Diethyl Ether → (alphaS)-alpha-Amino-4-nitrobenzenepropanamide

HRID 621762Notes

Reaction equation

Cl.C[NH:3][C@H:4]([C:15]([OH:17])=O)[CH2:5][C:6]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][CH:7]=1.C([N:20](CC)CC)C.CCOCC>CO>[N+:12]([C:9]1[CH:8]=[CH:7][C:6]([CH2:5][C@@H:4]([C:15]([NH2:20])=[O:17])[NH2:3])=[CH:11][CH:10]=1)([O-:14])=[O:13]

Participants

Conditions

Temperature: -10 °C

Procedure

A slurry of 1 (10.97 g, 42.1 mmol) in dry methanol (5 ml) was treated with triethylamine (6.45 ml). After clearing, anhydrous ether (200 ml) was added to the solution and cooled to -10° C. for one hour. Precipitated triethylamine hydrochloride was removed by filtration and the filtrate concentrated to a limpid yellow oil. The oil was added to dry methanol (250 ml) previously saturated with NH3 (g) at -10° C., tightly stoppered and left at -10° C. for 42 hours. The precipitated product was collected and dried under vacuum. The liquid filtrate was spotted on a TLC plate and developed with CHCl3 :MeOH (4:1) which revealed one spot at Rf =0.50, identical to that of the collected precipitate. The filtrate was therefore stripped to dryness and the remaining solid 2 combined with the precipitate (8.12 g, 92.3%): mp 160°-162° C.; 1H NMR (220 MHz, DMSO-d6), δ 8.07 (d, 2, J32 8.0), 7.5 (d, 2, J=8.0), 7.41 (s, 1), 7.00 (s, 1), 3.50 (t, 1, J=6.0), 3.09 (dd, 1, J=6.0, 16.0); 2.81 (dd, 1, J=6.0, 16.0) CI-MS 210 ((M+1)/z).

Workup

customPrecipitated triethylamine hydrochloride was removed by filtration
concentrationthe filtrate concentrated to a limpid yellow oil
additionThe oil was added to dry methanol (250 ml) previously saturated with NH3 (g) at -10° C.
customThe precipitated product was collected
customdried under vacuum

Sources & evidence

ORD record: ord-0c90999cc4794861a16f3a7d5922c800
Source dataset: uspto-grants-1989_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04824986

Reaction notes

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