A method for synthesizing 1,4-naphthoquinone cyclopropane compounds

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

Active Publication Date: 2021-08-24
浙江工业大学上虞研究院有限公司 +1
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  • Abstract
  • Description
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  • Application Information

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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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  • A method for synthesizing 1,4-naphthoquinone cyclopropane compounds
  • A method for synthesizing 1,4-naphthoquinone cyclopropane compounds
  • A method for synthesizing 1,4-naphthoquinone cyclopropane compounds

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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 in the reaction solution, and the solvent was removed by distillation under reduced pressure, and then the pure product as shown in the structural formula was obtained by column chromatography separation (in petroleum ether / 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....

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 its derivatives. The synthesis method uses the o-alkynyl chalcone compound represented by formula (I) as a starting material, ferric chloride or ferric nitrate as a catalyst, and under the condition of diiodine pentoxide as an oxidizing agent, in an organic solvent , react at a temperature of 80°C to 120°C for 0.1‑1 hour, and obtain the corresponding target product after separation and purification. The synthesis method of the invention has the characteristics of little harm to the environment, mild reaction conditions, easy operation 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 Patents(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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