Chaudhry, S. C.

Mahajan, R. K.

Malhotra, K. C.

English

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available, to the Computer Division, H'I', Kanpur,for help in analysing the data on IBM 7044 com-puter. One of the authors (L.B.) thanks CSIR,New Delhi, for financial support.References1. PETERSON, R. C., J. phys. cu« .. 64 (1960), 184.2. ASSARSSON, P. & EIRICH, F. R., J. pliy«. Chen i., 72(1968), 2710.3. ROHDEWALD. P. & MOLDNER. M., J. pbys. Chem., 77(1973), 373.4. SINGH, D., SINGH, N. P. & LAL BAHADUR. Indian J.Chem., 13 (1975), 1177.5. Fuoss, R. AI., J. phys. Chem., 79 (1975). 525.6. HARKNESS, A. C. & DAGGETT (Jr), H. 1'1., Call. J. Chem.,43 (1965), 1215.7. HAWES, J. L. & KAY, R. L., J. phys. Cheni., 69 (1965),2420.8. DAWSON, L. R., :N'EWELL. T. tlI. &. lIcCRE.-\RY, w. J.,J. Am. chem, Soc .• 76 (1954), 6024.9. DAGGETT. H. M., BAIR, E. T. & KRAl:S. C.. \., J. Am.chem. Soc., 73 (1951). 799.10. CHIU. Y. C. & Fuoss, R. M., J. phys. Cheni., 72 (1968),4123.11. Fuoss, R. M., (Personal communication).12. KAY, R. L.. J. phys. cu.«, 67 (1963). 1223.13. EVA:-1S.D. F. & KAY, R. L., J. phys. cu.« ..70 (1966), 366.14. LEE. M. D., J. niche, 10 (1972). 289.15. K.w, R. L. & EVANS, D. F., j. phys. cu,«, 70 (1966),2325.16. KAY, R. L., VIn.:ccIO,1'.. ZA\\'OYSKY. & EVAxs. D. F.,J. phys. CheJi/., 70 (1966). 2336.Phenol as a Non-aqueous SolventK. C. :'II."LHOTRA. R. K. MAHA]A='! & S. C. CHAUDHRYDepartment of Chemistry. Himachal Pradesh UniversitySimla 171001Received 18 December 1975; accepted 21 April 1976Organic tertiary bases form 1: 1 and 1: 2 adductswith phenol. Tetrachlorides of tin and titaniumform SnCI3(OC6H5).C6H.OH and TiCl3(OCGH5).C6H.OHwhen dissolved in phenol. Acid-base titrations oftetraphenoxides of tin and titanium against pyridineand sodium phenoxide have been carried out to estab-lish the auto ionization of phenol as 2C6H.OH ~C6H.OHi + CGH.O-.ORGANIC polar solvents have been extensivelyinvestigated as non-aqueous solvents. However,no such studies with phenol arc available in literaturethough some phcnoxidcs of tile me ..als have beenprepared. by the solvolysis of metal cl.Ioridcs inphcnolv".Phenol is slightly acidic ill nature (PK" = 1·0X 10-;0). Its physical properties like dielectric con-stant (9·78 at 45Cj, d.ipole moment (1·76 D) andspecific conductance (1·8 X 10-10 ohm+ crrr+) arecomparable to those of acetic acid {dielectric con-stant, 6·0; ctiple moment, 1·76 D). It has beensh.own4-6 that, in fluorosulphuric acid, phenol isprotonat ed at the ring rather than at the oxygenwhile in o isulphuric acio , it gets sulphonated". Itis amphoteric in nature. It is, therefore, of interestto investigate its solution chemistry and explorethe possibility of isolation of its actducts with Lewisacids and bases and characterize them.-OTE STABLE 1 - SPECIFIC CONDUCTANCES OF SOllIE SOLUTESIN PHENOL AT 50°Compound Cone.(mole/litre)Sp. conductanceX 10·(ohm:" cm+)Sodium phenoxidex-PicoliuePyridineTin(IV) chlorideAntimonytv) chlorideTitanium(IV) phenoxideTin(IV) phenoxide0·0120·0200·0390·0340·0310·0210·0387'671·961-472·522·382·813'09Phenol was purified by distilling it twice andcollecting the fraction boiling at 179°. It \I as crys-tallized twice by cooling in ice-water. Any tracesof moisture were removed by keeping it in vacuoover P20S for 48 hr. Samples of phenol havingm.p. 43° and specific conductance 1·8 X 10-8 ohrrr"ern? at 50° were used in this investigation. Theconductance measurements were carried out usinaa Tosliniwal conductivity bridge Sr Ko. 447. Allthe solutions were prepared in moisture-free atmo-sphere. IR spectra were recorded. in nujol on aPerkin-Elmer spectrophotometer No. 337.Dilute solutions of organic tertiary bases andalkali metal ph enoxirles in phenol are far more con-ducting than either of the components. Thoughthe specific conductance values of these solutionsare not very high (Table 1), yet these are quite sigrii-ficant in view of the low conductances of thecomponents and the low dielectric constant of themedium. This suggests that bases form complexeswith phenol, and at lower concentrations these areionized. TO solid compound of thes c bases withphenol could be isolated under the present experi-mental conditions suggesting weak interaction be-tween the two components. Nevertheless, conducto-metric studies on the mixture of the twocomponents show breaks in the conductance-com-position curves at the molar ratio (base: phenol) of1:1 and 2:1.IR spectral studies of the 1:1 liquid compoundshow that the spectral bands of the pure componentsundergo similar changes as are observed in the caseof pyridinium chlorides complexes of tertiary baseswith tellunum tetrachloride", acetyl chloride-s andselenium tetrach loride-". The oands at 1622, 1608,1503, 1480, 1385 and 1322 em+ are due to pyridi-nium ion. A new band observed at 1432 cm-l, notpresent in the pure components, may be assignedto 'IX-H. The bands at 1250, 1204, 1165, 1080, 993,890, 750 and 680 crrr" also supj.ort the formationof pyridinium ion. The broad band present at 3360,~m-l in ph enol, assigned to hydrogen-bonded OHgroup, shifts to 3160 ern> in these compounds. TheO-C stretching mode present at 1350 cm-l'n thephenol shifts to 1400 crrr+. These observationssuggest that OH group in phenol is retained and i~hydrogen-bonded to the nitrogen atom of the tertiarybase-s. The spectral changes in the compounds of1017INDIAN J. CHEM., VOL. 14A, DECE;\lBER 19765'0 &-A SnCI3(OC6H5)·C6HSOH versus C6H50NO.-. Ti(OC6HS)4- .C6HSOH versus C6H50NoQt-8 SnCI310C6HS)'C6H50H versus_ 40 ()-()Ti(OC6H5)4·C6H50H versus'E-"IEs:o"'-'~ 30x•."c2":::J1i! 2-0ou.~•..'u•.it 1·00'4 0'8 1·6 2·0 2'4 2-8 3·21·2Molar ratio Basel AcidFig. 1- Conductometric titrations between acids and basesin phenol at 50°other tertiary bases with phenol follow a similarpattern (unpublished data).Strong acceptor molecules such as antimonypentachloride, boron trichloride, aluminium trichlo-ride, etc., readily get solvolysed in fused phenol at45°. In the case of tetrachlorides of tin andtitanium, partially solvolysed products of composi-tionSnCI3(OC6H,,).C6HsOHand TiCI3(OC6Hs),C6HsOHare obtained. Complete solvclvsis of these com-pounds has been carried out to get Sn(OC6Hs)4 andTi(OCeH5l4,C6HsOH respectively (unpublished data).Acid-base t itrat ions of SnCi3(OC6H5),C6H50Hagainst C6H50Na or C5H5~ have been carried out.These t itrations have been iollowe.l both conducto-metrically and with the help of visual indicatorssuch as malachit e green anti crystal violet (Fig. 1).There are two breaks in the conductance-compositioncurves (Fig. 1) suggesting the dibasic character ofthe acid. Similarly tit rations of Ti(OC9H5)~.CeHsOHagainst pyridine or sodium phenoxide have alsobeen carried out. Compounds of compositionNa2Ti (OC6H5)6 and Ti(OC6H5)4.2CsH5~ have beenisolated from the solutions. Compounds of similarnature have already been reported in the case ofalkoxides13,14. The titrations apparently followreactions (1), (2) and (3).2C6HsOH'" +M(OCeH5)~- +Na+ +OC6HS-+CeHsOH~'" +NaM(OCeH5)&+2CeHsOH ... (1)CeH50Hi+ NaM(OCeHs)6+Na+ +OC6H5-+~a2[M(OCeR5)6J +2CeHsOH (2)Na2[M(OCeH6)6J~2Na+ +M(OC6H5H- (3)By analogy with the behaviour of methyl alcohol-sand acetic acidl6-18 and in the light of above observa-1018tions, the possible mode of ionization of phenol maybe postulated as2C6HsOH~C6H50H;+C6H50-References1. HARROD, J. F. & TAYLOR, K. R., Inorg. Chem., 14 (1975),1541.2. BIRD, P., FRASAR, A. R. & LAU, C. F., l norg, Chem., 12(1973), 1324.3. :'>lALHOTRA,K. c.. :\lAHAJA~, R. K. & CHAUDHRY, S. C.,J. inorg, uucl, Chem., (communicated).4. BIRCHALL, T., BOURxs, A. N., GILLESPIE, R. T. & S~ITH,P. J., Can. j. cio«, 43 (1964). 1433.5. PARRI~GTON, B. D. & CHILD, R. F., Chem, Comrnun.,(1970), 1581-6. BLACKSTOCK, S. :'II., RICHARD. K. E. & WRIGHT, G. J.,Can. j. Chem., 52 (1974), 331-7. MALHOTRA, K. C. 8: BALI, A. K., Indian J. Cliem., 13(1975). 699.8. GREENWOOD, N. N. & WADE, K., J. chem, Soc., (1958),1671.9. PA1:L, R. c., PA1:L, K. K. & :'>fALHOTRA,K. c., ChernyInd. (London), (1968), 1227.10. PAUL, R. C. & CHADHA, S. L., Spectroctrim, Acta, 22(1966), 615.11. CORDES, A. W. & HUGHES, T. V., l norg, Chem., 3 (1964),1640.12. HUNSHUGER, H., J. Am. chem, Soc., 72 (1950), 5626.13. MEHROTRA, R. C. & :'IIEHROTRA, A., Inorg, ci.«, 11(1972), 2170.14. PAUL, R. c., :'IIADAS, H. & CHADHA, S. L., J. inorg,nucl. Chem., 36 (1974), 737.1S. LUDMAN, C. J. & WADDINGTO:-:, T. c., J. chem. Soc.,(1966), 1816.16. PAUL, R. C., \'.~SISHT, S. K., 1\1.~LH9TRA, K. C. & PAHIL,S. S., .f. scient. indo Res., 21B (1962), 552.17. PAUL, R. c., YASISHT, S. K., :'>1.~LHOTRA,S. K. & PAHIL,S. S., A n al . Chem., 34 (1962), 820.18. PAUL, R. C., KAPOOR, K. R. & PAHIL, S. S., J. scient.indo Res., 21B (1962), 533.Co(II) Complexes of Pyridine-2-aldoxime &6-Methylpyridine-2- aldoximeS. K. BIIASIS & A. X. BHATDepartment of Chemistrv, Univcrsitv of Delhi, Delhi 110007Received 19] aiiuary 1976; accepted 26 April 1976The reaction in acetone of GoGI2.H20 with pyridine-2-aldoxime (HPOX) and 6-methylpyridine-2-aldoxime(HMePOX) in different stoichiometric ratios (1 : 2 andI : 3) in the absence and presence of hydrogen peroxidehas yielded different Go(lI) complexes. One of these,viz, Go(HPOX).GI2 is identical with that reportedearlier in literature [Aust. J. Chern., 27 (1974). 2475].The IR studies on these complexes indicate that in somecases, one ligand is ionized and the other unionizedwhereas in some cases both the Iigands in the complexesare unionized. All the complexes are cationic. Themeasured high magnetic moments rule out +3oxidation state of the metal ion in any of these COm-plexes.THE ligands pyridine-2-aldoxime (HPOX) and its6-methyl derivative (HMePOX) are usefulanalytical reagents':". Stability constants of theircomplexes with trivalent lanthanon ions have beenreported" and complexes of HPOX with Ni(II),Pt(II) , Pd(II)7,9 and CU(II)10,11 have also been

Phenol as a Non-aqueous Solvent

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Phenol as a Non-aqueous Solvent

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