Isopropanol → Tert-butyl 5-bromothiazol-2-yl(isopropyl)carbamate

HRID 2197552Notes

Reaction equation

HRID 2197552 reaction equation
[Br:1][C:2]1[S:6][C:5]([NH:7][C:8](=[O:14])[O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[N:4][CH:3]=1.[CH:15](O)([CH3:17])[CH3:16].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[Br:1][C:2]1[S:6][C:5]([N:7]([CH:15]([CH3:17])[CH3:16])[C:8](=[O:14])[O:9][C:10]([CH3:11])([CH3:13])[CH3:12])=[N:4][CH:3]=1

Participants

6

Reactant 4

HCID 3776IsopropanolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 21300388tert-butyl N-(5-bromo-1,3-thiazol-2-yl)carbamate

Product 1

HCID 58688351Tert-butyl 5-bromothiazol-2-yl(isopropyl)carbamateYield 90.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of tert-butyl 5-bromothiazol-2-ylcarbamate (3 g, 10.7 mmol), isopropanol (6.40 g, 107.4 mmol) and triphenylphosphine (5.63 g, 21.5 mmol) in THF (30 mL) was added diethyl azodicarboxylate dropwise at 0° C. The mixture was stirred at 0° C. and slowly warmed up to room temperature overnight. The solvent was evaporated. The residue was redissolved in dichloromethane (20 mL) and filtered to get rid of the undissolved solid. The filtrate was concentrated and purified by column chromatography on silica gel using 100% hexane to give a light yellow oil (3.10 g, 90% yield). LCMS (Conditions C): 4.19 min (RT); (M+H)+=267.01 (100%), 265.01 (95%), 224.95 (60%), 222.95 (60%). 1H NMR, 400 MHz, CDCl3: δ 7.34 (s, 1H), 5.29 (m, 1 H), 1.59 (s, 9 H), 1.45 (d, 6.8 Hz, 6 H).

Workup

  1. temperatureslowly warmed up to room temperature overnight
  2. customThe solvent was evaporated
  3. dissolutionThe residue was redissolved in dichloromethane (20 mL)
  4. filtrationfiltered
  5. customto get rid of the undissolved solid
  6. concentrationThe filtrate was concentrated
  7. custompurified by column chromatography on silica gel using 100% hexane

Sources & evidence

ORD record
ord-a159eff32cba48e09baa37b0a1b1a0b0
Source dataset
uspto-grants-2012_12
Patent number
US08338604B2

Reaction notes

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