Equilibrium pka Table (DMSO Solvent and Reference)

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Equilibrium pka Table (DM olvent and Reference) Copyright ans J. 2016 All Rights Reserved This pka table is on the web: http://www.chem.wisc.edu/areas/reich/pkatable/index.htm Ketones Ar = 26.5 52 19.8 58 24.6 27 18.7 CC 3 () 13.3 15.1 2 12.5 58 3 16.3 44 Py 11.8 44 Ar = 24.7 1 2-Py 23.6 4-Py 21.8 2-Furyl 23.9 2-Thienyl 24.0 = 24.7 52 24.4 58 17.7 58 C 14.2 58 C 13.4 42 C 10.2 6 F 21.7 52 21.1 34 22.9 34 2 20.3 2 23.6 57 3 14.6 6 Py 10.7 44 2 7.7 6 17.1 35 2 11.4 6 e 18.6 5 = 24.7 1 p- 25.2 p- 24.5 p- 25.7 50 m- 24.5 50 p- 2 27.5 50 m- 2 25.3 50 p-f 24.5 50 m-f 23.5 50 p-cl 23.8 50 m-cl 23.2 50 p-br 23.8 50 p- 23.8 50 p-() 23.2 p- 2 22.1 50 m- 2 23.0 50 p-c 22.0 50 p-cf 3 22.7 50 m-cf 3 22.8 50 Ketones n 3 28.2 n 4 24.9 5 25.8 6 26.7 58 7 27.7 8 27.4 n n 4 26.2 5 25.8 51 6 26.4 51 7 27.8 8 27.4 10 26.7 12 26.9 18.7 58 19.4 58 18.8 58 24.8 59 25.8 16.9 51 24.7 29.0 28.1 25.5 32.4 10.1 53 Ketones β-diketones Et 27.1 1 27.7 58 26.3 58 = 13.3 42 15.1 42 Et 15.3 43 Ac 8.6 43 Lactones 28.2 58 13.4 42 14.2 58 = 11.2 42 11.3 43 Ac 9.8 43 10.3 59 Esters t-bu t-bu Et Et =C 18.2 42 Malonate Esters 14.2 52 13.5 51 10.7 51 25.2 59 23.3 59 24.5 59 Et Et = 29.5 44 3 20.0 44 Py 14.1 44 22.7 18 C 13.1 18 () 21.4 52 2 CF 3 6.4 61 2 9.1 61 Et 30.3 23.6 18 16.9 51 18.7 51 16.9 51 19.5 38 14.2 58 20.9 11.5 59 = 16.4 42 3 11.8 44 Py 5.6 44 = 15.9 43 18.0 43 Et 18.5 43 C 2 10.8 43 CF 3 10.8 = 7.3 43 7.4 43 Et 7.6 43

Amides (C-) Et 2 Et 2 2 2 2 2 2 2 Ac 3 3 C 26.6 18 25.9 18 24.9 18 17.2 18 18.5 51 = 10.0 51 (35) 24.9 44 18.2 51 25.7 51 21.3 51 13.5 51 Equilibrium pka Table (DM olvent and Reference) Amides () R 2 R = 23.5 13 25.5 13 C 2 23.0 27 C 2 23.9 27 C 2 23.0 27 C 2 F 22.3 27 C 2 2 24.7 C 2 3 15.3 27 23.3 41 3-Py 22.0 27 4-Py 21.6 27 2-Fu 22.5 CF 3 17.2 52 Et 24.2 51 2 26.9 R C- 2 17.0 57 2 2 3,5-(CF 3 ) 2 2 R = 21.5 41 18.8 41 C 2 F 18.2 C 2 19.4 C 2 19.0 CF 3 12.6 25.9 57 18.5 41 = 23.3 = 16.9 41 16.9 41 = 24.2 51 = 13.3 18.5 51 = 10.0 51 14.7 15.0 48 Amides () itro 20.7 51 26.6 51 = 17.0 = 13.3 20.8 51 2 -C 2 - = 17.2 1 16.7 1 Et 17.0 12.2 9 11.8 10 2 7.1 6 C 7.7 6 C=C 2 11.3 2 16.9 2 2 n Carbamates () Et 2 Acetylenes 25.4 = 14.8 = 11.9 = 14.1 = F 12.7 24.2 51 n = 3 26.9 12 4 17.8 12 5 16.0 12 6 17.9 12 7 15.8 12 -C C- 28.8 1,23 itriles C = 31.3 1 32.5 5 21.9 9 C 6 F 5 15.8 37 2-Furyl 21.4 1-aphthyl 20.9 60 2-aphthyl 20.7 60 9-Anthryl 19.8 60 C 10.2 6 C- 17.2 18 C 2 Et 13.1 18 C 11.1 1 28.1 5 3 20.6 6 Py 16.5 44 20.8 5 24.3 36 2 12.0 6 C = 21.9 9,60 p- 22.9 60 3 24.6 p- 20.8 60 p-bz 16.0 60 p- 2 24.6 60 p- 23.8 60 m- 21.6 60 p-f 22.2 37,60 m-f 20.0 37,60 o-f 20.4 37 p-cl 20.6 60 m-cl 29.5 60 m-br 19.4 60 p-c 16.0 60 m-c 28.7 60 p- 2 12.3 60 m- 2 18.1 60 m-cf 3 19.2 60 p- 19.6 60 m- 10.4 60 p- 2 15.8 60 m- 2 18.5 60 (C) 2 CC 3 12.4 13 CC 2 17.5 9,60 CC(C 6 F 5 ) 2 8.0 37 C-Fl 8.3 1 C()C 23.0 60 Malononitriles C R C R = 11.1 1 12.4 13 4.2 pclc 6 4 3.1 pc 6 4 tbu 5.6 13.2 2 13.7 34 2

ydrocarbons C 4 (~56) 52 C 3 = (~43) 11 C 30.8 11 2 20.4 11 3 31.9 44 (~59) 19 Py 20.5 44 C 26.9 11 2 29.8 11 2 CF 3 24.0 11 = 31.1 30.6 30.2 ex 29.9 28.6 C 3 32.4 C 19.7 2 12.7 = 31.1 C 3 31.8 Cl 28.2 Br 28.4 C 20.0 2 13.2 2 C 2 32.3 3 (C 2 =C) 2 C 2 35. 19 (C 6 F 5 ) 2 C 2 22.0 37 (p- 2 -C 6 4 ) 2 C 2 15.2 54 3 C 30.6 1 (p-cl-c 6 4 ) 3 C 27.0 (p- 2 -C 6 4 ) 3 C 12.7 54 Equilibrium pka Table (DM olvent and Reference) ydrocarbons eteroaromatics 25.8 30.1 9 30.0 9 18.0 19 26.1 22 20.1 17 21.8 22 22.5 22 17.3 17 28.2 25.2 30.1 26.7 (35) 52 Fluorenes = Fl- = 22.6 1 22.3 1 Et 22.3 21 Pr 22.2 i Pr 23.2 21 t Bu 24.4 21 i-bu 21.6 C t 2 Bu 20.3 17.9 1 o-tol 18.8 p-tol 18.3 C 6 F 5 14.8 C 2 23.2 i 3 21.5 26 i 3 18.6 26 C() 10.0 C 2 10.3 1 C()Et 8.8 C() 2 14.8 C 8.3 1 C 12.3 52 2 7.1 2 22.1 34 2 22.5 34 3 17.8 33 Py 11.8 44 P 3 6.6 33 22.1 5 i Pr 21.4 5 tbu 21.3 5 19.9 5 18.0 7 i Pr 16.9 t Bu 15.9 15.5 5 () 15.1 ()Bn 15.7 ( 2 ) 12.8 ( 2 )Et 12.3 ( 2 ) t Bu 12.3 ( 2 ) 11.5 F 22.3 Cl 18.9 xazole Imidazolium ipr Thiazole Allyl ipr C 3 C 3 24.4 52 18.6 52 24. 49 29.4 52 16.5 30 27.0 52 30.3 52 13.9 40 C 2 =C-C 3 (44) 52 (C 2 =C) 2 C 2 35. 19 25.8 52 26.5 3 P -C 2 -C=C 2 18.5 29 3 P -C 2 -C=C 15.6 29 26.3 30.2 e e 26.3 2 -C 2 C=C 2 22.5 52 30.0 2 -C 2 C=C 2 11.3 20.2 51 Propargyl 2 -C 2 C C 22.1 2 -C 2 C C 17.8

Equilibrium pka Table (DM olvent and Reference) ulfides -C 3 (45) 52 -C 2 - = (42) 52 30.8 10 C 20.8 5 C 18.7 10 C 17.1 35 2 11.8 10 3 28.0 44 30.8 3 2 20.5 5 2 CF 3 11.0 10 P 2 24.9 -C 2-2 23.4 5 -Fl 18.0 7 -Fl 15.5 5 -C 2 -C 24.3 21 t-bu-c 2 -C 22.9 21 C 2 26.7 10 () 2 C 23.0 10 26.3 = (39) 23 30.7 10 29.0 23 C 2 20.8 23 C 19.1 23 () 3 C 22.8 10 (Pr) 3 C 31.3 52 elenides e 30.5 10 18.6 5 ec 2 27.5 (e) 2 C 2 31.3 ec 2 31.0 (e) 2 C 16.2 52 e ulfoxides Py 17.7 44 e 26.3 = 33. 15 27.2 18.2 = 35.1 1 29.0 29.0 1 ulfimides -Ts - 2 ulfonium alts 3 = 18.2 Fl- 2 27.6 30.7 16.3 17.8 32 6.5 32 ulfoximides (C-) -- 33.0 15 Ts --C 2 - = 24.5 15 Cl 20.7 Ts --C(i 3 ) 2 19.1 26 2-28.5 2-28.7 2 -- 14.4 15 ulfonates -- 25.2 C 2 -- 19.9 53 C 2 -- 19.1 C 2 --F 16.9 ulfonamides (C-) C 2 24.1 53 ulfones = 29.0 1 31.0 5 t-bu 31.2 5 23.4 1 α-aphth 22.5 β-aphth 22.3 1 2-Py 20.5 3-Py 21.6 4-Py 18.6 C=C 2 22.5 C=C 20.2 51 C C 22.1 C C 17.8 C 12.5 5 C 11.4 5 C 12.0 5 27.9 5 30.7 5 3 19.4 5 2 7.1 5 23.4 5 20.5 5 2 12.2 6 P 2 20.2 3 i 3 26.1 26 i 3 21.3 26 F 28.5 52 Cl 23.8 52-2 -i-pr 32.1-31.8 31.1 52 Et Et 32.8 9 ulfones CF 3-2 -C 3 18.8 2 CF 3-2 -Et 20.4 CF 3-2 -i-pr 21.8 2 CF 3-26.6 2 (CF 3-2 ) 2 C 2 2.1 52-2 -C 2 22.3 9 ( 2 ) 2 C 14.3 10 2 C(i 3 ) 2 20.4 26 2 C 3 29.8 CF 3 2 C 3 24.1 C 2 = t Bu C 2 CF 3 25.4 55 24.9 21 24.1 53 23.9 52 14.6 52 2 -C 2 C=C 2 22.5 52 20.2 51 2 -C 2 C C 22.1 2 -C 2 C C 17.8 11.8 51 ( 2 ) 2 C 2 15.0 21 10.1 53 C 2 24.6

Equilibrium pka Table (DM olvent and Reference) alides - 2 -C 2 - = 29.0 1 F 28.5 52 Cl 23.8 --C 2 -Cl 20.7 Ts --CCl 2 16.9 Ts () 2 P-C 2 Cl 26.2 F F ilanes (C-) = 29.0 1 i 3 26.1 26 i 3 21.3 26 Et P i 3 Et 20.2 52 28.7 52 2 C(i 3 ) 2 20.4 26 Ts --C(i 3 ) 2 19.1 26 = Fl- Ethers -C 3 (49) 52 -C 2 C 22.9 5 -C 2 C 21.1 5 -C 2 2 30.7 5 -C 2 2 27.9 5 -C 2 C 28.1 5 = Fl- = 22.6 21 17.9 52 22.1 5 ipr 21.4 5 tbu 21.3 5 19.9 5 = 31.1 30.6 30.2 osphines 2 P-C 2 -P 2 osphonium (As) alts 3 P -C 2-29.9 3 2 P-C 2-2 20.2 3 = 22.4 33 17.4 33 p-c 6 4 -C 13.0 29 p-c 6 4-2 11.0 29 p-c 6 4 -Et 18.8 29 14.9 33 C 2 Et 8.5 33 C 7.1 33 C 6.1 33 C 6.9 33 C 6.0 33 3 P -CC 2 Et 9.3 33 3 P -Pr-i 21.2 3 P -C 2 -C 6 4 C 13.0 29 3 As -C 2 -C 6 4 C 17.0 29 3 P -C 2 -C=C 2 18.5 29 3 P C 2 -C=C 15.6 29 3 P -Fl 6.6 33 osphonates Et P Et = 27.6 C 16.4 C 2 Et 18.6 Cl 26.2 i 3 28.7 52 P = Cl 26.2 P R R = 23.2 24.9 18.3 osphine xides P = 24.9 C 16.9 P C 16.3 P P 19.3 = 22.6 1 22.3 1 i 3 21.5 26 iet 3 21.4 26 i 3 18.6 26 Germanes (Ge-) 3 Ge- 23.1 63

Equilibrium pka Table (DM olvent and Reference) Amines (C) 2 20.3 52 Amines () 3 (41) 19 - = Fl- = 22.6 52 2 22.5 36 Et 2 21.4 36 ipr 2 22.5 36 2 18.2 36 (44) 19 = 30.6 11,54 m-c 3 31.0 11,54 p-ac 25.3 54 p-bz 24.4 54 p-f 30.7 54 o-f 28.7 54 o-cl 27.6 54 m-cl 28.5 54 p-cl 29.4 54 m-br 28.4 54 p-br 29.1 54 m- 30.5 54 p-c 25.3 11 m-c 27.5 11 p-c 24.4 11 p- 28.2 54 p- 2 24.9 11,54 p- 2 25.6 54 p-cf 3 2 21.8 54 p-cf 3 27.0 54 m-cf 3 28.2 54 p- 2 20.9 11,54 2 27.7 54 2 28.5 2 26.5 54 C- 2 17.0 19 2 25.0 16 Ammonium alts () 4 10.5 52 Bu 3 11.1 64 3 3.8 64 R 2 Et 3 Bn 3 Bn 2 Bn 3 9.0 47,64 3.7 46 9.8 45 8.9 45,64 2 2 7.5 45 Imides () R R = 13.1 48 R = 9.9 48 R R = 2.4 3.6 3.0 10.2 64 7.6 47 11.1 64 10.9 64 9.2 64 3.4 52 4.1 11.0 48 R = 15.1 48 R = 15.0 48 Ammonium alts (C) 3 -C 2 - = (42) 33,44 2 19.4 5 C 20.6 5 C 16.3 33 C 14.6 5 C 2 Et 20.0 33 CEt 2 24.9 18 CEt 2 15.3 27 31.9 33 28.0 33 1-Py -C 2 - = C 16.5 44 C 11.8 44 C 10.7 44 C 2 Et 14.1 44 CEt 2 24.9 18 20.5 44 17.7 44 3 -Fl 17.8 33 Py-Fl 11.8 44 Isocyanide C 2 =C 27.4 52 C 12.3 52 Imines (C) Et C 2 Imines () Et 14.4 26.5 24.3 52 22.1 31.0 41 Pyrrole, Indole (-) - 23.0 19 21.0 19 Azoles () - - - - - 2 Bu 19.9 19 18.6 52 19.8 52 14.8 52 13.9 52 8.2 52 16.4 52 15.3 ximes () 20.2 31 p- 2 -C 6 4 17.0 31 28.5 31 25.2 31 20.1 31 14.9 31 14.7

Equilibrium pka Table (DM olvent and Reference) Alcohols () 31.4 24 29.0 24 Et 29.8 24 i-pr 30.3 24 t-bu 32.2 24 CF 3 C 2 23.5 52 (CF 3 ) 2 C 17.9 (CF 3 ) 3 C 10.7 52 enols () = 18.0 25 18.9 25 19.1 Ac 14.1 2 19.8 2 10.8 CF 3 15.3 Cl 16.7 25 F 18.0 3 14.7 2 13.6 C 13.2 F 15.6 17.8 Ac 14.8 C 12.1 2 18.2 = Cl 15.8 25 F 15.8 25 C 14.8 25 2 14.4 25 Bu-t Thiols () = 10.3 20 11.2 20 Br 9.0 20 2 5.5 20 t-bu 17.9 n-bu 17.0 2 CC 2-12.9 C 2-15.3 C()- 5.2 62 -e 7.1 62 ydroxylamine (, ) Bn Bn 23.9 23.5 24.2 ydroxamic Acid (,) Bn 13.7 27 18.0 27 14.4 27 16.0 27 19.6 27 17.1 27 ydrazide () 2 2 18.9 52 2-2 17.1 52 2-2 15.8 52 (C=)- 2 21.8 27 Ac--Ac 16.7 56 (C=)- 2 19.7 (C=)- 2 18.9 27 (C=)- 2 19.7 27 3-Py(C=)- 2 17.5 27 Et 2 C- 2 22.2 56 =C( 2 ) 2 23.3 57 =C( 2 ) 2 16.6 57 15.3 56 ydrazone () - - - ulfonamide () 21.6 21.1 14.9-2 - 2 17.5 39 CF 3-2 - 2 9.7 39 R - 2-2 16.1 27 R= 14.9 56 - R= 15.2 56 2-15.4 57-2 - 12.9 2-2 17.1 27 12.7 56-2 - 2 15.8 57 -- 24.3 13.2 56 21.8 52 ydrazine () -- 26.2 56-2 28.8 56-2 24.5 56 2,4-( 2 ) 2 2 12.1 56 4-CF 3 2 25.7 56 4-C- 2 25.1 56 2 Bu-t 16.8 2 5.1 16.2 17.2 Inorganic Acids C 12.9 52 3 7.9 52 F 15. 52 Cl 1.8 52 Br 0.9 52 4 10.5 52 31.4 24 = 7.5 52 3 (41) 19 2 -C 16.9 52 Carboxylic Acids () 12.6 39 11.1 42 2 9.1 ulfinic Acids () 7.1 ulfonic Acids () 15.7-2 - 1.6 39

Amidine () 2 2 2 2 2 2 17.3 15.0 26.7 41 27.1 41 Guanidine () 2 2 2 2 2 Ureas () 2 2 2 2 19.4 28.5 41 26.9 41 19.5 41 21.0 41 Equilibrium pka Table (DM olvent and Reference) References (Bordwell et al.) 1. J. Am. Chem. oc. 1975, 97, 7006. 2. J. Am. Chem. oc. 1975, 97, 7160. 3. J. Am. Chem. oc. 1975, 97, 442. 4. J. Am. Chem. oc. 1967, 89, 2752. 5. J. rg. Chem. 1976, 41, 1885. 6. J. rg. Chem. 1976, 41, 1883. 7. J. rg. Chem. 1976, 41, 2786. 8. J. rg. Chem. 1976, 41, 2508. 9. J. rg. Chem. 1977, 42, 321. 10. J. rg. Chem. 1977, 42, 326. 11. J. rg. Chem. 1977, 42, 1817. 12. J. rg. Chem. 1978, 43, 3113. 13. J. rg. Chem. 1978, 43, 3095. 14. J. rg. Chem. 1978, 43, 1764. 15. J. rg. Chem. 1980, 45, 3884. 16. J. rg. Chem. 1980, 45, 3305. 17. J. rg. Chem. 1980, 45, 3325. 18. J. rg. Chem. 1981, 46, 4327. 19. J. rg. Chem. 1981, 46, 632. 20. J. rg. Chem. 1982, 47, 3224. 21. J. rg. Chem. 1982, 47, 2504. 22. J. Am. Chem. oc. 1983, 105, 6188. 23. J. Am. Chem. oc. 1986, 108, 7310. 24. J. rg. Chem. 1980, 45, 3295. 25. J. rg. Chem. 1984, 49, 1424. 26. J. Am. Chem. oc. 1995, 117, 602. 27. J. rg. Chem. 1995, 55, 3330. 28. J. Am. Chem. oc. 1996, 118, 8777. 29. J. rg. Chem. 1996, 61, 4103. 30. J. Am. Chem. oc. 1991, 113, 985. 31. J. rg. Chem. 1992, 57, 3019. 32. J. rg. Chem. 1998, 63, 7574. 33. J. Am. Chem. oc. 1994, 116, 968 34. J. Am. Chem. oc. 1989, 111, 7558 35. J. Am. Chem. oc. 1992, 114, 7623 36. J. Am. Chem. oc. 1994, 116, 973 37. J. rg. Chem. 1988, 53, 780. 38. J. Am. Chem. oc. 1988, 110, 8520 39. J. rg. Chem. 1976, 41, 2507. 40. J. Am. Chem. oc. 1990, 112, 792 41. J. Am. Chem. oc. 1991, 113, 8398. 42. J. rg. Chem. 1980, 45, 3299. 43. Arnett J. Am. Chem. oc. 1984, 106, 6759. 44. J. rg. Chem. 1993, 58, 3061. 45. Benoit Can. J. Chem. 1987, 65, 996. 46. Kreevoy J. ys. Chem. 1977, 81, 1924. 47. Kolthoff J. Am. Chem. oc. 1968, 90, 23. 48. Bausch J. rg. Chem. 1990, 55, 5806. 49. Alder Chem. Commun, 1995, 1267 50. J. rg. Chem. 1978, 43, 1763. 51. J. rg. Chem. 1991, 56, 4218. 52. Acc. Chem. Res. 1988, 21, 456, 463. 53. J. rg. Chem. 1991, 56, 4448. 54. J. Am. Chem. oc. 1988, 110, 2964. 55. J. Am. Chem. oc. 1974, 76, 1214. 56. J. Am. Chem. oc. 1997, 119, 9125. 57. J. rg. Chem. 1990, 55, 3337. 58. Can. J. Chem. 1990, 68, 1714. 59. Arnett J. Am. Chem. oc. 19874, 109, 809. 60. J. ys. rg. Chem. 1988, 1, 209. 61. Terrier J. rg. Chem. 2003, 68, 6566. 62. Courtet-Coupez Bull. oc. Chim. Fr. 1969, 1033. 63. Curtis J. Am. Chem. oc. 1969, 91, 6011 64. Crampton J. Chem. Res. () 1997, 22. All others are F. G. Bordwell, private communication. For a review, see: F. G. Bordwell Acc. Chem. Res. 1988, 21, 456, 463.

Equilibrium pka Table ( 2 olvent and Reference) Values outside the boxes were determined by approximate methods. xygen Acids itrogen Acids Carbon Acids CF 3 3 C 6 5 - C 6 5 -C C 6 5-12.4-7.8-6.5 C 3 (C 3 ) 2-5.4-4.4 (C 3 ) 2-3.8 C 3 - -2.6 C 3-2 -2.2-2.1 (C 3 ) 2 = -1.8 - -1.4 CF 3 -C 2-0.3 2 2 0.3 P 4-14. C 6 5 -C - -10.5 C 3 -C - -10. 2 2-9.3 3 2 C 6 5 - -C 6 5-2.9 (C 6 5 ) 2 2 0.8 C 3 -P 3 2.7 C 6 5-3 4.6 5.2 C-C 2 C 2-3 7.9 (C 3 C 2 ) 3 P 9.1 2 9.2 4 9.2-10.0 C 3 C 2 3 10.6 (C 3 C 2 ) 2 2 11.0 (C 3 C 2 ) 3 10.8 = 11.5 2 11.2 4 ( 2 ) 2 C 2 3.6 5.2 9.0 3 C- 9.1 C 3 10.0 1 2 -C 3 10.2 Et 10.7 (CF 3 ) 3 C 11. (C) 2 C 2 11.2 Et 12.2 6 Et 12.9 15. C 3 -C- 16.7 C 3 -C- 18.3 C 3 -C-C 3 19.3 20-24.8 C 3-24.3-18.5 3 C C 3 C 3-12.5 3 C C 3 2 (C 3 ) 2 e= 2.6 C 6 5 -C 2 4.2 C 3 C 2 4.8 C 2 6.3 C 6 5-6.5 C 2 =C() 8.0 2 C 6 5-10.0 C 3 10.3 R- 10.5 C 2 =C 10.5 C 2 =C(C 3 ) 10.9 11.7 2 15.7 C 3-16 (C 3 ) 3 C- 20 2 2 (C 3 ) 2 -C-(C 3 ) 2 13.6 15. C 6 5-2 28. ((C 3 ) 3 i) 2-30. (i-c 3 7 ) 2-36. 37. alogen Acids -I -5.2 -Br -4.7 -Cl -2.2 -F 3.2 C 6 5 -C 2 -C 21 C 6 5 -C C- 23 C 3 C 2 Et 24 -C C- 24 C 3 -C 25 29 CF 3-32 C 3 - C 3 33 (C 6 5 ) 3 C- 32 C 3 - C 3 33 C 6 5 -C 3 41 44 C 3 C 3 50

Gas ase Acidities Chem 842 δ acid (kcal/mol) 10 acid (kcal/mol) C 3 -C 3 (420.1) 2 2 C 2 (419.4) 2 C 4 (416.6) 1 ClC 3 (395.6) 3 C 3 (393.2) 3 3 ic 3 (390.9) 3 2 C=C-C 3 (387.2) 1 (408) 7 2 C=C 2 (409) 8 - (400.7) 4 2 PC 3 (384) 3 (386.9) 4 C (383) 8 2 =C=C 2 (381.1) 9 F C 3 (379.0) 1 F 3 C (377) 3 F C C- (377) 8 3 C- (375.6) 1 C (348.7) 5 FC 3 (409) 3 C 3 C 3 (407) 3 C 3 C 3 (372.7) 1 CC 3 (369) 7 C 3 CC 3 (368.8) 1 C 3 2 C 3 (366.6) 1 CC 3 (363.2) 1 2 C 3 (358.7) 1 CF 3 CC 3 (347.1) 5 (342.6) 5 (335.1) 5 F 2 C 2 (389) 7 Cl 2 C 2 (374.1) 3 ( 3 i) 2 C 2 (373) 3 ( 2 P) 2 C 2 (370) 3 2 C 2 (364.5) 1 (C 2 =C) 2 C 2 (359.7) 5 (356.1) 1 (348.5) 5 (C 3 C) 2 C 2 (342.6) 5 ( C) 2 C 2 (331.7) 5 3 C (413.1) 2 C 2 C 2 - (406) 7 1. Bartmess J. Am. Chem. oc. 1979, 101, 6046 2. Braumann, J. Am. Chem. oc. 1995, 117, 4905 3. Braumann J. Am. Chem. oc. 1998, 120, 2919 4. Tetrahedron Lett. 1997, 0, 8519 5. Kebarle J. Am. Chem. oc. 1976, 98, 3399 (add 3-4?) 6. Ellison 7. quires J. Am. Chem. oc. 1990, 112, 2517 8. Kass J. Am. Chem. oc. 2003, 125, 11746 9. Review: Kass Chem. Rev. 2013, 113, 6986. (398) C 2 C()- (387) 7 () 3 C- Cl 3 C- (356.7) 3 EtC 2 (345.2) 5 0-10 -20-30 -40-50 -60-70 C 2 (337.7) 5-80 FC 2 C 2 (335.6) 5 ClC 2 C 2 (333.6) 5 F 2 CC 2 (328.4) 5-90 -100 420 410 2 (400.4) 1 400 3 (399.6) 1 390 - (390.8) 1 380 - (380.6) 2 - (374.6) 6 F- (371.5) 1 370 P 3 (370.4) 1 2 (367.1) 1 360 (360.7) 1 - (356.9) 2 C- (353.1) 1 - (351.4) 1 350 - (351.2) 2 340 - (338.9) 1 e- (338.7) 1 Cl- (333.3) 1 330 Br- (323.6) 1 320 I- (314.3) 1 310 3 i- (383) 2 - (376.5) 6 i 4 (372.8) 2 3 Ge- (361.5) 2 Ge 4 (359) 2 3 n- (349) 2 2015-07