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
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
