Method for synthesizing o-alkenyl phenol derivate

A technology of o-alkenyl phenol and alkenyl phenol, which is applied in the field of synthesizing o-alkenyl phenol derivatives, can solve problems such as complex reactions and limited product structure diversity, and achieve simple reaction steps, strong reactivity, and high yield Effect

Inactive Publication Date: 2017-06-13
JIANGHAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, this method needs to use substituted salicylaldehyde as a raw material, and needs to introduce substituent groups on salicylaldehyde first, the reaction is complicated and the diversity of product structures is limited to a certain extent; and dangerous n-butylene is used in the reaction process. Lithium Reagent
At present, there is no safe and easy way to obtain phenolic compounds with o-alkenyl substitution structure

Method used

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  • Method for synthesizing o-alkenyl phenol derivate
  • Method for synthesizing o-alkenyl phenol derivate
  • Method for synthesizing o-alkenyl phenol derivate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037]

[0038] In this example: R 1 is methyl; R 2 For ethoxy.

[0039] Step: In 10mL reaction bottle, add compound I-1 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl 2 ] 2 (5mol%), AgSbF 6 (20mol%), Cu(OAc) 2(20mol%) and DMF (1mL), the mixture was reacted at 80°C, and TLC (thin-layer chromatography) detected that the reaction was complete. Post-processing purification: cooling to room temperature, concentration under reduced pressure. The crude product was separated and purified by silica gel column chromatography, and the mobile phase was a mixed solvent of V (petroleum ether): V (ethyl acetate) = 5:1 to obtain a pure product, a white solid, with a yield of 92%.

[0040] 1 H NMR (400MHz, CDCl 3 )δ8.20–8.15(m,1H),7.85(d,J=16.1Hz,1H),7.73-7.68(m,1H),7.56(d,J=8.0Hz,1H),7.04(d,J =8.0Hz, 1H), 7.01-7.69(m, 2H), 6.90(s, 1H), 6.43(d, J=16.1Hz, 1H), 4.20(q, J=7.1Hz, 2H), 2.35(s ,3H),1.28(t,J=7.1Hz,3H).

Embodiment 2

[0042]

[0043] In this example: R 1 is methoxy; R 2 For ethoxy.

[0044] Step: In a 10mL reaction flask, add compound I-2 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl 2 ] 2 (5mol%), AgSbF 6 (20mol%), Cu(OAc) 2 (20mol%) and DMF (1mL), the mixture was reacted at 80°C, and TLC (thin-layer chromatography) detected that the reaction was complete. Post-processing purification: cooling to room temperature, concentrated under pressure. The crude product was separated and purified by silica gel column chromatography, the mobile phase was a mixed solvent of V (petroleum ether): V (ethyl acetate) = 5:1, and the pure product was obtained as a yellow liquid with a yield of 88%.

[0045] 1 H NMR (400MHz, CDCl 3 )δ8.18(dd, J=4.7,1.6Hz,1H),7.82(d,J=16.1Hz,1H),7.72(ddd,J=8.3,7.3,2.0Hz,1H),7.61(d,J =8.8Hz,1H),7.03-6.97(m,2H),6.79(dd,J=8.8,2.6Hz,1H),6.62(d,J=2.5Hz,1H),6.36(d,J=16.1Hz ,1H), 4.19(d,J=7.1Hz,2H),3.79(s,3H),1.28(t,J=7.1Hz,3H).

Embodiment 3

[0047]

[0048] In this example: R 1 is N,N-dimethyl; R 2 Ethoxy.

[0049] Step: In a 10mL reaction flask, add compound I-3 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl 2 ] 2 (5mol%), AgSbF 6 (20mol%), Cu(OAc) 2 (20mol%) and DMF (1mL), the mixture was reacted at 80°C, and TLC (thin-layer chromatography) detected that the reaction was complete. Post-processing purification: cooling to room temperature, concentrated under pressure. The crude product was separated and purified by silica gel column chromatography, and the mobile phase was a mixed solvent of V (petroleum ether): V (ethyl acetate) = 5:1 to obtain a pure product, a yellow solid, with a yield of 85%.

[0050] Compound II-3 was tested:

[0051] 1 H NMR (400MHz, CDCl 3 )δ8.19(d,J=5.0Hz,1H),7.76(d,J=16.0Hz,1H),7.72–7.65(m,1H),7.55(d,J=8.9Hz,1H),7.01– 6.94(m,1H),6.92(d,J=8.3Hz,1H),6.56(dd,J=8.9,2.4Hz,1H),6.33(d,J=2.6Hz,1H),6.25(d,J =16.0Hz, 1H), 4.17(q, J=7.1Hz, 2H), 2.97(s, 6H), 1.26(t, J=7.1Hz, 3H).

[...

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Abstract

The invention discloses a method for synthesizing o-alkenyl phenol derivate. The synthesizing method is characterized in that Uhlmann C-O coupling reaction, olefin reaction and pyridine group removing reaction are carried out to prepare the o-alkenyl phenol derivate. According to the method, different R1 groups are selected to obtain different phenol derivate, and thus o-alkenyl phenol derivate of different types can be obtained; the phenol deviate raw materials which are low in price and easy to obtain are used, so that the raw material selecting range is expanded, and the cost is reduced. The reaction product obtained by the method are rich in functional groups, and high in reaction performance; if an R2 groups is a specific group, the reaction product can be further hydrolyzed to obtain an o-hydroxycinnamic acid derivate; meanwhile, the method is simple in reaction steps, mild in reaction conditions, free from dangerous agents, easy to operate, and high in practicability.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for synthesizing o-alkenylphenol derivatives. Background technique [0002] Phenol derivatives are a class of compounds with special hydroxyl groups, and are the core structures of many natural products and drug molecules with important biological activities. For example, picric acid, salicylic acid, phenolphthalein, etc. all have the structure of phenol. As an organic chemical raw material, phenol derivatives can be used to synthesize chemical products and intermediates such as phenolic resin, bisphenol A, and lactam. It plays an important role in the preparation of synthetic fibers, plastics, synthetic rubber, pesticides, spices, dyes and other fields. More importantly, most phenolic compounds have special odor and certain toxicity, and can be used to produce fungicides and antiseptics; in medical treatment, they can be used to sterilize surgical instruments and trea...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/30C07C69/732C07C231/12C07C235/34C07C315/04C07C317/18C07D213/643
CPCC07C67/30C07C231/12C07C315/04C07D213/643C07C69/732C07C235/34C07C317/18
Inventor 周林王亮谢浩浩张玉敏
Owner JIANGHAN UNIVERSITY
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