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Synthesis method of novel azacycloheptene

A technology of heterocycloheptenes and synthesis methods, which is applied in the field of synthesis of novel azepines, and can solve problems such as no literature reports

Pending Publication Date: 2021-12-21
CHENGDU UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] As far as we know, there is no literature report similar to this application

Method used

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  • Synthesis method of novel azacycloheptene

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Experimental program
Comparison scheme
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Embodiment 1

[0010] (E)-N'-benzylidene-4-toluenesulfonyl hydrazide (1mmol, 1.0equiv), bis(dibenzylideneacetone) palladium (0.05mmol, 0.05equiv) and triphenylphosphine (0.2mmol, 0.2 equiv) into an oven-dried 25mL test tube with a standard grinder fitting and equipped with a stir bar. After sealing the test tube with a rubber stopper and tape, the air in the test tube was evacuated with a vacuum pump, and then argon gas was injected (repeated 3 times). Then diethyl 2-vinylcyclopropane-1,1-dicarboxylate (1 mmol, 1 equiv) was dissolved in THF (5 mL), and injected into the test tube with a syringe. The reaction was stirred at high speed at room temperature. It was detected by TCL, and after the reaction was complete, the reaction mixture was quenched by adding saturated NaCl solution (10 mL). The reaction mixture was extracted with ethyl acetate (15 mL×3). Combined organic phases with MgSO 4 Dry, filter and concentrate under reduced pressure on a rotary evaporator. The resulting residue wa...

Embodiment 2

[0017] (E)-N'-(4-bromobenzylidene)-4-toluenesulfonylhydrazide replaces (E)-N'-benzylidene-4-toluenesulfonylhydrazide in Example 1 to obtain light Yellow waxy solid 2-(4-bromophenyl)-1-((4-methylphenyl)sulfonylamino)-1,2,4,7-tetrahydro-3H-aza-3,3- Diethyl dicarboxylate, the yield is 64.68%.

[0018] 1 H NMR (400MHz, Chloroform-d) δ7.79(d, J=8.0Hz, 2H), 7.60(s, 1H), 7.49(s, 4H), 7.30(d, J=8.0Hz, 2H), 5.65 (dt, J=14.3,6.8Hz,1H),5.52(dt,J=15.5,5.1Hz,1H),4.29(d,J=5.0Hz,2H),4.12(p,J=7.2Hz,4H) ,3.33(t,J=7.4Hz,1H),2.59(t,J=7.2Hz,2H),2.41(s,3H),1.21(t,J=7.1Hz,6H).

[0019] 13 C NMR(101MHz,Chloroform-d)δ168.63,144.20,143.39,134.78,133.22,131.79,129.85,129.60,128.74,128.11,126.17,124.08,61.56,61.47,61.38,51.53,48.98,31.26,14.09,14.04HRMS( ESI)m / z[M+H] + Calcd for C 25 h 30 BrN 2 o 6 S + 565.1002,found565.0988.HRMS(ESI)m / z[M+Na] + Calcd for C 25 h 29 BrN 2 NaO 6 S+ 587.0822,found 587.0810

Embodiment 3

[0021] (E)-N'-(4-ethynylbenzylidene)-4-toluenesulfonylhydrazide replaces (E)-N'-benzylidene-4-toluenesulfonylhydrazide in Example 1 to obtain light brown Gummy solid 2-(4-ethynylphenyl)-1-((4-methylphenyl)sulfonylamino)-1,2,4,7-tetrahydro-3H-aza-3,3- Diethyl dicarboxylate, the yield is 37.06%.

[0022] 1H NMR (400MHz, Chloroform-d) δ7.80(d, J=8.1Hz, 2H), 7.65–7.52(m, 3H), 7.47(d, J=8.0Hz, 2H), 7.30(d, J= 8.1Hz, 2H), 5.71–5.60(m, 1H), 5.52(dt, J=15.6, 5.0Hz, 1H), 4.32(d, J=4.9Hz, 2H), 4.22–4.01(m, 4H), 3.34(t, J=7.4Hz, 1H), 3.18(s, 1H), 2.59(t, J=7.2Hz, 2H), 2.41(d, J=15.7Hz, 3H), 1.20(t, J=7.1 Hz,6H).

[0023] 13 C NMR(101MHz,Chloroform-d)δ168.68,144.21,143.53,134.80,134.54,132.36,129.85,129.60,128.15,127.14,123.49,83.33,78.93,78.91,61.53,51.56,51.54,48.98,31.27,14.08,14.04 .

[0024] HRMS(ESI)m / z[M+H] + Calcd for C 27 h 31 N 2 o 6 S + 511.1897,found 511.1886

[0025] HRMS(ESI)m / z[M+Na] + Calcd for C 27 h 30 N 2 NaO 6 S + 533.1717,found 533.1703

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Abstract

Highly functionalized nitrogen-containing heterocyclic compounds widely exist in natural products, bioactive molecules and chiral drug molecules. However, traditional methods for obtaining the products have the defects of harsh conditions, limited substrate range and the like, and hinder the realization of potential applicability of the products. The invention develops an efficient, simple and convenient synthesis method of azacycloheptene. Under the argon protection condition, tetrahydrofuran is used as a solvent, vinyl cyclopropane and p-toluenesulfonylhydrazone are subjected to a [5+2] cycloaddition reaction, and azacycloheptene is synthesized in a wide substrate range with medium to good yield. The method has the advantages of mild reaction conditions, simplicity in operation, high reaction efficiency, great potential application value and the like.

Description

technical field [0001] The patent involves the research fields of organic synthesis, drug synthesis, and organic chemical industry. The specific method is to carry out vinyl cyclopropane and p-toluenesulfonylhydrazone in tetrahydrofuran under the action of bisdibenzylideneacetone palladium and triphenylphosphine. [5+2] One-step synthesis of azepine by cycloaddition reaction. Background technique [0002] Highly functionalized nitrogen-containing heterocycles are an important branch of organic chemistry. They are natural products, bioactive molecules [1] and chiral drug molecules (Yu, J.; Shi, F.; Gong, L.-Z., Asymmetric Multicomponent Reactions for the Facile Synthesis of Highly Enantioenriched Structurally Diverse Nitrogenous Heterocycles. Accounts of Chemical Research 2011, 44(11), 1156-1171). However, traditional methods to obtain these products have disadvantages such as harsh conditions and limited substrate scope, which hinder the realization of their potential appl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D223/06
CPCC07D223/06
Inventor 曾庆乐王一丁
Owner CHENGDU UNIVERSITY OF TECHNOLOGY