Methylamine → N-methyl-5-(morpholin-4-ylmethyl)-2-nitroaniline

HRID 2119334Notes

Reaction equation

[CH3:1][NH2:2].F[C:4]1[CH:5]=[C:6]([CH:14]=[CH:15][C:16]=1[N+:17]([O-:19])=[O:18])[CH2:7][N:8]1[CH2:13][CH2:12][O:11][CH2:10][CH2:9]1>CS(C)=O>[CH3:1][NH:2][C:4]1[CH:5]=[C:6]([CH2:7][N:8]2[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)[CH:14]=[CH:15][C:16]=1[N+:17]([O-:19])=[O:18]

Participants

Conditions

Temperature: 47 °C

Procedure

An aqueous solution of methylamine (40 wt %, 910 ml) at 30° C. is added to a 61° C. solution of 4-(3-fluoro-4-nitrobenzyl)morpholine (504 g) in DMSO (810 ml) followed by a DMSO rinse (150 ml) over ½ h. The mixture is allowed to reflux at 47 ° C. over 5 min then maintained at <51° C. by occasional ice bath cooling for remainder of the addition. The mixture is stirred at 50° C. for ¾ h and then water (2000 ml) is added. The mixture is cooled to 0° C. and the precipitate is collected by filtration, washed with water (1500 ml) and is dried in a nitrogen stream to give a bright orange solid (529 g). Physical characteristics: 1H NMR (400 MHz, DMSO-d6) δ2.35, 2.93, 3.44, 3.56, 6.63, 6.64, 7.78, 8.15; 13C NMR (100 MHz, DMSO-d6) δ29.95, 53.57, 62.27,66.54, 113.69, 115.76, 126.49, 130.16, 146.27, 148.07.

Workup

washrinse (150 ml) over ½ h
temperaturethen maintained at <51° C. by occasional ice bath
temperaturecooling for remainder of the addition
additionwater (2000 ml) is added
temperatureThe mixture is cooled to 0° C.
filtrationthe precipitate is collected by filtration
washwashed with water (1500 ml)
customis dried in a nitrogen stream

Sources & evidence

ORD record: ord-6da8db1285e74a26b75f9921d8c86fe4
Source dataset: uspto-grants-2004_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06686356B2

Reaction notes

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