Ethyl chloride synthesis

Direct Process. The preparation of organosilanes by the direct process, first reported in 1945, is the primary method used commercially (142,143). Organosilanes in the United States, France, Germany, Japan, and the CIS are prepared by this method, including CH SiHCl, (CH2)2SiHCl, and C2H SiHCl2. Those materials are utilized as polymers and reactive intermediates. The synthesis involves the reaction of alkyl haUdes, eg, methyl and ethyl chloride, with siUcon metal or siUcon alloys in a fluidized bed at 250—450°C ... 

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). 

Major uses of ethyl chloride are the manufacture of tetraethyl lead and the synthesis of insecticides. It is also used as an alkylating agent and as a solvent for fats and wax. 

Despite several attractive features in this method of direct halogen introduction and the obvious applications in the synthesis of deoxy sugars, its uses have not been further exploited by other groups of workers. Some new related methods have become available which reportedly eliminate the difficulties previously encountered such as rearrangement, unreactivity due to steric hindrance, and phosphonate ester formation. The reaction is based on the observation (28) that triethylphosphine reacts with ethanol and carbon tetrachloride to give ethyl chloride, chloroform, and triethylphosphite. In a new adaptation (76, 77) of this... 

The synthesis of ethyl chloride from ethylene and hydrogen chloride in the presence of methane (inert) was studied in a differential reactor by Thodos Stutzman (Ind Eng Chem 50 413, 1958) over zirconium oxychloride... 

Other important raw material uses of ethyl alcohol are conversion to esters and ethers, vinegar, ethyl chloride, butadiene, styrene, and chloral (for DDT). Nearly all the new developments in chemicals from ethyl alcohol, particularly the four-, six-, and eight-carbon derivatives are based on alcohol derived from petroleum. The butyl alcohol and butyl acetate so made supplement the production by fermentation and from oxidation of hydrocarbons and synthesis gas operations. The consumption of ethyl alcohol for all industrial uses (denatured alcohol) exceeded 1.2 billion pounds (100% basis) in 1950. More than 700,000,000 pounds of this were made from petroleum. 

The so-called integrated ethyl chloride process combines the abovementioned synthesis with an addition reaction. Hydrogen chloride formed in the thermal chlorination process is used in a separate step to add to ethylene, making the manufacture of ethyl chloride more economical. 1,1,1-Trichloroethane is an exceptional product in free-radical chlorination of higher hydrocarbons since the same carbon... 

The results of the study of the effect of synthesis conditions on the composition of poly(4-methyl-l-pentene) have shown that even under conditions most favorable for the successful competition of isomerization with propagation, i.e., —120° C, using EtAlCl2, in ethyl chloride, the polymer contains only 50% of the desired 1,4-structure. It appears that in the series (n— l)-methyl-l-alkenes as n increases the likelihood of obtaining completely isomerized products via cationic isomerization polymerization is decreased. This is supported qualitatively by results obtained in the cationic polymerization of 4-methyl-l-hexene, an (n—2)-methyl-1-alkene (17). 

The process of ethylchlorosilane preparation by copper-catalysed ethyl-chloride reaction with silicon is very complex, and the mechanism of this process has not been fully established. However, similarly to the synthesis of methylchlorosilanes, the direct synthesis of ethylchlorosilanes most... 

As was mentioned in Section 1, the first synthesis of an organolead compound was reported by Lowig 210>211), who synthesized tetraethyllead by the reaction of a sodium-lead alloy with ethyl iodide. Some 35 years later, Polis 247,248) prepared the first aryl lead derivative by the reaction of bromobenzene with a sodium-lead alloy. Since 1923, the sodium-lead alloy-ethyl chloride reaction has been used for the commercial production of tetraethyllead. A similar reaction has also been used for the commercial production of tetramethyllead since 1960. The sodium-lead alloy-alkyl chloride reaction is discussed in Section 6. 

Fittig and Tollens [27] obtained ethylbenzene by synthesis from chlorobenzene and ethyl chloride. At first they believed it was xylene (basing their view on its boiling point). However, the substance did not yield a crystalline product when nitrated, as in the case of xylene, but an oily one, from which they inferred that the ethylphenyl they had obtained was not xylene. 

TTie synthesis of ethyl chloride is accomplished by reacting ethylene with hydrogen chloride in the presence of an aluminum chloride catalyst ... 

Primary and secondary amides and thioamides react with alkyl chlorofoimates with loss of CO2 or COS, forming iminium chlorides (82 equation 52). In some cases this method is complementary to the Pinner imido ester hydrochloride synthesis. The iminium salt (83 Scheme 6) formed by action of ethyl chloroformate on DMF is labile and decomposes rapidly to ethyl chloride. If the reaction is performed in the presence of NaBp4, the iminium salt (85) is isolable. Aryl chlorofoimates react in the same fashion with DMF or DMA, but in these cases the aryloxymethyleneiminium compounds are fairly stable, so this reaction is an important method for the preparation of compounds of this type. - Succinic acid monoamides, phthalic acid monoamides and related compounds are cyclized to iminium salts (86 equation 53) by treatment with acetic anhydride and HC104. ° With the aid of trifluoromethanesulfonic anhydride lactams and amides can be converted to dication ether salts (87) and (88 Scheme 7).22i.222... 

Pepdde synthesis. The reagent (1) reacted readily with N-phthaloyl-t-phenyl-alanyl chloride (2) at room temperature with evolution of ethyl chloride and formation... 

Preparation of phosphonates for modeled Wittig reaction. In a typical synthesis benzyl chloride is added to triethyl phosphite to form benzyltriethylphosphonium chloride, which on brief refluxing loses ethyl chloride to form diethyl benzylphos-... 

In a related reaction, ethyl cyanoacetate is the source of the cyano(ethoxycarbonyl)methylene unit which is transferred to alkenes by a radical mechanism, e.g. synthesis of 3. This transformation is mediated by copper(II) chloride or acetate, accompanied by lithium chloride. Synthesis of diethyl cyclopropane-1,1-dicarboxylates from diethyl malonate and alkenes is much less efficient. ... 

Hydrogen chloride may be used as a chlorinating agent. It is sometimes employed in such a manner that it adds to the double bond as in the preparation of ethyl chloride from ethylene 75 or in the synthesis of vinyl chloride from acetylene 16. Kainer 48 has surveyed the patents dealing with the preparation of vinyl chloride. A review 21 of the patent literature and the apphcation of the Deacon reaction, which uses hydrogen chloride and air, has also been published. Some of the material on this reaction has been mentioned before 26, 82, 61. ... 

The synthesis of acetaldehyde, essentially intended for conversion to acetic acid, was the main outlet for ethanol until a few years ago. The industrial development of methanol carbonylation to acetic arid has relegated this application to the background. Ethanol is chiefly used today as a solvent and for the preparation of esters (ethyl acetate, ethyl chloride). It is also employed in cosmetics and pharmaceuticals. 

Diethylamine finds extensive use in the preparation of wetting and, dispersing agents and enters into many syntheses. Through its employment, the alkyl groups are introduced into procaine. Its preparation from ethanol and ammonia by ammonolysis is described in Chap. 8. Schwyzer also describes the synthesis from ethyl chloride and ammonia ... 

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