Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus esters
Reexamination Certificate
2000-03-09
2001-02-20
Ambrose, Michael G. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Phosphorus esters
C558S142000, C558S187000
Reexamination Certificate
active
06191298
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to a thioalkenyl phosphonic acid ester and to a process for the preparation thereof.
Thioalkenyl phosphonic esters are a group of compounds useful as intermediate compounds for the production of fine chemicals, because they can easily give, by Michael reaction with a nucleophile, a carbanion which in turn causes Horner-Emmons addition reaction with a carbonyl compound and because they can undergo a carbon—carbon bond-forming reaction by regio- or stereo-selective coupling with a vinyl halide, an aryl halide or Grignard reagent in the presence of a transitional metal catalyst.
At present, no methods have been known which can produce thioalkenyl phosphonic esters by a single stage reaction of a hydrocarbon. A reaction of a thioalkenyl halogen compound with a secondary phosphite under basic conditions may yield a thioalkenyl phosphonic ester. An addition of a secondary phosphite to a thioalkyne may also produce a thioalkenyl ether. These methods, however, are not advantageous from the industrial point of view, because the sulfur-containing raw materials are not easily obtainable.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a simple process which can produce a thioalkenyl phosphonic ester at low costs using an easily feasible starting material.
Another object of the present invention is to provide a novel thioalkenyl phosphonic ester.
In accordance with one aspect of the present invention, there is provided a process for the preparation of a thioalkenylphosphonic acid ester of the following formula (I):
R
1
C(SR
3
)═CHP(═O)(OR
2
)
2
(I)
wherein R
1
stands for a monovalent group selected from hydrogen atom, an alkyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, an alkenyl group and a silyl group, R
2
stands for an aryl group and R
3
stands for an aryl group, comprising reacting an acetylene compound of the following formula (II):
R
1
C≡CH (II)
wherein R
1
is as defined above, with a phosphorothioate of the following formula (III):
(R
2
O)
2
P(═O)SR
3
(III)
wherein R
2
and R
3
are as defined above, in the presence of a palladium complex catalyst.
In another aspect, the present invention provides a process for the preparation of a bis(thioalkenyl)phosphonic acid ester of the following formula (IV):
[P(═O)(OR
2
)
2
]CH═C(SR
3
)—R—C(SR
3
)═CH[P(═O)(OR
2
)
2
] (IV)
wherein R
2
stands for an aryl group, R
3
stands for an aryl group and R
4
stands for an alkylene group or a cycloalkylene group, comprising reacting an acetylene compound of the following formula (II):
HC≡C—R
4
—C≡CH (V)
wherein R
4
is as defined above, with a phosphorothioate of the following formula (III):
(R
2
O)
2
P(═O)SR
3
(III)
wherein R
2
and R
3
are as defined above, in the presence of a palladium complex catalyst.
The present invention also provides a thioalkenylphosphonic acid ester of the following formula (I):
R
1
C(SR
3
)═CHP(═O)(OR
2
)
2
(I)
wherein R
1
stands for a monovalent group selected from hydrogen atom, an alkyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, an alkenyl group and a silyl group and R
2
stands for an aryl group and R
3
stands for an aryl group.
The present invention further provides a bis(thioalkenyl)phosphonic acid ester of the following formula (IV):
[P(═O)(OR
2
)
2
]CH═C(SR
3
)—R
4
—C(SR
3
)═CH[P(═O)(OR
2
)
2
] (IV)
wherein R
4
stands for an aryl group, R
3
stands for an aryl group and R stands for an alkylene group or a cycloalkylene group.
Other objects, features and advantages of the present invention will become apparent from the detailed description of the preferred embodiments of the invention to follow.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
The phosphorothioate used as a raw material in the process of the present invention is represented by the formula (III):
(R
2
O)
2
P(═O)SR
3
(III)
wherein R
2
and R
3
each stand for an aryl group preferably having 6-14 carbon atoms, more preferably 6-12 carbon atoms. Illustrative of suitable aryl groups are phenyl, tolyl and napththyl.
The phosphorothioate is reacted with an acetylene compound of the formula (II) or (V)
R
1
C≡CH (II)
HC≡C—R
4
—C≡CH (V)
wherein R
1
stands for a monovalent group selected from
(a) hydrogen atom,
(b) an alkyl group preferably having 1-18 carbon atoms, more preferably 1-10 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl octyl or decyl,
(c) a cycloalkyl group preferably having 5-18 carbon atoms, more preferably 5-10 carbon atoms, such as cyclohexyl, cyclooctyl or cyclododecyl,
(d) a cycloalkenyl group preferably having 5-18 carbon atoms, more preferably 5-10 carbon atoms, such as cyclohexenyl, cyclooctenyl or cyclododecenyl,
(e) an aryl group preferably having 6-14 carbon atoms, more preferably 6-10 carbon atoms, such as phenyl, naphthyl, substituted phenyl (e.g. tolyl or benzylphenyl) or substituted naphthyl (e.g. methylnaphthyl),
(f) an aralkyl group preferably having 7-13 carbon atoms, more preferably 7-9 carbon atoms, such as benzyl, phenethyl, phenylbenzyl, naphthylethyl or naphthylmethyl,
(g) an alkenyl group preferably having 2-18 carbon atoms, more preferably 2-10 carbon atoms, such as vinyl, propenyl or 3-butenyl and
(h) a silyl group which may have 1-3 substituents such as a hydrocarbyl group having 1-18 carbon atoms, preferably 1-8 carbon atoms, such as an alkyl (e.g. methyl, ethyl, propyl, butyl or octyl), cycloalkyl (e.g. cyclohexyl), aryl (e.g. phenyl, tolyl, naphthyl) or aralkyl (e.g. benzyl, phenethyl or naphthylmethyl), and R
4
stands for
(i) an alkylene group preferably having 1-20 carbon atoms, more preferably 1-10 carbon atoms, such as methylene or tetramethylene, or
(j) a cycloalkylene group preferably having 5-18 carbon atoms, more preferably 5-10 carbon atoms, such as cyclopentylene or cyclohexylene.
Illustrative of suitable acetylene compounds are non-substituted acetylene, butyne, octyne, phenylacetylene, trimethylsilylacetylene, 1,8-nonadiyne, diethynylbenzene, hexynenitrile and cyclohexenylacetylene. It is without saying that the present invention is not limited to these acetylene compounds.
The above reaction is performed in the presence of a palladium complex catalyst.
Any known palladium complex catalyst may be used. Low valency palladium complexes, inclusive of zero-valent complexes, may be suitably used. Low valency palladium complexes having a tertiary phosphine or a tertiary phosphite as a ligand are especially suitably used.
In this case, a precursor substance which can form in situ a low valency palladium complex having a tertiary phosphine or a tertiary phosphite as a ligand during the reaction of the acetylene compound with the secondary phosphite may also be suitably used. For example, a palladium complex containing neither tertiary phosphine nor tertiary phosphite may be used in conjunction with a tertiary phosphine or a tertiary phosphite so that a low valency palladium complex having a tertiary phosphine or a tertiary phosphite as a ligand is formed in the reaction mixture. Further, a palladium complex containing a tertiary phosphine or tertiary phosphite may be used in conjunction with another tertiary phosphine or another tertiary phosphite.
A tertiary phosphine of the following formula may be suitably used as a ligand of the palladium complex catalyst:
wherein R
5
, R
6
and R
7
are each
(k) an alkyl group preferably having 1-18 carbon atoms, more preferably 1-12 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl octyl or decyl,
(l) a cycloalkyl group preferably having 4-6 carbon atoms, more preferably 5-6 carbon atoms, such as cyclopentyl or cyclohexyl,
(m) an aryl group preferably having 6-14 carbon atoms, more preferably 6-10 carbon atoms, such as phenyl,
Han Li-Biao
Tanaka Masato
Agency of Industrial Science and Technology
Ambrose Michael G.
Lorusso & Loud
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