US4263466A
Expired / Lapsed
US
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Coupling of aryl and heteroaryl mono chlorides
Assignee: BP Corp North America Inc
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Filing: 1979-09-11
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Granted: 1981-04-21
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Expires: 1999-09-11
Abstract
Abstract Aryl and heteroaryl mono chlorides are coupled in an aprotic solvent under an inert atmosphere by a catalyst mixture of a nickel compound and a ligand in the presence of a reducing metal.
Inventors
- 👤 Ismael Colon
- 👤 Louis M. Maresca
- 👤 George T. Kwiatkowski
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 05:34
CPC Classifications
C; C07; C07D; C07D213/00; C07D213/02; C07D213/04; C07D213/06; C07D213/22; B; B01; B01J; B01J31/00; B01J31/16; B01J31/18; B01J31/1805; B01J31/181; B01J31/1815; B01J31/24; B01J31/2404; B01J31/26; C07C; C07C1/00; C07C1/26; C07C209/00; C07C209/68; C07C41/00; C07C41/01; C07C41/18; C07C41/30; C07C43/00; C07C43/02; C07C43/20; C07C43/205; C07C43/2055; C07C45/00; C07C45/61; C07C45/67; C07C45/68; C07C45/72; B01J2231/00; B01J2231/40; B01J2231/42; B01J2231/4205; B01J23/00; B01J23/02; B01J23/06; B01J23/16; B01J23/32; B01J23/34; B01J2531/00; B01J2531/80; B01J2531/84; B01J2531/847; C07C2527/00; C07C2527/06; C07C2527/08; C07C2527/10; C07C2527/128; C07C2531/00; C07C2531/16; C07C2531/24; C07C2531/26; C07C2531/28; C07C2531/30
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
163 words
A method for coupling aryl and heteroaryl mono chlorides having 4 to 30 carbons which comprises contacting said aryl mono chlorides in an aprotic solvent with a catalyst mixture comprising an anhydrous nickel compound and at least one ligand selected from the group consisting of a triaryl phosphine having 6 to about 14 carbons in each aryl moiety and an aromatic bidentate compound containing at least one ring nitrogen atom and about 5 to about 30 carbon atoms in the presence of a reducing metal selected from the group consisting of zinc, magnesium or manganese, at a temperature of about 0° to about 250° C., wherein the ratio of gram atoms of nickel to moles of aryl chloride is in the range of about 0.0001 to about 0.5, the amount of ligand is about 0.1 to about 100 moles per gram atom of nickel and the amount of reducing metal is at least about 0.5 gram atoms per mole of reacted aryl chloride.
Claim 2
Independent Claim
163 words
A method for coupling aryl and heteroaryl mono chlorides having 4 to 30 carbons which comprises contacting said aryl mono chlorides in an aprotic solvent with a catalyst mixture comprising an anhydrous nickel compound and at least one ligand selected from the group consisting of a triaryl phosphine having 6 to about 14 carbons in each aryl moiety and an aromatic bidentate compound containing at least one ring nitrogen atom and about 5 to about 30 carbon atoms in the presence of a reducing metal selected from the group consisting of zinc, magnesium or manganese, at a temperature of about 0° to about 250° C., wherein the ratio of gram atoms of nickel to moles of aryl chloride is in the range of about 0.0001 to about 0.5, the amount of ligand is about 0.1 to about 100 moles per gram atom of nickel and the amount of reducing metal is at least about 0.5 gram atoms per mole of reacted aryl chloride.
Claim 3
Dependent Claim
31 words
A method as claimed in claim 1 wherein the reducing metal is a finely divided powder having a mesh size of 20 or finer when measured in the U.S. sieve scale.
Claim 4
Dependent Claim
14 words
A method as claimed in claim 1 wherein the nickel compound is nickel chloride.
Claim 5
Dependent Claim
14 words
A method as claimed in claim 1 wherein the ligand is a triaryl phosphine.
Claim 6
Dependent Claim
14 words
A method as claimed in claim 4 wherein the triaryl phosphine is triphenyl phosphine.
Claim 7
Dependent Claim
15 words
A method as claimed in claim 1 wherein the ligand is an aromatic bidentate compound.
Claim 8
Dependent Claim
14 words
A method as claimed in claim 6 wherein the aromatic bidentate compound is 2,2'-bipyridine.
Claim 9
Dependent Claim
27 words
A method as claimed in claim 1 wherein the ligand is a mixture of triaryl phosphine and an aromatic bidentate compound containing at least one ring nitrogen.
Claim 10
Dependent Claim
26 words
A method as claimed in claim 1 wherein at least 0.1 moles per gram atom of nickel of an inorganic salt is added as a promoter.
Claim 11
Dependent Claim
16 words
A method as claimed in claim 9 wherein the inorganic salt is an alkali metal iodide.
Claim 12
Dependent Claim
16 words
A method as claimed in claim 9 wherein the inorganic salt is an alkali metal bromide.
Claim 13
Dependent Claim
15 words
A method as claimed in claim 9 wherein the inorganic salt is alkali metal chloride.
Claim 14
Dependent Claim
13 words
A method as claimed in claim 1 wherein the aprotic solvent is dimethylacetamide.
Claim 15
Dependent Claim
14 words
A method as claimed in claim 1 wherein the aprotic solvent is dimethyl formamide.
Claim 16
Dependent Claim
104 words
A method as claimed in claim 1 wherein the aryl chloride has the formula: ##STR3## wherein R is a monovalent inert radical selected from the group consisting of alkyl, aryl, F, unsubstituted or substituted amino, --CN, --CHO, --Oaryl, --Oalkyl, --OCO--alkyl, --OCOaryl, --COOalkyl, --COOaryl, ##STR4## --SO 2 -alkyl, --SO 2 aryl, --SO 3 alkyl, --SO 3 aryl wherein the aryl contains 4 to about 30 carbons, the alkyl contains 1 to about 8 carbons and a is an integer having values of 0 to 4 with the proviso that no more than one R is in a position ortho to the Cl-containing ring carbon atom.
Claim 17
Dependent Claim
28 words
A method as defined in claim 15 wherein one or more of the carbon atoms of the benzene ring in formula (I) is replaced by N or P.
Claim 18
Dependent Claim
13 words
A method as claimed in claim 16 wherein the aryl chloride is 2-chloropyridine.
Claim 19
Dependent Claim
15 words
A method as claimed in claim 15 wherein R is methyl and a is 1.
Claim 20
Dependent Claim
19 words
A method as claimed in claim 15 wherein R is CH 3 CO 2 -- and a is 1.
Claim 21
Dependent Claim
19 words
A method as claimed in claim 1 wherein the temperature is from about 25° C. to about 120° C.
References Cited (Backward Citations)
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-04-20 | 1984-10-20 | 1985-04-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-04-20 | 1988-10-20 | 1989-04-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-04-20 | 1992-10-20 | 1993-04-21 | $7700.00 | Window Closed / Lapsed |