Final: Topic 1

Question 1

EArS: Sulfonation

Benzene + H2SO4 + SO3

Answer 1

=> Benzene-SO3H

Question 2

EArS: Halogenation

Benzene + FeX3 + X2

Answer 2

=> Benzene-X

Question 3

EArS: Nitration

Benzene + H2SO4 + HNO3

Answer 3

=> Benzene-NO2

Question 4

EArS: Friedel Crafts Acylation

Benzene + AlCl3 + R-Cl=O

Answer 4

=> Benzene=O-R

Question 5

EArS: Friedel Crafts Alkylation

Benzene + AlCl3 + RCl

Answer 5

=> Benzene-R

Question 6

Clemmensen Reduction

Answer 6

Used to reduce acylation products to avoid rearrangements from alkylation
Zn/Hg, HCl, reflux

Question 7

Wolff-Kischner Reduction

Answer 7

Used to reduce acylation products to avoid rearrangements from alkylation
H2NNH2, KOH, heat (delta)

Question 8

KMnO4, OH-, H3O+ against a ketone - -

Answer 8

Oxidizes to a carboxylic acid

Question 9

Diazonium:

NaNO2, HX, benzyl amine

Answer 9

Creates diazonium ion (+1): benzyl-N—N

Question 10

Grignard addition to ketones:

Ketone + 1) R’MgBr, ether 2) H3O+

Answer 10

3° Alcohol with R, R’ and R’’ groups from ketone and R’MgBr

Question 11

Grignard addition to esters:

Ester + 1)R’MgBr, ether 2) H3O+

Answer 11

3° alcohol with R, R’ and R’ groups + R’‘OH

Question 12

Addition of primary amines:

Carbonyl group + RNH2

Answer 12

Creates imine: (C=N-R) + H2O

Question 13

Addition of secondary amines:
Carbonyl group (H-C-C=O) + R2NH

Answer 13

Creates enamine: R

C=C-N+R and H2O

Question 14

Addition of hydroxylamine:

Carbonyl group + NH2OH

Answer 14

Creates oxime: C=NOH + H2O

Question 15

Conjugate addition of organocuprates:

Carbonyl (C=C-C=O) + 1) R2CuLi 2)H3O+

Answer 15

R-C-C-C=O

H

Question 16

Carboxylation of Grignard Reagents:

RMgBr + 1) CO2, ether 2) H3O+

Answer 16

Creates ester: OR’

R-C=O

Question 17

Reduction of Nitriles to amines:

RC=N + 1) LiAlH4 2) H3O+

Answer 17

R-C-NH2

H H

Question 18

Baeyer-Villiger Oxidation:

Ketone + mCPBA R-C=O-O-OH

Answer 18

Creates Ester:

R-C=O-O-R’

Question 19

Carboxylic acids to acid chlorides:

Carboxylic acid + SOCl2, CHCl3

Answer 19

Creates acid chloride, SO2, HCl

Question 20

Carboxylic acids to esters:

Carboxylic acid + R’OH + acid cat.

Answer 20

Creates ester w’ R’ + H2O

Question 21

Alcoholysis of acid chlorides to esters:

Acid chloride + R’OH

Answer 21

Creates ester + HCl

Question 22

Aminolysis of acid chlorides to amides:

Acid chloride + 2 NH3

Answer 22

Creates amide + NH4Cl

Question 23

Hydrolysis of esters to acids:

Ester + H3O+ or NaOH

Answer 23

Creates carboxylic acid + R’OH

Question 24

Transesterification:

Ester + R’‘OH + acid cat.

Answer 24

Creates ester with R’’, and R’OH

Question 25

Grignard Reaction with amides:

Amide + R’MgX + H3O+

Answer 25

Creates ketone

Question 26

Nucleophilic Aromatic Substitution:

O2N-Benzene-F + NaSR, DMF

Answer 26

Creates O2N-Benzene-SR + NaF

Question 27

Reduction: Aldehyde

Aldehyde + 1) NaBH4 2) H3O+

Answer 27

Creates 1° Alcohol: R-C-OH

Question 28

Reduction: Ketones

Ketone + 1)NaBH4 2) H3O+

Answer 28

Creates 2° Alcohol: R-C-R’

OH

Question 29

Reduction: Esters

O=C-OR + 1) LiAlH4 2)H3O+

Answer 29

Creates 1° Alcohol: R-C-OH + R’‘OH

Question 30

Tautomerization

Answer 30

=O to -OH in an enol, by -OH or H3O+,

Question 31

Halogenation of Aldehydes/Ketones

Answer 31

X2, Acid or Base, adds one X in alpha position

Question 32

Haloform Reaction

Answer 32

X3, OH- and H2O, creates -CX3 and then -O- and HCX3

Question 33

Halogenation of Carboxylic Acids

Answer 33

PX3 for Acid chloride, then X2 to add a secondary X, then H2O to return to carboxylic acid
Alternative: P, X2, H2O to add one X to non- OH side of carboxylic

Question 34

Alkylation of Ketones/Aldehydes

Answer 34

1. LDA, THF, -78°C -> to move double bond and create O- (carboxylate anion)
2. R’‘-X to finish alkylation and restore =O

Question 35

Alkylation of Esters

Answer 35

1. LDA, THF, -78°C (creates alpha anion)

2. R’‘-X

Question 36

Alkylation of beta-keto esters (Acetoacetic ester synthesis)

Answer 36

1. NaOEt, R-Br
2. OH-/heat, H3O+, heat
3. tBuOK, R’-Br
4. OH-, H3O+, heat

Question 37

Stork Enamine Synthesis (Alkylation of Enamines)

Answer 37

R’’–Br, H2O, heat

Question 38

Claisen Condensation

Answer 38

Ester + 1. NaOEt, another ester, 2. H3O+

Adds from OEt side of ester to alpha position

Question 39

Aldol Condensation 1

Answer 39

2 Aldehydes, NaOH, H2O

Question 40

Aldol Condensation 2

Answer 40

Aldehyde + ester, LDA, -78°C, NH4Cl, creates 3° Alcohol in alpha carbon with R’ groups