220
c. G. ~ V E R B E R G E R AND H. M A K ~
solvolyses of ANTI and NABA catalyzed by the imidazole-acrylic acid copolymer are most likely the result of ion pair formation between a substrate and a binding site in specific sequences. The enlarged selectivity of the imidazole-maleic acid copolymer, compared to the imidazole-acrylic acid copolymer, would be due to the increased electrostatic field potential around the polymer in solution. The results obtained in this investigation suggest that this is the first example of synthetic, polymeric catalysts
Macromolecules
which presumably involve both long and short-range electrostatic interactions in their solvolytic reactions. Acknowledgments. The authors are grateful to Dr. J. C. Salamone and Dr. I. Cho for their helpful discussions. They also wish to acknowledge financial support from the Research Laboratory, U. S. Army, Edgewood Arsenal, under Contract DAAA-15-67-C-0567, and the National Institutes of Health under Grant No. 2 R 0 1 G M 15256-02.
Cooperative Effects Involved in Esterolytic Reactions Catalyzed by Imidazole-Carboxylic Acid Copolymers C. G . Overberger and H. Maki’ Department of Chetnistry, The Unicersity of’Michigan, Ann Arbor, Michigun 48104. Receiced July 30, 1969
ABSTRACT: Studies of the esterolytic activities of copolymers of 4(5)-vinylimidazoleand vinylsulfonic acid, in comparison with those of 4(5)-vinylimidazoleand acrylic acid, were undertaken in order to elucidate the involvement of pendent carboxylate groups in the latter copolymers. It was found that the copolymers which were rich in vinylsulfonic acid were catalytically inactive. These results support the cooperative interaction of pendent imidazole and carboxylate functions in the imidazole-acrylic acid copolymer catalyzed reactions.
I
n the previous paper2 it was reported that copolymers of 4(5)-vinylimidazole with acrylic acid had high selectivity toward the positively charged substrate, 3-acetoxy-N-trimethylanilinium iodide (ANTI), and that this high selectivity could be attributed to that of a specific monomeric sequence along the copolymer chain, i.e., the sequence of carboxylate-neutral imidazole carboxylate (I).
COO-
KVh”
COO-
I It was previously reported from our group that basic pendent groups, such as neutral or anionic imidazole groups3 and phenoxide group^,^ could participate in the solvolytic reaction by interacting cooperatively with neutral, pendent imidazole groups in the solvolyses of esters. Since carboxylate anion has been known to catalyze hydrolyses of esters both intramolecularly5,6 (1) Taken from the dissertation submitted by H. Maki in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of The University of Michigan. (2) C. G. Overberger and H. Maki, Macromolecules, 3, 214 (1970). (3) (a) C. G. Overberger, T. St. Pierre, N. Vorchheimer, J. Lee, and S. Yaroslavsky, J . Amer. Chem. Soc., 87, 296 (1965); (b) C. G. Overberger, T. St. Pierre, and S. Yaroslavsky, ibid., 87, 4310 (1965); (c) C. G. Overberger, T. St. Pierre, C. Yaroslavsky, and S. Yaroslavsky, ibid., 88, 1184 (1966). (4) C. G. Overberger, J. C. Salamone, and S. Yaroslavsky, ibid., 89, 6231 (1967). (5) T. C. Bruice and S . J. Beiikovic, “Bioorganic Mechanisms,” W. A. Benjamin, Inc., New York, N. Y., 1966, pp 173186. (6) E. Gaetjens and H. Morawetz, J . Amer. Chem. Sot., 82, 5323 (1960).
and interm~lecularly,j~s it was anticipated that the pendent carboxylate groups in the imidazole-acrylic acid copolymers (such as in sequence I) might also participate in the catalytic action together with pendent imidazoie groups. This possibility was previously suggested2 in connection with the differences in the catalytic activities between the imidazole-acrylic acid copolymers and the imidazole homopolymer in the solvolysis of the neutral ester p-nitrophenyl acetate (PNPA). The former polymers, rich in the distribution of sequence I, were found to be significantly more active than the latter a t the same degree of dissociation of the pendent imidazolium groups. In order to elucidate the above possibility, copolymers of 4(5)-vinylimidazole with vinylsulfonic acid were prepared and their catalytic activities were compared with those of the imidazole-acrylic acid copolymers. The large difference in basicity and/or nucleophilicity between pendent carboxylate and pendent sulfonate groups in these copolymers were expected to reflect on the reactivity of the respective copolymers, if a pendent carboxylate group participates cooperatively with a pendent imidazole group in the solvolyses of esters. Experimental Section n-Butyl vinylsulfonate was prepared by the procedure of Whitmore and Landan.? Copolymerization of 4(5)-Vinylimidazole with n-Butyl Vinylsulfonate. 4(5)-Vinylimidazole, freshly distilled n-butyl vinylsulfonate (total amount of these monomers, 1.0 g) and azobisisobutyronitrile (0.02 g), was dissolved in 20 ml of reagent grade iz-butyl alcohol in polymerization tubes. After removing oxygen by flushing with dry nitrogen, the (7) W. F. Whitmore aiid E. F. Landan, ibid., 68, 1797 (1946).
COOPERATIVE EFFECTSINVOLVED IN ESTEROLYTIC REACTIONS221
Vol. 3, No. 2, MurcIi-April 1970
TABLE1" RESULTS OF THE PREPARATION OF COPOLYMERS OF 4( ~)-VINYLIMIDAZOLEWITH VINYLSULFONIC ACID ---Polymerizationconditions Feed composn, VIM mol
'Time, hr
9.4 53.0 95.5
25.0 5.0 5.0
1312II-
--
ResultsCopolymer Conversion, composn) wt % VIM mol % 9.9 59.5 25.7
A PNPA
IO9-
7
NABA
0 ANTI
8-
7-
38.6 52.5 83.9
a In n-butyl alcohol, at 60", AIBN as an initiator, with shaking during polymerization. Based on both nitrogen and sulfur contents in the hydrolyzed copolymers.
tubes were sealed and then shaken in a constant-temperature bath at 60" for a proper period. The formed polymers precipitated during polymerization. The obtained dispersions were added to 500 ml of acetone and left overnight. The precipitated polymers were collected by filtration, washed with acetone, and dried in a vacuum oven overnight. The results are summarized in Table I. Hydrolyses of the Copolymers of 4(S)-Vinylimidazole with ??-Butyl Vinylsulfonate. The above mentioned copolymers were placed in a 100-ml round-bottom flask with 50 ml of deionized water. The copolymers of compositions 38.6 and 52.0 mol in imidazole gradually dissolved in water but the other copolymei- (83.9 mol % in imidazole) only swelled. After refluxing overnight, the first copolymer remained in solution, while the osthers partly formed thin films on the walls of the flasks. After evaporating the solutions to a few milliliters, the copolymers were recovered by freeze-drying. The infrared spectra (KBr pellet) of these polymers exhibited a rather broad absorption at 114G1260 cm-1, but no absorption was observed ai 1340 and 1160 cm-'. These copolymers were hygroscopic and the infrared spectra indicated the presence of some water in the sample although almost no weight loss was observed by drying to constant weight at 100" under vacuum. Anul. Found: N, 21.72, 21.80; S, 4.29, 4.89 (83.9 mol in imidazole); N, 11.78; S, 11.37, 12.55 (52.0 mol % i n imidazole); N, 9.43, 9.19; S, 16.21, 17.82 (38.6 mol % in imidazole). Potentiometric Titration of the Copolymers. The method of potentiometric titrations previously reported2 was employed. No raiigeir of dissociation of pendent sulfonic acid groups were observed because of their low pK, values. The ranges of dissociation of the pendent imidazolium groups were found to be broader than those estimated for the imidazole-acrylic zcid copolymers.2 This effect could be due to the formation of zwitterions between the pendent sulfonate and imidazolium ions.8 The results of titrations are summarized in Table 11. Kinetic measurements were performed as previously described.233
0
1
2
c
3 4 lo4 (M)
5
L
6
Figure 1. Plots of k & r d cs. concentration of the imidazolesulfonic acid copolymer (83.9 mol % imidazole) at 26", in 28.5 ethanol-water, pH 9.0, ionic strength 0.02. TABLEII= RESULTS OF THE POTENTIOMETRIC TITRATIONS OF PENDENT IhlIDAZOLIUM IONSIN THE COPOLYMERS OF 4(5)-VINYLIblIDAZOLE WITH VINYLSULFONIC ACID Copolymer composn, VIM mol ?
