Diaryl thioether compound, and synthetic method and application thereof

A technology of diaryl sulfide and synthesis method, which is applied in the fields of sulfide preparation and organic chemistry, can solve the problems of incompatibility, unfavorable environmental protection of mercaptan, and poor atom economy of iodine salt, etc., and achieve good yield and low cost. The effect of wide applicability and simplified operation steps

Active Publication Date: 2016-08-03
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 in the early stage, and the sulfide has a poisonous effect on the metal catalyst and is incompatible with the oxidant in the later reaction; at the same time, the use of mercaptans with odor and toxicity is not conducive to environmental protection; A class of easy-to-prepare, stable compounds that are widely used as arylation reagents, and when traditional periodium salts are used as arylation reagents, usually only one of the aryl groups is used, which makes the atoms of periodium salts poor economy

Method used

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  • Diaryl thioether compound, and synthetic method and application thereof
  • Diaryl thioether compound, and synthetic method and application thereof
  • Diaryl thioether compound, and synthetic method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Synthesis of compound 2a:

[0042]

[0043] Reaction formula (1)

[0044] Under nitrogen protection, the Cu(OTf) 2 (3.6mg, 0.01mmol), 1,10-phen (2.2mg, 0.012mmol), K 3 PO 4 (42.5mg, 0.2mmol), KSAc (22.8mg, 0.2mmol), periodinium salt 1a (56.1mg, 0.1mmol) and dry DMSO (1mL) were added to a dry Schlenk reaction tube. After the reaction was stirred at 100°C for 12 hours, it was lowered to room temperature, 10 mL of water was added to the system for dilution, and ethyl acetate (10 mL*3) was added for extraction, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography to obtain a colorless Oil 2a (25.7 mg, 87%). 1 HNMR (400MHz, CDCl 3 ) 1 HNMR (400MHz, CDCl 3 )δ7.42(d, J=8.9Hz, 2H), 7.34(d, J=8.6Hz, 2H), 7.02(d, J=8.6Hz, 2H), 6.92(d, J=8.9Hz, 2H) ,3.83(s,3H); 13 CNMR (100MHz, CDCl 3 )δ160.2, 138.2, 135.6, 131.9, 129.5, 123.6, 119.4, 115.2, 55.4; -1 ;HRMS(EI)forC 13 h 11 OSBrCalculated: 293.9714, Found: 293.9718.

Embodiment 2

[0046] Synthesis of compound 2b:

[0047]

[0048] Reaction formula (2)

[0049] Under nitrogen protection, the Cu(OTf) 2 (3.6mg, 0.01mmol), 1,10-phen (2.2mg, 0.012mmol), K 3 PO 4 (42.5mg, 0.2mmol), KSAc (22.8mg, 0.2mmol), periodinium salt 1b (56.1mg, 0.1mmol) and dry DMSO (1mL) were added to a dry Schlenk reaction tube. After the reaction was stirred at 100°C for 12 hours, it was lowered to room temperature, 10 mL of water was added to the system for dilution, and ethyl acetate (10 mL*3) was added for extraction, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography to obtain a colorless Oil 2b (20.7 mg, 70%). 1 HNMR (400MHz, CDCl 3 )δ7.34(d,J=8.4Hz,2H),7.19-7.12(m,2H),7.01-6.92(m,2H),6.83(d,J=8.4Hz,2H),3.73(s,3H ); 13 CNMR (100MHz, CDCl 3 )δ160.4, 141.6, 136.1, 130.2, 129.9, 128.5, 126.0, 123.0, 122.7, 115.3, 55.4; -1 ;HRMS(EI)forC 13 h 11 OSBrCalculated: 293.9714, Found: 293.9718.

Embodiment 3

[0051] Synthesis of compound 2c:

[0052]

[0053] Reaction formula (3)

[0054] Under nitrogen protection, the Cu(OTf) 2 (3.6mg, 0.01mmol), 1,10-phen (2.2mg, 0.012mmol), K 3 PO 4 (42.5mg, 0.2mmol), KSAc (22.8mg, 0.2mmol), periodonium salt 1c (51.7mg, 0.1mmol) and dry DMSO (1mL) were added to a dry Schlenk reaction tube. After the reaction was stirred at 100°C for 12 hours, it was lowered to room temperature, 10 mL of water was added to the system for dilution, and ethyl acetate (10 mL*3) was added for extraction, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography to obtain a colorless Oil 2c (16.8 mg, 67%). 1 HNMR (400MHz, CDCl 3 )δ7.43(d, J=7.3Hz, 2H), 7.22(d, J=7.1Hz, 2H), 7.10(d, J=7.1Hz, 2H), 6.93(d, J=7.3Hz, 2H) ,3.82(s,3H); 13 CNMR (100MHz, CDCl 3 )δ160.1, 137.4, 135.5, 131.6, 129.3, 129.0, 123.8, 115.2, 55.4; -1 ;HRMS(EI)forC 13 h 11 OSCl Calculated: 250.0219, Found: 250.0222.

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Abstract

The invention discloses a diaryl thioether compound, and a synthetic method and an application thereof. Various diaryl thioether compounds can be obtained through a reaction of a reaction raw material high iodine salt in dimethyl sulfoxide at 60-100DEG C under the action of an odorless sulfuration reagent, an alkali, a metal catalyst and a ligand for 3-12h. Sulfur is introduced in the later stage, so poisoning of sulfur to the metal catalyst and incompatibility of an oxidant in the early stage reaction are 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 of the method is fully shown. The diaryl thioether compound prepared through the method can be further used to synthesize a photoelectric material BTBT and an anti-inflammatory drug zaltoprofen.

Description

technical field [0001] The invention belongs to the technical field of synthesis and application of organic compounds, in particular to the synthesis of functionalized diaryl sulfide compounds, and the preparation of material molecules [1]benzothieno-[3,2-b][1]benzo Thiophene (BTBT) and the anti-inflammatory drug Zaltoprofen (Zaltoprofen). Background technique [0002] Diaryl sulfide compounds are a very important class of compounds, especially cyclic diaryl sulfide compounds are widely used in material molecules and drug molecules, such as [1]benzothiophene of formula (C) And-[3,2-b][1]benzothiophene (BTBT), naphtho[2,3-b]naphth[2',3':4,5]thieno[2, 3-d]thiophene (DNTT), the anti-inflammatory drug Zaltoprofen of formula (E) 2-(10-oxo-10,11-dihydrodibenzo[b,f]thia -2-yl) propionic acid (Zaltoprofen). Therefore, it is particularly important to develop methods for synthesizing diaryl sulfide compounds with high efficiency, environmental protection and good compatibility. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C323/20C07C323/22C07C321/30C07C323/09C07C319/14C07D213/70C07D239/60C07D333/76C07D495/14C07D495/04C07D335/12C07D335/04C07D337/14C07D337/16
CPCC07C319/14C07C321/30C07C323/09C07C323/20C07C323/22C07D213/70C07D239/60C07D333/76C07D335/04C07D335/12C07D337/14C07D337/16C07D495/04C07D495/14
Inventor 姜雪峰王明魏建朋
Owner EAST CHINA NORMAL UNIV
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