carboxylic acid derivatives

Question 1

What are the four carboxylic acid derivatives? What are their relative stability and reactivity?

Answer 1

Acid chloride (least stable, most reactive)
Acid anhydride
Ester
Amides (most stable, least reactive)

Question 2

How does the leaving group influence the stabilization and destabilize the C of the carbonyl?

Answer 2

Inductive- L group is EWG (destabilizing)
Resonance- L group provides resonance and stabilization

Question 3

How does Cl in acyl chlorides affect C stability?

Answer 3

Cl is a EWG so it is destabilizing

Question 4

How does the O in esters affect the stability of C of carbonyl group?

Answer 4

OR is EDG through resonance which overcomes the e- withdrawal of OR

Question 5

How does O of anhydrides affect C stabilization in carbonyl?

Answer 5

Stabilizes both C through resonance

Question 6

How does the N of amides affect the stabilization of C of carbonyl group?

Answer 6

N is more willing to donate electrons since it is less electronegative and can bear the positive charge for much longer

Question 7

Reaction conditions to go from acyl chloride to carboxylic acid?

Answer 7

H2O

Question 8

What is the byproduct of all acyl chloride reactions?

Answer 8

HCl

Question 9

Reaction conditions to go from acyl chloride to anhydride?

Answer 9

Carboxylic acid | pyridine

Question 10

Reaction conditions to go from acyl chloride to ester?

Answer 10

R-OH | pyridine

Question 11

Reaction conditions to go from acyl chloride to amide?

Answer 11

R2NH | pyridine or 2R2NH

Question 12

Why do you need to use 2 eq of R2NH in amide formation from acyl chloride?

Answer 12

R2NH with HCl forms ammonium and Cl ion which is deactivated

Question 13

Reaction conditions to go from anhydride to carboxylic acid?

Answer 13

H2O. Can be catalyzed with acid or base dependent on R group size

Question 14

Reaction conditions to go from anhydride to ester?

Answer 14

R-OH | pyridine or H+

Question 15

Reaction conditions to go from anhydride to amide?

Answer 15

R2NH | pryidine or 2R2NH

Question 16

Reaction conditions (acidic) to go from ester to carboxylic acid? What is the other byproduct?

Answer 16

H2O, H+
Alcohol byproduct

Question 17

Reaction conditions (basic) to go from ester to carboxylic salt? Why is it special? What is the byproduct?

Answer 17

H2O | NaOH
It is irreversible!!
Alcohol byproduct

Question 18

Reaction conditions to go from ester to amide?

Answer 18

Reactants: ester + NH3, 1º/2º amide
Conditions: heat
Product: amide + alcohol

Question 19

Reaction conditions to go from thiol esters to esters?

Answer 19

Reactant: Thiol ester
Conditions: alcohol | HCl or pyridine
Product: ester and thiol

Question 20

Reaction conditions of grignard addition to esters?

Answer 20

Reactant: ester + 2 eq grignard
Conditions: 1) ether 2) H3O+
Product: tertiary alcohol

Question 21

Reaction conditions of acyl chloride to amide?

Answer 21

2R2NH or R2NH| pyridine

Question 22

Reaction conditions of anhydride to amide?

Answer 22

2R2NH or R2NH| pyridine

Question 23

Reaction conditions to go from ester to amide?

Answer 23

R2NH | heat

Question 24

Reaction conditions to go from carboxylic acid to amide?

Answer 24

CA with SOCl2 to acyl chloride with 2R2NH to amide

Question 25

Reaction conditions of acidic hydrolysis of amides to carboxylic acids?

Answer 25

H2O, H2SO4 | heat
Product: carboxylic acid and protnated amine

Question 26

Reaction conditions and product of basic hydrolysis of amides?

Answer 26

H2O, NaOH | heat
Product: carboxylate ion and amine

Question 27

Reaction conditions and restrictions to form nitriles?

Answer 27

Reactant: alkyl halide, R= methyl, 1º/2º. X=Cl, Br, I
Conditions: KCN | acetate or NaCN
Product: nitrile

Question 28

Reaction conditions of acidic nitrile hydrolysis? What intermediate is made?

Answer 28

Reactant: nitrile
Conditions: H2O, H2SO4 | heat
Product: carboxylic acid and ammonium ion
*amide intermediate

Question 29

Reaction conditions of basic hydrolysis of nitriles?

Answer 29

Reactant: nitrile
Conditions: 1) H2O, H2SO4, heat 2) H3O+
Product: carboxylic acid

Question 30

Reaction conditions of grignard with nitriles? What intermediate is formed?

Answer 30

Reactant: nitrile
Conditions: 1) grignard, ether 2) H3O+
Product: ketone
*imine intermediate