Process for functionalizing alkanes

• US 4,511,745 A
• Filed: 06/12/1984
• Issued: 04/16/1985
• Est. Priority Date: 06/12/1984
• Status: Expired due to Term

• Current Assignee: Chevron Research Company (Chevron Corp.)
• Original Assignee: United States Department of Energy (Government of the United States of America)
• Inventors: Bergman, Robert G., Janowicz, Andrew H., Periana-Pillai, Roy A.
• Primary Examiner(s): Williams, Howard S.
• Application Number:
  US06/619,886
• Time in Patent Office: 308 Days
• Field of Search: 570/1, 570/241, 570/252, 260/429 CY, 204/162 R
• US Class Current: 570/241
• CPC Class Codes: C07C 17/00 Preparation of halogenated hydrocarbons
• CPC Class Codes: C07C 19/01 containing chlorine
• CPC Class Codes: C07F 15/0073 Rhodium compounds

Abstract

Process for functionalizing saturated hydrocarbons selectively in the terminal position comprising:

(a) reacting said saturated hydrocarbons of the formula:

RH

where:

H represents a hydrogen atom, and

R represents a saturated hydrocarbon radical,

with a metal complex of the formula:

CpRhPMe.sub.3 H.sub.2

where:

Cp represents a pentamethylated cyclopentadienyl radical,

Rh represents a rhodium atom,

P represents a phosphorous atom,

Me represents a methyl group,

H represents a hydrogen atom,

in the presence of ultraviolet radiation at a temperature maintained at about -60° to -17° C. to form a hydridoalkyl complex of the formula:

CpRhPMe.sub.3 RH

(b) reacting said hydridoalkyl complex with a haloform of the formula:

CHX.sub.3

where:

X represents a bromine, iodine or chlorine atom,

at a temperature in the range of about -60° to -17° C. to form the corresponding haloalkyl complex of step (a) having the formula:

CpRhPMe.sub.3 RX; and,

(c) reacting said haloalkyl complex formed in (b) with halogen (X₂) at a temperature in the range of about -60° to 25° C. (i.e. ambient) to form a functional haloalkyl compound.

Claims

1. A process for functionalizing saturated hydrocarbons comprising:

(a) reacting said saturated hydrocarbons of the formula;

space="preserve" listing-type="equation">RH

where;

H represents a hydrogen atom, and

R represents a saturated hydrocarbon radical,

with a metal complex of the formula;

space="preserve" listing-type="equation">CpRhPMe.sub.3 H.sub.2

where;

Cp represents a pentamethylated cyclopentadienyl radical,

Rh represents a rhodium atom,

P represents a phosphorous atom,

Me represents a methyl group,

H represents a hydrogen atom,

in the presence of ultraviolet radiation at a temperature maintained at about -60°

to -17°

C. to form a hydridoalkyl complex of the formula;

space="preserve" listing-type="equation">CpRhPMe.sub.3 (R)(H)

(b) reacting said hydridoalkyl complex with a haloform of the formula;

space="preserve" listing-type="equation">CHX.sub.3

where;

X represents a halogen atom selected from bromine, iodine and chlorine,

at a temperature in the range of about -60°

to -17°

C. to form the corresponding haloalkyl complex of step (a) having the formula;

space="preserve" listing-type="equation">CpRhPMe.sub.3 (R)(X); and

,

(c) reacting said haloalkyl complex formed in (b) with halogen at a temperature in the range of about -60°

to 25°

C. to form the alkyl halide of said saturated hydrocarbon.

2. A process according to claim 1 wherein the temperatures are in the ranges as follows:

(a) -35°

to -20°

C.

(b) -35°

to -20°

C.

(c) 0°

to 20°

C.

3. A process according to claim 1 wherein X is bromine.

4. A process according to claim 1 wherein the dilution of said metal complex in step (a) is in the range of about 1×

10^-5 to 1×

10^-2.

5. A process according to claim 1 wherein excess saturated hydrocarbon reactant is employed as solvent.

6. A process according to claim 1 wherein R is at least one hydrocarbon radical of up to about 20 carbon atoms whereby RH is a liquid at reaction conditions.

7. A process according to claim 1 wherein R is an acyclic hydrocarbon radical.

8. A process according to claim 7 wherein said saturated hydrocarbon reactant has about 2-12 carbon atoms.

9. A process according to claim 1 wherein R is a cyclic hydrocarbon radical.

10. A process according to claim 1 wherein R is a liquid hydrocarbon radical of up to about 14 carbon atoms.

11. A process for functionalizing saturated hydrocarbons comprising:

(a) reacting said saturated hydrocarbons of the formula;

space="preserve" listing-type="equation">R.sub.1 H

where;

H represents a hydrogen atom, and

R₁ represents a saturated hydrocarbon radical,

with a metal complex of the formula;

space="preserve" listing-type="equation">CpRhP(R.sub.2).sub.3 H.sub.2

where;

Cp represents a pentamethylated cyclopentadienyl radical,

Rh represents a rhodium atom,

P represents a phosphorous atom,

R₂ represents a hydrocarbon radical,

H represents a hydrogen atom,

in the presence of ultraviolet radiation at a temperature maintained at about -60°

to -17°

C. to form a hydridoalkyl complex of the formula;

space="preserve" listing-type="equation">CpRhP(R.sub.2).sub.3 (R.sub.1)(H)

(b) reacting said hydridoalkyl complex with a haloform of the formula;

space="preserve" listing-type="equation">CHX.sub.3

where;

X represents a halogen atom selected from bromine, iodine and chlorine,

at a temperature in the range of about -60°

to -17°

C. to form the corresponding haloalkyl complex of step (a) having the formula;

space="preserve" listing-type="equation">CpRhP(R.sub.2).sub.3 (R.sub.1)(X); and

,

(c) reacting said haloalkyl complex formed in (b) with halogen at a temperature in the range of about -60°

to 25°

C. to form the alkyl halide of said saturated hydrocarbon.