tert-Butanol → tert-butyl N-(5-methylthiophen-2-yl)carbamate

HRID 422581Notes

Reaction equation

C[C:2]1[S:6][C:5]([C:7](O)=O)=[CH:4][CH:3]=1.CC[N:12]([CH2:15]C)CC.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:24])C=CC=CC=1.[C:34]([OH:38])([CH3:37])([CH3:36])[CH3:35]>>[CH3:7][C:5]1[S:6][C:2]([NH:12][C:15](=[O:24])[O:38][C:34]([CH3:37])([CH3:36])[CH3:35])=[CH:3][CH:4]=1

Participants

Reactant 4

HCID 6386tert-Butanol

HCID 8471Triethylamine

HCID 747135-Methylthiophene-2-carboxylic acid

HCID 199401P,P-Diphenylphosphinic azide

Product 1

HCID 716045tert-butyl N-(5-methylthiophen-2-yl)carbamateYield 75%

Conditions

Temperature: 65 °C

Procedure

To a solution of 5-methylthiophene-2-carboxylic acid (5 g, 35.2 mmol) in tert-butanol (99 mL) was added Et3N (3.91 g, 38.7 mmol) and diphenyl phosphoryl azide (10.65 g, 38.7 mmol). The reaction mixture was heated to 65° C. for 4 h, then refluxed for 4 h. The volatiles were removed under reduced pressure and the residual crude material was purified by flash chromatography on silica gel (DCM/MeOH: 98/2) to give the title compound (7 g, 75%): 1HNMR (DMSO) δ 10.10 (s, 1H), 6.43 (d, J=2 Hz, 1H), 6.29 (d, J=2 Hz, 1H), 2.30 (s, 3H), 1.42 (s, 9H).

Workup

temperaturerefluxed for 4 h
customThe volatiles were removed under reduced pressure
customthe residual crude material was purified by flash chromatography on silica gel (DCM/MeOH: 98/2)

Sources & evidence

ORD record: ord-5fd495a4cb0d425fa1be03a277f9be67
Source dataset: uspto-grants-2012_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08101645B2

Reaction notes

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