Gamma-hydrazino cyanide compound and synthesis method thereof

A technology for a cyanide compound and a synthesis method, which is applied in the field of γ-hydrazine cyanide compounds and the synthesis thereof, can solve problems such as blank synthesis methods, and achieve the effects of simple operation, mild reaction conditions and strong compatibility

Active Publication Date: 2021-03-09
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] The present invention aims at overcoming the blank problem of the synthesis method of gamma-hydrazino cyanide c

Method used

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  • Gamma-hydrazino cyanide compound and synthesis method thereof
  • Gamma-hydrazino cyanide compound and synthesis method thereof
  • Gamma-hydrazino cyanide compound and synthesis method thereof

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preparation example Construction

[0055] A kind of synthetic method of described gamma-hydrazine cyanide compound comprises following synthetic steps:

[0056] (1) Under inert gas protection conditions, azodicarboxylate and α-iminooxy acid are mixed and dissolved in a solvent (acetonitrile, tetrahydrofuran, toluene, acetone, 1,4-dioxane, dichloromethane, 1,2-dichloroethane or N,N-dimethylformamide), under the action of cerium chloride heptahydrate and alkali (cesium carbonate, potassium carbonate or sodium carbonate), react for 36-48h to obtain the formula The γ-hydrazine cyanide of structure shown in I; The ratio of the amount of substance of described α-iminooxyacid, azodicarboxylate, catalyst, alkali is 1: 1-3: 0.05-0.15: 0.2- 1;

[0057] The α-iminooxyacid has a structure shown in formula II:

[0058]

[0059]

[0060] Wherein, the definitions of R1, R2, Y and n are consistent with those in the formula I.

[0061] The azodicarboxylate has the structure shown in formula III~1-III~4:

[0062]

...

Embodiment 1

[0066]

[0067] 2-((cyclobutenylamino)oxy)-2-methylpropionic acid (34.2mg, 0.2mmol), di-tert-butyl azodicarboxylate (69.1mg, 0.3mmol), cerium chloride heptahydrate (7.4mg, 0.02mmol) and potassium carbonate (5.5mg, 0.04mmol) were added to an argon-protected reaction flask, and finally acetonitrile (2.0mL) was added, and then reacted at room temperature under 460nm blue light for 48h. Chromatography (eluent: petroleum ether / ethyl acetate volume ratio 5:1) isolated 42.1 mg with a yield of 70%.

[0068] like figure 1 As shown, product characterization: white solid; m.p.59-60°C; 1H NMR (500MHz, CDCl3) δ6.49(m, 1H), 3.52(m, 2H), 2.43(m, 2H), 1.88(t, J =6.35Hz, 2H), 1.43(s, 18H)

Embodiment 2

[0070]

[0071] 2-Methyl-2-(((3-phenylcyclobutenyl)amino)oxy)propanoic acid (49.4mg, 0.2mmol), di-tert-butyl azodicarboxylate (69.1mg, 0.3mmol) , cerium chloride heptahydrate (7.4mg, 0.02mmol) and potassium carbonate (5.5mg, 0.04mmol) were added to the reaction flask protected by argon, and finally acetonitrile (2.0mL) was added, and then reacted at room temperature under 460nm blue light for 48h , after the reaction, separated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio of 5:1) to obtain 51.4mg, the yield was 68%.

[0072] like figure 2 As shown, product characterization: brown oil; 1H NMR (500MHz, CDCl3) δ7.36-7.24 (m, 5H), 6.65-6.54 (m, 1H), 3.99 (m, 1H), 3.61-3.49 (m, 1H ), 3.32 (s, 1H), 2.90-2.68 (m, 2H), 1.46 (t, J=8.5Hz, 18H).

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Abstract

The invention relates to the technical field of organic synthesis, and discloses a gamma-hydrazino cyanide compound and a synthesis method thereof, aiming at the problem that the synthesis method of the gamma-hydrazino cyanide compound in the prior art is blank, and the synthesis method comprises the steps: (1) under the protection of inert gas, mixing azodicarboxylate and alpha-imino oxoacid, dissolving in a solvent, and reacting under the action of a catalyst and alkali, to obtain gamma-hydrazino cyanide with the structure shown in the formula I; and (2) carrying out post-treatment on the reaction product to obtain a finished product. The gamma-hydrazino cyanide compound and the synthesis method thereof have the beneficial effects that (1) cerium trichloride which is low in price and easy to obtain is used as a photocatalyst, so that other expensive photocatalysts are prevented from being used; (2) the reaction only needs a catalytic amount of alkali, the reaction conditions are mild, the operation is simple, and the compatibility of substrate functional groups is strong; and (3) a high-activity imine free radical intermediate is generated by utilizing an LMCT strategy, and a hydrazination reaction is developed, so that an efficient and simple method is provided for introducing a long-chain cyano functional group into an organic small molecular compound.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a gamma-hydrazino cyanide compound and a synthesis method thereof. Background technique [0002] Hydrazine derivatives are widely used in pharmaceutical, agricultural, photographic and dye industries, as well as precursors of heterocyclic compounds (such as pyrazole, pyrazine, indole, etc.). Hydrazine unit fragments exist in many pharmacologically active compounds, such as phenelzine, prochlorhydrazine, saffron, etc. Among them, the antiretroviral atazanavir has been proved to have significant curative effect in the treatment of HIV-1 infection, and the dopa decarboxylase inhibitor benserazide has been used in the treatment of Parkinson's disease. [0003] [0004] Ligand-metal charge transfer (LMCT) catalytic strategy is to use light energy to efficiently realize the oxidation of organic molecules through the photocatalytic ligand-to-metal electronic transition pat...

Claims

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Application Information

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IPC IPC(8): C07C281/02B01J23/10
CPCC07C281/02B01J23/10B01J35/004C07C2602/08
Inventor 李小青闫晓雨许响生
Owner ZHEJIANG UNIV OF TECH
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