U.S. patent application number 09/923493 was filed with the patent office on 2002-01-10 for process for the synthesis of perfluorosulphonamides, of perfluorosulphonimides and of their salts, and a sulphonylation reagent.
Invention is credited to Gilbert, Laurent, Marx, Emmanuel, Pevere, Virginie.
Application Number | 20020004613 09/923493 |
Document ID | / |
Family ID | 9506986 |
Filed Date | 2002-01-10 |
United States Patent
Application |
20020004613 |
Kind Code |
A1 |
Pevere, Virginie ; et
al. |
January 10, 2002 |
Process for the synthesis of perfluorosulphonamides, of
perfluorosulphonimides and of their salts, and a sulphonylation
reagent
Abstract
The invention concerns a method of sulphonation characterized in
that it consists in contacting a nucleophile whose nucleophilic
atom is a nitrogen atom with a reagent comprising by successive or
simultaneous addition: a heavy sulphonyl halide (i.e. whose atomic
number is not less than that of chlorine), advantageously suphonyl
chloride; and an organic base both not capable of alkylation and
lipid soluble; and the organic part of said sulphonyl is
perfluorinated on the carbon carried by the sulphur. The invention
is applicable to organic synthesis.
Inventors: |
Pevere, Virginie; (Lyon,
FR) ; Marx, Emmanuel; (Chatillon D'Azergues, FR)
; Gilbert, Laurent; (Lyon, FR) |
Correspondence
Address: |
RHODIA INC.
CN-7500
259 Prospect Plains Road
Cranbury
NJ
08512
US
|
Family ID: |
9506986 |
Appl. No.: |
09/923493 |
Filed: |
August 7, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09923493 |
Aug 7, 2001 |
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09423486 |
Nov 9, 1999 |
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6297398 |
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Current U.S.
Class: |
564/84 ;
564/95 |
Current CPC
Class: |
C07C 303/38 20130101;
C07C 303/38 20130101; C07C 311/48 20130101 |
Class at
Publication: |
564/84 ;
564/95 |
International
Class: |
C07C 311/01; C07C
311/15 |
Foreign Application Data
Date |
Code |
Application Number |
May 16, 1997 |
FR |
97/06064 |
Claims
1. (Perfluoro)sulphonylation process, characterized in that it
comprises a stage in which a nucleophile, the nucleophilic atom of
which is a nitrogen, is brought into contact with a reactant
comprising, for successive or simultaneous addition: a sulphonyl
heavy halide, advantageously sulphonyl chloride, and; an organic
base which simultaneously cannot be alkylated and is liposoluble;
and with the condition that, when the nitrogen, the nucleophilic
atom of the substrate, does not already carry a sulphonyl
functional group for which the carbon adjoining the sulphur is
perfluorinated, the organic part of the said sulphonyl heavy halide
is perfluorinated on the carbon carried by the sulphur.
2. Process according to claim 1, characterized in that the said
nucleophile, in the neutral or anionic form, has, as associated
acid, an acid for which the pK.sub.a is at most equal to
approximately 7, advantageously to 6, preferably to 5.
3. Process according to claims 1 and 2, characterized in that the
said nitrogen of the said nucleophile is connected to an
electron-withdrawing group, advantageously a sulphonyl group,
advantageously the said nucleophile is chosen from sulphamides of
sulphonic acids in which the sulphur is bonded to an aryl or from
sulphamides of sulphonic acids in which the sulphur is bonded to an
aliphatic residue, including alkyls, preferably from sulphamides of
sulphonic acids in which the sulphur is bonded to an aliphatic
residue which are perfluorinated on the carbon adjoining the
sulphur.
4. Process according to claims 1 to 3, characterized in that the
said nucleophile is a salt of sulphonamide (sulphamide) and of an
organic base which cannot be alkylated.
5. Process according to claims 1 to 4, characterized in that the
said nucleophile is a sulphonamide (sulphamide) in the form of a
liposoluble salt with the said organic base which simultaneously
cannot be alkylated and is liposoluble.
6. Process according to claims 1 to 5, characterized in that the
said organic base which cannot be alkylated is chosen from hindered
dialkylphosphines, trialkylphosphines, phosphonium hydroxides,
hindered dialkylamines, trialkylamines or ammonium hydroxides.
7. Process according to claims 1 to 6, characterized in that the
said base which simultaneously cannot be alkylated and is
liposoluble is chosen from hindered dialkylphosphines,
trialkylphosphines, phosphonium hydroxides, hindered dialkylamines,
trialkylamines or ammonium hydroxides.
8. Process according to claims 1 to 7, characterized in that the
said base which simultaneously cannot be alkylated and is
liposoluble exhibits at least a significant (symbol "s" in the
Handbook of Chemistry and Physics) solubility in benzene,
advantageously a high (symbol "v" in the Handbook of Chemistry and
Physics) solubility in benzene.
9. Process according to claims 1 to 8, characterized in that the
said organic base exhibits at least a significant (symbol "s" in
the Handbook of Chemistry and Physics) solubility in benzene,
advantageously a high (symbol "v" in the Handbook of Chemistry and
Physics) solubility in benzene.
10. Process according to claims 1 to 9, characterized in that the
pK.sub.a of the acid associated with the said organic base is
greater than or equal to that of the said sulphonamide.
11. Process according to claims 1 to 10, characterized in that the
pK.sub.a of the acid associated with the said base which cannot be
alkylated and is liposoluble is greater than or equal to that of
the said sulphonamide.
12. Process according to claims 1 to 11, characterized in that,
when the said nucleophile is a salt of sulphonamide (sulphamide)
and of an organic base which cannot be alkylated, the said organic
base which cannot be alkylated and the said base which
simultaneously cannot be alkylated and is liposoluble are
identical.
13. Process according to claims 1 to 12, characterized in that the
said operation of bringing into contact is carried out in an
organic solvent, advantageously of low polarity, preferably of low
miscibility with water (at most 10% by mass, advantageously at most
5% by mass, preferably at most 2% by mass).
14. Process according to claims 1 to 13, characterized in that the
said operation of bringing into contact is carried out in an
organic solvent which is chosen so that the said salt is soluble
therein, advantageously to a concentration level of at least 0.05M,
preferably of at least 0.2M.
15. Process according to claims 1 to 14, characterized in that the
amount of the said base which cannot be alkylated and is
liposoluble introduced during the reaction is at least equal to the
amount necessary to neutralize the hydrohalic acid given off.
16. Process according to claims 1 to 15, characterized in that the
organic part of the said sulphonyl chloride is perfluorinated on
the carbon carried by the sulphur.
17. Process according to claims 1 to 16, characterized in that the
organic part of the said sulphonyl chloride is the same as that of
the said sulphonamide.
18. Process according to claims 1 to 17, characterized in that the
organic parts, which are alike or different, of the said sulphonyl
chloride and of the said sulphonamide are chosen from radicals of
formula (Rf): --(CX.sub.2).sub.p--EWG where: the X groups, which
are alike or different, represent a fluorine or a radical of
formula C.sub.nF.sub.2n+1, with n an integer at most equal to 5,
preferably to 2; p represents an integer at most equal to 2; EWG
represents an electron-withdrawing group, the possible functional
groups of which are inert under the reaction conditions,
advantageously fluorine or a perfluorinated residue of formula
C.sub.nF.sub.2n+1, with n an integer at most equal to 8,
advantageously to 5. The total carbon number of Rf is
advantageously between 1 and 15, preferably between 1 and 10.
19. Process according to claims 1 to 18, characterized in that the
said nucleophile in which the nucleophilic atom is a nitrogen is a
salt of sulphonamide (sulphamide) and of an organic base which
cannot be alkylated and in that the said process comprises, after
an optional purification and/or isolation stage, a stage of
treatment with lithium hydroxide or a basic lithium salt.
20. Reactant of use in the implementation of the process according
to claims 1 to 19, characterized in that it comprises, for
successive or simultaneous addition: a sulphonyl heavy halide (that
is to say, in which the atomic number of the halogen is at least
equal to that of chlorine), advantageously sulphonyl chloride, and;
an organic base which simultaneously cannot be alkylated and is
liposoluble; a solvent of low polarity; and in that the organic
part of the said sulphonyl is perfluorinated on the carbon carried
by the sulphur.
21. Reactant according to claim 20, characterized in that the said
solvent, including mixture of solvent, of low polarity is chosen
from those exhibiting a low solubility in water and not exhibiting
a chlorinated aliphatic chain.
22. Reactant according to claims 20 and 21, characterized in that
the said solvent of low polarity is chosen from those for which the
polarity (E.sup.f.sub.t, expressed in kcal per mol) is at most
equal to 40 (advantageously two significant figures).
23. Reactant according to claims 20 to 22, characterized in that
the said solvent of low polarity is chosen from oxygen-containing
organic compounds (in particular ethers, esters, even ketones),
hydrocarbons (including petroleum fractions) or ring-halogenated
aromatic hydrocarbons.
24. Reactant according to claims 20 to 23, characterized in that
the said solvent of low polarity is chosen from substituted
benzenes and ring-halogenated [lacuna] hydrocarbons.
Description
[0001] The subject-matter of the present invention is a process for
the synthesis of perfluorosulphonamides and of
perfluorosulphonimides. The latter can be obtained in the form of
their salts. The present invention is also targeted at a
perfluorosulphonylation reagent.
[0002] It more particularly relates to a reaction for the
sulphonylation of a nitrogenous functional group carrying an
electron-withdrawing radical. It is also particularly targeted at
the sulphonation of a sulphonamide, in particular a fluorinated
sulphonamide. The synthesis of sulphamides is in particular
targeted at the case where the sulphamide is prepared with the aim
of a subsequent sulphonation (in a second stage, in the same
reactor, or simultaneously in situ).
[0003] Fluorinated sulphonimide derivatives are increasingly being
developed for electrical applications and in particular for forming
batteries and for their catalytic power. The most frequently used
compound derived from these sulphonimides is the lithium
derivative, that is to say the salt of this imide, an imide which
is itself very acidic.
[0004] The synthesis of these sulphonimides has already been
carried out but employs processes which are particularly
problematic and difficult to use.
[0005] The inserted Application WO 97/23.448 describes a process
which, like all those which have preceded it (cf. FR-A-2,724,380),
uses perfluoroalkanesulphonyl fluorides, the reactivity of which is
very specific and the by-product of which is the fluoride ion,
which requires the use of equipment which is resistant thereto and
thus expensive, as well as exhaustive removal before discharge of
the effluents. The very high volatility and the operating
conditions result, in the commonest cases, in the operation being
carried out under relatively high pressures. To cap it all, the
sensitivity to water of perfluoroalkanesulphonyl fluorides seems,
in the light of this document, particularly high.
[0006] A few trials have been carried out on sulphonyl halides but
have resulted in failures (for the problems relating to these
syntheses, see Application WO 90/11.999, in particular page two,
lines 30 to 35 et passim). This is in particular the case with
bistrifluoromethylsulphinimi- de, which seems particularly
difficult to prepare from trifluoromethanesulphonyl chloride. This
is why one of the aims of the present invention is to provide a
process which makes it possible to obtain fluorinated imides of the
above type by using heavy sulphonyl halides (that is to say,
halides corresponding to a halogen with an atomic number at least
equal to that of chlorine).
[0007] It is preferable, for economic reasons, to use sulphonyl
chlorides. This aim and others which will become apparent
subsequently are achieved by means of a synthetic process which
comprises a stage in which a nucleophile, the nucleophilic atom of
which is a nitrogen, is brought into contact with a reactant
comprising, for successive or simultaneous addition: a sulphonyl
heavy halide (that is to say, in which the atomic number of the
halogen is at least equal to that of chlorine), advantageously
sulphonyl chloride; and an organic base which simultaneously cannot
be alkylated and is liposoluble;
[0008] and with the condition that, when the nitrogen, the
nucleophilic atom of the substrate, does not carry a sulphonyl
functional group for which the carbon adjoining the sulphur is
perfluorinated, the organic part of the said sulphonyl heavy halide
is perfluorinated on the carbon carried by the sulphur. However, in
all cases, the process is particularly advantageous when the
organic part of the said sulphonyl heavy halide is chosen so that
it is perfluorinated on the carbon carried by the sulphur.
[0009] Thus, the present invention provides a process for the
synthesis of perfluorosulphonamides and of sulphonimides which
exhibits at least one, advantageously two, sulphonyl group for
which the carbon adjoining the sulphur is perfluorinated.
[0010] The salts of these imides are prepared from these imides in
a way known per se. The process according to the present invention
can comprise a stage of preparation of these salts (as in the
examples).
[0011] The notion of organic base which simultaneously cannot be
alkylated and is liposoluble is explained subsequently.
[0012] The said nitrogen of the nucleophilic functional group
advantageously carries a hydrogen or a negative charge (anion).
[0013] It is preferable for the said nitrogen of the nucleophilic
functional group to carry two hydrogens (and even 3 in the specific
case of ammonia or aqueous ammonia, which makes it possible to
synthesize the preferred category of substrates, namely
sulphamides, advantageously perfluorinated on the carbon adjoining
the sulphur, preferably corresponding to the definition of Rf) or
else to carry one hydrogen and one negative charge (anion).
[0014] In particular, the nucleophile can be a sulphonamide
(sulphamide), in particular in the form of a salt, advantageously
of an organic base which cannot be alkylated. The process is
suitable in particular even when the organic part of the said
sulphonamide (sulphamide) is perfluorinated on the carbon carried
by the sulphur.
[0015] Conventional sulphamides (corresponding to
non-perfluorinated sulphonic acids, such as Ar--SO.sub.3H, with Ar
representing an aryl, and RSO.sub.3H, with R representing an alkyl)
does not warrant being in the salt form, a salt which would
furthermore be difficult to obtain with the preferred bases of the
invention. In the present description, ALK-yl is taken in its
etymological sense of hydrocarbon-comprising residue of an
ALK-ohol, with the alcohol (or ohol) functional group being
ignored.
[0016] The nucleophilic substrate thus exhibits, as nucleophilic
functional group, a functional group advantageously chosen from
sulphamides of sulphonic acids in which the sulphur is bonded to an
aryl or an aliphatic residue, including alkyls, preferably to an
aliphatic residue which are perfluorinated on the carbon adjoining
the sulphur. In general, the carbon number of the nucleophilic
substrate varies from 1 to 15 and even from 1 to 10.
[0017] Thus, from the above and from the study which has led to the
present invention, it is evident that the nucleophiles (in the
neutral form or especially in the anion form) for which the
problems, because they are difficult, are particularly well solved
by the present invention are those for which the associated acid
exhibits a pKa at most equal to approximately 7, advantageously to
6, preferably to 5.
[0018] Ammonia constitutes a case apart and can, in the case of
ammonia, result in an imide by two successive in situ
condensations.
[0019] The condensation of the sulphonyl heavy halides targeted by
the present invention with ammonia or aqueous ammonia can
constitute a stage prior to the condensation of the amides.
[0020] In the present description, the term "approximately" is
employed to underline the fact that the values which follow it have
been rounded off mathematically and in particular that when the
figure or figures furthest to the right of a number are zeros,
these zeros are positional zeros and not significant figures,
except, of course, when otherwise specified.
[0021] The said organic base which cannot be alkylated is
advantageously chosen from hindered dialkylphosphines,
trialkylphosphines, phosphonium hydroxides, hindered dialkylamines,
trialkylamines or ammonium hydroxides. It is also possible to
envisage phosphorus-comprising and nitrogen-comprising rings
exhibiting an appropriate basicity (see infra). For example nuclei
of the pyridine type, but, according to the present invention and
in contrast to standard techniques, these basic functional groups
of aromatic heterocycles do not constitute the preferred bases.
[0022] It is desirable for the said base which simultaneously
cannot be alkylated and is liposoluble to be chosen from hindered
dialkylphosphines, trialkylphosphines, phosphonium hydroxides,
hindered dialkylamines, trialkylamines or ammonium hydroxides.
[0023] It is recommended that the said base which simultaneously
cannot be alkylated and is liposoluble should exhibit at least a
significant (symbol "s" in the Handbook of Chemistry and Physics)
solubility in benzene, advantageously a high (symbol "v" in the
Handbook of Chemistry and Physics) solubility in benzene.
[0024] It is recommended that the substrate should exhibit at least
a significant (symbol "s" in the Handbook of Chemistry and Physics)
solubility in benzene, advantageously a high (symbol "v" in the
Handbook of Chemistry and Physics) solubility in benzene.
[0025] Likewise, according to the present invention, it is
preferable to see to it that the nucleophilic substrate is in the
form of a salt of an organic base which cannot be alkylated, this
optional saline compound between the organic base and the said
substrate (when it is acidic, as in the case of
perfluorosulphonamide) exhibits at least a significant (symbol "s"
in the Handbook of Chemistry and Physics) solubility in benzene,
advantageously a high (symbol "v" in the Handbook of Chemistry and
Physics) solubility in benzene.
[0026] In the preceding cases, it is, of course, particularly
satisfactory for the solubility to be such that the benzene and the
bases targeted above are miscible in all proportions (symbol
".infin." in the Handbook of Chemistry and Physics).
[0027] In choosing the base, it is advisable to observe basicity
restrictions, thus, it is desirable for the pK.sub.a of the acid
associated with the said organic base (forming the optional salt
with the nucleophile) to be greater than or in the region of that
of the said nucleophile [for example sulphonamide (which in
principle carries two hydrogens on the nitrogen)].
[0028] Likewise, it is also desirable for the pK.sub.a of the acid
associated with the said base which cannot be alkylated and is
liposoluble to be equal to and preferably greater than that of the
said sulphonamide.
[0029] When they are not the same, it is desirable for the
difference between the pK.sub.a values of the associated acids and
that of the said nucleophile (to be at least equal to 1,
advantageously to 2, preferably to 3.
[0030] Although this is not preferred, the bases can be mixtures of
bases, provided which the mixture meets the restrictions and, even
preference, specified hereinabove.
[0031] It can be specified that, when the said nucleophile is
sulphamide, for reasons of ease of handling, it is preferable for
the said organic base which cannot be alkylated and the said base
which simultaneously cannot be alkylated and is liposoluble to be
identical. The reaction can be carried out without solvent, in
particular when the organic bases are chosen from the preferred
ones, that is to say particularly liposoluble and not very polar
bases (for example and in particular, trialkylamines with a carbon
number greater than 6; trialkylamines with a carbon number of less
than 7 but exhibiting at least one secondary or tertiary radical,
advantageously two, or hindered dialkylamine).
[0032] As regards an advantageous implementation of the said stage,
the operation of bringing into contact is carried out in an organic
solvent, advantageously of low [lacuna] advantageously at most 5%
by mass, preferably at most 2% by mass).
[0033] The reaction temperature is advantageously at least equal to
the finishing melting point (apart from insolubles and in
particular salts [hydrohalide, and the like]) of the reaction
mixture and advantageously at most 100.degree. C. (advantageously
two significant figures, preferably 3), advantageously to a
temperature at most equal to approximately 50.degree. C.,
preferably to 40.degree. C. and advantageously at least equal to 0.
Thus, the reaction temperature is advantageously situated within
the closed range defined by the finishing melting point and
100.degree. C. Preferably within the range 0.degree. C. and
50.degree. C., more preferably within the range 0 and 40.degree. C.
Although the reaction can be carried out under a different
pressure, it is easier to carry it out at atmospheric pressure. In
this case, it may be opportune to choose solvents so that there is
a possible reflux at a temperature chosen within the above
temperature ranges.
[0034] In order to obtain good kinetics of reaction, it is
recommended to carry out the said operation of bringing into
contact in an organic solvent which is chosen so that, when the
said nucleophile is sulphamide salt, the said salt-is soluble
therein, advantageously to a concentration level of at least 0.05M,
preferably of at least 0.2M.
[0035] To obtain the above solubilities, it is also possible to
vary the said organic base which cannot be alkylated. It is also
possible to vary the solvent and the organic base
simultaneously.
[0036] The bases employed in the present invention advantageously
exhibit from 3 to approximately 40 carbon atoms, preferably from 6
to approximately 30 carbon atoms, more preferably from 8 to 25
carbon atoms. In particular, when the carbon number is low (that is
to say less than 7), it is preferable for at least one of the
substituents of the basic atom to be at least secondary. These
bases are, for economic reasons, advantageously amines.
[0037] The bases can also be polyfunctional bases (for example,
substituted ethylenediamines and in particular
tetramethylethylenediamine- ), in which case the above restriction
must be reduced to the number of useful basic functional
groups.
[0038] The most useful solvents are solvents of relatively low
polarity, of the chlorine solvent or aromatic solvent type,
provided that, preferably, the said optional salt is sufficiently
soluble therein.
[0039] The said solvent of low polarity, which, it should be
remembered, can be a mixture, is advantageously chosen from those
for which the polarity (E.sup.f.sub.t expressed in kcal per mol) is
at most equal to 40 (advantageously two significant figures).
However, for reasons of industrial hygiene and of environmental
protection [some are already banned], non-aromatic chlorinated
derivatives, in particular aliphatic chlorinated derivatives (such
as methylene chloride or chloroform) or alkenic chlorinated
derivatives (for example trichloroethylene), are generally to be
avoided as solvent. Furthermore, although giving good results, they
do not constitute the family with the best performance (thus, the
solubility in water of methylene chloride is of the order [lacuna]
2% by volume, i.e. 2.6% by mass).
[0040] Taking into account the above, the said solvent of low
polarity is advantageously chosen from oxygen-comprising organic
compounds (in particular ethers, esters, even ketones),
hydrocarbons (including petroleum fractions) or ring-halogenated
aromatic hydrocarbons.
[0041] Preferably, the said solvent of low polarity can
advantageously be chosen from substituted benzenes and
ring-halogenated [lacuna] hydrocarbons.
[0042] Respecting the stoichiometry of the reaction is desirable as
regards the sulphonyl halide and the sulphonamide (sulphamide). A
tolerance of plus or minus 20% is entirely acceptable and depends
essentially on the respective cost of the reactants.
[0043] As regards the amount of the said base which cannot be
alkylated and is liposoluble introduced during the reaction, it is
at least equal to the amount necessary to neutralize the hydrohalic
acid given off.
[0044] When the nitrogen of the substrate carries two hydrogens
(three in the very particular case of ammonia, which makes it
possible to synthesize, in particular in situ, the preferred
category of substrates, namely sulphamides, advantageously
perfluorinated on the carbon adjoining the sulphur, preferably
corresponding to the definition of Rf; of course, in the case of an
in situ synthesis, it is necessary to take into account the
sulphonylation reaction of ammonia) and when the nucleophile is not
in the salt form, it can be advantageous to bring the amount of
base(s) introduced during the reaction to a value at least equal to
twice the amount necessary to neutralize the hydrohalic acid given
off.
[0045] In other words and more specifically, it is preferable for
the sum of the bases (base of the substrate salt [see supra] and
liposoluble organic base which cannot be alkylated) to be at least
equal to the sum of the acidity given off in the form of hydrohalic
acid and of the acidity of the sulphone compounds (in particular
sulphonimides) being formed.
[0046] Thus, taking into account the above, it is desirable for the
total amount of base(s) to be at least equal to one times [lacuna]
amount stoichiometrically necessary to neutralize the hydrohalic
acid given off, advantageously at least equal to the sum of the
acidity given off in the form of hydrohalic acid and of the acidity
of the sulphone compounds (in particular sulphonimides); more
specifically, it is recommended to use an amount of base
(expressed, of course, as equivalent) at least equal to the sum of
the acidity of the sulphone compounds and of one and a quarter
times the amount stoichiometrically necessary to neutralize the
hydrohalic acid given off, advantageously at least equal to the sum
of one and a half times the acidity given off in the form of
hydrohalic acid and of the acidity of the sulphone compounds.
[0047] It is also preferable to avoid an excessively large excess
of base(s); this is why it is desirable for the sum of the bases
(base of the substrate salt [see supra] and liposoluble organic
base which cannot be alkylated) to exhibit an excess, with respect
to the sum of the acidity given off in the form of hydrohalic acid
and of the acidity of the sulphone compounds being formed, at most
equal to 3 times, advantageously to two times, preferably to one
times the amount of hydrohalic acid given off.
[0048] The process with respect to the present invention is
particularly advantageous for the synthesis of compounds obtained
from sulphonyl chloride in which the organic part is perfluorinated
(that is to say, corresponds to CX.sub.2, see infra) on the carbon
carried by the sulphur.
[0049] The present invention is targeted in particular at the case
where the organic part of the said sulphonyl chloride is the same
as that of the said sulphonamide.
[0050] The present invention is also targeted at the case where the
organic part of the said sulphonyl chloride carries, at least
transiently in the form of a reaction intermediate, the
sulphonamide functional group. Which makes it possible to prepare
cyclic products or polymeric products. As is well known generally
to a person skilled in the art for condensation reactions,
cyclization or polycondensation takes place according to the number
of chain members separating the two functional groups and according
to the dilution of the reaction mixture (this well known phenomenon
is recalled, inter alia, in the inserted application WO
97/23448).
[0051] The present invention is particularly useful for carrying
out the condensation of the present invention when the organic
parts, which are alike or different, of the said sulphonyl chloride
and of the said sulphonamide are chosen from radicals of formula
(Rf):
--(CX.sub.2).sub.p--EWG
[0052] where:
[0053] the X groups, which are alike or different, represent a
fluorine or a radical of formula C.sub.nF.sub.2n+1, with n an
integer at most equal to 5, preferably to 2;
[0054] p represents an integer at most equal to 2;
[0055] EWG represents an electron-withdrawing group, the possible
functional groups of which are inert under the reaction conditions,
advantageously fluorine or a perfluorinated residue of formula
C.sub.nF.sub.2n+1, with n an integer at most equal to 8,
advantageously to 5.
[0056] The total carbon number of Rf is advantageously between 1
and 15, preferably between 1 and 10.
[0057] EWG can be or carry a sulphonyl heavy halide functional
group. Which makes it possible to prepare, in situ, compounds
carrying both the nucleophilic functional group and the sulphonyl
heavy halide functional group, compounds where the organic part of
the said sulphonyl chloride carries the sulphonamide functional
group. Which makes it possible to prepare cyclic products or
polymeric products.
[0058] As was indicated above, the most advantageous compounds
obtained from the imides synthesized according to the present
invention are lithium derivative0s, the said process advantageously
comprises, after an optional purification and/or isolation stage, a
stage of treatment with lithium hydroxide or a basic lithium
salt.
[0059] According to the present invention, the starting
sulphonamides can advantageously be synthesized by the action of
the same sulphonyl halide as that used for the synthesis of the
imide. This synthesis can be carried out in protic or aprotic polar
solvents, provided that they have no tendency to be alkylated. In
particular, the reaction can be carried out in symmetrical or
unsymmetrical, cyclic or non-cyclic ethers.
[0060] Another aim of the present invention is to provide a
reactant which is useful in the processes of the above type.
[0061] This aim, and others which will become apparent
subsequently, is achieved by means of a reactant which comprises,
for successive or simultaneous addition:
[0062] a sulphonyl heavy halide (that is to say, in which the
atomic number of the halogen is at least equal to that of
chlorine), advantageously sulphonyl chloride, and;
[0063] an organic base which simultaneously cannot be alkylated and
is liposoluble;
[0064] advantageously a solvent of low polarity;
[0065] and by the fact that the organic part of the said sulphonyl
is perfluorinated on the carbon carried by the sulphur.
[0066] Another aim of the present invention is to provide for the
use of sulphonyl chloride, perfluorinated on the carbon carried by
the sulphur, that is to say adjoining it, in the mono- and
bissulphonylation of ammonia, aqueous ammonia or amide, including
sulphamide. And this advantageously in the presence of an organic
base which cannot be alkylated and is liposoluble. And this in
particular in the syntheses resulting in salts, advantageously
alkaline salts, of imide carrying at least one, preferably two,
sulphone groups perfluorinated on the aliphatic carbon (that is to
say sp3 carbon) adjoining the sulphur.
[0067] One of the advantages of the use of the chloride is a low
sensitivity to side reactions with water.
[0068] In order to better understand the invention, the following
typical reactions can be given by way of indication:
Rf--SO.sub.2Cl+NuH+B.fwdarw.Rf--SO.sub.2Nu+BHCl
[0069] or
Rf--SO.sub.2Cl+Nu.sup.-.fwdarw.+Cl.sup.-+Rf--SO.sub.2Nu
[0070] and if, as is preferred, Nu is Nu'H in nature (or, more
specifically, if the nucleophilic functional group under
consideration of Nu has the structure --NH-- [that is to say, the
structure NH.sup.- or NH.sub.2])
Rf--SO.sub.2Nu'H+B.fwdarw.Rf--SO.sub.2Nu'.sup.-BH.sup.+
[0071] NuH and Nu.sup.- respectively represent the nucleophile in
the neutral and anionic form.
[0072] The most advantageous substrates are those where Nu is
chosen from Ar--SO.sub.2--NH--, in particular R--SO.sub.2--NH--,
including and preferably Rf--SO.sub.2--NH--.
[0073] The following non-limiting examples illustrate the
invention:
EXAMPLE 1
[0074] Preparation of Trifluoromethanesulphonamide:
CF.sub.3SO.sub.2NH.sub.2
[0075] Reaction in Anhydrous Medium:
[0076] 15.3 g of trifluoromethanesulphonyl chloride, in solution in
103 g of anhydrous isopropyl ether, are charged to a reactor. The
mixture is cooled to 5.degree. C. and ammonia is slowly added over
2 h. After stirring for 5 h at 5.degree. C., 24.8 g of water are
added in order to dissolve the salts. The mixture is subsequently
acidified by addition [lacuna] 20.7 g of a 36% aqueous hydrochloric
acid solution.
[0077] After a further addition of 13 g of water, the phases are
separated. The aqueous phase is washed with 50 g of isopropyl
ether. The organic phases are combined and the solvent is removed
under reduced pressure.
[0078] 10.15 g of trifluoromethanesulphonamide as a white solid are
thus obtained.
[0079] Melting [lacuna] (Koffler)=119.degree. C.
[0080] Reaction in Aqueous Medium:
[0081] The reaction is carried out analogously by using a 30%
aqueous ammonia solution.
EXAMPLE 2
[0082] Preparation of Lithium Bistrifluoromethylsulphinimide
[0083] 1 l of monochlorobenzene and 164.6 g of
trifluoromethanesuphonamide- , prepared according to the preceding
example, are charged to a reactor. 224.6 g of triethylamine are
subsequently added to this suspension. The solution obtained is
cooled to 5.degree. C. A solution of 187 g of
trifluoromethanesulphonyl chloride in 191 g of monochlorobenzene is
subsequently added over 40 min at 0-5.degree. C.
[0084] The temperature is subsequently brought to 28.degree. C.
After reacting for 4 h, the reaction mixture is filtered.
[0085] The filtrate is degassed by bubbling nitrogen and then
washed with 436 g of water. The 2 lower organic phases are
recovered and again washed with 507 g of water.
[0086] These organic phases are subsequently treated with a
solution of 46.7 g of lithium hydroxide hydrate in 216 g of water.
The mixture obtained contains two phases.
[0087] The aqueous phase is recovered and extracted with 226 g of
isopropyl ether.
[0088] The latter organic phase is evaporated under reduced
pressure to result in 206 g of crude lithium
bistrifluoromethanesulphonimide in the form of a yellowish
solid.
[0089] Yd=60%
[0090] 19F NMR=-1.8 ppm
EXAMPLE 3
[0091] Reaction in the Presence of Diisopropylethylamine
[0092] 11.2 g (0.079 M) of the amide of trifluoromethanesulphonic
acid in 73 g of monochlorobenzene are charged to a reactor. After
addition of 20.7 g (0.16 M) of diisopropylethylamine, 14.7 g (0.087
M) of trifluoromethanesulphonyl chloride, in solution in 15 g of
monochlorobenzene, are run in at 10.degree. C. for 45 min. The
mixture is subsequently stirred for 4 h at 30.degree. C.
[0093] The treatment is carried out as in the preceding example and
results in 20.4 g of lithium bistrifluoromethanesulphonimide
assaying at 98% (yd=[(20.4/303)/0.079].times.0.98=83% [lacuna].
EXAMPLES 11 TO 13
[0094] Role of the Solvent
[0095] To give a better demonstration of the role of the solvents,
use was made of a base, the salt of which exhibits mediocre
solubility:
1 Exam- ple No. Reactants Solvent Conditions Results 4
CF.sub.3SO.sub.2NH.sub.2 = CH.sub.2Cl.sub.2 Addition
CF.sub.3SO.sub.2Cl Conversion 1.6 g at 0.degree. C.
CF.sub.3SO.sub.2NH.sub.2 = CF.sub.3SO.sub.2Cl = Reaction 13 h at
80% 1 eq. 20.degree. C. Yield = 43% NEt.sub.3 = 2 eq. 5
CF.sub.3SO.sub.2NH.sub.2 = CH.sub.2Cl.sub.2 Introduction Conversion
3.1 g CH.sub.2Cl.sub.2 + CF.sub.3SO.sub.2NH.sub.2 =
CF.sub.3SO.sub.2Cl = CF.sub.3SO.sub.2NH.sub.2 + 76% 1 eq. 1 eq.
NET.sub.3 Yield = 31% NEt.sub.3 = 2 eq. Addition CF.sub.3SO.sub.2Cl
at 0.degree. C. Run in 1 eq. NET.sub.3 at 0.degree. C. Reaction 3 h
at 20.degree. C. 6 CF.sub.3SO.sub.2NH.sub.2 = DIPE Addition
CF.sub.3SO.sub.2Cl Conversion 1.4 g at 0.degree. C.
CF.sub.3SO.sub.2NH.sub.2 = CF.sub.3SO.sub.2Cl = Reaction 3 h at 80%
1 eq. 20.degree. C. Yield = 33% NEt.sub.3 = 2 eq. 7
CF.sub.3SO.sub.2NH.sub.2 = MCB Addition CF.sub.3SO.sub.2Cl
Quantitatively 1 g at 0.degree. C. determined CF.sub.3SO.sub.2Cl =
Reaction 13 h at yield = 67% 1 eq. 20.degree. C. NEt.sub.3 = 2 eq.
8 CF.sub.3SO.sub.2NH.sub.2 = CH.sub.2Cl.sub.2 Addition
CF.sub.3SO.sub.2Cl Conversion 1.85 g at 0.degree. C.
CF.sub.3SO.sub.2NH.sub.2 = CF.sub.3SO.sub.2Cl = Reaction 7 h at 35%
1 eq. 30.degree. C. Yield = 24% Pyridine = Autogenous 2 eq.
pressure 9 CF.sub.3SO.sub.2NH.sub.2 = DIPE Addition
CF.sub.3SO.sub.2Cl Conversion 1.62 g at 0.degree. C.
CF.sub.3SO.sub.2NH.sub.2 = CF.sub.3SO.sub.2Cl = Reaction 7 h at 30%
1.1 eq. 30.degree. C. Yield = 3% Pyridine = Autogenous 2 eq.
pressure 10 CF.sub.3SO.sub.2NH.sub.2 = MCB Addition
CF.sub.3SO.sub.2Cl Conversion 1.02 g at 0.degree. C.
CF.sub.3SO.sub.2NH.sub.2 = CF.sub.3SO.sub.2Cl = Reaction 7 h at 63%
1.1 eq. 30.degree. C. Yield = 4% Pyridine = Autogenous 2 eq.
pressure 11 CF.sub.3SO.sub.2NH.sub.2 = CH.sub.2Cl.sub.2 Addition
CF.sub.3SO.sub.2Cl Conversion 1.91 g at 0.degree. C.
CF.sub.3SO.sub.2NH.sub.2 = CF.sub.3SO.sub.2Cl = Reaction 7 h at 92%
1.1 eq. 20.degree. C. Yield = 85% DIPEA = 2 eq. 12
CF.sub.3SO.sub.2NH.sub.2 = Addition CF.sub.3SO.sub.2Cl Conversion
1.28 g at 0.degree. C. CF.sub.3SO.sub.2NH.sub.2 >
CF.sub.3SO.sub.2Cl = Reaction 8 h at 91% 1.2 eq. 20.degree. C.
Yield = 90% DIPEA = 2 eq. 13 CF.sub.3SO.sub.2NH.sub.2 = MCB
Addition CF.sub.3SO.sub.2Cl Conversion 1.2 g at 0.degree. C.
CF.sub.3SO.sub.2NH.sub.2 > CF.sub.3SO.sub.2Cl = Reaction 8 h at
98% 1.2 eq. 20.degree. C. Yield = 97% DIPEA = 2 eq. DIPE:
diisopropyl ether MCB: monochlorobenzene DIPEA:
diisopropylethylamine *The analyses of the various tests were
carried out by fluorine NMR spectroscopy with internal
standard.
* * * * *