Carmen

Question 1

Conditions for the Tiffeneau-Demjanov rearrangement?

Answer 1

NaNO2, HCl
(migrating group anti peri planar to LG)

Question 2

Conditions for 1,2 hydride/alkyl shift

Answer 2

H+

Question 3

Conditions for the pinacol rearrangement

Answer 3

H2SO4
Unsymmetrical, more stable carbonate formed

Question 4

Conditions for semi-pinacol rearrangement

Answer 4

TsCl, Py
OTs as LG on less hindered C- give pinacol for less stable carbo cat

Question 5

Pyridine into an N-oxide?

Answer 5

H2O2

Question 6

Conditions for Paal-Knorr synthesis (making pyrroles)

Answer 6

NH3
(H+ for O, P2S5 for S)
+6 C di carbonyl

Question 7

Conditions for vilsmeier reaction (pyrrole+amide-‘acylation’)

Answer 7

i) POCl3
ii) Na2CO3, H2O (turns C=N into C=O)

Question 8

Conditions of chichibabin reaction (amination of pyridine)?

Answer 8

i) NaNH2, NH3(l)
ii) H+

Question 9

How to make diazonium salts (N2+Cl-)?

Answer 9

i) Nitrated benzene + Sn/HCl to NH2
ii) NaNO2/HCl (0-5 degrees, H2O)