DE2434922A1 - ISOTHIAZOLYL URUBE, METHOD FOR THEIR MANUFACTURING AND USE AS HERBICIDES - Google Patents

Description

DIPL.-CHEM. DR. VOLKER VOSSIUS

PATENT ADVOCATE

MONKS 86, SIEBERTSTRASSE 4 PHONE: 47 4075

CABLE ADDRESS: BENZOL PATENT MÖNCHEN TELEX 5-29453 VOPAT D

? 9- JuH Wh

2434912

U ₉ Zs K 909 (Vo / ko) Case: 4257 FMC Corporation New York, N ₀ Y ₀ (V ₀ St.A.)

¹¹ Isothiazolylureas ₉ Process for their preparation and their use as herbicides "

_ 1 ' ι ι, 1 _{TM | L} .— with— ■

Priority? July 19, 1973, V ₀ St.A ₀ , No. 380 893 June 10, 1974, V ₀ St ₈ A ₀ , No. 477 778

The invention relates to that characterized in the claims Object,

Embodiments (a) and (b) of the process according to the invention are represented by the following reaction scheme

U "Ά

JR-I ι, .ι A

ben:

Ri

-NH ₂

H 0

S. I. R2-N = C = O κι I. i * - ι ι *
• s I! H-NR ₂ R ₃ [J- S. - ^ NCNR ₂ 5 / Ί4 33 Ii I II
HIGH ! I
/ \ NCN
I Il 40988 I Il
HO

The 4-carbamoyl compounds of the general formula I can by acid hydrolysis of the corresponding 4-cyano compounds of the general formula IV.

The aminoisothiazoles used according to the process can be prepared according to the following reaction scheme:

H ₂ C- (CN) ₂ OH Cl

I '"■ I

"* ■ - * R ₁ -C = C- (CN) ₂ - * Ri-C = C- (CN) ₂ ⁰ I

(Ri-C) ₂ O NH ₂ S NH ₂ ,

■ I Il I

• ■ Ri-C = CC-NH ₂ ^ -Ri-C = C- (CN) ₂

CN

FT

The preparation of their intermediates is explained below.

2-cyano-3-hydroxy-4-methyl- 2-pentene-nitrile

A mixture of 132.1 g of malonic acid "" ⁴ ^ nitrile and 3 ^ 5 »6 g

Liters
Potassium carbonate in methylene chloride is mixed with 316 kg of isobutyric anhydride over the course of 2 hours, and the mixture warms up to the reflux temperature during the addition. After the addition has ended, the reaction mixture becomes more

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Heated under reflux for 6 1/2 hours. After that, the re-

Action mixture stirred for 15 hours at room temperature and then cooled to -10 ° C. The cold mixture will

liter

1 / concentrated hydrochloric acid is carefully added at a temperature below 10 C. The acidic mixture is filtered and the layers are separated. The aqueous phase is extracted twice, each time with 300 ml of methylene chloride. The combined methyl chloride extracts are washed with saturated sodium chloride solution, dried, filtered and evaporated. The solid residue is washed with pentane and dried. Yield 195.5 g of the title compound “* with a melting point of 9k to 96 ° C. When the filtrate and the washing solutions are evaporated, a further 37 g of the compound with a melting point of 87 to 90 ° C. are obtained.

The 2-cyano-3-hydroxy-2-hexen-nitrile is produced in a similar way Boils 100 ° C / 9 Torr. Furthermore, in the manner described above, the 2-C3> -an-3-hydroxy-4,4-dimethyl-2-pentenenitrile manufactured from m.p. 15 to 162 ° C.

3-chloro-2-cyano-4,4-dimethyl-2-pentene-nitrile

A solution of 69.6 g of 2-cyano-3-hydroxy-4,4-dimethyl-2-pentene-nitrile in 6OO. ml of methylene chloride is mixed with 104.1 g of phosphorus pentachloride in small portions. The mixture is stirred for 22 hours at room temperature. Sulfur dioxide is then passed through the mixture for 20 minutes

^L A09885 / U33

and the mixture was stirred for an additional hour. After that -will
evaporated the mixture and poured the concentrate into 500 ml of crushed ice. After stirring for one hour, the
cold mixture filtered, the filter residue washed with cold water and dried for 60 hours at room temperature under reduced pressure. Yield 68.8 g of the title compound with a melting point of 52 to 53 ° C.

In a similar way, the 3-chloro-2-cyano-2-hexen-nitrile, Bp. 73 ° C / 1.2 Torr, and the 3-chloro-2-cyano-4-methyi-2-pentenenitrile, B.p. 52 to 58 ° C / 0.3 torr.

3-Amino-2-cyano-1- methyl-2-pentene-nitrile

A solution of 191 »3 g of 3-chloro-2-cyano-4-methyl-2-pentenenitrile in 300 ml of ethanol is mixed within 75 minutes at a temperature below hO ° C with a mixture of 800 ml of concentrated aqueous ammonia solution and 1000 ml of ethanol offset. The mixture is stirred for 3 hours and then poured into 2 liters of crushed ice. The resulting solid is filtered off, washed with water and dried, yield
122.0 g of the title compound with a melting point of 186 to 188 ° C,

In the same way, the 3-amino-2-cyano-2-hexen-nitrile
from 133 to 135 ° C and the 3-amino-2-cyano-4,4-dimethyl-2-penten-nitx> ll from 163 to 164 ° C.

^L '409885 / U33

3-amino-2-cyano-2-pentene-nitrile

A mixture of 352.5 g of triethyl orthoester and propionate 122.1 .g Malonsäuredrini tril is 22 hours under reflux heated. Then the mixture is dissolved in 200 ml of ethanol, and 85 g of gaseous ammonia are introduced at a temperature of the solution below 50.degree. The ammoniacal mixture is stirred for 1 hour at room temperature, then evaporated and the residue from a mixture of ethanol and Recrystallized water. Yield 222.1 g of the title compound from 152 to 155 ° C.

3-Amino-2-cyano-4-methyl-2-pentene-thioamide

Hydrogen sulfide gas is passed into a solution of 122.0 g of 3-amino-2-cyano-4-methyl-2-pentenenitrile and 91.5 g of triethylamine in 122 ml of pyridine at a temperature below k5 C for two hours with stirring. Then the mixture is stirred for 1 hour at room temperature and hiera ^^ f in

liter
2 / Poured crushed ice. The resulting solid is filtered off, washed with barrels, dried and recrystallized from a mixture of ethanol and water. Exhausted 128.3 g of the title compound with a melting point of 112 to 114 ° C.

In a similar way, the 3-amino-2-cyano-4, k- dimethyl-2-pentene-thioamide with a melting point of 129 to 131 ° C., the 3-AmInO ^ -cyan-2-pentene-thioamide with a melting point of 152 up to 155 ° C and the 3-amino-2-cyano-2-hexen-thioamide with a melting point of 133 to 135 ° C.

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5-amino-3-isopropylisothiazole-4-earbonitrile

A solution of 128.3 g of 3-amino-2-cyano-4-methyl-2-pententhioamide in 600 ml of anhydrous ethanol is added dropwise with 86.1 g of 30 percent hydrogen peroxide solution at a temperature below 50 ° C. while stirring. The mixture is then stirred at room temperature for 19 hours, filtered and evaporated to about half its volume. Water is added to the residue until it becomes cloudy and the mixture is left to stand. The resulting crystals are filtered off and dried. Yield 123.0 g of the title compound from. P-. 133 to 135 ^q C.

The following connections are made in a similar manner: 5-Amino-3-ethylisothiazole - ^ - carbonitrile, mp 148 to 150 ° C; 5-Amino-3-propyl-isothiazole- ^ f-carbonitrile, F, 85 to 88 C and S-Amino-O-tert-butylisothiazole- ^ carbonitrile, mp 133-13 ° C

(4 * cyano-3-isopropyl-5-isothiazolyl) "phenyl carbate

A mixture of 33.2 g of 5-amino-3-propylisothiazole-4-carbonitrile and 70.6 g of phenyl chloroformate in 150 ml Toluene is heated on a steam bath for 90 minutes after hydrogen chloride gas has been bubbled into the toluene solution for 5 minutes.

liter

was tet. The hot mixture is poured onto 1 / crushed ice and filtered. The filtrate is extracted twice with 300 ml of chloroform each time. The chloroform extracts are evaporated in vacuo and the residue becomes

A09885 / U33

_ ₇

combined with the originally filtered solid. After recrystallization from ethanol, 45.1 g of the title compound are obtained obtained from m.p. 187 to 191 ° C.

The following compounds are prepared in a similar manner: (4-cyano-3-propyl-5-isοthiazolyl) -carbamic acid phenyl ester, M.p. 193 to 194 ° C;

(4-cyano-3-ethyl-5-isothiazolyl) -carbamic acid phenyl ester, F. 217 to 218 ⁰ C and '

(4-cyano-3-tert-butyl-5-isothiazolyl) -carbamic acid phenyl- ester, m.p. 13CK to 131 ° C.

(4-Cyano-3-methyl ~ 5-isothiazolyl) -carbamic acid phenyl ester

A 0 C cold solution of 15 ^, 2 g of phenoxycarbonyl isothiocyanate is added dropwise at a temperature below 5 C. a solution of 66.8 g of 3-aminocrotononitrile in 3OO ml of acetonitrile is added. After that, the mixture is 1 hour stirred at room temperature and then poured into 3 / water. The resulting yellow solid is filtered off, washed with water, dried and dissolved in 300 ml of ethanol. The ethanol solution is cooled in an ice bath and added dropwise while cooling with 93.0 g of 30 percent hydrogen peroxide solution offset. The mixture is then warmed to room temperature within 15 1/2 hours, calmly. The yellow colored mixture is then refluxed for 1 hour, then cooled to room temperature and the resulting solid is filtered off and dried

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net; M.p. 216 to 219 ° C. The solid is 17 hours in A Soxhlet-Tbctm ktor extracted with hot ethanol. Of the The extract is cooled and the title compound which has crystallized out is filtered off. Yield 6o.6 g of mp 232 to 235 ° C.

The ethanol extract is evaporated and the residue again placed in the extraction thimble and extracted for 17 hours. There will be a further 10 g of the Ti te! Connection from M.p. 23O to 232 ° C.

The examples illustrate the preparation of the inventive Links.

example 1

1 - (4-ethoxy carbonyl --3-methyl ~ 5-is ο thiazolyl) -3-isopropylurea

A mixture of 8.9 g (Ji-Ä

thiazolyl) ~ carbamic acid ph.enyl ester (prepared according to • Goerdeler and Horn, Chem. Ber., Vol. 96 (1963), p. 155 ¹ ) 18.0 g of isopi-opylamine in 100 ml of dimethylformamide is 90 minutes in a 200 ml pressure-resistant vessel heated to 40 ° C. The mixture is then cooled in an ice bath, the vessel opened and the contents poured into 300 ml of water. The resulting solid is filtered off, washed with water and dried. Yield 6.1 g of the title compound with a melting point of 172 to 175 ° C. After crystallization from aqueous acetic acid, the compound melts at 173 bis

L - »

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Γ Π

175 ° C.

Example 2 T- (4-cyano-3-methyl-5-isothiazolyl) -3,3-dinethy! Urea

10 g (^ -Cyan-3-methyl-5-isothiazolyl) -carbamic acid phenyl ester are introduced into a saturated solution of dimethylamine in 100 ml of dimethylformamide. The mixture is heated and stirred for 90 minutes at kO C in a pressure-resistant vessel. The mixture is then cooled, the vessel opened and the contents poured into 300 ml barrels. The aqueous mixture is acidified with 10 percent hydrochloric acid, and the resulting solid is filtered off, washed with water and dried. M.p. 209 to 215 ° C. Based on the NMR spectrum, the solid consists of a mixture of about 2 parts of the title compound and about 1 part of the starting compound. A mixture of 3.9 g of the solid and 5.0 g of (4-cyano-3-inethyl-5-isothiazolyl) -carbamic acid phenyl ester is dissolved in a saturated solution of dimethylamine in 7 ° ^m l of dimethylformamide. The mixture is heated in a pressure-resistant vessel on a steam bath for 4 hours and heated. The mixture is then worked up in the manner described above. Yield 6.5 g of the Titolverbindung mp 230-233 ⁰ C ₀ After recrystallization from aqueous acetic acid the melting point rises to 236 C to 233, -

4Q9885 / U33

Example 3 1- (4-Cyano-3-methyl-5-isοthiazolyl) -3-isopropylurea

A mixture of 10.0 g (4-cyano-3-methyl-5-isothiazolyl) -carbamic acid phenyl ester and 23.0 g of isopropylamine in 70 ml of dimethylformamide is 2 hours in a pressure-resistant Vessel heated on a steam bath. The vessel is then cooled in an ice bath and opened. The content is in Poured 300 ml of water, the aqueous mixture acidified to pH 2 with concentrated hydrochloric acid and the The resulting solid is filtered off, washed with water and dried. The crude product melts at 191 to 195 ° C. After recrystallization from aqueous acetic acid, crystals are obtained which are essentially complete at 188.degree melt.

The implementation is repeated. A solid with a melting point of 180 to 183 ° C. is obtained. After treatment with ethanol the melting point rises to 184 to 187 ° C. The two Products are combined and re-crystallized from aqueous ethanol. Yield 7.0 g of the Tite compound from F. 184 up to 187 ° C.

Example 4 T - (4-cyano-3-methyl-5-isothiazolyI) »3-methiourea

A solution of 12.0 g of methylamine in 70 ml of dimethylformamide, by introducing the methylamine into the solvent

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-30 C was prepared, 10.0 g (^ -Cyan ^ -methyl-5-isothiazolyl) -carbamic acid phenyl ester are added. The mixture is kept in a pressure-resistant vessel for 19 hours
hO C heated and stirred and then cooled in an ice bath. The vessel is opened and the contents poured into 300 ml barrels. The aqueous solution is concentrated with
Hydrochloric acid acidified to pH 2 and the resulting solid filtered off, washed with water and dried. The product melts at 218 to 222 ° C. After recrystallization from. Ethanol, 5 g of the title compound with a melting point of 230 ° to 231 ° C. are obtained. After another Unilcri

crystallization, the melting point rises to 238 to 2 ^ 0 C.

Example 5
1- (4-cyano-3-isopropyl-5-isοthiazolyl) -3-methylurea

contains löin mixture of 6.7 g of 5-amino ~ 3-isopropylisothiazol-4-carbonitrile and 35 ml of methyl isocyanate in 35 nil tetrahydrofuran lh drops DibutyJzinndiacetat, 1.6 hours, heated under reflux. Thereafter, the volatile components under reduced pressure and at a
Distilled off at a temperature of below 35 ° C. The residue is digested with 75 ml of hot methanol, the mixture is filtered and the filtrate is cooled to room temperature. the
The resulting white crystals are filtered off. Yield 7.2 g of the title pre-binding with a melting point of 232 to 235 ° C.

^L. 409885 / U33

Example6

1- (4-Carbamoyl-3-isopropyl-5-isothiazolyl) -3-methylurea

A mixture of 5-4 g of 1- (4-cyano-3-isopropyl-5-isothiazolyl) -3-methylurea and 25 ml of concentrated sulfuric acid is heated on a steam bath for 1 hour and then poured into 200 ml of crushed ice. The dark colored The solution is adjusted to a pH of 8 with concentrated aqueous ammonia solution, and the crystals formed are filtered off, dried and recrystallized twice from methanol. Yield 2.7 g of the title compound with a melting point of 217 to 219 ° C.

Example 7 ^ .. (4..Cyan-3-isopropyl.5-isothiazol3'-l) -3-isop * Opy! Urea

A mixture of 10 g of (4-cyano-3-iso] TTopyl-5-isothiazolyl) -carbamic acid phenyl ester and 20.6 g of isopropylamine in 60 ml of dimethylformamide is heated to 40 ° C. for 22 hours. After working up according to Example k and recrystallization from 50 percent aqueous ethanol, 7 »0 g of the title compound with a melting point of 185 ° to 188 ° C. are obtained.

Example 8 1- (J | -Carbamoyl-3-isopropyl-5-i-thiazolyl) -urist off

A mixture of 4.1 g of 1 - (> l-cyano-3-isopropyl-5-isothia7: olyl) -

L. ■ -J

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3-isopropylurea and 20 ml of concentrated sulfuric acid are heated and stirred on a steam bath for 90 minutes. The reaction mixture is then poured onto 200 ml of crushed ice. The dark colored solution is adjusted to a pH value of 7 with concentrated aqueous ammonia solution, and the resulting crystals are filtered off, dried and dissolved in ethanol. The ethanol is distilled off under reduced pressure. The residue melts at 227 to 230 ° C. The test substance is suspended in 200 ml of hot methanol, the hot mixture is filtered and the filtrate is evaporated vigorously. The resulting crystals are collected by filtration, yield 1.8 g of the title compound, melting at 238 to 2JL-O ⁰ C.

Game 9

1- (4-Ethoxycarbonyl-3-methyl-5-isothiazolyl) -3,3-dimethylurea

A mixture of 5 g (4-ethoxycarbonyl-3-methyl-5-isothiazolyl) -carbaraxnsäurephenylester and a saturated solution of dimethylamine in 65 ml of dimethylformamide is heated in a pressure-resistant reaction vessel on a steam bath for 6 hours. The vessel is then cooled and the contents poured into 300 ml of water. The aqueous mixture is extracted three times with 200 ml of diethyl ether each time. The ether extracts are combined and dried over sodium sulfate. Thereafter, the ether is distilled off under reduced pressure at 0 C and the residue is dissolved in chloroform. The IR absorption

409885 / U33

. "1

spectrum shows the presence of the title compound. The chloroform solution it is evaporated, diethyl ether is added to the residue, and undissolved solids are filtered off. That The filtrate is diluted with diethyl ether and the ether solution is washed with 1% sodium hydroxide solution and saturated sodium chloride solution and dried over sodium sulfate. Then the ether solution is evaporated and the solid residue with the one before isolated solid residue combined. The solids are recrystallized from methylcyclohexane. Yield 0.3g of the title compound with a melting point of 128 to 129 ° C.

Example 10 1_ (4-cyano-3-isopropyl-5-isothiazolyl) -3,3-dimethyl urea

A mixture of 4.5 g (4-cyano-3-isopropyl-5-isothiazolyl) -carbamic acid phenyl ester and a saturated solution of dimethylamine in 40 ml of dimethylformamide is heated to 80 ° C. for 4 hours in a pressure-resistant reaction vessel. The solution is then evaporated to dryness under reduced pressure and the residue is taken up in hot aqueous ethanol. Crystals separate on cooling and are filtered off. F. I30 to 134 ° C. The filtrate is left to stand, whereupon more crystals of F _; Separate I30 to 135 ° C. The amounts of crystals are combined and recrystallized from methylcyclohexane. Yield 1.4 g of the title compound with a melting point of up to 134 ° C.

409 8 85 / U3 3

Example 11 1- (4-Cyano-3-propyl-5-isothiazolyl) -3-methy! Urea

A mixture of 13 »4 S S-carbonitrile and " JO ml of methyl isocyanate in 70 ml of tetrahydrofuran containing 30 drops of dibutyl zinc diacetate is refluxed for 20 hours. The reaction mixture is then evaporated under reduced pressure and the residue is dissolved in hot methanol The solution is filtered while hot and allowed to cool to room temperature, the resulting crystals are filtered off with cold metha

nol washed and dried. Yield 10.2 g of the title compound from 194 to 195 ° C. The filtrate becomes a

Another amount of 2.4 g of the title compound with a melting point of 192 ° to 193 ° C. was obtained. ^p

Example 12 1, (4-cyano-3-ethyl-5-isothiazolyl) -3-methy! Urea

A mixture of 10.4 g of 5-amino-3-ethylisothiazole-4-carbonitrile and 50 ml of methyl isocyanate in 50 ml of tetrahydrofuran, which contains 23 drops of dibutyltin diacetate is heated under reflux and stirred for 16 hours. After that, will the reaction mixture was evaporated under reduced pressure and the residue was obtained from methanol with the addition of activated charcoal recrystallized. Yield 11.8 g of the title compound with a melting point of 220 to 221 ° C. ·

A09885 / U33

Example 13 1- (4-carbamoyl-3-ethyl-5-isothiazolyl) -3-methyl urea

A mixture of 7.8 g of 1- (4-cyano-3-ethyl-5-isothiazolyl) -3-methylurea and 35 ml of concentrated sulfuric acid is heated to 100 ° C. for 75 minutes and stirred. The hot The mixture is poured onto 300 ml of crushed ice, the aqueous Mixture 15 minutes-stirred and then with concentrated Aqueous ammonia solution adjusted to a pH of 8. The mixture is then cooled to -5 ° C. and filtered and the isolated solid with cold water see. Then the solid is dissolved in hot methanol, the hot solution filtered and allowed to cool slowly. The resulting crystals are filtered off. yield 5.6 g of the title compound at F.215-216 ° C.

Example 1 4 1- (4-Carbamoyl-3-propyl-5-isothiazolyl) -3-diethyl urea

A mixture of 8.6 g of 1- (4-cyano-3-propyl-5-isothiazolyl) -3-methylurea and 10 ml of concentrated sulfuric acid is reacted according to Example 13 * Yield 6.9 g of the title compound from F, 204 to 205 ° C.

Example 15 1- (3-tert -Butyl-4-cyano-5-isothiazolyl) -3-methylurea

A mixture of 12.7 g of 5-amino-3-tert.-butylisothiazole- * l -

409885/1433

carbonitrile and 50 ml of methyl isocyanate in 50 ml of tetrahydrofuran, containing 25 drops of dibutyltin diacetate is refluxed and stirred for 24 hours. After that, that will Reaction mixture evaporated under reduced pressure, the The residue was dissolved in hot methanol and filtered while it was still hot. The filtrate is allowed to cool slowly. There will be 3 Crystal fractions isolated:

I. from 220 to 221 ° C .;
II, from mp 183 to 187 ° C and
III. from 217 to 222 ° G.

Due to the thin layer chromatography and the IR and According to the NMR spectrum, fraction I is almost pure 1- (3-tert-butyl-4-cyano-5-isothiazolyl) ) -3-methyl-3- (niethylcarbamoyl) urea and fraction III almost pure title compound. Fraction II is a mixture of almost equal parts of the two compounds.

After recrystallization of fraction III from ethanol, 1.5 g of pure title compound with a melting point of 232 ° to 233 ° C. are obtained.

Example 16

1- (3-tert-Butyl-4-carbamoyl-5-isothiazolyl) -3-methyl urea

A mixture of 4.1 g of 1- (3-tert-but3'-l-4-cyano-5-isothiazolyl) -3-methyl-3- (methylcarbamoyl) urea and 20 ml of concentrated sulfuric acid is heated to 100 ° C for 75 minutes and

409886/1433

stirs. The hot mixture is poured into 200 ml of ice water and stirred for 1 hour. The aqueous solution is concentrated with aqueous ammonia solution adjusted to a pH value of 8 and cooled to 5 C. The resulting solid is filtered off. It is only partially soluble in most solvents. The solid is in a Soxhlet extractor extracted with hot ethanol. The extract is cooled and the resulting crystals are filtered off, Yield 1.5 g of the title compound from mp 332 to 333 ° C.

Example17 *

1- (4-cyano-3-propyl-5-isothiazolyl) -3,3-dimethyl urea

A solution of 11.5 g of phenyl (4-cyano-3-propyl-5-isothiazolyl) carbamic acid and 3.7 g of dimethylamine in 10 ml of dimethylformamide is reacted according to Example 10. A brown liquid is obtained which has solidified after standing for 15 to 18 hours. After recrystallization from aqueous methanol, 6.8 g of the title compound from F, • 117 to 118 ° C. are obtained.

Example 18

1 - (3-tert- butyl-fy-cyano-5-isothiazolyl) -3 ₁ 3-dimethyl urea

A mixture of 12.2 g (3-tert-butyl-A-cyano-5-isothiazolyl) -carbamic acid phenyl ester and 3.7 g of dimethylamine in 40 ml of dimethylformamide are reacted according to Example 10. the

409885 / U33

resulting white crystals are obtained from aqueous ethanol tuncrystallized. Yield 8.7 g of the title compound with a melting point of 167 to 168 ° C.

Example 1 9 1 - (4-cyano-3-ath.yl-5.-is ο thiazolyl) -3,3-dimethylurea f

A mixture of 11.1 g (4-cyano-3-ethyl-5-isothiazolyl) -carbamic acid phenyl ester and 3 »7 S dimethylamine in 40 ml dimethylformamide is reacted according to Example 10. The resulting gray-brown solid is crystallized from ethanol. Yield 7.2 g of the title compound with a melting point of 156 ° to 157 ° C.

Example 2-0

1, (4_carbamoyl-3-propyl-5-isothiazolyl) -3,3-dimethyl urea

4.0 g of ice-cold 1- (4-cyano-3-propyl-5-isothiazolyl) -3,3-dimethylurea 8 ml of concentrated sulfuric acid are carefully added. The mixture will slowly rise Allowed to warm to room temperature and then heated to 50 ° C for 2 hours. The hot solution is poured into 75 ml of ice water and stirred for 15 minutes. A precipitate forms. Then another 75 ml of ice water are added, and that. The mixture is stirred and then filtered. The precipitate is washed with cold water. The filtrate is with concentrated aqueous ammonia solution to pH

409 8 85/143 3

set from 7. A further amount of solid separates out in the process. The solids are isolated. Because of of thin layer chromatography are the two solids. identical. They are combined and recrystallized from ethanol. Yield 3.3 g of the title compound of mp 173-174 ° C.

Example 2 1

1- (4-carbamoyl-3-ethyl-5-isothiazolyl) -3,3-dimothy / urea

A mixture of 4.0 g of 1- (4-cyano-3-ethyl-5-isothiazolyl) - ■> 3,3-dimethylurea and 9 ml of concentrated sulfuric acid is reacted according to Example 20. Yield J, k g of the title compound from 195 to 196 C.

Example22

1- (3-tert-Butyl-4-carbamoyl ~ 5-isothiazolyl) -3,3-dimethylurea

A mixture of 5.4 g of 1- (3-tert-butyl-4-cyano-5-isothiazolyl) -3,3-dimethylurea and 11 ml of concentrated sulfuric acid is reacted according to Example 20. The resulting white Crystals are recrystallized from acetic acid and then from ethanol. Yield 1.8 g of the title compound from F. 335 to 336 ° C.

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Example 2 3

1- (4-carbamoyl-3-isopropyl-5-isothiazolyl) -3, 3-dimethyl urea

A mixture of 5 »0 g of 1- (4-cyano-3-isopropyl-5-isothiazolyl) -3» 3-dimethylurea and 11 ml of concentrated sulfuric acid is reacted according to Example 20. The initially received Precipitation from the F. 216 C is digested with ethanol. The insoluble one Solid with a melting point of 195 to 196 C is a by-product, that is discarded. The ethanol solution is on for 2 hours

heated in a steam bath with 10 percent hydrochloric acid / and then cooled. The resulting solid is filtered off and dried. Yield 1.3 g of the title compound.

The originally strongly acidic mixture of ice and water is brought to a pH value with concentrated aqueous ammonia solution set from 7 to 8. This gives a further amount of the title compound which, after recrystallization, is obtained Ethanol melts at 183 to 184 ° C.

Example 24

1- (4 ~ cyano-3-isopropyl-5-risothiazolyl) -3-ynethoxy-3-methylurea

A mixture of 4.3 g (4-cyano-3-isopropyl-5-isothiazolyl) -carbamic acid phenyl ester and 0.9 g of N, O-dimethylhydroxylamine in 20 ml of dimethylformamide is heated to 100 ° C for 5 hours in a 200 ml pressure-resistant vessel and

409885 / U33

touched. Then the contents of the vessel are allowed to cool slowly to room temperature. The mixture is evaporated under reduced pressure. The residue solidifies on standing and is recrystallized from ethanol. Yield 3 »3 S of the title compound with a melting point of 106-107 ° C.

Similarly, 1- (3-tert-butyl-4-cyano-5-isothiazolyl) -3-methoxy-3-methylurea from F, 68 to 70 C. The hydrolysis of this compound with concentrated Sulfuric acid provides 1- (3-tert-butyl-4-carbamoyl-5-isothiazolyl) -3-niethoxy-3-methylurea of mp 133 ° C (decomposition).

The following compounds are also produced in the manner described in Example 2:

Example connection F. , C.

25 1- (4-cyano-3-isopropyl-5-isothiazolyl) -3-cyclopentylurea I6I-I63

26 1- (4-cyano-3-isopi- * opyl-5-isothiazolyl) -3-cyclopropylurea 201-203

27 3,3-dibutyl-1- (4-cyano-3-isopropyl-

5-isοthiazolyl) urea oil

28 1- (4-cyano-3-isopropyl-5-isothiazolyl) -3,3-di- (isopropyl) urea '. 209-210

29 N- (4-cyano-3-isopropyl-5-isothiazyllyl) - · morpholine-1-carboxamide 155-156

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Γ Π

N- (4-cyano-3-isopropyl-5-isothiazolyl) -piperidine-1-carboxamide 170-171

N- (4-cyano-3-isopropyl-5-isothiazolyl) -pyrrolidine-1-carboxamide . I6I-I62

N- (4-cyano-3-isopropyl-5-isothiazolyl) -

2,5-dimethylpyrrolidine-1-carboxamide 129-130

3 »3-diallyl-1- (4-cyano-3-isopropy1-5-isothiazolyl) urea 59-60

3-selc.-butyl-1- (4-cyano-3-isopropyl-5-isothiazolyl) urea 176-178

1- / 2 * -carbamoyl-3- (i-methylbutyl) -5- ' isothiazolyl7-3-methylurea 216-217

1- (3-Butyl-4-carbamoyl ~ 5-isothiazolyl) -3-methylurea I96-I98

1- (3-sec-butyl-4-carbamoyl-5-

isοthiazolyl) -3-methylurea 213-21 h

1 - / ^ - carbamoyl-3- (i-methylbutyl) -5-isothiazolyl / -3,3-dimethylurea I3O-I3I

39 1 - / ^ - Carbamoyl-3- (i-methylbutyl) -5-

isothiazolyl7-3-ethylurea 206-207

1- (4-Carbaraoyl-3-isobutyl-5-isothiazolyl) ~

3,3-dimethylurea 182-183

ki 1- (4-cyano-3-isobutyl-5-isothiazolyl) -

3,3-dimethylurea 168-169

. 1- / 4-carbamoyl-3- (i-ethylpentyl) -5-

isothiazoly37-3,3-dimethy! urea 114-115 1- (3-so-butyl-4-cyano-5-isothiazolyl) -3-methylurea - 195-197

A098857 143 3

44 3-Butyl-1- (4-cyano-3-isopropyl-5-isothiazolyl) urea 129-130

45 1- (4-Ethoxycarbonyl-3-diethyl-5-isothiazolyl) -3-ethylurea 138-141

46 1— (4-ethoxycarbonyl — 3-methyl-5—

isothiazolyl) -3-methyl-urea 189-192

47 '1- (3-butyl-4-carbamoyl-5-isothiazolyl) -

3-ethylurea 220-221

48 1- / 4-Cyano-3- (1,1-dimethy! Butyl) -5-isothiazolyl7-3,3-dimethylurea IO8-IO9

49 1- (3-Butyl-4-carbamoyl-5-isothiazolyl) -> 3-methoxy-3-methylurea 163

50 1- (4-Carbamoyl-3-pentyl-5-isothiazolyl) -3-methoxy-3-methylurea 157-159

The compounds of general formula I are valuable Herbicides. The following experiments have shown this. In pre-emergence experiments, haricot beans (Phaseolus lunatus), Corn (Zea mays), wild oats (Avena fatua), garden lettuce (Lactuca sativa), mustard (Brassica juncea) and finger millet (Digitaria sanguinalis) in flat flower bowls measuring 20 15 χ 7.5 cm, which are about 5 to 7 »5 cm high were filled with sandy loam soil, sown in rows. Within 24 hours after sowing, an aqueous one becomes Acetone solution of the compound to be investigated is sprayed onto the ground in an amount of 9 kg per hectare.

liter
volume corresponds to 757 / per ha. The flower bowls are

under normal growing conditions about 3 weeks in one

409885 / U33

Greenhouse left standing. The herbicidal activity of the compound under investigation is then determined. Individual plants are examined in comparison with untreated plants. Table I summarizes the results. The numbers represent the percent kill at a dose of 9 kg per ha,

Post-emergence experiments use the same seeds as the pre-emergence attempts, and the untreated Flower bowls grow to the three-leaved stage of the bean plants left in the greenhouse. The plants are then treated with an aqueous acetone solution to be examined Connection injected as well as in the pre-emergence attempt. The plants are kept in the greenhouse for 3 more weeks under normal Left to grow conditions. The herbicidal activity of the compound is then determined. In Table II are the results summarized. The numbers mean the percentage of death at a dose of .9 kg per ha.

4Q9885 / U3?

- 26 Table I.

link At all Corn riug- garden mustard Finger- of example th iaf he lettuce millet Bean 100 100 1 90 * 30 - "- - _ 100 100 100 2 100 o-x - 100 100 100 3 75 * O - 100 100 50-x k 100 100 - 80 * 100 100 5 100 30 * 100 100 100 100 6th 100 O - 100 100 100 7th 100 O - 100 100 95 * 8th 100 O - 100 0 90 * 9 **. 50 o-x - 0 100 20th 10 100 70 - "- - 100 100 100 11 loo 100 100 100 100 100 12th 100 100 100 100 100 100 13th 100 100 100 100 100 100 • 14 100 100 100 100 100 100 15th 100 100 100 100 100 100 16 100 100 100 100 100 100 17th 100 100 100 100 100 100 18th 100 100 100 100 100 100 19th 100 100 100 100 100 100 2Q 100 100 100 100 100 100 21 100 O 100 100 100 100 22nd 100 100 100 100 100 10 23 100 loo 100 100 100 100 Zk 100 0 100 100 100 100 25th O 100 0 80 * 100 30th '26 100 0 100 100 30th 100 27 O 0 10 20th 0 0 28 25th 0- * 0 0 100 0 29 100 0 50 100 100 100 30th 50 0 10 100 100 10 31 100 0 100 100 100 80 * 32 50 * 0 0 100 100 100 33 50 0 0 100 100 70 *. 3 k 100 50 100 80 *

* surviving plants severely damaged, so that they probably no longer recover.
ψ ¥ dose 2.25 kg / ha.

409885 / U33

- 27 - '
Table II

link At all Corn lying garden 100 mustard finger of example th afer lettuce 100 millet Bean 30 * 1 _ 100 100 1 100 100 " 100 100 100 2 100 O - 100 100 100 3 100 70 - 100 100 100 H 100 100 - 100 100 100 5 100 100 100 100 100 100 6th 100 O - 100 100 100 7th 100 O - 100 100 80 * 8th 100 O • - 100 100 80 * 9 * * ■ 100 100 - 100 100 4o 10 100 70 - 100 100 100 11 100 100 100 100 100 100 12th 100 100 100 100 100 100 13th 100 100 100 100 100 100 14th 100 100 100 100 100 100 15th 100 100 100 100 100 100 16 100 ■ 100 100 100 100 100 17th 100 100 100 . 100 100 100 18th 100 100 100 100 100 100 19 · 100 100 100 100 100 100 20th 100 100 100 100 100 100 21 - 100 30 * 100 100 100 100 22nd 100 100 100 100 100 30th 23 100 100 100 100 100 100 24 100 O 100 80 * 100 100 '25 100 100 10 50 100 10 26th 100 O 100 100 100 100 27 50 O O 100 100 20th 2 8 100 O 50 100 100 10 • 29 100 O 30th 100 100 70 30th 100 30th O 100 100 »10 31 100 O 50 100 100 4o 32 100 O O 100 80 * 33 100 30th 20th 100 60 34 100 70 100

M surviving plants severely damaged, so that they probably no longer recover
* · Dose 2.25 kg / ha.

AO9 88 5/1433

The compounds of general formula I can be used as herbicides together with the usual carriers and / or diluents and / or auxiliaries are used in the form of herbicidal agents, for example as granules, wettable powders, emulsifiable concentrates or solutions.

Granules are particularly suitable for use from aircraft. The granules can be of various types. At.impregnated Granules is the active ingredient on large particles of an absorbent carrier such as attapulgite or Kaolin, corn on the cob or expanded mica and usually applied in the form of a solution in a solvent. Surface coated Granules can be prepared by spraying the molten active ingredient on the surface of in general non-absorbent particles or by spraying a solution of the active ingredient in a solvent will. The core can be made of a water-soluble material, such as fertilizers in pellet form or insolubles, like sand, marble granules or coarse talc, especially Granules can be used in which a wettable powder is used as Surface coating on sand or other insoluble particles is applied so that the wettable powder can be dispersed upon contact of the granules with moisture. Granules can be prepared in a manner known per se from dusts or powders by compacting with rollers by extrusion or can be produced on granulating disks. The active ingredient concentration in thin granules can be in a relatively wide range. The granules can contain 0.5 to 95 products

409885 / H33

percent of the active ingredient.

Wettable powders are also useful pre-emergence and sewage accumulation means. They are in the form of finely divided Particles that easily disperse in water or other liquids. The wettable powder will be on the soil or the plants to be destroyed either in finely divided dry form or as an emulsion in water or another liquid applied. Typical carriers for wettable powders are fuller's earth, kaolin, and silica and other highly absorbent, easily wettable inorganic diluents. Contain the wettable powders generally about 5 to 80 percent of the active ingredient, depending on the absorbency of the carrier. Also included they generally also contain a small amount of a wetting, dispersing or emulsifying agent. For example, contains a suitable wettable powder 80.8 parts 1 - (4-carbamoyl-3 * - isOpropyl-5-isothiazolyl) -3-methy / urea, 17-9 parts Pa'lmettoton, 1.0 part sodium lignosulfonate and 0.3 part a sulfonated aliphatic polyester as a wetting agent *

Other useful herbicidal agents are emulsifiable concentrates, which represent homogeneous liquids or pastes which are dispersible in water or other liquids and which either only consist of the active ingredient and a liquid or solid emulsifying agent or which still contain a liquid Contain a carrier such as xylene, a heavy gasoline, isophorone or another, non-volatile organic solvent.

409885/1433

Typical wetting, dispersing and emulsifying agents used in agricultural Chemicals that can be used are alkyl and alkylaryl sulfonates and sulfates and their sodium salts, Polyethylene oxides, sulfonated oils, fatty acid esters of polyhydric alcohols, and other types of surfactants Compounds, The surfactant compounds are generally used in an amount of 1 to 15 percent by weight of the herbicidal agent used "

These herbicidal agents can be used without further dilution or as dilute solutions, emulsions or suspensions in water ser or other suitable diluents can be used. The funds are either applied to the area to be treated sprayed or poured onto the surface of the soil or mechanically when using solid herbicidal agents spread the floor. The material applied to the ground can also be worked into the ground.

The compounds of the invention can be used together with insecticides den, fungicides, nematocides, plant growth regulators, fertilizers and other agricultural chemicals.

409885 / H33

Claims (1)

Patent claims 1 . Isothiazolylureas of the general formula I R ₁ "^, ___A ² ^ S ^ ³ N - C - H 0 in which R _{1 is} a straight or branched alkyl radical with 1 to 8 carbon atoms, R "is a hydrogen atom, an alkyl, alkoxy or alkenyl radical with up to h carbon atoms or a cycloalkyl radical with 3 to 6 carbon atoms and R" is a hydrogen atom, an alkyl or Alken3 '"lrest up mean to h carbon atoms, or R and R' together with the nitrogen atom to which they are attached form a 5- to 7gli ^e drigen heterocyclic radical which may contain an oxygen or nitrogen ring atom, and a represents a cyano, alkoxycarbonyl or a carbamoyl group which is optionally substituted by one or two alkyl or alkenyl radicals and the alkoxy, alkyl and alkenyl radicals contain up to h carbon atoms. 2, compounds according to claim 1 of the general formula I, in which (A) R and R are methyl or ethyl groups when A is a Represents cyano group or. '* (b) A is an alkoxycarbonyl radical and R «is a hydrogen atom and R contains ₁ h to 8 carbon atoms. L -J 409885/1433 3. Compounds according to claim 1 of general formula I, in which R ₂ and R contain a total of 1 to k carbon atoms and A represents a cyano or carbamoyl group. 4. Compounds according to claim 3 »characterized in that R _{1 contains} 1 to 5 carbon atoms. 5 · 1- (4-ethoxycarbonyl-3-methyl ~ 5-isothiazolyl) -3-isopropylurea. 6. 1- (4-Cyano-3-methyl-5-isothiazolyl) -3,3-dimethylurea. 7. 1- (4-cyano-3-methyl-5-isothiazolyl) -3-methyl-urea, 8. 1- (4-Cyano-3-isopropyl-5-isothiazolyl) -3-diethylurea. 9. 1- (4-Carbamoyl-3-isopropyl-5-isothiazolyl) -3-methylurea. 10. 1- (4-Cyano-3-isopropyl-5-isothiazolyl) -3,3-dimethylureas 11. l - ('3-tert-Butyl-4-cyano-5-isothiazolyl) -3-methylurea. 12. 1- (3-tert -Butyl-4-cyano-5-isothiazolyl) -3,3-dimethylurea. 409885/1433 13 · 1- {4-cyano-3-isopropyl-5-isothiazolyl) -3-niethoxy-3 ~ methyl urine. 14. 1- (4-Carbamoyl-3-ethyl-5-isothiazolyl) -3-methylurea. 15 x 1- (4-carbamoyl-3-propyl-5-isothiazolyl) -3-diethylurea. · 16. 1- (4-Cyano-3-propyl-5-isothiazolyl) -3,3-dimethylurea. ',. 17 · 1 - (4-cyano-3-diethyl ~ 5-isothiazolyl) -3-isopropylurea. 18. 1 ~ / 5 + -carbamoyl-3- (i-methylbutyl) -5-isothiazolyl7-3-me thylharns t ο ff. 19 "» 1- (3-butyl ~ 4-carbamoyl-5-isothiazolyl) -3-methylurea. 20. 1- (3-s eic.-Butyl-4-carbamoyl-5-i s o thiazolyl) -3 ~ methyl urine t of f. 21, a process for the preparation of the compounds according to claim 1, characterized in that either in a known manner (a) an isothiazolylcarbamic acid phenyl ester of the general 409885 / U33. Formula II n '1 (II) N-C-O- C ^ H- Il H 0 30 minutes to 2k hours at temperatures from 25 to 100 ° C with an amine of the general formula • HNR ₂ R ₃
implements or (b) for the preparation of compounds of the general formula I, in which R_ means a Fassstoffatom, an Amxnoisothiazol of the general formula III 30 minutes to 2k hours at temperatures of 25 to 10O ⁰ C with an isocyanate of the general formula R ₂ NCO implements or (c) for the preparation of compounds of the general formula I, in which A is a —CONH_ group, a 4 — cyano-isothiazolylurea of the general formula IV R. ' CN. (IV) "2 ^R 3 Saponified for 30 minutes to 24 hours at temperatures of 25 to 100 ° C. 409885/1433 22. Use of the compounds according to claim 1 as Herbicides, 409886 / .U33