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Preparation method of nickel-catalyzed trifluoromethyl diaryliodonium

A technology of trifluoromethyl aryl and fluoromethyl aryl, which is applied in the field of preparation of trifluoromethyl aryl selenide, can solve the problems of narrow application range of substrates, difficult acquisition of catalysts, poor atom economy, etc., and achieves The effect of wide application range of substrates, high yield, and low requirements for equipment

Active Publication Date: 2017-09-01
WUHAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although there are no drugs containing trifluoromethaneselenyl, selenium is widely believed to have certain antitumor effects (Redman, C.; Scott, J.A.; Baines, A.T.; Basye, J.L.; Clark, L.C.; Calley, C. ; Roe, D.; Payne, C.M.; Nelson, M.A.Cancer Lett.1998,125,103), and there are a variety of selenium-containing health products on the market, so the compounds containing trifluoromethylselenium are screened for biological activity, and they are investigated in Applications in the field of life sciences are of great research value
[0004] At present, the trifluoromethylthiolation method on the aromatic ring is very mature, but there are few studies on the introduction of trifluoromethylselenyl group into the aromatic substrate.
Although some progress has been made in metal-involved trifluoromethylselenylation methods in recent years, these methods suffer from poor atom economy (Chen, C.; Ouyang, L.; Lin, Q.; Liu, Y.; Hou , C.; Yuan, Y.; Weng, Z.Chem.-Eur.J.2014,20,657–661), catalysts are not readily available, or substrates are narrowly applicable (Aufiero,M.; Sperger,T.; Tsang, A.-K; Schoenebeck, F.Angew.Chem.Int.Ed.2015,54,10322–10326) etc.

Method used

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  • Preparation method of nickel-catalyzed trifluoromethyl diaryliodonium
  • Preparation method of nickel-catalyzed trifluoromethyl diaryliodonium
  • Preparation method of nickel-catalyzed trifluoromethyl diaryliodonium

Examples

Experimental program
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Effect test

Embodiment 1

[0041]

[0042] At room temperature, in a 100mL nitrogen-protected reaction flask, add 4-iodoanisole (4.68g, 20mmol), tetramethylammoniumtrifluoromethylselenide (5.33g, 24mmol), 2,2'-bipyridine (0.31 g, 2mmol) and bis-(1,5-cyclooctadiene)nickel (0.28g, 1mmol), then add tetrahydrofuran (50mL) with a syringe, and react at room temperature for 2 hours. The reaction solution was spin-dried, and the residue was subjected to silica gel column chromatography (n-hexane eluent) to obtain 4-trifluoromethylselenoanisole (4.69 g, 92%).

[0043] 1 H NMR (400MHz, CDCl 3 )δ7.66(d, J=8.8Hz, 2H), 6.91(d, J=8.8Hz, 2H), 3.83(s, 3H); 19 F NMR (376MHz, CDCl 3 )δ-37.2(s,3F); 13 C NMR (100MHz, CDCl 3 )δ161.4, 138.9, 122.5 (q, J = 333.0Hz), 115.2, 112.9, 55.3.

Embodiment 2

[0045]

[0046] At room temperature, in a 100mL nitrogen-protected reaction flask, add 4-iodoacetophenone (4.92g, 20mmol), tetramethylammoniumtrifluoromethylselenide (5.33g, 24mmol), 2,2'-bipyridine (0.31 g, 2mmol) and tetrakis(triphenylphosphine)nickel (1.11g, 1mmol), then tetrahydrofuran (50mL) was added by syringe, and reacted at room temperature for 2 hours. The reaction solution was spin-dried, and the residue was subjected to silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain 4-trifluoromethylselenoacetophenone (3.47g , 65%).

[0047] 1 H NMR (400MHz, CDCl 3 )δ7.95(d, J=8.3Hz, 2H), 7.83(d, J=8.2Hz, 2H), 2.62(s, 3H); 19 F NMR (376MHz, CDCl 3 )δ-35.2(s,3F); 13 C NMR (100MHz, CDCl 3 )δ197.2, 138.2, 136.6, 129.1, 128.2, 122.3 (q, J = 332.9Hz), 26.6.

Embodiment 3

[0049]

[0050] At minus 80 degrees Celsius, in a 100mL nitrogen-protected reaction flask, add ethyl 4-iodobenzoate (5.52g, 20mmol), tetramethylammoniumtrifluoromethylselenide (5.33g, 24mmol), 2,2'- Pyridine (0.31g, 2mmol) and bis-(1,5-cyclooctadiene)nickel (0.28g, 1mmol), and tetrahydrofuran (50mL) were added by syringe, and reacted at 0°C for 2 hours. The reaction solution was spin-dried, and the residue was subjected to silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain ethyl 4-trifluoromethylselenobenzoate (4.16 g, 70%).

[0051] 1 H NMR (400MHz, CDCl 3 )δ8.04(d, J=8.4Hz, 2H), 7.80(d, J=8.2Hz, 2H), 4.39(q, J=7.0Hz, 2H), 1.40(t, J=7.1Hz, 3H) ; 19 F NMR (376MHz, CDCl 3 )δ-35.3(s,3F); 13 C NMR (126MHz, CDCl 3 )δ165.7, 136.4, 132.2, 130.4, 127.9, 122.4 (q, J=332.4Hz), 61.4, 14.2. 1447,1396,1369,1302,1284,1273,1179,1130,1098,1066,1015,964,853,784,759,739,690cm -1 .HRMS-EIcalcd.for C 10 h 9 f 3 o 2 74 Se: 291.9779; F...

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Abstract

The invention discloses a preparation method of nickel-catalyzed trifluoromethyl diaryliodonium. The method comprises the following steps of mixing aryl halide, trifluoromethyl selenium-based tetramethyl ammonium, a nickel catalyst and an organic phosphine ligand or dipyridyl compound, reacting at -80 DEG C to 10 DEG C for 5min to 48h, separating and purifying to obtain the trifluoromethyl diaryliodonium. The aryl halide comprises an antidepressant moclobemide or fenofibrate for treating adult hyperlipidaemia. The preparation method is available in raw materials, mild in condition, good in reaction selectivity, high in yield, good in functional group compatibility, wide in substrate application range (suitable for aryl chloride), low in demands on instruments and equipment and simple in technological operation.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of trifluoromethyl aryl selenide. Background technique [0002] Fluorine atoms have the characteristics of the largest electronegativity, atomic radius equivalent to that of hydrogen atoms, and good fat solubility. The introduction of fluorine atoms into drug molecules can usually increase the pharmacological activity, metabolic stability, fat solubility, and bioavailability of the original molecule. . In the 1950s and 1960s, the advent of Fluphenazine and 5-Fluorouracil marked the beginning of the application of fluorine-containing compounds in medicine. After decades of development, fluorine-containing organic compounds have occupied an important position in anesthetics, antipsychotics, steroidal anti-inflammatory drugs, anti-infectives, cardiovascular drugs, anti-tumor drugs, enzyme inhibitors, diagnostic drugs, etc. According to statistics, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C391/00C07C391/02C07D207/325C07D209/08C07D209/42C07D215/16C07D231/14C07D263/56C07D277/64C07D295/04C07D295/13C07D307/91C07D311/22C07D317/14C07D333/54C07D335/16
CPCC07C391/00C07C391/02C07D207/325C07D209/08C07D209/42C07D215/16C07D231/14C07D263/56C07D277/64C07D295/04C07D295/13C07D307/91C07D311/22C07D317/14C07D333/54C07D335/16
Inventor 张成潘韩家斌杨炼董涛
Owner WUHAN UNIV OF TECH
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