GB1579771A

GB1579771A - 1-thiazolyl imidazolidin-ones their preparation and use

Info

Publication number: GB1579771A
Application number: GB23189/77A
Authority: GB
Original assignee: Velsicol Chemical LLC
Current assignee: Velsicol Chemical LLC
Priority date: 1976-06-01
Filing date: 1977-06-01
Publication date: 1980-11-26
Also published as: AU2572977A; MX4638E; FR2353548B1; IL52091A; NL7705992A; AT354442B; DE2724614A1; JPS6134434B2; NZ184081A; AU505106B2; IL52091A0; ATA388477A; FR2353548A1; CH634201A5; JPS52148072A; CA1078391A; BR7703562A

Abstract

A herbicidal composition contains, as active ingredient, at least one novel compound of the formula <IMAGE> in which the substituents are as described in Claim 1. Processes for the preparation of the novel compounds are described. The herbicide is suitable, in particular, for controlling weeds since it is not toxic to useful plants.

Description

(54) 1-THIAZOLYL IMIDAZOLIDINONES, THEIR PREPARATION AND USE (71) We, VELSICOL CHEMICAL CORPORATION, a corporation organised and existing under the laws of the State of Delaware, United States of America, of 341 East Ohio Street, Chicago, Cook County, State of Illinois 60611, United States of America, (assignee of FRANK WU and JOHN KRENZER), do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to new compositions of matter and more specifically relates to new chemical compounds of the general formula

wherein X is halogen or alkylsulfonyl; Rl is alkyl, alkenyl, haloalkyl or

wherein R4 is hydrogen or alkyl; R5 is hydrogen or alkyl; Q is

R2 is hydrogen, alkyl, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl or

R6 is alkyl, alkenyl, haloalkyl, alkynyl, alkoxyalkyl, cycloalkyl or

p isO or 1; Y is alkyl, alkoxy, aklylthio, halogen, haloalkyl, nitro or cyano; and m is 0 or an integer from 1 to 3; R3 is hydrogen, alkyl, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl or

The compounds of the present invention are useful as herbicides.

In a preferred embodiment of the present invention X is chlorine, bromine, or lower alkylsulfonyl; R' is lower alkyl, lower alkenyl, lower haloalkyl or R4 - C - C CH R5 wherein R4 is hydrogen or alkyl of up to 3 carbon atoms; R5 is hydrogen or alkyl of up to 3 carbon atoms; R2 is hydrogen, lower alkyl, lower alkenyl, lower haloalkyl, lower hydroxyalkyl, lower alkoxyalkyl, cycloalkyl of from 3 to 7 carbon atoms or

R3 iS hydrogen, lower alkyl, lower alkenyl, lower haloalkyl, lower hydroxyalkyl, lower alkoxyalkyl, cycloalkyl of from 3 to 7 carbon atoms or

R6 is lower alkyl, lower alkenyl, lower haloalkyl, lower alkoxyalkyl, cycloalkyl of from 3 to 7 carbon atoms or

p isO or 1; Y is lower alkyl, lower alkoxy, lower alkylthio, halogen, lower chloroalkyl, lower bromoalkyl, trifluoromethyl, nitro or cyano; and m is 0 or an integer from 1 to 3.

The term "lower" as used herein designates a straight or branched carbon chain of up to 6 carbon atoms.

The compounds of the present invention wherein Q is

can be prepared by reacting a compound of the formula

wherein X and Rl are as heretofore described, with an amine of the formula

wherein R2 and R3 are as heretofore described. This reaction can be effected by combining the compound of formula II with an about equimolar amount or excess molar amount of the amine of formula III in an inert reaction medium, such as heptane of toluene, and then heating the reaction mixture, with stirring, at its reflux temperature and azeotropically removing the water of reaction. After this time the reaction mixture can be cooled, and the desired product can be recovered by filtration if formed as a precipitate or upon evaporation of the organic reaction medium if soluble therein. The product can then be purified by conventional means such as recrystallization.

The compounds of the present invention wherein

can be prepared by reacting the compound of formula II with an acid chloride of the formula

wherein R6 is as heretofore described, in the presence of an acid acceptor such as a tertiary amine. This reaction can be effected by slowly adding the acid chloride of formula VIII with stirring to a solution of an about equimolar amount of the compound of formula II in an inert organic solvent, in the presence of the acid acceptor, at a temperature of 10 to 30"C.

After the addition is completed, the reaction mixture can be heated at a temperature ranging up to the reflux temperature of the mixture to ensure completion of the reaction.

The desired product can then be recovered by first filtering the reaction mixture to remove acid acceptor chloride, followed by stripping off the solvent if the product is soluble therein, or, if formed as a prbcipitatc, by filtration and subsequent washing and purification.

The compounds of this invention wherein

can also be prepared by reacting a compound of formula II with an acid anhydride of the formula

wherein R6 is as heretofore described, in the presence of a catalytic amount of p-toluenesulfonic acid. This reaction can be effected by combining the reactants and the catalyst at room temperature in an inert organic reaction medium and then heating the reaction mixture on a steam bath with stirring for a period of from 1/2 to 4 hours. After this time the reaction mixture can be cooled, and the desired product can be recovered by filtration if formed as a precipitate or upon evaporation of the organic reaction medium if soluble therein. In some instances the acid anhydride can be used as a solvent for the compound of formula 1I, obviating the use of an inert solvent as the reaction medium.

When lower alkanoic anhydrides are used, water can be added to the reaction mixture to precipitate the desired product upon completion of the reaction. The product can then be purified by conventional means such as recrystallization. In some instances the foregoing reaction results in the formation of a mixture of products consisting of the desired compound of this invention and dehydrated starting material of the formula

wherein X and R' are as described. In these instances the desired product can be isolated by fractional precipitation.

The compound of formula ll can be readily prepared by heating a compound of the formula

wherein X and R' are as heretofore described, in a dilute, acidic reaction medium for a period of from 10 to 60 minutes. Temperatures of from 60"C to the reflux temperature of the reaction mixture can be utilized. The reaction medium can comprise a dilute, aqueous inorganic acid such as hydrochloric acid at a concentration of from 0.5 to 10 percent. Lower water-miscible alkanols can also be suitably added to the reaction medium to aid in the dissolution of the starting materials. After completion of the reaction the desired product can be recovered upon evaporation of the solvents used if soluble therein or by filtration if formed as a precipitate. This product can then be used as such or can be further purified by standard techniques such as trituration. recrystallization and washing.

The compounds of formula lV can be prepared by reacting a molar amount of an isocyanate dimer of the formula

wherein X is as heretofore described, with about two molar amounts of a dimethyl acetal of the formula

wherein R1 is as heretofore described. This reaction can be effected by combining the isocyanate dimer of formula V, dissolved in an inert organic solvent such as benzene, with the acetal of formula VI at room temperature and stirring the resulting mixture for a period of 1/2 to 4 hours. After this time the reaction mixture can be filtered and the filtrate stripped of solvent to yield the desired product. This product can be used as such or further purified if desired by standard techniques.

The isocyanate dimer of formula V can be prepared by reacting a thiazole of the formula

wherein X is as heretofore described, with phosgene. This reaction can be effected by adding a slurry or solution of the benzothiazole in a suitable organic solvent such as ethyl acetate to a solution of phosgene in a similar solvent. The resulting mixture can then be heated at reflux for a period of from 1/2 to 2 hours. The desired product can then be recovered by filtratioh if formed as a precipitate or upon evaporation of the organic solvent if soluble therein.

Exemplary suitable compounds of formula VI for preparing the compounds of the present invention are the dimethyl acetal of 2-methylaminoacetaldehyde, the dimethyl acetal of 2-ethylaminoacetaldehyde, the dimethyl acetal of 2-propylaminoacetaldehyde, the dimethyl acetal of 2-allylaminoacetaldehyde, the dirnethylacetal of 2-chloromethylaminoacetaldehyde, the dimethyl acetal of 2-ss-bromoethylaminoacetaldehyde or the dimethyl acetal of 2-propargylaminoacetaldehyde.

Exemplary suitable compounds of formula VII for preparing the compounds of this invention are 2-amino-5-chlorothiazolë, 2-amino-5-bromothiazole and 2-amino-5fluorothiazole.

Exemplary suitable compounds of formulae VIII and IX for preparing the compounds of the present invention are the acid chlorides or anhydrides of the following acids; acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, octanoic acid, dodecanoic acid, octadecanoic acid, acrylic acid, butenoic acid, pentenoic acid, chloroacetic acid, bromoacetic acid, ss-chlorobutanoic acid, cyclohexylcarboxylic acid, cyclopropylcarboxylic acid, benzoic acid, toluic acid, 4-chlorobenzoic acid, 3-bromobenzoic acid, 4-fluorobenzoic acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4-chloromethylbenzoic acid, 4trifluoromethylbenzoic acid, 3,4,5,-trichlorobenzoic acid, 3-methyl-thiobenzoic acid, 3ethylthiobenzoic acid, 4-butylthiobenzoic acid, phenylacetic acid, 4-methylphenylacetic acid, propynoic acid, butynoic acid, methoxyacetic acid, 5-methoxypropionic acid and y-ethoxybutanoic acid. The present invention also comprises a herbicidal composition comprising a compound of the invention together with a carrier and also a method of controlling weeds which comprises contacting the weeds with an effective amount of a compound of the invention, preferably in this form of a composition with a carrier.

The manner in which the compounds of the present invention can be prepared is more specifically illustrated in the following examples, some of which are included to illustrate the preparation of intermediates.

EXAMPLE 1 Preparatiorl of 5-brotnodiiazol-2-yI isocyanate dimer 2-Amino-5-bromothiazole (19.0 grams) and a saturated solution of phosgene in ethyl acetate (200 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture was heated at reflux with stirring for a period of about 3 hours. After this time the reaction mixture was cooled and filtered to recover the desired product 5-bromothiazol-2-yl isocyanate dimer as a fine yellow powder.

EXAMPLE 2 Preparation of the dimethyl acetal of 2-Ji -rnellzyl-3- (5-bronzotliiazol-2-y!) ureido]- acetaldehyde 5-Bromothiazol-2-yl isocyanate dimer (17.0 grams), benzene (70 ml) and the dimethyl acetal of 2-methylamino-acetaldehyde (13.5 grams) were charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture was then stirred at room temperature for a period of about one hour. After this time the reaction mixture was filtered, and the filtrate was stripped of solvent under reduced pressure, leaving an oil. This oil was chromatographed on silica gel using ethyl acetate as the diluant.

The eluant was dissolved in an ethanol-water mixture and the solution was filtered. The filtrate was then stripped of solvents under vacuum to yield the desired product the dimethyl acetal of 2-[1-methyl-3-(5-bromothiazol-2-yl)unedo]acetaldehyde as a crystalline solid having a melt point of 72 to 730C.

EXAMPLE 3 Preparation of 1-(5-bromothiazol-2-yl)-3-methyl-5-hydroxy-13-imidazolidin-2-one The dimethyl acetal of 2-[1-methyl-3-(5-bromothiazol-2-yl)ureido]acetaldehyde (10 grams), ethanol (80 ml), water (80 ml) and concentrated hydrochloric acid (8 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction vessel was purged with nitrogen gas, and the reaction mixture was heated at reflux with stirring for a period of about 15 minutes. After this time the reaction mixture was stripped of solvents under reduced pressure, and the residue was dissolved in ethyl acetate. The resulting solution was washed with saturated aqueous sodium bicarbonate and dried over anhydrous sodium sulfate. The dried solution was then filtered, and the filtrate was stripped of solvent, leaving an oil. This oil solidified upon standing to yield the desired product 1-(5-bromothiazol-2-yl)-3-methyl-5-hydroxy-1,3imidazolidin-2-one.

EXAMPLE 4 Preparation of 1-(5-bromothiazol-2-yl)-3-methyl-5-ethylamino-1,3-imidazolid in-2-one 1-(5-Bromothiazol-2-yl)-3-methyl-5-hydroxy- 1 ,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. Ethylamine (0.1 mole) is added to the reaction vessel, and the mixture is heated at reflux while removing the water as it is formed.

After no more water is given off, the reaction mixture is stripped of solvent under reduced pressure to yield the desired product 1-(5-bromothiazol-2-yl)-3-methyl-5-ethylamino-1,3imidazolidin-2-one as the residue.

EXAMPLE 5 Pre,paration of 1 - (5-bromot/1iazol-2-)l) -3-nl et/lyl-S-acetyloxX-I ,3-iniidazohdi,i-2-one 1-(5-bromothiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), acetyl chloride (0.11 mole) and pyridine (O.11 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is stirred for a period of about 15 minutes and is then allowed to stand for a period of about 2 hours. After this time water (100 ml) and hexane (30 ml) are added to the mixture. The organic phase is then separated from the aqueous phase and is dried over anhydrous magnesium sulfate.

The dried solution is then filtered and stripped of solvent under reduced pressure to yield the desired product l-(5-bromothiazol-2-yl)-3-methyl-5-acetyloxy-1,3-imidazolidin-2-one.

EXAMPLE 6 Prepalation of 5-chlorot/1iazol-2-vl isocyanate dimer 2-Amino-5-chlorothiazole (l9.0 grams) and a saturated solution of phosgene in ethyl acetate (200 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux with stirring for a period of about 3 hours. After this time the reaction mixture is cooled and filtered to recover the desired product 5-chlorothiazol-2-yl isocyanate dimer.

EXAMPLE 7 Preparation of the dimethyl acetal of 2-Ji -ethyl-3- (5-chlorothiazol-2-yl) ureido]acetaldehyde 5-Chlorothiazol-2-yl isocyanate dimer (17.0 grams), benzene (70 ml) and the dimethyl acetal of 2-ethylaminoacetaldehyde (13.5 grams) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is then stirred at room temperature for a period of about one hour. After this time the reaction mixture is filtered, and the filtrate is stripped of solvent under reduced pressure, leaving an oil. This oil is dissolved in an ethanol-water mixture, and the solution is filtered. The filtrate is then stripped of solvents under vacuum to yield the desired product the dimethyl acetal of 2- [ 1-ethyl-3-(5-chlorothiazol-2-yl)ureido acetaldehyde.

EXAMPLE 8 Preparation of 1-(5-chlorothiazol-2-yl)-3-ethyl-5-hydroxy-1,3-imidazolidin-2-one The dimethyl acetal of 2-[1-ethyl-3-(5-chlorothiazol-2-yl)ureido]acetaldehyde (10 grams), ethanol (80 ml), water (80 ml) and concentrated hydrochloric acid (8 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction vessel is purged with nitrogen gas, and the reaction mixture is heated at reflux with stirring for a period of about 15 minutes. After this time the reaction mixture is stripped of solvents under reduced pressure, and the residue is dissolved in ethyl acetate. The resulting solution is washed with saturated aqueous sodium bicarbonate and dried over anhydrous sodium sulfate. The dried solution is then filtered, and the filtrate is stripped of solvent to leave the desired product 1-(5-chlorothiazol-2-yl)-3-ethyl-5-hydroxy1 ,3-imidazolidin-2-one.

EXAMPLE 9 Preparation of 1- (5-chlorothiazol-2-yl)-3-ethyl-5-t-butylamino-1, 3-imidazolidin-2-one 1-(5-Chlorothiazol-2-yl)-3-ethyl-5-hydroxy-1 ,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. t-Butylamine (0.1 mole) is added to the reaction vessel, and the mixture is heated at reflux while removing the water as it is formed. After no more water is given off, the reaction mixture is stripped of solvent under reduced pressure to yield the desired product 1-(5-chlorothiazol-2-yl)-3-ethyl-5-t- butylamino-1,3-imidazolidin-2-one as the residue.

EXAMPLE 10 Preparation of 1-(5-chlorothiazol-2-yl) -3-ethyl-5-acryloyloxy-1, 3-imidazolidin-2-one 1-(5-Chlorothiazol-2-yl)-3-ethyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), acryloyl chloride (0.11 mole) and pyridine (0.11 mole) are charged into a glass reaction vessel equipped with a mechanical stirred and thermometer. The reaction mixture is stirred for a period of about 15 minutes and is then allowed to stand for a period of about 2 hours. After this time water (100 ml) and hexane (30 ml) are added to the mixture. The organic phase is then separated from the aqueous phase and is dried over anhydrous magnesium sulfate.

The dried solution is then filtered and stripped of solvent under reduced pressure to yield the desired product 1-(5-chlorothiazol-2-yl)-3-ethyl-5-acryloyloxy-1,3-imidazolidin-2-one as the residue.

EXAMPLE 11 Preparation of 5-fluoroíhiazol-2-yl isocyanate dimer 2-Amino-5-fluorothiazole (19.0 grams) and a saturated solution of phosgene in ethyl acetate (200 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux with stirring for a period of about 3 hours. After this time the reaction mixture is cooled and filtered to recover the desired product 5-fluorothiazol-2-yl isocyanate dimer.

EXAMPLE 12 Preparation of the dimethyl acetal of 2-[1-allyl-3-(5-fluorothiazol-2-yI)ureido]acetaldehyde 5-Fluorothiazol-2-yl isocyanate dimer (17.0 grams), benzene (70 ml) and the dimethyl acetal of 2-allylaminoacetaldehyde (13.5 grams) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is then stirred at room temperature for a period of about one hour. After this time the reaction mixture is filtered, and the filtrate is stripped of solvent under reduced pressure, leaving an oil. This oil is dissolved in an ethanol-water mixture, and the solution is filtered. The filtrate is then stripped of solvents under vacuum to yield the desired product the dimethyl acetal of 2-[ 1-allyl-3-(5-fluorothiazol-2-yl)ureido]acetaldehyde.

EXAMPLE 13 Preparation of 1-(5-fluorothiazol-2-yl)-3-allyl-5-hydroxy-1,3-imidazolidin-2-one The dimethyl acetal of 2-[1-allyl-3-(5-fluorothiazol-2-yl)ureidojacetaldehyde (10 grams), ethanol (80 ml), water (80 ml) and concentrated hydrochloric acid (8 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction vessel is purged with nitrogen gas, and the reaction mixture is heated at reflux with stirring for a period of about 15 minutes. After this time the reaction mixture is stripped of solvents under reduced pressure, and the residue is dissolved in ethyl acetate. The resulting solution is washed with saturated aqueous sodium bicarbonate and dried over anhydrous sodium sulfate. The dried solution is then filtered, and the filtrate is stripped of solvent to leave the desired product 1-(5-fluorothiazol-2-yl)-3-allyl-5-hydroxy1,3-imidazolidin-2-one.

EXAMPLE 14 Preparation of 1 - (5-fluorothiazol-2-yl) -3-allyl-5-allylamino-1, 3-imidazolidin-2-one 1.(5-Fluorothiazol-2-yl)-3-allyl-5-hydroxy-1 ,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. Allylamine (0.1 mole) is added to the reaction vessel, and the mixture is heated at reflux while removing the water as it is formed.

After no more water is given off, the reaction mixture is stripped of solvent under reduced pressure to yield the desired product 1-(5-fluorothiazol-2-yl)-3-allyl-5-allylamino-1,3 imidazolidin-2-one as the residue.

EXAMPLE 15 Preparation of I - (S-fluorothiazol-2-yl) -3-allyl-5-a-chloroacetyloxy-1 ,3-imidazolid in-2-one 1-(5-Fluorothiazol-2-yl)-3-allyl-5-hydroxy-1 ,3-imidazolidin-2-one (0.1 mole), achloroacetyl chloride (0.11 mole) and pyridine (0.11 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is stirred for a period of about 15 minutes and is then allowed to stand for a period of about 2 hours.

After this time water (100 ml) and hexane (30 ml) are added to the mixture. The organic phase is then separated from the aqueous phase and is dried over anhydrous magnesium sulfate. The dried solution is then filtered and stripped of solvent under reduced pressure to yield the desired product 1-(5-fluorothiazol-2-yl)-3-allyl-5-a-chloroacetyloxy-1,3imidazolidin-2-one as the residue.

EXAMPLE 16 Preparation of 5-iodothiazol-2-yl isocyanate dimer 2-Amino-5-iodothiazole (19.0 grams) and a saturated solution of phosgene in ethyl acetate (200 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux with stirring for a period of about 3 hours. After this time the reaction mixture is cooled and filtered to recover the desired product 5-iodothiazol-2-yl isocyanate dimer.

EXAMPLE 17 Preparation of the dimethyl acetal of 2-[1-propargyl-3-(5-iodothiazol-2-yl)ureidol- acetaldehyde 5-lodothiazol-2-yl isocyanate dimer (17.0 grams), benzene (70 ml) and the dimethyl acetal of 2-propargylamino-acetaldehyde (13.5 grams) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is then stirred at room temperature for a period of about one hour. After this time the reaction mixture is filtered, and the filtrate is stripped of solvent under reduced pressure, leaving an oil. This oil is dissolved in an ethanol-water mixture, and the solution is filtered. The filtrate is then stripped of solvents under vacuum to yield the desired product the dimethyl acetal of 2-[ 1 -propargyl-3-(5-iodothiazol-2-yl)ureido]acetaldehyde.

EXAMPLE 18 Preparation of I - (5-iod othiazol-2-yl) -3-propargyl-5-hyd roxy-1 ,3-imidazolid in-2-one The dimethyl acetal of 2-[l- ropargyl-3-(5-iodothiazol-2-yl)ureidojacetaldehyde (10 grams), ethanol (8() ml), water (XO ml) and concentrated hydrochloric acid (8 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction vessel is purged with nitrogen gas, and the reaction mixture is heated at reflux with stirring for a period of about 15 minutes. After this time the reaction mixture is stripped of solvents under reduced pressure, and the residue is dissolved in ethyl acetate. The resulting solution is washed with saturated aqueous sodium bicarbonate and dried over anhydrous sodium sulfate. The dried solution is then filtered. and the filtrate is stripped of solvent to leave the desired product 1-(5-iodothiazol-2-yl)-3-propargyl-5- hydroxyl- 1 ,3-imidazolidin-2-one.

EXAMPLE 19 Preparation of 1-(5-iodothiazol-2-yl) -3.propargyl-5-(3-chloroethylamino-1,3-imidazolidin-2- one 1-(5-Iodothiazol-2-yl)-3-propargyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. -Chloroethylamine (0.1 mole) is added to the reaction vessel, and the mixture is heated at reflux while removing the water as it is formed. After no more water is given off, the reaction mixture is stripped of solvent under reduced pressure to yield the desired product 1-(5-iodothiazol-2-yl)-3-propargyl-5-ss- chloroethylamino-1,3-imidazolidin-2-one as the residue.

EXAMPLE 20 Preparation of 1-(5-iodothiazol-2-yl)-3-propargyl-5-propynoyloxy-1,3-imidazolidin-2-one 1-(5-Iodothiazol-2-yl)-3-propargyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), propynoyl chloride (0.11 mole) and pyridine (0.11 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is stirred for a period of about 15 minutes and is then allowed to stand for a period of about 2 hours. After this time water (100 ml) and hexane (30 ml) are added to the mixture. The organic phase is then separated from the aqueous phase and is dried over anhydrous magnesium sulfate.

The dried solution is then filtered and stripped of solvent under reduced pressure to yield the desired product 1-(5-iodothiazol-2-yl)-3-propargyl-5-propynoyloxy-1,3-imidazolidin-2- one.

EXAMPLE 21 Preparation of the dimethyl acetal of 2-[1 -chloromethyl-3- (5- bromothiazol-2-yl) ureido]- acetaldehyde 5-Bromothiazol-2-yl isocyanate dimer (17.0 grams), benzene (70 ml) and the dimethyl acetal of 2-chloromethyl-aminoacetaldehyde (13.5 grams) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is then stirred at room temperature for a period of about one hour. After this time the reaction mixture is filtered, and the filtrate is stripped of solvent under reduced pressure, leaving an oil. This oil is dissolved in an ethanol-water mixture, and the solution is filtered. The filtrate is than stripped of solvents under vacuum to yield the desired product the dimethyl acetal of 2-[1-chloromethyl-3-(5-bromothiazol-2-yl)ureido]acetaldehyde.

EXAMPLE 22 Preparation of 1-(5-bromothiazol-2-yl)-3-chloromethyl-5-hydroxy-1,3-imidazolidin-2-one The dimethyl acetal of 2-[1-chloromethyl-3-(5-bromothiazol-2-yl)ureido]acetaldehyde (10 grams), ethanol (80 ml), water (80 ml) and concentrated hydrochloric acid (8 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction vessel is purged with nitrogen gas, and the reaction mixture is heated at reflux with stirring for a period of about 15 minutes. After this time the reaction mixture is stripped of solvents under reduced pressure, and the residue is dissolved in ethyl acetate. The resulting solution is washed with saturated aqueous sodium bicarbonate and dried over anhydrous sodium sulfate. The dried solution is then filtered, and the filtrate is stripped of solvent to leave the desired product 1-(5-bromothiazol-2-yl)-3-chloromethyl-5hydroxy-1 ,3-imidazolidin-2-one .

EXAMPLE 23 Preparation of I-(5-bromothiazol-2 1-(5-bromothiazol-2-yl)-3-chloromethyl-5-ss-hydroxyethylamino-1,3- imidazolidin-2-one 1-(5-Bromothiazol-2-yl)-3-chloromethyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. -Hydroxyethylamine (0.1 mole) is added to the reaction vessel, and the mixture is heated at reflux while removing the water as it is formed. After no more water is given off, the reaction mixture is stripped of solvent under reduced pressure to yield th 1-(5-Bromothiazol-2-yl)-3--chloroethyl-5-hydroxy-1,34midazolidin-2-one (0.1 mole), amethoxyacetyl chloride (0.11 mole) and pyridine (0.11 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is stirred for a period of about 15 minutes and is then allowed to stand for a period of about 2 hours. After this time water (100 ml) and hexane (30 ml) are added to the mixture. The organic phase is then separated from the aqueous phase and is dried over anhydrous magnesium sulfate. The dried solution is then filtered and stripped of solvent under reduced pressure to yield the desired product 1-(5-bromothiazol-2-yl)-3-ss-chloroethyl-5-a- methoxyacetyloxy-1 ,3-imidazolidin-2-one.

EXAMI'LE 25 Preparation of 5-methylsulfonylthiazol-2-yl isocyanate dimer A saturated solution of phosgene in ethyl acetate (200 ml) is charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. 2-Amino-5- methylsulfonylthiazole (0.1 mole) is added with stirring. After the addition is completed, the reaction mixture is heated at reflux for a period of about one hour. After this time the mixture is cooled, and the solid product formed is recovered by filtration. The solid is then dried to yield the desired product 5-methylsulfonylthiazol-2-yl isocyanate dimer.

EXAMPLE 26 Preparation of the dimethyl acetal of 2-[1-ss-bromoethyl-3-(5-methylsulfonylthiazol-2- yl)ureido]acetaldehyde 5-Methylsulfonylthiazol-2-yl isocyanate dimer (0.1 mole), the dimethyl acetal of 2-ss-bromoethylaminoacetaldehyde (0.2 mole) and benzene (100 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is stirred at ambient temperatures for a period of about hour. After this time the reaction mixture is filtered, and the filtrate is stripped of solvent to yield the desired product the dimethyl acetal of 2-[1-ss-bromoethyl-3-(5-methylsulfonylthiazol-2-yl)ureido]- acetaldehyde as the residue.

EXAMPLE 27 Preparation of 1-(5-methylsulfonylthiazol-2-yl)-3-ss-bromoethyl-5-hydroxy-1,3- imidazolidin -2-one The dimethyl acetal of 2-[1 -ss-bromoethyl-3-(5-methylsulfonylthiazol-2- yl)urcido]acetaldchyde (15 grams), water (200 ml), methanol (200 ml) and concentrated hydrochloric acid (10 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of about 15 minutes. After this time the reaction mixture is stripped of solvents under reduced pressure, leaving a residue. This residue is recrystallized to yield the desired product 1-(5-methylsulfonylthiazol-2-yl)-3-P-bromoethyl-5-hydroxy-1,3imidazolidin-2-one.

EXAMPLE 28 Preparation of 1- (5-methylsulfonylthiazol-2-yl) -3-ss-bromoethyl-5-methoxymethylamino-1, 3 imidnzolidin -2-one 1-(5-MethylSulfonylthiazol-2-yl)-3-ss-bromoethyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) are charged into a glass reaction vessel equipped with a mechanical stirrcr, thermometer, Dean-Stark trap and reflux condenser. Methoxymethylaminc (0.1 mole) is added to the reaction vessel, and the mixture is heated at reflux while removing the water as it is formed. After no more water is given off, the reaction mixture is stripped of solvent under reduced pressure to yield the desired product 1-(5-methyl sulfonylthiazol-2-yl)-3--bromoethyl-5-methoxymethylamino-1 ,3-imidazolidin-2-one as the residue.

EXAMPLE 29 Preparation of 1-(5-methylsulfonylthiazol-2-yl)-3-ss-bromoethyl-5-benzoyloxy-1,3- iniidazohdhi-2-o,ie 1-(5-MethylSulfonylthiazol-2-yl)-3-ss-bromoethyl-5-hydroxy-1,3-imidazolidin-2-one (0.1 molc), benzoyl chloride (O.11 mole) and pyridine (0.11 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The reaction mixture is stirred for a period of about 15 minutes and is then allowed to stand for a period of about 2 hours. After this time water (l00 ml) and hexane (30 ml) are added to the mixture. The organic phase is then separated from the aqueous phase and is dried over anhydrous magnesium sulfate. The dried solution is then filtered and stripped of solvent under reduced pressure to yield the desired product 1-(5-methylsulfonylthiazol-2-yl)-3-ss-bromoethyl-5- benzoyloxy- 1 ,3-imidazolidin-2-one as the residue.

The new compounds of this invention are particularly valuable for weed control because they are toxic to many species and groups of weeds while they are relatively non-toxic to many beneficial plants. The exact amount of compound required will depend on a variety of factors, including the hardiness of the particular weed species, weather, type of soil, method of application and the kind of beneficial plants in the same area. Thus, while the application of up to only one or two ounces of active compound per acre may be sufficient for good control of a light infestation of weeds growing under adverse conditions, the application of ten pounds or more of an active compound per acre may be required for good control of a dense infestation of hardy perennial weeds growing under favorable conditions.

EXAMPLE 30 The herbicidal toxicity of the new compounds of this invention can be demonstrated by the following established testing techniques known to the art, pre- and post-emergence testing.

The herbicidal activity of the compounds of this invention was demonstrated by experiments carried out for the pre-emergence control of a variety of weeds. In these experiments small plastic greenhouse pots filled with dry soil were seeded with the various weed seeds. Twenty-four hours or less after seeding the pots were sprayed with water until the soil was wet and the test compound, 1-(5-bromothiazol-2-yl)-3-methyl-5-hydroxy-1,3imidazolidin-2-one (product of Example 3), formulated as an aqueous emulsion of an acetone solution containing emulsifiers was sprayed at the indicated concentrations on the surface of the soil.

After spraying, the soil containers were placed in the greenhouse and provided with supplementary heat as required and daily or more frequent watering. The plants were maintained under these conditions for a period of 21 days, at which time the condition of the plants and the degree of injury to the plants was rated on a scale of from 0 to 10, as follows: 0 = no injury, 1,2 = slight injury, 3,4 = moderate injury, 5,6 = moderately severe injury, 7,8,9 = severe injury and 10 = death. The effectiveness of these compounds is demonstrated by the data in Table I.

TABLE I Injury rating Rate in Weed species Ibs/acre: 8 4 1 1/4 1/8 1/16 Yellow nutsedge 2 2 0 -- -- - Wild oats 10 10 10 6 0 0 Jimsonweed 5 5 4 3 0 0 Velvetleaf 10 10 10 9 0 0 Johnsongrass 10 10 7 4 0 0 Pigweed 10 10 10 10 10 0 Wild mustard 10 10 10 10 10 6 Yellow foxtail 10 10 9 8 4 2 Barnyardgrass 10 10 10 2 0 0 Crabgrass 10 9 7 3 0 0 Cheatgrass 10 10 10 3 0 0 Morningglory 10 10 10 9 0 0 Sprangletop -- -- -- 6 0 0 Bindweed -- -- -- 0 0 0 Quackgrass -- -- -- 10 0 0 The herbicidal activity of the compounds of this invention was also demonstrated by experiments carried out for the post-emergence control of a variety of weeds. In these experiments the test compound, 1-(5-bromothiazol-2-yl)-3-methyl-5-hydroxy-1,3imidazolidin-2-one (product of Example 3), was formulated as an aqueous emulsion and sprayed at the indicated dosage on the foliage of the weeds that had attained a prescribed size. After spraying, the plants were placed in a greenhouse and watered daily or more frequently. Water was not applied to the foliage of the treated plants. The severity of the injury was determined 14 days after treatment and was rated on the scale of from 0 to 10 heretofore described. The effectiveness of these compounds is demonstrated by the data in Table II.

TABLE II Injury rating Rate in Injury rating Weed species Ibs/acre: 8 2 1 Pigweed 10 10 10 Crabgrass 10 5 4 Barnyardgrass 10 10 10 Jimsonweed 10 10 10 Wild mustard 10 10 10 Johnsongrass 10 10 10 Morningglory 10 10 10 Bindweed 10 10 10 Yellow foxtail 10 10 10 Yellow nutsedge 4 5 0 Wild oats 10 10 10 WHAT WE CLAIM IS:1. A compound of the general formula

wherein X is halogen or alkylsulfonyl; R' is alkyl, alkenyl, haloalkyl or

where R4 is hydrogen or alkyl; R5 is hydrogen or alkyl; Q is

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

TABLE II Injury rating Rate in Injury rating Weed species Ibs/acre: 8 2 1 Pigweed 10 10 10 Crabgrass 10 5 4 Barnyardgrass 10 10 10 Jimsonweed 10 10 10 Wild mustard 10 10 10 Johnsongrass 10 10 10 Morningglory 10 10 10 Bindweed 10 10 10 Yellow foxtail 10 10 10 Yellow nutsedge 4 5 0 Wild oats 10 10 10 WHAT WE CLAIM IS:1. A compound of the general formula

wherein X is halogen or alkylsulfonyl; R' is alkyl, alkenyl, haloalkyl or

where R4 is hydrogen or alkyl; R5 is hydrogen or alkyl; Q is

R2 is hydrogen, alkyl, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl or

R3 iS hydrogen, alkyl, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl or

R6 is alkyl, alkenyl, haloalkyl, alkynyl, alkoxyalkyl, cycloalkyl or

p is 0 or 1; Y is alkyl, alkoxy, alkylthio, halogen, haloalkyl, nitro or cyano; and m is0 or an integer from 1 to 3.
2. The compound of Claim 1, 1-(5-bromothiazol-2-yl)-3-methyl-5-acetyloxy-1,3- imidazolidin-2-one.
3. The compound of Claim 1, 1-(5-chlorothiazol-2-yl)-3-ethyl-5-acryloyloxy-1,3- imidazolidin-2-one.
4. The compound of Claim 1, 1-(5-fluorothiazol-2-yl)-3-allyl-5-a-chloroacetyloxy-1,3- imidazolidin-2-one.
5. The compound of Claim 1, 1-(5-iodothiazol-2-yl)-3-propargyl-5-propynoyloxy-1,3imidazolidin-2-one.
6. The compound of Claim 1, 1-(5-bromothiazol-2-yl)-3-ss-chloroethyl-5-a- methoxyacetyloxy-1 ,3-imidazolidin-2-one.
7. The compound of Claim 1, 1-(5-fluorothiazol-2-yl)-3-methyl-5 cyclopropylcarbonyloxy-1 ,3-imidazolidin-2-one.
8. The compound of Claim 1, 1-(5-methylsulfonyl-thiazol-2-yl)-3-ss-bromoethyl-5- benzoyloxy-1 ,3-imidazolidin-2-one.
9. The compound of Claim 1, 1-(5-bromothiazol-2-yl)-3-methyl-5-benzoyloxy-1,3- imidazolidin-2-one.
10. The compound of Claim 1, 1-(5-bromothiazol-2-yl)-3-methyl-5-hydroxy-1,3imidazolidin-2-one.
11. The compound of Claim 1, 1-(5-chlorothiazol-2-yl)-3-ethyl-5-hydroxy-1,3imidazolidin-2-one.
12. The compound of Claim 1, 1-(5-fluorothiazol-2-yl)-3-allyl-5-hydroxy-1,3imidazolidin-2-one.
13. The compound of Claim 1, 1-(5-iodothiazol-2-yl)-3-propargyl-5-hydroxy-1,3 imidazolidin-2-one.
14. The compound of Claim 1, 1-(5-bromothiazol-2-yl)-3-chloromethyl-5-hydroxy-1,3imidazolidin-2-one.
15. The compound of Claim 1, l-(5-bromothiazol-2-yl)-3-methyl-5-ethylamino-1,3imidazolidin-2-one.
16. The compound of Claim 1, 1-(5-chlorothiazol-2-yl)-3-ethyl-5-t-butylamino-1,3- imidazolidin-2-one.
17. A compound as claimed in claim 1, in which X is chlorine, bromine, or lower alkylsulfonyl; R' is lower alkyl, lower alkenyl, lower haloalkyl or

wherein R4 is hydrogen or alkyl of up to 3 carbon atoms; RS is hydrogen or alkyl of up to 3 carbon atoms; and R2 is hydrogen. lower alkyl, lower alkenyl, lower haloalkyl, lower hydroxyalkyl, lower alkoxyalkyl, cycloalkyl of from 3 to 7 carbon atoms or

R3 iS hydrogen, lower alkyl, lower alkenyl, lower haloalkyl, lower hydroxyalkyl, lower alkoxyalkyl, cycloalkyl of from 3 to 7 carbon atoms or

R6 is lower alkyl, lower alkenyl, lower haloalkyl, lower alkoxyalkyl, cycloalkyl of from 3 to 7 carbon atoms or

p isO or 1; Y is lower alkyl, lower alkoxy, lower alkylthio, halogen, lower chloroalkyl, lower bromoalkyl, trifuoromethyl, nitro or cyano; and m is 0 or an integer from 1 to 3.
18. A compound of the general formula given in claim 1, wherein X is halogen or alkylsulfonyl; R1 is alkyl, alkenyl, haloalkyl or

wherein R4 is hydrogen or alkyl, R5 is hydrogen or alkyl, and Q is

wherein R2 is hydrogen, alkyl, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl or

R3 is hydrogen, alkyl, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl or

wherein p isO or 1, Y is alkyl, alkoxy, alkylthio, halogen, haloalkyl, nitro or cyano; and mis 0 or an integer of from 1 to 3.
19. A compound of the general formula given in claim 1 wherein X is halogen or alkysulfonyl; Rl is alkyl, alkenyl, haloalkyl; or propargyl and

wherein R6 is alkyl, alkenyl, haloalkyl, alkynyl, alkoxyalkyl, cycloalkyl or

wherein p is 0 or 1; Y is alkyl, halogen, haloalkyl, alkoxy, alkylthio, nitro or cyano; and m is 0 or an integer of from 1 to 3.
20. A compound of the general formula 1 given in claim 1, wherein X is halogen, R1 is alkyl, alkenyl, haloalkyl or

wherein R4 is hydrogen or alkyl, R5 is hydrogen or alkyl; Q is - OH
21. A process for the preparation of a compound of the general formula I as claimed in claim 1 wherein Q is

which comprises reacting a compound of the formula

wherein X and R1 are as defined in claim 1, with an amine of the formula

wherein R2 and R3 are as defined in claim 1.
22. A process for the preparation of a compound of the general formula I as claimed in claim 1. wherein

which comprises reacting the compound of formula II with ah acid chloride of the formula

wherein R2 is as defined in claim 1, in the presence of an acid acceptor.
23. A process for the preparation of a compound of general formula I as defined in claim 1 wherein Q is

which comprises reacting a compound of formula II as defined in claim 18 with an acid anhydride of the formula

wherein R6 is as defined in claim 1, in the presence of a catalytic amount of p-toluenesulfonic acid.
24. A process as claimed in claim 22 or 23 wherein R' is alkyl, alkenyl, haloalkyl or propargyl.
25. A process for the preparation of a compound as claimed in claim 1, in which Q is -OH which comprises heating a compound of the formula

wherein X and R' have the meanings given in claim 1 in a dilute acidic reaction medium for 10 to 60 minutes.
26. A process as claimed in claim 25, wherein X is halogen.
27. A herbicidal composition comprising a compound as claimed in claim 1 together with a carrier.
28. A herbicidal composition comprising a compound as claimed in claim 18, together with a carrier.
29. A herbicidal composition comprising a compound as claimed in claim 19, together with a carrier.
30. A herbicidal composition comprising a compound as claimed in claim 20, together with a carrier.
31. A method for the control of weeds which comprises contacting the weeds with an effective amount of compound of general formula I as claimed in claim 1.
32. A method for the control of weeds which comprises contacting the weeds with an effective amount of compound of general formula I as claimed in claim 18.
33. A method for the control of weeds which comprises contacting the weeds with an effective amount of compound of general formula I as claimed in claim 19.
34. A method for the control of weeds which comprises contacting the weeds with an effective amount of compound of general formula I as claimed in claim 20.
35. A method as claimed in claim 31, in which the compound of general formula I is in the form of a herbicidal composition as claimed in claim 27.
36. A method as claimed in claim 32, in which the compound of the general formula I is in the form of a herbicidal composition as claimed in claim 28.
37. A method as claimed in claim 33, in which the compound of the general formula I is in the form of a herbicidal composition as claimed in claim 29.
38. A method as claimed in claim 34, in which the compound of the general formula I is in the form of a herbicidal composition as claimed in claim 30.
39. A compound as claimed in claim 1 substantially as hereinbefore described in any one of the foregoing Examples 3,8,13,18,22, or 27.
40. A compound as claimed in clam 1 substantially as hereinbefore described in any one of the foregoing Examples 4,9,14,19,23, or 28.
41. A compound as claimed in claim 1 substantially as hereinbefore described in any one of the foregoing Examples 5,10,15,20,24, or 29.
42. A process for the preparation of a compound of general formula I, substantially as hereinbefore described in any one of the foregoing Examples 3,8,13,18,22, or 27.
43. A process for the preparation of a compound of general formula 1, substantially as hereinbefore described in any one of the foregoing Examples 4,9,14,19,23, or 28.
44. A process for the preparation of a compound of general formula I, substantially as hereinbefare described in any one of the foregoing Examples 5,10,15,20,24, or 29.
45. A herbicidal composition according to claim 27 substantially as hereinbefore described in Example 3().
46. A method of controlling weeds according to claim 31 substantially as hereinbefore described in Example 3().