Ethylene, direct reaction with

If a diol is oxidatively dehydrogenated to form a diacid via an intermediate with one Off group, then a first order plot based on hydrogen evolution can exhibit some curvature. This is because the slope at any time will reflect the instantaneous concentrations of the diol and intermediate as well as their intrinsic reactivities. First order plots for the reaction of ethylene glycol, 1,4-butanediol and diethanolamine are shown in Figure 2. All plots are reasonably linear, consistent with reaction via an intermediate with a rate constant rather similar to that of the starting diol (or a direct reaction with no intermediate whatsoever). 

Porter108 has made a careful study of the photooxidation at 3650 A. at both room temperature and at 160°C. At room temperature the quantum yield of products were very small (e.g., fao = 0.03) and the product ratios were rather different from those given when 2700 A. radiation was used. It seems that, in contrast to biacetyl photooxidation, the main role of oxygen was in deactivating ketene molecules but there was some direct reaction with the electronically excited ketene molecules. At 160°C. there was a chain oxidation similar to that when 2700 A. radiation was used, but the ethylene forming step appeared to be different. 

Preparation and use in exchange ketal formation (dioxolonation). The yields are sometimes higher and the selectivity greater than in direct reaction with ethylene glycol. In the steroid series the order of reactivity is saturated 3- and 20-ketones > a/3-unsaturated 3- and 20-ketones > 2- or 4-bromo-3-ketones (no reaction) 17-ketones, 2,4-dibromo-3-ketones. ... 

In the absence of light, most polymers are stable for very long periods at ambient temperatures. However, above room temperature many polymers start to degrade in an air atmosphere even without the influence of light. For example, a number of polymers show a deterioration of mechanical properties after heating for some days at about 100 °C and even at lower temperatures (e.g., polyethylene, polypropylene, poly(oxy methylene), and poly(ethylene sulfide)). Measurements have shown that the oxidation at 140 °C of low-density polyethylene increases exponentially after an induction period of 2 h. It was concluded that thermal oxidation, like photooxidation, is caused by autoxidation, the difference merely being that the radical formation from the hydroperoxide is now activated by heat. The primary reaction can be a direct reaction with oxygen (Van Krevelen and Nijenhuis 2009) ... 

Polychloroprenes differ from other polydienes in that conventional sulphur vulcanization is not very effective. The double bonds are deactivated by the electronegative chlorine atoms and direct reaction with sulphur is limited. The vulcanization of polychloroprenes is normally achieved by heating at about 150°C with a mixture of zinc and magnesium oxides W type neoprenes also require an organic accelerator (commonly either a diamine or ethylene thiourea) but G types cure quite rapidly without acceleration. The mode of reaction has not been established with certainty, but it is generally supposed that cross-linking occurs at the tertiary allyUc chloride structures generated by 1,2-polymerization (see Section 18.8.3) and that a 1,3-allylic shift is the first step. The metal oxides may lead to ether cross-links as follows ... 

We were interested in obtaining long chain polyether derivatives of a-ZrP and the ethylene oxide method did not appear to be the correct way to attain this end. Therefore, we decided to prepare polyethylene oxide (PEO) phosphates for direct reaction with Zr(IV). These phosphates were synthesized by the following sequence of reactions ... 

When usiag HF TaF ia a flow system for alkylation of excess ethane with ethylene (ia a 9 1 molar ratio), only / -butane was obtained isobutane was not detectable even by gas chromatography (72). Only direct O -alkylation can account for these results. If the ethyl cation alkylated ethylene, the reaction would proceed through butyl cations, inevitably lea ding also to the formation of isobutane (through /-butyl cation). 

Direct Chlorination of Ethylene. Direct chlorination of ethylene is generally conducted in Hquid EDC in a bubble column reactor. Ethylene and chlorine dissolve in the Hquid phase and combine in a homogeneous catalytic reaction to form EDC. Under typical process conditions, the reaction rate is controlled by mass transfer, with absorption of ethylene as the limiting factor (77). Ferric chloride is a highly selective and efficient catalyst for this reaction, and is widely used commercially (78). Ferric chloride and sodium chloride [7647-14-5] mixtures have also been utilized for the catalyst (79), as have tetrachloroferrate compounds, eg, ammonium tetrachloroferrate [24411-12-9] NH FeCl (80). The reaction most likely proceeds through an electrophilic addition mechanism, in which the catalyst first polarizes chlorine, as shown in equation 5. The polarized chlorine molecule then acts as an electrophilic reagent to attack the double bond of ethylene, thereby faciHtating chlorine addition (eq. 6) ... 

Alternatively, thermal cracking of acetals or metal-catalyzed transvinylation can be employed. Vinyl acetate or MVE can be employed for transvinylation and several references illustrate the preparation especially of higher vinyl ethers by such laboratory techniques. Special catalysts and conditions are required for the synthesis of the phenol vinyl ethers to avoid resinous condensation products (6,7). Direct reaction of ethylene with alcohols has also been investigated (8). 

Benzyl chloride readily forms a Grignard compound by reaction with magnesium in ether with the concomitant formation of substantial coupling product, 1,2-diphenylethane [103-29-7]. Benzyl chloride is oxidized first to benzaldehyde [100-52-7] and then to benzoic acid. Nitric acid oxidizes directly to benzoic acid [65-85-0]. Reaction with ethylene oxide produces the benzyl chlorohydrin ether, CgH CH20CH2CH2Cl (18). Benzylphosphonic acid [10542-07-1] is formed from the reaction of benzyl chloride and triethyl phosphite followed by hydrolysis (19). 

Ethyl Chloride. Previously a significant use for industrial ethanol was the synthesis of ethyl chloride [75-00-3] for use as an intermediate in producing tetraethyllead, an antiknock gasoline additive. Ethanol is converted to ethyl chloride by reaction with hydrochloric acid in the presence of aluminum or zinc chlorides. However, since about 1960, routes based on the direct addition of hydrochloric acid to ethylene or ethane have become more competitive (374,375). 

The saturated 3-ketone can also be protected as the ethylene ketal, which is prepared directly by reaction with ethylene glycol or by exchange dioxo-lanation. Selective formation of 3-ethylenedioxy compounds is also possible, but the former method is not particularly effective in the presence of 6-, 17- or 20-ketones. However, the exchange dioxolanation technique is more sensitive to steric effects and good selectivity at C-3 can be achieved in the presence of a 17-ketone, provided the reagent does not contain glycol. ... 

The indirect deactivation in 2-amino-4-chloroquinoline (187) requires vigorous conditions (potassium hydroxide in hot ethylene glycol, or boiling propanolic propoxide for 16 hr) to displace the chloro group, which is stable to aqueous alkali and to hydriodic acid. The direct deactivation in 5-amino-2-chloro-3-cyano-6-methyl-pyridine (188) prevents reaction with alkoxide ion under conditions which produce smooth reaction of the des-amino analog. 

An alternative route to PET is by the direct reaction of terephthalic acid and ethylene oxide. The product bis(2-hydroxyethyl)terephthalate reacts in a second step with TPA to form a dimer and ethylene glycol, which is released under reduced pressure at approximately 300°C. 

Telescope the Process by Combining Stages. This has been done successfully in the conversion of propylene to acrylonitrile by direct ammoxidation rather than oxidation to acrolein followed by reaction with ammonia in a separate stage, as was described in the earlier patent literature. The oxychlorination of ethylene and HC1 directly to vinyl chloride monomer is another good example of the telescoping of stages to yield an economic process. 

NaH, NaNH2) or with smaller amounts of RLi, but in these cases side reactions are common and the orientation of the double bond is in the other direction (to give the more highly substituted alkene). The reaction with Na in ethylene glycol is called the BamfordStevens reaction. For these reactions two mechanisms are possible—a... 

The kinetics of ethylene hydrogenation on small Pt crystallites has been studied by a number of researchers. The reaction rate is invariant with the size of the metal nanoparticle, and a structure-sensitive reaction according to the classification proposed by Boudart [39]. Hydrogenation of ethylene is directly proportional to the exposed surface area and is utilized as an additional characterization of Cl and NE catalysts. Ethylene hydrogenation reaction rates and kinetic parameters for the Cl catalyst series are summarized in Table 3. The turnover rate is 0.7 s for all particle sizes these rates are lower in some cases than those measured on other types of supported Pt catalysts [40]. The lower activity per surface... 

In the production of dichloroethane (EDC) by oxyhydrochlorination of ethylene, the products from the reaction are quenched by direct contact with dilute HC1 in a quench tower. The gaseous stream from this quench tower is fed to a condenser and the uncondensed vapours recycled to the reactor. A typical composition for this stream is shown in the diagram below operating pressure 4 bar. Calculate the outlet stream compositions leaving the condenser. 

Reactivity of a number of solid acid catalysts that include zeolites, resin, nafion and HP As was determined for the direct reaction of ethylene with acetic acid to produce ethyl acetate (Table 1). It was established that the Keggin HSiW supported on silica is very active for the vapom phase reaction of acetic acid with ethylene at about 180°C, 145 psig with a high molar ratio of ethylene to... 

Copper olefin complexes are usually generated by the direct reaction of a Cu(l) source, the ligand, and the corresponding olefin. Copper ethylene complexes are of interest in view of their biochemical importance,98,98a-98e their applications in organic chemistry,99,99a,99b and industrial applications.100 100 Because of this, many copper alkene complexes have been reported, with different nuclearity, in compounds with one, two, or even three C=C units coordinated to a given copper center. 

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