Hexamethylphosphoramide → Ethyl 1,4-dihydro-1-ethyl-7-(3-pyridinyl)4-oxo-3-quinolinecarboxylate

HRID 1032729

Reaction equation

HRID 1032729 reaction equation
Br[C:2]1[CH:11]=[C:10]2[C:5]([C:6](=[O:19])[C:7]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:8][N:9]2[CH2:12][CH3:13])=[CH:4][CH:3]=1.C[Sn](C)(C)[C:22]1[CH:23]=[N:24][CH:25]=[CH:26][CH:27]=1.CN(C)P(N(C)C)(N(C)C)=O.C(Cl)(Cl)Cl.CCO>O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:12]([N:9]1[C:10]2[C:5](=[CH:4][CH:3]=[C:2]([C:22]3[CH:23]=[N:24][CH:25]=[CH:26][CH:27]=3)[CH:11]=2)[C:6](=[O:19])[C:7]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:8]1)[CH3:13]

Participants

7

Reactant 4

HCID 12679HexamethylphosphoramideHCID 108684453-(Trimethylstannyl)pyridineHCID 14851995Ethyl 7-bromo-1-ethyl-4-oxo-1,4-dihydroquinoline-3-carboxylateHCID 21889567Chloroform ethanol

Product 1

HCID 21790907Ethyl 1,4-dihydro-1-ethyl-7-(3-pyridinyl)4-oxo-3-quinolinecarboxylateYield 56.3%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

A suspension of 10.0 g ethyl 7-bromo-1,4-dihydro-1-ethyl-4-oxo-3-quinolinecarboxylate (U.S. Pat. No. 3,753,993), 0.64 g dichlorobis(triphenylphosphine)palladium, 10.9 g 3-trimethylstannylpyridine and 6.5 ml hexamethylphosphoramide in 40 ml dioxane was heated at reflux under nitrogen for 48 hrs. The reaction mixture was filtered through neutral alumina, eluted with chloroform, washed with water, and dried over potassium carbonate. The solid product obtained by concentration in vacuo was subjected to chromatography (MPLC; 10:1 CHCl3/EtOH) to give 5.6 g of ethyl 1,4-dihydro-1-ethyl-7-(3-pyridinyl)4-oxo-3-quinolinecarboxylate, which was hydrolyzed by refluxing with 150 ml 3N hydrochloric acid for 1.5 hrs. The product which separated (3.9 g) was dried to give 1,4-dihydro-1-ethyl-7-(3-pyridinyl)-4-oxo-3-quinolinecarboxylic acid, m.p. 268-269° C.

Workup

  1. temperatureat reflux under nitrogen for 48 hrs
  2. filtrationThe reaction mixture was filtered through neutral alumina
  3. washeluted with chloroform
  4. washwashed with water
  5. dry with materialdried over potassium carbonate
  6. customThe solid product obtained by concentration in vacuo

Sources & evidence

ORD record
ord-79c42d546171496696d100287e0aafdc
Source dataset
uspto-grants-1990_09
Patent number
US04959363

Linked notes

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