TW200800881A - An electrochemical process to prepare a halogenated carbonyl group-containing compound - Google Patents

Abstract

The present invention provides a process to prepare a halogenated carbonyl group-containing compound by electrochemically reacting the corresponding carbonyl group-containing compound with a hydrogen halide H-X, an organic halide R'-X and/or a halide salt Mn+-Xn- under substantially water-free conditions, wherein X is a chlorine, bromine or iodine atom, R' is an alkyl or aryl group that may be linear or branched, optionally containing one or more heteroatoms such as oxygen, nitrogen, chloride, bromide, fluoride or iodide of which the halogen atom X can be electrochemically split off, Mn+ is a quaternary ammonium, alkaline earth metal, alkali metal or metal cation, and n is an integer of 1 to 5, depending on the valency of the metal cation Mn+.

Description

200800881 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel electrochemical process for preparing a carbonyl-containing compound such as a carboxylic acid. In a particular embodiment, it is a process for the chlorination of acetic acid to produce monochloroacetic acid. [Prior Art] In the industry, monochloroacetic acid is prepared by reacting acetic acid with chlorine. This process for the preparation of monochloroacetic acid is well known and is usually carried out under anhydrous conditions in a mixture of liquid acetic acid (HAc) and chlorine in a reactor. Many compounds are available to form such anhydrous conditions. If acetic anhydride is used, it can be immediately converted to ethyl chloroform with hydrogen acid, which is the catalyst for this process. This method is usually carried out at a pressure of 1 to 6 bai*A and a temperature of 80 to 180 T:. In the reactor, monochloroacetic acid (MCA) and gas HC1 and by-products are formed, wherein examples of by-products are dichloroacetic acid (DCA) and trichloroacetic acid (TCA). The reaction product mixture containing MCA has passed through the reaction. After the catalyst and catalyst recovery zone, DCA is present in significant amounts (typically about 3-10%). The MCA/DCA containing product mixture is then directed to a unit to reduce the amount of DCA in the MCA. This can be carried out by physical separation (such as melt crystallization) or by chemical conversion (such as reduction of DCA by hydrogen in the presence of a hydrogenation catalyst (e.g., a metal-based catalyst). However, this catalyst not only restores the DCA, but also restores the MCA to a certain extent, which is of course undesirable. Moreover, the reduction unit and its operation are expensive and thus increase the manufacturing cost of the MCA end product. 12I033.doc 200800881 The low boiling component is then removed from the MCA by conventional vacuum distillation. The method of preparing MCA by electrochemical method has been developed by Α·Youtz et al.

Polarization 〇f the Chlorine Electrode by Organic mpounds is disclosed in J. 6W, 1924, 46, 549. The method encompasses reacting 7 % acetic acid in an aqueous solution with hydrochloric acid to produce chloroacetic acid. The electrochemical process for preparing a halogenated carboxylic acid (derivative) in a water content of 3% has the disadvantage that only a small amount of the (mono)halogenated carboxylic acid is formed. In addition, the main product of electrolysis in the =aqueous chloride environment is usually gas, which is not a problem because it is an additional waste stream and in addition the combination of chlorine and hydrogen may make the reaction off-gas mixture susceptible to explosion.

[Summary of the Invention] Ben! One of the objectives of X is to provide a method of preparing, deciding, containing a plurality of radicals by using inexpensive and commercially available starting impurities' without post-treatment of the simultaneously produced compounds. Another object of the present invention is to provide a process for producing a carbonylated compound containing a single compound. The compound has less di-, tri- or polyhalogenated by-product content relative to the above-described industrial process. The same is true of the present invention - the object of the present invention is that it can be easily integrated into existing hardware used in the case of the above-described industrial method of the prior art without requiring strict physical conditions. Further, in order to provide a method for producing a compound containing a group, the compound is selectively halogenated at a sub-portion (i.e., a carbon atom adjacent to «). Further, it is intended to provide, for example, a product which has an improved yield compared to the aqueous electrochemical method of Υ_ et al., and which provides a by-product of good value, 121033.doc 200800881. The present invention now provides a process for the preparation of a halogenated carbonyl-containing compound by electrochemically reacting the corresponding carbonyl-containing compound with a hydrogen halide HX, an organic halide R'-X and/or a tooth salt under substantially anhydrous conditions. Where X is a chlorine, bromine or iodine atom, and R' may be a linear or branched alkyl or aryl group, optionally containing one of oxygen, nitrogen, chlorine, bromine, fluorine or iodine. Or a hetero atom in which the halogen atom X can be electrochemically separated, Mn+ is a quaternary ammonium, an alkaline earth metal, an alkali metal or a metal cation, and η is an integer of 1 to 5 depending on the valence of the metal ion Μη+ . The perhydrated anhydrous condition is defined as having less than 1 weight/in the reaction mixture. Preferably, it is less than 〇·1% by weight, more preferably about zero water; these conditions are preferably completely anhydrous, which can be achieved when the reaction mixture contains a compound which is used as a water scavenger. Seven people are surprised that _X is only selected from the group of gas, bromine and iodine because it is not fluorinated by the method of the present invention. In this technique, see • (for example) Ρ·Sartori, Ν·Ignat, ev,"The Actual _e 〇f surgery ledge about mechanism of electrochemical fluorination anhydrous hydrogen fluoride (Simons process)% Journal • 〇f Fluorine Chemistry 87 (1998), pp. 57_i62, 矣 Reveals • The method of fluorination of dry organic compounds in counties; however, normal reactions such as these produce polyfluorination reactions' and do not produce specific carbon fluorination. When using the method of the present invention, no halogen gas (such as chlorine) is required, but hydrogenated hydrogen, organic dentate or halogen salt is used as the &<RTIgt;</RTI> And cheap. Process of the Invention 121033.doc 200800881 A halogenated containing group-containing compound and hydrogen are produced as reaction products. This is also true of any unreacted compound containing a compound that is readily recoverable and unreacted by the source. The by-product hydrogen formed can be readily separated and can be used, for example, as a source or starting compound for other purposes, and thus exhibits commercial value. ", 7 people L ^ mantle, found that only a very small amount of dihalogenated and / or more halogenated fluorenyl compounds; usually in the halogenated carboxylic acid, the amount of dihalogenated Wei acid is lower than 〇. 3% by weight, and the amount of the trihalogenated or higher halogenated acid (even when formed) is lower than the limit of the energy value (ie, less than 5 〇卯 (4). Because the reaction by-product is hydrogen (ie, Bubbles, so the reaction mixture remains well mixed and does not require agitation, which is also beneficial. In the process of the invention, a current yield of 80% of the cleavage of the singly carboxylic acid (derivative) has been achieved. Higher current yields. In contrast, electrochemical chlorination of acetic acid in aqueous environments produces low current yields typically below 1%. Current production (also known as current efficiency) is referenced by Bard_stratman,

Encyclopedia 〇f Electrochemistry, Organic Electrochem. > Volume 8, m, page is described. In short, current efficiency or current production means the fraction of the battery current used to form the product or the fraction of the transferred charge (integrated over time). Surprisingly, it has been found that in the process of the invention it is also possible to efficiently convert a dihalogenated and/or higher halogenated carbonyl containing compound to a monohalogenated carbonyl containing compound. Thus, in one embodiment, the starting material may be a mixture of a carbonyl-containing compound (RX) comprising at least a bidentate and/or higher halogenated compound and a carbonyl-containing compound not halogenated 121033.doc 200800881, wherein The amount of the carbonyl-containing compound which is and/or more halogenated is preferably at most the molar amount of the carbonyl-containing compound which is not halogenated. It has been found that the use of this starting mixture still produces a reaction product comprising a predominantly monohalogenated containing group-containing compound, or in other words, the amount of carbonyl-containing compound which is produced by dihalogenation and/or higher halogenation is extremely low. This is due to the fact that the dihalogenated and/or higher halogenated carbonyl containing compound electrochemically reacts at the cathode to form hydrogen halide in situ.

In two documents, that is, LN Nekrasov et al., "Effect of small amounts of tetramethyl- and tetraethylammonium ions on electroreduction kinetics of certain organic compounds in solutions of tetrabutylammonium salts 1% Elektrokkimiya 5 Vol. 24, No. 4, Page 560-563, 1988 and A. Inesi, L. Rampazzo "Electrochemical reduction of halogen containing compounds at a mercury cathode: chloroacetic, dichloroacetic acids and corresponding ethylesters in dimethylformamide,!? Electroanalytical Chemistry and Interfacial Elelctrochemistry^ 44 (1973 ), pp. 25-35, discloses that tris-acetic acid can be reduced to di-glycolic acid by using an electrochemical method, but it is not disclosed or suggested that the compound can be used as a halogen source containing a carbonyl compound (i.e., Used as a defined compound R'-X) to prepare a monohalogenated carbonyl-containing compound. [Embodiment] Accordingly, in one embodiment of the present invention, a method is provided wherein the organic halide R|-X is dihalogenated. And/or higher halogenated carbonyl containing compounds Or in other words, a method for preparing a halogenated carbonyl-containing compound, I21033.doc -10- 200800881 β method hunting by substituting a corresponding group-containing compound under anhydrous conditions on a real f: halogenation and/or The electrochemical grouping of a high-n-containing compound containing a compound (as appropriate, HX, another organic halide, and/or a tooth salt) can be achieved, wherein hydrazine is a chlorine, bromine or argon atom, and r, alkane Base or aromatic, Gan.. ^ ^ ^ m : square base may optionally contain one or more heteroatoms, such as

"f chlorine' odor, fluorine or iodine, the bovine halogen atom X can be electrochemically knives away from ' Μ into four grades, soil test metals, metal or metal cations, and the price of the metal cations The integer of (1). The method of the present invention can also be used as the H in the conventional method for preparing a monounzine containing group-containing compound by the reaction of a read-based compound (tetracycline). The method of the present invention can be used to treat a mother liquor produced by separating a monolithic lysine (derivative) from a reaction mixture comprising a monohalogenated and a sulfonated and/or more deuterated k (he organism), the mother liquor then containing the remaining A mixture of a single shouldered acid (street organism) and a relatively large amount of a slow acid (or a derivative thereof) which is oxidized and/or more painfully. Separation methods include conventional separation methods available to those skilled in the art, such as distillation, extraction, and crystallization, with crystallization being optimal. This aspect of the invention provides a method of preparing a sequestered compound containing a compound by first chemically reacting a compound containing a group with a chlorine, moth or moth molecule and then according to the electrochemical method disclosed above The electrochemical treatment of the reaction mixture is achieved, and the present invention provides a method wherein the starting mixture is such that the monodentate containing compound and the monodentate containing compound are bidentate and/or The mother liquor obtained upon separation of the higher-toothed reaction mixture containing the group of compounds 121033.doc 200800881. In the case of a mixture containing a certain group of compounds and a corresponding mixture of a plurality of compounds containing a group of compounds, (4) ~ more two-toothed and / or higher-yield containing a μ / '# reaction as a dihalogenation, ^ The reaction of the tick-based compound with the corresponding carbonyl-containing character produces a mono-methane-containing compound. An embodiment comprising a conventional method, an electrochemical method which is inconspicuous and has an important thermal invention; a person: a product of a conventional method (ie, a functional hydrogen and a compound containing a few groups) The base 'and: the second halogenated carbonyl containing meridian, the mixture of the chemical and/or the compound is the starting material of the electrochemical step. Therefore, there is no need to process the product stream of the conventional method. '·Or, the product of the conventional method~ can be directly used as the starting material stream in the electrochemical step. Suitably, 'higher drawing means up to 10, and preferably 3 to 6 chlorine, /odor And/or an iodine group is present in the carbonyl-containing compound. This (4) further provides a device for carrying out the above method. In this aspect, the device is provided, and the device comprises an outlet (7) and, depending on the situation, the outlet (7), 3) and (4) a chemical reactor (4) connected to the f-chemical reactor (8), wherein the reactor (B) is connected to the physical separation unit (C) via a 屮〇/〇, 志 J outlet (9). The apparatus is illustrated in Figure 1. The reactor (A) can be a reaction valley of a suitable material (e.g., glass crucible steel) (example) , heating and/or cooling and/or isolation. The chemical reactor preferably contains internal components such as mechanical agitators, heat exchanger tubes, inlet tubes (eg, for feedstock and recycle streams), and/or contains Inductors (such as 'degree sensor, pressure sensor, liquid level sensor). Chemical reaction - (A) can be used to convert halogen gas into halogen atom from] 21033.doc • 12, 200800881 illuminating members, such as uv lamps. See Figure 1 for more details. 'The bismuth compound, the cleavage compound, the catalyst as appropriate and the electrolyte as appropriate, respectively, via the inlet (1), (2 (3) and

(4) supplied to the chemical reactor (VIII), two or more of which may be combined into one inlet to react with the intermediate product, and the inter-product is supplied to the electrochemical reactor (Β) via the outlet (7). It can be formed in the chemical reaction (Α) and reacts with the chemical! The (Α) separated gas component is also introduced partially or completely into the electrochemical reactor (Β) via the outlet (4), in which case the outlet (6) can be combined with the outlet (5) to form an outlet. More or even all of the group-containing compounds, catalysts and electrolytes may be fed into the electrochemical reactor (8) from the inlets (7), (7) and (4), respectively, and two or more of the inlets may be combined into one inlet. . In one embodiment, the electrochemical reactor (Β) may be provided with an additional inlet stream (7) containing a halide (gas or liquid).电化学 An electrochemical reactor (Β) is a device containing at least one anode and at least one cathode of any suitable material as described above and preferably placed therein with a suitable geometry (such as a parallel plate or concentric cylinder, filled) A container for the anode and cathode of a bed or a body bed. In a more preferred embodiment, the electrochemical reactor contains one or more battery separators (such as a vibrating membrane or membrane). In another preferred embodiment, the electrochemical reactor (Β) is a reactor containing parallel electrodes in a vessel with or without internal or external fluid recirculation. The anode and cathode are connected to a direct current source that supplies current to the electrodes. The electrodes can be connected to a power supply in a unipolar configuration or in a bipolar configuration. In a preferred embodiment, the electrochemical reactor (B) simultaneously halogenates 121033.doe -13 - 200800881 starting material at the anode and denitatizes the diphthonated and higher-toothed compound at the cathode. In the example of the formation of the monomeric compound m, hydrogen is separated from the reaction enthalpy via the outlet w at the cathode at the electrochemical reaction. The substantially reduced dihalogenated and/or higher halogenated product is supplied from the electrochemical reactor (Β) to the physical separation unit (c) via the outlet (9). The hydrogen halide and other, and the damage, and the two formed in the chemical reaction ||' (A) and/or the electrochemical reactor (B) are separated from the product by the outlet (11), and may be exported via the outlet (as appropriate) 10) Return to the chemical reactor (A) and/or the electrochemical reactor (B). In addition, the electrolyte can be fed into the chemical reactor via the inlet (4): (A) and/or electrochemical reactor (B), which can separate the reaction product and the reactants in the physical separation unit (c) and Depending on the situation, it may be returned to reactors A and B via an outlet (1). The physical separation unit (C) is a device which may comprise one or more distillation columns, extraction columns, absorption columns or combinations thereof, the device being adapted to be passed through an outlet (9) The electrochemical reactor product entering unit C is separated into a deuterated product stream containing the predominantly monohalogenated and dihalogenated carbonyl groups exiting the apparatus of the invention via outlet (11). derivative. In another embodiment, the apparatus comprises an additional separation unit (D) for separating the monohalogenated compound from the corresponding dihalogenated and higher halogenated compound. This device is illustrated in Figure 2. Referring in more detail to Figure 2 'in the apparatus of this embodiment, the product from the chemical reactor (Α) is introduced via an outlet (5) to the physical separation unit (C) as described above to form a chemical reactor The electrolyte and other components or products in the crucible are separated from the monodentate via the outlet (12) to the separation unit, a mixture of 121033.doc -14-200800881 monohalogenated and/or a more halogenated carbonyl product. . The separation unit u comprises a separation member capable of separating the monohalogenated compound from the corresponding bidentate compound which is more halogenated. These separation members can be = steamed towers, crystallization units, extraction units or any combination of such members to provide the desired separation. The rinsing agent N produces a purified monohalogenated product separated by an outlet (14) and a substantially enriched dihalogenated and/or higher halogenated product stream, which is introduced into the chemistry via an outlet (9) In reactor (B). Tingjiang Power In the apparatus of the embodiment shown in Fig. 2, the substantially enriched mono-product obtained from the electrochemical reactor (Β) can be introduced into the chemical reactor (4) via the outlet (1). The stream containing the electrolyte and other components may optionally be passed from the physical separation unit to the human electrochemical reactor (8) and/or the chemical reactor (VIII). Depending on the situation, it is also possible to use a population (7) and an inlet (7) to separate a stream containing a halide (gas or liquid) and a substance containing a person with a county character into a human electrochemical unit (Β), where σ(7) and population (7) can be combined into one ° ° In an electrochemical reactor (Β), hydrogen can be produced at the cathode and separated from the reactor via an outlet (8). In a preferred embodiment, the process of the invention is carried out in the substantial absence of solvent. "Substantially solvent free" means that at most 5 are present in the reaction mixture. /. Solvent. The solvent is intended to cover at least any substance that is soluble in the starting material of the reaction but does not include the reactants/products. In the process of the invention, the reaction mixture preferably contains less than 2% solvent. The solvent of about (4) is optimally present. The purifying reaction occurring in the method of the present invention can be understood as: 121033.doc •15- 200800881 HX + R-COY XR-coy + ^ R'-X + R-COY ...> x_R_c〇Y + r,h Or MXn -fn R-COOH (XRC〇〇)nM -f nH2 " The compound containing R-COY or R-COOH to be A can be any compound containing α-carbon• hydrogen atoms' preferably at the reaction temperature The bottom is liquid. The carbonyl-containing compound R-C〇Y may be a warp, a sputum, a tickic acid, a tartile liver or a sputum-based tooth. R-(3)Y and R_C00H preferably have a "compound, which" is a 9-, nitrogen- or aryl group having a-nitrogen group and may be linear, cyclic or branched, optionally as it is - or a plurality of heteroatoms such as oxygen, nitrogen, gas, desert or iodine, and γ is hydrogen, a radical, a tooth atom or a group R" or 〇c〇R", wherein each is independently a hydrogen atom or an alkyl group, an alkylene group Base or aryl. More preferably, γ is a hydroxyl group, a halogen atom, a group R" or OCOR", R in the oxime, is Ci_Ci. A thiol or a stretching group and R is a CVC26 alkyl group or a Ci_C26 stretching group. It is an unsubstituted CVC26 carboxylic acid, more preferably acetic acid, propionic acid or a fatty acid, and most preferably acetic acid. A fatty acid is defined as a carboxylic acid having a hydrocarbon group containing hydrazine to "one carbon atom, preferably from 22 carbon atoms". It can be saturated or unsaturated, linear or branched. Falsely known fatty acids from natural fats and oils have at least 8 carbon atoms. Preferred fatty acids in the present invention are unbranched humic acids and are more preferably A (e.g., CJW·ffa ookiChemi _ physics, • 1989 edition, group D_22). The compound is a vapor, a desert or a barrier, which is more preferably a chloride or a bromide, most preferably a chloride. The organic compound R'_X can be any compound which can be deuterated by an electrochemical step, for example Lund, Hammerich, 〇rg, C, C, Heart, 121033.doe -16- 200800881 4th edition, Chapter 8, ''Halogenated organic compounds' (Marcel Dekker, 2001). -X is preferably a halogenated hydrocarbon compound which may contain other substituents (e.g., nitrogen or oxygen). RT-X is preferably a dihalogenated and/or more halogenated carbonyl containing compound. Halogen salt Mn+-Xn Preferably, the ruthenium is a soil test metal, a metal or a metal cation, and the ruthenium is preferably a Na, ruthenium, Li, Mg, Ca, Ba cation, and more preferably a metal cation, preferably a lithium, sodium or potassium cation. a salt of ii. In a more preferred embodiment, the reaction mixture comprises substantially only reactants, And the auxiliaries, that is to say more than 5% by weight of the reaction mixture are starting materials, products and auxiliaries, and preferably comprise more than 99% by weight of the reaction mixture. The auxiliaries can be defined as being functionally present in the invention. Reagents in the process, such as catalysts and supporting electrolytes. In principle, as long as sufficient current can pass through the fluid under the processing conditions, no supporting electrolyte is required in the process. In a preferred embodiment, the supporting electrolyte is present in the reaction mixture. The electrolyte is a mixture of non-aqueous compounds which are sufficiently soluble and provide sufficient electrical conductivity in the applied reaction mixture, can be easily separated and recovered, and can sufficiently stably resist oxidation and reduction. Examples can be, for example, F. Beck, Elektroorganische Chemie, Verlag Chemie GmbH? Weinheim, 1974, Chapter 3.3 '104-110 or 〇.?161:(:1161*,^[77/7^(^ 1^*^ in Electrode Processes, The Electrochemical Consultancy, Alresford Press Ltd., 1991, Chapter 2.3, pages 57-72, any combination of ions given, and may be included Including ions, such as ΟΗ_, Γ, Bf, Cl·, F, NO, SO, HCO3·, Fe(CN)63·, CIO, BF4_121033.doc -17- 200800881 PF6, Η, Li, Na+ , K+, Rb+, Ca2+, Mgh, Al3+,

La3+, Ag+, NH/, [N(CH3)4]+, barrier ay'. More preferably, the electrolyte is a salt which is soluble in the carboxylic acid to be halogenated, and the salt does not participate in the characterization reaction or participates in the dentation reaction and then contains the same halogen anion as the halogen source of the reaction to prevent formation of a different halogenated carbonyl group. Compound. In a more preferred embodiment, the electrolyte is a halogen salt such as NaCl, NaBr, Nal, KC1, KBr, cesium, UC1, LiBr, Lil, MgCl2, MgBr2, Mgl2, CaCl2, CaBr2, Cal2.

BaCl2, BaBr2, Bai2. In a preferred embodiment, the metal salt is used as a supporting electrolyte. In another preferred embodiment, a reaction accelerating compound (also referred to herein as a "catalyst") is present in the reaction mixture. In a more preferred embodiment, the compound is a carboxylic acid anhydride (derivative) to be halogenated or an acid salt thereof. In an embodiment comprising a two-step process (ie, a chemical halogenation step followed by an electrochemical step), the above acid halide catalyst can be formed in the reaction mixture, and thus it is not necessary to use a product in the chemical step, such as PCL. Or s〇Ci2 or S〇2Cl2, COC12, anhydride or sulfur (used as a catalyst) can be added. As indicated above briefly, these anhydride and acid halide type compounds have the additional advantage that they scavenge water to produce a tickic acid and thus enable the reaction conditions to be completely anhydrous. The catalyst is used in a typical amount between 2 and 30% by weight of the total reaction mixture. An additional advantage of the process of the present invention is that the catalyst compound is not degraded by the water present in the reaction mixture because the electrochemical reaction is carried out in a non-aqueous environment. 121033.doc -18- 200800881

The electrode used may be selected from any material that does not degrade in the reaction mixture to produce undesirable by-products under the reaction conditions. In this aspect, the choice of anode material is particularly important' because the anode is most susceptible to degradation during processing conditions. In a quarterly parent embodiment, the anode is carbon (such as boron doped diamond, graphite, glassy carbon), ceramic (such as magnetite, that is, ^^4 or Eb〇nex8, that is, mixed titanium oxide ), a metal alloy (such as 铭/钌) or a noble metal (such as Au, gossip, Pd, Pt, Ti), which may optionally contain a mixed metal oxide such as IrOVRuO2 (for example, iIr〇2/Ru〇2 on titanium) , shape-stabilized anode: still a8 electrode), and the cathode is carbon (such as boron-doped diamond, graphite, glass-carbon metal (such as nickel, lead, mercury, titanium, iron, chromium), metal alloy (such as stainless steel (such as a-Ni-Fe), Monel (Cu_Ni), yellow steel (cu_zn) or metal oxide (such as Pb/Pb〇2)) or any other as long as it is stable in the system and does not produce significant amounts of improper by-products Electrode. Examples of electrode materials are mentioned in the reference AJ BardAM. Stratmann^ > Encyclopedia of Electrochemistry^~(9)Heart (10)·, Volume 8, Chapter 2, page pp. The electrode is preferably selected such that its specific surface area k can be 冋 and the cathode and the anode The distance between them is as small as possible. For those who are familiar with this technology, there will be no problem of selecting φ 'ife JtK 1 to select the electrode suitable for this purpose. The same life is the polar electrode, parallel plate electrode, packed bed The electrode, fluidized bed electrode can be described as a non-limiting example of an electrode that satisfies more than one standard. The electrode configuration can be monopolar or bipolar. Preferably, during the method of the present invention. The current density of 5 and 4 kA/m2 is usually between (^丨 and ? kA/m2' and is best between 12 and 103 s.doc -19-200800881 between i and 2 kA/m2. Battery voltage (main but not exclusively) Depending on the applied current density, the conductivity of the reactive fluid and the distance between the electrodes, the method of the invention, typically at 1 and 10 volts, can be combined with a UV treatment step whereby a halogen gas is added to the reaction system by UV irradiation. Conversion to an imine atom and also enabling it to react with a carbonyl-containing compound to produce a carbonyl-containing compound to be halogenated. The process of the invention may be a batch, semi-batch or continuous process; it is a continuous process. Usually in the range of 1 to 10 barA The method is carried out; the pressure is preferably between 0.9 and 5 barA, preferably about 1 to 2 bar A. BarA means absolute bar. Usually between 11 and 200 t:, preferably between 20 and 150 T: More preferably, the process is carried out between 75 and 140 ° C, preferably between 80 and 120 ° C. The invention is further illustrated by the following examples and comparative examples. Example Example 1 uses HC1 to gasify acetic acid. A reaction vessel containing a graphite anode and a cathode (material type 6503, Le Carbonne Lorraine, Rotterdam, The Netherlands) having an effective anode area of 580 cm2 and an effective cathode area of 530 cm2 will contain 7 wt% anhydrous calcium chloride (JT) · Baker, 0070, 95% by weight minimum), 69% acetic acid (Fluka, 45 73 1 , > 99.8 wt%) and 24 wt% B. Mixture of 800 g of chlorine (Fluka, No. 00990, > 99%) 121033.doc -20- 200800881 Preheated to 70 ° C and electrolyzed at an average current of 20 amps. Hydrogen chloride gas was added to the reaction mixture during the electrolysis process. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). Table 1 shows the measurement of one chloroacetic acid (MCA) concentration and dichloroacetic acid (DCA) concentration (by weight % relative to the sum of acetic acid (HAc), MCA and DCA amounts) by HPLC and transfer in the process Comparison of the amount of charge. Table 1: Comparison of the concentration of monochloroacetic acid (MCA) and dichloroacetic acid (DCA) with the amount of charge transferred during the initial electrolysis of a mixture containing acetic acid, acetamidine, calcium chloride and hydrogen chloride (Example 1) Sample transfer charge [ A, h] MCA content [% by weight] DC A content [% by weight] 1 5 0.6 0.003 2 16 2.6 0.007 3 34 7.1 0.013 4 51 10.7 0.020 5 59 12.3 0.024 6 78 16.1 0.029 7 107 21.6 0.044 8 140 27.4 0.054

Example 2 Using CaCl2 (when HCl was absent) to gasify acetic acid In a reactor as mentioned in Example 1, 72% by weight of acetic acid (Fluka, 4573 No. 1, > 99.8% by weight), 21% by weight 650 g of a mixture of acetonitrile (Fluka, No. 00990, > 99%) and 7 wt% of anhydrous calcium chloride (JT·Baker, 0070, minimum 95% by weight) was preheated to 70 ° C and Electrolysis at a current between 5 and 20 amps. In contrast to Example 1, no hydrogen chloride gas was added to the reaction mixture in this example. 121033.doc -21 - 200800881 A sample obtained from the electrolyte during the electrolysis process was analyzed by high performance liquid chromatography (HPLC). The results of the analysis show that MCA can also be produced from the mixture in the absence of hydrogen chloride. Table 2 shows the concentration of gaseous acetic acid (MCA) and dichloroacetic acid (DCA) measured by HPLC (in % by weight relative to the sum of the amounts of acetic acid (HAc), MCA and DCA) and the charge transferred during the process. The comparison of the amount. Table 2: Comparison of the concentration of chloroacetic acid (MCA) and dichloroacetic acid (DCA) with the amount of charge transferred during the electrolysis of the mixture containing acetic acid, ethyl chloroform and calcium hydride (Example 2) ] MCA content [% by weight] DC A content [% by weight] 1 0.5 0.6 0.003 2 2.6 1.4 0.007 3 7.3 2.7 0,010 4 12.5 4.1 0.018 5 16.8 5.0 0.019 6 26.6 7.6 0.026 Example 3 uses di-acetic acid to gasify acetic acid in In the reactor mentioned in Example 1, 60% by weight of acetic acid (Fluka, 45731, > 99.8% by weight), 19% by weight of acetonitrile (Fluka, 00990, > 99%), 5% by weight of anhydrous calcium chloride (JT·Baker, 0070, minimum 95% by weight) and 16% by weight of dichloroacetic acid (Acros Chemicals, Lot A0220473, 99+%) of 700 gram of mixture preheated to 70° C and electrolysis at a current of 20 amps. Hydrogen chloride is added to the reaction mixture. A sample obtained from the electrolyte 121033.doc -22^ 200800881 during the electrolysis process was analyzed by high performance liquid chromatography (HPLC). The analysis showed that the yield of MCA was almost twice as high as that of Example 2 as compared with Example 2. The acetic acid is chlorinated and the DCA is hydrogenated to MCA. Table 3 shows the concentration of one of chloroacetic acid (MCA) and dichloroacetic acid (DCA) by HPLC (in terms of % by weight relative to the sum of the amounts of acetic acid (HAc), MCA and DCA) and between the processes A comparison of the amount of transferred charge. Table 3: Concentrations of acetic acid (HAc), monochloroacetic acid (MCA) and dichloroacetic acid (DCA) with the initial mixture containing acetic acid, ethyl chloroform, chloroacetic acid, dichloroacetic acid and vaporized W calcium during electrolysis Comparison of the amount of charge (Example 3) Sample transfer charge [Ah] HAc content [% by weight] MCA content [% by weight] DCA content [% by weight] 1 0.0 80.4 2.0 17.6 2 28 74.2 12.1 13.7 3 60 68.1 22.7 9.2 4 95 61.7 33.3 5.0 5 123 57.2 40.1 2.6 6 140 54.8 43.5 1.7 Example 4 Gasification of propionic acid using HCI In a reactor as mentioned in Example 1, 65 wt% propionic acid (Fluka, lot number 1241470, > 99 weight) %), 840 g of a mixture of 30% by weight of propionic anhydride (Aldrich, batch 05 003 HC-026, 97%) and 5% by weight of anhydrous calcium chloride (JT·Baker, 0070, minimum 95% by weight) Heat to 70 ° C and electrolyze at a current between 1 and 9 amps. Hydrogen chloride gas is added to the reaction mixture during the electrolysis process. A sample obtained from the electrolysis of the electrolysis process was analyzed by high performance liquid chromatography (HPLC). The results of the analysis show that 1-chloropropionic acid can be produced from the mixture. 121033.doc -23- 200800881 Table 4 shows the propionic acid concentration and K-chloropropionic acid concentration (in weight % relative to the sum of the amounts of propionic acid and 1-chloropropionic acid) measured by HPLC and in the process A comparison of the amount of charge transferred during the period. Table 4: Comparison of the concentration of propionic acid and 1-chloropropionic acid with the amount of charge transferred during the initial electrolysis of a mixture of propylene, propionic anhydride and calcium chloride (Example 4) Sample transfer charge [A_h] Propionic acid content [% by weight ] 1-Chloro-propionic acid [% by weight] 1 "αό ~^ 99.9 0.1 2 "〇1 ~^ 100.0 0.0 3 "09 ~^ 99.8 0.2 4 Ύϊ ~ 99.5 0.5 5 Τ3 ~~~~ 98.8 1.2 6 Ύι ~ 98.2 1.8 7 1L8 '~— 97.1 2.9 8 15.3 ~J 96.6 3.4 9 19.4 95.6 4.4 10 94.6 5.4 11 *29^9 ~~— 93.4 6.6 12 *373 ~Η 91.3 T7 Comparative Example 5 Gasification in an aqueous environment Acetic acid A mixture containing 500 ml of hydrogen chloride (1% by weight of HCl in water) was charged into a 1 liter beaker and electrolyzed at a current of 2 amps at room temperature to produce chlorine gas. After two hours of electrolysis, 15 〇 ml of acetic acid (7 〇 wt%) was added to the reaction mixture, which was further electrolyzed at 2 amps for 15 hours at room temperature. The samples obtained during this process were measured by H-NMR. Only the MCA in the flaw can be detected by nmr. The amount of DCA is lower than the detection limit (the detection limit of MCA and DCA of the wake-up R instrument is about 5 〇 ppm). Example 6: Preparation of bromoacetic acid using LiBr There are graphite anodes and cathodes in 5 (material type 65〇3 Le for (10) to 121033.doc 200800881

The reaction vessel of Lorraine, Rotterdam, The Netherlands), which has an effective anode area of 580 cm2 and an effective cathode area of 530 cm2, will contain 11% anhydrous lithium bromide, 33% ethidium bromide and 56% acetic acid (Fluka 00990, &gt 99%) of the 900 gram mixture was preheated to 70 ° C and electrolyzed at an average current of 20 amps. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). After the charge of 83 A-h passed through the electrode, 12.97% bromoacetic acid and 0.017% dibromoacetic acid were formed. Example 7: Gasification of sodium bismuth as electrolysis for HC1 to vaporize acetic acid in a reaction vessel containing a graphite anode and cathode (material type 6503 L, e Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 580 cm2 And the effective cathode area was 530 cm2, and the mixture containing 11% of anhydrous sodium carbonate, 33% acetic anhydride and 56% acetic acid (Fluka 00990, >99%) was preheated to 70 ° C and Electrolysis at an average current of 3.8 amps. Hydrogen chloride gas is added to the reaction mixture during the electrolysis process. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). After passing the electrode at 15.9 A-h, 3.66% MCA and 0.043% DCA were formed. Example 8: Gasification of Lithium as Electrolyte Using HC1 to gasify acetic acid in a reaction vessel containing a graphite anode and a cathode (Material Type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 580 cm2 and an effective cathode An area of 530 cm2, preheated a mixture containing 1.3% anhydrous lithium chloride, 6.6% ethyl chlorinated chloride and 92.1% acetic acid (Fluka 00990, > 99%) to 70 ° C and at 20 amps. Electrolysis at the average current. During the electrolysis process, "chlorinated nitrogen gas · 121033.doc -25 - 200800881 was added to the reaction mixture. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). After passing through the electrode, it formed 22.76% MCA and 0.108% DCA. Example 9 · Using potassium hydride as electrolyte to vaporize acetic acid with HC1

In a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 580 cm2 and an effective cathode area of 530 cm2, it will contain 10% anhydrous potassium chloride, 24%. A mixture of acetonitrile and 66% acetic acid (Fluka 00990, > 99%) in an amount of 808 g was preheated to 70 ° C and electrolyzed at an average current of 10 amps. Hydrogen chloride gas is added to the reaction mixture during the electrolysis process. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). After the charge of 57.7 A-h passed through the electrode, 13.39% MCA & 0.57% DCA was formed. Example 10: Gasification of acetic acid using tris-acetic acid and HC hydrazine in a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 580 cm2 and an effective cathode area of 530 cm2, preheated a mixture containing 11.9% trichloroacetic acid (TCA), 4.8% anhydrous lithium chloride, 11.9% ethyl chloroform, and 71.4% acetic acid (Fluka 00990, > 99%) to 808 grams. Electrolysis was carried out at 70 ° C and at an average current of 30 amps. Hydrogen chloride gas is added to the reaction mixture during the electrolysis process. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). The results in Table 5 indicate that at the end of the process, the DCA content and the TCA content of 121033.doc -26 - 200800881 have all decreased and the MCA content has increased. Table 5: Monogastric acid (MCA), dichloroacetic acid (DC A), and trichloroacetic acid (!) concentrations of Example 10 as measured by HPLC (in comparison to acetic acid (^ 〇, MCA, TCA, and DCA) Comparison of the weight % of the sum of the amounts and the amount of charge transferred during the process Ah MCA content (%) DCA content (%) TCA content (%) 0 0.13 0.00 13.32 16 3.69 2.85 9.47 30.5 7.34 5.13 5.99 47.5 11.69 6.51 3.18 63,5 16.04 6.82 1.51 86 22.00 5.96 0.42 118.5 30.00 3.96 0.05 135.5 33.96 3.01 0.02 152 37.33 2.19 0.01 170 40.51 1.50 0.00 186 43.33 1.06 0.00 211.5 47.18 0.63 0.00

Example 11: Lithium chloride was used as an electrolyte to reduce the mother liquor (using two gas acetic acid and HC1 to vaporize acetic acid) in a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands), wherein The effective anode area is 580 cm2 and the effective cathode area is 530 cm2. It will contain 30% dichloroacetic acid (DCA), 5% anhydrous gasification, 15% ethyl chloroform, 30% chloroacetic acid (MCA) and 20% acetic acid. The mixture of 1,007 grams (Fluka 00990, > 99%) was preheated to 70 ° C and electrolyzed at an average current of 30 amps. Hydrogen chloride gas is added to the reaction mixture during the electrolysis process. A sample obtained by electrolysis from the electrolysis process 1210B.doc -27- 200800881 was analyzed by high performance liquid chromatography (HPLC). The results in Table 6 show that both HAc and DCA levels are reduced and MCA levels are increased at the end of the process. Table 6: Monochloroacetic acid (MCA), dichloroacetic acid (DCA), and acetic acid (HAc) concentrations of Example 11 as measured by HPLC (in weight % relative to the sum of the amounts of HAc, MCA, and DCA) and Comparison of the amount of charge transferred during the process Ah MCA content (%) DCA content (%) HAc content (%) 0 32.34 32.48 35.18 208 75.33 8.34 16.33 Example 12: Calcination of calcium is used as electrolysis to reduce the mother liquor (use Diacetic acid and BEC1 to gasify acetic acid) In a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands), the effective anode area is 580 cm2 and the effective cathode area is 530 cm2. Containing 30% dichloroacetic acid (DCA), 5% anhydrous calcium chloride, 15% ethyl chloroform, 30%-chloroacetic acid (MCA) and 20% acetic acid (Fluka 00990, > 99%) The mixture of 〇〇7 g was preheated to 70 ° C and electrolyzed at an average current of 30 amps. Hydrogenated gas is added to the reaction mixture during the electrolysis process. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). The results in Table 7 indicate that at the end of the process, both the HAc content and the DCA content decreased while the MCA content increased. Table 7: Monochloroacetic acid (MCA), dichloroacetic acid (DCA), and acetic acid (HAc) concentrations of Example 12 as measured by HPLC (in weight % relative to the sum of the amounts of HAc, MCA, and DCA) and Comparison of the amount of charge transferred during this process 121033.doc -28- 200800881 Ah MCA content (%) DCA content (%) HAc content (%) 0 32.08 32.17 35.75 216 71.63 10.76 17.25 Example 13: Use of magnesium gasification Electrolyte to reduce the mother liquor (using dichloroacetic acid and HC1 to chlorinate acetic acid)

In a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 580 cm2 and an effective cathode area of 530 cm2, it will contain 30% digastric acid (DCA), 5.2% anhydrous magnesium chloride, 15% ethyl hydrazine chloride, 30%-gas acetic acid (MCA) and 20% acetic acid (Fluka 00990, > 99%), 1 〇〇 7 g of the mixture preheated to 70 ° C And electrolysis at an average current of 30 amps. Hydrogen chloride gas is added to the reaction mixture during the electrolysis process. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). The results in Table 8 indicate that at the end of the process, 5 HAc content and DCA content decreased while MCA content increased.

Table 8: Monochloroacetic acid (MCA), dichloroacetic acid (DCA), and acetic acid (HAc) concentrations of Example 13 as measured by HPLC (in weight % relative to the sum of the amounts of HAc, MCA, and DCA) and Comparison of the amount of charge transferred during the process Ah MCA content (%) DC A content (%) HAc content (%) 0 32.67 32.76 34.57 186 67.32 11.34 18.28 Example I4 ··Gasification of zinc as electrolyte for HC1 Acetic acid, in a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands), with an effective anode area of 580 cm2 and an effective cathode area of 530 cm2, will contain .5% anhydrous chlorination A mixture of 1,607 g of zinc, 13% ethyl chloroform and 82% acetic acid (Fluka 00990 121033.doc -29-200800881, >99%) was preheated to 70 ° C and electrolyzed at an average current of 25 amps. . Hydrogen chloride gas is added to the reaction mixture during the electrolysis process. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). After the charge of 162 A-h passed through the electrode, 15.67% MCA & 0.10% DCA was formed. Example 15: Gasification of acetic acid by using gasified iron (111) as an electrolyte

In a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 580 cm2 and an effective cathode area of 530 cm2, it will contain 5% anhydrous ferric chloride (III). A mixture of 13% acetamidine chloride and 82% acetic acid (Fluka 00990, > 99%) in an amount of 1,607 g was preheated to 70 ° C and electrolyzed at an average current of 30 amps. Hydrogen chloride gas is added to the reaction mixture during the electrolysis process. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). After the charge of 192 A-h passes through the electrode, it forms 4.73 ° /. MCA and 0.10% DCA. Example 16: Aluminum chloride was used as an electrolyte to vaporize acetic acid. In a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands), the effective anode area was 580 cm2 and was effective. The cathode area was 530 cm2, and a mixture containing 5% anhydrous aluminum chloride, 13% ethyl chloroform, and 82% acetic acid (Fluka 00990, > 99%) in an amount of 1,607 g was previously heated to 70 ° C and Electrolysis was carried out at an average current of 30 amps. Hydrogen chloride gas is added to the reaction mixture during the electrolysis process. Samples obtained from the electrolyte during the electrolysis process were analyzed by high performance liquid chromatography (HPLC). After passing the electrode at the charge of '119 A-h 121033.doc -30- 200800881, 12.29% MCA and 0.02% DCA were formed. Example 17: Gasification of dimethyl pentanone using HC1

In a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 47 cm2 and an effective cathode area of 16 cm2, it will contain 6% anhydrous lithium gas, 94% A 61 g mixture of 2,4-dimercapto ketone was preheated to 70 ° C and electrolyzed at an average current of 0.3 amps. During the electrolysis process, ruthenium chloride gas is added to the reaction mixture. A sample obtained from the electrolyte during the electrolysis process was analyzed by NMR. The results in Table 10 indicate that at the end of the process, 2-chloro-2,4-dimethylpentanone was formed. Table 10: 2,4-Dimercaptopurone and 2-chloro-2,4-dimethylpentanone concentrations from Example 17 by NMR (in % of moles) Ah 2,4-II Methyl pentanone 2-chloro-2,4-dimethylpentanone 0 100 0.00 6 98.5 1.5 Comparative Example 18 · Use of trifluoroacetic acid (TFA) to fluorinate acetic acid in a graphite anode and cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) has an effective anode area of 47 cm2 and an effective cathode area of 16 cm2, which will contain 4% anhydrous lithium chloride, 35.4% TFA, 35.4% acetic acid and 25.2% ethyl chloroform. The 99 g-gram mixture was preheated to 70 ° C and electrolyzed at an average current of 2 amps. Samples obtained from the electrolyte during the electrolysis process were analyzed by NMR. No evidence of formation of monofluoroacetic acid or difluoroacetic acid was found in the sample. Only MCA and a small amount of DCA were found. 121033.doc -31 - 200800881 Comparative Example 19: Using KF to fluorinate acetic acid

In a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 47 cm2 and an effective cathode area of 16 cm2, it will contain 4.3% anhydrous potassium fluoride, 68.5%. A mixture of acetic acid and 99.6% of an anthracene gas of 99.5% was preheated to 70 ° C and electrolyzed at an average current of 0.4 ampere. Samples obtained from the electrolyte during the electrolysis process were analyzed by NMR. No evidence of formation of monofluoroacetic acid or difluoroacetic acid was found in the sample. Only MCA and a small amount of DCA were found. Example 2: LiCl was used as an electrolyte to vaporize dodecanoic acid with HC1 in a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 47 cm2 and effective The cathode area is 16 cm2 and will contain 4.9% anhydrous lithium chloride, 35.3% acetic acid, and 35.3. A mixture of 92 g of decanoic acid and 24.5% acetamidine chloride was preheated to 70 ° C and electrolyzed at an average current of 1 ampere. Samples obtained from the electrolyte during the electrolysis process were analyzed by NMR. After the charge of 3·4 A-h passed through the electrode, 1.3 mol% of 2-chloro-dodecanoic acid was formed. Example 21: Gasification of octadecanoic acid using HC1 in a reaction vessel containing a graphite anode and a cathode (material type 6503 Le Carbonne Lorraine, Rotterdam, The Netherlands) with an effective anode area of 47 cm2 and an effective cathode area of 16 cm2, The mixture containing 92% of anhydrous copper chloride, 38.3% acetic acid, 33.6% octadecanoic acid and 23.4% acetyl chloride was preheated to 70 ° C and at 1 amp level 121033.doc -32 - 200800881 Electrolysis under average current. Samples obtained from the electrolyte during the electrolysis process were analyzed by NMR. After the charge of 3·2 A-h passed through the electrode, 13 mol c/〇 of 2-chloro-octadecanoic acid was formed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a device for producing a halogenated carbonyl derivative according to the present invention, which comprises a chemical reactor (A), an electrochemical reactor (B) and a physical separation unit (C). Figure 2 shows an apparatus for preparing a halogenated carbonyl derivative according to the present invention, which uses a chemical reactor (A), an electrochemical reactor (B), a physical separation unit (C), and a monodentate compound. Separation unit (D) separated from the corresponding dihalogenated and higher halogenated compound. [Main component symbol description] 2 3

Entrance Entrance π Entrance 5 6 7 8 9 10 11 12 Export Exit Import Export Export Export Export 121033.doc -33- 200800881

13 14 15 A B C D Outlet Outlet Outlet Chemical Reactor Electrochemical Reactor Physical Separation Unit Separation Unit

121033.doc -34-

Claims (1)

200800881 X. Applying for a patent: 2. 3. 4. A method for preparing a halogenated carbonyl-containing compound by reacting a corresponding carbonyl-containing compound with a hydrogen halide HX, an organic halide R'-X and/or a halogen salt under substantially anhydrous conditions. An electrochemical reaction, which is again a chlorine, bromine or iodine atom, and R, which may be a linear or branched alkyl or aryl group, optionally containing one of oxygen, t, chlorine, molybdenum, fluorine or iodine. Or a plurality of heteroatoms, wherein the halogen atom is electrochemically separated, and is a tetra, an or alkaline earth metal, an alkali metal or a metal cation, and the ruthenium is determined by the valence of the metal cation Mn+ An integer of 5. The method of claim 1, wherein the organic halide R, -X is a dihalogenated and/or higher carbonyl containing compound. The method of claim 1 or claim 2, wherein the halogenated group-containing compound prepared is a mono-chemical compound. The method of the invention of claim 1 or 2 wherein the group-containing compound of m prepared is i-formed at the α-carbon atom. 5. 6. A method for preparing a 'based compound of a humanized Xinshangan &human", which firstly contains a few base compounds of a sputum heart "milk desert or moth molecular chemical reaction and then according to The method of item 1 is to electrochemically treat the reaction mixture. According to the method of claim 2, the starting mixture is such that the monobasic compound containing the monolayer is related to the ancient sm. a mother liquor obtained by separating a benzyl compound with a reaction mixture of a dihalogenated and/or a higher halogen S-rotoryl compound. An additional carbonyl containing compound is added to the method starting from the method of claim 6. The method of any one of items 1, 2, 5, 6 and 7, wherein χ is a chlorine atom 0# which contains a few 9 · If the item 1, 2, 5, ό The method according to any one of the preceding claims, wherein the base compound is acetic acid or propionic acid or a fatty acid, wherein the reaction 10 is additionally present in the method mixture of any one of claims 2, 5, 6 and 7 wherein the electrolyte is present. • If you request any of items 1, 2, 5, 6 and 7 The method of the method is a chloride salt, wherein the method of any one of the claims 1, 2, 5, 6 and 7 is provided: the catalyst of the group of base teeth and (iv) anhydride is externally added to the reaction mixture. The method of any one of the claims 2, 5, 6 and 7 wherein substantially no solvent is present. 14. A device suitable for the method of any of the claims a13, the skirt comprising - via π (5) and optionally D (2), (7) and (4) connected = to - electrochemical reactor (B) chemical reactor (A), reducer (B), The outlet (9) is connected to a physical separation unit (c). 15. The apparatus of claim 14, which additionally comprises a separation unit (9) for the mono-deuterated compound and the corresponding bi-function Separation of higher and higher compounds. 121033.doc 200800881 VII. Designation of representative drawings: (1) The representative representative of the case is: (1). (2) Simple description of the symbol of the representative figure: 1 Entrance 2 inlet k 3 inlet * 4 inlet 5 outlet 7 outlet inlet 8 outlet 9 outlet 10 outlet 11 outlet A chemical reactor B Chemical reactor • c eight physical separation means, when the case if the formula, please show most features disclosed invention of formula (no) 121033.doe