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Monobromide NOTE S K. Jankowski, J. Kirchnerova, G. Perreault and to (lit." m.p. 125°); Ph2SnNp2, m.p. 208° (lit." m.p- J. Belanger for discussions. Grants from the Faculty 209-10°). of Graduate Studies and Research (McGill Iodine monobromide", cyanogen bromide" and Uiversity), CIL, and help from faculty members thiocyanogen" were prepared and purified by litera- McGill University are also acknowledged. ' ture methods. Anhydrous carbon tetrachloride was References used .as the solvent and moisture excluded during the reactions. 1. WERNER, A. E., J. chern. Soc., 101 (1912), 2180. One typical experiment is described below. Others 2. COADE, M. E. & WERNER, A. E., J. chern. Soc. (Transactions) 103 (1913), 1221. ' are given in Table 1. 3. RmD, J. H., Q. Rev., 15 (1961), 418. Reaction of Ph3SnNp with IBr (in I : I ratio) - A 4. H~I.CHINSON, K. & BOLTZ, D. F., Analyt. Chem., 30 (1958), solution of IBr (2.07 g, 0.01 mol) in CCl4 (30 ml) was 5. US Pat., 3 886 010 (27 May, 1975) to Ireco Chemicals slowly added to a stirred solution of triphenylnaph- Company. ( thyltin (4.77 g, 0.01 mol) in CCl4 (100 ml) at room 6. EDMONDS, A., KIRCHNEROVA, J., MATIS, T. C. & PAR~, temperature. The blood red colour of IBr solution J. R. J., CDN Pat. No. 1096172 (1981). 7. Foss, 0., JOHNSEN, J. & TVEDTEN, O. Acta chem scand. gradually disappeared after each addition. After the 12 (1958), 1782. ", addition was over the mixture was stirred and war- 8. PERROT, J. R., STEDMAN, G. & UYSAL, N., J. chern. Soc. med for 30 min. The solvent was removed completely (Dalton), (1976), 2058. and the residue distilled under reduced pressure to 9. COOLlNGS, P., Al-MALLAH, K. & STEDMAN, G., J. chem, 0 Soc. (Perkin II), (1975), 1734. give a-naphthyl iodide (1.7 g, 70 %), b.p. 160 /8mm 10. SAHASRABUDHEY, R. H., J. Indian chern. Soc., 27 (1950) (lit.! b.p. 305°/760 mm), further characterised by 515; 28 (1951), 119. ' CO-IR with an authentic sample. The residue was 11. OAn~E, S., FuKUSHIMA, D. & KIM, Y. H., Chern. Lett., (1978) , recrystallized from cold pet. ether (60-80°) and 12. PERRIN, D. D., Dissociation constants of organic bases in identified as triphenyltin bromide (3.4 g, 80 %), aqueous solutions (Butterworths, London), 1965. m.p. 120 (lit." m.p. 122°). Though it has been established- that the metal- aryl bond is preferentially cleaved over the metal- alkyl bond, however, when two different aryl groups Reactions of Tin-Naphthyl Bond with Halogens & are present as in this system, there is the possibility Pseudohalogens of one undergoing preferential cleavage over the other. In the case of triphenylnaphthyltin or diphenyl- S. N. BHATIACHARYA* & ISHRAT HUSAIN dinaphthyltin, the naphthyl group is found to be Department of Chemistry, University of Lucknow, more reactive and hence it is cleaved before identically Lucknow 226 007 placed tin-phenyl bonds. This is due to the fact that in naphthyl group the ec-carbon atom attached to Received 6 January 1981; revised and accepted 23 February 1981 metal has greater electron density due to greater Reactivity of Sn-phenyl or Sn-naphthyl bond in tetraorga- magnitude of self-polarisability and hence more readily attacked by electrophiles than the phenyl notins, Ph SnNP4_n (Ph = phenyl, Np = ex-naphthyl; n = 2,3) n group in which the self-polarisability at all positions towards halogens (Br2 and 1 ), interhalogens (mr and ICI), 2 is equal", interpseudohalogens (BrCN and leN) and pseudohalogen (SCN)2 Both Br2 and ICI are strong electrophilesv" and has been studied. It is found that the Sn-Np bond is preferen- invariably cleave two organic groups from tially cleaved yielding in most cases phenyltin derivatives along Ph SnNp4_n at lower temperature (-5°) irrespective with the corresponding ex-naphthyl halides. n of the ratio of the electrophile used to give diphenyl- tin dihalide, Ph2SnX2 (X = Cl, Br) along with the REACTIONS of symmetrical (R4M) and unsy- corresponding amount of cx.-naphthyl- and phenyl- mmetrical (RnMR' 4-n) tetraorgano derivatives halides. In the case of Ph2SnNp2 both the naphthyl of Group IV metals (M = Si, Ge, Sn and Pb) with groups are preferentially cleaved (Eq. 1). various electrophilic reagents have been reviewed'. We now report some reactions of tetraorganotin Ph2SnNp2 + 2ICl -+ Ph2SnCl2 + 2NpI .. (1) derivatives, PhnSnNp4_n (n = 2 or 3 and Np = ec-naphthyl) with halogens and psuedohalogens. The Attempts to prepare the monohalide, PhnNp3-n main object of this work was (i) to study the extent snX (X = Cl, Br; n = 2 or 3) by slow addition of and relative ease of the cleavage of Sn-Np or Sn-Ph one mol of Br2 or ICI at _5° have not been success- bond, (ii) to characterise the organotin reaction pro- ful and unreacted Ph"SnNp4-n (n = 2 or 3) (50%) ducts and the corresponding aryl halides, RX (R = is recovered in each case. phenyl or ex-naphthyl; X = Br, I, SCN) and (iii) to Reactions with IBr and 12 are less facile. Thus compare the reactivities of strong (ICl, Br2), medium 1 : 1 molar reactions of IBr and 12 with Ph3SnNp [12, IBr, (SCN)2] and weak (lCN, BrCN) electrophiles afford Ph3SnBr and Ph3SnI respectively at room towards the system in the absence of a Lewis acid temperature (Eq. 2). IBr and 12 cleave one more catalyst. phenyl group from Ph3SnX on further refluxing for Triphenylnaphthyl- and diphenyldinaphthyl-tins 30 min in CCI4• Diphenyldinaphthyltin furnishes were prepared by reacting cx.-naphthylmagnesium bro- diphenylnaphthyltin iodide with one mol of 12 and mide and phenyltin chloride initially in ether follo- with two mol of IBr or 12 it affords diphenyltin- wed by refluxing in toluene: Ph3SnNp, m.p. 125° dihalide at refluxing temperature of CCl4 (Eq. 3). 1119 INDIAN J. CHEM., VOL. 20A, NOVEMBER 1981 TABLE 1 - REACTIONSOF Ph., SnNp4_" (Ph = phenyl, Np = «-naphthyl; n = 2 or 3) WITH X2, IX, XCN AND (SCN). (X = Cl, Br, I) Electrophile (XY) Molar ratio Reaction time (hr), Productsts) Yield m.p.tlits.m.p.) ---------------- XY/PhnSnNp4_n and temp. (0C) (%) (0C) X Y REACTIONSWITH Ph3SnNp Br Br 2:1 1, (-5) Ph2SnBr.(b) 75 35 (38) I I 1:1 I, (25) Ph3SnI 80 121 (121) I I 2:1 1, (70) Ph.SnI2(b) 76 71 (72) I C) 1:1 !, (0 to -5) Ph2SnCI2(c) 78 42 (44) I Cl 2:1 t, (0 to -5) Ph.3nCl.(b) 80 41-42 (44) I Br 2:1 1, (10) Ph2SnBr.(b) 72 36 (38) I CN 1:1 2, (70) Ph3SnCN 80 255 (256) Br CN 1:1 2, (70) Ph3SnCN 80 254 (256) SCN SCN 1:1 1, (0) Ph3SnNCS 58 173 (174-75) REACTIONSWITH Ph2SnNp2 Br Br 1:1 I, (-5) Ph.SnBr.(c) 68 37 (38) Br Br 2:1 1,(-5) Ph2SnBr2 75 36 (38) I I 1:1 !, (25) Ph2NpSnI<d) 70 135 I I 2:1 1, (70) Ph2SnI2 70 70 (72) I Cl 1:1 t, (0 to -5) Ph2SnCI. 75 42 (44) I Cl 2:1 t, (0 to -5) Ph2SnCl2 80 42 (44) I Br 2:1 1, (25) Ph2SnBr. 65 36 (38) (a) Corresponding amounts of NpX (X = Br, I, NCS) were also obtained, the b.p. of which agree well with those reported in literature'. (b)NpX (X=Br, I) also contained some phenyl halides which were not individually separated. (clUnreacted PhnSnNp4-n (n = 2 or 3) was also isolated. (d)Found : C, 50.06; H, 3.12; Sn, 22.41. C.2H'7SnI requires C, 50.14; H, 3.21; Sn, 22.52 % Ph3SnNp + IBr --+ Ph3SnBr + NpI .. (2) of AICl3 (ref. 6,8). CICN is ineffective towards Si-C bond even in the presence of AICl (ref. 8). Ph SnNp2 212 --+ Ph SnI 2NpI .. (3) 3 2 + 2 2 + However, in the present investigation it is observed The mechanism of such reactions possibly involves that tin-naphthylbond in Ph3SnNp is prone to attack a four-centered transition state (A) in which nucleo- by cyanogen bromide or iodide producing triphenyl- philic attack on metal atom by incipient halide ion is tin cyanides in the absence of any Lewis acid catalyst. synchronous with electrophilic attack by iodonium When excess of cyanogen halide is employed, no ion on carbon. cleavage of phenyl group is observed due to electron withdrawing nature of CN group introduced in Ph3SnCN which will have a strong deactivating effect on the remaining Sn-phenyl bonds and will ©Jf) discourage substitution by further cyanogen halide +, ,+ molecule". Ph3Sn<" ,,>1 '.•/... The cleavage of metal-carbon bond by (SCN)2 )( is consistent with its pseudohalogen character but it (X=Cl,Br) seems less reactive than even the interhalogens and ( A) more reactive than inter-pseudohalogens=". Thus, with Ph3SnNp, tin-naphthyl bond is cleaved by Similar mechanism has earlier been suggested for freshly prepared (SCN)z (1 : 1 ratio or excess) at ice- the cleavage of M-C, M-P and M-As (M = Si, Sn, bath temperature. Further warming or prolong stirr- Pb) bonds by halogens>" amd interhalogens=". ing with excess of (SCN)2 favours polymerization of The fission of second Sn-C bond in these reactions the electrophile precluding the cleavage of phenyl is less facile due to reduced nucleophilic character of group. The formation ofPh3SnNCS may be explained Sn-C bond in triorganotin derivatives (because of on the lines proposed by Bullpit and Kitching". the presence of an electronegative group attached to Financial assistance from State Council of Science tin) as compared to tetraorganotin compounds, and Technology, Lucknow is gratefully acknow- coupled with the less polar nature of IBr and 12 ledged. which behave as weak electrophiles.
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