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A kind of terminal alkene halogenated 1,3-enyne compound and its preparation and application

A compound, the technology of alkenyl halogenation, applied in the field of terminal alkenyl halogenation, can solve the problems of complex synthesis routes and few alternative methods, and achieve broad application prospects and good inhibitory selectivity

Active Publication Date: 2021-10-15
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Terminally halogenated 1,3-enynes have pharmaceutical activity and are widely used as synthetic precursors and pharmaceutical intermediates, but their synthetic pathways are complicated and there are very few alternative methods

Method used

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  • A kind of terminal alkene halogenated 1,3-enyne compound and its preparation and application
  • A kind of terminal alkene halogenated 1,3-enyne compound and its preparation and application
  • A kind of terminal alkene halogenated 1,3-enyne compound and its preparation and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Embodiment 1: the preparation of alkyne halide (I)

[0031] (1) Preparation of phenyl alkyne chloride (I-1)

[0032] The reaction formula is as follows:

[0033]

[0034] Add phenylacetylene (II-1) (2.042g, 20mmol), cesium carbonate (3.84g, 22mmol), tetra-n-butylammonium chloride (278mg, 1mmol) into a round-bottomed flask of carbon tetrachloride, at 70 The reaction was stirred and stirred at °C for 7 hours. After the reaction, add n-hexane (100 mL) to dilute, filter, collect the filtrate, use a rotary evaporator to evaporate the solvent under reduced pressure in a water bath at 40°C. Finally, column chromatography (mobile phase is petroleum ether) yielded a colorless target compound (I-1) with a yield of 83.0%. Its structure is characterized as follows:

[0035] 1 H NMR (600MHz, CDCl 3 )δ7.36-7.33(m,2H),7.24-7.20(m,3H). 13 C NMR (150MHz, CDCl 3 ) δ131.9,128.6,128.3,122.1,69.4,68.0.GC-MS(EI):m / z 136[M + ],138[(M+2) + ].

[0036] The preparation methods of ...

Embodiment 2

[0049] Example 2: Preparation of 1,3-enyne compound (III-1) with terminal alkenyl chloride

[0050] The reaction formula is as follows:

[0051]

[0052] Add IPrAuCl (5mol%, 9.3mg, 0.015mmol) in reaction bottle, NaBArF 4 (10mol%, 26.6.3mg, 0.03mmol), first dissolved with 2.0mL dichloroethane, and added phenylalkyne chloride (I-1) (41.0mg, 0.3mmol) into the reaction flask at 15°C, and started stirring , to which phenylacetylene (II-1) (30.6 mg, 0.3 mmol) was added, stirred and reacted at 15° C. for 10 hours, and the reaction process was monitored with a TLC plate. After the reaction, filter, wash the filter cake with dichloromethane (0.6mL×2), combine the filtrates, evaporate the solvent, and finally use column chromatography (mobile phase is n-hexane, Rf=0.5-0.7) to purify the terminal alkenes Chlorinated 1,3-enynes (III-1), yield 91%.

[0053] Its structure is characterized as follows:

[0054] 1 H NMR (600MHz, CDCl 3 )δ7.66(d,J=1.2Hz,1H),7.65-7.62(m,3H),7.42(dd,J=9....

Embodiment 3

[0055] Example 3: Preparation of 1,3-enyne compound (III-2) with terminal alkenyl chloride

[0056] The reaction formula is as follows:

[0057]

[0058] The phenylacetylene (II-1) (30.6mg, 0.3mmol) in Example 2 was replaced by p-chlorophenylacetylene (II-2) (41.0mg, 0.3mmol), other operations were the same as in Example 2, and finally the terminal Alkenyl-chlorinated 1,3-enynes (III-2), yield 91%. Its structure is characterized as follows:

[0059] 1 H NMR (600MHz, CDCl 3 )δ7.55(d, J=7.0Hz, 2H), 7.46(d, J=8.5Hz, 2H), 7.36-7.28(m, 5H), 6.82(s, 1H). 13 C NMR (150MHz, CDCl 3 )δ135.65, 134.92, 132.98, 128.74, 128.71, 128.65, 126.85, 126.18, 124.16, 121.19, 97.34, 85.64. GC-MS (EI): m / z 272 [M + ].IRν max (cm -1 ):3414,1627,1486,1388,1093,828,696.

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Abstract

The present invention provides a terminal alkenyl halogenated 1,3-enyne compound represented by formula (III). The present invention synthesizes terminal alkenyl halogenated 1,3-enynes through the catalytic reaction of aryl alkyne chloride and aryl alkyne in one step. 1,3-enyne compound is simple and convenient. This type of terminal alkenyl-halogenated 1,3-enyne compound has anti-tumor activity and has broad application prospects in the drug development system, in order to provide a more effective way;

Description

(1) Technical field [0001] The present invention relates to terminal alkenyl halogenated 1,3-enynes and their preparation and application. (2) Background technology [0002] The 1,3-enyne structure is a very useful precursor substance for organic synthesis, the basis for constructing multi-substituted aromatic rings, the basic unit for many biologically active substances, and a drug intermediate. Xerulin, Bupleurynol, Terbinafine and Oxamflatin are representative substances of conjugated 1,3-enyne structures, among which Xerulin is used to inhibit the biological activity of enzymes, Bupleurynol is a natural bioactive drug, and Terbina Terbinafine can treat superficial fungal infection very well, and Oxamflatin can well inhibit DNA synthesis and cell proliferation. [0003] 1,3-enyne compounds (III) with terminal alkenyl halogenation are widely used as synthetic precursors and pharmaceutical intermediates. Halogen atoms can affect the spatial structure of the compound, the h...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C22/04C07C25/24C07C69/78C07C17/275C07C17/278C07C67/347A61P35/00
CPCA61P35/00C07C17/275C07C17/278C07C22/04C07C25/24C07C67/347C07C69/78
Inventor 王宇光李静蔡东霖
Owner ZHEJIANG UNIV OF TECH
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