Europäisches Patentamt *EP001052258B1* (19) European Patent Office Office européen des brevets (11) EP 1 052 258 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: C07D 307/33, C07D 307/32 of the grant of the patent: 03.03.2004 Bulletin 2004/10 (86) International application number: PCT/JP1998/005840 (21) Application number: 98961502.6 (87) International publication number: (22) Date of filing: 24.12.1998 WO 1999/033817 (08.07.1999 Gazette 1999/27) (54) PROCESS FOR PRODUCING BETA-HYDROXY-GAMMA-BUTYROLACTONE DERIVATIVES AND BETA-(METH)ACRYLOYLOXY-GAMMA-BUTYROLACTONE DERIVATIVES VERFAHREN ZUR HERSTELLUNG VON BETA-HYDROXY-GAMMA-BUTYROLACTON-DERIVATEN UND BETA-(METH)ACRYLOXY-GAMMA-BUTYROLACTON-DERIVATEN PROCEDE DE PRODUCTION DE DERIVES DE BETA-HYDROXY-GAMMA-BUTYROLACTONE ET DE DERIVES DE BETA-(METH)ACRYLOYLOXY-GAMMA-BUTYROLACTONE (84) Designated Contracting States: (74) Representative: HOFFMANN - EITLE DE FR GB Patent- und Rechtsanwälte Arabellastrasse 4 (30) Priority: 25.12.1997 JP 35771597 81925 München (DE) (43) Date of publication of application: (56) References cited: 15.11.2000 Bulletin 2000/46 JP-A- 2 129 645 JP-A- 10 212 283 JP-A- 54 095 558 US-A- 4 968 817 (73) Proprietor: Mitsubishi Rayon Co., Ltd. Tokyo 108-8506 (JP) • SAME-TING CHEN ET AL: "PREPARATION OF OPTICALLY ACTIVE TERTIARY ALCOHOLS BY (72) Inventors: ENZYMATIC METHODS" JOURNAL OF • MURATA, Naoshi, Mitsubishi Rayon Co., Ltd. ORGANIC CHEMISTRY, AMERICAN CHEMICAL Otake-shi, Hiroshima 739-0693 (JP) SOCIETY. EASTON, US, vol. 62, 1997, pages • SAKANO, Kunihiko, Mitsubishi Rayon Co., Ltd. 4349-4357, XP002087684 ISSN: 0022-3263 Otake-shi, Hiroshima 739-0693 (JP) • IKEMOTO, Tetsuya, Mitsubishi Rayon Co., Ltd. Otake-shi, Hiroshima 739-0693 (JP) Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 052 258 B1 Printed by Jouve, 75001 PARIS (FR) EP 1 052 258 B1 Description TECHNICAL FIELD 5 [0001] The present invention relates to a process for preparing β-hydroxy-γ-butyrolactone and β-methyl-β-hydroxy- γ-butyrolactone (hereinafter referred to as "β-hydroxy-γ-butyrolactones"), and a process for preparing β-(meth)acryloy- loxy-γ-butyrolactone and β-methyl-β-(meth)acryloyloxy-γ-butyrolactone (hereinafter referred to as "β-(meth)acryloy- loxy-γ-butyrolactones") which are useful as a constituent component monomer of paints, adhesives, sticking agents, resins for ink,-and the like. 10 BACKGROUND ART [0002] As a process for preparing β-hydroxy-γ-butyrolactones used as a precursor of β-(meth)acryloyloxy-γ-butyro- lactones, for example, a process of reacting glycidol with carbon monoxide at high temperature under high pressure 15 using a noble metal catalyst as a catalyst (U.S. Patent No. 4,968,817) and a process of lactonizing an epoxidized product, obtained by reacting 3-butenoic acid with hydrogen peroxide in the presence of a platinum catalyst, after hydrating the epoxidized product (Angew. Chem., Int. Ed. Eng. 994-1000 (1966)) are known, but both of them are methods with high risk of explosion. [0003] Since it was difficult to industrially prepare β-hydroxy-γ-butyrolactones as described above, β-(meth)acryloy- 20 loxy-γ-butyrolactones using these compounds as a raw material have never been produced industrially, regardless of its expected use for various purposes For such a reason, it has been desired to develop a process for preparing β-hydroxy-γ-butyrolactones in a safe and simple manner, and a process for preparing β-(meth)acryloyloxy-γ-butyrolactones. 25 DISCLOSURE OF THE INVENTION [0004] It is an object of the present invention to provide a process for preparing β-hydroxy-γ-butyrolactones in a safe and simple manner, and a process for preparing β-(meth)acryloyloxy-γ-butyrolactones, which are useful as a constituent component monomer of paints, adhesives, sticking agents, resins for ink, and the like, using β-hydroxy-γ-butyrolactones 30 obtained by the above process. [0005] That is, the present invention provides a process for preparing corresponding β-hydroxy-γ-butyrolactone or β-methyl-β-hydroxy-γ-butyrolactone represented by the formula (1) : 35 40 wherein R1 represents a hydrogen atom or a methyl group, which comprises cyanating glycidol or 2-methyl-2,3-epox- ypropanol, followed by hydrolysis and further lactonization. [0006] The present invention also provides a process for preparing corresponding β-(meth)acryloyloxy-γ-butyrolac- 45 tone or β-methyl-β-(meth)acryloyloxy-γ-butyrolactone represented by the formula (2): 50 55 wherein R1 and R2 independently represent a hydrogen atom or a methyl group, which comprises preparing β-hydroxy- γ-butyrolactone or β-methyl-β-hydroxy-γ-butyrolactone by the process of claim 1, and reacting the resulting β-hydroxy- γ-butyrolactone or β-methyl-β-hydroxy-γ-butyrolactone with (meth)acrylic acid chloride, (meth)acrylic acid or (meth) 2 EP 1 052 258 B1 acrylic ester. [0007] In the process of the present invention, glycidol or 2-methyl-2,3-epoxypropanol is cyanated, first, in order to prepare β-hydroxy-γ-butyrolactone or β-methyl-β-hydroxy-γ-butyrolactone represented by the formula (1), which are referred to as β-hydroxy-γ-butyrolactones. The process of cyanation is not specifically limited, but cyanation is usually 5 performed by the reaction with hydrocyanic acid or hydrocyanate. [0008] The process of cyanating using hydrocyanic acid includes, for example, a process of reacting glycidol or 2-methyl-2,3-epoxypropanol with hydrocyanic acid in the presence of a basic catalyst. The basic catalyst used in the reaction is not specifically limited, but an inorganic alkali salt such as sodium hydroxide, sodium carbonate and potas- sium carbonate is preferred because of easy control of the reaction and cheap price. 10 [0009] Furthermore, the process of cyanating using hydrocyanate includes, for example, a process of reacting gly- cidol or 2-methyl-2,3-epoxypropanol with hydrocyanate in a weak acidic solution such as aqueous magnesium sulfate solution or acetic acid. The hydrocyanate used in the reaction includes various metal salts, but cheap potassium cyanate and sodium cyanate are preferably used. [0010] The reaction temperature for cyanation is preferably from -20 to 70°C, and the reaction is performed, more 15 preferably, at a temperature ranging from -10 to 40°C for the purpose of inhibiting the side reaction. The resulting 3,4-dihydroxybutanenitrile or 3,4-dihydroxy-3-methylbutanenitrile can be used in the following reaction without being purified, but may also be purified by a conventional process. [0011] Then, the resulting 3,4-dihydroxybutanenitrile or 3,4-dihydroxy-3-methylbutanenitrile is hydrolyzed to obtain 3,4-dihydroxybutanoic acid or 3,4-dihydroxy-3-methylbutanoic acid. Hydrolysis can be performed under an acid or 20 alkali condition, but the alkali condition is preferred in view of the yield. As an alkali used in the reaction, sodium hydroxide and potassium hydroxide are preferred because of cheap price. The reaction temperature for hydrolysis is preferably from 0 to 120°C, and more preferably from 50 to 100°C in view of the yield. The resulting alkali salt of 3,4-dihydroxybutanoic acid or 3,4-dihydroxy-3-methylbutanoic acid is neutralized by adding acid. As the acid used in this case, general mineral acids can be used. But it is preferred to use cheap sulfuric acid and hydrochloric acid, and 25 to use an acidic ion exchange resin which is easy to remove. [0012] The 3,4-dihydroxybutanoic acid or 3,4-dihydroxy-3-methylbutanoic acid thus obtained is lactonized to obtain β-hydroxy-β-methyl-γ-butyrolactone or β-hydroxy-γ-butyrolactone. The lactonization reaction proceeds spontaneously in a usual concentration process, but may also be performed at 0-100°C under the acidic condition. As the acid used in this case, general mineral acids can be used. But it is preferred to use cheap sulfuric acid and hydrochloric acid, 30 and to use an acidic ion exchange resin which is easy to remove. The resulting β-hydroxy-γ-butyrolactones may be purified by a conventional process, if necessary. [0013] The process for preparing β-hydroxy-γ-butyrolactones, comprising cyanating glycidol or 2-methyl-2,3-epoxy- propanol, followed by hydrolysis and further lactonization was described above with reference to the respective steps, but these steps can also be performed in a single vessel without being purified during the steps according to the present 35 invention. This means that the present invention relates to a process capable of preparing β-hydroxy-γ-butyrolactones using a simple apparatus, which is economically excellent. [0014] In the present invention, in order to obtain β-(meth)acryloyloxy-γ-butyrolactone and β-methyl-β-(meth)acry- loyloxy-γ-butyrolactones represented by the formula (2), which are referred to as β-(meth)acryloyloxy-γ-butyrolactones, β-hydroxy-γ-butyrolactones obtained by the above process are esterified with (meth)acrylic acid chloride or (meth) 40 acrylic acid, or ester-interchanged with (meth)acrylate. The β-(meth)acryloyloxy-γ-butyrolactones thus obtained may also be purified by a conventional process, if necessary. [0015] In the case of esterifying with (meth) acrylic acid chloride, a basic catalyst is usually used. The basic catalyst may be any one capable of neutralizing an acid to be produced and is not specifically limited , and examples thereof include triethylamine, pyridine and sodium hydrogencarbonate. The reaction temperature is usually from -80 to 100°C, 45 and is preferably controlled to 0°C or lower to inhibit the side reaction, and more preferably from -80 to -20°C.