Orgo II Exam 3 reactions

Question 1

Acid Catalyzed Ketone-Enol interconversion

Answer 1

Ketone –(H3O+ ,H2O)–> enol

Question 2

Base Catalyzed Ketone-enol interconversion

Answer 2

Ketone –(OH-, H2O)–> enol

Question 3

Acid Promoted Enolate Halogenation

Answer 3

Enolate–(Br2, H3O+)–> carbonyl halogenated at the a-Carbon

Question 4

Kinetic Enolate alkylation

Answer 4

Enolate–1. LDA, -78 C 2. R-X–> faster/less stable a-Carbon alkylation

Question 4

Base Promoted Enolate Halogenation

Answer 4

Enolate–(Br2 XS, NaOH)–> halogenation of all a-H’s

Question 5

Thermodynamic Enolate alkylation

Answer 5

Enolate–1. LDA, 0-25 C C 2. R-X–> slower/more stable a-Carbon alkylation

Question 6

HVZ

Answer 6

Carboxylic acid –1. PBr3, Br2 2. H2O–> monobromonation at a-carbon

Question 7

Alpha Carbon Enamine Alkylation

Answer 7

Enamine – 1. R-X 2. H2O, HCl–> less substituted ketone

Question 8

Alpha Carbon Enamine Acylation

Answer 8

Enamine– 1. acyl chloride 2. HCl, H2O–> diketone

Question 9

Stork Enamine Synthesis

Answer 9

enamine –1. a-B-unsat 2. HCl, H2O–> 1, 5 dicarbonyl

Question 10

Decarboxylation in Basic Conditions

Answer 10

carboxylate ion – heat–> ketone ion +CO2

Question 11

Decarboxylation in Acidic Conditions

Answer 11

ester/carboxylic acid–H3O+, heat–> ketone
Malonic acid need 135 C

Question 12

Acetoacetic Ester Synthesis

Answer 12

ketone-ethyl ester –1. NaOEt 2. R-X 3. HCl, H2O, heat–> methyl ketone

Question 13

Basic Aldol addition

Answer 13

2 aldehyde/ketone– OH-, H2O–> ketone-alcohol

Reversible with OH-, H2O, heat

Question 13

Malonic Ester Synthesis

Answer 13

diester–1. NaOR 2. R-X 3. H3O+ , H2O, heat–> carboxylic acid

Can dialkylate by repeating 1 and 2

Question 14

Aldol Condensation

Answer 14

aldol addition product –H3O+ or OH-, heat–> a-B-unsat + H2O

Question 15

Haloform Reaction

Answer 15

Ketone –X2, NaOH(xs)–> carboxylate

H3O+ in 2nd step to form carboxylic acid

Question 16

Crossed Aldol Method 1

Answer 16

Carbonyl w/o a-H + OH –1. carbonyl w/ a-H (add slowly) 2. HCl –> 4 different addition products

Question 17

Claisen Condensation Reaction

Answer 17

2 Esters –1. NaOR 2. HCl –> ketone-ester + ROH

Question 17

Crossed Aldol Method 2

Answer 17

intended enolate –LDA, THF–> enolate –1. other carbonyl (add slowly) 2. HCl –> 4 different addition products

Question 18

Dieckmann Reaction

Answer 18

Intramolecular claisen condensation

Question 19

Grignard Alkylation

Answer 19

a-B-unsat –1. RMgBr 2. H3O+ –> attacks corbonyl carbon to create alcohol

Question 20

Gilman Alkylation

Answer 20

a–unsat –1. R2CuLi 2. H3O+ B-alkylated ketone

Question 21

Michael Reaction

Answer 21

a-B-unsate (acceptor) + B-dicarbonyl (donor) –OR-, ROH–> adds to acidic H

Question 22

Robinson Annulation

Answer 22

Michael donor –1. NaOH 2. Michael acceptor 3. NaOH, heat–> cyclic formation