Ampliación de Química Orgánica.

Curso 2023-2024

Bulletin N. 4. Nitrogen Containing Organic Compounds

1. Draw the structures of the intermediates A–D in this synthetic sequence:

i. Pr2NH, CHCl3, 40oC iii. NaOH 50% v. KOH/EtOH 2 productos

A B C may + D min
NO2 ii. iv. H2SO4

2. Complete the following sequences for the following transformations (a and b)

O
NaOH
(a) H + (b) HNMe2

NaNO2 NaOH EtOH

NCO
Br

NH2 (d)
(c)
?
NH2

NH2

3. Propose a sequence of reactions to perform the following transformations: (a) from 3-tert-butyl-3,4,4-
trimethylpent-1-ene to 2,2,3,4,4-pentamethylpentan-3-amine, (b) from 2-methylpropanoic acid to 1-
chloro-3-methylbutan-2-one, (c) from 2-nitrobutane to 4-amino-2,4-dimethylhexan-3-ol.

4. Propose structures for all compounds whose formulas are presented in the following scheme:

O
NH MeOH IMe (2 eq.) i. LiAlH4, ii. H3O+
C7H15NO2 C9H19NO2 C9H21NO3S
iii. CH3SOCl, Et3N

iii. NaOH aq, 50% O NaNO2

C12H23NO2 C12H24N2O3 C8H18N2O2
iv. HCl, H2O CHCl3 DMSO
KOH
EtOH
H2O2 50oC O
C12H21NO C12H21NO2
 Ampliación de Química Orgánica. Curso 2023-2024

5. Complete the synthetic sequence and identify each of the products, explaining their formation in a
reasoned manner.
O CH2N2
H
1) Ag2O (2 equiv)
a b
2) SOCl2

1) H2O 1) NaN3
2) CH2N2 2) H2O, ∆ hν

c d e
6. The reaction of nitromethane and benzaldehyde in the presence of a base leads to nitroolefin Q, which
reacts by heating with cyclopentadiene to give compound R (C13N13NO2). Treatment of an ethanolic
solution of R with a catalytic amount of platinum(IV) oxide in hydrogen atmosphere yields compound
S (C13N17N). S reacts with ethanal (1 equivalent) followed by catalytic hydrogenation of the
intermediate, leading to the T (C15H21N compound). On the other hand, compound R is treated with
50% sodium hydroxide and then compound U is obtained with concentrated sulphuric acid. Determine
all the structures of the compounds involved in the synthetic sequence.

7. Propose a synthesis for the following compounds from benzene or toluene (four to choose from):
CH3 NH2 CH3
NO2
(a) (b) (c) (d)
Br Br NO2 CO2H
Cl

CH3 NH2 COOH NH2

(e) (f) (g) (h)

NO2 NH2 Cl
NO2 Br NO2

8. Propose a sequence of reactions required to perform the following transformations. Write down the
structures of the intermediate compounds (a and b).

H Ph
N Ph
OH
(a) O (b) Ph Ph
O

NH2

(d) NH2
(c) NO2 NH2
OH Cl

9.Complete the formulas for compounds A–E and the final product of the following synthesis.
 Ampliación de Química Orgánica. Curso 2023-2024
O

HO LiAlH4 1) MsCl, Et3N, CH2Cl2 NaNO2

A B NO2
Et2O 2) NaI, acetona DMSO

O
i-Pr2NH, CHCl3, 40 °C

H2, Lindlar KOH 1) NaOH 50%

? EtOAc
E
EtOH
D
2) H3O+
C