Dimethylformamide → HCID 131724657, compound

HRID 2416405Notes

Reaction equation

HRID 2416405 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5](C)=[CH:4][CH:3]=1.[C:9]([C:13]1[CH:14]=[C:15]([CH:34]=[C:35]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:36]=1)[CH:16]=[CH:17][C:18]1[CH:23]=[CH:22][C:21]([CH:24]=[CH:25][C:26]2[CH:31]=[CH:30][C:29]([CH:32]=[CH2:33])=[CH:28][CH:27]=2)=[CH:20][CH:19]=1)([CH3:12])([CH3:11])[CH3:10].C([O-])([O-])=O.[K+].[K+].CN(C=O)C>[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].C1C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:9]([C:13]1[CH:14]=[C:15]([CH:34]=[C:35]([C:37]([CH3:40])([CH3:39])[CH3:38])[CH:36]=1)[CH:16]=[CH:17][C:18]1[CH:23]=[CH:22][C:21]([CH:24]=[CH:25][C:26]2[CH:27]=[CH:28][C:29]([CH:32]=[CH:33][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)=[CH:30][CH:31]=2)=[CH:20][CH:19]=1)([CH3:12])([CH3:10])[CH3:11]

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 122074-IodotolueneHCID 73990326HCID 73990326, compound

Product 1

HCID 131724657HCID 131724657, compoundYield 71%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 241BenzeneSolvent

Conditions

Temperature
90 °C

Procedure

A 50 mL round bottom flask was charged with a Teflon coated stir bar, 4-iodophenylmethane (408 mg, 2.0 mmol), 1-(3′5′-di-tert-butylstyryl)-4-(4′-vinylstyryl)benzene (0.84 g, 2.0 mmol), Pd(OAc)2 (22.45 mg, 0.1 mmol), K2CO3 (690 mg, 5.0 mmol), n-Bu4NBr (665 mg, 2.0 mmol) and DMF (16 mL). The mixture was degassed with 4 freeze-pump-thaw cycles and heated at 90° C. for 48 hours. The reaction was cooled to room temperature, diluted with CH2Cl2, washed with brine, dried over MgSO4 and the solvent was removed under reduced pressure. The crude product was purified on a silica gel column (20% CH2Cl2/hexanes) to give a yellow greasy solid which contains cis-trans isomers. The isomers were dissolved in 150 mL benzene and degassed with 4 freeze-pump-thaw cycles. The solution was irradiated with Blak-Ray long UV lamp for 60 minutes and the solvent was removed under reduced pressure. The isomerized product was repurified on a silica gel column (20% CH2Cl2/hexanes) to give a yellow solid (yield 71%). 1H NMR (CDCl3): δ 7.51-7.54 (overlapping signals, 9H), 7.35-7.39 (overlapping signals, 5H), 7.28 (t, J=7.50 Hz, 1H), 7.19 (d, J=16.3 Hz, 1H), 7.13 (complex, 4H), 7.10 (d, J=16.3 Hz, 1H), 1.37 (s, 18H). 13C NMR (CDCl3): δ 151.28, 137.54, 136.66, 129.96, 128.93, 128.78, 128.49, 128.20, 127.76, 127.09, 127.04, 127.01, 126.73, 121.09, 31.69. Exact Mass (FAB, NBA) for M+ (C38H40): calculated 496.3143; found 496.3189.

Workup

  1. additionA 50 mL round bottom flask was charged with a Teflon coated stir bar
  2. customThe mixture was degassed with 4 freeze-pump-thaw cycles
  3. temperatureThe reaction was cooled to room temperature
  4. additiondiluted with CH2Cl2
  5. washwashed with brine
  6. dry with materialdried over MgSO4
  7. customthe solvent was removed under reduced pressure
  8. customThe crude product was purified on a silica gel column (20% CH2Cl2/hexanes)
  9. customto give a yellow greasy solid which
  10. customdegassed with 4 freeze-pump-thaw cycles
  11. customThe solution was irradiated with Blak-Ray long UV lamp for 60 minutes
  12. customthe solvent was removed under reduced pressure
  13. customThe isomerized product was repurified on a silica gel column (20% CH2Cl2/hexanes)

Sources & evidence

ORD record
ord-ade98e8047244ddd8a0d3458bd6580d0
Source dataset
uspto-grants-2004_11
Patent number
US06824890B2

Reaction notes

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