Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
1999-10-07
2003-03-11
Geist, Gary (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
Reexamination Certificate
active
06531626
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a method for producing cyclopropanecarboxylates.
DESCRIPTION OF THE RELATED ART
As a method for producing cyclopropanecarboxylic acid ester, there has been disclosed a transesterification method in which cyclopropanecarboxylic acid ester compounds having various alcohol residues have been produced by using sodium alkoxide or Ti alkoxide as a catalyst from a cyclopropanecarboxylic acid ester having a lower alcohol residue and a desired alcohol GB Patent 15581/76, DE Patent 2822472, GB Patent 2005269).
However, said sodium alkoxide catalyst has problems in that it affects stereochemistry such as cis-trans ratio of the resulting ester compounds, and these methods are not always satisfactory for industrial production due to a large amount of by-products formed during the reaction.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a method for producing desired cyclopropanecarboxylic acid esters by transesterification with a corresponding monohydroxy compound in good yield.
The present invention provides:
a method for producing cyclopropanecarboxylate of the formula (3):
wherein R
1
, R
2
, R
3
, R
4
and R
5
each independently represent:
a hydrogen atom, halogen atom,
an optionally substituted alkyl group,
an optionally substituted alkenyl group,
an optionally substituted aralkyl group or
an optionally substituted aryl group; and
R
7
represents:
an optionally substituted alkyl group,
an optionally substituted aralkyl group, or
an optionally substituted aryl group,
which comprises:
reacting a cyclopropanecarboxylate of the formula (1)
wherein R
1
, R
2
, R
3
, R
4
and R
5
are as defined above, and
R
6
represents an alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group, with a monohydroxy compound of the formula (2):
R
7
OH (2)
wherein R
7
is the same as defined above, in the presence of a lanthanoid metal alkoxide.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the present invention at least one lanthanoid metal alkoxide selected from alkoxide compounds of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu can be used. Lanthanum alkoxide or Samarium alkoxide, which is industrially readily available, is preferably used.
The lanthanoid metal alkoxide of the present invention include multimers in addition to monomers depending on the kind of metal species and alkyl groups, and these multimers can also be used in the present invention.
Examples of the lanthanoid metal alkoxide include a compound of the formula (4):
Ln(OR
8
)(OR
9
)(OR
10
) (4)
wherein, Ln represents a lanthanoid metal element, R
8
, R
9
and R
10
are the same or different and independently represent an alkyl group having 1 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms for R
8
, R
9
and R
10
may independently represent a straight, branched or cyclic alkyl group, and may bond together at their terminals to form a divalent or trivalent alkoxide residue.
Examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
As the alkoxide group, methoxide, ethoxide, n-propoxide, i-propoxide, butoxide and the like are preferred since preparation thereof is easy n-Propoxide, i-propoxide and butoxide are more preferred because of solubility, and i-propoxide is most preferred because of preparation cost, advantageous production operation, and the like.
These lanthanoid metal alkoxide can be obtained by known preparation methods.
The wonohydroxy compound (2) can be allowed to react with the above-described lanthanoid metal alkoxide and then the resulting can be used in reacting the cyclopropanecarboxylate of the formula (1) with the monohydroxy compound (2).
An amount of a lanthanoid metal alkoxide is not particularly restricted but may be catalytic, and is usually in the range of 0.001 to 200 mol %, preferably 0.1 to 10 mol % based on cyclopropanecarboxylate (1).
In the cyclopropanecarboxylate of the formula (1), R
1
, R
2
, R
3
, R
4
and R
5
each independently represent a hydrogen atom, halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aralkyl or an optionally substituted aryl group.
The optionally substituted alkyl group includes, for example, an optionally substituted straight, branched or cyclic alkyl groups having 1 to 10 carbon atoms, which may be optionally substituted with a member selected from a halogen atom (e.g., fluorine, chlorine, bromine, idodine), a (C1-C3)alkoxy group, a (C1-C5)alkoxylcarbonyl group, a (C1-C5)alkylsulfonyl group and a hydroxyimino group of which hydrogen atom in the hydroxy group may be replaced by a member selected from a phenyl group, a (C1-C3)alkyl group, a (C3-C6)alkenyl group and a (C3-C6)alkynyl group.
Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, menthyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 2-bromoethyl, 1,2-dichloroethyl, 1,2-di-bromoethyl, 2,2,2-trichloroethyl, 2,2,2-tribromoethyl, methoxymethyl, 2-methoxyethyl, phenoxyiminomethyl, methoxyiminomethyl, allyoxyiminomethyl, propargyloxyiminomethyl, hydroxyiminomethyl and the like.
The optionally substituted alkenyl group include a (C2-C5)alkenyl group optionally substituted by a member selected from a halogen atom, a phenyl group, a halo-substituted (C2-C4)alkylene group, a (C1-C5)alkoxycarbonyl group, a (C1-C5)alkylsulfonyl group, a (C1-C3)alkylsulfonyloxy group and a hydroxyimino group of which hydrogen atom in the hydroxy group may be replaced by a member selected from a phenyl group, a (C1-C3)alkyl group, a (C3-C6)alkenyl group and a (C3-C6)alkynyl group.
Specific examples thereof include vinyl, 1-methylvinyl, 1-propenyl, 2-methyl-1-propenyl, 2,2-dichlorovinyl, 2,2-dibromovinyl, 2 -chloro-2-fluorovinyl, 2-chloro-2-trifluoromethylvinyl, 2-bromo-2-tribromomethylvinyl and the like.
The optionally substituted aralkyl group include a phenyl- or naphthyl-substituted (C1-C2)alkyl group which may be optionally substituted by a member selected from (C1-C10)alkyl group and a (C1-C6)alkoxy group (e.g., methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, cyclohexloxy and the like) or a halogen atom and the like on the phenyl or naphthyl ring.
Specific examples thereof include benzyl, diphenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl and the like
The optionally substituted aryl group include a phenyl or naphthyl group which may be optionally substituted with the above-described (C1-C10)alkyl group and/or a (C1-C10)alkoxy group or halogen atom and the like on the phenyl or naphthyl ring.
Specific examples thereof include phenyl, 1-naphthyl, 2-naphthyl and the like.
In the formula (1), R
6
represents an alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group.
The alkyl group having 1 to 10 carbon atoms may be straight, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, menthyl and the like. Methyl and ethyl are preferred.
The phenyl group may be optionally substituted by a group selected from (C1-C10)alkyl group and (C1-C10)alkoxy group or a halogen atom and the like.
Specific examples of the cyclopropanecarboxylate (1) include methyl cyclopropanecarboxylate, methyl 2-fluorocyclopropanecarboxylate, methyl 2,2-dichlorocyclopropanecarboxylate, methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, methyl 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate, methyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate, methyl 2,2-dimethyl-3-(3-methyl-2-butenyl)cyclopropanecarboxylate, methyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate, methyl 2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate, methyl 2,2
Oda Yoshiaki
Yako Makoto
Birch & Stewart Kolasch & Birch, LLP
Deemie Robert W.
Geist Gary
Sumitomo Chemical Company Limited
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