The synthesis of some heterocyclic sulphonium salts

摘要

1972 899The Synthesis of some Heterocyclic Sulphonium SaltsBy R. M. Acheson and J. K. Stubbs, Department of Biochemistry, South Parks Road, Oxford OX1 3QUA number of heterocyclic sulphur compounds and their sulphoxides have been S- and O-alkylated respectively, withsilver perchlorate and alkyl halides. 5-Methoxydibenzothiophenium and 1 O-methoxyphenoxathiinium per-chlorates reacted with amines to give 5- and 1 O-arninosulphonium salts, respectively, and with certain carbanionsto give zwitterionic compounds.WHEREAS aliphatic sulphides react readily with alkylhalides to give stable sulphonium salts, aromatic andheterocyclic sulphides are much less nucleophilic. Apartial order of reactivity 19, is Me,S Ph,S phen-oxathiin dibenzothiophen benzothiophen thio-phen.The less reactive compounds may be alkylatedby the use of trialkyloxonium tetrafluoroborates or byalkyl halides in the presence of silver salts., Thesulphonium salts then produced are themselves alkylat-ing agents, and are toxic, probably for this reason. Inconnection with possible biological applications it washoped to prepare sulphonium salts which would beweaker, more selective, alkylating agents than the S-alkylthiophenium salts prepared earlier.,Silver perchlorate, or its complex with acetonitrile,was used in dichloroethane to effect the alkylation ofdibenzothiophen, phenoxathiin, thioxanthene, and N-acetyl- and N-phenyl-phenothiazine. Because of therisk of explosion,2 silver perchlorate was only used whenits acetonitrile complex proved ineffective.Neitherreagent was effective in attempts to cyclise compound(31) or (32) to a sulphonium salt. Unlike the U.V.spectra of S-alkylbenzothiophenium salts,, the spectraof our S-alkylsulphonium salts in cold water or alcoholwere unchanged after 24 h, showing the stability of thecompounds under these conditions. Compounds (24)and (25) were observed to alkylate hexadeuteriodi-methyl sulphoxide; the n.m.r. spectra of solutions inthis solvent changed rapidly to that of a mixture ofN-acetylphenothiazine and the corresponding alkoxy-dimethylsulphonium salt.For compounds (10)-(30), if a non-coplanar ring-system is assumed and the bonds to sulphur are arranged' Methoden der Organischen Chemie,' vol.9, ed. E. Muller,Georg Thieme, Stuttgart, 1955, pp. 175, 176.R. M. Acheson and D. R. Harrison, J . Chern. SOC. (C), 1970,1764.trigonally, as in the case of l-alkylbenzothiopheniumsalts,, the possibility of two configurations occurs, the/obsol;(1) 5-CHZI (6) 5-O*CH,CH-CH,(3) 5-PPh, (7) 5-N*CH.J,.CHZ(4) 5-OMe (8) B-NH.CHZ.CH,Ph(2) 6-CH,C02Me m(5) 6-OEt (9) 5-NH*CHzCHz.~HEt2 C10,-1 O-Me (16) 10-Et-2,8-Brz10-Et (17) 10-CH,I-2,8-Brz1 O-CH2I (18) IO-OMelO-CH,.CO,Me (19) 10-NH.CH,3.NEt,lO-CH,-CH,Br (20) lO-NH-CH,CH,*GHEt, C10,-10-CH23-10'10(21) 10-CH21(23) 10-CH,*CO*NHz(22) lO-CH,.CO,Me(24) 5-Me-lO-Ac (28) 5-CHZI-10-Ph(26) 5-Me-10-Ph (30) 5-Et- lO-(P-OzN*C,HJ(27) 5-Et-10-Ph(25) 5-Et-10-Ac (29) 5-CH2*CO,Me- 10-P900 J.C.S.Perkin IS-alkyl group being ' axial ' or ' equatorial '. However,in polar solvents the inversion rate of these compoundsappears to be rapid; according to Andersen et aL3 then.m.r. signal due to the methylene group of S-methyl-thioxanthenium tetrafluoroborate appears as a doubletin tetrachloroethane, but as a singlet in acetonitrile.The n.m.r. spectrum of compound (18) in chloroformshowed the methyl signal as two peaks (A 3.6 Hz) ofsimilar height, but as a singlet in acetonitrile or in tri-fluoroacetic acid solution, No splitting was observedwith compounds (10)-(17) and (21)-(23), whose n.m.r.spectra were recorded for solutions in polar solvents forsolubility reasons.Phenothiazine is reported* to give a salt on heatingwith 10-chlorophenoxarsine (33). Unsuccessful attemptswere made to extend this reaction of (33) to form saltswith dibenzothiophen or phenoxathiin by the use of(31) X = Br(32) X = IC l(33)0OMe ClOi OMe CLO(34) (35)silver perchlorate.These failures suggest that thephenothiazine derivative of 10-chlorophenoxarsine iscloser to a rc-complex than a salt. However, chlorodi-phenylphosphine reacted at low temperature with di-benzothiophen and silver perchlorate to give a lowyield of the phosphinosulphonium salt (3).Sulphoxides are sufficiently nucleophilic to be alkyl-ated at the oxygen atom by the reagents mentionedabove ; for example dimethyl sulphoxide is methylatedby methyl iodide and silver perchlorate5 and diary1sulphoxides are ethylated by triethyloxonium tetra-fluor~borate.~~~ Dibenzothiophen amp;oxide reactedK.K. Andersen, M. Cinquini, and N. E. Papanikolaou, J .* S. J . Strycker, U.S.P. 3,117,123/1964 (Chem. Abs., 1964, 61,6 N. J. Leonard and C . R. Johnson, J . Amer. Chern. Soc.,Org. Chem., 1970, 35, 706.667).1962, 84, 3704.readily with a number of alkyl halides in the presenceof silver perchlorate (acetonitrile complex). The salts(4) and (5) were stable in a dry atmosphere, but salt(6) decomposed within a few weeks, and the products fromphenethyl bromide and from ethyl bromoacetate de-composed rapidly to the sulphoxide on exposure to theatmosphere. The sulphoxides of phenoxathiin, thi-oxanthone, and dibromobenzothiophen suffer alkylationsimilarly.From their behaviour in trial experiments thealkoxysulphonium salts produced appeared to behydrolysed much faster than the corresponding alkyl-sulphonium salts, giving the sulphoxides.Whereas alkylsulphonium salts are hydrolysed by anS N ~ process in neutral solution, or by nucleophilic attackon the carbon atom,2 alkoxysulphonium salts appear tobe hydrolysed by nucleophilic attack on the sulphur atom.This is shown by the inversion of configuration whichoccurs on alkaline hydrolysis.6 The reaction of Grignardreagents with diar-'-thoxysulphonium salts to givetriarylsulphonium Id- 3 clearly involves nucleophilicattack at the sulphur atom.It was therefore of interest to treat some other baseswith the alkoxysulphonium salts. The 5-methoxydi-benzothiophenium salt (4) was recovered from treatmentwith aniline, hydrazine, or phenylhydrazine at roomtemperature, but the compounds (4) and (18) reactedreadily with aliphatic amines, the methoxy-group beingdisplaced to give, respectively, the aminosulphoniumsalts (7), (S), and (9), and (19) and (20).The saltsshowedthe strong i.r. absorption near 1100 cm-l characteristicof the perchlorate ion. The n.m.r. spectrum of thepiperidine derivative (7) in hexadeuteriodimethyl sul-phoxide showed the piperidyl protons as two broadsignals at T 7.08 and 8.53, corresponding to four and sixprotons, respectively. The aromatic region was similarto that of 5-alkyldibenzothiophenium salts,2 and wassimulated to 0.1 Hz accuracy by use of the seven-spinn.m.r.computer program of Klopfenstein.' Compounds(34) and (35), and methoxydimethylsulphonium per-chlorate gave only the sulphoxides when treated withpiperidine. In the last case, piperidinium perchlorate(not N-methylpiperidinium perchlorate) was isolated,suggesting the intermediate formation and hydrolysisof an aminosulphonium salt.5-Methoxydibenzothiophenium perchlorate (4), ontreatment with sodium cyclopentadienide, gave azwitterionic compound (36), and the salt (18) similarlyreacted with dimethyl sodiomalonate to give the ylide(37), methanol being eliminated in each case. The n.m.r.spectra showed the replacement of the original methoxy-signal by a narrow, symmetrical four-proton multipletin the cyclopentadienide (36), and by a relatively high-field six-proton singlet for the ester methyl groups in theylide (37).Compound (36) was thermally unstable anddifficult to purify, but (37) formed salt-like crystals of* C. R. Johnson and D. McCants, jun., J . Amer. Chem. Suc.,1965, 87, 5404.7 C. L. Wilkins and C. E. Klopfenstein, J . Chem. Educ., 1966,43, 10; translated into Egtran by P. C. Bell, Part 11, Thesis,Oxford University, 19671972 901high m.p. Some related sulphonium methylides, pre- General Procedures for A ZkyZations.-(A ) Silver per-pared by other methods, have been chlorate (0.1 mol) and the sulphur-containing compound(0-1 1-0-18 mol) were stirred in dichloroethane (300 ml) andEXPERIMENTAL the alkyl halide (0.2-0.6 mol) was added dropwise. Stir-ring was continued for a day or longer; the precipitate ofinstrument at 6 0 MHz.U.V. absorption spectra were silver halide was then filtered off and washed with aceto-measured with a Perkin-Elmer Ultracord instrument. 1.r. nitrile. The combined filtrates were concentrated in vucuoN.ni.r. spectra were measured with a Perkin-Elmer R 1 2TABLE 1N.m.r. spectra (z values; J in Hz; Me4Si as internal standard)Compound Solvent ArH SubstituentsMeCN 1.6-2-4 (SH, m)(CD,),SO 1.6-2.6 (SH, m)MeCN 1.7-2-45 (8H, m)(CD,),SO 0.86-3.0 (18H, m)PhNO,PhNO,(CD,),SO 1.5-2.5 (SH, m)(CD,),SO 1.6-2.5 (8H, m)CDC1, 1.86-3-1 (13H, m)(CD,),SO 1.55-2.4 (SH, m)CH,Cl, 1.95-2.7 (SH, m)CH,CI, 1.9-2.7 (SH, m)(CD,),SO 1.8-2.65 (SH, m)CDCI, 1.7-2.6 (8H, m)MeCN 1.9-2.65 (SH, m)(CD,),SO 1-9-2-7 (16H, m)(CD,),SO 2.51 (2H, d, 1-, 9-H); 2.64 (2H, q, 3-, 7-H);3.03 (2H, d, 4-, 6-H); J3.4 8.4; J1.3 2.52.49 (2H, d, 4-, 6-H), J3.4 8.8; J1.3 2.4MeCNCDCI, 1.65-2-5 (SH, m)MeCN 1.6-2.46 (SH, m)CF,-CO,H 1.6-2-35 (8H, m)CDC1, 2.06-2.7 (SH, m)(CD,),SO 1-8-2.6 (SH, m)MeCN 1.85-2.5 (SH, m)MeCN 1.8-2-53 (8H, m)MeCN 1-9-2.6 (SH, m)(CD,),SO 1.8-2.8 (SH, m)(CD,),SO 1.8-2-8 (8H, m)MeCN 2-0-2.9 (11H, m ) ; 3.25 (2H, 9); J 8 and 2CH,Cl, 2.0-2-7 (11H, m) ; 3-25 (2H, q) ; J 8 and 2MeCN 2-0-2.9 (11H, m); 3-27 (2H, q ) ; J 8 and 2MeCN 2.0-2.7 (11H, m); 3.22 (2H, 9); J 8 and 2MeCN 1.95-2.8 ( l l H , m); 3-22 (2H, 9); J 8 and 2MeCN 1.88-2.8 (8H, m) ; 1.45 (2H, d) ; 3-38 (2H,CDCI, 24-2.9 (SH, m)CDCl, 2.4-2.9 (SH, m)(CD,),SO 1.65-2.25 (SH, m)(CD,),SO 1.9-2.6 (4H, m)CDC1, 1.95-2.7 (SH, m)CDCI, 2.36-3.0 (SH, m)1-86 (2H, d, 1-, 9-H) ; 1.94 (2H, q, 3-, 7-H,d ) ; J 94.79 (2H, CH,I)4-50 (2H, CH,I)6.41 (2H, CH,) ; 6-25 (3H, OCH,)6.28 (3H, OCH,)5-80 (2H, q, OCH,); 8.60 (3H, t , CH,)5-55 ( l H , q.Ha) ; 6.23 (lH, q, HI,) ; 6.78 (lH, m, H,) ; 7.21(IH, t, Hd) ; 7-42 (1H, q, H e ) ; J a , b 8.7; Ja,c 2.1; Jbvc7.2; Jc,d 7.0; J d , e 7.07.08 (4H, m) ; 8-53 (6H, m)3.35br (lH, NH) ; 7.26 (4H, apparent s, aliphatic H)7-04 (4H, q, NCH,*CH,); 7-09 (4H, apparent s, aliphatic6.74 (3H, CH,)6.41 (2H, q, CH,) ; 8.73 (3H, t , CH,); J 7.04.91 (2H, CH,I)5.41 (2H, CH,) ; 6.26 (3H, OCH,)6.02 (2H, t , CH,CH,Br) ; 6.56 (2H, t, CH,-CH,Br) ; J 6.56.37 (4H, m, aliphatic H); 8.57 (2H, m, aliphatic H)5.72 (2H, q, CH,) ; 8.69 (3H, t , CH,) ; J 7.25.12 (2H, CH,I)6.52, 6.58 (3H, apparent d, OCH,)6.66 (3H.OCH,)H ) ; 8.95 (6H, t , N*CH,*CH,)6.63 (3H; O*CHJ1.08 ( l H , NH); 7.08 (4H, 9); 7.188.38 (2H, m); 8.80 (6H, t ) ; J ca.7.04 (4H, apparent s, aliphatic H) ; 7.8-98 (6H, t, N*CH,.CH,) ; J 7.05.28 (2H. CHVI) ; 5.51 (2H. 9-H,)7-54 (2H, t ) ;caseN*CH,*CH,) ;5.48 (2H; CH,) :. 5.50 (2H,.9-H2jlsquo;; 6.23 (3H, OCH,)3.7br (2H, NH,) ; 5-66 (4H, apparent s, CH, and 9-H,)6.51 (3H, CH,) ; 7.60 (3H, COCH,)6.42 (2H, CH,); 7.60 (3H, COCH,); 8.74 (3H, t, CH,);7-06 (3H, CH,)6.56 (2H, q, CH,) ; 8.72 (3H, t, CH,); J 7.26.62 (2H, q, CH,); 8.83 (3H, t, CH,); J 7 and 25.38 (2H, CH,I)5.68 (2H, CH,); 6.33 (3H, OCH,)6.43 (2H, 9, CH,); 8.88 (3H, t, CH,) ; J 7.26.43 (2H, t ) ; 7.01 (2H, t ) ; J 6.76.93 (4H, m)6.29 (3H, OCH,)6.36 (3H, OCH,)3.80 (4H, m)6.44 (6H, OCH,)J 7.5iromatic region (acetonitrile as solvent; 100 MHz) was simulated t o 0.1 Hz accuracy by use of the folowing parameters:7 1.8:- ,--H), 2.256 (2-H), 2.087 (3-H), 1.824 (4-H): J1.2 7.8, J1.3 1.2, J 1 , d 0.6, J2.3 7.7, J2.4 1-43 J9.4 7.7.spectra were measured with a Perkin-Elmer 257 spectro-photometer for Nujol mulls.All the perchlorate saltsshowed characteristic intense absorption near 1100 cm-l;other peaks of interest and the peaks in the region 1000-650cm-l are recorded. M.p.s were measured with a Reicherthot-stage apparatus. Acetonitrile and dichloroethane weredried by refluxing for 1 h with 2 (w/w) of powderedcalcium hydride, and distilled.G.Seitz, Chem. Ber., 1968, 101, 685.H. Nozaki, D. Tunemoto, S. Matabara, and K. Icondo,Tetrahedron, 1967, 23, 545.and the residue triturated with ether. The solid wasfiltered off, washed with a little water to remove silver per-chlorate, dried thoroughly, and recrystallised by dissolvingin acetonitriIe (treating with charcoal if necessary), filtering,and diluting slowly with ether. When the solution becameslightly turbid, it was seeded and set aside to crystallise.(B) Silver perchlorate-acetonitrile complex (1 : 4 molar;prepared as described lo) (0.1 mol) and the sulphur-contain-ing compound (0- 1 mol) were dissolved in dichloroethanel o T. E. Young and R.A. Lazarus, J . Org. Chew., 1968, 38,3774 (footnote)902 J.C.S. Perkin I(250 ml) and the alkyl halide was added dropwise. Whenthe reaction was complete, the product was isolated as inprocedure A except that it was unnecessary to wash withwater.The halides used were : di-iodomethane, methyl bromo-acetate, chlorodiphenylphosphine, methyl iodide, ethylTABLE 2U.V. absorption spectra (solutions in methanol)Compound hmax./nm (10-4c)211 (3.3), 241 (3.3), 270infl (0.74), 324 (0.2)211 (4.0), 233 (2-7), 264 (1.8). 315 (0.21)213 (4.2), 239 (5.3), 269 (3.7), 213infl (0.8)207 (2-1), 222 (2-6), 244infl (3.4). 249 (3-5), 281 (0.32),209 (2-4), 238infl (2.8), 242 (3*1), 266 (0~63)~ 333 (0.13)209 (4*0), 239 (3*6), 332 (0.17)210 (2-9), 232infl (2*8), 238 (3.1).328 (0.16)213 (3-7), 287 (0.61)214 (3-4), 290 (0.50)213 (4-7), 294 (0.53)212 (4-3), 280 (0.87)212 (6.6), 292 (0.84)217 (4.0), 250infl (1.2), 300 (0.46)220 (4.8), 258 (1-6), 310 (0.63)212 (2*8), 224 (3-2), 304 (0-37), 317 (0.37)212 (4.5), 281infl (0*31), 301 (0.46)212 (4.7), 286infl (0.32), 302 (0.48)210 (2*7), 266 (0.90)212 (2-1), 268 (1.3)212( 2-0), 270 (1.3)212 (2*9), 278 (0*44), 293 (0.45)218 (3.6), 275 (0*87), 326 (0.88)222 (5.4), 277 (1*0), 337 (1.1)218 (4.0), 265 (0*78), 329 (0.82)215 (2-2), 228 (2*1), 262 (1.1)230 (2*9), 328 (0.37)210 (2*2), 247 (0.68)356 (0.13)211 (2.7), 227 (1.8), 234 (leg), 264 (1.7), 285infl (1.4)iodide, 1,2-epoxy-3-iodopropane, 1,2-dibromoethane, and1,3-di-iodopropane.5-A Zkylaminodibenzo bd thiopheniunz Perchlorates .-5-Methoxydibenzothiophenium perchlorate (4) (0-315 g)was dissolved in acetonitrile (2-3 ml) and stirred in acarbon dioxide-carbon tetrachloride cooling bath; a solu-tion of piperidine (85 mg) in acetonitrile (1 ml) was added,and the mixture was allowed to warm to room temperature.After 0-5 h, dry ether was added slowly and the crystallineprecipitate was filtered off and recrystallised, by dissolvingin acetonitrile and adding ether, to give the perchlorate (7)(0.26 g, 70y0), plates, m.p.174" (decomp.). Similarlyphenethylamine (121 mg) gave the perchlorate (8) (0.24 g,go), needles, m.p. 133-133.5", and 2-(diethylamino)-ethylamine (1 16 mg) gave 5-(2-diethyZavninoethylamino)di-benzothiopheniuwz perchlorate hydroperchlorate (9) (0.18 g,36y0), rhombs, m.p.210-212".1 O-A lkylami~aophenoxathiiniu~~ PerchZorates.-These wereprepared by the method used for compound (7) : 10-meth-oxyphenoxathiinium perchlorate (18) (0.66 g) and 3-(di-ethy1amino)propylamine (0.26 g) in acetonitrile (4 ml),mixed at -30" and left overnight at room temperature,gave the perchlorate (19) (0.64 g, 74), needles, m.p. 104".Similarly 2-(diethy1amino)ethylamine (1 16 mg) gave 10-(2-diethyZaminoethyZamino)phenoxathiinium perchlorate hydro-pevchlorate (20) (0.1 g, 20), needles, m.p. 155-156".10- (3-BromopropionyZ)phenothiazine (3 1) .-Recrystallisedphenothiazine (2.0 g), anhydrous sodium carbonate (4.0 g),and 3-bromopropionyl chloride (2-5 g) were stirred in drydioxan (50 ml) a t 100" for 45 min; the mixture was thencooled, diluted, and neutralised.The crude product wasfiltered off and recrystallised from ethanol to give compound(31) (2.6 g, 77) pale yellow plates, m.p. 141-142" (1it.,l1144-145O).lo-( 3-Iodo~ropionyZ)~henothiazine (32) .-10-(3-Bromopro-piony1)phenothiazine (31) (3-0 g) and sodium iodide (10 g)in AnalaR acetone (40 ml) were stirred and refluxed for 12 h;the hot solution was then diluted and allowed to cool.Recrystallisation of the precipitate from ethanol gave thephenothiazilze (32) (2.5 g) as yellow-green needles, m.p.Thioxanthen-5-one lO-Oxide.-Thioxanthen-5-0ne hasbeen oxidised to the sulphoxide with iodosylbenzene di-acetate,12 but controlled oxidation with hydrogen peroxidewas found to be more convenient.Thioxanthen-amp;one(9.0 g) in glacial acetic acid (100 ml) was stirred and refluxed147-148".TABLE 3Alkylation productsRe-actionPro- time YieldProduct cedure (days) () M.p. ("C)3 40 160-164 t1 6 277-2791 70 144-1451 77 152-1531 22 157-1588 59 136t(1) A"( 2)(3) Ba(4)( 5 ) B(6)(10) B(11) B(12) A(13) A(16) A(17) A(18) B(21) A(22) A(23) A(24) B(25) A(26) B(27) B(29) A(30)(34) B1 86 198t6 46 214t7 80 173t3 58 131-132t13 29 154--155t 1;;; 3 41 196-197t5 (10 170-176t19 13 19571 67 1179 19 19872 48 175t2 24 175t1 29 14177 (10 216-217t2 76 183-1841-2 39 181-1827(28) A 10 65 220710 77 190tG 40 195-2001-2 67 155-1607(35) 1 46 122tsilver perchlorates (3), phenoxathiin (5).* Mixed at - 70".i Decomp.Proportions used:DescriptionPlatesPlatesPale yellow prismsPale yellow platesPale yellow prismsPale yellow platesPrismsPrismsPrismsPrismsPrismsNeedlesPrismsPrismsPlatesNeedlesNeedlesPrismsNeedlesNeedlesPrismsPrismsPrismsPrismsPale green needlesNeedlesYellow prismsdi-iodopropane (I),vigorously on an oil-bath (bath temp.l40"), and 30hydrogen peroxide (1 8 ml) was added through the condenser.The mixture soon became homogeneous; it was refluxedvigorously for 2 min and then poured into hot water (500nil) and cooled. The precipitate was filtered off, dried(8.5 g), dissolved in chloroform (40 ml), and applied to acolumn of silica (300 ml) prepared in benzene.Elutionwith benzene gave first thioxanthen-5-one (2.0 g), vmx. 1645cm-1, then thioxanthen-5-one sulphone (ca. 1 g), vmX 1680cm-1. Elution with chloroform gave thioxanthen-amp;one10-oxide (4.8 g), m.p. 201-202" (1it.,l2 202-204"), v,,1670 cm-l (CO).R. Dahlbom, Acta Chem. Scund., 1963, 7, 873.12 J. P. A. Castrillon and H. H. Szmant, J. Ovg. Chem., 1967,32, 9761972 9032,3-Dibronzobenzobthiophen 1-Oxide.-This was pre- 10-Methoxyphenoxathiinium perchlorate (18) (0.66 g) dis-solved in acetonitrile (2 ml) was cooled to -20" and asolution of dimethyl malonate (0.3 ml) in methanol (3 ml)containing sodium (46 mg) was added slowly. The mixturewas kept for 20 min at -20" and for 20 min at room tem-perature, then an excess of water was added to precipitatepared as described in ref.13 and had m.p. 156" (frombenzene) (lit. ,13 156-5-157.5").Dibenzothiophenium Cyclopentadienide (36) .-5-Methoxy-dibenzothiophenium perchlorate (4) (1.58 g) dissolved inacetonitrile (10 ml) was cooled to -20", and a solution ofFormulaC13HloC1104SC2,H1,C1O4PSCl,lH13C105SC15H13C106SC,,Hl,C1N04SC2,H,,C1N04SC13HllC105SC15H13C106SC13H11C105SC16H24C12N206SC14H13C105SC13H1,C110,SC15H13C107SC1,H,,BrC1O5SCl,HllBr2C105SC13H,Br2C1105SCl,H25C1N,05SC14Hl,C1104SC15Hl,C1N05SC~15H14C1N0,SC16H16C1N05SCl,H16C1N04SC2,H,,C1N04SC,9H15C11N0,SC2,Hl,C1N06SC27H22C12010S2C13H11C106SC16H24C12N209SC16H15C106SC20H17C1N206SC,,H,,lNOSC,H7Br2C105S C14H11C106SC17H12SC17H105STABLE 4Analyses and i.r.spectraFound () Required ()--- A IC H N S C H N S VIu*m./C1n-l36-8 2-6 36-7 2.4 782w, 762, 758, 706w50.5 3.8 9-2 50.5 3.6 9.0 1731, 975, 955, 912, 893, 780~1, 760, 7 5 0 ~ , 70561.6 3.4 7-0 61.5 3.8 6.8 810, 781, 760, 739, 721, 70450.0 4.0 10.2 49-6 3.5 10.2 949, 7 9 2 ~ , 771, 762, 722, 710, 6 8 8 ~51.1 4.5 10.2 51.2 4-0 9-75 985, 870, 780w, 770, 761, 745, 70851.0 3.9 9.1 50.5 3.6 9.0 917, 901, 870, 862, 784, 772, 762w, 71055.9 5.0 4.0 55.5 4.9 3-8 960w, 940w, 918w, 858, 837w, 764, 760, 71059.7 4.6 3.7 59.5 4-5 3.5 3190 (NH), 930, 893w, 763, 739, 711w, 69843-6 4.9 5.8 43.3 4.8 5.6 3180, 3120 (NH), 955, 932, 760, 70950.3 3-6 10.4 49-9 3-5 10.2 9 9 0 ~ , 885, 8 2 0 ~ , 76751.4 3.8 10.0 51.2 4-0 9.75 9 6 8 ~ , 959w, 930w, 880, 8 7 1 ~ , 812w, 780w, 768,35-9 2.5 35.5 2.3 890, 806w, 770w, 76248.8 3-6 S-9 48.4 3.5 8.6 1735, 987w, 913w, 891, 882, 817w, 782, 764, 7 5 4 ~42.0 3-0 41.3 3.0 958w, 883, 839w, 815w, 776, 76350.7 3-7 12.5 50.5 3-4 10.0 955w, 887, 881, 813w, 770, 76134.8 2-3 34.5 2.3 965w, 913w, 870w, 851, 840, 825, 783w, 762, 73226.5 1.6 26.1 1.3 870w, 841, 823, 73247-5 3.6 10.1 47.2 3.3 9.7 952, 940, 893, 777, 770, 720, 710, 67563.4 5.9 6.7 53.2 5.8 6.5 2420 (NH), 992, 887, 848, 770w, 75242.1 4.9 5.6 42.0 4.7 5.4 3200, 3110 (NH), 955w, 930, 892, 75338.8 2.6 7.6 38.4 2.7 7.3 8 2 8 ~ , ~OOW, 75552.1 3-8 8.9 51.8 4.0 8.6 1733, 983, 969w, 927w, 914, 896, 830, 768, 751, 7 1 1 ~50.6 4.0 4.0 50.6 3.9 3.9 3400, 3300, 3240 (NH), 1680, 980w, 915w, 830w,51.0 4.1 8.9 50.6 3.9 9.0 1690, 993w, 982w, 791, 75852.2 4.4 3.8 52.0 4.3 3-8 1683, 902w, 778, 758, 733w54.7 4.2 3.4 58.5 4.1 3-6 972w, 760, 722, 70960.5 4-6 3.6 59.5 4.5 3.5 glow, 781, 763, 723, 711, 70245.1 3.1 44-2 2.9 942w, glow, 800w, 793w, 759, 768, 722, 711, 700w56.2 4.5 56.4 4.0 1740, 989, 942w, 909, 892, 783, 762, 722, 710, 69653.5 3.9 6-5 53.5 3.8 6-2 920, 850, 755, 720, 7041673, 946w, 872w, 772, 766, 753, 133, 724w, 697w47.6 3.3 3.6 47.3 3.2 3.7 1681, 980w, 920, 850w, 769, 763, 73249.1 3.1 9.8 49.1 3.2 9.4 1678, 942, 935w, 810, 771, 760, 752, 732, 685, 67226.0 1-8 25.6 1.7 981w, 935, 765, 721w62.1 4-3 61.8 4.2 1679, 1648, 965, 940w, 853w, 782, 761, 743709w777, 77012.7 12.9 753, 705cyclopentadiene (0.5 g) in methanol (5 ml) containing the product.Recrystallisation from methanol gave thesodium (115 mg) was added slowly. After 20 min a t -20" nzethylide (37) (0-48 g, 72), cubic crystals, m.p. 225".the mixture was allowed to warm slowly to room tempera-ture, and the product precipitated. After 0-5 h the mixturewas cooled, water (z ml) was added, and the crude cyczo-fientadienide was filtered off and dried. RecrystallisationWe thank the S.R.C. for a studentship (to J. K. s.),Pfizer Ltd. for financial assistance, and Mrs. E. E. Richardsfor the loo MHz n'm*r. spectrum'amp;om acetonitrile gave yellow-brown needles (0.5 g, 40) ,11i.p. ca. 114" (decomp.).1 0-Phenoxathiiniunz Bis(unethoxycarbony1)methyZide (37) .-1/2175 Received, 17th Novembev, 1971113 H. D. Hartough and S. L. Meisel, ' Condensed Thiophenes,'Interscience, New York, 1954, p. 155