Synthesis method of aryl thiophthene derivative

A technology of thiophene derivatives and synthesis methods, which is applied in the general synthesis of aryl thiophene derivatives, in the field of aryl thiophene derivatives, can solve the problems of expensive catalysts and low functional group tolerance, and achieve simple and easy experimental equipment and operation The effect of scientific and reasonable synthetic method and high yield

Inactive Publication Date: 2011-05-25
PEKING UNIV
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Problems solved by technology

But the catalyst of the former method is expensive, and the latter method has low functional group tolerance

Method used

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  • Synthesis method of aryl thiophthene derivative
  • Synthesis method of aryl thiophthene derivative
  • Synthesis method of aryl thiophthene derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Embodiment 1——preparation of formula IIIa (R 1 =R 2 =Thienyl (Thiophenyl)) compound:

[0030]

[0031] Add 1mmol of compound Ia to a 20mL reaction tube under nitrogen protection, add 5mL of 1,4-dioxane, use an ice-water bath to keep the reaction temperature at 0°C, add 10mmol of TiCl 4 , after the addition, the temperature was naturally raised to 25°C, and the reaction was carried out with magnetic stirring for half an hour. Add 10 mmol of zinc powder, raise the temperature to 110°C, and react for nine hours. Add water to quench the reaction, extract the aqueous phase three times with dichloromethane, combine the organic phases, wash with saturated sodium chloride solution, add anhydrous magnesium sulfate to the organic phase after liquid separation, dry for 30 minutes, filter under normal pressure, and concentrate the filtrate. Decolorization and separation on a silica gel column, using dichloromethane as the eluent, yielded 0.112 g of benzothiophene derivative I...

Embodiment 2

[0032] Embodiment 2——preparation of formula IIIb (R 1 =R 2 = Propyl (Pr)) compound:

[0033]

[0034] The synthetic route is basically the same as in Example 1, and the aftertreatment is the same. The difference is that this synthesis uses 1mmol Ib as the starting material, and the TiCl used 4 and zinc powder are both 5mmol, raised to 130°C for six hours in the reaction step b) and reacted for six hours to obtain 0.095g of pure product IIIb with an isolated yield of 28%. The NMR data of this compound are as follows: 1 H NMR (300MHz, CDCl 3 , Me 4 Si, 25°C): δ=1.04-1.14 (m, 6H, CH 3 ), 1.72-1.83 (m, 4H, CH 2 ), 2.86(t, J=7.6Hz, 2H, CH 2 ), 3.10(t, J=7.9Hz, 2H, CH 2 ), 7.32-7.47(m, 2H, CH), 7.85(d, J=7.8Hz, 1H, CH), 8.19(d, J=7.8Hz, 1H, CH); 13 C NMR (75MHz, CDCl 3 , Me 4 Si, 25°C): δ = 13.69 (1 CH 3 ), 13.90 (1 CH 3 ), 24.81 (1 CH 2 ), 25.17 (1 CH 2 ), 30.86 (1 CH 2 ), 31.15 (1 CH 2 ), 122.61(1 CH), 123.33(1 CH), 123.38(1 CH), 124.44(1 CH), 130.52(1 quat.C)...

Embodiment 3

[0035] Embodiment 3——preparation of formula IIIc (R 1 = R 2 = phenyl (Ph)) compound:

[0036]

[0037] The synthetic route is basically the same as in Example 2, and the aftertreatment is the same. The difference is that this synthesis uses 1 mmol Ic as a starting material, and finally obtains 0.200 g of pure product IIIc with an isolated yield of 63%. The NMR data of this compound are as follows: 1 H NMR (300MHz, CDCl 3 , Me 4 Si, 25°C): δ=5.74-5.77 (m, 1H, CH), 6.63-7.51 (m, 13H, CH); 13 C NMR (75MHz, CDCl 3 , Me 4 Si, 25°C): δ=122.64(1 CH), 123.38(1 CH), 123.51(1 CH), 124.05(1 CH), 127.42(1 CH), 128.14(1 CH), 128.30(2 CH), 128.72(2 CH), 129.11(2 CH), 131.20(2 CH), 131.55(1 quat.C), 132.24(1 quat.C), 133.77(1 quat.C), 134.37(1 quat.C), 136.41(1 quat.C), 137.18(1 quat.C), 139.87(1 quat.C), 140.96(1 quat.C), 141.51(1 quat.C), 142.84(1 quat.C).HRMS calcd .for C 24 h 14 S 3 [M+H] + : 399.03304, found 399.03243.

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Abstract

The invention discloses a synthesis method of an aryl thiophthene derivative, which belongs to the field of organic synthesis. The method comprises the following steps of: a) mixing and reacting a compound shown as a formula I and a compound shown as a formula II in an ether solvent, wherein a reaction temperature is between the freezing point of the solvent and room temperature; b) adding zinc powder, raising the reaction temperature to be between 110 DEG C and the boiling point of the solvent and reacting so as to obtain the aryl thiophthene derivative shown as a formula III, wherein R1 and R2 independently represent substituted or unsubstituted alkyl with 1 to 18 carbon atoms, naphthenic base with 3 to 6 carbon atoms, aryl with 6 to 12 carbon atoms or heterocyclic aryl with 2 to 12 carbon atoms; Ar represents aryl with 6 to 12 carbon atoms or heterocyclic aryl with 2 to 12 carbon atoms; and X represents halogen. The synthesis method can be applied to organic photoelectric materials and relevant fields.

Description

technical field [0001] The invention relates to aryl thiophene derivatives, in particular to a general synthesis method for aryl thiophene derivatives with various substituents, and belongs to the field of organic synthesis. Background technique [0002] Oligothiophene, polythiophene, and arylthiophene derivatives with various substituents are important organic optoelectronic materials with excellent optoelectronic properties, and are important raw materials for a new generation of organic field effect transistors and organic semiconductor materials. At present, among the synthetic methods of arylthiophene derivatives, late-transition metal-catalyzed coupling, electrophile-induced electrophilic cyclization reactions are the most common. However, the catalyst of the former method is expensive, and the latter method has low functional group tolerance. The present invention provides a method for synthesizing arylthiophene derivatives starting from general chemical raw material...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D495/04C07D495/14C07D333/52
Inventor 张文雄王子涛耿巍芝王涵柳席振峰
Owner PEKING UNIV
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