CH321866A - Process for the preparation of a, B-epoxycarbonitriles - Google Patents

Description

  

  Process for the production of a, ss.epoxycarbonitriles It is known to produce esters of a, f -epoxycarboxylic acids from the a.liphatic or mixed aliphatic-aromatic series by a process that is described by Darzen (see, inter alia, Organic Reactions, Roger Adams, Part V, page 413, uf).

   According to this procedure, an ester of an α-halocarboxylic acid is left with. an aldehyde or ketone from the aliphatic or ge miseht aliphatiseh-aromatic series under anhydrous conditions and using a condensing agent such. B. sodium tritimätbylat or lithium amide, react.



  The present invention relates. relate to the production of a, ss-epoxy carbonitriles, which compounds have not been previously described.



  In the process according to the invention, the α, / T-epoxy carbonite.rile is produced by allowing aldehydes or ketones to react under anhydrous conditions with a halogen aeetonitrile using a condensation agent such as sodium ethylate or lithium amide.



  In general, those connections come with. an aldehyde or ketone group in question, which do not contain any other groups that easily. can react with the halogen atom or the cy an group of haloacetonitriles.



  For carrying out the process according to the invention, among others, saturated aliphatic or mixed vliphatic aromatic aldehydes or ketones are suitable. Alicyclic or mixed aliphatic-alicyclic aldehydes or ketones, such as cyclohexanone, cyclopentane-methanol,

      also heterocyclic or mixed aliphatic-heterocyclic aldehydes or ketones, e.g. B. nicotinaldehyde, can with. Halogen-acetonitrile react in the presence of a condensation agent with the formation of a, ss \ epoxy carbonitriles.



  It was found that chloroacetonitrile delivers better yield than bromo- or .todacetonitrile.



  The amounts of the reaction components are preferably chosen such that 1 1101 aldehyde (or ketone), 1 mol of condensation agent and about 1.5 mol of haloacetonitrile react with one another.

   Although solvents such as benzene or petroleum ether can be used, they are not recommended in all cases. The reaction components are preferably combined at a low temperature, in particular at about -ä0 C. a ,, B - Epoxycarbonitriles can be used as intermediates in the preparation of therapeutically important compounds. will.



  <I> Example I </I> A mixture of 30 g of benzaldehyde and 27 g of chloroacetonite was added with stirring and introduction of nitrogen at a temperature of -10 C in smaller amounts 17.5 g of sodium methylate. The reaction mixture was during the addition of the sodium methylate with. 50 em3 anhydrous diethyl ether diluted to prevent the mixture from coagulating.

   After all the sodium methylate has been added. the mixture was further stirred for 4 hours at a low temperature, and then poured into ice water acidified with acetic acid. The obtained liquid. was extracted with the help of ether and the ethereal layer was on top of it with. an aqueous solution of 30g sodium bisulfite to remove unchanged benzaldehyde and then shaken with water.

   The washed ethereal solution was getxocknet on sodium sulfate. Purified phenylglycidic acid nitrile was obtained in that the excess of the aforementioned. Solution, from which the ether was removed by evaporation, was subjected to vacuum distillation at a pressure of 2 mm. The boiling point of the substance obtained was 104 to 106; the yield was 24.5 g.

   This product was distilled in vacuo with the yield of the same reaction in which 150 g of benzaldehyde were used. Here at 2 fractions arose, of which the first fraction had a boiling point in the range between 102 and 107 C and the second fraction between 108 and 118 C. The ultraviolet absorption spectrum of both fractions showed a maximum at 220 mu and a second maximum at 285 mcc.



  <I> Example </I> II 85 g of sodium methoxide were added to a mixture of 150 g of acetophenone and 18 g of chloroacetonitrile with stirring and introduction of nitrogen at a temperature of about -10 ° C. During the reaction, 50 g of anhydrous diethyl ether were added to the reaction mixture in order to prevent it from coagulating.

   The reaction mixture was poured into water acidified with acetic acid and then purified and processed in the manner described in Example I. The obtained crude product was subjected to vacuum distillation to give a yield of 121 g which had a boiling point at 3 mm of mercury. in the range between 102 and 106 C. The ultraviolet = absorption spectrum of this substance had a maximum at 220 my, the extinction f (egg%) being 427.

 

Claims (1)

<B> PATENT CLAIM </B> Process for the production of α, γ-epoxy carbonitriles, characterized in that aldehydes or ketones are reacted under anhydrous conditions with a haloacetonitrile using a condensing agent. SUBClaims 1. Method according to claim, characterized in that aliphatic aldehydes or ketones are reacted with a halogen aeetonitrile. becomes. 2. Method according to patent claim, characterized in that mixed. aliphatic-aromatic aldehydes or ket: one with a haloacetonitrile for reaction ge., is brought. 3. The method according to claim, da .. characterized in that alicyclic alde hyde or ketones with. a halo-aeetonitrile is reacted. 4th Method according to claim, characterized in that mixed aliphatic-alicyclic aldehydes or ketones are reacted with a halogen aeetonitrile. 5. The method according to claim, characterized in that da.ss heterocyclic aldehydes or ketones are reacted with a halogen aeetonitrile. 6th The method according to the patent claim, characterized in that mixed aliphatic-heterocyclic aldehydes or ketones are reacted with a haloacetonitrile. 7. The method according to claim, characterized in that an aldehyde or ketone with. Chloracetonitrile is brought to the reaction. B. Process according to patent claim, characterized in that 1 mol of aldehyde or ketone, 1: VIol of condensing agent and about 1.5 mol of 1-halogeno-acetonitrile are reacted with one another. 9. The method according to claim and dependent claim 8, characterized in that benzaldehyde is reacted with halogen aeetonitrile. 10. The method according to claim and dependent claim 8, characterized in that aeetophenone is reacted with halogen acetonitrile. 11. The method according to claim, characterized in that the reaction components are put together at a temperature below a C.