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A kind of selenocyanation reagent, its preparation and application

A technology of selenocyanide and selenocyanide, which is applied in the field of preparation of selenocyanide compounds, can solve the problems of human body and environmental damage, side reactions, and increased costs, and achieve high stereoselectivity, high reactivity, and low toxicity. Effect

Active Publication Date: 2022-03-11
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The direct introduction method can be divided into two categories: one method is to use anionic selenocyanide reagents such as potassium selenocyanate, and the substrate must have a leaving group to allow nucleophilic substitution reactions to occur. , so that the structure of the substrate is relatively high, and the leaving group must be introduced in advance; There may be other side reactions on the substrate molecule, and transition metals are used in some reactions. If transition metals are used in the late modification of drugs, the transition metals are more toxic, and the removal of transition metals will also increase the cost.
Another method is to use a cationic selenocyanation reagent, although the use of this type of reagent does not require the substrate molecule to introduce a leaving group in advance, or to add an oxidizing agent, but the currently used cationic selenocyanation reagents such as ( SeCN) 2 and Se(SeCN) 2 In the reaction, it is easy to generate highly toxic selenocyanic acid, which can be further decomposed into hydrocyanic acid, which is very harmful to the human body and the environment.

Method used

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  • A kind of selenocyanation reagent, its preparation and application
  • A kind of selenocyanation reagent, its preparation and application
  • A kind of selenocyanation reagent, its preparation and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] The specific preparation steps of selenocyanation reagent nitrogen-selenocyanatosaccharin are as follows:

[0029] Nitrogen-chlorosaccharin (2.17g) and silver selenocyanate (2.24g) were reacted in acetonitrile (35mL) at room temperature (10°C-35°C, the same below) for 1h, filtered through diatomaceous earth and then rotated under reduced pressure The solvent was removed by evaporation to obtain light yellow solid nitrogen-selenocyanosaccharin (2.45g, yield 85%). The specific synthetic route is as follows:

[0030]

[0031] The characterization results of the nitrogen-selenocyanatosaccharin prepared in this example are as follows: mp (melting point): 225-227°C; 1 H NMR (400MHz, CDCl 3 )δ:8.06(d,J=7.2Hz,1H,Ar–H),7.93–7.91(m,2H,Ar–H),7.89–7.84(m,1H,Ar–H), such as figure 1 shown; 13 C{1H}NMR (100MHz, CDCl 3 )δ: 159.7, 139.4, 135.4, 134.4, 127.3, 125.5, 121.2, 90.3 (SeCN) ppm, such as figure 2 Shown; IR (KBr): 2151 (SeCN), 1712, 1589, 1572cm –1 ; HRMS(ESI): calcula...

Embodiment 2

[0033] The specific preparation steps of (2-selenocyano-beta-tetralone adamantyl ester) are as follows:

[0034] Under air conditions, β-tetralone adamantyl ester (16mg, 0.05mmol) and nitrogen-selenocyanosaccharin (18mg, 0.06mmol) were dissolved in dichloromethane (1.0mL), and stirred at room temperature for 12h, then reduced The solvent was removed by rotary evaporation under pressure, and the residue was purified by a flash silica gel column to obtain 2-selenocyano-β-tetralone adamantyl ester (20 mg, yield 93%), and its purity was greater than 95% as determined by hydrogen spectroscopy.

[0035] The characterization results of 2-selenocyano-β-tetralone adamantyl ester prepared in this example are as follows: mp: 109-111°C; 1 H NMR (400MHz, CDCl 3)δ:8.00(dd, J=7.6,1.2Hz,1H,Ar–H),7.58(dt,J=7.7,1.2Hz,1H,Ar–H),7.36(t,J=7.6Hz,1H, Ar–H), 7.27(d,J=8.8Hz,1H,Ar–H),3.22–3.04(m,3H,CH 2 ),2.75–2.68(m,1H,CH 2 ),2.15(s,3H,Ad–H),2.07(s,6H,Ad–H),1.62(s,6H,Ad–H); 13 C{1H}NMR (100MHz, ...

Embodiment 3

[0037] The specific preparation steps of (2-selenocyano-7-chloro-beta-tetralone adamantyl ester) are as follows:

[0038] Dissolve 7-chloro-β-tetralone adamantyl ester (18mg, 0.05mmol) and nitrogen-selenocyanosaccharin (18mg, 0.06mmol) in dichloromethane (1.0mL) under air condition, and stir the reaction at room temperature After 12 hours, the solvent was removed by rotary evaporation under reduced pressure, and the residue was purified by a flash silica gel column to obtain 2-selenocyano-7-chloro-β-tetralone adamantyl ester (19 mg, yield 81%), the purity of which was verified by The hydrogen spectrum identification is greater than 95%.

[0039] The characterization results of the proton nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum, infrared spectrum and high-resolution mass spectrum of the 2-selenocyano-7-chloro-beta-tetralone adamantyl ester prepared in the present embodiment are as follows: mp: 142 –144°C; 1 H NMR (400MHz, CDCl 3 )δ: ...

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Abstract

The invention relates to a selenocyanation reagent, its preparation and application, and belongs to the technical field of selenocyanation compound preparation. The selenocyanation reagent of the present invention is nitrogen-selenocyanogen saccharin, which belongs to a cationic selenocyanation reagent, which is relatively safe in use, has low toxicity and high reactivity, and can not only synthesize selenocyano-containing compound, and under the catalytic action of the catalyst, chiral selenocyano-containing compounds with high stereoselectivity can also be synthesized.

Description

technical field [0001] The invention relates to a selenocyanation reagent, its preparation and application, and belongs to the technical field of selenocyanation compound preparation. Background technique [0002] Selenium is one of the essential trace elements for the human body, and exists mainly in the form of selenoproteins in the human body. Medical research has proved that many diseases such as liver disease, cataract, muscle atrophy, myocardial necrosis and decreased immunity are related to human selenium deficiency. As bioactive molecules, selenium-containing compounds have excellent performance in anti-oxidation and anti-cancer. Selenium-cyano compounds have also attracted widespread attention as anti-cancer and anti-oxidative biomolecules. In addition, cyano group is an important intermediate in the field of organic synthesis, which can be converted into other functional groups, and selenocyano-containing compounds can be converted into other selenium-containing ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D275/06C07C391/00
CPCC07D275/06C07C391/00C07C2602/10
Inventor 陈甫雪吴迪
Owner BEIJING INSTITUTE OF TECHNOLOGYGY