Convenient methods for the preparation of di(1‐alkynyl) sulfides, sulfoxides and sulfones, and application of the sulfoxides and sulfones in the formation of novel heterocyclic systems

Abstract

W . Verboom et al. J Convenient methods for the preparation of di(1-alkynyl) sulfides, sulfoxides and sulfones 6-Phenyl-ZH-pyran-2,4(3 H J -dione (8)A solution of 3-acetyl-6-phenyl-2H-pyran-2,4(3H)-dione (6, 2 g) in 90% sulfuric acid (10 ml) was heated in an oil bath (bath temp. 1700) to 135-148 for one minute. The solution was cooled and poured on ice. The separated pyrandione (8) was recrystallized from ethanol, 1.1 g (6873, m.p. 246248" (decomp.)15. The analytical sample was recrystallized from ethanol, colourless prisms with the same m.p. Mixed m.p. with 6-phenyl-2H-pyran-2,4(3H)-dione obtained from dehydrobenzoylacetic acid (4b) showed no depression. C,,H,O, (188.18) calcd. C 70.21, H 4.29; found C 70.09, H 4.60. -Phenylhexane-l ,S,S-trioneA solution of 2-methyl-6-phenyl-4-pyrone (0.95 g, 5 mmol) in methanol (40 ml) and 45 % aqueous potassium hydroxide (10 ml) was heated on a water bath for 20 minutes, cooled, diluted with water (200 ml), acidified with concentrated hydrochloric acid to pH 4, and extracted with ether (3 x 10 ml). After removal of the solvent, the residue was crystallized from methanol and the pale yellow needles (0.48 g, 49 %) of I-phenylhexane-1,3,5-trione, m.p.102-103°, were obtained. The compound'6 described earlier had the m.p. 10&107° (brown needles). C I Z H I 2 O 3 (204.22) calcd.C 70.58, H 5.92; found C 70.69, H 5.80. Oxidation of an equimolar mixture of octane-2,4.5,7-tetrone (la) and I ,6-diphenylhexane-l,3,4,6-tetrone (lb) with lead tetraacetateAbstract. Di( I-alkynyl) sulfides and the corresponding sulfoxides are obtained in high yields from lithium alkynides and sulfur dichloride or thionyl chloride, respectively. The di( I-alkynyl) sulfoxides and also the corresponding sulfones (prepared by oxidation of di( I-alkynyl) sulfides with m-chloroperbenzoic acid) react very rapidly with disodium sulfide, selenide or telluride to form six-membered heterocyclic compounds.

One‐Pot Preparation of Arylethynyl Sulfides and Bis(arylethynyl) Sulfides

“…After stirring at this temperature for 1 h, the reaction was quenched with an aqueous NH 4 Cl solution. 13 2924, 2853, 2171(CϵC), 1580, 1478, 1439, 1388, 1005 9 H,Ar) ppm. The organic layer was washed with brine, dried with MgSO 4 , and filtered.…”

“…Then, ClP(O)(OEt) 2 (0.31 mL, 2.2 mmol) was added dropwise at -78°C, and the resulting mixture was warmed to room temperature and stirred for 30 min. 13 = 2963= , 2926= , 2868= , 2856= , 2155= (CϵC), 1596= , 1499= , 1453= , 1375= , 1258= , 1056= , 1018 2963, 2928, 2868, 2839, 2158(CϵC), 1600, 1498, 1481, 1461, 1389, 1269, 1237, 1031 2966, 2926, 2895, 2830, 2162(CϵC), 1602, 1503, 1487, 1439, 1332, 1246, 1203, 1129, 1098, 1039 = 3058, 2999= 3058, , 2833= 3058, , 2165= 3058, (CϵC), 1867= 3058, , 1604= 3058, , 1578= 3058, , 1498= 3058, , 1441= 3058, , 1307= 3058, , 1230= 3058, , 1165= 3058, , 1045= 3058, , 1023 = 8.4 Hz,2 H,Ar), 7.24 (t, J = 7. After stirring at this temperature for 1 h, the re...…”

“…The mixture was extracted with AcOEt (3 ϫ 30 mL). 13 3061, 21693061, (CϵC), 15823061, , 14883061, , 14783061, , 14423061, , 13973061, , 10923061, , 10233061, , 1014 Then, ClP(O)(OEt) 2 (0.32 mL, 2.2 mmol) was added dropwise at -78°C, and the resulting mixture was warmed to room temperature and stirred for 30 min. The solvent was evaporated in vacuo, and the residue was subjected to flash column chromatography (petroleum ether) to give arylethynyl sulfide 1.…”

“…The most fruitful methodologies involve the use of arylacetylenes for the preparation of arylethynyl sulfides. [13] Herein, we wish to report a new and effective one-pot strategy for the preparation of arylethynyl sulfides 1 and bis(arylethynyl) sulfides 2 from arylethanonyl sulfides and bis(arylethanonyl) sulfides, respectively, without the use of terminal arylacetylenes. [6b] We have also demonstrated a convenient methodology for the preparation of arylethynyl methyl sulfides, which starts from methylthiomethyl phenyl sulfone (MP-S) [7] and an aromatic aldehyde in a one-pot protocol.…”

“…d, J = 7.2 Hz, 2 H, Ar) ppm 13. C NMR (100 MHz, CDCl 3 ): δ = 15.98 (d, J P,C = 7.1 Hz, CH 3 ), 17.25 (SCH 3 ), 64.55 (d, J P,C = 5.8 Hz, CH 2 ), 115.82 (d, J P,C = 7.4 Hz, =CH), 124.89 (CH), 128.09 (CH), 128.24 (CH), 134.59 (C), 143.67 (d, J P,C = 9.0 Hz, =C-O) ppm.…”