CS240246B1 - 4,9-diamantane-bischloroacetic acid and its preparation - Google Patents

Abstract

4,9-Diamantane-bischloroacetic acid and a method for its preparation. This acid can serve as a monomer for the preparation of special polymers with increased thermal stability, resistance to short-wave radiation and resistance to abrasion. It is prepared by the reaction of monosubstituted or disubstituted diamondate derivatives from trichloroethylene in the presence of sulfuric acid. For its preparation, such mono- and disubstituted diamondate derivatives are suitable, the substituents of which are OH, Cl, Br, NO2, ONO2, CHC1COOH.

Description

The invention relates to 4,9-diamantane-bis-chloroacetic acid and to a process for its preparation.

4,9-Diamantanebischloroacetic acid can serve as a monomer for the preparation of special polymers characterized by increased thermal stability, shortwave resistance and abrasion resistance. The preparation of this compound has not yet been described.

4,9-Diamantanebischloroacetic acid has the structural formula I shown in the Annex. The method of its preparation consists in that the diamantane derivatives of the general formula II, wherein X = OH, Cl, Br, NO ₂ , NO ₂ , CHCl ₃ -COOH, and Y = H, OH, Cl, Br, NO ₂ , ONO ₂ or mixtures thereof is reacted with trichlorethylene in the presence of sulfuric acid at a temperature of -10 to +60 ° C, the molar ratio of H ₂ SO ₄ : CCl ₂ - CHCl: diamantane derivatives of the general formula II is 10 to 1000: 1 to 100 The sulfuric acid concentration may be 60 to 100% by weight.

The monosubstituted and unsubstituted diamantane derivatives of the general formula II listed in the Annex may serve as raw materials for the preparation of this compound. These compounds provide a mixture of products from which 4,9-diamantanebisloroacetic acid as the least soluble can be readily obtained by crystallization from a suitable organic solvent. The byproducts of the reaction are diamantane, 1-chlorodiamantane, 4-diamantanchloroacetic acid, hydroxydianamantane chloroacetic acid and chlorodiamantane chloroacetic acid. These substances, with the exception of diamantane, give 4,9-diamantanebisloroacetic acid by further reaction with trichlorethylene, so that the crystallization residue after isolation of this compound from the crude reaction mixture can be used for the next reaction.

The yield of 4,9-diainantane-bischloroacetic acid depends primarily on the nature of the starting material. Generally, higher yields (almost quantitative) yield disubstituted derivatives, monosubstituted derivatives provide lower yield. The yield further depends on the nature of the substituent and the reaction time. A mixture of the above compounds may also be used for the reaction.

The reaction is carried out by stirring the mixture of raw materials in a suitable reaction vessel for 5 minutes to 10 hours, depending on the nature of the starting material, then quenching by pouring on ice or water and sucking off the crude product and drying or extracting with a suitable organic solvent such as ether . The crude product is boiled with a suitable solvent such as chloroform, benzene, and the like, and upon cooling, the insoluble 4,9-diamantanebischloroacetic acid is aspirated. The reactions may be carried out at a temperature of from -10 ° C to + 60 ° C, preferably from 0 ° C to 30 ° C. At higher temperatures, other by-products are formed which are difficult to separate from the 4,9-diamantanebischloroacetic acid and which cannot be converted to this by further reaction.

The process according to the invention is illustrated in more detail in the examples below.

P.example 1 and d 1

To 50 g of concentrated H ₂ SO ₄ cooled to 0 ° C was added 2.05 g of 1-hydroxydiamantane and, with stirring, 9.2 ml CCl ₂ = CHCl was added in portions. The reaction mixture was stirred at room temperature for 8 hours, quenched by pouring onto ice and extracted with ether. The ether extract was washed with water, dried and the ether was distilled off. 40 ml of chloroform are added to the residue, heated to boiling for 15-20 minutes and, after cooling, the insoluble matter is filtered off with suction. 1.05 g of 4,9-diamantane-bischloroacetic acid is obtained. (··

After distilling off the chloroform, there is obtained 2.1 grams of a crystallization residue containing diamantane, chlordiamantane, 4-diamantane chloroacetic acid and chlordiamantane chloroacetic acid and hydroxydiamantane chloroacetic acid.

Example 2

To 200 g of concentrated H ₂ SO ₄ cooled to 0 ° C was added dropwise a solution of 1.0 g of 4-hydroxydiamantanu in 50 ml of CC1 ₂ = CHCl, and the reaction mixture was stirred for 8 h at room temperature. It was then poured onto ice and extracted with ether. The ether solution was shaken with 5% aqueous ammonia, water, dried and the ether was distilled off. 1.0 g of a neutral fraction is obtained containing diamantane and chlordiamantane. The alkaline waters were acidified with HCl, the precipitated product was filtered off with suction, washed with water and dried. 0.4 g of a mixture containing 5% of diamantane chloroacetic acid, 18% of chloro- and hydroxydiamantane chloroacetic acid and 77% of 4,9-diamantanebischloroacetic acid is obtained.

Example 3

To 90 g of concentrated H ₂ SO ₄ cooled to 0 ° C, a solution of 3.8 g of 1-chlorodiamantane in 15 ml of CCl ₂ = CHCl was added dropwise with stirring.

Example 9

To 100 g of concentrated H ₂ SO ₄ at room temperature were added 5.0 g of the crystallization residue of Example 1 and 15 ml of CCl ₂ -CHCl. The reaction mixture was stirred at the same temperature for 8 h and treated in the same manner as in Example 1. 1.6 g of 4,9-diamantanebischloroacetic acid and 3.1 g of crystallization residue were obtained. The melting point of 4,9-diamantane-bischloroacetic acid is greater than 360 degrees Celsius, the melting point of the dimethyl ester of 4,9-diamantane-bischloroacetic acid is 153.2 to 154.7 ° C.

Claims (3)

SUBJECT 1. 4,9-Diamantanebischloroacetic acid of the formula I. 2. A process for the preparation of 4,9-diamantane-bischloroacetic acid of the formula I according to claim 1, characterized in that the diamantane derivatives of the general formula II are: X = OH, Cl, Br, NO ₂ , ONO ₂ , CHCl-COOH and Y - H, OH, Cl, Br, NO ₂ , ONO ₂ optionally OF THE INVENTION mixtures thereof, reacting with trichlorethylene in the presence of sulfuric acid at a temperature of -10 ° C to + 60 ° C, wherein the molar ratio of sulfuric acid: trichlorethylene: diamantane derivatives of formula II is 10 to 1000: 1 to 100: 1. 3. A process according to claim 1, wherein the concentration of sulfuric acid is 60-100%. wt.