Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus containing
Utility Patent
1998-11-23
2001-01-02
Vollano, Jean F (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Phosphorus containing
Utility Patent
active
06169209
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for preparing an organic phosphonium chloride. In particular, the invention relates to a process for preparing an organic phosphonium chloride from its corresponding organic phosphonium bromide.
BACKGROUND OF THE INVENTION
The organic phosphonium chloride is of value as a catalyst for various reactions, for instance, an interphasic transfer catalyst, a polymerization catalyst, and a trans-halogenation catalyst.
It is known that the organic phosphonium chloride can be prepared starting from a corresponding organic phosphonium bromide.
J. Am. Chem. Soc., 70, pp. 737 (1948) describes a process for preparing an organic phosphonium chloride by treating an organic phosphonium bromide with an ion exchange resin. This process, however, some drawbacks in that a great amount of ion exchange resin is required, the ion exchange resin has to be regenerated every cycle, and a great amount of aqueous waste such as an aqueous solution containing a chloride ion and a bromide ion is produced. Moreover, the obtained organic phosphonium chloride has to be recrystallized from an appropriate organic solvent for purification, and the yield is up to 79%.
Nippon Kagaku Zasshi (Chemistry Magazine of Japan, in Japanese), 86, pp. 112 (1965) describes a process for preparing an organic phosphonium chloride by the steps of converting an organic phosphonium bromide to its corresponding organic phosphonium fluoroborate and treating the fluoroborate with potassium chloride to give the desired phosphonium chloride. This process, however, has drawbacks in that an expensive silver borofluoride is required in a stoichiometric amount for the desired conversion, and that the produced phosphonium chloride has to be repeatedly recrystallized from an appropriate organic solvent.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved process for preparing an organic phosphonium chloride from an organic phosphonium bromide.
Specifically, it is an object of the invention to provide a process for the preparation of an organic phosphonium chloride in a high yield, using no expensive chemical compound and no complicated procedures.
The present invention resides in a process for preparing an organic phosphonium chloride which comprises bringing an organic phosphonium bromide into contact with a chloride ion in a heterogeneous mixture solution comprising water and an organic solvent.
DETAILED DESCRIPTION OF THE INVENTION
The organic phosphonium bromide employed in the process of the invention is represented by the following formula (I):
In the formula (I), R
1
, R
2
, R
3
and R
4
independently represents an aryl group, an aralkyl group, an alkyl group, or a heterocyclic group.
The organic phosphonium bromide can be prepared by the known reaction between a tertiary phosphine and a bromine-containing compound. See Chem. Ber. 99, pp. 2782 (1966).
Details of the organic phosphonium bromide having the formula (I) are given below.
The aryl group can have 6 to 14 carbon atoms. Examples of the aryl groups include phenyl, biphenyl, and naphthyl.
The aralkyl group can have 7 to 15 carbon atoms. Examples of the aralkyl groups include benzyl, phenethyl, cinnamyl, and naphtylmethyl.
The alkyl group can be a straight, branched or cyclic alkyl group, can contain an unsaturated bonding, and can have 1 to 16 carbon atoms. Examples of the alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylmethyl, vinyl, propenyl, butenyl, and 1,3-butadienyl.
The heterocyclic group can contain a sulfur atom, an oxygen atom or a nitrogen atom as a ring member and can have 4 to 16 carbon atoms. Examples of the heterocyclic groups include thienyl, furyl, and pyridyl.
In the formula (1), R
1
, R
2
, R
3
and R
4
can be the same or different from each other. Two of R
1
, R
2
, R
3
and R
4
can be combined to form a heterocyclic group containing the phosphor atom as a ring member.
R
1
, R
2
, R
3
and R
4
can be any isomeric group and can have one or more substituents. Examples of the substituents include an alkoxy group preferably having 1 to 12 carbon atoms, a thioalkoxy group preferably having 1 to 12 carbon atoms, an aralkyloxy group preferably having 7 to 13 carbon atoms, an aryloxy group preferably having 6 to 16 carbon atoms, a thioaryloxy group preferably having 6 to 16 carbon atoms, an acyl group preferably having 1 to 12 carbon atoms, an alkoxycarbonyl group preferably having 2 to 16 carbon atoms, a carboxyl group, an amino group, an alkyl-substituted amino group preferably having 2 to 16 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and a halogen atom (e.g., fluorine, chlorine, or bromine).
In the case that one of R
1
, R
2
, R
3
and R
4
is an aromatic ring-containing group such as aryl group, an aralkyl group, or a heterocyclic group, the aromatic group can have one or more of the above-mentioned substituents or can have one or more alkyl groups (preferably having 1 to 12 carbon atoms) which can have a ring (which can be a heterocyclic ring) or an unsaturated bonding. In the case that one of R
1
, R
2
, R
3
and R
4
is a heterocyclic group, the heterocyclic group can have, as a substituent, an aryl group preferably having 6 to 16 carbon atoms.
Examples of the organic phosphonium bromides are described below.
(1) Phosphonium bromide in which all of R
1
, R
2
, R
3
and R
4
are alkyl groups
tetraethylphosphonium bromide, tetrabutylphosphonium bromide, and hexadecyltributylphosphonium bromide.
(2) Phosphonium bromide in which some of R
1
, R
2
, R
3
and R
4
are aryl groups and others are alkyl groups
methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, hexyltriphenylphosphonium bromide, heptyltriphenylphosphonium bromide, tetradecyltriphenylphosphonium bromide, cyclopropyltriphenylphosphonium bromide, allyltriphenylphosphonium bromide, 1,3-butadienyltriphenylphosphonium bromide, and dimethyldiphenylphosphonium bromide.
(3) Phosphonium bromide in which some of R
1
, R
2
, R
3
and R
4
are aryl groups and others are alkyl groups having substituent group(s)
1) The substituent of alkyl is a heterocyclic group
(1,3-dioxolan-2-yl)methyltriphenylphosphonium bromide, 2-(1,3-dioxolan-2-yl)ethyltriphenylphosphonium bromide, and 2-(1,3-dioxan-2-yl)ethyltriphenylphosphonium bromide.
2) The substituent of alkyl is a halogen atom
bromomethyltriphenylphosphonium bromide.
3) The substituent of alkyl is a carboxyl group
4-carboxybutyltriphenylphosphonium bromide and 2-carboxyallyltriphenylphosphonium bromide.
4) The substituent of alkyl is an alkoxycarbonyl group
4-ethoxycarbonylbutyltriphenylphosphonium bromide.
5) The substituent of alkyl is an alkyl-substituted amino group
2-dimethylaminomethyltriphenylphosphonium bromide.
6) The substituent of alkyl is an acyl group
phenacyltriphenylphosphonium bromide.
(4) Phosphonium bromide in which some of R
1
, R
2
, R
3
and R
4
are aryl groups and others are aralkyl groups
benzyltriphenylphosphonium bromide, 4-ethoxybenzyltriphenylphosphonium bromide, and cinnamyltriphenylphosphonium bromide.
(5) Phosphonium bromide in which all of R
1
, R
2
, R
3
and R
4
are aryl groups
tetraphenylphosphonium bromide, p-biphenyltriphenylphosphonium bromide, 1-naphthyltriphenylphosphonium bromide, and 2-naphthyltriphenylphosphonium bromide.
(6) Phosphonium bromide in which all of R
1
, R
2
, R
3
and R
4
are aryl groups having substituent(s)
1) The substituent of aryl is an alkyl group
o-methylphenyltriphenylphosphonium bromide, m-methylphenyltriphenylphosphonium bromide, p-methylphenyltriphenylphosphonium bromide, p-isopropylphenyltriphenylphosphonium bromide, p-t-butylphenyltriphenylphosphonium bromide, m-trifluoromethylphenyltriphenylphosphonium bromide, and 2,4,6-trimethylphenyltriphenylphosphonium bromide.
2) The substituent of aryl is a halogen atom
p-chlorophenyltriphenylphosphonium bromide.
3) The substituent of aryl is an alkoxy
Harada Katsumasa
Kashiwagi Koichi
Niida Sadao
Sugise Ryoji
McAulay Nissen Goldberg & Kiel, LLP
Ube Industries Ltd.
Vollano Jean F
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