Padmavathi, V

Reddy, D Bhaskar

Reddy, M V Ramana

NOPR

Indian Journal of ChemistryVol. 318, February 1998, pp. 167 - 171Preparation of some 5,7-diarylcyclo-hexeno[3,4-dJ-l-selena-2,3-diazolyl-6-spiro-5'-(2',3'-pyrazolidine I 2',3'-oxazo-lidine)-l ',4'-diones and 5,7-diaryl-cyclohexeno[3,4-d]-1-thia-2,3-diazolyl-6-spiro-5'(2',3'-pyrazolidine/2',3'-oxazolidine )-1 ',4'-dionesD Bhaskar Reddy", M V Ramana Reddy & V PadmavathiDepartment of Chemistry, Sri Venkateswara University,Tirupati 517 502, IndiaReceived 15 May 1997; accepted (revised) II November 1997Synthesis of the title compounds has beenaccomplished through dimethyl-2.6-diaryl-4-oxocyclo-hexane-I, l-dicarboxylates 1. The latter on condensationwith NH2NH2.H20 and NHPH.HCI give 6,lO-diaryl-2,3-diazaspiro( 4,5)decane-1 ,4,8-triones and 6, IO-diaryl-2-oxa-3-azaspiro( 4,5)decane-l ,4,8-triones 2 and 3. Thesemicarbazones 4 and 5 of 2 and 3 on reaction withSeOl and SOCll give '5,7-diaryl cyclobexeno[3,4-d]-l-selena-Z, 3-diazolyl-6-spiro-5'-(2', 3'-pyrazolidine/2', 3'-oxazolidine)-l ',4'-diones 6,7 and 5,7-diaryl cyclo-hexeno[3A-d)-I-thia-2,3-diazolyl-6-spiro-5'-(2', 3'-pyra-zolidine/2',3'-oxazolidine)-l',4'-diones 8,9. The IR andNMR spectral data correlate to the structures of all thenew compounds.We have been extensively investigating thesynthetic potential of dimethyl-2,6-diaryl-4-oxocyclohexane-l,l-dicarboxylates 1 as a sourceof a variety of heterocyclic systems I.... It is wellknown that a number of heterocyclic compoundscontaining nitrogen and sulfur' possess differentpharmacophoric properties. However, reportsabout selenium containing heterocycles arerelatively less'", although some of them are usedas chemotherapeutic agents'". In continuation ofour ongoing programme it is felt desirable toincorporate sulfur/selenium as hetero atoms so thata new class of condensed spiro-heterocycleshaving 2,3-pyrazolidine/2,3-oxazolidine-dionemoieties in combination with I-selenall-thia-2,3-diazoles could be obtained.Infact, the synthetic intermediates'? 1 have beenNoteobtained by the Michael addition of dimethylmalonate to 1,5-diaryl-l ,4-pentadien-3-ones. The6, 10-diaryl-2, 3-diazaspiro-( 45)decane-l 4 8-triones 2 and 6,10-diaryl-2-oxa-3-azaspiro-(4,5)decane-I,4,8-triones 3 nave been prepared oncondensation of 1 with hydrazine hydrate andhydroxylamine hydrochloride, respectively':'. Thecarbonyl group of 2 and 3 is exploited to constructI-selenall-thia-2,3-diazoles. This has beenachieved by the condensation of 2/3 withsemicarbazide hydrochloride to get semicarba-zones 4/5 of 2/3. The IR spectrum (vmax em") of 4showed absorption bands at 1675.and 3200 (C=Oand NH) of pyrazolidinedione moiety and at 3245(NHCO), 3450 (CONH2), 1660 (CONH2) and 1450(C=N) of semicarbazone moiety. The absence of aband at 1700 for carbonyl group of cyclohexanoneconfirms the formation of 4. The compound 5 alsoexhibited absorption bands nearly in the similarregions. Besides this, it also exhibited band in theregion 1780 (C=O of 2,3-oxazolidinedione).Compounds 4 and 5 on cyclization with SeOz andSOCl2 gave 6/7 and 8/9, respectively. The absenceof bands corresponding to semicarbazone unit in 6-9 and the presence of bands due to N=N (1520-1545) in 6-9 and C-S (690-700) in 8 and 9confirms that the cyclization indeed has takenplace in 4 and 5 (see Scheme I, Table I).The IH NMR spectra (&, ppm) of 4 and 5 can berationalized by presuming that the two aryl groupsat 6 and 10 positions are in true cis-I,3-arrangement in the preferred rigid chairconformation of cyclohexane moiety'", althoughnumber of dynamic forms do exist. The methine(H.J and methylene (HMand Hx) protons of 4 and5 constitute AMX splitting pattern. The HAdue tocoupling with HMand H, appears as a doublet ofdoublet in the downfield region. The HMdue togeminal and vicinal couplings also appear as adoublet of.doublet in between HAand Hx. The Hxalso experiences a similar effect and display adoublet of doublet in slightly upfield region of thespectrum. A broad singlet for NH is observed notonly in 4 but also in 5. However, the resonance168 INDIAN J CHEM, SEC. B, FEBRUARY 19980 0R~R(i) (ii)~ ~R RH3COOC COOCH3 0 0HN-X1 2 X=NH3 X =0(iii)•••6 X= NH7 X=O1-9 R• Ce~b 4-OCH3CeH.c 4-CICeH.4&5(iv)~1-8 Rd 4-N(CHy,CeH.• --I[)S(i) NH2NH2 OR NH20H I NaOMa I MaOH(ii) NH2CONHNH2' CH3COONa , MaOHsignal for NH2 is merged with aromatic protons asis evidenced by its disappearance on exchangewith D20. The NH of 2,3- pyrazolidinedione and2,3-oxazolidinedione in 4 and 5 appeared as asinglet. The 'H NMR spectra of 6-9 exhibited threesets of signals for methine (Cs-H and C7-H) andmethylene (C.-H) protons of cyclohexene unit. TheC7-H appears as a singlet while Cs-H a triplet andC.-H a multiplet (see Table I).Experimental SectionMelting points were determined in opencapillaries and are uncorrected. The purity of thecompounds was ascertained by TLC (silica gel-G,Scheme INNHCONH2R4 X=NH5 X=OR Ro 0HN-X8 X=NH9 X=O(iii) 8a02' AcOH 160-700c(iv) SOCI2' GH2CI2' -10°cBDH, hexane-ethyl acetate, 2: 1). IR spectra ofcompounds were taken in KBr (vrnax, em") onPerkin-Elmer FT-IR spectrometer and IH NMRspectra in CDCI) on a varian EM-390 (90 MHz)spectrometer using TMS as an internal standard(chemical shift in 8, ppm). The mass spectra (70eV) of some of the compounds were obtained enJeol JMS-D 300 spectrometer. Microanalyticaldata were obtained from University of Poona,Pune, India.lbe dimethyl-2,6-diaryl-4-oxocyc1ohexane-l, 1-dicarboxylates'" were obtained by the Michaeladdition of dimethyl malonate to 1,S-diaryl-l ,4-pentadien-3-ones. The compounds were purifiedNOTES 169Table I-Characterization data of compounds 4a-e to 9a-eMol. formulat" IH NMR (0, ppm in CDCI3)Compel. Yield m.p.(%) °C4a 70 228-294b 72 215-18 C23H2SNsOs4c 69 220-22 CZIH19C12Ns034d 72 240-42 C2sH31N7034e 70 198-200 C17H17NSO)SZSa 68 235-37 C21H20N.O.Sb 69 220-21 Cz3H2.N.06Sc 67 225-28 CZ1HlsC12N.O.Sd 68 210-12 CZSH30N603Se 66 202-04 C17HI6N.O,S26a 70 146-48 CzoH16N•02Se6b 71 11O-I3(d) CnHzoN.04Se6c 66 138-40 CzoHl.C12N.02Se6d 69 120-22 C24Hz6N60ZSe6e 70 129-31 C16H12N.OzSzSe7a 70 176-78 CZoH1SN303Se7b 68 126-28 CnHI9NpsSe7c 69 165-68 C1oH\3CI1NP3Se7d 68 140-42 Cl.HzsNs03Se7e 69 130-33 CI6Hl!Np3SZSe8a 60 100-03(d) C2oHI6N•OZS8b 63 125-28@ CnHzoN.O.S8c 61 115-17 C~I.CI1NPzS8d 63 130-32 C2oHzSN602S8e 62 142-44 CI6HI2N.OZS32.85 (dd,2H, 7H.&9H.), 3.15 (dd,2H, 7H.&9H.), 4.20 (dd,2H,6H& 10H),7.56-7.65 (m,12H,Ar-H&NHz),7.70 (s,IH,CONH), 9.30 (s,2H,NH of2,3-pyrazolidinedione)2.74 (dd,2H,7H.&9H.), 3.12 (dd,2H,7H.&9H.), 3.34 (s,6H,Ar-OCH3)' 4.24(dd,2H, 6H&IOH), 7.58-7.69 (m,IOH,Ar-H&NHz},7.72 (s,IH,CONH), 9.92(s,2H,NH of 2,3-pyrazolidinedione)2.82 (dd,2H,7H.&9H.), 3.20 (dd,2H,7H.&9H.), 4.16 (dd,2H,6H&10H),7.44-7.59 (m,8H, Thiophene-H&NHz), 7.70 (s,2H,CONH), 9.76 (s,2H,NHof 2,3-pyra-zolidinedione)2.62 (dd,2H,7H.&9H.), 2.98 (dd,2H,7H.&9H.), 4.15 (dd,2H,6H& 10H),7.50-7.68 (m,12H,Ar-H&NHz),7.75 (5, 1H,CONH), 9.82 (5,IH,NH of2,3-oxazolidinedione)2.90 (dd,2H, 7H.&9H.), 3.22 (dd,2H, 7H.&9H.), 4.12 (dd,2H,6H& 1OH),7.00-7.42 (m,IOH,Ar-H&NHz),7.74 (s,IH,CONH), 9.84 (5,IH,NH of2,3-oxazolidinedione)2.78 (dd,2H,7H.&9H.), 3.14 (dd,2H,7H.&9H.), 4.22 (dd,2H,6H&IOH),7.45-7.60 (rn,8H, Thiophene-Heebl+l.), 7.65 (s,IH,CONH), 9.52 (s,IH,NHof 2,3-oxazolidinedione)3.25-3.40 (rn, 2H, C.-H), 4.10 (t,1 H, C~-H), 5.25 (s, 1H, C7-H), 7.10-7.50(m,1 OH,Ar-H), 9.28 (s,2H,NH of 2,3-pyrazolidinedione)3.18-3.32 (m, 2H, C.-H), 3.50 (s,6H,Ar-OCH3)' 4.25 (t,1 H, Cs-H), 5.28(5,1H, C7-H), 7.02-7.48 (m,8H,M-H), 9.18 (s,2H,NH of 2,3-pyrazolidinedione)3.24-3.40 (rn, 2H, C,-H), 4.20 (t, 1H, Cs-H), 5.35 (s,1 H, C7-H), 7.14-7.52(m,oH, Thiophene-H), 9.28 (s,2H,NH of 2,3-pyrazolinedione)3.38-3.52 (m,2H, C,-H), 4.48 (t,1 H, Cs-H), 5.52 (s, JH, C7-H), 7.20-7.45(m, 1OH, Ar-H), 10.35 (5,1H,NH of 2,3-oxazolidinedione)3.45-3.60 (m, 2H, C.-H), 4.36 (t, IH, Cs-H), 5.48 (s,1 H,C7-H), 7.34-7.58(m8H, Ar-H), 10.40 (s, IH,NH of 2,3-oxazolidinedione)3.42 -3.57 (m,2H, C.-H), 4.37 (t,1 H, Cs-H), 5.52 (5,1H, C7-H), 7.02-7.38(m,6H, Thiophene-H), 10.42 (s,1 H,NH of 2,3-oxazolidinedione)3.28-3.38 (m,2H, C.-H), 4.45 (t,IH, Cs-H), 5.32 (s,IH, C7-H), 7.05-7.48(m,IOH, Ar-H),9.25 (s,2H,NH of2,3-pyrazolidinedione)3.35-3.50 (rn, 2H, C.-H), 4.48 (t,1 H, Cs-H), 5.40 (s,1 H, C7-H), 7.15-7.50(m,8H, Ar-H), 9.30 (s,2H,NH of 2,3-pyrazolidinedione)3.24-3.32 (rn, 2H, C.-H), 4.46 (t, JH, Cs-H), 5.25 (s, JH, C7-H), 7.00-7.42(m,6H, Thiophene-H), 9.24 (s,2H,NH of 2,3-pyrazolidinedione)Contd170 INDIAN J CHEM, SEC. B, FEBRUARY 1998Table I-Characterization data of compounds 4a-e to 9a+-ContdMol. formulal" IH NMR (0, ppm in CDCI3)C2JilSNP3S 3.35-3.51 (m, 2H, C.-H), 4.52 (t,IH, Cs-H), 5.65 (s,IH, C7-H), 7.05-7.34(m, IOH, Ar-H), 10.34 (s,IH,NH of2,3-oxazolidinedione)3.28-3.40 (m,2H, C.-H), 3.46 (s,6H,Ar-OCH3)' 4.44 (t,tH, Cs-H), 5.62(s,IH, C7-H), 7.00-7.35 (m,8H,Ar-H),10.32 (s,IH,NH of2,3-oxazolidinedione)Compd Yield m.p.(%) °C9a 61 112-149b 63 \o2-05(d) C22HI9N30SS60 118-20 C20HI3CI2NP3S62 127-29 C2.H2SNSO)S60 104-06 CI6HIIN)O)S)9c9dge 3.37-3.50 (m.2H. C.-H), 4.58 (t.1H, Cs-H), 5.45 (s.IH, C7-H), 7.04-7.40(m,6H,Thiophene-H), 10.30 (s,1 H,NH of 2,3-oxazolidinedione)"Satisfactory microanalyses were obtained for 4a, 4d, Sb, 6a, 6c, 6e, 7b, 8b, 9a and ge: C± 0.24%, H± 0.15%, N ± 0.18%.'Molecular ions were observed for 4a, Se, 6e, 7a, 8a and ge at 391, 404, 434, 423, 376 and 389 respectively at 70 eV.by recrystallization from methanol [ld: m.p. 140-41°C, yield 65%. Cal. (Found): C, 69.00 (69.21);H, 7.12 (7.05). Ie: m.p. 148-49°C, yield 75%. Cal.(Found): C, 57.12 (56.95); H, 4.79 (4.87)].The 6,1 0-diaryl-2,3-diazaspiro( 4,5)decane-l, 4,8-triones/6, 10-diaryl-2-oxa-3-azaspiro( 4, 5)-de-cane-l,4,8-triones (2 and 3) were prepared by thecondensation of I with NH2NH2.H20 andNH20H.HCI3.4. The compounds were purified byrecrystallization from methanol [2d: m.p. 225-27°C, yield 69%. Cal (Found): C, 68.55 (68.35); H,6.71 (6.78); N, 13.32 (13.50). 2e: m.p. 199-01°C,yield 70%. Cal (Found): C, 55.47 (55.62); H, 4.07(4.14). 3d: m.p. 186-87°C, yield 65%. Cal(Found): C, 68.39 (68.19); H, 6.45 (6.37); N, 9.96(9.85). 3e: m.p, 204-06°C, yield 67%. Cal.(Found): C, 55.31 (55.52); H, 3.77 (3.85)].8-Semicarbazono-6, lO-diaryl-2, 3-diazaspiro-(4,5)decane-l,4-diones/6, lO-diaryl-2-oxa-3-aza-spiro(4, 5)decane-l, 4-diones 4/5. General pro-cedure. Semicarbazide hydrochloride (0.017 mole)and sodium acetate trihydrate (0.03 mole) weredissolved in ethanol (40 mL) and the solid, if any,formed was filtered off. To this, compound 2(0.0029 mole) in ethanol was added and thecontents were refluxed for 4-5 hr on a steam-bath.The reaction mixture was then concentrated,cooled and poured onto crushed ice. The separatedsolid was filtered, washed thoroughly with coldwater, dried and recrystallized from ethanol to getpure 4/5.5,7-Diarylcyclobexeno[3, 4-d]-I-selena-2,3-di-azolyl-6-spiro-5' -(2' ,3' -pyrazolidine/2', 3' -oxa-zolidine)-l ',4'-diones 617. General procedure.The semicarbazone 3 (0.0025 mole) in glacialacetic acid (20 mL) was warmed while stirring inorder to get a clear solution. Selenium dioxidepowder (0.0025 mole) was then added in portionsand continued the stirring while maintaining thetemperature at 60-70°C until the evolution of gasceased. The reaction mixture was then allowed toattain room temperature and the depositedselenium was removed by filtration. When thefiltrate was poured on crushed ice, a solid productwas separated. It was filtered and washedthoroughly with cold water and sodiumbicarbonate solution. The product obtained waspurified by chromatography.5,7-Diaryl cyclobexeno[3, 4-d]-1-tbia-2, 3-di-azolyl-6-spiro-5' -(2', 3' -pyrazolidine/2', 3' -oxa-zolidine)-l ',4'-diones 8/9. General procedure.The semicarbazone 3 (0.0025 mole) was addedportion-wise to an excess of thionyl chloride (5ml.) maintained at -5 to -10°C and allowed toreach the room temperature where it was kept for afurther period of 1-2 hrs. The reaction mixture wasdiluted with 30 mL of dichloromethane and treatedwith ice-cold solution of sodium carbonate. Theorganic layer was separated and w.ashed repeatedlywith water and then dried over anhydrous sodiumsulfate. Evaporation of the solvent gave a gummysubstance which was solidified by triturating withpetroleum ether (40-60°). The crude productobtained was purified by column chromatography.AcknowledgementOne of the authors (MVRR) gratefullyacknowledges the authorities of Sri VenkateswaraUniversity, Tirupati for the award of "NSRCUI"Research Fellowship.References1 Bhaskar Reddy D, Ramana Reddy M V & Padinavathi V,Indian J Chem, (in press).2 Bhaskar Reddy D, Padmavathi V & Padmaja A, Indian JHeterocyclic Chem, 2,1993,229.3 Bhaskar Reddy D, Padmavathi V & Ramana Reddy P V,Indian J Chem, 31B, 1992, 774 and references citedtherein.NOTES 1714 Bhaskar Reddy D, Padmavathi V, Seenaiah B & RamanaReddy M V, Org Prep Proced Int. 24,1992,21.5 Sharma K S & Sing S P, Indian J Chem, 3IB, 1992,396.6 Lalezari 1,Shafiee A & Yazdani S, J Pharma Sciences, 63,1974,628 and references cited therein.7 Sharma K S, Sarita & Sharda Kumari, Indian J Chem, 4,1994,137.8 Klayman D L & Guntur W H H, Organic SeleniumCompounds. Their Chemistry and Biology (Washington,New York), ]972.9 Shafiee A, Lalezari I, Yazdany S & Poumorouz A, JPharm Sciences, 62,1973,839.10 Bhaskar Reddy D, Padmavathi V & Muralidhar Reddy M,Indian J Chern,31B, 1992,407.

Preparation of some 5,7-diarylcyclohexeno[3,4-d]-l-selena-2,3-diazolyl-6- spiro-5'-(2',3'-pyrazolidine / 2',3'-oxazolidine)-l ',4'-diones and 5,7-diarylcyclohexeno[3,4-d]-1-thia-2,3-diazolyl-6-spiro-5'(2',3'-pyrazolidine/2',3'-oxazolidine )-1',4'-diones

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Preparation of some 5,7-diarylcyclohexeno[3,4-d]-l-selena-2,3-diazolyl-6- spiro-5'-(2',3'-pyrazolidine / 2',3'-oxazolidine)-l ',4'-diones and 5,7-diarylcyclohexeno[3,4-d]-1-thia-2,3-diazolyl-6-spiro-5'(2',3'-pyrazolidine/2',3'-oxazolidine )-1',4'-diones

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