Benzoic acid, 2-iodo-, methyl ester → Methyl 2-(3-(3-(2-(7-chloroquinolin-2-yl)vinyl)phenyl)-3-oxopropyl)benzoate

HRID 249040Notes

Reaction equation

HRID 249040 reaction equation
[Cl:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8]([CH:12]=[CH:13][C:14]3[CH:15]=[C:16]([CH:20]([OH:23])[CH:21]=[CH2:22])[CH:17]=[CH:18][CH:19]=3)=[N:9]2)=[CH:4][CH:3]=1.[Li]OC(C)=O.O.O.[Li+].[Cl-].I[C:34]1[CH:43]=[CH:42][CH:41]=[CH:40][C:35]=1[C:36]([O:38][CH3:39])=[O:37]>[N+](CCCC)(CCCC)(CCCC)CCCC.[Cl-].CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8]([CH:12]=[CH:13][C:14]3[CH:15]=[C:16]([C:20](=[O:23])[CH2:21][CH2:22][C:34]4[CH:43]=[CH:42][CH:41]=[CH:40][C:35]=4[C:36]([O:38][CH3:39])=[O:37])[CH:17]=[CH:18][CH:19]=3)=[N:9]2)=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 69132Benzoic acid, 2-iodo-, methyl esterHCID 433294Lithium ChlorideHCID 534062851-(3-(2-(7-Chloro-2-quinolinyl)ethenyl)phenyl)-2-propen-1-olHCID 178526966lithium;acetate;dihydrate

Product 1

HCID 53394881Methyl 2-(3-(3-(2-(7-chloroquinolin-2-yl)vinyl)phenyl)-3-oxopropyl)benzoate

Reagents, catalysts & solvents 3

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A degassed suspension of the product of Step 1 (50.3 g, 156 mmol), n-Bu4NCl (86.0 g, 312 mmol), LiOAc.2H2O (41.2 g, 390 mmol), LiCl (6.84 g, 156 mmol), Pd(OAc)2 (1.00 g, 4.7 mmol), and methyl 2-iodobenzoate (41.00 g, 156 mmol) in DMF (300 mL) was stirred for 3 hours at 90° C. The dark red solution was then cooled to r.t. and poured into 2 L of ice cold H2O. The product was extracted with hot EtOAc, dried over Na2SO4, filtered and concentrated to dryness. It was dissolved in 600 ml of hot toluene and filtered through a small silica pad (1 L). The title product was finally recrystallized from EtOAc:hexane 1:1 (1.2 L). The title product was finally recrystallized from EtOAc:hexane 1:1 (1.2 L). Recrystallization of the mother liquors in EtOAc:hexane 1:3 ( 400 mL) afforded a second crop of the title compound.

Workup

  1. temperatureThe dark red solution was then cooled to r.t.
  2. extractionThe product was extracted with hot EtOAc
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated to dryness
  6. dissolutionIt was dissolved in 600 ml of hot toluene
  7. filtrationfiltered through a small silica pad (1 L)
  8. customThe title product was finally recrystallized from EtOAc:hexane 1:1 (1.2 L)
  9. customThe title product was finally recrystallized from EtOAc:hexane 1:1 (1.2 L)
  10. customRecrystallization of the mother liquors in EtOAc:hexane 1:3 ( 400 mL)

Sources & evidence

ORD record
ord-2d1b4dea5a214a1abaeccd00afac8b2a
Source dataset
uspto-grants-1993_05
Patent number
US05212180

Reaction notes

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