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

HRID 76292

Reaktionsgleichung

Reaktionsgleichung von HRID 76292
[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]

Komponenten

10

Edukt 5

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

Produkt 1

HCID 87184151ethyl (NZ)-N-(4-butyl-2-tert-butyl-1,2-thiazol-5-ylidene)carbamateAusbeute 67,7 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 887MethanolLösungsmittelHCID 1049PyridineLösungsmittelHCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

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)+.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-3416ea4b658f4ecfbab6ccd9fe06e383
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08835475B2

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