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Organic Reactions of Reduced Species of Sulfur Dioxide' 5750 J. Org. Chem. 1988,53, 5750-5756 lation at the STO-3G level and find that neutral ascorbate Acknowledgment. We thank Joyce Wilde for assis- has a higher electron density at 02 than at 03. An ex- tance with NMR spectra and Lucile Blanchard for assis- perimental indication comes from consideration of the tance with the preparation of the manuscript. The NMR dianion; in the dianion, it is clear that 02is about 4 powers spectrometer was purchased, in part, by a grant from the of 10 more basic than 03. There is synthetic evidence that Dreyfus Foundation. in the dianion, reaction at 02 is more rapid.6 Registry No. 1, 15042-01-0;2, 116565-54-9; 3, 116565-55-0; It is also clear that long reaction times or addition of 4, 32643-49-5; 5, 116565-56-1; 6, 14200-03-4; 7, 116565-57-2;8, protic solvents results in high yields of 2-ester. A reaction 116565-58-3;9, 116565-59-4; 10,116565-60-7; 11, 29881-30-9; 12, mixture which was predominantly 3-ester was converted 109620-91-9; 13, 116565-61-8; 14, 116565-62-9; 15, 116565-63-0; to 2-ester if methanol was deliberately added. Therefore PhzP(O)Cl, 1499-21-4. there is evidence that one reason for production of 2-esters is that a 3-ester can be initially produced but converted (47) Cabral, J.; Haake, P., manuscript in preparation on rearrange- to a 2-e~ter.~~~~~ ment of 3-esters to 2-esters. Organic Reactions of Reduced Species of Sulfur Dioxide'" William F. Jarvis,lb Michael D. Hoey, Alfred L. Finocchio, and Donald C. Dittmer* Department of Chemistry, Syracuse University, Syracuse, New York 13244 Received September 24, 1987 Rongalite (sodium hydroxymethanesulfinate or sodium formaldehydesulfoxylate) reacts with organic halides in a variety of ways depending on the structure of the organic compound. Benzyl and other alkyl halides give sulfones in generally good yields; but in several cases, reduction (2,4-dinitrobenzylbromide, phenacyl halides) or coupling @-nitrobenzylbromide under basic conditions, phenacyl bromide or iodide) of the halide occurs. Addition of sodium iodide to the mixture of Rongalite and phenacyl chloride changed the reaction from one of complete reduction to acetophenone to one of mainly dimerization to 1,4-diphenyl-l,4-butanedione.The amount of acetophenone from phenacyl bromide depends on the water content of the reaction mixture, more dimer being formed when little water is present. Diphenacyl sulfone is formed from phenacyl bromide and Rongalite in the presence of excess sulfur dioxide. The intermediate @-ketosulfinate is believed to normally lose sulfur dioxide very readily to give the enolate anion, which either is protonated to give acetophenone or reacts with phenacyl halide to give the butanedione. In the presence of excess sulfur dioxide, the loss of sulfur dioxide from the sulfiiate is suppressed, allowing sulfone formation to occur by reaction of the sulfinate with phenacyl halide. o-Xylylene dibromide gave o-xylylene, trapped as the Diels-Alder adduct with norbornene, along with the expected cyclic sulfone and cyclic sulfinate ester (sultine). A convenient synthesis of the sultine in 78% yield is achieved by treatment of cup'-dichloro-o-xylenewith Rongalite and sodium iodide. Treatment of Rongalite in DMF-H20 with sulfur dioxide gives the blue anion radical complex (SOz)(S0,'-). Anion radicals are produced from p-dinitrobenzene and p-nitrobenzoate ion when they are treated with Rongalite. Introduction oxide with organic compounds has been widely investigated Reduced species of sulfur dioxide such as SOz'- and and while much significant and fascinating chemistry has SO?- are formed by the interaction of sulfur dioxide with been discovered: there has been relatively little attention the dihydropyridine coenzyme NADPH2 and also with paid to the organic chemistry of reduced species of sulfur l-ben~yl-l,4-dihydronicotinamide,~a model for the im- di~xide.~,"The potential biological significance of these portant pyridine nucleotide coenzymes. The production species is one reason for the study of their reactivity with of these anions by the interaction of sulfur dioxide with organic compounds. In addition, these anions may be biological reducing agents may be significant with respect useful intermediates in organic chemistry. to the toxic effects of this common pollutant on plants and In a search for a more accessible laboratory source of animals, particularly since SOz'- is said to be formed in reduced species of sulfur dioxide (other than sulfur dioxide an aqueous medi~m.~~~While the reaction of sulfur di- (6) For examples, see: (a) Burgess, E. M.; Zoller, U.; Burger, R. L., Jr. J. Am. Chem. SOC.1984,106,1128. (b) Masilamini, D.; Manahan, E. H.; (1) (a) Reported in part at the 189th National Meeting of the Amer- Vitrone, J.; Rogic, M. M. J. Org. Chem. 1983,48,4918. (c) El Sheikh, S. ican Chemical Society, Miami, FL, April 1985; Abstract ORGN 51. (b) I. A.; Smith, B. C.; Soebir, M. E. Angew. Chem., Int. Ed. Engl. 1970,9, Taken in part from the Ph.D. Thesis of W. F. Jarvis, Syracuse University, 308. 1988. (7) Reactions of electrochemicallyreduced SOz: (a) Knittel, D. Mon- (2) Gause, E. M.; Greene, N. D.; Meltz, M. L.; Rowlands, J. R. Bio- atsh. Chem. 1982, 113, 37. (b) Wille, H. J.; Knittel, D.; Kastening, B. J. logical Effects of Environmental Pollutants; Lee, S. D., Ed.; Ann Arbor Appl. Electrochem. 1980,10,489. (c) Knittel, D.; Kastening, B. J. Appl. Science: Ann Arbor, 1977; p 273. Electrochem. 1973, 3, 291. (d) Kastening, B.; Gostisa-Mihelcic, B.; Di- (3) Jarvis, W. F.; Dittmer, D. C. J. Org. Chem. 1983, 48, 2784. visek, J. Faraday Discuss. Chem. SOC.1973, 56, 341. (e) Knittel, D.; (4) Eickenroht, E. Y.; Gause, E. M.; Rowlands, J. R. Environ. Lett. Kastening, B. Ber. Bunsen-Ges. Phys. Chem. 1973, 77, 833. (f) Knittel, 1975, 9, 279. D. Monatsh. Chem. 1986, 117, 359. (5) Aqueous solutions of sulfur dioxide consist of hydrated sulfur (8) (a) Gibson, H. W.; McKenzie, D. A. J. Org. Chem. 1970,35,2994. dioxide. There is no evidence for the hypothetical sulfurous acid: Purcell, (b) The kinetics of the decompositionof Rongalite to SO?- and reduction K. F.; Kotz, J. C. Inorganic Chemistry; Saunders: Philadelphia, 1977; of an azo dye has been investigated: Polenov, U. V.; Labutin, A. N.; p 345. Steudel, R. Chemistry of the Non-Metals; English Ed.; Nachod, Tsareva, A. A.; Budanov, V. V. Izv. Vyssh. Uchebn. Zaued., Khim. Khim. F. C.; Zuckerman, J. J., Ed.; de Gruyter: Berlin, 1977; p 222. Tekhnol. 1987,30, 63; Chem. Abstr. 1988, 108, 130843. 0022-3263/88/1953-5750$01.50/0 0 1988 American Chemical Society Organic Reactions of Reduced Sulfur Dioxide J. Org. Chem., Vol. 53, No. 24, 1988 5751 Table I. Reactions of Halides (RX)with Rongalite R X products (yields) PhCHz Br (PhCH2)ZSOz (86-88)' (44)b (74)' (63)d PhCHz c1 (PhCH2)ZSOz (72); PhCHzSO~CHZOCHzPh(2)e 4-BrC6H4CHz Br (4-BrC6H4CHz)zS0z(70)' (52)b (56Ic 4-ClC6H4CHz Br (~-C~C~H~CHZ)~SOZ(70)' 4-FCsH4CHz Br (4-FC6H4CHz)zSOz (62)" 4-CHsCnHdCH2 Br (4-CHsCfiHdCH2)2SO2(65)' (54)' 2-CH,C;H;CH, Br (2-CH~C~H,CH&SO~(77)' I-NCCcHACH, Br (4-NCCnHACH,),S0, (45)b 3-02N&H4C& Br (3-OzN'&&CHzjzSdz 4-CF3CBH4CHZ Br (~-CF~C~H~CHZ)ZSOZ(47)b CH~(CH~)ZCH~ Br [CH~(CH~)~IZSOZ(46)" Br(CHz)6 Br CH~(CHZ)~SOZ(43)" CHZ=CHCHz Br (CHz=CHCH&30z (20)' (3): CHz=CHCH3 (trace)b 4-OzNC6H4CHz Br (4-0zNC&CHz)2 (34); (4-0zNC6H4CHz)zSOz (78)b (83)' 2,4-(0zN)zC~H3CHz Br 2,4-(0zN)zC6H3CH3(59)' PhCOCHp c1 PhCOCH3 (93)b (30): (PhCOCHJz (70)' PhCOCH(Ph) c1 PhCOCHzPh (58)" (72)' PhCOCHz Br (PhCOCH2)Z (19)' (52)b (75): PhCOCH3 (70)" (43)b (25)h (30); (PhCOCH2)ZSOZ (55)' 4-PhC6H4COCHz Br 4-PhC6H4COCH3 (66)' (51),b (4-PhCsH4COCHZ)z (20)' (40),b (4-PhCeH4COCHz)ZSOz (55)j "DMF (1.8)-&0 (11, KHCO3, Nz, 80 "C. bDMF (1.8)-Hz0 (11, Nz, 80 "C. 'DMF (l.8)-Hz0 (l),N2,50 OC. dHzO, [CH3(CHz)s]N+(CH3)3, Br-, Nz, 50 OC. eEtOH (l)-HzO (l),NaOH, 95 OC. 'DMF (l)-HzO (l),room temperature. gDMF, NaI (lo%),room temperature. hDMF, room temperature. 'DMF (1.8)-Hz0 (l), Nz, 25 "C. 'DMF, SOz, room temperature. itself either in combination with electrochemistry or a result of a Meerwein-Ponndorf-Verley reduction ensuing dihydropyridine), we turned to Rongalite, sodium hy- from ambient alcohol solvent.16a The only aromatic droxymethanesulfinate dihydrate (also called sodium halides reported to react with Rongalite to give an aryl formaldehydesulfoxylate) , the trade name being derived sulfinate are 1-bromo- and l-chlorobenzanthrone.16bThese from its use as a discharge ("rongeage" in French) or de- reactions probably proceed by an SNArmechanism because colorizing agent in cloth printing. Rongalite may be con- of the presence of the activating carbonyl group. sidered an adduct of sodium hydrogen sulfoxylate (NaH- SOz) with formaldehyde and is a possible source of HS02- Results and Discussion and S022-,8bpurported intermediates that we have pre- In order to determine if Rongalite could produce the viously trapped in the reduction of sulfur dioxide by a same sulfur intermediates formed in the reduction of sulfur dihydr~pyridine.~These anions may be good nucleophiles dioxide by l-benzyl-1,4-dihydronicotinamide,we treated because of the alpha effectg and also may be one-electron it with sulfur dioxide under similar conditions. A deep blue donors to appropriate substrates. solution of the sulfur dioxide complex of SOz'- was ob- tained, identified by electron spin resonance and ultraviolet HHJ! spectra"Js as being the same species observed in the di- - CH2O HOCH~SO;- HSO; A hydronicotinamide rea~tion.~This indicates that Ron- galite, or one of the sulfur anions derived from it, is acting as an electron donor to SOz.
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