P-Phenylenediamine → Benzyl N-(4-aminophenyl)carbamate

HRID 2201719Notes

Reaction equation

[C:1]1([NH2:8])[CH:6]=[CH:5][C:4]([NH2:7])=[CH:3][CH:2]=1.C(N(C(C)C)CC)(C)C.Cl[C:19]([O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:20]>ClCCl>[CH2:22]([O:21][C:19](=[O:20])[NH:7][C:4]1[CH:5]=[CH:6][C:1]([NH2:8])=[CH:2][CH:3]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

Conditions

Temperature: 0 °C

Procedure

1,4-Phenylenediamine (10 g, 0.093 mol) was stirred rapidly in dichloromethane (800 mL) with diisopropylethylamine (16 mL, 0.093 mol) and the solution cooled to 0° C. A solution of benzyl chloroformate (13 mL, 0.093 mol) in dichloromethane (100 mL) was added very slowly via a dropping funnel. The reaction was left to warm to room temperature over 16 h and concentrated in vacuo. The remaining residue was purified by column chromatography on silica eluting with ethyl acetate/petroleum ether (using a gradient from 25% to 80%) to give 1 as a cream solid (15.5 g, 69.6%). 1H NMR (CDCl3, 400 MHz) δ 3.56 (s(br), 2H, NH2), 5.18 (s, 2H, CH2), 6.45 (s(br), 1H, NH), 6.64 (d, 2H, J=8.8 Hz, ArH), 7.15 (d, 2H, J=6.9 Hz, ArH), 7.36 (m, 5H, ArH).

Workup

waitThe reaction was left
temperatureto warm to room temperature over 16 h
concentrationconcentrated in vacuo
customThe remaining residue was purified by column chromatography on silica eluting with ethyl acetate/petroleum ether (

Sources & evidence

ORD record: ord-2e995e1f33fe4e9ca569f8aa1da770c0
Source dataset: uspto-grants-2016_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09365508B2

Reaction notes

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