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A preparation method for obtaining methane functionalized products based on combined iron/photocatalysis

A technology of functionalization and products, applied in the preparation of organic compounds, chemical instruments and methods, preparation of carboxylic acid nitrile, etc., can solve the problems of low methane carbon utilization efficiency, put the process into practice, slow progress, etc. A wide range of substrates, the effect of strong applicability

Active Publication Date: 2022-08-02
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Unfortunately, O 2 The presence of leads to irreversible over-oxidation, resulting in a large amount of thermodynamically stable product CO 2 and H 2 O generation, therefore, the carbon utilization efficiency of methane remains low
Currently, progress in finding new catalysts to address this problem has been slow, and no economically viable process has yet been put into practice

Method used

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  • A preparation method for obtaining methane functionalized products based on combined iron/photocatalysis
  • A preparation method for obtaining methane functionalized products based on combined iron/photocatalysis
  • A preparation method for obtaining methane functionalized products based on combined iron/photocatalysis

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024]

[0025] In the high pressure photoreactor, add magneton, benzylidene malononitrile (3.1mg, 0.02mmol), FeCl 3 ·6H 2 O (0.6 mg, 10% mol) and 1 mL of acetonitrile (CH 3 EN). Assemble the high pressure photoreactor, replace the gas atmosphere in the reactor with methane gas (5000kPa), operate 5 times, and then fill the reactor with methane gas to 5000kPa. Finally, irradiate with a 70W 365nm light source and stir at room temperature. After 14 hours, the reaction was diluted with ether, washed with deionized water, and the organic layer was concentrated in vacuo. The crude reaction product was purified and isolated by silica gel column chromatography to obtain the target product (colorless oil 3.2 mg, 95%). 1 H NMR (400MHz, CDCl 3 )δ7.48-7.32(m, 5H), 3.88(d, J=6.2Hz, 1H), 3.48(quint, J=6.9Hz, 1H), 1.68(d, J=7.1Hz, 3H); 13 C NMR (101MHz, CDCl 3 )δ138.20, 129.28, 128.88, 127.25, 111.98, 111.70, 41.22, 31.24, 17.79; HRMS (ESI - ):calcd for C 11 H 9 N 2 [M-H] - 16...

Embodiment 2

[0027]

[0028] In a high pressure photoreactor, add magnon, 2-(4-trifluoromethyl-benzylidene)malononitrile (4.4mg, 0.02mmol), FeCl3·6H2O (0.6mg, 10%mol) and 1mL acetonitrile (CH 3 EN). Assemble the high pressure photoreactor, replace the gas atmosphere in the reactor with methane gas (5000kPa), operate 5 times, and then fill the reactor with methane gas to 5000kPa. Finally, irradiate with a 70W 365nm light source and stir at room temperature. After 10 hours, the reaction was diluted with ether, washed with deionized water, and the organic layer was concentrated in vacuo. The crude reaction product was purified and isolated by silica gel column chromatography to obtain the target product (colorless oil 4.6 mg, 97%). 1 H NMR (400MHz, CDCl 3 )δ7.71(d,J=8.2Hz,2H),7.51(d,J=8.1Hz,2H),3.92(d,J=6.1Hz,1H),3.56(p,J=6.9Hz,1H) ,1.70(d,J=7.1Hz,3H). 13 C NMR (101MHz, CDCl 3 )δ141.96,131.21(q,J=33.3Hz),127.88,126.29(q,J=3.7Hz),123.76(q,J=275.7Hz),111.54,111.36,40.90,30.86,17.74.HR...

Embodiment 3

[0030]

[0031] In the high pressure photoreactor, add magneton, 2,2-dicyanovinyl-benzoic acid methyl ester (4.2mg, 0.02mmol), FeCl 3 ·6H 2O (0.6 mg, 10% mol) and 1 mL of acetonitrile (CH 3 EN). Assemble the high pressure photoreactor, replace the gas atmosphere in the reactor with methane gas (5000kPa), operate 5 times, and then fill the reactor with methane gas to 5000kPa. Finally, irradiate with a 70W 365nm light source and stir at room temperature. After 10 hours, the reaction was diluted with ether, washed with deionized water, and the organic layer was concentrated in vacuo. The crude reaction product was purified and isolated by silica gel column chromatography to obtain the target product (colorless oil 4.4 mg, 97%). 1 H NMR (400MHz, CDCl 3 )δ8.10(d,J=8.4Hz,2H),7.44(d,J=8.3Hz,2H),3.97-3.91(m,4H),3.54(p,J=6.9Hz,1H),1.69( d, J=7.1Hz, 3H). 13 C NMR (101MHz, CDCl 3 )δ166.39,142.98,130.76,130.52,127.44,111.66,111.43,52.34,41.06,30.84,17.74.HRMS(ESI - ):calcd for...

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Abstract

The invention belongs to the field of organic synthetic chemistry, and relates to a preparation method for obtaining a methane functional product based on iron / photo combined catalysis. Specifically, the transition metal iron salt ferric chloride (FeCl 3 ) instead of traditional photosensitizers as the photosensitive center, the photo-induced ligand-to-metal charge transfer (LMCT) process of Fe-Cl complexes is used to generate chlorine radicals, and then the higher hydrogen atom transfer (HAT) of chlorine radicals is utilized. ) ability to realize the hydrocarbon activation of methane, and the unsaturated olefin raw material is used as a trapping agent to quickly and efficiently convert C(sp3)-H bonds into C-C bonds to obtain a variety of methane functionalized products.

Description

technical field [0001] The invention belongs to the field of organic synthetic chemistry, and relates to a preparation method and application of a methane functionalized product based on iron / light combined catalysis, in particular to the use of cheap transition metal iron salts ferric chloride or ferrous chloride as photosensitizers through light The reaction enables direct functionalization of methane. Background technique [0002] In nature, light alkanes, especially methane, are widely distributed and abundant. At present, this kind of organic carbon source with huge reserves and low cost is usually used as a fuel for energy. While increasing carbon emissions, its economic value is not very prominent, and its application in organic synthesis has not been fully developed. Realizing the direct conversion of methane to value-added chemicals has high atomic economy and great environmental significance, but due to CH 4 The high C-H bond strength (434 kJ / mol), negligible ele...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C253/30C07D207/408C07D213/57C07C255/33C07C255/35C07C255/41C07C255/51C07B37/02
CPCC07C253/30C07D207/408C07D213/57C07B37/02C07C255/33C07C255/35C07C255/41C07C255/51
Inventor 金云鹤张晴晴段春迎
Owner DALIAN UNIV OF TECH