Water → trans-4,4'-Bis(m-tolylphenylamino)stilbene

HRID 1387194Notes

Reaction equation

HRID 1387194 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[C:10]2[CH:15]=[CH:14][C:13](Br)=[CH:12][CH:11]=2)=[CH:4][CH:3]=1.[CH3:17][C:18]([CH3:21])([O-])[CH3:19].[Na+].[C:23]1([CH3:36])[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=1[C:29]1[CH:30]=[C:31]([NH2:35])[CH:32]=[CH:33][CH:34]=1.O.[C:38]1([CH3:44])[CH:43]=[CH:42][CH:41]=[CH:40]C=1>C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C(N(CCCCCCCC)C1C=CC(C=CC2C=CC(N(CCCCCCCC)CCCCCCCC)=CC=2)=CC=1)CCCCCCC.CCOCC>[C:23]1([CH3:36])[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=1[C:29]1[CH:30]=[C:31]([NH:35][C:2]2[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[C:10]3[CH:15]=[CH:14][C:13]([NH:35][C:31]4[CH:30]=[CH:29][CH:19]=[C:18]([C:21]5[CH:40]=[CH:41][CH:42]=[CH:43][C:38]=5[CH3:44])[CH:17]=4)=[CH:12][CH:11]=3)=[CH:4][CH:3]=2)[CH:32]=[CH:33][CH:34]=1

Participants

9

Reactant 5

HCID 962WaterHCID 1140TolueneHCID 15159823-Amino-2'-methylbiphenylHCID 7020566Trans-4,4'-dibromostilbeneHCID 23676156Sodium t-butoxide

Product 1

HCID 86586575trans-4,4'-Bis(m-tolylphenylamino)stilbeneYield 94%

Reagents, catalysts & solvents 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 544306514,4'-Bis-dioctylaminostilbeneCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
95 °C

Procedure

Pd2dba3 (Example 52) (963 mg, 1.05 mmol) and bis(diphenylphosphino)ferrocene (833 mg, 1.33 mmol) were stirred under nitrogen in dry toluene (500 mL) for 15 min. Trans-4,4′-dibromostilbene (15.00 g, 44.4 mmol) was added against a counterflow of nitrogen and the reaction was stirred for an additional 15 min; sodium tert-butoxide (13.00 g, 135 mmol) was then added and m-tolylphenylamine (16.8 mL, 97.6 mmol) was added from a syringe. After 30 min at room temperature, the reaction mixture was warmed to 95° C. for 24 h, at which time, the reaction appeared complete by thin layer chromatography. The reaction mixture was transferred to a separating funnel together with water (1 L) and ether (500 mL). The aqueous layer was extracted with ether until the extracts were almost colorless. The combined organics were dried over magnesium sulfate, filtered and concentrated by rotary evaporation. The resulting material was dissolved in benzene and passed through a silica plug. The benzene solution was concentrated under reduced pressure and heated. Addition of methanol followed by cooling afforded trans-4,4′-bis(m-tolylphenylamino)stilbene as an NMR-pure yellow powder (22.59 g, 41.6 mmol, 94%). 1H NMR (d6-acetone) δ 7.47 (d, J=8.6 Hz, 4H), 7.34-7.27 (m, ca. 6H), 7.19 (t, J=7.7 Hz, 2H), 7.10-6.85 (m, ca. 16H), 2.24 (s, 6H); 13C NMR (75 MHz, d6-acetone) δ 148.5, 148.4, 148.0, 139.9, 132.9, 130.2, 130.0, 128.1, 127.3, 125.9, 125.0, 124.9, 124.2, 123.8, 122.5, 21.4; UV (TBF) λmax 305 (ε305 26000), 387 (ε387 51000) nm; UV (acetone) λmax 386 nm; UV (ethanol) λmax 304, 386 nm; High resolution LSIMS calcd. for C40H34N2 M+ 542.2722, found 542.2716.

Workup

  1. waitAfter 30 min at room temperature
  2. extractionThe aqueous layer was extracted with ether until the extracts
  3. dry with materialThe combined organics were dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated by rotary evaporation
  6. dissolutionThe resulting material was dissolved in benzene
  7. concentrationThe benzene solution was concentrated under reduced pressure
  8. temperatureheated
  9. additionAddition of methanol
  10. temperatureby cooling

Sources & evidence

ORD record
ord-173f4a75c019445ba98a3b3d35c184ba
Source dataset
uspto-grants-2001_07
Patent number
US06267913B1

Reaction notes

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