JP2015527483A - Anodization of organic substrates in the presence of nucleophiles - Google Patents

Abstract

The present invention relates to a liquid comprising an organic compound having at least one carbon bonded to a hydrogen atom, a nucleophile, and an ionic liquid in a proportion of at least 10% by mass in an electrochemical cell having a cathode and an anode. The present invention relates to a method for anodic substitution, which comprises a step of electrolyzing a reaction medium, wherein the hydrogen atom is at least partially substituted with a nucleophilic group of a nucleophile. A gas diffusion layer electrode is preferably used as the anode.

Description

  The present invention relates to a liquid comprising an organic compound having at least one carbon bonded to a hydrogen atom, a nucleophile, and an ionic liquid in a proportion of at least 10% by mass in an electrochemical cell having a cathode and an anode. The present invention relates to a method for anodic substitution, which comprises a step of electrolyzing a reaction medium, wherein the hydrogen atom is at least partially substituted with a nucleophilic group of a nucleophile. In a preferred embodiment of the present invention, a gas diffusion layer electrode is used as the anode. Preferred nucleophiles are aliphatic alcohols and aliphatic carboxylic acids. Preferred ionic liquids are quaternary ammonium compounds having a melting point of less than 200 ° C. under atmospheric pressure (1 bar).

  Anodization of a substrate in the presence of a nucleophile (also referred to as electrochemical oxidation in the context of the present invention) is an important reaction type in organic electrochemistry that allows anodic displacement. Various nucleophiles have been used in electrolysis important for this synthesis (Eberson & Nyberg, Tetrahedron 1976, 32, 2185). By using an alcohol such as methanol, the alkoxylation of the substrate can be carried out (EP 1348043B, EP 1111094A).

By using an acid such as HCOOH, CH ₃ COOH or CF ₃ COOH, the acyloxylation of the substrate becomes possible (EP 1111094A). In addition, fluorination is known as one means for selective introduction of fluorine (Fuchigami, Organic Electrochemistry, 4th edn., (Eds .: Lund & Hammerich), Dekker, New York, 2001, p. 1035. ). In the first step, when sufficiently stable cation radicals are provided by removal of electrons from the substrate, substitution products can be obtained by attack with nucleophiles, and this anodic substitution usually proceeds well.

  Anodic substitution is utilized on an industrial scale, for example, in the second methoxylation of a methyl-substituted aromatic compound, the corresponding acetal is obtained. In 1 cell / 1 step, ether is obtained as an intermediate in the first methoxylation step and acetal is obtained by further methoxylation. By this elegant method, aromatic aldehydes are synthesized from toluene derivatives, for example, p-tert-butylbenzaldehyde is synthesized from p-tert-butyltoluene (DE 2848397).

  However, this electrolytic synthesis also has the disadvantage that, for example, the range of substrates for acetalization of methyl-substituted aromatic compounds is limited. Acetalization of p-substituted toluene derivatives is effective only in the above industrial examples when the substituent is an electron donating group such as a tert-butyl group. Even when the p-substituent is not an electron donating group, its selectivity is very low. This problem has been unresolved for decades.

  A trivial problem with anodic substitution is when the reaction between the nucleophile and the substrate causes undesired reaction pathways, for example, ring opening due to the reaction between a cyclic compound such as ethylene carbonate and the nucleophile. Thus, substitution on the ring of ethylene carbonate is usually not carried out by a nucleophile, but by a radical route.

  Unexpectedly, a method to improve normal anodic substitution by using high concentration of ionic liquid electrolyte (conversion rate, selectivity, current yield and easy implementation in a wide range of organic compounds for anodic substitution) ) Was found.

  This method also makes it possible to perform anodic substitution with an organic compound that tends to cause a reaction on the nucleophile side, for example, a ring-opening reaction of a cyclic carbonate.

The present invention
a) providing an organic compound having at least one hydrogen atom bonded to a carbon atom;
b) providing a liquid reaction medium comprising the organic compound and a nucleophile in an electrochemical cell having a cathode and an anode;
c) electrolyzing the liquid reaction medium to replace at least some of the hydrogen atoms and nucleophilic groups of the nucleophile;
And the liquid reaction medium further comprises an ionic liquid in a proportion of at least 10% by mass.

  This method of replacing the anode is a special case of electrochemical oxidation. An important feature of the process according to the invention is the use of a liquid reaction medium comprising an ionic liquid in a proportion of at least 10% by weight.

  In the context of the present invention, the term ionic liquid means a salt (a compound of a cation and an anion) having a melting point of less than 200 ° C., preferably less than 150 ° C., particularly preferably less than 100 ° C. under atmospheric pressure (1 bar). means. The ionic liquid can also include a mixture of different ionic liquids.

The ionic liquid preferably contains an organic compound as a cation (organic cation). Depending on the valence of the anion, the ionic liquid can contain further cations including metal cations in addition to the organic cation. Particularly preferred cations of the ionic liquid are exclusively organic cations or, in the case of multivalent anions, a mixture of different organic cations.
Suitable organic cations have in particular heteroatoms such as nitrogen, sulfur, oxygen or phosphorus; in particular, the organic cations are ammonium groups (ammonium cations), oxonium groups (oxonium cations), sulfonium groups (sulfonium cations) Or it has a phosphonium group (phosphonium cation).

In a special embodiment, the organic cation of the ionic liquid is an aluminum cation, and the aluminum cation in the present invention is
A non-aromatic compound having a nitrogen atom in which a positive charge is localized, for example a compound having a tetravalent nitrogen (quaternary ammonium); or a compound having a trivalent nitrogen, of which one bond is A compound which is a double bond; or-an aromatic compound in which no positive charge is localized in an aromatic ring system and which has at least one nitrogen atom, preferably 1 to 3 nitrogen atoms;
It is.

Preferred organic cations are quaternary ammonium cations, which have 3 or 4 aliphatic substituents (optionally substituted with hydroxyl groups) on the nitrogen atom. And a C ₁ -C ₁₂ -alkyl group is particularly preferred.

In the context of the present invention, C ₁ -C ₁₂ - alkyl expressions, C ₁ -C ₁₂ linear or branched in and saturated or unsaturated - containing alkyl group. Preferred C ₁ -C ₁₂ - alkyl group is an alkyl group of saturated.

  Similarly, in a preferred embodiment, the organic cation has a heterocyclic ring system, and the heterocyclic ring system has 1 to 3, particularly 1 or 2, nitrogen atoms as the structure of the heterocyclic ring system. . All heterocyclic systems are possible, monocyclic, bicyclic, aromatic or non-aromatic. As examples of such ring systems, mention may be made of the bicyclic systems described in WO2008 / 043837. The bicyclic system described in WO 2008/043837 is a diazabicyclo derivative, preferably formed by a 7-membered ring and a 6-membered ring having an amidinium group, in particular 1,8-diazabicyclo (5.4.0)- Mention may be made of the cation of 7-undencene.

  The ammonium cation is particularly preferably a quaternary ammonium cation, an imidazolium cation, a pyrimidinium cation or a pyrazolium cation.

  The ionic liquid can contain inorganic or organic anions, such anions are described, for example, in the above-mentioned WO 03/029329, WO 2007/076979, WO 2006/000197 and WO 2007/128268.

Preferred anion embodiments include the following groups:
Formula R ^a OSO ₃ ⁻ [wherein, R ^a is a C ₁ -C ₁₂ -alkyl group, C ₁ -C ₁₂ -perfluoroalkyl group or C ₆ -C ₁₀ -aryl group, preferably C _1- An alkyl sulfate of a C ₆ -alkyl group, a C ₁ -C ₆ -perfluoroalkyl group or a C ₆ -aryl group (tosylate)];
An alkyl sulfonate of the formula R ^a SO ₃ ⁻ , wherein R ^a is a C ₁ -C ₁₂ -alkyl group, preferably a C ₁ -C ₆ -alkyl group;
Formula (R ^a SO ₂ ) ₂ N ⁻ [wherein, R ^a is a C ₁ -C ₁₂ -alkyl group or a C ₁ -C ₁₂ -perfluoroalkyl group, preferably a C ₁ -C ₆ -alkyl group. Or a C ₁ -C ₆ -perfluoroalkyl group].
Halides, in particular chloride, bromide or iodide;
Pseudohalides such as thiocyanate, dicyanamide;
A carboxylate of the formula R ^a COO ⁻ , wherein R ^a is a C ₁ -C ₁₂ -alkyl group, preferably a C ₁ -C ₆ -alkyl group, in particular an acetate;
Phosphates, in particular, wherein R ^a R ^b PO ₄ ^-
[Wherein, R ^a and R ^b are each independently a C ₁ -C ₆ -alkyl group, and in particular, R ^a and R ^b are the same alkyl group (eg, dimethyl phosphate or diethyl phosphate). dialkyl phosphates of a]; and phosphonates, in particular, wherein R ^a PO ₃ ^-
Wherein R ^a is a C ₁ -C ₆ -alkyl group;
From the anion.

  Suitable ionic liquids in the context of the present invention are, for example, ammonium tetraalkylalkyl sulfate (eg methyltributylammonium methylsulfate (MTBS)) or ammonium tetraalkylbis (alkylsulfonyl) imide (eg methyltributylammonium). Bis (trifluoromethylsulfonyl) imide (MTB-TFSI) or tetraoctylammonium bis (trifluoromethylsulfonyl) imide).

  The proportion of the ionic liquid or mixture thereof should be high with respect to the total amount of the liquid reaction medium, at least 10% by weight, preferably at least 25% by weight, more preferably at least 50% by weight, in particular at least 65% by weight. It is.

  Any electrode suitable for the electrochemical oxidation process can be used as the anode and cathode. One skilled in the art can determine the appropriate electrode.

  In a preferred embodiment of the present invention, at least one gas diffusion layer electrode is used as the anode.

  Gas diffusion layer (GDL) electrodes are known from fuel cell technology and consist of a substrate and a microporous layer containing carbon particles as the main component. Suitable GDLs are described in particular in US 4,748,095, US 4,931,168 and US 5,618,392. The teachings of these documents are incorporated by reference in the present invention. Suitable GDLs can be found, for example, in SGL Group Ballard Power Systems Inc. , Freudenberg FCCT KG (eg, g of the H2315 series).

  GDL typically includes a fiber layer or substrate and a microporous layer composed of carbon particles bonded together. The degree of hydrophobization can be varied by such methods that wettability and gas permeability can be adjusted.

  The GDL electrode for the method of the present invention preferably contains no supported catalyst on the surface of the electrode. The GDL electrode includes a base material and a microporous layer containing carbon particles as a main component, preferably carbon black. The GDL electrode can be manufactured according to US 6,103,077, and finally it is possible to use components that are commercially available as substrates and carbon particles.

  The cathode is selected from felt materials such as Pt, Pb, Ni, graphite, coal or graphite felt, stainless steel and GDL electrodes.

  The organic compound provided in step a) of the process according to the invention can be any organic compound having at least one hydrogen atom which is usually bonded directly to a carbon atom, the carbon atom being a condition for anodic substitution. Below, it can be substituted by a nucleophilic group. Of course, it is also possible to use mixtures of organic compounds. In order to allow the electrode to effect anodic substitution, it exhibits ionic conductivity by a combination of at least one nucleophile, a proportion of at least 10% by weight of ionic liquid, and optionally a solvent and / or additive. Organic compounds capable of forming a liquid reaction medium are suitable.

  The hydrogen atom is preferably directly bonded to the carbon atom, and more preferably part of an alkyl group. In the present invention, 1, 2 or 3 hydrogen atoms are directly bonded to a carbon atom. The carbon atom is a tertiary carbon atom of an alkane or cycloalkane, an allylic carbon atom of an alkene or cycloalkene or corresponding diene, a carbon element located at the α position with respect to the arene site of an alkylarene, or a nitrogen atom of an amide. The carbon element located at the α-position or the carbon element located at the α-position with respect to the oxygen atom of the ether is preferred.

The organic compound in the present invention preferably represents an alkyl group or an alkylene group having at least one hydrogen atom directly bonded to a carbon atom. Particularly preferred organic compounds are
(I) an alkane or cycloalkane having at least one hydrogen atom directly bonded to a tertiary carbon atom, (ii) an alkene or cycloalkene having at least one hydrogen atom directly bonded to an allyl carbon atom, or The corresponding diene, (iii) an alkylarene having at least one hydrogen atom bonded directly to the carbon atom located in the α position relative to the arene moiety, and (iv) a carbon atom located in the α position relative to the nitrogen atom An amide having at least one hydrogen atom directly bonded to (v), or (v) an ether, an ester, a carbonate having at least one hydrogen atom directly bonded to a carbon atom located α-position to the oxygen atom, or Acetal.

  The organic compound may have a functional group that is almost stable under the reaction conditions. Suitable functional groups include carbonyl, thiocarbonyl, ester, thioester, amide, oxycarbonyloxy, urethane, urea, hydroxyl, sulfonyl, sulfinate, sulfonate, sulfate, ether, amine, nitrile and the like and combinations thereof.

［式中、
Ｘは、Ｏ、Ｎ−Ｒ³又はＣＲ⁴Ｒ⁵であり、
Ｒ¹は、Ｃ₁−Ｃ₆−アルキル、Ｃ₁−Ｃ₆−アルコキシ−Ｃ₁−Ｃ₆−アルキル、ホルミル、Ｃ₁−Ｃ₆−アルキルカルボニル及びＣ₁−Ｃ₆−アルキルオキシカルボニルから選択され、
ＸがＣＲ⁴Ｒ⁵基である場合、Ｒ¹はＣ₁−Ｃ₆−アルコキシであってもよく、
ＸがＮ−Ｒ³又はＣＲ⁴Ｒ⁵基である場合、Ｒ¹はＣ₁−Ｃ₆−アルキルカルボニルオキシであってもよく、
Ｒ²は、水素、Ｃ₁−Ｃ₆−アルキル、Ｃ₁−Ｃ₆−アルコキシ−Ｃ₁−Ｃ₆−アルキル、Ｃ₆−Ｃ₁₀−アリール−Ｃ₁−Ｃ₆−アルキル、Ｃ₃−Ｃ₁₂−シクロアルキル及びＣ₆−Ｃ₁₀−アリールから選択され、
Ｒ³は、水素、Ｃ₁−Ｃ₆−アルキル、Ｃ₁−Ｃ₆−アルコキシ−Ｃ₁−Ｃ₆−アルキル、ホルミル、Ｃ₁−Ｃ₆−アルキルカルボニル及びＣ₁−Ｃ₆−アルキルオキシカルボニルから選択され、
Ｒ⁴及びＲ⁵は、独立して、水素、Ｃ₁−Ｃ₆−アルキル、Ｃ₁−Ｃ₆−アルコキシ−Ｃ₁−Ｃ₆−アルキル及びＣ₁−Ｃ₆−アルコキシから選択されるか、又は、
Ｒ¹及びＲ²は、それらが結合しているＸ−（Ｃ＝Ｏ）−Ｏ基と一緒になって、５〜７員のヘテロシクロ環を形成し、当該ヘテロシクロ環は、Ｏ、Ｓ、ＮＲ^c若しくはＣ＝Ｏから選択され、Ｒ^cが水素、アルキル、シクロアルキル及びアリールから選択される、ヘテロ原子又はヘテロ原子を有する基の少なくとも１つを更に含んでいてもよく、或いは、
Ｘは、ＣＲ⁴Ｒ⁵基であり、かつＲ¹及びＲ⁴は、それらが結合している炭素原子と一緒になって、３〜７員のカルボシクロ環を形成する］の化合物から選択される。好ましくは、Ｘは、Ｏ、ＣＨ₂又はＮＲ³であって、Ｒ³は、Ｃ₁−Ｃ₄−アルキル又はＣ₁−Ｃ₄−アルキルカルボニルである。 In one aspect of the invention, the organic compound provided in step a) has the general formula I

[Where:
X is O, N—R ³ or CR ⁴ R ⁵ ;
R ¹ is selected from C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, formyl, C ₁ -C ₆ -alkylcarbonyl and C ₁ -C ₆ -alkyloxycarbonyl And
When X is a CR ⁴ R ⁵ group, R ¹ may be C ₁ -C ₆ -alkoxy,
When X is a N—R ³ or CR ⁴ R ⁵ group, R ¹ may be C ₁ -C ₆ -alkylcarbonyloxy;
R ² is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl-C ₁ -C ₆ -alkyl, C ₃ -C ₁₂ - is selected from aryl, - cycloalkyl and C ₆ -C ₁₀
R ³ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, formyl, C ₁ -C ₆ -alkylcarbonyl and C ₁ -C ₆ -alkyloxycarbonyl Selected from
R ⁴ and R ⁵ are independently selected from hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl and C ₁ -C ₆ -alkoxy, Or
R ¹ and R ² they are attached X- (C = O) together with the -O group, to form a heterocyclo ring having 5 to 7 membered, said heterocyclo ring, O, S, NR may further comprise at least one heteroatom or a group having a heteroatom selected from ^c or C═O and R ^c selected from hydrogen, alkyl, cycloalkyl and aryl, or
X is a CR ⁴ R ⁵ group, and R ¹ and R ⁴ together with the carbon atom to which they are attached form a 3-7 membered carbocyclo ring] . Preferably X is O, CH ₂ or NR ³ and R ³ is C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkylcarbonyl.

In a further preferred embodiment, R ¹ and R ² together with the X— (C═O) —O group to which they are attached form a 5-7 membered heterocyclo ring, wherein the heterocyclo ring is It may further comprise at least one heteroatom or a group having a heteroatom selected from O, S, NR ^c or C═O and R ^c selected from hydrogen, alkyl, cycloalkyl or aryl. In this embodiment, preferably X is O, CH ₂ or NR ³ and R ³ is C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkylcarbonyl. Further, in this embodiment, R ¹ and R ² together, wherein _{-CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 2 - and _{-CH (C x H 2x + 1} ) -CH _2- (x is 1, 2, 3 or 4).

［式中、
Ｘは、Ｏ、ＣＨ₂又はＮＲ³であって、Ｒ³は、Ｃ₁−Ｃ₄−アルキル又はＣ₁−Ｃ₄−アルキルカルボニルであり、
Ａは、−ＣＨ₂−、−ＣＨ₂−ＣＨ₂−、−ＣＨ₂−ＣＨ₂−ＣＨ₂−、−ＣＨＲ⁷−、−ＣＨＲ⁷−ＣＨ₂−、−ＣＨ₂−ＣＨＲ⁷−、−ＣＨＲ⁷−ＣＨ₂−ＣＨ₂−、−ＣＨ₂−ＣＨＲ⁷−ＣＨ₂−及び−ＣＨ₂−ＣＨ₂−ＣＨＲ⁷−から選択されるアルキレン基であって、Ｒ⁷は、Ｃ₁−Ｃ₆−アルキルであり、
Ｒ⁶は、水素又はＣ₁−Ｃ₆−アルキルである］の化合物から選択される。好ましくは、ＸはＯ又は−ＣＨ₂−、Ａは−ＣＨ₂−又は−ＣＨＲ⁷−であって、Ｒ⁷は、Ｃ₁−Ｃ₄−アルキルであり、かつＲ⁶は、水素又はＣ₁−Ｃ₄−アルキルである。 In a further preferred embodiment, the organic compound provided in step a) has the general formula Ia

[Where:
X is O, CH ₂ or NR ³ , R ³ is C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkylcarbonyl,
A _{is, -CH 2 -, - CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CHR 7 -, - CHR 7 -CH 2 -, - CH 2 -CHR 7 -, - CHR ^{_{7 -CH 2 -CH 2 -, -}} CH 2 -CHR 7 -CH 2 - and -CH ₂ -CH ₂ -CHR ⁷ - an alkylene group selected from, R ⁷ is, C ₁ -C ₆ - Alkyl,
R ⁶ is hydrogen or C ₁ -C ₆ -alkyl]. Preferably, X is O or —CH ₂ —, A is —CH ₂ — or —CHR ⁷ —, R ⁷ is C ₁ -C ₄ -alkyl, and R ⁶ is hydrogen or C ₁ -C ₄ - alkyl.

  Examples of suitable organic compounds of general formula I and general formula Ia are ethylene carbonate, propylene carbonate (4-methyl-1,3-dioxan-2-one) and γ-butyrolactone.

In one aspect of the invention, the organic compound provided in step a) has the general formula II
Z-CHR ⁸ R ⁹ (II)
[Where:
Z is selected from C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl, C ₁ -C ₆ -allyl, —NR ¹⁰ R ¹¹ group and C ₁ -C ₆ -alkoxy;
R ⁸ is selected from hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl,
When Z is C ₆ -C ₁₀ -aryl or C ₁ -C ₆ -allyl, R ⁸ may be C ₁ -C ₆ -alkoxy;
R ⁹ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ - aryl, C ₆ -C ₁₀ - aryl -C ₁ -C ₆ - alkyl and C ₃ -C ₁₂ - is selected from cycloalkyl, or,
R ⁸ and R ⁹ together form C ₄ -C ₇ -alkylene or C ₄ -C ₇ -alkenylene;
R ¹⁰ and R ¹¹ are independently selected from hydrogen, C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl and C ₁ -C ₆ -alkylcarbonyl Or
Wherein Z, R ⁸ and R ⁹ are independently C ₁ -C ₆ -alkyl].

Preferably Z is C ₆ -C ₁₀ -aryl or substituted C ₆ -C ₁₀ -aryl and R ⁸ and R ⁹ are independently hydrogen, C ₁ -C ₆ -alkyl and C ₁ -C ₆ - is selected from alkoxy, particularly preferably, Z is, C ₆ -C ₁₀ - aryl or substituted C ₆ -C ₁₀ - aryl, and R ⁸ and R ⁹ are, independently, Selected from hydrogen, C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy.

Further, Z is, C ₁ -C ₆ - alkoxy, R ⁸ is hydrogen and C ₁ -C ₆ - is selected from alkyl, and R ⁹ is hydrogen, C ₁ -C ₆ - alkyl, C ₁ - It is equally preferred that it is selected from C ₆ -alkoxy, C ₆ -C ₁₀ -aryl and substituted C ₆ -C ₁₀ -aryl, particularly preferably Z is C ₁ -C ₄ -alkoxy, R ⁸ is selected from hydrogen and C ₁ -C ₄ -alkyl and R ⁹ is hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₆ -C ₁₀ -aryl and substituted Or C ₆ -C ₁₀ -aryl.

  Examples of suitable compounds of the general formula II are toluene, benzyl methyl ether and benzaldehyde dimethyl acetal.

In the context of the present invention, the expression C ₁ -C ₆ -alkyl includes straight-chain or branched and saturated or unsaturated C ₁ -C ₆ -alkyl groups. Preferred C ₁ -C ₆ -alkyl groups are saturated alkyl groups. Examples of C ₁ -C ₆ -alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl and n-hexyl. The above remarks regarding alkyl also apply to the alkyl moiety in alkoxy.

  In the context of the present invention, the term “cycloalkyl” usually denotes a cycloaliphatic radical having 3 to 12 carbon atoms, preferably 5 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, Examples include cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, bicyclo [2.2.2] octyl or adamantyl.

In the context of the present invention, the term C ₆ -C ₁₀ -aryl means a monocyclic or polycyclic aromatic hydrocarbon group. Preferred C ₆ -C ₁₀ - aryl is phenyl or naphthyl.

In the context of the present invention, the term substituted C ₆ -C ₁₀ -aryl means a monocyclic or polycyclic aromatic hydrocarbon group having 1 to 3 aromatic hydrogen atoms. Preferred substituents are independently, C ₁ -C ₆ - is selected from alkoxy - alkyl and C ₁ -C _6. The substituent is preferably in the p position. Examples of such substituents are p-methoxy, p-tert-butyl or p-methyl.

  In step b) of the process according to the invention, a liquid reaction medium is provided comprising an ionic liquid in a proportion of at least 10% by weight, an organic compound and a nucleophile.

  The nucleophile used in step b) can be any reagent or mixture of reagents that provides a stable nucleophile under electrolysis conditions, and the nucleophile is organic while the anode is replaced. It is sufficient if the hydrogen atom of the compound can be replaced with a nucleophilic group.

The general formula for anode substitution in the present invention is:
R−H + Nu ⁻ → R−Nu + H ⁺ + 2e ⁻
Where R—H is an organic compound as defined above and Nu ⁻ is a nucleophile. What is important is not the fact that two electrons are removed from this system, but the left-hand side of this equation includes two types that do not react with each other. The nucleophile represented by Nu ⁻ need not be negatively charged. The nucleophile in the context of the present invention may be, for example, pyridine (C ₅ H ₅ N). In such a case, a positively charged substitution product is obtained.

A nucleophile in the context of the present invention is a compound having a nucleophilic group. The nucleophilic group or nucleophile itself can act as a nucleophile in a nucleophilic substitution reaction with an organic compound having at least one hydrogen atom bonded to an electrophilic carbon atom. During the nucleophilic substitution reaction, the hydrogen atom is replaced with a nucleophilic group. In certain cases, the nucleophilic group is the same as the nucleophile (eg, pyridine (C ₅ H ₅ N)). In the context of the present invention, the term nucleophile is intended to be an attack reagent (eg C ₅ H ₅ N, RO ⁻ and RCOO ⁻ , as well as ROH, RCOOH), whereas the term nucleophilic group , the substituent (e.g., RO ^- or RCOO ^- and is, ROH, is not in RCOOH) is intended.

Preferred nucleophiles of the present invention are HO ⁻ , RO ⁻ , ROH, RCOO ⁻ , RCOOH, NO ₂ ⁻ , NO ₃ ⁻ , N ₃ ⁻ , OCN ⁻ , SCN ⁻ , RSO ₃ ⁻ , SeCN ⁻ , CN ⁻ , R − is selected from the group consisting of Cl ⁻ , Br ⁻ and I ⁻ , while R is represented by an alkyl group or an aryl group, preferably an alkyl group. Particularly preferred nucleophiles of this ^invention, RO - a or RCOOH ^-, ROH, RCOO.

Anodic displacement with HO ⁻ , RO ⁻ , RCOO ⁻ or NO ₃ ⁻ nucleophiles results in the formation of C—O bonds:
R—H + R′COO ⁻ → R—OCOR ′ + H ⁺ + 2e ⁻ (acyloxylation of anode)
R−H + R′O ⁻ → R−OR ′ + H ⁺ + 2e ⁻ (alkoxylation of anode)
R−H + HO ⁻ → R−OH + H ⁺ + 2e ⁻ (Anode hydroxylation)
R−H + NO ₃ ⁻ → R−ONO ₂ + H ⁺ + 2e ⁻ (nitration of anode)
R—H + R′SO ₃ ⁻ → R—OSO ₂ R ′ + H ⁺ + 2e ⁻ .

Anodic displacement with a nucleophile of N ₃ ⁻ , OCN ⁻ or NO ₂ ⁻ results in the formation of a C—N bond:
R−H + N ₃ ⁻ → R−N ₃ + H ⁺ + 2e ⁻ (Azide of anode)
R−H + OCN ⁻ → R−NCO + H ⁺ + 2e ^{−
_{R-H + NO 2 - →}} R-NO 2 + H + + 2e - ( nitration of the anode).

CN ^- anode substitution with a nucleophilic reagent results in the formation of C-C bonds:
R—H + CN ⁻ → R—CN + H ⁺ + 2e ⁻ (anode cyanation).

Nucleophile in the context of the present invention is a compound having a nucleophilic group, the nucleophilic group, for example, water (nucleophile HO ^- having), alcohols (e.g., nucleophilic groups RO ^- having the formula alcohols ROH), carboxylic acids (e.g., nucleophile RCOO ^- carboxylic acid) of the formula RCOOH with nitrite or a salt thereof (nucleophile NO ₂ ^- having), nitric acid or a salt thereof (nucleophile NO ₃ ^- having), hydrazoic acid or a salt thereof (nucleophile N ₃ ^- having) isocyanic acid or a salt thereof (nucleophile OCN ^- having), isothiocyanate or a salt thereof (nucleophile SCN ^- a ), Sulfonic acid (for example, sulfonic acid of formula RSO ₃ H having a nucleophilic group RSO ₃ ^— ), isoselenocyanic acid or a salt thereof (having a nucleophilic group SeCN ⁻ ), hydrogen cyanide or a salt thereof (nucleophilic group) CN ^- A), hydrogen chloride or a salt thereof (nucleophile Cl ^- with a), hydrogen bromide or a salt thereof (nucleophile Br ^- having), or hydrogen iodide or a salt thereof (nucleophilic groups I ^- having a) In the formula of each nucleophilic group, R represents an alkyl group or an aryl group.

Preferred nucleophiles of the invention are of formula III
R ¹² OH (III)
Or an alcohol of formula IV
R ¹³ COOH (IV)
R ¹² and R ¹³ are C ₁ -C ₁₂ -alkyl or perfluorinated C ₁ -C ₁₂ -alkyl, preferably C ₁ -C ₆ -alkyl or perfluorinated C _1- C ₆ -alkyl, particularly preferably C ₁ -C ₆ -alkyl.

In a preferred embodiment of the present invention, F ^- it is excluded from the nucleophile. Thus, in a particular embodiment, F ^- compound providing (fluoro agent) are excluded from the nucleophile. In this particular embodiment, such fluorinating agents are also excluded from ionic liquids.

  The molar ratio of nucleophile (including those considered as nucleophilic groups) to organic compound is preferably in the range of 1: 1 to 99: 1 (nucleophile: organic compound), more preferably 2: 1. ~ 99: 1.

In a special embodiment of the invention, the organic compound provided in step a) has the general formula V
Y-CH ₂ R ¹⁴ (V)
[Where:
Y is selected from C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl, C ₁ -C ₆ -allyl and —NR ¹⁰ R ¹¹ groups;
R ¹⁴ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ - aryl, substituted C ₆ -C ₁₀ - aryl and C ₃ -C ₁₂ - is selected from cycloalkyl,
R ¹⁰ and R ¹¹ are as defined above] and the nucleophile is an alcohol of formula III as defined above, while during the anodic displacement process Two hydrogen atoms are subsequently replaced by an —OR ¹² group, resulting in a compound of formula VI
Y-C (OR ¹² ) ₂ R ¹⁴ (VI)
Of acetal is obtained.

In one aspect, the present invention provides a method for producing an acetal of general formula VI as defined above by anodic substitution, wherein the anodic substitution comprises:
a) providing an organic compound of the general formula V as defined above;
b) providing in a electrochemical cell having a cathode and an anode a liquid reaction medium comprising said organic compound and an alcohol of the general formula III as defined above;
c) electrolyzing the liquid reaction medium to form an acetal of the general formula VI;
The liquid reaction medium further includes an ionic liquid in a proportion of at least 10% by mass.

  It is preferred that at least one gas diffusion layer electrode is used as the anode.

  An example of such an acetalization process is the conversion of toluene to benzaldehyde dimethyl acetal using methanol.

In a special embodiment of the invention, the organic compound provided in step a) has the general formula V
Y-CH ₂ R ¹⁴ (V)
[Where:
Y is selected from C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl, C ₁ -C ₆ -allyl and —NR ¹⁰ R ¹¹ groups;
R ¹⁴ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ - aryl, substituted C ₆ -C ₇ - aryl and C ₃ -C ₁₂ - chosen from cycloalkyl,
R ¹⁰ and R ¹¹ are as defined above] and the nucleophile is an alcohol of formula III as defined above, while during the anodic displacement process Two hydrogen atoms are subsequently replaced by an —OR ¹² group, resulting in a compound of formula VI
Y-C (OR ¹² ) ₂ R ¹⁴ (VI)
Of the formula VI and the acetal of formula VI is subsequently hydrolyzed to give the formula VIa
Y-COR ¹⁴ (VIa)
Aldehydes or ketones are obtained.

In one embodiment, the present invention provides a process for producing an aldehyde or ketone of general formula VIa as defined above by anodic substitution, wherein the anodic substitution comprises:
a) providing an organic compound of the general formula V as defined above;
b) providing in a electrochemical cell having a cathode and an anode a liquid reaction medium comprising said organic compound and an alcohol of the general formula III as defined above;
c) electrolyzing the liquid reaction medium to form an acetal of the general formula VI;
d) hydrolyzing the acetal of general formula VI to form the aldehyde or ketone of general formula VIa;
The liquid reaction medium further includes an ionic liquid in a proportion of at least 10% by mass.

  It is preferred that at least one gas diffusion layer electrode is used as the anode.

  An example of such a production method is the formation of benzaldehyde by subsequent hydrolysis of benzaldehyde dimethyl acetal after conversion of toluene into benzaldehyde dimethyl acetal using methanol. The hydrolysis step can be carried out according to methods conventionally known to those skilled in the art.

  In the context of the present invention, the expression “liquid reaction medium” refers to a reaction medium having a liquid phase under anodic displacement reaction conditions. This liquid phase contains a sufficient amount of organic compound to allow anodic replacement. As long as a sufficient amount of the organic compound is brought into contact with the electrochemical cell, in particular the anode electrode, the liquid phase need not contain the organic compound in the form of a homogeneous solution. Thus, the liquid reaction medium may contain an organic compound in the form of a homogeneous solution, colloidal solution, molecular dispersion solution, emulsified phase or dispersed phase. Eventually, it is also possible to introduce a gas fluid containing an organic compound into the liquid reaction medium.

  The liquid reaction medium in the electrochemical oxidation cell includes an ionic liquid contained at a ratio of at least 10% by mass with respect to the total amount of the liquid reaction medium, an organic compound in an amount dissolved in the liquid reaction medium, and the liquid. An amount of nucleophile dissolved in the reaction medium.

  The method in the present invention does not require any additional solvent or additive to establish an anodic displacement reaction that exhibits high conversion and good selectivity. In particular, the ionic liquid also has a function as a conductivity salt (electrolyte).

  In one aspect of the invention, the liquid reaction medium is essentially free of additional solvents or other additives, so the proportion of solvent and other additives is the total amount of liquid reaction medium. Is less than 1% by mass.

  When the liquid reaction medium comprises an organic solvent, the organic solvent is preferably selected from acetonitrile, ether, halogenated alkanes, sulfonates and mixtures thereof.

  In a particular embodiment of the invention, the liquid reaction medium contains at least one further additive as redox mediator and / or supporting electrolyte.

  Redox mediators are used in indirect electrolysis. Typical examples of redox mediators include 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), triarylamines such as tris (2,4-dibromophenyl) amine, or bromides or iodides. It is a halide (Steckhan, Agewandte Chemie 1986, 98, 681-699).

  In the present invention, preferred redox mediators are bromide salts or iodide salts, in particular bromide salts such as alkaline bromide salts or bromide salts of tetraalkylammonium.

  In a particular embodiment of the invention, the liquid reaction medium contains bromide or iodide salts as further additives. In this particular embodiment, preferably a GDL electrode is used as the anode and the ionic liquid is used in a proportion of 30 to 70% by weight, preferably 40 to 50% by weight, based on the total amount of the liquid reaction medium.

In this particular embodiment, the organic compound provided in step a) is preferably of the general formula VII
Y-CR ¹⁵ ₂ H (VII)
[Where:
Y is defined as above,
R ¹⁵ is C ₁ -C ₁₂ -alkoxy, preferably C ₁ -C ₆ -alkoxy], and the nucleophile is an alcohol of formula III as defined above, On the other hand, during the anodic replacement process, the hydrogen atom is replaced by the —OR ¹² group, resulting in the formula VIII
Y-CR ¹⁵ ₂ (OR ¹² ) (VIII)
The ortho-ester is obtained.

In one aspect, the present invention provides a process for preparing an ortho-ester of general formula VIII as defined above by anodic substitution, wherein the anodic substitution comprises:
a) providing an organic compound of the general formula VII as defined above;
b) providing in a electrochemical cell having a cathode and an anode a liquid reaction medium comprising said organic compound, a bromide salt or an iodide salt and an alcohol of the general formula III as defined above;
c) electrolyzing the liquid reaction medium to form the acetal of the general formula VII;
The liquid reaction medium further includes an ionic liquid in a proportion of at least 10% by mass.

  It is preferred that at least one gas diffusion layer electrode is used as the anode.

  Such a method of acetal alkoxylation mediated to ortho-esters is mediated by the current yield reported in the prior art document (Grosse Brinkhaus et al., Tetrahedron, 1986, 42, 553-560). Improved compared to the alkoxylation process.

In one aspect of the invention, the organic compound provided in step a) is a compound of general formula Ia as defined above and the nucleophile is of formula (IV) as defined above. Carboxylic acid. The nucleophilic acid in this embodiment is of the formula IV where R ¹³ is C ₄ -C ₁₂ -alkyl, preferably C ₄ -C ₆ -alkyl having a tertiary carbon atom in the α-position. Carboxylic acid. This method of the present invention provides for the ring opening of organic compounds of formula Ia, for example, ethylene carbonate using a nucleophile, even if the acid is a poorly nucleophile. Enables anodic substitution (acyloxylation) with ethylene carbonate or propylene carbonate having a carboxyl group that easily causes.

［式中、
Ｘ、Ａ及びＲ⁶は、一般式Ｉａの文脈において上記に定義されている通りであり、
Ｒ¹³は、Ｃ₁−Ｃ₁₂−アルキル又はペルフルオロ化されたＣ₁−Ｃ₁₂−アルキル、好ましくは、Ｃ₁−Ｃ₆−アルキル又はペルフルオロ化されたＣ₁−Ｃ₆−アルキル、特に好ましくは、α位に第三級炭素原子を有するＣ₄−Ｃ₆−アルキルである］のアシルオキシル化された有機化合物を、陽極置換により製造する方法を提供し、当該陽極置換は、
ａ）上記に定義されるような一般式Ｉａの有機化合物を提供する工程；
ｂ）陰極と陽極を有する電気化学セル中に、前記有機化合物と、上記に定義されるような一般式ＩＶのカルボン酸とを含む液体反応媒体を提供する工程；
ｃ）前記液体反応媒体を電気分解して、前記一般式Ｉｂのアシルオキシル化された有機化合物を形成する工程；
を含み、前記液体反応媒体は、イオン液体を少なくとも１０質量％の割合で更に含むことを特徴としている。 Thus, in one aspect, the invention provides a compound of general formula Ib

[Where:
X, A and R ⁶ are as defined above in the context of general formula Ia;
R ¹³ is C ₁ -C ₁₂ -alkyl or perfluorinated C ₁ -C ₁₂ -alkyl, preferably C ₁ -C ₆ -alkyl or perfluorinated C ₁ -C ₆ -alkyl, particularly preferably , Is a C ₄ -C ₆ -alkyl having a tertiary carbon atom at the α-position], and provides a method for producing an acyloxylated organic compound by anodic substitution,
a) providing an organic compound of general formula Ia as defined above;
b) providing a liquid reaction medium comprising, in an electrochemical cell having a cathode and an anode, the organic compound and a carboxylic acid of the general formula IV as defined above;
c) electrolyzing the liquid reaction medium to form the acyloxylated organic compound of the general formula Ib;
The liquid reaction medium further includes an ionic liquid in a proportion of at least 10% by mass.

  An overview of the structural possibilities of electrolytic cells that are suitable as electrochemical oxidation cells for the method of the present invention can be found in, for example, Pletcher & Walsh, Industrial Electrochemistry, 2nd Edition, 1990, London, pp. 60ff. Can be found from within.

  Electrochemical cells suitable for electrochemical oxidation are undivided cells and divided cells. A non-divided cell typically has only one electrolyte portion, and a split cell has two or more such electrolyte portions. The individual electrodes can be connected in parallel (monopolar) or in series (bipolar). In a suitable embodiment, the electrochemical cell used for electrochemical oxidation is a unipolar cell having one GDL anode and one cathode. In a more suitable embodiment, the electrochemical cell used for electrochemical oxidation is a cell having a bipolar electrode with a continuous stacked electrode.

  In a preferred embodiment, the electrochemical oxidation cell is a plate and frame cell. The plate and frame cells used in the method of the present invention preferably include at least one GDL electrode. This type of cell usually consists essentially of a rectangular electrode plate and a frame surrounding it. The frame can be made of a polymer material such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene fluoride, and PTFE. The electrode plate and the accompanying frame are joined to each other in an overlapping manner to form an assembly unit. By pressing together a plurality of such plate and frame units, a stack assembled according to the filter press construction style is obtained. Further frame units may be inserted into the stack, for example frame units for receiving the spacing gauge.

  In the process according to the invention, the anodic displacement by electrolysis of the liquid reaction medium can be carried out according to known methods, but the liquid reaction medium used contains an ionic liquid in a proportion of at least 10% by weight. And at least one hydrogen atom bonded to the carbon atom is substituted with a nucleophilic group.

  One or more anodes and one or more cathodes are disposed in the liquid reaction medium. According to the invention, at least the anode is preferably a GDL electrode. A potential (voltage) is established between the anode and the cathode, and an oxidation reaction (anodic substitution, that is, substitution of one or more hydrogen atoms bonded to carbon and a nucleophilic group bonded to carbon) occurs at the anode, and the cathode The reduction reaction (mainly hydrogen generation) occurs.

  The anodic displacement reaction is preferably carried out with a constant current, ie a constant voltage and a constant current flow. It is also possible to interrupt the current through a current cycle as described in US 6,267,865.

The current density applied in step c) is in a range known to those skilled in the art. The current density used in step c) is preferably in the range of 10~250mA / cm ^2, the range of 10 to 100 / cm ² is more preferable.

  The anodic displacement product can be separated from the reaction medium by conventional methods, preferably by distillation. Distillation of the reaction effluent can be carried out by conventional methods known to those skilled in the art. Suitable devices for fractionation by distillation include distillation columns such as plate columns, such as bubble caps, sieve plates, sieve trays, packing, internals, valves, side offtakes. ) Etc. can also be provided. A divided distillation column (a divided distillation column which may be provided with a side discharge port), a recirculation device and the like are particularly suitable. A combination of two or more distillation columns can be used for distillation. Further suitable devices are, for example, thin film evaporators, falling film evaporators, evaporators such as Sambay evaporators, and combinations thereof.

  In the method of the present invention, the use of a liquid reaction medium containing an ionic liquid in a proportion of at least 10% by weight is based on the selectivity of nucleophilic substitution, conversion rate of nucleophilic substitution reaction, current yield, space time yield, It has an advantageous effect on at least one of lifetime parameters and a wide range of feasibility parameters for organic compounds for anode replacement. This advantageous effect becomes more pronounced when GDL is additionally used as the anode. Without being limited to any theory, intermediates in nucleophilic substitution reactions of organic compounds, for example, cation radicals generated during the anodization process, are stabilized by the ionic liquid, and this stabilization is achieved when the ionic liquid is GDL. When used in combination with an anode, it is expected to be even better.

Examples The following examples are intended to further illustrate the present invention.

Comparative Example 1
In 100 ml of an undivided electrolytic cell, 6.5 g of toluene, 34.1 g of methanol, and 2.6 g of methyltributylammonium methyl sulfate (MTBS, 6% by mass) as a supporting electrolyte were added to a graphite anode (10 cm ^2). ) And a stainless steel cathode (10 cm ² ). The applied current density was 34 mA / cm ² . GC analysis showed 65% toluene conversion, 7% benzaldehyde dimethyl acetal selectivity and 2% current yield. The results of this example are summarized in Table 1.

Example 2
In 100 ml of an undivided electrolytic cell, 7.5 g of toluene, 17.0 g of methanol, and 25.5 g of methyltributylammonium methyl sulfate (MTBS, 51% by mass) as a supporting electrolyte were added to a graphite anode (10 cm ^2). ) And a stainless steel cathode (10 cm ² ). The applied current density was 34 mA / cm ² . GC analysis showed 88% toluene conversion, 32% benzaldehyde dimethyl acetal selectivity and 15% current yield. The results of this example are summarized in Table 1.

Example 3
In 100 ml of an undivided electrolytic cell, 13.1 g of toluene, 29.5 g of methanol, and 9.8 g of methyltributylammonium methylsulfate (MTBS, 12% by mass) as a supporting electrolyte, and GDL (10 cm ² ) as an anode ) And a stainless steel cathode (10 cm ² ). The current density was 34 mA / cm ² . GC analysis showed 87% toluene conversion, 22% benzaldehyde dimethyl acetal selectivity and 9% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black. The results of this example are summarized in Table 1.

Example 4
In 100 ml of an undivided electrolytic cell, 13.1 g of toluene, 29.5 g of methanol, and 9.8 g of methyltributylammonium methylsulfate (MTBS, 25 mass%) as a supporting electrolyte were used as GDL (10 cm ^2). ) And a stainless steel cathode (10 cm ² ). The current density was 34 mA / cm ² . GC analysis showed 89% toluene conversion, 29% benzaldehyde dimethyl acetal selectivity and 13% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black. The results of this example are summarized in Table 1.

Example 5
In 100 ml of an undivided electrolysis cell, 13.1 g of toluene, 29.5 g of methanol, and 9.8 g of methyltributylammonium methyl sulfate (MTBS, 51% by mass) as a supporting electrolyte were used as anodes and commercially available GDL ( H2315 IX11CX45 Freudenberg, 10 cm ² ) and a stainless steel cathode (10 cm ² ) and electrolysis at 8F. The current density was 34 mA / cm ² . GC analysis showed 98% toluene conversion, 45% benzaldehyde dimethyl acetal selectivity and 21% current yield. The results of this example are summarized in Table 1.

Example 6
In 100 ml of an undivided electrolytic cell, 7.9 g of toluene, 17.9 g of methanol, and 26.9 g of methyltributylammonium methylsulfate (MTBS, 51% by mass) as a supporting electrolyte were used as commercially available GDL ( Electrolysis was performed at 7F using a Siglacet GDL25BC SGL group, 10 cm ² ) and a stainless steel cathode (10 cm ² ). The current density was 34 mA / cm ² . GC analysis showed 96% toluene conversion, 45% benzaldehyde dimethyl acetal selectivity and 23% current yield. The results of this example are summarized in Table 1.

Example 7
In 100 ml of an undivided electrolytic cell, 7.6 g of toluene, 17.2 g of methanol, and 25.8 g of methyltributylammonium methylsulfate (MTBS, 51 mass%) as a supporting electrolyte were used as anodes with GDL (10 cm ² ) And a stainless steel cathode (10 cm ² ). The current density was 34 mA / cm ² . GC analysis showed 97% toluene conversion, 48% benzaldehyde dimethyl acetal selectivity and 25% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black. The results of this example are summarized in Table 1.

Example 8
In 100 ml of an undivided electrolytic cell, 8.1 g of toluene, 18.3 g of methanol, and 27.4 g of methyltributylammonium methylsulfate (MTBS, 51% by mass) as a supporting electrolyte were used as GDL (10 cm ^2). ) And a stainless steel cathode (10 cm ² ). The current density was 65 mA / cm ² . GC analysis showed 94% toluene conversion, 49% benzaldehyde dimethyl acetal selectivity and 27% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black. The results of this example are summarized in Table 1.

Example 9
In 100 ml of an undivided electrolytic cell, 4.9 g of toluene, 10.9 g of methanol, and 36.8 g of methyltributylammonium methyl sulfate (MTBS, 70% by mass) as a supporting electrolyte were added to a graphite anode (10 cm ^2). ) And a stainless steel cathode (10 cm ² ). The applied current density was 34 mA / cm ² . GC analysis showed 81% toluene conversion, 30% benzaldehyde dimethyl acetal selectivity and 15% current yield. The results of this example are summarized in Table 1.

Example 10
In 100 ml of an undivided electrolytic cell, 5.2 g of toluene, 11.7 g of methanol, and 39.4 g of methyltributylammonium methyl sulfate (MTBS, 70% by mass) as a supporting electrolyte were used as GDL (10 cm ² ) as an anode. ) And a stainless steel cathode (10 cm ² ). The current density was 34 mA / cm ² . GC analysis showed 93% toluene conversion, 50% benzaldehyde dimethyl acetal selectivity and 28% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black. The results of this example are summarized in Table 1.

Example 11
In 100 ml of an undivided electrolytic cell, 5.9 g of toluene, 13.2 g of methanol, and 1-ethyl-3-methyl-imidazolium bis (trifluoromethylsulfonyl) imide (EMimid-TFSI, 70 mass) as a supporting electrolyte %) and 44.4 g, and electrolysis 6F with the GDL (cathode 10 cm ²⁾ and stainless steel (10 cm ²⁾ as an anode. The applied current density was 34 mA / cm ² . GC analysis showed 98% toluene conversion, 50% benzaldehyde dimethyl acetal selectivity and 30% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black. The results of this example are summarized in Table 1.

Example 12
In 100 ml of an undivided electrolytic cell, 5.6 g of toluene, 12.7 g of methanol, and 42.8 g of methyltributylammonium bis (trifluoromethylsulfonyl) imide (MTB-TFSI, 70% by mass) as a supporting electrolyte. and electrolysis 6F with the GDL cathode (10 cm ²⁾ and stainless steel (10 cm ²⁾ as an anode. The applied current density was 34 mA / cm ² . GC analysis showed 98% toluene conversion, 50% benzaldehyde dimethyl acetal selectivity and 32% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black. The results of this example are summarized in Table 1.

Example 13
In 100 ml of an undivided electrolytic cell, 6.0 g of toluene, 13.5 g of methanol, and 45.4 g of methyltributylammonium bis (trifluoromethylsulfonyl) imide (MTB-TFSI, 70% by mass) as a supporting electrolyte. It was electrolyzed at 5.5F with the GDL cathode (10 cm ²⁾ and stainless steel (10 cm ²⁾ as an anode. The applied current density was 60 mA / cm ² . GC analysis showed 95% toluene conversion, 54% benzaldehyde dimethyl acetal selectivity and 35% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black. The results of this example are summarized in Table 1.

Comparative Example 14
In 100 ml of an undivided electrolytic cell, 6.7 g of benzaldehyde dimethyl acetal, 37.6 g of methanol, 0.45 g of sodium bromide (1% by mass) as a mediator / supporting electrolyte, and graphite (10 cm ² ) as an anode And a stainless steel cathode (10 cm ² ) at 2.5 F. The applied current density was 34 mA / cm ² . GC analysis showed 18% benzaldehyde dimethyl acetal conversion, 49% benzoic acid ortho-ester selectivity and 7% current yield.

Comparative Example 15
In 100 ml of an undivided electrolytic cell, 6.1 g of benzaldehyde dimethyl acetal, 33.9 g of methanol, 0.82 g of tetrabutylammonium bromide (2% by mass) as a mediator / supporting electrolyte, and graphite (10 cm ² ) as an anode ) And a stainless steel cathode (10 cm ² ) at 2.5 F. The applied current density was 34 mA / cm ² . GC analysis showed 24% benzaldehyde dimethyl acetal conversion, 59% benzoic acid ortho-ester selectivity and 11% current yield.

Example 16
In 100 ml of an undivided electrolytic cell, 5.2 g of benzaldehyde dimethyl acetal, 21.2 g of methanol, 23.1 g of methyltributylammonium methylsulfate (MTBS, 45% by mass), tetrabutylammonium bromide (4 a mass%) 2.2 g, and electrolysis 5F by using the GDL (cathode 10 cm ²⁾ and stainless steel (10 cm ²⁾ as an anode. The applied current density was 34 mA / cm ² . GC analysis showed 72% benzaldehyde dimethyl acetal conversion, 68% benzoic acid ortho-ester selectivity and 20% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black.

Example 17
In 100 ml of an undivided electrolytic cell, 4.9 g of benzaldehyde dimethyl acetal, 20.2 g of methanol, 21.8 g of methyltributylammonium methylsulfate (MTBS, 42% by mass), and tetrabutylammonium bromide (10 a mass%) 5.1 g, and electrolysis 5F by using the GDL (cathode 10 cm ²⁾ and stainless steel (10 cm ²⁾ as an anode. The applied current density was 34 mA / cm ² . GC analysis showed 31% benzaldehyde dimethyl acetal conversion, 83% benzoic acid ortho-ester selectivity and 10% current yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black.

Example 18
In 100 ml of an undivided electrolytic cell, 5.6 g of ethylene carbonate, 27 g of pivalic acid, and 22.3 g of tetraoctylammonium bis (trifluoromethylsulfonyl) imide (41% by mass) as a supporting electrolyte were used as anodes with GDL. Electrolysis was performed at 4.7 F using (10 cm ² ) and a stainless steel cathode (10 cm ² ). The applied current density was 10 mA / cm ² . NMR and GC analysis showed 67% ethylene carbonate conversion and 18% 4- (tert-butyl) carbonyloxy-1,3-dioxolan-2-one yield. The GDL electrode was manufactured according to US 6,103,077 using carbon black.

Claims (19)

a) providing an organic compound having at least one hydrogen atom bonded to a carbon atom;
b) providing a liquid reaction medium comprising the organic compound and a nucleophile in an electrochemical cell having a cathode and an anode;
c) electrolyzing the liquid reaction medium to replace at least some of the hydrogen atoms and nucleophilic groups of the nucleophile;
The method according to claim 1, wherein the liquid reaction medium further comprises an ionic liquid in a proportion of at least 10% by mass.   The method of claim 1, wherein the anode is a gas diffusion layer electrode.   The method according to claim 2, wherein the gas diffusion layer electrode includes a base material and a microporous layer containing carbon particles as a main component.   The method according to claim 2, wherein the gas diffusion layer electrode includes a substrate and a microporous layer containing carbon black as a main component.   The method according to claim 1, wherein the ionic liquid contains an organic cation having an ammonium group. The organic compound is
(I) an alkane or cycloalkane having at least one hydrogen atom directly bonded to a tertiary carbon atom,
(Ii) alkenes or cycloalkenes or corresponding dienes having at least one hydrogen atom bonded directly to an allylic carbon atom,
(Iii) an alkylarene having at least one hydrogen atom directly bonded to a carbon atom located at the α-position relative to the arene moiety;
(Iv) an amide having at least one hydrogen atom directly bonded to a carbon atom located in the α-position relative to the nitrogen atom, and (v) directly bonded to a carbon atom located in the α-position relative to the oxygen atom. 6. The process as claimed in claim 1, wherein the process is selected from the group consisting of ethers, esters, carbonates or acetals having at least one hydrogen atom. The organic compound is of formula I

[Where:
X is O, N—R ³ or CR ⁴ R ⁵ ;
R ¹ is selected from C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, formyl, C ₁ -C ₆ -alkylcarbonyl and C ₁ -C ₆ -alkyloxycarbonyl And
When X is a CR ⁴ R ⁵ group, R ¹ may be C ₁ -C ₆ -alkoxy,
When X is a N—R ³ or CR ⁴ R ⁵ group, R ¹ may be C ₁ -C ₆ -alkylcarbonyloxy;
R ² is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl-C ₁ -C ₆ -alkyl, C ₃ -C ₁₂ - is selected from aryl, - cycloalkyl and C ₆ -C ₁₀
R ³ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, formyl, C ₁ -C ₆ -alkylcarbonyl and C ₁ -C ₆ -alkyloxycarbonyl Selected from
Are R ⁴ and R ⁵ independently selected from hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, and C ₁ -C ₆ -alkoxy? Or
R ¹ and R ² they are attached X- (C = O) together with the -O group, to form a heterocyclo ring having 5 to 7 membered, said heterocyclo ring, O, S, NR may further comprise at least one heteroatom or a group having a heteroatom selected from ^c or C═O and R ^c selected from hydrogen, alkyl, cycloalkyl and aryl,
Or
Wherein X is a CR ⁴ R ⁵ group, and R ¹ and R ⁴ together with the carbon atom to which they are attached form a 3-7 membered carbocyclo ring. Item 6. The method according to any one of Items 1 to 5. Said organic compound is of formula Ia

[Where:
X is O, CH ₂ or NR ³ , R ³ is C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkylcarbonyl,
A _{is, -CH 2 -, - CH 2} -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CHR 7 -, - CHR 7 -CH 2 -, - CH 2 -CHR 7 -, - CHR ^{_{7 -CH 2 -CH 2 -, -}} CH 2 -CHR 7 -CH 2 - and -CH ₂ -CH ₂ -CHR ⁷ - an alkylene group selected from, R ⁷ is, C ₁ -C ₆ - Alkyl,
R ⁶ is hydrogen or C ₁ -C ₆ - which is a compound of a is] alkyl, any one process of claim 1 to 5. The organic compound is of formula II
Z-CHR ⁸ R ⁹ (II)
[Where:
Z is selected from C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl, C ₁ -C ₆ -allyl, —NR ¹⁰ R ¹¹ group and C ₁ -C ₆ -alkoxy;
R ⁸ is selected from hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl,
When Z is C ₆ -C ₁₀ -aryl or C ₁ -C ₆ -allyl, R ⁸ may be C ₁ -C ₆ -alkoxy;
R ⁹ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ - aryl, C ₆ -C ₁₀ - aryl -C ₁ -C ₆ - alkyl and C ₃ -C ₁₂ - is selected from cycloalkyl, or,
R ⁸ and R ⁹ together form C ₄ -C ₇ -alkylene or C ₄ -C ₇ -alkenylene;
R ¹⁰ and R ¹¹ are independently selected from hydrogen, C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl and C ₁ -C ₆ -alkylcarbonyl Or
Where
Z, R ⁸ and R ⁹ are independently, C ₁ -C ₆ - which is a compound of alkyl as, any one process of claim 1 to 5.   The nucleophilic agent is water, alcohol, carboxylic acid, nitrous acid or salt thereof, nitric acid or salt thereof, hydrazoic acid or salt thereof, isocyanic acid or salt thereof, isothiocyanic acid or salt thereof, sulfonic acid, isoselenocyanocyanate. The acid or salt thereof, hydrogen cyanide or salt thereof, hydrogen chloride or salt thereof, hydrogen bromide or salt thereof, and hydrogen iodide or salt thereof, and any one of claims 1 to 9 the method of. The nucleophile is
Formula III
R ¹² OH (III)
Alcohols of formula IV
R ¹³ COOH (IV)
Selected from the group consisting of:
R ¹² and R ¹³ are, C ₁ -C ₁₂ - alkyl or perfluorinated C ₁ -C ₁₂ - alkyl, any one process of claim 1 to 9.   10. The method according to any one of claims 1 to 9, wherein a fluorinating agent is excluded as a nucleophile.   13. A method according to any one of claims 1 to 12, wherein the liquid reaction medium further comprises an additive selected from the group consisting of bromide salts and iodide salts.   The method according to claim 1, wherein the electrochemical cell is an undivided cell.   15. A method according to any one of the preceding claims, wherein the cathode is selected from the group consisting of felt materials such as Pt, Pb, Ni, graphite, coal or graphite felt, stainless steel and GDL electrodes. Formula V
Y-CH ₂ R ¹⁴ (V)
Starting from organic compounds of general formula VI
Y-C (OR ¹² ) ₂ R ¹⁴ (VI)
A method for producing an acetal by anodic substitution,
Y is selected from C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl, C ₁ -C ₆ -allyl and —NR ¹⁰ R ¹¹ groups;
R ¹² is, C ₁ -C ₁₂ - alkyl or perfluorinated C ₁ -C ₁₂ - alkyl,
R ¹⁴ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ - aryl, substituted C ₆ -C ₁₀ - aryl and C ₃ -C ₁₂ - is selected from cycloalkyl,
R ¹⁰ and R ¹¹ are independently selected from hydrogen, C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl and C ₁ -C ₆ -alkylcarbonyl And
The anode replacement is
a) providing an organic compound of general formula V as defined above;
b) providing in a electrochemical cell having a cathode and an anode a liquid reaction medium comprising said organic compound and an alcohol of general formula III as described in claim 11;
c) electrolyzing the liquid reaction medium to form an acetal of the general formula VI;
Including
Said method, wherein said liquid reaction medium further comprises an ionic liquid in a proportion of at least 10% by weight. Formula V
Y-CH ₂ R ¹⁴ (V)
Starting from organic compounds of general formula VIa
Y-COR ¹⁴ (VIa)
A method for producing an aldehyde or ketone by anodic substitution,
Y is selected from C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl, C ₁ -C ₆ -allyl and —NR ¹⁰ R ¹¹ groups;
R ¹² is C ₁ -C ₁₂ -alkyl or perfluorinated C ₁ -C ₁₂ -alkyl;
R ¹⁴ is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl-C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ - aryl, substituted C ₆ -C ₁₀ - aryl and C ₃ -C ₁₂ - is selected from cycloalkyl,
R ¹⁰ and R ¹¹ are independently selected from hydrogen, C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl, substituted C ₆ -C ₁₀ -aryl and C ₁ -C ₆ -alkylcarbonyl And
The anode replacement is
a) providing an organic compound of general formula V as defined above;
b) providing in a electrochemical cell having a cathode and an anode a liquid reaction medium comprising said organic compound and an alcohol of general formula III as described in claim 11;
c) electrolyzing the liquid reaction medium to form an acetal of the general formula VI;
d) hydrolyzing the acetal of general formula VI to form the aldehyde or ketone of general formula VIa;
Including
Said method, wherein said liquid reaction medium further comprises an ionic liquid in a proportion of at least 10% by weight. Formula VII
Y-CR ¹⁵ ₂ H (VII)
Starting from organic compounds of general formula VIII
Y-CR ¹⁵ ₂ (OR ¹² ) (VIII)
A process for producing an ortho-ester of
Y is defined as above,
R ¹² is C ₁ -C ₁₂ -alkyl or perfluorinated C ₁ -C ₁₂ -alkyl;
R ¹⁵ is C ₁ -C ₁₂ -alkoxy;
The anode replacement is
a) providing an organic compound of the general formula VII as defined above;
b) In a electrochemical cell having a cathode and an anode, a liquid reaction medium comprising the organic compound, a bromide salt or an iodide salt and an alcohol of the general formula III as described in claim 11 is provided. Process;
c) electrolyzing the liquid reaction medium to form the acetal of the general formula VII;
Including
Said method, wherein said liquid reaction medium further comprises an ionic liquid in a proportion of at least 10% by weight. Starting from an organic compound of the general formula Ia as described in claim 8

A method for producing an acyloxylated organic compound of
X, A and R ⁶ are as described in the definition of general formula Ia in claim 8;
R ¹³ is, C ₁ -C ₁₂ - alkyl or perfluorinated C ₁ -C ₁₂ - alkyl,
The anode replacement is
a) providing an organic compound of general formula Ia as described in claim 8;
b) providing a liquid reaction medium comprising, in an electrochemical cell having a cathode and an anode, the organic compound and a carboxylic acid of the general formula IV as described in claim 11;
c) electrolyzing the liquid reaction medium to form the acyloxylated organic compound of the general formula Ib;
Including
Said method, wherein said liquid reaction medium further comprises an ionic liquid in a proportion of at least 10% by weight.