Patent US3939147A successfully refreshed from Google Patents.
US3939147A
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Novel 1,2-diaza-1,5,9-cyclo dodecatrienes and 1,2-diaza-1-cyclododecenes
Assignee: Novartis Corp
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Filing: 1973-06-14
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Granted: 1976-02-17
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Expires: 1993-06-14
Abstract
Abstract New unsaturated 1,2-diazacyclododecanes, more particularly 1,2-diazacyclododecatrienes-1,5,9 and 1,2-diazacyclododecanes-1 and a novel process for the preparation thereof are disclosed which process comprises reacting a 1,3-diolefin with an azine in the presence of certain nickel catalysts. Said process unexpectedly yields 12-membered ring compounds only, and more especially oligomerization products of 2 mols of a 1,3-diolefin and 1 mol of an azine, while deactivation of the nickel catalyst by the -N=N-bond is avoided.
Inventors
- 👤 Bernard Hugelin
- 👤 Eduard Troxler
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 22:28
CPC Classifications
C; C07; C07D; C07D245/00; C07D245/02
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
139 words
A 1,2-diaza-1,5,9-cyclododecatriene or 1,2-diaza-1-cyclododecene of the formula ##EQU4## wherein R 1 and R 1 ' independently of one another denote alkyl of one to six carbon atoms; alkenyl of up to four carbon atoms; alkyl of one to four carbon atoms substituted by phenyl; alkenyl of up to four carbon atoms substituted by phenyl; cyclohexyl; phenyl; phenyl substituted in the 4-position by a halogen atom, an alkyl of one to four carbon atoms or an alkoxy of one to four carbon atoms; 1-naphthyl; or 3,4-methylenedioxyphenyl; R 2 and R 2 ' independently of one another denote hydrogen; alkyl of one to four carbon atoms; or R 1 and R 2 , or R 1 ' and R 2 ', together with the carbon atoms to which they are bonded form a cycloalkyl ring of five to 12 carbon atoms.
Claim 2
Dependent Claim
139 words
A 1,2-diaza-1,5,9-cyclododecatriene or 1,2-diaza-1-cyclododecene of the formula ##EQU4## wherein R 1 and R 1 ' independently of one another denote alkyl of one to six carbon atoms; alkenyl of up to four carbon atoms; alkyl of one to four carbon atoms substituted by phenyl; alkenyl of up to four carbon atoms substituted by phenyl; cyclohexyl; phenyl; phenyl substituted in the 4-position by a halogen atom, an alkyl of one to four carbon atoms or an alkoxy of one to four carbon atoms; 1-naphthyl; or 3,4-methylenedioxyphenyl; R 2 and R 2 ' independently of one another denote hydrogen; alkyl of one to four carbon atoms; or R 1 and R 2 , or R 1 ' and R 2 ', together with the carbon atoms to which they are bonded form a cycloalkyl ring of five to 12 carbon atoms.
Claim 3
Dependent Claim
83 words
A compound according to claim 1 wherein R 1 and R 1 ' independently of one another denote alkyl of one to six carbon atoms; cyclohexyl; phenyl; 1-naphthyl; 4-methoxyphenyl; 3,4-methylenedioxyphenyl; 4-chlorophenyl; 4-methylphenyl; or styryl, R 2 and R 2 ' independently of one another denote hydrogen or methyl, or R 1 and R 2 , or R 1 ' and R 2 ', together with the carbon atoms to which they are bonded form a cycloalkyl ring of five to 12 carbon atoms.
Claim 4
Dependent Claim
40 words
A compound according to claim 1 wherein R 1 and R 1 ' each represent alkyl of one to six carbon atoms; cyclohexyl; phenyl; 1-naphthyl; 4-methoxyphenyl; 3,4-methylenedioxyphenyl; 4-chlorophenyl; 4-methylphenyl; or styryl, and R 2 and R 2 ' are hydrogen.
Claim 5
Dependent Claim
28 words
A compound according to claim 1 wherein R 1 , r 1 ', r 2 and R 2 ' each represent alkyl of one to four carbon atoms.
Claim 6
Dependent Claim
43 words
A compound according to claim 1 wherein R 1 and R 2 as well as R 1 ' and R 2 ' each form, together with the carbon atom to which they are bonded, a cycloalkyl ring of five to 12 carbon atoms.
Claim 7
Dependent Claim
7 words
A compound according to claim 1, 3,12-diethyl-1,2-diaza-1,5,9-cyclododecatriene.
Claim 8
Dependent Claim
7 words
A compound according to claim 1, 3,12-diphenyl-1,2-diaza-1,5,9-cyclododecatriene.
Claim 9
Dependent Claim
7 words
A compound according to claim 1, 3,12-di(4-methoxyphenyl)-1,2-diaza-1,5,9-cyclododecatriene.
Claim 10
Dependent Claim
7 words
A compound according to claim 1, 3,3,12,12-tetramethyl-1,2-diaza-1,5,9-cyclododecatriene.
Claim 11
Dependent Claim
7 words
A compound according to claim 1, 3,12-diphenyl-1,2-diaza-1-cyclododecene.
Claim 12
Dependent Claim
10 words
A compound according to claim 1 having the formula ##SPC18##
Claim 13
Dependent Claim
257 words
A process for the manufacture of the 1,2-diaza-1,5,9-cyclododecatrienes according to claim 1 which comprises reacting 1,3-butadiene with an azine of the formula ##EQU5## wherein R 1 and R 1 ' independently of one another denote alkyl of one to six carbon atoms; alkenyl of up to four carbon atoms; alkyl of one to four carbon atoms substituted by phenyl; alkenyl of up to four carbon atoms substituted by phenyl; cyclohexyl; phenyl; phenyl substituted in the 4-position by a halogen atom, an alkyl of one to four carbon atoms or an alkoxy of one to four carbon atoms; 1-naphthyl; or 3,4-methylenedioxyphenyl; R 2 and R 2 ' independently of one another denote hydrogen; alkyl of one to four carbon atoms; or R 1 and R 2 , or R 1 ' and R 2 ', together with the carbon atoms to which they are bonded form a cycloalkyl ring of five to 12 carbon atoms; at a temperature below 100°C, under an inert atmosphere, in an anhydrous inert organic solvent, in the presence of previously isolated bis-cyclooctadiene-(1,5) nickel (0) complex catalyst or in the presence of a catalyst obtained by the reduction of a nickel compound, which is free of carbon monoxide, selected from the group consisting of nickel acetylacetonate, nickel dimethylglyoxime, nickel formate and dicyclopentadienyl nickel, with an organometallic compound free of halogen, in the presence of an electron donor Lewis base selected from the group consisting of cyclic ethers, alkylphosphines, arylphosphines, alkyl phosphites, aryl phosphites and the corresponding alkyl and aryl compounds of arsenic and antimony.
Claim 14
Dependent Claim
21 words
A process for the manufacture of the 1,2-diaza-1-cyclododecenes according to claim 1 which comprises reducing the corresponding 1,2-diaza-1,5,9-cyclododecatriene by catalytic hydrogenation.
Claim 15
Dependent Claim
26 words
A process according to claim 13 wherein said nickel compound is nickel acetylacetonate, said organometallic compound is ethoxy-diethyl-aluminum, and the Lewis base electron donor is triphenylphosphine.
Claim 16
Dependent Claim
19 words
The process according to claim 14 wherein the reaction is carried out at a temperature between 20° and 40°C.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1979-02-16 | 1979-08-18 | 1980-02-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-02-16 | 1983-08-18 | 1984-02-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-02-16 | 1987-08-18 | 1988-02-17 | $7700.00 | Window Closed / Lapsed |