Some Reactions of Methanesulfinyl Chloride¹

Abstract

SOME REACTIONS OF METHANESULFINYL CHLORIDE 805 160°/16 mm.; n2¿ 1.6112. On redistillation, through a 30cm. Fenske ring-packed column at a reflux ratio of 1:10, the product obtained possessed the following constants: b.p. 135-137°/4 mm.; n2Ds 1.6110; 1.1040.3-Isopropylidene-3-pentenenitrile9 (VIII). Acetone was condensed with 3-pentenenitrile in the same manner as described above for benzaldehyde. The product was distilled through a 76-cm. Nester spinning band column at a reflux ratio of 1:10. The liquid product melted at -8°. The compound added oxygen readily, and it was stored under nitrogen prior to analysis. Low results, particularly for carbon, were obtained until it was discovered that the analytical sample had to be burned very slowly.The compound showed infrared absorption at 3.4µ for saturated CH, 3.5µ for unsaturated CH, 4.5µ for conjugated nitrile, 6.17µ for conjugated unsaturation, 7.25µ for CH3, and 10.45µ for a trans internal double bond.2-Isopropylidene-3-pentenenitrile proved difficult to hydrolyze. In contrast with 3-pentenenitrile, no acid or lactone formed when it was boiled with concentrated hydrochloric acid. The nitrile was hydrolyzed by boiling two days with 17% aqueous sodium hydroxide. On acidification and distillation, about 10% of 3-pentenoic acid and about 10% of crude liquid 2-isopropylidene-3-pentenoic acid were recovered. Following a procedure employed by Whyte and Cope10 to hydrolyze hindered nitriles, 48 g. of 2-isopropylidene-3-pentenenitrile was stirred 15 hr. at reflux temperature with a mixture of 45 g. of potassium hydroxide, 20 g. of water, and 100 ml. of diethylene glycol. After acidification and fractional distillation, 1.7 g. of a straw-colored liquid

Methyl Sulfinates as Electrophiles in Friedel–Crafts Reactions. Synthesis of Aryl Sulfoxides

“…The Friedel–Crafts sulfinylation of aromatic compounds to form diaryl or alkyl aryl sulfoxides is relatively unexplored given that the synthesis of phenyl p -tolyl sulfoxide from benzene and p -toluenesulfinyl chloride was reported in 1926 . More than 30 years later, Douglas et al reported a 26% yield of methyl phenyl sulfoxide by reaction of benzene with methanesulfinyl chloride in the presence of anhydrous aluminum chloride, and Replogle and Maynard described low yields of the corresponding sulfoxides for the direct electrophilic sulfinylation of the azulene ring with alkane or arenesulfinyl chlorides. Olah and Nishimura have reported the high selectivity of the aluminum chloride catalyzed arenesulfinylation of benzene and polymethylbenzenes with substituted benzenesulfinyl chlorides in nitromethane solution, whereas Chasar and Pratt prepared a number of 2- and 4-hydroxydiaryl sulfoxides by the direct arenesulfinylation of substituted phenols in the presence of anhydrous aluminum chloride.…”

The hetero-Friedel-Crafts-Bradsher Cyclizations with Formation of Ring Carbon-Heteroatom (P, S) Bonds, Leading to Organic Functional Materials

“…The above strategy was utilized in syntheses of not only "small molecules" but also polymeric systems (5) starting from polysulfoxides (6) as substrates (Scheme 2). The first illustration of this new methodology was synthesis of dibenzothiophene (7) and dibenzo[b,b']thieno[2,3-f :5,4-f ']bis [1]benzothiophene (DBTBT, 8) reported by Sirringhaus and coworkers. The syntheses proceeded via the acid-induced intramolecular cyclization reaction of arenes containing methyl sulfoxide groups, i.e., methylsulfinylbiphenyl (9) and 3,7-bis(methylsulfinylo phenyl)dibenzothiophene.…”

“…The first literature report concerning intermolecular Friedel-Crafts sulfinylation of aromatic compounds, starting from diaryl or alkyl aryl sulfoxides, was published in 1926 by Farah and coworkers [ 6 ]. After 30 years, Douglas et al reported the synthesis of methyl phenyl sulfoxide from benzene and methanesulfinyl chloride in the presence of AlCl 3 [ 7 ]. Also, Gupta published the synthesis of aromatic N , N -dialkylsulfonamides via the reaction of dialkylsulfamyl chlorides with aromatic hydrocarbons in the presence of AlCl 3 [ 8 ].…”

A Convenient Alkyl, Cycloalkyl and Aralkyl Disulfides Synthesis from Aliphatic and Aromatic Aldehydes, Aliphatic Ketones and Cycloketones

“…Other important fragments Yn/e were observed at 182 (26, $-H~NSC-CGH~-CH~-S) ; 150(37, P-HzNSC-C6H4--CHs) ; 148 (13, NC-C6H4-CH2-S) ; 122 (26, CsH4CH2-S) ; 102 (10, NC-CsH4) ; 90 (47, C6H4-CH2) ; 60 (16,H2NSC).…”