Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-05-04
2002-06-25
Coleman, Brenda (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
06410741
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to optically active bisoxazoline compounds, a process for producing them and a process for producing optically active cyclopropanecarboxylic acid derivatives using them.
2. Description of Related Arts
The optically active cyclopropanecarboxylic acid esters are important compounds as intermediates for pharmaceuticals and pesticides. For example, (+)-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid, also known as chrysanthemum-monocarboxylic acid, constitutes the acid component of synthetic pyrethroid insecticides.
Conventionally, as the methods for directly producing optically active cyclopropanecarboxylic acid esters by synthetic technique, for example, a method has been known in which a prochiral olefin is reacted with a diazoacetic acid ester in the presence of an asymmetric copper complex using an optically active bis[2-(4,5-diphenyl-1,3-oxazolinyl)]methane as the ligand (Tetrahedron Lett., 32, 7373 (1991)).
Since, however, this method has problems that the raw material used for synthesizing the ligand is expensive and that the method for synthesizing the ligand is complicated, this method can not always be said to be an industrially advantageous method.
The present inventors have completed the present invention as the result of an extensive study conducted for the purpose of providing optically active bisoxazoline compounds useful as asymmetric ligands for copper complexes which are used in preparing optically active cyclopropanecarboxylic acid esters by reacting an olefin with a diazoacetic acid ester.
SUMMARY OF THE INVENTION
The present invention provides:
1. an optically active bisoxazoline compound of the formula [I]:
wherein
R
1
represents alkyl group, cycloalkyl group, aralkyl group, phenyl group which may be substituted or alkoxy group and the geminal alkyl groups may be joined together to form a cyclic structure;
R
2
represents alkyl group, cycloalkyl group, aralkyl group, or phenyl group which may be substituted,
R
3
represents a hydrogen atom, (C2-C4)alkyl group or cycloalkyl group and the asterisk * represents an asymmetric carbon atom;
2. a process for producing the optically active bisoxazoline compound of the formula [I] which comprises reacting an optically active 2-amino alcohol of the formula [II]:
wherein R
1
, R
2
and the asterisk * are as defined above, with a malonic acid derivative of the formula (3):
wherein R
3
is as defined above and R
4
represents alkoxy group or halogen atom,
to give a bisamido alcohol compound of the formula [IV]:
wherein R
1
, R
2
and R
3
are as defined above,
and then subjecting the compound of the formula [IV] to cyclization reaction in the presence of a Lewis acid catalyst; and
3. a process for producing an optically active cyclopropanecarboxylic acid derivative of the formula [VII]:
wherein R
5
, R
6
, R
7
and R
8
are the same or different and represent hydrogen atom, halogen atom, alkyl group, aralkyl group, aryl group, alkenyl group, alkyl group substituted with halogen atom or alkenyl group substituted with halogen atom, with the proviso that when R
5
and R
6
represent the same group, then R
7
and R
3
represent different groups, and R
9
represents alkyl group, cycloalkyl group or phenyl group which may be substituted,
which comprises reacting a prochiral olefin of the formula [V]:
wherein R
5
, R
6
, R
7
and R
8
are as defined above, with a diazoacetic acid ester of the formula [VI]:
N
2
CHCO
2
R
9
[VI]
wherein R
9
is as defined above, in the presence of a copper complex prepared from an optically active bisoxazoline compound of the formula [I] and a copper compound.
DETAILED DESCRIPTION
In the optically active bisoxazoline compounds [I] according to the present invention, the alkyl group represented by R
1
and R
2
includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-amyl group, neopentyl group, n-hexyl group, n-octyl group, n-nonyl group and the like, and the cycloalkyl group includes cyclohexyl group, menthyl group and the like.
Examples of the (C2-C4)alkyl group for R
3
includes an ethyl, n-propyl group, n-butyl group, isobutyl group.
When R
1
is alkyl group, two geminal alkyl groups may be joined together to form a cyclic structure containing 4 to 7 carbon atoms.
In the substituent R
1
, the alkoxy group includes methoxy group, ethoxy group, n-propoxy group, t-butoxy group and the like. The aralkyl group includes benzyl group, 2-phenylethyl group, 2-naphthylethyl group, diphenylmethyl group and the like. The phenyl group which may be substituted includes phenyl group, alkylphenyl group, alkoxyphenyl group, alkylalkoxyphenyl group and the like. These alkylphenyl group, alkoxyphenyl group, alkylalkoxyphenyl group include, for example, phenyl group substituted with 1-3 alkyl and/or alkoxy groups, respectively, described above at ortho-, meta- or para-position.
The optically active bisoxazoline compounds [I] according to the present invention have two asymmetric carbon atoms, as indicated by the asterisk *, and include at least two kinds of optical isomers resulting from the asymmetric carbon atoms. The optically active bisoxazoline compounds [I] according to the present invention contain such optical isomers.
The optically active bisoxazoline compounds [I] according to the present invention are novel, and can be synthesized, for example, by the following process.
The optically active bisoxazoline compound [I] can be obtained by reacting an optically active 2-amino alcohol of the formula [II]:
wherein R
1
, R
2
and the asterisk * are as defined above, with a malonic acid derivative of the formula [III]:
wherein R
3
is as defined above and R
4
represents alkoxy group or halogen atom,
to give a bisamido alcohol compound of the formula [IV]:
wherein R
1
, R
2
and R
3
are as defined above, and then subjecting this compound to cyclization in the presence of a Lewis acid catalyst.
The optically active 2-amino alcohol [II] includes: for example,
(R)-2-amino-1,1-dimethylpropanol,
(R)-2-amino-1,1-diethylpropanol,
(R)-2-amino-1,1-di-n-propylpropanol,
(R)-2-amino-1,1-di-i-propylpropanol,
(R)-2-amino-1,1-dicyclohexylpropanol,
(R)-2-amino-1,1-dimethoxypropanol,
(R)-2-amino-1,1-diethoxypropanol,
(R)-2-amino-1,1-diphenylpropanol,
(R)-2-amino-1,1-di-(2-methylphenyl)propanol,
(R)-2-amino-1,1-di-(3-methylphenyl)propanol,
(R)-2-amino-1,1-di-(4-methylphenyl)propanol,
(R)-2-amino-1,1 di-(2-methoxyphenyl)propanol,
(R)-2-amino-1,1-di-(3-methoxyphenyl)propanol,
(R)-2-amino-1,1-di-(4-methoxyphenyl)propanol,
1-(1-(R)-aminoethyl)cyclobutanol,
1-(1-(R)-aminoethyl)cyclopentanol,
1-(1-(R)-aminoethyl)cyclohexanol,
1-(1-(R)-aminoethyl)cycloheptanol,
(R)-2-amino-3-methyl-1,1-dimethylbutanol,
(R)-2-amino-3-methyl-1,1-diethylbutanol,
(R)-2-amino-3-methyl-1,1-di-n-propylbutanol,
(R)-2-amino-3-methyl-1,1-di-i-propylbutanol,
(R)-2-amino-3-methyl-1,1-dicyclohexylbutanol,
(R)-2-amino-3-methyl-1,1-diphenylbutanol,
(R)-2-amino-3-methyl-1,1-di-(2-methylphenyl)butanol,
(R)-2-amino-3-methyl-1,1-di-(3-methylphenyl)butanol,
(R)-2-amino-3-methyl-1,1-di-(4-methylphenyl)butanol,
(R)-2-amino-3-methyl-1,1-di-(2-methoxyphenyl)butanol,
(R)-2-amino-3-methyl-1,1-di-(3-methoxyphenyl)butanol,
(R)-2-amino-3-methyl-1,1-di-(4-methoxyphenyl)butanol,
1-(1-(R)-amino-2-methyl-n-propyl)cyclobutanol,
1-(1-(R)-amino-2-methyl-n-propyl)cyclopentanol,
1-(1-(R)-amino-2-methyl-n-propyl)cyclohexanol,
1-(1-(R)-amino-2-methyl-n-propyl)cycloheptanol,
(R)-2-amino-4-methyl-1,1-dimethylpentanol,
(R)-2-amino-4-methyl-1,1-diethylpentanol,
(R)-2-amino-4-methyl-1,1-di-n-propylpentanol,
(R)-2-amino-4-methyl-1,1-di-i-propylpentanol,
(R)-2-amino-4-methyl-1,1-dicyclohexylpentanol,
(R)-2-amino-4-methyl-1,1-diphenylpentanol,
(R)-2-amino-4-methyl-1,1-di-(2-methylphenyl)pentanol,
(R)-2-amino-4-methyl-1,1-di-(3-methyl
Itagaki Makoto
Suzukamo Gohfu
Coleman Brenda
Sumitomo Chemical Company Limited
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