N‐halosuccinimide‐mercaptoethanol cohalogenation of olefinic fatty methyl esters: Synthesis of β‐halo thioethoxylates

Abstract

Olefinic fatty methyl esters, undec-10-enoate (1), octadec-Z-9-enoate (2), methyl-12 hydroxy octadec-Z-9-enoate (3), on reaction with N-halosuccinimides (4,5), that is, N-bromosuccinimide (4) or N-chlorosuccinimide (5) and 2-mercaptoethanol (6) in benzene, gave β-bromo-or β-chlorothioethoxylates (8-13). β-Halothioethoxylates so formed were acetylated with acetyl chloride in CH 2 Cl 2 to form the respective acetylated products (20-25).

Synthesis of Wax Esters from α-Olefins

“…The reaction has been applied to terminal olefins. The terminal olefins (1-2), when reacted with NBS (3) and long-chain fatty acids (i.e., lauric acid (4), myristic acid (5), or palmitic acid (6)) resulted in ∼50% conversion of the R-olefin to the respective wax esters (7)(8)(9)(10)(11)(12). The structure of these wax esters has been established by their mass spectra, infrared (IR) spectra, and 1 H and 13 C nuclear magnetic resonance (NMR) analyses.…”

“…The co-halogenation of alkenes with halogens and nucleophilic solvents such as water, diemethylsulfoxides, dimethylformamide, carboxylic acids, alcohols, nitriles, and ethers is well-documented. 9 In our earlier work, we have reported the synthesis of β-haloethers, 10 haloethoxylates, 11 and β-halothioethoxylates 12 from olefinic fatty methyl esters. In continuation of our research, an attempt has been made to prepare wax esters using the co-halogenation reaction of N-bromosuccinimide (NBS, 3) and long-chain fatty acids (such as lauric acid (4), myristic acid (5), or palmitic acid (6)) on the R-olefins (i.e., 1-octadecene (1) and 1-hexadecene (2)).…”

Synthesis of Gemini Surfactants from N-Halosuccinimide−Dimercaptoethane Cohalogenation of Olefinic Fatty Methyl Esters

“…13 A recent report 14 described the reaction of N-bromosuccinimide and dimercaptoethane in diethyl ether to form β,β′-dibromodithioethers from alkenes. In our earlier work, we reported a new synthetic strategy for the synthesis of β-haloethoxylates 15 and β-halothioethoxylates 16 from olefinic fatty methyl esters. In continuation of our research, an attempt has been made to prepare gemini surfactants using the cohalogenation reaction of N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS) followed by the addition of dimercaptoethane to the olefinic fatty methyl esters, i.e., undec-10-enoate, octadec-Z,9-enoate, and methyl 12hydroxyoctadec-Z,9-enoate.…”