Roformate estersNIH-PA Author Manuscript NIH-PA Author IKK-β review ManuscriptCan Chem Trans. Author manuscript; available in PMC 2014 May well 06.D’Souza et al.PageNIH-PA Author ManuscriptScheme two.NIH-PA Author Manuscript NIH-PA Author ManuscriptA attainable unimolecular solvolytic pathway for chloroformate estersCan Chem Trans. Author manuscript; offered in PMC 2014 May possibly 06.D’Souza et al.PageTableSpecific rates of solvolysis (k) of 3 at 35.0 and 5 at 25.0 in quite a few pure and binary solvents respectively. Also listed would be 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) three; 104k, s-1b six.49 ?0.27 7.24 ?0.10 eight.18 ?.11 14.five ?0.6 21.five ?0.1 25.five ?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 two.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 5; 104k, s-1b 54.3 ?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 two.83 2.85 2.90 two.96 1.24 0.63 -0.48 -1.42 five.17 four.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 linked common deviation.Ref [36, 37]. Ref [38?1].dCan Chem Trans. Author manuscript; accessible in PMC 2014 May possibly 06.TableD’Souza et al.A comparison of the particular rates of solvolysis (105k, s-1) of mGluR6 Gene ID methyl chloroformate (MeOCOCl) [21], ethyl chloroformte (EtOCOCl) [20], 3 [28], 4 [32], five, 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 common solvents at 25.0EtOCOCl 8.24 2.26 7.31 0.023 0.611 0.838 three.29 30.9 0.591 19.7 0.481 0.062 12.3 0.086 42.0 711 2264 7.92 3.92 8.17 7.37 25.eight 231 543 2.20 1.09 2.36 2.39 85.7 605 5093 8.88 four.19 9.89 eight.51 three four five n-PrOCOCl i-PrOCOCl i-BuOCOCl n-OctOCOClSolvent ( )MeOCOClMeOH15.EtOH3.80EtOH17.97TFECan Chem Trans. Author manuscript; readily available in PMC 2014 May possibly 06.70TFE0.NIH-PA Author ManuscriptPageNIH-PA Author ManuscriptNIH-PA Author ManuscriptTableCorrelation with the particular prices of solvolysis of three, four, and five (this study) and quite a few other chloroformate esters (values in 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.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 3.21 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 three.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.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.