CS252846B2 - Method of new 6-chlorobenzazolyloxyacetamides production - Google Patents

Description

It is an object of the present invention to provide a process for the preparation of the novel 6-chlorobenzazolyloxyacetamides of formula (I), comprising:

Cl (II) wherein

X is as defined above and

A denotes an electron withdrawable group, acting on glycolic acid amides of the general formula III h- _2- co-n (III) in which 1 2

R and R are as defined above, optionally in the presence of a diluent and optionally in the presence of an acid-binding agent, and optionally in the presence of a catalyst. *

The novel 6-chlorobenzazolyloxyacetamides of the formula (I) produced by the process according to the invention surprisingly show considerably better herbicidal activity against dicotyledonous weed control with comparably high tolerability by important crop plants and at the same time better fungicidal activity compared to benzazolyloxyacetamides such as N-methyl-2. -benzthiazolyloxyacetanilide, known in the art, which are the closest chemical and comparable compounds in terms of activity.

In addition to the compounds exemplified in the Examples, the following compounds of formula I may be mentioned in Table 1 below

Table

Cl, R ¹ 'R ² (I)

CH _O

CH ~

O oCHCH-

CH,

0, N

CH 2

CH,

CH_

F, C or N-R ^{2 C} 2 ^H 5

CH ₂ = CH-CH ₂ CH,

CH,

-nQ ^ -ch ₃ ο ₂ η ₅

CHHC C = _N-CH

Table 1 - continued if applicable

-N

O CH, O C.H - CH-

0 _{(CH3) 2} CHO- C ₂ H ₅ O-CH ₂ CH, 0 ch ₃ Cl 0 CH ₃ cf ₃ with CH ₃ CH ₃ O-CH ₂ - with CH _n HCsC-CH with CH ₃ O with CH ₃ O with ch ₃ F ₃ ^c - ^ch 2- with CH ₃ ^CF 3 with ch ₃ F Cl s * \ CHj Q · ch ₃ OjN. with CH ₃ ch ₃ with CHj ^f 3 ^c -

with CH ₃ O- CH-CH-1 CH ₃ 'with (CH ₃₎ CHO (ch ₃ ) ₂ ch- with ^C 2 ^H 5 CH ₂ = CH-CH ₂ - with CH ₂ -CH-CH ₂ - CH ₂ = CH-CH ₂ -

Table 1 - continued

R 'optionally

ch ₃

-N. ) ^C 2 ^h 5

-N

-N, I c ₂ h ₅ c ₂ h ₅

0 CH ch ₂ = ch-ch ₂ - with ^CH 3 CH ₂ = CH-CH ₂ - 0 CH ₃ O-CH ₂ - c, h, -ch- 3η ₃ with CH ₃ O-CH ₂ - C, H, -CH- k ₃ 0 CH ₃ (CH ₂ ) ₃ - CH ₃ (CH ₂ ) ₃ - with CH ₃ (CH _{2) 3} - CH ₃ < ^CH 2) ₃ - 0 ^C 2 ^H 5- _{(CH3) 2} CH-, with ^C 2 ^H 5 ^_ (ch ₃ ) ₂ ch- 0 (ch ₃ ) ₂ ch- C ₂ H ₅ OCH ₂ CH ₂ -O- with (ch ₃ ) ₂ ch- C ₂ H ₅ OCH ₂ CH ₂ -O-

►p

Table 1 - continued

X R ¹ R ² _R 1 or -B - **, R ^Z 0 ^CH 3- o-O- with ch ₃ - ^c, gc with ^CH 3- with ch ₃ - F 0 ch ₃ - ^f O ~ with ^CH 3 " ^ch 3 ^s “®— 0 ^CH 3 CK ₃ s - <g> - CH, S with ^ch 3 ~ with ^CH 3- ° 2 ^N ^ C}> - 0 ^CH 3- 0 ck ₃ nC ₄ H ₉ - with 0 with ^CH 3- nC ₄ H _g - -O -O 0 ^C 2 ^H 5 - CH ₂ = CH-

In the process according to the invention, 0.1 to 10 mol, preferably 0.8 to 1.2 mol of glycolic acid amide (III) and 0.5 to 10 mol, preferably 0.5 to 1.2 mol, 3 mol base. The order of addition of the reactants may be varied as desired, and all reactants may also be fed simultaneously to the reaction vessel. The reaction may be carried out continuously or discontinuously. The reaction mixture is worked up in the usual manner.

The following examples further illustrate the invention but do not limit its scope in any way.

Example 1

To a mixture of 3.3 g (0.02 mol) of N-methylanilide glycolic acid and 1.2 g (0.02 mol) of powdered potassium hydroxide in 50 ml of isopropyl alcohol is added a solution of 4 g (0.02) at -15 ° C. mol) of 2,6-dichlorobenzothiazole in 10 ml of acetonitrile and the reaction mixture is stirred for an additional 15 hours at -5 ° C after the addition is complete. For working-up, the reaction mixture was poured into water, the precipitated solid was filtered off, washed with water, then dried. and recrystallized from a 1: 1 mixture of acetic acid and petroleum ether. 4 g (75% of theory) of 2- (6-chlorobenzothiazol-2-yl) -N-methyloxyacetanilide of melting point 108 DEG C. are obtained.

Example 2

To a mixture of 8.2 g (0.05 mol) of N-methylanilide glycolic acid and 3.1 g (0.05 mol) of powdered potassium hydroxide in 80 ml of isopropyl alcohol, a solution of 9.4 g is added dropwise with stirring at -10 ° C. (0.05 mol) 2,6-dichlorobenzoxazole in 20 ml isopropanol and after the addition was complete the reaction mixture was stirred at -5 ° C for a further 15 hours. For work-up, the reaction mixture is poured into water, the precipitated solid is filtered off, washed with water and dried.

13 g (82% of theory) of 2- (6-chlorobenzoxazol-2-yl) -N-methyloxyacetanilide of melting point 139 DEG C. are obtained.

Accordingly, the following compounds of formula I are also prepared as described in the preceding examples and according to the general production data:

If, for example, 2,6-dichlorobenzoxazole and glycolic acid N-methylanilide are used as starting materials, the reaction scheme can be illustrated by the following reaction scheme:

The 6-chlorobenzazoles required as starting materials in the process of the invention are generally defined by Formula II. In this formula (II), A is preferably halogen, in particular chlorine or bromine, or alkylsulphonyl or aralkylsulphonyl, in particular methylsulphonyl or ethylsulphonyl.

The 6-chlorobenzazoles are known (cf., for example, EP-OS 43 573 or DE-OS 30 25 910) or can be prepared simply in an analogous manner according to principally known methods.

The glycolic acid amides which are further required as starting materials for carrying out the process of the invention are generally defined by formula III. Glycolic acid amides of formula III are also known (cf., for example, DE-OS 29 04 490, EP-OS 5501, EP-OS 29 171, DE-OS 30 38 598, DE-OS 32 44 956).

Suitable diluents for the reaction according to the invention are organic or inorganic solvents. They are preferably hydrocarbons such as toluene or cyclohexane, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane or chlorobenzene, ketones such as acetone or methyl isobutyl ketone, ethers such as diethyl ether, diisopropyl ether or methyl tert-butyl ether, alcohols such as methanol, ethanol or isopropanol, amides such as dimethylformamide or dimethylacetamide, sulfoxides such as dimethyl sulfoxide, water or aqueous salt solutions.

The salts used are preferably alkali metal or alkaline earth metal chlorides or sulphates, such as sodium chloride, potassium chloride or calcium chloride. Sodium chloride is particularly preferred.

The process according to the invention is preferably carried out using acid-binding agents.

As such, strongly basic alkali and alkaline earth metal compounds such as oxides such as sodium oxide, potassium oxide, magnesium oxide and calcium oxide, hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide and / or carbonates are preferably used. , such as sodium carbonate, potassium carbonate, magnesium carbonate, and calcium carbonate.

In some cases, the addition of 0.01 to 10% by weight (based on the glycolic acid amide of formula III used) of the phase transfer catalyst has proven advantageous. Examples of such catalysts are:

tetrabutylammonium chloride, tetrabutylammonium bromide, tributylmethylphosphonium bromide, trimethyl-C 1 -C 6 -alkyllammonium chloride, dibenzyldimethylammonium methylsulfate, dimethyl-C 1 -C 6 -alkylbenzylammonium chloride, tetrabutylammoniumbenzylbenzylammoniumbenzyl, monobutylbenzyl ammoniumbenzamide, 6-methylbenzylammoniumbenzamide,

The reaction temperatures can be varied within a wide range in the process according to the invention. They are generally between -50 ° C and +100 ° C, preferably between -20 ° C and +100 ° C.

The process according to the invention is generally carried out at atmospheric pressure, but can also be carried out at elevated or reduced pressure, for example at a pressure of 0.01 to 1.0 MPa.

Table 2 Example R ¹ number _R 1 2 X ^K R or -N V X Temperature melting point (° C)

3 4 CH ₃ CH ₃ (CH _{2) 3} - ch, P. 0 0 78 to 79 112 5 -P 0 82 ch ₃ 6 -O 0 118 7 ^C 2 ^H 5 ^C 2 ^H 5 0 80 8 CH ₃ ch ₃ 0 9 CH ₃ (CH ₂ ) ₂ - ^CH 3 ^(CH 2> 2- 0 10 CH ₃ O 0 11 ch ₃ CH ₃ with 160 12 ^C 2 ^H 5 ^C 2 ^H 5 with 76 13 CH ₃ ^CH 3 ^<CH 2> 3- with 94 14 Wz * CH ₃ (CH ₂ ) ₂ - with 71 15 Dec CH ₃ O ch ₃ with 16 -P with 78 ch ₃ 17 -P with 98 18 -Ό with 84 19 Dec CH ₂ = CH-CH ₂ - CH ₂ = CH-CH ₂ - with 70 20 May ^ch 3 with 88

Table 2 - continued

Example R ¹ R ² number

\ r ²

X Melting point <° C)

CH ₃ O- C ₂ H ₅ -CH ₃

CH ₃ - CH ₃ C-CH ₂ S 144

S 115

S 142

S 162

26 CH 27 Mar: CH 28 CH. 29 CH,

^CH 3 ^(CH 2> 2CH ₃ OCH ₂ Cl

WITH

S 77

S 123

S 126

30 CH ₃ (CH _{2) 3} - CH ₃ (CH _{2) 3} - with 67 31 ^C 2 ^H 5 ' ch ₂ = ch- with 78 32 CH ₂ = CH-CH ₂ - CH ₂ = CH-CH ₂ - 0 82 33 ^OBJECTIVE 3 O- 0 65 34 (ch ₃ ) ₂ ch- c ₇ h _r o-ch ₇ -ch ₇ -o 0 n ²⁰ = 1.5274 35 ^CH 3- - ^with - ^C 4 ^H 9 0 79 36 ^_n O ~ ^ch3 0 98 37 ^CH 3 ^- ch ₃ - 0 120 38 ch ₃ < ^c h ₂ ) ₂ - CH ₃ (CH ₂ ) ₂ - 0 59

Claims (1)

Process for the preparation of the novel 6-chlorobenzazolyl oxyacetamides of the formula I X represents an oxygen atom or a sulfur atom, 1 2 R @ 1 and R @ 2 are each independently straight or branched (C1 -C6) alkyl, straight or branched (C2 -C6) alkenyl, straight or branched (C2 -C6) alkynyl, optionally one to three times, the same or (C až-C 7) cycloalkyl or cycloalkenyl of various groups, in each case methyl or ethyl-substituted, C až-C přím straight or branched alkoxy, C nebo-C alko straight or branched alkoxyalkyleneoxy, straight or branched alkoxy C 1 -C 6 alkoxy and alkyl, straight or branched (C 1 -C 6) alkylthio, straight or branched (C 1 -C 6) haloalkyl, (C 1 -C 5) halogen, benzyl and optionally once up to three times, the same or differently substituted phenyl, wherein substituents are selected from the group consisting of methyl, ethyl, methoxy, methylthio, trifluoromethyl, trifluromethoxy, trifluoromethylthi, fluoro, chloro or nitro, or 1 2 R and R together with the nitrogen atom to which they are attached, optionally one to three times the same or different methyl, ethyl and phenyl, are substituted heterocycles of the formula characterized in that the 6-chlorobenzazoles of formula XI (II) in which X is as defined above and A represents an electron withdrawable group, for example a halogen atom, acts by glycolic acid amides of formula III (III) in which 1 2 R and R are as defined above, optionally in the presence of a diluent and optionally in the presence of an acid-binding agent, and optionally in the presence of a catalyst.