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

HRID 1958477Notes

Reaction equation

HRID 1958477 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, 1 H), 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-45af2ab1f3c94020a67123db43cec226
Source dataset
uspto-grants-2013_04
Patent number
US08410128B2

Reaction notes

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