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Terminal alkenyl halogenated 1,3-enyne compound as well as preparation method and application thereof

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

Active Publication Date: 2019-03-22
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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  • Terminal alkenyl halogenated 1,3-enyne compound as well as preparation method and application thereof
  • Terminal alkenyl halogenated 1,3-enyne compound as well as preparation method and application thereof
  • Terminal alkenyl halogenated 1,3-enyne compound as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: Preparation of alkyne halide (I)

[0031] (1) Preparation of phenylalkyne chloride (I-1)

[0032] The reaction formula is as follows:

[0033]

[0034] Phenylacetylene (II-1) (2.042 g, 20 mmol), cesium carbonate (3.84 g, 22 mmol), and tetra-n-butylammonium chloride (278 mg, 1 mmol) were added to a round-bottomed flask of carbon tetrachloride at 70 The reaction was stirred at °C for 7 hours. After the reaction was completed, n-hexane (100 mL) was added to dilute, and the filtrate was collected by filtration. The filtrate was evaporated under reduced pressure in a 40° C. water bath using a rotary evaporator to remove the solvent. Finally, column chromatography (mobile phase: petroleum ether) obtained the 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 ...

Embodiment 2

[0049] Example 2: Preparation of terminal alkene chlorinated 1,3-enyne compound (III-1)

[0050] The reaction formula is as follows:

[0051]

[0052] To the reaction flask was added IPrAuCl (5mol%, 9.3mg, 0.015mmol), NaBArF 4 (10mol%, 26.6.3mg, 0.03mmol), first dissolve with 2.0mL dichloroethane, add phenylacetylene chloride (I-1) (41.0mg, 0.3mmol) to the reaction flask at 15°C, and stir , phenylacetylene (II-1) (30.6 mg, 0.3 mmol) was added thereto, and the reaction was stirred at 15° C. for 10 hours. The reaction process was monitored by TLC plate. After the reaction is completed, filter, wash the filter cake with dichloromethane (0.6 mL×2), combine the filtrates, evaporate the solvent, and finally purify by column chromatography (mobile phase is n-hexane, Rf=0.5-0.7) to obtain terminal alkene Chlorinated 1,3-enyne compound (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...

Embodiment 3

[0055] Example 3: Preparation of terminal alkene chlorinated 1,3-enyne compounds (III-2)

[0056] The reaction formula is as follows:

[0057]

[0058] The phenylacetylene (II-1) (30.6 mg, 0.3 mmol) in Example 2 was replaced with p-chlorophenylacetylene (II-2) (41.0 mg, 0.3 mmol), and other operations were the same as in Example 2, and finally the terminal was obtained. Alkenyl chlorinated 1,3-enyne compound (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 invention provides a terminal alkenyl halogenated 1,3-enylene compound shown by a formula (III). According to the invention, a terminal alkenyl halogenated 1,3-enayne compound is synthesized in one step through a catalytic reaction between aryl alkyne chlorine and aryl alkyne, and the synthesis is concise and convenient; the terminal alkenyl halogenated 1,3-enayne compound has anti-tumor activity, has a wide application prospect in a drug development system, and is expected to provide a more effective approach for treatment of related diseases; (as described in the specification).

Description

(1) Technical field [0001] The present invention relates to terminal alkene halogenated 1,3-enyne compounds and their preparation and application. (2) Background technology [0002] The 1,3-enyne structure is a very useful precursor for organic synthesis, the basis for the construction of polysubstituted 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 structure, among which Xerulin is used to inhibit the biological activity of enzymes, Bupleurynol is a natural biologically active drug, terbinafine Terbinafine can be excellent in the treatment of superficial fungal infections, and Oxamflatin can better inhibit DNA synthesis and cell proliferation. [0003] Terminal alkene halogenated 1,3-enyne compounds (III) are widely used as synthetic precursors and pharmaceutical intermediates. Physiological properties and physicochemica...

Claims

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Application Information

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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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