Process for production of thioalkylamine derivatives

Details Process for production of thioalkylamine derivatives Process for production of thioalkylamine derivatives

2002-05-29

2003-10-28

Vollano, Jean F. (Department: 1621)

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

Organic compounds

Amino nitrogen containing

C564S500000

Reexamination Certificate

active

06639109

ABSTRACT:

This application is a 371 of PCT/JP00/06673 filed Sep. 27, 2000, now Ser. No. WO 01/23350.
TECHNICAL FIELD
The present invention relates to thioalkylamine derivatives represented by general formula (I) which are useful as intermediates of medicines, agrochemicals, chemical products, etc., and a process for production of the derivatives.
BACKGROUND ART
Thioalkylamine derivatives are useful as intermediates for synthesis of agrochemicals, medicines, chemical products, etc. or starting materials for them. When used in agrochemicals, the derivatives are useful compounds as, for example, starting compounds for the agricultural and horticultural insecticide disclosed in Japanese Patent Application No. 11-338715 filed by the same applicant as the present applicant.
Thioalkylamines can be classified into thiols and sulfides according to chemical structure. As a process for producing any of the thiols and the sulfides, the following processes have been reported.
(1) A process in which a thiol is produced by hydrolyzing a thiazoline or thiazolidinone derivative (for example, J. Med. Chem., 1965, 8, 762; JP-A-59-231064; Bull. Soc. Chim. Fr. 1967, 3637; and Z. Naturforsch., B: Chem. Sci. 1987, 42, 348). (2) A process in which a sulfide is produced by reacting an oxazoline or oxazolidinone derivative with a thiol (for example, J. Org. Chem., 1992, 57,6257; and J. Med. Chem., 1984, 27, 1354). (3) A process in which a sulfide or a thiol is produced by reacting an aziridine with a sulfur compound such as a mercaptan (for example, Tetrahedron, 1992, 48, 2359; J. Am. Chem. Soc., 1986, 108,.3811; Inorg. Chem., 1984, 23, 3404; and Tetrahedron Lett., 1983, 24, 2131). (4) A process in which a sulfide is produced by hydrolyzing an amide obtained by reacting an amino alcohol with a mercaptan in a carboxylic acid (for example, Neth. Appl. 6, 404, 644). (5) A process in which a thiol is produced by reacting an amino alcohol sulfate ester with ammonium hydrogensulfide (for example, Journal of Chemical Society of Japan, 1979, 149). (6) A process in which a thioalkyl alcohol is converted to a thioalkylamine by Ritter reaction and hydrolysis (for example, Ger. Offen. 2,045,905).
A desired compound in the present invention is a sulfide as a thioalkylamine. Therefore, of the above prior arts, the production processes (2), (3), (4) and (6) are closely concerned with the desired compound. However, the process (2) involves, for example, the following problem: it requires a hydrolysis step because the product is obtained as an amide, and the reaction does not take place if a substituent such as an alkyl group is present in the oxazolidine ring of the starting compound. This process is also disadvantageous in that only an aromatic sulfide can be produced owing to the acidity of a mercapto group. The process (3) is not suitable for industrial adoption from the viewpoint of safety and facilities because the aziridine whose toxicity tends to affect the health of production workers is used after its production and isolation. The process (4) is disadvantageous, for example, in that the product is limited to a thiol because the reaction is carried out with heating under pressure for a long period of time. Moreover, this process is disadvantageous, for example, in that like the process (2), it requires hydrolysis because the product is obtained as an amide. The process (6) is disadvantageous, for example, in that an excess of prussic acid is used which is very toxic and requires great care in handling and after-treatment, or that the hydrolysis is not easy when an easily handleable nitrile is used.
Although the processes (1) and (5) are production processes of a thiol and are not directly concerned with a process for producing a sulfide intended according to the present invention, they involve the following problems. That is, the process (1) is industrially disadvantageous from the viewpoint of the number of steps and yield because the thiazoline or thiazolidinone derivative should be produced. The process (5) is industrially disadvantageous in that it entails high cost in view of facilities and production efficiency because the reaction is carried out in a sealed tube for a long period of time.
The present invention avoids, for example, the following various problems in prior arts: a reaction is carried out at a high temperature and a high pressure for a long period of time; an additional step such as hydrolysis is needed; there are various restrictions on introducible substituents; and the toxicity of a starting material used and the like is so high that safety and facilities required for handling and after-treatment of the staring material and the like cost a great deal. Thus, the present invention provides a production process which is simple and short, can be generally adopted, can be safely practiced, and is economically advantageous.
DISCLOSURE OF THE INVENTION
In order to solve the above problems and develop a novel process for producing a thioalkylamine, the present inventors earnestly investigated and consequently found that the above object can be achieved by producing a sulfate ester represented by general formula (III) by the reaction of an amino alcohol represented by general formula (II) with sulfuric acid, and reacting the sulfate ester with a mercaptan under basic conditions, whereby the present invention has been accomplished.
The present invention relates to a thioalkylamine derivative represented by general formula (I):
wherein each of R
1
and R
2
, which may be the same or different, is a hydrogen atom; a (C
1
-C
4
)alkyl group; a (C
3
-C
8
)cycloalkyl group; a (C
3
-C
8
)cycloalkyl(C
1
-C
4
)alkyl group; a hydroxy-(C
1
-C
4
)alkyl group; a phenyl group; a substituted phenyl group having 1 to 5 substituents which may be the same or different and each of the substituents is selected from a halogen atom, a cyano group, a nitro group, a (C
1
-C
4
)alkyl group, a halo(C
1
-C
4
)alkyl group, a (C
3
-C
8
)cycloalkyl group, a (C
1
-C
4
)alkoxy group, a halo(C
1
-C
4
)alkoxy group, a (C
1
-C
4
)alkylthio group, a halo(C
1
-C
4
)alkylthio group, a (C
1
-C
4
)alkylsulfinyl group, a halo(C
1
-C
4
)alkylsulfinyl group, a (C
1
-C
4
)alkylsulfonyl group, a halo(C
1
-C
4
)alkylsulfonyl group, a carboxyl group, a (C
1
-C
4
)alkoxycarbonyl group, a (C
1
-C
4
)alkoxy(C
1
-C
4
)alkyl group, R
7
—C(═O)— (wherein R
7
is a (C
1
-C
4
)alkyl group, a halo(C
1
-C
4
)alkyl group, a phenyl group or a phenoxy group), an amino group, and a substituted amino group having one or two substituents which may be the same or different and are selected from (C
1
-C
4
)alkyl groups; a substituted phenyl group having as the substituent a (C
3
-C
4
)alkylene group or a (C
1
-C
2
)alkylenedioxy group, which forms a ring together with a pair of adjacent carbon atoms in the benzene ring; a phenyl(C
1
-C
4
)alkyl group; or a substituted phenyl(C
1
-C
4
)alkyl group having on the ring 1 to 5 substituents which may be the same or different and each of the substituents is selected from a halogen atom, a cyano group, a nitro group, a (C
1
-C
4
)alkyl group, a halo(C
1
-C
4
)alkyl group, a (C
3
-C
8
)cycloalkyl group, a (C
1
-C
4
)alkoxy group, a halo(C
1
-C
4
)alkoxy group, a (C
1
-C
4
)alkylthio group, a halo(C
1
-C
4
)alkylthio group, a (C
1
-C
4
)alkylsulfinyl group, a halo(C
1
-C
4
)alkylsulfinyl group, a (C
1
-C
4
)alkylsulfonyl group and a halo(C
1
-C
4
)alkylsulfonyl group; R
1
and R
2
may form a (C
2
-C
5
)alkylene group by binding to each other; R
1
and R
3
or R
5
may form a (C
3
-C
5
)alkylene group by binding to each other,
each of R
3
and R
4
, which may be the same or different, is a hydrogen atom or a (C
1
-C
4
)alkyl group; R
3
and R
4
may form a (C
4
-C
6
)alkylene group by binding to each other; R
3
and R
5
may form a (C
2
-C
4
)alkylene group by binding to each other,
each of R
5
and R
6
, which may be the same or different, is a hydrogen atom; a (C
1
-C
4
)alkyl group; a phenyl group; a substituted phenyl group having 1 to 5 substituents which may be the same or different and each of the substituents is sele

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