Diethyl Ether → HCID 59253011, compound

HRID 884750Notes

Reaction equation

HRID 884750 reaction equation
[C:1]([O:5][C:6](=[O:21])[NH:7][N:8]1[C:17]([CH3:18])=[CH:16][C:15]2[C:10](=[C:11]([F:19])[CH:12]=[CH:13][CH:14]=2)[C:9]1=[O:20])([CH3:4])([CH3:3])[CH3:2].[Br:22]N1C(=O)CCC1=O.CCOCC>CN(C)C=O>[C:1]([O:5][C:6](=[O:21])[NH:7][N:8]1[C:17]([CH3:18])=[C:16]([Br:22])[C:15]2[C:10](=[C:11]([F:19])[CH:12]=[CH:13][CH:14]=2)[C:9]1=[O:20])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 67184N-bromobutanimideHCID 59252970HCID 59252970, compound

Product 1

HCID 59253011HCID 59253011, compoundYield 18.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of (8-fluoro-3-methyl-1-oxo-1H-isoquinolin-2-yl)-carbamic acid tert-butyl ester (501.9 mg, 1.717 mmol) and N-bromosuccinimide (366.0 mg, 2.056 mmol) in N,N-dimethylformamide (5 mL) was stirred at r.t. for 60 min. It was poured into 50 ml ether, washed with 5% aq. NaHCO3 two times, then with water 3 times, white precipitate formed, which was filtered and washed with ether to give 118 mg of the pure title product. Supernatant gave 490 mg more of the title product as a colourless solid; total yield 95.4%. LC-MS (m/z) 271.5 and 273.3 (major fragment, M-Boc), tR=1.39. 1H NMR (500 MHz, CDCl3) 1.51 (br. s, 9H, tBu), 2.64 (s, 3H, Me), 7.11 (dd, J=8.2 Hz, J=10.6 Hz, 1H, C7H), 3.67 (br. s, 1H, NH), 7.63 (dt, J (d)=4.95 Hz, J (t)=8.1 Hz, 1H, C6H), 7.68 (d, J=8.1 Hz, 1H, C5H). 19F NMR (470.59 MHz, CFCl3=0 ppm), 4:96 mixture of rotamers, −108.9 (br. s, 0.04F), −109.98 (br. s, 0.96F). 13C APT NMR (CDCl3=77.43 ppm): 20.15 (Me), 28.47 (tBu), 83.47 (C of tBu), 113.44 (C), 114.24 (d, J=21.4 Hz, C7H), 122.57 (d, J=4 Hz, C5H), 134.68 (d, J=10.3 Hz, C6H), 138.31 (s, C), 142.69 (s, C), 155.91 (C), 158.42 (C), 161.63 (s, C), 163.74 (s, C).

Workup

  1. washwashed with 5% aq. NaHCO3 two times
  2. customwith water 3 times, white precipitate formed
  3. filtrationwhich was filtered
  4. washwashed with ether

Sources & evidence

ORD record
ord-c777be3eb60742c9a10bc5672773bc54
Source dataset
uspto-grants-2012_08
Patent number
US08242134B2

Reaction notes

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