The preparation of the title compounds as a new type of stable S-ylides has been described. The reaction of 1-dimethylsulfuranylidene-1-phenylsulfonyl-2-propanone (IIb) with lithium aluminium hydride was found to result in the formation of trans-phenylpropenylsulfone (IV), phenylsulfonyl-2-propanone (Ib), and an unidentified paraffin as major products

Masuike, Taketosi

Takeda, Akira

Torii, Sigeru

Uno, Takaaki

Wada, Satosi

English

Okayama University Scientific Achievement Repository

MEMOIRS OF THE SCHOOL OF EKCINEERI:-;C OKAYAMA U:-;IVERSITY, Vol. 3, 1\'0. I, SEPTEMBER, 1968New Stable Sulfonium Ylides. I-Dimethylsulfuranylidene-l-phenylsulfonyl-2-propanone and Related Compounds*Akira TAKEDA, Satosi WADA, Takaaki U:,\o, Taketosi M.\SGIKE, **and Sigeru TORII***Department oj Synthetics Chemistry(Received March 15, 1968)The preparation of the title compounds as a new type of stable S-ylideshas been described. The reaction of I-dimethylsulfuranylidene-I.phenylsul-fonyl-2-propanone (II b) with lithium aluminium hydride was found to result inthe formation of trans-phenylpropenylsulfone (IV), phenylsulfonyl-2-propanone(Ib), and an unidentified paraffin as major products.While it has been well-known12 3) that di-methylsulfoxide (DMSO) readily reacts witha variety of active methylene compounds inthe presence of dehydrating agents to givestable So ylides, the reactivity of such com-pounds as to have a methylene group, whichis located between carbonyl and sulfonylgroups, has not been investigated. We wish toreport here the results of our studies on thepreparation and the ylide formation of activemethylene compounds (I) such as n-butylsul-fonyl-2-propanone (Ia), 6) phenylsulfonyl-2-propanone (Ib),8) and tetrahydrothiapyran-3-one-I,I-dioxide (Ic)9) (see Scheme I).Scheme Io1.1R-C.~CHzR'-S'OzI+/ CH3O<-S·... Cfh(CH3CO)ZO_._- .-,IIa, R = CH3; R' = n-C4Hsc, R=R'=-(CH2)3-e, R=OCZH5; R'=C6H5The condensation was carried out as usualby standing a mixture of DMSO and activemethylene compounds in the presence ofacetic anhydride for several days, at roomtemperature. The products (IIa-c) were isolatedas stable crystalls giving correct analyticalvalues, which correspond to those calculatedfor the proposed structure (II). Yields, physi-cal and analytical data of these S-ylides are* Presented at the Chugoku Sikoku Local ~Ieetingof the Chcmical Society of Japan, Okayama,Japan, Octobcr II, 1967.** Department of Applied Chemistry, Fuculty ofEngineering, Osaka City University, Sakai,Osaka, Japan.*** Department of Industrial Chemistry, School ofEngineering, Okayama Cniversity.b, R=CH3; R'=CsH5e1, R=OCzH5; R'=n-C4Hslisted in Table I. The presence of ylidecarbonyl group is comfirmed by IR absorptionbands at 1570 (IIa), 1580 (lIb), and 1550 cm-1(lIe), 2.3.11) as shown in Figure 1.To the contrary, ethyl n-butylsulfonylacetate(Id)IO) and ethyl phenylsulfonylacetate (Ie)7)did not give the ylides but were recovered un-changed at the reactions carried out as usual.Moreover, when the reaction mixture waskept at reflux temperature, Id gave a smallamount of C-acetylated product (III). Thefailure of the ability to form the stable ylidesof these compounds (Id, Ie) is apparently dueto the weak activating effect of carbethoxygroup as compared to acetyl group.As a part of the study on the reactivity ofS-ylides, the reaction of lIb, which was most119120 A. TAKEDA, S. WADA, T. UNO, T. MASUIKE and S. TORI! (Vol. 3,Table 1. S-Ylides"R~CO (, EB /C113"C-SR'~ S02/ ' CH3~Calcd, 96~R R' Mp, DCYield,% C H c HlIa CH3In-C4Hs 67.5-72.0 I 43.0 45.29 7.43 I 45.68 7.61lIb CH3 C6H5 122-124I77.5 50.97 5.51I51.13 5.46lIe -(CH2)J- 209-212 (dec) 63.7 40.82 5.81 40.36 5.81._--- ------emf-----:1J:''''':1 2~-" 1'::') 1~") 1/:) :2CO lC:;O 8~O1---'- ! -,---,- - i - t --,- ~ --~ 1--- .j---- .; ---~ :.-'-'-'-1il~···_··YV~tl""{i\I - -'-~\()I:[ry\_I- - __ I ~ __Figure I. IR spectra of: (a) l-dimethylsulfuranylidene-I-n-butylsulfonyl-2-propanone(IIa), nujol; (b) l-dimethylsulfuranylidene-l-phenylsulfonyl-2-propanone (II b), nujol;(c) 2-dimethylsulfuranylidene-tetrahydrothiapyran-3-one-l, I-dioxide (IIe), nujol.readily accessible, with excess lithium alu-minium hydride in tetrahydrofuran was thenattempted (see Scheme II). A yellow liquiddistilling at 180° (oil bath)/l mm Hg was ob-tained, when it was discontinued after 0.5 hrof refluxing. IR spectrum of this liquid wasquite similar when observed before and afterthe distillation, and showed a moderate ab-sorption at 1645 em-I, indicating the presenceof olefinic linkage. Thin layer chromato-graphy (tlc) of this fraction revealed thepresence of three components (A, B, and C) inroughly equal portions. By means of prepara-tive tlc, Ib (A), unidentified paraffin (C), andas a third component, an oil (B), which readily" All the eomj:ocmds listed here are new.solidified to yellow crystal melting at 57-59°,were separated. From IR data and mixed mp,the substance B was identified as tralls-phenyl-propenylsulfone (IV).4) As a whole, the re-actions like route 1(nucleophilic substitution atC.l) and route 2 (nucleophilic addition to C-2)are expected to compete, for the hydride anioncan attack either C-2 or Col of IIb. Evidencedby the fact that IV was not produced by theaction of lithium aluminium hydride on lb,route 2 rather than route 1 has now been pos-tulated as a reasonable reaction mechanism ofthe formation of IV. It is also assumed thatby the formation of the metal salt of Ib inroute 1, the electron density at C-2 would in-crease, hence the nucleophilic addition of the1968) New Stable SuljOnium Yliaes.Scheme II121rhoS -, /'002 c; __ cf"(CHa12SE±> 'CHa(II b)(H:~ M!fl ~ metal hydride)second hydride amon to C-2 becomes sup-pressed.Experhnental SectionAll melting and boiling points are uncor-rected. Thin layer chromatography (tlc) andpreparative tlc were effected using silica gelG (E. Merck) as a support and chloroform asa developer, and the spots were visualizedwith a potassium permanganate-sulfuric acidsolution.n-Butylsulfonyl-2-propanone (Ia). - Thiscompound was prepared by the reaction ofsodium n-butanesulfinate5) with chloroacetonein a 18.7% yield, bp 137 -140° (4 mm) (lit. 6)bp 136-13]0 (4 mm)]; IR, 1320 (II S02), and1720 cm- l (II C = 0).Phenylsulfonyl-2-propanone (Ib). - Thiscompound was prepared in a 20.5 96 yield bythe reaction of sodium benzenesulfinate7) withchloroacetone, in the same manner as above,mp 53-55° (lit. 8) mp 57°); IR, 1310, 1160 (IIS02), and 1725 cm-! (II C = 0). It gave correctanalyses.Tetrahydrothiapyran-3-one-I, I-dioxide(Ie). - This compound was prepared by theoxidation of tetrahydrothiapyran-3-one9) in a42.996 yield, mp 138.5-140° (lit. 9) mp 140-140.5°); IR, 1315, 1125 (II S02), and 1725cm-1(II C=O).I-DiInethyIsulfuranylidene-I-n-butyI.sulfonyl-2-propanone (IIa). - A mixture otn-butylsulfonyl-2-propanone (4. Og, 0.023 mole),dimethylsulfoxide (17.6 g, 0.23 mole), andacetic anhydride (23.0 g, 0.23 mole) was kept forthree days at room temperature, using a cal-I'h-S '" _II02 C c:~H/ . CHa(IV)cium chloride tube to avoid moisture. Afterremoving the solvent in vacuo, the residualgummy material was recrystallized from car-bon tetrachloride to afford 2.3g (43.0%) ofIIa, mp 67.5-72.0°; IR, 1330, 1130 (II S02),and 1570 cm- l (ylide II C = 0). Anal. Calcd forC.H1sO.Sz: C, 45.68; H, 7.61. Found: C,45.29; H, 7.43.I-Ditnethylsulfuranylidene-I-phenyl-sulfonyl-2-propanone (lIb). - In a similarmanner as described in the above paragraph,from a mixture of phenylsulfonyl-2-propanone(26.9g, 0.136mole), dimethylsulfoxide (l06g,1. 36 mole), and acetic anhydride (l09 g, 1. 36mole), a brownish oil was obtained, whichcrystallized upon scratching. Recrystallizationfrom ethanol gave 27.2 g (77.5 %) of lIb, mp122°; IR, 1310, 1150 (II S02), and 1580 cm- t(ylide II C = 0). Anal. Calcd for C ll H 140"S2:C, 51.14; H, 5.46. Found: C, 50.97; H,5.51.2-DhnethyIsulfuranylidene-tetrahydro-thiapyran-3-one-I, I-dioxide (lIe). - Amixture of tetrahydrothiapyran-3-one-l, I-di-oxide (l.Og, 0.0068 mole), dimethylsulfoxide(5.3g, 0.068 mole), and acetic anhydride(7.0g,0.068 mole) was kept for two days. The result-ing precipitate was filtered and recrystallizedfrom ethanol to yield O. 9g (63.7%) of lIe, mp209-212° (dec); IR, 1340, 111O(vS02), and1550 cm-! (ylide II C = 0). Anal. Calcd forCiH:203S2: C, 40.36; H, 5.81. Found: C,40.82; H, 5.81.Reaction of Ethyl n-ButylsulfonyIaee-tate with Dhnethylsulfoxide. - A mixtureof ethyl n-butylsulfonylacetate10) (2.1g, 0.01122 A. TAKEDA, S. WADA, T. UNO, T. MASUlKE and S. TORlimole), dimethylsulfoxide (7.8 g, 0.1 mole) andacetic anhydride (5.0 g, 0.05 mole) was reflux-ed for 1.5 hr at 165 0 • The reaction was con-tinued for additional 0.5hr after 5.0g of aceticanhydride was added. Slightly yellow oil (0.2g,bp 131.5° (0.06 mm)], was obtained after theremoval of solvent in vacuo. Identification asethyl 2-n-butylsulfonylacetoacetate (III): IR,1735 (ester J,J C = 0), 1725 (ketone J,J C = 0),1325, and 1115cm-1 (J,J SOz). Anal. CaIcd forC IOH IS06S: C, 47.99; H,7.63. Found: C,47.61; H, 7.57.Reaction of I-Dhnethylsulfuranylidene-I-phenylsulfonyl-2-propanone (lIb) withExcess LithiutTl AlutTliniutTl Hydride. -A mixture of lIb (2.0 g, 0.0077 mole) andlithium aluminium hydride (0 .46g, 0.012 mole)suspended in 20 ml of THF was refluxed for0.5 hr. After the removal of the solvent underreduced presure, 1.2 g of a crude product wasobtained. On vacuum distillation, it gave ayellow liquid (ca. 0.5g) boiling at 180° (oilbath)/l mmHg. The infrared spectrum of thisliquid was identical with that of the crudeproduct.The constituents of the distillate were sepa-rated by preparative tlc. R f : A, 0.30; B, 0.45;hydrocarbon, 0.99. By the comparison of theweight of each components collected from thespots on tIc plates, the following ratio wasroughly estimated: A/B/hydrocarbon-l/ 1/1.The substance A, mp 49-52°, mixed mp 52-54°, IR bands at 1725, 1310, and 1160 em-I.Authentic sample of phenylsulfonyl-2-propanoneBl : IR, 1725, 1310, and 1160 em-I. Thesubstance B, mp57-59°, mixed mp 61-63°, IRbands at 1645 (double bond), 1310, 1155 (J,J SOz),and 965 cm- I (trans disubstituted olefin). Au-thentic sample of trans-phenylpropenylsul-fone4l : IR, 1645, 1310, 1155, and 965 em-I.Characterization of the hydrocarbon was byIR data.Reaction of Phenylsulfonyl-2-pro-panone (Ib) with LithiutTl AlutTliniutTl Hy-dride. - In the same manner as described inthe above experiment, a mixture of Ib (1. 5g,0.0077 mole) and lithium aluminium hydride(0.46 g, 0.012 mole) suspended in 20 ml of THFwas refiuxed for 0.5 hr. The constituents ofthe yellow oil (ca. 0.5g), which was obtainedby the distillation (180° (oil bath)/ I mmHg]of the crude product, was treated by prepara-tive tIc as usual. R r : A', 0.27; B', 0.40; hy-drocarbon, 0.99. The following ratio wasroughly estimated for the constituents: A'/BI /hydrocarbon-l/6/3. The substance A' wasidentified as the starting material. The oilysubstance BI had strong bands at 1310 and1165, and weak bands at 1725 and 1590, noabsorption at 1645 em-I. Characterization ofthe hydrocarbon was by IR data.References1) R. GOMPPER and H. EUCHNER: Ber. 99, (1966)527.2) R. aDA and Y. HAYASHI: 1'\ippon Kagaku Zasshi87, (1966) 104.3) H. NOZAKI, Z. MORITA, and K. KONDO:Tetrahedron Letters (1966) 2913.4) £.1'\. KARAULOVA, D. S. l\!EILANOVA, and E. D.GAL'PERN: Zhur. Obshchei khim. 27,(1957) 3034.5) W. J. HUMPHLET and R. W. LAMON: J. Org.Chern. 29, (1964) 2148.6) E. A. FEHNEL and M. CARMACK: J. Am. Chern.Soc. 71, (1949) 237.7) W. C. ASHLEY and R. L. SHRINER: iLid. 54,(1932) 4410.8) R. OTTO and W. OTTO: J. Prakt. Chern. C2J36, (1887) 403.9) E. A. FEHNEL: J. Am. Chern. Soc. 74, (1952)1569.10) S. CHODROFF and W.1'. WHITMORE: ibid. 72,(1950) 1073.11) K. W. RATTS and A. N. YAO: j. Org. Chem.31, (1966) 1185.

CHODROFF and W.1'.

Obshchei khim.

Tetrahedron Letters

New Stable Sulfonium Ylides. 1-Dimethylsulfuranylidene-l-phenylsulfonyl-2-propanone and Related Compounds

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New Stable Sulfonium Ylides. 1-Dimethylsulfuranylidene-l-phenylsulfonyl-2-propanone and Related Compounds

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