Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Reexamination Certificate
2003-06-19
2004-11-09
Desai, Rita (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
C560S179000, C560S184000, C562S512000, C562S579000, C562S586000
Reexamination Certificate
active
06815559
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to processes for producing 3,3,3-trifluoro-2-hydroxypropionic acid and its derivatives, which are useful intermediates for medicines and liquid crystals.
There are known the following first to fourth processes for producing 3,3,3-trifluoro-2-hydroxypropionic acid, which is represented by the formula 2.
In the first process, it is derived from 3,3,3-trifluoro-2-hydroxypropanol or 3,3,3-trifluoropropene-1,2-oxide (see Synlett, 7, pp. 507-508 (1994); and Japanese Patent Application Publications 5-078277 and 5-078278).
In the second process, it is derived from trifluoropyruvate (see Chem. Ber., 125(12), pp. 2795-2802 (1992)).
In the third process, it is derived from trifluoroacetaldehyde (see Japanese Patent Application Publication 3-148249).
In the fourth process, it is derived from hexafluoroisopropanol (see Nippon Kagaku Kaishi No. 9, pp. 1576-1586 (1989)).
Other processes for producing 3,3,3-trifluoro-2-hydroxypropionic acid are disclosed in Japanese Patent Application Publications 2002-080429 and 2001-226316; Organic Letters, 3(3), pp. 457-459 (2001); Tetrahedron Letters, 41(23), pp. 4603-4607 (2000), and Tetrahedron Letters, 41(22), pp. 4507-4512 (2000).
Although it is possible to obtain 3,3,3-trifluoro-2-hydroxypropionic acid with a relatively high yield by the above conventional processes, the raw materials (i.e., trifluoromethyl-containing compounds) used in these processes have very high prices. Therefore, these processes are not suitable for industrially producing 3,3,3-trifluoro-2-hydroxypropionic acid.
The following reaction scheme is taught in WO 02/00601 corresponding to European Patent Application EP 1300391 A1; WO 00/55113 corresponding to U.S. Patent Application Publication 2002/0026081 A1; Huaxue Gongcheng (Xilan, China), 28(4), pp. 44-45, 51 (2000); Japanese Patent Application Publication 10-139724; WO 98/07687 corresponding to U.S. Pat. No. 6,020518; J. Indian Chem. Soc., 66(4), pp. 239-240 (1989); J. Antibiot., 40(11), pp. 1555-1562 (1987); Tetrahedron, 37(17), pp. 3061-3065 (1981); Yukagaku, 28(7), pp. 501-502 (1979); and German Patent Application Publication 2648300 corresponding to U.S. Pat. No. 4,052,460.
Furthermore, it is disclosed in Chem. Ber., 125(12), pp. 2795-2802 (1992) that 3,3,3-trifluoro-2-hydroxypropionic acid alkyl ester is protected at its hydroxyl group (bonded to the second carbon) with a THP (tetrahydropyranyl) group, and then its alkoxycarbonyl group (—COOR) is reduced to a hydroxymethyl group (—CH
2
OH) using lithium aluminum hydride. Then, it is necessary to conduct a deprotection to produce 3,3,3-trifluoro-2-hydroxypropanol. Thus, the process of this publication is cumbersome for industrial production.
Japanese Patent Application Publication 2000-063306 discloses that 1,1-dichloro-3,3,3-trifluoroacetone is hydrolyzed in the presence of disodium hydrogenphosphate to trifluoropropanetetraol. It is further disclosed in this publication that the hydrolysis is conducted at a pH of from 2 to 9.
Japanese Patent Application Publication 5-70406 discloses a process for producing a &bgr;, &bgr;,&bgr;-trifluorolactic acid ester by reacting &bgr;,&bgr;,&bgr;-trifluorolactic acid with an alcohol (having a carbon atom number of at least 3) in the presence of a catalyst.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for efficiently producing 3,3,3-trifluoro-2-hydroxypropionic acid or its derivative(s), which are useful intermediates for medicines and liquid crystals.
According to the present invention, there is provided a process for producing 3,3,3-trifluoro-2-hydroxypropionic acid represented by the formula 2. This process includes the step of (a) bringing a 1,1-dihalogeno-3,3,3-trifluoroacetone represented by the formula 1 into contact with a basic aqueous solution (for example, having a pH of 12 or higher),
wherein X is Cl, Br or I.
The above raw material, 1,1-dihalogeno-3,3,3-trifluoroacetone, is industrially available with a low price.
It is possible to convert 3,3,3-trifluoro-2-hydroxypropionic acid into 3,3,3-trifluoro-2-hydroxypropanol represented by the formula 4 almost quantitatively, by a process including the steps of:
(b) reacting the 3,3,3-trifluoro-2-hydroxypropionic acid, which has been obtained by the above step (a), with a lower alcohol represented by the formula 5, under an acidic condition, thereby producing a 3,3,3-trifluoro-2-hydroxypropionate represented by the formula 3; and
(c) reacting the 3,3,3-trifluoro-2-hydroxypropionate with a hydride reducing agent, thereby producing the 3,3,3-trifluoro-2-hydroxypropanol,
wherein R is a C
1
-C
6
lower alkyl group.
It is possible by the above step (c) to efficiently reduce the alkoxycarbonyl group (—CO
2
R) into the hydroxymethyl group (—CH
2
OH) using a hydride reducing agent (e.g., sodium borohydride), without necessity of protecting the hydroxyl group (bonded to the second carbon) of the raw material, 3,3,3-trifluoro-2-hydroxypropionate and without necessity of the following deprotection. Thus, it is possible to easily obtain 3,3,3-trifluoro-2-hydroxypropanol with high yield and less load in industrial production.
The above-mentioned exemplary hydride reducing agent, sodium borohydride, is low in price and easy for handling. Thus, this sodium borohydride is considerably superior in safety and economy to lithium aluminum hydride.
REFERENCES:
patent: 4052460 (1977-10-01), Dickore et al.
patent: 6020518 (2000-02-01), Matsumoto et al.
patent: 2002/0026081 (2002-02-01), Onishi et al.
patent: 2648300 (1977-07-01), None
patent: 1300391 (2003-04-01), None
patent: 3148249 (1991-06-01), None
patent: 5070406 (1993-03-01), None
patent: 5078277 (1993-03-01), None
patent: 5078278 (1993-03-01), None
patent: 10139724 (1998-05-01), None
patent: 10287609 (1998-10-01), None
patent: 10330308 (1998-12-01), None
patent: 11001451 (1999-01-01), None
patent: 2000063306 (2000-02-01), None
patent: 2001226316 (2001-08-01), None
patent: 2002080429 (2002-03-01), None
patent: 98/07687 (1998-02-01), None
patent: 00/55113 (2001-09-01), None
patent: 02/00601 (2002-01-01), None
Nippon Kagaku Kaishi, (1989) vol. 9, pp. 1576-1586.*
Toshimasa Katagiri, et al., “Synthesis of Trifluorolactic Acid from 1,2-Epoxy-3,3,3-Trifluoropropane.—One Pot Tandem Ring Opening-Oxidation Reaction of Epoxide-” Synlett, vol. 7, pp. 507-508, 1994.
C. Huennefeld, et al., “Ergiebige Herstellung von (R)- und (S)-3,3,3-Trifluormilschsaeure und von (R)- und (S)-(Trifluormethyl)oxiran” Chem. Ber., vol. 125, No. 12, pp. 2795-2802, 1992.
Nippon Kagaku Kaishi No. 9, pp. 1576-1586, 1989.
Yoshichika Kuroki, et al., Enantioselective Rhodium(I)-Catalyzed Hydrogenation of Trifluoromethyl Ketones Organic Letters, vol. 3, No. 3, pp. 457-459, 2001.
Yoshichika Kuroki, et al., “Enantioslective synthesis of 1,1,1-trifluoroalkan-2-ols by ruthenium-catalzed hydrogenation” Tetrahedron Letters, vol. 41, pp. 4603-4607, 2000.
Nicholas J. Lawrence, et al., “An efficient protocol for the reduction of ketones with tin(II) complexes and PMHS” Tetrahedron Letters, vol. 41, pp. 4507-4512, 2000.
Huaxue Gongcheng (Xilan, China), 28(4) pp. 44.45, 2000.
A. Bandyopadhyay, et al., “A New Route for Synthesis of Aromatic -Keto Acid” J. Indian Chem. Soc. vol. 66, pp. 239-240, 1989.
Alberto Sala, et al., “Synthesis and Antibacterial Properties of 7-[2-(3-Substituted-5-Isoxazolyl)-2-Methoxyiminoacetamido]Cephalosporanic Acid Derivatives” The Journal of Antibiotics vol. 40, No. 11, pp. 1555-1562, 1987.
Peter Lugosi, et al., “Synthesis of 3-Haloisoxazoles by Novel Oxidative Degradation of the Side-Chain of 3.(3.Halo-Isoxazol-5-Yl) Propionic Acids” Tetrahedron Letters, vol. 37, No. 17, pp. 3061-3065, 1981.
Toshiyuki Tanaka, et al., “Synthesis of Lactic Acid from 1,1-Dichloroacetone” vol. 28, No. 7, pp. 501-502, 1979.
Inomiya Kenjin
Ishii Akihiro
Kanai Masatomi
Kuriyama Yokusu
Yasumoto Manabu
Central Glass Company Limited
Desai Rita
Reyes Hector M.
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