N-bromobutanimide → HCID 54459406, compound

HRID 2257444Notes

Reaction equation

HRID 2257444 reaction equation
C1C(=O)N([Br:8])C(=O)C1.[CH3:9][C@H:10]([O:17][C:18]1[CH:23]=[CH:22][C:21]([CH3:24])=[C:20]([N+:25]([O-:27])=[O:26])[CH:19]=1)[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16]>ClCCl>[Br:8][CH2:24][C:21]1[CH:22]=[CH:23][C:18]([O:17][C@@H:10]([CH3:9])[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])=[CH:19][C:20]=1[N+:25]([O-:27])=[O:26]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 53973427HCID 53973427, compound

Product 1

HCID 54459406HCID 54459406, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A suspension of 6.1 g (34.4 mmol) of NBS and 4 g of silica gel in 125 ml of dry dichloromethane was stirred under argon for 30 min. Then a solution of 4.56 g (17.2 mmol) of (S)-4-(1-methylheptyloxy)-2-nitro-toluene in 150 ml of dichloromethane was added via syringe. The reaction mixture was stirred at room temperature for 72 h. The resulting suspension was filtered through a short silica gel pad and the pad was washed several times with dichloromethane. The solvent was evaporated and the crude product extracted with a mixture of hexanes/ethyl acetate [95/5]. The suspension was filtered, the solvent removed and the residue was purified by flash chromatography using hexanes as eluent, affording 4.6 g (78%) of (S)-α-Bromo-4-(1-methylheptyloxy)-2-nitrotoluene (Compound 35, Scheme VI, R1 =(S)-OCH(CH3)C6H13) as a yellow liquid; Rf [hexanes/ethyl acetate 98/2]: 0.26; 1H NMR (300 MHz, CDCl3): δ 0.86(t, 3H, J=6.7 Hz), 1.18-1.48(m, 8H), 1.30(d, 3H, J=6.1 Hz), 1.58(m 1H), 1.70(m, 1H), 4.40(m, 1H), 4.77(s, 2H), 7.06(dd, 1H, J=2.7 Hz, J=8.5 Hz), 7.40(d, 1H, J=8.5 Hz), 7.50(d, 1H, J=2.7 Hz); 13C NMR (300 MHz, CDCl3): δ 13.98, 19.36, 22.50, 25.28, 29.10, 29.25, 31.67, 36.12, 75.00, 111.93, 121.08, 124.14, 133.61, 148.69, 158.92; IR (CHCl3): 3020, 2930, 2850, 1625, 1525, 1500, 1350, 1320, 1250, 1100, 975, 850, 825 cm-1 ; Mass spectrum, m/z(rel.intensity): 345(M+ +1 1.38), 343(M+ -1 1.35), 264(37), 152(100), 112(28), 71(59), 57(93), 55(38), 43(93), 41(70).

Workup

  1. stirringThe reaction mixture was stirred at room temperature for 72 h
  2. filtrationThe resulting suspension was filtered through a short silica gel pad
  3. washthe pad was washed several times with dichloromethane
  4. customThe solvent was evaporated
  5. extractionthe crude product extracted with a mixture of hexanes/ethyl acetate [95/5]
  6. filtrationThe suspension was filtered
  7. customthe solvent removed
  8. customthe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-41a11e5a238b4e3293e6b5e5eaa26024
Source dataset
uspto-grants-1997_08
Patent number
US05658493

Reaction notes

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