U.S. patent application number 10/994228 was filed with the patent office on 2005-05-26 for process for the preparation of carboxylic acid esters.
This patent application is currently assigned to Sumitomo Chemical Company, Limited. Invention is credited to Iwakura, Kazunori, Souda, Hiroshi.
Application Number | 20050113581 10/994228 |
Document ID | / |
Family ID | 34544852 |
Filed Date | 2005-05-26 |
United States Patent
Application |
20050113581 |
Kind Code |
A1 |
Souda, Hiroshi ; et
al. |
May 26, 2005 |
Process for the preparation of carboxylic acid esters
Abstract
There is provided a process for preparing a carboxylic acid
ester of formula (3): R.sup.2COOR.sup.1 (3) wherein R.sup.1 is an
alkyl group which may be substituted, an alkenyl group which may be
substituted, an alkynyl group which may be substituted, an aralkyl
group which may be substituted, or a heteroarylalkyl group which
may be substituted, and R.sup.2 is an alkyl group which may be
substituted, an alkenyl group which may be substituted, an alkynyl
group which may be substituted, an aryl group which may be
substituted, a heteroaryl which may be substituted, an aralkyl
group which may be substituted, or a heteroarylalkyl group which
may be substituted, which process is characterized by the steps of
reacting a monohydroxy compound of formula (1): R.sup.1OH (1)
wherein R.sup.1 is as defined above, with a zirconium compound of
formula (6): Zr(OR.sup.8).sub.4 (6) wherein R.sup.8 is an alkyl
group or an aryl group which may be substituted and is not the same
as R.sup.1, to prepare a zirconium catalyst, and reacting a
carboxylic acid of formula (2): R.sup.2COOH (2) wherein R.sup.2 is
as defined above, with the monohydroxy compound of formula (1) in
the presence of the zirconium catalyst.
Inventors: |
Souda, Hiroshi; (Osaka,
JP) ; Iwakura, Kazunori; (Osaka, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Assignee: |
Sumitomo Chemical Company,
Limited
|
Family ID: |
34544852 |
Appl. No.: |
10/994228 |
Filed: |
November 23, 2004 |
Current U.S.
Class: |
546/315 ;
548/530; 560/103; 560/208; 560/231 |
Current CPC
Class: |
C07F 7/003 20130101;
B01J 31/0212 20130101; C07C 67/08 20130101; C07C 67/08 20130101;
C07C 69/747 20130101 |
Class at
Publication: |
546/315 ;
548/530; 560/103; 560/208; 560/231 |
International
Class: |
C07C 069/76; C07C
069/02; C07D 213/46 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 26, 2003 |
JP |
2003-395147 |
Claims
1. A process for preparing a carboxylic acid ester of formula (3):
R.sup.2COOR.sup.1 (3) wherein R.sup.1 is an alkyl group which may
be substituted, an alkenyl group which may be substituted, an
alkynyl group which may be substituted, an aralkyl group which may
be substituted, or a heteroarylalkyl group which may be
substituted, and R.sup.2 is an alkyl group which may be
substituted, an alkenyl group which may be substituted, an alkynyl
group which may be substituted, an aryl group which may be
substituted, a heteroaryl which may be substituted, an aralkyl
group which may be substituted, or a heteroarylalkyl group which
may be substituted, which process comprises the steps of reacting a
monohydroxy compound of formula (1): R.sup.1OH (1) wherein R.sup.1
is as defined above, with a zirconium compound of formula (6):
Zr(OR.sup.8).sub.4 (6) wherein R.sup.8 is an alkyl group or an aryl
group which may be substituted and is not the same as R.sup.1, to
prepare a zirconium catalyst, and reacting a carboxylic acid of
formula (2): R.sup.2COOH (2) wherein R.sup.2 is as defined above,
with the monohydroxy compound of formula (1) in the presence of the
zirconium catalyst.
2. A process according to claim 1, wherein the carboxylic acid of
formula (2) is a cyclopropanecarboxylic acid compound of formula
(4) 3wherein, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 each
independently represents a hydrogen atom, a halogen atom, an alkyl
group which may be substituted, an alkenyl group which may be
substituted, an alkynyl group which may be substituted, an aralkyl
group which may be substituted, an aryl group which may be
substituted, or a heteroaryl group which may be substituted, and
the resultant carboxylic acid ester is a cyclopropanecarboxylic
acid ester of formula (5) 4wherein R.sup.1, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 are as defined.
3. A process according to claim 2, wherein R.sup.3, R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 are the same or different and
independently represent hydrogen, halogen, phenyl, methyl, ethyl,
dimethoxymethyl, 1-propenyl, 2-methyl-1-propenyl,
3-methyl-2-butenyl, 2,2-dichlorovinyl, 2,2,2-trichloroethyl,
2-chloro-2-fluorovinyl, 2-bromovinyl, 2,2-dibromovinyl,
1,2,2,2-tetrabromoethyl, 1,2-dibromo-2,2,-dichloroethyl- ,
2-chloro-3,3,3-trifluoro- 1-propenyl,
3,3,3-trifluoro-2-(trifluoromethyl- )-1-propenyl,
2-phenyl-1-propenyl, 2-phenylvinyl, 2-methyl-3-phenyl-2-bute- nyl,
2,2-difluorocyclopropylidene)methyl, 2-(tert-butoxycarbonyl)vinyl,
2-fluoro-2-(methoxycarbonyl)vinyl,
2-fluoro-2-(ethoxycarbonyl)vinyl,
2-fluoro-2-(tert-butoxycarbonyl)vinyl,
2-{2,2,2-trifluoro-1-(trifluoromet- hyl)ethoxycarbonyl}-vinyl,
2-aza-2-methoxyvinyl, 4-aza-4-methoxy-3-methylb-
uta-1,3-dienyl,2-{(tert-butyl)-sulfonyl}-2-(tert-butoxycarbonyl)vinyl,
2,2,2-tribromo-1-(methylsulfonyloxy)ethyl, or
2,2-dibromo-2-(hydroxysulfi- nyl)-1-(methoxy)ethyl.
4. A process according to claim 2, wherein the
cyclopropanecarboxylic acid compound of formula (4) is
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane- carboxylic acid,
2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxyli- c acid,
or 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylic acid.
5. A process according to claim 1 or 3, wherein the monohydroxy
compound of formula (1) is a primary alcohol.
6. A process according to claim 2, wherein the monohydroxy compound
of formula (1) is a benzyl group which may be substituted.
7. A process according to claim 2 or 3, wherein R.sup.1 represents
a C.sub.7-20 aralkyl group which may be substituted with at least
one member selected from the group consisting of a halogen atom,
and C.sub.1-14 alkyl, phenyl, phenoxy, C.sub.1-4 alkoxy and
C.sub.2-4 alkoxyalkyl groups which may be substituted with a
halogen atom, a propargyl group, a cyano group, a nitro group, and
a C.sub.3 haloacyloxy-methyl group.
8. A process according to claim 7, wherein R.sup.1 is a benzyl
group which may be substituted with at least one member selected
from the group consisting of a halogen atom, a methyl group, a
phenyl group, a phenoxy group, a halo-phenoxy group, a propargyl
group, a halomethyl, a halomethoxy group, a cyano group, nitro, a
methoxymethyl group and a halogen-substituted methoxymethyl
group.
9. A process according to claim 2, 3 or 4, wherein the monohydroxy
compound of formula (1) is 4-(2-thienyl)indan-2-ol,
(2,3,6-trifluoro-4-pyridyl)methane-1-ol,
(1-prop-2-ynyl-2-methylindole-3-- yl)methane-1-ol, {
1-prop-2-ynyl-2-(trifluoromethyl)indole-3-yl}methane-1-- ol,
2-furylmethyl alcohol, 3-furylmethyl alcohol,
(5-phenoxy-3-furyl)methy- l alcohol,
(5-benzyl-3-furyl)methane-1-ol, {5-(difluoromethyl)-3-furyl}met-
hane 1-ol, 5-propargylfurfuryl alcohol,
(5-methylisoxazol-3-yl)methane-1-o- l,
1-{2-(trifluoromethyl)-1,3-thiazol-4-yl}prop-2-yne-1-ol, 1-
{2-(trifluoromethoxy)-1 ,3-thiazol-4-yl}prop-2-yne-1-ol,
1-{1-prop-2-ynyl-5-(trifluoromethyl)pyrrole-3-yl}prop-2-yne-1-ol,
(1-prop-2-ynylpyrrole-3-yl)methane-1-ol,
3-(hydroxymethyl)-1-propynyl-imi- dazolidin-2,4-dione,
2-(hydroxymethyl)-4,5,6,7-tetrahydroisoindole-1,3-dio- ne,
{1-(2-propynyl)pyrrole-3-yl}methane-1-ol,
5-(hydroxymethyl)-4-methyl-(- 2-propynyl)-1,3-thazolin-2-one,
{1-(2-propynyl)-5-(trifluoromethyl)-4-pyra- zolyl}methane-1-ol,
1-{1-(2-propynyl)-5-(trifluoromethyl)pyrrole-3-yl}prop-
-2-yne-1-ol,
1-{2-(trifluoromethyl)-1,3-thiazol-4-yl}prop-2-yne-1-ol, or
1-{2-(trifluoromethoxy)-1,3-thiazol-4-yl}prop-2-yne-1-ol.
10. A process according to claim 6, wherein the monohydroxy
compound of formula (1) is a benzyl alcohol substituted with a
halogen atom.
11. A process according to any of claim 1, wherein the zirconium
compound of formula (6) is any one selected from the group
consisting of tetramethoxyzirconium, tetraethoxyzirconium,
tetrapropoxyzirconium and tetrabutoxyzirconium.
12. A process according to claim 11, wherein the reaction of the
monohydroxy compound of formula (1) with the carboxylic acid of
formula (2) is conducted after removing a hydroxy compound of
formula (7): R.sup.8OH (7) wherein R.sup.8 has the same meanings as
above, which is by-produced by reacting the zirconium compound of
formula (6) with the monohydroxy compound of formula (1).
13. A process according to claim 12, wherein the hydroxy compound
of formula (7) is removed in the presence of a solvent.
14. A process according to claim 13, wherein the solvent is a
solvent having higher boiling point than that of the hydroxy
compound of formula (7), a solvent which can make an azeotrope with
the hydroxy compound of formula (7), or a mixture of the
solvent.
15. A process for preparing a zirconium catalyst, which comprises
reacting a zirconium compound of formula (6): Zr(OR.sup.8).sub.4
(6) wherein R.sup.8 is an alkyl group or an aryl group which may be
substituted and is not the same as R.sup.1, with the monohydroxy
compound of formula (1): R.sup.1OH (1) wherein R.sup.2 is an alkyl
group which may be substituted, an alkenyl group which may be
substituted, an alkynyl group which may be substituted, an aryl
group which may be substituted, a heteroaryl which may be
substituted, an aralkyl group which may be substituted, or a
heteroarylalkyl group which may be substituted.
16. A zirconium catalyst composition prepared by reacting a
zirconium compound of formula (6): Zr(OR.sup.8).sub.4 (6) wherein
R.sup.8 is an alkyl group or an aryl group which may be substituted
and is not the same as R.sup.1, with the monohydroxy compound of
formula (1) as defined in claim 15.
17. A zirconium compound of formula (8):
Zr(OR.sup.1).sub.n(OR.sup.8).sub.- 4-n (8) wherein R.sup.1 is an
aralkyl group which may be substituted, and R.sup.8 is an alkyl
group which may be substituted or an aryl group which may be
substituted, and n is an integer of 1 to 4.
18. A zirconium compound according to claim 17, wherein R.sup.1 is
a benzyl group which may be substituted with at least one member
selected from the group consisting of a halogen atom, a propargyl
group, and methyl, methoxy, phenyl, phenoxy and methoxymethyl
groups which may be substituted, a cyano group and a nitro
group.
19. A zirconium compound according to claim 18, wherein R.sup.1 is
a benzyl group which may be substituted with at least one member
selected from the group consisting of a halogen atom, and methyl,
methoxy and methoxymethyl groups which may be substituted with
halogen.
20. A zirconium compound according to claim 19, wherein R.sup.1 is
a benzyl group substituted with a halogen atom.
21. A zirconium compound according to any one of claims 18 or 20,
wherein n=4.
22. A zirconium compound according to any one of claims 18 to 20,
wherein R.sup.8 is C.sub.1-4 alkyl group.
Description
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] The present invention relates to a process for the
preparation of carboxylic acid esters, in particular of a
cyclopropanecarboxylic acid with an alcohol.
[0002] There have been known esterification reactions of a
carboxylic acid with a hydroxyl compound thorough dehydration using
an acid catalyst such as sulfuric acid, or p-toluenesulfonic
acid(e.g., JP-A No. H09-188649 and JP-A No. H11-228491.), or using
dicyclohexylcarbodiimide or diisopropylcarbodiimide(e.g., JP-A No.
S60-64945).
[0003] It is also known that such reaction can be conducted by
using certain zirconium compound as a catalyst (JP-A No.
2002-293759).
SUMMARY OF THE INVENTION
[0004] According to the present invention, an esterification
reaction by condensing a monohydroxy compound with a carboxylic
acid can be carried out in good selectivity.
[0005] The present invention provides
[0006] a process for preparing a carboxylic acid ester of formula
(3):
R.sup.2COOR.sup.1 (3)
[0007] wherein R.sup.1 is
[0008] an alkyl group which may be substituted,
[0009] an alkenyl group which may be substituted,
[0010] an alkynyl group which may be substituted,
[0011] an aralkyl group which may be substituted, or
[0012] a heteroarylalkyl group which may be substituted, and
R.sup.2 is
[0013] an alkyl group which may be substituted,
[0014] an alkenyl group which may be substituted,
[0015] an alkynyl group which may be substituted,
[0016] an aryl group which may be substituted,
[0017] a heteroaryl which may be substituted,
[0018] an aralkyl group which may be substituted, or
[0019] a heteroarylalkyl group which may be substituted,
[0020] which process comprises the steps of reacting a monohydroxy
compound of formula (1):
R.sup.1OH (1)
[0021] wherein R.sup.1 is as defined above, with a zirconium
compound of formula (6):
Zr(OR.sup.8).sub.4 (6)
[0022] wherein R.sup.8 is an alkyl group or an aryl group which may
be substituted and is not the same as R.sup.1, to prepare a
zirconium catalyst, and
[0023] reacting a carboxylic acid of formula (2):
R.sup.2COOH (2)
[0024] wherein R.sup.2 is as defined above, with the monohydroxy
compound of formula (1) in the presence of the zirconium
catalyst.
[0025] Next, the step of preparing the zirconium catalyst by
reacting a zirconium compound with the monohydroxy compound of
formula (1) (hereinafter, referred to as monohydroxy compound (1).)
is described.
[0026] The zirconium compound of formula (6) (hereinafter, referred
to as zirconium compound (6)):
Zr(OR.sup.8).sub.4 (6)
[0027] wherein R.sup.8 is an alkyl group or an aryl group which may
be substituted and R.sup.8 is not the same as R.sup.1, is
described.
[0028] Examples of the alkyl group represented by R.sup.8 include,
for example,
[0029] a C.sub.1-6 straight or branched chain or cyclic alkyl group
such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl,
sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl.
[0030] Examples of the aryl group include, for example, phenyl, and
naphthyl(1-naphthyl, and 2-naphthyl), and preferred is a phenyl
group.
[0031] The aryl group may be substituted with an alkyl group such
as a C1-4 alkyl group (e.g., methyl, ethyl, n-propyl, i-propyl) or
butyl(e.g. t-butyl)).
[0032] Preferred R.sup.8 is C.sub.1-4 alkyl.
[0033] Typical examples of the zirconium compound (6) include, for
example, tetramethoxyzirconium, tetraethoxyzirconium,
tetrapropoxyzirconium, tetraisopropoxyzirconium,
tetrabutoxyzirconium, tetra(tert-butoxy)zirconium, tetraphenoxy
zirconium or mixture of two or more of them. In view of
ready-availability, any one tetraalkoxyzirconium selected from the
group consisting of tetramethoxyzirconium, tetraethoxyzirconium,
tetrapropoxyzirconium and tetrabutoxyzirconium is preferably
used.
[0034] The zirconium compound (6) may be used in a powder or solid
form, or may be used in a form of solution just as it is available.
Also, it may be used as a complex with a compound having a
coordination property such as tetrahydrofuran or
tetramethylethylenediamine.
[0035] Examples of the alkyl group, which may be substituted,
represented by R.sup.1, in the monohydroxy compound (1) include,
for example, a C.sub.1-10 straight, branched or cyclic alkyl group
such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl,
cyclopropylmethyl, sec-butyl, tert-butyl, pentyl, hexyl,
cyclohexyl, heptyl, octyl, nonyl, decyl or menthyl, and
[0036] a C.sub.1-10 straight, branched or cyclic alkyl group
substituted with halogen (e.g., fluorine, chlorine, bromine and
iodine).
[0037] Specific examples of the monohydroxy compound (1), wherein
R.sup.1 is an alkyl which may be substituted, referred to as the
alkyl alcohol, include, for example, methyl alcohol, ethyl alcohol,
propyl alcohol, isopropyl alcohol, butyl alcohol, sec-butyl
alcohol, tert-butyl alcohol, pentyl alcohol, neopentyl alcohol,
amyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol,
fluoroethyl alcohol, difluoroethyl alcohol, trifluoroethyl alcohol,
tetrafluoroethyl alcohol, pentafluoroethyl alcohol,
3,3-dibromo-2-propen-1-ol, perfluoropropyl alcohol,
hexafluoroisopropyl alcohol, perfluorobutyl alcohol,
perfluoropentyl alcohol, perfluorohexyl alcohol, perfluorooctyl
alcohol, and perfluorodecyl alcohol.
[0038] Examples of the alkenyl group which may be substituted,
represented by R.sup.1, include, for example, a C.sub.3-10
straight, branched or cyclic alkenyl group which may be substituted
with a group selected from the group consisting of a C1-4 alkyl
group, a C.sub.2-4 alkenyl group, a C.sub.2-4 alkynyl group and an
oxo group. Specific examples thereof include, for example,
hydroxycyclopentenone compound such as
[0039] 4-hydroxy-3-methyl-2-(2-propenyl)-2-cyclopenten-1-one,
or
[0040] 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopenten-1-one.
[0041] Examples of the alkynyl group which may be substituted,
represented by R.sup.1, include, for example, a straight, branched
or cyclic C.sub.3-10 alkynyl group which may be substituted with a
halogen and may contain a double bond such as
[0042] 4-methylhept-4-ene-1-yne-3-ol or
[0043] 4-fluorohept-4-ene-1-yne-3-ol.
[0044] Examples of the aralkyl group which may be substituted,
represented by R.sup.1, include, for example, a C.sub.7-20 aralkyl
group such as benzyl, phenylethyl, phenylpropyl, naphthylmethyl,
naphthylethyl, or anthracenylmethyl, and a C.sub.7-20 aralkyl group
substituted with at least one member selected from the group
consisting of a halogen atom, and C.sub.1-14 alkyl, phenyl,
phenoxy, C.sub.1-4 alkoxy and C.sub.2-4 alkoxyalkyl groups which
may be substituted with a halogen atom, a propargyl group, a cyano
group, a nitro group and a C.sub.3 haloacyloxy-methyl group(e.g.,
trifluoroacetyloxy-methyl).
[0045] Preferably, R.sup.1 is a benzyl which may be substituted,
and more preferably R.sup.1 is a benzyl group which may be
substituted with at least one member selected from the group
consisting of a halogen atom, a methyl group, a phenyl group, a
phenoxy group, a halo-phenoxy group, a propargyl group, a
halomethyl, a halomethoxy group, a cyano group, a nitro group, a
methoxymethyl group and a halogen-substituted methoxymethyl
group.
[0046] Furthermore preferably, R.sup.1 is a benzyl group which may
be substituted with at least one member selected from the group
consisting of a halogen atom, a methyl group, a halomethyl, a
halomethoxy group, a methoxymethyl group and a halogen-substituted
methoxymethyl.
[0047] Yet furthermore preferably, R.sup.1 is benzyl group
substituted with a halogen atom.
[0048] Specific examples of the aralkyl alcohol having the aralkyl
group which may be substituted, represented by R.sup.1, include,
for example, benzyl alcohol, 2-methyl-3-phenylbenzyl alcohol,
[0049] 2,3,5,6-tetrafluorobenzyl alcohol,
[0050] 2,3,5,6-tetrafluoro-4-methylbenzyl alcohol,
[0051] 2,3,5,6-tetrafluoro-4-methoxybenzyl alcohol,
[0052] 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol,
[0053] 2,3,5,6-tetrafluoro-4-propargylbenzyl alcohol,
[0054] 2,3,5,6-tetrafluoro-4-(difluoromethyl)benzyl alcohol,
[0055] 2,3,5,6-tetrafluoro-4-(difluoromethoxy)benzyl alcohol,
[0056]
2,3,5,6-tetrafluoro-4-(2,2,2-trifluoroacetyloxy)methyl-benzyl
alcohol, 4-(trifluoromethyl)benzyl alcohol,
[0057] 2,3,4,5-tetrafluoro-6-methylbenzyl alcohol, 3-phenylbenzyl
alcohol, 2,6-dichlorobenzyl alcohol, 3-phenoxybenzyl alcohol,
[0058] 2-hydroxy-2-(3-phenoxyphenyl)ethanenitrile,
[0059] 2-hydroxy-2-{4-(methoxymethyl)phenyl}ethanenitrile,
[0060] 2-{3-(4-chlorophenoxy)phenyl}2-hydroxyethanenitrile,
[0061]
2-(4-amino-2,3,5,6-tetrafluorophenyl)-2-hydroxyethanenitrile,
[0062] 2-(4-fluoro-3-phenoxyphenyl)-2-hydroxyethanenitrile,
[0063] (2-methylphenyl)methyl alcohol, (3-methylphenyl)methyl
alcohol, (4-methylphenyl)methyl alcohol,
[0064] 2,3-dimethylphenyl)methyl alcohol,
[0065] 2,4-dimethylphenyl)methyl alcohol,
[0066] (2,5-dimethylphenyl)methyl alcohol,
[0067] (2,6-dimethylphenyl)methyl alcohol,
[0068] (3,4-dimethylphenyl)methyl alcohol,
[0069] (2,3,4-trimethylphenyl)methyl alcohol,
[0070] (2,3,5-trimethylphenyl)methyl alcohol,
[0071] (2,3,6-trimethylphenyl)methyl alcohol,
[0072] (3,4,5-trimethylphenyl)methyl alcohol,
[0073] (2,4,6-trimethylphenyl)methyl alcohol,
[0074] (2,3,4,5-tetramethylphenyl)methyl alcohol,
[0075] (2-3,4,6-tetramethylphenyl)methyl alcohol,
[0076] (2,3,5,6-tetramethylphenyl)methyl alcohol,
[0077] (pentamethylphenyl)methyl alcohol, (ethylphenyl)methyl
alcohol, (propylphenyl)methyl alcohol,
[0078] (isopropylphenyl)methyl alcohol, (butylphenyl)methyl
alcohol, (sec-butylphenyl)methyl alcohol, (tert-butylphenyl)methyl
alcohol, (pentylphenyl)methyl alcohol,
[0079] (neopentylphenyl)methyl alcohol, (hexylphenyl)methyl
alcohol, (octylphenyl)methyl alcohol, (decylphenyl)methyl
alcohol,
[0080] (dodecylphenyl)methyl alcohol, (tetradecylphenyl)methyl
alcohol, naphthylmethyl alcohol, anthracenylmethyl alcohol,
[0081] 1-phenylethyl alcohol, 1-(1-naphthyl)ethyl alcohol,
[0082] 1-(2-naphthyl)ethyl alcohol,
[0083] 4-(prop-2-ynyl)phenylmethane-1-ol,
[0084] 3-(prop-2-ynyl)phenylmethane-1-ol,
4-prop-2-enylindan-1-ol,
[0085] 4-phenylindan-2-ol, and
[0086] alkoxyaralkyl alcohol obtained by replacing the halogen atom
of the aforementioned halo-aralkyl alcohol to methoxy, ethoxy,
propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy and the like,
cyanoaralkyl alcohol and nitroaralkyl alcohol.
[0087] Examples of the heteroarylalkyl alcohol having the
heteroarylalkyl group which may be substituted represented by
[0088] R.sup.1 include, for example, 4-(2-thienyl)indan-2-ol,
[0089] (2,3,6-trifluoro-4-pyridyl)methane-1-ol,
[0090] (1-prop-2-ynyl-2-methylindole-3-yl)methane-1-ol,
[0091]
{1-prop-2-ynyl-2-(trifluoromethyl)indole-3-yl}methane-1-ol,
[0092] 2-furylmethyl alcohol, 3-furylmethyl alcohol,
[0093] (5-phenoxy-3-furyl)methyl alcohol,
[0094] (5-benzyl-3-furyl)methane-1-ol,
[0095] {5-(difluoromethyl)-3-furyl)methane-1-ol,
[0096] 5-propargylfurfuryl alcohol,
[0097] (5-methylisoxazol-3-yl)methane-1-ol,
[0098] 1-(2-(trifluoromethyl)-1,3-thiazol-4-yl)prop-2-yne-1-ol,
[0099]
1-(2-(trifluoromethoxy)-1,3-thiazol-4-yl)prop-2-yne-1-ol,
[0100]
1-{1-prop-2-ynyl-5-(trifluoromethyl)pyrrole-3-yl)prop-2-yne-1-ol,
(1-prop-2-ynylpyrrole-3-yl)methane-1-ol,
[0101] 3-(hydroxymethyl)-1-propynyl-imidazolidin-2,4-dione,
[0102] 2-(hydroxymethyl)-4,5,6,7-tetrahydroisoindole-1,3-dione,
[0103] {1-(2-propynyl)pyrrole-3-yl}methane-1-ol,
[0104]
5-(hydroxymethyl)-4-methyl-(2-propynyl)-1,3-thazolin-2-one,
[0105]
(1-(2-propynyl)-5-(trifluoromethyl)-4-pyrazolyl}methane-1-ol,
[0106]
1-{1-(2-propynyl)-5-(trifluoromethyl)pyrrole-3-yl}prop-2-yne-1-ol,
[0107] 1-{2-(trifluoromethyl)-1,3-thiazol-4-yl)prop-2-yne-1-ol,
and
[0108]
1-(2-(trifluoromethoxy)-1,3-thiazol-4-yl}prop-2-yne-1-ol.
[0109] Among the monohydroxy compound (1), preferred is a primary
alcohol.
[0110] The zirconium catalyst thus prepared includes, for example,
a zirconium compound of formula (8) (hereinafter, referred to as
zirconium compound (8)):
Zr(OR.sup.1).sub.n(OR.sup.8).sub.4-n (8)
[0111] wherein R.sup.1 is as defined in connection with formula
(1), and R.sup.8 is as defined in connection with formula (6), and
n is an integer of 1 to 4, or mixtures thereof, which is obtained
by reacting the zirconium compound (6) with the monohydroxy
compound (1). The reaction is usually accompanied by by-production
of a monohydroxy compound of formula (7):
R.sup.8OH (7)
[0112] wherein R.sup.8is as defined, hereinafter, referred to as
monohydroxy compound (7).
[0113] The more amount of the monohydroxy compound (1) is employed,
the larger n in the zirconium compound (8) is, thus the monohydroxy
compound (7) is produced more. Zirconium compounds (8) having
different n may also be included in the reaction system.
[0114] A preferred zirconium compound is a zirconium compound (8)
wherein R.sup.1 is an aralkyl group which may be substituted and
R.sup.8 is an alkyl group which may be substituted or an aryl group
which may be substituted, and n is an integer of 1 to 4, and
[0115] a zirconium compound (8) wherein R.sup.1 represents a
heteroarylalkyl group which may be substituted such as
[0116] (1-prop-2-ynyl-2-methylindole-3-yl)methane-1-yl,
[0117]
(1-prop-2-ynyl-2-(trifluoromethyl)indole-3-yl}methane-1-yl,
[0118] 4-(2-thienyl)indan-2-yl,
[0119] (2,3,6-trifluoro-4-pyridyl)methane-1-yl,
[0120] 2-furylmethyl, 3-furylmethyl, (5-phenoxy-3-furyl)methyl,
[0121] (5-benzyl-3-furyl)methyl,
[0122] {5-(difluoromethyl)-3-furyl}methyl, 5-propargylfurfuryl,
[0123] (5-methylisoxazol-3-yl)methyl,
[0124] 1-{2-(trifluoromethyl)-1,3-thiazol-4-yl}prop-2-yne-1-yl,
[0125]
1-{2-(trifluoromethoxy)-1,3-thiazol-4-yl}prop-2-yne-1-yl,
[0126]
1-{1-prop-2-ynyl-5-(trifluoromethyl)pyrrole-3-yl}prop-2-yne-1-yl,
(1-prop-2-ynylpyrrole-3-yl)methyl,
[0127] 1-propynyl-imidazolidin-2,4-dione-3-methyl,
[0128] 3-methyl-2-(2-propenyl)-2-cyclopenten-1-one-4-yl,
[0129] 3-methyl-2-(2-propynyl)-2-cyclopenten-1-one-4-yl,
[0130] 4,5,6,7-tetrahydroisoindole-1,3-dione-2-methyl,
[0131] {1-(2-propynyl)pyrrole-3-yl}methyl, or
[0132] 4-methyl-(2-propynyl)-1,3-thazolin-2-one-5-methyl, and
R.sup.8 is an alkyl group which may be substituted or an aryl group
which may be substituted, and n is an integer of 1 to 4.
[0133] In the preferred embodiments above, more preferably, R.sup.8
is a C.sub.1-4 alkyl group, and
[0134] R.sup.1 is a benzyl alcohol which may be substituted, and
still more preferably R.sup.1 is a benzyl group which may be
substituted with at least one member selected from the group
consisting of a halogen atom, a propargyl group, and methyl,
methoxy, phenyl, phenoxy and methoxymethyl groups which may be
substituted, a cyano group and nitro.
[0135] Furthermore preferably, R.sup.1 is a benzyl group which may
be substituted with at least one member selected from the group
consisting of a halogen atom, and methyl, methoxy, and
methoxymethyl groups which may be substituted with halogen.
[0136] Yet furthermore preferably, R.sup.1 is benzyl alcohol
substituted with a halogen atom.
[0137] The by-produced monohydroxy compound (7) is preferably
removed from the reaction system by distillation or the like as it
is produced. A solution of the zirconium compound (6) in the
monohydroxy compound (7) may be available and is used as such
solution, but the monohydroxy compound (7) may also be removed from
a reaction system by a suitable operation including the
above-mentioned operation to reduce a side-reaction in the
esterification reaction step.
[0138] The above operation may be carried out with or without
solvent, and has no limitation in the amount of the solvent when
used.
[0139] Preferably used is a solvent having higher boiling point
than that of the monohydroxy compound (7), or a solvent that forms
an azeotropic mixture with the monohydroxy compound (7) or water
produced by the esterification reaction, or a mixture of the
solvents. Examples of the solvent include, for example, a
halogenated hydrocarbon solvent such as dichloromethane, chloroform
and 1,2-dichloroethane; aliphatic hydrocarbon solvent such as
hexane, heptane, octane and nonane; aromatic hydrocarbon solvent
such as benzene, toluene, xylene and chlorobenzene; and ether
solvent such as tert-butylmethyl ether, dibutyl ether, dioxane and
tetrahydrofuran.
[0140] The reaction is usually conducted under an atmosphere of
inert gas such as argon and nitrogen, and may be conducted under a
normal, pressurized or reduced pressure, preferably under normal or
reduced pressure.
[0141] The reaction is usually conducted in a temperature range of
approximately from 20 to 200.degree. C. Preferably, the reaction is
conducted at such a temperature that the monohydroxy compound (7)
can be removed by distillation or distilled as an azeotropic
mixture with a suitable solvent.
[0142] The monohydroxy compound (1) is preferably used in the
amount of not less than 5 moles per mol of the zirconium compound
(6), thereby a zirconium compound (7) wherein n=4 is obtained as a
major component. Alternatively, the monohydroxy compound (1) may be
used in an excess amount as a solvent.
[0143] In the above operation, the reaction of a zirconium compound
(6) with a monohydroxy compound (1) and the removal of a hydroxy
compound (7) produced may, for example, be conducted concurrently
or sequentially. Here, "sequentially" means the case that after
reacting the zirconium compound (6) with the monohydroxy compound
(1), the removal of the hydroxy compound (7) is conducted. In the
case of using a zirconium compound (6) as solution, the hydroxy
compound (7) usually used as solvent thereof may firstly removed,
and then the resultant zirconium compound (6) may be reacted with
the monohydroxy compound (1). Of course, the removal of the hydroxy
compound (7) in that case may be conducted concurrently or
sequentially.
[0144] Specific examples of the zirconium compound (8) include, for
example, benzyloxy-trimethoxyzirconium,
[0145]
2,3,5,6-tetrafluoro-4-methylbenzyloxy-trimethoxyzirconium,
[0146]
2,3,5,6-tetrafluoro-4-(methoxymethyl)-benzyloxy-trimethoxyzirconium-
, benzyloxy-triethoxyzirconium,
[0147]
2,3,5,6-tetrafluoro-4-methylbenzyloxy-triethoxyzirconium,
[0148]
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy-triethoxyzirconium,
benzyloxy-tripropoxyzirconium,
[0149]
2,3,5,6-tetrafluoro-4-methylbenzyloxy-tripropoxyzirconium,
[0150]
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy-tripropoxyzirconium,
benzyloxy-triisopropoxyzirconium,
[0151]
2,3,5,6-tetrafluoro-4-methylbenzyloxy-triisopropoxyzirconium,
[0152]
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy-triisopropoxyzirconi-
um, benzyloxy-tributoxyzirconium,
[0153]
2,3,5,6-tetrafluoro-4-methylbenzyloxy-tributoxyzirconium,
[0154]
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy-tributoxyzirconium,
benzyloxy-tri(tert-butoxy)zirconium,
[0155]
2,3,5,6-tetrafluoro-4-methylbenzyloxy-tri(tert-butoxy)zirconium,
[0156]
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy-tri(tert-butoxy)zirc-
onium, dibenzyloxy-dimethoxyzirconium,
[0157]
di(2,3,5,6-tetrafluoro-4-methylbenzyloxy)dimethoxyzirconium,
[0158]
di{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}dimethoxyzirconiu-
m, dibenzyloxy-diethoxyzirconium,
[0159]
di(2,3,5,6-tetrafluoro-4-methylbenzyloxy)diethoxyzirconium,
[0160] di{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}diethoxy
zirconium, dibenzyloxy-dipropoxyzirconium,
[0161]
di(2,3,5,6-tetrafluoro-4-methylbenzyloxy)dipropoxyzirconium,
[0162] di{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}dipropoxy
zirconium, dibenzyloxy-diisopropoxyzirconium,
[0163]
di(2,3,5,6-tetrafluoro-4-methylbenzyloxy)diisopropoxyzirconium,
[0164]
di{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}-diisopropoxyzirc-
onium, dibenzyloxy-dibutoxyzirconium,
[0165]
di(2,3,5,6-tetrafluoro-4-methylbenzyloxy)dibutoxyzirconium,
[0166]
di{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}dibutoxyzirconium-
, dibenzyloxy-di(tert-butoxy)zirconium,
[0167]
di(2,3,5,6-tetrafluoro-4-methylbenzyloxy)di(tert-butoxy)zirconium,
[0168]
di{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}di(tert-butoxy)zi-
rconium,
[0169] tribenzyloxy-methoxyzirconium,
[0170]
tri(2,3,5,6-tetrafluoro-4-methylbenzyloxy)methoxyzirconium,
[0171]
tri{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}methoxyzirconium-
, tribenzyloxy-ethoxyzirconium,
[0172]
tri(2,3,5,6-tetrafluoro-4-methylbenzyloxy)ethoxyzirconium,
[0173]
tri{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}ethoxyzirconium,
tribenzyloxy-propoxyzirconium,
[0174]
tri(2,3,5,6-tetrafluoro-4-methylbenzyloxy)propoxyzirconium,
[0175]
tri{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}propoxyzirconium-
, tribenzyloxy-isopropoxyzirconium,
[0176]
tri(2,3,5,6-tetrafluoro-4-methylbenzyloxy)isopropoxyzirconium,
[0177]
tri(2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy)isopropoxyzircon-
ium, tribenzyloxy-butoxyzirconium,
[0178]
tri(2,3,5,6-tetrafluoro-4-methylbenzyloxy)butoxyzirconium,
[0179]
tri{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}butoxyzirconium,
tribenzyloxy(tert-butoxy)zirconium,
[0180]
tri(2,3,5,6-tetrafluoro-4-methylbenzyloxy)(tert-butoxy)zirconium,
[0181]
tri{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}(tert-butoxy)zir-
conium,
[0182] tetra(benzyloxy)zirconium,
[0183] tetra(2,3,5,6-tetrafluoro-4-methylbenzyloxy)zirconium,
and
[0184] tetra{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}zircon
ium. Preferred are the zirconium compounds (8) wherein n=4 such as
tetra(benzyloxy)zirconium,
[0185] tetra(2,3,5,6-tetrafluoro-4-methylbenzyloxy)zirconium,
and
[0186]
tetra{2,3,5,6-tetrafluoro-4(methoxymethyl)benzyloxy}-zirconium.
[0187] The zirconium catalyst prepared by the present step may be
isolated from the reaction system, and then used in the subsequent
esterification reaction step, or may be used as a solution or
slurry obtained. The esterification catalyst may be prepared for
every batch of the esterification reaction step, or may be prepared
for a plurality of batches at one time and used in the
esterification reaction step in a suitable amount.
[0188] Next, the step of reacting the monohydroxy compound (1) with
the carboxylic acid of formula (2) (hereinafter, referred to as
carboxylic acid (2)) in the presence of the zirconium catalyst to
obtain the carboxylic acid ester of formula (3) (hereinafter,
referred to as carboxylic acid ester (3)) is described.
[0189] Examples of the alkyl group represented by R.sup.2 include,
for example, a straight, branched or cyclic C.sub.1-20 alkyl group
such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl,
sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, menthyl, heptyl,
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and
icosanyl.
[0190] Examples of the alkenyl group represented by R.sup.2include,
for example, a straight, branched or cyclic C.sub.2-10 alkenyl
group such as vinyl, 1-methylvinyl, 1-propenyl,
2-methyl-1-propenyl, 1-butenyl, 3-methyl-2-butenyl, hexenyl,
heptenyl, octenyl nonenyl or decenyl.
[0191] Examples of the alkynyl group represented by R.sup.2
include, for example, a straight or branched C.sub.2-10 alkynyl
group such as propargyl, butynyl, pentynyl, hexynyl, heptynyl,
octynyl, nonynyl or decynyl.
[0192] Examples of the aralkyl group represented by R.sup.2
include, for example, a C.sub.7-20 aralkyl group such as benzyl,
naphthylmethyl, or anthracenylmethyl.
[0193] Examples of the aryl group represented by R.sup.2 include,
for example, a C.sub.6-20 aryl group such as phenyl, 1-naphthyl or
2-naphthyl.
[0194] Examples of the heteroaryl group represented by
R.sup.2include, for example, pyridyl, thienyl and qunilyl
groups.
[0195] Examples of the heteroarylalkyl group represented by R.sup.2
include, for example, a furanylmethyl, pyridylmethyl,
imidazolylmethyl, pyrazolylmethyl, oxazolylmethyl, thizolylmethyl,
isoxazolylmethyl, thienylmethyl, indolylmethyl, pyrrolylmethyl and
quinolylmethyl.
[0196] The alkyl, alkenyl and alkynyl groups, represented by
R.sup.2 may be substituted with a member selected from Group A
consisting of a halogen, a carboxyl group, an aryl, alkoxy,
alkoxyalkyl, and alkoxycarbonyl groups which may be substituted
with a halogen atom, alkoxyimino, alkylsulfonyl, alkylsulfonyloxy
and alkylsulfinyl.
[0197] The aralkyl, aryl and heteroarylalkyl groups, represented by
R.sup.2 may be substituted with a member selected from Group B
consisting of a halogen, a carboxyl group, and alkyl, alkenyl,
alkynyl, aryl aralkyl, alkoxy, alkoxyalkyl and alkoxycarbonyl
groups which may be substituted with a halogen atom, and
alkylenedioxy(e.g., methylenedioxy).
[0198] Examples of the halogen atom in Group A and B include, for
example, fluorine, chlorine, bromine and iodine.
[0199] Examples of the alkoxy group in Group A and B include, for
example, a C.sub.1-10 alkoxy group such as methoxy, ethoxy,
propoxy, isopropoxy, butoxy, sec-butoxy or tert-butoxy;
[0200] Examples of the alkoxycarbonyl group which may be
substituted with halogen in Group A and B include, for example, a
C.sub.2-10 alkoxycarbonyl group such as methoxycarbonyl,
ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl,
butoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl, and a
halo-substituted C.sub.3-10 alkoxycarbonyl group such as
2,2,2-trifluoro-1-(trifluoromethyl)ethoxycarbonyl, and preferred is
a C.sub.3-5 alkoxycarbonyl group which may be substituted with
halogen.
[0201] Examples of the alkoxyimino group in Group A include, for
example, a C.sub.1-10 alkoxyimino group such as methoxyimino,
ethoxyimino or propoxyimino, and preferred is C.sub.1-3 alkoxyimino
group.
[0202] Examples of the alkylsulfonyl group in Group A include, for
example, a C.sub.1-10 alkylsulfonyl group such as methylsulfonyl,
ethylsulfonyl, propylsulfonyl, isopropylsulfonyl or
tert-butylsulfonyl, and preferred is a C.sub.1-4 alkylslfonyl
group.
[0203] Examples of the alkylsulfonyloxy group in Group A include,
for example, a C.sub.1-10 alkylsulfonyloxy group such as
methylsulfonyloxy, ethylsulfonyloxy, propylsulfonyloxy,
isopropylsulfonyloxy or tert-butylsulfonyloxy, and preferred is a
C.sub.1-4 alkylsulfonyloxy group.
[0204] Examples of the alkyl group in Group B include, for example,
C.sub.1-20 alkyl group as defined above, and typical examples
thereof include, for example, methyl, ethyl, propyl, isopropyl,
cyclopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl,
cyclohexyl and menthyl, and preferred is a C.sub.1-6 aklyl.
[0205] Examples of the alkenyl group in Group B include, for
example, C.sub.2-10 alkenyl group as defined above and typical
examples thereof include, for example, vinyl, 1-methylvinyl,
1-propenyl, 2-methyl-1-propenyl, 1-butenyl and 3-methyl-2-butenyl,
and preferred is a C.sub.2-5 alkenyl.
[0206] Examples of the alkynyl group in Group B include C.sub.2-10
alkynyl group as defined above, and typical examples thereof
include, for example, propargyl.
[0207] Examples of the aryl group in Group A and B include, for
example, a C.sub.6-20 aryl group as defined above, and typical
examples thereof such as phenyl, 1-naphthyl or 2-naphthyl.
[0208] Examples of the alkenyl group which may be substituted with
halogen, represented by R.sup.2, include, for example,
2,2-dichlorovinyl, 2,2-dibromovinyl, 2-chloro-2-fluorovinyl,
2-chloro-2-trifluoromethylvinyl- , 2-bromo-2-tribromomethylvinyl,
and the like.
[0209] Examples of the carboxylic acid (2) include, for example,
acetic acid, propionic acid, butyric acid, isobutyric acid, valeric
acid, isovaleric acid, pivalic acid, hexanoic acid, heptanoic acid,
octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic
acid, palmitic acid, stearic acid, acrylic acid, propiolic acid,
methacrylic acid, crotonic acid, isocrotonic acid, fumaric acid,
maleic acid, mesaconic acid, citraconic acid, cinnamic acid,
benzoic acid, naphthoic acid, toluic acid, anisic acid, piperonylic
acid, nicotinic acid, isonicotinic acid, phenylacetic acid,
2-phenylpropionic acid and the like.
[0210] Examples of the carboxylic acid (2) also include, as a
cyclopropane compound, for example, cyclopropanecarboxylic acid
compound of formula (4) (hereinafter, referred to as
cyclopropanecarboxylic acid compound (4)): 1
[0211] wherein, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 each
are independently a hydrogen atom, a halogen atom,
[0212] an alkyl, alkenyl, alkynyl, aralkyl or aryl group which may
be substituted.
[0213] In the cyclopropanecarboxylic acid compound (4), with
respect to the definitions of the halogen atom, and the alkyl,
alkynyl, alkenyl, aryl and aralkyl groups which may be substituted
represented by R.sup.3 to R.sup.7, the definitions of the same
groups defined in connection with R.sup.2 are referred to.
[0214] Examples of the cyclopropanecarboxylic acid compound (4)
include, for example, cyclopropanecarboxylic acid,
[0215] 2-fluorocyclopropanecarboxylic acid,
[0216] 2,2-dichlorocyclopropanecarboxylic acid,
[0217] 2,2-dimethyl-3-(dimethoxymethyl)cyclopropanecarboxylic
acid,
[0218] 2,2,3,3-tetramethylcyclopropanecarboxylic acid,
[0219] 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylic acid,
[0220] 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic
acid,
[0221] 2,2-dimethyl-3-(3-methyl-2-butenyl-)cyclopropanecarboxylic
acid,
[0222] 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic
acid,
[0223] 2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylic
acid, 2,2-dimethyl-3-(2-chloro-2-fluorovinyl)cyclopropanecarboxylic
acid,
[0224] 2,2-dimethyl-3-(2-bromovinyl)cyclopropanecarboxylic
acid,
[0225] 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylic
acid,
2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylic
acid,
[0226]
2,2-dimethyl-3-(1,2-dibromo-2,2,-dichloroethyl)-cyclopropanecarboxy-
lic acid,
[0227]
2,2-dimethyl-3-(2-chloro-3,3,3-trifluoro-1-propenyl)cyclopropanecar-
boxylic acid,
[0228]
2,2-dimethyl-3-{3,3,3-trifluoro-2-(trifluoromethyl)-1-propenyl}cycl-
opropanecarboxylic acid,
[0229] 2,2-dimethyl-3-(2-phenyl-1-propenyl)cyclopropanecarboxylic
acid, 2,2-dimethyl-3-(2-phenylvinyl)cyclopropanecarboxylic
acid,
[0230]
2,2-dimethyl-3-(2-methyl-3-phenyl-2-butenyl)cyclopropanecarboxylic
acid,
[0231]
2,2-dimethyl-3-{(2,2-difluorocyclopropylidene)methyl)cyclopropaneca-
rboxylic acid,
[0232]
2,2-dimethyl-3-(2-(tert-butoxycarbonyl)vinyl)cyclopropanecarboxylic
acid,
[0233]
2,2-dimethyl-3-{2-fluoro-2-(methoxycarbonyl)vinyl}cyclopropanecarbo-
xylic acid,
[0234]
2,2-dimethyl-3-(2-fluoro-2-(ethoxycarbonyl)vinyl}cyclopropanecarbox-
ylic acid,
[0235]
2,2-dimethyl-3-{2-fluoro-2-tert-butoxycarbonyl}vinyl)cyclopropaneca-
rboxylic acid,
2,2-dimethyl-3-[2-{2,2,2-trifluoro-1-(trifluoromethyl)ethox-
ycarbonyl}-vinyl]cyclopropanecarboxylic acid,
[0236] 2,2-dimethyl-3-(2-aza-2-methoxyvinyl)cyclopropanecarboxylic
acid,
[0237]
2,2-dimethyl-3-(4-aza-4-methoxy-3-methylbuta-1,3-dienyl)-cyclopropa-
necarboxylic acid,
[0238]
2,2-dimethyl-3-[(2-{(tert-butyl)sulfonyl}-2-(tert-butoxycarbonyl)vi-
nyl]cyclopropanecarboxylic acid,
[0239]
2,2-dimethyl-3-(2,2,2-tribromo-1-(methylsulfonyloxy)ethyl)cycloprop-
anecarboxylic acid,
[0240]
2,2-dimethyl-3-(2,2-dibromo-2-(hydroxysulfinyl)-1-(methoxy)ethyl)cy-
clopropanecarboxylic acid,
[0241]
2,2-dimethyl-3-{2,2,2-tribromo-1-(methylsulfonyloxy)ethyl}cycloprop-
anecarboxylic acid,
[0242] 2-methyl-2-ethyl-3-(1-propenyl)cyclopropanecarboxylic
acid,
[0243] 2,2-diethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic
acid,
[0244]
2-methyl-2-phenyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic
acid and the like.
[0245] Preferably R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7
are the same or different and independently represent hydrogen,
halogen, phenyl, methyl, ethyl, dimethoxymethyl, 1-propenyl,
2-methyl-1-propenyl, 3-methyl-2-butenyl, 2,2-dichlorovinyl,
2,2,2-trichloroethyl, 2-chloro-2-fluorovinyl, 2-bromovinyl,
2,2-dibromovinyl, 1,2,2,2-tetrabromoethyl,
1,2-dibromo-2,2,-dichloroethyl,
[0246] 2-chloro-3,3,3-trifluoro-1-propenyl,
[0247] 3,3,3-trifluoro-2-(trifluoromethyl)-1-propenyl,
[0248] 2-phenyl-1-propenyl, 2-phenylvinyl,
[0249] 2-methyl-3-phenyl-2-butenyl,
[0250] 2,2-difluorocyclopropylidene)methyl,
[0251] 2-(tert-butoxycarbonyl)vinyl,
[0252] 2-fluoro-2-(methoxycarbonyl)vinyl,
[0253] 2-fluoro-2-(ethoxycarbonyl)vinyl,
[0254] 2-fluoro-2-(tert-butoxycarbonyl)vinyl,
[0255] 2-{2,2,2-trifluoro-1-(trifluoromethyl)ethoxycarbonyl}-vinyl,
2-aza-2-methoxyvinyl,
[0256]
4-aza-4-methoxy-3-methylbuta-1,3-dienyl,2-{(tert-butyl)-sulfonyl}-2-
-(tert-butoxycarbonyl)vinyl,
[0257] 2,2,2-tribromo-1-(methylsulfonyloxy)ethyl, or
[0258] 2,2-dibromo-2-(hydroxysulfinyl)-1-(methoxy)ethyl, and more
preferably R.sup.5 and R.sup.6 represent methyl, and R.sup.7
represents hydrogen.
[0259] Suitably used cyclopropanecarboxylic acid compound (4)
are
[0260] 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic
acid,
[0261] 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic
acid and 2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylic
acid.
[0262] The zirconium catalyst can be used in a catalytic amount and
it is usually used in an amount of approximately 0.001 to 20 mol %
in terms of the zirconium atom contained per mol of the carboxylic
acid (2), preferably approximately 0.1 to 10 mol %
[0263] Then amount of the monohydroxy compound (1) that may be used
is usually in an excess amount, for example, not less than 1 mol
per mol of the carboxylic acid (2). The monohydroxy compound (1)
may be used in excess, if necessary, and may be used as
solvent.
[0264] Alternatively, the monohydroxy compound (1) may be used in
an amount of less than 1 mol per mol of the carboxylic acid (2) and
after completion of the reaction the unreacted carboxylic acid (2)
may be removed or recovered by distillation, and/or extraction.
[0265] The reaction step is usually carried out under an atmosphere
of inert gas such as argon and nitrogen. The reaction maybe
conducted under a normal, pressurized or reduced pressure.
[0266] The reaction is preferably conducted under normal or reduced
pressure. The reaction is preferably conducted by continuously
removing by-produced water by distillation.
[0267] The reaction may be conducted with or without solvent, and
has no limitation in the amount of the solvent. Examples of the
solvent that may be used include, for example, a halogenated
hydrocarbon solvent such as dichloromethane, chloroform or
1,2-dichloroethane; an aliphatic hydrocarbon solvent such as
hexane, heptane, octane or nonane; an aromatic hydrocarbon solvent
such as benzene, toluene, xylene or chlorobenzene; an ether solvent
such as diethyl ether or tetrahydrofuran. A suitable solvent that
makes an azeotropic mixture with water, is used to continuously
remove by-produced water.
[0268] The reaction is usually conducted in the temperature range
of approximately from 20 to 200.degree. C., and preferably, at the
temperature where by-produced water can be removed by distillation
or as an azeotropic mixture with the suitable solvent employed.
[0269] The reaction is usually conducted by mixing the zirconium
catalyst, the monohydroxy compound (1) and the carboxylic acid (2)
all at once and heating. Any two components of them are mixed first
and heated and then the other component is added thereto, or any
one component of them is heated and thereafter the other two
components are added thereto simultaneously.
[0270] After completion of the reaction, the zirconium catalyst can
be removed from the resulting carboxylic acid ester of formula (3)
(hereinafter, referred to as carboxylic acid ester (3)), for
example, by washing with water or acidic water. The separated
carboxylic acid ester (3) may be further purified by such
operations as distillation, recrystallization, and/or column
chromatography, if necessary.
[0271] Examples of the carboxylic acid ester (3) includes, for
example, ethyl acetate, ethyl propionate, ethyl butyrate, ethyl
isobutyrate, ethylvalerate, ethyl isovalerate, ethyl pivalate,
ethyl hexanoate, ethyl heptanoate, ethyl octanoate, ethyl
nonanoate, ethyl decanoate, ethyl laurate, ethyl myristate, ethyl
palmitate, ethyl stearate, ethyl acrylate, ethyl propiolate, ethyl
methacrylate, ethyl crotonate, ethyl isocrotonate, ethyl fumarate,
ethyl maleate, ethyl mesaconate, ethyl citraconate, ethyl
cinnamate, ethyl benzoate, ethyl naphthoate, ethyl toluate, ethyl
anisate, ethyl piperonylate, ethyl nicotinate, ethyl isonicotinate,
phenylethyl acetate and 2-phenylethyl propionate; those that have
an alkyl group which may be substituted such as a methyl group and
an n-propyl group instead of an ethyl group in ester moiety; and
those that have an aralkyl group which may be substituted such as a
benzyl group, a 2,3,5,6-tetrafluoro-4-methylbenzyl group and a
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl group instead of an
ethyl group in ester moiety.
[0272] The process of the invention is suitably used for the
production of the cyclopropanecarboxylic acid ester of formula (5)
(hereinafter, referred to to as cyclopropanecarboxylic acid ester
(5)): 2
[0273] wherein, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are
as defined in connection with formula (4) above, and R.sup.1 is as
defined in connection with formula (1) or as defined so far as
preferable.
[0274] Examples of the cyclopropanecarboxylic acid ester (5)
include, for example, ethyl cyclopropanecarboxylate,
[0275] ethyl 2-fluorocyclopropanecarboxylate,
[0276] ethyl 2,2-dichlorocyclopropanecarboxylate, ethyl
2,2-dimethyl-3-(dimethoxymethyl)cyclopropanecarboxylate,
[0277] ethyl 2,2,3,3-tetramethylcyclopropanecarboxylate,
[0278] ethyl
2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate,
[0279] ethyl
2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate,
[0280] ethyl
2,2-dimethyl-3-(3-methyl-2-butenyl)cyclopropanecarboxylate,
[0281] ethyl
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate,
[0282] ethyl
2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate, ethyl
2,2-dimethyl-3-(2-chloro
-2-fluorovinyl)cyclopropanecarboxylate,
[0283] ethyl
2,2-dimethyl-3-(2-bromovinyl)cyclopropanecarboxylate,
[0284] ethyl
2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate,
[0285] ethyl
2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxyla-
te,
[0286] ethyl
2,2-dimethyl-3-(1,2-dibromo-2,2,-dichloroethyl)cyclopropaneca-
rboxylate,
[0287] ethyl
2,2-dimethyl-3-(2-chloro-3,3,3-trifluoro-1-propenyl)cycloprop-
anecarboxylate,
[0288] ethyl
2,2-dimethyl-3-{3,3,3-trifluoro-2-(trifluoromethyl)-1-propeny-
l}cyclopropanecarboxylate,
[0289] ethyl
2,2-dimethyl-3-(2-phenyl-1-propenyl)cyclopropanecarboxylate,
[0290] ethyl
2,2-dimethyl-3-(2-phenylvinyl)cyclopropanecarboxylate,
[0291] ethyl
2,2-dimethyl-3-(2-methyl-3-phenyl-2-butenyl)cyclopropanecarbo-
xylate,
[0292] ethyl
2,2-dimethyl-3-{(2,2-difluorocyclopropylidene)methyl)cyclopro-
panecarboxylate,
[0293] ethyl
2,2-dimethyl-3-(2-(tert-butoxycarbonyl)vinyl}cyclopropanecarb-
oxylate,
[0294] ethyl
2,2-dimethyl-3-{2-fluoro-2-(methoxycarbonyl)vinyl}cyclopropan-
ecarboxylate,
[0295] ethyl
2,2-dimethyl-3-(2-fluoro-2-(ethoxycarbonyl)vinyl)cyclopropane-
carboxylate,
[0296] ethyl
2,2-dimethyl-3-{2-fluoro-2-(tert-butoxycarbonyl)vinyl}cyclopr-
opanecarboxylate,
[0297] ethyl 2,2-dimethyl-3-
[2-{2,2,2-trifluoro-1-(trifluoromethyl)ethoxy-
carbonyl}vinyl]cyclopropanecarboxylate,
[0298] ethyl
2,2-dimethyl-3-(2-aza-2-methoxyvinyl)cyclopropanecarboxylate,
[0299] ethyl
2,2-dimethyl-3-(4-aza-4-methoxy-3-methylbuta-1,3-dienyl)cyclo-
propanecarboxylate,
[0300] ethyl 2,2-dimethyl-3-
[2-{(tert-butyl)sulfonyl}-2-(tert-butoxycarbo-
nyl)vinyl]cyclopropanecarboxylate,
[0301] ethyl
2,2-dimethyl-3-{2,2,2-tribromo-1-(methylsulfonyloxy)ethyl}cyc-
lopropanecarboxylate,
[0302] ethyl
2,2-dimethyl-3-{2,2-dibromo-2-(hydroxysulfinyl)-1-(methoxy)et-
hyl}cyclopropanecarboxylate,
[0303] ethyl
2-methyl-2-ethyl-3-(1-propenyl)cyclopropanecarboxylate,
[0304] ethyl
2,2-diethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate,
[0305] ethyl
2-methyl-2-phenyl-3-(2-methyl-1-propenyl)cyclopropanecarboxyl- ate;
those that have an alkyl group which may be substituted such as a
methyl group or an n-propyl group instead of the ethyl group in the
ester moiety; and those that have the aralkyl group which may be
substituted such as a benzyl group, a
2,3,5,6-tetrafluoro-4-methylbenzyl group or a
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl group instead of the
ethyl group in the ester moiety.
[0306] The monohydroxy compound (1) and the carboxylic acid (2) may
have an asymmetric carbon atom or atoms, and may have not less than
two stereoisomers respectively, but any of them may be used in the
present invention. According to the present process, the
configurations of the alcohol compound and the
cyclopropanecarboxylic acid are retained and the corresponding
cyclopropanecarboxylic acid ester (5) having the same
configurations as their sources is usually obtained.
EXAMPLE
[0307] The following examples illustrate the present invention
further in detail, but these do not limit the scope of the present
invention. In the following examples, analysis was conducted by
using gas chromatography (hereinafter, referred to as GC). Yields
were determined by GC internal standard method, and contents of
by-products were GC area percentage values without solvent.
Example 1
[0308] To 500 ml four-neck flask, 186 g of xylene, 1.70 g of a
solution of tetrapropoxyzirconium in propanol (75% in content) and
44.8 g of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol were
charged, and the resultant solution was heated to 143 to
145.degree. C. under stirring at a normal pressure, and then 18.6 g
of a mixture of propanol and xylene was distilled off to obtain a
solution containing an zirconium catalyst.
[0309] The resultant solution was cooled below 80.degree. C., and
then 37.0 g of
2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropane-carboxylic acid,
18 g of xylene and 0.74 g of 2,6-di-tert-butyl-4-methylphenol as
stabilizing agent were charged.
[0310] To the reactor, Dean-Stark trap was equipped, and the
reaction was conducted under stirring for eight hours at 145 to
147.degree. C., removing water by-produced during the reaction into
the trap, and a solution containing
[0311] 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl
2,2-dimethyl-3-(2-methy- l-1-propenyl) cyclopropanecarboxylate was
obtained.
[0312] Yield: 97% (based on
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol) Content of
by-product: 0.5% of propyl 2,2-dimethyl-3-(2-methyl-1-
-propenyl)cyclopropanecarboxylate
Comparative Example 1
[0313] To 500 ml four-neck flask, 186 g of xylene and 1.70 g of a
solution of tetrapropoxyzirconium in propanol (75% in content) were
charged, and the resultant solution was heated to 143 to
145.degree. C. under stirring at a normal pressure, and then 18.6 g
of a mixture of propanol and xylene was distilled off.
[0314] The resultant solution was cooled below 80.degree. C., and
then 44.8 g of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol,
37.0 g of
2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid, 18
g of xylene and 0.74 g of 2,6-di-tert-butyl-4-methylphenol as
stabilizing agent were charged.
[0315] To the reactor, Dean-Stark trap was equipped, and the
reaction was conducted under stirring for eight hours at 145 to
147.degree. C., removing water by-produced during the reaction into
the trap, and a solution containing
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl
2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was
obtained.
[0316] Yield: 97% (based on
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol.
[0317] Content of by-product: 5.2% of propyl
2,2-dimethyl-3-(2-methyl-1-pr- openyl)cyclopropanecarboxylate.
Example 2
[0318] To 500 ml four-neck flask, 186 g of xylene and 1.70 g of a
solution of tetrapropoxyzirconium in propanol (75% in content)were
charged. In the resultant solution, 0.42 g of propanol as solvent
was contained.
[0319] The resultant solution was heated to 143 to 145.degree. C.
under stirring at a normal pressure, and 15.9 g of a mixture of
propanol and xylene was distilled off. Analysis of the distilled
mixture by GC internal standard method showed that 0.38 g of
propanol was contained therein.
[0320] The resultant solution was cooled below 80.degree. C., and
then 44.8 g of 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol,
10 g of xylene and 0.74 g of 2,6-di-tert-butyl-4-methylphenol as
stabilizing agent were charged. The mixture was heated to 143 to
145.degree. C. under stirring at a normal pressure, and 68.3 g of a
mixture of propanol and xylene was distilled off to obtain a
solution containing a zirconium catalyst. Analysis of the distilled
mixture by GC internal standard method showed that 0.94 g of
propanol was contained therein. A theoretical amount of propanol
produced by exchanging all propoxide contained in
tetrapropoxyzirconium is 0.92 g. Thus, it is clear that, by this
stage of operations, propanol in the solution was almost entirely
distilled off, a ligand exchange was progressed quantitatively, and
tetra{2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyloxy}zircon ium was
contained as main constituent in the solution.
[0321] The resultant solution was cooled below 80.degree. C., and
then 37.0 g of
2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid was
charged thereto.
[0322] To the reactor, Dean-Stark trap was equipped, and the
reaction was conducted with stirring for eight hours at 145 to
147.degree. C., removing water by-produced during the reaction into
the trap, and a solution containing
[0323] 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl
2,2-dimethyl-3-(2-methy- l-1-propenyl)cyclopropanecarboxylate was
obtained.
[0324] Yield: 98% (based on
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl alcohol.
[0325] Content of by-product: propyl
2,2-dimethyl-3-(2-methyl-1-propenyl)c- yclopropanecarboxylate was
not detected (detection lower limit: 0.04%).
* * * * *