Process for preparing .beta.-hydroxy-.gamma.-butyrolactones and .beta.-(meth)acryloyloxy-.gamma.-butrolactones

The present invention provides a process for preparing .beta.-hydroxy-.gamma.-butyrolactone or .beta.-methyl-.beta.-hydroxy-.gamma.-butyrolactone represented by the formula (1): ##STR1## wherein R.sup.1 is hydrogen or methyl, which entails a) cyanating glycidol or 2-methyl-2,3-epoxypropanol, b) hydrolyzing the product of step a), and c) lactonizing the product of step b).

BACKGROUND OF THE INVENTION
 1. Field of the Invention
 The present invention relates to a process for preparing
 .beta.-hydroxy-.gamma.-butyrolactone and
 .beta.-methyl-.beta.-hydroxy-.gamma.-butyrolactone (hereinafter referred
 to as ".beta.-hydroxy-.gamma.-butyrolactones"), and a process for
 preparing .beta.-(meth)acryloyloxy-.gamma.-butyrolactone and
 .beta.-methyl-.beta.-(meth)acryloyloxy-.gamma.-butyrolactone (hereinafter
 referred to as ".beta.-(meth)acryloyloxy-.gamma.-butyrolactones") which
 are useful as a constituent component monomer of paints, adhesives,
 sticking agents, and resins for ink, for example.
 2. Description of the Background
 .beta.-hydroxy-.gamma.-butyrolactones, which are used as a precursor of
 .beta.-(meth)acryloyloxy-.gamma.-butyrolactones, for example, may be
 prepared by reacting glycidol with carbon monoxide at high temperature
 under high pressure using a noble metal as a catalyst (U.S. Pat. No.
 4,968,817) and by 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)). However, both methods are attended by a high risk
 of explosion.
 Due to this risk, it is difficult to industrially prepare
 .beta.-hydroxy-.gamma.-butyrolactones, hence,
 .beta.-(meth)acryloyloxy-.gamma.-butyrolactones have never been producing
 industrially using these compounds as a raw material, despite the expected
 use for various purposes.
 Therefore, it has been considered desirable to develop a process for
 preparing .beta.-hydroxy-.gamma.-butyrolactones in a safe and simple
 manner, as well as a process for preparing
 .beta.-(meth)acryloyloxy-.gamma.-butyrolactones.
 SUMMARY OF THE INVENTION
 Accordingly, it is an object of the present invention to provide a process
 for preparing .beta.-hydroxy-.gamma.-butyrolactones in a safe and simple
 manner, as well as a process for preparing
 .beta.-(meth)acryloyloxy-.gamma.-butyrolactones, which are useful as a
 constituent component monomer of paints, adhesives, sticking agents, and
 resins for ink, for example, using .beta.-hydroxy-.gamma.-butyrolactones
 obtained by the above process.
 In particular, the present invention provides a process for preparing
 corresponding .beta.-hydroxy-.gamma.-butyrolactone or
 .beta.-methyl-.beta.-hydroxy-.gamma.-butyrolactone represented by the
 formula (1):
 ##STR2##
 wherein R.sup.1 represents a hydrogen atom or a methyl group, which entails
 cyanating glycidol or 2-methyl-2,3-epoxypropanol, followed by hydrolysis
 and then lactonization.
 The present invention also provides a process for preparing corresponding
 the .beta.-(meth)acryloyloxy-.gamma.-butyrolactone or
 .beta.-methyl-.beta.-(meth)acryloyloxy-.gamma.-butyrolactone represented
 by the formula (2):
 ##STR3##
 wherein R.sup.1 and R.sup.2 independently represent a hydrogen atom or a
 methyl group, which entails preparing .beta.-hydroxy-.gamma.-butyrolactone
 or .beta.-methyl-.beta.-hydroxy-.gamma.-butyrolactone by the above
 process, and then reacting the resulting
 .beta.-hydroxy-.gamma.-butyrolactone or
 .beta.-methyl-.beta.-hydroxy-.gamma.-butyrolactone with (meth)acrylic acid
 chloride, (meth)acrylic acid or (meth)acrylic ester.

EXAMPLE 1
 Synthesis of .beta.-hydroxy-.gamma.-butyrolactone
 To a glass flask equipped with a stirrer, a dropping funnel, a thermometer,
 a Dimroth condenser and an alkali trap of aqueous sodium hydroxide
 solution, magnesium sulfate heptahydrate (123.2 g, 0.5 mol), potassium
 cyanate (32.6 g, 0.5 mol) and 300 ml of water were added, and then
 glycidol (37.0 g, 0.5 mol) was added dropwise from the dropping funnel
 with ice cooling. After stirring 7 hours, an aqueous solution obtained by
 adding 50 ml of water to sodium hydroxide (25 g, 0.625 mol) was added
 dropwise and the mixture was heated at reflux at an internal temperature
 of 90 to 100.degree. C. After about 1 hour, bubbles which are considered
 to be ammonia gas were observed. After heating for 16 hours, followed by
 air cooling and further ice cooling, concentrated hydrochloric acid (136
 g, 1.35 mol) was added dropwise. This reaction solution was concentrated
 by using an evaporator and water was distilled off, thereby to deposit a
 large amount of a salt. To the salt, 1 liter of acetone and 50 g of
 magnesium sulfuric anhydride were added and, after filtering together with
 the salt, the filtrate was concentrated to obtain 55 g of
 crude-.beta.-hydroxy-.gamma.-butyrolactone. This
 .beta.-hydroxy-.gamma.-butyrolactone was purified by silica gel column
 chromatography to obtain .beta.-hydroxy-.gamma.-butyrolactone (34.8 g,
 0.205 mol).
 The purity of the resulting .beta.-hydroxy-.gamma.-butyrolactone was 98%
 and the actual yield was 40% (on the basis of glycidol) Spectrum data of
 .sup.1 H-NMR of the product were as follows.
 .sup.1 H-NMR (CDCl.sub.3): 2.5 (1H, d, J=18.1 Hz), 2.8 (1H, dd, J=5.9 Hz,
 18.1 Hz), 3.5 (1H, br), 4.3 (1H, d, J=10.3 Hz), 4.4 (1H, dd, J=4.3 Hz,
 10.3 Hz), 4.7 (1H, ddd, J=2.0 Hz, 4.3 Hz, 5.9 Hz)
 EXAMPLE 2
 Synthesis of .beta.-hydroxy-.gamma.-butyrolactone
 In a 1 liter glass reaction vessel, glycidol (293.0 g, 3.8 mol), water
 (92.8 g, 5.2 mol) and potassium carbonate (8.7 g, 0.063 mol) were charged,
 and then a hydrocyanic acid gas (97.8 g, 3.6 mol) was fed with ice cooling
 over 10 hours. The reaction temperature was slowly raised within a range
 from 8 to 25.degree. C. An aqueous solution obtained by adding 6.6 g of
 water to potassium carbonate (3.3 g, 0.024 mol) was added twice, followed
 by aging at room temperature for 2 days. To the resulting reaction
 solution containing 3,4-dihydroxybutanenitrile, 1200 ml of water and an
 aqueous solution obtained by adding 500 ml of water to sodium hydroxide
 (197 g, 4.93 mol) were added dropwise and the mixture was heated at reflux
 at an internal temperature of 90 to 100.degree. C. After about 1 hour,
 bubbles which are considered to be ammonia gas were observed. After
 heating for 18 hours, followed by air cooling and further ice cooling,
 concentrated hydrochloric acid (592 g, 5.92 mol) was added dropwise. This
 reaction solution was concentrated by using an evaporator and water was
 distilled off, thereby to deposit a large amount of a salt.
 To the salt, 1 liter of acetone and 100 9 of magnesium sulfuric anhydride
 were added and, after filtering together with the salt, the filtrate was
 concentrated to obtain 348 g of crude
 .beta.-hydroxy-.gamma.-butyrolactone. This
 .beta.-hydroxy-.gamma.-butyrolactone was purified by silica gel column
 chromatography to obtain .beta.-hydroxy-.gamma.-butyrolactone (212.1 g,
 2.08 mol).
 The purity of the resulting .beta.-hydroxy-.gamma.-butyrolactone was 98%
 and the actual yield was 51% (on the basis of glycidol) Spectrum data of
 .sup.1 H-NMR of the product were as follows.
 .sup.1 H-NMR (CDCl.sub.3): 2.5 (1H, d, J=18.1 Hz), 2.8 (1H, dd, J=5.9 Hz,
 18.1 Hz), 3.5 (1H, br), 4.3 (1H, d, J=10.3 Hz), 4.4 (1H, dd, J=4.3 Hz,
 10.3 Hz), 4.7 (1H, ddd, J=2.0 Hz, 4.3 Hz, 5.9 Hz)
 EXAMPLE 3
 Synthesis of .beta.-methacryloyloxy-.gamma.-butyrolactone
 In a glass flask equipped with a stirrer, two dropping funnels, a
 thermometer and a Dimroth condenser, .beta.-hydroxy-.gamma.-butyrolactone
 (91.1 g, 0.875 mol) having a purity of 98% obtained by repeating the
 process of Example 1 and 500 ml of dry dichloromethane were charged, and
 then triethylamine (117.5 g, 1.16 mol) was charged in one dropping funnel
 and methacrylic acid chloride (112 g, 1.071 mol) was charged in another
 dropping funnel. The atmosphere in the glass flask was replaced by
 nitrogen and then cooled to -60 to -70.degree. C. in a dry ice-acetone
 bath. While stirring in the glass flask, triethylamine and methacrylic
 acid chloride were added dropwise with adjusting so that the amount of
 triethylamine becomes small excess to that of methacrylic acid chloride.
 After the completion of the dropwise addition, stirring was continued for
 3 hours. To the reaction solution, 300 ml of water was added and a small
 amount of Celite was added, followed by filtration. The filtrate was
 washed three times with 300 ml of water using a separatory funnel and
 dried by adding 80 g of magnesium sulfate and, after filtering, the
 filtrate was concentrated to obtain 175 g of crude
 .beta.-methacryloyloxy-.gamma.-butyrolactone. This
 .beta.-methacryloyloxy-.gamma.-butyrolactone was purified by silica gel
 column chromatography to obtain
 .beta.-methacryloyloxy-.gamma.-butyrolactone (106.3 g, 0.625 mol).
 The purity of the resulting .beta.-methacryloyloxy-.gamma. butyrolactone
 was 97% and the actual yield was 69% (on the basis of
 .beta.-hydroxy-.gamma.-butyrolactone) Spectrum data of .sup.1 H-NMR of the
 product were as follows.
 .sup.1 H-NMR(CDCl.sub.3): 2.1 (3H, s), 2.8 (1H, d, J=18.4 Hz), 3.0 (1H, dd,
 J=6.8 Hz, 18.4 Hz), 4.5 (1H, d, J=10.8 Hz), 4.7 (1H, dd, J=4.8 Hz, 10.8
 Hz), 5.6 (1H, dd, J=4.8 Hz, 6.8 Hz), 5.8 (1H, s), 6.3 (1H, s)
 According to the process of the present invention,
 .beta.-hydroxy-.gamma.-butyrolactones can be produced in a safe and simple
 manner. Furthermore, by using .beta.-hydroxy-.gamma.-butyrolactones
 obtained by the present invention,
 .beta.-(meth)acryloyloxy-.gamma.-butyrolactones, which are useful as a
 constituent component monomer of paints, adhesives, sticking agents, and
 resins for ink, for example, can be produced.
 Having described the present invention, it will be apparent that many
 changes and modifications may be made to the above-described embodiments
 without departing from the spirit and the scope of the present invention.