NL8001243A - TETRAHYDROBENZOTHIADIAZOLYLIMIDAZOLIDINONES. - Google Patents

Description

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Tetrahydrobenzothiadiazolylimidazolidinones.

This invention relates to new compounds, namely compounds of the general formula 1, in which X is alkyl, alkoxy, alkylthio, halogen, dialkylamino and / or cyano, n can be a number from 0 to 4 and R is alkyl, alkenyl, halogen -5 is alkyl and / or alkynyl. These compounds have been found to be surprisingly useful as herbicides, especially for controlling already emerging weeds.

Preferably, the alkyl and alkenyl groups of the substituents X and R are lower alkyl and alkenyl-10 groups, the alkynyl is preferably propargyl and the halogen is preferably chlorine or bromine.

The compounds of this invention are readily prepared by heating a compound of formula 2, wherein X, n and R have the aforementioned meanings, in a dilute aqueous acidic reaction medium for 10 to 90 minutes to temperatures between 60 ° C and boiling point of the reaction mixture. The reaction medium can contain, for example, 0.5 to 5% hydrochloric acid, and acid water-ethanol mixtures can also be used. After the reaction has ended, the desired product can be separated as precipitate or as a residue after cooling or evaporating the reaction mixture. This product can be used as such, but can also be further purified in the usual manner, for example by recrystallization.

The compounds of formula 2 can be prepared by reacting a carbamate of formula 3, in which Z is methyl or ethyl and X and n have the aforementioned meanings, with an acetal of formula 4, wherein R is the previously 800 1 2 43 2 has the meanings mentioned. This reaction can be accomplished by dissolving a compound of formula 3 in stoichiometric amount or in small excess in the acetal of formula 4 and heating that mixture for 12 to 48 hours to a temperature between 90 ° and 130 ° C while shielding with an inert gas. The reaction product can be recovered by distilling off unreacted starting material, and it can be used as such or purified by standard techniques if desired.

The compounds of formula 3 are known in the literature, but if they are not readily available, they can be prepared from a compound of formula 4 in which Z and n have the aforementioned meanings, by leaving them with methyl or ethyl chloroformate comment. This reaction can be accomplished by slowly adding the chloroformate to a solution of the compound of formula 3 in an organic solvent in the presence of an acid scavenger.

The latter can itself serve as a solvent, for example pyridine. After everything has been added, stirring is continued for a while to ensure completeness of the reaction. The product can then be separated and purified by conventional techniques, such as washing to remove the hydrochloride from the acid scavenger, recrystallization, etc.

Insofar as the compounds of formula 5 are not available, they can be prepared in the manner described in U.S. Pat. No. 3,682,945.

The compounds of formula 2 may also be prepared by reacting an isocyanate dimer of formula 6, wherein X and n have the previously given meanings, with a dimethyl acetate of the formula 4 wherein R has the previously given meanings. This reaction can be accomplished by heating a mixture of the isocyanate dimer and the acetal in an inert organic reaction medium such as toluene to boiling point. 2 to 30 minutes may be required to complete the reaction. Thereafter, the desired product is obtained by evaporating the reaction mixture, and it can be used either as such or after further purification in a known manner.

800 1 2 43 «Λ * 3

The isocyanate dimer of formula 6 can be prepared by reacting the tetrahydrobenzothiazole of formula 5 with phosgene. This reaction can be accomplished by adding a suspension or solution of the benzothiazole in a suitable organic liquid such as ethyl acetate to a solution of phosgene in a suitable organic liquid such as ethyl acetate. The mixture can then be stirred at room temperature for 4 to 24 hours. The unused phosgene is then blown out of the solution with, for example, nitrogen. The desired product can be obtained by filtration (if it were a precipitate) or else by evaporating the solution to dryness. It can be used as such and after further purification.

Examples of tetrahydrobenzothiazoles of formula 5, suitable for preparing compounds of the invention are: 2-amino-4,5,6,7-tetrahydrobenzothiazole 2-amino-4-chloro-4,5,6,7- tetrahydrobenzothiazole 2-amino-5-methyl-4,5,6,7-tetrahydrobenzothiazole 2-amino-7-ethyl-4,5,6,7-tetrahydrobenzothiazole 20 2-amino-5-hexyl-4,5,6, 7-tetrahydrobenzothiazole 2-amino-5-methoxy-4,5,6,7-tetrahydrobenzothiazole 2-amino-5-cyano-4,5,6,7-tetrahydrobenzothiazole 2-amino-5-methylthio-4,5,6 7-tetrahydrobenzothiazole 2-amino-5,5-diethy1-4,5,6,7-tetrahydrobenzothiazoo1 25 2-amino-5-methyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazole 2-amino-5 -propylthio-4,5,6,7-tetrahydrobenzothiazole.

Examples of suitable acetals of formula 4 are the dimethylacetals of 2-methylaminoacetaldehyde, 2-ethylaminoacetaldehyde, 2-propylaminoacetaldehyde, 2-butyl-30 aminoacetaldehyde, 2-pentylaminoacetaldehyde and 2-hexylaminoacetaldehyde.

The invention is now further illustrated by the following examples.

Example I

35 Preparation of 2-amino-5,5,7,7-tetramethyl-4,5,5,7,7-tetrahydrobenzothiazole 800 1 2 43 * 4

In a three-necked flask equipped with stirrer and dropping funnel, a mixture of 9.9 g of 3,3,5,5-tetramethyl-cyclohexanone, 2.1 g of cyanamide, 1.6 g of sulfur and 8 ml of methanol was added dropwise with 5 ml of diethylamine the mixture 5 was cooled such that the temperature remained below 45 ° C. After everything was added, the mixture was heated at 40-45 ° C for an additional 2 hours. It was then poured into 100 ml of water and acidified to pH = 4 with hydrochloric acid. The mixture was washed with ether and in the aqueous phase the pH was adjusted to 9 with NaOH and then extracted again with ether. This extract was dried over anhydrous MgSO4 and evaporated to give the desired product as a material melting at 120-122 ° C.

Example II

Preparation of ethyl N- (5,5,7,7-tetramethyl-4,5,6,7-tetrahydro-15-benzothiazolyl-2) carbamate

Stirrer and dropping funnel were added to a solution of 16 g (75 mgmol) of 2-amino-5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazole in 100 ml pyridine in a three-necked flask with stirring. and cooling 11 g (100 mg mol) of ethyl chloro-20 formate are added dropwise. After all was added, stirring was continued for about 1 hour with the reaction mixture warming to room temperature. The reaction mixture was then poured into ice water to give a white precipitate. This was filtered off, dried and recrystallized from methanol. Thus, the desired product with a melting point of 124-125 ° C was obtained.

Example III

Preparation of the dimethyl acetal of 2- / 1-methyl-3- (5,5,7,7-tetra-methyl-4,5,6,7-tetrahydrobenzothiazolyl-2) urido / acetaldehyde

In a three-necked flask equipped with magnetic stirrer, reflux condenser and gas inlet tube, a mixture of 2 g of ethyl 1-N- (5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazol-2) carbamate was added and 20 ml of dimethyl acetal of 2-methylaminoacetaldehyde under nitrogen and heated at 120 ° C for 50 hours. The reaction mixture was then distilled under reduced pressure to remove 35 unchanged starting materials to leave a brown oily residue. This was purified by column chromatography using ethyl acetate as the running liquid. The solvent was evaporated from the appropriate fractions to give the desired compound as a colorless substance having a melting point of 108 ° C.

Example IV

Preparation of 1- (5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothia-zolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone-2

In 25 ml of 3.7% hydrochloric acid, 2.5 g of dimethyl acetal of 2 / / 1-methyl-3- (5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde dissolved, and this solution was heated to 85 ° C for about 10 minutes, causing a precipitate. A further 15 ml of hydrochloric acid were added and the mixture was stirred for an additional 90 minutes. Then the resulting precipitate was filtered off, washed with water and dried to give the desired compound with a mp. 135-138 ° C.

Example V

Preparation of the dimer of 5,5,7-trimethyl-4,5,6,7-tetrahydro-benzothiazolyl-2-isocyanate

200 ml of phosgene saturated ethyl acetate and 6.0 g of 2-amino-5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazole were placed in a glass flask equipped with stirrer and reflux condenser. This was refluxed for 5 hours, then solvent and unreacted starting materials were evaporated to give the desired dimer as a brown crystalline substance.

Example VI

Preparation of the dimethyl acetal of 2- / 1-methyl-3- (5,5,7-tri-methyl-4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde

In a glass flask equipped with stirrer and reflux condenser, a mixture of 7.5 g of dimer of 5,5,7-tri-30 methyl-4,5,6,7-tetrahydrobenzothiazolyl-2-isocyanate, 5 g of dimethyl acetal of 2- methylaminoacetaldehyde and 15 ml of toluene under stirring and reflux for 1 hour. After cooling, the reaction mixture was filtered, and the filtrate was washed with water, dried and evaporated to dryness leaving the desired acetal as a brown oil.

800 1 2 43 6

Example VII

Preparation of 1- (5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone-2 # In a glass flask, equipped with stirrer Thermometer and reflux condenser, a mixture of 8.5 g of dimethyl acetal of 2- / 1-methyl-3- (5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde, 25 ml of water, 25 ml of ethanol and 8.5 ml of concentrated hydrochloric acid are refluxed for 10 minutes. The solvents were then evaporated to give the desired product as a brown matter.

Example VIII

Preparation of ethyl N- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) carbamate

In a glass flask equipped with stirrer, thermometer and dropping funnel, stirring and cooling in a solution of 0.10 gmole of 2-amino-5,7-dimethoxy-4,5,6,7-tetrahydro-benzothiazole in 125 ml pyridine 0.12 gmoles of ethyl chloroformate were dropped. After all had been added, the reaction mixture was allowed to warm to room temperature and stirred for an additional 1 hour. The entire mixture was then poured into ice water to form a precipitate. This was filtered, dried and recrystallized to give the desired carbamate.

Example IX

Preparation of the dimethyl acetal of 2- / 1-ethyl-3- (5,7-dimethoxy-25 4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde

In a glass flask equipped with stirrer, reflux condenser and gas inlet tube, a mixture of 80 mgmoles of ethyl N- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) carbamate and 30 ml of dimethyl acetal of 2-ethylaminoacetaldehyde 8 heated to 125 ° C under nitrogen shielding for 30 hours. The reaction mixture was then distilled to remove excess starting material. The residue was purified by column chromatography using ethyl acetate as the running liquid. The solvent was evaporated from the appropriate fractions to give the desired acetal.

80 0 1 2 43 35 7

Example X.

Preparation of 1- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-ethyl-5-hydroxy-1,3-imidazolidinone-2

In a glass flask equipped with stirrer 5 and thermometer, a mixture of 50 mg mole of 2- / 1-ethyl-3- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde and 25 ml 3% hydrochloric acid heated to about 85 ° C for 45 minutes, causing a precipitate. This precipitate was filtered and dried to be the desired product.

Example XI

Preparation of ethyl N- (5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothiazolyl-2) carbamate

In a glass flask equipped with stirrer, thermometer and dropping funnel, stirring and cooling in a solution of 100 mgmole of 2-amino-5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothiazole in 125 ml pyridine 120 mgmoles of ethyl chloroformate were dropped. After all was added, the mixture was allowed to warm to room temperature and stirred for about 1 hour. Then the reaction mixture was poured into ice water to form a precipitate. This was filtered, dried and recrystallized to give the desired product.

Example XII

Preparation of the dimethyl acetal of 2- / 1-allyl-3- (5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothiazolyl-2) ureido / acetaldehyde 25 In a glass flask equipped with stirrer, reflux condenser and gas inlet tube a mixture of 80 mg mol ethyl-N- (5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzo thiazolyl-2) -carbamate and 30 ml dimethyl acetal of 2-allylaminoacetaldehyde was shielded for 8 hours at 125 g ° C heated. Then the reaction mixture was distilled to remove unreacted starting materials. The residue was purified by column chromatography using ethyl acetate as the running liquid. The solvent was evaporated from the appropriate fractions to give the desired dimethyl acetal.

Example XIII

Preparation of 1- (5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothiazolyl- 80 0 1 2 43 8 2) -3-ally1-5-hydroxy-1,3-imidazolidinone-2

In a glass flask equipped with a stirrer and thermometer, a mixture of 50 mg mol dimethyl acetal of 2- / 1-allyl-3- (5,5-diethyl-4,5,6,7-tetrahydrobenzothiazoly1-2) -5 urea / acetaldehyde and 25 ml of 3% hydrochloric acid were heated to about 85 ° C for about 45 minutes, resulting in a precipitate. This precipitate was filtered and dried to be the desired product. Example XIV

Preparation of ethyl N- (7-methylthio-4,5,6,7-tetrahydrobenzothia-10 zolyl-2) carbamate

Into a glass flask equipped with stirrer, thermometer and dropping funnel, a solution of 100 mg mol of 2-amino-7-methylthio-4,5,6,7-tetrahydrobenzothiazole in 125 ml of pyridine was added with stirring and cooling, 120 mg mol of ethyl chloroformate. . After all was added, the reaction mixture was allowed to warm to room temperature and stirred for about 1 hour. The reaction mixture was then poured into ice water, causing a precipitate. This was filtered, dried and recrystallized to give the desired carbamate.

Example XV

Preparation of the dimethyl acetal of 2- / 1-g-chloroethyl-3- (7-methylthio-4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde

In a glass flask equipped with stirrer, reflux condenser and gas inlet tube, a mixture of 80 mgmole of ethyl-N- (7-methylthio-4,5,6,7-tetrahydrobenzothiazoly1-2) -carbamate and 30 ml of dimethyl acetal of 2-g- chloroethylaminoacetaldehyde heated at 125 ° C for 8 hours under shielding with nitrogen gas. Excess starting material was then distilled off and the residue was purified by column chromatography using ethyl acetate as the running liquid. The solvent was evaporated from the appropriate fractions to give the desired dimethyl acetal.

Example XVI

Preparation of 1- (7-methylthio-4,5,6,7-tetrahydrobenzothiazoly1-2) -3-g-chloroethyl-5-hydroxy-1,3-imidazolidinone-2 In a glass flask equipped with stirrer and thermometer a mixture of 50 mg mol dimethyl acetal of 800 1 2 43 9 2- / 1-g-chloroethyl-3- (7-methylthio-4,5,6,7-tetrahydrobenzothia-zolyl-2) urea / acetaldehyde and 25 ml 3% hydrochloric acid heated to about 85 ° C for 45 minutes, causing a precipitate. This precipitate was filtered and dried to be the desired product.

Example XVII

Preparation of ethyl N- (5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazolyl-2) carbamate

In a glass flask equipped with stirrer, thermometer and dropping funnel, 10 2-amino-5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazole in 125 ml pyridine was stirred and cooled in a solution of 100 mgmol 120 mgmol ethyl chloroformate dripped. After all was added, the reaction mixture was allowed to warm to room temperature and stirring was stirred for about 1 hour.

The reaction mixture was now poured into ice water, causing a precipitate to form. This was filtered, dried and recrystallized to give the desired carbamate.

Example XVIII

Preparation of the dimethyl acetal of 2- / 1-but-3-enyl-3- (5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde In a glass flask equipped with a stirrer,

reflux condenser and gas inlet tube was a mixture of 80 mgmoles of ethyl N- (5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazolyl-2) -carbamate and 30 ml of dimethyl acetal of 2-but-3-enylaminoacetaldehyde Heated at 125 ° C with nitrogen gas for 8 hours and then distilled to remove excess starting material. The residue was purified by column chromatography using ethyl acetate as the running liquid. The solvent was evaporated from the appropriate fractions to give the desired dimethyl acetal. Example XIX

Preparation of 1- (5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-but-3-enyl-5-hydroxy-1,3-imidazolidinone-2

In a flask equipped with a stirrer and thermometer, a mixture of 50 mg mol dimethyl acetal of 2- / 1-but-3-enyl-3- (5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothia-35 zolyl-2) ureido / acetaldehyde and 25 ml of 3% hydrochloric acid heated to about 85 ° C for 45 minutes, causing a precipitate. This precipitate 80 0 1 2 43

V

10 was filtered and dried to be the desired product.

Example XX

Preparation of ethyl N- (5-hexyl-7-propoxy-4,6,6,7-tetrahydro-benzothiazolyl-2) carbamate 5 In a glass flask equipped with stirrer, thermometer and dropping funnel in a solution of 100 mgmol 2 - amino-5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazole in 125 ml pyridine while stirring and cooling 120 mg mol ethyl chloroformate. After all was added, the reaction mixture was allowed to warm to room temperature for 10 hours and stirred for an additional 1 hour.

The whole was then poured into ice water to form a precipitate. This was filtered, dried and recrystallized to give the desired product.

Example XXI

Preparation of the dimethyl acetal of 2- / 1-propyl-3- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde

In a glass flask equipped with stirrer, reflux condenser and gas inlet tube, a mixture of 80 mg mol ethyl-N- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) -20 carbamate and 30 ml dimethyl acetal of 2-propylaminoacetaldehyde heated to 125 ° C under shielding with nitrogen gas for about 8 hours, after which the mixture was distilled to remove excess starting materials. The residue was purified by column chromatography using ethyl acetate as the running liquid. The solvent was evaporated from the appropriate fractions to give the desired dimethyl acetal. Example XXII

Preparation of 1- (5-Hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-propyl-5-hydroxy-1,3-imidazolidinone-2

In a flask equipped with stirrer and thermo-30 meters, a mixture of 50 mg mol dimethyl acetal of 2- / 1-propyl-3- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde and 25 ml of 3% hydrochloric acid heated to about 85 ° C for 45 minutes, resulting in a precipitate. This precipitate was filtered and dried to be the desired product.

Example XXIII

800 1 2 43 11

Preparation of ethyl N- (5-ethylthio-4,5,6,7-tetrahydrobenzothiazolyl-2) carbamate

In a flask equipped with stirrer, thermometer and dropping funnel, 120 mgmol ethyl chloroformate was added dropwise to a solution of 100 mg mol 5 2-amino-5-ethylthio-4,5,6,7-tetrahydrobenzothiazole in 125 ml pyridine with stirring and cooling. After all was added, the reaction mixture was allowed to warm to room temperature and stirred for about 1 hour. Then the reaction mixture was poured into ice water to form a precipitate. This was filtered, dried and recrystallized to give the desired carbamate.

Example XXIV

Preparation of the dimethyl acetal of 2- / 1-bromomethyl-3- (5-ethyl-thio-4,5,6,7-tetrahydrobenzothiazolyl-2) ureido / acetaldehyde In a glass flask equipped with stirrer, reflux condenser and gas inlet tube. mixture of 80 mgmol ethyl-N- (ethylthio-4,5,6,7-tetrahydrobenzothiazolyl-2) carbamate and 30 ml dimethyl acetal of 2-bromomylaminoacetaldehyde heated at 125 ° C for 8 hours under shielding with nitrogen gas, after which the reaction mixture was distilled to remove excess starting materials. The residue was purified by chromatography using ethyl acetate as the running liquid. The solvent was evaporated from the appropriate fractions to give the desired dimethyl acetal.

Example XXV

Preparation of 1- (5-ethylthio-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-bromomethyl-5-hydroxy-1,3-imidazolidinone-2

In a flask equipped with stirrer and thermometer, a mixture of 50 mg mol dimethyl acetal of 2- / 1-bromomethyl-1-3- (5-ethylthio-4,5,6,7-tetrahydrobenzothiazolyl-2) urido / -30 acetaldehyde and 25 ml of 3% hydrochloric acid was heated to about 85 ° C for 45 minutes, causing a precipitate. This precipitate was filtered and dried to be the desired product.

Example XXVI

Preparation of ethyl N- (4,5,6,7-tetrahydrobenzothiazolyl-2) -35 carbamate

Into a glass flask equipped with stirrer, 800 1 2 43 12 thermometer and dropping funnel, 120 mg mol of ethyl chloroformate were added dropwise to a solution of 100 mg mol of 2-amino-4,5,6,7-tetrahydrobenzothiazole in 125 ml of pyridine with stirring and cooling. After all had been added, the reaction mixture was allowed to warm to room teraper temperature and stirred for about 1 hour. The reaction mixture was then poured into ice water to form a precipitate. This precipitate was filtered off, dried and recrystallized to give the desired carbamate.

Example XXVII

Preparation of the dimethyl acetal of 2- / 1-methyl-3- (4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde

In a flask equipped with stirrer, reflux condenser and gas inlet tube, a mixture of 80 mgmoles of ethyl N- (4,5,6,7-tetrahydrobenzothiazolyl-2) carbamate and 30 ml of dimethyl-15 acetal of 2-methylaminoacetaldehyde was stirred for 8 hours shield with nitrogen gas to 125 ° C, after which the mixture was distilled to remove excess starting materials. The residue was purified by column chromatography using ethyl acetate as a solvent. From the appropriate fractions, the solvent was evaporated to give the desired dimethyl acetal.

Example XXVIII

Preparation of 1- (4,5,6,7-tetrahydrobenzothiazolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone-2

In a glass flask equipped with stirrer and thermometer, a mixture of 50 mg mole dimethyl acetal of 2- / 1-methyl-3- (4,5,6,7-tetrahydrobenzothiazolyl-2) urea / acetaldehyde and 25 ml 3 % hydrochloric acid heated to about 85 ° C for 45 minutes, causing a precipitate. This precipitate was filtered and dried to be the desired product.

Other compounds which can be prepared in the same manner according to the invention are: 1- (5-propylthio-4,5,6,7-tetrahydrothiazoly1-2) -3-6-iodbutyl-5-hydroxy-1,3 imidazolidinone-2,1- (5-butylthio-4,5,6,7-tetrahydro-thiazolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone-2,1- (7-pentyl- 35 thio-4,5,6,7-tetrahydrothiazolyl-2) -3-butyl-5-hydroxy-1,3-imidazolidinone-2,1- (7-hexylthio-4,5,6,7-tetrahydrothiazolyl -2) -3-pen ~ 800 1 2 43 13 ty1-5-hydroxy-1,3-imidazolidinone-2,3- (5,7-diethoxy-4,5,6,7-tetrahydrothiazolyl-2) -3 -hexyl-5-hydroxy-1,3-imidazolidinone-2,1- (5-butoxy-4,5,6,7-tetrahydrothiazolyl-2) -3-pent-4-enyl-5-hydroxy-1,3 imidazolidinone-2,1 - (7-hexyloxy-4,5,6,7-tetrahydro thazolyl-2) -5 3-hex-3-enyl-5-hydroxy-1,3-imidazolidinone-2,1 ( 5,7-dibutyl-4,5,6,7-tetrahydrothiazolyl-2) -3-B-fluoroethyl-5-hydroxy-1,3-imidazolidi-non-2,1 (5,5,7-triethyl-) 4,5,6,7-tetrahydrothiazoly1-2) -3-6-chloro-hexy1-5-hydroxy-1,3-imidazolidinone-2,1 (5,5,7-trimethyl-7-cyano-4, 5,6,7-tetrahydrothiazolyl-2) -3- methyl-5-hydroxy-1,3-imidazolidi-10 non-2,1- (5-cyano-5,7-dimethyl-4,5,6,7-tetrahydrothiazoly1-2) -3-methyl-5-hydroxy -1,3-imidazolidinone-2,1 - (5-dimeth.ylamina-4,5,6,7-tetrahydrothiazolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone-2,1- ( 5-diethylamino-4,5,6,7-tetrahydrothiazolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone, 1- (7-dibutylamino-4,5,6,7-tetrahydro-15 thiazolyl -2) -3-propargy1-5-hydroxy-1,3-imidazolidinone-2,1- (5,5,7-trimethyl-4,5,5,7,7-tetrahydrothiazolyl-2) -3-propargyl-5- hydroxy-1,3-imidazolidinone-2,1- (5-bromo-4,5,6,7-tetrahydrothiazolyl-2) -3-propargyl-5-hydroxy-1,3-imidazolidinone-2.

For practical use as herbicides, the compounds of the invention are generally converted into a composition consisting of an inert carrier and a herbicidal amount of its compound. Such preparations, also called "formulations", allow the active compound to be applied easily and effectively to the weed-infested areas. These formulations can be solids such as dusting powders, granules and wettable powders, but also liquids such as solutions, aerosols and self-emulsifying concentrates.

For example, a dusting powder can be prepared by mixing and grinding the active compound together with an inert carrier such as talc, clay, silicate, pyrophyllite or the like. Granules can be prepared by drenching a granular carrier (for example of attapulgite or vermiculite, usually with dimensions between 0.3 and 1.5 mm) with a solution of the active compound. Wettable powders, which can be dispersed to any desired concentration of active compound in water or oil, can be prepared by applying wetting agents to concentrated dusting powders.

In some cases, the active compounds are sufficiently soluble in common organic solvents such as petroleum or xylene to use them directly as solutions in these liquids. Often solutions of these herbicides can be sprayed under elevated pressure, such as aerosols.

Preferably, however, liquid herbicidal preparations are emulsifiable concentrates containing the active compound of the invention, a solvent as a carrier and an emulsifying agent. Such concentrates can be diluted with water and / or oil to any desired active compound concentration before being sprayed on site. The most commonly used emulsifiers are the nonionic or the mixtures of nonionic with anionic surfactants. Some emulsifier systems allow the creation of a reverse emulsion (water in oil) for direct application to weed infestations.

A typical preparation according to the invention is, for example, a mixture of 10 parts by weight of the product of Example 20 with 90 parts of talcum powder. These components are ground together into a homogeneous, easily spreadable powder of the desired particle size, which as such is directly applicable.

The compounds of the invention can be used as herbicides in any manner known in the art. One is that at the site where those weeds grow, enough of the herbicidal compound is applied because weeds die. The concentration of the herbicides of the invention in the compositions containing them may vary within very wide limits, but will generally be between 0.05 and 95 wt%, preferably between 5 and 75 wt%. These preparations may also contain other substances, such as other pesticides (insecticides, nematocides, fungicides, etc.), stabilizers, dispersants, activators, inactivators, synergites, adhesives, fertilizers, etc., etc.

The compounds of the invention are also useful in combination with other herbicides and / or defoliation agents, dewatering agents, growth inhibitors and the like in the herbicidal compositions already described above. These other substances can make up 5% to 95% of the preparation. Combining the compounds of the invention with these other herbicides and / or defoliators, dewatering agents, etc. results in formulations that are even more effective in suppressing weeds and sometimes give results that cannot be achieved with the individual formulations of the different herbicides. These other herbicides, defoliants, dewatering agents and plant growth inhibitors with which the compounds of the invention can be combined include 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, etc .; carbamates such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, etc.; thiocarbamates and dithiocarbamates such as CDEC, metham sodium, EPTC, diallate, PEBC, perbulate, vernolate, etc.; substituted ureas such as norea, siduron, dichloral urea, chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron, monolinuron, neburon, buturon, trimeturon and the like; symmetrical triazines such as simazine, chlorazine, atraon, desmetryne, norazine, ipazine, prometryn, atrazine, trietazine, simetone, prometone, propazine, ametryne, etc.; chloroacetamides such as α-chloro-N, N-dimethyl-acetamide, CDEA, CDAA, α-chloro-N-isopropylacetamide, 2-chloro-N-isopropylacetanilide, 4- (chloroacetyl) morpholine, 1- (chloro-25-acetyl) piperidine , ed; chlorinated aliphatic acids such as TCA, dalapone, 2,3-dichloropropionic acid, 2,2,3-TPA and the like; chlorinated benzoic acids and phenylacetic acids, such as 2,3,6-TBA, 2,3,5,6-TBA, dicamba, tricamba, amiben, phenac, PBA, 2-methoxy-3,6-dichloro-phenylacetic acid, 3-methoxy- 2,6-dichlorophenylacetic acid, 2-methoxy-30 3,5,6-trichlorophenylacetic acid, 2,4-dichloro-3-nitrobenzoic acid and the like and such compounds as aminrtriazole, maleic hydrazide, phenyl mercury acetate, endothal, biuret, technical chlorodane, dimethyl-2, 3,5,6-tetrachloroterephthalate, diquat, erbon, DNC, DNBP, dichlobenil, DPA, diphenamide, dipropalin, trifluraline, solan, 35 dicryl, merphos, DMPA, DSMA, MSMA, potassium azide, acroleins, benefin, bensulacil, AMS, bromide 2- (3,4-dichlorophenyl) -4 ”methyl-1,2,4-800 1 2 45 16 oxadiazolidine-3,5-dione, bromxynil, cacodyl acid, CMA, CPMF, cypro-mid, DCB, DCPA, dichlon, diphenatrile, DMTT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocil, potassium cyanate, MAA, MAMA, MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP, picloram, DPA, PCA, pyrichlor, 5 seson, terbacil, terbutol, TCBA, brominil, CP-50144, H-176-1 , H-732, M-2901, planavin, sodium tetraborate, calcium cyanamide, DEF, ethylxanthogen disulfide, sindon, sindon B, propanil and the like.

More herbicides of this type can also be used in combination with the compounds according to the invention as salts, esters, amides and other derivatives, of course insofar as these compounds make this possible.

Weeds are unwanted plants that grow where they are not wanted, have no economic value and interfere with the production of useful crops, with the cultivation of ornamental plants or with the breeding of livestock. Many weeds are known, including annuals such as pig grass, goosefoot, fox tail, annual meadow grass, wild mustard, field cherry, ryegrass, bird wall, wild oats, Abutilon, purslane, coot, knotweed, bollard, buckwheat, kochia, caterpillar, wormwood, various species of thistles, coffee fever, ragwort, cevid, ragwort, hemp nettle, euphorbia, spurrie, wild rice, fountain herb, day flower, bedstraw and nymph herb, biennials such as wild carrot, feverfew, wild barley, cuckoo flower, chamomile, burdock, moth candle and moth -leaf mallow, road thistle, dog tongue and spear thistle, and perennial plants such as perennial ryegrass, cultivation, field thistle, bindweed, field bindweed, palm grass, sheep sorrel, curled sorrel, pearl grass, bird wall, dandelion, various types of bluebell, Mesquita, flax snapdragon, yarrow, asters, pearl seed, horsetail, hardy, Sesbania, cattail and loosestrife.

30 Often all the weeds are divided into broad-leaved herbs and grasses. It is economically desirable to control the growth of such herbs without harming beneficial plants or livestock.

The new compounds of the invention are especially valuable for weed control because they are toxic to many weeds and relatively little harmful to many beneficial plants. How much of one compound to apply exactly depends on several factors, including the hardness of the different plant species, the weather, the type of soil, the method of application, which 5 useful crops are in the same plot, etc. While using of only one or two kg / ha of active substance can be enough to control a light occupation with weeds that the conditions do not have for a good control of a dense occupation with hard annuals that grow under favorable conditions. 10 kg / ha or more are required.

The herbicidal action of the new compounds according to the invention can be achieved with many previously developed testing techniques, both on weeds that are yet to emerge and on weeds that are already there. The herbicidal activity of the compounds according to the invention has been shown by tests on weeds that have yet to germinate. In addition, small plastic flower pots with dry earth were provided with seeds of various types of plants, and 24 hours or less afterwards, these pots were sprayed with water until the earth was moist, after which the compounds to be tested were used as aqueous emulsions or as solutions in acetone was sprayed on the surface of this soil in certain amounts. Then these pots with soil were kept in greenhouses, in which the necessary heat, light and water were provided. After 15 to 21 days, the degree of damage to these plants was recorded in a scale from 0 to 10: 0 is no damage, 1 or 2 is minor damage, 3 or 4 is moderate damage, 5 or 6 is fairly serious damage, 7, 8 and 9 is heavy damage and 10 is dead. The effect of these compounds is seen in the accompanying Tables A and B. Numbers with a decimal point result from averaging two or more repeated experiments.

The herbicidal action of the compounds according to the invention was also found in tests on weeds that were already above the ground. In addition, the compounds to be tested were formulated as aqueous emulsions and sprayed in certain dosages over different types of plants that had reached a certain size. These plants were then placed in greenhouses 800 1 2 43 18 and watered daily or (if necessary) more often. No water was applied to the leaves of the treated plants. Damage severity 10 to 15 days after treatment was noted on the scale given above. The effect of these compounds in curative application is shown in Tables C and D. Numbers with decimal points are again the result of averaging repeated tests.

10 800 1 2 43 19

Table A

Tests with the compound of example IV Damage to not yet germinated plants Dosage in kg / ha 5 Species 8.8 2.2 1.1 0.55 '0.28 0.14

Yellow sedge 5 0 0.0 -

Wild oats 10 10 6.7 5.0 2.5 1.0

Thorn apple 10 10 10.0 - 4.0 5.0

Abutilon 10 10 9.0 8.5 10.0 8.5 10 Jansen grass 9 10 7.7 6.5 2.5 2.0

Pig grass 9 9 7.0 3.5 1.5 1.0

Wild mustard 10 10 10.0 10.0 10.0 4.0

Sea green needle 10 8 7.0 5.5 2.0 1.5

Hanepoot 30 30 9.3 10.0 7.0 0.0 15 Hand grass 9 8 8.0 7.0 3.0 1.5

Dravik 10 9 7.0 5.0 3.5 0.5

Day flower 8 10 8.3 7.0 4.0 4.5

Field bindweed - - 10.0 5.0 3.0 1.5

Breeding - - 5.5 4.5 4.0 2.5 20 Kortaar - - 10.0 9.0 4.5 3.5

Pinto beans - - 9.5 6.5 3.0 2.5

Sugar beet - - 9.0 8.5 8.0 9.5

Wheat - - 9.5 8.0 7.5 2.5

Rice - - 4.0 3.5 3.0 2.0 25 Soybeans - - 6.5 4.0 1.0 1.0

Cotton - - 10.0 5.0 2.5 0.5

Millet - - 10.0 10.0 5.0 4.5

Corn - - 7.0 5.5 3.0 0.5

Lucerne - - 10.0 3.5 2.0 1.0 30 Hayer - - 6.5 2.5 2.0 1.0 80 0 1 2 43 20

Table B

Tests with the compound of Example VII Damage to plants not yet germinated Dosage in kg / ha

Type 2.2 1.1_0.55_0.28_0.14

Yellow sedge 3.0 0.0 0.0

Wild oats 10.0 9.3 2.7 0.0 0.0

Thorn apple 10.0 4.0 2.5 4.0 1.0

Abutilon 10.0 10.0 8.5 5.5 1.0

Jansen grass 10.0 6.5 3.2 0.0 0.0

Pig grass 10.0 6.0 3.5 0.0 0.0

Wild mustard 10.0 9.0 10.0 1.0 0.5

Sea green sewing 9.0 9.0 2.2 2.2 0.5 0.5

Cinnabar 10.0 5.7 5.2 2.0 1.0

Hand grass 6.0 4.5 1.7 1.5 2.0

Dravik 10.0 6.7 1.7 0.5 0.0

Day flower 10.0 7.6 8.4 5.0 1.5

Field bindweed - 10.0 5.5 3.0 0.0

Culture - 10.0 6.0 2.5 0.0

Kortaar - 5.0 2.5 0.0 0.0

Pinto beans - 6.0 3.0 0.0 0.0

Sugar beet - 10.0 10.0 8.0 6.0

Wheat - 9.5 5.5 1.5 1.0

Rice - 4.0 2.5 3.5 0.0

Soybeans 6.0 3.7 0.7 0.3 1.0

Cotton 2.0 1.7 0.0 0.0 0.0

Millet - 10.0 4.0 2.0 1.0

Corn - 3.0 0.5 0.0 0.0

Lucerne - 5.0 0.0 0.0 0.0

Oats - 4.0 0.0 0.0 0.0

Bollard 7.0 2.0 1.0 0.0 800 1 2 43 21

Table C

Tests with the compound of Example IV

Damage to already standing plants_

Dosage in kg / ha 5 Species 2.2 1.1 0.55_0.28_0.14

Wild mustard 10.0 10.0 10.0 10.0 10.0

Wild oats 10.0 3.5 4.0 2.0 1.0

Field bindweed 10.0 10.0 10.0 10.0 3.0

Cinnabar 10.0 10.0 10.0 10.0 5.0 10 Palm grass 9.0 9.5 9.5 10.0 10.0

Sea green needle needle 9.0 10.0 10.0 6.0 4.0

Jansen grass 10.0 9.5 8.0 3.0 2.0

Dayflower 10.0 10.0 10.0 10.0 10.0

Thorn apple 10.0 10.0 10.0 10.0 5.0 15 Yellow sedge 5.0 2.0 2.0

Pig grass 10.0 10.0 10.0 10.0 10.0

Abutilon - 10.0 10.0 10.0 10.0

Culture - 10.0 6.0 4.0 2.0

Kortaar - 10.0 10.0 4.0 3.0 20 Dravik - 10.0 10.0 2.0 2.0

Pinto beans - 10.0 10.0 10.0 10.0

Millet - 10.0 10.0 10.0 10.0

Wheat - 10.0 5.0 10.0 1.0

Rice - 5.0 4.0 4.0 2.0 25 Cotton - 10.0 10.0 10.0 10.0

Corn - 7.0 10.0 4.0 3.0

Lucerne - 10.0 10.0 10.0 10.0

Oats - 2.0 2.0 0.0 0.0

Soybeans - 10.0 10.0 10.0 10.0 30 Sugar beet - 10.0 10.0 10.0 10.0 80 0 1 2 43 22

Table D

Tests with the compound of Example VII Damage to field plants already in the field Dosage in kg / ha 5 Species 2.2 1.1 0.55 0.28 0.14 0.07

Wild mustard 10.0 10.0 10.0 10.0 6.5 2.0

Wild oats 10.0 5.0 2.0 0.0 0.0 0.0

Field bindweed 10.0 10.0 9.0 5.5 1.0 0.0

Hanepoot 10.0 10.0 7.2 6.0 3.5 2.0 10 Hand grass 10.0 8.7 6.2 4.5 2.0 0.0

Sea green needle 10.0 5.7 5.7 2.5 1.0 0.0

Jansen grass 10.0 8.0 6.0 5.5 3.5 5.0

Dayflower 10.0 10.0 10.0 6.5 10.0 5.0

Thorn apple 10.0 9.3 9.2 8.5 8.5 10.0 15 Yellow sedge 2.0 0.5 0.0 - - -

Pig grass 10.0 8.3 7.5 6.0 4.0 3.0

Abutilon - 10.0 10.0 10.0 8.5 7.0

Culture - 10.0 10.0 7.0 2.0 2.0

Kortaar - 10.0 6.0 5.5 1.0 0.0 20 Dravik - 10.0 5.0 5.0 0.0 0.0

Pinto beans - 5.0 10.0 7.0 7.0 3.0

Millet - 10.0 5.0 1.0 1.0 0.0

Wheat - 2.0 1.5 1.0 0.0 0.0

Rice - 7.0 5.5 10.0 0.5 0.0 25 Cotton - 10.0 10.0 8.5 7.5 10.0

Corn - 4.0 3.0 0.5 0.5 0.0

Lucerne - 10.0 10.0 9.5 9.5 4.0

Oats - 2.0 0.5 1.0 0.5 0.0

Soybeans 10.0 10.0 7.0 4.5 3.5 3.0 25 Sugar beet - 10.0 10.0 8.5 6.5 2.0 80 0 1 2 43

Claims (10)

1. Compounds of general formula 1 wherein X is alkyl, alkoxy, alkylthio, halogen, dialkylamino and / or cyano, n may be a number from 0 to 4 and R is alkyl, alkenyl, haloalkyl, and / or alkynyl . 2. The compound 1- (5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone-2. 3. The compound 1- (5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone-2. 4. The compound 1- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-ethyl-5-hydroxy-1,3-imidazolidinone-2. 5. The compound 1- (5,5,7-trimethyl-7-cyano-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone-2. 6. The compound 1- (5-cyano-5,7-dimethyl-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-methyl-5-hydroxy-1,3-imidazolidinone-2. 7. The compound 1- (5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-but-3-enyl-5-hydroxy-1,3-imidazolidinone-2. 8. The compound 1- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazolyl-2) -3-propyl-5-hydroxy-1,3-imidazolidinone-2. Herbicidal composition, which contains as active substance a compound according to any one of the preceding claims. 10. Method for controlling weeds, characterized in that in a place where weeds are present or where weeds can emerge, sufficient of one or more compounds 30 according to any one of claims 1 to 8 is applied, optionally in the form of a formulation. 800 1 2 43 OH stainless steel I. s C -.- cN-CH.-C "H 0 R OCH3 2 Ϋ__ C- N— C- 0 — ZI 'I v SH 0 3, OCH} H - N - CH, - CH I \ 4 R OCHj z Rjf / c ~ Nrii 5 J. a 800 1 2 43 Velsicol Clieinical Corporation Chicago, Illinois, USA St. America