Cesium carbonate → HCID 86668105, compound

HRID 474246Notes

Reaction equation

[OH:1][C:2]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].C([O-])([O-])=O.[Cs+].[Cs+].Br[CH2:20][CH2:21][NH:22][C:23](=[O:29])[O:24][C:25]([CH3:28])([CH3:27])[CH3:26]>CN(C=O)C>[C:4]([C:3]1[CH:6]=[CH:7][C:8]([N+:10]([O-:12])=[O:11])=[CH:9][C:2]=1[O:1][CH2:20][CH2:21][NH:22][C:23](=[O:29])[O:24][C:25]([CH3:28])([CH3:27])[CH3:26])#[N:5]

Participants

Conditions

Temperature: 0 °C

Procedure

To a stirred solution of 2-hydroxy-4-nitrobenzonitrile (5.0 g, 30.48 mmol) in DMF (25 mL) was added Cs2CO3 (14.89 g, 45.7 mmol). The mixture was cooled to 0° C., and tert-butyl (2-bromoethyl)carbamate (7.17 g, 32 mmol) was added at rt. The reaction mixture was stirred for 12 h at 90° C. under nitrogen. The reaction mixture was cooled to rt and DMF was removed in vacuo. The residue was treated with ethyl acetate (50 mL) and washed with brine (30 mL). The organic layer was dried over anhydrous sodium sulphate and concentrated in vacuo. The residue was taken up in dichloromethane (10 mL) and silica (5 g). The resultant slurry of the compound on silica was subjected to flash chromatography using a Teledyne Isco instrument (40 g RediSep silica column, 50% ethyl acetate in pet-ether) to get tert-butyl (2-(2-cyano-5-nitrophenoxy)ethyl)carbamate (4 g, 42.7%) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.90 (1H, d, J=8.4 Hz), 7.82 (1H, s), 7.76 (1H, d, J=8.4 Hz), 5.04 (1H, br s), 4.27-4.24 (2H, m), 3.66-3.60 (2H, m), 1.45 (9H, s).

Workup

temperatureThe reaction mixture was cooled to rt
customDMF was removed in vacuo
additionThe residue was treated with ethyl acetate (50 mL)
washwashed with brine (30 mL)
dry with materialThe organic layer was dried over anhydrous sodium sulphate
concentrationconcentrated in vacuo

Sources & evidence

ORD record: ord-0a3a9196fe2046ab94cf08d4b5fe55a4
Source dataset: uspto-grants-2014_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08637523B2

Reaction notes

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