Ns. Author manuscript; readily available in PMC 2014 May perhaps 06.Figure 5.The plot of
Ns. Author manuscript; obtainable in PMC 2014 May 06.Figure five.The plot of log (k/ko)five against log (k/ko)PhOCOClD’Souza et al.PageCB1 Modulator Source NIH-PA Author ManuscriptScheme 1.A carbonyl addition approach for chloroformate estersNIH-PA Author Manuscript NIH-PA Author ManuscriptCan Chem Trans. Author manuscript; readily available in PMC 2014 May 06.D’Souza et al.PageNIH-PA Author ManuscriptScheme 2.NIH-PA Author Manuscript NIH-PA Author CYP51 Inhibitor review ManuscriptA possible unimolecular solvolytic pathway for chloroformate estersCan Chem Trans. Author manuscript; offered in PMC 2014 May possibly 06.D’Souza et al.PageTableSpecific prices of solvolysis (k) of three at 35.0 and five at 25.0 in numerous pure and binary solvents respectively. Also listed are the literature values for NT and YClSolvent ( )a 100 EtOH 90 EtOH 80 EtOH one hundred MeOH 90 MeOH 80 MeOH 70 MeOH 90 Acetone 80 Acetone 70 Acetone 97 TFE (w/w) 90 TFE (w/w) 3; 104k, s-1b 6.49 0.27 7.24 0.10 eight.18 .11 14.five 0.6 21.five 0.1 25.5 0.2 30.1 0.7 1.27 0.07 two.11 0.09 two.48 0.08 0.00217 0.00022 0.0150 0.0009 0.215 0.000 1.77 0.01 0.165 0.009 0.0839 0.0021 0.319 0.007 2.59 0.00 ten.two 0.0 1.59 0.17 0.00178 0.00023 0.00273 0.00021 0.0858 0.0024 three.09 0.01 three.62 0.08 18.1 0.1 five; 104k, s-1b 54.three 0.eight 118 3 226 5 509 two 682 0 953 1 NTc 0.37 0.16 0.00 0.17 -0.01 -0.06 -0.40 -0.35 -0.37 -0.42 -3.30 -2.55 -2.19 -1.98 -1.34 -0.94 -0.34 0.08 -5.26 -3.84 -2.94 YCld -2.50 -0.90 0.00 -1.2 -0.20 0.67 1.46 -2.39 -0.83 0.17 2.83 two.85 2.90 two.96 1.24 0.63 -0.48 -1.42 5.17 4.41 three.NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author Manuscript80 TFE (w/w) 70 TFE (w/w) 70T-30E 60T-40E 40T-60E 20T-80E 97 HFIP (w/w) 90 HFIP (w/w) 70 HFIP (w/w) aSubstrate concentration of ca. 0.0052 M; binary solvents on a volume-volume basis at 25.0 , except for TFE-H2O and HFIP-H2O solventswhich are on a weight-weight basis. T-E are TFE-ethanol mixtures. b c With connected common deviation.Ref [36, 37]. Ref [381].dCan Chem Trans. Author manuscript; obtainable in PMC 2014 May perhaps 06.TableD’Souza et al.A comparison with the particular prices of solvolysis (105k, s-1) of methyl chloroformate (MeOCOCl) [21], ethyl chloroformte (EtOCOCl) [20], 3 [28], 4 [32], 5, n-propyl chloroformate (n-PrOCOCl) [24], iso-propyl chloroformate (i-PrOCOCl) [22,27], iso-butyl chloroformate (i-BuOCOCl) [30], and n-octyl chloroformate (n-OctOCOCl) [53] in frequent solvents at 25.0EtOCOCl 8.24 two.26 7.31 0.023 0.611 0.838 3.29 30.9 0.591 19.7 0.481 0.062 12.3 0.086 42.0 711 2264 7.92 3.92 eight.17 7.37 25.8 231 543 two.20 1.09 2.36 two.39 85.7 605 5093 8.88 4.19 9.89 8.51 3 four five n-PrOCOCl i-PrOCOCl i-BuOCOCl n-OctOCOClSolvent ( )MeOCOClMeOH15.EtOH3.80EtOH17.97TFECan Chem Trans. Author manuscript; out there in PMC 2014 May perhaps 06.70TFE0.NIH-PA Author ManuscriptPageNIH-PA Author ManuscriptNIH-PA Author ManuscriptTableCorrelation of your distinct prices of solvolysis of three, 4, and five (this study) and numerous other chloroformate esters (values in the literature), applying the extended Grunwald-Winstein equation (equation 1)lb 1.66 0.05 0.03 0.07 0.08 0.20 1.59 0.09 1.56 0.09 0.69 0.13 1.57 0.12 0.40 0.12 1.35 0.22 0.28 0.04 1.82 0.15 1.76 0.14 0.36 0.ten 0.69 0.05 1.43 0.15 1.52 0.08 1.99 0.23 0.62 0.12 0.19 0.17 three.21 0.953 49 A-E 0.55 0.03 0.13 0.06 2.76 0.962 178 A-E 0.38 0.ten 0.17 0.13 3.76 0.963 96 A-E 0.95 0.03 0.18 0.05 0.72 0.987 521 SN1 0.81 0.14 -2.79 0.33 0.44 0.938 18 SN1 0.48 0.06 0.14 0.08 3.67 0.977 226 A-E 0.53 0.05 0.18 0.07 three.43 0.957 82 A-E 0.59 0.04 -0.32 0.06 0.47 0.982 176 Ig 0.40 0.05 0.18 0.07 three.3.