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Halogenated conjugate 1,3-eneyne compound and preparation method and application thereof

A compound and conjugation technology, applied in halogenated conjugation 1, can solve the problems of complex synthetic route of halogenated conjugated enynes and few alternative methods, and achieve the effect of simple and convenient method and broad application prospects

Active Publication Date: 2019-03-01
ZHEJIANG UNIV OF TECH
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  • Abstract
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Problems solved by technology

[0005] Halogenated conjugated 1,3-enynes are widely used as synthetic precursors and pharmaceutical intermediates, and have good pharmaceutical activity, but the synthesis route of halogenated conjugated enynes is complicated and there are very few alternative methods

Method used

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  • Halogenated conjugate 1,3-eneyne compound and preparation method and application thereof
  • Halogenated conjugate 1,3-eneyne compound and preparation method and application thereof
  • Halogenated conjugate 1,3-eneyne compound and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Embodiment 1: the preparation of alkyne halide (I)

[0035] (1) Preparation of phenyl alkyne chloride (I-1)

[0036] The reaction formula is as follows:

[0037]

[0038] 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 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:

[0039] 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) + ].

[0040] The preparation methods of other substitu...

Embodiment 2

[0053] Example 2: Preparation of chloroconjugated 1,3-enynes (III-1)

[0054] The reaction formula is as follows:

[0055]

[0056] Add IPrAuCl (5mol%, 9.3mg, 0.015mmol) in reaction bottle, NaBArF 4 (10mol%, 26.6.3mg, 0.03mmol), first dissolve with 2.0mL dichloroethane, add phenylacetylene (II-1) (30.6mg, 0.3mmol) in the reaction flask at 40°C, start stirring, and add Add phenylalkyne chloride (I-1) (41.0 mg, 0.3 mmol) and stir for 2 hours, and monitor the reaction process with a TLC plate. After the reaction is finished, filter and wash the filter cake with dichloromethane (0.6mL×2), combine the filtrates, evaporate the solvent, and finally purify by column chromatography (mobile phase is petroleum ether or n-hexane, Rf=0.6) to obtain chlorine Substituting conjugated 1,3-enynes (III-1) with a yield of 85%. Its structure is characterized as follows:

[0057] 1 H NMR (600MHz, CDCl 3 )δ7.66(dd, J=7.8,1.8Hz,2H),7.53(dd,J=6.7,3.0Hz,2H),7.40-7.37(m,3H),7.34(dd,J=7.0,2.8Hz ...

Embodiment 3

[0058] Example 3: Preparation of halogenated conjugated 1,3-enynes (III-2)

[0059] The reaction formula is as follows:

[0060]

[0061] Phenylacetylene (II-1) (30.6mg, 0.3mmol) in Example 2 was replaced by p-fluorophenylacetylene (II-2) (33.0mg, 0.3mmol), other operations were the same as in Example 2, and finally chlorine Substituting conjugated 1,3-enynes (III-2) with a yield of 83%. Its structure is characterized as follows:

[0062] 1 H NMR (600MHz, CDCl 3 )δ7.53(d, J=8.1Hz, 2H), 7.49(dd, J=8.3,5.6Hz, 2H), 7.17(d, J=8.1Hz, 2H), 7.02(t, J=8.5Hz, 2H), 6.38(s, 1H), 2.36(s, 3H). 13 C NMR (150MHz, CDCl 3 )δ162.72 (d, J=249), 142.76, 139.98, 133.79, 133.60 (d, J=7.5), 129.28, 126.22, 119.34 (d, J=18), 115.73 (d, J=22.5), 105.73 ,94.48,86.04,21.27.IRν max (cm -1 ):3415,1593,1496,1388,1225,823,803; GC-MS(EI):m / z256[M + ].

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Abstract

The invention provides a halogenated conjugate 1,3-eneyne compound shown by a formula (III). By means of catalytic reaction of aryl acetylene chlorine and aryl acetylene, the halogenated conjugate 1,3-eneyne compound is synthesized through one step, the operation is simple and convenient, the halogenated conjugate 1,3-eneyne compound has antineoplastic activity, has a wide application prospect ina drug development system and is expected to provide more effective ways for treatment of relevant diseases.

Description

(1) Technical field [0001] The invention relates to a halogenated conjugated 1,3-enyne compound, a preparation method and application thereof. (2) Background technology [0002] The conjugated 1,3-enyne structure is a very useful precursor 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] Halogenated conjugated 1,3-enyne compounds (III) are widely used as synthetic precursors and pharmaceutical intermediates. Halogen atoms can affect the spatial structure of the compound, the hydrophi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C25/24C07C22/04C07C17/278C07C17/275C07D333/12A61P35/00
CPCA61P35/00C07C17/275C07C17/278C07C22/04C07C25/24C07D333/12
Inventor 王宇光刘贝蔡东霖姚恩琪
Owner ZHEJIANG UNIV OF TECH
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