5. Substitutionen an Aromaten 5-A1 2,4,6-Tribromanilin aus Anilin NH2 NH2 Br Br BrBr2 AcOH NH2 Br Br NH2 Br H NH2 Br H NH2 Br H NH2 Br H NH2 Br NH2 Br Br Br- H 5-A2 2-Amino-4’-nitrobiphenyl aus 2-Aminobiphenyl NH2 NH2 NO2 HNO3, H2SO4 HO N O O H2SO4 H2O N O O HSO4 -H2O NH3 NH3 NO2 5 weitere GF -H NH3 NO2 Phenyl: +M NH2: -I, +M ortho sterisch gehindert para O N O Macht den Aromaten weniger reaktiv 5-A3 Bis(4-methoxyphenyl)phenylmethylchlorid aus Benzotrichlorid und Anisol CCl3 OMe Cl MeO AlCl3 MeO OMe CCl3 AlCl3 Cl2 C OMe -H dto. Cl MeO MeO Cl 5-A4 b,b-Diphenylpropiophenon aus Benzalacetophenon und Benzol O O AlCl3 O AlCl3 O AlCl3 O AlCl3 O AlCl3H ~ H O - AlCl3 5-A5 4-Chloracetophenon aus Chlorbenzol und Benzoylchlorid AlCl3 Cl COCl O Cl C Cl O AlCl3 C Cl O AlCl3 C Cl O AlCl3 C Cl O AlCl4 Cl O Cl Cl AlCl3 H O Cl AlCl3 Cl O Cl AlCl4 5-A6 4-(Dimethylamino)benzophenon aus Benzanilid und N,N-Dimethylanilin NHPh O O NMe2 POCl3 NMe2 5-A6 NHPh O P O Cl Cl Cl P O Cl Cl Cl O NH Ph P O Cl O NH Ph Cl + Cl NH Cl O Ph P O Cl Cl N Cl PhH Ph PO2Cl2 NMe2 SEAr NMe 2 Cl PhNPh H NMe2 Ph N H Ph H2O NMe2 H2O PhNPh H ~ H NMe2 Cl Cl HO PhH2NPh NH2 + NMe2 HO Ph - H NMe2 O Ph 5-A7 1,3,5-Tribrombenzol aus 2,4,6-Tribromanilin NH2 Br Br Br Br BrBr 1) NaNO2, H2SO4 2) DMF, FeSO4 NH2 Br Br Br NaNO2, H2SO4 -H2O N Br Br Br N radikalischer Mechanismus Br Br Br Et O H Br BrBr Et O 5-A8 1,4-Dinitrobenzol aus 4-Nitroanilin NH2 NO2 O2NO2N 1) NaNO2, H2SO4 2) NaNO2, ? NH2 O2N NaNO2, H2SO4 -H2O N O2N N -N2 O2N NO2 NO2 O2N 5-B1 3-Bromacetophenon aus Acetophenon CH3 O CH3 O Br Br2, AlCl3 st?ch. CH3 O Br Br CH3 O H Br CH3 O H Br CH3 O H Br - H CH3 O Br COCH3: -I, -M meta AlCl3 5-B2 3-Nitroanilin und 4-Nitroanilin aus Anilin NH2 NH2 NO2 NH2 O2N NaNO3 + H2SO4 5 : 3 HNO3 + H2SO4 H2NO3 + HSO4 -H2O NO2 H2N NH2 O2N H NH2 O2N -H 5-B3 Phenylcyclooctan aus Benzol und Cycloocten H2SO4 H H H -H 5-B4 1,2,2-Triphenylpropions?ure aus 1,2-Dibrom-3- phenylpropions?ure Br CO2H Br CO2H AlBr3 CO2H Br Br AlBr3 CO2H Br AlBr4 CO2H Br H -H CO2H 5-B5 4-Bromacetophenon aus Brombenzol Br Br CH3 O CH3COCl, AlCl3 1,2-Dichlorethan , ? H3C C Cl O AlCl3 H 3C C Cl O AlCl3 H3C C Cl O AlCl3 H3C C O AlCl4 BrBr H H3C O AlCl4 Br CH3 O AlCl4 H 5-B6 Indol-3-carbaldehyd aus Indol N H N H CHO 1) DMF, POCl3 2) NaOH, H2O P O Cl Cl Cl C NMe2 O H Cl P O O Cl Cl C NMe2 H Cl P O O Cl C NMe2 H Cl Cl P O O Cl C NMe2 HCl Cl P O O Cl Cl C NMe2 H H NMe 2 NaOH H2ON H CHO N H N H H NMe 2 N H H H NMe 2 N H 5-B7 3-Nitrophenol aus 3-Nitroanilin NH2 NO2 OH NO2 1) NaNO2, H2SO4 2) H2O, H2SO4, ? NH2 NO2 1) NaNO2, H2SO4 - H2O N NO2 N NO2 N2 NO2 H2O NO2 O H H -H OH NO2 5-B8 2,4-Dihydroxybenzoes?ure aus Resorcin OH CO2H OHOH OH CO 2 , KHCO3 OH OH O C O OH OH H O O OH OH OO +H OH CO2H OH 5-C1/2 p-Toluolsulfonylchlorid und o-Toluolsulfonylchlorid aus Toluol CH3 CH3 CH3 SO2Cl SO2ClClSO3H + CH3 Cl SO3H CH2 SO3H2 -H2O CH2 SO2 H Cl -H CH3 SO2Cl 5-C3 1,3,5-Tri-tert-butylbenzol aus 1,4-Di-tert- butylbenzol tert-C4H9Cl, AlCl3 -40 bis -5 °C H H Cl -H 5-C4 (4-Aminophenyl)triphenylmethan aus Triphenylchlormethan und Anilinhydrochlorid NH2 NH3 Cl 1) Ph3CCl, AcOH, ? 2) NaOH Ph3CCl -Cl Ph3C gut stabilisiertes Carbeniumion Ph3C NH3 Cl NH3 Cl CPh3 -H NH3 Cl CPh3 OH NH2 5-C5 4’-Methylbenzophenon-2-carbons?ure aus Phthals?ureanhydrid und Toluol 5-C6 2-Methylanthrachinon aus 4’-Methylbenzophenon- 2-carbons?ure O CH3 O O O CH3 AlCl3 CO2H O O CH3 H2SO4* SO3 5C6 5C5 O O O AlCl3 O O O AlCl3 CH3 O CH3CO2 H 2O -OH O CH3CO2H 5C5 5C6: O CH3CO2H H O CH3C O O H H O O CH3H O O CH3 5-C7 Tetraphenylmethan aus (4- Aminophenyl)triphenylmethan NH2 1) NaNO2, H2SO4 2) DMF, FeSO4 R NH2 NaNO2, H2SO4 R N N -N2 R 2Fe2+ -2Fe3+ -H R H 5-C8 4,4’-Difluorbiphenyl aus Benzidin F F H2N NH2 1) NaNO2 2) HF/Pyridin H2N NH2 H2SO4NaNO2 -2H2O N N NN F 2F F F 5-D1 2,6-Dibrom-4-nitroanillin aus 4-Nitroanillin Br NH2 O2N NH2 BrO2NAcOH Br2 O2N NH2 Br Br NH2 Br HNO2 Br NH2 BrO2N 5-D2 2,4,5,7-Tetranitrofluorenon aus 9-Fluorenon O O NO2 NO2NO2 O2NHNO3, H2SO4 HNO3 + H2SO4 H2NO3 + HSO4 -H2O NO2 O NO2 O H NO2 O NO2 O NO2 NO2NO2 O2N 5-D3 Bis(4-methoxy-1-naphtyl)methan aus 1-Methoxynaphthalin OCH3 CH=O, H2SO4 Dioxan H3CO OCH3 HC O H H2SO4 C OH H H C OH H H OCH3 OCH3 H CH2OH ~H H2C OH2 H3CO OCH3 5-D4 1-(Chlormethyl)naphthalin aus Naphthalin CH2Cl CH2O, HCl HC H O H HC H OH H H OH H ~H OH2 H H H H Cl CH2Cl 5-D5 Chinizarin aus Hydrochinon und Phthals?ureanhydrid O O O OH OH O O OH OH H2SO4, ? O O O H O O O H OH OH O O HO OH O H O O OH OHOH H O O OH OHOH2 O O OH OH 5-D6 4-Pentylbenzoylchlorid aus Pentylbenzol ClCl O O AlCl3 CH2CL2 O Cl ClCl O O AlCl3 COCl2 + CO C Cl Cl O O Cl H -H O Cl 5-D7 1,2,3-Tribrom-5-nitrobenzol aus 2,6-Dibrom-4- nitroanilin Br NH2 Br BrO2NBrO2N Br1) NaNO2, H2SO4, AcOH 2) CuBr, HBr Sandmeyer: Br NH2 BrO2N NaNO2, H2SO4 Br N BrO2N N CuBr Br N BrO2N N +CuBrHSO4 Br BrO2N N2 Br BrO2N +CuBrHSO4 Br BrO2N CuBrHSO4 Br BrO2N BrCuHSO 4 5-D8 2,4,6-Tribromiodbenzol aus 2,4,6-Tribromanilin NH2 Br BrBr NaNO 2, H2SO4, AcOH; KI I Br BrBr NH2 Br BrBr NaNO 2, H2SO4, N Br BrBr N Br BrBr I I Br BrBr 5-E1Brommesitylen aus Mesitylen BrBr 2 , CCl4 Br Br Br H H Br 5-E2Ioddurol aus Durol I I2 , H2IO6, H2SO4 5-E2 I2 I2 + 2 e Oxidation H2IO6 + 2H 2 e+ H2IO5 + H2O Reduktion I2H2IO6 + + 2H I2 + H2IO5 + H2O + I I H 2 GF - H I 5-E3 1,1-Bis(4-hydroxyphenyl)-3,3,5- trimethylcyclohexan aus 3,3,5-Tri-methylcyclohexanon und Phenol O OH OHHO H2SO4, ? O H OH OH OH H -H H -H2O OH OH OHHO 5-E4 9-Anthracencarbonitril aus Anthracen O C NSO2Cl O NHSO2Cl DMF CN O C NSO2Cl O NSO2Cl +H O H N S Cl O O O NMe2H O H N S O O O NMe2 H + Cl O H N S O O O NMe2 Cl H - SO3 O NH + NMe2 Cl H O NH Cl H NMe2 - Cl Me2N O H- NH - H N 5-E5mono-Deuteromesitylen aus Brommesitylen 1) Mg, EtBr (kat.) 2) D2O Br D Br Mg SET MgBr D O D -MgBr OD D 5-E6 2-(2,3,5,6-Tetramethylphenyl)-2-propanol aus Ioddurol I 1) Mg, Et2O OH 2) Me2C=O I Mg SET MgI Me Me O -MGI O Me Me H OH 5-E7/8 Dinatrium-[8-amino-2-(4-nitrophenylazo)-1- naphthol-3,6-disulfonat] und Dinatrium-[8-amino-7-(4- nitrophenylazo)-1-naphthol-3,6-disulfonat aus Dinatrium-[8- Amino-1-naphthol-3,6-disulfonat] und p-Nitroanilin OH NH2 OH NH2 N N NO2 OH NH2 NN O2N NO2 N2 Cl pH >7 pH < 7 SO3NaNaO3S SO3NaNaO3S SO3 Na NaO3S + pH>7: NH2 O SO3HHO3S NO2 N2 Cl+ O NH2 NN O2N SO3O3S H OH NH2 NN O2N SO3 Na NaO3S pH <7: OH NH2 SO3NaNaO3S NO2 N2 Cl OH NH2 N N NO2 SO3NaNaO3S H St?rkerer Donor OH NH2 N N NO2 SO3NaNaO3S 5-F1Pikrins?ure aus Phenol OH H2SO4 OH SO3H SO3H OH NO2 NO2 O2NHNO3, H2SO4 2H2SO4 H3SO4 HSO4 -H2O HSO3 OH OH SO3H H OH SO3HH SO3H HNO3 H2SO4 H2NO3 HSO4 -H2O NO2 OH SO3HH SO3H NO2 OH SO3HNO2 SO3H OH NO2 NO2 O2N 5-F2 4,4’-Diodbiphenyl aus Biphenyl I I I2 , HIO4, H2SO4 I I δ δ I- HI I I SEAr 5-F3 Kristallviolett aus Michlers Keton und Dimethylanilin NMe2Me 2N O NMe2 ClH NMe2 PCl5, ? Me2N Me2N NMe2Me 2N O P Cl Cl Cl Cl Cl -Cl R R O PCl4 Ar NMe2 Cl4P O NMe2 R R PCl4 O NMe2 ClH Me2N Me2N 5-F4 p-tert-Butyl[4]calixaren aus p-tert-Butylphenol und Formaldehyd t-Bu t-Bu t-Bu t-Bu OH OH OH HO t-Bu OH HCHO NaOH, H2O 5-F4 t-Bu OH t-Bu O OH-H2O H H O H2O t-Bu OH OH OH OH -H2O t-Bu O OH t-Bu O CH2 t-Bu O t-Bu O t-Bu O H2O OH t-Bu OH t-Bu OH dto. t-Bu t-Bu t-Bu t-Bu OH OH OH HO 5-F5 2-Pyrrolcarbaldehyd aus Pyrrol N H N H CHO 1) Me2NCHO/POCl3 2) NaOAc, H2O, ? P O Cl Cl Cl C NMe2 O H Cl P O O Cl Cl C NMe2 H Cl P O O Cl C NMe2 H Cl Cl P O O Cl C NMe2 HCl Cl P O O Cl Cl C NMe2 H N H -H N H C NMe2 H OH N H C NMe2 H OH H2O -OH N H C NMe2 O H H HNH C H OH + Me2NH + 5-F6 tert-Butylphenylether aus Brombenzol Br O tBuOK tBuOH, DMSO, ? Br H tBuOH O OtBu OH ~H 5-F7 Methylorange aus Sulfanils?ure und N,N- Dimethylanilin NMe2 N NHO3S N N NaO3S NMe2 Cl N NO3S N NO3S NMe2 N N O3S NMe2 N N O3S NMe2 H 5-F8 1-Phenylazo-2-naphthol aus 2-Naphthol und Anilin NPhN2 Cl OH OH N N N N N OH N OH N