胺化芳胺化反应综述
合集下载
相关主题
- 1、下载文档前请自行甄别文档内容的完整性，平台不提供额外的编辑、内容补充、找答案等附加服务。
- 2、"仅部分预览"的文档,不可在线预览部分如存在完整性等问题,可反馈申请退款(可完整预览的文档不适用该条件!)。
- 3、如文档侵犯您的权益，请联系客服反馈,我们会尽快为您处理(人工客服工作时间：9:00-18:30)。
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
I
37 mmol 8 ml
N
+3
N
KOH, Cu, n-Decane
1.23 g
I
I 1来自百度文库 mmol
N
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%).
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
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.
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
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
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.
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
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: 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
I
37 mmol 8 ml
N
+3
N
KOH, Cu, n-Decane
1.23 g
I
I 1来自百度文库 mmol
N
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%).
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
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.
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
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
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.
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
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%)