Diethyl Ether → HCID 131715090, compound

HRID 542209Notes

Reaction equation

HRID 542209 reaction equation
[CH2:1]([N:8]1[CH2:13][CH2:12][N:11]([C:14](=[N:16][C:17]2[CH:22]=[C:21]([O:23][CH3:24])[C:20]([O:25][CH3:26])=[CH:19][C:18]=2[C:27]#[N:28])[CH3:15])[CH2:10][CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC[O:31]CC.[OH-:34].[Na+].C(Cl)[Cl:37]>CC(N(C)C)=O.[Cl-].[Zn+2].[Cl-]>[OH2:23].[ClH:37].[ClH:37].[NH2:28][C:27]1[C:18]2[C:17](=[CH:22][C:21]([O:23][CH3:24])=[C:20]([O:25][CH3:26])[CH:19]=2)[N:16]=[C:14]([N:11]2[CH2:12][CH2:13][N:8]([CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[CH2:9][CH2:10]2)[CH:15]=1.[OH2:31].[OH2:34].[NH2:28][C:27]1[C:18]2[C:17](=[CH:22][C:21]([O:23][CH3:24])=[C:20]([O:25][CH3:26])[CH:19]=2)[N:16]=[C:14]([N:11]2[CH2:12][CH2:13][N:8]([CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[CH2:9][CH2:10]2)[CH:15]=1.[ClH:37].[ClH:37]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 13359982HCID 13359982, compound

Product 1

HCID 131715090HCID 131715090, compound

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalyst2×HCID 31374DimethylacetamideSolvent

Procedure

N-[1-(4-Benzylpiperazin-1-yl)ethylidene]-2-cyano-4,5-dimethoxyaniline (13.5 g) and zinc chloride (4.86 g) in dimethylacetamide (90 ml) were stirred under reflux for 21/2 hours; further zinc chloride (0.5, 0.2 g) was added after 1/2 and 11/2 hours respectively. The mixture was cooled, treated with ether (700 ml, 2×100 ml) and the supernatant discarded each time. The residual tar was then treated with sodium hydroxide solution (2N, 100 ml) and methylene chloride (100 ml) and the mixture was stirred at room temperature for 5 minutes. The organic layer was separated, the aqueous phase extracted with methylene chloride and the total organic extracts washed with water. The dried (Na2SO4) extracts were evaporated in vacuo and the brown residue (~13 g) purified by chromatography on silica gel (Merck 9385, 250 g) eluting with chloroform-methanol (100:0→88:12). A sample of the pure product (6.95 g) was taken up in ethanol, treated with ethereal hydrogen chloride and evaporated in vacuo. The residue was recrystallised from methanol to give 4-amino-6,7-dimethoxy-2(4-benzylpiperazin-1-yl)quinoline dihydrochloride sesquihydrate, m.p. 260°-263°.

Workup

  1. temperatureunder reflux for 21/2 hours
  2. temperatureThe mixture was cooled
  3. customThe organic layer was separated
  4. extractionthe aqueous phase extracted with methylene chloride
  5. washthe total organic extracts washed with water
  6. dry with materialThe dried (Na2SO4) extracts
  7. customwere evaporated in vacuo
  8. customthe brown residue (~13 g) purified by chromatography on silica gel (Merck 9385, 250 g)
  9. washeluting with chloroform-methanol (100:0→88:12)
  10. additiontreated with ethereal hydrogen chloride
  11. customevaporated in vacuo
  12. customThe residue was recrystallised from methanol

Sources & evidence

ORD record
ord-dc89b541f99c46e08cd5a1ed7a6fb618
Source dataset
uspto-grants-1987_04
Patent number
US04656174

Reaction notes

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