Methylamine → 1,2,3-Thiadiazole-4-carboxamide, N-methyl-5-(phenylamino)-
Reaction equation
[NH2:1][CH3:2].[Li]CCCC.C(O[C:11]([C:13]1[N:14]=[N:15][S:16][C:17]=1[NH:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:12])C.[NH4+].[Cl-]>C1CCCCC1.CCOC(C)=O>[CH3:2][NH:1][C:11]([C:13]1[N:14]=[N:15][S:16][C:17]=1[NH:18][C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)=[O:12]Participants
Conditions
- Temperature
- -30 °C
Procedure
To a solution of 2 M NH2CH3 in cyclohexane (2 mL) at −40° C. was added 0.8 mL of 2 M n-BuLi in cyclohexane under argon. A white precipitate was immediately observed. The mixture was stirred at −30° C. for 0.5 hours, and 5-phenylamino-[1,2,3]thiadiazole-4-carboxylic acid ethyl ester (60 mg, 0.24 mmole) in 1 mL of cyclohexane was slowly added. Greenish solution was immediately obtained. The reaction was slowly warmed up to room temperature and TLC showed a total disappearance of the starting material. A mixture of 7 mL of saturated NH4Cl solution and 7 mL of EtOAc was added to the ice-cooled flask and the solution was stirred for 30 minutes. The aqueous layer was neutralized to pH ˜7 and then extracted with EtOAc. The organic layer was absorbed with silica gel, loaded to a 53 g silica gel column, and eluted with hexane:EtOAc=5:1. A 25 mg white powder was obtained (45%). 1H NMR (ppm, DMSO-d6): 11.00 (br. s, 1H), 8.92 (br. q, 1H), 7.46 (t, 2H), 7.34 (d, 2H), 7.20 (t, 1H), 2.85 (d, 3H).
Workup
- customGreenish solution was immediately obtained
- temperatureThe reaction was slowly warmed up to room temperature
- temperaturecooled flask
- stirringthe solution was stirred for 30 minutes
- extractionextracted with EtOAc
- customThe organic layer was absorbed with silica gel
- washeluted with hexane
Sources & evidence
- ORD record
- ord-8c3c08c970a94fdc85a592a8898b4243
- Source dataset
- uspto-grants-2007_10
- Patent number
- US07288556B2
Reaction notes
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