January, 1971] Studies on Heteroaromaticity. XLIV.” BULLETIN OF THE CHEMICAL soctETY OF JAPAN, VoL, 44, 185—169(1971) 185 Reactivities of Benzoyl Cyanide N-Oxide and Some Derivatives Therefrom Tadashi Sasaki, Tos ‘osuioxa, and Yasuyuki SuzuKI Institute of Applied Organic Chemistry, Faculty of Enginering, Nagoya Univesity, Chikusa-hu, Nagoya (Received July 13, 1970) ‘o-Chloroisonitrosoacetophenone was treated isoxazolinines and -isoxazoles, respectively 5-(mnitrophenyl)-1,2,f-oxadiazole. duced were converted to the corresponding 1,2,3-triazoles thermally or by the treatment with a base. phenylisoxazole afforded 2-benzoyl-5-phenyloxazole. line afforded a new type of induced rearrangement of 3-benzoyl- chloroisonitrosoacetophenone with azi benzoyloxazoline. It is surprising that there have been no reports on the preparation and reactions of benzoyl cyanide N-oxide (I) in contrast to abundant reports on benzo- nitrile oxide, though a-chloroisonitrosoacetophenone (IL, phenylglyoxylyl chloride oxime) is a readily availa~ ble compound? and is regarded as its precursor. Holle- man® postulated the intermediary formation of I in the preparation of 1,5-dibenzoylfuroxan from aceto- phenone. Because of the presence of a carbonyl con- Jugated with the nitrile oxide group, I is thought to be stabilized by the resonance, but presumably reactive enough to undergo the I,3-dipolar cycloaddition re~ actions. In this paper, the results in the 1,3-dipolar cycloaddition reactions are discussed in comparison wit those in similar reactions of benzonitrile oxide. The thermal and basic rearrangement of the phenylhy- drazones of 3-benzoylisoxazole and -oxadiazole thus produce and the photo-induced rearrangement of 3- Dbenzoylisoxazole are discussed. The ring-enlargement of the aziridine adduct of I is also described. Results and Discussion 1,3-Dipolar Cyeloadditivity In order to examine 1,3-dipolar cycloaddition reactivity, II was treated in ther with triethylamine in the presence of a dipolaro- phile (styrene, for example) according to the general procedure for preparing the nitrile oxides." ‘The oily product was characterized as 3-benzoyl-5-phenylisoxazo- line (I11) after conversion to its crystalline picrate on the basis of analytical and spectral evidences. A further evidence was provided by its conversion to crystalline B-benzoylisoxazole (XVIII) with N-bromosuccinimide (NBS). A similar treatment of II with acrylonitrile afforded 3-benzoyl-5-cyanoisoxazoline (IV); IV showed xo nitril absorption in the IR spectrum, which supports S-cyano structure.® An attempt to convert it to isoxazole K, Kanematsy, Y. Org. Chem in pres. 1 Gol. Vol. 8, 191 (1955). 3) fan, Ber 208, 3359 (1887); 20B, 2835 (1888), 4) For instance, see Huigen and W. Mack, Terabedon Let, 1961, 583. 5) The quenching effect of nitrile absorption intensity is greater when the oxygen-containing group i attached to the same earbon ftom as the nitrile, ce LJ. Bellamy, “The Infra-red. Spectra of | Complex Molecules,” Methuen & Ca, Ld, New York (1969), p. 266. ith ethylenic and acetylenic di ‘With m-nitrobenzaldoxime or m-nitrobenzonitrle, it yielded 3-benzoyl- ‘The phenylhydrazones of the 3-benzoylisoxazole and -oxodiazole thus pro- larophiles to afford 3-benzoyl- ‘The photo- Treatment of wo idine oximes, which was converted to 2- with NBS was unsuccessful, th sulfuric acid gave benzoic acid, while 3-(5-nitro- 2-furyl)-5-cyanoisoxazole (V) was convertible to the corresponding amide under similar conditions. Treat- ment of II with two equivalent amounts of I-mor- pholino-2-cyanocthylene in ether at room temperature afforded 3-benzoyl-4-cyanoisoxazole (VI) similar to the 1,3-dipolar cycloaddition of aromatic hydroxamoyl chlo- rides to the enamine after spontaneous elimination of a morpholine molecule from the initial 1 : 1 adduct.” VI was hydrolyzed to amide under acidic conditions. Treatment of II with o-aminophenol and methyl ane thranilate afforded linear adducts, N-phenylglyoxylyl- e-aminophenol oxime (VII) and methyl N-phenyle glyoxylylanthranilate oxime (VIII), respectively, but with o-phenylenediamine, a cyctized product, 3-benzoyl- IAdihydro-1,2,4-benzotriazine (IX), instead of the expected benzoxazole” or quinazoline” and benzimida- zole?! in the similar reactions of aromatic hydroxamoyl chlorides. VILL was cyclized, however, to 3-hydroxy- 4-0x0-2-benzoyl-3,4-dihydroquinazoline (X) on treat~ ment with hydrochloric acid. With I-eyano-2-diethyl- aminoacetylene,” II afforded 3-benzoyl-4-cyano-5-i- ethylaminoisoxazole (XI) as in the case of arom hydroxamoyl chlorides,” but with ammonium thio- cyanate in methanol, ‘II unexpectedly'® yielded N- benzoylthiourethane (XII). Since the products IIT and IV could be obtained by the thermal 1,3-dipolar cycloaddition reactions of II in almost quantitative yields, the thermal reactions were performed using several dipolarophiles; the results are summarized in ‘Table 1. As seen from this table, ethylenic and acetylenic olarophiles reacted with IL to give the corresponding. isoxazolidines, III, IV, and XIII—XV, and isoxazoles, XVI-XX, respectively; the yield of the latter was lower because of the thermal instability. It should bbe mentioned that the yield of the former was almost quantitative In order to compare the reactivity of If with that Acidic hydrolysis of 1V and ‘T. Yoshioka, "This Bulletin, 41, 2212 (1968). ind ‘F. Yoshioka, iid, 42, 3595 (1959), 8) T, Sawaki and T. Yoshioka, bid 41, 2206 (1968). 9) T, Sauk’ and A. Kojima, J. Chem. Soc, C, 1970, 476. 10), Musante, Gaz. Chin. Hal 68, 331 (1998); T. Sasaki sand T. Youhioks, Vukigosei Kagaku Kyotai-shi, 27, 877 (1968). 11). Sasaki and T. Yoshika, his Bulletin, 40, 2604 (1967),106 ‘Tadashi Sasaxs, Toshiyuki Youoxa, and Yasuyuki Suzvxt [Vol 44, No. 1 BgN— e819 —e ag & Sy btecat a oN ou Bee a, EB son $B en Bae es son sree, area Eit-ex — Econ, Ho—cH CH,C0-, NP-ON-E 6, ReGHCOC- Be ©” Sou Sou ‘Tames 1. Trnwat1,3-omrotax evetosnpmiow oF TL we FeO va NMR (GOGH) «Mp (coupling con Cy Dipolaopites Products Pte " 6% H% N% Biiplnie as — Styrene Ti 16g) GI.9F 3.85 16.08 1655 4.50 6.70 262 (35900) (61.25 3.97 16.24) (10.5 #12) 233 (21900) Acrylonitrile vo 134 0 65.95 4.15 19,90 1610 4,54 6.19 (65.99 4.03 13.99) (10.5 Hz) Acenaphthylene = XI 132,30 80.45 4.15 4.68 1610 9.38 4.27 (00.25 4138 4.68) (9H) Tndene XIV 91-92 6 85 78.00 5.05 5.48 1640 3.79. 5.49 (77135 4.98 5.32) (12 He) Acrylic acid XV 106-22 8-59.85 4105 6.45 1610 4.79 6.95 6.68 (CH,) (60.27 4.14 6.39) (9.8142) Acctlnie. Phenylacetylene XVI. 91 Bg") 77.26 4.95 5.91 1650 2.982 (7.09 4.45. 5.62) Diphenylacetylene = XVI MBS BLLBZ 4.50 451650 (arn 4.65 4.31) Propargyl alhol = XVIT_ oil) 7 9055.70 3.45 19.15 1650 (55.59 3.57 19.07) Propargyl bromide XIX 6015-8 «49.40 3.07 5.25 1650 (19.65 3.03 5.27 LEthynyl cyclohexanol XX oil 1240.71.05 6.45. 5.20 1650 — 3.30 (70.83 6.32 5.16) 4) quantiave yields 6) analyzed as pcrate Analyzed as dnitophenyibydrazone mp 19640 for XVIL and mp 250°C for XX. of hydroxamoyl chlorides, II was treated with benzami- affords the corresponding dioxazole.® Even taking dine to afford 55% yield of 24,6-triphenyl-1,3,5-triazine, fa trimer of benzamidine. This indicates no reactivity, of IT with benzamidine, with which hydroxamoyl chlo- Fides are known to afford oxadiazoles.” With m- nitrobenzonitrile II afforded 15% yield of 3-benzoyl- 5-(m-nitrophenyl)-1,2,4-oxadiazole (XX1), while the same compound was prepared from I and m-nitro- benzaldoxime in 50% yield. With m-nitrobenzaldchyde, IT underwent no cycloaddition, while benzonitrile oxide into consideration these different reactivities from benz hydroxamoyl chloride, IT might be concluded to be a good starting material for the preparation of 3- benzoylisoxazolines and -isoxazoles. Br-C—N RON+1 —+ N G-R — Il} R-CH-NOH Nor XXIJanuary, 1971] Rearrangement of 3-Benzoplisoxazole and 3-Benzoyloxadi- azole. a) Thermal and Basic Treatments: Boulton at al® have reported on the interesting thermal rearrangement reactions of one heterocycle to another as exemplified by those of 3-acetylisoxazole to 1,2,3+ triazole via the phenylhydrazone and to 1,2,3-oxadiazole via the oxime. According to the modified procedure by Kano and Yamazaki,!® p-nitrophenylhydrazone of XVIII was melted with copper powder to afford a quantitative yield of 2-(p-nitrophenyl)~4-phenyl-5-phen- acyl-1,2,3-triazole (XXII), which was also obtained quantitatively by such a basic treatment as ammo- nia Similarly, 2,4-diphenyl-5-phenacyl-1,2,3-triazole (XXII) was obtained from the phenylhydrazone of XVIII in 50% yield by thermal treatment. Thermal and basic treatments of the f-nitrophenylhydrazone of 3-benzoyl-1,2,4-oxadiazole (XXI) afforded 1,2,3-triazole (XXIV) in 60 and 90% yields, respectively. “A similar rearrangement of f-nitrophenylhydrazone of VI failed, presumably because of the presence of a 4-substituent; thermal treatment afforded tarry polymer and the basic treatment resulted in recovery of the starting material, Attempts to obtain the oxime and the semicarbazone of XVIII were unsuccessful in contrast to the results given by Spiro and Ajello.** Studies on Heteroaromaticity. XLIV 187 4) Photochemical Treatment: One feature in the photo- induced rearrangement of five-membered heterocycles, is that two vicinal heteroatoms can interchange their positions to 1,3-system when irradiated with ultraviolet, light. ‘This example involves the photo-induced re- arrangement of 3,5-diphenylisoxazole to 2,5-diphenyl- oxazole" and that of benzisoxazole to benzoxazole," but not that of 3-acylisoxazoles. Thus, XVIIL (UV. 2888 ma (s): 262 (35900) and 233 (21900) was irr diated at room temperature under nitrogen stream, Chromatography of the reaction mixture afforded 2- benzoyl-S-phenyloxazole (XXV), N-benzoylbenzoyl- acetamide, dibenzoylacetonitrile, benzoic acid. andjor benzamide. ‘The product distributions under different conditions are summarized in Table 2. ‘The thermal and basic rearrangement reactions of XVIII and XXI might be explained by the radical and ionic mechanisms proposed by Kano and Yama- zaki and Ullman and Singh. For photoinduced rearrangement of XVIII, a similar explanation for that from 3,5-diphenylisoxazole to 2,5-diphenyloxazole™™ can be applied by postulating the intermediacy of 2,3- dibenzoylaziridine (A) andjor N-benzoylbenzoylketen- imine (B) after its benzoyl migration (+). ‘The exclusive formation of benzoic acid in the reaction of XVIII in ethanol might be originated from hydrolytic photo- cleavage by contaminated water in the solvent. ra Beg cie mag te —> xr Se Bai-C-cilbe—a—> Tec 8) N 1? BAMEOCILRe B+ bans ms Ring-enlargement. TI was treated with two equi- valent amounts of aziridine in ether at room tem= perature to afford oily N-phenylglyoxylylaziridine oxime (XXVI), which was converted to erystalline O-p-nitro- benzoate (XXVI). Since XXVI is regarded as a new type of azividine oximes,”) ring-enlargement was GH, C—C-NHCOG,Hy-m-NO, carried out, Thus, XXVI was refluxed in acetone = with a catalytic amount of sodium iodide to give an Sy oily amine, which was characterized as 2-benzoyloxazo- Ro XXIV: R’=p-NO,-GHe- line (XXVIII) after conversion tothe erytalline pcrate, ‘amis 2, Porocimnsray op Sanexzovi-S-muenveoxszous (XVII) (Wields % based on the converted XVIID) Produ dsibatons Reaction Recorred ying Solvent Mercury lam ‘ime Benzoyl — “mee he XVI xy “benno tte Mag enamide Benzene 6O-Wlow pressure. 42. 23 28 Esher 6O.Wlowpremre 1829 BD Ethanol 60.Wlow presure 24 oS Benzene 100.Whigh presure?” 8070 2) Using alii iter No 5. A. Schonberg, “Preparative Organic Photochemistry, vip 8 12) A.J. Boulton, A. R. Kauitahy, and A. M, Hamid, J. Ohm Soe, ©, 1967, 2005, 18} H. Kano and B. Yamazaki, Titrobedon, 2,159, 461 (1964). 14), V. Spiro and E, Ajello, dns Chin, (Rome), 58, 128 (1968). 13}, EP. Ullman and B. Singh, J. Amer. Chem. Soc, 88, 1844 (1966); 89, 6911 (1967). D. W, ‘Kure and H. Shechtcr, Chon Commun, 1966, 689 16) M. Ogata, HL. Matsuno, and H. Kano, Abstract of the ‘Symposium on the Chemistry of Heterocyclic Compounds P. 157 (Osaka, Oct, 1968) 17) T, Sataki and T. Yoshioka, ‘This Bulletin, 42, 556 (1969)188 ‘Tadashi Sasaxt, Toshiyuki Yosuoxa, and Yasuyuki Suzuxt ‘The yield of the conversion to XXVIII was improved up to 60% by treating with coned. hydrochloric acid in acetone at room temperature." BeC-NOH BzC-NOCOG,H,p-NO, B2C—_O NX a cH” xxv XXVINI Experimental AAll_ melting points were determined on a Yanagimoto electric micromelting point apparatus and are uncorrected. ‘The ultraviolet (UV) and infrared spectra (IR) were record clon a Jeoleo Model ORD/UV-5 and a Jasco Model IRS fpectrometer. ‘The NMR. spectra were determined on a Varian A-60 and a Jeoleo Miva, with tetramethylsilane as an internal standard and the peak postions are expressed bby revalues. Column chromatography was carsied out on a slieangel (Mallinckrodt, 100 mesh) using benzene as an ‘huent ‘$-Benzpl-S-phapliosazoline (I) 4) Nivile Oxide Method: ‘To a stirred solution of 184g (0.01 mol) of om chloroionitrxoacetophenone (11) and 1.04 (0.01 mol) of styrene in 50 mi of ether was added a solution of 1.2 ¢ (0.012 rol) of tiethylamine in 10 mf of ether under cooling with fceowater. "The reaction mixture wat sired at room tem perature overnight. The resulting precipitates (triethyl: Amine hydrochloride) were removed andthe flrate was con- centrated. The residual oil was converted to the erystaline Pierate, mp 219—220°C, and analyzed (Table 1). ‘The Yield was 30%, 4) Theat Treatment: A solution of the samme amounts of the two components as above in 50 mi of toluene was refluxed, for IGhbr. ‘The solvent was removed and the residual cil was purified as above to give a quantitative yield of IIT (Table 1). 1s Goncersion to 9-BenzoylS-phenliaxazale (XVII). solution of 10g of IIT and 0.75 g of N-bromesuccinimide (NBS) in 20 ml of carbon tetrachloride was refluxed in the presence of a trace of azobisizobutyronitrile (AIBN) for 3 he ‘The reaction mixture twened from red to pale yellow. The mixture was filtered and the filtrate was concentrated. The residue was treated with a solution of 0.25 ¢ of potassium hydroxide in 10m! of methanol to afford 0.5 (50%) of XVIIT, mp 91°C, which was identical with a specimen pre pared from IT and phenylacetylene (Table 1. Phenylhydra- zone, mp 106—107°C. Found: C, 77.935 H, 5.605 N, 12.54%. ON, G, 77.85; H, 5.05; Ny 12.38%, pNitrophenylbydrazone, mp 191—192°C. UV AU mye (0): 396 (31700), 278 (16500) and 250 (22100) ound: C, 68.953 H, 4.35; N, 14.45%. Caled for Gy O.Ne: C, 68.745 1, 420; N, 14.50%, ‘s-Bimspl-Sgensiosasoline (IV). IV was obtained fiom 11 and acrylonitrile by the avile oxide method in 30% Yield, but by dhe thermal procedure quantitatively. (Table 1) 3-(B-Nit2fupl)-S-yanosxazaline (V) and Is. Conversion lo Amide. "Thermal treainants A solution of 0.95 @ (3 mmol) of S-nitro2-furylhydroxamoyl chloride™ and. 10g 20 mmol) of acrylonittile in 40 ml of woluene was refluxed for I5he. The chromatography afforded 0.74. (70%) of YV, mp 109°C, by reerystallzation from ethanol. TR (KBs): le absorption at around 2200—2400 em Found: ©, 46.53; H, 2.575 N, 20.41%. Caled for CyH,- OWN: G, 46.585 H, 243; N, 20.29%. Caled for CxsHe [Vol. 44, No. 1 ‘The same compound was obtained in 65% yield by the nitrile oxide method. Conversion of V to the amide was carried out as follows a solution of 0.3 ¢ of V in 4mi of coned. sulfuric acid was stirred at room temperature for 2 days. The reaction mix- ture was poured onto ice-water and the resulting yellow crys- tals were collected and recrystallized from ethanol~THF 10 afford the amide in 75% yield, mp 225°C, which was identical ‘with a specimen! by TR comparison. S-Benzoyl-d-epenvioxazole (V1). solution of 1.84 g (0.01 mol) of IK and 2.8 (0.02 mol) of I-morpholino-2- cyanocthylene! in 50 mf of ether was stirred at room tem- perature for one week. ‘The resulting precipitates were filtered and the solvent was removed from the filtrate. ‘The residual solid was recrystallized from n-hexane to give 60% Yield of VI, mp 73—74°C. IR (KBr) emt: 2250 (Vey), and 1660 (ye). NMR (CDCL) +: 0.09 (6, 1H, CH). Found: C; 67.04; H, 3.25; N, 14.07%. Caled for CuH- ON, C, 66.663 H, 3.05; N, 14.14%, “is Cowersion to Amide. Similar as in the case of V, VI was treated with eoned, sulfuric acid to afford the amide, mp I74—175°G, in 70% yield. IR (KBr) em: 3400, 3350 (uu) ane 1670 (veo) Found: C, 60.89; H, 8.805 N, 13.09%. O.Ng: © 61.11; H, 3.33: N, 12.96%. N-Pharylatyosybl-o-aminophenol Osine (VIL). ‘Treatment of IT with two equivalent amounts of e-aminophenol in ether at room temperature for 1 day afforded 70% yield of VII, mp 162—163°C, by reerystallization from a 10 :| mixture of benzene and ethanol. IR (KBr) em": 1660 (ve). Found: C, 66.17; H, 4.913 N, 10.57%. Caled for Clr OWN: G, 65.625 H, 4.725 N, 10.93% “Metiy! N-Pherlghexylslantianilate Oxime (VII). Sienix larly, a solution of 0.92 g (5 mmol) of [and 1.51 g (10 mmol of methyl anthranilate in 70-mi of ether was left standing at room temperature for two months. Chromatography of the filrate afforded 0.5 ¢ (30%) of VIII, mp 162—164°C, by recrystallization from ethanol. TR (KBr) emt: 3340 (rq) and 1675 (be) Found: C, 64.955 H, 4.75; N, 9.38! 1G, 6842; H, 4.73; N, 9.39%, S-BenzgleLstaibio-1,2,4-bonzoriasie (IX). A simi lar treatment of II with e-phenylenediamine for 3 days affor- ded. 75% yield of IX, mp 223—225°C, by recrystallization from a3 1 mixture of benzene and ethanol. IR (KBr) em 3200 (yyy) and 1640 (ye) Found: 71.03; Hy 403; Ny 17.57%. ONg: C, 70.875 H, 4.675 N, 17.71%. Cancers of VIE to 9-Hydrxy-f-ono-2-benzyl-34-dibydro- quinazolie (X).—_A solution of 0.2 g of VII in I al of coned, hydrochloric acid was warmed at 60—70°C in a sealed tube for 20 min, After cooling, the resulting crystals were collected and recrystallized from benzene « petroleum ether to afford 0-1 g (50%) of X, mp 76—78°C. IR (KBr) ex": 3450, 2250 (broad bound vay!), 1670 and 1650 (9) Found: G, 67.753 H, 3.82; N, 10.60%. Caled for Cyl Ny: G, 67.665 H, 3.79; N, 10.52% ‘S-Benzeyl-t-cyono-5-dethylaminoioxasole (XI) Treats ment of 184g (0.01 mol) of II and 22. (0.02 mol) of di cthylaminoeyanoacetylene! in 50 mf of ether at room tem perature for one week afforded 40% yield of XI, mp 133— 134°C, on chromatography. IR (KBr) em: 2240 (Vo) and 1650 (¥eo)- Caled for CH Caled for Cyt Caled for CHa 18). Sasaki, T. Yoshioka, and K. Shoji, J Glam. Sac, C, 1969, 1086, 19)" A. Domer and K. Fisher, Chem. Ber, 99, 72 (1966).January, 1971] Found: C, 66.905 H, 5.685 N, 15.6294. OWNs: G, 66.905 H, 5.61; N, 15.61% N-Benzoylthiowethane (XII). A solution of 045 ¢ (2.5 ‘mmel) of Hin 10 mi of methanol was added to a stirred solu- tion of 0.35 g (5 mmol) of ammonium thiocyanate in 10 mf ‘of methanol at room temperature. Chromatography afforded, 0.3 g (70%) of XIT, mp 98—99°C from benzene - petroleum, ether, which was identical with a specimen prepared from benzoyl syanate and methanol.) Reaction of HE with Benzamidine. "To a stirred mixture of a solution of 1.0 g of II in 30 mf of ether and a solution of 0.9 g of benzamidine hydrochloride in 20ml of water was added a 5% aqueous potassium carbonate (1.6) under ice-cooling. Stirring was continued for I2hr. Ether layer ‘was separated, from which 0.6 ¢ (85%) of 2,4,6-triphenyl- 1,3,5-triazine, mp 240°C (lit 239°C) was isolated. Found: C, 81.39; H, 5.03; N, 13.66%. Caled for CyHs- Nay: G, 81.53; H, 4.89; N, 13.58%. ‘B-Benzoyi-5-(rm-nitrophenyl)-1,2,4-oxadiazole (XX1). This ‘was prepared by refluxing in toluene for 20hr of II with menitrobenzaldoxime and m-nitrobenzonitrle in 50 and 15% yields, respectively. Mp 174—175°C. IR (KBr) em-*: 1673 (a) Found: C, 61.00; H, 3.21; N, 13.98%, OWNs: G, 61.025 H, 3.07; N, 14.25%. ‘The pnitrophenylhydrazone: mp 294—295°C. Found: C, 58.65; H, 3.35; N, 19.47%. Caled for CyyHy- OWNg: G, 58.60; H, 3.28; N, 19.58%. ‘Thermal Rearrangement of The Hydrazones of XVIII. Gen- eral procedure: the hydrazone was melted with 1/3 of its weight of copper powder in a vacuum at a temperature slightly higher than the melting point for 10min. The residue was extracted with hot ethanol to give the corres- ponding triazole. ‘Thus, 24-diphenyl-5-phenacyl-1,2,8-triazole (XXIII) was ob- tained in 50% yield at an oil from the phenylhydrazone of XVI. TR (KBr) cm: 1685 (gq). NMR (CDC) +: 5.42 (2H, -CH,-). Its 2,4-dinitrophenylhydrazone, mp 210— aire, Found: C, 64.875 H, 4.225 N, 18.52%, OWNs: G, 64.795 H, 4.08; N, 18.69%. ‘A Similar treatment ofthe p=nitrophenylhydrazone of XVIII afforded a quantitative yield of 2-(p-nitrophenyl)-4-phenyl- S.phenacyl-1,2,3-triazole (XXI), mp 137—138°C. UV 253! ‘me (e): 332 (22300), 242 (14800), and 230 (14200). IR (KBr) NMR (CDCI) 1: 5.38 (6, 2H, -CH,-). Found: C, 68.753 H, 4.333 N, 14.449). Caled for OFae- OWNe: G, 68.745 H, 4.20; N, 14.5895. Basic Rearrangement. ‘The p-nitrophenylhydrazone of XVIIT was dissolved in a minimum amount of acetone con- taining one drop of coned. ammonium hydroxide. ‘The solu tion was refluxed for 5 hr; during that time the solution was kept alkaline by occasional addition of coned. ammonium hydroxide to the solution. By this procedure a quantitative yield of XXII was obtained. Thermal and Basie Treatment of The p-Nitrophenyliydrazone of Caled for CysH Caled for CH Caled for CagHar- XX. ‘Similar thermal and basic weatments afforded, XXIV, mp 280—261°C. IR (KBr) em: 3180 (vgq) and 1670 (Weo)- Found: 58.95; H, 3.54; N, 19.25%, OWNg: ©, 58.60; H, 3.285 N, 19.53%. Photochemistry of XVIH.’ General procedure: A 0.01 ‘mol! solution of XVIII rn solvent was irradiated at Caled for CHa 20) P. Miguel, An. Chim, [vp 11, 346 (1877). 21) BLW. Frizmmon, C. Hewlet and R.A See, 1565, 47779, amy J Chem, Studies on Hetcroaromaticity. XLIV 189 room temperature under nitrogen stream for a given reaction time. The resulting precipitates were filtered and recrystalli zed fom ethanol benzene to afford XXV, mp 134—136°C. IR (KBr) emt: 1650 (¥9)- Found: C, 16.77; H, 4.495 N, 9.17%. (ON: C, 77.095 H, 445; N, 5.629, "The solvent was removed from the filtrate and the residue was chromatographed. The first fraction gave unreacted starting material. Then, dibenzoylacetonitrle, mp 160°C, XXV and benzoic acid were succesively isolated. Dibenzoylacetonitrile. IR (KBr) emt: 3400 (broad, )®) and 2220 (vey). Found: C, 77.32; H, 4475 N, 5.85%. Caled for CH ON: G, 77.095 H, 4.453 N, 5.62% ‘When XVIII was irradiated with a 60-W low pressure ‘mercury lamp in benzene, the main produet was A-benzoyl- benzoylacetamide, mp 170°C." TR (KBr) em 1705 and. 1680 (veg). NMR (DMSO-4,) and 542 (CH, Found: G, 71.553 H, 4.865 N, 5.53%. ‘OWN: G, 71.905 H, 4.90; N, 5.24%, “The results are summarized in ‘Table 2. N-Pheryleljxpblaciridine Oxine (AXVI) and ls O-p-Nitrn bencoate (XVI). To a stirred solution of 0.92 (0.005, mol) of HI in 50 mf of ether was added dropwise a solution of Imi of azividine in 50 mf of ether under ice-cooling. ‘The mixture was stirred for 30 min at this temperature and then for 24 hr at room temperature. After removal of the prec pitates, the filtrate was concentrated to give 80% yield of XXVI as an oil IR (neat) em: 3925 (vq). NMR (CDCL,) +: 7.64 (5 1H, OH) and 7.74 (5, 4H, ~CH,-CH,-)) ‘To a stirred solution of 0.5 ¢ (0.0025 mol) of XXVI and 0.5 g (0.05 mol) of triethylamine in 40 ml of dry benzene was added & solution of 0.5 5 (0.0025 mol) of pnitrobenzoyl chloride in 20m of dry benzene under ice-cooling. The reaction mixture was let standing overnight. After the solu- tion was saturated with dry hydrogen chloride gas, the preci- pitates were filtered and the filtrate was concentrated. The residue was chromatographed to afford 01 g (50%) of, XXVI, mp 147—149°C, by reerystalligation fom benzene = petroleum ether. IR (KBr) cm: 1750 and 1665 (veo). NMR (CDCI) 1: 742 (5, 44, ~CHy-CH,-)) Found: C, 59.935 H, 8.94; N, 12.40%, Caled for CysF- OWNs: C 60.175 Hy 3:86; N, 12.39%. 2-Benzoyloxazaline (XVII). A solution of 0.7 g of | XXVI in 30 mf of acctone was refluxed in the presence of 0.2 of sodium iodide for 30 min. The filtered solution was concentrated and chromatographed to give an oil (XXVIIL). IR (neat) cm-t: 1640 (Vg) and 1610 (e.y)-_ Its pierate, mp 179—180°C; the yield was 0.3 g (25%). NMR (DMSO-<,) 448-56 (m, 4H, ~CH,-CH,)") and 18-25 (m, 5H, phenyl protons) Found: C, 47.103 H, 3.243 N, 14.43%, OWNg: G, 47.295 H, 3475 Ny 13.79%, 22) ‘Mp 165°C: B. v. Mayer, J. pratt. Clem, [2], 42, 267 (180), 28) ‘This indicates the presence of the tautomerism: CH.CO GHC ‘ = c-cN ao cage 20% GH,co ‘OH 24) Mp 190°C: G, Sugowdls and G. Shaw, J. Chm. Soc, 1958, 65. 25) Equivalent two methylene protons of the azirine sing are characterities in these compounds, ‘See H Kesler, Ange. Clem, 82, 237 (1970) 26) Non-equivalent two methylene protons are a good proof of the azirdine ring rupture. Caled for CHa Caled for CyB Caled for C,H