..
'2 0
the microscale laboriitory
. stating from Moo3powder, which is cheaper than the eon-
. ventional (NH4)6M07024. 4H20.
using the common 24% (13 M) instead of 15% (8 M)NH1-
solution.
adding the reagents kquentially by weighing, which facili-
tates the work up.
ending the washings with diethyl ether so that drying the
prcduct is more rapid.
i Aluminum chloride is a very common chemical that may
A Typical Run
In a 5-mL conical vial (on an electronic balance) is
placed 0.25 g (1.7 mmole) of Moo3 powder, 0.40 g H20 and
0.40 g (5.5 mmole) 24% NHs (Pasteur pipet). The mixture
is stirred with a glass rod for about one min to obtain a
clear colorless solution (exothermic reaction). Then, 0.75 g
(7.5 mmole) of 2,4-pentanedione is added. and the mixture
is stirred; however, two phases remain: Finally, 1 g (10
mmole) of 63% HN03 is added dropwise (exothermic reac-
tion). The mixture is cooled to mom temperature while
stirring and the solid formed is ground until a yellow pow-
der results. (Powdering the initially lumpy precipitate im-
proves the purity of the product and requires less than 5
min.) The product is filtered through a Hirsch funnel,
washed consecutivelvwith distilled water (4 x 2 mL). etha-
nol ( 2 x 2 mL)and peroxide-free diethyl ether (2 x 2 mL),
and dried in air. Washings also may be done by decanting.
The powder settles sufficiently in less than 1 min so that
more than 75% of the liquid can be removed. Using a Pas-
teur pipet is advisable in this case to reduce product losses
because M ~ O ~ ( a .c aforms
c ) ~ a supernatant skin every time
water is added.
The entire process requires about 30 min. About 0.19 g of
a light yellow finely powdered product melting at 179 f 1
"C (the reported value) is obtained. The IR spectrum of the
compound shows two strong bands at 900 and 930 cm-I
corresponding to the stretching vibrations characteristic of
the cis-~00'arran~ement. &nglets a t 2.12 and 2.14 6
(CD2C12, room temperature), assignable to the two sets of
inequivalent methyl groups (see drawing), are observable
in the 'H NMR spectrum.
Acknowledgement
I am grateful to the editor for helpful
comments.
Llteratum Cited
1. See, e. g.: (a1 Srivastava,A.; Ma.Y.; Panhayatselvan,R.;
D i n e , W.;Nicholss, K M. J C k m . Soe.,C k m . Com-
mun. lssP,853.~bIB~to~,C.;Mmzur,C.;CerriUo,n.;
Robert, F:Oaueerh, P.I n o n Chem. 1984.33, 1421.
2. chakrsvorti, M. c.;~ ~ ~ dn. ~ ~synth.~
l s s ~29,129.
, Schematicdiagramsfor (a)the preparation and (b) washing of AiCI, under an inert atrnospheri
A8 Journal of Chemical Education
I "F
._
Microscale Preparation of AICI)
Francisco J. Arndlz
Laboratorio de Quirnica lnorgtmica
Universidad de Burgos
09001 Burgos (Spain)
be prepared by several procedures ( I ) , including that re-
cently reported for the synthesis of a number of anhydrous
halides (2).AlC13is rarely prepared to be used as starting
material for other experiments because it is available at
low cost. However, it is very moisture sensitive, and special
care is required in handling pure samples. Purification
prior to use (usually by sublimation) is frequent. When a
small amount of anhydrous MC13 is needed for microscale
synthesis (or as a catalyst for reactions that might be
aborted with deactivated MCls), the method described
here represents a convenient alternative to others. It is
based on the reaction of aluminum iodide, prepared in situ,
with alkylchlorides (31, as represented in simplified form
(CH& is formed and the excess Al is reacted) in the equa-
tion below.
Al + 3/2 I, + 3 CH2CI2-t AlC1, + 3 CH,ICI
Anhydrous CHzClz is the solvent of choice by availability
and low cost, but especially because the reaction proceeds
smoothly. The reaction can be conducted conveniently with
inexpensive materials. A typical run is described.
A 5-mL ampoule is charged consecutively with 50 mg
(1.85 mmol) of pure aluminum foil cut in fine strips (10-15
pieces), 2 mL of CH2C12,and 650 mg (2.56 mmol) of dry Iz.
The ampoule (A) is connected to a T tubing (T) that is fur-
ther assembled (the figure, part a) to the gas line (or to an
inflated balloon) and to a 50-cm long bent tubing (kc.)as
an air condenser and connected to a bubbler (B).
The system is flushed with 1-2 L of an inert gas (argon,
nitrogen, or dry air), the clamp (C) is closed, the reactant
, - ;, , . , . , . .'
8
b)
I~ d h ~ ~ ~ ,
mixture is refluxed until all iodine is consumed (15-30
min, visual color loss) and then for an additional 30 min to
insure that the aluminum excess is dissolved. During this
process a significant amount of CHzClzmay be lost (the air
condenser is not very effective with this volatile solvent);if
so, a new portion of solvent should be added (e.g., by injec-
tion through a rubber connection) to restore the original
volume. The white powdered microcrystalline product
(AICIJ is washed with CH2Clz(three 2-mL portions) and
dried in vacuo. The washing may be achieved conveniently
in a dry atmosphere once the giass tubing is disconnected
bv removing the solvent with a Pasteur pipet. The pipet
should havea glass wool plug, as shown in the figure part
b. Paper or cotton plugs are unadvisable because AlC13re-
acts with, and strongly adheres to, these materials. 180 mg
of pure AlC13 were obtained. Anal. Calcd for AlC13: Al,
20.23; Cl, 79.77. Found: Al, 20.1; CI, 79.5. Iodine test (Hz02
on the solid) negative.
Literature Cited
In ring substitution of aromatic amines, the amino group
acts as a powerful activator and an ortho-/para- director.
However, in the strongly acidic nitration media, the amine
is converted into anilinium ion; substitution is thus con-
trolled not by the -NH2 but by the -NH3+ group which, be-
cause of its positive charge, is a strong ring deactivator and
directs
~ ~ - - much
~ ~ -~ ~of the substitution to the meta- oosition (4.
~
. .
5).I t is possible, however, to direct the nitration reaction to
the ortho- position by first protecting the amino group in
the acetanilido form (i.e., acylation),carrying out the nitra-
tion reaction. then de~rotectingthe amino group by hy-
drolysis (see reaction).

Microscale Electrophilic Aromatic Substitution

of pToluidine
lsmail 0. Kady
East Tennessee State University
Johnson City, TN 37614

Although many organic chemistry experiments deal

with electrophilic aromatic substitution, few illustrate the
principles of group protection, substituents' effect on reac-
tivity, and reaction orientation ( 1 3 ) .In this paper we pre-
sent microscale experiments that allow first-year organic
chemistry students to apply group protection and study
the effect of ring substistuents on the reaction orientation
in the nitration of disubstituted aromatic amines. These
experiments incorporate common synthetic organic trans-
formations and techniques which involve: (a) nitration of
unprotected p-toluidine, (b) protection of amino group, (c)
nitration of protected p-toluidine, and (dl deprotection of
amino group.
Most of the reactions involved are relatively fast and are
complete in 30 min. In each experiment, it is possible for
the student to determine the extent of the reactions by
comparing the physical and spectral properties of reac-
tants and products. Although the methods and techniques
presented are adapted from basic organic chemistry labo-
ratory texts such as those of Marmor ( I ) and Brewster (21,
these experiments use simple glassware, common chemi-
cals, and standard microscale procedures. All reactions CH3
give good yields of products to allow recrystallization and 6
proton NMR analysis. Comparison of physical and spectral Experimental
properties of the products enable the student to demon-
strate the relationship between ring activation and reac- Nitration of p-Toluidine
tion orientation in electrophilicaromatic substitution. Pro-
cedures for the microscale reactions and purification of Dissolve 107 mg (1.0 mmole) of p-toluidine in 0.2 mL of
products are described below. Therefore, these experi- concentrated HzS04 in a dry micro test tube. Shake the
ments can be incorporated easily into a first-year mi- tube until all the solid dissolves; then cool in ice. Carefully
croscale organic laboratory cumculum. and dropwise add 0.4 mL of a solution consisting of concen-
trated HN03 (0.3 mL) and concentrated HzS04 (0.1 mL),
This paper was presented in part at the 13th Biennial Conference while keeping the temperature of the reaction mixture be-
on Chemical Education, Lewisburg, PA, 1994. low 5 "C. After the addition is complete, allow the reaction

Volume 72 Number 1 January 1995 A9