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

HRID 1811067Notes

Reaction equation

HRID 1811067 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

Procedure

Step 2 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 treated with diethyl azodicarboxylate (3.74 g, 21.5 mmol) dropwise at 0° C. and was stirred overnight while warming slowly to rt. The mixture was concentrated and the residue was dissolved in DCM (20 mL), filtered to remove undissolved solid and concentrated. The residue was purified by column chromatography (eluting with hexane) to give tert-butyl 5-bromothiazol-2-yl(isopropyl)carbamate as a light yellow oil (3.10 g, 90%). 1H NMR (400 MHz, chloroform-d) δ 7.34 (s, 1H) 5.29 (m, 1H) 1.59 (s, 9H) 1.45 (d, 6.8 Hz, 6H). Mass spectrum m/z 265, 267 (M+H—C4H9)+.

Workup

  1. concentrationThe mixture was concentrated
  2. dissolutionthe residue was dissolved in DCM (20 mL)
  3. filtrationfiltered
  4. customto remove undissolved solid
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography (eluting with hexane)

Sources & evidence

ORD record
ord-f349b0cb22154c5cafd7a4d8d1d94cc9
Source dataset
uspto-grants-2013_01
Patent number
US08362065B2

Reaction notes

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