IL42103A - 6-amino-s-triazine-2,4-(1h,3h)-diones and corresponding 4-thio compounds,their preparation and their use as herbicides - Google Patents

Abstract

1435585 6-Amino-s-triazin-2,4[1H,3H]-dione derivatives E I DU PONT DE NEMOURS & CO 23 May 1973 [24 May 1972 5 April 1973 (2)] 24677/73 Headings A5E E1C5J E1C5P E1C5M E1C14A E1C15D3 E1A3B ElA3Cand E1A5B3 Novel compounds have the Formula I wherein R 1 is selected from (a) alkyl of 2 to 8 carbon atoms, alkenyl of 3 to 6 carbon atoms, alkynyl of 3 to 6 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, cycloalkenyl of 5 to 8 carbon atoms, cycloalkylmethyl of 4 to 9 carbon atoms, cycloalkenylmethyl of 6 to 9 carbon atoms, bicycloalkyl or bicycloalkenyl of 7 to 10 carbon atoms and bicycloalkylmethyl or bicycloalkenylmethyl of 8 to 11 carbon atoms, trimethylcyclohexyl and tetramethylcyclohexyl; (b) the above alkyl groups substituted with one methoxy, ethoxy, methylthio or ethylthio group; (c) the above cycloalkyl groups substituted with one alkyl group of 2 to 4 carbon atoms, 1 or 2 methyl groups, 1 or 2 chlorine or bromine atoms, one methoxy or one ethoxy group; and (d) a group of Formula wherein Q is hydrogen, fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms, alkoxy of alkylthio of 1 or 2 carbon atoms, nitro or a trifluoromethyl group; Y is hydrogen, chlorine or methyl; and Z is hydrogen or chlorine; R 2 is hydrogen, alkyl of 1 to 3 carbon atoms or a cation selected from Na<SP>+</SP>, Li<SP>+</SP>, K<SP>+</SP>, (Ca/2)<SP>+</SP>, ammonium and dimethylammonium; R 2 is hydrogen, methyl or ethyl; R 4 is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, or methoxy; and X is oxygen or sulphur; provided that when X is sulphur, neither R 2 nor R 3 is hydrogen. The compounds of Formula I are prepared, for example, by reaction of a corresponding 6- methylthio compound with an amine of Formula R 3 R 4 NH or, in the case of a 4-thio derivative, by reaction of P 2 S 5 with the corresponding 2,4-dione derivative. The compounds of Formula I in which R 2 is alkyl [=R<SP>1</SP> 2 ] are also obtained by cyclization, in the presence of a base (an alkali metal C 1-4 alkoxide), of a compound of Formula CH 3 O-CO-NR<SP>1</SP> 2 -C(NR 3 R 4 )=N-CX-NHR 1 These latter starting materials are themselves obtained by reacting methoxycarbonyl-cyanamide with an alkylating agent of Formula R<SP>1</SP> 2 -Q [Q = chloride, bromide, iodide or -O-SO 2 OR<SP>1</SP> 2 ] to form N-methoxycarbonyl-N-alkylcyanamide, reacting the latter with an amine of Formula R 3 R 4 NH to form a compound of Formula CH 3 O-CO-NR<SP>1</SP> 2 -C(NR 3 R 4 )=NH and then reacting this intermediate with an isocyanate or isothiocyanate of Formula R 1 NCX. The compounds of Formula I are herbicides. [GB1435585A]

Claims (3)

1. CLAIMS : 1. Compounds of the formula: wherein is selected from alkyl of 2 through 8 carbon atoms, alkenyl of 3 through 6 carbon atoms, alkynyl of 3 through through 6 carbon atoms, cycloalkyl of 4 through 8 carbon atoms, cycloalkenyl of 5 through 8 carbon atoms, cycloalkylmethyl of k through 9 carbon atoms, cyclo- alkenylmethyl of 6 through 9 carbon atoms, bicyclo- alkyl or blcycloalkenyl of 7 through 10 carbon atoms and bicycloalkylmethyl or bicy cloalkenylmethyl of 8 through 11 carbon atoms, trimethylcyclohexyl and tetramethylcyclohexyl; the above alkyl groups substituted with one methoxy, ethoxy, methylthio or ethylthio group; the above cycloalkyl groups substituted with one alkyl of 2 through carbon atoms, 1 through 2 methyl groups, 1 through 2 chlorines or bromines, one methoxy or one ethoxy group; and Q wherein Q is hydrogen, fluorine, chlorine, bromine, alkyl of 1 through 4 carbon atoms, alkoxy or alkyl- thio of 1 through 2 carbon atoms, nitro or a trifluoromethyl group; Y is hydrogen, chlorine, or methyl; and Z is hydrogen or chlorine; R2 is hydrogen, alkyl of 1 through 3 carbon atoms or + + + + a cation selected from Na , Li , κ , (Ca/2) , ammonium and dimethylammonium; R3 is hydrogen, methyl or ethyl; is alkyl of 1 through 4 carbon atoms, alkenyl of 3 through h carbon atoms, alkynyl of 3 through 4 carbon atoms, or methoxy; and X is oxygen or sulfur; provided that when X is sulfur, neither R2 nor R^ is hydrogen.
2. 2. Compounds of Claim 1 wherein: R1 is alkyl to 3 through 6 carbon atoms, cycloalkyl of 5 through 8 carbon atoms, or cycloalkyl of 5 through 8 carbon atoms substituted with one methyl group; R2, R^ and R^ are methyl; and X is oxygen or sulfur. 3. Compounds of Claim 1 wherein: is cyclopentyl, methylcyclopentyl , cyclohexyl or methylcyclohexyl; 2, R^ and R^ are methyl; and X is oxygen. Compound of Claim 1: l-Methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2, lH,3H)-dione. 5. Compound of Claim 1: l- ethyl-3-cyclopentyl-6-dimethylamino-s-triazine-2,4(lH,3H)-dione. 6. A method of controlling undesired vegetation which comprises applying to the locus to be protected a herbi-cidally effective amount of a compound of Claim 1. 7. A method o controlling undesired vegetation which comprises applying to the locus to be protected a herbicidally effective amount of a compound of Claim 2. 8. A method of controlling undesired vegetation which comprises applying to the locus to be protected a herbicidally effective amount of a compound of Claim 3· 9. A method of controlling undesired vegetation which comprises applying to the locus to be protected a herbicidally effective- amount of a compound of Claim 4. 10. A method of controlling undesired vegetation which comprises applying to the locus to be protected a herbicidally effective amount of a compound of Claim 5. 11. A composition for controlling undesired vegetation which comprises a compound of Claim 1 and at least one 12. A composition for controlling undesired vegetation which comprises a compound of Claim 2 and at least one of a) a surfactant and b) an inert carrier material. 13. A composition for controlling undesired vegetation which comprises a compound of Claim 3 and at least one of a) a surfactant and b) an inert carrier material. 1 . A composition for controlling undesired vegetation which comprises a compound of Claim 4 and at least one of a) a surfactant and b) an inert carrier material. 15. A composition for controlling undesired vegetation which comprises a compound of Claim 5 and at least one of a) a surfactant and b) an inert carrier material. 16. A method of making a compound of the formula: which comprises reacting an alkylating agent of the formula R Z with a compound of the formula: followed by reacting the latter compound with an amine of the formula R^R^ H , wherein ^R.-,, and R^ are as defined in Claim 1, R 2 is that part o QR2 (defined in Claim 1) limited to alkyl, Z is iodide or -0-S-OR'2, and M' is alkali metal. 0 17. Method of Claim 16 wherein R]L is alkyl of 3 through 6 carbon atoms, cycloalkyl of 5 through 8 carbon atoms, or cycloalkyl of 5 through 8 carbon atoms substituted with one methyl group, and R'2, R3 and R^ are methyl. 18. Method of Claim 16 wherein R^ is cyclopentyl, methylcyclopentyl, cyclohexyl or methylcyclohexyl , and R 2, R- and R,. are methyl. Method of Claim l6 wherein R1 is cyclohexyl and R,. are methyl. 0. Method of Claim 16 wherein 1 is cyclopentyl and R. are methyl. 21. A method of making a compound of the formula: which comprises reacting a compound of the formula: with an amine of the formula R^R^ H, wherein R^, R^ and R^ are as defined in Claim 1 and R . Is that part of R2 (defined in Claim 1) limited to alkyl. 22. Method of Claim 21 wherein R^ is alkyl of 3 through 6 carbon atoms, cycloalkyl of 5 through 8 carbon atoms or cycloalkyl of 5 through 8 carbon atoms substituted with one methyl group, and R'2, R3 and R^ are methyl. 23. Method of Claim 21 wherein R-j^ is cyclopentyl, methylcyclopentyl, cyclohexyl or methylcyclohexyl , and R 2> R^ and R^ are methyl. 24. Method of Claim 21 wherein R-L is cyclohexyl and R 2, R^ and R^ are methyl. 25. Method of Claim 21 wherein R^ is cyclopentyl and R R- and R are methyl. 26. A method of making a compound of the formula: wherein R^, R^ and R^ are as defined in claim 1; which comprises reacting an amine of the formula R^R^ H with a compound of the formula followed by acidification. 27. Method of Claim 26 wherein R-^ is alkyl of 3 through 6 carbon atoms, cycloalkyl of 5 through 8 carbon atoms, or cycloalkyl of 5 through 8 carbon atoms substituted with one methyl group, and R^ and R^ are methyl. 28. Method of Claim 26 wherein is cyclopentyl, methylcyclopentyl , cyclohexyl or methylcyclohexyl, and R^ and R^ are methyl. 29. Method of Claim 26 wherein R1 is cyclohexyl and R^ and R^ are methyl. 30. Method of Claim 26 wherein R^ is cyclopentyl and R_ and R, are methyl. method of making salts of the formula which comprises reacting an amine of the formula with a compound of the formula: H wherein R^ is as defined in Claim 1, R2 is dimethylammoni and R and R, are each methyl. 32. Method of Claim 31 wherein R. is alkyl to 3 through 6 carbon atoms, cycloalkyl of 5 through 8 carbon atoms, or cycloalkyl of 5 through 8 carbon atoms substituted with one methyl group. 33· Method of Claim 31 wherein ^ is cyclopentyl, methylcyclopentyl, cyclohexyl or methylcyclohexyl. 34. Method of Claim 31 wherein R, is cyclohexyl. Method of Claim 31 wherein R, is cyclopentyl 36. A method of making salts of the formula: wherein Rj, R^ and R^ are as defined in Claim 1, and R 2 ie which comprises reacting a compound of the formula: with a base selected from ammonia, dimethylamine , and the hydroxides of sodium, lithium, potassium, and calcium. 37. Method of Claim 36 wherein R^ is alkyl of 3 through 6 carbon atoms, cycloalkyl of 5 through 8 carbon atoms, or cycloalkyl of 5 through 8 carbon atoms substituted with one methyl group, and R^ and R^ are methyl. 38. Method of Claim 36 wherein R^ is cyclopentyl, methylcyclopenty1, cyclohexyl or methylcyclohexyl , and R^ and Rjj are methyl. 39. Method of Claim 36 wherein R1 is cyclohexyl and R^ and R^ are methyl. 40. Method of Claim 36 wherein R1 is cyclopentyl and R~ and R,. are methyl. A method of making a compound of the formula S which comprises reactlne phosphorus pentasulfide with a compound of the formula: wherein R-L and R^ are as defined in Claim 1, R 2 is that portion of R2 defined in Claim 1 limited to alkyl, and R ^ is that portion of R^ defined in Claim 1 limited to methyl and ethyl. 42. Method of Claim 41 wherein R1 is alkyl of 3 through 6 carbon atoms, cycloalkyl of 5 through 8 carbon atoms . or cycloalkyl of 5 through 8 carbon atoms substituted with one methyl group, and R'2> 1^ and R^ are methyl.
3. 3. Method of Claim 41 wherein R^^ is cyclopentyl, methylcyclopentyl, cyclohexyl or methylcyclohexyl , and t ? R 5, R -j and R,. are methyl. Method of Claim 41 wherein R^ is cyclohexyl and RL are methyl. Method of Claim 41 wherein R, is cyclopentyl and R 5, R _ and R^ are methyl. Ί6. A process for preparation of compounds of the formula: which comprises the following steps in sequence: A: reacting a methylating agent of the formula CH^ with irethoxycarbonyl- cyanamide to form N-methoxycarbonyl- N-methylcyanamide ; B: reacting the product of step A with an amine of the formula R^R^NH to form a compound of the formula: NH II CH-OC-N-C-NR-R,. (7); J II I J " 0 CH„ C: reacting the product of step B with an isocyanate or isothlocyanate of the formula R^NCX to form a compound of the formula: X N-C-NHR. II CH-OC-N-C-NR-Rj. J II t J 4 0 CH- D. treating the product of step C with a base M'OR to cyclize and form the desired product; in the above formulae:. is Cg-Cg alkyl, C^-Cg cycloalkyl, norbornyl, methylcyclohexyl, methyl- cyclopentyl, phenyl, or chlorophenyl; is hydrogen or methyl; ^ is C^C^ alkyl; X is oxygen or sulfur; provided that when X is sulfur, R^ is methyl; Z is iodide or -O-SC^-OCH^; M' is alkali metal; and R is hydrogen or C^-C^ alkyl. f . Process of Claim 6 wherein step B is carried out in aqueous solution using a hydrochloride or sulfate salt of tht; amine R^R^NH, whereby a solution of the corresponding salt of the product is formed. 48. Process of Claim ^7 wherein, between steps B and C, the reaction medium is treated with alkali to liberate the free bases of the unreacted R^R^ H and the product, the resulting solution is immediately subjected to distillation at a temperature below 50°C to remove R^R^NH and the residual solution is immediately treated with sulfuric or hydrochloric acid to again form the corresponding salt of the product. 49. Process of Claim 48 wherein step D is carried out in a solvent selected from benzene, chlorobenzene , toluene and xylene in the presence of 1 to 2.5 moles of anhydrous R-R^NH. 50. Process of Claim 49 wherein R1 is cyclohexyl, oxygen, and R and R. are both methyl. For the Applicants DR. REINHOID COHN AND PARTNERS