DE2917893A1 - N- (ALKOXY- OR ALKOXYCARBONALALKYL) - N-HYDROXYACETYL- BZW. PROPIONYL-ANILINE DERIVATIVES AS PLANT FUNGICIDES - Google Patents

Description

Dr. F. Zuinstein Sr. - Dr. Ξ. Assma-.n - Dr, P. Koenigsbefcgfef 7893 Dipl.-Phys. R. Holzbauer - Dipl.-Iny. F. KUritjseisen ■ Dr. F. Zumstein jun.

PATENT LAWYERS
80OO Munich 2 * Bräuhausstrasse 4 · Telephone collective no. 225341 - Telegrams Zumpat ■ Telex 529979

CIBA-GEIGY AG 5-10706 / 1 + 2 / =

Basel, Switzerland)

N- (alkoxy- or alkoxycarbonylalkyl) -N-hydroxyacetyl or propionylaniline derivatives as plant fungicides

The present invention relates to compounds of the formula I. / l

_v T C-CHOH
⁴ R ₂ II!

^0R 6

wherein R C -C -alkyl, C -C -alkoxy or halogen, R ₂ hydrogen, CC-alkyl, C ₁ -C -AlkOXy or halogen, R. hydrogen, C -C -alkyl or halogen, R, hydrogen or methyl are, where the total number of carbon atoms of the substituents R ,, R ₂ , R ₃ and R ^ must not be more than 8.

X -CH ₂ - or -CH-

R _{5 represents} -COOCH ₃ J COOC ₂ H ₅ or -CH ₂ OCH ₃ , and R _{5 represents} hydrogen or methyl, processes for the preparation of these compounds and their use for controlling pests and agents which contain these compounds as active components.

030046/0 242

Under alkyl or as an alkyl part of an alkoxy group are each according to the number of carbon atoms specified, the following group is to be understood: methyl, ethyl, n-propyl, iso-propyl, η-butyl, iso-butyl, sec-butyl and tert-butyl. Halogen stands for fluorine, chlorine, bromine or iodine.

The compounds of formula I are according to the invention A) by acylation of a compound of formula II

-NH-XR ₅ (II)

⁴ rows
^R 2

with a compound of the formula III

Shark'-CO-CH-O-CO-R- (III)

^R 6

and mild alcoholysis in the presence of alcoholate at room or slightly elevated temperature , where R "represents a lower aliphatic radical, preferably methyl or ethyl, or

B) by initial monohaloacylation of a compound of formula II to a compound of the formula IV

(* (IV)

"^, CO-CH-HaI"

^R 4

and replacing the halogenatoiss Hai "with the acid residue of an acid

HOCO-R., With the help of the acid itself or one of its salts, preferably /

their alkali or alkaline earth salt, and ansenliessands tired alcoholysis in the presence of alcoholate at room temperature or slightly elevated temperature where in formulas II, III and IV R to R _{fi have} the meaning given for formula I, while Hai 'and Hai "halogen , Preferential

030046/0242

wise chlorine or bromine.

The conversions can be in the presence or absence of opposite the reactants inert solvents or diluents are carried out. For example, the following are possible: aliphatic or aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, Ethylene chloride, chloroform; Ether and ethereal compounds such as dialkyl ethers, t-butyl methyl ether, dioxane, tetrahydrofuran; Nitriles such as acetonitrile; Ν, Ν-dialkylated amides such as dimethylformamide; Dimethyl sulfoxide, ketones such as methyl ethyl ketone and mixtures of these Solvents among each other.

For the monohaloacetylation according to variant B, the corresponding Carboxylic acids themselves and their esters, but advantageously use the acid anhydrides or the acid halides. As acid halides the acid chlorides or acid bromides are preferred.

The reaction temperatures are between 0 ° and 120 ⁰ C, preferably between 0 ° and 50 ⁰ C. In some cases, the use advantageously of acid-binding agents or condensation agents. Tertiary amines such as trialkylamines (eg triethylamine), pyridine and pyridine bases, or inorganic bases such as the oxides and hydroxides, hydrogen carbonates and carbonates of alkali and alkaline earth metals and sodium acetate are suitable as such.

The manufacturing process starting from compounds of the formula II A and the acylation step leading to compounds of the formula IV can also be carried out without acid-binding agents, in which case nitrogen is passed through to drive them off of the hydrogen halide formed is indicated. In other cases it is an addition of dimethylformamide as a reaction catalyst is very advantageous.

030046/0242

The compounds of the formula II can be prepared analogously to methods known per se.

See J. Org. Chem. 30, 4101 (1965), Tetrahedron 1967 , 487
Tetrahedron 1967 , 493

In the compounds of the formula I there are two possible asymmetric carbon atoms present, which are at positions 1 and 2 in the following Formula can be found:

.R- τ *
/1

> <7 »ω

C-CHOH * R Il I

^0R 6

/ TTT

1 * asymmetrical, if X means -CH-
2 * asymmetric, if R stands for methyl.

The pure optical isomers can be produced, for example, by using already separate antipodes of the starting materials. These are e.g. by salt formation with optically active bases with subsequent fractional crystallization and release of the corresponding Antipodes preserved.

Regardless of the optical isomer, atropisomerism about the phenyl -N ^ axis is usually observed in cases where the Phenyl ring asymmetrical to this axis (possibly also through the presence of additional substituents) is substituted.

Unless a specific synthesis for the isolation of pure isomers is carried out, one product usually falls as a mixture of all of them Isomers.

030046/0242

The compounds of the formula I can be used alone or together be used with suitable supports and / or other aggregates. Suitable carriers and aggregates can be solid or liquid and correspond to the substances commonly used in formulation technology such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

The content of active ingredient in marketable products is between 0.1 to 90%.

For administration, the compounds of the formula I can be in the following working-up forms (the percentages by weight represent advantageous amounts of active ingredient in brackets):

Fixed forms of processing; Dust and grit (up to 10%)

Granules, coated granules, impregnation granules and homogeneous granules (1 to 80%);

Liquid work-up forms;

a) Active substance concentrates dispersible in water:

Wettable powders and pastes (25-90 % in the commercial pack, 0.01 to 15% in the ready-to-use solution); Emulsion and solution concentrates (10 to 50%; 0.01 to 15% in ready-to-use solution) ι

b) solutions (0.1 to 20%); Aerosols

030046/024 2

2317893

The compounds of the formula I have a microbicidal spectrum for protecting crop plants which is very favorable for practical requirements. For the purposes of the present invention, crops are, for example, cereals, corn, rice, Geaiüse, sugar beet, soy, peanuts, fruit trees, ornamental plants, but especially vines, hops, cucumber plants (cucumbers _s pumpkin ρ melons) 5 Solanaceae such as potatoes, tobacco and Tomatoes, as well as banana, cocoa and natural rubber plants.

The active ingredients of formula 1 can be used to ^{contain or destroy the fungi that occur on plants or plant parts (fruits, B 1} UtSn ₅ foliage, stems, tubers, roots) of these and related crops, with plant parts that grow later also being spared from such fungi. The active ingredients are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes: Basidiomycetes such as rust mushrooms in particular; Fungi imperfecti such as Cercospora? but then especially against those of the Ooiaycetes class such as Phytophthora, Peronospora, Pseudoperonospora _5, Pythium or Plasmopara. In addition, the compounds of formula 1 have a systemic effect. They can also be used as a dressing agent for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections and against phytopathogenic fungi that occur in the soil.

A group of interest because of their action is formed by those compounds of the formula I in which R, methyl or methoxy, R "methyl, Aethylj chlorine or bromine, R_ hydrogen, methyl, chlorine or bromine and R, hydrogen or methyl.

Preferred plant fungicides are compounds of the formula I in which R is methyl, R_ is methyl or ethyl, R ₃ and R are hydrogen or methyl. R «is preferably in the ortho position to the amino group.

Compounds in which R 1 is hydrogen are to be emphasized.

0300A6 / 02A2

-JT-

In formula I and especially within these four groups those compounds are preferred in which X - CH- and

R-COOCH represent.

Combinations of the various groups of compounds with one another are of particular interest.

The following examples serve to explain the invention in more detail without restricting the same. The temperature data relate to degrees Celsius, the pressure data to millibars. Unless otherwise noted, when an active ingredient of the formula I _{5 is mentioned,} which can occur in optically active forms, the racemic mixture is always meant.

0 30 OA 6/0 2-4 t

Manufacturing examples

Example 1 : Preparation of N- (l '~ methoxycarbonyl-ethyl) -N-hydroxyacetyl- * 2,6-dimethylaniline of the formula

CI-X

CH!

/ - »(CH-COOCH
«/ \, _ _N (Verb. No. 1)

· = · CCH OH
CH ₃ I!
0

28 _S 7 g of N- (l-methoxycarbonyl-ethyl) -N-acetoxyacetyl-2,6-dimethylaniline in 100 ml of abs. Methanol was added dropwise at room temperature to a stirred methylate solution prepared from 2.8 g of sodium and 180 tal of methanol. After 60 hours of standing at room temperature wnTde the methanol was evaporated, the reaction mixture poured onto 400 ml of ice water and made neutral with dilute hydrochloric acid, with a tail of the reaction product precipitated as a solid ", which was filtered off. The filtrate was extracted twice with methylene chloride, the combined extracts were washed with water, dried over sodium sulfate, filtered and the methylene chloride was evaporated. The residue was recrystallized together with the solid precipitate from ethyl acetate-petroleum ether (4O-6O ^c ). The crystals then melt between 94-95 ° C.

Example 2 ; Preparation of N- (l ^{l-methyl-2'-me} £ hosyäthyl) -N-hydroxyacetyl-2,6-dimethylaniline

/ V _N

CH, Il

³ 0 ·

29.3 g of N- (I'-methyl-2-methoxyethyl) -N-acetoxyacetyl-2,6-dimethylaniline in 47 ml of methanol at room temperature were converted into one of 1 g of sodium methylate and 10 g abs. Methanol prepared solution with stirring

0300 4 6/02 4 2

After 40 hours of standing at room temperature, the methanol was evaporated, the reaction mixture was poured onto 100 ml of ice water and neutralized with dilute hydrochloric acid. The precipitated was filtered off Realctionsprodukt _s the filtrate extracted twice with methylene chloride, the combined extracts washed with water, dried over sodium sulfate, filter and evaporate the methylene chloride. The residue and the precipitated precipitate were recrystallized from diethyl ether. The white crystals melt at 73-75 ^o C

In an analogous manner or by one of the methods described herein the following compounds of the formula I can be prepared:

Table I.

Verb. R ₁ ^R 2 ^R 3 R ₄ ^R 5 ^R 6 Physically. No. constant 1 CH ₃ 6-CH ₃ H H -OCH ₃ H M.p. 94-95 ° C 2 CH ₃ 6-C ₂ H ₅ H H -OCH ₃ H M.p. 118-121 ° C 3 CH ₃ 6-CH ₃ H H -OC ₂ H ₅ H 4th CH ₃ 6-Cl H H -OCH ₃ H 5 CH ₃ 6-C ₂ H ₅ H H -OC ₂ H ₅ H 6th C ₂ H ₅ 6-C ₂ H ₅ H H -OCH ₃ H 7th Br 6-Br 4-CH ₃ H -OCH ₃ H 8th CH ₃ 6-Br 3-CH ₃ 4-Br -OCH ₃ H 9 CH ₃ 6-CH ₃ H H -OCH ₃ -CH ₃ 10 CH ₃ 6-Cl H H -OC ₂ H ₅ H 11 CH ₃ 6-Cl 3-CH ₃ 4-Cl -OCH ₃ H 12th CH ₃ 6-CH ₃ H H -OC ₂ H ₅ -CH ₃ 13th CH ₃ 6-Br H H -OCH ₃ H 14th OCH ₃ 6-Cl H H -OCH ₃ H 15th CH ₃ 6-Cl 4-CH ₃ H -OC ₂ H ₅ H 16 CH ₃ 6-CH ₃ 3-CH ₃ 5-CH ₃ -OCH ₃ H 17th Cl 6-Cl 4-CH ₃ H -OCH ₃ H 18th OCH ^ 6-Br H H -OCH ₃ H

030046/02

-yr-

Verb.
No. ^R l ^R 2 ^R 3 ^R 4 S. ^R 6 Physically.
constant 19th CH ₃ 6-C ₂ H ₅ H H -OCHg -CH ₃ 20th Cl 6-Cl H H -OCHg H 21st CHg 6-CHg 3-CH 5-CH -OC ₂ H ₅ H 22nd
23 CHg
Cl 6-CnHc
6-Cl FC FC FC FC -OC ₂ H ₅
-OC ₂ H ₅ -CHg
H 24 CH ₃ 6-CH ₃ 3-Br H -OCH ₃ H 25th CHg 6-Br 3-CH ₃ 4-Br -OC ₂ H ₅ H 26th Cl 6-Cl 3-CHg 4-Cl -OCH ₃ H 27 CHg 4-OC ₄ H ₉ H H -OCH ₃ H (sec.) 28 CH ₃ 6-Cl H H -OCH ₃ -CHg 29
30th CH ₃
CHg 6-Cl
6-CH ₃ 4-CHg
3-CH ₃ H
H -OCH ₃
-OCH ₃ H
H τξ ² = 1.5303 31 CH ₃ 6-CH ₃ 3-CH ₃ H -OC ₂ H ₅ H 32 CHg 6-CH ₃ 3-CH ₃ H -OCH ₃ -CHg 33
34 FC FC
LO LO 6-CH ₃
6-C ₂ H ₅ 3-CH ₃
3-CH ₃ H
H -OC ₂ H ₅
-OCH ₃ -CHg
H 35 CHg 6-C ₂ H ₅ 4-Cl H -OCHg H 36 Br 6-Br 3-CHg 4-Br -OCHg H 37 CHg 6-C ₂ H ₅ 4-Cl H -OCH ₃ -CH ₃ 38 CHg 6-Cl 4-Cl 5-CH ₃ -OCH ₃ H 39 CHg 6-CH ₃ 3-Cl H -OCHg H 143-151 ° C (dec.) 40 CHg 6-C ₂ H ₅ 4-Br H -OCHg H 41 CH ₃ 6-CH ₃ 4-Cl H -OCHg -CH ₃ 42 CH ₃ 6-CH ₃ 4-CHg H -OCHg H 43 CH ₃ 6-Br 4-Br 5-CHg -OCHg H 44 CH ₃ 6-CH ₃ 4-Br H' -OCH ₃ -CHg 45 CH ₃ 6-Br 4-CHg H -OCH ₃ . H 46 CH ₃ 6-Cl 4-Cl H -QCH ₃ -CHg 47 CH ₃ - 6-Br 4-CI H -OCH ₃ -CH ₃ 48 CH ₃ 6-Br 4-Cl H -OCH ₃ H 49 CH ₃ 6-CH ₃ 4-Cl H -OCH ₃ H ;

Θ30046 / ί> 242

-κ-

Verb.
No. ^R l R ₂ ^R 3 ^R 4 ^R 5 ^R 6 50 CH ₃ 6-Br 3-Cl 4-Br -OCH ₃ H 51 CH ₃ 6-Br 4-Cl H -OC ₂ H ₅ -CH ₃ 52 CH ₃ 6-CH ₃ 4-Cl H -OC ₂ H ₅ H 53 CH ₃ 6-Cl 4-CH ₃ H -OCH ₃ " ^CH 3 54 CH ₃ 6-CH ₃ 4-Br H -OCH ₃ H 55 CH ₃ 6-Cl 4-Cl H -OCH ₃ H 56 C ₂ H ₅ 6-OCH ₃ 4-Cl H -OCH ₃ H 57 CH ₃ 6-Br 4-Br H -OCH ₃ H 58 CH ₃ 6-CH ₃ 3-CH ₃ 5-CII ₃ -OCH ₃ -CH ₃

Table II (R ₅ = hydrogen, -XR ₅ = -

ft

^R l ^R 2 ^R 3 ^R 4 ^R 5 Verb.
No. ^ 3 6-CH ₃ H H -OCH ₃ 59 ^CH 3 6-C ₂ H ₅ H H -OCH ₃ 60 CH ₃ 6-CH ₃ 3-CH ₃ H -OCH ₃ 61 CH ₃ 6-Cl 4-Cl H -OCH ₃ 62

Table III (-XR ₅ = -CHCH ₂ OCH ₃ ; R ^ = hydrogen)

Verb. R ₁ 6-CH ₃ - R ₃ V Physically. No. 6-CH ₃ : constant 63 ■ CH ₃ 6-C ₂ H ₅ H . H M.p. 73-75 C 64 CH ₃ 6-CH _3; 3-CH ₃ 5-CH ₃ 65 CH ₁ η: "H 66 CH ₃ : 3-CH ₃ H Bp. 130-132 ° / O, 08 torr

-Ü

Verb.
No. ^R l ^R 2 ^R 3 ^R 4 67 CH ₃ 6-CH ₃ 4-Cl H 68 ^CH 3 6-Cl 4-Cl H 69 ^CH 3 6-Cl H H 70 CH ₃ 6-CH ₃ 3-Cl H

Formulation examples

Example 3 : Dust : To produce a) 5% and b) 2% dust, the following substances are used:

a) 5 parts of active ingredient
95 parts of talc .;

b) 2 parts of active ingredient

1 part of highly dispersed silica,
97 parts of talc;

The active ingredients are mixed and ground with the carrier substances and can be dusted in this form for use.

Example 4 : Granules : The following substances are used to produce 5% granules:

5 parts of active ingredient

0.25 part of epichlorohydrin,

0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol

91 parts of kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin or with 6 Parts of acetone dissolved, then folyethylene glycol and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin ^, and then the acetone is evaporated in vacuo. Such a thing

Micro granulate is particularly suitable for floor application.

Example 5 : Wettable powder : To produce a) 70% b) 40% c) and d) 25% e) 10% wettable powder, the following ingredients are used:

a) 70 parts of active ingredient

5 parts of sodium dibutyl naphthyl sulfonate,

3 parts naphthalenesulfonic acids-phenolsulfonic acids-formaldehyde-

dehyde condensate 3: 2: 1,

10 parts kaolin,

12 parts of champagne chalk;

b) 40 parts of active ingredient

5 parts of lignin sulfonic acid sodium salt,

1 part dibutylnaphthalenesulfonic acid sodium salt,

54 parts of silica;

c) 25 parts of active ingredient

4.5 parts calcium lignosulfonate,

1.9 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1),

1.5 parts sodium dibutyl naphthalene sulfonate,

19.5 parts of silica,

19.5 parts of champagne chalk,

28.1 parts of kaolin;

d) 25 parts of active ingredient

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol;

1.7 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1),

8.3 parts sodium aluminum silicate,

16.5 parts of kieselguhr,

46 parts of kaolin; - ■

0-3FET (R β / 0 ^ 2

e) 10 parts of active ingredient

3 parts mixture of the sodium salts of saturated fatty alcohol sulfates,

5 parts of naphthalenesulfonic acid / formaldehyde condensate, 82 parts of kaolin;

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. The wettability and suspension properties obtained are wettable powders, which can be mixed with water to form any desired suspensions Dilute concentration and use especially for foliar application permit.

Example 6 : Emulsifiable concentrates : The following substances are used to produce a 25% emulsifiable concentrate:
25 parts of active ingredient

2.5 parts of epoxidized vegetable oil, 10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether

Mixture,

5 parts of dimethylformamide,
57.5 parts of xylene.

This concentrate can be diluted with water to produce emulsions of any desired concentration, which are particularly suitable for foliar application.

The compounds of formula I can adapt to them under the given circumstances adapt to broaden their spectrum of activity with other suitable pesticides, such as fungicides, insecticides, acaricides, Nematicides, rodenticides, herbicides or active ingredients which influence the vegetation, and also fertilizers can be used together.

Biological examples

Example 7 : Action against Phytophthora infestans on tomatoes

a) Curative effect Tomato plants of the "Red Gnome" variety were sprayed with a zoospore suspension of the fungus after three weeks of cultivation ^{and incubated in a cabin at 18 to 20 °} C. and saturated atmospheric humidity. Interruption of humidification after 24 hours. After the plants had dried, they were sprayed with a broth containing the active substance formulated as a wettable powder in a concentration of 0.06%. After the spray coating had dried on, the plants were again placed in the humid cabin for 4 days. The number and size of the typical leaf spots that appeared after this time were the yardstick for assessing the effectiveness of the substances tested.

b) Preventive systemic action The active substance formulated as a wettable powder was applied in a concentration of 0.006% (based on the soil volume) to the soil surface of three-week-old potted tomato plants of the "Red Gnome" variety. After a three-day waiting period, the underside of the leaves of the plants was sprayed with a zoospore suspension of Phytophthora infestans. They were then kept 5 days in a spray booth at 18 to 20 ⁰ C and saturated humidity. After this time, typical leaf spots formed, the number and size of which are used to assess the effectiveness of the substances tested.

Compounds of formula I such as No. 1 and 30 inhibited the infestation to less than 20% compared to control plants.

Example 8 ; Action against Plasmopara vitieola (Bert, et Curt.) Berl. et DeToni) on vines

Residual preventive effect Vine cuttings of the "Chasselas" variety were grown in the greenhouse. In the 10-leaf stage, 3 plants were sprayed with a broth (0.06% active ingredient) prepared from the active ingredient formulated as a wettable powder. After the spray coating had dried on, the plants on the underside of the leaves were evenly infected with the spore suspension of the fungus. The plants were then kept in a humid chamber for 8 days. After this time, clear symptoms of disease appeared on the control plants. The number and size of the infection sites on the treated plants served as an assessment standard for the effectiveness of the substances tested.

Example 9 : Action against Pythium debaryanum on sugar beets

Effect after soil application The fungus was cultivated on sterile oat grains and added to a mixture of soil and sand. The soil infected in this way was filled into flower pots and sown with sugar beet seeds. Immediately after sowing, the test preparation, formulated as a wettable powder, was poured over the soil as an aqueous suspension (20 ppm of active ingredient based on the volume of soil). The pots were placed on it for 2-3 weeks in a greenhouse at about 20 ⁰ G. The earth was always kept evenly moist by lightly showering over it.

When evaluating the tests, the emergence of the sugar beet plants and the proportion of healthy and diseased plants is determined.

When using compounds of the formula I, including compounds No. 1 and 30, the infestation was reduced to less than 20% -inhibits.

Claims (6)

-Vf- claims 1. Compounds of formula I ^y - A ⁴ R Il I
RHI ^0R 6 c-choh wherein R _{1 is} C ₁ -C ₄ -AlUyI, C ₁ -C ₄ -AlkOXy or halogen, R _{2 is} hydrogen, C ₃ -C ₃ -alkyl, C ₁ -C ₄ -AlkOXy or halogen, R _{3 is} hydrogen, Cj-C ^ Alkyl or halogen, R _{4 are} hydrogen or methyl, the total number of carbon atoms in the substituents R ₁ , R ₂ , R ₃ and R _{4 being} not more than 8. fs X -CH ₂ - or -CH- R represents -COOCH ₃ , COOC ₂ H ₅ or -CH ₂ OCH ₃ , and R represents hydrogen or methyl « 2. Compounds according to claim 1 in which in the formula IR, methyl or methoxy, R _{2 is} methyl, ethyl, chlorine or bromine, R _{3 is} hydrogen, methyl, chlorine or bromine and R is hydrogen or methyl. 3. Compounds according to claim 2 wherein in the formula IR ₁ methyl R ₂ in the ortho position
Mean methyl. in the ortho position methyl or ethyl and R "and R, hydrogen or 4. Compounds according to any one of claims 1 to 3 wherein in the C ¹ H
Formula I -XR ₅ for 3 -CHCOOCH ₃
stands. 5. Fungicidal agents containing as at least one active component a compound according to any one of claims 1 to 4. 030046 / 02A2 6. Process for the preparation of compounds of the formula I marked
A) by acylation of a compound of formula II > -NH-X-R. (II). R ^ T ^4th H with a compound of the formula III Shark'-CO-CH-O-CO-R (III) ^R 6 and mild alcoholysis in the presence of alcoholate at room or slightly lower temperature, where R _{7 is} a lower aliphatic radical, preferably methyl or ethyl, or B) by initial monohaloacylation of a compound of formula II to a compound of the formula IV / ^X ~ ^R 5 ^N CO-CH-HaI " " ^{2 R} 6 and exchange of the halogen atom Hal "for the acid residue of an acid HOCO-R ₇ with the aid of the acid itself or one of its salts, preferably its alkali or alkaline earth salt, and subsequent mild alcoholysis in the presence of alcoholate at room temperature or slightly elevated temperature, with in the formulas II, III and IV have R ₁ to R which are for 1 0 Formula I given meaning, while Hal ¹ and Hal "denote halogen, preferably chlorine or bromine. FO 7.5 NOR / rö * Q30CU6 / 0242