U.S. patent application number 14/779581 was filed with the patent office on 2016-02-25 for bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, ammonium salt thereof, and method for producing same.
This patent application is currently assigned to KURARAY CO., LTD.. The applicant listed for this patent is HOKKO CHEMICAL INDUSTRY CO., LTD.. Invention is credited to Eriko HONDA, Hitoshi KOIZUMI, Nobumichi KUMAMOTO, Kyoko SUGITA, Tomoaki TSUJI, Tatsuya YOSHIKAWA.
Application Number | 20160052948 14/779581 |
Document ID | / |
Family ID | 51624366 |
Filed Date | 2016-02-25 |
United States Patent
Application |
20160052948 |
Kind Code |
A1 |
HONDA; Eriko ; et
al. |
February 25, 2016 |
BIS(6-METHYL-3-SULPHOPHENYL)(2-METHYLPHENYL)PHOSPHINE, AMMONIUM
SALT THEREOF, AND METHOD FOR PRODUCING SAME
Abstract
Provided are a water-soluble triarylphosphine for a palladium
catalyst, which has high selectivity in a telomerization reaction
and is easily recovered with efficiency, an ammonium salt thereof,
and a method for efficiently producing the same. Specifically,
provided are bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine;
a bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt obtained by reacting the phosphine with a tertiary
amine having a total of 3 to 27 carbon atoms in groups bonded to
one nitrogen atom; and a method for producing the same.
Inventors: |
HONDA; Eriko; (Okayama-shi,
JP) ; YOSHIKAWA; Tatsuya; (Kamisu-shi, JP) ;
TSUJI; Tomoaki; (Kamisu-shi, JP) ; KOIZUMI;
Hitoshi; (Hiratsuka-shi, JP) ; SUGITA; Kyoko;
(Atsugi-shi, JP) ; KUMAMOTO; Nobumichi;
(Atsugi-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HOKKO CHEMICAL INDUSTRY CO., LTD. |
Chuo-ku, Tokyo |
|
JP |
|
|
Assignee: |
KURARAY CO., LTD.
Kurashiki-shi, Okayama
JP
HOKKO CHEMICAL INDUSTRY CO., LTD.
Chuo-ku, Tokyo
JP
|
Family ID: |
51624366 |
Appl. No.: |
14/779581 |
Filed: |
March 26, 2014 |
PCT Filed: |
March 26, 2014 |
PCT NO: |
PCT/JP14/58666 |
371 Date: |
September 24, 2015 |
Current U.S.
Class: |
502/162 ;
568/13 |
Current CPC
Class: |
B01J 31/0225 20130101;
C07C 211/05 20130101; C07C 211/08 20130101; C07F 9/5022 20130101;
B01J 31/0271 20130101; C07C 211/07 20130101; B01J 31/0267 20130101;
B01J 2231/20 20130101 |
International
Class: |
C07F 9/50 20060101
C07F009/50; B01J 31/02 20060101 B01J031/02 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 27, 2013 |
JP |
2013-067276 |
Claims
2. A bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt obtained by reacting the
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine of claim 1
with a tertiary amine having a total of 3 to 27 carbon atoms in
groups bonded to one nitrogen atom.
3. The bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt of claim 2, wherein the tertiary amine is
trimethylamine, triethylamine, tripropylamine, triisopropylamine,
tributylamine, triisobutylamine, tri-s-butylamine,
tri-t-butylamine, tripentylamine, triisopentylamine,
trineopentylamine, trihexylamine, triheptylamine, trioctylamine,
triphenylamine, tribenzylamine, N,N-dimethylethylamine,
N,N-dimethylpropylamine, N,N-dimethylisopropylamine,
N,N-dimethylbutylamine, N,N-dimethylisobutylamine,
N,N-dimethyl-s-butylamine, N,N-dimethyl-t-butylamine,
N,N-dimethylpentylamine, N,N-dimethylisopentylamine,
N,N-dimethylneopentylamine, N,N-dimethylhexylamine,
N,N-dimethylheptylamine, N,N-dimethyloctylamine,
N,N-dimethylnonylamine, N,N-dimethyldecylamine,
N,N-dimethylundecylamine, N,N-dimethyldodecylamine,
N,N-dimethylphenylamine, N,N-dimethylbenzylamine,
N,N-diethylmonomethylamine, N,N-dipropylmonomethylamine,
N,N-diisopropylmonomethylamine, N,N-dibutylmonomethylamine,
N,N-diisobutylmonomethylamine, N,N-di-s-butylmonomethylamine,
N,N-di-t-butylmonomethylamine, N,N-dipentylmonomethylamine,
N,N-diisopentylmonomethylamine, N,N-dineopentylmonomethylamine,
N,N-dihexylmonomethylamine, N,N-diheptylmonomethylamine,
N,N-dioctylmonomethylamine, N,N-dinonylmonomethylamine,
N,N-didecylmonomethylamine, N,N-diundecylmonomethylamine,
N,N-didodecylmonomethylamine, N,N-diphenylmonomethylamine,
N,N-dibenzylmonomethylamine, N,N-dipropylmonomethylamine,
N,N-diisopropylmonoethylamine, N,N-dibutylmonoethylamine,
N,N-diisobutylmonoethylamine, N,N-di-s-butylmonoethylamine,
N,N-di-t-butylmonoethylamine, N,N-dipentylmonoethylamine,
N,N-diisopentylmonoethylamine, N,N-dineopentylmonoethylamine,
N,N-dihexylmonoethylamine, N,N-diheptylmonoethylamine,
N,N-dioctylmonoethylamine, N,N-dinonylmonoethylamine,
N,N-didecylmonoethylamine, N,N-diundecylmonoethylamine,
N,N-didodecylmonoethylamine, N,N-diphenylmonoethylamine,
N,N-dibenzylmonoethylamine, and trinonylamine.
4. A mixture, comprising: 5% by mole or less of
bis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 80% by mole
or more of bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine,
and 15% by mole or less of
tris(6-methyl-3-sulphophenyl)phosphine.
5. A mixture, comprising: 80% by mole or more of a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt obtained by reacting the mixture of claim 4 with a
tertiary amine having a total of 3 to 27 carbon atoms in groups
bonded to one nitrogen atom.
6. A method for producing the
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine of claim 1,
comprising: reacting 2.5 moles to 4.5 moles of sulphur trioxide
with 1 mole of tris(2-methylphenyl)phosphine in the presence of
concentrated sulphuric acid, thereby producing a sulphonation
reaction liquid, and diluting the obtained sulphonation reaction
liquid with water, thereby producing a diluted liquid; neutralizing
the diluted liquid with an alkali metal hydroxide, thereby
producing an aqueous solution; and bringing the aqueous solution
into contact with a strongly acidic cation exchange resin.
7. A method for producing a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt. the method comprising: reacting the
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine of claim 1
with a tertiary amine having a total of 3 to 27 carbon atoms in
groups bonded to one nitrogen atom.
Description
TECHNICAL FIELD
[0001] The present invention relates to
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, an ammonium
salt thereof, and a method for producing the same.
BACKGROUND ART
[0002] A palladium catalyst comprised of a phosphorous compound and
a palladium compound is useful as a catalyst for a telomerization
reaction between two conjugated alkadiene molecules and a
nucleophilic reactant. Specifically, it is useful as a catalyst for
production of 2,7-octadien-1-ol by reacting two butadiene molecules
with one water molecule in the presence of carbon dioxide and a
tertiary amine to perform a telomerization reaction. 7-Octenal can
be derived from 2,7-octadien-1-ol thus obtained by an isomerization
reaction and 1,9-nonanedial can be derived from 7-octenal by a
hydroformylation reaction. From the viewpoint that
1,9-nonanediamine which is useful as a raw material for a monomer
for a polymer can be derived from 1,9-nonanedial by a reductive
amination reaction, the 2,7-octadien-1-ol is of a high industrial
value, and it is therefore important to develop a catalyst
advantageous for the production thereof.
[0003] In order to produce 2,7-octadien-1-ol in an industrially
advantageous manner, it is preferable to recover palladium as a
noble metal in the telomerization reaction and reuse it in the
reaction. As such a method for producing 2,7-octadien-1-ol, there
are two methods using a telomerization reaction, as followings:
[0004] (A) a method for producing 2,7-octadien-1-ol, in which
butadiene and water are subjected to a telomerization reaction in
the presence of a palladium catalyst comprised of a palladium
compound and a water-soluble phosphine in an aqueous sulfolane
solution including a carbonate of a tertiary amine and a
bicarbonate of a tertiary amine to generate 2,7-octadien-1-ol, at
least part of the reaction mixed liquid is extracted with a
saturated aliphatic hydrocarbon or the like to separate the
2,7-octadien-1-ol by extraction, and at least a part of the
sulfolane eluent including the palladium catalyst is recycled and
used in the reaction (see PTLs 1 to 3), and
[0005] (B) a method for producing 2,7-octadien-1-ol, in which a
tertiary amine having a function as a surfactant capable of
compensating for a low reaction rate due to low solubility of
butadiene in water coexists therewith in a two-phase system
including an aqueous phase having a palladium catalyst comprised of
a palladium compound and a water-soluble phosphorus-containing
compound dissolved in water and an organic phase which is
butadiene, and then butadiene and water are subjected to a
telomerization reaction (see PTL 4 and NPL 1).
[0006] In the method (A), 2,7-octadien-1-ol is extracted by adding
a saturated aliphatic hydrocarbon to a telomerization reaction
liquid, and it is thus necessary to install equipment for
distillation and recovery of the saturated aliphatic hydrocarbon,
which results in an increase in cost burden associated with the
equipment. Further, sulfolane is more expensive than ordinary
hydrocarbon-based solvents, such as hexane, and accordingly, it is
necessary to recover the sulfolane by subjecting the
2,7-octadien-1-ol phase obtained by extraction to washing with
water, or the like. In addition, since sulfolane is a sulphur
atom-containing substance, in a case of incineration disposal of
sulfolane, an incinerator having desulphurization equipment is
required. Therefore, there is a demand for a method for
conveniently recovering most of a palladium catalyst after a
telomerization reaction while not using sulfolane in the
telomerization reaction.
[0007] In the method (B), dimethyldodecylamine, for example, is
used as a tertiary amine. Since the dimethyldodecylamine has a
function as a surfactant, complicated operations such as multiple
extraction and recovery, or distillation and separation are
required so as to increase the recovery of a tertiary amine.
Further, according to Examples, it can be said that the method (B)
is a method having low selectivity for 2,7-octadien-1-ol.
Therefore, there is also a demand for a method in which the
tertiary amine to be easily recovered can be used, and the
selectivity for 2,7-octadien-1-ol is high.
[0008] Moreover, as a method for producing a water-soluble
triarylphosphine which can be used in a telomerization reaction,
the following methods are known:
[0009] (1) a method for producing a
bis(3-sulphonatophenyl)phenylphosphine disodium salt, by dissolving
triphenylphosphine in sulphuric acid, and then reacting the
solution with sulphur trioxide in fuming sulphuric acid (see NPLs 2
and 3),
[0010] (2) a method for producing a
bis(3-sulphonatophenyl)phenylphosphine disodium salt by
sulphonation of triphenylphosphine using an anhydrous mixture of
sulphuric acid and orthoboric acid (see PTL 5),
[0011] (3) a method in which triarylphosphine having an electron
donating group such as a methyl group and a methoxy group in an
aromatic ring is reacted with sulphur trioxide in the presence of
sulphuric acid (see NPL 4), and
[0012] (4) a method in which triarylphosphine having an electron
donating group such as a methyl group and a methoxy group in each
of three aromatic rings is reacted with sulphur trioxide in the
presence of sulphuric acid (see NPL 5).
[0013] In the case of using the alkali metal salt of a
triarylphosphine having a sulphonate group, obtained by these
methods, in a telomerization reaction, there is a problem in that
inorganic salts such as hydrogen carbonate of an alkali metal are
accumulated in the reaction system, thus blocking pipes. It is
known that as a method to avoid this problem, it is preferable to
use an ammonium salt obtained by reacting a triarylphosphine having
a sulphonate group with a tertiary amine as a catalyst for a
telomerization reaction (see PTL 6).
[0014] In the method (1) for producing a water-soluble
triarylphosphine, a bis(3-sulphonatophenyl)phenylphosphine disodium
salt can be produced by sulphonating triphenylphosphine having a
benzene ring as an equivalent aromatic ring relative to one
phosphorus atom, bonded thereto with sulphur trioxide, followed by
neutralization with sodium hydroxide, but the yield is as low as
60%. This is mainly caused by by-production of a
tris(3-sulphonatophenyl)phosphine trisodium salt, indicating that
it is difficult to selectively introduce only "two" sulpho groups
with respect to the equivalent aromatic ring.
[0015] The method (2) for producing a water-soluble
triarylphosphine is a method in which orthoboric acid is used
instead of sulphur trioxide during a sulphonation reaction. The
bis(3-sulphonatophenyl)phenylphosphine disodium salt is acquired
with a yield of 94%, but in order to remove boric acid completely,
toluene and triisooctylamine are added to a sulphonation reaction
liquid once to cause a desired amine salt to be present in an
organic phase, the organic phase is sufficiently washed with water,
and the aqueous phase obtained by adding an aqueous sodium
hydroxide solution to the washed organic phase is neutralized with
sulphuric acid, and then concentrated. Then, methanol is added
thereto to obtain a supernatant, from which methanol is removed,
thereby acquiring a bis(3-sulphonatophenyl)phenylphosphine disodium
salt. Although the yield is high, it is necessary to repeat washing
to remove boric acid. Therefore, this method is difficult to carry
out industrially.
[0016] The method (3) for producing a water-soluble
triarylphosphine is a method in which a triarylphosphine in which
an electron donating group such as a methyl group and a methoxy
group is introduced in advance to an aromatic ring is reacted with
sulphur trioxide in the presence of sulphuric acid. The method
simply shows that only in the case where a triarylphosphine having
a non-equivalent aromatic ring such as
bis(4-methoxyphenyl)phenylphosphine or the like is used as a raw
material, the number of the introduced sulpho groups of the
bis(4-methoxy-3-sulphonatophenyl)phenylphosphine disodium salt or
the like can be controlled, but does not show that the number of
the introduced sulpho groups in tris(2-methylphenyl)phosphine
having an equivalent aromatic ring can be controlled.
[0017] The method (4) for producing a water-soluble
triarylphosphine shows that a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine disodium
salt can be acquired, but does not disclose specific production
methods and yields thereof, which means the method simply shows the
probability of isolating the present compound.
[0018] As a method for producing an ammonium salt of a
triarylphosphine having a sulphonate group, methods in which an
alkali metal salt of a triarylphosphine having a sulphonate group
is used as a raw material, a counter-cation is converted into a
desired ammonium salt by an ion exchange process in the following
manner are known. The methods are as follows:
[0019] a method in which sulphuric acid is added to an aqueous
solution of a diphenyl(3-sulphonatophenyl)phosphine sodium salt,
4-methyl-2-pentanone is then added thereto, and triethylamine is
added to the obtained organic phase, thereby precipitating a
solid-state diphenyl(3-sulphonatophenyl)phosphine triethylammonium
salt (see PTL 6); and
[0020] a method in which a diphenyl(3-sulphonatophenyl)phosphine
sodium salt is pressurized with carbon dioxide in the presence of
triethylamine, ethanol, and 2-propanol, and a desired product is
acquired from a filtrate of the reaction liquid (see PTL 7).
CITATION LIST
Patent Literature
[0021] [PTL 1] JP-A-64-25739
[0022] [PTL 2] JP-A-3-232831
[0023] [PTL 3] JP-A-6-321828
[0024] [PTL 4] JP-T-8-501800
[0025] [PTL 5] JP-A-8-176167
[0026] [PTL 6] JP-A-2002-371088
[0027] [PTL 7] JP-A-2003-171388
Non Patent Literature
[0028] [NPL 1] Journal of Molecular Catalysis A: Chemical, vol. 97,
1995, pp. 29 to 33
[0029] [NPL 2] Tetrahedron Letters, 2000, vol. 41, pp. 4503 to
4505
[0030] [NPL 3] Organic Process Research & Development, 2000,
vol. 4, pp. 342 to 345
[0031] [NPL 4] Tetrahedron Letters, vol. 43, 2002, pp. 2543 to
2546
[0032] [NPL 5] Advanced Synthesis & Catalysis, 2008, vol. 350,
pp. 609 to 618
SUMMARY OF INVENTION
Technical Problem
[0033] In the ion exchange method described in PTL 6, according to
the investigations of the present inventors,
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine was
insufficiently extracted with an acyclic ketone solvent, and
therefore, the yield was as low as 30% or less.
[0034] In the ion exchange method described in PTL 7, according to
the investigations of the present inventors, when the same
operation was carried out using a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine disodium
salt, the ion exchange rate of the counter-cation was as low as 20%
or less.
[0035] Therefore, it is an object of the present invention to
provide a water-soluble triarylphosphine for a palladium catalyst,
which has high selectivity in a telomerization reaction and is
easily recovered with efficiency, and a method for producing the
same efficiently.
Solution to Problem
[0036] The present inventors have conducted extensive studies, and
as a result, they have found that the selectivity for desired
products is increased in a telomerization reaction of two molecules
of an alkadiene such as butadiene with a nucleophilic reactant such
as water by using a palladium catalyst comprised of a specific
ammonium salt of
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine and a
palladium compound. Further, they have also found that in the case
of using the palladium catalyst in a telomerization reaction,
products can be extracted from the organic phase by adding an
organic solvent having a specific dielectric constant to the
obtained telomerization reaction liquid, while recovery of the
palladium catalyst from the aqueous phase can be carried out with
high yield, thereby completing the present invention.
[0037] That is, the present invention relates to [1] to [7]
below.
[0038] [1]
Bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine.
[0039] [2] A
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt obtained by reacting the
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine according to
[1] with a tertiary amine having a total of 3 to 27 carbon atoms in
groups bonded to one nitrogen atom.
[0040] [3] The
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt according to [2], wherein the tertiary amine is
trimethylamine, triethylamine, tripropylamine, triisopropylamine,
tributylamine, triisobutylamine, tri-s-butylamine,
tri-t-butylamine, tripentylamine, triisopentylamine,
trineopentylamine, trihexylamine, triheptylamine, trioctylamine,
triphenylamine, tribenzylamine, N,N-dimethylethylamine,
N,N-dimethylpropylamine, N,N-dimethylisopropylamine,
N,N-dimethylbutylamine, N,N-dimethylisobutylamine,
N,N-dimethyl-s-butylamine, N,N-dimethyl-t-butylamine,
N,N-dimethylpentylamine, N,N-dimethylisopentylamine,
N,N-dimethylneopentylamine, N,N-dimethylhexylamine,
N,N-dimethylheptylamine, N, N-dimethyloctylamine,
N,N-dimethylnonylamine, N,N-dimethyldecylamine,
N,N-dimethylundecylamine, N,N-dimethyldodecylamine,
N,N-dimethylphenylamine, N,N-dimethylbenzylamine,
N,N-diethylmonomethylamine, N,N-dipropylmonomethylamine,
N,N-diisopropylmonomethylamine, N,N-dibutylmonomethylamine,
N,N-diisobutylmonomethylamine, N,N-di-s-butylmonomethylamine,
N,N-di-t-butylmonomethylamine, N,N-dipentylmonomethylamine,
N,N-diisopentylmonomethylamine, N,N-dineopentylmonomethylamine,
N,N-dihexylmonomethylamine, N,N-diheptylmonomethylamine,
N,N-dioctylmonomethylamine, N,N-dinonylmonomethylamine,
N,N-didecylmonomethylamine, N,N-diundecylmonomethylamine,
N,N-didodecylmonomethylamine, N,N-diphenylmonomethylamine,
N,N-dibenzylmonomethylamine, N,N-dipropylmonomethylamine,
N,N-diisopropylmonoethylamine, N,N-dibutylmonoethylamine,
N,N-diisobutylmonoethylamine, N,N-di-s-butylmonoethylamine,
N,N-di-t-butylmonoethylamine, N,N-dipentylmonoethylamine,
N,N-diisopentylmonoethylamine, N,N-dineopentylmonoethylamine,
N,N-dihexylmonoethylamine, N,N-diheptylmonoethylamine,
N,N-dioctylmonoethylamine, N,N-dinonylmonoethylamine,
N,N-didecylmonoethylamine, N,N-diundecylmonoethylamine,
N,N-didodecylmonoethylamine, N,N-diphenylmonoethylamine,
N,N-dibenzylmonoethylamine, or trinonylamine.
[0041] [4] A mixture comprising 5% by mole or less of
bis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 80% by mole
or more of bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine,
and 15% by mole or less of
tris(6-methyl-3-sulphophenyl)phosphine.
[0042] A mixture containing 80% by mole or more of a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt obtained by reacting the mixture according to [4]
with a tertiary amine having a total of 3 to 27 carbon atoms in
groups bonded to one nitrogen atom.
[0043] [6] A method for producing bis
(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, having; a step
of reacting 2.5 moles to 4.5 moles of sulphur trioxide with 1 mole
of tris(2-methylphenyl)phosphine in the presence of concentrated
sulphuric acid to obtain a sulphonation reaction liquid, and
diluting the obtained sulphonation reaction liquid with water to
obtain a diluted liquid; a step of neutralizing the diluted liquid
with an alkali metal hydroxide; and a step of bringing the aqueous
solution obtained in the neutralization step into contact with a
strongly acidic cation exchange resin.
[0044] [7] A method for producing a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt by reacting
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine with a
tertiary amine having a total of 3 to 27 carbon atoms in groups
bonded to one nitrogen atom.
Advantageous Effects of Invention
[0045] According to the present invention, high selectivity in a
telomerization reaction can be accomplished by using a
water-soluble triarylphosphine for a palladium catalyst, and the
palladium catalyst after use can be efficiently recovered. Further,
a water-soluble triarylphosphine, which will be a raw material for
a palladium catalyst, can be selectively produced by the production
method of the present invention.
DESCRIPTION OF EMBODIMENTS
[0046] First, in the present specification, the restrictive wording
with "being preferable" can be arbitrarily adopted, and a
combination of restrictive wordings with "being preferable" can be
said to be more preferred.
[0047] The present invention provides
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine and an
ammonium salt thereof. The ammonium salt thereof is more
specifically a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt.
[0048] These can be produced efficiently by the following steps,
but the invention is not particularly limited to the following
steps.
[0049] [1. Sulphonation Step]
[0050] A step of reacting 2.5 moles to 4.5 moles of sulphur
trioxide with 1 mole of tris(2-methylphenyl)phosphine in the
presence of concentrated sulphuric acid to obtain a sulphonation
reaction liquid, and diluting the obtained sulphonation reaction
liquid with water to obtain a diluted liquid is included.
[0051] [2. Neutralization Step]
[0052] A step of neutralizing the diluted liquid with an alkali
metal hydroxide to obtain an aqueous solution including a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phsphine dialkali
metal salt.
[0053] [3. Ion Exchange Step]
[0054] A step of bringing the aqueous solution obtained in the
neutralization step into contact with a strongly acidic cation
exchange resin to form
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine.
[0055] The bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine
can be produced by the steps hitherto described. Further, for the
production of a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt, the following steps are further required.
[0056] [4. Ammonium Salt Forming Step]
[0057] A step of reacting
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine with a
tertiary amine having a total of 3 to 27 carbon atoms in groups
bonded to one nitrogen atom to form a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt.
[0058] Furthermore, the steps will be described in detail below,
but from the viewpoint that the phosphine compound is easily
oxidized by oxygen, although not being clearly described,
operations in the steps are carried out in an inert gas atmosphere
in principle. Furthermore, from the same viewpoint, in the case of
using a solvent, it is preferable to use a solvent having dissolved
oxygen included in the solvent is purged with an inert gas.
Examples of the inert gas include nitrogen, helium, and argon, and
from the viewpoint of high industrial availability, it is
preferable to use nitrogen gases.
[0059] [1. Sulphonation Step]
[0060] The method for producing tris(2-methylphenyl)phosphine is
not particularly limited, and the tris(2-methylphenyl)phosphine can
be produced according to a known method. For example, a reaction of
phosphorous trichloride with a Grignard reagent obtained from
2-bromotoluene (see Journal of Organic Chemistry, 1978, vol. 43,
pp. 2941 to 2956) and the like are known.
[0061] Furthermore, as the tris(2-methylphenyl)phosphine, those
that are commercially distributed can be used, and for example,
"TOTP" (registered trademark) manufactured by Hokko Chemical
Industry Co., Ltd., and the like can be purchased and used.
[0062] The operation sequence in the reaction of
tris(2-methylphenyl)phosphine with sulphur trioxide in the presence
of concentrated sulphuric acid is not particularly limited, but for
example, tris(2-methylphenyl)phosphine can be sulphonated by
dissolving tris(2-methylphenyl)phosphine in concentrated sulphuric
acid, followed by reaction with sulphur trioxide.
[0063] Furthermore, sulphonation can also be carried out by the
reaction with orthoboric acid instead of sulphur trioxide.
According to the findings of the present inventors, in the case of
using orthoboric acid, from the viewpoint that the removal of
orthoboric acid from the sulphonation reaction liquid is
complicated, it is preferable to use sulphur trioxide, and it is
more preferable to use fuming sulphuric acid including sulphur
trioxide and sulphuric acid.
[0064] The sulphonation step can be carried out using a continuous
stirred tank reactor equipped with a jacket. The continuous stirred
tank reactor as mentioned herein is a reactor designed such that
raw materials supplied to the reactor are mixed in a substantially
homogeneous dispersion state without any delay.
[0065] The material for the reactor is preferably stainless steel,
Hastelloy C, titanium, or the like, and further, as a material for
an inner wall of a reactor, a glass-lined material may be used.
From the viewpoint of avoiding the incorporation of metal ions
originating from the reactor into a desired product, it is
preferable to use glass-lined material for the inner wall. Further,
the glass lining process is a method in which two materials, a
metal and glass, are fused to perform surface modification of the
metal.
[0066] The sulphonation step can be carried out in any of a batch
mode (including a semi-continuous mode) and a flow and continuous
mode. In some cases, it can also be carried out in a flow and
continuous mode by connecting two or three continuous stirred tank
reactors in series. From the viewpoint that simplification of
equipment results from dilution of a sulphonation reaction liquid
with water as described later and the subsequent neutralization
step, both carried out in one reaction tank, it is preferable to
carry out the process in a batch mode (including a semi-continuous
mode).
[0067] Concentrated sulphuric acid serves to dissolve
tris(2-methylphenyl)phosphine. As the concentrated sulphuric acid,
one having a high content of sulphuric acid is preferred, and from
the viewpoint of industrial availability, one having a
concentration of 96% by mass or more is more preferably used. A
higher content of sulphuric acid in concentrated sulphuric acid is
preferable since it can inhibit the hydrolysis of sulphur trioxide
in fuming sulphuric acid. From the viewpoint that fuming sulphuric
acid is more expensive than sulphuric acid, it is economically
preferable to inhibit the hydrolysis of sulphur trioxide.
[0068] Since concentrated sulphuric acid used for sulphonation is
generally subjected to a disposal treatment by forming a sulphuric
acid alkali metal salt by neutralization with an alkali metal
hydroxide or the like, production conditions for reducing the
amount of sulphuric acid used are preferred. From this viewpoint,
the amount of sulphuric acid used is preferably about an amount
which allows tris(2-methylphenyl)phosphine to be dissolved, and
more preferably an amount which adjusts the amount of
tris(2-methylphenyl)phosphine to be from 20% by mass to 70% by
mass. Within this range, the amount of sulphuric acid to be
disposed of can be reduced, it becomes possible to perform a
reaction with sulphur trioxide in a sufficiently mixed state due to
low viscosity of the prepared mixed solution, and in addition, the
yield of the desired product is enhanced.
[0069] The temperature at a time of preparation of a concentrated
sulphuric acid solution of tris(2-methylphenyl)phosphine is
preferably from 0.degree. C. to 100.degree. C., and more preferably
from 20.degree. C. to 40.degree. C. Within this range, the
oxidation reaction of tris(2-methylphenyl)phosphine does not
proceed, it becomes possible to perform a reaction with sulphur
trioxide in a sufficiently mixed state due to low viscosity of the
prepared mixed solution, and in addition, the yield of the desired
product is enhanced.
[0070] Sulfur trioxide is preferably used for the reaction in the
form of a fuming sulphuric acid in which sulphur trioxide is
dissolved in sulphuric acid. The concentration of sulphur trioxide
in fuming sulphuric acid is preferably from 10% by mass to 60% by
mass, and more preferably from 20% by mass to 50% by mass. Within
this range, the amount of sulphuric acid practically used can be
reduced, and the time required for the sulphonation step can be
shortened due to a fact that the sulphur trioxide concentration in
the reaction system can be maintained at a certain level or
higher.
[0071] The amount of sulphur trioxide used is preferably from 2.5
moles to 4.5 moles, and more preferably from 3.0 moles to 4.0
moles, with respect to one mole of phosphorous atoms contained in
tris(2-methylphenyl)phosphine. Within this range, the yield of the
desired product is high. Further, the numerical value range is a
numerical value not considering the consumption by hydrolysis. In
the case where consumption by hydrolysis is considered, it is
preferable to increase the amount of sulphur trioxide used
according to the amount.
[0072] The reaction temperature for the sulphonation step is
preferably from 0.degree. C. to 100.degree. C., more preferably
from 10.degree. C. to 50.degree. C., and still more preferably from
20.degree. C. to 50.degree. C. Within this range, even in the state
where the reaction time is short, the yield of a desired product is
high.
[0073] It is preferable to add fuming sulphuric acid to a
concentrated sulphuric acid solution of
tris(2-methylphenyl)phosphine slowly, and the time taken for the
addition is preferably from 0.25 hours to 5 hours, and more
preferably from 0.5 hours to 3 hours. Within this range, the
reaction time is not too long, and the yield of a desired product
is high. Further, it is preferable that after the addition of
fuming sulphuric acid, the flow path of the fuming sulphuric acid
is washed with concentrated sulphuric acid, and a washing liquid
thus obtained is mixed with the reaction solution.
[0074] The reaction time after the completion of addition of fuming
sulphuric acid is preferably from 2 hours to 20 hours, and more
preferably from 2 hours to 8 hours. In the case of this range, the
yield of a desired product is high.
[0075] (Water Dilution Operation)
[0076] Unreacted sulphur trioxide can be hydrolyzed by diluting the
sulphonation reaction liquid obtained by the operation above with
water, whereby it is possible to stop the sulphonation
reaction.
[0077] Furthermore, water used for the dilution serves to remove
the dilution heat of concentrated sulphuric acid and the hydrolysis
reaction heat of sulphur trioxide, and also serves as a solvent in
the neutralization step of the next step.
[0078] The temperature of water used for dilution may be any
temperature at which water does not freeze, and it is preferably
from 1.degree. C. to 40.degree. C., and more preferably from
2.degree. C. to 25.degree. C. Among the temperatures in this range,
a lower temperature is preferred since heat can be efficiently
removed.
[0079] The amount of water used may be at least any amount in which
unreacted sulphur trioxide can be hydrolyzed, but from the
viewpoint of control of the temperature in the neutralization step
as described later, it is from 1 time to 20 times by mass that of
the sulphonation reaction liquid. Within this range, heat removal
is easy and the amount of waste water in the neutralization step as
described later can be reduced.
[0080] The liquid temperature at the time of dilution with water is
preferably from 0.degree. C. to 100.degree. C., and more preferably
from 1.degree. C. to 40.degree. C. Within this range, operations
such as lowering the temperature of the liquid at a time of
starting the neutralization step are not required, and thus, the
productivity can be improved.
[0081] [2. Neutralization Step]
[0082] In the neutralization step, the reactor used in the
sulphonation step is used as it is, and further, it is preferable
to continuously carry out the step in a batch mode (including a
semi-continuous mode) from the viewpoint of simplification of
equipment.
[0083] Examples of the alkali metal hydroxide used in the
neutralization step include lithium hydroxide, sodium hydroxide,
and potassium hydroxide. Among these, potassium hydroxide and
sodium hydroxide are preferred, and sodium hydroxide is more
preferred.
[0084] By using the alkali metal hydroxide, a high ion exchange
rate from bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
dialkali metal salt to
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine with a
strongly acidic cation exchange resin can be accomplished.
[0085] The alkali metal hydroxide may be used in the form of a
solid and may be used as an aqueous solution. However, from the
viewpoints of avoiding local heat generation at a time of
neutralization and increasing the heat removal efficiency, the
alkali metal hydroxide is preferably used as an aqueous solution.
The concentration of the aqueous alkali metal hydroxide solution is
not particularly limited, and the aqueous alkali metal hydroxide
solution is preferably used at a concentration of 10% by mass to
50% by mass, and more preferably used at a concentration of 20% by
mass to 40% by mass. Within this range, the liquid amount after the
neutralization is low, and thus, the amount of waste water can be
reduced. Further, it is preferable that the aqueous alkali metal
hydroxide solution is slowly added to the sulphonation reaction
liquid obtained in the sulphonation step, and in some cases, the
aqueous alkali metal hydroxide solution can be added in several
separate portions. Further, after using the aqueous alkali metal
hydroxide solution in the concentration range, aqueous alkali metal
hydroxide solutions having different concentrations, for example,
an aqueous alkali metal hydroxide solution (usually an aqueous
alkali metal hydroxide solution having a low concentration) having
a concentration out of the range may be used later.
[0086] The amount of alkali metal hydroxide used is not
particularly limited as long as it can neutralize sulphuric acid
and bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, and it
is preferably an amount such that the pH of the aqueous solution at
25.degree. C. after the completion of neutralization is preferably
from 7.0 to 9.5, and more preferably from 7.5 to 8.5. Within this
range, most of sulphuric acid can be induced to a sulphuric acid
alkali metal salt. Further, excess alkali metal hydroxide can be
converted to water in the ion exchange step as described later.
[0087] The neutralization temperature is not particularly limited,
and usually, it is preferably from 0.degree. C. to 40.degree. C.,
and more preferably from 1.degree. C. to 25.degree. C. in order to
promote desirable precipitation of alkali metal sulphate. When the
neutralization temperature is 0.degree. C. or higher, the amount of
energy consumed, relevant to cooling, can be reduced, which is thus
preferable. Further, when the neutralization temperature is
40.degree. C. or lower, precipitation of the alkali metal sulphate
during the transportation of the liquid can be inhibited, and
therefore, there is no concern about pipes becoming blocked.
[0088] The time required for the neutralization is any time as long
as it is in a range suitable for the heat removal ability of a
reactor used. Specifically, the time is preferably from 0.5 hours
to 20 hours, and more preferably from 2 hours to 5 hours. When the
time is 0.5 hours or longer, it is possible to remove
neutralization heat efficiently. As a result, it is economically
advantageous since it is not necessary to use a continuous stirred
tank with high efficiency in heat removal. When the time is 20
hours or shorter, the increase in the amount of energy consumed for
maintenance of the set temperature can be inhibited, which is thus
preferable.
[0089] The aqueous solution formed by the neutralization in the
present step (hereinafter referred to as a neutralized liquid) has
a bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
dialkali metal salt and an alkali metal sulphate as a main
component.
[0090] The solubility in an alcohol, such as methanol, ethanol, and
1-propanol, of the
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine dialkali
metal salt is higher than that of the alkali metal sulphate, and
thus, by using the difference in solubility, the alkali metal
sulphate can be separated out. Although it is possible to
precipitate the alkali metal sulphate by directly adding an alcohol
to the neutralized liquid, it is preferable to evaporate as much
water as possible from the neutralized liquid in advance, and it is
more preferable to evaporate 90% by mass to 98% by mass of the
water in the neutralized liquid, from the viewpoints of reducing
the amount of alcohol used and inhibiting the incorporation of the
alkali metal sulphate into a desired product. In this manner, an
approach in which the alcohol is added to a concentrate obtained by
evaporating water to separate out the alkali metal sulphate is
preferred.
[0091] Examples of the alcohol include methanol, ethanol, and
1-propanol, and from the viewpoint of reducing the amount of the
alcohol, it is preferable to use methanol.
[0092] The amount of the alcohol used for the separation of the
alkali metal sulphate is not particularly limited, and is
preferably from 0.5-fold by mass to 80-fold by mass, and more
preferably from 5-fold by mass to 20-fold by mass, with respect to
the concentrate. Within this range, at a time of isolation of a
desired product, the amount of alcohol evaporated can be reduced,
and further, the alkali metal salt can be sufficiently
precipitated.
[0093] An insoluble material of the alcohol solution is the alkali
metal sulphate, which may be separated and removed by filtration or
decantation. The temperature for filtration or decantation is
preferably from 0.degree. C. to 50.degree. C., and more preferably
from 1.degree. C. to 25.degree. C. Within this range, it is
possible to precipitate only the alkali metal sulphate selectively,
and thus, the yield of a desired product is high.
[0094] In the case where the alkali metal sulphate is incorporated
into the alcohol solution obtained as described above, the obtained
alcohol solution may be concentrated and be dissolved in an alcohol
again to repeat the operation for separation and removal of the
alkali metal sulphate.
[0095] By evaporating the alcohol from the alcohol solution, it is
possible to acquire a mixture of 5% by mole or less of a
bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine alkali
metal salt, 80% by mole or more of a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine dialkali
metal salt, and 15% by mole or less of a
tris(6-methyl-3-sulphonatophenyl)phosphine trialkali metal salt as
a solid. This mixture will be hereinafter abbreviated as a mixture
of alkali metal salts.
[0096] In order to increase the content of the
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine dialkali
metal salt in the mixture of alkali metal salts, column
chromatography using a mixed solvent including water,
tetrahydrofuran, and the like as a mobile phase, which is passed
through columns packed with silica gel, can be used. Alternatively,
a method in which an aqueous solution of a mixture of alkali metal
salts is prepared and washed with an organic solvent such as
2-butanone can also be used.
[0097] [3. Ion Exchange Step]
[0098] By reacting the mixture of alkali metal salts obtained in
the neutralization step with a strongly acidic cation exchange
resin, bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine can be
derived from the
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine dialkali
metal salt.
[0099] According to the investigations of the present inventors, in
a known method including reacting a triarylphosphine in which a
counter-cation of a sulpho group is an alkali metal with a tertiary
amine and carbon dioxide in the presence of an alcohol solvent, and
a known method including reacting a triarylphosphine in which a
counter-cation of a sulpho group is an alkali metal with a protonic
acid in a solvent such as an acyclic ketone, the yield of a desired
product is lowered in any case. Therefore, it is crucial to use a
strongly acidic ion exchange resin, and according to the method,
the yield of a desired product is increased.
[0100] It is also possible to bring an alcohol solution of the
mixture of alkali metal salts as it is into contact with a strongly
acidic cation exchange resin, but since the solubility of the
mixture of alkali metal salts in an alcohol is lower than that in
water, it is preferable to bring the mixture of alkali metal salts
from an aqueous solution into contact with a strongly acidic cation
exchange resin to undergo a reaction.
[0101] By using a strongly acidic cation exchange resin as a cation
exchange resin, the alkali metal ions can be sufficiently converted
to protons even with a small amount of the ion exchange resin.
[0102] As the strongly acidic cation exchange resin, those in which
a sulpho group is introduced to a copolymer of styrene and
divinylbenzene, a copolymer of perfluorosulphonic acid and
tetrafluoroethylene, and the like can be preferably used.
[0103] Examples of the strongly acidic cation exchange resin
include those which are non-aqueous and aqueous, either of which
may be used. According to the kind of a substrate, a macroporous
type substrate, a gel type substrate, and the like can be
mentioned, either of which may be used. As the strongly acidic
cation exchange resin, those in which the counterion of a sulpho
group contained in the resin is a proton or a sodium ion are
generally known. In the case where the counterion is a sodium ion,
the sodium ion is converted into a proton by carrying out a
pre-treatment with a protonic acid such as hydrochloric acid and
sulphuric acid, then the pretreated resin is used. In the case of a
resin in which the counterion is a proton, it can be used without a
pre-treatment.
[0104] The strongly acidic cation exchange resin may have a powder
shape or particulate shape, but from the viewpoint of avoiding
damage due to friction in the state of use, it is preferable to use
a resin having a particulate shape. In the case of using a resin
having a particulate shape, the average particle diameter is not
particularly limited, and is preferably from 0.3 mm to 3 mm, and
more preferably from 0.5 mm to 1.5 mm. When the average particle
diameter is 0.3 mm or more, it is difficult for the resin to be
incorporated into a product, whereas when the average particle
diameter is 3 mm or less, a large contact area of the resin with
the aqueous solution of the mixture of alkali metal salts can be
maintained, and as a result, the amount of the strongly acidic
cation exchange resin used can be reduced.
[0105] Examples of the strongly acidic cation exchange resin formed
by introducing a sulpho group into a copolymer of styrene and
divinylbenzene, which satisfies the above, include Amberlyst 15,
Amberlyst 16, Amberlyst 31, Amberlyst 32, and Amberlyst 35[in which
Amberlyst is a registered trademark], all manufactured by Rohm and
Haas Company, Dowex 50W, Dowex 88, and Dowex G-26 [in which Dowex
is a registered trademark], all manufactured by Dow Chemical
Company, and Diaion SK104, Diaion SK1B, Diaion PK212, Diaion PK216,
and Diaion PK228 [in which Diaion is a registered trademark], all
manufactured by Mitsubishi Chemical Corporation.
[0106] Examples of the strongly acidic cation exchange resin as a
copolymer of perfluorosulphonic acid and tetrafluoroethylene
include Nafion SAC-13 and Nafion NR-50 [in which Nafion is a
registered trademark], both manufactured by E. I. du Pont de
Nemours and Company.
[0107] The strongly acidic cation exchange resins may be used alone
or in combination of two or more kinds thereof.
[0108] The ion exchange step can be carried out in either a flow
mode or a batch mode. In the case of carrying out in a flow mode
using a column, a fixed bed reactor, or the like, damage due to the
friction of the strongly acidic cation exchange resin can be
inhibited, and further, there is an effect that the equilibrium
reaction is biased, whereby the amount of the strongly acidic
cation exchange resin used can be reduced.
[0109] From the viewpoint of making the flow of the aqueous
solution uniform, it is preferable that the reactor has a tubular
structure. The tube diameter is not particularly limited, but it is
preferably from 50 mm to 500 mm from the viewpoint of making the
exchange operation of the strongly acidic cation exchange resin
convenient. The length and number of the reactor tube as a reactor
are not particularly limited, but are preferably appropriately set
from the viewpoint of the production cost, strongly acidic cation
exchange resin and the like, which the resin is required to achieve
a desired production capacity of the reactor.
[0110] In addition, the laminar flow may be in a down-flow mode for
supplying the aqueous solution from the top of a reactor or an
upflow mode for supplying from the bottom of a reactor when the
reactor is a fixed bed reactor.
[0111] The concentration of the mixture of alkali metal salts in
the aqueous solution of the mixture of alkali metal salts is
preferably from 1% by mass to 30% by mass, and more preferably from
5% by mass to 20% by mass. Within these ranges, it is possible to
convert 99% by mole or more of the alkali metal ions into protons
even with a small amount of water used.
[0112] The temperature of the aqueous solution of the mixture of
alkali metal salts is preferably from 10.degree. C. to 120.degree.
C., and more preferably from 15.degree. C. to 40.degree. C. If the
temperature is 10.degree. C. or higher, there is no reduction in
the ion exchange rate, and the increase in the amount of the
strongly acidic cation exchange resin used can be avoided. Further,
if the temperature is 120.degree. C. or lower, the pores of the
resin can be inhibited from being closed by the deformation of the
ion exchange resin, and in addition, the reduction in the rate of
ion exchange can be inhibited.
[0113] The amount of the strongly acidic cation exchange resin used
preferably corresponds to 1.5 times or more the theoretical
ion-exchangeable amount which is calculated from the amount of the
alkali metal ions to be preliminarily exchanged. By this, it is
possible to exchange 99% by mole or more of the alkali metal ions
included in the mixture of alkali metal salts with protons. In
addition, in the case where a higher ion exchange rate is desired,
the alkali metal ions may undergo a reaction repeatedly with the
strongly acidic cation exchange resins.
[0114] The flow rate of the aqueous solution of the mixture of
alkali metal salts is not particularly limited, but the liquid
hourly space velocity (LHSV), a value obtained by dividing a volume
velocity (m.sup.3/hr) of the aqueous solution supplied by a volume
(m.sup.3) of a resin layer including the strongly acidic cation
exchange resin, is preferably from 5 hr.sup.-1 to 30 hr.sup.-1, and
more preferably from 10 hr.sup.-1 to 20 hr.sup.-1. Within this
range, the ion exchange efficiency is high.
[0115] By evaporating water from an aqueous solution which has been
brought into contact with the strongly acidic cation exchange
resin, it is possible to acquire a mixture of 5% by mole or less of
bis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 80% by mole
or more of bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine,
and 15% by mole or less of tris(6-methyl-3-sulphophenyl)phosphine,
as a solid. This mixture will be hereinafter abbreviated as an ion
exchanged mixture.
[0116] [4. Ammonium Salt Forming Step]
[0117] It is possible to derive a corresponding ammonium salt by
allowing a sulpho group included in the ion exchanged mixture
obtained in the ion exchange step to undergo a reaction with the
same number of moles of a tertiary amine.
[0118] It is preferable that the ion exchanged mixture is dissolved
in water, and from the viewpoint of reducing the amount of the
solvent evaporated, the ion exchanged mixture is preferably used as
an aqueous solution including 3% by mass to 25% by mass of the ion
exchanged mixture.
[0119] The appropriate amount of the tertiary amine can be
confirmed by potentiometric titration. In the case of adding excess
tertiary amine, the excess tertiary amine may be evaporated.
[0120] The amount of tertiary amine used is preferably 1-fold by
mole to 3-fold by mole, more preferably 1.1-fold by mole to 2-fold
by mole, and still more preferably 1.1-fold by mole to 1.5-fold by
mole of that of the sulpho groups included in the ion exchanged
mixture.
[0121] By concentrating a solution obtained by reacting the ion
exchanged mixture with the tertiary amine to dryness, a desired
product as a solid can be isolated, and by evaporating a part of
the water, a concentrated aqueous solution can be acquired or the
solution may be used as it is.
[0122] By directly adding the tertiary amine to the aqueous
solution of the ion exchanged mixture, and sufficiently mixing them
at 10.degree. C. to 30.degree. C. over 0.5 hours to 3 hours, the
reaction with the corresponding ammonium sufficiently proceeds.
[0123] Furthermore, as the tertiary amine, a tertiary amine having
a total of 3 to 27 carbon atoms in alkyl groups bonded to one
nitrogen atom is used.
[0124] Examples of the tertiary amine include trimethylamine,
triethylamine, tripropylamine, triisopropylamine, tributylamine,
triisobutylamine, tri-s-butylamine, tri-t-butylamine,
tripentylamine, triisopentylamine, trineopentylamine,
trihexylamine, triheptylamine, trioctylamine, triphenylamine,
tribenzylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine,
N,N-dimethylisopropylamine, N,N-dimethylbutylamine,
N,N-dimethylisobutylamine, N,N-dimethyl-s-butylamine,
N,N-dimethyl-t-butylamine, N,N-dimethylpentylamine,
N,N-dimethylisopentylamine, N,N-dimethylneopentylamine,
N,N-dimethylhexylamine, N,N-dimethylheptylamine,
N,N-dimethyloctylamine, N,N-dimethylnonylamine,
N,N-dimethyldecylamine, N,N-dimethylundecylamine,
N,N-dimethyldodecylamine, N,N-dimethylphenylamine,
N,N-dimethylbenzylamine, N,N-diethylmonomethylamine,
N,N-dipropylmonomethylamine, N,N-diisopropylmonomethylamine,
N,N-dibutylmonomethylamine, N,N-diisobutylmonomethylamine,
N,N-di-s-butylmonomethylamine, N,N-di-t-butylmonomethylamine,
N,N-dipentylmonomethylamine, N,N-diisopentylmonomethylamine,
N,N-dineopentylmonomethylamine, N,N-dihexylmonomethylamine,
N,N-diheptylmonomethylamine, N,N-dioctylmonomethylamine,
N,N-dinonylmonomethylamine, N,N-didecylmonomethylamine,
N,N-diundecylmonomethylamine, N,N-didodecylmonomethylamine,
N,N-diphenylmonomethylamine, N,N-dibenzylmonomethylamine,
N,N-dipropylmonomethylamine, N,N-diisopropylmonoethylamine,
N,N-dibutylmonoethylamine, N,N-diisobutylmonoethylamine,
N,N-di-s-butylmonoethylamine, N,N-di-t-butylmonoethylamine,
N,N-dipentylmonoethylamine, N,N-diisopentylmonoethylamine,
N,N-dineopentylmonoethylamine, N,N-dihexylmonoethylamine,
N,N-diheptylmonoethylamine, N,N-dioctylmonoethylamine,
N,N-dinonylmonoethylamine, N,N-didecylmonoethylamine,
N,N-diundecylmonoethylamine, N,N-didodecylmonoethylamine,
N,N-diphenylmonoethylamine, N,N-dibenzylmonoethylamine, and
trinonylamine. These may be used alone or as a mixture of two or
more kinds thereof.
[0125] The total number of carbon atoms in groups bonded to one
nitrogen atom is preferably from 3 to 24, more preferably from 5 to
24, still more preferably from 5 to 10, and particularly preferably
from 5 to 7. Further, as the group bonded to one nitrogen atom, an
alkyl group, an aryl group, and an aryl-substituted alkyl group are
preferred, and an alkyl group is more preferred.
[0126] Among those, as the tertiary amine, triethylamine,
N,N-dimethylisopropylamine, and trioctylamine are preferred, and
from the viewpoints of easy availability and production cost,
triethylamine and N,N-dimethylisopropylamine are more
preferred.
[0127] By evaporating water from the reaction mixed solution after
completion of the reaction, it is possible to acquire a mixture of
5% by mole or less of a
bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine ammonium
salt, 80% by mole or more of a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt, and 15% by mole or less of a
tris(6-methyl-3-sulphonatophenyl)phosphine triammonium salt, as a
solid. This mixture will be hereinafter abbreviated as a mixture of
ammonium salts.
[0128] In order to increase the content of the
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt in the mixture of ammonium salts, column
chromatography using a mixed solvent including water,
tetrahydrofuran, and the like as a mobile phase, which is passed
through a column packed with silica gel, can be used.
Alternatively, a method in which an aqueous solution of a mixture
of alkali metal salts is prepared and washed with an organic
solvent such as 2-butanone can also be used.
[0129] A palladium catalyst comprised of the
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt obtained as above, or a mixture containing the
same, and a palladium compound is excellent as a catalyst for a
telomerization reaction. Examples of the telomerization reaction
include a reaction in which butadiene is reacted with water in the
presence of a palladium catalyst, a tertiary amine, and carbon
dioxide to obtain 2,7-octadien-1-ol. In the telomerization
reaction, the selectivity for 2,7-octadien-1-ol is improved and the
recovery of the palladium catalyst is high, and therefore, the
industrial availability is very high.
[0130] Furthermore, preferred examples of the palladium compound
include 0-valent palladium compounds such as
bis(t-butylisonitrile)palladium (0), bis(t-amylisonitrile)palladium
(0), bis(cyclohexylisonitrile)palladium (0),
bis(phenylisonitrile)palladium (0), bis(p-tolylisonitrile)palladium
(0), bis(2,6-dimethylphenylisonitrile)palladium (0),
tris(dibenzylideneacetone) dipalladium (0),
(1,5-cyclooctadiene)(maleic anhydride)palladium (0),
bis(norbornene)(maleic anhydride)palladium (0), bis(maleic
anhydride)(norbornene)palladium (0),
(dibenzylideneacetone)(bipyridyl)palladium (0),
(p-benzoquinone)(o-phenanthroline)palladium (0),
tetrakis(triphenylphosphine)palladium (0),
tris(triphenylphosphine)palladium (0),
bis(tritolylphosphine)palladium (0),
bis(trixylylphosphine)palladium (0),
bis(trimesitylphosphine)palladium (0),
bis(tritetramethylphenyl)palladium (0), and
bis(trimethylmethoxyphenylphosphine)palladium (0); and divalent
palladium compounds such as palladium (II) chloride, palladium (II)
nitrate, tetraammine dichloropalladium (II), disodium
tetrachloropalladium (II), palladium (II) acetate, palladium (II)
benzoate, palladium (II) .alpha.-picolinate,
bis(acetylacetone)palladium (II), bis(8-oxyquinoline)palladium
(II), bis(allyl)palladium (II), (.eta.-allyl)
(.eta.-cyclopentadienyl)palladium (II),
(.eta.-cyclopentadienyl)(1,5-cyclooctadiene)palladium (II)
tetrafluoroborate, bis(benzonitrile)palladium (II) acetate,
di-.mu.-chlorodichlorobis(triphenylphosphine)dipalladium (II),
bis(tri-n-butylphosphine)palladium (II) acetate, and 2,2-bipyridyl
palladium (II) acetate.
[0131] Furthermore, in the case where the telomerization reaction
is carried out industrially, a step of mixing the telomerization
reaction liquid obtained in the telomerization reaction step with
an organic solvent having a dielectric constant of 2 to 18 at
25.degree. C., followed by performing phase separation in the
presence of carbon dioxide, thereby obtaining 2,7-octadien-1-ol
from an organic phase (product separation step), and a step of
recovering an aqueous phase including the palladium catalyst with
high efficiency (catalyst recovery step) are preferably carried
out. At this time, in the case of using the
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt or the mixture containing the same, of the present
invention, as a raw material for a palladium catalyst, the
selectivity for a desired product and the recovery of the palladium
catalyst are higher, as compared with other palladium catalysts,
and therefore, the production cost is reduced, which is thus
preferable.
[0132] Furthermore, examples of the organic solvent having a
dielectric constant of 2 to 18 at 25.degree. C. include n-dodecane,
cyclohexane, 1,4-dioxane, benzene, p-xylene, m-xylene, toluene,
dibutyl ether, diisopropyl ether, propanenitrile, ethylphenyl
ether, diethyl ether, methyl-t-butyl ether, cyclopentylmethyl
ether, fluorobenzene, 2-methyltetrahydrofuran, tetrahydrofuran,
2-heptanone, 4-methyl-2-pentanone, cyclopentanone, 2-hexanone,
2-pentanone, cyclohexanone, 3-pentanone, and acetophenone. Further,
the dielectric constant of the organic solvent is preferably from 3
to 10.
EXAMPLES
[0133] Hereinafter, the present invention will be described in more
detail with reference to Examples, but the present invention is not
limited to such Examples in any case.
[0134] Hereinafter, in the production of various water-soluble
triarylphosphines, the production was carried out at room
temperature, at normal pressure, or under a nitrogen atmosphere
unless otherwise specified, and as the solvent, those which had
been purged with nitrogen in advance were used.
[0135] In addition, the water-soluble triarylphosphine obtained by
sulphonating triarylphosphine is a mixture of those in which the
number of sulpho groups introduced is 1 to 3, and may further
include oxides formed by oxidation of the phosphorus.
[0136] The composition ratios (mass ratios) thereof in the
water-soluble triarylphosphine were quantified from peak areas of
.sup.31P obtained by measurement using a nuclear magnetic resonance
apparatus "AVANCE III 400 USPlus" (manufactured by Bruker BioSpin
K. K.) with a dimethylsulphoxide-d.sub.6 (hereinafter referred to
as DMSO-d.sub.6) solution prepared such that the concentration of
the produced water-soluble triarylphosphine is 0.05 mol/L. The
chemical shift of .sup.31P in this case is a value at 305 K in the
case where the chemical shift of the DMSO-d.sub.6 solution prepared
to have a concentration of the phosphoric acid of 0.05 mol/L is set
to 0 ppm.
[0137] Furthermore, the structure of the water-soluble
triarylphosphine is determined from the chemical shifts and the
peak areas of .sup.31P and .sup.1H obtained by measurement using a
nuclear magnetic resonance apparatus "AVANCE III 600 USPlus"
(manufactured by Bruker BioSpin K. K.) with a deuterium oxide
solution prepared to have a concentration of 10 mmol/L. The
chemical shift of .sup.31P in this case is a value at 300 K in the
case where the chemical shift of a deuterium oxide solution
prepared to have a concentration of the phosphoric acid of 10
mmol/L is set to 0 ppm. The chemical shift of .sup.1H in this case
is a value at 300 K in the case where the chemical shift of a
deuterium oxide solution prepared to have a concentration of
trimethylsilylpropanoic acid-d.sub.4 (hereinafter abbreviated as
TSP) of 5 mmol/L is set to 0 ppm.
[0138] Sodium ions were quantified using an atomic absorption
spectrophotometer "AA-7000F" (manufactured by Shimadzu
Corporation).
[0139] For the operation for purifying a desired product, a high
performance liquid chromatographic system (manufactured by Nihon
Waters K.K., DELTA 600 MULTI-SOLVENT Systems, 2998 Photodiode Array
Detector, Column Heater, Chromatography Data Software Empower 1)
was used. Further, as a reversed phase chromatography column,
"TSKgel ODS-80Ts" (particle diameter of 5 .mu.m, inner diameter of
20 mm, and length of 250 mm) manufactured by Tosoh Corporation, was
used.
[0140] <Production of Water-Soluble Triarylphosphine>
Example 1
[0141] Production of
Bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine
[0142] A sulphonation reaction was carried out in a batch mode. A
50 L glass-lined reactor equipped with a thermometer, a stirring
device, and a jacket was used. 9.84 kg of concentrated sulphuric
acid at a concentration of 97.4% by mass was placed in the reactor
and cooled to 16.degree. C. under stirring. Subsequently, 10.91 kg
(35.84 mol) of tris(2-methylphenyl)phosphine (hereinafter
abbreviated as TOTP) was introduced thereinto over 1 hour so as to
maintain the temperature at 30.degree. C. or lower. Thereafter,
37.60 kg (131.50 mol in terms of sulphur trioxide) of fuming
sulphuric acid containing 28% by mass of sulphur trioxide was added
thereto over 3 hours, while controlling the liquid temperature such
that it was in a range of 30.degree. C. to 40.degree. C.
Subsequently, the flow path of fuming sulphuric acid was washed
with 1 kg of concentrated sulphuric acid at a concentration of
97.4% by mass. The reaction was carried out at a liquid temperature
of from 20.degree. C. to 30.degree. C. over 4 hours.
[0143] On the other hand, 70 kg of ion-exchanged water was placed
in a 200 L glass-lined reactor equipped with a thermometer, a
stirring device, and a jacket, and the total amount of the above
sulphonation reaction liquid was transferred thereto over 1 hour.
Further, the flow path of the sulphonation reaction liquid was
washed with 10 kg of ion-exchanged water, and the resultant was
added to the above diluted liquid. In addition, the liquid
temperature was controlled such that it was in a range of
20.degree. C. to 40.degree. C., thereby acquiring 137.80 kg of a
diluted sulphonation reaction liquid.
[0144] 27.50 kg (7.15 mol in terms of phosphorous atoms) of a
diluted sulphonation reaction liquid and 5 kg of ion-exchanged
water were added to a 200 L glass-lined reactor equipped with a
thermometer, a stirring device, and a jacket. 24.10 kg of an
aqueous 30.2%-by-mass sodium hydroxide solution was supplied
thereto over 3 hours while controlling the liquid temperature such
that it was in a range of 10.degree. C. to 30.degree. C. Further,
1.66 kg of an aqueous 4%-by-mass sodium hydroxide solution was
added thereto over 1.7 hours. Thus, a neutralized liquid at pH 7.99
was acquired.
[0145] The neutralized liquid was allowed to exist in the range of
80 kPa to 100kPa at 35.degree. C. to 65.degree. C. and concentrated
over 4.5 hours, and 37 kg of water was evaporated therefrom. 45 kg
of methanol was added to the concentrate, followed by stirring at
40.degree. C. for 1 hour. Further, the mixture was allowed to exist
in the range of 4 kPa to 55 kPa at 40.degree. C. to 55.degree. C.
and concentrated over 2.4 hours, and 45 kg of methanol was
evaporated therefrom. 147 kg of methanol was added to the
concentrate, followed by stirring at 40.degree. C. to 60.degree. C.
for 1 hour. Thereafter, the mixture was cooled to 30.degree. C. or
lower.
[0146] The methanol solution was allowed to pass through a pressure
filter made of SUS304 in which 5 kg of "Celpure (registered
trademark) S1000" manufactured by Advanced Minerals Corporation, as
a high-purity diatomite filter aid was placed, thereby acquiring a
filtrate. In addition, the filter aid was washed with 30 kg of
methanol and the filtrate was combined with the above filtrate.
[0147] The total amount of the above acquired methanol solution was
put into a 100 L glass-lined reactor equipped with a thermometer, a
stirring device, and a jacket, allowed to exist in the range of 4
kPa to 55 kPa at 40.degree. C. to 55.degree. C., and concentrated
to dryness over 18 hours, thereby acquiring 3.56 kg of a white
solid (hereinafter referred to as an acquisition 1).
[0148] The acquisition 1 was a mixture including 0.13 kg (0.33 mol)
of a bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine
sodium salt as a mono-form, 2.91 kg (5.72 mol) of a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine disodium
salt as a di-form, and 0.52 kg (0.85 mol) of a
tris(6-methyl-3-sulphonatophenyl)phosphine trisodium salt as a
tri-form.
[0149] From the viewpoint that 3.56 kg (6.90 mol in terms of
phosphorous atoms) of the acquisition 1 could be acquired from
27.50 kg (7.15 mol in terms of phosphorous atoms) of a diluted
sulphonation reaction liquid, the yield based on the phosphorous
atoms ranging from the sulphonation step to the neutralization step
was 96.5%.
[0150] A column made of an acrylic resin (100 mm in diameter and
760 mm in height), packed with 5 kg of a strongly acidic cation
exchange resin "Dowex G-26", was prepared. 12 kg of an aqueous
solution including the acquisition 1 at 8.6% by mass (1044.0 g in
terms of the acquisition 1, 2023.4 mmol in terms of phosphorous
atoms) was allowed to pass from the upper part of the column at a
linear velocity of 9.3 m/hr to 12.5 m/hr. The obtained aqueous
solution was concentrated to dryness in the range of 35.degree. C.
to 70.degree. C. at 4 kPa to 55 kPa to obtain 914.5 g of a white
solid (hereinafter referred to as an acquisition 2).
[0151] .sup.31P-NMR (400 MHz, 305 K, DMSO-d.sub.6, phosphoric acid,
ppm) .delta.: bis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine
as a mono-form showed a peak at -28.72,
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine as a di-form
showed a peak at -26.00, and tris(6-methyl-3-sulphophenyl)phosphine
as a tri-form showed a peak at -18.85.
[0152] The acquisition 2 was a mixture containing 35.3 g (91.9
mmol, 4.73% by mole) of
bis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 749.4 g
(1613.4 mmol, 83.01% by mole) of
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine, and 129.8 g
(238.3 mmol, 12.26% by mole) of
tris(6-methyl-3-sulphophenyl)phosphine.
[0153] According to the atomic absorption analysis of the
acquisition 2, the sodium content included in the acquisition 2 was
23 ppm or less in terms of sodium atoms. From the viewpoint that
the number of sulpho groups contained in 1.0 kg of the acquisition
2 was 4410.6 mmol and the content of the sodium atoms was 1.0 mmol,
99.98% by mole or more of the sulphonate groups had been converted
to sulpho groups.
[0154] From the viewpoint that 914.5 g (1943.6 mmol in terms of
phosphorous atoms) of an acquisition 2 could be acquired by using
1044.0 kg (2023.4 mmol in terms of phosphorous atoms) of the
acquisition 1, the yield based on the phosphorous atoms in the ion
exchange step was 95.5%.
Example 2
[0155] Purification of
Bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine
[0156] Using a high performance liquid chromatographic system
equipped with a reversed phase chromatography column, a mixed
liquid containing 70% by mass of water and 30% by mass of
acetonitrile as a mobile phase was passed through the system at 5.0
mL/minute in the state where a column oven temperature was
controlled to be 40.degree. C.
[0157] 1 g of an aqueous solution including 1% by mass of the
acquisition 2 of Example 1 was prepared, and injected. The
photodiode array detector was set to 275 nm and a distillate with a
retention time of 17.5 minutes to 20.0 minutes was recovered. This
operation was repeated 10 times. The collected distillate was
concentrated to dryness in the range of 35.degree. C. to 70.degree.
C. and 4 kPa to 56 kPa to acquire 55.5 mg of
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine as a white
solid.
[0158] .sup.31P-NMR (400 MHz, 305 K, DMSO-d.sub.6, phosphoric acid,
ppm) .delta.: -26.00 (s)
[0159] .sup.31P-NMR (600 MHz, 300 K, deuterium oxide, phosphoric
acid, ppm) .delta.: -24.69 (s)
[0160] .sup.1H-NMR (600 MHz, 300 K, deuterium oxide, TSP, ppm)
.delta.: 2.35 (s, 9 H), 6.84 (t, 6.2 Hz, 1 H), 7.18 (t, 7.6 Hz, 1
H), 7.21 (dd, 2.8 Hz, 1.8 Hz, 2 H), 7.35 (t, 6.3 Hz, 1 H), 7.41 (t,
7.4 Hz, 1 H), 7.45 (dd, 3.2 Hz, 4.7 Hz, 2 H), 7.80 (dd, 6.1 Hz, 1.8
Hz, 2 H)
[0161] From the viewpoint that 55.5 mg (0.118 mmol in terms of
phosphorous atoms) of a desired product could be acquired by using
100.0 mg (0.213 mmol in terms of phosphorous atoms) of the
acquisition 2, the yield based on the phosphorous atoms in the
purification was 55.6%.
Example 3
[0162] Production of Bis
(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(triethylammonium) salt
[0163] 500 g of an aqueous solution including 10% by mass of the
acquisition 2 of Example 1 was prepared. Further, this aqueous
solution included 50.0 g of the acquisition 2 with 106.3 mmol in
terms of phosphorous atoms and 221.4 mmol of sulpho groups. An
aqueous solution of the acquisition 2 was placed in a 3-neck flask
having an inner capacity of 1 L, equipped with a thermometer, a
stirring device, a dropping funnel, and a nitrogen gas line, and
24.6 g (243.5 mmol) of triethylamine was added thereto through the
dropping funnel, followed by stirring in the range of 20.degree. C.
to 30.degree. C. over 1 hour, thereby performing a reaction.
[0164] Thereafter, the reaction liquid was concentrated to dryness
in the range of 35.degree. C. to 70.degree. C. and 4 kPa to 56 kPa,
thereby acquiring 68.2 g of a white solid (hereinafter referred to
as an acquisition 3).
[0165] .sup.31P-NMR (400 MHz, 305 K, DMSOd.sub.6, phosphoric acid,
ppm) .delta.: a
bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine
triethylammonium salt as a mono-form showed a peak at -28.12, a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(triethylammonium) salt as a di-form showed a peak at -25.00, and
a tris(6-methyl-3-sulphonatophenyl)phosphine tri(triethylammonium)
salt as a tri-form showed a peak at -19.98.
[0166] The acquisition 3 was a mixture containing 2.3 g (4.7 mmol,
4.73% by mole) of a
bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine
triethylammonium salt, 55.5 g (83.2 mmol, 82.99% by mole) of a
bis(6-methyl-3-sulphonatoephenyl)(2-methylphenyl)phosphine
di(triethylammonium) salt, and 10.4 g (12.3 mmol, 12.28% by mole)
of a tris(6-methyl-3-sulphonatophenyl)phosphine
tri(triethylammonium) salt.
[0167] From the viewpoint that 68.2 g (100.2 mmol in terms of
phosphorous atoms) of the acquisition 3 could be acquired by using
50.0 g (106.3 mmol in terms of phosphorous atoms) of the
acquisition 2, the yield based on the phosphorous atoms in the
ammonium salt forming step was 94.3%.
Example 4
[0168] Purification of
Bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(triethylammonium) salt
[0169] 100 g of an aqueous solution including 50% by mass of the
acquisition 3 of Example 3 was prepared. Further, the present
aqueous solution included 50.0 g of the acquisition 3 with 73.5
mmol in terms of phosphorous atoms. An aqueous solution of the
acquisition 3 was placed in a 3-neck flask having an inner capacity
of 300 L, equipped with a thermometer, a stirring device, a
dropping funnel, and a nitrogen gas line. To an aqueous solution of
the acquisition 3 was added 100 g of 2-butanone, followed by
stirring for 30 minutes, and the mixture was left to stand for 30
minutes, and an operation of removing a 2-butanone phase was
repeated three times. By concentrating the obtained aqueous phase
to dryness in the range of 35.degree. C. to 70.degree. C. and 4 kPa
to 56 kPa, 41.7 g of a white solid was acquired.
[0170] The acquisition was a mixture containing 0.5 g (1.0 mmol,
1.69% by mole) of a
bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine
triethylammonium salt, 34.1 g (51.2 mmol, 84.53% by mole) of a bis
(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(triethylammonium) salt, and 7.1 g (8.3 mmol, 13.78% by mole) of
a tris(6-methyl-3-sulphonatophenyl)phosphine tri(triethylammonium)
salt.
[0171] From the viewpoint that 41.7 g (60.5 mmol in terms of
phosphorous atoms) of a desired product could be acquired by using
50.0 g (73.5 mmol in terms of phosphorous atoms) of the acquisition
3, the yield based on the phosphorous atoms in the purification was
82.4%.
Example 5
[0172] Production of Bis
(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(tri-n-octylammonium) salt
[0173] By carrying out the same operation as in Example 3 except
that 86.1 g (243.5 mmol) of tri-n-octylamine was used instead of
triethylamine, 123.0 g of a pale orange high-viscosity liquid was
acquired.
[0174] .sup.31P-NMR (400 MHz, 305 K, DMSO-d.sub.6, phosphoric acid,
ppm) .delta.: a
bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine
tri-n-octylammonium salt as a mono-form showed a peak at -28.60, a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(tri-n-octylammonium) salt as a di-form showed a peak at -25.00,
and a tris(6-methyl-3-sulphonatophenyl)phosphine
tri(tri-n-octylammonium) salt as a tri-form showed a peak at
-17.67.
[0175] The acquisition was a mixture containing 3.6 g (4.9 mmol,
4.80% by mole) of a
bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine
tri-n-octylammonium salt, 99.2 g (84.6 mmol, 82.87% by mole) of a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(tri-n-octylammonium) salt, and 20.2 g (12.6 mmol, 12.33% by
mole) of a tris(6-methyl-3-sulphonatophenyl)phosphine
tri(tri-n-octylammonium) salt.
[0176] From the viewpoint that 123.0 g (102.1 mmol in terms of
phosphorous atoms) of a desired product could be acquired by using
50.0 g (106.3 mmol in terms of phosphorous atoms) of the
acquisition 2, the yield based on the phosphorous atoms in the
ammonium salt forming step was 96.0%.
Example 6
[0177] Production of
Bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(dimethylisopropylammonium) salt
[0178] By carrying out the same operation as in Example 3 except
that 21.2 g (243.5 mmol) of N,N-dimethylisopropylamine was used
instead of triethylamine, 67.5 g of a white solid was acquired.
[0179] .sup.31P-NMR (400 MHz, 305 K, DMSO-d.sub.6, phosphoric acid,
ppm) .delta.: a
bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine
dimethylisopropylammonium salt as a mono-form showed a peak at
-28.17, a bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(dimethylisopropylammonium) salt as a di-form showed a peak at
-25.25, and a tris(6-methyl-3-sulphonatophenyl)phosphine
tri(dimethylisopropylammonium) salt as a tri-form showed a peak at
-21.50.
[0180] The acquisition was a mixture containing 2.4 g (5.0 mmol,
4.81% by mole) of a
bis(2-methylphenyl)(6-methyl-3-sulphonatophenyl)phosphine
dimethylisopropylammonium salt, 54.8 g (85.9 mmol, 82.85% by mole)
of a bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
di(dimethylisopropylammonium) salt, and 10.3 g (12.8 mmol, 12.34%
by mole) of a tris(6-methyl-3-sulphonatophenyl)phosphine
tri(dimethylisopropylammonium) salt.
[0181] From the viewpoint that 67.5 g (103.6 mmol in terms of
phosphorous atoms) of a desired product could be acquired by using
50.0 g (106.3 mmol in terms of phosphorous atoms) of the
acquisition 2, the yield based on the phosphorous atoms in the
ammonium salt forming step was 97.5%.
[0182] <Telomerization Reaction>
[0183] Hereinafter, it is shown that the water-soluble
triarylphosphine of the present invention is useful for a
telomerization reaction with reference to Reference Examples.
Further, the present invention is not limited to such Reference
Examples in any case.
[0184] Moreover, the concentrations of the palladium compounds and
the phosphorus compounds included in the aqueous phase acquired by
an extraction operation were quantified by subjecting a wet
decomposition product to analysis using a polarized Zeeman atomic
absorption spectrophotometer "Z-5300 Type" (manufactured by
Hitachi, Ltd.).
[0185] In addition, organic materials such as a tertiary amine and
2,7-octadien-1-ol included in the telomerization reaction liquid or
the aqueous phase including the palladium catalyst were analyzed
and quantified by gas chromatography under the following
measurement conditions.
[0186] (Analysis Conditions for Gas Chromatography)
[0187] Apparatus: GC-14 A (manufactured by Shimadzu
Corporation)
[0188] Column used: G-300 (1.2 mm in internal diameter.times.20 m
in length, and a film thickness of 2 .mu.m),
[0189] (Materials) manufactured by Chemicals Evaluation, and
Research Institute, Japan
[0190] Analysis conditions: an inlet temperature of 220.degree. C.
and a detector temperature of 220.degree. C.
[0191] Sample injection amount: 0.4 .mu.L
[0192] Carrier gas: helium (260 kPa) is flowed at 10 mL/minute.
[0193] Column temperature: maintained at 60.degree. C. for 5
minutes.fwdarw.raised at 10.degree. C./minute.fwdarw.maintained at
220.degree. C. for 9 minutes
[0194] Detector: hydrogen flame ionization detector (FID)
Reference Example 1
[0195] The telomerization reaction was carried out in a batch mode.
A 3 L autoclave equipped with a SUS316 electromagnetic induction
stirring device including a 96 mL pressure container made of glass,
for pumping a palladium catalyst, a 96 mL pressure container made
of glass, for pumping a solvent, and a sampling port was used as a
reactor. Further, the reaction was carried out at a stirring
rotation speed of 500 rpm, and from the viewpoint that the reaction
results at this time were not different from those at 1,000 rpm, a
sufficient stirring state could be achieved.
[0196] 17.69 g of a tetrahydrofuran solution including 94.74 mg
(0.422 mmol in terms of palladium atoms) of palladium (II) acetate,
and then 21.46 g of an aqueous solution including 1.440 g (2.116
mmol in terms of trivalent phosphorous atoms) of the phosphorous
compound obtained in Example 3 were introduced into a pressure
container made of glass and stirred for 60 minutes to prepare a
palladium catalyst liquid.
[0197] 30.06 g of distilled water, 80.10 g of triethylamine, 97.50
g of 2,7-octadien-1-ol, and 114.95 g (2.13 mol) of butadiene were
put into the autoclave, followed by stirring at 500 rpm in a closed
system and warming to 70.degree. C. Thereafter, the palladium
catalyst liquid was pumped from the pressure container made of
glass through carbon dioxide within 10 seconds, while the total
pressure was set to 1.2 MPa (gauge pressure). Further, a time point
at which pumping of the palladium catalyst liquid was completed was
defined as 0 hours at initiation of reaction.
[0198] In addition, the ratio of the trivalent phosphorus atoms to
the palladium atoms at a time of preparation of a catalyst was
5.01, and in the telomerization reaction, the amount of the
palladium atoms with respect to 1 mol of butadiene was 0.198 mmol,
the mass ratio of triethylamine to water was 1.55, and the mass
ratio of a mixture of butadiene and 2,7-octadien-1-ol to water was
4.12.
[0199] For the telomerization reaction liquid after a predetermined
reaction time, the product was quantified by gas chromatography
analysis.
[0200] The conversion of the butadiene was calculated by the
following Equation 1. Further, the respective units in the
equations are mol.
Butadiene conversion (%)=100.times.{1-(Amount of butadiene in
reaction liquid/ Amount of butadiene introduced)} [Equation 1]
[0201] Examples of the respective products include
2,7-octadien-1-ol, 1,7-octadien-3-ol, 1,3,6-octatriene,
1,3,7-octatriene, 2,4,6-octatriene, and 4-vinylcyclohexene.
However, 1,3,6-octatriene, 1,3,7-octatriene, and 2,4,6-octatriene
are collectively referred to as octatrienes. The selectivities of
the respective products were calculated by the following Equation
2. Further, the respective units in the equations are mol.
Selectivity for each product (%)=50.times.(Amount of each product
in reaction liquid/Amount of butadiene reacted) [Equation 2]
[0202] The selectivities for high-boiling-point products which
could not be sufficiently quantified by gas chromatography were
calculated by the following Equation 3. Further, the respective
units in the equations are mol.
Selectivity for high-boiling-point product (%)=100-(Total sum of
selectivities of the respective products, calculated by Equation 2)
[Equation 3]
[0203] After 8 hours of the reaction, the butadiene conversion was
81.6%, the selectivity for 2,7-octadien-1-ol was 92.5%, the
selectivity for 1,7-octadien-3-ol was 3.2%, the selectivity for
octatrienes was 2.6%, and the selectivity for the
high-boiling-point products was 1.7%. Further, the selectivity for
4-vinylcyclohexene was 0.01% or less.
[0204] The autoclave was cooled to 25.degree. C., and a reaction
consumption-equivalent amount of water and 330.23 g (a volume at
25.degree. C. of 463.2 mL) of diethyl ether were pumped through
carbon dioxide, using a 96 mL pressure container made of glass, for
pumping a solvent. The mixture was stirred for 1 hour while being
pressurized to a total pressure of 3 MPa (gauge pressure) with
carbon dioxide. This mixed liquid was transferred to a pressure
container equipped with a glass window, which had been pressurized
to 3 MPa (gauge pressure) with carbon dioxide using a pump, to
carry out phase separation. The aqueous phase was suitably
recovered into a pressure container made of glass, which had been
pressurized to 1 MPa (gauge pressure) with carbon dioxide,
connected to a pressure container equipped with a glass window. The
pressure container made of glass was taken out, separated, and
opened at normal pressure, and the weight of the aqueous phase was
measured, while the acquired aqueous phase was used for various
types of analysis.
[0205] In addition, the mass ratio of diethyl ether to the
telomerization reaction liquid was 0.84.
[0206] The content of palladium included in the aqueous phase was
calculated from the concentration of palladium as demonstrated by
the analysis with a polarized Zeeman atomic absorption
spectrophotometer using a wet decomposition product of the aqueous
phase and the weight of the recovered aqueous phase. The recovery
of the palladium atoms was calculated by the following Equation 4.
Further, the units of the respective amounts in the equations are
mol.
Recovery of palladium atoms (%)=(Amount of palladium in aqueous
phase/Amount of palladium introduced).times.100 [Equation 4]
[0207] The content of phosphorous included in the aqueous phase was
calculated from the concentration of phosphorous as demonstrated by
the analysis with a polarized Zeeman atomic absorption
spectrophotometer using a wet decomposition product of the aqueous
phase and the weight of the recovered aqueous phase. The recovery
of the water-soluble triarylphosphine was calculated by the
following Equation 5. Further, the units of the respective amounts
in the equations are mol.
Recovery of water-soluble triarylphosphine (%)=100.times.(Amount of
phosphorous atoms in aqueous phase/Amount of phosphorous atoms
introduced) [Equation 5]
[0208] The tertiary amine included in the aqueous phase was
quantified by analyzing the aqueous phase using gas chromatography.
The recovery of the tertiary amine was calculated by the following
Equation 6. Further, the units of the respective amounts in the
equations are mol.
Recovery of tertiary amine (%)=100.times.(Amount of tertiary amine
in aqueous phase/Amount of tertiary amine introduced) [Equation
6]
[0209] The recovery of the palladium atoms into the aqueous phase
was 87.6%, the recovery of phosphorous atoms was 80.7%, and the
recovery of triethylamine was 70.1%. Further, the amount of diethyl
ether incorporated into the aqueous phase was 0.1% by mass or
less.
Reference Example 2
[0210] The same operation as in Reference Example 1 except that
1.457 g (2.115 mmol in terms of trivalent phosphorous atoms) of the
phosphorous compound obtained in Example 4 was used instead of the
phosphorous compound obtained in Example 3 was carried out.
Further, the ratio of the trivalent phosphorous atoms to the
palladium atoms at a time of preparation of the catalyst was
5.01.
[0211] After 8 hours of the reaction, the butadiene conversion was
80.2%, the selectivity for 2,7-octadien-1-ol was 92.7%, the
selectivity for 1,7-octadien-3-ol was 3.1%, the selectivity for
octatrienes was 2.5%, and the selectivity for the
high-boiling-point products was 1.7%. Further, the selectivity for
4-vinylcyclohexene was 0.01% or less.
[0212] The recovery of the palladium atoms into the aqueous phase
was 88.9%, the recovery of phosphorous atoms was 84.6%, and the
recovery of triethylamine was 70.8%. Further, the amount of diethyl
ether incorporated into the aqueous phase was 0.1% by mass or
less.
Reference Example 3
[0213] The same operation as in Reference Example 1 except that
2.545 g (2.113 mmol in terms of trivalent phosphorous atoms) of the
phosphorous compound obtained in Example 5 was used instead of the
phosphorous compound obtained in Example 3 was carried out.
Further, the ratio of the trivalent phosphorous atoms to the
palladium atoms at a time of preparation of the catalyst was
5.01.
[0214] After 6 hours of the reaction, the butadiene conversion was
74.4%, the selectivity for 2,7-octadien-1-ol was 93.1%, the
selectivity for 1,7-octadien-3-ol was 3.1%, the selectivity for
octatrienes was 2.7%, and the selectivity for the
high-boiling-point products was 1.1%. Further, the selectivity for
4-vinylcyclohexene was 0.01% or less.
[0215] The recovery of the palladium atoms into the aqueous phase
was 86.9%, the recovery of phosphorous atoms was 76.8%, and the
recovery of triethylamine was 76.9%. Further, the amount of diethyl
ether incorporated into the aqueous phase was 0.1% by mass or
less.
Reference Example 4
Comparative
[0216] The same operation as in Reference Example 1 except that
2.120 g (2.120 mmol in terms of trivalent phosphorous atoms) of a
diphenyl(3-sulphonatophenyl)phosphine triethylammonium salt (with a
provision that it included 4.40% by mole of oxides) was used
instead of the phosphorous compound obtained in Example 3 was
carried out. Further, the ratio of the trivalent phosphorous atoms
to the palladium atoms at a time of preparation of the catalyst was
5.02.
[0217] After 4 hours of the reaction, the butadiene conversion was
77.6%, the selectivity for 2,7-octadien-1-ol was 88.2%, the
selectivity for 1,7-octadien-3-ol was 5.1%, the selectivity for
octatrienes was 5.1%, and the selectivity for the
high-boiling-point products was 1.6%. Further, the selectivity for
4-vinylcyclohexene was 0.01% or less.
[0218] The recovery of the palladium atoms into the aqueous phase
was 28.2%, the recovery of phosphorous atoms was 48.8%, and the
recovery of triethylamine was 65.5%. Further, the amount of diethyl
ether incorporated into the aqueous phase was 0.1% by mass or
less.
Reference Example 5
Comparative
[0219] The same operation as in Reference Example 1 except that
1.015 g (2.113 mmol in terms of trivalent phosphorous atoms) of a
diphenyl(6-methyl-3-sulphonatophenyl)phosphine triethylammonium
salt (with a provision that it included it included 4.58% by mole
of oxides) was used instead of the phosphorous compound obtained in
Example 3 was carried out. Further, the ratio of the trivalent
phosphorous atoms to the palladium atoms at a time of preparation
of the catalyst was 5.01.
[0220] After 4 hours of the reaction, the butadiene conversion was
85.0%, the selectivity for 2,7-octadien-1-ol was 88.8%, the
selectivity for 1,7-octadien-3-ol was 5.0%, the selectivity for
octatrienes was 4.4%, and the selectivity for the
high-boiling-point products was 1.8%. Further, the selectivity for
4-vinylcyclohexene was 0.01% or less.
[0221] The recovery of the palladium atoms into the aqueous phase
was 12.0%, the recovery of phosphorous atoms was 28.3%, and the
recovery of triethylamine was 76.5%. Further, the amount of diethyl
ether incorporated into the aqueous phase was 0.1% by mass or
less.
[0222] According to Example 1, it is apparent that a mixture of 5%
by mole or less of
bis(2-methylphenyl)(6-methyl-3-sulphophenyl)phosphine, 80% by mole
or more of bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine,
and 15% by mole or less of tris(6-methyl-3-sulphophenyl)phosphine
can be acquired with high yield.
[0223] Furthermore, according to Example 2, it is apparent that
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine can be
isolated and purified by column chromatography.
[0224] According to Examples 3, 5, and 6, it is apparent that a
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt can be acquired with high yield by reacting
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine with a
tertiary amine having a total of 3 to 27 carbon atoms in groups
bonded to one nitrogen atom.
[0225] According to Example 4, it is apparent that the
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt can be made to have increased purity by washing
with a ketone solvent or the like.
[0226] According to Reference Examples 1 to 5, it is apparent that
the bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt provided by the present invention can be obtained
with higher selectivity in the telomerization reaction and the
recovery of the palladium catalyst is higher, as compared with
other water-soluble triarylphosphines, and therefore, it is useful
when carrying out industrial telomerization reactions.
INDUSTRIAL APPLICABILITY
[0227] The
bis(6-methyl-3-sulphonatophenyl)(2-methylphenyl)phosphine
diammonium salt obtained by using
bis(6-methyl-3-sulphophenyl)(2-methylphenyl)phosphine of the
present invention is useful for a telomerization reaction of two
molecules of an alkadiene such as butadiene with a nucleophilic
reactant such as water.
* * * * *