O
O
O H
N+
H
C–
N
O
O
O
H
H
O
ON O
O
H
H
H
H
C–
H
H
O
HO N+
H N
+ C–
N
+
C–
N+
C–
N+
C–
O H
N+–C
C– H
+N
C–
N+
C–
N+
C–
+N
C–
N+
–C
N
+
C–
N+
–
C
C–
+N
C–
N
+ O
+N
C–
N+
–C
+N
C–
O–C
N+ C–
+N
–C
+N
N
C–
+N
C–
O
H
HO H
H
H
H
N
N
O
O
O
O
H
O
H
H
NH
O
O
O
H
HO
H
H
H
H
N
O
N
O
OH
H
H
H
O
OHO
H
OH
H
H
H
H
N
NH
O
HO
HH
H
H
N
O
NH
O
O
HO O
H
O
H
H
N
NH
O
O
HO
O
HOH
HH
HH
N
NH
O
O
O
H
HO
H
H
H
H
N
NH
O
O
H
H
H
18
H
18
O
18
1
8
OH
O
HO
H
HO
H
HO
H
O
OH
H
HO
HO
HHO
H
HO
H
OH
OH
H
HO
HO
H
OH
HO
H
H
HO
H
OH
H
HO
H
O
OHH
OH
OH
H
HO
O
H
H O
OH
H
HO
O
HO
H
HO
H
OH
H
H
HO
HO
H
H
O
OH
H
Meik Wissert,Marco Frey,Dominic Kramer,
Alexander Drechsle,Christoph Fik
Vorwort
1,5 Tage (18 Stunden) 4,5 Personen,5,5 Computer 8 Kannen
Kaffee c,a,10000 Kcal
Bei diesem Skript ist zu beachten:
Bei sich in analoger Weise wiederholenden
Whelandkomplexen wurde aus Zeit- und Platzgründen auf die
mesomeren Grenzformeln verzichtet,Gleiches trifft auch auf
die meisten übergangszust?nde bei SN-Reaktionen zu.
Auch wurde nur in dem Versuch 2E1 die Diazotierung
vollst?ndig ausformuliert,da sie sich von den anderen
Beispielen nicht unterscheidet.
Die angebotenen Mechanismen sind als L?sungsvorschl?ge zu
verstehen und basieren auf der Begleitvorlesung zum OGP
(Wintersemester 02/03),gehalten von Dr,Rainer Haag.
Fehler und Irrtümer sind nicht auszuschlie?en.
1,Radikalische Substitution am ges?ttigten C-Atom
1-A1 α,α′-Dibrom-ο-xylol aus ο-Xylol
1-A1
CH2
CH3
CH2Br
CH2Br
,hν
Br2
Br Br hν 2BrStart:
Propagation:
H
+ Br HBr +
CH3
CH2
CH3
CH3
CH3
CH2
Br Br+ Br +
CH3
CH2Br
CH2
CH2Br
CH2Br
CH2Br
+ Br
H
1-A2 3-Bromcyclohexen aus Cyclohexen
1-A2
Br
NBS
CCl4,AiBN,D
Start,NC N N CN 2 NC +N2?
Propagation,NC + NBr
O
O
NBr
O
ONC
N
O
ONC
+ B
r
+ Br
H
HBr +
HBr + NBr
O
O
ionisch,
rasch
Br Br
+ NH
O
O
+
Br Br
Br
+ Br
1-A3 1-Chloradamantan aus Adamantan
SO2Cl2
SO2
Cl
Start,Initiator 2R
Propagation,R S
O
O
ClCl+ RCl + SO2Cl
H
SO2Cl+ + SO2 + HCl
+ S
O
O
ClCl
Cl
+ SO2Cl
1-B1 α,α,α′,α′-Tetrabrom-p-xylol aus p-Xylol
,hνH3C
CH3 CHBr2
Br2HC
Br2
Br Br 2BrhνStart
Propagation
H3C
H2
C
H Br
H3C
CH2
HBr
H3C
CH2
Br Br
H3C
CH2Br
Br
CHBr2
Br2HC
1-B2 trans-4-Bromcrotons?ureethylester aus
Crotons?ureethylester
1-B2
NBSCO2Et CO2EtBr
CCl4,AiBN,?
Start,NC N N CN 2 NC +N2?
Propagation,NC + NBr
O
O
NBr
O
ONC
N
O
ONC
+ Br
CO2EtHBr + HBr + CO2Et
HBr + NBr
O
O
ionisch,
rasch Br Br + NH
O
O
CO2EtBr Br + CO2EtBr + Br
und nicht CO2Et
Br
da dies mit einem Verlust von
Konjugationsenergie einher gehen würde
1-B3 (1-Chlor-1-methylethyl)benzol aus Cumol
AiBN/?
CH3
H2C
CH3
CH2Cl
CH
CH3
Cl
SO2Cl2
Start,NC N N CN? 2 CN N2
Propagation:
NC NC Cl
SO2Cl
H
SO2 + HCl +
SO2Cl2
CH2Cl
CH
CH3
Cl SO2Cl
SO2Cl
O
S Cl
O
Cl
1-C1 Brommalons?urediethylester aus
Malons?urediethylester
H2C
CO2Et
CO2Et
CH
CO2Et
CO2Et
Br
CCl4,?/hν
Br2
Br Br 2Brhν
Br CH
CO2Et
CO2Et
Start
Propagation
H HBr HC
CO2Et
CO2Et
HC
CO2Et
CO2Et
Br Br CH
CO2Et
CO2Et
Br Br
1-C2 trans-3,6-Dibromcyclohexen aus Cyclohexen
Start,NC N N CN? 2 CN N2
NC N
O
O
Br N
O
O
Br
N
O
O
Br
NBS
CCl4,AiBN,?
Br
H
Br HBr
Br Br*
*
HBr N
O
O
Br ionisch Br Br HN
O
O
Br
Br
Br
Der 2,Schrit verl?uft analog.
NC
NC
1-C3 1-Chlor-4-(chlormethyl)benzol aus 4-Chlortoluol
1-C3AiBN/?
SO2Cl2
CH3
Cl
CH2Cl
Cl
Start,NC N N CN 2 NC +N2
Propagation:
NC + S
O
O
ClCl NC Cl + SO2Cl
CH2
Cl
H
+ SO2Cl
CH2
Cl
+ SO2 + HCl
CH2
Cl
+ S
O
O
ClCl
CH2Cl
Cl
+ SO2Cl
1-D1 4-Brom-2,2,4-trimethylpentan aus iso-Octan
1-
D1
CCl4,?/hν Br
Br2
Br Br hν 2Br
+ Br
H
+ HBr
Br Br+
Br
+ Br
Start:
Propagation:
Hohe Regioselektivit?t am terti?ren C-Atom (Hammond-Postulat)
1-D2 4-Brom-β-ionon aus β-Ionon
CCl4,AiBN,?
O O
Br
NBS
1-D2
Start,NC N N CN 2 NC +N2?
Propagation,NC + NBr
O
O
NBr
O
ONC
N
O
ONC
+ Br
O
Br +
H
HBr +
O
HBr
+
+ NBr
O
O
ionisch,
rasch Br Br + NH
O
O
Br Br +
O O
Br
+ Br
O
und nicht
O
Br
und kein
(Verlust der Konjugation)
1-D3 1-Chlor-4-(dichlormethyl)benzol aus 4-Chlortoluol
1-D3AiBN/?
SO2Cl2
Cl
CH3
Cl
Cl
Cl
Start,NC N N CN 2 NC +N2
Propagation:
NC + S
O
O
ClCl NC Cl + SO2Cl
CH2
Cl
H
+ SO2Cl
CH2
Cl
+ SO2 + HCl
CH2
Cl
+ S
O
O
ClCl
CH2Cl
Cl
+ SO2Cl
CHCl
Cl
H
+ SO2Cl
Cl
H
C Cl + SO
2 + HCl
Cl
H
C Cl
+ S
O
O
ClCl
Cl
Cl
Cl
+ SO2Cl
2,Nucleophile Substitution am ges?ttigten C-Atom
2-A1 1 Bromoctan aus 1 Octanol
OH HBr,H2SO4
Br
OH H Br OH2 Br
OH2
Br
Br
2-A2 1-Brom-3-methyl-2-buten aus 2-Methyl-3-buten-2-
ol
2-A2
OH
BrHBr,(aq.)
RT
OH
+H
OH2 -H2O
+Br
Br
h?her substituierte Doppelbindung ist thermodynamisch begünstigt
2-A3 2,7-Dihydro-3-benzothiophen aus α,α′-Dibrom-o-
xylol (1-A1)
CH2Br
CH2Br
Na2S,DMF S
H
H
Br
H Br
H
S2- -Br
H
H
S
H
H
Br
-Br
S
2-A4 1,2-Bis(mercaptomethyl)benzol aus α,α′-Dibrom-o-
xylol (1-A1)
S
H2N NH2CH2Br
CH2Br
SH
SH
1)
2) KOH/H2O
Br
Br
S
H2N NH2
H2
C
H2C
S C
NH2
NH2
S C
NH2
NH2
2 2 OH
H2
C
H2C
S C
NH2
NH2
S C
NH2
NH2
O
O
H
H
H2
C
H2C
S C
NH2
NH2
S C
NH2
NH2
S
SH2N NH2
O H2 O
H2N NH2
SH
SH
2-B1 Terephthalaldehyd aus α,α,α′,α′-Tetrabrom-p-xylol
(1-B1)
Br2HC
CHBr2 CHO
OHC2) H
2O
1) H2SO4,?T
CH Br
Br
CH Br
Br
O S OH
O
O
CO
H
CH Br
Br
S O S
O
O
OH
O
O
HO
2 HBr
H2O
C OO
H H
CH Br
Br
S
O
O
HO - HSO
4
-H
- H
- HSO4
HC
O
CH Br
Br
CHO
OHC
2-B2 cis-1-tert-Butyl-4-chlorcyclohexan aus trans-4-tert-
Butylcyclohexanol
Cl
OH
PCl5
O PCl
Cl Cl
ClClH O H
PCl4
Cl
H
Cl
2-B3 trans-1-tert-Butyl-4-chlorcyclohexan aus trans-4-
tert-Butylcyclohexanol
OH Cl
ZnCl2,HCl
2-B2
OH
ZnCl2
OH
ZnCl2
HCl
OH2
ZnCl2
Cl
-H2O,
-ZnCl2
Cl
Cl
Angriff in?quatorialer Stellung,weil dadurch ein stabileres Produkt gebildet
wird
2-B4 cis-4-Acetoxy-tert-butylcyclohexan aus trans-tert-
Butylcyclohexylchlorid (2-B3)
2-B4
OAcKOAc/AcOH
Cl
Cl
H OAc
H
AcO
Cl
-Cl
O
Ac
H
2-C1 (Phthalimido)malons?urediethylester aus Phthalimid
und Brommalon-s?urediethylester (1-C1)
NH
O
O
1.) KOH,EtOH
2.)
Br
CO2Et
CO2Et
N
O
O
CO2Et
CO2Et
N
O
O
KOH N
O
O
Br CO2EtCO
2Et
N
O
O
CO2Et
CO2Et
-I-Effekt von C
OEt
H
2-C2 4-Chlorbenzylfluorid aus 1-Chlor-4-
(chlormethyl)benzol (1-C3)
2-C2
Cl
Cl
Cl
F
KF,?
DMF
Cl
Cl
F
Cl
Cl
F
Cl
F
SN2
Substitution an genannten Kohlenstoffatom,weil eine Stabilisierung der Zwischenstufe durch
konjugiertes aromatisches System stabilisiert wird,
2-C3 4-Chlorbenzaldehyd aus 1-Chlor-4-
(dichlormethyl)benzol (1-D3)
Cl
Cl
Cl
Urotropin,?
EtOH,H2O
Cl
OH
OH
Cl
O
Cl
Cl
Cl
Urotropin,?
EtOH,H2O
Cl
O
2-C4a E-1-Chlor-3,7-dimethyl-2,6-octadien aus Geraniol
Cl
2) Pyridin
OH 1) MeSO2Cl
O S Cl
O
CH
H
H
N NH
Cl
S CH2
O
O
Sulfen
OHO
H
S
O
O CH2
O
S OO
CH3
Mesylat
NH
Cl
Cl
O S CH3
O
O
Methansulfonation
2-C4b E-1-Chlor-3,7-dimethyl-2,6-octadien aus Nerol
Cl
1) MeSO2Cl
OH
2) Pyridin
OH
Me S Cl
O
O
OH
S O
O
Me
Cl
O
S
Me
OO
Cl
Cl
O S Me
O
O
gute Abgangsgruppe
2-D1 (S)-(-)-2-Brom-3-hydroxypropions?ure aus L-Serin
2-D2 Kalium-(R)-2,3-epoxypropionat aus (S)-(-)-2-Brom-
3-hydroxy-propions?ure (2-D1)
2-D3 R-Glycids?urebenzylester aus Kalium-(R)-2,3-
epoxypropionat (2-D2)
2-D2
2-D3
CO2
HO
NH3
HBr,NaNO2
CO2H
HO
Br
K
O
CO2
O
CO2CH2Ph
C6H5CH2Br
CH3CN,
Dibenzo-18-krone-6
(2-D4)
2-D1
KOH
EtOH
HO C
NH3
OH
O
HO CO
2H
Br
2 mal Inversion Rentention
2-D1
K
O
CO2
Br
O
CO2CH2
Ph
KBr
CO2H
HO
Br
2KOH
CO2
O
Br
-2H2O K
K
-KBr
SN2
2-D2
2-D3
HO C
N2
OH
O
HO
O
OH
- N2s,2-E1
2-D4 Dibenzo-18-krone-6 aus Brenzcatechin und Bis(2-
chlorethyl)ether
2-D4
OH
OH
O
O
O
O
O
O
O
NaOH,?
ClCl
+
n-Butanol
OH
OH
OH
O
O
ClCl
OH
O
O
Cl-Cl
O
O
O
O
O
O
+OH
-H2O
Na
Templateffekt
2-E1(S)-2-Chlorpropions?ure aus L-Alanin
2-E2(R)-2-(Pyrrolidin-1-yl)propions?ure aus (S)-2-
Chlorpropions?ure (2-E1)
2-E1
2-E2
O2C CH3
Cl
O2C CH3
NH3
O2C CH3
Cl
O2C CH3
N
NH
NaNO2 / HCl
(2-E1)
HO N
O + H
H2O N
O
N O N O
H
O2C CH3
NH3
HOOC CH3
NH2 N
O
HOOC CH3
NH2
N
O
~ H
HOOC CH3
NH
N
OH
HOOC CH3
NH
N
OH
~ H
HOOC CH3
N
N
OH2
CH3
N
N
O
OH
O
HO
CH3
H O
HO
CH3
H
Cl
O2C CH3
Cl
- H
2-E1
NH
SN22-E2
O2C CH3
N H
2-E3 1,4-Diiodbutan aus Tetrahydrofuran
2-E3
O I I
KI,H3PO4,?
O H O H
I I OH H
I OH2
I -H2O
I I
*
*mit H3PO4 Polyphosphate
2-E4 S-2-(Pyrrolidin-1-yl)propions?ure aus L-Alanin und 1,4-
Diodbutan (2-E3)
2-E4
O2C CH3
NH3
O2C CH3
N
NaHCO3 / Toluol
I I
(2-E3)
O2C CH3
NH3
+OH
-H2O
O2C CH3
NH2
I
I
-I
O2C CH3
HN
SN2
I
SN2
-I
O2C CH3
N
H
H
2-F1Pentaerythrittetrabenzolsulfonat aus Pentaerythrit
2-F1
OH
HO
HO
OH
OSO2Ph
PhO2SO
PhO2SO
OSO2PhPhSO2Cl
Pyridin
O
HO
HO
OH
Ph S Cl
O
O
-Cl
O
HO
HO
OH
S
O
O
Ph
OSO2Ph
PhO2SO
PhO2SO
OSO2Ph
H OH
HO
HO
O S
H O Cl
O Ph
OH
HO
HO
O S
H O
O Ph
N
2-F2 1,3-Diiod-2,2-bis(iodethyl)propan aus
Pentaerythrittetrabenzolsulfonat (2-F1)
OSO2Ph
PhO2SO
PhO2SO
OSO2Ph
2-F2
OSO2Ph
PhO2SO
PhO2SO
OSO2Ph
I
I
I
INaI
DMF
+
- OSO2Ph
I
PhO2SO
PhO2SO
OSO2Ph
I
I
I
I
I
2-F3(S)-(+)-γ-Butyrolacton-γ-carbons?ure aus L-
Glutamins?ure
HO
NH3O
CO2
NaNO2,H2SO4
O
O
COOH
H
HO
NH3O
CO2
NaNO2,H2SO4
-2H2O
HO
NO
N
-N2
HO
O O
HO CO2
OHO CO2H
O
O
COOH
H
O
O
O
O
2-F4 2,2-Dimethyl-5-pentyltetrahydrofuran aus 2-Methyl-2,5-
decandiol (6-A2)
2-F4
OOH
Pent
OH Pent
H3PO4
OH
Pent
OH
+H
OH2
Pent
OH -H2O
Pent
OH
- H
OPent
SN1
intramolekulare Reaktion sind immer schneller als intermolekulare Reaktionen
3,Additionen an olefinische C=C-Bindungen
3-A1
HO
HO
Br2
BrBr
HO
Br Br HO Br
Br
HO
BrBr
Der Angriff am C-Atom ist aufgrund der
Methyl-
gruppe erschwert und aufgrund des H-Atoms
unten erfolgt der Angriff von oben,
keine Diastereomere
AcOH
3-A2 trans-1,2-Cyclohexandiol aus Cyclohexen
OH
OH
H2O2
HCO2H,H2O
HO OH C H
O
HO
H O O C
O
H
HO C H
O
O
H2O
OH
OH
HO
O H
H OH
O
- H2O
H
O
O
O
H
3-A3 cis-1,2-Cyclohexandiol aus Cyclohexen
OH
OH
O
N
O
,K2OsO2(OH)4
kat.
Os
O
O O
O O
Os
O O
O
H2O
O
OsO
OH2
O
O
OH
Os
O
dto.
OH
OH
Os
O
O
HO
HO
VIII VI
O
O
OH
O
N
O
VI
Os
O
O O
O
VIII
O
N
- H2O
3-A4 1,1-Dichlor-2-phenylcyclopropan aus Styrol
Cl
ClHCCl3,NaOH
3-A4
HCCl3 + OH H2O + CCl3
-Cl
CCl2
Phasentransferkatalysator
CCl2+
Cl
Cl
racemisch
3-B1 trans-3,4-Dibromcumarin aus Cumarin
O O O O
Br
BrBr2,CHCl3
O O
Br Br
O O
Br
Br
O O
Br
Br
3-B2 cis-3,4-Dibromcumarin aus o-Hydroxyzimts?ure
CO2H
OH O
Br
Br
O
Br2,CCl4
CO2H
OH Br Br
CO2H
OH
Br
Br
O
Br
Br
O
OH
H O
Br
Br
O
H2O
Ringschlu? ist Entropiegetrieben ( zwei Teilchen)
3-B3 2-Octanon aus 1-Octen
O2,PdCl2,CuCl2 O
β-Cyclodextrin/Wasser
Cl Pd Cl
Pd
H
R
H H
Cl H
2O
H
H
Pd
OH2
R
H
Cl - Pd°
- HCl
H
H
HO
R
H
H
O
R
Bdg,etwas l?nger
Cl
3-B4 cis-Cyclooctenoxid aus cis-Cycloocten
O
H2O2,KHCO3
MeOH/MeCN
HO OH H2O + CO2 + OOH
N C CH3 OOH N CH3
OOH
H
HN CH3
OOH
Peroxyimids?ure
H
O O
NH
CH3 O
meso - Form
C
O
H2N
CH3
O
O OH
3-C1 (+),(-)-Dibrombernsteins?ure aus Maleins?ure
COOH
H
H
COOH
COOH
COOH
HBr
BrH
COOH
COOH
H Br
Br H
Br2
+
COOH
H
H
COOH
Br Br Br
COOH
COOH
H
H
Br
COOH
COOH
H Br
Br H
racemisch
3-C2 meso-Dibrombernsteins?ure aus Fumars?ure
COOH
HOOC
H
H
COOH
COOH
BrH
BrH
Br2
COOH
HOOC
H
H
Br Br Br
COOH
H
HOOC
H
Br
COOH
COOH
BrH
BrH
3-C3 2,3-Epoxygeraniol aus Geraniol
in Emulsion aus
Octanol/Hexan/Wasser
(Octadecyl)2(Me)2NCl
OH OH
O
m-Cl-C6H4-CO3H
Im Zweiphasigen System wird bevorzugt die
Doppelbindung am polaren Ende des Moleküls
angegriffen
OH
CO
OO
H
Cl
OH
O C
OH
O
C
l
3-C4 6,7-Epoxygeranylacetat aus Geranylacetat
OAc OAcm-Cl-C6H4-CO3H
CH2Cl2
O
Die e--reichere Doppelbindung wird in L?sung
bevorzugt angegriffen
e--arm
e--reich
3-D1a erythro-9,10-Dibromstearins?ure aus?ls?ure
3-D1b threo-9,10-Dibromstearins?ure aus Elaidins?ure
COOH COOHBr
Br
Br2
3-D1a
Br Br +
COOH COOHBr
+ Br
COOH
BrBr + COOH
Br
Br
racemisch
COOH
COOHBr2 Br
Br 3-D1b
COOHBr Br
+
CO
OHBrBr
+
COOH
Br
Br
^=
COOHBr
Br
HR1
Br
racemisch
Br
H R2^=
R1
R2
Br
Br
3-D2 1-Chlorindan aus Inden
Cl
H Cl
HCl
H Cl
benzylst?ndige positive Ladung
Cl
3-D3 10-Brom-11-hydroxy-10,11-dihydrofarnesylacetat
aus Farnesylacetat
OCOCH3
HO
OCOCH3
Brtert.-ButOH/H2O
NBS
OCOCH3
N OO
Br
OCOCH3
Br
l?nger und damit schw?cher
OH
N
O
O
HO
OCOCH3
Br
N
O
O
H2O HN
O
O
OH
3-D4 Malons?ure-di-tert-amylester aus 2-Methyl-2-buten
und Malons?ure
O
O
O
O
H2SO4
OH
O
OH
O
2 H2SO4 H
OH
O
OH
O
O
O
O
O
H
H
-2H
O
O
O
O
3-E1 exo-cis-Bicyclo[2.2.1]heptan-2,3-diol aus 2-Norbornen
3-E2 endo-cis-1,7,7-Trimethylbicyclo[2.2.1]heptan-2,3-diol
aus 2-Bornen
3-E3 endo-cis-1,7,7-Trimethyl-3-tert-
amyloxybicyclo[2.2.1]heptan-2-ol aus endo-cis-1,7,7-
Trimethylbicyclo[2.2.1]heptan-2,3-diol (3-E2)
OH
KMnO4,NaOH
OH
OOH H2SO4
KMnO4,NaOH
OH
OH
3-E1
3-E2
3-E3
3-E1
Mn
O
O
O
O
O Mn
O
O
O
OH
O
Mn
O
OO
OH
+H
O
Mn
OH
OO
OH
OH
OH
Mn
O
O
HO
HO
Einflug des Permanganats von der weniger stark gekrümmten (konkaven) Seite (exo)
Angriff von oben?quatoriale Position der Hydroxidgruppen
3-E2
Mn
O
O
O
O
O Mn
O
OH
O
OH
OH
OH Mn O
O
HO
HO
3-E3
H
H
OH
OH
H
OH
HO
-M
OOH
Sterisch leichter Zug?nglich
3-E4β-Ionon aus Pseudoionon
O O
H2SO4
3-E4
O
~H
OH
O
H
-H
O
4,β-Eliminierungen
4-A1 1,3-Cyclohexadien aus 3-Bromcyclohexen
Br
N
Br
H N
H
N
4-A2 1,3-Cyclohexadien aus trans-1,2-Dibromcyclohexan
Br
Br
NaOH
CH3-O-CH2-CH2-OH
H
HH
Br
Br
HH
OH + CH3-O-CH2-CH2-OH
H2O + O-CH2-CH2-O-CH3
H
H
H
H
Br
OR
statt,weil dann Br
und H im Winkel von 60°
statt 180° zueinander
stehen.Br
4-A3 1-Bromcyclohexen aus trans-1,2-Dibromcyclohexan
Br
Br BrNaNH
2
tert-BuOH
Br
Br
H
Na
O Br
HO-tBu + Na Br
4-A4a 3-Menthen und 2-Menthen aus (+)-
Neomenthyltosylat mit Natriummethanolat
NaOMe
OTs
+
OTs
NaOHMe
H
TsO
Isopropyl ist ein konformativer Anker.
4-A4b 2-Menthen und 3-Menthen aus (+)-
Neomenthyltosylat mit Kalium-tert-butylat
OTs
+
4-A4b
tert-BuOK
H
OTs
H
CH3
Ot-Bu
H
CH3-OTs
+
E2,KOt-Bu sterisch anspruchsvolle Base Hofmann
Aber OTs gute Abgangsgruppe E1 auch Saytzew
4-B1 3-Methyl-2-methylenbutters?ure-tert-butylester aus
2-Brom-2,3-dimethylbutters?ure-tert-butylester
CO2-tert-Bu
H3C
CH3
CO2-tert-Bu
CH2
H3C
CH3
Br
CH3
tert-BuOK
tert-BuOK ist eine anspruchsvolle Base,deshalb erfolgt der Angriff an einem peripheren
C-Atom
CO2-tert-Bu
H3C
CH3
Br
CH2 O
H
tertBuOH
CO2-tert-Bu
CH2
H3C
CH3
Br
4-B2 2,3-Dimethyl-2-butens?ure-tert-butylester aus 2-
Brom-2,3-dimethyl-butters?ure-tert-butylester
CO2-tert-Bu
CH3
H3C
CH3
NCO2-tert-Bu
H3C
CH3
Br
CH3
CO2-tert-Bu
H3C
CH3
Br
CH3
N
H
CO2-tert-Bu
CH3
H3C
CH3
Saytzew
DBU ist eine schwache Base kleiner
Energiegewinn sp?ter üZ hohe
Regioselektivit?t
4-B3 2-Phenylpropen aus (1-Chlor-1-methylethyl)-benzol
Cl
N
N
,
4-B3
Cl
H
H
H
ba (DBU)
4-B4 1-Cyanocyclohexen aus Cyclohexanoncyanhydrin
CNHO CN
SOCl2
CNHO
Cl S Cl
O
-HCl
CNOS
Cl
O
H
CN
+ HCl + SO2
eventuell aber auch E1 über,CN
HO S Cl
O
4-C1 Bromfumars?ure aus (+),(-)-Dibrombernsteins?ure
HOOC
COOHBr
H
COOHHOOC
Br
Br
H2O,?
COOHHOOC
Br
Br
H H2O,? HOOC
COOHBr
H
HBr
HBr ist die Triebkraft ( Entropie)
4-C2 Brommaleins?ure aus meso-Dibrombernsteins?ure
HOOC
HBr
COOH
COOHHOOC
Br
Br
H2O,?
COOHHOOC
Br
Br?T HOOC
COOH
H
H
Br
HOOC
HBr
COOH
4-C3 3-Menthen und 2-Menthen aus (-)-Menthylacetat
O
O 450°C
+
O
O
H
O
O Saytzew-Produkt
Tschugajev Eliminierung cyclischer
übergangszust?nde
4-C4 3-Menthen und 2-Menthen aus O-(-)-Menthyl-S-
methylxanthogenat
O SMe
S 140-150°C
+
4-C4
H O
MeS
S
Me
H
H
Me
+
MeS
SH
O
iPr konformativer Anker syn-Eliminierung
4-D1 3-Menthen aus (-)-Menthol
OH
H2SO4
OH
H
OH2 H
-H
4-D2 2-Menthen aus (-)-Menthylchlorid
Cl
KO tBu
Dibenzo-18-krone-6
(2-D4)
Petrolether
Cl
H K O tBu
H H
H
Cl Mindermengenkonformer
erkl?rt Regioselektivit?t,
weil H-Atom und Cl-Atom
periplanar zueinander stehen,
4-D3 trans,trans-Mucons?urediethylester aus 2,5-
Dibromadipin?urediethylester
EtO2C
CO2Et
Br
Br
EtO2C CO
2Et
Pyridin
EtO2C
CO2Et
Br
Br
N
H
H
EtO2C
CO2
Et
Br
EtO2C CO
2Et
4-D4 1,1-Diphenylethylen aus 1,1-Diphenylethanol
OH
H2SO4
4-D4
OH
+H
OH2 E
1
-H2o
H2C
H
-H
Wasser fungiert als Base zur Protonenübertragung
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,D
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,D
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,D
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,D
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,D
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-E1 Brommesitylen aus Mesitylen
BrBr
2,CCl4
Br Br Br
H
H
Br
5-E2 Ioddurol 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,D
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-E5 mono-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
p H > 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-F1 Pikrins?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
d d
I- HI
I I
SEAr
5-F3 Kristallviolett aus Michlers Keton und
Dimethylanilin
NMe2Me
2N
O
NMe2
ClH
NMe2
PCl5,D
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,D
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,D
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
6,Nucleophile Substitutionen an Carbons?urederivaten
6-A1 Pivalins?urepyrrolidid aus Pivaloylchlorid und
Pyrrolidin
6-A2 tert-Butylcyclohexenylketon aus
Pivalins?urepyrrolidid (6-A1) und dem von 1-
Bromcyclohexen (4-A3) abgeleiteten Grignard-Reagenz
NHO
Cl
O
NCHCl3,Pyridin
O
Mg Br
6-A2
6-A1
O
Cl
NH
Cl
O
N
-Cl
O
N
6-A
1
Mg Br
+
N
O
MgBr
HCl
O
NH
O
6-A2
H -H
H
-H,
NH-
6-A3 (R)-3-Hydroxybutters?uremethylester aus Poly-[(R)-
3-hydroxybutters?ure]
ClCH2CH2Cl / CH3OH
H2SO4
O O
H
HO
n
OMe
OOH
6-A3
O OH
H
HO
n MeOH
O OH
H
HO
nOH
Me
~H O OH
H
OH2nO
Me
O
OMe
OH
O OH
HO
n-1
- -H2O
6-A4 2-Methyl-2,5-decandiol aus -Pentyl- -butyrolacton
O
nC5H11
O
OH
HO
nC5H11
MeMgI
6-A4
O
nC5H11
O
Me MgI
O
nC5H11
O
Me MgI
OO
nC5H11
Me MgI
MgI
O
O
nC5H11MgI
MgI
OH
HO
nC5H11
+NH4Cl -2 NH3,-2 MgICl
6-B1 Fluoren-9-carbaldehyd aus Fluoren
CHO
NaH,HCO2Et
6-B1
HH
NaH
-H2
Na
O
H OEt
OEtH
O
H
O
H OEt
H
-HOEt
O
H
-H
6-B2 Sebacins?uredichlorid aus Sebacins?ure
6-B3 Sebacins?urediamid aus Sebacins?uredichlorid (6-
B2)
O
Cl (CH2)8 Cl
O
O
OH (CH
2)8
HO
O
SOCl2
O
H2N (CH2)8 NH2
O
NH3 (wrig)
6-B2
6-B3
O
OH (CH
2)8
HO
O S Cl
O
Cl
O
OH (CH
2)8
O
O
S
O
Cl
+Cl
H
O
OH (CH
2)8
O
O
S
O
Cl
+Cl +
H
O
OH (CH
2)8 O
O
S
O
Cl
Cl
H +
-HCl / -SO2
O
OH (CH
2)8 Cl
O
O
Cl (CH2)8 Cl
Oanalog
O
Cl (CH2)8 Cl
O NH
3
O
Cl (CH2)8 Cl
O
NH3
O
Cl (CH2)8 NH3
O
Cl
O
Cl (CH2)8 NH2
O
O
H2N (CH2)8 NH2
O
analog
- HCl
6-B4 Octanal aus N-Formylpiperidin und dem
Grignardreagenz aus 1-Bromoctan (2-A1)
1) Mg,Et2O
2)
Hept Br Hept
O
NO 6-B4
Hept Br
Mg
(SET)
Hept MgBr
Hept MgBr
N
O
NHept
OH MgBr
NHHept
OH MgBr
H
Hept O
-HN
6-C1 Acetylsalicyls?ure aus Salicyls?ure
CO2H
HO
CO2H
OAc
O OO
H2SO4
6-C1
CO2H
HO
O OHO
CO2H
O
H O
O O
~H
CO2H
O
O
O O
H- HOAc
CO2H
OAc
6-C1
6-C2 Sebacins?uremonomethylester aus
Sebacins?ures?uredimethylester
6-C3 10-Methyl-10-hydroxy-undecans?ure aus
Sebacins?uremonomethylester (6 C2)
6-C4 Sebacins?ureethylmethylester aus
Sebacins?uremonomethylester (6-C2)
O
MeO (CH2)8 OH
OO
MeO (CH2)8 OMe
O
1) Ba(OH)2
2) H3O
1) MeMgI
OH
(CH2)8 OH
O
1) Cl-CO-OEt
2) EtOH
O
MeO (CH2)8 OEt
O
2) NH4Cl/H2O
6-C2
6-C3
6-C4
O
MeO (CH2)8 OMe
O OH O
MeO (CH2)8 OMe
O
OH
O
MeO (CH2)8
O
OH
+ OMe
O
MeO (CH2)8
O
O -HOMe
+H
O
MeO (CH2)8 OH
O
6-C2
O
O (CH2)8 OMe
O
6-C2
Me MgI O
O (CH2)8 OMe
O MgI
+NH4 / -NH3
H
Me MgI
-CH4
O
O (CH2)8 OMe
O MgI
H
-HOMe
O
O (CH2)8
O
Me MgI
O
O (CH2)8
O H OH
(CH2)8 OH
O
6-C3
O
OH(H2C)8MeO
O
6-C2
+ NEt3
- HNEt3
O
O(H2C)8MeO
O
O
Cl OEt
O
O(H2C)8MeO
O
O
ClO
Et
O
O(H2C)8MeO
O
O
OEt
Cl
O
O(H2C)8MeO
O
O
OEtCl (H2C)8MeO
O
Cl
O
EtOH
(H2C)8MeO
O
Cl
O
OH
Et
(H2C)8MeO
O O
OEt
H
-H
O
MeO (CH2)8 OEt
O
6-C4
+ O
O
OEt
- CO2/OEt
6-D1 (S)-Hydroxybernsteins?uredimethylester aus (S)-
pfels?ure
HO
O
H O
O
O H
MeO
O
OMe
O
HOH+ (Ionen-
austauscher)
MeOH
6-D1
HO
O
H O
O
O H
H HO
O
H O
OH
O H
CH3OH
HO
O
H O
OH
O H O
Me
H
~HHO
O
H O
OH2
O H O
Me
HO
O
O H
OH
OMe
-H2O
-H HO
O
OMe
O
HO
MeO
O
OMe
O
HO
6-D2 1-(Phenylacetyl)imidazol aus Phenylessigs?ure und
1,1‘-Carbonyldiimidazol
N
O
N
O
N NN N
6-D2
O
O H
O
O H
O
N NN N
O
O +
O
N NN N H
O
O
O
N
N N
N
H
O
O
O
N
N
N
N
H
O
N
O
N
N
O
N
H
~H O
N
O
N
N
O
N
H
-CO2/ -N
N
H
O
N
N
6-D3 Benzylethylketon aus 1-(Phenylacetyl)imidazol (6-
D2) und Ethylmagnesiumbromid
O
N
N
EtMgBr
6-D3
O
O
N
N Et MgBr
O
N
NEt
MgBr
H
O
NH
NEt
MgBr
O N
N H
6-D4 Fumars?ure-tert-butylethylester aus
Fumars?uremonoethylester,tert-Butanol und DCC
N NC
COOH
EtOOC
COOtBu
EtOOC 6-C4
t-BuOH
EtOOC
O
O
N NC
N
N
C
H
H
EtOOC
O
O +
EtOOC
N NC
O
O
EtO2C
N
HN
O
O
H
HO
O
O
EtO2C
NH
NHO O
O
EtO2C
N
NHOH
~H
O
EtO2C O + O
NH
NH
6-E1/2 1-Chlor-2-methyl-1-(piperidin-1-yl)propen aus iso-
Butters?urepiperidid
O
N
Cl
N
Cl
Cl
N Et3N
6-E1/2
ClCl
O O
O
N
O
N
ClCl
O O O
Cl
O
O
Cl
N
O
O
Cl
N
O
ClO
O
Cl
N
O
Cl
-CO2/-CO
Cl
N
Cl
H
Et3N
Cl
N
-HEt3N
6-E3N-Boc-L-Alanin-(N-methoxy-N-methylamid aus N-Boc-
L-Alanin
6-E4(S)-4-(tert-Butoxycarbonylamino)-1-pentin-3-on aus N-
Boc-L-Alanin-(N-methoxy-N-methylamid (6-E3)
O
HO
H3C
BocNH
O
N
CH3
BocNH OCH3
CH3
1) ClCOOCH3
2) CH3ONHCH3
O
CH3
BocNH [Li *NH2CH2CH2NH2]
6-E3
6-E4
O
HO
H3C
BocNH Cl
O
OMe
O
O
H3C
BocNH
H
O
Cl
OMe
O
O
H3C
BocNH
O
OMe
+Cl +H
-CO2/-HOMe
O
H3C
BocNH Cl
NH
Me
OMe
O
CH3
BocNH
Cl
NH
OMe
Me -Cl -H
CH3
BocNH NH
OMe
Me
O O
N
CH3
BocNH OC
H3
CH3
6-E3
O
N
CH3
BocNH OCH3
CH3
6-E3
Li
*NH2CH2CH2NH2
O
NBocNH OCH3
CH3
6-E3
Li
NH2
NH2
H
O
NBocNH OCH3
CH3
H
O
CH3
BocNH
6-E4
6-F1L-Phenylalaninmethylester-hydrochlorid aus L-
Phenylalanin
Cl
SOCl2/MeOH
H3N CO2
Ph
H3N
Ph
O
OMe
6-F1
H3N
Ph
O
O
S O
Cl
Cl
H3N
Ph
O
O
Cl
S
O
Cl
H3N
Ph
O
O
Cl
S
O
ClH
3N
Ph
O
ClCl
MeOH
H3N
Ph
O
Cl
O
Me H
Cl -HCl
H3N
Ph
O
O
Cl
Me
H3N
Ph
OMe
O
Cl
-SO2
6-F2 N-(Benzyloxycarbonyl)-L-asparagins?ure aus L-
Asparagins?ure
6-F3 N-(Benzyloxycarbonyl)-L-asparagins?ureanhydrid
aus N-Benzyloxycarbonyl-L-asparagins?ure (6-F2)
6-F4 N-(Benzyloxycarbonyl)-aspartam aus N-
(Benzyloxycarbonyl)-L-asparagins?ureanhydrid (6-F3) und L-
Phenylalaninmethylester (6-F1)
2) PhCH2OCOCl
1) MgO/H2O/Et2O
OH
OH
O
O
NH2
OH
OH
O
O
NHO
O
Ph
NHO
O
Ph
O
O
O
Ac2O
H2N
Ph
O
OMe
N
H
Ph
O
OMe
O
CO2H
NH
(aus
6-F1)
O
O
6-F2
3) HCl
6-F4
Ph
OH
OH
O
O
NH2
Ph O
O
Cl
MgO
-H2O O
O
O
O
H2N
Mg
O
O
O
O
NH2
Mg
Cl
O
O
Ph
-H
O
O
O
O
NH
Mg
Cl
O
O
Ph
O
O
O
O
NH
Mg
OOPh
+2H2O
-Mg(OH)2OH
OH
O
O
NHO
O
Ph
6-F2
OH
OH
O
O
NHO
O
Ph O
OO
O
OH
O
O
NHO
O
Ph
O
O
O
O
OH
O
O
NHO
O
Ph
O
O
O
~H
H
O
OH
O
O
NHO
O
Ph
O - HOAc
H
OH
NHO
O
Ph
O
O O
~H
O
NHO
O
Ph
O
O O
H
- HOAc
O
NHO
O
Ph
O
O
H2N
Ph
O
OMe
O
NHO
O
Ph
O
O
NHO
O
Ph
O
O
O NH2 O
OM
e
Ph
~H
NHO
O
Ph
O
O
O NH O
OM
e
Ph
6F-3
HNHO
O
Ph
O
O
NH
OMeO
Ph
H
O
6F-4
O
O
NHO
O
Ph
O
O O O
H
O
7,Umwandlungen von Carboxylverbindungen und Nitrilen
ineinander
7-A1 Malons?ure aus Cyanessigs?ure
CN
CO2H
2) CaCl2 CO
2
CO2
CO2H
CO2HHCl
Ca2
1) NaOH
C
CO2H
N
+
C
CO2
N
Na OH
Na
+H2O
-OH C
CO2
HNOH
OH
+OH -H2O
C
CO2
NH
O
+H2O
-OH
C
CO2
NH2
O
HO
C
CO2
NH2O
OH
+H2O -OH
C
CO2
NH3O
OH
C
CO2
O
OH
-NH3 C
CO2
O
OH
2) CaCl2
+OH / -H2O
C
CO2
O
O
Ca2+2 HCl
-CaCl2
CO2H
CO2H
7-A2 Glycinethylesterhydrochlorid aus 1,3,5-
Tris(cyanmethyl)-1,2,3,4,5,6-perhydrotriazin (9-A3)
NH3EtO2C
Cl
HCl gasN
N
N CNNC
CN
EtOH abs,7-A2
N
N
N CNNC
CN
H
N
N
N CNC
CN
NH
EtOH
N
N
N CNC
CN
NH
OEt
H
~HN
N
N CNC
NC
NH2
OEtH2ON
N
N CNC
NC
NH3
OEt
~H
O H
-NH3,
-H N
N
N CNC
NC
OEt
O +H N
N
N C
NC
NC
OEt
O
H
N
N
N
H2C
C
NC
NC
OEt
O
H
H2ON
N
N C
NC
NC
OEt
O
H OH
-H
N
N
N C
NC
NC
OEt
O
H
OH+H
H N
N
N C
NC
NC
OEt
O
H
H + O H
H H
O
H H
3x+H3N C
OEt
O
Cl
3x
7-B1 Sebacins?uredinitril aus Sebacins?urediamid (6-B3)
O
H2N (CH2)8 NH2
O
NC
(CH2)8
CN
SOCl2
7-B1
O
H2N (CH2)8 NH2
O
+
Cl S Cl
O -Cl
O
H2N (CH2)8 NH2
O S
O
Cl
-HO
H2N (CH2)8 NH
O S
O
Cl-SO2 / -Cl
O
H2N (CH2)8 NH
-H O
H2N (CH2)8 N
+SOCl2,-2HCl / -SO2 NC
(CH2)8
CN
7-B2 Pentaacetyl-D-glucons?urenitril aus D-Glucoseoxim
(9-B3)
7,B-2
NaAc,HOAcCHNOH
HO
OH
O H
HO
OH
CN
OAc
AcO
AcO
AcO
OAc
Ac2O
C
H
HO
OH
O H
HO
OH
O
O O
N OH
C
HO
OH
O H
HO
OH
N O
O
H
+
O
O
H
~H
C
HO
OH
O H
HO
OH
N +
HO
O
O
O O
C
HO
OH
O H
HO
OH
N
O
O O
~H
C
HO
O
O H
HO
OH
N
O
O OH
-CH3COOH
C
HOAcOO H
HO
OH
NCN
OAc
AcO
AcO
AcO
OAc
(1)
(1)
(2)
(2)
2
7-C1/2 Methylbernsteins?ure aus 3-Cyanbutans?ure
CO2HNC CO2O2C
Ba(OH)2
CO2HHO2C
HNO3
CO2Et
NaCN
EtOH,H2O H2O,?
Ba2
7-C1/C2
C
CO2H
H
C
N
+OH
CO2
C
NHO
+OH,-H2O
H2O
-OHCO2
C
NHHO
+OH -H2O
CO2
C
NHO +H2O
-OH CO2
C
NH2O +OH
CO2
C NH2O
OH
+H2O -OH
CO2
C NH3O
OH
-NH3
CO2
C
O OH+OH
-H2O
CO2
C
O O Ba2+
+HNO3
CO2H
C
O OH
O
OEt
CN
C
O
OEt
CN +H2O
-OH C
O
OEt
CN H
C
O
OEt
CN OH
C
O
OEt
CN
OH
-OEt
7-D1 (1-Naphthyl)acetonitril aus 1-
(Chlormethyl)naphthalin (5-D4)
7-D2 (1-Naphthyl)acetamid aus (1-Naphthyl)acetonitril
(7-D1)
NaCN
EtOH,H2O
Cl CN
HCl /H2O
O
NH2
7-D1 b)
7-D2
Cl
CN
SN2
CN
+ Cl
C N
+H Cl C N H
+ Cl
H2O C N H
OH2 Cl
C
N H
OH
HCl +
C
N H2
OH
Cl
-HCl
C
N H2
O
O
NH2
7-E1 D-Gulons?ure- -lacton aus D-Xylose
O
OH OH
O
O
H
O
1) Ba(OH)2*6 H2O
HO
OH
OH
OH
OH
CN
3) kristallisieren
aus MeOCH2CH2OH
2) H2SO4NaCN
HO CHO
OH
OH
OH NH4Cl
HO CHO
OH
OH
OH
+NH4
-NH3
HO
OH
OH
OH
O
CN
HO
OH
OH
OH
OH
C
N
+OH
HO
OH
OH
OH
OH
C
N
HO
H2O
HO
OH
OH
OH
OH
C
N
HO
H
+OH -H2O
HO
OH
OH
OH
OH
C
N
O
H +H2O
-OH
HO
OH
OH
OH
OH
C
NH2
O
HO
OH
O
OH
OH
C
NH2
OH
~H
HO
OH
O
OH
OH
C
NH3
O
-OH
HO
OH
O
OH
OH
C
NH3
O
-
7-E2 Pyridin-3-carbonitril aus Pyridin-3-carboxamid
CH2Cl2N
NH2
O
N
CN
7-E2
Cl3CCOCl / NEt3
N
NH2
O
Cl CCl3
O
+
N
NH2
O C
O
Cl
CCl3
N
NH2
O C
O
C
Cl
3
Cl
-HCl
N
NH
O C
O
CCl3
-CO2-CCl3
N
NH +
-HCCl3
N
CN
7-F1 -Phenylalanin aus 2-Amino-2-phenylpropionitril
(9-F4)
7-F1
1) HCl / H2O /?
2) Pyridin
(9,F-4)
CNH2N CO2H3N
CH2N N 2HCl
-2Cl
CH3N NH
H2O
CH3N NH
OH2
~H
CH3N NH2
H2O
OH
CH3N NH2
OH2
OH
~H
CH3N NH3
OH
OH
CH3N NH3
OH
OH
+
-NH4Cl
CO2H3N
8,Umwandlungen von Kohlens?urederivaten und
Heterocumulenen ineinander
8-C3 Natrium-(S)-2-amino-6-guanidinocapronat aus S-
Ethylthiouronium-bromid und L-Lysin
8-C2
S
H2N NH2
S
H3N NH
Et
Br NaH2N CO2
NH3
4
2)
1) NaOH
CO2
NH2
4
H
NHN
NH2
EtBr
S
H2N NH2
Et Br S
H2N NH2
Et
Br
S
H3N NH
Et
Br
H2N CO
2
NH3
4
S
H2N NH2
Et
Br
H2N CO
2
NH3
4
-SEt H2N
NH2 Br
H2N CO2
NH3
4
-H
-H-H
Na
CO2
NH2
4
H
NHN
NH2
8-D3 3-[3-(Dimethylamino)propyl]-1-ethylcarbodiimid
aus Ethylisocyanat und 3-Dimethylamino-1-propylamin
2) p-TsCl,Et3N
NEtCO
1)
NMe2H2N
NMe2N
C
NEt 8-D3
+ NEt3
NMe2H2N
HNEt3 + NMe2HN
NEt
C
O
+ Cl S
O
O
CH3 S
O
O
CH3OCNEt
NMe2HN
NMe2NCEtN
Cl
-Cl
OTs
+NEt3
-HNEt3,-OTs
NMe2NCEtN H
8-E3/4 (4-Methoxyphenyl)isothiocyanat aus p-Anisidin
8-E3/4
MeO
NH2 CS
2
Et3N MeO
H
N
S
S
EtNH3
ClCO2Et
Et3N MeO
N C S
MeO
NH2
C
S
S
MeO
H2
N
S
S
MeO
H2
N
S
S
Et3N
OMe
H
N
S
S
EtNH3
Cl OEt
O
- EtNH3OMe
N
S
SEtO
O
H
Et3N -Et3NH
MeO
N C S
+ SEtO
O
Et3NH SHEtO
O
SEtHO
O
EtOH + S C O
8-E3
(1)(2)
8-F2 1,3-Di-(tert-butoxycarbonylamino)benzol aus m-
Phenylendiamin mit Di-tert-butyldicarbonat
8-F3 m-Phenylendiisocyanat aus 1,3-Di-(tert-
butoxycarbonylamino)benzol (8-F2)
8-F2
8-F3
H2N NH2
t-BuO O Ot-Bu
O O
N
H
N
H
Ot-Bu
O
t-BuO
O
N N
BCl3,NEt3
C OCO
H2N NH2
t-BuO O Ot-Bu
O O
N
H2
H2N
Ot-Bu
O
O
O
Ot-Bu
Boc-Anhydrid!
O
O
Ot-
Bu-
N
H2
H2N
O
Ot-Bu-HN
H
H2N
O
Ot-Bu
N
H
N
H
Ot-Bu
O
t-BuO
O
N
H
Nt-BuO
O
Ot-Bu
O
BCl3
H8-F2
BCl3
+NEt3
-HNEt3,
-BCl3,
N
H
Nt-BuO
O
C O
-Ot-Bu
N N C OCO
dto.
9,Umsetzung von Hetero-Nucleophilen mit Aldehyden
bzw,Ketonen
9-A3 1,3,5-Tris(cyanmethyl)-1,2,3,4,5,6-perhydrotriazin
aus Formaldehyd
N
N
N CNNC
CN
C
O
/ NH4ClCH3COOH
NaCN
H H
9-A3
C
O
H H
NH4
C
OH
H H
+ NH3
NH3
H OH
H
~H
NH2
H
OH2HNH2
HHH3N
NH2
HH
NH3
- H
H2N NH2
OH
H H
H2N NH2
OH
~H H
2N NH
OH2
- H2O
H2N NHH
3N CH
2
H2N NH
H3N
O
HHH2N NH
H2NHO
~H
HN NH
H2NH2O
- H2O HN NH
N
H2
- H HN NH
N
H
O
HH
HN NH
N
HO
H
~HHN NH
N
H2O
CN
HN NH
N
NC
N N
N
NC
CNNC
analog
-H
H
9-A4 1,2:5,6-Diisopropyliden-D-mannit aus D-Mannit
HO
OH
OH
OH
OH
OH
MeO OMe
O
O
HO
OH
O
O
SnCl2
9-A4
MeO OMe + SnCl
2
O OMe
SnCl2Me
MeO + MeOSnCl2
HO
OH
OH
OH
OH
OH
MeO
HO
OH
OH
OH
OH
O OMe
H
~H
HO
OH
OH
OH
OH
O OMe
H
HO
OH
OH
OH
OH
O
- MeOH
HO
OH
OH
OH
O
O
H
- H HO
OH
OH
OH
O
O
O
O
HO
OH
O
O
9-B3 D-Glucoseoxim aus D-Glucose
CHNOH
OH
HO
HO
HO
OH65 °C
NH2OH
9,B-3
O
HO
HO
HO
OH
OHCHO
OH
HO
HO
HO
OH
OH
HO
HO
HO
OH
O
H
NH2OH OH
HO
HO
HO
OH
O
H
NH2-OH
~H
OH
HO
HO
HO
OH
OH2
H
N-OH- H2O
OH
HO
HO
HO
OH
N OH
O
HO
HO
HO
OH
H
N OH
9-B4 Chinoxalin aus o-Phenylendiamin und Glyoxal
9,B-4
+
1)
NaHSO3
,H2O
2) Na2CO3 N
NNH2
NH2 O
O
NH2
NH2 O
HO
+
H2
N
NH2
OH
H
O
~H
H
N
NH2
OH2
H
O
H
N
NH2 O
- H
N
NH2 O
analog
N
N
9-C4 Meldrum’s S?ure aus Aceton und Malons?ure
O
O
O
OOH
OH
O
O
Me2C=O,Ac2O,H2SO4
9-C4
OH
OH
O
O
O
O
O
OH
OH
O
O
OH
O
O
H
OH
OH
O
O
OH
+
O
O- HOAc
OH
OH
O
O
O
O
OH
OH
O
O
O
O
OH
OH
O
O
O
O
O
O
HO
HO O
O
O
O
HO
OH
O
O
O
O
O
OH
-HOAc
-H
O
O
O
O
9-D4 2,5-Dimethylpyrrol aus 2,5-Hexandion
9-D4
O O NH
(NH4)2CO3
O O
NH4
O O
H
+ NH3
NH3
OHO
~HNH
2
OH2O
-H2O
O NH2 O NH O NH2 O NH2
~H
-H
N
H
HO
+H
N
H
H2O
-H2O
N N
H
H
H
-H
9-F4 2-Amino-2-phenylpropionitril aus Acetophenon
NaCN,NH4Cl
9-F4
O CNH
2N
O
NH4
OH
+ NH3
OH
NH3~H
OH2
NH2
-H2O
NH2
CN
CNH2N
10,Praktikumswoche
10,Addition von H-Nucleophilen oder Metallorganylen an
Aldehyde bzw,Ketone
10-A3 endo-1,3,3-Trimethylbicyclo[2.2.1]heptan-2-ol aus
(-)-Fenchon
10-A3O
OH
NaBH4
O H
Angriff an der weniger konkaven
Seite
O
H
H
OH
10-A4 syn-2,2-Dimethyl-4-phenyl-3-pentanol aus 2-
Phenylpropionaldehyd
Rac Rac
Rac
10-A4
O
H
OH
t-Bu
1) t-BuMgBr
2) HCl,H2O
O
H
BrMg
Angriff von vorne
O
t-Bu
PhH
Me
OH
Nu-
10-B1 (9-Fluorenyl)methanol aus Fluoren-9-carbaldehyd
(6-B1)
10-B1
OHO
NaBH4
O
H
O
H
H
10-B2 Cyclohexylcarbinol aus Formaldehyd und dem
Grignardreagenz aus Chlorcyclohexan
10-B2
MgCl
2) H2O / H2SO4
CH2OHO
H H
1)
O
H H
MgCl C H
H
O
H
10-B3 endo-1,3,3-Trimethylbicyclo[2.2.1]heptan-2-ol aus
(-)-Fenchon
10-B3O
OH
1) EtMgBr
2) HCl,H2O
O
MgBr
H
H H H2C CH2
O
O
H
Mg
Br
sechsgliedrig
10-B4 anti-2,2-Dimethyl-4-phenyl-3-pentanol aus 2,2-
Dimethyl-4-phenyl-3-pentanon
Rac Rac 10-B4
O
t-Bu
OH
t-Bu
NaBH4
O
t-Bu
H OH
t-Bu
PhH
Me
Ot-Bu
Nu-
10-C1/2 Bis[4-(dimethylamino)phenyl]phenylmethanol und
Malachitgrün aus 4,4’-Bis(4-dimethylamino)benzophenon
10-C2 a)
O
NMe2
NMe2
OH
MgBr
2) NH4Cl,H2O
1)
Me2N
Me2N
NMe2
BF4
HBF4,Ac2O
Me2N
10-
C1
O
Me2N
Me2N
BrMg
NMe2
O
Me2N
NH4Cl
NMe2
OH
Me2N
H
NMe2Me2N
NMe2
Me2N
-H2O
10-C3 endo-1,2,3,3-Tetramethylbicyclo[2.2.1]heptan-2-ol
aus (-)-Fenchon
O OH
1) MeMgI
2) HCl,H2O
10-C3
O
H3C MgI
O
Alkylierung,da kein β H
10-C4 syn- und anti-2-Phenyl-3-pentanol aus 2-
Phenylpropionaldehyd
Rac Rac Rac
10-C4
O
H CH3
1) CH3MgI
2) HCl,H2O
OH OH
+
7,3
CH3
O
H
H3C MgI
CH3
O
Haups?chlich
Cram
10-D1/2 1-Phenyl-3,4-tetrahydro-1-naphthol und 3,4-
Dihydro-1-phenyl-naphthalin aus a-Tetralon
10-D1
O
HO
2) NH4Cl,H2O
1) PhMgBr
(CH3CO)2O10-D2 a)
O
BrMg
O
HO
NH4Cl
O
O
O
O
O
O
O
O
O
O
O
H
O
O
H
- H
E1
10-D3 exo-2-Ethyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-
ol aus (+)-Campher
10-D3
O
OH1) EtMgBr
2) NH4Cl,H2O
O
Et MgBr
O
10-D4 anti- und syn-2-Phenyl-3-butanol aus 2-Phenyl-3-
pentanon
RacRac Rac
10-D4
O
Me Me Me
OH OH
+
7,3
NaBH4
O
Me
H
Me
O H
10-E1/2 Vinyl-b-ionol und Anhydro(vinyl-?-ionol) aus b-
Ionon (3-E4)
10-E1
O
MgBr
OH
2) NH4Cl,H2O
1)
5n H2SO4
4h RT10-E2 a)
O MgBr O
NH4Cl
H2O
OH
H
OH2
H
-H2O
-H
10-E3 (+)-Isoborneol aus (+)-Campher
10-E3O
OH
NaBH4
O
H
O
HCl
OH
10-E4 trans- und cis-4-tert-Butylcyclohexanol aus 4-tert-
Butylcyclohexanon
10-E4
O
NaBH4
t-Bu t-But-Bu
H
OH H
OH
+
8,2
O
t-Bu
H
H
H
H
H
t-Bu
H
O
t-Bu
H
O
+
10-F1 threo- und erythreo-1-(3,4-Dihydro-2H-pyran-2-yl)-
1-propanol aus 3,4-Dihydro-2H-pyran-2-aldehyd
Rac Rac
O O
EtMgBr;
HCl,H2O
O OH O OH
H
O
O HMg
Et
H
O
Mg
Et
OH
O O
MgBr
O O O O
10-F2 cis-1-Ethinyl-4-tert-butylcyclohexanol aus 4-tert-
Butylcyclohexanon
t-Bu
O
NH2
NH2
O
Li
t-Bu
OH
OH
H
H
H
H
Li
NH2
NH2
O
H
NH
NH2
Li
10-F3 (+)-Isoborneol aus (+)-Campher
O
OH
1) i-BuMgBr
2) NH4Cl,H2O
O
H
H3C
Mg Br
O OH
H
H3C
10-F4 cis,cis-3,5-Diphenylcyclohexanol aus cis-3,5-
Diphenylcyclohexanon
10-F4
O
NaBH4
Ph
Ph
OHPh
Ph
O
Ph
Ph
H OPh
Ph
OHPh
Ph
H2O
11,Praktikumswoche
11,Umsetzung von Heteroatom-stabilisierten C-
Nucleophilen mit Aldehyden bzw,Ketonen
11-A1 trans-4-Bromzimts?ureethylester aus 4-
Brombenzaldehyd und Triethylphosphonacetat
11-A1
CHO CO2Et
BrBr
C
Br
O
H
EtO C
H2
P
O O
OEt
OEt
EtO
P
O O
OEt
OEt
NaH,THF
NaH
EtO C
H
P
O O
OEt
OEt EtO C
H
P
O O
OEt
OEt
Ylen
Na
Br
O P(OEt)
2
O
OEt
O
Br
O P(OEt)
2
O
OEt
O
- H2
CO2Et
Br O
P
O
OEt
OEt
11-B1 cis-4-Bromzimts?ureethylester aus 4-
Brombenzaldehyd und
(Ethoxycarbonyl)methylphosphons?urediphenylester
11-B1
CO2Et
("TRITON B")
P CO2Et
PhO OPh
O
BrBr
O
PhCH2(CH3)2N+OH-,MeOH
EtO C
H2
P
O O
OEt
OEt
NaH
EtO C
H
P
O O
OPh
OPh EtO CH
P
O O
OPh
OPh
Ylen
Na
- H2
Br
O
Br
O P(OPh)
2
O
OEt
O
Br
O P(OPh)
2
O
OEt
O
CO2Et
Br O
P
O
OPh
OPh
11-C1 1,3-Bis(4-phenylbutadienyl)benzol aus Zimtaldehyd
und m-Xylylen-bis(triphenylphosphoniumchlorid)
11-C1
Ph3P PPh3
Cl Cl
LiOMe,EtOH
O
Ph3P PPh3 O Me
H
Ph3P PPh3
O
Ph3P PPh3
O PPh3
PPh3
PPh3
11-D1 3-(3-Methyl-2-buten-1-yl)indol aus
Indolcarbaldehyd (5-B6) und dem Instant-Ylid
Isopropylidentriphenylphosphoran
11-D1"Instant-Ylid"
[Me2CHP(C6H5)3Br
+ NaNH2]
O
O
Me2C PPh3
H
NH2
+ NH3Me2C PPh3 Me2C PPh3
Me2C PPh3
O
Ph3
P
+
O PPh3
11-E1 trans,E-5,9-Dimethyl-2,4,8-decatriens?ureethylester
aus Geranial und
(Ethoxycarbonylmethylen)triphenylphosphoran
O
CO2Et
11-E1
Ph3P
CO2Et
O
Ph3P
CO2Et
Ph3P
CO2Et
PPh3O
CO2Et
CO2Et
OPPh3
11-F1 E,E-2,5,9-Trimethyl-2,4,8-decatriens?ureethylester
aus Geranial und
[1-(Ethoxycarbonyl)ethyliden]triphenylphosphoran
O
CO2Et
Ph3P
CO2Et
11-F1
O
Ph3P
CO2Et
Ph3P
CO2Et
PPh3O
CO2EtCO2Et
OPPh3
12,Chemie von Enaminen und Enolen
12-A2 1-(N-Morpholino)cylopenten aus Cyclopentanon
und Morpholin
12-A3 2-(2-Methylbutyliden)cyclopentanon aus 1-(N-
Morpholino)cylopenten (12-A2) und Isovaleraldehyd
12-A3
O
N
H
O
N
O
+?
12-A2
O
2) HCl
1)
-H2O
O
N
H
O
+
N
O
O
H
~ H
+ H
N
O
OH2
- H2O
N
O
H
N
O
N
O
O
~ H
H
O
O
Analog gehen auch 12-B2/B3,12-E2/E3 und 12-F2/F3,allerdings dort Protonierung mit pTsOH !!
N
O
OH N
O
- OH
N
O
OH2
H
O H
~ H
N
O
O
H
H
O
H
- H
O
12-A4 (Acetamido)malons?urediethylester aus
Malons?urediethylester
12-A4
EtO2C
EtO2C
NH
OAc2O/AcOH
EtO2C
EtO2C
EtO2C
EtO2C
NOH
AcOH/H2O
NaNO2 Zn
EtO2C
EtO2C
H
O OEt
EtO
O
N O H
O OEt
EtO
O N
O
O OEt
OEt
O
N
O
- H
O OEt
OEt
O
N
O
H
H
O OEt
OEt
O
N
OH2
- H- H2O
O OEt
OEt
O
N
Zn
SET
Zn
O OEt
OEt
O
NH
e
H
2 e
2 H
O OEt
OEt
O
NH2
H
O
OEt
OEt
O
N
H2
HO
O O
O
O
O O
OEt
OEt
O
N
H2
H
O
O
O
O OEt
OEtO
N
H2
H O
O
O
O OEt
OEt
O
N
H
O
HO
O
12-B2 1-(N-Morpholino)cyclohexen aus Cyclohexanon und
Morpholin
12-B3 2-Oxocyclohexan-1-carbons?ureethylester aus 1-(N-
Morpholino)cyclohexen (12-B2)
12-B2
12-B3
N
H
O
N
O
+
Η+,Toluol,?
O
(-H2O)
O
OEt
O 1) Cl
OEt
O
2) 2n HCl
Mechanismus siehe 12 A2/3
12-B3
N
O
O
OEt
O1) Cl
OEt
O
2) 2n HCl
N
O
Cl
OEt
O N
O
Cl
OEt
O
O
OEt
O
vgl,12-C4
12-B4 Phenacylbromid aus Acetophenon
12-B4
CH3
O
CH2Br
O
Br2,AcOH
CH3
O
Br BrCH2
OH
- Br
H C
OH
H
HH
- H
CH2Br
OH
- HCH2Br
O
12-C2 2-Methyl-1,3-cyclopentandion aus Bernsteins?ure
und Propionylchlorid
12-C3 2-Methyl-2-(3-oxobutyl)-1,3-cyclopentandion aus 2-
Methyl-1,3-cyclopentandion (12-C2) und Methylvinylketon
12-C4 (7aS)-7a-Methyl-2,3,5,6,7,7a-hexahydro-1H-inden-
1-on aus 2-Methyl-2-(3-oxobutyl-1,3-cyclopentandion (12-
C3)
12-C3
12-C2
Cl
O
O
OH
O
HO
+
O
O
O
HO
O
O
O
AlCl3
12-C4
H2N
CO2
H
O
O
2) H2SO4
DMF
1)
HO
OH
O
OH
Cl
O
AlCl3
HO OH
O OH
O
Cl
- HCl
O
OH
O
OH
O
~ H
O
OH
O OH
HO
O
HO
O
OH
OH
O
O O
O
H
- CO2 O
O
O
HO
OHO
H
O
O
OH
O
O
O
- H
HO
O
O
H2N
CO2
H
O
O
N
HO2C H
O
N
HO2C H
O
O
N
O2C H
OH
~ H
H O
H
O
N
O2C
H
HO
H2O
ONH
O2C H
HO
HO
~ H
ONH
O2C H
HO
HO
H2N
CO2
H
O
HO
O
H
- H2O
O
O
- H
O
O
12-D2 2-Pyrrolidino-3,4-dihydro-6-methoxynaphthalin aus
6-Methoxy-2-tetralon
12-D3 6-Methoxy-1-benzyl-2-tetralon aus 2-Pyrrolidino-
3,4-dihydro-6-methoxynaphthalin (12-D2)
O
OMe
N
OMe
N
H
Toluol,?
(-H2O) 12-D2
12-D3
O
OMe 2) AcOH,H2O
1) PhCH2Br
O
OMe NH
O
OMe
NH
Ph
~ H
OH
OMe
N
OMe
N
H
- H2O
BrSN2
OMe
N H3O
vgl,12-C4
O
OMe
Ph
12-D4 2,5-Dibromadipins?urediethylester aus Adipins?ure
12-D4
EtO2C
CO2Et
Br
Br
HO2C
CO2H
1) SOCl2,Br2
2) EtOH
HO2C
C
O
OH
S
O
ClCl
HO2C
C
O
OH
S
O
ClCl
HO2C
C
O
OH
S
O
Cl
Cl
- Cl-
- SO2
HO2C
C
OH
Cl
HO2C
C
O
Cl
- H
C
C
O
Cl
Cl
O
C
C
O
Cl
Cl
OH
Br BrC
C
O
Cl
Cl
OH
Br
- H
HOC C
O
Cl
Cl
O
Br
C
C
O
Cl
Cl
O
Br
Br
- Cl-
(1)
(1)
(2)
(2)
C
C
O
H
O
Cl
O
Br
Br
- HC
C
O
O
Cl
O
Br
Br
C
C
O
O
O
O
Br
Br
12-E2 1-(N-Pyrrolidino)cyclohexen aus Cyclohexanon und
Pyrrolidin
12-E3 3-(2-Oxocyclohexyl)propions?ureethylester aus 1-
(N-Pyrrolidino)cyclohexen (12-E2) und Acryls?ureethylester
12-E2
N
O
N
H
OEt
O
1)
O
CO2Et
2) H2O,?
+
Η+,Toluol,?
(-H2O)
12-E3
Mechanismus siehe unter 12 A2/3
12-E4 2,4-Dibrom-3-pentanon aus 3-Pentanon
12-E4
O O
Br Br
Br2,PBr3 (kat)
-10 bis 0°C
O P
Br
Br
Br
O P
Br
Br
Br
H
- H
O P
Br
Br
Br
Br Br
- Br
O P
Br
Br
Br
Br
- PBr3
O
Br
O
Br Br
12-F2 1-(N-Piperidino)cyclohexen aus Cyclohexanon und
Piperidin
12-F3 1,10-Bis-(2-oxocylohexyl)-1,10-decandion aus 1-
(N-Piperidino)cyclohexen (12-F2) und Sebacins?uredichlorid
(6-B2)
12-
F2
N
H
N
+
Η+,Toluol,?
O
(-H2O)
Mechanismus siehe unter 12 A2/3
12-F3
O O O O
8
O O
8Cl Cl
1),Et3N
2) HCl/H2O
12-F4 -Brom- -butyrolacton aus -Butyrolacton
12-F4
O
O
O
O
Br
Br2,P
O
Br
Br
Br
H2O
3 Br2 + 2 P 2 PBr3
O O
P Br
Br
Br
O
O
Br
P
Br
Br
Br
- PBr3
O
Br
HO
OH
Br
HO
H
H
OH
Br
H2O
Br
Br Br
- H2O; -Br
- HO
Br
Br
Br
H
O H
Br
O
Br
H2O
Br
- H
OH
Br
O
Br
- Br
O
OH
Br
- H
O
O
Br
13,Chemie von Aldeyd-,Keton- und Esterenolaten
13-A1 Acetylbernsteins?urediethylester aus Acetessigester
und Chloressigs?ureethylester
O
CO2Et
OEt
O
O
OEt
O
1) Na,EtOH
2) ClCH2CO2Et
Na Na OEt 0.5H2
OEt
O O
H
OEt
HOEt
OEt
O O
HOEt
OEt
O ONa Cl
OEt
O
Na Cl
OEt
OONa Na
O
CO2Et
O
OEt
Weniger wichtige meso,GF,
da 14 kcal/mol
Ester-Mesomerie fehlt!!!
13-A2 4-Oxopentancarbons?ureethylester aus
Acetylbernsteins?urediethylester (13-A1)
O
CO2Et
OEt
O
O CO2EtH3BO3
O
CO2Et
O
OEt B
OH
OH
OH
δ+
CO2Et
O
OEt
O
B
HO OH
OH
δ+
δ?δ?δ?
CO2Et
O
OEt
O
B
HO OH
OH
δ+
δ? O
OEt
O
B
HO OH
OH
EtO2C
OH2
~H
O
O
O
B
HO OH
OH
EtO2C
OH
H
Et
H3BO3
HOEt
O
O
OH
O
O
Et
H2O
O
O
O
Et
O
O
H
OH
O
O
Et
OH
O
O
Et
O
O
O
Et
CO2
13-A3 Sorbins?ure aus Malons?ure und Crotonaldehyd
13-A3
CHO CO2H
+
Pyridin,DO
HO
HO
O
O
OHHO
O
H H N
O
OH OH
O
H
O
OHOH
O
H
N
H
H
H
O
H
O
OH OH
O
H
N
H
H
H
O OH
OH
OHO
H
N
H
H
HO OH
OH
OHO
N
N
H
H
HO
OH
O
OH
O
N
H
OH
H
H
O
O
HO
OH
H CO2
H
H
O
O
H
H
~H
H
H
H
H
O
O
H
H
H
H
H
H
O
O
H
H
H
13-A4 3-Hydroxy-2-methylpentanal aus Propionaldehyd
13-A4
CHO
OH
CHO KOH,MeOH
H
O
H
H
H
O
H H
O
H
H
O
H
O
H
K
KH
H3O
H2O
H
OHO
H
OH O
=
OH H2O
13-B1 5-(1-Hydroxy-2-phenylethyliden)-2,2-dimethyl-1,3-
dioxan-4,6-dion aus Meldrums S?ure (9-C4) und
Phenylessigs?urechlorid
O
O
O
O
+
O
O
O
O
OH
Cl
O Pyridin
CH2Cl2
O
O
O
O
H
H N O
O
O
O
H
H
N
Cl
O
O
O
O
O
H
Cl
O NH ~H
N
O
O
O
O
H
Cl
OH
N
O
O
O
O
Cl
OH
N
H
~H3O
H2O
H-Cl
N
O
O
O
O
OH
13-B2 3-Oxo-4-phenylbutters?uremethylester aus 5-(1-
Hydroxy-2-phenylethyliden)-2,2-dimethyl-1,3-dioxan-4,6-
dion (13-B1)
13-B1 13-B2
O
O
O
O
OH
MeOH,?
O
OMe
O
O
O
O
O
HO
MeOH
O
O
O
HO
OH
Me
O
O
OH
O
HO
O
O
~H
O
HO
O
HO O
O
O
O
HO O
O
O
H
OH
O
HO O
O
O
~H
~H
O
O
O
H
CO2
H
O
O
O
H
O
O
O
O
O
HO O
O
H
~H
13-B3 1,2,4,5-Tetraphenylpentan-1,5-dion aus
Desoxybenzoin
Ph
OPh
Ph
O
Ph
O Ph
Ph
CH2O,KOH
13-B3
Ph
O Ph
OH
H
H H
2O
Ph
O Ph
H
K
K O
H
O
Ph
O
H Ph
K
H2O
OH
H
HO Ph
O
H Ph
OH
H2O
H
HO Ph
O
Ph
K
K
OH
Ph
O
Ph
K
Ph
O
Ph
Ph
O
Ph
O Ph
Ph
Ph
O
Ph
O Ph
Ph
+H
13-B4 2-Methyl-3-oxo-pentans?ureethylester aus
Propions?ureethylester
OEt
OEt
O
O O
Na
13-B4
OEt
O
H
H
Na
SET
-H OEt
O
H SET
-H OEt
O
H
OEt
O
H
H2
OEt
O
OEt
O O
OEt
-OEt
OEt
O O
13-C1 2-Oxo-5,6-diphenyl-3-cyclohexen-1-
carbons?ureethylester aus Benzalacetophenon und
Acetessigs?ureethylester
13-C2 3,5-Diphenyl-2-cyclohexen-1-on aus 2-Oxo-5,6-
diphenyl-3-cyclohexen-1-carbons?ureethylester (13-C1)
13-C3 1-Ethyl-2-oxocyclopentan-1-carbons?ureethylester
aus 2-Oxocyclopentan-1-carbons?ureethylester
13-C4 3-Ethyl-2-oxocyclopentan-1-carbons?ureethylester
aus 1-Ethyl-2-oxocyclopentan-1-carbons?ureethylester (13-
C3)
13-D1 1-Phenyl-1-penten-3-on aus Benzaldehyd und
Ethylmethylketon
13-D2 6-Methyl-5-hepten-2-on aus Citral
13-D3 Curcumin aus Vanillin und Acetylaceton
13-D4 Dimedon aus Mesityloxid und
Malons?urediethylester
13-E1 Indan-1,3-dion aus Phthals?urediethylester und
Essigs?ureethylester
13-E2 (+)-3-(Trifluoracetyl)campher aus (+)-Campher und
Trifluoressigs?ureethylester
13-E3 3-Cyclopenten-1,1-dicarbons?ure aus
Malons?uredimethylester und cis-1,4-Dichlor-2-buten
13-E4 4-Hydroxy-4-methyl-2-pentanon aus Aceton
13-F1 (3-Oxocyclohexyl)essigs?ure aus
Malons?urediethylester und 2-Cyclohexen-1-on
13-F2 3-(Methylthio)-1-(phthalimido)propan-1,1-
dicarbons?urediethylester aus
(Phthalimido)malons?urediethylester (2-C1)
13-F3 rac-Methionin 3-(Methylthio)-1-
(phthalimido)propan-1,1-dicarbons?urediethylester (13-F2)
13-F4 7,16-Dioxodocosandis?ure aus 1,10-Bis(2-
oxocylohexyl)-1,10-decandion (12-F3)
O
O H
N+
H
C–
N
O
O
O
H
H
O
ON O
O
H
H
H
H
C–
H
H
O
HO N+
H N
+ C–
N
+
C–
N+
C–
N+
C–
O H
N+–C
C– H
+N
C–
N+
C–
N+
C–
+N
C–
N+
–C
N
+
C–
N+
–
C
C–
+N
C–
N
+ O
+N
C–
N+
–C
+N
C–
O–C
N+ C–
+N
–C
+N
N
C–
+N
C–
O
H
HO H
H
H
H
N
N
O
O
O
O
H
O
H
H
NH
O
O
O
H
HO
H
H
H
H
N
O
N
O
OH
H
H
H
O
OHO
H
OH
H
H
H
H
N
NH
O
HO
HH
H
H
N
O
NH
O
O
HO O
H
O
H
H
N
NH
O
O
HO
O
HOH
HH
HH
N
NH
O
O
O
H
HO
H
H
H
H
N
NH
O
O
H
H
H
18
H
18
O
18
1
8
OH
O
HO
H
HO
H
HO
H
O
OH
H
HO
HO
HHO
H
HO
H
OH
OH
H
HO
HO
H
OH
HO
H
H
HO
H
OH
H
HO
H
O
OHH
OH
OH
H
HO
O
H
H O
OH
H
HO
O
HO
H
HO
H
OH
H
H
HO
HO
H
H
O
OH
H
Meik Wissert,Marco Frey,Dominic Kramer,
Alexander Drechsle,Christoph Fik
Vorwort
1,5 Tage (18 Stunden) 4,5 Personen,5,5 Computer 8 Kannen
Kaffee c,a,10000 Kcal
Bei diesem Skript ist zu beachten:
Bei sich in analoger Weise wiederholenden
Whelandkomplexen wurde aus Zeit- und Platzgründen auf die
mesomeren Grenzformeln verzichtet,Gleiches trifft auch auf
die meisten übergangszust?nde bei SN-Reaktionen zu.
Auch wurde nur in dem Versuch 2E1 die Diazotierung
vollst?ndig ausformuliert,da sie sich von den anderen
Beispielen nicht unterscheidet.
Die angebotenen Mechanismen sind als L?sungsvorschl?ge zu
verstehen und basieren auf der Begleitvorlesung zum OGP
(Wintersemester 02/03),gehalten von Dr,Rainer Haag.
Fehler und Irrtümer sind nicht auszuschlie?en.
1,Radikalische Substitution am ges?ttigten C-Atom
1-A1 α,α′-Dibrom-ο-xylol aus ο-Xylol
1-A1
CH2
CH3
CH2Br
CH2Br
,hν
Br2
Br Br hν 2BrStart:
Propagation:
H
+ Br HBr +
CH3
CH2
CH3
CH3
CH3
CH2
Br Br+ Br +
CH3
CH2Br
CH2
CH2Br
CH2Br
CH2Br
+ Br
H
1-A2 3-Bromcyclohexen aus Cyclohexen
1-A2
Br
NBS
CCl4,AiBN,D
Start,NC N N CN 2 NC +N2?
Propagation,NC + NBr
O
O
NBr
O
ONC
N
O
ONC
+ B
r
+ Br
H
HBr +
HBr + NBr
O
O
ionisch,
rasch
Br Br
+ NH
O
O
+
Br Br
Br
+ Br
1-A3 1-Chloradamantan aus Adamantan
SO2Cl2
SO2
Cl
Start,Initiator 2R
Propagation,R S
O
O
ClCl+ RCl + SO2Cl
H
SO2Cl+ + SO2 + HCl
+ S
O
O
ClCl
Cl
+ SO2Cl
1-B1 α,α,α′,α′-Tetrabrom-p-xylol aus p-Xylol
,hνH3C
CH3 CHBr2
Br2HC
Br2
Br Br 2BrhνStart
Propagation
H3C
H2
C
H Br
H3C
CH2
HBr
H3C
CH2
Br Br
H3C
CH2Br
Br
CHBr2
Br2HC
1-B2 trans-4-Bromcrotons?ureethylester aus
Crotons?ureethylester
1-B2
NBSCO2Et CO2EtBr
CCl4,AiBN,?
Start,NC N N CN 2 NC +N2?
Propagation,NC + NBr
O
O
NBr
O
ONC
N
O
ONC
+ Br
CO2EtHBr + HBr + CO2Et
HBr + NBr
O
O
ionisch,
rasch Br Br + NH
O
O
CO2EtBr Br + CO2EtBr + Br
und nicht CO2Et
Br
da dies mit einem Verlust von
Konjugationsenergie einher gehen würde
1-B3 (1-Chlor-1-methylethyl)benzol aus Cumol
AiBN/?
CH3
H2C
CH3
CH2Cl
CH
CH3
Cl
SO2Cl2
Start,NC N N CN? 2 CN N2
Propagation:
NC NC Cl
SO2Cl
H
SO2 + HCl +
SO2Cl2
CH2Cl
CH
CH3
Cl SO2Cl
SO2Cl
O
S Cl
O
Cl
1-C1 Brommalons?urediethylester aus
Malons?urediethylester
H2C
CO2Et
CO2Et
CH
CO2Et
CO2Et
Br
CCl4,?/hν
Br2
Br Br 2Brhν
Br CH
CO2Et
CO2Et
Start
Propagation
H HBr HC
CO2Et
CO2Et
HC
CO2Et
CO2Et
Br Br CH
CO2Et
CO2Et
Br Br
1-C2 trans-3,6-Dibromcyclohexen aus Cyclohexen
Start,NC N N CN? 2 CN N2
NC N
O
O
Br N
O
O
Br
N
O
O
Br
NBS
CCl4,AiBN,?
Br
H
Br HBr
Br Br*
*
HBr N
O
O
Br ionisch Br Br HN
O
O
Br
Br
Br
Der 2,Schrit verl?uft analog.
NC
NC
1-C3 1-Chlor-4-(chlormethyl)benzol aus 4-Chlortoluol
1-C3AiBN/?
SO2Cl2
CH3
Cl
CH2Cl
Cl
Start,NC N N CN 2 NC +N2
Propagation:
NC + S
O
O
ClCl NC Cl + SO2Cl
CH2
Cl
H
+ SO2Cl
CH2
Cl
+ SO2 + HCl
CH2
Cl
+ S
O
O
ClCl
CH2Cl
Cl
+ SO2Cl
1-D1 4-Brom-2,2,4-trimethylpentan aus iso-Octan
1-
D1
CCl4,?/hν Br
Br2
Br Br hν 2Br
+ Br
H
+ HBr
Br Br+
Br
+ Br
Start:
Propagation:
Hohe Regioselektivit?t am terti?ren C-Atom (Hammond-Postulat)
1-D2 4-Brom-β-ionon aus β-Ionon
CCl4,AiBN,?
O O
Br
NBS
1-D2
Start,NC N N CN 2 NC +N2?
Propagation,NC + NBr
O
O
NBr
O
ONC
N
O
ONC
+ Br
O
Br +
H
HBr +
O
HBr
+
+ NBr
O
O
ionisch,
rasch Br Br + NH
O
O
Br Br +
O O
Br
+ Br
O
und nicht
O
Br
und kein
(Verlust der Konjugation)
1-D3 1-Chlor-4-(dichlormethyl)benzol aus 4-Chlortoluol
1-D3AiBN/?
SO2Cl2
Cl
CH3
Cl
Cl
Cl
Start,NC N N CN 2 NC +N2
Propagation:
NC + S
O
O
ClCl NC Cl + SO2Cl
CH2
Cl
H
+ SO2Cl
CH2
Cl
+ SO2 + HCl
CH2
Cl
+ S
O
O
ClCl
CH2Cl
Cl
+ SO2Cl
CHCl
Cl
H
+ SO2Cl
Cl
H
C Cl + SO
2 + HCl
Cl
H
C Cl
+ S
O
O
ClCl
Cl
Cl
Cl
+ SO2Cl
2,Nucleophile Substitution am ges?ttigten C-Atom
2-A1 1 Bromoctan aus 1 Octanol
OH HBr,H2SO4
Br
OH H Br OH2 Br
OH2
Br
Br
2-A2 1-Brom-3-methyl-2-buten aus 2-Methyl-3-buten-2-
ol
2-A2
OH
BrHBr,(aq.)
RT
OH
+H
OH2 -H2O
+Br
Br
h?her substituierte Doppelbindung ist thermodynamisch begünstigt
2-A3 2,7-Dihydro-3-benzothiophen aus α,α′-Dibrom-o-
xylol (1-A1)
CH2Br
CH2Br
Na2S,DMF S
H
H
Br
H Br
H
S2- -Br
H
H
S
H
H
Br
-Br
S
2-A4 1,2-Bis(mercaptomethyl)benzol aus α,α′-Dibrom-o-
xylol (1-A1)
S
H2N NH2CH2Br
CH2Br
SH
SH
1)
2) KOH/H2O
Br
Br
S
H2N NH2
H2
C
H2C
S C
NH2
NH2
S C
NH2
NH2
2 2 OH
H2
C
H2C
S C
NH2
NH2
S C
NH2
NH2
O
O
H
H
H2
C
H2C
S C
NH2
NH2
S C
NH2
NH2
S
SH2N NH2
O H2 O
H2N NH2
SH
SH
2-B1 Terephthalaldehyd aus α,α,α′,α′-Tetrabrom-p-xylol
(1-B1)
Br2HC
CHBr2 CHO
OHC2) H
2O
1) H2SO4,?T
CH Br
Br
CH Br
Br
O S OH
O
O
CO
H
CH Br
Br
S O S
O
O
OH
O
O
HO
2 HBr
H2O
C OO
H H
CH Br
Br
S
O
O
HO - HSO
4
-H
- H
- HSO4
HC
O
CH Br
Br
CHO
OHC
2-B2 cis-1-tert-Butyl-4-chlorcyclohexan aus trans-4-tert-
Butylcyclohexanol
Cl
OH
PCl5
O PCl
Cl Cl
ClClH O H
PCl4
Cl
H
Cl
2-B3 trans-1-tert-Butyl-4-chlorcyclohexan aus trans-4-
tert-Butylcyclohexanol
OH Cl
ZnCl2,HCl
2-B2
OH
ZnCl2
OH
ZnCl2
HCl
OH2
ZnCl2
Cl
-H2O,
-ZnCl2
Cl
Cl
Angriff in?quatorialer Stellung,weil dadurch ein stabileres Produkt gebildet
wird
2-B4 cis-4-Acetoxy-tert-butylcyclohexan aus trans-tert-
Butylcyclohexylchlorid (2-B3)
2-B4
OAcKOAc/AcOH
Cl
Cl
H OAc
H
AcO
Cl
-Cl
O
Ac
H
2-C1 (Phthalimido)malons?urediethylester aus Phthalimid
und Brommalon-s?urediethylester (1-C1)
NH
O
O
1.) KOH,EtOH
2.)
Br
CO2Et
CO2Et
N
O
O
CO2Et
CO2Et
N
O
O
KOH N
O
O
Br CO2EtCO
2Et
N
O
O
CO2Et
CO2Et
-I-Effekt von C
OEt
H
2-C2 4-Chlorbenzylfluorid aus 1-Chlor-4-
(chlormethyl)benzol (1-C3)
2-C2
Cl
Cl
Cl
F
KF,?
DMF
Cl
Cl
F
Cl
Cl
F
Cl
F
SN2
Substitution an genannten Kohlenstoffatom,weil eine Stabilisierung der Zwischenstufe durch
konjugiertes aromatisches System stabilisiert wird,
2-C3 4-Chlorbenzaldehyd aus 1-Chlor-4-
(dichlormethyl)benzol (1-D3)
Cl
Cl
Cl
Urotropin,?
EtOH,H2O
Cl
OH
OH
Cl
O
Cl
Cl
Cl
Urotropin,?
EtOH,H2O
Cl
O
2-C4a E-1-Chlor-3,7-dimethyl-2,6-octadien aus Geraniol
Cl
2) Pyridin
OH 1) MeSO2Cl
O S Cl
O
CH
H
H
N NH
Cl
S CH2
O
O
Sulfen
OHO
H
S
O
O CH2
O
S OO
CH3
Mesylat
NH
Cl
Cl
O S CH3
O
O
Methansulfonation
2-C4b E-1-Chlor-3,7-dimethyl-2,6-octadien aus Nerol
Cl
1) MeSO2Cl
OH
2) Pyridin
OH
Me S Cl
O
O
OH
S O
O
Me
Cl
O
S
Me
OO
Cl
Cl
O S Me
O
O
gute Abgangsgruppe
2-D1 (S)-(-)-2-Brom-3-hydroxypropions?ure aus L-Serin
2-D2 Kalium-(R)-2,3-epoxypropionat aus (S)-(-)-2-Brom-
3-hydroxy-propions?ure (2-D1)
2-D3 R-Glycids?urebenzylester aus Kalium-(R)-2,3-
epoxypropionat (2-D2)
2-D2
2-D3
CO2
HO
NH3
HBr,NaNO2
CO2H
HO
Br
K
O
CO2
O
CO2CH2Ph
C6H5CH2Br
CH3CN,
Dibenzo-18-krone-6
(2-D4)
2-D1
KOH
EtOH
HO C
NH3
OH
O
HO CO
2H
Br
2 mal Inversion Rentention
2-D1
K
O
CO2
Br
O
CO2CH2
Ph
KBr
CO2H
HO
Br
2KOH
CO2
O
Br
-2H2O K
K
-KBr
SN2
2-D2
2-D3
HO C
N2
OH
O
HO
O
OH
- N2s,2-E1
2-D4 Dibenzo-18-krone-6 aus Brenzcatechin und Bis(2-
chlorethyl)ether
2-D4
OH
OH
O
O
O
O
O
O
O
NaOH,?
ClCl
+
n-Butanol
OH
OH
OH
O
O
ClCl
OH
O
O
Cl-Cl
O
O
O
O
O
O
+OH
-H2O
Na
Templateffekt
2-E1(S)-2-Chlorpropions?ure aus L-Alanin
2-E2(R)-2-(Pyrrolidin-1-yl)propions?ure aus (S)-2-
Chlorpropions?ure (2-E1)
2-E1
2-E2
O2C CH3
Cl
O2C CH3
NH3
O2C CH3
Cl
O2C CH3
N
NH
NaNO2 / HCl
(2-E1)
HO N
O + H
H2O N
O
N O N O
H
O2C CH3
NH3
HOOC CH3
NH2 N
O
HOOC CH3
NH2
N
O
~ H
HOOC CH3
NH
N
OH
HOOC CH3
NH
N
OH
~ H
HOOC CH3
N
N
OH2
CH3
N
N
O
OH
O
HO
CH3
H O
HO
CH3
H
Cl
O2C CH3
Cl
- H
2-E1
NH
SN22-E2
O2C CH3
N H
2-E3 1,4-Diiodbutan aus Tetrahydrofuran
2-E3
O I I
KI,H3PO4,?
O H O H
I I OH H
I OH2
I -H2O
I I
*
*mit H3PO4 Polyphosphate
2-E4 S-2-(Pyrrolidin-1-yl)propions?ure aus L-Alanin und 1,4-
Diodbutan (2-E3)
2-E4
O2C CH3
NH3
O2C CH3
N
NaHCO3 / Toluol
I I
(2-E3)
O2C CH3
NH3
+OH
-H2O
O2C CH3
NH2
I
I
-I
O2C CH3
HN
SN2
I
SN2
-I
O2C CH3
N
H
H
2-F1Pentaerythrittetrabenzolsulfonat aus Pentaerythrit
2-F1
OH
HO
HO
OH
OSO2Ph
PhO2SO
PhO2SO
OSO2PhPhSO2Cl
Pyridin
O
HO
HO
OH
Ph S Cl
O
O
-Cl
O
HO
HO
OH
S
O
O
Ph
OSO2Ph
PhO2SO
PhO2SO
OSO2Ph
H OH
HO
HO
O S
H O Cl
O Ph
OH
HO
HO
O S
H O
O Ph
N
2-F2 1,3-Diiod-2,2-bis(iodethyl)propan aus
Pentaerythrittetrabenzolsulfonat (2-F1)
OSO2Ph
PhO2SO
PhO2SO
OSO2Ph
2-F2
OSO2Ph
PhO2SO
PhO2SO
OSO2Ph
I
I
I
INaI
DMF
+
- OSO2Ph
I
PhO2SO
PhO2SO
OSO2Ph
I
I
I
I
I
2-F3(S)-(+)-γ-Butyrolacton-γ-carbons?ure aus L-
Glutamins?ure
HO
NH3O
CO2
NaNO2,H2SO4
O
O
COOH
H
HO
NH3O
CO2
NaNO2,H2SO4
-2H2O
HO
NO
N
-N2
HO
O O
HO CO2
OHO CO2H
O
O
COOH
H
O
O
O
O
2-F4 2,2-Dimethyl-5-pentyltetrahydrofuran aus 2-Methyl-2,5-
decandiol (6-A2)
2-F4
OOH
Pent
OH Pent
H3PO4
OH
Pent
OH
+H
OH2
Pent
OH -H2O
Pent
OH
- H
OPent
SN1
intramolekulare Reaktion sind immer schneller als intermolekulare Reaktionen
3,Additionen an olefinische C=C-Bindungen
3-A1
HO
HO
Br2
BrBr
HO
Br Br HO Br
Br
HO
BrBr
Der Angriff am C-Atom ist aufgrund der
Methyl-
gruppe erschwert und aufgrund des H-Atoms
unten erfolgt der Angriff von oben,
keine Diastereomere
AcOH
3-A2 trans-1,2-Cyclohexandiol aus Cyclohexen
OH
OH
H2O2
HCO2H,H2O
HO OH C H
O
HO
H O O C
O
H
HO C H
O
O
H2O
OH
OH
HO
O H
H OH
O
- H2O
H
O
O
O
H
3-A3 cis-1,2-Cyclohexandiol aus Cyclohexen
OH
OH
O
N
O
,K2OsO2(OH)4
kat.
Os
O
O O
O O
Os
O O
O
H2O
O
OsO
OH2
O
O
OH
Os
O
dto.
OH
OH
Os
O
O
HO
HO
VIII VI
O
O
OH
O
N
O
VI
Os
O
O O
O
VIII
O
N
- H2O
3-A4 1,1-Dichlor-2-phenylcyclopropan aus Styrol
Cl
ClHCCl3,NaOH
3-A4
HCCl3 + OH H2O + CCl3
-Cl
CCl2
Phasentransferkatalysator
CCl2+
Cl
Cl
racemisch
3-B1 trans-3,4-Dibromcumarin aus Cumarin
O O O O
Br
BrBr2,CHCl3
O O
Br Br
O O
Br
Br
O O
Br
Br
3-B2 cis-3,4-Dibromcumarin aus o-Hydroxyzimts?ure
CO2H
OH O
Br
Br
O
Br2,CCl4
CO2H
OH Br Br
CO2H
OH
Br
Br
O
Br
Br
O
OH
H O
Br
Br
O
H2O
Ringschlu? ist Entropiegetrieben ( zwei Teilchen)
3-B3 2-Octanon aus 1-Octen
O2,PdCl2,CuCl2 O
β-Cyclodextrin/Wasser
Cl Pd Cl
Pd
H
R
H H
Cl H
2O
H
H
Pd
OH2
R
H
Cl - Pd°
- HCl
H
H
HO
R
H
H
O
R
Bdg,etwas l?nger
Cl
3-B4 cis-Cyclooctenoxid aus cis-Cycloocten
O
H2O2,KHCO3
MeOH/MeCN
HO OH H2O + CO2 + OOH
N C CH3 OOH N CH3
OOH
H
HN CH3
OOH
Peroxyimids?ure
H
O O
NH
CH3 O
meso - Form
C
O
H2N
CH3
O
O OH
3-C1 (+),(-)-Dibrombernsteins?ure aus Maleins?ure
COOH
H
H
COOH
COOH
COOH
HBr
BrH
COOH
COOH
H Br
Br H
Br2
+
COOH
H
H
COOH
Br Br Br
COOH
COOH
H
H
Br
COOH
COOH
H Br
Br H
racemisch
3-C2 meso-Dibrombernsteins?ure aus Fumars?ure
COOH
HOOC
H
H
COOH
COOH
BrH
BrH
Br2
COOH
HOOC
H
H
Br Br Br
COOH
H
HOOC
H
Br
COOH
COOH
BrH
BrH
3-C3 2,3-Epoxygeraniol aus Geraniol
in Emulsion aus
Octanol/Hexan/Wasser
(Octadecyl)2(Me)2NCl
OH OH
O
m-Cl-C6H4-CO3H
Im Zweiphasigen System wird bevorzugt die
Doppelbindung am polaren Ende des Moleküls
angegriffen
OH
CO
OO
H
Cl
OH
O C
OH
O
C
l
3-C4 6,7-Epoxygeranylacetat aus Geranylacetat
OAc OAcm-Cl-C6H4-CO3H
CH2Cl2
O
Die e--reichere Doppelbindung wird in L?sung
bevorzugt angegriffen
e--arm
e--reich
3-D1a erythro-9,10-Dibromstearins?ure aus?ls?ure
3-D1b threo-9,10-Dibromstearins?ure aus Elaidins?ure
COOH COOHBr
Br
Br2
3-D1a
Br Br +
COOH COOHBr
+ Br
COOH
BrBr + COOH
Br
Br
racemisch
COOH
COOHBr2 Br
Br 3-D1b
COOHBr Br
+
CO
OHBrBr
+
COOH
Br
Br
^=
COOHBr
Br
HR1
Br
racemisch
Br
H R2^=
R1
R2
Br
Br
3-D2 1-Chlorindan aus Inden
Cl
H Cl
HCl
H Cl
benzylst?ndige positive Ladung
Cl
3-D3 10-Brom-11-hydroxy-10,11-dihydrofarnesylacetat
aus Farnesylacetat
OCOCH3
HO
OCOCH3
Brtert.-ButOH/H2O
NBS
OCOCH3
N OO
Br
OCOCH3
Br
l?nger und damit schw?cher
OH
N
O
O
HO
OCOCH3
Br
N
O
O
H2O HN
O
O
OH
3-D4 Malons?ure-di-tert-amylester aus 2-Methyl-2-buten
und Malons?ure
O
O
O
O
H2SO4
OH
O
OH
O
2 H2SO4 H
OH
O
OH
O
O
O
O
O
H
H
-2H
O
O
O
O
3-E1 exo-cis-Bicyclo[2.2.1]heptan-2,3-diol aus 2-Norbornen
3-E2 endo-cis-1,7,7-Trimethylbicyclo[2.2.1]heptan-2,3-diol
aus 2-Bornen
3-E3 endo-cis-1,7,7-Trimethyl-3-tert-
amyloxybicyclo[2.2.1]heptan-2-ol aus endo-cis-1,7,7-
Trimethylbicyclo[2.2.1]heptan-2,3-diol (3-E2)
OH
KMnO4,NaOH
OH
OOH H2SO4
KMnO4,NaOH
OH
OH
3-E1
3-E2
3-E3
3-E1
Mn
O
O
O
O
O Mn
O
O
O
OH
O
Mn
O
OO
OH
+H
O
Mn
OH
OO
OH
OH
OH
Mn
O
O
HO
HO
Einflug des Permanganats von der weniger stark gekrümmten (konkaven) Seite (exo)
Angriff von oben?quatoriale Position der Hydroxidgruppen
3-E2
Mn
O
O
O
O
O Mn
O
OH
O
OH
OH
OH Mn O
O
HO
HO
3-E3
H
H
OH
OH
H
OH
HO
-M
OOH
Sterisch leichter Zug?nglich
3-E4β-Ionon aus Pseudoionon
O O
H2SO4
3-E4
O
~H
OH
O
H
-H
O
4,β-Eliminierungen
4-A1 1,3-Cyclohexadien aus 3-Bromcyclohexen
Br
N
Br
H N
H
N
4-A2 1,3-Cyclohexadien aus trans-1,2-Dibromcyclohexan
Br
Br
NaOH
CH3-O-CH2-CH2-OH
H
HH
Br
Br
HH
OH + CH3-O-CH2-CH2-OH
H2O + O-CH2-CH2-O-CH3
H
H
H
H
Br
OR
statt,weil dann Br
und H im Winkel von 60°
statt 180° zueinander
stehen.Br
4-A3 1-Bromcyclohexen aus trans-1,2-Dibromcyclohexan
Br
Br BrNaNH
2
tert-BuOH
Br
Br
H
Na
O Br
HO-tBu + Na Br
4-A4a 3-Menthen und 2-Menthen aus (+)-
Neomenthyltosylat mit Natriummethanolat
NaOMe
OTs
+
OTs
NaOHMe
H
TsO
Isopropyl ist ein konformativer Anker.
4-A4b 2-Menthen und 3-Menthen aus (+)-
Neomenthyltosylat mit Kalium-tert-butylat
OTs
+
4-A4b
tert-BuOK
H
OTs
H
CH3
Ot-Bu
H
CH3-OTs
+
E2,KOt-Bu sterisch anspruchsvolle Base Hofmann
Aber OTs gute Abgangsgruppe E1 auch Saytzew
4-B1 3-Methyl-2-methylenbutters?ure-tert-butylester aus
2-Brom-2,3-dimethylbutters?ure-tert-butylester
CO2-tert-Bu
H3C
CH3
CO2-tert-Bu
CH2
H3C
CH3
Br
CH3
tert-BuOK
tert-BuOK ist eine anspruchsvolle Base,deshalb erfolgt der Angriff an einem peripheren
C-Atom
CO2-tert-Bu
H3C
CH3
Br
CH2 O
H
tertBuOH
CO2-tert-Bu
CH2
H3C
CH3
Br
4-B2 2,3-Dimethyl-2-butens?ure-tert-butylester aus 2-
Brom-2,3-dimethyl-butters?ure-tert-butylester
CO2-tert-Bu
CH3
H3C
CH3
NCO2-tert-Bu
H3C
CH3
Br
CH3
CO2-tert-Bu
H3C
CH3
Br
CH3
N
H
CO2-tert-Bu
CH3
H3C
CH3
Saytzew
DBU ist eine schwache Base kleiner
Energiegewinn sp?ter üZ hohe
Regioselektivit?t
4-B3 2-Phenylpropen aus (1-Chlor-1-methylethyl)-benzol
Cl
N
N
,
4-B3
Cl
H
H
H
ba (DBU)
4-B4 1-Cyanocyclohexen aus Cyclohexanoncyanhydrin
CNHO CN
SOCl2
CNHO
Cl S Cl
O
-HCl
CNOS
Cl
O
H
CN
+ HCl + SO2
eventuell aber auch E1 über,CN
HO S Cl
O
4-C1 Bromfumars?ure aus (+),(-)-Dibrombernsteins?ure
HOOC
COOHBr
H
COOHHOOC
Br
Br
H2O,?
COOHHOOC
Br
Br
H H2O,? HOOC
COOHBr
H
HBr
HBr ist die Triebkraft ( Entropie)
4-C2 Brommaleins?ure aus meso-Dibrombernsteins?ure
HOOC
HBr
COOH
COOHHOOC
Br
Br
H2O,?
COOHHOOC
Br
Br?T HOOC
COOH
H
H
Br
HOOC
HBr
COOH
4-C3 3-Menthen und 2-Menthen aus (-)-Menthylacetat
O
O 450°C
+
O
O
H
O
O Saytzew-Produkt
Tschugajev Eliminierung cyclischer
übergangszust?nde
4-C4 3-Menthen und 2-Menthen aus O-(-)-Menthyl-S-
methylxanthogenat
O SMe
S 140-150°C
+
4-C4
H O
MeS
S
Me
H
H
Me
+
MeS
SH
O
iPr konformativer Anker syn-Eliminierung
4-D1 3-Menthen aus (-)-Menthol
OH
H2SO4
OH
H
OH2 H
-H
4-D2 2-Menthen aus (-)-Menthylchlorid
Cl
KO tBu
Dibenzo-18-krone-6
(2-D4)
Petrolether
Cl
H K O tBu
H H
H
Cl Mindermengenkonformer
erkl?rt Regioselektivit?t,
weil H-Atom und Cl-Atom
periplanar zueinander stehen,
4-D3 trans,trans-Mucons?urediethylester aus 2,5-
Dibromadipin?urediethylester
EtO2C
CO2Et
Br
Br
EtO2C CO
2Et
Pyridin
EtO2C
CO2Et
Br
Br
N
H
H
EtO2C
CO2
Et
Br
EtO2C CO
2Et
4-D4 1,1-Diphenylethylen aus 1,1-Diphenylethanol
OH
H2SO4
4-D4
OH
+H
OH2 E
1
-H2o
H2C
H
-H
Wasser fungiert als Base zur Protonenübertragung
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,D
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,D
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,D
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,D
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,D
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-E1 Brommesitylen aus Mesitylen
BrBr
2,CCl4
Br Br Br
H
H
Br
5-E2 Ioddurol 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,D
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-E5 mono-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
p H > 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-F1 Pikrins?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
d d
I- HI
I I
SEAr
5-F3 Kristallviolett aus Michlers Keton und
Dimethylanilin
NMe2Me
2N
O
NMe2
ClH
NMe2
PCl5,D
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,D
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,D
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
6,Nucleophile Substitutionen an Carbons?urederivaten
6-A1 Pivalins?urepyrrolidid aus Pivaloylchlorid und
Pyrrolidin
6-A2 tert-Butylcyclohexenylketon aus
Pivalins?urepyrrolidid (6-A1) und dem von 1-
Bromcyclohexen (4-A3) abgeleiteten Grignard-Reagenz
NHO
Cl
O
NCHCl3,Pyridin
O
Mg Br
6-A2
6-A1
O
Cl
NH
Cl
O
N
-Cl
O
N
6-A
1
Mg Br
+
N
O
MgBr
HCl
O
NH
O
6-A2
H -H
H
-H,
NH-
6-A3 (R)-3-Hydroxybutters?uremethylester aus Poly-[(R)-
3-hydroxybutters?ure]
ClCH2CH2Cl / CH3OH
H2SO4
O O
H
HO
n
OMe
OOH
6-A3
O OH
H
HO
n MeOH
O OH
H
HO
nOH
Me
~H O OH
H
OH2nO
Me
O
OMe
OH
O OH
HO
n-1
- -H2O
6-A4 2-Methyl-2,5-decandiol aus -Pentyl- -butyrolacton
O
nC5H11
O
OH
HO
nC5H11
MeMgI
6-A4
O
nC5H11
O
Me MgI
O
nC5H11
O
Me MgI
OO
nC5H11
Me MgI
MgI
O
O
nC5H11MgI
MgI
OH
HO
nC5H11
+NH4Cl -2 NH3,-2 MgICl
6-B1 Fluoren-9-carbaldehyd aus Fluoren
CHO
NaH,HCO2Et
6-B1
HH
NaH
-H2
Na
O
H OEt
OEtH
O
H
O
H OEt
H
-HOEt
O
H
-H
6-B2 Sebacins?uredichlorid aus Sebacins?ure
6-B3 Sebacins?urediamid aus Sebacins?uredichlorid (6-
B2)
O
Cl (CH2)8 Cl
O
O
OH (CH
2)8
HO
O
SOCl2
O
H2N (CH2)8 NH2
O
NH3 (wrig)
6-B2
6-B3
O
OH (CH
2)8
HO
O S Cl
O
Cl
O
OH (CH
2)8
O
O
S
O
Cl
+Cl
H
O
OH (CH
2)8
O
O
S
O
Cl
+Cl +
H
O
OH (CH
2)8 O
O
S
O
Cl
Cl
H +
-HCl / -SO2
O
OH (CH
2)8 Cl
O
O
Cl (CH2)8 Cl
Oanalog
O
Cl (CH2)8 Cl
O NH
3
O
Cl (CH2)8 Cl
O
NH3
O
Cl (CH2)8 NH3
O
Cl
O
Cl (CH2)8 NH2
O
O
H2N (CH2)8 NH2
O
analog
- HCl
6-B4 Octanal aus N-Formylpiperidin und dem
Grignardreagenz aus 1-Bromoctan (2-A1)
1) Mg,Et2O
2)
Hept Br Hept
O
NO 6-B4
Hept Br
Mg
(SET)
Hept MgBr
Hept MgBr
N
O
NHept
OH MgBr
NHHept
OH MgBr
H
Hept O
-HN
6-C1 Acetylsalicyls?ure aus Salicyls?ure
CO2H
HO
CO2H
OAc
O OO
H2SO4
6-C1
CO2H
HO
O OHO
CO2H
O
H O
O O
~H
CO2H
O
O
O O
H- HOAc
CO2H
OAc
6-C1
6-C2 Sebacins?uremonomethylester aus
Sebacins?ures?uredimethylester
6-C3 10-Methyl-10-hydroxy-undecans?ure aus
Sebacins?uremonomethylester (6 C2)
6-C4 Sebacins?ureethylmethylester aus
Sebacins?uremonomethylester (6-C2)
O
MeO (CH2)8 OH
OO
MeO (CH2)8 OMe
O
1) Ba(OH)2
2) H3O
1) MeMgI
OH
(CH2)8 OH
O
1) Cl-CO-OEt
2) EtOH
O
MeO (CH2)8 OEt
O
2) NH4Cl/H2O
6-C2
6-C3
6-C4
O
MeO (CH2)8 OMe
O OH O
MeO (CH2)8 OMe
O
OH
O
MeO (CH2)8
O
OH
+ OMe
O
MeO (CH2)8
O
O -HOMe
+H
O
MeO (CH2)8 OH
O
6-C2
O
O (CH2)8 OMe
O
6-C2
Me MgI O
O (CH2)8 OMe
O MgI
+NH4 / -NH3
H
Me MgI
-CH4
O
O (CH2)8 OMe
O MgI
H
-HOMe
O
O (CH2)8
O
Me MgI
O
O (CH2)8
O H OH
(CH2)8 OH
O
6-C3
O
OH(H2C)8MeO
O
6-C2
+ NEt3
- HNEt3
O
O(H2C)8MeO
O
O
Cl OEt
O
O(H2C)8MeO
O
O
ClO
Et
O
O(H2C)8MeO
O
O
OEt
Cl
O
O(H2C)8MeO
O
O
OEtCl (H2C)8MeO
O
Cl
O
EtOH
(H2C)8MeO
O
Cl
O
OH
Et
(H2C)8MeO
O O
OEt
H
-H
O
MeO (CH2)8 OEt
O
6-C4
+ O
O
OEt
- CO2/OEt
6-D1 (S)-Hydroxybernsteins?uredimethylester aus (S)-
pfels?ure
HO
O
H O
O
O H
MeO
O
OMe
O
HOH+ (Ionen-
austauscher)
MeOH
6-D1
HO
O
H O
O
O H
H HO
O
H O
OH
O H
CH3OH
HO
O
H O
OH
O H O
Me
H
~HHO
O
H O
OH2
O H O
Me
HO
O
O H
OH
OMe
-H2O
-H HO
O
OMe
O
HO
MeO
O
OMe
O
HO
6-D2 1-(Phenylacetyl)imidazol aus Phenylessigs?ure und
1,1‘-Carbonyldiimidazol
N
O
N
O
N NN N
6-D2
O
O H
O
O H
O
N NN N
O
O +
O
N NN N H
O
O
O
N
N N
N
H
O
O
O
N
N
N
N
H
O
N
O
N
N
O
N
H
~H O
N
O
N
N
O
N
H
-CO2/ -N
N
H
O
N
N
6-D3 Benzylethylketon aus 1-(Phenylacetyl)imidazol (6-
D2) und Ethylmagnesiumbromid
O
N
N
EtMgBr
6-D3
O
O
N
N Et MgBr
O
N
NEt
MgBr
H
O
NH
NEt
MgBr
O N
N H
6-D4 Fumars?ure-tert-butylethylester aus
Fumars?uremonoethylester,tert-Butanol und DCC
N NC
COOH
EtOOC
COOtBu
EtOOC 6-C4
t-BuOH
EtOOC
O
O
N NC
N
N
C
H
H
EtOOC
O
O +
EtOOC
N NC
O
O
EtO2C
N
HN
O
O
H
HO
O
O
EtO2C
NH
NHO O
O
EtO2C
N
NHOH
~H
O
EtO2C O + O
NH
NH
6-E1/2 1-Chlor-2-methyl-1-(piperidin-1-yl)propen aus iso-
Butters?urepiperidid
O
N
Cl
N
Cl
Cl
N Et3N
6-E1/2
ClCl
O O
O
N
O
N
ClCl
O O O
Cl
O
O
Cl
N
O
O
Cl
N
O
ClO
O
Cl
N
O
Cl
-CO2/-CO
Cl
N
Cl
H
Et3N
Cl
N
-HEt3N
6-E3N-Boc-L-Alanin-(N-methoxy-N-methylamid aus N-Boc-
L-Alanin
6-E4(S)-4-(tert-Butoxycarbonylamino)-1-pentin-3-on aus N-
Boc-L-Alanin-(N-methoxy-N-methylamid (6-E3)
O
HO
H3C
BocNH
O
N
CH3
BocNH OCH3
CH3
1) ClCOOCH3
2) CH3ONHCH3
O
CH3
BocNH [Li *NH2CH2CH2NH2]
6-E3
6-E4
O
HO
H3C
BocNH Cl
O
OMe
O
O
H3C
BocNH
H
O
Cl
OMe
O
O
H3C
BocNH
O
OMe
+Cl +H
-CO2/-HOMe
O
H3C
BocNH Cl
NH
Me
OMe
O
CH3
BocNH
Cl
NH
OMe
Me -Cl -H
CH3
BocNH NH
OMe
Me
O O
N
CH3
BocNH OC
H3
CH3
6-E3
O
N
CH3
BocNH OCH3
CH3
6-E3
Li
*NH2CH2CH2NH2
O
NBocNH OCH3
CH3
6-E3
Li
NH2
NH2
H
O
NBocNH OCH3
CH3
H
O
CH3
BocNH
6-E4
6-F1L-Phenylalaninmethylester-hydrochlorid aus L-
Phenylalanin
Cl
SOCl2/MeOH
H3N CO2
Ph
H3N
Ph
O
OMe
6-F1
H3N
Ph
O
O
S O
Cl
Cl
H3N
Ph
O
O
Cl
S
O
Cl
H3N
Ph
O
O
Cl
S
O
ClH
3N
Ph
O
ClCl
MeOH
H3N
Ph
O
Cl
O
Me H
Cl -HCl
H3N
Ph
O
O
Cl
Me
H3N
Ph
OMe
O
Cl
-SO2
6-F2 N-(Benzyloxycarbonyl)-L-asparagins?ure aus L-
Asparagins?ure
6-F3 N-(Benzyloxycarbonyl)-L-asparagins?ureanhydrid
aus N-Benzyloxycarbonyl-L-asparagins?ure (6-F2)
6-F4 N-(Benzyloxycarbonyl)-aspartam aus N-
(Benzyloxycarbonyl)-L-asparagins?ureanhydrid (6-F3) und L-
Phenylalaninmethylester (6-F1)
2) PhCH2OCOCl
1) MgO/H2O/Et2O
OH
OH
O
O
NH2
OH
OH
O
O
NHO
O
Ph
NHO
O
Ph
O
O
O
Ac2O
H2N
Ph
O
OMe
N
H
Ph
O
OMe
O
CO2H
NH
(aus
6-F1)
O
O
6-F2
3) HCl
6-F4
Ph
OH
OH
O
O
NH2
Ph O
O
Cl
MgO
-H2O O
O
O
O
H2N
Mg
O
O
O
O
NH2
Mg
Cl
O
O
Ph
-H
O
O
O
O
NH
Mg
Cl
O
O
Ph
O
O
O
O
NH
Mg
OOPh
+2H2O
-Mg(OH)2OH
OH
O
O
NHO
O
Ph
6-F2
OH
OH
O
O
NHO
O
Ph O
OO
O
OH
O
O
NHO
O
Ph
O
O
O
O
OH
O
O
NHO
O
Ph
O
O
O
~H
H
O
OH
O
O
NHO
O
Ph
O - HOAc
H
OH
NHO
O
Ph
O
O O
~H
O
NHO
O
Ph
O
O O
H
- HOAc
O
NHO
O
Ph
O
O
H2N
Ph
O
OMe
O
NHO
O
Ph
O
O
NHO
O
Ph
O
O
O NH2 O
OM
e
Ph
~H
NHO
O
Ph
O
O
O NH O
OM
e
Ph
6F-3
HNHO
O
Ph
O
O
NH
OMeO
Ph
H
O
6F-4
O
O
NHO
O
Ph
O
O O O
H
O
7,Umwandlungen von Carboxylverbindungen und Nitrilen
ineinander
7-A1 Malons?ure aus Cyanessigs?ure
CN
CO2H
2) CaCl2 CO
2
CO2
CO2H
CO2HHCl
Ca2
1) NaOH
C
CO2H
N
+
C
CO2
N
Na OH
Na
+H2O
-OH C
CO2
HNOH
OH
+OH -H2O
C
CO2
NH
O
+H2O
-OH
C
CO2
NH2
O
HO
C
CO2
NH2O
OH
+H2O -OH
C
CO2
NH3O
OH
C
CO2
O
OH
-NH3 C
CO2
O
OH
2) CaCl2
+OH / -H2O
C
CO2
O
O
Ca2+2 HCl
-CaCl2
CO2H
CO2H
7-A2 Glycinethylesterhydrochlorid aus 1,3,5-
Tris(cyanmethyl)-1,2,3,4,5,6-perhydrotriazin (9-A3)
NH3EtO2C
Cl
HCl gasN
N
N CNNC
CN
EtOH abs,7-A2
N
N
N CNNC
CN
H
N
N
N CNC
CN
NH
EtOH
N
N
N CNC
CN
NH
OEt
H
~HN
N
N CNC
NC
NH2
OEtH2ON
N
N CNC
NC
NH3
OEt
~H
O H
-NH3,
-H N
N
N CNC
NC
OEt
O +H N
N
N C
NC
NC
OEt
O
H
N
N
N
H2C
C
NC
NC
OEt
O
H
H2ON
N
N C
NC
NC
OEt
O
H OH
-H
N
N
N C
NC
NC
OEt
O
H
OH+H
H N
N
N C
NC
NC
OEt
O
H
H + O H
H H
O
H H
3x+H3N C
OEt
O
Cl
3x
7-B1 Sebacins?uredinitril aus Sebacins?urediamid (6-B3)
O
H2N (CH2)8 NH2
O
NC
(CH2)8
CN
SOCl2
7-B1
O
H2N (CH2)8 NH2
O
+
Cl S Cl
O -Cl
O
H2N (CH2)8 NH2
O S
O
Cl
-HO
H2N (CH2)8 NH
O S
O
Cl-SO2 / -Cl
O
H2N (CH2)8 NH
-H O
H2N (CH2)8 N
+SOCl2,-2HCl / -SO2 NC
(CH2)8
CN
7-B2 Pentaacetyl-D-glucons?urenitril aus D-Glucoseoxim
(9-B3)
7,B-2
NaAc,HOAcCHNOH
HO
OH
O H
HO
OH
CN
OAc
AcO
AcO
AcO
OAc
Ac2O
C
H
HO
OH
O H
HO
OH
O
O O
N OH
C
HO
OH
O H
HO
OH
N O
O
H
+
O
O
H
~H
C
HO
OH
O H
HO
OH
N +
HO
O
O
O O
C
HO
OH
O H
HO
OH
N
O
O O
~H
C
HO
O
O H
HO
OH
N
O
O OH
-CH3COOH
C
HOAcOO H
HO
OH
NCN
OAc
AcO
AcO
AcO
OAc
(1)
(1)
(2)
(2)
2
7-C1/2 Methylbernsteins?ure aus 3-Cyanbutans?ure
CO2HNC CO2O2C
Ba(OH)2
CO2HHO2C
HNO3
CO2Et
NaCN
EtOH,H2O H2O,?
Ba2
7-C1/C2
C
CO2H
H
C
N
+OH
CO2
C
NHO
+OH,-H2O
H2O
-OHCO2
C
NHHO
+OH -H2O
CO2
C
NHO +H2O
-OH CO2
C
NH2O +OH
CO2
C NH2O
OH
+H2O -OH
CO2
C NH3O
OH
-NH3
CO2
C
O OH+OH
-H2O
CO2
C
O O Ba2+
+HNO3
CO2H
C
O OH
O
OEt
CN
C
O
OEt
CN +H2O
-OH C
O
OEt
CN H
C
O
OEt
CN OH
C
O
OEt
CN
OH
-OEt
7-D1 (1-Naphthyl)acetonitril aus 1-
(Chlormethyl)naphthalin (5-D4)
7-D2 (1-Naphthyl)acetamid aus (1-Naphthyl)acetonitril
(7-D1)
NaCN
EtOH,H2O
Cl CN
HCl /H2O
O
NH2
7-D1 b)
7-D2
Cl
CN
SN2
CN
+ Cl
C N
+H Cl C N H
+ Cl
H2O C N H
OH2 Cl
C
N H
OH
HCl +
C
N H2
OH
Cl
-HCl
C
N H2
O
O
NH2
7-E1 D-Gulons?ure- -lacton aus D-Xylose
O
OH OH
O
O
H
O
1) Ba(OH)2*6 H2O
HO
OH
OH
OH
OH
CN
3) kristallisieren
aus MeOCH2CH2OH
2) H2SO4NaCN
HO CHO
OH
OH
OH NH4Cl
HO CHO
OH
OH
OH
+NH4
-NH3
HO
OH
OH
OH
O
CN
HO
OH
OH
OH
OH
C
N
+OH
HO
OH
OH
OH
OH
C
N
HO
H2O
HO
OH
OH
OH
OH
C
N
HO
H
+OH -H2O
HO
OH
OH
OH
OH
C
N
O
H +H2O
-OH
HO
OH
OH
OH
OH
C
NH2
O
HO
OH
O
OH
OH
C
NH2
OH
~H
HO
OH
O
OH
OH
C
NH3
O
-OH
HO
OH
O
OH
OH
C
NH3
O
-
7-E2 Pyridin-3-carbonitril aus Pyridin-3-carboxamid
CH2Cl2N
NH2
O
N
CN
7-E2
Cl3CCOCl / NEt3
N
NH2
O
Cl CCl3
O
+
N
NH2
O C
O
Cl
CCl3
N
NH2
O C
O
C
Cl
3
Cl
-HCl
N
NH
O C
O
CCl3
-CO2-CCl3
N
NH +
-HCCl3
N
CN
7-F1 -Phenylalanin aus 2-Amino-2-phenylpropionitril
(9-F4)
7-F1
1) HCl / H2O /?
2) Pyridin
(9,F-4)
CNH2N CO2H3N
CH2N N 2HCl
-2Cl
CH3N NH
H2O
CH3N NH
OH2
~H
CH3N NH2
H2O
OH
CH3N NH2
OH2
OH
~H
CH3N NH3
OH
OH
CH3N NH3
OH
OH
+
-NH4Cl
CO2H3N
8,Umwandlungen von Kohlens?urederivaten und
Heterocumulenen ineinander
8-C3 Natrium-(S)-2-amino-6-guanidinocapronat aus S-
Ethylthiouronium-bromid und L-Lysin
8-C2
S
H2N NH2
S
H3N NH
Et
Br NaH2N CO2
NH3
4
2)
1) NaOH
CO2
NH2
4
H
NHN
NH2
EtBr
S
H2N NH2
Et Br S
H2N NH2
Et
Br
S
H3N NH
Et
Br
H2N CO
2
NH3
4
S
H2N NH2
Et
Br
H2N CO
2
NH3
4
-SEt H2N
NH2 Br
H2N CO2
NH3
4
-H
-H-H
Na
CO2
NH2
4
H
NHN
NH2
8-D3 3-[3-(Dimethylamino)propyl]-1-ethylcarbodiimid
aus Ethylisocyanat und 3-Dimethylamino-1-propylamin
2) p-TsCl,Et3N
NEtCO
1)
NMe2H2N
NMe2N
C
NEt 8-D3
+ NEt3
NMe2H2N
HNEt3 + NMe2HN
NEt
C
O
+ Cl S
O
O
CH3 S
O
O
CH3OCNEt
NMe2HN
NMe2NCEtN
Cl
-Cl
OTs
+NEt3
-HNEt3,-OTs
NMe2NCEtN H
8-E3/4 (4-Methoxyphenyl)isothiocyanat aus p-Anisidin
8-E3/4
MeO
NH2 CS
2
Et3N MeO
H
N
S
S
EtNH3
ClCO2Et
Et3N MeO
N C S
MeO
NH2
C
S
S
MeO
H2
N
S
S
MeO
H2
N
S
S
Et3N
OMe
H
N
S
S
EtNH3
Cl OEt
O
- EtNH3OMe
N
S
SEtO
O
H
Et3N -Et3NH
MeO
N C S
+ SEtO
O
Et3NH SHEtO
O
SEtHO
O
EtOH + S C O
8-E3
(1)(2)
8-F2 1,3-Di-(tert-butoxycarbonylamino)benzol aus m-
Phenylendiamin mit Di-tert-butyldicarbonat
8-F3 m-Phenylendiisocyanat aus 1,3-Di-(tert-
butoxycarbonylamino)benzol (8-F2)
8-F2
8-F3
H2N NH2
t-BuO O Ot-Bu
O O
N
H
N
H
Ot-Bu
O
t-BuO
O
N N
BCl3,NEt3
C OCO
H2N NH2
t-BuO O Ot-Bu
O O
N
H2
H2N
Ot-Bu
O
O
O
Ot-Bu
Boc-Anhydrid!
O
O
Ot-
Bu-
N
H2
H2N
O
Ot-Bu-HN
H
H2N
O
Ot-Bu
N
H
N
H
Ot-Bu
O
t-BuO
O
N
H
Nt-BuO
O
Ot-Bu
O
BCl3
H8-F2
BCl3
+NEt3
-HNEt3,
-BCl3,
N
H
Nt-BuO
O
C O
-Ot-Bu
N N C OCO
dto.
9,Umsetzung von Hetero-Nucleophilen mit Aldehyden
bzw,Ketonen
9-A3 1,3,5-Tris(cyanmethyl)-1,2,3,4,5,6-perhydrotriazin
aus Formaldehyd
N
N
N CNNC
CN
C
O
/ NH4ClCH3COOH
NaCN
H H
9-A3
C
O
H H
NH4
C
OH
H H
+ NH3
NH3
H OH
H
~H
NH2
H
OH2HNH2
HHH3N
NH2
HH
NH3
- H
H2N NH2
OH
H H
H2N NH2
OH
~H H
2N NH
OH2
- H2O
H2N NHH
3N CH
2
H2N NH
H3N
O
HHH2N NH
H2NHO
~H
HN NH
H2NH2O
- H2O HN NH
N
H2
- H HN NH
N
H
O
HH
HN NH
N
HO
H
~HHN NH
N
H2O
CN
HN NH
N
NC
N N
N
NC
CNNC
analog
-H
H
9-A4 1,2:5,6-Diisopropyliden-D-mannit aus D-Mannit
HO
OH
OH
OH
OH
OH
MeO OMe
O
O
HO
OH
O
O
SnCl2
9-A4
MeO OMe + SnCl
2
O OMe
SnCl2Me
MeO + MeOSnCl2
HO
OH
OH
OH
OH
OH
MeO
HO
OH
OH
OH
OH
O OMe
H
~H
HO
OH
OH
OH
OH
O OMe
H
HO
OH
OH
OH
OH
O
- MeOH
HO
OH
OH
OH
O
O
H
- H HO
OH
OH
OH
O
O
O
O
HO
OH
O
O
9-B3 D-Glucoseoxim aus D-Glucose
CHNOH
OH
HO
HO
HO
OH65 °C
NH2OH
9,B-3
O
HO
HO
HO
OH
OHCHO
OH
HO
HO
HO
OH
OH
HO
HO
HO
OH
O
H
NH2OH OH
HO
HO
HO
OH
O
H
NH2-OH
~H
OH
HO
HO
HO
OH
OH2
H
N-OH- H2O
OH
HO
HO
HO
OH
N OH
O
HO
HO
HO
OH
H
N OH
9-B4 Chinoxalin aus o-Phenylendiamin und Glyoxal
9,B-4
+
1)
NaHSO3
,H2O
2) Na2CO3 N
NNH2
NH2 O
O
NH2
NH2 O
HO
+
H2
N
NH2
OH
H
O
~H
H
N
NH2
OH2
H
O
H
N
NH2 O
- H
N
NH2 O
analog
N
N
9-C4 Meldrum’s S?ure aus Aceton und Malons?ure
O
O
O
OOH
OH
O
O
Me2C=O,Ac2O,H2SO4
9-C4
OH
OH
O
O
O
O
O
OH
OH
O
O
OH
O
O
H
OH
OH
O
O
OH
+
O
O- HOAc
OH
OH
O
O
O
O
OH
OH
O
O
O
O
OH
OH
O
O
O
O
O
O
HO
HO O
O
O
O
HO
OH
O
O
O
O
O
OH
-HOAc
-H
O
O
O
O
9-D4 2,5-Dimethylpyrrol aus 2,5-Hexandion
9-D4
O O NH
(NH4)2CO3
O O
NH4
O O
H
+ NH3
NH3
OHO
~HNH
2
OH2O
-H2O
O NH2 O NH O NH2 O NH2
~H
-H
N
H
HO
+H
N
H
H2O
-H2O
N N
H
H
H
-H
9-F4 2-Amino-2-phenylpropionitril aus Acetophenon
NaCN,NH4Cl
9-F4
O CNH
2N
O
NH4
OH
+ NH3
OH
NH3~H
OH2
NH2
-H2O
NH2
CN
CNH2N
10,Praktikumswoche
10,Addition von H-Nucleophilen oder Metallorganylen an
Aldehyde bzw,Ketone
10-A3 endo-1,3,3-Trimethylbicyclo[2.2.1]heptan-2-ol aus
(-)-Fenchon
10-A3O
OH
NaBH4
O H
Angriff an der weniger konkaven
Seite
O
H
H
OH
10-A4 syn-2,2-Dimethyl-4-phenyl-3-pentanol aus 2-
Phenylpropionaldehyd
Rac Rac
Rac
10-A4
O
H
OH
t-Bu
1) t-BuMgBr
2) HCl,H2O
O
H
BrMg
Angriff von vorne
O
t-Bu
PhH
Me
OH
Nu-
10-B1 (9-Fluorenyl)methanol aus Fluoren-9-carbaldehyd
(6-B1)
10-B1
OHO
NaBH4
O
H
O
H
H
10-B2 Cyclohexylcarbinol aus Formaldehyd und dem
Grignardreagenz aus Chlorcyclohexan
10-B2
MgCl
2) H2O / H2SO4
CH2OHO
H H
1)
O
H H
MgCl C H
H
O
H
10-B3 endo-1,3,3-Trimethylbicyclo[2.2.1]heptan-2-ol aus
(-)-Fenchon
10-B3O
OH
1) EtMgBr
2) HCl,H2O
O
MgBr
H
H H H2C CH2
O
O
H
Mg
Br
sechsgliedrig
10-B4 anti-2,2-Dimethyl-4-phenyl-3-pentanol aus 2,2-
Dimethyl-4-phenyl-3-pentanon
Rac Rac 10-B4
O
t-Bu
OH
t-Bu
NaBH4
O
t-Bu
H OH
t-Bu
PhH
Me
Ot-Bu
Nu-
10-C1/2 Bis[4-(dimethylamino)phenyl]phenylmethanol und
Malachitgrün aus 4,4’-Bis(4-dimethylamino)benzophenon
10-C2 a)
O
NMe2
NMe2
OH
MgBr
2) NH4Cl,H2O
1)
Me2N
Me2N
NMe2
BF4
HBF4,Ac2O
Me2N
10-
C1
O
Me2N
Me2N
BrMg
NMe2
O
Me2N
NH4Cl
NMe2
OH
Me2N
H
NMe2Me2N
NMe2
Me2N
-H2O
10-C3 endo-1,2,3,3-Tetramethylbicyclo[2.2.1]heptan-2-ol
aus (-)-Fenchon
O OH
1) MeMgI
2) HCl,H2O
10-C3
O
H3C MgI
O
Alkylierung,da kein β H
10-C4 syn- und anti-2-Phenyl-3-pentanol aus 2-
Phenylpropionaldehyd
Rac Rac Rac
10-C4
O
H CH3
1) CH3MgI
2) HCl,H2O
OH OH
+
7,3
CH3
O
H
H3C MgI
CH3
O
Haups?chlich
Cram
10-D1/2 1-Phenyl-3,4-tetrahydro-1-naphthol und 3,4-
Dihydro-1-phenyl-naphthalin aus a-Tetralon
10-D1
O
HO
2) NH4Cl,H2O
1) PhMgBr
(CH3CO)2O10-D2 a)
O
BrMg
O
HO
NH4Cl
O
O
O
O
O
O
O
O
O
O
O
H
O
O
H
- H
E1
10-D3 exo-2-Ethyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-
ol aus (+)-Campher
10-D3
O
OH1) EtMgBr
2) NH4Cl,H2O
O
Et MgBr
O
10-D4 anti- und syn-2-Phenyl-3-butanol aus 2-Phenyl-3-
pentanon
RacRac Rac
10-D4
O
Me Me Me
OH OH
+
7,3
NaBH4
O
Me
H
Me
O H
10-E1/2 Vinyl-b-ionol und Anhydro(vinyl-?-ionol) aus b-
Ionon (3-E4)
10-E1
O
MgBr
OH
2) NH4Cl,H2O
1)
5n H2SO4
4h RT10-E2 a)
O MgBr O
NH4Cl
H2O
OH
H
OH2
H
-H2O
-H
10-E3 (+)-Isoborneol aus (+)-Campher
10-E3O
OH
NaBH4
O
H
O
HCl
OH
10-E4 trans- und cis-4-tert-Butylcyclohexanol aus 4-tert-
Butylcyclohexanon
10-E4
O
NaBH4
t-Bu t-But-Bu
H
OH H
OH
+
8,2
O
t-Bu
H
H
H
H
H
t-Bu
H
O
t-Bu
H
O
+
10-F1 threo- und erythreo-1-(3,4-Dihydro-2H-pyran-2-yl)-
1-propanol aus 3,4-Dihydro-2H-pyran-2-aldehyd
Rac Rac
O O
EtMgBr;
HCl,H2O
O OH O OH
H
O
O HMg
Et
H
O
Mg
Et
OH
O O
MgBr
O O O O
10-F2 cis-1-Ethinyl-4-tert-butylcyclohexanol aus 4-tert-
Butylcyclohexanon
t-Bu
O
NH2
NH2
O
Li
t-Bu
OH
OH
H
H
H
H
Li
NH2
NH2
O
H
NH
NH2
Li
10-F3 (+)-Isoborneol aus (+)-Campher
O
OH
1) i-BuMgBr
2) NH4Cl,H2O
O
H
H3C
Mg Br
O OH
H
H3C
10-F4 cis,cis-3,5-Diphenylcyclohexanol aus cis-3,5-
Diphenylcyclohexanon
10-F4
O
NaBH4
Ph
Ph
OHPh
Ph
O
Ph
Ph
H OPh
Ph
OHPh
Ph
H2O
11,Praktikumswoche
11,Umsetzung von Heteroatom-stabilisierten C-
Nucleophilen mit Aldehyden bzw,Ketonen
11-A1 trans-4-Bromzimts?ureethylester aus 4-
Brombenzaldehyd und Triethylphosphonacetat
11-A1
CHO CO2Et
BrBr
C
Br
O
H
EtO C
H2
P
O O
OEt
OEt
EtO
P
O O
OEt
OEt
NaH,THF
NaH
EtO C
H
P
O O
OEt
OEt EtO C
H
P
O O
OEt
OEt
Ylen
Na
Br
O P(OEt)
2
O
OEt
O
Br
O P(OEt)
2
O
OEt
O
- H2
CO2Et
Br O
P
O
OEt
OEt
11-B1 cis-4-Bromzimts?ureethylester aus 4-
Brombenzaldehyd und
(Ethoxycarbonyl)methylphosphons?urediphenylester
11-B1
CO2Et
("TRITON B")
P CO2Et
PhO OPh
O
BrBr
O
PhCH2(CH3)2N+OH-,MeOH
EtO C
H2
P
O O
OEt
OEt
NaH
EtO C
H
P
O O
OPh
OPh EtO CH
P
O O
OPh
OPh
Ylen
Na
- H2
Br
O
Br
O P(OPh)
2
O
OEt
O
Br
O P(OPh)
2
O
OEt
O
CO2Et
Br O
P
O
OPh
OPh
11-C1 1,3-Bis(4-phenylbutadienyl)benzol aus Zimtaldehyd
und m-Xylylen-bis(triphenylphosphoniumchlorid)
11-C1
Ph3P PPh3
Cl Cl
LiOMe,EtOH
O
Ph3P PPh3 O Me
H
Ph3P PPh3
O
Ph3P PPh3
O PPh3
PPh3
PPh3
11-D1 3-(3-Methyl-2-buten-1-yl)indol aus
Indolcarbaldehyd (5-B6) und dem Instant-Ylid
Isopropylidentriphenylphosphoran
11-D1"Instant-Ylid"
[Me2CHP(C6H5)3Br
+ NaNH2]
O
O
Me2C PPh3
H
NH2
+ NH3Me2C PPh3 Me2C PPh3
Me2C PPh3
O
Ph3
P
+
O PPh3
11-E1 trans,E-5,9-Dimethyl-2,4,8-decatriens?ureethylester
aus Geranial und
(Ethoxycarbonylmethylen)triphenylphosphoran
O
CO2Et
11-E1
Ph3P
CO2Et
O
Ph3P
CO2Et
Ph3P
CO2Et
PPh3O
CO2Et
CO2Et
OPPh3
11-F1 E,E-2,5,9-Trimethyl-2,4,8-decatriens?ureethylester
aus Geranial und
[1-(Ethoxycarbonyl)ethyliden]triphenylphosphoran
O
CO2Et
Ph3P
CO2Et
11-F1
O
Ph3P
CO2Et
Ph3P
CO2Et
PPh3O
CO2EtCO2Et
OPPh3
12,Chemie von Enaminen und Enolen
12-A2 1-(N-Morpholino)cylopenten aus Cyclopentanon
und Morpholin
12-A3 2-(2-Methylbutyliden)cyclopentanon aus 1-(N-
Morpholino)cylopenten (12-A2) und Isovaleraldehyd
12-A3
O
N
H
O
N
O
+?
12-A2
O
2) HCl
1)
-H2O
O
N
H
O
+
N
O
O
H
~ H
+ H
N
O
OH2
- H2O
N
O
H
N
O
N
O
O
~ H
H
O
O
Analog gehen auch 12-B2/B3,12-E2/E3 und 12-F2/F3,allerdings dort Protonierung mit pTsOH !!
N
O
OH N
O
- OH
N
O
OH2
H
O H
~ H
N
O
O
H
H
O
H
- H
O
12-A4 (Acetamido)malons?urediethylester aus
Malons?urediethylester
12-A4
EtO2C
EtO2C
NH
OAc2O/AcOH
EtO2C
EtO2C
EtO2C
EtO2C
NOH
AcOH/H2O
NaNO2 Zn
EtO2C
EtO2C
H
O OEt
EtO
O
N O H
O OEt
EtO
O N
O
O OEt
OEt
O
N
O
- H
O OEt
OEt
O
N
O
H
H
O OEt
OEt
O
N
OH2
- H- H2O
O OEt
OEt
O
N
Zn
SET
Zn
O OEt
OEt
O
NH
e
H
2 e
2 H
O OEt
OEt
O
NH2
H
O
OEt
OEt
O
N
H2
HO
O O
O
O
O O
OEt
OEt
O
N
H2
H
O
O
O
O OEt
OEtO
N
H2
H O
O
O
O OEt
OEt
O
N
H
O
HO
O
12-B2 1-(N-Morpholino)cyclohexen aus Cyclohexanon und
Morpholin
12-B3 2-Oxocyclohexan-1-carbons?ureethylester aus 1-(N-
Morpholino)cyclohexen (12-B2)
12-B2
12-B3
N
H
O
N
O
+
Η+,Toluol,?
O
(-H2O)
O
OEt
O 1) Cl
OEt
O
2) 2n HCl
Mechanismus siehe 12 A2/3
12-B3
N
O
O
OEt
O1) Cl
OEt
O
2) 2n HCl
N
O
Cl
OEt
O N
O
Cl
OEt
O
O
OEt
O
vgl,12-C4
12-B4 Phenacylbromid aus Acetophenon
12-B4
CH3
O
CH2Br
O
Br2,AcOH
CH3
O
Br BrCH2
OH
- Br
H C
OH
H
HH
- H
CH2Br
OH
- HCH2Br
O
12-C2 2-Methyl-1,3-cyclopentandion aus Bernsteins?ure
und Propionylchlorid
12-C3 2-Methyl-2-(3-oxobutyl)-1,3-cyclopentandion aus 2-
Methyl-1,3-cyclopentandion (12-C2) und Methylvinylketon
12-C4 (7aS)-7a-Methyl-2,3,5,6,7,7a-hexahydro-1H-inden-
1-on aus 2-Methyl-2-(3-oxobutyl-1,3-cyclopentandion (12-
C3)
12-C3
12-C2
Cl
O
O
OH
O
HO
+
O
O
O
HO
O
O
O
AlCl3
12-C4
H2N
CO2
H
O
O
2) H2SO4
DMF
1)
HO
OH
O
OH
Cl
O
AlCl3
HO OH
O OH
O
Cl
- HCl
O
OH
O
OH
O
~ H
O
OH
O OH
HO
O
HO
O
OH
OH
O
O O
O
H
- CO2 O
O
O
HO
OHO
H
O
O
OH
O
O
O
- H
HO
O
O
H2N
CO2
H
O
O
N
HO2C H
O
N
HO2C H
O
O
N
O2C H
OH
~ H
H O
H
O
N
O2C
H
HO
H2O
ONH
O2C H
HO
HO
~ H
ONH
O2C H
HO
HO
H2N
CO2
H
O
HO
O
H
- H2O
O
O
- H
O
O
12-D2 2-Pyrrolidino-3,4-dihydro-6-methoxynaphthalin aus
6-Methoxy-2-tetralon
12-D3 6-Methoxy-1-benzyl-2-tetralon aus 2-Pyrrolidino-
3,4-dihydro-6-methoxynaphthalin (12-D2)
O
OMe
N
OMe
N
H
Toluol,?
(-H2O) 12-D2
12-D3
O
OMe 2) AcOH,H2O
1) PhCH2Br
O
OMe NH
O
OMe
NH
Ph
~ H
OH
OMe
N
OMe
N
H
- H2O
BrSN2
OMe
N H3O
vgl,12-C4
O
OMe
Ph
12-D4 2,5-Dibromadipins?urediethylester aus Adipins?ure
12-D4
EtO2C
CO2Et
Br
Br
HO2C
CO2H
1) SOCl2,Br2
2) EtOH
HO2C
C
O
OH
S
O
ClCl
HO2C
C
O
OH
S
O
ClCl
HO2C
C
O
OH
S
O
Cl
Cl
- Cl-
- SO2
HO2C
C
OH
Cl
HO2C
C
O
Cl
- H
C
C
O
Cl
Cl
O
C
C
O
Cl
Cl
OH
Br BrC
C
O
Cl
Cl
OH
Br
- H
HOC C
O
Cl
Cl
O
Br
C
C
O
Cl
Cl
O
Br
Br
- Cl-
(1)
(1)
(2)
(2)
C
C
O
H
O
Cl
O
Br
Br
- HC
C
O
O
Cl
O
Br
Br
C
C
O
O
O
O
Br
Br
12-E2 1-(N-Pyrrolidino)cyclohexen aus Cyclohexanon und
Pyrrolidin
12-E3 3-(2-Oxocyclohexyl)propions?ureethylester aus 1-
(N-Pyrrolidino)cyclohexen (12-E2) und Acryls?ureethylester
12-E2
N
O
N
H
OEt
O
1)
O
CO2Et
2) H2O,?
+
Η+,Toluol,?
(-H2O)
12-E3
Mechanismus siehe unter 12 A2/3
12-E4 2,4-Dibrom-3-pentanon aus 3-Pentanon
12-E4
O O
Br Br
Br2,PBr3 (kat)
-10 bis 0°C
O P
Br
Br
Br
O P
Br
Br
Br
H
- H
O P
Br
Br
Br
Br Br
- Br
O P
Br
Br
Br
Br
- PBr3
O
Br
O
Br Br
12-F2 1-(N-Piperidino)cyclohexen aus Cyclohexanon und
Piperidin
12-F3 1,10-Bis-(2-oxocylohexyl)-1,10-decandion aus 1-
(N-Piperidino)cyclohexen (12-F2) und Sebacins?uredichlorid
(6-B2)
12-
F2
N
H
N
+
Η+,Toluol,?
O
(-H2O)
Mechanismus siehe unter 12 A2/3
12-F3
O O O O
8
O O
8Cl Cl
1),Et3N
2) HCl/H2O
12-F4 -Brom- -butyrolacton aus -Butyrolacton
12-F4
O
O
O
O
Br
Br2,P
O
Br
Br
Br
H2O
3 Br2 + 2 P 2 PBr3
O O
P Br
Br
Br
O
O
Br
P
Br
Br
Br
- PBr3
O
Br
HO
OH
Br
HO
H
H
OH
Br
H2O
Br
Br Br
- H2O; -Br
- HO
Br
Br
Br
H
O H
Br
O
Br
H2O
Br
- H
OH
Br
O
Br
- Br
O
OH
Br
- H
O
O
Br
13,Chemie von Aldeyd-,Keton- und Esterenolaten
13-A1 Acetylbernsteins?urediethylester aus Acetessigester
und Chloressigs?ureethylester
O
CO2Et
OEt
O
O
OEt
O
1) Na,EtOH
2) ClCH2CO2Et
Na Na OEt 0.5H2
OEt
O O
H
OEt
HOEt
OEt
O O
HOEt
OEt
O ONa Cl
OEt
O
Na Cl
OEt
OONa Na
O
CO2Et
O
OEt
Weniger wichtige meso,GF,
da 14 kcal/mol
Ester-Mesomerie fehlt!!!
13-A2 4-Oxopentancarbons?ureethylester aus
Acetylbernsteins?urediethylester (13-A1)
O
CO2Et
OEt
O
O CO2EtH3BO3
O
CO2Et
O
OEt B
OH
OH
OH
δ+
CO2Et
O
OEt
O
B
HO OH
OH
δ+
δ?δ?δ?
CO2Et
O
OEt
O
B
HO OH
OH
δ+
δ? O
OEt
O
B
HO OH
OH
EtO2C
OH2
~H
O
O
O
B
HO OH
OH
EtO2C
OH
H
Et
H3BO3
HOEt
O
O
OH
O
O
Et
H2O
O
O
O
Et
O
O
H
OH
O
O
Et
OH
O
O
Et
O
O
O
Et
CO2
13-A3 Sorbins?ure aus Malons?ure und Crotonaldehyd
13-A3
CHO CO2H
+
Pyridin,DO
HO
HO
O
O
OHHO
O
H H N
O
OH OH
O
H
O
OHOH
O
H
N
H
H
H
O
H
O
OH OH
O
H
N
H
H
H
O OH
OH
OHO
H
N
H
H
HO OH
OH
OHO
N
N
H
H
HO
OH
O
OH
O
N
H
OH
H
H
O
O
HO
OH
H CO2
H
H
O
O
H
H
~H
H
H
H
H
O
O
H
H
H
H
H
H
O
O
H
H
H
13-A4 3-Hydroxy-2-methylpentanal aus Propionaldehyd
13-A4
CHO
OH
CHO KOH,MeOH
H
O
H
H
H
O
H H
O
H
H
O
H
O
H
K
KH
H3O
H2O
H
OHO
H
OH O
=
OH H2O
13-B1 5-(1-Hydroxy-2-phenylethyliden)-2,2-dimethyl-1,3-
dioxan-4,6-dion aus Meldrums S?ure (9-C4) und
Phenylessigs?urechlorid
O
O
O
O
+
O
O
O
O
OH
Cl
O Pyridin
CH2Cl2
O
O
O
O
H
H N O
O
O
O
H
H
N
Cl
O
O
O
O
O
H
Cl
O NH ~H
N
O
O
O
O
H
Cl
OH
N
O
O
O
O
Cl
OH
N
H
~H3O
H2O
H-Cl
N
O
O
O
O
OH
13-B2 3-Oxo-4-phenylbutters?uremethylester aus 5-(1-
Hydroxy-2-phenylethyliden)-2,2-dimethyl-1,3-dioxan-4,6-
dion (13-B1)
13-B1 13-B2
O
O
O
O
OH
MeOH,?
O
OMe
O
O
O
O
O
HO
MeOH
O
O
O
HO
OH
Me
O
O
OH
O
HO
O
O
~H
O
HO
O
HO O
O
O
O
HO O
O
O
H
OH
O
HO O
O
O
~H
~H
O
O
O
H
CO2
H
O
O
O
H
O
O
O
O
O
HO O
O
H
~H
13-B3 1,2,4,5-Tetraphenylpentan-1,5-dion aus
Desoxybenzoin
Ph
OPh
Ph
O
Ph
O Ph
Ph
CH2O,KOH
13-B3
Ph
O Ph
OH
H
H H
2O
Ph
O Ph
H
K
K O
H
O
Ph
O
H Ph
K
H2O
OH
H
HO Ph
O
H Ph
OH
H2O
H
HO Ph
O
Ph
K
K
OH
Ph
O
Ph
K
Ph
O
Ph
Ph
O
Ph
O Ph
Ph
Ph
O
Ph
O Ph
Ph
+H
13-B4 2-Methyl-3-oxo-pentans?ureethylester aus
Propions?ureethylester
OEt
OEt
O
O O
Na
13-B4
OEt
O
H
H
Na
SET
-H OEt
O
H SET
-H OEt
O
H
OEt
O
H
H2
OEt
O
OEt
O O
OEt
-OEt
OEt
O O
13-C1 2-Oxo-5,6-diphenyl-3-cyclohexen-1-
carbons?ureethylester aus Benzalacetophenon und
Acetessigs?ureethylester
13-C2 3,5-Diphenyl-2-cyclohexen-1-on aus 2-Oxo-5,6-
diphenyl-3-cyclohexen-1-carbons?ureethylester (13-C1)
13-C3 1-Ethyl-2-oxocyclopentan-1-carbons?ureethylester
aus 2-Oxocyclopentan-1-carbons?ureethylester
13-C4 3-Ethyl-2-oxocyclopentan-1-carbons?ureethylester
aus 1-Ethyl-2-oxocyclopentan-1-carbons?ureethylester (13-
C3)
13-D1 1-Phenyl-1-penten-3-on aus Benzaldehyd und
Ethylmethylketon
13-D2 6-Methyl-5-hepten-2-on aus Citral
13-D3 Curcumin aus Vanillin und Acetylaceton
13-D4 Dimedon aus Mesityloxid und
Malons?urediethylester
13-E1 Indan-1,3-dion aus Phthals?urediethylester und
Essigs?ureethylester
13-E2 (+)-3-(Trifluoracetyl)campher aus (+)-Campher und
Trifluoressigs?ureethylester
13-E3 3-Cyclopenten-1,1-dicarbons?ure aus
Malons?uredimethylester und cis-1,4-Dichlor-2-buten
13-E4 4-Hydroxy-4-methyl-2-pentanon aus Aceton
13-F1 (3-Oxocyclohexyl)essigs?ure aus
Malons?urediethylester und 2-Cyclohexen-1-on
13-F2 3-(Methylthio)-1-(phthalimido)propan-1,1-
dicarbons?urediethylester aus
(Phthalimido)malons?urediethylester (2-C1)
13-F3 rac-Methionin 3-(Methylthio)-1-
(phthalimido)propan-1,1-dicarbons?urediethylester (13-F2)
13-F4 7,16-Dioxodocosandis?ure aus 1,10-Bis(2-
oxocylohexyl)-1,10-decandion (12-F3)
