FI57940B - SAOSOM HERBICIDER ANVAENDBARA 6-AMINO-S-TRIAZINE-2,4- (1H, 3H) DIONER SAMT FOERFARANDE FOER FRAMSTAELLNING AV DESSA - Google Patents

Description

Ι * | £ * »· Ι rBl ANNOUNCEMENT [-πλ, λ jgri [B] (11) utlAqGNIN0S $ kr, ft 5/940 ^ (45) Patent granted 10 11 1900 Patent meddelat ^ (51) K * .ik. Wa.3 o 07 D 251/46, A 01 N 43/64 ENGLISH — F1N LAN D (21) f ***** "*" ** - ρ »· λ« «βιολ ** i66t / T3 (22 ) HakMitapUvt — AMMcnln ^ d ^ 23.05.73 (23) Alkupllvl — GHtlfhuttdag 23.05-73 (41) Tullut Julktokil - ÄMvlt offuncllg 25.11.73

Patantti · Ja rukisterihallltus (44) Nlhtivtktlpanon] a kuL | ulkml »un pvm. -

Patent- oeh registaratyralMn 'Aiwtkan uth «d oeh utUkrifton pubifcund 31.07.80' (32) (33) (31) Pjnrfutty« tuolkuu · —Buglrt prlorltut 2U.05.72 05.0l *. 73, 05.0U.73 USA (US) 2562U9, 3U8321, 3U832U Proven-Styrkt (71) E.I. du Pont de Nemours and Company, Wilmington, Delaware, USA (72) Kang Lin, Newark, Delaware, Joel Benjamin Wommack, Jr., Wilmington, Delaware, Julius Jakob Fuchs, Wilmington, Delaware, USA (US) ( 74) Oy Kolster Ab (54) 6-Amino-s-triazine-2, U- (1H, 3H) -diones useful as herbicides and method for their preparation - Säsom herbieider använd-bara 6-amino-s-triazin-2, U The present invention relates to 6-amino-s-triazine-2, U- (1H, 3H) -diones of the formula R1, which are useful as herbicides.

N 3 5-N

1 6 [l R

0 N ^ 3 r2 \ 2 57940 where R. | represents an alkyl group having 2 to 8 carbon atoms which may be substituted by a methoxy, ethoxy, methylthio or ethylthio group, an alkenyl group having 3 to U carbon atoms, a cycloalkyl group having U to 8 carbon atoms which may be substituted by an alkyl group having 2 to U carbon atoms, With 1 or 2 methyl groups, 1 or 2 chlorine atoms or one bromine atom, a cyclohexenyl, cyclohexylmethyl, trimethylcyclohexyl, tetramethylcyclohexyl or bicycloalkyl group having 7 to 8 carbon atoms, a fluoro-chloro group according to Q, wherein - or a bromine atom, an alkyl group having 1 carbon atom, an alkoxy or alkylthio group having 1 to 2 carbon atoms, or a nitro or trifluoromethyl group, and Y is a hydrogen or chlorine atom or a methyl group, »·« ··· * + + 4 · is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or Na, Li, K, (Ca / 2) +, ammonium and dimethylammonium ion, is a hydrogen atom or a methyl or ethyl group, R 1 is an alkyl group having 1 to U carbon atoms , An alkenyl group containing a 3-U carbon atom, a propargyl or methoxy group, and X is an oxygen or sulfur atom, provided that when X is a sulfur atom, neither of the groups and R 1 is a hydrogen atom.

The invention also relates to a process for the preparation of these compounds. Neumayer et al. list in their article "Pesticides," Chemical Week, April 12 and 26, 1969, commercial and experimental s-triazine herbicides. Among these are two well-known products, atrazine and simazine: C1 Cl

N N

, N N

JL jl / CH I .1

CH3CH2 «N JJCH \ CH CH N ^ N N-CH CH

H H xch3 3 2h h 2 3

Atrazine Simazine 3,57940

U.S. Patent Nos. 3,505,323 and 3,505,057 to Luckenbaugh disclose tetrahydro-s-triazinones of formula A below and their use as herbicides. The German Offenlegungsschrift 1 962 797 describes s-triazinones of formula B below and their use as herbicides.

"Sr \ A. x A

<'N> —N N-R, NN

.'W k J KK

Y R, ^ N / xn-R0 'J H ^

R H

(A) (B) Q = S or 0 X = S or 0 X = halogen R1, R? and R 1 = H or alkyl Y = H, halogen, alkyl, etc. R and R = alkyl n = 1 or 2

Chemische Berichte 10¾ (1971) 1606 relates to the preparation of s-triazine ions by cyclocondensation of ethoxycarbonyl isothiocyanate with amidines, isoureas, isothioureas and guanidines:

S

/ V

HN N

λ Λ

ON "X H

wherein X is, inter alia, (C-H_) ON-, (C_HCHO) ON- or (C

"d? d d p d d Op2

Preferred are those compounds of formula I in which R1 is an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms substituted by one methyl group, R1, and R1 are methyl groups. and X is an oxygen or sulfur atom.

57940 4

Even more preferred are those compounds of formula I having a cyclopentyl, methylcyclopentyl, cyclohexyl or methylcyclohexyl group; lij and are o ethyl groups? and X is an oxygen atom.

Most preferred are the following two compounds: 3-cyclohexyl-1-methyl'-6-dimethylamino-α-triazine-2,4 (1H (1H) -dicin) and 3-cyclopentyl-1-methyl-6-dimethylamino-β-triazine-2 > 4 (lH, 3B) -dione. Manufacture of compounds

The compounds of formula I are prepared by the methods described and exemplified in the following reaction scheme:

The first described method starts from cyanamide and comprises the reaction steps 1-5 · 0 ° shown below

(1) H N-CM + CH3OCCl -> CH3OCNHCN

Il I

o o

(2) CH 2 OCNHCN + R'2Z - * CH 2 O-CN

R, 2 3 h 5.

O O MM

(3) CH OC-N-CN + R * Rj, NH-> CH-OC-N-C-NR ^ B's R'2 5 6 7 0 O NH O N-C-NHR ^ (¾) CH3OC-N-C-NR3R1 | + R 1 NCO-> Cl 2 OC-N-C-NR 2 R, 2 R, 2 1 l i 5 57940

o N-S-rnHj A

(5) CH3OC-N-C-HR3nlj + MOR—> V N.

r * 2 ^ NR-IU

t 5 * <10 R, £ R 2 11 ^ (compound I, where X is oxygen atom and

Rg is an alkyl group) O NH5

"" O N-C-NJfR

(Ib) CH 0 OC-N-C-NR 'R, + R * NCS-> „1 5» 5 M 1 CH 2 OC-N-C-NR' Rk

R * 3 J

R, 2 and 13'S ® O N-C-NHRj R1 \ n ^ k (2b) CHjOC-N-C-NR '^ + M * OR—, y R »nAn ^ \ / RI3 R 2 10 0.

"Compound I wherein X is a sulfur atom. And R 2 and R 1 are alkyl groups) wherein R 1, R 2 and are as defined above, R is a hydrogen atom or an alkyl group containing 1-U carbon atoms, R 9 ' is a lower alkyl group, R 1 * is a lower alkyl group, M * is an alkali metal and Z is an iodine atom or a group 0 -O-S-QR 'M 7

O

A process for the preparation of methyl cyanocarbamates (Compound 3) ο / οη <Ό5 <ίίyt · 6 57940 (Compound 1) and methyl chloroformate (Compound 2) is described in U.S. Patent 5,657,445 (Equation 1).

An aqueous solution of the sodium salt of Compound 5 containing 15-55 ° C and preferably 20-50 ° C of Compound 5 is reacted at 10-70 ° C and preferably 25 ° C to 45 ° C 0.9-1 * 4 and preferably 1.0 ° C. With -1.2 molecular equivalents of alkylating agent 4 (e.g. dimethyl sulfate) for 2-16 hours and preferably 4-8 hours (Equation 2). As the reaction proceeds, a second phase of compound 5 is formed. After the reaction has continued for the desired time, the upper layer of compound 5 containing some water is separated and the lower aqueous layer is contacted with an organic solvent selected from the group consisting of methylene chloride, dichloroethane, triclene, benzene, toluene and xylene and toluene is recommended. . Other dialkyl sulfates (or alkyl halides) may be used in place of dimethyl sulfate, with sulfates being preferred for economic reasons.

The extract and the upper layer are analyzed for compound 5 by gas chromatography and added to an aqueous solution containing 15-75 # and preferably 25-50 μl of compound 6 hydrochloride or sulfate, preferably sulfate (Equation 5). · The molar ratio of amine salt to compound 5 may be between 1 -5 and preferably between 1.5-2.5 · The extraction solvent used (e.g. toluene) is removed by either azeotropic or conventional distillation depending on the boiling point. The remaining aqueous mixture is then stirred for 5-10 hours at 50-110 ° C and preferably 65-95 ° 0: 88a (Equation 5) · Higher temperatures require shorter reaction times and vice versa *

The reaction mass obtained contains compound 7 and, as a by-product, trisubstituted guanidine and unreacted compound 6, all present as salts. Before proceeding with the reaction between compound 7 and compound 8, it is necessary to liberate the free bases and remove excess compound 6 to prevent the formation of a by-product urea. This procedure can be performed by adding 50 of aqueous sodium hydroxide to an amount corresponding to the amount of compounds 6 and 7 present as determined by gas chromatographic analysis and extracting as an organic solvent such as methylene chloride and then distilling off some of the organic solvent to remove excess compound 6 or removing compound 6 directly from the aqueous solution. gas after the addition of a base to form the free amine. The latter procedure is recommended. Compound 7 is relatively unstable in aqueous solution when present as the free base and tends to decompose to the corresponding trisubstituted guanidine. The rate of decomposition is directly proportional to pH and temperature. Therefore, when 7,57940 is removed from compound 6 by direct distillation or stripping of water, it is preferable to use a vacuum or to carry out the operation as quickly as possible.

The water distillation process described above can be carried out batchwise or continuously. It is preferable to carry out the operation continuously so that the exposure of compound 7 to high temperature and high pH is minimized. This is accomplished by adding an aqueous solution of the alkali metal hydroxide to the product from reaction 3 in a tubular reactor or by passing the product and the alkali metal hydroxide into a small mixing vessel with a short residence time, 0-10 min. and preferably 0-2 minutes. If the concentration of the amine salt used is such that the sodium salt precipitates during this neutralization, more water must be added to keep this salt in solution. The upstream flow from this vessel is fed to a distillation column operating under vacuum.

^ The column is heated by feeding steam to its bottom; compound 6 and water are removed as a distillate (upstream) and the aqueous solution of compound 7 and trisubstituted guanidine as a base product.

There are several conditions under which the column can be used and they depend to some extent on the nature of compound 6. In general, however, the conditions are selected so that the temperature of the liquid fed to the column does not exceed 50 ° C. This makes it necessary to cool the product of formula 3 to about 30 ° C before adding the base. The column operates at a pressure of 25-300 mmHg and preferably 50-150 mmHg and the amount of steam fed to the bottom of the column is adjusted so that the amount of water taken upstream together with compound 6 corresponds to the weight of the reaction mass of 5 ~ 25 ^ equation 3.

The bottom products of the above distillation are fed to a storage tank maintained at pH 5-7 by the continuous addition of either sulfuric or hydrochloric acid; sulfuric acid is recommended. The concentration of compound 7 in the neutralized solution is kept between 15-50 and preferably between 20-40. The concentration depends on the strength of the basic and acid solutions of the brine of compound 6 used in the previous steps and the amount of concentration or dilution that occurred during distillation. The temperature of this solution is maintained between 25-45 ° C and preferably between 25-35 ° C, either by cooling the base products in a continuous type condenser before neutralization or by cooling the neutralization vessel itself.

Reaction 4 is carried out by preparing a mixture of the above solution and a solvent such as benzene, chlorobenzene, toluene or xylene; xylene is recommended. The amount of solvent added should be sufficient to dissolve the entire amount of compound 9 formed. In general, the amount of solvent used is about 7 to 10 times the amount of compound 7 present in aqueous solution.

e 57940

The amount of compound 8, which corresponds stoichiometrically to 85-100 96 and preferably 92-96 ° fo, is now added to the amount of compound 7 present in the aqueous layer, and with good stirring the addition of an aqueous solution of 50 # base is started while maintaining the temperature between -5 and + 50 ° C and preferably between 5-35 ° C with external cooling. The addition of the base is carried out as rapidly as the heat can be removed to maintain the desired temperature and is continued until an amount stoichiometrically corresponding to the amount of acid used to neutralize compound 7 has been added. If the solid phase of the sodium salt is now present, sufficient water must be added to dissolve it. The reaction is allowed to proceed after the addition of base is complete until the pH of the aqueous solution is almost constant.

This requires an addition time of about 1-5 hours. Alternatively, the compound Θ and the aqueous base may be added simultaneously while maintaining the pH of the reaction mass at 9-10 and preferably between 9-3-3-7- 1-4 hours and preferably 2-5 hours. The addition of aqueous sodium hydroxide solution is then continued until the pH is almost constant. Stirring is stopped and the layers are allowed to separate. The lower aqueous layer is removed and the upper organic layer is evaporated at a pressure of 50-760 mmHg and preferably 100-500 mmHg until a clear distillate is obtained (indicating that all water has been removed). The remaining solution or slurry containing compound 9 is cooled to 25-45 ° C, if necessary, while amine 6 (e.g. dimethylamine) is added either as a gas or as a liquid. It is recommended to add amine 6 at 25-55 ° C, but higher or lower temperatures may be used depending on the solubility of amine 6 in that solvent. It is important that the mixture contains at least 1.0 and preferably 1.0-2.5 moles of amine 6.

Next, a ring-forming catalyst is added (Compound 10, Equation 5) · The catalyst is an alkali metal alkoxide (or hydroxide) and can be added either as a dry solid or as a solution in an alkanol. Dry sodium methoxide or methanolic sodium methoxide solution is the preferred catalyst. The amount of catalyst required is 0.1-5 * 0 mol-96 of compound 9 · Higher concentrations are not desirable as side reactions begin to interfere. The preferred concentration of compound 10 is 1.0-2.0 moles of compound 9. The temperature is not critical and the ring-forming reaction can take place at temperatures of 0-120 ° C, provided that the amine 6 remains in the reaction system. The reaction is normally exothermic and the solution may be cooled if a lower temperature is required to keep the amine 6 in solution. It is essential that amine 6 remain present until ring formation is approximately complete.

After the catalyst is added, the reaction mass is maintained for 0.1-2.0 hours to ensure completion of the ring formation support. The reaction is rapid and normally completed in less than 1.0 hour.

The amine 6, by-product methanol and part of the solvent are then removed by distillation under either normal or reduced pressure. Water is then added and the rest of the solvent is removed by azeotropic distillation. Water entering the front container can be discarded or returned to the system as desired. The amount of water remaining in the residue is not critical and may vary from 0.1 to 5 or more parts of water per part of compound 11 depending on how the compound 11 is to be isolated. Isolation can occur by crystallization followed by filtration or centrifugation, spray drying, phase separation to separate the bulk of the water, or other conventional methods.

Alternatively, compound 11 can be recovered without distilling all of the methanol, amine 6 and solvent. If a poorly soluble compound 11, such as hexane, is added to the reaction mixture, compound 11 precipitates and can be recovered by conventional methods.

The following examples further illustrate this method for synthesizing the compounds of this invention.

In the examples, all proportions are by weight and all temperatures are in degrees Celsius unless otherwise indicated. Refractive indices indicated by

2C Q

are values at 25 ° C.

Example 1 Synthesis of 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,5- (1H, 3H) -dione A. Synthesis of N-methoxycarbonyl-N-methylcyanamide (Equations 1 and 2)

To a solution of 50¾ parts of a 50% aqueous solution of cyanamide in 825 parts of water at 25 ° C is added over a period of 90 minutes and at a pH of 6.9 ~ 7> 1 simultaneously 572 parts of methyl chloroformate and 9 ^ 5 parts of 50% aqueous sodium hydroxide solution. As the addition of reagents progresses, the reaction temperature is allowed to rise to 53-55 ° C and is maintained in this range with cooling. At the end of the addition, the reaction mass is cooled to 25 ° C, whereupon crystallization of methoxycarbonyl cyanamide takes place. Dimethyl sulfate (775 parts) is then added and stirring of the reaction mass is continued while maintaining the pH between 7 ~ 7 »1 by dropwise addition of about 25 parts of 50% aqueous sodium hydroxide solution. After 6.5 hours, the biphasic solution obtained is repeatedly extracted with methylene chloride and the extract is dried. Half of the methylene chloride extract is then evaporated in vacuo and the residue is distilled at 50 ° C / 0.5 rH. 237.6 parts of N-methoxycarbonyl-N-methylcyanamide are obtained (69.5% yield).

10 57940 B. Synthesis of N-methoxycarbonyl-N, N ', Ν'-trimethylguanidine (Equation 3)

A solution of 339 parts of diraethylamine hydrochloride in 500 parts of water is heated to 50 ° C, and the remaining half of the above methylene chloride extract is gradually added thereto while removing methylene chloride by distillation. The resulting biphasic mixture is then heated to 0 ° C for about 20 hours, after which the starting N-methoxycarbonyl-N-methylcyanamide is almost completely gone. The solution is then cooled to 0 ° C and 336 parts of 50 μS aqueous sodium hydroxide solution are added. Repeated extraction of the reaction solution with methylene chloride and evaporation of the methylene chloride in vacuo gives 228.6 parts of (crude) N-methoxycarbonyl-N, N ', N'-trimethylguanidine of% purity, from which the pure product is isolated by distillation at T2 ° C / 0.5 mmH .

C. Synthesis of methyl N- (N-cyclohexylcarbamoyl-N, N1-dimethylamidino) -N-methylcarbamate (Equation 1+) to 11+, 8 g of the above impure N-methoxycarbonyl-N, Ν ', N' -trimethylguanidine dissolved in 50 parts of methylene chloride is added 11.0 parts of cyclohexyl isocyanate. The temperature of the solution reaches boiling point and when the temperature has dropped to 25 ° C, the solvent is evaporated in vacuo to give an oil which crystallizes on trituration with ether. Recrystallization from a mixture of carbon tetrachloride and Petro-ether gives pure methyl N- (N-cyclohexylcarbamoyl-N ', N'-dimethylamidino) -N-methylcarbamate, m.p. 93_9 * + 0 °.

Table II

Following the general procedure of Example Ie, using the appropriate isocyanate or isothiocyanate as reagents with an appropriately substituted methoxycarbonylguanidine, the following compounds can be prepared:

Methyl N- (N-cyclohexylthiocarbamoyl-N ', N'-dimethylamidino) -N-methylcarbamate, m.p. 122-123 ° C, and methyl N- (N- (p-fluorophenylthiocarbamoyl) -N ', N'-dimethylamidino) -N-methylcarbamate, m.p. 132-133 ° C.

D. Synthesis of 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,1 * - (1H, 3H) -dione (Equations 2, 3, U, 5) 10-stoichiometric excess of dimethyl sulfate (906 parts) ) is added at 25 ° C with stirring to 3,050 parts of an aqueous solution containing 797 parts of the sodium salt of compound 3, the pH of which has been adjusted to 7 with 50- $ 50 of aqueous sodium hydroxide solution. The reaction is allowed to proceed for 6 hours while maintaining the temperature at 25 ° C with external cooling and pH 7 by adding the required amount of 50- $ aqueous sodium hydroxide solution. During the reaction, a separate phase formed by compound 5 (R'g = CH 2) is formed.

11 57940

When the reaction is almost complete, stirring is stopped and the layers are allowed to separate. The upper layer of compound 5 (R'2 = CH2) is removed and the lower aqueous layer is extracted with 2,000 parts of toluene. The supernatant and extract are added to 3,300 parts of a stirred solution containing 920 parts of dimethylammonium sulfate in a vessel equipped with a solvent outlet. The resulting mixture is heated to 90 ° C and a vacuum is applied to remove toluene by azeotropic distillation. Distillation requires one hour and the reaction is continued for another 5 hours at 90 ° C. The reaction mass is then cooled to 30 ° C.

The above solution (3 MO parts) is analyzed for dimethylamine and compound 5 (R * 2 = CH 2) by gas chromatography and is found to contain 261 parts of dimethylamine and 625 parts of compound 7 (R 2 '= ^ 3 = ^ 1 * = CH). The solution is then fed to the vessel with stirring together with 50% aqueous sodium hydroxide solution at a rate of 28.6 parts of solution and 6.0 l of 50% aqueous sodium hydroxide solution per minute (This amount of sodium hydroxide releases compounds 6 and 7 from its salts;

Rg * = R ^ = R ^ = CH ^) · The residence time in this vessel is two minutes. The effluent from this vessel is fed to the top of the packed column, which operates at an absolute pressure of 100 mmHg and has a total effluent. Steam from normal pressure is fed to the bottom of the column at such a rate that the volume of H 2 O distilled over is 5 parts / min. The stripped solution leaving the bottom of the column (into a vessel containing 800 parts of 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 removed and h 700 parts of toluene and U70 parts of cyclohexyl isocyanate (approximately 90% of theory) are added to the neutralized distillation column bottoms and 50% aqueous sodium hydroxide solution is added to the bottom of the distillation column used. the amount of sulfuric acid, during half an hour while the temperature at the time maintained at 30 ° C by external cooling. The reaction is allowed to proceed for a further 3 hours until the pH becomes almost constant at 8.8. The temperature is adjusted to 3 ° C and maintained for 10 minutes, after which the stirrer is stopped and the layers are allowed to separate. The lower aqueous layer is removed and the toluene layer is distilled at 100 mmHg until a clear distillate is obtained.

Dimethylamine (375 parts) is fed to the residue while maintaining the temperature at 25 ° C with external cooling. Then 15> 9 parts of a 25% methanol solution of sodium methoxide are added with good stirring. The reaction is slightly exothermic and the temperature rises to 35 ° C in 15 minutes. The reaction is allowed to continue for another half hour. The solution is then concentrated at 100 mmHg until 1,000 parts of toluene is removed. Water (1,900 parts) is added and distillation is continued until the toluene is completely removed. The water obtained upstream is returned to the distillation vessel through 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 to give 7 + + 5 parts (1 + 5.3% based on compound 3) of compound 11 (R 1 = cyclohexyl group; R 2 = = R 1 = methyl group), m.p. 97 ~ 100.5 ° C. The aqueous filtrate can be recycled to reduce product 11 losses.

Alternative isolation of compound 11 from aqueous solution is as follows: The aqueous residue from distillation is heated to 60 ° C. This results in the formation of a two-phase system. The lower organic layer is separated from the upper water layer. The amount of the organic phase is 1,070 parts and contains 762 parts of compound 11. The aqueous phase contains 77 parts of compound 11 and can be recycled to the distillation vessel to obtain a higher overall yield.

The following s-triazinediones are prepared by cyclization of the appropriate methyl N- (N-substituted carbamoyl or thiocarbamoyl-N ', N'-dialkylamidino) -N-alkyl carbamate by the method described above.

Table III

1-methyl-3-cyclopentyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 126-129 ° C, 1-ethyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, = 1,579,7,1-methyl-3-cyclohexyl-6-dimethylamino -s-triazine-1 + -thio-2, U- (1H, 3H) -dione, m.p. 210-212 ° C, 1-methyl-3- (p-fluorophenyl) -6-dimethylamino-s-triazine-U-thio-2,1 + - (1H, 3H) dione, m.p. 221 + -226 ° C, and 1-methyl-3- (m-fluorophenyl) -6-dimethylamino-s-triazine-1 + -thio-2,1 + (1H, 3H) -dione, m.p. 20l + -206 ° C.

E. Alternative Synthesis of Methyl N- (N-Cyclohexylcarbamoyl-N ', N'-dimethylamidino) -N-methylcarbamate (Formula 1+)

The solution of the sulfate salt of product 7 prepared in Example 1D is mixed with 1 + 700 parts of toluene, and 1 + 70 parts of cyclohexyl isocyanate are added over 2 hours while maintaining the pH at 9.5 by continuous addition of aqueous 50- $ sodium hydroxide solution. The addition of sodium hydroxide is continued for a further 3 hours until the pH becomes approximately constant at 9.5 <The temperature is maintained at 30 ° C throughout the reaction. The reaction mixture is purified as in Example 1D to give methyl N- (N-cyclohexylcarbamoyl-N ', N'-dimethylamidino) -N-methylcarbamate in approximately the same yield.

, 3 57940

Formulas 1b and 2b illustrate how to prepare those compounds of this invention wherein X is a sulfur atom.

Formula 1b:

The methoxycarbonylguanidine derivative 7h reacts with the isothiocyanate (12) in an inert solvent (such as tetrahydrofuran) from about room temperature to 100 ° C for about 1-12 hours to form methoxycarbonylallophanimidate 13. This intermediate can be isolated by further evaporation of the solvent by evaporation of the solvent. and the intermediate can be used directly without isolation in the next step (2b).

Formula 2b:

Methoxycarbonylallophanimidate 13 dissolved in an inert solvent (such as toluene) is treated with an alkali metal alkoxide or hydroxide (such as sodium or potassium methoxide or hydroxide) and the mixture is heated to cyclize compound 13 to the triazine-U-thione. Compound 1U can be isolated by cooling the reaction mixture and filtering off the precipitated product 1U. If desired, product 1 can be further purified by recrystallization from an inert solvent (such as ethyl acetate).

Example 2 Synthesis of 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-1 * -thio-2,1 + -dione

A mixture of 100 parts of N-methoxycarbonyl-N, N ', Ν'-trimethylguanidine, 89 parts of cyclohexyl isothiocyanate and 0.5 parts of dibutyltin dilaurate prepared in Example 1B is kept for 8 hours at 70 ° C and 1000 parts of toluene. The clear, yellow solution is heated to reflux and 50 parts of toluene are distilled off. A 12.5 portion portion of a 0.5 M methanolic sodium methoxide solution is added over 30 minutes to allow toluene to distill off from the reaction mixture. At the end of the addition, the toluene is further distilled off until 500 parts of toluene have been removed. The reaction mixture is cooled and the resulting pale yellow product, 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-N-thio-2H- (1H, 3H) -dione, crystallizes. Filtration and drying gives 113 parts of product, m.p. 210-212 ° C.

The intermediate methyl N- (N-cyclohexylthiocarbamoyl-N ', N'-dimethylamidido) -N-methylcarbamate can be isolated by removing toluene under reduced pressure and crystallizing the crude solid from ethyl acetate to give the pure intermediate, m.p. 122-123 ° C;

In some cases, it is not necessary to add a base (sodium methoxide) to effect ring formation, e.g. in the preparation of the first two triazine U-thions of Table IV.

I1 * 57940

In a similar manner, the following compounds can be prepared using appropriate reagents.

Table IV

1-methyl-3-ethyl-6-dimethylamino-s-triazine-1H-thio-2,0- (1H, 3H) -dione, m.p. 139-140 ° C, 1-methyl-3- (n-butyl) -6-dimethylamino-s-triazine-H-thio-2,1- (1H, 3H) -dione, m.p. 12-126 ° C, 1-methyl-3-phenyl-6-dimethylamino-s-triazine-U-thio-2,1 + - (1H, 3H) -dione, m.p. 209-211 ° C, 1-methyl-3- (o-fluorophenyl) -6-dimethylamino-s-triazine-4-thio [4,4- (1H, 3H) dione, mp 220-221 ° C, 1- methyl 3- (m-fluorophenyl) -6-dimethylamino-s-triazine-H-thio-2,1- (1H, 3H) dione, mp 201 + -206 ° C, 1-methyl-3- (p-fluorophenyl) ) -6-dimethyl-s-triazine-H-thio-2,0- (1H, 3H) -dione, mp 22i + -226 ° C, 1-methyl-3- (2-methylcyclohexyl) -6-dimethylamino-s- triazine-4-thio-2,0- (1H, 3H) -dione, mp 139-110 ° C, 1-methyl-3- (3-methylcyclohexyl) -6-dimethylamino-s-triazine-4-thio- 2.1 + - (1H, 3H) dione, mp 1-1-16 ° C, and 1-methyl-3-cycloheptyl-6-dimethylamino-s-triazine-H-thio-2,1- (1H, 3H) -diones, mp 20H-205.5 ° C.

An alternative process for preparing the compounds of this invention begins with a 2-methyl-2-thiopseudourea salt such as sulfate or hydrochloride. A schematic representation of this method is illustrated in Equations 6-12.

NH 0 NH

11 il f 2 (6) H2N-C-SCH3 + C1CO2CH3 ---> CH3OC-N = C-SCH3 every 2 15 NH 0 NH2 (6a) H2N-C-SCH3 + R ^ CO -> R ^ C-N-C-SCHg

JA 8 J5a O

0 NH 0 NH-CNHR

n f έ tl I * (7) CH30C-N = C-SCH3 + R ^ NCO - => CH3OC-N = C-SCH3 15 8 0 rt

0 NH 0 NHCOCJI

»R I ** ft *> <(> x) h + 0100, citv ---------- ^ h.nhc-n ^ j-scii.

i> 2 _1_6 15 57940 o '9

0 NH-C-NHR ^ R

(8) CH3OC-N * C-SCH3 + M * OR - = * - 0 M 'SCH3 16 10 17 0

(9) ^ Ji + R’2z -i · N

0Λ: Λ30 „3 i R, 2 ii.

18 v Λ Rl y ^.

(10> X I + r3vr -> 0ΪΛ ¥, 0 N SCH0 '5' • 3 R »R'2 £ 2 08. Ϋ ri ^ An

. 1 N N, N N

ΛΛ-, ^ AA », II 19 16 57940 o o R R1 \ 1 N N n (12) ^ ^ R3VH}

O N 'SCH O N SCH

H J 0 R3RUNH2 + 12. 20 R '\ R, v Av

NN H + ^ N N

ο ^ νΛ * Λ 0 ^ ΛιηΑ H ^ R3R14NH2 + 21 22 where R ^, Rg '»R ^ j R, M' and Z are the same as defined above.

A suspension or solution of compound II + is prepared in the chosen solvent and treated with methyl chloroformate or an isocyanate of formula R 1 NCO (Equations 6 and 6a) until the reaction is complete. The product, 1-carbomethoxy-2-methyl-2-thiopseudourea (Compound 15) or 1-cyclohexyl-1-methyl-1 + -thiopseudourea (Compound 15a) is treated with an isocyanate of formula R 1 NCO (Equation 7) or methyl chloroformate (Equation 7). 7a) to give compound 16. A solution of compound 16 in a suitable solvent is treated with an alkali metal alkoxide to give salt 17 (Equation 8). A solution or slurry of compound 17 in the selected solvent is reacted with an alkylating agent to give compound 18 (Equation 9). A suspension or solution of compound 18 in the chosen solvent is treated with amine 6 to give compound 11. The product, s-triazine-2, t- (1H, 3H) dione, can be isolated by the conventional technique described above in connection with Equation 5.

To prepare the compounds of this invention in which R 1 is a hydrogen atom, the reactions of Equations 11 and 12 are performed. Compound 17 is acidified with mineral acid to Compound 19 (Equation 11), which is then reacted in Equation 12 with an amine shown above for Compound 18. . The product formed is an amine salt 21 which can be used in the process of this invention or can be acidified to give compound 22. Compound 22 reacts with appropriate bases (such as ammonia, dimethylamine and hydroxides of lithium, sodium, potassium and calcium) to form salts of the compound of formula I.

17 57940

Solvents that can be used in these reactions include water, toluene, benzene, xylenes, monochlorobenzene, nitrobenzene, methylene chloride, triclene, perclene, or mixtures of these organic solvents with water, i.e., the solvent need not be anhydrous.

In connection with the above-mentioned solvents, it is practical to use a ratio of compound 11+ to solvent of 1: 3-1: 10 and preferably 1: 3-1: 6. The most preferred solvents in this group, given their low cost and greater stability when used in the process of this process, are water, toluene, xylene and benzene.

The most preferred solvent for the reaction according to Equation 6 is water. Mixtures of water and the organic solvents listed above can also be used. In connection with the above-mentioned solvents, it is practical to use a ratio of water to organic solvent of 1: 1 to 1: 6 and preferably 1: 1 to 1: 2.

The two-solvent system is most preferred for the reaction according to Equation 6a, since the isocyanate 8 reacts with water to form undesired by-products. The yield of product 15a from the isocyanate may be significantly reduced due to these side reactions.

The ratios of 1: 1: 1 and 1U: 8 can be varied between 1: 0.1-1: 3, preferably between 1: 0.8-1: 2 and most preferably between 1: 1-1: 1.3.

Reactions 6 and 6a can be carried out at a temperature of -10 to + 50 ° C, but preferably between 0-30 ° C and most preferably between 0-25 ° C.

In reactions 6, 6a and Ja, the pH can be varied, preferably between 6.5 and 11, and most preferably between 7-8.5 ·

Methyl chloroformate and isocyanate The order of addition of the R 1 NCO reagents relative to the addition of the aqueous base solution can be varied. Methyl chloroformate or isocyanate may be added first and then aqueous base. However, it is recommended to add methyl chloroformate or isocyanate and aqueous base simultaneously. A suitable base is Li, Na or K hydroxide. The strength of the base to be added may vary between 10-50%, but a higher of these concentrations is most preferred due to the smaller reaction volume per amount of product.

This simultaneous addition of methyl chloroformate or isocyanate R 2 CO and an aqueous solution of 50- # base gives a larger product to yield 15 or 15a due to the controlled pH conditions and the shorter contact time required to complete the reaction with water.

1β 57940

Reactions 7 and 7a are preferably carried out at a temperature between 0-50 ° C and most preferably between 15-35 ° C.

The ratio of methyl chloroformate to product 15a may be 1: 1 to 4: 1 »preferably 1» 5: 1 to 5: 1 and most preferably 2: 1 to 2.5 * 1. The ratio of isocyanate to product 15 is preferably 1: 1 »1 to 1: 1.5 and most preferably 1: 1.05 to 1: 1.15 to achieve a high 15% conversion of compound 16 without the use of an unnecessary excess of isocyanate or long reaction time. -tioaikaa.

The time required to complete the reaction is preferably 0.5 to 12 hours for both equations 6a and 7a, and most preferably it is ΙΑ hours. The reaction time depends on the nature and amount of the solvent and reagents, the temperature and the mixing method used.

The reaction time required for the addition of methyl chloroformate or isocyanate is not critical and may range from 0.1 to 10 hours, preferably from 0.1 to 4 hours, and most preferably from 0.25 to 1.5 hours.

Compound 16 is preferably treated with 0.6-1.2 equivalents and most preferably 0.9-1.1 equivalents of alkali metal alkoxide. The alkoxide can be used as the pure base or, preferably, as a solution in a suitable solvent, and most preferably as a solution of $ 15-35 in the corresponding alcohol.

A 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 ring formation occurs.

The cyclization of compound 16 to compound 17 (Equation 8) preferably takes place at 25-70 ° C, but most preferably at 45-70 ° C.

Removal of the solvent to provide a slurry of compound 17 can be performed under reduced pressure or normal pressure at a temperature of 20 to 135 ° C, but most preferably between 25 to 50 ° C under reduced pressure and 65 to 100 ° C under normal pressure.

Alkylation of 17 (Equation 9) with alkylating agent 4 (Z-halogen, alkyl sulfate) can be performed in a solvent such as water, toluene, benzene, xylene, chlorobenzene, nitrobenzene, acetonitrile, triclene or perclene.

The preferred solvent is water due to the low cost, simplicity of the process, and ease of isolation of the product 18. In this case, the product can be isolated by filtration and drying, or it can be used directly as a wet solid in the next reaction by suspending it in an organic solvent and removing water by azeotropic distillation.

«57940

When dialkyl sulfate is used to alkylate compound 17, the pH of the aqueous solution or slurry is best maintained between 7-11.5 and most preferably between 9-10.5 to prevent acidification of compound 17 to give compound 18 wherein R 'is H.

The ratio of alkylating agent to compound 17 is preferably between 0.8: 1 and 1.5: 1, but most preferably between 1.1 and 1.3: 1. The reaction can be carried out at a temperature of 15 to 135 ° C if it takes place in an organic solvent, and most preferably between 25 to 90 ° C.

When water is used as the solvent, a temperature range of 15 to 80 ° C and a range of 25 to 0 ° C are most preferred.

Conversion of 6-methylthio-s-triazine-2,1 * - (1H, 3H) -dione (Compound 18) to 6-amino-s-triazine-2,1 + - (1H, 3H) -dione 11 can best be performed in a solvent such as in toluene, xylene, benzene, monochlorobenzene, triphenylene, percene, nitrobenzene, methylene chloride and 1,2-dichloroethane. The most preferred solvent is toluene.

The preferred ratio of compound 18 to amine is preferably 1: 1-1: 6 and most preferably due to complete conversion to compound 11 and the shorter reaction time required, 1: 2-1: 3. The amine can in some cases be used as a solvent.

The conversion of 18 to 11 can be carried out at temperatures of 5 to 135 ° C, but most preferably in the range of 25 to 60 ° C.

The following examples illustrate the methods of Equations 6-12.

Example 3 Synthesis of 3-isopropyl-6-dimethylamino-s-triazine-2,1 * - (1H, 3H) -dione A. Methyl N- (1-amino-1-methylthiomethylene) carbamate (Equation 6)

To a solution of 69.5 parts of 2-methyl-2-thiopseudourea sulfate and "17 parts of methyl chloroformate in 1,000 parts of water at 0 ° C is added dropwise 56.9 parts of potassium hydroxide dissolved in 200 parts of water. The reaction mixture is stirred at room temperature for 3 hours and then extracted with methylene chloride The methylene chloride extract is dried and the solvent is evaporated on a rotary evaporator to give U5 part of methyl N- (1-amino-1-methylthiomethylene) carbamate, mp 72-77 ° C.

B. Synthesis of methyl 4-isopropyl-N-methoxycarbonyl-1-thioallophanimidate (Equation 7)

A solution of 7 * + parts of methyl N- (1-amino-1-methylthiomethylene) carbamate and k * part of isopropyl isocyanate in 300 parts of methylene chloride is stirred overnight. The solvent is evaporated on a rotary evaporator to give 113.6 parts of methyl isopropyl-N-methoxycarbonyl-1-thioallophanimidate, m.p. 129-132 ° C.

2 ° 57940

The compounds of Table V are prepared in a similar manner.

Table V

Methyl 1+ -cyclohexyl-N-methoxycarbonyl-1-thioallophanimidate, m.p. 85-86 ° C, methyl 1- (p-chlorophenyl) -N-methoxycarbonyl-1-thioallophanimidate, m.p. 127-128 ° C, methyl k- (3-chlorocyclobutyl) -N-methoxycarbonyl-1-thioallophanimidate, m.p. 173-17¾.5 ° C, and methyl 1+ -cyclohexylmethyl-N-methoxycarbonyl-1-thioallophanimidate, m.p. 132-13J4 ° C.

C. Synthesis of 3-isopropyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) dione (Equations 8 and 11)

One hundred parts of methyl 1 + -isopropyl-N-methoxycarbonyl-1-thioallophanimidate are refluxed for 1 hour with 27 parts of sodium methoxide in 200 parts of methanol.

The methanol is removed on a rotary evaporator and the residue is dissolved in 200 parts of water. The aqueous solution is neutralized with hydrochloric acid, the solid is filtered off and dried to give 55 parts of 3-isopropyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) dione, m.p. 188-190 ° C.

By the above method, the appropriate thioallophan imidates can be cyclized to the triazinediones shown below.

Table VI

3-cyclohexyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 255-257 ° C, 3-cyclopentyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) dione, m.p. 201-20 [deg.] C., 3- (p-chlorophenyl) -6-methylthio-s-triazine-2+ + (1H, 3H) dione, m.p. 292-295 ° C, 3- (m-chlorophenyl) -6-methylthio-s-triazine-2,0- (1H, 3H) dione, m.p. 192-195.5 ° C, 3-phenyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) dione, m.p. 235-21 + 5 ° C, 3- (3-chlorocyclobutyl) -6-methylthio-s-triazine-2,1 + - (1H, 3H) dione, m.p. 167-169 ° C, 3- (1-methylcyclopentyl) -6-methylthio-s-triazine-2,0- (1H, 3H) dione, m.p. 192-195.5 ° C, and 3-cyclohexylmethyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 177,5-17ö ° C.

D. Synthesis of 1-methyl-3-isopropyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione (Equation 9)

To a solution of 32 parts of sodium methoxide in 1 + 00 parts of methanol is added 132 parts of 3-isopropyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) dione. The solution is evaporated in vacuo and the white solid is triturated with methylene chloride and filtered to give 110 parts of sodium 3-isopropyl-6-methylthio-s-triazine-2, U- (1H, 3H) -dione, m.p. above 300 ° C.

21 57940

Eighty parts of sodium 3-isopropyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) dione and 1 + 9 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, 5 * + parts of a mixture of 1-chlorobutane and hexane to give 1-methyl-3-isopropyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) dionia, m.p. jk-JJ ° C.

Using the appropriate 6-methylthio-s-triazinedione, a variety of compounds can be prepared by the above method, which are set forth below.

Table VII

1-methyl-3-cyclopentyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 80-83 ° C, 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) dione, m.p. 135-137 ° C, 1-methyl-3- (2-methylcyclohexyl) -6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 98-100 ° C, 1-methyl-3- (3-methylcyclohexyl) -6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione, n-1.5372, 1-methyl-3 -cycloheptyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 98-101 ° C, 1-methyl-3- (1-methylcyclopentyl) -6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 81 + -36 ° C, 1-methyl-3-cyclohexylmethyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 102.5-10 l + ° C, 1-methyl-3-phenyl-6-methylthio-s-triazine-2,1 + - (1H, 3H) dione, m.p.

232.5-233 ° C, 1-methyl-3- (p-chlorophenyl) -6-methylthio-s-triazine-2,1 + - (1H, 3H) dione, m.p. 11 + 6.5-1 * 8.50 ° C, 1-methyl-3- (m-chlorophenyl) -6-methylthio-s-triazine-2,1 + - (1H, 3H) dione, 297-297.5 ° C, 1-methyl-3- (3,5-dimethylcyclohexyl) -6-methylthio-s-triazine-2,1 + - (1H, 3H) dione, n-δ 1.5 ° C, and 1-methyl -3- (p-methylthiophenyl) -6-methylthio-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 193-195 ° C.

E. Synthesis of 3-isopropyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione (Equation 12)

Ten parts of 3-isopropyl-6-methylthio-s-triazine-2+ + (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 impure solid after filtration. The crude product is recrystallized from acetonitrile to give 2 parts of dimethylammonium-3-isopropyl-6-dimethylamino-s-triazine-2, U- (1H, 3H) -dione, m.p. 213-215 ° C.

To two parts of the above salt is added 10 parts of 1-N hydrochloric acid.

The solution is extracted with chloroform and the chloroform extract is dried and evaporated to give 1 part of 3-isopropyl-6-dimethylamino-s-triazine-2,8- (1H, 3H) -dione, m.p. 213-21U ° C.

F. Synthesis of Sodium 3-Isopropyl-6-dimethylamino-s-triazine-2,1 * - (1H, 3H) -dione

Dissolved in six parts of sodium methoxide in 60 parts of methanol, 20 parts of 3-isopropyl-6-dimethylamino-s-triazine-2,1- (1H, 3H) dione are added. The solution is distilled and the residue is triturated with ether to give, after filtration, 18 parts of sodium 3-isopropyl-6-dimethylamine-s-triazine-2,8- (1H, 3H) -dione, m.p. above 300 ° C.

Using the above methods, 6-alkylamino-s-triazines and their salts can be prepared. Some examples are:

Table VIII

3- (tert-butyl) -6-methylamino-s-triazine-2,0- (1H, 3H) -dione, 3-cyclohexyl-6-dimethylamino-s-triazine-2,1- (1H, 3H) -dione , sp. 279 ° C, dec., 3- (tert-butyl) -6-dimethylamino-s-triazine-2, k- (1H, 3H) dione, m.p.

206-209 ° C, 3- (sec-butyl) -6-methylamino-s-triazine-2,1- (1H, 3H) -dione, m.p. 161-16 ° C, 3- (p-chlorophenyl) -6-dimethylamino-s-triazine-2,6- (1H, 3H) -dione, m.p. 265-2β7 DEG, 3- (3-pentyl) -6-dimethylamino-s-triazine-2,1- (1H, 3H) -dione, m.p. 1-18-151 ° C, 3- (3,1-dimethylcyclohexyl) -6-dimethylamino-s-triazine-2,5- (1H, 3H) -dione, m.p. 23 DEG-237 DEG C. 3- (1 + -tert-butylcyclohexyl) -6-dimethylamino-s-triazine-2,1- (1H, 3H) -dione, m.p. 283-285 ° C, 3- (1-methylcyclopentyl) -6-dimethylamino-s-triazine-2H- (1H, 3H'-dione mp 10H-106 ° C, 3-isopropyl-6-dimethylamino-3- trialsin-2, L- (111.3) dione, mp 213-21 U ° C, 3-isopropyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione dimethylamine salt, mp 213-215 ° C, 23,57940 Lithium salt of 3-isopropyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, mp> 300 ° C, 3-isopropyl-6-methylamino- 1/2 calcium salt of s-triazine-2,1 + - (1H, 3H) -dione, mp> 300 ° C, and 3-isopropyl-6-methylamino-s-triazine-2,1 + - (1H , 3H) sodium salt of dione, mp> 300 ° C.

G. Synthesis of 1-methyl-3-isopropyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione (Equation 10)

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

Example 1+

A modified manner for the preparation of compounds in which the spacing group is in the 3-position (R 1 in formula I) using methyl chlorothiol formate 1-methyl-3- (tert-butyl) -6-dimethylamino-s-triazine-2,1 + - ( 1H, 3H) dione (equations 6a, 7a (modified), 8, 9 and 10)

To a solution of 278 parts of 2-methyl-2-thiopseudourea sulfate in 2,000 parts of a 50- $ methanol aqueous solution at 0 ° C is added dropwise 176 parts of 50- $ sodium hydroxide followed by 10,000 parts of tert-butyl isocyanate dissolved 1 + 00 parts of tetrahydrofuran. The solution is partially evaporated on a rotary evaporator and the slurry is filtered to give, after drying, 180 parts of methyl 1- + (tert-butyl) -1-thioallophanimidate, m.p. + 102-10l ° C.

To a solution of 113 parts of the above compound and 80 parts of triethylamine in 1,000 parts of methylene chloride at 0 ° C is added dropwise 66 parts of methyl chlorothiol formate dissolved in 100 parts of methylene chloride. The solution is stirred overnight, washed once with water, dried and evaporated to give 76 parts of methyl 1- + (tert-butyl) -N-methylthiolecarbonyl-1-thioallophanimidate, m.p. 102-105 ° C.

50 parts of the above compound are refluxed for 1 hour with 30 parts of sodium methoxide in 500 parts of methanol. The reaction mixture is then cooled and the methanol is evaporated off on a rotary evaporator. The residue is washed with ether to give 30 parts of sodium 3- (tert-butyl) -6-methylthio-s-triazine-2,1- (1H, 3H) dione.

2b 5 7 9 4 0 2k parts of sodium 3- (tert-butyl-6-methylthio-s-triazine-2,1- (1H, 3H) -dione and 15.5 parts of methyl iodide are refluxed overnight in 200 parts of acetonitrile. The solvent is evaporated off and the residue is dissolved in methylene chloride, the methylene chloride solution is washed with water, dried and evaporated to give, after recrystallization, 15 parts of 1-methyl-3- (tert-butyl) -6-methylthio-s-triazine from 1-chlorobutane. 2, h- (1H, 3H) dione, mp 138-110 ° C.

A solution of 5 parts of the above substance in 50 parts of tetrahydrofuran o ....... ...

At 0 ° C, saturated with dimethyl amine. The reaction mixture is allowed to warm to room temperature and stand overnight. The solvent is evaporated and the residue is triturated with ether to give U part of 1-methyl-3- (tert-butyl) -6-dimethylamino-s-triazine-2, U- (1H, 3H) dione, m.p. 161-163 ° C.

Example 5 1-Methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2, k- (1H, 3H) -dione A. 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2, h- (1H , 3H) dione preparation (equations 6, 7, 8 and 9)

To a solution of 56 parts of 2-methyl-2-thiopseudourea sulfate in 300 parts of water at 0 ° C are added dropwise simultaneously 37.5 parts of methyl chloroformate and 62 parts of 50- $ 50 aqueous sodium hydroxide solution. Methyl chloroformate is added over 0.5 hours and 50- $ aqueous sodium hydroxide is added as needed to maintain the pH of the reaction mass at 8.5. When the additions are complete, the reaction mixture is brought to room temperature (25-28 ° C) and kept for 2 hours.

To this 1-carbomethoxy-2-methyl-2-thiopseudourea suspension at 25-28 ° C is added 300 parts of toluene. Cyclohexyl isocyanate (parts per month) is added over 0.5 hours and the mixture is then stirred at 25-30 ° C for a further 2 hours. The toluene layer is then separated and 76 parts of 25% sodium methoxide solution are added. The solution is then refluxed for 1 hour (65-70 ° C) and then the methanol-toluene mixture is distilled off until a bottom temperature of 88-90 ° C is reached.

This slurry of the sodium salt of 3-cyclohexyl-6-methylthio-s-triazine-2α- (1H, 3H) -dione is then stirred with 650 parts of water for 0.15 hours. The aqueous layer is separated and the mixture is allowed to react at 25-30 ° C for 0.25 hours with 57 parts of dimethyl sulfate. After the addition of dimethyl sulfate, the pH of the reaction mixture is maintained between 9 ~ 9.5 by adding a total of 7.5 parts of 50- $ 50 aqueous sodium hydroxide solution. The total reaction time is 1.8 hours, after which time 70 parts of white 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2, k- (1H, 3H) dione are obtained by filtration and drying, m.p. 137-139 ° C.

B. Preparation of 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,1- (1H, 3H) -dione (Equations 6a, 7a, 8 and 9)

To a solution of 70 parts of 2-methyl-2-thiopseudourea sulfate in 375 parts of water and 1.00 parts of toluene at 10 ° C is added 62.5 parts of cyclohexyl 57940 acyl isocyanate over 1 hour. The pH is maintained at 8.5 by adding 80 parts of 50% aqueous sodium hydroxide solution over 1-1.5 hours. This two-phase system is then reacted with 99 parts of methyl chloroformate and 8U of a 50% aqueous sodium hydroxide solution for 1 hour. The temperature is maintained between 25-30 ° C. After the addition is complete, the reaction mixture is stirred at 25-28 ° C for an additional 3 hours. The toluene layer is separated and treated as in Example 5A to give 76 parts of 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2, U- (1H, 3H) -dione, m.p. 136-138 ° C.

C. Preparation of 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,5- (1H, 3H) -dione (Equation 10) A suspension of 300 parts of 1-methyl-3-cyclohexyl-6 -methylthio-s-triazine-2,1 + - (1H, 3H) -dione in 887 parts of toluene, stirred at 25-30 ° C for three hours with 15Ο parts of dimethylamine. Toluene is distilled from the reaction mixture until a bottom temperature of 125 ° C is reached. The reaction mass is cooled to 50 ° C, after which 1 + 80 parts of hexane are added over a period of 0.66 hours. The slurry at 25 ° C is filtered to give 282 parts of crystalline 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,5- (1H, 3H) -dione, m.p. 110-115 ° C.

The following aminotriazine diones can be prepared by the methods of Examples 3, 1 and 5 using appropriate reagents.

Table IX

1-methyl-3-ethyl-6-dimethylamino-s-triazine-2,3 * - (1H, 3H) -dione, m.p. 10-106 ° C, 1-methyl-3-propyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 106-109 ° C, 1-methyl-3-isopropyl-6-dimethylamino-s-triazine-2,1 '- (1H, 3H) dione, m.p. 10i + -106 ° C, 1-methyl-3-isobutyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 87-89 ° C, 1-methyl-3-butyl-6-dimethylamino-s-triazine-2,1- (1H, 3H) -dione, m.p. 63-65 ° C, 1-methyl-3- (sec-butyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. n * 5 1.5198, 1-methyl-3-isobutyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 87-89 ° C, 1-methyl-3- (tert-butyl) -6-dimethylamino-s-triazine-2H- (1H, 3H) -dione, m.p. 161-163 ° C, 1-methyl-3-neopentyl-6-dimethylamino-s-triazine-2,3- (1H, 3H) -dione, m.p. 1U1 - LifU ° C, 26 57940

p C

1-methyl-3-hexyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, 1,51130,1-methyl-3-allyl-6-dimethylamino-s-triazine-2, 1 + - (1H, 3H) dione, m.p. Mp -75 ° C, 1-methyl-3- (2-methallyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 9k-96 ° C, 1-methyl-3- (3,1 + -dichlorophenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 211-212 ° C, 1-methyl-3- (2,5-dichlorophenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 191- [18] + ° C, 1-methyl-3- (p-chlorophenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 238-239 ° C, 1-methyl-3- (m-chlorophenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 11 * 1-11 + 3 ° C, 1-methyl-3- (o-chlorophenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 205-207 ° C, 1-methyl-3- (m-fluorophenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 157-159 ° C, 1-methyl-3- (o-fluorophenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 179-182 ° C, 1-methyl-3- (3-chloro-1 + -fluorophenyl) -6-dimethylamino-s-triazine-2,1 + (1H, 3H) -dione, m.p. 195-198 ° C, 1-methyl-3- (3-chloro-6-methylphenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 155 DEG-157 DEG C., 1-methyl-3- (3-chloro-1 + -methylphenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 189.5-190.5 ° C, 1-methyl-3- (m- (trifluoromethyl) phenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, mp 11 + U-1U8 ° C, 1- methyl-3- (m-nitrophenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, mp 207-209 ° C, 1-methyl-3-phenyl-6-dimethylamino-s- triazine-2,1 + - (1H, 3H) dione, mp 208-210 ° C, 1-methyl-3- (nitrolyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, mp 159-162 ° C, 1-methyl-3- (p-tolyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, mp 237-2l + 0 ° C, 1-methyl-3- (3,1 + -xylyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, mp 176-118 ° C, 1-methyl- 3- (p-ethylphenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, mp 200-203 ° C, 57940 27 1-methyl-3- (p-isopropylphenyl) - 6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, mp 189-191 ° C, 1-methyl-3- (3-chloro-1 + -methylphenyl) -6-dimethylamino-s- triazine-2,1 + - (1H, 3H) dione, mp 189.5-190.5 ° C , 1-methyl-3- (p-methoxyphenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 162-167 ° C, 1-methyl-3- (p-methylthiophenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 152-156 ° C, 1-methyl-3- (1 + -chloro-3- (trifluoromethyl) phenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 180-181 ° C, 1-methyl-3- (3-methoxypropyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 56 DEG-56 DEG C., 1-methyl-3- (3-methylthiopropyl) -6-diraethylamino-s-triazine-2,1 + - (1H, 3H) -dione, n = J = 1.551 + 5.1 -methyl-3- (2-cyclohexen-1-yl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, IR 3,500, 2,900, 1,730, 1,650 cm-1 , 1-methyl-3- (3-cyclohexen-1-yl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 11 + - 118 ° C, 1-methyl-3- (2-norbornylmethyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 117-131 ° C, 1-methyl-3- (1-methylcyclopentyl) -6-dimethylamino-s-triazine-2,1 + (1H, 3H) dione, m.p. 101 + -106 ° C, 1-methyl-3-cyclopentyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 126-129 ° C, 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 101.5-10l + ° C, 1-methyl-3- (2-methylcyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 125-126.5 ° C, 1-methyl-3- (3-methylcyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 91-93 ° C, 1-methyl-3- (1 + -methylcyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 131-132 ° C, 1-methyl-3- (2,3-dimethylcyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 120-122 ° C, 1-methyl-5- (1S, N-dimethylcyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, n-δ 1.5288, 1-methyl-3 - (2,6-dimethylcyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, np 1,521 + 1 +, 1-methyl-3- (2,3-dimethylcyclohexyl) -6 -dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, 1,58383, ae 57940 1-Methyl-3- (1 + -methoxy-cyclohexyl) -6-dimethylamino--triazine -2,1+ - (1H, 3H) dione, ηζ5 1.5305, 1-methyl-3-cycloheptyl-6-dimethylamino-s-triazine-2,1- (1H, 3H) dione, m.p. Mp 6-118 ° C, 1-methyl-3-cyclooctyl-6-dimethylamino-s-triazine-2,0- (1H, 3H) -dione, m.p. 133-133.5 ° C, 1-methyl-3- (3-chlorocyclobutyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 160 ° C, 1-methyl-3- (3,1 + -dichloro-cyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 89-90 ° C, 1-methyl-3- (N-isopropylcyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 128-130 ° C, 1-methyl-3- (2-decahydronaphthyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -1-dione, m.p. 208-211 ° C, 1-ethyl-3-isopropyl-6-dimethylamino-s-triazine-2,1 * - (1H, 3H) -dione, m.p. 63-65 ° C, 1-propyl-3-isopropyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, n-5 1,5056, 1-ethyl-3-cyclohexyl-6 -dimethylamino-s-triazine-2H- (1H, 3H) -dione, n * 5 1.5279, 1-methyl-3-ethyl-6-methylamino-s-triazine-2, U- (1H, 3H) dioni, sp. 206-207 ° C, 1-methyl-3- (sec-butyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 199 200 ° C, 1-methyl-3- (tert-butyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 235 "235.5 C, 1-methyl-3-phenyl-6-methylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 293-296 C, 1-methyl-3 - (p -chlorophenyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) -dione, mp> 300 ° C, 1-methyl-3- (3,1 + -dichlorophenyl) -6-methylamino-s- triazine-2,1 + - (1H, 3H) -dione, mp> 300 ° C, 1-methyl-3- (o-chlorophenyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H ) dione, mp> 300 ° C, 1-methyl-3- (o-fluorophenyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) dione, mp> 300 ° C, 1-methyl -3- (m-nitrophenyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) -dione, mp> 300 ° C, 29,579.9 1-methyl-3- (m -trifluoromethylphenyl) -6-methylamino-s-triazine-2,4- (1H, 3H) dione, mp 24-1423 ° C, 1-methyl-3-isopropyl-6-methylamino-s-triazine-2, U - (1H, 3H) dione, mp 223-222 ° C, 1-ethyl-3-isopropyl-6-methylamino-s-triazine-2,4- (1H, 3H) dione, mp 240-241 ° C , 1-propyl-3-isopropyl-6-methylamino-s-triazine-2,4- (1H, 3H) -dione, mp 166-167 ° C, 1-propyl-3- (p-chlorophenyl) -6- methylamino-s-triazine-2,4- (1H, 3H) dione, m.p. . 261-263 ° C, 1-methyl-3-cycloheptyl-6-methylamino-s-triazine-2,4- (1H, 3H) -dione, m.p. 273-27 ° C, 1-methyl-3-cyclopentyl-6-methylamino-s-triazine-2,4- (1H, 3H) dione, m.p. 220-221.5 ° C, 1-methyl-3- cyclooctyl-6-methylamino-s-triazine-2,4- (1H, 3H) -dione, mp> 300 ° C, 1-methyl-3- (2-methylcyclohexyl) -6-methylamino-s-triazine- 2.1 + - (1H, 3H) -dione, mp 246-248.5 ° C, 1-methyl-3-neopentyl-6-methylamino-s-triazine-2,1 + - (1H, 3H) -dione , mp 253-255 ° C, 1-ethyl-3-cyclohexyl-6-methylamino-s-triazine-2,4- (1H, 3H) -dione, mp 226-227 ° C, 1-methyl-3- (3-methylcyclohexyl) -6-methylamino-s-triazine-2,4- (1H, 3H) -dione, mp 255-258 ° C, 1-methyl-3- (m-tolyl) -6-methylamino- s-triazine-2,4- (1H, 3H) -dione, mp 280-282 ° C, 1-methyl-3- (3-chloro-p-tolyl) -6-methylamino-s-triazine -2,4- (1H, 3H) -dione, mp 321.5-322.5 ° C, 1-methyl-3- (2-methyl-5-chlorophenyl) -6-methylamino-s-triazine-2 , 4- (1H, 3H) dione, mp 268-270 ° C, 1-methyl-3- (3-pentyl) -6-methylamino-s-triazine-2,4- (1H, 3H) dione, m.p. 179-182 ° C, 1-methyl-3- (3,4-dimethylcyclohexyl) -6-methylamino-s-tria cis-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, 30 5 7 9 4 0 1-methyl-3- (2,1 + -dimethylcyclohexyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 21 U-216 ° C, 1-methyl-3- (1 + -isopropylcyclohexyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 298-300 ° C, 1-methyl-3- (3,5-dimethylcyclohexyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 250-252 ° C, 1-methyl-3- (1-methylcyclopentyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 236-238 ° C, 1-methyl-3- (3-chlorocyclobutyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 235-236 ° C, 1-methyl-3-octyl-6-methylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 89-91 ° C, 1-methyl-3- (p-methylthiophenyl) -6-methylamino-s-triazine-2,4- (1H, 3H) -dione, m.p. 31H-31T ° C, 1-methyl-3- (2-methyl-1 + -chlorophenyl) -6-methylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 293 DEG-295 DEG C., 1-methyl-3- (ρ-tolyl) -6-methylamino-s-triazine-2,5 (1H, 3H) dione, m.p. 237-211 ° C, 1-methyl-3-isobutyl-6-methylamino-s-triazine-2,1 * - (1H, 3H) -dione, m.p. 206-209 ° C, 1-methyl-3-cyclohexyl-6-ethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 209-211 ° C, 1-methyl-3-cyclohexyl-6-isopropylamino-s-triazine-2,0- (1H, 3H) -dione, m.p. 213-215 ° C, 1-methyl-3-ethyl-6- (tert-butylamino) -s-triazine-2,1 + - (1H, 3H) dione, m.p. 182-183.5 ° C, 1-methyl-3-isopropyl-6-isopropylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 181-181 + C, 1-methyl-3-isopropyl-6-propylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 158-161 ° C, 1-methyl-3-isopropyl-6- (tert-butylamino) -s-triazine-2,1 + - (1H, 3H) -dione, m.p. 185-186.5 ° C, 1-methyl-3-ipropyl-6-allylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 11 + 3,5-U + 5 ° C, 1-methyl-3-isopropyl-6-propargylamino-s-triazine-2,1 + - (1H, 3H) dione, νζ 1.55520, 1-ethyl-3 -isopropyl-6-ethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 170-173 ° C, 3.57940 1-methyl-3-isopropyl-6-diethylamino-s-triazine-2,1 + - (1H, 3H) -dione 25 χζ 1.5129, 1-methyl-3-ipropyl. 6- (N-butyl-N-methylamino) -s-triazine -2,1+ - (1H, 3H) -dione η 5 1,5102,1-methyl-3-cyclohexyl-6- (N- methyl-N-propylamino) -1-ricin-2,1+ - (1H, 3H) -dione η 5 1.5335,1-methyl-3- (n-octyl) -6-dimethylamino-s- triazine-2,1 + - (1H, 3H) dione, m.p. 89-91 ° C, 1-methyl-3- (2-ethoxyethyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 110-113.5 ° C, -1-methyl-3- (2,1 + -dimethylphenyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 192 DEG-19 DEG C., 1-methyl-3-cyclopropyl-6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 171 + -180 ° C, 1-methyl-3- (1 + -tert-butylcyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 173-17 + +C, 1-methyl-3- (3,5'-dimethylcyclohexyl) -β-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 73-76 ° C, 1-methyl-3- (2,1 + -dimethylcyclopentyl) -6-dimethylamino-s-triazine-2,1 + (1H, 3H) -dione, = 1.5363, 1-methyl-3- (3,1 + -dimethylcyclopentyl) -6-dimethylamino-s-triazine -2,1 + - (1H, 3H) -dione, = 1,5210,1-methyl-3- (3-methylcyclopentyl) -6 -dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, = 1.5120, 1-methyl-3- (2,3-dimethylcyclopentyl) -6-dimethylamino-s-triazine-2.1 + - (1H, 3H) -dione, n® = 1.5258, 1-methyl-3-cyclohexylmethyl-6-dimethylamino-s-triazine-2,1+ - (1H, 3H) -dione, m.p. 93-96 ° C, 1-methyl-3- (2-norbornyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 1OO-II + 3.5 ° C, 1-methyl-3- (bicyclo [2.2.2] oct-2-yl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, mp. 101 + -107 ° C, 1-methyl-3- (n-propyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) -dione, m.p. 189-191 ° C, 1-methyl-3- (n-butyl) -6-dimethylamino-s-triazine-2,1 - (1H, 3H) dione, m.p. 167-168 ° C, 1-methyl-3- (n-hexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, δ = 1.5130, 32 5 7 9 4 0 1-methyl-3- (2-ethoxyethyl) -6-dimethylamino-s-triazine-2,1- (1H, 3H) -dione, m.p. 1UU-1U6 ° C, 1-methyl-3- (3,1 + -cimethylphenyl) -6-dimethylamino-s-triazine-2, n- (1H, 3H) -dione, m.p. 202 ° (decomposes), 1-methyl-3- (p-ethylphenyl) -6-dimethylamino-s-triazine-2 -, (1H, 3H) -dione, m.p. 28 DEG-286 DEG C., 1-methyl-3- (m-chlorophenyl) -6-dimethylamino-s-triazine-2,14- (1H, 3H) -dione, m.p. 26 DEG-26 DEG C., 1-methyl-3- (m-fluorophenyl) -6-dimethylamino-s-triazine-2,1- (1H, 3H) -dione, m.p. 268-269 ° C, 1-methyl-3- (3-chloro-1-fluorophenyl) -6-dimethylamino-s-triazine-2,5- (1H, 3H) -dione, m.p. 292-291 + ° C, 1-methyl-3- (o-trifluoromethylphenyl) -6-dimethylamino-s-triazine-2,1 - (1H, 3H) dione, m.p. 2i + 1-2l + 3 ° C, 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine'-2,1 + - (1H, 3H) -dione, m.p. 266.5-268 ° C, 1-methyl-3-cyclopropyl-6-dimethylamino-s-triazine-2,5- (1H, 3H) -dione, m.p. 266-267 ° C, 1-methyl-3- (2,6-dimethylcyclohexyl) -6-dimethylamino-s-triazine-2,5- (1H, 3H) dione, m.p. 128-130 ° C, 1-methyl-3- (2-ethylcyclohexyl) -6-dimethylamino-s-triazine-2,6- (1H, 3H) -dione, m.p. 180-181 ° C, 1-methyl-3- (U-methylcyclohexyl) -6-dimethylamino-s-triazine-2,1 * - (1H, 3H) dione, m.p. 272-273 ° C, 1-methyl-3- (U-tert-butylcyclohexyl) -6-dimethylamino-s-triazine-2,1 - (1H, 3H) dione, m.p. 355-35 ° C (1-methyl-3 - (- methoxycyclohexyl) -6-dimethylamino-s-triazine-2,1 + - (1H, 3H) dione, m.p. 271-27 ° C, 1-methyl-3- (3,5-dichlorocyclohexyl) -6-dimethylamino-s-triazine-2,1 * - (1H, 3H) dione, m.p. 201 + -205 ° C, 1-methyl-3- (2,4-dimethylcyclopentyl) -6-dimethylamino-s-triazine-2,1- (1H, 3H) dione, m.p. 211-213 ° C, 1-methyl-3- (3H-dimethylcyclopentyl) -6-dimethylamino-s-triazine-2,8- (1H, 3H) -dione, m.p. 2U7-2U8 ° C, 1-methyl-3- (3-methylcyclopentyl) -6-dimethylamino-s-triazine-2, U- (1H, 3H) -dione, m.p. > 260 ° C, 1-methyl-3- (2,3-dimethylcyclopentyl) -6-dimethylamino-s-triazine-2,1 * - (1H, 3H) dione, m.p. 225-227 ° C, 33,57940 1-methyl-3- (2-ethylcyclopentyl) -6-dimethylamino-s-triazine-2,4 (1H, 3H) -dione, m.p. 206-208 ° C, 1-methyl-3- (3-cyclohexen-1-yl) -6-dimethylamino-s-triazine-2,4 (1H, 3H) -dione, m.p. 244-245 ° C, 1-methyl-3- (2-decahydronaphthyl) -6-dimethylamino-s-triazine-2,4 (1H, 3H) -dione, m.p. 302-307 ° C, 1-methyl-3- (2-norbornyl) -6-dimethylamino-s-triazine-2,4 (1H, 3H) -dione, m.p. 223-229 ° C, N-methyl-3- (2-norbornylmethyl) -6-dimethylamino-s-triazine-2,4 (1H, 3H) -dione, m.p. 240-244 ° C, 1-methyl-3- (bicyclo [2.2.2] -1 + [17-oct-2-yl) -6-dimethylamino-s-triazine-2,4 (1H, 3H) -dione , sp. 261-265 ° C, 3-isopropyl-6-dimethylamino-s-triazine-2,4 (1H, 3H) -dione, calcium salt, m.p. > 300 ° C, 3- (s-butyl) -6-dimethylamino-s-triazine-2,4 (1H, 3H) -dione, m.p. 161-16 5 ° C, 3- (4-methoxycyclohexyl) -6-dimethylamino-s-triazine-2,4 (1H, 3H) -dione, m.p. 205-209 ° C, 1-methyl-3-cyclohexyl-6- (2-methylallyl) -s-triazine-2,4 (1H, 3H) -dione, m.p. 219-220 ° C, 1-methyl-3- (n-heptyl) -6-dimethylamino-s-triazine-4-thio-2,4 (1H, 3H) -dione, m.p. 59-60 ° C, 1-methyl-3-allyl-6-dimethylamino-s-triazine-4-thio-2,4 (1H, 3H) -dione, m.p. 98-99 ° C, 1-methyl-3-isopropyl-6-dimethylamino-s-triazine-4-thio-2,4 (1H, 3H) -dione, m.p. 141-146 ° C, 1-methyl-3- (p-nitrophenyl) -6-dimethylamino-s-triazine-4-thio-2,4 (1H, 3H) -dione, m.p. 252-253 (dec.) And 1-methyl-3-cyclohexyl-6-isopropylamino-s-trialsin-4-thio-2,4 (1H, 3H) -dione, m.p. 283-284 ° C.

57940 3k

An alternative method for preparing those compounds of this invention in which X is a sulfur atom is represented by the equation 13: 0 a R 'nA t + p * s ^ R' ys «AV3 o ^» Ar, 3! A, · \ R, 2 11 E'2 Λ (compound 11 in which R1 is an alkyl group) in which R1, R * 2, ^ * 3 and 8 ^ are the same as described above.

The diones of formula II + s-triazine-1-thio-2,1 + - (1H, 3H) can be prepared by heating the corresponding oxygen analogs 11b with phosphorus pentasulfide at about 25 ~ 150 ° C for about 1-12 hours in a solvent such as pyridine. The product can be isolated by diluting the reaction mixture with a suitable hydrocarbon solvent (such as toluene), separating the solids (e.g., by filtration) and further extracting the solids with a hydrocarbon solvent and then crystallizing the product from hydrocarbon solvent extracts, or treating the product with water and treating the product with water. as above.

The following example and Table IX illustrate this procedure.

Example 6 Synthesis of 1-methyl-3'-cyclohexyl-6-dimethylamino-s-triazine-1 + -thio-2,2- (1H * 3H) -dione in 25 parts of 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine- When dissolved in 2,1- (1H, 3H) -dione, 200 parts of phosphorus pentasulfide are added to 200 parts of pyridine. The mixture is refluxed for six hours under a nitrogen atmosphere. The hot reaction mixture is diluted with 250 parts of toluene and the supernatant is decanted. The residue is stirred twice with 250 parts of hot toluene and the supernatant is decanted. The combined supernatant is concentrated in vacuo 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-1-thio-2,1- (1H, 3H) -dione, m.p. 210-212 ° C.

In a similar manner 1-methyl-3-cyclopentyl-6-dimethylamino-s-triazine-1-thio-2,1- (1H, 3H) -dione can be prepared, m.p. 181,5_186 ° C.

35 57940

compositions

The compounds of formula I are useful in controlling unwanted vegetation. They can be used whenever general weed control is needed, such as in industrial areas, railway tracks, and areas adjacent to farmland in agricultural areas.

The exact amount of 6-aminotriazinedione to be used in any given situation will vary depending on the desired result, the particular use, the plant and soil, the mixture recipe used, the mode of use, the prevailing weather conditions, the density of foliage, and so on. Because so many variables affect the issue, it is not possible to present a usage rate that would suit all situations. Broadly speaking, the compounds of the invention are used in amounts ranging from about 1/2 kg / ha to about 25 kg / ha.

The compounds of formula I may be combined with other herbicides and are particularly useful for bromosil (3-sec-butyl) -5-bromo-6-methyl-uracil, diuron (3- (3,3-dichlorophenyl) -1,1-dimethylurea). ), paraguate (1,1 * -dimethyl-1,1,1'-bipyridinium ion), m- (3,3-dimethylureido) phenyl tert-butyl carbamate, L-amino-6-tert-butyl-3 in connection with itmethylthio-as-triazin-5 - (UH) -one and s-triazines such as 2-chloro-L-ethylamino-6-isopropylamino-s-triazine in the control of various weeds.

The compounds of formula I can be mixed in various ways which are customary for herbicides with similar physical properties. Useful recipes include wettable and soluble powders, suspensions and solutions in solvents and oils, aqueous dispersions, dust granules, spheres and very concentrated mixtures. Broadly speaking, these recipes consist essentially of about 1 to 99 weight-weighting herbicide active ingredients (containing at least one compound of formula I effective as a herbicide) and at least one a) about 0.1 to 20 weight-weighting surfactant b) about 5 ~ 99 weight-dispute solid or liquid diluent. More specifically, different types of recipes generally contain the following approximate amounts of these ingredients.

weight Percent

Herbicide Diluent Surfactant

Wetted powders 25 ~ 90 0-7U 1-10

Suspensions or solutions 5 ~ 50 1 + 0-95 0-10

Aqueous dispersions 10-50 1 + 0-89 1-10 Dusts 1-25 70-99 0-5

Granules and spheres 1-35 65-99 0-15

Highly concentrated mixtures 90-99 0-10 0-2 36 5 7 9 4 0

The actual percentages that can be achieved with each compound of Equation I depend on the the physical properties of the compound.

The manner in which such herbicidal compositions are prepared and used is described in several patents (U.S. Patent No. 3,309,192, U.S. Patent No. 3,235,357 »U.S. Patent No. 2,655 1 * 55, U.S. Patent 2,863,752, U.S. Patent No. No. 3,079 2hkt U.S. Patent No. 2,891,855 and U.S. Patent No. 2,6k2 35 ^) ·

Many of the compounds of this invention have an unusually high Liu hardness in water, up to several percent. This offers the advantage that, for example, the growth of shrubs and other deep-rooted perennial weeds can be curbed. An example of a highly water-soluble compound of this invention is 1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,1 * - (1H, 3H) -dione; the solubility of this compound in water is about 3.2% at 25 ° C.

Example 7

Solution of 1-1-methyl-3-cyclohexyl-6-dimethylamino-s-triazine-2,5- (1H, 3H) dione 37%

Ethylene glycol monobutyl ether 35

Methanol 9

Water 19

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

Example 8

Wettable powder 1-methyl-3-cyclopentyl-6-dimethylamino-s-triazine-2, h- (1H, 3H) dione 25%

Dairy 71.5

Dioctyl sodium sulfosuccinate 1.5

Low viscosity methylcellulose 2

The ingredients are thoroughly mixed together and passed through a hammer mill to form particles, most of which are less than 100 microns in size.

Determination of Weed Killing Activity The herbicidal activity of the compounds of this invention was determined in a greenhouse experiment. In this experiment, crawling weeds (Digitaria spp.), Yard grass (Echinochloa crusgalli), wild oats (Avena fatua), small oysters (Cyperus rotundus), Cassia tora, morning glow (impomoea spp.), Mustard (Bassica spp.), Radish (Radass) were planted. ), calendula (Tagetes spp.), salt grass (Rumex crispus) seeds and small-leaved tubers were planted in growth medium and treated with two amounts (2.2 and 0.1 * 1 * kg / ha) of these chemicals dissolved in a non-toxic solvent for the plants before emergence. Simultaneously, 37,57940 were treated with Johnson grass (Sorghum halepense) with four leaves, creeping weeds and yard grass with three leaves and tuberous small ryegrass (Cyperus rotundus) with two leaves after emergence at 2.2 kg / ha. Treated plants and control plants were kept in a greenhouse for sixteen days, at which time all species were compared to control plants and visually classified for treatment-induced reactions. Quantitative classification was made on a scale of 0-10; a value of 10 means complete destruction, a value of 0 means damage. Qualitative classification (type of damage) was also performed; the letter "C" means fading and the letter "G" means growth retardation. Reviews of some of the preferred compounds of this invention in this experiment are set forth in Tables I, II, and III. As shown in Table III, the compounds of the invention are more potent than the known herbicide, atrazine.

—- 38 57940

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3 · Ρ · Η -P, Π ajÖiH ^ tC '-' (VJ -H-—

• H Jm g H · Η to-H e O tO'H · Η CO · Η ·> Ό tC

I — I -Ρ 3 [> j C i> i ö * h -h so C i — I (—I td I co to I -n ϊοο-ροόό-ρο ιό te f '· *' - no *> 4 ίΟ · Η M h -P · Ρ CU -H II CU · Η <- ίο - | ffi -pc i S dt) g ti 0 Ό tn_p Orvo O to 01 · Η | IPC-Hl Αί_ρ Ai "-P-— 39 57940

Table II

Biological potency of 6-aminotriazinedione; dose 2.2 kg / ha, unless otherwise stated; column A - yard, after emergence column B - creeping weed, before emergence, column C - weed, before emergence, column D - Cassia, before emergence, column E - mustard, before emergence; C and G have the same meaning as above.

0 * \

N N

I il CH

C C / CH 3

I CH

CH

R1 A B C D E

ethyl 6C JC 9C 8C 10C

n-propyl 6C 9C 10C 10C 10C

n-butyl 10C 10C 10C 10C 10C

isobutyl 9C 10C 10C 10C 10C

t-butyl 9C 9C 10C 10C 10C

neopentyl 10C 10C 10C 10C 10C

allyl 10C 10C 10C 10C 10C

n-hexyl 10C 10C 10C 10C 10C

2-methallyl 6C 10C 8c 10C 10C

3-methoxypropyl 1C 9C JC 10C 10C

3-methylthiopropyl 3C 10C 10C 10C 10C

2-ethoxy ethyl 1C 8C 1 * C 10C 10C

phenyl 2C / 6G 10C 10C 10C 10C

m-tolyl 9C 10C 10C 10C 10C

p-tolyl 7C 9C 10C 10C 10C

BJU-dimethylphenyl-9C 9C 10C 10C

p-ethylphenyl 6c 10C 10C 10C 10C

3, 4-dichlorophenyl JC 10C 10C 10C 10C

2,5-dichlorophenyl + C 10 C 9 C 10 C 10 C

3-trifluoromethyl-U-

chlorophenyl 1B 10C 10C 10C 10C

jD-chlorophenyl 3B 10C 10C 10C 10C

m-chlorophenyl 10C 10C 10C 10C 10C

o-chlorophenyl 6c 10C 10C 10C 10C

m-fluorophenyl 10C 9C 10C 10C 10C

3-chloro-U-fluorophenyl 7C 10C 10C 10C 10C

3-chloro-6-methylphenyl 6C 9C 9C 10C 10C

continues 1.0 57940

R1 Λ B C D E

3-chloro-4-methylphenyl 8C IOC 10C IOC IOC

3-Trifluoromethylphenyl 6C IOC ICC IOC 1GC

3-nitrophenyl 5C 9C IOC IOC 1GC

E-methylthiophenyl IB 6G 1C IOC IOC

cyclooctyl IOC IOC IOC IOC IOC

cycloheptyl IOC IOC IOC IOC IOC

cyclopropyl 1C 3C 2C IOC IOC

2,4-dimethylcyclohexyl IOC IOC IOC IOC IOC

£ -isopropyylisyklo-

hexyl IOC IOC IOC IOC IOC

3,4-dimethylcyclo-

hexyl IOC IOC IOC IOC IOC

2,6-dimethylcyclohexyl

hexyl '' 9C 9C IOC IOC IOC

2,3-dimethylcyclohexyl IOC IOC IOC IOC IOC

3-chlorocyclobutyl IOC IOC IOC IOC IOC

E-methylcyclohexyl IOC IOC IOC IOC IOC

E - isopropoylcyclohexyl - gc 8C gc 10C 10c 3,5-dimethylcyclohexyl

hexyl IOC IOC IOC IOC IOC

3,4-dichlorocyclohexyl

li IOC IOC IOC IOC IOC

p-methoxycyclohexyl IOC IOC IOC IOC IOC

2,4-dimethylcyclo-

pentyl IOC IOC IOC IOC

3,4-dimethylcyclo-

pentyl IOC IOC IOC IOC

* 3-methylcyclopentyl 9C IOC IOC IOC

2,3-dimethylcyclo-

pentyl 5C IOC IOC IOC

3-cyclohexen-1-yl IOC IOC IOC IOC IOC

2-cyclohexen-1-yl IOC IOC IOC IOC IOC

cyclohexylmethyl IOC IOC IOC IOC IOC

2-decahydronaphthyl 0 7G 9C IOC IOC

2-norbornyl IOC IOC IOC IOC IOC

2-norbornylmethyl IOC IOC IOC IOC IOC

* Bicyclo / 2.2.21,47o1t-2-

yl 0 8C 9C IOC

1-methylcyclopentyl IOC IOC IOC IOC IOC

dose 0.44 kg / ha - not studied (continued) ut 5,794 0 0

1 N N

I i

C C

0 * ^ \ n / nNHGH3 CH3

R1 A B C D E

ethyl 8C 7G 6C 8C 10C

n-propyl 7C 9C IOC IOC 10C

n-butyl 8C 9C IOC IOC 10C

s-butyl 4C 9C 9C IOC 10C

- isobutyl 8C 9C IOC IOC 10C

t-butyl.i 6C IOC 8C IOC 10C

neopentyl * + C IOC IOC IOC 10C

n-octyl 10C O O O 3C

n-hexyl IOC IOC IOC IOC 10C

3-pentyl 6C IOC 9C IOC 10C

phenyl IOC IOC IOC IOC 10C

m-tolyl O 8C 9C IOC 10C

3,4-dimethylphenyl 2C 7C 8C IOC 10C

E-isopropylphenyl IB 8G 9C IOC 10C

E-ethylphenyl O 7C 8C IOC 10C

m-chlorophenyl 8C 9C IOC IOC 10C

o-chlorophenyl O 3G 1C IOC 10C

m-fluorophenyl IOC 9C IOC IOC 10C

o-fluorophenyl 5C IOC 9C IOC 10C

3-chloro-4-fluorophenyl 7C 9C IOC IOC 10C

3,4-dichlorophenyl O 8C 7C IOC 10C

3-chloro-6-methylphenyl 1C 3G O IOC 10C

U-chloro-6-methylphenyl O 1C O 9C 9C

2-trifluoromethylphenyl 4C 9C 9C IOC 10C

3-nitrophenyl O 6C 6C IOC 10C

N-methylthiophenyl O 2 G O 1 C 7 C

cyclohexyl IOC 9C IOC IOC 10C

2-methylcyclohexyl IOC IOC IOC IOC 10C

cyclooctyl IOC IOC IOC IOC 10C

cyclopropyl 1C O 2G 8C 9C

cyclopentyl IOC IOC IOC IOC 10C

3-methylcyclohexyl IOC IOC IOC IOC 10C

cycloheptyl IOC IOC IOC IOC 10C

(continued) 1.2 57 9 40

Rj .ABODE

3,4-dimethylcyclohexyl IOC 9C IOC IOC IOC

2,3-dimethylcyclohexyl 7C IOC IOC IOC IOC

4-isopropylcyclohexyl 3C 9C IOC IOC IOC

2, β-dimethylcyclohexyl IOC 6C 6C IOC IOC

3,5-dimethylcyclohexyl 5C IOC IOC IOC IOC

p-chlorophenyl 8C 9C IOC IOC IOC

3-trifluoromethylphenyl 9C 9C 9C IOC IOC

2-ethylcyclohexyl 9C IOC 9C IOC IOC

3-chlorocyclobutyl IOC IOC IOC IOC IOC

1-methylcyclopentyl IOC IOC IOC IOC IOC

U-methylcyclohexyl IOC IOC IOC IOC IOC

U-t-butylcyclohexyl 00 0 IOC IOC

p-methoxycyclohexyl 1C 9C 8C IOC IOC

3,4-dichlorocyclohexyl 4C IOC IOC IOC IOC

2,4-dimethylcyclopentyl IOC IOC IOC IOC

3, k-dimethylcyclopentyl IOC IOC IOC IOC

'S-methylcyclopentyl IOC IOC IOC IOC

2,3-dimethylcyclopentyl IOC IOC IOC IOC

2-ethylcyclopentyl IOC IOC IOC IOC

3-cyclohexen-1-yl IOC IOC IOC. IOC

? -decahydronaphthyl 5C 9C IOC IOC IOC

2-norbornyvli IOC IOC IOC IOC IOC

2-norbornylmethyl 6C IOC IOC IOC IOC

bicyclo / 2.2.2.4.4 / oct-2-yl 0 5G 7C IOC

3-chloro-ε-tolyl 0 6C 8C IOC IOC

- not studied (continued) 1 * 3 57940 o

II

N N

I I! C __.- R-

° 'Y

R2>

R ± R2 R3 'R4 A BCD E

isopropyl 1/2 Ca ++ methyl methyl IOC 10C IOC IOC 10C

"isopropyl Li + methyl methyl IOC IOC 1GC IOC 10C

isopropyl methyl methyl IOC 9C IOC IOC 10C

t-butyl H methyl methyl IOC IOC IOC IOC 10C

- t-butyl H methyl methyl IOC IOC IOC IOC 10C

neopentyl H methyl methyl IOC IOC IOC IOC 10C

isopropyl Na + H methyl 9C 9C IOC IOC 10C

isopropyl ethyl H ethyl 9C 3C 2C 4C 9C

isopropyl methyl ethyl ethyl 3C 8C 7C IOC 10C

isopropyl methyl methyl butyl ** C 7C 7C IOC 10C

isopropyl n-propyl H methyl 1C 7C 5C IOC 10C

isopropyl ethyl H methyl ** C 7 C 8 C 8 C 10 C

E-chlorophenyl H methyl methyl 9C 7C 10C 9C 5C

cyclohexyl H methyl methyl IOC IOC IOC IOC 10C

3,4-dichlorocyclo-

hexyl H methyl methyl 9C IOC IOC IOC 10C

t-butylcyclohexyl H methyl methyl 0 6G 4G IOC 9C

1-methylcyclohexyl

pentyl H methyl methyl IOC IOC IOC IOC 10C

£ -methoxycyclohexyl

hexyl H methyl methyl 9C 9C IOC IOC 10C

cyclohexyl methyl H ethyl 8C IOC IOC IOC 10C

cyclohexyl methyl H isopropo- 5C IOC UC IOC 10C

pyy li

cyclohexyl methyl methyl n-propyl IOC 9C IOC IOC 10C

cyclohexyl ethyl H methyl 9C IOC IOC IOC 10C

cyclohexyl ethyl methyl methyl IOC IOC IOC IOC 10C

isopropyl ethyl methyl methyl 8C 9C IOC IOC 10C

isopropyl n-propyl methyl methyl 0 8C 7C IOC 10C

isopropyl methyl H isopropyl 1C 3C 1C 7C 9C

pyyii

isopropyl methyl H n-propyl o 2C 0 3C 10C

isopropyl methyl H allyl 8C 7C 5C 9C 10C

isopropyl methyl H propargyl-3C 8G 7C 10C 10C

(continued) 57940 p

II

Sr λ i i Y ^ R2

^ ^ 2 R3 Ri »A B C D E

* 3-methylcyclo- 11 11 methyl methyl 10C IOC IOC 10C - hexyl * cycloheptyl methyl methyl methyl IOC IOC IOC 10C -

Jt. · Isopropyl methyl methyl methyl 6C 9C IOC 10C -

cyclopentyl methyl methyl methyl IOC IOC IOC IOC 10C

o-fluorophenyl methyl methyl methyl 8C IOC IOC IOC 10C

2-nitrophenyl methyl methyl methyl 0 7G 7C IOC 10C

2-methyl-cyclohexane

hexyl methyl methyl methyl 10C 10C IOC IOC 10C

cyclohexyl methyl H isopropyl 0 10C 10C 10C 10C

E-fluorophenyl methyl methyl methyl 9C 10C IOC IOC 10C

m-fluorophenyl methyl methyl methyl 10C IOC IOC IOC 10C

- not studied * dose 0.4 * »kg / ha.

k5 57940

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The particularly advantageous properties of the triazinediones according to the invention compared with the well-known herbicide, atrazine, are shown in Tables IV and V.

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Claims (3)

1. As herbicides useful 6-amino-5-triazine-2, M1H, 3H) -diones of Formin R 1 5S 2 1 61 R_ A- lA 0. N> h "where R represents an alkyl group of 2-8 carbon atoms which may be substituted *" by a methoxy, ethoxy, methylthio or ethylthio group, an alkenyl group of 3. carbon atoms, a cycloalkyl group of U-8 carbon atoms , which may be substituted by an alkyl group having 2-U carbon atoms, 1 or 2 methyl groups, 1 or 2 carbon atoms or a bromine atom, cyclohexenyl, cyclohexylmethyl, trimethylcyclohexyl, tetramethylcyclohexyl or a bicycloalkyl group having T-8 carbon atoms, or further may be a phenyl group of formula wherein Y is a hydrogen, fluorine, chlorine or bromine atom, an alkyl group of 1-U carbon atoms, an alkoxy or alkylthio group of 1-2 carbon atoms, a nitro or a trifluoromethyl group, and Y is a hydrogen or chlorine atom or a methyl group, R 2 is a hydrogen atom, an alkyl group having 1-3 carbon atoms or Na, Li, K, 4 * (Ca / 2), ammonium or dimethylammonium ion, R 2 is a hydrogen atom or a methyl or ethyl group, R 2 is an alkyl group of 1-U carbon atoms, an alkenyl group of 3-t carbon atoms, p ropargyl or methoxy group, and X is an oxygen or sulfur atom, provided that X is a sulfur atom, are neither nor R Process for the preparation of compounds according to claim 1, characterized in that it comprises the following successive steps: