Method for synthesizing 1,4-naphthoquinone cyclopropane compound

A synthesis method and technology of cyclopropane, which is applied in the field of synthesis of organic compounds, can solve the problems of unfavorable industrial production and large quantities, and achieve the effects of good substrate adaptability, mild reaction conditions and low operation risk

Active Publication Date: 2019-06-18
浙江工业大学上虞研究院有限公司 +1
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Problems solved by technology

[0009] Aiming at the drawbacks of the traditional synthesis of cyclopropane compounds, Kazuhiko Takai recently used alkenes and I 2 CHB(OR) 2 Synthesis of boriridine compounds under chromium chloride catalyzed conditions [see Org.Lett., 2017, 19(22), pp6104–6107], however, this method requires the addition of 6 times the equivalent of chromium dichloride, which will A large amount of metal waste is generated, which is not conducive to industrial production

Method used

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  • Method for synthesizing 1,4-naphthoquinone cyclopropane compound
  • Method for synthesizing 1,4-naphthoquinone cyclopropane compound
  • Method for synthesizing 1,4-naphthoquinone cyclopropane compound

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Experimental program
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Effect test

Embodiment 1

[0036]

[0037] Add 0.3mmol (E)-3-phenyl-1-(2-(phenylethynyl)phenyl)prop-2-en-1-one, 0.06mmol ferric chloride, 0.9mmol diiodine pentoxide to In a 15mL thick-walled pressure-resistant reaction tube, add 3mL of 1,4-dioxane as a solvent. Next, magnetic stirring was performed at 100° C. for 0.5 hours. After being cooled to room temperature, two spoonfuls of column chromatography silica gel (100-200 mesh) were added to the reaction solution, and the solvent was removed by distillation under reduced pressure, and the pure product (in petroleum ether) was obtained by column chromatography separation as shown in the structural formula / ethyl acetate=20:1 as eluent). The material was a white solid, 68% yield.

[0038] Characterization data: 1 H NMR (500MHz, CDCl 3 ): δ8.21-8.18(m, 1H), 8.15, -8.12(m, 1H), 7.84-7.80(m, 2H), 7.27-7.24(m, 3H), 7.17-7.09(m, 5H), 6.78(d, J=7Hz, 2H), 3.69(d, J=6Hz, 1H), 3.45(d, J=6Hz, 1H)

[0039] 13 C NMR (125MHz, CDCl 3 ):δ192.73,191.06,134.48,1...

Embodiment 2

[0041]

[0042]0.3mmol (E)-1-(2-(phenylethynyl)phenyl)-3-(o-tolyl)prop-2-en-1-one, 0.06mmol iron nitrate, 0.9mmol diiodine pentoxide Add it into a 15mL thick-walled pressure-resistant reaction tube, and then add 3mL of 1,4-dioxane as a solvent. Next, magnetic stirring was performed at 100° C. for 0.5 hours. After being cooled to room temperature, two spoonfuls of column chromatography silica gel (100-200 mesh) were added to the reaction solution, and the solvent was removed by distillation under reduced pressure, and the pure product (in petroleum ether) was obtained by column chromatography separation as shown in the structural formula / ethyl acetate=20:1 as eluent). The material was a white solid, 51% yield.

[0043] Characterization data: 1 H NMR (500MHz, CDCl 3 ): δ8.25-8.20(m, 1H), 8.17-8.12(m, 1H), 7.84-7.79(m, 2H), 7.22-7.17(m, 3H), 7.15-7.11(m, 3H), 7.06- 7.03(m, 1H), 6.86(t, J=8Hz, 1H), 6.54(d, J=8Hz, 1H), 3.87(d, J=8Hz, 1H), 3.50(d, J=8Hz, 1Hz) ,2.40(s,3H). ...

Embodiment 3

[0046]

[0047] 0.3mmol (E)-3-(2-methoxyphenyl)-1-(2-(phenylethynyl)phenyl)prop-2-en-1-one, 0.03mmol ferric chloride, 0.9 Add mmol diiodine pentoxide to a 15 mL thick-walled pressure-resistant reaction tube, and then add 3 mL of 1,4-dioxane as a solvent. Next, magnetic stirring was performed at 100° C. for 0.5 hours. After being cooled to room temperature, two spoonfuls of column chromatography silica gel (100-200 mesh) were added to the reaction solution, and the solvent was removed by distillation under reduced pressure, and the pure product (in petroleum ether) was obtained by column chromatography separation as shown in the structural formula / ethyl acetate=20:1 as eluent). The material was a white solid in 78% yield.

[0048] Characterization data: 1 H NMR (500MHz, CDCl 3 ): δ8.23-8.19(m, 1H), 8.14-8.10(m, 1H), 7.81-7.77(m, 2H), 7.22-7.17(m, 5H), 7.13-7.10(m, 1H), 6.80 (d, J=8Hz, 1H), 6.61(t, J=8Hz, 1H), 6.52(dd, J 1 =7.5Hz,J 2 =1Hz, 1H)3.82(s, 3H), 3.77-3.74(m,...

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Abstract

The invention provides a method for synthesizing 1,4-naphthoquinone cyclopropane and a derivative thereof. The synthesis method is characterized by taking an o-alkynyl chalcone compound shown in a formula (I) as an initiator, taking ferric chloride or ferric nitrate as a catalyst, reacting for 0.1-1 hours at the temperature of 80 DEG C-120 DEG C in an organic solvent under the condition of takingdiiodine pentoxide as an oxidant, and performing separation and purification to prepare a corresponding target product. The synthesis method provided by the invention has the characteristics that theharm to environment is little; the reaction conditions are mild; the operation is convenient; and the like.

Description

technical field [0001] The invention relates to a method for synthesizing organic compounds, in particular to a method for synthesizing 1,4-naphthoquinone cyclopropane compounds. Background technique [0002] Due to its unique properties, 1,4-naphthoquinone has been widely used in dyes and organic pharmaceutical intermediates, and has become a hot spot. In industrial production, 1,4-naphthoquinone is an important raw material in fine chemicals, widely used in intermediates of dyes, medicines, spices, pesticides, plasticizers, etc., and is a polymerization regulator for synthetic rubber and resins. Important substances of paper cooking aids, such as 1,4-naphthoquinone is an important intermediate for the synthesis of naphthoquinone dyes and their derivatives, anthraquinone, tetrahydroanthraquinone, high-purity 1-aminoanthraquinone, and antineoplastic drugs. It is a raw material for the synthesis of 2,3-dihydro-1,4-anthraquinone series dyes, and can be used as a polymerizatio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C46/02C07C50/16C07C50/24C07C50/34C07D333/22C07C253/30C07C255/56
Inventor 刘运奎郑立孟鲍汉扬金红卫
Owner 浙江工业大学上虞研究院有限公司
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