Carboxylic Acid Derivatives

condensation water hydroxyl

Gen Formula: RCONR2 -oic acid suffix replaced with -amide suffix alkyl substituents on the nitrogen atom are prefixes specified with the letter N ex: N-ethyl-N-methylbutanamide synthesized by carboxylic acid + amine/ammonia only primary and secondary amines cyclic amides are called lactams

lower same level H bonding

carboxylic acid + alcohol Prefix is the substituent bonded to the Oxygen with suffix -oate ex: ethyl ethanoate cyclic esters are called lactones

under acidic conditions carboxylic acids and alcohols will condense in esters 1) carbonyl O attacks H+ 2) alcohol O attacks carbonyl carbon and pi bond electrongs go to carbonyl O making alcohol 3) carboxylic hydroxyl takes H from newly attached alcohol 4) water leaves as carbonyl is formed again by top O losing H

cyclic amides

cyclic esters

lack lower

storage of fats esters of long chain cab=rboxylic acids and glycerol

regenerates

condensation dimers of 2 carboxylic acids Gen For: RC(O)OC(O)R (two carbonyls seperated by O in middle) symetrical anhydrides are named by changing acid to anhydride ex: ethanoic anyhydride asymmetrical anhydrides are named by labeling chains alphabetically and then adding anhydride ex: ethanoic propanoic anyhydride

1) carboxylic hydroxyl attaks carbonyl carbon which gives pi electrongs to carbonyl Oxygen 2) H+ comes and bonds to hydroxyl group and takes away water, O- not gives electrons back for the double bond

heating carboxylic acids increased stability 5 6

higher increased weight

Most to least reactive anyhydrides > esters > amides resonance stabilization + 3 electron withdrawing oxygens are very electrophilic lack one less elecron withdrawing oxygen amino group is electron donating which is less reactive

size of substituents impact reaction can be used to advantage as if we want an Sn1 reaction, we can use a tertiary substrate ad to ceate protecting groups sizee and substitution of the leaving group of carboxylic acid derivative can affect ability of nucleophile to access the carbonyl carbon

distribution of charge across pi bonds dipoles are made as electrons from pi bond may be pulled more closely to the electronegative atom this dipole being made can increase chance for nucleophillic attack (+ for the carbonyl carbon) hence Anyhydrides > Amides as N is less electronegative than oxygen so the carbonyl carbon is more positive for the anhydride

presence of alternating single and multiple bonds all atoms are either sp2 or sp hybridized and have unhybridized p orbitals this causes delocalization of electrons as p orbitals align leading to resonance and sharing of electrons and more stable compounds ***once nucelophile bonds, this allows for positive charge stabilization so the compounds are more susceptible to nucelophilic attacks

certain lactams and lactones are more reactive to hydrolysis because they contain more strain ex: 4 membered rings have significantly high ring strain ring strain and reactivity is increased by fusion to a second ring by reducing resonance and making hydrolysis more likely

splits anyhdride in two with a carboxylic acid leaving group with ammonida, formation is amide + carboxylic acid with an alcohol, formation is ester + carboxylic acid with water, formation is 2 carboxylic acids 1) nucelophile (say ammonia) attacks a carbonyl carbon, carbonyl oxygen becomes O- 2) center O strips H from the nucleophile 3) positive OH splits off with a carbonyl carbon to make carboxylic acid, O- gives back electrons to form pi bond in this case results are a carboxylic acid and amide

alcohol acts as nuclephile to displace an esterifying group aka new ester is made with a new R’

under acidic conditions via nucleophilic substitution carbonyl ocygen becomes protonated making it more susceptible to nucleophilic attack by water produces carboxylic acid and ammonia (literally reverse of amide formation) 1) water attacks carbonyl carbon and pi bonds go make protonated carbonyl O to just OH 2) proton protonates NH2 to NH3 making it a leaving group and first OH gives electrons to make pi bond 3) H from positive carbonyl O dissociates Hydrolysis can occur in basic conditions bu oxygen isnt protonated, nucleophile is a hydroxide ion, and the product is deprotonated carboxylate anion instead of carboxylic acid