US3906045A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Homogeneous ruthenium catalysts useful in the selective reduction of nitroaromatics to amines
Assignee: Texaco Inc
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Filing: 1974-04-22
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Granted: 1975-09-16
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Expires: 1994-04-22
Abstract
Abstract This invention concerns the use of solubilized homogeneous ruthenium catalysts to initially and sequentially reduce the nitro group in mononitroaromatic substrates to the corresponding amine. The reduction must be carried out in a two component mixture consisting essentially of the mononitroaromatic and a mononitro ortho-substituted polyalkylaromatic component. In order to minimize the reduction of said nitropolyalkylaromatic component, the reduction should be halted when between about 80 to 95 % of the mononitroaromatic substrate present is reduced to the corresponding amine.
Inventors
- 👤 John F Knifton
- 👤 Robert M Suggitt
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 02:22
CPC Classifications
C; C07; C07F; C07F15/00; C07F15/0006; C07F15/0046; C07F15/0053; C07C; C07C209/00; C07C209/30; C07C209/32; C07C209/36
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
83 words
ADMIXING ONE MONONITROAROMATIC SUBSTRATES SELECTED FROM THE GROUP CONSISTING OF NITROBENZENE, P-NITROTOLUENE, M-NITROTOLUENE, P-NITROETHYLBENZENE, 1,2-DIMETHYL4-NITROBENZENE, 1,2-DIMETHYL-3-NITROBENZENE, 1,4DIMETHYL-2-NITROBENZENE, 1,3-DIMETHYL-4-NITROBENZENE, 1,3-DIMETHYL-5-NITROBENZENE-1-NITRONAPHTHALENE, 2NITRONAPHTHALENE, 4-NITROBIPHENYL AND 9-NITROANTHRACENE, WITH ONE MONONITRO ORTHO SUBSTITUTED POLYALKYLAROMATIC SUBSTRATE SELECTED FROM THE GROUP CONSISTING OF 2NITROMESITYLENE, NITRODURENE, 1,3-DIMETHYL-2-NITROBENZENE AND 1,3-DIETHYL-2-NITROBENZENE IN THE PRESENCE OF INERT, NON-AQUEOUS, NON-OXIXIZING SOLVENT ENVIRONMENT, WITH AT LEAST A CATALYTIC QUANTITY OF A HOMOGENEOUS, SOLUBILIZED RUTHENIUM CATALYST SELECTED FROM THE GROUP CONSISTING OF RUCL2(P(C6H5)3L3, (RU(CO)3CL2)2, RUCL2(CO)2(P(C6H5)3)2, RUCL3(AS(C6H5)3)2, RUCL2(SB(C6H5)3)3, RUCL2(P(P-CH3,C6H4)3L3, RUCLH(P(C6H5)3)3 AND RUCL2(P(CH3)2C6H5)2 TO FORM A REACTION MIXTURE, AND
Claim 2
Dependent Claim
83 words
ADMIXING ONE MONONITROAROMATIC SUBSTRATES SELECTED FROM THE GROUP CONSISTING OF NITROBENZENE, P-NITROTOLUENE, M-NITROTOLUENE, P-NITROETHYLBENZENE, 1,2-DIMETHYL4-NITROBENZENE, 1,2-DIMETHYL-3-NITROBENZENE, 1,4DIMETHYL-2-NITROBENZENE, 1,3-DIMETHYL-4-NITROBENZENE, 1,3-DIMETHYL-5-NITROBENZENE-1-NITRONAPHTHALENE, 2NITRONAPHTHALENE, 4-NITROBIPHENYL AND 9-NITROANTHRACENE, WITH ONE MONONITRO ORTHO SUBSTITUTED POLYALKYLAROMATIC SUBSTRATE SELECTED FROM THE GROUP CONSISTING OF 2NITROMESITYLENE, NITRODURENE, 1,3-DIMETHYL-2-NITROBENZENE AND 1,3-DIETHYL-2-NITROBENZENE IN THE PRESENCE OF INERT, NON-AQUEOUS, NON-OXIXIZING SOLVENT ENVIRONMENT, WITH AT LEAST A CATALYTIC QUANTITY OF A HOMOGENEOUS, SOLUBILIZED RUTHENIUM CATALYST SELECTED FROM THE GROUP CONSISTING OF RUCL2(P(C6H5)3L3, (RU(CO)3CL2)2, RUCL2(CO)2(P(C6H5)3)2, RUCL3(AS(C6H5)3)2, RUCL2(SB(C6H5)3)3, RUCL2(P(P-CH3,C6H4)3L3, RUCLH(P(C6H5)3)3 AND RUCL2(P(CH3)2C6H5)2 TO FORM A REACTION MIXTURE, AND
Claim 3
Dependent Claim
39 words
A PROCESS FOR SELECTIVELY AND SEQUENTIALLY HYDROGENATING THE NITRO GROUP OF A MONONITROAROMATIC SUBSTRATE CONTAINED IN A TWO COMPONENT NITROAROMATIC SUBSTRATE MIXTURE CONSISTING ESSENTIALLY OF ONE MONONITROAROMATIC SUBSTRATE AND ONE MONONITRO ORTHO-SUBSTITUTED POLYALKYLAROMATIC SUBSTRATE, SAID PROCESS CONSISTING ESSENTIALLY OF:
Claim 4
Dependent Claim
39 words
A PROCESS FOR SELECTIVELY AND SEQUENTIALLY HYDROGENATING THE NITRO GROUP OF A MONONITROAROMATIC SUBSTRATE CONTAINED IN A TWO COMPONENT NITROAROMATIC SUBSTRATE MIXTURE CONSISTING ESSENTIALLY OF ONE MONONITROAROMATIC SUBSTRATE AND ONE MONONITRO ORTHO-SUBSTITUTED POLYALKYLAROMATIC SUBSTRATE, SAID PROCESS CONSISTING ESSENTIALLY OF:
Claim 5
Dependent Claim
11 words
The process of claim 1 wherein the ruthenium catalyst is RuCl2(P(C6H5)3)3.
Claim 6
Dependent Claim
68 words
heating said reaction mixture between about 50*C to about 135*C with at least sufficient hydrogen gas to hydrogenate the nitro group of the one mononitroaromatic said hydrogen gas being supplied at superatmospheric pressure ranging from about 100 psig to about 2000 psig and continuing heating the pressurized reaction mixture until from about 80% to 95% of said nitro group of the mononitroaromatic is converted to the corresponding amine.
Claim 7
Dependent Claim
68 words
heating said reaction mixture between about 50*C to about 135*C with at least sufficient hydrogen gas to hydrogenate the nitro group of the one mononitroaromatic said hydrogen gas being supplied at superatmospheric pressure ranging from about 100 psig to about 2000 psig and continuing heating the pressurized reaction mixture until from about 80% to 95% of said nitro group of the mononitroaromatic is converted to the corresponding amine.
Claim 8
Dependent Claim
68 words
HEATING SAID REACTION MIXTURE BETWEEN ABOUT MIXTURE, AND ABOUT 135*C WITH AT LEAST SUFFICIENT HYDROGEN GAS TO HYDROGENATE THE NITRO GROUP OF THE ONE MONONITROAROMATIC SAID HYDROGEN GAS BEING SUPPLIED AT SUPERATMOSPHERIC PRESSURE RANGING FROM ABOUT 100 PSIG TO ABOUT 2000 PSIG AND CONTINUING HEATING THE PRESSURIZED REACTION MIXTURE UNTIL FROM ABOUT 80% TO 95% OF SAID NITRO GROUP OF THE MONONITROAROMATIC IS CONVERTED TO THE CORRESPONDING AMINE.
Claim 9
Dependent Claim
68 words
HEATING SAID REACTION MIXTURE BETWEEN ABOUT MIXTURE, AND ABOUT 135*C WITH AT LEAST SUFFICIENT HYDROGEN GAS TO HYDROGENATE THE NITRO GROUP OF THE ONE MONONITROAROMATIC SAID HYDROGEN GAS BEING SUPPLIED AT SUPERATMOSPHERIC PRESSURE RANGING FROM ABOUT 100 PSIG TO ABOUT 2000 PSIG AND CONTINUING HEATING THE PRESSURIZED REACTION MIXTURE UNTIL FROM ABOUT 80% TO 95% OF SAID NITRO GROUP OF THE MONONITROAROMATIC IS CONVERTED TO THE CORRESPONDING AMINE.
Claim 10
Dependent Claim
11 words
The process of claim 1 wherein the ruthenium catalyst is (Ru(CO)3Cl2)2.
Claim 11
Dependent Claim
11 words
The process of claim 1 wherein the ruthenium catalyst is RuCl2(CO)2(P(C6H5)3)2.
Claim 12
Dependent Claim
11 words
The process of claim 1 wherein the ruthenium catalyst is RuCl3(As(C6H5)3)2.
Claim 13
Dependent Claim
11 words
The process of claim 1 wherein the ruthenium catalyst is RuCl2(Sb(C6H5)3)3.
Claim 14
Dependent Claim
11 words
The process of claim 1 wherein the ruthenium catalyst is RuCl2(P(p-CH3.C6H4)3)3.
Claim 15
Dependent Claim
11 words
The process of claim 1 wherein the ruthenium catalyst is RuClH(P(C6H5)3)3.
Claim 16
Dependent Claim
11 words
The process of claim 1 wherein the ruthenium catalyst is RuCl2(P(CH3)2C6H5)3.
Claim 17
Dependent Claim
13 words
THe process of claim 1 in which the mixture is 1,2-dimethyl-4-nitrobenzene and 1,3-dimethyl-2-nitrobenzene.
Claim 18
Dependent Claim
13 words
The process of claim 1 in which the mixture is nitrobenzene and 2-nitromesitylene.
Claim 19
Dependent Claim
13 words
The process of claim 1 in which the mixture is 1-nitronaphthalene and 2-nitromesitylene.
Claim 20
Dependent Claim
13 words
The process of claim 1 in which the mixture is 1,3-dimethyl-5-nitrobenzene and 1,3-dimethyl-2-nitrobenzene.
Claim 21
Dependent Claim
29 words
The process of claim 1 in which the nonaqueous, substantially non-oxidizing solvent media is selected from the group consisting of aromatics, alkylated aromatics, chlorinated aliphatic hydrocarbons and mixtures thereof.
Claim 22
Dependent Claim
22 words
The process of claim 1 wherein the nonaqueous solvent media contains a solvating agent which is polar and contains a hydroxyl group.
Claim 23
Dependent Claim
19 words
The process of claim 15 in which the solvating agent is a mono or polyhydric aliphatic or aromatic alcohol.
Claim 24
Dependent Claim
24 words
The process of claim 1 in which the used catalyst is recovered by precipitation after stripping off a substantial quantity of the solvent media.
References Cited (Backward Citations)
US3110747A
Cited
US3694509A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-09-15 | 1979-03-17 | 1979-09-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-09-15 | 1983-03-17 | 1983-09-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-09-15 | 1987-03-17 | 1987-09-16 | $7700.00 | Window Closed / Lapsed |