub.6-alkyl)aminocarbonyl, phenylcarbonyl and phenoxycarbonyl, wherein phenyl in the last 8 mentioned radicals are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; R.sup.2 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, (C.sub.1-C.sub.6-cycloalkyl)-C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, C.sub.3-C.sub.6-cycloalkoxy, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkoxy, where the aliphatic and cycloaliphatic parts of the radicals are unsubstituted, partly or completely halogenated; R.sup.3 is selected from the group consisting of H, halogen, CN, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; R.sup.4 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, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkenyl and C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, where the aliphatic and cycloaliphatic parts of the radicals are unsubstituted, partly or completely halogenated; R.sup.3 and R.sup.4 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-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, three- to six-membered saturated or partially unsaturated heterocyclyl, and the moiety >C═CR.sup.xR.sup.y, where R.sup.x and R.sup.y are hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl or CR.sup.xR.sup.y form a 3 to 6 membered cycloalkyl; R.sup.5 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.1-C.sub.6-alkynyl, (C.sub.1-C.sub.6-cycloalkyl)-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl)-carbonyl C.sub.2-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)carbonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl and (C.sub.1-C.sub.6-alkoxy)sulfonyl, where the aliphatic and cycloaliphatic parts of the radicals are unsubstituted, partly or completely halogenated, phenyl, phenylsulfonyl, phenylaminosulfonyl, phenylaminocarbonyl, phenyl(C.sub.1-C.sub.6-alkyl)aminocarbonyl, phenyl-C.sub.1-C.sub.6 alkyl, phenoxy, phenylcarbonyl and phenoxycarbonyl, wherein phenyl in the last 9 mentioned radicals is unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.2-C.sub.6-haloalkoxy; R.sup.6 is phenyl or a 5- to 6-membered heteroaryl, which is unsubstituted or carries 1, 2, 3, 4 or 5 radicals R.sup.6A which are 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, 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.2-C.sub.6-alkenyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkylthio, (C.sub.1-C.sub.6-alkyl)sulfinyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkyl)amino, di(C.sub.1-C.sub.6-alkyl)amino, (C.sub.1-C.sub.6-alkyl)-carbonyl, (C.sub.2-C.sub.6-alkoxy)-carbonyl, (C.sub.1-C.sub.6-alkyl)-carbonyloxy, C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkyl, (C.sub.3-C.sub.6-cycloalkyl)-C.sub.1-C.sub.4-alkoxy, where the aliphatic and cycloaliphatic parts of the radicals are unsubstituted, partly or completely halogenated and where the cycloaliphatic parts of the radicals may carry 1, 2, 3, 4, 5 or 6 methyl groups, it being possible that R.sup.6A are identical or different; R.sup.7 and R.sup.7′ are independently selected from the group consisting of hydrogen, halogen, OH, CN, NO.sub.2, SH, NH.sub.2, NH(C.sub.1-C.sub.6-alkyl), N(C.sub.1-C.sub.4-alkyl).sub.2, NH—SO.sub.2—C.sub.1-C.sub.4-alkyl, 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, C.sub.1-C.sub.6-halogenalkoxy, C.sub.3-C.sub.6-cycloalkyl; and wherein the aliphatic moieties of R.sup.7 and R.sup.7′ are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R.sup.7a or R.sup.7′a which independently of one another are selected from: R.sup.7a, R.sup.7′a halogen, OH, CN, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halogencycloalkyl, C.sub.1-C.sub.4-halogenalkoxy and C.sub.1-C.sub.6-alkylthio wherein the cycloalkyl moieties of R.sup.7 and R.sup.7 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R.sup.7b or R.sup.7′b which independently of one another are selected from: R.sup.7, R.sup.7′b halogen, OH, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-halogenalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halogencycloalkyl, C.sub.1-C.sub.4-halogenalkoxy and C.sub.1-C.sub.6-alkylthio; including their agriculturally acceptable salts or derivatives.

2. The compound of claim 1, wherein Q is selected from the group consisting of a O, CH.sub.2, S, S(O) and S(O).sub.2.

3. The compound of claim 1, wherein R.sup.a is selected from the group consisting of halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy and C.sub.1-C.sub.4-haloalkoxy.

4. The compound of claim 1, wherein R.sup.b is selected from the group consisting of halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy and C.sub.1-C.sub.4-haloalkoxy.

5. The compound of claim 1, wherein R.sup.1 is selected from the group consisting of H, CN, C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)carbonyl, (C.sub.3-C.sub.6-cycloalkyl)-carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, C.sub.1-C.sub.6-alkoxy, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl, where the aliphatic parts of the radicals are unsubstituted, partly or completely halogenated, phenyl, phenylcarbonyl and phenyl-C.sub.1-C.sub.6 alkyl, wherein phenyl in the last 3 mentioned radical is unsubstituted or substituted by 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy.

6. The compound of claim 1, wherein R.sup.2 is selected from the group consisting of hydrogen, fluorine, CrCr-alkyl and C.sub.2-C.sub.6-alkoxy; R.sup.3 is selected from the group consisting of hydrogen, fluorine, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; R.sup.4 is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, 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; or R.sup.3 and R.sup.4 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-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl and three- to six-membered saturated or partially unsaturated heterocyclyl.

7. The compound of claim 1, wherein R.sup.5 is selected from the group consisting of H, CN, C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkoxy)-C.sub.1-C.sub.6-alkyl, (C.sub.1-C.sub.6-alkyl)carbonyl, (C.sub.1-C.sub.6-alkyl)sulfonyl, (C.sub.1-C.sub.6-alkoxy)carbonyl, (C.sub.1-C.sub.6-cycloalkyl)-carbonyl, (C.sub.1-C.sub.6-alkylamino)carbonyl, di(C.sub.1-C.sub.6-alkyl)aminocarbonyl, (C.sub.1-C.sub.6-alkylamino)sulfonyl, di(C.sub.1-C.sub.6-alkyl)aminosulfonyl, where the aliphatic parts of the radicals are unsubstituted, partly or completely halogenated, phenyl, phenylcarbonyl and C.sub.1-C.sub.6 alkylphenyl, wherein phenyl in the mentioned radicals is unsubstituted or substituted by 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-alkoxy.

8. The compound of claim 1, wherein R.sup.6 is phenyl, which is unsubstituted or carries 1 or 5 radicals RM.

9. The compound of claim 1, wherein R.sup.6 is 5- to 6-membered heteroaryl, which is unsubstituted or carries 1 or 5 radicals R.sup.6A.

10. The compound of claim 1, wherein R.sup.6A, if present, is selected from the group consisting of halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy and C.sub.3-C.sub.6-cycloalkyl.

11. The compound of claim 1, wherein R.sup.7 is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-halogenalkoxy, C.sub.3-C.sub.6-cycloalkyl.

12. The compound of claim 1, wherein R.sup.7′ is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-halogenalkoxy, C.sub.3-C.sub.6-cycloalkyl.

13. 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, optionally, at least one surface-active substance.

14. A method of controlling unwanted vegetation comprising use a compound as claimed in claim 1 as a herbicide or for desiccation/defoliation of plants.

15. The compound of claim 3 wherein R.sup.a is fluorine or chlorine.

16. The compound of claim 4 wherein R.sup.b is fluorine, chlorine, bromine, or methyl.

Description

A PREPARATION EXAMPLES

Example 1: N4-(2-benzyloxy-6-fluoro-phenyl)-6-(1-methoxy-1-methyl-ethyl)-1,3,5-triazine-2,4-diamine

Step 1: 1-Benzyloxy-3-fluoro-2-nitro-benzene

[0511] ##STR00072##

[0512] K.sub.2CO.sub.3 (25.3 g, 183 mmol, 1.2 eq) was added to a solution of 3-fluoro-2-nitro-phenol (24.0 g, 153 mmol, 1.0 eq) in 100 ml DMF. Benzylbromide (26.1 g, 153 mmol, 1.0 eq) was added to the suspension at ambient temperature. The mixture was stirred for 18 h overnight. Water is added to the reaction mixture to dissolve any salts. The solution was extracted three times with 100 ml EtOAc. The combined organic layers were washed with water, dried with Na.sub.2SO.sub.4 and then evaporated. The solid residue was used without further purification in the following step.

[0513] LC/MS RT: 1.204. LC/MS (m/z): no ionization of the molecule observed .sup.1H-NMR (400 MHz, CDCl.sub.3) δ 5.2 (s, 2H), 6.8-6.9 (m, 2H), 7.3-7.4 (m, 6H)

Step 2: 2-Benzyloxy-6-fluoro-aniline

[0514] ##STR00073##

[0515] Zinc powder (52.9 g, 809 mmol, 4.0 eq) was suspended in 400 ml acetic acid. 1-Benzyloxy-3-fluoro-2-nitro-benzene (50 g, 202 mmol, 1.0 eq) dissolved in 80 ml EtOAc was slowly added so that the temperature of the reaction mixture does not exceed 40° C. The mixture was stirred over the weekend at ambient temperature and then diluted with 300 ml EtOAc. After filtration, water was added. The organic layer was washed with a saturated NaHCO.sub.3 solution and then evaporated. The crude material was purified over column chromatography (silica, cyclohexane/EtOAc) to obtain the desired product (29.7 g, 67% yield) as a light-yellow oil.

[0516] LC/MS RT: 1.051. LC/MS (m/z): 217.9 [M+H.sup.+]

[0517] .sup.1H-NMR (400 MHz, CDCl.sub.3) δ 3.2-4.1 (br, 2H), 5.08 (s, 2H), 6.55-6.75 (m, 3H), 7.3-7.5 (m, 5H)

Step 3: 4-(1-methoxy-1-methyl-ethyl)-6-methylsulfanyl-1,3,5-triazin-2-amine

[0518] ##STR00074##

[0519] 2-Methoxy-2-methyl-propanoic acid (5.4 g, 45.7 mmol, 1.01 eq) was dissolved in 10 ml CH.sub.2C.sub.2. After adding 3 drops of DMF, oxalyl dichloride 5.8 g, 45.7 mmol, 1.01 eq) was added at ambient temperature. After 1 h, when gas evolution is no longer observed, the solution is added slowly to a solution of 1-carbamimidoyl-2-methyl-isothiourea hydroiodide (11.8 g, 45.4 mmol, 1.0 eq) and triethylamine (13.78 g, 136 mmol, 3.0 eq) in 70 ml dioxane. After stirring at 60° C. for 4 h water and EtOAc were added. The organic phase was separated, dried over Na.sub.2SO.sub.4 and evaporated to give 9.4 g of crude product, which was used without further purification in the next step.

[0520] LC/MS RT: 0.742. LC/MS (m/z): 215.1 [M+H.sup.+]

[0521] .sup.1H-NMR (400 MHz, DMSO-d6) δ1.41 (d, 6H), 2.44 (s, 3H), 3.05 (s, 3H), 7.53 (d, 2H)

Step 4: 4-chloro-6-(1-methoxy-1-methyl-ethyl)-1,3,5-triazin-2-amine

[0522] ##STR00075##

[0523] To a solution of 4-(1-methoxy-1-methyl-ethyl)-6-methylsulfanyl-1,3,5-triazin-2-amine (9.4 g, 43.9 mmol, 1.0 eq) in 100 ml EtOAc/CHCl.sub.3, chlorine gas was introduced for 30 min at ambient temperature. Due to incomplete conversion of the starting material, chlorine gas was introduced for additional 30 minutes. After this period the solution was purged with N.sub.2 gas and concentrated. The solid residue is treated with water and the precipitated solid was filtered and dried to give 5.7 g of the crude product that was used in the next step.

[0524] LC/MS RT: 0.736. LC/MS (m/z): 203.0 [M+H.sup.+] 1.40 (s, 6H), 3.07 (s, 3H), 8.12, (d, 2H)

[0525] .sup.1H-NMR (400 MHz, DMSO-d6) δ

Step 5: N4-(2-benzyloxy-6-fluoro-phenyl)-6-(1-methoxy-1-methyl-ethyl)-1,3,5-triazine-2,4-diamine

[0526] ##STR00076##

[0527] 2-Benzyloxy-6-fluoro-aniline (400 mg, 1.8 mmol, 1.0 eq) and 4-chloro-6-(1-methoxy-1-methyl-ethyl)-1,3,5-triazin-2-amine (373 mg, 1.8 mmol, 1.0 eq) were suspended in 5 ml dioxane. Hydrogen chloride in dioxane (4.1 ml, 4.0 molar solution, 3.0 eq) was added and the mixture was heated to 90° C. for 2 h and then cooled to ambient temperature. After adding water and EtOAc the organic phase was separated, dried over Na.sub.2SO.sub.4 and evaporated to give the crude product, which was purified over column chromatography (silica, cyclohexane/EtOAc) to obtain the desired product (163 mg, 23% yield).

[0528] LC/MS RT: 0.921. LC/MS (m/z): 384.0 [M+H.sup.+]

[0529] .sup.1H-NMR (400 MHz, DMSO-d6) δ 2.5 (s, 6H), 3.3 (s, 3H), 5.1 (s, 2H), 6.75-6.9 (m, 3H), 6.93 (d, 1H), 7.15-7.35 (m, 6H)

Example 2: N4-(2-benzyloxy-6-fluoro-phenyl)-6-(1-fluoro-2-methyl-propyl)-1,3,5-triazine-2,4-diamine

Step 1: 1-(2-Benzyloxy-6-fluoro-phenyl)-3-carbamimidoyl-guanidine hydrochloride

[0530] ##STR00077##

2-Benzyloxy-6-fluoro-aniline (20 g, 92 mmol, 1.0 eq) and 1-cyanoguanidine (9.3 g, 110.5 mmol, 1.2 eq) were mixed in 150 ml acetonitrile. Hydrochloric acid (10.7 g, 37.5 wt-%, 1.2 eq) was added and the mixture was heated to 75° C. for 6 h. After cooling to ambient temperature, the precipitated solid was filtered and washed with acetonitrile and pentane. The solid was dried under vacuum to obtain 23.7 g of the HCl salt. The free base can be obtained by treatment with a sodium hydroxide solution and EtOAc extraction of the aqueous mixture.

[0531] LC/MS RT: 0.761. LC/MS (m/z): 301.9 [M+H.sup.+]

Step 2: N4-(2-benzyloxy-6-fluoro-phenyl)-6-(1-fluoro-2-methyl-propyl)-1,3,5-triazine-2,4-diamine

[0532] ##STR00078##

[0533] 2-Fluoro-3-methyl-butanoic acid (1.1 g, 9.31 mmol, 1.0 eq) was dissolved in 30 ml CH.sub.2Cl.sub.2. At −78° C. DAST (3.0 g, 18.6 mmol, 2.0 eq) was slowly added. After self-heating to ambient temperature overnight the mixture was added to a solution of 1-(2-benzyloxy-6-fluoro-phenyl)-3-carbamimidoyl-guanidine and triethylamine in 60 ml dioxane. The reaction mixture was stirred at 50° C. for 3 h. After cooling to ambient temperature, the mixture is poured onto water and extracted with additional CH.sub.2Cl.sub.2. After solvent evaporation, the crude product was purified over column chromatography (silica, cyclohexane/EtOAc) to obtain the desired product (45 mg, 1.3% yield) as a white solid.

[0534] LC/MS RT: 1.061. LC/MS (m/z): 385.9 [M+H.sup.+]

[0535] .sup.1H-NMR (500 MHz, DMSO-d6) 0.85 (b, 6H), 2.1-2.3 (b, 1H), 4.6-4.85 (d, 1H), 5.1 (s, 2H), 6.8-7.4 (m, 10H), 8.75 (b, 1H)

[0536] The compounds listed below in table 3 (examples 3 to 263) have been prepared similarly to the examples mentioned above:

##STR00079##

TABLE-US-00007 TABLE 3 ex.no. R.sup.2R.sup.3R.sup.4 R.sup.a R.sup.b1 R.sup.b2 R.sup.b3 R.sup.6R.sup.7R.sup.7′ MS HPLC 3. CFMe.sub.2 F H H H (3,5-dimethylphenyl)methyl 1.131 399.9 4. CFMe.sub.2 F H H H benzyl 0.997 372.2 5. 1-fluorocyclopentyl F H H H benzyl 1.051 398.1 6. CFMe.sub.2 F H H H (4-fluorophenyl)methyl 1.000 390.1 7. CFMe.sub.2 F H H H (4-nitrophenyl)methyl 0.979 417.1 8. CFMe.sub.2 F H H H [4-(trifluoromethyl)phenyl]methyl 1.082 440.1 9. CFMe.sub.2 F H H H p-tolylmethyl 1.04 386.1 10. CFMe.sub.2 F H H H (3-methoxyphenyl)methyl 0.993 402.1 11. CFMe.sub.2 F H H H (3-fluorophenyl)methyl 0.999 390.1 12. 1-fluorocyclopentyl F H H H (4-fluorophenyl)methyl 1.035 416.1 13. 1-fluorocyclopentyl F H H H (4-nitrophenyl)methyl 1.022 443.0 14. 1-fluorocyclopentyl F H H H (3-methoxyphenyl)methyl 1.074 412.1 15. 1-fluorocyclopentyl F H H H p-tolylmethyl 1.028 428.1 16. 1-fluorocyclopentyl F H H H (4-methoxyphenyl)methyl 1.025 428.1 17. 1-fluorocyclopentyl F H H H [4-(trifluoromethyl)phenyl]methyl 1.114 466.1 18. 1-fluorocyclopentyl F H H H (3-fluorophenyl)methyl 1.035 416.1 19. 1-fluorocyclopentyl F H H H (2-fluorophenyl)methyl 1.034 416.1 20. CFMe.sub.2 F H H H (4-methoxyphenyl)methyl 0.989 402.1 21. CFMe.sub.2 F H H H 3-pyridylmethyl 0.707 373.1 22. CFMe.sub.2 F H H H 3-thienylmethyl 0.961 378.1 23. CFMe.sub.2 F H H H 1-phenylethyl 1.023 386.2 24. CFMe.sub.2 F H H H [3-(trifluoromethyl)phenyl]methyl 1.061 440.1 25. CFMe.sub.2 F H H H (3-nitrophenyl)methyl 0.981 417.1 26. CFMe.sub.2 F H H H m-tolylmethyl 1.052 386.1 27. CFMe.sub.2 F H H H (2-fluorophenyl)methyl 1.007 390.0 28. CFMe.sub.2 F H H H (2-nitrophenyl)methyl 0.994 417.1 29. CFMe.sub.2 F H H H [2-(trifluoromethyl)phenyl]methyl 1.093 440.0 30. CFMe.sub.2 F H H H o-tolylmethyl 1.038 386.1 31. 1-fluorocyclohexyl F H H H benzyl 1.092 412.1 32. 1-methylcyclohexyl F H H H benzyl 1.064 408.1 33. t-Bu F H H H benzyl 0.976 368.0 34. 1-hydroxypropyl F H H H benzyl 0.882 370.0 35. 1-fluoropropyl F H H H benzyl 1.013 372.0 36. CFMe.sub.2 F H H H thiazol-2-ylmethyl 0.862 379.0 37. CFMe.sub.2 F H H H (2-methylthiazol-5-yl)methyl 0.823 393.0 38. CFMe.sub.2 F H H H (5-methoxycarbonyl-2-furyl)methyl 0.912 420.0 39. CFMe.sub.2 F H H H (2-chlorothiazol-5-yl)methyl 1.035 412.0 40. CFMe.sub.2 F H H H (3-methylisoxazol-5-yl)methyl 0.871 377.0 41. CFMe.sub.2 F H H H 1,3,4-oxadiazol-2-ylmethyl 0.76 364 42. CFMe.sub.2 F H H H (3-cyclopropyl-1,2,4-oxadiazol-5-yl)methyl 0.926 404 43. CFMe.sub.2 F H H H (3,5-difluorophenyl)methyl 1.048 408 44. CFMe.sub.2 F H H H (3-bromophenyl)methyl 1.081 449.9 45. CFMe.sub.2 F H H H (3,4-difluorophenyl)methyl 1.008 408 46. CFMe.sub.2 F H H H (3-iodophenyl)methyl 1.058 497.9 47. CFMe.sub.2 F H H H (3-chlorophenyl)methyl 1.029 406 48. CFMe.sub.2 F H H H (3-chloro-4-methoxy-phenyl)methyl 1.056 435.9 49. CFMe.sub.2 F H H H (3-chloro-5-fluoro-phenyl)methyl 1.095 424 50. CFMe.sub.2 F H H H (4-methoxycarbonyloxazol-2-yl)methyl 0.847 421.1 51. CFMe.sub.2 F H H H (5-methyl-1,3,4-oxadiazol-2-yl)methyl 0.784 378 52. 1-methylcyclobutyl F H H H benzyl 1.008 380.1 53. CFMe.sub.2 F H H H (3-chloro-5-methoxy-phenyl)methyl 1.082 435.9 54. CFMe.sub.2 F H H H (3-fluoro-5-methoxy-phenyl)methyl 1.039 420.0 55. CFMe.sub.2 F H H H (3-chloro-4-fluoro-phenyl)methyl 1.070 424.0 56. CFMe.sub.2 F H H H (3-fluoro-4-methyl-phenyl)methyl 1.070 404.0 57. CFMe.sub.2 F H H H (3,5-dichlorophenyl)methyl 1.090 440.0 58. CFMe.sub.2 F H H H [3-(difluoromethoxy)phenyl]methyl 1.016 438.1 59. CFMe.sub.2 F H H H (3-methylsulfonylphenyl)methyl 0.888 449.9 60. CFMe.sub.2 F H F H benzyl 1.008 390.0 61. CFMe.sub.2 F Br H H benzyl 1.008 380.1 62. CFMe.sub.2 F H H H (3-fluoro-4-methoxy-phenyl)methyl 1.001 420.0 63. CFMe.sub.2 F H H H [3-(difluoromethoxy)-5-fluoro-phenyl]methyl 1.061 456.1 64. CFMe.sub.2 F H H H thiazol-5-ylmethyl 0.816 378.9 65. 1-fluoro-2-methyl-propyl F H H H benzyl 1.061 385.9 66. CFMe.sub.2 F H H H (3-methyl-1,2,4-oxadiazol-5-yl)methyl 0.842 378.0 67. 1-fluorocyclopent-3-en-1-yl F H H H benzyl 1.037 396.0 68. CFMe.sub.2 F H H H (3-chloro-4-methylsulfanyl-phenyl)methyl 1.100 452.0 69. CFMe.sub.2 F F F H benzyl 1.096 408.0 70. CFMe.sub.2 F H H H oxazol-2-ylmethyl 0.819 363 71. CFMe.sub.2 F H H H (4-methoxycarbonylthiazol-2-yl)methyl 0.877 437.0 72. CFMe.sub.2 F H H F benzyl 1.041 390.0 73. CFMe.sub.2 F H H H (3,5-difluoro-4-methoxy-phenyl)methyl 1.046 438.1 74. CFMe.sub.2 F H H H (2,3,5-trifluorophenyl)methyl 1.042 426.0 75. CFMe.sub.2 F H H H (3,5-dimethoxyphenyl)methyl 1.012 432.0 76. 1-(fluoromethyl)cyclopropyl F H H H benzyl 0.961 383.9 77. 1-fluorobutyl F H H H benzyl 1.091 386.0 78. CFMe.sub.2 F H H H (2,6-dichlorophenyl)methyl 1.067 440.0 79. CFMe.sub.2 F H H H (3-chloro-4-ethoxy-phenyl)methyl 1.103 450.1 80. CFMe.sub.2 F H H H (3-isopropylphenyl)methyl 1.152 414.1 81. CFMe.sub.2 Br H H H benzyl 1.01 433.9 82. CFMe.sub.2 H H H H benzyl 1.060 354.0 83. CFMe.sub.2 F H H H difluoro(phenyl)methyl 1.098 408.4 84. CFMe.sub.2 F H H H (3-cyanophenyl)methyl 0.961 397.0 85. CFMe.sub.2 Cl H H H benzyl 1.035 388.4 86. CFMe.sub.2 F H H H (4-vinylphenyl)methyl 1.084 398.4 87. CFMe.sub.2 F H H H [4-(methylcarbamoyl)phenyl]methyl 0.84 429.0 88. CFMe.sub.2 F H H H (4-methoxycarbonylphenyl)methyl 0.986 430.1 89. CFMe.sub.2 F H H H (3-methoxycarbonylphenyl)methyl 0.984 430.1 90. CFMe.sub.2 F H H H 2-pyridylmethyl 0.739 373.0 91. CMe2OMe F H H H benzyl 0.943 384.1 92. CFMe.sub.2 F H H H 4-pyridylmethyl 0.675 372.9 93. CFMe.sub.2 F H H H (3-carboxyphenyl)methyl 0.880 416.0 94. CFMe.sub.2 F H H H (4-ethylphenyl)methyl 1.114 400 95. CFMe.sub.2 F H H H (3,4-dimethylphenyl)methyl 1.087 400.0 96. CF.sub.2Me F H H H benzyl 1.088 376.0 97. CFMe.sub.2 F F F H (3-fluorophenyl)methyl 1.067 425.9 98. CFMe.sub.2 F F F H (3-methoxyphenyl)methyl 1.063 438.0 99. CFMe.sub.2 F H H H (2,6-difluorophenyl)methyl 1.067 425.9 100. CFMe.sub.2 F H H H (2-methoxyphenyl)methyl 0.999 402.0 101. CFMe.sub.2 F H H H [4-(difluoromethyl)phenyl]-difluoro-methyl 1.087 457.9 102. CFMe.sub.2 F H H H (3-fluoro-2-methyl-phenyl)methyl 1.023 403.9 103. CFMe.sub.2 F H H H (4-carboxyphenyl)methyl 0.886 416.0 104. CFMe.sub.2 F H H H (4-chlorophenyl)-difluoro-methyl 1.15 442.0 105. CFMe.sub.2 F H H H (5-methoxycarbonyl-3-thienyl)methyl 0.977 436.0 106. CFMe.sub.2 F H H H (5-methyl-3-thienyl)methyl 1.033 392.0 107. CFMe.sub.2 F H H H (2-chloro-3-thienyl)methyl 1.047 412.0 108. CFMe.sub.2 F F H H benzyl 1.056 390.0 109. CFMe.sub.2 F H H H (3-fluoro-2-methoxycarbonyl-phenyl)methyl 1.027 448.0 110. CFMe.sub.2 F H H H (5-chloro-3-thienyl)methyl 1.073 411.9 111. CFMe.sub.2 F H H H (4-methyl-3-thienyl)methyl 1.045 391.9 112. CFMe.sub.2 F H H H (2,5-dichloro-3-thienyl)methyl 1.158 445.9 113. CFMe.sub.2 F H H H benzyl 1.063 388.0 114. CMe.sub.2OMe F H H H (3-fluorophenyl)methyl 0.926 401.9 115. CMe.sub.2OMe F H H H (3-methoxyphenyl)methyl 0.924 414.0 116. CFMe.sub.2 F F F H difluoro(phenyl)methyl 1.171 444.0 117. CMe.sub.2OMe F H H H difluoro(phenyl)methyl 0.971 420.1 118. CFMe.sub.2 F H H H benzyl 0.969 420 119. CFMe.sub.2 F H H H (5-acetyl-3-thienyl)methyl 0.898 420.0 120. CFMe.sub.2 F H H H (5-chloro-2-thienyl)methyl 1.046 411.9 121. CFMe.sub.2 F H H H (2-cyano-3-thienyl)methyl 0.942 402.9 122. CFMe.sub.2 F H H H (2-cyano-3-fluoro-phenyl)methyl 0.977 414.9 123. CFMe.sub.2 F H H H benzyl 0.909 403.9 124. CFMe.sub.2 F H H H (5-cyano-3-thienyl)methyl 0.939 402.9 125. CFMe.sub.2 F H H H (2,5-dimethyl-3-thienyl)methyl 1.068 405.9 126. CFMe.sub.2 F H H H (4-cyano-3-thienyl)methyl 0.903 402.9 127. CFMe.sub.2 H F H H benzyl 1.153 371.9 128. CFMe.sub.2 CN H H H benzyl 0.98 379 129. CFMe.sub.2 F F F H difluoro-(3-fluorophenyl)methyl 1.193 461.9 130. CFMe.sub.2 F H H H difluoro-(3-fluorophenyl)methyl 1.098 425.9 131. CMe.sub.2OMe F H H H difluoro-(3-fluorophenyl)methyl 0.998 437.9 132. CFMe.sub.2 F H H H (3-isopropoxyphenyl)methyl 1.101 430.0 133. CFMe.sub.2 F H H H (3-isobutoxyphenyl)methyl 1.182 444.1 134. CFMe.sub.2 F H H H [3-(2,2,2-trifluoroethoxy)phenyl]methyl 1.096 470.0 135. CMe.sub.2OMe F H H F benzyl 0.970 402.0 136. CFMe.sub.2 F H H H [3-(trifluoromethoxy)phenyl]methyl 1.108 456.0 137. CFMe.sub.2 F H H H (4-cyanophenyl)methyl 0.970 397.0 138. CFMe.sub.2 F H H H (4-chlorophenyl)methyl 1.064 405.9 139. CFMe.sub.2 F H H F (3-methoxyphenyl)methyl 1.038 420.0 140. CFMe.sub.2 F H H F (4-ethylphenyl)methyl 1.148 418.0 141. CFMe.sub.2 F H H F p-tolylmethyl 1.053 404.0 142. CFMe.sub.2 F H H F difluoro(phenyl)methyl 1.068 426.0 143. CFMe.sub.2 F H H H (4-isopropylphenyl)methyl 1.147 414.1 144. CFMe.sub.2 F H H F (2-chlorothiazol-5-yl)methyl 0.985 430.8 145. CFMe.sub.2 F H H H [3-(cyclopropylmethoxy)phenyl]methyl 1.109 442.0 146. CFMe.sub.2 F H H H (3-~{tert}-butoxyphenyl)methyl 1.128 488.1 147. CFMe.sub.2 F H H H [3-(2,2-difluoroethoxy)phenyl]methyl 1.047 452.1 148. CFMe.sub.2 F H H Cl benzyl 1.088 405.9 149. CFMe.sub.2 F H H H (3-ethoxyphenyl)methyl 1.056 416.1 150. CFMe.sub.2 F H H H [3-(2-methoxy-2-oxo-ethoxy)phenyl]methyl 1.070 no ionization 151. CFMe.sub.2 F H H H (3-acetoxyphenyl)methyl 0.981 429.9 152. 1-fluoro-2-methyl-prop-1-enyl F H H H benzyl 1.022 383.9 153. CFMe.sub.2 F H H H (1-methyhmidazol-2-yl)methyl 0.659 375.9 154. CFMe.sub.2 F H H H 2-thienylmethyl 0.946 377.9 155. CFMe.sub.2 F F H F benzyl 1.086 408.0 156. CF.sub.2Me F F F H benzyl 1.154 411.9 157. CFMe.sub.2 F H H H [3-(cyclopropoxy)phenyl]methyl 1.059 428.3 158. (~{E})-1- F H H H benzyl 1.179 397.9 fluoro-3-methyl-but-1-enyl 159. 1-fluoro-2-methyl-prop-1-enyl F F F H benzyl 1.098 419.9 160. 1-fluoro-2-methyl-prop-1-enyl F H H F benzyl 1.038 401.9 161. CHFMe F H H H benzyl 0.989 357.9 162. CFMe2 F H H H (4-cyclopropylphenyl)methyl 1.119 412 163. CFMe2 F Br H F benzyl 1.166 469.7 164. CFMe2 F F H F (3-methoxyphenyl)methyl 1.086 437.9 165. CFMe2 F F H F (2,6-difluorophenyl)methyl 1.093 443.9 166. CFMe2 F H H F (4-cyclopropylphenyl)methyl 1.131 430.0 167. CFMe2 F H H F (2,6-difluorophenyl)methyl 1.032 425.9 168. 1-fluorovinyl F H H H benzyl 1.089 356.2 169. 1-fluorobutyl F F F H benzyl 1.179 422.0 170. 1-fluorobutyl F H H F benzyl 1.133 404.0 171. CHFMe F H H H difluoro(phenyl)methyl 1.054 393.9 172. CFMe2 F H H F (2-fluorophenyl)methyl 1.040 408.0 173. CFMe2 F H H F (2-methoxyphenyl)methyl 1.066 420.0 174. CFMe2 F H H F 3-thienylmethyl 1.017 396.0 175. CFMe2 F H H Me benzyl 1.029 385.9 176. CFMe2 F F H H (2-chloro-6-fluoro-phenyl)methyl 1.087 441.8 177. CFMe2 F H H H (2-chloro-6-fluoro-phenyl)methyl 1.036 423.9 178. CFMe2 F F H H (2-methoxyphenyl)methyl 1.124 438.0 179. 1-fluorobutyl F H H H difluoro(phenyl)methyl 1.160 421.9 180. CFMe2 F F H F (4-methoxyphenyl)methyl 1.089 438.1 181. CFMe2 F F H F o-tolylmethyl 1.122 422.0 182. CFMe2 F F H F m-tolylmethyl 1.142 422.0 183. CFMe2 F F H F p-tolylmethyl 1.133 422.1 184. 1-F-cPr F H H H benzyl 1.016 369.9 185. CFMe2 F F H H (3-methoxyphenyl)methyl 1.047 419.9 186. CFMe2 F F H H (4-methoxyphenyl)methyl 1.043 420.0 187. 1-F-cPr F H H F benzyl 1.042 387.9 188. CFMe2 F H F F benzyl 1.083 407.9 189. cyclopropyl(fluoro)methyl F H H F benzyl 1.070 401.9 190. 1-methoxyethyl F H H H benzyl 0.926 369.9 191. 1-methoxyethyl F H H F benzyl 0.940 387.9 192. CFMe2 F H H F (4-methoxyphenyl)methyl 1.039 419.9 193. CFMe2 F H H F (4-ethoxyphenyl)methyl 1.100 433.9 194. i-Pr F H H H benzyl 0.958 354.0 195. 1-chloroethyl F H H H benzyl 1.069 374.0 196. CHFMe F H H F benzyl 1.001 375.9 197. 1-fluoro-2-methyl-prop-1-enyl F H H H difluoro(phenyl)methyl 1.107 419.9 198. CFMe2 F F H H (2-methoxyphenyl)methyl 1.077 419.9 199. 1-fluorocyclopentyl F F H F benzyl 1.141 433.9 200. t-Bu F F H F benzyl 1.074 403.9 201. 1-methylcyclobutyl F F H F benzyl 1.063 416.0 202. cyclopentyl(fluoro)methyl F H H H benzyl 1.144 412.0 203. CFMe2 F F H F (2-fluorophenyl)methyl 1.089 425.9 204. CFMe2 F F H F (3-fluorophenyl)methyl 1.094 426.0 205. CFMe2 F F H F (4-fluorophenyl)methyl 1.096 426.0 206. CFMe2 F F H F (2-chlorophenyl)methyl 1.136 441.8 207. CFMe2 F F H F (4-chlorophenyl)methyl 1.142 441.8 208. CFMe2 F F H F (2-isopropylphenyl)methyl 1.227 449.9 209. CHFMe F F H F benzyl 1.054 394.0 210. CHFMe F F H F (2-methoxyphenyl)methyl 1.090 424.0 211. CHFMe F F H F (3-methoxyphenyl)methyl 1.056 424.0 212. CHFMe F F H F (4-methoxyphenyl)methyl 1.054 424.0 213. CMe2OMe F F H F benzyl 1.001 420.0 214. CMe2OMe F F H F (2-methoxyphenyl)methyl 1.027 450.1 215. CMe2OMe F F H F (3-methoxyphenyl)methyl 1.006 450.1 216. CFMe2 F F H F (4-ethylphenyl)methyl 1.204 435.9 217. CFMe2 F F H F (3-chlorophenyl)methyl 1.148 441.8 218. CFMe2 F F H F (2-cyclopropylphenyl)methyl 1.196 447.9 219. CFMe2 F F H F [3-(methoxymethyl)phenyl]methyl 1.096 451.9 220. CFMe2 F F H F [4-(methoxymethyl)phenyl]methyl 1.089 451.9 221. CFMe2 F H H H [4-(methoxymethyl)phenyl]methyl 1.000 416.0 222. CFMe2 F F H Br benzyl 1.157 468.0 223. CFMe2 F H H Br benzyl 1.102 452.0 224. CFMe2 F F H F [2-(methoxymethyl)phenyl]methyl 1.095 451.9 225. CMe2OMe F F H F (4-methoxyphenyl)methyl 1.013 449.9 226. CMe2OMe F F H F o-tolylmethyl 1.040 433.9 227. CMe2OMe F F H F m-tolylmethyl 1.051 433.9 228. CMe2OMe F F H F p-tolylmethyl 1.057 433.9 229. CHFMe F F H F o-tolylmethyl 1.092 407.9 230. CHFMe F F H F m-tolylmethyl 1.104 407.9 231. CHFMe F F H F p-tolylmethyl 1.109 407.8 232. CFMe2 F F H F (2-bromophenyl)methyl 1.150 486.0 233. 1-fluoro-3-methyl-butyl F H H H benzyl 1.141 400.0 234. CFMe2 F F H Cl benzyl 1.140 424.0 235. CFMe2 F Br H Br benzyl 1.209 529.9 236. CFMe2 F F F F benzyl 1.138 426.0 237. 1-methoxyethyl F F H F o-tolylmethyl 0.986 419.9 238. 1-methoxyethyl F F H F m-tolylmethyl 1.009 419.9 239. 1-methoxyethyl F F H F p-tolylmethyl 0.997 419.9 240. 1-methoxyethyl F F H F (2-fluorophenyl)methyl 0.981 424.0 241. 1-methoxyethyl F F H F (3-fluorophenyl)methyl 0.993 424.0 242. 1-methoxyethyl F F H F (4-fluorophenyl)methyl 0.991 424.0 243. 1-methoxyethyl F F H F (2-chlorophenyl)methyl 1.022 440.0 244. 1-methoxyethyl F F H F (3-chlorophenyl)methyl 1.030 440.0 245. 1-methoxyethyl F F H F (4-chlorophenyl)methyl 1.028 440.0 246. 1-chloro-1-methyl-ethyl F F H F benzyl 1.215 423.9 247. 1-fluoro-1-methyl-propyl F F H F benzyl 1.128 421.9 248. CMe2OMe F F H F (2-fluorophenyl)methyl 1.015 438.0 249. CMe2OMe F F H F (3-fluorophenyl)methyl 1.023 438.0 250. CMe2OMe F F H F (4-fluorophenyl)methyl 1.023 438.0 251. CMe2OMe F F H F (2-chlorophenyl)methyl 1.050 454.0 252. CMe2OMe F F H F (3-chlorophenyl)methyl 1.060 454.1 253. CMe2OMe F F H F (4-chlorophenyl)methyl 1.058 454.0 254. i-Pr F F H F benzyl 0.973 389.9 255. CHFMe F F H F (2,6-dimethylphenyl)methyl 1.135 421.9 256. 1-fluorocyclohexyl F F H F benzyl 1.208 448.1 257. CFMe2 F H H H benzyl 1.046 369.9 258. 1-fluorocyclohexyl F H H CN benzyl 1.093 436.9 259. CFMe2 F H H CN benzyl 1.000 397.1 260. 1-fluorocyclopentyl Cl H H Br benzyl 1.186 494.0 261. CFMe2 Cl H H Br benzyl 1.143 468.0

B USE EXAMPLES

[0537] The herbicidal activity of the azines of formula (I) was demonstrated by the following greenhouse experiments:

[0538] 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.

[0539] 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.

[0540] 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.

[0541] Depending on the species, the plants were kept at 10-25° C. or 20-35° C., respectively.

[0542] 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.

[0543] 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.

[0544] The plants used in the greenhouse experiments were of the following species:

TABLE-US-00008 Bayer code Scientific name ABUTH Abutilon theophrasti ALOMY Alopercurus myosuroides AMARE Amaranthus retroflexus APESV Apera spica-venti CAPBP Capsella bursa-pastoris CHEAL Chenopodium album ECHCG Echinocloa crus-galli GERDI Geranium dissectum LAMPU Lamium purpureum LOLMU Lolium multiflorum MATIN Matricaria maritima POAAN Poa annua POLCO Polygonum convolvulus SETFA Setaria faberi SETVI Setaria viridis STEME Stellaria media THLAR Thlaspi arvense VIOAR Viola arvensis

[0545] Example 4 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0546] Example 5 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 98%, 100% and 98% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0547] Example 6 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0548] Example 9 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 95%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0549] Example 10 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0550] Example 11 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0551] Example 14 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 90% and 80% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0552] Example 18 applied by pre-emergence method at an application rate of 250 g/ha, showed 70%, 70%, 70% and 85% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0553] Example 19 applied by pre-emergence method at an application rate of 250 g/ha, showed 70%, 80% and 85% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus and Setaria faber respectively.

[0554] Example 20 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 98%, 100% and 95% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0555] Example 22 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi.

[0556] Example 23 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% and 75% herbicidal activity against Echinocloa crus-galli and Setaria faberi respectively.

[0557] Example 26 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 80% and 70% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faberi respectively.

[0558] Example 27 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faberi.

[0559] Example 28 applied by post-emergence method at an application rate of 125 g/ha, showed 75%, 85% and 75% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria viridis respectively.

[0560] Example 30 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi.

[0561] Example 31 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 75% and 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Echinocloa crus-galli respectively.

[0562] Example 33 applied by pre-emergence method at an application rate of 250 g/ha, showed 75% and 60% herbicidal activity against Alopercurus myosuroides and Echinocloa crus-galli respectively.

[0563] Example 35 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi.

[0564] Example 36 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% and 75% herbicidal activity against Amaranthus retroflexus and Echinocloa crus-galli respectively.

[0565] Example 39 applied by pre-emergence method at an application rate of 250 g/ha, showed 90%, 80%, 100% and 90% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi respectively.

[0566] Example 42 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% and 80% herbicidal activity against Amaranthus retroflexus and Abutilon theophrasti respectively.

[0567] Example 43 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Abutilon theophrasti and Echincloa crus-galli.

[0568] Example 44 applied by pre-emergence method at an application rate of 250 g/ha, showed 70% and 70% herbicidal activity against Setaria faberi and Abutilon theophrasti respectively.

[0569] Example 45 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 70% and 80% herbicidal activity against Alopercurus myosuroides, Setaria faberi and Echinocloa crus-galli respectively.

[0570] Example 47 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 100% and 80% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Echinocloa crus-galli respectively.

[0571] Example 52 applied by pre-emergence method at an application rate of 250 g/ha, showed 90% and 85% herbicidal activity against Echinocloa crus-galli and Setaria faberi.

[0572] Example 54 applied by pre-emergence method at an application rate of 250 g/ha, showed 90% and 100% herbicidal activity against Alopercurus myosuroides and Echinocloa crus-galli.

[0573] Example 56 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% and 95% herbicidal activity against Lolium multiflorum and Echinocloa crus-galli.

[0574] Example 58 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 90% and 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi respectively.

[0575] Example 60 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi respectively.

[0576] Example 61 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 100% and 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi respectively.

[0577] Example 65 applied by pre-emergence method at an application rate of 250 g/ha, showed 95% and 95% herbicidal activity against Alopercurus myosuroides and Echinocloa crus-galli respectively.

[0578] Example 69 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi.

[0579] Example 70 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Echinocloa crus-galli.

[0580] Example 72 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi.

[0581] Example 73 applied by pre-emergence method at an application rate of 250 g/ha, showed 70% and 75% herbicidal activity against Amaranthus retroflexus and Echinocloa crus-galli respectively.

[0582] Example 74 applied by pre-emergence method at an application rate of 250 g/ha, showed 80% and 85% herbicidal activity against Amaranthus retroflexus and Echinocloa crus-galli respectively.

[0583] Example 77 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 100% and 100% herbicidal activity against Abutilon theophrasti, Setaria faberi and Echinocloa crus-galli respectively.

[0584] Example 78 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 100% and 75% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faberi respectively.

[0585] Example 83 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faberi.

[0586] Example 85 applied by pre-emergence method at an application rate of 250 g/ha, showed 70%, 70% and 90% herbicidal activity against Setaria faberi, Alopercurus myosuroides and Abutilon theophrasti respectively.

[0587] Example 91 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi.

[0588] Example 94 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% and 70% herbicidal activity against Alopercurus myosuroides and Amaranthus retroflexus respectively.

[0589] Example 96 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 100%, 100% and 95% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi respectively.

[0590] Example 97 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi.

[0591] Example 98 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 90%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi respectively.

[0592] Example 99 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 100%, 90% and 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi respectively.

[0593] Example 100 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 100% and 80% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Abutilon theophrasti respectively.

[0594] Example 102 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 100% and 85% herbicidal activity against Setaria faberi, Echinocloa crus-galli and Abutilon theophrasti respectively.

[0595] Example 107 applied by pre-emergence method at an application rate of 250 g/ha, showed 75%, 75%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi respectively.

[0596] Example 108 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faberi.

[0597] Example 110 applied by pre-emergence method at an application rate of 250 g/ha, showed 90% and 80% herbicidal activity against Echinocloa crus-galli and Setaria faber respectively.

[0598] Example 111 applied by post-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti and Amaranthus retroflexus.

[0599] Example 111 applied by pre-emergence method at an application rate of 250 g/ha, showed 80% and 85% herbicidal activity against Apera spica-venti and Echinocloa crus-galli respectively.

[0600] Example 112 applied by post-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti and Amaranthus retroflexus.

[0601] Example 112 applied by pre-emergence method at an application rate of 250 g/ha, showed 80% herbicidal activity against Apera spica-venti and Echinocloa crus-galli.

[0602] Example 114 applied by pre-emergence method at an application rate of 250 g/ha, showed 90% herbicidal activity against Echinocloa crus-galli and Setaria faberi.

[0603] Example 116 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0604] Example 117 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0605] Example 120 applied by pre-emergence method at an application rate of 250 g/ha, showed 75%, 100% and 90% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0606] Example 121 applied by post-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti and Amaranthus retroflexus.

[0607] Example 121 applied by pre-emergence method at an application rate of 250 g/ha, showed 80% herbicidal activity against Amaranthus retroflexus.

[0608] Example 125 applied by pre-emergence method at an application rate of 250 g/ha, showed 85% and 100% herbicidal activity against Apera spica-venti and Echinocloa crus-galli respectively.

[0609] Example 128 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 90% and 90% herbicidal activity against Amaranthus retroflexus, Setaria faber and Abutilon theophrasti respectively.

[0610] Example 129 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0611] Example 130 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Setaria faber and Echinocloa crus-galli.

[0612] Example 131 applied by pre-emergence method at an application rate of 250 g/ha, showed 90%, 85% and 90% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Setaria faber respectively.

[0613] Example 132 applied by pre-emergence method at an application rate of 250 g/ha, showed 90%, 90% and 100% herbicidal activity against Amaranthus retroflexus, Setaria faber and Echinocloa crus-galli respectively.

[0614] Example 134 applied by pre-emergence method at an application rate of 250 g/ha, showed 95%, 90% and 90% herbicidal activity against Apera spica-venti, Echinocloa crus-galli and Setaria faber respectively.

[0615] Example 135 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Setaria faber and Echinocloa crus-galli.

[0616] Example 136 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 85% and 80% herbicidal activity against Apera spica-venti, Echinocloa crus-galli and Setaria faber respectively.

[0617] Example 139 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0618] Example 140 applied by pre-emergence method at an application rate of 250 g/ha, showed 98% and 100% herbicidal activity against Echinocloa crus-galli and Setaria faber respectively.

[0619] Example 141 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100% and 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0620] Example 142 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0621] Example 143 applied by pre-emergence method at an application rate of 250 g/ha, showed 90% and 100% herbicidal activity against Alopercurus myosuroides and Amaranthus retroflexus respectively.

[0622] Example 148 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0623] Example 149 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 90% and 75% herbicidal activity against Alopercurus myosuroides, Setaria faber and Echinocloa crus-galli respectively.

[0624] Example 152 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% and 90% herbicidal activity against Amaranthus retroflexus and Setaria faber respectively.

[0625] Example 154 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0626] Example 160 applied by pre-emergence method at an application rate of 250 g/ha, showed 85% and 75% herbicidal activity against Alopercurus myosuroides and Setaria faber respectively.

[0627] Example 161 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Echinocloa crus-galli and Setaria faberi.

[0628] Example 163 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber.

[0629] Example 164 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber.

[0630] Example 165 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli.

[0631] Example 167 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Setaria faber.

[0632] Example 169 applied by pre-emergence method at an application rate of 250 g/ha, showed 80% and 85% herbicidal activity against Amaranthus retroflexus and Setaria faber respectively.

[0633] Example 170 applied by pre-emergence method at an application rate of 250 g/ha, showed 90%, 100% and 90% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0634] Example 171 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 85% and 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0635] Example 172 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber.

[0636] Example 173 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Echinocloa crus-galli.

[0637] Example 174 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber.

[0638] Example 175 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 100% and 95% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0639] Example 176 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 100% and 80% herbicidal activity against Echinocloa crus-galli and Setaria faberi, Amaranthus retroflexus respectively.

[0640] Example 177 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 100% and 95% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0641] Example 178 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0642] Example 180 applied by pre-emergence method at an application rate of 250 g/ha, showed 90%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0643] Example 181 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0644] Example 182 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0645] Example 183 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faberi.

[0646] Example 184 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 95% and 98% herbicidal activity against Alopercurus myosuroides, Amaranthus retroflexus and Echinocloa crus-galli respectively.

[0647] Example 185 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0648] Example 186 applied by pre-emergence method at an application rate of 250 g/ha, showed 85% and 98% herbicidal activity against Alopercurus myosuroides, and Echinocloa crus-galli respectively.

[0649] Example 187 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0650] Example 188 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli.

[0651] Example 189 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0652] Example 191 applied by pre-emergence method at an application rate of 250 g/ha, showed 95%, 100% and 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0653] Example 192 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Echinocloa crus-galli and Setaria faberi.

[0654] Example 193 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 95% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0655] Example 194 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% and 70% herbicidal activity against Echinocloa crus-galli and Setaria faber respectively.

[0656] Example 196 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0657] Example 198 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100% and 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0658] Example 199 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli.

[0659] Example 200 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faberi.

[0660] Example 201 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber.

[0661] Example 202 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 80% and 85% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0662] Example 203 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faberi.

[0663] Example 204 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides, Echinocloa crus-galli and Setaria faberi.

[0664] Example 205 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber.

[0665] Example 206 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides, Echinocloa crus-galli and Setaria faberi.

[0666] Example 207 applied by pre-emergence method at an application rate of 250 g/ha, showed 90%, 100% and 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0667] Example 208 applied by pre-emergence method at an application rate of 250 g/ha, showed 90% and 80% herbicidal activity against Abutilon theophrasti and Amaranthus retroflexus respectively.

[0668] Example 209 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0669] Example 210 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0670] Example 211 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0671] Example 212 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0672] Example 213 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0673] Example 214 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 98% and 90% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Setaria faber respectively.

[0674] Example 215 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 98% and 98% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0675] Example 216 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 98% and 100% herbicidal activity against against Abutilon theophrasti, Alopercurus 30 myosuroides and Setaria faber respectively.

[0676] Example 217 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100% and 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0677] Example 218 applied by pre-emergence method at an application rate of 250 g/ha, showed 95%, 85% and 100% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0678] Example 219 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 85% and 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0679] Example 220 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 95% and 90% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0680] Example 222 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 100% and 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0681] Example 223 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 95% and 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0682] Example 224 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 90% and 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0683] Example 226 applied by pre-emergence method at an application rate of 250 g/ha, showed 90%, 100% and 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli respectively.

[0684] Example 227 applied by pre-emergence method at an application rate of 250 g/ha, showed 90%, 75% and 85% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0685] Example 228 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 100% and 90% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli respectively.

[0686] Example 229 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli.

[0687] Example 230 applied by pre-emergence method at an application rate of 250 g/ha, showed 95%, 95% and 95% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0688] Example 231 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 98% and 98% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli respectively.

[0689] Example 232 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faberi.

[0690] Example 233 applied by pre-emergence method at an application rate of 250 g/ha, showed 75%, 80% and 95% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli respectively.

[0691] Example 234 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 90% and 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli respectively.

[0692] Example 235 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 90% and 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0693] Example 236 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 95% and 100% herbicidal activity against Abutilon theophrasti, Alopercurus myosuroides and Echinocloa crus-galli respectively.

[0694] Example 237 applied by pre-emergence method at an application rate of 250 g/ha, showed 95%, 100% and 95% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0695] Example 238 applied by pre-emergence method at an application rate of 250 g/ha, showed 80%, 98% and 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0696] Example 240 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 90% and 95% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0697] Example 241 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 85% and 85% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber respectively.

[0698] Example 243 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 85% and 85% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively. Example 244 applied by pre-emergence method at an application rate of 250 g/ha, showed 85%, 75% and 75% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Setaria faber respectively.

[0699] Example 246 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus, and Echinocloa crus-galli.

[0700] Example 247 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0701] Example 248 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus, and Echinocloa crus-galli.

[0702] Example 249 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faberi.

[0703] Example 250 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus, and Echinocloa crus-galli.

[0704] Example 251 applied by pre-emergence method at an application rate of 250 g/ha, showed 98%, 95% and 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faber respectively.

[0705] Example 252 applied by pre-emergence method at an application rate of 250 g/ha, showed 100%, 95% and 100% herbicidal activity against Abutilon theophrasti, Amaranthus retroflexus and Setaria faber respectively.

[0706] Example 254 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faberi.

[0707] Example 255 applied by pre-emergence method at an application rate of 250 g/ha, showed 90%, 95% and 90% herbicidal activity against Alopercurus myosuroides, Echinocloa crus-galli and Setaria faber respectively.

[0708] Example 256 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus, Echinocloa crus-galli and Setaria faber.

[0709] Example 257 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Abutilon theophrasti, Echinocloa crus-galli and Setaria faberi.

[0710] Example 259 applied by pre-emergence method at an application rate of 250 g/ha, showed 100% herbicidal activity against Amaranthus retroflexus and Setaria faberi.