Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Patent
1998-01-28
2000-03-21
Siegel, Alan
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
570257, 558357, 558370, 560226, 560227, C07C 2118, C07C 1732, C07C25500, C07C 6963
Patent
active
060404876
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
This invention relates to a process for the manufacture of halogenated alkanes by the catalytic reaction of haloalkanes with halogenated olefins.
BACKGROUND
The catalyzed radical addition of haloalkanes to olefins is a well known reaction. Typically, however, when a haloalkane (e.g., AB, where A is a substituted carbon atom and B is a halogen other than fluorine) is added to an olefin (e.g., CH.sub.2 .dbd.CHR) to form the saturated adduct (e.g., CH.sub.2 ACHBR), the products (i.e., halogenated addition compounds) also include varying amounts of telomers (e.g., A(CH.sub.2 CHR).sub.n B, where n is equal to 2 or more). For example, Canadian Pat. No. 2,073,533 discloses a process for the manufacture of CCl.sub.3 CH.sub.2 CCl.sub.3 by reacting carbon tetrachloride with vinylidene chloride using copper catalysts in acetonitrile. The selectivity for CCl.sub.3 CH.sub.2 CCl.sub.3 with respect to converted vinylidene chloride was 87%. It has been shown in the art that the major by-product is the C.sub.5 telomer, CCl.sub.3 (CH.sub.2 CCl.sub.2).sub.2 Cl.
The halogenated adducts are useful intermediates for the production of fluoroalkanes, particularly, hydrofluoroalkanes. These latter compounds are useful as refrigerants, fire extinguishants, heat transfer media, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents, propellants, foaming agents and power cycle working fluids. There is an interest in developing more efficient processes for the manufacture of hydrofluoroalkanes.
SUMMARY OF THE INVENTION
A liquid phase process is provided in accordance with this invention for producing halogenated alkane adducts of the formula CAR.sup.1 R.sup.2 CBR.sup.3 R.sup.4 wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from the group consisting of H, Br, Cl, F, C.sub.1 -C.sub.6 alkyl, CN, CO.sub.2 CH.sub.3, CH.sub.2 Cl, and aryl (e.g., phenyl), provided that only two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 can be selected from C.sub.1 -C.sub.6 alkyl, CN, CO.sub.2 CH.sub.3, CH.sub.2 Cl, and aryl; A is selected from the group consisting of CX.sub.3, CH.sub.3-a X.sub.a, C.sub.n H.sub.(2n+1)-b X.sub.b and CH.sub.c X.sub.2-c R, where R is C.sub.n H.sub.(2n+1)-b X.sub.b (e.g., CF.sub.3 and CCl.sub.2 CF.sub.3), each X is independently selected from the group consisting of Br, Cl and I, a is an integer from 0 to 3, n is an integer from 1 to 6, b is an integer from 1 to 2n+1, and c is an integer from 0 to 1; and B is selected from the group consisting of Br, Cl and I; provided that (1) when A is CX.sub.3 then only one of X is I, (2) when A is CH.sub.3-a X.sub.a, then each X is B and a is an integer from 1 to 2 when B is Br, a is 2 when B is Cl, and a is an integer from 0 to 2 when B is I, and (3) when A is C.sub.n H.sub.(2n+1)-b X.sub.b, then each X is independently selected from Cl and F, and B is I. The process comprises contacting a halogenated alkane of the formula AB (where A and B are as indicated above) with an olefin of the formula CR.sup.1 R.sup.2 .dbd.CR.sup.3 R.sup.4 (where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are as indicated above) in the presence of a catalyst system containing (i) at least one catalyst selected from the group consisting of monovalent and divalent copper, and (ii) at least one promoter selected from the group consisting of aromatic or aliphatic heterocyclic compounds which contain at least one carbon-nitrogen double bond in the heterocyclic ring.
This invention further provides a process for producing hydrofluoroalkanes (e.g., CF.sub.3 CH.sub.2 CHF.sub.2). This process comprises (a) producing a hydrochlorofluoroalkane (e.g., CCl.sub.3 CH.sub.2 CHCl.sub.2) by reacting a halogenated alkane of the formula AB (e.g., CCl.sub.4) and an olefin of the formula CR.sup.1 R.sup.2 .dbd.CR.sup.3 R.sup.4 (e.g., CH.sub.2 .dbd.CHCl) as indicated above (provided that B and X are Cl and at least one of said reactants contains hydrogen), and (b) reacting the hydr
REFERENCES:
patent: 5446217 (1995-08-01), Van Der Puy
patent: 5574192 (1996-11-01), VanDerPuy et al.
Baker Ralph Thomas
Petrov Viacheslav Alexandrovich
Rao Velliyurnott Mallikarjuna
E. I. Du Pont de Nemours and Company
Siegel Alan
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