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

HRID 253653ノート

反応式

HRID 253653 の反応式
[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]

参加物

10

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 4

HCID 887Methanol溶媒HCID 1049Pyridine溶媒HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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, 3H), 1.27-1.47 (m, 5H), 1.54-1.73 (m, 11H), 2.59-2.74 (m, 2H), 4.28 (q, J=7.1 Hz, 2H), 7.78 (s, 1H). MS (DCI/NH3) m/z 285 (M+H)+.

後処理

  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

出典と根拠

ORDレコード
ord-9d9dab8647a74fe29d2f1d43f029f11c
出典データセット
uspto-grants-2011_01
特許番号
US07872033B2

反応ノート

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