Indian Journal of Chemistry Vol. 23A. March 1984, pp. 246·247 Reactions of Naphthoxides of Titanium (IV) with a-Hydroxyaldehydes & Ketones K C MALHOTRA*, K C MAHAJANzyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA & S C CHAUDHRY Department of Chemistry. Himachal Pradesh University. Slimmer Hill, Shimla 171005zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA Received 20 July 1983; revised and accepted 28 September 1983 Monochloro-. dichloro- and trichloro-titanium (IV) naphthoxides react with benzoin, 2-hydroxyacetophenone and salicylaldehyde in appropriate molar ratios and fonn compounds of compositions Ti(OClOH,bL. TiCI(OC:,H·), Land Ti(OC 'O H7lz.2L: and TiCliOC! "H.). Land TiCI(OC I "H -i.2L respec nvely. Based upon elemental anal) ses. conductance. cryC'SCOPlCand Infrared spectral measureme:i -. vJs'.!blc structures have been suggested. Mehrotra and coworkers 1 have extensively studied the reactions of alkoxides of titanium (IV) and zirconium (IV) With salicylaldehyde. z-Hydroxvcarboxylic acids and salicylic acids also react with alkoxides of these metals+:'. Benzoin and substituted benzoins form stable chelates with halides of titanium (IV),l Salicylaldehydooxotitanium monoalkoxide has been prepared by Gopinathan and coworkers'. In our earlier communication, we have explored the acceptor properties of naphthoxides of titanium (IV)I'. We now report the reaction products "I' naphthoxides of titanium (IV) with «-hydroxyaldehydes and ketones. Titanium (IV) naphthoxide-. T1CI(OC tpH,).I' TiCI/OC loH7h and TiCI 3 (OC !\,H-) were prepared by the methods reported earlier' Benzoin, 2-hy· droxyacetophenone a nd salicylaldehyde were purified before use. Compounds of composiuons TI(OC loH7hL, TiCI(OC1llH')2 Land Tl(OC10H')2.2L; and TiCI 2 (OC 1o H7).L and TiCI(OC\()H-)2L were pre- pared by refluxing the ligands such as benzoin (benzH), 2-hydroxyacetophenonc (hapH) or salicylaldehyde (sall-l) with monochloro-, dichloro- or trichloro- titanium (IV) naphthoxides, in dry benzene in predetermined molar ratios till there was no more evolution of hydrogen chloride gas. The compounds were isolated as solids either by the addition of pet. ether to the resulting solutions or by cooling. The solid compounds were filtered. washed and dried in vacuo. Stoichiometric compositions of the compounds arc given in Table 1. Possible reactions showing the formation of the products may be postulated as follows: TiCJ~(OC: OHC)2+ LH --+ TiCl(OC loH.,h.L+ HCl TiC1 7 \OC :,J-I-)2 + 2LH --+ Ti(OC loH,h.2L + 2HCl Table I-Analytical Data of the Chelates of Naphthoxides of Titanium ,IV) with Benzoin, 2-Hydroxyacetophenone and Sahcylaldehyde Compound Colour mp Titaruum I ,) (I i'ol Mol. wtNMLKJIHGFEDCBA (C) In nitrobenzene Found Calc. Found Calc ------------ found' Calc. Ti(OC,,,H.),benz Light 197 6.93 6.90 brow'} TiCI(OC 1(,H.),.benz Brown 225-226 8.19 ~~- 6.0' ~) : 2 i 127 1161 Ti(OC ,oH-),.2benz Do 165 (d) 6.31 {d:, 719 756 TiCI,(OC ,oH.).benz Do 10S 10.01 10.1·; iU9 " (;1 902 946 TiCI(OC ,oH .).2benz Do ! rs 7.28 ;' 4{, 5.41 i I Ti(OC,,,H-hhap Reddish 226·227 no - Xc, 1197 1224 brown TiCI(OC loH-),.hap Do 25lJ (d) 9.:19 lJ51 t,91 ,J, Ti(OC 'O H,),.2hap Do 140 :.;)7 7.95 5-9 604 T1Cl,(OC,oH,).hap Red 220 i z:» 12.09 1:.81 ~il 7": 794 ." TiCI(OC loH,).2hap Do 158 (d) 9.<:~ 9.6 7 0.95 440 496.5 Ti(OC,oH,j,.sal Mustard 178 7 '14 8.03 TiCI(OC,oH,),.sal Do 172 (d) 9.72 9.79 7.1 i ~1.24 949 981 nOC, oH ,),.2sai Do '1)(1 8.21 R.D TiCI,(OC,oH,).sal Do 220 12.41 12.53 18.47 18.53 TiCI(OC I oH, ).2sal Do 150 10.19 10.25 7.47 7.58 422 468.5 *Values reported are the mean of three determinations each, Benz = benzoin; hap = 2-hydroxyacetophenone; and sal = salicylaldehyde . 246 . _------------------------------ ---- ,----- ----------------