Process for preparation of 1,3-dioxolane-4-methanol compounds

Details Process for preparation of 1,3-dioxolane-4-methanol compounds Process for preparation of 1,3-dioxolane-4-methanol compounds

1999-02-08

2000-11-07

Dentz, Bernard

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

549331, C07D31720, C07D49310

Patent

active

061439088

DESCRIPTION:

BRIEF SUMMARY
TECHNICAL FIELD

The present invention relates to a process for preparation of 1,3-dioxolane-4-methanol compounds useful as an intermediate of medicines, agricultural chemicals, etc.


BACKGROUND ART

1,3-Dioxolane-4-methanol compounds are used as an intermediate of medicines, agricultural chemicals, etc. and following processes for preparation of them are known: (i) A process for preparation of them by reacting glycerin and an acetonide reagent (Synth. Commun., 22, 2653(1992), (ii) a process for preparation of them from mannitol (Biochem. Prep., 2, 31(1952)), (iii) a process for preparation of them from an ascorbic acid (J. Am. Chem. Soc., 102, 6304(1980), (iv) a process for preparation of them 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 preparation of them by reacting glycerin and 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 chemically equivalent amount of lead tetraacetate or sodium periodic 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 for preparation of them from L-ascorbic acid or D-isoascorbic acid of (iii), because 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 like in case of (ii) and furthermore in case of reduction of the carboxylic acid, the reagent which is difficult to be dealt with in mass production such as lithium aluminum hydride etc. 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, any process mentioned above contains many steps and is not practical. Therefore, a more efficient process for preparation of a 1,3-dioxolane-4-methanol was desired.


DISCLOSURE OF INVENTION

The present inventors engaged extensively in solving above problems, and found a novel process for preparing the above objective compound from a 3-halogeno-1,2-propanediol.
The present invention relates to a process for preparing a 1,3-dioxolane-4-methanol compound 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, which is characterized in acetalizing a 3-halogeno-1,2-propanediol of the formula ##STR3## wherein X is halogen atom, with an acetalizing agent in the presence of an acid catalyst to prepare a 4-halogenomethyl-1,3-dioxolane of the formula ##STR4## wherein R.sup.1, R.sup.2 and X are as defined above, and reacting it with an alkali metal salt or alkaline earth metal salt of a carboxylic acid or an alcohol of the formula ##STR5## wherein R, R.sup.1 and R.sup.2 are as defined above, and when R is acyl in the formula (4), subjecting it to hydrolysis, and when R is aralkyl or allyl in the formula (4) 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 as a starting material, there is obtained

REFERENCES:
patent: 4861764 (1989-08-01), Samour et al.
Partali et al, Tetrahedron: Asymmetry, vol. 3, No. 1, pp. 65-72, 1992.
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.

Affiliated with

Also associated with

Rating

Process for preparation of 1,3-dioxolane-4-methanol compounds does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for preparation of 1,3-dioxolane-4-methanol compounds, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for preparation of 1,3-dioxolane-4-methanol compounds will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-1642645