9
92
N. A. Al-Awadi, M. Abdelkhalik, M. Patel and H. H. Dib
Vol 44
Calcd. for C H Cl N O (655.54): C 62.30, H 4.31, N 12.82.
3H, CH ), 2.51 (s, 3H, CH ), 6.09 (s, 1H, 6-H), 7.82 (d, 2H,
34
28
2
6
4
3
3
Found C 61.93, H 4.66, N 13.06.
,6,10,12-Tetramethyl-2,8-dioxo-1,7-bis-(3-oxo-3-thiophen-
-yl-propylideneamino)-1,7-diazacyclododeca-3,5,9,11-tetra-
arom. H, J = 8.4 Hz), 8.02 (d, 2H, arom. H, J = 8.4 Hz),
9.05 (s, 1H, 2-H).
4
2
4,6-Dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (16).
.
+1
1
ene-3,9-dicarbonitrile (11b). This compound was obtained as
MS: m/z = 149 (M ), C H N O (148.16). H NMR (CDCl ): ꢀ =
8 8 2 3
yellow crystals from DMF in yield (87 %, 5.2 g); mp 188-189
2.42 (s, 3H, CH ), 2.51 (s, 3H, CH ), 6.47 (s, 1H), 12.05 (br s,
3
3
°
C; ir: 3258 (NH) and 2216 (CN), 1669 (CO); MS: m/z = 599
1
H, NH D O exchangeable).
2
+
1
(M ). H NMR (DMSO): ꢀ = 2.32 (s, 6H, 2CH ), 2.40 (s, 6H,
3
3-(4-Chlorophenyl)-3-oxo-propionitrile (17a). MS: m/z =
2
7
CH ), 5.79 (d, 2H, 2-H, J = 8 Hz), 6.46 (s, 2H, 5-H and 11-H),
.+1
1
3
180 (M ), C H ClNO (179.61). H NMR (CDCl ): ꢀ = 4.02 (s,
9 6 3
2
H, J = 8.0 Hz).
-Oxo-3-thiophen-2-yl-propionitrile (17b). MS: m/z = 152
.15 (t, 2H, thienyl 3-H, J = 5.0 Hz), 7.74-7.91 (m, 6H, vinyl 3-
H, CH ), 7.54 (d, 2H, arom. H, J = 8.0 Hz), 7.88 (d, 2H, arom.
2
H, thienyl 2-H and 4-H), 10.08 (br s, 2H, 2NH). Anal. Calcd.
for C H N O S (598.69): C 60.18, H 4.38, N 14.04, S 10.71.
3
0
26
6
4
3
Found C 59.92, H 4.28, N 14.20, S 10.59.
,6,10,12-Tetramethyl-2,8-dioxo-1,7-bis-(3-oxo3-p-tolylro-
ylideneamino]-1,7-diazacyclododeca-3,5,9,11-tetraene-3,9-
dicarbonitrile (11c). This compound was obtained as yellow
crystals from DMF in yield (88 %, 5.4 g); mp 211-212 °C; ir:
.
+1
1
(M ), C H NOS (151.18). H NMR (CDCl ): ꢀ = 4.02 (s, 2H,
7
5
3
4
CH ), 7.15 (t, 1H, thienyl 3-H, J = 5.0 Hz), 7.74-7.82 (m, 2H,
thienyl 2-H and 4-H).
2
Acknowledgement. This work was supported by Kuwait
University through research grant # SC02/03 and ANALAB and
SAF grants # GS01/01 and GS03/01. The authors appreciate
very much Professor M. H. Elnagdi interest in reading and
revising the work.
.
+1
3
069 (NH) and 2216 (CN), 1671 (CO); MS: m/z = 615 (M ),
1
H NMR (DMSO): ꢀ = 2.31 (s, 6H, 2CH ), 2.37 (s, 6H, 2CH ),
3
3
2
5
.51 (s, 6H, 2CH ), 5.80 (d, 2H, 2-H, J = 8.0 Hz), 6.46 (s, 2H,
3
-H and 11-H), 7.25 (d, 4H, arom. H, J = 8.4 Hz), 7.72 (d, 4H,
arom. H, J = 8.4 Hz), 7.87 (d, 2H, 3-H, J = 8.0 Hz), 10.05 (br s,
2
5
H, 2NH). Anal. Calcd. for C H N O (614.70): C 70.34, H
36 34 6 4
.58, N 13.67. Found C 69.80, H 5.36, N 13.89.
REFERENCES
General procedure for Flash Vacuum Pyrolysis (FVP) of 11a-c.
The apparatus used is similar to that described in our recent
publications [10-11]. The sample was volatilized from a tube in a
Büchi Kugelrohr oven through a 30 x 2.5 cm horizontal fused quartz
tube. This was heated externally by a Carbolite Eurotherm tube
furnace MTF-12/38A to a temperature of 650 °C, the temperature
being monitored by a Pt/Pt-13%Rh thermocouple situated at the
center of the furnace. The products were collected in a U-shaped trap
cooled in liquid nitrogen. The whole system was maintained at a
[
1]
I.; Abdel-Khalik, M. M. Int. J. Chem. Kinet. 1996, 28, 741-748.
2] Al-Awadi, N. A.; Ibrahim, Y.; Kaul, K.; Dib, H. J. Phys.
Org. Chem. 2001, 14, 521-524.
3] Al-Etaibi, A.; Abdullah, M. R.; Al-Awadi, N.; Ibrahim,
Y.; Hasan, M. J. Phys. Org. Chem. 2004, 17, 49-55.
4] George, B. J.; Dib, H. H.; Abdallah, M. R.; Ibrahim, M.
R.; Khalil, N. S.; Ibrahim, Y. A.; Al-Awadi, N. A. Tetrahedron 2006,
2, 1182-1192.
Al-Awadi, N. A.; Elnagdi, M. H.; Mathew, T.; El-Gamry,
[
[
[
-2
pressure of 10 Torr by an Edwards Model E2M5 high capacity
rotary oil pump, the pressure being measured by a Pirani gauge
situated between the cold trap and the pump. Under these conditions
the contact time in the hot zone was estimated to be ꢁ 10 ms. The
different zones of the products collected in the U-shaped trap were
6
[
5]
6]
Ried, M. Chem. Ber. 1957, 90, 2841-2846.
[
Al-Saleh, B.; El-Apasery, M. A.; Abdel-Aziz, R. S.;
Elnagdi, M. H. J. Heterocyclic Chem. 2005, 42, 563.
7] Miller, B. Advanced Organic Chemistry 2 nd edition,
Prentice hall, upper Saddle River, NJ, 2004, pp 88.
8] Elnagdi, M. H.; Elmoghayer, M. R. H., Elgemeie, G. E. H.
Synthesis 1984, 1-25.
[
1
analyzed by H nmr, LCMS and GC-MS. Relative and percent yields
1
were determined from H NMR. Identities of compounds obtained
[
1
were confirmed by comparison of their H-NMR spectra with data of
products separated from preparative HPLC.
[9]
Al-Awadhi, H.; Al-Omran, F.; Elnagdi, M. H.; Infantes,
L.; Foces-Foces, C.; Jagerovic, N.; Elguero; J. Tetrahedron 1995, 51,
MS and NMR Characterization for Compounds 14, 16 and
1
2745-12762.
10]
Org. Chem. 2000, 13, 499-504.
1
7a,b.
[
Al-Awadi, N.; Kaul, K.; El-Dusouqui, O. M. E. J. Phys.
5
,7-Dimethyl-3-(4-methylbenzoyl)-pyrazolo[1,5-a]pyri-
+
dine-4-carbonitrile (14). MS: m/z = 289 (M ), C H N O
289.34). H NMR (CDCl ): ꢀ = 2.42 (s, 3H, CH ), 2.46 (s,
[11]
Ibrahim, Y. A.; Al-Awadi, N. A.; Ibrahim, M. R.
1
8
15
3
1
(
Tetrahedron 2004, 60, 9121-9130.
3
3