Reference of 61881-19-4,Some common heterocyclic compound, 61881-19-4, name is 2,2,2-Trifluoro-N-phenylacetimidoyl chloride, molecular formula is C8H5ClF3N, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.
Alcohol 15* (136 mg, 0.19 mmol) was dissolved in CH2CI2(2 mL). Levulinic acid (0.1 mL, 0.96 mmol), 4-dimethylaminopyridine (140 mg, 1 .15 mmol) and di-/sopropylcarbodiimide (0.15 mL, 0.96 mmol) were added. The reaction mixture was stirred at r.t. overnight. The mixture was diluted with CH2CI2, washed with brine and then concentrated in vacuo. The crude product was purified by chromatography column on silica gel (Hexanes/EtOAc = 1 :1 ) to afford the levulinate ester (150 mg, 97%). The levulinate ester (161 mg, 0.199 mmol) was dissolved in acetone and water (6.25 mL, v/v = 4/1 ) at 0 C. TCCA (46 mg, 0.199 mmol) was added. The reaction mixture was allowed to warm to r.t. overnight. The reaction mixture was diluted with ethyl acetate, washed with sat NaHCO3 and brine. The organic layer was dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by column chromatography on silica gel (Hexanes/EtOAc = 1/2) to give the hemiacetal (121 mg, 79%). To a solution of hemiacetal (121 mg, 0.158 mmol) in acetone (3 mL) was added K2CO3(66 mg, 0.48 mmol) and PhN=C(CI)CF3(98 mg, 0.48 mmol). The mixture was stirred overnight at r.t.. The solution was filtered and concentrated in vacuo. The residue was purified by column chromatography on silica gel (Hexanes/EtOAc = 2.2/1 to 1/1 ) to give the imidate 24* (139 mg, 94%). [a]D25= 59.57 (c = 0.25, CHCIs);1H NMR (400 MHz, CDCI3) delta 7.31 -7.25 (m, 16H), 7.19 (m, 1 H), 7.09 (m, 1 H), 6.73 (m, 3 H), 5.42 (brs, 1 H), 5.31 (dd, J = 2.0, 10.8 Hz, 1 H), 4.97 (br, 1 H), 4.86 (d, J = 10.8 Hz, 1 H), 4.74-4.56 (m, 6 H), 4.37 (d, J = 1 1 .2 Hz, 1 H), 4.01 (dd, J = 2.8, 10.4 Hz, 1 H), 3.79 (s, 3 H), 3.77 (m, 1 H), 3.68 (m, 1 H), 3.36 (t, J = 9.6 Hz, 1 H), 2.89-2.69 (m, 3 H), 2.52 (m, 1 H), 2.18 (s, 3 H), 2.1 1 (s, 3 H), 1 .29 (d, J = 6.4 Hz, 3 H);13C NMR (101 MHz, CDCI3) delta 206.31 , 172.54, 170.44, 167.16, 143.40,138.75, 138.08, 137.33, 128.88, 128.64, 128.53, 128.38, 128.23, 128.20, 127.89,127.76, 127.67, 127.61 , 124.44, 1 19.45, 100.57, 79.70, 77.76, 77.31 , 75.19, 73.1 1 , 72.07, 72.01 , 71 .75, 71 .18, 68.94, 68.86, 52.79, 37.97, 29.81 , 27.86, 21 .27, 18.08; HRMS (ESI): calcd for C49H52F3NOi4Na [M + Na]+: 958.3238, found: 958.3303.
These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 2,2,2-Trifluoro-N-phenylacetimidoyl chloride, its application will become more common.
Reference:
Patent; MAX-PLANCK-GESELLSCHAFT ZUR FOeRDERUNG DER WISSENSCHAFTEN E.V.; SEEBERGER, Peter; PEREIRA, Claney Lebev; XIAO, Guozhi; KHAN, Naeem; ANISH, Chakkumkal; (120 pag.)WO2016/156338; (2016); A1;,
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