DERIVES DE L'ACIDE .beta.-SULFOPROPIONIQUE ET PROCEDE POUR SA FABRICATION

.beta.-SULFO-PROPIONIC ACID COMPOUNDS AND PROCESS

Abrégé anglais

ABSTRACT OF THE DISCLOSURE: New .beta.-sulfo-propionic acid compounds
and a process for their manufacture by reaction of alcohols,
acid amides or amines with .beta.-sulfo-carboxylic acid anhydrides.
The compounds are textile assistants, e.g. washing, cleaning or
wetting agents, dishwashing detergents, hair shampoos, emulsifiers,
flotation agents, plasticizers and starting materials for th
manufacture of such agents, as well as for the manufacture of
dyes and pesticides.

Revendications

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. .beta.-sulfo-propionic acid compounds of the formula
<IMG>
where R1 is a straight-chain, alkyl of 4 to 26 carbon atoms,
alkenyl of 4 to 26 carbon atoms, alkylcarbonyl of 4 to 26 carbon atoms,
aralkyl of 7 to 26 carbon atoms, or 2-ethylhexyl, the individual
R2's may be identical or different and each is hydrogen or alkyl
of 1 to 4 carbon atoms, R3 is oxygen or R4 where R4 is hydrogen,
'
-N-
alkyl of 1 to 4 carbon atoms or hydroxyethyl, Z is a hydrogen ion,
<IMG>
an alkali metal ion or <IMG> , the individual R5's being identical
or different and each being an alkyl of 1 to 26 carbon atoms,
hydroxyethyl or hydrogen, n is O or an integer from 1 to 100,
and if n is O,R1 and R3 may also together be
<IMG>
R6 being hydroxyethyl or hydrogen and R2 having the meanings given
above, and the above radicals being optionally further be substituted
by one or more substituents selected from carboxylic acid amide,
cyano, nitro, chlorine, bromine, carbalkoxy and acylamido each of
2 to 4 carbon atoms, or alkyl and alkoxy each of 1 to 4 carbon atoms.
16

2. A process for the manufacture of a .beta.-sulfo-propionic
acid of the formula
Ia
<IMG>
where R is a straight-chain aliphatic radical of at least 4 carbon
atoms, an araliphatic radical, or 2-ethyl-hexyl, the individual
R2's are identical or different and each is hydrogen or an aliphatic
radical, R3 is oxygen or R4, R4 being hydrogen or an aliphatic
'
-N-
radical, n is O or an integer from 1 to 100 and if n is O,R1 and
R3 may also together be.
<IMG>
R6 being hydroxyethyl or hydrogen and R2 having the meanings given
above, by reaction of an alcohol, acid amide or amine with an acid
anhydride, wherein an alcohol, acid amide or amine of the formula
<IMG> II
where R1, R2, R3 and n have the meanings given in claim 1 is reacted
with a .beta.-sulfocarboxylic acid anhydride of the formula
<IMG> III
where R2 has the above meanings.
17

3. A process as claimed in claim 2, wherein the
resulting .beta.-sulfo-propionic acid Ia is reacted with a base
selected from alkali, morpholine and basesof the formula
<IMG> IV
where R5 has the meanings given in claim 1, to give a .beta.-sulfo-
propionic acid compound of the formula
<IMG> Ib
in which R1, R2, R3 and n have the meanings given in claim l and
Y is <IMG>, an alkali metal ion or <IMG>
the individual R5's being identical or different and each being
an aliphatic radical or hydrogen.
4. A process as claimed in claim 2, wherein the
reaction between starting materials II and III is carried out
using from 0.5 to 2.5 moles of starting material II per mole of
starting material III.
5. A process as claimed in claim 2, wherein the
reaction between starting materials II and III is carried out
at from 0 to 120°C.
6. A process as claimed in claim 2, wherein the
reaction between starting materials II and III is carried out
at from 20 to 90°C.
7. .beta.-sulfo-propionic acid compounds of the formula
<IMG>
18

where R1 is straight-chain alkyl of 8 to 24 carbon atoms, straight-
chain alkenyl of 8 to 24 carbon atoms, straight-chain alkylcarbonyl
of 8 to 24 carbon atoms, aralkyl of 10 to 24 carbon atoms or 2-
ethylhexyl, the individual R2's are identical or different and
each is hydrogen or alkyl of 1 to 4 carbon atoms, R3 is oxygen
or R4 , R4 being hydrogen,alkyl of 1 to 4 carbon atoms or hydroxy-
'
-N-
ethyl, Z is a hydrogen ion,
<IMG>
a sodium or potassium ion or <IMG> , the individual R5's being
identical or different and each being alkyl of 8 to 24 carbon
atoms, hydroxyethyl or hydrogen, n is O or an integer from 2
to 80 and if n is O,R1 and R3 may also together be
<IMG>
R6 being hydroxyethyl or hydrogen and R2 having the meanings
given above, and the above radicals being optionally further
substituted by one substituent selected from carboxylic
acid amide, cyano, nitro, chlorine, bromine, carbalkoxy and
acylamido each of 2 to 4 carbon atoms or alkyl and alkoxy each
of 1 to 4 carbon atoms.
8. A process as claimed in claim 2, wherein the reaction
is carried out with n-butyl alcohol, 2-ethyl-hexanol, n-octanol,
decanol, dodecanol, tetradecyl alcohol, octadecyl alcohol, stearic
acid ethanolamide, the glycol half-ester of lauric acid, octyl-
phenol, nonylphenol, dodecylphenol, butylamine, decylamine, dode-
cylamine, octadecylamine, dibutylamine, methylbutylamine, methyl-
benzylamine, methyltetradecylamine, N-ethanol-N-butylamine,
19

n-nonanol, n-undecanol, n-tridecanol, n-pentadecanol, n-hexadecanol,
n-heptadecanol, n-tetracosanol, octadecenyl alcohol, 2-undecyl-5-
hydroxyethyl-imidazoline, n-nonylamine, oleylamine, 2-ethylhexyl-
amine, hexacosanol or lauric acid ethanolamide, or any of the
above alcohols oxyalkylated with 2, 3, 4, 5, 25, 80 or 100 moles
of ethylene oxide or propylene oxide or moles of a mixture of
ethylene oxide and propylene oxide (in the ratio of from 0.1 to
20 moles of propylene oxide per mole of ethylene oxide), nonyl-
phenyl-tris-oxyethyl alcohol
<IMG> , a mixture of two or
more of those compounds, as the starting material II, and with
.beta.-sulfo-propionic anhydride, .beta.-sulfopivalic anhydride or the
anhydride of 2-ethylhexane-1-sulfonic acid -2-carboxylic acid as
the starting material III.
9. A process as claimed in claim 3, wherein the
reaction of the .beta.-sulfo-propionic acid Ia is carried out at
from 0 to 80°C using from 1 to 4 equivalents of base per mole
of product Ia, the base being selected from sodium hydroxide,
potassium hydroxide, morpholine, ammonia, dimethylamine, methylamine,
trimethylamine, triethylamine, diethylamine, monoethylamine,
propylamine, dipropylamine, tripropylamine, dibutylamine,
butylamine, tributylamine, nonylamine, dinonylamine, trinonylamine,
tetracosylamine, isopropylamine, diisopropylamine, triisopropyla-
mine, stearylamine, distearylamine, tristearylamine, ethanolamine,
diethanolamine, triethanolamine, butyldiethanolamine and
dimethylethanolamine.

Description

1060444
The invention relates to new ~-sulfo-propionic acid
compounds and a process for their manufacture by reaction of
alcohols, acid amides or amines with ~-sulfo-carboxylic acid .
anhydrides.
The reaction of ~-sulfo-propionic anhydride with methanol,
ammonia or amines to give the corresponding ester or amide, respecti-
vely, is disclosed in J. Amer. Chem. Soc., 62 (1940), 2,395 - 2,397.
We have found new ~-sulfo-propionic-acid compounds of the
formula - 2 2
/ ~ R \ O R o
~ C-C ~ ~3-C-C-C 2-5~ Z
where R is a straight-chain, alkyl of 4 to 26 carbon atoms,
alkenyl of 4 to Z6 carbon atoms, alkylcarbonyl of 4 to 26 carbon
3 atoms, aralkyl of 7 to 26 carbon atoms, or 2-ethylhexyl, the
~ndividual R2'~ may be identical or different and each is hydrogen
or alkyl of 1 to 4 carbon atoms, R3 is oxygen or R4 where R4 is
,
: -N-
hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyethyl, Z is
, a hydrogen ion,
, , ~/C~2-C~
H2N ~
~: C}12- H2
, : .
R5
i an alkali metal ion or R5-N-H , the individual R5's being identical
.~ R5
J. or different and each being an alkyl of 1 to 26 carbon atoms,
hydroxyethyl or hydrogen, n is O or an integer from 1 to 100,
and if n is 0,Rl and R3 may also together be
H
: H Cl --- C - R6
N ~ / N -
R H
~7 1 ~
L
- ^i^. .

1060444
R6 being hydroxyethyl or hydrogen and R2 ha~ing the meanings
given above, and the above radicals being optionally further be
substituted by one or more substituents selected f~om carboxylic
acid amide, cyano, nitro, chlorine, bromine, carbalkoxy and acy-
lamido each of 2 to 4 carbon atoms, or alkyl and alkoxy each of
1 to 4 carbon atoms.
Further, we have found that ~-sulfo-propionic acids
of the formula
H R2 R2
C-~ ~ R3-c-c-cH2-so3H Ia
1~ ~ n R
wherein R is a straight-chain, alkyl of 4 ,to 26 carbon atoms,
alkenyl of 4 to 26 carbon atoms, a~kylcarbonyl of 4 to 26 carbon
atoms, aralkyl of 7 to 26 carbon atoms or 2-ethylhexyl , the
individual R~'s may be identical or different and each is hydrogen
or alkyl of 1 to 4 carbon atoms, R3 is oxygen or R4 where R4 is
-N-
hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyethyl, n is 0
or an integer from 1 to 100 and if n is 0, Rl and R3 may also
together be
H---C C R6 , where R6 is hydroxyethyl or
, .
N N
.~, \C/
, R 2
hydrogen and R has the above meanings, may be obtained advanta-
geously by reaction of alcohols, acid amides or amines with acid
anhydrides if alcohols, acid amides or amines of the formula
; 30
L.
.... ~

1060444 ooæO 30,756
~ H R ~
Rl ~-C C ~ R3~H II
wher-e Rl, R2, R3 and n have the above meanings, are reacted
with ~-sulfocarboxylic acid anhydrides of the formula
O R2
.~ ~
C - C - CH2 - SO2 III
R2
. O
where R2 ha~ the above meanings~
Further, we have found that an advantageous embodiment of
the process is to react the resulting ~-sulfo-propionic acids Ia
with alkali, morpholine or a base of the formula
R5
. R5 - N IV
R5
where R5 has the above meanin~s, to give ~-sulfo-propionic acid
~ compounds Or the formula
3 ~ H R2\ O R2 ~
1 Rl _ ~ C-C ~ R -C-C2CH2 S 3 y~ Ib
1 in which Rl, R2, R3 and n have the above meaning~ and Y is
- ",CH2 CH~ R5
~ CH2-CH2 , an alkali metal ion or R5-N-H~, where
R
the individual R5's may be identical or different and each is
an aliphatic radical or hydrogen.
Where sulfo-propionic anhydride, dodecyl alcohol and morpholine
. are used, the reaction may be represented by the following equation:
C12H25 OH ~ olc-cH2-cH2-so2 ~~~~ C12H25 o-C-CH2-CH2-S3H
~ H2-C~
+HN ~ O
CEI2-CH2
-3~ /

10609~44
CH C~
Cl2H25-OCO-C~2-CH2-S03 H2N o
CH2-CH2
Compared to the state of the art, the process of the
invention gives a large number of new ~-sulfo-propionic acid
compounds, in the form of esters, monoacylamides and diacylamides,
simply and economically and in good yield and purity.
The starting materials II and III can be reacted in
stoichiometric amounts or in excess (of one material), preferably
in a ratio of from 0.5 to 2.5 moles of starting material II per
mole of starting material III. Preferred starting materials II,
III and IV and accordingly preferred products I, Ia and Ib are
those wherein R is advantageously straight-chain alkyl of 8
to 24, and especially of 12 to 24, carbon atoms,especially
straight-chain alkenyl of 8 to 24, carbon atoms,advantageously
straight-chain alkylcarbonyl of 8 to 24, and especially of 12 to 24,
carbon atoms, advantageously aralkyl of 10 to 24 and especially of 10
.~ to 18 carbon atoms, in particular nonylphenyl, isooctylphenyl
or octylphenyl, or 2-ethylhexyl, the individual R 's may be
: 20 identical or different and each is hydrogen or alkyl of 1 to 4
carbon atoms, R is oxygen or R where R is hydrogen, alkyl of
. N
1 to 4 carbon atoms or hydPoxyethyl, Z is a hydrogen ion,
,,/CH2-CH~ ,
. H2N~ ~ O , - .
C~ 2 - C H2
. sodium or potassium or R5 , where the individual R5's may be
.' R5-N-H
R5
identical or different and each is advantageously an alkyl
of 8 to 24, and especially of 12 to 24, carbon atoms, hydroxyethyl
or hydrogen, n is 0 or an integer from 2 to 80, and if n is 0,
and R3 may also together be H
. H-C______c_~6
N N -
c/
. ~. 4

1060444 oOzO 30,756
where R6 is hydroxyethyl or hydrogen and R2 has the above meaningsO
The above radicals can further be substituted by groups
and/or atoms which are inert under the reaction conditions, eOgO
carboxylic acid amide, cyano, nitro, chlorine, bromine, carb-
alkoxy and acylamido each of 2 to 4 carbon atoms, or alkyl and
alkoxy each of 1 to 4 carbon atomsO It is also possible, and
advantageous, to react mixtures of ~traight-chain alcohols, e.g.
those obtained from the oxo ~ynthesis, and further process the
resulting mixtureR of products I directly9 eOg~ to give surfactants.
This i~ economically advantageous because it saves isolating the
individual alcohols from the mixtures, which in most cases is a
laborious operation entailing heavy lossesO A rurther range of
very valuable alcohols for the reaction with the sulfocarboxylic
acid anhydride is obta;ned by oxyalkylation of straight-chain
alcohols with epoxides, e.g. ethylene ox;de and/or propylene
oxide, which are reacted with the alcohols in the ratio of rrom
1 to 100 moles Or alkylene oxide or a mixture o~ the epoxides per
mole Or alcohol. If mixtures of amines, e~gO fatty amines such
as laurylamine, are u~ed as starting materials, mixtures of the
sul~onates of these amines with the corresponding ~-sui~opropionic
acid amides are obtainedO
Examples of suitable starting materials II are n-butyl
, alcohol, 2-ethylhexanol, n-octanol, decanol, dodecanol, tetra-
decyl alcohol, octadecyl alcohol, stearic acid ethanolamide,
the glycol half-e~ter o~ lauric acid, octylphenol, nonylphenol
and dodecylphenol; butylamine, decylamine, dodecylamine, octa-
decylamine, dibutylamine, methylbutylamine, methylbenzylamine,
methyltetradecylamine and N-ethanol-N-butylamine; n-nonanol,
n-undecanol, tridecanol, pentadecanol, hexadecanol, heptadecanol,
3o n-tetracosanol, octadecenyl alcohol 9 2-undecyl-5-hydroxyethyl-
imidazoline5 n-nonylamine, oleylamine, 2-ethylhexylamine, hexa-
cosanol and lauric acid ethanolamide; the above alcohols oxyalkylated
with 2, 3, 4, 5, 25, 80 or 100 moles of ethylene oxide or
propylene oxide or moles of ethylene oxide and propylene oxidé (in
:: ~5-
.

-- ~060444 oOzO 30,756
the ratio Or rrom 0.1 to 20 moles o~ propylene oxide per mole Or
ethylene oxide), e~gO nonylphenyl tris oxyethyl alcohol
C9H19 ~ ~CH2 CH2 ~ H ; and appropriate
mixturesO
Possible starting materials III are ~-sulfopropionic
anhydride, ~-sulfopivalic anhydride and the anhydride of 2-
ethylhexane-1-sulfonic acid-2-carboxylic acidO
The reaction is a~ a rule carried out at from 0 to 120C,
prererably from 20 to 90C, under atmospheric or superatmospheric
pressure, continuously or batchwiseO Preferably, no solvent is
used. However it iæ also possible to use organic solvents which
are inert under the reaction conditions, such as chlorohydro-
carbons, e~g. ethylene chloride and chloroform, cyclic ethers,
' e~g. dioxane and tetrahydrofuran, and aliphatic or aromatic
hydrocarbons, eOgc toluene, heptane and petroleum etherO
The reaction may, eOgO, be carried out as ~ollows:
the appropriate etarting material II i8 added to the sulfocarb-
oxy}ic acid anhydride III, optionally in a solvent, whilst
~tirring well~ The mixture is then kept ror a further 2 to 3
hours at the reaction temperature. The product is isolated by
conventional methods, eOgo by distillationO It is, however, more
advantageous to neutralize the sulfonic acid Ia which has been
.7
formed with bases IV, alkali or morpholine and to isolate the
product Ib by conventional methods, eOgO by crystallization ~rom
suitable solvents such as alkanols, e.~. ethanol and isobutanol,
~ halohydrocarbons, eOgO ethylene chloride and chloroform, tetra-
- ~ hydrofuran, acetone, ethyl acetate and diethyl ether. Where amines
: ~
~ II are used, neutralization is conveniently efrected by using an
., :
. ~ -
appropriate excess Or amine II. In general, the neutralization is
. ~ .
~0 effe¢ted at ~rom 0 to 80C, under atmospheric or superatmospheric
~; pressure, continuously or batchwise, over the course Or ~rom 0.1
to 12 hours, using from 1 to 4, prererably from 106 to 3, equiva-
~ lents of base per mole o~ product Ia. Preferred bases are sodium
'~ -6-
~ .

1060444 oOzO 30,756
and potassium compoundsg especially sodium hydroxide and
potassium hydroxide, morpholine9 ammonia, pr;mary, secondary
or tertiary alkylamines of 1 to 26, advanta~eously of 1 to 4
or 8 to 24, carbon atoms per alkyl group, eOgO dimethylamine,
methylamine, trimethylamine, triethylamine, diethylamine, mono-
ethylamine, propylamine, dipropylam;ne, tripropylamine, dibutyl-
amine, butylamine, tr;butylamine, nonylamine, dinonylamine, tri-
nonylamine, tetracosylamine, isopropylamine, diisopropylamine,
triisopropylamine, stearyIamine, distearylamine and tristearyl-
amine, and amine~ containing hydroxyethyl groups, eOgO ethanolamine,diethanolamine, triethanolamine, butyldiethanolamine and dimethyl-
ethanolamineO After neutralization, the salt ;s isolated by con
~entional methods, eOgO by filtrationO
The new products I which can be manufactured by the process
Or the invention are text;le assistants, eOgO washing, cleansing
or wetting agents, dishwashing detergents, hair shampoos, emulsi-
~iers, ~lotation agents, plasticizers and ~aluable starting
materials ror the manufacture of such a~sistants, as well as ror
the manufacture of dyes and pesticidesO Thus, with all products
of the examples which ~ollow, eOgO with a mixture Or sodium
,' (dodecyl-dioxyethyl propionate)-B-sulfonate and sodium (tetra-
decyl-dioxyethyl propionate)-B-sulfonate (in the ratio Or ~
a very good wetting erfect on cellulos;c material and a very good
~ detergent action when laundering cotton fabrics and washing
J~ woolen article~, impregnated with oli~e oil or ~ineral oil, i8
achieved at concentrations o~ only from 10 to.100 parts per 1,000
parts o~ water~ Furthermore, all the products Or the examples
which follow, eOgO the mixture of sodium (dodecyl-tris-oxyethyl
propionate)-~-sulfonate and ~odium (octadecyl-tri~-oxyethyl propio-
nate)-R-sulfonate tin the ratio of 1 : 1) can be used in dish-
washing detergents of moderate foaming power, having, eOg., the
following composition:
5 parts o~ diethanQlamine alkylbenzenesulfonate
--7--

~06~444
O.Z0 30,756
5 parts of nonylphenol condensed with 10 moles of ethylene
oxide
5 parts of ~odium (dodecyl/octadecyl-tris-oxyethyl propionate)-
~-sulfonate (1 : 1)
5 parts Or isopropanol
5 parts of tetrapotassium pyropho~phate
75 parts of water
In the Examples which follow, parts are by weight.
EXAMPLE 1
29.6 parts Or n-butanol are added to a melt o~ 5405 parts
o~ ~-sulropropionic anhydride at 65C, whilst stirring~ A~ter
stirring ror a rurther two hours at 70C, the sulfonic acid I
which i6 formed is neutralized by adding 51.7 parts Or butyl-
diethanolamine. 122 parts (8~.8% Or theory) of butyldiethanol-
, ammonium ~butyl propionate)-~-~ulfonate are obtained as a brown
; oil. n20 ~ 1.47120
EXAMPLE 2
~ 130 parts o~ 2-ethylhexanol are added ~lowly to a melt of
`! 163 parts o~ ~-sul~opropionic anhydride at 75C A~ter stirring
for a further three hours at 80C, the mixture i~ adjusted to pH
~ 5 with 90 parts Or 50 per cent strength by weight sodium hydroxide
¦ ~olution at 50C, whilst ~tirring. Sodium (2-ethylhexyl propionate)-
A-sulronate is obtained in the rorm of a 64 per cent strength by
weight paste which is readily water-soluble. Yield: 265 parts
(9005% of theory)0 n20 - 1.4589.
EXAMPLE 3
(a) 130 parts Or dodecyl alcohol are added slowly to a melt Or
95 parts of ~-sulPopropionic anhydride at from 75 to 80C, whilst
¦; stirring and slightly cooling the mixture. A~ter stirring ror a
¦ 3 further three hours at 85C~ 225 parts of (dodecyl propionate)-~-
sulronic acid Or melting point 36 - 38C (arter recry~tallization
rom ethylene chloride) are obtained.
-8-
:

106~444 o ~z o 30,756
(b) 28.6 parts of morpholine are added to 9608 parts of the
sul~onic acid I at 40C, whilst stirringO The mixture is diluted
with 100 parts of ethylene chloride and stirred for 2 hours at
60C. After adding 800 parts of petroleum ether, the morpholinium
(dodecyl-propionate)-~-sulfonate which has crystallized out is
rilt;ered of~ and recrystallized from ethanolO Melting point 74 -
77C; yield: 100 parts (81~5% of theory)0
EXAMPLE 4
65.5 parts of ~-sulfopivalic anhydride are introduced into
74.5 parts of dodecyl alcohol at 25C, whil~t stirring. When the
- exothermic reaction ha~ ended, the mixture is slowly warmed to
70C and stirred at this temperature for 3 hours~ The (dodecyl
pivalate)-~-sulfonic acid is ob~ained in the form of a yellow
; oil Or n20 = lo 45630
37 parts of morpholine are added slowly to the product Io
Arter dilution with 250 part~ o~ petroleum ether, the mixture i8
stirred ~or one hourO ~he ~uspension obtained is cooled and the
product is then filtered Or~ and re¢rystallized ~rom acetoneO
Melting point 7005 ~ 72C; yield-146 parts (74o2%-0~ theory)
20 Or morpholinium (dodecyl pivalate)~ ulfonate.
I EXAMPLE 5
,~ 48D5 parts of a mixture o~ straight-chain alcohols, con-
l taining 2705% by weight Or nonyl alcohol, 12% by weight o~ decyl
!
alcohol and 6005% of undecyl alcohol are added to a melt o~ 41
parts of ~-sulfopropioni~ anhydride at 65C, whilst stirring.
~ ~:
ll~ After stirring for a further three hours at 70C, the mixture is
~ .:,pr,
cooled and neutralized-with 48 parts o~ 25 per cent strength by
weight sodium hydroxide solution at 30QC. A water-soluble paste
'~ containing 137 parts (100% o~ theory) of sodium (nonyi, decyl and
30 undecyl propionate)-~-sulfonate of melting point 280 - 285C
i (with decomposition) (after recrystallization rrom acetone) is
obtainedO The ratio of the esters corresponds to the ratio Or
the alcohols used.
'~

1060444 o zO 30,756
EXAMPLE 6
64 parts o~ a mixture of straight-chain alcohols con-
taining 2805% by weight of dodecanol, 27% by weight of tri-
decanol, 23% by weight of tetradecanol and 210 5% b~ wei~ht of
pentadecanol are added to a melt of 41 parts of sulfopropionic
anhydride at ~rom 70 to 80C After stirring for a further
three hours at 70C, the sulfonic.acid.I, which is in.the ~orm
of a dark brown oil, is neutralized by adding 2605 parts Or
50 per cent strength by weight sodium hydroxide solution.
130 parts (100% of theory) o~ ~odium.(tridecyl, dodecyl,
tetradecyl and pentadecyl propionate)-~-sulfonate o~ nD =
1 4613 are obtained. The ratio of the esters corresponds to
the ratio of the alcohols usedO
EXAMPLE 7
78 parts Or a mixture of n-hexadecyl alcohol and n-
octadecyl alcohol (2: 1) are added to a melt of 41 parts Or
~-sul~opropionic anhydride, whilst stirring~ Arter ~tirring
~or a further three hours at 75C, the brown melt is.taken up
in 350 parts of ethylene chloride and 29 parts o~ morpholine
20 are added whilst stirring at from 50 to 70~0 The ethylene
¢hloride is distilled off under. reduced.pressure .and the re~i-
due i8 recrystallized ~rom ethanolO 142 parts (96% Or theory)
o~ morpholinium (hexadecyl/octadecyl propionate)~-sulronate
are obtained in the form o~ light brown: crystals. rlelting
point 76 ~ 80Co The ratio of the esters corresponds to the
ratio o~ the alcohols used.
EXAMPLE 8
68.5 parts o~ a fatty alcohol mixture containing 41%
by weight of dodecanol, 30% by weight of tetradecanol, 18% by
30 weight of hexadecanol and 11% by weight Or octadecanol are
added to a melt of 41 parts of sulfopropionic anhydride at
from 60 to 70C J whilst stirring After stirring ror a
further three hours, the sulfonic acid T iS obtained as a
--10--

60444
O.Z0 30,756
brown oil which is neutralized by adding 26~4 part~ o~ 50 per
cent strength by weight sodium hydroxide solution at 30C~
Precipitation with acetone gives 93 parts of sodium (dodecyl,
tetradecyl, hexadecyl and octadecyl/propionate)-~-sulfonate)
a~ white cry~tals which give a clear solution in waterO Melting
point ~00C (with decomposition)0 The ratio of the esters corres-
pond~ to the ratio o~ the alcohol~ used.
EXAMPLE 9
99.5 parts o~ a mixture,of n-dodecyl alcohol and n-tetra-
decyl alcohol (55.5 : 4505) oxyethylated with 3 mole~ of ethylene
oxide are added to a melt of 41 parts of R-~ulfo-propionic anhy-
dride at from 50 to 70C~ whilst stirring. A~ter stirring for a
~ùrther three hours at 70C, 2806 parts,or morpholine are added
to the mixture at ~rom 40 to 70C and the batch i8 stirred for
a ~urther ~ hours. 159 part~ (94% o~ theory) Or morpholinlum
~do~ecyl/tetradecyl-tri~-oxyethyl propionate)-~-sulronabe are
obtiined as a light brown pasteO n20 - 1.4598~.The.lratio o~ the
e~torB ¢orre~pond~ to the ratio Or the.alcohols used.
EXAMPLE 10
6~.5 parts o~ ~-sul~opi~alic anhydride,are introduced.in~o
133 parts of a mixture o~ n-dodecyl-..and n~tetradecyl-tris-oxyethyl
alcohol (55 ; 45) at from 60 to 70C. 198 parts (a practically
quantitative yield) o~ the ~ulfonic acid-I are obtained:as a
red-brown oil-o~ nD = 1.4613.
The mixture i3 neutralized by adding ~9.5 parts Or 50 per
.
cent strength by weight sodium hydroxide solution. 237 parts
~, (a practically.quantitative yield) of sodium,(dodecyl/tetradecyl-
tris-oxyethyl pivalate)-~-sulfonate are obtained,as a 91.6 per
cent strength.a~ueous solution. The ratio.of the e~ters corresponds
~0 to the ratio of the alcohols u~ed.
EXAMPLE 11
9.5 parts o~ sulfopropionic anhydri~e are-added to 227-parts
o~ a mixture.o~ straight-chain alcohol~, containin~.65% by weight
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OOZo 30,756
of hexadecanol and 35% by weight of octadecanol, which has been
oxyethylated with 80 moles o~ ethylene oxide. After stirring for
a rurther three hours at rrom 75 to 80C, the (propionic acid
e~ter)-sulronic acids I are obtained as a brown oil (n50 _ 1.4617).
Thi~ is neutralized by adding 236 parts of water and 10 parts o~
50 per cent strength by weight sodium hydroxide solution at from
30 to 40C. 482 parts of the sodium (propionic acid ester)-~-
sulronate based on the above alcohol mixture are obtained as an
aqueous paste. The ratio of the esters corresponds to the ratio
Or the alcohols used.
, EXAMPLE 12
378 part~ Or n-nonanol which has been oxyalkylated with
moles Or ethylene oxide and 2 moles Or propylene oxide are
added to a melt of 129 parts of ~-sul~opropionic anhydride at
from 70 to 80C, whilst stirring. Arter stirring for a further
two hours at 80~, 508 parts (a practically quantitative yield)
o~ (nonylpentaoxyethyl propionate)-~-sulfonic acid,are obtained
~ as a brown oil (n30 = 104590)o The product i8 nçutralized by
', adding 57 parts of 50 per cent strength by weight sodium hydroxide
~olution and 250 parts of water, 815 parts (a practically quanti-
I tative yield) of the sodium salt are obtained in the form o~ a
1 66 per cent strength aqueous solutionO
j EXAMPLE 13
i ~ 106 parts of n tetracosanol are added to a melt Or 41 parts
~-sulfopropionic anhydride at from 60 to 70C,,whilst stirring.
1 A~ter stirring for a further four hours at 70C, 147 parts (a
¦~ practically quantitative yield) of (tetracosyl propionate)-~-
f sul~oni,c acid are obtained as a brown oil (n50~= 104537). Arter
;~ dilution with 260 parts of water, the mixture is neutralized with
24 parts o~ 50 per cent strength by weight sodium hydroxide soiution.
430 parts (a practically quanti~ative yield) or the sodium salt
are obtained in the rorm Or a 35 per cent strength aqueous oil.
`:
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EXAMPLE 14
78 parts Or n-octadecenyl alcohol are added to 41 parts
Or sulfopropionic anhydride at 60C, whilst stirring~, Arter
~tirring ror a further three hours at 70C, 119 parts (a prac-
tically quantitative yield) of (octadecenyl propionate)-~-
~ulfonic acid are obtained as a brown oil (nD = 1.4550). 45 parts
Or triethanolamine are added at 70Co The mixture is stirred for
a further 2 hours at 70C, 163 parts (a practically quantitative
yield) Or pasty triethanolamine salt are obtained.
EXAMPLE 15
1180 5 parts of nonylphenol which has been oxyalkylated with
4 moles Or ethylene oxide are added to 41:parts of,~-sulropro-
pionic anhydride at 70C, whilst stirring. After stirring for a
rurther two hours at 75C, 4208 parts Or dibutylamine, are added
at ~rom 40 to 60C and the mixture is stirred ror a rurther 2
hour~ at 70C. 192 part~ (97% o~ theory) Or dibutylan~onium
~nonylphenyl-tetraoxyethyl propionat:e)-~-~ulronate.are: obtained
, a~ a brown oil (n20 - 1.4904).
~,, EXANPI,E 16
13.6 parts of~ ~-sulfopro.pionic anhydride .are added at 70C,
~, whilst stirring, to 130.6 parts of .-isooctylphenol which ba~ been
oxyalkylated with 25 moles Or ethylene oxideO Arter 3.hours at
70C, 144 D2 parts (a practically quantibative yield) of product
.' I (n20 ~ 1.4847) are obtained" A~ter adding.2.70 parts o~ water,
12 parts Or 50 per cent strength by weight sodium hydroxide solution
, are introduced and the mixture is stirred for 2 hours at 40~.;, 426 parts (a practically quantitative yield) o~ sodium (isooctyl-
'~ phenyl propionate)~ ul~onate:are obtained as. a light brown 35
per cent strength aqueous oil.
EXAMPLE 17
;- i34 parts Or 2-undecyl-5-hydroxyethyl-imidazoline are added
, to 68 part~ o~ ~-sulropropionic.anhydride at 80~ he mixture is
stirred ror a further 4 hours at 80C, givin~;.l98.part~ (98% Or
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theory) of N-(2-undecyl-5-hydroxyethyl~imidazolinyl)-propionic
acid-R-sulfonic acidO
EXAMPLE 18
54O5 parts of ~ulfopropionic anhydride are added to a
solution Or 120 part~ of n-nonylamine in 250 parts Or ethylene
chloride at 40C, whil~t stirringO After stirring for a further
two hours at 45C, the suspension is riltered and the crystalline
product is recrystallized from ethylene-chlorideO 86 parts
' (71.4% of theory) of nonylammonium (propionyl-nonylamide)-~-
sulfonate are obtained as colorless crystals of melting point
/ 167 ~ 169Co
:, EXAMPLE 19
41 parts of sulfopropionic anhydride are added to a solution
:, of 160 parts Or oleylamine in 200,parts Or ethylene,chloride at
from 50 to 60C. Arter one hour, 25 parts Or 50,per cent strength
,~ by weight ~odium hydroxide so}ution are added to the red-brown
,~ oil obtained, and the mixture is stirred for,one hour at 80C.
A~ter cooling, the suspension is riltered and the,re~idue is
heated with acetone at 56C,ror halr an hourO 167 parts (650~%
.~ 20 of theory) of sodium (propionyl-oleylamide)-~-sulfonate Or melting
point 304 - 309C are obtainedO
EXANPLE 20
3~ 144 parts o~ di-(2-ethylhexyl)-,amine are added to 41 parts
Or sulfopropionic anhydride at-70 - B0C, whilst ~tirringO After
~: stirring for a further two hour~ at 130C, 176,parts (70% Or
: '~
: ~ theory) Or di-(2-ethylhexyl)-ammoniwn (propionyl-di-(2-ethylhexyl)-
, ~ amide)-~-sulfonate are obtained as a brown. oil of nD s 1.4724.
EXAMPLE 21
~, 243 parts of lauric acid ethanolamide are added to 136 parts
30 of ~-sulfopropionic anhydride at from 70 to 80C, whilst stirring.
After stirring for a furkher three hours at 80C, 379 parts
(practically the quantitative yield) Or (propionyl-lauroylethanol-
amide)~ ulfonic acid of n50 = 1.4719 are obtained.
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106044~ oOz. 30,756
After dilution with 250 parts of water, the mixture is
neutralized with 120 parts of 50 per cent strength by weight
sodium hydroxide solution. 743 parts (a practically quantitative
yield) of the sodium salt are obtained in the form of a 55 per
cent strength white paste.
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