PROCESS FOR PREPARING TERTIARY AMINES

PREPARATION D'AMINES TERTIAIRES

English Abstract

Abstract of the disclosure:
Process for preparing tertiary amines of the
formula
< IMG >
in which R1 denotes C8-C26-alkyl or C9-C18-alkylaryl,
R2 denotes C1-C22-alkyl, and n is a number from 1 to 15,
by reacting 2 moles of a compound of the formula
R1-(OCH2CH2)n-X
in which X denotes halogen or -OSO3Na or -OSO3K, and
R1 and n are as defined above, with 1 to 1.4 moles of a
compound of the formula
R2-NH2
where R2 denotes a C1-C22-alkyl radical,
at temperatures of 100 to 200°C, preferably 160 to 185°C,
in a solvent or solvent mixture, preferably in water, in
the presence of an at least equimolar amount of a strong
base.

Claims

- 7 -
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing a tertiary amine of the
formula
< IMG >
in which R1 denotes C8-C26-alkyl or C9-C18-alkylaryl, R2 denotes
C1-C22-alkyl, and n is a number from 1 to 15, which comprises
reacting 2 moles of a compound of the formula
R1-(OCH2CH2)n-X
in which X denotes halogen or -OSO3Na or -OSO3K, and R1 and n
are as defined above, with 1 to 1.4 moles of a compound of the
formula
R2-NH2
where R2 denotes a C1-C22 alkyl radical,
at a temperature of 100 to 200°C in a solvent or solvent mixture
in the presence o-f an at least equimolar amount of a strong base.
2. The process of claim 1 wherein the compounds are
reacted at a temperature of 160 to 185°C.

- 8 -
3. The process of claim 1 wherein the solvent is water.

Description

~L~225~
-- 2 --
HOE 83/F 223
The invention relates to the preparation of
tertiary amine of the general formula
Rescission 2
( OUCH on
on which R1 denotes C8-C26-alkyl or C9-C1~-alkylaryl,
R2 denotes C1-C22-alkyl, and n is 1 - 15.
Compounds of this type can be prepared from the
corresponding alcohols aldehydes or kittens and primary
alkylamines by aminolysis (DE 3,034~433). These come
pounds can also be synthesized by alkylating secondary
ether-amines which are Likewise accessible by aminolysis
(Use U.S. 3~373~204~ Use 2~928~877)~ However,
the reactions in these methods of synthesis do not proceed
uniformly. They produce mixtures of primary, secondary and
tertiary amine which are very difficult to separate even if
15 the R1 and R2 radicals and n are very small. In add-
ton, cleavage reactions produce a nearer of undesirable
byproducts such as low-boiling ammonias which are an coo-
logical hazard. For this reason, this process has little
industrial feasibility, if any in -the case of compourlds with
20 relatively big R1 and R2 radicals, and in most cases is
likely to be uneconomical
It is also known to react oc~adecyl~mine wit

(ox
-- 3 -- -
2 moles of 2 methyl -chloroethyl ether JOY 71 01 587).
However this reaction works with an only weakly basic
alkali compound (~2C03) and takes 30 to 50 hours.
It has now been found that the desired tertiary
amine can be prepared in a controlled manner and in high
yields by alkylating primary alkylam;nes at relatively
high temperatures and on the presence of strong bases.
The invention accordingly provides a process for
preparing tertiary amine of the formula
Rl~(OCH2CH2)n 2
N-R
-occasion
on which R1 denotes C~-~C26~alkyl or Cg-C18-alkylaryl,
I denotes C1 Colloquial and no it a number from 1 to 15,
which comprises reacting 2 moles of a compound of the
formula
Rescission
in which X denotes halogen, preferably chlorine, or
-Ozone or -OS03K, and R1 and n are as defined above
with 1 to I moles of a compound of the formula
RUN Ho
jury R2 denotes a C1-Cz2-alkyl radical,
at temperatures of 100 to 200Cf preferably 1~0 to 185C,
in a solvent or solvent mixture in the presence of an at
least equimolar amount of a strong base.
The reaction is preferably carried out with water
as the solvent. The strong base is preferably potassium

I
- 4
hydroxide or sodium hydroxide These bases are used in
at least equimolar amounts, based on the compound to be
alkylated. The base is preferably used in an excess of
10 to 30%. The reaction generally takes 3 to ED hours.
The end product can be isolated from the aqueous solution
or emulsion without problems at temperatures above their
cloud points, possibly by adding salts. The tertiary
amine obtained according to the invention serve as start-
in compounds for preparing the corresponding qua ternary
ammonium compounds.
The surprising feature about the process according
to the invention us that the starting halide or sulfate
is hydrolyzed to a much smaller extent in the strongly
alkaline solution and at the high reaction temperatures
than might have been expected in particular since the
reactive centers in the starting compounds are made
soluble in water by the oxyethylene units and hence are
easily accessible to the hydroxyl ions. A further
surprising feature of thus process is the selectivity of
the reaction: it leads directly to the tertiary amine in
yields of above 85%. Although no excess of halide or sulk
fate is used, the end product unexpectedly contains very
little, of any, of the corresponding secondary amine
formed as an intermediate. The following examples are
intended to demonstrate the possibilities of the process
according to the invention.
Example 1
-
~is~cocoalkyl~ x ) ~ylamine
460 9 ~1.0 mole) of cocoalky~pentaoxyethyl

- 5 -
chloride, 38.8 g (0.5 mole) of 40X strength methyl amine
solution, 48 g (1.2 moles) of Noah and 450 ml of deionized
water are introduced into a 2 liter pressure autoclave
and the mixture is stirred at 175C for 10 hours. Thy
organic layer is separated off and the water which has
remained therein is removed by distillation under reduced
pressure. The result is 420 g t95.7X of theory of
tertiary amine
Tertiary nitrogen: found 1.5% calculated 1.6%
Example 2
Bis(isotridecylpentaoxyeth~)octylamine
140 g (0.32 mole) of îsotridecylpentaoxyethyl
chloride, 20.6 9 (0.10 mole) of n-octylamine~ 15.4 g
(0.38 mole) of Allah and 600 ml of deionized water are
introduced into a pressure autoclave, and the mixture is
stirred at 175C for 10 hours. The reaction mixture is
worked up as in Example 1.
yield: 133 9 (88% of theory)
Tertiary nitrogen: found 1.4 calculated 105
i3is~no~_phenylhexaoxyethyl)methylamine
_ _ _
482 g (1.û mole) of nonylphenylhexaoxye~hyl
chloride, 40 g (0.52 mole) of methyl amine solution (40%)~
48 9 of Noah and 500 ml of isopropanol are stirred at
175C in an autoclave for 10 hours. The salt is filtered
off with suction, and the solvent is distilled of, in
vacua.
Yield: 437 g ~94.8X of theory)
Tertiary nitrogen: found 1~4 calculates US

1~5~
C
I,
E ample 4
is me
12/14
750 9 moles) of sodium C12/14 alkyltrioxy
ethyl sulfate t70%), 45~7 9 (0.5~ mole) of mailmen
solution t40X~, 48 9 (1.2 moles of Noah and DO ml of
deionized water are reacted and blocked up as described in
Example 1. Yield 366 g (9't.1X of theory.
Tertiary nitrogen: found 1.95 calculated 2.1
Example 5
10 BiStc2o/22~yethyl)methylam;ne
390 9 t1.0 mole) of C20/22alkyldioxyethyl color-
ode, 46.5 9 Tao mole) of methyl amine solution ~40%), 48 9
(1.2 moles) of Noah and boo ml of deionized water are
reacted and worked up as described in Example 1, except
that in this case the reaction takes 5 hours,
Yield: 342 9 (92.7% of theory
Tertiary nitrogen: found 1.6 calculated 1~75