DE3007556A1 - TETRAHYDROBENZOTHIAZOLYLIMIDAZOLIDINONE AND THEIR USE AS HERBICIDES - Google Patents

Description

DR. BERG DIFL -ING. STAPF DIPL.-ING. SCHWABF DR. DR. 3ANDMAIR

PATENT LAWYERS 3007

P.O. Box 860245 8000 Munich 86

Attorney file: 30 712

VELSICOL CHEMICAL CORPORATION CHICAGO, ILLINOIS 60611 / USA

Tetrahydrobenzothiazolylimidazolidinones and their uses as herbicides

030037/0731

t (OW) 981272 Tdetrunme: 'Btnkkonten: Hypo-Bink Munich 4410122850

918273 BEROSTAPFPATENT Munich, (BLZ 70020011) Swffl Code: HYPO DE MM

988274 TELEX: Btytc Vereinibuik Munich 453100 (BLZ 70020270)

983310 0524560BEROd Pcitjcneck Munich 65343-808 (BLZ 70010080)

description

The invention relates to new substance preparations. In particular it relates to new chemical compounds of formula I.

-R (I)

wherein X is selected from alkyl, alkoxy, alkylthio, halogen, dialkylamino or cyano is chosen, η is an integer from 0 to U, and R is selected from alkyl, alkenyl, haloalkyl, or alkynyl.

The compounds of the invention are unexpectedly useful as herbicides and particularly effective in post-emergence control of weeds.

In a preferred embodiment of the invention, X from lower alkyl, lower alkoxy, lower alkylthio, chlorine, bromine, di- (lower alkyl) amino or cyano, and R from lower alkyl, Lower alkenyl, Nxedrigchloralkyl or Propargyl selected.

The compounds of the present invention can be easily prepared by adding a compound of formula II ,,.

030037/0731

- C - N - CH "-

OCH, ι

CH

OCH.

CII)

in which X, η and R have the meaning given above, heated for about 10 to 90 minutes in a dilute, aqueous, acidic reaction medium. Temperatures between about 60 ^° C. and the return temperature of the reaction mixture can be used. The reaction medium can contain a dilute, aqueous inorganic acid, such as, for example, hydrochloric acid, in a concentration of about 0.5 to 5%. Acid water-ethanol mixtures can also be used. When the reaction is complete, the desired product can be obtained as a precipitate or residue by cooling or evaporating the reaction mixture. This product can be used as such or further purified by conventional means such as recrystallization and the like.

The compounds of the formula II can by reacting a carbamate of the formula III

C-O-Z

(III)

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- / 6

30075S6

wherein Z is methyl or ethyl, and X and η are those given above Have meaning with an acetal of the formula IV

/ ^0CH 3
HN- CH ₀ - CH <(IV)

I \

R ^0CH 3

in which R has the meaning given above. This reaction can be carried out by dissolving the compound of the formula III in an equimolar amount or in an excess of the acetal of the formula IV and the resulting mixture for 12 to 18 h at a temperature of about 90 ^° C. to 130 ^° C. in one with Inert gas covered reaction vessel is heated. The reaction product can then be recovered by distillation to remove unreacted starting material and used as such or, if desired, further purified using standard methods.

The compounds of the formula III are known from the literature; if they are not available, then they can go out a compound of formula V

-N

I Il

- / 7

030037/073

■ _ *

wherein Z and η have the meaning given above, prepared by reaction with methyl or ethyl chloroformate will. This reaction can be carried out by slowly adding the chloroformate to a solution of the compound of formula III in an organic solvent, wherein an acid acceptor is present. This can even act as a solvent serve, for example in the case of pyridine. After the addition is complete, the reaction mixture can be stirred further to ensure full implementation. Then the desired product can be obtained and with cleaned using conventional methods, e.g. by washing out the acid acceptor hydrochloride, recrystallization, and the like

If the compounds of Formula V are not readily available, they can be prepared using the procedures described in US Pat. No. 3,682,945 getting produced.

The compounds of formula II can also be prepared by adding a molar amount of an isocyanate dimer Formula VI

C-N = C = O

(VI)

J2

-/8th

030037/073

wherein X and η have the meaning given above, with about two molar amounts of a dimethylacetal of the formula VII

OCH ₀

I ³

HN-CH ₀ -CH (VII)

I ² I

R OCH ₃

2
converts, in which R has the meaning given above. This reaction can be carried out by heating a mixture of the isocyanate dimer and the acetal in an inert organic reaction medium, such as, for example, toluene, at the reflux temperature of the reaction mixture. Heating under reflux can be continued for about 2 to 30 minutes, so that complete conversion is ensured. The desired product can then be obtained by evaporating the reaction medium and used as such or further purified using known methods.

The isocyanate dimer of the formula VI can be obtained by reacting the Tetrahydrobenzothiazole of the formula V can be prepared with phosgene. This reaction can be carried out by a slurry or solution of the benzothiazole in a suitable one organic solvent such as ethyl acetate to a saturated solution of phosgene in a suitable solvent like ethyl acetate there. The resulting mixture can be stirred for about 4 to 2 hours at room temperature. To the distance of unconverted phosgene can the reaction mixture

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810037/0731

then purged with nitrogen gas. The desired product, if it has formed as a precipitate, can then be filtered off or can be obtained by evaporation of the organic solvent used, if it is soluble therein. The product can be used as such or further purified as desired.

Tetrahydrobenzothiazole compounds of the formula V, which are used for the production of the compounds according to the invention are suitable, are e.g .:

2-amino-4,5,6,7-tetrahydrobenzothiazole 2-amino-4-chloro-4,5,6,7-tetrahydrobenzothiazole 2-amino-5-methy1-4,5,6,7-tetrahydrobenzothiazole 2-amino -7-ethyl-4,5,6,7-tetrahydrobenzothiazole 2-amino-5-hexy1-4,5,6,7-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-diethyl-4,5,6,7- tetrahydrobenzothiazole 2-amino-5-methyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazole
2-amino-5-propylthio-4,5,6,7-tetrahydrobenzothiazole

Acetals of the formula IV suitable for the preparation of the compounds according to the invention are, for example, the dimethyl acetal of 2-methylaminoacetaldehyde, the dimethyl acetal of 2-ethylaminoacetaldehyde, the dimethyl acetal of 2-propylaminoacetaldehyde,

030037/073 · _ _{/ 10}

the dimethyl acetal of 2-butylaminoacetaldehyde, the dimethyl acetal des 2-pentylaminoacetaldehyde and the dimethylacetal of 2-hexylaminoacetaldehyde.

The production possibilities of the compounds according to the invention are described in more detail in the following examples.

example 1

Preparation of 2-amino-5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazole

9.9 g of 3,3,5,5-tetramethylcyclohexanone, 2.1 g of cyanamide, 1.6 g of sulfur and 8 ml of ethanol were placed in a glass reaction vessel equipped with a mechanical stirrer and an addition funnel. Then, 5 ml of diethylamine was added dropwise to the reaction mixture; it was cooled in order to keep the reaction mixture below about 45 ⁰ C. After the addition was complete, the reaction mixture was ^{heated at HO to 45 °} C. for 2 h. The reaction mixture was then poured into 100 ml of water and acidified to pH 4 with hydrochloric acid. The mixture was then washed out with ether, the aqueous phase was drawn off and adjusted to pH 9 with aqueous sodium hydroxide. The resulting mixture was extracted with ether. The ether extract was then dried over anhydrous magnesium sulfate and evaporated to give the desired product 2-amino-5.5.7 _t 7-tetramethyl-

- / 11

• 10097/0711

4,5,6,7-tetrahydrobenzothiazole as a solid, mp. 120-122 ⁰ C.

Example 2

Preparation of ethyl N- (5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate

16 g (0.075 mol) of 2-amino-5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazole, dissolved in 100 ml of pyridine, were placed in a glass reaction vessel with a mechanical stirrer and addition funnel. Then, 11 g (0.1 mol) of ethyl chloroformate was added dropwise while stirring and cooling the reaction mixture. When the addition was complete, the reaction mixture was allowed to warm to room temperature and stirring was continued for about 1 hour. After this point the reaction mixture was poured into ice water, which resulted in a white precipitate. The precipitate was filtered off, dried and recrystallized from methanol to give the desired product ethyl N- (5,5,7,7-tetramethy1-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate, m.p. 124-125 ⁰ C.

Example 3

Preparation of the dimethylacetal of 2- [l-methyl-3- (5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl) -ureido] acetaldehyde

2 g of ethyl N- (5,5,7,7-tetramethyl 1-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate and 20 ml of dimethyl acetal of 2-methylamine

- / 12

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noacetaldehyde were placed in a glass reaction flask with a magnetic stirrer, reflux condenser and gas supply pipe. The reaction mixture was blanketed with nitrogen gas and heated ^{at 120 ° C. for about 50 h.} The reaction mixture was then distilled under reduced pressure in order to remove excess unreacted starting material; a brown oily residue remained. This residue was purified by elution chromatography using ethyl acetate as the eluant. The chromatographed solution was then stripped from the solvent and gave the desired product dimethylacetal des 2- [l-methyl-3- (S, 5, 7,7-tetramethy1-4,5,6,7-tetrahydrobenzothiazol-2-y1) -ureidq] acetaldehyde as a colorless solid, mp. 108 ⁰ C.

Example U

Preparation of 1- (5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one

2.5 g of dimethyl acetal des 2- £ 1-methyl 1-3- (5,5,7,7-tetramethy1-1,5,6,7-tetrahydrobenzothiazol-2-y1) -ureidq] acetaldehyde were diluted in 25 ml Dissolved 3.7% hydrochloric acid. ^{The solution was heated at 85 °} C. for about 10 minutes, which led to the formation of a precipitate. A further 15 ml of hydrochloric acid were added and stirring was continued for about 90 minutes. The precipitate was then filtered off, washed out with water and

dried to give the desired product 1- (5,5,7,7-tetramethyl-U, 5,6,7-tetrahydrobenzothiazol-2-yl) -3-methyl-5-hydroxy

030037/0738 - / 13

Or «

1,3-imidazolidin-2-one, m.p. 135-138 C.

Example 5

Preparation of 5,5 »7-trimethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl-isocyanate dimer

200 ml of saturated solution of phosgene in ethyl acetate and 6.0 g of 2-amino-5,5,7-trimethy1-1,5,6,7-tetrahydrobenzothiazole were placed in a glass reaction vessel with a mechanical stirrer and reflux condenser. The reaction mixture was heated at reflux temperature for about 5 h. The reaction mixture was then released from the solvent and unreacted starting material stripped what that desired product 5,5,7-trimethyl-H, 5,6,7-tetrahydrobenzothiazol-2-yl-isocyanate dimer as a brown crystalline solid.

Example 6

Preparation of the dimethyl acetal of 2- [[1-methyl 1-3- (5,5,7-trimethyl- ¹ *, 5,6,7-tetrahydrobenzothiazol-2-yl) -ureideq] acetaldehyde

7.5 g ojo ^

isocyanate dimer, 5 g of dimethyl acetal of 2-methylaminoacetaldehyde and 15 ml of toluene were placed in a glass reaction vessel with a mechanical stirrer and reflux condenser

- / 14

030037/0738

given. The reaction mixture was then stirred for about Heated for 1 h. The mixture was then cooled and filtered off. The filtrate was washed out with water, dried and evaporated, giving the desired product dimethylacetal of 2- [l-methyl-3- (5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl) -ureidoJ-acetaldehyde as a brown oil.

Example 7

Preparation of l- (5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one

8.5 g of dimethyl acetal des 2 [1-methyl-3- (5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl) -ureidoj-acetaldehyde, 25 ml of water, 25 ml of ethanol and 8.5 ml of concentrated hydrochloric acid were in a glass reaction vessel with mechanical Agitator, thermometer and reflux condenser are given. The reaction mixture was then refluxed for about 10 minutes heated. The reaction mixture was then stripped of solvents and gave the desired product 1- (5,5,7-Trimethyl-H, 5,6,7-tetrahydrobenzothiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one as a brown solid.

Example 8

Production of ethyl N- (5,7-dimethoxy- »f, 5,6,7-tetrahydrobenzothiazol-2-yl) carbamate

- / 15

030037/0730

0.10 mol of 2-amino-5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazole, dissolved in 125 ml of pyridine, are placed in a glass reaction container given with mechanical stirrer, thermometer and addition funnel. 0.12 mol of ethyl chloroformate then added dropwise to the reaction mixture with stirring and cooling. After the addition is complete, the reaction mixture is left warm to room temperature and stir for about 1 hour. Then the reaction mixture poured into ice water, where a precipitate forms. The precipitate is filtered off, dried and recrystallized and gives the desired product ethyl N- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate.

Example 9

Preparation of the dimethylacetal of 2- [l-ethyl-3- (5, 7-dimethoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) ureido] acetaldehyde

0.08 mol of ethyl N- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate and 30 ml of dimethylacetal of 2-ethylaminoacetaldehyde are placed in a glass reaction vessel with a stirrer, reflux condenser and gas duct given. The reaction mixture is blanketed with nitrogen gas and heated ^{at 125 ° C. for about 8 h.} The reaction mixture is then distilled to remove excess starting material. The residue is purified by elution chromatography using ethyl acetate as the eluant

030037/0736 _ _{/ l6}

cleaned. The chromatographed solution is then removed from the solvent stripped and gives the desired product dimethylacetal of 2- [1-ethyl-3- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) -ureidq] -acetaldehyde.

Example 10

Preparation of l- (5,7-dimethoxy-H, 5,6,7-tetrahydrobenzothiazol-2-yl) -3-ethyl-5-hydroxy-1,3-imidazolidin-2-one

0.05 mol of dimethyl acetal des 2- [1-ethyl-3- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazol-2-y1) -ureidq] acetaldehyde and 25 ml of dilute 3% hydrochloric acid placed in a glass reaction vessel with a mechanical stirrer and thermometer. The reaction mixture is heated for about 45 minutes at about 85 ^° C., which leads to the formation of a precipitate. The precipitate is then filtered off and dried and gives the desired product 1- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazol-2-y1) -3-ethy1-5-hydroxy-1,3-imidazolidine- 2-on.

Example 11

Production of ethyl N- (5-ethyl-7-chloro - «+, 5,6,7-tetrahydrobenzothiazol-2-y1) carbamate

0.10 mol of 2-amino-5-ethyl-7-chloro - ^, 5,6,7-tetrahydobenzothiazole, dissolved in 125 ml of pyridine, is placed in a glass reaction container with a mechanical stirrer, thermometer and

030037/0738

3OO7 & 58

Added funnel. 0.12 mol of ethyl chloroformate then added dropwise to the reaction mixture with stirring and cooling. After the addition is complete, the reaction mixture is left warm to room temperature and stir for about 1 hour. Then the reaction mixture poured into ice water so that a precipitate forms. The precipitate is filtered off, dried and recrystallized and gives the desired product ethyl N- (5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate.

Example 12

Preparation of the dimethyl acetal of 2- (JL-allyl-3- (5-ethyl-7-chloro-1,5,6 , 7-tetrahydrobenzothiazol-2-yl) -ureidcT) -acetaldehyde

0.08 mol of ethyl N- (5-ethyl-7-chloro-H, 5,6,7-tetrahydrobenzothiazol-2-yl) carbamate and 30 ml of dimethylacetal of 2-allylaminoacetaldehyde are placed in a glass reaction vessel with a stirrer and reflux condenser and gas supply pipe given. The reaction mixture is blanketed with nitrogen gas and heated ^{at 125 ° C. for about 8 h.} The reaction mixture is then distilled to remove excess starting material. The residue is purified by elution chromatography using ethyl acetate as the eluent. The chromatographed solution is then stripped from the solvent and gives the desired product dimethylacetal of 2- [l-allyl-3- (5-ethyl-7-chloro-

030037/0738 - / 18

30075S6

4,5,6,7-tetrahydrobenzothiazol-2-yl) ureido] acetaldehyde.

Example 13

Preparation of 1- (5-Ethy1-7-ChIOr-HjS, 6,7-tetrahydrobenzothiazol-2-yl) -3-allyl-5-hydroxy-1,3-imidazolidin-2-one

0.05 mol of dimethyl acetal des 2- [l-allyl-3- (5,5-diethy1-4,5, 6,7-tetrahydrobenzothiazol-2-yl) ureideq] acetaldehyde and 25 ml of dilute 3% hydrochloric acid placed in a glass reaction vessel with a mechanical stirrer and thermometer. The reaction mixture is heated for about 45 minutes at about 85 ^° C., which leads to the formation of a precipitate. Then the precipitate is filtered off and dried and gives the desired product 1- (5-Ethy1-7-chloro-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-allyl ~ 5-hydroxy-1,3 imidazolidin-2-one.

Example 14

Preparation of Ethyl N- (7-methylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate

0.10 mol of 2-amino-7-niethylthio-4,5,6,7-tetrahydrobenzothiazole, dissolved in 125 ml of pyridine, are placed in a glass reaction container given with mechanical stirrer, thermometer and addition funnel. 0.12 mol of ethyl chloroformate then added dropwise to the reaction mixture with stirring and cooling. After the addition is complete, the

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3P07556

The reaction mixture warms to room temperature and stirring is continued for about an hour. Then the Poured the reaction mixture into ice water so that a Precipitation forms. This is filtered off, dried and recrystallized and gives the desired product Ethyl N- (7-methylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate.

Example 15

Preparation of the dimethylacetal of 2- [l-ß-chloroethy1-3- (7-methylthio-'4,5,6,7-tetrahydrobenzothiazol-2-yl) -ureidcQ-acetaldehyde

0.08 mol of ethyl N- (7-methylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate and 30 ml of dimethyl acetal of 2-ß-chloroethylaminoacetaldehyde are placed in a glass reaction vessel with a stirrer, reflux condenser and gas supply tube given. The reaction mixture is blanketed with nitrogen gas and heated ^{at 125 ° C. for about 8 h.} The reaction mixture is then distilled to remove excess starting material. The residue is purified by elution chromatography using ethyl acetate as the eluent. The chromatographed solution is then stripped from the solvent and gives the desired product dimethyl acetal of 2- [l-ß-chloroethyl-3- (7-methylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) ureido] acetaldehyde .

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Example 16

Preparation of l- (7-methylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-ß-chloroethyl-5-hydroxy-1,3-imidazolidin-2-one

0. OS mol of dimethyl acetal of 2- [l-ß-chloroethyl-3- (7-methylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) ureido] acetaldehyde and 25 ml of dilute 3% hydrochloric acid placed in a glass reaction vessel with a mechanical stirrer and thermometer. The reaction mixture is heated for about 45 minutes at about 85 ^° C., which leads to the formation of a precipitate. The precipitate is then filtered off and dried and gives the desired product 1- (7-methylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-ß-chloroethyl-5-hydroxy-1,3-imidazolidine- 2-on.

Example 17

Production of ethyl N- (3-propyl-7-cyano-H, 5,6,7-tetrahydrobenzothiazol-2-yl) carbamate

0.10 mol 2-AmXnO-O-PrOPyI ^ -CyMO-H, 5,6,7-tetrahydrobenzothiazole, dissolved in 125 ml of pyridine, are placed in a glass reaction container with a mechanical stirrer, thermometer and Added funnel. 0.12 mol of ethyl chloroformate are then added dropwise to the reaction mixture with stirring and cooling. After the addition is complete, the reac is left tion mixture warm to room temperature, and it will

830037/0738

Stirred for about 1 hour. The reaction mixture is then poured into ice water, so that a precipitate forms forms. This is filtered off, dried and recrystallized and gives the desired product ethyl-N- (5-propyl-7 cyano - ^, 5,6,7-tetrahydrobenzothiazol-2-yl) carbamate.

Example 18

Preparation of the dimethylacetal of 2- [1-but-3-enyl-3- (5-propyl-7-cyaho-4,5,6,7-tetrahydrobenzothiazol-2-yl) -ureidoQ-acetaldehyde

0.08 mol of ethyl N- (5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate and 30 ml of dimethylacetal of 2-but-3-enylaminoacetaldehyde are in a glass reaction vessel with stirrer, reflux condenser and gas supply pipe. The reaction mixture is covered with a blanket of nitrogen gas and heated ^{at 12 5 ° C. for about 8 h.} The reaction mixture is then distilled to remove excess starting material. The residue is purified by elution chromatography using ethyl acetate as the eluent. The chromatographed solution is then stripped from the solvent and gives the desired product dimethylacetal des 2- [1-but-3-enyl-3- (5-propyl-7-cyano-U, 5,6,7-tetrahydrobenzothiazol-2-yl) ) -ureido3-acetaldehyde. '

- / 22

030037/0736

. 26 3Q07556

Example 19

Preparation of 1- (5-propyl-7-cyano-4,5 »6,7-tetrahydrobenzothiazol-2-yl) -3-but-3-enyl-5-hydroxy-1,3-imidazolidin-2-one

0.05 mol of dimethyl acetal des 2- [1-but-3-enyl-3- (5-propyl-7-cyano-U, 5,6,7-tetrahydrobenzothiazol-2-yl) ureideq] acetaldehyde and 25 ml dilute 3% hydrochloric acid are placed in a glass reaction vessel with a mechanical stirrer and thermometer. The reaction mixture is heated for about 45 minutes at about 85 ^° C., which leads to the formation of a precipitate. The precipitate is then filtered off and dried and gives the desired product 1- (5-Propy1-7-cyano-1,5,6,7-tetrahydrobenzothiazol-2-yl) -3-but-3-enyl-5-hydroxyl, 3-imidazolidin-2-one.

Example 20

Preparation of ethyl N- (5-hexyl-7-propoxy-H, 5,6,7-tetrahydrobenzothiazol-2-yl) carbamate

0.10 mol of 2-amino-5-hexyl-7-propoxy-H, 5,6,7-tetrahydrobenzo ~ thiazole, dissolved in 125 ml of pyridine, are in a glass reaction container with a mechanical stirrer, thermometer and Added funnel. 0.12 mol of ethyl chloroformate are then added dropwise to the reaction mixture with stirring and cooling given. When the addition is complete, the reaction mixture is allowed to warm to room temperature and it becomes Stirred for about 1 hour. Then the reaction

050037/0736

mixed poured into ice water, so that a precipitate forms forms. This is filtered off, dried and recrystallized and gives the desired product ethyl N- (5-hexyl-7-propoxy-H, 5,6,7-tetrahydrobenzothiazol-2-yl) carbamate.

Example 21

Preparation of the dimethylacetal of 2- [i-propyl-3- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) ureido] acetaldehyde

0.08 mol of ethyl N- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate and 30 ml of dimethyl acetal of 2-propylaminoacetaldehyde are placed in a glass reaction vessel with a stirrer and reflux condenser and gas supply pipe given. The reaction mixture is blanketed with nitrogen gas and heated ^{at 125 ° C. for about 8 h.} The reaction mixture is then distilled to remove excess starting material. The residue is purified by elution chromatography using ethyl acetate as the eluent. The chromatographed solution is then stripped from the solvent and gives the desired product dimethylacetal of 2- £ l-propyl-3- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) -ureidq] -acetaldehyde.

Example 22

Preparation of 1- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-propyl-5-hydroxy-1,3-imidazolidin-2-one

- / 2 4

030037/0736

0.05 mol of dimethyl acetal des 2-l-propyl-3- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) ureideq] acetaldehyde and 25 ml of dilute 3% strength Hydrochloric acid are placed in a glass reaction vessel with a mechanical stirrer and thermometer. The reaction mixture is ^{kept at about 85 °} C. for about 45 minutes, which leads to the formation of a precipitate. The precipitate is then filtered off and dried, giving the desired product 1- (5-hexyl-7-propoxy-U, 5,6,7-tetrahydrobenzothiazol-2-yl) -3-propyl-5-hydroxy-1,3- imidazolidin-2-one.

Example 23

Production of ethyl N- (5-ethylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate

0.10 mol of 2-amino-5-ethylthio-4,5,6,7-tetrahydrobenzothiazole, dissolved in 125 ml of pyridine, are placed in a glass reaction container with a mechanical stirrer, thermometer and addition funnel given. 0.12 mol of ethyl chloroformate are then added dropwise to the reaction mixture with stirring and cooling given. When the addition is complete, the reaction mixture is allowed to warm to room temperature and it takes about 1 hour further stirred. The reaction mixture is then poured into ice water, so that a precipitate forms. This is filtered off, dried and recrystallized and gives the desired product ethyl-N- (5-äthylthio-4,5,6,7-tetrahy-

- / 2 5

030037/073

drobenzothiazol-2-yD-carbamate.

Example 24

Preparation of the dimethylacetal of 2- {_l-bromomethyl-3- (5-ethylthio74,5,6,7-tetrahydrobenzothiazol-2-yl) -ureideq] acetaldehyde

0.08 mol of ethyl N- (äthylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) carbaniate and 30 ml of dimethylacetal of 2-bromomethylaminoacetaldehyde are placed in a glass reaction vessel with a stirrer, reflux condenser and gas supply pipe. The reaction mixture is blanketed with nitrogen gas and heated ^{at 125 ° C. for about 8 h.} The reaction mixture is then distilled to remove excess starting material. The residue is purified by elution chromatography using ethyl acetate as the eluent. The chromatographed solution is stripped from the solvent and gives the desired product dimethylacetal of 2- [l-bromomethyl-3- (5-ethylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) -ureidq] -acetaldehyde.

Example 25

Preparation of 1- (5-ethylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-bromomethyl-5-hydroxy-1,3-imidazolidin-2-one ·

0.05 mol of dimethyl acetal of 2- [i-bromomethyl-3- (5-ethylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) ureido] acetaldehyde

- / 2 6

030037 / 073e

and 25 ml of dilute 3% hydrochloric acid are placed in a glass reaction vessel with a mechanical stirrer and thermometer. The reaction mixture is heated for about 45 minutes at about 85 ^° C., which leads to the formation of a precipitate. This is then filtered off and dried and gives the desired product 1- (5-ethylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-bromomethyl-5-hydroxy-1,3-imidazolidin-2-one .

Example 26

Preparation of Ethyl N- (4,5,6,7-tetrahydrobenzothiazol-2-yl) carbamate

0.10 mol of 2-amino-4,5,6,7-tetrahydrobenzothiazole, dissolved in 12 5 ml of pyridine are placed in a glass reaction container with a mechanical stirrer, thermometer and addition funnel given. 0.12 mol of ethyl chloroformate are then added dropwise added to the reaction mixture with stirring and cooling. After the addition is complete, the reaction mixture is allowed to stand warm to room temperature and stir for about 1 hour. The reaction mixture is then poured into ice water poured so that a precipitate forms. The precipitate is filtered off, dried and recrystallized and gives the desired product ethyl N- (4,5,6,7-tetrahydrobenzothiazol-2-yl) -earbamate.

- / 27

030037/0731

Example 27

Preparation of the dimethylacetals of 2- [l-methy 1-3-0,5,6,7-tetrahydrobenzothiazol-2-yl) -ureidcT] -acetaldehyde

0.08 mol of ethyl N- (U, 5,6,7-tetrahydrobenzothiazol-2-yl) carbamate and 30 ml of dimethyl acetal of 2-methylaminoacetaldehyde are placed in a glass reaction vessel with a stirrer, reflux condenser and gas supply pipe. The reaction mixture is covered with nitrogen gas and heated at 125 C for about 8 h. The reaction mixture is then distilled to remove excess starting material. The residue is purified by means of elution chromatography purified using ethyl acetate as the eluant. The chromatographed solution is then removed from the solvent stripped and gives the desired product dimethylacetal of 2-jjL-methyl-3- (4,5,6,7-tetrahydrobenzothiazol-2-yl) -ureido3 -acetaldehyde.

Example 28

Preparation of 1- (4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one

0.05 mol of dimethyl acetal des 2- [1-methyl-3- (4,5,6,7-tetrahydrobenzothiazol-2-yl) ureido]] acetaldehyde and 25 ml of dilute 3% hydrochloric acid are placed in a glass reaction vessel given with mechanical stirrer and thermometer.

- / 28

030037/0736

-ir-11

The reaction mixture is ^{heated at 85 °} C. for about 45 minutes, which leads to the formation of a precipitate. The precipitate is then filtered off and dried to give the desired product l- (4,5,6, 7-tetrahydrobenzothiazole-2-yD-3-methyl-5-hydroxy-l _t 3-imidazolidin-2-on.

Further compounds according to the invention which are prepared using the processes described in the examples above can are:

1- (5-propylthio-4,5,6,7-tetrahydrothiazol-2-yl) -3-6-iodobutyl-5-hydroxy-1,3-imidazolidin-2-one, l- (5-Butylthio-4,5,6,7-tetrahydrothiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one, 1- (7-pentylthio-4,5,6,7-tetrahydrothiazol-2-yl) -3-butyl-5-hydroxy-1,3-imidazolidin-2-one, 1- (7-Hexylthio-4,5,6,7-tetrahydrothiazol-2-yl) -3-pentyl-5-hydroxy-1,3-imidazolidin-2-one, 1- (5,7-diethoxy-4,5,6,7-tetrahydrothiazol-2-yl) -3-hexyl-5-hydroxy-1,3-imidazolidin-2-one, 1- (5-Butoxy-4,5,6,7-tetrahydrothiazol-2-yl) -3-pent-4-enyl-5-hydroxy-l , 3-imidazolidin-2-one, 1- (7-hexyloxy-4,5,6,7-tetrahydrothiazol-2-yl) -3-hex-3-enyl-5-hydroxy-1,3-imidazolidin-2 -on, 1- (5,7-Dibutyl-4,5,6,7-tetrahydrothiazol-2-yl) -3-ß-fluoroethyl-5-hydroxy-1,3-imidazolidin-2-one, l- (5,5,7-triethyl-4,5,6,7-tetrahydrothiazol-2-yl) -3-6-chlorhexyl-5-hydroxy-1,3-imidazolidin-2-one, 1- (5,5,7-Trimethyl-7-cyano-4,5,6,7-tetrahydrothiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one, 1- (5-cyano-5,7-dimethyl-4,5,6,7-tetrahydrothiazole-2-

- / 29

630037/0730

- & ύ ^ WW / 556

yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one, 1- (5-dimethylamino-4,5,6,7-tetrahydrothiazol-2-yl) -3-methyl-5-hydroxy - 1,3-imidazolidin-2-one, 1- (5-diethylamino-4,5,6,7-tetrahydrothiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one, 1- (7-Dibutylamino-4,5,6,7-tetrahydrothiazol-2-yl) -3-propargyl-5-hydroxy-1,3-imidazolidin-2-one, l- (5,5,7-trimethyl-4,5, 6,7-tetrahydrothiazol-2-yl) -3-propargyl-5-hydroxy-1,3-imidazolidin-2-one, 1- (5-Bromo-4,5,6,7-tetrahydrothiazol-2-yl) -3-propargyl-5-hydroxy-1,3-imidazolidin-2-one.

For practical use as herbicides are those according to the invention Compounds generally included in herbicide preparations, which are an inert carrier and contain a herbicidally toxic amount of such a compound. In such herbicidal preparations or formulations the active ingredient can be conveniently applied to the weed infestation site in any desired amount. The preparations can Solids such as dusts, granules or wettable powders, or liquids such as solutions, aerosols or emulsifiable Be concentrates.

Dust can be generated, for example, by grinding and mixing the active ingredient with a solid inert carrier such as talc, clay, silica, pyrophyllite and the like. Granulate preparations are prepared by the compound usually dissolved in a suitable solvent on or in impregnated granular carriers, such as attapulgites or

830037/0736 - / 3o

3OO7 55 & '34

Vermiculite with a particle size of usually about 0 »3 to 1.5 µm. Wettable powders that are in water or oil Can be dispersed up to any desired concentration of active ingredient, you can by the inclusion of wetting agents in concentrated dust preparations.

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. Often herbicide solutions can be sprayed under overpressure as aerosols. However, preferred liquid herbicide preparations are emulsifiable concentrates, which contain an active ingredient according to the invention and, as an inert carrier, a solvent or an emulsifying agent. Such emulsifiable concentrates can be diluted with water and / or oil to any desired active ingredient concentration and used as a spray at the weed site. As an emulsifier in such concentrates am most often nonionic or mixtures of nonionic and anionic surfactants are used. With some emulsifying systems an inverted emulsion (water in oil) can be made for direct application to the weed.

A typical herbicidal preparation according to the invention is described in the following example. The stated amounts are parts by weight.

- / 3i

030037/0736

Example 29

Making a dust

Product according to given example 10 talc powder 90

The above ingredients are mixed in a mechanical mill-mixer ground until a homogeneous, free-flowing dust of the desired particle size is produced. This dust can be applied directly to the location of the weed infestation.

The compounds according to the invention can be in any recognized Way to be used as herbicides. One method of weed control is that at the location of the weed infestation a herbicidal formulation is applied which comprises an inert carrier and, as an essential active ingredient, one according to the invention Contains compound in a herbicidally toxic amount for these weeds. The concentration of the new invention Compounds in the herbicide preparations vary largely depending on the type of preparation and intended use, In general, however, the herbicide preparations contain about 0.05 to 95% by weight of the active ingredient according to the invention. In a preferred embodiment of the invention contain the Herbicidal preparations about 5 to 75% by weight of active ingredient. The preparations can also contain additional substances, e.g. other pesticides such as insecticides, nematocides, fungi

- / 32

030037/0736

- I *, 3ÖD7bbb

cides and the like. \ Stabilizers, distributing agents, deactivators, adhesives, tackifiers, fertilizers, activators, synergists and the like.

The compounds of the invention are also useful when they in the mentioned herbicide preparations with other herbicides and / or defoliants, desiccants, Growth inhibitors and the like. Be combined. These other substances can make up about 5 to 95% of the active ingredients in the herbicide preparations turn off. Combinations of these other herbicides and / or defoliants, desiccants, etc. with the compounds according to the invention result in herbicide preparations, which are more effective for weed control and often give results that with separate formulations of the individual herbicides cannot be achieved. Herbicides, defoliants, and desiccants Growth inhibitors with which the compounds according to the invention for weed control in herbicide preparations can be used include:

Chlorophenoxy herbicides such as 2, U-D, 2, H, 5-T, MCPA, MCPB, 4 (2, H-DB), 2, U-DEB, H-CPB, U-CPA, U-CPP, 2, U, 5-TB, 2, U, 5-TES, 3, U-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, dialate, PEBC, perbulate, vernolate, and the like; substituted

- / 33

030037/0736

Urea herbicides such as norea, siduron, dichloralurea, Chloroxuron, Cycluron, Fenuron, Monuron, Monuron TCA, Diuron, Linuron, Monolinuron, Neburon, Buturon, Trimeturon and the like. »Synunetric triazine herbicides such as simazine, chlorazine, Atraon, Desmetryn, Norazin, Ipazin, Prometryn, Atrazine, Trietazine, Simeton, Prometon, Propazine, Ametryn and like; Chloroacetamide herbicides such as a-chloro-N, N-dimethylacetamide, CDEA, CDAA, ct-chloro-N-isopropylacetamide, 2-chloro-N-isopropylacetanilide, ^ - (ChloracetyD-morpholine, l- (chloroacetyl) -piperidine and the like; chlorinated aliphatic acid herbicides such as TCA, Dalapon, 2,3-dichloropropionic acid, 2,2,3-TPA and the like; chlorinated benzenic acid and phenylacetic 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, H-dichloro-3-nitrobenzenic acid and the like; as well as compounds such as aminotriazole, maleic acid hydrazide, Phenyl-Mercury-II-Acetate, Endothal, Biuret, technical chlordane, dimethyl-2,3,5,6-tetrachloroterephthalate, Diquat, Erbon, DNC, DNBP, Dichlobenil, DPA, Diphenamid, Dipropalin, Trifluralin, Solan, Dicryl, Merphos, DMPA, DSMA, MSMA, potassium azide, acrolein, benefin, bensulide, AMS, bromacil, 2- (3,4-dichlorophenyD-4-methy 1-1,2, U-oxadiazolidine-3,5-dione, Bromoxynil, Cacodylic Acid, CMA, CPMF, Cypromid, DCB, DCPA, Dichlone, Diphenatril, DMTT, DNAP, EBEP, EXD, HCA, Ioxynil, IPX, Isocil, Potassium Cyanate, MAA, MAMA, MCPES, MCPP,

- / 3

030037/0? 3β

MH, Molinat, NPA, OCH, Paraquat, PCP, Picloram, DPA, PCA, Pyrichlor, Seson, Terbacil, Terbutol, TCBA, Brominil, CP-501im, H-176-1, H-732, M-2901, Planavin, sodium tetraborate, Calcium cyanamide, DEF, ethyl xanthogen disulfide, Sindon, Sindon B, propanil and the like.

These herbicides can also be used in the processes and preparations according to the invention in the form of their salts, esters, amides and other derivatives are used insofar as these can be produced from the respective basic products.

Weeds are unusable plants in undesirable places, with no economic value, which the production of crops, disrupt the growth of ornamental plants and the welfare of livestock. Many types of weeds are known e.g. annual plants such as chenopodium, foxtail, brine, wild mustard, pennywort, ryegrass, bedstraw, chickweed, wild oats, Malvaceae, purslane, barnyard grass, persicaria, knotweed, burdock, wild buckwheat, kochia, Medicago, corn wheel, Ambrosiaceae, Sonchus, coffee herb, croton, cuphea, hop silk, earth smoke, ragwort, hollow tooth, Spurge, Sparrow, Emex, Panicum colonum, Laichkraut, Anthemis cotuta, Mollugo verticillata, bindweed, duckweed; biennial plants such as wild carrot, matricaria, wild barley, Light carnation, chamomile, burdock, mullein, round-leaved mallow, Cirsium lanceolatum, dog's tongue, Verbascum Blattaria

- / 35

630037/0736

- Y5 - \ (

and purple thistle furthermore perennial plants such as white wheels, perennial rye grass, couch grass, sorghum halepense, thistle, Hedgehog, Cynodon dactylon, Rumex acetosella, dock, chickweed, dandelion, bellflower, field winch, Russian knotweed, Prosopis juliflora, toadflax, yarrow, Aster, Ackersteinsame, Horsetail, Vernonia, Sesbania, large bulrush, bulrush and winter cress.

These weeds can also be divided into broad-leaved or grassy weeds. It's from economic Desirable reasons to control weed growth without harming crops or livestock.

The new compounds of the invention are particularly valuable for weed control because they are toxic to many species and groups of weeds, but are relatively non-toxic to many crops. The exact required amount of the compound will depend on a variety of factors, such as the strength of the respective weed species, weather, soil type, application method, the type of crops in the same area, etc. While for example the use of only _up. 30 to 60 g of active ingredient per 0.4 ha can be sufficient to control light weed infestation under unfavorable growth conditions tenacious perennial weeds that grow under favorable conditions.

»« 0037/0731 ~ ^{/ U}

The herbicidal toxicity of the new compounds according to the invention can be proven with many of the proven test procedures, e.g. with pre- and post-emergence tests.

The herbicidal activity of the compounds according to the invention was demonstrated with tests relating to the pre-emergence control a number of weeds were carried out. In small greenhouse plastic pots with dry earth were placed sown the various weed seeds. 2t hours or less after sowing, the pots were sprayed with water until the soil was wet and the test compounds in shape of aqueous emulsions of acetone solutions, the emulsifying agents were sprayed onto the surface of the earth in the specified concentrations.

The containers were then placed in the greenhouse and, as required, with additional warmth and daily or more frequently Provide irrigation. The plants were kept under these conditions for 15 to 21 days; at that point it was the condition of the plants and the degree of damage are rated on a scale from 0 to 10 as follows:

0 = no damage, 1.2 = slight damage, 3.4 = moderate damage, 5.6 = moderately severe damage, 7,8,9 = severe damage Damage, 10 = total loss. The effectiveness of these compounds is shown with the data compiled in Tables I and II. Numbers with decimal places are the through

- / 3 7

030037/0736

- X -

average score of two or more reviews from repeat try.

The herbicidal activity of the compounds according to the invention has also been demonstrated by tests) with respect to the Post-emergence controls of a number of weeds were carried out. For these experiments the compounds to be tested were Prepared as aqueous emulsions and in the specified dosage on the leaves of the various weed species sprayed that had reached a set size. Then the plants were brought into the greenhouse and watered daily or more frequently. No water was placed on the leaves of the treated plants. The severity of the damage was found 10 to 15 days after treatment and scored according to an index of 0 to 10 as described above. The effectiveness of these compounds can be seen from the data summarized in Tables III and IV. values with decimal places are again average values from repeated attempts.

&& 0037 / Q73 · " ^{/ 38}

Table I - Product according to Example 4 Pre-emergence test: evaluation of the damage

concentration 2.2 - kg / ha 0.56 0.28 0.14 Weed species 9.0 0 1.1 - - - Yellow sedge 5 10 0.0 5.0 2.5 1.0 Wild oats 10 10 6.7 - 4.0 5.0 Thorn apple 10 10 10.0 8.5 10.0 8.5 Malvaceae 10 10 9.0 6.5 2.5 2.0 Sorghum halepense 9 9 7.7 3.5 1.5 1.0 Goosefoot 9 10 7.0 10.0 10.0 4.0 Wild mustard 10 8th 10.0 5.5 2.0 1.5 Yellow foxtail 10 10 7.0 10.0 7.0 0.0 Barnyard grass 10 8th 9.3 7.0 3.0 1.5 Brine 9 9 8.0 5.0 3.5 0.5 Wrong grain 10 10 7.0 7.0 4.0 4.5 Winch 8th - 8.3 5.0 3.0 1.5 Knotweed - - 10.0 4.5 4.0 2.5 Couch grass - - 5.5 9.0 4.5 3.5 Sprangeltop - - 10.0 6.5 3.0 2.5 Beans - - 9.5 8.5 8.0 9.5 Sugar beet - - 9.0 8.0 7.5 2.5 wheat - - 9.5 3.5 3.0 2.0 rice - - • +, 0 1.0 1.0 1.0 Soybeans - - 6.5 5.0 2.5 0.5 cotton - - 10.0 10.0 5.0 4.5 Sorghum - - 10.0 5.5 3.0 0.5 Corn - - 7.0 3.5 2.0 1.0 alfalfa - - 10.0 2.5 2.0 1.0 oats - 6.5

»30037/0731

- / 39

Table II - Product according to Example 7 Pre-emergence test: evaluation of the damage

concentration 1.1 - kg / ha 0, , 28 O, , 14 Weed species 2.2 0.0 0.56 1, Yellow sedge 3.0 9.3 0.0 0, "O 1, , 0 Wild oats 10.0 4.0 2.7 4, , 0 O, , 0 Thorn apple 10.0 10.0 2.5 5, , 5 O, 0 Malvaceae 10.0 6.5 8.5 O. , 0 0, 0 Sorghum
halepense 10.0 6.0 3.2 O, , 0 0, 0 Goosefoot
growths 10.0 9.0 3.5 1, , 0 1, 5 Wild mustard 10.0 6.7 10.0 O, , 5 2, 5 Yellow fox
tail 9.0 5.7 2.2 2, , 0 O, 0 Barnyard grass 10.0 4.5 5.2 1, , 5 1, 0 Brine 6.0 6.7 1.7 O, 5 0, 0 Wrong Ge
grain 10.0 7.6 1.7 5, 0 - 5 Winches 10.0 10.0 8.4 3, 0 O, 0 Knotweed - 2.0 5.5 O, 0 O, Burdock 7.0 10.0 1.0 2, 5 O, 0 Couch grass - 5.0 6.0 O, 0 6, 0 Sprangletop - 6.0 2.5 O, 0 1, 0 Beans - 10.0 3.0 8th, 0 O, 0 Sugar beet - 9.5 10.0 1, 5 1, 0 wheat - 4.0 5.5 3, 5 O, 0 rice - 3.7 2.5 O, 3 1, 0 Soybeans 6.0 1.7 0.7 O, 0 O, 0 cotton 2.0 10.0 0.0 2, 0 O, 0 Sorghum - 3.0 4.0 O, 0 O, 0 Corn - 5.0 0.5 O, 0 0 alfalfa - 4.0 0.0 O, 0 0 oats - 0.0

030037/0736

- / Ho

- fa

Table III - Product according to Example 4 Post-emergence test: evaluation of the damage

3OÜ75b6

Weed species

Concentration - kg / ha 0.56

0.28

Wild mustard 10.0 10.0 10.0 10.0 10.0 Wild oats 10.0 3.5 4.0 2.0 1.0 Winches 10.0 10.0 10.0 10.0 3.0 Barnyard grass 10.0 10.0 10.0 10.0 5.0 Brine 9.0 9.5 9.5 10.0 10.0 Yellow one
Foxtail 9.0 10.0 10.0 6.0 4.0 Sorghum
halepense 10.0 9.5 8.0 3.0 2.0 Winches
(Morningglory; 10.0
> 10.0 10.0 10.0 10.0 Thorn apple 10.0 10.0 10.0 10.0 5.0 Yellow reed
grass 5.0 2.0 2.0 - - Goosefoot
grows 10.0 10.0 10.0 10.0 10.0 Malvaceae - 10.0 10.0 10.0 10.0 Couch grass - 10.0 6.0 4.0 2.0 Sprangletop - 10.0 10.0 4.0 3.0 Wrong Ge
grain - 10.0 10.0 2.0 2.0 Beans - 10.0 10.0 10.0 10.0 Sorghum - 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 cotton - 10.0 10.0 10.0 10.0 Corn - 7.0 10.0 4.0 3.0 alfalfa - 10.0 10.0 10.0 10.0 oats - 2.0 2.0 0.0 0.0 Soybeans - 10.0 10.0 10, Ο 10.0 Sugar beet - 10.0 10.0 ΙΟ, 0 10.0

130037/0736

- / 4 1

Table IV - Product of Example 7 Post-emergence Test: Damage Rating Concentration - kg / ha

Weed species
Wild mustard
Wild oats
Winches
Barnyard grass
Brine

Yellow foxtail

Sorghum
halepense

Winches

(Mornxngglory) thorn apple

Yellow sedge

Goosefoot

Malvaceae

Couch grass

Sprangletop

Wrong
grain

Beans

Sorghum

wheat

cotton

alfalfa

oats

Soybeans

Sugar beet

2.2

10.0 10.0 10.0 10.0 10.0

10.0

10.0

1.1 10.0

5.0 10.0 10.0

8.7

5.7

0.56 10.0 2.0 9.0 7.2 6.2

5.7

10.0 8.0 6.0 0.28
10.0
0.0
5.5
6.0

2.5

5.5

0.13
6.5
0.0
1.0
3.5
2.0

1.0
3.5

0.070

2.0

0.0

0.0

2.0

0.0

0.0 5.0

10, 0 10 , 0 10, 0 6, 5 10, 0 5, 0 10, 0 9 , 3 9, 2 8th, 5 8th, 5 10, 0 2, 0 0 , 5 O, 0 - - -

10.0

8.3 7.5 6.0 4.0 3.0 10.0 10.0 10.0 8.5 7.0 10.0 10.0 7.0 2.0 2.0 10.0 6.0 5.5 1.0 0.0 10.0 5.0 5.0 0.0 0.0 5.0 10.0 7.0 7.0 3.0 10.0 5.0 1.0 1.0 0.0 2.0 1.5 1.0 0.0 0.0 7.0 5.5 10.0 0.5 0.0 10.0 10.0 8.5 7.5 10.0 ■ 4.0 3.0 0.5 0.5 0.0 10.0 10.0 9.5 9.5 4.0 2.0 0.5 1.0 0.5 0.0 10.0 7.0 *, 5 3.5 3.0 10.0 10.0 8.5 6.5 2.0

190037/0736

Claims (10)

DR. BERG DIPI -ING. STAPF DIPL.-ING. SCHWABE DR. DK. S aNDMATR Postfach 860245-8000 München 86 Attorney's files: 30,712 patent claims 1. Compound of formula OH characterized in that X is selected from alkyl, alkoxy, alkylthio, halogen, dialkylamino or cyano is selected, η is an integer from 0 to 4, and R is selected from alkyl, alkenyl or haloalkyl. 2. A compound according to claim 1, characterized in that it l- (5,5,7-Trimethy1-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-methyl-5-hydroxy-l, 3- imidazolidin-2-one is. 3. A compound according to claim 1, characterized in that it l- (5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imida- zolidin-2-one is. ? 3Ö r (019) 988272 Telegrams: Bank accounts: Hypo-Birk Munich 4410122850 988273 BERQSTAPFPATENT Munich (BLZ 7OO2OOII) Swif Code: HYPO DE MM 981274 TELEX: Bayet Vereintbtnlc Munich 453100 (BLZ 70020270) 983310 0524560BERGd PMItcheck Munich 65343-808 (BLZ 70010080) . ₂ . 3üü7bb6 4. A compound according to claim 1, characterized in that it l- (5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-ethyl-5-hydroxy-1,3-imidazolidine 2-on is. 5. A compound according to claim 1, characterized in that it l- (5,5,7-trimethyl-7-cyano-4,5,6, 7-tetrahydrobenzothiazol-2-yl) -3-methyl-5-hydroxy-1,3-imidazolidin-2-one is. 6. A compound according to claim 1, characterized in that it l- (5-cyano-5,7-dimethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-methyl-5-hydroxy-l, 3-imidazolidin-2-one is. 7. A compound according to claim 1, characterized in that that they are 1- (5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-but-3-enyl-5-hydroxy-1,3-imidazolidin-2-one is. 8. A compound according to claim 1, characterized in that it l- (5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl) -3-propyl-5-hydroxy-l, 3- imidazolidin-2-one is. 9. Herbicide preparation, characterized that they are an inert carrier and, - / 3 030037/073 « contains as an essential active ingredient a compound according to claim 1 in an amount toxic to weeds. 10. Method of controlling weeds, thereby marked that the weed with a Herbicidal preparation is brought into contact, which is an inert carrier and, as an essential active ingredient, contains a compound of claim 1 in an amount toxic to weeds. -M 030037/073