One-step synthesis of esters of aliphatic .beta.-chloro sulfonic acids. Their sequential conversion to other sulfonic acid derivatives

Abstract

CH?c c , E ( e V ) < 4 b 5 4b0 E B i n d i n g E n e r g y B i n d i n g E n e r g y Flgure 4. X-ray photoelectron spectrum of I I I f : (a) N(ls) energy region, (b) C(1s) energy region. a pressure of less than lo-* torr. Samples were mounted on aluminum mesh at room temperature. ( a ) Reaction of Arylhydrazone -N -carboxylic Esters ( I ) and Hydrazlne Hydrate. A mixture of the hydrazone ester (0.01 mol) and the hydrazine hydrate (0.01 mol) in 50 mL of ethanol was refluxed on a water bath for a period of 5 h. Evaporation of the solvent left a viscous oil, which proved to be the arylhydrazone (I I). Crystallization of I I a from petroleum ether (60-80 "C) gave pale yellow crystals, mp 62 " C . The other hydrazones gave oily materials. ( b ) Reactlon of Arythydrazones ( I I a -g ) and Hydrochloric AcM. A mixture of the arylhydrazone (0.01 mol) in ethanol (20 mL) and 6 N HCI (5 mL) was warmed on a water bath for 5 min. A heavy solid was precipitated, which was filtered off and crystallized from ethanol to give azines of thiophene-2carboxaldehyde (I IIa), furan-2-carboxaldehyde (I1 Ib), pyrrole-2carboxaldehyde (I I IC), 5-methylthiophene-2-carboxaldehyde ( I 1 Id), indole-3-carboxaldehyde (I I Ie), N-methylpyrrole-2carboxaldehyde (I I If), and pyridine-4-carboxaldehyde (I I Ig).Azine I I I a was also prepared by refluxing an alcoholic solution of the arylhydrazone-N-carboxylic ester Ia and aqueous sodium hydroxide (10%) for 1 h. The alcohol was evaporated, and the product was crystallized from petroleum ether (60-80 "C) to give a product, which proved to be identical with IIa. This product was treated with hydrochloric acid, as mentioned above, to yield azine IIIa.( c ) Preparation of Authentlc Samples.(1) Hydrazone I I a was prepared by refluxing equimolecular amounts of thiophene-2-carboxaldehyde and hydrazine hydrate in ethanol for a period of 5 h and then worked up as described previously. (2) Azines IIIa-g were prepared by refluxing the corresponding heterocyclic aldehyde (2 mol) and hydrazine hydrate (1 mol) in ethanol and then worked up. The products proved to be identical with those obtained from procedure b.Elemental analyses were performed and submitted for review. Reglstry No. la,A one-step synthesis of methyl 2thiorohexane-1-and 2-chlorooctane-1-sulfonate by the novel free-radical addition of methyl chlorosulfonate to 1-hexene and 1-octene, respectively, Is reported. These products were converted by standard techniques into the corresponding sodium and benzylthiuronlum P-chiorosulfonlc acid salts and sulfonyl chlorides. Dehydrochlorination of these latter products with triethylamine afforded reglospecific formation of trans-a,p-unsaturated sulfonyl chlorides, which were transformed by conventional methods into sodium and benzylthiuronlum unsaturated and saturated sulfonlc acid salts. Eleven new compositions of matter are reported. Seven l-phenyl-2-[2-( 6-substituted qulnolyl)]ethanoneswere synthesized by the condensatlon of 2methyl-6-substkuted qulnollnes and methyl benzoate wlth sodlum hydrlde as the con...

Characteristic Vibrational Spectral Change Observed for the π-Conjugated Structure of Sulfonated Polyethylene

“…We synthesized or purchased the following compounds and measured the FTIR spectra for the SO 3 Na and SO 3 H species. The procedure of synthesizing these compounds is described in Scheme 1. − These compounds correspond, respectively, to the chain segments of zero, one, two, and three CC conjugated units connected to the sulfonate group. Figures −11 show the FTIR spectra of the three compounds a − c with SO 3 Na or SO 3 H groups.…”

Chemoselective Reactions of Functionalized Sulfonyl Halides

“…[298] Several elimination reactions tolerated the presence of SO 2 Cl moiety. To be more specific, acid-promoted dehydration of amides [207,299] and β-hydroxycarbonyl compounds, [207,299] dehydrochlorination [300,301] or -bromination [302] in the presence of a base were reported (Scheme 43). In addition to that, nucleophile-promoted SO 2 / HCl elimination of one of two SO 2 Cl groups present in the substrate molecule (formally as SO 2 /HCl) with further nucleophilic attack at the remaining one was reported.…”

Radical-mediated vicinal addition of alkoxysulfonyl/fluorosulfonyl and trifluoromethyl groups to aryl alkyl alkynes

“… 11 In this context, alkoxysulfonyl radicals (ROSO 2 ˙) 12 were found to add to alkenes in hot benzene. 13 Later, other groups reported the cyclization of alkoxysulfonyl radicals tethered to alkenes and alkynes. 14,15 Unfortunately, these methods either suffer from narrow substrate scope or restriction to intramolecular processes, limiting their applicability in the context of late-stage functionalization of complex molecules.…”