1-Decene synthesis

C30 oil, homopolymer of 1-decene, Ethyl Corp., Inc.) served as the start-up solvent for the experiments. The catalyst (ca. 5-8 g) was added to start-up solvent (ca. 300 g) in the CSTR. The reactor temperature was then raised to 270°C at a rate of l°C/min. The catalyst was activated using CO at a space velocity of 3.0 sl/h/g Fe at 270°C and 175 psig for 24 h. FTS was then started by adding synthesis gas mixture (H2 CO ratio of 0.7) to the reactor at a space velocity of either 3.1 or 5.0 sl/h/g Fe. The conversions of CO and H2 were obtained by gas chromatography (GC) analysis (HP Quad Series Micro-GC equipped with thermal conductivity detectors) of the product gas mixture. The reaction products were collected in three traps maintained at different temperatures—a hot trap (200°C), a warm trap (100°C), and a cold trap (0°C). The products were separated into different fractions (rewax, wax, oil, and aqueous) for quantification by GC analysis. However, the oil and the wax (liquid at room temperature) fractions were mixed prior to GC analysis. 

FIGURE 9.24 Molar radioactivity of the reaction products when co-feeding n-hexa-decene-(l)-(l-14C) together with the synthesis gas to FT synthesis on cobalt. Catalyst 100Co-18Th02-100Kieselguhr (by weight), precipitated, 190°C, 1 bar, H2/CO = 2, Xc0 = 70%, 0.1 vol% of hexadecene-14C in the synthesis gas. 

Polymers Catalytic reactions involving C=C bonds are widely used for the conversion of unsaturated fatty compounds to prepare useful monomers for polymer synthesis. Catalytic C-C coupling reactions of unsaturated fatty compounds have been reviewed by Biermann and Metzger [51]. Metathesis reactions involving unsaturated fatty compounds to prepare co-unsaturated fatty acid esters have been applied by Warwel et al. [52], Ethenolysis of methyl oleate catalyzed by ruthenium carbenes developed by Grubb yields 1-decene and methyl 9-decenoate (Scheme 3.6), which can be very useful to prepare monomers for polyolefins, polyesters, polyethers and polyamide such as Nylon 11. 

EFFICIENT SYNTHESIS OF BROMIDES FROM CARBOXYLIC ACIDS CONTAINING A SENSITIVE FUNCTIONAL GROUP DEC-9-ENYL BROMIDE FROM 10-UNDECENOIC ACID (1-Decene, 10-bromo-)... 

The key step in Fiirstner s elegant synthesis of racemic 153 furnishing a Z E=7 3 mixture, used an intramolecular metathesis reaction of the ester A [292]. Employing optically active 9-decene-2-ol will certainly produce the desired enantiomer (Fig. 7). 

The 3/Rh catalyst formed in situ (P/Rh = 4 1, substrate/Rh = 1000 1) has been applied to the aqueous-organic biphasic hydroformylation of 1-decene. The conversion of olefin and yield of aldehyde were 99.5 and 99.0%, respectively, after 5 h at 120 °C and 5.0 MPa of synthesis gas. Recycling tests showed that the aldehyde yield was still higher than 94.0% even after the catalyst had been recycled 20 times. 

It was also reported by PruP et al. [31] that in situ formed cobalt(III) complexes of pyridine-4-ylmethyl-propyl-amine (PYPA) on preformed organomodified HMS are active as catalysts in the aerobic oxidation of styrene and also 1-decene (Figure 3). Incorporation of PYPA may be achieved by following several routes viz. sol-gel synthesis, post modification of sol-gel AMP-HMS, and grafting. The authors proposed that all materials are able to act as... 

Simple synthesis of E)-A -oxo-2-decenal and homologues, which are common components of the defensive secretions of true bugs (Hemiptera)... 

The second synthesis is based on the conversion of undecanal into 2-methyleneundecanal by reaction with formaldehyde in the presence of catalytic amounts of amines [15]. Hydrogenation of 2-methyleneundecanal yields methylnonylacetaldehyde. A convenient process starts from 1-decene hydroformylation gives a mixture consisting mainly of undecanal and 2-methyldecanal. Reaction of the crude product with formaldehyde in the presence of dibutylamine yields a mixture containing over 50% 2-methyleneundecanal. After hydrogenation of the double bond, pure 2-methylundecanal is separated from by-products by fractional distillation [16]. 

Lin, J.M., Fay, L.B., Welti, D.H., and Blank, 1.1999. Synthesis of trans-4,5-epoxy-(E)-2-decenal and its deuterated analog used for the development of a sensitive and selective quantification method based on isotope dilution assay with negative chemical ionization. Lipids 34 1117-1126. 

Majetich reports a general intramolecular Lewis acid allylation protocol for the synthesis of bicy-clo[5.4.0]undecen-3-ones (168) and bicyclo[4.4.0]decen-3-ones (170), which are 1,6-addition products (Scheme 27). The same precursors, (167) and (169), when submitted to the fluoride ion cyclization protocol, also afford 1,2- and 1,4-addition products.73 Typically, ethylaluminum dichloride, a proton sponge Lewis acid, is used in order to minimize adventitious protonic desilylation. Other 0,y-unsatu-rated silanes also undergo similar intramolecular Lewis acid catalyzed additions for example, the si-lylpropargylic enones (171) undergo intramolecular cyclization to the allenylspiro system (172).74... 

The synthesis of several hydrogensulphate and tetrakis(hydrogensulphato)borate ionic liquids has been described by our group [29]. Mixtures of these ionic liquids with sulphuric acid were used as non-volatile acidic phases with tuneable solubility properties for catalytic applications such as e.g. the alkylation of benzene with 1-decene. 

In the synthesis of an epoxide from an alkene with TBHP/Mo, the stereochemistry of the alkene is retained in the epoxide. It has been suggested that the reaction proceeds through the transition state (124). ° 1-Decene and the alkene (115) (see equation 42) have been epoxidized with TBHP/Mo (equations 45 and 46). The epoxidation of (115) is regio- as well as stereo-selective the reagent approaches the electron-rich double bond from the less hindered face. 

Terminal double bonds are selectively oxidized to methyl ketones. A typical procedure for the oxidation of 1-decene to 2-decanone in 65-73% yield with PdCWCuCl is given in Organic Synthesis Although there are several known synthetic methods for methyl ketone preparation, the PdCh-catalyzed oxidation of terminal alkenes seems to be one of the best. In other words, terminal alkenes can be regarded as precursors of methyl ketones, or as masked methyl ketones based on this reaction. This re-... 

The ability of a methanesulphonate substituent to function as a leaving group (compare equation 124, Section VI.E.2) in an intermediate cyclopropane permits transformation of a bicyclo[4.4,0]decene derivative into a compound with a hexahydroazulene skeleton having potential for sesquiterpene synthesis(equation 76). 

The resulting spiro[4.5]decen-2-one (203) is not only a constituent of Vetiver oil of economical importance but also constitutes the key intermediate for the synthesis of other spirovetivane-sesquiterpenes ... 

The Merck Frosst group has prepared LTB (107) by a novel route where the key synthon, methyl (6 ,8Z)-10-bromo-6-r-butyldimethylsilyloxydecadieneoate (125), previously used in the synthesis of 5-HETE, was converted to the phosphonium salt 126 and reacted with the LTB4 synthon (27 )-r-butyldimethyl-silyloxy-(4 )-decen-l-al (127) to provide a 3 1 mixture of the (10 )- and (10 -adducts 128 and 129. The unusual preponderance of the rrons-isomer was attributed to steric hindrance in the normal kinetically favored erythro betaine caused by the bulky a-siloxy function (Scheme 5.36). 

For the synthesis of flavocristamide A (160), ( >iodoalkene (I) was necessary. This was prepared from 9-decen-l-ol (F). Chain elongation of F yielded G, whose double bond was converted to a triple bond to give H. Subsequent hydroalumination of H was followed by quenching with iodine to give the desired iodoalkene I. 

Another example is the synthesis of the enantiopuxe a-tocopherol side chain [43]. Thus,the C15 allylamine, ( )(71 )-l-dimethylamino-3,7,ll-trimethyl-2-do-decene 60, was isomerized to the corresponding Cl 5 (l ,l )-enamine 61 with very high selectivities of 98% ee and 96% de (Scheme 11). 

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