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Preparation method of alkyl aromatic compound based on alkenyl ether Friedel-Crafts reaction

A technology of aromatic compounds and alkenyl ethers, which is applied in pharmaceutical and chemical intermediates and related chemical fields, can solve the problems of less research on new alkylation reagents and catalytic systems, harsh reaction conditions, complex products, etc., and achieve a wide range of substrate applications , high selectivity, good selectivity effect

Active Publication Date: 2020-07-14
LIUPANSHUI NORMAL UNIV
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Problems solved by technology

However, this type of method has the following disadvantages: there are carbocation rearrangement reactions and disproportionation reactions that lead to complex products; the use of excessive catalysts makes it difficult to handle after the reaction; the reaction conditions are harsh, etc.
Other Friedel-Crafts alkylation reaction systems have also been developed [see: (a) Rueping, M.; Bootwicha, T.; Kambutong, S.; Sugiono, E.Chem.-Asian J.2012,7,1195 -1198. (b) Wang, C.; Xie, S.; Xie, Z. Chinese J. Org. Chem. 2013, 33, 1919-1931. (c) Montesinos-Magraner, M.; Vila, C.; Blay, G.; Pedro, J.R. Synthesis 2016, 48, 2151-2164. (d) Bahr, S.; Oestreich, M. Angew. Chem. Int. Ed. 2017, 56, 52-59. (e) Heravi, M.M.; Zadsirjan, V.; Saedi, P.; Momeni, T. RSC Adv. 2018, 8, 40061-40163. (f) Maji, B. Adv. Synth. Catal. ) Yang, T.; Lu, H.; Shu, Y.; Ou, Y.; Hong, L.; ) Mohammadian, R.; Amini, M.M.; Shaabani, A.Catal.Commun.2020,136, DOI:10.1016 / j.catcom.2019.105905.], but there are few studies on new alkylating reagents and catalytic systems

Method used

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  • Preparation method of alkyl aromatic compound based on alkenyl ether Friedel-Crafts reaction
  • Preparation method of alkyl aromatic compound based on alkenyl ether Friedel-Crafts reaction
  • Preparation method of alkyl aromatic compound based on alkenyl ether Friedel-Crafts reaction

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Experimental program
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Effect test

Embodiment 1

[0036] Embodiment 1: the synthesis of diphenylmethane (3a)

[0037]

[0038] Accurately weigh benzene (78.1mg, 1.0mmol), vinylbenzyl ether (134.2mg, 1.0mmol), zinc chloride (6.8mg, 0.05mmol), and sequentially add to a 50mL Schlenk bottle, add 1,4 - Dioxane (2.0 mL), placed in an oil bath at 60° C. for 16 h. After the reaction was completed, the solvent was distilled off under reduced pressure, and petroleum ether was used as an eluent, and silica gel column chromatography was used for separation, and the yield of diphenylmethane was >99%. 1 H NMR (600MHz, CDCl 3 )δ7.42-7.39(m,4H),7.33-7.31(m,6H),4.10(s,2H); 13 C NMR (151MHz, CDCl 3 ) δ 141.2, 129.1, 128.6, 126.2, 42.1.

Embodiment 2

[0039] Example 2: Synthesis of 4-ethyl-1,1'-biphenyl (3b)

[0040]

[0041] Accurately weigh biphenyl (1.54g, 10.0mmol), vinylbenzyl ether (1.44g, 20.0mmol), and p-toluenesulfonic acid (19.2mg, 0.1mmol), and add them to a 100mL Schlenk bottle in turn, add methyl tert-butyl ether (60.0 mL), placed in an oil bath at 90°C for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and petroleum ether was used as an eluent, and silica gel column chromatography was used for separation. The yield of the alkylated product was 94%. 1 H NMR (600MHz, CDCl 3 )δ7.65(dd, J=8.1,0.9Hz,2H),7.59(d,J=8.1Hz,2H),7.49(t,J=7.7Hz,2H),7.39(t,J=7.4Hz, 1H), 7.34(d, J=8.1Hz, 2H), 2.76(q, J=7.6Hz, 2H), 1.35(t, J=7.6Hz, 3H); 13 C NMR (151MHz, CDCl 3 ) δ 143.4, 141.3, 138.7, 128.8, 128.3, 127.13, 127.06, 127.0, 28.6, 15.6.

Embodiment 3

[0042] Embodiment 3: the synthesis of 2-propylphenol (3c)

[0043]

[0044] Accurately weigh phenol (94.1mg, 1.0mmol), vinyl propyl ether (172.0mg, 2.0mmol), silver acetate (8.4mg, 0.05mmol), and sequentially add to a 25mL Schlenk bottle, add trifluoroethanol ( 5.0 mL), placed in an oil bath at 110°C for 18 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and petroleum ether / ethyl acetate was used as the eluent, and silica gel column chromatography was used for separation. The yield of the alkylated product was 87%. 1 H NMR (600MHz, CDCl 3 )δ7.17(d,J=7.5Hz,1H),7.13(d,J=7.7,1H),6.96-6.89(m,1H),6.81(dd,J=8.0,0.7Hz,1H),5.11 (s,1H),2.67-2.62(m,2H),1.72-1.67(m,2H),1.03(t,J=7.4Hz,3H); 13 C NMR (151MHz, CDCl 3 ) δ 153.5, 130.3, 128.5, 127.1, 120.8, 115.3, 32.0, 23.0, 14.0.

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Abstract

The invention discloses a preparation method of an alkyl aromatic compound based on an alkenyl ether Friedel-Crafts reaction, and belongs to the technical field of pharmaceutical and chemical intermediates and related chemistry. According to the method, alkenyl ether and an aromatic compound are used as raw materials, and green and efficient synthesis of the alkyl-substituted aromatic compound isrealized under the catalytic action of Lewis acid or protonic acid. The method has the advantages of high selectivity, mild reaction conditions, good functional group compatibility, the wide substraterange, environmental friendliness and the like. The alkyl-substituted aromatic compound is an important organic synthesis intermediate and has very wide application in the fields of organic synthesisand pharmacy, so that the alkyl-substituted aromatic compound has relatively high application value and social and economic benefits.

Description

technical field [0001] The invention relates to pharmaceutical chemical intermediates and related chemical technical fields, and relates to a Friedel-Crafts alkylation reaction based on aromatic compounds and alkenyl ethers, and preparation of alkyl-substituted aromatic compounds using aromatic compounds and alkenyl ethers as raw materials method. Background technique [0002] Alkyl-substituted aromatic compounds are important intermediates for the synthesis of natural products, pharmaceuticals or optoelectronic materials, and have a wide range of applications in the field of organic synthesis. Alkyl-substituted aromatic compounds, especially in the synthesis of optoelectronic materials, show great use, so the synthesis of alkyl-substituted aromatic compounds is one of the current research hotspots. The alkylation of aromatic compounds with alkyl halides, alcohols, and alkenes is an important method to synthesize alkyl-substituted aromatic compounds. The classical preparati...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C15/16C07C2/86C07C37/11C07C39/15C07C39/06C07C15/14C07C15/24C07C209/68C07C211/47C07D215/06
CPCC07C2/865C07C37/11C07C209/68C07D209/08C07C15/16C07C39/15C07C39/06C07C15/14C07C15/24C07C211/47
Inventor 陈霞周晓玉刘海龙陈定梅
Owner LIUPANSHUI NORMAL UNIV
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