Methyl iodide → Tert-butyl 2-methyl-4-(trifluoromethyl)phenylcarbamate

HRID 913805노트

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HRID 913805 반응식
[F:1][C:2]([F:18])([F:17])[C:3]1[CH:8]=[CH:7][C:6]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[CH:5][CH:4]=1.[C:19]([Li])(C)(C)C.IC>>[CH3:19][C:7]1[CH:8]=[C:3]([C:2]([F:17])([F:18])[F:1])[CH:4]=[CH:5][C:6]=1[NH:9][C:10](=[O:16])[O:11][C:12]([CH3:13])([CH3:14])[CH3:15]

참가 물질

4

반응물 3

HCID 6328Methyl iodideHCID 112307451,1-Dimethylethyl N-[4-(trifluoromethyl)phenyl]carbamateHCID 178418306HCID 178418306, 화합물

생성물 1

HCID 53420019Tert-butyl 2-methyl-4-(trifluoromethyl)phenylcarbamate수율 15.5%

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온도
0 °C

실험 절차

To a solution of tert-butyl 4-(trifluoromethyl)phenylcarbamate (13.2 g, 50.5 mmol) at −78° C. was added tert-butyllithium (1.7 in pentane, 62.4 mL, 106 mmol). The reaction was allowed to gradually warm to −20° C. in the ice bath (ca. 1 h). The reaction was recooled to −78° C. and treated with iodomethane (3.79 mL, 61 mmol). The reaction was allowed to gradually warm to 0° C. and held there for 15 min. The reaction was quenched by addition of saturated ammonium chloride. The mixture was poured onto diethyl ether, washed with water (3×), then brine, dried over magnesium sulfate, and concentrated. The solid was triturated with pentane and filtered to collect a first crop (10.4 g, 75%). The mother liquor gave a second crop of solid (2.15 g, 15%) which was again collected by filtration. 1H-NMR (CDCl3, 500 MHz) δ 8.06 (d, J=8.2 Hz, 1H), 7.44 (d, J=8.9 Hz, 1H), 7.38 (s, 1H), 6.40 (bs, 1H), 2.28 (s, 3H), 1.53 (s, 9H); 13C-NMR (CDCl3, 126 MHz) δ 152.5, 139.8, 127.2 (q, J=3.8 Hz), 126.2, 125.0 (q, J=33 Hz), 124.4 (q, J=272 Hz), 124.2 (q, J=3.8 Hz), 119.5, 81.3, 28.4, 17.7. Mass spec.: 298.00 (MNa)+.

후처리

  1. customwas recooled to −78° C.
  2. customThe reaction was quenched by addition of saturated ammonium chloride
  3. additionThe mixture was poured onto diethyl ether
  4. washwashed with water (3×)
  5. dry with materialbrine, dried over magnesium sulfate
  6. concentrationconcentrated
  7. customThe solid was triturated with pentane
  8. filtrationfiltered
  9. customto collect a first crop (10.4 g, 75%)

출처 및 근거

ORD 기록
ord-16b48441633e43899472cff6a33be816
출처 데이터셋
uspto-grants-2011_09
특허 번호
US08026257B2

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