Ethyl Acetate → HCID 59770237, compound

HRID 2218640Notes

Reaction equation

HRID 2218640 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:21]=[CH:22][CH:23]=1)[CH:5]=[C:6]1[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=2[CH2:10][CH2:9][C:8]2[CH:17]=[CH:18][CH:19]=[CH:20][C:7]1=2.[C:24]([Cu])#[N:25].CCOC(C)=O>CN1CCCC1=O.[Cu]I>[CH:17]1[C:8]2[CH2:9][CH2:10][C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=3[C:6](=[CH:5][C:4]3[CH:21]=[C:22]([CH:23]=[CH:2][CH:3]=3)[C:24]#[N:25])[C:7]=2[CH:20]=[CH:19][CH:18]=1

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 59769885HCID 59769885, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 59770237HCID 59770237, compoundYield 71.5%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

Purge a solution of 5-(3-bromo-benzylidene)-10,11-dihydro-5H-dibenzo-[a,d]cycloheptene (4.2 g, 11.6 mmol) in N-methylpyrrolidinone (80 mL) with nitrogen for 10 minutes. Add CuI (6.7 g, 35 mmol) and CuCN (3.1 g, 35 mmol) and heat to 130° C. After 1 hour, cool the reaction to ambient temperature and shake with aqueous FeCl3 (200 mL) and EtOAc (200 mL). Wash the organic layer with water, dry with MgSO4 and concentrate to obtain 6.4 g crude product. Purify on silica gel using EtOAc/hexane to obtain 2.55 g (71%) title compound as a white solid, mp 115.7° C. 1H NMR (CDCl3) δ 3.02 (br d, 2H), 3.40 (br d, 2H), 6.77 (s, 1H), 6.93 (dd, 1H), 7.02-7.49 (m,11H); MS (EI) 307. HPLC shows 98% purity.

Workup

  1. temperaturecool
  2. customthe reaction to ambient temperature
  3. washWash the organic layer with water
  4. dry with materialdry with MgSO4
  5. concentrationconcentrate
  6. customto obtain 6.4 g crude product
  7. customPurify on silica gel

Sources & evidence

ORD record
ord-4e0935dcf2e64316ac4748fae2387434
Source dataset
uspto-grants-2008_08
Patent number
US07411072B2

Reaction notes

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