N-Dodecene

Figure 7.4. Molar paraffin-to-aldehyde yield ratios in hydroformylation of n-dodecene catalyzed by HCo(CO)3Ph at 185°C as function of H2-to-CO ratio at different total pressures [11].

Hydroesterification with Co catalysts most commonly utilize pyridine or alkyl pyr-idines such as -y-picoline as cocatalysts. In a massive screening study, Co with pyridine promotors, unsubstituted in the ortho positions, gave the highest proportion of linear esters with either 1-octene oi a mixture of isomeric internal n-dodecenes. The promoter comparison was conducted at 160 C and 16.0 MPa for octene and 170°C and 18.0 MPa for the internal dodecenes, in both cases in an excess of CH3OH. The maximum rate for... 

In the case of 1-dodecyne, reaction with the same dialdehyde in the presence of niobium(V)chloride led to a variety of products, including 2-n-decylnaphthalene (23%), a minor proportion of 2-n-decyl-1-naphthol (14%), 2-n-decylnaphthalene-1,4-diol (2%) and 1-n-dodecene (ref.78). 

To do this, measurements of relaxation time (spin-spin) and T2 (spin-spin) were accomplished by means of a Bruker type SXP 4/100 pulsed spectrometer. Measurements of were carried out by the method of iii5)ulse application II-T-n/2. Impulse length H/2 was 2-3 ys, and field frequency - 90 MHz. The relaxation time T2 spin-spin was determined by the "solid echo" method, when the relaxation time was in the range of 10-200 ps, and if the relaxation time was of the order of 1 ms, the Gill-Meiboom>s method was used. Separation of relaxation time components was effected using the graphical method described by Me Brierty. In order to study the specific interactions between PAN and unsaturated elastomers the mixtures of model substances, i.e. n-dodecene-1, n-dodecane and n-butyronitrile in infrared and ultraviolet were investigated by means of Pye-Unicam spectrophotometer of the SP-700 type. 

K, and using the van t Hoff s equation, the enthalpy of complex formation was calculated to be -AH = 16.7 4.3 kJ/mol. It was found, moreover, that the absorption intensity in ultraviolet at wavenumber of v = 35 000 cm is the greatest at equimolar concentration of the substances tested. Therefore in the complex one n-butyro-nitrile molecule corresponds to one n-dodecene-1 molecule (Fig. 13). 

Table 6. Effect of ferric octoanate concentration on the ratio disulphide sulphide in the oxidation of l- -dodecanethiol in the presence of 1-n-dodecene ...

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)... 

Alkylphenols / Arylphenols Phenols + Olefins (propylene, n-butenes, wobutylene, nonenes, dodecenes etc.) styrene, alphamethyl styrene... 

A series of water-soluble polyether-substituted triphenyl phosphines (PETPPs) la-c has been successfully employed by Jin et al. [11] in the thermoregulated hydroformylation of 1-dodecene in the biphasic water/toluene system. The catalysts exhibit very good catalytic properties with conversions up to 93% and about 85% selectivity for aldehyde formation. The catalyst derived from rhodium(III) chloride and ligand Ic could be reused in four consecutive cycles without significant loss of activity or chemoselectivity. The n-selectivity of the product aldehydes was not determined. 

Rh/76 (Table 4 n=l, x=0, R= Me, Bu), which should be able to induce micelle formation, were used as catalysts in the biphasic hydroformylation of 1-dodecene.371 The conversion was 80%, the n/i ratio 60/40 with no carry-over of the rhodium catalyst into the organic phase.371... 

An interesting phenomenon of macromolecular isomorphism was detected in copolymers of a-butene with a-M-hexene, a-M-octene, a-n-decene, a-w-dodecene, and a- -octadecene (<5). In these copolymers isomorphous replacement occurs between the butene units and the methylene sequences of the side groups in both the known modifications I and II of poly-a-butene. 

Dimethylcarbene The usual methods for generation of carbenoids lead to poor results in the case of dimethylcarbene. The most satisfactory method involves generation in the presence of an alkene by a-elimination with n-butyllithium from 2,2-dibromopropane (which must be completely free from acetone or 2-bromoacetone), used after a detailed study of cyclopropanation of tetramethylethylene (equation I). n-Butyllithium is superior to methyl- or isopropyllithium. Addition of TMEDA or KOC(CH3)3 completely supresses cyclopropanation. Yields are improved by a lower reaction temperature. In all experiments, 35-45% of the alkene is recovered. Yields decrease with a decrease of alkyl substituents on the double bond thus the yield is only 9% in the case of l-dodecene. No cyclopropane was obtained from 2-norbomene. 

Compounds with 6 to 18 carbons are the most common alpha olefins (a-olefins) and Ziegler catalysts are used in this process. Certain olefins such as nonene (C9) and dodecene (C12) can also be made by cracking and dehydrogenation of n-paraffins, as practiced in the petrochemical section of a refinery. 

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 . 

An Arrhenius plot of log rate constant vs. reciprocal temperature (Figure 6) indicates an activation energy of 61.9 1.3 kcal/mol for dodecene cracking. This is similar to the activation energies measured for n-paraffin cracking and is somewhat higher than previously measured values for alpha-olefins (6). 

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