Ethyl chloride, hydrolysis

Ethyl chloride can be dehydrochlorinated to ethylene using alcohoHc potash. Condensation of alcohol with ethyl chloride in this reaction also produces some diethyl ether. Heating to 625°C and subsequent contact with calcium oxide and water at 400—450°C gives ethyl alcohol as the chief product of decomposition. Ethyl chloride yields butane, ethylene, water, and a soHd of unknown composition when heated with metallic magnesium for about six hours in a sealed tube. Ethyl chloride forms regular crystals of a hydrate with water at 0°C (5). Dry ethyl chloride can be used in contact with most common metals in the absence of air up to 200°C. Its oxidation and hydrolysis are slow at ordinary temperatures. Ethyl chloride yields ethyl alcohol, acetaldehyde, and some ethylene in the presence of steam with various catalysts, eg, titanium dioxide and barium chloride. 

It is essential that there be suffieient alkali present, either combined with the cellulose, or free, to neutralise the acid formed by both the main reaction and in a side reaction which involves the hydrolysis of ethyl chloride. 

A product which contains about 2.5 ethoxy groups (47—48%) is thermoplastic and is suitable for commercial and military uses its sp gr is 1.07—1.18, nD 1.47 and softening point 240—45°. It can be prepd in a laboratory, by slowly adding (with stirring) to the pulped filter paper (suspended in 44% aq NaOH so In maintained at 100°) an excess of ethyl chloride (usually 6 moles per one mole of cellulose) and allowing to stand for a while Note In order to obviate to some extent the side reactions of hydrolysis, the procedure is conducted in the presence of large amount of NaCl... 

The gaseous products formed on thermal decomposition of ethylene-platinous chloride are ethylene, hydrogen chloride, vinyl chloride, ethyl chloride, ethylene dichloride and ethylidine dichloride. The half life for the decomposition at 130° is 4.5 days, at 172° it is 1.7 hours 98). The hydrolysis of Zeisc s salt K[PtCl3(C2H4)] by water and dilute acids has been studied ... 

Thiophosphoryl chloride dissolves sulphur and phosphorus freely when hot, but only sparingly when cold.2 Since the liquid is immiscible with water the hydrolysis proceeds only on the surface at first, as is usual with phosphorus halides. In this case the products are phosphoric acid, hydrogen chloride and sulphide and a little sulphur. It reacts with ethyl alcohol, giving ethyl chloride and ethyl thiophosphate ... 

Hydrolysis L, = 40.0 d was estimated at pH 7 from ethyl chloride data in water at an unspecified temperature (Brown et al. 1975 quoted, Howard 1989) ... 

The reactions represented are the combination of hydrogen and chlorine, the decomposition of mercury cyanide, the hydrolysis of acetyl chloride, and the reaction of ethyl chloride with anamonia to form ethylamine and hydrogen chloride. The reagents are shown left and right the products are separated by the horizontal line and by a vertical line where necessary.—O.T.B.]... 

In support of the theory that the intermediate formation of alkyl esters occurs when dilute adds are used is the fact that olefins readily form addition compounds, because of thdr unsaturated nature, with certain substances and the claims that have been made for the hydrolysis of ethyl esters to ethanol. Almost 100 per cent yields of ethanol are daimed for the interaction of a mixture composed of 1 part of ethyl chloride and 10 parts of water by weight at 250° C. in the presence of catalysts composed of zinc, copper or cadmium sulfate or zinc chloride supported on active charcoal.58 In such processes as this, high yields can only be obtained by redrculation of the unconverted alkyl halide, or by the use of abnormally long times of contact at the low temperature, with removal of hydrochloric add. 

At ordinary temperatures the oxidation and hydrolysis of ethyl chloride take place slowly. In (he absence of air and water, it can be used with most common metals up to 200°C (392 F). Ethyl chloride burns with a green-edged flame, producing hydrogen chloride, carbon dioxide and water. It is thermally stable to 400 C (752 F) thermal flitting yields ethylene and hydrogen chloride. The reactivity of ethyl chloride as an intermediate is often based on the affinity of alkali metal atoms for its chlorine atom. 

In the reaction of M0CI5 with ethanol it was shown that the presence of the 0x0 ligands in the product [Cl2(0)Mo( i-OEt)2(At-HOEt)Mo(0)Cl2] was due to elimination of ethyl chloride. However, hydrolysis by water produced by reaction of ethanol with HCl cannot be ruled out (Eq. 5.8). 

A comparable sequence starting from 2,5-dimethylthiophene (Scheme 32) [52] utilised ethyl glutaryl chloride, hydrolysis of the first product giving 5-(2,5-dimethylthien-3-yl)valeric acid which in turn was converted into cyclohepta [c]thiophene 30 by cyclisation using polyphosphoric acid. The bicyclic ketone was used to make a series of l//-pyrazolo[3,4-c]cyclophepta[l,2-c]thiophenes, being a unique structural class of dopamine D4-selective ligands (Scheme 32) [52]. 

The influence of reaction time at 110° on ethyl chloride consumption, D.S. and ethylation efficiency is depicted in figure 2. The composition of the organic by-product mixture was monitored by gas chromatography the accuracy of this technique was not high but general trends could be ascertained. The ratio of ethyl ether to ethanol was approximately 10 1 indicating that hydrolysis of ethyl chloride was slow relative to the rate of ether formation. Therefore, two equivalents of base were consumed per mole of byproduct formed. Titration of residual sodium hydroxide provided a technique for evaluating efficiency, which is defined as follows ... 

In our system, the acid chloride as the acylating agent was not applicable due to the basic conditions of the proposed transformation and the internal free nitrogen of the piperidyl moiety. However, the trioxifene acylation was adapted by preparing the phenyl ester of 5. Therefore, the required phenyl 4-[2-(l-piperidinyl)ethoxy]benzoate (9) was prepared by alkylating methyl 4-hydroxybenzoate with 2-(l-piperidinyl)ethyl chloride (6). Hydrolysis of the methyl ester provided the carboxylic acid that was converted to the acid chloride (8) using SOCI2 in a mixture of 1,2-dichloroethane and toluene. Acid chloride 8 was then reacted with sodium phenolate to provide 9 as a stable crystalline solid in 64% overall yield from the carboxylic acid. 

Hydrolysis of Potassium Ethyl Sulphate. Dissolve about i g. of the crystals in about 4 ml. of cold distilled water, and divide the solution into two portions, a) To one portion, add barium chloride solution. If pure potassium ethyl sulphate were used, no precipitate should now form, as barium ethyl sulphate is soluble in water. Actually however, almost all samples of potassium ethyl sulphate contain traces of potassium hydrogen sulphate formed by slight hydrolysis of the ethyl compound during the evaporation of its solution, and barium chloride almost invariably gives a faint precipitate of barium sulphate. b) To the second portion, add 2-3 drops of concentrated hydrochloric acid, and boil the mixture gently for about one minute. Cool, add distilled water if necessary until the solution has its former volume, and then add barium chloride as before. A markedly heavier precipitate of barium sulphate separates. The hydrolysis of the potassium ethyl sulphate is hastened considerably by the presence of the free acid Caustic alkalis have a similar, but not quite so rapid an effect. 

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