Chlorides reaction with ethylene

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). 

This reaction can proceed by 1,1-proton abstraction to form a carbene radical anion, but can also occur by l,n-abstraction to form the negative ion of a diradical. Thus, reaction of O with methylene chloride results in the formation of CCI2 (Eq. S.Sa), reaction with ethylene gives vinylidene radical anion, H2CC (Eq. 5.8b), and the reaction with acetonitrile gives the radical anion of cyanomethylene, HCCN (Eq. 5.8c) Investigations of these ions have been used to determine the thermochemical properties of dichlorocarbene, CCI2, vinylidene, and cyanomethylene. ... 

Functionalization of these reactive anionic chain ends can be achieved by a variety of methods all based on the general concepts of carbanion chemistry. For example, reaction with C02 or succinnic anhydride leads to the carboxy terminated derivatives [10], while hydroxy-terminated polymers can be easily obtained by reaction with ethylene oxide (Scheme 3) [11]. In select functionalization reactions, such as alkylation with p-vinyl benzyl chloride, the nucleophilicity of the carbanionic species may be necessary and this can be achieved by reaction of the chain end with 1,1-diphenylethene followed by functionalization [12,13]. 

Crosslinked resins of polyethylene imine structure have been prepared by various methods, including the reactions of polyethylene imine with epichlorohydrine 14), with allyl chloride 15), with ethylene dibromide, 6) or dichloride 17), and with toluene diisocyanate l8>. 

It may be concluded that primary alkyl chlorides undergo peroxide-induced, hydrogen chloride-promoted, alkylation with ethylene to yield products formed by alkylation at a tertiary carbon atom, at a penultimate secondary carbon atom, or at a primary carbon atom holding a chlorine atom. In the absence of hydrochloric acid, n-butyl chloride underwent little peroxide-induced reaction with ethylene presumably because hydrogen chloride is necessary for propagating the reaction chain via abstraction of hydrogen from the hydrogen chloride to produce the ethylated product and a chlorine atom which maintains the chain by abstraction from the alkyl chloride. 

Cleavage of lactones and carbonates. Lactones and carbonates react with bromotrimethylsilane to afford bromocarboxylic acid derivatives (equation I) and bromohydrin trimethylsilyl ethers (equation II), respectively acyclic, aliphatic esters do not react with bromotrimethylsilane. lodotrimethylsilane reacts in an analogous fashion with lactones, but in reaction with ethylene carbonate the main product is 1,2-diiodoethane (equation III). The >-bromocarboxylate derivatives are converted into acid chlorides by reaction with SOCL (equation I). 

Incandescent reaction with ethylene + heat, nitrogen + metal chlorides (e.g., chromium trichloride, zirconium tetrachloride, nitryl fluoride (at 200°C)). Incompatible with atmospheric gases,... 

During this first step PdCl2 reacts in a stoichiometric reaction with ethylene, water, and carbon monoxide forming acrylic acid, hydrogen chloride and Pd°. 

The macromonomers were prepared by anionic polymerization of 2-vinylpyridine followed by reaction with ethylene oxide and methacrylic acid chloride [111] as shown in Scheme 1. MALDI-TOF mass spectroscopy was utilized in order to determine the absolute molar mass and the degree of end-functionalization as given in Table 4. The sample code MM-PVPXY comprises the polymerizable unit (MM=methacrylate), the side chain (PVP=polyvinylpyridine) and the side chain degree of polymerization XY. 

Engel and Rakhit found that selective ketalization of the 12-keto group of the 12,20-diketone (1) by reaction with ethylene glycol and boron trifluoride etherate proceeds best with methylene chloride present as co-solvent to provide a homogeneous medium. Without the cosolvent, the yield was 57%. 

The process is fed with three streams ethane, ethylene, and chlorine. The ethane and ethylene streams have the same molar flow rate, and the ratio of chlorine to ethane plus ethylene is 1.5. The ethane/ethylene stream also contains 1.5 percent acetylene and carbon dioxide. (For this problem, just use 1.5 percent carbon dioxide.) The feed streams are mixed with an ethylene recycle stream and go to the first reactor (chlorination reactor) where the ethane reacts with chlorine with a 95 percent conversion per pass. The product stream is cooled and ethyl chloride is condensed and separated. Assume that all the ethane and ethyl chloride go out in the condensate stream. The gases go to another reactor (hydrochlorination reactor) where the reaction with ethylene takes place with a 50 percent conversion per pass. The product stream is cooled to condense the ethyl chloride, and the gases (predominately ethylene and chlorine) are recycled. A purge or bleed stream takes off a fraction of the recycle stream (use 1 percent). Complete the mass balance for this process. 

A modification of this reaction provides a useful route to jS-tetralones. Burck-halter and Campbell4 found that phenylacetyl chlorides condense with ethylene under the influence of aluminum chloride (CS2, ice cooling) to give /3-tetralones in good yield. The intermediate /Tchloroethyl ketones are cyclized under the reaction conditions. In the original procedure 6-methoxy-2-tetralone was obtained... 

Polytetramethylene glycol of molecular weight 2000 was freeze-dried from benzene in a vacuum. The bromoethylated prepolymer was obtained by reaction of the glycol, first with adipoyl chloride, then with ethylene bromohydrin (Table II) and precipitation in water and n-hexane. Nitromethane solution of the poly-THF dioxolenium salt was prepared after filtration of silver bromide from the reaction product of bromoethylated poly-THF with silver perchlorate in nitromethane. 

Reaction of PTG and adipoyl chloride was carried out for 12 hours at room temperature further reaction with ethylene bromohydrin was for 12 hours. 

In fact, one important parameter is the water content of the medium, which causes the undesirable production of acetaldehyde by its reaction with ethylene in the presence of palladium chloride, or by the hydrolysis of the vinyl acetate formed. This operating variable can be adjusted to make the acetate production plant self-sufficient in terms of acetic acid. In this case, die acetaldehyde co-produced is oxidized to the arid in a separate section. It is the water content of the acetic arid employed, controlled by the degree of purification of the by-product arid which is recycled, which ultimately serves to determine the vinyl acetate to acetaldehyde ratio. Longer reridence time in the reactor or higher temperature also favors the formation of acetaldehyde. 

SILICON FLUORIDE (7783-61-1) Noncombustible gas. Reacts in moist air, producing a white cloud and hydrogen chloride. Decomposes in water, forming silicic acid and hydrogen chloride. Potentially violent reaction with ethylene oxide (causes explosive polymerization), fluorine, silicon tetrahydride. Reacts with acids, alkalis, alcohols, alkali metal. Attacks glass and siliceous materials. 

Russel [142] developed a method based on the conversion of chlorine, bromine and iodine ions into the corresponding halogenated ethanols by reaction with ethylene oxide. Belcher et al. [143] offer a method for determining trace amounts of chloride ions, based on reaction with mercury phenylnitrate to give phenylmercury chloride, which is chromatographed with flame-ionization detection. 

The thus established stereocenter served in the following steps. Conversion of 50 to 51 was achieved by acyl chloride formation followed by Friedel-Crafts reaction with ethylene and A1C13. Addition of the lithium enolate of t-butylacetate occurred from the less-hindered face of the cyclic ketone to give, after reduction and tosylation, adduct 52. Tosylate displacement with amine 53, esterification with methoxyacetylchloride, and addition of HC1 gave mibefradil 54. 

---