Padmaja, A

Reddy, D Bhaskar

Reddy, K Ramachandra

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Indian Journal of ChemistryVoI.36B, July 1997, pp.608 - 611Carbenoid addition to u, ~-ethylenicsulfones under PTC-A stereospecificsynthesisD Bhaskar Reddy", K Ramachandra Reddy & A PadmajaDepartment of Chemistry, S V University, Tirupati 517 502,IndiaReceived 14 October 1996;revised and accepted 25 March 1997Cyclopropanation of aryl styryl sulfones 1 with aryl-thiocarbenes and chlorocarbenes under PTC condi-tions results in the formation of 1, 2-diarylsulfonyl-3-ary1cyclopropanes 3 and 1-arylsulfonyl-2-aryl-3,3-dichlorocyclopropanes 4 respectively. The latterhave been characterized by spectral parameters.Amongst the various methods known for the syn-thesis of cyclopropanes, cycloaddition of carbenesto ethylenic systems has been found to be a versa-tile technique 1-4. The carbenes are highly unstableand are generated in situ necessiating an inert me-dium and rigorous reaction conditions I. On theother hand, the addition of halocarbenes to ole-fins proceeds through an intermediate trihalocar-banion which displays an increased reactivity to-wards the double bond as compared to halogenfree carbanion". Carbenes as well as dihalocar-benes add to olefins in a stereospecific manner 1.6.The generation of dihalocarbenes-Y and arylthio-carbenes=P in situ normally requires anhydrousconditions in order to avoid their rapid hydrolysisbut under phase transfer conditions they displayan enhanced reactivity since they" are formed inthe vicinity of reactant. In fact, several substituteda1kenes were cyclopropanated with phenylthioand halocarbenes under phase transfer condi-tions 13-16. However, exploitation of a, ~-ethylenicsulfones for this purpose is limited. Our sustainedinterest in this field led us to report the cycle-propanation of aryl styryl sulfones with arylthio-carbene and dichlorocarbene adopting phasetransfer conditions. Thus 1, 2-diarylsulfonyl-3-arylcyclopropanes 3 and I-arylsulfonyl- 2-aryl- 3,3-dichlorocyclopropanes 4 have been obtained bythe cycloaddition of arylthiocarbenes and dichlo-rocarbenes to aryl styryl sulfones 1 respectively(Scheme I, Table I). The substrates used in thepresent study are considered to possess E-Notegeometry". Hence, the addition of dichloro/aryl-thiocarbene generated in situ to the substratesfurnished trans products, thus retaining thegeometry of the former6•9•1O• Many a time a num-ber of side reactions would occur but a carefulmonitoring of the reaction process under phasetransfer conditions lead to their successful synthe-SIS.The IR spectra of compounds 3 and 4 exhibit-ed strong bands in the region 1030-1010 em - 1characteristic of cyclopropane ring deformationmode (Table I) and at 1110-1090 and 950-920em -I indicating E....geometry'P-". They also dis-played strong bands in the region 1335-1310 and1145-1115 ern -I for asymmetric and symmetricstretching vibrations of sulfonyl group. In com-pounds 4, the spectra also contained bands dueto C - Cl in the region 775-750 em -I (ref. 19).The 1H NMR spectra of 3 exhibited an AMXpattern for cyclopropy] ring protons (Figure 1)and each one of them appeared as doublet ofdoublet at 3.85-3.94 (HA), 3.48-3.68 (HM) and3.32-3.42 ppm (Hx) (Table I). The signal at higherbH value is assigned to HA which is more desh-ielded than HM and Hx (ref. 20). In general, insubstituted cyclopropanes all substituents tend tocause protons cis to them to appear at higherfields than those trans to them". Thus amongstHM and Hx, the HM appeared at downfield regionrelative to Hx as the former is trans to aryl moie-ty at C-3. A perusal of the J values from theTable I indicates that the geometry assigned tocyclopropane ring is in conformity with such as-signments. In the case of 4 the cylcopropyl ringprotons exhibit an AX splitting pattern (Figure 2).The methine protons HA and H; appeared asdoublets at 3.56-3.72 and 3.38-3.58 ppm respect-ively. The higher bH value is. ascribed to HA sinceit experiences deshielding effect and the J valuesindicate that they also possess E-geometry.The 70 eV mass spectra of 3a and 4a indicateslow intense molecular ion peaks at 398 and 326respectively. a-Cleavage process of the molecularions is commonly observed. Stepwise eliminationof S02 or phenylsulfonic acid moiety is a uniquefeature observed in the fragmentation of molecu-lar ion 3a16. However, in case of 4a moderate in-tense peaks due to M + 1, M - CI and M - Cl2 areobserved. Peaks corresponding to M + 2 andM + 4 were also observed due to CJ37isotope.4NOTES 60923( I ) R2 Cc;lLSCH2CUSO% aq.NaOHIBTEAC/CH2Ch( ii )H2021 AcOH( iii )CHCh/SO% aq.NaOHIBTEAC/CH2ChR RI Rl R Rlill a H H H IV a H Hb H H 4-CH3 b H 4-CH3C H H 4-Cl c H 4-Cld H 4-CH3 4-Cl d H 3,4-(OCH3ne 4-CH3 4-CH3 H e 4-CH3 Hf 4-CH3 4-CH3 4-CH3 f 4-CH3 4-Clg 4-CH3 4-Cl H g 4-OCH3 Hh 4-Cl H H h 4-OCH3 4-OCH34-Cl H 4-CH3 4-Cl H4-Cl H 4-Cl j 4-Cl 3,4-{OCH3nk 4-Br H1 4-Br 4-Clm 3,4 -Ch Hn 4-Cl,3-CH3 H0 5-CJ,2-CH3 HArS'7CIFigure 1 Figure 2Scheme IExperimental SectionMelting points were determined on a Mel-Tempapparatus and are uncorrected. The IR spectra(KBr) were recorded on a Perkin-Elmer gratinginfrared spectrophotometer model 337, IH NMRspectra on a Bruker spectrospin NMR spectrome-ter operating at 200 MHz with TMS as an inter-nal standard and mass spectra on Jeol JMS-D300 mass spectrometer at 70 eV. The microana-6\0 INDIAN J.CHEM.SEC B. JULY 1997Table I-Characterization data of the compounds 38-j and 48-0Compd Yield m.p. Mol. formula IR (KBr) em - I 'H NMR (CDCI3, 0, ppm) Coupling constants (Hz)%) (OC)S02 Ring defor- HA HM Hx lAM lAX lMXmationmode38 64 135-36 C2,H1XS2O. 1310,1125 1025 3.89 3.54 3.36 9.85 6.80 4.903b 62 143-44 C22H2"S20• 1315,1125 1020 3.86 3.48 3.37 9.85 6.82 4.943c 68 167-68 C2IHI7S20.Ci 1325, 1130 1020 3.91 3.62 3.39 9.80 6.79 4.923d 72 183-84 C22H1.S2O.Cl 1315, 1120 10253e 60 226-27 C23H22S2O. 1320, 1125 1020 3.85 3.56 3.32 9.84 6.80 4.943f 65 234-35 C2.H2.S2O. 1315, 1115 10153g 70 197-98 C22H17S2O.Cl 1325, 1125 1030 3.94 3.52 3.35 9.85 6.81 4.903h 75 247-49 C2IH17S2O.Ci 1320, 1120 1025 -;3i 64 189-90 C22H19S20.Ci 1325, 1130 10203j 68 258-59 C2,HI6S10.Cil 1325,1125 1025 3.90 3.68 3.42 9.82 6.80 4.9348 58 145-46 CI5H12S02Ci2 1320, 1140 10204b 62 164-65 C 16HI.S02C12 1320,1145 1015 3.60 3.50 4.804c 65 158-59 CI5HIIS02Ci3 1325, 1150 1025 3.68 3.52 4.814d 60 169-70 C17HI6SO.Ci2 1315,1125 10104e 59 153-54 C'6H,.SOlCi2 1325, 1125 1015 3.56 3.52 4.814f 64 172-74 CI6H13S02Clj 1325, 1145 1020 3.59 3.58 4.824g 66 168-69 C16HI.S03C12 1320,1130 1010 3.62 3.54 4.824h 60 149-50 C17HI6S04C12 1320, 1135 10204i 63 183-84 CI5HIIS02Ci3 1335, 1145 10254j 65 192-94 C17H,sSO.CI3 1335,1140 10204k 68 143-44 CI5HIIS02Ci2Br 1330, 1135 1020 3.72 3.54 4.8141 62 165-66 CI5HIIlS02CljBr 1335, 1145 10254m 65 169-71 CI5HwS02Cl. 1335, 1140 1015 3.66 3.38 4.8040 58 144-45 C'6HI3S01Ci3 1325,1135 101040 64 139-40 CI6H13S02Clj 1330,1130 1020Satisfactory elementary analyses were obtained C ± 0.36, H ± 0.18.lyses were performed at CECRI, Karaikudi. Pur-ity of the compounds was checked by TLC usingsilica gel H(BDH) and hexane-ethyl acetate (3:2)as an eluant.1, 2-Diarylsulfonyl- 3-arylcyclopropanes 3:General procedure. A mixture of aryl styryl sul-fone (5 mmol)21,22 1 and aryl chloromethyl sul-fide" (6 mmol) in methylene chloride (30 mL)and 50% aq. NaOH (20 mL) was stirred well toobtain a clear two-phase system. Then, benzyl-triethylammonium chloride (BTEAC) (100 mg)was added and stirring was continued at roomtemperature for 10-12 hr. After completion of thereaction, the contents were diluted with water.The organic layer separated was washed with wa-ter, brine and then dried. Removal of the solventgave crude thiocyclopropanes 2 as viscous liquidswhich were subsequently oxidized with 10 mL of30% hydrogen peroxide (10 mL) in glacial aceticacid (20 mL) at reflux temperature. The contentswere allowd to cool and poured onto crushed icewith stirring. The solid separated was collected,washed with water, dried and recrystallized fromethanol or 2-propanol to obtain pure 3.1 - Arylsulfonyl - 2 - aryl - 3, 3 - dichlorocyc-lopro panes 4: General procedure. A mixture ofaryl styryl sulfone 1 (5 mmol) andchloroform (50 mL) was stirred with 50% aq.NaOH (20 mL) till a clear two-phase system wasobtained. To this, benzyltriethylammonium chlo-ride (BTEAC) (100 mg) was added and the mix-ture stirred at 45°C for 8-10 hr. The progress ofthe reaction was monitored by TLC. The contentswere diluted with water and the organic layer sep-arated was washed with water, brine and dried.Evaporation of the solvent gave a solid which wasrecrystallized from benzene or glacial acetic acidto get pure 4.AcknowledgementOne of the authors (KRR) thanks UGC, NewDelhi for the award of FIP fellowship.References1 Skell P S & Woodworth R C, JAm Chem Soc, 78, 1956,4496.2 Van Leusen A M & Strating J, Quart Rep Sulfur Chern,5,1970,67.3 Kirmse W, Carbene Chemistry (Academic Press, NewYork),1971.4 Weber A, Sabbioni G, Galli R, Staemptli U & Wander MN, Helv Chim Acta; 71,1988,2026.5 Doering W V E & Hoffmann A K, J Am Chem Soc, 76,1954,6162.6 Skell P S & Gamer A Y, J Am Chem Soc, 78, 1956,3409.7 Parham W E, Christensen L, Groen S H & Dodson R M.J Org Chern, 29,1964,2211.8 Poon C D, Yuen P W, Man T 0, Li C S & Chan T L, JChem Soc, Perkin TralLY-l, 1984, 1561 and referencescited therein.9 Schoellkopf U & Lehman G J, Tetrahedron Len, 1961,165.NOTES 61110 Truce W E & Badiger V V, JOrg Chern, 29, 1964,3277.11 Saquet M, C R Acad Sci Ser C, 275, 1972,283.12 Balaji T & Bhaskar Reddy D, Bull Chem Soc Japan, 52,1979,3434.13 Boche G & Schneider D R, Tetrahedron Lett, 1975,4247.14 Bhaskar Reddy D, Gopal Reddy G & Padmavathi V, S~fur Lett; 5,1987, 123.15 Dehmlow E V & Dehmlow S S, Phase Transfer Catalysis(VCH: Weinheim), 1993.16 Bhaskar Reddy D, Ramana Reddy P V & Padmavathi V,Phosphorus, Sulfur and Silicon, 90, 1994, 1 and refer-ences cited therein.17 Truce W E & Goldhamer D L, J Am Chem S(H., 81,1959,5798.18 Truce W E & Goralski C T, J Org Chern, 33, 1968,3849.19 Sioboin Y M, Ashkinazi L A & Klim Chuk G N, Zh OrgKhim. 20, 1984, 1001.20 Goralski C; T,.] Org Chern, 37, 1972,2354.21 Bhaskar Reddy D, Sankaraiah 8 & Balaji T, Indian JChern, 198, 1980,563, and references cited therein.22 Bhaskar Reddy D, Sankaraih 8 & 8alilji T, Phosphorousand Sulfur, 16, 1983,293.

Carbenoid addition to ɑ, β-ethylenic sulfones under PTC-A stereospecific synthesis

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Carbenoid addition to ɑ, β-ethylenic sulfones under PTC-A stereospecific synthesis

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