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)
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)
