Exam 2 O Chem 3 (redone flashcards)

Flashcards for exam 2, organic chemistry 3 (5/2/2026)

result of fisher esterification

carboxylic acid → ester

result of alkylation of carboxylic acids

carboxylic acid → ester

what reagent is used in alkylation of carboxylic acids

diazomethane H2C-N- - -N

result of reacting thionyl chloride with a carboxylic acid

carboxylic acid → acyl chloride

what 2 things are required for synthesis of anhydrides

2 equ carboxylic acid and a dehydrating agent (such as P2O5)

what is needed for synthesis of cyclic anhydrides

only heat because the process is intramolecular

What reagent is used for reduction of carboxylic acids?

LiAlH4

result of carboxylic acid reduction

carboxylic acid → primary alcohol

what is required for decarboxylation to occur?

a ketone at the beta position

what three categories were discussed for decarboxyliation

beta-ketoacids, malonic acids, carbonic acids

name the substituent

acetoxy

how to name carboxylate salts

name the counter ion first, then name the ion and use the suffix “ate”.

how to name esters

name the substiuent on the carboxylic oxygen first, then name the rest of the chain and use the suffix “oate”

what is a lactone?

a cyclic ester

how to name lactones

use a greek symbol to indicate the position of the ester, then count the number of carbons in the ring and use the suffix “lactone”

how to name acid halides?

name the chain and add the suffix “yl”, then name the halide

name the compound

acetic anhydride

how to name mixed anhydrides?

name either side of the anhydride (alphabetically) and then anhydride

how to name nitriles?

name the r group, then use the suffix “onitrile”

how to name primary amides

name r group, then add suffic “amide”

how to name secondary amides

use (N) then name the amide substituent, then the r group, then use suffix “amide”

how to name tertiary amides

use (N,N) and name amide substituent groups, then name the R group, then use suffix “amide”

what is a lactam?

a cyclic amide

how to name lactams

use greek letter to indicate position of nitrogen, then count number of carbons in ring and add suffix “lactam”

what functional groups utilize dicarboxylic acid nomenclature?

imides and anhydrides

list the priority of the discussed principal groups

carboxylic acid > anhydride > ester > acyl halide > amide > nitrile > aldehyde > ketone > alcohol > thiol

name the compound

carbonic acid

name the compound

phosgene

name the compound

urea

key thing to note about amide IR spec

amides exhibit significant C-O single bond character due to resonance stabilization resulting in a weakened bond reading, and therefore a lower IR stretch

orientation of Z-amides

carbonyl oxygen and amide substituents on the same side

orientation of E amides

carbonyl oxygen and amide substituent on opposite sides (steric interaction occurs between substituents)

rank the boiling points of carboxylix acids, amines, esters and ketones

amine > carboxylic acid > ester > ketone

key characteristic of ester IR spectrum

inductive effected strengthen the C=O bond, resulting in a higher than expected IR stretch

are ketones or esters more reactive?

ketones are more reactive than esters

rank the basicity of esters, nitriles, and amides

most basic = amides > ester > nitrile = most acidic

reaction category: carbonyl oxygen

SOCl2 addition

reaction category: carbonyl carbon

acyl substitution

reaction category: reactions are the alpha carbon

halogenation of the alpha carbon

result of saponification of esters

ester → carboxylic acid

what two reactions are the reverse of each other?

fisher esterification and saponification

why is hydrolysis of esters favored under basic conditions (saponification) over acidic conditions

acidic conditions require a strong acid and are very slow

what happens overtime following lactone ring opening?

the ring will collapse again

result of hydrolysis of primary amides

amide → carboxylic acid

result of hydrolysis of secondary amides

amide → aniline

result of nitrile hydrolysis

nitrile → carboxylic acid

requirement for hydrolysis under basic conditions

an additional workup step

stereochemistry of hydrolysis of cyclic anhydrides?

stereochemistry is preserved

reank the reactivity of the discussed functional groups

nitriles < amides < esters/carboxylic acids « anhydrides < acyl chlorides

what explains the reactivity of amides and acid chlorides

resonance structures: amides experience significant C-O single bond character making them less reactive and stabilizing the amide ground state whereas positive charge is poorly stabilized by chlorine in acid chlorides raising the ground state

What is the impact of the stability of the tetrahedral intermediate for amides vs. acyl chlorides

when x = Cl the intermediate is stabilized, when x = N the intermediate is destabilized

relationship between intermediate stability and reaction favorability

the more stable the intermediate, the more favorable a reaction is to occur

result of reacting acid chlorides with a amine

acid chloride → primary amide

why does pyridine act as a catalyst in addition of amines to acyl chlorides but triethyl amine does not

triethyl amine is too bulky to act as a catalyst

what can accelerate the reaction of pyridine addition to acid chlorides?

making the ring electron rich such as DMAP (the N(Me)2 pushes electron density into the ring and can be used as a catalyst)

result of alcohol addition to acid chlorides

acid chloride → ester

result of acid chloride reaction with carboxylate

acid chloride → anhydride

result of anhydride + phenol

anhydride → ester

result of cyclic anhydride + alcohol

cyclic anhydride → acyclic ester

result of anhydride plus amine

anhydride → amide

result of ester plus aniline

ester → amide

result of ester plus alkoxide

ester → ester

result of beta-lactams + alcohol

ring opening (serine example: addition of serine results in covalent linkage of the inhibited enzyme and leads to bacterial death)

what reagent is used to reduce esters, amides, and nitriles

LiAlH4

why is NaBH4 note used to reduce esters?

it is very slow

result of reduction of esters

ester → 2 alcohols

result of reduction of amides

amide → amine

result of reduction of nitriles

nitrile → amine

result of reduction of acid chlorides

acid chloride → aldehyde

what reagent is used for reduction of acid chlorides

LTTBA (lithium tri(tertbutoxide) aluminum hydride

what happens in reduction of acid chlorides if NaBH4 is used instead of LTTBA

is NaBH4 is used, the acid chloride will be reduced to the alcohol instead of the aldehyde

result of grignard addition to esters

ester → tertiary alcohol

result of grignard addition to acid chlorides

acid chloride → ketone

what is added to go from arachidonic acid to anadamide?

adding the enzyme goes to anadamide

what is added to go from anadamide back to arachidonic acid?

FAAH (breaks down amide product)

what is the c-centered enolate?

negative charge on alpha carbon

what is the o centered enolate

negative charge on the oxygen (alpha carbon neutral)

what are alpha, beta unsaturated carbonyls?

carbonyls which contain at least a double bond between the alpha and beta carbon

do ester or ketone enolates have a lower pka?

Ketone enolates have a lower pka because they are more stable through resonance when deprotonated. The conjugate base of esters is destabilized by the donation of an electron pair from the alpha oxygen creating repulsive negative charges in the c-centered enolate

what carbons are deuterated in alpha H/D exchange with dioxane and D2O?

all alpha carbons

exceptions where the enol form is favored over the ketone form and why

phenols (resonance stabilization) and beta-dicarbonyls (intramolecular hydrogen bonding and conjugation) are the exceptions

Kequ when the enol vs keto form is favored

enol favord: Kequ > 1. keto favored: Kequ < 1.

result of beta halogenation in acidic conditions

ketone → beta-haloketone

result of beta-halogenation in basic conditions

ketone → carboxylic acid

rate determining step in acidic beta-halogenation

concentration of acid

rate law for acidic beta-halogenation

rate = k[ketone][H3O+] (Br2 is not in the rate law and therefore does not effect rate of reaction)

what can alpha halogenation reaction be used for?

synthesis of ylides (wittig reagent)

are SN2 reactions faster with or without carbonyl chemistry?

SN2 reactions are faster with a carbonyl carbon

what product is formed during an aldol addition reaction

the beta-hydroxycarbonyl

the betahydroxy carbonyl product indicate what reaction occured

the aldol addition reaction

the alpha,beta-unsaturated carbonyl indicates what kind of reaction occured?

an aldol condensation reaction

what product is formed during an aldol condensation reaction

an alpha,beta-unsaturated carbonyl

What does E1CB stand for

elimination unimolecular conjugate base