CN111809195B - Electrochemical catalytic oxidation coupling synthesis method of alpha-disulfide dicarboxylic acid compound - Google Patents
Electrochemical catalytic oxidation coupling synthesis method of alpha-disulfide dicarboxylic acid compound Download PDFInfo
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Abstract
The invention relates to an electrochemical catalytic oxidative coupling synthesis method of an alpha-disulfide dicarboxylic acid compound with a structural formula as shown in the specification:
the main process is as follows: in a 50mL single-chamber electrolytic cell, α -mercaptocarboxylic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and the mixture was dissolved with stirring at 29 ℃. Using graphite flake as anode and graphite flake as cathode, at 7.9mA/em2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound with the yield of 69-95%.
Description
The invention relates to an electrochemical catalytic oxidation coupling synthesis method of an alpha-disulfide dicarboxylic acid compound.
Disulfide compounds have wide application in the fields of food additives, biomedicines, rubber industry and the like, so that the synthesis method of the compounds is always concerned by people.
The oxidative coupling method is one of the methods for synthesizing alpha-dithioether dicarboxylic compounds. Gastaldi et al (St. phane Gastaldi, St. phanie Escube, Vanthuyne N, et al. dynamic Kinetic Resolution of Amines investigating Biocatalysis and in Situ Free radial synthesized Racemization [ J ]. Organic Letters, 2007, 9 (5): 837- > 839.) report a chemical oxidative coupling synthesis of 2, 2' -dithiodipropionic acid. The method is to synthesize the alpha-disulfide dicarboxylic acid compound by using sodium thiosulfate as a nucleophilic reagent, using an iodine simple substance as an oxidation coupling reagent and using water as a reaction solvent system under the condition of neutral temperature and under the condition of 100 ℃. The main problems of this method are as follows:
(1) sodium thiosulfate is used as a nucleophilic reagent, an iodine simple substance is used as an oxidation coupling reagent, the post-treatment is complicated, and the reaction yield is low due to more byproducts;
(2) the reaction time is long and the reaction needs to be carried out under the condition of high temperature;
(3) the iodine simple substance has higher price and is not suitable for large-scale synthesis;
at present, the synthesis method of the alpha-disulfide dicarboxylic acid compound through electrochemical catalytic oxidation coupling is not reported in domestic and foreign documents.
The invention aims to provide an electrochemical catalytic oxidative coupling synthesis method of alpha-disulfide dicarboxylic acid compounds, which has the advantages of high efficiency, low cost, simple operation and relatively small environmental pollution.
The invention provides an electrochemical oxidation coupling synthesis method of an alpha-disulfide dicarboxylic acid compound, which comprises the steps of taking a compound 1 as a raw material in a single-chamber electrolytic cell, taking 0.5 equivalent of ammonium halide or alkali metal halide as an electrolyte and an electrocatalyst at the same time in a solvent system, wherein the reaction temperature is 29 ℃, a graphite sheet is taken as an anode, the graphite sheet is taken as a cathode, and the current density is 5.6-13.5 mA/cm2After passing through 1.0F/mol of electricity, the target compound 2 is obtained, and the reaction formula is as follows:
wherein R is1Represents Me-, Et-, i-Pr-, n-Bu-, Ph-, 2-ClPh-; 3-ClPh-; 4-ClPh-; 4-FPh-; 4-BrPh-.
The solvent system is DMSO, DMF, DME, methanol, ethanol, acetonitrile, methanol DME (2: 1), methanol DME (7: 2), methanol DME (8: 1), preferably methanol DME (2: 1).
The above ammonium halide or alkali metal halide is ammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, sodium bromide, sodium chloride, potassium iodide, preferably sodium iodide.
The anode of the electrolysis adopts a graphite electrode, and the cathode adopts a graphite electrode.
The reaction temperature is preferably 29 ℃.
The current density is preferably 7.9mA/cm2。
The amount of electricity passed above is preferably 1F/mol.
Compared with the prior art, the method of the invention has the following effects:
(1) the device is simple and the experiment operation is convenient.
(2) The constant current electrolysis method is adopted, the equipment cost required by the method is low, and meanwhile, the constant current electrolysis is more suitable for industrial production.
(3) The working electrode is a graphite electrode, and is cheap and easy to obtain.
(4) The reaction temperature is 29 ℃, and the conditions are mild.
The invention relates to an electrochemical catalytic oxidative coupling synthesis method of an alpha-disulfide dicarboxylic acid compound with a structural formula as shown in the specification:
the main process is as follows: in a 50mL single-chamber electrolytic cell, α -mercaptocarboxylic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheet as cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound with the yield of 69-95%.
The structure of the alpha-dithioether dicarboxylic acid compounds electrochemically prepared from alpha-mercaptocarboxylic acids in the process of the present invention was confirmed by nuclear magnetic resonance. The results of the analysis are appended to the examples.
Detailed Description
Example 1: oxidation coupling reaction for synthesizing alpha-mercaptopropionic acid under electrochemical condition
In a 50mL single-chamber electrolytic cell, α -mercaptopropionic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME ═ 2: 1, and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode,The graphite flake is used as a cathode and is at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound 2 a. Yield: 89 percent.1H NMR(DMSO-d6300MHz) (non-corresponding isomer mixture): δ 12.80(br, 2H), 3.63(q, J ═ 7.2Hz, 1H), 3.62(q, J ═ 7.2Hz, 1H), 1.37(d, J ═ 7.2Hz, 6H);13C NMR(DMSO-d6，75MHz)δ 173.05，47.28，46.97，17.04，16.90。
example 2: oxidation coupling reaction for synthesizing alpha-mercaptobutyric acid under electrochemical condition
In a 50mL single-chamber electrolytic cell, α -mercaptobutyric acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheet as cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound 2 b. Yield: 79 percent.1H NMR(DMSO-d6300MHz) (non-corresponding isomer mixture): δ 12.81(br, 2H), 3.48-3.34(m, 2H), 1.78-1.73(m, 4H), 0.90(t, J ═ 7.2Hz, 6H);13C NMR(DMSO-d6，75MHz)：δ172.54，172.52， 54.36，54.31，24.21，24.11，11.39，11.35.
example 3: the oxidative coupling reaction of alpha-mercaptohexanoic acid is realized by synthesis under electrochemical conditions
In a 50mL single-chamber electrolytic cell, α -mercaptohexanoic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheet as cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound 2 c. Yield: 71 percent.1H NMR(DMSO-d6300MHz) (non-corresponding isomer mixture): δ 12.77(br, 2H), 3.49-3.42(m, 2H), 1.76-1.67(m, 4H), 1.29-1.22(m, 8H), 0.84(t, J ═ 6.6Hz, 6H);13C NMR(DMSO-d6，75MHz)：δ172.67，172.64，52.92，52.70，30.61，30.58，28.73，21.86，13.84.
example 4: oxidation coupling reaction of 2-mercapto-3-methylbutyric acid is realized by synthesis under electrochemical conditions
In a 50mL single-chamber electrolytic cell, 2-mercapto-3-methylbutyric acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheet as cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound 2 d. Yield: 83 percent.1H NMR(DMSO-d6300MHz) (non-corresponding isomer mixture): δ 12.74 (s, 2H), 3.30(d, J ═ 6.6Hz, 1H), 3.27(d, J ═ 6.6Hz, 1H), 2.07-1.97(m, 2H), 1.02(d, J ═ 6.6Hz, 1H), 0.95(d, J ═ 6.6Hz, 1H);13C NMR(DMSO-d6，75MHz)：δ172.38，172.36，61.25，60.56，29.73， 29.60，20.04，20.01，20.00，19.89.
example 5: the oxidative coupling reaction of alpha-mercaptophenylacetic acid is realized under the electrochemical condition
In a 50mL single-chamber electrolytic cell, α -mercaptophenylacetic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheet as cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound 2 e. Yield: 95 percent.1H NMR(DMSO-d6，300MHz)：δ13.22(s，2H)，7.37(m，10H)，4.78(s， 1H)，4.69(s，1H)；13C NMR(DMSO-d6，75MHz)：δ171.16，171.10，135.84，135.81，129.49，128.81， 128.76，128.54，128.49，57.49，57.30.
Example 6: the oxidation coupling reaction of alpha-mercapto o-chlorophenylacetic acid is realized under the electrochemical condition
In a 50mL single-chamber electrolytic cell, α -mercaptoo-chlorophenylacetic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheet as cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound 2 f. Yield: and 69 percent.1H NMR(DMSO-d6300MHz) (non-corresponding isomer mixture): δ 13.42(s, 2H), 7.50-7.34(m, 8H), 5.22(s, 1H), 5.18(s, 1H);13C NMR(DMSO-d6，75MHz)：δ170.18，170.12， 133.68，133.66，133.32，133.24，130.80，130.69，130.17，129.92，129.86，127.65，55.66，55.21.
example 7: the oxidative coupling reaction of alpha-mercapto m-chlorophenylacetic acid is realized by synthesis under electrochemical conditions
In a 50mL single-chamber electrolytic cell, α -mercaptom-chlorophenylacetic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheet as cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain 2g of the target compound. Yield: 88 percent.1H NMR(DMSO-d6300MHz) (non-corresponding isomer mixture): δ 13.40 (s, 2H), 7.49-7.34(m, 8H), 4.86(d, J ═ 2.4, 1H), 4.80(d, J ═ 2.7, 1H);13C NMR(DMSO-d6，75 MHz)：δ170.59，138.18，138.15，133.31，130.72，128.63，128.81，127.44，127.39，56.49，56.22.
example 8: the oxidative coupling reaction of alpha-mercapto-p-chlorophenylacetic acid is realized under the electrochemical condition
In a 50mL single-chamber electrolytic cell, α -mercapto-p-chlorophenylacetic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheetAs cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound for 2 h. Yield: 89 percent.1H NMR(DMSO-d6300MHz) (non-corresponding isomer mixture): δ 13.39 (s, 2H), 7.47-7.37(m, 8H), 4.89(s, 1H), 4.84(s, 1H);13C NMR(DMSO-d6，75MHz)：δ170.83， 170.42，134.86，133.25，130.61，128.84，56.41，56.18.
example 9: the oxidative coupling reaction of alpha-mercapto-p-bromophenylacetic acid is realized by synthesis under electrochemical conditions
In a 50mL single-chamber electrolytic cell, α -mercaptophenylacetic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME ═ 2: 1, and the mixture was dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheet as cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound 2 i. Yield: 86 percent.1H NMR(DMSO-d6300MHz) (non-corresponding isomer mixture): δ 13.43(s, 2H), 7.61-7.58(m, 4H), 7.33-7.29(m, 4H), 4.87(s, 1H), 4.82(s, 1H);13C NMR(DMSO-d6，75MHz)：δ170.73，135.26，131.75，130.89，121.80，56.40，56.15.
example 10: the oxidation coupling reaction of alpha-mercapto-p-fluorophenylacetic acid is realized by synthesis under electrochemical conditions
In a 50mL single-chamber electrolytic cell, α -mercaptophenylacetic acid (1mmol) and sodium iodide (0.5mmol) were added to a mixed solvent system of 9mL methanol: DME (2: 1), and dissolved with stirring at 29 ℃. Using graphite sheet as anode and graphite sheet as cathode, at 7.9mA/cm2Electrolyzing under the condition of constant current, and stopping electrolysis when the passing electric quantity reaches 1.0F/mol. Removing solvent, adding appropriate amount of 5% Na2S2O3Solution, acidification, anhydrous ether extraction (20mL x 3), salt washing, anhydrous MgSO4Drying and concentrating to obtain the target compound 2 j. Yield: 75 percent.1H NMR(DMSO-d6300MHz) (non-corresponding isomer mixture): δ 13.34 (s, 2H), 7.44-7.20(m, 8H), 4.85(s, 1H), 4.79(s, 1H);13C NMR(DMSO-d6，75MHz)：δ170.89， 161.99(d，J＝243.8Hz)，132.05，130.83(d，J＝7..5Hz)，115.70(d，J＝21.8Hz)，56.26，55.05.
Claims (1)
1. an electrochemical catalytic oxidation coupling synthesis method of an alpha-disulfide dicarboxylic acid compound comprises the steps of taking a compound 1 as a raw material in a single-chamber electrolytic cell, taking 0.5 equivalent of ammonium halide or alkali metal halide as an electrolyte and an electrocatalyst at the same time in a mixed solvent system of ethylene glycol dimethyl ether and methanol, wherein the reaction temperature is 29 ℃, the graphite sheet is taken as an anode, the graphite sheet is taken as a cathode, and the current density is 5.6-13.5 mA/cm2After passing through 1.0F/mol of electricity, the target compound 2 is obtained, and the reaction formula is as follows:
wherein R is1Represents Me-, Et-, i-Pr-, n-Bu-, Ph-, 2-ClPh-; 3-ClPh-; 4-ClPh-; 4-FPh-; 4-BrPh-.
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