2332 J.C.S. Perkin INitrogen Heterocycles. Part 7. Some Reactions of 2-Anilinophthalimi-dine Derivatives tBy Valerio Scartoni, lvano Morelli, Antonio Marsili, and Serena Catalano, lstituti di Chimica Farrnaceuticae di Chimica Organica della FacoltB di Farrnacia dell'UniversitA di Pisa, via Bonanno, 6, 561 00 Pisa, Italy2-Anilino-3-benzyl-3-hydroxyphthalimidine ( I ) gives, on treatment with acids under various conditions, themethoxy-derivative (2). 2-anilino-3-benzylidenephthalimidine (3). 2-(o-carbamoylphenyl)-3-phenylindole (7).and 1 I -phenylisoindolo2,1 -a indol-6-one (8). Compound (8) may be obtained also by pyrolytic rearrangementof (3). Pyrolysis of (1) affords 4-benzyl-3-phenylphthalizinium-3-olate (1 I ) , which can be transformed into anumber of compounds, including the cycloadduct (1 2) with dimethyl but-2-ynedioate. Bromination of (3) gives2- (p-bromoanilino) -3-benzylidenephthalimidine (5) and 3-bromo-2- (p-bromoanilino) -3- (a-bromobenzyl) -phthalimidine (1 6), which, by reaction with methanol or ethanol, affords the alkoxy-derivative (I 7) or (1 8).Compounds (1) or (3).(5). (17). and (18) are converted by bases into the corresponding phthalazinones (19)-(22).3-( CC-BROMOBENZYLIDENE)PHTHALIMIDINE and Some Of itsderivatives bearing appropriate N-substituents rearrangeor cyclise under a variety of conditions.lP2 We now re-port the results obtained with 2-anilino-3-benzyl-3-hydroxyphthalimidine (1), the adduct formed by reactionof 3-benzylidenephthalide with aniline, and of some com-pounds derived from it.Treatment of compound (1) with hydrochloric acidin methanol at 0 "C gave the methoxy-derivative (Z),mixed with a small amount of 2-anilino-3-benzylidene-phthalimidine (3); the latter was obtained as the main7 Presented in part to the Tascan Section of the ItalianChemical Society, Pisa, December 14, 1972; Chimica e Industria,1973, 55, 380.product by heating (1) or (2) with acids in methanol.Acet ylat ion of (3) gave 2- (N-ace t ylanilino) -3-benzylidene-phthalimidine (4), which afforded the known 2-(N-acetylani1ino)phthalimide (6) on ozonolysis.Although by analogy with the results obtained fromother 3-benzylidenephthalimidine derivatives * and inview of the fact that a rather bulky N-substituent ispresent one could tentatively propose an E-configurationfor (4), the spectral data of this compound and those of(3) also did not permit a sure attribution of configuration.geli, J.C.S.Perkin I, 1977, 969.Part 6, A. Marsili, V. Scartoni, I. Morelli, and P. Pieran-A. Marsili and V. Scartoni, Gazzettn, 1974, 104, 165.F. D. Chattaway and W. Tesh, J. Chem. SOC., 1920,117, 711.A. Marsili and V. Scartoni, Gazzetta, 1972, 102, 8061977 2333When compound (1) was refluxed with hydrobromicacid in acetic acid solution the two indole derivatives (7)and (8) were isolated. The latter was formed also byheating (3) at 300-350 ldquo;C. The formation of (7) is inagreement with the mechanism proposed for the Fischerindole ~ynthesis,~ the ammonia remaining bonded to thecarbonyl group during the 3,3 sigmatropic rearrange-ment of the enehydrazide (3).The indoloisoindolone(8) is derived from (7) by pyrolytic cyclisation. Treat-ment of (8) with $-nitroperbenzoic acid led to N-(o-benzoylphenyl) phthalimide (9) ; compound (8) wasformed also by photolysis of 3-( a-bromobenzylidene)-2-phenylphthalimidine (10). *( 1 ) R = O H ( 3 ) Rrsquo;= H , R 2 = H( 2 ) R =OMe ( 4 1 Rrsquo; = Ac, R2 = H( 5 1 Rrsquo; = H, R2 = Bra C o ) - N P h bsol; I( 6 )co Accorsquo;( 8 )CONH,( 7 )PhCO aZ1-QCBrPh@,NPh co10 )When solutions of compound (1) in acetic acid or incyclohexanone were heated at reflux, conversion into thebet aine ( 1 1) (4-benz yl-3-phen ylpht halazinium- 1 -olat e)took place. This thermal rearrangement of 2-anilino-3-hydroxyphthalimidines has been described before.6 The1,3-dipolar character of (11) was confirmed by reactionwith dimethyl butynedioate to obtain the cycloadduct(12), in agreement with Katritzkyrsquo;s findings for similarcompo~nds.~ In addition, the betaine (11) underwentthe following transformations : with acetic anhydride itgave the acetate (13) also obtained directly from (1) withAttemptedpreparation of this compound from 2,3-dihydro-2-phenyl-phthalazine-1,4-dione and acetic anhydride led, however, to (14).Equilibria of this kind, involving valence-bond tautomerism,have been discussed recently (see N.Dennis, A. K. Katritzky, andH. Wilde, f.C S. Perkin I , 1976, 2338, and references cited there-* Work in progress in this laboratory.t An N-acetyl isomer of (14) bas been de~cribed.~inbsol;acetic anhydride, which was ozonolysed to the acetoxy-phthalazinone (14) ; t methanolic hydrogen bromide(12 1CH,Ph CHPhamp;yPh C Y P h / N C Y P h / N/ NOAc OAc OH rsquo;lsquo;amp;-NHa13r CHRPh( 1 6 ) R = Br(171 R = OMe(18) R = OEtcaused conversion into the hydroxyphthalazinium bro-mide (15); hydrochloric acid at 180 ldquo;C transformed (11)into (8); and photolysis in methanol led to compoundThe last two reactions suggest that the betaine (11)is in equilibrium with the diaziridine (23),: which could(2) *Ph-CH,(23)either rearrange to (3), and hence to (8), or react withmethanol to give (2).Treatment of (3) with an equimolar amount of brominein chloroform afforded the 9-bromoanilino-derivative( 5 ) ; this compound easily added one further moleculeof bromine to give the unstable tribromo-derivative (16),also obtainable from (3) and 2 mol.equiv. of bromine.When (16) was treated with methanol or ethanol, or elsewhen (3) was brominated in the presence of these twoalcohols, the stable 3-( a-alkoxybenzyl)-3-bromo-2-(~-bromoani1ino)phthalimidines (17) and (18) were obtained.We have shown previously 17234 that bromination of 3-benzylidenephthalimidine and N-aralkyl-3-benzylidene-phthalimidines leads to products 3- (a-bromobenzyl-idene)phthalimidines derived from a substitution reac-tion at vinylic carbon. In the case of compound (5)formed from (3) by aryl substitution only addition ofM. K. Eberle and L.Rrzechffa, J . Org. Chem., 1976,41, 3775.H. Lund, Tetrahedron Lettevs, 1965, 3973.N. Dennis, A. R. Katritzky, and M. Ramaiah, J.C.S.Perkin I, 1976, 22812334 J.C.S. Perkin Ibromine to the double bond has been observed. If oneconsiders the electrophilic step of the bromination pro-cess,* which in these compounds involves two benzyliccarbon atoms, a carbocation at C-3 may be stabilised byelectron-releasing substituents at the ring nitrogen ;therefore proton elimination may occur. On the otherhand, the electron-withdrawing P-bromoanilino-substitu-ent of (5) must exert a destabilising effect on such acarbocation, thus favouring initial electrophilic attack atC-3 and completion of the reaction by attack of eitherbromide or alkoxide ions at the exocyclic benzylic car-bon.The action of ethanolic potassium hydroxide on (1) and(3) led to the known phthalazinone (19) ; analogously,treatment of ( 5 ) , and of (17) and (18), with base causedCHR'Phconversion into the phthalazinone derivatives (20)-(22),respectively. This base-catalysed transformation prob-ably involves an anionic intermediate such as (24), whichcould rearrange through the tautomeric hydroxydiaziri-dine anion (25).In the case of (3) and (5) , the rearrange-ment mechanism is probably analogous, the last stepbeing protona.tion of a carbanion such as (26).' P hV C O1 X = OH, or Br. Y = H, OMe, or OEt-CHPh CHYPhamp;Y CO"Ar( 2 6 )Compounds (l), (2), (3), and (8) were tested both foranti-inflammatory and analgesic activity (in vivo) andfor antibacterial activity (in vitru).Whereas (2) and(8) were inactive, (1) showed inhibiting action on Strep-tococcus Pyogenes haemolyticus, and (3) analgesic activity.None of these compounds was considered interestingenough for further study.EXPERIMENTALM.p.s were determined with a Kofler apparatus; i.r.spectra were recorded for Niijol miills with a Perkin-Elmer137 spectrophotometer ; U.V. spectra were determined forsolutions in 95 ethanol with a Zeiss PMQ I1 spectrophoto-meter; n.m.r. spectra were recorded for solutions in CDCl,(unless otherwise indicated) with a JEOL C-60 HL spectro-meter (Me,Si as internal standard).2-Anilino- 3-benzyl-3-hydroxyphthalimidine ( 1) .-Phenyl-hydrazine (19 ml) in ethanol (20 ml) was added in portions t oa hot solution of 3-benzylidenephthalide (20 g) in ethanol(40 ml).The mixture was refluxed for 1 h, then left over-night a t room temperature. The precipitate (1) (17.4 g)crystallised from methanol as prisms, m.p. 188-190 "C(Found: C, 76.15; H, 5.45; N, 8.2. C,lH,,N,O, requires C,76.35; H, 5.5; N, 8.5), v,,,. 3 333 (OH, NH) and 1669cm-l (CO), 6 3.1 (1 H, m, OH), and 3.02, 3.25, 3.52, and 3.75(2 H, ABq,CH,). Addition of water to the mother liquorcaused precipitation of a further crop (4.4 g).2-Anilino-3-benzyl-3-methoxyphthalimidine (2) .-Concen-trated hydrochloric acid (8 ml) was added to a stirred solu-tion of (1) (5.4 g) in methanol (150 ml) a t 0 "C. After 90 minthe precipitate (2) (3.5 g) was removed, and crystallised frombenzene-liexane as p ~ i s m s , m.p.168-170 "C (Found: C,76.85; H, 6.1; N, 7.9. C,,H,,N,O, requires C, 76.7; H,5.85; N, 8.15), v,,,,,, 3 289 (NH) and 1 701 cm-l (CO), 6(CD,),SO 2.9 (3 H, s, CH,), 3.02, 3.25, 3.47, and 3.70 (2 H,ABq, CH,), and 8.25 (1 H, s, NH). Addition of water to thefiltrate, extraction with ether, and evaporation afforded aresidue (1.5 g) consisting of mainly (2) and a little (3).2-Anilino-3-benzylidenephthaZ2mZdine (3) .-(a) From corn-pound (1). Concentrated hydrochloric acid (20 ml) and (1)(30 g) in methanol (180 ml) were refluxed for 15 niin. Thesolid (3) (21 g) formed a t room temperature crystallised fromchloroform-methanol as yellow platelets, n1.p. 192-194 "C(Found: C, 80.75; H, 5.1; N, 8.65.C,,H,,N20 requiresC, 80.75; H, 5.15; N, 8.95), v,,~,. 3 290 (NH) and 1 695cni-l (CO), A,. 275 (log E 4.05) and 331 nm (4.13).A solution of compound (2) (0.5g) in methanol (9 ml) and concentrated hydrochloric acid ( 1nil) was refluxed for 10 min and cooled to obtain (3) (0.4 g).(4) .-Compound (3) (0.5 g) in acetic anhydride ( 5 ml) was refluxeclfor 10 11. Evaporation and treatment of the residue withmethanol afforded (4) (0.5 g) as $risms, m.p. 152-154 "C(Found: C, 77.75; H , 5.25; N, 7.85. C,,H,,N,O, requiresC, 77.95; H, 5.1; N, 7.90/:), vnYax, 1 718 and 1 695 cm-l (CO),A, 266sh (log E 4.07) and 329 nni (4.16), 6 2.2 (3 H, s, CH,)and 6.77 (1 H, s, olefinic H). When (4) (0.2 g) in ethanol( 3 ml) containing 10 sodium hydroxide (2 nil) was heatedfor 10 min a t reflux, dilution with water gave compound (3)N- (N-A cetylanilino)phthnlirnide (6) .-A stream of oxygen-ozone was bubbled for 3 h into a solution of compound (4)(0.5 g) in methanol (30 ml) and dichloromethane (100 ml)at -70 "C.The solution was treated with climethyl sul-phide in ether a t 0 "C, and after 20 11 a t room temperaturewas evaporated. The oily residue crystallised from ethanol-water to afford compound (6) (0.2 g), n1.p. 201-203 "C2-(o-Carbamoylphenyl)-3-phenyZindole (7) and 1 l-Phenyl-isoindoZo2,l-aindoZ-6-one (8) .--A solution of compound (1)(2.0 g) in 3 : 1 acetic acid-concentrated hydrobromic acid (8ml) was heated a t 100 "C for I h. After cooling, the precipi-tate (8) (0.6 g) was removed and crystallised from methanol(b) From compound (2).N- (N-A cetylanilino) - 3-benzylidenefihthalzw~idine(0.12 g).(iit.,3 198 oc).a R.C. Fahey, Topics Stereochem., 1868, 3, 237.J . Tiphraim, Rrv., 1893, 26, 13761977as yellow needles, m.p. 223-226 "C (Found: C, 85.3; H,4.65; N , 4.6. C,,H1,NO requires C, 85.4; H, 4.45; N,4.75), v,,,,. 1721 cm-l (CO). The filtrate was carefullydiluted with water; after several hours compound ( 7 ) (0.2g) was collected and crystallised from benzene--light petro-leum as needles, m.p. 196-197 "C (Found: C, 80.5; H, 5.25;N, 8.65. C,,H,,N,O requires C, 80.75; H, 5.15; N, 8.95y0),v,. 3 225 and 3 460 (NH) and 1 640 and 1 670 cm-l (CO).Other Preparations of Compound ( 8 ) .--(a) From compound( 7 ) .Compound ( 7 ) ( 1 .O g ) was heated a t 300-350 "C for 15min. After cooling, extraction of the crude product withchloroform, evaporation, and treatment of the residue withmethanol afforded (8) (0.7 g).(b) From compound ( 3 ) . Pyrolysis of ( 3 ) ( 1 . 1 g) andwork-up as described above yielded (8) (0.9 g). Alternative-ly, a solution of compound ( 3 ) ( 2 g) in acetic acid (30 ml) andconcentrated hydrobromic acid (10 ml) was heated a t 100 "Cfor 2 h. The usual work-up afforded ( 8 ) (1.1 g).(c) From compound ( 4 ) . A suspension of ( 4 ) (0.2 g) inacetic acid ( 3 ml) and concentrated hydrobromic acid ( 1 ml)was heated for 2 h a t 100 "C. Dilution with water afforded(d) From 3- (a-bromobenzylidene) -2-fihenylphthalimidine(10). A solution of (10) ( 1 g) in benzene (100 ml) was ir-radiated for 20 h a t room temperature with a 70 W high-pressure mercury lamp (Hanau TQ 81) equipped with animmersion well system (Pyrex glass).The residue fromevaporation crystallised from methanol to give (8) (0.5 g).N-(o-Benzoylpheny1)phthalzmide (9) .-A solution of ( 8 )(0.36 g) and p-nitroperbenzoic acid (0.6 g) in chloroform(20 ml) was kept a t room temperature for 4 days. Theprecipitated p-nitrobenzoic acid was filtered off, and thefiltrate was washed with 2~-sodium carbonate and evapor-ated. The residue ( 9 ) (0.2 g) crystallised from methanol asprisms, m.p. 203-205 "C (Found: C, 77.0; H, 4.15; N, 4.15.C,,H,,NO,requires C, 77.05; H, 4.0; N, 4.3), v,. 1 669,1 724, and 1 812 cm-l (CO).The same product (0.5 g ) wasobtained by refluxing for 30 min a mixture of phthalicanhydride (0.4 g) and o-aminobenzophenone (0.3 g) in aceticacid ( 5 ml) .4-Benzyl-3-~henylphthalaziniulcn-l-olate ( 1 1) .-(a) A sus-pension of compound ( 1 ) ( 1 g) in acetic acid ( 5 ml) was re-fluxecl until a clear solution was obtained (10 min). Addi-tion of water (10 ml) and an excess of 10 sodium hydroxidecaused precipitation of (11) (0.6 g), which crystallised frommethanol-ether as prisms, m.p. 214-216 "C (Found: C,80.65; H, 5.3; N , 8.75. C,,H,,N,O requires C, 80.75; H,5.15; N , 8.95y0), vmax. 1613 cm-l (CO), A,. 260infl. (log E4.17) and 344 nm (3.98), 8 4.45 ( 2 H , s, CH,).(b) Compound ( 1 ) (0.5 g) in cyclohexanone ( 5 ml) wasrefluxed for 30 min.Evaporation and crystallisation of theoily residue gave (11) (0.3 g).Dimethyl 5-Benzyl-2,5-dihydro- l-oxo- 10-phenyl-2,B-imino-lH-2-benzaze$ine-3,4-dicarboxyZate ( 1 2) .-A mixture of ( 1 1 )(0.5 g) and dimethyl butynedioate (0.5 ml) in benzene ( 5 ml)was refluxed for 10 h. The precipitate (12) (0.05 g) crystal-lised from methanol as yellow neeales, m.p. 171-173 "C(Found: C , 71.1; H, 4.7; N , 6.45. C,,H,,N,O, requiresC , 71.35; H, 4.9; N, 6.150/), v,,,,~ 1 664 and 1 721 cm-l (CO),63.78(6H,s,CH,),and4.15,4.37,4.60,and4.82(2H,ARq,CH,). Evaporation of the mother liquor and treatment ofthe residue with methanol afforded (12) (0.05 g).1 -A cetoxy-4-benzylidene- 3,4-dihydro- 3-phenylphthalazine(13) .-(a) Compound ( 1 ) ( 1 g) in acetic anhydride ( 5 ml) wasrefluxed for I 11.After cooling, addition of ether-light(8) (0.08 g).2335petroleum caused separation of (13) (0.55 g ) , which crystal-ised from ethanol-light petroleum as needles, m.p. 183-184"C (Found: C, 77.8; H, 5.25; N , 8.1. C,,H,,N,O, requiresC, 77.95; H, 5.1; N, 7.9y0), vmaX. 1 695 and 1 724 cm-I (CO),A,,,,. 262 (log E 4.26), 287 (4.'21), and 325sh nm (4.04), 8 2.57( 3 H , s, CH,) and 6.70-8.15 (15 H, vinylic and aromatic).(b) Compound ( 1 1 ) (0.25 g ) in acetic anhydride (1.2 ml) wasrefluxed for 1 h. After cooling, addition of light petroleum-ether caused separation of (13) (0.2 g). When a suspensionof (13) (0.2 g) in acetic anhydride ( 3 ml) and concentratedhydrobromic acid ( 1 ml) was heated a t 100 "C for 2 h, andtreated with water (10 ml) and 10 sodium hydroxide,compound ( 1 1 ) (0.16 g) was formed.4-Acetoxy-2-phenylphthalazin- 1 (2H)-one ( 14) .-Compound(13) (0.5 g) was submitted to ozonolysis as described for ( 4 )to give the phthalazinone (14) (0.2 g), m.p.132-134 "C(Found: C, 68.65; H, 4.1; N, 10.0. C,,H,,N,O, requiresC, 68.6; H, 4.3; N, 10.Oyo), vInaX. 1 672 and 1 779 cm-l (CO).4-Benzyl- 1-hydroxy-3-plaenylphthalazinium Bromide ( 15).-A solution of compound ( 1 1) ( 1 g) in methanol ( 5 ml) wastreated with an excess of methanolic hydrogen bromide atroom temperature. Addition of ether afforded ( 15) (1.1 g),which crystallised from methanol-ether as needles, m.p.220-225 "C (Found: C, 63.9; H, 4.35; N, 7.2. C,,H,,-BrN,O requires C, 64.15; H, 4.35; N , 7.17(,), 8 (CF,CO,H)4.9 ( 2 H, s, CH,).Alternatively, compound (13) ( 1 g) inmethanol ( 5 ml) was treated with an excess of methanolichydrogen bromide and worked-up as described above toobtain (15) ( 1 g).Conversion of Compound ( 11) into ( 8 ) .-A suspension of(11) ( 1 g) in 2~-hydrochloric acid (10 ml) was heated a t180 "C for 6 h in a sealed glass tube. After cooling the in-soluble material crystallised from methanol to give (8) (0.5Photolysis of Compound ( l l ) . - A solution of (11) (0.5 g)in methanol (100 ml) was irradiated for 4 h a t room temp-erature as described for the conversion of (10) into (8). Con-centration of the mixture gave ( 2 ) (0.4 g).3-Benzylidene-2- (p-bromoanilino)phthalimidine (5) .-To astirred solution of ( 3 ) (3.1 g) in ethanol-free chloroform (40ml) a solution of bromine (0.53 ml) in chloroform (5 ml) wasadded dropwise a t 0 "C.The usual work-up and crystallis-ation of the residue from chloroform-methanol afforded (5)(2.7 g) as pale yellow plates, m.p. 246-248 "C (Found:C, 64.25; H, 4.0. C,,H,,BrN,O requires C , 64.45; H,3.850/,), vnlax. 1698 (CO) and 3 279 cm-l (NH).3-Bromo- 2- (p-bromoanilino) - 3- (a-bromobenzy l)phthalimi-dine (16).-Compound ( 3 ) (2.0 g) was treated with 2 mol.equiv. of bromine under the same conditions as described for( 5 ) . An amorphous unstable solid (1.9 g) was obtained,which was purified by precipitation from benzene solutionwith hexane and dried (P,O,) in uacuo (Found: Br, 43.25.Calc. for C,,H,,Br,N,O: Br, 43.5).3- (or-A lkoxybenzyl) -3-bromo-2- (p-brovnoanillno)phthalimi-dines (17) and (18).---The phthalimidine ( 3 ) or (5) was treatedwith bromine ( 2 or 1 mol.equiv., respectively), and to thestirred solution was added an excess of methanol or ethanol.After 30 min the usual work-up afforded a residue, which wascrystallised from benzene-hexane. Yields varied from 80to goo/,. Compound (17) formed needles, m.p. 174-175 "C(Found: C, 52.8; euro;3, 3.8. C,,H,,Br,N,O, requires C, 52.6;H, 3.6), vmax. 1 715 (CO) and 3 300 cm-I (NH), 6 3.02 ( 3 H,s, CH,), 5.75 ( 1 H, s, C H ) , and 6.25 ( 1 H, s, NH). Compound(18) gave needles. m.p. 172-174 "C (Found: C, 54.3; H,3.65. C,,H,,Br,N,O, requires C, 53.5; H, 3.9)), vmax.g)J.C.S.Perkin I1712 (CO) and 3 300 cm-l (NH), 6 1.08 (3 H, t, CH,, J 6.7Hz), 3.3 (2 H, q, CH,, J 6.7 Hz), 5.67 (1 H, s, CH), and 5.71(1 H, s, NH).4-BenzyE-2-$henylphthalazin- 1 (2H) -one ( 19) .--This com-pound (0.9 g), m.p. 170 "C (1it.,lo 171 "C), was obtained byrefluxing for 1 h compound (1) or (3) (1.0 g) with ethanolic10 potassium hydroxide (10 ml) and diluting the solutionwith water.4-Benzyl-2-(p-brornophenyZ)j1hthalazin-l(2H)-one (20) .-This compound (0.6 g) was obtained by treatment of com-pound (5) (1.0 g) with potassium hydroxide as described for( 19). Crystallisation from chloroform-methanol gave leaf-lets, m.p. 108-110 "C (Found: C, 64.7; H, 3.6. C21H,,-BrN,O requires C, 64.45; H, 3.850/amp;), vlnaX. 1 658 cm-l (CO),6 4.35 (2H, s, CH,). Alternatively, a mixture of o-phenyl-acetylbenzoic acid (2.4 g), fi-bromophenylhydrazine ( 1.8 g) ,and ethanol (20 ml) was refluxed for 1 h. Dilution withwater caused separation of (20) (2.0 g).4-(a-A1koxybenzyl) -2-(p-bronzoaniZino)phthalazzn- 1 (2H) -ones (21) and (22) .-A suspension of compound (17) or (18)(0.5 g) was refluxed for 30 min with ethanolic 10 potassiumhydroxide (10 ml). Addition of water t o the resulting solu-tion caused separation of (2 1) or (22), which crystallisedfrom benzene-hexane. Yields varied from 40 to 50.Compound (21) gave needles, m.p. 180-182 "C (Found: C,62.45; H, 4.1. C,,H,,BrN,O, requires C, 62.7; H, 4.05),vmx. 1664 cm-l (CO), 6 3.56 (3 H, s, CH,) and 5.65 (1 H, s,CH). Compound (22) formed firisms, m.p. 113-115 "C(Found: C, 63.6; H, 4.5. C,,H19BrN,0, requires C, 63.45;H, 4.40/,), vmax. 1 669 cm-l (CO), 6 1.3 (3 H, t, CH,, J 6.7 Hz),3.75 (2 H, q, CH,, J 6.7 Hz), and 5.76 (1 H, s, CH).We thank Dr. P. I,. Barili for the n.m.r. spectra and Dr. V.Thanks are also due t oThisNuti for the elemental analyses.Carlo Erba Co. for the pharmacological screenings.work was supported by a grant from the CNR.7/799 Rpceived, 9th May, 197710 Copyright 1977 by The Chemical Societ
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