R-Olefins (1-octadecene (1) and 1-hexadecene (2)), when reacted with N-bromosuccinimide (NBS (3)) and long-chain fatty acids (such as lauric acid (4), myristic acid (5), or palmitic acid (6)) in dichloromethane at room temperature, resulted in ca. 50% conversion of the R-olefin, yielding the wax esters: dodecanoic acid 1-bromomethyl heptadecyl ester (7a)/dodecanoic acid 2-bromomethyl octadecyl ester (7b); tetradecanoic acid 1-bromomethyl heptadecyl ester (8a)/tetradecanoic acid 2-bromomethyl octadecyl ester (8b); hexadecanoic acid 1-bromomethyl heptadecyl ester (9a)/hexadecanoic acid 2-bromomethyl octadecyl ester (9b); dodecanoic acid 1-bromomethyl pentadecyl ester (10a)/dodecanoic acid 2-bromomethyl hexadecyl ester (10b); tetradecanoic acid 1-bromomethyl pentadecyl ester (11a)/tetradecanoic acid 2-bromomethyl hexadecyl ester (11b); and hexadecanoic acid 1-bromomethyl pentadecyl ester (12a)/hexadecanoic acid 2-bromomethyl hexadecyl ester (12b).
Olefinic fatty methyl esters [undec-10-enoate (1 1), octadec-Z-9-enoate (2 2), methyl-12 hydroxy octadec-Z-9-enoate (3 3)], on reaction with an N-halosuccinimide (4 4--5 5)-i.e., N-bromosuccinimide (NBS; 4 4) or N-chlorosuccinimide (NCS; 5 5)-in the presence of diols such as mono-, di-, tri-, and tetraethylene glycols (6 6--9 9), gave the respective β-bromo-or β-chloroethoxylates (1 11 1--3 34 4).Paper no. S1476 in JSD 9, 51-56 (Qtr. 1, 2006)., ethylene glycols (mono-, di-, tri-, and tetra-), methyl esters, octadec-Z-9-enoic acid, polyethers, undec-10-enoic acid.Alkyl ethoxylates are well known for their use as nonionic surfactants (1). The ethoxylates also serve as starting materials for the formation of alkyl ether sulfate, a product used extensively for the manufacture of shampoos. These ethoxylates are generally prepared by an ethoxylation reaction of fatty alcohol with ethylene oxide. The cohalogenation of alkenes with halogens and nucleophilic solvents such as water, diomethylsulfoxides, dimethylformamide, carboxylic acids, alcohols, nitriles, and ethers is well documented (2). Dinulescu et al.(3) also reported the cohalogenation with ethereal solvents such as diethyl ether, tetrahydrofuran, dioxane, and ethylene oxide, leading to substituted β-haloether. A recent report by Younes et al. (4) describes the reaction of Nbromosuccinimide (NBS) and dimercaptoethane in diethyl ether to form β,β ′ -dibromodithioethers. To date, no reports have appeared on the utilization of cohalogenation reactions in fatty acid or vegetable oil chemistry. However, Ahmed and Singh (5) reported the cohalogenation of carboxylic acids on fatty methyl esters in a previous work. In the present study, we attempted to use the cohalogenation reaction of NBS and N-chlorosuccinimide (NCS) on olefinic fatty methyl esters to prepare potentially useful β-bromoethoxylates and β-chloroethoxylates. EXPERIMENTAL PROCEDURESMaterials and methods. Undec-10-enoic acid, octadec-Z-9-enoic acid, and NCS were purchased from Loba Chemicals (Mumbai, India). NBS was purchased from Central Drug House (New Delhi, India). 12-Hydroxy octadec-Z-9-enoic acid was isolated from castor oil using the partitioning method of Gunstone (6). Mono-, di-, tri-, and tetraethylene glycols were procured from M/S Sisco Chem. (Bombay, India) and were air-dried in an oven at a temperature of 120°C for 4 h, followed by cooling and storage in a desiccator. Thin-layer chromatography (TLC) was carried out on silica gel G-coated (0.25-mm thick) plates with petroleum ether/diethyl ether/acetic acid (80:20:1 or 60:40:1) as the mobile phase. Spots were visualized by iodine. Infrared spectra were recorded on a Shimadzu FT-IR 8400s instrument. 1 H nuclear magnetic resonance (NMR) spectra were recorded on a Brucker-200 spectrometer, and 13 C NMR spectra were recorded on a Jeol FT-NMR spectrometer at 300 MHz (AL-300). Mass spectra were recorded on a Jeol SX-102 [electron impact/chemical ionization/fast atom bombardment (FAB)] at the Central Drug Research Institute (CDRI) in Lukhnow, India. G...
Olefinic fatty methyl esters (undec-10-enoate (1), octadec-Z,9-enoate (2), methyl 12-hydroxyoctadec-Z,9-enoate (3)), on reaction with N-halosuccinimides (4 and 5), i.e., N-bromosuccinimide (NBS, 4) or N-chlorosuccinimide (NCS, 5), and dimercaptoethane (6) in diethylether gave the gemini surfactants (β,β‘-dibromodithioethers) (7−12).
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).
Reacting methyl isoricinoleate with N-bromosuccinimide in the presence of excess diols [mono-, di-, tri-, and tetraethylene glycol] gave the 1,4-epoxy derivative in 80% yield along with the respective β-bromoethoxylates as minor products (20%). However, when the reaction was carried out with Nchlorosuccinimide, the yield of 1,4-epoxy derivative was reduced to 20%, and formation of β-chloroethoxylates was increased to 80%.Paper no. S1528 in JSD 9, 259-265 (Qtr. 3, 2006).
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