Tris(1,1-dimethylethyl)phosphine → HCID 67159432, compound

HRID 84997Notes

Reaction equation

HRID 84997 reaction equation
C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.Br[C:15]1[CH:37]=[CH:36][C:18]([N:19]([C:28]2[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=2)[C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=2)=[CH:17][CH:16]=1.[Si:38]([O:45][CH2:46][CH2:47][CH2:48][O:49][C:50]1[CH:64]=[CH:63][C:53]([NH:54][C:55]2[CH:60]=[CH:59][C:58]([O:61][CH3:62])=[CH:57][CH:56]=2)=[CH:52][CH:51]=1)([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:40])[CH3:39].CC(C)([O-])C.[Na+]>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].C(OCC)(=O)C>[Si:38]([O:45][CH2:46][CH2:47][CH2:48][O:49][C:50]1[CH:64]=[CH:63][C:53]([N:54]([C:55]2[CH:60]=[CH:59][C:58]([O:61][CH3:62])=[CH:57][CH:56]=2)[C:15]2[CH:16]=[CH:17][C:18]([N:19]([C:28]3[CH:29]=[CH:30][C:31]([O:34][CH3:35])=[CH:32][CH:33]=3)[C:20]3[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=3)=[CH:36][CH:37]=2)=[CH:52][CH:51]=1)([C:41]([CH3:42])([CH3:44])[CH3:43])([CH3:40])[CH3:39]

Participants

7

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 105961614-Bromo-4',4''-dimethoxytriphenylamineHCID 23676156Sodium t-butoxideHCID 667303054-(3-(tert-butyldimethylsilyloxy)propoxy)-N-(4-methoxyphenyl)aniline

Product 1

HCID 67159432HCID 67159432, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

6. Anhydrous toluene (30.0 mL) was degassed by sparging with nitrogen for 10 minutes in a dry 200 mL schlenk flask. Tri(tert-butyl) phosphine (0.187 g; 0.924 mmol) and Pd2(dba)3 (0.283 g, 0.309 mmol) were added and the mixture was allowed to stir. After 10 minutes, 4-bromo-N,N-bis(4-methoxyphenyl)aniline (5.92 g; 15.4 mmol), 4-(3-(tert-butyldimethylsilyloxy)propoxy)-N-(4-methoxyphenyl)aniline (6.00 g; 15.4 mmol), and sodium tert-butoxide (2.08 g, 21.6 mmol) were added. The reaction was allowed to stir at 90° C. while being monitored by TLC (5:1 hexanes:ethyl acetate). Upon the disappearance of the starting materials the mixture was filtered through Celite eluting with ethyl acetate. The product was purified by flash chromatography (silica gel, 5:1 hexanes:ethyl acetate). The solvent was removed under reduced pressure. The residual solvent was removed in vacuo (9.06 g, 90.6%). 1H NMR (300 MHz, C3D6O) δ 6.98 (m, 8H), 6.86 (m, 8H), 6.82 (s, 4H), 4.06 (t, J=6.3 Hz, 2H), 3.83 (t, J=6.3 Hz, 2H), 3.76 (s, 9H), 1.95 (q, J=6.0 Hz, 2H), 0.890 (s, 9H), 0.058 (s, 6H). 13C {1H} NMR (300 MHz, C3D6O, δ): 156.40, 155.83, 143.65, 142.31, 126.24, 123.78, 116.04, 115.41, 65.28, 60.09, 55.63, 33.27, 26.23, −5.27. HRMS-EI (m/z): [M]+ calcd for C42H50N2O5Si, 690.35; found, 690.6). Anal. Calcd for C42H50N2O5Si: C, 73.01; H, 7.29; N, 4.05. Found: C, 73.25; H, 7.43; N, 4.01.

Workup

  1. custom6. Anhydrous toluene (30.0 mL) was degassed
  2. customby sparging with nitrogen for 10 minutes in a dry 200 mL schlenk flask
  3. stirringto stir at 90° C.
  4. filtrationUpon the disappearance of the starting materials the mixture was filtered through Celite
  5. washeluting with ethyl acetate
  6. customThe product was purified by flash chromatography (silica gel, 5:1 hexanes:ethyl acetate)
  7. customThe solvent was removed under reduced pressure
  8. customThe residual solvent was removed in vacuo (9.06 g, 90.6%)

Sources & evidence

ORD record
ord-e744c4fc5e2344229292c4ae812e12af
Source dataset
uspto-grants-2014_09
Patent number
US08846978B2

Reaction notes

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