Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1999-02-08
2000-09-26
McKane, Joseph
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
549341, 549453, C07D31712, C07D31714, C07D31772
Patent
active
061244791
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to a process for preparation of 1,3-dioxolane-4-methanols useful as an intermediate in making medicines, agricultural chemicals, etc.
BACKGROUND ART
1,3-Dioxolane-4-methanols are used as an intermediate of medicines, agricultural chemicals, etc. and the following processes for their preparation are known: (i) A process for their preparation is by reacting glycerin and an acetonide reagent (Synth. Commun., 22, 2653(1992), (ii) a process for their preparation from mannitol (Biochem. Prep., 2, 31(1952)), (iii) a process for their preparation from an ascorbic acid (J. Am. Chem. Soc., 102, 6304(1980), (iv) a process for their preparation from serine (Japanese Patent Publication B No. 6-62492), (v) an optical resolution of them by using an enzyme (J. Chem. Soc., Perkin Trans. I 23, 3459(1994) and so on.
These processes, however, have industrially following disadvantages:
According to the process for their preparation by reacting glycerin with an acetonide reagent of (i), a mixture of a compound acetalized between positions 1 and 2 and a compound acetalized between positions 1 and 3 is produced and it is hardly difficult to separate each compound from the mixture. According to the method of (ii), because a chemically equivalent amount of lead tetraacetate or sodium hyperiodic acid is used in case of cleavage of 1,2-diol compounds, it takes high costs and in case of preparing an optical isomer, only a (S)-form is obtained because only D-mannitol is present in nature. According to the process from L-ascorbic acid or D-isoascorbic acid of (iii), because a chemically equivalent amount of lead tetraacetate or sodium periodic acid is used, it takes high costs like in case of (ii). According to the method from serine of (iv), in case of preparing an optical isomer, only a (R)-form is obtained because only a (L)-form is present in nature as in case of (ii) and furthermore, in the reduction of the carboxylic acid, the reagent is difficult to deal with in mass production, such as lithium aluminum hydride, must be used. According to the process by the biochemically optical resolution method of (v), purity of one of optical isomers is high, but purity of the other is low, and in some cases, in order to separate an optically active alcohol and an optically active ester which are prepared from a racemic alcohol, separation by column chromatography is necessary and therefore, it is not suitable for mass production. Furthermore, all the processes mentioned above contain many steps and are not practical. Therefore, a more efficient process for preparation of a 1,3-dioxolane-4-methanols was desired.
DISCLOSURE OF INVENTION
The present inventors engaged extensively in solving the above problems, and found a novel process for preparing the instant compound from a 3-halogeno-1,2-propanediol or glycidol.
The present invention relates to a process for preparing a 1,3-dioxolane-4-methanol of the formula ##STR2## wherein R.sup.1 and R.sup.2 are the same or different and are hydrogen atom, alkyl having 1 to 4 carbon atoms or phenyl, and R.sup.1 and R .sup.2 may form a cycloalkyl ring having 3 to 6 carbon atoms with the adjacent carbon atoms, formula ##STR3## wherein X is halogen atom, or glycidol of the formula ##STR4## with a alcohol of the formula formula ##STR5## wherein R is as defined above, and acetalizing it with an acetalizing agent in the presence of an acid catalyst to prepare a 4-alkoxymethyl-1,3-dioxolane of the formula ##STR6## wherein R, R.sup.1 and R.sup.2 are as defined above, and then subjecting it to hydrogenolysis in the presence of a reduction catalyst.
According to the present invention, in case of using an optically active 3-halogeno-1,2-propanediol or glycidol as a starting material, there is also obtained an optically active 1,3-dioxolane-4-methanol.
BEST MODE FOR CARRYING OUT THE INVENTION
The reaction of the present invention is schematically shown as follows. ##STR7## , in the above formulae X, R.sup.1, R.sup.2 and R are as defined above.
Each step is expla
REFERENCES:
patent: 4861764 (1989-08-01), Samour et al.
He et al., Synthetic Communications, 22(18), 2653-2658 (1992), "Studies on Carbohydrates X A New method for the Preparation of Isopropylidene Saccharides."
Baer et al., J. Biol. Chem, "L-.alpha.-Glycerophosphoric Acid" 135, 321 (1940).
Jung et al., J. Am. Chem. Soc., "Total Synthesis of (R)-Glycerol Acetonide and the Antiepileptic and Hypotensive Drug(-)-.gamma.-Amino-.beta.-hydroxybutyric Acid (GABOB): Use of Vitamin C as a Chiral Starting Material", 1980, 102, 6304-6311.
Vanttinen et al., J. Chem. Soc. Perkin Trans., "Lipase-catalysed Transesterification in the Preparation of Optically Active Solketal," 1994, 3459-3463.
Furukawa Yoshiro
Hinoue Kazumasa
Daiso Co. Ltd.
McKane Joseph
Solola Taofiq A.
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