4-Isopropylaniline → HCID 86620567, compound

HRID 386363Notes

Reaction equation

HRID 386363 reaction equation
Br[C:2]1[CH:19]=[CH:18][C:17]2[C:16]3[C:7](=C4C(=CC=3)C=CC=C4)[CH:6]=[CH:5][C:4]=2[C:3]=1Br.[CH:21]([C:24]1[CH:30]=[CH:29][C:27]([NH2:28])=[CH:26][CH:25]=1)([CH3:23])[CH3:22].P([C:40]([CH3:43])([CH3:42])[CH3:41])(C(C)(C)C)C(C)(C)C.BrC1C=CC2C3C(=[C:51]4[C:56](=[CH:57][CH:58]=3)[CH:55]=[CH:54][CH:53]=[CH:52]4)C=CC=2C=1Br.[NH2:64][C:65]1[CH:70]=[CH:69]C=[CH:67][CH:66]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH:21]([C:24]1[CH:30]=[CH:29][C:27]([NH:28][C:57]2[CH:58]=[C:3]3[C:2](=[C:55]4[C:56]=2[CH:51]=[CH:52][CH:53]=[CH:54]4)[CH:19]=[C:18]([NH:64][C:65]2[CH:70]=[CH:69][C:43]([CH:40]([CH3:41])[CH3:42])=[CH:67][CH:66]=2)[C:17]2[CH:16]=[CH:7][CH:6]=[CH:5][C:4]3=2)=[CH:26][CH:25]=1)([CH3:23])[CH3:22]

Participants

8

Reactant 5

HCID 74644-IsopropylanilineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23083793HCID 23083793, compoundHCID 23676156Sodium t-butoxideHCID 86620568HCID 86620568, compound

Product 1

HCID 86620567HCID 86620567, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent2×

Procedure

In the drybox, a 500 mL one-neck round-bottom flask was charged with dibromochrysene (9 g, 23.3 mmol), 4-iso-propylaniline (6.61 g, 48.9 mmol) and 200 mL of dry toluene. In a separate 100 ml flask, Pd2(dba)3 (0.192 g, 0.21 mmol), P(t-Bu)3 (0.085 g, 0.42 mmol) were dissolved in 25 ml of dry toluene, stirred for 10 minutes and then added to the dibromochrysene/aniline solution. After ten minutes of stirring, sodium tert-butoxide (4.48 g, 46.6 mmol) was added in one portion. The reaction flask was brought out of the drybox, capped with a nitrogen inlet and stirred in an 80° C. oil bath overnight (18 h). Next day, reaction mixture was cooled to room temperature, poured onto 15 g of silica gel and 15 g of celite, swirled around for a few minutes and filtered through a 4 inch plug of silica gel, washing with 5.5 liters of toluene. Volatiles were removed under vacuum to give a dark yellow solid. The solid was triturated with diethyl ether, vacuum filtered and washed with minimal amount of ether. The resulting yellow solid was dried on a high vacuum line. Yield 8.68 g (75.5%). The compound was confirmed by NMR analysis.

Workup

  1. stirringAfter ten minutes of stirring
  2. customcapped with a nitrogen inlet
  3. stirringstirred in an 80° C. oil bath overnight (18 h)
  4. customNext day, reaction mixture
  5. additionpoured onto 15 g of silica gel and 15 g of celite
  6. customswirled around for a few minutes
  7. filtrationfiltered through a 4 inch plug of silica gel
  8. washwashing with 5.5 liters of toluene
  9. customVolatiles were removed under vacuum
  10. customto give a dark yellow solid
  11. customThe solid was triturated with diethyl ether, vacuum
  12. filtrationfiltered
  13. washwashed with minimal amount of ether
  14. customThe resulting yellow solid was dried on a high vacuum line

Sources & evidence

ORD record
ord-1656e51fa3204eb193e4ff71e3870513
Source dataset
uspto-grants-2013_02
Patent number
US08372525B2

Reaction notes

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