NO140268B - 6-AMINO-S-TRIAZINONDE DERIVATIVES WITH HERBICID EFFECT AND A PROCEDURE FOR THE MANUFACTURE - Google Patents

Description

The present invention relates to a new group of 6-amino-s-triazinone derivatives with herbicidal action and a method for their production.

Neumayer et al., "Pesticides", Chemical Week, April 12 and 26, 1969, list several commercial and experimental s-triazinherbicides. Among these, two well-known products are atrazine and simazine:

US Patents 3,505,323 and 3,505,057 disclose a class of tetrahydro-s-triazinones of formula A below and their use as herbicides. DAS 1,962,797 discloses a class of s-triazinones of the formula B below and their use as herbicides.

Q = S or O

X = halogen X = S or O

Y = H, halogen, alkyl etc. R-^R 2 and R 3 =Or alkyl R and Rj = alkyl

n m 1 or 2

Chem. Pray. 104, 1606 (1971) states the preparation of s-tri-azinethiones by cyclocondensation of ethoxycarbonyl isothiocyanate with amidines, isoureas, isothioureas and guanidines:

where X can mean, among other things, (C2H5)2N-, (C2H5CH2)2N- or (C6H5)2N-.

The present invention relates to new compounds

with herbicidal action with the formula:

where R^means alkyl with 2-8 carbon atoms, cycloalkyl with 4 -

8 carbon atoms, cyclohexenyl, norbornyl, norbornyl, methylcyclohexyl or tetramethylcyclohexyl, or the above-mentioned cycloalkyl groups substituted by one alkyl group with 2-4 carbon atoms, 1-2 methyl groups or 1-2 chlorine or bromine atoms, or R^

where Q is hydrogen, fluorine, chlorine, bromine, nitro or trifluoromethyl, Y is hydrogen, chlorine or methyl,

R is hydrogen, methyl or a cation comprising Na<+>, Li<+>, K<+>, (Ca/ 2) , ammonium or dimethylammonium,

R is hydrogen or methyl,

R^ is alkyl with 1-4 carbon atoms, and

X is oxygen or sulphur,

with the proviso that when X is sulfur, neither R nor R is hydrogen.

The invention also includes a method for the production of the above-mentioned 6-aminotriazinones.

Of the compounds covered by formula I, those are preferred where R 1 is alkyl with 3-6 carbon atoms, cycloalkyl with 5-8 carbon atoms or cycloalkyl with 5-8 carbon atoms, substituted with a methyl group, and where R 2 , R 3 and R 4 are methyl and X is oxygen or sulphur.

More preferred are the compounds of formula I where R 1 is cyclopentyl, methylcyclopentyl, cyclohexyl or methylcyclohexyl, and where R 2 , R 3 and R 4 are methyl and X is oxygen.

Most preferred is

1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione.

The compounds of formula I are prepared according to the invention by the following sequence of steps: A: react a methylating agent of the formula CH^Z, where Z is iodine or -O-SC^-OCH^, with methoxycarbonylcyanamide to give N-methoxycarbonyl-N-methylcyanamide, B: react the product of step A with an amine of the formula R^R^NH where R^ and R^ are as above, to give the compound of the formula:

where R^ and R^ are as indicated above,

C:. reacting the product of step B with an isocyanate or isothiocyanate of the formula R^NCX, where R^ and X are as above, to give a compound of the formula:

where R^, R^j R^ and X are as indicated above, and

D: treat the product obtained in step C with a base of the formula M<*>OR, where R is hydrogen or alkyl of 1-4 carbon atoms, and M' is an alkali metal, for cyclization to obtain the desired product. ;The procedure can be illustrated by the equations: ; where: R^ , R^ and R^ have the meanings previously indicated, R is hydrogen or alkyl with 1-4 carbon atoms, R'^ is methyl, M' is an alkali metal and Z is iodine or ; A method for the production of methyl cyanocarbamate (compound 1) from cyanamide and methyl chloroformate is described in - US patent no. 3,657,443-; An aqueous solution of the sodium salt of compound 1, containing 15 - 35% of 1, preferably 20 - 30%, is reacted at 10 - 70°C, preferably at 25 - 45°C, with 0.9 - 1.4, preferably 1.0 - 1.2, molecular equivalents of a methylating agent (e.g. dimethylsulphate) during 2 - 16 hours, preferably 4-8 hours (reaction A). During the course of the reaction, a second phase of N-methoxycarbonyl-N-methylcyanamide is formed. After the reaction has proceeded for the desired time, the upper layer of compound 3, which contains some water, is separated and the lower aqueous layer is contacted with an organic solvent such as methylene chloride, dichloroethane, triolene, benzene, toluene or xylene, and where toluene is preferred. Instead of dimethylsulphate, methyl iodide can also be used. The sulfate is preferred for economic reasons. The extract and the upper layer are analyzed with respect to compound 3 by gas chromatography and added to an aqueous solution containing 15 - 75%, preferably 25 - 50% of the hydrochloride or sulphate of compound 4/preferably the sulphate (reaction step B). The molar ratio of amine salt to compound 3 can be 1-3, preferably 1.5-2.5. The extraction solvent used (e.g. toluene) is removed either by azeotropic or simple distillation, depending on the boiling point. The remaining aqueous mixture is stirred for 3 - 10 hours at 50 - 110° C, preferably 85 - 95° C (reaction equation B). Higher temperatures give a shorter reaction time and vice versa. The reaction mixture obtained contains compound 5 and as by-product trisubstituted guanidine as well as unreacted compound 4, which are all present as salts. Before compound 5 can be reacted with compound 6, it is necessary to liberate the free base and remove excess compound 4 to prevent the formation of urea by-products. This operation can be carried out by adding 50% aqueous sodium hydroxide solution in an amount equivalent to the amounts of compounds 4 and 5 present, as determined by gas chromatography analyses, and extracting with an organic solvent such as methylene chloride, followed by distillation of a portion of the organic solvent to remove excess compound 4/or by removing compound 4 directly from the aqueous solution by distillation or stripping with an inert gas after the base is first added to form the free amine. The latter method is preferred. ;Compound 5 is relatively unstable in aqueous solution when it is present as a free base and has a tendency to split into the corresponding trisubstituted guanidine. The rate of decomposition is directly proportional to pH and temperature. Therefore, when the excess of compound 4 is removed by direct distillation or stripping of water, it is advantageous to use a vacuum in order to carry out the operation as quickly as possible. ;The water distillation process described above can be carried out simultaneously or continuously. It is preferred to carry out the operation in a continuous manner so that compound 5 is exposed to a high temperature and high pH as little as possible. This can be achieved by adding a solution of aqueous alkali metal hydroxide to the reaction product from reaction B, in a pipeline reactor, or by introducing the product and the alkali metal hydroxide into a slightly stirred vessel with a short residence time, for example 0-10 minutes, preferably 0-2 minutes . If the concentration of the amine salt used is such that the sodium salt is precipitated during neutralization, additional water must be added to keep this salt in solution. The overflow from this vessel is led to a distillation column which operates under vacuum. The column is heated by supplying steam at the bottom and compound 4 and water are drawn off as distillate (overhead) and a. aqueous solution of compound 5 and trisubstituted guanidine are removed as bottom fractions. The conditions under which the column can be operated are manifold and depend to a certain extent on the nature of the connection. However, the conditions will generally be such that the temperature of feed material to the column does not have a temperature above 50° C. This necessitates cooling the product from reaction equation B to approx. 30° C before alkali is added. The column is allowed to work at a pressure of 25 - 300 mm Hg, preferably 50 - 150 mm Hg and the amount of steam supplied to the bottom of the column is adjusted so that the amount of water taken out as distillate together with compound 4f corresponds to 5-25% by weight of the reaction product from reaction equation B. The bottom fractions from the above-mentioned distillation are taken to a holding tank and kept at a pH of 5 - 7 by a continuous addition of either sulfuric acid or hydrochloric acid, sulfuric acid being preferred. The concentration of compound 5 in the neutralized solution is kept at 15-50%, preferably 20-40%. The concentration will depend on the strength of the salt solution of compound 4, the base and acid used in the previous steps and the degree of concentration that takes place during the distillation. The temperature of this solution is kept at 25 - 45° C, preferably 25 - 35° C, either by cooling the bottom fractions in a continuous type cooler before neutralization or by cooling the neutralization vessel itself. Reaction C is carried out by preparing a mixture of the above-mentioned solution and a solvent such as benzene, chlorobenzene, toluene or xylene, toluene being preferred. The amount of solvent added must be sufficient to dissolve the amount of compound 7 that will be formed. In general, the amount of solvent used will be 7-10 times the amount of compound 5/ which is present in the aqueous solution. An amount of compound 6, which is stoichiometrically equivalent to 85-100%, preferably 92-98%, of compound 5 present in the aqueous layer was added with good stirring and a solution of 50% aqueous alkali metal hydroxide is started while the temperature is maintained at -5 - 50° C, preferably 5 - 35° C, by means of external cooling. The addition of alkali metal hydroxide is done as quickly as heat can be removed to maintain the desired temperature and is continued until an amount has been added that is stoichiometrically equivalent to the amount of acid used in the neutralization of compound 5- If a solid phase of sodium salt appears at this stage, sufficient water should be added to dissolve it. The reaction is allowed to proceed after the addition of alkali metal hydroxide is complete and until the pH of the aqueous solution is almost constant. For this, an additional time of 1 - 3 hours is required. Alternatively, compound 6 and the aqueous solution of alkali metal hydroxide can be added simultaneously while the pH of the reaction mass is kept at 9-10, preferably 9.3-9.7, during 1-4 hours, preferably 2-3 hours. Addition of aqueous sodium hydroxide is continued until the pH of the solution is almost constant. The stirring is stopped and the layers are allowed to separate. The aqueous layer is removed and the upper organic layer is evaporated at a pressure of 50-760 mmHg, preferably 100-300 mmHg, until a clear distillate is obtained (indicating that all water has been removed). ;The remaining solution or suspension, containing compound 7, is cooled if necessary to 25 - 45° C, while the anhydrous amine 4 (e.g. dimethylamine) is added either in the form of a gas or a liquid. It is preferred to add amine 4 at 25 - 35°C, but higher or lower temperatures can be used depending on the solubility of amine 4 in the particular solvent. It is important to have at least 1.0, preferably 1.0 - 2.5 mol of the amine 4; Then the ring-closing catalyst (compound 8) is added (reaction equation D). The catalyst is an alkali metal alkoxide (or hydroxide) and it can be added either as a dry solid or as a solution in the alkanol used. Dry sodium methoxide or a solution of sodium methoxide in methanol is the preferred catalyst. The amount of the catalyst that is necessary is 0.1 - 5.0 mol% of compound 7. Higher concentrations are not desirable because side reactions intervene disturbingly. A preferred concentration of compound 8 is 1.0 - 2.0 mol% of compound 7. The temperature is not critical and the cyclization reaction can proceed at a temperature in the range 0 - 120° C, provided that amine 4 is kept inside the reaction system. The reaction is normally exothermic and the solution can be cooled if a lower temperature is required to retain the amine 4 . It is critical that the amine 4 is allowed to remain present until the ring closure is almost complete. ;After the catalyst has been added, the reaction mixture is held for 0.1 - 2 hours to ensure complete cyclization. The reaction proceeds quickly and is completely normal within a time of less than 1 hour. The amine 4 > the by-product methanol and part of the solvent are removed by distillation, either at atmospheric pressure or under reduced pressure. Water is then added and the remainder of the solvent is removed by azeotropic distillation. The distilled water can either be thrown away or returned to the system, depending on what is desired. The amount of water that remains in the residue is not critical and can amount to 0.1-5 parts or more per part of the connection 9, depending on how the connection 9 is to be isolated. Isolation can take place by recrystallization followed by filtration or centrifugation, by spray drying, by phase separation to remove most of the water or by other conventional methods. ;Alternatively, the compound 9 can be removed without distillation of all the methanol, the amine 4 and the solvent. If a solvent in which compound 9 is poorly soluble, such as hexane, is added to the reaction mixture, compound 9 will precipitate and can be removed by conventional methods. The following examples further illustrate the method for producing the compounds according to the present invention. ;In all examples, all parts are parts by weight and refractive indices are given as nD 2 5 are values determined at 25° C. ;Example 1 ;Preparation of starting material ;For a solution of 504 parts of a 50% aqueous cyanamide solution in 825 parts water at 25° C is added during 90 minutes and at a pH of 6.9 - 7.1 at the same time 572 parts of methyl chloroformate and 945 parts of a 50% aqueous sodium hydroxide solution. While the addition of the reactants proceeds, the temperature of the reaction mixture is allowed to rise to 53 - 55° C and is kept within this range by cooling. When the addition is complete, the reaction mass is cooled to 25° C, whereby the crystallization of the sodium salt of methoxycarbonylcyanamide takes place. A. Preparation of N-methoxycarbonyl-N-methylcyanamide; (reaction equation A) ;To the obtained sodium salt of methoxycarbonylcyanamide, dimethyl sulfate (775 parts) is added, and the reaction mixture is still stirred while the pH is kept at 7 - 7.1 by dropwise addition of approx. 25 parts of a 50% aqueous sodium hydroxide solution. After 6.5 hours, the obtained two-phase solution is repeatedly extracted with methylene chloride and the extract is dried. Half of the methylene chloride extract is evaporated under vacuum and the residue is distilled at 50°C at 0.5 mm Hg. 237.6 parts of N-methoxycarbonyl-N-methylcyanamide are obtained (69.5% yield). B. Preparation of N-methoxycarbonyl-N,N<1>,N'-trimethylguanidine ; (reaction equation 3) ;A solution of 339 parts of dimethylamine hydrochloride in 500 parts of water is heated to 50° C and the remaining half of the above-mentioned methylene chloride extract is gradually added, while the methylene chloride is simultaneously removed by distillation. The resulting two-phase mixture is heated for approx. 20 hours at 80° C., after which time the starting compound N-methoxycarbonyl-N-methylcyanamide has almost completely disappeared. The solution is then cooled to 0° C. and 336 parts of a 50% aqueous sodium hydroxide solution is added. Repeated extractions of the reaction solution with methylene chloride and evaporation of the methylene chloride under vacuum yield 228.6 parts of crude N-methoxycarbonyl-N,N<1>,N'-trimethylguanidine with a purity of 84.4%, from which the pure product is isolated by distillation at 72° C at 0.5 mm Hg. C. Preparation of methyl-N-(N-cyclohexylcarbamoyl-N',N'-dimethyl-amidino)-N-methylcarbamate (reaction equation C); To 14.8 parts of the above-mentioned raw N-methoxycarb-nyl-N,N ',N'-trimethylguanidine in 50 parts of methylene chloride is added to 11.0 parts of cyclohexyl isocyanate. The temperature of the solution rises to the boiling point and when the temperature has fallen to 25° C the solvent is evaporated under vacuum whereby an oil is obtained which is crystallized by trituration with ether. Recrystallization from a mixture of carbon tetrachloride and petroleum ether gives pure methyl-N-(N-cyclohexylcarbamoyl-N',N'-dimethylamidino)-N-methylcarbamate, m.p. 93 - 94° C. ;Table II ;By following the general procedure according to example ;1C using the appropriate isocyanate such as isothiocyanate which is reacted with suitably substituted methoxycarbonylguanidine, the following compounds can be prepared. ;methyl-N-(N-cyclohexylthiocarbamoyl-N',N'-dimethylamidino)-N-methylcarbamate, m.p. 122 - 123° C; methyl-N-(N-(p-fluorophenylthiocarbamoyl)-N1,N'-dimethylamidino)-N-methylcarbamate, m.p. 132 - 133 C;D. Preparation of l-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2, 4(1H,3H)-dione (reaction equations A, B, C, D); A 10% stoichiometric excess of dimethyl sulfate; 906 parts) is added at 25° C with stirring to 3050 parts of an aqueous solution containing 797 parts of the sodium salt of compound 1, and where the pH of the solution is adjusted to 7 using aqueous sodium hydroxide. The reaction is allowed to proceed for 6 hours while the temperature is kept at 25° C by external cooling and at pH 7 by the addition of a 50% aqueous sodium hydroxide solution if necessary. ;During the reaction, a separate phase of compound 3 is formed. ;When the reaction is almost complete, the stirring is stopped and the layers are allowed to separate. The upper layer of compound 3 is removed and the lower aqueous layer is extracted with 2000 parts of toluene. The upper layer and the extract are added to 3300 parts of a stirred solution containing 920 parts of dimethylammonium sulphate in a vessel equipped for removing the solvent. The resulting mixture is heated to 90° C. and placed under vacuum to remove toluene by azeotropic distillation. For the distillation, 1 hour is allowed and the reaction is continued for a further 5 hours at 90° C, after which the reaction mass is cooled to 30° C. ;The above-mentioned solution (3440 parts) was analyzed for dimethylamine and compound 3 by means of gas chromatography and was found to contain 264 parts of dimethylamine and 625 parts of compound 5 (R 3 = R 4 = CH 3 ). The solution is introduced into a stirred vessel together with a 50% aqueous sodium hydroxide solution at a rate corresponding to 28.6 parts of the solution and 6.04 parts of a 50% aqueous sodium hydroxide solution per my. (This amount of sodium hydroxide liberates compounds k and 5 from their salts, R3= R4= CH3.) The residence time in this vessel is 2 min. The effluent from this vessel is led to the top of a packed column which is operated at 100 mm Hg absolute pressure with total removal. Steam at atmospheric pressure is introduced into the bottom of the column at such a rate that the volume of water distilling above is 5 parts/min. The stripped solution emerging from the bottom of the column (into a vessel containing 800 parts water) is continuously neutralized to pH 6.5 with concentrated sulfuric acid and cooled to 30° C by external cooling. When the distillation is complete, the vacuum is broken and 4700 parts of toluene and 470 parts of cyclohexyl isocyanate (approx. 90% of the theoretical amount) are added to the neutralized bottom fractions and 50% aqueous sodium hydroxide solution, corresponding to the amount of sulfuric acid used for neutralizing the bottom fractions , is added over the course of 30 minutes, while the temperature is kept at 30° C by external cooling. ;The reaction is allowed to proceed for a further 3 hours until the pH value becomes almost constant at 8.8. The temperature is set to 34° C and held at this temperature for 10 minutes, after which the agitator is switched off and the layers are allowed to separate. The lower aqueous layer is removed and the toluene layer is distilled at 100 mm Hg until a clear distillate is obtained. ;Dimethylamine (375 parts) is injected into the residue while the temperature is kept at 25° C by external cooling. 15.9 parts of a 24% solution of sodium methoxide in methanol are then added with good stirring. The reaction is slightly exothermic and the temperature rises within 15 min to 35° C. The reaction is allowed to proceed for a further 30 min. The solution is then concentrated at 100 mm Hg until 4000 parts of toluene have been removed. Water (1900 parts) is added and distillation continues until the removal of toluene is complete. Distilled water is returned to the still via a water separator. The residue is cooled to 15° C and stirred until precipitation of the product is complete. The solids are collected by filtration and dried, thereby obtaining 745 parts (45.3% calculated on compound 1) of compound 9 (R-^ = cyclohexyl, R^= R^ = ;methyl), m.p. 97 - 100.5° C. ;The aqueous filtrate can be recycled to reduce the loss ;of product 9. ;An alternative isolation method for compound 9 from the aqueous solution is as follows: The aqueous residue from the distillation is heated to 60° C. This results in the formation of a two-phase system, and the lower organic layer is separated from the upper aqueous layer. The organic phase amounts to 1070 parts and contains 762 parts of compound 9. The aqueous phase contains 77 parts of compound 9 and can be recycled back to the still to achieve a higher overall recovery. The following s-triazinediones are prepared by cyclization of the appropriate methyl-N-(N-substituted carbamoyl or thiocarbamoyl-N',N'-dialkylamidino)-N-alkylcarbamate, by the method shown above. ;Table III ;1-methyl-3-cyclopentyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 126 - 129 C; 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-4-thio-2,4-(1H,3H)-dione, m.p. 210 - 212° C; 1-methyl-3-(p-fluorophenyl)-6-dimethylamino-s-triazine-4-thio-2,4-(1H,3H)-dione, m.p. 224 - 226° C; 1-methyl-3-(m-fluorophenyl)-6-dimethylamine 6-s-triazine-4-thio-2,4-(1H,3H)-dione, m.p. 204 - 206° C;E. Alternative procedure for the preparation of methyl-N-(N-cyclo-hexylcarbamoyl-N<1>,N'-dimethylamidino)-N-methylcarbamate (Equation C); A solution of the sulfate salt of 5/ as prepared in example ID, is mixed with 4700 parts of toluene and 470 parts of cyclohexyl isocyanate are added over the course of 2 hours, while the pH is kept at 9.5 by continuous addition of a 50% aqueous solution of sodium hydroxide. The sodium hydroxide addition is continued for another 3 hours until the pH remains constant at 9.5. ;The temperature is kept at 30° C during the entire reaction time. The reaction mixture is worked up as indicated in example ID to give methyl-N-(N-cyclohexylcarbamoyl-N<1>,N<1->dimethylamidino)-N-methylcarbamate with approximately the same yield. The reaction equations Cb and Db describe how the compounds according to the invention are prepared when X is sulphur. ;Reaction equation cb: The methoxycarbonylguanidine derivative 5b is reacted with an isothiocyanate (10) in an inert solvent (such as tetrahydrofuran) at a temperature from room temperature to 100°C during 1 - 12 hours to obtain methoxycarbonylallophanimidate 11. This intermediate can is isolated by evaporation of the solvent and further purified, if desired, by recrystallization, or the intermediate product can be used directly without isolation in the next step (Db). ;Reaction Equation Db: Methoxycarbonylallopanimidate 11, in an inert solvent (such as toluene) is treated with an alkali metal alkoxide or hydroxide (such as methoxy or hydroxide of sodium or potassium) and the mixture is heated to promote cyclization of compound 11 to triaizin-4-thione 12. Compound 12 can also be isolated by cooling the reaction mixture and filtering off the precipitated compound 12. If desired, 12 can be further purified by recrystallization from an inert solvent (such as ethyl acetate). ;Example 2 ;Preparation of 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-4-thio-2,4(1H,3H)-dione;A mixture of 100 parts of N-methoxycarbonyl-N,N' N'-trimethylguanidine, as prepared according to IB, 89 parts of cyclohexyl isothiocyanate and 0.5 parts of dibutyltin dilaurate are heated for 8 hours at 70° C. in 1000 parts of toluene. The clear, yellow solution is heated to the reflux temperature and 50 parts of toluene are distilled off. A 12.5 aliquot portion of 0.5 M sodium methoxide in methanol solution is added over the course of 30 min, during which time toluene is allowed to distill from the reaction mixture. After the addition is complete, additional toluene is distilled off until 500 parts of toluene have been removed. The reaction mixture is cooled and the resulting light yellow product, 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-4-thio-2,4(1H,3H)-dione, is crystallized. Filtration and drying give 113 parts of the product, m.p. 210 - 212° C. ;The intermediate methyl-N-(N-cyclohexylthiocarbamyl-N',N1 - dimethylamidino)-N-methylcarbamate can be isolated by removing toluene under reduced pressure and obtaining the impure solid from ethyl acetate, which gives the purified intermediate , sm.p. 122 - 123° C. In certain cases it is not necessary to add the base (sodium methoxide) to promote cyclization, for example to the first two triazine-4-thiones given in the following list. Similarly, the following compounds can be prepared using suitable reactants. ;Table IV ;1-methyl-3-ethyl-6-dimethylamino-s-triazine-4-thio-2,4-(1H,3H)-dione, m.p. 139 - 140° C; 1-methyl-3-(n-butyl)-6-dimethylamino-s-triazine-4-thio-2,4-(1H,3H)-dione, m.p. 124 - 126° C; 1-methyl-3-phenyl-6-dimethylamino-s-triazine-4-thio-2,4-(1H,3H)-dione, m.p. 209 - 211° C; 1-methyl-3-(o-fluorophenyl)-6-dimethylamino-s-triazine-4-thio-2,4-(1H,3H)-dione, m.p. 220 - 221° C; 1-methyl-3-(m-fluorophenyl)-6-dimethylamino-s-triazine-4-thio-2,4-(1H,3H)-dione, m.p. 204 - 206° C; 1-methyl-3-(p-fluorophenyl)-6-dimethylamino-s-triazine-4-chloro-2,4-(1H,3H)-dione, m.p. 224 - 226° C ; In an alternative method for producing the compounds according to the present invention, a 2-methyl-2-thiopseudourea salt, such as the sulfate or the hydrochloride, is used as starting material. A schematic representation of this method is shown using the reaction equations E - K.; wherein: ;<R>2' R-j,<R>4, R, M<1>and Z have the previously indicated meanings. A suspension or solution of compound 14 is prepared in the chosen solvent and treated with methyl chloroformate (reaction equation E) or an isocyanate of formula R-^CO (reaction equation E) until the reaction is complete. The product obtained, a l-carbomethoxy-2-methyl-2-thiopseudourea (compound 15) or a l-cyclohexyl-4-methyl-4-thiopseudobiuret (compound 15a) is treated with an isocyanate of the formula R-^NCO (reaction equation F ) or methyl chloroformate (reaction equation Fa) to obtain compound 16. A solution of compound 16, in a suitable solvent, is treated with an alkali metal alkoxide to give the salt 17 (reaction equation G). A solution or suspension of compound 17, in the chosen solvent, is reacted with an alkylating agent to give compound 18 (reaction equation h). A suspension or solution of compound 18, in the chosen solvent, is treated with an amine (4) to give compound 9. The product obtained, an s-triazine-2,4(1H,3H)-dione, can isolated by conventional techniques is described above in connection with the discussion of reaction equation D. The solvents that can be used in these reactions are water, toluene, benzene, xylene, monochlorobenzene, nitrobenzene, methylene chloride, triolene, perclene or mixtures of these organic solvents with water, i.e. the solvent need not be anhydrous. With the above solvents it is practical to use a ratio of compound 14 to solvent of 1:3 to 1:10, preferably 1:3 to 1:6. The most preferred among this group of solvents are water, toluene, xylene and benzene due to their low price and applicability for use in the method in this process. The most preferred solvent for this reaction according to reaction equation E is water. Mixtures of water and the previously mentioned organic solvents can be used. With the above-mentioned solvents, it is practical to use a water/organic solvent ratio of 1:1 to 1:6, most preferably 1:1 to 1:2. The two-solvent system is most preferred for the reaction according to reaction equation Ea because the isocyanate 6 reacts with water to form unwanted by-products. The yield of product 15a from isocyanate can be seriously reduced by these side reactions. The ratios between compounds 14:2 and 14:8 can be varied from 1:0.1 to 1:3, preferably from 1:0.8 to 1:2, most preferred is 1:1 to 1:1.3. ;The reactions E and Ea can be carried out at a temperature from -10° C to 50° C, preferably at 0 - 30° C and most preferably in the range 0 - 25° C. The pH in the reactions E, Ea and Fa can preferably be varied from 6.5 to 11 and more preferably in the range 7 - 8.5. The order of addition of the reactants methyl chloroformate and the isocyanate R-^NCO versus addition of the aqueous base can be varied. The methyl chloroformate or isocyanate may be added first, followed by the aqueous base. But most preferred is the simultaneous addition of methyl chloroformate or isocyanate and the aqueous base. The base can be chosen from lithium, sodium and calcium hydroxide. The concentration of added bases can be varied from 10 - 50%, but a higher concentration of the base is preferred due to the low reaction volume for a given amount of product. This simultaneous addition of methyl chloroformate or the isocyanate R^NCO and the 50% aqueous base gives a higher yield of product 15 or 15a due to the controlled pH conditions and the reduced contact time with water required for a complete reaction. ;Reactions F and Fa are preferably carried out at 0 - 50° C and more preferably at 15 - 35° C. ;The ratio of methyl chloroformate to 15a can be 1:1 to 4:1, preferably 1.5:1 to 3:1, most preferably 2:1 to 2.5:1. The ratio of the isocyanate of 15 is preferably 1:1.1 to 1:1.5 and most preferably 1:1.05 to 1:1.15, in order to achieve a high percentage conversion of the ratio 15 to the compound 16 without the use of no excess of isocyanate or long reaction time necessary. The required reaction time for an almost complete conversion is preferably 0.5 - 12 hours for both reaction equations Ea and Fa and more preferably 1-4 hours. The reaction time depends on the nature and amount of solvent and reactants, temperature and the type of mixing used. The reaction time required for the addition of methyl chloroformate or isocyanate is not critical and can be varied within the range of 0.1 - 10 hours, preferably within the range of 0.1 - 4 hours and most preferably within the range of 0.25 - 1.5 hours. Compound 16 is preferably treated with 0.6 - 1.3 equivalents of alkali metal alkoxide and more preferably with 0.9 - 1.1 equivalents. The alkoxide can be used as the pure base or preferably as a solution in a suitable solvent and most preferably as a 15-35% solution in the corresponding alcohol. The solution of compound 16 can be cyclized to compound 17 using an alkali metal hydroxide, but an alcoholic solvent must be added to dissolve the hydroxide before cyclization takes place. ;The cyclization of compound 16 to compound 17 (reaction equation G) is preferably carried out at 25 - 70° C, but most preferred is 45 - 70° C. ;The removal of the solvent to give a suspension ;of compound 17 can be carried out under reduced pressure or atmospheric pressure at a temperature of 20 - 135° C, but most preferably at 25 - 50° C under reduced pressure and at 65 - 100° C at atmospheric pressure. The alkylation of the compound -17 (reaction equation H) with the alkylating agent 2 (Z = halogen, alkyl sulfate) can be carried out in a solvent such as water, toluene, benzene, xylene, chlorobenzene, nitrobenzene, acetonitrile, triolene or perclene. The preferred solvent is water because of the low price, simplicity of the manufacturing operation and the easy isolation of the product 18. The product can in this case be isolated by filtration and drying or it can be used directly as a wet dry substance in the next reaction by the suspension in an organic solvent and removal of water by azeotropic distillation.; In the case where a dialkyl sulfate is used to alkylate compound 17, the pH of the aqueous solution or suspension should preferably be kept at 7 - 11.5 and more preferably at 9 - 10.5*, to avoid acidification of compound 17 to give compound 18 where R 2 is H.

The ratio of alkylating agent to compound 17 is preferably 0.8:1 to 1.5:1, but most preferably 1.1 to 1.3:1. The reaction can be carried out at a temperature of 15 - 135° C, if it is carried out in an organic solvent and preferably at 25 - 80° C.

When water is used as solvent, the preferred temperature range is 15 - 80° C and the most preferred is 25 - 40° C.

The conversion of 6-methylthio-s-triazine-2,4-(1H,3H)-dione (compound 18) to the 6-amino-s-triazine-2,4(1H,3H)-dione 9 can preferably be carried out in a solvent selected from toluene, xylene, benzene, monochlorobenzene, triolene, perclene, nitrobenzene, methylene chloride and 1,2-dichloroethane. The most preferred solvent is toluene.

The preferred ratio of compound 18 to the amine is preferably 1:1 to 1:6 and more preferably, due to the complete conversion of 9 and the required shorter reaction time, is 1:2 to 1:3. In special cases, the amine can be used as a solvent.

The conversion of compound .18 to compound 9 can be carried out at a temperature in the range 5 - 135° C, but more preferably in the range 25 - 60° C.

The following examples illustrate the methods according to the reaction equations E - K.

Example 3

A. Preparation of methyl-N-(1-amino-l-methylthiomethylene)-carbamate ( Reaction equation B )

To a solution of 69.5 parts of 2-methyl-2-thiopseudourea sulfate and 47 parts of methyl chloroformate in 1000 parts of water at 0° C, 56.9 parts of potassium hydroxide in 200 parts of water are added dropwise. The reaction mixture is stirred at room temperature for 3 hours and extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated in a rotary evaporator to give 45 parts of methyl N-(1-amino-1-methylthiomethylene)-carbamate, m.p. 72 - 77° C.

B. Preparation of methyl-4-isopropyl-N-methoxycarbonyl-l-thio-allofanimidate (Reaction equation 7) 74 parts of methyl-N-(1-amino-1-methylthiomethylene)-carbamate and 47 parts of isopropyl isocyanate in 300 parts of methylene chloride are stirred over the night. The solvent is evaporated in a rotary evaporator to give 113.6 parts of methyl 4-isopropyl-N-methoxycarbonyl-1-thio-allophanimidate, m.p. 129 - 132° C.

In a similar manner, compounds are prepared as indicated in Table V

Table V

methyl 4-cyclohexyl-N-methoxycarbonyl-1-thioallofanimidate,

sm.p. 85 - 86° C

methyl 4-(p-chlorophenyl)-N-methoxycarbonyl-1-thioallophanimidate,

sm.p. 127 - 128° C

methyl 4-(3-chlorocyclobutyl)-N-methoxycarbonyl-1-thioallophanimidate, m.p. 173 - 174.5° C

methyl-4-cyclohexylmethyl-N-methoxycarbonyl-1-thioalphanimidate, m.p. 132 - 134°C

C. Preparation of 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione (Reaction Equations G and J)

100 parts of methyl-4-isopropyl-N-methoxycarbonyl-1-thialo-phanimidate are refluxed for 1 hour with 27 parts of sodium methoxide in 200 parts of methanol. The methanol is distilled off in a rotary evaporator and the residue is dissolved in 200 parts of water. The aqueous solution is neutralized with hydrochloric acid and the dry matter is filtered off and dried to give 55 parts of 3-isopropyl-6-methylthio-s-triazine-2,4-(1H,3H)-dione, m.p. 188 - 190° C.

By the method shown above, the appropriate thioallophanimidate can be cyclized to the triazinediones indicated below.

Table VI

3-cyclohexyl-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 255 - 257° C

3-cyclopentyl-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 201 - 204° C

3-(p-Chlorophenyl)-6-methylthid-s-triazine-2,4(1H,3H)-dione,

sm.p. 292 - 295° C

3-(m-chlorophenyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 192 - 195.5° C

3-phenyl-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 235 - 245° C

3-(3-chlorocyclobutyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 167 - 169° C

3-(1-methylcyclopentyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione, m.p. 192 - 195.5° C

3-cyclohexylmethyl-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 177.5 - 178° C

D. Preparation of l-methyl-3-isopropyc-6-methylthio-s-triazine-2, 4(1H,3H)-dione (Reaction equation H)

To a solution of 32 parts of sodium methoxide in 400 parts of methanol, 132 parts of 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione are added. The solution is evaporated under vacuum and the white solid triturated with methylene chloride and filtered to give 110 parts of sodium 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione, m.p. about. 300° C. 80 parts of sodium 3-isopropyl-6-methylthio-s-triazine-2,4-(1H,3H)-dione and 49 parts of methyl iodide are refluxed overnight in 700 parts of acetonitrile. The solvent is evaporated and the residue is dissolved in methylene chloride. The methylene chloride solution is washed with water, dried and evaporated to give after recrystallization from 1-chlorobutane: Hexane 54 parts 1-methyl-3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione, sm. p. 74 - 77° C.

By the above procedure and using the appropriate 6-methylthio-s-triazinedione, a number of compounds can be prepared, as illustrated below.

Table VII

1-methyl-3-cyclopentyl-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 80 - 83° C

1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 135 - 137° C

1-methyl-3-(2-methylcyclohexyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione, m.p. 98 - 100° C

1-methyl-3-(3-methylcyclohexyl)-6-methylthio-s-triazine-2,4(1H-3H)-25

dione, nQ 1.5372

1-methyl-3-cyclopehtyl-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 98 - 101° C

1-methyl-3-(1-methylcyclopentyl)-6-methylthio-s-triazine-2,4-(1H,3H)-dione, m.p. 84 - 86° C

1-methyl-3-cyclohexylmethyl-6-methylthio-s-triazine-2,4(1H,3H)-dione,

dion, sm.p. 102.5 - 104°C

1-methyl-3-phenyl-6-methylthio-s-triazine-2.4(1H,3H)-dione,

sm.p. 232.5 - 233° C

1-methyl-3-(p-chlorophenyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione, m.p. 146.5 - 148.5° C

1-methyl-3-(m-chlorophenyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione,

sm.p. 297 - 297.5° C

1-Methy]-3-(3,5-dimethylcyclohexyl)-6-methylthio-s-triazine-2,4~

(1H,3H)-dione, n^<5>1.5400

1-methyl-3-(p-methylthiophenyl)-6-methylthio-s-triazine-2,4-(1H,3H)-dione, m.p. 193 - 195° C

E. Preparation of 3-isopropyl-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione

(Reaction equation K)

10 parts of 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione, 10 parts of dimethylamine and 50 parts of dioxane are heated in a bomb at 150° C. for 3 hours. The reaction mixture is cooled and filtered to give 5 parts of a crude solid after filtration. The crude product is recrystallized from acetonitrile to give 2 parts of dimethylammonium-3-isopropyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 213 - 215° C. 2 parts of the salt obtained above are added to 10 parts IN hydrochloric acid. The solution is extracted with chloroform and the chloroform extract is dried and evaporated to give 1 part of 3-isopropyl-6-dimethyl-amino-s-triazine-2,4(1H,3H)-dione, m.p. 213 - 214° C.

F. Preparation of sodium 3-isopropyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione

To 6 parts of sodium methoxide in 60 parts of methanol, 20 parts of 3-isopropyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione are added. The solution is stripped and the residue triturated with ether to give, after filtration, 18 parts of sodium 3-isopropyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. above 300°C.

Using the method given above, 6-alkylamino-s-triazines and their salts can be prepared. Some examples are as follows.

Example VIII

3-cyclohexyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 279° C (decomposition)

3-(tert-butyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 206 - 209° C

3-(sec,-butyl)-6-methylanino-s-triazin-2,4(1H,3H)-dione,

sm.p. 161 - 164° C

3-(p-chlorophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 265 - 267° C

3-(3-pentyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 148 - 151° C

3-(3,4-dimethylcyclohexyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 234 - 237° C

3-(4-tert-butylcyclohexyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 283 - 283°C

3-isopropyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 213 - 214°C

3-isopropyl1-6-dimethylamino-s-triazine-2,4(1H,3H)-dione-dimethyl1 -

amine salt, m.p. 213 - 215 C

3-isopropyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione lithium salt, m.p. >300°C

3-isopropyl-6-methylamino-s-triazine-2,4(1H,3H)-dione-^-calcium salt,

sm.p. > 300°C

3-isopropyl-6-methylamino-s-triazine-2,4(1H,3H)-dione sodium salt.

sm.p. > 300°C

G. Preparation of J.-Methyl-3-isopropyl-6-dimethylamino-s-triaziB_2 4{1H>3H)-dione

(Reak's ionic equation

A solution of 10 parts of 1-methyl-3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione in 100 parts of tetrahydrofuran at 0° C. is saturated with dimethylamine. The reaction is allowed to proceed until heating at room temperature and allowed to stand overnight. The solvent is evaporated and the residue triturated with ether to give 9 parts of 1-methyl-3-isopropyl-6-dimethylamino-s-triazine-2,4dH,3H)-dione, m.p. 104 - 106° C.

Example 4

Modified route for compounds with a bulky group in the 3-position (R-^ in formula I) using methyl chlorothioformate

l-methyl-3-(tert-butyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione ( Reaction equations Ea, Fa (modified), G, H, I)

To a solution of 278 parts of 2-methyl-2-thiopseudourea sulfate in 2000 parts of 50% aqueous methanol at 0° C, 176 parts of a 50% sodium hydroxide solution are added dropwise, followed by 180 parts of tert-butyl isocyanate in 4 00 parts tetrahydrofuran. The solution is partially evaporated in a rotary evaporator and the resulting suspension is filtered to give, after drying, 180 parts of methyl 4-(tert-butyl)-1-thioallophanimidate, m.p. 102 - 104° C.

To a solution of 113.4 parts of the above-mentioned compound and 80 parts of triethylamine in 1000 parts of methylene chloride at 0° C, 66 parts of methylchlorothiolformate in 100 parts of methylene chloride are added dropwise. The solution is stirred overnight, washed once with water, dried and evaporated to give 76 parts of methyl 4-(tert-butyl)-N-methylthiolcarbonyl-1-thioallophanimidate, m.p. 102 - 105° C. 50 parts of the above-mentioned compound are refluxed for 1 hour with 30 parts of sodium methoxide in 500 parts of methanol. The reaction mixture is cooled and the methanol is distilled off in a rotary evaporator. The residue is washed with ether to give 30 parts of sodium 3-(tert-butyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione. 24 parts of sodium 3-(tert-butyl)-6-methyl-thio-s-triazine-2,4(1H-3H)-dione and 15.5 parts of methyl iodide are refluxed overnight in 200 parts of acetonitrile. The solvent is evaporated and the residue is dissolved in methylene chloride. The methylene chloride solution is washed with water, dried and evaporated whereby, after recrystallization from 1-chlorobutane, 15 parts of 1-methyl-3-(tert-butyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione are obtained , sm.p. 138 - 140° C.

A solution of 5 parts of the above-mentioned compound in 50 parts of tetrahydrofuran at 0° C. is saturated with dimethylamine. The reaction is allowed to proceed until heating to room temperature and allowed to stand overnight. The solvent is evaporated and the residue triturated with ether to give 4 parts of 1-methyl-3-(tert-butyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 161 - 163° C.

Example 5

A. Preparation of 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2',4(1H,3H)-dione

(The reaction equations E, F, G, H)

To a solution of 56 parts of 2-methyl-2-thiopseudourea sulfate in 300 parts of water at 0° C, 37.5 parts of methyl chloroformate and 62 parts of a 50% aqueous sodium hydroxide solution are added dropwise at the same time. The methyl chloroformate is added over 0.5 hours and the 50% aqueous sodium hydroxide solution as needed to keep the pH of the reaction mixture at 8.5. After complete addition, the reaction mixture is brought to the ambient temperature (25 - 28° C) and kept at this temperature for 2 hours.

300 parts of toluene are added to this suspension of 1-carbomethoxy-2-methyl-2-thio-pseudourea at 25 - 28° C. Cyclohexyl isocyanate (44 parts) is added over the course of 30 minutes and the reaction mixture is stirred at 25 - 30° C. for a further 2 hours. The toluene layer is then separated and 76 parts of a 25% sodium methoxy solution are added. The solution is then boiled under reflux for 1 hour (65 - 70° C) and the methanol-toluene mixture is distilled off until the temperature in the distillation vessel reaches 88 - 90° C.

This toluene slurry of the sodium salt of 3-cyclohexyl-6-methylthio-s-triazine-2,4(1H,3H)-dione is stirred with 650 parts of water for 0.15 hours. The aqueous layer is separated and reacted at 25 - 30° C, during 15 minutes, with 57 parts of dimethylsulphate. After adding the dimethylsulphate, the pH of the reaction mixture is kept at 9-9.5 by adding a total of 7.5 parts of 50% aqueous sodium hydroxide solution. The total reaction time is 1.8 hours, at which time filtration and drying give 70 parts of white 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4(1H,3H)-dione, m.p. . 137 - 139° C.

B. Preparation of 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4(1H,3H)-dione

(The reaction equations Ea, Fa, G, H)

To a solution of 70 parts of 2-methyl-2-thiopseudourea sulfate in 375 parts of water and 400 parts of toluene at 10° C, 62.5 parts of cyclohexyl isocyanate are added over the course of 1 hour. The pH of the mixture is kept at 8.5 by adding 80 divides 50% aqueous sodium hydroxide solution within 1 - 1.5 hours. The formed two-phase system is reacted with 99 parts of methyl chloroformate and 84 parts of a 50% aqueous sodium hydroxide solution over the course of 1 hour. The temperature is kept at 25 - 30° C. After complete addition, the reaction mixture is stirred at 25 - 28° C for a further 3 hours. The toluene layer is separated and treated as indicated in Example 5A for. to give 76 parts of 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4-(1H,3H)-dione, m.p. 136 - 138° C.

C. Preparation of 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione

(Reaction equation I)

A suspension of 300 parts of 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4(1H,3H)-dione in 887 parts of toluene is stirred at 25 - 30° C. for 3 hours with 150 parts of dimethylamine. The toluene is distilled off from the reaction mixture until the temperature in the distillation vessel reaches 125° C. The reaction mixture is cooled to 50° C, at which point 480 parts of hexane are added over the course of 0.66 hours. The resulting suspension is filtered at 25°C to give 282 parts of crystalline 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 110 - 115° C.

The following aminotriazinediones can be prepared by the methods of Examples 3, 4 and 5 using suitable reactants.

Table IX

1-methyl-3-ethyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 104 - 106° C

1-methyl-3-propyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 106 - 109° C

1-methyl-3-isopropyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 104 - 106° C

1-methyl-3-isobutyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 87 - 89° C

1-methyl-3-(2-cyclopenten-1-ylmethyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione

1-methyl-3-butyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 63 - 65° C

1-methyl-3-(sec-butyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

25

sm.p. nQ 1.5198

1-methyl-3-isobutyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 87 - 89° C

1-methyl-3-(tert-butyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 161 - 163° C

1-methyl-3-neopentyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 141 - 144° C

1-methyl-3-hexyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

25

n" 1.5130

1-methyl-3-allyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 74 - 75° C

1-methyl-3-(3,4-dichlorophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 211 - 212° C

1-methyl-3-(2,5-dichlorophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 191 - 194° C

1-methyl-3-(p-chlorophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 238 - 239° C

1-methyl-3-(m-chlorophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione m.p. 141 - 143° C

1-methyl-3-(o-chlorophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 205 - 207° C

1-methyl-3-(m-fluorophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 157 - 159° C

1-methyl-3-(o-fluorophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 179 - 182° C

l-methyl-3-(p-fluorophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione l-methyl-3-(3-chloro-6-methylphenyl)-6-dimethylamine- s-triazine-2,4-(1H,3H)-dione, sm.-. 155 - 157° C

1-methyl-3-(3-chloro-4-methylphenyl)-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 189.5 - 190.5° C

1-methyl-3-(m-(trifluoromethyl)-phenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 144 - 148° C

1-methyl-3-(m-nitrophenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 207 - 209° C

1-methyl-3-phenyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 208 - 210° C

1-methyl-3-(m-tolyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 159 - 162° C

1-methyl-3-(p-tolyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 237 - 240° C

1-methyl-3-(p-isopropylphenyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 18§ - 191° c

1-methyl-3-(3-chloro-4-methylphenyl)-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 189.5 - 190.5° C

1-methyl-3-(1-methylcyclopentyl)-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 104 - 106° C

1-methyl-3-cyclopentyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 126 - 129° C

1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 101.5 - 104° C

1-methyl-3-(2-methylcyclohexyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 125 - 126.5° C

1-methyl-3-(3-methylcyclohexyl)-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 91 - 93° C

1-methyl-3-(2,4-dimethylcyclohexyl)-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 120 - 122°C.

1-methyl-3-(3,4-dimethylcyclohexyl)-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione, 25. 1.5288

nD

1-methyl-3-(2,6-dimethylcyclohexyl)-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione, n^<5>1.5244

1-methyl-3-(2,3-dimethylcyclohexyl)-6-dimethyl-s-triazine-2,4-(1H,3H)-dione, n^<5>1.5283

1-methyl-3-(4-methoxycyclohexyl)-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione, n^<5>1.5305

1-methyl-3-cycloheptyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 116 - 118° C

1-methyl-3-cyclooctyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 133 - 133.5° C 1-methyl-3-(3-chlorocyclobutyl)-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, m.p. 160°C

1-methyl-3-(4-isopropylcyclohexyl)-6-dimethylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 128 - 130° C

1-ethyl-3-isopropyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, sm.p. 63 - 65° C l-propyl-3-isopropyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, n^<5>1.5056 l-ethyl-3-cyclohexyl-6- dimethylamineb-s-triazine-2,4(1H,3H)-dione,

n£<5>1.5279

1-methyl-3-ethyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 206 - 207° C

1-methyl-3-(sec-butyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 199 - 200° C

1-methyl-3-(tert-butyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 235 - 235.5° C

1-methyl-3-phenyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 293 - 296° C

1-methyl-3-(p-chlorophenyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. >300°C

1-methyl-3-(3,4-dichlorophenyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione, m.p. >300°C

1-methyl-3-(o-chlorophenyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. >300°C

1-methyl-3-(o-fluorophenyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. >300 C

1-methyl-3-(m-nitrophenyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. >300°C

1-methyl-3-(m-trifluoromethylphenyl)-6-methylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 141 - 243° C

1-methyl-3-isopropyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 223 - 224 C

1-ethyl-3-isopropyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 240 - 241° C

1-propyl-3-isopropyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 166 - 167° C 1-propyl-3-(p-chlorophenyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 261 - 263° C

1-methyl-3-cycloheptyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 273 - 274° C

1-methyl-3-cyclopentyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 220 - 221.5° C

1-methyl-3-cyclooctyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. >300°C

1-methyl-3-(2-methylcyclohexyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione, m.p. 246 - 248.5° C

1-methyl-3-ne6pentyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 253 - 255° C

1-ethyl-3-cyclohexyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 226 - 227° C

1-methyl-3-(3-methylcyclohexyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione, m.p. 255 - 258° C

1-methyl-3-(m-tolyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 280 - 282° C

1-methyl-3-(3-chloro-p-tolyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione, m.p. 321.5 - 322.5° C

1-methyl-3-(2-methyl-5-chlorophenyl)-6-methylamino-s-triazine-2,4(1H-3H)-dione, m.p. 268 - 270° C

1-methyl-3-(3-pentyl)-6-methylamino-s-triazine-2,4(1H-3H)-dione,

sm.p. 179 - 182° C

1-methyl-3-(3,4-dimethylcyclohexyl)-6-methylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 295 - 298° C

1-methyl-3-(p-isopropylphenyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione, m.p. 284 - 286° C

1-methyl-3-(2,3-dimethylcyclohexyl)-6-methylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 223 - 225° C

1-methyl-3-(2,4-dimethylcyclohexyl)-6-methylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 214 - 216° C

1-methyl-3-(4-isopropylcyclohexyl)-6-methylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 298 - 300° C

1-methyl-3-(3,5-dimethylcyclohexyl)-6-methylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 250 - 252° C

1-methyl-3-(1-methylcyclopentyl)-6-methylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 236 - 238° C

1-methyl-3-(3-chlorocyclobutyl)-6-methylamino-s-triazine-2,4-(1H,3H)-dione, m.p. 235 - .236° C

1-methyl-3-octyl-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 89 - 91° C

1-methyl-3-(p-methylthiophenyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione, m.p. 314 - 317° C

1-methyl-3-(2-methyl-4-chlorophenyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione, m.p. 293 - 295° C

1-methyl-3-(p-tolyl)-6-methylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 237 - 2400c

1-methyl-3-isobutyl-6-methylamino-s-triazine-2,4(1h,3H)-dione,

m.p. 206-209° C

1-methyl-3-cyclohexyl-6-ethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 209 - 211° C

1-methyl-3-cyclohexyl-6-isopropylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 213 - 215° C

1-methyl-3-ethyl-6-tert. -butylamino!)-s-triazine-2,4(1H,3H)-dione,

sm.p. 182 - 183.5° C

1-methyl-1-3-isopropyl-6-isopropylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 181 - 184° C

1-methyl-3-isopropyl-6-propylamino-s-triazine-2,4(1H-3H)-dione,

sm.p. 158 - 161° C

1-methyl-3-isopropyl-6-(tert-butylamino)-s-triazine-2,4(1H,3H)-dione,

sm.p. 185 - 186.5° C

1-methyl-3-isopropyl-6-allylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 143.5 - 145° C

1-methyl-3-isopropyl-6-propargylamino-s-triazine-2,4(1H,3H)-dione,

n^<5>1.5520

1-ethyl-3-isopropyl-6-ethylamino-s-triazine-2,4(1H,3H)-dione,

sm.p. 170 - 173° C

1-methyl-3-isopropyl-6-diethylamino-s-triazine-2,4(1H,3H)-dione,

N^5 1.5129

1-methyl-3-isopropyl-6-(N-butyl-N-methylamino)-s-triazine-2,4(1H,3H)-dione, N^<5>1.5182

1-raethyl-3-cyclohexyl-6-(N-methyl-N-propylamino)-s-triazine-2,4-(1H,3H)-dioneN^<5>1.5335

An alternative method for the preparation of the compounds according to the present invention, where X is sulphur, is shown by reaction equation L:

(compound 9 where R3 is alkyl)

where Rlfog R^ have the previously indicated meanings.

s-triazine-4-thio-2,4(1H,3H)-dione 12 can be prepared by heating the corresponding oxygen analogues 9b with phosphorus pentasulfide at 25 - 150° C for 1 - 12 hours in a solvent such as pyridine or picoline. The product can be isolated by diluting the reaction mixture with a suitable hydrocarbon solvent (such as toluene) and separating the solids (for example by filtration) and further extracting the solid with a hydrocarbon solvent, followed by crystallization of the product from the hydrocarbon solvent extracts, or the reaction mixture can be treated with water and the product extracted and crystallized as above indicated.

The following examples and table X illustrate this procedure.

Example 6

Preparation of l-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-4-thio-2,4(1H,3H)-dione

To 25 parts of 1-methyl-3-cyclohexyl-6-dimethylamino-s-trizine-2,4(1H,3H)-dione in 200 parts of pyridine, 45 parts of phosphorus pentasulphide are added. The mixture is boiled under reflux for 6 hours below

a nitrogen atmosphere. The hot reaction mixture is diluted with 250 parts of toluene and the supernatant is poured off. The residue is mixed twice with portions of 250 parts of hot toluene and the supernatant liquid is decanted. The combined decanted liquids are evaporated to dryness and extracted with hot toluene. The hot extract is filtered and cooled to give 18 parts of 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-4-thio-2,4(1H,3H)-dione, m.p. 210 - 212° C.

Table X

Similarly, 1-methyl-3-cyclopentyl-6-dimethyl-amino-s-triazine-4-thio-2,4(1H,3H)-dione, m.p. 184.5 - 186°C is produced.

Composition and application of the compounds

The compounds of formula I are useful for controlling unwanted vegetation. They can be used at any time when general weed control is required, such as in industrial areas, in connection with railway lines and in areas adjacent to cultivated fields in agricultural areas.

The exact amount of 6-aminotriazinediones to be used in a given situation will vary according to the particular desired end result, the method used, the soil involved and the plant in question, the composition of the product, method of application, prevailing weather conditions, leaf density and similar factors .

As so many variables come into play, it is not possible to specify an application amount that is suitable for all situations. In general, it can be established that the compounds according to the present invention are used in quantities of 0.5 - 25 kg/hectare.

The compounds according to formula I can be combined with other herbicides and are particularly useful in connection with "bromacil"

(3-(sec-butyl)-5-bromo-6-methyluracil), "diuron" (3-(3,4-dichloro-phenyl)-1,1-dimethylurea), paraquat (1,1'-dimethyl -4,4<1->bipyridinium ion), m-(3,3-dimethylureido)phenyl-tert-butylcarbamate 4-amino-6-tert-butyl-3-methylthio-as-triazine-5(4H )-one and s-triazines such as 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, for controlling a broad spectrum of weeds.

The compounds of formula I can be formulated in various ways conventional for herbicides with similar physical properties. Useful formulations include wettable and soluble powders, suspensions and solutions in solvents and oils, aqueous dispersions, dusts, granules, pills and high concentration compositions. In general, these formulations essentially comprise 1-99% by weight of herbicidally active material (including at least one compound of formula I in a herbicidally effective amount) and at least one of a) approx. 0.1 - 20% by weight of surfactant and b) 5 - 99% by weight of a solid or liquid diluent. More particularly, the different types of compositions will generally contain these components in the following approximate proportions.

The actual percentage ratios that can be obtained with a special compound of formula I will depend on its physical properties.

The method of making and using such herbicidal compositions is described in the following US patents: 3,309,192, 3,235,357, 2,655,445, 2,863,752, 3,079,244, 2,891,855 and 2,642,354.

Many of the compounds according to the present invention exhibit an unusually high water solubility, up to several percent. This offers many advantages, for example when controlling brush and other perennial, perennial weeds. An example of a highly water-soluble compound according to the present invention is 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione, this compound exhibits a solubility in water of approx. .'3.2% at 25° C.

Example 7

Resolution

The ingredients are combined and mixed to give a solution that can be diluted with water for spraying.

Example 8

Wettable powder

These ingredients are carefully mixed and passed through a hammer mill to give particles substantially of a particle size below 100 µm.

The herbicidal activity of the compound according to the present invention was demonstrated in greenhouse experiments. In this experiment, seeds were lost

Digitaria spp., Echinochloa crusgalli, Avena fatua, Cuperus r-otundus, Cassia tora, Ipomoea spp., Brassica spp.., Raphanus spp., Tagetes spp., Rumex crispus and Cyperus rotundus cuttings were planted in a growth medium and retained before germination in two application rates (2.2 and 0.4 4 kg per ha) with chemicals dissolved in a non-phytotoxic solvent. At the same time, Sorghum halepense, with four leaves, Digitaria spp. and Echinochloa crusgalli with three leaves and Cyperus rotundus bled from cuttings with two leaves treated after germination with a dose of 2.2 kg/ha. Treated plants and control plants were kept in the greenhouse for 16 days after which all species were compared with the control plants and visually assessed for the effect of the treatment. A quantitative grading was done on a scale from 0-10, where a grading of 10 means that the plant in question has been completely killed and a grading of 0 means that no damage could be detected.

A qualitative grading (type of damage) was also performed, with the letter "C" indicating chlorosis and the letter "G" indicating growth inhibition. Grading in this test for some of the preferred compounds was as follows:

Claims (3)

1. 6-amino-s-triazinor derivatives with herbicidal action, characterized by the general formula: where R^means alkyl with 2-8 carbon atoms, cycloalkyl with 4-8 carbon atoms, cyclohexenyl, norbornyl, norbornylmethyl, tri-methylcyclohexyl or tetramethylcyclohexyl, or the above-mentioned cycloalkyl groups substituted by one alkyl group with 2-4 carbon atoms, 1-2 raethyl groups or 1-2 chlorine or bromine atoms, or R^ where Q is hydrogen, fluorine, chlorine, bromine, nitro or trifluoromethyl, Y is hydrogen, chlorine or methyl, R 2 is hydr°9ene-methyl or a cation comprising Na<+>, Li<+>, K<+>, (Ca/2) , ammonium or dimethylammonium, R^ is hydrogen or methyl, R^ is alkyl with 1-4 carbon atoms, and X is oxygen or sulphur, with the proviso that when X is sulfur, neither R2 nor R^ is hydrogen. 2. Connection according to claim 1, characterized in that it is 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,4~(1H,3H)-dione 3.Procedure for the preparation of compounds according to claim 1 or 2 with the general formula: where R^means alkyl with 2-8 carbon atoms, cycloalkyl with 4-8 carbon atoms, cyclohexenyl, norbornyl, norbornylmeth hy 1, tri-methylcyclohexyl or tetramethylcyclohexyl, or the above-mentioned cycloalkyl groups substituted with one alkyl group with 2-4 carbon atoms, 1-2 methyl groups or 1-2 chlorine or bromine atoms, or R where Q is hydrogen, fluorine, chlorine, bromine, nitro or trifluoromethyl, Y is hydrogen, chlorine or methyl, Rg is hydrogen or methyl, R^ is alkyl with 1-4 carbon atoms. and X is oxygen or sulphur, with the proviso that when X is sulphur, R^methyl is characterized by the following sequence of steps: A: react a methylating agent of the formula CH^Z, where Z is iodine or -O-SO,,-OCH^, with methoxycarbonylcyanamide to give N-methoxycarbonyl-N-methylcyanamide, B: react the product of step A with an amine of the formula R 3 R 4 , NH where R^ and R^ are as above, to give the compound of the formula: where R^ and R^ are as indicated above, C: react the product of step B with an isocyanate or iso thiocyanate of the formula R^NCX, where and X are as indicated above, to give a compound of the formula: where , R^> and X are as above, and D: treat the product obtained in step C with a base of the formula M'OR, where R is hydrogen or alkyl with 1-4 carbon atoms, and M' is an alkali metal, for cyclization to obtain the desired product.