With Cyanogen Bromide & Iodide

Indian Journal of Chemistry Vol. 15A, September 1977, pp. 799-801

Reactions of Tetraorgano Derivatives of Ge(IV), Sn (IV) & Pb (IV) with Cyanogen Bromide & Iodide

S. N. DHATTACHARYA* & PREl\I RAJ Chemistry Department, Lucknow University. Lucknow 226007

Received 11 October 1976; accepted 3 February 1977

The Ar'IM compounds (Ar = phenyl and p-tolyl; M = Ge and Sn) and Bu3PhSn were fo~nd

to react with cyanogen bromide and iodide in the presence of AIGI3 to produce the cor-responding arylhalides. Ar.Pb compounds did not react with either of the reagents in the absence of AlGI" under various conditions.

LEAV AGE. of .metal-carhon bonds i~l tetr~- organo der ivatives of group IV metals (M=SI, TABLE 1 - RJ::ACTIONSOF ICN AND DrCN WITH TETRAARYL- C Ge. SI1 and Pb) by clcctrophilic reagell~s GER~rANlUM AND -Trx \Ar.M) COMPOUNDS{a) have been extensively studied both from synthetic Ar.M XCN{b) ArX(c) b·p·flit.18 b.p, and mechanistic point of view-. In recent years, Ar = X= (% yield) °C several reports have appeared regard~ng ~he cleavage of group IV metal-aryl bonds with inter- and Ge(IV) pseudo-halides, e.g. ICI. IBr (ref. 2, 3), (S~N)2 Ph I 50 184/184-86 (ref. 4, 5) and Se(ScCN)z .(ref: 6). These r~actl.on;':i, P-Tolyl I 52 208/211-12 are useful for functionalization of aromatic nngs Ph Br 43 155/157 at predetermined posit icns- and for synthesizing p-Tolyl Dr 47 180/182-84

R MX or R2MX2 derivatives in onc-st eps-". , Sn(IV) Thongh the reactions involving inter-pseudohalJdes such as cyanogen halides XCN (X=Cl, Dr. I), Ph I 60 184/184-86 cyanogen azide (CNNal. iodine azide (IN3) , and p-Tolyl I 63 208/211-12 Ph Br 54 155f157 iodine cvanatc (INCa) have been extensively p-Tolyl 13r 58 180/182-84 studied f~r stereospecific addition to olefins", rCJ:>O,rts regarding their action on compounds contammg (a) One mole of cyanogen halides was employed in each case along with one mole of AIel,. metal-carbon bonds arc rare. Challenger et al.8•9 (b) Reactants were mixed at 0° and were then allowed to studied the interaction of Ph3E compounds (E=P. attain the room temperature over a period of 1 hr under As, Sb and Bi) with cvanogen halides and f?llIld constant stirring.

that while ICN adds oxidativelv to yield Ph3EICN (c) Calculated on the basis of mono-cleavage.

(E= P, As and Sb), it yielcl~ PhI with Ph3Di. The corresponding reactions of CNCl and CNUr with Ph3Bi produce PhCN. Recently ... Eaborn Two representative experiments are described ei al.1U investigated the cleavage of aryl-xilicon and below. The data on other reactions are summariz- aryl-tin bonds with C~CI and CNBr, in the pre.se,:ce ed in Table 1. of AIC1 and observed that CNCl ,YIelds arylJ1lt,nle.s 3 Reaction of Bu SnPh with XCN in the presence of while BrCN gives the corresponding arvlbromides. 3 AlCl - Cyanogen bromide (1·70 g, 0·016 mol) was Grignard reaaents have also been reported to 3 . b, hl'd II car, fully added with stirring and exclusion of mois- behave diffcrentlv WIth these cyanogen a 1 eo. . ture to a solution of phenyltributyltin (5·50 g, In view of such contrasting' behaviour of cyanogen 0·015 mol) and finely powdered anhydrous alumi- halides and of our interest in the group IV metal- nium' chloride (2·4 g, 0·018 mol) in dichloro- . h elect hili t ·3 5 12 13 aryl bond cleavages WIt e ec 'rop I ICreagen s .. . , me thane kept at ODe. On allowing the mixture to we report here the interaction of aryl-metal (M=Ge, warm up to the room temperature, a moderately Sn and Pb) bonds with BrCN and ICN. exothermic reaction set in. After stirring for 1 hr Materials and Methods at room temperature, the mixture was poured over crushed ice. The organic layer was separated, Phenvltributvlt inw, tetraarylgermanillm, -tin and washed with O'IM NaOH solution to destroy resi- 15 -lead compounds+-" and cyanogen bromick were dual BrCN followed by water, dried over sodium prepared by previously reported methods. Cyanogen sulphate and fractionally distilled to give bromo- iodide (Eastman Organic Chemicals) was ~ecrystal- benzene. b.p. 1550 (1·45 g, 62%). identical (IR) Iized before use. The solvents were purified and with an authentic specimen. To examine the resi- dried before use. dual part for the presence of Bu3SnCN, it was 0 *To whom correspondence should be addressed. refluxed with pet. ether (b.p. 60-80 ). filtered, the 799 INDIAN J. CHEM., VOL. 1SA, SEPTEMBER 1977 filtrate concentrated and cooled; but the material obtained could neither be identified nor did it exhibit the characteristic IR band for nitrile function-s. Similarly, phenyltributyltin (5·50 g, 0·015 mol) in dichlorornethane and cyanogen iodide (2·44 g, 0·016 mol) in the same solvent in the presence of

AICl3 (2'4 g, 0·018 mol) produced iodobenzene, (WhereY=Hcr p-CH ;X:8r c r- 1) b.p. 184° (2'02 g, 66%). . 3 Reaction of Ph Pb and XCN in. the absence of Chort 1 4 --+-- AlCl3 - To a stirring suspe~sion of Ph4Pb (1:43. g, 0·0027 mol) in chloroform (bO ml), cyanogen iodide philic cleavage of such bonds increases with the (0·43 g, 0·0028 mol) in the same solvent (30 ml) increase in the polarity of the bond. was added dropwise during 30 min at ice tempera- The mechanism of such reactions may possibly ture. The reaction mixture was stirred for a further involve a four-centred transition state (Chart 1) period of 2 hr. Chloroform was .distilled. off and in which nucleophilic attack on the metal atom the residual white solid washed with a mixture of (facilitated by the availability of vacant d-orbitals) dichlorornethane and ether (3 X 10 ml) to remove by the incipient cyanide ion is synchronous with unreacted cvanocen iodide. The solid residue was electrophilic attack by incipient halonium ion on characterize-d as 'Ph4Pb, m.p. 228° (lip7 m.p. 229°C) carbon atom of the aromatic ring. An argument and unreacted ICN from filtrate was recovered in favour of such a transition state has been based quantitatively. on the observation that a similar reagent iodine The above reaction was also attempted unsuccess- mono chloride reacts with phenyltrimethylsilane (to fully (i) at room temperature over a week with cons- give iodobenzene) about 8-times as fast as does tant stirring, (ii) at reflux temperature of CH2Cl2 chlorinet". The presence of AICI3 in the above (35°), CHCl~ (58-60°) and CCI4 (76-79~) for about reactions induces some degree of polarization in 3 hr and (iii)by heating the reactants 111 CCl4 solu- cyanogen halides, X+ (AICI3.CN)- and thereby tion at 100° in a sealed tube for 72 hr. increasing their electrophilic character towards Similar results were obtained when the reactions C--M+ bond(s). were attempted with cyanogen bromide under It appears that both ICN and BrCN are much conditions described above. weaker electrophiles as compared to halogens2,3,12, Results and Discussion intcrhalogens--", or pseudohalides+" which are all reported to react with these metal-aryl bonds in Reactions of tetraorgano-germanium and -tin the absence of a catalyst. compounds were carried out with BrCN and ICN Being relatively weak -electrophilcs and in view in CH Cl2 in the presence of AICI3. Both the of an earlier reported work-" where considerable cyanogen halides were found to yield the correspond- amounts of aryltrimethyltins were obtained un- ing isomerically pure aryl halides confirmed by changed it is reasonable to assume that the cleavage GLC which show in each case the presence of a in the present read ions is confined to only one single constituent in yields ranging f~om 43 to 52% metal-aryl bond in tetraaryl-gerrnanium and -tin for Ar Ge and 54 to 660;" for the t in compounds. compounds. No appreciable increase in the yields Thus, ieactions with tetra-p-tolylmctallic derivatives of the aryl halides was observed when an excess yielded pure p-tolyl halides. (Table 1). No tr~ces (> 1 mole) of cyanogen halides was employed. of arylnitriles were detected 111 any of the~e reactions Furthermore, the CN group once introduced in as evidenced bv the absence of absorption for the R3MCN compounds will have a strong deactivating C=N grouplO. -Since the aryl halides were obtained effect on the three remaining M-aryl bonds due to through hydrolysis of the reaction products the its electron withdrawing nature decreasing the organometallic species could not be isolated as they polarity of M-aryl bonds, and thus will discourage were not expected to survive during work-up. substitution by further cyanogen halide moleculesw, Furthermore, Ar3SnCN are known to be very From the facts that (i) under identical conditions susceptible to moisture-". the percentage yields of aryl halides (Table 1) are As the tetraorganolead compounds undergo vigo- alwavs higher with ICN than BrCN, (ii) ICN reacts rous reaction with AICl3 even under mild conditions unde-r milder conditions with Ph.Bi than BrCN8,9 yielding a mixture of organolea? chlorides-'', the and (iii) CICN does not react with the Si-Ar bond reactions of BrCN and ICN WIth tetraarylleads while BrCN does10, it is reasonable to arrange these were conducted under various conditions in different cvanogen halides in the following decreasing order solvents in the absence of a catalyst. The arvl- of reactivity: INC>BrCN>CICN, which is also lead bonds remained unaffected with either of the the decreasing order of their bond polaritye- and reagents and the reactants were recovered quanti- thus lends support to the mechanism proposed above tativelv in each case. where electrophiles with greater bond polarity are The -cleavage of aryl-MR3 bonds (demetallations) expected to be more reactive. by electrophilic reagents. ar~ closely analogous to Acknowledgement familiar aromatic substitutions": 111 the latter, the aryl-H bond is broken in the direction C--H~, 'vVe are thankful to the CSIR, New Delhi, for and in the demetallation the aryl-MR3 bond IS the award of a senior research fellowship (to P.R.), broken in the direction C--MR:;. The ease of electro- to Nitto Kasei Kogyo Co., Osaka, for tributyltin

800 BHATTACHARYA & RAJ: CLEAVAGE OF M-C BOND IN ORGANOMETALLICS chloride, to Prof. T. N. Srivastava of this Depart- 11. GRIGNARD, V. & PERRICHON, H., Ann. Chim., 5 (1926) 5. ment for cyanogen iodide and to Dr R. C. Srivastava 12. SRIVASTAVA, T. N. & BHATTACHARYA, S. N., Z. anorg. allgem. Chem., 102 (1966), 344. for helpful discussions. 13. BHATTACHARYA, S. N., EABORN, C. & WALTON, D. R. M., J. chem, Soc., (C) (1969), 1367. References 14. INGHAM, R. K., ROSENBERG, S. D. & GILMAN, H., Chem, 1. EABORN, C., J. organomeial, Chem., 100 (1975), 43. Rev., 60 (1960), 471. 2. FOLARANMI, A., MCLEAN, R. A. N. & WADIBIA, N., 15. HARTMAN, W. W. & DREGEV, E. E., Org. Syntli., Call. J. organometal, cu«, 73 (1974), 59. Vol. II (1943). 150. . 3. BHATTACHARYA, S. N., PREM RAJ & SRIVASTAVA, R. C., 16. SRIVASTAVA, T. N., BHATTACHARYA, S.N. & BAJPAI, K.K., J. organometal. Chem., 105 (1976),45. J. Indian chem, sc«, 49 (1972), 1143. 4. BULLPITT, M. L. & KITCHING, W., J. organometal. cie«; 17. WILLEMSENS, L. C. & VAN DER KERK, G. J. M., 34 (1972). 321. Investigation in the field of organolead chemistry (Intern. 5. BHATTACHARYA, S. N., PREM RAJ & SRIVASTAVA, R. C., Lead Zinc. Res. Organ., New York), 1965, 122. J. organometal; cu-«, 87 (1975), 279. 18. VOGEL, A. I., Practical organic chemistry (Long mans, 6. AYNSLEY, E. E., GREENWOOD, N. N., HUNTER, G. & Green, London). 1971. SPARGUE, M. J.. J. chem, Soc., (A) (1966). 1344. 19. SHAPIRO, H. & FREY, F. W., The organic compounds of 7. FIESER, L. F. & FIESER, M., Reagents for organic synthesis lead (John Wiley, London). 1968, 82. (John Wiley, New York). 1968. 20. STOCK, L. M. & SPECTOR, A. R., J. org. Chem., 28 (1963), 8. CHALLENGER, F. & ALLPRESS, C. F., J. chem, Soc., (1915), 3272. 16. 21. PREM RAJ, Ph.D. Thesis, Electrophilic cleavage and 9. WILKINSON, J. F. & CHALLENGER, F., J. chem. Soc., related reactions of group IV metal-carbon bonds, Uni- (1924), 854. versity of Lucknow, 1977. 10. BARTLETT; E. H., EABORN, C. & WALTON, D. R. M., 22. McDANIEL, D. H. & YINGST, A., J. Am. chem, Soc., 86 J. organometal. cs-«, 46 (1972). 267. (1964), 1334.

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