Preparation method of cyanated or thiocyanated indolizine and derivatives thereof

A derivative, cyanation technology, applied in chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, chemical/physical processes, etc. To achieve the effect of simple operation, wide application range and good regional selectivity

Active Publication Date: 2021-11-02
GUANGDONG PHARMA UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these methods usually have disadvantages: need a large dose of oxidant; produce a large amount of heavy metal waste

Method used

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  • Preparation method of cyanated or thiocyanated indolizine and derivatives thereof
  • Preparation method of cyanated or thiocyanated indolizine and derivatives thereof
  • Preparation method of cyanated or thiocyanated indolizine and derivatives thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0218] Put 19.3mg (0.1mmol) 2-phenylindolizine, 1.1mg-10.2mg (0.001mmol-0.01mmol) Bengal rose, 4.6mg-22.8mg (0.06mmol-0.3mmol) ammonium thiocyanate in 25ml In a test tube with a stirring bar, add 1mL of 1,2-dichloroethane at room temperature, then add 3.4mg-5.1mg (0.1mmol-0.15mmol) of hydrogen peroxide, stir for 6 hours under blue light irradiation, spin dry After flash column chromatography, the target product was obtained in 76% yield.

[0219]

[0220] 1H NMR (400MHz, Chloroform-d) δ8.27(d, J=6.9Hz, 1H), 7.81(d, J=7.7 Hz, 2H), 7.51–7.44(m, 3H), 7.39(t, J= 7.4Hz, 1H), 7.06–6.98(m, 1H), 6.81(t, J = 6.8Hz, 1H), 6.68(s, 1H).

[0221] 13C NMR (101MHz, Chloroform-d) δ137.5, 136.6, 132.4, 128.96, 128.4, 127.4, 125.2, 122.5, 119.2, 114.8, 113.1, 99.7, 92.5.

[0222] HR-ESI-MS m / z calcd.for C15H10N2[M+H]+:219.0922,found:219.0922.

Embodiment 2

[0224] Put 18.3mg (0.1mmol) 2-furyl indolizine, 1.1mg-10.2mg (0.001mmol-0.01mmol) Rose Bengal, 4.6mg-22.8mg (0.06mmol-0.3mmol) ammonium thiocyanate in 25ml In a test tube with a stirring bar, add 1mL of 1,2-dichloroethane at room temperature, then add 3.4mg-5.1mg (0.1mmol-0.15mmol) of hydrogen peroxide, stir for 6 hours under blue light irradiation, spin dry After flash column chromatography, the target product was obtained in 64% yield.

[0225]

[0226] 1H NMR (400MHz, Chloroform-d) δ8.21 (d, J = 6.9Hz, 1H), 7.52 (d, J = 1.5 Hz, 1H), 7.45 (d, J = 9.0Hz, 1H), 7.04–6.97 (m,1H),6.92(d,J=3.4Hz,1H),6.79 (t,J=6.8Hz,1H),6.68(s,1H),6.52(dd,J=3.3,1.8Hz,1H) .

[0227]13C NMR (101MHz, Chloroform-d) δ147.3, 142.6, 136.6, 127.8, 125.2, 122.6, 119.2, 114.2, 113.2, 111.8, 108.1, 97.5, 91.0.

[0228] HR-ESI-MS m / z calcd. for C13H8N2O[M+H]+: 209.0719, found: 209.0715.

Embodiment 3

[0230] 27.1mg (0.1mmol) 2-(4-bromophenyl) indolizine, 1.1mg-10.2mg (0.001mmol-0.01mmol) Bengal rose, 4.6mg-22.8mg (0.06mmol-0.3mmol) thiocyanate Ammonium chloride is placed in a 25ml test tube with a stirring bar, after adding 1mL of 1,2-dichloroethane at room temperature, then add 3.4mg-5.1mg (0.1mmol-0.15mmol) of hydrogen peroxide, and stir under blue light irradiation After 6 hours, the target product was obtained by flash column chromatography after spin-drying, with a yield of 63%.

[0231]

[0232] 1H NMR (400MHz, Chloroform-d) δ8.28(d, J=6.9Hz, 1H), 7.68(d, J=8.2 Hz, 2H), 7.60(d, J=8.4Hz, 2H), 7.50(d ,J=8.9Hz,1H),7.07–7.01(m,1H),6.85 (t,J=6.8Hz,1H),6.66(s,1H).

[0233] 13C NMR (101MHz, Chloroform-d) δ136.7, 136.3, 132.2, 131.5, 129.0, 125.4, 122.8, 122.6, 119.3, 113.4, 99.7.

[0234] HR-ESI-MS m / z calcd. for C15H9BrN2[M+H]+: 297.0029, found: 297.0027.

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Abstract

The invention provides a preparation method of cyanated or thiocyanated indolizine and derivatives thereof, and belongs to the technical field of organic synthesis. Namely, direct cyanation or thiocyanation is realized through visible light catalytic oxidation carbon-hydrogen bond activation. The cyanated or thiocyanated indolizine is synthesized from basic raw materials such as ammonium thiocyanate, hydrogen peroxide, rose bengal and the like which are commercially available. Compared with the traditional cyanation reaction, the method has the advantages that the cyano source is safe and non-toxic, visible light is used as energy, the method is environment-friendly, the reaction conditions are green, mild and efficient, the selective thiocyanation reaction is realized by regulating and controlling the oxidizing agent, and a new way for synthesizing cyano compounds is provided for organic chemistry researchers. The prepared indolizine has a good luminous effect and has a potential application prospect in the field of fluorescent materials.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of cyanated or thiocyanated indolizine and derivatives thereof. Background technique [0002] The cyano group exists in a variety of therapeutic drugs and plays a unique role [1-3] . As a multifunctional functional group, the cyano group can be easily converted into many other useful functional groups, such as carbamoyl, carboxyl, aminomethyl, carbonyl, nitrogen-containing heterocycle, etc., so it has a wide range of applications in organic synthesis [4-8] . On the other hand, heterocyclic compounds undoubtedly occupy an extremely important position in organic compounds, especially in medicinal chemistry. Therefore, the synthesis of heterocyclic nitrile compounds has aroused great interest among organic synthesis workers in the past few decades. big concern. The direct cyanation reaction of heterocyclic rings is the main way to obtai...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D471/04C09K11/06B01J31/02
CPCC07D471/04C09K11/06B01J31/0232C09K2211/1029C09K2211/1088B01J35/39Y02P20/584
Inventor 曹华余跃张宇
Owner GUANGDONG PHARMA UNIV
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