SU883009A1 - Method of preparing dipropargylic esters of unsaturated dicarboxalic acids - Google Patents

Description

(5) METHOD OF OBTAINING DIPROPARGIL ETHERS OF UNLIMITED DICARBONIC ACIDS

The invention relates to a process for the preparation of the dipropargyl esters of unsaturated dicarboxylic acids of the general formula j-COOCH CrCCH COOCHiC CH and R CH which can be used as starting materials in the industry of organic synthesis, and the same in polymer chemistry. A known method of producing propargyl esters of acrylic and methacrylic acids by the action of acrylic chloride (methacrylyl) on propargyl alcohol in pyridine at 70-80 ° C. The outputs are: for propargylacrylate 30, for propargylmethacrylate. The disadvantages of the method include: a multistage process (obtaining acrylyl chloride or methacrylyl), carrying out the reaction in pyridine, the low yield of the target product. There is also known a method for producing maleic acid dipropargyl ester by heating maleic anhydride and propargyl alcohol in benzene at boiling in npi cyT p-toluene sulfonic acid for 17-20 hours at an anhydride: 1: 2 molar ratio. Output - 50% of theory 2J. The disadvantages of this method are the low yield of the desired product, the reaction in benzene, and the duration of the process. The closest to the proposed technical essence and the achieved effect is the method of obtaining the dipropargyl esters of unsaturated dicarboxylic acids of the general formula COOCH СгСН COOCHiCrCH a. by the interaction of the corresponding CHIH anhydrides of unsaturated dicarbonic acids and propargyl alcohol, taken in a molar ratio of 1: 2 at EO-EZ C for 4 hours in the presence of a catalyst of sulfuric acid, followed by treatment of the reaction product with a saturated soda solution, water and alcohol solution caustic soda and water, yield b5% of theoretical GZ. The disadvantages of this method include the relatively low yield of the target product, the complexity of the processing and extraction of the target product. The purpose of the invention is to simplify the process technology and increase the yield of target products. The delivered goal is achieved by the method of preparing dipropargyl: 1-unsaturated dicarboxylic acids of the general formula coaxial with COOCHiCsCH R CH, by reacting the corresponding anhydrides of unsaturated dicarboxylic acids and propargyl alcohol, taken in a molar ratio of 1: 3-6 at 50: 75%; which use phosphorus oxychloride in an amount of 3-7 wt. based on anhydride. Distinctive features of the proposed method are the use of phosphorus oxychloride as a catalyst in the amount of weight D. based on the anhydride and the reaction carried out at the indicated molar ratio and temperature. The method is carried out by the interaction of propargyl alcohol with maleic anhydrides, cyclohexene 4 and bicycloheptenedicarboxylic acids in the presence of phosphorus oxychloride as a catalyst at 50-75 s for 6-8 hours. The molar ratio of anhydride of non-specific dicarboxylic acid and propargyl alcohol 1: 3-6. Example 1. A method of producing male-f-iiriir tlVif | iiril ' b 4 IX 7SHG11 |, / (L flOJ 14 GI n V / DW acid) dipropargyl ether. In a four-necked flask equipped with a mechanical stirrer, a dropping funnel, a reflux condenser and a thermometer are placed 9.8 g (0.1 mol of maleic anhydride and 28.0 g (0.5 mol) of propargyl alcohol). While stirring for 20 minutes, 0.5 g (5 eec.jPOClj is added from the dropping funnel, maintaining the temperature, then continue stirring for another 8 hours at a temperature of 60 ° C; the crystals of alum which precipitate out after the distillation of the propargyl alcohol are distilled off by crystallization from sulfuric ether, 18.2 g of Die ether are obtained, mp 36-37 ° C. Yield relative to the theory Found:% C 61.99, H 5.30 CioH804 Calculated, 0: C about 2.50, H 4 , 19, IR cm -V 1 720, l) 1650,;, nsajV rc 2Uo, v. 3290. Example 2: 15.2 g of the preparation of dipropargyl ester of cyclohexene dicarboxylic acid. , 1 mol) of cyclohexene dicarboxylic anhydride and 28.0 g (0.5 mol) of propargyl alcohol. About 7b g of 5 wt. 1 POCl 3 are fed from the dropping funnel and after the whole amount is fed the mixture is heated at 60 ° C for 8 h. After distilling off the excess alcohol, the residue is extracted with sulfuric ether, washed with water, and dried with NanS04. The ether is distilled off and the remaining part is distilled under vacuum. This gives 22.6 g (yield 91.8% of theory) of ether 2 with bp. 1 7t-l 7bs / 5 mm. Upon cooling, white crystals with a melting point of 40–41 ° C were found. Found% C 68.67, H 6.06 (4 Calculated,%: C 68.29; H 5.72. IR cm:% o.s. 11bO-j with C 1740, Vj, (; 2135, Vc-H 3300. Example 3. A method for producing bicycloheptenedicarboxylic acid dipropargyl ester. 8 set up analogically to example 1 and placed 6, kg (0.1 mol) of bicycloheptenedicarboxylic anhydride and 28.0 g of propargyl alcohol. 0.82 g of 5 wt.% POCI are fed from the dropping funnel. At the end of the feed, the mixture is heated for 8 hours at 60 ° C. After the excess alcohol is distilled off, the residue is extracted with sulfuric ether, washed with water, and dried. ether, then the main product under vacuum.To receive 2t, 2 g (yield of EZ, relative to theory) of ether 3 with the following characteristics: bp 1591MI characteristics: mm, P 1.5081, df 1.1661,: / 1 mm , P 1.5081, 1 Ml 66.68 (calculated 67.17) Found,%: C 69.76, H 5.6. 4 Calculated,%: C 69.91, H 6.17. IR (C, , Qc l60, V (,, 1bcho, l) 213b, Vc o1720, V Ha-2880, ic-H 3300. Example. A method for producing the dipropargyl maleic ester of Example 1, but using an amount of 3 wt.% Catalyst ( 0.29 g) per anhydride. Yield 88.0%.

The proposed method in comparison with the known allows significantly

Claims (3)

increase the yield of the target pro / uktov (up to 90-95%) and simplify the technology 96 EXAMPLE 5. The method for producing maleic acid dipropargyl ester of Example 1, but using a catalyst in an amount of 7 DG (0.68 g) on anhydride. The output of 80.4%. With similar amounts of catalyst (3 wt.%) And (7 wt.%) Dipropargyl esters of cyclohexene dicarboxylic acid 2 and bicycloheptenedicarboxylic acid 3 were obtained with yields of 75, U, 8t, 5 and 79.6%, and 86.0%, respectively. Analogously to example 1, experiments were performed to determine the effect of temperature and ratio of reagents on the yield of esters 1, 2 and 3. The results are shown in the table. As can be seen from the table, the optimal molar ratio of anhydride of a supernuminal dicarboxylic acid: propargyl alcohol is a ratio of 1: 5 and a temperature of 60 ° C. The amount of catalyst taken is optimally 5% by weight of anhydride. The change of this amount in the direction of decreasing the yield of the target product decreases, and with an increase in - the product is tarred. 78 as a result of eliminating the processing steps of the reaction product with a solution of sodium hydroxide, sodium hydroxide and water. Claims The method of producing the dipropargyl esters of unsaturated dicarboxylic acids of the general formula COOCHiCf CH COOCHiCsCH by reacting the corresponding anhydrides of unsaturated dicarboxylic acids and propargyl alcohol at elevated temperatures in the presence of a catalyst, characterized in that, in order to simplify the process technology and increase the yield of the target products, the resultant products are unalterable. catalyst use phosphorus oxychloride in an amount of 3-7weight. in the calculation of the anhydride and the interaction is carried out at a molar ratio of anhydride: propargyl alcohol 1: 3-6 and temperature 5075 C. Sources of information / taken into account in the examination 1. M. Ilkhamov and others. Synthesis of propargyl esters of acrylic acids and dimerization of propargyl methacrylate . -Uzbek Chemical Journal, 1967 № 3, p. 39 2. Medvedeva L.I. and others. Cyclic polymerization of unsaturated acid propargyl esters. High Molecular Compounds, A IX, 1967, No. 9, p. 2042. 3. Korshak V.V. et al. Synthesis and study of the properties of polyesters containing triple bonds in a chain. - Uzbek Chemical Journal, 1964, No. 1, p. b7 (prototype).