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Efficient preparation method of 1-aryl-4-butene compound

A compound and aryl technology, applied in the field of fine chemicals and related chemistry, to achieve the effects of high yield, easy operation and mild reaction conditions

Active Publication Date: 2020-05-08
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This synthetic method can only obtain aromatic hydrocarbon allylation products, but involves the direct coupling reaction of halomethyl aromatic compounds and allyl boron compounds catalyzed by transition metal palladium to prepare 1-aryl-4-butene compounds The method has not been reported yet

Method used

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  • Efficient preparation method of 1-aryl-4-butene compound
  • Efficient preparation method of 1-aryl-4-butene compound
  • Efficient preparation method of 1-aryl-4-butene compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] Embodiment 1: the synthesis of p-methyl-3-butenylbenzene

[0048] In a 25mL reactor, add 4-methylbenzyl chloride (0.028g, 0.2mmol), allylboronic acid pinacol ester (0.067g, 0.4mmol), palladium acetate (2.2mg, 0.01mmol), cesium fluoride (0.091g, 0.6mmol), 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (8.7mg, 0.015mmol), stirred at 80°C for 12h under nitrogen. Column chromatography separation (silica gel, 200-300 mesh; developer, petroleum ether) gave 0.023 g of p-methyl-3-butenylbenzene with a yield of 83%.

[0049] p-Methyl-3-butenylbenzene

[0050] colorless oily liquid; 1 H NMR (400MHz, CDCl 3):δ7.09(s,4H),5.92–5.80(m,1H),5.08–4.94(m,2H),2.67(t,J=8.0Hz,2H),2.36(q,J=8.0Hz, 2H), 2.32(s, 3H); 13 C NMR (100MHz, CDCl 3 ): δ139.8, 138.2, 135.2, 128.9, 128.3, 114.8, 35.6, 34.9, 21.0.

Embodiment 2

[0051] Embodiment 2: the synthesis of p-ethyl-3-butenylbenzene

[0052] The operation was the same as in Example 1, and 0.024 g of p-ethyl-3-butenylbenzene was obtained from the reaction of 4-ethylbenzyl chloride and allylboronic acid pinacol ester, with a yield of 79%.

[0053] p-Ethyl-3-butenylbenzene

[0054] colorless oily liquid; 1 H NMR (400MHz, CDCl 3 ):δ7.11(s,4H),5.92–5.90(m,1H),5.09–4.95(m,2H),2.68(t,J=8.0Hz,2H),2.62(q,J=8.0Hz, 2H), 2.36(q, J=8.0Hz, 2H), 1.22(t, J=8.0Hz, 3H); 13 C NMR (100MHz, CDCl 3 ): δ141.7, 139.1, 138.3, 128.4, 127.8, 114.8, 35.6, 34.9, 28.5, 15.7.

Embodiment 3

[0055] Embodiment 3: the synthesis of p-tert-butyl-3-butenylbenzene

[0056] The operation is the same as in Example 1, and 0.030 g of p-tert-butyl-3-butenylbenzene is obtained by reacting 4-tert-butylbenzyl chloride with allylboronic acid pinacol ester, and the yield is 82%.

[0057] p-tert-Butyl-3-butenylbenzene

[0058] colorless oily liquid; 1 H NMR (400MHz, CDCl 3 ):δ7.35(d, J=8.0Hz, 2H), 7.18(d, J=8.0Hz, 2H), 5.98–5.96(m, 1H), 5.14–4.99(m, 2H), 2.76–2.69( t,J=8.0Hz,2H), 2.44–2.39(m,2H),1.36(s,9H); 13 C NMR (100MHz, CDCl 3 ): δ148.6, 138.8, 138.3, 128.1, 125.2, 114.8, 35.5, 34.8, 34.4, 31.4.

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Abstract

The invention belongs to the technical field of fine chemicals and related chemistry, and provides an efficient preparation method of a 1-aryl-4-butene compound. The 1-aryl-4-butene compound can be obtained by taking halogen-containing methyl aromatic hydrocarbon and derivatives thereof as raw materials, taking cesium fluoride as an alkali in the presence of a palladium catalyst and a ligand and reacting with allyl boronic acid pinacol ester for 12 hours at the temperature of 80-100 DEG C under the condition of an anhydrous organic solvent. The method has the beneficial effects that the selectivity is high, the reaction conditions are mild, the operation is simple and convenient, the possibility of industrialization is realized, and the 1-aryl-4-butene compound is obtained at a relativelyhigh yield; the 1-aryl-4-butene compound synthesized by the method can be further functionalized to obtain various compounds, and is applied to development and research of natural products, functionalmaterials and fine chemicals.

Description

technical field [0001] The invention belongs to the field of fine chemicals and related chemical technologies, and provides a highly efficient preparation method of 1-aryl-4-butene compounds. Background technique [0002] 1-aryl-4-butene compounds are an extremely important structural unit in organic chemistry, and they are very important in the fields of medicine, pesticides, dyes, spices and functional materials [Macromolecules2011,44,4167-4179] application value. Among them, 1-phenyl-4-butene is used as the core raw material for the synthesis of antihypertensive drug fosinopril sodium. [0003] The reported synthesis methods of 1-aryl-4-butene compounds include Grignard reaction method [Org.Lett.2014,16,1610-1613], electrocatalytic alkylation method [Org.Lett.2017,19, 2022-2025], alkyne reduction method [Chem.Lett.2011,40,405-407], etc. [0004] The Grignard reaction method is the most common synthetic method, that is, the raw material containing allyl is reacted with ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C1/32C07C15/44C07C15/50C07C253/30C07C255/50C07C67/343C07C69/76C07C15/58
CPCC07C1/321C07C67/343C07C253/30C07C2531/22C07C15/44C07C15/50C07C15/58C07C255/50C07C69/76
Inventor 张胜尹俊超包明冯秀娟
Owner DALIAN UNIV OF TECH
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