Iodine → Tert-butyl (2-chloro-3-iodopyridin-4-YL)carbamate

HRID 1432950

반응식

HRID 1432950 반응식
C([Li])(C)(C)C.[C:6]([O:10][C:11](=[O:20])[NH:12][C:13]1[CH:18]=[CH:17][N:16]=[C:15]([Cl:19])[CH:14]=1)([CH3:9])([CH3:8])[CH3:7].[I:21]I>C1COCC1>[C:6]([O:10][C:11](=[O:20])[NH:12][C:13]1[CH:18]=[CH:17][N:16]=[C:15]([Cl:19])[C:14]=1[I:21])([CH3:9])([CH3:7])[CH3:8]

참가 물질

5

반응물 3

HCID 807IodineHCID 21858447tert-butyl N-(2-chloropyridin-4-yl)carbamateHCID 178418306HCID 178418306, 화합물

생성물 1

HCID 44721300Tert-butyl (2-chloro-3-iodopyridin-4-YL)carbamate수율 85.9%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-78 °C

실험 절차

tert-Butyllithium (36.3 mL, 1.7M in pentane) is added dropwise to a solution of (2-chloro-pyridin-4-yl)-carbamic acid tert-butyl ester (6.00 g, 26.2 mmol) in THF (46 mL) at −78° C. under Ar. The yellow/orange mixture is stirred for 2 h at −78° C. then warmed to −40° C. for 1 h then cooled to −78° C. before dropwise addition of I2 (15.65 g, 61.7 mmol) in THF (49 mL). The reaction mixture is stirred for 1.5 h at −78° C. then at −10° C. for 30 minutes. The reaction is quenched with saturated NH4Cl solution then diluted with CH2Cl2 and washed with saturated NH4Cl, saturated sodium thiosulfate, water then brine. The organic layer is dried over MgSO4, filtered and concentrated to dryness. The crude product is chromatographed eluting with 1-2% MeOH/CH2Cl2 to yield the title product (7.96 g, 22.5 mmol) as a bright yellow solid. 1H NMR (CDCl3, 300 MHz) δ8.14 (d, 1H), 8.02 (d, 1H), 7.32 (bs, 1H), 1.60 (s, 9H). EI MS [M]+=354, 356, Cl pattern.

후처리

  1. temperaturethen warmed to −40° C. for 1 h
  2. stirringThe reaction mixture is stirred for 1.5 h at −78° C.
  3. waitat −10° C. for 30 minutes
  4. customThe reaction is quenched with saturated NH4Cl solution
  5. additionthen diluted with CH2Cl2
  6. washwashed with saturated NH4Cl, saturated sodium thiosulfate, water
  7. dry with materialThe organic layer is dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated to dryness
  10. customThe crude product is chromatographed
  11. washeluting with 1-2% MeOH/CH2Cl2

출처 및 근거

ORD 기록
ord-83fc020bb3b84962a65c34a03a627800
출처 데이터셋
uspto-grants-2009_11
특허 번호
US07612075B2

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