CH625520A5 - Process for the preparation of novel 1-thiadiazolyl-5-alkylamino, -arylamino- and -cycloimino-substituted imidazolidinones - Google Patents

Description

The present invention relates to a process for the preparation of new l-thiadiazolyl-5-alkylamino, arylamino and cycloimino substituted imidazolidinones.

The inventive method for the preparation of new compounds of formula I.

R-

N-

N

R1 - C

/

N - R I

CH CH,

wherein R1 and R2 have the meaning given above, with an equimolar amount or a molar excess of an amine or cyclic imine of the formula III

25th

H —N

R3

R4

(III)

- N

\

(I)

■ N - R

wherein R1 is an alkyl, cycloalkyl, alkenyl, haloalkyl, alkoxy, alkylthio, alkylsulfonyl or akylsulfinyl radical, R2 is an alkyl, alkenyl or haloalkyl radical or a radical of the formula

R5

I.

- C - - C = CH

I.

R6

wherein Rr 'and R6 are hydrogen or alkyl, and R3 and R4 are hydrogen, an alkyl radical having up to 18 carbon atoms, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl or cycloalkyl radical or a radical of the formula

(5-n)

"(CH2> m in an inert organic solvent at the reflux temperature of the reaction mixture with azeotropic removal of the water of reaction.

The new compounds which can be prepared according to the invention are surprisingly generally useful as herbicides.

According to a preferred embodiment of the invention, R1 is an alkyl radical having up to 18 carbon atoms, cycloalkyl radical having 3 to 7 carbon atoms, lower alkenyl, lower chloroalkyl, lower bromoalkyl, trifluoromethyl, lower alkoxy, lower alkylthio, never-40 whose alkylsulfonyl or lower alkylsulfinyl radical, R2 a lower alkyl, lower alkenyl, lower haloalkyl or the propargyl radical, R3 and R4 are hydrogen, lower alkyl, lower alkenyl, lower haloalkyl, lower hydroxyalkyl, lower alkoxyalkyl or cycloalkyl radicals with 45 3 to 7 carbon atoms or radicals

(5-n)

50

"(CH2> m

55

wherein X is a lower alkyl or lower alkoxy group, halogen, a lower haloalkyl group, the nitro or 60 cyano group or a lower alkylthio group, n is an integer from 0 to 3 and m is the number 0 or 1, provided that at most one of the radicals R3 and R4 is an aromatic radical, or R3 and R4 together with the nitrogen atom represent a cycloimine radical having 2 to 6 carbon atoms.

“Lower” residues are usually understood to mean straight or branched carbon chains with up to 6 carbon atoms.

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4th

The new compounds are obtained by using a compound of the formula in which R1 has the meaning given above, with about two moles of a dimethylacetal of the formula

N

• N

/

OH

I.

CH

CH,

R - C

C - N

\ /

\

OR7

H - N - CH2 - CH

I I

R2 OR8

(VI)

(II)

-NO

wherein R1 and R2 have the meaning given above, with an amine or cyclic imine of the formula

R3

H-N -R4

(III)

wherein R3 and R4 have the meaning given above, implemented. The reaction is carried out by bringing the compound of the formula II together with an approximately equimolar amount or a molar excess of the compound III in an inert organic medium, for example heptane or toluene, whereupon the reaction mixture is heated to the reflux temperature with stirring and the water of reaction is azeotropic away. The reaction mixture is then normally cooled and the desired product is filtered off if it has formed as a precipitate, or the organic medium is evaporated off if the product is soluble in it. The cleaning can be carried out in a conventional manner, for example by recrystallization and the like.

The compounds of formula II are easily obtained if, for example, a compound of formula

10 wherein R2, R7 and R8 have the meaning given above. The reaction can be carried out by heating a mixture of the isocyanate dimer and the acetal in an inert organic medium such as benzene to the reflux temperature of the reaction mixture. The mixture is usually refluxed for about 2 to about 30 minutes in 15 to ensure complete implementation. The product can be obtained by evaporation of the reaction medium, it can be used as such or it can be purified by standard methods.

20 The isocyanate dimer of the formula V is obtained, for example, if a thiadiazole of the formula

N-

■ N

25th

30th

R1 - C

V /

C - NH,

(VII)

N-

-N

R1 - C

\ / S

C-N-C-N- CH- -

H

OR I

CH I, OR '

(IV)

8th

wherein R1 and R2 are as defined above and RT and R8 are methyl or ethyl, heated in a dilute aqueous, acidic medium for about 10 to about 60 minutes. Temperatures from about 70 ° C. to the reflux temperature of the reaction mixture are used. The reaction medium can contain a dilute aqueous inorganic acid such as hydrochloric acid in a concentration of about 0.5 to about 5%. After the reaction has ended, the product is usually obtained as a precipitate on cooling the reaction mixture. It can be used as such or cleaned in a conventional manner, for example by recrystallization and the like.

The compounds of formula IV can be obtained by adding a molar amount of an isocyanate dimer of the formula

N

N

O =

C = N - C C-R

■ V

(V)

wherein R1 has the meaning given above, reacted with phosgene. This reaction is accomplished by conveniently adding a slurry or solution of the thiadiazole in a suitable organic solvent 35 such as ethyl acetate to a phosgene solution in an organic solvent such as ethyl acetate. The resulting mixture is usually stirred at room temperature for about 2 to about 24 hours. The reaction mixture can be flushed with 40 nitrogen to remove unreacted phosgene. The product, if it has formed as a precipitate, is preferably filtered off or obtained by evaporation of the solvent if it is soluble in the latter. It can be used as such or, if necessary, further cleaned.

45 Examples of thiadiazoles of the formula VII which are suitable for the preparation of the new compounds are 5-methyl-2-amino-1,3,4-thiadiazole, 5-ethyl-2-amino-1,3,4-thiadiazole , 5-propyl-2-amino-l, 3,4-thiadiazoI, 5-t-butyl-2-amino-l, 3,4-thiadiazole, 5-allyl-2-amino-l, 3,4- thiadiazoI, 5-pent-3-enyI-50 -2-amino-l, 3,4-thiadiazole, 5- (ß-chloroethyl) -2-amino-l, 3,4-thiadiazole, 5- (Y- Chloropropyl) -2-amino-l, 3,4-thiadiazole, 5-trifluoromethyl-2-amino-l, 3,4-thiadiazole, 5-methoxy-2-amino-l, 3,4-thiadiazole, 5- Ethoxy-2-amino-l, 3,4-thiadiazole, 5-propoxy-2-amino-l, 3,4-thiadiazole, 5-butyloxy-2-amino-55-1,3,4-thiadiazole, 5- Hexyloxy-2-amino-l, 3,4-thiadiazole, 5-methylthio-2-amino-1,3,4-thiadiazole, 5-ethylthio-2-amino-1,3,4-thiadiazole, 5 Propylthio-2-amino-l, 3,4-thiadiazole, 5-butylthio-2-amino-1,3,4-thiadiazole, 5-methylsulfonyl-2-amino-1,3,4-thiadiazole, 5-ethylsulfonyl-2-amino-l, 3,4-thiadiazole, 60 5-butylsulfonyl-2-amino-l, 3,4-thiadiazole, 5-methylsulfinyl-2 - amino-1,3,4-thiadiazole, 5-ethylsulfinyl-2-amino l, 3,4-thia-diazole, 5-propylsulfinyl-2-amino-1,3,4-thiadiazole, 5-butyl-sulfinyl-2-amino-l, 3,4-thiadiazole, and the like.

Examples of acetals of the formula VI for the preparation of the 65 new compounds are the dimethyl acetal of 2-methylaminoacetaldehyde, the dimethyl acetal of 2-ethyaminoacetaldehyde, the dimethylacetal of 2-propylaminoacetal dehyde, the dimethylacetal of 2-butylaminoacetaldehyde,

5

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the dimethylacetal of 2-pentylaminoacetaldehyde and the dimethylacetal of 2-hexylaminoacetaldehyde.

Examples of suitable amines of the formula III are methylamine, ethylamine, propylamine, butylamine, isopropylamine, sec-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, dioctylamine, didodadylylamine, dioctylamine -amine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, N-methyl-N-ethylamine, N-ethyl-N - hexylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, ß-chloroethylamine, y- Bromopropylamine, 8-chlorobutylamine, S, 8-dichlorobutylamine, allylamine, but-3-enylamine, pent-4-enylamine, hex-4-enylamine, methoxymethylamine, methoxyethylamine, ethoxy-methylamine, methoxypropylamine, ethoxypropylamine, phenylamine, 3-chlorophenylamine, 4-bromophenylamine, 2-methoxyphenylamine, 4-trifluoromethylphenylamine, 3-methylthiophenylamine, 4-nitrophenylamine, 4-cyanophenylamine, 3,4-di-chlorobenzylamino, 2-methyl-4-chlorobenzylamine, 3, 4,5-tri-chlorophenylamine, N-methyl-N- (3,4-dibromophenyl) amine, ethyleneim in, trimethyleneimine, tetramethyleneimine, pentamethyleneimine, hexamethyleneimine and the like.

The following examples illustrate the preparation of the new compounds.

example 1

Preparation of 5-trifluoromethyl-l, 3,4-thiadiazol-2-yl iso-cyanate dimer:

100 ml of saturated solution of phosgene in ethyl acetate are introduced into a glass reaction vessel equipped with a mechanical stirrer. A slurry of 45 g of 5-trifluoromethyl-2-amino-l, 3,4-thiadiazoI in 300 ml of ethyl acetate is added and the resulting mixture is stirred for about 16 hours to give a precipitate. The reaction mixture is then purged with nitrogen to remove unreacted phosgene. Filtration gives 48 g of a white solid which is recrystallized from dimethylformamide. The desired 5-trifluoromethyl-l, 3,4-thiadiazol-2-yl iso-cyanate dimer is obtained.

Example 2

Preparation of the dimethyl acetal of 2- [l-methyl-3- (5-tri-

fluoromethyl-1,3,4-thiadiazol-2-yl) ureido] acetaldehyde:

A mixture of 9.5 g of 5-trifluoromethyl-l, 3,4-thiadiazol-2-yl isocyanate dimer, 5.8 g of the dimethylacetal of 2-methylaminoacetaldehyde and 60 ml of benzene is placed in a mechanical stirrer and reflux cooler filled reaction vessel made of glass. The reaction mixture is refluxed for about 15 minutes, then the benzene is stripped off under reduced pressure to give a solid as a residue. This product is recrystallized from heptane, giving the dimethyl acetal of 2- [l - methyl-3- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -ureido] acetaldehyde of mp 101 to 102 ° C.

Example 3

Preparation of 1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one:

15 g of the dimethylacetal of 2- [l-methyl-3- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, 400 ml of water and 4 ml of hydrochloric acid are mixed in a mechanical stirrer , Thermometer and reflux condenser filled with glass. The reaction mixture is refluxed for about 15 minutes, then filtered while hot, and the filtrate is cooled to give a precipitate. The precipitate is filtered off, dried and recrystallized from ethyl acetate / hexane, giving 1 - (5-trifluoromethyl 1 l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-5 - 1,3-imidazolidin-2-one, mp 136 to 138 ° C.

Example 4

Preparation of 1- (5-trifluoromethy 1-1,3,4-thiadiazol-2-yl) -3-methyl-5-t-butylamino-J, 3-imidazolidin-2-one:

10th

13.1 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one and 100 ml of heptane are combined in one Reaction vessel made of glass filled with mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. 7.0 g of t-butylamine are added and the mixture is heated to reflux while the water formed is removed. As soon as water is no longer released, the reaction mixture is cooled, a crystalline solid precipitating. This is filtered off and recrystallized from heptane, giving the desired product 1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-t-butylamino-l, 3- imidazolidin-2-one, melting point 113 to 115 ° C.

25 Example 5

Preparation of 5-t-butyl-l, 3,4-thiadiazol-2-yl isocyanate dimer:

100 ml of a saturated solution of phosgene in ethyl 30 acetate are introduced into a glass reaction vessel equipped with a mechanical stirrer. A slurry of 10 g of 5-t-butyl-2-amino-l, 3,4-thiadiazole in 300 ml of ethyl acetate is added and the resulting mixture is stirred for about 16 hours to form a precipitate. Then the reaction mixture is flushed with nitrogen to remove unreacted phosgene and then filtered, the product being 5-t-butyl-l, 3,4-thiadiazol-2-yl-iso-cyanate dimer as a solid F. 261 to 263 ° C.

40

Example 6

Preparation of the dimethylacetal of 2- [l-methyl-3- (5-t-butyl-1,3,4-thiadiazol-2-yl) ureido] acetaldehyde:

45 A mixture of 6 g of 5-t-butyl-l, 3,4-thiadiazol-2-yl-iso-cyanate dimer, 3.9 g of the dimethyl acetal of 2-methylamino-acetaldehyde and 50 ml of benzene is mixed in a mechanical stirrer and reflux condenser filled glass reaction vessel. The reaction mixture is heated under reflux for about 5 minutes with stirring, then the benzene is stripped off, giving an oil which solidifies on standing. The resulting solid is recrystallized from pentane, giving the dimethyl acetal of 2- [l - methyl-3- (5-t-butyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde 55 of F. 80 to 82 ° C.

Example 7

Preparation of 1- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one:

60

16 g of the dimethylacetal of 2- [l-methyl-3- (5-t-butyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, 10 ml of concentrated hydrochloric acid and 500 ml of water are combined in a mechanical stirrer, thermometer and reflux cooler made of -65 glass reaction vessel. The reaction mixture is heated to reflux for about 15 minutes, then filtered while hot, the filtrate is cooled, a precipitate being formed. The precipitate is filtered off, dried

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net and recrystallized from benzene / hexane. This gives the l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one from. M. 133 to 134 ° C.

Example 8

Preparation of 1- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hexylamino-l, 3-imidazolidin-2-one:

13.4 g of l- (5-t-butyl-l, 3,4-thiadiazoI-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 6.0 g Hexylamine and 100 ml of heptane are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction being removed azeotropically. As soon as no more water is released, the solvent is stripped off and an oil is obtained as a residue. A vacuum is applied, whereby the oil solidifies. The resulting solid is recrystallized from hexane to give l- (5-t-butyl-l, 3,4-thia-diazol-2-yl) -3-methyl-5-hexylamino-l, 3- imidazolidin-2-one, melting point 62 to 64 ° C.

Example 9

Preparation of 1- (5-trifluoromethyl l-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hexylamino-l, 3-imidazolidin-2-one:

13.4 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 6.0 g of hexylamine and 100 ml of heptane are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated under reflux and the water of reaction is removed as an azeotrope. As soon as no more water is released, the solvent is stripped off and an oil is obtained as a residue. This oil is dissolved in pentane and the solution is passed through a Florex column, the eluate is stripped off and dried in vacuo. The product obtained is l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yI) -3-methyl-5-hexylamino-l, 3-imidazolidin-2 - one.

Example 10

Preparation of 1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-anilino-l, 3-imidazolidin-2-one:

13.4 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 100 ml of heptane and 6 ml of aniline are filled into a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux for about 8 hours, and the water of reaction is removed as it is. The solvent is then stripped off, leaving a solid residue which is recrystallized from isopropanol. The l- (5-tri-fluoromethyl-1,3,4-thiadiazol-2-yl) -3-methyl-5-anilino-1,3-imidazolidin-2-one of mp 142 to 144 is obtained ° C.

Example 11

Preparation of 1- (5-trifluoromethyl l-l, 3,4-thiadiazol-2-yl) -3-methyl-5-benzylamino-l, 3-imidazolidin-2-one:

8 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 4.5 g of benzylamine and 100 ml of heptane are filled into a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction is removed as it is formed. When water is no longer formed, the mixture is cooled to give a solid. This is filtered off and consists of the desired 1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-benzylamino-1,3-imidazolidin-2-one of F. 97 to 99 ° C.

Example 12

Preparation of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-

-methyl-5 - $ - hydroxyethylamino-l, 3-imidazolidin-2-one:

8 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolin-2-one, 5 g of β-hydroxyethylamine and 75 ml of benzene are filled into a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The mixture is heated to reflux and the water of reaction is removed as it is. As soon as no more water is released, the solvent is stripped off and an oil is obtained which is filtered through Celite. It consists of the product l- (5-trifluoromethy] -l, 3,4-thiadiazol-2-y]) - 3-methyl-5 - ß-hydroxyethylamino-l, 3-imidazolidin-2-one.

Example 13

Preparation of 1- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) -3-methyl-5-diethylamino-1,3-imidazolidin-2-one:

8 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 3 g of diethylamine and 50 ml of benzene are added a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap is filled. The reaction mixture is heated to reflux, the water of reaction is removed as it is formed. As soon as no more water is released, the solvent is stripped off and an oil is obtained. This is dissolved in pentane and the resulting solution is passed through a Florex column. The pentane is stripped off from the eluate, giving an oil which is dried in vacuo. The l- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) -3-methyl-5-diethylamino-1,3-imidazolidin-2-one is obtained.

Example 14

Preparation of 1- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-β-hydroxy cithylamino-l, 3-imidazolidin-2-one:

8 g of l- (5-t-butyl-l, 3,4-thiadiazoI-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 3 g of β-hydroxyethylamine and 75 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction is removed as it is formed. As soon as water is no longer formed, the benzene is stripped off, leaving a solid. This is recrystallized from ethyl acetate to give l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-ß-hydroxväthylamino-l, 3-imidazolidin-2 -on from F. 128 to 130 ° C.

Example 15

Preparation of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (2-methoxyisopropylamino) -l, 3-imidazolidin-2-one:

8 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 5 g of 2-methoxyisopropylamine and 70 ml of benzene are filled into a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction is removed as it is formed. As soon as no more water formed

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the solvent is stripped off and an oil is obtained. This is filtered through Celite, the desired l- (5-trifluoromethyl-l, 3,4-thiadiazoI-2-yI) -3-methyl-5- (2-methoxyisopropylamino) -l, 3-imidazolidine being obtained -2-one.

Example 16

Preparation of 5-hexyl-l, 3,4-thiadiazol-2-yl isocyanate dimer:

A saturated solution of phosgene in ethyl acetate (100 ml) is poured into a glass vessel equipped with a mechanical stirrer. Then a slurry of 40 g of 5-hexyl-2-amino-l, 3,4-thiadiazole in 300 ml of ethyl acetate is added and the resulting mixture is stirred for about 16 hours to give a precipitate. The reaction mixture is then purged with nitrogen to remove unreacted phosgene, then the precipitate is filtered off and recrystallized to obtain the title compound.

Example 17

Preparation of the dimethylacetal of 2- [l-ethyl-3- (5-hexyl-1,3,4-thiadiazol-2-yl) ureido] acetaldehyde:

A mixture of 0.05 mol of 5-hexy 1-1,3,4-thiadiazol-2-yl-isocyanate dimer, 0.1 mol of 2-ethylaminoacetaldehyde dime-thylacetal and 60 ml of benzene is placed in a mechanical stirrer and glass-filled reaction vessel. The reaction mixture is heated to reflux for about 15 minutes, then the benzene is stripped off under reduced pressure, leaving a solid. This is recrystallized, whereby the title compound is obtained.

Example 18

Preparation of 1- (5-hexyl-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-hydroxy-1,3-imidazolidin-2-one:

15 g of the dimethyl acetal of 2- [l-ethyl-3- (5-hexyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, 400 ml of water and 4 ml of hydrochloric acid are placed in a with a mechanical stirrer, Thermometer and reflux condenser equipped glass reaction vessel. The reaction mixture is refluxed for about 15 minutes and then filtered while hot, the filtrate is cooled, a precipitate being formed. This is filtered off, dried and recrystallized, giving the title compound.

Example 19

Preparation of 1- (5-hexyl-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-allylamino-1,3-imidazolidin-2-one:

0.1 mol of l- (5-hexyl-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-hydroxy-l, 3-imidazolidin-2-one, 0.11 mol of allylamine and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux and the water of reaction is removed as it arises. When water is no longer formed, the solvent is stripped off under reduced pressure to give the title compound as a residue.

Example 20

Preparation of 5-methoxy-l, 3,4-thiadiazol-2-yl isocyanate dimer:

A saturated solution of phosgene in ethyl acetate (100 ml) is introduced into a glass reaction vessel equipped with a mechanical stirrer. Then a slurry of 40 g of 5-methoxy-2-amino-l, 3,4-thiadiazole in 300 ml of ethyl acetate is added and the resulting mixture is stirred for about 16 hours to form a precipitate.

Then the reaction mixture is flushed with nitrogen to remove unreacted phosgene, then the precipitate is filtered off and recrystallized, whereby the title compound is obtained.

Example 21

Preparation of the dimethyl acetal of 2- [l-ethyl-3- (5-methoxy-1,3,4-thiadiazal-2-yl) ureido] acetaldehyde;

A mixture of 0.05 mol of 5-methoxy-l, 3,4-thiadiazol-2 - yl-isocyanate dimer, 0.1 mol of 2-ethylaminoacetaldehyde di-methyl acetal and 60 ml of benzene is mixed in with a mechanical stirrer and Refilled condenser filled glass reaction vessel. The reaction mixture is refluxed for about 15 minutes, then the benzene is stripped off under reduced pressure to give a solid as a residue. This is recrystallized and gives the title compound.

Example 22

Preparation of 1- (5-methoxy-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-hydroxy-l, 3-imidazolidin-2-one:

15 g of the dimethyl acetal of 2- [l-ethyl-3- (5-methoxy-l, 3,4 ~ thiadiazol-2-yl) ureido] acetaldehyde, 400 ml of water and 4 ml of hydrochloric acid are placed in a with a mechanical stirrer, Thermometer and reflux condenser filled glass reaction vessel. The reaction mixture is refluxed for about 15 minutes and then filtered while hot. When the filtrate is cooled, a precipitate is formed which is filtered off, dried and recrystallized. This gives you the title link.

Example 23

Preparation of 1- (5-methoxy-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-cyclopropylamino-l, 3-imidazolidin-2-one:

0.1 mol of 1- (5-methoxy-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-hydroxy-l, 3-imidazolidin-2-one, 0.11 mol of cyclopropylamine and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction is removed as it is formed. As soon as no more water is formed, the solvent is stripped off under reduced pressure and the title compound is obtained as residue.

Example 24

Preparation of 5-methylthio-l, 3,4-thiadiazol-2-yl isocyanate dimer:

A saturated solution of phosgene in ethyl acetate (100 ml) is introduced into a glass reaction vessel equipped with a mechanical stirrer. Then a slurry of 45 g of 5-methylthio-2-amino-l, 3,4-thiadiazole in 300 ml of ethyl acetate is added, and the resulting mixture is stirred for about 16 hours to form a precipitate. The reaction mixture is then flushed with nitrogen in order to remove unreacted phosgene, and the precipitate is then filtered off. The title compound is obtained on recrystallization.

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Example 25

Preparation of the dimethylacetal of 2- [l-propyl-3- (5-methylthio-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde:

A mixture of 0.05 Moi 5-methylthio-l, 3,4-thiadiazol-2-yl-isocyanate dimer, 0.1 mol 2-propylaminoacetaldehyde-dimethylacetal and 60 ml benzene is placed in a mechanical stirrer and reflux condenser equipped reaction vessel made of glass. The reaction mixture is then refluxed for about 15 minutes, then the benzene is stripped off under reduced pressure, a solid being obtained as the residue. This is recrystallized, the title compound being obtained.

Example 26

Preparation of 1- (5-methylthio-1,3,4-thiadiazol-2-yl) -3-propyl-5-hydroxy-l, 3-imidazolidin-2-one:

15 g of dimethyl acetal of 2- [l-propyl-3- (5-methylthio-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, 400 ml of water and 4 ml of hydrochloric acid are mixed in a mechanical stirrer, thermometer and glass-filled reflux condenser, then the reaction mixture is heated to reflux for about 15 minutes. The mixture is filtered while hot, and a precipitate forms when the filtrate is cooled. This is filtered off, dried and recrystallized, whereby the title compound is obtained.

Example 27

Preparation of 1- (5-M ethylthio-1,3,4-thiadiazol-2-yl) -3-propyl-5- "f-chloropropylamino-1,3-imidazolidin-2-one:

0.1 mol of 1- (5-methylthio-l, 3,4-thiadiazol-2-yl) -3-propyl-5-hydroxy-1,3-imidazolidin-2-one, 0.11 mol of y-chloropropyl -amine and 100 ml of benzene are introduced into a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. Then the reaction mixture is heated under reflux, the water of reaction is removed as it arises. As soon as water is no longer formed, the solvent is stripped off under reduced pressure, the l- (5-methyl-thio-l, 3,4-thiadiazol-2-yl) -3-propyl-5-y-chloropropylamino -l, 3-imidazolidin-2-one obtained as a residue.

Example 28

Preparation of 5-methylsulfonyl-l, 3,4-thiadiazol-2-yl isocyanate dimer:

A saturated solution of phosgene in ethyl acetate (100 ml) is placed in a glass reaction vessel equipped with a mechanical stirrer, then a slurry of 50 g of 5-methylsulfonyl-2-amino-l, 3,4-thiaediazole in 300 ml of ethyl acetate is added and the resulting mixture is stirred for about 16 hours, during which a precipitate forms. Then the reaction mixture is flushed with nitrogen to remove unreacted phosgene, then the precipitate is filtered off and recrystallized, whereby the title compound is obtained.

Example 29

Preparation of the dimethylacetal of 2- [l-allyl-3- (5-methyl-sulfonyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde:

A mixture of 0.05 mol of 5-methylsulfonyl-l, 3,4-thia-diazol-2-yl isocyanate dimer, 0.1 mol of 2-allylaminoacetalde-hyd-dimethylacetal and 60 ml of benzene is in a mechanical stirrer and glass-filled reflux condenser, the reaction mixture is heated under reflux for about 15 minutes. Then the benzene is stripped off under reduced pressure to give a solid residue. This gives the 5 title compound on recrystallization.

Example 30

Preparation of l- (5-methylsulfonyl-l, 3,4-thiadiazol-2-yl) -3-10 -allyl-5-hydroxy-l, 3-imidazolidin-2-one:

15 g of the dimethyl acetal of 2- [l-Allyl-3- (5-methylsulfonyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, 400 ml of water and 4 ml of hydrochloric acid are mixed in a mechanical 15 Stirrer, thermometer and reflux condenser equipped reaction vessel made of glass. The reaction mixture is refluxed for about 15 minutes, then filtered while hot. When the filtrate is cooled, a precipitate is formed which is filtered off, dried and recrystallized. This gives 20 l- (5-methylsulfonyl-1,3,4-thiadiazol-2-yl) -3-allyl-5-hydroxy-1,3-imidazolidin-2-one.

Example 31

25 Preparation of 1- (5-methylsulfonyl-l, 3,4-thiadiazol-2-yl) -3- ~ allyl-5- (N-methyl-N-cyclohexylamino) -l, 3-imidazolidin-2-one:

0.1 mol of 1- (5-methylsulfonyl-l, 3,4-thiadiazol-2-yl) -3-allyl-5-hydroxy-1,3-imidazolidin-2-one, 0.11 mol of N-methyl -N-30 -cyclohexylamine and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction being removed as it is formed. If water is no longer formed, the solvent is stripped off under reduced pressure to give the title compound.

40 Example 32

Preparation of 5-methylsulfinyl-l, 3,4-thiadiazol-2-yl isocyanate dimer:

A saturated solution of phosgene in ethyl acetate (100

45 ml) is poured into a glass reaction vessel equipped with a mechanical stirrer. A slurry of 50 g of 5-methylsulfinyl-2-amino-1,3,4-thiadiazole in 300 ml of ethyl acetate is then added and the resulting mixture is stirred for about 16 hours. stirred, resulting in a precipitate.

50 The reaction mixture is then purged with nitrogen to remove unreacted phosgene, then the precipitate is filtered off and recrystallized, whereby the title compound is obtained

55

Example 33

Preparation of the dimethylacetal of 2- [l-methyl-3- (5-methyl-sulfinyl-1,3,4-thiadiazol-2-yl) ureido jacetaldehyde:

60 A mixture of 0.05 mol of 5-methylsulfinyl-l, 3,4-thia-diazol-2-yl isocyanate dimer and 0.1 mol of 2-methylamino-acetaldehyde dimethylacetal and 60 ml of benzene is mixed in a mechanical Stirrer and reflux condenser equipped reaction vessel made of glass. The reaction mixture is

65 refluxed for about 15 minutes, then the benzene is stripped off under reduced pressure to give a solid residue. After recrystallization, this gives the title compound.

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Example 34

Preparation of 1- (5-methylsulfinyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one:

15 g of the dimethyl acetate of 2- [l-methyl-3- (5-methyl-sulfinyl) -l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, 400 ml of water and 4 ml of hydrochloric acid are mixed in a mechanical Stirrer, thermometer and reflux condenser equipped reaction vessel made of glass. The reaction mixture is heated to reflux for about 15 minutes, then it is filtered while hot. When the filtrate is cooled, a precipitate is formed which is filtered off, dried and recrystallized. This gives you the title link.

Example 35

Preparation of 1- (5-methylsulfinyl-l, 3,4-thiadiazol-2-yl) -

-3-methyl-5- (2-methylanilino) -l, 3-imidazolidin-2-one:

0.1 mol of l- (5-methylsulfinyl-l, 3,4-thiadiazoI-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 0.11 mol of 2- Methyl aniline and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction is removed as it is formed. When water is no longer formed, the solvent is stripped off under reduced pressure to give the title compound as a residue.

Example 36

Preparation of 5-cyclopropyl-l, 3,4-thiadiazol-2-yl isocyanate dimer:

A saturated solution of phosgene in ethyl acetate (100 ml) is placed in a glass reaction vessel equipped with a mechanical stirrer, then a slurry of 6 g of 5-cyclopropyl-2-amino-l, 3,4-thiadiazole in 100 ml of ethyl acetate is added and the resulting mixture is stirred for about 16 hours to form a precipitate. The reaction mixture is then purged with nitrogen to remove unreacted phosgene. The precipitate is then filtered off, giving the title compound.

Example 37

Preparation of the dimethyl acetal of 2- [l-propargyl-3- (5-

-cyclopropyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde:

A mixture of 7 g of 5-cyclopropyl-l, 3,4-thiadiazol-2-yl-isocyanate dimer, 5 g of 2-propargylaminoacetaldehyde dime-thylacetal and 50 ml of ethyl acetate is discharged into a reaction vessel equipped with a mechanical stirrer and reflux condenser Glass filled. The reaction mixture is refluxed for about 2 hours, then the solvent is stripped off under reduced pressure to give the title compound as an oil.

Example 38

Preparation of 1- (5-cyclopropyl-l, 3,4-thiadiazol-2-yl) -3-propargyl-5-hydroxy-l, 3-imidazolidin-2-one:

The dimethyl acetal obtained according to Example 37, 400 ml of water and 4 ml of hydrochloric acid are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated under reflux for about 15 minutes, then the mixture is filtered while hot. When the filtrate cools, a

Precipitate which is filtered off, dried and recrystallized from ethyl acetate to give the title compound.

5 Example 39

Preparation of 1- (5-cyclopropyl-l, 3,4-thiadiazol-2-yl) -3-

-propargyl-5- (2-methoxyanilino) -l, 3-imidazolidin-2-one:

0.1 mole l- (5-cyclopropyl-l, 3,4-thiadiazol-2-yl) -3-pro-io pargyl-5-hydroxy-l, 3-imidazolidin-2-one, 0.11 mole 2 -Methoxy-aniline and 100 ml of benzene are placed in a reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, with the reaction water being removed as it is formed. When water is no longer formed, the solvent is stripped off under reduced pressure to give the title compound as a residue.

20 Example 40

Preparation of 5-cyclohexyl-l, 3,4-thiadiazol-2-yl isocyanate dimer:

A saturated solution of phosgene in ethyl acetate (500-25 ml) is poured into a glass reaction vessel equipped with a mechanical stirrer, then 6 g of 5-cyclohexyl-2-amino-l, 3,4-thiadiazole are added and the resulting mixture is heated under reflux for about 4 hours with stirring, a precipitate being formed. The reaction mixture is then flushed with nitrogen in order to remove unreacted phosgene, and the precipitate is then filtered off. It is recrystallized from a mixture of dimethylform amide and water, giving the 5 - cyclohexyl-l, 3,4-thiadiazol-2-yl isocyanate dimer of mp 237 35 to 239 ° C.

Example 41

Preparation of the dimethylacetal of 2- [l-methyl-3- (5-cyclo-40 hexyl-l, 3,4-thiadiazol-2-yl) ureido jacetaldehyde:

A mixture of 12 g of 5-cyclohexyl-l, 3,4-thiadiazol-2-yl isocyanate dimer, 6.9 g of 2-methylaminoacetaldehyde dimethyl acetal and 60 ml of benzene is mixed in with a mechanical stirrer and glass-filled reaction vessel. The reaction mixture is refluxed for about 15 minutes, then the benzene is stripped off under reduced pressure to give a solid residue. This is recrystallized from methanol to give the dimethyl acetal of 2- [l-methyl-3- (5-cyclohexyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, mp 133 to 134 ° C.

Example 42

55 Preparation of 1- (5-cyclohexyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one:

15 g of the dimethylacetal of 2- [l-methyl-3- (5-cyclohexyl-l, 3,4-thiadiazol-2-yl) ureidolacetaldehyde, 400 ml of water and 60 4 ml of hydrochloric acid are placed in a with mechanical stirrer, thermometer and glass-filled reaction vessel. The reaction mixture is heated under reflux for about 15 minutes, then filtered while hot and the filtrate is cooled. A precipitate is formed, 65 which is filtered off, dried and recrystallized from methanol, the desired 1- (5-cyclohexyl-l, 3,4-thia-diazol-2-yl) -3-methyl-5-hydroxy- l, 3-imidazolidin-2-one of mp 154 to 155 ° C.

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Example 43

Preparation of l- (S-cyclohexyl-l, 3,4-thiadiazol-2-yl) -3-

-methyl-5- (3,4-dichloroanilino) -l, 3-imidazolidin-2-one:

0.1 mol of l- (5-cyclohexyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 0.11 mol of 3.4 -Dichloraniline and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction is removed and it is formed. As soon as water is no longer formed, the solvent is stripped off under reduced pressure, the l- (5-cyclohexyl-l, 3,4-thiadiazol-2-yl> -3-methyl-5- (3,4-dichloroanilino -l, 3-imidazolidin-2-one obtained as a residue.

Example 44

Preparation of 5-cyclopentyl-l, 3,4-thiadiazol-2-yl isocyanate dimer:

A saturated solution of phosgene in ethyl acetate (100 ml) is introduced into a glass reaction vessel equipped with a mechanical stirrer. Then a slurry of 50 g of 5-cyclopentyl-2-amino-l, 3,4-thiadiazole in 300 ml of ethyl acetate is added and the resulting mixture is stirred for about 16 hours to give a precipitate. Then the reaction mixture is flushed with nitrogen to remove unreacted phosgene, then the precipitate is filtered off and recrystallized, giving the desired product 5-cyclopentyl-l, 3,4-thiadiazol - 2-yl isocyanate dimer.

Example 45

Preparation of the dimethyl acetal of 2- / 7-methyl-3- (5-cyclopentyl-1,3,4-thiadiazol-2-yl) ureido] acetaldehyde:

A mixture of 0.05 mol of 5-cyclopentyl-l, 3,4-thiadiazol - 2-yI-isocyanate dimer, 0.1 mol of 2-methylaminoacetaldehyde - dimethylacetal and 60 ml of benzene is placed in a mechanical stirrer and reflux condenser equipped reaction vessel made of glass. The reaction mixture is refluxed for about 15 minutes, then the benzene is stripped off under reduced pressure to give a solid residue. Upon recrystallization, this gives the dimethyl acetal of 2- [l-methyl-3- (5-cyclopentyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde.

Example 46

Preparation of 1- (5-cyclopentyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one:

15 g of the dimethyl acetal of 2- [l-methyl-3- (5-cyclopentyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, 400 ml of water and 4 ml of hydrochloric acid are mixed in with a mechanical stirrer , Thermometer and reflux condenser equipped glass reaction vessel. The reaction mixture is refluxed for about 15 minutes and then filtered while hot. The filtrate is cooled to give a precipitate which is filtered off, dried and recrystallized. This gives the desired l- (5-cyclopentyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one.

Example 47

Preparation of l- (5-cyclopentyl-l, 3,4-thiadiazol-2-yl) -3-me-

thyl-5- (4-trifluoromethylanilino) -l, 3-imidazolidin-2-one:

0.1 mol of 1- (5-cyclopentyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolin-2-one, 0.11 mol of 4-trifluoromethyl -

Aniline and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the reaction water is removed as soon as it is formed. As soon as water is no longer formed, the solvent is stripped off under reduced pressure and the desired 1- (5-cyclopentyl-1,3,4-thiadiazol-2-yl) -3-methyl-5- (4-trifluoro) is obtained -methylanilino) -l, 3 ~ imidazoIidin-2-one as residue.

10th

Example 48

Preparation of 1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-ß-methoxyethylamino-l, 3-imidazolidin-2-one:

15 8.0 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl - 5-hydroxy-l, 3-imidazolidin-2-one and 75 ml of benzene are combined in one Glass reaction vessel filled with mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. Then 5.0 g of β-methoxyethylamine are added to-20 and the mixture is heated to reflux, the water formed being removed. As soon as no more water is released, the reaction mixture is cooled, a solid precipitating out. This is filtered off and recrystallized from hexane to give l- (5-trifluoro-25 methyl-1,3,4-thiadiazol-2-yJ) -3-methyl-5-ß-methoxyethyf-amino-1,3 -imidazolidin-2-one from F. 82 to 84 ° C.

Example 49

Preparation of 5-allyl-l, 3,4-thiadiazol-2-yl isocyanate dimer:

30th

A saturated solution of phosgene in ethyl acetate (100 ml) is placed in a glass reaction vessel equipped with a mechanical stirrer. Then a slurry of 50 g of 5-allyl-2-amino-l, 3,4-thiadiazole in 300 ml of 35 ethyl acetate is added and the resulting mixture is stirred for about 16 hours to give a precipitate. The reaction mixture is then purged with nitrogen to remove unreacted phosgene, then the mixture is filtered and the resulting precipitate is crystallized by -40 to obtain the title compound.

Example 50

Preparation of the dimethyl acetal of 2- [l-methyl-3- (5-allyl-1,3,4-thiadiazol-2-yl) ureido] acetaldehyde:

45

A mixture of 0.05 mol of 5-allyl-l, 3,4-thiadiazol-2-yl-isocyanate dimer, 0.1 mol of 2-methylaminoacetaldehyde-dime-thylacetal and 60 ml of benzene is placed in a mechanical stirrer and Reaction vessel 50 equipped with a reflux condenser made of glass. The reaction mixture is refluxed for about 15 minutes, then the benzene is stripped off under reduced pressure to give a solid residue. Upon recrystallization, this gives the dimethylacetal of 2- [l-methyl-3- (5-allyl-l, 3,4-thiadiazol-2-yl) ureido] acetalde-55 hyds.

Example 51

Preparation of 1- (5-allyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one:

6o 15 g of the dimethylacetal of 2- [l-methyl-3- (5-allyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, 400 ml of water and 4 ml of hydrochloric acid are mixed in with a mechanical stirrer , Thermometer and reflux condenser filled reaction vessel. The reaction mixture is heated under reflux for about 15 minutes and then filtered while hot, and the filtrate is cooled. The resulting precipitate is filtered off, dried and recrystallized, whereby the title compound is obtained.

11

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Example 52

Preparation of 1- (5-allyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5 - (3-nitroanilino) -l, 3-imidazolidin-2-one:

0.1 mol of l- (5-alyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 0.11 mol of 3- Nitroaniline and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction is removed and it is formed. When water is no longer formed, the solvent is stripped off under reduced pressure to give the title compound as a residue.

Example 53

Preparation of 5-pentyl-l, 3,4-thiadiazol-2-yl isocyanate dimer:

A saturated solution of phosgene in ethyl acetate (100 ml) is placed in a glass reaction vessel equipped with a mechanical stirrer. Then a slurry of 40 g of 5-pentyl-2-amino-l, 3,4-thiadiazole in 300 ml of ethyl acetate is added, and the resulting mixture is stirred for about 16 hours to form a precipitate. The reaction mixture is then purged with nitrogen to remove unreacted phosgene. The precipitate is then filtered off and recrystallized, giving the title compound.

Example 54

Preparation of the dimethylacetal of 2- [l-ethyl-3- (5-pentyl-1,3,4-thiadiazol-2-yl) ureido] acetaldehyde:

A mixture of 0.05 mol of 5-pentyl-l, 3,4-thiadiazol-2-yl-isocyanate dimer, 0.1 mol of 2-ethylaminoacetaldehyde-dime-thylacetal and 60 ml of benzene is mixed in with a mechanical stirrer and A reaction vessel made of glass filled with a reflux condenser. The reaction mixture is refluxed for about 15 minutes, then the benzene is stripped off under reduced pressure to give a solid residue. The title compound is obtained from this during recrystallization.

Example 55

Preparation of 1- (5-pentyl-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-hydroxy-l, 3-imidazolidin-2-one:

15 g of the dimethyl acetal of 2- [l-ethyl-3- (5-pentyl-l, 3,4-thiadiazol-2-yl) ureido] acetaldehyde, 400 ml of water and 4 ml of hydrochloric acid are placed in a with a mechanical stirrer, Thermometer and reflux condenser equipped reaction vessel made of glass. The reaction mixture is heated to reflux for about 15 minutes, then the filtrate is cooled, a precipitate being formed. This is filtered off, dried and recrystallized, giving the title compound.

Example 56

Preparation of 1- (5-pentyl-l, 3,4-thiadiazol-2-yl) -3-ethyl-5 - [N-methyl-N- (3-bromobenzyl) amino] -1, 3-imidazolidine 2-on:

0.1 mol of 1- (5-pentyl-l, 3,4-thiadiazoI-2-yl) -3-ethyl-5-hydroxy-1,3-imidazolidin-2-one, 0.11 mol of N- Methyl-N- (3-bromobenzyl) amine, 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction being removed as soon as it is formed. When water is no longer formed, the solvent is stripped off under reduced pressure to give the title compound as a residue.

Example 57

Preparation of 1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (4-cyananilino) -l, 3-imidazolidin2-one:

0.1 mol of 1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one, 0.11 mol of 4- Cyananiline and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux and the water of reaction is removed as it is formed. As soon as water is no longer formed, the solvent is stripped off under reduced pressure, the title compound being obtained as a residue.

Example 58

Preparation of l- (5-trifluoromethyl l-l, 3,4-thiadiazol-2-yl) -3-methyl-5-octylamino-l, 3-imidazolidin-2-one:

13.1 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl - 5-hydroxy-l, 3-imidazolidin-2-one and 100 ml of heptane are combined in one mechanical stirrer, thermometer, Dean Stark trap and reflux condenser equipped reaction vessel made of glass. Then 10.0 g of octylamine are added and the mixture is heated to reflux while the water formed is removed. As soon as water is no longer released, the solvent is stripped off, giving the title compound.

Example 59

Preparation of 1- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) -3-methyl-5-dodecylamino-1,3-imidazolidin-2-one:

13.1 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one and 100 ml of heptane are combined in one Glass reaction vessel filled with mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. Then 14.0 g of dodecylamine are added and the mixture is heated under reflux, the water formed being removed. As soon as water is no longer released, the solvent is stripped off, giving the title compound.

Example 60

Preparation of 1- (5-trifluoromethyl l-l, 3,4-thiadiazol-2-yl) -3-methyl-5-octadecylamino-l, 3-imidazolidin-2-one:

13.1 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one and 100 ml of heptane are combined in one mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser filled reaction vessel made of glass, then 20.0 g octadecylamine are added and the mixture is heated to reflux, the water being removed as it arises. As soon as water is no longer released, the solvent is stripped off, giving the title compound.

Example 61

Preparation of l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-dodecylamino-l, 3-imidazolidin-2-one:

13.4 g of l- (5-t-butyI-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 12.0 g Dodecylamine and 100 ml of heptane are placed in a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

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12th

Glass reaction vessel filled, the reaction mixture is heated to reflux and the water of reaction is removed and it is removed azeotropically. As soon as water is no longer released, the solvent is stripped off, giving the title compound.

Example 62

Preparation of 1- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-octadecylamino-l, 3-imidazolidin-2-one:

13.4 g of l- (5-t-butyl-l, 3,4-thiadiazol-2-yI) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 6.0 g Octadecylamine and 100 ml heptane are filled into a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux and the water of reaction is removed azeotropically as soon as it is formed. As soon as water is no longer released, the solvent is stripped off, giving the title compound.

Example 63

Preparation of 1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-tetramethyleneimino-l, 3-imidazolidin-2-one:

13.4 g of l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl - 5-hydroxy-l, 3-imidazolidin-2-one and 100 ml of heptane are mixed in a mechanical Stirrer, thermometer, Dean Stark trap and reflux condenser equipped reaction vessel made of glass. Then 4.0 g of tetramethyleneimine are added and the mixture is heated to reflux, removing the water as it is formed. As soon as water is no longer released, the reaction mixture is cooled, a crystalline solid being formed. This is filtered off and recrystallized from heptane, giving the title compound of melting point 97 to 99 ° C.

Example 64

Preparation of 1- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-tetramethyleneimino-1,3-imidazolidin-2-one:

8.0 g of l- (5-t-butyl-l, 3,4-thiadiazoI-2-yI) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one, 3.0 ml Tetramethyleneimine and 100 ml of heptane are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction being removed as soon as it is formed. As soon as water is no longer released, the solvent is stripped off, giving an oil as a residue which solidifies under vacuum. The solid is recrystallized from hexane, giving the title compound of mp 103 to 105 ° C.

Example 65

Preparation of 1- (5-hexyl-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-ethylenimino-l, 3-imidazolidin-2-one:

0.1 mol of 1- (5-hexyl-l, 3,4-thiadiazol-2-yI) -3-ethyI-5-hydroxy-l, 3-imidazolidin-2-one, 0.11 mol of ethyleneimine and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux and the water of reaction is removed as it is formed. As soon as water is no longer formed, the solvent is stripped off under reduced pressure, the title compound being obtained as a residue.

Example 66

Preparation of 1- (5-methoxy-1,3-thiadiazol-2-yl) -3-ethyl-5-trimethyleneimino-1,3-imidazolidin-2-one:

5 0.1 mol of 1- (5-methoxy-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-hydroxy-1,3-imidazolidin-2-one, 0.11 mol of trimethyleneimine and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction being removed as it arises. As soon as water is no longer formed, the solvent is stripped off under reduced pressure, giving the title compound.

15

Example 67

Preparation of 1- (5-methylthio-1,3,4-thiadiazol-2-yl) -3- "propyl-5-pentamethyleneimino-1,3-imidazolidin-2-one:

20 0.1 mol of 1- (5-methylthio-l, 3,4-thiadiazoI-2-yI) -3-propyl - 5-hydroxy-l, 3-imidazolidin-2-one, 0.11 mol of pentamethylene Imine and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is then heated to reflux, removing the water of reaction as it forms. As soon as water is no longer formed, the solvent is stripped off under reduced pressure, giving the title compound.

30th

Example 68

Preparation of 1- (5-methylsulfonyl-l, 3,4-thiadiazol-2-yl) -3-allyl-5-hexamethyleneimino-l, 3-imidazolidin-2-one:

35 0.1 mol of 1- (5-methylsulfonyl-3,4-thiadiazol-2-yl) -3-allyl-5-hydroxy-1,3-imidazolidin-2-one, 0.11 mol of hexamethylene Imine and 100 ml of benzene are placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer, reflux condenser and Dean-Stark trap. The reaction mixture is heated to reflux, the water of reaction being removed as it is formed. As soon as water is no longer formed, the solvent is stripped off under reduced pressure and the title compound is obtained. Further novel compounds which can be prepared according to the invention and which can be prepared by the processes of the preceding examples are 1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-amino

-1,3-imidazolidin-2-one,

1 - (5-t-butyI-l, 3,4-thiadiazol-2-yl) -3-methyl-5-amino-1,3-50-imidazolidin-2-one,

1- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-propyl-

amino-1,3-imidazolidin-2-one, 1 - (5-methyl-1,3,4-thiadiazol-2-yl) -3-butyl-5- (N, N-dimethylamino) -l, 3-imidazolidin-2-one, 55 l- (5-ethylI-l, 3,4-thiadiazoI-2-yI) -3-pentyI-5- (N, N-dipropylamino) -l, 3-imidazolidine -2-one, l- (5-isopropyl-l, 3,4-thiadiazol-2-yl) -3-hexyl-5- (N, N-dihexyl-

amino) -l, 3-imidazolidin-2-one, l- (5-pentyl-l, 3,4-thiadiazol-2-v]) - 3-but-3-enyl-5- (N-methyl-60 -N-butylamino) -l, 3-imidazolidin-2-one,

1 - (5-Hexyl-l, 3,4-thiadiazol-2-yl) -3-pent-4-enyl-5- (N-ethyI-

-N-phenylamino) -1,3-imidazolidin-2-one, 1- (5-cyclobutyl-l, 3,4-thiadiazol-2-yl) -3-hex-4-enyl-5- (N-ethyl --N-benzylamino) -l, 3-imidazolidin-2-one, 65 l- (5-cyclopentyl-l, 3,4-thiadiazol-2-yl) -3-ß-chloroethyl-5- (N-- methyl-N-but-3-enylamino) -l, 3-imidazolidin-2-one, l- (5-cycloheptyl-l, 3,4-thiadiazol-2-yl) -3-ß-bromoethyl-5-hex --4-enylamino-1,3-imidazolidin-2-one,

13

625520

l- (5-But-3-enyl-l, 3,4-thiadiazoI-2-yl) -3-Y-chloropropyl-5-ß-

-ethoxyethylamino-l, 3-imidazolidin-2-one, 1 - (5-pent-4-enyl-1,3,4-thiadiazol-2-yl) -3-S-chlorohexyl-5-y-

-ethoxypropylamino-l, 3-imidazolidin-2-one, l- (5-hex-4-enyl-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-8-propoxy-

butylamino-l, 3-imidazolidin-2-one, l- (5-ß-bromoethyI-l, 3,4-thiadiazol-2-yl) -3-methyl-5-w-meth-

oxyhexylamino-l, 3-imidazolidin-2-one, l- (5-Y-chloropropyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-cyclo-

butylamino-1,3-imidazolidin-2-one, l- (5-8-chlorobutyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-cyclo-

pentyIamino-l, 3-imidazolidin-2-one, l- (5-ß-bromohexyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-cycIo-

hexylamino-l, 3-imidazolidin-2-one, l- (5-ethoxy-l, 3,4-thiadiazol-2-yl) -3-methyl-5-cycloheptyl-

amino-l, 3-imidazolidin-2-one, l- (5-butoxy-l, 3,4-thiadiazol-2-yl) -3-methyl-5-ß-hydroxy-

ethylamino-1,3-imidazolidin-2-one, l- (5-hexyloxy-l, 3,4-thiadiazol-2-yl) -3-methyl-5-Y-hydroxy-

propylamino-l, 3-imidazolidin-2-one, l- (5-ethylthio-l, 3,4-thiadiazol-2-yl) -3-methyl-5-ß-hydroxy-

hexylamino-l, 3-imidazolidin-2-one, l- (5-propylthio-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (2-ethyl-

anilino) -1,3-imidazolidin-2-one, l- (5-hexylthio-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (2-propyl-

anilino) -l, 3-imidazolidin-2-one, l- (5-ethylsulfonyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (4-hexyl-

anilino) -1,3-imidazolidin-2-one, l- (5-butylsulfonyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (4-

-ethoxyanilino) -l, 3-imidazolidin-2-one, l- (5-hexylsulfonyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (4-hexyl-

oxyanilino) -l, 3-imidazolidin-2-one, 1 - (5-ethyisulfinyI-1,3,4-thiadiazol-2-yl) -3-methyl-5- (4-iodine)

aniIino) -l, 3-imidazolidin-2-one, l- (5-propylsulfinyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (4-fluoro-

anilino) -l, 3-imidazolidin-2-one, l- (5-hexylsulfinyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (3,4-di-

bromanilino) -l, 3-imidazolidin-2-one, l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (3,4,5-trichloro-

anilino) -l, 3-imidazolidin-2-one, l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (3-

-chlonnethylanilino) -l, 3-imidazolidin-2-one, l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (3-ß-chloroethyl-

anilino) -l, 3-imidazolidin-2-one, l- (5-trifluoromethyl-l, 3,4-thiadiazoI-2-yl) -3-methyl-5- (4-co-

-chlorhexylanilino) -1,3 -imidazolidin2-one, l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (2-ethylthio-

anilino) -1,3-iraidazolidin-2-one, l- (5-trifluoromethyl-l, 3,4-thiadiazoI-2-yl) -3-methyl-5- (3-

-propylthioauilino) -l, 3-imidazolidin-2-one, l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5- (4-butylthio-

anilino) -1,3 -imidazolidin-2-one, 1 - (5-trifluoromethyl-1,3,4-thiadiazol-2-yl) -3-methyl-5- (3-hexyl-

thioaniIino) -l, 3-iniidazolidin-2-one,

1 - (5-t-Butyl-1,3) 4-thiadiazol-2-yI) -3-methyl-5- [N- (2-methyl-

-4-chlorobenzyl) amino] -l, 3-imidazolidin-2-one, l- (5-trifluoromethylil-l, 3,4-thiadiazol-2-yl) -3-methyl-5- [N - ethyI- N- (2,6-dimethylbenzyl) amino] -1,3-imidazolidin-2 - one,

1- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-heptylamino

-l, 3-imidazolidin-2-one, l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-octylamino-

-1,3-imidazolidin-2-one, l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-nonylamino-

-l, 3-imidazolidin-2-one, l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-decylamino-1,3-imidazolidin-2- on,

- (5-t-Butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-undecylamino-

-l, 3-imidazolidin-2-one,

- (5-t-Butyl-1,3,4-thiadiazol-2-yl) -3-methyl-5-tridecylamino-

-l, 3-imidazolidin-2-one, - (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-tetradecyl-

amino-1,3-imidazolidin-2-one, - (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-pentadecyl-

amino-1,3-imidazolidin-2-one, - (5-t-butyl-1,3,4-thiadiazol-2-yl) -3-methyl-5-hexadecyl-

amino-1,3-imidazolidin.-2-one, - (5-t-butyl-l, 3,4-thiadiazoI-2-yl) -3-methyl-5-heptadecyI-

amino-1,3-imidazolidin-2-one, - (5-trifluoromethyl-l, 3,4-thiadiazoI-2-yl) -3-ethyl-5-ethylene-

imino-l, 3-imidazolidin-2-one, - (5-methyl-l, 3,4-thiadiazol-2-yl) -3-butyl-5-trimethyleneimino-

-1,3-imidazolidin-2-one, - (5-ethyl-l, 3,4-thiadiazol-2-yl) -3-pentene-5-tetramethylene

imino-1,3-imidazolidin-2-one, - (5-isopropyl-l, 3,4-thiadiazol-2-yl) -3-hexyl-5-pentamethylene-

imino-l, 3-imidazolidin.-2-one, - (5-pentyl-l, 3,4-thiadiazol-2-yl) -3-but-3-enyl-5-hexamethy-

lenimino-l, 3-imidazolidin-2-one, - (5-hexyl-1,3,4-thiadiazol-2-yl) -3-pent-4-enyl-5-ethylene-

imino-1,3-imidazolidin-2-one, - (5-cyclobutyl-l, 3,4-thiadiazol-2-yl) -3-hex-4-enyl-5-trime-

thylenimino-1,3-imidazolidin-2-one, - (5-cyclopentyl-l, 3,4-thiadiazol-2-yl) -3-ß-chloroethyl-5-tetra-

methylenimino-l, 3-imidazolidin.-2-one, - (5-cycloheptyl-l, 3,4-thiadiazol-2-yl) -3-ß-bromoethyl-5-

-pentamethyleneimino-l, 3-imidazolidin-2-one, - (5-but-3-enyl-1,3,4-thiadiazol-2-yl) -3-Y-chloropropyl-5-hexa-

methylenimiiio-l, 3-imidazolidiii-2-one, - (5-pent-4-enyl-l, 3,4-thiadiazol-2-yl) -3-8-chlorohexyl-5-

-ethyleneimino-1,3-imidazolidin-2-one, - (5-hex-4-enyl-l, 3,4-thiadiazol-2-yl) -3-ethyl-5-trimethylene-

imino-l, 3-imidazolidin-2-one, - (5-ß-bromoethyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-tetra-

methylenimino-l, 3-imidazolidin-2-one, - (5-Y-chloropropyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-penta-

methylenimino-l, 3-imidazolidin-2-one, - (5-8-chlorobutyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hexa-

methylenimino-1,3-imidazolidin-2-one, - (5-ß-bromohexyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-ethylene

imino-1,3-imidazolidin-2-one, - (5-ethoxy-1,3,4-thiadiazol-2-yl) -3-methyl-5-trimethylene-

imino-1,3-imidazolidin-2-one, - (5-butoxy-l, 3,4-thiadiazol-2-yl) -3-methyl-5-tetramethylene-

imino-1,3-imidazolidin-2-one, - (5-hexyloxy-l, 3,4-thiadiazol-2-yI) -3-methyl-5-pentamethy-

lenimino-1,3-imidazolidin-2-one, - (5-ethylthio-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hexamethylene-

imino-1,3-imidazolidin.-2-one, - (5-propylthio-l, 3j4-thiadiazol-2-yI) -3-methyl-5-ethylene-

imino-l, 3-imidazolidin-2-one, - (5-hexylthio-l, 3,4-thiadiazoI-2-yI) -3-methyl-5-trimethylene-

imino-l, 3-imidazolidin-2-one, - (5-ethylsulfonyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-tetra-

methylenimino-l, 3-imidazolidin-2-one, - (5-butylsulfonyl) -l., 3,4-thiadiazol-2-yl) -3-methyl-5-penta-

methylenimino-l, 3-imidazolidin-2-one, - (5-hexylsulfonyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hexa-

methylenimino-1,3-imidazolidin-2-one, - (5-ethylsulfinyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-ethylene

imino-l, 3-imidazolidin-2-one, - (5-propylsulfinyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-trimethyl

lenimino-l, 3-imidazolidin-2-one, - (5-hexyisulfinyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-tetra-methylenimino-l, 3-inxidazolidin-2-one and the same.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

625520

14

For practical use as herbicides, the novel compounds which can be prepared according to the invention are generally incorporated into herbicide mixtures which contain an inert carrier and a herbicidally toxic amount of the compound in question. In these herbicidal formulations, the active ingredient can be conveniently applied in any amount to the weed site. The formulations can be solids such as dusts, granules or wettable powders or liquids such as solutions, aerosols or emulsifiable concentrates.

Dusts can be produced, for example, by mixing and grinding the active ingredient with a solid inert carrier such as talc, clay, silica, pyrophyllite or the like. Granules are obtained by impregnating a granular carrier such as attapulgite or vermiculite, usually with a particle size of about 0.3 to 1.5 mm, with the active ingredient, which is generally dissolved in a suitable solvent. Wetting powders, which can be dispersed in water or oil at any concentration of active ingredient, are usually obtained by adding wetting agent to concentrated dusts.

In some cases, the active ingredients are sufficiently soluble in common organic solvents such as kerosene or xylene, so that they can be used directly as solutions in these solvents. Herbicide solutions are often dispersed as aerosols at excess pressure. However, the preferred liquid formulations are emulsifiable concentrates which contain a novel active ingredient which can be prepared according to the invention and, as an inert carrier, a solvent and an emulsifier. These emulsifiable concentrates can be diluted with water and / or oil to any concentration of active substance which is suitable for application to the site of weed infestation. The most common emulsifiers used in these concentrates are non-ionic or mixtures of non-ionic and anionic surfactants. With some emulsifier systems, a water-in-oil emulsion can be created for direct application to the weeds.

A typical herbicide mixture is illustrated by the following example:

Example 69 Preparation of a dust

Product acc. Example 4 10 parts by weight

Talc powder 90 parts by weight

The above components are mixed in a mechanical grinder / mixer and ground until a homogeneous free-flowing dust of the desired particle size is obtained. This is suitable for direct application to the area of weed infestation.

The novel compounds which can be prepared according to the invention can be used as herbicides in a manner known per se. One method of controlling weeds is, for example, to treat the site of the infestation with a herbicide which comprises an inert carrier and, as an active ingredient, a herbicide-toxic amount of a new compound which can be prepared according to the invention. The concentration of the new compounds which can be prepared according to the invention in the herbicide mixtures depends, for example, on the type of formulation and the purpose pursued. In general, however, the herbicide mixtures contain about 0.05 to about 95% by weight of new active ingredient which can be prepared according to the invention. According to a preferred embodiment, the herbicide mixtures contain about 5 to about 75% by weight of active ingredient. Such substances may also contain other substances such as other pesticides, for example insecticides, nematocides, fungicides and the like, stabilizers, spreading agents, deactivators, adhesives and adhesives, fertilizers, activators, synergists and the like.

The novel compounds 5 which can be prepared according to the invention are generally also useful in combination with other herbicides and / or defoliants, drying agents, growth inhibitors and the like. These further constituents can make up about 5 to about 95% of the active compounds in the herbicide mixture. The use of combinations of such other herbicides and / or defoliants, drying agents and the like and novel compounds which can be prepared according to the invention usually leads to herbicide mixtures which achieve even more effective weed control, and results are often achieved which cannot be obtained with separate agents from the individual herbicides reached. These other herbicides, defoliants, drying agents and growth inhibitors with which the novel compounds which can be prepared according to the invention can be combined in herbicide mixtures include, for example, chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB , 4 (2,4-DB), 2,4-DEB, 4-CPB, 4-CPA, 4-CPP, 2,4,5-TB, 2,4,5-TES, 3,4-DA, Silvex and the like, carbamate herbicides such as IPC, CIPC, Swep, Barban, BCPC, CEPC, CPPC and the like, thiocarbamate and dithiocarbamate herbicides such as CDEC, metham sodium, EPTC, dialates, PEBC, Perbulate, Vernolate and the like , substituted urea herbicides such as norea, siduron, dichloral urea, chloroxuron, cycluron, fenuron, monuron, monuron-TCA, diuron, linuron, monolinuron, Ne-30 buron, buturon, trimeturon and the like, symmetrical triazine herbicides such as simazine, Chlorazin, Atraon, Desme-tryn, Norazin, Ipazin, Prometryn, Atrazin, Trietazin, Simeton, Prometon, Propazin, Ametryn and the like, Chloracet-amid-Her bicidal such as a-chloro-N, N-dimethylacetamide, CDEA, 35 CDAA, a-chloro-N-isopropyl / acetamide, 2-chloro-N-isopropyl-acetaniline, 4- (chloroacetyI) morpholine, l- (chloroacetyI) -piperidine and the like, herbicides from chlorinated aliphatic acids such as TCA, Dalapon, 2,3-dichloropropionic acid, 2,2,3-TPA and the like, chlorinated benzoic acid and phenyl-40 acetic acid herbicides such as 2,3,6 -TBA, 2,3,5,6-TBA, Dicamba, Tricamba, Amiben, Fenac, PBA, 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dichlorophenylacetic acid, 2 - methoxy- 3,5,6-trichlorophenylacetic acid, 2,4-dichloro-3-nitro-benzoic acid and the like and other compounds such as 45 aminotriazole, maleic acid hydrazide, phenylmercury acetate, endothal, biuret, technical chlorordane, dimethyl-2,3,5,6-- tetrachloroterephthalate, Diquat, Erbon, DNC, DNBP, Di-chlobenil, DPA, Diphenamid, Dipropalin, Trifluralin, Solan, Dicryl, Merphos, DMPA, DSMA, MSMA, Kaliumazid, 50 Acrolein, Benefin, Bensulid, AMS, Bromacil, 2- ( 3,4-dichlorophenyl) -4-methyl-l, 2,4-o xadiazoIidin-3,5-dione, bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, di-chlone, diphenatril, DMTT, DNAP, EBEP, EXD, HCA, ioxynil, OPX, isocil, potassium cyanate, MAA, MAMA, MCPES, 55 MCPP, MH, Molinat, NPA, OCH, Paraquat, PCP, Pi-chloram, DPA, PCA, Pvrichlor, Sesone, Terbacil, Terbutol, TCBA, Brominil, CP-50144, H-176-1, H-732 , M-2901, Plana-vin, sodium tetraborate, calcium cyanamide, DEF, ethyl xanthogen disulfide, Sindone, Sindone B, Propanil, and the-6o same.

Weeds are generally undesirable plants that grow in an unsuitable place, are of no economic benefit and affect the production and growth of crops and ornamental plants or the health of cattle. Numerous weeds are known, for example the annuals such as amaranth, white goose foot, foxtail, blood millet, field mustard, pennywort, loophole, sticky herb, gauchheil, airport oats, woolly honey grass,

15

625520

Purslane, millet, water pepper, knotweed, common The effectiveness of the producible according to the invention

Burdock, wild buckwheat, kochia, black clover, grain - new compounds show e.g. the values from table I. rade, ragwort, pork thistle, croton, cuphea, steamer,

Teufelszwirn, Erdrauch, common ragwort, field down,

Milkweed, knotweed, emex, wild rice, pondweed, cumin, winch, millet, water nymph, rye horseradish, common thorn apple, witch grass, wild beet, the two-year-olds such as wild carrot, matricaria, wild barley, fire clove, chamomile, small mallow, cotton herb , Ox thistle, dog's tongue, moth cottonweed and purple thistle or the multi-year-old weeds such as perennial loophole, queens, Johnson grass, field thistle, fence winch, loophole, bermuda grass, sorrel, curly sorrel, hornbill, dandelion,

Bellflower, field winch, Russian knapweed, proso-pis, linseed, yarrow, asters, field stone seeds, chess stalks, vernonia, sesbania, rump, reed, winter cress, horse nettle, sceria, spurge.

These weeds are also generally classified as broad-leaved or grass-like weeds. The control of the growth of these weeds should preferably take place for economic reasons without damaging the useful plants or the cattle.

The new compounds which can be prepared according to the invention are generally particularly suitable for weed control,

as they are toxic to numerous weed species and relatively non-toxic to numerous crops. The exact amount required in each case depends on various factors, for example the hardness of the weed in question, the weather, the type of soil, the method of application, the type of crop plants 30 present at the same time and the like. While the application of only about 70 to 140 g of active ingredient per hectare can be sufficient to adequately combat a weak infestation with weeds living under unfavorable conditions, the application of 11 kg / ha or more can be used to effectively combat a dense infestation with hard, perennial weeds that grow under favorable conditions may be required.

The herbicidal toxicity of the novel compounds which can be prepared according to the invention can be demonstrated in various recognized test procedures, for example in the pre-and post-procedure.

The herbicidal activity of the novel compounds which can be prepared according to the invention was demonstrated, for example, on various weeds in the preliminary process. In these tests, small weed seeds filled with dry soil were generally placed in small plastic pots. 24 hours after sowing, the pots were normally sprayed with water until the soil was moist, and the test compounds were sprayed onto the surface of the earth in aqueous emulsions of emulsifier-containing acetone solutions in the concentrations indicated.

After spraying, the containers were conveniently placed in the greenhouse and provided with the necessary heat and watered daily or more frequently. 55 The plants were usually kept under these conditions for 21 days, then the extent of the damage to the plants was rated on a scale from 0 to 10 as follows:

60

0 = no damage,

1, 2 = slight damage,

3.4 = moderate damage,

5.6 = moderate to severe damage, 65

7, 8, 9 = severe damage and

10 = kill.

TABLE I

Test verb. Amount of weed

^ Bdspfelf855 kg / ha YNSG W0AT IMWD VTLF JNGS PIGW WMSTD YLFX BNGS CBGS CTGS MNGY BDWD SPGT QKGS

8.96

5

10th

10th

10th

9

10th

10th

9

10th

9

10th

10th

-

-

-

4.48

5

10th

10th

10th

9

10th

10th

9

10th

9

10th

10th

-

-

-

2.24

3rd

10th

10th

10th

10th

10th

10th

9

10th

9

10th

10th

-

-

-

1.12

4th

10th

10th

10th

10th

10th

10th

9

10th

4th

10th

10th

-

-

-

0.56

-

10th

9

10th

10th

10th

10th

9

10th

0

10th

10th

10th

10th

10th

0.28

-

10th

9

10th

10th

10th

10th

9

10th

0

10th

10th

6

6

10th

0.14

-

9

9

10th

10th

10th

10th

6

8th

0

4th

10th

3rd

3rd

10th

0.07

-

8th

9

10th

5

10th

10th

0

3rd

0

0

10th

0

0

9

8.96

5

10th

10th

10th

5

10th

10th

10th

10th

10th

10th

8th

-

_

4.48

5

10th

10th

10th

8th

10th

10th

10th

10th

10th

10th

10th

-

-

-

2.24

5

10th

10th

10th

8th

10th

10th

9

10th

8th

10th

10th

-

-

-

1.12

5

10th

5

10th

9

10th

10th

10th

10th

9

10th

10th

-

-

-

0.28

3rd

10th

8th

10th

9

10th

10th

10th

10th

9

10th

10th

10th

10th

-

0.14

0

10th

7

10th

9

10th

10th

6

10th

7

6

10th

10th

10th

-

0.07

0

6

3rd

10th

7

10th

10th

4th

8th

0

0

6

4th

0

-

0.035

0

2nd

2nd

10th

0

4th

5

0

0

0

0

5

0

0

-

8.96

4th

10th

6

10th

10th

10th

10th

7

10th

9

10th

10th

-

-

4.48

5

10th

5

10th

8th

10th

9

9

10th

9

10th

10th

-

-

-

2.24

5

10th

10th

10th

10th

10th

10th

8th

10th

8th

10th

10th

-

-

-

1.12

4th

10th

10th

10th

10th

10th

10th

10th

10th

4th

10th

10th

-

-

-

0.56

-

10th

8th

10th

10th

10th

10th

10th

10th

6

10th

10th

10th

10th

10th

0.28

-

10th

6

10th

8th

10th

10th

9

10th

3 •

10th

10th

0

4th

10th

0.14

-

10th

7

10th

7

10th

10th

9

10th

2nd

9

10th

0

4th

10th

0.07

-

5

8th

10th

0

5

10th

0

8th

0

0

5

0

2nd

5

TABLE I (continued)

Test verb. Product according to the example:

Amount kg / ha

YNSG

WOAT

JMWD

VTLF

INGS

PIGW

Weed WMSTD YLFX

BNGS

CBGS

CTGS

MNGY

BDWD

SPGT

QKGS

11

0.56

-

10th

10th

10th

9

10th

10th

9

10th

4th

10th

10th

10th

10th

9

0.28

-

10th

10th

10th

9

10th

10th

9

10th

3rd

10th

10th

8th

8th

10th

0.14

-

9

7

10th

8th

10th

10th

9

9

0

10th

10th

3rd

5

10th

0.07

-

9

6

10th

3rd

10th

10th

7

9

0

3rd

10th

3rd

4th

10th

12th

0.56

-

10th

6

10th

9

10th

10th

9

10th

5

10th

10th

10th

10th

10th

0.28

-

10th

7

10th

9

10th

10th

9

10th

4th

10th

10th

9

10th

10th

0.14

-

10th

5

10th

7

10th

10th

9

10th

3rd

10th

10th

3rd

4th

10th

0.07

-

9

3rd

9

0

10th

10th

5

0

6

0

10th

0

0

3rd

14

0.28

0

10th

6

10th

9

10th

10th

9

10th

9

10th

10th

9

10th

-

0.14

0

9

10th

10th

9

10th

10th

8th

10th

7

10th

10th

8th

10th

-

0.07

0

10th

7

10th

8th

10th

10th

9

10th

6

10th

10th

7

10th

-

0.035

0

4th

5

4th

3rd

10th

7

4th

3rd

4th

6

10th

0

0

-

15

0.56

-

10th

7

10th

9

10th

10th

8th

10th

4th

10th

10th

10th

10th

10th

0.28

-

9

8th

10th

9

10th

10th

9

10th

0

9

10th

10th

7

10th

0.14

-

6

5

10th

6

10th

10th

9

9

0

10th

10th

4th

7

5

0.07

-

6

4th

10th

3rd

10th

10th

4th

4th

0

3rd

10th

3rd

0

3rd

48

0.56

-

10th

8th

8th

9

10th

10th

9

10th

4th

10th

10th

9

10th

10th

0.28

-

10th

8th

7

9

10th

10th

9

10th

4th

10th

10th

4th

9

10th

0.14

-

10th

7

8th

6

10th

10th

9

10th

3rd

7

10th

0

7

10th

0.07

-

9

5

8th

4th

10th

10th

9

7

2nd

6

10th

0

3rd

7

63

8.96

5

10th

6

10th

10th

10th

10th

10th

10th

9

10th

10th

-

-

-

4.48

4th

10th

10th

10th

10th

10th

10th

9

10th

9

10th

10th

-

-

-

2.24

4th

10th

6

10th

9

10th

10th

9

10th

6

10th

10th

-

-

-

1.12

4th

10th

10th

10th

10th

10th

10th

9

10th

4th

10th

10th

-

-

-

625520

18th

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The herbicidal activity of the novel compounds which can be prepared according to the invention has also been demonstrated, for example, in the weed method on a number of weeds. In these experiments, the test compounds 5 were usually formulated in an aqueous emulsion and sprayed in the stated doses onto the foliage of the weeds which had reached a prescribed size. After spraying, the plants were usually kept in the greenhouse and watered daily or more frequently. No water was preferably applied to the foliage of the treated plants. The severity of the damage was normally determined 14 days after treatment and rated from 0 to 10 on the above scale. The effectiveness of the new compounds which can be produced according to the invention is shown, for example, by the values of Tables II and III.

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TABLE II

Test verb, acc. Example: -

Amount kg / ha

YNSG

WOAT

PIGW

JNGS

BDWD

WMSTD

Weed YLFX BNGS

CBGS

MNGY

JMWD

SPGT

CTGS

VTLF

4th

0.56

-

10th

10th

10th

10th

10th

10th

9

4th

10th

10th

10th

10th

10th

0.28

-

9

10th

10th

10th

10th

10th

9

3rd

10th

10th

7

10th

10th

0.14

-

6

10th

7

6

10th

7

9

2nd

10th

10th

4th

7

8th

0.07

-

0

10th

6

3rd

10th

0

0

0

10th

10th

3rd

0

7

8th

8.96

10th

10th

10th

10th

10th

10th

10th

10th

10th

10th

10th

——

i

4.48

9

10th

10th

10th

10th

10th

10th

10th

10th

10th

10th

_

.

2.24

10th

10th

10th

10th

10th

10th

10th

10th

10th

10th

10th

1.12

10th

10th

10th

9

10th

10th

9

10th

10th

10th

10th

0.56

-

10th

10th

8th

9

10th

10th

10th

-

10th

10th

.

10th

0.28

0

10 *

10 *

9 *

10 *

10 *

10 *

10 *

8th

10 *

10 *

10th

10th

10 *

0.14

0

8.5 *

10 *

7.5 *

. 5.5 *

10 *

8.5 *

10 *

9

10 *

6.5 *

9

7

10 *

0.07

0

5.5 *

10 *

4.5 *

4.5 *

10 *

4.5 *

6.5 *

0

9 *

5 *

5

0

10 *

0.035

0

0

3rd

4th

0

4th

0

4th

0

4th

3rd

3rd

0

3rd

9

8.96

6

10th

10th

10th

10th

10th

10th

10th

10th

10th

10th

_

4.48

8th

10th

10th

10th

10th

10th

10th

10th

10th

9

10th

.

.

2.24

8th

10th

10th

10th

10th

10th

10th

10th

9

10th

10th

-

1.12

5

10th

10th

10th

10th

10th

10th

10th

9

9

10th

-

.

0.56

-

10 *

10 *

9.5 *

10 *

10 *

10 *

10 *

10th

9 *

10 *

10th

10th

10 *

0.28

-

10 *

10 *

9.5 *

8th*

10 *

10 *

9.5 *

8th

10 *

10 *

10th

10th

10 *

0.14

-

7.5 *

10 *

8.5 *

10 *

10 *

9 *

8th*

5

10 *

10 *

10th

10th

10 *

0.07

-

4 *

10 *

3 *

8th*

10 *

4 *

3.5 *

2nd

10 *

10 *

3rd

3rd

5 *

11

0.56

-

9

10th

10th

6

10th

10th

9

4th

10th

10th

8th

10th

9

0.28

-

9

10th

10th

7

10th

9

9

3rd

10th

9

5

7

10th

0.14

-

3rd

10th

3rd

4th

10th

0

7

0

10th

9

7

2nd

9

0.07

3rd

10th

4th

0

10th

0

0

0

9

10th

3rd

3rd

4th

*) Average from two attempts

TABLE II (continued)

Test verb. Amount of weeds acc. Example: kg / ha YNSG WOAT PIGW JNGS BDWD WMSTD YLFX BNGS CBGS MNGY JMWD SPGT CTGS VTLF

12

0.56

-

9

10th

10th

10th

10th

10th

9

7

10th

10th

10th

10th

6

0.28

-

10th

10th

10th

10th

10th

10th

9

6

10th

10th

3rd

10th

5

0.14

-

9

10th

3rd

10th

10th

9

7

0

10th

10th

3rd

9

6

0.07

-

3rd

10th

4th

10th

10th

3rd

5

0

10th

9

3rd

6

5

14

0.28

3rd

10th

10th

9

10th

10th

10th

10th

10th

10th

10th

10th

10th

10th

0.14

0

10th

10th

9

9

10th

8th

10th

5

10th

6

3rd

4th

10th

0.07

0

4th

5

8th

5

10th

0

7

0

6

8th

5

0

10th

0.035

0

0

2nd

5

0

5

0

0

0

4th

0

0

0

10th

15

0.56

-,

10th

10th

10th

10th

10th

10th

9

2nd

10th

10th

10th

10th

10th

0.28

-

9

10th

10th

10th

10th

10th

9

2nd

10th

10th

9

10th

7

0.14

-.

5

10th

4th

10th

10th

3rd

7

0

10th

8th

2nd

7

6

0.07

-

3rd

10th

4th

10th

10th

3rd

3rd

0

8th

10th

0

3rd

6

48

0.56

,

10th

10th

10th

9

10th

10th

9

5

10th

10th

10th

10th

10th

0.28

-

9

10th

10th

8th

10th

8th

9

5

10th

10th

10th

10th

10th

0.14

-

10th

10th

7

6

10th

9

7

4th

10th

10th

2nd

10th

10th

0.07

-

0

10th

8th

3rd

10th

7

3rd

0

10th

7

4th

7

10th

63

0.56

10th

10th

10th

10th

10th

10th

9

5

10th

10th

10th

10th

10th

0.28

-

9

10th

9

10th

10th

10th

9

4th

10th

10th

10th

10th

10th

0.14

-

9

10th

9

4th

10th

10th

6

0

10th

10th

6

4th

10th

0.07

-

4th

7

5

5

10th

0

4th

0

10th

10th

3rd

2nd

10th

64

0.28

4th

10th

10th

9

10th

10th

10th

10th

8th

10th

10th

10th

10th

10th

0.14

3rd

10th

10th

9

10th

10th

9

10th

9

10th

9

10th

10th

10th

0.07

0

9

10th

6

9

10th

8th

10th

0

10th

4th

10th

3rd

5

0.035

0

3rd

10th

3rd

0

7

0

5

0

3rd

10th

4th

0

4th

YNSG = yellow Sceria BDWD = winch CBGS = millet SPGT = (sprangletop) balsamines

WOAT = airport oat WMSTD = field mustard MNGY = field winch CTGS = rye horseman (bromus)

PIGW = Amaranth YLFX = Gilbfennich JMWD = Common Thorn Apple VTLF = Cotton Grass

JNGS = sorghum BNGS = chicken millet

21st

TABLE III

625520

Product 'amount of weeds acc. Example: kg / ha GTFX FXMT WTRGS LMQR TFES QKGS A BLUE

8 0.56 10 10 10 10 10 10 10 0.28 10 10 10 10 10 10 10 0.14 10 8 10 10 9 7 10 0.07 5 3 5 9 0 7 10

9 0.56 10 10 10 9 10 10 10 0.28 10 10 10 9 10 10 10 0.14 10 10 10 9 10 10 10 0.07 10 10 7 9 6 7 10

GTFX = Risenfoxtail FXMT = Foxtail Millet WTRGS = Water Grass

LMQR = goose foot

TFES = large meadow fescue

QKGS = couch grass

A BLUE = annual grass

Claims (12)

625520 2nd PATENT CLAIMS 1. Process for the preparation of new compounds of formula I. Excess of an amine or cyclic imine of the formula III R3 H —N (III) N- N R - C C V R * (I) NO wherein R1 is an alkyl, cycloalkyl, alkenyl, haloalkyl, alkoxy, alkyithio, alkylsulfonyl or alkylsulfinyl radical, R- an alkyl, alkenyl or haloalkyl radical or a radical of the formula R5 I. - C - C - CH R6 wherein R5 and R "are hydrogen or alkyl, and R 'and R4 are hydrogen, an alkyl radical having up to 18 carbon atoms, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl or cycloalkyl radical or a radical of the formula - (CH9) 2. represent m, where X is an alkyl or alkoxy radical, halogen, haloalkyl or alkylthio radical, the nitro or cyano group, n is an integer from 0 to 3 and m is the number 0 or 1, below provided that at most one of the residues R! or R4 is an aromatic radical, or in which R3 and R4 together with the nitrogen atom form a cycloimino radical having 2 to 6 carbon atoms, characterized in that a compound of the formula II N " • N R - C / OH I. CH- in an inert organic solvent at the reflux temperature of the reaction mixture with azeotropic removal of the water of reaction. io 2. The method according to claim 1, characterized in that l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl - 5-t-butylamino-1,3-imidazolidine 2-one manufactures. 3. The method according to claim 1, characterized in that l- (5-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-hexyl- 15 amino-l, 3-imidazolidin-2-one produces. 4. The method according to claim 1, characterized in that l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl - 5-hexylamino-l, 3-imidazolidin-2-one manufactures. 5. The method according to claim 1, characterized in that l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl- -5-anilino-l, 3-imidazolidin-2-one. 6. The method according to claim 1, characterized in that l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl - 5-benzylamino-l, 3-imidazolidin-2-one manufactures. 7. Process according to claim 1, characterized in that l- (5-trifluoromethyl-l, 3,4-thiadiazol ~ 2-yl) -3-methyl - 5-ß-hydroxyethylamino-l, 3-imidazolidin-2 -on manufactures 8. The method according to claim 1, characterized in that l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yI) -3-methyl- 30 -5-diethylamino-l, 3-imidazolidin-2 ~ one produces 9. The method according to claim 1, characterized in that l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) -3-methyl - 5-tetramethylenimino-l, 3-imidazolidin-2-one manufactures. 10. The method according to claim 1, characterized in that l- (5-t-butyl-l, 3,4-thiadiazol-2-yl) -3-methyl-5-tetra- methyleniminol, 3-imidazolidin-2-one produces. 11. Use of the new compounds of formula I. 40 45 N- N / N - R I CH CH. R - C C V / - N \ (I) 50 C. II o -NO wherein R1 is an alkyl, cycloalkyl, alkenyl, haloalkyl, 55 alkoxy, alkythio, alkylsulfonyl or alkylsulfinyl radical, Rz is an alkyl, alkenyl or haloalkyl radical or a radical of the formula CH. C - N \ / \ (II) 60 -NO R5 - C - C = CH I. R8 wherein R1 and R2 have the meaning given above, with an equimolar amount or a molar 65 wherein Rs and R6 are hydrogen or alkyl, and R3 and R4 are hydrogen, an alkyl radical having up to 18 carbon atoms, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl or cycloalkyl radical or a radical of the formula 3rd 625520 2. represent m, wherein X is an alkyl or alkoxy radical, halogen, haloalkyl or alkylthio radical, the nitro or cyano group, n is an integer from 0 to 3 and m is the number 0 or 1, provided that at most one of the radicals R3 or R4 is an aromatic radical, or in which R3 and R4 together with the nitrogen atom form a cycloimino radical having 2 to 6 carbon atoms, as an active component in herbicidal compositions. represent in which X is an alkyl or alkoxy radical, halogen, haloalkyl or alkylthio radical, the nitro or cyano group, n is an integer from 0 to 3 and m is the number 0 or 1, provided that at most one of the R "'or R4 is an aromatic radical, or wherein R3 and R4 together with the nitrogen atom form a cycloimino radical having 2 to 6 carbon atoms, is characterized in that a compound of the formula II 10th OH N- ■ N / CH- CH. 15 R- _ C - N \ s / \ (II) 20th C- II o -NO