Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
1999-11-09
2001-10-02
O'Sullivan, Peter (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C560S012000, C564S086000, C564S096000, C564S097000
Reexamination Certificate
active
06297398
ABSTRACT:
This application is an application under 35 U.S.C. Section 371 of International Application Number PCT/FR98/00973, filed on May 15, 1998.
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.
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).
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.
The synthesis of these sulphonimides has already been carried out but employs processes which are particularly problematic and difficult to use.
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.
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 bistrifluoromethylsulphinimide, 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).
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;
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.
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.
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).
The notion of organic base which simultaneously cannot be alkylated and is liposoluble is explained subsequently.
The said nitrogen of the nucleophilic functional group advantageously carries a hydrogen or a negative charge (anion).
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).
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.
Conventional sulphamides (corresponding to non-perfluorinated sulphonic acids, such as Ar—SO
3
H, with Ar representing an aryl, and RSO
3
H, 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.
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.
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.
Ammonia constitutes a case apart and can, in the case of ammonia, result in an imide by two successive in situ condensations.
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.
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.
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.
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.
It is recommended that the said base which simultaneously cannot be alkylated and is lipo
Gilbert Laurent
Marx Emmanuel
Pevere Virginie
O'Sullivan Peter
Rhodia Chimie
Seugnet Jean-Louis
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