Chem 2124 Amine practice problems

1. Draw the structure of the following compounds. a. pyridine

N b. piperidine

N H c. o-toluidine CH3 NH2 d. 2,3-dimethyl-2-butanamine

NH2 2. Give an acceptable name for each of the following compounds. N CH3
4

CH3 N,N-dimethylbenzylamine

N Cl-

tetrabutylammonium chloide

3. How might the presence of an NH functionally be indicated using NMR spectroscopy?

The N-H hydrogen can be exchanged with deuterium by simply adding D2O to the sample. This will cause the N-H signal to disappear from the 1H NMR spectra.

4. Circle the stronger base in the pair below, and briefly explain your choice.

NH2

NH2

The lone pair of electrons on the nitrogen in aniline are delocalized into the aromatic ring, which reduced the ability of aniline to donate electron (be a base). 5. Provide a detailed, stepwise mechanism for the reaction of acetyl chloride with n-propylamine.
O CH3 C Cl + H2NCH2CH2CH3 O CH3 C Cl H N CH2CH2CH3 H O CH3 C H + Cl H N CH2CH2CH3

O CH3 C H N CH2CH2CH3 + HCl

6. Complete the following reaction sequences. a. 1) Ag2O 2) heat N CH3 CH3 3) CH3I 4) Ag2O 5) heat

b. NH2 CH3I (excess) NaHCO3 N(CH3)3 I

c. O Cl CH3CH2NH2 NaHCO3 O NCH2CH3 H

d. CH H 3

e. O2N Br

f.
H NH2

g.
O CN

h. + HBr N N H

+ Br

i. H3C N CH3 H2O2 H3C O N CH3

j. O Cl 1) CH3NH2 O NHCH3 2) LiAlH4 3) H2O NHCH3

k. Give an efficient method for preparing 1-pentanamine from 1-butene.

HBr peroxide Br NaCN acetone 1) LAH CN 2) pH adjust NH2

l. Give an efficient method for preparing ethylisopropylamine from ethylamine. acetone / H lose of water 1) LAH 2) pH adjust H N

NH2

m. Devise an efficient method for preparing only 1-pentanamine from 1-chloropentane. Cl xs NH3 NH2

n. Complete the short synthesis below by providing the necessary reagents. NH2 1) NaNO2 / HCl 2) CuCN 3) LAH NH2

7. Circle the following amines that could be formed by reduction of an amide? 1) benzylamine 2) isopropylamine 3) aniline 4) triethylamine The answer is #1 and #4. 8. Provide a detailed, stepwise mechanism for the acid-catalyzed condensation reaction between benzaldehyde and methylamine.
O H
+

O H

H H2NCH3 H

H NHCH3 H

Base

CH3 N H

H NHCH3 H

H NHCH3

Base

N CH3

The base is either the amine or water.

9. Circle the most basic compound in each of the following pairs. O NH2 A. or NH2 B. H N or O

The answer is A and B. 10. Propose a synthetic route to prepare p-nitroaniline from aniline.
NH2 NH2

NO2

O 1) CH3 C Cl / NaHCO3 2) HNO3 / H2SO4 3) H+ / H2O / heat

11. A compound with the formula C11H16N2 gave the following IR and 1H NMR spectra. The proton at 1.6 ppm disappears on shaking with D2O. Propose a structure for the compound and show how your structure accounts for the observed spectra data.

5H

2H 4H 4H 1H

5 aromatic hydrogens (mono substituted benzene). Isolated CH2 at 3.5 ppm attached to aromatic ring and nitrogen. Peak @ 1.6 ppm is a N-H, since there is only one hydrogen this is a 2 amine. The other nitrogen must be a 3 amine. The peaks at 2.4 and 2.8 ppm indicate symmetrical ethylene groups CH2CH2-.

CH2 N

NH