Kinetics and Mechanism of Acetoxymercuration and Acid-Catalysed Hydration of α-Alkylstyrenes
Abstract
:Introduction
Results and Discussion
Acetoxymercuration
c | Me | Et | Pr | Bu | Pe | isoBu | isoPr | sec-Bu | tert-Bu |
262 | 270 | 268 | 269 | 268 | 270 | 268 | 262 | 260 | |
5.00 10-3 | 9.90 10-5 | 3.12 10-4 | 1.88 10-4 | 2.19 10-4 | 2.66 10-4 | 6.90 10-5 | 2.47 10-5 | 2.24 10-5 | 6.07 10-5 |
6.67 10-3 | 1.44 10-4 | 4.01 10-4 | 2.40 10-4 | 2.86 10-4 | 3.33 10-4 | 8.83 10-5 | 3.20 10-5 | 2.86 10-5 | 9.00 10-5 |
7.67 10-3 | 1.51 10-4 | 4.83 10-4 | 2.84 10-4 | 3.29 10-4 | 3.73 10-4 | 9.80 10-5 | 3.77 10-5 | 2.66 10-5 | 1.08 10-4 |
8.33 10-3 | 1.72 10-4 | 5.24 10-4 | 2.96 10-4 | 3.52 10-4 | 4.08 10-4 | 1.06 10-4 | 4.00 10-5 | 3.60 10-5 | 1.04 10-4 |
9.00 10-3 | 1.88 10-4 | 5.62 10-4 | 3.18 10-4 | 3.84 10-4 | 4.44 10-4 | 1.19 10-4 | 4.30 10-5 | 3.88 10-5 | 1.10 10-4 |
1.00 10-2 | 2.02 10-4 | 5.75 10-4 | 3.39 10-4 | 4.15 10-4 | 4.87 10-4 | 1.27 10-4 | 5.43 10-5 | 3.65 10-5 | 1.21 10-4 |
1.17 10-2 | 2.26 10-4 | 6.73 10-4 | 3.88 10-4 | 4.84 10-4 | 5.73 10-4 | 1.46 10-4 | 6.30 10-5 | 4.25 10-5 | 1.35 10-4 |
1.33 10-2 | 2.63 10-4 | 7.22 10-4 | 4.42 10-4 | 5.46 10-4 | 6.67 10-4 | 1.60 10-4 | 6.80 10-5 | 4.79 10-5 | 1.55 10-4 |
1.43 10-2 | 2.77 10-4 | 7.49 10-4 | 4.58 10-4 | 5.71 10-4 | 8.25 10-4 | 1.71 10-4 | 7.50 10-5 | 5.18 10-5 | 1.78 10-4 |
1.50 10-2 | 2.87 10-4 | 7.96 10-4 | 4.88 10-4 | 5.84 10-4 | 8.35 10-4 | 1.75 10-4 | 8.37 10-5 | 5.76 10-5 | 1.69 10-4 |
1.60 10-2 | 2.96 10-4 | 8.55 10-4 | 5.16 10-4 | 6.38 10-4 | 8.93 10-4 | 1.87 10-4 | 8.90 10-5 | 6.07 10-5 | 1.67 10-4 |
1.67 10-2 | 3.13 10-4 | 8.86 10-4 | 5.23 10-4 | 6.44 10-4 | 9.04 10-4 | 1.91 10-4 | 9.63 10-5 | 6.62 10-5 | 1.73 10-4 |
1.80 10-2 | 3.32 10-4 | 9.08 10-4 | 5.57 10-4 | 6.92 10-4 | 1.08 10-3 | 2.04 10-4 | 1.06 10-4 | 8.16 10-5 | 1.90 10-4 |
2.00 10-2 | 3.73 10-4 | 9.93 10-4 | 6.03 10-4 | 7.46 10-4 | 1.20 10-3 | 2.18 10-4 | 1.04 10-4 | 1.26 10-4 | 1.97 10-4 |
n = 9, s = 0.058, R = 0.995.
Acid-Catalysed Hydration of α‑Alkylstyrenes
c | Me | Et | Pr | Bu | Pe | isoBu | isoPr | sec-Bu | tert-Bu |
250 | 242 | 242 | 246 | 250 | 240 | 238 | 240 | 226 | |
1.00 | 2.64 10-4 | 2.44 10-4 | 5.39 10-5 | 1.13 10-4 | 1.46 10-4 | 1.15 10-4 | |||
1.50 | 6.16 10-4 | 5.59 10-4 | 4.93 10-4 | 1.21 10-4 | 2.68 10-4 | 3.90 10-4 | 2.50 10-4 | ||
2.00 | 1.34 10-3 | 1.19 10-3 | 9.26 10-4 | 2.50 10-4 | 5.62 10-4 | 7.26 10-4 | 4.96 10-4 | ||
2.50 | 2.61 10-3 | 2.24 10-3 | 1.83 10-3 | 5.59 10-4 | 1.10 10-3 | 1.40 10-3 | 1.03 10-3 | ||
3.01 | 6.59 10-3 | 4.95 10-3 | 3.82 10-3 | 1.41 10-3 | 2.94 10-3 | 3.26 10-3 | 2.65 10-3 | ||
3.08 | 1.57 10-3 | ||||||||
3.39 | 1.36 10-3 | ||||||||
3.50 | 1.11 10-2 | 9.84 10-3 | 6.85 10-3 | 4.60 10-3 | 6.64 10-3 | 4.27 10-3 | |||
3.56 | 1.21 10-2 | 9.92 10-3 | 9.18 10-3 | 4.62 10-3 | 6.55 10-3 | 6.72 10-3 | |||
3.89 | 2.63 10-3 | ||||||||
4.09 | 2.62 10-2 | 1.83 10-2 | 1.68 10-2 | 6.19 10-3 | 1.06 10-2 | 1.39 10-2 | 8.49 10-3 | 6.28 10-5 | |
4.44 | 3.04 10-2 | 3.08 10-2 | |||||||
4.51 | 4.21 10-2 | 3.62 10-2 | 2.79 10-2 | 9.68 10-3 | 1.89 10-2 | 2.03 10-2 | 1.92 10-2 | 1.08 10-4 | |
4.82 | 4.24 10-2 | 4.16 10-2 | 2.93 10-2 | ||||||
5.00 | 9.78 10-2 | 6.88 10-2 | 4.36 10-2 | 1.13 10-2 | 3.42 10-2 | 5.55 10-2 | 3.39 10-2 | 2.28 10-4 | |
5.10 | 8.38 10-3 | ||||||||
5.56 | 7.89 10-3 | ||||||||
5.97 | 1.72 10-2 | ||||||||
6.89 | 5.12 10-3 | ||||||||
7.33 | 2.02 10-2 |
c | Et | Pr | Bu | Pe | isoBu |
2.00 | 1.16 10-4 | 1.87 10-4 | |||
2.06 | 1.35 10-3 | ||||
3.01 | 6.24 10-4 | ||||
3.50 | 9.08 10-4 | 1.06 10-3 | |||
4.09 | 2.31 10-3 | 3.59 10-3 | 2.30 10-3 | 1.57 10-2 | |
4.51 | 3.33 10-3 | 4.86 10-3 | 5.89 10-3 | 2.09 10-2 | |
5.00 | 1.24 10-2 | 1.28 10-2 | 2.50 10-2 | 3.74 10-2 | |
5.56 | 3.34 10-2 | ||||
5.97 | 5.48 10-2 | ||||
6.50 | 9.66 10-2 |
n = 5, s = 0.0204, R = 0.9933.
R | kHgAc | kH1 | m‡m* | kH2 |
Me | (1.35±0.03) 10-2 | (1.12±0.06) 10-4 | 1.35±0.01 | Indiscernible |
Et | (3.80±0.07) 10-2 | (9.00±0.47) 10-5 | 1.13±0.14 | (2.08±0.55) 10-5 |
Pr | (2.27±0.05) 10-2 | (7.60±0.33) 10-5 | 1.32±0.13 | (2.83±0.43) 10-5 |
Bu | (2.79±0.05) 10-2 | (2.20±0.21) 10-5 | 1.02±0.27 | (3.66±0.22) 10-5 |
Pe | (3.86±0.07) 10-2 | (1.22±0.08) 10-5 | 0.73±0.35 | (1.17±0.16) 10-4 |
iso-Bu | (8.30±0.03) 10-3 | (6.04±0.06) 10-5 | 1.25±0.11 | (1.21±0.12) 10-4 |
iso-Pr | (3.81±0.03) 10-3 | (4.62±0.58) 10-5 | 1.27±0.14 | very slow |
sec-Bu | (3.05±0.03) 10-3 | (4.51±0.17) 10-5 | 1.31±0.19 | very slow |
tert-Bu | (7.83±0.03) 10-3 | (2.29±0.07) 10-8 | 3.28±0.97 | Insensitive |
Experimental
Syntheses of Compounds Studied
R | b.p.[°C]/press[torr], exp. | b.p.[°C]/press[torr], lit. | nD (20 °C), exp. | nD (20 °C), lit. | Yield, % |
Me | 59-61/20 | 52-60/15 [47] | 1.525 | 1.536 [53] | 78 |
Et | 76-79/20 | 73-74/15 [48] | 1.525 | 1.527 [54] | 60 |
Pr | 78-82/10 | 77-78/10 [49] | 1.514 | 1.521 [55] | 68 |
Bu | 80-85/05 | 89-90/10 [50] | 1.523 | 1.523 [56] | 83 |
Pe | 65-70/ 1 | 93-95/10 [51] | 1.511 | 1.510 [57] | 90 |
iso-Pr | 72-78/10 | 71-72/10 [49] | 1.514 | 1.518 [57] | 51 |
iso-Bu | 74-79/ 5 | 83-84/10 [49] | 1.511 | 1.510 [58] | 48 |
sec-Bu | 74-80/ 5 | - | 1.510 | - | 42 |
tert-Bu | 84-90/10 | 73/10 [52] | 1.502 | 1.499 [59] | 14 |
Kinetic Measurements
Mathematical-Statistical Treatment of Results
Acknowledgements
References
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Svoboda, J.; Pelcová, M.; Nevěčná, T.; Pytela, O. Kinetics and Mechanism of Acetoxymercuration and Acid-Catalysed Hydration of α-Alkylstyrenes. Int. J. Mol. Sci. 2005, 6, 30-44. https://doi.org/10.3390/i6010030
Svoboda J, Pelcová M, Nevěčná T, Pytela O. Kinetics and Mechanism of Acetoxymercuration and Acid-Catalysed Hydration of α-Alkylstyrenes. International Journal of Molecular Sciences. 2005; 6(1):30-44. https://doi.org/10.3390/i6010030
Chicago/Turabian StyleSvoboda, Jan, Monika Pelcová, Taťjana Nevěčná, and Oldřich Pytela. 2005. "Kinetics and Mechanism of Acetoxymercuration and Acid-Catalysed Hydration of α-Alkylstyrenes" International Journal of Molecular Sciences 6, no. 1: 30-44. https://doi.org/10.3390/i6010030