Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2002-06-28
2002-11-26
Barts, Samuel (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S354000
Reexamination Certificate
active
06486352
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for the preparation of polyalkylphenoxyaminoalkanes. More particularly, this invention relates to a process for the preparation of polyalkylphenoxyaminoalkanes which comprises the aminoethylation of a polyalkylphenol compound with &bgr;-amino alcohol and dialkyl carbonate.
BACKGROUND OF THE INVENTION
Polyalkylphenoxyaminoalkanes are known fuel additives useful in the prevention and control of engine deposits. U.S. Pat. Nos. 5,669,939 and 5,851,242 describe a process for preparing these compounds. The process involves initially hydroxylating a polyalkylphenol with an alkylene carbonate in the presence of a catalytic amount of an alkali metal hydride or hydroxide, or alkali metal salt, to provide a polyalkylphenoxyalkanol which is subsequently reacted with an appropriate amine to provide the desired polyalkylphenoxyaminoalkane.
2-oxazolidinones or derivatives thereof are well described in the art. For example, Martin E. Dyen and Daniel Swern,
Chemistry Reviews
(1967), pages 197-246 describes 2-oxazolidinones in detail. The use of 2-oxazolidinones or derivatives thereof in the aminoethylation of phenols is well known in the art. This same reference also describes the preparation of both carbamate derivatives and 2-oxazolidinones using various &bgr;-amino alcohols and dialkyl carbonates.
U.S. Pat. No. 4,381,401 discloses the reaction of 2-oxazolidinone or N-substituted derivatives thereof with aromatic amine hydrochlorides at elevated temperatures to produce 1,2-ethanediamines. The 1,2-ethandiamines produced are an important class of materials which are useful as intermediates for the production of pharmaceuticals, photographic chemicals and other compositions.
Japanese Patent Publication No. JP 2592732 B2 discloses a method of producing phenoxyethylamines by reacting, under base conditions, low molecular weight phenols and 2-oxazolidinone. Phenoxyethylamines are important raw materials for pharmaceuticals and pesticides.
German Patent Publication DE 19711004 A1 discloses the use of 2-oxazolidinone to prepare phenoxyaminoalkanes from low molecular weight phenols. 2-4-(Phenoxyphenoxy)ethylamine and ethyl 2-(phenoxyphenoxy)ethylcarbamate are sequentially prepared in high yield and selectivity by the aminoethylation of 4-phenoxyphenol with 2-oxazolidinone under inert atomsphere, followed by amidation of 2-4-(phenoxyphenoxy)ethylamine with carbonate derivatives.
U.S. Pat. No. 6,384,280 teaches the use of 2-oxazolidinone or a derivative thereof in aminoethylation transformations involving high molecular weight polyalkylphenols to provide polyalkylphenoxyaminoalkanes of the type disclosed in U.S. Pat. Nos. 5,669,939 and 5,851,242. There has heretofore not been any teaching wherein the combination of &bgr;-amino alcohol and dialkyl carbonate or a derivative thereof has been used in aminoethylation transformations involving high molecular weight polyalkylphenols.
SUMMARY OF THE INVENTION
The present invention provides a novel process for the preparation of polyalkylphenoxyaminoalkanes which comprises the aminoethylation of a polyalkylphenol compound in the presence of a basic catalyst with a &bgr;-amino alcohol or derivative thereof having the following formula:
R
1
NH—CHR
2
—CH
2
—OH
wherein R
1
and R
2
are independently hydrogen, lower alkyl having 1 to about 6 carbon atoms, hydroxyalkylene, phenyl, alkaryl or aralkyl;
and a dialkyl carbonate having the following formula:
(R
3
O)
2
CO
wherein R
3
is lower alkyl having 1 to about 6 carbon atoms and wherein the polyalkyl group of said polyalkylphenol has an average molecular weight in the range of about 600 to 5,000.
Optionally, the aminoethylation reaction may be carried out with an alcohol co-solvent.
The aminoethylation reaction of the present invention readily occurs using a basic catalyst selected from the group consisting of alkali metal lower alkoxides, alkali hydrides or alkali metal hydroxides in the temperature range of about 100° C. to 250° C., wherein the molar ratio of &bgr;-amino alcohol and dialkyl carbonate to polyalkylphenol compound is about 0.9-5:0.9-5:1, wherein the molar ratio of the optional alcohol co-solvent to polyalkylphenol compound, when it is used, is about 0.2:1 to 5:1 and wherein the number of equivalents of basic catalyst per equivalent of polyalkylphenol is about 0.05:1 to 1:1.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
Prior to discussing the present invention in detail, the following terms will have the following meanings unless expressly stated to the contrary.
The term “alkyl” refers to both straight- and branched-chain alkyl groups.
The term “alkaryl” refers to the group:
wherein R
a
and R
b
are each independently hydrogen or an alkyl group, provided at least one of R
a
and R
b
is alkyl. Typical alkaryl groups include, for example, tolyl, xylyl, cumenyl, ethylphenyl, butylphenyl, dibutylphenyl, hexylphenyl, octylphenyl, dioctylphenyl, nonylphenyl, decylphenyl, didecylphenyl, dodecylphenyl, hexadecylphenyl, octodecylphenyl, icosphenyl, tricontylphenyl, and the like.
The term “alkylphenyl” refers to an alkaryl group of the above formula in which R
a
is alkyl and R
b
is hydrogen.
The term “aralkyl” refers to the group:
Wherein R
c
and R
d
are each independently hydrogen or a lower alkyl group, and R
e
is an alkylene group. Typical aralkyl groups include, for example, benzyl, methylbenzyl, ethylbenzyl, propylbenzyl, dimethylbenzyl, phenethyl, and the like.
The term “hydroxyalkylene” refers to the group:
HO—R
f
wherein R
f
is a lower alkylene group as defined below.
The term “lower alkyl” refers to alkyl groups having 1 to about 6 carbon atoms and includes primary, secondary and tertiary alkyl groups. Typical lower alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cycloalkyl such as cyclopentyl, cyclohexyl and the like.
The term “lower alkylene” refers to an alkylene group having 1 to about 6 carbon atoms, such as methylene, ethylene, propylene, butylene, pentylene, and hexylene.
The term “polyalkyl” refers to an alkyl group which is generally derived from polyolefins which are polymers or copolymers of mono-olefins, particularly 1-mono-olefins, such as ethylene, propylene, butylene, and the like. Preferably, the mono-olefin employed will have about 2 to 24 carbon atoms, and more preferably, about 3 to 12 carbon atoms. More preferred mono-olefins include propylene, butylene, particularly isobutylene, 1-octene and 1-decene. Polyolefins prepared from such mono-olefins include polypropylene, polybutene, especially polyisobutene, and the polyalphaolefins produced from 1-octene and 1-decene.
As noted above, the present invention provides a novel process for the preparation of polyalkylphenoxyaminoalkanes which comprises an aminoethylation of a polyalkylphenol compound in the presence of a basic catalyst with &bgr;-amino alcohol or derivative thereof having the following structure:
R
1
NH—CHR
2
—CH
2
—OH
wherein R
1
and R
2
are independently hydrogen, lower alkyl having 1 to about 6 carbon atoms, hydroxylalkylene, phenyl, alkaryl, or aralkyl;
and a dialkyl carbonate having the following formula:
(R
3
O)
2
CO
wherein R
3
is lower alkyl having 1 to about 6 carbon atoms; and wherein the polyalkyl group of said polyalkylphenol has an average molecular weight in the range of about 600 to 5,000.
Optionally, the aminoethylation reaction may be carried out with an alcohol co-solvent. The optional alcohol co-solvent has the structure R
4
—OH wherein R
4
is an alkyl group having about 4 to 13 carbon atoms.
The reaction may be illustrated by the following:
wherein R is a polyalkyl group having a molecular weight in the range of about 600 to 5,000, and R
1
, R
2
and R
3
are as herein described.
Polyalkylphenoxyaminoalkanes may be prepared by the process of the present invention which comprises an aminoethylation of a polyalkylphenol compound with &bgr;-amino alcohol or derivative thereof having the following formula:
R
1
NH—CHR
2
—CH
2
—OH
and a di
Chevron Oronite Company LLC
Lee Steven G. K.
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