Hydrochloric Acid → HCID 178465847, compound

HRID 222558Notes

Reaction equation

HRID 222558 reaction equation
BrC1C2[NH:23][C:4](=[C:5]([C:35]3[C:40]([CH3:41])=[CH:39][C:38]([CH3:42])=[CH:37][C:36]=3[CH3:43])[C:6]3[CH:7]=[CH:8][C:9]([N:34]=3)=[C:10]([C:27]3[CH:32]=[CH:31][C:30]([CH3:33])=[CH:29][CH:28]=3)[C:11]3[NH:15][C:14]([CH:16]=[C:17]4[N:24]=[C:20](C=2)[CH2:19][C:18]4([CH3:26])[CH3:25])=[CH:13][CH:12]=3)[CH:3]=1.Cl.[CH2:45](Cl)Cl.[CH2:48]1[CH2:52][O:51][CH2:50][CH2:49]1>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>[C:50]([C:49]1[C:48]2[NH:23][C:4](=[C:5]([C:35]3[C:40]([CH3:41])=[CH:39][C:38]([CH3:42])=[CH:37][C:36]=3[CH3:43])[C:6]3[CH:7]=[CH:8][C:9]([N:34]=3)=[C:10]([C:27]3[CH:28]=[CH:29][C:30]([CH3:33])=[CH:31][CH:32]=3)[C:11]3[NH:15][C:14]([CH:16]=[C:17]4[N:24]=[C:20]([CH:52]=2)[CH2:19][C:18]4([CH3:26])[CH3:25])=[CH:13][CH:12]=3)[CH:3]=1)(=[O:51])[CH3:45]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6344DichloromethaneHCID 8028TetrahydrofuranHCID 16083798HCID 16083798, compound

Product 1

HCID 178465847HCID 178465847, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 178418476HCID 178418476, compoundCatalyst

Procedure

Following a procedure for Stille coupling on aromatic compounds (Kosugi, M. et al., Bull. Chem. Soc. Jpn. 1987, 60, 767-768), a mixture of 6 (75 mg, 0.12 mmol), 7 (80 μL, 0.24 mmol) and (PPh3)2PdCl2 (9.0 mg, 0.013 mmol) was refluxed in THF (12 mL) for 20 h in a Schlenk line. The reaction mixture was treated with 10% aqueous HCl (4 mL) at room temperature for 2 h. CH2Cl2 was added and the organic layer was separated. The organic layer was washed with saturated aqueous NaHCO3, water, and brine. The organic layer was dried (Na2SO4), concentrated and chromatographed [silica, CH2Cl2/hexanes (1:1)], affording a purple solid (50 mg, 71%): 1H NMR δ-0.98 (brs, 2H), 1.86 (s, 6H), 2.02 (s, 6H), 2.61 (s, 3H), 2.66 (s, 3H), 3.05 (s, 3H), 4.56 (s, 2H), 7.24 (s, 2H), 7.50 (d, J=7.8 Hz, 2H), 7.96 (d, J=7.8 Hz, 2H), 8.23 (d, J=4.4 Hz, 1H), 8.31 (d, J=4.4 Hz, 1H), 8.68 (d, J=4.4 Hz, 1H), 8.69 (s, 1H), 8.70 (d, J=4.4 Hz, 1H), 8.86 (s, 1H), 9.98 (s, 1H); LD-MS obsd 590.8; FAB-MS obsd 590.3052, calcd 590.3046 (C40H38N4O); λabs 422, 661 (logs ε=4.67) nm, λem 668, 711, 714 nm (Φf=0.23).

Workup

  1. customthe organic layer was separated
  2. washThe organic layer was washed with saturated aqueous NaHCO3, water, and brine
  3. dry with materialThe organic layer was dried (Na2SO4)
  4. concentrationconcentrated
  5. customchromatographed [silica, CH2Cl2/hexanes (1:1)]

Sources & evidence

ORD record
ord-cf7cd4b29bf64330ae6289e6e25354ff
Source dataset
uspto-grants-2012_06
Patent number
US08207329B2

Reaction notes

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