A kind of preparation method of cyanated or thiocyanated indolizine and derivatives thereof

A derivative, the technology of pyrazine, which is applied in the field of organic synthesis, can solve the problems of large doses of oxidants and heavy metal waste, and achieve the effects of wide application range, simple operation and good regioselectivity

Active Publication Date: 2022-07-08
GUANGDONG PHARMA UNIV
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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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  • A kind of preparation method of cyanated or thiocyanated indolizine and derivatives thereof
  • A kind of preparation method of cyanated or thiocyanated indolizine and derivatives thereof
  • A kind of preparation method of cyanated or thiocyanated indolizine and derivatives thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0218] Place 19.3mg (0.1mmol) 2-phenylindolizine, 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 1 mL of 1,2-dichloroethane at room temperature, then add 3.4 mg-5.1 mg (0.1 mmol-0.15 mmol) of hydrogen peroxide, stir under blue light for 6 hours, spin dry The target product was obtained by post-flash column chromatography 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 1 mL of 1,2-dichloroethane at room temperature, then add 3.4 mg-5.1 mg (0.1 mmol-0.15 mmol) of hydrogen peroxide, stir under blue light for 6 hours, spin dry The target product was obtained by post-flash column chromatography 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) Rose Bengal, 4.6mg-22.8mg (0.06mmol-0.3mmol) thiocyanate Ammonium acid was placed in a 25ml test tube with a stirrer, and 1mL of 1,2-dichloroethane was added at room temperature, followed by 3.4mg-5.1mg (0.1mmol-0.15mmol) hydrogen peroxide, and stirred under blue light irradiation. After 6 hours, the target product was obtained by flash column chromatography after spin-drying in 63% yield.

[0231]

[0232] 1H NMR(400MHz, Chloroform-d)δ8.28(d,J=6.9Hz,1H),7.68(d,J=8.2Hz,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 of cyanated or thiocyanated indolizine and derivatives thereof, belonging to the technical field of organic synthesis. That is, direct cyanation or thiocyanation activated by visible light-catalyzed oxidation of carbon-hydrogen bonds. The cyanation / thiocyanation indolizine is synthesized from commercially available basic raw materials such as ammonium thiocyanate, hydrogen peroxide, and rose bengal. Compared with the traditional cyanation reaction, the method has the advantages of safe and non-toxic source of cyano group, using visible light as the energy source, green temperature and high efficiency for environment-friendly reaction conditions, and realizing the selective thiocyanation reaction through the regulation of the oxidant. Organic chemistry researchers have provided a new way to synthesize cyano compounds. The indolizine prepared by the invention has good luminescence effect and has 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 a cyanated or thiocyanated indolizine and a derivative thereof. Background technique [0002] The cyano group is present in a variety of therapeutic drugs and plays a unique role [1-3] . As a multifunctional functional group, 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 synthesizers in the past few decades. Great attention. Direct cyanation of heterocycles is the main route to obtain heterocyclic ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D471/04C09K11/06B01J31/02
CPCC07D471/04C09K11/06B01J31/0232B01J35/004C09K2211/1029C09K2211/1088Y02P20/584
Inventor 曹华余跃张宇
Owner GUANGDONG PHARMA UNIV
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