A DiazotizationCoupling Reaction: The Preparation of Methyl

Orange
Formation of a diazonium ion
Azote is an old word for nitrogen. Hence, the presence of azo in the name
of a chemical implies that nitrogen is present in the structure. Therefore, diazo
means two nitrogen atoms. When combined with onium, we have diazonium,
which means two nitrogen atoms and a positive charge (i.e., N
2
+
. !iazonium ions
are produced when an ar"l amine reacts with cold nitrous acid. Nitrous acid is
unstable and is prepared #ust prior to its use b" a reaction between sodium nitrite
and h"drochloric acid. $igure % shows the conversion of aniline into the positive
benzene diazonium ion.
NH
2
+ HNO
2
N N Cl
-
aniline
nitrous acid
benzene
diazoniu chloride
HCl
+
! "
!
O
#igure $% The diazotization of aniline.
Substitution Reactions of Diazonium Ions
& diazonium ion is the cation of a salt, and it is a reactive intermediate that
undergoes substitution or coupling reactions. Table % shows some groups that ma"
substitute for a diazo group bonded to an arene (&rN
2
+
.
Table $% 'roups that substitute for N
2
+
in &rN
2
+
.
(eagent 'roup )roduct
*u+r (H+r
*u*l (H*l
*u*N (,*N
+r
*l
*N
&r+r
&r*l
&r*N
,- - &r-
*u
2
., *u(N.
/

2
, H
2
. .H &r.H
H
/
).
2
H &rH
Lab 13 %
& generalized e0uation for a substitution reaction is shown below in which
the reagent can be an" reagent in Table % and 1 an" group.
N
2
+
reagent
X
Coupling Reactions of Diazonium Ions
*ompounds such as aniline and phenol, which contain strong electron
donating groups (e.g., 2.H and 3NH
2
that activate the ortho and para positions on
a benzene ring, can undergo coupling reactions with a diazonium ion. & coupling
reaction is one in which two ar"l rings are #oined b" an azo group. These
coupling reactions usuall" occur at the para position of the o,p director. $igure 2
shows the coupling of benzene diazonium ion with phenol at the para position of
phenol.
+
benzene
diazoniu chloride
+ "Cl N N Cl
-
OH H N N OH
phenol
diazo product
#igure !% *oupling reaction with phenol.
&niline ma" serve as the substrate for the formation of a diazonium ion as
shown in $igure %, and it ma" serve as the substrate for a coupling reaction with
the diazonium ion as shown in $igure /.
+
benzene
diazoniu chloride
+ "Cl N N Cl
-
NH
2
H N N NH
2
aniline
diazo product
#igure &% *oupling reaction with aniline.
The mechanism for a coupling reaction is shown in $igure 4. The reaction is
an electrophilic aromatic substitution reaction5 therefore, the mechanism is similar
Lab 13 2
to that for the nitration of benzene (i.e., it is a two2step reaction in which the first
step is rate determining.
+
benzene
diazoniu ion
N N OH H
N N OH
phenol
diazo product
N N OH
H
slow
fast
#igure '% 6echanism of coupling.
The Experimental Reaction
-n this e7periment, sulfanilic acid is the primar" ar"l amine that will be
diazotized, and N,N2dimeth"laniline is the ring2activated benzene derivative to
which the diazonium ion will couple in the para position. $igure 8 shows the
structures of aniline, N,N2dimeth"laniline and sulfanilic acid. +oth reactants are
derivatives of aniline.
SO
3
H
NH
2
N
H
3
C CH
3
NH
2
aniline N(N)diethylaniline sulfanilic acid
#igure *% &niline derivatives.
Lab 13 /
9ulfanilic acid contains a sulfonic acid group (9.
/
H and an amino group
(NH
2
5 therefore, it undergoes an internal acid2base reaction to form a di2ionic
species. 9odium carbonate acts as a base and deprotonates the 0uaternar"
ammonium ion. The ensuing sulfonate salt is diazotized with cold nitrous acid, as
shown in $igure :.
SO
3
H
NH
2
sulfanilic acid
SO
3
-
NH
3
H
+
transfer Na
2
CO
3
SO
3
-
NH
2
HNO
2
cold
SO
3
-
N
2
+
diazotized
sulfanilic acid
#igur
e +% !iazotization of sulfanilic acid.
The diazotized sulfanilic acid couples with N,N2dimeth"lamine, as shown in
$igure ;. &d#ustment of the pH to about 4 b" the addition of Na.H "ields an
orange product <nown as meth"l orange. 6eth"l orange is the well2<nown acid=
base indicator and is an e7ample of an anil, an aniline2based d"e. -f the pH is not
properl" ad#usted a dar< red compound helianthin might be isolated instead of
meth"l orange.
diazotized
sulfanilic acid
+
-
O
3
S N N N(CH
3
)
2
N(N)diethylaniline
-
O
3
S N N N(CH
3
)
2
H
H
+
transfer
-
O
3
S N N N(CH
3
)
2
H
NaOH
helianthin ,red-
NaO
3
S N N N(CH
3
)
2
ethyl orange
Lab 13 4
Procedure
Preparation of the Diazonium Ion of Sulfanilic Acid
%. Weigh >.:2g anh"drous sodium carbonate and transfer it to a 282m? @rlenme"er
flas<.
2. &dd 82m? water to the @rlenme"er and dissolve the solid completel".
/. Weigh >.22g sulfanilic acid and transfer it to the @rlenme"er.
4. $ill a %8>2m? bea<er half full of water and heat to boiling on a hot plate.
8. -mmerse the @rlenme"er flas< in the hot2water bath, using a pair of tongs or test
tube holder.
:. &fter all of the sulfanilic acid dissolves completel", remove the @rlenme"er
flas< and allow it to cool to room temperature on the bench top.
;. Weigh >.>A2g sodium nitrite, NaN.
2
, and transfer it to the cooled @rlenme"er
flas<5 stir the solution until the solid dissolves.
A. *ool the 282m? @rlenme"er flas< in an ice2water bath for %> min.
B. &dd five drops of concentrated h"drochloric acid to the @rlenme"er while it
remains in the ice bath.
The diazonium salt of sulfanilic acid precipitates as a finel di!ided" #hite
solid$ %eep the suspension in the ice bath until needed in Step & belo#$
Preparation of the Diazo De 'ethl (range
%. &dd four drops of N,N2dimeth"laniline and two drops of glacial acetic acid to a
small test tube.
2. Transfer the solution of N,N2dimeth"laniline from 9tep % to the 282m?
@rlenme"er flas< in the ice bath. ,eep the @rlenme"er in the ice bath.
/. 9tir the mi7ture vigorousl" with a stirring rod.
A red precipitate of helianthin forms$
4. ,eep the @rlenme"er flas< in the ice bath for %> min.
Lab 13 8
8. 9lowl" add %.82m? %>C sodium h"dro7ide to the @rlenme"er while it remains
in the ice bath.
:. (emove the @rlenme"er from the ice bath, dr" it with a paper towel, place it on
the hot plate and heat the mi7ture to boiling.
;. (emove the @rlenme"er from the hot plate and add >.82g sodium chloride to the
hot solution.
A. &llow the @rlenme"er to cool on "our bench for two min., and then place the
flas< in an ice2water bath. &fter cr"stallization is complete, collect the d"e on a
pre2weighed filter paper in a +Dchner funnel.
B. (inse the @rlenme"er flas< with / m? of an ice2cold, saturated solution of
sodium chloride5 swirl the @rlenme"er and pour this solution into the +Dchner
funnel.
%>. &llow the d"e to dr" on its filter paper, and then re2weigh the filter paper to
determine the "ield of meth"l orange. *alculate the percent "ield.
If our next experiment is an un)no#n sugar" continue #ith the
follo#ing procedure" other#ise s)ip to Step * belo#$
Preparation of Solution for Specific Rotation
,To be conducted one .ee/ before obser0ing the rotation-
%. .btain an un<nown sugar, show the instructor the number of the un<nown and
record it in "our lab noteboo<.
2. ,eep about >./ g of the un<nown for ne7t wee<Es e7periments.
/. Tare a 282m? volumetric flas< on an anal"tical balance that measures to four
decimal places (instrument room.
4. Transfer the remainder of the un<nown sugar (about / g to the volumetric flas<
and record the mass of the un<nown.
8. &dd distilled water to the volumetric flas< until the water level reaches about 2
cm below the etched mar< on the flas<.
Lab 13 :
+ater #ill be added to the mar) at the next lab meeting$ The sugar #ill
undergo mutarotation during this time$
:. 9topper the volumetric flas<, mar< it with "our initials, and save it in the
designated location until ne7t wee<.
;. *lean the glassware, ensure the balance area is clean and the balances are turned
off. @nsure the sin<s are clean with no solid materials left in them.
Lab 13 ;
Diazotization 1uestions
?ast nameFFFFFFFFFFFFFFFFFFFFFFFFFFF, $irst nameFFFFFFFFFFFFFFFFFFFFFFFF
%. !raw the structure of m2bromo2N,N2dieth"laniline.
2. *onsider the structure of sulfanilic acid. -t has two functional groups, one is an
acid and the other is a base. Write the formula for the partial structure that
constitutes the acid part of sulfanilic acid. FFFFFFFFFFFFF Write the formula for
the partial structure that constitutes the base part of sulfanilic acid. FFFFFFFFFFFFF
$rom what inorganic acid and base are these partial structures derivedG
FFFFFFFFFFFFFFFFFFFFFF and FFFFFFFFFFFFFFFFFFF
-f "ou answer these 0uestions correctl", "ou should 0uic<l" realize wh" these two
groups react.
/. Wh" is the amino group in aniline an o,p directorG
4. !raw resonance structures that support "our answer to problem /.
8. Write an e0uation for the diazotization of aniline.
Lab 13 A
*omplete the following e0uations b" inserting the reagent or product.
:.
;.
A.
B.
%>.
N N
+
N N
+
,-
N N
+
NH
2
N N
+
.H
N N
+
*N
Lab 13 B