1-trifluoromethyl-tetrasubstituted cyclopentene derivatives as well as preparation method and application thereof

A kind of technology of trifluoromethyl and cyclopentene, applied in the field of chemical substances and preparation thereof

Active Publication Date: 2017-11-07
EAST CHINA NORMAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the prior art, there are few reports about the synthetic method of trifluoromethyl-substituted cyclopentene compounds. In view of the importance and potential application value of trifluoromethyl-substituted cyclopentene compounds, the development of novel and efficient Synthesis of trifluoromethyl-substituted cyclopentene compounds is particularly important

Method used

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  • 1-trifluoromethyl-tetrasubstituted cyclopentene derivatives as well as preparation method and application thereof
  • 1-trifluoromethyl-tetrasubstituted cyclopentene derivatives as well as preparation method and application thereof
  • 1-trifluoromethyl-tetrasubstituted cyclopentene derivatives as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] First weigh (3-(trifluoromethyl)but-3-en-1-ynyl)benzene (0.5mmol), silver nitrate (50mol%) in a dry reaction tube, add toluene under nitrogen atmosphere, and then Inject triethylamine (0.5 mmol) and 1,3-dicarbonyl compound - acetylacetone (1 mmol). Then, react at room temperature, and monitor the reaction by thin-layer chromatography silica gel (TLC) and ultraviolet during the reaction until (3-(trifluoromethyl)but-3-en-1-ynyl)benzene completely disappears. After the reaction was completed, it was filtered with diatomaceous earth and the solvent was removed by rotary evaporation under low pressure, and then the crude product was separated and purified by column chromatography (petroleum ether: ethyl acetate = 50:1) to obtain 1-trifluoromethyl-3-benzene Diacetyl-4,4-diacetyl-1-cyclopentene III-1 (70 mg, 47%).

[0039]

[0040] white solid. Mp 58.9-60.1°C. 1 H NMR (400MHz, CDCl 3 )δ7.32–7.25(m,3H),7.13–7.09(m,2H),6.21-6.18(m,1H),5.08-5.03(m,1H),3.81(dd,J=17.4,1.4Hz...

Embodiment 2

[0042] With 4-formyl-(3-(trifluoromethyl)but-3-en-1-ynyl)benzene (0.5mmol), 1,3-dicarbonyl compound——acetylacetone (1mmol) as raw materials, For other operations refer to Example 1, the reaction was stirred for 24 hours, purified by silica gel column chromatography (petroleum ether: ethyl acetate = 20:1), to obtain 1-trifluoromethyl-3-(4-formylphenyl)-4,4 - Diacetyl-1-cyclopentene III-2 (126 mg, 78%).

[0043]

[0044] white solid. Mp 77.7-79.4°C. 1 H NMR (500MHz, CDCl 3 )δ9.98(s,1H),7.81(d,J=7.8,2H), 7.31(d,J=7.8Hz,2H),6.18(s,1H),5.17(s,1H),3.79(d ,J=17.4Hz,1H),2.78(d,J=17.4Hz,1H),2.22(s,3H),1.58(s,3H). 13 C NMR (126MHz, CDCl 3 )δ202.42(s), 201.81(s), 191.41(s), 144.06(s), 135.94(s), 135.59(q, J=4.8Hz), 131.13(q, J=34.2Hz), 130.06( s), 129.75(s), 121.65 (q, J=269.9Hz), 78.99(s), 53.73(s), 34.92(s), 28.14(s), 26.60(s). 19 F NMR (471MHz, CDCl 3 )δ -66.11(s).HRMS(ESI) calcd for C 17 h 15 f 3 NaO 3 :347.0865,found:347.0863.

Embodiment 3

[0046] With 4-cyano-(3-(trifluoromethyl)but-3-en-1-ynyl)benzene (0.5mmol), 1,3-dicarbonyl compounds——acetylacetone (1mmol) as raw materials, For other operations refer to Example 1, the reaction was stirred for 24 hours, purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10:1), to obtain 1-trifluoromethyl-3-(4-cyanophenyl)-4,4 - Diacetyl-1-cyclopentene III-3 (115 mg, 72%).

[0047]

[0048] white solid. Mp 92.0-94.1°C. 1 H NMR (500MHz, CDCl 3 )δ7.57(d, J=8.5Hz, 2H), 7.23(d, J=8.5Hz, 2H), 6.16-6.14(m, 1H), 5.12(d, J=1.9Hz, 1H), 3.72( dd,J=17.4,1.2Hz,1H),2.77 (dd,J=17.4,1.3Hz,1H),2.19(s,3H),1.57(s,3H). 13 C NMR (126MHz, CDCl 3 ( q, J=270.1Hz), 118.13(s), 112.04(s), 78.84(s), 53.59(s), 34.89(s), 28.11(s), 26.63(s). 19 F NMR (471MHz, CDCl 3 )δ-66.15(s).MS(70eV):M / Z(%):321,43(100).HRMS(EI)calcd for C 17 h 14 f 3 o 2 N:321.0977,found:321.0976.

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Abstract

The invention discloses 1-trifluoromethyl-tetrasubstituted cyclopentene derivatives shown as the formula (III) in the description as well as a preparation method and an application thereof. The 1-trifluoromethyl-tetrasubstituted cyclopentene derivatives are prepared from 2-trifluoromethyl-1,3-conjugated enyne compounds in the formula (I) in the description and 1,3-dicarbonyl compounds in the formula (II) in the description through a cyclization reaction in an organic solvent under the action of a base and a catalyst. The method adopts mild reaction conditions, is simple to operate and has great significance in synthesis of polyfunctional group substituted fluorine-containing cyclopentene compounds in the formula (III).

Description

technical field [0001] The invention relates to a preparation method of a trifluoromethyl cyclopentene derivative, in particular to a preparation method of a 1-trifluoromethyl-tetrasubstituted cyclopentene derivative, and belongs to the technical field of chemical substances and their preparation. Background technique [0002] Cyclopentene and its derivatives are the core skeleton of many biologically active compounds, and are an important class of five-membered carbocyclic compounds. In view of their unique biological importance, a series of methods for the synthesis of such structures have been reported. Among them, including organic or metal catalyzed cyclization reactions, metal or thermodynamically promoted rearrangements, etc. ) K. Krohn, In Organic Synthesis Highlights; VCH: Weinheim, 1990; pp 97-104; c) R.C. Hartley, S.T. Caldwell, J. Chem. Soc., Perkin Trans. 12000, 477–501; d) L.F. Silva, Tetrahedron 2002, 58, 9137–9161; e) S. Das, S. Chandrasekhar, J.S. Yadav, R...

Claims

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Application Information

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IPC IPC(8): C07C45/69C07C49/567C07C49/583C07C49/792C07C49/577C07C253/30C07C255/56C07C67/293C07C67/347C07C69/76C07C69/145C07C69/757C07C201/12C07C205/45C07D333/22
CPCC07B2200/07C07C45/69C07C49/567C07C49/577C07C49/583C07C49/792C07C67/293C07C67/347C07C69/145C07C69/757C07C69/76C07C201/12C07C205/45C07C253/30C07C255/56C07D333/22
Inventor 肖元晶曾雨黄超乾胡岸靖程化毓赵秋华张俊良
Owner EAST CHINA NORMAL UNIVERSITY
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