1-Dodecene oxidation

Blankenship [3] prepared polyethylene glycol carbamate, (II), as paint thickeners containing poIy(ethyIene oxide-b-propylene oxide-b-ethylene oxide) and either 1,6-hexamethyIene diisocyanate or 4,4 -methyIene bis-(isocyanatocy-clohexane). Polycarbamates were also prepared by Bauer [4] using a block polymer initiated by stearyl alcohol and consisting of poly(ethylene oxide-b-propylene oxide-b-butylene oxide-b-dodecene oxide-b-tetradecene oxide) coupled with the diisocyanate, Desmodur N . 

The first materials produced by this method which have obtained commercial importance are monoepoxides such as octylene oxide, dodecene oxide, and a mixture of 1,2-epoxy hexadecane and 1,2-epoxy octadecane. These epoxides are used as stabilizers for vinyl polymers and as diluents for epoxy resins. 

Sulphated zirconia catalysts can be acidic or superacidic depending on the method of treatment. A variety of acid-catalysed reactions, referred to earlier in this section, can be carried out with sulphated zirconia. Yadav and Nair (1999) have given a state-of-the art review on this subject. Examples of benzylation of benzene with benzyl chloride / benzyl alcohol, alkylation of o-xylene with. styrene, alkylation of diphenyl oxide with 1-dodecene, isomerization of epoxides to aldehydes, acylation of benzene / chlorobenzene with p-chloro benzoylchloride, etc. are covered in the review. 

Biological. Dodecane may biodegrade in two ways. The first is the formation of dodecyl hydroperoxide which decomposes to 1-dodecanol. The alcohol is oxidized forming dodecanoic acid. The other pathway involves dehydrogenation to 1-dodecene, which may react with water, giving 1-dodecanol (Dugan, 1972). 

Several efficient procedures for alkene epoxidation using Oxone were reported, such as Oxone/aqueous NaOH, Oxone/acetone, Oxone/water , Oxone/PTC/benzene/ aqueous buffer solution or Oxone/2-butanone system. Thus, sorbic acid can be regioselectively oxidized using Oxone/aqueous NaOH to 4,5-epoxy-2-hexenoic acid in 84% yield. Similarly, cyclooctene is oxidized to cyclooctene oxide in 81% yield, just by stirring it with Oxone in water . 1-Dodecene is epoxidized in good yield by Oxone/PTC in benzene aqueous buffer solution. It is otherwise difficult to epoxidize 1-dodecene by other oxidizing reagents. ... 

Under the same conditions the 6,7-dodecanedione bishydrazone is converted to 36% 6-dodecyne and 19% 6-dodecene (35% Z, 65% E) . Remarkably no hexanonitrile is found in this case. In the oxidation of 1,2-bishydrazones to alkynes so far the chemical oxidants copper(II)salts mercuric oxide or nickel peroxide are superior to the nickel hydroxide electrode. 

The inefficient trapping of thiyl radicals by dodecene-1 was attributed to the effective interception of the radicals by Mn(III), resulting in electron transfer oxidation to the thioxonium ion. By contrast, thiyl radicals formed in the oxidation of thiols by the weaker oxidant, ferric octanoate, were scavenged by dodecene-1. Disulfide was formed by dimerization of thiyl radicals.352 Thus, the mechanism for disulfide formation is dependent on the nature of the metal oxidant. 

Dodecene is an intermediate for surfactants, mainly through two routes. One, the larger user, produces dodecylbenzene sulfonate for anionic detergents. The other goes through the oxo process to tridecyl alcohol, which then is converted into a nonionic detergent by the addition of alkylene oxides. 

A successful ruthenium-catalyzed oxidative coupling and subsequent cyclization between 2-aminobenzyl alcohol and secondary alcohols in the presence of KOH and 1-dodecene leading to quinolines has been reported <03T7997>. After optimization of conditions, yields were fair to good. The reaction is widely applicable to a large series of 2-substituted quinolines. 

Orchin and colleagues have studied (239, 325, 326, 514, 543-545) extensively the platinum complexes traws-(olefin)(4-ZC5H4NO)PtCl2 (212) in which the 4-substituent, Z, on pyridine-iV-oxide is OCH3, CH3, H, Cl, CO2CH3, CN, or NO2. The olefins have included ethylene (239), styrene, and 3- or 4-substituted styrenes (239, 544), 1-dodecene (544),... 

Figure 2, a) AFM image of silicon oxide nanostructure on dodecene-terminated silicon b) wide field microscope image of the dye treated nanostiucture under light excitation (514 nm),... 

The mass spectrometric characterization of an AEO siufactant (dodecyl alcohol with 9 EO) by means of multi-stage ion-trap MS-MS was reported by Levine et al. [34]. The fragmentation observed include (a) consecutive losses of ethylene oxide luiits, (b) loss of dodecene followed by consecutive losses of ethylene oxide units, (c) loss of dodecanol followed by consecutive losses of ethylene oxide units, and (d)... 

Failure of aliphatic aldehydes to be produced in high yields by application of this steam distillation method to estragole and 1-dodecene may be attributed to the increased stability of the intermediate hydroperoxides toward hydrolysis. In other words, the conversion rates of the corresponding intermediates, V to VI to VII, are so slow that the hydroperoxides are either steam distilled and/or undergo the relatively more rapid oxidative rearrangement to VIII and subsequent conversion to IX. 

Poly(ethylene glycol)-supported manganese porphyrins were tested in the epoxidation of cyclooctene, 1-dodecene, cyclohexene, styrene, and indene with PhIO or H2O2 in the presence of N-alkylimidazoles as axial ligands [51]. The polymers were soluble in the reaction mixtures and could be precipitated and reused. Epoxide yields from 80 to 100%, except for 1-dodecene (38% yield), were obtained using PhIO as oxidant. 

A series of polymer-anchored epoxidation catalysts was obtained by modifying Merrifield resin with imidazole [61], diphosphines [62], or piperazine [63] followed by treatment with UV-activated Mo(CO)6. High activities in the epoxidation of cyclic (cyclooctene, cyclohexene, indene, and a-pinene) as well as linear alkenes (styrene, a-methylstyrene, 1-heptene, 1-dodecene, cis- and frans-stilbene) were observed using TBHP as oxidant. The catalysts were recovered and reused up to 10 times in the epoxidation of cyclooctene without loss of activity. 

Diphenyl oxide+7-dodecene [BMIM]C1/A1C13 [53] Monododecyl diphenyl - 90 -... 

Interestingly, the presence of two distinct phases did not hamper the oxidation of the alkene dissolved in the organic solvent. However, a high stirring rate (1300 min ) is required. Furthermore, the catalyst solution could be reused for a further reaction run leading to the same result. Terminal olefins such as 1-dodecene require a longer reaction time after 14 h only 48% conversion was observed. 

Selectivity in the dehydration of olefins is improved with pillared clays. Clays with aluminum oxide or mixed aluminum and iron oxide pillars converted isopropyl alcohol to propylene with more than 90% selectivity.256 A small amount of isopropyl ether was formed. When zeolite Y is used, the two products are formed in roughly equal amounts. A tantalum-pillared montmorillonite converted 1-butanol to butenes at 500°C with 100% selectivity at 41% conversion.257 The product contained a 17 20 16 mixture of 1 -butene/c/s-2-butene/fra/ s-2-butene. No butyraldehyde or butyl ether was formed. A pillared clay has been used for the alkylation of benzene with 1-dodecene without formation of dialkylated products.258 The carbonylation of styrene proceeded in 100% yield (6.50).259... 

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