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Novel preparation method of sulfonium salt derivatives with stilbene as conjugated system

A technology of stilbene and conjugated systems, which is applied in the field of preparation of sulfonium salt derivatives, can solve the problems of expensive raw materials and long reaction steps, and achieve the effects of convenient purification, simple operation and wide source of raw materials

Inactive Publication Date: 2017-12-29
TONGJI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Both the preparation of styrene in these reactions and the Pd-catalyzed Heck reaction involve expensive raw materials and the reaction steps are long.

Method used

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  • Novel preparation method of sulfonium salt derivatives with stilbene as conjugated system
  • Novel preparation method of sulfonium salt derivatives with stilbene as conjugated system
  • Novel preparation method of sulfonium salt derivatives with stilbene as conjugated system

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Example 1: Synthesize the target sulfonium salt molecule containing methoxy group according to the following route

[0024]

[0025] (a): K 2 CO 3 , DMF, 100°C, 4h;

[0026] (b): reflux, 4h;

[0027] (c): NaH, DMF, room temperature, 12h;

[0028] (d): Methyl trifluoromethanesulfonate (or dimethyl sulfate); sodium hexafluoroantimonate, dichloromethane, room temperature, 24h.

[0029] 1. Synthesis of 4-benzylmercaptobenzaldehyde

[0030] In a 250mL three-neck flask, add K 2 CO 3 (20.37g, 0.15mol) and 75mL DMF, vacuum the system and fill with N 2 After three times, it was placed in an oil bath at 100°C, and 4-fluorobenzaldehyde (12.20 g, 0.1 mol) and benzyl mercaptan (12.40 g, 0.1 mol) were injected sequentially, respectively, and stirred for 4 h. Slowly add the system to 10 times the volume of distilled water with stirring, collect the precipitate by filtration, and store it in a vacuum oven at 40°C. Yield 91.0%.

[0031] 1 H NMR (400MHz, CDCl 3 )δ: 9.91(s,...

Embodiment 2

[0038] Example 2: The target sulfonium salt molecule containing N,N-diphenylamino was synthesized according to the following route

[0039]

[0040] (a): toluene, reflux, 24h;

[0041] (c): Potassium tert-butoxide, THF, room temperature, 12h;

[0042] (d): Methyl trifluoromethanesulfonate, dichloromethane, room temperature, 24h.

[0043] 1. Synthesis of Phosphate Salt

[0044] Take a dry 250mL round bottom flask, add 4-N,N-dimethylaminobenzyl bromide 3.38g (10mmol, 1equ) to it, and 30mL anhydrous toluene, then add 2.02g (10mmol, 1equ) to the reaction system 1equ) Tri-n-butylphosphine. The reaction was refluxed for 24h. After the reaction was over, the reaction flask was lifted and cooled to room temperature. Then put the flask into the refrigerator to freeze for 2h. After freezing, a white solid appeared in the flask, and it was suction-filtered at low temperature and washed twice with toluene to obtain 4.84 g of a white powder product with a yield of 70%.

[0045] ...

Embodiment 3

[0055] Embodiment 3: Synthesize the target sulfonium salt molecule containing a methyl group according to the following route

[0056]

[0057] (a): K 2 CO 3 , DMF, 100°C, 4h;

[0058] (b): reflux, 4h;

[0059] (c): NaH, DMF, room temperature, 12h;

[0060] (d): Methyl trifluoromethanesulfonate (or dimethyl sulfate), potassium hexafluorophosphate, dichloromethane, room temperature, 24h.

[0061] 1. Synthesis of 4-benzylmercaptobenzaldehyde

[0062] The steps are the same as the synthesis process in Example 1.

[0063] 1 H NMR (400MHz, CDCl 3 )δ: 9.91 (s, 1H), 7.74 (d, 2H), 7.41-7.27 (m, 7H), 4.24 (s, 2H).

[0064] 2. Synthesis of 4-(4-methylphenyl)vinylphenylbenzyl sulfide

[0065] Take the reaction product (2.91g, 12mmol) of p-methylbenzyl chloride and excess triethyl phosphite in a three-necked flask, add NaH (1.23g, 50mmol) and 100mL DMF at room temperature, find that there is gas generation, and then add 4 -Benzylmercaptobenzaldehyde (2.25g, 10mmol), after sti...

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Abstract

The invention provides a novel preparation method of sulfonium salt derivatives with stilbene as a conjugated system. The method comprises steps as follows: firstly, benzyl halides (Hal denotes halogen atom) substituted with different groups react with organic phosphate, a product reacts with benzaldehyde substituted with different sulfydryl under the alkaline condition, a high-yield disubstituted stilbene intermediate shown in (I)-a is prepared, and finally, the intermediate shown in (I)-a produces final sulfonium salt under the action of silver salt and alkyl halide or silver salt and alkyl acid ester; when different negative ions are required to be replaced, a salt exchange method is adopted to realize replacement. The provided scheme has the benefits, as examples but not confined, as follows: no noble metal catalyst is required, the raw materials are easy to obtain, and the cost is low; the reaction is performed at the room temperature, operation is simple and purification is convenient; favorable conditions are provided for large-scale industrial production of the sulfonium salt derivatives with stilbene as the conjugated system.

Description

technical field [0001] The invention relates to a preparation method of a sulfonium salt derivative with a relatively large conjugated system that can use LED as an excitation light source, can be used in photolithography, photoinitiator cationic polymerization, two-photon microstructure, etc. A method for preparing a class of sulfonium salt derivatives whose main conjugated system is substituted stilbene. Background technique [0002] Sulfonium salt compounds are a class of important fine organic chemical materials; in the field of radiation curing technology using ultraviolet light (UV) or visible light or LED (i.e. Light-Emitting Diode) as light source, in semiconductor fields such as photoresists, It can generate strong acid under light irradiation conditions, and is widely used as a photoinitiator in the field of cationic photocuring. Photoinitiators play a decisive role in the photocuring rate. Cationic photopolymerization, because of its small volume shrinkage durin...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C381/12C07C319/14C07C323/22C07C323/18C07C323/31C07C321/28C07F9/40C07F9/54C07C17/263C07C17/35C07C22/04C07C319/20C07C209/74C07C211/56
CPCC07C381/12C07C17/263C07C17/35C07C209/74C07C319/14C07C319/20C07F9/4056C07F9/4075C07F9/5456C07C323/22C07C323/18C07C321/28C07C22/04C07C323/31C07C211/56
Inventor 金明周茹春潘海燕万德成
Owner TONGJI UNIV
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