Unlock instant, AI-driven research and patent intelligence for your innovation.

Preparation method of selenium thioether compounds

A compound and technology of selenium sulfide, applied in the field of preparation of selenium sulfide compound, can solve problems such as no one reported, and achieve the effects of improving environmental friendliness, wide application range, simple and easy operation

Inactive Publication Date: 2019-01-04
SUN YAT SEN UNIV
View PDF2 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Despite these research works, the oxidative cleavage of S-S(Se-Se) bonds in disulfide(selenium)ethers by azo compounds has not been reported yet.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Preparation method of selenium thioether compounds
  • Preparation method of selenium thioether compounds
  • Preparation method of selenium thioether compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Put 25.2mg (0.15mmol) 4-phenyl-3-butenoic acid and 19.8mg (0.09mmol) diphenyl disulfide in a 20ml reaction flask with a stirrer, and add 3mL dichloromethane at room temperature , Then add 14.4uL (0.09mmol) diethyl azodicarboxylate and 0.7uL (0.0075mmol) TfOH respectively, stir at room temperature for 12 hours, spin dry and flash column chromatography to obtain the target product with 99% yield.

[0024]

[0025] 1 H NMR(400MHz, CDCl 3 )δ7.56–6.98(m,10H), 5.31(d,J=5.8Hz,10H), 3.80(dd,J=13.9,7.0Hz,1H), 2.99(dd,J=18.0,8.2Hz,1H ), 2.62(dd,J=18.0,7.0Hz,1H).

[0026] 13 C NMR(101MHz, CDCl 3 )δ174.25,137.40,133.37,133.30,131.80,129.44,128.87,128.83,128.57,125.50,85.17,76.84,49.91,35.45.

[0027] HR-ESI-MS m / z calcd.for C 16 H 15 O 2 S[M+H] + :271.0787;found:271.0786.

Embodiment 2

[0029] Put 22.2mg (0.15mmol) of the enol shown below and 19.8mg (0.09mmol) of diphenyl disulfide into a 20ml reaction flask with a stirrer. After adding 3mL of dichloromethane at room temperature, add 14.4 uL (0.09mmol) of diethyl azodicarboxylate and 1.3uL (0.015mmol) of TfOH, stirred at room temperature for 12 hours, spin-dried, flash column chromatography to obtain the target product, 88% yield.

[0030]

[0031] 1 H NMR(400MHz, CDCl 3 )δ7.36–7.28(m,6H), 7.22(dt,J=14.5,6.4Hz,4H), 4.77(d,J=5.7Hz,1H), 4.25–4.16(m,1H),4.08(q ,J=7.8Hz,1H),3.61(dd,J=12.7,5.7Hz,1H), 2.45(dq,J=15.4,7.7Hz,1H),2.07(td,J=12.0,5.0Hz,1H) .

[0032] 13 C NMR(101MHz, CDCl 3 )δ141.41,134.87,131.61,129.08,128.49,127.83,127.13,125.91,85.73,68.00,53.71,33.9.

[0033] HR-ESI-MS m / z calcd.for C 16 H 17 OS[M+H] + :257.0994; found:257.0994.

Embodiment 3

[0035] Put 45.2mg (0.15mmol) of enamine and 19.8mg (0.09mmol) of diphenyl disulfide as shown below in a 20ml reaction flask with a stirrer, add 3mL of dichloromethane at room temperature, and then add 14.4 uL (0.09mmol) of diethyl azodicarboxylate and 0.7uL (0.0075mmol) of TfOH, stirred at room temperature for 12 hours, spin-dried and flash column chromatography to obtain the target product, 95% yield.

[0036]

[0037] 1 H NMR(400MHz, CDCl 3 )δ7.70(d,J=7.8Hz,2H),7.41-7.01(m,12H), 4.64(s,1H), 3.78(t,J=7.9Hz,1H), 3.60(dd,J=17.9 , 7.8Hz, 2H), 2.45 (s, 3H), 2.36-2.21 (m, 1H), 1.83-1.70 (m, 1H).

[0038] 13 C NMR(101MHz, CDCl 3 )δ143.51,141.68,134.56,133.58,132.30,129.58,129.13,128.51,127.86,127.71,127.52,126.04,68.75,55.55,47.93,29.26,21.65.

[0039] HR-ESI-MS m / z calcd.for C 23 H 24 O 2 NS 2 [M+H] + :410.1243; found:410.1239.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a preparation method of selenium thioether compounds. According to the method, S-S (Se-Se) bonds can be effectively oxidized and cracked under the action of catalytic amount oftrifluoromethanesulfonic acid and diethyl azodicarboxylate, positive sulfur ions or positive selenium ions are generated, and the positive ions receive attack of different nucleophilic reagents, so that various types of selenium thioether compounds can be acquired. Cyclized alkyl selenium thioether compounds can be efficiently acquired by the method when olefine acid and olefinic alcohol or enamine serve as substrates. Asymmetric aryl selenium thioether compounds can be synthesized by the method when arylboronic acid or aromatic rings serve as a substrate. The preparation method is simple andeasy to operate, rapid, convenient, mild in condition, good in region-selectivity and high in yield, metal participation is omitted, and various types of selenium thioether compounds can be efficiently synthesized.

Description

Technical field: [0001] The invention relates to a preparation method of a selenium sulfide compound. Background technique: [0002] Organic selenium sulfur compounds are ubiquitous in natural products, drugs and biologically active molecules ((a) Dunbar, KL; Scharf, DH; Litomska, A.; Hertweck, C. Chem. Rev. 2017, 117, 5521.(b) Chauhan, P.; Mahajan, S.; Enders, D. Chem. Rev. 2014, 114, 8807. (c) Reich, HJ; Hondal, RJ; ACSChem. Biol. 2016, 11, 821.). It is an important way to construct organic selenium-sulfur compounds through the formation of direct CS (C-Se) bonds ((a) Liu, H.; Jiang, X. Chem. Asian J. 2013, 8, 2546. (b) Shen,C.; Zhang,P.; Sun,Q.; Bai,S.; Hor,TSA; Liu,X.Chem.Soc.Rev.2015,44,291. (c)Yu,J.-S.; Huang , H.-M.; Ding, P.-G.; Hu, X.-S.; Zhou, F.; Zhou, J. ACS Catal. 2016, 6, 5319.). In the past few decades, the formation of C-S (C-Se) bonds by the electrophilic functionalization of sulfide ions (selenium cations) has attracted the attention of researchers. There ar...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): C07C391/02C07D207/48C07D307/18C07D307/33C07B45/06
CPCC07B45/06C07C391/02C07D207/48C07D307/18C07D307/33
Inventor 赵晓丹刘想安锐
Owner SUN YAT SEN UNIV