Regioselectivity Control in Diels−Alder Reactions of Surfactant 1,3-Dienes with Surfactant Dienophiles

Abstract

The ability of surfactant aggregate−H2O interfaces to control the regioselectivity of Diels−Alder reactions has been investigated. Cycloadditions of surfactant 1,3-dienes 2-[[3-(dimethyldodecylsilyl)-1,3-butadien-2-yl]thio]-N,N,N-trimethyl-1-ethanaminium iodide (1a) and 6-[[3-(dimethyloctylsilyl)-1,3-butadien-2-yl]thio]-N,N,N-trimethyl-1-hexanaminium iodide (1b) with surfactant dienophiles (E)-2-[[[2-(dodecoxycarbonyl)ethenyl]carbonyl]oxy]-N,N,N-trimethyl-1-ethanaminium iodide (2a) and (E)-6-[[[2-(octoxycarbonyl)ethenyl]carbonyl]oxy]-N,N,N-trimethyl-1-hexanaminium bromide (2b) within their aqueous mixed micelles have been performed at 25(35) °C. The cycloaddition of 1a and 2a gave a 30:1 ratio of trans-1-[(2-trimethylammonio)ethylthio]-2-(dimethyldodecylsilyl)-4-(dodecoxycarbonyl)-5-[(2-trimethylammonio)ethoxycarbonyl]-1-cyclohexene dihalide (15a) and trans-1-[(2-trimethylammonio)ethylthio]-2-(dimethyldodecylsilyl)-4-[(2-trimethylammonio)ethoxycarbonyl]-5-(dodecoxycarbonyl)-1-cyclohexene dihalide (16a), respectively, and that of 1b and 2b a 6.6:1 ratio of trans-1-[(6-trimethylammonio)hexylthio]-2-(dimethyloctylsilyl)-4-(octoxycarbonyl)-5-[6-(trimethylammonio)hexoxycarbonyl]-1-cyclohexene dihalide (15b) and trans-1-[(6-trimethylammonio)hexylthio]-2-(dimethyloctylsilyl)-4-[6-(trimethylammonio)hexoxycarbonyl]-5-(octoxycarbonyl)-1-cyclohexene dihalide (16b), respectively. The excess of 15 over 16 is consistent with the reaction of 1 and 2 within mixed aggregates in their preferred orientations at the aggregate−H2O interface. The greater regioselectivity obtained in the reaction of 1a and 2a is ascribed to the shorter tether between their reactive functional groups and quaternary ammonium headgroups. A monolayer study of 15a and 16a was also performed.

Synthesis and properties of novel fluorescent‐tagged polyacrylate‐based scale inhibitors

“…120–125 °С (literature values: m.p. 90–130 °С from MeOH); 1 H‐NMR (300.21 MHz, D 2 O, δ/ppm, J /Hz): 2.94 (с, 6H, N(CH 3 ) 2 ), 3.50–3.56 (m, 2H, CH 2 N), 4.50–4.56 (m, 2H, CH 2 O), 6.47 (d, 1H, J = 15.8, CH a CH b ), 6.91 (d, 1H, J = 15.8, CH a CH b ). 13 C‐NMR (100.61 MHz, D 2 O, δ/ppm): 172.72, 166.35, 143.38,128.95, 58.78, 57.07, 43.36; elemental analysis (calc.…”

Radical polymeric photoinitiators bearing side‐chain camphorquinone moieties linked to the main chain through a flexible spacer

“…The amine‐containing monomer DMAHM was obtained by reaction of 6‐(dimethylamino)hexane‐1‐ol8 with methacryloyl chloride. Both the monomers MHCQ and DMAHM were fully characterized by 1 H‐ and 13 C NMR, as well as by FT‐IR.…”

New technique for the fabrication of conductive polymer/insulating polymer composite films

“…6‐(Dimethylamino)hexane‐1‐ol was prepared from 6‐chlorohexane‐1‐ol by reacting with 1,1 N , N ‐dimethyl hydrazine according to the literature8 in 65% yield.…”