2508 J . Org. Chem,., Vol. 43, No. 12, 1978
Spagnolo, Tundo, and Zanirato
and Y. Gopichand, Tetrahedron Lett., 3093 (1976). methoxyphenyl azide, 2101-87-3; 4-chlorophenyl azide, 3296-05-7; (3) E. Gaydou, G. Peiffer, and A. Guillemonat, Tetrahedron Lett., 239 3,4-dichlorophenyl azide, 66172-16-5; 2,4,6-trimethylphenyl azide, 97 1). 14213-00-4; 5-methyl-3-[2,2,2-trifluoro-l-(trifluoromethyl)ethyl]- (4) (1 W. J. Middleton and W. H. Sharkey. J. Org. Chem., 30, 1384 (1965). 2,1-benzisothiazole, 66172-17-6; N-ethy1-2-[3,3,3-trifluoro-Z-(tri- (5) Y. Ogata, M. Yamashita, and M. Mizutani, Tetrahedron, 30, 3709 fluoromethyl)propyl]aniline, 66172-00-7; methyl fluorosulfonate, (1974). 421-20-5; 2-[2,2,2-trifluoro-1-(trifluoromethyl)ethyl]benzothiazole, (6) 2. Yoshida, T. Kawase, and S. Yoneda, Tetrahedron Lett., 235 (1975). (7) Y. A. Cheburkov and I. L. Knunyants, Fluorine Chem. Rev., 1, 120 66172-01-8 2-aminobenzenethiol, 137-07-5; trimethyl phosphite, (1967). 121-45-9; triphenyl phosphite, 101-02-0; diphenyl 5,5-bis(trifluo( 8 ) M. S. Raasch, J. Org. Chem., 40, 161 (1975). romethyl)-2-(hexafluoroisopropylidene)-1,3-dithiolane-4-phospho- (9) M. S. Raasch, U S . Patent 3 752 827 (1973); Chem. Abstr., 76, 59456a nate, 66172-02-9; hexamethylbenzene, 87-85-4; durene, 95-93-2; 2(1972). [l,l-bis(trifluoromethyl)-2-(2,4,5-trimethylphenyl)ethyl]-4-(hexa- (IO) E. Schaumann, Chem. Ber., 109,906 (1976). (11) N. Lozac'h in Adv. Heterocycl. Chem., 13, 161-234 (1971). fluoroisopropylidene)-1,3-dithietane, 66172-03-0; p-methylanisole, (12) H.G. Hertz,G. G. Traverso, and W. Walter, Justus Liebigs Ann. Chem., 625, ~ ( p-methoxyphenyl)ethyl]104-93-8; 2-[1 , lbis(trifluoromethyl)-243 (1959);Y. Mollier, N. Lozac'h, and F. Terrier, Bull. SOC. Chim. Fr., 157 4-(hexafluoroisopropylidene)-1,3-dithietane, 66172-04-1; p-cresol, (1963). 106-44-5; p-tolyl 3,3,3-trifluoro-2-(trifluoromethyl)thiopropionate, (13) PCR, Inc., Gainesville, Fla. 66172-05-2; butadiene, 106-99-0; 6-(hexafluoroisopropy1idene)- (14) R. E. Lutz, P. S.Bailey, et ai., J. Org. Chem., 12, 760 (1947). (15) D. Y. Curtin, E. J. Grubbs, and C. G. McCarty, J. Am. Chem. SOC.,88,2775 5,6-dihydro-2H-thiopyran,24515-61-5; 2,3-dichlorobutadiene, 1653-19-6; 3,4-dichloro-6-(hexafluoroisopropylidene)-5,6-dihydro- (16) (1966). A. Burawoy and J. P. Critchley, Tetrahedron, 5, 340 (1959). 2H-thiopyran, 66172-06-3; pentamethyl-5-vinylcyclopentadiene, (17) A. Senier and R. B. Forster, J. Chem. Soc., 107, 1171 (1915). 20145-47-5; 3-(hexafluoroisopropylidene)-1,4,5,6,7-pentamethyl- ( 1 8 ) D. C. England and C. G. Krespan, J. Am. Chem. SOC., 88,5582 (1966). (19) R. 0. Lindsay and C. F. H. Allen in "Organic Syntheses", Collect. Vol. ill, 7-vinyl-2-thiabicycl0[2.2.1] hept-5-ene, 35012-44-3; spiro[4.4]nonaE. C. Horning. Ed., Wiley, New York, N.Y., 1955, pp 710-711. 1,3-diene, 766-29-0; 3-(hexafluoroisopropylidene)spiro[2-thiabicy(20) This experiment was carried out by P. H. Harvey. clo[2.2.l]hept-5-ene-7,1'-cyclopentene,35012-45-4; 6,6-diphenyl(21) Prepared using the procedure of P. A. S. Smith and J. H. Boyer in "Organic fulvene, 2175-90-8; 7-(diphenylmethylene)-3-(hexafluoroisopropySyntheses", Collect. Vol. IV, N. Rabjohn, Ed., Wiley, New York, N.Y., 1963, lidene)-2-thiabicyclo[2.2.l]hept-5-ene, 24515-65-9; 1,3-cyclohexapp 75-78. (22) E. Lieber, T. S. Chao, and C. N. R. Rao, J. Org. Chem., 22, 854 (1957):J. diene, 592-57-4: anthracene, 120-12-7; 12-(hexafluoroisopropyliE. Leffler and R. D. Temple, J. Am. Chem. SOC.,89, 5235 (1967). dene)-ll-thia-9,10-dihydro-9,lO-ethanoanthracene, 24515-64-8; (23) I. Ugi, A. Periinger, and L. Behringer, Chem. Ber.. 91, 2330 (1958). cyclooctatetraene, 629-3-0-9; 1,3-diphenylisobenzofuran, 5471-63-6; (24) Polysciences, Inc., Warrington, Pa. 1,2,4,7-tetrakis(methylene)cyclooctane, 35061-75-7; 3-(hexafluo(25) W. Schafer and H. Hellmann, Angew. Chem., 79, 566 (1967); Angew. roisopropylidene)-2-thiabicyclo[2.2.l]heptane, 35012-42-1; 4-(hexChem., Int. Ed. Engl., 6, 518 (1967). (26) E. 0. Fischer and H.Werner, Chem. Ber., 93, 2075 (1960);R. Y. Levina afluoroisopropylidene)-3-thiatricyclo-[4.2.2.02~~]deca-9-ene, 66172and T. I. Tantsyreva, Dokl. Akad. Nauk SSSR, 89, 697 (1953):R. E. R. Craig, 07-4. Diss. Abstr., 22, 2193 (1962). (27) Aldrich Chemical Co., Inc., Milwaukee, Wis. (28) F. Arndt, P. Nachtwey, and J. Pusch, Ber. Dtsch. Chem. Ges., 58, 1633 References and Notes (1925);S. Bezzi, M. Mammi, and C. Garbuglio. Nature (London), 182, 247 Contribution No. 2541. (1958). (a)M. S.Raasch, J. Org. Chem., 35, 3470 (1970);(b)ibid,, 37, 1347 (1972). (29) R. E . Benson and R. V. Lindsey, Jr., J. Am. Chem. SOC.,81,4247 (1959); New syntheses for (CF3)2C=C=S dimer have appeared: (c) (CF3)pS. Otsuka, A. Nakamura, T. Yamagata, and K. Tani, ibid., 94, 1037 (1972): C%=S dimer from(CF&C%F, and dithiocarbamates or salts of other R . J. De Pasquale, J. Organomet. Chem., 32, 381 (1971). (30) J. M. Brinkley and L. Friedman, Tetrahedron Lett., 4141 (1972). thiol acids: D. C. England, M. S. Raasch, and W. A. Sheppard, US. Patent (31) A reviewer suggests as another possible mechanism electron transfer from 3 694460 (1972); Chem. Abstr., 78, 161612 (1973). (d) (CF& aromatic to thioketene followed by proton (or H atom)transfer and fragment C=C=S dimer from (CF3)&=CF2 and KSPS(OEt),or S pius KF: B. L. recombination. Dyatkin, S. R . Sterlin, L. G. Zhuravkova, B. I. Martynov,E. i. Mysov, and i . (32) N-Ethylation of amines with ethanol and Raney nickel is well known: G. R. L. Knunyants, Tetrahedron, 29, 2759 (1973).(e)(CF3)2c%=S dimer from (CF%LC=CF+and salts of thiol acids: S. R. Sterlin. L. G. Zhuravkova. B. Petiit and E. E. van tamelen in "Organic Reactions", A. C. Cope, Ed., Wiley, New York, N.Y., 1962, pp 360-361; R. G. Rice and E. J. Kohn in "Organic i: Efatkin, ind i. L . Knunyants, lzv. Akad. Nauk SSSR, Ser. Khim., 2517 (1971); Bull. Acad. Sci. USSR, Div. Chem. Sci., 2386 (1971). (f) Syntheses", Collect, Vol. IV, N. Rabjohn, Ed., Wiley, New York, N.Y., 1963, (CF3)&=C=S dimer from (CF3),C=C=0 and imidazolethiones: H. Kohn pp 283-285; K. Venkataraman, J. Indian Chem. SOC.,35, 1 (1958).
Intramolecular Addition of Aryl Azides to the Azo Group. 2.' Synthesis and Properties of Benz[ cdlindazole N-Arylimines Piero Spagnolo,* Antonio Tundo, and Paolo Zanirato Jstituto di Chinzica Organica dell'liniuersitd, Viale Risorgimento 4, 40136 Bologna, Italy Received November 14,1977 Thermal and photochemical decomposition of 8-azido-1-arylazonaphthalenes results in intramolecular addition to the azo group to give previously unknown benz [cd]indazole N-arylimines in good yields by 1,5-cyclization. Only has also been observed. Chemical and spectroin one case 1,6-cyclization leading to a 2-arylnaphtho[l,8-de]triazine scopic properties of all N-imines are in accord with the proposed structures containing the stable 1,3-dipolar azimine system. Formation of products is discussed in terms of a possible concerted process not involving nitrene intermediates.
In a previous paper1 we have reported what appears to be the first definite example of addition of aryl azides to the azo g r o u p leading to the formation of azimines, 1,3-dipolar valence tautomers of unknown triaziridines, presumably through the intermediacy of nitrenes. Photochemical decomposition of a number of 2-azido-2'-arylazobiphenyls (1, Ar = aryl) was in fact found to afford benzo[c]cinnoline N arylimines (2) as major products as well as minor amounts of
4-arylazocarbazoles (3), 2-amino-2-arylazobiphenyls (4), and benzo[c]cinnoline ( 5 ) . These results prompted us to prepare a series of l-azido8-arylazonaphthalenes (6) and t o investigate their thermal and photochemical decomposition in the hope that analogous intramolecular additions of the azido group (or nitrene) to the peri azo group would lead to the formation of 2-arylnaphtho[l,8-de]triazines (7) and/or benz[cd]indazole N -
0022-3263/78/1943-2508$01.0Q/O O 1978 American Chemical Society
J . Org. Chem., Vol. 43, No. 12, 1978 2509
Intramolecular Addition of Aryl Azides to the Azo Group -
N=N,+/N-Ar
1
2
N,== N -Ar
'N'
N -Ar
N,=
\ "2
I H
4
3
N=N,
5
arylimines (8) by 1,6- or 1,5-cyclization, respectively. Reactions of peri-substituted 1-naphthyl azides are and the stereochemistry appears to be favorable for intramolecular reaction in these cases. Whereas several 2-substituted naphtho[l,8-de]triazines [7, Ar = alkyl or aryl; R = HI have been reported4 and have been shown to be formed by alkylation and arylation of the 1Hnaphtho[l,B-de] triazine: benz[cd]indazoles N-arylimines (8) (if formed at all) would provide the first examples of the as yet unknown benz[cd]indazoles N-imines [8, Ar = H, alkyl, or aryl; R = HI, which appear to be particularly interesting as members of heterocyclic N-imineW containing the rare 1,3-dipolar azimine f u n c t i ~ n . ~Moreover, !s benz[cd]indazole N-arylimines (8) would be representatives of the benz[cd]indazole system whose synthesis has not as yet succeeded in spite of several attempts Although several of its dihydro derivatives are known,3 so far the only authenticated examples of the benz[cd]indazole system are offered by the mono-2 and di-N-oxide.2 Azides 6a-c were obtained by diazotization of the readily available 1-amino-8-azidonaphthalene: coupling of the diazonium salt with phenol or l - and 2-naphthol, and methylation. Azides 6d-f were prepared by coupling of the appropriate aryldiazonium chloride with 8-azido-2-naphthol and subsequent methylation of the coupling products with methyl iodide-silver oxide. Attempted preparation of 8-azido-larylazonaphthalenee (6) by condensation of 1-amino-8-azidonaphthalene with aryl nitroso compounds was unsuccessful. S,
N=N--Ar
Ar
6
II
-
hii(a)
-N,
JmRmR A+
4 'y-
NI = N +/N-Ar I
4 \
/.i 6
\
8
R = I
