?0.17 0.00178 ?0.00023 0.00273 ?0.00021 0.0858 ?0.0024 3.09 ?0.01 three.62 ?0.08 18.1 ?0.1 five; 104k, s-1b 54.3 ?0.eight 118 ?3 226 ?five 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 –

?0.17 0.00178 ?0.00023 0.00273 ?0.00021 0.0858 ?0.0024 3.09 ?0.01 three.62 ?0.08 18.1 ?0.1 5; 104k, s-1b 54.3 ?0.8 118 ?three 226 ?five 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 2.96 1.24 0.63 -0.48 -1.42 5.17 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 related common deviation.Ref [36, 37]. Ref [38?1].dCan Chem Trans. Author manuscript; out there in PMC 2014 May perhaps 06.TableD’Souza et al.A comparison in the specific prices of solvolysis (105k, s-1) of methyl chloroformate (MeOCOCl) [21], ethyl chloroformte (EtOCOCl) [20], three [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 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 three.92 eight.17 7.37 25.eight 231 543 2.20 1.09 two.36 2.39 85.7 605 5093 eight.88 four.19 9.89 8.51 three 4 five n-PrOCOCl i-PrOCOCl i-BuOCOCl n-OctOCOClSolvent ( )MeOCOClMeOH15.EtOH3.80EtOH17.97TFECan Chem Trans. Author manuscript; offered in PMC 2014 May well 06.70TFE0.NIH-PA Author ManuscriptPageNIH-PA Author ManuscriptNIH-PA Author ManuscriptTableCorrelation with the particular prices of solvolysis of 3, 4, and five (this study) and quite a few other chloroformate esters (values from the literature), working with the extended Grunwald-Winstein equation (equation 1)lb 1.2-Octyldecanoic acid Order 66 ?0.P(t-Bu)3 Pd G4 supplier 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 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 3.43 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 two.79 0.947 83 A-E 0.82 ?0.16 -2.40 ?0.27 0.84 0.946 17 SN1 0.55 ?0.03 0.19 ?0.24 2.84 0.967 179 A-E 0.58 ?0.05 0.16 ?0.PMID:24633055 07 two.74 0.977 171 A-E 0.59 ?0.05 0.06 ?0.08 0.14 0.985 133 Ig 0.48 ?0.04 -0.10 ?0.09 0.06 0.971 130 Ig 0.56 ?0.03 0.15 ?0.07 two.95 0.980 568 A-Ef mb cb l/m Rc Fd MechanismD’Souza et al.SubstratenaPhOCOCle2-AdOCOCle1-AdOCOCleMeOCOCleEtOCOClen-PrOCOClei-PrOCOClei-BuOCOCleneoPOCOClePhSCSCle18hCan Chem Trans. Author manuscript; accessible in PMC 2014 May perhaps 06.32ian will be the quantity of solvents.bWith connected standard error.c Many Correlation Coefficient.dF-test value.e See text for references providing the supply of this information.Pagef Addition-elimination.NIH-PA Author ManuscriptNIH-PA Author ManuscriptNIH-PA Author ManuscriptD’Souza et al.Ionization-fragmentation.PageghiNo 90 HFIP, 90 TFE.No 97 HFIP.NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptCan Chem Trans. Author manuscript; accessible in PMC 2014 Could 06.
NIH Public AccessAuthor Manu.