Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1998-07-20
1999-10-12
Richter, Johann
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
549520, 549521, 549554, 549555, 549556, 549560, C07D30334
Patent
active
059657537
DESCRIPTION:
BRIEF SUMMARY
FIELD OF ART
The present invention relates to an improved process for preparation of a glycidyl sulfonate derivative. The glycidyl sulfonate derivative is useful as an intermediate for medicines, agricultural chemicals and biologically active substances.
BACKGROUND OF ART
A glycidyl sulfonate derivative is generally prepared by reacting glycidol with a sulfonyl chloride in the presence of a tertiary amine in a solvent selected from an aromatic hydrocarbon and a halogenated hydrocarbon. For example, methods of the reaction in dichloromethane or toluene are known (J. Org. Chem., 51, 3710 (1986), J. Org. Chem., 54, 1295 (1989) and U.S. Pat. No. 4,946,974). However, according to these methods, glycidol as a starting material is unstable and the side-reaction such as dimerization occurs. The product, therefore is produced with many impurities. To obtain the product with high purity, rectification or repeated recrystallization is required and eventually decrease of the yield occurs. As these methods have many demerits in the industrial scale as mentioned above, an effective method has been desired. Recently a method for preparing the product by reacting glycidol with an organic sulfonyl halide in the presence of a tertiary amine in a two phase solution consisting of water and toluene has been proposed (Japanese Patent Publication A No. 306067/1994). But the reaction rate is low and purity of the product is not satisfied. And after preparing glycidol, an intermediate, further to extract it with water is necessary and the procedure is inconvenient. To solve these inconveniences the present inventors have proposed a method for preparing glycidyl tosylate by treating 3-chloro-1,2-propanediol with an alkali metal carbonate in an organic solvent and without isolation of the resulting glycidol, subjecting it to reaction with p-toluenesulfonyl chloride, a tertiary amine and 4-dimethylaminopyridine to produce glycidyl tosylate (Japanese Patent Publication A No. 165743/1995). However, the method has following practical disadvantages: The reaction rate is low in case of treating with an alkali metal carbonate, side-reaction occurs to give the compound with many impurities and further the viscosity of the reaction mixture is too increased in case of using a solvent except for a halogenated solvent.
The present inventors, further extensively engaged in study for solving the above problems to find that an objective glycidylsulfonate with high purity and in good yield was obtained by using a two phase solvent consisting of an organic solvent and water and in the presence of a specific inorganic base and a tertiary amine or a pyridine derivative in case of reacting glycidol with a sulfonyl halide and thus this invention was completed. The present inventors, further found the method for preparing an objective glycidyl sulfonate derivative more conveniently and efficiently by reacting glycidol, an intermediate, with 3-chloro-1,2-propanediol under the specific basic condition in an aqueous solvent and without separating the resulting glycidol, subjecting it to reaction with the above sulfonyl halide.
DISCLOSURE OF INVENTION
The present invention provides to an improved process for preparation of a glycidylsulfonate derivative which is characterized in reacting glycidol with a sulfonyl halide in a two phase solvent consisting of an organic solvent and water in the presence of at least one in organic base selecting from of an alkali metal or alkaline earth metal hydroxide, an alkali metal or alkaline earth metal carbonate and an alkali metal or alkaline earth metal hydrogen carbonate, and a tertiary amine or a pyridine derivative.
The preferable mode of this invention relates to a process for preparation of a glycidyl sulfonate derivative in one reaction vessel which is characterized in reacting with 3-chloro-1,2-propanediol in an aqueous solvent in the presence of at least an inorganic base selecting from an alkali metal or alkaline earth metal hydroxide, an alkali metal or alkaline earth metal carbonate and an alkali metal
REFERENCES:
patent: 4946974 (1990-08-01), Sharpless et al.
patent: 5252759 (1993-10-01), Shum
Klunder et al., J. Org. Chem, 1989, 54, 1295-1304, "Arenesulfonate Derivatives of Homochiral glycidol Versatile Chiral Building Blocks for Organic Synthesis."
Klunder et al., J. Org. Chem., 1986, 51, 3710-3712, "Asymmetric Epoxidation of Allyl Alcohol: Efficient Routes to Homochiral .beta.-Adrenergic Blocking Agents."
Furukawa Yoshiro
Masaki Midori
Takenaka Keishi
Daiso Co. Ltd.
Dolan John F.
Richter Johann
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