芳胺化反应综述

1、芳胺化反应报告人：张 俊 祥SchemeRNH2RYRNRNR1R2YRNR1R2R+Met.Cat., BaseSolventMet.Cat., BaseSolvent二芳胺化合物Diarylamines were prepared by the condensation of an aniline with an arenesulfonic acidCondt.: NaNH2 (5.36 mol), KCl (5.36 mol), n-decane, heated to 195 C and stirred for 4 h, Workup: The mixture was filtered

2、and excess aniline removed under reduced pressure. Reduced pressure distillation yielded an orangeyellow oil. Recrystallisation from hexane gave the title compound (74%)J. Chem. Soc., Perkin Trans. 1, 2000, 26952701(1.56 mol)(8.90 mol)二芳胺化合物Base: K2CO3Cat.: CuI (0.25 mmol) Sol.: ethoxyethyl ether (2

3、5 mL) Condt.: 1,3-dibromobenzene (10 mmol), K2CO3 (10 mmol), reflux for 24 hWorkup: filtered, filtrate thoroughly washed with EtOAc. Vacuum distillation, and the crude product was purified by chromatography ,recrystallization from hexane/EtOAc, providing Y: 51%10 mmolJ. Am. Chem. Soc. 1996, 118, 106

4、26-10628Cat.: copper 6 gSol.: 12 ML Soltrol.RTM. 170 (a mixture of C13 C15 aliphatic hydrocarbons from Phillips Chemical Com.). Condt.: 160.degree. C. about 5 hours. Workup: Column chromatographed with toluene as eluent and recrystallized from n-octane to yield colorless crystals, Y:85%.0.02 mole0.0

5、8 mole0.16 moleUS 4,764,625 Xerox Cop.NIINN+KOH, CuSoltrol.RTM. 170三芳胺化合物Base: KOHIIINNNN+3KOH, Cu, n-Decane2.06 mmol12 mmol37 mmol1.23 g8 mlCondt.: 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 pro

6、duct. filtered off, dissolved in CH2Cl2 and filtered. Purified by flash chromatograph. PEdichloromethane eluted the title compound (65%).J. Chem. Soc., Perkin Trans. 1, 2000, 26952701三芳胺化合物Base: KOH Ullmann condensation of diarylamines with iodobenzenes has been investigated under homogeneous and he

7、terogeneous 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 iodobenzenes p = -0.25; for substituted diphenylamines p = 1.09) but quite sens

8、itive 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.三芳胺化合物J. Am. Chem. SOC. 1987, 109, 1496-1502Base: KOH三芳胺化合物Cat.: copper 4.5 gSol.: 150 ml PhNO2 Condt.: ref

9、luxed together for 22 hoursWorkup: Removed by steam distillation, dissolved in 1 1. of benzene, saturated with dry hydrogen chloride. A tarry precipitate was discarded. Chromatographed to remove tars. Sublimation on the steam-bath in a vacuum desiccator removed di-p-tolylamine. The residue from the

10、sublimation was recrystallized from acetic acid togive white crystals, m.p. 110-117, Y: 11%.1.79 mol0.84 molNNH2IK2CO3+1 moleJ. Am. Chem. Soc. 1955, 77, 5999-6002Base: K2CO3NFFFFNHFFIK2CO3+三芳胺化合物Cat.: copperSol.: without a solvent Condt.:Workup: Extraction with benzene, and evaporation gave 13 g. of

11、 crude crystals. Chromatographed and the product crystallized from benzene/ethanol. The resulting white crystals melted. Y: 37%.0.13 mol0.11 molJ. Am. Chem. Soc. 1955, 77, 5999-6002Base: K2CO3三芳胺化合物Cat.: copper 3 gSol.: 50 ml sulfolane Condt.: 220.degree.-225.degree. C. for 24 hoursWorkup: Methanol

12、to participated, Column chromatographed with toluene and recrystallized from n-octane to yield colorless crystals, Y:未知.0.1 mol0.05 mol0.15 moleUS 4,306,008 Xerox Cop.NIINNK2CO3+, CuBase: K2CO3三芳胺化合物Cat.: copper, and 18-crown-6 (0.20 g)Sol.: o-dichlorobenzene (100 ml)Condt.: 180 C and stirred under

13、nitrogen for 90 hWorkup: Cooled and slurried with CH2Cl2 and filtered. The remaining brown residue was dissolved in THF and added slowly to MeOH with stirring. A brown solid precipitated. Column chromatography, eluting with CH2Cl2cyclohexane gave a yellow solid. Crystallisation from CH2Cl2- cyclohex

14、ane yielded (22 %).3.72 mmol3.72 mmol3.72 mmolTetrahedron 59 (2003) 467346857.40 mmolNINK2CO3NN+, CuBase: K2CO3INNNNK2CO3+, CuTPDCat.: copper, and 18-crown-6 (10.0 g)Sol.: o-dichlorobenzene (200 ml)Condt.: 170 C and stirred under nitrogen for 48 hWorkup: Cooled and slurried with CH2Cl2 and filtered.

15、 The remaining brown residue was dissolved in THF and added slowly to MeOH with stirring. A brown solid precipitated. Column chromatography, eluting with CH2Cl2cyclohexane gave a yellow solid. Crystallisation from CH2Cl2- cyclohexane yielded (50%).664 mmol213 mmol635 mmolJ. Chem. Soc., Perkin Trans.

16、 1, 2001, 254825521.02 molBase: K2CO3三芳胺化合物 n-BuLiCat.: CuI(0.07 mmol)Sol.: Ph2O (15 mL)Condt.: 200 C and stirred under nitrogen for 48 h.Workup: Cooling, ethyl acetate (50 mL) was added and the reaction mixture was filtered over hyflo, washed with NH4Cl, and dried. flash column chromatography and r

17、ecrystallization from benzene afforded Y: 61%.1.6 mmol0.7 mmol1.4 mmolJ. Am. Chem. Soc. 1997, 119, 4492-4501Base: n-BuLi三芳胺化合物Cat.: CuI 0.1 mmol), Sol.: Ph2O (10 mL)Condt.: 1,4-diiodobenzene (0.5 mmol), 200 C and stirred under nitrogen for 48 h.Workup: Cooling, ethyl acetate (50 mL) was added and th

18、e reaction mixture was filtered over hyflo, washed with NH4Cl, and dried. flash column chromatography and recrystallization from benzene afforded Y: 51%.1.1 mmolJ. Am. Chem. Soc. 1997, 119, 4492-4501NaH2 mmolBase: NaH三芳胺化合物Cat.: CuI (0.6 mmol), Sol.: Ph2O (25 mL)Condt.: 1,4-diiodobenzene (0.5 mmol), 200 C and stirred under nitrogen for 48 h.