J. Chem. Soc., Perkin Trans. 1, 2000, 2695–2701
三芳胺化合物 Base: KOH
Ullmann condensation of diarylamines with iodobenzenes has been investigated under homogeneous and heterogeneous catalytic conditions with cuprous and curpic salts, as well as powdered copper metal. Copper catalyzed condensation of diarylamines with iodoaromatics is relatively insensitive to substituent (for substituted
芳胺化反应
报告人：张 俊 祥
Scheme
R'
+ NH2 R
Y Met.Cat., Base
Solvent
R
N
R'
R1
+ R2
N
R
Met.Cat., Base R1 Y
Solvent
R2 N
R
二芳胺化合物
Diarylamines were prepared by the condensation of an aniline with an
arenesulfonic acid
(8.90 mol)
(1.56 mol)
Condt.: NaNH2 (5.36 mol), KCl (5.36 mol), n-decane, heated to 195 C and stirred for 4 h,
Workup: The mixture was filtered and excess aniline removed under reduced pressure. Reduced pressure distillation yielded an orange–yellow oil. Recrystallisation from hexane gave the title compound (74%)
三芳胺化合物 Base: KOH
0.16 mole
+I
N
KOH, Cu
I
N
N
Soltrol.RTM . 170
0.08 mole
0.02 mole
Cat.: copper 6 g
Sol.: 12 ML Soltrol.RTM. 170
(a mixture of C13 –C15 aliphatic hydrocarbons from Phillips Chemical Com.). Condt.: 160.degree. C. about 5 hours.
iodobenzenes p = -0.25; for substituted diphenylamines p = 1.09) but quite sensitive to halogen ( k I / k B , > 200).
This hypothesis rationalizes many of the perplexing results which typify the literature associated with copper catalyzed nucleophilic aromatic substitution.
I
37 mmol 8 ml
N
+3
N
KOH, Cu, n-Decane
1.23 g
I
I 12 mmol

N
2.06 mmol
Condt.: Refluxed 48 h or until only one product spot could be detected by TLC.
Workup: Cooled and addition of methanol (50 cm3) which precipitated the crude product. filtered off, dissolved in CH2Cl2 and filtered. Purified by flash chromatograph. PE–dichloromethane eluted the title compound (65%).
Workup: Column chromatographed with toluene as eluent and recrystallized from n-octane to yield colorless crystals, Y:85%.
US 4,764,625 Xerox Cop.
三芳胺化合物 Base: KOH
J. Chem. Soc., Perkin Trans. 1, 2000, 2695–2701
二芳胺化合物 Base: K2CO3
10 mmol Cat.: CuI (0.25 mmol) Sol.: ethoxyethyl ether (25 mL) Condt.: 1,3-dibromobenzene (10 mmol), K2CO3 (10 mmol), reflux for 24 h Workup: filtered, filtrate thoroughly washed with EtOAc. Vacuum distillation, and the crude product was purified by chromatography ,recrystallization from hexane/EtOAc, providing Y: 51% J. Am. Chem. Soc. 1996, 118, 10626-10628
J. Am. Chem. SOC. 1987, 109, 1496-1502
三芳胺化合物 Base: K2CO3
1 mole
NH2 +
K2CO3 I
N
0.84 mol
1.79 mol
Cat.: copper 4.5 g
Sol.: 150 ml PhNO2 Condt.: refluxed together for 22 hours