US4480140A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for alkylating phenolic compounds to produce ortho or para-monoalkylated or 2,4- or 2,6-dialkylated phenols
Assignee: Koppers Inc
•
Filing: 1983-03-16
•
Granted: 1984-10-30
•
Expires: 2003-03-16
Abstract
Abstract Phenols alkylated in the ortho and/or para positions are produced in good yields and in the absence of isomers from phenolic compounds having at least two alkylateable ortho-ortho or ortho-para positions open. The phenolic compound is first partially chlorinated or brominated and the desired halogenated phenol having at least one open position ortho or para is reacted with an aldehyde having one to four carbon atoms and a secondary non-aromatic amine. The reaction is conducted in the liquid phase with a stoichiometric amount of the phenolic compound and stoichiometric or excess of stoichiometric amounts of the aldehyde and the amine. The reaction is performed at a temperature of from about 0° C. to about 100° C. to produce an aminoalkylated halogenated phenolic compound. This aminoalkylated halogenated phenolic compound is contacted with hydrogen in the presence of a metal catalyst at a temperature of about 100° C. to about 175° C. and at a hydrogen pressure of less than 500 psig to produce the desired phenol having at least one alkyl group ortho or para and at least one open position ortho or para.
Inventors
- 👤 Gerd Leston
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 01:49
CPC Classifications
C; C07; C07C; C07C37/00; C07C37/62; C07C37/50
Claims Analysis
Total Claims: 42
Claim 1
Independent Claim
223 words
A process for alkylating a phenolic compound having at least two hydrogens available in the ortho-ortho or ortho-para positions to produce a monoalkylated or dialkylated phenol comprising: (a) introducing into the phenolic compound a halogen selected from the group consisting of chlorine and bromine to produce a halogenated phenolic compound having from about six to about twenty two carbon atoms and still containing at least one free hydrogen in the ortho or para position and isolating the halogenated phenolic compound which still has one or two hydrogens at the ortho-para positions; (b) reacting the isolated halogenated phenolic compound with a saturated aliphatic aldehyde having one to about four carbon atoms and a secondary amine having two to about eight carbon atoms, wherein the halogenated phenolic compound is in a stoichiometric amount and the amounts of aldehyde and of amine are in stoichiometric or excess of stoichiometric amount and in the liquid phase and at a temperature in the range of about 0° C. to about 100° C. to produce a Mannich base type aminoalkylated halogenated phenol; (c) contacting the Mannich base type aminoalkylated halogenated phenol with hydrogen in the presence of a hydrogenation catalyst to produce the desired mono or dialkylated phenol and the secondary amine; and (d) separating the secondary amine from the mixture to produce the desired monoalkylated or dialkylated phenol.
Claim 2
Dependent Claim
223 words
A process for alkylating a phenolic compound having at least two hydrogens available in the ortho-ortho or ortho-para positions to produce a monoalkylated or dialkylated phenol comprising: (a) introducing into the phenolic compound a halogen selected from the group consisting of chlorine and bromine to produce a halogenated phenolic compound having from about six to about twenty two carbon atoms and still containing at least one free hydrogen in the ortho or para position and isolating the halogenated phenolic compound which still has one or two hydrogens at the ortho-para positions; (b) reacting the isolated halogenated phenolic compound with a saturated aliphatic aldehyde having one to about four carbon atoms and a secondary amine having two to about eight carbon atoms, wherein the halogenated phenolic compound is in a stoichiometric amount and the amounts of aldehyde and of amine are in stoichiometric or excess of stoichiometric amount and in the liquid phase and at a temperature in the range of about 0° C. to about 100° C. to produce a Mannich base type aminoalkylated halogenated phenol; (c) contacting the Mannich base type aminoalkylated halogenated phenol with hydrogen in the presence of a hydrogenation catalyst to produce the desired mono or dialkylated phenol and the secondary amine; and (d) separating the secondary amine from the mixture to produce the desired monoalkylated or dialkylated phenol.
Claim 3
Dependent Claim
120 words
A process for the synthesis of 2,3,6-trimethylphenol comprising: (a) halogenating m-cresol with a halogen selected from the group consisting of chlorine, bromine, sulfuryl chlorine and sulfuryl bromide and separating 4-halo-m-cresol from other halogenated m-cresols; (b) reacting the 4-halo-m-cresol with formaldehyde and a secondary amine having two to about eight carbon atoms in the liquid phase at a temperature from about 0° C. to 100° C. to produce 2,6-diaminomethyl-4-halo-m-cresol; (c) contacting the Mannich base type 2,6-diaminomethyl-4-halo-m-cresol with hydrogen in the presence of a hydrogenation catalyst to produce one or more phenolic compounds, including the desired 2,3,6-trimethylphenol, and the secondary amine; and (d) separating the secondary amine from the mixture to isolate a mixture of phenolic compounds and then isolating 2,3,6-dimethylphenol therefrom.
Claim 4
Dependent Claim
120 words
A process for the synthesis of 2,3,6-trimethylphenol comprising: (a) halogenating m-cresol with a halogen selected from the group consisting of chlorine, bromine, sulfuryl chlorine and sulfuryl bromide and separating 4-halo-m-cresol from other halogenated m-cresols; (b) reacting the 4-halo-m-cresol with formaldehyde and a secondary amine having two to about eight carbon atoms in the liquid phase at a temperature from about 0° C. to 100° C. to produce 2,6-diaminomethyl-4-halo-m-cresol; (c) contacting the Mannich base type 2,6-diaminomethyl-4-halo-m-cresol with hydrogen in the presence of a hydrogenation catalyst to produce one or more phenolic compounds, including the desired 2,3,6-trimethylphenol, and the secondary amine; and (d) separating the secondary amine from the mixture to isolate a mixture of phenolic compounds and then isolating 2,3,6-dimethylphenol therefrom.
Claim 5
Dependent Claim
162 words
A process for alkylating a halogenated phenolic compound having from about six to about twenty two carbon atoms and having one or two hydrogens at the ortho-para positions comprising: (a) reacting the isolated halogenated phenolic compound with a saturated aliphatic aldehyde having one to about four carbon atoms and a secondary amine having two to about eight carbon atoms, wherein the halogenated phenolic compound is in a stoichiometric amount and the amounts of the aldehyde and of amine is in stoichiometric or excess of stoichiometric amount and in the liquid phase and at a temperature in the range of about 0° C. to about 100° C. to produce a Mannich base type aminoalkylated halogenated phenol; (b) contacting the Mannich base type aminoalkylated halogenated phenol with hydrogen in the presence of a hydrogenation catalyst to produce the desired mono or dialkylated phenol and the secondary amine; and (c) separating the secondary amine from the mixture to produce the desired monoalkylated or dialkylated phenol.
Claim 6
Dependent Claim
162 words
A process for alkylating a halogenated phenolic compound having from about six to about twenty two carbon atoms and having one or two hydrogens at the ortho-para positions comprising: (a) reacting the isolated halogenated phenolic compound with a saturated aliphatic aldehyde having one to about four carbon atoms and a secondary amine having two to about eight carbon atoms, wherein the halogenated phenolic compound is in a stoichiometric amount and the amounts of the aldehyde and of amine is in stoichiometric or excess of stoichiometric amount and in the liquid phase and at a temperature in the range of about 0° C. to about 100° C. to produce a Mannich base type aminoalkylated halogenated phenol; (b) contacting the Mannich base type aminoalkylated halogenated phenol with hydrogen in the presence of a hydrogenation catalyst to produce the desired mono or dialkylated phenol and the secondary amine; and (c) separating the secondary amine from the mixture to produce the desired monoalkylated or dialkylated phenol.
Claim 7
Dependent Claim
93 words
A process for the synthesis of 2,3,6-trimethylphenol comprising: (a) reacting 4-halo-m-cresol with formaldehyde and a secondary amine having two to about eight carbon atoms in the liquid phase at a temperature from about 0° C. to 100° C. to produce 2,6-diaminomethyl-4-halo-m-cresol; (b) contacting the Mannich base type 2,6-diaminomethyl-4-halo-m-cresol with hydrogen in the presence of a hydrogenation catalsyt to produce one or more phenolic compounds, including the desired 2,3,6-trimethylphenol, and the secondary amine; and (c) separating the secondary amine from the mixture to isolate a mixture of phenolic compounds and then isolating 2,3,6-dimethylphenol therefrom.
Claim 8
Dependent Claim
93 words
A process for the synthesis of 2,3,6-trimethylphenol comprising: (a) reacting 4-halo-m-cresol with formaldehyde and a secondary amine having two to about eight carbon atoms in the liquid phase at a temperature from about 0° C. to 100° C. to produce 2,6-diaminomethyl-4-halo-m-cresol; (b) contacting the Mannich base type 2,6-diaminomethyl-4-halo-m-cresol with hydrogen in the presence of a hydrogenation catalsyt to produce one or more phenolic compounds, including the desired 2,3,6-trimethylphenol, and the secondary amine; and (c) separating the secondary amine from the mixture to isolate a mixture of phenolic compounds and then isolating 2,3,6-dimethylphenol therefrom.
Claim 9
Dependent Claim
16 words
The process according to claim 3 wherein the secondary amine used is a secondary aliphatic amine.
Claim 10
Dependent Claim
16 words
The process according to claim 3 wherein the secondary amine used is a secondary alicyclic amine.
Claim 11
Dependent Claim
22 words
The process according to claim 3 wherein the Mannich base type aminoalkylated halogenated phenol is contacted with hydrogen in a glass-lined vessel.
Claim 12
Dependent Claim
40 words
The process according to claim 7 wherein the Mannich base type aminoalkylated halogenated phenol is contacted with hydrogen in the presence of a noble metal catalyst selected from the group consisting of palladium, platinum, rubidium, rhodium, indium, and mixtures thereof.
Claim 13
Dependent Claim
37 words
The process according to claim 8 wherein the Mannich base type aminoalkylated phenol is contacted with hydrogen at a pressure of less than 500 psig and at a temperature of about 100° C. to about 175° C.
Claim 14
Dependent Claim
20 words
The process according to claim 4 wherein the Mannich base type 2,6-diaminomethyl-4-halo-m-cresol is contacted with hydrogen in a glass-lined vessel.
Claim 15
Dependent Claim
38 words
The process according to claim 10 wherein the Mannich base type 2,6-diaminomethyl-4-halo-m-cresol is contacted with hydrogen in the presence of a noble metal catalyst selected from the group consisting of palladium, platinum, rubidium, rhodium, indium and mixtures thereof.
Claim 16
Dependent Claim
37 words
The process according to claim 11 wherein the Mannich base type aminoalkylated phenol is contacted with hydrogen at a pressure of less than 500 psig and at a temperature of about 100° C. to about 175° C.
Claim 17
Dependent Claim
23 words
The process according to claim 3 wherein the separated amine is recycled to be reacted with the halogenated phenolic compound and the aldehyde.
Claim 18
Dependent Claim
21 words
The process according to claim 4 wherein the separated amine is recycled to be reacted with the 4-halo-m-cresol and the aldehyde.
Claim 19
Dependent Claim
37 words
The process according to claim 1 wherein the undesirable halogenated phenols are subjected to hydrogenolysis either by themselves or mixed with the starting phenol so as to convert the undesirable halogenated phenols to the unhalogenated starting phenol.
Claim 20
Dependent Claim
45 words
The process according to claim 1 wherein the undesirable halogenated phenols either by themselves or mixed with the starting phenol are first combined with the aminoalkylated halogenated phenol and subjected to hydrogenolysis and then separation of starting phenol from the alkylated phenolic product is effected.
Claim 21
Dependent Claim
28 words
The process according to claim 8 wherein the noble metal catalysts are supported on materials selected from the group consisting of porous and non-porous carbon blacks and silica.
Claim 22
Dependent Claim
28 words
The process according to claim 11 wherein the noble metal catalysts are supported on materials selected from the group consisting of porous and non-porous carbon blacks and silica.
Claim 23
Dependent Claim
21 words
The process according to claim 15 wherein the catalyst is filtered from the reaction product and recycled to the hydrogenolysis reaction.
Claim 24
Dependent Claim
22 words
The process according to claim 3 wherein the seconary amine is added to the halogenated phenolic compound before the aldehyde is added.
Claim 25
Dependent Claim
20 words
The process according to claim 4 wherein the secondary amine is added to the 4-halo-m-cresol before the aldehyde is added.
Claim 26
Dependent Claim
24 words
The process according to claim 3 wherein the reacting of the halogenated phenolic compound with the amine and the aldehyde is performed in methanol.
Claim 27
Dependent Claim
22 words
The process according to claim 4 wherein the reacting of the 4-halo-m-cresol with the amine and the aldehyde is performed in methanol.
Claim 28
Dependent Claim
19 words
The process according to claim 3 wherein the catalyst used for the hydrogenation is a palladium on carbon catalyst.
Claim 29
Dependent Claim
17 words
The process according to claim 3 wherein the aldehyde used is a 37 percent aqueous formaldehyde solution.
Claim 30
Dependent Claim
12 words
The process according to claim 3 wherein the aldehyde used is paraformaldehyde.
Claim 31
Dependent Claim
34 words
The process according to claim 3 wherein the amine is separated from the mixture by contacting the mixture with an acid and then extracting the phenolic compounds with an organic solvent immiscible with water.
Claim 32
Dependent Claim
25 words
The process according to claim 3 wherein the separated amine is recycled to the reaction of the halogenated phenolic compound, the amine and the aldehyde.
Claim 33
Dependent Claim
23 words
The process according to claim 4 wherein the separated amine is recycled to the reaction of the 4-halo-m-cresol, the amine and the aldehyde.
Claim 34
Dependent Claim
22 words
The process according to claim 3 wherein the secondary amine is selected from the group consisting of dimethylamine, diethylamine, piperidine and morpholine.
Claim 35
Dependent Claim
16 words
The process according to claim 4 wherein the secondary amine used is a secondary aliphatic amine.
Claim 36
Dependent Claim
16 words
The process according to claim 4 wherein the seconary amine used is a secondary alicyclic amine.
Claim 37
Dependent Claim
21 words
The process according to claim 16 wherein the catalyst is filtered from the reaction product and recycled to the hydrogenolysis reaction.
Claim 38
Dependent Claim
19 words
The process according to claim 4 wherein the catalyst used for the hydrogenation is a palladium on carbon catalyst.
Claim 39
Dependent Claim
17 words
The process according to claim 4 wherein the aldehyde used is a 37 percent aqueous formaldehyde solution.
Claim 40
Dependent Claim
12 words
The process according to claim 4 wherein the aldehyde used is paraformaldehyde.
Claim 41
Dependent Claim
34 words
The process according to claim 4 wherein the amine is separated from the mixture by contacting the mixture with an acid and then extracting the phenolic compounds with an organic solvent immiscible with water.
Claim 42
Dependent Claim
22 words
The process according to claim 4 wherein the secondary amine is selected from the group consisting of dimethylamine, diethylamine, piperidine and mopholine.
References Cited (Backward Citations)
US2194215A
Cited
US2452154A
Cited
US2494993A
Cited
US2842595A
Cited
US3413347A
Cited
US3592951A
Cited
US3726882A
Cited
US3946086A
Cited
US4072724A
Cited
US4122287A
Cited
US4215229A
Cited
US4309407A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-10-30 | 1988-04-30 | 1988-10-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-10-30 | 1992-04-30 | 1992-10-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-10-30 | 1996-04-30 | 1996-10-30 | $7700.00 | Window Closed / Lapsed |