Method for preparing tris(ether-amine)

Details Method for preparing tris(ether-amine) Method for preparing tris(ether-amine)

2001-07-23

2002-06-11

Davis, Brian J. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C564S401000, C564S402000, C564S445000, C564S447000, C564S474000, C564S475000, C564S478000

Reexamination Certificate

active

06403834

ABSTRACT:

The present invention relates to an improved process for preparing tertiary amines which can be used as sequestering agents for solubilising organic or inorganic metal salts in organic solvents. These tertiary amines may also be used as emulsifiers.
The tertiary amines prepared by the process according to the invention have the general formula (I):
N[A—O—(B—O)
n
—R]
3
  (I)
wherein:
R denotes an alkyl radical having 1 to 24 carbon atoms, optionally substituted by one or more C
1-12
-alkoxy radicals; a saturated carbocyclic, monocyclic or polycyclic radical having 3 to 10 carbon atoms, optionally substituted by one or more C
1-12
-alkoxy radicals; an alkyl radical having 1 to 12 carbon atoms and carrying a saturated carbocyclic, monocyclic or polycyclic group having 3 to 10 carbon atoms, the alkyl part optionally being substituted by one or more C
1-12
-alkoxy radicals and the saturated carbocyclic group optionally being substituted by one or more C
1-12
-alkyl groups or C
1-12
-alkoxy groups; an aromatic carbocyclic, monocyclic or polycyclic radical having 6 to 22 carbon atoms and optionally substituted by one or more C
1-12
-alkoxy or C
1-12
-alkyl groups; and an alkyl radical having 1 to 12 carbon atoms and carrying an aromatic carbocyclic, monocyclic or polycyclic group having 6 to 18 carbon atoms, the alkyl part optionally being substituted by one or more C
1-12
-alkoxy groups and the aromatic group optionally being substituted by one or more C
1-12
-alkyl groups or C
1-12
-alkoxy groups; p A and B, which may be identical or different, independently denote a straight alkylene chain having 1 to 24 carbon atoms optionally substituted by one or more groups selected from among C
1-12
-alkyl and C
1-12
-alkoxy; and
n denotes from 0 to 12.
The value of amines of this kind is the subject matter of French Patent Application 79 05438.
Numerous preparation processes have been described in the art for preparing tertiary amines of this kind. Reference may be made, for example, to EP161459, EP5094, EP18884 and the work by Pétrov which appeared in Zh. Obsch. Khim (1970), 40(7), 1611-1616.
However, the methods described have two serious drawbacks: the yields are low and the products are difficult to purify.
From the point of view of the yields obtained, the method of synthesis described in EP18884 is particularly advantageous. It consists in using ammonolysis, in liquid phase, of an alkyleneglycol monoether of formula F1:
HO—A—O—(B—O)
n
—R   F1
wherein:
R denotes (C
1-24
)alkyl, cyclohexyl, phenyl or (C
1-12
)alkylphenyl;
A and B, which may be identical or different, independently represent a straight alkylene chain (C
2-3
) in which the carbon atoms are optionally substituted by methyl or ethyl; and
n denotes an in between 0 and 4;
in the presence of a hydrogenation/dehydrogenation catalyst at between 100 and 250° C., the ammonolysis operation being carried out by contacting the ammonolysis agent or agents with a mixture consisting of the above-mentioned alkyleneglycol monoether and the catalyst.
According to this publication, the ammonolysis agents are selected from ammonia and the ether-amines of formula F2:
H
3-p
N[A—O(B—O)
n
—R]
p
  F2
wherein:
R denotes (C
1-24
)alkyl, cyclohexyl, phenyl or (C
1-12
)alkylphenyl;
A and B, which may be identical or different, independently denote a straight (C
2-3
)alkylene chain wherein the carbon atoms are optionally substituted by methyl or ethyl; and
n denotes an integer between 0 and 4; and
p is an integer equal to 1 to 2.
In spite of the low cost of the raw materials, this process is not economical. At the end of the reaction, the reaction medium is separated from the catalyst by filtration. In fact, the operation of filtration is not easy and requires special filtration equipment which is expensive both to buy and maintain, as the hydrogenation/dehydrogenation catalyst is pyrophoric and abrasive.
Furthermore, the elimination of the catalyst is a laborious task which is frequently incomplete. Thus, there is a substantial reduction in the yield in as much as traces of catalyst in the crude tertiary amine cause it to decompose during subsequent steps of purification by distillation.
Finally, the method according to the prior art is not well suited to industrialisation of the process as it would require the use of excessive quantities of catalyst, which is particularly expensive.
The process according to the invention sets out to overcome the disadvantages of the prior art process.
More precisely, the invention relates to a process for preparing tris(ether-amines) of formula (I) as defined hereinbefore comprising reacting, in liquid phase, an alkyleneglycol monoether of formula (II):
HO—A—O—(B—O)
n
—R   (II)
wherein:
R denotes an alkyl radical having 1 to 24 carbon atoms, optionally substituted by one or more C
1-12
-alkoxy radicals; a saturated carbocyclic, monocyclic or polycyclic radical having 3 to 10 carbon atoms, optionally substituted by one or more C
1-12
-alkoxy radicals; an alkyl radical having 1 to 12 carbon atoms and carrying a saturated carbocyclic, monocyclic or polycyclic group having 3 to 10 carbon atoms, the alkyl part optionally being substituted by one or more C
1-12
-alkoxy radicals and the saturated carbocyclic group optionally being substituted by one or more C
1-12
-alkyl groups or C
1-12
-alkoxy groups; an aromatic carbocyclic, monocyclic or polycyclic radical having 6 to 22 carbon atoms and optionally substituted by one or more C
1-12
-alkoxy or C
1-12
-alkyl groups; and an alkyl radical having 1 to 12 carbon atoms and carrying an aromatic carbocyclic, monocyclic or polycyclic group having 6 to 18 carbon atoms, the alkyl part optionally being substituted by one or more C
1-12
-alkoxy groups and the aromatic group optionally being substituted by one or more C
1-12
-alkyl groups or C
1-12
-alkoxy groups;
A and B, which may be identical or different, independently denote a straight alkylene chain having 1 to 24 carbon atoms optionally substituted by one or more groups selected from among C
1-12
-alkyl and C
1-12
-alkoxy; and
n denotes from 0 to 12;
with an ammonolysis agent selected from among ammonia and an ether-amine of formula (I′):
H
3-p
N[A—O—(B—O)
n
—R]
p
  (I′)
wherein A, B, n and R are as hereinbefore defined for formula (I) and p denotes 1 or 2, at a temperature between 100 and 250° C. by contacting the reagents with a hydrogenation/dehydrogenation catalyst.
According to the invention, the term saturated carbocyclic, monocyclic or polycyclic radical denotes a radical made up of one or more cycloalkyl nuclei. When said saturated carbocyclic radical comprises a plurality of cycloalkyl nuclei, the latter form condensed or bridged structures, indicating that each cycloalkyl nucleus has at least two carbon atoms in common with at least one other cycloalkyl nucleus.
Examples of condensed structures include, in particular, perhydronaphthylene and perhydroindane.
Similarly, an example of a bridge structure is norbornane.
However, saturated monocyclic carbocyclic radicals of the (C
3-8
)cycloalkyl type are preferred, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Within the scope of the invention the alkyl radicals are straight-chained or branched. The preferred alkyl radicals are the C
1-10
-alkyl radicals, better still (C
1-6
)alkyl, and especially methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl.
The aromatic carbocyclic radicals are monocyclic or polycyclic.
The polycyclic aromatic carbocyclic radicals have condensed aromatic nuclei.
Of these, the preferred ones are the mono- and bicyclic aromatic carbocyclic radicals having 6 to 10 carbon atoms, such as phenyl or napthyl.
Special examples of alkyl radicals carrying an aromatic carbocyclic radical are the (C
6-10
)aryl-(C
1-12
)alkyl groups and more particularly the (C
6-10
)aryl-(C
1-6
)alkyl groups such as benzyl or naphthylmethyl.
Within the scope of the invention, the preferred definitions

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