CN113956174A - One-pot reduction acylation method of light-induced nitro compound - Google Patents

One-pot reduction acylation method of light-induced nitro compound Download PDF

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CN113956174A
CN113956174A CN202111406586.8A CN202111406586A CN113956174A CN 113956174 A CN113956174 A CN 113956174A CN 202111406586 A CN202111406586 A CN 202111406586A CN 113956174 A CN113956174 A CN 113956174A
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nitro compound
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CN113956174B (en
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夏远志
陈佳佳
陈建辉
罗燕书
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Wenzhou University
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Abstract

The invention discloses a one-pot reduction acylation method of a photoinduced nitro compound, which comprises the following steps: adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 6-15 hours at room temperature, and after the reaction is finished, sequentially performing post-treatment and silica gel chromatographic column purification to obtain the amide compound. The invention has the following advantages: (1) the raw materials are cheap and easy to obtain; (2) the range of the substrate is wide; (3) no additional photosensitizer or catalyst is needed; (4) the reaction condition is mild, and the operation is simple; (5) the reaction yield is high.

Description

One-pot reduction acylation method of light-induced nitro compound
Technical Field
The invention relates to a one-pot reduction acylation method of a photoinduced nitro compound, belonging to the field of green organic synthesis.
Background
Amides are a very important class of organic molecules, which are widely found in natural products, pharmaceuticals, and pesticides. The condensation reaction of carboxylic acids or carboxylic acid derivatives with amine compounds is a traditional method for the construction of amide bonds. The nitro compound is a main precursor of the amine compound, has the characteristics of simple synthesis, low price, easy obtaining and the like, and has important significance in the aspects of theory, production and application when the amide compound is prepared by reducing and acylating the nitro compound.
In 2015, Hosseini-Sarvari et al disclosed a Pd/ZnO nanoparticle catalyzed nitro reduction reaction and a one-pot amide synthesis reaction (appl. surf. Sci. 2015,324, 265-274). Hydrazine hydrate is used as a reducing agent in the reaction, and a series of amine compounds are obtained under the catalysis of Pd/ZnO nano particles. If acetic acid is further added into the system, the amine compound can be subjected to acylation reaction to obtain the acetamide compound, and the reaction formula is as follows:
Figure BDA0003372479640000011
in the same year, Kazemi et al disclose a TiO2-P25-catalyzed one-pot reductive acylation of nitro compounds (J.Photochem.Photobiol.B-biol.2015,152, 58-62). The reaction takes ethanol as a reducing agent and acetic anhydride as an acylating reagent, and synthesizes a series of acetamide compounds under the induction of sunlight, wherein the reaction formula is as follows:
Figure BDA0003372479640000021
in 2020, Ochoa-Puentes et al expressed as SnCl2·2H2O is a reducing agent, acid anhydride is an acylating agent, and the conversion of the nitro compound into acetamide is realized by a one-pot two-step method (RSC adv.,2020,10(66), 40552-:
Figure BDA0003372479640000022
2021, Wu et al disclosed a Rh catalyzed amide synthesis by nitro reductive acylation (chem. Commun.,2021,57(15), 1955-1958). Under the participation of Rh catalyst, tungsten hexacarbonyl and water, nitro is firstly reduced into amino, and then under the catalysis of Rh, dimethyl carbonate is used as an acyl precursor to acidylate the amino, wherein the reaction formula is as follows:
Figure BDA0003372479640000023
as described above, although methods for synthesizing amide compounds from nitro compounds by reduction-acylation methods have been reported, these methods generally require the reduction of nitro groups under the action of a metal catalyst, and then react with an additionally added acylating agent to obtain a product, which has disadvantages of more reaction steps, complex conditions, and the like. Therefore, the development of a novel efficient method for reductive acylation of nitro compounds is an urgent problem to be solved.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a one-pot reduction acylation method of a photoinduced nitro compound. According to the method, a nitro compound which is cheap and easy to obtain is directly used as a raw material, thiocarboxylic acid is used as a reducing agent and an acyl source, a series of amide compounds are efficiently synthesized through a one-pot reaction, no additional photosensitizer is needed in the reaction, the process is simple, and the yield is high. The raw materials of the reaction are simple and easy to obtain, and a metal catalyst is not needed, so that the green and efficient synthesis of the series of amide compounds is realized.
The technical scheme is as follows: the one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 6-15 hours at room temperature, and after the reaction is finished, sequentially performing aftertreatment and silica gel chromatographic column purification to obtain an amide compound, wherein:
the molar ratio of the nitro compound, the thiocarboxylic acid and the ammonium bicarbonate is 1: 2-6: 1-3;
the dosage of the solvent is 3-8 mL/mmol based on the molar weight of the nitro compound.
Further, the structural formula of the nitro compound is R1-NO2Wherein R is1Is phenyl or phenyl containing substituent.
Furthermore, the substituent of the phenyl group containing the substituent is one of alkyl, alkoxy, halogen, carbonyl, hydroxyl and cyano.
Further, the structure formula of the thiocarboxylic acid is R2COSH, wherein R2Alkyl, phenyl containing substituent, heterocycle.
Furthermore, the substituent in the phenyl containing the substituent is one of alkyl, alkoxy, halogen, acyl and ester group;
the heterocycle is one of pyridyl, furyl, thienyl and indolyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the solvent is one of tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, toluene, dichloromethane and water, and tetrahydrofuran is preferred.
Further, the additive is any one of triethylamine, ammonium acetate, ammonium formate, potassium carbonate, potassium bicarbonate and ammonium bicarbonate, and preferably ammonium bicarbonate.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
In the reaction system, the nitro compound is activated by light induction, so that the oxidability of the nitro compound is enhanced, the nitro compound is subjected to reduction reaction under the action of thiocarboxylic acid to obtain an amino compound, and the amino compound is further subjected to nucleophilic substitution reaction with thiocarboxylic acid in the system to realize acylation reaction.
Has the advantages that: the one-pot reduction acylation method of the photoinduced nitro compound disclosed by the invention has the following beneficial effects:
(1) the raw materials are cheap and easy to obtain;
(2) the range of the substrate is wide;
(3) no additional photosensitizer or catalyst is needed;
(4) the reaction condition is mild, and the operation is simple;
(5) the reaction yield is high.
Description of the drawings:
FIG. 1 is a flow chart of a one-pot reduction acylation method of a photoinduced nitro compound disclosed by the invention.
The specific implementation mode is as follows:
the following describes in detail specific embodiments of the present invention.
The reaction formula of the invention is as follows:
Figure BDA0003372479640000051
wherein: the structural formula of the nitro compound is R1-NO2Wherein R is1Is phenyl or phenyl containing substituent;
the substituent in the substituent-containing phenyl is one of alkyl, alkoxy, halogen, carbonyl, hydroxyl and cyano.
The structure of the thiocarboxylic acid is R2COSH, wherein R2Is alkyl, phenyl containing substituent, heterocycle;
the substituent in the substituent-containing phenyl is one of alkyl, alkoxy, halogen, acyl and ester group;
the heterocycle is one of pyridine, furan, thiophene and indole.
Example 1
Figure BDA0003372479640000052
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction vessel, irradiating by using an LED lamp under the protection of nitrogen, reacting for 12 hours at room temperature, and after the reaction is finished, carrying out aftertreatment and silica gel chromatographic column purification to obtain a corresponding amide compound, wherein the yield is 87%, and the method comprises the following steps:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is phenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ7.98(s,1H),7.50(d,J＝7.8Hz,2H),7.28(t,J＝7.9Hz,2H),7.08(t,J＝7.4Hz,1H),2.13(s,3H)。
example 2
Figure BDA0003372479640000061
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 12 hours at room temperature, and after the reaction is finished, carrying out post-treatment and purification by using a silica gel chromatographic column to obtain the corresponding amide compound. The yield was 85%, where:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 2: 1;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 4-methylphenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(400MHz,CDCl3)δ7.50(s,1H),7.37(d,J＝8.3Hz,2H),7.10(d,J＝8.1Hz,2H),2.30(s,3H),2.14(s,3H)。
example 3
Figure BDA0003372479640000071
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 12 hours at room temperature, and after the reaction is finished, carrying out post-treatment and purification by using a silica gel chromatographic column to obtain the corresponding amide compound. The yield was 87%, wherein:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 3-methylphenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ7.83(s,1H),7.34(s,1H),7.28(d,J＝8.0Hz,1H),7.17(t,J＝7.8Hz,1H),6.90(d,J＝7.5Hz,1H),2.30(s,3H),2.13(s,3H)。
example 4
Figure BDA0003372479640000081
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, and reacting for 12 hours at room temperature. After the reaction is finished, the corresponding amide compound is obtained after post-treatment and silica gel chromatographic column purification. The yield was 57%, wherein:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 2-methylphenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ7.71(d,J＝7.9Hz,1H),7.23–7.15(m,2H),7.08(t,J＝7.4Hz,2H),2.24(s,3H),2.18(s,3H)。
example 5
Figure BDA0003372479640000091
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, and reacting for 12 hours at room temperature. After the reaction is finished, the corresponding amide compound is obtained after post-treatment and silica gel chromatographic column purification. The yield was 82%, where:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 4-ethylphenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ7.82(s,1H),7.40(d,J＝8.3Hz,2H),7.11(d,J＝8.2Hz,2H),2.59(q,J＝7.6Hz,2H),2.13(s,3H),1.20(t,J＝7.6Hz,3H)。
example 6
Figure BDA0003372479640000101
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction vessel, irradiating by using an LED lamp under the protection of nitrogen, reacting for 12 hours at room temperature, and after the reaction is finished, carrying out aftertreatment and silica gel chromatographic column purification to obtain a corresponding amide compound, wherein the yield is 90 percent:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 4-methoxyphenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ7.51(s,1H),7.38(d,J＝8.9Hz,2H),6.83(d,J＝8.9Hz,2H),3.78(s,3H),2.13(s,3H).
example 7
Figure BDA0003372479640000111
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 12 hours at room temperature, and after the reaction is finished, carrying out post-treatment and purification by using a silica gel chromatographic column to obtain the corresponding amide compound. The yield was 84%, where:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 4-fluorophenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ7.58(s,1H),7.44(dd,J＝8.9,4.8Hz,2H),6.99(t,J＝8.6Hz,2H),2.15(s,3H)。
example 8
Figure BDA0003372479640000121
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 12 hours at room temperature, and after the reaction is finished, carrying out post-treatment and purification by using a silica gel chromatographic column to obtain the corresponding amide compound. The yield was 81%, wherein:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 4-chlorophenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,DMSO)δ10.07(s,1H),7.62(d,J＝8.8Hz,2H),7.34(d,J＝8.8Hz,2H),2.05(s,3H)。
example 9
Figure BDA0003372479640000131
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction vessel, irradiating by using an LED lamp under the protection of nitrogen, reacting for 12 hours at room temperature, and after the reaction is finished, carrying out aftertreatment and silica gel chromatographic column purification to obtain a corresponding amide compound with the yield of 73%, wherein:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 4-methylphenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is phenyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ7.92(s,1H),7.84(d,J＝7.8Hz,2H),7.54–7.48(m,3H),7.44(t,J＝7.5Hz,2H),7.14(d,J＝8.1Hz,2H),2.33(s,3H)。
example 10
Figure BDA0003372479640000141
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, and reacting for 12 hours at room temperature. After the reaction is finished, the corresponding amide compound is obtained through post-treatment and silica gel chromatographic column purification, wherein the yield is 63 percent:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 4-methylphenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is 4-methylphenyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ7.87(s,1H),7.75(d,J＝8.0Hz,2H),7.51(d,J＝8.2Hz,2H),7.24(d,J＝8.2Hz,2H),7.14(d,J＝8.2Hz,2H),2.40(s,3H),2.32(s,3H)。
example 11
Figure BDA0003372479640000151
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, and reacting for 12 hours at room temperature. After the reaction is finished, the corresponding amide compound is obtained through post-treatment and silica gel chromatographic column purification, and the yield is 59%, wherein:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 4-methylA phenyl group.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is 2-furyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ8.01(s,1H),7.52(d,J＝8.1Hz,2H),7.49(s,1H),7.21(d,J＝2.7Hz,1H),7.15(d,J＝7.9Hz,2H),6.54(d,J＝1.6Hz,1H),2.33(s,3H)。
example 12
Figure BDA0003372479640000161
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a tetrahydrofuran solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 12 hours at room temperature, and after the reaction is finished, carrying out post-treatment and purification by using a silica gel chromatographic column to obtain the corresponding amide compound. The yield was 86%, wherein:
the molar ratio of the nitro compound to the thiocarboxylic acid to the ammonium bicarbonate is 1: 4: 2;
the dosage of the organic solvent is 5mL/mmol based on the molar amount of the nitro compound;
the structural formula of the nitro compound is R1-NO2Wherein R is1Is 4-methylphenyl.
The thiocarboxylic acid has the formula R2COSH, wherein R2Is phenethyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(500MHz,CDCl3)δ7.31–7.25(m,4H),7.22–7.16(m,3H),7.06(d,J＝8.1Hz,2H),3.01(t,J＝7.6Hz,2H),2.61(t,J＝7.7Hz,2H),2.28(s,3H).
example 13
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 6 hours at room temperature, and after the reaction is finished, sequentially performing aftertreatment and silica gel chromatographic column purification to obtain an amide compound, wherein:
the molar ratio of the nitro compound, the thiocarboxylic acid and the ammonium bicarbonate is 1: 2: 1;
the amount of the solvent used was 3mL/mmol based on the molar amount of the nitro compound.
Further, the structural formula of the nitro compound is R1-NO2Wherein R is1Is phenyl.
Further, the structure formula of the thiocarboxylic acid is R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the solvent is tetrahydrofuran.
Further, the additive is ammonium bicarbonate.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
Example 14
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 15 hours at room temperature, and after the reaction is finished, sequentially performing aftertreatment and silica gel chromatographic column purification to obtain an amide compound, wherein:
the molar ratio of the nitro compound, the thiocarboxylic acid and the ammonium bicarbonate is 1: 6: 3;
the amount of the solvent used was 8mL/mmol based on the molar amount of the nitro compound.
Further, the structural formula of the nitro compound is R1-NO2Wherein R is1Is benzyl.
Further, the structure formula of the thiocarboxylic acid is R2COSH, wherein R2Is a pyridyl group.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the solvent is acetonitrile.
Further, the additive is ammonium acetate.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
Example 15
The one-pot reduction acylation method of the light-induced nitro compound comprises the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 8 hours at room temperature, and after the reaction is finished, sequentially performing aftertreatment and silica gel chromatographic column purification to obtain an amide compound, wherein:
the molar ratio of the nitro compound, the thiocarboxylic acid and the ammonium bicarbonate is 1: 4: 2;
the amount of the solvent is 5mL/mmol based on the molar amount of the nitro compound.
Further, the structural formula of the nitro compound is R1-NO2Wherein R is1Is phenyl.
Further, the structure formula of the thiocarboxylic acid is R2COSH, wherein R2Is methyl.
Further, the LED lamp is a purple LED lamp, and the wavelength of the purple LED lamp is 390 nm.
Further, the solvent is 1, 4-dioxane.
Further, the additive is potassium carbonate.
Further, the work-up was dichloromethane extraction and magnesium sulfate drying.
Further, the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
Examples 16 to 24
Is substantially the same as example 13 except that R1The difference is as follows:
R1
example 16 Benzyl radical
Example 17 Phenylethyl group
Example 18 2-methoxyphenyl radical
Example 19 3-methoxyphenyl radical
Example 20 2-chlorophenyl group
Example 21 3-fluorophenyl group
Example 22 4-hydroxyphenyl group
Example 23 4-cyanophenyl group
Example 24 N, N-dimethylcarbamoyl
Examples 25 to 40
Is substantially the same as example 13 except that R2The difference is as follows:
Figure BDA0003372479640000201
Figure BDA0003372479640000211
examples 41 to 46
Same as example 13, except that the solvent was different:
solvent(s)
EXAMPLE 41 Acetonitrile
Example 42 1, 4-dioxane
Example 43 N, N-dimethylformamide
Example 44 Toluene
Example 45 Methylene dichloride
Example 46 Water (W)
Examples 47 to 51
The same as example 13, except for the additives:
additive agent
Example 47 Triethylamine
Example 48 Ammonium acetate
Example 49 Ammonium formate
Example 50 Potassium carbonate
Example 51 Potassium bicarbonate
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (10)

1. The one-pot reduction acylation method of the light-induced nitro compound is characterized by comprising the following steps:
adding a nitro compound, thiocarboxylic acid, ammonium bicarbonate and a solvent into a reaction container, irradiating by using an LED lamp under the protection of nitrogen, reacting for 6-15 hours at room temperature, and after the reaction is finished, sequentially performing aftertreatment and silica gel chromatographic column purification to obtain an amide compound, wherein:
the molar ratio of the nitro compound, the thiocarboxylic acid and the ammonium bicarbonate is 1: 2-6: 1-3;
the dosage of the solvent is 3-8 mL/mmol based on the molar weight of the nitro compound.
2. The method for one-pot reductive acylation of a light-induced nitro compound as claimed in claim 1, wherein the nitro compound has the formula R1-NO2Wherein R is1Is phenyl or phenyl containing substituent.
3. The method for one-pot reductive acylation of a light-induced nitro compound as claimed in claim 2, wherein the substituent of the substituent-containing phenyl group is one of alkyl, alkoxy, halogen, carbonyl, hydroxy, and cyano.
4. The method for one-pot reductive acylation of a light-induced nitro compound of claim 1 wherein said thiocarboxylic acid has the formula R2COSH, wherein R2Alkyl, phenyl containing substituent, heterocycle.
5. The method for one-pot reductive acylation of a light-induced nitro compound as claimed in claim 4, wherein the substituent of said substituent-containing phenyl group is one of alkyl, alkoxy, halogen, acyl, and ester group;
the heterocycle is one of pyridyl, furyl, thienyl and indolyl.
6. The method for one-pot reductive acylation of a light-induced nitro compound as claimed in claim 1, wherein said LED lamp is a violet LED lamp with a wavelength of 390 nm.
7. The method for one-pot reductive acylation of a light-induced nitro compound according to claim 1, wherein the solvent is one of tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, toluene, dichloromethane, water, preferably tetrahydrofuran.
8. The method for one-pot reductive acylation of a light-induced nitro compound as claimed in claim 1, wherein said additive is any one of triethylamine, ammonium acetate, ammonium formate, potassium carbonate, potassium bicarbonate, ammonium bicarbonate, preferably ammonium bicarbonate.
9. The method for one-pot reductive acylation of a light-induced nitro compound as claimed in claim 1 wherein the work-up is dichloromethane extraction and magnesium sulfate drying.
10. The one-pot reductive acylation method of light-induced nitro compounds according to claim 1, wherein the specific steps of silica gel chromatographic column purification are as follows:
packing a chromatographic column;
sampling;
eluting with ethyl acetate/petroleum ether eluent.
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