Aromatic &Enolate

Question 1

Carbonyl -> alkyl

Answer 1

Clemmenson reaction

Zn, HCl

Question 2

Nitro -> amine

Answer 2

H2, Pd (cat)

Question 3

Activating groups

Answer 3

Phenol + phenylamine (e- donation)

Question 4

Deactivating groups

Answer 4

Nitro, carbonyl, nitrile
+ve charge eg NMe3+
Halogens (ortho/para directing)

Question 5

Amine -> amide

Answer 5

CH3CO(O)COCH3

Reduces reactivity

Question 6

Amide-> amine

Answer 6

HCl

Acid

Question 7

Making lithium enolate

Answer 7

LDA, THF, -78°C

Forms least substituted enolate

Question 8

Limitations of lithium enolates

Answer 8

Don’t work with aldehydes

Don’t work with hindered alkylating agents

Question 9

Making silyl enol ether

Answer 9

Me3SiCl, Et3N, heat

Question 10

Regioselectivity of silyl enol ethers

Answer 10

More substituted enolate

Question 11

Pro of silyl enol ethers

Answer 11

More stable than lithium enolates

Question 12

Con of silyl enol ethers

Answer 12

Less reactive than lithium enolates

- will only react with good electrophiles eg carbocations

Question 13

Lithium enolate to silyl enol ether

Answer 13

Me3SiCl

Question 14

Silyl enol ether to lithium enolate

Answer 14

MeLi

Question 15

Carbonyl to imine

Answer 15

1° amine, acid

Question 16

Carbonyl to enamine

Answer 16

2° amine, acid

Question 17

Enamine to carbonyl

Answer 17

Br-R, H2O

Stork enamine alkylation

Question 18

Features of stork enamine alkylation

Answer 18

Favours less substituted enamine

Works well with Sn2- reactive alkylating agents

Question 19

Removing ester from dicarbonyl

Answer 19

1) NaOH, H20

2) HCl, heat

Question 20

Making B- dicarbonyl

Answer 20

Claisen reaction

1) Ester + NaOEt
2) +H+