Diphenylamine → HCID 18544379, compound

HRID 1268492Notes

Reaction equation

HRID 1268492 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2C3C(=CC(Br)=CC=3)[C:5]([CH2:19][CH:20]=[CH2:21])([CH2:16][CH:17]=[CH2:18])[C:4]=2[CH:3]=1.[C:22]1([NH:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>C1(C)C=CC=CC=1.O.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].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]>[Br:1][C:2]1[CH:3]=[C:4]2[C:12]([C:32]3[CH:33]=[CH:34][C:29]([N:28]([C:2]4[CH:14]=[CH:13][CH:12]=[CH:4][CH:3]=4)[C:22]4[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=4)=[CH:30][C:31]=3[C:5]2([CH2:19][CH:20]=[CH2:21])[CH2:16][CH:17]=[CH2:18])=[CH:13][CH:14]=1

Participants

7

Reactant 2

HCID 11487DiphenylamineHCID 23539493HCID 23539493, compound

Product 1

HCID 18544379HCID 18544379, compoundYield 48%

Reagents, catalysts & solvents 4

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
93 °C

Procedure

A mixture of 2,7 dibromo-9,9-diprop-2-enylfluorene (40.4 g, 0.1 mol), diphenylamine (8.5 g, 0.05 mol), bis(dibenzylideneacetone)palladium(0) (0.3 g, 0.522 mmol), bis(diphenylphosphino)ferrocene (0.32 g, 0.57 mmol) sodium t-butoxide (5.6 g, 0.058 mol) and toluene (350 mL) was heated at 93° C. for 18 hours under nitrogen, and cooled. The mixture was diluted with toluene and water, and the toluene phase was dried and concentrated. The residue was chromatographed over 850 g of alumina. Elution with heptane led to the recovery of unreacted dibromo-diallylfluorene, 13.38 g, 33%, m.p. 134-137° C. Elution with 10% toluene-heptane yielded the desired product, m.p. 151-153° C., 11.74 g, 48% yield. Two successive recrystallizations from hexanes did not raise the m.p., 150.4-152.8° C. Mass Spec: m/z 491,493 (M+). IR (KBr): 3068, 2977,1639,1589,1489 cm−1. Anal. Calcd. for C31H26BrN; C, 75.61%; H, 5.32%; N, 2.84%; Br, 16.23%. Found: C, 75.56%; H, 5.27%; N, 2.68%. (Br- 17.1%). This reaction also produced some 2,7-bis(diphenylamino)-9,9-diallylfluorene, 1.09 g, m.p. 179-183° C. Mass Spec: m/z 580 (M+).

Workup

  1. temperaturecooled
  2. dry with materialthe toluene phase was dried
  3. concentrationconcentrated
  4. customThe residue was chromatographed over 850 g of alumina
  5. washElution with heptane
  6. washElution with 10% toluene-heptane

Sources & evidence

ORD record
ord-f8f203411eef482a9533d52acc2c0fbe
Source dataset
uspto-grants-2003_04
Patent number
US06555682B1

Reaction notes

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