Potassium Phosphate, Tribasic → benzhydrylidene-{2-methyl-5-[3-((E)-styryl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazol-6-yloxy]-phenyl}-amine

HRID 724448Notes

Reaction equation

HRID 724448 reaction equation
P([O-])([O-])([O-])=O.[K+].[K+].[K+].[C:9](=[N:22][C:23]1[CH:24]=[C:25]([OH:30])[CH:26]=[CH:27][C:28]=1[CH3:29])([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.I[C:32]1[CH:40]=[C:39]2[C:35]([C:36](/[CH:49]=[CH:50]/[C:51]3[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=3)=[N:37][N:38]2[CH2:41][O:42][CH2:43][CH2:44][Si:45]([CH3:48])([CH3:47])[CH3:46])=[CH:34][CH:33]=1.C1(C2C=CC=CC=2)C=CC=CC=1P(C(C)(C)C)C(C)(C)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC1C=CC=CC=1C>[C:9](=[N:22][C:23]1[CH:24]=[C:25]([O:30][C:32]2[CH:40]=[C:39]3[C:35]([C:36](/[CH:49]=[CH:50]/[C:51]4[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=4)=[N:37][N:38]3[CH2:41][O:42][CH2:43][CH2:44][Si:45]([CH3:46])([CH3:47])[CH3:48])=[CH:34][CH:33]=2)[CH:26]=[CH:27][C:28]=1[CH3:29])([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1

Participants

7

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 27342152-(Di-tert-butylphosphino)biphenylHCID 218772551H-Indazole, 6-iodo-3-[(1E)-2-phenylethenyl]-1-[[2-(trimethylsilyl)ethoxy]methyl]-HCID 218775913-(Benzhydrylidene-amino)-4-methyl-phenol

Product 1

HCID 21877404benzhydrylidene-{2-methyl-5-[3-((E)-styryl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazol-6-yloxy]-phenyl}-amineYield 146.4%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 7237O-XyleneSolvent

Conditions

Temperature
100 °C

Procedure

A round bottom flask was charged with potassium phosphate (5.5 g, 26.0 mmol, 2.0 eq), 3-(benzhydrylidene-amino)-4-methyl-phenol (3.9 g, 13.6 mmol, 1.1 eq), 6-iodo-3-((E)-styryl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazole (6.2 g, 13.0 mmol, 1.0 eq) and o-xylene (130 mL). The resultant slurry was degassed, purged with argon and treated with a mixture of tris(dibenzylideneacetone)dipalladium(0) (916 mg, 1.1 mmol, 8 mol %) and biphenyl-2-yl-di-tert-butyl-phosphane (656 mg, 2.2 mmol, 16 mol %). The flask was immersed in an oil bath and stirred at 100° C. for 18 hours. The black slurry was cooled to room temperature, filtered through celite and concentrated. The black oil was dissolved in chloroform, washed with water, brine, dried over magnesium sulfate, filtered and concentrated to give a black oil (12.1 g). The crude product was purified by flash chromatography on silica gel using 10–15% ether-cyclohexane as the eluant to give_benzhydrylidene-{2-methyl-5-[3-((E)-styryl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazol-6-yloxy]-phenyl}-amine as a yellow foam from ether (1.4 g, 16%): HPLC Rt=24.3 min.; TLC Rf=0.5 (20% ether-cyclohexane); 1H NMR (300 MHz, DMSO-d6) δ 8.10 (d, 1H, J=8.8 Hz), 7.75–7.66 (m, 4H), 7.53–7.31 (m, 11H), 7.14–7.08 (m, 4H), 6.62 (dd, 1H, J=8.8, 2.0 Hz), 6.55 (dd, 1H, J=8.2, 2.5 Hz), 6.20 (d, 1H, J=2.4 Hz), 5.64 (s, 2H), 3.51 (t, 2H, J=7.8 Hz), 2.12 (s, 3H), 0.78 (t, 2H, J=7.7 Hz), −0.14 (s, 9H).

Workup

  1. customThe resultant slurry was degassed
  2. custompurged with argon
  3. customThe flask was immersed in an oil bath
  4. temperatureThe black slurry was cooled to room temperature
  5. filtrationfiltered through celite
  6. concentrationconcentrated
  7. dissolutionThe black oil was dissolved in chloroform
  8. washwashed with water, brine
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-201cea23b7aa4f10b563c45344aa9304
Source dataset
uspto-grants-2006_11
Patent number
US07141587B2

Reaction notes

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