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Патент USA US2134711

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2,134,7i1
Patented Nov. 1, 1938
2,134,711
PRODUCTION OF NUCLEAR ALKYL DERIVA
TIVES 0F PHENOLS
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. 42,158
_10 Claims.
This invention relates to the production of
chemical compounds suitable for use as deter
gents, foaming agents, wetting agents, and the
like. It relates more particularly to a method
5 of making products which are nuclear alkyl de
rivatives of phenol sulfonic acids in which the
alkyl group contains at least 12 carbon atoms,
more particularly 12 to 23 carbon atoms, and
especially 14 to 19 carbon atoms.
According to. the present invention, an alkyl
10
halide containing at least 12 carbon atoms (pref
erably 12 to 23, and especially 14 to 19, carbon
atoms) is condensed with phenol or a cresol,
preferably with the aid of a metal halide con
15 densing agent, to produce the corresponding nu
(Cl. 260-512)
whether a primary, secondary or tertiary alkyl
group).
The said alkyl- phenol sulfonates may be used
instead of the usual soaps for scouring, cleaning,
washing and toilet purposes as well as for other
purposes for which ordinary soaps have hereto
fore been employed. They also may be employed
in conjunction with ordinary soaps, since it has
been found that the presence of the said alkyl
phenol sulfonic acid compounds serves to prevent
objectionable precipitates from forming in hard
0
water or in acid treating baths or in salt baths.
They have the further advantages of being in'
general better wetting agents and more soluble
than the usual soaps, and of leaving the washed Id 5
clear alkyl phenol, and the resulting alkyl phenol - goods with a soft feel. Inasmuch as the water
solutions of said components in the form of their
is sulfonated.
The alkyl phenol sulfonic acid compounds re
sulting from the process of the present invention,
20 in the form of the free sulfonic acid or a salt
thereof, correspond with the general formula
OH
A
igjnam
in which A represents hydrogen or a methyl
group, R represents an alkyl hydrocarbon radi
cal (which may be straight or branched, primary,
secondary or tertiary) containing at least 12 car
bon atoms (preferably 12 to 23, and especially
14.- to 19 carbon atoms) and M represents hydro
gen or a metal, particularly an alkali metal, or
' an ammonium or organic ammonium radical.
The said alkyl phenol sulfonic acid compounds
are derivatives of phenol (hydroxybenzene) and
of the cresols (1.2-,‘1.3-, and IA-methyl-hy
droxybenzene) in which the alkyl hydrocarbon
40 radical represented by R in the foregoing for
mula is directly linked to a nuclear carbon atom
and in which the sulfonate group (represented
in the foregoing formula by —-SO2OM) is also
directly linked to a nuclear carbon atom. For
45 convenience they will be hereinafter referred to
as “alkyl phenol sulfonates”, which term generi
cally includes the phenol and cresol derivatives,
in the form of the free acids or the salts. The
alkyl phenol sulfonates preferably employed in
5 O accordance with the present invention are those
in which the alkyl group contains a branched
carbon chain, whether linked to the benzene nu
cleus by an end carbon atom (an alpha carbon
55 atom) or an intermediate carbon atom (that is,
alkali metal salts are neutral in reaction, the lat
ter may be safely used for the washing of delicate
silks and other line fabrics as well as for per
sonal toilet purposes.
The said alkyl phenol sulfonates are also val
uable wetting agents useful in the textile and
related ?elds and as insecticidal, fungicidal,
emulsifying, dispersing and/or tanning agents.
The invention- will be illustrated‘by the fol
lowing speci?c examples in which the parts are
by weight and temperatures are in degrees cen
tigradel It will be understood by those skilled
in the art that the scope of the invention is not 30
limited to these speci?c examples. '
Example 1.-Sodium cetyl phenol sulfonate
A mixture of 80 parts of cetyl chloride (pre
pared from commercial cetyl alcohol and boil
35
ing within the range of 160° to 210“ at 5 mm.
pressure), 80 parts of phenol and 10 parts of
anhydrous zinc chloride, while being agitated
vigorously, is heated to a temperature of 175°
and then is maintained for 6 hours at a tem 40
perature of 175° to 185°. ' The reaction mixture
is all-owed to cool, and the oil is decanted off
and fractionally distilled in a vacuum. The frac
tion of the distillate boiling from 190° to 250° at
5 mm. of mercury pressure is separately col
45
lected. The product, which comprises cetyl phe
nol, is a viscous oil which is partially solid at
room temperature and completely solid at 5°. '
An equal weight of ‘100% sulfuric acid is added
to the product at a temperature of 10° to 25°. 50
The reaction mass is agitated while maintaining
this temperature until a test portion is not turbid
in dilute alkaline solution. After drowning in
ice water the solution is neutralized with aqueous
sodium ‘hydroxide and evaporated to dryness.
55
2
2,184,711
Example 2.--Sodium myristyl paral-cresol
sulfonate
respect to the phenol may vary; but preferably
the proportion of alkyl halide employed with re
A mixture of 120 parts of myristyl bromide
(prepared from the alcohol and boiling within
spect to the phenol is such that not more than
two of the said alkyl radicals of the type repre
sented by R in the foregoing formula are con
tained in the resulting alkyl phenol and prefer
ably only one. Thus, at least 1.25 mols of phenol
per mol. of alkyl halide is preferably employed
the range of 150° to 170° at 6 mm. pressure), 102
parts of para-cresol and 10 parts of zinc chloride
(as a condensing agent) is agitated and heated
at a temperature of about 175° (: 5°) for 16
hours. After cooling, myristyl-para-cresol is ob- . in the condensation.
10 tained from the mass by decantation, fractional
distillation in a vacuum, andcollection of the
fraction boiling from 175° to 235° at a pressure
of 5 mm. of mercury. The product is a light
brown viscous oil. An equal weight of 100%
15 sulfuric acid is added to the product at a tem
perature of 10° to 25°. The reaction mass is
agitated while maintaining this temperature
until a test portion is not turbid in dilute alkaline
solution. After drowning in ice water, the solu
20 tion is neutralized with aqueous sodium hy
droxide'and evaporated to dryness.
Emample 3.-—Sodium lauryl phenol sulfonate
A mixture of 185 parts of lauryyl chloride (pre
25 pared from commercial lauryl alcohol), 100 parts
of phenol and 30 parts of zinc chloride (as a
condensing agent) is heated with agitation at a
temperature of 170° to 180° under a re?ux con
denser for 20 hours. The reaction mixture is
30 allowed to cool and the oil which separates is
decanted off and fractionally distilled in a vac
uum. The fraction of the distillate boiling be
tween 150" and 230° at 4 mm. pressure of mer
cury is separately collected.
It consists chie?y
35 of lauryl ‘phenol in admixture with other alkyl
phenols. To 20 parts of the lauryl phenol prod
uct thus obtained, there is slowly added with
agitation 20 parts of sulfuric acid monohydrate,
‘ and the mixture is maintained at a temperature
40 of 30° to 35° for 3 hours or until the desired
sulfonation is effected. The mass is diluted with
400 parts of water, and the solution thus ob
tained is neutralized with caustic soda and evap
orated to dryness. The product thus obtained
45 comprises a mixture of alkyl phenol sulfonates
together with some sodium sulfate, of which a
predominant compound is the sodium salt of
' lauryl phenol sulfonate having the probable
formula:
.
OE
50
0101121
CH—
55
It will be realized by those skilled in the art
that changes may be made in the processes here
inbefore described, without departing from the
scope 'of the invention.
60
Thus, phenol, ortho-, meta-, or para-cresol or
‘
Various alkyl halides containing at least 12
carbon “atoms may be employed; as for example,
chlorides and bromides of the saturated and un
65
saturated'hydrocarbons of the ‘aliphatic class,
including straight-chain and branched-chain
monochlorides and monobromides in which the
halogen atom is linked to an end carbon atom or
an intermediate carbon atom. Those in which
70 the hydrocarbon radical of the halide contains a
branched carbon chain or which result in a
product in which the radical represented by R
in the foregoing formula contains a branched
carbon chain are preferred.
75
yield of the resulting alkyl phenol containing
one alkyl radical of the said type represented by
R will be less. .
-
As condensing agents there may be employed
anhydrous zinc chloride, anhydrous aluminum 15
chloride, anhydrous antimonic chloride, anhy- .
drous ferric chloride, zinc, zinc oxide, copper,
magnesium, etc. During the condensation with
zinc or zinc oxide, a zinc halide is probably
formed and hence also with these substances the
condensation appears to take place in the pres
ence of a zinc halide. In general, anhydrous
zinc chloride is preferably employed as thecon
(lensing agent since, on the whole, it gives more
205
uniform products and better yields, as well as
sulfonated products of superior color and quality. 25
While the zinc chloride and other metal halide
condensing agents mentioned have been referred
to as “anhydrous”, it is noted that said con
densing agents may be employed in partially hy 30
‘drated condition containing small amounts of
water, for instance such as are absorbed from
the surrounding atmosphere or otherwise in com
mercial operation, but insu?icient to interfere
with their action as condensing agents. Even 35
when the zinc chloride contains an equal weight
of water it functions as a'condensing agent; but
such large amounts of water are preferably
avoided.
The condensation may be carried out at vari 40
ous temperatures; for example, room tempera
ture to the boiling point of the reaction mixture,
or higher. Temperatures from about 60° to
about 180° C., or to the somewhat higher re
?uxing temperatures, and especially above 100°
C.. are preferably employed with zinc chloride
as the condensing agent.
The amount of condensing agent employed
may vary. For example, in using zinc chloride
as the condensing agent and a long-chain alkyl
chloride about 5 to about 20 per cent of anhy 50
drous zinc chloride, based on the weight of the
alkyl chloride, is su?icient.
—BO:N8
OHi
their mixtures may be employed.
A molar ratio as low as
1 .to 1, or even lower, may be employed, but the 10
The proportion of alkyl halide employed with
The time during which the condensation re
action of the alkyl halide and the phenol may 55
be carried out also may be varied. In general
the condensation of a long-chain alkyl chloride
with phenol or a cresol is satisfactorily complete
in about 1 hour at re?uxing temperature (ap
proximately 180° C.) or in about 3 to 6 hours 60
at 135° C., but is'continued for a longer time for
best results in preparing a detergent. With zinc
chloride as the condensingv agent, the period of
heating at re?uxing temperature may be ex
tended to 16 hours or more without seriously 65
harming the quality or substantially decreasing
the yield»~ of the alkyl phenol.
The-crude alkyl phenol resulting from the con
densation is preferably puri?ed, as for example,
by fractional distillation at pressures not exceed
ing 30 mm., and the puri?ed compound is prefer
ably employed for sulfonation, when the product
'is to be employed as a- detergent, in view of the
resulting superior detergent properties.
As sulfonatingagents there may be employed
3 .
2,134,711
sulfuric acids of various strengths (e. g., 66° Bé.
sulfuric acid, sulfuric acid monohydrate, oleum)
chlorsulfonic acid, etc.
The sulfonation may be carried out in the pres
ence or absence of aninert organic solvent or
diluent and in the presence or absence of a sul
jointly isolated from the reaction mixture and
employed as such. If it is desired to produce a
salt of the sulfonated alkyl phenol or cresol in a
fonation assistant. As solvents or diluent there
may be employed any inert organic, liquid which
is not readily sulfonated, such as halogenated
hydrocarbons of the aliphatic and aromatic
series, as for example, carbon tetrachloride, di
chlorethane, tetrachlorethane, dichlorbenzene,
form substantially free from inorganic salts (for
etc. As sulfonation assistants there may be em
ployed the lower organic acids and/ or their anhy
drides, as
for example,
acetic
anhydride, etc.
acid, acetic
_
The temperature at which the sulfonation is
carried out may vary within wide limits. For ex
ample, temperatures as low as about 0° C., and as
high as about 140° C. may be employed. In gen
example, inorganic sulfates) this may be accom
plished by taking advantage of the solubility of
the salts of the sulfonated products in alcohol 10
and other organic solvents. Thus a mixture of
a salt of the sulfonated product and an inorganic
sulfate, such as obtained by the processes of the
above examples, may be extracted with alcohol,
and the resulting extract may be evaporated to 15
leave a residue of the purified salt of the sul
fonated product.
The sulfonated products in the form of metallic
salts or salts of inorganic bases are usually yele
lowish to white, friable solids; and in the form
lower is the preferred temperature. Ordinarily
of salts of organic bases vary from viscous oils to
semi-solids to solids. In general, the salts are
the completion of the sulfonation is carried out at
atemperature in the neighborhood of about 25°
to about 80° C. The ratio of sulfonating agent
employed with respect to the alkyl phenol also
may be varied. While the preferred amounts
acid or alkaline) solutions to form solutions
which are faintly colored brown or yellow, which
are of a soapy nature and which form readily.
Certain of the salts, such as the salts of the arc
eral the more vigorous the sulfonating agent the _
readily soluble in water and in aqueous (neutral,
are given in the above examples, an amount of
matic monoamines and the aliphatic and aro- ,
sulfuric acid or other sulfonating agent equiva
lent to from 1 to about 5 parts by weight of s'ul
furic acid monohydrate per part by weight of the
matic polyamines, are oils which generally are
alkyl phenol may be employed.
The extent to which the sulfonation is carried
out may vary with the individual material being
sulfonated and the use to be made of the sul
fonated product. In general the extent of sul
fonation of the alkyl phenol treated is such as to
form chie?y the monosulfonic acid of the alkyl
phenol, and to sulfonate impurities as well, if
40
mixture of the salt of the sulfonated alkyl phenol
or cresol and the other inorganic and/or organic
salt (as for example, sodium sulfate) may be
present.
The alkyl phenol sulfonates may be prepared
in accordance with the present invention in the
form of their free s'ulfonic acids or in the form of
salts of metals (as for example, of the alkali
metals) or of organic bases, or of ammonia, etc.
The salts may be obtained in any suitable man
ner, for example, by reacting the sulfonated
product, either in the crude form resulting from
the sulfonation or in a puri?ed form, with a metal
oxide or hydroxide, ammonia or an organic base,
or of a suitable salt of one of these, in an amount
insoluble in water, probably due to the presence 30
of small amounts of unsulfonated water insoluble
impurities, 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).
85
This application is a continuation-in-part of
my applications Serial Nos. 691,081 and 691,082,
?led September 26, 1933.
I claim:
-
1. A method of producing a nuclear aikyl deriv 40
ative of a sulfonated phenol, which comprises
condensing a member of the group consisting of ‘
phenol and its monomethyl derivatives with an
alkyl halide containing at least 12 carbon atoms
with the aid of a condensing agent, and sulfonat
ing the resulting product.
I
2. A method of producing a nuclear alkyl deriv
ative of a sulfonated phenol, which comprises
forming a phenol compound containing a ‘higher
alkyl substituent by condensing a phenol com 50
pound of the group consisting of phenol and its
adapted to form a neutral product. Among the
bases, oxides and salts which may be combined
with the sulfonated products to produce salts use
ful as detergents and otherwise are, for example,
monomethyl derivatives with an alkyl halide con
taining at least 12 carbon atoms in the presence
of a metal halide condensing agent, the amount
sodium, potassium and ammonium hydroxides;
to produce monoalkylation of the phenol com
pound and sulfonating the alkylated phenol com
sodium, potassium and ammonium carbonates
and bicarbonates; ammonia; magnesium oxide;
ethylamine; pyridine; triethanolamine; propanol
amines; butanolamines; diamino propanol; ethyl
enediamine; triethylene tetramine, etc.
The reaction mixtures resulting from the sul
fonation of the alkyl phenol or cresol may also be
45
of alkyl halide not exceeding about that required 55
pound.
_
3. A method of producing a nuclear alkyl deriv
ative of a sulfonated phenol, which comprises 60
condensing one mol of a phenol compound of the
group consisting of phenol and its monomethyl
derivatives with not more than one mol of a satu
directly employed for the formation of mixed
rated open-chain aliphatic halide containing at
products, as for example mixtures of salts of the
least 12 carbon atoms with the aid of a zinc halide 65
as a condensing agent, and sulfonating the result
alkyl phenol sulfonic acid and of other acids
present in said reaction mixtures, which mixtures
of salts are also‘ useful as such.
Thus, the sul
fonation reaction mixture resulting from the
treatment of the alkyl phenol or cresol with an
amount of sulfonating agent in excess of that
theoretically required to effect the desired degree
of sulfonation may be treated with a suitable
inorganic or organic base or basic salt (as for ex
75 ample, one of those mentioned) and the resulting
ing product.
4. A method of producing a nuclear alkyl deriv
ative of a sulfonated phenol, which comprises
forming a phenol compound containing a higher 70
alkyl substituent by condensing a phenolcom
pound of the group consisting of phenol and its
monomethyl derivatives with a saturated open
chain aliphatic monohalide containing 12 to 23
carbon atoms with the aid of a condensing agent,
4
2,13%,711
the amount of alkyl halide not exceeding about
that required to produce monoalkylation of the
phenol compound and sulfonating the alkylated
condensing one mol of a phenol compound of
phenol compound.
the group consisting of phenol and its mono
5. A method of producing a nuclear alkyl deriv
ative of a sulfonated phenol, which comprises
condensing one mol of a phenol compound of the
methyl derivatives with not more than one mol
group consisting of phenol and its monomethyl
with the aid of a metal halide condensing agent,
whereby “the corresponding alkyl phenol com
pound is produced, and sulfonating said alkyl
derivatives with not more than one mol of a satu
10 rated open-chain aliphatic monohalide contain
of an open-chain aliphatic chloride containing
at least 12 .carbon atoms in a branched chain,
ing 12 to 23 carbon atoms in the presence of a
phenol compound.
metal halide condensing agent, and sulfonating
the resulting product.
9. A method of producing a nuclear alkyl deriv
ative of a sulfonated phenol, which comprises
6. A method of producing a nuclear alkyl deriv
15 ative of a sulfonated 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 a satu
rated open-chain aliphatic monohalide contain
20 mg 14 to 19 carbon atoms with the aid of a zinc
halide as a condensing agent, and sulfonating the
resulting product.
7. A method of producing a nuclear alkyl deriv
ative 'of a sulfonated phenol, which comprises
25 condensing a member of the group consisting of
phenol and its monomethyl derivatives with an
alkyl chloride containing at least 12 carbon atoms
so
8. A method of producing a nuclear alkyl deriv
ative of a sulfonated phenol, which comprises
with the aid of anhydrous zinc chloride, whereby
the corresponding alkyl phenol compound is pro
duced, and sulfonating said alkyl phenol com
pound.
-
condensing at least 1.25 mols of a phenol com
pound of the group consisting of phenol and its 15
monomethyl derivatives with one mol of an open
chain aliphatic monochloride containing 14 to 19
carbon atoms in a branched chain, with the aid’
of anhydrous zinc chloride, whereby the corre
sponding alkyl phenol compound is produced, and
sulfonating said alkyl phenol compound.
20
10. A method of producing a nuclear alkyl
derivative of a sulfonated phenol, which com
prises condensing one mol of phenol with not
more than one mol of an alkyl mono-chloride 25
containing 12 to 23 carbon atoms, with the aid of
zinc chloride as a condensing agent, whereby the
corresponding alkyl phenol is produced, and sul
fonating said alkyl phenol.
LAWRENCE H. FLETT.
30
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