CS246816B1 - 4,9-Dianantanebisacetic acid and its preparation - Google Patents

Abstract

The solution relates to 4,9-dianantane· bisacetic acid and a method for its preparation. This compound can serve as a nonone for the preparation of special polymers with increased thermal stability, resistance to short-wave radiation and abrasion resistance. It is prepared by the reaction of non-substituted or disubstituted dianantane derivatives with β 1,1-dichloroethylene in the presence of sulfuric acid. For its preparation, such dianantane derivatives are suitable, the substituents of which are chlorine, bromine, hydroxyl group, nitro group, nitrate group or carboxyethyl.

Description

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

4,9-Diamantanebisacetic 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 been described yet.

4,9-Diamantanebiacetic acid has the structural formula I in the appendix. The essence of the process is to prepare mono-substituted or diaubetitected diamantane derivatives of the general formula H, also listed in the appendix, where X is chlorine or bromine or hydroxyl or nitro or nitrate or carboxymethyl, and Y represents a hydrogen or chlorine atom or a bromine atom or a hydroxyl group or a nitro or nitrate group, or a mixture thereof and 1,1-dichloroethylene in the presence of 60 to 100% by weight of acid. at a temperature of -20 to + 32 ° C. The molar ratio of sulfuric acid 1,1-dichloroethylene II used is 10 to 1000 µL to 100 µL.

this reaction results in the formation of products from which acid can be formed

4,9-diamantanebisacetate as least soluble obtained by crystallization from a suitable solvent. By-products of the reaction are diamantane, 1-chlorodiamantane, 4-diamantaneacetic acid, chlordiamantaneacetic acid and hydroxydiamantaneacetic acid. These compounds provide further reaction with 4,9-diamantanebisacetic acid with 1,1-dichloroethylene so that the crystallization residue after isolation of this compound from the reaction mixture can be used for the next reaction.

The yield of 4-9-diamantanebisacetic acid depends primarily on the nature of the starting compound. Higher yields (almost quantitative) yield disubetitected derivatives, monosubetituated derivatives yield lower yields. The yield further depends on the nature of the substituent and the reaction time.

The reaction is carried out by stirring the raw material mixture for 5 minutes to 10 hours depending on the starting compound. The reaction ae is carried out at a temperature of -20 to + 32 ° C, preferably at -10 to + 2 ° C. The reaction mixture is then quenched by pouring onto ice or water and the crude reaction product is filtered off with suction or extracted with a suitable solvent such as ether or chloroform. The product obtained is boiled with a suitable solvent, e.g. hexane, benzene, chloroform and the like, and upon cooling, undissolved 4,9-diamantanebisacetic acid is suctioned off. • J246 816

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

Example 1 y

To 100 g of 96% HgSO4 cooled to OfC was added 2.2 g

Of 4,9-dihydroxydiamantane and 10 ml of CCl8 CH2 and stirred at OrC for 30 min. It is then poured onto ice, the precipitated product is filtered off with suction, washed with water, dried and boiled with 25 ml of benzene for 20 minutes. After cooling, the insoluble matter is filtered off with suction. 2.3 g of 4,9-diamantanebisacetic acid of 4. 338 339.5 40 and 0.8 g of crystallization residue

Example 2

100 g of 96% SiO2, 3.5 g of a mixture of dibromodiamantanes and 10 ml of CCl2 CH2 are used for the reaction. The reaction was carried out and worked up as in Example 1. Roba reaction for 5 h. 1.9 g of acid were obtained

4,9-diamantanebisacetate and 1.2 g of crystallization residue.

Example 3

250 g of H 2 SO 4, 5 g of 1-hydroxydiamantane and 25 µl of CCl 3 · OH 6 are used for the reaction. The extract was washed with water, dried and the ether was distilled off. The distillation residue is boiled with 50 ml of benzene and the product is filtered off with suction after cooling. 2.5 g of acid are obtained

4,9-diamantanebisacetic and 3.7 g of crystallization residue *

Example 4

100 g of HgSO4, 2 g of 1-nitrodiamantane and 10 ml of CCl5SsCHg are used for the reaction. The reaction is carried out and worked up as in Example 3. Reaction time 5 ^h . 0.85 S of 4,9-diamantanebisacetic acid and 1.7 g of crystallization residue are obtained.

Example 5

250 g of H 2 SO 4, 5 S of the crystallization residue according to Example 3 and 25 ml of OCl 3 S 5 CH 3 were used for the reaction. The reaction was carried out and worked up as in Example 1. Reaction time 10 h. 3.1 g of 4,9-diamantanebisacetic acid and 1 g of crystallization residue were obtained.

Claims (2)

OBJECT OF THE INVENTION 1 * 4,9-Diamantanebisacetic acid of formula I · 246 816 2. A process for the preparation of 4,9-diamantanebisacetic acid of the formula I as claimed in claim 1, characterized in that the diemantane derivatives of the general formula II are those in which X is chlorine or bromine or hydroxyl or nitro or nitrate or carbozymethyl; a hydrogen atom or a chlorine atom or a bromine atom or a hydroxyl group or a nitro group or a nitrate group, optionally mixtures thereof, with 1,1-dichloroethylene in the presence of sulfuric acid at a concentration of 60 to 100% by weight at -20 to + 32 ° C; wherein the molar ratio of sulfuric acid: 1,1-cichlorethylene: II is 10 to 1000: 1 to 100: 1