Title of Invention	"A PROCESS FOR PREPARING AN (E)-[R]-2-ALKYL-4-(2,2,3-TRIMETHYLCYCLOPENT-3-EN-1-YL)-2-BUTEN-1-OL, PERFUME COMPOSITION"
Abstract	A process for preparing an (E)-(R)-2-alkyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)-2-buten-l-ol represented by formula (I): wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms, comprising hydrogenating an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-al represented by formula (II): wherein R is as defined above, in the presence of a ruthenium-phosphine complex as a catalyst, a base comprising an alkali metal or an alkaline earth metal, and an amine of the kind such as hereindescribed at a temperature of from -30 to 250° C and at a pressure of about 1 to 200 atm.

Title of Invention

"A PROCESS FOR PREPARING AN (E)-[R]-2-ALKYL-4-(2,2,3-TRIMETHYLCYCLOPENT-3-EN-1-YL)-2-BUTEN-1-OL, PERFUME COMPOSITION"

Abstract

A process for preparing an (E)-(R)-2-alkyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)-2-buten-l-ol represented by formula (I): wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms, comprising hydrogenating an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-al represented by formula (II): wherein R is as defined above, in the presence of a ruthenium-phosphine complex as a catalyst, a base comprising an alkali metal or an alkaline earth metal, and an amine of the kind such as hereindescribed at a temperature of from -30 to 250° C and at a pressure of about 1 to 200 atm.

Full Text	FIELD OF THE INVENTION This invention relates to an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol which is a novel optically active compound, a process for preparing the same, and a perfume composition containing the same. An (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)-2-buten-l-ol has a fine sandalwood-like odor, and a perfume composition containing it is useful in various cosmetics, fragrances, toiletries, and other hygienic goods. BACKGROUND OF THE INVENTION Sandalwood oil is an essential oil obtained from sandalwood tree occurring in the east of India and is highly valued as a perfume component. However, production of sandalwood oil is being decreased because, felling of the sandalwood tree is restricted from the standpoint of environmental and resources conservation pressures. Therefore synthetic sandalwood oil fragrance materials have been developed for substitution. It is known that the main components responsible for the odor of natural sandalwood oil are a-santalol and ß-santalol. Santalol is difficult to synthesize in quantities because of its chemical structure. In recent years, substances different from santalol in chemical structure but very similar in odor to santalol have been synthesized. Among such substances are 2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol derivatives (see JP-B-56-361676 and JP-A-55-139330, the term "JP-B" as used herein means an "examined Japanese patent publication", and the term "JP-A" as used herein means an "unexamined published Japanese patent application"). 2-Methyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol is available from Taiyo Koryo K.K. under the trade name of "Santalinol", and 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol from International Flavor and Fragrance (hereinafter abbreviated as IFF) under the registered trademark "Bacdanol". There is found no report on synthesis of an optically active 2-ethyl-4- (2,2, 3-trimethylcyclopent-3-en-l-yl) -2-buten-l-ol . R. Reinhardt, et al. have reported in J. Chromatog. A, Vol. 697, No. 7, pp. 475-484 (1995) that the resolution of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol was not successful by gas chromatography using a chiral column. Thus, there is no report on the isolation or synthesis of an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol, i.e., an optically active compound of a 2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol in which the trimethylcyclopentene ring and the and strong sandalwood-like odor; the (IS)-isomer (mixture of diastereomers in which the 2-position is racemic) is drier than the (1R)-isomer and has a sandal cedar note; the (IS,2S)-isomer has a milky and strong sandalwood oil odor with a faint animal note; the (IS,2R)-isomer has a weak and flat sandalwood-like odor; the (1R,2S)-isomer has a more pleasant odor than the (1R,2R)-isomer and bears the odor of the (1R)-isomer (diastereomer mixture in which the 2-position is racemic); and a (2S)-isomer (mixture of diastereomers in which the 1-position is racemic) has a pleasant odor. Accordingly the present invention relates to a process for preparing an (E)-(R)-2-alkyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)-2-buten-l-ol represented by formula (I): (Formula Removed) wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms, comprising hydrogenating an (E)-(R)-2-alkyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)-2-buten-l-al represented by formula (II): (Formula Removed) wherein R is as defined above, in the presence of a ruthenium-phosphine complex as a catalyst, a base comprising an alkali metal or an alkaline earth metal, and an amine of the kind such as hereindescribed at a temperature of from -30 to 250° C and at a pressure of about 1 to 200 atm. SUMMARY OF THE INVENTION An object of the present invention is to provide an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-1-ol which is different from known racemic mixtures and has an excellent odor and a perfume composition containing the same. As a result of extensive study, the inventors of the present invention have found that an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol can easily be obtained by hydrogenating an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-al (hereinafter sometimes referred to as the (E-R) compound) in the presence of a base, an amine, and a ruthenium-phosphine complex catalyst. They have synthesized an (E)-(S)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol, which is an antipode of the (E-R)-compound, and have these optical hydroxymethyl group are in a trans configuration. Several reports are found with respect to the relation between the configurations of the side chain of fragrance substances having a trimethylcyclopentene ring and the odor. For example, (1) concerning the relation between odor and the absolute configuration of the asymmetric carbon atom on the 1-position of the cyclopentene ring in compounds having a (2,2,3-trimethyl-3-cyclopenten-l-yl)alkanol skeleton, U.S. Patent 4,052,341 and U.S. Patent 4,610,813 have reported that the (R)-isomer and the (S)-isomer have the same odor as the racemate, that is, the absolute configuration has no influence on odor. (2) As for 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten- l-yl)-4-penten-2-ol, U.S. Patent 4,696,766 has disclosed that the relationship of the odor and relative configuration of 2 and 3-positions that a mixture of anti-diastereomers is 500 times that of a syn-form diastereomer mixture, but has no mention of the relation between the absolute configuration of the 1-position of the trimethylcyclopentene ring and the odor. (3) Regarding the four optical isomers and diastereomer mixtures of (E)-3,3-dimethyl-5-(2,2,3- trimethylcyclopent-3-en-l-yl)-4-penten-2-ol, U.S. Patent 5,512,543 has described that the (IR)-isomer (mixture of diastereomers in which the 2-position is racemic) has a milky WE CLAIM: 1. A process for preparing an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol represented by formula (I): (Formula Removed) wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms, comprising hydrogenating an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-i-yl)-2-buten-l-al represented by formula (II): (Formula Removed) wherein R is as defined above, in the presence of a ruthenium-phosphine complex as a catalyst, a base comprising an alkali metal or an alkaline earth metal, and an amine at a temperature of from -30 to 250° C and at a pressure of about 1 to 200 atm, 2. A perfume composition containing about 0.1 to 50% by weight based on the total composition of (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol represented by formula (I): (Formula Removed) wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms. 3. A perfume composition containing an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-o3-en-l-yl)-2-buten-l-ol represented by formula (I): (Formula Removed) wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms, and having an optical purity of 5O%e.e. or higher. 4. A process for preparing an (E)-[R]-2-alkyl-4-(2,2,3- trimethylcyclopent-3en-l-yl]-2-buten-l-ol substantially as herein described with reference to the foregoing examples. 5. A perfume composition substantially as herein described with reference to the foregoing examples.

Full Text

FIELD OF THE INVENTION
This invention relates to an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol which is a novel optically active compound, a process for preparing the same, and a perfume composition containing the same.
An (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)-2-buten-l-ol has a fine sandalwood-like odor, and a perfume composition containing it is useful in various cosmetics, fragrances, toiletries, and other hygienic goods.
BACKGROUND OF THE INVENTION
Sandalwood oil is an essential oil obtained from sandalwood tree occurring in the east of India and is highly valued as a perfume component. However, production of sandalwood oil is being decreased because, felling of the sandalwood tree is restricted from the standpoint of environmental and resources conservation pressures. Therefore synthetic sandalwood oil fragrance materials have been developed for substitution.
It is known that the main components responsible for the odor of natural sandalwood oil are a-santalol and ß-santalol. Santalol is difficult to synthesize in quantities because of its chemical structure. In recent years, substances different from santalol in chemical structure but

very similar in odor to santalol have been synthesized.
Among such substances are 2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol derivatives (see JP-B-56-361676 and JP-A-55-139330, the term "JP-B" as used herein means an "examined Japanese patent publication", and the term "JP-A" as used herein means an "unexamined published Japanese patent application"). 2-Methyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol is available from Taiyo Koryo K.K. under the trade name of "Santalinol", and 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol from International Flavor and Fragrance (hereinafter abbreviated as IFF) under the registered trademark "Bacdanol".
There is found no report on synthesis of an optically active 2-ethyl-4- (2,2, 3-trimethylcyclopent-3-en-l-yl) -2-buten-l-ol .
R. Reinhardt, et al. have reported in J. Chromatog. A, Vol. 697, No. 7, pp. 475-484 (1995) that the resolution of 2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol was not successful by gas chromatography using a chiral column.
Thus, there is no report on the isolation or synthesis of an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol, i.e., an optically active compound of a 2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol in which the trimethylcyclopentene ring and the

and strong sandalwood-like odor; the (IS)-isomer (mixture of diastereomers in which the 2-position is racemic) is drier than the (1R)-isomer and has a sandal cedar note; the (IS,2S)-isomer has a milky and strong sandalwood oil odor with a faint animal note; the (IS,2R)-isomer has a weak and flat sandalwood-like odor; the (1R,2S)-isomer has a more pleasant odor than the (1R,2R)-isomer and bears the odor of the (1R)-isomer (diastereomer mixture in which the 2-position is racemic); and a (2S)-isomer (mixture of diastereomers in which the 1-position is racemic) has a pleasant odor.
Accordingly the present invention relates to a process for preparing an (E)-(R)-2-alkyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)-2-buten-l-ol represented by formula (I):
(Formula Removed)
wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms,
comprising hydrogenating an (E)-(R)-2-alkyl-4-(2,2,3-
trimethylcyclopent-3-en-l-yl)-2-buten-l-al represented by formula
(II):
(Formula Removed)

wherein R is as defined above,
in the presence of a ruthenium-phosphine complex as a catalyst, a base comprising an alkali metal or an alkaline earth metal, and an amine of the kind such as hereindescribed at a temperature of from -30 to 250° C and at a pressure of about 1 to 200 atm.

SUMMARY OF THE INVENTION
An object of the present invention is to provide an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-1-ol which is different from known racemic mixtures and has an excellent odor and a perfume composition containing the same.
As a result of extensive study, the inventors of the present invention have found that an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol can easily be obtained by hydrogenating an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-al (hereinafter sometimes referred to as the (E-R) compound) in the presence of a base, an amine, and a ruthenium-phosphine complex catalyst. They have synthesized an (E)-(S)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol, which is an antipode of the (E-R)-compound, and have these optical
hydroxymethyl group are in a trans configuration.
Several reports are found with respect to the relation between the configurations of the side chain of fragrance substances having a trimethylcyclopentene ring and the odor.
For example, (1) concerning the relation between odor and the absolute configuration of the asymmetric carbon atom on the 1-position of the cyclopentene ring in compounds having a (2,2,3-trimethyl-3-cyclopenten-l-yl)alkanol skeleton, U.S. Patent 4,052,341 and U.S. Patent 4,610,813 have reported that the (R)-isomer and the (S)-isomer have the same odor as the racemate, that is, the absolute configuration has no influence on odor.
(2) As for 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-
l-yl)-4-penten-2-ol, U.S. Patent 4,696,766 has disclosed that
the relationship of the odor and relative configuration of 2
and 3-positions that a mixture of anti-diastereomers is 500
times that of a syn-form diastereomer mixture, but has no
mention of the relation between the absolute configuration of
the 1-position of the trimethylcyclopentene ring and the
odor.
(3) Regarding the four optical isomers and
diastereomer mixtures of (E)-3,3-dimethyl-5-(2,2,3-
trimethylcyclopent-3-en-l-yl)-4-penten-2-ol, U.S. Patent
5,512,543 has described that the (IR)-isomer (mixture of
diastereomers in which the 2-position is racemic) has a milky

WE CLAIM:
1. A process for preparing an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol represented by formula (I):

(Formula Removed)
wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms,
comprising hydrogenating an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-i-yl)-2-buten-l-al represented by formula (II):

(Formula Removed)

wherein R is as defined above,
in the presence of a ruthenium-phosphine complex as a catalyst, a base comprising an alkali metal or an alkaline earth metal, and an amine at a temperature of from -30 to 250° C and at a pressure of about 1 to 200 atm,
2. A perfume composition containing about 0.1 to 50% by weight based on the total composition of (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)-2-buten-l-ol represented by formula (I):

(Formula Removed)
wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms.
3. A perfume composition containing an (E)-(R)-2-alkyl-4-(2,2,3-trimethylcyclopent-o3-en-l-yl)-2-buten-l-ol represented by formula (I):

(Formula Removed)
wherein R represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms,
and having an optical purity of 5O%e.e. or higher.

4. A process for preparing an (E)-[R]-2-alkyl-4-(2,2,3-
trimethylcyclopent-3en-l-yl]-2-buten-l-ol substantially as herein
described with reference to the foregoing examples.
5. A perfume composition substantially as herein described with
reference to the foregoing examples.

Documents:

2612-del-1997-abstract.pdf

2612-del-1997-claims.pdf

2612-del-1997-correspondence-others.pdf

2612-del-1997-correspondence-po.pdf

2612-del-1997-description (complete).pdf

2612-del-1997-form-1.pdf

2612-del-1997-form-13.pdf

2612-del-1997-form-19.pdf

2612-del-1997-form-2.pdf

2612-del-1997-form-3.pdf

2612-del-1997-form-4.pdf

2612-del-1997-form-6.pdf

2612-del-1997-gpa.pdf

2612-del-1997-petition-137.pdf

2612-del-1997-petition-138.pdf

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Patent Number

232508

Indian Patent Application Number

2612/DEL/1997

PG Journal Number

13/2009

Publication Date

27-Mar-2009

Grant Date

17-Mar-2009

Date of Filing

12-Sep-1997

Name of Patentee

TAKASAGO INTERNATIONAL CORPORATION

Applicant Address

19-22, TAKANAWA 3-CHOME, MINATO-KU, TOKYO, JAPAN.

Inventors:

#	Inventor's Name	Inventor's Address
1	TAKASHI AIDA	C/O TAKASAGO INERNATIONAL CORPORATION,CENTRAL RESEARCH LABORATORY,4-11,NISHIYAWATA 1-CHOME,HIRATSUKA-SHI,KANAGAWA,JAPAN
2	MAKOTO HARADA	C/O TAKASAGO INERNATIONAL CORPORATION,CENTRAL RESEARCH LABORATORY,4-11,NISHIYAWATA1-CHOME,HIRATSUKA-SHI,KANAGAWA,JAPAN
3	HISAO EWAI	C/O TAKASAGO INERNATIONAL CORPORATION,CENTRAL RESEARCH LABORATORY,4-11,NISHIYAWATA1-CHOME,HIRATSUKA-SHI,KANAGAWA,JAPAN
4	AKIRA AMANO	C/O TAKASAGO INERNATIONAL CORPORATION,CENTRAL RESEARCH LABORATORY,4-11,NISHIYAWATA1-CHOME,HIRATSUKA-SHI,KANAGAWA,JAPAN
5	TETSURO YAMASAKI	C/O TAKASAGO INERNATIONAL CORPORATION,CENTRAL RESEARCH LABORATORY,4-11,NISHIYAWATA1-CHOME,HIRATSUKA-SHI,KANAGAWA,JAPAN
6	TAKESHI YAMAMOTO	C/O TAKASAGO INTERNATIONAL CORPORATION OF 19-22 TAKANAWA 3-CHOME, MINATO-KU, TOKYO, JAPAN.

PCT International Classification Number

C07C 33/02

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	HEI-8-244842	1996-09-17	Japan
2	Hei-9-98760	1997-04-16	Japan