U.S. patent application number 10/760523 was filed with the patent office on 2004-08-05 for process for producing carbonyl or hydroxy compound.
This patent application is currently assigned to Sumitomo Chemical Company, Limted. Invention is credited to Hagiya, Koji, Kurihara, Akio, Takano, Naoyuki.
Application Number | 20040152592 10/760523 |
Document ID | / |
Family ID | 27554829 |
Filed Date | 2004-08-05 |
United States Patent
Application |
20040152592 |
Kind Code |
A1 |
Hagiya, Koji ; et
al. |
August 5, 2004 |
Process for producing carbonyl or hydroxy compound
Abstract
There are disclosed are a method for producing at least one
compound selected from a carbonyl compound and a hydroxy adduct
compound by an oxidative cleavage or addition reaction of an
olefinic double bond of an olefin compound, which contains reacting
an olefin compound with hydrogen peroxide, utilizing as a catalyst,
at least one member selected from (a) tungsten, (b) molybdenum, or
(c) a tungsten or molybdenum metal compound containing (ia)
tungsten or (ib) molybdenum and (ii) an element of Group IIIb, IVb,
Vb or VIb excluding oxygen, and a catalyst composition.
Inventors: |
Hagiya, Koji; (Ibaraki-shi,
JP) ; Takano, Naoyuki; (Ibaraki-shi, JP) ;
Kurihara, Akio; (Suita-shi, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Assignee: |
Sumitomo Chemical Company,
Limted
|
Family ID: |
27554829 |
Appl. No.: |
10/760523 |
Filed: |
January 21, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10760523 |
Jan 21, 2004 |
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09925523 |
Aug 10, 2001 |
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6703528 |
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Current U.S.
Class: |
502/305 |
Current CPC
Class: |
C07C 409/04 20130101;
C07C 409/14 20130101; C07C 67/333 20130101; C07C 407/00 20130101;
B01J 23/30 20130101; C07C 29/03 20130101; C07C 2601/02 20170501;
C07C 2602/20 20170501; B01J 21/02 20130101; C07C 49/258 20130101;
B01J 23/28 20130101; C07C 51/31 20130101; C07C 45/294 20130101;
C07B 41/00 20130101; C07C 45/53 20130101; C07C 67/31 20130101; C07C
45/28 20130101; C07C 45/53 20130101; C07C 49/258 20130101; C07C
51/31 20130101; C07C 59/347 20130101; C07C 51/31 20130101; C07C
55/14 20130101; C07C 67/31 20130101; C07C 69/757 20130101; C07C
67/333 20130101; C07C 69/757 20130101; C07C 407/00 20130101; C07C
409/04 20130101; C07C 407/00 20130101; C07C 409/14 20130101; C07C
29/03 20130101; C07C 35/28 20130101 |
Class at
Publication: |
502/305 |
International
Class: |
B01J 023/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 11, 2000 |
JP |
2000-244277 |
Oct 27, 2000 |
JP |
2000-328816 |
Oct 27, 2000 |
JP |
2000-328812 |
Nov 6, 2000 |
JP |
2000-337152 |
Nov 6, 2000 |
JP |
2000-337151 |
Nov 6, 2000 |
JP |
2000-337150 |
Claims
What is claimed is:
1. An oxidation catalyst composition obtained by reacting aqueous
hydrogen peroxide with at least one member selected from (a) a
tungsten or molybdenum metal compound comprising (ia) tungsten or
(ib) molybdenum and (ii) an element of Group IIIb, IVb, Vb or VIb
excluding oxygen, provided that said tungsten metal compound is not
tungstencarbide.
2. An oxidation catalyst composition obtained by reacting aqueous
hydrogen peroxide with at least one member selected from (a)
tungsten, (b) molybdenum, or (c) a tungsten or molybdenum metal
compound comprising (ia) tungsten or (ib) molybdenum, and (ii) an
element of Group IIIb, IVb, Vb or VIb excluding oxygen, and
containing an organic solvent.
3. The oxidation catalyst according to claim 1 or 2, wherein the
metal compound is tungsten boride, tungsten disulfide or molybdenum
boride.
4. The oxidation catalyst according to claim 2, wherein the organic
solvent is t-butanol or methyl t-butyl ether.
5. The oxidation catalyst according to claim 4, which is
dehydrated.
6. The oxidation catalyst according to claim 5, wherein dehydrating
is conducted by using anhydrous magnesium sulfate.
Description
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] The present invention relates to an oxidation catalyst and
methods using the same for producing carbonyl compounds and hydroxy
adduct compounds by oxidative cleavage of an olefinic double bond
or addition reaction thereto.
[0002] A method for producing adipic acid by reacting, in the
presence of sodium tungstate and trioctylmethylammonium sulfate,
cyclohexene with an aqueous hydrogen peroxide is known (JP-A
2000-86574), and a method for producing an aldehyde by reacting an
olefin with hydrogen peroxide, using heteropolyacid containing
phosphorus or germanium, is also known (JP-B 6-84324).
[0003] However, yields of the desired products in these methods
were not always satisfactory for an industrial scale of
production.
SUMMARY OF THE INVENTION
[0004] According to the present invention, carbonyl compounds and
hydroxy adduct compounds can be obtained by using a readily
available oxidation catalyst, which can selectively provide desired
compounds in an improved yield.
[0005] Thus, the present invention provides:
[0006] 1. a method for producing at least one compound selected
from a carbonyl compound and a hydroxy adduct compound by an
oxidative cleavage or addition reaction of an olefinic double bond
of an olefin compound,
[0007] which comprises
[0008] reacting an olefin compound with hydrogen peroxide,
utilizing as a catalyst, at least one member selected from
[0009] (a) tungsten,
[0010] (b) molybdenum or
[0011] (c) a tungsten or molybdenum metal compound comprising
[0012] (ia) tungsten or (ib) molybdenum and
[0013] (ii) an element of Group IIIb, IVb, Vb or VIb excluding
oxygen;
[0014] 2. an oxidation catalyst composition obtained by reacting
aqueous hydrogen peroxide with at least one member selected
from
[0015] a tungsten or molybdenum metal compound comprising
[0016] (ia) tungsten or (ib) molybdenum, and
[0017] (ii) an element of Group IIIb, IVb, Vb or VIb excluding
oxygen, provided that said tungsten metal compound is not tungsten
carbide;
[0018] 3. an oxidation catalyst composition
[0019] obtained by
[0020] reacting aqueous hydrogen peroxide with at least one member
selected from
[0021] (a) tungsten,
[0022] (b) molybdenum, or
[0023] (c) a tungsten or molybdenum metal compound comprising
[0024] (ia) tungsten or (ib) molybdenum, and
[0025] (ii) an element of Group IIIb, IVb, Vb or VIb excluding
oxygen, and containing an organic solvent;
[0026] 4. a method for producing a carbonyl compound of formula
(II):
R.sub.aR.sub.bC.dbd.O (II)
[0027] wherein a and b respectively represent 1 and 2, or 3 and 4,
which comprises subjecting a hydroxy adduct compound of formula
(III):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (IIIa)
[0028] wherein X is a hydroperoxide group, and R.sub.1 to R.sub.4
represent a hydrogen atom or an organic residue, to a decomposition
reaction;
[0029] 5. a method for producing a hydroxy adduct compound of
formula (IIIb):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (IIIb)
[0030] wherein X is a hydroxy group and R.sub.1 to R.sub.4
independently represent a hydrogen atom or an organic residue,
which comprises reacting a hydroxy adduct compound of formula
(IIIa):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (IIIa)
[0031] wherein X is a hydroperoxide group, and R.sub.1 to R.sub.4
are the same as defined above, with a reducing agent;
[0032] 6. a hydroxy adduct compound of formula (III):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (III)
[0033] wherein X is a hyroperoxide group or a hydroxy group,
R.sub.1 and R.sub.2 represent a methyl group, R.sub.3 represents a
hydrogen atom, and R.sub.4 represents a group of formula: 1
[0034] wherein R' is an alkyl, aryl or aralkyl group; and
[0035] 7. a hydroxy adduct compound of formula (IIIa):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (IIIa)
[0036] wherein X represents a hyroperoxide group, R.sub.1
represents a methyl group, R.sub.3 represents a hydrogen atom, and
R.sub.2 and R.sub.4 form a group of formula: 2
DETAILED DESCRIPTION OF THE INVENTION
[0037] First, the method for producing at least one compound
selected from a carbonyl compound and a hydroxy adduct compound by
an oxidative cleavage or addition reaction of an olefinic double
bond of an olefin compound is described.
[0038] The method is conducted, for example, by reacting the olefin
compound and the metal or the metal compound, which is utilized as
a catalyst, with hydrogen peroxide, or it may be conducted in such
a manner that the metal or the metal compound is reacted with
aqueous hydrogen peroxide to form a catalyst composition and
subsequently the olefin compound is reacted with hydrogen peroxide
in the presence of the catalyst composition so produced. Thus the
production method may be conducted by reacting hydrogen peroxide
with the metal or the metal compound, and reacting the olefin
compound with hydrogen peroxide, simultaneously in the same
reactor, or in the presence of the catalyst composition.
[0039] The metal or the metal compound is described below.
[0040] Examples of the tungsten metal compound comprising tungsten
and an element of Group IIIb include tungsten boride and the like.
Examples of the tungsten metal compound comprising tungsten and an
element of Group IVb include tungsten carbide, tungsten silicide
and the like. Examples of the tungsten metal compound comprising
tungsten and an element of Group Vb include tungsten nitride,
tungsten phosphide. Examples of the tungsten metal compound
comprising tungsten and an element of Group VIb other than oxygen
include tungsten sulfide and the like. Preferred are tungsten,
tungsten boride, tungsten carbide and tungsten sulfide.
[0041] Example of the molybdenum metal compound comprising
molybdenum and an element of Group IIIb include molybdenum boride,
Examples of the molybdenum metal compound comprising molybdenum and
an element of Group IVb include molybdenum carbide, molybdenum
silicide and the like. Examples of the molybdenum metal compound
comprising molybdenum and an element of Group Vb include molybdenum
nitride, molybdenum phosphide and the like. Examples of the
molybdenum metal compound comprising molybdenum and an element of
Group VIb other than oxygen include molybdenum sulfide and the
like. Preferred are molybdenum and molybdenum boride.
[0042] Any shape of the metal compounds can be used in the present
invention. Preferred are those of smaller particle. A catalytic
amount of the metal or metal compound may be used in the present
production method. A typical amount thereof may be 0.001 to 0.95
mole per mol of the olefin compound.
[0043] Hydrogen peroxide is usually used in a form of an aqueous
solution. A solution of hydrogen peroxide in an organic solvent may
also be used. Any concentration of hydrogen peroxide in an aqueous
solution or in an organic solvent solution may be used, and
preferred concentration is 1 to 60% by weight. For example,
commercially available aqueous hydrogen peroxide may be used
without any modification, or, if necessary, it may be used after
adjustment of its concentration by dilution, concentration or the
like.
[0044] The solution of hydrogen peroxide in an organic solvent can
be prepared, for example, by such means as extracting of an aqueous
hydrogen peroxide solution with an organic solvent or removing
water by distillation of the aqueous solution, preferably in the
presence of an appropriate organic solvent, which includes such a
solvent that may form an azeotrope with water. Examples of the
organic solvent include ether type solvents such as diethyl ether,
methyl tert-butyl ether, tetrahydrofuran or the like, ester
solvents such as ethyl acetate or the like, alcohol solvents such
as methanol, ethanol, tert-butanol or the like, and alkylnitrile
solvents such as acetonitrile, propionitrile or the like. Any
amount of organic solvents may be used, and is typically not more
than 100 parts by weight per 1 part by weight of the olefin
compound. Preferred organic solvent is an inert organic solvent and
is for example, t-butanol or methyl t-butyl ether.
[0045] The amount of hydrogen peroxide that may be used is usually
not less than 1 mole per mol of the olefin compound. There is no
particular upper limit of the amount of hydrogen peroxide that may
be used, but a preferred amount thereof is not more than 50 moles
per mol of the olefin compound, and a preferred amount thereof may
be set for the olefin compound and the desired products therefrom
as below.
[0046] The oxidation catalyst composition of the present production
method can be obtained by reacting aqueous hydrogen peroxide with
at least one metal or metal compound as described above to form the
catalyst composition as a homogeneous solution or a suspension,
both of which can be used. The amount of the hydrogen peroxide is
preferably 5 moles or more per mol of the metal or the metal
compound. The organic solvent as described above may be used to
produce the catalyst composition containing the organic solvent,
which may be further dehydrated prior to use, if necessary. Typical
examples of the dehydrating agents include anhydrous magnesium
sulfate, anhydrous sodium sulfate, anhydrous boric acid,
polyphosphoric acid, diphosphorous pentaoxide and the like.
[0047] The reacting of the metal or the metal compound with
hydrogen peroxide may be conducted at any temperature, and
preferably at -10 to 100.degree. C.
[0048] In the present production method, the carbonyl compound and
the hydroxy adduct compound can be obtained by an oxidative
cleavage and addition reaction of an olefinic double bond of an
olefin compound.
[0049] The carbonyl compound, which results in the oxidative
cleavage of the olefin double bond, optionally followed by further
oxidation, include ketone, aldehyde, and a carboxylic acid, and the
hydroxy adduct compound include diol or .beta.-hydroxyhydroperoxide
compound.
[0050] The olefin compound that may be used include an olefin
compound of formula (I):
R.sub.1R.sub.2C.dbd.CR.sub.3R.sub.4 (I),
[0051] wherein R.sub.1 to R.sub.4 are the same or different and
represent a hydrogen atom or an organic residue, and two geminal
groups or two groups which are in syn position among the R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 groups may form a divalent organic
residue, provided that R.sub.1 to R.sub.4 do not simultaneously
represent a hydrogen atom.
[0052] The carbonyl compound that may be produced includes a
carbonyl compound of formula (II):
R.sub.aR.sub.bC.dbd.O (II),
[0053] wherein a and b respectively represent 1 and 2, or 3 and 4,
or R.sub.b represents a hydroxy group.
[0054] The carbonyl compound of formula (II) above include a
compound of formula (IV):
R.sub.1R.sub.2C.dbd.O, and R.sub.3R.sub.4C.dbd.O (IV)
[0055] wherein R.sub.1 to R.sub.4 are the same as defined
above.
[0056] The hydroxy adduct compound that may be produced include a
compound of formula (III):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (III)
[0057] wherein X represents a hydroxy group or a hydroperoxide
group.
[0058] Substituent groups R.sub.1 to R.sub.4 are described
below.
[0059] Examples of the organic residue include alkyl, alkoxy, aryl,
aryloxy, aralkyl and aralkyloxy groups, alkylcarbonyl,
arylcarbonyl, aralkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl,
aralkyloxycarbonyl, carboxyl and carbonyl groups, all of which may
be substituted.
[0060] The divalent organic residue means a group formed by the
above described groups and specific examples thereof include an
alkylene, oxaalkylene, arylene, oxaarylene, aralkylene,
oxaaralkylene, alkylenecarbonyl, arylenecarbonyl,
aralkylenecarbonyl, alkyleneoxacarbonyl, arylenoxacarbonyl,
aralkylenoxacarbonyl groups or the like, all of which may be
substituted.
[0061] Preferred organic residue are alkyl, aryl, aralkyl,
alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkoxycarbonyl,
aryloxycarbonyl, aralkyloxycarbonyl, carboxyl and carbonyl groups,
all of which may be substituted and corresponding divalent organic
residues, which may be substituted.
[0062] The alkyl groups in the alkyl, alkoxy, aralkyl, aralkyloxy,
alkylcarbonyl, aralkylcarbonyl, alkoxycarbonyl and
aralkyloxycarbonyl groups include a linear, branched or cyclic
alkyl group having 1 to 20 carbon atoms such as a methyl group, an
ethyl group, a n-propyl group, an isopropyl group, a n-butyl group,
an isobutyl group, a sec-butyl group, a tert-butyl group, a
n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group,
a n-nonyl group, a n-decyl group, a cyclopropyl group, a
2,2-dimethylcyclopropyl group, a cyclopentyl group, a cyclohexyl
group and a menthyl group.
[0063] Examples of the aryl groups in the aryl, aryloxy, aralkyl,
aralkyloxy, arylcarbonyl, aralkylcarbonyl, aryloxycarbonyl and
aralkyloxycarbonyl groups include a phenyl group, a naphthyl group
and the like.
[0064] The aralkyl group means a group comprising the ary group and
the alkyl group as described above.
[0065] The alkoxy, aryoxy and aralkyloxy groups mean groups that
respectively comprising corresponding alkyl, aryl and aralkyl
groups and an oxy group.
[0066] The alkylcarbonyl, arylcarbonyl, aralkylcarbony,
alkoxycarbonyl, aryoxycarbonyl, aralkyloxycarbony groups mean
groups respectively comprising alkyl, aryl, aralkyl, alkoxy, aryoxy
and aralkyloxy groups and a carbonyl group.
[0067] Examples of the alkyl groups, which may be substituted, for
example, include an alkyl group substituted with the alkoxy,
aryloxy or aralkyloxy group, the halogen atom, the alkylcarbonyl,
arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl,
carboxyl or carbonyl group as described above.
[0068] The alkyl moieties of the alkoxy, alkoxycarbonyl,
alkylcarbonyl may also be substituted as the alkyl groups described
above.
[0069] Examples of the halogen atoms include a fluorine atom, a
chlorine atom, a bromine atom and the like.
[0070] Specific examples of the alkyl groups, which may be
substituted include, for example, a chloromethyl group, a
fluoromethyl group, a trifluoromethyl group, a methoxymethyl group,
an ethoxymethyl group, a methoxyethyl group, a carbomethoxymethyl
group and the like.
[0071] The aryl groups in the aryl, aryloxy, aralkyl, aralkyloxy,
arylcarbonyl, aralkylcarbonyl, aryloxycarbonyl and
aralkyloxycarbonyl groups may be substituted with the alkyl, aryl,
alkoxy, aralkyl, aryloxy or aralkyloxy group or a halogen atom as
described above.
[0072] Specific examples of the aryl groups, which may be
substituted include, for example, a phenyl group, a naphthyl group,
a 2-methylphenyl group, a 4-chlorophenyl group, a 4-methylphenyl
group, 4-methoxyphenyl group, a 3-phenoxyphenyl group and the
like.
[0073] Specific examples of the aryloxy group, which may be
substituted include, for example, a phenoxy group, a
2-methylphenoxy group, a 4-chlorophenoxy group, a 4-methylphenoxy
group, a 4-methoxyphenoxy group and a 3-phenoxyphenoxy group.
[0074] Specific examples of the aralkyl group, which may be
substituted include, for example, a benzyl group, a 4-chlorobenzyl
group, a 4-methylbenzyl group, a 4-methoxybenzyl group, a
3-phenoxybenzyl group, a 2,3,5,6-tetrafluorobenzyl group, a
2,3,5,6-tetrafluoro-4-methylbenzyl group, a
2,3,5,6-tetrafluoro-4-methoxybenzyl group, a
2,3,5,6-tetrafluoro-4-methoxymethylbenzyl group and the like.
[0075] Examples of the alkylcarbonyl, arylcarbonyl, and
aralkylcarbonyl groups respectively include, for example, a
methylcarbonyl group, an ethylcarbonyl group, a phenylcarbonyl
group, a benzylcarbonyl group and the like.
[0076] Examples of the alkoxycarbonyl, aryloxycarbonyl and
aralkyloxycarbonyl groups respectively include, for example, a
methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl
group, a benzyloxycarbonyl group and the like.
[0077] Specific examples of the linear, branched or cyclic alkoxy
groups having 1 to 20 carbon atoms include a methoxy group, an
ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy
group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group,
a n-pentyloxy group, a n-decyloxy group, a cyclopentyloxy group, a
cyclohexyloxy group, a menthyloxy group and the like.
[0078] Examples of the alkoxy group, which may be substituted
include, for example, a chloromethoxy group, a fluoromethoxy group,
a trifluoromethoxy group, a methoxymethoxy group, an ethoxymethoxy
group, a methoxyethoxyl group and the like.
[0079] Specific examples of the aralkyloxy group, which may be
substituted include a benzyloxy group, a 4-chlorobenzyloxy group, a
4-methylbenzyloxy group, a 4-methoxybenzyloxy group, a
3-phenoxybenzyloxy group, a 2,3,5,6-tetrafluorobenzyloxy group, a
2,3,5,6-tetrafluoro-4-methylbenzylo- xy group, a
2,3,5,6-tetrafluoro-4-methoxybenzyloxy group, a
2,3,5,6-tetrafluoro-4-methoxymethylbenzyloxy group and the
like.
[0080] Examples of the olefin of formula (I) wherein three of the
R.sub.1 to R.sub.4 groups represent a hydrogen atom, which are
referred to as "mono-substituted olefin" include 1-hexene,
1-heptene, 1-octene, 1-undecene, styrene, 1,7-octadiene and allyl
benzyl ether. Further examples of the olefin compound, which are
referred to as "di-substituted terminal olefin", include
2-methylpropene, 2-methyl-4,4-dimethyl-1-propen- e,
2-ethyl-1-butene, 2-methyl-1-pentene, .alpha.-methylstyrene,
.alpha.-phenylstyrene, methylenecyclobutane, methylenecyclopentane,
methylenecyclohexane, .beta.-pinene, camphene,
1,3,3-trimethyl-2-methylin- dorine and
.alpha.-methylene-.gamma.-butyrolactone.
[0081] Examples of the olefin of formula (I) wherein two groups of
R.sub.1 to R.sub.4 groups represent a hydrogen atom, which are
referred to as "di-substituted internal olefin, include
cyclopentene, cyclohexene, cycloheptene, cyclooctene,
3-methylcyclopentene, 4-methylcyclopentene,
3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene,
3,4,5-trimethylcyclopentene, 3-chlorocyclopentene,
3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene,
3,5-dimethylcyclohexene, 3,4,5-trimethylcyclohexene, 2-hexene,
3-hexene, 5-dodecene, norbornene, phenanthrene,
1,2,3,4-tetrahydrophthalic anhydride, dicyclopentadiene, indene,
methyl 3,3-dimethyl-2-(1-propenyl)-cyclopropanecarboxylate, ethyl
3,3-dimethyl-2-(1-propenyl)-cyclopropanecarboxylate and the
like.
[0082] Examples of the olefin compound of formula (I) wherein one
of the R.sub.1 to R.sub.4 groups represents a hydrogen atom, which
are referred to as "tri-substituted olefin", include
2-methyl-2-pentene, 3-methyl-2-pentene, 3-ethyl-2-pentene,
2-methyl-2-hexene, 3-methyl-2-hexene, 2-methyl-1-phenylpropene,
2-phenyl-2-butene, 1-methylcyclopentene, 1,3-dimethylcyclopentene,
1,4-dimethylcyclopentene, 1,5-dimethylcyclopentene,
1,3,5-trimethylcyclopentene, 1,3,4-trimethylcyclopentene,
1,4,5-trimethylcyclopentene, 1,3,4,5-tetramethylcyclopentene,
1-methylcyclohexene, 1,3-dimethylcyclohexene,
1,4-dimethylcyclohexene, 1,5-dimethylcyclohexene- ,
1,3,5-trimethylcyclohexene, 1,3,4-trimethylcyclohexene,
1,4,5-trimethylcyclohexene, 1,3,4,5-tetramethylcyclohexene,
isophorone, 2-carene, 3-carene, .alpha.-pinene, methyl
3,3-dimethyl-2-(2-methyl-1-pro- penyl)-cyclopropanecarboxylate,
ethyl 3,3-dimethyl-2-(2-methyl-1-propenyl)-
-cyclopropanecarboxylate, isopropyl
3,3-dimethyl-2-(2-methyl-1-propenyl)-c- yclopropanecarboxylate,
tert-butyl 3,3-dimethyl-2-(2-methyl-1-propenyl)-cy-
clopropanecarboxylate, cyclohexyl
3,3-dimethyl-2-(2-methyl-1-propenyl)-cyc- lopropanecarboxylate,
menthyl 3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopr-
opanecarboxylate, benzyl
3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropane- carboxylate,
(4-chlorobenzyl) 3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopr-
opanecarboxylate, (2,3,5,6-tetrafluorobenzyl)
3,3-dimethyl-2-(2-methyl-1-p- ropenyl)-cyclopropanecarboxylate,
(2,3,5,6-tetrafluoro-4-methylbenzyl)
3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate,
(2,3,5,6-tetrafluoro-4-methoxybenzyl)
3,3-dimethyl-2-(2-methyl-1-propenyl- )-cyclopropanecarboxylate,
(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)
3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarboxylate,
(3-phenoxybenzyl)
3,3-dimethyl-2-(2-methyl-1-propenyl)-cyclopropanecarbox- ylate and
the like.
[0083] Examples of the olefin compound of formula (I) wherein
R.sub.1 to R.sub.4 groups do not represent a hydrogen atom, which
are referred to as "tetra-substituted olefin", include
2,3-dimethyl-2-butene, 1,2-dimethylcyclopenteen,
1,2-dimethylcyclohexene, 1,2,3,4,5,6,7,8-octahydronaphthalene,
1-isopropylidene-2-carboethoxy-3-me- thylcyclopentane,
cyclohexylidenecyclohexane, tetraphenylethylene,
2,3-dimethyl-4-methoxyindene, 2,3-di(4-acetoxyphenyl)-2-butene,
pulegone and the like.
[0084] The reaction of the olefin compound with hydrogen peroxide
is typically conducted at a temperature range of from 0 to
200.degree. C. and the reaction temperature may be preferably set
as below within the range in view of the olefin compound and the
desired products of the reaction.
[0085] For example, the carbonyl compound of formula (IV) wherein
R.sub.1 to R.sub.4 represent an organic residue can be produced, as
a major product, by reacting the olefin compound of formula (I)
with hydrogen peroxide preferably in the presence of an organic
solvent and a dehydrating agent and at 30 to 100.degree. C.,
wherein the amount of hydrogen peroxide is preferably 2 to 10 moles
per mol of the olefin compound.
[0086] The carbonyl compound of formula (IV) wherein at least one
of R.sub.1 to R.sub.4 groups represents a hydrogen atom, can be
produced, as a major product, by reacting the olefin compound of
formula (I) with hydrogen peroxide preferably in the presence of an
organic solvent and a dehydrating agent and at 30 to 65.degree. C.,
wherein the amount of hydrogen peroxide is preferably 2 to 10 moles
per mol of the olefin compound.
[0087] The carbonyl compound of formula (II) wherein R.sub.b
represents a hydroxy group, can be produced, as a major product, by
reacting the olefin compound of formula (I) wherein at least one
group of R.sub.1 to R.sub.4 represents a hydrogen atom, with
aqueous hydrogen peroxide preferably at 65 to 100.degree. C.,
wherein the amount of hydrogen peroxide is preferably 4 moles or
more per mol of the olefin compound.
[0088] The method of the present invention may also be carried out
in the presence of a boron compound such as boric anhydride,
Examples of the boron compound include boric anhydride, metaboric
acid, orthoboric acid, alkali metal salts of metaboric acid,
alkaline earth metal salts of metaboric acid, alkali metal salts of
orthoboric acid and alkaline earth metal salts of orthoboric acid.
Any amount of such a compound may be used, but it usually not more
than 1 mole per mol of the olefin compound.
[0089] The hydroxy adduct compound of formula (IIIb):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (IIIb)
[0090] wherein X represents a hydroxy group and R1 to R4 represent
the same as defined above, can be produced, as a major product,
preferably by reacting the olefin of formula (I) with aqueous
hydrogen peroxide at 0 to 65.degree. C., wherein the amount of
aqueous hydrogen peroxide is preferably 1 to 2 moles per mol of the
olefin compound.
[0091] The .beta.-hydroxyhydroperoxide compound of formula (III)
wherein X represents a hydroperoxide group, can be produced, as a
major product, preferably in the presence of an organic solvent and
a dehydrating agent at 0 to 45.degree. C., wherein the amount of
hydrogen peroxide is preferably 2 to 10 moles per mol of the olefin
compound.
[0092] Examples of the dehydrating agent include, for example,
anhydrous magnesium sulfate, sodium sulfate. The amount of such a
dehydrating agent that may be used is not particularly limited, and
preferably such an amount of the dehydrating agent that can absorb,
as crystal water, water that may be present in an aqueous hydrogen
peroxide solution.
[0093] Next the olefin compound of formula (I) is described.
[0094] Examples of the olefin compound include, for example, a
mono-substituted olefin such as 1-hexene or a di-substituted
internal olefin such as cyclohexene, the carbon-carbon double bond
in the olefin is cleaved by oxidation to yield an aldehyde and a
carboxylic acid.
[0095] Further examples of the olefin compound include, for
example, di-substituted terminal olefins such as
methylenecyclohexane and the like, and the carbon-carbon double
bond in the olefin is cleaved by oxidation to yield ketone. Yet
further examples of the olefin compound include, for example,
tri-substituted olefins such as 2-methyl-2-pentene and the like,
which is reacted to yield a ketone, an aldehyde and a carboxylic
acid by oxidative cleavage of the carbon-carbon double bond.
Moreover, examples of the olefin compound include tetra-substituted
olefins such as 2,3-dimethyl-2-butene or the like, which is
oxidized to yield ketone.
[0096] The progress of the reaction can be checked by conventional
analyzing means such as gas chromatography, high performance liquid
chromatography, thin layer chromatography, NMR and IR.
[0097] After completion of the reaction, the desired compound can
be separated by subjecting the reaction solution as-obtained or
that resulting after decomposition of the remaining hydrogen
peroxide with a reducing agent such as sodium sulfite, to
concentration, crystallization or the like. Moreover, the resulting
compounds can also be separated by adding, if necessary, water
and/or a water-immiscible organic solvent to the reaction mixture,
then extracting and subsequently concentrating the resulting
organic layer. The desired compound separated may further be
purified by such a means as distillation and/or column
chromatography.
[0098] Examples of the water-immiscible organic solvent include
aromatic hydrocarbon solvents such as toluene and xylene,
halogenated hydrocarbon solvents such as dichloromethane,
chloroform and chlorobenzene, ether solvents such as diethyl ether,
methyl tert-butyl ether and tetrahydrofuran and ester solvents such
as ethyl acetate. The amount of such solvents that may be used is
not particularly limited.
[0099] The filtrate resulting from the separation of the desired
compound by crystallization and the separated aqueous layer
resulting from the extraction of the reaction solution that contain
the present catalyst composition used in the reaction and can be
reused as a recovered catalyst composition, directly or after being
subjected to some treatment such as concentration if required, in
the reaction according to the present invention.
[0100] The carboxylic acid produced may be further decarboxylated
in the reaction system, to give, for example, a carboxylic acid
having one less carbon atoms such as the case of isophorone.
[0101] Furthermore, when optical isomers are used as the organic
compound, an optically active product can be obtained according to
the position of the asymmetric carbon.
[0102] The .beta.-hydroxyhydroperoxide of formula (III) obtained in
the present method can be further derivatized to carbonyl compound
of formula (IV):
R.sub.1R.sub.2C.dbd.O, and R.sub.3R.sub.4C.dbd.O
[0103] wherein R.sub.1 to R.sub.4 independently represent a
hydrogen atom or an organic residue. The reaction process comprises
decomposing a hydroxy adduct compound of formula (IIIa):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (IIIa)
[0104] wherein X is a hyroperoxide group, and R.sub.1 to R.sub.4
are the same as defined above.
[0105] The decomposition reaction is conducted by contacting the
hydroxy adduct compound with a catalyst selected from a metal
compound comprising an element of Group Va, VIII, Ib, IIb, IIIb,
IVb, Vb or lanthanide or by heating.
[0106] Examples of the metal compound comprising an element of
Group Va include vanadium metal, vanadium oxide, vanadium chloride,
vanadium carbide, ammonium vanadate, an composition obtained by
reacting aqueous hydrogen peroxide with vanadium, niobium, niobium
chloride, niobium oxide, niobium ethoxide.
[0107] Examples of the metal compound comprising an element of
Group VIa include rhenium metal, rhenium carbonyl, rhenium
chloride.
[0108] Examples of the metal compound comprising an element of
Group VIII include iron metal, iron carbonyl, iron chloride, iron
acetylacetonate, ruthenium, ruthenium carbonyl, ruthenium
acetylacetonate, ruthenium chloride,
tris(triphenylphosphine)ruthenium chloride, cobalt metal, cobalt
acetate, cobalt bromide, rhodium metal, rhodium acetate, rhodium
carbonyl, iridium metal, iridium chloride, nickel metal, nickel
acetylacetonate, palladium metal, palladium acetate, palladium on
activated carbon.
[0109] Examples of the metal compound comprising an element of
Group I b include copper metal, copper bromide, copper chloride,
copper acetate.
[0110] Examples of the metal compound comprising an element of
Group II b include zinc metal, zinc chloride.
[0111] Examples of the metal compound comprising an element of
Group IIIb include boron trichloride, boron trifluoride, aluminum
metal, aluminum chloride.
[0112] Examples of the metal compound comprising an element of
Group IVb include tin metal, zinc chloride.
[0113] Examples of the metal compound comprising an element of
Group Vb include bismuth metal, bismuth chloride, antimony metal,
antimony bromide.
[0114] Examples of the metal compound comprising an element of
lanthanide include dysprosium metal, dysprosium chloride.
[0115] Preferred are vanadium compound, copper compound, ruthenium
compound, palladium compound and mixtuere of them.
[0116] The amount of the catalyst for the decomposition reaction is
usually 0.001 to 0.95 mole per mol of the
.beta.-hydroxyhydroperoxide. The reaction temperature is usually
-20 to 100.degree. C.
[0117] The reaction is preferably conducted in the presence of an
organic solvent that can dissolve the peroxide. Examples of the
organic solvent include the ether solvent, alcohol solvent,
alkylnitrile solvent as described above.
[0118] Alternatively, a hydroxy adduct compound of formula
(IIIb):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (IIIb)
[0119] wherein X is a hyroxy group and R.sub.1 to R.sub.4
independently represent a hydrogen atom or an organic residue can
be produced by a process, which comprises reacting a hydroxy adduct
compound of formula (IIIa):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (IIIa)
[0120] wherein X is a hyroperoxide group, and R.sub.1 to R.sub.4
are the same as defined above, with a reducing agent.
[0121] Examples of the reducing agent include an inorganic salt
having reducing activity such as sodium thiosulfate and an organic
compound having reducing activity such as dimethylsulfide,
triphenylphosphine and the like.
[0122] The reduction reaction is usually carried out at -10 to
100.degree. C. in an organic solvent. Examples of the organic
solvent include those described above for the decomposition
reaction of the hydroxy adduct compound (III).
[0123] Typical examples of the hydroxy adduct compounds include a
hydroxy adduct compound of formula (III):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (III)
[0124] wherein X is a hyroperoxide group or a hydroxy group,
R.sub.1 and R.sub.2 represent a methyl group, R.sub.3 represents a
hydrogen atom, and R.sub.4 represents a group of formula; 3
[0125] wherein R' represents an alkyl, aryl, or aralkyl group;
and
[0126] a hydroxy adduct compound of formula (III):
X--(R.sub.1)(R.sub.2)C--C(R.sub.3)(R.sub.4)OH (III)
[0127] wherein X is a hyroperoxide group, R.sub.1 represents a
methyl group, R.sub.3 represents a hydrogen atom, and R.sub.2 and
R.sub.4 form a group of formula: 4
[0128] The alkyl, aralkyl or ary group represented by R' in the
above described compounds respectively means the same group as
defined for R.sub.1 to R.sub.4 above.
[0129] In the above-described reduction or decomposition reaction
of the .beta.-hydroxyhydroperoxide, the reaction mixture or
solution after completion of the reaction can be treated in a
similar manner to separate the desired product.
[0130] Examples of the ketone that is obtained in such a manner
include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl
ketone, acetophenone, cyclobutanone, cyclopentanone, cyclohexanone,
camphenilone, norpinene, 1,3,3-trimethylindorinone,
dihydro-2,3-furandione, benzophenone, 2,6-hexanedione,
2,7-octanedione, 1,6-cyclodecanedione, 4-acetoxyacetophenone,
2-methoxy-6-(propan-2-one)acetophenone,
2-carboethoxy-3-methylcyclopentanone, 4-methyl-1,2-cyclohexanedione
and the like.
[0131] Examples of the aldehyde include formaldehyde, acetaldehyde,
propionaldehyde, butylaldehyde, pentylaldehyde, hexylaldehyde,
heptylaldehyde, decylaldehyde, undecanylaldehyde, benzaldehyde,
5-oxohexylaldehyde, 2-methyl-5-oxohexylaldehyde,
4-methyl-5-oxohexylaldeh- yde, 3-methyl-5-oxohexylaldehyde,
2,4-dimethyl-5-oxohexylaldehyde, 3,4-dimethyl-5-oxohexylaldehyde,
2,3-dimethyl-5-oxohexylaldehyde,
2,3,4-trimethyl-5-oxohexylaldehyde, 6-oxoheptylaldehyde,
2-methyl-6-oxoheptylaldehyde, 4-methyl-6-oxoheptylaldehyde,
2,4-dimethyl-6-oxoheptylaldehyde, 2,3-dimethyl-6-oxoheptylaldehyde,
3,4-dimethyl-6-oxoheptylaldehyde,
2,3,4-trimethyl-6-oxoheptylaldehyde, glutaraldehyde, adipoaldehyde,
heptanedialdehyde, octanedialdehyde, 2-chloroglutaraldehyde,
2-methylglutaraldehyde, 3-methylglutaraldehyde,
2,3-dimethylglutaraldehyde, 2,4-dimethylglutaraldehyde,
2,3,4-trimethylglutaraldehyde, 2-methyladipoaldehyde,
3-methyladipoaldehyde, 2,3-dimethyladipoaldehyde,
2,4-dimethyladipoaldehy- de, 2,3,4-dimethyladipoaldehyde,
cyclopentane-1,3-dicarboaldehyde, diphenyl-2,2'-dicarboaldehyde,
1-(formylmethyl)cyclopentene-2,3,4-tricarb- oaldehyde,
1,2-bis(formylmethyl)succinic anhydride,
1,4-diformylbutane-2,3-dicarboxylic acid,
(2-formylmethyl)benzaldehyde,
2,2-dimethyl-3-(2-oxopropyl)cyclopropaneacetaldehyde,
2,2-dimethyl-3-(3-oxobutyl)cyclopropylaldehyde,
2,2-dimethyl-3-(2-oxoethy- l)cyclobutaneacetaldehyde, methyl
3,3-dimethyl-2-formylcyclopropanecarboxy- late, ethyl
3,3-dimethyl-2-formylcyclopropanecarboxylate, isopropyl
3,3-dimethyl-2-formylcyclopropanecarboxylate, tert-butyl
3,3-dimethyl-2-formylcyclopropanecarboxylate, cyclohexyl
3,3-dimethyl-2-formylcyclopropanecarboxylate, menthyl
3,3-dimethyl-2-formylcyclopropanecarboxylate, benzyl
3,3-dimethyl-2-formylcyclopropanecarboxylate, (4-chlorobenzyl)
3,3-dimethyl-2-formylcyclopropanecarboxylate,
(2,3,5,6-tetrafluorobenzyl)
3,3-dimethyl-2-formylcyclopropanecarboxylate,
(2,3,5,6-tetrafluoro-4-meth- ylbenzyl)
3,3-dimethyl-2-formylcyclopropanecarboxylate,
(2,3,5,6-tetrafluoro-4-methoxybenzyl)
3,3-dimethyl-2-formylcyclopropaneca- rboxylate,
(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)
3,3-dimethyl-2-formylcyclopropanecarboxylate and (3-phenoxybenzyl)
3,3-dimethyl-2-formylcyclopropanecarboxylate.
[0132] Examples of the carboxylic acid include acetic acid,
propionic acid, butanoic acid, pentanoic acid, hexanoic acid,
6-oxoheptanoic acid, 2-methyl-6-oxoheptanoic acid,
3-methyl-6-oxoheptanoic acid, 4-methyl-6-oxoheptanoic acid,
5-methyl-6-oxoheptanoic acid, 2,3-dimethyl-6-oxoheptanoic acid,
2,4-dimethyl-6-oxoheptanoic acid, 3,4-dimethyl-6-oxoheptanoic acid,
2,3,4-trimethyl-6-oxoheptanoic acid, 5-oxohexanoic acid,
2-methyl-5-oxohexanoic acid, 3-methyl-5-oxohexanoic acid, 4-
methyl-5-oxohexanoic acid, 2,3-dimethyl-5-oxohexanoic acid,
2,4-dimethyl-5-oxohexanoic acid, 3,4-dimethyl-5-oxohexanoic acid,
2,3,4-trimethyl-5-oxohexanoic acid, 3,3-dimethyl-5-oxohexanoic
acid, heptanoic acid, glutaric acid, adipic acid, pimelic acid,
suberic acid, 2-methylglutaric acid, 3-methylglutaric acid,
3-chloroglutaric acid, 2,3-dimethylglutaric acid,
2,4-dimethylglutaric acid, 2-methyladipic acid, 3-methyladipic
acid, 2,3-dimethyladipic acid, 2,4-dimethyladipic acid,
3,4-dimethyladipic acid, 2,3,4-trimethylglutaric acid,
cyclopentane-1,3-dicarboxylic acid, biphenyl-2,2'-dicarboxylic
acid, meso-1,2,3,4-tetracarboxylic acid, benzoic acid,
1-(carboxymethyl)cyclope- ntane-2,3,4-tricarboxylic acid,
homophthalic acid, benzyloxyacetic acid,
3-(3-oxobutyl)-2,2-dimethylcyclopropanecarboxylic acid,
3-(2-oxopropyl)-2,2-dimethyl-1carboxymethylcyclopropane,
3-(2-oxoethyl)-2,2-dimethyl-1-carboxymethylcyclobutane, methyl
3,3-dimethyl-2-carboxycyclopropanecarboxylate, ethyl
3,3-dimethyl-2-carboxycyclopropanecarboxylate, isopropyl
3,3-dimethyl-2-carboxycyclopropanecarboxylate, tert-butyl
3,3-dimethyl-2-carboxycyclopropanecarboxylate, cyclohexyl
3,3-dimethyl-2-carboxycyclopropanecarboxylate, menthyl
3,3-dimethyl-2-carboxycyclopropanecarboxylate, benzyl
3,3-dimethyl-2-carboxycyclopropanecarboxylate, (4-chlorobenzyl)
3,3-dimethyl-2-carboxycyclopropanecarboxylate,
(2,3,5,6-tetrafluorobenzyl- )
3,3-dimethyl-2-carboxycyclopropanecarboxylate,
(2,3,5,6-tetrafluoro-4-me- thylbenzyl)
3,3-dimethyl-2-carboxycyclopropanecarboxylate,
(2,3,5,6-tetrafluoro-4-methoxybenzyl)
3,3-dimethyl-2-carboxycyclopropanec- arboxylate,
(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)
3,3-dimethyl-2-carboxycyclopropanecarboxylate, (3-phenoxybenzyl)
3,3-dimethyl-2-carboxycyclopropanecarboxylate and the like.
EXAMPLES
[0133] The present invention is further described in detail below
with reference to examples, but the invention is not limited to
these examples.
1 Gas chromatography method(hereinafter referred to as GC method)
Column: DB-1 (Length: 30 m, i.d.: 0.25 mm, Film thickness: 1.0
.mu.m) Oven temperature: Initial temp.: 100.degree. C. (0
min).fwdarw.Rate: 2.degree. C./min.fwdarw. Second temp.:
180.degree. C. (0 min).fwdarw.Rate: 10.degree. C./min.fwdarw. Final
temp.: 300.degree. C.(10 min) Run time: 62 min Injection temp:
250.degree. C., Detection temp: 250.degree. C. Carrier gas: He,
constant flow 1.0 ml/min Injection vol.: 1.0 .mu.l, Split ratio:
1/10 Liquid chromatography method(herein after referred to as LC
method) Column: Sumipax ODS-A212(Length: 15 cm, i.d.: 6 mm, 5.0
.mu.m) Carrier: A 0.1 vol % trifluoroacetic acid/water B 0.1 vol %
trifluoroacetic acid/acetonitrile Initial A/B = 90/10(volume ratio)
(0 min) .fwdarw. after 40 min A/B = 10/90(volume ratio) (20 min),
flow: 1.0 ml/min Injection vol.: 10 .mu.l, Detector: 220 nm,
Example 1
[0134] Two grams of a 30 wt % aqueous hydrogen peroxide solution
and 97 mg of metallic tungsten were charged into a 50 mL flask
equipped with a magnetic rotor and a reflux condenser. The mixture
was heated to an inner temperature of 60.degree. C. and then was
stirred and maintained at the temperature for 0.5 hour. To the
mixture, 3.5 g of isophorone and 25.8 g of a 30 wt % aqueous
hydrogen peroxide solution were added dropwise over 20 minutes.
After completion of the addition, the reaction solution was heated
and stirred for 6 hours on an oil bath inner temperature of which
was 95.degree. C. After completion of the reaction, the mixture was
cooled to an inner temperature of 25.degree. C. and was analyzed by
gas chromatography. The analysis confirmed that
3,3-dimethyl-5-oxohexanoic acid (areal percentage of chromatogram:
55%) was formed.
Example 2
[0135] Two grams of a 30 wt % aqueous hydrogen peroxide solution
and 30 mg of metallic tungsten were charged into a 50 mL flask
equipped with a magnetic rotor and a reflux condenser. The mixture
was heated to an inner temperature of 60.degree. C. and then
stirred and maintained at the temperature for 0.5 hour. To the
resulting mixture, 3.0 g of methyl
[0136] 3,3-dimethyl-2-(2-methyl-1propenyl)cyclopropanecarboxylate
and 7.3 g of a 30 wt % aqueous hydrogen peroxide solution were
charged. After the charge, the reaction solution was heated and
stirred for 6 hours on an oil bath inner temperature of which was
95.degree. C. After completion of the reaction, the mixture was
cooled to an inner temperature of 25.degree. C. and was analyzed by
an internal standard method by gas chromatography. The analysis
confirmed that 3,3-dimethyl-2-carbomethoxycy- clopropanecarboxylic
acid (areal percentage: 43%) was formed.
Example 3
[0137] Two grams of a 30 wt % aqueous hydrogen peroxide solution
and 90 mg of metallic tungsten were charged into a 50 mL flask
equipped with a magnetic rotor and a reflux condenser. The mixture
was heated to an inner temperature of 60.degree. C. and then was
stirred and maintained at the temperature for 0.5 hour. To the
mixture, 4.7 g of 1-methylcyclohexene and 25.6 g of a 30 wt %
aqueous hydrogen peroxide solution were added. The reaction
solution was thereafter heated and stirred for 10 hours on an oil
bath inner temperature of which was 95.degree. C. After completion
of the reaction, the mixture was cooled to an inner temperature of
25.degree. C. and was analyzed by an internal standard method by
gas chromatography. The analysis confirmed that 6-oxohexanoic acid
(yield: 92%) was formed.
Example 4
[0138] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 200 mg of a 30 wt % aqueous hydrogen peroxide
solution and 40 mg of tungsten boride were added. The mixture was
heated to an inner temperature of 40.degree. C. and then was
stirred and maintained at the temperature for 0.5 hour. After
cooling of this solution to an inner temperature of 25.degree. C.,
530 mg of anhydrous magnesium sulfate, 530 mg of a 30 wt % aqueous
hydrogen peroxide solution and 1.5 g of tert-butanol were added and
then stirred and maintained at the temperature for 1 hour.
Thereafter a mixed solution comprising 350 mg of 3-carene and 1.5 g
of tert-butanol was added dropwise over 10 minutes. The mixture was
stirred and maintained at an inner temperature of 25.degree. C. for
24 hours, to this solution 10 g of toluene and 5 g of water was
added, and separated to give 9.4 g of the toluene solution. Gas
chromatography analysis (an internal standard method) and a liquid
chromatography analysis of this reaction solution confirmed that
the yield of 4-hydroxy-3-hydroperoxycarene was 70.4% and the yield
of 3,4-carenediol 21.7%.
[0139] The liquid chromatographys' elution time of
4-hydroxy-3-hydroperoxy- carene is 20.9 min. and the mass spectrum
showed M+186.
[0140] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 200 mg of a 30 wt % aqueous hydrogen peroxide
solution and 20 mg of vanadium metal were charged. The mixture was
stirred and maintained at the temperature for 0.5 hour. After
cooling this solution to an inner temperature of 25.degree. C., the
toluene solution of 4-hydroxy-3-hydroperoxycarene was added and
then was stirred and maintained at that temperature for 16 hour and
then was heated to an inner temperature of 60.degree. C. and then
further stirred and maintained at the temperature for 3 hour. Gas
chromatography analysis (an internal standard method) and a liquid
chromatography analysis of this reaction solution confirmed that
the yield of 2,2,-dimethyl-3-(2-oxopropy- l)cyclopropane
acetaldehyde was 71.4% (in terms of used 3-carene).
Example 5
[0141] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 200 mg of a 30 wt % aqueous hydrogen peroxide
solution, 0.8 g of tert-butanol and 22 mg of tungsten boride were
charged. The mixture was heated to an inner temperature of
60.degree. C. and then was stirred and maintained at the
temperature for 1 hour. After cooling this solution to 25.degree.
C., 530 mg of anhydrous magnesium sulfate was added and thereafter
a mixed solution comprising 270 mg of 1-methylcyclohexene, 1.0 g of
tert-butanol and 500 mg of a 30 wt % aqueous hydrogen peroxide
solution was added dropwise over 20 minutes. After the addition,
the mixture was stirred and maintained at an inner temperature of
25.degree. C. for 20 hours. Analysis of the reaction solution by
gas chromatography confirmed that 6-oxoheptylaldehyde (areal
percentage: 77.0%) was formed.
Example 6
[0142] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 3 g of tert-butanol, 600 mg of a 30 wt % aqueous
hydrogen peroxide solution, 2.3 g of magnesium sulfate, 300 mg of
boric anhydride and 40 mg of tungsten boride were charged. The
mixture was heated to an inner temperature of 60.degree. C. and
then was stirred and maintained at the temperature for 1 hour.
After cooling to an inner temperature of 6.degree. C., a mixed
solution comprising 400 mg of methyl
trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,
600 mg of a 30 wt % aqueous hydrogen peroxide solution and 1.8 g of
tert-butanol was added dropwise over 20 minutes. The mixture was
stirred and maintained at an inner temperature of 6.degree. C. for
4 days, to give a reaction solution containing methyl
trans-3,3-dimethyl-(1-hydroxy-2-hydro-
peroxy-2-methylpropyl)cyclopropane-carboxylate and methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gas
chromatography analysis (an internal standard method) and a liquid
chromatography analysis of this reaction solution confirmed that
the yield of
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-c-
arboxylate was 55% and the yield of methyl
trans-3,3-dimethyl-2-formylcycl- opropanecarboxylate was 5%.
Example 7
[0143] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 200 mg of a 30 wt % aqueous hydrogen peroxide
solution and 45 mg of tungsten boride were charged. The mixture was
heated to an inner temperature of 40.degree. C. and then was
stirred and maintained at that temperature for 1 hour. After
cooling this solution to an inner temperature of 20.degree. C., 530
m g of anhydrous magnesium sulfate, 400 mg of a 30 wt % aqueous
hydrogen peroxide solution and 1.5 g of tert-butanol was added and
then stirred and maintained at the temperature for 2 hour.
Thereafter a mixed solution comprising 400 mg of methyl
trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,
and 0.8 g of tert-butanol was added dropwise over 20 minutes. The
mixture was stirred and maintained at an inner temperature of
25.degree. C. for 16 hours, to give a reaction solution containing
methyl
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-c-
arboxylate and methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gas
chromatography analysis (an internal standard method) and a liquid
chromatography analysis of this reaction solution confirmed that
the yield of
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclo-
propane-carboxylate was 60.8% and the yield of methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 6% .
Example 8
[0144] Into a 50 mL flask, 3 g of tert-butanol, 200 mg of a 30 wt %
aqueous hydrogen peroxide solution, 16 mg of boric anhydride and 40
mg of metallic tungsten (powder) were charged. The mixture was
heated to an inner temperature of 60.degree. C. and then was
stirred and maintained at the temperature for 1 hour. After the
cooling this solution to an inner temperature of 25.degree. C., 530
mg of magnesium sulfate was added and thereafter a mixed solution
comprising 400 mg of methyl
trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropane-carboxylate,
600 mg of a 30 wt % aqueous hydrogen peroxide solution and 1.8 g of
tert-butanol was added dropwise over 20 minutes. The mixture was
stirred and maintained at an inner temperature of 25.degree. C. for
16 hours, to give a reaction solution containing methyl
trans-3,3-dimethyl-(1-hydroxy--
2-hydroperoxy-2-methylpropyl)-cyclopropanecarboxylate and methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gas
chromatography analysis (an internal standard method) and liquid
chromatography analysis of this reaction solution confirmed that
the yield of
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-c-
arboxylate was 54.8% and the yield of methyl
trans-3,3-dimethyl-2-formylcy- clopropanecarboxylate was 6%
Example 9
[0145] Into a 100 mL flask, 10 g of tert-butanol, 2.0 g of a 30 wt
% aqueous hydrogen peroxide solution and 215 mg of tungsten boride
were charged. The mixture was heated to an inner temperature of
60.degree. C. and then was stirred and maintained at that
temperature for 1 hour. After cooling to an inner temperature of
20.degree. C., a mixed solution comprising 4 g of methyl
trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclop-
ropanecarboxylate, 4 g of a 30 wt % aqueous hydrogen peroxide
solution and 10 g of tert-butanol was dropped over 20 minutes. The
mixture was stirred and maintained at an inner temperature of
20.degree. C. for 48 hours, to give a reaction solution containing
methyl trans-3,3-dimethyl-(1-hydroxy--
2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylate and methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gas
chromatography analysis (an internal standard method) and a liquid
chromatography analysis of this reaction solution confirmed that
the yield of
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-c-
arboxylate was 36% and the yield of methyl
trans-3,3-dimethyl-2-formylcycl- opropanecarboxylate was 4%
Example 10
[0146] Into a 50 mL flask, 3 g of tert-butanol, 200 mg of a 30 wt %
aqueous hydrogen peroxide solution and 40 mg of metallic tungsten
(powder) were charged. The mixture was heated to an inner
temperature of 60.degree. C. and then was stirred and maintained at
th temperature for 1 hour. After cooling to an inner temperature of
25.degree. C., a mixed solution comprising 400 mg of methyl
trans-3,3-dimethyl-2-(2-methyl-1-pro-
penyl)cyclopropanecarboxylate, 400 mg of a 30 wt % aqueous hydrogen
peroxide solution and 1.8 g of tert-butanol was added dropwise over
20 minutes. The mixture was stirred and maintained at an inner
temperature of 25.degree. C. for 24 hours, to give a reaction
solution containing methyl
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopr-
opane-carboxylate and methyl
trans-3,3-dimethyl-2-formylcyclopropanecarbox- ylate. Gas
chromatography analysis (an internal standard method) and a liquid
chromatography analysis of this reaction solution confirmed that
the yield of
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)c-
yclopropanecarb oxylate was 45% and the yield of methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%
Example 11
[0147] Into a 50 mL flask, 3 g of methyl tert-butyl ether, 1.2 g of
a 30 wt % aqueous hydrogen peroxide solution and 40 mg of tungsten
boride were charged. The mixture was heated to an inner temperature
of 50.degree. C. and then was stirred and maintained at the
temperature for 1 hour. Subsequently, 2.3 g of magnesium sulfate
was added and thereafter a mixed solution comprising 400 mg of
methyl trans-3,3-dimethyl-2-(2-methyl-1prop-
enyl)cyclopropanecarboxylate and 1.8 g of methyl tert-butyl ether
was added dropwise over 20 minutes. The mixture was stirred and
maintained at an inner temperature of 50.degree. C. for 2 hours, to
give a reaction solution containing methyl
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2--
methylpropyl)cyclopropane-carboxylate and methyl
trans-3,3-dimethyl-2-form- ylcyclopropanecarboxylate. Gas
chromatography analysis (an internal standard method) and a liquid
chromatography analysis of this reaction solution confirmed that
the yield of trans-3,3-dimethyl-(1-hydroxy-2-hydr-
operoxy-2-methylpropyl)cyclopropane-carboxylate was 37% and the
yield of methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate
was 4%
Example 12
[0148] Into a 50 mL flask, 3 g of tert-butanol, 2.3 g of magnesium
sulfate, 300 mg of boric anhydride and 40 mg of tungsten boride
were charged. After heating to an inner temperature of 60.degree.
C., a mixed solution comprising 400 mg of methyl
trans-3,3-dimethyl-2-(2-methyl-1-pro-
penyl)cyclopropanecarboxylate, 600 mg of a 30 wt % aqueous hydrogen
peroxide solution and 1.8 g of tert-butanol was added dropwise over
20 minutes and the resulting mixture was stirred and maintained at
an inner temperature of 60.degree. C. for 2 hours, to give a
reaction solution containing methyl
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpro-
pyl)cyclopropane-carboxylate and methyl
trans-3,3-dimethyl-2-formylcyclopr- opanecarboxylate. Gas
chromatography analysis (an internal standard method) and a liquid
chromatography analysis of this reaction solution confirmed that
the yield of trans-3,3dimethyl-(1-hydroxy-2-hydroperoxy-2--
methylpropyl)cyclopropane-carboxylate was 42.2% and the yield of
methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was
5%
Example 13
[0149] Into a 50 mL flask, 3 g of tert-butanol and 51 mg of
tungsten sulfide were charged. After heating to an inner
temperature of 60.degree. C., a mixed solution comprising 400 mg of
methyl trans-3,3-dimethyl-2-(2--
methyl-1-propenyl)cyclopropanecarboxylate, 1.5 g of a 30 wt %
aqueous hydrogen peroxide solution and 1.8 g of tert-butanol was
dropped over 20 minutes and the resulting mixture was stirred and
maintained at an inner temperature of 60.degree. C. for 2 hours, to
give a reaction solution containing methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gas
chromatography analysis of this reaction solution confirmed that
the areal percentage of methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxy- late was 23.8%.
Example 14
[0150] A reaction solution containing methyl
trans-3,3-dimethyl-2-formylcy- clopropanecarboxylate was obtained
through operations conducted as in Example 13 except that 50 mg of
tungsten silicide was used in place of 51 mg of tungsten sulfide.
Gas chromatography analysis of this reaction solution confirmed
that the areal percentage of methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 29.8%.
Example 15
[0151] A reaction solution containing methyl
trans-3,3-dimethyl-2-formylcy- clopropanecarboxylate was obtained
through operations conducted in the same manner as Example 13
except that 41 mg of tungsten carbide was used in place of 51 mg of
tungsten sulfide. Gas chromatography analysis of this reaction
solution confirmed that the areal percentage of methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 27.7%.
Example 16
[0152] Into a 50 mL flask 20 mg of metallic molybdenum (powder) was
charged and then 200 mg of a 30 wt % aqueous hydrogen peroxide
solution was added, followed by the addition of 530 mg of magnesium
sulfate. Furthermore, a mixed solution comprising 400 mg of methyl
trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,
600 mg of a 30 wt % aqueous hydrogen peroxide solution and 1.5 g of
tert-butanol was added dropwise over 20 minutes and the resulting
mixture was stirred and maintained at an inner temperature of
25.degree. C. for 40 hours, to give a reaction solution containing
methyl trans-3,3-dimethyl-(1-hydroxy--
2-hydroperoxy-2-methylpropyl)cyclopropane-carboxylate and methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. Gas
chromatography analysis (an internal standard method) and a liquid
chromatography analysis of this reaction solution confirmed that
the yield of
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropane-c-
arboxylate was 51.7% and the yield of methyl
trans-3,3-dimethyl-2-formylcy- clopropanecarboxylate was 5%. The
analysis also revealed that 18.2% (GC areal percentage) of the
starting methyl trans-3,3-dimethyl-2-(2-methyl-1-
-propenyl)cyclopropanecarboxylate remained.
Example 17
[0153] A reaction solution containing methyl
trans-3,3-dimethyl-2-formylcy- clopropanecarboxylate was obtained
in a similar manner as in Example 16 except that the amount of the
metallic molybdenum (powder) and the reaction time were changed to
40 mg and 20 hours, respectively. Gas chromatography analysis (an
internal standard method) of this reaction solution confirmed that
the yield was 62.7%. The analysis also revealed that 6% (GC areal
percentage) of the starting methyl
trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate
remained.
Example 18
[0154] A reaction solution containing methyl
trans-3,3-dimethyl-2-formylcy- clopropanecarboxylate was obtained
in a similar manner as in Example 16 except that 22 mg of
molybdenum boride was used in place of 20 mg of metallic
molybdenum. Gas chromatography analysis (an internal standard
method) and a liquid chromatography analysis of this reaction
solution confirmed that the yield of
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-
-methylpropyl)cyclopropane-carboxylate was 36.5% and the yield of
methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 4%
The analysis also revealed that 20% (GC areal percentage) of the
starting methyl
trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate
remained.
Example 19
[0155] A reaction solution containing methyl
trans-3,3-dimethyl-2-formylcy- clopropanecarboxylate was obtained
in a similar manner as in Example 16 except that methyl tert-butyl
ether was used in place of tert-butanol. Gas chromatography
analysis (an internal standard method) and a liquid chromatography
analysis of this reaction solution confirmed that the yield of
trans-3,3-dimethyl-(1-hydroxy-2-hydroperoxy-2-methylpropyl)cyclo-
propane-carboxylate was 47.2% and the yield of methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5% The
analysis also revealed that 20% (GC areal percentage) of the
starting methyl
trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate
remained.
Example 20
[0156] Twenty grams of a 30 wt % aqueous hydrogen peroxide solution
and 895 mg of metallic tungsten powder were charged into a 1 L
flask equipped with an induction stirrer and a reflux condenser and
the inner temperature was elevated to 60.degree. C. After heating
and maintaining of the mixture at the temperature for 0.5 hour, 40
g of cyclohexene and 228 g of a 30 wt % aqueous hydrogen peroxide
solution were added dropwise over 20 minutes. After completion of
the dropping, the reaction solution was heated and stirred for 8
hours on an oil bath inner temperature of which was 100.degree. C.
The inner temperature of the reaction solution was elevated from
72.degree. C. to 95.degree. C. After completion of the reaction,
the mixture was cooled to an inner temperature of 5.degree. C., and
the crystals formed were separated by filtration and dried, to give
57.3 g of white crystals. The analysis of the crystals with 1H-NMR
confirmed that they were adipic acid of high purity. The
measurement of the melting point of the crystals confirmed the
melting point was 151 to 152.degree. C. The analysis of the
filtrate by gas chromatography (the internal standard method)
showed that the filtrate contained 9.6 g of adipic acid. The total
yield of adipic acid resulting from the separated crystals of
adipic acid and the adipic acid in the filtrate was 94%.
Example 21
[0157] The filtrate obtained in Example 20 was concentrated to 188
g. The concentrated filtrate was charged into a 1 L flask equipped
with an induction stirrer and a reflux condenser, and 40 g of
cyclohexene and 250 g of a 30 wt % aqueous hydrogen peroxide
solution were added dropwise over 20 minutes. After the dropping,
the mixture was heated and stirred for 9 hours on an oil bath inner
temperature of which was 100.degree. C. The inner temperature of
the reaction solution was elevated from 72.degree. C. to 95.degree.
C. After completion of the reaction, the mixture was cooled to an
inner temperature of 0.degree. C., and the crystals formed were
separated by filtration and dried, to give 57.2 g of white crystals
of adipic acid. Melting point: 151 to 152.degree. C. The filtrate
was concentrated to 130 g and cooled to an inner temperature of
0.degree. C. The crystals formed were separated by filtration and
dried, to give 5.0 g of white crystals of adipic acid. Melting
point: 151 to 152.degree. C. The yield of the crystals of adipic
acid obtained was 87.5%.
Example 22
[0158] Into a 1 L flask equipped with an induction stirrer and a
reflux condenser, 122 g of the filtrate obtained in Example 21 was
charged, and then 40 g of cyclohexene and 250 g of a 30 wt %
aqueous hydrogen peroxide solution were further dropped over 20
minutes. After the addition, the mixture was heated and stirred for
11.5 hours on an oil bath inner temperature of which was
100.degree. C. The inner temperature of the reaction solution was
elevated from 72.degree. C to 95.degree. C. After completion of the
reaction, the mixture was cooled to an inner temperature of
0.degree. C., and the crystals formed were separated by filtration
and dried, to give 57.5 g of white crystals of adipic acid. Melting
point: 151 to 152.degree. C. The filtrate was concentrated to 128 g
and cooled to an inner temperature of 0.degree. C. The crystals
formed were further separated by filtration and dried, to give 5.2
g of white crystals of adipic acid. Melting point: 151 to
152.degree. C. The yield of the crystals of adipic acid obtained
was 88.2%.
Example 23
[0159] Into a 1 L flask equipped with an induction stirrer and a
reflux condenser, 103 g of the filtrate obtained in Example 22 was
charged, and then 40 g of cyclohexene and 250 g of a 30 wt %
aqueous hydrogen peroxide solution were further added dropwise over
20 minutes. After the addition, the mixture was heated and stirred
for 10.5 hours on an oil bath inner temperature of which was
100.degree. C. The inner temperature of the reaction solution was
elevated from 72.degree. C. to 95.degree. C. After completion of
the reaction, the mixture was cooled to an inner temperature of
0.degree. C., and the crystals formed were separated by filtration
and dried, to give 55.7 g of white crystals of adipic acid. Melting
point: 151 to 152.degree. C. The analysis of the filtrate by gas
chromatography (internal standard method) showed that the filtrate
contained 11.6 g of adipic acid. The yield of adipic acid was 88.9%
except the adipic acid contained in 103 g of the filtrate obtained
in Example 22.
Example 24
[0160] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 2 g of a 30 wt % aqueous hydrogen peroxide
solution and 97 mg of metallic tungsten powder were charged and
heated to an inner temperature of 60.degree. C. After the heating
and maintaining of the mixture at the temperature for 0.5 hour, 4 g
of cyclohexene and 25.8 g of a 30 wt % aqueous hydrogen peroxide
solution were added dropwise over 20 minutes. After the addition,
the mixture was heated and stirred for 6 hours on an oil bath inner
temperature of which was 100.degree. C. The inner temperature of
the reaction solution was elevated from 72.degree. C. to 95.degree.
C. After completion of the reaction, the mixture was cooled to an
inner temperature of 5.degree. C., and the crystals formed were
separated by filtration and dried, to give 5.3 g of white crystals.
The analysis of the crystals with 1H-NMR confirmed that they were
adipic acid of high purity. The analysis of the filtrate by gas
chromatography (an internal standard method) showed that the
filtrate contained 1.4 g of adipic acid. The total yield of adipic
acid was 94%.
Example 25
[0161] Through the operations conducted in a similar manner as
those in Example 24 except that 96 mg of tungsten carbide was used
in place of 97 mg of the metallic tungsten powder, 4.5 g of
crystals of adipic acid were obtained. The filtrate contained 1.2 g
of adipic acid. The total yield of adipic acid was 80%.
Example 26
[0162] Through the operations conducted in a similar manner as
those in Example 24 except that 96 mg of tungsten boride was used
in place of 97 mg of the metallic tungsten powder, 3.6 g of
crystals of adipic acid were obtained. The yield of adipic acid:
51%.
Example 27
[0163] Through the operations conducted in a similar manner as
those in Example 24 except that 121 mg of tungsten sulfide was used
in place of 97 mg of the metallic tungsten powder, 5.0 g of
crystals of adipic acid were obtained. The filtrate contained 1.12
g of adipic acid. The total yield of adipic acid: 86%.
Example 28
[0164] Through the operations conducted in a similar manner as
those in Example 24 except that 3.2 g of cyclopentene was used in
place of 4 g of cyclohexene, 4.2 g of crystals of glutaric acid
were obtained. The filtrate contained 0.93 g of glutaric acid. The
total yield of adipic acid resulting from the combination of the
separated crystals of glutaric acid and the glutaric acid in the
filtrate was 80%.
Example 29
[0165] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 0.5 g of a 30 wt % aqueous hydrogen peroxide
solution and 37 mg of metallic tungsten were charged. The mixture
was heated to an inner temperature of 60.degree. C. and then was
stirred and maintained at the temperature for 0.5 hour. To the
mixture were charged 2.0 g of 1-heptene and 7.5 g of a 50 wt %
aqueous hydrogen peroxide solution. After that, the reaction
solution was heated and stirred for 20 hours on an oil bath the
inner temperature of which was 95.degree. C. After completion of
the reaction, the reaction solution was cooled to an inner
temperature of 25.degree. C. and analyzed by gas chromatography (an
internal standard method). The analysis showed that 1.2 g of
hexanoic acid was formed. Yield: 49%.
Example 30
[0166] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 2 g of a 30 wt % aqueous hydrogen peroxide
solution and 70 mg of metallic tungsten were charged. The mixture
was heated to an inner temperature of 60.degree. C. and then
stirred and maintained at that temperature for 0.5 hour. To the
mixture were charged 4 g of styrene and 15 g of a 40 wt % aqueous
hydrogen peroxide solution. The mixture was heated and stirred for
30 hours on an oil bath the inner temperature of which was
95.degree. C. After completion of the reaction, the reaction
solution was cooled to an inner temperature of 25.degree. C., to
give 4.3 g of white crystals of benzoic acid. An analysis by gas
chromatography confirmed that the purity of the crystals obtained
was 98% (areal percentage).
Example 31
[0167] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 200 mg of a 30 wt % aqueous hydrogen peroxide
solution, 1.5 g of tert-butanol and 40 mg of metallic tungsten
powder were charged. The mixture was heated to an inner temperature
of 60.degree. C. and then was stirred and maintained at the
temperature for 1 hour. After cooling of this solution to an inner
temperature of 25.degree. C., 530 mg of anhydrous magnesium sulfate
was added and then a mixed solution comprising 150 mg of
cyclopentene, 1.5 g of tert-butanol and 350 mg of a 30 wt % aqueous
hydrogen peroxide solution was added dropwise over 20 minutes.
After stirring and maintaining the mixture at an inner temperature
of 25.degree. C. for 16 hours, gas chromatography analysis (an
internal standard method) and a liquid chromatography analysis of
this reaction solution confirmed that the yield of
1-hydroxy-2-hydroperoxy-cyclopentane was 80.7%. Almost no
by-production of the diol compound was recognized.
Example 32
[0168] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 200 mg of a 30 wt % aqueous hydrogen peroxide
solution, 1.5 g of tert-butanol, 20 mg of boric anhydride and 40 mg
of metallic tungsten powder were charged. The mixture was heated to
an inner temperature of 60.degree. C. and then was stirred and
maintained at that temperature for 1 hour. After cooling of this
solution to an inner temperature of 25.degree. C., 530 mg of
anhydrous magnesium sulfate was added and then a mixed solution
comprising 180 mg of cyclohexene, 1.5 g of tert-butanol and 350 mg
of a 30 wt % aqueous hydrogen peroxide solution was added dropwise
over 20 minutes. After stirring and maintaining the mixture at an
inner temperature of 25.degree. C. for 16 hours, gas chromatography
analysis (an internal standard method) and a liquid chromatography
analysis of this reaction solution confirmed that the yield of
1-hydroxy-2-hydroperoxy-cyclohexane was 54.7%.
Example 33
[0169] Through the operations conducted in a similar manner as
those in Example 32 except that 220 mg of 1-heptene was used in
place of 180 mg of cyclohexene and that the mixture was stirred and
maintained at an inner temperature of 25.degree. C. for 48 hours,
55 mg of hexylaldehyde was obtained. Yield: 25%.
Example 34
[0170] Through the operations conducted in a similar manner as
those in Example 32 except that 230 mg of styrene was used in place
of 180 mg of cyclohexene and that the mixture was stirred and
maintained at an inner temperature of 60.degree. C. for 6 hours, 47
mg of benzaldehyde was obtained. Yield: 20%.
Example 35
[0171] Through the operations conducted in a similar manner as
those in Example 32 except that 370 mg of 5-dodecene was used in
place of 180 mg of cyclohexene, that 22 mg of tungsten boride was
used in place of 40 mg of metallic tungsten powder and that the
mixture was stirred and maintained at an inner temperature of
25.degree. C. for 39 hours, 112 mg of heptylaldehyde (yield: 44%)
and pentylaldehyde (yield: 44%) were obtained.
Example 36
[0172] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 200 mg of a 30 wt % aqueous hydrogen peroxide
solution, 40 mg of metallic tungsten powder and 15 mg of boric
anhydride and were charged and the mixture was heated to an inner
temperature of 60.degree. C. After stirring and maintaining at the
temperature for 0.5 hour, the mixture was cooled to an inner
temperature of 25.degree. C. After addition of 1.5 g of
tert-butanol and 530 mg of anhydrous magnesium sulfate, a mixed
solution comprising 230 mg of 2,3-dimethyl-2-butene, 1.5 g of
tert-butanol and 350 mg of a 30 wt % aqueous hydrogen peroxide
solution was added dropwise over 20 minutes. After completion of
the addition, the mixture was stirred and maintained at an inner
temperature of 25.degree. C. for 20 hours. Analysis of the reaction
solution by gas chromatography confirmed formation of 243 mg of
acetone. The yield was 77% of the theoretical value.
Example 37
[0173] Into a 50 mL flask equipped with a magnetic rotor and a
reflux condenser, 200 mg of a 30 wt % aqueous hydrogen peroxide
solution, 1.5 g of tert-butanol, 16 mg of boric anhydride and 40 mg
of metallic tungsten powder were charged and the mixture was heated
to an inner temperature of 60.degree. C. After stirring and
maintaining at the temperature for 1 hour, 530 mg of anhydrous
magnesium sulfate was added and thereafter a mixed solution
containing 247 mg of 2,4,4-trimethyl-1-pentene, 1.5 g of
tert-butanol and 350 mg of a 30 wt % aqueous hydrogen peroxide
solution was added dropwise over 20 minutes. After the addition,
the mixture was stirred and maintained at an inner temperature of
60.degree. C. for 6 hours. Analysis of the reaction solution by gas
chromatography confirmed the formation of 4,4-dimethylpentane-2-one
(areal percentage in the gas chromatogram: 51.0%). The
by-production of an epoxy compound was also recognized (areal
percentage in the gas chromatography analysis: 25.0%).
Example 38
[0174] To a 100 mL flask equipped with magnetic rotor and a reflux
condenser were added 4.2 g of metallic tungsten boride powder, 25 g
of water, andl 8 grams of a 60 wt % aqueous hydrogen peroxide
solution were added thereto under stirring at 40.degree. C. over 2
hours. The mixture was kept at 40.degree. C. for 2 hours to yield a
clear solution with a slight white crystals floating on the surface
of the solution. After the solution was cooled to room temperature
and hydrogen peroxide was decomposed with platinum net, the
solution was evaporated to remove water at room temperature to give
white crystals, which was dried at room temperature under open air
until the weight thereof became constant. 6.4 g of solid crystal
was finally obtained.
[0175] UV Absorbtion of the solution (before concentration)
.lambda..sup.H.sup..sub.2.sup.Omax: 200, 235(s) nm. IR v.sub.max
(solution before concentration) (4000.about.750 cm.sup.-1): 3350,
2836, 1275, 1158, 965, 836 cm.sup.-1 IR v.sub.max (KBr) (Solid
crystal): 3527, 3220, 2360, 2261, 1622, 1469, 1196, 973, 904.5,
884, 791, 640, 549 cm.sup.-1 Elemental Analysis (found): W: 51.2,
O: 39.0, H: 2.2, B: 3.98
Example 39
[0176] A pale yellow clear solution was obtained in a similar
manner as described in Example 38 except that 12 g of water was
used and 5.4 g of tungsten sulfide was used in place of tungsten
boride. A 10.1 g of a pale yellow solid was obtained after
drying.
[0177] UV Absorbtion of the solution before concentration:
.lambda..sup.H.sup..sub.2.sup.O max 200, 240 (s) nm IR (aqueous
solution before concentration) v .sub.max (aqueous solution)
(4000.about.750 cm.sup.-1): 3373, 1187, 1044, 974, 878, 837
cm.sup.-1 IR (Solid), v.sub.max (KBr): 3435, 3359, 1730, 1632,
1320, 1285, 1178, 1103, 1070, 1008, 981, 887, 839, 851, 660, 615,
578 cm.sup.-1 Elemental Analysis(found): W: 35.3, O: 47.4, H:3.0,
S:12.4.
[0178] A yellowish solution was obtained in a similar manner as
described in Example 38 except that 12 g of water was used and 2.3
g of molybdenum boride was used in place of tungsten boride and 12
g of 60% hydrogen peroxide was used.
[0179] UV Absorbtion of the solution before concentration:
.lambda..sup.H.sup..sub.2.sup.O.sub.max: 200, 310 (s) nm IR
(Solid), v.sub.max (KBr): 3221, 2520, 2361, 2262, 1620, 1463, 1439,
1195, 965, 927, 887, 840, 799, 674, 634, 547, 529 cm.sup.-1
Elemental Analysis (found): Mo: 35.5, O: 51.0, H: 2.9, B: 4.1
Example 40
[0180] To a 50 mL flask equipped with magnetic rotor and a reflux
condenser were added 80 mg of metallic tungsten powder, and 400 mg
of a 30 wt % aqueous hydrogen peroxide solution were added and
reacted under stirring for 0.5 hour. The mixture was cooled to
25.degree. C., and 2 g of t-butanol and 800 mg of 30wt % hydrogen
peroxide were added thereto and stirred for 1 hour. To this
solution was added dropwise a mixed solution of 2.0 g of t-butanol
and 600 mg of 3-carene over 10 minutes and reacted for 24 hours
under stirring at 25.degree. C. The resulting solution was
subjected to a reduction reaction by using 27 g of 5 wt % of sodium
thiosulfate and analyzed by GC to find that 3,4-carene-diol was
produced in 70.0% yield.
Example 41
[0181] Into a 500 mL flask equipped with a magnetic rotor and a
reflux condenser and charged with 1. g of tungsten metal powder and
7.5 g of water were added dropwise 7.5 g of a 60 wt % aqueous
hydrogen peroxide solution at 60.degree. C. over 1 hour under
stirring. The resulting reaction mixture was reacted under stirring
at the same temperature for 1 hour to give a clear solution. The
solution was cooled to room temperature and 38 g of t-butanol and
13.3 g of anhydrous magnesium sulfate were added thereto and
stirred for 14 hours at room temperature. To the obtained slurry
solution was dropwise added a mixed solution of 10 g of methyl
trans-3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxy- late
and 12 g t-butanol over 20 minutes and reacted at 25.degree. C. for
24 hours. 60 g of water was added to the reaction mixture and
extracted twice with 50 g of toluene to give 137.4 g of toluene
solution.
[0182] The toluene solution was analyzed by LC to show that methyl
trans-3,3-dimethyl-2-(1-hydrpoxy-2-hydroperoxy-2-methylpropyl)cyclopropan-
e-carboxylate and methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylat- e were
produced.
[0183] Methyl
trans-3,3-dimethyl-2-(1-hydrpoxy-2-hydroperoxy-2-methylpropy-
l)-cyclopropanecarboxylate: LC Retention time: 17.8 min., LC-MS :
M.sup.+=232.
[0184] .sup.1H-NMR spectrum: .delta. 8.82 ppm, bs(--OOH).
[0185] GC and LC analysis (internal standard method) showed that
the yield of methyl
trans-3,3-dimethyl-2-(1-hydrpoxy-2-hydroperoxy-2-methylpropyl)c-
yclopropane-carboxylate was 52,6% and that of methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 5%.
[0186] The toluene solution (167 g) was subjected to a
decomposition reaction as below.
[0187] Into a 500 mL flask equipped with a magnetic rotor and a
reflux condenser were charged 500 mg of vanadium pentoxide and 100
g of toluene, and the toluene solution obtained above was dropwise
added thereto at 60.degree. C. over 2 hours and kept at the
temperature for 1 hour. The obtained solution was were analyzed by
LC to show that disappearance of the peak of methyl
trans-3,3-dimethyl-2-(1-hydrpoxy-2-hydroperoxy-2-methy-
lpropyl)cyclopropane-carboxylate in chromatogram and a peak of
methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was
detected. Yield of methyl
trans-3,3-dimethyl-2-formylcyclopropanecarboxylate was 54.5%.
Example 42
[0188] Into a 100 mL flask equipped with a magnetic rotor and a
reflux condenser were charged 400 mg of tungsten metal powder and 3
g of water, and 3 g of a 60 wt % aqueous hydrogen peroxide were
added thereto at 40.degree. C., over 1 hour under stirring, and
reacted for 1 hour at the same temperature under stirring to
produce a clear homogeneous solution. The solution was cooled to
room temperature and 15 g of t-butanol and 5.3 g of anhydrous
magnesium sulfate were added thereto and stirred for 1 hour at room
temperature. To the obtained slurry solution was dropwise added a
mixed solution of 4 g of methyl trans-3,3-dimethyl-2-(2-methyl-1--
propenyl)cyclopropanecarboxylate and 8 g t-butanol over 20 minutes
and reacted at 25.degree. C. for 24 hours. A 50 g of 5 wt % aqueous
sodium thiosulfate solution was added to the reaction mixture and
stirred for 24 hours at room temperature. Then the mixture was
extracted twice with 20 g of toluene to give 83.7 g of a toluene
solution. The toluene solution was analyzed by GC to show that the
toluene solution contains methyl
trans-3,3-dimethyl-2-(1,2-dihydrpoxy-2-methylpropyl)cyclopropanecarboxyla-
te, the yield of which was 80.0% (internal standard method).
[0189] The basic foreign Applications filed on Aug. 11, 2000,
No.2000-244277,
[0190] filed on Oct. 27, 2000, No.2000-328816,
[0191] filed on Oct. 27, 2000, No.2000-328812,
[0192] filed on Nov. 6, 2000, No.2000-337152,
[0193] filed on Nov. 6, 2000, No.2000-337151, and
[0194] filed on Nov. 6, 2000, No.2000-337150 in Japan are hereby
incorporated by reference.
* * * * *