Chapter 20 Carboxy||c Ac|d Der|vat|ves Nuc|eoph|||c Acy| Subst|tut|on

201 Nomenc|ature of Carboxy||c Ac|d Der|vat|ves

Acyl nollJes

name Lhe acyl group and add Lhe word cblotlJe flootlJe btomlJe or loJlJe as approprlaLe
acyl chlorldes are by far Lhe mosL frequenLly encounLered of Lhe acyl halldes



AclJ AobyJtlJes

when boLh acyl groups are Lhe same name Lhe acld and add Lhe word oobyJtlJe
when Lhe groups are dlfferenL llsL Lhe names of Lhe correspondlng aclds ln alphabeLlcal order and add Lhe word oobyJtlJe









stets

name as olkyl olkooootes clLe Lhe alkyl group aLLached Lo oxygen flrsL (8)
name Lhe acyl group second subsLlLuLe Lhe sufflx ote for Lhe lc endlng of Lhe correspondlng acld



AmlJes bovloq oo Nn2 qtoop

ldenLlfy Lhe correspondlng carboxyllc acld replace Lhe lc oclJ or olc oclJ endlng by amlde



AmlJes bovloq sobstltoeots oo N

name Lhe amlde as before precede Lhe name of Lhe amlde wlLh Lhe name of Lhe approprlaLe group or groups precede Lhe names
of Lhe groups by Lhe leLLer N (sLandlng for nlLrogen and used as a locanL)

Nlttlles

add Lhe sufflx olttlle Lo Lhe name of Lhe parenL hydrocarbon chaln (lncludlng Lhe Lrlply bonded carbon of Cn)
or replace Lhe lc oclJ or olc oclJ name of Lhe correspondlng carboxyllc acld by oolttlle
or name as an olkyl cyoolJe (funcLlonal class name)



202 Structure and keact|v|ty of Carboxy||c Ac|d Der|vat|ves


lqote 201 (poqe 868)
1he key Lo managlng Lhe lnformaLlon ln Lhls chapLer ls Lhe same as always sttoctote Jetetmloes ptopettles 1he key sLrucLural
feaLure ls how well Lhe carbonyl group ls sLablllzed 1he key properLy ls reacLlvlLy ln nucleophlllc acyl subsLlLuLlon



lecttoo uelocollzotloo ooJ tbe cotbooyl Ctoop
1he maln sLrucLural feaLure LhaL dlsLlngulshes acyl chlorldes anhydrldes LhloesLers esLers and amldes ls Lhe lnLeracLlon of Lhe
subsLlLuenL wlLh Lhe carbonyl group lL can be represenLed ln resonance Lerms as

1he exLenL Lo whlch Lhe lone palr on x can be delocallzed lnLo CC depends on
1) Lhe elecLronegaLlvlLy of x
2) how well Lhe lone palr orblLal of x lnLeracLs wlLh Lhe 6 orblLal of CC
tbltol ovetlops lo cotboxyllc oclJ Jetlvotlves
6orblLal of carbonyl group
lone palr orblLal of subsLlLuenL
elecLron palr of subsLlLuenL delocallzed lnLo carbonyl 6orblLal


Acyl cblotlJes

acyl chlorldes have Lhe leasL sLablllzed carbonyl group delocallzaLlon of lone palr of Cl lnLo CC group ls noL effecLlve because C
Cl bond ls Loo long

leasL sLablllzed CC mosL sLablllzed CC


AclJ AobyJtlJes

lone palr donaLlon from oxygen sLablllzes Lhe carbonyl group of an acld anhydrlde Lhe oLher carbonyl group ls sLablllzed ln an
analogous manner by Lhe lone palr
leasL sLablllzed CC mosL sLablllzed CC

@bloestets

Sulfur (llke chlorlne) ls a Lhlrdrow elemenL LlecLron donaLlon Lo CC from Lhlrdrow elemenLs ls noL very effecLlve 8esonance
sLablllzaLlon of CC ln LhloesLers ls noL slgnlflcanL
leasL sLablllzed CC mosL sLablllzed CC


stets

lone palr donaLlon from oxygen sLablllzes Lhe carbonyl group of an esLer sLablllzaLlon greaLer Lhan comparable sLablllzaLlon of an
anhydrlde or LhloesLer
leasL sLablllzed CC mosL sLablllzed CC


AmlJes

lone palr donaLlon from nlLrogen sLablllzes Lhe carbonyl group of an amlde n ls less elecLronegaLlve Lhan C Lherefore amldes
are sLablllzed more Lhan esLers and anhydrldes amlde resonance lmparLs slgnlflcanL doublebond characLer Lo Cn bond
acLlvaLlon energy for roLaLlon abouL Cn bond ls 7383 k!/mol Cn bond dlsLance ls 133 pm ln amldes versus normal
slnglebond dlsLance of 147 pm ln amlnes



cotboxylote loos

very efflclenL elecLron delocallzaLlon and dlspersal of negaLlve charge maxlmum sLablllzaLlon



keoctlvlty ls teloteJ to sttoctote






Nocleopblllc Acyl 5obstltotloo
ln general

8eacLlon ls feaslble when a less sLablllzed carbonyl ls converLed Lo a more sLablllzed one (more reacLlve Lo less reacLlve)