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Патент USA US2134712

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. Patented Nov. 1, 1938
UNITED STATES
2,134,712
PRODUCTION OF ALKYL PHENOL
SULPHONATES
Lawrence H. Flett, Hamburg, N. Y., assignor to
National Aniline & Chemical Company, Inc.,
New York, N. Y., a corporation of New York
No Drawing. Application September 25, 1935,
Serial No. 42,159
15 Claims. (Cl. 260-512) .
This invention relates to the production of
chemical compounds suitable for use as deter
gents,foamingagents,wettingagents and the like.
It relates more particularly to a method of mak
5 ing products which are nuclear alkyl derivatives
of ‘phenol sulphonic acids in which the alkyl
group contains at least 12 carbon atoms, more
particularly 12 to 23 carbon atoms and especial
ly 14 to 19 carbon atoms.
According to the present invention an ole?ne
hydrocarbon containing at least 12 carbon atoms
(preferably 12 to 23, and especially 14 to 19, car
bon atoms) is condensed with phenol or a cresol,
_ preferably with the aid of a metal halide con
or
densing agent,, to produce the corresponding
nuclear alkyl phenol, and the resulting alkyl
phenol is sulphonated.
The alkyl phenol sulphonic. acid com unds,
obtained in accordance with the present in
vention, are derivatives of phenol (hydroxyben
Zene) and of the cresols (1.2-, 1-3- and 1.4
methyl-hydroxybenzene) corresponding with the
general formula
[3 bl
30 in which A represents hydrogen or a methyl
group, R represents an alkyl hydrocarbon radi
cal linked to the nucleus of the phenol by a non
terminal carbon atom of the alkyl hydrocarbon
radical and containing 12 or more (preferably 12
-» to 23, and especially 14 to 19) carbon atoms, and
M represents hydrogen or a metal, particularly
an alkali metal, or an ammonium or organic
40
ammonium radical. For convenience they will
be hereinafter referred to as “alkyl phenol sul
phonates”, which term generically includes the
phenol and cresol derivatives in the form of the
free acids or their salts.
4
The invention is particularly concerned with
the production of alkyl phenol sulphonates from
double bond, even when the double bond is be
tween the ultimate and penultimate carbon at
oms, condense, in accordance with the present
invention, with phenol and its monomethyl de
rivatives to produce alkyl phenols and cresols in
which the alkyl radical is not linked to the phenol
nucleus by an end carbon atom but by an inter
mediate carbon atom. It has been found when
the said alkyl phenols are sulphonated and the
resulting alkyl phenol sulphonates are employed 10
in the art, particularly in the form of their solu
ble salts, and especially their alkali metal salts,
very advantageous detergent, wetting and foam
ing action is obtained. Without limiting the in
vention to any theoretical considerations, it ap
pears the branched carbon chain alkyl radical
which results from the process of the present
invention, contributes to the valuable properties
of the products. The invention is accordingly
of particular advantage in that it permits the
production of branched chain nuclear alkyl de
rivatives of phenol and cresol sulphonic acids
from readily available, straight-chain ole?ne hy
drocarbons which, in turn, can be obtained from
natural products, such as higher fatty acids and
their esters (as for example by decarboxylation,
pyrolysis, etc.) The invention is also of value
in permitting the obtainment of branched-chain,
nuclear alkyl derivatives of phenol and cresol
sulphonicacids from readily available hydrocar
bon material containing straight- or branched
chains, such as petroleum distillates, as for ex
ample, by halogenation followed by dehalogena
‘ tion.
The invention will be illustrated by the fol
lowing speci?cexamples in which the parts are
by weight and temperatures are in degrees cen
tigrade. It will be understood by those skilled
in the art that the scope of the invention is not
limited to these speci?c examples.
40
Example l.-700 parts of an ole?ne with a
boiling point ranging from 237° to 262° and hav
ing an average carbon content of 14 to 15 carbon
bon atoms, and preferably containing at least 7
atoms (and obtained by the dechlorination of the
monochlor hydrocarbon separated by fractiona 45
tion from the products resulting from chlorin
of said carbon atoms in a straight chain, and
ation of petroleum distillates which boil at ap~
' ole?ne hydrocarbons containing at least 12 car
prepared, for example, by the decarboxylation
of higher fatty acids or esters, the dehydration
of an alcohol containing at least 12 carbon
atoms, the removm of hydrogen halide from an
alkyl halide containing at least 12 carbon atoms,
or in any other manner.
Ole?ne hydrocarbons containing at least 12
55 carbon atoms in a straight chain and having a
proximately 250° at atmospheric pressure), 700
parts of phenol, and 350 parts of anhydrous zinc
chloride are mixed and heated together while
agitated under a reflux condenser at a tempera
ture around 180° to 190° for from 5 to 16 hours.
The condensed mass is diluted and washed with
water until reasonably free of water-soluble im
purities, and the crude brownish oil is distilled
2,184,712
2
in vacuo. .The distillate boiling between 195°
and 240° at 15 mm. pressure is collected. It is
a faintly colored to water-white oil, insoluble in
water and dilute caustic soda.
100 parts by weight of the resulting oil are
mixed with 148 parts by weight of- sulphuric acid
monohydrate at 30°, then heated to 70°-75° and
held there until a sample is completely soluble
in water and in neutral, acid or alkaline aqueous
10 solutions, and a neutral 0.2 per cent solution
does not precipitate calcium salts from a soluble
calcium salt solution containing the equivalent
of 0.224 gram calcium oxide per liter. The sul
phonation mix is poured into water, diluted to a
.15 ?nal volume of 450 to 600 parts, and made neu
. tral (for example, to delta paper, Congo paper,
50°.
Thereafter, the temperature is slowly
raised to 90°—95° and held there until a. sample
of the sulphonation mass is soluble in water and
does not precipitate calcium salts. The sulfo
nation mass is diluted with water to approxi
mately 450 to 600 parts and neutralized with al
kali. The solution is clari?ed by ?ltration, if
necessary, and evaporated to dryness. The
product is similar to that obtained in Example 1.
Emmple 5.—To 100 parts of the alkyl phenol
used in Example 1, while being agitated, 64
parts of 65% oleum are added slowly. The tem
perature during addition of oleum is held at
30° while the ?nishing temperature is not al
lowed to exceed 45°. The sulfonation is com
plete when a sample is completely soluble in wa
ter and does not precipitate calcium salts from
dilute solutions. The sulphonation mass is di
brilliant yellow, or brom-phenol-blue) with al
kali, for example caustic soda, or potashor their
equivalents. The neutral solution is evaporated luted, neutralized, ?ltered and evaporated to
20 to dryness. If desired, the neutral solution can dryness as described in previous examples.
The products of the above examples contain .
be clari?ed by ?ltration'before being evaporated
‘ inorganic salts (alkali metal sulphates) in ad
to dryness.
mixture _with the alkyl phenol sulphonates.
The product thus obtained is a mixture of al
kyl phenol sulphonates, sodium sulphate and When it is desired to employ the alkyl phenol
25 some impurities.
The chief components are
sulphonates in a form free from inorganic salts, 25
alkyl phenol sulphonates having the probable
they may be obtained from the mixed products
formula
produced by such processes as are given in the
on
above speci?c examples by taking advantage of
the solubility of the alkyl phenol sulphonate salts
in alcohol and other organic solvents.
Thus a
mixture of a salt of the sulphonated product
35 wherein Re represents an aliphatic hydrocarbon
group, M represents an alkali metal or equivalent
derived from the base used for neutralization,
and p is 1 or 2 but mainly 1. For the most part,
the alkyl phenol sulphonates contain branched
40 carbon chains in the groups represented by Re
and these groups are connected to the phenol
nucleus by primary, secondary or tertiary car
bon atoms. The chief components of the mix
ture contain 14"or 15 carbon atoms in the alkyl
group represented by Re.
Imthe form‘ 01- the alkali metal and alkaline
earth metal salts it is a friable solid, faintly
and an inorganic sulphate may be extracted
with alcohol, and the resulting extract may be
evaporated to leave a residue of the puri?ed salt
of the sulphonated product, as illustrated by 35
the following speci?c examples.
Example 6.—'I'he sulphonation mixture result
ing Jrom the process of above Example 2 is di
luted with 1750 parts of 70% denatured alcohol,
and neutralized with solid soda ash (NazCOa). 40
The mixture is ?ltered and the ?ltrate evapo
rated to dryness to obtain the sodium salt of the
alkyl phenol sulphonic acid practically free from
salts of inorganic acids. The resulting product
is similar to that obtained in Examples 1 and 2
but it does not contain the inorganic salts pres
ent in that product, and it is soluble in benzene,
colored light brown to white, readily reduced
alcohol and other organic solvents.
to a comminuted or powdery form (resembling
Example 7.-—The neutralized solution of the
sulphonic acid obtained by the process of above
Example 5 is treated with such an amount of al
cohol that the resulting alcohol solution in water
contains more than 50% alcohol. The solution
is ?ltered to remove precipitated impurities
which are mostly inorganic salts, and the ?ltrate
50 powdered soap) and readily solube in water.
Exampe 2.—The sulphuric acid monohydrate
in Example 1 is substituted by 200 parts of 66°
Bé. sulphuric acid which is fed slowly to the agi
tated alkyl phenol at a temperature of 65°-70°.
The mixture is slowly heated to 90°-100° and
held at this temperature for one hour, or until a
sample is completely soluble in water and does
not precipitate calcium salts (as in Example 1).
Example 3.--100 parts of the alkyl phenol em
ployed in Example 1 are mixed slowly with 50
parts of chlorsulphonic acid, and the mix is
heated to 70°-90° until evolution of hydrochloric
acid practically ceases and a sample of the sul
fonation mass is completely soluble in water
and does not precipitate calcium salts (as in Ex
ample 1). The sulphonation mass is then di
luted with water, "neutralized with alkali, ?l
tered and evaporated to dryness, etc., as in Ex
ample 1. The resulting alkyl phenol sulphonate
is similar to that produced in Example 1.
Example 4.—100 parts of the alkyl phenol
used in Example 1 are mixed with 24 parts of
acetic anhydride, and while the mass is agitated,
132 parts of 26% oleum are added slowly, so
75 that the temperature of the mix does not exceed
'
5
containing the sulphonate is evaporated to dry
ness to yield the dry sulphonate practically free
from inorganic salts. The product, which is sim
ilar to that obtained in Example 6, is suitable for
use in organic solvents as a cleaning composition 60
and is an excellent emulsi?er.
Instead of adding alcohol to the dilution mass,
the dry crude sulphonate may be repeatedly ex
tracted with alcohol, and the alcohol extracts
combined, ?ltered and evaporated to dryness.
65
Example 8.--A mixture of 15 parts zinc chlo
ride, 150 parts of the ole?ne used in Example 1,
and 100 parts of phenol is re?uxed with agitation
for 15 hours at 170° to 175°. The mixture is
cooled, and the liquid portion is decanted there 70
from and distilled in vacuo. The distillate boil
ing between 150° and 225° at 7 mm. pressure is
collected. It is an oil comprising an alkyl phenol
mixture in which the alkyl group contains an
averagev of 14 to 15 carbon atoms.
75
%
2,134,712
by R in the foregoing formula are contained in
To 20 parts of this-oil there is slowly added,
with agitation, 20 parts of sulphuric acid mono
the resulting alkyl phenol and preferably only
one. Thus, at least 1.25 mols of phenol per mol
of olefine is preferably employed in the condensa
hydrate, the temperature being maintained at
28° to 30°.
The mixture is stirred at 30° to 35°
tion.
. for 2 hours or until the sulphonation is com
pleted, then diluted with 800 parts of water, neu
tralized with caustic soda, and evaporated to
dryness. The product is similar to that obtained
in Example 1.
Example 9.-To 100 parts of an alkyl phenol
10
obtained by condensing phenol with an ole?ne of
boiling range 232° to 255° (and derived from
phenol containing one long alkyl group will be
less.
As condensing agents there may be employed
anhydrous zinc chloride, anhydrous aluminum 10
chloride, anhydrous antimonic chloride, anhy
drous ferric chloride, sulphuric acid (66° Bé.
monohydrate, oleum), etc. Anhydrous zinc chlo
ride is preferred. While the zinc chloride and
other metal halide condensing agents mentioned 15
chlorinated petroleum distillates of about the
same boiling range), as per methods described
15 herein, 64 parts of 65% oleum are added at such
have been referred to as "anhydrous”, it is noted
that said condensing agents may be employed in
a rate that the temperature of the mixture does
not exceed 30°. The temperature thereafter is
raised to 35° to 45° and held at that point till a
sample of the sulphonation mass is completely
20 soluble in water and does not precipitate calcium
a partially hydrated condition containing small
amounts of water, for instance such as are ab
sorbed from the surrounding atmosphere or 20
otherwise in commercial operation, but insuffi
salts from dilute solutions. The mass is diluted
with water, and the resulting solution is neu
vcient to interfere with their action as condens
ing agents.
tralized with caustic soda, ?ltered and evaporated
condensing agent, the period of heating may be
extended to 16 hours or more without seriously
harming the quality or decreasing the yield of 30
the alkyl phenol.
alkyl group contains about 14 to 15 carbon atoms
but averages somewhat lower than the product
of Example 1.
Instead of the alkyl phenol product employed
in the above examples for the production of alkyl
phenol sulphonates, other alkyl phenols and cre
sols may be employed. The following additional
examples in which the parts are by weight and
the temperatures are in degrees centigrade, il
lustrate the preparation of such alkyl phenol
products.
Example 10.—-An admixture of 50 parts of
cetcne (obtained by pyrolysis of spermaceti), 50
parts of phenol and 50 parts of fused, powdered
zinc chloride is re?uxed and agitated for 16 hours.
The reaction mass is washed with water and
fractionally distilled. The fraction boiling be
tween 238° to 252° at 13 mm. is separately col
lected. It is a white oil, insoluble in water and
has a speci?c gravity less than 1.
Example 11.--A mixture of 50 parts of phenol,
50 parts of 1.2-heptadecene (obtained by distil
lation of a mixture of oleic acid and sodium
ethylate), and 25 parts of anhydrous zinc chlo
ride is heated with stirring at 90° to 120° .for‘ 15
The ‘resulting reaction mass is washed
with water and then subjected to fractional dis
tillation. The portion boiling between 220° and
It is a
colorless, or nearly so, oil consisting mostly of
heptadecyl phenol.
.
The time during which the condensation re 25
action of the ole?ne and phenol may be carried
out also may be varied. With zinc chloride as the
to yield an alkyl phenol sulphonate practically
free from inorganic salts, as described in Ex
amples 6 and '1 above. The resulting product is
chie?y an alkyl phenol sulphonate in which the
270° at 15 mm. is separately collected.
The amount of condensing agent
employed may vary.‘
to dryness. Or, the solution or ?nal product may
be extracted with alcohol of greater strength
.25
than 50% and the extract evaporated to dryness
55 hours.
A ratio as low as 1 to l or even lower may
be employed, but the yield of the resulting alkyl
‘
By carrying out the condensation in the pres
ence of 10 parts of concentrated sulphuric acid
at 6° to 12°, in place of zinc chloride, followed by
washing and distilling the resulting product and
collecting, the fraction distilling between 220°
and 270° heptadecyl phenol is also obtained.
As above indicated, changes may be made in
'
The crude alkyl phenol resulting from the con
densation is preferably puri?ed, as for example,
by fractional distillation and collecting a middle
fraction having in general a boiling point range 35
of not more than 100° C. and the puri?ed com
pound is preferably employed for sulphonation.
Distillation is preferably carried out at a pres
sure not exceeding 30 mm. to avoid decomposition.
In sulphonating the alkyl phenol or cre
40
sol, an inert solvent and/or a sulphonation as
sistant may or may not be used. As sulphonat
ing agents there may be employed sulphuric acids
of various strengths (e. g., 66° Bé., sulphuric
acid, sulphuric acid monohydrate,’ oleum), chlor 45
sulphonic acid, etc. As solvents or diluent there
may be employed any inert organic liquid which
is not readily sulphonated; such as halogenated
hydrocarbons of the aliphatic and aromatic se
ries, as for example, carbon tetrachloride, di 50
chlorethane, tetrachlorethane, dichlorbenzene,
etc.
As sulphonation assistants there may be
employed the lower organic acids and/or their
anhydrides, as for example, acetic acid, acetic
anhydride, etc.
55
The sulphonation may be carried out with the
aid of heating or cooling, as required, depending
upon the ease of sulphonation of the alkyl phenol
or cresol and the sulphonating power of the
sulphonating agent. For example, temperatures 60
as low as about 0° and as high as about 140° C.
may be employed. In general the more vigorous
the sulphonating agent the lower is the pre
ferred temperature.
Ordinarily the completion
of the sulphonation is carried out at a tempera
ture in the neighorhood of about 25° to about
ployed.
80° C. The ratio of sulphonating agent employed
with respect to the alkyl phenol also may be
varied. While the preferred amounts are given
in the above examples, an amount of sulphuric 70
acid or other sulphonating agent equivalent -to
from 1 to about 5 parts by weight of sulphuric
acid monohydrate per part by weight of the alkyl
with respect to the phenol is such that not more
phenol may be employed.
the process hereinbefore described without de
parting from the scope of the invention.
Thus
phenol, ortho-, meta-,or para-cresol may be em
Preferably the proportion of ole?ne employed
75 than two alkyl radicals of the type represented
'
The extent to which the sulphonation is car
75
4
2,134,712
ried out may vary with the individual material
being sulphonated and the use to be made of the
sulphonated product. In general the extent of
sulphonation of the alkyl phenol treated is such
as to form chie?y the monosulphonic acids of
the alkyl phenol, and to sulphonate impurities as
well, if present.
In some cases, a degree of sul
phonation which corresponds with a product
having maximum detergent properties is notv
10 completely soluble in water to form a clear solu
tion and/or may cause some precipitation of
lime salts. (An aqueous solution of calcium chlo
ride containing the equivalent of 0.224 gram of
calcium oxide per liter of solution is merely em
ployed in the above examples as a representative
hard water solution for test purposes. It is to
be noted that the invention is in no respect lim
ited thereto.)
The alkyl phenol sulphonates may be produced
20 in accordance with the present invention in the
form of their free sulphonic acids or in the form
of salts of metals (as for example, of the valkali
metals) or of organic bases, or of ammonia, etc.
The salts may be obtained in any suitable man
25 ner; for example by reacting the sulphonated
product, either in the crude form resulting ‘from
the sulphonation or in a puri?ed form, with a
metal oxide or hydroxide, ammonia or an or
ganic base, or of a suitable salt of one of these,
30 in an amount adapted to form a neutral product.
Among the bases, oxides and salts which may be
combined with the sulphonated products to pro
duce salts in accordance with the present inven
tion are, for example sodium, potassium and
35 ammonium hydroxides; sodium, ‘potassium and
ammonium carbonates and bicarbonates; am
monia; magnesium oxide; ethylamine; pyridine;
triethanolamine;
propanolamines;
butanola
mines; diamino propanol; ethylenediamine; tri
_ethylene tetramine; etc.
The reaction mixtures resulting from the sul
phonation' of the alkyl phenol or cresol may also
be directly employed for the formation of mixed
products, as for example, mixtures of salts of the
alkyl phenol sulphonic acid and of other acids
present in said reaction mixtures, which mixtures
of salts are also useful as such. Thus, the sul
phonation reaction mixture resulting from the
treatment of the alkyl phenol or cresol with an
amount of sulphonating agent in excess of that
theoretically required to effect the desired de
gree of sulphonation may be treated with a suit
able inorganic or organic base or basic salt (as
for example, one of those mentioned) and the
55 resulting mixture of the salt of the sulphonated
alkyl phenol or cresol and the organic and/or
inorganic salt (as for example, sodium sulphate)
may be jointly isolated from the reaction mix
ture and employed as such. If it is desired to
60 produce a salt of the sulphonated alkyl phenol
tain of the salts, such as the salts of the aromatic
monoamines and the aliphatic and aromatic poly
amines, are oils which generally are insoluble in
water but soluble in organic solvents (as for
example, benzene, gasoline, etc.) and in aqueous
solutions of alkalis (presumably by conversion to
the salts of the alkalis) .
This application is a continuation in part of my
applications'Serial Nos. 691,081 and 691,082, ?led
September 26, 1933.
~
I claim:
1. Avmethod of producing a nuclear alkyl de~
rivative of a sulphonated phenol, which comprises
condensing a member of the group consisting of
phenol and its monomethyl derivatives with an
ole?ne hydrocarbon containing at least 12 carbon
atoms with the aid ‘of a metal halide condensing
agent, and sulphonating the resulting product.
2. A method of producing a nuclear alkyl de
rivative of a sulphonated phenol, which comprises
condensing a member of the group consisting of
phenol and its monomethyl derivatives with an
ole?ne hydrocarbon containing at least 12 carbon
atoms of' which at least 7 are in a straight chain,
with the aid of a metal halide condensing agent,
and sulphonating the resulting product.
3. A method of producing a nuclear alkyl de
rivative of a sulphonated phenol, which com
prises forming a phenol compound containing a
high alkyl substituent by condensing a phenol
compound of the group consisting of phenol and
its monomethyl derivatives with an ole?ne hydro
carbon containing at least 12 carbon atoms in a
straight chain, with the aid of a condensing
agent, the amount of ole?ne hydrocarbon not ex— :
ceeding about that required to produce mono
alkylation of the phenol compound, and sul
phonating the resulting product.
4. A method of producing a nuclear alkyl de
rivative of a sulfonated phenol which comprises
forming a phenol compound containing a high
alkyl substituent by condensing a phenol com
pound of the group consisting of phenol and its
monomethyl derivatives with an ole?ne hydro
carbon containing at least 12 carbon atoms in a
branched, open-chain with the aid of a condens
ing agent, the amount of ole?ne hydrocarbon not
exceeding about that required to produce mono
alkylation of the phenol compound, and sul
phonating the alkylated phenol compound.
a.
'
5. A method of producing a nuclear alkyl de In
revative of a sulphonated phenol, which com
prises forming a phenol compound containing a
high alkyl substituent by condensing a phenol
compound of the group consisting of phenol and
its monomethyl derivatives with an open-chain
ole?ne hydrocarbon containing at least 12 carbon
atoms and having a double bond‘ between the
ultimate and penultimate carbon 'atoms, in the
presence of a metal halide condensing agent, the
or cresol in a form substantially free from inor- . amount of ole?ne hydrocarbon not exceeding
ganic salts (for example, inorganic sulfates)
about that required to produce monoalkylation of
this may be accomplished by taking advantage the phenol compound, and sulphonating the al
of the solubility of the salts of the sulphonated kylated phenol compound.
65 products in alcohol and other organic solvents
6. A method of producing a nuclear alkyl de
as disclosed in the above examples.
rivative of a sulphonated phenol, which comprises
The sulphonated products in the form of metal
condensing one mol of a phenol compound of the
lic salts or salts of inorganic bases are usually yel
group consisting of phenol and its monomethyl de
lowish to white, friable solids; and in the form of rivatives with not more than one mol of an ole?ne
70 salts of organic bases vary from viscous oils to hydrocarbon containing at least 12 carbon atoms
semi-solids to solids. In general, the salts are with the aid of a zinc halide as a condensing 71
readily soluble in water and in aqueous (neutral, agent, whereby an alkyl phenol compound is pro
acid or alkaline) solutions to form solutions which duced, and sulphonating said alkyl phenol com—
are faintly colored brown or yellow, which are pound.
76 of a soapy nature and which foam readily. Cer
7. A method of producing a nuclear alkyl de
./
5
2,134,719
rivative of asulphonated phenol, which comprises
condensing one mol of a phenol compound of the
group consisting of phenol and its monomethyl
10
derivatives with not more than one mol of an
12. A method of producing a nuclear alkyl de
rivative of a sulphonated phenol, which comprises
open-chain ole?ne hydrocarbon containing 12 to
condensing at least 1.25 mols of a phenol com
23 carbon atoms with the aid of a condensing
pound of the group consisting of phenol and its
agent, whereby an alkyl phenol compound is pro
duced, and sulphonating said alkyl phenol com
monomethyl derivatives with one mol. of an ole
?ne hydrocarbon containing 14 to 19 carbon atoms
pound.
in a straight chain and having a double bond be
_
8. A method of producing a nuclear alkyl de
rivative of a sulphonated phenol, which come
prises condensing one mol of a phenol compound
of the group consisting of phenol and its mono
methyl derivatives with not more than one mol of
15 an open-chain ole?ne hydrocarbon containing 12
to 23 carbon atoms, of which at least seven are in
a straight chain, with the aid of a condensing
agent, whereby an alkyl phenol compound is pro
duced, and sulphonated said alkyl phenol com
20 pound.
9. A method of producing a nuclear alkyl de
rivative of a sulphonated phenol, which com
prises condensing one mol. of a phenol compound
of the group consisting of phenol and its mono
methyl derivatives with not more than one mol.
of an open-chain ole?ne hydrocarbon containing
12 to 23 carbon atoms and having a double bond
between the ultimate and penultimate carbon
atoms, in the presence of a metal halide condens
80 lng agent, whereby an alkyl phenol compound is
produced, and sulphonating said alkyl phenol
compound.
10. A method of producing a nuclear allgvl de
rivative of a sulphonated phenol, which comprises
35 condensing one mol. of a phenol compound of the
group consisting of phenol and its monomethyl
tween the ultimate and penultimate carbon 10
atoms, with the aid of anhydrous zinc chloride,
whereby the corresponding alkyl phenol com—
pound is produced, and sulphonating said alkyl
phenol compound.
13. A method of producing a nuclear alkyl de 15
rivative of a sulphonated phenol, which comprises
condensing at least 1.25 mols of a phenol com
pound of the group consisting of phenol and its
monomethyl derivatives with one mol. of an ole
?ne hydrocarbon containing 12 to 23 carbon atoms 20
and resulting from the removal of hydrogen chlo
ride from a chlorinated aliphatic hydrocarbon,
with the aid of anhydrous zinc chloride, whereby
the corresponding monoalkyl phenol compound
is produced, ‘and sulphonating said monoalkyl
phenol compound.
condensing at least 1.25 mols of a phenol com—
pound of the group consisting of phenol and its 30
monomethyl derivatives with one mol. of a mix
ture of ole?ne hydrocarbons containing 12 to 23
carbon atoms and resulting from the removal of
hydrogen chloride from a mixture of chlorinated
aliphatic hydrocarbons, with the aid of anhy 35
drous _zinc chloride, whereby a mixture of the
corresponding monoalkyl phenol compounds is
produced, and sulphonating said monoalkyl phe
atoms, of which at least '7 are in a straight chain,
with the aid of a zinc halide as a condensing
nol compounds.
agent, whereby an alkyl phenol compound is pro
duced, and sulphonating said alkyl phenol com
rivative of a sulphonated phenol, which com
prises condensing at least 1.25 mols of a phenol
compound of the group consisting of phenol and
pound.
-
11. A method of producing a nuclear alkyl de
rivative of a sulphonated phenol, which comprises
condensing at least 1.25 mols of a phenol com
pound of the group consisting of phenol and its
monomethyl derivatives with one mol. of an ole
25
14. A method of producing a nuclear alkyl de
rivative of a sulphonated phenol, which comprises
ole?ne hydrocarbon containing 14 to 19 carbon
derivatives with not more than one mol. of an
45
ing alkyl phenol compound is produced, and sul
phonating said alkyl phenol compound.
1
15. A method of producing a nuclear alkyl de
40
its monomethyl derivatives with one mol. of a
mixture oi.’ ole?ne hydrocarbons containing 14 45
to 19 carbon atomsand resulting from the re
moval of hydrogen chloride from a mixture of
chlorinated aliphatic hydrocarbons, with the aid
fine hydrocarbon containing at least 12 carbon
of anhydrous zinc chloride, whereby a mixture of ,
atoms, of which at least 7 are in a straight chain
the corresponding alkyl phenol compounds is pro
duced, and sulphonating said alkyl phenol com 60
and penultimate carbon atoms, with the aid of
anhydrous zinc chloride, whereby the correspond
pounds.
50 and having a double bond between the ultimate
'
LAWRENCE‘ H. FLE'I'I‘.
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