CS207598B2 - Method of making the oxiran deerivatives - Google Patents

Description

(54) A method for producing oxirane derivatives

The present invention relates to a process for the preparation of oxirane derivatives which are used as intermediates in the production of dihalvinyl-t-butyrolactones.

Dihialoigenvinyl-γ-hutyrolactones are valuable intermediates for the preparation of the partially known dihalogeninyl cyclopropanecarboxylic acid esters which are used as insecticides. These manufacturing processes are described in DOS No. 2,710,974.

The woolly-substituted γ-butyrolactones as well as the process for their preparation are already known (see also DOS 2 461 525 and 2 509 576). However, the processes described in this literature are not economical and are furthermore limited to vinyl-substituted or dialkyl-substituted-γ-butyrolactones.

In addition, it is known that 4-methyl-3- (2 ', 2'-dichlororynyl) -yl-ile-oleolactone is formed as a by-product of saponification of 2,2'-dimethyl-3- (2', 2 ' (Dichlorvinyl) cyclopropane-1-carboxylic acid (see Pestic. Sci. 1974, 5, 792-793).

Furthermore, it is known to produce 4- (2 2, 2‘-dihalogeinvinyl) -3,3-dimethyl-γ-butyirolactones (Miz DOS 2 62,3 777). The dimedoma-based process can only be carried out uneconomically and, moreover, does not lead to S-dihalinyl-γ-butyrolacttoins.

We have now found a process for preparing the partially known dihialogenvinyl-γ-butyrolakites of the general formula I

in which

Hal means the same or different fluorine, chlorine or thunder atoms,

R ¹ and R ² represent the same or different radicals from the group consisting of hydrogen or (C 1 -C 4) -alkyl or together with the adjacent carbon atom form a cycloaliphatic ring of up to 7 carbon atoms, characterized in that the compound of formula (II)

in which

Hal, R ^1, R ² have the abovementioned meaning and

R ³ is hydrogen, C 1 -C 4 alkyl, optionally heated in the presence of a base and optionally in the presence of a diluent to 0 to 250 ° C.

Compounds of formula II in which Hal, R ^1, R ² and R ³ have the abovementioned meaning, are nioyé. Compounds of formula II in which Hal, R ¹ and R ² have the above meanings and R ³ is hydrogen, are produced that compounds of formula II wherein R ³ is an alkyl group having 1 to 4 carbon atoms, Soap. Those compounds of formula (II) in which R @ ³ is C1 -C4 alkyl are prepared by the formation of an oxirane of formula (IV) in which:

Hal, R ¹ and R ² have the above meanings, is reacted with a malonic acid ester of formula V

COOR ³

OF

CH2, \

COOR ³ (V) where

R ³ has the abovementioned meaning, in the presence of a base and optionally in the presence of a diluent.

If 2,2-dimethyl-3- (2 ‘, 2‘-dich, liolvinyl) oxirane and malonic acid diethyl ester are used as starting materials in this process, the reaction scheme can be illustrated as follows:

XcOOC / tf

In the course of this process, compounds of formula (II) are formed as intermediates but are not isolated in this process.

The starting materials used in this process are defined by formulas IV and V. Also preferably used herein are compounds wherein R ¹ and R ² are methyl and R ³ is preferably methyl or ethyl. The compounds of formula IV are novel and their preparation is described below.

Compounds of formula V are known substances.

The preparation of the compounds of formula II is carried out by first preparing the sodium or potassium salt of the malonic acid ester of formula V, which is usually carried out with alkoxides, such as sodium methoxide or sodium ethoxide. Alcohols such as methanol or ethanol are preferably used as solvents. The oxirane (IV) is then added dropwise at a temperature of from 20 to 100 [deg.] C., preferably at 35 to 50 [ ^deg.] C., and the reaction solution is maintained at the selected temperature for some time, usually about 1 to 6 hours. It forms sloučelnina formula II wherein R ³ znameiná alkyl having 1 to 4 carbon atoms. The saponification ester component of the compound of formula II is now carried out in the reaction medium by allowing the reaction mixture to cool, adding water or an aqueous solution of an alkali metal hydroxide, such as sodium or potassium hydroxide, until a pH of> 10 is reached. The reaction mixture is stirred at 0 to 100 ° C for up to 4 hours.

Thereafter, the alcohol present as solvent is distilled off and then acidified to pH <1 with an acid such as hydrochloric acid or sulfuric acid to give a water-insoluble product, where R ³ is hydrogen. This is preferably filtered off.

Oxinany general formula IV wherein Hal, R ¹ and R ² have the abovementioned meaning, are novel compounds.

According to the invention, oxiranes of the general formula IV, in which

Hal, R ¹ and R ² are as defined above by producing compounds of formula VI

HR ¹

HalsC-CH-C-C-R ^2,

Hal OH (VI) in which

Hal, R ¹ and R ² have the above meanings, in the presence of a dehydrohalogenating diluent and a catalyst at a temperature of 50-100 C.

Compounds of formula (VI) in which:

R ¹ and R ² represent a methyl group,

Hal are the same or different and are fluorine, chlorine or bromine, with the proviso that no more than 2 fluorine atoms can be present in the molecule of formula (VI).

These novel compounds of formula (VI) are prepared by treating a compound of formula (VII)

Rl

OF

CH 2 = CH - C - R ² , (JX (Vlij in which

O

AND)

X is hydrogen or the radical —C — R ³ , and

R ¹ , R ² and R ³ are as defined above, with a carbon tetrachloride of the formula VIII

CHaU, (VIII) in which

Hal is as defined above.

If 2-imethyl-3,5,5,5-tetuachlonpentan-2-ol is used as the starting material in the process of the invention, the reaction scheme can be illustrated as follows:

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

Hat ^ c-eu, f 'R ‘(IX) in which

Hal, R and R ² have the above meanings, and cleaving other halogenoyodíku to give compounds of formula IV.

While cleavage of the first mole of hydrogen halide was expected to give compounds of formula IX, it was surprising that cleavage of hydrogen halide from the compound of formula IX also took place in good yield and without. significant side reactions for the following reasons:

Oxirans are alkali sensitive and lead to further reactions (Houben-Weyl, Metboden der Oirganiscien Chemie, Stuttgart 1965, Vol. VI, 3, Stir. 376).

Oxiranes are readily re-opened by the action of bases (nucleophilic reagents); diols (Houben-Weyl, Vol. VI, 3, p. 457 J) are formed during water catalysis, with amino alcohols with amines.

If the oxirane contains a target. an oxygen atom adjacent to oxygen, as in a particularly preferred case where R 1 = R 2 = CH 3, then hydrolytic cleavage already occurs at room temperature (Houben-Weyl, Vol. VI, 3, p. 454 J.

Therefore, it could be expected that due to the base by which the compounds of the formula IX are to be cleaved off the hydrogen halide, the oxiranoic ring is again cleaved and the hydrogen halide is not cleaved.

Trihalomethyl groups do not react with bases mostly to cleave hydrogen halide. but ethers, carboxylic acids or the like are formed (see U.S. Pat. No. 2,561,925, lines 57 to 62J). Thus, it is particularly surprising that a smooth conversion of compounds of formula IX to compounds of formula IV is possible. .

The process according to the invention is carried out by reacting 1 mol of the compound of the formula VI with at least 2 mol of the base, optionally in the presence of a catalyst. When only 1 mole of base is used, compounds of formula IX are obtained.

The process according to the invention is preferably carried out in aqueous solution, but the use of inert organic solvents such as a hydrocarbon such as benzene or toluene, chlorinated hydrocarbons such as c, chlorobenzene as well as an ether is without any disadvantages.

Preferably, the process of the invention is carried out using suitable catalysts. As such, compounds of formulas X or XI are used:

(B)

A — L ⁽⁺⁾ —C

D γ (-) (X)

(B)

Y-N-C (xil.

in which

L is nitrogen or phosphorus and

A, B, C and D are each independently an optionally substituted alkyl, aralkylo or aryl group, or two adjacent residues A, B, C and D together with the central atom L and optionally other heteroaphoms form a heteirocycluis and

Y represents a halide, hydrogen sulphate or hydroxyl anion.

Catalysts of formula (X) are partially known or can be prepared according to known methods (Houben-Weyl, Vol. XI, 2, p. 587 et al.; Georg-Thieme-Verlag, Stuttgart 1958).

Preference is given to catalysts of the general formula X in which

A, B, C and D are C 1 -C 18 alkyl, especially methyl, ethyl, propyl, butyl, hexyl, dodecyl, octadecyl, benzyl, optionally substituted with C 1 -C 4 alkyl, alkoxy, or halogen.

Further preferred catalysts are compounds of formula XI wherein:

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

Particularly preferred catalysts used in the process of the present invention include:

tetramethylammonium chloride, tetrabutylammonium bromide, tetrabutylphosphonium chloride, tetrahutylammonium ticlide, beinzyltriethylammonium chloride, phenylbenzyldimethylammonium chloride, benzyldodecyldimethylammonium chloride,. benzyltributylammoniumohlaride, tiriethylamine, tripiropylamine, tributylamine, trihexylamine, benzylmethylamine.

The amount of catalyst can vary within wide limits. It is generally 0.1 to 10% by weight, preferably 0.3 to 6% by weight, based on the weight of the compounds of the general formula VI used.

The base is preferably sodium hydroxide or potassium hydroxide. Preferably, the process is carried out as follows:

The compounds of formula (V) are introduced and then, at temperatures between -20 and 50 ° C, preferably at 0 to 30 ° C, 1 to 1.2 equivalents of the aqueous base are added dropwise. The concentration of the base is not critical here, but it is advisable not to work too dilute and to use about 25-500 / ₀ base solutions. The base should be added as slowly as possible.

The progress of the reaction is monitored by measuring the pH value,

When the pH is 7 to 8, the catalyst and an additional 1 to 1.2 equivalents of the aqueous base are added. The concentration of the aqueous base used should be between 1 and 50%, preferably between 5 and 25%.

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

The end of the reaction is preferably determined by controlling the pH. When the pH is approximately neutral, the reaction mixture is allowed to cool and, after separation of the organic phase, is purified by distillation.

As already mentioned, the compounds of formula (VI) are known in part. The second and known compounds can be prepared as described above.

If 3-methyl-.alpha.-buteinol and carbon tetrachloride are used as starting materials in this process, the reaction scheme may be illustrated as follows:

CH 2 = CH-C-CH 3 + CC 14 ->

AND

OH

CH3

- »CCl 3 —CH3 —CHCl — C — CH3

OH

The starting materials useful in this process are defined in formulas VII and VIII. These compounds are known. The following compounds of the general formula (VII) are used:

isobutyl alcohol (3-methyl-1-buten-3-ol), allylalkohoil, 1-hutet-3-ol, 1-peltenen-3-ol, 3-meithyl-1-piperidin-3-ol, 3-ethyl -1-penten-3-ol, 1-vinylcyclopentam-1-ol

1-vinylcyclohexan-1-ol, and esters thereof, such as acetates.

Preferably, the following compounds of formula VIII are used:

CC14,

CBr4,

CC, 13Br,

CFžBr2,

CFB'1’3,

CCIBn,

CCI3F.

The reaction may be carried out in the absence or preferably in the presence of a solvent. Excess carbon tetrachloride, but also hydrocarbons such as toluene are preferably used as solvents. Acetonitrile is particularly preferred. The use of alcohols such as propainol, butanol or pemtanol is also preferred. The reaction is carried out at temperatures of about 50 to 150 ° C, optionally under pressure.

Preferably, the process for preparing the compounds of formula VI is carried out using suitable catalysts. As such, the following may be considered:

Substances which form free radicals, such as benzoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, tert-butyl hydropeiroxiide and aisoisobutyronitrile. Generally, a catalytic amount of a radical-forming substance is sufficient, but a larger amount is not harmful.

2. Metal salts in the presence of organic amines. Suitable metal salts are, for example, copper and iron salts, such as copper (II) chloride, copper (II) chloride, iron (II) sulfate, iron (III) chloride. Examples of suitable amines are pyrrolidine, piperidine, n-hutylamine, cyclohexylamine, triethylamine, dimethylamine. They can also be used in the form of their salts, such as hydrochlorides. A catalytic amount of catalyst is also sufficient for the reaction. Larger amounts accelerate the reaction.

3. The reaction can also be carried out under irradiation with UV light and / or irradiation.

The following examples illustrate the procedure of the example. However, these examples do not limit the invention.

Example 1

Dissolve 11.5 g of sodium in 250 ml of ethanol, add dropwise at room temperature 80 g of malonic acid diethyl ether and then in one hour at 30 to 35 ° C 128 g of 2 ₁ 2-dimethyl-3- (2 ' ₎ 2 dibromo-vinyl oxoxamine. The temperature was then maintained at 35 ° C for 4 hours.

To saponify the resulting 4-methyl-3- (2 ', 2'-dihromivinyl) -ylamino-2-carboxylic-2-carboxylic acid ethyl ester, 800 mL of 10% sodium hydroxide solution was added to the reaction solution, and the mixture was stirred at room temperature for 12 hours. . Ethainol was distilled off and the reaction solution was acidified with concentrated hydrochloric acid to pH 1. 4-Methyl-2- (2 ‘, 2‘-diibromoyl) -yl-valeroilakitone-2-carboxylic acid precipitated with a melting point of 140 ° C. This acid is filtered off and suspended in o-dichloro-benzene and heated with stirring at 170-180 ° C for 2 hours. After cooling, 91 g (61%) of 4-methyl-3- (2 3-, 2‘-dibrominyl) -yl-valerolactone crystallized, m.p. 115 ° C.

Example 1 a d 2

11.5 g of sodium are dissolved in 250 ml of ethanol, 80 g of malonic acid diethyl ester are added dropwise at room temperature and then 83.5 g of 2,2-dimethyl-3- (2 ', 2') are added at 40 ° C over one hour. -dichlorvinyl) oxirane. The temperature is then maintained at 40 DEG C. for 3 hours, after which 800 g of 10% sodium hydroxide solution are added. The mixture was then heated to boiling for 2 to 3 hours, the ethainol was distilled off and the pH adjusted to 1 with concentrated hydrochloric acid. 2-carboxylic acid melting at 138 ° C after drying.

Example 1 a d 3

To a mixture of 480 g, 1-dimethyl-2,4,4,4-tetrachlorobutainol and 10 ml of triethylamine was added dropwise 195 g of 45% sodium hydroxide solution at room temperature. The mixture is stirred at room temperature for 3 hours, then: 3000 ml of water, 20 g of tetrabutylaminium chloride and 112 g of potassium hydroxide are added and heated to boiling for 8 hours. After cooling, the organic phase is separated, the aqueous phase is extracted with methylene chloride, and the combined organic phases are fractionated in vacuo. There were obtained 294 g (88% of theory) of 2,2-dimethyl-3- (2 ', 2'-dichlorvilnyl) oxirane the · b.p. 63-65 ^C C / / 2000 mbar. n _D ²⁰ = 1.4752.

He attaches

To a mixture of 480 gl, l-dimethyl-2,4,4,4-tetrachlorbutainolu tributylamimu and 10 ml at room temperature, 195 g přiikape 45o / _o sodium hydroxide. The mixture is stirred at room temperature for 3 hours, then 3000 ml of water, 20 ml of tributylamine and 112 g of potassium hydroxide are added and the mixture is heated at reflux for 12 hours. After cooling, the organic phase is separated, 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'-dichloro-vinyl) -oxirane of vial temperature 62-63 ° C / 1866 Pa are obtained.

Example 5

To a mixture of 480 g of 1,1-dimethyl-2,4,4,4,4-tetra-chlorobutanol and 10 ml of triethylamine was added dropwise 19.5 g of 45% sodium hydroxide solution at room temperature over 2 hours. The mixture was stirred at room temperature for 5 hours, water was added to the precipitated sodium chloride to dissolve and the pH was adjusted to neutral. The organic phase was separated, the aqueous phase was extracted with methylene, hiloride and the combined organic phases were firacomized in vacuo. Yielding 3-81 g (94%) of 2,2-dimethyl-3- (2 ', 2', 2'-oxirane-trlQhilioreiťhylJ b.p. 8-2 to 84 ° Cels-a / 1733 Pa. N _D ²⁰ = 1.4690.

203.5 g of 2,2-dimethyl-3- (2 ', 2', 2'-trichloroethylhexyl), 150-0 m -1 of water, 56 g of potassium hydroxide and 10 g of tetrabutylammonium bromide are heated with stirring for 10 hours After cooling, the organic phase is separated off, the aqueous phase is extracted with methyleine alcohol and the combined organic phases are fractionated in vacuo to give 144 g (86% _of theory) of 2,2-dimethyl-3-ol. - (2 ', 2'-di-chlorvinyl) oxirane, boiling point 68 ° C / 2266 Pa.

Example 6

430 g (5 mol) of 3-methyl-1-butem-3-ol, 2500 ml of carbon tetrachloride and 40 g of water-containing benzoylporoxide are heated to boiling for 10 hours using a water trap. After the addition of 40 g of wet benzoyl peroxide, the mixture was boiled again for 10 hours using a water separator. After cooling, the reaction solution was washed with cold 1 N sodium hydroxide solution to remove the benzoic acid formed. The solvent is then distilled off. The residue was distilled in an oil pump vacuum. 971 g (81% of theory) of 1,1-dimethyl-2,4,4,4-tetrafluorobutanol are obtained, b.p. 75 DEG-85 DEG C./0.3 mbar. The structure was provided by IC- and NMR spectra. n _D ²⁰ = 1.4975.

Example 7

12-0 g of 1,1-dimethyl-2-propenylacetate, 332 grams of carbon bromide, 16 g of n-butylamine and 14 g of ferric chloride (hexahydrate) in 220 g of acetonitrile are heated at 1-0- for 12 hours. Low: 14 ° C. After cooling, the mixture is filtered, the solvent is distilled off and 168 g of potassium hydroxide in 2000 ml of water are added dropwise at room temperature. Thereafter, 20 g of tetrabutylammonium chloride is added and the mixture is heated at 80 DEG C. for 1 hour, after cooling the pH is brought to neutral and extracted with methyleine chloride. Fractional distillation is then carried out. 159 g (62% of theory) of 2,2-dimethyl-3- (2 ', 2'-dibromivinyl) -oxane are obtained at a boiling point of 86-88 ° C / 2000 Pa. n _D ²⁰ = 1.533.2. Nuclear Magnetic Resonance Spectrum (δ in CDCl 3): δ S (ppm) = 1.3 to 1.4 (d, 6 protons), 3.25 and 3.4 (d, 1 P); 6.2 and 6.35 (d, IP).

Claims (1)

PftEDMBT A process for the preparation of oxirane derivatives of the general formula IV (IV Ynalezu or together with an adjacent carbon atom forms a cycloaliphatic ring of up to 7 carbon atoms, characterized in that the compounds of the general formula (VI) H Ri ABC-H-CH2-C - C-R ^2, - ... i r Ha-1 OH in which Hal means the same or different fluorine, chlorine or bromine atoms, R ¹ and R ² represent identical or different radicals from the group formed-Reine hydrogen or alkyl (hydrocarbyl of 1 to 4 carbon atoms (VI) -němž Hal, R ¹ and R ² have the above meanings, in the presence dehydírohíalogenují base and optionally in the presence of a diluent and a catalyst at a temperature of 50 to 100 ^C C.