CS257330B1 - Process for preparing 1-tricyclo (3,3,1,13,7) decanecarboxylic acid - Google Patents

Abstract

1-Tricyclo(3,3,1,13'7)decanecarboxylic acid is an intermediate for the preparation of pharmacologically active substances. Tricyclo(3,3,1,13'7)decane is oxidized with chlorine under iodine catalysis in a medium of concentrated sulfuric acid and methylene chloride, after which formic acid is added and the reaction is completed. After neutralization and reduction, methylene chloride is distilled from the reaction mixture. Filtration gives 1-tricyclo-(3,3,1,13'7)decanecarboxylic acid in high yield and purity.

Description

The invention relates to a process for the preparation of 1-tricyclo (3,3,1,1, 1 '(decanecarboxylic acid of formula (I))

C

ΧΟΗ (I)

7 by carboxylation of tricyclo (3,3,1,1 '(decane).

7

1-Tricyclo (3,3,1,1,1) -decanecarboxylic acid is an intermediate for the preparation of pharmaceutically active substances.

7

So far, 1-tricyclo (3,3,1,1 ') decanecarboxylic acid has been prepared from tricyclo (3,3,3,7)

1,1 ') of the dean by its carboxylation with formic acid in sulfuric acid and carbon tetrachloride under the action of tert-butyl alcohol in a yield of 50 to 70% (Stetter H., Rauscher E., chem.

Ber., 93, 2054/1960 /), or carboxylation 1-tricyclo (3,3,1, l ^{3 '7)} decane, and 20% oleum (polis J. Raquel BP, USSR, 401, 132/1975 /) .

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A disadvantage of these production methods is the low yield of 1-tricyclo (3,3,1,1 '(decanecarboxylic acid and the use of concentrated sulfuric acid or oleic acid in molar feeds 2 to 4 orders of magnitude larger than the stoichiometric feed), which complicates the reaction mixture considerably, disproportionately increases the salinity of wastes and reduces the productivity of the production equipment

1-tricyclo (3,3,1, l ^{3 '7)} -dekankarboxylové acid can be obtained by carboxylation of 1-bromo or 7 13

-hydroxy-tricyclo (3,3,1,1 ') decane with formic acid or carbon monoxide. However, it is desirable to prepare 1-bromo or 1-hydroxy-tricyclo (3,3,1,1 ') decane for this production method.

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Disadvantages of the above methods for the preparation of 1-tricyclo (3,3,1,1 '(decanecarboxylic acid 37) substantially eliminates the process for the preparation of 1-tricyclo (3,3,1,1') decanecarboxylic acid, by carboxylation of tricyclo (3 (3,1,1 ') decane formic acid or carbon monoxide according to the invention, characterized in that tricyclo (3,3,1,1 * ⁵ '} decane is oxidized by chlorine under catalysis with iodine in sulfuric acid and methylene chloride and / or 1,2-dichloroethane, followed by the addition of formic acid and / or carbon monoxide and the reaction is complete.

7 at a temperature of 1 to 48 hours, the reaction mixture is neutralized and the precipitated 1-tricyclo (3,3,1,1 ') decanecarboxylic acid is filtered. Yield of product was 25%. 85 to 95%. The beneficial effect of 3 7 oxidation of tricyclo (3,3,1,1 '(dean by chlorine during iodine catalysis) is due to the high selectivity of oxidation. The beneficial effect of methylene chloride is that it excellently dissolves the chlorination products of tricyclo (3,3,1,1') The advantageous effect of sulfuric acid is that it does not affect the activity of the iodine catalyst during chlorination, removes the influence of catalytic poisons such as water or alcohols or strong Lewis acids on the selectivity of the effect of the iodine catalyst during chlorination, The whole reaction can be carried out at a temperature of -10 to 40 ° C, preferably at a temperature of 10 to 20 ° C. concentrated sulfuric acid preferably 500 to 1500 weight percent, for methylene chloride preferably 120 to 240 weight percent, for iodine preferably 2 to 4 weight percent %, for chlorine preferably 53 to 65% by weight and for formic acid (conc. 90%), preferably 50 to 100 weight percent. An appropriate amount of carbon monoxide can be used instead of formic acid. The methylene chloride can be reused into the following batch after being trapped in the freezer.

The preparation according to the invention is simple, safe, inexpensive and relatively easy to process; In practically one step, the product is obtained in high yield from tricyclo (3,3,1,1 ') decane. The reaction proceeds at room temperature and is particularly suitable for larger batches of raw materials.

The process according to the invention is explained in more detail by means of the following example.

Example 1

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A suspension of 2.5 g of tricyclo (3.3.1.1 ') decane, 5 g of methylene chloride, 37 g of concentrated sulfuric acid and 0.09 g of iodine was stirred for 30 minutes, then at 15-20 ° C for 2 hours 1.5 g of chlorine was introduced, then 2 g of formic acid (90% concentration) were added and the mixture was stirred at 20 ° C for 24 hours. After neutralization, reduction and distillation of methylene chloride, 2.9 g of 1-tricyclo (3,3,1,1 ') decanecarboxylic acid were obtained by filtration. The melting point in the sealed capillary tube was 173 ° C.

Claims (2)

SUBJECT OF THE INVENTION A process for the preparation of 1-tricyclo (3,3,1,1,4-d) decanecarboxylic acid of formula (I) OF OH (X) 3 7 by carboxylation of tricyclo (3,3,1,1 ') dean with formic acid, characterized in that tricyclo (3,3,3 1,1 ') the decane is oxidized with chlorine under catalysis with iodine in a medium of sulfuric acid and methylene chloride and / or 1,2-dichloroethane, then formic acid and / or carbon monoxide are added and the reaction is completed.