Title of Invention

"SULPHONYLATION PROCESS FOR THE PREPARATION OF A SULPHONATED PRODUCT"

Abstract The invention concerns a method and a reagent useful for the synthesis of perhalogenated sulphanilide on the carbon borne by the sulphur atom of the sulphanilide function. Said perfluoroalkane sulphonylation method is characterised in that it comprises a step which consists in contacting a nucleophile whereof the nucleophilic atom is a nitrogen, with a reagent comprising by successive or simultaneous addition a heavy sulphonyl halide, advantageously sulphonyl chloride, and an organic base comprising a metalloid atom having resonance with a $g(p) bond, and the organic part of said sulphonyl is perhalogenated, advantageously perfluorinated, on the carbon borne by the sulphur. The invention is applicable to intermediate synthesis for organic c...
Full Text The present invention relates to a sulphonylation process for the preparation of a sulphonated product.
The present invention relates to a process for sulphonylating various nucleophiles, in particular nitrogenous nucleophiles. The invention relates more particularly to the sulphonylation of amines and more particularly anilines in the broad sense, i.e. amines linked to an aromatic ring.
The reaction is also directed towards a perhaloalkanesulphonylating reagent. Thus, the present invention relates more particularly to a sulphonylation reaction of an amine bearing an electron-withdrawing radical, especially when its amino functions are made soft, for example by the presence of an aryl radical (the amine then falling into the sub-category of anilines).
The present invention is also directed towards the perhalosulphonylation of the very specific amine which is ammonia, to give either the amide or the imide.
The synthesis of these derivatives of sulphonamide type is often difficult, especially when the starting material used is a sulphonyl halide. Direct reactions usually fail, in particular with i sulphonyl chlorides, especially when the organic part of the sulphonyls is highly electron-withdrawing, as is the case in particular when the atom bearing the
sulphur of the sulphonyl function is perhalogenated, and more particularly when it is perfluorinated.
The explanation for these failures appears to be associated with the oxidizing nature of sulphonyl halides, in particular of trifluoromethanesulphonyl halides, which, like sulphuryl chloride, is an efficient oxidizing agent.
Accordingly, one of the aims of the present invention is to provide a process for obtaining sulphonamides of the above type using sulphonyl halides, in particular when these halides are heavy halides (i.e. halides corresponding to a halogen with an atomic number at least equal to that of chlorine).
It is preferred to use sulphonyl chlorides, for both economic and technical reasons. Specifically, it should be pointed out firstly that the iodide is difficult to obtain, and occasionally its existence is even doubtful, and secondly that the bromide is relatively unstable. The technique has also been transposed to the synthesis of perfluorosulphonimides, in one or two steps.
These aims and others which will become apparent hereinbelow are achieved by means of a sulphonylation process comprising a step of placing a nucleophile, whose nucleophilic atom is advantageously a nitrogen, in contact with a reagent comprising, for successive or simultaneous addition:

a heavy halide (i.e. a halide whose atomic number is at least equal to that of chlorine), of sulphonyl, advantageously sulphonyl chloride, and
an organic base comprising a saturated metalloid atom, having a resonance with a n bond linking two atoms, at least one of which is an atom from column VB, advantageously an organic base comprising a trivalent atom from column VB (the nitrogen column in the Mendeleev table), the lone pair of this atom being conjugated directly or indirectly to a 71 bond linking two atoms, at least one of which is an atom from column V, and
by the fact that the organic part of the said sulphonyl is perhalogenated (with at least one, preferably two fluorines), advantageously perfluorinated, on the carbon borne by the sulphur.
The metalloid atoms with a resonance (directly or indirectly via double bond(s), advantageously carbon-carbon double bond(s)) with a 71 bond, in general a doublet conjugated with a n bond, are advantageously chosen from those having a strong donating mesomeric effect, i.e. those which, with their possible substituents has a factor R (contribution of the resonance; see in particular "March", third edition, Table 6 of page 248) which is signficantly negative, more specifically not more than -0.4, advantageously not more than -0.6; preferably not more than -1.5; more preferably not more than -2. When there
are several metalloid atoms with the above resonance properties, a sum of the said factors R may then be determined, the said sum then being advantageously not more than -0.5, preferably -0.8 and more preferably not more than -2.
It is desirable for the said atom from column VB (as defined in the Periodic Table of the Elements published in the supplement to the bulletin of the French Chemical Society in January 1966, with four or three hydrocarbon-based chains, respectively) of the said organic base has a higher donor number than that of pyridine.
For the definition of the donor number, reference may be made to the book by Christian Reinhardt, Solvents and solvents effects in organic chemistry, p. 19 (1988), in which the definition is given as the negative enthalpy (-AH expressed in kilocalories/mol) of the interaction between the solvent and antimony pentachloride in a dilute dichloromethane solution.
The metalloid atoms are advantageously chosen from the atoms from column VB and from the chalcogens. Those of the first rows (especially nitrogen and oxygen) have the advantage of being sparingly oxidizable.
The terms "sparingly reducible" or "sparingly oxidizable" mean herein that the oxidation of the
reagents is zero or slow relative to the sulphonylation reaction kinetics.
When it is desired to prevent the said metalloid atom itself from being sulphonylated, an alkylated base should be chosen such that the said metalloid atom no longer contains hydrogen.
Although less satisfactory than the chloride, sulphonyl bromide may also be used.
The present invention is particularly advantageous for nucleophiles whose associated acid has a pKa of not more than about 7, advantageously 6, preferably 5 and more preferably 4. It is also advantageous for the oxidizable nucleophiles and more generally when it is desired to use an oxidizable reagent.
Specifically, these nucleophiles are in general particularly difficult to sulphonylate. In particular, the invention is advantageous for nucleophiles whose nucleophilic atom, often a nitrogen, is linked to an aryl or an electron-withdrawing group or, more generally, to an electron-withdrawing combination of substituents, i.e. the sum of their Hammett constants σp is at least equal to 0.2, advantageously 0.3 and preferably 0.5.
This electron-withdrawing group may be chosen in particular from aryls, advantageously electron-poor aryls, and acid residues, advantageously oxygenated
acid residues, such as phosphoryl, phosphonyl, acyl and especially sulphonyl residues.
The said organic base comprising a saturated metalloid atom, having a resonance with a π bond, may be used either as a base or as a catalyst for the reaction.
Specifically, the sulphonylation reaction releases a hydrohalic acid which often salifies the nucleophile and thus makes the nucleophile more or less inert. In addition, the sulphonylation product is often a stronger acid than the conjugated acid of the base; in this case, neutralization of this acid should also be envisaged.
Thus, it is desirable to add bases (in an amount and of a nature) which will make it possible to release the nucleophile of the various acids present in the reaction medium such that it displays its role as a nucleophile fully.
The said organic base comprising a saturated metalloid atom, having a resonance with a 7t bond, is advantageously such that the said metalloid atom is a trivalent atom from column VB, which is preferably a trisubstituted atom forming a tertiary base.
According to one particularly advantageous embodiment of the present invention, the said π bond linking two atoms is the n bond of an imine function.
It is preferable for this imine function to be arranged such that the atoms of nitrogen and of the
said metalloid are as far apart as possible, in other words and for example, such that the nitrogen of the imine function is that of the two atoms linked via the π bond which is furthest from the trivalent atom from column V. That which has just been stated regarding the imine function is general for all the atoms from column VB linked via the 71 bond, when the 7C bond comprises a carbon atom and an atom from column V.
According to the present invention, it is preferable for the organic base comprising a trivalent atom from column VB, whose lone pair is conjugated to a n bond, to have a sequence or skeleton of formula >N-[C = C]n-C = N- with n = 0 or an integer chosen in the closed range (i.e. comprising the limits) 1 to 4, advantageously from 1 to 3, preferably from 1 to 2. Preferably, the above sequence corresponds to the formula >N-[C(R1) = C (R2) ] n-C (R3) = N- with n = 0 or an integer chosen in the closed range (i.e. comprising the limits) 1 to 4, advantageously from 1 to 3, preferably from 1 to 2, and in which Rl, R2 and R3, which may be identical or different, are chosen from hydrocarbon-based derivatives, advantageously alkyl derivatives containing not more than 4 carbon atoms, and hydrogen. Advantageously, according to the process, the said trivalent atom from column VB forms or constitutes a tertiary amine.
More specifically, it is desirable for the said organic base comprising a trivalent atom from
column VB, whose lone pair is conjugated to a π bond, to constitute a molecule of the following formula (R5) (R4)N-[C(R!) = C(R2)]n-C = N-R6 with n = 0 or an integer chosen in the closed range (i.e. comprising the limits) 1 to 4, advantageously from 1 to 3, preferably from 1 to 2, and in which Rlr R2 and R6, which may be identical or different, are chosen from hydrocarbon-based groups, advantageously alkyl groups containing not more than 4 carbon atoms, and hydrogen, and in which R4 and R5, which may be identical or different, are chosen from hydrocarbon-based groups, advantageously alkyl groups containing not more than 4 carbon atoms, one or two of the substituents R1, R2, R3, R4, R5 and R6 being able to be linked to other substituent(s) remaining to form one or more rings.
The observed catalytic effect is particularly pronounced when the said n bond linking two atoms is endocyclic, especially when it is endocyclic in an aromatic ring. This is particularly the case for pyridine rings and rings derived therefrom such as quinoline or isoquinoline. Thus, the pyridine nuclei enriched by the presence of one or more metalloid atoms, in particular when the sum of the R (see above) is not more than -1.5, advantageously -2, constitutes catalysts that are particularly satisfactory.
More specifically, the organic base comprising a saturated metalloid atom, having a resonance with a π bond, may be chosen advantageously
from dialkylaminopyridines, in particular in the para-or ortho- position (i.e. in position 2 or 4 of the pyridine); DBU (diazabicycloundecene) also gives an advantageous result.
Although the present invention can be used to form common sulphonimides, this reaction is particularly advantageous in the case of the formation of an amide or imide function starting with a nucleophilic substrate, in particular one consisting of an aniline, and more particularly when this aniline is linked to an electron-depleted aromatic ring.
This depletion can be correlated to the introduction of a hetero atom into the ring (in the case of 6-membered rings) or by the presence of substituents on the ring bearing the aniline function to be sulphonylated, of substituent(s) which are electron-withdrawing overall.
In the case of an electronic depletion of a 6-membered ring by means of the introduction of a hetero atom, it should be pointed out that the substrate, or more specifically the substrates, can be autocatalytic, i.e. they may not require the presence of a catalyst, often of an amine, according to the present invention.
As regards depletion by the substituents, it may be indicated as a guide that the invention is particularly suitable for treating arylamines in which the substituents, excluding the nucleophilic function
to be sulphonylated, of the ring bearing the nucleophilic atom are such that the sum of their Hammett σp constants is at least equal to 0.14, advantageously to 0.20, preferably to 0.30.
When this sum of the Hammett constants reaches values of greater than 1, the reaction becomes particularly sluggish, and as such it is preferable for the sum of the Hammett constants for the ring bearing the amine function to be not more than 1, preferably not more than 0.9, more preferably not more than 0.7.
When the organic base comprising a saturated metalloid atom is used as catalyst (i.e. it is used in sub-stoichiometric amounts, more generally in an amount of between l°/oo and 1/5 of the SA [stoichiometric amount] necessary to neutralize the acids released by the reaction, advantageously between 1/100 and 1/10 of SA), it is then convenient to provide another base such that the reaction with respect to the nucleophilic substrate is as complete as possible.
In this case, the reagent used also comprises, for successive or simultaneous addition, an organic base, preferably one which cannot be alkylated. Non-alkylatable organic bases which may be chosen in particular are bulky dialkylphosphines, trialkylphosphines, quaternary phosphonium hydroxides, bulky dialkylamines, trialkylamines and quaternary ammonium hydroxides. The notion of bulkiness of bulky dialkylphosphines or dialkylamines such that they
cannot be alkylated is well known to those skilled in the art.
In a great many cases, and in particular when solvents are used, it is preferable for the said non-alkylatable base to be liposoluble and to have at least one solubility in benzene which is significant (symbol "s" in the "Handbook of Chemistry and Physics"), and advantageously high (symbol "v" in the "Handbook of Chemistry and Physics").
As has been seen previously, it is usually desirable to carry out the placing in contact in an organic solvent. This solvent is advantageously relatively non-polar and preferably relatively immiscible with water. More particularly, it is desirable for not more than 10% by mass, advantageously not more than 5% and preferably not more than 2% by mass, to be miscible with water.
The amounts of base to be added and the amount of non-alkylatable base used during the reaction is advantageously at least equal to the amount required to neutralize the hydrohalic acid released.
In other words, the amount of base must be sufficient to ensure that the nucleophile is always at least partially present in free form (i.e. in true nucleophilic form) throughout the reaction. When the bases are oxidizable, such as amines, it is preferable to limit the co-existence of the free base with the sulphonyl halide.
This may be achieved either by limiting the stoichiometric excess relative to the acids they are supposed to neutralize to once and preferably to half the SA, or by a gradual addition of the base, or both means at the same time. The sulphonyl halide may also be added gradually.
The techniques towards which the present invention is directed are particularly suited to sulphonylation with perfluorinated alkylsulphonyl chlorides, which are perfluorinated in particular on the carbon borne by the sulphur.
The chloride which can most commonly be used is triflyl chloride (CF3SO2C1) . More generally, the organic part of the sulphonyl chloride corresponds to the formula (Rf).
Rf means a radical of formula:
(Formula Removed)
- in which the groups X, which may be identical or different, represent a chlorine, a fluorine or a radical of formula CnF2n+1 where n is an integer of not more than 5, preferably not more than 2, with the condition that at least one of the groups X is fluorine, fluorine advantageously borne by the carbon linked to the sulphur;
- in which p represents an integer of not more than 2;
- in which EWG represents an electron-withdrawing group (i.e. sigma p greater than zero, advantageously greater than 0.1, preferably gretaer than 0.2) whose possible
functions are inert under the reaction conditions, advantageously fluorine or a perfluoro residue of formula CnF2n+1 with n being an integer of not more than 8, advantageously not more than 5.
The total number of carbons in Rf is advantageously between 1 and 15, preferably between 1 and 10.
The present invention is also directed towards a reagent which is useful for carrying out the process according to the invention. This reagent comprises, for successive or simultaneous addition:
• a heavy halide (i.e. a halide whose atomic number is
at least equal to that of chlorine), of sulphonyl,
advantageously sulphonyl chloride,
and:
• an organic base comprising a saturated metalloid
atom, having a resonance with a n bond linking two
atoms, at least one of which is an atom from column
VB, advantageously a nitrogen atom;
the organic part of the said sulphonyl being perhalogenated, advantageously perfluorinated, on the carbon borne by the sulphur.
The said saturated metalloid atom is advantageously a trivalent atom from column VB (the nitrogen column) whose lone pair is conjugated directly or indirectly to a π bond linking two atoms, at least one of which is an atom from column VB.
The reagent according to the present invention may in addition comprise, also for successive or simultaneous addition, an organic base which is different from the said organic base comprising a saturated metalloid atom. In general, in this case, the ratio in equivalents between the organic base comprising a saturated metalloid atom (numerator) and the said different base (denominator) is within the closed range 1 per thousand 1/5, advantageously between 0.5% and 1/10.
The reagent according to the present invention can also comprise, again for successive or simultaneous addition, a solvent. This solvent, including a mixture of solvents, is advantageously relatively non-polar and chosen from those which have low solubility in water. In certain cases, chlorinated aliphatic chains are not satisfactory.
As a touchstone for the polarity, it may be pointed out that the said relatively non-polar solvent is chosen from those, or mixtures of those, whose polarity (E expressed in kcal/mol) is not more than 40 (advantageously to two significant figures).
• These relatively non-polar solvents are usually chosen from oxygenated organic compounds, in particular ethers, esters or even ketones, hydrocarbons, including petroleum fractions, and aromatic hydrocarbons which are generally halogenated. The latter solvents are particularly advantageous, in
particular substituted benzenes and hydrocarbons which are halogenated on the ring.
That which has just been described above is particularly suitable for anilines, in particular those in which the said nitrogen atom is linked to a 6-membered aromatic ring, preferably a homocyclic ring, preferably a non-fused benzenic ring, are advantageously electron-depleted as has already been pointed out above. Overall, given the possible substituents which are particularly suited to amines linked to an aryl whose electron-richness is not more than that of a para-chlorophenyl (richness evaluated by means of the Hammett sigma p constants).
Among the electron-withdrawing groups which are most commonly used, mention may be made of halogens (chlorine and fluorine), esters (of CO-OR type), ketones, amides not liable to interfere with the sulphonylation, alkyls which are perhalogenated on the carbon linked directly to the ring, in particular alkyls which are perfluorinated on the atom next to the ring, nitriles, and groups containing a sulphone or phosphone function directly linked to the ring.
The technique is directed especially to the sulphonylation of anilines in the broad sense (i.e. amines borne by an aryl), but this teaching has also been transposed to the sulphonamidation of (aqueous) ammonia and the sulphimidation of sulphamides.
In this case, the latter are advantageously in the form of a salt of a non-alkylatable organic base (it is the base which is non-alkylatable).
Under these conditions, the nitrogen bears a hydrogen or, more preferably, a negative charge (anion), whereas, in the case of anilines which has been targeted above, the aniline function comprises at least one hydrogen, preferably two, for reasons of steric hindrance.
The use of the said organic base comprising a saturated metalloid atom having a resonance with a n bond makes it possible to carry out, in good yield, the double sulphonylation of nucleophiles which can be substituted twice (such as ammonia and primary amines). The preferred operating conditions are those described in the international patent application published by WIPO under the No. WO 98/52886, using, at least partially as base, the said organic base comprising a saturated metalloid atom having a resonance with a n bond.
For reasons of work hygiene, chlorinated aliphatic derivatives are generally to be avoided, although they constitute a family of solvents which gives good results, even though it is not the family which gives the best performance, since their solubility, and in particular that of methylene chloride, is of the order of 2% by volume, i.e. 2.6% by weight.
As regards the solvents, solvents with a reducing nature should be avoided as much as possible.
The reaction can be carried out from -2 0 to about 200°C, more generally from 0° to about 100°C.
It is easier to work at ambient temperature and pressure, but it is also possible to be at different, higher pressures. It is also possible to work in a closed chamber (such as an autoclave or sealed tube) and under autogenous pressure.
The non-limiting examples below illustrate the invention.
EXAMPLES
Preparation of 5-acetamido-2,4-dimethyltrifluoro-
methanesulphonanilide
- Reaction in the presence of a catalyst:
350 g of dichloromethane, 50.1 g of 5-amino-2,4-dimethylacetanilide and 6.9 g of 4-dimethylamino-pyridine are successively loaded into a reactor. The suspension obtained is then stirred and cooled to 10°C. 57.4 g of triethylamine are then added over 15 min at 10°C.
A solution of 56.8 g of trifluoromethanesulphonyl chloride in 59 g of dichloromethane is then added over 2 h while keeping the temperature of the medium at 10°C.
The medium is then kept stirring for 2 h at 10°C and is then allowed to warm to a temperature of 20°C and stirring is continued for 2 h.
The medium is acidified in the reactor by-addition of 265 g of aqueous 4.2% HCl solution.
The precipitate formed is then filtered off and rinsed (3 times) with deionized water and then with dichloromethane. It is then dried at 95°C under reduced pressure.
67 g of a beige solid are thus obtained, i.e. an isolated yield of 77%.
Characteristic of the compound: melting point = 180°C.
- Reaction in the absence of catalyst:
The above conditions are repeated, but in the absence of 4-dimethylaminopyridine.
Analysis of the reaction medium shows a 90% degradation of the trifluoromethanesulphonyl chloride.
Yield of expected product very much less than 10%.
Preparation of methyl 5-chloro-2-(N-trifluoromethyl-sulphonyl)aminobenzoate
- Reaction in the presence of a catalyst:
17 g of methyl 5-chloroanthranilate, 120 g of dichloromethane, 2.26 g of 4-dimethylaminopyridine and then 18.5 g of trifluoromethanesulphonyl chloride are
successively loaded into a reactor. The solution is stirred at 15°C and a solution of 18.7 g of triethylamine in 19 g of dichloromethane is added over 3 h. After addition, the medium is stirred for 3 h at 15°C and then for 10 h at room temperature.
The medium is then washed successively with 150 g of deionized water, with 100 g of concentrated hydrochloric acid solution and then again with 160 g of deionized water.
The solvent is removed under reduced pressure.
27.7 g of a yellowish solid are thus obtained, i.e. a crude isolated yield of 95%.
Characteristic of the compound: melting point = 81°C.
- Reaction in the absence of catalyst:
1/ Reaction with triethylamine:
The above conditions are repeated, but in the absence of 4-dimethylaminopyridine.
Analysis of the reaction medium shows a total degradation of the trifluoromethanesulphonyl chloride.
The expected product was not formed.
2/ Reaction with diisopropylethylamine:
In the same manner, the test in the absence of catalyst and in the presence of
diisopropylethylamine does not lead to the expected
product.
3/ Reaction with 1,4-diazabicyclo[2,2,2]octane or DABCO:
Again, the expected product is not formed.
Preparation of trialkylammonium bis(trifluoromethane-
sulphonimide)
- Catalysed reaction:
Example 1:
9.3 g of triethylamine (0.092 M), 0.56 g of 4-dimethylaminopyridine and 45 g of dichloromethane are loaded into a reactor. 1.38 g (0.092 M) of ammonia are then added. The solution obtained is stirred at 0°C.
Trifluoromethanesulphonyl chloride (15.5 g, i.e. 0.092 M) diluted in 10 ml of dichloromethane is then added over 2 h at 0°C, after which the reaction is continued for 3 h at room temperature.
Analysis of the reaction medium shows a trifluoromethanesulphinate impurity content of 2%.
The reaction medium is treated twice with 15 ml of aqueous 12% HCl solution and then 3 times with 15 ml of water. The residual organic phase is concentrated under reduced pressure, which thus gives 13.65 g of triethylammonium
bis(trifluoromethanesulphonimide) in liquid form, equivalent to an isolated yield of 80%. The purity of the compound obtained is 98%.
Example 2:
The procedure of Example 1 is repeated, but replacing the dichloromethane with dioxane. The reaction medium is analysed after dilution with water: the yield of bis(trifluoromethanesulphonimide) at the end of the reaction is 51% with a trifluoromethanesulphinate content of 6%.
- Non-catalysed reaction:
Comparative Example 3:
The procedure of Example 1 is repeated, but without using 4-dimethylaminopyridine.
The yield of bis(trifluoromethanesulphonimide) at the end of the reaction is 47%, with a trifluoromethanesulphinate content of 21%.
Comparative Example 4:
Procedure 3 is repeated, but using diisopropyl ethylamine as base in replacement for the triethylamine.
The yield of bis(trifluoromethanesulphonimide) at the end of the reaction is 51%, with a trifluoromethanesulphinate content of 21%.
Comparative Example 5:
11.8 g of trifluoromethanesulphonyl chloride (0.07 M) are loaded into a reactor and 33.9 g of
triethylamine (0.0336 M) are then added at 0°C over
10 min.
The medium is stirred for a further 10 min at 0°C, followed by addition of 0.5 g of ammonia (0.029 M). The reaction is exothermic. The medium is then maintained at 65°C for 4 h.
Compounds resulting from the oxidative degradation of the amines are observed. The major product is the trifluoromethanesulphinate in a content of 57%.
The presence of bis(trifluoromethane-sulphonimide) is not revealed, which implies a reaction yield of less than 2%, or even zero.






WE CLAIM:-
Sulphonylation process for the preparation of a sulphonated product, characterized in that it comprises the steps of:
1) reacting a nitrogen nuclephile of the kind such as herein described with a reagent, said reagent comprising:
-sulphonyl halide having an organic part a group of formula (Rf):
(Formula Removed)
wherein the groups X, which are identical or different, represent a chlorine, a fluorine or a radical of formula CnF2n+1 where n is an integer of not more than 5, with the proviso that at least one of the groups X is fluorine;
p represents an integer of not more than 2; and
EWG represents an electron-withdrawing group being inert during step 1), the total number of carbons in Rf being between 1 and 15 and whose halogen atom has an atomic number at least equal to that of chlorine, -an organic base as herein described comprising a trivalent atom from column VB, whose lone pair is conjugated, directly or indirectly, to a bond linking two atoms, at least one of which is an atom from column VB; and in that the organic part of the said sulphonyl is perhalogenated, preferably perfluorinated, on the carbon borne by the sulphur; and 2) recovering the sulphonated product thus formed.
2. Process as claimed in claim 1, wherein said sulphonyl halide is a sulphonyl chloride.
3. Process as claimed in claim 1 or claim 2, wherein the conjugate acid of the said nucleophile has a pKa of not more than 7.
4. Process as claimed in claim 3, wherein said pKa is not more than 5.

5. Process as claimed in anyone of claims 1 to 4, wherein the said nitrogen of the said nucleophile is linked to an electron-withdrawing group.
6. Process as claimed in claim 5, wherein the said electron-withdrawing group is selected from aryls and sulphonyls.
7. Process as claimed in claim 6, wherein said electron-withdrawing group is an electron-depleted aryl or a sulphonyl group.
8. Process as claimed in anyone of claims 1 to 7, wherein said trivalent atom from column VB is a trisubstituted atom.
9. Process as claimed in claim 8 wherein the said trivalent atom from column VB is a trisubstituted nitrogen.
10. Process as claimed in anyone of claims 1 to 9, wherein the said bond linking two atoms is as imine bond.
11. Process as claimed in anyone of claims 1 to 10, wherein the said organic base comprises formula> N-[C = C]n = N wherein n = zero or an integer between 1 to 4, the limits being included.

12. Process as claimed in claim 11, wherein n = zero or an integer between 1 to 2.
13. Process as claimed in anyone of claims 1 to 10, wherein the said organic base comprises formula >N-[C(R1)=C(R2)]n-C(R3) = N-wherein n = zero or an integer between 1 to 4, the limits being included, and wherein R1, R2 and R3 which are identical or different, are hydrocarbon groups containing not more than 4 carbon atoms, or hydrogen.
14. Process as claimed in claim 13, wherein R1, R2 and R3 are alkyl groups.
15. Process as claimed in anyone of claims 1 to 14, wherein the said trivalent atom forms a tertiary base.
16. Process as claimed in claim 15, wherein the said trivalent atom forms a tertiary amine.
17. Process as claimed in claim 16, wherein the said tertiary amine comprises formula
(Formula Removed)
with n=0 or an integer between 1 to 4, the limits being included, R1, R2 and R6, which are identical or different, are hydrocarbon groups containing not more than 4 carbon atoms, or hydrogen, and R4 and R5, which are identical or different, are hydrocarbon groups containing not more than 4 carbon atoms, optionally one or two of the substituents Ri, R2, R3, R4, Rs and R6 being able to be linked to other substituent(s) remaining to form one or more rings.
18. Process as claimed in claim 17 wherein R1, R2, R3, R4, Rs and R6 are alkyl groups.
19. Process as claimed in anyone of claims 1 to 18, wherein the said bond linking two atoms is endocyclic.
20. Process as claimed in claim 19, wherein the said bond is an aromatic
ring.
21. Process as claimed in claim 20, wherein the said ring is a pyridine ring.
22. Process as claimed in anyone of claims 1 to 21, wherein the said base is chosen from para- or ortho-dialkylaminopyridines and diazobicycloundecene (DBU).
23. Process as claimed in anyone of claims 1 to 22, wherein the said nucleophile has a nitrogen as nucleophilic atom.
24. Process as claimed in anyone of claims 1 to 23, wherein the said nucleophile is ammonia or a sulphonimide.
25. Process as claimed in anyone of claims 1 to 23, wherein the said nucleophile is ammonia and is perfluorosulphonated twice.
26. Process as claimed in anyone of claims 1 to 23, wherein the said nucleophile is an arylamine in which the substituents, excluding the nucleophilic function, of the ring bearing the nucleophilic atom are such that the sum of their Hammett σp constants is at least equal to 0.14, preferably to 0.20.
27. Process as claimed in any of claims 1 to 23, wherein the said reagent optionally comprises a non-alkylatable organic base.
28. Process as claimed in claim 27, wherein the said non-alkylatable organic base is chosen from bulky dialkylphosphines, trialkylphosphines, phosphonium hydroxides, bulky dialkylamines, trialkylamines and ammonium hydroxides.
29. Process as claimed in anyone of claims 1 to 28, wherein the said step 1) is carried out in an organic solvent which is relatively non-polar and not more than 10% by mass miscible with water.
30. Process as claimed in anyone of claims 1 to 29, wherein during step 1) hydrohalic acid is released and alkylatable liposoluble base is at least equal to the amount required to neutralize the hydrohalic acid released.
31. Process as claimed in anyone of claims 1 to 30, wherein the organic part of the said sulphonyl halide is perfluorinated on the carbon borne by the sulphur.
32. Process as claimed in anyone of the preceding claims, wherein n is not more than 2 and EWG is a perfluoro residue of formula CnF2n+1 with n being an integer of not more than 8, the total number of carbons in Rf being between 1 and 10.

Documents:

in-pct-2001-421-del-abstract.pdf

in-pct-2001-421-del-claims.pdf

in-pct-2001-421-del-correspondence-others.pdf

in-pct-2001-421-del-correspondence-po.pdf

in-pct-2001-421-del-description (complete).pdf

in-pct-2001-421-del-form-1.pdf

in-pct-2001-421-del-form-13.pdf

in-pct-2001-421-del-form-19.pdf

in-pct-2001-421-del-form-2.pdf

in-pct-2001-421-del-form-3.pdf

in-pct-2001-421-del-form-5.pdf

in-pct-2001-421-del-gpa.pdf

in-pct-2001-421-del-pct-210.pdf

in-pct-2001-421-del-pct-409.pdf

in-pct-2001-421-del-petition-137.pdf


Patent Number 240359
Indian Patent Application Number IN/PCT/2001/00421/DEL
PG Journal Number 20/2010
Publication Date 14-May-2010
Grant Date 05-May-2010
Date of Filing 18-May-2001
Name of Patentee RHODIA CHIMIE
Applicant Address 26, QUAI ALPHONSE LE GALLO, F-92512 BOULOGNE-BILLANCOURT CEDEX, FRANCE.
Inventors:
# Inventor's Name Inventor's Address
1 JEAN-ROGER DESMURS LA JONQUIERE-ROUTE DE TERNAY, COMMUNAY, F-69360 SAINT-SYMPHORIEN D'OZON, FRANCE.
2 ANDRE MILLET RUE 1'ALLON, F-69720 SAINT-LAURENT DE MURE, FRANCE.
3 VIRGINIE PEVERE 37, RUE BATAILLE, F-69008 LYON, FRNACE.
PCT International Classification Number C07B 45/00
PCT International Application Number PCT/FR99/02697
PCT International Filing date 1999-11-04
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 98/13863 1998-11-04 France
2 99/12453 1999-10-06 France