Chloroethyl ethyl ether

Dry hydrogen chloride is passed into 50 g. (0.48 mole) of styrene cooled to —80° until the gain in weight of the reaction mixture is 28 g. Freshly distilled styrene (b.p. 40°/12-13 mm.) is used. After it has been warmed slowly to room temperature, the product is distilled and gives 48.5 g. (68%) of a-chloroethylbenzene, b.p. 73°/ll mm. 

Dry hydrogen chloride (100 g., 2.75 moles) is passed into a mixture of 100 g. (0.76 mole) of paraldehyde and 100 g. (2.18 moles) of ethyl alcohol cooled in an ice bath. Hood.) The upper layer formed during the hydrogen chloride addition is separated and dried over calcium chloride. Distillation gives 162 g. (69%) of a-chloroethyl ethyl ether boiling at 93-96°. 

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Ethyl vinyl ether, CH2=CH0C2H5. Mol. wt. 72.10, b.p. 35.7° n D 1.3768. Suppliers A, B, E. Preparation from 1-chloroethyl ethyl ether by reaction with pyridine ... 

If less chlorine is used, this method gives 1-chloroethyl ethyl ether as main product, which is more easily separated from by-products by distillation than in the case of Henry synthesis (see page 232). Similarly chlorination of tetra-hydrofuran under UV-irradiation at —30° to —40° gives 2-chloro- and 2,5-dichloro-tetrahydrofuran,513 and that of dioxan in CC14 at —5° to —10° gives 2,5-dichlorodioxan.514 However, no definite product was isolated on low-temperature chlorination of diisopropyl ether.515... 

Whereas exhaustive chlorination of acetaldehyde dimethyl acetal (at not more than 60°) affords formaldehyde, 1-chloroethyl ethyl ether, trioxymethyl-ene, and HC1 as main products, exhaustive chlorination of the diethyl acetal (at 60-70°) gives a product that, on treatment with concentrated H2S04, affords chloral in good yield.629 The mixtures afforded by chlorination of acetals contain, inter alia, chloro ethers derived by reaction with the HC1 formed the chloro acetals are obtained by subsequent addition of ethoxide. 

The following, inter alia, can also be obtained by the Henry synthesis chlo-romethyl methyl ether from formaldehyde,518,993 paraformaldehyde,994 or s-trioxan 995 1-chloroethyl ethyl ether from paraldehyde 531,996 and similarly 1-bromo-992,997 and 1-iodo-alkyl ethers.993... 

For instance, 1-chloroethyl ethyl ether is obtained from acetaldehyde diethyl acetal and PC15,1057 chlorobenzyl methyl ether from benzaldehyde dimethyl acetal, acetyl chloride and SOCl21058 and 1-bromoalkyl ethers from the corresponding acetals.1059 1-Bromoalkyl ethers can also be prepared from 1-chloroalkyl ethers into which HBr is passed at about 20° 1-iodoalkyl ethers are obtained from the 1-chloro analogs by use of Nal in acetone. 

Chloroethyl ethyl ether 90.1 + 2.0 377.0 + 8.4 Derived from 1996N1ST... 

A. ot-Chloroelhyl ethyl ether. A mixture of 200 g. (201 ml.) of redistilled paraldehyde, b.p. 121-122.5° (equivalent to 4.54 moles of acetaldehyde), and 200 g. (254 ml., 4.34 moles) of absolute ethanol is placed in a 1-1. three-necked flask fitted with a mechanical stirrer and a gas inlet tube reaching to the bottom of the flask. The mixture is cooled to —5° in a mixture of Dry Ice and acetone, and dry hydrogen chloride (Note 1) is passed into the stirred reaction mixture maintained at about —5° until 200 g. (5.48 moles) has been absorbed. During this operation, which requires about 2 hours, the reaction mixture separates into two layers. The upper layer of crude a-chloroethyl ethyl ether is re-... 

Chloroethyl benzoate, 30,11 a-Chloroethyl ethyl ether, 36, 60 Chlorohydroquinone, 35, 27 -Chloromandelic acid, 35,14 Chloromethylation, 30, 68 2-Chloro-2-methylcyclohexanone, 37, 8... 

Ion-Formation from a-Chloroethyl Ethyl Ether and Antimony Pentachloride, P.H. Plesch and V.T. Stannett, Journal of Macromolecular Science Chemistry, 1982, A18, 425-430. 

Chemical/Physical. Chlorination of 2-chloroethyl vinyl ether to a-chloroethyl ethyl ether or P-chloroethyl ethyl ether may occur in water treatment facilities. The alpha compound is very unstable in water and decomposes almost as fast as it is formed (Summers, 1955). Although stable in NaOH solutions, in dilute acid solutions hydrolysis yields acetaldehyde and chlorohydrin (Windholz et al., 1983). At pH 7 and 25 °C, the hydrolysis half-life is 175 d (Jones and Wood, 1964). 

Four chloro ethers have been fluorinated over cobalt(III) fluoride at 110 150°C. With 2-chloroethyl ethyl ether most of the chlorine is retained114 and the major products (there are... 

On the other hand, if diethyl ether is treated at —20° or below with one equivalent of chlorine, a-chloroethyl ethyl ether is formed in 42% yield. Further chlorination at this low temperature leads to a,a -di-chlorodiethyl ether in 57% yield, the second chlorine atom entering a new alpha position in preference to an alpha position already substituted. The extension of this new technique to higher ethers is under way. Other methods are available for the preparation of a- and /3-halo ethers (see Chapter 6). 

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