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Light-catalyzed synthesis method of trans-stilbene compound

A technology of stilbenes and synthesis methods, which is applied in the preparation of organic compounds, organic compound/hydride/coordination complex catalysts, chemical instruments and methods, etc., can solve the problems of low yield, high price and long reaction time and other problems, to achieve the effect of good selectivity, high yield and mild reaction conditions

Active Publication Date: 2017-04-26
ZHEJIANG UNIV OF TECH
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Problems solved by technology

For example, Bedekar et al. (Tetrahedron. Lett., 2012, 53(45): 6100) catalyzed the synthesis of stilbene compounds with palladium acetate under light irradiation, wherein L-1 was added as an initiator, and the reaction 100% selectively synthesized trans-diphenyl Ethylene, but the reaction time is long and the yield is low, only 36% yield in 5 days
Waghmode et al. (New. J. Chem., 2013, 37(9): 2911) utilize PdCl 2 / TiO 2 As a photocatalyst, a heterogeneous photocatalytic Heck reaction is carried out, which mainly produces E-type (trans) stilbene compounds. Compared with direct use of visible light catalysis, there are disadvantages
Soni et al. (Catal. Sci. Technol., 2014, 4(2):510) utilized porous Pd / TiO 2 Nano photocatalyst, selectively catalyzes the Heck reaction under sunlight irradiation, and mainly generates Z-type (cis) stilbene compounds, but the reaction time is long and the selectivity is not good. It needs 3 days of visible light irradiation, Z:E=72 %: 22%, its structural formula is shown in formula L-1:

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Example 1 Derivative 6a (R a is 3-methoxy, 5-dimethoxy, R b for the synthesis of hydroxyl)

[0023] Add 3,5-dimethoxyiodobenzene (5 mmol) and pd(oAc) to a 25 mL one-necked flask 2 (1.0 mol%) / Eosin Y(1.5 mol%) was dissolved in 6 mL DMF (DMF:H 2 O=5:1) aqueous solution, then slowly drop p-hydroxystyrene (5.3mmol), react under light and stir for about 15 h at room temperature, and TLC detects that the reaction is complete. The reaction product was washed with water, separated, dried, filtered, concentrated, and recrystallized from ethyl acetate to obtain white crystals, namely derivative 6a. The melting point is 86~87°C, and the yield is 83.4%.

[0024] of the compound 1 H NMR and ESI-HRMS analysis data are described below,

[0025] 1 H NMR (500 MHz, DMSO-d 6 ): δ 3.77 (s, 6H, OCH 3 ), 6.37 (t, J = 2.0 Hz, 1H, Ar-H), 6.72 (d, J = 2.5 Hz, 2H, Ar-H), 6.75-6.79 (m, 2H, Ar-H), 6.95 (d , J =16.0 Hz, 1H, C=C-H), 7.16 (d, J = 16.0 Hz, 1H, C=C-H), 7.44-7.60 (m, 2H, Ar-H)...

Embodiment 2

[0026]Example 2 Derivative 6b (R a For 3-methoxy, 4-methyl, 5-dimethoxy, R b for the synthesis of H)

[0027] Add 3,5-dimethoxy-4-methyliodobenzene (5 mmol) and pd(oAc) to a 25 mL one-necked flask 2 (1.0 mol%) / Eosin Y(1.6 mol%) was dissolved in 6 mL DMF (DMF:H 2 O=5:1) aqueous solution, then slowly dropwise added styrene (5.6mmol), stirred under light at room temperature for about 10 h, and TLC detected the end of the reaction. The reaction product was washed with water, separated, dried, filtered, concentrated, and recrystallized from ethyl acetate to obtain a white solid, namely derivative 6b, with a yield of 87.2%.

[0028] of the compound 1 H NMR and ESI-HRMS analysis data are described below,

[0029] 1 H NMR (CDCl 3 , 500 MHz): δ 2.13 (s, Me-C(4)), 3.89 (s, MeO-C(3,5)), 6.72(s, H-C(2,6)), 7.09 (t, J = 16.5 Hz, H-C(7,8)), 7.27 (t, J = 7.3 Hz, H-C(4')), 7.37 (t, J = 7.7 Hz, H-C(3',5')), 7.53 (d, J = 7.3 Hz, H-C(2',6')). Positive ion ESI-HRMS: calcd for C 17 h 19...

Embodiment 3

[0030] Example 3 Derivative 6c (R a For 3-methoxy, 4-methyl, 5-dimethoxy, R b for the synthesis of 4-methoxy)

[0031] Add 3,5-dimethoxy-4-methyliodobenzene (5 mmol) and pd(oAc) to a 25 mL one-necked flask 2 (1.5 mol%) / Eosin Y(1.5 mol%) was dissolved in 6 mL DMF (DMF:H 2 O=5:1) aqueous solution, and then slowly dropwise added 4-methoxystyrene (5.15 mmol), stirred under light at room temperature for about 25 h, and TLC detected the end of the reaction. The reaction product was washed with water, separated, dried, filtered, concentrated, and recrystallized from ethyl acetate to obtain a white solid, namely derivative 6c, with a yield of 80.5%.

[0032] of the compound 1 H NMR and ESI-HRMS analysis data are described below,

[0033] 1 H NMR (CDCl 3 , 500 MHz): δ 2.14 (s, Me-C(4)), 3.86 (s, MeO-C(4')), 3.91(s, MeO-C(3,5)), 6.71 (s, H-C (2,6)), 6.93 (d, J = 8.7 Hz, H-C(3',5')), 6.97(d, J = 16.0 Hz, H-C(7)), 7.05 (d, J = 16.0 Hz, H-C(8)), 7.48 (d, J = 8.7 Hz,H-C(2',6...

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Abstract

The invention relates to a light-catalyzed synthesis method of a trans-stilbene compound. Substituted iodobenzene and a substituted styrene compound perform light-catalyzed reaction in a DMF solution in the presence of a catalytic system, the reaction process is monitored by TLC, reaction liquid is subjected to separation and purification to obtain the substituted stilbene compound after the reaction is completed. By the adoption of the technology, a common dye serves as a visible-light-induced photocatalyst for catalyzed synthesis of the trans-stilbene compound according to the novel method, and the method has the advantages that reaction conditions are mild, the photocatalyst is cheap and easy to obtain, the selectivity is good, the yield is high and the like and is suitable for industrial production and application.

Description

technical field [0001] The invention relates to a photocatalytic synthesis method of trans-stilbene compounds. Background technique [0002] Stilbene compounds generally refer to compounds with a stilbene parent structure in which two benzene rings are connected by a vinyl group (Nat. Prod. Res. Dev., 1994, 6(4): 71). As a monomer of natural stilbene compounds, it is divided into two types: cis and trans. The trans configuration exists more in natural plants as aglycones or glycosides. This type of compound has a wide range of biological activities, such as antioxidant ( J. Biol. Chem., 2001, 276(25): 22586), anti-inflammatory (Biochim.Biophys. Acta., 1985, 834(2): 275), anti-bacterial (Phytochemistry., 1993, 33(4): 813), antifungal (J. Am. Soc. Hortic. Sci.,1988, 113(2): 230), antitumor (Nutr. Cancer.,2001, 39(1): 102), anticardiovascular effects ( Chem. Pharm. Bull., 1987, 35(2): 887), anti-aging (WO 042231, 2001-06-14), and other activities, and has a wide range of appl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C41/30C07C43/215C07C43/225C07C43/23B01J31/22
CPCC07C41/30B01J31/2239B01J2231/4277B01J35/39C07C43/215C07C43/225C07C43/23
Inventor 翁建全戴小强朱亚波刘幸海
Owner ZHEJIANG UNIV OF TECH
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