Acetaldehyde chlorine atom reaction

In the reaction of acetaldehyde with dichlorine (Equation 4.16), hydrogen atoms are substituted for chlorine atoms to give mono-, di-, and trichloroacetaldehyde (chloral) chlorine does not displace the oxygen atoms. 

For the two investigated compounds with the chlorine atom substituted next to the double bond, the intensity of the nitroperoxy bands passed through a maximum while the nitroxy bands continued to increase during the course of the experiments. A carbonyl band at approximately 1750 cm was seen at the same time. This indicates that either a carbonyl nitrate compound or a nitrate and a carbonyl compound were formed through decomposition of the nitroperoxy nitrate intermediate. Small amounts of acetaldehyde and chloroacetaldehyde were found among the products formed from the reaction with l-chloro-2-butene. In the reaction with 3-chloro-l-butene, significant amounts of formaldehyde were formed. 

Niki, H., P.D. Maker, C.M. Savage, and L.P. Breitenbach (1985b), FTIR study of the kinetics and mechanism for chlorine-atom-initiated reactions of acetaldehyde, J. Phys. Chem., 89, 588-591. 

Seakins, P.W., J.J. Orlando, and GS. Tyndall (2004), Rate coefficients and production of vibrationally excited HCl from the reactions of chlorine atoms with methanol, ethanol, acetaldehyde and formaldehyde, Phys. Chem. Chem. Phys., 6, 2224—2229. 

Chloroacetaldehydes are produced by the reaction of acetaldehyde with chlorine by replacement of the hydrogen atoms of the methyl group. Chlorine reacts with acetaldehyde at room temperature to give mono-chloroacetaldehyde. Increasing the temperature to 70 to 80°C gives dichlor-oacetaldehyde, and at a temperature of 80 to 90°C trichloroacetadehyde, (chloral) is formed. 

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