Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-01-31
2002-01-29
Killos, Paul J. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S189000
Reexamination Certificate
active
06342626
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for the preparation of alkyl ester from commercial lactic acid. The present invention particularly relates to a catalyst-free improved process for the conversion of aqueous commercial lactic acid containing free acid, dimer or highpolymers of lactic acids to alkyl ester by reaction with alcohol.
BACKGROUND AND PRIOR ART REFERENCES
Esters of lactic acid are high boiling liquids with properties of interest as solvents and as plasticizers for cellulose plastics and vinyl resins. Butyl lactate is used as a high boiling solvent in lacquer formulations. The advantages of lactic acid and its esters in cosmetics and toiletries formulations have been reported (Manufac. Chem., 1999, May, 18-19). Lactate esters can be regarded as a new generation of skin whitening agents that have been shown to produce a synergistic effect when combined with other skin whitening agents (Purac Products—Brochures, www.purac.com.). Lactate esters are used to meet the high quality demands of semiconductor industry as a safe solvent in photoresist and in edgebead removal formulations (Purac Products—Brochures, www.purac.com.). A valuable way of producing butyl acrylate is by dehydration of butyl lactate (Manufacturing Chemist, 1999, May, 18-19; J. Chem. Tech. Biotech., 1994, 59, 149-156). Butyl lactate is used as a co-surfactant in preparation of microemulsions with anionic surfactants (J. Disp. Sci. Tech., 1997, 18, 161-175). Detergent compositions containing carbonate and/or lactate esters are useful for removal of pitch, wax polishing materials and protective films from the optical parts (CA, 1997, 126, 159058s). Lactate esters are used as non-inflammable and mild odor solvent cleaners (U.S. Pat. No. 5,604,196). Lactate esters especially calcium stearyl lactate enhances the shelf life and organoleptic characteristics of starchy food [JP 07,203,834]. Alkyl lactates are used for degreasing surfaces and defluxing of circuit boards contaminated by soldering fluxes (CA, 1990, 112, 58912c). Lactic acid esters are useful in the preparation of herbicidal formulations (CA, 1991, 115 29370z; WO, 91,00,278). Dopamine derivative formulated with lactic acid esters, fatty acid monoglycerides and/or higher alcohols showed high permeability through the rat skin in vitro (CA, 1991, 115, 239731u; EP-431942; JP-317, 343). An invention related to butyrate prodrugs prepared from methyl lactate and butyrylchloride is described (CA, 1997, 126, 321080s, WO 97 12,855). Ethyl lactate can be used in the treatment of acne and against seborrhoea [Acta Dermat. (Stockholm), 1972, 52, 406). Esterification of crude lactic acid and subsequent hydrolysis to produce lactic acid is reported as a procedure for purification of lactic acid.
Many methods are described in prior art for conversion of lactic acid to alkyl esters. Reaction between lactic acid and alcohols or carboxylic acids catalyzed by lipase from
Candida antarctica
with hexane as solvent was reported (Biotechnol. Lett. 1997, 19, 315-317). The authors found lactic acid to be a good acyl donor and esters of both primary and secondary alcohols were synthesized. Dimer formation due to lactic acid acting as both nucleophile and acyl donor was not observed. Butyl lactate was synthesized using heterogeneous supported hetero polyacid catalyst, PW
12
/SiO
2
(Huaxue Yu Nianhe, 1996, 3, 128-130). Japanese patents (JP-05, 155,816; JP-05, 140,039) describe preparation of ethyl lactate from lactonitrile with water and sulfuric or phosphoric acid followed by esterification with ethanol. U.S. Pat. No. 5,264,617 report synthesis of butyl lactate by depolymerization of polylactide by heating with butanol in the presence of p-toluene sulfonic acid. European Patent [EP 517,571] describes esterification of ammonium lactate with methanol at reduced pressure. Japanese Patent (JP 07,258,154) describes that autoclaving a mixture of lactamide, Zr oxide and methanol at 200° C. and 34 atm for 2 hr give methyl lactate in 97.8% selectivity at 94.3% conversion. A process for manufacture of ethyl lactate for use in food industry is described in a patent [CN 1,102,180] with a catalyst comprising of H-type acidic resin complex of glycerin or ethylene glycol and boric acid, sodium dihydrogen phosphate in weight ratio of 1:(0.5-1.0):(0.1-0.2). The process comprises reacting 80% lactic acid and ethanol (92-93%) in the presence of the catalyst. A research paper describes the kinetics of liquid phase synthesis and hydrolysis of butyl lactate catalyzed by cation exchange resin [J. Chem. Technol. Biotechnol, (1994) 59, 149-50]. Japanese Patent (JP 07,10,805) describes preparation of hydroxy carboxylic acid ester in a two phase system of aqueous lactic acid and alcohol like butanol in the presence of inorganic salt like sodium chloride and sulfuric acid catalyst at room temperature with vigorous stirring for 2 h to give yield of 70% butyl lactate and the yield was 37% without sodium chloride. n-Butyl lactate was synthesized with solid super strong acid catalyst derived from sulfuric acid and TiO
2
(CA, 1995, 122, 190924n). Method of producing lactic acid and lactic acid esters is described in European Patent (EP 614,983). The process involves fermentation of a culture medium with ammonia and adjusting pH of the culture medium with ammonia and to the resulting ammonium lactate solution is added butanol or pentanol and heating the resultant mixture thereby inducing esterification of lactic acid with alcohol and at the same time effecting liberation and recovery of ammonia and adding a mineral acid to promote complete esterification.
Synthesis of butyl lactate was studied by Chinese researchers [Synthetic Commu., 1994, 24, 3269-75] with super acid resin catalyst D001-AlCl
3
(sulfonated cross linked polystyrene macroporous strong acid cation exchange resin). German Patent [Ger Off DG 4,341,770] describes a process for preparation of high purity lactate esters via the lactic acid or its salts followed by esterification, wherein the fermented product is neutralized with alkaline earth carbonates or bicarbonates and byproducts removed by treatment with ammonia and CO
2
and the purified ammonium lactate solution is esterified. Catalytic synthesis of n-butyl lactate with rare earth sulfate was studied [Huaxue Shijie, 1998, 39, 199-201]. The esterification of n-butanol with lactic acid yielded >85% butyl lactate.
Japanese Patent [JP, 08 40,983] claims synthesis of lactic acid ester by reaction of lactide with alcohol in the presence of strong acidic ion exchange resin. Yet another patent [WO, 91-11527, CA, 1992, 116, 5328m] describes production of lactic acid esters which comprises (a) formation of ammonium lactates with lactic acid forming organisms in the presence of ammonia, (b) reacting ammonium lactate with alcohol and gaseous CO
2
to esterify ammonium lactate and (c) recovering pure lactic acid ester. Synthesis of lactates by using modified HZSM-5, as catalyst is reported (CA, 1995, 123,116189f). A new technique of preparation of ethyl lactate by rectification method was reported to increase the yield to over 95% (CA, 1996, 124, 235465y).
According to a Japanese Patent (JP 08,208,565) a mixture of aqueous lactic acid, ethanol and p-toluene sulphonic acid was heated at 160° C. and ethanol and water were removed by distillation to give a solution having acid value of 1.9 mg KOH/g which was mixed with NaOH/EtOH and distilled to give product having acid value 0.1 mg KOH/g with 85% yield. Lactic acid esters are prepared by hydrogenation of glycidic acid ester with Pd/C in EtOH at r.t. in 66% yield [JP-08,73,407]. Ethyl and butyl lactates were prepared in yield of >90% using strongly acidic cation exchanger 732 and D72 as catalyst by reacting the acid and alcohol in a molar ratio of 1:3.5 and the catalyst concentration was 60% that of lactic acid [Talyuan Gongye Faxue Xuebao, 1990, 21, 43-6].
Alpha-acetoxypropionic acid and methanol are fed
Kaimal Thengumpillil Narayana Balagopala
Laxmi Ayyagari Ananta
Ramalinga Bandi
Vijayalakshmi Penumarthy
Baker & Botts L.L.P.
Council of Scientific & Industrial Research
Killos Paul J.
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