References for Problems

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Chapter 1

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Chapter 2

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(1971).

Chapter 3

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2785 (1966). c. D. H. Williams and J. R. Kalman, J. Am. Chern. Soc. 99, 2768 (1977).

Sa. J. E. Baldwin and J. A. Reiss, J. Chern. Soc. Chern. Commun., 77 (1977). b. H. C. Brown, J. H. Kawakami, and S. Ikegami, J. Am. Chern. Soc. 92,6914 (1970). c. R. E. Lyle, E. W. Southwick, and J. J. Kaminski, J. Am. Chern. Soc. 94, 1413 (1972). d. E. C. Ashby and S. A. Noding, J. Am. Chern. Soc. 98, 2010 (1976). e. R. D. G. Cooper, P. V. DeMarco, and D. 0. Spry, J. Am. Chern. Soc. 91, 1528 (1969). 6. W. C. Neikam and B. P. Dailey, J. Chern. Phys. 38, 445 (1963).

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Chapter 4

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Chapter 5

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g, h. D. D. Roberts, 1. Org. Chern. 34, 285 (1969). i. K. L. Servis and J.D. Roberts, 1. Am. Chern. Soc. 87, 1331 (1965).

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g, h. M. Cherest, H. Felkin, J. Sicher, F. Sipos, and M. Tichy, 1. Chern. Soc., 2513 (1965). i. J. C. Martin and P. D. Bartlett, 1. Am. Chern. Soc. 79, 2533 (1957). j. S. Archer, T. R. Lewis, M. R. Bell, and J. W. Schulenberg, 1. Am. Chern. Soc. 83, 2386 (1961). k. D. A. Tomalia and J. N. Paige, 1. Org. Chern. 38, 422 (1973). I. P. Wilder, Jr., and W.-C. Hsieh, 1. Org. Chern. 40, 717 (1975).

m. C. W. Jefford, J.-C. Rossier, J. A. Zuber, S. r:. Suri, and G. Mehta, Tetrahedron Lett., 4081 (1980). 5. J. L. Fry, E. M. Engler, and P. v. R. Schleyer, 1. Am. Chern. Soc. 94, 4628 (1972). 6. F. G. Bordwell and W. T. Brannen, Jr., 1. Am .. Chern. Soc. 86, 4645 (1964). 7. R. Baird and S. Winstein, 1. Am. Chern. Soc. 85, 567 (1963). 8. J. B. Lambert and S. I. Featherman, 1. Am. Chern. Soc. 99, 1542 (1977).

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and R. K. Murray, Jr., 1. Org. Chern. 47, 2740 (1982). k. F. David, 1. Org. Chern. 46, 3512 (1981).

15. W. Franke, H. Schwarz, and D. Stahl, 1. Org. Chern. 45, 3493 (1980); Y. Apeloig, J. B. Collins, D. Cremer, T. Bally, E. Haselbach, J. A. Pople, J. Chandrasekhar, and P. v. R. Schleyer, 1. Org. Chern. 45, 3496 (1980).

16. J. S. Haywood-Farmer and R. E. Pincock, J. Am. Chern. Soc. 91, 3020 (1969). 17. G. A. Olah, A. L. Berrier, M. Arvanaghi, and G. K. Surya Prakash, 1. Am. Chern. Soc. 103, 1122

(1981). 18. J.P. Richard and W. P. Jencks, 1. Am. Chern. Soc. 104, 4689, 4691 (1982).

Chapter 6

1a. K. Yates, G. H. Schmid, T. W. Regulski, D. G. Garratt, H.-W. Leung, and R. McDonald, J. Am. Chern. Soc. 95, 160 (1973).

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2a. H. Wong, J. Chapuis, and I. Monkovic, 1. Org. Chern. 39, 1042 (1974). b. P. K. Freeman, F. A. Raymond, and M. F. Grostic, 1. Org. Chern. 32, 24 ( 1967). c. T. I. Crowell, R. T. Kemp, R. E. Lutz, and A. A. Wall, 1. Am. Chern. Soc. 90, 4638 (1968). d. L. C. King, L.A. Subluskey, and E. W. Stern, 1. Org. Chern. 21, 1232 (1956). e. M. L. Poutsma and P. A. Ibarbia, 1. Am. Chern. Soc. 93, 440 (1971). f. S. P. Acharya and 1-J. C. Brown, Chern. Commun. 305 ( 1968). g. A. Lewis and J. Azoro, 1. Org. Chern. 46, 1764 (1981). h. K. Yates and T. A. Go, 1. Org. Chern. 45, 2377 (1980). 3. D. Y. Curtin, R. D. Stolow, and W. Maya, 1. Am. Chern. Soc. 81, 3330 (1959). 4. W. H. Saunders and A. F. Cockerill, Mechanisms of Elimination Reactions, Wiley, New York,

1973, pp. 79, 80. 5. M. Anteunis ai]d H. L. Peeters . .1. Ore. Chern. 40. 307 ( 1975).

6ab. D. S. Noyce, D. R. Hartter, and R. M. Pollack, 1. Am. Chern. Soc. 90, 3791 (1968). c. C. L. Wilkins and T. W. Regulski, 1. Am. Chern. Soc. 94, 6016 (1972). 7. R. A. Bartsch, 1. Am. Chern. Soc. 93, 3683 (1971). 8. K. Oyama and T. T. Tidwell, 1. Am. Chern. Soc. 98, 947 (1976).

9a. K. D. Berlin, R. 0. Lyerla, D. E. Gibbs, and J. P. Devlin, Chern. Commun. 1246 (1970). b. R. 1. Abraham and J. R. Monasterios, 1. Chern. Soc. Perkin Trans. II, 574 ( 1975). c. H. C. Brown and K.-T. Liu, 1. Am. Chern. Soc. 97, 2469 (1975). d. D. J. Pas to and J. A. Gontarz, 1. Am. Chern. Soc. 93, 6902 (1971 ).

lOa. J. F. Bunnett and S. Sridharan, 1. Org. Chern. 44, 1458 (1979); L. F. Blackwell, A. Fischer, and 1. Vaughan, 1. Chern. Soc., B, 1084 (1967).

b. J. E. Nordlander, P. 0. Owuor, and J. E. Haky, ]. Am. Chern. Soc. 101, 1288 (1979). c. G. E. Heasley, T. R: Bower, K. W. Dougharty, J. C. Easdon, V. L. Heasley, S. Arnold, T. L.

Carter, D. B. Yaeger, B. T. Gipe, and D. F. Shellhamer, 1. Org. Chern. 45, 5150 (1980). d. P. Cramer and T. T. Tidwell, J. Org. Chern. 46,2683 (1981). e. R. C. Fahey and C. A. McPherson, 1. Am. Chern. Soc. 91, 3865 (1965); R. C. Fahey, M. W.

Monahan, and C. A. McPherson, J. Am. Chern. Soc. 92, 2810 (1970). f. C. H. DePuy and A. L. Schultz. 1. Org. Chern. 39,878 (1974).

11a. T. T. Coburn and W. M. Jones, 1. Am. Chern. Soc. 96, 5218 (1974). b. R. B. Miller and G. McGarvey, 1. Org. Chern. 44, 4623 (1979). c. P. F. Hudrlik and D. Peterson, 1. Am. Chern. Soc. 97, 1464 (1975). d. G. Bellucci, A. Marsili, E. Mastrorilli, I. Morelli, and V. Scartoni, 1. Chern. Soc. Perkin Trans. II,

201 (1974). 12. D. S. Noyce, D. R. Hartter, and F. B. Miles, 1. Am. Chern. Soc. 90, 3794 (1968). 13. Y. Packer, K. D. Stevens, and J. 1. Champoux, 1. Am. Chern. Soc. 91,4199 (1969). 14. M. F. Ruasse, A. Argile. and J. E. Dubois, 1. Am. Chern. Soc. 100, 7645 (J 978). 15. W. K. Chwang, P. Knittel, K. M. Koshy, and T. T. Tidwell, 1. Am. Chern. Soc. 99, 3395 (1977). 16. D. J. Pasto and J. F. Gadberry, 1. Am. Chern. Soc. 100, 1469 ( 1978).

Chapter 7

2b. G. L. Closs and L. E. Closs, 1. Am. Chern. Soc. 85, 2022 (1.963). f. R. Breslow, 1. Am. Chern. Soc. 79, 1762 (1957). g. K. Ogura and G. Tsuchihashi, Tetrahedron Lett., 3151 (1971). h. G. L. Closs and R. B. Larrabee, Tetrahedron Lett., 287 (1965). 1. R. B. Woodward and C. Wintner, Tetrahedron Lett., 2689 (1969). j. 1. A. Zoltewicz, G. M. Kauffman, and C. L. Smith, 1. Am. Chern. Soc. 90, 5939 (1968).

3a. T.-Y. Luh and L. M. Stock, 1. Am. Chern. Soc. 96, 3712 (1974).

b. H. W. Amburn, K. C. Kauffman, and H. Shechter, J. Am. Chern. Soc. 91, 530 (1969). 4a. G. A. Abad, S. P. Jindal, and T. T. Tidwell, 1. Am. Chern. Soc. 95, 6326 (1973).

b. A. Nickon and J. L. Lambert, J. Am. Chern. Soc. 84, 4604 (1962). 6. G. B. Trimitsis and E. M. Van Dam, J. Chern. Soc. Chern Commun., 610 (1974). 7. A. Streitwieser, Jr., W. B. Hollyhead, A. H. Pudjaatmaka, P. H. Owens, T. L. Kruger, P. A.

Rubenstein, R. A. MacQuarrie, M. L. Brokaw, W. K. C. Chu, and H. M. Niemeyer, 1. Am. Chern. Soc., 93, 5088 (1971).

8. F. G. Bordwell and F. J. Cornforth, 1. Org. Chern. 43, 1763 (1978). 9a. P. T. Lansbury, 1. Am. Chern. Soc. 83, 429 (1961).

b. D. W. Griffiths and C. D. Gutsche, 1. Am. Chern. Soc. 93, 4788 (1971). c. T. D. Hoffman and D. J. Cram, J. Am. Chern. Soc. 91, 1000 (1969). d. G. Biichi, D. M. Foulkes, M. Kurono, G. F. Mitchell, and R. S. Schneider, J. Am. Chern. Soc. 89,

6745 (1967). e. G. Stork, G. L. Nelson, F. Rouessac, and 0. Grigone, 1. Am. Chern. Soc. 93, 3091 (1971).

10. T. B. Thompson and W. T. Ford, J. Am. Chern. Soc. 101, 5459 (1979). 11. A. Streitwieser, Jr., R. G. Lawler, and C. Perrin, J. Am. Chern. Soc. 87, 5383 (1965); J. E.

Hofmann, A. Schriesheim, and R. E. Nichols, Tetrahedron Lett., 1745 (1965). 12. E. J. Stamhuis, W. Mass, and H. Wynberg, 1. Org. Chern. 30, 2160 (1965). 13. B. G. Cox, 1. Am. Chern. Soc. 96, 6823 (1974). 14. E. L. Eliel, A. A. Hartmann, and A. G. Abatjoglou, J. Am. Chern. Soc. 96, 1807 (1974); J.-M.

Lehn and G. Wipff, 1. Am. Chern. Soc. 98, 7498 (1976). 15. S. Danishefsky and R. K. Singh, 1. Am. Chern. Soc. 97, 3239 (1975). 16. R. B. Woodward and G. Small, Jr., 1. Am. Chern. Soc. 72, 1297 (1950).

17a. E. J. Corey, T. H. Topie, and W. A. Wozniak, 1. Am. Chern. Soc. 77,5415 (1955). b. E. W. Garbisch, Jr., 1. Org. Chern. 30, 2109 (1965). c. F. Caujolle and D. Q. Quan, C. R. Acad. Sci. C 265, 269 (1967). d. C. W. P. Crowne, R. M. Evans, G. F. H. Green and A. G. Long, J. Chern. Soc., 4351 (1956). e. N.C. Deno and R. Fishbein, 1. Am. Chern. Soc. 95, 7445 (1973).

18a. N. S. Mills, J. Shapiro, and M. Hollingsworth, 1. Am. Chern. Soc. 103, 1263 (1981). b. N. S. Mills, 1. Am. Chern. Soc. 104, 5689 (1982).

19. H. M. Walborsky and L. M. Turner, 1. Am. Chern. Soc. 94, 2273 (1972). 20. Y. Jasor, M. Gaudry, and A. Marquet, Tetrahedron Lett., 53 (1976).

Chapter 8

1. R. P. Bell, Adv. Phys. Org. Chern. 4, 1 (1966). 2a. A. Lapworth and R. H. F. Manske, 1. Chern. Soc. 1976 (1930).

b. T. H. Fife, J. E. C. Hutchins, and M.S. Wang, 1. Am. Chern. Soc. 97, 5878 (1975). c. K. Bowden and A.M. Last, Chern. Commun. 1315 (1970). d. P.R. Young and W. P. Jencks, 1. Am. Chern. Soc. 99, 1206 (1977).

3a,b. M. M. Kreevoy and R. W. Taft, Jr., 1. Am. Chern. Soc. 77, 5590 (1955). c,d. M. M. Kreevoy, C. R. Morgan, and R. W. Taft, Jr., 1. Am. Chern. Soc. 82, 3064 (1960).

e. T. H. Fife and L. H. Brod, 1. Org. Chern. 33, 4136 (1968). 4. R. G. Bergstrom, M. J. Cashen, Y. Chiang, and A. J. Kresge, J. Org. Chern. 44, 1639 (1979).

Sa. T. Maugh, II and T. C. Bruice, 1. Am. Chern. Soc. 93, 3237 (1971). b. L. E. Eberson and L.-A. Svensson, 1. Am. Chern. Soc. 93, 3827 (1971). c. A. Williams and G. Salvadori, 1. Chern. Soc. Perkin Trans. II 883 (1972). d. G.~- Rogers and T. C. Bruice, 1. Am. Chern. Soc. 96, 2463 (1974). e. K. Bowden and G. R. Taylor, 1. Chern. Soc. B 145, 149 (1971); M. S. Newman and A. L.

Leegwater, 1. Am. Chern. Soc. 90, 4410 (1968). f. T. C. Bruice and S. J. Benkovic, 1. Am. Chern. Soc. 85, 1 (1963). 6. E. H. Cordes and W. P. Jencks, 1. Am. Chern. Soc. 85, 2843, (1963). 7. E. Anderson and T. H. Fife, 1. Am. Chern. Soc. 95, 6437 (1973). 8. M. W. Williams and G. T. Young, J. Chern. Soc., 3701 (1964). 9. R. Breslow and C. McAllister, 1. Am. Chern. Soc. 93, 7096 (1971).

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Chapter 9

1. P. Reeves, T. Devon, and R. Pettit, J. Am. Chern. Soc. 91, 5890 ( 1969). 2a. H. L. Ammon and G. L. Wheeler. J. Am. Chern. Soc. 97. 2326 (1975).

b. W. v. E. Doering and C. H. DePuy, J. Am. Chern. Soc. 75, 5955 (1953). c. J. H. M. Hill, J. Org. Chern. 32, 3214 (1967). d. D. J. Bertelli, J. Org. Chern. 30, 891 (1965).

3a. C. K. Ingold and E. H. Ingold, J. Chern. Soc., 2249 ( 1928). b. R. J. Albers and E. C. Kooyman, Rec. Trav. Chim. 83, 930 (1964). c. J. R. Knowles and R. 0. C. Norman, J. Chern. Soc., 2938 (1961). d. A. Gastaminza, T. A. Modro, J. H. Ridd, and J. H. P. Utley, J. Chern. Soc. B, 534 (1968). e. J. R. Knowles, R. 0. C. Norman, and G. K. Radda, J. Chern. Soc., 4885 (1960). f. F. L. Riley and E. Rothstein, J. Chern. Soc., 3860 (1964). 4. T. C. van Hoek, P. E. Verkade, and B. M. Wepster, Rec. Trav. Chim. 77, 559 (1958); A. van

Loon, P. E. Verkade, and B. M. Wepster, Rec. Trav. Chim. 79,977 (1960). Sa. W. v. E. Doering and F. L. Detert, J. Am. Chern. Soc. 73, 876 (1951).

b. E. F. Jenny and J. D. Roberts, J. Am. Chern. Soc. 78, 2005 (1956). 6. J. E. Dubois, J. J. Aaron, P. Alcais, J. P. Doucet, F. Rothenberg, and R. Uzan, J. Am. Chern.

Soc. 94, 6823 ( 1972). 7. R. M. Roberts and D. Shiengthong, J. Am. Chern. Soc. 86, 2851 (1964). 8. G. A. Olah, S. J. Kuhn, S. H. Flood, and J. C. Evans, J. Am. Chern. Soc. 84, 3687 (1962). 9. R. L. Dannley, J. E. Gagen, and K. Zak, J. Org. Chern. 38, 1 (1973); R. L. Dannley and W. R.

Knipple, J. Org. Chern. 38, 6 (1973). 10. B. A. Hess, Jr., and L. J. Schaad, J. Am. Chern. Soc. 93, 305 (1971 ).

11 a. C. D. Gutsche and K. H. No. J. Org. Chern. 47, 2708 (1982). b. G. D. Figuly and J. C. Martin, J. Org. Chern. 45, 3728 (1980). c. K. Key, C. Eaborn, and D. R. M. Walton, Organomet. Chern. Synth. 1, 151 (1970-1971). d. S. Winstein and R. Baird, J. Am. Chern. Soc. 79, 756 (1957).

12. R. B. Moodie and K. Schofield, Ace. Chern. Res. 9, 287 ( 1976). 13. P. C. Myhre, M. Beug, and L. L. James, J. Am. Chern. Soc. 90,2105 (1968). 14. P. Rys, P. Skrabal, and H. Zollinger, Angew. Chern. Int. Ed. Engl. 11,' 874 (1972). 15. D. Bostwick, H. F. Henneike, and H. P. Hopkins, Jr., J. Am. Chern. Soc. 97, 1505 (1975). 16. C. K. Ingold, Structure and Mechanism in Organic Chemistry, Second Edition, Cornell University

Press, Ithaca, New York 1969, pp. 340-344; C. G. Swain and D. R. Crist, J. Am. Chern. Soc. 94, 3195 (1972).

17. M. L. Bird and C. K. Ingold, J. Chern. Soc., 918 (1938); J. D. Roberts, J. K. Sanford, F. L. J. Sixma, H. Cerfontain, and R. Zagt, J. Am. Chern. Soc. 76, 4525 (1954).

18. E. Baciocchi, F. Cacace, G. Ciranni, and G. Illuminati, J. Am. Chern. Soc. 94, 7030 (1972). 19. D. S. Noyce, P. A. Kittle, and E. H. Banitt, J. Org. Chern. 33, 1500 (1968). 20. T. Otsubo, R. Gray, and V. Boekelheide, J. Am. Chern. Soc. 100, 2449 (1978). 21. L. M. Jackman and V. R. Haddon, J. Am. Chern. Soc. 96, 5130 (1974); M. Gates, D. L. Frank,

and W. C. von Felten, J. Am. Chern. Soc. 96, 5138 (1974). 22. T. A. Modro and K. Yates, J. Am. Chern. Soc. 98, 424 7 (1976). 23. A. V. R. Rao, V. H. Deshpande, and N. L. Reddy, Tetrahedron Lett., 4373 (1982). 24. E. Vogel, H. Konigshofen, J. Wassen, K. Mullen, and J. F. M. Oth, Angew. Chern. Int. Ed. Engl.

13,732 (1974); J. F. M. Oth, K. Mullen, H.-V. Runzheimer, P. Mues, and E. Vogel, Angew. Chern. Int. Ed. Engl. 16, 872 (1977).

25. G. R. Stevenson and B. E. Forch, J. Am. Chern. Soc. 102, 5985 (1980).

Chapter 10

2a. E. Vogel, Justus Liebigs Ann. Chern. 615, 14 (1958). b. A. C. Cope, A. C. Haven, Jr., F. L. Ramp, and E. R. Trumbull, J. Am. Chern. Soc. 74, 4867

(1952). c. R. Pettit, J. Am. Chern. Soc. 82, 1972 (1960). d. M, Oda, M. Oda, and Y. Kitahara, Tetrahedron Lett., 839 (1976). e. K. M. Rapp and J. Daub, Tetrahedron Lett., 2011 (1976). f. E. J. Corey and D. K. Herron, Tetrahedron Lett., 1641 (1971). 3. A. G. Anastassiou, V. Orfanos, and J. H. Gebrian, Tetrahedron Lett., 4491 (1969); P. Radlick

and G. Alford, J. Am. Chern. Soc. 91, 6529 (1969). 4a. K. B. Wiberg, V. Z. Williams, Jr., and L. E. Friedrich, J. Am. Chern. Soc. 90, 5338 (1968).

b. P. S. Wharton and R. A. Kretchmer, J. Org. Chern. 33, 4258 (1968). c. R. L. Danheiser, C. Martinez-Davila, and J. M. Morin, Jr., J. Org. Chern. 45, 1340 (1980);

R. L. Danheiser, C. Martinez- Davila, R. J. Auchus, and J. T. Kadonaga, J. Am. Chern. Soc. 103, 2443 (1981).

d. R. K. Hill and M. G. Bock, J. Am. Chern. Soc. 100, 637 (1978). e. M. Newcomb and W. T. Ford, J. Am. Chern. Soc. 95, 7186 (1973).

Sa. L.A. Paquette and M. Oku, J. Am. Chern. Soc. 96, 1219 (1974). b. A. E. Hill, G. Greenwood, and H. M. R. Hoffmann, J. Am. Chern. Soc. 95, 1338 (1973). c. S. W. Staley and T. J. Henry, J. Am. Chern. Soc. 93, 1292 (1971). d. T. Kauffmann and E. Koppelmann, Angew. Chern. Int. Ed. Engl. 11, 290 (1972). e. C. W. Jefford, A. F. Boschung, and C. G. Rimbault, Tetrahedron Lett., 3387 (1974). f. M. F. Semmelhack, H. N. Weller, and J. S. Foos, J. Am. Chern. Soc. 99, 292 (1977). g. R. K. Boeckman, Jr., M. H. Delton, T. Nagasaka, and T. Watanabe, J. Org. Chern. 42, 2946 (1977). h. I. Hasan and F. W. Fowler, J. Am. Chern. Soc. 100, 6696 (1978). i. R. Subramanyan, P. D. Bartlett, G. Y. M. Iglesias, W. H. Watson, and J. Galloy, J. Org. Chern.

47, 4491 (1982). 6. A. Anastassiou and R. P. Cellura, Chern. Commun., 1521 (1969).

7a. L.A. Feiler, R. Huisgen, and P. Koppitz, J. Am. Chern. Soc. 96,2270 (1974). b. H. H. Wasserman, J. U. Piper, and E. V. Dehmlow, J. Org. Chern. 38, 1451 (1973-). c. D. A. Evans and A.M. Golob, J. Am. Chern. Soc. 97, 4765 (1975). d. K. Oshima, H. Takahashi, H. Yamamoto, and H. Nozaki, J. Am. Chern. Soc. 95, 2693 (1973). e. N. Shimizu, M. Tanaka, and Y. Tsuno, J. Am. Chern. Soc. 104, 1330 (1982). f. V. Cere, E. Dalcanale, C. Paolucci, S. Pollicino, E. Sandri, L. Lunazzi, and A. Fava, J. Org. Chern.

47, 3540 (1982). g. L.A. Paquette, and M. J. Wyvratt, J. Am. Chern. Soc. 96, 4671 (1974); D. McNeil, B. R. Vogt,

J. J. Sudol, S. Theodoropulos, and E. Hedaya, J. Am. Chern. Soc. 96, 4673 (1974). h. D. Bellus, H.-C. Mez, G. Rihs, and H. Sauter, J. Am. Chern. Soc. 96, 5007 (1974). i. W. Grimme, J. Am. Chern. Soc. 95, 2381 (1973).

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Chapter 11

1. C. C. Lee and D. Unger, Can. 1. Chern. 50, 593 (1972). 2a. E. Vogel, W. Grimme, and E. Dinne, Tetrahedron Lett., 391 (1965).

b. J. Meinwald and J. W. Young, 1. Am. Chern. Soc. 93, 725 (1971 ). c. D. M. Madigan and J. S. Swenton, 1. Am. Chern. Soc. 93, 6316 (1971 ). d. E. J. Corey and A. G. Hartmann, 1. Am. Chern. Soc. 85.4033 (1963).

e, f. K. M. Shumate, P. N. Neumann, and G. J. Fonken, 1. Am. Chern. Soc. 87, 3996 (1965); K. M. Shumate and G. J. Fonken, 1. Am. CheM. Soc. 88, 1073 (1966).

g. H. E. Zimmerman and M.-L. Viriot-Villaume, 1. Am. Chern. Soc. 95, 1274 (1973). h. R. L. Coffin, R. S. Givens, and R. G. Carlson, 1. Am. Chern. Soc. 96, 7554 (1974).

3a. 0. Rodriguez and H. Morrison, Chern. Commun., 6 79 (1971). b. W. G. Dauben and M.S. Kellogg, 1. Am. Chern. Soc. 93, 3805 (1971). c. D. H. R. Barton, D. L. J. Clive, P. D. Magnus, and G. Smith, 1. Chern. Soc. C, 2193 (1971 ).

4a. W. C. 'Agosta and A. B. Smith, Ill, f. Am. Chern. Soc. 93, 5513 (1971). b. W. Ferree, Jr., J. B. Grutzner, and H. Morrison, f. Am. Chern. Soc. 93, 5502 (1971). c. A. Wissner, f. Org. Chern. 42, 356 (1977). d. G. W. Shaffer and M. Pesaro, f. Org. Chern. 39, 2489 (1974). e. D. R. Morton and N.J. Turro, f. Am. Chern. Soc. 95, 3947 (1973). f. H. Hart and A. F. Naples, f. Am. Chern. Soc. 94, 3256 (1972). g. M. Pomerantz and G. W. Gruber, f. Am. Chern. Soc. 93,6615 (1971). h. 0. L. Chapman, G. W. Borden, R. W. King and B. Winkler, f. Am. Chern. Soc. 86, 2660 (1964);

A. Padwa, L. Brodsky, and S. Clough, f. Am. Chern. Soc. 94, 6767 (1972). i. R. K. Russell, R. E. Wingard, Jr., and L.A. Paquette, J. Am. Chern. Soc. 96, 7483 (1974). j. D. I. Schuster and C. W. Kim, f. Am. Chern. Soc. 96, 7437 (1974). k. W. G. Dauben, M. S. Kellogg, J. I. Seeman, and W. A. Spitzer, f. Am. Chern. Soc. 92, 1786

(1970). I. A. Padwa and W. Eisenberg, f. Am. Chern. Soc. 92, 2590 (1970).

m. D. H. R. Barton and G. Quinkert, f. Chern. Soc., 1 (1960). n. R. S. Cooke and G. D. Lyon, f. Am. Chern. Soc. 93, 3840 (1971). o. D. Bryce-Smith and J. E. Lodge, f. Chern. Soc., 695 (1963); E. Grovenstein, Jr., and D. V. Rao,

Tetrahedron Lett., 148 (1961). p. L. E. Friedrich and J. D. Bower, J. Am. Chern. Soc. 95, 6869 (1973). 5. T.-Y. Leong, T. Jmagawa, K. Kimoto, and M. Kawanisi, Bull. Chern. Soc. Jpn. 46, 596 (1973). 6. W. B. Hammond and T. S. Yeung, Tetrahedron Lett., 1173 (1975). 7. H. E. Zimmerman, R. S. Givens, and R. M. Pagni, f. Am. Chern. Soc. 90, 6096 (1968). 8. P. J. Wagner, P. A. Kelso, and R. G. Zepp, f. Am. Chern. Soc. 94, 7480 (1972).

10. N.J. Turro and D. S. Weiss, f. Am. Chern. Soc. 90, 2185 (1968). 11. S. Boue and R. Srinivasan, J. Am. Chern. Soc. 92, 3226 (1970); J. Saltiel eta/., Org. Photochem.

3, 1 (1973). 12. W. G. Dauben, K. Koch, S. L. Smith, and 0. L. Chapman, J. Am. Chern. Soc. 85, 2616 (1963). 13. F. D. Lewis, R. W. Johnson, and D. E. Johnson, f. Am. Chern. Soc. 96, 6090 (1974). 14. H. E. Zimmerman, Angew. Chern. Int. Ed. Engl. 8, 1 (1969). 15. K. R. Huffman, M. Burger, W. A. Henderson, Jr., M. Loy, and E. F. Ullman, f. Org. Chern. 34,

2407 (1969). 16. H. E. Zimmerman, R. J. Boettcher, N. E. Buehler, G. E. Keck, and M. G. Steinmetz, J. Am.

Chern. Soc. 98, 7680 ( 1976). 17. H. E. Zimmerman, R. J. Boettcher, and W. Braig, J. Am. Chern. Soc. 95, 2155 (1973). 18. J. R. Scheffer, K. S. Bhandari, R. E. Gayler, and R. A. Wostradowski, J. Am. Chern. Soc. 97,

2178 (1975). 19. C. W. Jefford and F. Delay, f. Am. Chern. Soc. 97,2272 (1975).

Chapter 12

1a. G. H. Cleland, Org. Synth. 51, 1 (1971). b. K. Fukunishi, Y. Inoue, Y. Kishimoto, and F. Mashio, f. Org. Chern. 40, 628 (1975). c. C. Walling and D. Bristol, f. Org. Chern. 37, 3514 (1972). d. D. H. Miles, P. Loew, W. S. Johnson, A. F. Kluge, and J. Meinwald, Tetrahedron Lett., 3019 (1972). e. K. Pedersen, P. Jakobsen, and S.-0. Lawesson, Org. Synth. V, 70 (1973). f. R. Dowbenko, Org. Synth. V, 93 (1973). g. W. H. Sharkey and C. M. Langkammerer, Org. Synth. V, 445 (1973). h. C. B. Warren, J. J. Bloomfield, J. S. Chickos, and R. A. Rouse, f. Org. Chern. 38, 4011 (1973). 3. L. H. Gale, J. Am. Chern. Soc. 88, 4661 (1961).

4a. W. H. Urry, D. J. Trecker, and H. D. Hartzler, f. Org. Chern. 29, 1663 (1964). b. H. Pines, N.C. Sih, and D. B. Rosenfield, J. Org. Chern. 31, 2255 (1966). c. D. D. Tanner, E. V. Blackburn, and G. E. Diaz, J. Am. Chern. Soc. 103, 1557 (1981). d. H. Driquez, J. M. Paton, and J. Lessard, Can. f. Chern. 55, 700 (1977). e. H. Feuer, J. Doty, and J. P. Lawrence, f. Org. Chern. 38, 417 (1973). f. E. A. Mayeda, f. Am. Chern. Soc. 97, 4012 (1975). g. X. Creary, J. Org. Chern. 45, 280 (1980). h. A. L. J. Beckwith and R. D. Wagner, f. Am. Chern. Soc. 101, 7099 (1979).

709 REFERENCES

FOR PROBLEMS


5. D. D. Tanner, H. Yabuuchi, and E. V. Blackburn, J. Am. Chern. Soc. ·93, 4802 (1971). 6. L. K. Montgomery and J. W. Matt, 1. Am. Chern. Soc. 89, 6556 (1967). 7. P. D. Bartlett, R. E. Pincock, J. H. Rolston, W. G. Schindel, and L.A. Singer, 1. Am. Chern. Soc.

87, 2590 (1965). 8. E. S. Huyser and B. Giddings, 1. Org. Chern. 27, 3391 (1962).

9a. E. Muller, Tetrahedron Lett., 1835 (1974). b. A. L. J. Beckwith and C. J. Easton, 1. Am. Chern. Soc. 103,615 (1981). c. H. C. Brown, M. S. Kharasch, and T. H. Chao, 1. Am. Chern. Soc. 62, 3435 ( 1940). d. P. J. Wagner, K.-C. Liu, andY. Noguchi, 1. Am. Chern. Soc. 103, 3837 (1981). e. A. Effio, D. Griller, K. U. Ingold, J. C. Scaiano, and S. J. Sheng, 1. Am. Chern. Soc. 102, 6063 (1980 f. N. 0. Brace, 1. Am. Chern. Soc. 86, 523 (1964).

10. N. C. Deno, W. E. Billups, R. Fishbein, C. Pierson, R. Whalen, and J. C. Wyckoff, 1. Am. Chern. Soc. 93, 438 (1971).

11. D. H. Levy and R. J. Myers, 1. Chern. Phys. 41, 1062 (1964). 12. J. K. Kochi and P. J. Krusic, 1. Am. Chern. Soc. 90, 7157 (1968). 13. E. I. Heiba, R. M. Dessau, and W. J. Koehl, Jr., 1. Am. Chern. Soc. 90, 5905 (1968). 14. C. L. Karl, E. J. Maas, and W. Reusch, 1. Org. Chern. 37, 2834 (1972). 15. P. R. Story, D. D. Denson, C. E. Bishop, B. C. Clark, Jr., and J.-C. Farine, J. Am. Chern. Soc.

90, 817 (1968). 16. K. J. Shea and P. S. Skell, 1. Am. Chern. Soc. 95, 6728 (1973). 17. W. A. Bonner and F. D. Mango, J. Org. Chern. 29, 430 (1964). 18. D.]. De Frees, R. J. Mciver, Jr., and W. J. Hehre, 1. Am. Chern. Soc. 102, 3334 (1980).

Index

ab initio molecular orbital calculations 18-19 on methane 28-31 of rotational barriers 134-137

acetaldehyde conformation of 135-136 hydration of 404

aceta Is formation from aldehydes and alcohols 406 hydrolysis of 406-411 intramolecular catalysis of hydrolysis 437-439 of salicylic acid, mechanism of hydrolysis 437-

438 acetylation

of alcohols and amines 433-437 of cis- and trans-4-tert-butylcyclohexanol 138-

139 by Friedel-Crafts reaction 515-517

acetylene and derivatives acidity of 378 addition reactions of 341-345 bonding in 5

acetyl nitrate, in aromatic nitration 505 acid anhydrides 433, 436, 440 acid chlorides, acylation reactions ·of 433-435,

515 acidity

of acetic acid and derivatives 15-17 of alcohols 211 of conjugate acids of nucleophiles (table) 265 of diastereotopic protons in benzyl methyl

sulfoxide 90 of hydrocarbons 373-382 kinetic versus thermodynamic 375 of phenols 21 0 of substituted benzoic acids 181-184

acidity functions 201-202, 250

acrolein conformation of Ill electron delocalization in 9 molecular orbitals of 47-48

acylation of alcohols and amines 433-436 of aromatic compounds 515-518

acylium ions, as intermediates in ester hydrolysis 423-424 in Friedel-Crafts reactions 515-516

acyl radicals addition to alkenes 669, 676 decarbonylation 640, 678-679 generation 669, 679

adamantane derivatives, nucleophilic substitution in 248, 260, 275-276

addition reactions of acetylenes 341-345 of alkenes

polar 323-341 radical 664-676

Diels-Alder 557-566 dipolar cycloaddition 567-569 of ketenes 569-571 photochemical 603, 607-610, 615

alcohols acylation of 433-436 dehydration of 361 gas phase acidity of 211-212 reaction with thionyl chloride, stereochemistry

of 287 aldehydes

acetal formation from 406 autoxidation of 661 conformation of II 0, 135-136 free-radical addition reactions of 669, 676

711

712

INDEX

aldehydes (cont.)

hydration equilibria for 404-405 nucleophilic addition to 403-420

Alder rule 558 alkenes

addition reactions of

with aldehydes, free-radical

with benzene, photochemical

with bromotrichloromethane,

free-radical 668-669 with dibromocarbene 80 epoxidation 79-80

669, 676 615-616

with formamide, free-radical 670 halogenation 333-339 hydration 330-332 with hydrogen halides, free-radical 664-666 with hydrogen halides, polar 324-330 with phenoxycarbene 81-82 polar, limiting mechanisms 323-324 with thiols, free-radical 664-666

bridgehead 145-146 conformation of 108-109 photochemistry of 604-607 relative stability of isomers 13-14 stereochemical descriptors E and Z 76, 77

alkoxy radicals 631, 635-636 alkylation

of a mines 79, 83 of aromatic compounds 512-514

a I k y lid enecyclo hex a nes

allylic strain in 123 optically active 67-68

alkyl halides

from alkenes and hydrogen halides 324-329, 664-666

formation in substitution reactions 287 allenes

optically active 67-68 resolution by kinetic method 74

allyl anion

molecular orbitals of 47, 49 resonance stabilization of 8, 378

allyl cation

cycloaddition reactions of 48-51, 566 formation of, by ring opening of cyclopropyl

cations 540-542 resonance stabilization of

allyl radical, stabilization of

allylic strain 123, 395 alpha effect 267 amide acetals. hydrolysis of

amides

from esters 426-430 hydrolysis of 431-432 resonance in 421

ammes

acylation of 433-436

8-9. 469 12-13. 649-653

428-429

deamination of 285-287 pyramidal inversion 63

amine oxides, allylic, rearrangements of 557 amino acids

absolute configuration of 65-68 asymmetric synthesis of 90-91

aminoethylene, molecular orbitals of 47 angle strain

in [I O]annulene 463 in bridgehead free radicals 640 in cyclobutanes 124 in cyclopropanes 6, 7. 124 definition 6, 100-10 I effect on reactivity 141-146

annulenes (see also benzene, cyclobutadiene,

cyclooctatetraene, etc.) 43, 44, 460-468 anomeric effect 130-133, 137 antarafaeial, definition 544 antiaromaticity

definition 459 of transition states 538, 546-547, 562, 603

antioxidants 646-647 aromatic substitution, general mechanism

for 481-488 aromaticity 455-459

of annulenes 460-468 of benzene 10, 457-459 of charged rings 468-474 Hiickel's rule 41-42, 455-457 of polycylic hydrocarbons 475 of transition states of concerted reactions 538,

546, 562 Arrhenius equation 177

aryl participation 295-297 aspirin, hydrolysis mechanism 438-440 asymmetric induction

Cram's rule 90 definition 82 in synthesis of amino acids 90-91

aufbau principle 24 autoxidation 660-662 axial dissymmetry 67, 68 azo compounds

as radical source 636 thermolysis of, activation parameters for 178

azulene hydrogen-deuterium exchange in

structure and stability 478-479

Baeyer-Villiger reaction 661 Baldwin's rules 148-150 barbaralane, rearrangement of 554

512

Barton reaction (see nitrite esters, photolysis)

basicity 264-266 effect on elimination reactions 353-354 of solvent-base systems 374-375

basis set. definition 19-20

benzene acidity of 378 aromaticity of 10, 457-459 bonding in l 0 delocalization energy 43, 457 molecular orbital description 42-43, 456 nitration 169-171, 504 photochemical reactions 614-615 radical anion of 629-631, 640 reso na nee in lO

benzocyclobutadiene 478 benzvalene 614 benzylic radicals, stabilization of 12-13, 649, 652 biaryls

optically active 67-68 racemization of 85

bicyclic rings, strain in 7, 142-146 bicyclo[ l.l.O]butane, reactivity 143 bicyclo[2.2.l]hept-2-ene systems

addition reactions of 153-154, 329 ?-substituted, rr-participation of 293-294

bicyclo[ 4.\.0]hepta-2,4-dienes, valence isomerism of 539

bicyclo[2.2.0]hexa-2,5-diene (see Dewar benzene) bifunctional catalysis 442 Birch reduction 640 bond angle, relationship to hybridization 4-7 bond dissociation energies

in hydrogen atom abstraction reactions 652-653

table II bond energies ll-13

in calculation of heats of reaction 653 table ll, 652

bonding in benzene l 0, 458-459 in diatomic molecules 24-28 in free radicals 637-641 in hydrogen 2 in methane 28-31

bond lengths in annulenes 462-467 and aromaticity 459 in cyclooctatetraenide dianion 471 in enols of {3-dicarbonyl compounds 392-393 strain energy associated with distortion I 00 table II

bond polarity, definition 14-17 Bredt's rule 145 bridged annulenes 464-466 bridged cations (see carbonium ions) bridgehead alkenes 145-146 bridgehead carbonium ions 261 bridgehead radicals 640 bromination

of acetylenes 344-345 of alkenes 333-339

of aromatic compounds 509-510 of 1,2-dimethylcyclopropane 143 free radical 655-656 kinetics of 336 of toluene 654-655

N-bromoamides, free radical reactions of 672 bromonium ions, as intermediates in

bromination 333, 335-336 N-l;lromosuccinimide, in bromination 659 bromotrichloromethane, radical addition to

alkenes 668-669, 675 Br\'lnsted catalysis law 199-200, 405 B-strain 276 bullvalene 554 1,3-butadiene

addition of allyl cation to 49-51 addition of halogens to 339 conformation of 109-110 derivatives, Diels-Alder reactions of 557-566

n-butane, conformation I 03-104 !-butene, conformation l 08-l 09 butenyl radical, formation from cyclopropyl

radical 630-632 ten-butyl cation

formation, in superacid 258 heat of formation 249

tert-butyl chloride, solvolysis of 178, 204 tert-butyl group, effect on cyclohexane

conformation 119 tert-butyl hypochlorite, chlorination

with 659-660 tert-butyl radical, structure 638 2-butyl tosylate, rearrangement during

solvolysis 299-300

Cahn-Ingold-Prelog convention (see sequence rule) capto-dative stabilization of radicals 651 carbanions

definition 373 stabilization by substituents 23, 382-390 structure of 379, 389-390

carbenium ions (see carbonium ions) carbodiimides, in acylation reactions 435 carbonium ions

allylic, structure of 254 benzylic, substituent effects on 254-255 cycloheptatrienyl 256, 468 cyclopropenyl 468-469 formation of

by Cu(II) oxidation of free radicals 663, 680-682

by electrooxidation 683 by Pb(IV) oxidation of carboxylic acids 682 in superacid media 257-260

heats of formation of 249 hydride affinity of 252-253

713 INDEX

714

INDEX

carbonium ions (coni.)

as intermediates in addition to alkenes 324, 325, 327-332, 337-

339, 344 electrophilic aromatic substitution 169-171,

484-493, 500-502,512-517 hydrolysis of acetals and ketals 407-411 nucleophilic substitution reactions 238-240 solvolysis reactions 239-240, 243-248, 284

norbornyl cation formation from cyclopentenylethyl

tosylate 295 hydride shifts in 309 as intermediate in additions to

norbornene 329 structure of 305-312

pentacoordinate 310 phenyl, structure of 262

pKR· values for 250-251 rearrangements of 258, 298-303 relative stability of 22-23, 252-256 stabilization of

cyclopropyl substituents 256, 260 norbornyl cation 311 resonance 249, 254-256 substituents 252-256, 298

triphenylmethyl, structure of 249 vinyl, stability of 262

carbon monoxide, molecular orbitals 25-28 carbon tetrabromide, radical addition reactions

of 666-669 carbon tetrachlorid~, radical addition reactions

of 666-669 carbonyl compounds

enolization of 384, 390-395 hydration of 404-406 photochemistry of 592-603 relative reactivity of 417-421 tetrahedral intermediates from 403, 411-414,

427-430 carboxylate salts

electrolytic decomposition of 683 oxidation by Pb(IV) acetate 682

carboxylic acid chlorides acylation reactions of 433-435

carboxylic acids activation toward acylation 433-437 as catalysts for enol ether hydrolysis 200, 391 oxidative decarboxylation of 682-683 substituent effects on ionization 15-16

catalysis 197-202 of acetal and ketal hydrolysis by

acids 407-411 by acids and bases 197-202 bifunctional 442 of Diels-Alder reactions by Lewis acids 566 in Friedel-Crafts reactions 512, 515-517 intramolecular 437-443

nucleophilic 424-425, 434, 439 tautomeric 442

chemically induced dynamic nuclear polarization (CIDNP) 632-634

chirality, definition 62 chlorination

of acetylenes 343-344 of alkanes 656-658 of alkenes 334-338 of aromatic compounds 507-508 of butane 648-649 by free-radical mechanism 656-658

CION P (see chemically induced dynamic nuclear polarization)

C!aisen rearrangement 178, 555-556 competition experiments, in free radical

reactions 648 concerted reactions

cycloadditions and cycloeliminations 557 -57! definition 529 electrocyclic reactions 530-544 sigmatropic reactions 178, 544-557

configuration definition 61 specification of

by Cahn-lngold-Prelog convention 65-67 by Fischer convention 64-65

conformation ofalkanes 107-108 of alkenes I 08-109 of carbonyl compounds 110-111 Curtin-Hammett principle in relation

to 219-220 of cyclohexane derivatives 112-123 of cyclooctatetraene 462 definition 61, 99 of d ienes I 09 effect on reactivity 137-141,218,219

conformational free energy, definition and table of 116-119

conjugation 8 conrotatory, definition 531 Cope elimination 81 Cope rearrangement 550-555 copper

as catalyst in decomposition of aryl diazonium ions 663 reactions of peroxy esters 680

organo-reagents, as intermediates 681 correlation diagrams 51

for Diels-Alder reactions 560-562 for electrocyclic processes 533-537 for photochemical 2 + 2 cycloaddition 588 for photochemical electrocyc!ic reactions

590 for thermal 2 + 2 cycloaddition 588

Coulomb integral 39 Cram's rule 90

crown ethers 207, 269 Curtin-Hammett principle 219-220 cyano compounds, acidity of 383, 387 cyanohydrins 192, 419-420 cycloaddition reactions 557-571

I ,3-dipolar 567-569 of ketenes 570-571 photochemical 588-589, 593 thermal 557-571

cycloalkanes conformations of 123-127 stereochemistry of substituted 71-72 strain energies of 124, 142

cycloalkenes photochemistry of 607 stability of isomeric 145

1 rans-cycloalkenes formation in photochemical reactions 607 optically active 67-68, 84-85 stability of 144-146

cyclobutadiene molecular orbitals of 42-43 preparation and reactions 460-461 structure and bonding of 456-457

cyclobutadienyl dication 471 cyclobutane derivatives

conformation 124-125 formation in cycloaddition reactions 588, 596-

597,608-609, 612, 614 cyclobutene derivatives, electrocyclic ring

opening 530-538, 590 cyclobutenyl cation, homoaromaticity of 474 cyclodecane, conformation 127 cyclodecapentaene ([ 1 0]-ann ulene) 463-464 cycloheptane, conformation 126 cycloheptatriene

acidity 470 valence isomerism 539, 549

cycloheptatrienyl cation 256, 470 lrans-cycloheptene 144 cyclohexadiene, photochemical ring opening 593,

611 cyclohexadienones, photochemical rearrangement

of 601-602 cyclohexanes, conformation of 111-123 cyclohexanols, stereochemical effects on

reactivity 138-140 cyclohexanones

conformation of 122 nucleophilic addition to 419 stereoselective reactions of 150-152

cyclohexenes conformation of 123 photochemical addition reactions of 607

4-cyclohexenyl tosylate, solvolysis of 300 cyclohexyl chloride, isolation of conformational

isomers 116

cyclohexyl iodide, determination of conformational equilibrium by NMR 116-117

cyclohexyl tosylate, nucleophilic substitution in 284

cyclononatetraene, anion of 470 cyclooctadienyllithium, electrocyclic ring closure

of 543 cyclooctane derivatives, conformations of 126 cycloocatetraene and derivatives

conformation of 462-463 reduction of 471,642 structure and stability of 461-462 tetramethyl, dication of 471 valence isomerism of 462-463

cyclooctatrienyl cation, homoaromaticity of 473-474

trans-cyclooctene 68, 84-85, 144 cyclopentadiene

acidity of 378, 470 dimerization of 177

cyclopentadienide anion 470 cyclopentadienyl cation 470-471 cyclopentane derivatives, conformations 125 cyclopentenones, photochemistry 599-600 cyclopentenyl cations, formation from pentadienyl

cations 542-543 cyclopentenyl tosylate, 1r-participation in

solvolysis 294-295 cyclopentyl tosylate, nucleophilic substitution

in 288 cyclopropane derivatives

bonding in 6, 7 protonated in carboni urn rearrangements 301,

310 ring-opening of 143, 631-632 solvolysis 540-542 vinyl, isomerization of 522-555

cyclopropanone, addition reaction of 567 cyclopropenyl cations

molecular orbitals of 43 stability of 256, 468-469

cyclopropyl cations, electrocyclic ring-opening of 540-542

cyclopropylmethyl cation 260 cyclopropylmethyl radical 630-632 L-cysteine, configuration of 67

dealkylation, during electrophilic aromatic substitution 519

deamination reactions (see diazonium ions) debromination, of vicinal dibromides 362-363 decalin derivatives

conformation of cis and trans 120-121 conformational effects on reactivity 137, 286

decarboxylation of acyloxy radicals 633, 635, 641, 681-683 by electrolytic oxidation 682-683

715 INDEX

716

INDEX

2,4,6,8-decatctraenes, electrocyclic reactions of 540

degenerate rearrangement, definition 553 dehalogenation

during electrophilic aromatic substitution 519 reductive, in preparation of

cyclobutadiene 460 of vicinal dihalides 362-363

dehydration, of alcohols 361 dehydrogenases, stereochemistry of reactions

of 87 dehydrohalogenation, of alkyl halides 79, 81,

346-360 delocalization, definition I 0 delocalization energy

for aromatic systems 457 from Hiickel MO calculations 40-43 in polyenes 40

d-orbital, in stabilization of carbanions and ylides 387-390

deoxymercuration 363 D and L descriptors 64, 66-67 Dewar benzene derivatives

in photolysis of benzene derivatives 615 synthesis and stability 538-539

diacyl peroxides, decomposition 635, 681 dialkyl peroxides, decomposition 635-637 diamagnetic ring current

in [!4]annulene 465 in [18]annu!ene 467 in bridged annulenes 466 as criterion of aromaticity 459 in homoaromatic systems 474

diamond-lattice conformations of cyc!oa!kanes 126-127

diastereomers definition 61 equilibration of 117, 119-121 examples of 69-76 specification of configuration of 69-71

diastereotopic faces 90-91 ligands 88-90

I ,3-diaxial interactions in cyclohexanes 114, 1!9, 121, 122 in 1,3-dioxanes 129 in 1,3-dithianes 130

diazonium ions alkyl, reactions of 273-274, 285-286 aryl

as electrophilic reagents 517-518 radicals from 662-663

dihromocarbene, stereochemistry of addition to alkencs 79, 80

dielectric constants of common solvents (table) 203

Diels-Alder reaction 558-566 catalysis of by Lewis acids 566

dimerization of cyclopentadiene by, activation parameters for 177

trapping of trans-cyc!oheptene hy 144 I ,3-dienes

addition reactions with hydrogen halides 328-329

conformations of 109-110 halogenation of 339 molecular orbitals for 565 photochemistry of 608-611

I ,4-dienes di-rr-methane rearrangement of 611-614 intramolecular photocycloaddition of 614

1 ,5-dienes, Cope rearrangement of 550-551 dienophilcs

molecular orbitals for 565 relative reactivity of 563-564

/3-diketones acidity of 383 enolization of 392-394

I ,3-dimethylallene, kinetic resolution of 74 dimethyl sulfoxide

acidity measurements in 374-376, 382 as aprotic dipolar solvent 268 basicity of base solutions in 374-375 solvent effect on nucleophilicity 268

di-rr-methane rearrangement 611-614 I ,3-dioxane derivatives, conformational equilibria

Jn 128-131 1,3-dioxolane, free radical addition to

alkenes 670 dipolar aprotic solvents 203 dipolar cycloaddition 567-568 I ,3-dipolar molecules

examples of 562-568 molecular orbitals for 569

dipole moments and anomeric effect 130 of azulene 479 of calicenes 480-481 of excited state of formaldehyde 593 table 15

diradical intermediates in photochemical reactions 597, 599-60 I, 603, 608-613

directed valence 3 dispersion forces I 02-103 disrotatory, definition 532 I ,3-dithiane

acidity of 387-388 derivatives, conformation of 129

cis-divinylcyclopropane rearrangements 552-555 dual substituent parameter equation 186-187 dynamic stereochemistry 76-85 dynamics, chemical 1

electrocyclic reactions 530-544 of annulenes 464 photochemical 589-592

electrolysis, of carboxylate salts 683 electron delocalization

in allylic cations 8, 9, 254 in anomeric effect 132-133 in benzene I 0, 456 in carbanions 378, 383 in carbonium ions 254-256 in cyclohexadienyl cations 9, 489-493 in enolates 8, 383 in free radicals 627-629, 638, 642-643,

649-652 in 2-methylallyl anion 8 in norbornyl cation 305-312 resonance description of 7-10 in SN2 transition state 240-242, 277-278 in a,,B-unsaturated carbonyl compounds 9

electron density calculation by MO methods 20-21 for ethylene 36-38 for substituted benzenes (table) 495

electronegativity (table) 14 electron paramagnetic resonance

spectroscopy 628-632, 637-642, 644 electron spin resonance spectroscopy (see electron

paramagnetic resonance spectroscopy) electron transfer reactions

metal ion catalyzed 679-683 in SRN I reactions 683-690

electrophilic aromatic substitution reactions 169-171,214,218,481-520

diazonium coupling 517-518 Friedel-Crafts reactions 512-517 general mechanism 482-488 halogenation 505-511 Hammond's postulate and intermediates

in 214-218, 499 intermediates and transition state for 169-171,

214-218 nitration 503-505 substituent effects on 215-218

elimination reactions general mechanisms for 345-351 orientation in 351-356 photochemical 597 stereochemistry of 78-80, 356-361

empirical force field calculations (see molecular mechanics)

enamines 395 hydrolysis of 416

enantiomeric relationships 62-68 enantiotopic

faces 87 ligands 86, 87

energy-level diagrams derivation from MO theory 24-28,31-35,

456 for electronic states in photochemical

processes 586, 606

energy level, molecular orbital for annulenes 42-44 for benzene 42, 456 for carbon monoxide 25-27 for cyclobutadiene 42, 456 for ethylene 31-35,45-47 for linear polyenes 40-41 for methane 28-31

energy of activation, definition 174 enolates

generation of 384-386 kinetic and thermodynamic control of

formation 213-214, 386 as reaction intermediates 172, 197, 644, 690 in SRN I reactions 689-690 stability of 311

enol ethers, hydrolysis of 200, 332 enolization

equilibria for 394 measurements of rates of 384, 385, 391

enols 390-395 equilibria involving 391-393 esters as acylating agents 436 formation of 390-394 from photoenolization 595-596 stability of 394

enthalpy 161-165 of activation 176-178 calculation of

for bromination of alkanes 653 for hydrogenation of /rans-2-butene 162-

163 entropy 161-162

of activation 177-179 epimerization, definition 78 erythro, as descriptor for diastereomers 70 erythrose 70 ESCA

application to structure of methane 30-31 application to structure of norbornyl

cation 311 definition 30

esters alcohol interchange of 426 hydrolysis of 421-426 reactions with amines and ammonia 426-429 resonance in 421 of salicylic acid, hydrolysis of 438-440 solvent effects on hydrolysis 208-209

ethane bromination of 653 rotational barrier of 53-55, 101-102, 135

ethers autoxidation of 661-662 formation in solvolysis by neighboring group

participation 291-292 ethylene

acidity of 378

717

INDEX

718 INDEX

ethylene (cont.)

bonding in 4-5 molecular orbitals of 31-36,45-47

ethyl fluoride, rotational barrier in 135 ethyl radical, EPR spectrum of 630-631 excited state

of formaldehyde, structure 593-594 lifetime and energy transfer in 584-588 for photoisomerization of stilbene 606-607

E and Z descriptors 76, 77

field effects 182, 186 Fischer convention

application to diastereomers 70 definition 64

fluorescence, definition 586 fluorination,

of alkanes 658 of alkenes 338 of aromatic compounds 510-511

fluoromethanol, conformation 137 fluorosulfonic acid 257 formaldehyde

excited state of 493 molecular orbitals of 45-46

formamide, free radical addition to alkenes 669-670

Franck-Condon principle 584 free energy 161-163

of activation, definition 144 relationship with equilibrium constant 104-

105, 162 free radicals

aryl, reactions of 662-663 bridgehead 640 charged 641-644 detection 628-634 fragmentation of 678-679 generation 634-637 intramolecular reactions of 671-676 rearrangements of 676-678 reorganization energy of 652-653 stability of 626-628, 649-652 structure of 637-641 vinyl 641

Friedel-Crafts reactions acylation 515-517 alkylation 512-514

frontier orbital analysis of cycloaddition reactions 48-5 I, 562-564 of electrocyclic reactions 532-534 of electrophilic aromatic substitution 493-

494 of photochemical 2 + 2 cycloaddition

reactions 589 of sigmatropic rearrangements 544-549

Frost's circle 43 fulvalene 480

fulvene 480 fumarase 88

gauche conformation of axial cyclohexane substituents 114, 120 of butane l 03-l 05 of fluoromethanol 137 of methoxymethyl fluoride 133

gauche effect 133, 13 7 general acid catalysis

definition 199 in hydration of alkenes 330-331 in hydrolysis of acetals and ketals 407-408,

437 in hydrolysis of enol ethers 199-200 in hydrolysis of esters 424, 439, 441-442 in imine formation 415

general base catalysis definition 198 in hydrolysis of esters 424, 439, 441-442 in imine formation 415

geometric isomers, as diastereomers 61, 76 glyceraldehyde

configuration of 66 as reference for Fischer convention 64, 70

H-, basicity constant 374 HR, acidity function 250 halogenation (see also bromination, chlorination)

of acetylenes 344-345 of aldehydes and ketones 385, 391 of alkenes 333-339 of aromatic compounds 505-511 by free radical mechanisms 655-660

a-haloketone effect 122-123 a-haloketones

as precursors of photochemical intermediates 601-602

reactivity towards nucleophilic substitution 277-278

halonium ions 333 Hammett equation 179-185, 188

bromination of aromatic compounds 509 bromination of substituted styrenes 337 bromination of substituted toluenes 655 chlorination of aromatic compounds 507 chlorination of arylacetylenes 343 cyanohydrin formation 420 electrophilic aromatic substitution 499-50 I hydration of acetylenes 343 hydration of substituted styrenes 330-331 hydrolysis of acetals 407-410 hydrogen-deuterium exchange of aromatic

compounds 511 mercuration of alkenes 340 solvolysis of 2-arylethyl tosylates 297

Hammond's postulate 214-218, 491, 499, 656 hard-soft-acid-base concept 266-267

heat of formation in calculation of heat of

hydrogenation 162-163 for isomeric hydrocarbons 12-13

heat of hydrogenation of alkenes (table) 13-14 calculation of 162-163

hemiacetal 406 hemiketal 406 heptafulvene 480 heptalene 479 heptatrienyl anion, electrocyclic ring closure

of 544 heterocyclic molecules, conformational analysis

of 128-133 heterotopic ligands, definition 86 hexaphenylethane 626 I ,3,5-hexatriene

electrocyclic ring-closure of 532-533, 538-539

molecular orbitals of 39-41 5-hexenyl radical, cyclization of 674-675, 683 Hofmann rule 353 Hofmann-Loeffler reaction 671 homoaromaticity 472-474 homotopic ligands, definition 86 homotropilidene 554 Hiickel and Mobius systems

in cycloaddition reactions 562 in electrocyclic reactions 538 in sigmatropic reactions 546

HUcke! molecular orbital calculations 37-44 HUcke! rule 41-44, 455-456, 472, 473 hybridization (see orbital hybridization) hydration

of acetylenes 343 of alkenes 330-332 of carbonyl compounds 404-405

hydrazone formation 415 hydride affinity 252 hydride shifts, in carbonium ions 298-303 hydrocarbons

acidity of 373-382 stability of isomeric 12-14

hydrogen atom abstraction in alkene photolysis 607 in free radical reactions 631, 637, 640-641,

653-662,664-666,670-675,677 in photochemical reactions of carbonyl

groups 594-597 from tin hydrides 677 from triethylsilane 63 7

hydrogen bonding, intramolecular in vic-diols I 06 in enolized dicarbonyl compounds 392-393 in 5-hydroxy-1 ,3-dioxolane 130

hydrogen halides, reactions with alkenes 324-330, 646-666

hydrogen molecule molecular orbitals for 24 structure for 3

hydrolysis of acetals and ketals 406-411, 437-438 of ami des 431-432 of enamines 416 of enol ethers 200-201 of esters 421-426, 438-442 ofimines 413-415

hydroperoxides, as intermediates in autoxidation 647, 660-661

hyperconjugation 51-53, 256 hyperfine splitting 629-630 hypochlorites, reactions of 659-660, 673, 679 hypochlorous acid, in aromatic chlorination 508 hypohalites, in aromatic halogenation 510

imines, hydrolysis of 413-417 iminium ions, as intermediates in reactions of

carbonyl compounds 417 induced decomposition 636 inductive effects

on acidity of acetic acid derivatives 15-17 on acidity of carbon acids 383 in aromatic substituent effects 182 in nucleophilic substitution reactions 277-

278 origin of 16

inhibition of free radical reactions 646 initiation of free radical reactions 646 intersystem crossing 584, 594 intramolecular catalysis 437-443 inversion of configuration, definition 78 iodination

of alkanes 658 of alkenes 338 of aromatic compounds 510

N-iodoamides, free radical reactions of 672 ionization potential 30-31 ion-pairs 244, 376

effect on kinetic acidity measurements 379-381

effect on stereochemistry of elimination reactions 360

as intermediates in addition reactions of alkenes 327

in nucleophilic substitution reactions 244-248, 283-284

solvent effects on 206-207 ipso-substitution 494, 520 isodesmic reactions

application to estimation of benzene resonance energy 458-459

definition 163 in evaluation of substituent effects in

electrophilic aromatic substitution 492 isomers, classification of 61

719

INDEX

720

INDEX

isotope effects 190-194 in alcohol dehydration 361 in bromination of aromatic compounds 509 in diazo coupling 518 in electrophilic aromatic substitution 485-486,

501-502 in enolization of cyclohexanone 391 in hydrogen abstraction by photoexcited

carbonylgroups 594 in hydrogen-deuterium exchange in

azulene 512 in nitration of aromatic compounds 504 secondary, in nucleophilic aliphatic

substitution 287-289 solvent 201, 330, 361, 407 isotopic labelling 220-221

in acylation reactions 434-435 in carbonium ion rearrangements 300, 302,

329, 365 in Claisen rearrangement 555 in debromination of vicinal dibromides 362 in detection of degenerate rearrangements 550,

632 in detection of ion-pair return 245 in detection of photoenolization 595-596 in detection of transannular hydride shifts 302 in determination of stereochemistry of enzyme

reactions 87-89 in ester hydrolysis 422, 424, 439 in hydration of carbonyl compounds 404 in hydration of styrenes 330 in hydrogen halide additions to

norbornene 329 in hydrolysis of aspirin 439 in measurement of kinetic acidity 376, 385 in photochemical di-rr-methane

rearrangement 612 in photochemistry of alkyl nitrites 673 in sigmatropic hydrogen migration 547 in solvolysis of benzhydryl benzoates 245 in solvolysis of isopropyl benzenesulfonate 245 in stereoisomerization of cyclopropanes 552 in study of phenylalanine hydroxylase 221

ketals (see also acetals) formation of 406 hydrolysis of 406-411

ketenes cycloaddition reactions of 570-571 as intermediates in acylation

reactions 434-435 as intermediates in photochemical

reactions 196 ketones

acidity of 383-386 conformations of II 0-111 enolization of 390-394 a-halo (see a-halo ketones)

photochemistry of cleavage reactions 596-597 cycloaddition reactions 603 hydrogen abstraction 594-595, 674

relative reactivity toward addition 419-420 a,/3-unsaturated, conformation of 111 a,/3-unsaturated, photochemistry of 597-600 /3, y-unsaturated, photochemistry of 600-601

ketyls 642-643 kinetic acidity 375 kinetic control, definition 212-213 kinetic resolution, definition 74 kinetics 165-179

of addition of hydrogen halides to alkenes 326 of bromination of alkenes 336 of chlorination of alkenes 337 of chlorination of anisole 508 of Friedel-Crafts alkylation 513 of nitration of benzene 169-171 of radical chain reactions 644-647 of S;\1 I substitution 238-239 of SN2 substitution 242

Kolbe electrolysis 683

lead tetraacetate, as oxidant 682 leaving groups

in elimination reactions 353-361 in nucleophilic substitution reactions 271-274

Lewis acids, as catalysts in aromatic halogenation 507-510 in Diels-Alder reaction 566 in Friedcl-Crafts reaction 513-517

Lewis structures, in depicting electron delocalization 3, 7-10

ligand transfer reactions 681 linear combination of atomic orbitals (LCAO)

approximation 18 linear free-energy relationships 179-190 lithium, organo- compounds, as bases 381-382 localization energy, definition 493 London forces (see also dispersion forces) 102

Markownioffs rule 325 matrix isolation 196, 457 McConnell equation 629-630 mercuric ion, in addition reactions of

alkenes 340-341 mercury, organo- compounds, elimination

reactions of 363-364 mero-stabilization of radicals 651 meso-configuration, definition 71 mesomerism 190 metal ions, reactions with alkenes 339-341 methane

acidity of 378 ESCA spectrum 31 molecular orbitals 28-30

methanol, rotational barrier 108

methylamine, rotational barrier l 08 methyl anion

energy as a function of geometry 21-22, 379 stabilization by substituents 23

methyl cation energy as a function of geometry 21-22 molecular orbitals of 21 substituent effects on stability of 23

methyl radical detection of 626 energy as a function of geometry 21-22 geometry 637-638

methylsilane, rotational barrier l 08 microscopic reversibility 176, 323 Mobius array

and aromaticity 467-468 for transition states in concerted reactions 537 of transition state of di-rr-methane

rearrangement 612 molecular mechanics I 00-l 04

calculation of cyclohexane conformational barrier 113

molecular orbital theory in analysis of concerted reactions 530-544 application to conformational

analysis 133-137 calculation methods 17-23

ab initio 18-19 CNDO 19 extended Hucke! 19 INDO 19 MIND0-3 19, 164 MNDO 19, 164

description of SN2 transition state 241, 277-278

description of substituent effects on radicals 650

estimation of substiuent effects on carbonium wns 254-256

Hucke! approximation 37-44 in description of aromaticity 455-456

interpretation of the anomeric effect 132-133 interpretation of butene conformation 109 interpretation of dipolar cycloaddition

reactions 568-569 interpretation of regioselectivity in the Diets

Alder reaction 514-515 interpretation of substituent effects in

electrophilic aromatic substitution 491-495

interpretation of substituent effects on structure of radicals 638

qualitative application of 23-36 reaction energy calculations by 164 transition state geometry from 176

Mosher's reagent 76

naphthalene, radical anion 642

neighboring group participation 289-297 neopentyl halides, nucleophilic substitution

in 283 nicotinamide adenine dinucleotide coenzyme 87 NIH shift 221 nitration

of aromatic compounds 503-505 of benzene, kinetics of 169-171

nitrite esters diazotization by 663 photolysis of 673

nitroalkanes acidity of 383, 386 anions of, in SRN l reactions 683-688 tertiary, reduction by methanethiolate 688

p-nitrobenzyl halides, SRN l reactions of 684-686

nitronium ion, as active nitrating species 483, 503-504

N-nitrosoamides, as sources of free radicals 637, 662

nitroso compounds, in spin-trapping 632 nitroxide radicals 628, 632 nonbonded interactions 100, 105-106 nonclassical carbonium ions 304-312, 329 nonradiative decay of excited states 586 norbornane derivatives

elimination reactions of 258 solvolysis reactions 304-309

norbornene addition of formic acid 79, 82 addition of hydrogen halides 329 free radical addition to 669 photochemistry of 607 stereochemistry of addition to 153

7-norbornenyl tosy1ate, acetolysis of 293-294 norbornyl cation 304-312 norcaradiene, equilibrium with

cycloheptatriene 549 nuclear magnetic resonance

as a criterion of aromaticity 459 (see also ring current)

in detection of degenerate rearrangements 553-555

determination of optical purity by 76 diastereotopic protons 89-90 direct observation of

benzenium ion 487 bromonium ions 335 carbonium ions 257-260 norbornyl cation 310 phenonium ions 297

in measurement of conformational free energies 114-116

site exchange processes 114-115 in study of carbonium ion rearrangements

258-260, 302-303 in study of cycloa1kane conformations 126

721 INDEX

722 INDEX

nucleophilic catalysis 424-425 in acylation reactions 434 in aspirin hydrolysis 439

nucleophilic substitution reactions, aliphatic borderline mechanism of 243-248 ion pair intermediates in 244-248 leaving group effects in 271-274 limiting mechanisms for 235-243 molecular orbital description of transition state

for 241 secondary kinetic isotope effects in 287-289 SRN I mechanism 683-690 steric effects 274-276

nucleophilicity description of 264-266, 269-271 solvent effects on 268-269

1,3,5, 7-octatetraenes, electrocyclic reactions 540 2-octyl tosylatc, stereochemistry of solvolysis

279 olefins (see alkenes) optical activity 62-64 optical purity, determination by NMR 76 optical rotatory dispersion 62 orbital hybridization 3-5, 378-379 orbital symmetry control

of cycloaddition reactions 557-571 of electrocyclic reactions 532-544 of photochemical reactions 588-592 of sigma tropic rearrangements 544-557

organometallic compounds (see metal, organa-, e.g., lithium, mercury, etc.)

oxidation of cis- and

trans-4-tert-butylcyclohexanol 139-140 of carboxylate anions 682-683 by oxygen, radical chain mechanism

for 660-662 stereochemistry of enzymatic 86-87

oximes formation 413-415,417 specification of stereochemistry 76

oxymercuration 340-341

paramagnetic ring current (see ring current) partial rate factors

for bromination 509 for chlorination 507 definition 497 example of calculation 498 in hydrogen-deuterium exchange 511-512 for nitration 505-506

pentadienyl anion, electrocyclic ring closure 543 pentadienyl cation, electrocyclic ring

closure 542-543 pentalene 4 79 pericyclic reactions, definition 529

peroxides decomposition of, as source of free

radicals 633-637 diacyl, reactions with copper salts 680-681

peroxy esters reactions with copper salts 680-681 thermal decomposition 635-636, 654, 6 78

persistent free radicals 628 phase transfer catalysis 207-208 phenols

acidity in gas phase 210 allyl ethers, Claisen rearrangement of 555-556 reactions with diazonium ions 518

phenonium ions, in solvolysis reactions 295-297 phenyl cation 262 phenylalanine ammonia lyase 88 phenylalanine hydroxylase 221 phosphines, chiral 63-64, 84 phosphonium ions, deprotonation 388-389 phosphorescence, definition 586 phosphorus ylides 388-389 photochemical synthesis

of [I O]annulene 464 of Dewar benzene 538-539

photoenolization 596 photoreduction 594-595 photosensitization 585

of butadiene derivatives 608 of stilbene isomerization 606-607

photostationary state 604 pH- rate profile

for hydrolysis of benzaldehyde disalicyl acetal 438

for hydrolysis of imines 414-416 pKR+· definition 250-252 pinacol rearrangement 303 tetra-3-pinanyldiborane, in kinetic resolution in

allenes 74 PMOtheory 44-51

application to electrophilic aromatic substitution 492

in interpretation of radical stability 650 polar effects, on free radical reactions

in bromination of toluene 635 in chlorination by chlorine atoms 656, 65X

polarity of covalent bonds 14-15 polarizability 203, 211

of leaving groups 272 of nucleophiles 265, 26 7

polycyclic hydrocarbons 475-481 polyenes

Hiickel molecular orbitals for 39-41 as references for definition of aromatic

stabilization 458, 4 75-4 76 potential energy diagrams 174-176, 238, 240,

247,353,500,502,511,591 three-dimensional 349-350, 407-410, 412

primary kinetic isotope effects 190-192 prochirality 85-89 propane, rotational barrier I 07 propene

acidity of 378 conformation of 135-136 orbital interactions in 52-53

propionaldehyde, conformation of 110 pro-Rand pro-S descriptors 86 proton exchange

by electrophilic aromatic substitution 511-512 by enolization 391 in measurement of kinetic acidity 375

pseudorotation in cycloalkanes 125 in heterocycles 128

pyramidal inversion 84

quantum yield definition and measurement 587 in photoreduction of benzophenone 595

quenching, in photochemistry 586

racemic mixture, definition 73 racemization

of carbon acids by internal return 376 definition 78 during nucleophilic substitution 245, 283-284 of pyramidal molecules by inversion 84 of radical intermediates 639

radical ions 641-644 radical pair model, in CIDNP 633 radicals (see free radicals) radiative transition, in photochemistry 586 rate constant, definition 165 rate-determining step, definition 166 rate laws 166-173 reaction constant p 181

for electrophilic aromatic substitution 501 table of 181

rearrangements in addition reactions of alkenes 328, 338 of carbonium ions 258-260, 298-303 of free radicals 676-678 photochemical

of cyclohexadienes 611 of cyclohexadienones 60 I di-1r-methane 611 of a,/3-unsaturated ketones 597-599

pinacol 303 in solvolysis of arylethyl tosylates 295-796

reduction of [12]annulene 472 of aromatic compounds by sodium 640 of cyclooctatetraene 471, 642

regioselectivity and regiospecificity in additions to alkenes 324-325

definition 324 in Diets-Alder reaction 563-565 in dipolar cycloaddition 568-569

reorganization energy 652-653 resolution of enantiomers

chromatographic methods 74-75 definition 73 enzymatic 75 kinetic method 74 of 2-phenyl-3-methylbutanoic acid 73

resonance of allyl cation 8-9 of allyl radical 649 of benzyl radical 649 in carbanions 383 in hydrogen 2 in hydrogen chloride 3 rulesfor 7-10 and substituent effects 182, 185-188

resonance energy of aromatic compounds 457 of benzene 10, 458 of conjugated cyclic hydrocarbons 475-481 in unsaturated carbonyl compounds 9

resonance integral 39 retention of configuration, definition 78 ring current, as criterion for aromaticity 459,

465-467,473-474 ring inversion 112-116 ring size, as a factor in reactivity 14 7-' !51 ring strain (see strain energy) rotational barriers

in acetaldehyde II 0, 136 in 1,3-butadiene 109 in n-butane 103-105 calculation of 133-137 in ethane 53-54, 101-102 in propene 52-53, 136 table 107

Rand S descriptors (see sequence rule)

salicy lie acid acetals, hydrolysis of 437-438 esters, hydrolysis of 438-442

saponification by BAc2 mechanism 421-423 of ethyl cis- and trans-4-tert

butylcyclohexanecarboxylate 140-141 solvent effects on rate 208-209 of substituted benzoates 179, 184, 188

Saytzeff rule 353 s-character

in acidity of hydrocarbons 378-379 in cyclopropane C-H bonds 6

Schri:idinger equation 17 secondary kinetic isotope effects 193-194

in nucleophilic substitution reactions 287-289

723 INDEX

724 INDEX

secondary orbital interactions 559 selectivity

in electrophilic aromatic substitution reactions 498-499

bromination 509 chlorination 507 Friedel-Crafts reaction 513-514, 516-517

in free radical reactions 648-649, 656 self-consistent field, definition 19 semicarbazone formation 189, 413 semidiones 643-644 semiquinones 643 sensitizer, in photochemistry 585 sequence rule

application to chiral molecules 65-67 application to diastereomers 69 application to geometric isomers at double

bonds 76 application to prochiral systems 86-88

L-serine, configuration of 67 sigmatropic rearrangements 544-557

of allylic sulfoxides 557 of amine oxides 557 of sulfonium salts 557

silanes aromatic ipso-substitution of 520 in generation of radicals 637 f:l-hydroxyalkyl, elimination reactions

of 363-364 vinyl, reactions with electrophiles 365

skew conformations, of dienes I 09-110 S:-.~-reactions

SNI 238-240 SN2 240-243 SNi 287 S RN I 683-690

sodium borohydride relative reactivity of carbonyl compounds

toward 417-419 stereoselectivity in reduction of ketones 153

solvent effects 202-209 in dipolar aprotic solvents 206-207 as a function of reaction charge type 205-206 on ionization step in SN I reactions 204 isotope effects 20 I, 330, 407 on nucleophilic substitution 268-269 on nucleophilicity of anions 248

solvents, nucleophilicity of 269-270 solvolysis

of tert-butyl chloride 178, 204 of cyclopropylmethyl tosylates 260 of diarylmethyl chlorides 188-189 of ethyl sulfonates and halides (table) 272 neighboring group participation in 289-297 of norbornyl systems 304-309 of 1-phenylethyl systems 243, 271, 284 of 2-phenylethyl systems 296-297

secondary kinetic isotope effects in 192, 287-289

stereochemistry of 278-287 special salt effect 246 specific acid catalysis 197-198, 407 specific base catalysis 198 spin-trapping 632 spiranes, chirality of 67-68 stable free radicals 626-628 stannanes

elimination reactions of 363-364 substitution reactions of aryl 520 triphenyl as hydrogen atom donor 677

steady-state approximation 168-169 application to free-radical chain reactions 646

stereochemical definitions 61 stereochemistry

of addition of hydrogen halides to acetylenes 342-343

of addition of methylmagnesium iodide to 2-phenylpropanal 82-83

of addition reactions to alkenes with dibromocarbene 79, 80 epoxidation 79, 80 free-radical, with

bromotrichloromethane 668-669 free-radical, with hydrogen bromide 665 halogenation 222, 333-335 polar addition of hydrogen halides 326-

327 of carbanion reactions 379-380, 389-390 in characterization of reaction

mechanisms 221-222 of Claisen rearrangements 556 of Cope rearrangements 551 of cycloaddition reactions involving

ketenes 570 of debromination of vicinal

dibromides 362-363 of diazonium ion substitution 286 of di-rr-methane rearrangement 613 of Diels-Aider reaction 558-559 of 1,3-dipolar cycloaddition 567-568 of electrocyclic reactions 530-544 of elimination reactions 356-361 of enzymatic reactions 86-87 of free radical reactions 639 of halogenation of acetylenes 344-345 of lithium aluminum hydride reduction of

cyclohexanones 83 and neighboring group participation 289-290,

293-296 of norbornyl solvolysis reactions 304 of nucleophilic substitution reactions 79, 81,

278-296 of photochemical 2 + 2 cycloaddition

reactions 589

stereochemistry (cont.) of photochemical electrocyclic

reactions 589-590 of sigma tropic rearrangements 548-551

stereoelectronic effects anomeric effect 132 in carbonium ion rearrangements 299 definition 100 in reactions of tetrahedral

intermediates 429-430 in stereoselective reactions of

cyclohexanones 152 stereoselective reactions, definition 78

examples (scheme) 82 stereospecific reactions, definition 78

examples (scheme) 80-81 steric effects

in Friedel-Crafts reaction 514,517 on kinetic acidity of ketones 384-385 in nucleophilic substitution 274-276 in reactions of bicyclo[2.2.1 ]heptenes !53

Stern-Volmer relationship 587 stilbene, photochemical cis-trans

isomerization 606-607 strain energy

of alicyclic compounds (table) 142 components of 100-101 of cycloalkanes (table) 124 definition 99 effect on reactivity 142-146 relation to hybridization 7

structure-reactivity relationships in free radical reactions 647-655

substituent constants j' 186 3t 186 a 181 a· 185 a1 187 aR 187 a~ 187 table of 183

substituent effects 179-190 on acetal hydrolysis 407 -4ll on acidity

of carboxylic acids 16 of hydrocarbons 376-379 of phenols 210 of substituted benzoic acids 179-184

on addition reactions of alkenes 331-332, 337 on alkane conformations 105-106 on bond-dissociation energies 652-655 on bromination of alkenes 333-337 on carbanion ion stability 383-390 on carbonium ion stability 251-256 on cyclohexane conformations 113-119 on the Diels-Alder reaction 563-565

in electrophilic aromatic substitution 214-218, 489-503

on elimination reactions 349-351 on enolization 390-393 on ester hydrolysis 422-424 field effects 182 on free-radical chlorination 656-658 on free-radical rearrangements 6 77 on gas phase reactions 209-212 on hydration of alkenes 330 on hydration of carbonyl compounds 404-405 inductive effects 182 and linear free-energy relationships 179-190 on norbornyl cation 308-309 in nucleophilic substitution 277-278 polar, on free radical reactions 655-658 on radical stability 647-655 on rate

of nucleophilic substitution reactions 239, 242

of racemization of optically active biaryls 85 of reduction of aldehydes and

ketones 418-419 on stability

of methyl anion 23 of methyl cation 23 of radicals 647-655

on structure of alkyl radicals 638 sulfonate esters, in nucleophilic substitution 245,

272,279 sulfones, deprotonation of 389-390 sulfoxides

allylic, sigmatropic rearrangements 556-557 chiral 63 racemization of 84 specification of configuration 67

sulfur substituents, stabilization of carbanions 387-388

sulfur ylides 388-390, 556-557 super acid media, carbonium ions in 257-261, 298,

302-303, 309-3ll suprafacial, definition 544 Swain-Lupton equation 186 symmetry elements

of orbitals in concerted reactions 531-536, 560-561

as a test of chirality 63, 72 syn and anti descriptors 78

tartaric acid, stereoisomers 71 tautomerism, definition 220 telomer formation, in addition of hydrogen

chloride to alkenes 665 tetrafluoroethylene, cycloaddition reactions

of 571 tetrahedral intermediates 403

in amide hydrolysis 431-432

725 INDEX

726 INDEX

tetrahedral intermediate (cont.)

in ester aminolysis 427-430 in ester hydrolysis 421-426 in reactions of carbonyl compounds with

amines 411-417 stereoelectronic effects on reactivity

of 429-430 tetrahedrane, derivatives 143-144 tetrahydropyran

anomeric effect in 130-132 conformation of 128

tetramethyllead 626 thermodynamic control, definition 212-213 thermodynamic equations 161-179 thiols, free-radical addition to alkenes 670-671 thionyl chloride, reaction with alcohols 287 L-threonine, configuration of 70 threo, as descriptor for diastereomers 70 threose, stereochemistry of 70 tin, organa- compounds (see stannanes) toluene

acidity of 376-377 bromination of 655 electrophile selectivity for 498, 507, 509, 511,

513,514,516 torsional angle, definition I 0 I torsional strain

in butane 103 definition I 0 I effects on reactivity 150-151 in reactions of cyclic ketones 150-151, 419

transannular processes hydride shifts in carbonium ions 302 neighboring group participation 292-293 in radical addition reactions 675-676

transition states aromaticity and antiaromaticity in concerted

reactions 537-538 theory for kinetics 173-176

transmission characteristics of photolysis equipment 583-584

triafulvene and derivatives 480-481 trifluoroacetic anhydride, in acylation

reactions 436 trifluoroacetyl hypohalites, halogenation

with 507 trifluoromethanesulfonate, as leaving group 272 triphenylmethyl cation 249 triphenylmethyl radical 625-626 triphenyltin hydride, as hydrogen atom

donor 677 triplet state, definition 584-585 tropane; cycloaddition reactions of 571

tropylium cation (see cycloheptatrienyl cation) twist conformation of cyclohexane 112 type-] photochemical reactions of ketones 596 type- II photochemical reactions of ketones 597

ultraviolet-visible spectroscopy absorption characteristics of organic molecules

(table) 584 detection of intermediates by 195, 249-250, 374

unsaturated ketones a,/3-unsaturated

conformations of Ill photochemistry of 598-600

f3;y-unsaturated, photochemical cleavage of 600

valence bond theory 2-10 valence number 2 valence tautomerism

of bullvalene 554 of cycloheptatrienes 539-540 definition 539 of vinylcyclopropanes 552-555

van der Waals forces attractive, in 11-propyl chloride I 05-106 as factor in conformation of 11-butane I 03-104 repulsive, of axial tert-butyl-groups 119, 129 repulsive, in dienes I 09

van der Waals radii of atoms (table) 103 variable transition state theory for elimination

reactions 348-351 vinyl cations 262, 343-344 vinyl radicals 641 vinylcyclopropanes, rearrangements of 552-555 vitamin O,, sigmatropic rearrangements in

549-550

Westheimer method (see molecular mechanics) Winstein-Grunwald equation 269 Woodward-Hoffmann rules

for cycloaddition reactions for eiectrocyclic reactions for photochemical reactions

562 530-544

588-593 for sigmatropic rearrangements 547

X-ray spectroscopy (see ESCA)

ylides, formation and structure 388-389 Yukawa-Tsuno equation 185-186 Y value, as a measure of solvent ionizing

power 204

zero point energy 191

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