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Патент USA US3100230

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United States Patent 0 " ice
Patented Aug. 6, 1963
degree, for example :by isomerisation. Thus, for exam
ple with the decomposition of ?uorosulphinic acid-nlbutyl
ester, relatively small quantities of 2-butyl and labutyl
?uorides are formed as Well as a large quantity of butene-l
Albrecht Zappel, Cologne-Starnmheirn, and Heinz Jonas,
Leverkusen, Germany, assignors to Farhentahriken
and butene-‘Z.
T‘ihe ?uorosulphinic acid esters can be prepared by
Bayer Aktiengeselischaft, Leverkusen, Germany, a cor
?uorination of the corresponding chlorosulphinic acid
No Drawing.
of Germany
Filed Dec. 19, 1960, Sex‘. ~ Nd. 76,403
esters with KSO2F.
The preparation of chlorosul?nic acid esters is described
Claims priority, application Germany Dec. 24, 1959
9 Claims. (Cl. 260—487)
in the following speci?cations:
Stahler and Sohirrn,
Berichte 44, page 321, or A. Streitwieser et al., Journ.
Am. Chem. Soc. 79 (1957), pages 379-381. The pro
The invention is concerned with a process for the pro—
duction of ?uorine-containing organic compounds by ther
duction ‘of potassium ?uorosul?nate (KSOZF) is described
mal decomposition of ?uorosulphinic acid esters. A par
by F. Seel et al., Angew. Chemie 67 v(1955), page
ticular advantage of the process is its versatility. Not
only can simple alkyl ?uorides be prepared in accord 15 32 et seq.
The invention is further illustrated by the following
ance path the process, but complicated componds with
functional groups, for example ethers or carboxylic acid
esters can also be prepared.
The decomposition proceeds in accordance with the fol
lowing reaction scheme
Example 1
(a) 0.1 mol of '?uorosulphinic vacid-mbutyl ester is
heated in a silver apparatus with a re?ux condenser. The
substance boils under re?ux at a sump temperature of
about 120° C. ‘90% 1of the substance introduced is unde
R standing for an organic radical.
composed after heating for 5 hours. Small quantities of
Concurrently with this reaction, there is a disproportion
ation reaction which is strongly pronounced with ?uoro 25 l—butyl and Z-butyl ?uorides as well as S02 can be de
sulphinic acid esters:
(b) 0.1 mol of ?uorosulphinic acid-n-butyl ester are
quickly heated to 180° C. in a :silver autoclave with a
capacity of ‘250 ml. and kept at this temperature for 1
Whereas the disproportion-anon predominates at rela—
tively low temperatures of up to approximately 150° C.,
the desired decomposition reaction proceeds substantially
more rapidly ‘at higher temperatures. The most favour
able temperature ‘for the decomposition into S02 and RF
differs from compound to compound and must be estab
hour. The volume or" the gases which are formed is meas
ured and the mixture is analysed by mass spectroscopy.
The ‘following gases were formed:
Percent yield
_______________________________________ __ 8 -9
Butene _____________________________________ __ 5-6
lished for each speci?c case. The temperature range with
in which the decomposition may be carried out is between
about 100° to about 300° C. preferably 150° and 220° C.
In order to avoid losses in the yield by disproportionation
___________________________________ __
(c) [0.1 mol of ?uorosul-phinic acid—n—butyl ester is
heated in the presence of 1% by weight of BF3-etherate
of the ?uorosulphinic acid ester, it is accordingly necessary
to heat rapidly up to the decomposition temperature. Gen
in a silver apparatus as in Example -1. The sump temper
ature is raised in 25 minutes to 190° C. The gases formed
are collected and analysed and the following are found:
erally speaking, this condition is particularly well ful?lled
in pressure vessels, as by using pressure vessels the entire
reaction zone can quickly be brought to the required
Percent yield
temperature. The product to be decomposed is thereby 45
not prevented from rapidly being ‘brought to a high tem
S02 _______________________________________ __ 90
perature, as occurs when boiling under re?ux is used as
a method of heating. A particularly suitable material ‘for
the decomposition apparatus is silver. Glass vessels are
1-C4H9F ___________________________________ __ 10
_______ __
____ __ 26
unsuitable, since ?uorosulphinic acid esters attack glass 50
Similar experiments in the presence of other acceptor
to a certain extent and in addition glass greatly acceler
such as AlF3, A1013, SnCl2, SnFz and ZnClg
ates the disprop-ortionation reaction.
teel vessels are
show in principle the same result.
harmful, since heavy metal halides can form on the sur
(d) 0.1 mol of ?uorosulphinic acid-n-butyl ester is
face, and as acceptor compounds, these unfavourably in
in the presence of 1% by weight of tributylamine
?uence the decomposition due to their catalytic action on
in the silver apparatus described in Example 1. This re
the ole?nic splitting of the organic ?uoride.
action ‘mixture boils for about 1 hour under re?ux at ‘a
As starting materials, ?uorosulphinic acid methyl ester
temperature [of ‘120° C.; with increasing decomposi
comes into consideration and also the corresponding ethyl,
temperature rises in 1 hour to 200° C. The
propyl, butyl, 'octyl, nonyl esters, but also ?uoro sulphinic
acid ?-methoxyethyl ester and ?uorosul-phinic acid a-car 60 gases which form are collected and analysed as is the
residue remaining in the reaction vessel. The result of
boxyet-hyl ester may be used.
experiment shows:
Donor compounds, such as tertiary amines which are
aliphatical'ly and/or aromatically substituted are suitable
57.6% yield \of S02
as catalytic additives.
Such donor compounds are e.g.
tributyla-mine, dimethyl aniline, pyridine.
3% yield of C4H8
Without the addition of donor compounds, and particu
larly when acceptor compounds, such as BF3, AlCl3,
46% disproportionation to S(OC4H9)2 and SOFZ
ZnClg, SnClZ and others ‘are added, the decomposition of
the organic ?uorine compounds into ole?nes and HP is
(e) 0.1 mol of ?uorosulphinic acid n-butyl ester is
very marked. In addition, the organic decomposition 70 heated in :a silver autoclave in the presence of 1% by
product may undergo transformation to a considerable
weight of dimethyl aniline in 1 hour to ‘200° C. and kept
for ‘a further hour at this temperature. 0n working up
Without decomposition catalysts and in the presence
of acceptor molecules, the decomposition proceeds in an
the reaction products the following products are obtained:
89% yield of S02
uncontrollable manner and with ‘only small yields of the
required oc-?uODOpDOpiOIliC acid ethyl ester. In the pres
‘5% yield of Cells
89% yield of l-C4H9F
ence of donors and when heating without pressure, it is
2-C4H9F cannot be detected.
Similar experiments with ‘other donor compounds in the
form of tertiary amines such as tributylarnine and pyridine
give similar results.
Example 2
(a) Fluorosulphinic acid-{i-menhoxyethyl ester
mainly the disproportionation reaction to SOF2 and
OS(OCH(CH3)COOC2H5)2 which takes place. Good
yields are ‘on the other hand obtained in the presence
of donor molecules such as tertiary amines and rapid
heating in a pressure vessel to the ‘decomposition temper
Using a 2510 ml. silver autoclave, 0.3 mol=55.2 g. of
FSOOCH(CH3)COOC2H5 and 0.5 g. of dimethyl aniline
are quickly heated in a few minutes to 200° C. and kept
at this temperature for 2 hours, a pressure of 27 atm.
is boiled under re?ux for 3 hours in a silver apparatus,
the sump temperature being 138° C. With the subsequent
fractional distillation, the major part, about 90% is re
cover without decomposition.
There are formed:
92% of theory of S02
63% of theory of CH3CHFCOOC2H5
'('b) 0.1 mol of FSOOCH2CH2OCH3 is quickly heated
to 200° C. in an autoclave lined with silver and kept
as well as 6% of C2l-l5F, 1.1% of 021-14 and products
of higher boiling point which cannot be identified. a-Fluo
ro-propionic acid ethyl ester is fractionally distilled in a
rotary band column. The boiling point at normal pres~
for 1 hour at this temperature. On working up, ‘(i-?uoro
ethyl methyl ether is obtained in a yield of approximately
‘20% and methyl fluoride in a yield ‘of about 7%. The
product introduced has certainly been quantitatively de
composed, but substance of ‘higher boiling point which
sure is 121° C.
We claim:
1. A process of preparing an organic ?uorine-contain
cannot :be identi?ed have in the main been formed.
(0) On heating FSOOCH2CH2OCH3 without pressure
ing compound selected from the group consisting of esters,
ethers, and alkyl ?uorides which comprises thermally de
in the form of its etherate, A-lCl3, Snclz, ZnCl2 etc., com~
plete decomposition occurs. It is mainly CH3F which 30 composing a ?uoro-sul?nic acid ester by heating said ester
to a temperature of from about 1010 to about 300° C. and
is formed, and ?-?uoroethyl methyl ether cannot be de
recovering the organic ?uorine-containing compound
tected. The decomposition does not proceed in the de
thereby formed.
sired manner.
2. Process according to claim 1, which comprises e?fect
(d) 0.1 mol of FSOOCH2CH2OCH3 is heated with 1%
ing said heating to a temperature of from about 150~
by weight of a donor compound, such as pyridine, di
220° C.
methylaniline, tributylamine or the like in a silver appa
3. Process according to claim 1, which comprises eiiect
ratus. The substance boils initially under re?ux at a
ing said heating in the presence of a tertiary amino.
sump temperature of about 130° C. During the experi
4. Process according to claim 3, wherein said tertiary
ment, which last 8 hours, the sump temperature rises to
about 200° C. On Workingup, a yield of 93% of bis43 40 amine is tributylamine.
5. Process according to claim 3, wherein said tertiary
metlroxyethyl sulphite OS(OCH2CH2OCH3)2 is found,
amine is dimethylaniline.
that is to say, the fluorosulphinic acid ester is almost
6. Process according to claim 3, wherein said tertiary
quantitively disproportionated.
amine is pyridine.
(e) 0.1 mol of FSOOCH2CH2OCH3 is quickly heated to
'7. A process of preparing l-buty'l?uoride, which com
gether with 1% by weight of tributylamine in a silver
in the presence of acceptor molecules ‘(1%) such as B133
prises thermally decomposing fluorosul?nic acid n-butyl
autoclave to ‘180° C. and kept at this temperature for 1
hour. A pressure of 15 aatm. results.
ester by heating said ester at a temperature of [about 200°
pressure (121320 1.3487, D420 0.94).
Example 3
Fluorosulphinic acid-a-carboethoxyethyl ester
ether thereby formed.
‘9. A process for preparing cx-?UOI‘OPl‘OplOHiC acid ethyl
ester which comprises thermally decomposing ?uorosul
?nic acid ot-carbo-ethoxy-ethyl ester by heating said ester
C. in the presence of about 1% by Weight of dimet-hyl
Working up gives a yield of 76% ‘of FCH2CH2OCH3.
aniline and recovering the l-Ibutyl?uoride thereby formed.
About 2% ott methyl ?uoride is formed.
8. A process of preparing ?-?uoroethyl methyl ether
(f) 0.5 mol of FS0OCH2CH2OCH3 is heated for 2
which comprises thermally decomposing ?uorosul?nic
hours to 200° C. as in Example 2e, the maximum pressure
acid-,B-methoxy ethyl ester by heating said ester to a.
being 48 ‘atm. ?-?uoroethyl methyl other is isolated in a
temperature ‘of about 180° C. at a pressure of about 15
yield of 65% and a yield of about 7% of CHgF is ob
atmospheres in the presence of about 1% by weight of
tained. FCH2CH2OCH3 boils at 57° C. under normal
tributylamine and recovering the B-iluoroethyl methyl
60 to a temperature of about 200° C. at a pressure of 27
atmospheres in the presence of about 1% by Weight of
which is obtained for example by ?uorination of the cor
responding c‘hlorosnlphilnic acid ester with KSOZF, has 1a
behaviour on decomposition which is quite similar to that
dimethylaniline and recovering the a-?uoro-propionic acid
ethyl ester thereby formed.
of the ?uorosulphinic acid-?érnethoxyethyl ester described
No references cited.
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