Experiment 4

CHEM 613
Experimental Organic Chemistry
2013
Anastazija Ristovska

Post-Lab
Microscale Preparation of Benzyl Quinoxaline
Quinoxaline derivatives such as 2,3-diphenylquinoxaline are an important
class of nitrogen-containing compounds that are widely used in pharmaceuticals,
dyes, electrical and photochemical materials. One method of preparing 2,3disubstituted quinoxalines is the Suzuki-Miyaura coupling reaction wherein
o-phenylenediamines (with or with no substituents on other positions of the Figure 1
benzene ring) are condensed with 1,2-dicarbonyl compounds as the one shown in
figure 1. Benzil is one such compound.
In our reaction the R substituents are phenyl, but generally they can vary.

Figure 2
Benzil, being an -diketone, can participate as the 1,2-dicarbonyl compound in a
condensation reaction with o-phenylenediamine. The reaction in fact resembles Diels-Alder
reactions. The purpose was to perform dehydration synthesis and obtain
2,3-diphenylquinoxaline. 100mg benzil and 100mg 1,2-phenylenediamine were placed in a
reaction tube which was then placed in a beaker filled 1/3 with water and heated on a heat plate
for 10min. Inside the beaker we also placed another reaction tube filled methanol so that both
tubes and the contents in them can be heated simultaneously for the same period of time
(10min). When 10min passed we added 2.5ml of the hot methanol to the reaction tube. Before
heating benzil appeared yellow in color and 1,2-phenylenediamine was hazel white-off color. The
powder-crystalline contents of the reaction tube during heating liquefied and turned orange.
Upon adding hot methanol a translucent orange solution was obtained. When transferred to an
ice-bath, white crystals formed in the test tube.

These crystals are our final product, and they were isolated using vacuum filtration. The
product was confirmed to be 2,3-diphenylquinoxaline via melting point, mass spectral, and FTIR
analysis. The melting point was found to be 122-124C. The theoretical yield was 185mg, and the
weight of the isolated crystals was 175.1mg. Thus the percent yield is 94.65%.

60

621 609

817802

929

731

1022
1076
978

1059

1442

Transmittance

851
872

1478

1129 1142
1155
1177
1220
1226
1248
1291
1315 1331

3057

957
9931001

1367
1496

1557

3026

40

20

763

1347

771
697

0
4000

3000

2000

1000

Wav enumber (cm-1)

Figure 3: 2,3-Diphenylquinoxaline synthesized (FTIR-KBr pellet)

The only non-aromatic stretch that should show up in the IR spectrum of
2,3-diphenylquinoxaline is the C-N bond vibration stretch. Tertiary amines do not give the same
vibration stretches as primary and secondary amines do since they have no N-H bonds, but only
C-N bonds. In the spectrum in figure 3 the C-N bond stretch can be clearly seen at 1347cm-1.
The C-H stretches from all the benzene rings show at 3026cm-1 and 3057cm-1.

282

100

N
50
N

50
0

26 32 39

0
10 20 30 40
50
(mainlib) Quinoxaline, 2,3-diphenyl-

179

76
62
60

86 93
70

80

90

103 112

126

140

152

163

190

205

100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290

Figure 4: 2,3-Diphenylquinoxaline Mass Spectrum

The molecular weight peak is given at m/z=282, and there is a peak of similar intensity at
m/z=281, probably caused by the loss of a proton. Since the molecular weight peak is way
stronger than all the rest of the peaks it can be concluded that the molecule analyzed is very
stable under the fragmentation technique of the spectrometer. The peak at m/z=179 is obtained
by cleaving off an N-C-Ph group. The peak at m/z=76 is obtained by cleaving off two N-C-Ph
groups, leaving only a benzene ring, or a benzene short of two protons. The m/z=283 peak
occurs because some portion of the molecules in the analyzed compounds had a hydrogen atom
attached to any one of the two nitrogen atoms in the molecule for a total +1 charge.

Figure 5: 1,2-Diaminobenzene FTIR (KBr pellet)

At 660-910cm-1 a very broad C-N bond stretch wag can be noticed. At 3190cm-1 a
primary amine N-H stretch is seen, and there is one also at 3287cm-1. The two sharp stretches at
3365cm-1 and 3386cm-1 are likewise N-H stretches. The C-N stretch is seen at 1274cm-1 with an
IR wavenumber value characteristic for aromatic amines, and the 1501cm-1 stretch characterizes
the C-C in-ring vibrations. At 1592cm-1 and 1633cm-1 there are two N-H bends characteristic for
primary amines. The three peaks from 3015cm-1 to 3039cm-1 come from the aromatic ring C-H
bond vibrations.
108

100

H2N
80

50

H2N

15

25

10
20
(mainlib) 1,2-Benzenediamine

28

81

53
30

39 41

30

40

43 45

55
50

61 63 65 67 69
60

70

74 76 78

82
80

91 93
90

105
100

110

120

Figure 6: 1,2-Diaminobenzene Mass Spectrum

3

The molecular weight peak shows up at m/z=108. The peak at m/z=80 occurs when the
benzene ring is cleaved into two parts, one consisting of the two carbon atoms at the 4 and 5
positions, and the other one being C-C(NH2)-C(NH2)-C.

Figure 7: Benzil FTIR (KBr) Spectrum

The benzil compound mass spectrum is expected to have a carbonyl stretch in the
1660cm-1 to 1760cm-1 range, and indeed we do see two carbonyl stretches, supposedly due to the
two carbonyl groups, one at 1660cm-1 and the other one at 1677cm-1. The 3064cm-1 stretch is
representative of the aromatic C-H bond vibrations. The 1579cm-1 and 1594cm-1 stretches are
the aromatic C-C in-ring vibrations. Between 696cm-1 and 676cm-1 there is an aromatic C-H
oop stretch.
105

100

77
50

51

27

39 43

20
30
40
50
(mainlib) Ethanedione, diphenyl-

74

57 61
60

70

85
80

117
90

100

110

120

149
130

140

150

165
160

210

181
170

180

190

200

210

220

Figure 8: Benzil Mass Spectrum

The molecular weight peak is at m/z=210 and it is very weak, meaning that the molecule
is not stable under the molecular fragmentation technique used in the mass spectrometer. The
m/z=77 peak comes from the phenyl fragments, i.e. just the benzene rings after they have been
cleaved off from the rest of the molecule. The strongest peak is at m/z=105 and comes from the
fragment obtained when the benzil molecule is cleaved exactly in half, i.e. the single bond
between the two carbonyl carbon atoms O=C-C=O is broken.
4