CH635333A5 - Process for the preparation of dihalovinyl-gamma-butyrolactones - Google Patents

Description

The present invention relates to a process for the preparation of partially known dihalogenvinyl-Y-bu-tyrolactones.

3rd

635333

in which

Hai, R1, R2 have the meaning given above and

R3 represents Cj-4-alkyl,

optionally in the presence of a base and optionally in the presence of a diluent.

The process according to the invention allows - starting from the new compounds II or III - an economical production of the partially known halovinyl-substituted Y-butyrolactones.

If 4-methyl - 3- (2 ', 2'-dichlorovinyl) -Y-valerolactone-2-carboxylic acid is used as the starting material in process variant a), the course of the reaction can be represented by the following formula:

elei

CH,

S

! OOH

CH,

The starting materials which can be used in process variant a) are defined by the general formula II. R1 and R2 are preferably methyl. The compounds of formula II are new, their preparation is described below.

Process variant a) is expediently carried out by heating the compounds of the general formula II, if appropriate in the presence of diluents, to, for example, 100-250 ° C., preferably at a pressure of 10 to 760 mm Hg.

Suitable diluents are:

Hydrocarbons such as toluene, xylene; Chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene; Ethers such as diethylene glycol dimethyl ether, glycol dibutyl ether or alcohols such as glycol.

In process variant a), the compounds of the formula II are heated without a diluent. The compounds of the formula I can be distilled off under a slight negative pressure (10-100 mm Hg) and thus purified at the same time. However, it is also possible to dispense with distillation and to purify the compounds of the formula I formed on heating the compounds of the formula II by recrystallization.

If 4-ethyl-3- (2 ', 2'-dibromovinyl) -Y-valerolactone-2-carboxylic acid ethyl ester is used as starting material in process variant b), the course of the reaction can be represented by the following reaction scheme:

ooc2h5

The starting materials used in process variant b) are defined by the general formula III,

COOR R1 and R2 are preferably methyl. The compounds of Formula III are new. Their manufacture is further described below.

Process variant b) is carried out by saponifying the compounds to give the carboxylic acid of the general formula II by one of the generally customary processes of ester hydrolysis, if appropriate in the presence of a diluent. The saponification can be carried out in a basic or acidic medium. It is preferably carried out in an alkaline medium at a pH> 10 and at temperatures between 0 and 100 ° C. It is distilled off from the alcohol formed and, after the saponification 15 has ended, acidified to a pH value> 1, as a result of which the acid of the general formula II is formed. After saponification, the procedure described in process variant a) is followed.

The following lactones can preferably be prepared by the process according to the invention:

4-methyl-3- (2 ', 2'-dichlorovinyl) -Y-valerolactone 3- (2', 2'-dichlorovinyl) -Y-valerolactone

3- (2 ', 2'-dichlorovinyl) -Y-butyrolactone

4-ethyl-3- (2 ', 2'-dichlorovinyl) -Y-valerolactone 25 4,4-diethyl-3- (2', 2'-dichlorovinyl) -Y-butyrolactone

4-methyl-3- (2 ', 2'-dibromovinyl) -Y-valerolactone 3- (2', 2'-dibromovinyl) -Y-valerolactone

3- (2>, 2'-dibromovinyl) -Y "butyrolactone

4-ethyl-3- (2 ', 2'-dibromovinyl) -Y-valerolactone 30 4,4-diethyl-3- (2', 2'-dibromovinyl) -Y-butyrolactone

4-methyl-3 (2'-chloro-2'-bromo) "Y-valerolactone 4-methyl-3- (2'-fluoro-2'-bromo) -Y-valerolactone.

As already mentioned, the compounds of general formula II are new. They are obtained according to process variant 35) by saponifying compounds of the general formula III by customary methods.

As already mentioned, the compounds of the general formula III are new. They can be obtained by using oxiranes of the general formula IV

40

-Hai

Shark

>

45

7

IV

in which

Hai, R1, R2 have the meaning given above, with malonic esters of the general formula V

50

COOR3

CH2;

COOR3 in which

55 R3 has the meaning given above, in the presence of a base and, if appropriate, in the presence of a diluent.

The oxiranes of the general formula IV are new. They can be obtained by connecting all-

60 someone Formula VI

H R1

I I

Hal3C-CH2-C-C-R2 VI

I I

65 shark OH

in which

Hai, R1, R2 have the meaning given above, in the presence of a diluent and a catalytic

635333

4th

dehydrohalogenated. If 2-methyl-3,5,5,5-tetrachloropentanol (2) is used as the starting material, the course of the reaction can be represented by the following formula:

CH3

I.

CC13-CH2-CHC1-C-CH3

OH

This course of the reaction was surprising. It proceeds by splitting off hydrogen halide from compounds of the general formula VI to give compounds of the general formula IX

> R1

"Ix

R

in which

Hai, R1, R2 have the meaning given above, and further elimination of hydrogen halide to give compounds of the general formula IV.

While the elimination of the first mole of hydrogen halide to give the compounds of the general formula IX could be expected, it was surprising that the elimination of hydrogen halide from the compound IX would also take place in good yield and without significant side reactions, for the following reasons:

Oxiranes are sensitive to alkalis and lead to further reactions (Houben-Weyl, Methods of Organic Chemistry, Stuttgart 1965, Volume VI, 3, page 376).

Oxiranes are easily reopened with bases (nucleophiles); This produces alkali-catalyzed diols with water (Houben-Weyl, Vol. VI, page 3 457), with amines to obtain amino alcohols.

If the oxiram contains a tertiary carbon atom adjacent to the oxygen, as in the particularly preferred example R1 = R2 = CH3, hydrolytic cleavage takes place even at room temperature (Houben-Weyl, Volume VI, 3; page 454).

It was therefore to be expected that under the influence of the base, which is intended to split off hydrogen halide from compounds of the general formula IX, the oxirane ring would split again and there would be no splitting off of hydrogen halide.

Trihalomethyl groups usually do not react with bases with elimination of hydrogen halide, but ethers, carboxylic acids or the like are formed (US Pat. No. 2,581,925, lines 57-62). It is therefore extremely surprising to note that a smooth conversion of the compounds of the general formula IX into compounds of the general formula IV is possible.

The oxiranes are conveniently obtained by

1 mole of a compound of formula VI with at least

2 mol of a base, if appropriate in the presence of a catalyst; if only one mole of a base is used, compounds of the general formula IX are obtained.

The oxiranes are preferably made in aqueous solution, but the use of inert organic solvents such as hydrocarbons, e.g. Benzene or toluene, chlorinated hydrocarbons such as chlorobenzene and ether without disadvantages.

The oximes are usually produced using suitable catalysts. Compounds of the general formula X or XI are preferably used as such:

B

I.

X A-N-C XI

in which

L represents nitrogen or phosphorus and the radicals io A, B, C and D independently of one another represent optionally substituted alkyl, aralkyl or aryl, or two adjacent radicals, A, B, C and D together with the central atom L and optionally further heteroatoms form a heterocycle 15 and

Y represents a halide, hydrogen sulfate or hydroxyl ion.

Some of the catalysts of the general formula X are known or can be prepared by known processes. 20 (Houben-Weyl, Volume XI, 2, page 587 ff .; Georg-Thieme-Veriag, Stuttgart 1958).

Catalysts of the general formula X in which

A, B, C, D for alkyl with 1-18 C atoms, in particular 25 methyl, ethyl, propyl, butyl, hexyl, dodecyl, octadecyl, for benzyl, which is optionally substituted by C1-C4-alkyl, alkoxy or halogen , stand.

Also preferred are catalysts of the general formula XI,

30 in which

A, B and C are alkyl with 1-18 C atoms, in particular methyl, ethyl, propyl, butyl, hexyl, dodecyl, octadecyl and benzyl.

The following are particularly preferred representatives of the catalysts to be used in the preparation of oxirane-35: tetraethylammonium chloride,

Tetrabutylammonium chloride,

Tetrabutylammonium bromide,

Tetrabutylphosphonium chloride, 40 benzyltriethylammonium chloride,

Phenylbenzyldimethylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltributylammonium chloride,

Triethylamine,

45 tripropylamine,

Tributylamine,

Trihexylamine,

Benzyldimethylamine.

The amount of catalyst can vary within wide limits. In general, 0.1 to 10 wt .-%, preferably 0.3 to 6 wt .-%, based on the weight of the compounds of general formula VI used.

Sodium hydroxide or potassium hydroxide solution is preferably used as the base. The preferred procedure is as follows:

Compounds of the general formula V are initially introduced and then one to 1.2 equivalents of the aqueous base are added dropwise at temperatures between −20 ° C. and 50 ° C., preferably 0-30 ° C. The concentration of the base does not play a decisive role, but it is advisable not to work too diluted and to use about 25-50% solutions of the bases. The base should be added as slowly as possible.

The course of the reaction is followed by measuring the pH-65 value.

When a pH of 7-8 is reached, the catalyst is added and a further 1-1.2 equivalents of an aqueous base. The concentration of the aqueous base used should

3 2

B

A — L (+> - C

I.

5 D

Y (-)

5

635333

are between 1 and 50%, preferably between 5 and 25%.

The reaction is preferably carried out at elevated temperature, usually between 50 and 100 ° C., preferably between 80 and 100 ° C.

The end of the reaction is expediently determined by checking the pH. When it has approximately reached the neutral point, it is allowed to cool and, after the organic phase has been separated off, it is purified by distillation.

Some of the compounds of the general formula VI are known. New and known compounds of the general formula VI

H R1

I I

HaljC-CH, -C-C-R2 VI

I I

Shark OH

in which

Hai, R1, R2 have the meaning given above, can be obtained by using a compound of general formula VII

/ R1

CH2 = CH-C-R2

\

VII

ox

25th

in which

O

X represents hydrogen or the radical —C — R3 and R1, R2, R3 have the meaning given above, with a carbon tetrahalide of the general formula VIII,

C Hal4 VIII

in which

Shark has the meaning given above. If 3-methyl-butenol (3) and carbon tetrachloride are used as starting materials, the course of the reaction can be represented by the following formula:

CH,

CH, = CH-C-CH3 + CCL

OH

CH,

CClj-CHs-CHCl-C-CHj

OH

The starting materials which can be used in this process are defined by the general formulas VII and VIII. You are known. The following compounds of the general formula VII are preferably used:

5 isoprene alcohol (3-methyl-l-buten-3-ol), allyl alcohol, l-buten-3-ol, l-penten-3-ol, 3-methyl-l-penten-3-ol, 3-ethyl- -l-penten-3-ol, 1-vinyl-cyclopentan-l-ol, 1-vinyl-cyclohexan-l-ol and their esters, such as the acetates.

The following compounds of the general formula VIII are preferably used:

CC14, CBr4, CCl3Br, CF2Br2, CFBr3, CClBr3, CC13F.

The reaction can be carried out in the absence or preferably in the presence of a solvent. Excess carbon-15 tetrahalide is preferably used as the solvent, or hydrocarbons such as toluene. Acetonitrile is particularly preferably used. The use of alcohols, for example propanol, butanol or pentanol, is also preferred. The reaction is usually carried out at temperatures of about 20 50-150 ° C, optionally under pressure.

The latter process is preferably carried out using suitable catalysts. For example, the following are possible:

1. Substances that form free radicals, such as benzoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide and azobisisobutyronitrile. In general, catalytic amounts of the radical generator are sufficient, but even larger amounts are not harmful. Metal salts in the presence of organic amines. Examples of suitable metal salts are copper and iron salts, such as copper (I) chloride, copper (II) chloride, iron (II) sulfate, iron (III) chloride. Examples of suitable amines are pyrrolidine, piperidine, n-butylamine, cyclohexylamine, triethylamine and dimethylamine. They can also be used in the form of their salts, for example the hydrochlorides. Catalytic amounts of the catalysts are also sufficient for the reaction. Larger quantities accelerate the reaction. The reaction can also be carried out by irradiation with UV light or Y rays.

As already mentioned, the dihalogenvinyl-Y-butyrolactones of the general formula I which can be prepared according to the invention serve as intermediates for the production of insecticidal active compounds. The production of these active ingredients can be illustrated by the following formula scheme:

cooc2h5

2nd

30th

35

40

: ooc2h5

cl \ _ Cl? "*

ch- ch-

2H5

+

Q "* z =.

,OH

635333

6

The 2,2-dimethyl-3 (2 ', 2'-dichlorovinyl) cyclo-propanecarboxylic acid m-phenoxybenzyl ester obtained in this way is a known insecticidal active ingredient (see German Offenlegungsschrift 2,326,077).

The following examples illustrate the process according to the invention without giving any restriction as to the breadth of its applicability:

Representation of y-butyrolactone by decarboxylation of a Y-butyrolactone carboxylic acid.

example 1

4-Methyl-3- (2 ', 2'-dichlorovinyl) -Y-valerolactone-2-carboxylic acid (91 g) is distilled at an oil bath temperature of 200 ° C in a water jet vacuum. 74 g of 4-methyl-3 - (2 ', 2'-dichlorovinyl) Y-valerolactone of kp23-30 = 160-172 ° C. mp: 118 ° C. are obtained.

Methods 1, 4 and 6: Preparation of the Y-butyrolactone by reacting an oxirane with a malonic ester.

Example 2

11.5 g of sodium are dissolved in 250 ml of ethanol, 80 g of diethyl malonate are added dropwise at room temperature and then 128 g of 2,2-dimethyl-3 (2 ', 2'-dibromovinyl) at 30-35 ° C. in the course of one hour. oxirane. Then hold at 35 ° C for 4 h.

To saponify the resulting 4-methyl-3- (2 ', 2' - dibromovinyl) -Y-valerolactone-2-carboxylic acid ethyl ester, 800 ml of 10% sodium hydroxide solution are added to the reaction solution and the mixture is stirred for 12 hours at room temperature. Ethanol is distilled off and the reaction solution is acidified to pH 1 with concentrated hydrochloric acid. It precipitates 4-methyl-3- (2 ', 2' - dibromovinyl) -Y-valerolactone-2-carboxylic acid, mp 140 ° C. This is filtered off and suspended in o-dichlorobenzene and heated to 170-180 ° C. for 2 hours with stirring. After cooling, 91 g (61% of theory) of 4-methyl-3 - (2 ', 2'-dibromovinyl) -Y-valerolactone crystallize from mp 115 ° C.

Production of oxirane

Example 3

195 g of 45% sodium hydroxide solution are added dropwise at room temperature to a mixture of 480 g of l, l-dimethyl-2,4,4,4-tetra-chlorobutanol and 10 ml of triethylamine. The mixture is stirred for 3 hours at room temperature, then 3000 ml of water, 20 g of tetrabutylammonium chloride and 112 g of potassium hydroxide are added and the mixture is heated to boiling for 8 hours. After cooling, the organic phase is separated off, the aqueous phase is extracted with methylene chloride and the combined organic phases are fractionated in vacuo. 294 g (88% of theory) of 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) oxirane with a bp = 63-65 ° / 15 mm are obtained. = 1.4752.

Example 4

195 g of 45% sodium hydroxide solution are added dropwise at room temperature to a mixture of 480 g of l, l-dimethyl-2,4,4,4-tetra-chlorobutanol and 10 ml of tributylamine. You stir

After 3 h at room temperature, 3000 ml of water, 20 ml of tributylamine and 112 g of potassium hydroxide are added and the mixture is heated to boiling for 12 h. After cooling, the organic phase is separated off, the aqueous phase is extracted with methylene chloride and the combined organic phases are fractionated in vacuo. 274 g (82% of theory) of 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) oxirane of bp = 62-63 ° C./14 mm are obtained.

Example 5

195 g of 45% sodium hydroxide solution are added dropwise to a mixture of 480 g of l, l-dimethyl-2,4,4,4-tetra-chlorobutanol and 10 ml of triethylamine at room temperature in the course of 2 hours. The mixture is stirred for 5 hours at room temperature, the sodium chloride which has separated out is brought into solution with water and neutralized. The organic phase is separated off, the aqueous phase is extracted with methylene chloride and the combined organic phases are fractionated in vacuo. 381 g (94% of theory) of 2,2-dimethyl-3- (2 ', 2', 2'-tri-20 chloroethyl) -oxirane with a bp = 82-84 ° C / 13 mm are obtained. n ^ 10 = 1.4690. b) 203.5 g of 2,2-dimethyl-3- (2 ', 2', 2'-trichloroethyl) oxirane, 1500 ml of water, 56 g of potassium hydroxide and 10 g of tetrabutylammonium bromide are heated to boiling for 10 hours with stirring . After cooling, the organic phase is separated off, the aqueous phase is extracted with methyl lerichloride and the combined organic phases are fractionated in vacuo. 144 g (86% of theory) of 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) oxirane of bp = 68 ° C./17 mm are obtained.

30 Representation of the compounds of formula IV

Example 6

430 g (5 mol) of 3-methyl-1-buten-3-one, 2500 ml of carbon tetrachloride and 40 g of water-containing benzoyl peroxide 35 are heated to boiling for 10 hours on a water separator. After adding another 40 g of moist benzoyl peroxide, boil again on the water separator for 10 hours. After cooling, it is washed with cold NaOH in order to remove the benzoic acid formed. The solvent is then distilled off. The remaining residue is distilled on the oil pump. 971 g (81% of theory) of l, l-dimethyl-2,4,4,4-tetrachlorobutanol with a bp = 75-85 ° C./0.1 mm are obtained. The structure was confirmed by IR and NMR spectra, n ^ ® = 1.4975.

45

Example 7

120 g of l, l-dimethyl-2-propenyl acetate, 332 g of carbon tetrabromide, 16 g of n-butylamine and 14 g of iron (III) chloride (hexahydrate) in 220 g of acetonitrile are heated at 100 ° C. for 12 hours. After cooling, the mixture is filtered off, the solvent is distilled off and 168 g of potassium hydroxide in 2000 ml of water are added dropwise to the residue at room temperature. Then 20 g of tetrabutylammonium chloride are added and the mixture is heated at 80 ° C. for 1 hour, is neutralized after cooling and extracted 55 with methylene chloride. Then it is fractionally distilled. 159 g (62% of theory) of 2,2-dimethyl-3- (2 ', 2'-dibromovinyl-oxirane with a bp = 86-88 ° C./15 mm. N20D = 1.5332. NMR (in CDClj): 5 (ppm) = 1.3-1.4 (d, 6 protons), 3.25 and 3.4 (d, 1 P); 6.2 and 6.35, d, 1 P ).

v

Claims (4)

635333 2nd PATENT CLAIMS 1. Process for the preparation of dihalogenvinyl-f-bu-tyrolactones of the general formula I Hal \ Hal ^ = o R in which Shark represents the same or different F, Cl or Br residues, R1 and R2 stand for identical or different radicals of the group hydrogen or C] -4 alkyl or together with the adjacent C atom form a cycloaliphatic ring with up to 7 C atoms, characterized in that a) a compound of general formula II COOH Dihalogenvinyl-Y-butyrolactones are valuable intermediates for the preparation of the partially known dihalogen-vinylcyclopropanecarboxylic acid esters which are used as insecticides. These manufacturing processes are the subject of another, unpublished, new application (Le A 17 866). Vinyl-substituted y-butyrolactones and processes for their preparation have already become known (see German Offenlegungsschriften 2,461,525 and 2,509,576). However, the processes described there are not very economical and are also limited to vinyl-substituted or dialkyl-vinyl-substituted y-butyrolactones. It has also become known that 4-methyl-3 - (2 ', 2'-dichlorovinyl) -Y-valerolactone as a by-product in the saponification of 2,2'-dimethyl-3- (2', 2'- dichlorovinyl) cyclopro-pan-l-carboxylic acid (see Pestic. Be. 1974 (5) pages 792-793). A process for the production of 4- (2 ', 2'-dihalovinyl) -3,3-dimethyl-Y "butyrolactones has also become known (see German Offenlegungsschrift 2,623,777). However, the process described there can only be carried out economically starting from dimedone and, moreover, does not lead to the desired 3-dihalovinyl-Y-bu-25 tyrolactones. The process according to the invention for the preparation of partially known dihalogenovinyl-Y-butyrolactones of the general formula I II in which Hai, R1, R2 have the meaning given above, is heated, or b) a compound of the general formula III 30th 35 Shark Shark. Shark > = < OOR- III in which 40 shark represents the same or different F, Cl or Br residues, R1 and R2 represent identical or different radicals of the group hydrogen or C 1-4 alkyl or together with the adjacent C atom form a cycloaliphatic ring 45 with up to 7 C atoms, is characterized in that a) a compound of the general formula II in which Hai, R1, R2 have the meaning given above and R3 is C ^ alkyl, is heated. 2. The method according to claim 1, characterized in that the heating according to process variant a) takes place in the presence of a diluent. 3. The method according to claim 1, characterized in that the heating according to process variant b) is carried out in the presence of a base. 4. The method according to any one of claims 1 and 3, characterized in that the heating according to process variant b) is carried out in the presence of a diluent. 50 55 OOH II in which 60 Hai, R1, R2 have the meaning given above, optionally in the presence of a diluent, or b) a compound of the general formula III 65