DE2326312A1 - TRIAZINDONE DERIVATIVES AND THEIR PREPARATION AND APPLICATION - Google Patents

Description

y patent attorneys:
Dr. Ing.Walter Abltz Dr. Dieter F. M ο rf Dr. Hans-Α. Brauns 8 Munich 86, Pienzenauaritr. 28

E. I. DU PONT DE NEMORS AND COMPANY 10th and Market Streets, Wilmington, Del. I9898, V.St.A,

Triazinedione derivatives and their preparation and application

Neumayer et al., "Pesticides", Chemical Week, April 12 and 26, 1969 j mention various commercial and experimental s-triazine herbicides; including Prometon and Prometryn's structural formula :

CH ₇ . IN CH ₃ . - CH ₃ . I || CH,

HC - N ^ ^ t - CH HC- N ^^ N ^{/ v} SiT - CH

ITT TTJ ITT TTt

CH, ^{a U} CH, CH _x ^{M Ά} CH,

3 -33 3

Prometon Prometryn

3.0 9849/1224

These and related compounds are described in U.S. Pat. No. 2,909-420.

In U.S. patent application serial no. 301,853 of October 30, 1972 and DT-OS 22 4-5 44-9 is a class of 1,3,5-triazinediones the general formula

described, in which E ¹ denotes hydrogen or certain organic groups, E "denotes certain organic groups and X denotes oxygen or sulfur. As described there, these compounds are suitable as selective herbicides.

Those described in this United States patent application and DT-OS Compounds represent intermediates in the manufacturing process the new class of highly active herbicides according to the present invention.

The invention represents a class of new, herbicidally more effective Compounds of the formula

1 i 3

^R 2
(D

309849/1224

available in what

R. alkyl with 3 'to 8 carbon atoms, cycloalkyl with 3 8 carbon atoms, methylcyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, irimethylcyclohexyl, tetramethylcyclohexyl, Cycloalkylalkyl with 4 to 7 carbon atoms, alkenyl with 3 "to 4 carbon atoms, alkynyl with 3 4 carbon atoms, benzyl or

-Y /

with

Y is hydrogen, halogen, alkyl with 1 to 4 carbon atoms, nitro, alkoxy with 1 to 4 carbon atoms, alkylthio with Λ to 4 carbon atoms, cyano or trifluoromethyl,

Z hydrogen, halogen, methyl, ethyl, nitr:>, alkoxy with 1 to 4 carbon atoms or alkylthio with 1 to 4 carbon atoms and
Q is hydrogen, halogen or methyl,

E _{2 is} alkyl having 1 to 4 carbon atoms, E ₃ is SE ₄ or OE ₄ with

E ^, equal to alkyl having 1 to 6 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkenyl with 3 to 4 carbon atoms, alkynyl with 3 to 4 carbon atoms or benzyl and

Xy, and Xp independently belong to the group oxygen and sulfur.

The invention further provides weed control agents which contain the above compounds as an active ingredient, and a method for controlling unwanted vegetation, including unwanted vegetation in crops, such as

3 0 9 8 n / a / Ί 2 2 U

Wheat, and soybeans, by applying the compounds and / or means.

Certain compounds of the formula I are preferred because of their higher herbicidal effectiveness and their ease of synthesis. These include compounds of the formula I where E ^ is alkyl with 3 to 6 carbon atoms or cycloalkyl with 5 to 8 carbon atoms, E ₂ is methyl, E ₅ is SE ^ or OE ^,

E. equals alkyl with 1 to 6 carbon atoms or alkenyl with 3 to 4 carbon atoms and and X ₂ equals oxygen.

The compounds of the formula I are particularly preferred because of their maximum herbicidal effectiveness and selectivity
E. equals alkyl with 3 to 4 carbon atoms or cycloalkyl

with 5 to 7 carbon atoms, E ₂ is methyl, E is SCH ,, SC ₀ H ₁ -, OCH, or OC ^ H ₁ . and

3 3 ^? 3 ^ P Χ ,, and X ₂ is oxygen.

Preferred herbicidal compounds of the above formula include:

i-methyl ^ -eyclopentyl-G-methylthio-s-triazine ^ j ^ -

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

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

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

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

- 4 30984y / 1224

B-8031 / -1 ^

1-methyl-3-cyclhexyl-6-ethylthio-s-triazine-2, ^ -

(1H, 3H) -dione
1-Metliyl - .. 3-cyGlopentyl-6-metho3q5r-s-triazine-2,4-

(1H, 5H) -dione
1-methyl ~ 5-cyclop entyl-6-ethoxy-stria zin-2,4-

(iH, 3H) -dione.

The compounds of formula I with X ^ equals X ₂ equals oxygen can be prepared using the method explained by the following equations:

? 3 °,

1) E ^ -N = C = O ₊ HNC = NH> E ^ -NCNC = NH

^{1 d 1} HH

ter-OE-, 0 tiary 0 E,

2) E -NCNC = NH + Cl-CX _x -CH _x E ^ ₁ -NCNC = NCX _x -CH-

1HH P> ¹ HH

■ E _x 0 E _x 0 *

1a) H ₂ ET-C = NH + Cl-CX-CH _x " ⁸

EO 0 E _x

NCH> ENCCC

2a) E.-NCO + H ₀ IT-C = NCX _x CH _x ---> E ^ -NCNC = NCX _x CH I ^ ί> Ο ¹ HH

HH

OE _x

3) E ^ -NCNC = NCX _x -CH _x ¹ HH 5 5 3

8 ^ 9/1224

B-8031 / -1

Herein, R. ,, Ep and E-, the above meaning is X ₇ . Oxygen or sulfur, M ^{1 is} an alkali metal and R is hydrogen or alkyl having 1 to 4 carbon atoms. The synthesis of 1-Thiοa11ophanimidaten and 1,3-Dithioallophanimidaten from thiopseudourea (equation 1) is analogous to. a procedure according to Organic Synthesis 4-2 , 87 (1962), which describes the preparation of methyl 4-phenyl-3-thioallophanimidate (1-phenyl-2-thio-4-methylisobiuret). . '

Leave the reaction products of Equation -1 at about 0 up to 45 ° C and atmospheric pressure in an inert, organic Solvents, e.g. B. methylene chloride, with one equivalent of a chlorofonate or chlorothiol format in the presence of an equivalent of an acid acceptor such as triethylamine or trimethylamine or dirnethylaniline, react (equation 2). After the reaction is complete, the methylene chloride solution is with Water washed and dried and the solvent evaporated to Alkoxycarbonyl thioallophanimi da ie, Alkylthiolcarbonylthioallophanimidaie, To obtain alkoxycarbonylallophanimidates and alkylthiolcarbonylallophanimidates.

The reaction products of Equation 2 are also obtained by adding the pseudourea or thiopseudourea first with a chloroformate or chlorothiolformate as in equation 1a and then the reaction products of equation 1a reacts with an isocyanate as in equation 2a.

The reaction products of equation 2 are then momentary refluxed with an alkali alkoxide or hydroxide such as sodium or potassium methoxide or hydroxide in methanol, to cause cyclization (Equation 3) · The solvent is evaporated under vacuum; the residue is washed with ether or dissolved in water and acidified. The acidification

3098Α9 / 122Λ

Β-8031 / -1

the aqueous solution usually leads to the precipitation of the desired s-triazinedione as an essentially pure solid. If the desired compound does not precipitate on acidification, it is taken up in methylene chloride. The solvent is then evaporated off and the dried residue is recrystallized. The essentially pure alkali salt (corresponding to the alkali metal in the alkoxide or hydroxide) is obtained by washing the residue with ether and filtering off the resulting solid. The same alkali salts are also obtained by dissolving the s-triazinediones in methanol containing one equivalent of alkali alkoxide or hydroxide, such as sodium methoxide or hydroxide, and then evaporating off methanol. The alkali salts of s-triazinediones react with alkyl halides, sulfates or tosylates to form the 1-alkyl analog compounds according to the invention (equation 4). Both components are refluxed for 5 to 10 hours at about 50 to 153 ° ^C. in an appropriate, inert, organic solvent such as tetrahydrofuran, dimethylformamide or acetonitrile. The solvent is evaporated and the residue is dissolved in methylene chloride. By washing the methylene chloride solution with water, drying and evaporation, the 1-alkyl analogue compounds according to the invention are obtained in an essentially pure state.

The compounds according to formula I can also be prepared by the process illustrated by the following equations:

? 3 '? 2? 3

5) R ₀ -NC = NH + R ^ -N = C = X ₀ ■> R "-NG -N = C -N-

d _E Ί d ' I _HH

- 7 8A-V / 12 24

B-8O3V-1?

? 2? 3

6) E.-KCK = CNR ₀ + ¹ EH ^

The synthesis of the 1,2-dialkylpseudourea or 1,2-dialkyl-2-thiopseudohamea takes place according to a procedure analogous to that in J. Chem. Soc, 3551 (1955)? described. The pseudourea is reacted with an isocyanate or isothiocyanate as in equation 1. The reaction product of equation is used to obtain the s-triazine-2,4- (iH, 3H) -diones, thio-striazine-2,4 (iH, 3H) -diones and s-triazine-2,4- (1H, 3H) -dithiones according to the invention with phosgene or thiophosgene at about 0 to 100 ° C in the presence of a:
Ή , N-Dimethy! Aniline, implemented.

0 to 100 ° C in the presence of a base such as triethylamine or

The s-triazine-4-thio-2,4 (iH, 3H) -diones and s-triazine-2,4- (1H, 3H) -dithiones According to the invention can also be produced by the method explained by the following equation:

To form the desired s-triazine-4-thio-2,4 (1H, 3H) -dione an s-triazine-2,4 (1H, 3H) -dione is used with phosphorus pentasulphide at about 25 to 125 ° C in a solvent such as Pyridine around. The solvent is evaporated and the residue recrystallized in a solvent such as benzene.

30 9 B -J -122 / »

B-893V-1 S.

The compounds according to the invention are valuable herbicides. Certain compounds can be used to control weeds in crops, such as wheat and soybean, without harm such crops are used »

j? The compounds can be used in the form of a pre-emergence treatment, targeted post-emergence treatment or, in certain special cases, general treatment after emergence. The application dose ranges from 1/4 to 10 kg / ha. The method and dose of application depend on factors such as the crop, soil type, climatic conditions and weed population. Ο It is important that the connections are evenly distributed.

The compounds can also be combined with other herbicides to control a wider range of weeds like Linuron, Terbutryn, Diuron, Terbacil and Paraquat.

The formulation of the compounds according to formula I can be based on the various physical properties that are similar for herbicides usual ways * to the formulations belong wettable and soluble powders, suspensions and oil solutions, aqueous dispersions, dusts, granules, pellets and highly concentrated compositions. Generally seen These formulations consist essentially of about 1 to 99% by weight of herbicidally active material (containing at least a compound of formula I in a herbiciden.Werk amount) and at least one component from group (a) about 0.1 to 20% by weight surfactant; and (b) about 5 to 99% by weight essentially biologically inert, solid or liquid diluent. The various Types of formulations generally contain these ingredients in the following approximate proportions:

8 /, S / 1 2 2 U

Herbicide weight%

Thinner surface agent active ingredient

Wettable powders 25-90 0-74 1-10

Oil suspensions or

solutions 5-35 55-94 1-10

Aqueous dispersions 10-50 40-89 1-10

Dusts 1-25 70-99 0-5

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

High concentrates 90-99 0-10 0-2

The exact percentages that can be achieved with a given compound of formula I depend on the physical Properties of the connection.

How such weed killers are made and used is described in numerous patents, e.g. U.S. Patents 3,309,192, 3,235,357, 2,655,445, 2 863 752, 3 079 244, 2 891 855 and 2 642 354.

Examples of formulations of compounds according to the invention are:

example 1

Solution weight%

1-methyl-3-cyclohexyl-6-methylthio-37

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

Ethylene glycol monobutyl ether 35

Methanol 9

Water 19

By combining and stirring the ingredients, a solution is obtained that can be diluted with water for spraying «

- 10 -

3 0 9 8 /. ■} / 1 2 2

Weight .% 25th 71 , 5 1 , 5 2

B-8031 / -1

Example 2

ITettable powder

1 -Methyl- 3-cyc lopentyl-6-methylthi o
s-triazine-2,4 (1H, JH) - dione

Diatomaceous earth dioctyl sodium sulfosuceinate low viscose methyl cellulose

By thoroughly mixing the ingredients and passing through By, a hammer mill, particles are formed that are essentially all are less than 100 microns in size.

The herbicidal activity of the compounds according to the invention has been examined in the greenhouse, with seeds of Digitaria sp., Echinochloa crusgalli, Avena fatua, Cassia tora, Ipomoea sp. , Brassica sp., Eaphanus sp., Tagetes sp., Rumex crispus and tubers of Cyperus sp. placed in a wax medium and before emergence with that in a non-phytotoxic Solvent dissolved chemical have been treated. Treated plants and control samples were im Held in the greenhouse, whereupon all species were compared with controls and visually for response to treatment were assessed, with a qualitative assessment (on the nature of the response of the plant) being made. Here means C chlorosis, G growth inhibition and S albinism. The symbol "x" means that the compound is in the named plant was not checked. In addition, a quantitative evaluation was carried out on the basis of a scale from 0 to 10, with 0 none Effect means and 10 maximum effect, e.g. complete destruction in the case of chlorosis. The for The following table lists some highly active compounds obtained according to the invention.

- 11 -

3 0 9 I, ' «■ 2 k

kg / ha

Before the emergence

'& CO
ο CO M. CD
•H co CO w CO X CO
• Η ijH
Ar-i P.
co B. co (D
O O ω
-P φ Ph O r- \ «Η ω 03 0 •H
CQ I. φ co
P. O co CO ft CO O W. barrel S. • Η • η ω pj O ft CO CO pi hO CD O 100 H (H co 100 • Η o Fh r * 60 100 100 pq ΊΟ0 90 [V] Q 0 100 100 100 100 100 100 2.2 100 90 100 10 100 100 100 100 100 100 0.44 100 80 90 0 100 100 100 100 100 90 2.2 100 100 100 O 100 100 100 100 90 60 -a 0.44 90 100 80 O 100 100 100 100 50 100 11 80 90 80 0 100 100 100 100 100 30th 2.2 60 60 0 100 100 100 90 20th 90 2.2 70 70 40 0 100 100 100 80 100 100 0.44 10 40 20th 0 100 100 100 100 100 100 11 90 100 90 20th 100 100 100 100 100 100 2.2 90 90 80 10 100 100 100 100 100 100 11 90 100 100 0 100. 100 100 100 100 90 2.2 90 100 100 0 100 100 100 100 100 90 11 90 100 100 0 100 100 100 100 100 90 2.2 90 100 100 0 100 100 100 90 11 90 90 90 ' 100 90 2.2 2G 40 60

1-methyl - ^ - cyclopentyl-δ-methylthio-S-triazine-2,2
2.4 (1H, 3H) -dione

i-methyl - ^ - cyclohexyl-e-ethoxy-s-triazine-2,4 (iH, 3H) -dione

1 -Methyl- 3-tert. -butyl-6-methylthio-s-triazine-11

2,4 (iH, 3H) -dione

1-methyl-3- (p -chlorophenyl) -6-methylthio-striazine-2,4 (1H, 3H) -dione

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

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

1-methyl-3-Cm-chlorophenyl) -6-methylthio-striazine-2,4 (iH, 3H) -dione

1-methyl-3- (o-fluorophenyl) -6-methylthio-striazine-2,4 (1H, 3H) -dione

kg / ha.

Before accruing (continued)

co

τ!

CO -P

• Η

• Η

CO

OH O CO

pi ω

co

• Ρ CO «Η

CO

CQ Φ ϋ

CO • Η CQ CQ CO O

cd φ ο

Ph H

CO

ϋ • Η

CQ CQ

CO

CQ

ti

ρ <

CO

CQ Φ • Ρ Φ

W CO

EH

1-methyl-3- (2-methylcyclohexyl) -6-methylthios-triazine-2,4 (1H, 3H) U

to 1-methyl-3-cycloheptyl-6-methylthio-s-tria-ο zin-2,4 (iH, 3H) -dione

co 1 -Methyl-3-cyclooctyl-6-methylthio- ' ^t s-triazine-2,4 (1H, 3H) -dione

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

, o 1-methyl-3- (3-methy1cyclohexyl) -6-methylthio- *. s-triazine-2,4 (1H, 3H) -dione

^/ ! -Methyl-3-neopentyl-6-methylthio-s-triazine-2,4 (1H, 3H) -dione

1-methyl-3-Cp-chlorophenyl) -6-methoxy-striazine-2,4C1H, 3H) -dione

i-methyl - ^ - isopropyl-δ-methylthio-s-triazine-2,4 (iH, 3H) -dione

2.2 90
0.44 70

2.2 100
0.44 100

2.2
0.44

2.2
0.44

2.2
0.44

2.2

0.44

11 100
2.2

90
80

100
90

100
90

7G

11
2.2

100

90

.80

90

80

100
90

100 100

100 90

100 100 80 80

100 100 4G 50

100 90

90

90

100
40

100
100

80

90

20th

90

SS

90 70

100 100 100 100 100 100 '100 100 100 100 100 90

100 100 100 100 100 100 100 100 100 100 100 100

60 100 100 100 100 80 30 100 100 80 60 50

10 100 100 100 100 100 0 100 100 100 6G 90

60 100 100 100 100 90 50 100 100 100 100 90

100 100 100 100 100 100 100 90 100 20 20 80

100 100 100 100 100 100 10c 90 90 90 so 10c

100 100 100 100 100 100 100 100 100 100 100 100

B-8031 / -1

With two compounds according to the invention there are further tests Have been carried out. In one test, seeds of wheat, Avena Fatua, Bromus tectorum and Bromus secalinus were found placed in pots containing soil and before emergence with 1-methyl-3-cyclopentyl-6-methyltMo-s-triazine-2,4 (iH, 3H) -dione treated in a non-phytotoxic solvent. The pots were kept in the greenhouse for one month. The samples were compared to control samples and visually assessed the response to treatment as rated above. Results:

kg / ha wheat Avena fatua. Bromus bromus

tectorum secalinus

2.20 4G 3C 1OC 1OG 1OC

1.10 2C 1OC 1OC 1OC

0.55 2C 1OC 1OC 1OC

0.27 0 1OC 1OC 90

In another test, seeds from the same plants as above were placed in greenhouse potted soil. After a week, the young plants were treated with 1-methyl-3-cyclopentyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione incorporated in a non-phytotoxic solvent with a wetting agent and a humectant. The pots were kept in the greenhouse for three weeks. The samples were compared to control samples and assessed visually for response on treatment as rated above. Results:

kg / ha wheat Avena fatua "Bromus Bromus

tectorum secalinus

0.55 1C 70 '1OC 1OC

0.27 0 0 20 60

0.13 0 0 0 1C

0.07 0 0 0 0

1-methyl-3-cyclopentyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione is therefore highly effective as a selective herbicide when used in wheat culture both before and after emergence.

- 14 309849/1224

In another experiment, seeds of Digitarla sp., Echinochloa crusgalli, Avena Fatua, Sorghum halepense, Paspalum dilatatum, Setaria faberii, Poa pratensis, Bromus rigidus, Eleusine indica, Brassica sp., Ssumex crispus, Amaranthus retroflexica, Cypereneus, Aeschynomeneus , Barbarea vulgaris, Sida spinosa, Datura stramonium-, Ipomoea and soybeans in containers with loamy, sandy Fallsington soil and before emergence with Λ -methyl- 3-cyclohexyl-6-methylthio-s-triazine-2, A- (iH, 3H) -dione treated in> a non-phytotoxic solvent. The treated containers were taken to a greenhouse and kept there for four weeks. The samples were compared to control samples and visually rated for response to treatment as above. Results:

3 0 9 8 / -J-, 152 2

B 1 8 6 O

O j * OO ο 03
Ω 100 8th DOU ro
Ω DOU

VD O Ω Ω

VJl νΧ)

ςι Ω

-Λ

03 O

Ω Ω

.Λ _Λ

O O

Ω Ω

VJl O

Q Ω

O O

Ω Ω

-Λ _Λ

O O

Ω Ω

-Λ -Λ

O O

Ω Ω

σ ο

Vn
Ω 100 Φ 100 DOU DOU DOU 03
Ω 100 DOU

Digitaria sp "
EcMnocliloa crusgalli

ο ο

A vena fatua

Sorghum halepense Paspalum dilitatum

Setaria faberii

Poa pratensis
Bromus rigidus

Eleusine indiea

Brassica sp.
Rumex crispus

Amaranthus retroflexus

Cyperus

Aeschynomene virginica

Beard> aria vulgaris

Sida spinosa

Datura stramonium.

Ipomoea

Soybean

ΖίίΒΖίΖ

Example?

1-methyl-3-isopropyl-6-methylthio-s-triazine-2,4 (1H, 5H) -dione

56.9 parts of potassium hydroxide in 200 parts of water are added dropwise to a solution of 69.5 parts of 2-methyl-2-thiiopseudo] iai ⁱ nsto ff sulfate iind 47 parts of methylchlorofoimate in 1000 parts of water at 0 C, and the reaction mixture is 3 hours. "Stirred at room temperature and then extracted with methylene chloride and then dried the methylene chloride extract and evaporated the solvent on a rotary switch, with 45 parts of methyl N- (i-amino-1-methylthiomethylene) carbamate, F. 72 to 77 ° C ₁ .

74 parts of the above compound and 47 parts of isopropyl isocyanate in JOO parts of methylene chloride are stirred overnight. By evaporating off the solvent on a rotary evaporator 113.6 parts of methyl-4-isopropyl-N-methoxycarbonyl-ithioallophanimidat, F. 129 to I32 ⁰ C, was obtained.

100 parts of the above compound are 1 hour with 27 parts Sodium methoxide is refluxed in 200 parts of methanol, whereupon the methanol is stripped off on a rotary evaporator, dissolve the kickstand in 200 parts of water, neutralize the aqueous solution with hydrochloric acid and filter off the solid and dries, 55 parts of 3-isopropyl-6-methylthio-s-triazine-2,4 (1H, 3H) -dione, F. 188 to 190 ° C.

A solution of 32 parts of sodium methoxide in 400 parts Methanol is mixed with 132 parts of 3-isopropyl-6-methylthio-striazine-2,4 (1H, 3H) -dione added and evaporated in vacuo, whereupon the white solid is triturated with methylene chloride and filtered, -um 110 parts of sodium 3-isopropyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione, F.> 300 ° C, to win.

- 17 309849/12

B-805V-1

J » . ■

80 parts of sodium 3-isopropyl-6-methyltliio-s-triazine-2,4- (iH, 5H) -dione and 49 parts of methylidide are refluxed overnight in 700 parts of acetonitrile, whereupon the solvent is evaporated and the residue is dissolved in methylene chloride , the methylene chloride solution washes with water, dries and evaporated in order, after recrystallization from chlorobutane / hexane, to produce 54 parts of 1-methyl-3-isopropyl-6-methylthio-s-triazine-2, ^z t- (1H, 3H) -dione, i ¹ ·. 74 to 77 ° C, to win .;

Example "4

1-methyl-5-phenyl-6-methylthio-s-triazine-2,4 (iH, 5H) -dione

26 parts of sodium 3-phenyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione (Obtained similarly to Example 1 for the preparation of sodium 3-iospropyl-6-methylthio-s-triazine-2,4 (1H, 3H) -dione described with the modification that the isopropyl isocyanate is replaced by phenyl isocyanate) and 16 parts Methyl iodide are refluxed in 200 parts of acetonitrile, whereupon the solvent is evaporated and the residue is dissolved in methylene chloride and the methylene chloride solution Washed with water, dried and evaporated to give 18 parts of 1-methyl-3-phenyl-6-methylthio-s-triazine-2,4 (1H, 3H) -dione, . 232.5 to 233 ° C.

Example 5

1-methyl-5-tert-butyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione

A solution of 278 parts of 2-methyl-2-thiopseudohamea sulfate in 2000 parts of 50% isene, aqueous methanol at 0 ° G is added dropwise with 176 parts of ^> 0% i. ^ Ev sodium hydroxide solution and then with 180 parts of tert-butyl isocyanate in 400 parts of tetrahydrofuran are added. The solution is partially evaporated on a rotary evaporator and filtered to obtain 180 parts of methyl 4-tert-butyl-1-thioallophanimidate, E. 102 to 104 ° C., after drying.

- 18 309849/1224

B-80J1 / -1 * ■ ■

A solution of 113.4 parts of the above compound and 80 Parts of triethylamine in 1000 parts of methylene chloride at 0 ° C 66 parts of methylchlorothiol formate in 100 parts of methylene chloride are added dropwise, whereupon the solution is added stirs over, washes once with water, dries and evaporates, by 76 parts of methyl-4-tert. -butyl -N-methylthiolearbonyl-1-thioallophanimidate, P. 102 to 105 ° C to win.

50 parts of the above compound are 1 hour with 30 parts I reflux sodium methoxide in 500 parts of methanol, whereupon the reaction mixture is cooled, the methanol is evaporated on a rotary evaporator and the residue is washed with ether washes to JO parts of sodium 3-tert-butyl-6-methylthio-striazine-2,4- (iH, 3H) -dione to obtain.

24 parts of sodium 3-tert-butyl-6-methylthio-s-triazine-2,4- (iH, 3H) -dione and 15.5 parts of methyl iodide are kept in 200 parts of acetonitrile are refluxed, whereupon the solvent is evaporated off, the residue in methylene chloride dissolves, the methylene chloride solution washes with water, dried and evaporated to after. Recrystallization from chlorobutane 15 Parts of 1-methyl-3-tert. -butyl-6-methyl thio-s-triazine-2,4- (1H, 3H) -dione, F. 138 to 140 ° C.

Example 6

1-methyl-3-cyclohe: xyl-6-methylthio-s-tri3zine-2,4 (1H, 3H) -dioii

84 parts of methyl IT- (1-amino-1-methyl thiomethylene) carbamate in 500 parts of methylene chloride with 71 parts of cyclohexyl isocyanate and a catalytic amount of dibutyl tin dilaurate offset. The solution is refluxed for 3 hours and cooled, and now with 3I parts of sodium methoxide in 300 parts Methanol is added, whereupon the solution is refluxed for 1 hour and the solvent is evaporated off on a rotary evaporator and triturated the residue with ether, about 71 parts

- 19 3 0 9 8 A -J / 1 2 2 4

Uatrium-3-cyclo] iexyl-6-meth.yltliio-s-triazine-2,4 (iH, 3H) -dione, F.> 300 ° C, to win.

A suspension of 26 parts of the above compound in 200 parts of acetonitrile containing 16 parts of methyl iodide is refluxed overnight, whereupon the solvent is evaporated off on a rotary evaporator, water and methylene chloride are added to the residue, the methylene chloride layer is dried and evaporated on a rotary evaporator in order, after trituration with pentane, 19 parts of i-methyl-3-cyclohexyl-6-methylthio-s-triazine-2, -4 (iH, 3H) -dione, Έ. 135 to 137 ° G, to win.

The product is also made using dimethyl sulfate as the alkylating agent. 4-39 parts of 3-cyclohexyl-6-methylthio-s-triazine-2,4- (iH, 3H) -dione sodium salt in 25OO parts of water at 25 ° C. and pH 9 to 9.5 are added dropwise in the course of a Hour with 284 parts of dimethyl sulfate, the solid that forms is filtered off and dried to remove 324 parts of crude 1-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4- (iH, 3H) -dione, i ^1st 154 to 138 ⁰ C to win.

Example 7

1-methyl-5-cyclopentyl-6-methylthio-s-triazine (2,4-C ^/ 1H, 5H) -dione

50 parts of sodium 3-cyclopentyl-6-methylthio-s-triazine-2,4- (iH, 3H) -dione (obtained similarly to Example 1 for the preparation of sodium-3-isopropyl-6-methylthio-s-triazine-2,4- (iH, 3H) -dione described, but replacing the isopropyl isocyanate by cyclopentyl isocyanate) and 3Ί parts of methyl iodide are refluxed in 400 parts of acetonitrile, whereupon the solvent is evaporated, the residue in methylene chloride dissolves, the methylene chloride solution washes with water, dried and evaporated and the residue in a chlorobutane / hexane mixture recrystallized to 24 parts of 1-methyl

- 20 -

3 0 9 8 A ¹ J / '1 2 2 U

B-803V-1 ■. *

3-Cyclopentyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione, ' 80 to 83 ° C.

Example 8

1-Meth.Yl-3-Cp-chlorophenyl) -6-methoxy-s-tri'azine-2,4 (iH, 5H) -dione

52 parts of 2-methylpseudourea hydrogen sulfate in 250 parts of water from 0 to 5 ° ^G are mixed with 31 parts of methyl chloroformate and then dropwise with 74 parts of 50% sodium hydroxide solution, whereupon the reaction mass is stirred for 3 hours at room temperature, then extracted with methylene chloride Methylene chloride extract dries and the solvent is evaporated and the residue is triturated with hexane to obtain 23 parts of methyl N-Ci-amino-i-methoxy-methylene ^ carbamate, mp 36 to 39 j 5 ° C.

130 parts of the above compound in 200 ml of mathylene chloride 150 parts of p-chlorophenyl isocyanate are added, whereupon the reaction mass is stirred overnight, then the solvent evaporated and the residue refluxed for 3 hours in 100 parts of methanol containing 54 parts of sodium methoxide and the mixture is now evaporated to dryness, around 3OO parts Sodium 3- (p-chlorophenyl) -6-methoxy-s-triazine-2,4 (iH, 3H) -dione, to win.

70 parts of the triazinedione sodium salt in 2 ^ 0 parts of dimethylformamide 54 parts of methyl p-toluenesulfonate are added, whereupon the mixture is stirred overnight at room temperature and then the solvent is evaporated off in vacuo Triturated residue with a 1% sodium carbonate solution and recrystallized the resulting solid from acetonitrile to obtain 30 parts of pure 1-methyl-3- (p-chlorophenyl) -6-methoxy-striazine-2 ^, 4 (iH, 3H) -dione, F. 185 to 187 ° C.

- 21 -

309849/1224

"Al

Example 9

The s-.Triazinediones mentioned in the following table are prepared according to the procedures of Example 3 to 8, by adding the 2-methylpseudourea and 2-methyl-2-thiopseudourea by the mentioned 2-substituted compounds replaced, used other isocyanates and the methyl p-toluenesulfonate and methyl iodide by said alkylating agents replaced.

- 22 309849/1224

Thiopseudoharristoff
or pseudourea

Isocyanate alkylating agent s-triazinediones

2-ethyl pseudourea isopropyl

isocyanate

2-MetJb.ylpseudourea m-fluorophenyl-

isocyanate

2-ethyl-pseudo-urine-ω material

ο 2-methyl-2-thio-
^m pseudourea

■ ~ i II

Methyl p-toluenesulfonate

m-Chlorophyll isocyanate

Cyclohexyl isocyanate

sec-butyl isocyanate

I-methylcyclopentyl isocyanate

Cycloheptyl isocyanate

2-methylcyclohexyl isocyanate

2,4-, 6-irimethyl

cyclohes ^ liso-

cyanate

J, 5-dimethylcyclo » hexyl isocyanate

2., 3,5,6-tetra

methylcyclohexyl-

isocyanate methylοοdid

1 -Methyl-3-i-sopropyl-6-ethoxy-stri: azine-2,4 ( ^/ 1H, 3H; -dione, Np = 1.4900

1-methyl-3- (m-fluorophenyl) -6-metho xys-triazine-2,4 (IH, 3H; -dione, F. I56 to 158 ⁰ C.

1-methyl-3- (m-chlorophenyl) ~ 6-methoxy-s-triazine-2,4 (1H, 3H) ~ dione, Έ. 186 to 188 ° G

1-methyl-3-cyclohe2cyl-6-ethoxy-striazine ^ 2,4 (1H, 3H) -dione, Ng5 = 1.5610

1-methyl-3-sec-butyl-6-methylthios-triazine-2,4 (1H, 3H) -dione, "" '= 1.5382

1-methyl 1-3- (1-methy1eyelopentyl) -6-methylthio-s-triazine-2,4 (1H, 3H) -dione, P. 84 to 86 ° G

1-methyl-3-cycloheptyl-6-methylthios-triazine-2,4 (1H, 3H) -dione, F. 98 to 1010 C.

1-methyl-3- (2-methylcyclohexyl) -6-methylthio-s-triazine-2,4 (1H ₅ 3H) -dioiij m.p. 98 to 100 ° C-. .

1-methyl-3- (2,4,6-trimethylcyclohexyl) ~ 6-methylthio-s-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (3,5-dimethylcyclohexyl) -6-methylthio-s-triazine-2,4 (iH, 3H) -dione, Ng ^ = 1.5400. &>

1-methyl-3- (2,3,5 _? 6 »tetramethylcyclo-- ^a) hexyl) -6-methylthio-s-triazine-2,4 ~ * (iH, 3H) -dione ¹ ^

Thiopseudourea
or pseudourea

2-methyl-2-thiopseudourea

Isocyanate alkylating agent s-triazinediones

ro
ί ¹ -

3,4-dimethyl

cyclohexyl

isocyanate

2,5-dimethylcyclo-

hexylisocya-

nat

Cyclooctyl isocyanate

3-methylcyclohexyl! socyanat

Methyl iodide

Heopentyl isocyanate

Isopropyl isocyanate

p-chlorophenyl-n-propyl iodide isocyanate

n-butylgodide

Isopropyl isocyanate

Methyl aodide

m-Trifluoromethylphenyli socyanat

m-Ni t rophenyl isocyanate

1-methyl-3- (3,4-dimethylcyclohexyl) -6-methylthio-s-triazine-2,4 (iH, 3H; -dione, P. 85 to 87 ° C

1-methyl-3- (2,5-dimethylcyclohexyl) -6-methy 1 thi o- s-1 ri a zin- 2,4 (1H, 3H) dione, Np = 1.5382

1-methyl-3-cyclooc tyl-6-methylthi os-triazine-2,4 (iH, 3H; -dione, P. 93 to

94.5 ° σ.

1-methyl-3- (3-methylcyclohexyl) -6-methylthio-s-triazine-2,4 (iH, 3H) -dione, P. 95 to 97 ° C

1-methyl-3-neopentyl-6-methylthio-striazine-2,4 (iH, 3H) -dione, P. 99 to 103 ° C

1-butyl-3-isopropyl-6-methylthio-striazine-2,4 (iH, 3H) -dione, Np = 1.5143

1-propyl-3- (p-chlorophenyl) -6-methylthio-s-triaain-2,4 (IH, 3H) -dione, mp 148-150 ° C

1-propyl-3-i propyl-.6-methyl thi> - striazine-2,4 (1H, -3H; -dione P. 92 to 96 ^s C

1-methyl-3-isopropyl-6-methylthios-triazine-2,4 (iH, 3H) -dione, Np = 1.5257

1-methyl-3- (m-trifluoromethylphenyl) -6-methylthio-s-triazine-2,4 (iH, 3H) -dione, F. 70.5 to 73 ° 0

1-methyl-3- (m-nitrophenyl) -6-methyl-

thio-s-triazine-2,4 (iH, 3H) -dione,

F. 239 to 2400 G

Ihiopseudourea or pseudourea

2-methyl-2-thiopseudourea

Isocyanate alkylating agent s-triazinediones

oo

VJl CO

Benzyl isocyanate methyl iodide

Butyl isocyanate

2,5-dichlorophenyl isocyanate

Cyclopropyl isocyanate

2,6-dimethyl-phenyl isocyanate

2-methyl-5-chlorophenyl isocyanate_

3-0hiοr-4-methylphenyl isocyanate

Phenyl isocyanate

Cyclohexyl isocyanate

o-5'luo2? phenyl isocyanate

o-nitrophenyl isocyanate ethyl iodide
Methyl iodide

1-methyl-3-benzyl-6-methylthio-striazine-2,4 (iH, 3H) -dione, P. 138 to 141 ° 0- '. β

1-methyl-3-butyl-6-methylthio-s- ι

triazine-2,4 (iH, 3H) -dione, P. 7SbXs, ^ 79 ° G

1-methyl-3- (2,5-dichlorophenyl) -6-methylthio-s-triazine-1,4 (iH, 3H) -dione, P. 255 to 258 ° C

1-methyl-3-cyclopropyl-6-methylthios-triazine-2,4 (1H, 3H) ~ dione, j>. 146 to

150 ⁰ c

1 -Methyl-3- (2,6-diine thylphenyl ") -6-methylthio-s-triazine-2,4 (1H, 3H) -dione, P. 178 to 181 ° C

1-methyl-3- (2-methyl-5-chlorophenyl) -6-methylthio-s-triazine-2,4 (iH, 3H; -dione, P 203.5 to 206 ° 0

1-methyl-3- (3-chloro-4-methylphenyl) -6-methylthio-s-triazine-2,4 (1H, 3H; -dione ^ F228 to 23Ο ⁰ 0

1-methyl-3-phenyl-6-methylthio-s ^! -triazine-2,4 (iH, 3H) -dione, P. 232.5 to 233 C

ethyl ^ cyclohexylem triazine-2,4 (iH, 3H) -dione,

p = 1.5424

1 -Methyl- 3 ~ (0- f luo! Phenyl) -6-rae thylthio-s-triazine-2,4 (1H, 3H) -dione, P. 129 to 132 ⁰ C

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

Ihiopseudourea or fseudo urea.

2-methyl-2-thiopseudo-oxygen

Isocyanate

Alkylating agents s-triazinediones

INJ!
PO

2-allyl-2-thio-

pseudourea

2-methyl pseudourea

Propyl isocyanate methyl iodide

m-tolyl isocyanate

Allyl isocyanate

3,4-dichlorophenyl isocyanate

p-fluorophenyl isocyanate

P-nitrophenyl isocyanate

p-bromophenyl isocyanate

o-chlorophenyl 'isocyanate

m-chlorophenyl isocyanate

Cyclohexylmethyl- "isocyanate Isopropylj ο di d
Iso "butylgodide

2-iodine "butane methyl iodide

Isopropyl isocyanate

Octyl isocyanate Methyl p-toluenesulfonate

1-methyl-3-propyl-6-methylthio-s- ' triazine-2,4 (iH, 3H7-dione, i \ 189 to ο C., ^

1-methyl-3 ^ (m-tolyl) -6-methylthio-s- ι triazine-2,4 (1H, 3H), - dione, I ¹ . 192.5 ^ to 195.5 ^Ö G

'1-Methyl-3-allyl-6-methylthio-striazine-2,4 (1H _? 3H) -di one, F 132 bis

133.50 c

1-methyl-3- (3,4-dichlorophenyl) -6-methylthio-s-triazine-2,4 (1H, 3H) -di one, Ϊ ¹ . 204.5 to 207 ° C

1-isopropyl-3- (p-fluorophenyl) -6- ^

methylthio-s-triazine-2,4 (iH, 3H) -dione

1-isobutyl-3- (p-nitrophenyl) -6-methyl-. thio-s-triazine-2,4 (1H, 3H) -dione

1-sec-butyl-3- (p-bromophenyl) -6-

methylthio-s-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (o-chlorophenyl) -6-methyithio-s-triazine-2,4 (1H, 3H) -dione, F. 152 to 154.5 ° C '■

1-methyl-3- (m-chlorophenyl) -6-methylthio-s-triazine-2,4 (1H, 3H) -dione, P. 297 to 297.5 ° G

1-methyl-3-cyclohexyl methyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione, Ϊ. 102.5 to 104 ° C

1-methyl-3-isopropyl-6-allylthio-striazine-2,4 (iH, 3H) -aei on

1-methyl-3-cotyl-6-methoxy-s-triazine ~ 2,4 (iH, 3H) -dione

K5 CO Ni

Thiopseudourea
or pseudoliar

2-methylpseu.dourea

Isocyanate alkylating agent s-triazinediones

2-Ethylp Seudoharnsto ff

£ J ^; 2 rMe thylpseudo-

urea

2-hexyl-2-thiophene urea

Cyclohexyl isocyanate

P-fluorophenyl isocyanate

sec-butyl isocyanate

p-chlorophenyl isocyanate Meth.yl p-toluenesulfonate

Isopropyl p-toluenesulfonate

Methyl p-toluenesulfonate

P-nitroplienyl "

isocyanate

p-bromophenyl "

isocyanate

3,4-dichloro "

phenyl isocyanate

p-methoxyphenyl " isocyanate

p-tolyl isocyanate " Benzyl isocyanate "

2,4-dichlorophenyl " isocyanate

Propyl isocyanate methylgodide y3yy
triazine-2,4 (1H, 3H) -dione

1-methyl-3- (p-fluoroplienyl) -6-methyl-oxy s-triazine-2,4- (iH, 3H; -dione

1 ~ methyl-3-sec-butyl-6-methoxy-striazine-2, ^ - (1H, 3H) -dione

1-Isopropyl-3- (p-ch.lorophenyl) -6-methoxy-s-triazine-2, A- (1H, 3.H) -dione

1-methyl-3- (p-chlorophenyl) -6-ethoxy-

s-triazine-2,4- (1H, 3H) -di.on

1-methyl-3- (p-nitrophenyl) -6-methoxy s-triazine-2,4- (1H, 3H ') - dlon

1 -Methyl- 3- (p-bromophenyl) ~ 6-methoxys-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (3,4-dichlorophenyl) -6-methoxy-s-triazine-2, ^ (iH, 3H; -diOn

1-Me thyl-3- (p-me tho xypheny 1) -6-me thoxy-s-triazine-2,4 (IH, 3H) -d ⁱ on

1-methyl-3- (p-tolyl) -6-methoxy-striazine-2,4- (1H, 3H; -dione

1-methyl-3-TDenzyl-6-methoxy-s-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (2,4-dichlorophenyl) -6-methoxy-s-triazine-2,4 (iH, 3H) -dioneF

1-methyl-3-pIΌpyl-6-hexyΓthio-striazine-2, ^ - (1H, 3H) -dione

Thiopseudourea or. Pseudourea

Isocyanate alkylating agent s-triazinediones

2-cyclopropyl-2-thio
pseudourea Cyclopropyl
isocyanate Methyl iodide dd 2-cyclohexyl-2-thio-
p seudourea Gyclooctyl-
isocyanate dd Methyl p-toluene
sulfonate 2-allyl-2-thio-
pseudourea Cyclopropylr-
methyl isocyanate dd Il 2- (2-butenyl) -2-thio
pseudourea Cyclohexyl
methyl isocyanate dd Methyl iodide co
* * 2-propargyl-2-thio-
pseudourea Allyl isocyanate dd It CO
OO
* ">, 2- (2-butynyl) -2-thio
pseudourea 2-butenyl isocyanate " dd IC '
---.ro
_λΟ0 2-benzyl-2-thio
pseudourea Propargylic
isocyanate ti ? v> ι
ro
* ■ » 2-methylpseudo-
urea 2-butynyl
isocyanate It 2-hexylpseudo-
urea < Benzyl isocyanate 2-methy1-2-thio
pseudourea p-iodophenyl "
isocyanate 2-ethyl-2-thio-
pseudourea 'm-Tolyl isocyanate ti p-butylphenyl
isocyanate It p-nitrophenyl
i socyanat ' ti ■ o-methoxyphenyl
isocyanate

1-methyl-3-CyClOPrOPyI-O-CyCIoPrOPyI- c thio-s ~ triazine-2,4 (iH, 3H) -dione ^

1-methyl-3-cyclooctyl-6-cyclohexyl- ^ thio-s-triazine-2,4 (iH, 3H) -di'on- J

ί1-Methyl-3-cyclopropylmethyl-6-allylthio-s-triazine-2,4 (1H, 3H) -dione

1-methyl-3-cyclohexylmethyl-6- (2-butenylthio) -s-triazine-2, A- (iH, 3H) -dione

· 1-Methyl-3-allyl-6-propargylthio-striazine-2,4 (1H, 3H) -dione

1-methyl-3- (2-butenyl) -6- (2-butynylthio) -s-triazine-2,4 (iH, 3H) -dione

1-methyl-3-propargyl-6-benzylthio-striazine-2,4 (iH, 3H; -dione

.1 -Methyl-3- C 2-butyny 1) -6-methoxy-s- ⁰ O triazine-2,4 (iH, 3H) -dione

■ 1 ^ methyl-3-benzyl-6-heχyloxy-s-triazine-2,4 (iH, 3H) -dl: on

1-methyl-3- (p -iodophenyl) -6-methylthios-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (m-tolyl) -6-ethylthio-striazine-2,4 (iH, 3H; -di.on

1-methyl-3- (p-butylphenyl) -6-ethyl-KJ thio-s-triazine-2,4 (iH, 3H) -dione "ω

1-methyl-3- (p-nitrophenyl) -6-ethyl- _OT thio-s-triazine-2,4 (iH, 3H) -dione co

1-methyl-3- (o-methoxyphenyl) -6-ethyl- ~ * thio-s-triazine-2,4 (1H, 3H) -dione ¹ ^

Thiopseudohamstoff
or pseudourea

2-ethyl-2-thiopseudourea

Isocyanate alkylating agent s-triazinediones

2-methyl-2-thio
p seudourea f

2-ethyl p seudo shark fabric

m-butoxyphenyl methyl iodide isocyanate

Cyclopentyl " isocyanate

p-methylthiophenylsocyanate

m-butylthiophenyl isocyanate

p-cyanophenyl isocyanate

m-trifluoromethylphenyl isocyanate

3,5-dichlorophenyl isocyanate

pi

phenyli socyana t

2-ChiΟΓ-4-methylphenyl isocyanate "

2-methyl-4-chloro- "phenyl isocyanate _f

2-ethylhexyl- " isocyanate

2-chloro-5-metho: xy-methyl-p-toluene phenyl isocyanate. sulfonate 1-methyl-3- (m-butoxyphenyl) -6-ethyl- ψ thio-s-triazine-2,4 (iH, 3H) -dione

1-methyl-3-cyclopentyl-6-ethylthio- "s-triazine-2,4 (iH, 3H) -dione, J ^1. 49 bis

C-Ί O ρ

P I «

1-methyl-3- (p-methyl-thiophenyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione

1-Methy1-3- (m-buty1thiopheny1) -6-methylthio-s-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (p -cyanophenyl) -6-methylthio-s-triazine-2,4 (iH, 3H) -dione

1-Methyl-3- (m-trifluormethy! Phenyl) -6-methylthio-s-triazine-2,4 (IH, 3H) -dlon, F. from 70.5 to 73 ° C

1-methyl-3- (3,5-dichloiphenyl) -6-methylthio-s-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (p-b jcom-m-chloiphenyl) -6-methylthio-s-triazine-2,4 (1H, 3H) -dione

1-methyl-3- (2-chloro-4-methylphenyl) - ' 6-methylthio-s-triazine-2,4 (iH, 3H; -di: one

1-methyl-3- (2-methyl-4-chlorophenyl) -6-methylthio-s-triazine-2,4 (1H, 3H) -dione, F 165 to 167 C

1-methyl-3- (2-ethylhexyl) -6-methyl-ro thio-s-triazine-2,4 (1H, 3H) -dione co

1-methyl-3- (2-chloro-5-methoxyphenyl) ~ q ^ 6-ethoxy-s-triazine-2,4 (1H, 3H; -di.on ^

Thiopseudourea
or pseudourea

Isocyanate

Alkylation using s-iriazinediones

2-ethylpseudo-
urea 3-methyl-4-bromo-methyl-p-toluene-
phenyl isocyanate sulfonate It It 2-B rom-4-nitro-
phenyl isocyanet ti It 2-nitro-4-chloro
phenyl isocyanate dd Il 2,4-dichlorophenyl
isocyanate dd 2-methylpseudo-
urea 2,4-dibromophenyl-.
isocyanate dd to dd 2 5-dichloro-4- CD
CO
OD dd nitrophenyliso-
cyanate dd ti 3,4-diethoxyphenyl-
isocyanate dd INJ dd 2,4-di fluorophenyl
isocyanate ti ti 2,5-dimethoxyphenyl-
isocyanate t! Il 3,5-dinitrophenyl
isocyanate ti dd 2-fluoro-4,6-dinitro-
phenyl isocyanate

3-nitro-4- fluorophenyl isocyanate

phenyli socyanate

2-Metlioxy-4-nitrophenyl isocyanate 1-methyl-3- (3-methyl-4-bromophenyl) - _ω

'■ * oo

1-Methy1-3- (2-bromo-4- nitrophenyl) -6-ethoxy-s-triazine-2,4 (-1H, 3H) -di: one ς *

1-methyl-3- (2-nitro-4-chlorophenyl) - i 6-ethoxy-s-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (2,4-dichlorophenyl) -6-ethoxy-s-triazine-2,4 (1H, 3H) -dione

1-methyl-3- (2,4-dibromophenyl) -6-methoxy-s-triazine-2,4 (1H, 3H) -dione

1-methyl-3- (2,5-dichloro-4-nitrophenyl) -6-methoxy-s-triazine-2,4 (iH, 3H) -di: one

Λ -Methyl 1-3- (2,5-dimethoxyphenyl) -6-methoxy-s-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (3,5-dinitrophenvl) -6-methoxy-s-triazine-2,4 (iH, 3HJ) -dione

1-methyl-3- (2-fluoro-4,6-dinitrophenyl) -6-methoxy-s-triazine-2,4- (iH, 3H) -dione

1-methyl-3- (3-nitro-4-fluorophenyl) - Κ3 6-methoxy-s-triazine-2,4 (iH, 3H) -di.on u)

1-methyl-3- (2-methyl-4-methoxyphenyl) - ^ 6-methoxy-s-triazine-2,4 (iH, 3H; -dione ^ ₀

1-methyl-3- (2-methoxy-4-nitrophenyl) - - ^Λ 6-methoxy-s-triazine-2,4 (1H, 3H; -dione ¹ ^

1-methyl-3- (3,4-diethoxyphenyl) -6-met'hoxy-s-triazine-2,4 (iH, 3H) -di: one

1-methyl-3- (2,4-difluorophenyl) -6-

Thiopseudourea
or pseudo shark fabric

2-methyl pseudourea

Isocyanate

Alkylating agents s-triazinediones

2-methyl-2-thiopseudohamea

2,4,5-trichloromethyl-p-toluene phenyl isocyanate sulfonate

2,4,6-trimethyl-- " phenyl isocyanate

o-chlorophenyl "isocyanate

2,4-dichlorophenyl " isocyanate

o-tolyl isocyanate "

■ 2,5-dibutoxy- " ρ heny 1 i so c y ana t

2,4-diethylphenyl " isocyanate

2,3-dimethylcyclo-methylodide hexyli socyanat

2,4-dimethylcyclohexyl isocyanate

Cyclopentyl isocyanate

P-ethylphenyl isocyanate

Ethyl iodide n-propyl iodide

n-butyl iodide methyl iodide 1-methyl-3- (2,4,5-trichlorophenyl) -6 ~ methoxy-s-triazine-2,4 ( ^/ 1H, $ H) -dione

1-methyl-3- (2,4,6-trimethylphenyl) -6-methoxy-s-triazine-2,4 (iH, 3H) -dione

1-methyl-3- (o-chlorophenyl) -6-methoxys-triazine-2,4 (iH, 3H ") -dione

1-methyl-3- (2,4-dichlorophenyl) -6-methoxy-s-triazine-2,4- (iH, 3Hj) di

1-methyl-3- (o-tolyl) -6-methoxy-striazine-2,4 (1H, 3H; -dione

1-methyl-3-C2,5-dibutoxyphenyl) -6-methylthio-s-triazine-2,4 (iH, 3H) -dione / ^

1-methyl-3- (2,4-ethylphenyl) -6-methylthio-s-triazine-2,4 (iH, 3H ) -dion

1-methyl-3- (2,3-dimethyicyclohexyl) -6-methylthio-s-triazine-2,4 (iH, 3H; -dione. Έψ = 1.5382

1-methyl-3- (2,4-dimethylcyclohexyl) -6 ₅ methylthio-s-triazine-2,4 (1H, 3H) -dio: i, ^ j / = 1.5332

1-ethyl-3-cyclop en tyl-6-me thylthi o-s-triazine-2,4 (IH, 3H) -dione, F 68 to 7O ⁰ C.

i-n-propyl-3-cyclopentyl-6-methylthio-

s-triazine-2,4 (iH, 3H) -dione, N§5 =

1.5444 ^υ x ^

1-n-butyl-3-cyclopentyl-6-methylthio-

s-triazine-2,4 (iH, 3H) -dione,

Ng5 = 1.5420

1-Methy1-3- (p-ethy! Phenyl) -6-methylthio-s-triazine-2,4 (iH, 3H) -dione, 195 Ms 198 ° C

Thiopseudourea
or pseudourea

2-methyl-2-thiopseudourea

Isocyanate alkylating agent s-triazinediones

ο
tr »oo

.γιο I

2-methylpseudo urea

3,4-xylyl isocyanate

4-chloro-3-trifluoromethylphenyl isocyanate

4-chloro-3-fluorophenyli socyanat

p-methoxyphenyl isocyanate

P-ethoxy phenyl isocyanate

2,4-dimethylphenyl isocyanate

m-iodophenyl isocyanate

p-Cyanophenyl isocyanate Methyljοaid

Cyclopentyl isocyanate Methyl p-toluenesulfonate

1-Methyl-3- (3, ^/ l ~ xylyl) -6-methylthios-triazine-2,4 (1H, '3H) -dione, mp 206 ° C

1-methyl-3- (4-chloro-3-trifluoromethyl- ς phenylV6-methylthio-s-t: riazine-2,4- ', (1H, 3H), dione, m.p. 207 Ms 212 ° C

1-methyl-3- (4-chloro-3-trifluorophenyl) -6-methylthio-s-triazine-2,4 (iH, 3H) -dione, M.p. 180 to 182 ° C

1-methyl-3- (p-methoxyphenyl) -6-methyl-'thio-s-triazine-2,4 (IH, 3H) -dione, mp 196-2010 C

1-methyl-3- (p-ethoxyphenyl) -6-methylthio-s-triazine-2,4 (1H, 3H) -dione, 196.5 Ms 199 ° C

1-methyl-3- (2,4-dimethoxyphenyl) -6-methylthio-s-triazine-2,4- (iH, 3H) -dione, Έ. 157 to 159 C

1-methyl-3- (m-iodophenyl) -6-methylthios-triazine-2,4 (iH, 3H) -dione, F. 168 to

1740 σ

1-methyl-3- (p-cyanophenyl) -6-methylthio-s-triazine-2,4 (1H, 3H) -dione, F. 212 to 214 ° G

1 -Methyl-3-cyclopentyl-6-methoxy-striazine-2,4 (1H, 3H) -dione, M.p. 96 to ho 97 ° C co

B-803V-1 *

Example 10

1-methyl- · 3-cyclolie3q7-l-6-met] iylthio-s-triaziii-4-tliio-2, Ψ- (iH, 3H) -dione

7 »8 parts of phospho- ^ pentasulfide are added to a mixture of 25.5 parts of 1-methyl-3-c ^ clohexyl-6-methylthio-e-triazine-2,4- (1H, 3H) -dione (obtained as in Example 6) add 60 parts of pyridine, refluxed the mixture for 12 hours, after cooling, 30 parts of the pyridine are removed by evaporation under reduced pressure, 100 parts of benzene are added to the residue, the mixture is heated to reflux, decanted, the supernatant material, the residue is mixed with 100 parts of fresh benzene and heated to reflux, the supernatant material is decanted again and the procedure is repeated a third time with 100 parts of benzene. The portions of the supernatant material obtained by decanting are combined and concentrated under reduced pressure, whereupon the resulting crude product is extracted with fresh benzene, the benzene solution is concentrated and placed in a chromatograph! ers column leads j which contains 700 parts of neutral aluminum oxide of activity level III. By the acid fresh benzene is fed and the eluate of the first 1250 parts of benzene is evaporated to dryness to give 18 ₅ 6 parts of 1-methyl-3-cyclohexyl-6-methylthio-s-triazin-4 thio ~ = 2.4 ( iH, 3H) -dione, i ¹ . 157 to 159 ° C ₅ to win =

The following s-triazine-4— "thio- = 2 _? 4 (iH ₉ 5H) -diones are obtained in a similar manner using the appropriate reactants:

1-methyl-3-cyclohe2grl-6-methylthio-4-tllio-s-triazine-2,4

(1H, 3H) -dione, m.p. 158-159 ° C

1-methyl-3-cyclopentyl-6-methylthio = -4 = -thio-s-triazine-2,4-

(1H, 3H) -dione, P. 99 to 102 ° C 1-methyl-3-isopropyl-6-methylthio-4-thio-s-triazine-2,4- (1H, 3H) -dione

308849/1224

B-8031 / -1 *

1 -Methyl ~ 3-tert. -butyl-6-methyl thio-4-thio- s- triazin-2 ", 4- (iH, 3H) -dione 1 -Methyl- 3-eyc 1 op entyl-6-methoxy-4— tlii o-s-tri a zin-2,4- (1H »3H) -dione 1-diethyl-3-cyclohexyl-6-metlioxy-4-thio-s-triazine-2,4 (1H, 3H) -dione 1-Methyl-3-cyclopentyl-6-ethylthio-4-thio-s-triazine-2 _i 4- (1H, 3H) -dione

example

1-methyl-3-cyclopentyl-6-methyl tliio-2-thio-s-t-riazine-2,4 (1H, 3H) - di on

This connection can be established as follows:

21 parts of methyl N-methyl-4-cyclopentyl-i-thioallophanimidate are added and 20 ropes of triethylamine in 200 parts of methylene chloride The reaction mixture is added dropwise to a solution of 12 parts of thiophosgene in 200 parts of methylene chloride at 0 ° C 1 hour at 0 ° C and then subject it to reflux treatment for 10 hours, the solution is now washed with water, dries, the solvent evaporates and the residue crystallizes from chlorobutane, whereby the 1-Methy1-3-eyelopentyl-6-methylthio-2-thio-s-triazine-2,4- (iH, 3H) -dione accrues.

Me following thio-s-triazine-2,4- (iH, 3H) -dione and s-triazine-2,4 (1H, 3H) -dithiones are obtained in a similar manner by using the appropriate reactants:

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

1-methyl-3-isopropyl-6-methylthio-2-thio-s-triazine-2,4- (iH, 3H) -

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

- 34- -

3098Λ9 / 122

1-MettLyl-3-cyclopentyl-6-metlioxy-2-tliio-s-triazine-

2,4 (iH, 3H) -dione

1-methyl-3-cycloliexyl-6-metlioxy-2-tliio-s-triaziii-2,4 (iH, 3H) -

1-methyl-3-cyclopentyl-6-ethylthio-2-tMo-s-triazine-2,4 (iH, 3H) -

1-Methyl-3-cyclohexyl-6-ynethylthio-s-triazine-2,4- (1H, 3H) di tMon 1-methyl-3-cyclohexyl-6-met] iylthio-s-triazine-2 , 4 (iH, 3H) -ditMoii 1-methyl-3-isopropyl-6-methylt3iio-s-triaciii-2,4- (iH, 3H) -ditMon 1-methyl-3-tert-butyl-6-methylthio -s-triaziii-2,4 (1H, 3H) -ditiiion 1-Meth.yl-3-cyclopentyl-6-metlioxy-s-triaziii-2,4- (1H, 3H) -ditliion 1-methyl-3- cyclolie2q7-l-6-ät] ioxy-s-triazine-2 _l 4- (iH, 3H) -dithione.

- 35 -

9.8 ^ .9 / 1 2 2 k

Claims (8)

Claims 1 <"compound of the formula IL · alkyl with 5 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, methylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, * ■ tetramethylcyelohexyl, cycloalkylalkyl with 4 to 7 carbon atoms, alkenyl with 3 ^ i ^{s 2} ^ carbon atoms, alkynyl with 3 to 4 Carbon atoms, benzyl or with Y is hydrogen, halogen, alkyl with 1 to 4 carbon atoms, Nitro, alkoxy with Ί to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, Cyano or trifluoromethyl, Z is hydrogen, halogen, methyl, ethyl, nitro, alkoxy with 1 to 4 carbon atoms or alkylthio with 1 up to 4 carbon atoms and - 36 - 3Q9849 / 1 224 B-803V-1 Q is hydrogen, halogen or methyl, Ep is alkyl of 1 to 4 carbon atoms, E ^ equals SE. or OE. with E. is alkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkenyl with 3 to 4 carbon atoms, alkynyl with 3 to 4 carbon atoms or benzyl and
X /, and X ₂ belong to the group oxygen and sulfur. 2. A compound according to claim 1, characterized in that E. Alkyl with 3 "to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, cycloalkylalkyl with 4 to 7 carbon atoms, alkenyl with 3 to 4 carbon atoms, Alkynyl with 3 "to 4 carbon atoms, benzyl or with Υ is hydrogen, halogen, alkyl with 1 to 4 carbon atoms. Nitro, alkoxy with 1 to 4 carbon atoms, Alkylthio with 1 to 4 carbon atoms, cyano or trifluoromethyl, Z is hydrogen, halogen, methyl, ethyl, nitro, alkoxy with 1 to 4 carbon atoms or alkylthio with 1 to 4 carbon atoms and Q is hydrogen, halogen or methyl. - 37 - 309849/1224 3 · Connection according to claim 1, characterized in that R ₁ is alkyl with 3 to 6 carbon atoms or cycloalkyl with 5 to 8 carbon atoms, S ₂ is methyl, R ^ is SR ₄ or GR ^, where R ^ is alkyl with 1 to 6 carbon atoms or alkenyl with 3 to 4 carbon atoms, and X ₁ and X ₂ are oxygen. k. Compound according to claim I _9, characterized in that R _{1 is} alkyl with 3 to 4 carbon atoms or cycloalkyl of 5 to 7 carbon atoms, R _{2 is} methyl and R _{3 is} SCH ,, SC ₂ H ₅ , -OCH, or OC ₃ H ₅ and X ₁ and X _{3 are} oxygen. 5. A compound according to claim 1 in the form of 1-methyl-3-tert-butyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione. 6. A compound according to claim 1 in the form of 1-methyl-3-isopropyl-6-methylthio-s-triazine-2,4 (iH, 3H) -dione. 7. Compound according to claim 1 in the form of i-methyl-3-cyclohexyl-6-methylthio-s-triazine-2,4 (1H, 5H) -dione. 8. A compound according to claim 1 in the form of i-methyl-3-cyclopentyl-6-methylthio-s-triazine-2 _? 4 (iH, 3H) -dione. . Compound according to Claim 1 in the form of 1-methyl-3-cyclohexyl-6-ethylthio-s-triazine-2,4 (1H, 3H) -dione. 10. A compound according to claim 1 in the form of 1-methyl-3-cyclopentyl-6-ethylthio-s-triazine-2 ₉ 4 (iH, 3H) -dione. 11. A compound according to claim 1 in the form of i-methyl-3-cyclopentyl-6-methoxy-s-triazine-2,4 (iH, 3H) -dione. 12. A compound according to claim 1 in the form of 1-methyl-3-cyclopentyl-6-ethoxy-s-triazine-2,4 (iH, 3H) -dione. 13. Compound of Formula Ϊ2 wherein E ₇ . Alkyl with 3 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, cycloalkyl alkyl with 4 to 7 carbon atoms, alkenyl with 3 to 4 carbon atoms, alkynyl with 3 to 4 carbon atoms, benzyl or phenyl
means, Ep is alkyl of 1 to 3 carbon atoms, E, equal to SE. with E ^ is alkyl of 1 to 4 carbon atoms is and X ₁ and Xp ^{belong to the} group oxygen and sulfur. Compound according to claim 13, characterized in that B ,, equals alkyl with 3 to 6 carbon atoms or Cycloalkyl with 5 to 7 carbon atoms, E ₂ is methyl, E is SE ₄ , where E _{4 is} alkyl having 1 to 4 carbon atoms, and
X ^. and Xq is oxygen. Λ 5. Process for the preparation of compounds of the formula - 39 - 309849/1224 B-8O3V-1 HO O R " O ■■ = wherein Ry, alkyl with 3 to 8 carbon atoms, cycloalkyl with 3 "to 8 carbon atoms, methylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tetramethylöaclohexyl, cycloalkylalkyl with 4 to 7 carbon atoms, alkenyl with 3 to 4 carbon atoms, alkynyl with 3 to 4 carbon atoms, benzyl with Y is hydrogen, halogen, alkyl with 1 to 4 carbon atoms, Nitro, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, Cyano or trifluoromethyl, Z is hydrogen, halogen, methyl, ethyl, nitro, alkoxy with 1 to 4 carbon atoms or alkylthio with 1 to 4 carbon atoms and
Q is hydrogenj halogen or methyl, Eo is alkyl of 1 to 4 carbon atoms, E is SE ₄ or OE ^ with E ^ is alkyl of 1 to 6 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkenyl with 3 to 4 carbon atoms, alkynyl with 3 to 4 carbon atoms - 40 - 30984a / 122Ä B-803V-1 Tl is fuel atoms or benzyl, characterized in that a compound of the formula with a compound of the formula EpJ, where M ' Alkali metal and iodine "means" 16. Process for the preparation of compounds of the formula X ₂ M ι 3 ¹ E ₂ wherein B ,, alkyl with 3 ^> is 8 carbon atoms, cycloalkyl with 3 "to 8 carbon atoms, methylcyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, trimethylcyclohexyl, iEetramethylcyclohesyl5 cycloalkylalkyl with 4 to 7 Carbon atoms, alkenyl with 3 to 4 carbon atoms, Alkynyl with 3 ^ is 4 carbon atoms, benzyl or 309849/122 B-80J1 / -1 ϊ with X is hydrogen, halogen, alkyl with 1 to 4 carbon atoms, Nitro, alkoxy with 1 "to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, Cyano or trifluoromethyl, Z is hydrogen, halogen, methyl, ethyl, nitro, alkoxy with 1 to 4 carbon atoms or alkylthio with 1 to 4 carbon atoms and Q is hydrogen, halogen or methyl, E ~ is alkyl of 1 to 4 carbon atoms, R ^ equals SE. or OR. with E. equals alkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkenyl with 3 to 4 carbon atoms, alkynyl of 3 to 4 carbon atoms or benzyl is and '. Xy. and Xp belong to the group oxygen and sulfur, characterized in that - that one is a compound of the formula H ^ ι 3 E. -NCN = CN- R ₀ • ι ι ι- Έ. H with a compound of the formula CX.Clp. 17. Process for the preparation of compounds of the formula - 42 - 309849/1224 B-8031 / -1 * £ | worm Ry, alkyl with 3 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, methylcyclopentyl, methylcyclohexyl, dimethyl cyclohexyl, trimethylcyclohexyl, tetramethylcyelohexyl, cycloalkylalkyl with 4 to 7 carbon atoms, alkenyl with 3 to 4 carbon atoms, alkynyl with 3 to 4 Carbon atoms, benzyl or with / Y is hydrogen, halogen, alkyl with 1 to 4 carbon atoms, Nitro, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, Cyano or trifluoromethyl, Z is hydrogen, halogen, methyl / ethyl, nitro, alkoxy with 1 to 4 carbon atoms or alkyl thio with 1 to 4 · carbon atoms and
Q is hydrogen, halogen or methyl, Is alkyl of 1 to 4 carbon atoms, equal to SS ^ or OR ^ with R ^ is alkyl with 1 to 6 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkenyl with - 4-3 3 0 9 8 k 97 1 2 2 4 B-8031 / -1 3 to 4 carbon atoms, alkynyl with 3 "to carbon atoms or benzyl and X _{1 is} oxygen or sulfur, characterized in that a compound of the formula ₁ I · Reacts with phosphorus pentasulfide.
1 8. Process for the preparation of compounds of the formula ti wherein E ^. equal to alkyl with 5 to 8 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, cycloalkylalkyl with M to 7 carbon atoms, alkenyl with 3 to 4 carbon atoms, alkynyl with 3 "to 4 carbon atoms, benzyl or phenyl, E _{2 is} alkyl of 1 to 3 carbon atoms and E., equals SE ^, where E ₂ , alkyl with Λ to 4 carbon atoms, characterized in that a compound of the formula 30984Ü / 1224 B-8031 / -1 t! where IL and Ep ^d ^ - ^{e have the} above meaning and M ^! Is alkali metal, with a compound of the formula EpJ ₅ in which Ep has the above meaning, reacts » 19 = weed control agent characterized by a content of a herbicidally effective amount of a compound according to Claim 1 to I ^ and an herbicidal adjuvant, 20 = agent according to claim 19 with particular suitability for combating weeds in useful crops, characterized by a content of a herbicidally effective amount of a compound according to claim 3 and of herbicidal adjuvans , 21. Composition according to claim 19 with particular suitability for combating weeds in useful crops _s characterized by a content of a herbicidally effective amount of a compound according to claim k and of herbicidal adjuvant. ο Agent according to claim 19 with particular suitability for combating weeds in soil crops _s characterized by a content of a herbicidally effective amount of a compound according to claim 1 ^! and on herbicidal adjuvantSo 23. Composition according to claim 22, characterized by a content of active ingredient with R ₁ being cycloalkyl with 5 to 7 carbon atoms. 309849/1224 B-8O31 / -1 2h. Agent according to claim 20 with particular suitability for combating weeds in soybean culture, characterized by a content of the compound according to claim 7 as active ingredient. 25 «Composition according to claim 20 especially suitable for controlling weeds in ways culture _s characterized by a content of the compound according to 'claim 8 as active ingredient. 26. Method of combating weeds _s characterized in that. that a herbicidally effective amount of a compound according to claims 1 to 1 is supplied to the location of the weeds. 303849/1224