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Fluorinated -Sultones.

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Fluorinated P-Sultones
By I. L. Knunyants and G. A. Sokolski[*'
Fluorinated p-sultones are formed on addition of sulfur trioxi- to fluorinated olefins. Tetrafluoroethanesultone has been studied particularly thoroughly. The title compounds are characterized by the ease with which they undergo ring cleavage to give, e. g., derivatives of a-sulfo
carboxylic acids, of sulfonic acids, of carboxylic acids, and of sulfuric acid. Fluorinated compounds of this type containing an a-hydrogen atom are especially valuable in preparative work.
1. Introduction
The name sultones refers to the inner esters of hydroxyalkanesulfonic acids, which may also be regarded as sulfur
analogs of lactones. As with lactones, there exist a-, p-, y-,
6-sultones and numerous other cyclic sulfonates of this
kind. Among the unsubstituted compounds, the y- and
6-sultoneshaving five- and six-membered rings, respectively,
are the most stable. Unsubstituted p-sultones decompose
Their formation by this reaction has been well studied for
numerous examples. Moreover, a synthesis via sulfene
intermediates has also been described['"!
2. Synthesis of p-Sultones
That sulfur trioxide reacts with olefins was demonstrated
as long ago as the beginning of the 19th Century for the
case of ethylene"b,2! The reaction was subsequently extended to a large variety of substituted ethylened3 61, to a
number of chloroolefin~[~
- 'I1, and fairly recently to fluorooIefins["- '*I.
~
extremely readily and have not yet been isolated. In contrast, fluorinated p-sultones of type (I), formed by addition
of sulfur trioxide to polyfluoroolefins, are relatively stable.
The reactions of sulfur trioxide with polar reagents of type
A-B can be described by a series of equilibria.
60 60
p]
Prof. Dr. I. L. Knunyants and Prof. Dr. G. A. Sokolski
Institute for Organoelement Compounds of the
Academy of Sciences of the USSR
Moscow V 312, U1. Vavilova 28 (USSR)
Angew. Chem. internat. Edit. 1 Vol. 11 (1972) 1 No. 7
6060
A-B + so,
= A-B-SO,-OO
0
B-SO,-0-A
The initial step in the reaction of sulfur trioxide with olefins
is an electrophilic attack by sulfur trioxide on the double
583
bond[6* I'. The intermediate n-complex isomerizes to
give a zwitterion in which the sulfur atom is bonded covalently to the carbon atom having an enhanced electron
density.
''9
\ /
\
/
c
bObO
/c=c\ + so3 * 6011----+S03
A
+
,o
I
/c-c-soz-o~
I
so,
Further reaction of the zwitterion is determined by the
properties of the starting olefin and the reaction conditions.
Apart from the p-sultones ( I ) , the eight- and six-membered
heterocycles (2) and (3), each containing two -SOz-Ogroups, and the 6-sultones ( 4 ) may be formed in individual
cases.
;23 -
+
isolate the highly unstable primary adducts formed by vinyl
fluoride['81and fluorotrichloroethylene[' were unsuccessful. Tetrafluoroethylene gives not only the p-sultone (If)
and the six-membered heterocycle (3b), but also the eightmembered cyclic compound ( 2 ~ ) ~we' ~were
~ ; unable to
confirm whether tetrafluoroethanesultone (If) is accompanied by tetrafluoro-1,3,2-dioxathiolane2-oxide["* 18].
This cyclic glycol sulfite was not isolated but merely
postulated to explain the results of alkaline hydrolysis of
(If) and the 19F-NMRspectra of its hydrolysis products.
It was later established[291that the observed deviations are
due to isomerization of the p-sultone (If) to the alkenyl
fluorosulfate(see Section 3).A similar explanation probably
applies to the unconfirmed r e p ~ r t [ ' ~that
,'~~
a mixture of
two p-sultones results on reaction of chlorotrifluoroethylene with sulfur trioxide. It is reasonable to assume that,
in this case too, only the a-chloro p-sultone ( I c) is formed
which then isomerizes to the alkenyl fluorosulfate.
- so, -0Q
Addition of sulfur trioxide to unsubstituted olefins proceeds
extremely readily and is so exothermic that the primary
adduct is very difficult to trap. It is therefore necessary to
subdue the electron-accepting properties of sulfur trioxide,
which is readily accomplished by using sulfur trioxide in the
form of its quasi-complexes, e.g. with dioxane (SuterBordwell method) or with pyridine (Terent'ev method).
The presence of electron-withdrawing substituents in the
olefin reduces its proclivity to add sulfur trioxide. Whereas
ethylene[*']and vinyl chloride["' even react with pyridinesulfur trioxide, addition to dichloro-, trichloro-, and tetrachloroethylene occurs only with free sulfur trioxide. 1,2Dichloroethylene reacts exothermally at room temperatureLgl but trichloroethylene[8.''] and especially tetrachloroethylene react only on heatingF7*
"]. Reaction products of p-sultones are formed in all these cases.
The opposite is observed on going from chloro- to fluorocompounds within the series of perhalogenoolefins: fluoroolefins react more readily with sulfur trioxide than do their
chlorine analogs. Thus tetrachloroethylene and fluorotrichloroethylene react with sulfur trioxide at 180-200
and 160-180°C~221respectively, symmetrical and unsymmetrical difluorodichloroethylene at 80°C['2r 5 s 18], and
tetrafluoroethylene at 40-50°C['71.
The data listed in Table 1 show that strict orientation
always prevails in the addition of sulfur trioxide to unsymmetrical polyfluoroolefins. This definite orientation
confirms the ionic character of the reaction and the intermediacy of a zwitterion (see above). Further evidence is
provided by the additional, and sometime predominating,
formation of six-membered cyclic compounds of type (3).
This is also the only possible explanation of the formation
of the eight-membered cyclic by-product ( 2 a ) on reaction
of tetrafluoroethylene with sulfur trioxide. Styrene and
sulfur trioxide are known to form a similar compound[301.
The stability of fluorinated p-sultones came as no surprise.
Many different types of polyfluorinated four-membered
ring compounds are already known, e. g . perfluorocyclobutane ( 6 ) and the extremely stable perfluorooxetane ( 7 ) ,
as well as the relatively stable polyfluorooxazetidines (8)
and polyfluorodiazetidines ( 9 ) .
'
The optimum temperatures for the reaction of various
fluoroethylenes with sulfur trioxide are given below :
F2C=CF,
40--50°C
FHC=CF2
20-30°C
H2C=CF,
0°C
HZC=CHF
-30°C
Finally, an alkoxy group in a fluoroolefin activates the
molecule so strongly that some of these compounds of
type ( 5 ) still even react with sulfur trioxide at -30°C[231.
Reaction of polyfluoroolefins correspondingly gave psultones or compounds of type (3) (Table 1). Attempts to
584
The comparatively high stability of fluorinated p-sultones
permits their large-scale production by heating a mixture
of sulfur trioxide and polyfluoroolefin in a pressure reactor
or passing the gaseous components through a heated tube.
The accessibility of fluorinated p-sultones was the main
reason for the detailed study of their chemical properties
and for their suggested use as intermediatesin the laboratory
and in industry.
Angew. Chem. internat. Edit.
Vol. I1 (1972) 1 No. 7
Table 1. Products of reactions between halogenoolefins .and sulfur trioxide.
Olefin
Product
Ref.
H,C=CF,
C1,C
= CF,
F2
;"c
FClC = CFX
F X
[12,15, IS]
[12-16,18]
c231
c231
X=Cl
X=F
X = OCH,
X=OC,H,
F,C
[13-16,18,25,26]
= CF,
c241
[is, 18,24,27]
F,C-CF
= CF,
[12-16,181
[15,18,28]
F3C-CC1 = CC1-CF,
(CF,),C
[121
= CF-OX
X = CH,
X = C,H,
~ 3 1
c231
XFC = CF,
X=H
X = FCl,C-CF,
X = F,ClC-CFCl-CF,
X = n-C,H,
X =n-C,F,
X = F,CIC-(CFC1-CF,)z
X = H-(CF,),
X =F,ClC-(CFC1-CF,),
X = F2ClC-(CFCl-CF2),
3. Possible Reactions of p-Sultones
Fluorinated J3-sultones dissolve readily in saturated hydrocarbons, in their fluoro and chloro derivatives, and in polyhalogenoolefins.With water and most inorganic and organic
compounds p-sultones undergo vigorous decomposition
to give derivatives of sulfonic acids or sulfuric acid, depending upon the nature of the reagent.
The hydrolysis of fluorinated p-sultones is very informative.
Thus alkaline hydrolysis of tetrafluoroethanesultone or
Angew. Chem. internat. Edit. 1 Vol. I 1 (1972j 1 No. 7
of I-chlorotrifluoroethanesultone gives dihalogenosulfoacetic acid ( l o ) ,whereas fluorosulfuric acid and glyoxylic
acid are obtained on hydrolysis with sulfuric acid.
&
,SOz - OH
+ 2 HF
FHalC.
'COOH
(10)
F
aq.
$3
HHal + 2 H F
+ HO-SO,-F
+ OHC-COOH
585
Various differences in dependence upon the pH value of
the solution are also observed in the hydrolysis of other
fluorinated p-sultones, e.g. 1,2,2-trifluoroethanesultone
( I i) and perfluoro-1,2-propanesultone ( 19).
Decomposition of a-fluoroalkyl sulfonates of type (13)
is also initiated by nucleophilic c o m p o u n d ~ [ ~ ~ - ~ ~ ] .
(:F@
R‘-SOp
SO, - OH
oHQ_
HFC’
+2
HF
‘COOH
2 HF
+ HO-SO,-F
OHC - COOH
Fez
F3C
OH@
F,C-CHF-SO,-OH
+ 2 H F + CO,
H F + HO-SO,-F + F,C-CHF-COOH
F,
The weH-known decomposition of a-halogeno alkyl esters
and thio esters of phosphoric acid, nitrous acid, and even
of carboxylic acids can be explained similarly. These reactions confirm the lability of esters bearing an a-halogen,
which class includes the fluorinated p-sultones.
Acyl
Gl)!
The reactivity and in particular the chemical properties of
fluorinated p-sultones on hydrolysis can be explained in
terms of Scheme l[31*321.
x,@
P
F
i
1
4
Acyl-Hal
+ X,C=O
X,C
The second kind of isomerization of fluorinated p-sultones
has so far been observed in one case only, uiz. conversion
of tetrafluoroethanesultone (If) into trifluorovinyl fluorosulfate (12aj which occurs on prolonged storage at room
temperature in the absence of water[”].
SQZ
FzLO
+
F,C=CF-O-SOz-F
(124
F,
(If)
Scheme 1
On prolonged heating, P-fluorinated p-sultones is0meriz.e
to a-fluorosu~fonyl
po~yfluoro carbonyl fluorides
1)tz.5, 31.331. Isomerhtion is initiated by nucleophj~ic
reagents including triethylarnine“5*l8], ammonia[341,and
d i o ~ a n e [ ~ ~Even
. ~ ~on
I . brief exposure to moist air some
isomerization is observed. The best catalysts for this reaction are hydrogen fluoride and alkali metal fluorides.
The process is accelerated by phase transitions, i. e. by
repeated crystallization and melting (between -40 and
ooc).It was assumedtzoJthat isomerization is facilitated by
the orientaticm of the p-sultone molecules [cf. (14)].
@&g
@3s
‘0 ............so
F
xe
F
F,
SO, - F
b_ XFCC
(11)
CO-F
The course of this isomerization and its initiation by nucleocan be represented as a
Philic
process
(Scheme 2) in which the fluoride ion-liberated from
fluorinated P-suItone-pIays the main role1351.
x so,
FFg FZ
x so,
Fq2
-
,SO,-Base
xFc\CO-F
SO, - F
XFC:
CO-F
F F
(11)
Scheme 2
586
-+
2 XFC=CF-O-S02-F
(12)
(14)
Such an orientation occurs randomly in the liquid phase
but regularly on crystallization :isomerization is therefore
incomparably slower in the former case than in the latter.
If crystalline tetrafluoroethanesultone is kept for a long
whose
time at - 78 ocit yields a polymer
is also attributable to the regular arrangement of molecules[39].
+ Fo
+ F@
On heating or in the presence of nucleophiles depolymerization sets in to give fluorosulfonyldifluoroacetyl
fluoride (11aj[391.
The combination of the sulfonyl group and a fluorine atom
in a strained four-membered ring is a particular feature of
Angew. Chem. internat. Edit. 1 Vol. I 1 (1972) No. 7
of the molar refraction of the fluorosulfonyl group bound
fluorinated p-sultones. These characteristics and the
thermodynamic stability of the fluorosulfonyl g r o ~ p [ ~ ~ , ~ 'to
I carbon: RF-So,= 10.54 cm3[501.
would suggest ready ring cleavage to form that group.
Mono- and polybasic aliphatic and aromatic acids have
been used to form mixed anhydrides with p-sultones. The
resulting mixed anhydrides of carboxylic and a-fluorosulfonyl polyfluoro carboxylic acids are effective acylating
agents for alcohols, phenols, and thiols15'I. Reaction yields
derivatives of the carboxylic
491.
If the process is initiated by nucleophilic attack by an
electron donor on the sulfonyl group, derivatives of a-sulfo
polyfluoro carboxylic acids of type (11) are formed by
heterolysis of the ester linkage. Under phase transition
conditions, on the other hand, heterolysis of the S-C bond
ensues giving sulfates of type (12) or polysulfates of type
(15). Transformations of this kind in stable compounds
under phase transition conditions represent a truly remarkable phenomenon.
3.1. Conversion of P-Sultones into Derivatives of
a-Sulfo Carboxylic Acids
Treatment of P-fluorinated p-sultones with nucleophilic
compounds containing mobile hydrogen atoms furnishes
derivatives of a-sulfo carboxylic acids. The p-sultone
initially isomerizes to a linear a-fluorosulfonyl polyfluoroacyl fluoride of type (11) that subsequently acylates the
nucleophile to give (16)[20*31,353
.The reactions summarized in Table 2 are in accord with this view.
o_ X2C\
CO-F
I
CH,O-CO-R
SO, - F
+
2
x,c/\
COOH
Only in those cases in which a strong carboxylic acid is
made to react with the 0-sultone does the acylation reaction
lead to a derivative of the a-fluorosulfonyl carboxylic acid
alongside the major product. The ratio of the strengths of
the two acids apparently determines which product is
formed in this process (SN1or S,2)L491. Thus the mixed
anhydride of fluorosulfonyldifluoroacetic acid and trifluoroacetic acid reacts with alcohols to give both expected
products in the approximate ratio 1:1.
Exhaustive ammonolysis of fluorinated p-sultones yields
the diamides (17) and the amidoamidines (is) whose
formation can be explained by repeated conversions involving p-sulfam derivatives[34!
+HNu
x2@
F2
1
CH,O- CO-R
,SOz-F
XZC\
CO-Nu
Table 2. Formation of a-fluorosulfonyl polyfluoro carboxylic acid
derivatives (16) from p-sultones (I).
x,c$!
Reagent
Ammonolysis undoubtedly starts with isomerization of the
p-sultone followed by formation of the a-fluorosulfonyl
carboxamide.
SO, - F
CO-Nu
F,
SO2- F
Reagent
Nu
Ref.
H2O
ROH
H2S
RSH
KSCN
R,NH
(NH2LCO
RCOOH
OH
OR
SH
[14-16,18,42,43]
[14-16,18,33,44-46]
[is, 181
114-16,18,47]
~151
[14-16,18,46]
~ 5 1
[48,49]
F,
SR
SCN
NR*
NH-CO-NH,
0-CO-R
Fluorosulfonylfluoroaceticacid and fluorosulfonyldifluore
acetic acid are isolable; they are stable and behave as strong
carboxylic acids. The fluorosulfonyl carboxylic acids can
be converted into anhydrides, acyl halides, esters, thio
esters, amides, hydrazides, etc. by the usual methods.
Synthesis and investigation of numerous derivatives of
a-fluorosulfonylcarboxylic acids have permitted derivation
Angew. Chem. internat. Edit. / Vof. 1I (1972)/ N o . 7
CO-F
CO-NH,
a-Fluorosulfonylperfluoropropionamidehas been isolated
and converted into the nitrile and the triazine derivative
(19)[52*531.
The nitrile is stable; it can yield the triazine
derivative only by way of the imidoyl chloride or the imidic
esterlS2'. It was concluded from this observation that the
simultaneous formation of nitrile and triazine on dehydration of the amide must be due to presence of the isomeric
imidic acid (20).
This peculiarity of the amide would also explain the result
of exhaustive ammonolysis reported above.
Fluorinated p-sultones can be made to react with nucleophilic compounds under conditions unfavorable for isomerization by liberated fluoride ions. An appropriate method
587
is to work with a large excess of the n u c l e ~ p h i l e [initial
~~~;
attack by an anion affords a derivative of the a-sulfo
carboxylic acid whose sulfonyl group bears a substituent
F\ ,SO,-F
C
F3C' \CN
F3C
CO-NH,
N\
sulfonyl carboxylic (25) as major product. If addition
is carried out in the reverse order the bis(2-fluoroethyl
ester) of the a-sulfo carboxylic acid (26) is formed. In both
cases reaction begins with a nucleophilic attack by ethylene
oxide with elimination of a fluoride ion.
Excess p-sultone is isomerized by fluoride ion ;the resulting
oc-fluorosulfonyl acyl fluoride ( I I ) cleaves the ethylene
oxide, as could also be confirmed in an independent experiment. The diester (26) is not formed[551.
N
Y
R
(19). R
SO,-F
= F,C-CF-SO,-F
-
,SOz-F
x2c\
SO,-F
-A
XZC\
CO-NH,
F,
SO, - F
,NH
'\OH
x2c\
+ HC1
G=
CO-0-CH,-CH,F
(20)
other than fluorine. The reaction of a p-sultone with an
excess of hydrogen chloride in ethereal solution to give
the a-chlorosulfonyl polyfluoro acyl fluoride (21) may
be cited as an example[35].
ROR
CO-F
If an excess of ethylene oxide is present it is cleaved by
fluoride ionEs6,"I ;the a-fluoroethoxy anion then converts
the p-sultone into a-(2-fluoroethoxysulfonyl) acyl fluoride
which reacts with ethylene oxide to give the diester (26).
By-products are naturally also formed by telomerization of
the ethylene oxidei5'].
[R20H]@ CI0
,:CP
SOZ-O-CH2-CHzF
Analogously, diesters of a-sulfo polyfluoro carboxylic acids
(22) are formed with an excess of alkali metal alkoxide
in an alcoholr35! On treatment with aqueous alkali,
fluorinated p-sultones are converted into salts of a-sulfo
carboxylic acids (23)[15* 541.
so, - 00
SO, - OR
X,C\
CO-OR
(221
x2c:
2 M@
co-00
(231
It proved possible to isolate free sulfodifluoroacetic acid as
a crystalline hydrate after hydrolysis of tetrafluoroethanesultone (If). The acid yields derivatives including a cyclic
dianhydride (24)['"1.
Competition between the nucIeophilic reagents is illustrated
particularly well by the reaction of fluorinated p-sultones
with ethylene oxide["]. Addition of ethylene oxide to the
p-sultone furnishes the 2-fluoroalkyl ester of the a-fluoro-
F F
CO-F
+
Fo
To summarize, it may be said that when reaction begins
with nucleophilic attack by the reagent the p-sultone ring
is always opened with elimination of fluoride ion and formation of an a-sulfo carboxylic acid derivative.
3.2. Conversion of p-Sultones into Derivatives of
Polyfluoroalkanesulfonic Acids
Hydrolysis of p-sultones based on hexafluoropropylene
and other higher fluoroolefins yields unstable a-fluorosulfonyl polyfluoro carboxylic acids which readily undergo
d e c a r b o x y l a t i ~ n [591.
~ ~Whereas
.
fluorosulfonylfluoroacetic
acid and fluorosulfonyldifluoroacetic give off carbon dioxide only on heatingfs9.601,higher homologs decarboxylate at room temperature to give a-monosubstituted
polyfluoroalkanesulfonyl fluorides
5 8 * s91.
Classical methods cannot always be used with these acids
for conversion of one derivative into anotheri61-64!
588
Angew. Chem. internat. Edit. 1 Vol. I 1 (1972) 1 No. 7
Thus attempts to synthesize esters from acyl halides were
unsuccessful. In neutral and acidic solution the acyl halides
are inactive towards alcohols; even in the presence of alkali
metal hydroxides or alkoxides as well as tertiary amines
they do not yield esters but salts of the sulfonic acid.
F 3 C C H F - SO, - F
F 3 C - C H F SO, C1
(F,C - C H F -SO, -0),Ba
F3C- C H F -SO, -OR
r
.1
F,C-CHF-SO,-OH
+
F,C-CFCl-SO,-F
(31)
(F,C-CHF-SO,),O
f 291
The methyl and ethyl esters can only be prepared by the
action of the sulfonic anhydride (29) on the corresponding
ether L6 I.
(F3C-CHF--S02),0
hydrogen in a-monosubstituted polyfluoroalkanesulfonyl
halides under base-solvolysis conditions. Thus a-chlorosulfonyl halides of type (31) could be prepared in the
presence of tertiary amines and chlorine or sulfuryl chloride; the halides could be converted into the sulfonic acids,
their anhydrides, esters, amides, and a few other derivatives[61,66,671.Derivatives of tetrafluoroethanesulfonic
acid containing bromine, nitroso, acyl groups, or cyano
in the a position were prepared similarly[61.661.
+ R-0-R
Of the compounds listed, particular attention attaches to
a-nitrosotetrafluoroethanesulfonyl fluoride (32) which is
characterized by the instability of the sulfonyl fluoride and
nitroso moieties. It was transformed into numerous novel
compounds, e. g. (33)-(35)[611.
F,C-CF(N0)-SO,-F
+
2F3C-CHF--SO,-OR
F3C-CF(N0,)--SO,-X
(331
(32)
(29)
F,C-CF(N=NR)-SO,-X
Aminolysis of the.sulfony1 fluoride (28) also took a surprising course :The expected sulfonamidesare accompanied
by P-aminoalkanesulfonamides, in some cases as major
product[611.
F,C-CHF--SO,-F
R,NH
F,C-CF(NR,)-SO,-X
134)
(35)
In addition, transition of the a-nitroso sulfonyl fluoride (32)
into relatively stable radicals, e. g. bis(a-fluorosulfonyltetrafluoroethy1)aminyl oxide (36j, was shown by the ESR
spectruml6’1.
(28)
The peculiarities shown by some of the reactions of these
1,2,2,2-tetrafluoroethanesulfonicacid derivatives were interpreted as being due to the mobility of the hydrogen
resulting from the inductive effect of the sulfonyl
and the trifluoromethyl group.
,SOz - F
F,C - C,F
N-0’
F,C-Ct
SO, - F
(36)
Finally, under conditions of base solvolysis 1,2,2,2-tetrafluoroethanesulfonyl fluoride (28) gives trimethylfluorosulfene1’]as a complex (37) with pyridine[65268!
Pyrolysis of 1,2,2,2-tetrafluoroethanesulfonylfluoride (28)
yields trifluoroethylenesulfonyl fluoride (30)[581which
readily adds nucleophiles.
0
F,C-eF-SO,-F
F,C=CF-SO,-F
<*:
H
+ R2NH
R,N-CF,-CHF-SO,-F
The lability of the C--H bond in the derivatives of 1,2,2,2tetrafluoroethanesulfonic acid is particularly obvious on
solvolysis with bases. The sulfonyl fluoride (28), like alkali
metal sulfonates, forms stable adducts with tertiary amines c6 51.
F,C--CF--SO,-F
HSR,
A method for the synthesis of a-substituted polyfluoroalkanesulfonyl compounds has been worked out on the
basis of similar compounds having carbanion character.
The method consists in the electrophilic substitution of the
Angew. Chem. internat. Edit.
F3C-CF=S0,
(37)
RO-CF,-CHF-SO,-F
f 30)
e
@
N
Vof. I I (1972) / N o . 7
Sulfenes have so far defied all attempts at isolation; they
have only been demonstrated as intermediates in the reactions of sulfonyl compounds[69,701. A similar complex
(38), which likewise is extremely unstable, could be
isolated on dehydrochlorination of methanesulfonyl chloride[71,721.
H,C-SO,-Cl
H,C-SO,-CH=SO,N(C,H,),
(38)
The detection of complexed trifluoromethylfluorosulfene
permits a new interpretation to be given for the reaction
[*] We suggest the name “sulfonenes” instead of “sulfenes” for such
compounds in order to emphasize the presence of both a sulfonyl group
and a double bond.
589
of 1,2,2,2-tetrafluoroethanesulfonylfluoride (28) with
nucleophilic reagents. The mechanistic alternatives for this
reaction are an sN2 substitution or elimination with subsequent addition (EA).
sw2
I
-
EA
F,C-CF=SOz
F,C-CHF-SO,-F
1
1
F,C-CHF-SO,-Nu
The thermodynamic stability of the sulfonyl fluoride
grOUp'40*411
makes the sN2 process appear highly unlikely.
The results of potentiometric titration of some sulfonyl
fluorides can be explained by invoking the EA reaction
mode[671.The rate constants of their alkaline hydrolysis in
the presence of potassium chloride are listed in Table 3,
Table 3. Rate constants of alkaline hydrolysis K , of sulfonyl fluorides
in the presence of potassium chloride at 25°C and pH 10.0.
R--SO,-F
Kc
(1 mol-'s-')
F,C-CFCl
3.3
8.2
18.3
46.1
912
923
R
C6H5
H,C=CH
H3C
C6H,-CH2
F,C-CHF
The success of the reaction is determined by two factors:
Firstly by the coordinative accessibility of the central atom
in the acid chloride and secondly by the acylating power
of this reagent. Thus silicon tetrachloride and titanium
tetrachloride do not react with fluorinated p-sultones
(up to 100°C). This observation was explained by the
coordinative saturation of silicon and titanium which
hinders formation ofa transition state with the p-s~ltones['~].
In contrast, reaction with nitrosyl chloride occurs at - 35 "C.
Similarly vigorous reactions are observed between psultones and methylphosphonyl dichloride (at - 10"C)
and phosphorus oxide trichloride (at - 20°C); the resulting
fluorochlorophosphoric acids can also react with p-sulThe reactions with chlorosulfuric acid derivatives[73-771
such as alkanesulfonyl chlorides[76*
771, alkyl chlorosulfates[76*
771, chlorosulfuric acid[75,771, and sulfuryl chloride'761proceed analogously. The reaction temperatures
required and the yields of alkenyl chlorosulfate are consonant with the acylating power of the chlorosulfonyl compounds (Table 4).
Table 4. Temperature and yield in the reaction
SO,
F z C O + X-SO,-Cl
-D
F,C=CF-0-SO,-CI
F,
from which it may be seen that sulfonyl fluorides having no
a-hydrogen atom react least readily with nucleophilic
reagents and which sulfonyl fluorides can only undergo
S,2 substitution. Methane and particularly o-tolueneand 1,2,2,2-tetrafluoroethanesulfonylfluorides are distinguished by their high rate constants. The reactivity
of these compounds is apparently due to the intermediacy
of a sulfene.
3.3. Conversion of fLSultones into Derivatives
of Alkenylsulfiuic Acids
X
TW)
Yield (%)
R
RO
HO
CI
20-60
30-80
80-100
100
90-95
65-80
70-80
20
The reaction of fluorinated p-sultones with alkyl chlorosulfates is the sole general method available for the preparation of aliphatic esters of fluorosulfuric acid
(RO-SO,--F)[~~~781.
x
Treatment of fluorinated p-sultones with some acyl chlorides or esters furnishes derivatives of fluoroalkenylsulfuric
acids (12) and acyl fluorides. The reaction must pass
through a transition state having both the sultone and the
reagent in favorable orientations. The transition state is
stabilized by cleavage of the sultone S-C bond.
+ Acyl-F
When carried out with an acyl chloride (acyl-X) the reaction
yields fluoroalkenyl chlorosulfate. In this way trifluorovinyl chlorosulfate was obtained from tetrafluoroethanesultone and pentafluoropropenyl chlorosulfate from hexafluoro-1,2-propanesultone.Derivatives of sulfuric acid and
sulfonic acids, nitrous acid, phosphoric and phosphonic
acids, and silicon- and titanium tetrachloride were used as
acid chlorides.
590
S?2
G O
l7
+
RO-SO,-Cl
-
F,
XFC=CF-O-SOZ-Cl
+
RO- SO, - F
This route was used to prepare methyl and n-hexyl fluorosulfate[761and thereby permitted estimation of the refraction of the fluorosulfate group: RF-SO,-O = 11.50 cm'.
Alkyl fluorosulfates are powerful alkylating agents.
Reaction of fluorinated p-sultones with sulfurous esters
gives esters of fluoroalkenylsulfuric acids (39)[77,
79* 'I.
Esters of trifluorovinylsulfuric acid were obtained from
tetraflu~roethanesultone[~~~
791 and esters of pentafluoropropenylsulfuric acid from hexafluoro-l,2-propanes u l t ~ n e ~the
~ ~refractions
~ ~ ~ ] ; of the polyfluoroalkenyl
groups are RF2,,,,=9.82
cm3 and RF,C-CF=CF=15.71
cm3.
Fo
X
+ (RO)zSO
Fz
+
XFC=CF-O-SO,-OR
(39)
+ [RO-SO-Fl
Angew. Chem. internat. Edit. 1 Vol. I1 (1972) 1 No. 7
Fluorinated p-sultones react with dialkyl sulfates to give
esters of fluorosulfuric acid and of fluoroalkenylsulfuric
acid ; however, this reaction is recommended only for the
preparation of fluoroalkenylsulfates of higher alcohols
because lower dialkyl sulfates are more typically alkylating
rather than acylating agentsLs1].This is particularly obvious from the reaction of fluorinated P-sultones with
unsymmetrical alkyl sulfates[731: The products are the
fluoroalkenylsulfate of the higher and the fluorosulfate of
the lower alcohol.
Fz@
+ RO-SOz-OCH3
F2C=CF-O-SOz-OR
-+
+
F,
starts with a nucleophilic attack on the sulfonyl group with
cleavage of the ester.
-!n
XFC=CF-O-SO, G R 3
Hal
-
0
XFE-CO-F
+
0
Hal-S02-NR3
What then ensues is determined by the reaction of the
carbanion with the sulfonylammonium ion. In the case
of a chlorosulfonylammonium ion attack is centered on the
chlorine atom and an a-chloro acyl fluoride (43) is formed;
with a fluorosulfonylammonium ion the sulfonyl group is
attacked and an a-fluorosulfonyl acyl fluoride (11) results.
133CO -SO,-F
or\
RSN-SOz-Cl
C.”
CXF CO F
+
RSN
+ SO, + C I X F C - C O - F
(43)
The derivatives of trifluorovinylsulfuricacid are characterized by their ability to react with nucleophiles; thus their
alkaline hydrolysis leads in a vigorous fashion to complete
decomposition of the reactantsfZ9~
7 5 , ‘I.
F2C=CF-O-S02-F
F2C=CF-O-S0,-Cl
F2C=CF-O-S02-OR
+ 4KOH
HOOC-CHO + 3 KF
+KOSO,F + H,O
+ 6 KOH + HOOC-CHO + 3 KF
KCl + K,SO, + 2 H 2 0
+ 4KOH -t HOOC-CHO + 3 K F
+ KOS0,OR + H,O
-t
+
If a similar reaction is carried out in sulfuryl fluoride
chloride solution-a source of fluorosulfonylcationsf851then a-fluorosuIfony1 fluorides are formed exclusively,
irrespective of which halide of fluoroalkenylsulfuricacid is
used. Reaction in sulfuryl chloride (source of chlorine
cations) likewise affords solely a-chloro acyl fluorides[84!
The initial step in their alcoholysis is substitution in the
vinyl
821.
F,C=CF-O-SO,-X
+ ROH
+
RO-CF=CF-0-SO,-X
S02FCI
X F C = C F - 0 - SO2-Hal
+ HF
F-SOz- C F X - C O - F
f11)
CIXFC-CO-F
(43)
Excess alcohol then adds to the product. Thus a bistalkoxy)
However, if a secondary m i n e is used to initiate decomcompound (40) could be isolated on reaction of trifluoroposition of fluoroalkenyl halogenosulfates one obtains
vinyl chlorosulfate[”! Only addition occurs to give comsulfamide and the amide of the correspondpounds like (41) and (42) on reaction with a ~ i d s [ ’ ~ * ~ ~tetrasubstituted
~.
ing carboxylic acid (44) having an a-hydrogen atom[77.82!
(RO),FC-CHF-O-SO,-CI
(40)
H3C-COO-CF2-CHF-O-S02-CI
CI-SO2-0-CF2-CHF-0-SO2-Cl
(41)
(42)
Derivatives of pentafluoropropenylsulfuric acid can also
react with n u c l e o p h i l e ~831.
~ ~The
~ ~results ofalkaline hydrolysis and alcoholysis show the double bond in these compounds to be polarized, unlike that in the trifluorovinyl
compounds. The trifluoromethyl group therefore appears
to exert a more pronounced effect than the sulfonyl group.
F3C-CF=CF-O-S02-CI
F3C-CF=CF-O-S02-OR
F,C-CF=CF-O-S02-X
+ 5KOH
+
XFC-CF-O-SO2-Hal
XHFC-CO-F
HNR,
+ Hal-SOz-NR2
w
[XFC-CO-F
HNR*
0
+ Hal-SO,-NHR,]
XHFC-CO-NRz
+ RzN-SO,-N
(44)
Derivatives of fluoroalkenylsulfuric acid are also very
unstable in the presence of acids. Thus their esters decompose on heating with strong mineral acids (sulfuric,
chlorosulfuric, and fluorosulfuric acid) to give fluorosulfates[861in a chain reaction (Scheme 3).
F,C-CFH-COOK
+ KF + K,SO, + KCl + 2 H 2 0
-
+ 3KOH F,C-CHF-COOK
+ KF + KOS0,OR + H,O
F,C-CHF-COOR
The behavior of fluoroalkenyl halogenosulfates towards
tertiary amines, which initiate decomposition of the chlorosulfates and isomerization of the fluorosulfates of these
acids, occupies a special place[841.In both cases the reaction
Angew. Chem. internal. Edit. 1 Vol. 11 (1972) J No. 7
RO-S?,
9
*
RO-SOP
+
+ [ X F C = C = O ] + RO-SO,-F
XFC=C
‘3@SOz-OR
Scheme 3
591
The instability of trifluorovinylsulfuricacid becomes readily
understandable in the Iight of these results. These acids,
which are formed from tetrafluoroethanesultone and
sulfuric acid at room temperatures, are converted into
difluoroketene (45) and fluorosulfuric acid on heating to
temperatures above 40°C in what is probably an autocatalytic reaction.
-
SO,
F,GO
+ H,SO,
FzC=CF-O-SOz-OH
He
F,C=C=O
Like the p-sultones, fluorinated p-disultones (1,3,2,4-dioxadithiane 2,2,4,4-tetroxides)are extremely reactive compounds. They can isomerize to sulfate- or sulfonate-type
derivatives.
+ F-SO,-OH
F,C=CF-0-SO,-OH
F,
4. Fluorinated j3-Disultones
+ F-SO,-OH
(474
(45)
At higher temperatures difluoroketene (45) decomposes
to tetrafluoroethylene and carbon monoxide[86.871.
In view
of these and the foregoing reactions and the conditions of
p-sultone synthesisit was deduced that the processes shown
in Scheme 4 take place when tetrafluoroethylene is passed
through heated disulfuric acid.
-
F,C=CF,+SO,
Fze$
f HzS04
SQz
F,Q
-+
F,
F,C=C=O + 2 F-SO,-OH
(451
F,
F,C=C=O
F,C=CF,
+2
-+
H,SZ07
In the case of the tetrafluoro compound ( 3 b) both possible
linear isomers were isolatedrz8! Treatment of (3b) with
potassium fluoride in catalyticamounts below 0°C furnishes
trifluorovinyl fluorodisulfate (46) ;heating of (3b) to over
130“C yields fluorosulfonyloxysulfonyldifluoroacetylfluoride (47a). Other fluorinated P-disultones have so far
only been isomerized to derivatives of type (47) r23*281.
I/,
F,C=CF, + CO
-+
4 F-SOz-OH
+2
CO
Hitherto only the reactions of fluorinated P-disultones
with nucleophilic compounds A-B have been studied.
After ring cleavage the linear isomer sulfonylates the
reagent I9*J.
P 6e
+ A-B
+ A-O-S02-X
Scheme 4
RO-SO,-0-SO,-X
The failure of previous attempts to isolate organofluorine
compounds after passage of polyfluoroolefins through
oleum can presumably be explained similarly[88].
Reaction of the tetrafluoro compound ( 3b ) with an excess
of potassium fluoride gives potassium fluorosulfate and
trifluorovinylfluorosulfate;with ethers, alkyl fluorosulfates
and alkyl trifluorovinyl sulfates are formed[z81.
The above reactions of fluorinated p-sultones with mineral
acids and their derivatives reveal the relatively labile
character of the S-C bond in the sultone ring, which also
determines the course of the following reactions.
+
RO-SO,-B
{
F,C= C F - 0-SO2-F
F, C=CF - 0- SO,
Passage ofdry hydrogen chloride through a cooled fluorinated p-sultone or hexafluoro-l,2-propanesultoneaffords
chlorosulfuric acid and the corresponding ~lefin[~’].
An
analogous reaction takes place with nitrosyl fluorides[s’!
- 0-SO,
-F
(46 a)
+ KO-SOz-F
(124
F,C=CF-0-SO,-OR
+ RO-SO,-F
Alkaline hydrolysis of compounds (3) also results in ring
Isomerization here follows the second
cleavagerz3.z4,
course. Similarly, alcoholysis initially gives a derivative of
a-sulfonyloxysulfonyl carboxylic acid ; the further course
of the reaction depends upon the structure of the compound
( 3 ) and the reaction conditions.
$3
-+
XFC=CF,
+ F-SQ-ON0
SO, - OK
F Z
KF
+ K,SO, + 3
HzO
(3)
Fluoroolefins are also eliminated on passage of ethylene
through ~-~ultones[~’!
FxS?,p
RO
592
+2
CO-OK
o’so2
+ 5 KOH
-
SO2-OK
XzC:
+ K F + ROH + KzSO,
CO-OK
Angew. Chem. intemat. Edit.
Vol. 11.(1972) 1 No. 7
+ 2 H,(
On alcoholysis of @-alkoxy derivatives ring opening is
followed by sulfonylation of the alcohol and formation of
the diester of the a-sulfo carboxylic acid of type (Z2)[231.
SO,- 0- SO, - F
+ R'OH
CO-OR
-
H
-
H,XH
P
4
RHXC-CH,-SOz-OH
(48)
R
SO2-OR'
+ HO-SO,-F
X,Cc
CO-OR
(22)
In the case of the p-fluoro derivative the alcohol is acylated
to compounds of type (47) by the acyl'fluoride formed.
/SOz - 0-SO, - F
XZC\
The formation of ethylenebis(su1fonic acid) on reaction of
tetrafluoroethanesultone with ethylene can be interpreted
in terms of the intermediacy of unsubstituted p-sultone
(see Section 3.3)LS9'.
SO,-0-SO,-F
+ ROH
CO-F
+ HF
X2C:
(47) Co-oR
The final reaction step is sulfonyIation of either the alcohol
(if present in excess) or the hydrogen fluoride (if insufficient
alcohol is present) by compound (47) ; depending on the
conditions one obtains either the diester (22) or the affuorosulfonyf carboxylic
9 1 * 92!
,SOz - 0-SO, - F
XZC\
CO-OR
+ HF
SO, - F
-+
X,C=
+ HO-S02-F
CO-OR
The reactions of bromine- and chlorine-containing olefins
with sulfur trioxide can be rationalized in a similar way1"].
(47)
5. Transformations of &Sultones Containing
No Fluorine
It was shown in Section 3 that the transformations of
fluorinated p-sultones lead to derivatives of a-sulfo carboxylic acids or sulfuric acid. Anions play an important role
in these
35, 731.
In contrast, j3-sultones containing hydrogen atoms are
characterized by their ability to undergo reactions involving
proton shiftsrzo1.The primary products of reaction between
olefins and sulfur trioxide- j3-suItones, P-disultones, and
6-sultones-are known to be extremely .unstable. Their
transformations result from the mobility of the a-hydrogen
atom in the sultone ring or of a hydrogen atom in the @alkyl group"". The failure of attempts to isolate p-sultones
can be explained by the ease of ring cleavage with concomitant shift of the proton to the oxygen.
H
*
--+
H'
RHC=CH-S02-OH
k
H z C 3
-+
RHC=CH-CH,-SO,-OH
H /c\
H R
Treatment of ofefin-sulfur trioxide adducts with water,
hydrogen halides, alcohoIs, thiols, and primary or secondary amines affords P-substituted sulfonic acids (48) ;with
tertiary amines one obtains salts of a$-unsaturated sulfonic
acids (49).
Angew. Chem. internat. Edit.
I Vol. I 1 (1972)1 No.7
Cl,C=CHCl+
so,
-
so
" G o
c1
c1,
If a 0-sultone molecule has a proton in the a-position and
halogen in the @-positionthe reaction can, in principle,
take two courses. In chlorinated or brominated p-sultones
reactions involving proton shifts predominate while fluorinated p-sultones preferentially undergo reactions with
participation of anions.
6. Applications
Although their study only began as late as 1957, fluorinated
p-sultones have already been thoroughly investigated and
numerous preparative methods have been worked but for
their synthesis. Their ready accessibility prompted a search
for possible applications.
Thus it has been reported that derivatives of a-sulfo poly-
fluoro carboxylic acids prepared from p-sultones inhibit
the growth of microorganism^^'^^. The derivatives (50) to
(53) exhibit the greatest bactericidal effect.
F -SO,-CFZ-CO-R
(501, R = NH-CO-NH2
( 5 1 ) . R = N(CH,)C,H,
(52). R = O-CH,-CH,-O-CO-CF,-SO,-F
(531, R = S-C6H5
593
Polyester and polyamides of a-sulfo polyfluoro carboxylic
acids such as (54) and (55) are noninflammable polymeric
materials‘’ ‘1.
[-O-SOz-CFX-CO-O-(CH2)n-],
(541
[-NH-SOz-CF,-CO-NH-(CH~)n-]~
(55)
Telomerization products of j3-sultones and fluorinated
epoxides are also characterized by high thermal
stability[93.941.
SO2-F
XFC:
C F z - 0 - ( C F X LC F 2 - 0 ) ” - CF,X’ CO- F
(56)
These polymers can be converted into highly stable ionexchange resins193].Copolymerization of alkenesulfonyl
fluorides with fluoroolefinshas also been utilized to produce
ion-exchange resins (57)[581.
%
FzXC F Z
F, /S02-F
C
FzXC’ ‘COOH
- CXF - CF2- C X F - C F -
1
FzXC-CHF-SO,-F
I-HF
$.
XFC-CF
2 XFC=CF-SO2-F
A method based on desulfurization of sultones and the
derivatives of a-sulfo polyfluoro carboxylic acids by the
action of sulfuric, fluorosulfuric, or chlorosulfuric acid has
been suggested for production of polyfluoro carboxylic
acids having an a-hydrogen atom and their derivatives[86,95,961
Finally, fluorinated p-sultones are so hygroscopic that
they, and the fluoroolefins from which they are formed,
can be used as stabilizers for liquid sulfur tri~xidel’~.
981.
Further research on fluorinated P-sultones will doubtless
suggest new preparative and industrial applications.
Received: April 5,1971 [A 885 IE]
German version: Angew. Chem. 84,623 (1972)
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595
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