Derived from Ethylene

Diols that bear two hydroxyl groups m a 1 2 or 1 3 relationship to each other yield cyclic acetals on reaction with either aldehydes or ketones The five membered cyclic acetals derived from ethylene glycol (12 ethanediol) are the most commonly encoun tered examples Often the position of equilibrium is made more favorable by removing the water formed m the reaction by azeotropic distillation with benzene or toluene... 

Carbon tetrachloride forms telomers with ethylene and certain other olefins (14—16). The mixture of Hquid products derived from ethylene telomerization may be represented CCl2(CH2CH2) Cl ia which nis 2l small number. Reaction of ethylene and carbon tetrachloride takes place under pressure and is induced by the presence of a peroxygen compound, eg, ben2oyl peroxide (17—19) or metal carbonyls (14,15). 

Many commercial products are derived from ethylene oxide by reacting with different reagents. The following reviews the production and the utility of these chemicals. 

As early as 1904, 1,2-Propanediol Dinitrate was proposed (Ref 3) as an additive to lower the freezing temp of NG, but its practical application on a large scale was hindered by lack of the raw material, propane-1,2-diol. It is only recently that the synthesis of glycol from ethylene led to the development of a method for producing methyl glycol from propylene via cnioro-hydrin. Even so, propylene-1,2-glycol is somewhat more expensive than glycols derived from ethylene (Ref 9)... 

LAB is derived exclusively from petroleum- or natural gas-based feedstocks. Thus, it is referred to as a petrochemical (or synthetic) surfactant intermediate. Feedstocks for LAB production are generally paraffins (carbon chain length in the range of C8-C14) derived from kerosene and benzene. Internal olefins derived from ethylene are sometimes used in place of paraffins. 

Most of the polymers are better known by their trivial names or trade names. Polymers prepared from single polymers are denoted by prefixing poly- to the name of the monomer, e.g., polyethylene, polypropylene, Polyacrylonitrile, polystyrene, etc. If the monomer has substituents or has a multi-worded name, the name of the monomer is enclosed in parenthesis after the prefix poly-, e.g., poly (methyl methacrylate), poly (vinyl alcohol), etc. Condensation polymers like that derived from ethylene glycol and terephthalic acid are named as poly (ethylene terephthalate). 

Grossmann K, Kwiatkowski J, Evidence for a causative role of cyanide, derived from ethylene biosynthesis, in the herbicidal mode of action of quinclorac in barnyard grass, Pestic Biochem Physiol 51 150-160, 1995. 

Over 100 billion lb of chemicals and polymers per year are made from ethylene, by far the most important organic chemical. Over 40% of all organic chemicals by volume are derived from ethylene. Unfortunately, we cannot describe the interesting chemistry and uses for all the important derivatives of ethylene. We will limit our detailed discussion to those chemicals made from ethylene that appear in the top 50, which amount to 8 important organic chemicals. These are listed in Table 9.1. 

Ethanol, Etbylol, Ethyl Alcohol or Alcohol (Alcool in Fr, Alkohol in Ger and Alkogol in Rus), CH.gCHaOH mw 46.07, colorless liq, sp gr 0.879 at 20°/4, fr p —114.5°, bp 78.4°, fl p of 95% ale 14°C(57°F), heat of combustion 327.6kcal/mole and heat of formation —66.4kcal/nole, miscible with w, eth, methanol 8c chlf sol in many other org solvents. It is a good solvent for many expls and its mixture with eth dissolves NC of 12%N. Alcohol can be derived from ethylene either by direct catalytic hydration or by means of ethyl sulfate as an intermediate. 

The large volume solvents, trichloroethylene and perchloroethylene, are still chiefly made from acetylene, but appreciable amounts of the former are derived from ethylene. The competitive situation between these source materials runs through the whole chlorinated hydrocarbon picture, and extends on to other compound classes as well—for example, acrylonitrile is just on the threshold of a severalfold expansion, as demand grows for synthetic fibers based thereon. Acrylonitrile can be made either from ethylene oxide and hydrogen cyanide, from acetylene and hydrogen cyanide, or from allylamines. The ethylene oxide route is reported to be the only one in current commercial use, but new facilities now under construction will involve the addition of hydrogen cyanide to acetylene (27). 

New copolymer diols derived from ethylene oxide and tetrahydrofuran yield linear polyurethanes of superior physical properties [16]. 

SAMPLE SOLUTION (a) The cyclic acetals derived from ethylene glycol contain a five-membered 1,3-dioxolane ring. 

It is also possible to use ethyl chloride, derived from ethylene and hydrogen chloride, as a starting material. Controlled chlorination of ethyl chloride produces 1,1,1-trichloroethane and 1,1,2-trichloroethane in an... 

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. 

Pentryl, or 2,4,6-trinitrophenyInitraminoethyI nitrate, is another explosive which is derived from ethylene. It is a nitric ester, an aromatic nitro compound, and a nitroamine. The substance was described in 1925 by Moran54 who prepared it by the action of mixed acid on 2,4-dinitrophenylethanolamine (large orange-yellow crystals from alcohol, m.p. 92°) procured by the interaction of dinitrochlorobenzene with ethanolamine. von Herz later prepared pentryl by the nitration of 0-hydroxyethylaniline, a material which is more commonly called phenylethanolamine and is now available commercially in this country, and was granted... 

The radicals derived from ethylene glycol and related compounds react with H202 in an alkaline medium (pH > 7.5), to give101 semidione (11) and carboxyalkyl radicals (12). 

Scheme I.—Reactions of Radicals Derived from Ethylene Glycol. [The G-values of products19 of a N,0-saturated, 0.1 Af solution of ethylene glycol at 20° and at a dose rate of 0.1 W.kg-1 are G(tetritol, 21) = 0.15, G(glycolaldehyde, 22) = 1.05, G(acetaldehyde, 24) = 1.2, G(2-deoxytetrose, 25) = 0.25, and G(succinaldehyde, 26) = 1.7],...

An MNDO calculation of six bromonium ions derived from ethylene, propene, 2-butene, isobutylene, 2-methyl-2-butene and tetramethylethylene, 49-54 shows energy minima corresponding to symmetrical bridged ions for symmetrically substituted systems 49-51 and highly asymmetric bridged ions for non-symmetrically substituted species 52-54107. 

These reactions are real tautomerization reactions, but the quite common water elimination reactions can also completely change the redox property of a radical. A case in point is the radical derived from ethylene glycol which is a reducing a-hydroxyalkyl radical which is transformed by water elimination into the fomylmethyl radical (see below) whose oxidizing property has been discussed above [reaction (20)]. Similarly, the phenol OH-adduct is a reason-... 

The complex derived from ethylene glycol, LCoraCH(OH)CH2OH, undergoes dehydration... 

In the second route an alpha olefin derived from ethylene reacts with hydrogen bromide and a free radical initiator resulting in an alkyl bromide. The alkyl bromide is reacted with dimethylamine providing the desired product [11,12] ... 

Acetic Acid. Acetic acid used to be derived from ethylene with acetaldehyde as an intermediate. The relatively high price of acetaldehyde compared to methanol and... 

Propylene Glycols. PO is converted to mono-, di-, and tri-glycols by a hydrolysis. It is similar to the hydrolysis of ethylene oxide to mono- and di-ethylene glycol. The propylene glycols are used for many of the same applications as the corresponding products derived from ethylene... 

A single crystal X-ray of the species derived from ethylene glycol, OsO(02C2H4)2, shows this to have a square-based pyramidal structure (Figure 29c).449-532... 

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