1 - ethylene bromination

N 8,2% oily liq, bn beginning nr 132° with a portion at l63-5°, d 1.78 was prepd from ethylene, bromine NaNOa soln, Before distillation the oil was washed with NaHCOa to remote any trace of HNO In the distillation the last trace exploded with the evolution of bm nitrous fumes(Refs 1 2)... 

The results are in substantial agreement with the data available from the hterature referring to the ethylene bromination in different polar solvents. 

Most of the chemical reactions as well as experimental structure determinations are performed in solutions. On the contrary, usual quantum chemical computations usually deal with isolated chemical species. This may lead to erroneous conclusions. For instance, the addition of bromine to an ethylenic hydrocarbon is known for having a different mechanism in the gas phase and in solution. In this example, the velocity constant vary by a factor of 10 when going from carbon tetrachloride to water as a solvent (Reichardt 1979), although the mechanism is the same These features are confirmed by appropriate quantum chemical computations which show that the transition state of ethylene-bromine would be dissymmetric and 55kcal/mol above the van der Waals complex in the case of the isolated species (Yamabe et al. 1988), while with a simple simulation of the solvent effect one finds a symmetric transition state lying 30.79 kcal/mol above the van der Waals complex in a non dipolar solvent and 0.02 kcal/mol in water (Assfeld 1994). 

Bromine is used in the manufacture of many important organic compounds including 1,2-dibromoethane (ethylene dibromide), added to petrol to prevent lead deposition which occurs by decomposition of the anti-knock —lead tetraethyl bromomethane (methyl bromide), a fumigating agent, and several compounds used to reduce flammability of polyester plastics and epoxide resins. Silver(I) bromide is used extensively in the photographic industry... 

Bromine. Slip slightly to one side the glass plate covering one jar of ethylene, add 2-3 ml. of bromine water (preparation, p. 525), restore the glass plate in position, and then shake the jar vigorously. The colour of the bromine rapidly disappears as 1,2-dibromoethanc is formed. Note that owing to the absorption... 

Bromine. Slip the glass cover of a jar momentarily aside, add 2-3 ml. of bromine water, replace the cover and shake the contents of the jar vigorously. Note that the bromine is absorbed only very slowly, in marked contrast to the rapid absorption by ethylene. This slow reaction with bromine water is also in marked contrast to the action of chlorine water, which unites with acetylene with explosive violence. (Therefore do not attempt this test with chlorine or chlorine water.)... 

The bromine adds on at the ethylenic linkage to form thedibromo compound (I), which easily loses hydrogen bromide to give the mono-bromo keto ester (II) ... 

It is essential to apply both tests, since some symmetrically substituted ethylenic compounds (e.g., ilbene C4H5CH=CHCjHj) react slowly under tbe conditions of the bromine test. With dilute permanganate solution the double bond is readily attacked, probably through the intermediate formation of a cis diol ... 

Much of the bromine output in the U.S. was used in the production of ethylene dibromide, a lead scavenger used in making gasoline antiknock compounds. Lead in gasoline, however, has been drastically reduced, due to environmental considerations. This will greatly affect future production of bromine. 

Furthermore, treatment of the aminopalladation product with bromine affords aziridines[176]. The aziridine 160 was obtained stereoselectively from methylamine and 1-decene in 43% yield. The aminopalladation of PdCl2 complexes of ethylene, propylene, and 1-butene with diethylamine affords the unstable ir-alkylpalladium complex 161, which is converted into the stable chelated acylpalladium complex 162 by treatment with CO[177],... 

Many of the features of the generally accepted mechanism for the addition of halogens to alkenes can be introduced by referring to the reaction of ethylene with bromine... 

Neither bromine nor ethylene is a polar molecule but both are polarizable and an induced dipole/mduced dipole force causes them to be mutually attracted to each other This induced dipole/mduced dipole attraction sets the stage for Br2 to act as an electrophile Electrons flow from the tt system of ethylene to Br2 causing the weak bromine-bromine bond to break By analogy to the customary mechanisms for electrophilic addition we might represent this as the formation of a carbocation m a bimolecular elementary step... 

Step 1 Reaction of ethylene and bromine to form a bromonium ion intermediate... 

FIGURE 6 12 Mechanism of electrophilic addition of bromine to ethylene... 

Ozone ALkenes, aromatic compounds, bromine, diethyl ether, ethylene, HBr, HI, nitric oxide, nitrogen dioxide, rubber, stibine... 

Bromoacetic acid can be prepared by the bromination of acetic acid in the presence of acetic anhydride and a trace of pyridine (55), by the HeU-VoUiard-Zelinsky bromination cataly2ed by phosphoms, and by direct bromination of acetic acid at high temperatures or with hydrogen chloride as catalyst. Other methods of preparation include treatment of chloroacetic acid with hydrobromic acid at elevated temperatures (56), oxidation of ethylene bromide with Aiming nitric acid, hydrolysis of dibromovinyl ether, and air oxidation of bromoacetylene in ethanol. 

Chlorination or bromination of methane, ethylene, etc Maleic anhydride (from butane)... 

Flame-Retardant Resins. Flame-retardant resins are formulated to conform to fire safety specifications developed for constmction as well as marine and electrical appHcations. Resins produced from halogenated intermediates (Table 5) are usually processed at lower temperatures (180°C) to prevent excessive discoloration. Dibromoneopentyl glycol [3296-90-0] (DBNPG) also requires glass-lined equipment due to its corrosive nature. Tetrabromophthahc anhydride (TBPA) and chlorendic anhydride (8) are formulated with ethylene glycols to maximize fiame-retardant properties reaction cycle times are about 12 h. Resins are also produced commercially by the in situ bromination of polyester resins derived from tetrahydrophthahc anhydride... 

In the manufacture of ethylene dibromide, gaseous ethylene is brought into contact with bromine by various methods, allowing for dissipation of the heat of reaction (100—102). Eree acids are neutralized and the product maybe fractionally distilled for purification. Typical specifications call for a clear Hquid with 99.5% purity min sp gr (25/25°C), 2.170—2.180 boiling range, 130.4—132.4°C APHA color, 200 max water, 200 ppm max acidity as HCl, 0.0004 wt % max and nonvolatile matter, 0.0050 wt % max. 

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