Experiment 3: Resolution of (+)-1-phenylethlamine and (-)-1

phenylethylamine, Part B




















Qualitative Observations
Observation
(-)-amine-(+)-tartrate salt white, solid, crystalline
NAOH-salt mixture with CH
2
Cl
2
(in seperatory
funnel)
Bi-layered liquid
Top layer: white, murky, opaque
Bottom layer: colorless, clear

Results
Compound MW
(g/mol)
Density
(g/mL)
Theoretical
Mass
(g)
Volume
(mL)
mmol
(+)- & (-)--phenylethylamine 121.180 0.9528 9.528 10.0 78.63
(+)-tartaric acid 150.09 12.0 79.95
(-)-amine-(+)-tartrate salt 271.27 39.315
Dichloromethane, CH
2
Cl
2
1.325

[Question 1]









[Question 2]
The yield of the final product, (-)--phenylethylamine, is 73%. A 100% yield of the resolved
amine would be undesirable as a high yield in a crystallization process for chiral resolution can
be an indication of low purity of the desired product or that some error has occurred during the
experiment. The maximum yield for resolution through crystallization is 50%.

Product Observed Mass
(g)
Theoretical Mass
(g)
% Yield
(Observed
Mass/Theoretical
Mass) x 100%


(-)--phenylethylamine
Beaker: 28.86
Beaker + Product: 32.34
Product: 32.34-28.86=
3.480
9.528/2 =


4.764
(3.480/4.764) x
100% =

73.05%


(-)-amine-(+)-tartrate salt


7.490
(39.315/1000) x
(271.27) =
10.665
(7.490/10.665) x
100% =
70.23%


Measurement of Optical Activity of Isolated Amine
Conditions:
Solvent System used in extraction: dichloromethane (CH
2
Cl
2
), water
Temperature: ~20
o
C
Optical Rotation: 589nm
Polarimeter cells light pathlength (l): 1dm
(-)--phenylethylamine density (): 0.9528g/mL

Optical Rotation of (-)--phenylethylamine:
Reported specific rotation: -40.40
o
+/- 0.2
o
(neat)
Observed rotation: -33.02
o

Calculated specific rotation = Observed rotation /( x l)
= -33.02/ (0.9528 x 1)
= -34.65
o
[Question 3]
% Optical purity = Calculated specific rotation / Reported specific rotation)
x 100%
= (-34.65/-40.40) x 100%
= 85.77%
[Question 4]
a) What is the specific purpose of adding the 2M NaOH solution during the extraction?
Addition of dilute, strong NaOH (basic) to ammonium salt (acidic) leads to the
abstraction of a proton from (-)-amine, which produces sodium tartrate, water, and the
recovery of free amine (-)--phenylethylamine.
b) What organic compound remains in the aqueous layer during the extraction? Why does this
compound dissolve easily in high pH solutions but not as much in low pH solutions?
The negatively charged tartrate ion stays in the aqueous layer during extraction. The ion
dissolves easily in high pH (basic) solutions but not as much in low pH (acidic) solutions
because tartrate ion acts as a weak acid. Weak acids can react with strong bases
(engaging in neutralization reaction) but do not readily participate in reactions with
strong acids because the negative charge on the ion makes it difficult for further
deprotonation in an acidic solution.
[Question 5]
If you wanted to isolate (+)--phenylethylamine, how could you change your experimental
procedure to accomplish this?
Upon addition of (R,R)-tartaric acid to the racemic mixture of -phenylethylamine to
produce diasteromeric amine salts, one is able to isolate (+)--phenylethylamine by the
addition of an optically pure acid to the amine salt. For example, (+)-lactic acid can be
used to react with (+)-amine and (-)-amine to produce the diastereomers:
(+)-amine and (+)-lactic acid
(-)-amine and (+)-lactic acid.
As diastereomers have different chemical and physical properties, the (+)-amine can be
separated through extraction into organic solvent.