U.S. patent application number 12/298539 was filed with the patent office on 2009-04-16 for potassium fluoride dispersion solution, and process for production of fluorinated organic compound using the same.
This patent application is currently assigned to SUMITOMO CHEMICAL COMPANY, LIMITED. Invention is credited to Koji Hagiya, Kazuaki Sasaki.
Application Number | 20090099387 12/298539 |
Document ID | / |
Family ID | 38655654 |
Filed Date | 2009-04-16 |
United States Patent
Application |
20090099387 |
Kind Code |
A1 |
Hagiya; Koji ; et
al. |
April 16, 2009 |
POTASSIUM FLUORIDE DISPERSION SOLUTION, AND PROCESS FOR PRODUCTION
OF FLUORINATED ORGANIC COMPOUND USING THE SAME
Abstract
A potassium fluoride dispersion essentially consisting of
potassium fluoride and an aprotic organic solvent having a boiling
point higher than that of methanol, which is obtainable by mixing a
mixture containing potassium fluoride and 5 to 50 parts by weight
of methanol per 1 part by weight of potassium fluoride with the
aprotic organic solvent followed by concentrating the obtained
mixture, and a process for producing a fluorine-containing organic
compound comprising contacting an organic compound having at least
one group capable of being substituted nucleophilically with a
fluorine atom with the potassium fluoride dispersion.
Inventors: |
Hagiya; Koji; (Osaka,
JP) ; Sasaki; Kazuaki; (Osaka, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
SUMITOMO CHEMICAL COMPANY,
LIMITED
Chuo-ku
JP
|
Family ID: |
38655654 |
Appl. No.: |
12/298539 |
Filed: |
April 26, 2007 |
PCT Filed: |
April 26, 2007 |
PCT NO: |
PCT/JP2007/059439 |
371 Date: |
October 27, 2008 |
Current U.S.
Class: |
560/83 ;
252/182.32 |
Current CPC
Class: |
C07B 39/00 20130101;
C07C 201/12 20130101; C07C 67/14 20130101; C07C 17/208 20130101;
C01D 3/02 20130101; C07C 67/14 20130101; C07C 17/208 20130101; C07C
201/12 20130101; C07C 22/08 20130101; C07C 69/76 20130101; C07C
205/12 20130101 |
Class at
Publication: |
560/83 ;
252/182.32 |
International
Class: |
C07C 69/76 20060101
C07C069/76; C09K 3/00 20060101 C09K003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 27, 2006 |
JP |
2006-123126 |
Jul 6, 2006 |
JP |
2006-186334 |
Claims
1: A potassium fluoride dispersion essentially consisting of
potassium fluoride and an aprotic organic solvent having a boiling
point higher than that of methanol, which is obtainable by mixing a
mixture containing potassium fluoride and 5 to 50 parts by weight
of methanol per 1 part by weight of potassium fluoride with the
aprotic organic solvent followed by concentrating the obtained
mixture.
2: The potassium fluoride dispersion according to claim 1, wherein
the mixture containing potassium fluoride and 5 to 50 parts by
weight of methanol per 1 part by weight of potassium fluoride is a
solution wherein potassium fluoride is dissolved perfectly in
methanol.
3: The potassium fluoride dispersion according to claim 2, wherein
potassium fluoride in the potassium fluoride dispersion is
potassium fluoride wherein a part or all of the initial particles,
of which particle diameter is 0.1 to 5 .mu.m, are flocculated to
form particles having 5 to 25 .mu.m of volumetric average particle
diameter.
4: A process for producing a potassium fluoride dispersion
essentially consisting of potassium fluoride and an aprotic organic
solvent having a boiling point higher than that of methanol, which
comprises mixing a mixture containing potassium fluoride and 5 to
50 parts by weight of methanol per 1 part by weight of potassium
fluoride with the aprotic organic solvent followed by concentrating
the obtained mixture.
5: The method according to claim 4, wherein the mixture containing
potassium fluoride and 5 to 50 parts by weight of methanol per 1
part by weight of potassium fluoride is a solution wherein
potassium fluoride is dissolved perfectly in methanol.
6: The method according to claim 4, wherein the concentration is
conducted while adding the mixture containing potassium fluoride
and 5 to 50 parts by weight of methanol per 1 part by weight of
potassium fluoride into the aprotic organic solvent having a
boiling point higher than that of methanol, which is adjusted at a
temperature which is the boiling point of methanol or more.
7: The method according to claim 4, wherein the aprotic organic
solvent is an aprotic polar solvent.
8: The method according to claim 7, wherein the aprotic polar
solvent is a sulfone solvent or a sulfoxide solvent.
9: The method according to claim 4, wherein the mixture containing
potassium fluoride and 5 to 50 parts by weight of methanol per 1
part by weight of potassium fluoride is a mixture obtainable by
mixing hydrogen fluoride with potassium hydroxide in methanol.
10: The method according to claim 9, wherein hydrogen fluoride is
hydrofluoric acid.
11: The method according to claim 5, wherein potassium fluoride in
the potassium fluoride dispersion is potassium fluoride wherein a
part or all of the initial particles, of which particle diameter is
0.1 to 5 .mu.m, are flocculated to form particles having 5 to 25
.mu.m of volumetric average particle diameter.
12: A process for producing a fluorine-containing organic compound
comprising contacting an organic compound having at least one group
capable of being substituted nucleophilically with a fluorine atom
with the potassium fluoride dispersion according to claim 1.
13: The process according to claim 12, wherein the group capable of
being substituted nucleophilically with a fluorine atom is a
chlorine atom, a bromine atom, an iodine atom, a nitro group, a
sulfo group, an optionally substituted alkylsulfonyloxy group, an
optionally substituted arylsulfonyloxy group or an optionally
substituted acyloxy group.
14: The process according to claim 12, wherein the organic compound
having at least one group capable of being substituted
nucleophilically with a fluorine atom is a compound wherein at
least one hydrogen atom of an optionally substituted aliphatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom.
15: The process according to claim 12, wherein the organic compound
having at least one group capable of being substituted
nucleophilically with a fluorine atom is a compound wherein at
least one hydrogen atom of an optionally substituted aromatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom.
16: The process according to claim 12, wherein the organic compound
having at least one group capable of being substituted
nucleophilically with a fluorine atom is a compound wherein at
least one hydrogen atom of an optionally substituted heteroaromatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom.
17: The process according to claim 15, wherein the compound wherein
at least one hydrogen atom of an optionally substituted aromatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom is
tetrachloroterephthalic dichloride, and the fluorine-containing
organic compound is tetrafluoroterephthalic difluoride.
18: The process according to claim 15, wherein the compound wherein
at least one hydrogen atom of an optionally substituted aromatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom is
2,4-dichloronitrobenzene, and the fluorine-containing organic
compound is 2,4-difluoronitrobenzene.
19: The process according to claim 15, wherein the compound wherein
at least one hydrogen atom of an optionally substituted aromatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom is
4-chloronitrobenzene, and the fluorine-containing organic compound
is 4-fluoronitrobenzene.
20: The process according to claim 16, wherein the compound wherein
at least one hydrogen atom of an optionally substituted
heteroaromatic hydrocarbon compound is substituted with a group
capable of being substituted nucleophilically with a fluorine atom
is 4,5,6-trichloropyrimidine, and the fluorine-containing organic
compound is 4,5,6-trifluoropyrimidine.
21: The process according to claim 14, wherein the compound wherein
at least one hydrogen atom of an optionally substituted aliphatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom is benzyl
bromide, and the fluorine-containing organic compound is benzyl
fluoride.
22: Use of the potassium fluoride dispersion according to claim 1
for fluorination of an organic compound having at least one group
capable of being substituted nucleophilically with a fluorine
atom.
23: Use of the potassium fluoride dispersion obtained according to
claim 4 for fluorination of an organic compound having at least one
group capable of being substituted nucleophilically with a fluorine
atom.
24: A method for fluorinating an organic compound comprising
contacting an organic compound having at least one group capable of
being substituted nucleophilically with a fluorine atom with the
potassium fluoride dispersion according to claim 1.
25: A method for fluorinating an organic compound comprising
contacting an organic compound having at least one group capable of
being substituted nucleophilically with a fluorine atom with the
potassium fluoride dispersion obtained according to claim 4.
Description
TECHNICAL FIELD
[0001] The present invention relates to a potassium fluoride
dispersion and a process for producing a fluorine-containing
organic compound using the same.
BACKGROUND ART
[0002] Potassium fluoride is useful as a fluorinating agent for an
organic compound. WO1987/004151 discloses that a method comprising
preparing a potassium fluoride dispersion by mixing potassium
fluoride with about 1.4 parts by weight of methanol per 1 parts by
weight of potassium fluoride and sulfolane followed by
concentrating methanol from the obtained mixture, and fluorinating
an organic compound using the prepared potassium fluoride
dispersion. However, an activity of the potassium fluoride
dispersion in a fluorination reaction is not necessarily enough and
it is necessary to conduct a fluorination reaction using an
expensive phase transfer catalyst.
DISCLOSURE OF THE INVENTION
[0003] The present invention is to provide
<1> A potassium fluoride dispersion essentially consisting of
potassium fluoride and an aprotic organic solvent having a boiling
point higher than that of methanol, which is obtainable by mixing a
mixture containing potassium fluoride and 5 to 50 parts by weight
of methanol per 1 part by weight of potassium fluoride with the
aprotic organic solvent followed by concentrating the obtained
mixture; <2> The potassium fluoride dispersion according to
<1>, wherein the mixture containing potassium fluoride and 5
to 50 parts by weight of methanol per 1 part by weight of potassium
fluoride is a solution wherein potassium fluoride is dissolved
perfectly in methanol; <3> The potassium fluoride dispersion
according to <2>, wherein potassium fluoride in the potassium
fluoride dispersion is potassium fluoride wherein a part of or all
of the initial particles, of which particle diameter is 0.1 to 5
.mu.m, are flocculated to form particles having 5 to 25 .mu.m of
volumetric average particle diameter; <4> A process for
producing a potassium fluoride dispersion essentially consisting of
potassium fluoride and an aprotic organic solvent having a boiling
point higher than that of methanol, which comprises mixing a
mixture containing potassium fluoride and 5 to 50 parts by weight
of methanol per 1 part by weight of potassium fluoride with the
aprotic organic solvent followed by concentrating the obtained
mixture; <5> The method according to <4>, wherein the
mixture containing potassium fluoride and 5 to 50 parts by weight
of methanol per 1 part by weight of potassium fluoride is a
solution wherein potassium fluoride is dissolved perfectly in
methanol; <6> The method according to <4>, wherein the
concentration is conducted while adding the mixture containing
potassium fluoride and 5 to 50 parts by weight of methanol per 1
part by weight of potassium fluoride into the aprotic organic
solvent having a boiling point higher than that of methanol, which
is adjusted at a temperature which is the boiling point of methanol
or more; <7> The method according to any one of <4> to
<6>, wherein the aprotic organic solvent is an aprotic polar
solvent; <8> The method according to <7>, wherein the
aprotic polar solvent is a sulfone solvent or a sulfoxide solvent;
<9> The method according to <4>, wherein the mixture
containing potassium fluoride and 5 to 50 parts by weight of
methanol per 1 part by weight of potassium fluoride is a mixture
obtainable by mixing hydrogen fluoride with potassium hydroxide in
methanol; <10> The method according to <9>, wherein
hydrogen fluoride is hydrofluoric acid; <11> The method
according to <5>, wherein potassium fluoride in the potassium
fluoride dispersion is potassium fluoride wherein apart of or all
of the initial particles, of which particle diameter is 0.1 to 5
.mu.m, are flocculated to form particles having 5 to 25 .mu.m of
volumetric average particle diameter; <12> A process for
producing a fluorine-containing organic compound comprising
contacting an organic compound having at least one group capable of
being substituted nucleophilically with a fluorine atom with the
potassium fluoride dispersion according to any one of <1> to
<3>; <13> The process according to <12>, wherein
the group capable of being substituted nucleophilically with a
fluorine atom is a chlorine atom, a bromine atom, an iodine atom, a
nitro group, a sulfo group, an optionally substituted
alkylsulfonyloxy group, an optionally substituted arylsulfonyloxy
group or an optionally substituted acyloxy group; <14> The
process according to <12>, wherein the organic compound
having at least one group capable of being substituted
nucleophilically with a fluorine atom is a compound wherein at
least one hydrogen atom of an optionally substituted aliphatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom; <15> The
process according to <12>, wherein the organic compound
having at least one group capable of being substituted
nucleophilically with a fluorine atom is a compound wherein at
least one hydrogen atom of an optionally substituted aromatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom; <16> The
process according to <12>, where in the organic compound
having at least one group capable of being substituted
nucleophilically with a fluorine atom is a compound wherein at
least one hydrogen atom of an optionally substituted heteroaromatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom; <17> The
process according to <15>, wherein the compound wherein at
least one hydrogen atom of an optionally substituted aromatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom is
tetrachloroterephthalic dichloride, and the fluorine-containing
organic compound is tetrafluoroterephthalic difluoride; <18>
The process according to <15>, wherein the compound wherein
at least one hydrogen atom of an optionally substituted aromatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom is
2,4-dichloronitrobenzene, and the fluorine-containing organic
compound is 2,4-difluoronitrobenzene; <19> The process
according to <15>, wherein the compound wherein at least one
hydrogen atom of an optionally substituted aromatic hydrocarbon
compound is substituted with a group capable of being substituted
nucleophilically with a fluorine atom is 4-chloronitrobenzene, and
the fluorine-containing organic compound is 4-fluoronitrobenzene;
<20> The process according to <16>, wherein the
compound wherein at least one hydrogen atom of an optionally
substituted heteroaromatic hydrocarbon compound is substituted with
a group capable of being substituted nucleophilically with a
fluorine atom is 4,5,6-trichloropyrimidine, and the
fluorine-containing organic compound is 4,5,6-trifluoropyrimidine;
<21> The process according to <14>, wherein the
compound wherein at least one hydrogen atom of an optionally
substituted aliphatic hydrocarbon compound is substituted with a
group capable of being substituted nucleophilically with a fluorine
atom is benzyl bromide, and the fluorine-containing organic
compound is benzyl fluoride; <22> Use of the potassium
fluoride dispersion according to any one of <1> to <3>
for fluorination of an organic compound having at least one group
capable of being substituted nucleophilically with a fluorine atom;
<23> Use of the potassium fluoride dispersion obtained
according to any one of <4> to <11> for fluorination of
an organic compound having at least one group capable of being
substituted nucleophilically with a fluorine atom; <24> A
method for fluorinating an organic compound comprising contacting
an organic compound having at least one group capable of being
substituted nucleophilically with a fluorine atom with the
potassium fluoride dispersion according to any one of <1> to
<3>; <25> A method for fluorinating an organic compound
comprising contacting an organic compound having at least one group
capable of being substituted nucleophilically with a fluorine atom
with the potassium fluoride dispersion obtained according to any
one of <4> to <11>.
BRIEF DESCRIPTION OF DRAWINGS
[0004] FIG. 1 This is a drawing showing volumetric particle size
distribution of the potassium fluoride dispersion obtained in
Example 14.
[0005] FIG. 2 This is a drawing showing volumetric particle size
distribution of the potassium fluoride dispersion obtained in
Comparative Example 3.
[0006] FIG. 3 This is a drawing showing volumetric particle size
distribution of the potassium fluoride dispersion obtained in
Comparative Example 4.
[0007] FIG. 4 This is a drawing showing volumetric particle size
distribution of the potassium fluoride dispersion obtained in
Example 15.
[0008] FIG. 5 This is an image of FE-SEM of potassium fluoride
particles in the potassium fluoride dispersion obtained in Example
14 (2,000-fold magnification for shooting).
[0009] FIG. 6 This is an image of FE-SEM of potassium fluoride
particles in the potassium fluoride dispersion obtained in Example
14 (5,000-fold magnification for shooting).
[0010] FIG. 7 This is an image of FE-SEM of potassium fluoride
particles in the potassium fluoride dispersion obtained in
Comparative Example 3 (2,000-fold magnification for shooting).
[0011] FIG. 8 This is an image of FE-SEM of potassium fluoride
particles in the potassium fluoride dispersion obtained in
Comparative Example 4 (1,000-fold magnification for shooting).
[0012] FIG. 9 This is an image of FE-SEM of potassium fluoride
particles in the potassium fluoride dispersion obtained in Example
15 (2,000-fold magnification for shooting).
[0013] FIG. 10 This is an image of FE-SEM of potassium fluoride
particles in the potassium fluoride dispersion obtained in Example
15 (5,000-fold magnification for shooting).
BEST MODE FOR CARRYING OUT THE PRESENT INVENTION
[0014] The potassium fluoride dispersion of the present invention
is a potassium fluoride dispersion obtainable by mixing a mixture
containing potassium fluoride and 5 to 50 parts by weight of
methanol per 1 part by weight of potassium fluoride with an aprotic
organic solvent having a boiling point higher than that of methanol
followed by concentrating the obtained mixture, and it essentially
consists of potassium fluoride and the aprotic organic solvent
having a boiling point higher than that of methanol.
[0015] A commercially available methanol may be used and one
produced by reacting potassium hydroxide with hydrogen fluoride may
be used. It may be an anhydride or a hydrate. Alternatively, a
hydrous one may be used.
[0016] From the economic viewpoint, one produced by reacting
potassium hydroxide with hydrogen fluoride is preferably used as
potassium fluoride. A commercially available potassium hydroxide is
usually used. An aqueous solution of potassium hydroxide may be
used and a solution of an organic solvent of potassium hydroxide
may be used. As the organic solvent, an alcohol solvent is
preferable and methanol is more preferable. An organic solvent
containing water may be used. A commercially available hydrogen
fluoride is usually used. Hydrogen fluoride gas may be used and
hydrofluoric acid may be used. The amount of hydrogen fluoride to
be used is usually 0.9 to 1.1 moles and preferably 0.99 to 1.01
moles per 1 mole of potassium hydroxide.
[0017] The reaction of hydrogen fluoride and potassium hydroxide is
usually conducted in an organic solvent, and an alcohol solvent is
preferable as the organic solvent and methanol is more
preferable.
[0018] Potassium fluoride can be isolated by a concentration of the
reaction mixture obtained by reacting hydrogen fluoride with
potassium hydroxide. When the above-mentioned reaction mixture does
not contain any organic solvent other than methanol, the obtained
reaction mixture may be used as it is for producing the potassium
fluoride dispersion.
[0019] When the reaction mixture containing potassium fluoride,
which is obtained by reacting hydrogen fluoride with potassium
hydroxide in methanol, is used as potassium fluoride for a
preparation of the potassium fluoride dispersion, the amount of
methanol to be used may be decided so that the amount of methanol
will become 5 to 50 parts by weight per 1 part of potassium
fluoride generated in the reaction.
[0020] As the mixture containing potassium fluoride and 5 to 50
parts by weight of methanol per 1 part by weight of potassium
fluoride, a solution wherein potassium fluoride is dissolved
perfectly in methanol is preferable. Depending on the preparing
temperature of the solution, 8 to 50 parts by weight of methanol
per 1 part of potassium fluoride is more preferably used in the
point of easy preparation of the solution.
[0021] The mixture containing potassium fluoride and 5 to 50 parts
by weight of methanol per 1 part by weight of potassium fluoride is
usually prepared by mixing potassium fluoride with the
pre-determined amount of methanol. The preparing temperature is
usually 0 to 100.degree. C. and preferably 20 to 70.degree. C.
[0022] The aprotic organic solvent having a boiling point higher
than that of methanol may be a nonpolar solvent or a polar solvent.
An aprotic polar solvent is preferable.
[0023] Examples of the aprotic polar solvent having a boiling point
higher than that of methanol include ether solvents such as
diisopropyl ether, dibutyl ether, dioxane, diethylene glycol
dimethyl ether and triethylene glycol dimethyl ether; sulfone
solvents such as sulfolane, dimethylsulfone and methyl ethyl
sulfone; sulfoxide solvents such as dimethylsulfoxide,
diethylsulfoxide and tetramethylenesulfoxide; amide solvents such
as N,N-dimethylformamide, N,N-dimethylacetamide and
N-methylpyrolidone; and nitrile solvents such as butyronitrile and
adiponitrile. Sulfone solvents, sulfoxide solvents and amide
solvents are preferable, and sulfone solvents and sulfoxide
solvents are more preferable.
[0024] Examples of the aprotic nonpolar solvent having a boiling
point higher than that of methanol include aliphatic hydrocarbon
solvents such as hexane, heptane, octane and cyclohexane; and
aromatic hydrocarbon solvents such as benzene, toluene and
xylene.
[0025] The aprotic organic solvent may be used alone, and two or
more thereof may be mixed to use.
[0026] The amount of the aprotic organic solvent having a boiling
point higher than that of methanol to be used may be usually 1 part
by weight or more per 1 part by weight of potassium fluoride. While
there is no upper limit particularly, since the volume efficiency
goes down when the amount thereof is too much, practical amount
thereof is 20 parts by weight or less.
[0027] The potassium fluoride dispersion of the present invention
can be produced by mixing a mixture containing potassium fluoride
and 5 to 50 parts by weight of methanol per 1 part by weight of
potassium fluoride with an aprotic organic solvent having a boiling
point higher than that of methanol followed by concentrating the
obtained mixture. In order for the easy removal of methanol in the
mixture containing potassium fluoride and 5 to 50 parts by weight
of methanol per 1 part by weight of potassium fluoride, a solvent
capable of forming an azeotrope with methanol may be used together.
Alternatively, the concentration may be conducted while adding the
mixture containing potassium fluoride and 5 to 50 parts by weight
of methanol per 1 part by weight of potassium fluoride into the
aprotic organic solvent adjusted at a temperature which is the
boiling point of methanol or more. Preferably, the concentration is
conducted while adding the mixture containing potassium fluoride
and 5 to 50 parts by weight of methanol per 1 part by weight of
potassium fluoride into the aprotic organic solvent adjusted at a
temperature which is the boiling point of methanol or more to
prepare the potassium fluoride dispersion.
[0028] Examples of the solvent capable of forming an azeotrope with
methanol include aromatic hydrocarbon solvents such as benzene,
toluene and xylene; and aliphatic hydrocarbon solvents such as
hexane and cyclohexane.
[0029] The operation pressure on concentrating is usually 0.7 to
200 kPa and concentrating temperature is usually 20 to 200.degree.
C.
[0030] The concentration is carried out until the potassium
fluoride dispersion essentially consisting of potassium fluoride
and the aprotic organic solvent having a boiling point higher than
that of methanol can be obtained.
[0031] The potassium fluoride dispersion thus obtained essentially
consists of potassium fluoride and the aprotic organic solvent
having a boiling point higher than that of methanol, and it is a
mixture wherein the fine powder of potassium fluoride is dispersed
in the aprotic organic solvent. The content of potassium fluoride
in the potassium fluoride dispersion is usually 5 to 70% by
weight.
[0032] Especially, potassium fluoride in the potassium fluoride
dispersion prepared by using the solution wherein potassium
fluoride is dissolved perfectly in methanol has 0.1 to 5 .mu.m of
particle diameter of the initial particles and a part or all of the
initial particles are flocculated to form particles having 5 to 25
.mu.m of volumetric average particle diameter.
[0033] The potassium fluoride dispersion thus obtained has a high
activity in a fluorination reaction.
[0034] Next, a process for producing a fluorine-containing organic
compound comprising contacting an organic compound having at least
one group capable of being substituted nucleophilically with a
fluorine atom (hereinafter, simply referred to as the organic
compound) with the potassium fluoride dispersion of the present
invention will be illustrated.
[0035] Examples of the group capable of being substituted
nucleophilically with a fluorine atom include a chlorine atom, a
bromine atom, an iodine atom, a nitro group, a sulfo group, an
optionally substituted alkylsulfonyloxy group, an optionally
substituted arylsulfonyloxy group and an optionally substituted
acyloxy group. When the organic compound has two or more groups
capable of being substituted nucleophilically with a fluorine atom,
they may be same or different from each other.
[0036] Examples of the optionally substituted alkylsulfonyloxy
group include an alkylsulfonyloxy group which may be substituted
with a fluorine atom or atoms such as a methanesulfonyloxy group,
an ethanesulfonyloxy group and a trifluoromethanesulfonyloxy group.
Examples of the optionally substituted arylsulfonyloxy group
include a p-toluenesulfonyloxy group, a benzenesulfonyloxyl group
and a 1-naphthalenesulfonyloxy group. Examples of the optionally
substituted acyloxy group include an acyloxy group which may be
substituted with a fluorine atom or atoms such as a
trifluoroacetoxy group, a pentafluoroethylcarbonyloxy group, a
tetrafluorobenzoyloxy group and a benzoyloxy group.
[0037] Examples of the organic compound include a compound wherein
at least one hydrogen atom of an optionally substituted aliphatic
hydrocarbon compound is substituted with a group capable of being
substituted nucleophilically with a fluorine atom, a compound
wherein at least one hydrogen atom of an optionally substituted
aromatic hydrocarbon compound is substituted with a group capable
of being substituted nucleophilically with a fluorine atom, and a
compound wherein at least one hydrogen atom of an optionally
substituted heteroaromatic hydrocarbon compound is substituted with
a group capable of being substituted nucleophilically with a
fluorine atom.
[0038] Examples of the optionally substituted aliphatic hydrocarbon
compound include a C1-C20 unsubstituted aliphatic hydrocarbon
compound such as methane, ethane, n-propane, isopropane, n-butane,
isobutene, n-pentane, n-decane, cyclopropane,
2,2-dimethylcyclopropane, cyclopentane and cyclohexane, and these
compounds of which at least one hydrogen atom is substituted with
an uninvolved substituent in the reaction. Examples of the
uninvolved substituent in the reaction include a fluorine atom; a
C1-C20 alkoxy group which may be substituted with a fluorine atom
or atoms such as a methoxy group, an ethoxy group, an n-propoxy
group, an isopropoxy group, an n-butoxy group, an isobutoxy group,
a sec-butoxy group, a tert-butoxy group and a trifluoromethoxy
group; a C6-C20 aryl group which may be substituted with at least
one selected from the group consisting of a fluorine atom, the
above-mentioned alkoxy group and the C6-C20 aryloxy group described
below such as a phenyl group, a 1-naphthyl group, a 2-naphthyl
group, a 4-methylphenyl group, a 4-methoxyphenyl group, a
3-phenoxyphenyl group, a 2,3,5,6-tetrafluorophenyl group, a
2,3,5,6-tetrafluoro-4-methylphenyl group, a
2,3,5,6-tetrafluoro-4-methoxyphenyl group and a
2,3,5,6-tetrafluoro-4-methoxymethylphenyl group; a C5-C20
heteroaryl group which may be substituted with at least one
selected from the group consisting of a fluorine atom and the
above-mentioned alkoxy group such as a 2-pyridyl group; a C6-C20
aryloxy group which may be substituted with at least one selected
from the group consisting of a fluorine atom, the above-mentioned
alkoxy group and the C6-C20 aryloxy group such as a phenoxy group,
a 2-methylphenoxy group, a 4-methylphenoxy group, a
4-methoxyphenoxy group and a 3-phenoxyphenoxy group; a C7-C20
aralkyloxy group which may be substituted with at least one
selected from the group consisting of a fluorine atom, the
above-mentioned alkoxy group and the above-mentioned aryloxy group
such as a benzyloxy 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-methylbenzyloxy group, a
2,3,5,6-tetrafluoro-4-methoxybenzyloxy group and a
2,3,5,6-tetrafluoro-4-methoxymethylbenzyloxy group; a C2-C20 acyl
group which may be substituted with at least one selected from the
group consisting of a fluorine atom, the above-mentioned alkoxy
group and the above-mentioned aryloxy group such as an acetyl
group, a propionyl group, a benzoyl group, a 2-methylbenzoyl group,
a 4-methylbenzoyl group, a 4-methoxybenzoyl group, a benzylcarbonyl
group, a 4-methylbenzylcarbonyl group and a 4-methoxybenzylcarbonyl
group; a carboxyl group; an aminosulfonyl group; a cyano group; and
a carbamoyl group.
[0039] Examples of the aliphatic hydrocarbon compound substituted
with the uninvolved substituent in the reaction include
fluoromethane, trifluoromethane, methoxymethane, ethoxymethane,
methoxyethane, toluene, 4-methoxybenzene, 3-phenoxybenzene,
2,3,5,6-tetrafluorotoluene, 2,3,5,6-tetrafluoro-4-methyltoluene,
2,3,5,6-tetrafluoro-4-methoxytoluene,
2,3,5,6-tetrafluoro-4-methoxymethyltoluene, 2-propyl-1-naphthalene,
methyl isobutyl ketone, acetophenone, 4-methylacetophenone and
phenylacetone.
[0040] Examples of the optionally substituted aromatic hydrocarbon
compound include a C6-C20 unsubstituted aromatic hydrocarbon
compound such as benzene, naphthalene and toluene, and these
compounds of which at least one hydrogen atom is substituted with
an uninvolved substituent in the reaction. Examples of the
uninvolved substituent in the reaction include the same as
described above. Alternatively, two neighboring substituents among
these uninvolved substituents in the reaction may be bonded to form
a ring together with the carbon atoms to which they are bonded.
[0041] Examples of the aromatic hydrocarbon compound substituted
with the uninvolved substituent in the reaction include
cyanobenzene, dicyanobenzene, fluorobenzene, difluorobenzene,
benzenesulfonamide, biphenyl, 2-phenylnaphthalene, phenoxybenzene,
benzophenone, 1,2-diphenylethanone and terephthalic acid.
[0042] Examples of the optionally substituted heteroaromatic
hydrocarbon compound include a C5-C20 unsubstituted heteroaromatic
hydrocarbon compound such as pyridine, methylpyridine, quinoline
and pyrimidine, and these compounds of which at least one hydrogen
atom is substituted with an uninvolved substituent in the reaction.
Examples of the uninvolved substituent in the reaction include the
same as described above. Alternatively, two neighboring
substituents among these uninvolved substituents in the reaction
may be bonded to form a ring together with the carbon atoms to
which they are bonded.
[0043] Examples of the heteroaromatic hydrocarbon compound
substituted with the uninvolved substituent in the reaction include
4-phenylpyridine and 3-methyl-5-trifluoromethylpyridine.
[0044] Specific examples of the organic compound include
1-chlorobutane, 1-bromobutane, 1-iodobutane, 1-chlorocyclobutane,
1-chloropentane, 1-bromopentane, 1-chlorocyclopentane,
1-chloro-4-bromobutane, 1-chlorohexane, 1-bromohexane,
1,6-dibromohexane, 1-chloroheptane, 1-bromoheptane,
2-chloroheptane, 2-bromoheptane, 1-chlorooctane, 1-bromooctane,
2-chlorooctane, 2-bromooctane, benzyl chloride, benzyl bromide,
(1-chloroethyl)benzene, (1-bromoethyl)benzene, 4-methoxybenzyl
chloride, 4-methylbenzylbromide, 3,4,5-trifluorobenzylbromide,
n-butyl p-toluenesulfonate, n-butyl methanesulfonate, n-pentyl
p-toluenesulfonate, n-pentyl methanesulfonate, n-hexyl
p-toluenesulfonate, n-hexyl methanesulfonate, n-heptyl
p-toluenesulfonate, n-heptyl methanesulfonate, n-octyl
p-toluenesulfonate, n-octyl methanesulfonate, n-butyl
trifluoroacetate, n-butyl tetrafluorobenzoate, n-octyl
trifluoroacetate, 4-chloronitrobenzene, 4-bromonitrobenzene,
2-chloronitrobenzene, 2-bromonitrobenzene,
2,4-dichloronitrobenzene, 2,6-dichloronitrobenzene,
3,5-dichloronitrobenzene, 4-cyanochlorobenzene,
4-cyanobromobenzene, 1-chloro-2,4-dinitrobenzene,
tetrachloroterephthalonitrile, tetrachloroisophthalonitrile,
tetrachloroorthophthalonitrile, 1,3-dichloro-4,6-dinitrobenzene,
2-chloroquinoline, 2-chloro-5-nitropyridine,
2-chloro-5-trifluoromethylpyridine and
4,5,6-trichloropyrimidine.
[0045] When the organic compound has two or more groups capable of
being substituted nucleophilically with a fluorine atom, the
fluorine-containing organic compound produced differs depending on
the reaction conditions. Only the highest reactive substituent
among groups capable of being substituted nucleophilically with a
fluorine atom is sometimes substituted with a fluorine atom and all
of the groups capable of being substituted nucleophilically with a
fluorine atom are sometimes substituted with fluorine atoms.
[0046] When the organic compound wherein two or more groups capable
of being substituted nucleophilically with a fluorine atom are
bonded to the aromatic hydrocarbon group is used, the group capable
of being substituted nucleophilically with a fluorine atom having a
stronger electron-withdrawing group on para- or ortho-position is
usually substituted preferentially with a fluorine atom. For
example, when 4-chloronitrobenzene is used as the organic compound,
the chlorine atom at 4-position having stronger
electron-withdrawing nitro group on para-position is preferentially
substituted with a fluorine atom and 4-fluoronitrobenzene is
selectively produced. By selecting reaction conditions such as use
of a large excess of the potassium fluoride dispersion,
1,4-difluorobenzene which the nitro group at 1-position can be also
substituted with a fluorine atom as well as the chlorine atom at
4-position can be obtained.
[0047] When the organic compound wherein two or more groups capable
of being substituted nucleophilically with a fluorine atom are
bonded to the heteroaromatic hydrocarbon group is used, the group
capable of being substituted nucleophilically with a fluorine atom
on 2-, 4- or 6-position against the heteroatom composed of the
heteroaromatic hydrocarbon group is usually substituted
preferentially with a fluorine atom. For example, when
2-chloro-3-nitropyridine is used as the organic compound, the
chlorine atom at 2-position against the nitrogen atom composed of
the pyridyl group is preferentially substituted with a fluorine
atom and 2-fluoro-3-nitropyridine is selectively produced. By
selecting reaction conditions such as use of a large excess of the
potassium fluoride dispersion, 2,3-Difluoropyridine which the nitro
group at 3-position can be also substituted with a fluorine atom as
well as the chlorine atom at 2-position can be obtained.
[0048] The amount of the potassium fluoride dispersion to be used
may be decided arbitrarily depending on the number of the groups
desired to substitute with a fluorine atom among groups capable of
being substituted nucleophilically with a fluorine atom, and
usually, the potassium fluoride containing 1 mole or more of
potassium fluoride per 1 mole of the group desired to substitute
with a fluorine atom is used. When the organic compound has one
group desired to substitute with a fluorine atom, the potassium
fluoride containing 1.5 to 5 moles of potassium fluoride per 1 mole
of the organic compound is preferably used from the viewpoint of
the reaction efficiency.
[0049] The contact of the potassium fluoride dispersion and the
organic compound is usually conducted by mixing the both as it is
or in the presence of a solvent. As the solvent, the
above-mentioned aprotic polar solvent is preferable.
[0050] When the contacting temperature is too low, the fluorination
reaction hardly proceeds and, when the contacting temperature is
too high, side reaction such as degradation of the starting
material or product may proceed. Therefore, the practical reaction
temperature is 20 to 250.degree. C.
[0051] The contact of the potassium fluoride dispersion and the
organic compound may be carried out under normal pressure or under
pressure.
[0052] The fluorination reaction of the organic compound proceeds
by contacting the potassium fluoride dispersion with the organic
compound, and the progress of the fluorination reaction can be
checked by a conventional analytical means such as gas
chromatography, high performance liquid chromatography, thin layer
chromatography, NMR and IR.
[0053] After completion of the fluorination reaction, the
fluorine-containing organic compound can be isolated, for example,
by removing in soluble matters from the obtained reaction mixture
by filtration followed by concentrating the obtained filtrate.
Alternatively, the fluorine-containing organic compound can also be
isolated by adding water and a solvent having a low compatibility
with water to the reaction mixture to conduct extraction followed
by concentrating the obtained organic layer. The
fluorine-containing organic compound isolated may be further
purified by a means such as distillation or column
chromatography.
[0054] Examples of the solvent having a low compatibility with
water include aromatic hydrocarbon solvents such as toluene, xylene
and chlorobenzene; aliphatic hydrocarbon solvents such as pentane,
hexane and heptane; halogenated hydrocarbon solvents such as
dichloromethane, dichloroethane and chloroform; ether solvents such
as diethyl ether, methyl tert-butyl ether and tetrahydrofuran; and
ester solvents such as ethyl acetate.
[0055] Examples of the fluorine-containing organic compound thus
obtained include 1-fluorobutane, 1-fluorocyclobutane,
1-fluoropentane, 1-fluorocyclopentane, 1,4-difluorobutane,
1-chloro-4-fluorobutane, 1-fluorohexane, 1,6-difluorohexane,
1-fluoroheptane, 2-fluoroheptane, 1-fluorooctane, 2-fluorooctane,
benzyl fluoride, (1-fluoroethyl)benzene, 4-methoxybenzyl fluoride,
4-methylbenzyl fluoride, 3,4,5-trifluorobenzyl fluoride,
4-fluoronitrobenzene, 2-fluoronitrobenzene,
2,4-difluoronitrobenzene, 2,6-dichlorofluorobenzene,
3,5-difluoronitrobenzene, 4-cyanofluorobenzene,
1-fluoro-2,4-dinitrobenzene, tetrafluoroterephthalonitrile,
tetrafluoroisophthalonitrile, tetrafluoroorthophthalonitrile,
1,3-difluoro-4,6-dinitrobenzene, 2-fluoroquinoline,
2-fluoro-5-nitropyridine, 2-fluoro-5-trifluoromethylpyridine,
4,6-difluoro-5-chloropyrimidine and 4,5,6-trifluoropyrimidine.
[0056] The fluorination reaction in which tetrachloroterephthaloyl
dichloride is used as the organic compound will be illustrated
below.
[0057] Tetrafluoroterephthaloyl difluoride can be produced by
contacting tetrachloroterephthaloyl dichloride with the potassium
fluoride dispersion.
[0058] Tetrachloroterephthaloyl dichloride can be produced, for
example, according to a known method described in JP 2-11571B or
the like.
[0059] The amount of the potassium fluoride dispersion to be used
may usually be the amount of the dispersion in which 6 moles or
more of potassium fluoride per 1 mole of tetrachloroterephthaloyl
dichloride is contained. While there is no specific upper limit,
the amount of the dispersion in which 10 moles or less of potassium
fluoride per 1 mole of tetrachloroterephthaloyl dichloride is
contained is preferable from the economic viewpoint.
[0060] The potassium fluoride dispersion is preferably contacted
with tetrachloroterephthaloyl dichloride at 120 to 200.degree.
C.
[0061] After completion of the reaction, tetrafluoroterephthaloyl
difluoride can be isolated, for example, by concentrating the
reaction mixture. Isolated tetrafluoroterephthaloyl difluoride may
be further purified by a conventional purification means such as
rectification.
[0062] Alternatively, the corresponding tetrafluoroterephthalic
acid diester can be also produced by reacting obtained
tetrafluoroterephthaloyl difluoride with an aliphatic alcohol
compound.
[0063] Tetrafluoroterephthaloyl difluoride may be reacted with the
aliphatic alcohol compound as it is without isolating from the
above-mentioned reaction mixture.
[0064] Examples of the aliphatic alcohol compound include a C1-C6
aliphatic alcohol compound such as methanol, ethanol, n-propanol,
isopropanol, n-butanol, tert-butanol and cyclohexanol.
[0065] The amount of the aliphatic alcohol compound to be used is
not particularly limited. While the excess amount thereof may be
used also to serve as the solvent, the practical amount thereof is
2 to 50 moles per 1 mole of tetrafluoroterephthaloyl
difluoride.
[0066] The reaction of tetrafluoroterephthaloyl difluoride with the
aliphatic alcohol compound is preferably carried out in the
presence of an organic solvent. Examples of the organic solvent
include aromatic hydrocarbon solvents such as toluene, xylene and
chlorobenzene; aliphatic hydrocarbon solvents such as pentane,
hexane and heptane; halogenated aliphatic hydrocarbon solvents such
as dichloromethane, dichloroethane and chloroform; ether solvents
such as diethyl ether and methyl tert-butyl ether; ester solvents
such as ethyl acetate; and the above-mentioned aliphatic alcohol
compounds. The amount of the organic solvent to be used is not
particularly limited.
[0067] The reaction of tetrafluoroterephthaloyl difluoride with the
aliphatic alcohol compound is usually conducted by mixing the both
and the mixing order thereof is not particularly limited.
[0068] The reaction temperature is usually 0 to 100.degree. C.
While the reaction is usually carried out under normal pressure,
the reaction may be conducted under pressure.
[0069] The progress of the reaction can be checked by a
conventional analytical means such as gas chromatography and high
performance liquid chromatography.
[0070] After completion of the reaction, the
tetrafluoroterephthalic acid diester can be isolated by
concentrating the reaction mixture, if necessary, after removing
insoluble matters by filtration, followed by mixing the obtained
concentrated residue with water to separate the precipitated solid
by filtration. Alternatively, the tetrafluoroterephthalic acid
diester can also be isolated by mixing the reaction mixture, water
and as necessary, a solvent having a low compatibility with water
to conduct extraction treatment followed by concentrating the
obtained organic layer. Examples of the solvent having a low
compatibility with water include aromatic hydrocarbon solvents such
as toluene, xylene and chlorobenzene; aliphatic hydrocarbon
solvents such as pentane, hexane and heptane; halogenated aliphatic
hydrocarbon solvents such as dichloromethane, dichloroethane and
chloroform; ether solvents such as diethyl ether and methyl
tert-butyl ether; and ester solvents such as ethyl acetate. The
amount thereof to be used is not particularly limited.
[0071] The tetrafluoroterephthalic acid diester isolated may be
further purified by a conventional purification means such as
crystallization and column chromatography.
[0072] Examples of the tetrafluoroterephthalic acid diester include
dimethyl 2,3,5,6-tetrafluoroterephthalate, diethyl
2,3,5,6-tetrafluoroterephthalate, di(n-propyl)
2,3,5,6-tetrafluoroterephthalate, diisopropyl
2,3,5,6-tetrafluoroterephthalate, di(n-butyl)
2,3,5,6-tetrafluoroterephthalate and di(tert-butyl)
2,3,5,6-tetrafluoroterephthalate.
EXAMPLES
[0073] The present invention will be illustrated in more detail by
Examples below. The present invention is not limited to these
Examples.
Example 1
[0074] Into a 500 mL flask equipped with a reflux condenser, 30 g
of potassium fluoride (purchased from NAKALAI TESQUE, INC.;
commodity code 28611-95) and 400 g of methanol were charged. The
obtained mixture was heated and refluxed for 30 minutes to prepare
a methanol solution of potassium fluoride. To the obtained methanol
solution of potassium fluoride, 100 g of toluene was added and the
obtained mixture was concentrated at 90 to 100.degree. C. to remove
200 g of a mixed solution of methanol and toluene. After 100 g of
toluene was added to the concentrate, the obtained mixture was
further concentrated at 90 to 100.degree. C. to remove 200 g of a
mixed solution of methanol and toluene. After 110 g of sulfolane
was added to the obtained concentrate, the obtained mixture was
concentrated at 130.degree. C. to remove a mixed solution of
methanol and toluene, and was further heated to 140.degree. C. to
continue the concentration until the distillate was hardly
distilled at all. After that, residual toluene was removed by
reducing to 6 kPa at 140.degree. C. to obtain a potassium fluoride
dispersion essentially consisting of potassium fluoride and
sulfolane.
[0075] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 22 g of tetrachloroterephthaloyl dichloride. The
obtained mixture was kept for 3 hours at 145.degree. C. with
stirring. The obtained reaction mixture was cooled to 100.degree.
C. and then, 100 g of toluene was added thereto to cool to room
temperature. A part of the obtained mixture was sampled to analyze
with gas chromatography mass spectrometry apparatus. The formation
of 2,3,5,6-tetrafluoroterephthaloyl difluoride as the main product
and the disappearance of tetrachloroterephthaloyl dichloride were
confirmed.
[0076] To the obtained reaction mixture, 15 g of methanol was added
dropwise and the mixture was stirred for 12 hours at room
temperature while removing hydrogen fluoride generated as
by-product out the flask using nitrogen gas. The precipitated solid
was separated by filtration and the separated solid was washed with
10 g of toluene. The filtrate and wash liquid were mixed and 100 g
of water was added thereto and 300 mg of potassium carbonate was
added thereto to adjust pH of the aqueous layer to 7. The obtained
mixture was separated to an organic layer and an aqueous layer. The
obtained organic layer was analyzed with gas chromatography
internal standard method. The yield of dimethyl
2,3,5,6-tetrafluoroterephthalate was 88%, the yield of dimethyl
2,3,5-trifluoro-6-chloroterephthalate was 8% and the yield of
dimethyl dichlorodifluoroterephthalate was 5%.
Example 2
[0077] Into a 200 mL flask equipped with a reflux condenser, 110 g
of sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the solution obtained by
dissolving 30 g of potassium fluoride, which was the same as used
in Example 1, in 350 g of methanol was added dropwise together with
removing distilled methanol out the system. The addition of all
amount of the methanol solution of potassium fluoride dropwise was
finished and methanol was hardly distilled out at all, and then, 50
g of toluene was added to the obtained concentrate. The
concentration was continued at the same temperature to remove a
mixed solution of methanol and toluene. After methanol was hardly
distilled out, residual toluene was removed by reducing to 6 kPa to
obtain a potassium fluoride dispersion essentially consisting of
potassium fluoride and sulfolane.
[0078] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 22 g of tetrachloroterephthaloyl dichloride. The
obtained mixture was kept for 3.5 hours at 145.degree. C. with
stirring. The obtained reaction mixture was cooled to 100.degree.
C. and then, 100 g of toluene was added thereto. After the obtained
mixture was cooled to room temperature, 15 g of methanol was added
dropwise and the mixture was stirred for 12 hours at room
temperature while removing hydrogen fluoride generated as
by-product out the flask using nitrogen gas. The precipitated solid
was separated by filtration and the separated solid was washed with
10 g of toluene. The filtrate and wash liquid were mixed and 100 g
of water was added thereto and 400 mg of potassium carbonate was
added thereto to adjust pH of the aqueous layer to 7. The obtained
mixture was separated to an organic layer and an aqueous layer. The
obtained organic layer was concentrated with an evaporator
(operation pressure: 10 to 100 kPa, water bath temperature: 30 to
50.degree. C.) to obtain the oily residue. The obtained residue was
mixed with 110 g of water and then, the obtained mixture was
further concentrated with an evaporator (operation pressure: 10 to
100 kPa, water bath temperature: 30 to 50.degree. C.) to remove an
azeotrope of toluene and water. The concentrated residue was cooled
to room temperature and the precipitated crystals were separated by
filtration. The obtained crystals were dried to obtain 17.2 g of
pale yellow crystals of dimethyl 2,3,5,6-tetrafluoroterephthalate.
The crystals were analyzed with gas chromatography area percentage
method. The purity of dimethyl 2,3,5,6-tetrafluoroterephthalate was
93%. Yield: 93%.
Example 3
[0079] Into a 200 mL flask equipped with a reflux condenser, 110 g
of sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the solution obtained by
dissolving 30 g of potassium fluoride, which was the same as used
in Example 1, in 350 g of methanol was added dropwise together with
removing distilled methanol out the system. The addition of all
amount of the methanol solution of potassium fluoride dropwise was
finished and methanol was hardly distilled out at all, and then,
the concentration was further continued at 160.degree. C. at 2.7
kPa to obtain a potassium fluoride dispersion essentially
consisting of potassium fluoride and sulfolane.
[0080] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 22 g of tetrachloroterephthaloyl dichloride. The
obtained mixture was kept for 3.5 hours at 145.degree. C. with
stirring. The obtained reaction mixture was cooled to 100.degree.
C. and then, 100 g of toluene was added thereto. After the obtained
mixture was cooled to room temperature, 15 g of methanol was added
dropwise to the cooled mixture and the resultant mixture was
stirred for 12 hours at room temperature while removing hydrogen
fluoride generated as by-product out the flask using nitrogen gas.
The precipitated solid was separated by filtration and the
separated solid was washed with 10 g of toluene. The filtrate and
wash liquid were mixed and 100 g of water was added thereto and 600
mg of potassium carbonate was added thereto to adjust pH of the
aqueous layer to 7. The obtained mixture was separated to an
organic layer and an aqueous layer. The obtained organic layer was
concentrated with an evaporator (operation pressure: 10 to 100 kPa,
water bath temperature: 30 to 50.degree. C.) to obtain the oily
residue. The obtained residue was mixed with 110 g of water and
then, the obtained mixture was further concentrated with an
evaporator (operation pressure: 10 to 100 kPa, water bath
temperature: 30 to 50.degree. C.) to remove an azeotrope of toluene
and water. The concentrated residue was cooled to room temperature
and the precipitated crystals were separated by filtration. The
obtained crystals were dried to obtain 17.4 g of pale yellow
crystals of dimethyl 2,3,5,6-tetrafluoroterephthalate. The crystals
were analyzed with gas chromatography area percentage method. The
purity of dimethyl 2,3,5,6-tetrafluoroterephthalate was 92%. Yield:
93%.
Example 4
[0081] Into a 50 mL flask equipped with a reflux condenser, 480 mg
of potassium fluoride, which was the same as used in Example 1, and
5 g of methanol were charged. The obtained mixture was heated and
refluxed for 30 minutes to prepare a methanol solution of potassium
fluoride. To the obtained methanol solution of potassium fluoride,
5 g of toluene was added and then, the obtained mixture was
concentrated at 90 to 100.degree. C. at normal pressure to remove a
mixed solution of methanol and toluene. After methanol was hardly
distilled at all, 1.7 g of dimethylsulfone was added to the
concentrate. The obtained mixture was further concentrated at
140.degree. C. to obtain a potassium fluoride dispersion
essentially consisting of potassium fluoride and
dimethylsulfone.
[0082] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 340 mg of tetrachloroterephthaloyl dichloride. The
obtained mixture was kept for 2 hours at 145.degree. C. with
stirring. The obtained reaction mixture was cooled to room
temperature and then, 10 g of methanol was added. The solids in the
obtained mixture were pulverized and then, the mixture was stirred
at room temperature for 1 hour. To the mixture, 10 g of ethyl
acetate was added and the resultant mixture was analyzed with gas
chromatography internal standard method. The yield of dimethyl
2,3,5,6-tetrafluoroterephthalate was 75%, the yield of dimethyl
2,3,5-trifluoro-6-chloroterephthalate was 12% and the yield of
dimethyl dichlorodifluoroterephthalate was 11%.
Comparative Example 1
[0083] Into a 50 mL flask equipped with a reflux condenser, 960 mg
of potassium fluoride, which was the same as used in Example 1, and
2 g of methanol were charged. Although the obtained mixture was
heated and refluxed for 30 minutes, potassium fluoride was not
dissolved perfectly in methanol. To the obtained mixture, 3 g of
sulfolane and 3 g of toluene were added and then, the obtained
mixture was concentrated at 130.degree. C. at normal pressure to
remove a mixed solution of methanol and toluene. After methanol was
hardly distilled at all, the mixture was further concentrated at
140.degree. C. to obtain a potassium fluoride dispersion
essentially consisting of potassium fluoride and sulfolane.
[0084] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 680 mg of tetrachloroterephthaloyl dichloride. The
obtained mixture was kept for 4 hours at 150.degree. C. with
stirring. The obtained reaction mixture was cooled to room
temperature and then, 5 g of methanol was added. The resultant
mixture was stirred at room temperature for 1 hour. To the obtained
mixture, 10 g of ethyl acetate was added and the resultant mixture
was analyzed with gas chromatography internal standard method. The
yield of dimethyl 2-fluoro-3,5,6-trichloroterephthalate was 1%, and
the yield of dimethyl 2,3,5,6-tetrachloroterephthalate was 98%. The
generation of dimethyl 2,3,5,6-tetrafluoroterephthalate, dimethyl
2,3,5-trifluoro-6-chloroterephthalate and dimethyl
dichlorodifluoroterephthalate could not be confirmed.
Example 5
[0085] Into a 50 mL flask equipped with a reflux condenser, 25 g of
sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the solution obtained by
dissolving 4.5 g of potassium fluoride, which was the same as used
in Example 1, in 60 g of methanol was added dropwise together with
removing distilled methanol out the system. The addition of all
amount of the methanol solution of potassium fluoride dropwise was
finished and methanol was hardly distilled out at all, and then, 10
g of toluene was added to the concentrate. The concentration was
further continued to remove a mixed solution of methanol and
toluene. After that, residual toluene was removed by reducing to 6
kPa at the same temperature to obtain a potassium fluoride
dispersion essentially consisting of potassium fluoride and
sulfolane.
[0086] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 5 g of 2,4-dichloronitrobenzene. The obtained
mixture was kept for 10 hours at 180.degree. C. with stirring. The
obtained reaction mixture was cooled to 100.degree. C. and then,
100 g of toluene was added thereto. The obtained mixture was cooled
to room temperature. The precipitated solid was separated by
filtration and the separated solid was washed with 10 g of toluene.
The filtrate and wash liquid were mixed and the obtained solution
was analyzed with gas chromatography internal standard method. The
yield of 2,4-difluoronitrobenzene was 92% and the yield of
chlorofluoronitrobenzene was 8%.
Example 6
[0087] Into a 50 mL flask equipped with a reflux condenser, 25 g of
sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the solution obtained by
dissolving 4.5 g of potassium fluoride, which was the same as used
in Example 1, in 60 g of methanol was added dropwise together with
removing distilled methanol out the system. The addition of all
amount of the methanol solution of potassium fluoride dropwise was
finished and methanol was hardly distilled out at all, and then,
the concentration was further conducted at 160.degree. C. at 2.7
kPa to obtain a potassium fluoride dispersion essentially
consisting of potassium fluoride and sulfolane. The potassium
fluoride dispersion was analyzed with gas chromatography area
comparison method. The amount of methanol was 0.02% by weight or
less per 1 part by weight of sulfolane.
[0088] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 5 g of 2,4-dichloronitrobenzene. The obtained
mixture was kept for 8 hours at 180.degree. C. with stirring. The
obtained reaction mixture was cooled to 100.degree. C. and then,
100 g of toluene was added thereto. The obtained mixture was cooled
to room temperature. The precipitated solid was separated by
filtration and the separated solid was washed with 10 g of toluene.
The filtrate and wash liquid were mixed and the obtained solution
was analyzed with gas chromatography internal standard method. The
yield of 2,4-difluoronitrobenzene was 90% and the yield of
chlorofluoronitrobenzene was 10%.
Example 7
[0089] Into a 50 mL flask equipped with a reflux condenser, 25 g of
dimethylsulfoxide was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the solution obtained by
dissolving 2.8 g of potassium fluoride, which was the same as used
in Example 1, in 40 g of methanol was added dropwise together with
removing distilled methanol out the system. The addition of all
amount of the methanol solution of potassium fluoride dropwise was
finished and methanol was hardly distilled out at all, and then,
residual methanol was removed together with 10 g of
dimethylsulfoxide by reducing to 6 kPa to obtain a potassium
fluoride dispersion essentially consisting of potassium fluoride
and dimethylsulfoxide.
[0090] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 5 g of 4-chloronitrobenzene. The obtained mixture
was kept for 4 hours at 185.degree. C. with stirring. The obtained
reaction mixture was cooled to 100.degree. C. and then, 100 g of
toluene was added thereto. The obtained mixture was cooled to room
temperature. The precipitated solid was separated by filtration and
the separated solid was washed with 10 g of toluene. The filtrate
and wash liquid were mixed and the obtained solution was analyzed
with gas chromatography internal standard method. The yield of
4-fluoronitrobenzene was 97% and the recovery of
4-chloronitrobenzene was 3%.
Example 8
[0091] Into a 50 mL flask equipped with a reflux condenser, 25 g of
N-methyl-2-pyrolidone was charged and the inner temperature thereof
was adjusted at 140.degree. C. To this, the solution obtained by
dissolving 2.8 g of potassium fluoride, which was the same as used
in Example 1, in 40 g of methanol was added dropwise together with
removing distilled methanol out the system. The addition of all
amount of the methanol solution of potassium fluoride dropwise was
finished and methanol was hardly distilled out at all, and then,
residual methanol was removed together with 10 g of
N-methyl-2-pyrolidone by reducing to 6 kPa to obtain a potassium
fluoride dispersion essentially consisting of potassium fluoride
and N-methyl-2-pyrolidone.
[0092] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 5.5 g of benzyl bromide. The obtained mixture was
kept for 4 hours at 120.degree. C., with stirring. The obtained
reaction mixture was cooled to 100.degree. C. and then, 100 g of
toluene was added thereto. The obtained mixture was cooled to room
temperature. The precipitated solid was separated by filtration and
the separated solid was washed with 10 g of toluene. The filtrate
and wash liquid were mixed and the obtained solution was analyzed
with gas chromatography internal standard method. The yield of
benzyl fluoride was 93% and the recovery of benzyl bromide was
3%.
Example 9
[0093] Into a 500 mL flask, 350 g of methanol and 29 g of potassium
hydroxide were charged. The mixture was stirred at room temperature
to prepare a methanol solution of potassium hydroxide. To the
prepared methanol solution of potassium hydroxide, 22 g of 47% by
weight hydrofluoric acid was added dropwise while cooling to keep
at an inner temperature of 30.degree. C. or less to prepare a
potassium fluoride solution.
[0094] Into a 200 mL flask equipped with a reflux condenser, 110 g
of sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the above-mentioned potassium
fluoride solution was added dropwise together with removing
distilled mixed solution of methanol and water. The addition of all
amount of the potassium fluoride solution dropwise was finished and
methanol and water were hardly distilled out at all, and then, 10 g
of toluene was added thereto. The concentration was further
continued to remove a mixed solution of methanol, water and
toluene. After the distillate was hardly distilled out, residual
toluene was removed at the same temperature by reducing to 6 kPa to
obtain a potassium fluoride dispersion essentially consisting of
potassium fluoride and sulfolane.
[0095] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 22 g of tetrachloroterephthaloyl dichloride. The
obtained mixture was kept for 4 hours at 145.degree. C. with
stirring. The obtained reaction mixture was cooled to 100.degree.
C. and then, 100 g of toluene was added thereto and the obtained
mixture was cooled to room temperature. To the obtained mixture, 15
g of methanol was added dropwise and the mixture was stirred for 12
hours at room temperature while removing hydrogen fluoride
generated as by-product out the flask using nitrogen gas. The
precipitated solid was separated by filtration and the separated
solid was washed with 10 g of toluene. The filtrate and wash liquid
were mixed and 100 g of water was added thereto and 600 mg of
potassium carbonate was added thereto to adjust pH of the aqueous
layer to 7. The obtained mixture was separated to an organic layer
and an aqueous layer. The obtained organic layer was concentrated
with an evaporator (operation pressure: 10 to 100 kPa, water bath
temperature: 30 to 50.degree. C.) to obtain the oily residue. The
obtained residue was mixed with 110 g of water and then, the
obtained mixture was further concentrated with an evaporator
(operation pressure: 10 to 100 kPa, water bath temperature: 30 to
50.degree. C.) to remove an azeotrope of toluene and water. The
concentrated residue was cooled to room temperature and the
precipitated crystals were separated by filtration. The obtained
crystals were dried to obtain 17.6 g of pale yellow crystals of
dimethyl 2,3,5,6-tetrafluoroterephthalate. The crystals were
analyzed with gas chromatography area percentage method. The purity
of dimethyl 2,3,5,6-tetrafluoroterephthalate was 87%. Yield:
89%.
Example 10
[0096] Into a 200 mL flask, 53 g of methanol and 4.4 g of potassium
hydroxide were charged. The mixture was stirred at room temperature
to prepare a methanol solution of potassium hydroxide. To the
prepared methanol solution of potassium hydroxide, 3.3 g of 47% by
weight hydrofluoric acid was added dropwise while cooling to keep
at an inner temperature of 30.degree. C. or less to prepare a
potassium fluoride solution.
[0097] Into a 50 mL flask equipped with a reflux condenser, 25 g of
sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the above-mentioned potassium
fluoride solution was added dropwise together with removing
distilled mixed solution of methanol and water out the system. The
addition of all amount of the potassium fluoride solution dropwise
was finished and methanol and water were hardly distilled out at
all, and then, the concentration was continued at 160.degree. C. at
2.7 kPa to remove residual methanol and water to obtain a potassium
fluoride dispersion essentially consisting of potassium fluoride
and sulfolane.
[0098] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 5 g of 2,4-dichloronitrobenzene. The obtained
mixture was kept for 10 hours at 180.degree. C. with stirring. The
obtained reaction mixture was cooled to 100.degree. C. and then,
100 g of toluene was added thereto and the obtained mixture was
cooled to room temperature. The precipitated solid was separated by
filtration and the separated solid was washed with 10 g of toluene.
The filtrate and wash liquid were mixed to analyze with gas
chromatography internal standard method. The Yield of
2,4-difluoronitrobenzene was 89% and the yield of
chlorofluoronitrobenzene was 9%.
Example 11
[0099] Into a 200 mL flask, 35 g of methanol and 2.7 g of potassium
hydroxide were charged. The mixture was stirred at room temperature
to prepare a methanol solution of potassium hydroxide. To the
prepared methanol solution of potassium hydroxide, 2 g of 47% by
weight hydrofluoric acid was added dropwise while cooling to keep
at an inner temperature of 30.degree. C. or less to prepare a
potassium fluoride solution.
[0100] Into a 50 mL flask equipped with a reflux condenser, 25 g of
N-methyl-2-pyrolidone was charged and the inner temperature thereof
was adjusted at 140.degree. C. To this, the above-mentioned
potassium fluoride solution was added dropwise together with
removing distilled a mixed solution of methanol and water out the
system. The addition of all amount of the potassium fluoride
solution dropwise was finished and methanol and water were hardly
distilled out at all, and then, residual methanol and water were
removed together with 10 g of N-methyl-2-pyrolidone by reducing to
6 kPa to obtain a potassium fluoride dispersion essentially
consisting of potassium fluoride and N-methyl-2-pyrolidone.
[0101] The potassium fluoride dispersion cooled at 100.degree. C.
was mixed with 5.5 g of benzyl bromide. The obtained mixture was
kept for 4 hours at 120.degree. C. with stirring. The obtained
reaction mixture was cooled to 100.degree. C. and then, 100 g of
toluene was added thereto. The obtained mixture was cooled to room
temperature. The precipitated solid was separated by filtration and
the separated solid was washed with 10 g of toluene. The filtrate
and wash liquid were mixed and the obtained solution was analyzed
with gas chromatography internal standard method. The yield of
benzyl fluoride was 94% and the recovery of benzyl bromide was
3%.
Example 12
[0102] Into a 500 mL flask equipped with a reflux condenser, 75 g
of sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the solution obtained by
dissolving 17.8 g of potassium fluoride, which was the same as used
in Example 1, in 209 g of methanol was added dropwise together with
removing distilled methanol out the system. The addition of all
amount of the methanol solution of potassium fluoride dropwise was
finished and methanol was hardly distilled out at all, and then,
the concentration was further conducted at 160.degree. C. at 2.7
kPa to obtain a potassium fluoride dispersion essentially
consisting of potassium fluoride and sulfolane.
[0103] To a 120 mL autoclave, 10.3 g of 4,5,6-trichloropyrimidine
was charged. The above-mentioned potassium fluoride dispersion was
added thereto and the autoclave was sealed. After the inner
pressure thereof was adjusted to 0.5 MPa at room temperature using
nitrogen, the reaction was conducted at an inner temperature of
220.degree. C. for 10 hours. The inner pressure after completion of
the reaction was 0.82 MPa at 220.degree. C. The reaction mixture
was cooled to room temperature and the supernatant solution was
analyzed with gas chromatography internal standard method (internal
standard: methyl isobutyl ketone). The yield of
4,5,6-trifluoropyrimidine was 50% and the yield of
4,6-difluoro-5-chloropyrimidine was 26%.
Example 13
[0104] Into a 200 mL flask equipped with a reflux condenser, 70 g
of sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the solution obtained by
dissolving 13.6 g of potassium fluoride (purchased from ALDRICH;
spray-dry products; commodity code 307599) and 1.0 g of water in
180 g of methanol was added dropwise together with removing
distilled a mixed solution of methanol and water out the system.
The addition of all amount of the potassium fluoride solution
dropwise was finished and methanol was hardly distilled out at all,
and then, the concentration was further conducted at 160.degree. C.
at 2.7 kPa to obtain a potassium fluoride dispersion essentially
consisting of potassium fluoride and sulfolane.
[0105] The potassium fluoride dispersion cooled at 140.degree. C.
was mixed with 10 g of tetrachloroterephthaloyl dichloride. The
obtained mixture was kept for 3 hours at 145.degree. C. with
stirring. The obtained reaction mixture was cooled to 100.degree.
C. and then, 20 g of toluene was added thereto. The obtained
mixture was cooled to room temperature. To the obtained mixture,
9.4 g of methanol was added dropwise and the mixture was stirred
for 1 hour at room temperature while removing hydrogen fluoride
generated as by-product out the flask using nitrogen gas out the
flask. The precipitated solid was separated by filtration and the
separated solid was washed with 50 g of toluene. The filtrate and
wash liquid were mixed and the obtained solution was analyzed with
gas chromatography internal standard method. The yield of dimethyl
2,3,5,6-tetrafluoroterephthalate was 82%, the yield of dimethyl
2,3,5-trifluoro-6-chloroterephthalate was 7% and the yield of
dimethyl dichlorodifluoroterephthalate was 5%.
Comparative Example 2
[0106] Into a 200 mL flask equipped with a reflux condenser, 13.6 g
of potassium fluoride, which was the same as used in the
above-mentioned Example 13, 1.0 g of water and 20 g of methanol
were charged. Although the obtained mixture was refluxed for 30
minutes, potassium fluoride was not dissolved perfectly to obtain
suspension of potassium fluoride. To the obtained suspension of
potassium fluoride, 70 g of sulfolane and 22 g of toluene were
added and then, the obtained mixture was concentrated at an inner
temperature of 130.degree. C. to remove a mixed solution of
methanol, water and toluene out the system. After methanol was
hardly distilled at all, the mixture was further concentrated at
140.degree. C. to obtain a potassium fluoride dispersion
essentially consisting of potassium fluoride and sulfolane.
[0107] The potassium fluoride dispersion cooled at 140.degree. C.
was mixed with 10 g of tetrachloroterephthaloyl dichloride. The
obtained mixture was kept for 3 hours at 145.degree. C. with
stirring. The obtained reaction mixture was cooled to 100.degree.
C. and then, 20 g of toluene was added thereto. The obtained
mixture was cooled to room temperature. To the obtained mixture,
9.4 g of methanol was added dropwise and the mixture was stirred
for 1 hour at room temperature while removing hydrogen fluoride
generated as by-product out the flask using nitrogen gas out the
flask. The precipitated solid was separated by filtration and the
separated solid was washed with 50 g of toluene. The filtrate and
wash liquid were mixed and the obtained solution was analyzed with
gas chromatography internal standard method. The yield of dimethyl
2,3,5,6-tetrafluoroterephthalate was 1%, the yield of dimethyl
2,3,5-trifluoro-6-chloroterephthalate was 10%, the yield of
dimethyl dichlorodifluoroterephthalate was 8%, the yield of
dimethyl 2-fluoro-3,5,6-trichloroterephthalate was 10% and the
yield of 2,3,5,6-tetrachloroterephthalate was 4%.
Example 14
[0108] Into a 500 mL flask equipped with a reflux condenser, 300 g
of sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the solution obtained by
dissolving 58 g of potassium fluoride, which was the same as used
in the above-mentioned Example 13, 3 g of water in 772 g of
methanol was added dropwise together with removing distilled mixed
solution of methanol and water out the system. The addition of all
amount of the potassium fluoride solution dropwise was finished and
methanol was hardly distilled out at all, and then, the
concentration was further conducted at 160.degree. C. at 2.7 kPa to
obtain a potassium fluoride dispersion essentially consisting of
potassium fluoride and sulfolane. The number of particles and the
volumetric particle size distribution of potassium fluoride in the
obtained potassium fluoride dispersion were measured using the FBRM
"D600L" to get particle size distribution data using a
data-processing system with "D600L". The obtained volumetric
particle size distribution data was shown in FIG. 1. The average
particle size of volumetric was 19.7 .mu.m.
[0109] After completion of the measurement, the potassium fluoride
dispersion was filtrated and the obtained particles of potassium
fluoride was washed with 100 g of ethyl acetate and dried at
80.degree. C. at 1.3 kPa. The dried particles of potassium fluoride
was subjected to the pretreatment by Pt--Pd evaporation method and
form observation was conducted under 10 kV of accelerating voltage
using FE-SEM "S-800" manufactured by HITACHI, Ltd. to confirm that
the particle diameter of the initial particles of potassium
fluoride was 0.1 to 5 .mu.m. The results were shown in FIG. 5 and
FIG. 6. FIG. 5 was a SEM image at 2,000-fold magnification for
shooting and FIG. 6 was a SEM image at 5,000-fold magnification for
shooting.
Comparative Example 3
[0110] Into a 500 mL flask equipped with a reflux condenser, 83 g
of potassium fluoride, which was the same as used in the
above-mentioned Example 13, 5 g of water and 119 g of methanol were
charged. Although the obtained mixture was refluxed for 30 minutes,
potassium fluoride was not dissolved perfectly to obtain suspension
of potassium fluoride. To the obtained suspension of potassium
fluoride, 300 g of sulfolane and 130 g of toluene were added and
then, the obtained mixture was concentrated at an inner temperature
of 130.degree. C. to remove a mixed solution of methanol, water and
toluene out the system. After methanol was hardly distilled at all,
the mixture was further concentrated at 140.degree. C. to obtain a
potassium fluoride dispersion essentially consisting of potassium
fluoride and sulfolane. The number of particles and the volumetric
particle size distribution of potassium fluoride in the obtained
potassium fluoride dispersion were measured using the FBRM "D600L"
to get particle size distribution data using a data-processing
system with "D600L". The obtained volumetric particle size
distribution data was shown in FIG. 2. The average particle size of
volumetric was 29.7 .mu.m.
[0111] After completion of the measurement, the potassium fluoride
dispersion was filtrated and the obtained particles of potassium
fluoride was washed with 150 g of ethyl acetate and dried at
80.degree. C. at 1.3 kPa. The dried particles of potassium fluoride
was subjected to the pretreatment by Pt--Pd evaporation method and
form observation was conducted under 10 kV of accelerating voltage
using FE-SEM "S-800" manufactured by HITACHI, Ltd. The result was
shown in FIG. 7. FIG. 7 was a SEM image at 2,000-fold magnification
for shooting.
Comparative Example 4
[0112] Potassium fluoride, which was the same as used in the
above-mentioned Example 13, was dispersed in sulfolane to prepare a
potassium fluoride dispersion. The number of particles and the
volumetric particle size distribution of potassium fluoride in the
obtained potassium fluoride dispersion were measured using the FBRM
"D600L" to get particle size distribution data using a
data-processing system with "D600L". The obtained volumetric
particle size distribution data was shown in FIG. 3. The average
particle size of volumetric was 127.2 .mu.m.
[0113] After completion of the measurement, the potassium fluoride
dispersion was filtrated and the obtained particles of potassium
fluoride was washed with 150 g of ethyl acetate and dried at
80.degree. C. at 1.3 kPa. The dried particles of potassium fluoride
was subjected to the pretreatment by Pt--Pd evaporation method and
form observation was conducted under 10 kV of accelerating voltage
using FE-SEM "S-800" manufactured by HITACHI, Ltd. The result was
shown in FIG. 8. FIG. 8 was a SEM image at 1,000-fold magnification
for shooting.
Example 15
[0114] Into a 500 mL flask equipped with a reflux condenser, 300 g
of sulfolane was charged and the inner temperature thereof was
adjusted at 140.degree. C. To this, the solution obtained by
dissolving 58 g of potassium fluoride, which was the same as used
in the above-mentioned Example 1, in 772 g of methanol was added
dropwise together with removing distilled methanol out the system.
The addition of all amount of the potassium fluoride solution
dropwise was finished and methanol was hardly distilled out at all,
and then, the concentration was further conducted at 160.degree. C.
at 2.7 kPa to obtain a potassium fluoride dispersion essentially
consisting of potassium fluoride and sulfolane. The number of
particles and the volumetric particle size distribution of
potassium fluoride in the obtained potassium fluoride dispersion
were measured using the FBRM "D600L" to get particle size
distribution data using a data-processing system with "D600L". The
obtained volumetric particle size distribution data was shown in
FIG. 4. The average particle size of volumetric was 20.2 .mu.m.
[0115] After completion of the measurement, the potassium fluoride
dispersion was filtrated and the obtained particles of potassium
fluoride was washed with 100 g of ethyl acetate and dried at
80.degree. C. at 1.3 kPa. The dried particles of potassium fluoride
was subjected to the pretreatment by Pt--Pd evaporation method and
form observation was conducted under 10 kV of accelerating voltage
using FE-SEM "S-800" manufactured by HITACHI, Ltd. to confirm that
the particle diameter of the initial particles of potassium
fluoride was 0.1 to 5 .mu.m. The results were shown in FIG. 9 and
FIG. 10. FIG. 9 was a SEM image at 2,000-fold magnification for
shooting and FIG. 10 was a SEM image at 5,000-fold magnification
for shooting.
INDUSTRIAL APPLICABILITY
[0116] The potassium fluoride dispersion of the present invention
has high reactivity and fluorine-containing organic compounds,
which are important as various chemicals such as pharmaceuticals
and agrichemicals and its synthetic intermediates, can be produced
efficiently without using an expensive phase transfer catalyst, and
therefore, it is industrially advantageous.
* * * * *