U.S. patent application number 10/773264 was filed with the patent office on 2004-08-12 for production process and use for propargyl alcohol and its intermediate.
This patent application is currently assigned to SHOWA DENKO K.K.. Invention is credited to Aoki, Takanori, Hiro, Toshitaka, Ishikami, Haruki, Ohe, Takami, Saito, Makoto.
Application Number | 20040158107 10/773264 |
Document ID | / |
Family ID | 27566965 |
Filed Date | 2004-08-12 |
United States Patent
Application |
20040158107 |
Kind Code |
A1 |
Aoki, Takanori ; et
al. |
August 12, 2004 |
Production process and use for propargyl alcohol and its
intermediate
Abstract
Processes are provided for producing propargyl alcohol in an
industrially advantageous manner. One of the processes comprises
reaction of 1,2,3-trichloropropane with 3 equivalents or more of an
alkali compound to produce propargyl alcohol. The other process
comprises (1) a first step of reaction of 2,3-dichloro-1-propanol
with an amine to produce chloroallyl alcohol, and (2) a second step
of reaction of the chloroallyl alcohol obtained in the above step
(1) with an alkali compound to produce propargyl alcohol.
Inventors: |
Aoki, Takanori;
(Kawasaki-shi, JP) ; Ohe, Takami; (Kawasaki-shi,
JP) ; Ishikami, Haruki; (Kawasaki-shi, JP) ;
Saito, Makoto; (Kawasaki-shi, JP) ; Hiro,
Toshitaka; (Kawasaki-shi, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 Pennsylvania Avenue, NW
Washington
DC
20037-3213
US
|
Assignee: |
SHOWA DENKO K.K.
|
Family ID: |
27566965 |
Appl. No.: |
10/773264 |
Filed: |
February 9, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10773264 |
Feb 9, 2004 |
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09822488 |
Apr 2, 2001 |
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6710213 |
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60230717 |
Sep 7, 2000 |
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60216521 |
Jul 6, 2000 |
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Current U.S.
Class: |
568/840 |
Current CPC
Class: |
C07C 29/124 20130101;
C07C 33/042 20130101; C07C 33/423 20130101; C07C 33/042 20130101;
C07C 33/423 20130101; C07C 29/124 20130101; C07C 29/124 20130101;
C07C 29/58 20130101; C07C 29/58 20130101; C07C 29/58 20130101 |
Class at
Publication: |
568/840 |
International
Class: |
C07C 029/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2000 |
JP |
2000-98454 |
Jun 5, 2000 |
JP |
2000-167604 |
Mar 19, 2001 |
JP |
2001-77641 |
Mar 19, 2001 |
JP |
2001-77642 |
Claims
What is claimed is:
1. A propargyl alcohol reduced in formaldchyde, wherein the
formaldehyde content is 1,000 ppm or less.
2. The propargyl alcohol as claimed in claim 1, wherein the
formaldehyde content is 100 ppm or less.
3. The propargyl alcohol as claimed in claim 1, wherein the
formaldehyde content is 5 ppm or less.
4. The propargyl alcohol as claimed in claim 1, further containing
a polymerization inhibitor.
5. The propargyl alcohol as claimed in claim 4, wherein the
polymerization inhibitor is at least one compound selected from the
group consisting of phenol compounds, vinyl compounds,
sulfur-containing compounds, nitrogen-containing compounds, and
metal compounds.
6. A resin, which is obtained by reaction of the propargyl alcohol
according to any one of claims 1 to 5.
7. A resin composition, comprising the resin according to claim
6.
8. A cationic electrodeposition coating composition containing the
resin composition according to claim 7.
9. The propargyl alcohol as claimed in any one of claims 1 to 3,
which is obtained by a process comprising reacting
1,2,3-trichloropropane with 3 equivalents or more of an alkali
compound in the presence of a quaternary ammonium salt and/or a
polymerization inhibitor, wherein said reaction comprises a first
step of reacting 1,2,3-trichloropropane with an alkali compound to
produce 2-chloroallyl alcohol and a second step of reacting said
2-chloroallyl alcohol with an alkali compound to produce propargyl
alcohol.
10. The propargyl alcohol as claimed in any one of claims 1 to 3,
which is obtained by a process comprising reacting
1,2,3-trichloropropane with an aqueous solution containing 3
equivalents or more of an alkali compound in the presence of a
quaternary ammonium salt and/or a polymerization inhibitor, wherein
said reaction comprises a first step of reacting
1,2,3-trichloropropane with an aqueous solution containing an
alkali compound to produce 2-chloroallyl alcohol and a second step
of reacting said 2-chloroallyl alcohol with an aqueous solution
containing an alkali compound to produce propargyl alcohol.
11. The propargyl alcohol as claimed in any one of claims 1 to 3,
which is obtained by a process comprising the following two steps:
(1) a step of reacting 2,3-dichloro-1-propanol with an amine to
produce chloroallyl alcohol, and (2) a step of reacting the
chloroallyl alcohol obtained in said step (1) with an alkali
compound to produce propargyl alcohol.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a Divisional Application of pending prior
application Ser. No. 09/822,488 filed Apr. 2, 2001, which is an
application filed under 35 U.S.C. .sctn.111(a) claiming benefit
pursuant to 35 U.S.C. .sctn.119(e)(1) of the filing date of
Provisional Application 60/230,717 filed Sep. 7, 2000 and
Provisional Application 60/216,521 filed Jul. 6, 2000 pursuant to
35 U.S.C. .sctn.111(b); the disclosures of all of which are
incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a process for producing
propargyl alcohol and its intermediate which are useful as a
starting material of organic products, and also relates to the use
thereof.
RELATED BACKGROUND ART
[0003] With respect to the process for producing propargyl alcohol,
for example, a method of reacting acetylene with formaldehyde is
known and described in JP-A-64-90145 (the term "JP-A" as used
herein means an "unexamined published Japanese patent
application").
[0004] However, this method has a problem in that highly explosive
acetylene is used.
[0005] In order to solve the problem, a method of producing
propargyl alcohol in which chloroallyl alcohol is
dehydrochlorinated by reacting with an alkali metal hydroxide is
known and described, for example, in U.S. Pat. No. 3,383,427, Khim.
Prom-st., 19, 59 (1987), and J. Org. Chem., 15, 654 (1950). With
respect to the process for producing chloroallyl alcohol used as a
starting material, a method of reacting 1,2,3-trichloropropane with
an alkali is known and described, for example, in U.S. Pat. No.
2,285,329.
[0006] However, for producing propargyl alcohol, a sufficiently
large amount of an amine compound or ammonia must be added in
addition to the alkali metal hydroxide. In the case of ammonia, the
ammonia is used in an amount as large as 5 to 20 mol per mol of
2-chloroallyl alcohol.
[0007] In such a process, the produced propargyl alcohol is liable
to decompose or polymerize to lower the productivity, and the
isolated and purified propargyl alcohol is also thermally unstable,
being liable to decompose or polymerize.
OBJECT OF THE INVENTION
[0008] The present invention has been made under these
circumstances and the object of the present invention is to provide
a process for producing propargyl alcohol and its intermediate
chloroallyl alcohol in an industrially advantageous manner.
DISCLOSURE OF THE INVENTION
[0009] As a result of extensive investigations to overcome the
above-described problems, the present inventors have found that
propargyl alcohol can be produced in a high yield by reacting
1,2,3-trichloropropane with 3 equivalents or more of an alkali
compound, and have completed the present invention (first
embodiment).
[0010] Also, the present inventors have found that a process for
producing propargyl alcohol through a step of reacting
2,3-dichloro-1-propanol with an amine to produce chloroallyl
alcohol can attain the object, and have completed the present
invention (second embodiment).
[0011] The present invention provides a production process and a
use for propargyl alcohol and its intermediate, described in (1) to
(41) below.
[0012] (1) A process for producing propargyl alcohol, comprising
reacting 1,2,3-trichloropropane with 3 equivalents or more of an
alkali compound.
[0013] (2) The process for producing propargyl alcohol as described
in (1) above, wherein the reaction is performed at a temperature
selected from the range of 20.degree. C. to 200.degree. C.
[0014] (3) The process for producing propargyl alcohol as described
in (1) or (2) above, wherein the reaction is performed under
pressure.
[0015] (4) The process for producing propargyl alcohol as described
in (1) above, wherein the reaction comprises a first step of
reacting 1,2,3-trichloropropane with an alkali compound to produce
2-chloroallyl alcohol and a second step of reacting the
2-chloroallyl alcohol with an alkali compound to produce propargyl
alcohol.
[0016] (5) The process for producing propargyl alcohol as described
in (4) above, wherein the first step and the second step are
continuously performed.
[0017] (6) A process for producing propargyl alcohol, comprising
reacting 1,2,3-trichloropropane with an aqueous solution containing
3 equivalents or more of an alkali compound.
[0018] (7) The process for producing propargyl alcohol as described
in (6) above, wherein the reaction is performed at a temperature
selected from the range of 20.degree. C. to 200.degree. C.
[0019] (8) The process for producing propargyl alcohol as described
in (6) or (7) above, wherein the reaction is performed under
pressure.
[0020] (9) The process for producing propargyl alcohol as described
in (6) above, wherein the reaction comprises a first step of
reacting 1,2,3-trichloropropane with an aqueous solution containing
an alkali compound to produce 2-chloroallyl alcohol and a second
step of reacting the 2-chloroallyl alcohol with an aqueous solution
containing an alkali compound to produce propargyl alcohol.
[0021] (10) The process for producing propargyl alcohol as
described in (9) above, wherein the first step and the second step
are continuously performed.
[0022] (11) The process for producing propargyl alcohol as
described in (1) or (6) above, wherein the alkali compound is at
least one compound selected from the group consisting of
hydroxides, oxides, carbonates, hydrogencarbonates, phosphates and
hydrogenphosphates of an alkali metal and/or an alkaline earth
metal.
[0023] (12) The process for producing propargyl alcohol as
described in (1) or (6) above, wherein the alkali compound is a
hydroxide, an oxide and/or a carbonate of an alkali metal and/or an
alkaline earth metal.
[0024] (13) The process for producing propargyl alcohol as
described in (1) or (6) above, wherein the reaction is performed in
the presence of a quaternary ammonium salt.
[0025] (14) A process for producing propargyl alcohol, comprising
the following two steps:
[0026] (1) a step of reacting 2,3-dichloro-1-propanol with an amine
to produce chloroallyl alcohol, and
[0027] (2) a step of reacting the chloroallyl alcohol obtained in
the step (1) with an alkali compound to produce propargyl
alcohol.
[0028] (15) The process for producing propargyl alcohol as
described in (14) above, wherein the steps (1) and (2) are
continuously performed.
[0029] (16) The process for producing propargyl alcohol as
described in (14) or (15) above, wherein the step (1) is performed
at a temperature of 20 to 300.degree. C. and the step (2) is
performed at a temperature of 20 to 200.degree. C.
[0030] (17) The process for producing propargyl alcohol as
described in (14) or (15) above, wherein the step (1) and/or (2) is
performed under pressure.
[0031] (18) The process for producing propargyl alcohol as
described in (14) or (15) above, wherein the alkali compound in the
step (2) is at least one compound selected from the group
consisting of hydroxides, oxides, carbonates, hydrogencarbonates,
phosphates and hydrogenphosphates of an alkali metal and an
alkaline earth metal.
[0032] (19) The process for producing propargyl alcohol as
described in (1) or (6) or (14) above, wherein the reaction is
performed in the presence of a polymerization inhibitor.
[0033] (20) The process for producing propargyl alcohol as
described in (1) or (6) or (14) above, wherein the process further
comprises a purification step performed in the presence of a
polymerization inhibitor.
[0034] (21) The process for producing propargyl alcohol as
described in (19) above, wherein the polymerization inhibitor is at
least one compound selected from the group consisting of phenol
derivatives, vinyl compounds, sulfur-containing compounds,
nitrogen-containing compounds, and metal compounds.
[0035] (22) A process for producing chloroallyl alcohol, comprising
reacting 2,3-dichloro-1-propanol with an amine.
[0036] (23) The process for producing chloroallyl alcohol as
described in (22) above, wherein the reaction is performed at a
temperature selected from the range of 20.degree. C. to 300.degree.
C. (24) The process for producing chloroallyl alcohol as described
in (22) or (23) above, wherein the reaction is performed under
pressure.
[0037] (25) The process for producing chloroallyl alcohol as
described in (22) above, wherein the reaction is performed in the
presence of a polymerization inhibitor.
[0038] (26) The process for producing chloroallyl alcohol as
described in (25) above, wherein the polymerization inhibitor is at
least one compound selected from the group consisting of phenol
derivatives, vinyl compounds, sulfur-containing compounds,
nitrogen-containing compounds, and metal compounds.
[0039] (27) Propargyl alcohol, containing a polymerization
inhibitor.
[0040] (28) The propargyl alcohol as described in (27) above,
wherein the polymerization inhibitor is at least one compound
selected from the group consisting of phenol derivatives, vinyl
compounds, sulfur-containing compounds, nitrogen-containing
compounds, and metal compounds.
[0041] (29) Propargyl alcohol reduced in formaldehyde, wherein the
formaldehyde content is 1,000 ppm or less.
[0042] (30) Propargyl alcohol reduced in formaldehyde, wherein the
formaldehyde content is 100 ppm or less.
[0043] (31) Propargyl alcohol reduced in formaldehyde, wherein the
formaldehyde content is 5 ppm or less.
[0044] (32) A resin composition, comprising a resin obtained using
the propargyl alcohol reduced in formaldehyde as described in any
one of (29) to (31) above.
[0045] (33) A resin composition, comprising a resin obtained using
the propargyl alcohol produced by the production process as
described in any one of (1), (6) and (14) above.
[0046] (34) The resin composition as described in (32) above,
wherein the formaldehyde content is 1,000 ppm or less.
[0047] (35) The resin composition as described in (32) above,
wherein the formaldehyde content is 100 ppm or less.
[0048] (36) The resin composition as described in (32) above,
wherein the formaldehyde content is 5 ppm or less.
[0049] (37) A resin composition for a cationic electrodeposition
coating, comprising a resin obtained using the propargyl alcohol
reduced in formaldehyde as described in any one of (29) to (31)
above.
[0050] (38) A resin composition for a cationic electrodeposition
coating, comprising a resin obtained using propargyl alcohol
produced by the production process as described in any one of (1),
(6) and (14) above.
[0051] (39) The resin composition for a cationic electrodeposition
coating as described in (37) above, wherein the formaldehyde
content is 1,000 ppm or less.
[0052] (40) The resin composition for a cationic electrodeposition
coating as described in (37) above, wherein the formaldehyde
content is 100 ppm or less.
[0053] (41) The resin composition for a cationic electrodeposition
coating as described in (37) above, wherein the formaldehyde
content is 5 ppm or less.
[0054] To be brief, the present invention provides "a process for
producing propargyl alcohol by reacting 1,2,3-trichloropropane with
3 equivalents or more of an alkali compound", "a process for
producing propargyl alcohol, comprising a step of reacting
2,3-dichloro-1-propanol with an amine to produce chloroallyl
alcohol and a step of reacting the chloroallyl alcohol obtained in
the previous step with an alkali compound to produce propargyl
alcohol", "a process for producing chloroallyl alcohol, comprising
reacting 2,3-dichloro-1-propanol with an amine", "propargyl alcohol
containing a polymerization inhibitor", "propargyl alcohol having a
formaldehyde content of 1,000 ppm or less", "a resin composition
comprising a resin obtained using propargyl alcohol produced by the
above-described process" and "a resin composition for a cationic
electrodeposition coating, comprising a resin obtained using
propargyl alcohol produced by the above-described process".
BEST MODE FOR CARRYING OUT THE INVENTION
[0055] The present invention is described in detail below.
[0056] [A] The first embodiment of the present invention is
described firstly.
[0057] The 1,2,3-trichloropropane for use in the present invention
is not particularly limited and may be a commercially or
industrially available product. Also, 1,2,3-trichloropropane
obtained by adding chlorine to an allyl alcohol or an allyl
chloride can be used. With respect to the purity,
1,2,3-trichloropropane is preferably purified to a high purity but
may contain impurities as long as these impurities have no effect
on the reaction and can be removed by the purification process.
[0058] The alkali compound for use in the present invention is
suitably a compound containing at least one element selected from
alkali metals and alkaline earth metals. The alkali metal is
selected from Li, Na, K, Rb and Cs, and the alkaline earth metal is
selected from Be, Mg, Ca, Sr and Ba. Examples of the compound in
which such an element is contained include hydroxides, oxides,
carbonates, hydrogencarbonates, phosphates, hydrogenphosphates,
oxyhalogenides, basic carbonates, carboxylates and organometal
complexes. The alkali metal is preferably Na or K, the alkaline
earth metal is preferably Mg or Ca, and the alkali compound is
preferably a hydroxide, an oxide, a carbonate, a hydrogencarbonate,
a phosphate or a carboxylate thereof. Out of these alkali
compounds, one compound may be used alone or two or more may be
used in combination at an arbitrary ratio.
[0059] In addition, the alkali compound for use in the present
invention may be ammonia or an organic base such as amine.
Furthermore, a mixture of a compound containing at least one
element selected from alkali metals and alkaline earth metals with
an organic base may also be used.
[0060] The alkali compound is used, in terms of the element
selected from alkali metals and alkaline earth metals, in 3
equivalents or more to 1,2,3-trichloropropane. The equivalent is
suitably 1 in the case of an alkali metal and it is suitably 2 in
the case of an alkaline earth metal. The alkali compound is
preferably used in the range from 3 to 20 equivalents, more
preferably from 3 to 12 equivalents, still more preferably from 3
to 8 equivalent. If the equivalent ratio of alkali
compound/1,2,3-trichloropropane exceeds 20, there arise problems,
for example, decomposition of propargyl alcohol occurs due to
excess alkali compound or recovery of a large amount of unreacted
alkali compound is necessary, whereas if the equivalent ratio of
alkali compound/1,2,3-trichloropropane is less than 3, there arise
problems, for example, recovery of unreacted intermediate is
necessary or the yield decreases.
[0061] The production process of the present invention can be
performed in the presence of a quaternary ammonium salt. The
quaternary ammonium salt is a compound represented by the formula
[R.sup.1R.sup.2R.sup.3R.sup.4N]X (wherein R.sup.1 to R.sup.4 each
represents a group selected from an alkyl group or an aryl group,
and X represents a monovalent anion), and specific examples thereof
include quaternary ammonium salts such as tetramethylammonium
chloride, benzyltriethylammonium chloride, tetrabutylammonium
chloride, trioctylmethylammonium chloride, trioctylallylammonium
chloride, phenyltriethylammonium chloride, tetraethylammonium
bromide, triethylcyclohexylammonium bromide, tetrabutylammonium
bromide and tetrabutylammonium hydrogensulfate. Out of these
compounds, one may be used alone or two or more may be used in
combination at an arbitrary ratio.
[0062] By adding the quaternary ammonium salt, production of
propargyl alcohol can proceed at a high rate and productivity is
improved. The molar ratio of the quaternary ammonium salt to the
1,2,3-trichloropropane (quaternary ammonium
salt/1,2,3-trichloropropane) is from 0.0001 to 10, preferably from
0.001 to 1.
[0063] The process of the present invention can be performed in the
presence of a solvent. As the solvent, water, an organic solvent,
or the mixtures of water and an organic solvent can be used.
Examples of the organic solvent used include hydrocarbon, ether,
ketone, amide, nitrile, ester and alcohol, however, the organic
solvent is not limited thereto as long as it exerts no effect on
the reaction. The solvent is preferably water, and the amount of
the water is appropriately selected according to the conditions
such as kind, amount of the alkali compound used or reaction
temperature. The mass ratio of the organic solvent to
1,2,3-trichloropropane (solvent/1,2,3-trichloropropane) is suitably
from 0 to 1,000, preferably from 0 to 100.
[0064] The production process of the present invention can be
performed in the presence of a polymerization inhibitor. The
polymerization inhibitor for use in the present invention includes
phenol derivatives, vinyl compounds, sulfur-containing compounds,
nitrogen-containing compounds, and metal compounds, but is not
limited thereto.
[0065] The phenol derivatives include phenol, 4-t-butylphenol,
4-methoxyphenol, 2,5-di-t-butylhydroquinone,
2-t-butyl-4-methylphenol, 2,6-di-t-butylphenol,
2,4,6-trimethylphenol, and 2-i-propyl-5-methylpheno- l, but are not
limited thereto.
[0066] The vinyl compounds include styrene, o-chlorostyrene,
m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene,
p-bromostyrene, o-nitrostyrene, m-nitrostyrene, p-nitrostyrene,
o-cyanostyrene, m-cyanostyrene, p-cyanostyrene, divinylbenzene,
p-styrenesulfonic acid, sodium p-styrenesulfonate, 2-vinylpyridine,
4-vinylpyridine, 2-vinyl-5-ethylpyridine, 2-methyl-5-vinylpyridine,
acrylamide, methyl acrylate, and methyl methacrylate, but are not
limited thereto.
[0067] The sulfur-containing compounds include phenothiazine,
2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, sodium
salt of 2-mercaptobenzothiazole, and thiourea, but are not limited
thereto.
[0068] The nitrogen-containing compounds include
N-nitroso-diphenylamine, 4-nitrosodiphenylamine,
2-methyl-2-nitrosopropane, .alpha.-phenyl(t-butyl)nitrone,
N-phenyl-N'-i-propylphenylenediamine,
5,5-dimethyl-N-phenyl-N'-i-propylphenylenediamine,
1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and nitrosobenzene, but
are not limited thereto.
[0069] The metals of the metal compounds include manganese, zinc,
lithium, iron, and copper, but are not limited thereto. The metal
compounds include halides, oxyhalides, phosphates,
hydrogenphosphates, oxides, hydroxides, carbonates,
hydrogencarbonates, basic carbonates, carboxylates, and organometal
complexes, but are not limited thereto.
[0070] The polymerization inhibitor may be used alone or two or
more may be used in combination at an arbitrary ratio.
[0071] The added polymerization inhibitor will prevent side
reactions such as decomposition and polymerization of propargyl
alcohol to improve the productivity, and may reduce formaldehyde
formation caused by decomposition, polymerization, or the like of
propargyl alcohol.
[0072] In the reaction of 1,2,3-trichloropropane with the alkali
compound in the present invention, the polymerization inhibitor is
used in a molar ratio of polymerization
inhibitor/1,2,3-trichloropropane ranging from 1.0.times.10.sup.-8
to 10.0, preferably from 1.0.times.10.sup.-7 to 1.0.
[0073] In the process of the present invention, the reaction
temperature during the production of propargyl alcohol is suitably
from 20.degree. C. to 200.degree. C., preferably from 50.degree. C.
to 170.degree. C. If the reaction temperature exceeds 200.degree.
C., decomposition, polymerization or the like of propargyl alcohol
takes place and this is not preferred, whereas if the reaction
temperature is less than 20.degree. C., the reaction proceeds at a
low rate and the productivity or the like disadvantageously
decreases.
[0074] The reaction pressure is suitably from 10 kPa to 1,000 kPa,
preferably from 50 kPa to 500 kPa. If the reaction pressure is less
than 10 kPa or exceeds 1,000 kPa, implementation of the production
process is industrially difficult and this is not preferred.
[0075] The process of the present invention can also be performed
through a first step of reacting 1,2,3-trichloropropane with an
alkali compound to produce 2-chloroallyl alcohol and a second step
of reacting the 2-chloroallyl alcohol with an alkali compound to
produce propargyl alcohol. At this time, the first step and the
second step may be performed respectively in the presence of the
solvent.
[0076] Also, the first step and the second step may be performed
continuously, namely in one stage, or may be performed stepwise by
varying the conditions as necessary. In each of the first step and
the second step, the reaction temperature can be selected from the
range of 20.degree. C. to 200.degree. C. and the pressure is from
10 kPa to 1,000 kPa.
[0077] The starting materials for use in the present invention each
may be introduced into a reactor by any known method and the method
is not particularly limited.
[0078] For example, a method of previously introducing
1,2,3-trichloropropane and an alkali compound into a reactor and
then initiating the reaction or a method of performing the reaction
while separately introducing 1,2,3-trichloropropane and an alkali
compound may be used. The alkali compound may also be introduced
after previously mixing it with 1,2,3-trichloropropane and for
example, a method of previously mixing an alkali compound and
1,2,3-trichloropropane by a static mixer (see, Kagaku Sochi
(Chemical Apparatus), 74-78 (May, 1994)) and then introducing the
mixture into a reactor may be used. In the case of using an organic
solvent, a method of introducing 1,2,3-trichloropropane and an
alkali compound after diluting them with an organic solvent may be
used.
[0079] In the production process of the present invention, the
reaction may be performed by initially adding 3 equivalents or more
of an alkali compound all at once but may also be performed
stepwise by adding the alkali compound in parts in the first step
where 1,2,3-trichloropropane is reacted with an alkali compound to
produce 2-chloroallyl alcohol and in the second step where the
2-chloroallyl alcohol is reacted with an alkali compound to produce
propargyl alcohol. The amount of the alkali compound added in each
step can be appropriately determined according to the conditions
such as reaction temperature.
[0080] The quaternary ammonium salt for use in the present
invention may be introduced into a reactor by any known method and
the method is not particularly limited. For example, a method of
previously introducing the quaternary ammonium salt into a reactor
and then initiating the reaction or a method of adding the
quaternary ammonium salt on demand may be used. Furthermore, as
described above, in the case of using water or an organic solvent
as a solvent, a method of introducing the quaternary ammonium salt
after diluting it with the solvent may be used.
[0081] In the present invention, the heat generated upon reaction
of 1,2,3-trichloropropane with an alkali compound may be discharged
out of the system using water, warm water or heating medium,
whereby the reaction temperature can be kept constant. Also, the
heat discharged with water, warm water or heating medium may be
used as a heat source for other equipment and this is
profitable.
[0082] As described above, the reaction in the practice of the
present invention may be performed by any known method and for
example, a batch system, a semibatch system or a continuous system
may used. The propargyl alcohol obtained by the present invention
can be separated and purified by a known method and for example, a
method such as distillation or rectification can be used. The
prodution process of the present invention may include a
purification step in the presence of a polymerization
inhibitor.
[0083] The polymerization inhibitor is used in the purification
step in a molar ratio of the polymerization inhibitor to the
propargyl alcohol (polymerization inhibitor/propargyl alcohol)
ranging from 1.0.times.10.sup.-8 to 10.0, preferably from
1.0.times.10.sup.-7 to 1.0. The propargyl alcohol may be separated
and purified in the presence of the polymerization inhibitor used
in the reaction of the 1,2,3-trichloropropane with the alkali
compound, or a polymerization inhibitor may be newly added. The
newly added polymerization inhibitor may be the same one as in the
reaction of the 1,2,3-trichloropropane with the alkali compound, or
may be different from that according to the conditions and
uses.
[0084] The polymerization inhibitor may be added to the propargyl
alcohol produced by the above-described process, or the propargyl
alcohol purified as described above in the present invention. The
polymerization inhibitor is added at a molar ratio of the
polymerization inhibitor to the propargyl alcohol (polymerization
inhibitor/propargyl alcohol) ranging from 1.0.times.10.sup.-8 to
10.0, preferably from 1.0.times.10.sup.-7 to 1.0. In the case where
the propargyl alcohol after purification retains the polymerization
inhibitor added in the purification step, an additional
polymerization inhibitor may be added newly or not be added. The
newly added polymerization inhibitor may be the same as the one
used in the production process or in the purification step, or
different from that according to the conditions or the use
thereof.
[0085] The addition of the polymerization inhibitor will retard
side reactions of the propargyl alcohol such as decomposition and
polymerization to improve the productivity, and further may reduce
the amount of formaldehyde formed by decomposition, polymerization,
or the like.
[0086] [B] The second embodiment of the present invention is
described in detail below.
[0087] The process for producing propargyl alcohol of the present
invention is characterized by comprising the following two steps,
where the step (1) is a novel reaction:
[0088] (1) a step of reacting 2,3-dichloro-1-propanol with an amine
to produce chloroallyl alcohol; and
[0089] (2) a step of reacting the chloroallyl alcohol obtained in
the above-described step with an alkali compound to produce
propargyl alcohol.
[0090] The chloroallyl alcohol obtained in the step (1) of the
present invention means 2-chloroallyl alcohol, cis-3-chloroallyl
alcohol, trans-3-chloroallyl alcohol or a mixture of two or more
thereof.
[0091] The 2,3-dichloro-1-propanol for use in the step (1) of the
present invention is not particularly limited and may be a
commercially or industrially available product. Also,
2,3-dichloro-1-propanol obtained by reacting an allyl alcohol with
chlorine or allyl chloride with hypochlorous acid in the production
process of epichlorohydrin may be used. With respect to the purity,
2,3-dichloro-1-propanol is preferably purified to a high purity but
may contain impurities as long as these impurities have no effect
on the reaction and can be removed by the purification process.
[0092] The amine for use in the step (1) of the present invention
is not particularly limited and may be a commercially or
industrially available product. An ammonia or a primary amine,
secondary amine or tertiary amine represented by the formula
NR.sup.1R.sup.2R.sup.3 may be used as the amine. The amine may also
contain an imino group and a polyamine having two or more amino
groups in the molecule, such as diamine or triamine, may be used.
Furthermore, a cyclic amine may also be used.
[0093] Specific examples of the monoamine include methylamine,
dimethylamine, trimethylamine, ethylamine, diethylamine,
triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine,
i-propylamine, di-i-propylamine, tri-i-propylamine, n-butylamine,
di-n-butylamine, tri-n-butylamine, i-butylamine, di-i-butylamine,
tri-i-butylamine, sec-butylamine, di-sec-butylamine,
tri-sec-butylamine, tert-butylamine, di-tert-butylamine,
tri-tert-butylamine, allylamine, diallylamine, triallylamine,
cyclohexylamine, dicyclohexylamine, tricyclohexylamine,
n-octylamine, di-n-octylamine, tri-n-octylamine, benzylamine,
dibenzylamine, tribenzylamine, diaminopropylamine,
2-ethylhexylamine, 3-(2-ethylhexyloxy)propylamine,
3-methoxypropylamine, 3-ethoxypropylamine,
3-(diethylamino)propylamine, bis(2-ethylhexyl)amine,
3-(dibutylamino)propylamine, .alpha.-phenylethylamine,
.beta.-phenylethylamine, aniline, N-methylaniline,
N,N-dimethylaniline, diphenylamine, triphenylamine, o-toluidine,
m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine,
o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline,
m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline,
p-nitroaniline, 2,4-dinitroaniline, 2,4,6-trinitroaniline,
p-aminobenzoic acid, sulfanilic acid, sulfanilamide,
monoethanolamine, diethanolamine and triethanolamine.
[0094] Examples of the diamine include 1,2-diaminoethane,
N,N,N',N'-tetraethyl-1,2-diaminoethane,
N,N,N',N'-tetraethyl-1,2-diaminoe- thane, 1,3-diaminopropane,
N,N,N',N'-tetramethyl-1,2-diaminopropane,
N,N,N',N'-tetraethyl-1,2-diaminopropane, 1,4-diaminobutane,
N-methyl-1,4-diaminobutane, 1,2-diaminobutane,
N,N,N',N'-tetramethyl-1,2-- diaminobutane,
3-aminopropyldimethylamine, 1,6-diaminohexane,
3,3-diamino-N-methyldipropylamine, 1,2-phenylenediamine,
1,3-phenylenediamine, 1,4-phenylenediamine and benzidine.
[0095] Examples of the triamine include 2,4,6-triaminophenol,
1,2,3-triaminopropane, 1,2,3-triaminobenzene 1,2,4-triaminobenzene
and 1,3,5-triaminobenzene. Examples of the tetramine include
.beta.,.beta.',.beta."-triaminotriethylamine.
[0096] Specific examples of the cyclic amine include pyrrole,
pyridine, pyrimidine, pyrrolidine, piperidine, purine, imidazole,
oxazole, thiazole, pyrazole, 3-pyrroline, quinoline, isoquinoline,
carbazole, piperazine, pyridazine, 1,2,3-triazine, 1,2,4-triazine,
1,3,5-triazine, 1,2,3-triazole, 1,2,5-triazole, 1,2,4-triazole,
1,3,4-triazole and morpholine. The amine for use in the present
invention is by no means limited to the above-described compounds
and, for example, an asymmetric compound having different kinds of
substituents, such as ethylmethylamine, may also be used. Also, one
amine may be used alone or two or more amines may be used in
combination at an arbitrary ratio.
[0097] Among these, preferred are ammonia, methylamine,
dimethylamine, trimethylamine, ethylamine, diethylamine,
triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine,
i-propylamine, di-i-propylamine, tri-i-propylamine, n-butylamine,
di-n-butylamine, tri-n-butylamine, i-butylamine, di-i-butylamine,
tri-i-butylamine, sec-butylamine, di-sec-butylamine,
tri-sec-butylamine, tert-butylamine, di-tert-butylamine,
tri-tert-butylamine, cyclohexylamine, dicyclohexylamine,
tricyclohexylamine, benzylamine, dibenzylamine, tribenzylamine,
diaminopropylamine, aniline, N-methylaniline, N,N-dimethylaniline,
diphenylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine,
m-anisidine, p-anisidine, o-chloroaniline, m-chloroaniline,
p-chloroaniline, p-aminobenzoic acid, sulfanilic acid,
ethylmethylamine, monoethanolamine, diethanolamine,
triethanolamine, 1,2-diaminoethane,
N,N,N',N'-tetramethyl-1,2-diaminoethane,
N,N,N',N'-tetraethyl-1,2-diaminoethane, 1,3-diaminopropane,
N,N,N',N'-tetramethyl-1,2-diaminopropane,
N,N,N',N'-tetraethyl-1,2-diamin- opropane, 1,4-diaminobutane,
N-methyl-1,4-diaminobutane, 1,2-diaminobutane,
N,N,N',N'-tetramethyl-1,2-diaminobutane,
3-aminopropyldimethylamine, 1,6-diaminohexane,
3,3-diamino-N-methyldiprop- ylamine, 1,2-phenylenediamine,
1,3-phenylenediamine, 1,4-phenylenediamine, benzidine,
2,4,6-triaminophenol, 1,2,3-triaminopropane, 1,2,3-triaminobenzene,
1,2,4-triaminobenzene, 1,3,5-triaminobenzene,
.beta.,.beta.',.beta."-triaminotriethylamine, pyrrole, pyridine,
pyrimidine, pyrrolidine, piperidine, purine, imidazole, oxazole,
thiazole, pyrazole, 3-pyrroline, quinoline, isoquinoline,
carbazole, piperazine, pyridazine, 1,3,5-triazine, 1,2,3-triazole,
1,2,5-triazole and morpholine.
[0098] In the step (1) of the process of the present invention, the
reaction temperature at the production of chloroallyl alcohol is
suitably from 20.degree. C. to 300.degree. C., preferably from
50.degree. C. to 250.degree. C. If the reaction temperature exceeds
300.degree. C., decomposition, polymerization or the like of
chloroallyl alcohol takes place, whereas if the reaction
temperature is less than 20.degree. C., the reaction proceeds at a
low rate and the productivity or the like disadvantageously
decreases.
[0099] The reaction pressure in the step (1) of the present
invention is suitably from 10 kPa to 10,000 kPa, preferably from 50
kPa to 5,000 kPa. If the reaction pressure is less than 10 kPa or
exceeds 10,000 kPa, implementation of the production process is
industrially difficult and this is not preferred.
[0100] The molar ratio between the 2,3-dicholo-1-propanol and the
amine (amine/2,3-dicholo-1-propanol) in the step (1) of the present
invention is suitably from 0.001 to 1,000, preferably from 0.01 to
100. If the molar ratio of amine/2,3-dicholo-1-propanol exceeds
1,000, there arise problems, for example, recovery of excess
unreacted organic base becomes necessary, whereas if the molar
ratio of amine/2,3-dichloro-1-propanol is less than 0.001, there
arise problems, for example, recovery of excess
2,3-dichloro-1-propanol becomes necessary. Furthermore, the amine
for use in the present invention is preferably used in a
stoichiometric amount or more, however, the present invention is
not limited thereto.
[0101] The step (1) of the present invention can also be performed
in the presence of a solvent. Examples of the solvent include
water, hydrocarbon, ether, ketone, amide, nitrile, ester and
alcohol, however, the solvent is not limited thereto and the
above-described amine can also be used as the solvent.
[0102] The mass ratio of the solvent to the 2,3-dichloro-1-propanol
(solvent/2,3-dichloro-1-propanol) is suitably from 0 to 10,000,
preferably from 0 to 1,000, however, the mass ratio is not limited
thereto.
[0103] The heat generated upon reaction of 2,3-dichloro-1-propanol
with an amine may be discharged out of the system using water, warm
water or heating medium, whereby the reaction temperature can be
kept constant. Also, the heat discharged with water, warm water or
heating medium may be used as a heat source for other equipment and
this is profitable.
[0104] In practicing the step (1) of the present invention, the
reaction may be performed by any known method and for example, a
batch system, a semibatch system or a continuous system may be
used, however, the method is not limited thereto. Also, the
starting material for use in the present invention may be
introduced into a reactor by any known method and the method is not
particularly limited. For example, a method of previously
introducing 2,3-dichloro-1-propanol and an amine into a reactor and
then initiating the reaction or a method of performing the reaction
while introducing 2,3-dichloro-1-propanol and an amine may be
used.
[0105] In addition, the amine may also be introduced after
previously mixing it with 2,3-dichloro-1-propanol and for example,
a method of previously mixing an amine and 2,3-dichloro-1-propanol
by a static mixer (see, Kagaku Sochi (Chemical Apparatus), 74-78
(May, 1994)) and then introducing the mixture into a reactor may be
used, however, the method is not limited thereto. A method of
separately introducing 2,3-dichloro-1-propanol and an amine may
also be used. With respect to the 2,3-dichloro-1-propanol, a method
of introducing it after the dilution with a solvent may also be
used, however, the method is not limited thereto.
[0106] The chloroallyl alcohol obtained by the present invention
includes 2-chloroallyl alcohol, cis-3-chloroallyl alcohol and
trans-3-chloroallyl alcohol. These three kinds of isomers can be
separated and purified by a known method and for example, a method
such as distillation or rectification can be used. However, in the
case of using these three kinds of isomers for the production of
propargyl alcohol in the step (2) of the present invention, the
mixture of chloroallyl alcohols obtained in the step (1) can be
used as the starting material without separating those three kinds
of isomers.
[0107] The step (2) in the production process of the present
invention is described below.
[0108] The step (2) is a step for producing propargyl alcohol by
reacting chloroallyl alcohol obtained in the above-described step
(1) with an alkali compound. The step (2) may be performed by any
known method. For example, propargyl alcohol can be produced by
reacting chloroallyl alcohol with an alkali compound in the same
manner as in U.S. Pat. No. 3,383,427, Khim. Prom-st., 4, 251
(1987), J. Org. Chem., 15, 654 (1950).
[0109] The alkali compound for use in the step (2) of the present
invention is not particularly limited and may be a commercially or
industrially available product. The alkali compound for use in the
present invention is suitably a compound containing at least one
element selected from alkali metals and alkaline earth metals. Out
of these alkali compounds, one compound may be used alone or two or
more may be used in combination at an arbitrary ratio.
[0110] The alkali compound for use in the step (2) of the present
invention may also be an ammonia or an amine. Furthermore, a
mixture of a compound containing at least one element selected from
alkali metals and alkaline earth metals with an ammonia or an amine
may also be used.
[0111] In the step (2) of the present invention, the reaction
temperature at the production of propargyl alcohol is suitably from
20.degree. C. to 200.degree. C., preferably from 50.degree. C. to
170.degree. C. If the reaction temperature exceeds 200.degree. C.,
decomposition, polymerization or the like of propargyl alcohol
takes place and this is not preferred, whereas if the reaction
temperature is less than 20.degree. C., the reaction proceeds at a
low rate and the productivity or the like disadvantageously
decreases.
[0112] The step (2) of the present invention can also be performed
in the presence of a solvent. Examples of the solvent include
water, hydrocarbon, ether, ketone, amide, nitrile, ester and
alcohol, however, the solvent is not limited thereto. In the case
of practicing the steps (1) and (2) in the presence of a solvent, a
solvent having no effect in either step, if possible, the same
solvent, is preferably selected. The mass ratio between the solvent
and chloroallyl alcohol (chloroallyl alcohol/solvent) is suitably
from 0 to 10,000, preferably from 0 to 1,000, however, the mass
ratio is not limited thereto.
[0113] The reaction pressure in the step (2) of the present
invention is suitably from 10 kPa to 10,000 kPa, preferably from 50
kPa to 5,000 kPa. If the reaction pressure is less than 10 kPa or
exceeds 10,000 kPa, implementation of the production process is
industrially difficult and this is not preferred.
[0114] The molar ratio between the chloroallyl alcohol and the
alkali compound (alkali compound/chloroallyl alcohol) for use in
the present invention is suitably from 0.001 to 1,000, preferably
from 0.01 to 100. If the molar ratio of alkali compound/chloroallyl
alcohol exceeds 1,000, there arise problems, for example, recovery
of excess unreacted alkali compound becomes necessary, whereas if
the molar ratio of alkali compound/chloroallyl alcohol is less than
0.001, there arise problems, for example, recovery of excess
chloroallyl alcohol becomes necessary. Furthermore, the alkali
compound is preferably used in a stoichiometric amount or more,
however, the present invention is not limited thereto.
[0115] The heat generated upon reaction of chloroallyl alcohol with
an alkali compound may be discharged out of the system using water,
warm water or heating medium, whereby the reaction temperature can
be kept constant. Also, the heat discharged with water, warm water
or heating medium may be used as a heat source for other equipment
and this is profitable.
[0116] In practicing the step (2) of the present invention, the
reaction may be performed by any known method and for example, a
batch system, a semibatch system or a continuous system may be
used. Also, the starting material may be introduced into a reactor
by any known method and the method is not particularly limited. For
example, a method of previously introducing chloroallyl alcohol and
an alkali compound into a reactor and then initiating the reaction
or a method of performing the reaction while continuously
introducing chloroallyl alcohol and an alkali compound may be
used.
[0117] The alkali compound may also be introduced after previously
mixing it with chloroallyl alcohol and for example, a method of
previously mixing an alkali compound and chloroallyl alcohol by a
static mixer (see, Kagaku Sochi (Chemical Apparatus), 74-78 (May,
1994)) and then introducing the mixture into a reactor may be used,
however, the method is not limited thereto.
[0118] A method of separately introducing chloroallyl alcohol and
an alkali compound may also be used. A method of introducing
chloroallyl alcohol after diluting it with a solvent may also be
used, however, the method is not limited thereto. In the same
manner, a method of introducing an alkali compound after diluting
it with a solvent may be used, however, the method is not limited
thereto.
[0119] The production process of propargyl alcohol of the present
invention is described above by referring to the case where the
step (1) and the step (2) are performed separately. However, in the
present invention, the first step (1) of reacting
2,3-dichloro-1-propanol with an amine to produce chloroallyl
alcohol and the second step (2) of reacting the chloroallyl alcohol
obtained in the step (1) with an alkali compound to produce
propargyl alcohol may also be continuously performed, namely in one
stage, and in this case, the reactions may be performed stepwise by
varying the conditions.
[0120] Both of the above two steps in the production process of the
present invention may be performed in the presence of a
polymerization inhibitor.
[0121] The polymerization inhibitor for use in the present
invention includes phenol derivatives, vinyl compounds,
sulfur-containing compounds, nitrogen-containing compounds, and
metal compounds, but is not limited thereto. The added
polymerization inhibitor will prevent side reactions such as
decomposition and polymerization of chloroallyl alcohol and
propargyl alcohol to improve the productivity, and may reduce the
formaldehyde formation caused by decomposition, polymerization, or
a like reaction of propargyl alcohol.
[0122] In the reaction of the 2,3-dichloro-1-propanol with the
amine in the present invention, the polymerization inhibitor is
used in a molar ratio of the polymerization inhibitor to the
2,3-dichloro-1-propanol (polymerization
inhibitor/2,3-dichloro-1-propanol) ranging from 1.0.times.10.sup.-8
to 10.0, preferably from 10.times.10.sup.-7 to 1.0. The
polymerization inhibitor may be used alone or two or more may be
used in combination at an arbitrary ratio.
[0123] The step (2) may be performed in the presence of the
polymerization inhibitor used in the step (1), or a polymerization
inhibitor may be added newly. The newly added polymerization
inhibitor may be the same one as in the reaction of the
2,3-dichloro-1-propanol with the amine, or may be different one
selected according to the conditions. The polymerization inhibitor
is used at a ratio to the chloroallyl alcohol (polymerization
inhibitor/chloroallyl alcohol) ranging from 1.0.times.10.sup.-8 to
10.0, preferably from 1.0.times.10.sup.-7 to 1.0.
[0124] The propargyl alcohol obtained according to the present
invention can be separated and purified by a known method and for
example, a method such as distillation or rectification can be
used. The production process of the present invention may include a
purification step in the presence of a polymerization inhibitor.
The polymerization inhibitor is used in the purification step at
the ratio to the propargyl alcohol (polymerization
inhibitor/propargyl alcohol) ranging from 1.0.times.10.sup.-8 to
10.0, preferably from 1.0.times.10.sup.-7 to 1.0 .
[0125] The propargyl alcohol may be separated and purified in the
presence of the polymerization inhibitor used in the reaction of
the chloroallyl alcohol with the alkali compound, or a
polymerization inhibitor may be newly added. The newly added
polymerization inhibitor may be the same one as used in the
reaction of the chloroallyl alcohol with the alkali compound, or
may be different from that according to the conditions and uses
thereof.
[0126] The added polymerization inhibitor will retard side
reactions of propargyl alcohol such as decomposition and
polymerization to improve the productivity, and further may reduce
the amount of formaldehyde formed by decomposition, polymerization,
or a like reaction of the propargyl alcohol.
[0127] To the propargyl alcohol obtained through the production
process or the purification step of the present invention, a
polymerization inhibitor may be added. The polymerization inhibitor
is used at the ratio to the propargyl alcohol (polymerization
inhibitor/propargyl alcohol) ranging from 1.0.times.10.sup.-8 to
10.0, preferably from 1.0.times.10.sup.-7 to 1.0.
[0128] If the propargyl alcohol after purification contains the
polymerization inhibitor added in the purification step, the
polymerization inhibitor need not be added, but may be newly added.
The newly added polymerization inhibitor may be the same one as in
the production process or the purification step, or may be
different from that according to the conditions and uses
thereof.
[0129] [C] The propargyl alcohol of the present invention (the
first embodiment and the second embodiment) is described below.
[0130] The propargyl alcohol of the present invention is
characterized in that the formaldehyde content is 1,000 ppm or
less. The formaldehyde content is preferably 500 ppm or less, more
preferably 100 ppm or less, most preferably 5 ppm or less.
Formaldehyde has strong chemical affinity and coagulates or
denatures proteins of cell protoplasm to adversely affect the human
body, for example, the cell is inhibited from all functions and
killed. Thus, from the standpoint of environmental issue, propargyl
alcohol containing formaldehyde is not preferred and propargyl
alcohol reduced in the formaldehyde content is demanded. The
propargyl alcohol of the present invention is not started from
formaldehyde, therefore, the formaldehyde content thereof can be
reduced to 1,000 ppm or less.
[0131] [D] The use of the propargyl alcohol obtained according to
the present invention (the first embodiment and the second
embodiment) is described below.
[0132] The propargyl alcohol of the present invention can be used
for the application fields, for example, described in
JP-A-5-239365. The propargyl alcohol can be used, for example
coating resin compositions, and curable resins useful as a molding
resin. The compositions and resins are advantageous because of high
resistance to humidity, water, saline solutions, solvent, alkali,
and acid; high suitability for multiple coating; low curing
temperature; and less volume constriction after curing.
[0133] Further the propargyl alcohol of the present invention can
be used, for example, in a resin containing a triple bond such as
ethynyl group or nitrile group within the molecule described in
WO98/03701. In this case, the present invention relates to a
cationic electrodeposition coating composition containing a resin
obtained using the propargyl alcohol produced by the process of the
present invention. The cationic electrodeposition coating can apply
the coating to fine parts even when the material coated has a
complicated shape, therefore, this is being used for general
purposes as an undercoating method in the coating of a material
having a large size and a complicated shape and required to have
high rust preventive property, such as vehicle body. This cationic
electrodeposition coating is favored with very high use efficiency
of the coating material as compared with other coating methods and
in turn ensures high profitability, therefore, is widespread as an
industrial coating method.
[0134] As described above, the propargyl alcohol of the present
invention is characterized in that the formaldehyde content is
1,000 ppm or less, therefore, use thereof is advantageous in view
of the effect on human body or the environmental issue.
[0135] The resin obtained by the use of the propargyl alcohol of
the present invention and the resin composition and the cationic
electrodeposition coating composition containing the resin are
characterized in that the formaldehyde content is 1,000 ppm or
less, therefore, use thereof is advantageous in view of the effect
on human body or the environmental issue.
EXAMPLES
[0136] The present invention is described in greater detail below
by referring to the examples, however, the present invention should
not be construed as being limited thereto.
[0137] The first embodiment is described by referring to the
following Examples.
Example A1
[0138] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 8.48 g (0.08 mol) of Na.sub.2CO.sub.3
and 35.0 g of H.sub.2O were charged, and the mixture was reacted in
a closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 4 hours. The reaction solution was
quantitated by gas chromatography (FID), as a result, the
conversion of 1,2,3-trichloropropane was 95% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 29%.
Example A2
[0139] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 8.48 g (0.08 mol) of Na.sub.2CO.sub.3
and 35.0 g of H.sub.2O were charged, and the mixture was reacted in
a closed system while thoroughly stirring at a reaction temperature
of 170.degree. C. for 4 hours. The reaction solution was
quantitated by gas chromatography (FID), as a result, the
conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 36%.
Example A3
[0140] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 8.48 g (0.08 mol) of Na.sub.2CO.sub.3
and 35.0 g of H.sub.2O were charged, and the mixture was reacted in
a closed system while thoroughly stirring at a reaction temperature
of 200.degree. C. for 4 hours. The reaction solution was
quantitated by gas chromatography (FID), as a result, the
conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 39%.
Example A4
[0141] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3
and 35.0 g of H.sub.2O were charged, and the mixture was reacted in
a closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 4 hours. The reaction solution was
quantitated by gas chromatography (FID), as a result, the
conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 35%.
Example A5
[0142] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
5.21.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of styrene and
35.0 g of H.sub.2O were charged, and the mixture was reacted in a
closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 4 hours. The reaction solution was
quantitated by gas chromatography (FID), as a result, the
conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 41%.
Example A6
[0143] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
5.79.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of lithium
phosphate and 35.0 g of H.sub.2O were charged, and the mixture was
reacted in a closed system while thoroughly stirring at a reaction
temperature of 150.degree. C. for 4 hours. The reaction solution
was quantitated by gas chromatography (FID), as a result, the
conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 43%.
Example A7
[0144] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
9.91.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of
N-nitrosodiphenylamine and 35.0 g of H.sub.2O were charged, and the
mixture was reacted in a closed system while thoroughly stirring at
a reaction temperature of 150.degree. C. for 4 hours. The reaction
solution was quantitated by gas chromatography (FID), as a result,
the conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 42%.
Example A8
[0145] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 5.30 g (0.05 mol) of Na.sub.2CO.sub.3,
4.0 g (0.10 mol) of NaOH and 35.0 g of H.sub.2O were charged, and
the mixture was reacted in a closed system while thoroughly
stirring at a reaction temperature of 150.degree. C. for 4 hours.
The reaction solution was quantitated by gas chromatography (FID),
as a result, the conversion of 1,2,3-trichloropropane was 100% and
the yield of propargyl alcohol based on 1,2,3-trichloropropane was
36%.
Example A9
[0146] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 9.54 g (0.09 mol) of Na.sub.2CO.sub.3,
0.80 g (0.02 mol) of NaOH and 35.0 g of H.sub.2O were charged, and
the mixture was reacted in a closed system while thoroughly
stirring at a reaction temperature of 150.degree. C. for 4 hours.
The reaction solution was quantitated by gas chromatography (FID),
as a result, the conversion of 1,2,3-trichloropropane was 100% and
the yield of propargyl alcohol based on 1,2,3-trichloropropane was
40%.
Example A10
[0147] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 9.54 g (0.09 mol) of Na.sub.2CO.sub.3,
0.80 g (0.02 mol) of NaOH and 35.0 g of H.sub.2O were charged, and
the mixture was reacted in a closed system while thoroughly
stirring at a reaction temperature of 150.degree. C. for 8 hours.
The reaction solution was quantitated by gas chromatography (FID),
as a result, the conversion of 1,2,3-trichloropropane was 100% and
the yield of propargyl alcohol based on 1,2,3-trichloropropane was
44%.
Example A11
[0148] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
1.14 g (0.005 mol) of benzyltriethylammonium chloride and 35.0 g of
H.sub.2O were charged, and the mixture was reacted while thoroughly
stirring at a reaction temperature of 150.degree. C. for 2 hours.
The reaction solution was quantitated by gas chromatography (FID),
as a result, the conversion of 1,2,3-trichloropropane was 100% and
the yield of propargyl alcohol based on 1,2,3-trichloropropane was
35%.
Example A12
[0149] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
1.61 g (0.005 mol) of tetra-n-butylammonium bromide and 35.0 g of
H.sub.2O were charged, and the mixture was reacted while thoroughly
stirring at a reaction temperature of 150.degree. C. for 2 hours.
The reaction solution was quantitated by gas chromatography (FID),
as a result, the conversion of 1,2,3-trichloropropane was 100% and
the yield of propargyl alcohol based on 1,2,3-trichloropropane was
34%.
Example A13
[0150] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
0.548 g (0.005 mol) of tetramethylammonium chloride and 35.0 g of
H.sub.2O were charged, and the mixture was reacted while thoroughly
stirring at a reaction temperature of 150.degree. C. for 2 hours.
The reaction solution was quantitated by gas chromatography (FID),
as a result, the conversion of 1,2,3-trichloropropane was 100% and
the yield of propargyl alcohol based on 1,2,3-trichloropropane was
32%.
Example A14
[0151] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3
and 35.0 g of H.sub.2O were charged, and the mixture was reacted in
a closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 4 hours. After cooling the reaction solution,
the pressure was returned to an atmospheric pressure and 4.0 g
(0.10 mol) of NaOH was added and further reacted while thoroughly
stirring at a reaction temperature of 100.degree. C. for 2 hours.
The resulting reaction solution was quantitated by gas
chromatography (FID), as a result, the conversion of
1,2,3-trichloropropane was 100% and the yield of propargyl alcohol
based on 1,2,3-trichloropropane was 58%.
Example A15
[0152] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3
and 35.0 g of H.sub.2O were charged, and the mixture was reacted in
a closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 4 hours. After cooling the reaction solution,
the pressure was returned to an atmospheric pressure and 8.0 g
(0.10 mol) of an aqueous 50 mass % NaOH solution was added and
further reacted at a reaction temperature of 100.degree. C. for 2
hours. The resulting reaction solution was quantitated by gas
chromatography (FID), as a result, the conversion of
1,2,3-trichloropropane was 100% and the yield of propargyl alcohol
based on 1,2,3-trichloropropane was 66%.
Example A16
[0153] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
5.21.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of styrene and
35.0 g of H.sub.2O were charged, and the mixture was reacted in a
closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 4 hours. After cooling the reaction solution,
the pressure was returned to an atmospheric pressure and 8.0 g
(0.10 mol) of an aqueous 50 mass % NaOH solution was added and
further reacted at a reaction temperature of 100.degree. C. for 2
hours. The resulting reaction solution was quantitated by gas
chromatography (FID), as a result, the conversion of
1,2,3-trichloropropane was 100% and the yield of propargyl alcohol
based on 1,2,3-trichloropropane was 71%.
Example A17
[0154] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
5.79.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of lithium
phosphate and 35.0 g of H.sub.2O were charged, and the mixture was
reacted in a closed system while thoroughly stirring at a reaction
temperature of 150.degree. C. for 4 hours. After cooling the
reaction solution, the pressure was returned to an atmospheric
pressure and 8.0 g (0.10 mol) of an aqueous 50 mass % NaOH solution
was added and further reacted at a reaction temperature of
100.degree. C. for 2 hours. The resulting reaction solution was
quantitated by gas chromatography (FID), as a result, the
conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 70%.
Example A18
[0155] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
9.91.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of
N-nitrosodiphenylamine and 35.0 g of H.sub.2O were charged, and the
mixture was reacted in a closed system while thoroughly stirring at
a reaction temperature of 150.degree. C. for 4 hours. After cooling
the reaction solution, the pressure was returned to an atmospheric
pressure and 8.0 g (0.10 mol) of an aqueous 50 mass % NaOH solution
was added and further reacted at a reaction temperature of
100.degree. C. for 2 hours. The resulting reaction solution was
quantitated by gas chromatography (FID), as a result, the
conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 72%.
Example A19
[0156] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 11.1 g (0.15 mol) of Ca(OH).sub.2 and
35.0 g of H.sub.2O were charged, and the mixture was reacted while
thoroughly stirring at a reaction temperature of 150.degree. C. for
4 hours. After cooling the reaction solution, the pressure was
returned to an atmospheric pressure and 8.0 g (0.10 mol) of an
aqueous 50 mass % NaOH solution was added and further reacted at a
reaction temperature of 100.degree. C. for 2 hours. The resulting
reaction solution was quantitated by gas chromatography (FID), as a
result, the conversion of 1,2,3-trichloropropane was 100% and the
yield of propargyl alcohol based on 1,2,3-trichloropropane was
58%.
Example A20
[0157] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 8.41 g (0.15 mol) of CaO and 35.0 g of
H.sub.2O were charged, and the mixture was reacted while thoroughly
stirring at a reaction temperature of 150.degree. C. for 4 hours.
After cooling the reaction solution, the pressure was returned to
an atmospheric pressure and 8.0 g (0.10 mol) of an aqueous 50 mass
% NaOH solution was added and further reacted at a reaction
temperature of 100.degree. C. for 2 hours. The resulting reaction
solution was quantitated by gas chromatography (FID), as a result,
the conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 59%.
Example A21
[0158] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.0 g (0.10 mol) of CaCO.sub.3 and 35.0
g of H.sub.2O were charged, and the mixture was reacted while
thoroughly stirring at a reaction temperature of 150.degree. C. for
4 hours. After cooling the reaction solution, the pressure was
returned to an atmospheric pressure and 8.0 g (0.10 mol) of an
aqueous 50 mass % NaOH solution was added and further reacted at a
reaction temperature of 100.degree. C. for 2 hours. The resulting
reaction solution was quantitated by gas chromatography (FID), as a
result, the conversion of 1,2,3-trichloropropane was 100% and the
yield of propargyl alcohol based on 1,2,3-trichloropropane was
46%.
Example A22
[0159] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
1.14 g (0.005 mol) of benzyltriethylammonium chloride and 35.0 g of
H.sub.2O were charged, and the mixture was reacted while thoroughly
stirring at a reaction temperature of 150.degree. C. for 4 hours.
After cooling the reaction solution, the pressure was returned to
an atmospheric pressure and 8.0 g (0.10 mol) of an aqueous 50 mass
% NaOH solution was added and further reacted at a reaction
temperature of 100.degree. C. for 2 hours. The resulting reaction
solution was quantitated by gas chromatography (FID), as a result,
the conversion of 1,2,3-trichloropropane was 100% and the yield of
propargyl alcohol based on 1,2,3-trichloropropane was 74%.
Example A23
[0160] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.6 g (0.10 mol) of Na.sub.2CO.sub.3,
1.14 g (0.005 mol) of benzyltriethylammonium chloride,
5.21.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of styrene and
35.0 g of H.sub.2O were charged, and the mixture was reacted while
thoroughly stirring at a reaction temperature of 150.degree. C. for
4 hours. After cooling the reaction solution, the pressure was
returned to an atmospheric pressure and 8.0 g (0.10 mol) of an
aqueous 50 mass % NaOH solution was added and further reacted at a
reaction temperature of 100.degree. C. for 2 hours. The resulting
reaction solution was quantitated by gas chromatography (FID), as a
result, the conversion of 1,2,3-trichloropropane was 100% and the
yield of propargyl alcohol based on 1,2,3-trichloropropane was
76%.
Example A24
[0161] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.60 g (0.10 mol) of Na.sub.2CO.sub.3
and 35.0 g of H.sub.2O were charged, and the mixture was reacted in
a closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 2 hours. After cooling the reaction solution,
the pressure was returned to an atmospheric pressure and 5.61 g
(0.10 mol) of KOH was added and reacted while thoroughly stirring
at a reaction temperature of 100.degree. C. for 2 hours. The
resulting reaction solution was quantitated by gas chromatography
(FID), as a result, the conversion of 1,2,3-trichloropropane was
100% and the yield of propargyl alcohol based on
1,2,3-trichloropropane was 78%.
Example A25
[0162] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.60 g (0.10 mol) of Na.sub.2CO.sub.3,
5.21.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of styrene and
35.0 g of H.sub.2O were charged, and the mixture was reacted in a
closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 2 hours. After cooling the reaction solution,
the pressure was returned to an atmospheric pressure and 5.61 g
(0.10mol) of KOH was added and reacted while thoroughly stirring at
a reaction temperature of 100.degree. C. for 2 hours. The resulting
reaction solution was quantitated by gas chromatography (FID), as a
result, the conversion of 1,2,3-trichloropropane was 100% and the
yield of propargyl alcohol based on 1,2,3-trichloropropane was
82%.
Example A26
[0163] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.60 g (0.10 mol) of Na.sub.2CO.sub.3,
5.79.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of lithium
phosphate and 35.0 g of H.sub.2O were charged, and the mixture was
reacted in a closed system while thoroughly stirring at a reaction
temperature of 150.degree. C. for 2 hours. After cooling the
reaction solution, the pressure was returned to an atmospheric
pressure and 5.61 g (0.10 mol) of KOH was added and reacted while
thoroughly stirring at a reaction temperature of 100.degree. C. for
2 hours. The resulting reaction solution was quantitated by gas
chromatography (FID), as a result, the conversion of
1,2,3-trichloropropane was 100% and the yield of propargyl alcohol
based on 1,2,3-trichloropropane was 81%.
Example A27
[0164] Into an SUS-made 100 ml-volume autoclave, 7.37 g (0.05 mol)
of 1,2,3-trichloropropane, 10.60 g (0.10 mol) of Na.sub.2CO.sub.3,
9.91.times.10.sup.-2 g (5.0.times.10.sup.-4 mol) of
N-nitrosodiphenylamine and 35.0 g of H.sub.2O were charged, and the
mixture was reacted in a closed system while thoroughly stirring at
a reaction temperature of 150.degree. C. for 2 hours. After cooling
the reaction solution, the pressure was returned to an atmospheric
pressure and 5.61 g (0.10 mol) of KOH was added and reacted while
thoroughly stirring at a reaction temperature of 100.degree. C. for
2 hours. The resulting reaction solution was quantitated by gas
chromatography (FID), as a result, the conversion of
1,2,3-trichloropropane was 100% and the yield of propargyl alcohol
based on 1,2,3-trichloropropane was 80%.
Example A28
[0165] A reaction solution was obtained in a scale 10 times larger
than that of Example A15 and neutralized with 35 mass %
hydrochloric acid. Thereto, 100 g of diethyl ether was added and
after vigorously stirring the resulting mixture, the organic phase
was sampled by liquid-liquid separation. The same extracting
operation was repeated twice and the organic phases obtained were
combined and subjected to distillation under atmospheric pressure.
First, diethyl ether as a fraction at the boiling point of 34 to
35.degree. C. was obtained from the top of distillation tower.
Subsequently, an azeotropic component comprising water and
propargyl alcohol as a fraction at the boiling point of 97 to
98.degree. C. was obtained. The distillation was further continued,
then, propargyl alcohol as a fraction at the boiling point of 114
to 115.degree. C. was obtained. The yield of propargyl alcohol was
15.7 g (0.28 mol) and the yield of propargyl alcohol based on
1,2,3-trichloropropane was 56%. From the analysis by gas
chromatography (TCD), the formaldehyde content was found to be 80
ppm.
Example A29
[0166] The same operation was performed as in Example A28 except
that the combined organic phase obtained by the extracting
operation was distilled with 0.521 g (5.0.times.10.sup.-3 mol) of
styrene added thereto under atmospheric pressure to obtain
propargyl alcohol as the fraction at the boiling point of 114 to
115.degree. C. The yield of propargyl alcohol was 17.7 g (0.32 mol)
and the yield of propargyl alcohol based on 1,2,3-trichloropropane
was 63%. From the analysis by high-performance liquid
chromatography (HPLC), the formaldehyde content was found to be 5
ppm or less which is the lower limit of detection.
Example A30
[0167] The same operation was performed as in Example A28 except
that the combined organic phase obtained by the extracting
operation was distilled with 0.579 g (5.0.times.10.sup.-3 mol) of
lithium phosphate added thereto under atmospheric pressure to
obtain propargyl alcohol as the fraction at the boiling point of
114 to 115.degree. C. The yield of propargyl alcohol was 17.0 g
(0.30 mol) and the yield of propargyl alcohol based on
1,2,3-trichloropropane was 61%. From the analysis by
high-performance liquid chromatography (HPLC), the formaldehyde
content was found to be 5 ppm or less which is the lower limit of
detection.
Example A31
[0168] The same operation was performed as in Example A28 except
that the combined organic phase obtained by the extracting
operation was distilled with 0.991 g (5.0.times.10.sup.-3 mol) of
N-nitrosodiphenylamine added thereto under atmospheric pressure to
obtain propargyl alcohol as the fraction at the boiling point of
114 to 115.degree. C. The yield of propargyl alcohol was 16.8 g
(0.30 mol) and the yield of propargyl alcohol based on
1,2,3-trichloropropane was 60%. From the analysis by
high-performance liquid chromatography (HPLC), the formaldehyde
content was found to be 5 ppm or less which is the lower limit of
detection.
Example A32
[0169] A reaction was performed in a scale about 10 times larger
than that of Example A16 and then distillation was performed in the
same manner as in Example A28, as a result, the yield of propargyl
alcohol was 17.4 g (0.31 mol) and the yield of propargyl alcohol
based on 1,2,3-trichloropropane was 62%. From the analysis by
high-performance liquid chromatography (HPLC), the formaldehyde
content was found to be 5 ppm or less which is the lower limit of
detection.
Example A33
[0170] A reaction was performed in a scale about 10 times larger
than that of Example A24 and then distillation was performed in the
same manner as in Example A28, as a result, the yield of propargyl
alcohol was 18.6 g (0.33 mol) and the yield of propargyl alcohol
based on 1,2,3-trichloropropane was 66%. From the analysis by gas
chromatography (TCD), the formaldehyde content was found to be 84
ppm.
Example A34
[0171] A reaction was performed in a scale about 10 times larger
than that of Example A25 and then distillation was performed in the
same manner as in Example A28, as a result, the yield of propargyl
alcohol was 19.6 g (0.35 mol) and the yield of propargyl alcohol
based on 1,2,3-trichloropropane was 70%. From the analysis by
high-performance liquid chromatography (HPLC), the formaldehyde
content was found to be 5 ppm or less which is the lower limit of
detection.
Example A35 (Stability Test A1)
[0172] To 5.61 g (0.10 mol) of propargyl alcohol obtained in the
same manner as in Example A32, 1.0.times.10.sup.-3 g
(1.0.times.10.sup.-5 mol) of styrene was added. The mixture was
heated at 60.degree. C. for 100 days. From the analysis of the
resulting propargyl alcohol by high-performance liquid
chromatography (HPLC), the formaldehyde content was found to be 5
ppm or less which is the lower limit of detection.
Example A36 (Stability Test A2)
[0173] To 5.61 g (0.10 mol) of propargyl alcohol obtained in the
same manner as in Example A32, 1.2.times.10.sup.-3 g
(1.0.times.10.sup.-5 mol) of lithium phosphate was added. The
mixture was heated at 60.degree. C. for 100 days. From the analysis
of the resulting propargyl alcohol by high-performance liquid
chromatography (HPLC), the formaldehyde content was found to be 5
ppm or less which is the lower limit of detection.
Example A37 (Stability Test A3)
[0174] To 5.61 g (0.10 mol) of propargyl alcohol obtained in the
same manner as in Example A32, 2.0.times.10.sup.-3 g
(1.0.times.10.sup.-5 mol) of N-nitrosodiphenylamine was added. The
mixture was heated at 60.degree. C. for 100 days. From the analysis
of the resulting propargyl alcohol by high-performance liquid
chromatography (HPLC), the formaldehyde content was found to be 5
ppm or less which is the lower limit of detection.
[0175] Next, the second embodiment of the present invention is
described by referring to the following Examples.
Example B1
[0176] Into an SUS-made 100 ml-volume autoclave, 12.90 g (0.10 mol)
of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine and
20.0 g of diethylene glycol di-n-butyl ether were charged, and the
mixture was reacted in a closed system while thoroughly stirring at
a reaction temperature of 150.degree. C. for 2 hours. After the
completion of reaction, the reaction solution was quantitated by
gas chromatography. The yield of chloroallyl alcohol based on
2,3-dichloropropanol and the composition ratio thereof (mol %) are
shown in Table 1.
Example B2
[0177] A reaction was performed in the same manner as in Example B1
except for using 18.54 g (0.10 mol) of tri-n-butylamine in place of
triethylamine. The results are shown in Table 1.
Example B3
[0178] A reaction was performed in the same manner as in Example B1
except for using 26.95 g (0.10 mol) of tri-n-hexylamine in place of
triethylamine. The results are shown in Table 1.
Example B4
[0179] A reaction was performed in the same manner as in Example B1
except for using 28.74 g (0.10 mol) of tribenzylamine in place of
triethylamine. The results are shown in Table 1.
Example B5
[0180] A reaction was performed in the same manner as in Example B1
except for using 7.31 g (0.10 mol) of diethylamine in place of
triethylamine. The results are shown in Table 1.
Example B6
[0181] A reaction was performed in the same manner as in Example B1
except for using 12.93 g (0.10 mol) of di-n-butylamine in place of
triethylamine. The results are shown in Table 1.
Example B7
[0182] A reaction was performed in the same manner as in Example B1
except for using 7.31 g (0.10 mol) of n-butylamine in place of
triethylamine. The results are shown in Table 1.
Example B8
[0183] A reaction was performed in the same manner as in Example B1
except for using 7.31 g (0.10 mol) of i-butylamine in place of
triethylamine. The results are shown in Table 1.
Example B9
[0184] A reaction was performed in the same manner as in Example B1
except for using 10.72 g (0.10 mol) of benzylamine in place of
triethylamine. The results are shown in Table 1.
Example B10
[0185] A reaction was performed in the same manner as in Example B1
except for using 7.91 g (0.10 mol) of pyridine in place of
triethylamine. The results are shown in Table 1.
Example B11
[0186] A reaction was performed in the same manner as in Example B1
except for using 6.01 g (0.10 mol) of 1,2-diaminoethane in place of
triethylamine. The results are shown in Table 1.
Example B12
[0187] A reaction was performed in the same manner as in Example B1
except for using 8.82 g (0.10 mol) of 1,4-diaminobutane in place of
triethylamine. The results are shown in Table 1.
Example B13
[0188] A reaction was performed in the same manner as in Example B1
except for using 11.62 g (0.10 mol) of 1,6-diaminohexane in place
of triethylamine. The results are shown in Table 1.
Example B14
[0189] A reaction was performed in the same manner as in Example B1
except for using 10.81 g (0.10 mol) of 1,2-phenylenediamine in
place of triethylamine. The results are shown in Table 1.
Example B15
[0190] A reaction was performed in the same manner as in Example B1
except for using 11.62 g (0.10 mol) of
N,N,N',N'-tetramethyl-1,2-diaminoethane in place of triethylamine.
The results are shown in Table 1.
Example B16
[0191] A reaction was performed in the same manner as in Example B1
except for using 8.61 g (0.10 mol) of piperazine in place of
triethylamine. The results are shown in Table 2.
Example B17
[0192] A reaction was performed in the same manner as in Example B1
except for using 12.12 g (0.10 mol) of N,N-dimethylaniline in place
of triethylamine. The results are shown in Table 2.
Example B18
[0193] A reaction was performed in the same manner as in Example B1
except for using 8.01 g (0.10 mol) of pyridazine in place of
triethylamine. The results are shown in Table 2.
Example B19
[0194] A reaction was performed in the same manner as in Example B1
except for using 6.91 g (0.10 mol) of 1,2,4-triazole in place of
triethylamine. The results are shown in Table 2.
Example B20
[0195] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of acetonitrile in place of diethylene
glycol di-n-butyl ether. The results are shown in Table 2.
Example B21
[0196] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of benzonitrile in place of diethylene
glycol di-n-butyl ether. The results are shown in Table 2.
Example B22
[0197] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of N,N-dimethylformamide in place of
diethylene glycol di-n-butyl ether. The results are shown in Table
2.
Example B23
[0198] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of 1,2-ethanediol in place of diethylene
glycol di-n-butyl ether. The results are shown in Table 2.
Example B24
[0199] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of 1,2-propanediol in place of diethylene
glycol di-n-butyl ether. The results are shown in Table 2.
Example B25
[0200] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of 1,4-butanediol in place of diethylene
glycol di-n-butyl ether. The results are shown in Table 2.
Example B26
[0201] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of dimethylsulfoxide in place of diethylene
glycol di-n-butyl ether. The results are shown in Table 2.
Example B27
[0202] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of 1,2-dicyanoethane in place of diethylene
glycol di-n-butyl ether. The results are shown in Table 2.
Example B28
[0203] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of 1,4-dicyanobutane in place of diethylene
glycol di-n-butyl ether. The results are shown in Table 2.
Example B29
[0204] A reaction was performed in the same manner as in Example B1
except for using 20.0 g of H.sub.2O in place of diethylene glycol
di-n-butyl ether. The results are shown in Table 2.
Example B30
[0205] A reaction was performed in the same manner as in Example B1
except for using 40.48 g (0.40 mol) of triethylamine. The results
are shown in Table 2.
Example B31
[0206] A reaction was performed in the same manner as in Example B1
except for using 5.06 g (0.05 mol) of triethylamine. The results
are shown in Table 3.
Example B32
[0207] A reaction was performed in the same manner as in Example B1
except for using 40.48 g (0.40 mol) of triethylamine and not using
diethylene glycol di-n-butyl ether. The results are shown in Table
3.
Example B33
[0208] A reaction was performed in the same manner as in Example B1
except for performing the reaction at a reaction temperature of
100.degree. C. for 2 hours. The results are shown in Table 3.
Example B34
[0209] A reaction was performed in the same manner as in Example B1
except for performing the reaction at a reaction temperature of
200.degree. C. for 2 hours. The results are shown in Table 3.
Example B35
[0210] A reaction was performed in the same manner as in Example B1
except for performing the reaction at a reaction temperature of
150.degree. C. for 6 hours. The results are shown in Table 3.
Example B36
[0211] Into an SUS-made 100 ml-volume autoclave, 12.90 g (0.10 mol)
of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine,
0.104 g (0.0010 mol) of styrene and 20.0 g of acetonitrile were
charged, and the mixture was reacted in a closed system while
thoroughly stirring at a reaction temperature of 150.degree. C. for
2 hours. The results are shown in Table 3.
Example B37
[0212] Into an SUS-made 100 ml-volume autoclave, 12.90 g (0.10 mol)
of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine,
0.116 g (0.0010 mol) of lithium phosphate and 20.0 g of
acetonitrile were charged, and the mixture was reacted in a closed
system while thoroughly stirring at a reaction temperature of
150.degree. C. for 2 hours. The results are shown in Table 3.
Example B38
[0213] Into an SUS-made 100 ml-volume autoclave, 12.90 g (0.10 mol)
of 2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine,
0.198 g (0.0010 mol) of N-nitrosodiphenylamine and 20.0 g of
acetonitrile were charged, and the mixture was reacted in a closed
system while thoroughly stirring at a reaction temperature of
150.degree. C. for 2 hours. The results are shown in Table 3.
Example B39
[0214] A reaction solution obtained in the scale 10 times larger
than that of Example B20 was subjected to distillation under
atmospheric pressure. As a result, from the top of distillation
tower, acetonitrile was first obtained and then a slight amount of
triethylamine was obtained. The distillation was further continued,
then, objective chloroallyl alcohol was obtained. The yield of
chloroallyl alcohol was 74.2 g (0.80 mol) and the yield of
chloroallyl alcohol based on 2,3-dichloro-1-propanol was 80%.
[0215] Into a reactor, 74.2 g (0.80 mol) of the thus-obtained
chloroallyl alcohol and 640.0 g (1.60 mol) of an aqueous 10 mass %
NaOH solution were charged, and the mixture was reacted under
atmospheric pressure while thoroughly stirring at a reaction
temperature of 100.degree. C. for 4 hours. The reaction solution
was quantitated by gas chromatography (FID), as a result, the
conversion of chloroallyl alcohol was 100% and the yield of
propargyl alcohol based on chloroallyl alcohol was 71%.
[0216] Furthermore, the above-described reaction solution was
neutralized with 35 mass % hydrochloric acid. Thereto, 100 g of
diethyl ether was added and after vigorously stirring the resulting
mixture, the organic phase was sampled by liquid-liquid separation.
The same extracting operation was repeated twice and the organic
phases obtained were combined and subjected to distillation under
atmospheric pressure. As a result, from the top of distillation
tower, diethyl ether as a fraction at the boiling point of 34 to
35.degree. C. was first obtained. Subsequently, an azeotropic
component comprising water and propargyl alcohol as a fraction at
the boiling point of 97 to 98.degree. C. was obtained. The
distillation was further continued, then, propargyl alcohol as a
fraction at the boiling point of 114 to 115.degree. C. was
obtained. The yield of propargyl alcohol was 28.6 g (0.51 mol) and
the yield of propargyl alcohol based on 2,3-dichloro-1-propanol was
51%. From the analysis of this propargyl alcohol by
high-performance liquid chromatography (HPLC), the formaldehyde
content was found to be 5 ppm or less which is the lower limit of
detection.
Example B40
[0217] The same operation was performed as in Example B39 except
that the combined organic phase obtained by the extracting
operation was distilled with 0.520 g (0.0050 mol) of styrene added
thereto under atmospheric pressure to obtain propargyl alcohol as a
fraction at the boiling point of 114 to 115.degree. C. The yield of
propargyl alcohol was 32.2 g (0.57 mol) and the yield of propargyl
alcohol based on the 2,3-dichloro-1-propanol was 57%. From the
analysis of this propargyl alcohol by high-performance liquid
chromatography (HPLC), the formaldehyde content was found to be 5
ppm or less which is the lower limit of detection.
Example B41
[0218] The same operation was performed as in Example B39 except
that the combined organic phase obtained by the extracting
operation was distilled with 0.579 g (0.0050 mol) of lithium
phosphate added thereto under atmospheric pressure to obtain
propargyl alcohol as a fraction at the boiling point of 114 to
115.degree. C. The yield of propargyl alcohol was 30.8 g (0.55 mol)
and the yield of propargyl alcohol based on the
2,3-dichloro-1-propanol was 55%. From the analysis of this
propargyl alcohol by high-performance liquid chromatography (HPLC),
the formaldehyde content was found to be 5 ppm or less which is the
lower limit of detection.
Example B42
[0219] The same operation was performed as in Example B39 except
that the combined organic phase obtained by the extracting
operation was distilled with 0.991 g (0.0050 mol) of
N-nitrosodiphenylamine added thereto under atmospheric pressure to
obtain propargyl alcohol as a fraction at the boiling point of 114
to 115.degree. C. The yield of propargyl alcohol was 31.3 g (0.56
mol) and the yield of propargyl alcohol based on the
2,3-dichloro-1-propanol was 56%. From the analysis of this
propargyl alcohol by high-performance liquid chromatography (HPLC),
the formaldehyde content was found to be 5 ppm or less which is the
lower limit of detection.
Example B43
[0220] Into a reactor, 9.25 g (0.10 mol) of the chloroallyl alcohol
obtained by the distillation in the same manner as in Example B39,
0.104 g (0.0010 mol) of styrene and 80.0 g (0.20 mol) of an aqueous
10 mass % NaOH solution were charged, and the mixture was reacted
under atmospheric pressure while thoroughly stirring at a reaction
temperature of 100.degree. C. for 4 hours. The reaction solution
was quantitated by gas chromatography (FID), as a result, the yield
of propargyl alcohol based on chloroallyl alcohol was 83%.
Example B44
[0221] Into a reactor, 9.25 g (0.10 mol) of the chloroallyl alcohol
obtained by the distillation in the same manner as in Example B39,
0.116 g (0.0010 mol) of lithium phosphate and 80.0 g (0.20 mol) of
an aqueous 10 mass % NaOH solution were charged, and the mixture
was reacted under atmospheric pressure while thoroughly stirring at
a reaction temperature of 100.degree. C. for 4 hours. The reaction
solution was quantitated by gas chromatography (FID), as a result,
the yield of propargyl alcohol based on chloroallyl alcohol was
82%.
Example B45
[0222] Into a reactor, 9.25 g (0.10 mol) of the chloroallyl alcohol
obtained by the distillation in the same manner as in Example B39,
0.198 g (0.0010 mol) of N-nitrosodiphenylamine and 80.0 g (0.20
mol) of an aqueous 10 mass % NaOH solution were charged, and the
mixture was reacted under atmospheric pressure while thoroughly
stirring at a reaction temperature of 100.degree. C. for 4 hours.
The reaction solution was quantitated by gas chromatography (FID),
as a result, the yield of propargyl alcohol based on chloroallyl
alcohol was 81%.
Example B46
[0223] Into a reactor, 9.25 g (0.10 mol) of the chloroallyl alcohol
obtained by the distillation in the same manner as in Example B39
and 112.2 g (0.20 mol) of an aqueous 10 mass % KOH solution were
charged, and the mixture was reacted under atmospheric pressure
while thoroughly stirring at a reaction temperature of 100.degree.
C. for 4 hours. The reaction solution was quantitated by gas
chromatography (FID), as a result, the yield of propargyl alcohol
based on chloroallyl alcohol was 80%.
Example B47
[0224] A reaction solution obtained in the scale 10 times larger
than that of Example B35 was subjected to distillation under
atmospheric pressure. As a result, triethylamine was first obtained
from the top of distillation tower. The distillation was further
continued, then, chloroallyl alcohol was obtained. The yield of
chloroallyl alcohol was 73.1 g (0.79 mol) and the yield of
chloroallyl alcohol based on 2,3-dichloro-1-propanol was 79%.
[0225] Into a reactor, 73.1 g (0.79 mol) of the thus-obtained
chloroallyl alcohol and 632 g (1.58 mol) of an aqueous 10 mass %
NaOH solution were charged, and the mixture was reacted under
atmospheric pressure while thoroughly stirring at a reaction
temperature of 100.degree. C. for 4 hours. The reaction solution
was quantitated by gas chromatography (FID), as a result, the yield
of propargyl alcohol based on chloroallyl alcohol was 72%.
[0226] Furthermore, the reaction solution obtained above was
neutralized with 35 mass % hydrochloric acid, 100 g of diethyl
ether was added thereto, and after vigorously stirring the
resulting mixture, the organic phase was sampled by liquid-liquid
separation. The same extracting operation was repeated twice and
the organic phases obtained were combined and subjected to
distillation under atmospheric pressure. As a result, diethyl ether
as a fraction at the boiling point of 34 to 35.degree. C. was first
obtained from the top of distillation tower. Subsequently, an
azeotropic component comprising water and propargyl alcohol as a
fraction at the boiling point of 97 to 98.degree. C. was obtained.
The distillation was further continued, then, propargyl alcohol as
a fraction at the boiling point of 114 to 115.degree. C. was
obtained. The yield of propargyl alcohol was 29.6 g (0.53 mol) and
the yield of propargyl alcohol based on 2,3-dichloro-1-propanol was
53%. From the analysis of this propargyl alcohol by
high-performance liquid chromatography (HPLC), the formaldehyde
content was found to be 5 ppm or less which is the lower limit of
detection.
Example B48
[0227] Into an SUS-made autoclave, 12.90 g (0.10 mol) of
2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine and
20.0 g of diethylene glycol di-n-butyl ether were charged, and the
mixture was reacted in a closed system while thoroughly stirring at
a reaction temperature of 150.degree. C. for 6 hours. After cooling
the reaction solution, the pressure was returned to atmospheric
pressure and 80.0 g (0.20 mol) of an aqueous 10 mass % NaOH
solution was added and further reacted at a reaction temperature of
100.degree. C. for 4 hours. The resulting reaction solution was
quantitated by gas chromatography (FID), as a result, the
conversion of 2,3-dichloro-1-propanol was 100% and the yield of
propargyl alcohol based on 2,3-dichloro-1-propanol was 74.8%.
Example B49
[0228] Into an SUS-made autoclave, 12.90 g (0.10 mol) of
2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine, 0.104
g (0.0010 mol) of styrene and 20.0 g of diethylene glycol
di-n-butyl ether were charged, and the mixture was reacted in a
closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 6 hours. After cooling the reaction solution,
the pressure was returned to atmospheric pressure and 80.0 g (0.20
mol) of an aqueous 10 mass % NaOH solution was added and further
reacted at a reaction temperature of 100.degree. C. for 4 hours.
The resulting reaction solution was quantitated by gas
chromatography (FID), as a result, the yield of propargyl alcohol
based on 2,3-dichloro-1-propanol was 83%.
Example B50
[0229] Into an SUS-made autoclave, 12.90 g (0.10 mol) of
2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine, 0.116
g (0.0010 mol) of lithium phosphate and 20.0 g of diethylene glycol
di-n-butyl ether were charged, and the mixture was reacted in a
closed system while thoroughly stirring at a reaction temperature
of 150.degree. C. for 6 hours. After cooling the reaction solution,
the pressure was returned to atmospheric pressure and 80.0 g (0.20
mol) of an aqueous 10 mass % NaOH solution was added and further
reacted at a reaction temperature of 100.degree. C. for 4 hours.
The resulting reaction solution was quantitated by gas
chromatography (FID), as a result, the yield of propargyl alcohol
based on 2,3-dichloro-1-propanol was 81%.
Example B51
[0230] Into an SUS-made autoclave, 12.90 g (0.10 mol) of
2,3-dichloro-1-propanol, 10.12 g (0.10 mol) of triethylamine, 0.198
g (0.0010 mol) of N-nitrosodiphenylamine and 20.0 g of diethylene
glycol di-n-butyl ether were charged, and the mixture was reacted
in a closed system while thoroughly stirring at a reaction
temperature of 150.degree. C. for 6 hours. After cooling the
reaction solution, the pressure was returned to atmospheric
pressure and 80.0 g (0.20 mol) of an aqueous 10 mass % NaOH
solution was added and further reacted at a reaction temperature of
100.degree. C. for 4 hours. The resulting reaction solution was
quantitated by gas chromatography (FID), as a result, the yield of
propargyl alcohol based on 2,3-dichloro-1-propanol was 82%.
Example B52 (Stability Test B1)
[0231] To 5.61 g (0.10 mol) of propargyl alcohol obtained in the
same manner as in Example B39, 0.0010 g (1.0.times.10.sup.-5 mol)
of styrene was added. The mixture was heated at 60.degree. C. for
100 days. From the analysis of resulting propargyl alcohol by
high-performance liquid chromatography (HPLC), the formaldehyde
content was found to be 5 ppm or less which is the lower limit of
detection.
Example B53 (Stability Test B2)
[0232] To 5.61 g (0.10 mol) of propargyl alcohol obtained in the
same manner as in Example B39, 0.0012 g (1.0.times.10.sup.-5 mol)
of lithium phosphate was added. The mixture was heated at
60.degree. C. for 100 days. From the analysis of resulting
propargyl alcohol by high-performance liquid chromatography (HPLC),
the formaldehyde content was found to be 5 ppm or less which is the
lower limit of detection.
Example B54 (Stability Test B3)
[0233] To 5.61 g (0.10 mol) of propargyl alcohol obtained in the
same manner as in Example B39, 0.0020 g (1.0.times.10.sup.-5 mol)
of N-nitrosodiphenylamine was added. The mixture was heated at
60.degree. C. for 100 days. From the analysis of resulting
propargyl alcohol by high-performance liquid chromatography (HPLC),
the formaldehyde content was found to be 5 ppm or less which is the
lower limit of detection.
The Effects of the Invention
[0234] According to the present invention (the first embodiment),
propargyl alcohol can be efficiently produced from
1,2,3-trichloropropane without isolating an intermediate.
[0235] Also, according to the present invention (the second
embodiment), propargyl alcohol can be efficiently produced from
chloroallyl alcohol obtained by reacting 2,3-dichloro-1-propanol
with an amine.
1 TABLE 1 Chloro- Composition ratio (mole %) Amine allyl alcohol
2-Chloro-allyl 3-cis-Chloro- 3-trans-Chloro- Example Solvent Yield
(%) alcohol allyl alcohol allyl alcohol B1 Triethylamine 60.3 81.4
9.7 8.9 Diethylene glycol di-n-butyl ether B2 Tri-n-butylamine 53.2
68.7 15.7 15.7 Diethylene glycol di-n-butyl ether B3
Tri-n-hexylamine 48.4 71.2 13.6 15.2 Diethylene glycol di-n-butyl
ether B4 Tribenzylamine 40.8 66.7 17.5 15.8 Diethylene glycol
di-n-butyl ether B5 Diethylamine 50.1 88.6 4.9 6.4 Diethylene
glycol di-n-butyl ether B6 Di-n-butylamine 55.5 73.2 11.1 15.8
Diethylene glycol di-n-butyl ether B7 n-Buthylamine 50.0 81.5 10.0
8.5 Diethylene glycol di-n-butyl ether B8 i-Butylamine 55.5 80.2
11.4 8.4 Diethylene glycol di-n-butyl ether B9 Benzylamine 44.2
83.2 8.4 8.6 Diethylene glycol di-n-butyl ether B10 Pyridine 21.0
88.2 6.2 5.6 Diethylene glycol di-n-butyl ether B11
1,2-Diaminoethane 40.2 73.5 12.8 13.7 Diethylene glycol di-n-butyl
ether B12 1,4-Diaminobutane 41.1 77.5 11.2 11.3 Diethylene glycol
di-n-butyl ether B13 1,6-Diaminohexane 46.9 77.4 11.3 11.3
Diethylene glycol di-n-butyl ether B14 1,2-Phenylenediamine 42.3
87.4 6.3 6.3 Diethylene glycol di-n-butyl ether B15
N,N,N',N'-Tetramethylethyl- enediamine 58.8 83.1 7.8 9.1 Diethylene
glycol di-n-butyl ether
[0236]
2 TABLE 2 Chloro- Composition ratio (mole %) Amine allyl alcohol
2-Chloro-allyl 3-cis-Chloro- 3-trans-Chloro- Example Solvent Yield
(%) alcohol allyl alcohol allyl alcohol B16 Piperazine 53.4 78.5
11.6 9.9 Diethylene glycol di-n-butyl ether B17 N,N-Dimethylaniline
30.1 85.6 7.3 7.1 Diethylene glycol di-n-butyl ether B18 Pyridazine
28.6 88.2 6.4 5.4 Diethylene glycol di-n-butyl ether B19
1,2,4-Triazole 29.2 89.5 5.4 5.1 Diethylene glycol di-n-butyl ether
B20 Triethylamine 89.8 72.6 13.8 13.7 Acetonitrile B21
Triethylamine 71.3 76.5 12.5 11.0 Benzonitrile B22 Triethylamine
61.4 76.2 11.9 11.8 N,N-Dimethylformamide B23 Triethylamine 76.2
89.3 5.1 5.6 1,2-Ethanediol B24 Triethylamine 70.5 90.2 4.8 5.0
1,2-Propanediol B25 Triethyalmine 85.4 66.6 17.0 16.3
1,4-Butanediol B26 Triethylamine 42.8 78.3 10.9 10.9 Dimethyl
sulfoxide B27 Triethylamine 81.8 75.2 12.7 12.1 1,2-Dicyanoethane
B28 Triethylamine 81.9 74.2 12.3 13.5 1,4-Dicyanobutane B29
Triethylamine 44.8 76.9 11.6 11.6 Water B30 Triethylamine 81.4 76.2
11.9 11.8 Diethylene glycol di-n-butyl ether
* * * * *