1- Dodecene

The trisannulation reagent 7-acetoxy-l,l l-dodecadien-3-one (134) is derived from the bisannulation reagent 124 in four steps. This reagent is a synthetic equivalent of l-dodecene-3,7,11-trione, and the two ketone groups of the trione are masked as an acetoxy and a terminal alkene. The synthesis of optically active D-homo-19-norandrosta-4-en-3-one (135) by the trisannulation reaction... 

Toxicological Information. The toxicity of the higher olefins is considered to be virtually the same as that of the homologous paraffin compounds. Based on this analogy, the suggested maximum allowable concentration in air is 500 ppm. Animal toxicity studies for hexene, octene, decene, and dodecene have shown Httle or no toxic effect except under severe inhalation conditions. The inhalation LD q for 1-hexene is 33,400 ppm for these olefins both LD q (oral) and LD q (dermal) are >10 g/kg. 

Propjiene (qv) [115-07-1] is the predominant 0x0 process olefin feedstock. Ethylene (qv) [74-85-1J, as well as a wide variety of terminal, internal, and mixed olefin streams, are also hydroformylated commercially. Branched-chain olefins include octenes, nonenes, and dodecenes from fractionation of oligomers of C —C olefins as well as octenes from dimerization and codimerization of isobutylene and 1- and 2-butenes (see Butylenes). 

Table 2. Isomer Distribution, wt %, of Dodecylbenzene from 1-Dodecene and Benzene...

Manufacture and Processing Alkylphenols of commercial importance are generally manufactured by the reaction of an alkene with phenol in the presence of an acid catalyst. The alkenes used vary from single species, such as isobutylene, to compHcated mixtures, such as propylene tetramer (dodecene). The alkene reacts with phenol to produce mono alkylphenols, dialkylphenols, and tri alkylphenols. The mono alkylphenols comprise 85% of all alkylphenol production. 

The relatively low capital cost of the simple batch reactor is its most enticing feature. The inabiUty to operate under pressure typically limits the simple batch reactor to use with the higher alkenes ie, octenes, nonenes, and dodecenes. For mainly economic reasons, these reactors are usually mn at phenol to alkene mole ratios of between 0.9 and 1.1 to 1. 

Detergents have been manufactured from long-chain alkenes and sulfuhc acid, especially those obtained from shale oil or cracking of petroleum wax. These are sulfated with 90—98 wt % acid at 10—15°C for a 5-min contact time and at an acid—alkene molar ratio of 2 1 (82). Dialkyl sulfate initially forms when 96 wt % acid is added to 1-dodecene at 0°C, but it is subsequently converted to the hydrogen sulfate in 80% yield upon the further addition of sulfuhc acid. The yield can be increased to 90% by using 98 wt % sulfuhc acid and pentane as the solvent at -15°C (83). 

Chemical Designations - Synonyms Dodecene (nonelinear) Tetrapropylene Chemical Formula ... 

Both methyltriethylphosphonium fluoride and methyltributylphospho-nium fluoride have been prepared The latter generates benzyl fluoride from benzyl chloride in 80% yield and ethyl fluoroacetate from ethyl bromoacetate in 53% yield Methyltnbutylphosphonium fluoride converts 1-bromododecane to a 50 50 mixture of 1-fluorododecane and 1-dodecene Methyltnbutylphosphonium fluoride also quantitatively forms styrene from 1-bromo-1-phenylethane [26] Methyl-tnbutylphosphonium fluonde is the reagent of choice for the conversion of N,N dimethylchloroacetamide to its fluoride, but it is not able to convert chloro-acetonitnle to fluoroacetomtrile Methyltnbutylphosphonium fluoride changes chloromethyl octyl ether to the crude fluoromethyl ether in 66% yield The stereoselectivity of methyltnbutylphosphonium fluoride is illustrated by the reac tions of the 2-tert-butyl-3-chlorooxiranes [27] (Table 2)... 

Difluorododecane is unaffected by sodium methoxide in methanol, but its treatment with potassium tert-butoxide in tetrahydrofuran eliminates hydrogen fluonde stereospecifically rneso and dl compounds give, respectively, ( )- and (2) 6 fluoro 6 dodecene [12] (equation 11)... 

The allcylation of a number of aromatic compounds through the use of a chloroa-luminate(III) ionic liquid on a solid support has been investigated by Holderich and co-workers [87, 88]. Here the allcylation of aromatic compounds such as benzene, toluene, naphthalene, and phenol with dodecene was performed using the ionic liquid [BMIM]C1/A1C13 supported on silica, alumina, and zirconia. With benzene, monoalkylated dodecylbenzenes were obtained (Scheme 5.1-56). 

Scheme 5.1-56 The alkylation of benzene with dodecene with an ionic liquid on a solid support.

The product distribution in the reaction of benzene with dodecene was determined for a number of catalysts (Table 5.1-4). As can be seen, the reaction with the zeolite H-Beta gave predominantly the 2-phenyldodecane, whereas the reaction in the pure ionic liquid gave a mixture of isomers, with selectivity similar to that of aluminium chloride. The two supported ionic liquid reactions (H-Beta / IL and T 350 / IL) again gave product distributions similar to aluminium(III) chloride (T350 is a silica support made by Degussa). 

Table 5.1-4 The product distribution dependency on the catalyst used for the reaction of benzene with dodecene. IL = [BMIM]CI/AICl3 (X(AICl3) = 0.6), Temperature = 80 °C, with 6 mol% catalyst and benzene to dodecene ratio = 10 1.

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