CS209945B2 - Herbicide means and method of making the active substance - Google Patents

Abstract

1. 4,5-Dichloroimidazole derivatives of the formula I see diagramm : EP0013905,P20,F1 in which X**1 represents hydrogen, chlorine, bromine or iodine, X**2, X**3 and X**4 in each case represent hydrogen, chlorine or bromine and X**5 represents hydrogen or chlorine, and in addition, X**1 and X**3 together can represents a C-C bond, and also X**2 and X**4 together can represent a C-C bond, or X**1 and X**2 together represent oxygen or the grouping =N-Y, Y represents hydroxyl and the radicals see diagramm : EP0013905,P21,F2 in which R represents hydrogen or alkyl with 1 to 4 carbon atoms, R**1 represents phenyl or naphthyl optionally substituted by fluorine, chlorine, bromine, alkyl with 1 or 2 carbon atoms, alkoxy with 1 or 2 carbon atoms, trichloromethyl, trifluoromethyl and/or nitro, Z represents oxygen or sulphur and R**2, R**3 and R**4 independently of one another represents hydrogen or chlorine, but wherein X**1, X**2, X**3, X**4 and X**5 do not simultaneously represent hydrogen.

Description

The invention relates to a herbicidal composition comprising, as an active ingredient, at least one of the novel 4,5-dichloroimidazodone derivatives. The invention furthermore relates to these novel herbicidally active derivatives of 4,5-dichloroimidazo ⁱ lu.

It is already known; It is claimed that certain 4,5-dichloroimidazole-2-carboxylic acid derivatives have herbicidal properties (cf. DOS 2,610,527). For example, 4,5-dichloroimidazole-6-carboxylic acid ethylamide can be used to control weeds. However, this substance is not always sufficiently effective and its selectivity is not always entirely sufficient.

We have now found novel 4,5-dichloroimidazole derivatives of formula (I)

X ¹ and X ³ can be taken together to represent a C-C bond as well

X ² and X ⁴ may together represent a C-C bond, or

X ¹ X ² а together represent oxygen or the group = N-Y, in which

Y is hydroxy and the radicals —NH — C — NHR,

From — NH — R1 or

Cl

Ct

I (Г)

in which

X ¹ is hydrogen, chlorine, bromine or iodine,

X ² , X ³ and X ⁴ are hydrogen, chlorine or bromine,

X ⁵ is hydrogen or, chloro, and furthermore in which

ЯЙивй ^^ · '

R is hydrogen or (C1-C4) -alkyl,

R ¹ represents an optionally substituted phenyl radical,

209943

Z is oxygen or sulfur and

R ² , R ³ and R ^{4 are} each independently hydrogen or chloro, but X ¹ , X ² , X ³ , X ⁴ and X ^{5 are} not simultaneously hydrogen.

Novel 4,5-Dichloroimidazole Derivatives! of formula I are prepared according to the invention by reacting 2-ethylimidazole of formula II in which

X ⁵ , X ⁶ and X ⁷ are as defined above, allowed to react with a hydrogen chloride cleavage agent in the presence of a diluent, or

d) 2,4,5-trichloro-2- [1,1-dichloroethyl] -2H-imidazole of formula V

or its hydrochloride with up to 7 moles of chlorine per 1 mol of 2-ethylamidazole in a solvent inert to the reactants. [The process of the invention will hereinafter be referred to as process a)].

Further, the compounds of formula (I) may be produced by:

b) a 4,5-dichloroimidazole derivative of the formula III

A A

I I

About CX ¹ ? ¹ й

X (lil) in which

X ⁶ is chlorine, bromine,

X ⁷ denotes chlorine or bromine, and

X ³ , X ⁴ and X ⁵ are as defined above, but X ³ , X ⁴ and X ^{5 do} not simultaneously represent hydrogen,

(a) hydrolyses with water or reacts with at least the stoichiometrically required quantity of dehalogenating agent, where appropriate in the presence of a diluent; or>

χ) react with at least stoichiometrically required amount! a metal hydride useful for hydrogenation in the presence of a diluent;

c) reacting the 4,5-dichloroimidazole derivative of the formula IV

(a) with a reducing agent in the presence of a diluent; or

´ ./3j with at least a 3 molar excess of alkali metal iodide or at least a 1.5 molar excess of alkaline earth iodide in the presence of a lower-aliphatic ketone as diluent, or

χ) with at least an equimolar amount of alkali metal bromide or at least an equivalent amount of an alkaline earth metal bromide in the presence of a lower ¹ aliphatic nitrile or lower aliphatic ketone as a diluent, or; se

(e) a 4,5-dichloroimidazole derivative of the formula VI ...

v nemiz

Hal means chlorine or iodine,

a) reacting with a hydrogen halide cleavage agent, optionally in the presence of a diluent, or i) hydrolyzing with water in the presence of a base or a basic salt, or

f) a 4,5-dichloroimidazoil derivative of the general formula VII

Cl

Cl

(VII) (IV) wherein χ3, χ4 and X ⁵ 'are as defined above, is reacted with a compound of formula -obecného

H ₂ N — Y '(VIII), in which

Y 'is amino, hydroxy, and —NH — C — NHR

II

Z or —NHR1 in which

Z is oxygen or sulfur,

R is hydrogen or (C 1 -C 4) alkyl and iR 1 is optionally halogen, alkyl, alkoxy, haloalkyl and / or nitro substituted aryl, in the presence of a diluent, or

g) 4,5-dichloro-2-ethynylimidazole of formula IX

C5CH (IX) is reacted with a chlorinating or brominating agent in the presence of a solvent which is inert under the reaction conditions;

h) 4,5-dichloroimidazole derivatives of formula X

Cl-. . _N [i Ί Ί / λ] ⁵

Ci (X) wherein ^{χ1, χ3,} and ^X4 have the previously listed Eny ^d, are reacted with chloračním- bromačním- činidlem- or in the presence of a solvent which is inert under reaction conditions, or -mi

JI lf | ' сг / C ~ CH-X *

HI (XI) wherein

X ⁶ and X ⁷ are as defined above - a

Hal 'means chlorine, bromine or iodine, thermally dehydrohalogenates in the presence of a lower aliphatic nitrile.

Finally, it was found that new derivatives

The 4,5-dichloroazazole of the formula I has potent herbicidal, in particular also selective herbicidal properties.

Surprisingly, the 4,5-dichloroimidazole derivatives of the general formula I according to the invention, with a very good weed control effect, show, in particular, better possibilities for use as selective weed control agents in important crops than ethylamide.

4,5-Dichloroimidazole-2-carboxylic acid, which is known in the art and which is a highly active substance of the same type of action. The compounds according to the invention thus represent a valuable enrichment of herbicidal compositions for the selective control of weeds.

The 4,5-dichloroimidazole derivatives of the invention are generally defined by the formula I. In this formula, the general symbols have the following preferred meanings:

χΐ - is preferably hydrogen, chlorine, bromine was not _O j d

X ² is preferably hydrogen, chlorine or bromine,

X ³ is also preferably hydrogen, chlorine or bromine; hydrogen, chlorine or bromine, and

X ⁵ is preferably hydrogen or chlorine, but X ¹ , χ 2, χ 3, χ 4 and X ⁵ do not all know hydrogen at the same time.

In formula I, the symbols - X * - and X ³ together together represent a carbon-carbon bond. Furthermore, X ² and χ 4 together represent a C-C bond. Preferably, in addition, χ ² and X ² together represent oxygen or = N-Y. In this case, Y is preferably a hydroxy group or the radicals-NH-C-NH-R,

From ’—NHR1 or—

i) reacting 4,5-dichloro ^o-Rim imidazol XI

209943

In these radicals, R is preferably hydrogen or C1 -C2 alkyl, in particular hydrogen. Z is preferably sulfur. R ¹ represents an optionally chlorine substituted phenyl group. The radicals R @ ² , R ^{@ 1} and R ^{@ 4} are preferably hydrogen.

In the process according to the invention [process aj] per mol of 2-ethylamldazole, 7 mol of chlorine is used, then the reaction sequence can be illustrated by the following reaction scheme:

HCt

If 4,5-dichloro-2-pentachloroethyl imidazole is used as the starting material and water is used as the hydrolyzing agent, process (b), variant a, according to the invention, can be seen by the following reaction scheme:

+ 2 HCt

C-CCk II

When 4,5-dichloro-2-pentachloroethylimidazole is used as the starting material and sodium iodide in acetone as the dechlorinating agent 1a, the reaction according to the process b), variant $) according to the invention can be illustrated by the following reaction scheme:

Ná-J

Ct-NC, Cl- ₅ acetone

I ^z

H

Ct + 2 Na Cl + J _L c = cci _z

If 4,5-dichloro-2-pentachloroethyl imildazole is used as the starting material and sodium borate is used as the hydrogenation agent, then

H

When 4,5-dichloro-2- (2,2,24-chloroethyl ethylididazole is used as starting material and triethylamine as the cleavage reagent, process b), variant χ) can be illustrated by the following reaction scheme:

+ 2 HCt сн ₂ са ₃ hydrogen, then the course of procedure cj can be illustrated by the following reaction scheme:

ct

Cl

N (Et) ₃

--------->

CH ₃ CCt ₃

+ HCt

CH = CCt _s

H

H, then the process flow d), variant a] can be illustrated by the following reaction scheme:

When 2,4,5-trichloro-2- [1,1-dichloroethyl) -2H-imidazole is used as the starting material and catalytically activated hydrogen as, re209945

'H ^{/ P} d

Cl -A-—

CCI = CH _b + ^2HCl toluene аГ с ^ = _сн г

H

If 2,4,5-trichloro-10-lOT-2- (1,1-dichloroethyl) -2H-imidazole and sodium iodide are used as starting materials, the procedure is as follows.

d), variants / 3), be represented by the following reaction scheme:

If 2,4,5-trichloro-2-1,1,1-dichloroethyl] -2H-imidazole and potassium bromide are used as starting materials, the process dj, variant χ) can be illustrated by the following reaction. by the scheme:

Cl. + 2 KBr

CCtgCH4. ~ 2KCl

Cl

Cl ·

- HBr

When imidazole is used as the starting material and triethylamine is used as a halogen splitting agent, the process (e), variant (a) can be illustrated by the following reaction scheme:

H

JN (Et) ₃ | - _the

C = CH _S ^-hj

If 4,5-dichloro-2-diimidinyl imidazole is used as the starting material and water as well as the sodium formate as the hydrolyzing agent, then the process (e), variant (3) can be illustrated by the following reaction scheme. :

<C-> _U , N & OOCH

FV -w --->

CL'W = C = CH, ^L

H

If 4,5-dichloro-2-acetylimidazoil and phenylhydrazine are used as starting materials, the reaction sequence f can be illustrated by the following reaction scheme:

When dis-dichloro-2-ethnylimidazole is used as the starting material and sulfuryl chloride as chlorinating agents, the process (g) may be illustrated by the following reaction scheme:

SO-CL —-—- Λ

The procedure h) is illustrated as follows. Reaction scheme:

Η

Smell

CHCL *

4,5-Michloro-24 (chloro-vinyl imidazod) as starting material and sulfonyl chloride are used as the chlorinating agent, then the reaction can be carried out.

^CCt £ ^CH Z ^Ct

If 4,5-dihydro-2- (l-lH-trifluoromethyl) imidazole is used as the starting material, the process (i) can be illustrated by the following reaction. by the scheme:

The thiimidimidazole or its hydrochloride, which is required as a starting material in process ai) according to the invention, is a known substance.

Chlorine gas is used as the chlorinating agent in process (a) according to the invention.

Suitable solvents for carrying out process a.) According to the invention are all customary solvents which are inert under the reaction conditions. These include, preferably, phosphorus oxychloride, 1,1,2,2-tetramethylaluminum, tetrachlorethylene, and thionyl chloride.

The reaction temperatures may vary according to the process according to the invention depending on the desired co-reaction product within a certain range. The media is synthesized with 4,5-dihalo-22-pentahloroethylimidazole, then working generally at temperatures between 90 and 150 ° C, preferably between 100 ° C and 130 ° C. In order to produce lower chlorinated compounds, it is generally carried out at temperatures between 60 ° C and 100 ° C, preferably between 70 and 90 ° C.

In carrying out process (a) according to the invention, 2-ethylimidazole or its hydrochloride is reacted, depending on the desired end product, with different amounts of chlorine. It is possible to prepare 4,5-dichloro-4-pentachloroethyl imidazole, then about 3 to 7 moles of chlorine is used per mole of 2-ethylimidazoil. To alleviate the strongly exothermic reaction reaction, the exothermic formation of the hydrochloride from 2-ethylimidazole and hydrogen chloride can also be avoided by using not 2-ethylimidazole alone but the hydrochloride as the starting material. Insulation; The reaction product is carried out by conventional methods. Generally, this is done. in such a way that the solvent is distilled off and the residue is stirred with formic acid at room temperature. The reaction product, which crystallizes out in the process, is decanted. However, it is also possible to freeze the reaction product from the solvent-free residue under vacuum, for example at 125 ° C / 1.3 Pa.

If, in process (a), a 4,5-dichloroimidazole derivative of Formula (I) is to be produced in which the side chain contains less than 5 chlorine atoms, then it is used per mole of 2-ethylimidazole or its 2-ethylimide. hydrochloride, up to 6 moles of chlorine, but the reaction temperature is kept lower than that of the ethyl group. Often, the reaction product is not formed in pure form but in a mixture with varying amounts of 4,5-dichloro-2-pentachloroethyl-amino-azole. However, the desired reaction product can be obtained in such a case in a pure state by conventional separation methods, such as (traction) crystallization, for example from acetone, or by chromatography.

The 4,5-dichloroimidazole derivatives which are required as starting materials in carrying out process b) are defined by formula III. In this formula, the symbols · χ3, χ4 and X ⁵ preferably represents those radicals which have already in connection with the description! of the compounds of the invention have been reported to be preferred for X ³ , χ 4 and X ^{5 5} . However, residues χ3, χ4 and χ5 do not simultaneously represent hydrogen. X6 and X7 are preferably chlorine or bromine.

The compounds of formula III were not known until now. However, they can be produced according to the process according to the invention optionally; according to other processes of the invention.

In carrying out process variant b), the 4,5-dichloroimidazole derivative of formula III is hydrolyzed with water. At the same time, water acts as a reaction medium and is therefore used in a considerable excess.

The reaction temperature may be varied within a certain range in carrying out process variant (b). In general, the reaction is carried out at temperatures between 70 ° C and 120 ° C, preferably at the boiling point of the reaction mixture.

The isolation of the reaction products is carried out in the reaction according to process variant (b) according to conventional methods. Generally, the reaction products precipitate in a crystalline state so that they can be filtered off.

In carrying out process variant (3) (b), all reagents which are usually used for such purposes are suitable as dehalogenating agents. Preferred useful dehalogenating agents are sodium iodide in acetone, cuprous chloride, zinc powder, iron powder, sulfur and phosphorus.

Possible diluents for variant (3) of step b) are all solvents which are usually used for such rain and logenation reactions. Conveniently. useful solvents are: acetone, toluene, chlorobenzene, 1,2-dichlorobenzene and 1,2,4-trichlorobenzene.

A particularly preferred dehalogenating agent is sodium iodide and acetone.

In process variant (3), the reaction temperatures can be varied within a wide range. In general, it is carried out at temperatures between 0 ° C and 200 ° C, preferably between 50 ° C and 150 ° C. The sodium iodide-acetone system is generally operated at temperatures between 0 ° C and 50 ° C, preferably between 20 ° C and 30 ° C.

When carrying out variant / 3) of the process b) was allowed to · · · reacting a ^{4,5-dichloirimidazo:} lu · vztrce III with at least a plurality stechiometriekým · dehalogenating agent. If sodium iodide is used, the reagent may be used in multiple excess without further dechlorination. The isolation of the reaction products is carried out by conventional methods.

In general, when sodium iodide is used as the chiloring agent, the reaction mixture is poured into ^; water, free iodine is removed by the addition of a reducing agent, such as an aqueous sodium bisulfite solution, and the crystalline product is filtered off.

In carrying out process variant (b), all of the customary (complex) metal hydrides are suitable as hydrogenation agents. Particular mention should be made of sodium borate.

Suitable diluents for process variant (b) (b) are all solvents customarily usable for such reactions. Particular mention should be made of water.

Particularly preferred is the sodium borate system and the water.

The reaction temperatures can be varied within a wide range in process variant (b). · · Are generally operated at temperatures between 0 ° ^C and · 50 ° C · · preferably between 10 ° C and 40 · C. When using the sodium borate-water system, the process is preferably carried out at room temperature or at a slightly lower temperature.

In process variant (b) of process (b), the 4,5-dichloroimidazole derivative of formula (III) is reacted with at least the stoichiometrically necessary amount of metal hydride. If sodium borate is used, then a larger excess, for example up to 10-fold excess, can be used without further undesirable hydrogenations. The reaction products are isolated by conventional methods. The use of sodium borate as the hydrogenation agent is generally carried out by first decomposing the excess sodium borate present by careful addition of the acid and dissolving any boric acid formed with hot water and removing it from the reaction mixture.

In carrying out process (c) as starting materials, the necessary 4,5-dichloroimidazole derivatives are defined by the general formula (IV). In this formula the symbol R · ⁵ · preferably hydrogen or chlorine, X ⁶ and X 7 are preferably chlorine or ·; bromine.

The compounds of formula IV have not been known. However, these compounds are produced according to process b), variant y).

In carrying out process (c), all of the reagents commonly used for such reactions are suitable as hydrogen halide cleavage reagents. These include inorganic and · organic bases, such as hydroxides, · optionally alkali metal and alkaline earth carbonates and bicarbonates, · aluminum oxides and organic amines, especially tertiary amines such as; for example triethylamine.

As; diluents are suitable in process c) for all solvents which are customary for such dehydrohatogenation reactions.

Preferred solvents are water or an amine which simultaneously serves as the hydrogen halide cleavage reagent and dioxane.

The reaction temperatures in process c) can be varied within a wide range. In general, it is carried out at temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C.

In carrying out process c), generally 1 to 1.2 mol of the dehydrohalogenating agent is used per mole of the 4,5-dichloroimidazole derivative of the formula IV. The reaction products are isolated by conventional methods. In general, the reaction mixture is acidified, optionally with water, and then the crystalline reaction product is filtered off.

The 2,4,5-trichloro-2- (1,1-dichloroethyl) -2H-imidazole of formula V, required as starting material in process d), is a known substance (cf. DOS 25 50-157).

Suitable reducing agents for process variant d) are preferably noble metals, such as platinum or palladium, activated. hydrogen or also reducing agents such as hydrogen iodide or hydrogen bromide, optionally in the presence of sulfur dioxide.

As a diluent, in variant a) of process d1), the diluents can be used, depending on the reduction used; various solvents. Thus, in the catalytic hydrogenation, aromatic hydrocarbons such as benzene, toluene and xylene, cyclic ethers such as dioxane and tetrahydrofuran are preferably used as diluents. When the reaction is carried out with chemicals such as hydrogen bromide or hydrogen iodide, suitable diluents are preferably inert, water-immiscible organic solvents, such as methylene chloride, chloroform or toluene.

The reaction temperatures can be varied within a certain range in process variant (a). In general, it is operated at temperatures between 0 ° C and 50 ° C, preferably between 10 ° C and 30 ° C.

In carrying out process variant a) d) is used per 1 mole of 2,4,5-trichloг ^{t2tl-l-dichloro:} rethyl) -2H-imidazole of formula V with either an excess of catalytically activated hydrogen, or · at least two moles of a chemical reducing agent, such as hydrogen bromide or hydrogen iodide. Hydrogen bromide and hydrogen iodide can be used advantageously in the form of their commercially available concentrated aqueous solutions (azeotropes). It has a favorable effect on the yield of the end products if the reaction mixtures are saturated with gaseous sulfur dioxide.

The isolation of the final product is carried out by conventional methods. In general, the solvent is first evaporated, the remaining residue is suspended in water, then neutralized. and .filtered. The product can be purified by overlapping, for example from acetonitrile or by sublimation in vacuo.

Suitable reactants for process variant d) are alkali metal iodides and alkaline earth metal iodides. These preferably include sodium iodide, potassium iodide and calcium iodide.

All conventional lower aliphatic ketones can be used as diluents in process variant d). Particularly preferred is acetone.

The reaction temperatures can be varied within a wide range in process variant d). In general, temperatures between -20 degrees Celsius and 4-100 ° C, preferably between 0 ° C and 60 ° C, are employed.

In carrying out variant (b) of process d), at least 1 mol of alkali metal iodide or at least 1.5 moles of alkali metal iodide is used per mole of 2,4,5-trichloro-2- (1 ₎ 1-dichloroethyl) -2H-midazole of formula mjol of an alkaline earth metal iodide. Preferably, a system consisting of a mixture of sodium iodide and acetone is used. Sodium iodide can be used in this process. a considerable excess without disturbing side reactions. The reaction product is isolated by conventional methods. In general, the reaction mixture is poured into water by the addition of a reducing agent such as aqueous sodium bisulfite solution to remove the free iodine present and then filtering the reaction mixture.

Suitable reactants for process variant d) are alkali metal bromides and alkali metal bromides. These preferably include sodium bromide, potassium bromide and calcium bromide. Particularly preferred is potassium bromide.

All conventional lower aliphatic nitriles or lower aliphatic ketones can be used as diluents in process variant d). Particularly preferred is acetonitrile or acetone.

The reaction temperatures can be varied within a wide range in process variant d). In general, temperatures between 50 ° C and 150 ° C, preferably between 70 ° C and 120 ° C, are employed.

When implementing variant y). In process d), at least 0.5 moles of alkaline earth metal bromide is used per mole of 2,4,5-1,5-bis-2- (1,1-dichloroethyl) -2H-imidazole of formula V. Particularly preferred are potassium bromide systems. and acetonitrile and sodium bromide and acetone. The alkali metal bromide is preferably used in a 5 to 10-fold molar excess. The reaction products are isolated by conventional methods. Usually, after cooling, the reaction mixture is poured into water (5-10 times the amount), the aqueous suspension is filtered, the residue is washed with water and dried.

The 4,5-dichloroimidazole derivatives required as starting materials for carrying out process e) are defined by the formula VI. In this formula, Hal is preferably chlorine or iodine.

The compounds of formula VI are not yet known. However, these compounds can be prepared according to variants (a) and (d) of process d).

Suitable dehydrohalogenating agents in process variant (e) are all the reagents which are usually used for such reactions. These include inorganic and organic bases, such as alkali metal hydroxides and alkaline earth metal hydroxides, and optionally carbonates and bicarbonates of alkali and alkaline earth metals, organic amines such as tertiary aliphatic amines, for example triethylamine. Particularly preferred are non-quaternizable aliphatic amines such as ethyldiisopropylamine (Hunig's base).

Suitable inert solvents in process variant a) are all inert organic solvents. Preference is given to ethers such as diethyl ether, dioxane or tetrahydrofuran. It is furthermore possible to use the amine used for the cleavage of hydrogen halide 209945 at the same time as solvent ¹ . In addition, water can also act as a diluent.

The reaction temperatures can be varied within a wide range in process variant (a). In general, temperatures between 0 ° C and 100 ° C, preferably between 10 ° C and 50 ° C, are employed.

In process variant (a), 1 mole or greater of ¹ to almost any excess dehydrohalogenating agent is used per mole of 4,5-dichlorotrimidazole VI derivative of formula VI. The reaction product is isolated by conventional methods. In general, the reaction mixture is poured into water, acidified and the resulting crystalline reaction product is filtered off.

In carrying out process variant β), the 4,5-dichloroimidazole derivative of formula VI is hydrolyzed with water. At the same time, the water acts as a reaction medium and can therefore be used in large quantities.

All of the usual bases or basic salts can be used as the acid-binding agents in process variant e). Preferred are the alkali metal salts of lower aliphatic carboxylic acids, with sodium formate being particularly preferred.

The reaction temperatures can be varied within a wide range in process variant e). In general, the reaction is carried out at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

When performing variant β) of the procedure. e) a considerable excess of water is used per 1 mol of the 4,5-dichloroimidazole derivative of the formula VI, in order to achieve complete conversion, the hydrohalogenic acid resulting from the hydrolysis must be continuously removed from the reaction mixture. In principle, this is achieved by the controlled addition of a total of 1 mol of any conventional base to a strongly acidic pH (pH 1 to 2 of the reaction mixture is adjusted to a weakly acid to neutral range (pH 5-7), the prevention of side reactions must in no case exceed pH 7. In a preferred embodiment of variant (b) of process (e), hydrolysis is carried out: in the presence of at least 1 mol of a lower alkali metal aliphatic carboxylic acid salt. Sodium formate, which can be used in any excess, is preferably used.

Isolation of the reaction product is accomplished by conventional methods. In general, the aqueous phase is separated off by heat, allowed to cool and the reaction product which precipitates in the crystalline state is filtered off.

The 4,5-dichloroimidazole derivatives required as starting materials in process fj are defined by Formula VII. In this formula, the symbols X ³ , X ⁴ and X ^{5 are} preferably those already mentioned in the description of the compounds of the formula I according to the invention as being preferred for these symbols.

The compounds of formula VII have not been known. However, these compounds can be produced according to process variant b) or process variant β).

The compounds that are further required in process f1 as starting materials are generally defined by Formula VIII. ¹ In this formula, Y 'preferably represent those radicals - which already in connection with the description of the compounds of formula I They report to the invention mentioned as preferred for Y, but are not a radical of formula

Further, Y 'is preferably amino.

The compounds of formula VIII are known or can be prepared in principle by known methods.

All conventional inert organic solvents as well as water can be used as diluents in process f).

In process f), the reaction temperatures can vary widely. range. Generally pracuje- at temperatures between 20 ° C and 120 ° C výhodně- between 80 ° C '-A 110 ^Q C.

In process f) at least 1 mole of the compound of formula VIII is used per mole of the 4,5-dichloroimidazole derivative of formula VII. The reaction products are isolated by conventional methods. In general, the procedure is to filter out the precipitate which is formed, if any, by the foregoing acidification. As the organic solvent, the reaction mixture is concentrated, water is added, the reaction mixture is heated, and then the process is carried out as described above.

The 4,5-dimethyl-2-ethyl-2-ethynylmethyloazoline, which is required as starting material in carrying out process (g), is defined by Formula IX. This substance has not been known yet. However, this substance can be prepared by the process ej, variant etc.

As the chlorinating or brominating agents, all of the agents normally usable for such purposes can be used in process gj. Preference is given to chlorine, sulfuryl chloride and straw.

All conventional inert organic solvents can be used as diluents in process g). Chloroform, methylene chloride and carbon tetrachloride are preferred.

The reaction temperatures in process g) can be varied within a wide range. SE- generally carried out at temperatures between 0 ° C and 50 ° C, preferably of between ¹⁰ ° C and 30 ° C.

In process g), a different amount of chlorinating agent or brominating agent drop is used to react with 4,5-dichloro-2-ethylimidazole of formula IX, depending on the desired reaction product. In order to produce a reaction product which is ^one in the side chain is saturated, then · used per 1 mole

Of 4,5-dichloro-2-ethynylimiduzoil (IX) with at least 2 moles of a chlorinating or brominating agent. If only 1 mol of 1a is used, then compounds with an unsaturated chlorination or bromination reagent side chain are formed. The reaction products are isolated by conventional methods. In many cases, the reaction product is obtained directly in crystalline form so that it can be filtered off.

The 4,5-dichloroimidazole derivatives required as a starting material in the process hj are defined by formula X. In this formula, χΐ is preferably hydrogen, chilior, bromine or iodine. X ³ and X ⁴ are preferably those already mentioned in the description of the compound of formula I according to the invention as being preferred for X 3 and X ⁴ .

4,5-Dichloroimidazole derivatives of formula X have not been known hitherto. However, these compounds can be prepared by the process of the invention.

All of the customary reagents useful for this purpose can be used as the chioring or brominating agents in process h). Chlorine, sulfuryl chloride and bromine are preferably used.

All conventional inert organic solvents can be used as diluents in process h). Chloroform, methylene chloride and carbon tetrachloride are preferred.

The reaction temperatures in process h) may vary widely. range. In general, the reaction is carried out at temperatures between 0 ° C and 50 ° C, preferably between 10 ° C and 30 ° C.

In carrying out process (h), 1 mol or also an excess of a chlorinating or brominating agent is used per mole of the 4,5-dichloroimidazole derivative of the formula. The work-up is carried out by conventional methods. In general, the reaction product is optionally filtered off after crystallization in the crystalline form.

The 4,5-4 dichloroidazolyl derivatives required as starting materials in process (i) are defined by formula XI. In this formula, Hal 'is preferably chlorine, bromine and iodine. X® and X ⁷ are preferably chlorine or bromine ·. and

The compounds of formula XI have not yet been known. However, these compounds can be prepared by the process of the invention.

Suitable solvents in process i) are all customary lower aliphatic nitriles. Preferably acetonitrile is used. ^J

The reaction temperatures can be varied within a wide range in process (i). In general, it is carried out at temperatures between 50 ° C and 150 ° C, preferably between 60 ° C and 100 ° C.

In process i), the compound of formula XI is heated for some time in a lower aliphatic nitrile. The reaction mixture is then worked up by conventional methods. In general, after cooling, the reaction mixture is filtered, then water is added and the resulting crystalline product is filtered off.

The active substances according to the invention influence the growth of the plants and can therefore be used as defoliation agents, desiccants, weed control agents, germination control agents and in particular as weed control agents. Weed, in the broadest sense, means all plants that grow where they are not desired. Whether the compounds of the invention act as total or selective herbicides depends essentially on the amount applied.

The active compounds according to the invention can be used, for example, in the following plants:

dicotyledonous weeds of genera:

mustard (Sinapis), watercress (Adhesives), bedstraw (Galium ·), chickweed (Stellaria.), chamomile (Matricaria), chamomile (Anthemis), five-leaf (Galinsog-a), goosefoot (Chenopodiúm), nettle (Urtica) (Senecio), Pigweed (Arnaranthus), Purslane (Portulaca), Beetle (Xanthium.), Bindweed (Convolvulus), Bitterwort (Ipomoea), Raspberry (Polygonum), Combination · [Sesbania], Ambrosia (Ambrosia), Thistle (Cirsium) , Thistle (Carduus), Milk (Sonchus), Eggplant (Solanum), Mustard (Rorippa), Riotala, Lindernia, Deadnettle (Lamium), Speedwell (.Veronica), Abutilon (Abutilon), Emex, Durman (Datura), Violet ( Viola, Galeiopsis, Poppy (Papaver), Cornflower (Cenitaurea).

dicotyledonous plants of genera:

cotton (Gossypium), soybean (Glycine), beet (Beta), carrot (Daucus), bean (Phaseolus), peas (Pisum), potatoes (Solanum), flax (Linum), bitterwort (Ipomoea), vetch (Vicia), tobacco (Nicotiana), tomato (Lycopercison), peanut (Arachis ·), kale (Brassica), lettuce (Lactuca), cucumber (Cucumis), gourd (Cucurbita).

monocotyledonous weeds of genera:

Hedgehog (Echinochloa), Shear (Setaria), Prosoi (Panicům), Dew [Digitaria], Blojjek. (Phleum), Meadow-grass (Poa), Ki-oyster (Festuca), eleusino (Eleusine), Brachiaria, Eyed (Lolium), Brome (Bromus), Oats (Avena), Cory (Cyperus), Sorghum (Sorghum), Cheese (Agropyron) ), trioskut (Cynodoin), Monochoria, Fimbristylis, arrowhead (Segittaria), Eteocharis, Scirpus, Paspalum, Ischaerbum, Sphenioclea, Dactyloctenium, distemper (Agrostis), fox (Alopecurus), chundelka (Apera).

monocotyledonous plants of genera;

rose (Oryza), maize (Zea), wheat (Triticum), barley (Hordeum), oats (Avena), rye (Secaile), sorghum (Sorghum), millet · (Panicum), sugarcane (Saccharum), pineapple (Ananas) ), asparagus (Asparagus), garlic (Allium).

However, the use of the active compounds according to the invention is in no way limited to these genera but also to other plants in the same way.

The compounds according to the invention are suitable, depending on the concentration, for the total control of weeds, for example on industrial and railway surfaces and on roads and squares, possibly with trees.

The compounds of the invention may also be used to control weeds in long-term crops such as forest crops, ornamental trees, fruit trees, vineyards, citrus, butternut, banana, coffee, tea, rubber, coconut, cocoa, berry and hop plants, and to selectively control weeds in annual crops.

In addition to the strong weed control, the active compounds according to the invention show in particular also a very good selective herbicidal activity in different crops. Thus, the active compounds according to the invention are suitable, for example, for the selective control of weeds in maize, cotton and cereals.

The active substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, dusts, pastes, soluble powders, granules, concentrates based on suspensions and emulsions, active substances impregnated with natural and synthetic substances, e-mail particles coated with polymeric substances.

These compositions are prepared in a manner known per se, for example by mixing the active compounds with the excipients, i.e. with liquid solvents and / or solid carriers, optionally using surfactants, e.g. emulsifiers and / or dispersants and / or foaming agents. If water is used as the carrier, organic solvents can also be used as co-solvents, for example. · As liquid solvents are essentially: aromatics, such as ^1, xylene, toluene, ^or! alkylnaphthalenes, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffinic hydrocarbons, for example petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanome, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water.

Suitable solid carriers are, for example, natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Crushed and fractionated natural stone materials, such as limestone, marble, pumice, sepicilite and dolomite, as well as synthetic granules of organic material such as sawdust, coconut shells, corn sticks and tobacco stems are suitable solid carriers for the preparation of granulates. . Suitable emulsifiers and / or foaming agents are nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty acid ethers, e.g. and methylcellulose.

The compositions of the invention may contain adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers, such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

. In addition, these compositions may contain colorants such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic colorants, such as alizarin dyes and metallic azo-phthalocyanine dyes, as well as trace elements, such as iron, manganese salts, Boron, copper, cobalt, molybdenum and zinc.

Concentrates generally contain between 0.1 and 96% by weight, preferably between 0.5 and 90% by weight, of active ingredient.

Effective Subclass ^la tk ^{y y} n and ^l in the cut can be employed for combating weeds alone or in farm · means and also as mixtures with known herbicides, and these substances may be admixed to the finished formulations or · immediately before application. Mixing with other known active ingredients, such as fungicides, insecticides, acaricides, nematocides, bird ozone control agents, growth agents, plant nutrients and soil conditioners is also possible.

Úiniré ^la t ^ky may aphkovai: as such, as their formulations or • in the use forms, prepared from these formulations, as the use solutions, suspensions, emulsions, powders, pastes and granules. The application is carried out in the usual manner, for example by pouring, spraying, dusting or sprinkling, etc.

The active compounds according to the invention can be applied both before and after the emergence of plants.

The application is preferably carried out pre-aggressively, i.e. before the emergence of the plants. The active compounds according to the invention can also be incorporated into the soil before sowing.

The amount of active ingredient used may vary within wide limits. This amount depends essentially on the type of effect desired. In general, the application rate is between 0.1 and 10 kg of active substance per ha, preferably between 0.1 and 5 kg / ha.

The good activity of the active compounds according to the invention results from the following examples.

In the following examples, the compounds of the formulas below are used:

(known substance) (4,5-dichloroimidazole-2-carboxylic acid ethylamide)

Example A

Preemergence test solvent: 5 parts by weight of acetone emulsifier: 1 part by weight of alkyl aryl polyglycol ether

Effective ^p rost ^of Formulation ^P and the ^straight Ravi SIMIS so that one part by weight of active compound with the stated amount of solvent added the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

The seeds of the test plants are sown in normal pore and after 24 hours they are covered with the active agent. The amount of water per unit area is! practically constant. The concentration of the active ingredient in the formulation is not important, only the consumption of active ingredient per unit area is critical. After three weeks, the degree of damage to the test plants is determined, expressed as a percentage of the development of the untreated control plants. · Means% = no effect (as in untreated control plants)

100 '% == total plant destruction.

^Úč in.né substance ^P · ^d of le vynátezu no. ^6, 9 and ^4, and 19 exhibit · · · This assay better efficacy than Compound A, which is known in the art.

The results are shown in Table A:

ω ω and o> сл

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000000000000 (DCOCDCOCOCOCDCOOOOOCOCO e

.2 o ril

CD OOOOOOOOOOO COCOCDCDOOOOOOOOCDcaČOCÓ

Pre-emergence test

44 'CD CD '0) bh ri ri > 6

'cd ~ s - <' S 'Э

N

2В

Post-emergence solvent test: 5 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether

The active ingredient is prepared by mixing 1 part by weight of the active compound with the indicated amount of solvent, adding the indicated amount of emulsifier and diluting the concentrate to the desired concentration in water.

Prepared; The test plants are sprayed with an active agent of 5 to 15 cm in height in order to achieve the desired consumption of active substance per unit area. The concentration of active ingredient in the spray is selected to consume 2000 liters of water per hectare, in which the required amount of active ingredient is present. After weeks, the degree of plant damage was assessed and expressed as the percentage of damage compared to the development of untreated control plants.

In doing so, it means:

% = no effect (as in untreated control plants)

100% = complete destruction of plants.

In this test, the compounds of Examples 6, 9, 14 and 19 according to the invention show better efficacy than the comparative substance A.

The test results are summarized in Table B below:

Table Β

Post-allergenic test effective amount used Echino- Galine- Stella- Urtica Matri- Dau- Siná- oves cotton wheat maize active substance chloa soga ria caria cus pis

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OOOO CO. Oo OO Ml

O O o

CD M O

O rH

O o CD M <

o o O OO oO ooooOoooo rH t — I Η H oooooooooo o o o Tj φ 77 o o tp t-I r-l r-l

CO ooooooooo 'Φ CM what CM yy Ф 1S yy Mi

LO iry ID LO tH o 'r-l o rH o r-l 0' r-l 0 ~ м3, <I ——Д O 3

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N

Examples illustrating the method of production of active ingredients:

Example 1

1

С £ Л ₅ H

a) 480 g [5 moles] of 2-ethylimidazole are added under stirring and cooling to lit 2 liters of x-phosphorus pentachloride pre-cooled to 5 ° C and then at a temperature between 20 and 40 ° C until the end of the exothermic reaction is introduced. hydrogen chloride gas. Thereafter, the reaction mixture is heated to reflux (about 107 ° C) and 2490 g (35 mol) of chlorine gas are introduced there for about 5 hours. After distilling off the phosphorus oxychloride in a vacuum-water pump up to a bath temperature of 100 ° C, the residue is slowly stirred at room temperature with 1.75 liters of formic acid. The colorless crystalline powder thus formed is filtered off, washed with formic acid and then thoroughly washed with water. After drying, 520 g (30.8% of theory) of 4,5-dichloro-2-pentachloroethylimidazole of melting point 232 DEG C. are obtained (long thin needles after recrystallization from gasoline for washing _; or from a small amount of anhydrous acetonitrile). .

IC spectrum - (KBr technique):

1540, 1450, 1410, 1358, 1250, 1205, 1040, 780, 665, 555 ^cm-first

(b) 125 g (1,3 mio-12-ethylimidazole) are added to 500 ml of phosphorus pentachloride pre-cooled to about 5 ° C with stirring and cooling, followed by heating the reaction mixture to reflux (about 107 ° C). 300 g (4.22 mol) of chlorine are introduced into this mixture over a period of 3 hours, the solvent is distilled off in vacuo and the residue is stirred at about 20 DEG C. with 400 ml of formic acid. as in a) and also represents 4,5-dichloro-4-pentachloroethyl imidazole.

Yield 63 g, corresponding to 38% of theory, based on the chlorine used in an amount less than the equimolar amount.

(c) A solution of 96 g (1,0-mol) of 2-ethylimidazole in 400 ml of 1,1,2,2-tetrachloroethane is introduced at a temperature of between 110 and 115 ° C for 480 hours (4,5 g) ( 6.75 mol) of chlorine. Thereafter, the tetrachloroethane is distilled off in a water pump vacuum to a bath temperature of 100 ° C. The cooled residue is stirred with 200 ml of pure formic acid, whereupon a colorless powder precipitates and, after suctioning, penetrates! Formic acid and drying afforded 4,5-dichloro (103 g, 31.6%)

- 2-pentachilomethyl-imidazole - which is identical to the compound obtained under (a). The pure compound is also obtained on reuse even if it is sublimated from the crude product at about 125 ° C / 1.3 Pa.

Example 2

a) To a stirred mixture consisting of 16.1 g (0.1 mol) of 4,5-dichloro-2-ethinylimidazole (preparation see Example 13) and 100 ml of chloroform are cooled for 1 hour at 15 to 20 °. C, 34 g (0.25 mol) of sulfuryl chloride was added dropwise. After stirring for 2 hours, the solid was filtered off and washed with a small amount of chloroform. There was thus obtained 4,5-dichloro-2- (1,1,2,2-tetrachloroethyl) imidazole of melting point 180 ° C.

IC spectrum (KBr technique):

1547, 1465, 1427, 1360, 1260, 1248, 1208, 1055, 1015, 830, 770, 740, 682, 596, 555 cm &^lt; -1 ^&gt;.

b) 120 g (1.25 mol) of 2-ethyilimidazole are added to 500 ml of thionyl chloride with stirring and cooling, then the reaction mixture is heated to reflux (76 DEG C.) and refluxed at this temperature for 5 hours. 530 g (7.5 mol) of chlorine are introduced in. After distilling off the thionyl chloride in a water pump vacuum up to a bath temperature of 100 [deg.] C., the residue is stirred at room temperature with about 300 ml of formic acid. This gives 72- g (19% of theory) of 4,5-dichloro-2- (1,1,2,2-tetrachloroethyl) imidazole, which is identical to the compound obtained in - above - and ).

Example 3

Cl

Cl

A suspension of 68 g (0.2 mol) of 4,5-di-chloro-2-pentachloroththylimidazole in 1.2 liters of water is heated to boiling and about 70 to 100 ml of water are boiled within 2 hours. . The reaction mixture is filtered and the residue on the filter is dried. 46 g (81% of theory) of 4,5- (dichloro-2-trichtoroacetylimidazole) are obtained.

IC spectrum (KBr technique):

1700, 1525, 1410, 1270, 1200, 1090, 1050,

977, 845, 810, 754, 700, 660, 621, 609, 527 (30.4

Example 7

In an analogous manner to that described in Example 3, 4,5-dichloro-2-dichloroacetylimidazole of melting point 1-2 DEG C. is obtained from 4,5-dichloro-2- (1,1,2,2-tetrachloroethyl) imidazole.

IC spectrum, (KBrj technique:

1692, 1535, 1423, 1412, 1190, 1075, 965, 808, 785, 758, 608 cm &^lt; -1 & gt ^; .

Example 1 a d 5

H

1 'II ^ct i II f HO

Analogous; as described in Example 3, 4,5-dicloro-2-chloroacetyrimidazole, m.p. 182 DEG C., is obtained from 4,5-dicMor-2- (1,1,2-trichloroethyl-imidazole (preparation see Example 21)). from a small amount of acetonitrile).

IC Spectrum! (KBr technique):

1683, 1415, 1329, 1185, 1062, 1045, 945, 781,740 cm ^-1 .

Example 1 a d 6

H

To a solution of 150 g (1 mol) of sodium iodide in 900 ml of acetone at room temperature with stirring is added 50 g (0.148 mol) of 4,5-dichloro-2-pentachloroethylimidazole. After lhodin; about 500 ml of acetone is distilled off by further stirring and 2 liters of water and 40% aqueous sodium bisulfite solution are added to the residue to completely disappear the brown color of iodine. Then the reaction mixture is filtered, the product is washed with water and dried.

Yield: 37 g (93.5% of theory) of 4,5-dichloro-2-trichlorvinylimidazole having a melting point of 168 degrees Celsius.

IR spectrum; (KBr technique):

1590, 1542, 1458, 1405, 1265, 1061, 1042,

965, 958, 869, 770, 700, 556 cm &^lt; -1 ^&gt;.

To a solution of 285 g (7.5 mol) of sodium borate in 1.3 liters of water is added 506 g (1.5 mol) of 4,5-dichloroethane with stirring and cooling at 15-25 ° C for about 5 hours. After stirring for 3 hours, the reaction mixture is acidified with hydrochloric acid to a pH of about 1 while cooling. The precipitate is filtered off, then boiled with about 4 liters of water with stirring, filtered boiling hot and the residue washed several times on the filter. After drying, 377 g (93.5% of theory) of 4,5-dichloro-2- (2,2,2-trichloroethyl) imidazole of melting point 224 DEG C. are obtained.

IR spectrum (KBr technique):

1557, .1425, 1370, 1248, 1222, 1194, 1045, 1035, 1011, 946, 840, 730, 709, 558 cm &^lt; -1 ^&gt;.

Example 8

Cl ct

In an analogous manner to that described in Example 7, 4,5-dichloro-2- (2,2-dichloroethyl) imidazole is obtained from 4,5-dichloro-2- (1,1,2,2-tetrachloroethyl Jimidazole), m.p. 143 ° C (from cyclohexane).

IR spectrum [KBr technique]:

1577, 1560, 1434, 1410, 1215, 1038, 1015, 925, 810, 720, 688, 648 cm &^lt; -1 ^&gt;.

Example 9

a) 45-Dichloro-2- [2,2,2-trichloroethyl) imidazole was added to an excess of saturated aqueous sodium bicarbonate solution and heated to boiling to give a clear solution. After cooling, the reaction mixture is acidified with dilute hydrochloric acid, the precipitate formed is filtered off ¹ , washed with water and dried. There was thus obtained 4.5209945

chloro-2- (2,2-dichlorovinyl) imidazo ^s lo, mp 134 ° C. The compound may sublimit at 110.0 / 1.3 Pa.

IC spectrum (KBr technique):

1625, 1550, 1465, 1414, 1235, 1035, 920, 835, 675, 539 cm @ -1.

T _W , ·

b] A mixture consisting of 67 g (0.25 mol) of 4,5-dichloro-2- (2,2,2-trichloroethyl) imidazole, 200 ml of diOxane and 28 g (0.277 mol) of triethylamine is stirred under reflux for 1 hour. reflux condenser. After cooling, the reaction mixture is poured into 1 liter of water, acidified with hydrochloric acid, the product is filtered off, washed with water and dried. Subsequent sublimation at 110 ° C / 1.3 Pa yielded 47.5 g (82% of theory) of 4,5-dichloro-2- (2,2-dichlorvinyl) imidazole, which was identical to the compound obtained under a).

He did

a) A solution of 50 g (0.186 mol) 2,4,5-trichloro-2- (1,1-dichloroethyl) -2H-imidazoil in 450 ml toluene was charged into a glass autoclave together with 5 g catalyst (5%). palladium-on-charcoal) and hydrated at about 20 ° C for 5 hours. The reaction mixture is then evaporated in vacuo to a residue. rotary evaporator to dryness, the residue is suspended in water and neutralized with aqueous sodium bicarbonate solution. The product is then filtered off, washed with water and dried. Subsequent extraction with hot acetonitrile gave, after cooling and optionally concentration of the filtered acetonitrile solution, 4,5-dichloro-2- (1-chloro-vinyl) imidazole as coarse colorless crystals, m.p. 210 DEG C. (decomposition). The compound can sublimate at 100 ° C / 13.3 Pa.

b) A mixture of 67 g (0.25 mol) of 2,4,5-trichloro-2- (1,1-dichloroethyl) -2H-imidazole, 28.3 g (0.275 ml) of sodium bromide and 350 ml of acetone is stirred for 1 hour. at reflux (58 ° C). After cooling, the reaction mixture is poured into 2 liters of water, the precipitate is filtered off, washed with water and dried. 41 g (85% of theory) of 4,5-dichloro-2- (1-chlorvinyl) imidazole are obtained, which is identical to the compound obtained under (a).

IC spectrum (KBr technique):

1622, 1550, 1477, 1430, 1355, 1265, 1120,

1050, 1009, 883, 795, 734 cm &^lt; -1 ^&gt;.

Included ^С * П)

Cl 2 N ^{C = CH} 2

H

To a stirred mixture consisting of 1600 g (10.6 mol) of sodium iodide in 2 liters of acetone is added. cooling during ¹ 2 hours at a maximum temperature of 50 ° C dropwise a solution of 806 g (3 mol) of 2,4,5-trichloro-2- (1,1-dichloroethyl) -2H-imidazole (for production see DOS 2 550157) in 1, 5 liters of acetone. The reaction mixture was then added to a mixture of 12 liters of water and 1600 g of a 40% aqueous solution of sodium bisulfite, filtered, washed with water and dried.

Yield: 770 g (89% of theory) of 4,5-dichloro-2- [1-iodinyl] imidazole. Decomposition temperature about 21.5 ° C.

Example 12

a) A mixture consisting of 400 g (3.36 mol) of potassium bromide, 135 g (0.5 mol) of 2,4,5-trichloro-2- (1,1-dichloroethyl) -2H-imidazole and

Acetonitrile (1.5 L) was stirred at reflux (81 ° C) for 10 hours. After cooling, the reaction mixture is poured onto 7.5 liters of water, the precipitate is filtered off, washed with water and dried. 121 g (87% of theory) of 4,5-dichloro-2- (1-chloro-2-bromovinyl) imidazole, m.p. 190 DEG C. (from toluene), were obtained.

IR spectrum (KBr technique):

1585, 1540, 1465, 1402, 1370, 1260, 1205, 10510, 895, 870, 775, 740, 690, 622, 540 cm ^-1 .

b) 3.58 g (0.01 mol) of the compound of the formula

(preparation see Example 22) was boiled in 30 ml of acetonitrile for 5 minutes. After cooling, the reaction mixture is poured onto 200 ml of water, the precipitate is filtered off, washed with water and dried. 2.60 g (94% of theory) of 4,5-dichloro-2- (1-chloro-2-bromovinyl) imidazole are obtained, which is identical to the compound obtained under (a).

Example 13

CU _N • c! L ct nc = cw

H

a) To a suspension of 28.9 g (0.1 mol) of 4,5-dichloro-2- (1-iodinyl) imidazole in 50 ml of dioxane Sie at room temperature add 25 g (0.25 mol) of triethylamine while heating a solution is formed. After stirring for half an hour, the reaction mixture was poured into 1 liter of water, the mixture was slightly acidified with dilute hydrochloric acid, the product was filtered off, washed with water and dried.

Yield: 11.1 g (69.0% of theory) of 4,5-dichloro-2-ethinyrimidazole. Decomposition temperature about 185 ° C. The compound is sublimable at 100 ° C / 1.3 Pa.

(b) To a solution of 28.9 g (0.1 mol) of 4,5-dichloro-2- (1-iodo vinyl) imidazoil in 150 ml of dioixah, 32.3 g (0.25 mol) are added at 20 ° C. ethyldiisopropylamine (Hunig's base). After stirring for 1 hour, the reaction mixture is poured into 750 ml of water and slightly acidified with dilute hydrochloric acid, the mixture is filtered, the product is washed with water and dried. 11.7 g of 4,5-dichloro-2-ethinylimidazole are obtained. The filtrate was concentrated in vacuo to about 1/3 of the original ¹ volume, and an additional 4.3 g of 4,5-dichloro-2-ethinylimidazole could be obtained. Total yield 16.0 g (99% of theory).

IC spectrum (KBr technique):

3295, 2125, 1563, 1545, 1470, 1390, 1050, 1020, 875, 702, 688, 610 cm ^-1 .

Example 14

C-CH.

I II ³ HO

а) To a stirred solution of 136 g (2 mol) of sodium formate in 4 liters of refluxing water, 289 g (1 mol) of 4,5-dichloro-2- (1-iodinyl) imidazole are added in portions and the mixture is further stirred reflux until dissolution. Thereafter, the still boiling solution is separated from the small amount of dark; oil at the bottom of the reaction flask and allow the clear solution to cool. Pale yellow needles of 1 cm in length are deposited and are filtered off cold, washed with a small amount of cold water and dried. Yield: 125 g (70% of theory) of 2-acetyl-4,5-dichloroimidazole, m.p. 162 DEG.

b) By repeating the entire process using the mother liquor obtained as described above, about 80% yield of 2-acetyl-4,5-dichloroimidazole is used instead of pure water.

(c) The procedure is analogous to (a) except that the appropriate molar amount of 4,5-dichloro-2- (1-chloro-vinyl) imidazole is used instead of 4,5-dichloro-2- (1-iodinyl) imidazole. wherein 2-acetyl-4,5-dichloroimidazole is also obtained in comparable yields.

IC spectrum (KBr technique):

1666, 1432, 1408, 1212, 1050, 993, 950, 785, 693, 619, 580, 552, 512, 492 cm ^-1 .

Example 15 ^C1 xi

Cl N C-CH 3

I и ³

H NOH

A mixture of 8.95 g (0.05 mol) of 2-acetyl-4,5-dichloroimidazod, 200 ml of water and 6.95 g (0.1 mol) of hydroxylamiine hydrochloride is first mixed with the addition of 4.60 g at room temperature. (0.055 mol) of sodium bicarbonate (in portions) and then the mixture is heated to boiling until a clear solution is obtained. The precipitate which crystallizes upon cooling is filtered off, washed with water and dried.

Yield: 8.7 g (97% of theory) of the oxime of the above formula. Melting point 213 degrees C (decomposition).

Example 16

8.95 g (0.1 mol) of 2-acetyl-4,5-dichloroimidazole are dissolved in a mixture of 20 g of hydrazine hydrate and 200 ml of water and heated briefly to boiling. After cooling, the mixture was acidified with hydrochloric acid and a precipitate formed. After filtration, washing with water and drying, the azine obtained above is obtained in a practically quantitative yield; The decomposition temperature of this compound is greater than 290 ° C.

^Cl X +

Cl N C = N-NH-C-NH

I и <·

H p

3β

17.9 g (0.1 billion) of 2-acetyl-4,5-dichloroimidazoil are dissolved in 800 ml of water while warm and a deep solution of 15 g (0.165 mol) of thiosemicarbazide in 200 ml of water is added. After about half a minute a colorless precipitate formed, which upon cooling was filtered off, washed with diiodium and dried. There is thus obtained a thiosemicarbazine of the above formula with a melting point above 290 ° C.

Example 1 8.

Dissolve 17.9 g (0.1 mol.) Of 2-acetyl-4,5-dichloroimidazole in hot water in 800 ml. Of water, add ¹ 14 g. boiling. After cooling, the reaction product is filtered off, washed with water and dried. Obtained in practically quantitative yield phenylhydrazone above structural formula · · ^1, mp 175 ° C.

Example 19

In an analogous manner, 4-chlorophenylhydrazone of the formula is obtained

O · C%

Ct H N (C) N-NH4 C (H) (prepared; see Example 21) was boiled in 50 ml of acetonitrile for 10 minutes. The precipitate which crystallizes upon cooling is filtered off, washed with a small amount of cold acetonitrile and dried. Thereafter, at about 20 ° C, the precipitate is stirred with water, filtered. The filter residue is washed with water and dried. There was obtained 4,5-dichloro-4'-dichloro-vinylamidazole, m.p. 198 DEG C. (from a small amount of toluene).

IR spectrum (KBr technique):

1591, 1545, 1468, 1407, 1375, 1257, 1055, 916, 694, 632, 548 cm ⁴ .

b) To a solution of 50 g (0.33 mol) of sodium iodide in 150 ml of acetone was added 26.8 g (0.0772 mol) of the compound. of formula —N CiBr |

The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture is poured into about 1.5 liters of water and the iodine is removed by addition of 40% aqueous. Sodium bisulfite solution until discoloration. Subsequent filtration, washing with water and drying afforded 17.1 g (95.5% of theory) of 4,5-dichloro-2- (1,2-diyl-1,2,3-diol-1-ol). (yl) imidazole, which is identical to the compound obtained under (a).

c) To a solution of 8.05 g (0.05 mol) of the compound of formula

Mp 240 ° C (dec.).

Example 20

C = CH

H

Cl

Cl

H a

C = CHCl

a) 13.4 g (0.05 mol) of the compound of the formula

Cl

Cl

(production see Example 13) in 50 ml of chloroform, a mixture of 6.75 g (0.05 mol) of sulfuryl chloride and 50 ml of chloroform was added dropwise at 1 to 10 ° C over 1 hour. Then the reaction mixture was further stirred for 2 hours. The chloroform is then evaporated off under vacuum, the residue is stirred with about 100 ml of water at 20 DEG C., the mixture is filtered, the residue on the filter is washed with water and dried. The crude product is subsequently sublimed at 1.0 ° C / 1.3 Pa for purification. Colorless crystals of 4,5-dichloro-1,2-dichloro-vinyl imidazole are obtained, which are identical to the compound obtained under a).

H Cl

Example 21

To a stirred mixture consisting of 19.75 g (0.1 mol / l) of 4,5 - ((R) -2-chloro-2 '(1' - (R) -vinyl) imidazole and 10 ml of pure chloroform was cooled while cooling at room temperature. 15.0 g (0.11 mol) of sulfuryl chloride in about 40 ml of pure chloroform are added dropwise over a period of about 2 hours, then the reaction mixture is further stirred for about 3 hours at room temperature. It was washed with chloroform and dried to give 19.5 g (72.5% of theory) of a colorless, crystalline phenyl 4,5 (dichloro (2- (1,1,2-trichloroethyl) Jimidazole, m.p. 140 ° C) (decomposition). Additional amounts of product can be obtained by concentrating the mother liquor.

IR spectrum (Or technique):

1545, 1465, 1420, 1360, 1254, 1215, 1185, 1075, 1040, 1010, 950, 812, 760, 735, 688, 590 cm @ -1.

EXAMPLE 2 ^C S — N Cl i if i с ч Г--В

Η ^βΓ

To a stirred mixture consisting of 19.75 g (0.1 mol) of 4,5-dichloro-2 '(11-chloro-vinyl) imide (zole and 100 ml of pure chloroform) was stirred at about 10 ° C for 1 hour. 18.0 g (0.112 mol) of bromine in 50 ml of pure chloroform are added dropwise, after stirring for 4 hours at room temperature, the reaction mixture is filtered, the product on the filter is washed with chloroform and dried to give 32.0 g (89%). 5% of theory) of crystalline 4,5-dichloro-2- (1-chloro-dibibrinomethyl) imidazole, m.p. 160 DEG C. (decomposition).

IR spectrum (KBr technique):

0.542, 1462, 1417, 1357, 1253, 1219, 1168, 1072, 1040, 1004, 918, 795, 760, 680, 647, 618, 575 cm ^1st

Example 23

C-to. - n ClBr

J 1 ¹ cl · N · C-CH i I ¹

H Cl Ch

In a similar manner to that described in Example 21, 4,5-dichloro-2- (1,1,2-trichloro) is obtained from 4,5-dichloro-1- (1 (Chloro (2- (bromo-vinyl)) -imidazole). 180 DEG C. (decomposition) (from toluene).

IR spectrum (KBr technique):

1545, 1462, 1425, 1357, 1257, 1208, 1170, 1050, 1011, 825, 809, 767, 747, 680, 655 cm @ -1.

Example 2 4

H and e, C-CH

Br Br

In a similar manner to that described in Example 22, starting from 4,5-dichloro-2- (1-chloro-2- (1-chloro-1H-tribromethyl) imidazole in 91.5% yield).

IR spectrum (KBr technique):

1540, 1455, 1415, 1350, 1253, 1204, 1034, 1005 ^cm-first

Example 25

Ct

Ct

In a similar way as described. in Example 22, 4,5-dichloro-2- (1,2-dichloro-1,2-dibromoethyl) imidazole is obtained from 4,5- (1,1-dichloro-1,2-dichloro-vinyl) imidazole. m.p. 150 DEG C. (decomposition).

IR spectrum (KBr technique):

1540, 1454, 1415, 1350, 1252, 1230, 1203, 1165, 1135, 1043, 1005 dm ^first

Example 26

Cl i

CH-CCl ₃

To a stirred mixture consisting of 5.9 g (0.0255 mol) of 4,5-dichloro (2 ((2,2-dichlorvinyl) imidazoil) and 50 ml of pure chloroform is added dropwise while cooling at about 10 ° C). 2 hours 6 g (0.044 mol) sulfuryl chloride in 30 ml chloroform After stirring for 2 hours, the clear solution is evaporated to dryness in vacuo on a rotary evaporator and the residue is recrystallized from acetonitrile to give colorless crystals 4.5. -dichloro-2- (1,22,2-tetrachloroethyl) imidazole, m.p. 230 ° C (dec.).

IR spectrum (KBr technique):

1540 1463 1449 1420 1391 1305 1260

1237, 1037, 782, 759, 699, 684, 625 cm @ ^-1 .

Example 27

1.79 g (0.005 mol) of 4,5-trans-2- (1 < 6 &gt; -1,2-dibrolomethyl) imidazole (for preparation see Example 22) were obtained; Stir in a solution of 3.4 g (0.05 mol) of sodium formate in 50 ml of water for 10 minutes at room temperature. The reaction product is then filtered off, washed with water and dried. 1.20 g (93% of theory) of .alpha., 5-dichloro-2-bromoacetyliniidazoil are obtained. After recrystallization from cyclohexane, this compound melts at 177 ° C.

IR spectrum (KBr technique):

1676, 1421, 1408, 1372, 1177, 1063, 1049, 949, 767, 669 cm ^-1 .

The compounds of the following examples were prepared by the procedures described in the above Examples.

example number formula melting point starting material production of analo- (° C) see example gicky podle (recrystallized from) number example number

28 Clb — n Four-C-CHB-Ct! II Him 128 (cyclohexane) 25 27 Mar: 29 CBřCHB ^ 150 (decomposition) 13 22nd H 30 Cl ^ N С-СНВк 1 II & 140 (cyclohexane) 29 27 Mar: 1 ** H 0 31 Ct H N CBr = CHBr H 191 (cyclohexane) 29 6 CL v- N 32 1 ¹ li Ct CHBb-CBrCl, 220 (decomposition) 9 22nd H (CC1 ₄ ) 33 Cl —ή 1! Ct. CH = CHCl 223 (toluene) 8 9 H

Claims (2)

I will invent the subject 1. A herbicidal composition characterized in that Jato active ingredient ^one at least one derivative of 4,5-dichlorimidazoIu formula I H (I) wherein X 1 represents hydrogen, chlorine, bromine or iodine, X ^2, X ³ and X ⁴ are each a hydrogen, chlorine or bromine ·, X ⁵ is hydrogen or chlorine, and in addition X 1 and X ³ may together represent a C-C bond as well X ² and X ⁴ may together represent a C-C bond, or X 1 and X 2 together represent oxygen or = N-Y in which Y is OH and the —NH — C — NHR, II —NH — R1 radicals or in which: R represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R 1 is an optionally substituted phenyl group, Z is oxygen or sulfur; and R 2, R 3 and R 4 are each independently hydrogen or chlorine, but X ¹ , X 2, X ³ , X 4 and X 5 are not simultaneously hydrogen. 2. A process for the preparation of an active ingredient according to the general formula (I). characterized by; reacting with 2-ethylium ^; A compound of formula II ^H (II) or its hydrochloride with up to 7 moles of chlorine per 1 mol of 2-ethylimidazole, in solvent ¹ , which is inert under the reaction conditions.