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Preparation method of terminal arylacetylenes

A technology of terminal alkynes and aryl groups, which is applied in the field of preparation of aryl terminal alkynes, can solve problems such as low yield and difficult separation, and achieve the effects of lowering reaction temperature, shortening reaction time, and mild reaction conditions

Active Publication Date: 2014-12-03
TAIYUAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the current disadvantage of this method is that the departure of the alkyne protecting group 2-hydroxyl-2-propyl needs very harsh conditions such as strong base, high temperature and long time, such as in potassium hydroxide, tert-butanol In the presence of potassium, sodium hydride or sodium hydroxide, react in boiling toluene (110°C) or n-butanol (118°C) for several hours to tens of hours
Such harsh conditions often cause many side reactions, resulting in low yields of aryl-terminal alkynes, especially polyfunctional aryl-terminal alkynes, and difficult separation.

Method used

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  • Preparation method of terminal arylacetylenes
  • Preparation method of terminal arylacetylenes
  • Preparation method of terminal arylacetylenes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Under nitrogen protection, 25 mL of triethylamine, 785 mg (5.0 mmol) of bromobenzene, 420 mg (5.0 mmol) of 2-methyl-3-butynyl-2-ol, and bis(triphenyl Phosphine) palladium dichloride (Pd(PPh 3 ) 2 Cl 2 )70mg (0.1mmol), triphenylphosphine (PPh 3 ) 105mg (0.4mmol), cuprous iodide (CuI) 38mg (0.2mmol), react at 65 ℃ until the thin-layer chromatography monitoring raw material bromobenzene spot disappears as the end point. The reaction solution was evaporated to dryness under reduced pressure, CH 2 Cl 2 Dissolved, washed successively with 5% dilute hydrochloric acid, saturated NaCl solution, anhydrous MgSO 4 Dry and filter. After the filtrate was evaporated to dryness under reduced pressure, the crude product was purified by column chromatography (eluent: petroleum ether: ethyl acetate = 10:1) to obtain 4-phenyl-2-methyl-3-butynyl-2- Alcoholic white solid 736mg (4.6mmol), yield 92%. 1 H NMR (CDCl 3 ) δ 7.40–7.43 (m, 2H), 7.28–7.30 (m, 3H), 2.07 (s, 1H), 1.62 (s, 6H);...

Embodiment 2

[0028] Under nitrogen protection, 25 mL of triethylamine, 1.415 g (5.0 mmol) of 4-bromoiodobenzene, 420 mg (5.0 mmol) of 2-methyl-3-butynyl-2-ol, and bis (Triphenylphosphine) palladium dichloride (Pd(PPh 3 ) 2 Cl 2 )70mg (0.1mmol), triphenylphosphine (PPh 3 ) 105mg (0.4mmol), cuprous iodide (CuI) 38mg (0.2mmol), reacted at 35 ℃ until the thin-layer chromatography monitoring raw material p-bromoiodobenzene spot disappears as the end point. The reaction solution was evaporated to dryness under reduced pressure, CH 2 Cl 2 Dissolved, washed successively with 5% dilute hydrochloric acid, saturated NaCl solution, anhydrous MgSO 4 Dry and filter. After the filtrate was evaporated to dryness under reduced pressure, the crude product was purified by column chromatography (eluent: petroleum ether: ethyl acetate = 10:1) to obtain 4-(4-bromophenyl)-2-methyl-3-butane Alkynyl-2-ol white solid 1.052g (4.4mmol), yield 90%. 1 H NMR (CDCl 3 ) δ 7.42 (d, J = 8.1 Hz, 2H), 7.26 (d, J ...

Embodiment 3～ Embodiment 32

[0033] The preparation method is the same as in Example 1, and the amount of each raw material and process parameters in the second step of deprotection group reaction are shown in Table 1.

[0034]

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Abstract

The invention discloses a preparation method of terminal arylacetylenes. The method comprises the following steps: obtaining an aryne component 4-aryl-2-methyl-3-butyne-2-alcohol with 2-hydroxy-2-popyl protection groups from ayl halide and 2-methyl-3-butyne-2-alcohol by Sonogashira cross coupling reaction, and then removing the protection groups to obtain terminal arylacetylenes products, wherein the deprotection reaction is carried out by taking methylbenzene as a solvent in the presence of NaOH and diethylene glycol ethyl ether. According to the preparation method of the terminal arylacetylenes disclosed by the invention, the reaction temperature can be greatly reduced, the reaction time is shortened, and the terminal arylacetylenes can be prepared with high yield and a controlled speed at a low temperature.

Description

technical field [0001] The invention relates to a preparation method of an aryl terminal alkyne, in particular to a method for preparing an aryl terminal alkyne by removing an alkyne protecting group 2-hydroxyl-2-propyl. Background technique [0002] Aryl-terminated alkynes are important intermediates in organic synthesis. Polyarynes, polyaryldiynes, and aryl-alkyne conjugated macromolecules obtained through aryl-terminated alkynes have important applications not only in pharmaceuticals and pesticides, but also in New organic functional materials and molecular electronic devices, such as organic light-emitting diodes, liquid crystal materials, nonlinear optical materials, gas separation membranes, molecular wires, molecular switches, and molecular computers, have broad application prospects. [0003] At present, the preparation method of aryl-terminal alkynes mainly uses aromatic halides as raw materials, and undergoes Sonogashira coupling reaction with acetylene derivatives...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/06C07C15/48C07C1/20C07C25/24C07C17/361C07C43/215C07C41/18C07C205/06C07C205/12C07C201/12C07C211/46C07C211/48C07C15/54C07C209/68C07C15/50C07C69/76C07C67/333C07F7/08
Inventor 李洁郭鹍鹏董清晨黄鹏程王华许并社
Owner TAIYUAN UNIV OF TECH
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