Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Reexamination Certificate
1998-12-15
2001-10-09
Siegel, Alan (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
C570S144000, C570S191000, C570S257000, C568S681000, C568S684000, C560S226000, C560S227000
Reexamination Certificate
active
06300532
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for the catalytic addition of haloalkanes to alkenes in the presence of an organophosphite catalyst compound.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 4,605,802 is directed to the addition of a haloalkane (carbon tetrachloride) to an alkene (ethylene) in the presence of a phosphite ester complexing agent (such as triethylphosphite) and an iron-containing catalyst material (such as powdered iron or iron chloride) to produce the haloalkane addition product (1,1,1,3-tetrachloropropane). This addition reaction occurs in the absence of solvent. The addition of 1,1,1-trichlorotrifluoroethane to ethylene using an iron/triethylphosphite co-catalyst system in the absence of a solvent was also reported in the
Journal of Fluorine Chemistry,
76 (1996) 49-54.
The addition of polyhaloalkanes to 1-octene by an oxidation-reduction addition in the presence of a copper chloride catalyst was reported in Burton et al.,
Journal of Organic Chemistry
(1970), pages 1339 to 1342. A similar type of oxidation-reduction addition was discussed earlier by Asscher et al in an article in the
Journal of the Chemical Society
(1963) at pages 1887 to 1895. Asscher et al. is directed to the addition of carbon tetrachloride to alkenes in the presence of a copper-containing or iron-containing catalyst. Asscher et al. reported that the use of the metal-containing catalyst effectively minimizes telomerization reactions, thereby producing a greater yield of the 1:1 addition adduct.
Others have generally taught the use of metal-containing catalysts to add haloalkanes across a carbon-carbon multiple bond. For example, T. Asahara et al., in two articles in volume 74 of Kogyo Kagaku Zasshi (1971), at pages 703 to 705 and 2288 to 2290, discuss the reaction of carbon tetrachloride with ethylene in the presence of a phosphite ester complexing agent and metal salts, particularly, iron chloride, to effect telomerization. The reactions proceed to various degrees, producing 1,1,1,3-tetrachloropropane along with relatively large amounts of higher telomers, as follows:
CCl
4
+CH
2
═CH
2
→CCl
3
(CH
2
—CH
2
)
n
Cl+CCl
2
[(CH
2
—CH
2
)
n
Cl]
2
wherein n is primarily 1 with significant amounts of n as 2 and 3.
T. Fuchikami et al., an article in
Tetrahedron Letters,
Vol. 25, No. 3 (1984), at pages 303 to 306, is directed to the use of a transition-metal complex catalyst in the addition of polyfluoroalkyl halides to carbon-carbon multiple bonds.
T. Ishihara et aL, an article in
Chemistry Letters
(1986), at pages 1895-1896, is directed to the perfluoroalkylation of alkynes with perfluoroalkyl iodides in the presence of a palladium catalyst.
Still others have employed initiators such as amines or amine salts (Brace,
J Org. Chem.,
44(2) 212-217 (1979)) or arenesulfonate and alkanesulfinate salts (Feiring,
J. Org. Chem.
50(18), 3269-3272 (1985)). Other prior art catalysts include Fe(CO)catalyst)
5
, Mn(CO)
10
, and RuCl
2
.
In these prior art examples, the reaction mechanism is thought to involve radical or radical-type intermediates formed by single electron transfer (SET) processes. The metal component of the catalyst is typically in an electron rich low valence state and transfers a single electron to the haloalkane to initiate the transformation. In other examples, similar addition reactions have been brought about by thermolysis, photolysis, electrolysis, or free radical initiation, for example, using organic peroxides such as benzoyl peroxide. These alternate addition methods all involve radical species as intermediates.
Use of such metal catalysts, however, generally suffer from several drawbacks; e.g., they may be expensive, they may lead to unwanted by-product formation, they may require removal from the final product and they may require special environmental handling and disposal procedures that are nonhazardous to the environment.
An article in the
Journal of Fluorine Chemistry,
50 (1990), W. Y. Huang et al., at pages 133-140, is directed to the use of phosphorus derivatives, including triethylphosphite, as catalysts in the presence of excess acetonitrile (i.e., present in an amount that exceeds the total amount of reactants and catalyst). The excess acetonitrile is said to be needed for successful addition of the perfluoroalkyl iodide to the alkene.
However, use of such additives (as in Huang et al) generally suffer from several drawbacks; e.g., the preferred excess component must be determined to maximize process performance, the productivity is lowered by the volume of the excess component carried through the process equipment, the excess component must be dry, and it may require removal in a separate step for recycle or disposal.
OBJECTS AND SUMMARY OF THE INVENTION
The present invention provides a process for the catalytic addition of haloalkanes (as defined below) to alkenes in the presence of a catalyst, wherein the catalyst is an organophosphite compound.
More specifically, the present invention provides a process for catalytic addition of a haloalkane to an alkene comprising the step of reacting the haloalkane with the alkene in the presence of a catalyst, wherein said catalyst consists of an organophosphite compound represented by the following formula: P(OR
a
)(OR
b
)(OR
c
), wherein R
a
, R
b
, and R
c
are each selected from the group consisting of an alkyl group and an aralkyl group; wherein said haloalkane is as follows:
(i) CR
1
R
2
R
3
R
4
, wherein (a) each of R
1
, R
2
, R
3
and R
4
is selected from the group consisting of a chlorine atom, a bromine atom or an iodine atom; or (b) R
1
is selected from the group consisting of a linear alkyl group; a halo-substituted linear alkyl group; an aralkyl group; an aralkyl group substituted with at least one of a halogen atom on the alkyl portion thereof or a halogen atom, alkyl group, alkoxy group or —CO
2
R
10
wherein R
10
is a C
1
-C
4
alkyl group on the aryl portion thereof; an aryl group and an aryl group substituted with at least one of a chlorine atom, a fluorine atom, an alkoxy group or a —CO
2
R
11
group, wherein R
11
is a C
1
-C
4
alkyl group; and R
2
, R
3
and R
4
are as follows: R
2
is an iodine atom and R
3
and R
4
are each a halogen atom except R
3
and R
4
are not each a bromine atom or R
2
and R
3
are each a bromine atom and R
4
is a halogen atom;
(ii) CR
5
R
6
R
7
I, wherein R
5
is a fluorine atom and R
6
and R
7
are each a halogen atom, except R
6
and R
7
are not each a bromine atom; or
(iii) CR
8
R
9
Br
2
, wherein R
8
is a fluorine atom and R
9
is a halogen atom;
and wherein the catalyzed addition of the haloalkane to the aikene proceeds without any other components present in an excess amount, by weight, of the combined amount of the haloalkane, alkene and organophosphite catalyst compound.
The present invention further provides a process for catalytic addition comprising adding a haloalkane to an alkene in the presence of an organophosphite catalyst compound, wherein said catalytic addition consists essentially of said haloalkane, alkene and organophosphite catalyst compound; said organophosphite catalyst compound consists of an organophosphite compound represented by the following formula: P(OR
a
)(OR
b
)(OR
c
), wherein R
a
, R
b
, and R
c
are each selected from the group consisting of an alkyl group and an aralkyl group; and said haloalkane is as follows:
(i) CR
1
R
2
R
3
R
4
, wherein (a) each of R
1
, R
2
, R
3
and R
4
is selected from the group consisting of a chlorine atom, a bromine atom or an iodine atom; or (b) R
1
is selected from the group consisting of a linear alkyl group; a halo-substituted linear alkyl group; an aralkyl group; an 20 aralkyl group substituted with at least one of a halogen atom on the alkyl portion thereof or a halogen atom, alkyl group, alkoxy group or —CO
2
R
10
wherein R
10
is a C
1
-C
4
alkyl group on the aryl portion thereof, an aryl group and an aryl group substituted with at least one of a chlorine atom, afluorine atom, an alkoxy group or a —CO
2
R
11
group, wherein
Demmin Timothy Rech
Puy Michael Van Der
Allied-Signal Inc.
Siegel Alan
Szuch Colleen D.
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