US3313717A - Electrolytic method for preparing dialkyl dicarboxylates - Google Patents

Electrolytic method for preparing dialkyl dicarboxylates Download PDF

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US3313717A
US3313717A US243830A US24383062A US3313717A US 3313717 A US3313717 A US 3313717A US 243830 A US243830 A US 243830A US 24383062 A US24383062 A US 24383062A US 3313717 A US3313717 A US 3313717A
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reaction
anodic
compartment
dicarboxylate
concentration
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Kuwata Tsutomu
Yoshikawa Sadao
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Soda Aromatic Co Ltd
Soda Koryo KK
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/29—Coupling reactions

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  • the present invention relates to a method of preparing dialkyl dicarboxylates and more particularly, to a method of synthesizing dialkyl dicarboxylates by means of electrolytic oxidation in which there has been utilized an anodic reaction.
  • this invention relates to a method of preparing dialkyl dicarboxylates which comprises forming dieste'rs (dialkyl dicarboxylates) by the electrolytic oxidation of an alkali salt solution of an alkyl hydrogen dicarboxylate, etiecting the electrolytic oxidation in a cell consisting of at least one cathodic compartment and one anodic compartment, feeding to said anodic compartment a neutral or slightly acidic solution containing the aforesaid alkali salt, and passing a current of electricity while maintaining said cathodic compartment in an alkaline state.
  • dialkyl dicarboxylates e.g., dlmethylthapsiate
  • dialkyl dicarboxylates e.g., dlmethylthapsiate
  • alkali salts of alkyl hydrogen dicarboxylate for example, the sodium salt of methyl hydrogen azelate
  • platinum wire as the anode in accordance with the following Equations 1, 2 and 3, namely:
  • one such method involves the use of an alkali salt of alkyl hydrogen dicarboxylate in a methyl alcohol solution as illustrated in the Journal of Chemical Soc., 1679 (1938) and 3326 (1950).
  • Still another method utilized an aqueous solution of a potassium salt prepared by using, based on the alkyl hydrogen dicarboxylate, potassium hydroxide in about its stoichiornetric quantity, neutralizing the potassium hydroxide that forms at the cathode, as the reaction proceeds, to prevent the pH of the reaction liquid to move to the alkaline side by replenishing the starting material alkyl hydrogen dicarboxylate monoester, While separating the diesters formed.
  • a cathode and an anode in a single electrolytic cell not partitioned by a bulkhead the material monoester (alkyl hydrogen dicarboxylate), and the esters which are formed as the pro-duct oil, being hydrolyzed by the alkali forming in the vicinity of the cathode form alkali salts or" acids.
  • the surface activity of the material liquid containing these alkali salts becomes intense to a marked degree so as to accelerate the solubilization of the neutral oil product whereby said oil accumulates in the reaction liquid.
  • the quantity that accumulates increases with the passage of time, and if the reaction is continued this brings about an increase in the electrical resistance.
  • Another object of the present invention is to provide a commercially advantageous and effective method of preparing in good yield and with regularity dialkyl dicarboxylates with low voltage and electric power while preventing the occurrence of undesirable side reactions.
  • Another object of the invention is to provide a method 05 of preparing dialkyl dicarboxylates in which the defects of the conventional methods can be overcome and in which a continuous operation with regularity can be carried out satisfactorily over an extended period of time without the need for complicated operating means.
  • cation-exchange membranes are used as partitions and at least one each of an anodic compartment and a cathodic compartment is constituted.
  • anodic compartment a solution of an alkali salt of an alkyl hydrogen dicarboxylate Whose pH has been adjusted to the vicinity of neutral or slightly acidic side is fed and while maintaining the cathodic compartment in an alkaline state electricity is passed.
  • electricity is passed to the first place, when considered from the nature of this type of electrolytic oxidation reaction, while it is one of the requisites that the pH of the reaction liquid does not become alkaline as the reaction proceeds, according to the method of this invention, as shown in FIG.
  • Equation 3 concomitant with the electric discharge of R-COO (wherein R is an alkyl group), the potassium ion K+, for example, passes through the cationexchange membrane 1 and moves to the cathode to form -KOI-I.
  • the carboxyl 6O radical loses a molecule of CO to produce an alkyl radical as in the foregoing Equation 2 and forms diesters as in Equation 3.
  • alkali salt of an alkyl hydrogen dicarboxylate that is used in this invention
  • compounds in which the monoester is composed of a dicarboxylic acid of 3-13 carbon atoms and a lower aliphatic alcohol of 1-3 carbon atoms and said alkali salt is an alkali metal salt, particularly a Na salt or a K salt are satisfactorily used.
  • dicarboxylic acids include, for example, the malonic, succinic, Z-methyl succinic,
  • the lower aliphatic alcohols for the esters thereof include methyl alcohol, ethyl alcohol and propyl alcohol (normal and iso).
  • the alkali salts of alkyl hydrogen dicarboxylates as used in the present invention include the Na and K salts of the alkyl hydrogen dicarboxyiate such as, for example, methyl hydrogen malonate, ethyl hydrogen malonate, methyl hydrogen adipate, ethyl hydrogen adipate, propyl (n-, iso-) hydrogen adipate, methyl hydrogen azelate, ethyl hydrogen azelate, propyl (11-, iso-) hydrogen azelate, methyl hydrogen sebacate, ethyl hydrogen sebacate, propyl (11-, iso-) hydrogen sebacate, methyl hydrogen pimelate, ethyl hydrogen pimelate, propyl hydrogen pimelate, methyl hydrogen suberate, ethyl hydrogen suberate, propyl hydrogen suberate, methyl hydrogen brassylate, ethyl hydrogen brassylate, methyl hydrogen-Z-methyl succinate, ethyl
  • the diesters which can be prepared with advantage include, for example, dirnethyl succinate, diethyl succinate, methdrogen sebacate, propyl (n-, iso-) hydrogen sebacate, dipropyl (n-, iso-) sebacate, methyl propyl (n-, iso-) sebacate, dimethyl brassylate, diethyl brassylate, dimethyl n-tridecane-l:13-dicarboxylate, diethyl n-tridecanelzl3-dicarboxylate, dimethyl thapsiate, diethyl thapsiate, methyl ethyl thapsiate, dimethyl n-hexadecane-lzlo-dicarboxylate, diethyl n-heXadecane-l:l6-dicarboxylate, dimethyl 3-methyl-n-tridecane dicarboxylate, diethyl n-heXade
  • the salts when preparing a neutral or slightly acidic solution of the alkali salts of an alkyl hydrogen dicarboxylate such as described hereinbefore, the salts may be dissolved in an aqueous solution or a water-water soluble lower aliphatic alcohol mixture and the pH adjusted with an alkyl hydrogen dicarboxylate, an alkali, and water or a water-water-soluble lower aliphatic alcohol mixture may be mixed so as to obtain the desired concentration and pH.
  • the alkali used in this instance include those which can form a sodium or a potassium salt such as, for example, caustic soda, caustic potassium, sodinm carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, etc.
  • water-soluble lower aliphatic alcohols included are, for example, methyl alcohol, ethyl alcohol, propyl alcohol (n-, iso-), butyl alco hol (n-, iso-, tert-), etc.
  • a water-water-soluble lower aliphatic alcohol mixture if the concentration of the alcohol is high, a minute amount of the alcohol passes through the partitioning membrane and moves into the cathodic cell where it disperses. To compensate for this portion the anodic liquid is suitably replenished with a minute amount of alcohol.
  • a cationexchange membrane is used.
  • a cation-exchange membrane which is either a homogeneous membrane, a heterogeneous membrane, or a united membrane may be used; for example, strongly acid cation-exchange resin membranes such as the polystyrene sulfonic acid resin membrane, the styrene sulfonic acid-butadiene type resin membrane, the polyethylene-styrene sulfonic acid type resin membrane, the interpolymeric resin membrane, etc.
  • the weakly acid cation-exchange resin membranes such as the divinyl benzene acrylate, the divinyl benzene methacrylate and the divinyl benzene maleic anhydride types may also be used.
  • compartments at their ends are made cathodic and, the compartments adjoining thereto anodic and thereby forming in alternation cathodic and anodic compartments. It is of course possible to make the compartments at their ends anodic, but since it is advantageous to use platinum as the anodes, and since only one surface of an expensive plate would be utilized, the compartments at the two ends should be made cathodic.
  • anodic cells To the thus constituted anodic cells is fed a neutral or slightly acidic solution containing an alkali salt of an alkyl hydrogen dicarboxylate, is fed to the anodic compartment and, the solution used as a concentration of 2040% by weight, preferably Z535% by weight, and a pH of preferably 6-7.
  • the cathodic compartments are maintained in an alkaline state. Since allralis are formed the cathodic compartments by the alkali metal ions which nave moved over from the anodic compartment by passing through the cationexchange membranes, the alkalinity of the former may be maintained merely by adding water during the continuance of the reaction to adjust the alkaline concentration preferably to 0.53% by weight.
  • Such an alkali may be, for example, caustic soda, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassiun bicarbonate.
  • the akali metal of the alkaline substance that is added to the cathodic compartment at the start may be the same or different from the alkali metal that is derived from the alkali salt of an alkyl hydrogen dicarboxylate of the anodic cells. drogen dicarboxylate of the anodic compartment.
  • the object of the present invention are satisfactorily attained by passing an electric current described above and carrying out the electrolytic oxidation. While the electric current used will be varied depending on the scale of the electrolytic compartments, the reaction temperature of the electrolytic oxidation of the anodic compartment, the concentration of the anodic liquid, the kind and dimensions of the partitioning membrane, etc., the method of this invention can be carried out continually over an extended period of time regularly at a low voltage and low power requirements which are of great advantage over the conventional methods. For example, in a hour operation for obtaining dimethyl thapsiate from an aqueous solution of a potassium salt of methyl hydrogen azelate, the voltage and power required by the conventional methods were on the order of 12.3 volts and l2.4 37.7 kWh.
  • the method of the present invention can be carried out satisfactorily by the use of a voltage of 9 volts and a consumption of power on the order of 4.62 kwh. (practically constant with the passage of time) per kg. of dimethyl thapsiate produced when operating for the same number of hours under identical conditions, the technical difiiculties of the conventional methods being moreover surmounted.
  • Such a continuous method may be carried out by feeding continuously, while passing an electric current, a neutral or slightly acidic solution containing an alkali salt of an alkyl hydrogen dicarboxylate to the anodic compartment and water to the alkaline solution in the cathodic compartment, taking out on the other hand the liquid containing the formed diesters from which the said-diesters are separated, then after deplenishing the residual liquid with the materials consumed and adjusting the pH in concomitance therewith, recycling said liquid again to the anodic compartment, While discharging continuously the cathodic compartment liquid.
  • any means by which the floating oil can be continuously taken out as quickly as possible can be utilized.
  • the removal by means of, for example, the overflow method is convenient.
  • the liquid phase containing the diesters collects at the bottom (on account of its pH or specific gravity) of the oil formed, it can be taken out by providing a suitable outlet at the bottom.
  • the extraction and separation may be per formed by using a methanol-insoluble lower aliphatic hydrocarbons, 'for example, hexane.
  • concentration of the alcohol is relatively low, for example, about 10% by weight, such a necessity does not arise.
  • the ad justment of the concentration and pH of the residual liquid may he carried out by adding an alkyl hydrogen dicarboxylate and an alkaline substance, or it can also be accomplished by the addition of an alkali salt of an alkyl hydrogen dicarboxylate and a small amount of an alkvl hydrogen dicarboxylate.
  • Cathode Thin plate of nickel, stainless steel or iron 19 cm. 20 cm., 380 cm.
  • one example comprises preparing by means of the material tank 1 and the adjusting tank 2 a neutral or slightly acidic solution containing in a suitable concentration an alkali salt of alkyl hydrogen dicarboxylate, which isused as the anodic compartments liquid of the electrolytic reaction vessel 3, and on the other hand, filling the cathodic compartments of the electrolytic reaction 3 at first with a dilute aqueous alkaline solution containing a small amount of an alkali, and then passing an electric current. An anodic liquid is introduced into the anodic compartment from the bottom thereof at the rate of 3-5 l./hr. from the material tank 1.
  • the oil produced containing the intended diesters which rises to the surface of the anodic compartment liquid along with the evolution of carbon dioxide that attends the progress of the reaction is caused to flow out from the overflow outlet at the top and is conducted to an oil and water separation tank 4.
  • the diesters which have been separated here are conveyed to a receiving tank 5, whereas the residual liquid after having its concentration and pH adjusted is recycled to the electrolytic reaction 'vessel 3 via the material tank 1.
  • the concentration of alkali of the cathodic solution becomes higher as the reaction proceeds resulting in a decrease in the selective permeability of the membrane so that the adjustment of the pH becomes difficult of accomplishment.
  • water is fed to the cathodic compartment to dilute the cathodic compartment liquid and thus maintain the concentration of alkali at 0.53%. In this case, the alkaline water which flow out from the cathodic compartment is recovered at the outside of the vessel.
  • the oil of the receiving tank 5 is adjusted to pH 9 by means of a caustic alkali solution, extracted with a solvents using aliphatic and aromatic hydrocarbons, preferably such as benzene, toluene, hexane, etc., after which the monoesters mixed in said oil is separated as an aqueous solution of alkali salt, the extract washed with water, and after recovering the solvent followed by dehydration, rectification is effected to obtain the intended purified diesters.
  • a caustic alkali solution extracted with a solvents using aliphatic and aromatic hydrocarbons, preferably such as benzene, toluene, hexane, etc.
  • Example 1 using 3,200 g. of methyl hydrogen azelate and 1,230 g. of potassium carbonate an aqueous solution having a concentration of 30% and a pH of 7 was prepared, and by operating as described in section B, above, with the electrolyzer described in A, above, employing a direct current of 9 volts and 20 amperes dimethyl thapsiate was obtained.
  • Rate of formation (g./ah.) 2. 90 3. 2. 99 2. 99 2. 97 Oil formed (g) l- 1, 160 2, 100 2, 090 2, 094 2, 080 9, 524 Methyl-7-octenoate (g) 50-70" C mm. 5 186 (16.0%) .557 (17.0%) 341 (16.3%) 355 (16.0%) 349 (16.8%) 1, 568 Methyl-S-oxyoctanoate (g) 120 C./5 mm.
  • Material monoester (g.) 1, 900 l Material monoester replenished (g.) 1, 006 2, 046 1, S21 10, 181 Reaction Conditions:
  • Rate of formation (g./ah.) 1. 59 1. 50 1. 24 0.93 O. Oil formed (g) 636 1, 050 865 650 664 3, 865 Mcthyl-Focteuoate (g.) (23.6%) 215 (20. 5%) 180 (20.8%) (23.8%) 159 (23.9%) 859 Methyl-S-oxyoctanoate (g). 163 (25.7%) 240 (22.9%) 192 (22.2%) 184 (28.3%) 194 (29. 2%) 973 Dimetliyl thapsiatc (g.) 323 (50. 7%) 495 (47. 1%) 385 (44. 5%) 228 (35. 2%) 225 (34. 0%) 1, 656 Y 1gligh boiling fractions (g.) 10D 9.5%) 103 (12.5%) 82 (12.7%) 86 (12.9%)
  • Example 2 A water-methanol solution (concentration of methanol 10% by weight) of the same composition, same concentration and same pH was used instead of the aqueous solution of Example 1. Except that a direct current of 10-11 volts was used while replenishing the anodic compartment with methanol to compensate for the minute quantity of the methanol which moves to the cathodic compartment, otherwise the same techniques were followed as in Example 1. After a reaction time of 150 hours, dimethyl thapsiate was likewise obtained satisfactorily. The yield was 59% of theory.
  • Example 3 Example 3.-Except that a water-methanol solution whose concentration of methanol was 50% was used and a direct current of 13-15 voltswas used, otherwise the same procedures were followed as in Example 2, Whereby was satisfactorily obtained likewise after a reaction time of 50 hours dimethyl thapsiate, the yield of which was 62% of theoretical yield.
  • the concentration of methanol is high, the oil formed containing the diesters does not rise to the top but forms a homogeneous layer. Consequently, instead of the oil and water separating tank 4 a continuous extractor using hexane as the extracting agent is employed, and the oil formed is transferred to the hexane.
  • the extracting agent may be any lower chain hydrocarbon that is substantially insoluble in methanol, the preferred being hexane. This operation is unnecessary when the concentration of methanol is so low that the oil operation performed is immiscible when the concentration of methanol is so low that the oil portion formed is immiscible, such operation is unnecessary.
  • Example 4 When the same techniques as in Example :1 were followed, except that an aqueous solution of the centration was 30% and having a pH of 7 was prepared using the potassium salt of methyl hydrogen brassylate and the potassium salt of methyl hydrogen Z-methyl succinate in a proportion of 1 mol of the former to 1 mol of the latter, and then the reaction was carried out for 30 hours at 9-11 volts and 20 amperes, whereby was obtained likewise satisfactorily dimethyl 3-methyl-n-tridecane dicarboxylate.
  • a method of preparing a dialkyl dicarboxylate which comprises converting an alkali salt of said dicarboxylate into a diester by means of electrolytic oxidation, in a cell consisting of at least one anodic compartment and one cathodic compartment and a cationic exchange membrane, feeding a solution of said alkali salt of an alkyl hydrogen carboxylate having a pH of 6 to 7 and a concentration of 20 to 40% by weight to said anodic compartment, maintaining said cathodic compartment in an alkaline state and having an alkaline concentration of 0.5 to 3% by weight and passing an electric current through the system to efiect electrolytic oxidation.
  • a method of preparing a dialkyl carboxylate which comprises converting an alkali salt of said dicarboxylate into a diester by means of electrolytic oxidation, in a cell consisting of at least tiree compartments using at least two cation exchange membranes, making the compartments on the two ends cathodic and the compartment adjacent thereto anodic, thus having cathodic and anodic compartments in alternation, feeding to said anodic compartment a solution of said alkali salt of an alkali hydrogen dicarboxylate having a pH of 6 to 7 and a concentration of 2G to 40% by weight, maintaining said cathodic compartments in an alkaline state and having an alkali concentration of 0.5 to 3% by weight and passing an electric current through the system to effect electrolytic oxidation.
  • a method of preparing a dialkyl dicarboxylate which comprises converting an alkali salt of said dicarboxylate into a diester by means of electrolytic oxidation, in a cell consisting of one anodic compartment and a cathodic compartment and an anionic exchange membrane, passing an electric current through the system, continuously feeding a solution of said alkali salt of an alkyl hydrogen dicarboxylate having a pH of 6 to 7 and a concentration of 20 to 40% by weight to said anodic compartment and water to said cathodic compartment containing an alkaline solution having an alkali concentration of 0.5 to

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415725A (en) * 1965-10-01 1968-12-10 B R Belleau Ltd Electrolytic preparation of trialkoxyalkanes and tetraalkoxyalkanes
US3879271A (en) * 1972-10-04 1975-04-22 Basf Ag Production of diesters of dicarboxylic acids by electrochemical condensation of monoesters of dicarboxylic acids
US4032416A (en) * 1976-03-10 1977-06-28 E. I. Du Pont De Nemours And Company Electrolytic oxidation process
RU2501889C2 (ru) * 2012-03-22 2013-12-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тамбовский государственный технический университет" (ФГБОУ ВПО "ТГТУ") Электролизер

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2439425A (en) * 1946-04-01 1948-04-13 Du Pont Process for preparing dialkyl esters of dicarboxylic acids
US2680713A (en) * 1953-03-16 1954-06-08 Du Pont Process for preparing diesters of unsaturated alpha, omega-dicarboxylic acids by electrolysis
US2867569A (en) * 1956-07-06 1959-01-06 Colgate Palmolive Co Electrolysis process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2439425A (en) * 1946-04-01 1948-04-13 Du Pont Process for preparing dialkyl esters of dicarboxylic acids
US2680713A (en) * 1953-03-16 1954-06-08 Du Pont Process for preparing diesters of unsaturated alpha, omega-dicarboxylic acids by electrolysis
US2867569A (en) * 1956-07-06 1959-01-06 Colgate Palmolive Co Electrolysis process

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415725A (en) * 1965-10-01 1968-12-10 B R Belleau Ltd Electrolytic preparation of trialkoxyalkanes and tetraalkoxyalkanes
US3879271A (en) * 1972-10-04 1975-04-22 Basf Ag Production of diesters of dicarboxylic acids by electrochemical condensation of monoesters of dicarboxylic acids
US4032416A (en) * 1976-03-10 1977-06-28 E. I. Du Pont De Nemours And Company Electrolytic oxidation process
DE2701453A1 (de) * 1976-03-10 1977-09-15 Du Pont Verfahren zur elektrolytischen oxydation von dialkyldithiocarbamaten zu tetraalkylthiuramdisulfiden
RU2501889C2 (ru) * 2012-03-22 2013-12-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тамбовский государственный технический университет" (ФГБОУ ВПО "ТГТУ") Электролизер

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