Method for synthesizing imino benzotriazole compound under photocatalysis condition

A technology of imino benzotriazoles and benzotriazoles, which is applied in the field of compound preparation, can solve the problems of harsh reaction conditions and need metal catalysts, and achieves the effects of improving yield, improving protonation process and wide sources.

Pending Publication Date: 2022-08-02
HENAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] In order to solve the existing problems of harsh reaction conditions and the need for metal catalysts for the synthesis of iminobenzotriazole compounds, the present invention provides a method for synthesizing

Method used

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  • Method for synthesizing imino benzotriazole compound under photocatalysis condition
  • Method for synthesizing imino benzotriazole compound under photocatalysis condition
  • Method for synthesizing imino benzotriazole compound under photocatalysis condition

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Example 1 Preparation of N-ethyl acetate-1-benzotriazolyl-2-methylimine

[0038] A 10 mL Schlenk tube was added with a magnetic stirrer, followed by 0.4 mmol of benzotriazole (CAS: 95-14-7) and 1.2 mmol of ethyl diazoacetate (CAS: 623-73-4) , 1.6 mmol of methanol (CAS: 67-56-1), and finally 4 mL of acetonitrile (CAS: 75-05-8) was added.

[0039] By using a double-row tube, a 10 mL Schlenk tube was filled with argon; stirred with a magnetic stirrer, irradiated with a blue LED (445 nm) light and heated to 60 °C for 12 h, the final product was detected by TLC, and finally separated by column chromatography The final product N-ethyl acetate-1-benzotriazolyl-2-methylimine was obtained in 83% yield. The reaction equation is as follows:

[0040]

[0041] The NMR spectrum of N-ethyl acetate-1-benzotriazolyl-2-methylimine is characterized as follows:

[0042] 1 H NMR (300MHz, CDCl 3 )δ8.57(d,J=8.3Hz,1H),8.05(d,J=8.3Hz,1H),7.55(t,J=7.7Hz,1H),7.41(t,J=7.7Hz,1H) ,4.43(s,2H...

Embodiment 2

[0045] The preparation of embodiment two N-benzyl acetate-1-benzotriazolyl-2-methylimine

[0046]A 10 mL Schlenk tube was added with a magnetic stir bar, followed by 0.4 mmol of benzotriazole, 1.2 mmol of benzyl diazoacetate, 1.6 mmol of methanol, and finally 4 mL of acetonitrile.

[0047] By using a double-row tube, a 10 mL Schlenk tube was filled with argon; stirred with a magnetic stirrer, irradiated with a blue LED (445 nm) light and heated to 60 °C for 12 h, the final product was detected by TLC, and finally separated by column chromatography The final product N-benzyl acetate-1-benzotriazolyl-2-methylimine was obtained in 65% yield. (Benzyl diazoacetate is a reference synthesis (Photocatalyticgem-Difluoroolefination Reactions by a Formal C-C Coupling / Defluorination Reaction with Diazoacetates.Angew.Chem.Int.Ed.10.1002 / anie.202111892)) reaction equation is as follows:

[0048]

[0049] The NMR spectrum of N-benzyl acetate-1-benzotriazolyl-2-methylimine is characterize...

Embodiment 3

[0053] Example 3 Preparation of N-propynyl acetate-1-benzotriazolyl-2-methylimine

[0054] A 10 mL Schlenk tube was added with a magnetic stir bar, then 0.4 mmol of benzotriazole, 1.2 mmol of propynyl diazoacetate, 1.6 mmol of methanol, and finally 4 mL of acetonitrile.

[0055] By using a double-row tube, a 10 mL Schlenk tube was filled with argon; stirred with a magnetic stirrer, irradiated with a blue LED (445 nm) light and heated to 60 °C for 12 h, the final product was detected by TLC, and finally separated by column chromatography The final product N-propynyl acetate-1-benzotriazolyl-2-methylimine was obtained in 61% yield. (Propynyl diazoacetate is a reference synthesis (N,N'-Ditosylhydrazine:A Convenient Reagent for Facile Synthesis of Diazoacetates.Org.Lett.2007,9,3195-3197)) The reaction equation is as follows:

[0056]

[0057] The H NMR characterization of N-propynyl acetate-1-benzotriazolyl-2-methylimine is as follows:

[0058] 1 H NMR (300MHz, CDCl 3 )δ8.6...

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Abstract

The invention belongs to the technical field of compound preparation, and discloses a method for synthesizing an imino benzotriazole compound under a photocatalytic condition, which comprises the following steps: by taking benzotriazole as shown in a formula I and diazoacetate as shown in a formula II as raw materials, reacting under the action of an additive and a solvent, thereby obtaining the imino benzotriazole compound. And reacting under the conditions of inert atmosphere and illumination to synthesize the imino benzotriazole compound as shown in the formula III. Under the illumination condition, benzotriazole, diazoacetate and nitriles are synthesized into the imino benzotriazole compound in one step. The raw materials used in the method are wide in source and low in price, and do not need to be treated too much. The whole reaction is carried out under an illumination condition, needs to be heated at a relatively low temperature, and is green and environment-friendly.

Description

technical field [0001] The invention belongs to the technical field of compound preparation, and relates to a method for synthesizing iminobenzotriazole compounds under photocatalytic conditions. Background technique [0002] Benzotriazole unit is a special compound containing a heterocyclic structure, which has been used in the synthesis of drugs or functional materials, and is widely used in organic synthesis. The synthesis of such compounds involves the regioselective N-alkylation of benzotriazoles because N 1 and N 2 Tautomeric equilibrium between benzotriazoles, this alkylation remains challenging because N is often obtained 1 and N 2 A mixture of alkylation products. Nevertheless, great progress has been made in the selective N-alkylation of benzotriazoles. Imidinobenzotriazoles are a class of nitrogen-containing heterocyclic compounds with good biomedical activity, which have shown good biological activities in anti-inflammatory, anti-tumor and anti-diabetic aspe...

Claims

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Application Information

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IPC IPC(8): C07D249/18C07D409/12
CPCC07D249/18C07D409/12Y02P20/584
Inventor 李盼赵静静朱柯勇
Owner HENAN UNIVERSITY
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