Olefins s. Ethylene derivatives

C-2,7-Octadien-l-ylation 26, 827 Olefins s. Ethylene derivs. a-Olefins s. Ethylene derivs., terminal Oligomerization... 

Olefins s. Ethylene derivatives a-Olefins s. Ethylene derivatives, terminal Oligonucleotides, removal of 0-prolective groups 21, 25 —, solid-phase synthesis 19, 33 suppl. 21 Orgaiiometallic compounds (s. a. under individual metals. Metal complex compounds)... 

Olefins s. Ethylene derivatives Oleic acid as reagent 16, 867 Oligopeptides... 

Olefins s. Ethylene derivatives a-Olefins s. Ethylene derivatives, terminal Oligomerization s. Cyclooligomerization, Di-merization, Tri-... 

Description The most predominant feed used to produce ethylene today is naphtha, as more than half of the world s ethylene is currently derived from cracking naphtha feed. The Advanced Catalytic Olefins (ACO) process is an alternative process that catalytically converts naphtha feed and is thus able to produce higher ultimate yields of light olefins (propylene plus ethylene) and at a higher P/E production ratio relative to steam cracking, typically about 1 1. 

A soln. of the startg. m. and 4 equivalents ketal heated ca. 8 hrs. at 100° in toluene containing 2,4-dinitrophenol as catalyst, and the intermediate ketone treated at 0° with NaBH4 in methanol > product. Y up to 81% purity 98%. -This olefinic ketal Claisen reaction is useful for preparing trans-disubst as well as trans-trisubst. olefinic bonds. The above producure is the last of a succession of 3 similar steps. F. e. and catalysts s. W. S. Johnson et al., Am. Soc. 92, 4463 (1970) Proc. Natl. Acad. Sci. U.S. 67, 1462, 1465, 1810, 1824 (1970) geospecific synthesis of ethylene derivs., review, s. J. Reucroft and P. G. Sammes, Quart. Rev. 25,135 (1971). 

A mixture of 3,6-diphenyl-si/m-tetrazine, diphenylacetylene, and toluene refluxed 3 days 3,4,5,6-tetraphenylpyridazine. Y 86%.—A variety of unsatd. compounds, inch aliphatic and alicyclic olefins, styrenes, acetylenes, butadienes, and allene give the above reaction. 3,6-Bis(polyfluoroalkyl)-sym-tetrazines react with particular ease. F. e., also from ethylene derivatives via 1,4-dihydropyridazines, s. R. A. Garboni and R. V. Lindsey, Jr., Am. Soc. 81, 4342 (1959). 

The poly(alkylene oxide)s are linear or branched-chain polymers that contain ether linkages in their main polymer chain structure and are derived from monomers that are vicinal cyclic oxides, or epoxides, of aliphatic olefins, principally ethylene and propylene and, to a much lesser extent, butylene. These polyethers are commercially produced over a range of molecular weights from a few hundred to several million for use as functional materials and as intermediates. Lower polymers are liquids, increasing in viscosity with molecular weight. The high polymers can be thermoplastic. Solubilities range from hydrophilic water-soluble polymers that are principally derived from ethylene oxide, to hydrophobic, oil-soluble polymers of propylene oxide and butylene oxide. A wide variety of copolymers is produced, both random copolymers and block copolymers. The latter may be used for their surface-active characteristics. 

It is convenient to divide the petrochemical industry into two general sectors (/) olefins and (2) aromatics and their respective derivatives. Olefins ate straight- or branched-chain unsaturated hydrocarbons, the most important being ethylene (qv), [74-85-1] propjiene (qv) [115-07-17, and butadiene (qv) [106-99-0J. Aromatics are cycHc unsaturated hydrocarbons, the most important being benzene (qv) [71-43-2] toluene (qv) [108-88-3] p- s.y en.e [106-42-3] and (9-xylene [95-47-5] (see Xylenes and ethylbenzene) There are two other large-volume petrochemicals that do not fall easily into either of these two categories ammonia (qv) [7664-41-7] and methanol (qv) [67-56-1]. These two products ate derived primarily from methane [74-82-8] (natural gas) (see Hydrocarbons, c -c ). 

Methanol dehydrogenation to ethylene and propylene. In some remote ioca-tions, transportation costs become very important. Moving ethane is almost out of the question. Hauling propane for feed or ethylene itself in pressurized or supercooled vessels is expensive. Moving naphtha or gas oil as feed requires that an expensive olefins plant with unwanted by-products be built. So what s a company to do if they need an olefins-based industry at a remote site One solution that has been commercialized is the dehydrogenation of methanol to ethylene and propylene. While it may seem like paddling upstream, the transportation costs to get the feeds to the remote sites plus the capital costs of the plant make the economics of ethylene and its derivatives okay. 

The chemical uses for ethylene prior to World War II were limited, for the most part, to ethylene glycol and ethyl alcohol. After the war, the demand for styrene and polyethylene took off, stimulating ethylene production and olefin plant construction. Todays list of chemical applications for ethylene reads like the WTiat s What of petrochemicals polyethylene, ethylbenzene (a precursor to styrene), ethylene dichloride, vinyl chloride, ethylene oxide, ethylene glycol, ethyl alcohol, vinyl acetate, alpha olefins, and linear alcohols are some of the more commercial derivatives of ethylene. The consumer products derived from these chemicals are found everywhere, from soap to construction materials to plastic products to synthetic motor oils. 

The olefins—ethylene, propylene, and the butylenes—are derived from natural gas and petroleum. Methane is the major constituent in natural gas. The aromatics— benzene, toluene, and the xylenes— are derived from petroleum. About 90% by weight of the organic chemicals in the world comes from natural gas and petroleum. But actually only 3% of this crude oil and 6% of refinery output in the U.S. is processed into chemicals, with the rest going as various fuels. Although we are a small user of the petroleum industry, this 3-6% going to petrochemical feedstock is important to us ... 

Styrene, one of the world s major organic chemicals, is derived from ethylene via ethylbenzene. Several recent developments have occurred with respect to this use for ethylene. One is the production of styrene as a co-product of the propylene oxide process developed by Halcon International (12). In this process, benzene is alkylated with ethylene to ethylbenzene, and the latter is oxidized to ethylbenzene hydroperoxide. This hydroperoxide, in the presence of suitable catalysts, can convert a broad range of olefins to their corresponding oxirane compounds, of which propylene oxide presently has the greatest industrial importance. The ethylbenzene hydroperoxide is converted simultaneously to methylphenyl-carbinol which, upon dehydration, yields styrene. Commercial application of this new development in the use of ethylene will be demonstrated in a plant in Spain in the near future. 

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