ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 10, pp. 1412–1421. © Pleiades Publishing, Ltd., 2014. Original Russian Text © V.I. Potkin, S.K. Petkevich, A.V. Kletskov, E.A. Dikusar, I.B. Rozentsveig, G.G. Levkovskaya, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 10, pp. 1430–1439. 1412 Synthesis of Functional Derivatives of Aryl Trichlorovinyl (Trichloroallyl) Ketones via Consecutive Transformations of the Carbonyl Group V. I. Potkin a , S. K. Petkevich a , A. V. Kletskov a , E. A. Dikusar a , I. B. Rozentsveig b , and G. G. Levkovskaya b a Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, ul. Surganova 13, Minsk, 220072 Belarus e-mail: potkin@ifoch.bas-net.by b Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk, 664033 Russia Received April 23, 2014 Abstract—An efficient procedure have been developed for the selective reduction of the carbonyl group in phenyl trichlorovinyl ketone and aryl trichloroallyl ketones by the action of NaBH 4 in propan-2-ol to obtain the corresponding alcohols. The hydroxy group in the latter was converted into amino by the Ritter reaction. Treatment of the alcohols and amines with 5-phenylisoxazole-3-carbonyl chloride and 4,5-dichloroisothiazole- 3-carbonyl chloride gave the corresponding esters and amides, and condensation of the amines with aromatic aldehydes afforded Schiff bases. Unsaturated chlorinated ketones, especially chloro- vinyl ketones (chloroenones), are widely used in organic synthesis due to their high synthetic potential which is determined by the presence in their molecules of several reactive fragments, carbonyl group, chlorine atoms, and C=C double bond [1–3]. Preparative proce- dures for the synthesis of various useful compounds, including biologically active substances, have been developed on the basis of reactions of such ketones [4, 5]. An important problem related to efficient use of accessible chloroenones consists of selective modifica- tion of different reactive centers in their molecules in order to ensure desired transformations and avoid side processes. Convenient methods for the synthesis of unsaturated chloro ketones from accessible lower chloroalkenes have been developed at the Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, and Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences [2, 6–8]. The goal of the present work was to find rational synthetic approaches to chlorinated unsaturated alco- hols, amines, and Schiff bases via successive trans- formations of the carbonyl group in aryl trichlorovinyl and aryl trichloroallyl ketones with retention of the other reaction centers. The products of these reactions attract interest as substrates for further transformations, as well as for biological testing. As starting compounds we used 2,3,3-trichloro-1-phenylprop-2-en-1-one (I) and 1-aryl-3,4,4-trichlorobut-3-en-1-ones II–V which were prepared as described in [2, 6]. In the first step of our study we tried to develop an efficient procedure for the selective reduction of the carbonyl group, not involving chlorine atoms and C=C bond. Various reagents and reagent systems have been proposed for the reduction of carbonyl group, e.g., metallic sodium in alcohol, LiAlH 4 , NaBH(AcO) 3 , NaBH 4 , and others. In our case, neither metallic sodium in alcohol nor sodium tetrahydridoborate can be used because of concurrent reactions involving the chlorine atoms and C=C double bond, which lead to complex mixtures of products. The reaction with sodium triacetoxyhydridoborate in anhydrous benzene in the presence of acetic acid was relatively slow, and the target alcohols were formed in low yield. The optimal procedure for the reduction of ketones I–V was their treatment with a slight excess of NaBH 4 in propan-2-ol. In this case, the reaction involved DOI: 10.1134/S1070428014100042