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Патент USA US2412909

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Patented
l7‘,~ 1948- ‘
2,412,909‘
7 UNITED 'srArEs PATENT OFFICE
2,412,909 ‘
ORGANIC COlt?’OUNDS AND METHODS OF
PREPARING SAME‘
'
Dwight James Potter, Allendale, N. 3., assignor to
Colgate-Palmolive-Peet Company, Jersey City,
IN. .I., a corporation of Delaware
No Drawing. Application April 24, 1942,
Serial No. 440,390
15 Claims. (01. coo-sin
, The present invention relates to a process of
‘producing novel organic sulphur compounds and,
more particularly, to a process of producing or- ,
ganic sulphur compounds having valuable deter
gent and foaming properties, and tothe novel
_
2
series of equations are suggested as a possible
explanation of the reaction mechanism, although >
it will 'be understood that the present disclosure
is neither bound thereby nor limited thereto :,
product of said process. '
It is an object of the present invention to’pro
vide a novel process for preparing valuable deter- ‘
. gent compositions.
Equation .1 indicates the dissociation of chlorine
It is‘ another object of this invention to pro 10 into two electrically neutral chlorine atoms or .
vide a novel process for preparing organic sul
free radicals. Equation '2 represents the reaction
phur' compounds from relatively inexpensive or
of‘ a chlorine atom or free radical upon an organic
ganic materials by reacting .said materials with ; compound,
wherein It represents an alkyl or sub
a halogen derivative of a loweroxidation product
stituted
alkyl
group linked to hydrogen. Accord
of sulphur in the presence 0! free radicals.
15 ing to this suggested reaction mechanism, the
_.It is also an object of the invention to provide
chlorine atom splits the hydrocarbon molecule to
a new and inexpensive process for preparing or
ganic sulphinate and/or sulphonate salts from; form. hydrogen chloride and to leave an alkyl or
substituted alkyl free radical. The free hydrocarbon
radical is thus available for reaction with
bons obtained from petroleum oils.
20 thionyl chloride or other halogen derivative of
The present invention also contemplates the
a lower oxidation product of sulphur, and, as
organic materials, including saturated hydrocar
provision of a simple and inexpensive method for '
shown in Equation 3, an organic sulphinyl chlo
_ ride and a free chlorine atom are produced. The
thereof for use in various chemical syntheses,
It is also within the contemplation of this in 25 free chlorine atom thus produced is then avail
able for opening up another molecule of the or
vention to provide novel organic sulphinic acids
ganic compound for sulphlnation. If we consider
and‘ sulphinates and derivatives thereof,‘ _
only Equations 2 and 3, it would appear that
The invention further provides novel organic
chlorine
serves merely‘ as‘ a catalyst in the reac:
sulphur compounds having valuable detergent,
'tion. However, the chlorine atom may react with
emulsifying and wetting properties.
Other objects and advantages of the invention 80 a hydrocarbon free radical, as formed according
to Equation 2, to produce a chlorineesubstituted
will be apparent from the following description.
organic compound, such as an alkyl chloride. and
. ‘According to the. present invention, organic
thus be removed from the cycle of the reaction.
compounds are'reacted with a halogen derivative
‘
It‘
will be-appreciated that this theory of reaction
of a lower oxidation product of sulphur, such as 35
is not necessary to an understanding of the pres
the thionyl halides, and a compound capable of
ent inventiomas disclosed herein, and that the
providing a free radical, that is, a particle having
same is advanced merely as an aid to the further
an unpaired valence electron, such as a halogen
development of the art.
'
in the presence of actinic light, toiorm organic
When
employing
a
thlonyl.
halide
as
the
react
sulphur compounds, such as organic sulphinyl 40
ant, a sulphinyl halide of the organic compound
‘halides. Unreacted and by-pmduct gaseous ma
is formed. This product can then be hydrolyzed
terials are then preferably removed. and the
to yield a sulphinic acid or it may be hydrolyzed
product is hydrolyzed with an alkaline agent and
and neutralized to produce a salt thereof. The
may optionally be oxidized to yield a sulphonate.
making organic sulphinio acids and derivatives
sulphination product, whether sulphinyl halide,
If_ desired, the product may be reacted with other 45 sulphinic
acid or sulphinate, can also be oxidized
to the corresponding sulphonation product. The
unoxidized product is soluble in alkali, but may
organic compounds to form secondary deriva
tives.
Although the mechanism of the reaction is not
thoroughly understood,v it is believed that the
separate out when the solution is acidi?ed, where,
upon’ it can be partially redissolved in alkali.
50
Even in dilute solutions, the product shows un
rine atom, acts upon the organic compound to
usual foaming, washing and wetting powers.
strip off a hydrogen atom, forming hydrogen
'In selecting organic compounds for treatment
chloride, and to leave the organic residue as a
according to the process of this'invention, it_is
free radical available for reaction with the or
preferred to use aliphatic hydrocarbons of any
ganic sulphur compound. Thus, the following
presence of a free radical, such as a nascent chlo
55
desired number of carbon atoms to the molecule, .
'
enraeoe
-
.
,
..,
s
‘
.
~
,
to
chlorine
mix thionyl
vapors into
chloride
said therewith
:uw ure inand
veryiinely
to
dispersed state in the presence of actinic rays.
Satisfactory detergent compounds have been pres
. (methyl cyanide), dlchlordiethyl ether, trimethyif
amine, trichlormethyl chloriormate, phosgene,
. stannic chloride, liquid hydrogen ?uoride, liquid
hydrogen chloride, boron tri?uoride dlhydrate,
nitrobenzene, i-nitropropane, 2-nitropropane,
cresol,‘ sulphur monochloride and various misci
ble mixtures or the foregoing solvents, the last
pared from straight chain hydrocarbons having
about 8 to about 26,, and preferably about 12 to
about 20, carbon atoms to the molecule. Cyclo
'
alkanes, alcohols, iatty acids, and other aliphatic
be
sulphinated
by
vorganic compounds can also
10
this process.
,
g
The molar proportion of the organic compound
.
,
,
to either the halogenderivative oi
thelower
oxi
?ve named being more eilective when used at
‘low temperatures. 0! these solvents.‘ some, such
as the nitro compounds, have a slight oxidizing
e?ect and thus tend to oxidize certain organic
sulphonyl halides; this tend
?lllphinyl halides'to
ency may or may not be of advantage, depending
dation product of sulphur or the compound fur-l nishing the free radical may be widely varied, as
desired. However, when employing a thionyl
halide and a halogen as thetreating materials, as
it is generally preferred to'halogenate a minimum .'
amount oi.’ the organic compound, it has been
found advantageous
to excecdthe stolchiometri'c,
I
upon whether organic sulphonates or sulphinates
are desired. The use of alcohols as preferential
solvents, as disclosed supra, may cause the esteri- .
iication or the sulphinyl halides,.but, ‘except for
possible loss-oi alcohol thereby in the succeeding
hydrolysis, the subsequent operations are not at
7 rected to any disadvantageous extent. when us
proportion of thionyl halide and to provide about‘ 20
2 to about}: mole, of thionyl halide for each .mol-J: .i
of organic material and,‘ conversely, to use only
I about-0.2 to about 0.5 mol oi’ halogen ‘per mol of
organic compound,
,
.
ing some or the aforementioned compounds, such
as the alcohols or acids, as selective solvents for
the sulphinyl halides, it is desirable .to have the
reaction mixture.’ substantially - tree of, thionyl
extracting in order to avoid side
as halide beforeWith
most of the solvents disclosed,
is preferably carried out withthionyl'chloride . reactions.
‘ extraction may be carriedout beioreor after
The treatment with thionyl
and chlorine at a temperature between about " , ' the
heating to remove thionyl halide.
25° C. and about 100° C. and for a length of time
The organic sulphinyl halides may be extracted
required for the desired degree of sulphinationj
with a preferential solvent. with or without the
halogenation
or
the‘
organic
material."
30
I and 01
. addition of an adluvant solvent or solvents im- ‘
When rescues-1 the materials in. thsumwrrsrt
or this temperature range or higher,,it is-ad
vantageous to operate under superatmospheric
miscible ‘or only slightly miscible with the ‘pro!
' ' erential solvent.
Liquid alkanes or low molecu
la!‘ weight, such as propane, butane, pentane.
heptane. octanemonane, and petroleum
to use chlorine and thionyl'chloride as treating 35 hexane.
and other su
ntially non-polar solvents
agents, .th‘ehalogen used. may also be ?uorine, - ether,
and mixtures thereof may be added to the reac
iodine orbromine, and thethionyluhalide may
tion mixture as adiu‘vant solvents. in this con
be a ?uoride or/bromide'. Selenious or tellurous
nection before, after and/or simultaneously with’
oxyhalides may replace the thionyl halide (sul
the preierentisl solvent. The use of a non-polar
phurous ox'yhalide) as a reactant, and the cor 40 solvent substantially immiscible with the prefer,
responding oxyc , rides, oxybromides and oxy
ential solvent provides greater selectivity._re
iiuorides are applicable for this purpose. The,
moval ofv the last traces of "non-sulphinated"
halogen may be replaced by other compounds
material from the polar solvent solution, and the
capable 01! providing free radicals, such as lead
maintenance ot. high-melting raiiinates in aliq-v
alkyls under thermal decomposition, etc,
uid condition when employing low-temperature
The sulphination product may be freed from
‘ unreacted material by heating to between about
Bytreating with aprei'erential solvent, a polar
100°.and about 125° C. to remove gaseous re
prei'erential solvent phase is formed, which can
actants, and known methods, including fractional . then be separated from the residue by drawing
‘ distillation, iractional crystallization, extraction '50 - oil’, decanting and/or centrifuging. Substan
and other separation procedures or any combi
tially all impurities are thereby removed, and
nation of these, may be employed for separate
the organic sulphinyl halides thereafter. sep-' .
ing theproduct from non-gaseous reactants and
arated from the‘ preferential solvent are sub
- impurities. 'A preferred method is to extract the '
stantially pure‘ and consequently more‘ desirable
55
organic sulphinyl halides with a selective solvent.
because of the unimpaired detergent properties
ior separating them from unreacted hydrocar
of the sulphinates and/or sulphonates derived
bons and/or hydrocarbon-like materials and
The low-boiling solvents, such as
from merely halogenated derivatives thereoi. ' therefrom.
methyl formate or liquid sulphur dioxide, may
The organic sulphinyl halides are relatively sol
be readily separated from the'organic sulphinyl
uble in solvents ior polar compounds, whereas 60 halides by vaporization and, may be condensed \
the unreacted or merely halogenated materials
and reused for treatment of additional material
pressure. or to re?ux. Although it is preferred.
operation.
I
are insoluble or sparingly soluble therein.
Among the solvents which may be employed as
preferential solvents in extracting the sulphina
tion product from the reaction mixture are liquid
sulphur dioxide, liquid carbon dioxide, nitroal- .
-
or tor any other purpose.
.
\
-
~
A preferred extraction procedure maybe per- ’
iormed by adding about an equal volume of an
oxygen-containing ‘preferential solvent for the
polar ‘sulphinyl halides, such as methyl formats
or liquid sulphur dioxide, to the‘ organic sul
phinyl halide reaction mixture and then an equal
slycolchlorhydrin,
- iuriuryl. alcohol, iuriural,
glycerol chlorhydrin, glycol, glycerol, dlmethyl 70 volume of immiscible non-polar solvent. such as
hexane. " The order of adding the solvents may
' sulphate, diethyl sulphate, dibutyl sulphate, phe
be reversed, or they may be ‘used simultaneously.
monoformate,
glycol
3
ml, methyl iormate, glycol
The mixture separates sharply into two liquid
dii‘ormat‘e, ethyl tormate, formic acid, methyl
phases. ‘One or the phases consists mainly of
acetate, glycol monoacetate, glycerol monoace
tote, acetic acid, acetic anhydride, aoetonltrile 75 polar solvent and contains the major portion 01'
hanes- including nitromethane and nitroethane. ‘
dry ethyl alcohol, wet methyl alcohol, pyridine, , ‘
2,419,909 I
6
the organic sulphinyl halide, and the other phase
4 The ‘organic sulphinyl halides are preferably -
contains, the non-polar solvent solution of hydro
carbon-like material and halogenated derivatives ‘
thereof. The oxygenated solvent layer, e. g., liq
_ uid sulphur dioxide, is usually more dense than‘
recovered from the selective .solvent by removal
of the solvent in gaseous form.v Thus, ‘the re‘
moval of solvents having a lowboiling point may
be accomplished by bubbling an inert gasnsuch,’
the non-polar solvent layer, e. g., hexane; hence,
as carbon dioxide, nitrogen, stack ‘gases,- etc.,
the latter forms the upper layer. It is desirable
through‘ the mixture‘ and/or .by' gentle heating.‘
t'o'i'orrn layers having widely different speci?c
and/or byother means. Suitable equipment may
gravities in order to promote separation. Either - be
provided for carryingout these operations,
solvent may be replaced by substantially miscible 10 whereby
the volatility of the low-boiling solvent,
mixed solvents performing in a manner sub
stantially similar to the solvent replaced.
such as liquid sulphur dioxide, may be increased, .
'
The polar solvent phase, such as the methyl ' as by reducing the pressure‘in‘ the system. Such
equipment may also be provided with condensing‘
formate or liquid sulphur dioxide layer, may be
separated by known methods, such as drawing 15 means, whereby the volatilized sulphur dioxide
and/or other solvents employed may be recovered
oil, decantation, centrifuging. or the like, and . for
reuse.
willbe found to contain most of the organic sul
The
sulphinyl halide product, thus .freed by
phinyl halides. It may be rewashed with'addii
extraction or otherwise from unreacted material
tional non-polar solvents, such‘ as hexane, to
cause'more, complete purification. The non-polar -20 and impurities, may then be hydrolyzed with
wateror with aqueous solutions oi'salts and/or
solvent solution ‘contains most ofgthe impurities
acids or alkalies, and preferably with an alkaline
and may be successively extracted or washed with
agent, such as a caustic solution. The use of an ,
additional polar solvent until it is substantially
alkaline
agent permits neutralization along with
free of organic. sulphinyl~ halides. , These non
polar solvents, which are immiscible and none . hydrolysis. Excess‘ gaseous reactants, by~prod
25
reactive with thepreferential solvent for the sul- - ucts and/or other gaseous material, if‘stillspres
ent, may be removed from the sulphin'ation prod- .
phinyl halides under the, reaction conditions, will
not, before or after hydrolysis, by blowing with"
substantially inert gases, such as nitrogen, carbon
‘ somewhat solublein the, liquid sulphur dioxide 30 ‘dioxide, sulphur dioxide, flue gases and/or steam.
or 1 other polar solvent. but which are less polar _ Air or other oxygen-containing gasmay be simi
larly employed, where the product is ultimately
than the sulphinyl halides.‘ ,
, _
to be oxidized to the sulphonate.
Continuous extraction procedures. ‘as by dilu
The hydrolyzed product may be extracted‘with
tion of the mixturewith one solvent and counter
assist in removing. nonesulphonated materials,
'e.'g.', aromatics, ole?ns and the like, which are
_ current washing withthe other solvent, may be 35 ether, gasoline or the like to remove any residual .
organic unsaponiilable materialtherefrom.‘ In
effectively and economically carried out. It is
organic salts added or formed during hydrolysis
and/or neutralization may be removed by extrac
tion of the product with ethyl alcohol, butyl alco
also contemplated that one or more preferential
solvents, such as liquid sulphur dioxide with an i
alkyl sulphate, may be employed, either with or
without one or'more other solvents which are 40 hol and the like, or the solution may be dialyzed
to obtain this result. Since certain inorganic
soluble in the selected polar solvent phase'and
which will increa se the solubility of the organic - salts which may be present, such as sodium chlo
ride, are soluble to ,an‘appreciable extent in these
sulphinyl halides'contained therein or will depress
solvents, the hydrolyzed products may be purified
the‘ solubility of the impurities in the polar
by adding an amount of a water-immiscible or
45 ganic solvent, such as benzol, toluol, or the xylols,
The extraction maybe carried out in simple,
capable of dissolving the salts of the organic
single or multiple contact; countercurrent mul- '
sulphur
compounds in the anhydrous state, but
tiple contact, and continuous countercurrent con
incapable
of dissolving appreciable amounts of
tact. ~Using either of the two last mentioned,
theinorganic salts. ‘The mixture is heated to
backwash or re?ux operation is preferably em
boiling’ to vaporize both the water and the or
I. ployed to obtain thorough extraction. Itis even
ganic
solvent,'and the vapors are condensed and
possible to conduct the continuous extraction
solvent.
‘
'
,
~
-
a
‘
'
separated. In‘this manner. the water can be
vprocedure simultaneously with the formation of
sulphinyl halides, although this may be undesir
. removed from the condensate, while the water- ’
able where the solvent or solvents employed enter
into reaction with the starting materials or prod
ucts under the reaction conditions. The extrac
tion of the impure sulphinyl halide product can
be conducted in several stages wherein the mix
ture is ?rst extracted with one solvent and the 00'
ra?lnate thereof extracted with the second sol
vent, or the solvent~free extract from the ?rst
stage of extraction maybe re-extracted with a
second solvent. This solvent; may be recovered
immiscible solvent is permitted to flow back into
the boiling mixture. Re?ux distillation is con
.tinued' until no more water separates, at which
time the organic solvent is the only liquid which .
remains in the distillation vessel. The organic
solvent containing the organic sulphur com
pounds in solution therein is then separated from
the ‘undissolved inorganic salts by ?ltration, de
cantation, and/or centrifuging or the like, and
the solvent is thereafter removed by known
methods.
‘
‘
from the extract and/or the ra?lnate by extrac 65 . While the reaction
may be carried out between .
tion with a suitable secondary solvent therefor.
broad temperature limits, such as from about
Extraction with a secondary solvent of relatively
—10° C. and below to about 200". C. and above,
low boiling point is particularly desirable in those
it .is advantageous to ‘conduct the sulphinatlon
cases where the primary extractant is high-boil
ing. The solvents may be recovered directly from 70 between about 25‘? c. and‘ about 100° 0. The'
preferred temperature rangemay be effected by
the extract, from the ra?inates or from the sec-.
applying suitable controls, depending upon the.
ondary solvents by anysuitable method, includ
rate of reaction and the heat evolved. Thus, the
reactants, diluents and/or vapors may be pre
ing distillation, evaporation, crystallization, salt?
ing-out or the like. The recovered solvents may
then ,be reused for‘fresh materials.
'
heated or precooled, the admixed liquids may be '
75 vaporized, and/or external heating or cooling of
r
‘
.
y
7
u
"ins agents of the present invention, the straight -
the reaction mixture may be provided. it is ad
vantageous to maintain the preferred temper
chain saturated aliphatic hydrocarbons have
been found to provide satisfactory, sulphination
ature range, which may vary for different ma
terials, since, with certain raw materials, the
products (and/or sulphonation products, after
' oxidation) , as aforesaid.
products tend'to decompose, to polymerize, to
A particularly desirable
‘ '
source of this material is in the petroleum frees‘
tions generally described as gas oil 'rractions.
Para?in base gas oils, such as are recovered from
discolor and/or to develop an undesirable odor
at higher temperatures. In such cases, temper- a.
ature control is very important in the produc- , crudes of the Pennsylvania andMichlgan?elds,
tion of materials of uniform properties.
are particularly desirable, and theindividug] con.
The sulphination reaction is affected by many 10 stituents of these gas oils, such as those having
factors, includingtheconcentration of ‘the re . from about 12 to about so, carbon atoms, and" ‘ '
the time of treatment, the reaction tem-'
- actants.
especially the straight chain saturatedhydrm
perature, the pressure, the organic materials be-'
carbons oi this n-docosane
class, including
and cetene,’
n-heptadecane,
provide, 2
ins treated, and the type and intensity of illumi
n-tetradecane,
nation or radiation employed to catalyse lthe re 15 very
satisfactory sulphination i'p'roducts ‘for' the?
action. Light- rays from that portion ofv the
spectrum extending from- the blue to the ultra
present‘.
cracked, gas
purpose.
oil ofHowever,
paraillnic,“either
violet are particularly e?ective in assisting the
naphthenic base or mixtures thereofwmaybpj
reaction‘.
>
'
,,
. >
The gas oil or otherpetroleum, mumssedmm
-
The process may be continuously carried out,
preferably by continuously passing the organic
‘be puri?ed or concentrated bye-‘any ofathewimown,
procedures before‘ 'sulphinating. For example,
sulphinated downwardly in an _
material to be
illuminated vessel'in countercurrent flow to a
the boiling range of the'gas oil may be narrowed‘
by fractional distillation, preferably under vac- y
uum and ‘in the presence of caustic ‘.soda' or‘
heated rising gas mixture including the thionyl
halide and halogen. If the thionyl halide is a
‘ liquid at the
'
other bases. ‘The gas oil may be given a pres.
liminary treatment witha small amount‘ of oleum '
or concentrated ' sulphuric . acid; or the like 'to
particular temperature employed.
it may be passed downwardly in concurrentnow
with the organic material. Similarly, if theor
ganic material is in the gaseous state, it may
remove resin-forming and othernnstable, con
stituents therefrom.v It, may also be admixed"v
be passed upwardly in contact with the other 80 with filter clay, silica gel, or decolorizing cal-born;
reactants. The reaction is preferably carried out
which materials may be separated therefrom by
in a tower containing a column of inert material '
settling, centrifuging, and/or filtering. A "para
ticularly desirable treatment; for obtaining better‘
capable of transmitting light, such as rings,
beads, bubble plates, ?bers, and/or various other
includes solvent, extraction to remove the
shapes of glass, plastic, rused silica, quartz and 85 results
more aromatic and/or unsaturated‘ constituents .
other llke..materials; The sulphinated product
of the gas oil, although the removed constitu-r
- may then be continuously or intermittently re‘- .
moved from the bottom of the tower and may be
continuously or intermittently hydrolyzed and
purified. Where a solvent or solvents are used
ents, including oleiinic and cycolapihatic mate
rials, may also be treated by the process of
40
thepresent invention.
to extract the reaction product, these may be
introduced into the top of thetower along with
the reactants, .as aforesaid,lf desired.
'
e
‘
‘
-
-
Among‘ the materials which maybe treated
alone or along ‘with one or more of the saturated
aliphatic‘ hydrocarbons or their mixtures, such as
~
a
gas oils," are‘ paraiiln'v hydrocarbons, including '
The sulphination products termed are readily
susceptible to oxidation, especially after hy
_
I ‘
. butane,
dodecane,
hexane," heptadecane,
octa
decane and hexadecane; petroleum hydrocarbons,
' drolysis, to form sulphonic acids or sulphonic
acid derivatives. , The oxidation may be accom
plished by any of a variety of means, with or
< without oxidation catalysts. A convenient meth- ‘
’ other oxygen-containing ‘r
od "is to blow air or
gas through the sulphinated material, and oxide
tion may thus be advantageously combined ,with
removal therefrom of excess gaseo'us reactants,
by-products and/or other gaseous material by ',
blowing, described supra. Other oxidizing agents,
including 'para?ln wax, ‘slack. wax, scale wax,
Asiatic wax, white oil, kerosene, lubricating oils
and’ railinates of ‘lubricating oil' and kerosene
extractions; hydrocarbons produced by the hy
drogenation of oxides of carbon; hydrogenated ‘
coal; oleilnes, includingdecene, hexene, cetene
and dodecene; tetraisobutylene and other poly
merized ole?nes; cyclic compounds, “including '
decalin,‘ cyclohexane, ‘methyl 'cyclohexane, do
decyi ,cyclohexane and cyclohexene; sterols, in
including nitric acid, the oxides of nitrogen, hys , ‘ eluding cholesterol, ‘phytosterol and the like;
drogen peroxide and other, peroxides, chlo-.
- rates, perchlorates, persulphates, perborates, etc.,
and/or mixtures thereof, may also be used, with
or without air blowing.
.
v
>
resins and fatty acidsand their monohydric and
full and partial polyhydi'ic alcohol esters, includ
ingstearic acid, rosin, spermaceti, tallow, tall oil
.60 and monoglycerides of coconut oil; ‘alcohols and
The sulphination products may also be reacted
with other organic compounds to form secondary
derivatives. Thus, the sulphinates readily react
with alkyl halides to form sulphones, and the.
organic sulphinyl halides react with amines, 65
their derivatives; the halogen and other'substi
vtuted derivatives of these materials, including
chlorinated paraiiin wax, chlorinated gas oil, cetyl
chloride'and oleilne halides; and various other
derivatives thereof, beta-keto-esters and other‘
thereof. It is preferred to treat the less expensive ‘
‘ and more‘ available saturated aliphatic‘ materials.
Where organic carboxylic acids are treated in _.
. phenols, alcohols, aromatic hydrocarbons and
active methylene compounds, etc. ; These sec
aliphatic or cycloaliphatic materials andmixtures
ondary derivatives are, like the sulphination
with thepresent invention, an amount
products themselves, useful as reducing and 70 accordance
of thionyl halide su?icientto form the carboxylic
bleaching agents. and they are also useful. as
acid halide and then ‘to convert this intermediate
dyes, plasticizers, tanning agents, drugs,'me_dicaa
product to- the sulphinyl halide is employed.
merits, stimulants, vesicants, poison gases and
when alcohols are treated, a su?icient excess ‘of
- industrial chemicals.
,
.
V
In preparing the valuable
detergents
and foamto thionyl halide to term alkyl halides and/9pm.’.
2,419,909 '
10
phites and. then to'produce sulphinyl halides,
‘
“therefrom is used.
4
signs of decomposition. The major fraction oom
l
prises cyclohexyl sulphinyl chloride, a light yellow ‘
oil with ‘a characteristic" odor. A portion of this
The .prmii‘fstmaybe in the form‘ of the acids‘
or the salts of sodium, potassium, calcium, mag
- product is hydrolyzed with sodium
nesium, aluminum, ammonia, mono-, di-, and
hydroxide and,'
on cooling, is crystallized out in ?at, shiny ?akes.
_Another portion of the product comprising cyclo
triethanolamine, - amino -" trimethylol - methane,
amyl-amines, methyL-amines, aniline, pyridine
hexyl sulphinyl chloride decolorizes dilute potas
sium permanganate, ‘dilute aqueous iodine and
aqueous brominesolutions. Bromine dissolved in
and like metals or co'mpounda. The bases cor
responding to the above metals or compounds
may be used for saponifying the sulphination
products. The salts may be interchanged by the - 10 a carbon tetrachloride is not decolorized.
The cyclohexyl sulphinyl chloride reacts vio-_
treatment- of a solution of‘ one salt of the novel
lently ‘with sodium peroxide, being neutralized
compounds in a solvent, such as acetone, ethyl
and oxidized to form the sodium sulphonateb
alcohol, isopropyl alcohol, butyl alcohol, dioxane,
sodium salt of the sulphonated product is
monoglycerides, Cellosolve and Carbitol, with a 15 The
readily soluble in water and in alkaline solutions
concentrated aqueous solution of a soluble salt
and has excellent detergent, wetting, emulsifying
of an ‘inorganic acid having a di?erent cation
from that of the- product to be treated. This
,
Example III
process also serves to remove'from- the product
the-inorganic salts, such as sodium chloride.
About 242 grams of a Pennsylvania white min
The following examples, described herein, are
eral oil are mixed with about 120 grams of'vthionyl merely illustrative of the present invention, and
chloride in a glass vessel, and chlorine gas is
it will be understood that‘ the invention isnot
slowly
bubbled in at .a rate such that substantially
limited‘ thereto.
_
‘all of the -gas is absorbed before reaching the
‘Emmple I
‘ surface of the reaction mixture. A mercury vapor
'
‘
.
"About 45 grams of an acid-re?ned gas oil of
para?inic base having a boiling range of about
500° to about 700° F. are mixed with about 71
grams of thionyl chloride, and the mixture ‘is
placed in a' reaction vessel illuminated by.a 250
watt, type H-2, General Electric mercury vapor
lamp placed about 3 inches away. About '71
grams of gaseous chlorine are ‘slowly passed into
-‘ ‘ the mixture over a period of about six and one
half hours. The temperature risesrapidly at
and
foaming
properties.
' '
-
‘
_
'
20
lamp at a distance‘ of about 3‘to about 4 inches‘
from'the vessel Provides illumination to catalyze g
the reaction.‘ The mineral oil and the thionyl
chloride are precooled, and a temperature of
about —10°, to about _+10° C. is maintained
throughout the entire run. When about 35 grams
of chlorine have been added, about 120 grams
more of precooled thionyl chloride areadded, and
the chlorine addition is continued until about 35
grams more ‘are consumedq At the end of three
‘ ?rst and is maintained at about 75° C., the color
hours, carbon dioxide is bubbled ‘throughthe
of the mixture remaining a light yellow during
this period. The mixture is thereafter heated
to about 115° C. and blown with nitrogen to expel
crude product containingsulphinyl chlorides is
unreacted thionyl chloride. Aqueous sodium hy
droxide is then added, and the mixture is heated,
causing a very vigorous hydrolysis to take place.
The mixture is extracted withgasoline to remove
- unsaponi?able material therefrom.
A quantity
of benzol'is then added, and the mixture is re
?uxed, using‘a trap to ‘remove water from the
. condensate before returning it to the distillation
reaction mass to sweep out excess gases, a'nd‘a
obtained as‘ detailed in the preceding examples.
40' Upon hydrolysis with a 5% solution of sodium
hydroxide, a vigorous reaction‘ ensues, and the
sodium salts of the mineral oil sulphinic acids
are obtained. The sodium salts are isolated from
the aqueous solution by a'benzol boiling, as in‘
45 Example I.
.‘r
-
Example IV I
'About '7 parts by weight of a Pennsylvania
‘
white '
vessel, wherebyinorganic salts‘ are precipitated.
mineral oil and about 10 parts by weight of‘thionyl
After decanting, the ,benzol is removed by dis
tillation, leaving an amorphous product.- The 50 chloride are run. continuously into a glass reaction‘
vessel ‘containing transparent beads, and abcutf'l
product is readily soluble in water, and even ‘dilute
part of chlorine gas is slowly bubbled into the ves-g
solutions show unusual foaming and detergent
properties.
'
l
.
'
'
sel in countercurrent to the down-?owing liquids;
The mineral oil and the thionyl chloride ‘are pie;
55
heated
to an extent .su?icient to maintain a tem‘“:
About 84 grams‘ of cyciohexane are mixed with
Example II ‘
about 119 grams ofthionyl chloride in ‘a glass
‘vessel. The ‘mixture is treated with about 35
grams of gaseous chlorine'overa period of about
perature'lof about 45° to about 65°. C. in the reace,
tion vessel, and a mercuryvapor lamp about,§,3,
inches from the vessel provides a source of ,actinici'
two and one-half hours, while exposed to a mer 60 uct,
light.chlorinated
_A mixtureoil;
of the
unreacted
sulphinyloil,_
chloride
and excess
cury-‘arc lamp. Excess gases are‘blown out of
thionyl chloride is withdrawn at‘the bottom of the?
_ the reaction mixturefwith carbon dioxide, and
vessel and passed to the central portion ofan ex;
the mixture is distilled in glass apparatus. ' The
traction column. _ A volume of ‘liquid sulphur di§v
material is heated to about 50° C. under‘40 milli
oxide about twice that ofthe mixture-is fed into
' meters of mercury absolute ‘pressure, :and thionyl
chloride‘ and unreacted cyclohexane are‘ thereby
removed. - ‘The distillation temperature 1 is i‘ then
65 the column ‘at theqtop. . he: I liquid sulphur , _ I '~
_‘OXlde dissolves the “reaction product andwexcess,
raised, collecting a'minor fraction between about ,‘ thionyl chloride and is removed at the bottom of;
thecolumn, while unreacted, and/or merely chlo-,
60° and about 70° ‘C., the‘ ‘fraction largelyicome
rinated oil is taken; oil at thetop. Thesulphur;
prising chloroyclohexa‘ne. ‘1 The system is ‘further 7o dioxide
solution‘ is then-subjected ‘to, vacuum di's:-.
evacuated to'about*3 to about ‘4 millimeters of
mercury pressure,‘ and the temperaturelis‘in
'
creased.) Amajorfraction,
‘
‘
boiling
between
‘about i
85° and about 110° C, is collected,=a last fraction
between about 110-” andabout :1l5°<C.1showing'
tillation, maintainingma "vacuum
of about ‘28- >
. inches, and the sulphurdioxide and excess‘thionyl‘
chloride are separately condensed ‘and recovered
for reuse... The sulphinylchloride ‘reaction ‘prod;
75 ,uctiis thereaiterhydrolyzed, as ldescribedvin. pre-i~
'
-
'-
..
' '
“
-
to out o, co
coiudlte
?le?gm.
_. .-
tion ore solid.‘
utdbgr
od and air
, solid to di » = 'd with out 1
i
' About 219 creamer‘ lcuroyl chloride ore so A
"
-
-'
.
*
by“ caused to seperotc.
-=‘ and
or these are put inbromide,
a
with
‘
‘tllerethrougb. Excess doses and t mm c
‘are thereby removed. The residue cont
weevil:
whereupon eer is added to the solution. Fine»
white lea?ets oi the sodium sulpete are tlieroe
:from‘e mercury arc 1p throughout the, reeled
tiou. The mixture is distilled at about 126° Q
under an absolute pressure or w~~
30
of mercury, while in
u, s -z,. .r
H1
in;
into
hours.
ycsseLeud
the mixture,
about
reaction
85
d ;~\ *-1
mixture
w eofperiod
is cexpo
or or to lit
-
=1
carbonate
is
with about 119 ore of tbionyl chloride in e. g =- :
cc. or
ut 2.35
end uebuteuol.
e :o 1.: we is re?uxed for about
due bouro
en ?lte
d is
allowed too, cud
‘= u
bot.
trate is
colcrless lea?ets of.
bone cote there
reacted luuroyl chloride
d lsyl culori ' ‘ pint-gal cycluml 5
irom -csc oiu
token up with col
lsulplilnyl chloride is hydrolyzed d
'»Hl“$\§._-s
dud
use
recryst
,1
The
'
with sodium hydroxide, and u sure
or. owuen
tols'tnus obtained ore found to melt r . .t; _
the
is then
sulphlndted'
bubbled tlu-ousb
product to
thethe
material
M1; to colt or‘
about/176° to 377°‘ C“ A ixture orthese '- . l '-=
the collide pruct;
=.~_ med by the treat
s ulphonotcd leuric acid.‘ This pllodllotis ud= _~ ' with
ment
or
cyclolieo
with
onyl
coridc cud
31d‘;
with sodium lute ‘food from
.
noted lauroyl chloride. A portion of
5“"“"'
. .
tlou
issepereted from inorganic suits by the procedure
described in Example I.
other portion cl time
product is selted out to yield a sub
free
teriel.
-
'
"‘"
ueut
‘M
reectloth psnltrobol br
all
1! '
also melts on
M
drolysis andsulpl
oycloheuyl
ueutmlicetion
c
e,to‘which,
sum
ide, yields cyclolieuyl sulpc ucld = w:
dro ~
cult.
can:
-
I Example yr
cyclones
About low r: w“: of cyclolieue are to ;.¢:-;i
u reaction tu wi about 292 u or oil tblcnyl
chloride, and menus for melntai5.a,~= the tru»
ture of the reaction mixture at about it" to
imilerly, smetricsl di~cyclohewlsulpbouyl-_
r» ‘>
a"; by means of the
w is synthetior, pre
d'reection and is com
at" G‘, are provided. A general Electric t m. »2
ercury vapor lamp located at e tunce or about
3 inches from the tube is employed to illuminate
the mixture, and about 65 grams of chlorine ere
bubbled in throughs iritted g1
‘£11.:-
res distributor
midc. Each
stslline product, as well
ture of the two, melts at about 155? Q.
.
1926881118 01 about 1 to about 2 millimeters oi mer
lmufy. and a fraction boiling between about 60°
' ‘
About 5 grams of this lractionis treated with
about 6 cc. of 5N sodium hydroxide. A vigorous
reaction ensues. resulting in the formation of a
mass or colorless crystals. The crystals are
washed with ether, ?ltered and dried. About 2.38 _
grams of sold crystals are then boiled for about
my; hours in a n-butanol with about 2.11 grams of
m-nitrobenzyl bromide. The reaction mixture is
then ?ltered, and the ?ltrate is allowed to cool.
Qrystals' are obtained which are then taken up
with ethanol and are recrystallized therefrom, the
gylsgglliéle product melting sharply at ‘about 1'16‘r
-.';l’a.ra-nitrobenzyl cyclohexyl sulphone is then
lllrepored synthetlcsllylnthc {allowing manner: .
moo-gent. ' About 100 cc; 0! liquid sulphur‘ dioxide '
dissolved in about 200 cc. 0! ether-‘ore then added
thereto.~ A solid separates during the addition
and is redissolved in excess sulphur dioxide-ether
_.<solutlon. The mixture is thereafter poured upon
nod eccorg to the present invention
s.
~-
aye
Wm
_
- trstiuucnd equalizing properti . Althoughthese
lhexane. ' The residue is distilled in vacuo at o
About 13.5 grams or magnesium turning; are
created with about 82.5 cc. of cyclohexyl bromide
tn about 250 cc. of dry othcrto make a Grisnard
._
a mix
waterc-soltcuing,
good wet. sombmung,
=»
date}
‘ 1:,‘ "~11.
‘contains a major part of the unreccted cyclo
-
-
The sulpllinate and sulpbonste products ob
"
reaction mixture is ‘heated to about now to about
110° C, under on absolute pressure of about 250
millimeters of mercury and in at carbon, dlomde
atmosphere, 0. distillate being collected which
{smells strongly of thionyl chloride and which also
and about 90° C. is recovered.
@
obtained by ll‘ting about 3- sr- or sodium
cycioheuyl culphincte prepd
the p w-wr-r of
this invention with about doc, of ethylene bro-I
over a period of about two hours. At the eudof
‘this time, the lamp is turned o? and the
ture
is blown with carbon dioxide gas to sweep out
‘hydrogen chloride and unreacted chlorine. The
with tbiou'yl
products may ‘advantageously be used in hard
as well as in solt water, whether hot or cold, and
‘ in the presence or absence of large quontitico of
inorganic
dium sulphate,»
salts, itsuch
is generally
as sodium
preferred
chlorideto employ
- the sulphonste products for use in hard water.‘
The sulphinate ' and/orv sulphonate products
herein disclosed may also be used in admixture
with other wettins and emulsliylns agents, in
cluding alkali metal, ammonium and amine
scope or latty acids, resins, long chain alcohol
sulphates, monoclyccrldc monosulphates. sul
phonated mineral oil extracts and Turkey red oil,
lecithin. slycerolaminea, vmonoethuuolamlue, di
‘ethanolamlne and triothanolamine and their "
sows: alkaline soap bmlders, water softeners,
and othersalts including box-ax, “sodium carbon
ate, diluted-phosphates, tctrapliospbate. pyro- ~ phosphate,“ hexamctaphosphatc. sulphate. chlo
_ ride. acetate, citrate, tcrtrste, bicarbonate, aeo- _‘
qulcsrboncte. thiosulphotc, 1nd hydrosulphite,
and their other alkali, ‘metal, ammonia,‘ and
amine salts or alkyl esters; aolds,'includinz borlc
. sold, citric cold ‘cud tartaric acid; coloring mate
. tor, including dyes.,lnkcs. plsments; ; sbnslves
and tillers, including silica, ‘pumice, feldspar.
precipitated chalk, ini'usorisl ourthrbcntonltc,
talc, starch, and oil‘; liquids; including carbon.
‘ tetrachloride‘, pcrchlorctbylene, trichlorethyle‘n , j
crushed ice. and magnesium carbonate is added ‘0 76 slycerine, ethyl ‘alcohol. tctrsbydrolurturyl ol
-
2,412,909
T '13.
cohol, phenol, 'cyclohexanol, water,‘ tetralin, .
decalin, pine " oil, mineral oil, mineral oil ex
tracts, and naphtha; perfumes and 'deodorants;
fats, oils; fatty acids, monoglycerides, vitamins,
waxes. gums, glue, resins; germicides, including
phenol, mercuric chloride, phenyl mercury ni
trate, phenyl mercury chloride; and/or styptics.
such as aluminum chloride, adrenalin and cepha
lin. The type of addition agent to be‘ used will
depend, of course, upon the ultimate use of the‘
new compositions.
_
The ?nal composition, with or without one
or more addition agents, may be formed into
.
.
14
'
scope of. the present speci?cation and within the ‘
purview of the appended claims.
I claim:
-
'
1. The process of preparing sulphinic deriva
tives
of
_
'
proportion of a halogen in the presence of actinic
rays.‘
-
2. The process of preparing sulphiniclderiva
‘tives of organic‘ compounds whichv comprises
an organic compound having van ali
phatic group with thionyl bromide and a minor
proportion of a halogen in the presence
of actinic
light.
‘
beads, ?akes, bars, chips, crystals, powders, so-f
lutions, liquid or plastic emulsions, pastes,
creams, salves, or any other forms‘desired. The '
3. The process of preparing sulphinic derivaingredients
may be mixed by any of the common
tives
of organic _' compounds which comprises
methods, such as grinding, stirring, kneading,
treating an organic compound having an aliphatic
crutching, fusing, and drying of mixed solutions
or dispersions by heated rolls, ‘spraying‘or other 20
means.
'
The various products and‘ compositions of this
invention may be used for various purposes,
such as laundry detergents and other textile
thionyl chloride and a minor proportion of chic
rine in the presence of actinic light.
agents including laundry blueing, bleaching,
dyeing, .mercerizing, softening,‘ lubricating, and
discharging ‘ compositions; drain, lavatory and
radiator cleaners; anti-oxidants for soaps and
other compositions; reducing agents; paint,
minor proportion. of bro
stain and grease removers; dry-cleaning compo
‘sitions; rug cleaners; water softeners; washing
mine in the presence of actinic light.
treating an organic aliphatic compound with a
painted surfaces; liquid, solid and paste tooth
and mouth detergents; shampoos; cosmetics;
depilatories; deodorants and perfumes; antisep
35
ganic sulphinyl halides, and removing said or
ganic sulphinyl halides with a selective solvent
tics; insecticides; dust-preventing compositions;
?re‘ extinguishing compositions;- anti-freezing,
therefor.
anti-fogging, and anti-corrosion compositions;
wood impregnants; electrolytic baths; metal
plating; metal pickling; etching compositions;
40
tanning agents. and fat-liquors for leather; pho
tographic solutions; petroleum de-emulsifying
compositions; lubricating oil and fuel composi
' ore ?otation; fat splitting; cements and
abrasive ' compositions;
"
6. The process of preparing sulphinic deriva
tives of organic compounds which comprises
compositions for fruit, fabric, wood, metal, stone,
glass, brick, masonry, and alkali sensitive and/or
.
'50
.60
-
‘
‘7. The process of preparing
tives of organic compounds
sulphonic deriva
I
actinic'light and
about eight to about twenty-six carbon atoms
with a thionyl halideand a minor proportion oi
-a halogen in the ~presence oi actinic light. ‘
a temperature of about 25‘ to ‘
about 100° C. toitorm organic sulphinylchlorides,
:and hydrolyzingand neutralizing said organic
sulphinyl chlorides with an alkaline material.
15. The process of preparing organic, 'sulm
' 13. The process of preparing sulphinic deriva
tives of organic , compounds ‘which comprisesv
treating an organic alip ‘ atic compound having
phonates. which comprises treating an organic
about twelve to about twenty carbon atoms with
' twenty carbonatomsw'ith fthionyl chloride and,
aliphatic compound having abouttwelve to ‘about
thionyl chloride and a minor proportional a halo
' chlorine in the presence'ofv actinic light and at a
gen in the presence of actinic light and at a tem-\ 10 temperature of about 253 to about 100° C. to form\
perature ‘of about -i-10° to about 200‘! C.
organic sulphinyl chlorides, hydrolyzing and neu
1 14. The‘ processv of preparing organic sul- ~ tralizing said organic sulphinyl chlorides with an
' phinates which comprises treating an organic
alkaline materialto form organic sulphinatesr and
aliphatic compound having about twelveto about
twenty carbon atoms with thionyl chloride and
a minor proportion of chlorine in the presence of
‘oxidizing said organic sulphinates.
is
DWIGHT‘ ‘JAMES Po'rrim.
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