A kind of benzylation synthetic method of phenolic compound

A technology of a phenolic compound and a synthesis method, which is applied in the field of benzylation synthesis of phenolic compounds, can solve the problems of low atom economy, complicated operation and high cost, and achieves complete conversion of raw materials, high reactivity and convenient separation. Effect

Active Publication Date: 2020-07-21
QINGDAO AGRI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] However, the above synthesis method requires an additional directing group to coordinate with the boron catalyst, and the directing group diazonium needs to be removed after the reaction is completed, resulting in low atom economy of this synthesis strategy.
In addition, this synthesis method requires the addition of precious metals or strong Lewis acids, which is costly and heavily polluting, and requires the pre-preparation of carbene groups, which is complex in operation and low in yield.

Method used

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  • A kind of benzylation synthetic method of phenolic compound
  • A kind of benzylation synthetic method of phenolic compound
  • A kind of benzylation synthetic method of phenolic compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040]

[0041] Weigh compound A 1 (Sesamol) 0.26mmol and Compound B 1 (2-Pyrrolidinylbenzaldehyde) 0.2mmol was placed in a 25mL high-pressure sealed tube, and 2mL of hexafluoroisopropanol HFIP was added, and stirred at room temperature for 12 hours.

[0042] Spotting on a TLC plate, compound B 1 After disappearing, add NaBH to the reaction system 4 (0.4 mmol) was stirred and reacted at room temperature for half an hour, then quenched by adding water, and the system reaction solution was extracted with ethyl acetate.

[0043] First wash the aqueous phase with ethyl acetate for 3 times, combine the two extracts, then add anhydrous sodium sulfate to dry, and concentrate by distillation under reduced pressure. After passing through the silica gel column, a white solid appears after concentration.

[0044] The isolated product was detected and analyzed, and the obtained product was the target product with a yield of 80%.

Embodiment 2

[0046] According to the reaction formula and reaction condition of embodiment 1, sample is spotted on the thin-layer chromatographic plate, compound B 1 After disappearance, the intermediate spiro compound was isolated.

[0047] Set up 4 parallel test groups, add 0.2mmol of the intermediate to the reaction flask, add 0.4mmol of different reducing agents and 2mL of solvent respectively, react at room temperature for 10min, concentrate the reduced product by rotary evaporation, and purify and separate it on a silica gel column.

[0048] The isolated product was detected and analyzed, and the yield of the target product varied with different reducing agents and solvents.

[0049] Table 1 Yield table of intermediate reduction reaction

[0050]

[0051]

[0052] Note: The yield is the isolated yield; the dosage ratio of reducing agent Hantzsch ester to (+ / -)-PA in Group 3 is 26:1.

Embodiment 3

[0055] Raw materials: sesamol, 2-pyrrolidinylbenzaldehyde

[0056] Chemical formula: C 18 h 19 NO 3

[0057] Exact molecular weight: 341.1576

[0058] Molecular weight:

[0059] Structural formula:

[0060] Yield: 80%

[0061] 1 H NMR (500MHz, CDCl 3 )δ10.94(s,1H),7.32(d,J=7.5Hz,1H),7.18(t,J=6.4Hz,2H),7.08(t,J=7.0Hz,1H),6.72(s, 1H),6.39(s,1H),5.80(s,2H),3.81(s,2H),3.17(s,4H),2.06(s,4H); 13 C NMR (126MHz, CDCl 3 )δ150.3, 146.9, 146.3, 140.4, 137.4, 130.7, 127.6, 125.9, 120.2, 119.3, 108.7, 100.7, 99.1, 54.1, 33.8, 23.8.; 13 C NMR (126MHz, CDCl 3 )δ150.3, 146.9, 146.3, 140.4, 137.4, 130.7, 127.6, 125.9, 120.2, 119.3, 108.7, 100.7, 99.1, 54.1, 33.8, 23.8.; high resolution mass spectrometry (ESI) calcd.for C 18 h 19 NO 3 [M+H] + :341.1576, actual value: 341.1580.

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Abstract

The invention discloses a benzylated synthetic method of a phenol framework structure through the property that hexafluoroisopropanol has strong hydrogen-bond donor ability and stable cationic speciesability. According to the benzylated synthetic method of the phenol compound disclosed by the invention, phenol and an amino-formaldehyde compound are subjected to tandem Friedel-Crafts alkylation / dehydration / hydrogen migration / cyclizing de-aromatization / aromatization in hexafluoroisopropanol at a room temperature, so that a target product is synthesized in a greenness and high-efficiency manner.Compared with a currently-known synthetic strategy such as Friedel-Crafts reaction, the synthetic method disclosed by the invention has the advantages that placeholder groups or halogen active sitesare not needed to be synthesized on a phenol framework in advance, a benzylated product area is high in selectivity, reaction test steps are simplified, and the economical efficiency of atoms is improved.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a benzylation synthesis method of phenolic compounds. Background technique [0002] There are many kinds of phenolic compounds, which widely exist in natural products, medicines, chemical raw materials and other synthetic molecules. Phenolic compounds have multiple active chemical reaction sites, which can undergo substitution reactions such as halogenation, hydrogenation, oxidation and alkylation (such as the classic Friedel-Crafts reaction), and their phenolic hydroxyl functional groups can undergo carboxylation, esterification, Etherification and other reactions. Due to the wide range of sources and active chemical properties, phenolic compounds are often used as raw materials and structural units for the construction of complex structural molecules. Furthermore, efficient control of the regioselectivity and chemoselectivity on the phenolic skeleton in ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D317/64C07D295/135C07D295/096C07F5/04
CPCC07D295/096C07D295/135C07D317/64C07F5/04
Inventor 肖建李帅帅朱帅
Owner QINGDAO AGRI UNIV
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