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Method for synthesizing beta-iodo-nitroolefin compound

A synthetic method and technology of nitroalkenes, applied in the direction of preparation of nitro compounds, organic chemical methods, formation/introduction of nitro/nitroso groups, etc., can solve the problems of inapplicability and few reports of synthetic methods, and achieve the goal of obtaining The effect of high efficiency, good substrate adaptability and mild reaction conditions

Inactive Publication Date: 2016-11-09
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But so far, there are few reports about the synthetic methods of these compounds.
It has been reported in the literature that Sornsiri, H.; Natthapol, S.; Tassaporn, S.; Manat, P.; Vichai, R.; Darunee, S.; .,2014,33,7433–7442., with potassium persulfate compound salt (Oxone) as oxidant, sodium nitrite (NaNO 2 ) is the source of nitro, and potassium iodide is the source of halogen, the corresponding β-iodonitroalkene compound can be obtained, but the use of strong oxidant Oxone makes some sensitive groups unsuitable for this type of reaction

Method used

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  • Method for synthesizing beta-iodo-nitroolefin compound
  • Method for synthesizing beta-iodo-nitroolefin compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Compound 1

[0028] Phenylacetylene (51mg, 0.5mmol), elemental iodine (63.5mg, 0.25mmol) and tert-butyl nitrite (103.1mg, 1mmol) were mixed in 2ml of tetrahydrofuran solvent and added to the flask, and reacted at 50°C for 4 hours. After the reaction was detected by TLC, 111.3 mg of (1-iodo-2-nitrovinyl) benzene (compound 1) was separated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 20:1) , yield 80.9%, E / Z, >99:1.

[0029] Product characterization: pale yellow liquid; 1 H NMR (500MHz, CDCl3) δ7.63 (s, 1H), 7.34–7.26 (m, 3H), 7.25–7.19 (m, 2H). 13 C NMR (125MHz, CDCl3) δ142.18, 137.44, 127.56, 127.52, 126.25, 112.77.

Embodiment 2

[0031] Compound 1

[0032] Phenylacetylene (51mg, 0.5mmol), elemental iodine (127mg, 0.5mmol) and tert-butyl nitrite (103.1mg, 1mmol) were mixed in 2ml of tetrahydrofuran solvent and added to the flask, and reacted at 50°C for 4 hours. After the reaction was detected by TLC, 112.4mg of (1-iodo-2-nitrovinyl)benzene (compound 1) was separated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 20:1) , yield 81.7%, E / Z, >99:1.

[0033] Product characterization: light yellow liquid; detected by TLC, the rf value is 0.26, which is the same as the rf value of compound 1 obtained in Example 1.

Embodiment 3

[0035] Compound 1

[0036] Phenylacetylene (51mg, 0.5mmol), elemental iodine (63.5mg, 0.25mmol) and tert-butyl nitrite (257.8mg, 2.5mmol) were mixed in 2ml of tetrahydrofuran solvent and added to the flask, and reacted at 50°C for 4 hours. After the reaction was detected by TLC, 108.7 mg of (1-iodo-2-nitrovinyl) benzene (compound 1) was separated by column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 20:1) , yield 79.1%, E / Z, >99:1.

[0037] Product characterization: light yellow liquid; detected by TLC, compared with compound 1 obtained in Example 1, the rf value is the same.

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PUM

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Abstract

The invention provides a method for synthesizing a beta-iodo-nitroolefin compound as shown in a formula (III). The method comprises: mixing substituted alkyne shown in a formula (I), an iodine source and tert-butyl nitrite shown in a formula (II) in a solvent for completely reacting to obtain reaction liquid, and after reacting for 4 to 6h at a temperature of 25 to 80 DEG C, processing the reaction liquid to obtain the beta-iodo-nitroolefin compound, wherein the solvent is tetrahydrofuran, acetonitrile, acetone or 1,2-dichloroethane, and a ratio of quantities of fed substances, i.e., the substituted alkyne shown in the formula (I), the iodine source and the tert-butyl nitrite shown in the formula (II), is 1 to (0.5 to 1) to (2 to 5). The method provided by the invention is high in substrate adaptability and mild in reaction condition, does not relate to use of an oxidizing agent and a metal catalyst, is safe and environmental-friendly, is simple in reaction operation, and is more beneficial to application in medicine synthesis. The formulas are shown in the description.

Description

(1) Technical field [0001] The invention relates to a method for synthesizing β-iodonitroalkenes. Using alkyne compounds, iodine sources and tert-butyl nitrite as raw materials, various β-iodonitroalkenes can be synthesized under mild conditions. (2) Background technology [0002] β-Iodonitroalkenes are an important class of reaction intermediates in organic synthesis, which can undergo various transformations to obtain different important chemicals. For example, the halogen iodine contained in its structure is very prone to cross-coupling reaction under the catalysis of palladium; the nitro group contained in the structure can be converted into amino group under the catalytic reduction system, and then further converted into various other organic substances. But so far, there are few reports on the synthetic methods of these compounds. It has been reported in the literature that Sornsiri, H.; Natthapol, S.; Tassaporn, S.; Manat, P.; Vichai, R.; Darunee, S.; .,2014,33,7433...

Claims

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Application Information

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IPC IPC(8): C07B43/02C07C205/09C07C205/32C07C205/11C07C201/06C07D333/12C07D213/26
CPCC07B43/02C07B2200/07C07C201/06C07D213/26C07D333/12C07C205/09C07C205/32C07C205/11
Inventor 李小青樊媛媛许响生
Owner ZHEJIANG UNIV OF TECH
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