CS201749B1 - Process for preparing 6-hydroxybicyclo [2.2.1] heptane-3,5-carbolactose-2-carboxylic acid - Google Patents

Abstract

The invention relates to a method for preparing 6-hydroxy-biocyclo[2,2,1]-heptan-3,5-carbolactoa-2-carboxylic acid by hydrolysis and hydration of biocyclo[2,2,1]-hept-5-ene-2-hydroxy-dicarboxylic acid and subsequent lactonization, whereby the resulting product is obtained in high yield and high purity. The reaction is carried out at a temperature of 40 to 90 °C for 3 to 5 hours in the presence of a hydroxylating and hydrating agent prepared from salts of transition metal elements of groups 5 and 6 of the Mendeleev periodic table of elements, hydrogen peroxide, water and tert. butanol, whereby the molar ratio of the starting material to hydrogen peroxide is in the range of 1 to 1.1 to 1. 1.6 and the resulting product is separated from the reaction mixture.

Description

201 749 1

The present invention provides a process for the preparation of 6-hydroxy-bicyclo [2.2.1] -heptane-3,5-carbolactone-2-carboxylic acid by hydrolysis and hydrotreating with a bicyclo [2.2.1] -hept-5- -en-2,3-anhydride-dicarboxylic acid, followed by lactone, the resulting product being obtained in high yield as well as with a high degree of purity of 6-hydroxy-bio-cyclo [2.2.1] -heptene-3 The 5-carbolactone-2-carboxylic acid was prepared by reacting the bicyclo [2.2.1] -hept-5-ene-2,3-anhydride-dicarboxylic acid with the addition of ootic acid and hydrogen peroxide in 4 hours. hours at 85 ° C (Alder K., McLle HHnAn. Chem., 11, 7 (1958)). 6-Hydroxy-bicyclo [2.2.1] -heptane-3,5-carbolactone-2-carboxylic acid spontaneously precipitates out of the reaction medium and, after recrystallization from acetonitrile, has a melting point of 196-197 ° C. A disadvantage of this process is the necessity of distilling off the water and regenerating it in the pro-o o circulating ootic acid, which is highly corrosive.

According to the present invention, there is provided a process for the preparation of 6-hydroxy-bicyclo [2.2.1] -heptane-3,5-carbolactone-2-carboxylic acid of formula (1).

by the action of the hydroxylating agent on the bicyclo [2.2.1] -hept-5-yn-2,3-enhydride-dicarboxylic acid is carried out by reacting at a temperature of 40 to 90 ° C for 3-5 hours in the presence of a hydroxylating and hydrating agent prepared from the salts of elements with transition moieties 5 · and 6 · of the Mendelian phenomenon of periodic elements, preferably tungsten, molybdenum and vanadium, hydrogen peroxide, water and tero. butanol, wherein the molar ratio of starting material to hydrogen peroxide is in the range of 1: 1.1 to 1: 1.6 and the resulting product is separated from the reaction mixture.

Thus, according to the invention, 6-hydroxy-bicyclo [2.2.1] -heptane-3,5-carbolactone-2-carboxylic acid (i) is prepared by hydrophilicity and hydroxylase (b). -hept-5-ene-2,3-anhydride-dicarboxylic acid (X1). As a hydrating and hydroxylating agent, a mixture of hydrogen peroxide, water, tero is used. butanol (t-BuOH) and transition metal salts of metal acids, followed by the lactonization of 5,6-dihydroxy-bio-cyclo- (2,2,1) -heptane-2,3-dicarboxylic acid (III) to 6-Hydroxy-Bicyclo [2.2.1] -heptane-3,5-carbolactone-2-carboxylic acid (i): 201,749

II III i

The molar ratio of the cyclo- / 2,2,1 H -hept-5-ene-2,3-ahydro-dicarboxylic acid to the cauldron peroxide is from 1 s to 1.1 to 1! 1.6. The advantage of the process is the possibility of using a commercially unavailable 30 uL solution of watery peroxide in water, which is not necessary to concentrate. The temperature optimum of the reaction is in the range of 40 to 90 ° C and in which the thermo-catalytic decomposition of the cauldron peroxide in the optimal temperature and ekonomiokomsúlade. The reaction time is between 3 and 5 hours. Incorporating the reaction® signals the occurrence of the oxidation potential of the reaction system. After the reaction has been quenched, the reaction precipitates to a temperature close to 0 DEG C., and the product reacts in crystalline form and is generally isolated by filtration.

Alkali and ammonium salts of transition element moieties from the 3 rd and 6 th groups of the Mendelian periodic system, preferably tungsten, molybdenum and vanadium, can be used as the reactivity catalyst in the amount of 0.7 to 3 percent of the reactive mass.

Transient molar acid salts of tartaric acid such as tungsten, molybdenum and vanadium with hydrogen peroxide and water provide the corresponding peroxy acids which have been used as the active hydroxyladders for hydroxylation of linear and cyclic alkenes and unsaturated carboxylic acids (Mugdan M., Young). P.i J. Cham. Soo., 2888 (1949)]. The resulting peroxyacid epoxidizes the double bond of the bicyclo [2.2.1] -hept-5-ene-2,3-anhydride-dicarboxylic acid or the bicyclo- [2,2,1] -hept-5-ene formed therefrom -2,3-dicarboxylic acid. The corresponding epoxide derivatives in aqueous medium hydrolyzed to the common product 5,6-dihydroxy-bio-cyclo- (2,2,1) -heptene-2,3-dicarboxylic acid which by intramolecular esterification yields 6-hydroxy-bio-cyclo- 2,2,1 / -heptane-3,5-carbolactone-2-dicarboxylic acid. The product was identified by mp 196-197 ° C, infrared, mass and NMR spectrometry. The product is of interest both because of its configuration and functional groups which allow interesting polymerization, condensation and other reactions, the added substances have rare mechanical-physical properties, with regard to configuration. The product can also be used as an intermediate for Saline syntheses. In particular, the advantage of the invention is the high product purity of up to 99.9 high product yield reaching up to the steohiometriocyst, a simple and technologically simple procedure. 201 749 3

The invention is explained in more detail in the appended claims, wherein the preamble of the invention is not exclusive to the examples. Example 1 25 wt. parts of bio-cyclo [2.2.1] -hept-5-ene-2,3-anhydride-dicarboxylic acid, 23.73 wt. parts of 30% hydrogen peroxide, 33.75 wt. tero. butanol and 0.96 parts by weight of NagVOI / HgO does not react for 5 hours at 70 ° C. The water peroxide feed is stirred for 15 minutes and kept so that the temperature is maintained at the desired value. Thereafter, the reaction mixture was cooled to 4 ° C and 24.83 parts by weight of 6-hydroxy-bio-cyclo [2.2.1] -heptane-3,5-carbolactone-2-carboxylic acid were precipitated in the form of crystals after 10-12 hours yielding 82.5% yield. The melting point of the thus obtained product is 196 ° C and its purity according to the chromatographic analysis is 99.6%. Example 2 25 wt. parts of bicyclo [2.2.1] -hept-5-ene-2,3-anhydride-dicarboxylic acid, 27.65 wt. parts of 30% hydrogen peroxide, 33.75 wt. tero. of butanol and 0.96 parts by weight of Na2SO4 .2H2 O by reaction at 75 DEG C. for 5 hours gives 29.53% by weight of Na2SO4. 6-hydroxy-bio-cyclo [2.2.1] -heptane-3,5-carbolactone-2-carboxylic acid (98.2% yield). Melting point 196 ° C purity 99.8 ¢. Example 3 25 wt. parts of bio-cyclo [2.2.1] -hept-5-ene-2,3-anhydride-dicarboxylic acid, 20.73 wt. parts of 30% hydrogen peroxide, 33.75 wt. tero. of butanol and 0.75 parts by weight of Na 2 MoO 2 · 2 H 2 O by reacting at 50 ° C for 4 hours gives 17.45 wt. a part product of which 12.68 wt. parts are 6-hydroxy-bio-cyclo [2.2.1] -heptane-3,5 ** carbolactone-2-carboxylic acid, which is 72.7 .mu.g / v. the biocyclo [2.2.1] -hept-5-ene-2,3-dicarboxylic acid. Example 4

Reakoia as in Example 1, except that the molar ratio of the bio-cyclo- / 2,2,1 / -hept-5-ene-2,3-anhydride-dicarboxylic acid to the hydrogen peroxide is 1: 1.5, the temperature of 70 ° C, 4 hours and 1% NagMoO2 yields 6-hydroxy-bio-cyclo [2.2.1] -heptane-3,5-carbolactone-2-carboxylic acid 78.5%, purity 99.5%. 5 °.

Claims (1)

Example 5 As in Example 4 and the difference that the molar ratio is equal to 1; 1.2} 70 [deg.] C. 4 hours and 99 [mu] l (NH4 [iota] OH) [delta] 75.5 [delta] purity. Example 6 As in Example 4, except that the molar ratio is equal to 1: 1.4, temperature 75 ° C, time 5 hours and 1% of Na2SO4.22O2O, yield 99.81%, purity 99.5% 5 Example 7 As in Example 4 and the difference that the molar ratio is equal to 1: 1.5} temperature 80 ° C} time 4 hours and 1% Na 2 MoO 2 · 2 0 0 0, yield 98.7%, purity 99.5 Example 8 As in Example 4 a the difference being that the molar ratio is 1: 1.2} the temperature of 80 ° C} the time of 4 hours and the 1% NagMoO 2 .HgO} yield of 99.8%, purity 99.9% 5 Example 9 As in Example 4 e the difference being that the molar ratio is 1: 1.4, the temperature of 75 ° C, the time of 5 hours, and the 1 µl of Na 2 O 3 → 2H 2 O, yield 99.9 ° C, the purity of 99.9 6-hydroxy-bio-2, 2, 2-Heptene-3,5-carbolactone-2-carboxylic acid It is possible to use it for oleic acid synthesis BEFORE THE INVENTION Preparation Method 6-Hydroxy-Bicyclo [2.2.1] -heptene-3,5-carbolactone - 2-carboxylic acid of formula By the addition of a hydroxylating agent to bicyclo [2.2.1] -hept-5-ene-2,3-ahydride-dicarboxylic acid, 201,749 5, the reaction is carried out at a temperature of 40 to 90 ° C after for a period of from 3 to 5 hours in the presence of a hydroxyladic and hydrating agent prepared from transition moieties of 5, and a group of Mandelaev's periodic constituents, preferably tungsten, molybdenum and van & ampoule, hydrogen peroxide, water and tero. butanol, the mole ratio of the yield raw material to hydrogen peroxide is between 1 and 1.1 to 1: 1.6 and the resulting product is separated from the reaction mixture.