Chloral alcoholate

Chloral hydrate is obtained by the action of chlorine upon ethyl alcohol. The solid chloral alcoholate is foimed, CClj.CHOH.OCjHj, which, when decomposed with sulphuiic acid, yields chloral, CCI3.COH, a licpiid which combines with water to form the ciystalline hydrate. 

Chloral hydrate and chloral alcoholate react with phosphine in the presence of HCi to give compound 4 in the form of its monohydrates The preparation of this compound from chloral hydrate and phosphonium iodide has been previously described by Girard... 

Dichlorovos may be prepared in several ways. Methanol is treated with chloral (CCI3-CHO) and PCI3 to get dimethyl-l-hydroxy-2,2,2-trichloroethyl phosphate (55), which is heated with 25% NaOH to yield dichlorovos (23) [60]. Alternatively, chloral alcoholate (56), the precursor of chloral prepared by passing chlorine into cooled ethanol, is allowed to react with (MeO)jP to form dichlorovos [61]. In another approach, methanol is treated with PCI3 to get (MeO)3P (57) [62]. This reaction may also be carried out in the presence of CuCl at - 10 C to yield the adduct (MeO)3P.CuCl (58) [63]. Reaction of 57 or 58 with chloral yields dichlorovos (23) [62,63]. 

The industrial manufacture of DDT is based on the synthesis described by Zeidler. Chloral, chloral alcoholate or chloral hydrate is reacted with chlorobenzene in the presence of sulfuric acid, oleum or chlorosulfonic acid (Rueggeberg and Torrance, 1946). The t hnical product thus obtained contains several impurities, including the ortho-para (2) and ortho-ortho (3) isomers, 2,2-bis-(p-chlorophenyl)-1,1 -dichloroethane (p,p -DDD, 4), its ortho-para isomer (o,p -DDD,... 

Alcoholate A salt in which alcohol aooears to replace the water of crystallization. as iS the case of certain chlorides, nitrates, etc., as chloral alcoholate, CCl 3CHO.C2H O. Some of them may be formed by simole solution and crystallization of the salt in alcohol. 

Oily liquid. Pungent, irritating odor d " 1.510 djs 1.5050. mp -57.5. bp , 97.8. n 1.45572 nft 1.45412. Freely sol in water forming chloral hydrate. Sol in alcohol forming chloral alcoholate sol in ether. Polymerizes under the influence of light and in presence of sulfuric acid forming a white solid trimer called metachloral. 

Chloral also comhines with alcohol, with elevation of temperature, to form a solid, crystalline body—chloral alcoholate ... 

The resulting product is called chloral alcoholate, as it can be formed by the direct union of chloral and alcohol. As the consequence of all these reactions, the product finally obtained when alcohol is treated with chlorine is a mixture which contains chloral hydrate, trichloroacetal, and chloral alcoholate. Chloral is set free from these compounds when the mixture is treated with concentrated sulphuric acid. 

Other process modifications include the replacement of ethanol with ethanol-acetic acid mixtures in the chlorination step270 with recycling of the less volatile byproducts, such as chloral acetate, chloral alcoholate, butyIchloral, and... 

Chloral alcoholate 10232 AT-Chloro-4-methylbenzenesulfon- C.I. Acid Green 3 5619... 

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