Propylene Oxide → 6-Methoxy-4-methyl-8-nitro-5-(7-phenylheptoxy)quinoline

HRID 1030180Notes

Reaction equation

HRID 1030180 reaction equation
[OH:1][C:2]1[C:11]([O:12][CH3:13])=[CH:10][C:9]([N+:14]([O-:16])=[O:15])=[C:8]2[C:3]=1[C:4]([CH3:17])=[CH:5][CH:6]=[N:7]2.Br[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C1OC1C.CCN(CC)CC>CN(P(N(C)C)(N(C)C)=O)C>[CH3:13][O:12][C:11]1[C:2]([O:1][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[C:3]2[C:8](=[C:9]([N+:14]([O-:16])=[O:15])[CH:10]=1)[N:7]=[CH:6][CH:5]=[C:4]2[CH3:17]

Participants

6

Reactant 4

HCID 6378Propylene Oxide2×HCID 8471Triethylamine2×HCID 27356031-Bromo-7-phenylheptaneHCID 1357785114-Methyl-5-hydroxy-6-methoxy-8-nitroquinoline

Product 1

HCID 6163856-Methoxy-4-methyl-8-nitro-5-(7-phenylheptoxy)quinolineYield 50%

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent

Procedure

To a stirred mixture of 5-hydroxy-6-methoxy-4-methyl-8-nitroquinoline (18 g, 0.077 mol) and 1-bromo-7-phenyl heptane [Example 1a] (15 g, 0.059 mol) in HMPA (45 ml) at 130° C., was added, dropwise, during 1 h, a solution of propylene oxide (18 ml) and Et3N (1 ml). After six more hours, second portions of propylene oxide (4 ml) and Et3N (1 ml) were added and heating was continued for 4 h. The cooled mixture was extracted successively with pet ether, Et2O and Me2CO. The residue returned 2.5 g of starting material (i.e., 5-hydroxy-6-methoxy-4-methyl-8-nitroquinoline). The combined pet ether and Et2O extracts were washed (H2O, dil NaOH, H2O) dried (Na2SO4) and concentrated to a viscous oil. This material was dissolved in CHCl3, placed on a silica gel column (200 g) and eluted with CHCl3. Concentration of the eluates and crystallization of the residue from pet ether (Darco) gave 12 g, (50%) of 6-methoxy-4-methyl-8-nitro-5-(7-phenyl heptoxy) quinoline as yellow crystals, mp 53°-54° C.

Workup

  1. additionwas added
  2. temperatureheating
  3. waitwas continued for 4 h
  4. extractionThe cooled mixture was extracted successively with pet ether, Et2O and Me2CO
  5. washThe combined pet ether and Et2O extracts were washed (H2O, dil NaOH, H2O)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated to a viscous oil
  8. dissolutionThis material was dissolved in CHCl3
  9. washeluted with CHCl3
  10. customConcentration of the eluates and crystallization of the residue from pet ether (Darco)

Sources & evidence

ORD record
ord-26f61b21e19042c8a9fe3e71694409ac
Source dataset
uspto-grants-1992_04
Patent number
US05104885

Reaction notes

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