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Chemical Structure| 916975-92-3 Chemical Structure| 916975-92-3

Structure of 916975-92-3

Chemical Structure| 916975-92-3

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Product Details of [ 916975-92-3 ]

CAS No. :916975-92-3
Formula : C11H8F3N3O2
M.W : 271.20
SMILES Code : FC(C1=CC([N+]([O-])=O)=CC(N2C=C(C)N=C2)=C1)(F)F
MDL No. :MFCD18800877

Safety of [ 916975-92-3 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H301-H411
Precautionary Statements:P264-P270-P301+P310-P321-P330-P405-P501
Class:6.1
UN#:2811
Packing Group:

Application In Synthesis of [ 916975-92-3 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 916975-92-3 ]

[ 916975-92-3 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 630125-49-4 ]
  • [ 822-36-6 ]
  • [ 916975-92-3 ]
YieldReaction ConditionsOperation in experiment
78.2% With isoquinolin-8-ol; copper(l) iodide; potassium carbonate; triethylamine; In N,N-dimethyl-formamide; at 100 - 140℃; for 5h; 13.5 g of <strong>[630125-49-4]3-bromo-5-nitro-trifluorotoluene</strong> (13.5 g, 0.05 mol), 5.0 g of 4-methyl-1H-imidazole (5.0 g, 0.06 mol), 1.42 g of cuprous iodide (1.42 g, 7.5 mmol), 2.2 g of 8-hydroxyisoquinoline (2.2 g, 7.5 mmol), 7.6 g of potassium carbonate (0.055 mol) and 50 mL of N,N-dimethylformamide were added to a 250 mL three-necked bottle, heated to 100 C., stirred to dissolve. Added with 0.75 g of triethylamine (0.75 g, 7.5 mmol), continued to heat to 140 C., reacted for 5 hours, to complete the reaction detected by TLC. Cooled down to 50-60 C., filtered, and the filter cake was washed with ethyl acetate, the filter liquor was washed with saline water and water, concentrated, then recrystallized by ethyl acetate and n-hexane (1:1), to get 10.6 g of yellow solid 3-(4-methyl-1H-imidazol-1-yl)-5-nitro-trifluorotoluene, with a yield of 78.2%, melting point 118-120 C., MS-ESI (m/z): 272(M+H), 1H NMR (400 MHz, CDCl3) delta 8.45(s, 2H), 7.95(s, 1H), 7.93(s, 1H), 7.16(s, 1H), 2.33(s, 3H).
53.3% Example 13 4-Methyl-1 -(3-nitro-5-tiotaf luoromethyl-phenyl)-1 H-imidazole (IX) (by aromatic substitution)4-Methylimidazole (10.5 g, 125.5 mmol) and potassium carbonate (12.0 g, 119.6 mmol) is suspended in Lambda/,Lambda/-dimethylformamide (80 mL) and stirred at 1000C for 1 hour. A solution of 1-fluoro-3-nitro-5-trifluoromethyl-benzene (12.5 g, 59.8 mmol) in EPO <DP n="26"/>ty/V-dimethylformamide (20 mL) is added over 10 minutes. The mixture is stirred at 1080C internal temperature for 3 hours. HPLC analysis shows complete consumption of the fluoride starting material. The mixture is cooled down to about 200C and water (200 mL) is added over 1 hour. The resulting suspension is filtered to give 17.5 g of wet solid (HPLC: 88.8 area% desired isomer, 8.9 area% undesired isomer/byproduct). A suspension of this material in water (100 mL) is stirred for 1 hour at room temperature. The solid is filtered, washed with water (100 mL) and dried at 50C under reduced pressure to give the crude product. HPLC analysis shows more than 90 area% of the desired product. Re-crystallization: A solution of above crude product (9.5 g) in ethyl acetate (50 mL) is treated for 2 hours at 700C with activated carbon (1 g) and filter aid (1 g) and, thereafter, is filtered, and the filtrate is evaporated to dryness to give 11.1 g of a residue. This material is dissolved in ethyl acetate (3.25 g) and heptane (50 mL) under reflux. The solution is seeded at 65C with 4-methyl-1-(3-nitro-5-trifluoromethyl-phenyl)-1H-imidazole and allowed to cool down to room temperature over night and afterwards stirred at 00C for 3 hours. The solid formed is filtered, washed with heptane (20 mL) and dried at 500C under reduced pressure to give 4-methyl-1-(3-nitro-5-trifluoromethyl-phenyl)-1 /-/-imidazole as a solid. Yield overall: 53.3% (HPLC purity: 98.2 area%), Melting point: 117-118C
21.1% With copper(l) iodide; potassium carbonate; ethylenediamine; In N,N-dimethyl-formamide; at 110℃; for 23h;Product distribution / selectivity; Example 10 4-Methyl-1-(3-nitro-5-trifluoromethyl-phenyl)-1H-imidazole (IX) (by catalyzed coupling)To a stirred suspension of <strong>[630125-49-4]1-bromo-3-nitro-5-trifluoromethyl-benzene</strong> (4.05 g, 15 mmol), 4-methyl-1 W-imidazole (2.01 g, 24 mmol, 98%) and potassium carbonate (3.73 g, 27 mmol) in Lambda/,Lambda/-dimethylformamide (10 mL) are added ethylenediamine (0.141 mL, 2.1 mmol) and copper(l) iodide (0.204 g, 1.05 mmol). The vigorously stirred mixture is heated to 110 0C for 23 hours. After that, most of the 1-bromo-3-nitro-5-trifluoromethyl- benzene is converted, and the suspension is allowed to cool down to room temperature. The mixture is diluted with terf-butyl methyl ether (30 mL) and 5% aqueous NaCI solution (30 mL) and isopropyl acetate (15 mL) are added. The aqueous layer is separated and extracted with a mixture of tert-buty methyl ether (10 mL) and isopropyl acetate (5 mL). The organic layers are combined and filtered. The filtrate is washed with water (10 mL), treated for 5 minutes with ethylenediamine (0.303 mL), washed with water (10 mL), 5% aqueous sodium EPO <DP n="24"/>metabisulfite solution (10 mL) and water (10 ml.) before it is treated with activated carbon (1.2 g) at room temperature for 1 hour. The suspension is filtered using filter aid, and the filtrate is evaporated to dryness under reduced pressure to give a clear, red-brown oil which solidifies upon standing at room temperature. The obtained solid is purified by column chromatography on silica gel eluting with a 4:5 mixture of ethyl acetate and hexane (in the presence of 0.5 volume% of triethylamine) to afford mainly 4-methyl-1-(3-nitro- 5-trifluoromethyl-phenyl)-1 /-/-imidazole as a pale yellow solid. Yield: 21.1% (HPLC purity: 96.7 area%) Melting point: 118-119C.
 

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