US4386209A
Expired / Lapsed
US
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Chichibabin reaction
Assignee: Vertellus Specialties Inc
•
Filing: 1982-04-08
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Granted: 1983-05-31
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Expires: 2002-04-08
Abstract
Abstract In a Chichibabin amination of a pyridine base by sodamide in an organic solvent, the improvement comprising conducting the reaction under pressure of at least about 50 psi in the gas phase above the reaction mixture and adding ammonia to the mixture sufficient to produce a partial pressure of ammonia of at least about 5 psi in the gas phase. Preferred temperature and pressure ranges are disclosed, as are catalysts and other preferred steps for practicing the reaction. Significant results are obtained including improved and changed yields from those classically expected in Chichibabin aminations, including new compositions of matter in at least one case.
Inventors
- 👤 Charles K. McGill
- 👤 James J. Sutor
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 03:36
CPC Classifications
C; C07; C07D; C07D213/00; C07D213/02; C07D213/04; C07D213/60; C07D213/72; C07D213/73; C07D213/74; C07D213/78; C07D213/79; C07D213/80; C07D213/81; C07D213/82
Claims Analysis
Total Claims: 51
Claim 1
Independent Claim
65 words
In a Chichibabin amination of a pyridine base by sodamide in an organic solvent, the improvement comprising the steps of: (a) conducting the reaction under pressure of at least about 50 psi in the gas phase above the reaction mixture; and (b) adding ammonia to the mixture sufficient to produce a partial pressure of ammonia of at least about 5 psi in the gas phase.
Claim 2
Dependent Claim
65 words
In a Chichibabin amination of a pyridine base by sodamide in an organic solvent, the improvement comprising the steps of: (a) conducting the reaction under pressure of at least about 50 psi in the gas phase above the reaction mixture; and (b) adding ammonia to the mixture sufficient to produce a partial pressure of ammonia of at least about 5 psi in the gas phase.
Claim 3
Dependent Claim
15 words
The Chichibabin amination of claim 1 in which said adding is prior to said conducting.
Claim 4
Dependent Claim
58 words
The Chichibabin amination of claim 2 comprising the additional steps of: (a) placing the gas phase above the mixture under pressure of at least about 100 psi prior to said conducting; and (b) maintaining the gas phase under pressure of at least about 300 psi with at least some partial pressure of ammonia being present during said conducting.
Claim 5
Dependent Claim
27 words
The Chichibabin amination of claim 3 in which said placing said maintaining include using the autogenous evolution of gases from the mixture to pressurize the gas phase.
Claim 6
Dependent Claim
26 words
The Chichibabin amination of claim 3 in which said adding is in addition to any autogenous pressure of ammonia generated in situ from the reaction mixture.
Claim 7
Dependent Claim
27 words
The Chichibabin amination of claim 3 in which said adding includes the step of preparing the sodamide in situ in excess liquid ammonia prior to said conducting.
Claim 8
Dependent Claim
21 words
The Chichibabin amination of claim 3 in which said adding includes the step of injecting gaseous ammonia into the reaction vessel.
Claim 9
Dependent Claim
48 words
The Chichibabin amination of claim 7 in which said placing and said maintaining and said conducting are in a substantially inert atmosphere, and said adding is sufficient to produce a partial pressure of ammonia of at least about 15-50 psi in the gas phase prior to said conducting.
Claim 10
Dependent Claim
18 words
The Chichibabin amination of claim 8 in which said conducting is at a temperature between about 130°-200° C.
Claim 11
Dependent Claim
33 words
The Chichibabin amination of claim 9 in which the pyridine base is selected from the group consisting of: 3-picoline; nicotinic acid; nicotinamide; 3-hydroxypyridine; 4-dimethylaminopyridine; 4-(5-nonyl)pyridine; 3-ethylpyridine; 3-propylpyridine; 3-isopropylpyridine; 3-butylpyridine; 3-(3-phenylpropyl)pyridine; 3-phenylpyridine; and 3,4-lutidine.
Claim 12
Dependent Claim
35 words
The Chichibabin amination of claim 9 in which the pyridine base is selected from the group consisting of: pyridine; 2-aminopyridine; 3-picoline; nicotinic acid; nicotinamide; 3-hydroxypyridine; 4-dimethylaminopyridine; 4-(5-nonyl)pyridine; 3-ethylpyridine; 3-propylpyridine; 3-isopropylpyridine; 3-butylpyridine; 3-(3-phenylpropyl)pyridine; 3-phenylpyridine; and 3,4-lutidine.
Claim 13
Dependent Claim
21 words
The Chichibabin amination of claim 9 in which said conducting is in the presence of a catalytic amount of an aminopyridine.
Claim 14
Dependent Claim
25 words
The Chichibabin amination of claim 9 in which said conducting is in the presence of a catalytic amount of a desired product of the reaction.
Claim 15
Dependent Claim
81 words
In a Chichibabin amination of a pyridine base by sodamide in an organic solvent, the improvement comprising the steps of: increasing pressure and adding ammonia in the gas phase above the reaction mixture sufficient to increase yield by at least about one third of a product expected in the Chichibabin amination or to produce a yield of at least about 10% of a product not expected in the Chichibabin amination, each yield being as a percent of total amination products obtained.
Claim 16
Dependent Claim
81 words
In a Chichibabin amination of a pyridine base by sodamide in an organic solvent, the improvement comprising the steps of: increasing pressure and adding ammonia in the gas phase above the reaction mixture sufficient to increase yield by at least about one third of a product expected in the Chichibabin amination or to produce a yield of at least about 10% of a product not expected in the Chichibabin amination, each yield being as a percent of total amination products obtained.
Claim 17
Dependent Claim
36 words
The Chichibabin amination of claim 14 in which said increasing is to a pressure of at least about 50 psi and said adding is to a partial pressure of ammonia of at least about 5 psi.
Claim 18
Dependent Claim
19 words
The Chichibabin amination of claim 15 comprising the additional step of conducting the reaction in a substantially inert atmosphere.
Claim 19
Dependent Claim
27 words
The Chichabibin amination of claim 16 in which said adding includes the step of preparing the sodamide in situ in excess liquid ammonia prior to said conducting.
Claim 20
Dependent Claim
21 words
The Chichibabin amination of claim 16 in which said adding includes the step of injecting gaseous ammonia into the reaction vessel.
Claim 21
Dependent Claim
21 words
The Chichibabin amination of claim 18 in which said conducting is in the presence of a catalytic amount of an aminopyridine.
Claim 22
Dependent Claim
25 words
The Chichibabin amination of claim 18 in which said conducting is in the presence of a catalytic amount of a desired product of the reaction.
Claim 23
Dependent Claim
36 words
The Chichibabin amination of claim 18 in which said increasing is to a pressure of at least about 200 psi and said adding is to a partial pressure of ammonia of at least about 15-50 psi.
Claim 24
Dependent Claim
21 words
The Chichibabin amination of claim 21 comprising the additional step of conducting the reaction at a temperature between about 130°-200° C.
Claim 25
Dependent Claim
33 words
The Chichibabin amination of claim 22 in which the pyridine base is selected from the group consisting of: 3-picoline; nicotinic acid; nicotinamide; 3-hydroxypyridine; 4-dimethylaminopyridine; 4-(5-nonyl)pyridine; 3-ethylpyridine; 3-propylpyridine; 3-isopropylpyridine; 3-butylpyridine; 3-(3-phenylpropyl)pyridine; 3-phenylpyridine; and 3,4-lutidine.
Claim 26
Dependent Claim
32 words
The Chichibabin amination of claim 23 in which said increasing is to a pressure of about 300 psi and said adding is to a partial pressure of ammonia of about 45 psi.
Claim 27
Dependent Claim
129 words
An improved Chichibabin amination, comprising the steps of: (a) combining an amount of pyridine base and at least a slight stoichiometric excess of sodamide in an organic solvent in a closed reaction vessel; (b) adding ammonia to the vessel to produce an initial partial pressure of ammonia of at least about 5 psi in the gas phase; (c) placing the gas phase in the vessel under pressure of at least about 50 psi with a partial pressure of ammonia being present at least equal to the autogenous pressure of ammonia generated in situ from the mixture; (d) bringing the resulting mixture to a temperature sufficient to cause amination to begin; and (e) maintaining the mixture at a temperature and for a period sufficient to cause substantial amination to occur.
Claim 28
Dependent Claim
129 words
An improved Chichibabin amination, comprising the steps of: (a) combining an amount of pyridine base and at least a slight stoichiometric excess of sodamide in an organic solvent in a closed reaction vessel; (b) adding ammonia to the vessel to produce an initial partial pressure of ammonia of at least about 5 psi in the gas phase; (c) placing the gas phase in the vessel under pressure of at least about 50 psi with a partial pressure of ammonia being present at least equal to the autogenous pressure of ammonia generated in situ from the mixture; (d) bringing the resulting mixture to a temperature sufficient to cause amination to begin; and (e) maintaining the mixture at a temperature and for a period sufficient to cause substantial amination to occur.
Claim 29
Dependent Claim
39 words
The Chichibabin amination of claim 25 in which said maintaining further includes maintaining the gas phase in the vessel under pressure of at least about 100 psi with at least some partial pressure of ammonia being present during amination.
Claim 30
Dependent Claim
26 words
The Chichibabin amination of claim 26 comprising the additional step of using the autogenous pressure of gases evolved in situ during amination to accomplish said maintaining.
Claim 31
Dependent Claim
18 words
The Chichibabin amination of claim 27 in which said adding is prior to said bringing and said maintaining.
Claim 32
Dependent Claim
30 words
The Chichibabin amination of claim 28 in which said adding includes the step of preparing the sodamide in situ in excess liquid ammonia in the vessel prior to said combining.
Claim 33
Dependent Claim
69 words
The Chichibabin amination of claim 28 in which said placing and said maintaining under pressure and said adding of ammonia are sufficient to increase yield by at least about one third of a product expected in the Chichibabin amination or to produce a yield of at least about 10% of a product not expected in the Chichibabin amination, each yield being as a percent of total amination products obtained.
Claim 34
Dependent Claim
19 words
The Chichibabin amination of claim 28 in which said placing and said maintaining are under a substantially inert atmosphere.
Claim 35
Dependent Claim
15 words
The Chichibabin amination of claim 31 in which said placing is prior to said bringing.
Claim 36
Dependent Claim
19 words
The Chichibabin amination of claim 32 in which said adding is to at least about 15-50 psi of ammonia.
Claim 37
Dependent Claim
17 words
The Chichibabin amination of claim 33 in which said maintaining is to at least about 300 psi.
Claim 38
Dependent Claim
30 words
The Chichibabin amination of claim 34 in which said bringing is to a temperature at which hydrogen gas is evolved, and said maintaining is until hydrogen evolution has substantially ceased.
Claim 39
Dependent Claim
21 words
The Chichibabin amination of claim 35 in which said bringing and said maintaining are to a temperature between about 130°-200° C.
Claim 40
Dependent Claim
21 words
The Chichibabin amination of claim 36 in which said combining is in the presence of a catalytic amount of an aminopyridine.
Claim 41
Dependent Claim
25 words
The Chichibabin amination of claim 36 in which said combining is in the presence of a catalytic amount of a desired product of the reaction.
Claim 42
Dependent Claim
17 words
The Chichibabin amination of claim 36 in which said maintaining is without refluxing of the reaction mixture.
Claim 43
Dependent Claim
21 words
The Chichibabin amination of claim 36 comprising the additional step of venting off excess pressure from gases evolved during said maintaining.
Claim 44
Dependent Claim
21 words
The Chichibabin amination of claim 40 in which said adding includes the step of injecting gaseous ammonia into the reaction vessel.
Claim 45
Dependent Claim
36 words
The Chichibabin amination of claim 41 in which said combining is of a pyridine base selected from the group consisting of: 3-picoline; nicotinic acid; nicotinamide; 3-hydroxypyridine; 4-dimethylaminopyridine; 4-(5-nonyl)pyridine; 3-ethylpyridine; 3-propylpyridine; 3-isopropylpyridine; 3-butylpyridine; 3-(3-phenylpropyl)pyridine; 3-phenylpyridine; and 3,4-lutidine.
Claim 46
Dependent Claim
35 words
The Chichibabin amination of claim 41 in which the pyridine base is selected from said group consisting of: pyridine; 2-aminopyridine; 3-picoline; nicotinic acid; nicotinamide; 3-hydroxypyridine; 4-dimethylaminopyridine; 4-(5-nonyl)pyridine; 3-ethylpyridine; 3-propylpyridine; 3-isopropylpyridine; 3-butylpyridine; 3-(3-phenylpropyl)pyridine; 3-phenylpyridine; and 3,4-lutidine.
Claim 47
Dependent Claim
20 words
The Chichibabin amination of claim 40 comprising the additional step of purging the vessel of air prior to said placing.
Claim 48
Dependent Claim
33 words
The Chichibabin amination of claim 44 comprising the additional steps of: (a) cooling the reaction mixture and venting the vessel to atmospheric pressure after said maintaining; and (b) recovering the desired reaction product.
Claim 49
Dependent Claim
13 words
The Chichibabin amination of claim 45 in which the pyridine base is 3-picoline.
Claim 50
Dependent Claim
9 words
A new composition of matter, comprising 2-amino-5-(3-phenylpropyl)pyridine or 2-amino-3-(3-phenylpropyl)pyridine.
Claim 51
Dependent Claim
9 words
A new composition of matter, comprising 2-amino-5-(3-phenylpropyl)pyridine or 2-amino-3-(3-phenylpropyl)pyridine.
References Cited (Backward Citations)
No citation records indexed.
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-05-30 | 1986-11-29 | 1987-05-31 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-05-30 | 1990-11-29 | 1991-05-31 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-05-30 | 1994-11-29 | 1995-05-31 | $7700.00 | Window Closed / Lapsed |