Roformate estersNIH-PA Author Manuscript NIH-PA Author ManuscriptCan Chem Trans. Author manuscript; offered in PMC 2014 Might 06.D’Souza et al.PageNIH-PA Author ManuscriptScheme two.NIH-PA Author Manuscript NIH-PA Author ManuscriptA possible unimolecular solvolytic pathway for chloroformate estersCan Chem Trans. Author manuscript; accessible in PMC 2014 May 06.D’Souza et al.PageTableSpecific rates of solvolysis (k) of three at 35.0 and 5 at 25.0 in a number of pure and binary MGMT Source solvents respectively. Also listed would be the literature HDAC11 Accession 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) three; 104k, s-1b six.49 ?0.27 7.24 ?0.ten 8.18 ?.11 14.5 ?0.six 21.five ?0.1 25.five ?0.2 30.1 ?0.7 1.27 ?0.07 two.11 ?0.09 2.48 ?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 two.59 ?0.00 10.2 ?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 54.3 ?0.8 118 ?3 226 ?5 509 ?2 682 ?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 two.83 2.85 two.90 2.96 1.24 0.63 -0.48 -1.42 five.17 4.41 3.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 related standard deviation.Ref [36, 37]. Ref [38?1].dCan Chem Trans. Author manuscript; offered in PMC 2014 Might 06.TableD’Souza et al.A comparison with the certain rates of solvolysis (105k, s-1) of methyl chloroformate (MeOCOCl) [21], ethyl chloroformte (EtOCOCl) [20], 3 [28], four [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 typical solvents at 25.0EtOCOCl eight.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 2.39 85.7 605 5093 eight.88 4.19 9.89 8.51 3 four 5 n-PrOCOCl i-PrOCOCl i-BuOCOCl n-OctOCOClSolvent ( )MeOCOClMeOH15.EtOH3.80EtOH17.97TFECan Chem Trans. Author manuscript; obtainable in PMC 2014 Might 06.70TFE0.NIH-PA Author ManuscriptPageNIH-PA Author ManuscriptNIH-PA Author ManuscriptTableCorrelation on the certain prices of solvolysis of 3, four, and five (this study) and quite a few other chloroformate esters (values from the literature), utilizing 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 ?0.10 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 two.76 0.962 178 A-E 0.38 ?0.10 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 3.38 0.960 35 A-E 0.64 ?0.13 -2.45 ?0.27 0.63 0.942 11 SN1 0.56 ?0.06 0.15 ?0.08 2.79 0.947 83 A-E 0.82 ?0.16 -2.40 ?0.27 0.84 0.946.
