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Патент USA US2408302

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Patented Sept. 24, 1946
. ‘Thomas Edward Dillon, New Castle, Del.,- assignor -
" to E; I. du'Pont de, Nemours & Company, Wil-l
mington, DeL, a corporation of Delaware
‘ -. seeming. ‘Application October 30, 1945,
_ ‘Serial ‘No. 625,085
’ > " 5 claims. ' (01. 260-513)’
said limiting quantity would normally beem‘:~
.This'iin'vention' relates tola method tor hy
drolyzing organic'sulphonyl chlorides. More-par
. I have found that the use of such auxiliary
~ quantities of an active organic nitrogenous base
. ticularly, this invention"deals with a process for
preparing- aliphatic sulphona'tes by alkaline hy-.
drolysis of aliphatic sulp'honyl chlorides.
- has the e?ect of lowering the hydrolysis tem
perature, shortening the timeof hydrolysis, pre-.
venting excessive foaming and decreasing-the
' .The mentioned aliphatic sulphonyl ‘chlorides ’
are generally prepared by reacting‘ with a gase
ous mixturev of sulphur dioxide and chlorine or;
alternatively. with sulphuryl ‘chloride and a'cata
lyst, in the presence: of actinic light, upon'satu
rated aliphatic hydrocarbons having various
viscosity of the reaction mass.“ All of theserij‘acy
tors, together have the further; effect of: increas
ing the active-ingredient contentotthe' product;
inasmuch ,as_'decomposition or desulphonationlof
the product _during;the hydrolysis step is held by:
chain lengths (from "4' ‘to '50'carbon atoms) and
' the above factors at a minimum. The saiddecom-U
' position of the ,sulphonyllchloride appears to be
these’p'roc’esses,’ among‘ which the following‘ may 15 a vfunction of the,;.temperature, and accordingv
being straightich'ained or branched. . Numerous‘
patents ,have issued describing‘ and claiming‘
tov my invention, hydrolysis proceeds su?icient
1y rapidly at lower temperatures so that. excessive;
decomposition is avoided.
be. mentioned 'as ‘typical: Reed, Re. $20,968; Reed,
2,174,492; Fox etal,‘ 2,174,506‘; Tinker et 2.1.,
2,174,507; Fox ‘et al., 2,174,508; Lockwood et;al.,
2,193,824; Henke et al., 2334364; and Kharasch,
~~The products‘fof'theabbveflreaction are gen-‘
In practice according to my ‘invention, the sul-_E
phonylated reaction mass may be fed gradually
into a mixtureV of the aqueous alkali and the seV
erally .mono-,' di- or "polyesulph'onyl' chlorides,
lected-nitrogenous base. Alternatively, a mixture -
generally ‘been-achieved by reacting upon said
sulphonyl chlorides'with' aqueous alkali, particu
and then add the aqueousalkali. .
of "the nitrogenous-base and the aqueous alkali
oftenihaving one or more chlorine atoms attached
mayvbe ‘fed slowly into the sulphonylation mass.
directly to carbon atoms in the molecule.
~ The hydrolysis of ‘the aforegoin'g compounds to 25 A third option is to enter ?rst the selected nitrog
enous baseinto the sulphonylated reaction mass.
the gcorresponding ' sulphonates ‘has hitherto
The temperature of the mass during the hy-:
larly aqueous caustic 'soda. . Typical procedures
drolysis step may‘ vary. from'room temperature.
forT-jthis. purpose have beenv described'in the above
mentioned U. S. Jpatents‘ ‘as well as in‘ Reed.
torl20PpC. or higher. But inasmuch as it is de-'
2,174,110 and‘Reed,v 2,276,090.
7 -
sirable to keep decomposition down .to a mini
mum,‘ it ispreferred in practice to effect hy-'
drolysis at as low a temperature asis consistent
with good speed, say within a range of 70° to
"'In‘TJ'. S. Patent" No.‘ 2,319,121, arproposallhas'
employ alcohols as? hydrolyzing’g
been ': made ' to
- The present invention"isFconcerned primarily
"Without limiting my invention, the following
with ‘the caustic alkali method vof hydrolysisPand'
' examples are given to illustrate my preferred
mode of operation.
it; is 'an‘object of this invention to improve said
method in a'general way,=wh'ereby_to facilitate
hydrolysis and to produce better quality products;
Other and further important‘objects of "this in
vent'ion will appear as ‘the ‘description proceeds."
"I' have found that several- ‘distinct improve-._
ments,_as_more_fully discussedbelow, are obtained
if the hydrolysis of ' thelabove indicated. organic
sulphonyl chlorides is‘ e?ected by the aid’ of
aqueous alkali inthe'presence of a small quan-.
tity ofzan aCtivebrganic nitrogenous base. ' By
“active? I means that‘ the'base will readily form,
a’, saltwith hydrogen chloride. By “small quan
Parts mentioned are "byv
Example 1
'A mixture of 336 parts of S02 and 267 parts
of chlorine was passed into 300 parts of molten
re?ned para?in .wax (M. R. ‘120-122? F., ‘A.’ S'; V
‘T. M.) while the mass was agitated and exposed
.‘ to actinic light as described in U.IS. Re. 20,968.
The product was then hydrolyzed by adding
gradually with agitation to a mixture of 262 parts
of 50% aqueous sodium hydroxide solution and
7.5 parts of Solvent P (the commercially‘ avail
able mixture . of I mono-, 'di-,' and vtri-ethanol
tity"~l_meanany quantity less than that which ._ I amines) ,‘ maintained at a temperature between 85
would byitseli su?lcetoefiect‘hydrolysis oi the ‘and 90° C. V The hydrolysis mass was noticeably‘
museum vor . sulphonyl ;.ch.1Qiide. although
thinner and-smoother throughout than in a‘ simi
in. the; were. .ordinarrrracticeless than. 20% ‘or; 55 . lav-hydrolysis in. absence of any amine. The _re_..
action was also completed in a much shorter
the product used had
190-210" C.
time, without foaming dii?culty, and the product
a boiling range of
The product was hydrolyzed by-adding grad
was obtained in better yield and quality.
Example 2
A ‘mixture ‘ofv 116 parts of S02 and. 83 parts of
C12 was passed into 324 parts of No. .40 white oil
ually to 294 parts of 40% aqueous NaOH con
taining 9.6 parts of pyridine while maintaining
the temperature in the range~95-105° C. The
hydrolysis mass was diluted with alcohol'and ?l
in a manner similar to that described in Exam
tered, unreacted oil was separated and the con-'
ple 1. This oil is a saturated petroleum fraction
‘centration of the remaining mass was adjusted
of boiling range 265-300° 0., sp. gr. 0.801 and 10 to 50% of active ingredient. The mass remained
Saybolt Universal Viscosity 36-37 sec. at 100° F.
thin and smooth during the hydrolysis, with no
The resulting product was hydrolyzed by add
foaming and a good yield of light colored prod
ing gradually to 242 parts of an aqueous 730% , uct'was obtained. Similar results were obtained
sodium hydroxide solution containing 4 parts of _
morpholine, while maintaining the temperature ,
at 75-85° C. The hydrolysis mass was further
diluted with water until the unreactedv oil;sepa-.:
rated. The latter was removed and the hydro
lyzed product, after addition of sodium sulphate
by .using'..9.6 parts of trimethylamine in place of
.the pyridine.
It will be understood that the details in the
above examples may be varied within wide lim-‘
its, without departing from the spiritof this
invention. Thus, the alkaline solution may be
and borax, was evaporated to dryness on a drum 20 heated to 70°-80° C. prior to neutralization or
dryer. Advantages similar to those described in
may be at room temperature before beginning
Example 1 were found in having the amine
the addition of sulphonyl chloride.
In place of the nitrogenous‘base's named in
Example 3
the examples, many others may be used, tonin
A- mixture of 95'parts of 902V and 76 parts of 25 stance, pyridine, -piperidine,-pic'oline', nion‘o-gr'die,
or tri-ethanolamine, morpholine, N-methylrmor
612- was passed into 270 parts of No.30 whitev oil
pholine, or diethyl-cyclohexyl amine. ‘In- general,
as previously described. This- oil is a‘ completely
it is believed that any nitrogen base which read
saturatedpetroleum fraction typically with a
ily forms a hydrochloride salt will assist inthe
boiling range of 210-2509 0., sp. gr. 0.781 and
neutralization of the aliphatic 'sulphoriyl "chlol
Saybolt-Universal Viscosity oi? 32-33 sec. at 100° F.
The sulphonylated product-was hydrolyzed as
ous NaOH-containing 2 parts o'f'monoethanola
mine, while.‘ maintaining‘ the temperature at
The mass‘was dilutedsoias to'contain '
about’ 22% of active ingredient, the. oil was sep
arated and‘the aqueous'product was used in this
form. The hydrolysis proceeded smoothly in the
presence-of the monoethanolaminea
Example 4
For some uses the small amounts 'of amine
previously d'escribedwith-1365 parts of 20% aque
left in the product may be objectionable if an
amine with an unpleasant odorsuch as the methyl
amines, pyridine, etc., is'used as thechydro'lysis
catalyst. For such uses it is‘usually, ‘preferable
to employ odorless ‘amines such as ,therethanol.
amines. On the other hand, the unpleasant
smelling amines may be removed or chemically
altered after the hydrolysis, in knownmanner'
such as by treatment with ethylene oxide, oxida
A mixture of-106 parts of re?ned; para?iin' wax
and 19 parts of petrolatum was treated‘ with. 88
tion; etc. Similarly, aromatic amines may'ibe
objectionable where the product is to be‘ us'ediin
parts of S02 and 49 parts of C12 :aspreviously
personal contact.
The hydrolysis was carried out with: 1125 parts‘
of 50% aqueous NaOH. in the presence of..5:. parts
for complete neutralization‘ of th’e'sulphonchlo;
ride. ‘However, 1-3%,on- the weight or the stile
phonylation mass" has‘ been found to produce‘ the:
of pip-eridine. The hydrolysis was startedat room
temperature and the temperature was allowed
to. rise to 70° C. during hydrolysis. 'Thehydrolye
sis' proceeded smoothly without formation or
lumps and the product was alight cream coloredv
paste ready for use.
Example 5
The concentration of the amine used in cata
lyzing the hydrolysis may vary from 1% up to‘
15% or 20% of the theoretical quantity required:
most‘ desired effect at minimum cost.
A mixture of 285 parts‘ of re?ned paraffin: wax
and 0.97 parts‘ of stearamide was ‘heated to$70° C.
and 428 parts of sulphuryl chloride was added
over a period of 4 hours while irradiating with
actinic light as described in U. S. 2,383,319.
To this mixture was added 15; parts of tri
by the above examples.
ethanolamine, then 192 parts of‘ 65% aqueous
when di-, and polysulphonates are being hy
_ The effects produced when-using the'auxiliary'
amines during hydrolysis are morenoticeable
NaOH was gradually‘ added with agitation "while
maintaining the temperature. in‘. the: range 85-95" ,
C. ‘The hydrolysis" proceeded smoothly‘ and- rapid’
1y, yielding a smooth cream colored’ paste.
Example. 6
A mixture‘ of 187: parts of SO‘zi'an‘d‘ 145 parts of
Cll.r was passed into320 parts'of “alkyllatio'n' bot
toms” with. agitation and irradiation.
“alkylation bottoms” ‘consists ot a mixtureloti'
saturated branched chain hydrocarbons-obtained
as". a: byproduct . from‘ isosocta‘ne' mama-aw
As for the alkali, potassium hydroxide, calcl-iim
hydroxide, or other metallic hydroxidesiwhich
react with sulphonyl chlorides maybe used for
actual vpractice,in however,
lieu of sodium
prob-ably the only one that would-normally‘ be‘
used. ,The concentration of the "alkali may vary"
appreciably, say from. 20% to 65%, as illustrated.
In general, all aliphatic hydrocarbon s‘lil'pl'ionyl
chlorides may be neutralized iii this'irianr‘iei'.
The advantages ofr‘my invention may‘ ‘now be
summarized- as follows‘; The aminfe catalyst keeps
the hydrolysis mass‘ thin‘, throughout and pre;
vents‘ formation and development‘ of local acidity.
Such local acidity causes‘ desulphonylation'
results in troublesome foaming; of the hydrolysis
mass asv well as-Ios'sin yield. ; With a'g-ivlenl degree‘
of; agitation ‘ and a given temperature "thétfmeof
hydrolysis is- considerably shortened, reducing- the"
cost of the product by increasing the capacity
' 'ing upon said sulphonyl chloride with an aque
of the equipment; alternatively, the same reaction
time may be achieved at a lower temperature.
ous solution of a‘caustic alkali in quantity sub
The disadvantage vof increasing temperature to
reduce the reaction time, rather than using the
catalyst, is that desulphonylation increases with
increasing temperature and this reduces yield and
quality of product. Also,- although the hydrolysis
is improved by improving the agitation such im
provement is often limited by the tendency to
foam. When proceeding according to my inven
tion, the tendency to foam is considerably re
stantially equalto that theoretically required for
complete hydrolysis and in the presence of less
than the stoichiometric quantity of an ‘organic
nitrogenous base .7 which is sufficiently basic to g
' form a salt with hydrogen chloride.
4. A process of hydrolyzing an aliphatic sul- '
phonyl chloride to produce a salt of the corre
sponding sulphonic acid, which comprises react
ing upon said sulphonyl chloride with aqueous
caustic alkali in quantity substantially su?icient
to e?ect by itself the desired hydrolysis, said
aqueous alkali containing further a quantity of
I claim as my invention:
1. In the process of hydrolyzing an aliphatic 15 an organic nitrogenous base corresponding in
molar proportion to not over 20% of the quantit
sulphonyl chloride by reacting "upon the same
of the caustic alkali employed.
with aqueous caustic alkali, the improvement
5. The process of hydrolyzing an aliphatic sul
which consists in effecting the reaction in the,
phonyl chloride to produce the corresponding so
presence of an organic nitrogenous base.
2. A process of hydrolyzing an aliphatic sul 20 dium sulphonate, which comprises entering said
organic sulphonyl chloride, at a temperature of
phonyl chloride to produce a salt of the corre
about 80° to _100° 0., into an aqueous solution of
syponding sulphonic acid, which comprises re
sodium hydroxide of 30% to 50% strength and
acting upon said sulphonyl chloride with a mix
containing a quantity of an organic nitrogenous
ture of a caustic alkali and an organic nitrog
corresponding to from 1% to 3% by weight
enous base in an aqueous medium.'
of the organic sulphonyl chloride to be treated.
3. A process of hydrolyzing an aliphatic sul
phonyl chloride to produce a salt of the’ corre
' spending sulphonic acid, which comprises react-'
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