Iodine → ethyl (NZ)-N-(4-butyl-2-tert-butyl-1,2-thiazol-5-ylidene)carbamate

HRID 76292

반응식

HRID 76292 반응식
[C:1]([N:5]=[CH:6][CH2:7][CH2:8][CH2:9][CH2:10][CH3:11])([CH3:4])([CH3:3])[CH3:2].[C:12]([N:17]=[C:18]=[S:19])(=[O:16])[O:13][CH2:14][CH3:15].II.C([O-])(O)=O.[Na+].CCOCC.C([O-])(O)=O.[Na+]>C1COCC1.CCOCC.N1C=CC=CC=1.CO>[CH2:8]([C:7]1=[CH:6][N:5]([C:1]([CH3:2])([CH3:3])[CH3:4])[S:19]/[C:18]/1=[N:17]\[C:12](=[O:16])[O:13][CH2:14][CH3:15])[CH2:9][CH2:10][CH3:11]

참가 물질

10

반응물 5

HCID 807IodineHCID 85320Ethyl isothiocyanatoformateHCID 516892Sodium BicarbonateHCID 11829679N-(tert-butyl)-N-hexylideneamineHCID 23682952Ether sodium bicarbonate

생성물 1

HCID 87184151ethyl (NZ)-N-(4-butyl-2-tert-butyl-1,2-thiazol-5-ylidene)carbamate수율 67.7%

시약·촉매·용매 4

HCID 887Methanol용매HCID 1049Pyridine용매HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매

실험 절차

To a solution of Example 1A (4.2 g, 27 mmol) in THF (100 mL) at room temperature under N2 was added O-ethyl carbonisothiocyanatidate (3.55 g, 27 mmol). The reaction mixture was stirred for 1 hour and iodine (6.8 g, 27 mmol), MeOH (100 mL) and pyridine (10 mL) were added. The reaction mixture was stirred for 2 hours. The reaction mixture was poured into saturated NaHCO3/Et2O and stirred for 30 minutes. Additional saturated NaHCO3 and Et2O were added and the organic layer was separated. The aqueous layer was extracted with Et2O (2×) and combined organics were dried (MgSO4) and concentrated in vacuo. Toluene and acetonitrile were added and evaporated to remove water and pyridine. The crude compound was purified by flash chromatography using 0-100% EtOAc in hexane as eluent to give 5.2 g of the title compound as yellow solid. 1H NMR (300 MHz, CDCl3) δ ppm 0.93 (t, J=7.3 Hz, 3 H), 1.27-1.47 (m, 5 H), 1.54-1.73 (m, 11 H), 2.59-2.74 (m, 2 H), 4.28 (q, J=7.1 Hz, 2 H), 7.78 (s, 1 H). MS (DCI/NH3) m/z 285 (M+H)+.

후처리

  1. stirringThe reaction mixture was stirred for 2 hours
  2. stirringstirred for 30 minutes
  3. customthe organic layer was separated
  4. extractionThe aqueous layer was extracted with Et2O (2×)
  5. dry with materialcombined organics were dried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. additionToluene and acetonitrile were added
  8. customevaporated
  9. customto remove water and pyridine
  10. customThe crude compound was purified by flash chromatography

출처 및 근거

ORD 기록
ord-3416ea4b658f4ecfbab6ccd9fe06e383
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08835475B2

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