Hull Exam 3 Review

Question 1

Out, in, endo, exo: which have the same stereochem (both wedge or both dash)?

Answer 1

Out & endo, in & exo

Question 2

Diels-Alder retrosynthesis: when you see an EWG what does it have to be?

Answer 2

Endo

Question 3

Reactant: phenol
Reagent: H2CrO4
Product:

Answer 3

p-benzoquinone (know what it looks like)

Question 4

Reactant: phenol
Reagents: K2CrO4, H2SO4
Product:

Answer 4

p-benzoquinone (know what it looks like)

Question 5

Reactant: hydroquinone (know what it looks like)
Reagents: K2CrO4, H2SO4
Product:

Answer 5

p-benzoquinone (know what it looks like)

Question 6

Reactant: 2-hydroxyphenol
Reagents: K2CrO4, H2SO4
Product:

Answer 6

ortho-quinone (know what it looks like)

Question 7

Reactant: 1°, 2°, or 3° (not 4°) benzylic C
Reagents: H2CrO4, 🔺
Product:

Answer 7

Benzylic C replaced by COOH

Question 8

Reactant: benzene
Reagents: Cl2, FeCl3
or Br2, FeBr3
or Br2, AlBr3
Product:

Answer 8

Chlorobenzene + HCl
or bromobenzene + HBr + FeBr3

Question 9

Reactant: benzene
Reagents: HNO3, H2SO4
Product:

Answer 9

Nitrobenzene (NO2) + H2O

Question 10

Reactant: benzene
Reagents: SO3, H2SO4
Product:

Answer 10

Benzene with SO3H on it

Question 11

Reactant: benzene
Reagents: RCl, AlCl3
Product:

Answer 11

Benzene-R + HCl

Question 12

When does Friedel-Crafts Alkylation and Acylation fail?

Answer 12

When meta directors are on the benzene ring

Question 13

Strongly activating o,p-directors

Answer 13

-NH2, -NHR, -NR2, -OH, -OR

Question 14

Moderately activating o,p-directors

Answer 14

-NH-ketone
-NH-carbonyl-Ar
-O-ketone
-O-carbonyl-Ar

Question 15

Weakly activating o,p-directors

Answer 15

-R, -phenyl

Question 16

Weakly deactivating o,p-directors

Answer 16

-F, -Cl, -Br, -I

Question 17

Moderately deactivating m-directors

Answer 17

-aldehyde
-ketone
-COOH
-COOR
-CONH2
-SO3H
-CN

Question 18

Strongly deactivating m-directors

Answer 18

-NO2, -NH3+, -CF3, -CCl3

Question 19

Reactant: nitrobenzene
Reagents: Fe/HCl
Product:

Answer 19

NH2 replaces NO2

Question 20

Reactant: nitrobenzene with ketone at meta position
Reagents: Pd-C, H2
Product:

Answer 20

Simultaneously reduces NO2 to NH2 and chops off double bond O

Question 21

Reactant: chlorobenzene
Reagents: NaNH2, NH3(l)
Product(s):

Answer 21

LG leaves, benzene w/ NH2 where LG was or adjacent to where it was (through benzyne intermediate)

Question 22

Reactant: chlorobenzene
Reagents: NaOH, H2O, 300 psi
Product(s):

Answer 22

LG leaves, benzene w/ OH where LG was or adjacent to where it was (through benzyne intermediate)

Question 23

Reactant: chlorobenzene
Reagents: Na2CO3, H2O, 🔺, 300 psi
Product(s):

Answer 23

LG leaves, benzene w/ OH where LG was or adjacent to where it was (through benzyne intermediate)

Question 24

Reactant: chlorobenzene
Reagents: NaOH, H2O, 300 °C then HCl work-up
Product(s):

Answer 24

LG leaves, benzene w/ OH where LG was or adjacent to where it was (through benzyne intermediate)

Question 25

Reactant: 2,4-dinitrochlorobenzene
Reagents: NH2NH2
Product:

Answer 25

HN-NH2 replaces Cl

Question 26

Reactant: 2,4-dinitrochlorobenzene
Reagents: NaOMe
Product:

Answer 26

-OMe replaces Cl

Question 27

Reactant: 4-nitrobromobenzene
Reagents: CN
Product:

Answer 27

CN replaces Br

Question 28

Reactant: 1,3-dinitrobenzene saturated with chlorines
Reagent: NaN3 (excess)
Product:

Answer 28

N3 replaces chlorines that are o,p- to the NO2s or ortho to both

Question 29

Reactant: 2,4-dinitrochlorobenzene
Reagents: 1. Na2CO3, H2O, 100 °C
2. HCl, H2O
Product:

Answer 29

OH replaces Cl

Question 30

Reactant: 2,4-dinitrochlorobenzene
Reagents: NaCN
Product:

Answer 30

CN replaces Cl

Question 31

Rank the groups from most EDG to most EWG

Answer 31

EDG
-NR2
-OMe
-tBu, -Me
-H
-Br, -Cl
-COOEt
-CF3
-NO2
EWG

Question 32

Reactant: nitrobenzene
Reagents: H2/Pd
Product:

Answer 32

NH2-benzene

Question 33

Reactant: NH2-benzene
Reagent: HNO2
Product:

Answer 33

N2+ -benzene

Question 34

Reactant: N2+ -benzene
Reagent: H2O
Product:

Answer 34

Phenol

Question 35

Reactant: phenol
Reagent: ClCOR (acid chloride)
Product:

Answer 35

Benzene-O-COR

Question 36

Reactant: benzene-N2+
Reagents: HBr, CuBr
Product:

Answer 36

Bromobenzene