IL26648A - Dioxolanes,oxathiolanes and their preparation - Google Patents

Description

PATENT ATTORNEYS Ί 11 REINHOLD COHN I Π 1 MICHAEL COHN I 3 3 D ISRAEL SHACHTER H 3 Dl File 25323 PATENTS AND DESIGNS ORDINANCE SPECIFICATION Oxathiolanes and their preparation on a German Limited of Haus Bensberg bei Germany do hereby declare the nature of this invention and in what manner the same is to he to he particularly described and ascertained in and the following statement This invention relates to novel chemical compounds and methods of preparing the More this invention is concerned with dioxolanes and oxathiolanes and novel derivatives thereof and processes for producing such According to this invention there is provided a novel class of compounds of the formula wherein and are independently phenyl or koxyphenyl or and together stand for a diphenylene is hydrogen or lower n is an integer of 1 to X is oxygen A is halogen or a group or where and are independently hydrogen or alkyl having up to 8 carbon or and form together with the nitrogen atom to which they are attached a saturated heterocyclic and their quaternary ammonium salts and the acid addition compounds of this invention possess spasmodic It is known that the antispasmodics presently in use act to develop either a pronounced tropic or neurotropic specificity of The known synthetically manufactured compounds are usually esters or ethers of benzilic acid or their hydrogenation products with certain amino The compounds of this invention surprisingly exhibit a good action in the above further they are easily soluble in water and are stable against attack acids or they stantially no harmful or adverse side effects having yet been observed following their The compounds this invention are prepared by a reaction between acid of the formula ll OH wherein and X have the significance previously assigned and a compound of the III R and A have the significance previously assigned and B represents a dihalogen methyl an aldehyde or a derivative for thioacetal or a bisulfite addition where A is the resultant product corresponding to Formula I can be if with a compound selected the group of compounds of the formula wherein and have the previously assigned and represents a member selected from the group consisting of hydrogen and alkali The bases represented here are useful as in the preparation of the salts also described in the The term as used herein is intended to include all or pharmacologically acceptable salts of the free including both the acid addition salts and the quaternary ammonium salts and organic bases of the foregoing type salts with a variety of inorganic and strong organic acids including and related They also form quaternary ammonium salts with a variety of organic esters of and aromatic sulfonic Among such esters are and benzyl chloride and dimethyl methyl benzene ethylene methallyl and the used the reaction benzilic thiobenzilie dicyelohexylglycolic acid and acid of the compounds of Formula III which may he used as reactants in this process are the diethylacetals pionaldehyde and The hitherto unknown diethylacetals of and are prepared and diethylasaine or piperidine by boiling the reactants together in an inert solvent or by direct heating of the reactants in a bomb acid addition salts may be suitably prepared directly from the reaction mixture by acidifying with dilute acid as hydrochloric alkyl halide quaternary salts are suitabl prepared by treating the base in an anhydrous solvent with an excess of the following examples given in order to more clearly disclose the nature of the present It should he that the examples are not intended to be a limitation of the scope of the EXAMPLE 1 23 g benzilic acid and g were dissolved in 200 ml glacial acetic Dry HOI gas was introduced with agitation at room temperature into the resulting solution to the saturation The mixture was allowed to stand for 1 After the glacial acetic acid had been removed evaporation at low temperature in a the reaction product was poured into the acid fractions neutralized with solid and the neutral substances extracted with Following drying and removal of the solvent by an oil It could be purified by column chromatography on silica gel diameter with by adding increasing amounts of which was established by thin layer chromatography on Silicagel plates using as the eluant to be a single was dissolved in absolute Dry gas was fed into the cooled solution thereby produced up to the saturation precipitated product could be purified by dissolution and crystallization out of a mixture of and 33 g acid and 22 g were dissolved by heating in 100 ml glacial acetic After cooling to a slow current of dry gas waa introduced with agitation into the solution fo a period of After removing the glacial acetic acid by evaporation in a the oil which remained was dissolved in and treated with solid When the evolution of had water was added and the organic phase neutralized with After the solvent was the remaining oil distilled over in a high of ram at was thereby This latter compound was boiled with 12 of dry piperidine in 120 ml of absolute benzene for 12 hours with A total of 6 g of hydrochloride was thereby precipitated The latter was removed by and the benaene solution remainin concentrated by The residue was dissolved with a little chloroform the solution was applied to a dry aluminum oxide column to It was then elutriated with After the solution had concentrated by an oil was which was dissolved with absolute diethyl The introduction of dry gas into the cooled solutio produced a precipitate was dissolved crystallized out of a mixture of isopropanol and Melting point The following compounds were prepared using an diphen Free base Oil Hydrochloride Oil Free base Oil S salt formed with Oil base Oil Hydrochloride Free base Hydrochloride Free base Oil Hydrochloride clohex Oil Hydrochloride Examples and t iobenzilic acid was used in the reaction instead of benzilic Free base Oil base Oil Hydrochloride Free base Oil Free base Oil Hydrochloride compounds listed above are characterised by an intense carbonyl absorption in the infrared spectral region In the case of the derivates it is located at 1800 and in the case of the derivates it is located at 1780 This property serves to Identify this class of compounds both qualitatively and can be used for their quantitative 10 insufficientOCRQuality

Claims (1)

1. CLAIMS DiQxolane oxathiolane of the formula and are independently phenyl or koxyphenyl or and together stand for a diphenylene is hydroge or lower n is an integer of 1 to is oxygen or A is halogen or a group or where and are independently hydrogen or having up to 8 carbon or and form together with the nitrogen atom to which they are attached a saturated heterocyclic and their quaternary salts and the acid addition diphen 5 11 2664S 2 5 Process for the manufacture of a compound in the base form as set out in Claim 1 which mprises reacting an acid of the formula II wherein and X are as above defined with a compound of the formula III wherein n and A have the above designated meaning and B represents a selected from the group consisting of dihalogen methylene aldehyde and their derivatives thioaoetal and bisulfite addition where A is theresultant product corresponding to formula I is reacted with a compound selected from the group consisting of 12 or 3 IV wherein and have the above meaning and stands for hydrogen or an alkali insufficientOCRQuality