机理

6-A1󰀀Pivalinsäurepyrrolidid󰀀aus󰀀Pivaloylchlorid󰀀und󰀀Pyrrolidin󰀀6-A2󰀀tert-Butylcyclohexenylketon󰀀aus󰀀Pivalinsäurepyrrolidid󰀀(6-A1)󰀀und󰀀dem󰀀von󰀀1-Bromcyclohexen󰀀(4-A3)󰀀abgeleiteten󰀀Grignard-Reagenz󰀀󰀀

OClCHCl3,󰀀󰀀PyridinMg󰀀BrON6-A1

6-A2NHOClClNH-HNO6-A1

Mg󰀀BrMgBrONO-Cl+HONH-H󰀀󰀀󰀀󰀀󰀀,OHCl6-A2

-NHONH󰀀󰀀

󰀀

6-A3󰀀(R)-3-Hydroxybuttersäuremethylester󰀀aus󰀀Poly-[(R)-3-hydroxybuttersäure]󰀀󰀀

HOnOOHHOnOOHOHnMe

~HMeOH󰀀󰀀

6-A4󰀀󰀀󰀀

OnC5H112-Methyl-2,5-decandiol󰀀aus󰀀-Pentyl--butyrolacton󰀀

nC5H11OHMeMgIO6-A4

󰀀

HOO-

HOHHOHOHHHOOClCH2CH2Cl󰀀/󰀀CH3OH

OHOOMeH2SO46-A3

OOHOOH2

nMe-H2O

n-1OHOOMe󰀀

MeMgInC5H11OnC5H11OOMeOMgI

MgI

O

nC5H11

nC5H11OMeMgIOOMgIMgI

+NH4Cl-2󰀀NH3,-2󰀀MgICl

nC5H11

HO

OH󰀀󰀀

6-B1󰀀󰀀

󰀀

Fluoren-9-carbaldehyd󰀀aus󰀀Fluoren󰀀

CHO

NaH,󰀀HCO2Et

6-B1

󰀀

H

H

NaH-H2

NaOHOHHOEt-HOEt

-H

OHHOH

OEt

OEt󰀀󰀀

󰀀

6-B2󰀀6-B3󰀀B2)󰀀󰀀

OOHSebacinsäuredichlorid󰀀aus󰀀Sebacinsäure󰀀

Sebacinsäurediamid󰀀aus󰀀Sebacinsäuredichlorid󰀀(6-OOOSOCl2(CH2)8

Cl

(CH2)8

ClOOH2N6-B3

(CH2)8

󰀀󰀀

OOClHOOO(CH2)8OOSOH󰀀+

OHO(CH2)8ClOClOHO(CH2)8O-HCl󰀀/󰀀-SO2

OOOanalogCl

Cl

(CH2)8

O(CH2)8

OOH(CH2)8HONH26-B2

NH3󰀀(wäßrig)󰀀

O

ClSOCl

+Cl

HSOHOHOSCl+Cl+H

Cl

󰀀

OOONHO3NH3Cl

(CH2)8ClCl

(CH2)8ClOOOO-󰀀HClCl

(CH2)8

NHCl

(CH2

2)8

NH3

analog

OOH2N(CH2)8NH2

󰀀󰀀

6-B4󰀀Octanal󰀀aus󰀀N-Formylpiperidin󰀀und󰀀dem󰀀Grignardreagenz󰀀aus󰀀1-Bromoctan󰀀(2-A1)󰀀󰀀󰀀

OHept

Br

1)󰀀󰀀󰀀󰀀Mg,󰀀󰀀Et2OHept

2)

ON6-B4

󰀀

Cl

󰀀

HeptBr

Mg

Hept

(SET)

MgBr

HeptMgBrHHeptNONMgBrOH

Hept

O

HONHMgBr-󰀀󰀀

6-C1󰀀󰀀󰀀

CO2HHOHN

Hept󰀀

Acetylsalicylsäure󰀀aus󰀀Salicylsäure󰀀

O

OH2SO4

O

CO2H

OAc6-C1

󰀀

CO2HHOHOOOCO2H

CO2HOOHOO

~H

CO2HOOOHOOAc6-C1

-󰀀HOAc

󰀀󰀀

6-C2󰀀Sebacinsäuremonomethylester󰀀aus󰀀Sebacinsäuresäuredimethylester󰀀6-C3󰀀10-Methyl-10-hydroxy-undecansäure󰀀aus󰀀Sebacinsäuremonomethylester󰀀(6C2)󰀀6-C4󰀀Sebacinsäureethylmethylester󰀀aus󰀀Sebacinsäuremonomethylester󰀀(6-C2)󰀀󰀀

O

MeO

O(CH2)8

O

1)󰀀Ba(OH)2OMe2)󰀀H3OMeO

(CH2)8

OH6-C2

OH

O(CH2)8OHO

MeO

O

1)󰀀󰀀Cl-CO-OEt(CH2)8OEt

2)󰀀󰀀EtOH

6-C4

1)󰀀󰀀MeMgI2)󰀀󰀀NH4Cl/H2O6-C3O

󰀀

󰀀

󰀀

O

MeO

O(CH2)8OMeOHMeO

O

OOH(CH2)8OMeO

MeO

O(CH2)8OO

-HOMe

MeO

+

O(CH2)8OHOMe+HO

MeO

O(CH2)8

OH6-C2

󰀀󰀀󰀀

O

HOMe

MgIO(CH2)8OMe6-C2

+NH4

Me-CH4MgIO

O

OMgI(CH2)8

OMe

󰀀

/-NH3

󰀀󰀀󰀀

󰀀

OO

O(CH2)8-HOMeOO

OMgI(CH2)8OMeHMeMgIOOO(CH2)8

H

OHO(CH2)8OH

6-C3

󰀀󰀀󰀀󰀀󰀀󰀀󰀀

O

MeO

(H2C)8

O

OH6-C2

ClOOEt+󰀀NEt3-󰀀HNEt3

MeO

O(H2C)8

O

O󰀀

O

MeO

(H2C)8ClOOOOEt

MeO

O(H2C)8

O

OOOEtCl󰀀

󰀀

O

MeO

(H2C)8OOClOOEtMeO

O(H2C)8OOCl+

OOEtEtOH-󰀀CO2/OEtO

MeO

(H2C)8

OOEtH-H

MeO

O(H2C)8OClOHEtO

MeO

O(CH2)8OEt

6-C4

󰀀󰀀

6-D1󰀀(S)-Hydroxybernsteinsäuredimethylester󰀀aus󰀀(S)-Äpfelsäure󰀀󰀀

O󰀀

austauscher)

HOOOHOOHHOMeOHH+󰀀(Ionen-MeOOOMe6-D1

󰀀

OHOOHOHOOH2HOOHOHOOMe

-H2O

OHHOOMeOHOH~H

-HOHHOOHOHOCH3OHOHHOOHOHOOHMeOHOOMeOOHOMeOOMeOOH󰀀

󰀀

6-D2󰀀1-(Phenylacetyl)imidazol󰀀aus󰀀Phenylessigsäure󰀀und󰀀1,1‘-Carbonyldiimidazol󰀀󰀀

OOOH

NNN

NON

N6-D2

ONNNOOHNOOO+NNNNH

OONOOOONHNNN

NNHN

󰀀

NNN

ONHN

O

O

NN~HOONOH󰀀

󰀀

HN

-CO2/󰀀-N

NN

O

󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

6-D3󰀀Benzylethylketon󰀀aus󰀀1-(Phenylacetyl)imidazol󰀀(6-D2)󰀀und󰀀Ethylmagnesiumbromid󰀀󰀀

NNO

EtMgBrO

6-D3

NNOEtMgBrEtO

NN

MgBrH

EtO

ON

NH

NNHMgBr󰀀󰀀

󰀀

6-D4󰀀Fumarsäure-tert-butylethylester󰀀aus󰀀

Fumarsäuremonoethylester,󰀀tert-Butanol󰀀und󰀀DCC󰀀󰀀

COOH

COOtBu

󰀀t-BuOHEtOOCNCNEtOOC6-C4

OOHEtOOCEtOOCOONCNN+CHN󰀀

OOEtO2CNCNHOO󰀀

NHNEtOOCHOOEtO2C

OONHNH~HEtO2C

OOOH

NNH

󰀀󰀀󰀀

󰀀

O

EtO2C

O

+

O

NHNH

󰀀󰀀

6-E1/2󰀀1-Chlor-2-methyl-1-(piperidin-1-yl)propen󰀀aus󰀀iso-Buttersäurepiperidid󰀀󰀀

ONClOClOCl

ClN

󰀀

ClNEt3N6-E1/2

ClClOClONOOClONOON󰀀

󰀀

OOOClNClClOONOCl-CO2/-CO

ClHClNEt3N-HEt3NClN󰀀󰀀6-E3󰀀N-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)󰀀󰀀󰀀

OHO󰀀

BocNHH3C1)󰀀ClCOOCH32)󰀀CH3ONHCH3

BocNHONOCH3

CH3CH36-E3

OBocNH6-E4

CH3

[Li*NH2CH2CH2NH2]󰀀

󰀀

OOOOOMeClOH3COClH3C-CO2/-HOMe

H3CMeNHOMeBocNHOClMe-ClONHCH3OMeBocNHNHCH3OMeMe

-HBocNHCH3

OOCNH3CH36-E3

NH2

OLiNBocNHONOCH3Li*NH2CH2CH2NH2

BocNHOCH3

CH3CH36-E3

CH36-E3

H

OOBocNH6-E4

CH3

BocNHHOCH3NCH3OBocNHHOBocNHClOMeBocNHH3CHOOOMeBocNH+Cl+HNH2

󰀀

6-F1󰀀L-Phenylalaninmethylester-hydrochlorid󰀀aus󰀀L-Phenylalanin󰀀󰀀

PhPhSOCl2/MeOH

H3NClOPhH3NCO2OMe6-F1

PhH3NOOClSOClH3NOOSClOClPhPhCl

H3NClO-SO2

H3NOOOSClClMeOHPhCl

H3NMe

OClOH

-HClH3NPhPhOMe

OClH3NOCl

OMe󰀀

󰀀

6-F2󰀀󰀀N-(Benzyloxycarbonyl)-L-asparaginsäure󰀀aus󰀀L-Asparaginsäure󰀀6-F3󰀀󰀀N-(Benzyloxycarbonyl)-L-asparaginsäureanhydrid󰀀aus󰀀N-Benzyloxycarbonyl-L-asparaginsäure󰀀(6-F2)󰀀6-F4󰀀󰀀N-(Benzyloxycarbonyl)-aspartam󰀀aus󰀀N-(Benzyloxycarbonyl)-L-asparaginsäureanhydrid󰀀(6-F3)󰀀und󰀀L-Phenylalaninmethylester󰀀(6-F1)󰀀󰀀󰀀

ONH2

OHOHOOPh

OONHOOPhH2NO(aus󰀀6-F1)

OMeOOPhNHONHCO2HPhOMeO6-F4

Ac2O1)󰀀MgO/H2O/Et2O2)󰀀PhCH2OCOCl3)󰀀HCl

OPh

OO

ONHOHOH6-F2

ONH2

OHOHOMgO-H2O

H2NOOMgOOPhOOCl󰀀

󰀀

OPh

O

ClNH2

OOMgOO-HPh

OOClNHOOMgOOOPh

OO

ONHOHOH6-F2

+2H2O-Mg(OH)2

PhO

O

ONHOMgOOOPh

OO

ONHOHOHOOOPh

OONHOOHOHOOOO

~HOPh

OO

ONHOHOO-󰀀HOAc

Ph

OONHOOHOOOOOH󰀀

󰀀󰀀󰀀

OHPh

ONHO

OOOO~HPh

ONHO

OOOOH

OOPh

OO

O6F-3

NHO-󰀀HOAc

Ph

OO

ONHOOOH

OPhOPh

OO

ONHOH2NOOMePh

OO

ONHONH2OPhOMeO~H

MeOPh

Ph

ONHO

ONHOOOONHPhOMeOPh

H

OO

NHOHO6F-4

󰀀

7.󰀀󰀀Umwandlungen󰀀von󰀀Carboxylverbindungen󰀀und󰀀Nitrilen󰀀ineinander󰀀󰀀󰀀

7-A1󰀀Malonsäure󰀀aus󰀀Cyanessigsäure󰀀󰀀

CO2H1)󰀀NaOH2)󰀀CaCl2

CO2HCl

Ca2

CO2HCNCO2

CO2HCO2HCO2+H2O-OH

NNa

HN

CO2+CNNaOHCOHCOH

+OH

-H2O

CO2CO2CO2OHCONH2

HOCONH2

+H2O

C-OHONH+H2O

-OH󰀀󰀀󰀀

󰀀

CO2CO2CO2OHCONH3

∆2)󰀀CaCl2

-NH3CO

OH

+OH󰀀/󰀀-H2OCO

OH

CO2HCO22󰀀HCl-CaCl2

Ca2+

CO2HCO

O󰀀󰀀

7-A2󰀀Glycinethylesterhydrochlorid󰀀aus󰀀1,3,5-Tris(cyanmethyl)-1,2,3,4,5,6-perhydrotriazin󰀀(9-A3)󰀀󰀀󰀀

NCN󰀀

CNHCl󰀀gasEtOH󰀀abs.󰀀

NEtO2CNCN

NH3Cl7-A2

󰀀

HNCN

ONNCNHNCOEtH2O~HNCNCOEtNH2

NNC

-NH3,NH3

NNC

NC

H2CH

OH

NN

NCCOEt

-HNCNC

+HOHHHNNC

H

NCNC3xH3NCl

OCOEt

+

NNOCOEtNONNCNN

COEtNCNC

HH2ONNCOEtNC

HN

NOCOEt

NC

3x

OH

H

N-HO+HHNONNNNNNCNCNNCNCNHEtOHNCN

NCNC

HOEtNCN

~HNH

NOCOEt

+

OH

HH

󰀀

7-B1󰀀󰀀󰀀

Sebacinsäuredinitril󰀀aus󰀀Sebacinsäurediamid󰀀(6-B3)󰀀

OH2N(CH2)8ONH2SOCl2NC

(CH2)8CN7-B1

O

OH2N(CH2)8ONH2+OClSCl-ClH2NSNH2O(CH2)8OCl

O-SO2󰀀/󰀀-Cl

(CH2)8SNH-HClOOH2NNHOH2N(CH2)8-HH2NO(CH2)8+SOCl2,󰀀󰀀󰀀󰀀-2HCl󰀀/󰀀-SO2NNC

(CH2)8CN󰀀󰀀

7-B2󰀀(9-B3)󰀀󰀀󰀀

7.󰀀B-2

󰀀

Pentaacetyl-D-gluconsäurenitril󰀀aus󰀀D-Glucoseoxim󰀀

Ac2OHOCHNOHOHNaAc,󰀀HOAcAcOAcOAcO󰀀

HOOHOHOAcCNOAc󰀀

(1)COHHHO(1)HON

HOOHCHON+2

OHO

~H

OOHCOOOOOOHCHOO~HOH

OHOHOHOOHCHOOHC󰀀󰀀

7-C1/2󰀀Methylbernsteinsäure󰀀󰀀aus󰀀3-Cyanbutansäure󰀀󰀀󰀀󰀀

Ba2CO2Et

NaCNEtOH,󰀀H2ONCCO2H

Ba(OH)2󰀀H2O,󰀀∆󰀀

HOOH

AcOAcOAcOOAcCNOAcAcON

O2CCO2HNO3HON

HOOHOOHOH(2)OO(2)OHOOHOHOHOHOHOHONH+OOHON

-CH3COOH

󰀀

HO2CCO2H

7-C1/C2

󰀀

OCOEtCNOCOEt+H2O-OHHCNOCOEtCNOCOEtOHCNOCOEtOH-OEtCN

HO

NHCCO2

H2O-OHHONCCO2

+OH+OH,󰀀-H2OCNCO2HHOH

+OHO

C

NH2CO2+OH󰀀󰀀󰀀󰀀-H2OOCCO2NH+H2O-OHOCCO2NH2OHO

COBa2+

+OH-H2O

O

COHCO2+H2ONH3CO2-OH∆-NH3

OCCO2+HNO3

O

COHCO2H

󰀀

󰀀

7-D1󰀀(1-Naphthyl)acetonitril󰀀aus󰀀1-(Chlormethyl)naphthalin󰀀(5-D4)󰀀7-D2󰀀(1-Naphthyl)acetamid󰀀aus󰀀(1-Naphthyl)acetonitril󰀀(7-D1)󰀀󰀀

Cl

NaCNEtOH,󰀀H2OOCN

7-D1󰀀b)

NH2HCl󰀀/H2O7-D2

󰀀󰀀󰀀󰀀

ClCN+󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀Cl

SN2CN

󰀀

󰀀󰀀󰀀󰀀ClOH2C

N+H󰀀󰀀󰀀ClCNH+󰀀󰀀󰀀󰀀ClNH󰀀󰀀󰀀󰀀ClNH2COHCHCl󰀀󰀀󰀀󰀀󰀀󰀀󰀀+OHH2OCNH

󰀀󰀀󰀀

󰀀

NH2-HClOCONH2

󰀀󰀀7-E1󰀀󰀀󰀀

OHHO󰀀

D-Gulonsäure--lacton󰀀aus󰀀D-Xylose󰀀

OHCNHOOHOHOH󰀀1)󰀀Ba(OH)2*6󰀀H2O

OOCHOOHOHNaCNNH4Cl2)󰀀H2SO43)󰀀kristallisierenaus󰀀MeOCH2CH2OH

OOHOHOHOHHOOHCHO+NH4-NH3HOOCNOHCHOOHOHNOHOHOHOHOHHOOHCHOOHOHHONHOHH2O-OHHOOHCOHOHNOH+OH+OH-H2OOOHCHOOHOHNHOH+H2O-OHHOOOHCOHOHNH2OHOOHOOHOHCNH3OH~HHOHOOCNH2OHOHOH󰀀󰀀󰀀

󰀀

-NH3

OHOCOOH󰀀󰀀󰀀7-E2󰀀󰀀󰀀

OHOH󰀀

Pyridin-3-carbonitril󰀀aus󰀀Pyridin-3-carboxamid󰀀

ONH2

N

Cl3CCOCl󰀀󰀀/󰀀󰀀NEt3CH2Cl2

ON

CN7-E2

ONH2N+ClOCCl3

NOCNH2ClCCl3OOCCClNH23NOOCNHCCl3

Cl-HClNH+-CCl3

N

-HCCl3

-CO2

NCNN

󰀀󰀀󰀀󰀀󰀀

󰀀

7-F1󰀀󰀀(9-F4)󰀀󰀀󰀀

-Phenylalanin󰀀aus󰀀2-Amino-2-phenylpropionitril󰀀

H2N

CN

󰀀1)󰀀󰀀HCl󰀀/󰀀H2O󰀀/󰀀∆H3NCO2

7-F1

2)󰀀󰀀Pyridin(9.󰀀F-4)

H2NCNH3N2HCl-2ClCNHH3NH2OOH2CNH~HOHH3NCNH3OH~HH3NOH2CNH2OHH2OH3NCNH2OHH3NOH+COH

H3NNH3

CO2

-NH4Cl

󰀀

󰀀

8.󰀀󰀀Umwandlungen󰀀von󰀀Kohlensäurederivaten󰀀und󰀀Heterocumulenen󰀀ineinander󰀀󰀀󰀀

8-C3󰀀Natrium-(S)-2-amino-6-guanidinocapronat󰀀aus󰀀S-Ethylthiouronium-bromid󰀀und󰀀L-Lysin󰀀󰀀

SH2NNH2󰀀EtBrH3NSEtNH1)󰀀󰀀NaOH2)H2N

NH34HN

HNNH2NH2

4CO2NaBrCO2

8-C2

SH2NNH2EtBrH2NSEtNH2H3NSEtNHBrBrNH3H2NSH2N4CO2EtNH2NH3

4Br-SEtH2NNH2BrNH3H2NCO2

H2N4CO2-HHN

HNNH2NH2

4CO2Na-H-H󰀀

󰀀

8-D3󰀀3-[3-(Dimethylamino)propyl]-1-ethylcarbodiimid󰀀aus󰀀Ethylisocyanat󰀀und󰀀3-Dimethylamino-1-propylamin󰀀󰀀

OCNEt

1)HN2NMe22)󰀀󰀀󰀀󰀀p-TsCl,󰀀Et3N

NCNEtNMe28-D3

H2N

NMe2+NEt3

HNEt3

+

HNNMe2NEtCOClCH3

EtN

OCOSOCH3+ClSOOHN-ClEtNCNMe2N

NMe2+NEt3-HNEt3,󰀀󰀀󰀀-OTsEtNCHNNMe2OTs󰀀󰀀

8-E3/4󰀀(4-Methoxyphenyl)isothiocyanat󰀀aus󰀀p-Anisidin󰀀󰀀

NH2

MeO

CS2Et3N

MeO

HNSEtNH3

8-E3/4

SClCO2EtEt3N

MeO

NCS

󰀀

󰀀

󰀀

NH2MeO

SCS

(1)OEtSMeO

H2NS

SMeO

H2NS8-E3

S

H

EtOOSSNOMe(2)OClHNS

OMe

Et3N

-EtNH3

EtNH3

Et3N-Et3NH

NCS

+

MeO

EtO

O

SEt3NHEtO

O

SH

EtHOOSEtOH󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀+

SCO

󰀀󰀀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)󰀀󰀀

O

OO

Ot-Bu

O

O

NHNH

Ot-Bu8-F2

󰀀

t-BuO

H2N

NH2

t-BuO

BCl3,󰀀NEt3OCN

8-F3

NCO

󰀀

󰀀

Boc-Anhydrid!Ot-BuOH2N

NH2

OOOt-BuH2N

OOt-BuNH2OOOt-Bu-OO

O

H2N

NH

Ot-Bu

-HH2N

NH2OOt-Bu

Ot-Bu

O

t-BuO

NH

NH

OOt-Bu

8-F2

BCl3

t-BuO

ONHNOBCl3Ot-Bu-HNEt3,-BCl3,-Ot-Bu

H+NEt3O

dto.

OCN

NCO

t-BuO

NH

NCO󰀀

󰀀

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󰀀󰀀󰀀

OH

C

H

OH

C

H

NH2HHNH3

-󰀀H󰀀󰀀󰀀󰀀󰀀󰀀

NaCNNCNNCN

N

CH3COOH/󰀀NH4Cl

CN

9-A3

NHNH4OH33

HOHH

C+󰀀󰀀󰀀󰀀NHHH

~H

NHNH22

HOH2

H3NHHH󰀀

H2NNH2HOHHH2NNH2

OH

~HH2N

NHOH2-󰀀H2O

HOH2NHOHN

2

NH

HH-HH2NH3NNHH3N

H2NNHCH2

~HHNH2OH2NNH-󰀀H2OHN

NH2

NH

-󰀀HHN

NHNHHOHHN

NNC

NH

HNNHN~HHN

NHO

NHH

CNH2Oanalog

NCNNNC

NCN

󰀀󰀀󰀀󰀀

9-A4󰀀1,2:5,6-Diisopropyliden-D-mannit󰀀aus󰀀D-Mannit󰀀

OHOHHOOHOHOHSnCl2MeOOMeOOHOOHOO9-A4MeMeOOMe+󰀀SnCl2

OSnCl2OMeMeO+󰀀MeOSnCl2

OHOHHOOHOHOHMeOHOOHOHOOHOHHOMe~H

OHOHHOOHOHO-󰀀MeOH

OHOHHOOHOHOOMeHOHOHHOOHOHO-󰀀HOHOHHOOHOOOOHOOHOO󰀀

9-B3󰀀󰀀󰀀

HOHOHOD-Glucoseoxim󰀀aus󰀀D-Glucose󰀀󰀀

NH2OH

OOHOHOHCHOOHHOHOHOHOHOHO65󰀀°C

OHCHNOHOH9.󰀀B-3

HOHOHOOHOOHHNH2OHHOHOHONH2-OHOHHOHO~H

HOHOHOOHOHHONOH

-󰀀H2OHOHOOHOH2OHHN-OHHOHOHOOOHHNOH

󰀀󰀀󰀀󰀀󰀀󰀀

9-B4󰀀

󰀀

Chinoxalin󰀀aus󰀀o-Phenylendiamin󰀀und󰀀Glyoxal󰀀󰀀

󰀀

NH2

+

OO

1)󰀀

NaHSO3,󰀀H2O2)󰀀Na2CO3

NN

9.󰀀B-4

NH2

NH2+NH2HOOH2NNH2

OHHO~H

HNNH2OHNNH2OH2HO-󰀀HNNH2Oanalog

NN

󰀀󰀀󰀀󰀀

9-C4󰀀

󰀀

Meldrum’s󰀀Säure󰀀aus󰀀Aceton󰀀und󰀀Malonsäure󰀀󰀀

OOH

O

OH

Me2C=O,󰀀Ac2O,󰀀H2SO4O

OOO

9-C4

OHOHOOOOOOHOOHOOHOOHOOHOOOH+

-󰀀HOAc

OHOOHO

OH

OOOOOOHOOOHO

OH

OOHO

O󰀀

󰀀

OH

OO

O

HOO-HOAc

OHO

O

O

-H

OHOOOHOOO

O

O

O󰀀󰀀󰀀

󰀀

󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

9-D4󰀀

󰀀

2,5-Dimethylpyrrol󰀀aus󰀀2,5-Hexandion󰀀󰀀

(NH4)2CO3OO

∆

NH

9-D4

NH4OO

OOH+NH3

󰀀

NH2

OOH2~H

O

NH3OH

-H2O

-HO

NH2

O

NH

ONH2ONH2~H

󰀀󰀀󰀀󰀀

󰀀

+HH2ONHHONH

-H2O

HNH-HNH

󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀󰀀

9-F4󰀀󰀀󰀀

O

2-Amino-2-phenylpropionitril󰀀aus󰀀Acetophenon󰀀󰀀

NaCN,󰀀NH4ClH2N

CN

9-F4󰀀

O

OHNH4OH2NH2

~H-H2O

NH2CN󰀀

+NH3

OH

NH3

H2N

CN

󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

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󰀀󰀀󰀀

󰀀󰀀NaBH4OOH10-A3

Angriff󰀀an󰀀der󰀀weniger󰀀konkavenSeiteOHHHOOH󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀󰀀󰀀󰀀󰀀󰀀󰀀

10-A4󰀀syn-2,2-Dimethyl-4-phenyl-3-pentanol󰀀aus󰀀2-Phenylpropionaldehyd󰀀󰀀󰀀

O1)󰀀t-BuMgBr2)󰀀HCl,󰀀H2O

Ract-BuOHHRac10-A4

BrMgOONu-MeHt-BuHHOPhAngriff󰀀von󰀀vorneRac󰀀󰀀󰀀󰀀󰀀

10-B1󰀀(6-B1)󰀀󰀀

󰀀

(9-Fluorenyl)methanol󰀀aus󰀀Fluoren-9-carbaldehyd󰀀󰀀

OOH

NaBH4

10-B1

OH

OH

H10-B2󰀀Cyclohexylcarbinol󰀀aus󰀀Formaldehyd󰀀und󰀀dem󰀀Grignardreagenz󰀀aus󰀀Chlorcyclohexan󰀀󰀀

󰀀

󰀀

MgCl

O

1)

CH2OH

HH

2)󰀀󰀀H2O󰀀/󰀀H2SO4

HOMgClOCHHHH10-B2

󰀀󰀀󰀀󰀀󰀀

󰀀

10-B3󰀀endo-1,3,3-Trimethylbicyclo[2.2.1]heptan-2-ol󰀀aus󰀀(-)-Fenchon󰀀󰀀󰀀

1)󰀀EtMgBr

O2)󰀀HCl,󰀀H2O

10-B3

OHHHOMgBrHOH2CCH2sechsgliedrig

HOMgBr10-B4󰀀anti-2,2-Dimethyl-4-phenyl-3-pentanol󰀀aus󰀀2,2-Dimethyl-4-phenyl-3-pentanon󰀀󰀀󰀀

󰀀

ONaBH4

OHt-But-BuRacRac10-B4

OHOHNu-Met-But-But-BuHPhO󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀

10-C1/2󰀀Bis[4-(dimethylamino)phenyl]phenylmethanol󰀀und󰀀Malachitgrün󰀀aus󰀀4,4’-Bis(4-dimethylamino)benzophenon󰀀󰀀󰀀

MgBr

O

1)

2)󰀀󰀀NH4Cl,󰀀H2O

OH

Me2N

Me2N

NMe2

Me2N

NMe2

10-C1

HBF4,󰀀Ac2ONMe2

10-C2󰀀a)

󰀀

BF4

Me2NOBrMgMe2NMe2NNMe2

Me2NNMe2

O

Me2N

NMe2

NH4Cl

H-H2OOHMe2NNMe2

󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

10-C3󰀀endo-1,2,3,3-Tetramethylbicyclo[2.2.1]heptan-2-ol󰀀aus󰀀(-)-Fenchon󰀀󰀀󰀀

1)󰀀MeMgI

10-C3

OHO2)󰀀󰀀HCl,󰀀H2O

H3CMgIAlkylierung,󰀀da󰀀kein󰀀β󰀀H

OO󰀀󰀀󰀀󰀀

󰀀

󰀀󰀀󰀀

10-C4󰀀syn-󰀀und󰀀anti-2-Phenyl-3-pentanol󰀀aus󰀀2-Phenylpropionaldehyd󰀀󰀀󰀀

O1)󰀀CH3MgI2)󰀀HCl,󰀀H2OCH3OHOH+

CH3HRacRac7󰀀󰀀󰀀󰀀󰀀󰀀󰀀:󰀀󰀀󰀀󰀀󰀀󰀀󰀀3Rac10-C4

OH3CHMgICH3OHaupsächlich󰀀Cram

󰀀

󰀀

󰀀

10-D1/2󰀀1-Phenyl-3,4-tetrahydro-1-naphthol󰀀und󰀀3,4-Dihydro-1-phenyl-naphthalin󰀀aus󰀀a-Tetralon󰀀󰀀󰀀

O

1)󰀀PhMgBr

HO

2)󰀀󰀀NH4Cl,󰀀H2O

10-D1

10-D2󰀀a)

󰀀󰀀(CH3CO)2OOONH4ClBrMgOOOOOOOHOOO󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀

OO

OHOE1

H-󰀀H

󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

10-D3󰀀exo-2-Ethyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol󰀀aus󰀀(+)-Campher󰀀󰀀

1)󰀀EtMgBr

OHO󰀀2)󰀀NH4Cl,󰀀H2O

10-D3

OEtOMgBr󰀀

10-D4󰀀anti-󰀀und󰀀syn-2-Phenyl-3-butanol󰀀aus󰀀2-Phenyl-3-pentanon󰀀󰀀󰀀

ONaBH4

MeOHOH+

MeMeRacRac7󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀:󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀3Rac10-D4

OHMeOHMe󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀

10-E1/2󰀀Vinyl-b-ionol󰀀und󰀀Anhydro(vinyl-ß-ionol)󰀀aus󰀀b-Ionon󰀀(3-E4)󰀀󰀀󰀀

O1)

MgBr

OH󰀀2)󰀀NH4Cl,󰀀H2O

10-E15n󰀀H2SO410-E2󰀀a)

4h󰀀RT

󰀀

OMgBrO

NH4ClH2OHOH2HOH-H2O-H󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀

10-E3󰀀󰀀

(+)-Isoborneol󰀀aus󰀀(+)-Campher󰀀󰀀

NaBH4OHO10-E3

HOOHClOH󰀀

󰀀

10-E4󰀀trans-󰀀und󰀀cis-4-tert-Butylcyclohexanol󰀀aus󰀀4-tert-Butylcyclohexanon󰀀󰀀󰀀

H

O

NaBH4

t-Bu

OH

OH

H

t-Bu

+

t-Bu

󰀀8󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀:󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀210-E4

HHOHHOO

+

t-Bu

H

t-BuHHt-Bu󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀

10-F1󰀀threo-󰀀und󰀀erythreo-1-(3,4-Dihydro-2H-pyran-2-yl)-1-propanol󰀀aus󰀀3,4-Dihydro-2H-pyran-2-aldehyd󰀀󰀀󰀀

EtMgBr;HCl,󰀀H2O

OOHOO

RacORacOHHEt

HEtHOHOMgOOMg

MgBrOOOOOO󰀀

󰀀

10-F2󰀀cis-1-Ethinyl-4-tert-butylcyclohexanol󰀀aus󰀀4-tert-Butylcyclohexanon󰀀󰀀󰀀

O

NH2NH2Li

t-Bu

t-Bu

OH

HHONH2

LiHHNH2

ONH2

Li

NH

HOH󰀀󰀀󰀀󰀀󰀀

󰀀

10-F3󰀀󰀀

(+)-Isoborneol󰀀aus󰀀(+)-Campher󰀀󰀀

1)󰀀i-BuMgBr

OHO󰀀2)󰀀NH4Cl,󰀀H2O

H

HOMgBr

OOHH3CH3C󰀀

10-F4󰀀cis,cis-3,5-Diphenylcyclohexanol󰀀aus󰀀cis-3,5-Diphenylcyclohexanon󰀀󰀀󰀀

ONaBH4

PhOHPhPhOHPhOPhH2O

PhPh󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

11.󰀀Praktikumswoche󰀀󰀀

Ph10-F4

PhOHPh󰀀

󰀀󰀀

11.󰀀Umsetzung󰀀von󰀀Heteroatom-stabilisierten󰀀C-Nucleophilen󰀀mit󰀀Aldehyden󰀀bzw.󰀀Ketonen󰀀󰀀󰀀󰀀

11-A1󰀀trans-4-Bromzimtsäureethylester󰀀aus󰀀4-Brombenzaldehyd󰀀und󰀀Triethylphosphonacetat󰀀󰀀󰀀

O

CHO

EtO

OEtBr

O

OEtPCO2Et

NaH,󰀀THF

Br

11-A1

O

O

OEtPNaH-󰀀H2

EtOOOOEtPCHOEtNaOOOEtPEtO

CH2

OEtEtOCHOEt

YlenOCH

Br

OOOP(OEt)2OP(OEt)2

OEtOEtBrOBrO󰀀󰀀󰀀

󰀀

CO2Et

O

OEtPO

OEtBr

󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

11-B1󰀀cis-4-Bromzimtsäureethylester󰀀aus󰀀4-Brombenzaldehyd󰀀und󰀀

(Ethoxycarbonyl)methylphosphonsäurediphenylester󰀀󰀀󰀀

O

O

PPhO

OPh

CO2Et

CO2Et

Br

PhCH2(CH3)2N+OH-,󰀀MeOH

(\"TRITON󰀀B\")

Br

11-B1

O

O

OEtPNaH-󰀀H2EtOOOOPhPCHOPhNaOOOPhPEtO

CH2

OEt

EtOCHOPhYlenOBr󰀀󰀀󰀀

󰀀

OOOP(OPh)2OEtOEtBrOOBrOP(OPh)2

O

OPh

CO2Et

Br

O

OPhP󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

11-C1󰀀1,3-Bis(4-phenylbutadienyl)benzol󰀀aus󰀀Zimtaldehyd󰀀und󰀀m-Xylylen-bis(triphenylphosphoniumchlorid)󰀀󰀀󰀀

O

ClPh3PClPPh3LiOMe,󰀀EtOH11-C1

Ph3PPPh3OMePh3PPPh3

H󰀀

󰀀

󰀀

OOPPh3PPh3

Ph3PPPh3

PPh3

󰀀󰀀󰀀

󰀀

11-D1󰀀3-(3-Methyl-2-buten-1-yl)indol󰀀aus󰀀Indolcarbaldehyd󰀀(5-B6)󰀀und󰀀dem󰀀Instant-Ylid󰀀Isopropylidentriphenylphosphoran󰀀

O

[Me2CHP(C6H5)3Br

+󰀀NaNH2]\"Instant-Ylid\"

11-D1

Me2C

PPh3

HMe2C

PPh3

NH2Me2C

PPh3

+󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀NH3

Ph3POOMe2CPPh3+

O

PPh3

󰀀

11-E1󰀀trans,󰀀E-5,9-Dimethyl-2,4,8-decatriensäureethylester󰀀aus󰀀Geranial󰀀und󰀀

(Ethoxycarbonylmethylen)triphenylphosphoran󰀀󰀀

󰀀󰀀󰀀󰀀

CO2Et

Ph3P

O

CO2Et

11-E1

CO2Et

Ph3P

Ph3PCO2EtOOCO2EtPPh3OPPh3

CO2Et

󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

11-F1󰀀E,󰀀E-2,5,9-Trimethyl-2,4,8-decatriensäureethylester󰀀aus󰀀Geranial󰀀und󰀀

[1-(Ethoxycarbonyl)ethyliden]triphenylphosphoran󰀀󰀀

CO2Et

OPh3P

CO2Et

11-F1

CO2Et

Ph3P

Ph3PCO2EtOOCO2Et

PPh3CO2Et

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󰀀󰀀

O

O

O

+

NH

∆-H2O

N

12-A2

O

1)O2)󰀀HCl

12-A3

Analog󰀀gehen󰀀auch󰀀12-B2/B3,󰀀12-E2/E3󰀀und󰀀12-F2/F3,󰀀allerdings󰀀dort󰀀Protonierung󰀀mit󰀀pTsOH󰀀!!

O

OOO

NH

NHO~󰀀H

OH2N++󰀀H

-󰀀H2OO

OONONNOHH

~󰀀H

󰀀

OOHOHO

OHN-󰀀OHNN

OH2

~󰀀H

OHOO-󰀀HHNOH󰀀󰀀

12-A4󰀀(Acetamido)malonsäurediethylester󰀀aus󰀀Malonsäurediethylester󰀀󰀀

EtO2C

NaNO2

EtO2C

NOH

EtO2C

AcOH/H2O

EtO2C

Ac2O/AcOH

EtO2C

Zn

EtO2C

NH

O

󰀀

12-A4

OEtO2C

HOEtNOH

O

O

EtON

O

N

OEt

O

OEt

-󰀀HOH

OEt

EtO2C

OO

EtO

OOEt

OOEtOOEt

OOEt

O

NH

OEt

eHZnONOEt-󰀀H2OZnSET

-󰀀HO

NOEt

OH2O

N

OEt

OH

󰀀

2󰀀e2󰀀H

󰀀

󰀀󰀀

OOHONH2OEtOEtOOO

OOEt

HOOOEtH

NH2

OEt

OOOONH2OEtOO

O

O

O

HO

OEt

OEt

O

O

OOEt

H

NH

O

O

OEtNH2

O

󰀀󰀀

12-B2󰀀󰀀1-(N-Morpholino)cyclohexen󰀀aus󰀀Cyclohexanon󰀀und󰀀Morpholin󰀀

12-B3󰀀2-Oxocyclohexan-1-carbonsäureethylester󰀀aus󰀀1-(N-Morpholino)cyclohexen󰀀(12-B2)󰀀󰀀󰀀

O

O

O

󰀀

Η+, Toluol,󰀀 ∆

N(-H2O)

+

NH

12-B2

OOO

1)OEt

ClOEt12-B3

Mechanismus󰀀siehe󰀀12󰀀A2/3

2)󰀀2n󰀀HCl

󰀀󰀀

󰀀

O

O

1)

N

Cl

OEt

OO

OEt

2)󰀀2n󰀀HCl

12-B3

OOONClOEtNClOOEtvgl.󰀀12-C4

OO

OEt

󰀀󰀀

12-B4󰀀󰀀

O

󰀀

Phenacylbromid󰀀aus󰀀Acetophenon󰀀󰀀

O

CH3Br2,󰀀AcOH

CH2Br

󰀀

󰀀

O

OHCH312-B4󰀀

OHHHHHC-󰀀HCH2BrBr-󰀀Br

󰀀

O

OHCH2Br

-󰀀HCH2Br

󰀀󰀀󰀀󰀀󰀀

12-C2󰀀2-Methyl-1,3-cyclopentandion󰀀aus󰀀Bernsteinsäure󰀀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)󰀀󰀀

O

O

HO

Cl

O

OOHOO

󰀀

AlCl3

OH

+

O12-C2

O

O12-C3

1)H2NHCO22)󰀀H2SO4ODMF

O󰀀󰀀󰀀

12-C4󰀀

OHHOOHHOOOClOOHAlCl3ClOOH-󰀀HCl

OOOHOOHOHOHOO

O

~󰀀HOHO

HOOH

HO󰀀

OOO󰀀

-󰀀CO2O

OHOOHOHHOOOOOH-󰀀H

O

O

O

HOOOH2NHCO2

󰀀󰀀

OHO2CHHO2CNONOHO~󰀀HOHH2OO2CNHOOHOHO2CHNOH~󰀀HHHOOO2CHO2CHONHNHOHOHOOOOH-󰀀H-󰀀H2OOOOH2NHOHCO2

󰀀󰀀

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)󰀀󰀀

ONH

N

󰀀

OMe

Toluol,󰀀 ∆

(-H2O)

OMe

󰀀󰀀

12-D2󰀀

Ph

O

1)󰀀PhCH2BrOMe

2)󰀀AcOH,󰀀H2O

12-D3

OO

NH

OMeNHOMe

󰀀

~󰀀H󰀀

HN-󰀀H2OOHNOMeOMeSN2BrPhONH3Ovgl.󰀀12-C4OMeOMe󰀀

12-D4󰀀󰀀

HO2C

2,5-Dibromadipinsäurediethylester󰀀aus󰀀Adipinsäure󰀀

1)󰀀SOCl2,󰀀Br2

CO2H

EtO2C

Br

2)󰀀EtOH

Br

CO2Et

12-D4

HO2CCClOSClOHOHO2CCOHClOSO

Cl

ClHO2CHO2C

C

Cl

COH-󰀀HOH-󰀀Cl--󰀀SO2OSOClO

HO2C

C

Cl

OOCl

CC

Cl

OHCCl

C

Cl

OHBrBrCClCOCl

BrO

-󰀀H

󰀀

OC

Cl

Br

CO

Cl

Cl󰀀

(1)OCCBrClHO(2)(2)-󰀀Cl-

(1)BrO󰀀󰀀

󰀀

OC

Cl

BrBr

O

OC

Cl

OBr

OBr

HOC

-󰀀H

C

OCO

Br

Br

OCO

󰀀󰀀

12-E2󰀀󰀀1-(N-Pyrrolidino)cyclohexen󰀀aus󰀀Cyclohexanon󰀀und󰀀Pyrrolidin󰀀

12-E3󰀀3-(2-Oxocyclohexyl)propionsäureethylester󰀀aus󰀀1-(N-Pyrrolidino)cyclohexen󰀀(12-E2)󰀀und󰀀Acrylsäureethylester󰀀󰀀

O

Η+, Toluol,󰀀 ∆

󰀀

N

+

NH

(-H2O)

12-E2

O

CO2Et

O1)OEt2)󰀀H2O,󰀀∆

12-E3

Mechanismus󰀀siehe󰀀unter󰀀12󰀀A2/3

󰀀󰀀󰀀󰀀󰀀

12-E4󰀀

󰀀

2,4-Dibrom-3-pentanon󰀀aus󰀀3-Pentanon󰀀

󰀀

O

Br2,󰀀PBr3󰀀(kat)-10󰀀bis󰀀0°C

BrO

Br12-E4

BrOPBrBrOBrPBrBrOBrPBrBr-󰀀HHBrBr-󰀀BrO

BrO

-󰀀PBr3OPBrBrBrBrBr

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󰀀Sebacinsäuredichlorid󰀀(6-B2)󰀀󰀀󰀀

O

Η+, Toluol,󰀀 ∆

󰀀

N+

(-H2O)

NH

󰀀󰀀󰀀

12-F2󰀀

OOO

OOO1)8

Cl,󰀀󰀀Et3N8Cl2)󰀀HCl/H2O12-F3

Mechanismus󰀀siehe󰀀unter󰀀12󰀀A2/3

󰀀󰀀

12-F4󰀀󰀀

O

󰀀

-Brom--butyrolacton󰀀aus󰀀-Butyrolacton󰀀

Br

Br2,󰀀P

BrH2O

O

Br

Br

O

O

O

12-F4

3󰀀Br2󰀀+󰀀2󰀀P

2󰀀PBr3

BrBrOBrOPBrBrBr

Br

OOBrP-󰀀PBr3HHO

Br

O

BrBrBrBr-󰀀H2O;󰀀-BrBrBrOHH2OBrOHHO

Br

OH

-󰀀HOHH󰀀󰀀󰀀

󰀀

Br

BrBrBr

-󰀀HBr

H2O

O

BrOOH-󰀀BrO-󰀀HOHO

O

󰀀

󰀀

13.󰀀Chemie󰀀von󰀀Aldeyd-,󰀀Keton-󰀀und󰀀Esterenolaten󰀀󰀀󰀀󰀀

13-A1󰀀Acetylbernsteinsäurediethylester󰀀aus󰀀Acetessigester󰀀und󰀀Chloressigsäureethylester󰀀󰀀

O

O

O

OEt

1)󰀀Na,󰀀EtOHOEt

2)󰀀ClCH2CO2Et

Na

HOEt

Na

OEt

0.5H2O

CO2Et

󰀀

OONa

OEtHOOO

Na

O

OEtHOEtOEtOEt

Weniger󰀀wichtige󰀀meso.󰀀GF,da󰀀14󰀀kcal/mol󰀀

Ester-Mesomerie󰀀fehlt!!!

ONaOO

ClOO

OEtOEtNaClOEt

CO2Et

󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀󰀀

13-A2󰀀4-Oxopentancarbonsäureethylester󰀀aus󰀀Acetylbernsteinsäurediethylester󰀀(13-A1)󰀀󰀀󰀀󰀀

OO

H3BO3

OEt

O

CO2Et

CO2Et

OH

HO

OH

󰀀

O

δ−

O

δ−

OHOBδ+δ−OOEt

δ+BOH

OH

OEt

CO2Et

CO2Et

OH

HO

OH

HO

BOδ+OH

OBOOH

δ−OH2OOEt~HOEtOH2CO2EtEtO2COH

O

HO

OH

BOOHOOHEtOOHO

Et

O

H3BO3HOEt

EtO2C󰀀

󰀀

HOOOH

OOEt

OCO2O

Et

OOHO

O

Et

O

O

O

Et

󰀀󰀀󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

13-A3󰀀󰀀

Sorbinsäure󰀀aus󰀀Malonsäure󰀀und󰀀Crotonaldehyd󰀀󰀀

HO

O

CHO

Pyridin,󰀀D

CO2H

+

O

HO

13-A3

OOH

NH

O

O

H

O

HOHHOHNOH

OH

O

OHOH

󰀀

HHOHHOOHOHHNOOHOHOHOHNHOHN

HHNOHONHOHHOOOHHOOOHOHHHOHHOOHHO~H

HHHHOOHCO2HHOHHHHOH

HH

O

H

HHOHHO

󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀

13-A4󰀀󰀀󰀀

3-Hydroxy-2-methylpentanal󰀀aus󰀀Propionaldehyd

CHO

KOH,󰀀MeOH

CHO

OH

13-A4

HHHOOOHHHOHH2O

HHKH

H

OO

H

H3OH2OK

H

H

=

O

OH

OH

O

󰀀󰀀󰀀󰀀󰀀󰀀

󰀀

󰀀

13-B1󰀀󰀀5-(1-Hydroxy-2-phenylethyliden)-2,2-dimethyl-1,3-dioxan-4,6-dion󰀀aus󰀀Meldrums󰀀Säure󰀀(9-C4)󰀀und󰀀Phenylessigsäurechlorid󰀀󰀀󰀀

O

O

O

O

Pyridin

CH2Cl2

OOH

+

O

O

Cl

O

O󰀀

OOHOOOHOOHNOHNOClOOHOClOON

OOOHNHOHN~HOClOONHOHO

~H3OH2OH-ClOOH

OOClO

O

N󰀀󰀀󰀀

󰀀

󰀀

13-B2󰀀󰀀3-Oxo-4-phenylbuttersäuremethylester󰀀aus󰀀5-(1-Hydroxy-2-phenylethyliden)-2,2-dimethyl-1,3-dioxan-4,6-dion󰀀(13-B1)󰀀󰀀󰀀

O

O

OH

MeOH,󰀀∆

O

OOMe

O

O

13-B1

13-B2󰀀

Me

OHOOO

HO

OOHMeOHOOO

O

~HOHOOOHHOOOOOOOHOO

HO

O

HOO

O

HO

O

~HOO

OH

O

HOHOOOHOO~HOOHCO2~H

HO

O

O

O

O

O

󰀀󰀀󰀀

13-B3󰀀1,2,4,5-Tetraphenylpentan-1,5-dion󰀀aus󰀀Desoxybenzoin󰀀󰀀󰀀

Ph

O

CH2O,󰀀KOH

Ph

O

O

Ph

Ph

PhPh

13-B3

OPhKHHPhOPhOKOHH2O

HPhHPhOHPhPhK

OH2OOHHOKOHH2OHPhHOPhOPhOPhHOPhKOH

HOKPhPhO

Ph

OO

Ph

Ph

Ph

+HPh

Ph

Ph

Ph

O󰀀

13-B4󰀀2-Methyl-3-oxo-pentansäureethylester󰀀aus󰀀Propionsäureethylester󰀀󰀀󰀀

O

Na

OEt

OEt

O

O

13-B4

OHOEtHNaOOSET-HHOEtSET-HHOEtH2HOOEtOO

OOEt

OO-OEtOEtOEtOEt󰀀󰀀󰀀󰀀󰀀

󰀀

13-C1󰀀2-Oxo-5,6-diphenyl-3-cyclohexen-1-carbonsäureethylester󰀀aus󰀀Benzalacetophenon󰀀und󰀀Acetessigsäureethylester󰀀󰀀

13-C2󰀀3,5-Diphenyl-2-cyclohexen-1-on󰀀aus󰀀2-Oxo-5,6-diphenyl-3-cyclohexen-1-carbonsäureethylester󰀀(13-C1)󰀀󰀀

13-C3󰀀󰀀1-Ethyl-2-oxocyclopentan-1-carbonsäureethylester󰀀aus󰀀2-Oxocyclopentan-1-carbonsäureethylester󰀀󰀀

13-C4󰀀󰀀3-Ethyl-2-oxocyclopentan-1-carbonsäureethylester󰀀aus󰀀1-Ethyl-2-oxocyclopentan-1-carbonsäureethylester󰀀(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󰀀Malonsäurediethylester󰀀󰀀

13-E1󰀀Indan-1,3-dion󰀀aus󰀀Phthalsäurediethylester󰀀und󰀀Essigsäureethylester󰀀󰀀

13-E2󰀀(+)-3-(Trifluoracetyl)campher󰀀aus󰀀(+)-Campher󰀀und󰀀Trifluoressigsäureethylester󰀀󰀀

13-E3󰀀3-Cyclopenten-1,1-dicarbonsäure󰀀aus󰀀

Malonsäuredimethylester󰀀und󰀀cis-1,4-Dichlor-2-buten󰀀13-E4󰀀4-Hydroxy-4-methyl-2-pentanon󰀀aus󰀀Aceton󰀀󰀀13-F1󰀀(3-Oxocyclohexyl)essigsäure󰀀aus󰀀

Malonsäurediethylester󰀀und󰀀2-Cyclohexen-1-on󰀀󰀀13-F2󰀀3-(Methylthio)-1-(phthalimido)propan-1,1-dicarbonsäurediethylester󰀀aus󰀀

(Phthalimido)malonsäurediethylester󰀀(2-C1)󰀀󰀀13-F3󰀀rac-Methionin󰀀3-(Methylthio)-1-(phthalimido)propan-1,1-dicarbonsäurediethylester󰀀(13-F2)󰀀13-F4󰀀7,16-Dioxodocosandisäure󰀀aus󰀀1,10-Bis(2-oxocylohexyl)-1,10-decandion󰀀(12-F3)󰀀󰀀󰀀

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