Calcium Carbonate → 4-morpholino-N-(4-nitrophenoxycarbonyl)aniline

HRID 657209Notes

Reaction equation

HRID 657209 reaction equation
[O:1]1[CH2:6][CH2:5][N:4]([C:7]2[CH:13]=[CH:12][C:10]([NH2:11])=[CH:9][CH:8]=2)[CH2:3][CH2:2]1.C([O-])([O-])=O.[Ca+2].Cl[C:20]([O:22][C:23]1[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=1)=[O:21]>C(Cl)Cl.C(Cl)Cl.CO>[N+:29]([C:26]1[CH:25]=[CH:24][C:23]([O:22][C:20](=[O:21])[NH:11][C:10]2[CH:12]=[CH:13][C:7]([N:4]3[CH2:3][CH2:2][O:1][CH2:6][CH2:5]3)=[CH:8][CH:9]=2)=[CH:28][CH:27]=1)([O-:31])=[O:30]

Participants

6

Reactant 3

HCID 10112Calcium CarbonateHCID 75655Benzenamine, 4-(4-morpholinyl)-HCID 821294-Nitrophenyl chloroformate

Product 1

HCID 227075274-morpholino-N-(4-nitrophenoxycarbonyl)anilineYield 35.9%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 21226129Dichloromethane methanolSolvent2×

Procedure

A mixture of 4-morpholinoaniline (1.01 g, 5.68 mmol) and CaCO3 (743 mg, 7.42 mmol) (10 micron powder) was treated with a solution of 4-nitrophenyl chloroformate (1.49 g, 7.39 mmol) in DCM (7.5 mL) in one portion under air on an ice bath. The thick, easily stirred reaction slurry was stirred for 1-2 min on the ice bath before stirring at rt for 1 h. The slurry was then diluted with 9:1 DCM/MeOH (7.5 mL) and directly applied to a flash silica column (95:5 DCM/MeOH) to provide 0.7 g of material. This was further purified by trituration with hot toluene (25 mL) to afford the title compound as a light olive green powder (444 mg, 23%). 1H NMR (300 MHz, CDCl3) δ 8.28 (m, 2H), 7.42-7.31 (m, 4H), 6.95-6.85 (m, 3H), 3.86 (m, 4H), 3.13 (m, 4H).

Workup

  1. customThe thick, easily stirred reaction slurry

Sources & evidence

ORD record
ord-2e3a303f9d0d4617abc0bd82f1eb4be9
Source dataset
uspto-grants-2011_12
Patent number
US08071768B2

Reaction notes

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