For carboxylic acids, replace the"e" with ____

"oic acid"

What is the pka values for CA's? What are the CB's called?

- 4-5 pka - CB: Carboxylate salts

For carboxylate salts, name the cation and replace the anion "ate" with _____

"ice acid"

For acid halides, replace the "oic acid" with _____

"oyl halide"

For anhydrides, name the 2 acids (if unsymmetric) follwed by _____

"anhydride"

What 2 types of anhydride are there?

Symmetric and asymmetric

For esters, what comes first as a substituent?

The oxygen substituent

For esters, the ending should be -______

"oate"

For primary amides (No N-sub), replace "oic acid" with ______

"amide" as part of the word

What's the difference in naming with primary vs secondary/tertiary?

Primary: no N-sub Secondary/Tertiary: has "N-" prefix

What are cyclic esters called?

Lactones

What are cyclic amides called?

Lactams

What solvents are used to convert nitriles to CA's

- H3O+, heat or - OH-/ H2O, heat

What are the common heteroatoms? 3

- O - N - X

What does inductive effects mean?

Pulls e- density away from carbonyl

When X in a carbonyl group has a low electronegativity, does it act as an inductive or resonance donating group?

Inductive - will make carbonyl carbon MORE reactive (e- poor/electrophilic)

Which heteroatoms are the most reactive? From most to least: Esters, Carboxylate anions, Amides, Anhydrides, Acid Halides, Ketones/aldehydes

1. Acid halides 2. Anhydrides 3. Ketones/Aldehydes 4. Esters 5. Amides 6. Carboxylate anions

Why is an acyl substitution classified as second order?

Both substrate (e- phile) and Nu are in TS of RDS

What is the rate equation of an acyl substitution rxn?

Rate = k [Nu] [RC(O)X]

What are the best to worst LG's: X-, NH2-, OR-, O2-, COOR-

1. X- 2. COOR- 3. OR- 4: NH2- 5: O 2-

What makes a good LG?

Very reactive

T/F: Less reactive compounds can be converted to more reactive ones

False

T/F: the larger R group is more susceptible for attack in anhydrides

False

What is saponificiation?

Conversion of ester to carboxylate under BASIC conditions

In basic solution _____ are deprotonated easily

acids

What are common nucleophiles in basic conditions? 2

- OH- - OR-

What are common products in basic conditions?

- Esters - CA's

Are CA's reactive under basic conditions? Why?

No - Deprotonation of the acid happens fast

What are common Nu's in neutral conditions? 5

- H2O - ROH - NH3 - RNH2 - R2NH

What are common products in neutral conditions? 3

- CA's - Esters - Amides

How many equivalents of the Nu are requires for amidation?

2

What can be used as a nucleophilic catalyst during esterification?

Pyridine

What are common nucleophiles in acidic conditions? 2

- H2O - ROH

What are common products in acidic conditions? 2

- Esters - CA's

T/F: the fisher esterification is reversible

True

How can an ester be converted back to an acid during the fisher esterification?

Using excess water

What is it called when one ester is converted to a diff ester? What do you need for this rxn?

- Transesterification - Excess alcohol

What solvent do you need for fisher/transesterification?

H2SO4

What is the difference between acid catatlysis and nucleophilic catalysts?

Acid: activate carbonyls towards Nu addn Nucleophilic: improve rxn rate by generating more reactive acyl intermediate

What kind of temperatures are required for amide hydrolysis?

- High temps - Carbonyl is not electrophilic and LG (NR2) is basic

Which conditions are better for amide hydrolysis? Why?

Acidic - Amine can be converted to better LG and carbonyl can be activated towards addn

What solvent would you need for amide hydrolysis under acidic conditions? 2

- H3O+ - Heat

T/F: Acyl rxns can happen under basic conditions Why?

False - acid base rxn happens first

How can OH be converted to a better LG? 2

- Fisher esterification - Use activating reagents to make more reactive carbonyl

What is an activating reagent? Examples?

- Converts SM to more reactive intermediate to simplify its conversion to a desired product - SOCl2, DCC

Describe SOCl2 as an activating reagent

- Intermediate is mixed anhydride that is susceptible to addn/elim by X- - Byproducts are gases = irreversible rxn

How can an amine and CA functional group be linked tg?

DCC

What do you use to stop a reduction? Why?

- Electrophilic hydride reagents - Nuc hydrides are very reactive and cannot be stopped during reduction of CA derivative - Ephilic's react faster w/ e- rich carbonyls = reacts well w/ carbonyls stabilized by resonance

What is the most common electrophilic hydride reagent?

DIBAL-H

Which functional groups are more reactive towards reduction with electrophilic hydrides?

Esters, amides, and nitriles

What do you need for a DIBAL-H reduction rxn?

- DIBAL-H - H3O+ (acidic workop)