Field and Resonance values according to Swain

Field and Resonance constants for substituent effects

Introduction

Swain and Lupton developed a method they called DOVE (→ Dual Obligate Vector Evaluation ) which is a forerunner to PCA (→ Principle Component Analysis).
They applied it to derive two-parameter equations with orthogonal parameters for substituent effects and for solvent effects.
The substituent constants are given below.
  1. C.G. Swain, S.H. Unger, N.R. Rosenquist, M.S. Swain, J. Am. Chem. Soc. 105 (1983) 492-502


Field and resonance components
NameSymbolF (Field)R (Resonance)
acetamido‐‐NHCOCH30.77-1.43
acetoxy‐‐OCOCH30.7-0.04
acetyl‐‐COCH30.50.9
acetylthio‐‐SCOCH30.530.68
amino‐‐NH20.38-2.52
bromo‐‐Br0.72-0.18
butoxy‐‐O(CH2)3CH30.72-2.16
carboxy‐‐COOH0.440.66
carboxylate‐‐COO⁻-0.270.4
chloro‐‐Cl0.72-0.24
cyano‐‐CN0.90.71
diazonium‐‐N22.362.81
dimethylamino‐‐N(CH3)20.69-3.81
dimethylsulfonium‐‐S⁺(CH3)21.620.52
ethoxy‐‐OCH2CH30.61-1.72
ethoxycarbonyl‐‐COOCH2CH30.470.67
ethyl‐‐CH2CH3-0.02-0.44
fluoro‐‐F0.74-0.6
hydrogen‐‐H00
hydroxy‐‐OH0.46-1.89
iodo‐‐I0.65-0.12
iodyl‐‐IO20.990.99
isopropoxy‐‐OCH(CH3)20.9-2.88
mercapto‐‐SH0.52-0.26
methoxy‐‐OCH30.54-1.68
methyl‐‐CH3-0.01-0.41
methylseleno‐‐SeCH30.28-0.39
methylsulfanyl‐‐SCH30.68-1.3
methylsulfinyl‐‐S(=O)CH30.80.45
methylsulfonyl‐‐S(=O)2CH30.880.85
nitro‐‐NO211
pentoxy‐‐O(CH2)4CH30.75-2.27
phenoxy‐‐OC6H50.76-1.29
phenyl‐‐C6H50.25-0.37
phosphonate‐‐PO3H⁻0.220.58
propoxy‐‐O(CH2)2CH30.63-1.77
sulfamoyl‐‐SO2NH20.551.07
sulfonate‐‐SO3-0.050.53
tert-butyl‐‐C(CH3)3-0.11-0.29
trifluoromethyl‐‐CF30.640.76
trimethylammonium‐‐N⁺(CH3)31.540
trimethylsilyl‐‐Si(CH3)3-0.10.16
trimethylsilylmethyl‐‐CH2Si(CH3)3-0.19-0.32