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Synthesis method of N, N' -diaryl benzoyl hydrazine compound

A technology of aryl benzoyl hydrazide and synthesis method, which is applied in the field of synthesis of N,N'-diaryl benzoyl hydrazide compounds and can solve the hydroacylation reaction between azobenzene compounds and α-keto acid No problems such as reports have been reported, and the effects of high yield, simple and easy method, and wide application of substrates are achieved.

Active Publication Date: 2020-11-24
GANSU AGRI UNIV
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Problems solved by technology

For the reaction of azobenzene compounds with α-keto acids, the literature has reported the ortho acylation reaction of azobenzene compounds co-catalyzed by palladium or palladium and photocatalyst (Chem. Eur. J. 2013, 19, 14432; J. Org. Chem. 2013, 78, 10414; >Chem. Eur. J. 2016,22,2236), but the hydroacylation reaction of azobenzene compounds with α-keto acids has not been reported

Method used

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  • Synthesis method of N, N' -diaryl benzoyl hydrazine compound
  • Synthesis method of N, N' -diaryl benzoyl hydrazine compound
  • Synthesis method of N, N' -diaryl benzoyl hydrazine compound

Examples

Experimental program
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Effect test

Embodiment 1

[0027] Example 1 A method for synthesizing N,N'-diarylbenzoic hydrazide compounds: the method refers to adding azobenzene 1a (36.4 mg, 0.2 mmol), benzene to dichloromethane (3.0 mL). Formic acid 2a (30.0 mg, 0.2 mmol, 1 equiv) was stirred at room temperature under 15 W blue LED irradiation to react for 24 h (complete reaction was monitored by TLC) to obtain a reaction mixture; the reaction mixture was distilled under reduced pressure to remove the solvent, After silica gel column chromatography, N,N'-diphenylbenzohydrazide (3aa) was obtained.

[0028]

[0029] White solid; yield: 55.9 mg (97%); m.p. 136‒138 ℃.

[0030] 1 H NMR (400 MHz, CDCl 3 ): δ = 7.56 (d, J = 7.6 Hz, 2H), 7.38 (t, J = 7.4Hz, 1H), 7.32–7.24 (m, 8H), 7.16 (t, J = 7.0 Hz, 1H), 7.09(s, 1H), 6.96–6.87(m, 3H).

[0031] 13 C NMR (150 MHz, CDCl 3 ): δ = 170.8, 147.1, 143.1, 134.8, 130.6, 129.2, 128.8, 128.5, 128.0, 126.1, 124.4, 121.2, 113.4.

[0032] HRMS (ESI): m / z [M+H] + calcd for C 19 H 1...

Embodiment 2

[0033] Example 2 A method for synthesizing N,N'-diarylbenzohydrazide compounds: the method refers to adding 4,4'-dimethylazobenzene 1b ( 43.0 mg, 0.2 mmol), benzoylformic acid 2a (30.0 mg, 0.2 mmol, 1 equiv), were stirred at room temperature under 15 W blue LED irradiation until the reaction was completed for 24 h (the reaction was monitored by TLC) to obtain a reaction mixture; The reaction mixture was distilled under reduced pressure to remove the solvent and subjected to silica gel column chromatography to obtain N,N'-bis(p-tolyl)benzohydrazide (3ba).

[0034]

[0035] White solid; Yield: 60.1 mg, (95%); m.p. 125–126 ℃.

[0036] 1 H NMR (600 MHz, CDCl 3 ): δ =7.53 (d, J= 7.8 Hz, 2H), 7.37–7.34 (m, 1H), 7.28–7.25 (m, 2H), 7.15 (d, J = 7.2 Hz, 2H), 7.04 (t, J = 7.5 Hz, 4H), 6.91(s, 1H), 6.86(d, J = 7.8 Hz, 2H), 2.28 (s, 3H), 2.26 (s, 3H).

[0037] 13 C NMR (150 MHz, CDCl 3 ): δ = 170.6, 144.7, 140.6, 136.0, 135.0, 130.7, 130.5, 129.8, 129.4, 128.6, 127.9, 124.6,...

Embodiment 3

[0039] Example 3 A method for synthesizing N,N'-diarylbenzoic hydrazide compounds: this method refers to adding 4,4'-di-n-butylazobenzene 1c to dichloromethane (3.0 mL). (58.9 mg, 0.2 mmol), benzoylformic acid 2a (30.0 mg, 0.2 mmol, 1 equiv), stirred at room temperature under 15 W blue LED irradiation until the reaction was completed for 24 h (the reaction was monitored by TLC) to obtain a reaction mixture ; After the reaction mixture was distilled under reduced pressure to remove the solvent and subjected to silica gel column chromatography, N,N'-bis(4-butylphenyl)benzohydrazide (3ca) was obtained.

[0040]

[0041] White solid; Yield: 68.1 mg (85%); m.p. 69‒70 ℃.

[0042] 1 H NMR (600 MHz, CDCl 3 ): δ = 7.52 (d, J = 7.8 Hz, 2H), 7.34 (t, J = 7.5Hz, 1H), 7.25 (t, J = 7.5 Hz, 2H), 7.17 (d, J = 7.8 Hz, 2H), 7.05 (t, J = 7.2Hz, 4H), 6.91 (s, 1H), 6.88 (d, J = 7.8Hz, 2H), 2.54 (q, J = 8.4 Hz, 4H), 1.57–1.53 (m, 4H), 1.36–1.30 (m, 4H), 0.92 (q, J =8.4 Hz, 6H). ...

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Abstract

The invention relates to a synthesis method of an N, N'-diaryl benzoyl hydrazine compound. The method comprises the following steps: adding an azobenzene compound and alpha-keto acid into dichloromethane, and stirring at room temperature under visible light irradiation until the reaction is complete to obtain a reaction mixture; and performing reduced pressure distillation on the reaction mixtureto remove a solvent, and performing silica gel column chromatography to obtain the N, N'-diaryl benzoyl hydrazine compound. According to the synthesis method disclosed by the invention, a large amountof N, N'-diaryl benzoyl hydrazine compounds are synthesized by virtue of a hydrogen acylation reaction of the azobenzene compound promoted by visible light and the alpha-keto acid for the first time,any catalyst, ligand and additive are avoided, the reaction temperature is room temperature, the yield is high, the atom economy is high, the byproduct is only carbon dioxide, and the requirements ofgreen chemistry and sustainable development are met.

Description

technical field [0001] The invention relates to the technical field of organic chemistry, in particular to a method for synthesizing N,N'-diarylbenzohydrazide compounds. Background technique [0002] Hydrazide compounds are not only widely used in medicine (such as antibacterial, antiviral, bactericidal, anti-inflammatory, anticonvulsant, diuretic, antimalarial, anticancer agents), pesticides and industrial fields (such as corrosion inhibitor), but also Important synthetic intermediates in organic synthesis. Among them, benzoyl hydrazide compounds can be used as enzyme inhibitors, fungicides, anti-tuberculosis and anti-cancer agents, pesticides, and fluorescent sensors. [0003] Benzoic hydrazides are usually prepared by reacting carboxylic acid derivatives such as acid chlorides, acid anhydrides with hydrazine ( Chem. Rev. 2014, 114, 2942). However, on the one hand, this method needs to use strong corrosive or toxic reagents, and the reaction conditions are relatively...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C241/04C07C243/38
CPCC07C241/04C07C243/38
Inventor 周红艳杨靖亚宋梦辉
Owner GANSU AGRI UNIV
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