6. Nucleophile Substitutionen an Carbonsaurederivaten 6-a1 Pivalinsaurepyrrolidid aus pivaloy chlorid und Pyrrolidine 6-A2 tert-Buty lcyclohexenylketon aus Pivalinsaurepyrrolidid ( 6-Al)und dem von I Bromcyclohexen(4-A3)abgeleiteten Grignard-Reagenz NH CHCI3, Pyridin 6-A1 6-A2 Mg br ⊙MgBr HCI
6. Nucleophile Substitutionen an Carbonsäurederivaten 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 NH O Cl O CHCl3 , Pyridin N 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-Hydroxybuttersauremethylester aus Poly-[(R)- 3-hydroxybuttersaure oO CICH,CH,CI/CH,OHOH O H H2SO4 OMe O OH O OH Meoh (PH 2 Me Me -H2O OH O OMe 6-A4 2-Methy l-2, 5-decandiol aus y-Pentyl-y-butyrolacton nCsH1 MeMel OH 6-A4
6-A3 (R)-3-Hydroxybuttersäuremethylester aus Poly-[(R)- 3-hydroxybuttersäure] ClCH2CH2Cl / CH3OH H2 SO4 O O H OH n OMe OH O 6-A3 O OH H OH n MeOH O OH H OH OH n Me ~H O OH H OH2 O n Me O OMe OH O O H OH n-1 - -H2O 6-A4 2-Methyl-2,5-decandiol aus -Pentyl- -butyrolacton O nC5H11 O HO OH nC5H11 MeMgI 6-A4
Me- Mgl nC5H11 nC5H11 Me-MgI MGl Mgl -2 NH3 +NHaCl-2 MgIC OH 6-bl Fluoren-9-carbaldehyd aus fluoren CHO NaH, HCO,Et
O nC5H11 O Me MgI O nC5H11 O Me MgI O O nC5H11 Me MgI MgI O O MgI nC5H11 MgI OH HO nC5H11 +NH4Cl -2 NH3 , -2 MgICl 6-B1 Fluoren-9-carbaldehyd aus Fluoren CHO NaH, HCO2Et 6-B1
NaH H OEt H .O H H-+QEt H OEt -HOEt
H H NaH -H2 Na O H OEt OEt H O H O H OEt H -HOEt O H -H
6-B2 Sebacinsauredichlorid aus sebacinsaure 6-B3 Sebacinsaurediamid aus Sebacinsauredichlorid(6- B2) SOCl2 (CH2)8 OH (CH2)8 CI 6-B2 NH3(waBrig) 6-B3 H+ +Ci+ -HCl/-sO2 analog
6-B2 Sebacinsäuredichlorid aus Sebacinsäure 6-B3 Sebacinsäurediamid aus Sebacinsäuredichlorid (6- B2) O Cl (CH2 )8 Cl O O HO (CH2 )8 OH O SOCl2 O H2N (CH2 )8 NH2 O NH3 (wäßrig) 6-B2 6-B3 O HO (CH2 )8 OH O S Cl O Cl O HO (CH2 )8 O O S O Cl +Cl H O HO (CH2)8 O O S O Cl +Cl + H O HO (CH2)8 O O S O Cl Cl H + -HCl / -SO2 O HO (CH2)8 Cl O O Cl (CH2)8 Cl analog O
NH NH3 HCI (CH2)8 NH (CH2)B NH CI (CH2)8 NH 6-B4 Octanal aus N-Formylpiperidin und dem Grignardreagenz aus 1-Bromoctan(2-Al) Hept、Br 1)Mg, EtO Hept 6-B4
O Cl (CH2 )8 Cl O NH3 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 O N 6-B4
Mg Hept、MgBr (SET) gbR H Hept、MgBt He N ⊙ Hept Hept 6-c1 Acety lsalicylsaure aus salicylsaure CO,H H2SO OAC 6-C1
Hept Br Mg (SET) Hept MgBr Hept MgBr O N N Hept O H MgBr NH Hept O H MgBr H Hept O - HN 6-C1 Acetylsalicylsäure aus Salicylsäure CO2H OH CO2H OAc O O O H2SO4 6-C1
cO, CO2H CO,H CO2H OAc HOAC 0:H 6-C1 6-C2 Sebacinsauremonomethylester aus Sebacinsauresauredimethylester 6-C3 10-Methy1-10-hydroxy-undecansaure aus Sebacinsauremonomethylester(6C2) 6-C4 Sebacinsaureethylmethylester aus Sebacinsauremonomethylester( 6-C2 1)Ba(Oh) Meo (CH2)8 OMe 2)H:Oo Meo (CH2)B OH 6-C2 OH O 1)MeMel (CH2)8 OH 2)NH4CI/H,O 6-C3 1)CI-CO-OEt Meo (CH2)8 OEt 2)EtoH
CO2H OH HO O O CO2H O H O O O ~H CO2H O O O O - HOAc H CO2H OAc 6-C1 6-C2 Sebacinsäuremonomethylester aus Sebacinsäuresäuredimethylester 6-C3 10-Methyl-10-hydroxy-undecansäure aus Sebacinsäuremonomethylester (6 C2) 6-C4 Sebacinsäureethylmethylester aus Sebacinsäuremonomethylester (6-C2) O MeO (CH2 )8 OH O O 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
OH Meo (CH2)8 OMe Meo home Meo (CH2)&OH Meo (CH2)8 OH 6-C2 o: Mgl Me-Mgl (CH2)8 OMe CH4 (CH2)8 OMe 6-C2 Me -Mgl +NH4
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
Mgl (CH2)8 HOMe ( CH2)8 COMe H Me—Mgl OH +Net MeO′(HzC) OH NETs MeO(H2C) Cl\ OEt MeO(H2C) O OEt MeO(H2C)
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 MeO (H2C)8 OH O 6-C2 + NEt3 - HNEt3 O MeO (H2C)8 O O O Cl OEt O MeO (H2C)8 O O O Cl O Et O MeO (H2C)8 O O O OEt Cl