Diaryl ring fused sulfides and diaryl ring fused selenides, and synthesis method and application thereof

A technology of episulfides and diaryls, which is applied in the field of synthesis of functionalized diaryls and episulfides and selenides, can solve the problems of poor economy of periodonium salt atoms, and achieve wide substrate universality and high yield High efficiency, avoid poisoning effect

Active Publication Date: 2017-02-15
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The traditional method is to introduce sulfur and selenium early under the action of transition metal catalysts and ligands; When used as an arylating agent, only one of the aryl groups is usually utilized, which makes periodonium salts less atom-economy

Method used

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  • Diaryl ring fused sulfides and diaryl ring fused selenides, and synthesis method and application thereof
  • Diaryl ring fused sulfides and diaryl ring fused selenides, and synthesis method and application thereof
  • Diaryl ring fused sulfides and diaryl ring fused selenides, and synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Synthesis of Compound 2a:

[0035]

[0036] Under nitrogen protection, the Cs 2 CO 3 (130.3mg, 0.4mmol), S 8 (12.8mg, 0.05mmol), periodinium salt 1a (42.8mg, 0.1mmol) and dry DMSO (1mL) were added to a dry Schlenk reaction tube. After the reaction was stirred at 100°C for 2 hours, it was lowered to room temperature, and 10 mL of water was added to the system for dilution, then ethyl acetate (10 mL*3) was added for extraction, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography to obtain a white solid 2a (16.4 mg, 89%). 1 H NMR (400MHz, CDCl 3 )δ8.22-8.11(m,2H),7.93-7.78(m,2H),7.51-7.41(m,4H); 13 C NMR (100MHz, CDCl 3 )δ139.5,135.6,126.7,124.4,122.8,121.6; IR(KBr)ν3448,2963,1437,1415,1262,1067,1025,801,744,701,496cm -1 ; MS(EI) m / z=184(100), 152(15), 139(20), 92(12), 79(9).

Embodiment 2

[0038] Synthesis of compound 2b:

[0039]

[0040] Under nitrogen protection, the Cs 2 CO 3 (130.3mg, 0.4mmol), S 8 (12.8mg, 0.05mmol), periodinium salt 1b (45.8mg, 0.1mmol) and dry DMSO (1mL) were added to a dry Schlenk reaction tube. After the reaction was stirred at 100°C for 2 hours, it was lowered to room temperature, and 10 mL of water was added to the system for dilution, then ethyl acetate (10 mL*3) was added for extraction, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography to obtain a white solid 2b (16.1 mg, 75%). 1 H NMR (400MHz, CDCl 3 )δ8.09-7.99(m,2H),7.81(dd,J=7.2,1.2Hz,1H),7.46-7.36(m,2H),7.33(d,J=2.3Hz,1H),7.06(dd ,J=8.7,2.4Hz,1H),3.91(s,3H); 13 C NMR (100MHz, CDCl 3 )δ159.1, 141.0, 138.6, 135.5, 129.1, 125.5, 124.4, 122.6, 122.2, 120.7, 113.4, 105.9, 55.6; -1 ; HRMS (EI) for C 13 h 10 OSCalculated: 214.0452,found: 214.0450.

Embodiment 3

[0042] Synthesis of compound 2c:

[0043]

[0044] Under nitrogen protection, the Cs 2 CO 3 (130.3mg, 0.4mmol), S 8 (12.8mg, 0.05mmol), periodinium salt 1c (48.0mg, 0.1mmol) and dry DMSO (1mL) were added to a dry Schlenk reaction tube. After the reaction was stirred at 100°C for 2 hours, it was lowered to room temperature, and 10 mL of water was added to the system for dilution, then ethyl acetate (10 mL*3) was added for extraction, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography to obtain a white solid 2c (23.3 mg, 97%). 1 H NMR (400MHz, CDCl 3 )δ8.15-8.05(m,2H),7.89-7.82(m,2H),7.53(dd,J=8.4,1.7Hz,1H),7.47-7.40(m,2H),1.43(s,9H) ; 13 C NMR (100MHz, CDCl 3 )δ150.3,139.6,139.4,135.5,133.1,126.2,124.2,122.8,122.4,121.3,121.1,119.1,35.1,31.5; IR(KBr)ν3058,2959,2866,1602,1453,1393,1031,1058,1 ,821,763,733,657cm -1 ; HRMS (EI) for C 16 h 16 S Calculated: 240.0973, Found: 240.0976.

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Abstract

The invention discloses a synthesis method of diaryl ring fused sulfides represented by formula (B) and diaryl ring fused selenides represented by formula (C). The method is characterized in that a reaction of a reaction raw material high-iodine salt is carried out in dimethyl sulfoxide under the action of an inorganic sulfuration reagent or selenylation reagent and an alkali at 60-100 DEG C to obtain the diaryl ring fused sulfides and the diaryl ring fused selenides. Sulfur or selenium is introduced in the later stage in the presence of a nonmetal catalyst, so poisoning of sulfur to a metal catalyst in the early stage reaction is avoided; the above inorganic sulfur source is nontoxic and odorless; and two aryl groups in the high-iodine salt are fully used, so the atom economy and the greenness of the method are fully shown. The diaryl ring fused sulfides and the diaryl ring fused selenides prepared through the method can be applied to synthesize photoelectric materials BTBT and BTBS.

Description

technical field [0001] The invention belongs to the technical field of organic compound synthesis and application, in particular to the synthesis of functionalized diaryl ring sulfides and selenides, and the preparation of material molecules [1]benzothieno-[3,2-b][1 ]benzothiophene (BTBT) and benzothieno-[3,2-b][1]benzoselenophene (BTBS). Background technique [0002] Diaryl episulfides and selenides are widely used in material molecules, such as [1]benzothieno-[3,2-b][1]benzothiophene (BTBT) of formula (D), (E) naphtho[2,3-b]naphtho[2',3':4,5]thieno[2,3-d]thiophene (DNTT), benzothieno-[ 3,2-b][1]Benzoselenophene (BTBS). Therefore, it is particularly important to develop efficient, environmentally friendly, and simple methods for the synthesis of diaryl episulfides and selenides. [0003] [0004] The traditional method of synthesizing diaryl ring sulfides and selenides is mainly through cross-coupling of aryl halides and aryl sulfide compounds, and then further coupli...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D333/76C07D335/12C07D337/14C07D337/16C07D495/04C07D345/00C07D517/04C09K11/06
CPCC07D333/76C07D335/12C07D337/14C07D337/16C07D345/00C07D495/04C07D517/04C09K11/06C09K2211/1092C09K2211/1096
Inventor 姜雪峰王明范巧玲
Owner EAST CHINA NORMAL UNIV
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