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
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
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.
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
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.
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