Propylene Oxide → 6-Methoxy-4-methyl-8-nitro-5-(9-phenylnonoxy) quinoline

HRID 1030190Notes

Reaction equation

HRID 1030190 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][CH2:26][CH2:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.CN(P(N(C)C)(N(C)C)=O)C.C1OC1C>CCN(CC)CC>[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][CH2:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=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 OxideHCID 12679HexamethylphosphoramideHCID 11119579Benzene, (9-bromononyl)-HCID 1357785114-Methyl-5-hydroxy-6-methoxy-8-nitroquinoline2×

Product 1

HCID 540302836-Methoxy-4-methyl-8-nitro-5-(9-phenylnonoxy) quinolineYield 32.1%

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Procedure

To a stirred mixture of 5-hydroxy-6-methoxy-4-methyl-8-nitroquinoline (4.7 g, 0.02 mol), 1 bromo-9-phenylnonane (4.2 g, 0.015 mol) and HMPA (10 ml), at 125°-130° C., was added dropwise, during 0.5 h, a mixture of propylene oxide (6 ml) and Et3N (1 ml). The reaction was continued for 6 h, allowed to cool and extracted successively with pet ether, Et2O and Me2CO leaving 1.9 g of insoluble starting material, 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. The residual oil was dissolved in CHCl3, placed on a silica gel column (100 g) and eluted with CHCl3. The eluates were concentrated, triturated with pet ether and crystallized from Et2O (Darco) to give 2.1 g of 6-methoxy-4-methyl-8-nitro- 5-(9-phenylnonoxy) quinoline as yellow crystals, mp 56°-56.5° C. This material was used without further purification.

Workup

  1. additionat 125°-130° C., was added dropwise, during 0.5 h
  2. temperatureto cool
  3. extractionextracted successively with pet ether, Et2O and Me2CO
  4. customleaving 1.9 g
  5. washThe combined pet ether and Et2O extracts were washed (H2O, dil NaOH, H2O)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. dissolutionThe residual oil was dissolved in CHCl3
  9. washeluted with CHCl3
  10. concentrationThe eluates were concentrated
  11. customtriturated with pet ether
  12. customcrystallized from Et2O (Darco)

Sources & evidence

ORD record
ord-79f959f4c2bf458784eb011b0dce2371
Source dataset
uspto-grants-1992_04
Patent number
US05104885

Reaction notes

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