J. Chem. Eng. Data 1982, 27, 103-104
Acknowledgment Thanks are due to the Director, H. B. Technological Institute, Kanpur, for providing facilities. A.K.D. is thankful to CSIR, New Dehi, for the award of SRF. N.K.M. is thankful to Principal DBS College, Kanpur, for grantlng research facilitles.
Literature Cited (1) Tewarl, R. S.; Dubey, A. K. J . Chem. Eng. Data 1980, 25, 91. ( 2 ) Tewarl, R. S.; Dubey. A. K. Indian J . Chem., Sect. 8 1980, 19, 153.
109
(3) Tewarl, R. S.; M k a , N. K.; Dubsy, A. K. J . H9terocyde. Chem. 1981, 17, 953. (4) Sasakl, T.; Kanematw, K.; Yukknoto, Y. J. Chem. Soc. 1970, C-481; 1975, 594. (5) Bask&, N.; Piunkett, A. 0. Chem. Commun. 1971, 1578. (6) Kobayashl, Y; Kutsuma, T.: Seklne, Y. Tetmhec+on Len. 1472, 32, 3325. (7) Kobayashl, K.; Kumadak1,-I.; Seklne, Y.; Kutsuma, T. Chem. P a m . Bull. 1978. 21, 1118. (8) Henerlck, C. A.; Rltchle, E.; Taylor, W. C. Aust. J . Chem. 1967, 20, 244 1.
Recslved for revlew July 13, 1981. Accepted September 28, 1981. N.K.M. Is thankful to New Delhl for flnanclal aselstance.
Reactions with Heterocyclic Diazonium Salts. Synthesis of Several New Fused Azolotriazine Derivatives Husseln Salama El-Kashef, Kamal Usef Sadek, and Mohamed Hllmy Elnagdl’ Chemistry Department, Faculty of Science, Mi& University, Mink and Cairo University, Giza, A.R. Egypt
Hlkmat Husseln Alnlma Chemistry Department, College of Education, Sulaimaniyah University, Sulaimanlyah, Iraq
A variety of azolo-1,2,4-triazine derivatives were prepared via coupling dlazotlzed aminoheterocyciic derivatives with activated nttriies. Coupling of diazotized amino heterocycles with a-chloroacetylacetone and/or ethyl a-chloroacetoacetate afforded fused 1,2,4-triazoks. The Intermediately formed heterocycllc hydrazonyi halides could be isolated in m e cases.
I n continuation of our work aiming to explore the synthetic potentialities of heterocyclic diazonium salts ( 7 -3),we report here our further results in this direction. Thus, the diazotized aminoheterocyciic derivatives Ia,b, 11, and I11 coupled with activated nitriles to yield the azoiotriazine derivatives IVa-f, Va,b, and VIa-c. Similarly diazotized Ia,b coupled with achioroacetylacetone to yleld the thiazolo [3,2-c ] 1,2,4-triazole derivatives VIIa,b. On the other hand, the hydrazonyl chlorides VIIIa,b were obtained on coupling diazotized I1 with a-chloroacetylacetone and with ethyl a-chloroacetoacetate. Also compound III coupled with a-chloroacetylacetone to yield the hydrazone IX. Compound VIIIa could be cyclized into the benzimidazo[ 1,2-~]-1,2,4-triazolederivative X. On the other hand, VIIIb cyclized into the benzimMazo[ 1,2-c]-as-trlazine derivative X I by the action of phenylhydrazine. Slmilar to previous work (3),diazotized 5-amino-3-phenylpyrazole (XII) coupled with the 2-pyrazolln-5-one derivatives XIIIa,b to yield the hydrazones XIVa,b. Compounds XIVa,b did not cyclize into pyrazolotriazines under conditions reported to effect cyclization of structurally related hydrazones. The structures of the synthesized products were established on the basis of analytical and spectral data.
-
Experimental Section All melting points are uncorrected. I R spectra were recorded (KBr) with a Beckman spectrophotometer. ’H NMR spectra were obtained on an E M 9 0 9 M H z spectrophotometer using QQ21-9568/82/ l727-0l03$01.25/O
I V a . R = H . X=NH.YzCN
_.
b, R :CkHc, X: N H , Y :CN H
c,R:CH X:O.Y:CN 6 5’ d , R: H . X - 0 ,YI;COCH~
e, R: C,H,.X:
”.
Vo, X
0 , Y :COCH
1 , R:H.X:NH.Y:COPh
1
:
NH
b , X : O
NH
V I a , X:CN b. X i CO E l
c , XzCOPh
i l NoN02/H2S0, t11
X - CH2-CN
lX=CN.CO2EI wCOPh1
QR NU2
Io,R:H
Ill
F1
b,R:Ph
4
mR STNIX N-N
HC1
V I 1 0 , R:H , X i COCH) b R:C6H5 .X?COCH3
Ph
q.:
3c
XI1
X I V o . R:H b R:C6H5
Me,Si as internal Indicator, and chemical shifts are expressed in ppm. Analytical data were obtained from the analytical data unit at Cairo Universlty. React&ndD&zotk.dIa,b, I I , I I I , a n d X I I wlthActive Hydrogen A solution of 0.01 mol of diazotized Ia,b and 111 (prepared following the procedure described by
-.
0 1982 Amerlcan Chemlcal Society
104 Journal of Chemical and Engineering Data, Vol. 27, No. 1, 1982
Table I. List of the Products of Coupling Diazotized Ia,b, 11,111, and XI1 with Active Hydrogen Compounds (cry; solv)
yield, %
IVa
280 (a)
80
IVb
280 (b)
80
1625 (C=N); 2240 (CN); 3270, 3140, 3100 (NH) 1650 (C=N); 2210 (CN); 3580,3180 (NH)
N C
Nd
280 (c) 280 (d)
75 75
1700 (C=O); 2200 (CN) 1600 (C=N); 1680-1720 (CO) br
IVe
130 (a)
75
1580 (C=N); 1680-1720 (CO) br
IV f
200 (c)
70
Va Vb VIa
140 (e) 250 ( c ) 300 (c)
70 70 70
VIb
247 (c)
54
1620 (C=N); 1720 (CO); 3400, 3290, 3190,3360 (NH) 1680 (C=N); 2200 (CN); 3360 (NH) 1630 (C=N); 1680 (CO); 2200 (CN) 1660 (C=N); 2240 (CN); 3360-3300, 3070-3000(NH) 1630 (C=N); 1690 (CO); 3440 (NH)
VIC VIIa VIIb VIIIa
274 280 280 279
(c) (b) (e) (c)
50 60 60 60
1630 (C=N); 1650 (C=N); 1630 (C=N); 1610 (6NH);
VIIIb
146 (c)
60
1660 (CO); 3480-3460, 3140-3080 (NH)
IX
185 (c)
50
1680 (CO), 3330 (NH)
X
242 (c)
60
1640 (C=N); 1690 (CO)
XI
304 (c)
70
XIVa XIVb
260 (c) 255 (c)
60 50
1630 (SNH); 1670 (C=N); 1710 (CO); 3480,3380 (NH) 1680 (CO); 3350 (NH) 1670 (CO); 3300-3330 (NH)
compd"
IR, cm-'
'H NMR, ppm
7.2-8.0 (m, 4 H, aromatic protons); 10.2 (s, br, 1 H, NH) 7.2-7.8 (m, 4 H, aromatic protons); 10.0 (s, br, 1 H, NH)
1.3(t,3H,CH3);4.3(q,2H,CH,;7.2-8.0(m,4H,
1660 (CO); 3480-3460 (NH) 1700 (CO) 1670 (CO) 1640 (C=N); 1715 (CO)
" Satisfactory elemental analyses were found.
7.42 (d. 1 H. J = 6: thiazole H-5): 8.16 (d. . , 1 H.,J = 6: thiazole H14); 10.5 (s, br, 1 H,'NH) 7.4-7.8 (m, 6 H, aromatic and thiazole proton); 10.5 (s, br, 1 H, NH) 7.2-7.8 (m, 6 H, aromatic and thiazole proton) 7.38 (d, 1 H , J = 6 ; thiazoleH-5);8.12(d, 1 H , J = 6 ; thiazole H-4); 2.1 (s, 3 H, COCH,) 7.4-8.0 (m, 6 H, aromatic and thiazole proton); 2.0 (s, 3 H,COCH,)
aromatic protons); 11.2 (s, br, 1 H, NH) 7.1-8.2 (m, aromatic and NH protons) 2.1 (s, 3 H, CH,); 7.2-7.6 (m, 4 H, aromatic protons); 11.0 (s, br, 2 H, NH protons)
1.3(t,3H,CH3);4.2(q,2H,CH,);7.2-7.7(m,4H, aromatic protons); 10.9 (s, br, 2 H, NH, protons) 2.0 (s, 3 H, COCH,); 7.2-7.8 (m, 4 H, aromatic protons); 11.5 (br, 2 H, NH protons) 2.2 (s, 3 H, COCH,); 7.2-8.2 (m, 4 H, aromatic protons); 12.0 (s, br, NH) 7.2-8.0 (m, 9 H, aromatic protons); 11.5 (m, br, 2 H, NH and HC1)
a = acetone-water, b = DMF-water, c = ethanol, d = acetone, e = ethanol-water.
Morgan and Morrow (4)) and I I and X I I (prepared following the procedure described by us (2)) was added to a solution of appropriate active hydrogen compound in ethanol. (The diazonium salts should be used directly. Gradual decomposition in solution takes place on standing. Cautlon: Care shouid be taken on attempted isolation of the diazonlum salts or the diazo compounds in the solid state as some of these diazo compounds explode readily.) The solid product so formed on standing was collected by filtration and crystallized from the proper solvent (cf. Table I). I n the case of the products of coupling of diazotized Ia,b, the SdUHon was concentrated to half its volume and left to cool. The solid product so formed was collected by filtration and crystallized from the proper solvent (cf. Table I). 3,4-Dlkubsmuted Indsrolo[3,2-c]-ss-trlazlms( V l a - c ) . The experimental procedure described above for the reaction of diazotized I I I with malononitrile was adopted utilizing ethyl cyanoacetate and benzoylacetonitrile as coupling component, and the resulting coupling product was boiled in acetic acid under reflux for 4 h. The resulting sokrtlon was then evaporated and triturated with ethanol. The solid product so formed was collected by flltration and crystallized from the proper solvent (cf. Table I). 3 -Phenylhydrazlm -4-oxo -3,4 -dhydmberuhldazo [2,1c)-ss-tr/azh (XI).A solution of VIIIb (0.01 mol) in ethanol
(50 mL) and phenylhydrazine (0.01 mol) was refluxed for 3 h. The reaction mixture was then evaporated under vacuum, and the remaining product was triturated with water. The solid product so formed was collected by flitration and crystallized from ethanol. (cf. Table I). 6enz/"azo[2,l-c]-l,t,4-trlazo/e (X). A solution of VIIIa (0.01 mol) in benzene (50 mL) was treated with triethylamine (2.0 mL), and the reactlon mixture was refluxed for 2 h. The solvent was then evaporated under vacuum, and the remaining solld product was then collected by filtration and crystallized from the proper solvent (cf. Table I). Literature Cited (1) Elnagdl, M. H.; Elmoghayer. M. R. H.;Flelta, D. H.;Paher, E. A.; Fahmy, S. M., J . Oug. Chem. 1876, 4 1 , 3781. (2) Elmgdl. M. H.: E h ~ h a y e rM. , R. H.; Elfahham, H. A,; %Ham, M. M.; Alnima, H. H. J . Mterowc/k C h m . 1080. 17, 209. (3) Elnagdl, M. H.; Ebnoghayw, M. R. H.;Kandeel, E. M.; Ibrahlm, M. K. A. J . Heterocycl. Chem. 1977, 14, 227. (4) Morgan, G. T.; Morrow, G. V. J . Chem. Soc.1811, 107, 1294.
Received for review M y 15, 1981. Accepted September 29, 1981.
