CN116262976B - Electrochemical synthesis method of benzaldehyde derivative - Google Patents

Electrochemical synthesis method of benzaldehyde derivative Download PDF

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CN116262976B
CN116262976B CN202310319423.9A CN202310319423A CN116262976B CN 116262976 B CN116262976 B CN 116262976B CN 202310319423 A CN202310319423 A CN 202310319423A CN 116262976 B CN116262976 B CN 116262976B
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benzaldehyde
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CN116262976A (en
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沈海伟
郑明月
蒋华良
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Hangzhou Institute of Advanced Studies of UCAS
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Abstract

The application provides an electrochemical synthesis method of benzaldehyde derivatives, and relates to the technical field of synthesis of pharmaceutical and chemical intermediates. An electrochemical synthesis method of benzaldehyde derivatives comprises the following steps: mixing raw materials including toluene compounds, electrolyte and solvent to obtain a reaction solution, respectively inserting an anode and a cathode into the reaction solution in a non-discrete electrolytic tank, reacting under constant current, and performing column chromatography to obtain benzaldehyde derivatives; the structural general formula of the toluene compound is as follows:the structural general formula of the benzaldehyde derivative is as follows:wherein R is 1 Is H, C C4 alkyl, C3-C6 cycloalkyl, C6-C8 aryl or heteroaryl; r is R 2 Is H, C C1-C4 alkyl, halogen, C3-C6 cycloalkyl, C6-C8 aryl or heteroaryl. The electrochemical synthesis method of the benzaldehyde derivative provided by the application has the advantages of readily available raw materials, simplicity in operation, high selectivity, safety and rapidness.

Description

Electrochemical synthesis method of benzaldehyde derivative
Technical Field
The application relates to the technical field of synthesis of pharmaceutical and chemical intermediates, in particular to an electrochemical synthesis method of benzaldehyde derivatives.
Background
Benzaldehyde derivatives are widely used as important pharmaceutical intermediates in the synthesis of various natural products, pharmaceuticals, agrochemicals, bioactive compounds, for example: the preparation method is used for preparing important chemical raw materials such as laural, lauric acid, phenylacetaldehyde, benzyl benzoate and the like, and is also an intermediate of herbicide difenoconazole and plant growth regulator trinexapac-ethyl. Therefore, efficient synthesis thereof is one of the hot spots of current research. The traditional synthesis method mainly comprises the steps of synthesizing benzaldehyde derivatives by using toluene chlorination and re-hydrolysis method, benzyl alcohol oxidation method, toluene direct oxidation method and benzene as raw materials, and reacting benzene with carbon monoxide and hydrogen chloride under the actions of pressurization and aluminum trichloride. However, it is not easy to obtain various substituted benzaldehydes by these methods.
In the last decades, the directed C-H direct selective oxidation reaction has progressed considerably, wherein the C-H activity of the allylic position, benzylic position (active C-H), hetero atom (O, N, etc.) adjacent alpha position is higher, and the direct C-H is easier to be selectively oxidized, thus thoroughly changing the framework to open the compoundThis also makes the oxidation of the C-H bond a powerful tool for the development of new drugs. Therefore, the synthesis of benzaldehyde derivatives through direct selective oxidation of C-H bonds is a relatively efficient and simple method. For example: in 2019 Wu et al reported a method of oxidizing K in the presence of an oxidizing agent 2 S 2 O 8 In the presence of Co (OAc) 2 4H2O method for synthesizing benzaldehyde derivative by oxidizing C-H bond at benzyl position in solvent of trifluoroacetic acid and trifluoroacetic anhydride (RSC adv.,2019,9,20879-20883.). Furthermore, 2022, wang et al reported a method of obtaining benzaldehyde derivatives using electrochemical catalytic oxidation of toluene compounds followed by hydrolysis with hydrochloric acid (j.org.chem., 2022,87,7806-7817.). The oxidation process described above has some drawbacks: the use of metal catalysts and stoichiometric oxidants increases cost, steps are cumbersome, substrate applicability is poor, etc.
Therefore, the development of a synthesis method of benzaldehyde derivatives which has the advantages of easily available raw materials, simple operation, high selectivity, safety and rapidness is particularly necessary.
Disclosure of Invention
The present application is directed to an electrochemical synthesis method of benzaldehyde derivatives, so as to solve the above problems.
In order to achieve the above purpose, the present application adopts the following technical scheme:
an electrochemical synthesis method of benzaldehyde derivatives comprises the following steps:
mixing raw materials including toluene compounds, electrolyte and solvent to obtain a reaction solution, respectively inserting an anode and a cathode into the reaction solution in a non-discrete electrolytic tank, reacting under constant current, and performing column chromatography to obtain benzaldehyde derivatives;
the structural general formula of the toluene compound is as follows:
the structural general formula of the benzaldehyde derivative is as follows:
wherein R is 1 Is H, C C4 alkyl, C3-C6 cycloalkyl, C6-C8 aryl or heteroaryl; r is R 2 Is H, C C1-C4 alkyl, halogen, C3-C6 cycloalkyl, C6-C8 aryl or heteroaryl.
Preferably, the positive electrode and the negative electrode are each independently selected from any one of a platinum electrode, a nickel electrode, a magnesium electrode, a stainless steel electrode, a zinc electrode, a reticulated vitreous carbon electrode, and a graphite felt electrode.
Preferably, the electrolyte includes at least one of lithium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium iodide, tetrabutylammonium bromide, and tetrabutylammonium fluoride.
Preferably, the electrolyte is used in an amount of 80 to 150mol% based on the amount of the toluene compound.
Preferably, the solvent comprises one or more of methanol, ethanol, isopropanol, trifluoroethanol, hexafluoroisopropanol, toluene, chlorobenzene, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, dioxane, dichloromethane, 1, 2-dichloroethane, acetone, tetrahydrofuran, ethyl acetate, N-hexane.
Preferably, the constant current is 5-40mA.
Preferably, the temperature of the reaction is 25-75 ℃.
Preferably, the molar concentration of the toluene compound in the reaction solution is 0.1 to 0.5mol/L.
Preferably, the molar concentration of the toluene compound in the reaction solution is 0.2 to 0.6mol/L.
Preferably, the column chromatography adopts silica gel column chromatography, and the volume ratio of the eluent is 10:1 in a mixture of n-hexane and ethyl acetate.
Compared with the prior art, the beneficial effects of this application include:
the electrochemical synthesis method of the benzaldehyde derivative provided by the application has the advantages that the benzaldehyde derivative is generated by oxidizing the toluene compound, the method is a green electrochemical synthesis method, the defect that raw materials are not easy to obtain in the prior art is overcome, in addition, any metal catalyst and oxidant are not needed, electrocatalytic oxidation is used, the byproduct is only hydrogen, and the method is more green and environment-friendly, is easy to obtain in raw materials, simple to operate, high in reaction chemical selectivity, environment-friendly and the like, has larger implementation value and social and economic benefits, and accords with the development of green chemistry and society.
Detailed Description
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1: preparation of Paracetabulum (Ia)
P-methylacetophenone (68 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio) to obtain 61mg of colorless liquid p-acetyl benzaldehyde (Ia), yield: 82%, ia has the formula:
the characterization information is as follows:
1 H NMR(500MHz,CDCl 3 )δ10.10(s,1H),8.09(d,J＝7.1Hz,2H),7.97(d,J＝7.1Hz,2H),2.66(s,3H). 13 C NMR(125MHz,CDCl 3 )δ197.51,191.72,141.35,139.18,129.95,128.95,27.10.HRMS(ESI-TOF):m/z calcd for C 9 H 9 O 2 [M+1] + :149.0597,found 149.0599。
example 2: preparation of Paracetabulum (Ia)
P-methylacetophenone (68 mg,0.5 mmol), tetrabutylammonium hexafluorophosphate (194 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and 58mg of p-acetyl benzaldehyde (Ia) was isolated as a colorless liquid by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio), yield: 78%.
Example 3: preparation of Paracetabulum (Ia)
P-methylacetophenone (68 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and acetonitrile (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio) to obtain 11mg of colorless liquid p-acetyl benzaldehyde (Ia), yield: 15%.
Example 4: preparation of Paracetabulum (Ia)
P-methylacetophenone (68 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a graphite felt electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and 60mg of p-acetyl benzaldehyde (Ia) was isolated as a colorless liquid by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio), yield: 80%.
Example 5: preparation of Paracetabulum (Ia)
P-methylacetophenone (68 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 10ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio) to obtain 41mg of colorless liquid p-acetyl benzaldehyde (Ia), yield: 55%.
Example 6: preparation of Paracetabulum (Ia)
P-methylacetophenone (68 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 50 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio) to obtain 47mg of colorless liquid p-acetyl benzaldehyde (Ia), yield: 63%.
Example 7: preparation of 3-acetylbenzaldehyde (Ib)
3' -methylacetophenone (68 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio) to give colorless liquid 3-acetyl benzaldehyde (Ib) 55mg, yield: 74, ib are shown in the structural formula:
1 H NMR(500MHz,CDCl 3 )δ10.10(s,1H),8.44(s,1H),8.23(d,J＝7.7Hz,1H),8.09(d,J＝7.6Hz,1H),7.73-7.60(m,1H),2.68(s,3H). 13 C NMR(125MHz,CDCl 3 )δ192.52,191.61,137.96,136.82,133.88,133.78,129.71,129.67,26.85.HRMS(ESI-TOF):m/z calcd for C 9 H 9 O 2 [M+1] + :149.0597,found149.0595。
example 8: preparation of 2-acetyl benzaldehyde (Ic)
2' -methylacetophenone (68 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio) to give colorless liquid, 2-acetyl benzaldehyde (Ic) 48mg, yield: 66, ic is as follows:
1 H NMR(500MHz,CDCl 3 )δ10.22(s,1H),7.86(d,J＝7.6Hz,1H),7.72(d,J＝7.4Hz,1H),7.70-7.57(m,2H),2.64(s,3H). 13 C NMR(125MHz,CDCl 3 )δ201.10,192.32,140.68,136.33,133.12,131.97,129.77,128.58,28.91.HRMS(ESI-TOF):m/z calcd for C 9 H 9 O 2 [M+1] + :149.0597,found 149.0598。
example 9: preparation of 4-acetyl-3, 5-dimethylbenzaldehyde (Id)
2',4',6' -trimethylacetophenone (81 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio) to obtain colorless liquid, 4-acetyl-3, 5-dimethylbenzaldehyde (Id) 60mg, yield: 68%, id has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ9.95(s,1H),7.54(s,2H),2.50(s,3H),2.32(s,6H). 13 C NMR(125MHz,CDCl 3 )δ207.27,192.10,148.04,136.31,133.56,129.33,31.84,19.11.HRMS(ESI-TOF):m/z calcd for C 11 H 13 O 2 [M+1] + :177.0910,found 177.0911。
example 10: preparation of 4-acetyl-2-methylbenzaldehyde (Ie)
2, 4-dimethyl acetophenone (74 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio) to give colorless liquid 4-acetyl-2-methylbenzaldehyde (Ie) 47mg, yield: 58, ie has the structural formula:
1H NMR(500MHz,CDCl 3 )δ10.31(s,1H),8.37(s,1H),8.06(d,J＝5.5Hz,1H),7.38(d,J＝5.5Hz,1H),2.73(s,4H),2.64(s,3H). 13 C NMR(100MHz,CDCl 3 )δ196.81,191.99,145.88,135.53,134.14,132.77,132.36,131.99,26.58,19.86.HRMS(ESI-TOF):m/z calcd for C10H11O2[M+1] + :163.0754,found 163.0752。
example 11: preparation of 1, 4-diacetylbenzene (If)
P-ethylacetophenone (74 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant flow 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio) to obtain 61mg of colorless liquid 1, 4-diacetylbenzene (If), yield: 75%, if has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ8.02(s,4H),2.64(s,6H). 13 C NMR(125MHz,CDCl 3 )δ197.61,140.30,128.62,27.02.HRMS(ESI-TOF):m/z calcd for C 10 H 11 O 2 [M+1] + :163.0754,found 163.0755。
example 12: preparation of 4-acetyl-2-bromobenzaldehyde (Ig)
3 '-bromo-4' -methylacetophenone (107 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio) to give a colorless liquid, 4-acetyl-2-bromobenzaldehyde (Ig) 66mg, yield: 58%, ig has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ10.41(s,1H),8.21(s,1H),8.06-7.92(m,2H),2.64(s,3H). 13 C NMR(125MHz,CDCl 3 )δ191.33,186.19,153.69,137.75,133.83,130.28,127.52,127.26,27.05.HRMS(ESI-TOF):m/z calcd for C 9 H 7 BrO 2 [M+1] + :226.9702,found 226.9705。
example 13: preparation of 4-acetyl-2-nitrobenzaldehyde (Ih)
3-nitro-4-methylacetophenone (90 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio) to give colorless liquid 4-acetyl-2-nitrobenzaldehyde (Ih) 50mg, yield: 52%, ih has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ10.47(s,1H),8.65(s,1H),8.32(d,J＝7.0Hz,1H),8.04(d,J＝7.5Hz,1H),2.72(s,3H). 13 C NMR(125MHz,CDCl 3 )δ194.94,187.57,149.78,141.03,134.21,133.31,130.55,124.35,27.03.HRMS(ESI-TOF):m/z calcd for C 9 H 7 NO 4 [M+1] + :194.0448,found 194.0445。
example 14: preparation of 1- (4-formylphenyl) propan-1-one (Ii)
P-methyl propiophenone (74 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and colorless liquid 1- (4-formylphenyl) propan-1-one (Ii) 65mg was isolated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio), yield: 80%, ii has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ10.10(s,1H),8.10(d,J＝8.6Hz,2H),7.97(d,J＝8.7Hz,2H),3.04(q,J＝7.3Hz,2H),1.24(t,3H). 13 C NMR(125MHz,CDCl 3 )δ200.29,191.79,141.29,139.07,129.97,128.63,32.49,8.17.HRMS(ESI-TOF):m/z calcd for C 10 H 10 O 2 [M+1] + :163.0754,found 163.0758。
example 15: preparation of terephthalaldehyde (Ij)
P-methylbenzaldehyde (60 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio) to give 48mg of terephthalaldehyde (Ij) as a colorless liquid, yield: 71, ij has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ10.14(s,2H),8.06(s,4H). 13 C NMR(125MHz,CDCl 3 )δ191.62,140.18,130.29.HRMS(ESI-TOF):m/z calcd for C 8 H 6 O 2 [M+1] + :135.0441,found 135.0444。
example 16: preparation of 4-benzoylbenzaldehyde (Ik)
4-methylbenzophenone (98 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio) to give colorless liquid 4-benzoyl benzaldehyde (Ik) 68mg, yield: 65%, ik has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ10.13(s,1H),8.00(d,J＝7.5Hz,2H),7.92(d,J＝7.7Hz,2H),7.80(d,J＝7.6Hz,2H),7.63(t,J＝7.3Hz,1H),7.56-7.45(m,2H). 13 C NMR(125MHz,CDCl 3 )δ195.94,191.75,142.69,138.60,136.86,133.26,130.44,130.24,129.62,128.67.HRMS(ESI-TOF):m/z calcd for C 14 H 10 O 2 [M+1] + :211.0754,found 211.0750。
example 17: preparation of 9, 10-dioxo-9, 10-dihydro-anthracene-2-carbaldehyde (Il)
2-methylanthraquinone (111 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and colorless liquid 9, 10-dioxo-9, 10-dihydroanthracene-2-carbaldehyde (Il) 80mg was obtained by separation through silica gel column chromatography (eluent: ethyl acetate=10:1, volume ratio), yield: 68, il has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ10.23(s,1H),8.79(s,1H),8.47(d,J＝7.8Hz,1H),8.40-8.32(m,2H),8.30(d,J＝7.9Hz,1H),7.93-7.79(m,2H). 13 CNMR(125MHz,CDCl 3 )δ190.95,182.56,182.28,140.01,137.05,134.79,134.75,134.30,133.50,133.48,133.22,129.68,128.34,127.66.HRMS(ESI-TOF):m/z calcd for C 15 H 9 O 3 [M+1] + :237.0546,found 237.0548。
example 18: preparation of methyl paraformylbenzoate (Im)
Methyl p-methylbenzoate (75 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio) to give 71mg of methyl p-formylbenzoate (Im) as a colorless liquid, yield: 86%, im is as follows:
1 H NMR(500MHz,CDCl 3 )δ10.10(s,1H),8.19(d,J＝7.9Hz,2H),7.95(d,J＝8.1Hz,2H),3.96(s,3H). 13 C NMR(125MHz,CDCl 3 )δ191.82,166.23,139.29,135.25,130.35,129.68,128.39,52.74.HRMS(ESI-TOF):m/z calcd for C 9 H 9 O 3 [M+1] + :165.0546,found 165.0548。
example 19: preparation of 4-formylbenzamide (In)
Para-toluamide (68 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio) to give colorless liquid 4-formylbenzamide (In) 66mg, yield: 88%, in has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ10.10(s,1H),8.15-7.78(m,4H),6.18(s,1H),5.86(s,1H). 13 C NMR(125MHz,CDCl 3 )δ191.47,169.23,140.98,138.16,129.90,128.08.HRMS(ESI-TOF):m/z calcd for C 8 H 8 NO 2 [M+1] + :150.0550,found 150.0553。
example 20: preparation of ethyl 2- (4-formylphenyl) -2-oxoacetate (Io)
Ethyl-4-methylbenzoyl (96 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent n-hexane: ethyl acetate=10:1, volume ratio) to obtain 77mg of colorless liquid, 2- (4-formylphenyl) -2-oxoethyl acetate (Io), yield: 75%, the structural formula of Io is:
1 H NMR(500MHz,CDCl 3 )δ10.13(s,1H),8.19(d,J＝8.2Hz,2H),8.02(d,J＝8.3Hz,2H),4.48(q,J＝7.2Hz,2H),1.44(t,J＝7.2Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ191.48,185.54,163.06,140.16,136.85,130.76,129.95,62.92,14.23.HRMS(ESI-TOF):m/z calcd for C 11 H 11 O 4 [M+1] + :207.0652,found 207.0655。
example 21: preparation of Parbromobenzaldehyde (Ip)
P-bromotoluene (86 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio) to obtain a colorless liquid, p-bromobenzaldehyde (Ip) 40mg, yield: 43%, ip is as follows:
1 H NMR(500MHz,CDCl 3 )δ9.97(s,1H),7.74(d,J＝8.6Hz,2H),7.68(d,J＝8.1Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ191.18,135.21,132.57,131.10,129.91.HRMS(ESI-TOF):m/z calcd for C 7 H 6 BrO[M+H] + :184.9597,found184.9595。
example 21: preparation of p-nitrobenzaldehyde (Iq)
Para-nitrotoluene (69 mg,0.5 mmol), tetrabutylammonium tetrafluoroborate (165 mg,0.5 mmol) and hexafluoroisopropanol (5 mL) were added to a reaction flask, a reticulated vitreous carbon electrode and a platinum electrode were inserted, the current was adjusted to constant current 5ma, and the mixture was reacted at 25 ℃ for 6 hours, and the mixture was separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate=10:1, volume ratio) to obtain 42mg of colorless liquid para-bromobenzaldehyde (Iq), yield: 56, iq has the structural formula:
1 H NMR(500MHz,CDCl 3 )δ10.16(s,1H),8.39(d,J＝8.3Hz,2H),8.07(d,J＝8.3Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ190.42,151.26,140.18,130.61,124.44.HRMS(ESI-TOF):m/z calcd for C 7 H 6 NO 3 [M+H] + :152.0342,found 152.0344。
finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (1)

1. A preparation method of formyl benzamide comprises the following steps: 68mg of p-toluamide, 0.5mmol, 165mg of tetrabutylammonium tetrafluoroborate, 0.5mmol and 5mL of hexafluoroisopropanol are added into a reaction bottle, a reticular glassy carbon electrode and a platinum electrode are inserted, the current is regulated to be constant current of 5mA, the reaction is carried out for 6 hours at 25 ℃, and the reaction is carried out through silica gel column chromatography, wherein the eluent is n-hexane with the volume ratio: ethyl acetate = 10:1, to obtain a colorless liquid, 66mg of 4-formylbenzamide, yield: 88%, the structural formula is:。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1249362A (en) * 1999-08-25 2000-04-05 福建师范大学 Process for synthesizing o-, meta-, or p-methoxylbenzaldehyde by electrolysis
US6468414B1 (en) * 2001-02-16 2002-10-22 Hydro-Quebec Method of purification of a redox mediator before electrolytic regeneration thereof
CN102600892A (en) * 2012-02-17 2012-07-25 北京工业大学 Application of triarylimidazole compound serving as catalyst in electroorganic synthesis
CN104230688A (en) * 2013-06-24 2014-12-24 淄博职业学院 Catalyzed synthesis method for m-phenoxy benzaldehyde
CN110724107A (en) * 2019-10-17 2020-01-24 浙江工业大学 Preparation method and application of diallyl ionic liquid
KR20210033281A (en) * 2019-09-18 2021-03-26 한국과학기술연구원 Method for preparing benzaldehyde

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1249362A (en) * 1999-08-25 2000-04-05 福建师范大学 Process for synthesizing o-, meta-, or p-methoxylbenzaldehyde by electrolysis
US6468414B1 (en) * 2001-02-16 2002-10-22 Hydro-Quebec Method of purification of a redox mediator before electrolytic regeneration thereof
CN102600892A (en) * 2012-02-17 2012-07-25 北京工业大学 Application of triarylimidazole compound serving as catalyst in electroorganic synthesis
CN104230688A (en) * 2013-06-24 2014-12-24 淄博职业学院 Catalyzed synthesis method for m-phenoxy benzaldehyde
KR20210033281A (en) * 2019-09-18 2021-03-26 한국과학기술연구원 Method for preparing benzaldehyde
CN110724107A (en) * 2019-10-17 2020-01-24 浙江工业大学 Preparation method and application of diallyl ionic liquid

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