Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
i ~1 63~7~
Subject of the invention are quaternary alkylamino-di-
alkylcarboxylic acid di-esters of the formula 1
13
1\ ~ ~(CH2)m-co-(o-cH2-cH) -O-R5 xe (1)
R2 (CH2)n-CO-(O-CH2-CH)p-O-R6
R4
wherein Rl and R2 are alkyl or hydroxyalkyl wlth from 1 to 4 C-atoms
or benzyl, R3 and R4 are hydrogen or methyl, R5 and R6 are alkyl or
alkenyl w.ith from 8 to 24 C-atoms, m and n are numbers from 1 to 4,
o and p are numbers from 0 to 10 and X is a halogen, methosulfate,
ethosulfate or alkylphosphate anion.
Preferred compounds of formula 1 are those, wherein Rl
and R2 are alkyl or hydroxyalkyl with 1 or 2 C-atoms, R3 and R4 are
hydrogen/ R5 and R6 are alkyl or alkenyl with from 16 to 22 C-atoms,
X is Cle, Bre or CH3SO4e, m and n are 1 or 2 and o and p are
numbers from 0 to 5.
Especially preferred are those compounds of formula 1,
wherein Rl and R2 are methyl, R3 and R4 are hydrogen, R5 and R6
are C16-C22-alkyl, X is Cl , m and n are 1 and p and o are numbers
from 0 to 2.
These compounds are manufactured by first reacting a
compound of the formula 2
Rl\
R ~ ~2)
with a compound of the formula 3
X~(cH2)m-co-(o-cH2-cH)o~O~R5 (3)
R3
f~.
~ ~ 6 3 .~
- 3 - HOE 79/F 168
wherein X ~eans halogen. Thereby a compound of the formula
R1\
N-(CH2) -CO-(oCH2C~H)o 5
R2 3
is obtained, which subsequently is reacted further with a
compound of the formula ~
X-(CH2)n-CO-lOcH2lcH)p OR6
The a~ine of the formula 2 could initially be reac-
ted also with the halogenocarboxylic acid ester of the
formula 4 and afterwards with the halogenocarboxylic acid
ester of the formula 3. If the symbols m and n, o and p t
R3 and R4 and R5 and R6 are identical, the compounds of
the formulae 3 and 4 are also identical and the amine 2
will at first be reacted with half of the necessary amount
of halogenocarboxylic acid ester and subsequently in the
second stage with the other half.
In the first stage this reaction is carried out in an
inert solvent, such as benzene, toluene, xylene or a paraf-
fin hydrocarbon or their mixtures, at temperatures of about
-20C to about 100C. The reaction vessel is first charged
with the dialkylamine of the formula 2 in the solvent and
intensively cooled. Subsequently, the halogenocarboxylic
acid ester of the formula 3 is added and the temperature
is slowly increased, whereby a possible excess of unreacted
dialkylamine escapes For taking up the literated hydro-
gen hallde an appropriate excess of the dialkylamine is used
and the resulting ammonium salt is separated by filtration.
From this salt the dialkylamine can be regenerated and used
a~ain. After distillation of the inert solvent the diaikyl-
aminoalkane carbo~ylic acid ester is obtained with a puri-
ty of more than 95 %. In the case of the dimethylaminoacetic
acid esterr.the product can also be purified by high vacuum
aistillation .
The dialkylaminoalkane carboxylic acid esters are sub-
sequently dissolved in an alcohol or preferably dispersed in
3~75
- 4 - HOE 79/F 168
water and reacted again with a halogenoalkane carboxylic
acid ester of the formula 3 or 4, at temperatures below
100C, preferably at temperatures from 40 - 80C. The
reaction, however, can also be performed without any sol-
vent. ~fter distillation of water or the solvent, the purecompounds of the formula 1 are obtained. According to a
preferred embodiment the reaction is carried out in an
aqueous dispersion, whereby about 20 % of aqueous disper-
sion of the compounds 1 are obtained which, after further
dilution with water, can directly be used as fabric softe-
ners.
Another possibility for manufacturing the compounds
of formula 1 consists in first reacting 1 mol of a mono-
alkylamine of the formula 5
R1 ~ NH2 (5)
with 2 mols of a halogenoalkane carboxylic acid ester of
the formula 3 or 4 and quaternizing the reaction product
with a compound of the formula
R2_Y or (R20)2S02
~ in which Y means halogen. The reaction of the monoalkylamine
with the halogenoalkane carboxylic esters is carried out
under the same conditions as in the first stage of the
above described process. For neutralizing the resulting
hydrogen halide in this case a second amine is used, such
as triethylamine or pyridine, and the resulting amine
salt is separated by filtration, too. This reaction can
also be carried out with a mixture of two different halo-
genoalkane carboxylic acid esters of the formulae 3 and 4
or with 2 mols of only one of these compounds. The sub-
sequent quaternization is carried out as above described
35 at about 40 - 100~C in an alcohol, but preferably in wa-
ter with an alkyl halide or with a dlalkyl sulfate, which
serves to introduc2 the radical R2 when the mDnoalkylam~e
5 already contains the radical R1. Vice versa, a monoalkyl-
amine 5 which already contains the radical R2 can, of course,
i ~ 6327~
- 5 - ~lo~ 79/~ 168
be used as staxtiny material ancl during the final quaterni-
zation the radical R1 is then introduced. The quaterniza-
tion can also be carried out wit:hout any solvent.
The~-halogenoalkane carboxylic acid esters of the
formulae 3 and 4 used as starting materials, can be oh~
tained by known methods by reacting an acid of the for-
mula
X-(CH2)m-COOH or X-(CH2)n-cOOH
or the corresponding acid chloride with an oxalkylated
alcohol of the formula
H(OCH2CH)o-OR5 or H(ocH2cH)p-oR6
R R
Suitable alcohols are branched or unbranched, satura-
ted or unsaturated alcohols with from 8 to 24 C-atoms,
for example dodecyl, myristyl, cetyl, oleyl or preferably
stearyl and behenyl alcohol or mixtures of those alcohols.
Because of economic reasons, mixtures of alcohols, ob-tained
from natural fats on the basis of coco nut oil or tallow
or in the form of distillation fractions of synthetic
alcohols (Ziegler- or oxoalcohols) are preferred. Before
the reaction with the halogeno carboxylic acid derivative,
the alcohol is oxalkylated in known manner with propylene
oxide or preferably with ethylene oxide.
The compounds of formula 1 according to the inven-
tion can be used as fabric softeners and are added, after
washing the textile material, into the last cleansing
bath in the form of aqueous dispersions with a content of
active substance from 1 to 15 % by weight, preferahly 4
to 10 ~ by weight of the compounds of formula 1. Subse-
quently, the textile material is dried. These fabric sof-
teners can also contain`othe~ substances and auxiliariesas generally used in fabric softeners. Such su~stances are,
for example, cationic or non-lonic surface-active substances~
electrolytes, neutralizing agents, organic complexing agents,
63275
- 6 - HOE 79/F 168
optical brighteners or dissolving intermediaries, as well
as dyestuffs and perfumes. The products are used for an
additional influencing of the fabric feel or of other pro-
perties of the treated textiles or for adjusting the vis-
cosity, the pH regulation or for improving the stability
at low temperatures of the solutions.
The compounds according to the invention provide
an agreable and smooth feel to any textile materials,
especially those of natural or regenerated cellulose, wool,
cellulose acetate, triacetate, polyamide, polyacrylo-
nitrile, polyester, polypropylene. Of special advantage
is the use as aftertreatment agent for friction cloth and
lingerie.
The advantage of these compounds consists in that
they are obtained in the form of aqueous dispersions,
which, after further dilution, can directly be used, whilst
the dialkyldimethylammonium salts, commonly used in practice
for this purpose, in the preferred commercial form of a
concentrated solution contain a combustible alcohol. There-
fore, because of the low point of ignition these products
fall within the regulations for dangerous working materials
for transportation, storage and processing. Such a limita-
tion does not exist for the compounds of the present inven-
~ tion.
The following examples illustrate the invention:
Example 1:
410 parts by weight of a chloroacetic acid ester,
manufactured from chloroacetyl chloride and a Ziegler al-
cohol of the chain distribution of 60 % C20-alkyl and 40 ~
C22-alkyl are dissolved in 500 parts by weight of toluene
and at 20C they are dropped to a solution of 220 parts by
weight of dimethylamine in 250 parts by weight of toluene.
Stirring is continued for 5 hours at room temperature and
subsequently for 3 hours at 70C. After cooling the preci-
pitated dimethylamine hydrochloride is filtered off with
suction and the - solvent is expelled in vacuo.
420 parts by weight of a yellowish oil are obtained. At
70C, 430 parts by weight of a chloroacetic acid ester,
~ ~ ~3 L ' 7 5
- 7 - HOE 79/F 16
manufactured froM chloroacetyl chloride and a Ziegler
alcohol of the chain distribution of 65 % C16-alkyl and
35 ~ C18-alkyl which before had been reacted with 2 mols
ethylenc oxide, are added. While thoroughly stirring
the mixture is poured into 3, 400 parts by weight of
distilled water of 70C and stirring is continued for 15
hours at this temperature. After ~his time, no free amine
can be observed. The chloride content is more than 9S % of
the expected value. A 20 % white, stable, pourable disper-
sion of a compound of the formula
C~3 ~ /CH2-C--R5 Cl~3
CH3 CH2-C0-(0C~l2cH2)2 R6
R5 C20/C22 ~lkyl~ R6 = c16/C18-~lkyl
is obtained. The pure compound can be obtained by distil-0 lation of the water.
Example 2:
According to the process described in example 1,
340 parts by weight of a chloroacetic acid ester from a
Ziegler alcohol with 65 ~ oE C16-alkyl and 35 ~ of C18-
5 alkyl are reacted in 400 parts by weight of benzene with
220 parts by weight of dimethylamine in 250 parts by weigllt
of benzene.
There are obtained 350 parts by weight of the corres-
ponding dimethylaminoacetic acid ester which can be distilled
at 150-170C at a pressure of 0.05 mbar. The product is
reacted to a quaternary product with 340 parts of the
C16(C18-chloracetic acid ester used before under the
conditions indicated in example 1. A stable aqueous dis-
persion of the compound of the formula
- 8 -
C~J3 ~ C1I2-C0-OR5
~ N\ Cl
C~13 C~l~-C0-OR6
55 R6 = ~16/C1~-Alky]
is obtained.
By dis~illation of water, this compound can be ob-
tained in pure form.
10Example 3:
Analoguously to example 2, 495 parts by weight of achloroaceticacid ester from an alcohol with 60 % C20-alkyl
and 40 % C22-alkyl, whose alcohol component before had
been reacted with 2 mols of ethylene oxide, 365 parts of
diethylamine and again 495 parts of the same chloroacetic
acid ester are reacted. The solvent used in the first reac-
tion step is toluene, in the second water.
20 3 2 \ ~ / C~12C-(C~2C~12)~-0P~5 Cl~
C~3 2 \ C~2cO-(OC~l2C~)2 OR6
R5 = R6 = C20/
The isolation of the com~ound is ~erformed as indi-
cated in example 2.
Exam~le 4:
340 parts by weight of a chloroacetic acid ester,
produced from a native, hydrogenated tallow fatty alcohol
of the chain distribution of 65 % C18-alkyl and 35 % of C16-
alkyl, are reacted analogously to example 1 in 700 parts
by weight of toluene with 220 parts by weiqht of dimethyl-
amine in 250 parts of toluene. As q~terni~ation components
there are used 385 parts by weight of chloroacetic acid
ester of the same tallow fatty alco~ol which before, however,
~ ~ 63275
- 9 - HOE 79/F 168
had been reacted with 1 mol of ethylene oxide. The qua-
ternization is carried out in such an amount of water
that a 20 ~ dispersion of the compound of the formula
CH3 ~ CH2COOR5 Cl~
C1~3 \ Cl-l2Co-oc~l2cTl2 6
1 0
is obtained. The isolation of this compound is also per-
formed by distillation of the water.
Example 5:
680 parts by weight of chloroacetic acid ester from
an alcohol with 60 % of C20-alkyl and 40 % of C22-alkyl,
whose alcohol component had been reacted with 2 mols of
ethylene oxide in 1250 parts by weight of toluene, are
dropped to a solution of 31 parts by weight of methylamine
and 20~ parts by weight of triethylamine in 250 parts by
weight of toluene at 20C. Stirring is continued for 1
hour at 20C and subsequently 7 hours at 60C, the pro-
duct is filtered at 40C to separate the precipitated
triethylamine hydr~chloride and the solvent is e~pelled in
the vacuo. There are obtained 720 parts of crude methyl-
iminodiacetic acid diester which is dispersed in 3,400 partsby weight of water of 50C while vigorously stirring.
126 parts of dimethyl sulfate are dropped into the pro-
duct. The temperature of 70C should not be exceeded.
A 20 ~ stab]~ dispersion of the quaternary compound of the
30 formula
CH3 ~ CH2-CO-(Oc~2c~l2)2-oR5
N C~130S03
C~13 Cll2-CO-(OCH2C~I2)2 OR6
R5 ~ ~6 = C20/C22-Alkyl
~ ~ ~3275
- 10 - HOE 79/F 168
is obtained. The pure compound is also obtained by distil-
lation of the water.
