FR2844265A1 - Use of organic salts comprising a charged group, organic residues, heteroatoms and an interconnecting group together with a counter-ion, as reactants in industrial electrochemical reactions - Google Patents

Abstract

Organic salts comprising a charged group, counter-ion, organic residues, a group which can be substituted, group containing a heteroatom and a group connecting the heteroatom and the charged group. The salt conforms to the general formula (1) R1R2ZC-T-Q-X Y (1) X = a charged group; Y = a counter-ion; Z = a group which can be substituted; R1, R2 = organic residues; T = a group containing a heteroatom from N-R4, O and S; R4 = H or an organic residue; Q = a connecting group between the heteroatom and the charged group. An Independent claim is also included for the use of the salt.

Description

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 The present invention relates to the use of organic compounds as reagents in electrochemical reactions and a process for producing an organic product comprising an electrochemical reaction step.

 Electrochemical reactions are used industrially to produce certain conveniences such as for example adipodinitrile, certain fine chemicals such as anisaldehyde or anthraquinone and certain specialties such as cysteine or picolinic acid.

 Important technical criteria for the economics of such processes include, inter alia, high chemical yield, high electrochemical efficiency, low energy consumption, high concentration of starting materials in the electrochemical reaction medium, a high level of good stability of the electrodes, a long life of membranes, ease of insulation of the product and the possibility of recycling the electrolyte comprising solvent and a conductive salt.

 The patent application DE-2842760 describes the methoxylation in position α of N-alkylated urethanes by electrochemical oxidation in methanolic solution in the presence of a conductive salt.

 It was desirable to find an electrochemical reaction usable in the manufacture of products and meeting a maximum of the aforementioned criteria.

The invention therefore relates to the use of an organic compound salt of general formula
A-XY (I) wherein A is an organic residue, X is a charged moiety and Y is a counter ion as a reagent in an electrochemical reaction.

 It has been found, surprisingly, that the use according to the invention makes it possible to improve the efficiency of electrochemical reactions, in particular with regard to their chemical and electrochemical efficiency and their energy consumption. The use according to the invention makes it possible to carry out reactions

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 Electrochemicals in a medium with a high concentration of reagent.

The use according to the invention ensures a good conductivity of the reaction medium of the electrochemical reaction. The electrochemical reaction can be carried out in the substantial absence of conductive salts. The isolation of the product of the reaction can be carried out easily, the latter often being in a crystallizable form.

 By reagent is meant a compound which is used as such in the reaction. This is different from the formation of charged species that may occur during an electrochemical reaction from organic compounds other than salts.

 By electrochemical reaction is meant in particular a reaction comprising an electron transfer between the organic compound salt and an electrode and the formation or cleavage of at least one covalent bond of the salt of the organic compound having undergone the electron transfer. Typical reactions include formation of a C-H bond, a C-C bond or a C-heteroatom bond. The formation of C-O bonds is preferred.

 In the organic compound salt, the group A is an organic residue.

 By organic residue is meant any group which may contain linear or branched alkyl or alkylene groups, which may include hetero atoms such as in particular boron, silicon, nitrogen, oxygen and sulfur. It may also include cycloalkyl or cycloalkylene groups, heterocycles and aromatic systems. The organic residue may comprise double or triple bonds and functional groups.

 The organic residue comprises at least 1 carbon atom. Often it comprises at least 2 carbon atoms. Preferably, it comprises at least 3 carbon atoms. More preferably, it comprises at least 5 carbon atoms.

 The organic residue generally comprises at most 100 carbon atoms. Often, it comprises at most 50 carbon atoms. Preferably, he

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 comprises at most 40 carbon atoms. More preferably, it comprises at most 30 carbon atoms.

 By alkyl group is meant in particular a linear or branched alkyl substituent comprising 1 to 20 carbon atoms, preferably 1,2,3,4,5,6, 7,8, 9 or 10 carbon atoms. Specific examples of such substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert. butyl, n-pentyl, isopentyl, n-hexyl, 2-hexyl, n-heptyl, n-octyl and benzyl.

 By cycloalkyl group is meant in particular a substituent comprising at least one saturated carbocycle of 3 to 10 carbon atoms, preferably 5.6 or 7 carbon atoms. Specific examples of such substituents are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

 By alkylene group or cycloalkylen group is meant in particular the bivalent radicals derived from alkyl or cycloalkyl groups as defined above.

 When the organic residue contains one or more double bonds, it is often chosen from an alkenyl or cycloalkenyl group comprising from 2 to 20 carbon atoms, preferably 2, 3, 4, 5, 6, 7, 8, 9 or 10 atoms. of carbon. Specific examples of such groups are vinyl, 1-allyl, 2-allyl, n-but-2-enyl, isobutenyl, 1,3-butadienyl, cyclopentenyl, cyclohexenyl and styryl.

@
When the organic residue has one or possibly more than one triple bond, it is often chosen from an alkinyl group comprising from 2 to 3. 20 carbon atoms, preferably 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Specific examples of such groups are ethinyl, 1-propinyl, 2-propinyl, n-but-2-inyl, and 2-phenylethinyl.

 When the organic residue comprises one or possibly more aromatic systems, it is often an aryl group comprising from 6 to 24 carbon atoms, preferably from 6 to 12 carbon atoms. Specific examples of such groups are phenyl, 1-tolyl, 2-tolyl, 3-tolyl, xylyl, 1naphthyl and 2-naphthyl.

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 Heterocycle is understood to denote in particular a ring system comprising at least one saturated or unsaturated ring formed of 3, 4, 5, 6, 7 or 8 atoms, at least one of which is a heteroatom. The heteroatom is often selected from B, N, O, Si, P, and S. More often it is selected from N, O and S.

dans laquelle J et L sont choisis indépendamment parmi C, N, 0 et S et m et n valent indépendamment de 0 à 4, de préférence 1, 2 ou 3. The heterocycle often responds to the formula

wherein J and L are independently selected from C, N, O and S and m and n are independently 0 to 4, preferably 1, 2 or 3.

 Specific examples of such heterocycles are aziridine, azetidine, pyrrolidine, piperidine, morpholine, 1,2,3,4-tetrahydroquinoline, 1,2,3,4 tetrahydroisoquinoline, perhydroquinoline, perhydroisoquinoline, (1H) -indole, isoxazolidine, pyrazoline, imidazoline, thiazoline, furan, tetrahydrofuran, thiophene, tetrahydrothiophene, pyran, tetrahydropyran and dioxane.

 The organic residues as defined above may be unsubstituted or substituted with functional groups. By functional group is meant in particular a substituent comprising or consisting of a heteroatom. The heteroatom is often selected from B, N, O, Al, Si, P, S, Sn, As and Se and halogens. More often, it is chosen from N, O, S and P, in particular N, O and S.

 The functional group generally comprises 1, 2, 3, 4, 5 or 6 atoms.

 As functional groups, there may be mentioned, for example, halogens, a hydroxyl group, an alkoxy group, a mercapto group, an amino group, a nitro group, a carbonyl group, an acyl group, an optionally esterified carboxyl group or a carboxamide group. , a urea group, a urethane group and the

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 thiolated derivatives of the groups comprising a carbonyl group mentioned above, a phosphine, phosphonate or phosphate group, a sulphoxide group, a sulphonated group or a sulphonate group.

 In particular, the group A may also form a ring system with the group X. An A group comprising nitrogen and / or oxygen atoms, and in particular heterocycles comprising these atoms is preferred. The group A is generally an organic residue containing at least one activated atom for an electrochemical reaction.

 In the organic compound salt, the X group is a cationic or anionic group. A cationic group is preferred.

The group X often comprises at least one atom of groups 13,
15 or 16 of the periodic table of the elements. A group X comprising at least one atom of groups 13 or 15 of the periodic table of elements is. prefer. Among these atoms, those of the second and third period are more particularly preferred. An X group comprising at least one nitrogen or sulfur atom is very particularly preferred.

 In a first particular aspect, the group X corresponds to the formula N-C (= NH) -NH 2 +. Particular examples of organic compound salt comprising this group are chosen from arginine derivatives, in particular N-protected amides of arginine, for example with a heterocycle comprising nitrogen as defined above.

In a second particular aspect, the group X satisfies the formula
SR 2 + in which R denotes organic residues, in particular as defined above, it being understood that these residues may be identical or different or form a ring with each other or with the group A. Particularly as R are alkyl, cycloalkyl or aryl and more particularly a methyl group. Particular examples of organic compound salt comprising this group are chosen from S-alkylmethionine derivatives, in particular N [alpha] -protected amides of S-methyl-methionine, optionally enantiopur, for example with a heterocycle comprising nitrogen as defined above.

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 When the group X is a cationic group, it preferably corresponds to the formula -NR 3 + in which R is one or more organic residues, in particular as defined above, it being understood that these residues may be identical or different or form a cycle between they or with the group A are particularly suitable as R alkyl, cycloalkyl or aryl groups or groups forming with nitrogen a heterocycle, as defined above. Alkyl groups and groups forming with nitrogen a heterocycle are more particularly preferred.

 Among the trialkylamino groups, the trimethylamino, triethylamino, diethylmethylamino and diethylisopropylamino groups are preferred.

 Among the groups forming with nitrogen heterocycle those corresponding to the formula (II) above comprising a nitrogen atom carrying an alkyl group as defined above, in particular selected from methyl and ethyl are preferred.

(III) dans laquelle R est comme défini ci-avant, m est 0, 1, 2 ou 3 n est 1 ou 2, L est choisi parmi C, 0, S et N et A' est une partie du résidu A. Among the groups forming a ring with the group A let us mention in particular those corresponding to the formula

(III) wherein R is as defined above, m is 0, 1, 2 or 3 n is 1 or 2, L is selected from C, O, S and N and A 'is a part of residue A.

 The groups of formula -NR 3 + above can be obtained for example from trisubstituted amines by reaction with a precursor containing a group capable of being substituted by nucleophilic substitution, such as Cl.

 In the organic compound salt, the Y group is generally an external counterion, i.e., it is not bound by a covalent bond to the A-X moiety.

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 The Y moiety is at least one cation or at least one anion having the opposite polarity to that of the X moiety. An anionic moiety is preferred.

Monovalent anions are particularly preferred.

 As anions, there may be mentioned in particular halogens, complex inorganic anions such as polyfluorinated anions or polyoxo, organic anions such as in particular organic sulfonates. The group Y may be chosen, preferably from Br-, Cl-, ClO4-, BF4-, PF6-, toluenesulfonate (Tos ') and benzenesulfonate (PhSO3'). A Y group selected from Cl-, ClO4-, BF4, and PF6- is particularly preferred.

 As cations, mention may in particular be made of inorganic or organic cations. An organic cation is preferred. A tetraalkylammonium cation, such as tetraethylammonium or tetra (n-butyl) ammonium is particularly preferred.

 In a first variant of the use according to the invention, the group Y comprises at least one anion or at least one cation, in particular a monovalent cation, which is inert under the conditions of the electrochemical reaction.

Among the anions which are generally stable under conditions of the electrochemical reaction, mention may in particular be made of complex inorganic anions such as polyfluorinated anions or polyoxo anions, and organic anions such as, in particular, organic sulfonates. BF4-, PF6-, toluenesulfonate (Tos-) and benzenesulfonate (PhSO3-) anions are preferred As cations, the above-mentioned tetraalkylammonium cations are well suited.

 In this variant, the anion content or inert cation is generally greater than or equal to 50% by weight of the total weight of the Y group. This content is often greater than or equal to 75% by weight of the total weight of the Y group.

This content is preferably greater than or equal to 90% by weight of the total weight of the Y group. In this variant, the Y group may consist essentially of an anion or an inert cation.

 It has been found that this variant makes it possible to obtain particularly good electrochemical and chemical yields and makes it possible to reach a particularly high concentration of organic compound salt in organic solvents.

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 In a particular aspect, the content of anion or inert cation is less than or equal to 99.5% by weight of the total weight of the Y group. In this aspect, the content of anion or inert cation is preferably less than or equal to 97%. by weight of the total weight of the Y group. In this particular aspect, the residual part of the Y group advantageously consists of at least one anion or at least one cation that can be converted into a reactive species under the conditions of the reaction. electrochemical. Examples of such anions are halogens, especially Br "and Cl- and in particular Cl-.

Preferably, the group Y is a mixture consisting essentially of on the one hand at least one ion selected from ClO4-, BF4-, @
PF6-, Tos and PhS03- and on the other hand Cl-.

 This particular aspect makes it possible to improve the selectivity and productivity of indirect electrochemical reactions in which an active species such as an oxidation or reduction means, capable of reacting with an organic compound, is generated in situ electrochemically. This aspect also makes it possible to work in the absence of additional quantities of anion or cation capable of being converted into a reactive species, extrinsic to the Y group of the organic compound salt.

 The invention also relates to the organic compound salt according to the first variant of the use according to the invention and to this particular aspect.

In a second variant of the use according to the invention, the organic compound salt corresponds to the formula R1R2R3C-TQX Y (IV) in which R1R2R3C denotes a substituted carbon atom capable of reacting in the electrochemical reaction;
T denotes an activating group for the electrochemical reaction and;
Q denotes a connector group connecting the activating group T and the charged group X.

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 In the group R1R2R3C, R1 and R2 independently signify hydrogen atoms, organic residues as defined above or R1 and R2 together form organic residues as defined above. At least one of R 1 or R 2 can form a ring with the group X, the group Q or the group T.

 The group R3 is a group that can be modified during the electrochemical reaction. R3 can mean, for example, a double bond formed with the group T or one of the groups R1 or R2. R3 is preferably selected from -C.OOH and a hydrogen atom. A hydrogen atom is more particularly preferred.

 The activating group T is generally a heteroatom, as described above in the context of the description of the functional groups. The group T is preferably chosen from NR 4, O and S. An NR 4 group is very particularly preferred.

 R4 denotes a hydrogen atom or an organic residue as defined above. R4 can form a ring with the substituent R1 or R2. Preferably, R4 is chosen from an alkyl or cycloalkyl group as defined above.

Particularly preferably, R 4 forms with R 1 or R 2 a heterocycle corresponding to the above formula.

 The connector group Q is generally chosen from a linear or branched alkylene or cycloalkylene group as defined above, preferably comprising from 1 to 12 carbon atoms, optionally substituted by a functional group as described above.

 Preferably, the group Q is an optionally substituted polymethylene group comprising 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms.

Such a group comprising 1, 2, 3 or 4 carbon atoms is very particularly preferred.

 The group Q preferably comprises a functional group as described above which binds it to the group T par. It has been found that the presence of a functional group linking the group Q to the group T is particularly useful when one wishes to carry out subsequent reactions with the product of the electrochemical reaction aiming, for example, to separate the

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 group loaded. The functional group may also exert an additional activating effect and a stabilizing effect during the electrochemical reaction.

 Particular examples of functional groups linking the group Q to the group T are chosen from - (C = O) -, -N- (C = O) -, -O- (C = O) -, - (S = O) -, -N- (S = O) -, -SO2-, -N-SO2-, - (C = S) - and -N- (C = S) -. A functional group selected from - (C = O) -, -N- (C = O) -, -O- (C = O) - and -SO 2 - is preferred. A functional group chosen from - (C = O) - and -SO 2 -, which is very particularly preferred. It is meant that the right-side linkage of the functional groups as indicated above is linked to the T group.

In a particularly preferred embodiment, the organic compound salt has the formula
R1R2R3C-NR4-Q-NR3 + Y-, (V) the substituents being defined above. Particularly preferred examples of the organic compound salt are of the following formulas wherein the substituents are as defined above:

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In a third variant of the use according to the invention, the organic compound salt comprises at least one stereogenic center, in particular the organic compound salt and comprises a center of chirality.

This variant is particularly useful when during the electrochemical reaction or during any subsequent reactions one or more stereogenic centers are formed. The diastereomers formed can then be separated easily and benefit from diastereoselective reactions.
In the third variant of the use according to the invention, the organic compound salt is preferably enantiopur.

 The term "enantiopure organic compound salt" is intended to denote a chiral organic compound salt consisting essentially of an enantiomer. The enantiomeric excess (ee) is defined as: ee (%) = 100 (X1-X2) / (X1 + X2) with xi> X2; xi and X2 represent the content of the enantiomeric mixture 1 or 2 respectively.

 In general, an enantiopure organic compound salt is used whose enantiomeric excess is greater than or equal to 99%. An enantiopure organic compound salt whose enantiomeric excess is greater than or equal to 99.5% is preferred. In a particularly preferred manner, an enantiopure organic compound salt is used whose enantiomeric excess is greater than or equal to 99.9%.

 The use of an enantiopure organic compound salt provides access to organic compounds and in particular to electrochemical reaction products having a high enantiomeric excess.

 Specific examples of enantiopure organic compound salts are, for example, amides of trialkyl betaines of natural or unnatural amino acids such as in particular amides of stachydrine or carnitine.

Other amino acid derivatives having a charged group are mentioned above.

 The invention also relates to a process for the manufacture of an organic compound comprising (a) a step in which a solution comprising an organic compound salt as described above in a solvent (b) a step in which the solution is electrolyzed in the presence of at least one co-reactant under conditions sufficient to form the reaction product of the organic compound salt with the co-reactant.

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 In the process according to the invention, step (b) may for example be electroreduction or electrooxidation. Preferably step (b) is an electrooxidation.

 In the process according to the invention, step (b) can be carried out in a compartmentalized or non-compartmentalized cell.

 The electrodes used in step (b) must be resistant to the conditions of the electrochemical reaction. Suitable materials are selected in particular from metals, metal oxides and graphite.

Particularly suitable metals are chosen from among steel, iron or titanium and in particular from platinum group metals and their oxides, or electrodes coated with these latter materials. Platinum or rhodium is preferred. An electrode comprising platinum is particularly suitable.

 The distance between the electrodes is generally at least 0.2 mm.

Often this distance is at least 0.5 mm. Preferably, it is at least
1 mm. The distance between the electrodes is generally at most 20 mm.

 Often this distance is at most 10 mm. Preferably, it is at most 5 mm.

 In the process according to the invention, step (b) is generally carried out at a current density greater than or equal to 0.1 A / dm 2. Often the current density is greater than or equal to 1 A / dm2. Preferably it is greater than or equal to 3 A / dm2. In the process according to the invention, step (b) is generally carried out at a current density of less than or equal to 50 A / dm 2. The current density is less than or equal to 30 A / dm 2. Preferably it is less than or equal to 20 A / dm 2.

 In the process according to the invention, step (b) is generally carried out at a temperature greater than or equal to -50 ° C. Often the temperature is greater than or equal to -20 ° C. Preferably it is greater than or equal to 0 ° C. .

In the process according to the invention, step (b) is generally carried out at a temperature of less than or equal to 100 ° C. Often the temperature is less than or equal to 80 ° C. Preferably it is less than or equal to 60 ° C.

 In the process according to the invention, the concentration of organic compound salt in the solution used in step (b) is generally greater than or equal to 0.1 mol / L. Often this concentration is greater than or equal to 0.2 moI / L. Preferably it is greater than or equal to 0.25 mol / L. In the process according to the invention, the concentration of organic compound salt in the solution used in step (b) is generally less than or equal to 3

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 mol / L. Often this concentration is less than or equal to 2 mol / L. Preferably it is less than or equal to 1 mollL.

 Solvents for use in the process according to the invention are generally capable of completely dissolving the desired amount of organic compound salt at the temperature of the reaction. Examples of usable solvents include water, polar organic solvents and homogeneous mixtures of water with polar organic solvents.

 In a first aspect, the solvent is inert under the conditions of the electrochemical reaction. In this case, the solution generally also comprises a co-reagent capable of reacting with the electron-transferring organic compound salt.

In a second aspect, the solvent is itself a co-reactant. In this aspect, the solvent is preferably essentially co-reactive
It has been found that it is possible to limit the number of constituents of the reaction medium of the process according to the invention to a minimum and to further facilitate the separation and purification of the product of the electrochemical reaction.

 The co-reactant which can be a solvent is often chosen from water, alcohols and carboxylic acids, and mixtures thereof. The co-reagent is preferably selected from water, methanol and ethanol. Methanol is especially preferred.

 In a very particularly preferred variant of the process according to the invention, the organic compound salt is in accordance with formula (V) and the coreactant is methanol.

 The process according to the invention can be carried out in the substantial absence of conductive salt. In this case, the concentration of conductive salt is generally less than 0.01 mol / l of solution used. Preferably, the conductive salt concentration is less than 0.001 mol / L. The solution used may be substantially free of conductive salt.

 The product of step (b) is often a modified organic compound salt.

If necessary to obtain the desired final product, subsequent reactions can be carried out starting from the modified organic compound salt, for example to remove the charged group or to modify certain substituents, for example by nucleophilic or electrophilic substitution.

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The invention also relates to an organic compound salt having the formula R1R2ZC-TQX Y (XXIII) in which
X is a charged group as defined above;
Y is a counterion as defined above;
Z is a group likely to be substituted; R1 and R2 denote organic residues as defined above;
T denotes a group containing a heteroatom selected from N-R4, O and S, NR4 being as defined above;
Q denotes a connector group connecting the heteroatom and the charged group, as defined above.

 It has been found that the organic compound salt according to the invention is an effective intermediate product for. production of organic products, having significant advantages regarding its solubility in reaction solvents and allowing separation and easy purification of the products obtained.

When the organic compound salt according to the invention is an enantiopur product, it is an effective intermediary for asymmetric synthesis.

 The substituent Z denotes in particular a group capable of being substituted by nucleophilic substitution. Such groups may be chosen for example from halogens, in particular chlorine or bromine, esters and alkoxy groups. Esters within the Z group are often selected from fluorinated esters such as fluoroacetates, fluoroalkylsulfonates or alkyl- or arylsulfonates. Preferably, the esters are chosen from trifluoroacetate and trifluoromethanesulphonate and ptolylsulphonate. Alkoxy groups often include 1, 2,3 or 4 carbon atoms. Methoxy and ethoxy groups are preferred. A methoxy group is most preferred as the Z substituent.

 It is understood that the combinations and preferences indicated above for the use according to the invention also apply, insofar as they are applicable, to the organic compound salt according to the invention.

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 The organic compound salt according to the invention can be obtained by the process according to the invention.

 The organic compound salt according to the invention, in particular when Z is methoxy, may be used in substitution reactions, in particular catalyzed by acids, in particular Lewis acids, preferably with a silylated reagent such as allyltrimethylsilane. or trimethylsilyl cyanide (TMSCN) or with aromatics.

 Particular examples of organic compounds obtained from the organic compound salt according to the invention include natural or non-natural amino acids such as proline and P-proline.

 The following examples intend to illustrate the invention without limiting it.

N,N,N-triéthy1ethanaminium tétrafluoroborate LI) Exemple 2 Fabrication de 3-N-pipéridine-N,N,N-

iriéthylammoniopropanesulfonamide tétrafluoroborate (2) Par des procédures analogues à l'exemple 1, le composé (2) a été obtenu au départ de pipéridine, de chlorure d'acide 3-chloropropylsulfonique et de triéthylamine. EXAMPLE 1 Manufacture of 2- (N-pyrrolidine) -N, N, N-triethylethanammonium tetrafluoroborate (1) 3.82 moles of pyrrolidine were added to a solution of 1.92 moles of chloroacetyl chloride in 600 ml of dichloromethane . The temperature was maintained at 0 ° C. The organic phase was washed with sodium hydrogen sulfate and sodium carbonate solution and dried. After evaporation of the solvent, 242 g of N- (2-chloroacetyl) pyrrolidine were obtained. 1.64 mol of this compound was dissolved in 500 mL of toluene and 231 mL of triethylamine was added. Refluxed for 3 h and after cooling, 311.5 g of product was isolated as a precipitate. 119.07 g of the product obtained was dissolved in 250 ml of dichloromethane to boiling in the presence of 7.21 g of HBF4 (54% by weight in diethyl ether) and 112.55 g of 2- (N-pyrrolidine) was isolated. -

N, N, N-triethylethanaminium tetrafluoroborate LI) Example 2 Production of 3-N-piperidine-N, N, N-

Ethylammoniopropanesulfonamide tetrafluoroborate (2) By procedures analogous to Example 1, compound (2) was obtained from piperidine, 3-chloropropylsulfonic acid chloride and triethylamine.

 Examples 3 and 4 Electrochemical Methoxylation Compound (1) or (2) was dissolved in methanol. This solution was introduced into a non-compartmentalized cell with a volume of 150 ml provided with a platinum cylindrical anode having an internal diameter of 9 mm, an outside diameter of 11 mm and a useful length of 27.5 cm. cathode steel. The distance between cathode and anode was 2mm. The reaction was

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 arrested at the time of the appearance of secondary products (selectivity of the order of 100%).

synthèse de 2-(N-2'méthoxypyrroIidine)-N,N,N-tnéthylethananimonmm tétrafluoroborate (la) et 3-N-2'méthoxy pipéridine-N,N,Ntriéthylammoniopropanesulfonamide tétrafluoroborate (2a) respectivement :

Le produit méthoxylé (la) ou (2a) respectivement a été isolé de manière aisée par évaporation du méthanol. Sa pureté était suffisante pour permettre sa mise en #uvre pour des réactions ultérieures.-
Exemple 5 On a dissout à 0 C 1,06 g de (la) dans 3 mL de dichlorométhane en présence de 0,9 mL de cyanure de triméthylsilyl et 100 l de SnC14 et on a agité pendant h. On a soumis la solution obtenue à une hydrolyse avec 6 mL de 6NHC1 à une température de 100 C. On a filtré sur une colonne échangeuse d'ions acide et élué avec du NH3 aqueux (5%). On a isolé un produit brut contenant 0,25 g. Under the conditions indicated, the following results were obtained for the

synthesis of 2- (N-2'methoxypyrrolidine) -N, N, N-methylethanammonium tetrafluoroborate (1a) and 3-N-2'methoxypiperidine-N, N, N-triethylammonopropanesulfonamide tetrafluoroborate (2a) respectively:

The methoxylated product (la) or (2a) respectively was easily isolated by evaporation of methanol. Its purity was sufficient to allow its implementation for subsequent reactions.
EXAMPLE 5 1.06 g of (Ia) in 3 ml of dichloromethane was dissolved at 0 ° C. in the presence of 0.9 ml of trimethylsilyl cyanide and 100 μl of SnCl.sub.4 and stirred for hr. The resulting solution was hydrolyzed with 6 mL of 6NHCI at a temperature of 100 ° C. It was filtered through an acid ion exchange column and eluted with aqueous NH3 (5%). A crude product containing 0.25 g was isolated.

(57%) of praline.

Claims (10)

1 - Organic compound salt corresponding to the formula R1R2ZC-T-Q-X Y in which X is a charged group Y is a counter-ion Z is a group likely to be substituted; R1 and R2 denote organic residues; T denotes a group containing a heteroatom selected from N-R4, O and S wherein R4 denotes a hydrogen atom or an organic residue; Q denotes a connector group connecting the heteroatom and the charged group.  2 - Organic compound salt according to claim 1, wherein the group T is N-R4.  3 - organic compound salt according to claim 1 or 2 wherein the Q group is selected from a linear or branched alkylene group or a cycloalkylene group, optionally substituted with a functional group, preferably comprising from 1 to 12 carbon atoms and optionally linked to the group T by a functional group chosen from

 - (C = O>, -N- (C = O) -, -O- (C = O) -, - (5 = O) -. -N- (S = O) -, -SO2-, - N-SO2- ?, (C = S) - and -N- (C = S) -.  4 - organic compound salt according to claim 3 wherein the Q group is linked to the group T by a functional group selected from - (C = O) -, -N- (C = O) -, -O- (C = O) -, -SO2-, and -N-SO2-.  5 - organic compound salt according to any one of claims 1 to 4, wherein the group X is a cationic group- <Desc / Clms Page number 20> 6 - An organic compound salt according to any one of claims 1 to 5, wherein the X group is NR3 + and R -signal organic residues.  7 - The organic compound salt according to any one of claims 1 to 6, wherein the Y group is selected from Br-, Cl-, C104, BF4-, PF6-, Toset PhS03-.  8 - organic compound salt according to any one of claims 1 to 7, wherein the Z group is methoxy.  9 - "organic compound salt according to any one of claims 1 to 8, comprising at least one stereogenic center.  -Use of an organic compound salt according to any one of claims 1 to 9 as a starting material for a substitution reaction.