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An inert cycloalkane c(sp 3 )-h bond functionalization method

A cycloalkane, functionalization technology, applied in organic chemistry, oxidation to prepare carbonyl compounds, condensation to prepare carbonyl compounds, etc., can solve the problem of difficult metal atom orbital interaction, etc., and achieve mild reaction conditions, low price, and high yield. Effect

Active Publication Date: 2019-11-15
NINGBO UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the C(sp of inert naphthenes 3 )-H bonds have no empty low-energy orbitals and filled high-energy orbitals, and are not easy to interact with metal atomic orbitals, making inert cycloalkanes C(sp 3 )-H bond direct functionalization is more challenging

Method used

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  • An inert cycloalkane c(sp  <sup>3</sup> )-h bond functionalization method
  • An inert cycloalkane c(sp  <sup>3</sup> )-h bond functionalization method
  • An inert cycloalkane c(sp  <sup>3</sup> )-h bond functionalization method

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Experimental program
Comparison scheme
Effect test

Embodiment 13

[0032]

[0033] Add 41.6mg (0.4mmol) of styrene, 5.1mg (0.04mmol) of ferrous chloride, 144.0mg (1.6mmol) of tert-butanol peroxide, 110.4mg (0.8mmol) of potassium carbonate, and cyclic Heptane (2 mL), and the reaction flask was stirred at 100° C. for 24 h. After the reaction was completed, the reaction solution was filtered through a glass dropper containing silica gel, rinsed with ethyl acetate, the filtrate was spin-dried, and separated by column chromatography to obtain the target product, a colorless oily liquid, with a yield of 61%.

Embodiment 14

[0035]

[0036] Add 55.2 mg (0.4 mmol) of p-chlorostyrene, 5.1 mg (0.04 mmol) of ferrous chloride, 144.0 mg (1.6 mmol) of tert-butanol peroxide, and 110.4 mg (0.8 mmol) of potassium carbonate into a dry 10 mL schlenk bottle , cyclohexane (2mL), and the reaction bottle was stirred at 100°C for 24h. After the reaction was completed, the reaction solution was filtered through a glass dropper containing silica gel, rinsed with ethyl acetate, the filtrate was spin-dried, and separated by column chromatography to obtain the target product, a colorless oily liquid, with a yield of 71%.

Embodiment 15

[0038]

[0039] Add 53.6 mg (0.4 mmol) of p-methoxystyrene, 5.1 mg (0.04 mmol) of ferrous chloride, 144.0 mg (1.6 mmol) of tert-butanol peroxide, and 110.4 mg (0.8 mmol) of potassium carbonate into a dry 10 mL schlenk bottle. mmol), cyclohexane (2mL), and the reaction flask was stirred at 100°C for 24h. After the reaction was completed, the reaction solution was filtered through a glass dropper containing silica gel, rinsed with ethyl acetate, the filtrate was spin-dried, and separated by column chromatography to obtain the target product, a colorless oily liquid, with a yield of 77%.

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Abstract

The invention belongs to the field of organic synthesis, and particularly relates to an inert naphthenic hydrocarbon C(sp3)-H bond functionalization method. The method comprises the following steps: adding substituted styrene as shown in Formula Ia, catalyst ferrous chloride, oxidizer and alkali into a dry reaction bulb; adding naphthenic hydrocarbon as shown in Formula IIa; putting the reaction bulb under a condition of 100-120 DEG C, and reacting for 12-24 hours; and after the reaction is completed, filtering the reaction solution through glass dropper containing silica gel, flushing with ethyl acetate, performing spin-drying on the filtrate, and separating through column chromatography to obtain a target product as shown in Formula I. The reaction formula is shown in the specification.

Description

technical field [0001] The application belongs to the field of organic synthesis, in particular to a kind of inert cycloalkane C(sp 3 )-H bond functionalization method. Background technique [0002] C-H bond activation is the "holy grail" in the field of contemporary organic synthesis, and it is the most active research field in contemporary organic synthesis, reflecting the modern synthesis concept of high efficiency, high atom economy and environmental friendliness. With the flexible use of transition metals in the field of C–H bond activation, direct functionalization of various C–H bonds has been reported. Compared with traditional reactive functionalization reactions, the direct conversion of inert C–H bonds reduces the pre-functionalization of starting materials, making organic reactions more efficient and greener. Lazy C(sp 3 The direct functionalization of )-H bonds has not been studied much, so there is a lot of room for research. [0003] In 2015, Wang's resear...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C49/792C07C49/813C07C49/84C07C45/45C07C45/28
CPCC07C45/28C07C45/45C07C49/792C07C49/813C07C49/84
Inventor 黄依铃魏文廷朱文明应炜炜许恺怡杨晨光陈卫东
Owner NINGBO UNIV