1356909 10 5 25 30 35 45 PATENT SPECIFICATION (21) Application No. 10763/73 G1) Convention Application No, 004237 (G3) Swiczezland (CH) a (51) International Classification CO7C 49/30 (52) Index at acceptance C2C_ 221 225 227 22Y 305 30Y 351 353 366 368 387 43X 635 638 668 UF ‘Complete Specification published 19 June 1974 ay (54) PROCESS FOR THE PREPARATION OF SUCCINYLOSUCCINIC ACID DIESTERS (7) _ We, LONZA LTD., of Gampel/ Valais, Switzetiand, a Joint-Stock Company organized under the laws of Switzeriand, do hereby declare the invention, for which’ we pray that a patent may be granted to us, find the method by which it is to be per formed to be particularly described ia and by the following statemen The present invention is concemed with a process for the preparation of succinylosuccinic Acid dsr from yhaloaeoacts aid esr, Te is Known to prepare succinylosuccinic acid. dase from Jpeflorotetoatic estes in water, using sodium phenolate, yields of 589% thereby being obtained (see Bull. Soc. Chim, France, 29, 402—406/1921). Iris also known to prepare succinglosuccinic acid diesters using diethyl succinate as start= ing material, In this case, the reaction is car- cied out with the use of sodium ethylate, The highest yields which have thereby been achieved ‘were about 80% (see U.S. Patent Specification No, 3,024,268). However, a di advantage of this process is that the isolation of the succinylosuccinic acid diester is extremely laborious and time-consuming. Furthermore, large quantities of solvents are needed. Tt is an object of the present invention to prepare succinylosuccnic acid diesters from ‘rhaloacetoacetic acid esters by means of a simple process and in high yields, ‘Thus, according t¢ the present invention, there is provided a process for the preparation of succinylosuccinic acid diesers from »-halo- acetoacetic acid esters in water, wherein the reaction of the y-haloacetoacetc ester is cart ‘out in an aqueous buffer solution of inorgai salts at a pH value of $10. ‘The pH value which must be maintained ting the reaction is between 8 and 10 and is preferably about 9.5, This pH value of 8 to 10 and preferably’ of about 9.5, is main- tained during the reaction by the use of an aqueous buffer solution of inorganic salts. AS buffer mixture, there are preferably used mix- tures of sodium carbonate and sodium bicar~ [Price 259] bonate or of sodium bicarbonate and sodium hydroxide or of borax and sodium hydroxide. Th the case of mixtures of sodium carbonate and sodium bicarbonate, it i preferred to use a ratio of 0.5 to 1.5 mole sodium carbonate t0 15 to 05 ‘mole sodium bicarbonate, in the case of mixtures of sodium bicarbonate and sodium hydroxide, it is preferred to use a ratio of 1 mole sodium bicarbonate t0 0.2 19 0.8 mole sodium hydroxide and in the case of borax and sodium hydroxide, it is preferred to use a ratio of 1 mole borax to 0.08 to 1.5 ‘mole sodium hydroxide. ‘The preferred y-haloacetoacetic acid esters are the y-chloroacetoacetc esters but itis also possible to use, for example, the y-bromoaceto- Acetic esters. The alcoho! component. of the ester used a8 starting material depends ‘upon the succinylosuccinic acid diester to be pre- pared. Preferably, however, there are used esters, the alcobol component of which con~ tains up to 4 carbon atoms, the methyl and ethyl esters being especially” preferred. ‘The reaction temperature used is prefer- sbly ~10 to +10°C. and more preferably =2 to 0°C. After completion of the reaction, the suc- cinylosuccinic acid diester can be isolated by filtering off or by centrifuging off. The product obtained is white to slightly yellowish and has a degree of purity of more than 99%. Succinylosucinic acid diester can’be used, for example, for the production of polymers and also for the preparation of quinacridone dyestuffs, The following Examples are given for the purpose of illustrating the present invention: — Example 1 11.50 g, (0.108 mole) anhydrous sodium carbonate and 3.10 g. (0.036 mole) sodium bicarbonate were dissolved in water and 11.88 8. (0.072 mole) ethyl y-chlorcacetoacetate Were introduced at —1.5°C, while stirring. After 24 hours at —15°C, the precipitate ‘was filtered off with suction, sluried with 150 mil, water, again filtered off with suction 1356909 50 70 B 80 8510 15 25 35 1,356,909 2 and dried, There were obtained 6.951 g. diethyl. suecinylosuccinate, which correspond to a yield of 75.1% of theory. The product hhad a purity of 99.8%, and a melting point of 1263—126.4°C, Example 2 11.738 g. Methyl »-chloroacetoacetate were reacted ina manner analogous to that des- cribed in Example 1, There were obtained 6.233 g, dimethyl succinylosuceinate, the yield ‘being 70.1% of theory. The product had a melting point of 153.4°C. Example 3 12.395 g. isopropyl y-chloroacetoacetate were reacted in 2 manner analogous to that described in Example 1. There were obtained +g. diisopropyl succinylosuccinate, the yield being 63.9%, of theory. The product had ‘a melting point of 102.8°C. Analysi CyHaOp found: C5935 H7.19%5 0 33.6% (by difference) cale.: 59.14% 7.05% 5 33.76%. Example 4 15.20 g, (0.18 mole) sodium bicarbonate and 430g. (0.108 mole) sodium hydroxide were dissolved in 200 ml. water and mixed at =15°C, while stirring, with 11.712 g, ethyl spchlorogcetoacetate, After 24 hours at 15°C, the precipitate was filtered off with suction “slurried in 150 ml, water, again filtered off with suction and dried, There were obtained 6.746 g. diethyl succinylosuccinate, the yield being 74.0% of theory. WHAT WE CLAIM IS:— 1, Process for the preparation of succinylo- succinic acid diesters from y-haloacetoacetic acid esters in water, wherein the reaction of the y-haloncetoscetic acid ester is carried out in an aqueous buffer solution of inorganic salts ata pH value of $10, 2, Process according to claim 1, wherein, 25 buffer solution, there is used an aqueous sokue tion of sodium carbonate and sodium bice bonate in a ratio of 0.5 10 1.5 mole sodium carbonate t0 15 to 0.5 mole sodium bicar- Donate. 3. Process according to claim 1, wherein, 0 buffer solution, there i used an aqueous solu tion of sodium bicarbonate and sodium hydroxide in a ratio of 1 mole sodium bicar- bonate to 02 to 0.8 mole sodium hydroxide. 4, Brocess according to claim 1, wherein as buffer solution, there is used an aqueous solu- 55 tion of borax and sodium hydroxide in a ratio of 1 mole borax t0 0.08 to 1.5 mole sodium hydroxide. 5. Process according to any of the preseding claims, wherein the reaction is carried out at 60 a temperature of —10 to +10°C. 6. Process according to claim 5, wherein the reaction is carried out at @ temperature of =2 to °C. 7. Process according to any of the preceding 65 claims, wherein the alcohol component of the -phaloacetorcetic acid ester contains up to + Earbon atoms. 8, Process according to claim 7, wherein a ‘etinyl or ethyl >-haloaceroacerate is used. 9, Process according 10 claim 1 for the preparation of succinylosuccinic acid diesters, substantially 5 hereinbefore described and exemplified. 10. Succinylosuccinic acid diesters, when- 75 ever prepared by the process according to any of claims 1 to 9. 50 0 VENNER, SHIPLEY & CO, ‘Chartered Patent Agents, Rugby Chambers, 2 Rugby Street, Printed for Her Majesty's Stationery Office, by the Cuurier Pros, Leamington Spa, 1974. ‘Bubliied by Te Patent Oficn, 29 Southampton Buildings, owdon, WC2A 1A, from ‘phich copes may be obtained,