Process for alkylating phenolic compounds to produce ortho- or para-monoalkylated phenols or 2,4- or 2,6-dialkylated phenols

Claim 2

A process for alkylating a phenolic compound having from about six to about ten carbon atoms and having at least two hydrogens in the ortho-ortho or ortho-para positions to produce another phenolic compound having one or two alkyl groups in the ortho or para or ortho-ortho or ortho-para positions comprising: (a) converting the phenolic compound to a mono- or di-t-alkylated phenol derivative which still has one or two hydrogens in the ortho, para, ortho-ortho or ortho-para positions; (b) reacting the t-alkylated compound formed in step (a) with a saturated aliphatic aldehyde having one to four carbon atoms and a secondary non-aromatic amine having two to about eight carbon atoms, wherein the amount of the t-alkylated phenolic compound is a stoichiometric amount and the amounts of the aldehyde and amine are at least stoichiometric amounts, and at a temperature in the range of about 0° C. to about 100° C. to produce a Mannich base type aminoalkylated t-alkylated phenolic compound; (c) contacting the Mannich base type aminoalkylated t-alkylated phenolic formed in step (b) with hydrogen in the presence of a hydrogenation catalyst to produce an alkylated t-alkylated phenolic compound; and (d) contacting the alkylated t-alkylated phenolic compound formed in step (c) with an acid or an acid reacting substance at a temperature from about 25° C. to about 300° C. to produce a phenolic compound which is selected from the group consisting of a monoalkylated phenolic compounds alkylated in the ortho- or para-positions and dialkylated phenolic compounds alkylated in the ortho-ortho, ortho- or ortho-para-positions and having at least one ortho- or para-position unsubstituted.

Claim 3

A process for alkylating a phenolic compound having from about six to about ten carbon atoms and having at least two hydrogens in the ortho-ortho or ortho-para positions to produce another phenolic compound having one or two alkyl groups in the ortho or para or ortho-ortho or ortho-para positions comprising: (a) converting the phenolic compound to a mono- or di-t-alkylated phenol derivative which still has one or two hydrogens in the ortho, para, ortho-ortho or ortho-para positions; (b) reacting the t-alkylated compound formed in step (a) with a saturated aliphatic aldehyde having one to four carbon atoms and a secondary non-aromatic amine having two to about eight carbon atoms, wherein the amount of the t-alkylated phenolic compound is a stoichiometric amount and the amounts of the aldehyde and amine are at least stoichiometric amounts, and at a temperature in the range of about 01° C. to about 100° C. to produce a Mannich base type aminoalkylated t-alkylated phenolic compound; (c) contacting the aminoalkylated t-alkylated phenolic compound formed in step (b) with an acid or an acid reacting substance at a temperature from about 25° C. to about 300° C. to produce an aminoalkylated phenolic compound which is selected from the group consisting of aminoalkylated phenolic compounds, aminoalkylated in the ortho- or para-positions and diaminoalkylated phenolic compounds aminoalkylated in the ortho-ortho, ortho or ortho-para positions and having at least one ortho- or para-position unsubstituted; and (d) contacting the Mannich base type aminoalkylated phenol compound formed in step (c) with hydrogen in the presence of a hydrogenation catalyst to produce an alkylated phenolic compound having at least one ortho- or para-position unsubstituted.

Claim 4

A process for alkylating a phenolic compound having from about six to about ten carbon atoms and having at least two hydrogens in the ortho-ortho or ortho-para positions to produce another phenolic compound having one or two alkyl groups in the ortho or para or ortho-ortho or ortho-para positions comprising: (a) converting the phenolic compound to a mono- or di-t-alkylated phenol derivative which still has one or two hydrogens in the ortho, para, ortho-ortho or ortho-para positions; (b) reacting the t-alkylated compound formed in step (a) with a saturated aliphatic aldehyde having one to four carbon atoms and a secondary non-aromatic amine having two to about eight carbon atoms, wherein the amount of the t-alkylated phenolic compound is a stoichiometric amount and the amounts of the aldehyde and amine are at least stoichiometric amounts, and at a temperature in the range of about 01° C. to about 100° C. to produce a Mannich base type aminoalkylated t-alkylated phenolic compound; (c) contacting the aminoalkylated t-alkylated phenolic compound formed in step (b) with an acid or an acid reacting substance at a temperature from about 25° C. to about 300° C. to produce an aminoalkylated phenolic compound which is selected from the group consisting of aminoalkylated phenolic compounds, aminoalkylated in the ortho- or para-positions and diaminoalkylated phenolic compounds aminoalkylated in the ortho-ortho, ortho or ortho-para positions and having at least one ortho- or para-position unsubstituted; and (d) contacting the Mannich base type aminoalkylated phenol compound formed in step (c) with hydrogen in the presence of a hydrogenation catalyst to produce an alkylated phenolic compound having at least one ortho- or para-position unsubstituted.

Claim 5

A process for alkylating a mono- or di-t-alkylated phenolic compound having from about ten to about twenty four which has two hydrogens in the ortho, para, ortho-ortho or ortho-para positions comprising: (a) reacting the t-alkylated phenolic compound with a saturated aliphatic aldehyde having one to four carbon atoms and a secondary non-aromatic amine having two to about eight carbon atoms, wherein the amount of the t-alkylated phenolic compound is a stoichiometric amount and the amounts of the aldehyde and amine are at least stoichiometric amounts, and at a temperature in the range of about 0° C. to about 100° C. to produce a Mannich base type aminoalkylated t-alkylated phenolic compound; (b) contacting the Mannich base type aminoalkylated t-alkylated phenolic compound formed in step (a) with hydrogen in the presence of a hydrogenation catalyst to produce an alkylated t-alkylated phenolic compound; and (c) contacting the alkylated t-alkylated phenolic compound formed in step (b) with an acid or an acid reacting substance at a temperature from about 25° C. to about 300° C. to produce a phenolic compound which is selected from the group consisting of monoalkylated phenolic compounds alkylated in the ortho- or para-positions and dialkylated phenolic compounds alkylated in the ortho-ortho, ortho or ortho-para positions and having at least one ortho- or para-position unsubstituted.

Claim 6

A process for alkylating a mono- or di-t-alkylated phenolic compound having from about ten to about twenty four which has two hydrogens in the ortho, para, ortho-ortho or ortho-para positions comprising: (a) reacting the t-alkylated phenolic compound with a saturated aliphatic aldehyde having one to four carbon atoms and a secondary non-aromatic amine having two to about eight carbon atoms, wherein the amount of the t-alkylated phenolic compound is a stoichiometric amount and the amounts of the aldehyde and amine are at least stoichiometric amounts, and at a temperature in the range of about 0° C. to about 100° C. to produce a Mannich base type aminoalkylated t-alkylated phenolic compound; (b) contacting the Mannich base type aminoalkylated t-alkylated phenolic compound formed in step (a) with hydrogen in the presence of a hydrogenation catalyst to produce an alkylated t-alkylated phenolic compound; and (c) contacting the alkylated t-alkylated phenolic compound formed in step (b) with an acid or an acid reacting substance at a temperature from about 25° C. to about 300° C. to produce a phenolic compound which is selected from the group consisting of monoalkylated phenolic compounds alkylated in the ortho- or para-positions and dialkylated phenolic compounds alkylated in the ortho-ortho, ortho or ortho-para positions and having at least one ortho- or para-position unsubstituted.

Claim 7

A process for alkylating a mono- or di-t-alkylated phenolic compound having from about ten to about twenty four carbon atoms and which has two hydrogens in the ortho, para, ortho-ortho or ortho-para positions comprising: (a) reacting the t-alkylated compound with a saturated aliphatic aldehyde having one to four carbon atoms and a secondary non-aromatic amine having two or about eight carbon atoms, wherein the amount of the t-alkylated phenolic compound is a stoichiometric amount and the amounts of the aldehyde and amine are at least stoichiometric amounts, and at a temperature in the range of about 0° C. to about 100° C. to produce a Mannich base type aminoalkylated t-alkylated phenolic compound; (b) contacting the aminoalkylated t-alkylated phenolic compound formed in step (a) with an acid or an acid reacting substance at a temperature from about 25° C. to about 300° C. to produce an aminoalkylated phenolic compound which is selected from the group consisting of aminoalkylated phenolic compounds, aminoalkylated in the ortho- or para-positions and diaminoalkylated phenolic compounds aminoalkylated in the ortho-ortho, ortho or ortho-para positions and having at least one ortho- or para-position unsubstituted; and (c) contacting the Mannich base type aminoalkylated phenol compound formed in step (b) with hydrogen in the presence of a hydrogenation catalyst to produce an alkylated phenolic compound having at least one ortho- or para-position unsubstituted.

Claim 8

A process for alkylating a mono- or di-t-alkylated phenolic compound having from about ten to about twenty four carbon atoms and which has two hydrogens in the ortho, para, ortho-ortho or ortho-para positions comprising: (a) reacting the t-alkylated compound with a saturated aliphatic aldehyde having one to four carbon atoms and a secondary non-aromatic amine having two or about eight carbon atoms, wherein the amount of the t-alkylated phenolic compound is a stoichiometric amount and the amounts of the aldehyde and amine are at least stoichiometric amounts, and at a temperature in the range of about 0° C. to about 100° C. to produce a Mannich base type aminoalkylated t-alkylated phenolic compound; (b) contacting the aminoalkylated t-alkylated phenolic compound formed in step (a) with an acid or an acid reacting substance at a temperature from about 25° C. to about 300° C. to produce an aminoalkylated phenolic compound which is selected from the group consisting of aminoalkylated phenolic compounds, aminoalkylated in the ortho- or para-positions and diaminoalkylated phenolic compounds aminoalkylated in the ortho-ortho, ortho or ortho-para positions and having at least one ortho- or para-position unsubstituted; and (c) contacting the Mannich base type aminoalkylated phenol compound formed in step (b) with hydrogen in the presence of a hydrogenation catalyst to produce an alkylated phenolic compound having at least one ortho- or para-position unsubstituted.

Claim 9

The process according to claim 3 wherein the Mannich base type aminoalkylated phenolic compound is contacted with hydrogen in a glass-lined vessel.

Claim 10

The process according to claim 5 wherein the Mannich base type aminoalkylated phenolic compound is contacted with hydrogen in the presence of a noble metal catalyst selected from a group consisting of palladium, platinum, rubidium, rhodium, indium and mixtures thereof.

Claim 11

The process according to claim 6 wherein the Mannich base type aminoalkylated phenolic compound is contacted with hydrogen at a pressure less than 500 psig and at a temperature in the range of about 100° C. to about 140° C.

Claim 12

The process according to claim 3 wherein the separated secondary amine is recycled to be reacted with the t-alkylated phenolic compound and aldehyde.

Claim 13

The process according to claim 6 wherein the noble metal catalysts are supported on materials selected from the group consisting of porous or non-porous carbon blacks, or silica.

Claim 14

The process according to claim 3 wherein the catalyst is filtered from the reaction product and recycled to the hydrogenolysis reaction.

Claim 15

The process according to claim 3 wherein the amine is added to the t-alkylated phenolic compound before the aldehyde is added.

Claim 16

The process according to claim 3 wherein the reacting of the t-alkylated phenolic compound with the amine and the aldehyde is performed in methanol.

Claim 17

The process according to claim 3 wherein the catalyst used for the hydrogenation is a palladium on carbon catalyst.

Claim 18

The process according to claim 3 wherein the t-alkylated phenolic compound is a t-butylated phenolic compound.

Claim 19

The process according to claim 3 wherein the aldehyde used is formaldehyde.

Claim 20

The process according to claim 14 wherein the formaldehyde used is a 37 percent aqueous formaldehyde solution.

Claim 21

The process according to claim 14 wherein the formaldehyde used is paraformaldehyde.

Claim 22

The process according to claim 3 wherein the secondary nonaromatic amine is selected from a group consisting of dimethylamine, diethylamine, diisopropylamine and piperidine.

Claim 23

The process according to claim 3 wherein the t-alkylated phenolic compound is 4-t-butyl-m-cresol and the aldehyde is formaldehyde and the final product is 2,3,6-trimethylphenol.

Claim 24

The process according to claim 3 wherein the t-alkylated phenolic compound is 6-t-butyl-m-cresol, the aldehyde is formaldehyde and the final phenolic compound is 2,3,4-trimethylphenol.

Claim 25

The process according to claim 3 wherein the t-alkylated phenolic compound is 4-t-butyl-2,5-xylenol, the aldehyde is formaldehyde and the final phenolic product is 2,3,6-trimethylphenol.

Claim 26

The process according to claim 3 wherein the t-alkylated phenolic compound is 6-t-butyl-2,3-xylenol, the aldehyde is formaldehyde and the final phenolic compound is 2,3,4-trimethylphenol.

Claim 27

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 water-immiscible solvent.

Claim 28

The process according to claim 3 wherein the secondary amine is selected from the group consisting of dimethylamine or diethylamine.

Claim 29

The process according to claim 1 wherein step (a) is carried out by t-alkylation.

Claim 30

The process according to claim 1 wherein step (a) is carried out by trans alkylation.

Claim 31

The process according to claim 1 wherein step (a) is carried out by partial de-t-alkylation.