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Reactivity of Benzenesulfonic Acids in the Hydrogen-Isotope Exchange Reaction

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Reactivity of Benzenesulfonic Acids in the Hydrogen-Isotope Exchange Reaction RADIOISOTOPES,52,57-64(2003) Original Reactivity of Benzenesulfonic Acids in the Hydrogen-Isotope Exchange Reaction Dongyu ZHAO, Hiroshi IMAIZUMI* and Naoki KANO* Graduate School of Science and Technology, Niigata University *Department of Chemistry and Chemical Engineering , Faculty of Engineering, Niigata University 8050 Ikarashi 2-Nocho, Niigata-shi, Niigata Pref. 950-2181, Japan Received September 2, 2002 In order to reveal the reactivity of a functional group in an aromatic compound having two substituents in the aromatic ring, the hydrogen-isotope exchange reaction (T for-H exchange reaction) between tritiated water vapor (HTO vapor) and 3-amino-4-methoxybenzenesulfonic acid (and 2-aminotoluene-5-sulfonic acid) was dynamically observed at 50•Ž (and 70•Ž) in a gas-solid system. Consequently, the specific activity of the acid increased with time, and it showed that the T for-H exchange reaction occurred. Applying the A•h-McKay plot method to the data observed, the rate constant of each functional group for the reaction was obtained. After the additive property of the Hammett's rule was applied to this work; the new substituent constants were obtained. From the above-mentioned, the following four items have been confirmed. (1) The reactivity of the functional groups can be dynamically analyzed, and the A•h-McKay plot method is useful to analyze the reactivity. (2) The additive property of the Hammett's rule is applicable to quantitative comparison of the reactivity of the functional groups. (3) The reactivity of the functional groups can be simultaneously analyzed by using the A•h-McKay plot method in the T-for-H exchange reaction. (4) The method used in this work is also useful for analyzing the reactivity of a certain material having some kinds of functional groups. Key Words : trisubstituted aromatic compound, gas-solid reaction, T-for-H exchange reaction, Hammett's rule, the A•h-McKay plot method, rate constant, benzenesulfonic acid society, now it seems that the more the 1. Introduction number of nuclear power plants (the reprocess- Recently, environmental pollution by ing plants for spent nuclear fuel, and advanced radioactive materials becomes a serious study of nuclear fusion) are, the more is the problem around the world. Tritium (3H or T) amount of T. The total radiation doses of contamination is one type of pollution. T is a tritium are relatively great among the radioisotope of hydrogen. Since the maximum radionuclides in atmospheric nuclear testy. So energy of the radiation (i.e., ƒÀ-ray) from T is the study of tritium-impact on environment very low (18.6 keV), the external exposure (and human being) turns more and more from T is not so important. However, if T is important. The exchange reaction between incorporated into human body, the following tritiated-water vapor and an aromatic problem must be considered since the half-life compound in gas-solid system had been studied of T is relatively long (12.3y) compared with for last twenty years. To determine the rate the human mean life. With development of constants (k) for the compound, the A•h-McKay (3) 58 RADIOISOTOPES Vol.52, No.2 plot method was applied to the data obtained. scintillation counter. The specific activity was Some Hammett plots were made using both k corrected by calculation every three months values and the substituent constants, and the because the specific activity decreased with effect of the substituents on the reactivity was radioactive decay. revealed. With regard to monosubstituted 2)-5), The samples of 3-amino-4-methoxybenzene- disubstituted (except ortho-position) 6)-8), and sulfonic acid and 2-amino-5-sulfonic acid were 1, 3, 5-trisubstituted aromatic compounds9), purchased from Aldrich Chemical Company, the rate constants and the substituent Inc. and Wako Pure Chemical Industries, Ltd., constants were well fitted on the Hammett plot. respectively. The samples were sufficiently As for trisubstituted aromatic compound powdered in an agate mortar, and then sieved having substituent (s) in ortho-position, the to obtain a grain size between 53 and 75 ƒÊm in applicability to the Hammett's rule has not diameter. Then the sieved samples were dried been so far clarified. So the compounds of 3- in a vacuum oven at 70•Ž till constant weight. amino-4-methoxybenzenesulfonic acid (and After that, the sample was preserved in a 2-aminotoluene-5-sulfonic acid) were selected desiccator containing silica gel. Each sample to employ the T-for-H exchange reaction with thus prepared was used for the gas-solid HTO water in a gas-solid system. exchange reaction. In this work, the following aims were chosen : (1) to quantitatively clarify the 2.2 The method of observation reactivity of NH2 and S03H groups in a Using the sample materials above-mentioned compound, (2) to clarify the effect of the and the vacuum line12), the hydrogen-isotope temperature (and the substituents) on the exchange reaction (i.e., T-for-H exchange reactivity of the functional group, (3) to reaction) was observed in a gas-solid system at ascertain whether the A•h-McKay plot method 50•Ž (and 70•Ž). The method of the is applicable to clarify the reactivity of the observation was roughly followings : (1) the groups, and (4) to ascertain whether the mass of each solid sample used was 12 mg per Hammett's rulelo),11) is useful to analyze the run ; (2) after the reaction, distilled water was reactivity of aromatic compounds which have used to dissolve the solid materials used in the three kinds of functional groups (i.e., two sub- T-for-H exchange reaction ; (3) the activity of stituents and one functional group). the resulting solution was measured with a liquid scintillation counter. The data observed 2. Experimental was analyzed with the A•h-McKay plot method, 2.1 Sample materials and k for each solid sample material used was HTO water whose specific activity is 5•~10-3 obtained. Ci g-1 was purchased from Japan Radioisotope Previously2), it was found that H atoms Association, and was diluted to 1.6•~10-5 directly bonded to benzene ring could not Ci g-1 (i.e., 6•~105 Bq g-1) with distilled water. exchange with T atoms in HTO vapor in the T- The HTO water thus prepared was used in for-H exchange reaction. Accordingly, it was this work, whose specific activity was considered that only H atoms in the NH2 and determined accurately with a liquid S03H groups of the solid sample material used (4) Feb. 2003 Z. Dongyu et al.: Reactivity of benzenesulfonic acids in the hydrogen-isotope exchange reaction 59 in this work could exchange with T in HTO A; (b) the latter reaction continued, and the vapor. Prior to the observation, it was latter one was also attained equilibrium at confirmed (by calculation and experiment) that Point B; (c) the T-diffusion reaction into the three conditions3),8) for applying the A•h- inner phase of the sample occurred. McKay plot method were satisfied. Consequently, the first part in Fig. 1 corresponds to Reactions (1) and (2) shown as 3. Results and Discussion follows, the second one corresponds to 3.1 The reactivity of amino and sulfonic Reaction (3), and the third corresponds to the acid groups diffusion reaction. In order to clarify the reactivity of NH2 and HO3S-C6H3(CH3)NH2+HTO•¬ SO3H groups in a trisubstituted aromatic TO3S-CsH3(CH3)NH2+H2O(1) compound, the T-for-H exchange reaction H03S-CsH3(CH3)NH2+HTO•¬ between 3-amino-4-methoxybenzene sulfonic HO3S-CsH3(CH3)NHT+H2O(2) acid (or 2-aminotoluene-5-sulfonic acid) and TO3S-C6H3(CH3)NH2+HTO•¬ HTO vapor was observed at 50•Ž (and 70•Ž). TO3SC6H3(CH3)NHT+ H2O(3) The time-dependence of the exchange reaction In order to apply the A•h-McKay plot method at each temperature and each sample material to the data shown in Fig. 1, x•‡(F2) is initially was similar with each other. For the simplicity, calculated. Where, x•‡(F2) means the specific only the relation between the reaction time and activity of T in the NH2 group in the surface of specific activity of T in 2-aminotoluene-5- the sample when the exchange reaction sulfonic acid at 70•Ž was given in Fig.l. The between HTO vapor and the NH2 group figure showed that the reaction did occur attained equilibrium because the reactivity of because the activity of T in 2-aminotoluene-5- the SO3H group was much larger than that of sulfonic acid increased with time. Figure 1 consists of the following three parts : (a) the first part is the area from the origin to Point A; (b) the second one is the area from Point A to Point B; (c) the third is the area from Point B to the right end of the line. Previously13), it was found that the reactivity of the SO3H group was much larger than that of the NH2 group when the two groups existed in the same molecule. Accordingly, the three parts mentioned above correspond to the following three reactions, respectively: (a) two reactions (between HTO vapor and the SO3H group (and the NH2 one) at the surface of the solid sample) proceed at the same time, and the Fig.1 Specific activity vs. time for the reaction former reaction between HTO vapor and the between 2-aminotoluene-5-sulfonic acid and SO3H group was attained equilibrium at Point HTO vapor at 70•Ž. (5) 60 RADIOISOTOPES Vol.52, No.2 Fig. 2 A•h-McKay plot of NH2 group for Fig. 3 A•h-McKay plot of SO3H group for 2-aminotoluene-5-sulfonic acid at 70•Ž.
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