Exam 3 Sigman

Question 1

Carboxylic Acid + SOCl2

Answer 1

Acid Chloride

Question 2

Acid Chloride + Carboxylate Ion

Answer 2

Anhydride

Question 3

Linear carboxylic acids + heat

Answer 3

Ring Anhydride

Question 4

Acid Chloride + Water and pyridine

Answer 4

Carboxylic Acid

Question 5

Anhydride + Water

Answer 5

2 Carboxylic Acids

Question 6

Ester + Water (Acidic Conditions)

Answer 6

Carboxylic Acid

Question 7

Ester + Water (Basic Conditions)

Answer 7

Carboxylate Ion + ROH

Question 8

Amide + Water (Acidic Conditions)

Answer 8

Carboxylic Acid + Amine Ion

Question 9

Amide + Water (Basic Conditions)

Answer 9

Carboxylate Ion + Amine

Question 10

Acid Chloride + R’OH and pyridine

Answer 10

Ester (RCOOR’)

Question 11

Anhydride + R’OH

Answer 11

Ester + Carboxylic Acid

Question 12

Carboxylic Acid + R’OH (Acidic Conditions)

Answer 12

Ester (RCOOR’) + H2O

Question 13

Acid Chloride + NH3

Answer 13

Amide + NH4+

Question 14

Anhydride + NH3

Answer 14

Amide + Carboxylate Ion + NH4+

Question 15

Carboxylic Acid + NH3 and heat

Answer 15

Amide + H2O

Question 16

Carboxylic Acid + R’NH2 in DCC

Answer 16

Amide + H2O

Question 17

Ester + NH3

Answer 17

Amide + R’OH

Question 18

Nitrile + H2O (Acidic Conditions)

Answer 18

Carboxylic Acid

Question 19

Nitrile + H2O (Basic Conditions)

Answer 19

Carboxylate Ion

Question 20

Nitrile + LAH and H2O

Answer 20

Amine (primary amine)

Question 21

Nitrile + DIBAL-H and H2O

Answer 21

Aldehyde

Question 22

Nitrile + R’MgX or R’Li and H2O

Answer 22

Ketone

Question 23

Why is the thermodynamic enolate lower in energy?

Answer 23

Because it is the more substituted enolate

Question 24

What conditions favor the Kinetic Enolate?

Answer 24

strong, non-nucleophilic base (LDA), polar aprotic solvent (THF), and low temperature (-78C)

Question 25

What conditions favor the Thermodynamic Enolate?

Answer 25

Strong Base (EtO-, KOtBu), Protic Solvent (EtOH or other alcohols), and room temperature (25C)

Question 26

Carbonyl + X2, Acid

Answer 26

Monosubstitution of Halogen X, enol intermediate

Question 27

Carbonyl (not methyl ketone) + X2 (excess), Base

Answer 27

Polysubstitution of Halogen X, enolate intermediates

Question 28

Carbonyl (methyl ketone) + X2 (excess), Base

Answer 28

Carboxylate Ion + HCX3

Question 29

alpha halo carbonyl + Li2CO3, LiBr, DMF

Answer 29

E2 Elimination…Ketone including alkene

Question 30

alpha halo carbonyl + Nucleophile

Answer 30

SN2 Substitution

Question 31

Ketone + Base, RX

Answer 31

Alkylation at alpha carbon (LDA used as base to form intermediate enolate, later an SN2 mechanism)

Question 32

STUDY Malonic Ester Synthesis and Acetoacetic Ester Synthesis

Answer 32

OK

Question 33

What are the steps in the Aldol Reaction?

Answer 33

1. Make an enolate of the ketone/aldehyde
2. Attack the electrophilic carbonyl carbon
3. Protonate the O- to get the alcohol

Question 34

What are the steps in the Claisen Reaction

Answer 34

1. Make the enolate of the ester
2. Attack the electrophilic carbonyl carbon
3. reform the carbonyl as you push off the Oxygen-carbon leaving group of the ester

Question 35

What is a Dieckmann Reaction?

Answer 35

An intramolecular claisen reaction

Question 36

What is a Michael Reaction?

Answer 36

Enolate attacking an alpha, beta unsaturated carbonyl compound (Think 1, 4 addition)

Question 37

What is a Robinson Annulation?

Answer 37

Combines a michael reaction with an intramolecular aldol reaction.

Question 38

Aldehyde or Ketone + -OH, H2O

Answer 38

Aldol Reaction (Be prepared to do the condensation reaction)

Question 39

Ester + NaOR’, H3O+

Answer 39

Claisen Reaction (ketone + ester)

Question 40

alpha beta unsaturated carbonyl + ketone + -OR’ or -OH and H2O

Answer 40

Michael Reaction

Question 41

alpha beta unsaturated carbonyl + ketone + -OR’ or -OH and H2O

Answer 41

Robinson Annulation (Ring formation)