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US3975439A
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Preparation and amination of iodoaniline
Assignee: EIDP Inc
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Filing: 1973-07-26
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Granted: 1976-08-17
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Expires: 1993-07-26
Abstract
Abstract Described is a cyclic process for preparing p-phenylenediamine from aniline and ammonia including aminating iodoaniline, recovering the iodide from the amination, and electrolyzing the iodide with aniline back to iodoaniline. Also described are the two basic reactions of the cyclic process, a new process for preparing phenylenediamines by the amination of the corresponding iodoanilines with ammonia in the presence of copper metal or a copper(I) salt and a new process for preparing p-iodoaniline by electrolysis of aniline with ammonium iodide as well as a new compound useful in the amination.
Inventors
- 👤 Ulrich Klabunde
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 07:00
CPC Classifications
B; B01; B01J; B01J23/00; B01J23/70; B01J23/72
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
110 words
A cyclic process of producing p-phenylenediamine from ammonia and aniline which comprises: a. electrolyzing aniline with aqueous sodium iodide in an electrolytic cell having a cationic membrane to form an anolyte containing iodoaniline; b. reacting the organic portion of the anolyte with ammonia at a molar ratio of ammonia to iodoaniline of at least 1:1 in the presence of a Cu(I) salt catalyst to form a liquid containing phenylenediamine, ammonium iodide and the 1:1 copper(I) iodide-p-phenylenediamine complex; c. reacting the liquid from step (b) with sodium hydroxide; d. recovering ammonia and p-phenylenediamine from the product of step (c); and e. returning sodium iodide recovered after step (c) to step (a).
Claim 2
Dependent Claim
110 words
A cyclic process of producing p-phenylenediamine from ammonia and aniline which comprises: a. electrolyzing aniline with aqueous sodium iodide in an electrolytic cell having a cationic membrane to form an anolyte containing iodoaniline; b. reacting the organic portion of the anolyte with ammonia at a molar ratio of ammonia to iodoaniline of at least 1:1 in the presence of a Cu(I) salt catalyst to form a liquid containing phenylenediamine, ammonium iodide and the 1:1 copper(I) iodide-p-phenylenediamine complex; c. reacting the liquid from step (b) with sodium hydroxide; d. recovering ammonia and p-phenylenediamine from the product of step (c); and e. returning sodium iodide recovered after step (c) to step (a).
Claim 3
Dependent Claim
22 words
The process of claim 1 in which the product of step (c) is extracted with aqueous sodium hydroxide to recover sodium iodide.
Claim 4
Dependent Claim
17 words
The process of claim 1 in which step (b) is carried out in the presence of hydrazine.
Claim 5
Dependent Claim
20 words
The process of claim 1 in which the 1:1 copper(I) iodide.p-phenylenediamine complex is recovered from step (b) and recycled thereto.
Claim 6
Dependent Claim
13 words
The process of claim 1 wherein phenylenediamine is extracted by means of aniline.
Claim 7
Dependent Claim
61 words
A process of producing a phenylenediamine which comprises reacting the corresponding iodoaniline with ammonia carried out in solution containing up to about 5% by weight of water, the molar ratio of ammonia to iodoaniline being at least 1:1, in the presence of a catalytic amount of copper or a copper(I) salt, and at a temperature in the range of about 0°-160°C.
Claim 8
Dependent Claim
61 words
A process of producing a phenylenediamine which comprises reacting the corresponding iodoaniline with ammonia carried out in solution containing up to about 5% by weight of water, the molar ratio of ammonia to iodoaniline being at least 1:1, in the presence of a catalytic amount of copper or a copper(I) salt, and at a temperature in the range of about 0°-160°C.
Claim 9
Dependent Claim
12 words
The process of claim 6 wherein the ammonia solution is anhydrous ammonia.
Claim 10
Dependent Claim
10 words
The process of claim 6 carried out in nonaqueous solvent.
Claim 11
Dependent Claim
11 words
The process of claim 8 wherein the non-aqueous solvent is aniline.
Claim 12
Dependent Claim
23 words
The process of claim 9 wherein the solution contains a copper(I) salt and, in addition, 0.1-1.0 mole of hydrazine per mole of copper(I).
Claim 13
Dependent Claim
12 words
The process of claim 6 wherein the catalyst is a cuprous halide.
Claim 14
Dependent Claim
11 words
The process of claim 11 wherein the catalyst is cuprous iodide.
Claim 15
Dependent Claim
14 words
The process of claim 11 wherein the catalyst is the 1:1 copper(I) iodide.p-phenylenediamine complex.
Claim 16
Dependent Claim
18 words
The process of claim 6 wherein the catalyst is generated by in situ reduction of a cupric salt.
Claim 17
Dependent Claim
32 words
The process of claim 6 wherein the temperature is in the range of about 40°-140°C. and the molar ratio of ammonia to iodoaniline is within the range of about 6:1 to 40:1.
Claim 18
Dependent Claim
15 words
The process of claim 6 wherein the iodoaniline is p-iodoaniline and the product is p-phenylenediamine.
Claim 19
Dependent Claim
28 words
The process which comprises electrolyzing aqueous ammonium iodide or aqueous alkali metal iodide with aniline at a temperature in the range of about 0°-80°C. and thereby producing p-iodoaniline.
Claim 20
Dependent Claim
28 words
The process which comprises electrolyzing aqueous ammonium iodide or aqueous alkali metal iodide with aniline at a temperature in the range of about 0°-80°C. and thereby producing p-iodoaniline.
Claim 21
Dependent Claim
21 words
The process of claim 17 including the additional step of aminating the p-iodoaniline with ammonia to form p-phenylenediamine and ammonium iodide.
Claim 22
Dependent Claim
19 words
The process of claim 18 including the additional steps of recovering iodide ion and electrolyzing the same with aniline.
Claim 23
Dependent Claim
15 words
The process of claim 17 wherein the temperature is in the range of about 20°-50°C.
Claim 24
Dependent Claim
60 words
The process of claim 6 wherein: a. the temperature is in the range of about 40°-140°C.; b. the catalyst is at least one of cuprous iodide and the 1:1 copper(I) iodide, p-phenylenediamine complex, c. the reaction is carried out in aniline as solvent, and d. the ratio of ammonia to iodoaniline is within the range of about 6:1 to 40:1.
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) | 1979-08-17 | 1980-02-16 | 1980-08-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-08-17 | 1984-02-16 | 1984-08-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-08-17 | 1988-02-16 | 1988-08-17 | $7700.00 | Window Closed / Lapsed |