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Kinetics of the Reaction Between Triphenylphosphine and Some Haloalkanes

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Kinetics of the Reaction Between Triphenylphosphine and Some Haloalkanes Indian Journal of Chemistry Vol. 30A, November 1991, pp.929-935 Kinetics of the reaction between triphenylphosphine and some haloalkanes DV S Jain* & R Chadha Department of Chemistry, Panjab University, Chandigarh 160014 Received 27 February 1991; accepted 8 July 1991 Kinetics of reactions RX + (C6Hs)3P- (C6Hs)3PR+X-(R = CCI3,CBr3,CH2Br, C4H9 and X = Br, Cl, Ii have been studied at different temperatures and in different dielectric media. The values of second or- der rate constants of the reactions with tetrahalomethanes are much higher than those with partially hal- ogenated alkanes. This suggests that the reaction may be of charge transfer type with tetrahalomethanes while with other haloalkanes it is simple nucleophilic substitution reaction of SN2 type. A mixture of triphenylphosphine (TPP) and tetra- used as such. I-BB and l-lB were prepared in the halo methane (CX4) (especially X = CI or Br) has laboratory. Carbon tetrachloride was dried over been widely used as a versatile reagent for halogena- phosphorus pentoxide and the middle fraction, b.p. tion, dehydration, for creating P-N linkage and for 349 K was used. Acetonitrile was purified as de- replacing a hydroxyl group with halogen':" under scribed earlier". Tribromomethyltriphenylphos- mild conditions. lnspite of such wide applications of phonium bromide was prepared as described earli- TPP/CX4 systems, there have been few detailed kin- er". Trichloromethyltriphenylphosphonium chlo- etic and mechanistic studies of the reactions between ride and trichloromethyltriphenylphosphonium TPP and CX4. We report herein the results of kinetic bromide were prepared by adding TCM (3.06 g) studies of the reactions of TPP with (CX4) such as and BTCM (1.98 ~ to TPP solution in acetonitrile CCI4, CBr4 and CBrCl3 in different solvents at dif- (5 mI) respectively. The first mixture was heated at ferent temperatures. For comparison we have stud- 323 K forS hr under nitrogen atmosphere while the ied the kinetics of the reaction of partially haloge- second mixture was stirred for 30 min at room tem- nated alkanes, viz. dibromomethane (DBM), perature. Precipitates started separating out in both l-bromobutane (I-BB) and l-iodobutane (l-lB) cases. The precipitates were filtered and recrystal- with TPP. lized from acetonitrile. These were analysed for The reactions between TPP and CX4 have been [(C6H5)3PCCl3]+Cl-, m.p. 448 K (lie m.p. 451 K) shown to lead to formation of various products de- and [(C6H5hPCCI3]+Br- m.p. 458 ± 2 K, respec- pending upon the ratioI.2,5.6in which the reactants tively. are mixed and to some extent on the manner? in Bromomethyltriphenylphosphonium bromide which the reactants are mixed. These complications was prepared by adding DBM (1.57 g) to a stirred arise from the consecutive reactions at higher molar solution of TPP (2.92 g) in dry toluene (10 mI) and ratios of (C6H5)3P/CX4.lt seems that trihalomethyl- mixture refluxed for 20 hr under nitrogen atmos- triphenylphosphonium halide is the initial product phere. The solid obtained was recrystallized from so long as the concentrations of both the reactants acetonitrile" m.p. 510 K (lit" m.p. 513 K).lt analysed are very low and the ratio (C6H5hP/CX4 is less than for [(C6H5)3PCH2Br]+Br-. l-Butyltriphenyl- unity. Therefore, in order to understand the com- phosphonium bromide and I-butyltriphenylphos- plex kinetics of the system it was decided to study ph onium iodide were prepared by refluxing 1-BB the kinetics of the initial reaction (1): (1.37 g) and l-lB (1.84 g) separately with TPP (2.62 g) in dry benzene (10 mI) at 353 K. The solids were CX (C6H5)3P--[(C6H5)3PCX,]+X- ... (1) 4 + recrystallized from acetonitrile. These were ana- The progress of the reaction was studied conduc- lysed for [(C6H5)3PC4H9]+Br-(m.p. 503 K) and tometrically as the product is ionic and the conduc- [(C6H5)3PC4H9]+I- (m.p. 493 K), respectively. tance increases with time. Kinetic study Materials and Methods The progress of the reaction was followed con- Triphenylphosphine (TPP)(Sisco Research Labo- ductometrically. In order to determine [phosphoni- ratories), TBM (BDH) and DBM (Fluka AG) were um salt] conductometrically the standard curves 929 INDIAN J CHEM, SEC.A, NOVEMBER 1991 were obtained between specific conductance and ious [reactants] and temperatures are given in Table corresponding [phosphonium salt]. The stock solu- 1. The reaction between TBM and TPP is extremely tions of desired [TPP] and [haloalkanes ] were pre- fast at room temperature therefore the kinetics of pared in dry acetonitrile (or any other solvent). Af- the reaction was studied in the temperature range of ter prethermostating the reactant solutions separ- 263 to 281 K. Activation energies of the reactions ately these were mixed in the reaction vessel and were determined from the Arrhenius plots and are conductance was measured at different intervals of given in Table 2 along with the frequency factors time. The conductance data were converted into the and entropies of activation. corresponding [phosphonium salt] with the help of The effect of dielectric constant of the medium on standard curves. the rate constants for the reactions of TPP with TBM and TCM was studied by carrying out the Results and Discussion reaction in mixtures of acetonitrile and l,4-dioxane The order of the reaction: (£ = 13.58 to 35.94). The dependence of rate con- (C6H:;hP+ RX -+ [(C6HshPR]+ X stant of a reaction on dielectric constant is generally (R = CBr3, CCl3, CH2Br, C4H9) with respect to the given by Eq.(2). reactants was established by Ostwald's method. The lnk= In kg + 3/8kT(1- ell + e )(,u;/rl reaction was found to be first order in each reactant. 2 3 2/ 3) The values of the second order rate constants at var- + ,uB/rB -,u. r , ...(2) Table 1- Values of second order rate constants of the reactions of TPP with halo alkanes T{K) [TPPJ [TBMJ k T{K) [TPPJ [TBMJ k J 3 (mol dm-3) (mol dm-·l) (drrr' mol-I S-I) (mol dm- ) (moldm- ) (dm-'mol-Is-I) TPP+ TBM; E = 19.58 E = 24.71 263 0.10 0.20 0.12 263 0.05 0.50 0.33 0.10 0.50 0.14 0.10 0.10 0.34 ~·O.lO 1.00 0.11 0.10 0.20 0.36 0;20, 0.50 0.14 0.10 0.50 0.37 0.40· 0.50 0.15 0.20 0.50 0.36 0.14 ± 0.02 0.35 ± 0.02 273 0.05 0.20 0.25 273 0.05 0.20 0.74 0.05 0.50 0.25 0.05 0.50 0.74 0.10 0.10 0.28 0.10 0.10 0.80 0.10 0.20 0.28 0.10 0.20 0.75 0.10 0.50 0.27 0.10 0.50 0.75 0.10 1.00 0.27 0.10 1.00 0.74 0.20 0.20 0.30 0.20 0.20 0.78 0.20 0.50 0.3\ 0.20 0.50 0.76 0.76 ± 0.Q2 0.28 ±0.02 281 0.05 0.10 0.48 281 0.05 0.10 1.28 0.48 0.05 0.20 0.05 0.20 1.23 0.49 0.05 0.50 0.05 0.50 1.02 0.10 0.10 0.50 0.10 0.10 1.26 0.10 0.20 0.49 0.10 0.20 1.21 0.10 0.50 0.49 0.10 0.50 1.23 1.00 0.10 0.50 0.10 1.00 1.14 0.20 0.20 0.52 0.20 0.20 1.23 0.20 0.50 0.50 0.20 0.50 1.17 0.50± 0.Q2 1.26 ± 0.07 Contd. 930 JAIN et al.: KINETICS OF TRIPHENYLPHOSPHINE-HALOALKANES REACTION Table l=-Values of second order rate constants of the reactions of TPP with haloalkanes- Contd T(K) J02 x [TPP] J02x [TBM] k T(K) [TPP][TeM] 10) k (mol drn t') (mol dm-3) (dm3mol-'s-') (mol dm-3) (mol dm-.l) (drn ' mol-' s-') e = 35.95 313 0.02 0.20 0.57 263 0.02 0.10 1.41 0.05 0.05 0.68 0.05 0.40 1.47 0.05 0.1"0 0.66 0.10 0.10 l.38 0.05 0.20 0.61 0.10 0.20 1.47 0.05 0.50 0.47 0.10 0.40 1.40 0.10 0.20 0.57 0.10 0.80 1.41 0.20 0.20 0.55 0.20 0.20 l.34 0.59 ±0.06 1.41 ± 0.04 318 0.02 0.20 0.71 273 0.02 0.10 2.59 0.05 0.05 0.86 0.05 0.10 2.56 0.05 0.05 0.86 0.05 0.20 2.51 0.05 0.10 0.76 0.40 0.05 2.67 0.05 0.20 0.75 0.10 0.10 2.83 0.05 0.50 0.63 0.10 0.20 2.91 0.10 0.20 0.71 2.70 ± 0.17 0.20 0.20 0.72 281 0.01 0.20 3.87 0.74 ±0.06 0.02 0.10 3.67 0.05 0.10 4.31 e = 19.58 0.05 0.20 4.09 303 0.01 0.10 0.57 0.05 0.40 4.34 0.02 0.05 0.65 0.10 0.10 4.60 0.02 0.10 0.61 0.20 0.20 4.37 0.02 0.20 0.56 4.17 ± 0.26 0.02 0.50 0.61 0.05 0.10 0.61 T(K) [TPP] [TCM] 10-' k 0.10 0.10 0.56 (mol dm-3) (mol dm-J) (drrr' mol-' s-') 0.59 ± 0.04 TPP+TCM; f= 13.82 308 0.01 0.10 0.76 303 0.02 0.20 0~29 0.02 0.05 0.84 0.05 0.05 0.36 0.02 0.10 0.77 0.05 0.02 0.33 0.02 0.20 0.75 0.05 0.50 0.28 0.02 0.50 0.66 0.10 0.20 0.33 0.05 0.10 0.80 0.20 0.20 0.32 0.10 0.10 0.76 0.32 ± 0.Q3 0.76 ± 0.05 308 0.02 0.20 0.43 0.05 0.05 0.53 313 0.01 0.10 1.08 0.05 0.10 0.50 0.02 0.05 1.l6 0.05 0.20 0.45 0.02 0.10 1.l6 0.05 0.50 0.37 0.02 0.20 ).02 0.10 0.20 0.42 0.02 0.50 0.94 0.20 0.20 0.40 0.10 0.10 1.00 0.45 ± 0.04 1.06 ± 0.Q7 (Contd.i 931 INDIAN J CH~M, SEC.A.
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