Synthesis method of cyclopropyl allene derivatives

A technology of cyclopropyl allene and synthesis method, which is applied in the direction of organic chemistry methods, chemical instruments and methods, hydrocarbons, etc., and can solve the problem of difficulty in synthesizing cyclopropyl allene derivatives, expensive terminal alkynes, terminal alkyne Limited types of hydrocarbons, etc.

Inactive Publication Date: 2012-08-01
YANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] The disadvantage of this method is that the raw materials are not easy to obtain
In the chemical market, the types of terminal alkynes that can be purchased are limited. Except for the common phenylacetylene, other terminal alkynes are generally expensive
Therefore, using the current synthetic route, it is difficult to synthesize a wide variety of cyclopropyl allene derivatives with various substituents

Method used

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  • Synthesis method of cyclopropyl allene derivatives
  • Synthesis method of cyclopropyl allene derivatives
  • Synthesis method of cyclopropyl allene derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032]

[0033] The specific feeding table of this embodiment is as figure 1 shown.

[0034] Add 0.72g of magnesium powder, a grain of iodine and a stirring bar into a 50mL round bottom flask, vacuumize at room temperature (20°C), blow nitrogen, add 30mL of anhydrous ether, dropwise add bromoethane 2.2mL and stir. The reaction solution gradually turned light gray. After 1.5 h, 2.5 mL of cyclopropyne was added and stirring was continued, and bubbles were released. After 1.5 hours, 0.75 g of ground polyoxymethylene was added to the reaction vessel and reacted overnight. The next day, 20 mL of 1 mol / L dilute hydrochloric acid was added to the system and the reaction solution was extracted (extractant: ethyl acetate, 30 mL×3). The extract was spin-dried and transferred to a 50mL flask, and a stirring bar and 1mL of water were added. Weigh 1 g of sodium hydroxide and dissolve it in 5 mL of water, transfer it to a flask, add 1.2 mL of dimethyl sulfate dropwise, and heat to re...

Embodiment 2

[0037] Use other bases to replace ethylmagnesium bromide, others are the same as Example 1, and the results are as follows image 3 The effect of different bases is shown. The results show that using n-butyllithium yield is slightly higher, but considering the convenience of operation and low cost, preferably ethylmagnesium bromide is used as alkali.

Embodiment 3

[0039] Use other methods to protect the hydroxyl group of cyclopropyl propargyl alcohol, others are the same as Example 1, and the results are as follows Figure 4 Effect of different protecting groups shown. The results show that the use of dimethyl sulfate protects the highest yield (Example 1), high atom economy and cheap reagents.

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Abstract

The invention relates to a synthesis method of cyclopropyl allene derivatives. According to the method, cyclopropyl acetylene is used as starting materials for preparing metal cyclopropylacetylide and takes reaction with aldehyde for preparing cyclopropyl propargyl alcohol derivatives, hydroxyls of the cyclopropyl propargyl alcohol derivatives are protected to prepare cyclopropyl propargyl ether or cyclopropyl propargyl ester, and the cyclopropyl propargyl ether or the cyclopropyl propargyl ester takes reaction with Grignard reagents under the metal catalysis, and cyclopropyl allene is finally obtained. The method provided by the invention solves the problems of the existing method that raw materials cannot be easily obtained, the price is high, and the like. The method provided by the invention has the advantages that the raw materials are easy to obtain, in addition, the cyclopropyl is firstly introduced, and various substituent functional groups are then introduced, the variable of the synthesis of various kinds of cyclopropyl allene depends on the aldehyde and the Grignard reagents adopted in the reaction in the last step, and the Grignard reagents are prepared from halogenated hydrocarbon which is cheap and is easy to obtain (the varieties are many), so the method provided by the invention is more suitable for the synthesis of a series of cyclopropyl allene with various substituent groups.

Description

technical field [0001] The invention relates to a synthesis method of cyclopropyl allene derivatives. More specifically, the present invention relates to the multi-step synthesis of cyclopropyl allene derivatives from readily available cyclopropyne and aldehydes. Background technique [0002] Allenes (also known as allenes) are a class of highly reactive organic molecules due to their cumulative double bonds. They can undergo various organic reactions with high selectivity under mild conditions, thereby constructing various useful organic molecular frameworks. Therefore, allenes are novel and useful building blocks for organic synthesis. [0003] Cyclopropyl allene is a type of allene. The introduction of a three-membered carbocyclic ring with higher ring tension makes the reaction of cyclopropyl allene more complex than that of allene. During the reaction, the three-membered carbocycle breaks down due to high ring strain, enabling the generation of a series of useful co...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C1/32C07C13/28C07B49/00
CPCY02P20/55
Inventor 俞磊易容陈天
Owner YANGZHOU UNIV
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