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Патент USA US2120557

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Patented June 14, 1938
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UNITED stares ems? orrics
SULPHONIC ACIDS 0F CARBOXYLIC ACID
ADIIDES AND PROCESS FOR rm PRO
DUCTION THEREOF
,
Hans Haussmann, Mannheim, Germany, . as
signor to I. G. Farbenindustrie Aktiengesell
schaft, Frankfort-on-the-Main, Germany
- No Drawing.
Application May 6, 1936.
Serial
No. 78,196. In Germany May 16, 1935’
20 Claims.‘ (Cl. 260—124)
The present invention relates to-a process for
the production of sulphonic acids of carboxylic
resin acids, bile acids and naphthenic acids may
be employed. »
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acid amides which are suitable as assistants in
' The conversion‘ of the said initial materials
the textile and related industries.
,
into halogenated carboxylic acids or their con
I have found that especially valuable washing, - version products, such as fatty acid chlorides, 5
wetting, cleansing, dispersing and like agents
are obtained by condensing halogen-containing
aliphatic carboxylic acids or their derivatives,
maybe effected ‘by known methods; whenintro- .
ducing halogen into saturated initial materials,
the‘ reaction may be accelerated by increasing
such as halides, anhydrides or esters, with amino ‘ the‘temperature, by the action of light or by the
10 sulphonic acids the amino groups of which still addition of catalysts. vUnsaturated carboxylic 10 .
contain at least one replaceable hydrogen atom
and the sulphonic group of which is- combined
to an aromatic radicle. In the present case the
term aliphatic carboxylic acid is intended to
15 comprise open chain as well as’ cycloaliphatic
carboxylic acids. -
‘
‘
acids generally speaking absorb the necessary
amounts of halogen under very mild conditions.»
As amino-sulphonic acids having aromati
cally-combined sulphonic groups may be men
tioned in particular the aromatic amino-sul- '15
phonic acids, as for example sulphanili'c acid,
Suitable halogenated carboxylic acids or carboxylic acid derivatives for the process accord,ing to this invention are in particular the halo20 genated chloride of saturated or unsaturated
fatty acids from naturally-occurring fatty acid
metanilic acid, , N-ethyl-metanilic acid, ortho
aminobenzene sulphonic acid, toluidine sulphonic
acids and naphthylaminosulphonic acids as well
as their derivatives or substitution products. In 20
many cases those amino-sulphonic acids the
containing substances for example oils, fats,
waxes or resins, such as coconut oil, palm kernel
oil, olive oil, soy bean oil, castor oil, hydro25 genated train‘ oil (which may still contain un-
nitrogen atoms of which only contain one re
placeable hydrogen atom and the second hydro-‘
gen atoms of which are replaced by aromatic,
saturated acids), tallow or Montan wax or 001-
ophony.
Products which contain fatty acid
radicles having a long carbon chain in the molecule have a specially good‘ action. The degree
30 of halogenation may be of any desired value
depending on the nature of the condensation
products and the purpose for which they are to
be employed. Generally speaking it is advantageous when employing fatty acids of high movi lecular weight to introduce up to two or more
.5
aliphatic, cycloaliphatic, aliphatic-aromatic or 25
radicles are especially valuable.
heterocyclic
Polynuclear amino-sulphonic acids of the said
kind may also be employed in the same way and
also amino-sulphonic acids which still contain
hydroxy, carboxylic, ether, ester or nitro groups 30
or which are substituted by halogen atoms.
Amino-sulphonic acids which contain two or
more basic groups of which at least one con
tains a replaceable hydrogen atom, or which
contain two or more, sulphonic groups are also 35
atoms of halogen into the aliphatic or‘ cyclo-
suitable for the process according to this inven
valiphatic radicle of the carboxylic acid; when
employingv carboxylic acids of low molecular
tion. For example dimethyl-para-phenylenedi
amine sulphonic acid, naphthylaminedisulphonic
weight, a smaller content of halogen is frequent40 1y sufficient in order to obtain products having
Valuablé propel‘ties- When employing fatty acid
acids and naphthylamine-trisulphonic acids may
be mentioned. The amino-sulphonic acids to be 40
employed according to this invention may also
mixtures as the initial material it is sometimes be interrupted in the chains or between are
sui?cient to halogenate only a part of the fatty ' matic rings or both by hetero atoms or atomic
acids.
'45
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'
Instead/of simple aliphatic carboxylic acids or
groups._ The amino groups may also have a
purely aliphatic character, as for example in 45v
their derivatives; substituted carboxylic acids or
benzylamine sulphonic acid or in compounds of
their derivatives may be employed or also carbox he acids which contain hetero atoms, such
as gxygen or sulphur, or hetero-atomic groups,
the composition:
50 such as carboxylic amide groups, in the aliphatic
"radicles. Carboxylic acids having branched
chains and the like may also be employed for
the process according to this invention; for example carboxylic acids obtainable by the oxi55 dation of para?in wax and the like, and also
,
_
NHZ'CH2'CHZ'O'CGH4'SO3NQ‘
The said interruption may occur in any desired 50
manner, as for example by oxygen or sulphur
atoms or by carboxylic amide groups or other
atomic groups or also by tertiary nitrogen
atoms.
7
The reaction of the halogenated fatty acid de- 55
2
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'
2,120,587
rivatives with the amino-sulphonic acids con
sorption of 50 parts has taken place. The re- '
taining aromatic sulphonic groups may be car
sulting chlorination product is freed from dis- '
ried out under the working conditions usual for , solved hydrochloric acid by leading in air and
the Schotten-g-Baumann reaction is so far as then introduced at a temperature of zero C. into
5 acid chlorides and acid anhydrides are employed.
In ‘this case, the condensation may also be car
ried out in organic solvents with an addition of
agents combining with acids. vIn the reaction
of fatty acids or fatty acid esters with amino
10 sulphonic acids or their salts it is preferable to
work in the presence of organic solvents; butanol
for example is suitable for this purpose. It is
preferable to employ salts of the amino-sul
phonic acids which are soluble in organic sol
15 vents, as for example those ‘of tertiary bases,
such as triethylamine or dimethylaniline; pyri
dine may also be employed in many, cases. In
some cases the said bases themselves are suitable
' 20
as solvents.
The products obtained in the said ‘manner have
an excellent washing power for- substances of all
kinds. They have a high stability when em
a solution of 173 parts of metanilic acid rendered 5
alkaline with sodium carbonate. The mixture
is stirred for some time at ordinary temperature
and the resulting paste is- evaporated to dryness.
A very active. washing agent is obtained which is
stable in hard water.
.
~
Instead of metanilic acid also N-ethyl meta
nilic acid can be employed; in this manner a.
product is obtained which possesses a high wash
ing power.
'
10
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Example 2
15
Chlorine is led into. 200 parts of coconut oil
fatty acid chloride at about 90° C. until an in
, crease in weight of 40 parts hastaken place. The
resulting acid chloride is condensed in the man
ner described in Example 1 with 223 parts of 20
naphthionic acid and worked up. A product is
ployed in hard water; when the content of halo- ' obtained which has in particular a very good
gen is su?icient, their aqueous solutions give no [emulsifying power.
Example 3
25 deposits in the cold even in very hard water.
By reason of their valuable properties they may
"70 parts of chlorine are led into 300 parts of 25
be employed in a very general and varied manner oleic acid chloride while cooling with ice. The
and they are especially suitable for all domestic resulting product is reacted with 300 parts of an
and industrial purposes. They may also fre
amino-sulphonic. acid having the formula:
30 quently be employed for the production of prep~
arations. Since they also have an excellent dis
persing power for liquid and solid substances, it
is possible for example to convert large amounts
of solvents, oils, fats and waxes into aqueous solu
35 tions with their aid. The said- products may also
at a temperature of from 25° to 30° C., the reac
tion being alkaline to phenolphthalein and being
among these may be mentioned for example in
organic salts, such as waterglass, Glauber’s salt,
kept so by the addition of corresponding amounts
of caustic soda solution. When the reaction is
completed, the reaction mixture is heated for 35
some time at from" 45° to 50° C.,~neutralized and
evaporated to dryness. A product is obtained
perborates, ortho-, pyro- and meta-phosphates,
which is eminently suitable especially for dis
be employed together with other . substances;
40 organic salts, such as soaps, sodium salts of tetra- . persing calcium soaps.
hydronaphthalene sulphonic acids or Turkey red
oils, or other wetting and cleansing agents, as for
example salts of fatty alcohol sulphuric esters or
which comprises condensing an aliphatic carbox
true aliphatic sulphonic acids.
ylic ‘acid substance selected from the class con
Organic sub
What I claim is:
40
1. The. process for the production of amides '
45 stances of a colloidal nature are also suitable as sisting of carboxylic acids, carboxylic halides, an
' additions, as for example glue, starch, traga
hydrides and ,esters, containing outside the car
,canth, reaction products of ethylene oxide on ' boxylic group. at least one halogen atom with an
organic compounds which contain reactive hy aromatic amino sulphonic acid the amino group
drogen atoms, as for example in the form of of which contains at least one replaceable hydro
50 hydroxy, carboxyl amino or mercapto groups, gen atom and the sulphonic group of which is
50
and also ?llers, such as clay, china clay and ben
attached to‘ an aromatic nucleus.
,
tonite may be employed with the said products.
.2. The process for the production of amides
Mixtures of the said products with disinfecting
or pharmaceutical substances can be prepared to
55 a greater extent than in the case of soaps. '
The products according to this invention may
be converted into all the forms known for the
use of soaps. In particular, ?akes, threads, cut
tings, coarse and ?ne powders, solid pieces, such
60 as hand and grained soap, or concentrated solu
tions, as for example liquid soaps may be pre
pared therefrom. Generally speaking the sodium
salts of the said products are most suitable for
the said purposes, but the other alkali salts and
65 in particular the saltswith ammonia or water
soluble organic bases, as for example hydroxy
alkylamines, are distinguished by an excellent
activity.
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The following examples will further illustrate
70 the nature of this invention but the invention is
‘not restricted to these examples. I The parts are
by weight.
Example 1
Chlorine is vled into 300 parts of stearic acid
76 chloride at a temperature of 90° C. until an ab
which comprises condensing a soap-forming ali
phatic carboxylic acid substance selected from
the class consisting of carboxylic acids, carbox
ylic halides, ,anhydrides and esters, containing
outside the carboxylic group at least one halogen
atom with an aromatic amino sulphonic acid the
amino group of which contains at least one re
placeable hydrogen atom and the sulphonic group 60
of which is attached to an aromatic nucleus.
3. The process‘ for the production of amides
which comprises condensing a halogen-contain
ing aliphatic acid obtainable from high molecular
organic substances of natural origin with an aro
matic amino sulphonic acid -the amino group 65
of which contains at least one replaceable hydro
gen atom and the sulphonic group of which is
attached to an aromatic nucleus.
4. The process for the production of amides 70
which comprises condensing a derivative of an
aliphatic carboxylic acid selected from the class
consisting of ,carboxylic halogenides, anhydrides ,
and esters, containing outside the carboxylic
groups at least one halogen atom with an aromat- 75
3
. 3,120,557
ic amino sulphonic acid the amino group of which the class consisting of carboxylic acids, carboxylic
5
contains atleast one replaceable hydrogen atom
halides, anhydrides and esters, containing outside
and the sulphonic group of which is attached to
an aromatic nucleus.
with an amino sulphonic acid containing at least
5. The process for the production of amides
which comprises condensing a halogen-contain
ing hydrogenated fatty acid obtained from un
saturated fatty acids with an aromatic amino
sulphonic acid the amino group of which con
10 tains at least one replaceable hydrogen atom and
'
the sulphonic group of which is attached to an
aromatic nucleus.
_
one alkyl radicle and the amino group of which
contains at least one replaceable hydrogen atom
and the sulphonic group of which is attached to
an aromatic radicle. '
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11. The process for the production of amides
which comprises condensing a halogen-contain
ing soap-forming aliphatic carboxylic acid sub
stance selected from the class consisting of car
».. 6. The process for the production of amides
boxylic acids, carboxylic halides, anhydrides and
which comprises ‘condensing a halogen-contain
esters, containing outside the carboxylic group
15 ing hydrogenated train oil fatty acid with an
aromatic amino sulphonic acid the amino group
of which contains at least one replaceable hydro
gen atom and the sulphonic group of which is
attached to an aromaticnucleus.
20 " '7. The process for the production of amides
which comprises condensing’ a soap-forming ali
phatic carboxylic acid substance selected from
the class consisting of carboxylic acids, carboxylic
halides, anhydrides and esters, containing out
25 side the carboxylic group at least one halogen
atom with an aromatic amino mono sulphonic
acid the amino gsoup of which contains at least
one replaceable hydrogen atom and the sulphonic
group of which is attached to an aromatic nucleus.
80 8. The process for the production of amides
which comprises condensing a soap-forming ali
phatic carboxylic acid substance selected from
the class consisting of carboxylic acids, carboxylic
at least one halogen atom with a toluidine sul
phonic acid.
12. A colorless carboxylic acid amide derived
from a halogen-containing aliphatic carboxylic ‘
acid with at least eight carbon atoms containing
in the amino radicle at least one aromatic radicle 20
and at least one sulphonic group attached to the
aromatic radicle.
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13. A colorless amide of a halogenated soap
forming acid containing in the amino radicle at
least one aromatic radicle and at least one sul
phonic group attached to the aromatic radicle‘.
14. A colorless amide of a halogenated soap
forming acid containing in the amino‘ radicle at
least one mono-nuclear aromatic radicle and at
least one sulphonic group attached to the arc 30
matic radicle.
15. A colorless amide of a halogenated soap
forming acid and metanilic acid.
‘
halides, anhydrides and esters, containing outside
' 16. A colorless amide of a halogenated soap
the carboxylic group at least one halogen atom
forming acid and amino-sulphonic acids contain 35
with a mono nuclear amino mono sulphonic acid
ing in the amino radicle at least one aromatic
radicle and at least one 'alkyl radicle and a sul
phonic group attached to the aromatic radicle.
the amino group of'which contains at least one
_ replaceable hydrogen atom and the sulphonic
40
the carboxylic group at least one halogen atom
group of which is attached to the nucleus.
9. The process for the production of amides
which comprises condensing a soap forming ali
phatic carboxylic acid substance selected from
17. A colorless amide of a halogen-containing
soap-forming acid and —N-ethyl metanilic acid. .40
18. A colorless amide of a halogen-containing
' the class consisting of carboxylic acids, car
soap-forming acid and toluidine sulphonic acid.
19. A colorless amide of halogen-containing
boxylic halides, anhydrides and esters, contain
_ hydrogenated train oil fatty acids and metanilic.
45 ing outside the carboxylic ‘group at least one
halogen atom with metanilic acid.
10. The process for the production ofv amides
which comprises condensing a soap-forming alla
‘phatic carboxylic acid substance selected from
acid.
45
20. A colorless amide of halogen-containing
hydrogenated train oil fatty acids and toluidine
sulphonic acid.
HANS HAUSSMANN.
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