INDEX 1969 Applications-of-Nuclear-Magnetic-Resonance-Spectroscopy-in-Organi - Leitura (2024)

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INDEX Absorption intensity see Intensity Absorption signals 27 Acenaphthenes 197, 233 Acenaphthylene 188 Acetaldehyde 164 diethylacetal 166 Acetamide 164 axial and equatorial derivatives 240 derivatives 176 N,N-dimethyl 178 N-ethyl 164 N-methyl 164 N-/so-propyl 164 N-rt-propyl 164 Acetates 176 axial and equatorial 240 Acetic acid chemical shift 164 methyl ester 164 Acetic anhydride 177 Acetone chemical shift 164 cyanohydrin 166 dimethylketal 166 solvent effects of 106 Acetonitrile benzene solvent effect for 111 chemical shift 164 solvent effects for 106 Acetophenone 164 Acetylacetone, tautomerism 177 Acetyl bromide 177 Acetyl chloride 177 Acetylene analysis of 13C-satellite spectrum 140 ' I3C.H 141 long-range shielding in 73 Acetylenes chemical shifts 164, 193 conjugated 187 spin-spin coupling 328 Acid anhydrides, stereochemistry from sol-vent shifts 248 Acidinium ions 262 Acridines, chemical shifts 212 Acrylic acid, ß, ^-dimethyl derivatives 171 Acrylonitrile, analysis of spectrum of 143 Acylation shift 176 Acyl cations 262 Adamantane, 1-substituted, correlation of σ * with chemical shifts 66 Admantanes 196,232 Adamantyl carbonium ion 251 Alcohols chemical shifts 164, 176, 179 chemical shifts of OH 215 spin-spin coupling of OH groups 298 Aldehydes aromatic, restricted rotation 362 benzene solvent effects with 111 chemical shifts 164, 191 conformation from spin-spin coupling 284 long-range spin-spin coupling 333 α,β-unsaturated, spin-spin coupling 284, 324, 333 vicinal spin-spin coupling 284 Aliphatic hydrocarbons, chemical shifts 168 Alkanes, chemical shifts 168 Alkenes chemical shifts 164, 171, 187 conformation 364 cyclic, chemical shifts 188 Alkenyl carbonium ions 252 Alkylamines, N-methyl 178 Alkyl carbonium ions 250 Alkyl derivatives, chemical shifts 164 Alkyl halides, chemical shifts 164 Alkyl nitrites 227 Alkyl zinc derivatives 265 Alkynyl carbonium ions 252 Aliènes chemical shifts 190 geminal spin-spin coupling 278 long-range spin-spin coupling 328 non-equivalence 378 vicinal spin-spin coupling 284 Allyl carbonium ions 252 Allylic anions 263 Allylic groups, cyclic, chemical shifts 188 Allylic méthylène and methine groups, che-mical shifts 172 Allylic protons, chemical shifts 170 441 442 Index Amides chemical shifts 164, 215 exchange with D 2 0 360 partial double bond character 361 protonation 384 spin-spin coupling 328, 360 stereochemistry from solvent shifts 248 Amines acylation shift 180 average spectra 259 chemical shifts 164, 178, 180 chemical shifts of NH 215, 359 exchange of — NH 181 nitrogen inversion 366 protonation 180 spin-spin coupling of NH groups 298 Analysis of spectra 122 first order 124 use of 13C satellites 140 use of contact shifts 144 use of deuterium substitution 142 use of field variation 139 use of solvent effects 144 use of spin decoupling 145 Androstanes, chemical shifts of angular methyl groups 242 Anhydrides, cyclic, /i3CfH 141 Aniline derivatives 203, 359 N,N-dimethyl 178 N,N-dimethyl-/>-nitro 178 N,N-dimethyl-p-nitroso 227 N-methyl 178 substituted, correlation of chemical shift with o~ 66 Anisole chemical shifts 164 derivatives 180,203 [18]Annulene 97 Annulenes, spin-spin coupling 309 Anthracene, 9,10-dihydro 197 Anthracenes chemical shifts 205 spin-spin coupling 306 Anthrone 197 9,9-dimethyl 100 9-spirocyclopropane, chemical shifts 100 Arenonium ions 254 Aromatic anions 265, 266 Aromatic cations 261 Aromatic compounds benzene solvent effects 111 chemical shifts 201 nonbenzoid, chemical shifts 205 para-disubstituted 221 solvent effects 204 spin-spin coupling 305, 330, 338 Aromaticity and the chemical shift 98 Aryl carbonium ions 251 Asymmetry and spin-spin coupling 314 Axial and equatorial groups, chemical shifts 240 Axial and equatorial protons chemical shifts 199, 200, 238 spin-spin coupling 288, 338 Azaindolizine, chemical shifts 210 Azapolynuclear derivatives, chemical shifts 214 Azetidine 199 2-phenyl, spin-spin coupling 272 Aziridines chemical shifts 100 inversion 366 steroidal, chemical shifts 101 Azobenzenes 224 Azoxy compounds 178 Azulenes, chemical shifts 205 Azulenonium ions 254 Benzaldehyde, substituted, correlation of Hammett σ-constants with chemical shifts in 66 Benzazines, chemical shifts 212 Benzene, solvent effect of 111 Benzene derivatives chemical shifts 201 correlation of Hammett cr-constants with chemical shifts in 66 influence of substituents on chemical shifts 202 Jl3c.H 1 4 1 polysubstituted 170 solvent effects 106, 108 spin-spin coupling 306 Benzenonium ions 254 Benzimidazole, N-acetyl 177 spin-spin coupling 308 1 jfiT-Benz[e]indene, 2,3-dihydro-l-oxo, che-mical shifts 91 Benzoates 164, 179 Benzocyclobutenes 224 chemical shifts 235 Bsnzofuran, 2,2-dimethyldihydro 168 Bsnzofurans chemical shifts 209 spin-spin coupling 308 Benzoic acid, methyl ester 164 Benzopyrazoles chemical shifts 210 spin-spin coupling 308 /7-Benzoquinone derivatives 189 Benzothiophens chemical shifts 210 spin-spin coupling 308 Index 443 Bentylacetone, spectrum of 136 Benzyl alcohol, spectra of 131 Benzyl chloride derivatives 175 Benzylic methyl groups, chemical shifts 173 Benzylic protons, chemical shifts 170, 173 Benzyllithium 265 Beyerol, 15/?,16ß-oxido-, chemical shifts 99 Biacetyl 177 Bicyclic compounds, chemical shifts 196 Bicyclo[2.2.1]heptanes chemical shifts 100, 229 vicinal spin-spin coupling 289, 335 Bicyclo[2.2.1]heptanols, chemical shifts 79 Bicyclo[2.2.1 Jheptene effect of substituents on chemical shifts 64 vicinal spin-spin coupling 289 Bicyclo[2.1.1]hexanes, spin-spin coupling 276, 288, 335 Bicyclo[2.2.2]octanes chemical shifts 229, 232 spin-spin coupling 288, 335 Bicyclo[2.1.3]octanes, spin-spin coupling 335 Bicyclo[2.2.2]octenes, chemical shifts 232 Biphenylenes chemical shifts 206 spin-spin coupling 309 Bisdehydro[14]annulene, chemical shifts 97 Bond order and allylic coupling 322 and hom*oallylic coupling 325 and side-chain coupling 331 and vicinal spin-spin coupling 303 Bromine, solvent effects for 106 Bromochloromethane, solvent effects for 106 Bromocyclohexane, axial and equatorial protons 239 Bromoform, solvent effects for 106 N-Bromosuccinimide 200 Bromotrichloromethane, solvent effects for 106 Buckingham's theory of solvent effects 107 Bulk susceptibility, correction for 104 Bullvalene 362 Butadiene derivatives chemical shifts 187, 225 spin-spin coupling 285, 341 Butanal 164 Butane 2,3-diacetoxy 163 2,3-dibromo 163 2,3-dichloro 163 2,3-diphenyl 163 n-Butanol 3-methoxy 166 spectrum of 143 te/7-Butanol 164 But-1-ene 164 3,3-dimethyl 164 3-methyl 164 But-2-ene 2-methyl 171 solvent effects for eis and trans 106 Butènes 171 spin-spin coupling 323 Butenolides 188 spin-spin coupling 317 tert -Butyl acetate 164 teri-Butylamine 164 ter/-Butylbenzene 164, 168 tert -Butyl benzoate 164 ter/-Butyl bromide 164 teri-Butyl chloride 164 ter/-Butyl cyanide 164 tert-Butyl derivatives, chemical shifts 164, 168 ter/-Butyl iodide 164 tert -Butyl isocyanide 164 tert -Butyl mercaptan 164 terf-Butyl methyl ketone 164 But-1-yne 164 3,3-dimethyl 164 3-methyl 164 But-2-yne, solvent effects for 106 wo-Butyramide 164 rt-Butyramide 164 /so-Butyric acid 164 Λ-Butyric acid 164 2-bromo 166 methyl ester 164 Butyrolactam 198 Butyrolactone 198 13C chemical shifts 64, 77 coupling constants 77, 345 satellites 140 Calibration of spectra 43 side band technique 43 wiggle beat technique 43 Camphor derivatives 233 Carbanions 262 Carbonates, cyclic, chemical shifts 235 Carbon disulphide, solvent effects for 106 444 Index Carbonium ions 249 non-classical 256 Carbon tetrachloride, solvent effects for 106 Carbonyl compounds conformation 364 cyclic 192derivatives, chemical shifts 226 hydrates 384 α,β-unsaturated, chemical shifts 170, 171,187, 190,192,223 α,β-unsaturated, coupling constants 285, 323 Carbonyl group, influence on chemical shifts 88, 207 Carboxylic acids, chemical shifts 164,216, 359 CAT (computer of averaged transients) 41 Chemical exchange effect on line shapes 56 measurement of rate by double reso-nance 157 Chemical shift 11 additivity rules 160 applications 159 average over a number of conformations 60 bar-graphs 161 classification systems 162 compilations 159 highly accurate determination by spin decoupling 155 limitations to correlations 159 Chlorobenzene, solvent effects for 106 Chlorocyclohexane, axial and equatorial protons 239 Chlorodibromomethane, solvent effects for 106 Chloroform, solvent effects for 106 Chromene 189 2,2-dimethyl and derivatives 169 Chromones and analogs, chemical shifts 213 Chrysenes, chemical shifts 205 Cinnolines chemical shifts 212 spin-spin coupling 309 Clerodin, spectrum of 156 Collision complex 109, 246 Complex formation, and vicinal spin-spin coupling 304 Computer of averaged transients 41 Configuration, threo-erythro from spin-spin coupling 291 Conformation ethane derivatives 368 from chemical shifts 245 from vicinal spin-spin coupling 289 Conformational inversion 60, 364 and symmetry 365 Contact shifts 102 Cotton-Mouton effect 75 Coumarin 188 Coupling see Spin-spin coupling Coupling path 269 Cresols 175 Cubane, chemical shift 71 Cumulenes, spin-spin coupling 328 Curvature 31 Cycl[3,2,2]azine chemical shifts 211 spin-spin coupling 309 Cycling 32 Cycloalkanes 196 Cyclobutane, chemical shift 196 Cyclobutanes chemical shifts 235 1,2-dione-3,4-dimethyl 172 geminal spin-spin coupling 276 long-range spin-spin coupling 336 stereochemistry from chemical shifts 234 vicinal spin-spin coupling 287 Cyclobutanone 198 shielding by the carbonyl group in 91 Cyclobutene derivatives 188 1-methyl 172 spin-spin coupling in derivatives 287, 303, 320 Cyclodecene, vicinal spin-spin coupling 303 Cycloheptane, chemical shift 196 Cycloheptanone 198 derivatives 169 Cycloheptatrienes 172, 188 Cycloheptane, vicinal spin-spin coupling 303 Cycloheptenone 192 Cyclohexa-l,3-diene, vicinal spin-spin coupling 285 Cyclohexadienes 188 Cyclohexadienones, vicinal spin-spin coupling 285 Cyclohexane axial and equatorial protons 239 chemical shift 196 conformation from chemical shifts 239 4-te/Y-butyl derivatives 239 1,2-diphenyl 224 solvent effects for 106 Cyclohexane derivatives axial and equatorial protons from spin-spin coupling 288 Index 445 Cyclohexane derivatives (cont.) conformational inversion 364 geminal spin-spin coupling 275 influence of substituents on chemical shifts 237 long-range spin-spin coupling 337 stereochemistry from chemical shifts 234 vicinal spin-spin coupling 290 Cyclohexane thiol axial and equatorial protons 239 Cyclohexanol axial and equatorial protons 239 4-/-butyl, spin-spin coupling 290 c/s-4-f-butyl, chemical shifts 79 /rart.s-4-f-butyl, chemical shifts 79 conformation from spin-spin coupling 290 c/s-2-c/s-6-dimethyl, chemical shifts 79 trans-2-trans-6-dimGthy\, chemical shifts 79 2,2-dimethyl-cw-4-/-butyl, chemical shifts 79 2,2-dimethyl-/ra«.s-4-/-butyl, chemical shifts 79 3,3-dimethyl, chemical shifts 79 trans-3-trans-5'dimethy\, chemical shifts 79 c/s,c/s-3,5-dimethyl, chemical shifts 79 trans-2-methyl, chemical shifts 79 c/s-2-methyl-c/s-4-/-butyl, chemical shifts 79 c/s-2-methyl-/rarts-4-/-butyl, chemical shifts 79 /ratf.s-2-methyl-cw-4-/-butyl, chemical shifts 79 trans-l-methyl-trans-^t-butyl, chemical shifts 79 c/s-3-methyl, chemical shifts 79 3,3,5,5-tetramethyl, chemical shifts 79 cw-3,3,5-trimethyl, chemical shifts 79 Cyclohexanone 198 2-bromo, conformation from vicinal coupling 291 derivatives 169, 241 Cyclohexene chemical shifts 188, 238 2,4-dimethyl 172 vicinal spin-spin coupling 303 Cyclohexenone 188, 192 derivatives 168, 172 Cyclohexenyl carbonium ion 252 Cyclohexyl acetate, axial and equatorial protons 239 Cyclohexyl amine axial and equatorial protons 239 N,N-dimethyl 178 N-methyl, axial and equatorial protons 239 Cyclohexyl derivatives 238 Cyclononene, vicinal spin-spin coupling 303 Cyclooctane 196 Cyclooctanone 198 Cyclooctatetraene, spin-spin coupling 285 Cyclooctatetraenyl dianion 266 Cyclooctene 188 vicinal spin-spin coupling 303 Cyclopentadiene chemical shifts 188 vicinal spin-spin coupling 285 Cyclopentadienyl an ion 266 Cyclopentane chemical shift 85, 196 1,2-diphenyl 224 solvent effects for 106 Cyclopentane derivatives conformation from spin-spin coupling 287 geminal spin-spin coupling 275 stereochemistry from chemical shifts 234 vicinal spin-spin coupling 287 Cyclopentanone 198 derivatives 168 Cyclopentene chemical shifts 83 derivatives 188 vicinal spin-spin coupling 303 Cyclopentenones, chemical shifts 168, 172, 188, 192, 235 Cyclopentenyl carbonium ion 252 Cyclopropane chemical shift 196 ring current in 98 Cyclopropane derivatives chemical shifts 197, 228 geminal spin-spin coupling 276 ^13C >H 1 4 1 stereochemistry from chemical shifts 227 vicinal spin-spin coupling 286 Cyclopropanone 198 Cyclopropene chemical shifts 101 derivatives 188 1-methyl 172 vicinal spin-spin coupling 303 Cyclopropenium cations 262 Cyclopropyl carbonium ions 253 Dailey-Shoolery relation 65 Decalones, axial and equatorial protons 241 446 Index 1,4-Decamethylenebenzene, chemical shift 97 Deceptively simple spectra 136, 147, 150 Delta scale 48 Deuterium exchange 53, 215, 299, 359 Deuterochloroform, purification and fast exchange 299 Diacetylene, solvent effects for 106 Diamagnetic anisotropy 72 and solvent effects 105 determination 74 determination from chemical shift 77 of acetylenes 93 of aromatic systems 94 of benzene 96 of carbon-carbon double bonds 83 of carbon-carbon single bonds 78 of carbon-halogen bonds 80 of carbon-hydrogen bonds 78 of the carbonyl group 88 of cyclopropane 98 of formaldehyde 88 of nitrile groups 93 of nitro groups 94 of nitrogen (sp2) atoms 82 of nitrogen (sp3) atoms 81 of ether oxygen atoms 81 of iodine 80 Diamagnetic shielding 61 Diaziridines, long-range shielding by 101 Dibenzo-[cf][l,2]-diazepin-ll-one, spectrum of 24 Dibenzyl 182 1,1 -Dibromo-2,2-dicyanoethane 58 1,2-Dibromoethylene-cw and trans, solvent effects on chemical shifts 109 Dibromemethane, chemical shift 160 Di-ter/-butyl disulphide 164 D i-tert-butyl ether 164 ß-Dicarbonyl derivatives, tautomerism 382 Dichloroacetaldehyde, double resonance spectra of 152 1,2-Dichloroethylene, eis and trans, solvent effects on chemical shifts 109 Dichloromethane, chemical shift 160 Dicyanoacetylene, solvent effects for 106 Dicyanomethane 182 Dielectric constant and polar solvent shifts 107 Diethyl disulphide 164 Diethyl ether 164 solvent effects for 106 Difluoromethane, chemical shift 160 Dihedral angle, definition 280 1,4-Dihydrobenzenes, spin-spin coupling 321 Dihydrodeoxycodeine-D 82 2,5-Dihydrofuran chemical shifts 188 spin-spin coupling 328 2,3-Dihydrofurans chemical shifts 188, 235 spin-spin coupling 304, 317 Dihydroindoles, chemical shifts 236 Dihydroisoindoles, chemical shifts 236 2,3-Dihydropyran, vicinal spin-spin coup-ling 304 D ihy dr opyr ans 188 Dihydropyridines spin-spin coupling 339 vicinal spin-spin coupling 304 D ihydropyrone 169 2,5-Dihydropyrrole, spin-spin coupling 328 Diphydrothiophens 188 2,5-Dihydroxypropiophenone 103 hydrogen bonding in 103 Diiodomethane, chemical shift 160 ^-Diketones chemical shifts 177 tautomerism 382 Dimethoxymethane 182 Dimethyl disulphide 164 Dimethyl ether 164 Dimethyl sulphate 177 Dimethyl sulphide 164 Dimethyl sulphite 177 Dimethyl sulphone 177 Dimethyl sulphoxidechemical shift 177 solvent effects 111 solvent effects for alcohols 299 Dinitromethane 182 2,4-Dinitrophenylhydrazones, chemical shifts 217 para-Dioxan 200 solvent effects 10 meta-Dioxans chemical shifts 237, 240 spin-spin coupling 273 1,2-Diphenylpropionic acid 143 Diphenyls, non-equivalence 378 Dipolar broadening 37 in solids 8 Dipole moment, influence on chemical shift 68 Di-/stf-propyl disulphide 164 Di-H-propyl disulphide 164 Di-wo-propyl ether 164 Di-jz-propyl ether 164 Dwso-propyl sulphide 164 Di-/i-propyl sulphide 164 Dispersion signals 27 Disulphides, dialkyl, chemical shifts 164 Index AM Diterpenes 244 DOG technique 42 Double irradiation see Spin decoupling Effective shielding coefficients 181 Electronegativity and spin-spin coupling to 13C 347 correlations of chemical shifts with 64, 66 influence on geminal coupling constants 276, 278 influence on proton chemical shifts 63 influence on vicinal spin-spin coupling 283, 302 Electrostatic effects, influence on proton shielding 67, 79 Enamines, chemical shifts 191 Enol acetates, chemical shifts 187 Enols 216 Episulphides, steroidal, chemical shifts 101 Epoxides see Oxirane Equivalence accidental, definition 119 and internal rotation 368 and symmetry 368 ff. chemical, definition 119 magnetic, definition 119 Esters chemical shifts 164, 176, 179 inorganic, chemical shifts 176 Ethane 1-amino-l-phenyl 166 chemical shift 164 Cotton-Mouton effect in 80 coupling constants 280 diamagnetic anisotropy of 76 1,1-dibromo 166 1,1-diphenyl 182 /i3Ci„ 141 monosubstituted, chemical shifts 64 Ethanol chemical shifts 164 low resolution spectrum of 13 proton exchange in 17 spectra of mixtures with water 18,19 spectrum of 14 spin-spin coupling 15, 299 Etherification shift 179 Ethers 179 chemical shifts 164, 179 cyclic, chemical shifts 189 Ethyl acetate 164 solvent effects of 106 Ethyl acetoacetate, tautomerism 177 Ethylamine, chemical shifts 164 Ethyl benzene 164 4-substituted 175 substituted, correlation of chemical shifts with Hammett σ-constants 66 Ethyl benzoate 164 Ethyl bromide 164 Ethyl chloride 164 Ethyl cyanate 178 Ethyl derivatives, chemical shifts 164 Ethylene analysis of the spectrum of partially deuterated ethylene 143 'i3C.„ 141 Ethylene carbonate 200 Ethyleneimine 199 Ethyleneimines, chemical shifts 229 Ethylene oxide 199 chemical shift 100 Ethylene sulphide 199 chemical shift 100 Ethylene sulphides, chemical shifts 229 Ethyl fluoride 164 Ethyl iodide 164 Ethyl isocyanate 178 Ethyl isocyanide 164 Ethyl isothiocyanate 178 Ethyl lithium 265 Ethyl mercaptan 164 Ethyl methyl ketone 164 Ethyl methyl sulphone 177 Ethyl nitrate, solvent effects for 106 Ethyl nitrite 177 Ethyl orthoformate 182 Ethyl phenyl ketone 164 Ethyl thiocyanate 177 Ethyl /7-toluenesulphonate 164 Exchange processes 55, 59, 358 of labile protons 215 External lock spectrometer 29 External references for spectra 44 Fast exchange in carbonium ions 253, 256 Ferrocenes chemical shifts 206 spin-spin coupling 309 Ferromagnetic impurities, removal of 36 Field-frequency lock 29 Field gradients 31 Field sweep 26 First order analysis 125 First order spectra, definition 124 Fluorene 197 Fluorenyl anion 266 Fluorine derivatives, spin-spin coupling in 348 448 Index Formaldehyde, diamagnetic anisotropy of 88 Formamide, N-alkyl, benzene solvent effects 111 Formamides, chemical shifts 191 Formates 191 chemical shifts 191 long-range spin-spin coupling in 343 Formyl protons, chemical shifts 191 Frequency response 38 Frequency sweep 26 Fulvenes, chemical shifts 206 Functional groups, influence on a-protons 176 Furanoquinolines, chemical shifts 213 Furans chemical shifts 207, 209, 214 /13c.„ HI methyl derivatives 173 spin-spin coupling 306 Furazan, chemical shifts 209 Furenidones, spin-spin coupling 342 Furoxans, isomerization 364 Gans-Mrowka relation 76 Gases, chemical shifts for 105 Gauche and trans interactions 29Γ Geminal spin-spin coupling see Spin-spin coupling, geminal /?-Z>-Glucopyranosides, aryl tetra-0-acetyl 113 Grignard reagents chemical shifts 263 ligand exchange 360 Gyromagnetic ratio 3 H—C—X, chemical shifts 174 H—C—C—X, chemical shifts 167 H—C—CO—X, chemical shifts 176 H—C—O—X, chemical shifts 176 Half-height width and vicinal coupling 288 Hamiltonian, spin 122 Hammett σ-constants, correlation with che-mical shifts 66 Helmholtz coils 26 Heterocyclic compounds chemical shifts 207 protonation 384 saturated, chemical shifts 199, 240 solvent effects 208 spin-spin coupling 305, 331 substituent effects on chemical shifts 208 tautomerism 383 Heterocyclopropanes chemical shifts 197, 224 geminal spin-spin coupling 276 stereochemistry from chemical shifts 227 vicinal spin-spin coupling 287 rt-Hexane, solvent effects for 106 Hex-2-en-4-onal, spectrum of 148 Hindered rotation, effect on n.m.r. line shapes 58 hom*oaromatic anions 266 hom*ogeneity 30 automatic control of 30 hom*otropylium cations 262 Hiickel's rule 98 Hybridization from / i 3 C H 347 influence on chemical shifts 70 Hydrazine derivatives, chemical shifts 217 Hydrazones chemical shifts 226 spin-spin coupling 344 Hydrido compounds, spin-spin coupling 344 Hydroaromatic compounds 197, 207 Hydrogen bonding 359 effect on chemical shifts 103, 216 Hydrogen exchange 359 Hydroxyl groups averaged spectra 359 axial and equatorial 240 chemical shifts 215 long-range spin-spin coupling 341 spin-spin coupling 298 Hydroxymethylene compounds, tautomer-ism 383 Imidazole N-acetyl 177 derivatives, chemical shifts 209 derivatives, spin-spin coupling 307 methyl derivatives 173 Indane 197 Indanones, chemical shifts 197, 223 Indazoles chemical shifts 210 spin-spin coupling 308 Indene chemical shifts 188 spin-spin coupling 317 Indenyl anion 266 Indole and derivatives, chemical shifts 209 and derivatives, spin-spin coupling 308 N-methyl 178 methyl derivatives 174 Index 449 Indolizines, spin-spin coupling 309 Inductive effects, influence on chemical shift 69 Integration of spectra 49 Intensity 13 factors influencing the measurements of 52 measurement of 49 Interatomic diamagnetic shielding 63 Internal lock spectrometer 29 Internal references for spectra 49 for acidic systems 249 Intrinsic non-equivalence 373 lodocyclohexanc, axial and equatorial 239 Isobutane 164, 168 chemical shifts 71 Isobutyric acid methyl ester 164 Isochronous nuclei 120 Isoeugenol, spectra of eis and trans 135 Isomerism cis-trans, from chemical shifts 224 cis-trans, from coupling constants 301 rapid, cis-trans 362 syn-anti, from chemical shifts 226 Isonitriles chemical shifts 164 spin-spin coupling to 1 4 N 354 Isopropyl chloride, spectrum of 128 Isoquinolines chemical shifts 212 spin-spin coupling 308 Isothiazoles, chemical shifts 213 Isothiocyanates 178 Isoxazoles, chemical shifts 213 Karplus equation 281 examples 294 ff. limitations 292 Ketals cyclic, chemical shifts 190, 236 formation equilibria 384 Ketene dimer, spin-spin coupling 317 Ketimines 226 Ketones benzene and toluene solvent effects 112 chemical shifts 164, 180, 195 cyclic, chemical shifts 188, 190, 198, 207 a-halogeno, conformation from spin-spin coupling 291 stereochemistry from solvent shifts 248 Ä,/?-unsaturated, chemical shifts 170, 187, 190, 192, 223 Λ,/3-unsaturated, benzene solvent effects 111 Lactams 198 N-acetyl 198 N-methyl 198 partial double bond character 362 ^-Lactams geminal spin-spin coupling 276 vicinal spin-spin coupling 287 Lactones 188, 198 spin-spin coupling 317 stereochemistry from solvent shifts 248 Larmor precession 61 Lewis acids, complex formation with 181 Line shapes, theory of the effect of chemical exchange on 57 Liquid crystals for the study of diamagnetic anisotropy 75 Lithium alkyls264 Local diamagnetic shielding 62 Local paramagnetic shielding 62 Longitudinal relaxation time, 7\ see Spin-spin lattice relaxation time Long-range shielding 63 by acetylene triple bonds 92 by aromatic rings 94 by carbon-carbon double bonds 83 by carbon-carbon single bonds 78 by carbon-hydrogen bonds 78 by carbonyl groups 88 by diazirine rings 101 by ether oxygen atoms 80 by furan nuclei 97 by halogens 80 by hydroxyl groups 80 by nitrile groups 93 by nitro groups 94 by s/?2-nitrogen atoms 82 by 5/?3-nitrogen atoms 81 by thiophene nuclei 97 by three-membered rings 98 in oximes 82 in Schiff's bases 82 in α,β-unsaturated acids and esters 91 in α,β-unsaturated acid chlorides 91 in α,β-unsaturated amides 91 in α,β-unsaturated ketones 91 point dipole approximation for 74 oc-Lumicolchicine, chemical shifts 92 M-rule 334 Magnetic field hom*ogeneity of 22 stabilization of 22 Magnetic shielding 61 Magnets 22 Maleic anhydride 188 Meisenheimer complexes 266 450 Index Mesomeric effect, influence on chemical shifts 70 Methacrylic acid and derivatives 171 Methane chemical shift 164 monosubstituted, chemical shifts 64 Methanethiol 164 Methanol, chemical shift 164 Methine protons, chemical shifts 165 Methoxybenzenes, correlation of Hammett σ-constants with chemical shifts 66 Methoxyl groups 180 axial and equatorial 240 long-range coupling to 243 Methylacetylene, / i 3 C H 141 Methylacroleins, ji*zCM 1 4 1 Methylamine 164 Methyl bromide chemical shift 160,164 solvent effects for 106 Methyl chloride, chemical shift 160, 164 Methylcyclohexane 169 Méthylène bromide, solvent effects for 106 Méthylène chloride, solvent effects for 106 Methylenedioxy group chemical shifts 200 spin-spin coupling 273, 277 Méthylène group chemical shifts 165 exocyclic, chemical shifts 190 non-equivalence 372 Méthylène iodide, solvent effects for 106 Methyl esters 180 Methyl ethers 180 Methyl fluoride, chemical shift 160, 164 Methyl groups angular, chemical shifts 244 attached to nitrogen, chemical shifts 178 attached to sulphur, chemical shifts 177 axial and equatorial 240 ß in enones 223 chemical shifts 164, 168 chemical shifts of angular 244 configuration from spin-spin coupling 298 effect on chemical shifts in aromatic systems 208 long-range coupling to 337 virtual coupling 298 Methyl isocyanide 164 Methyl iodide chemical shift 160, 164 solvent effects for 106 Methyl isothiocyanate 178 Methyl iso-propyl ketone 164 Methyl w-propyl ketone 164 Methyl thioacetate 177 Methyl thiocyanate 177 Methylthiophenes, correlation of Hammett σ-constants with chemical shifts 66 Methyl vinyl sulphide, spin-spin coupling 342 Microcells 40 Molecular Zeeman effect and diamagnetic anisotropy 74 Monascin 153 Monosaccharides 241 Morpholine 200 Multiple irradiation see Spin decoupling 15N Labels 383 NH groups averaged spectra 359 chemical shifts 217 spin-spin coupling 298, 355 Naphthalenes chemical shifts 205 ff. methyl derivatives, chemical shifts 173, 174 a- and β-nitro, chemical shifts 94 spin-spin coupling 306 Neighbouring paramagnetic shielding 63 Neohexylorganometallic compounds 263 Neopentane, solvent effects for 106 Neutron, magnetic properties of 1 Nickel(II) N,N'-di(6-quinolyl)-aminotro-poneiminate, spectrum of 102 Nitriles, chemical shifts 164, 225 Nitroalkenes 187 Nitrobenzene, solvent effects for 106 Nitro compounds aromatic 203, 204 chemical shifts 164 Nitrocyclohexane, axial and equatorial protons 239 Nitroethane 164 solvent effects for 106 Nitrogen, spin-spin coupling to protons 354 Nitromethane 164 solvent effects for 106 eis- and /rdrts-1-Nitropropene 94 N-Nitrosoamines 226 Non-benzenoid aromatic compounds, che-mical shifts 205 Non-equivalence 3 68 ff. solvent effects 221 Norbornadiene 188 Norbornadienyl cation 261 Index 451 Norbornane, derivatives, chemical shifts 100,230 2-Norbornanone 100 Norbornene, derivatives, chemical shifts 230 2-Norbornene, 7-methyl, syn and anti, che-mical shifts 84 5-Norbornene-2-carbonitrile, exo and endo, chemical shifts 84 5-Norbornene-2-carboxylic acid exo and endo, chemical shifts 84 2-methyl, exo and endo, chemical shifts 84 2-Norbornen-7-ol, syn and anti, chemical shifts 84 5-Norbornen-2-ol, endo and exo, chemical shifts 84 Norbonyl cation 260 Nuclear induction 27 Nuclear magnetic moment 1 Nuclear Overhauser effect 157 Nuclear quadrupole moment 1 1 7 0 labels 384 Olefms chemical shifts 184 cyclic, chemical shifts 188 cyclic, spin-spin coupling 285,303,339 geminal spin-spin coupling 277 ' 1 3 C . H 1 41 long-range coupling 323 vicinal spin-spin coupling 301 Onsager model, use for estimating polar solvent effects 107 Organometallic compounds, ligand ex-change 360 Overhauser effect see Nuclear Overhauser effect Oxazoles, chemical shifts 213 Oxetane 199 N-Oxides, heterocyclic, chemical shifts 213 Oximes, chemical shifts 191, 216, 226 Oxirane, chemical shift 100 Oxiranes chemical shifts 224, 228 solvent effects of chloroform on chemical shifts of 101 stereochemistry from chemical shifts 227 steroidal, chemical shifts 101 vicinal spin-spin coupling 287 4-Oxo-l,2,3,4-tetrahydrophenanthrene, chemical shifts 91 Oxygen, paramagnetic broadening by 31 Ozonides 200 Palmarin 157 Paramagnetic broadening 9 by oxygen 31 Paramagnetic impurities, removal of 37 Paramagnetic substances 367 Partial double bond character 361 Pentalenyl dianion chemical shifts 266 spin-spin coupling 309 «eo-Pentane 168 Pent-3-ene-l-yne-4-methyl 171 Pent-1-yne 164 Peri effects 204, 208, 214, 225, 244 Phase sensitive detection 29 Phenanthrene derivatives, chemical shifts 204, 205 derivatives, spin-spin coupling 306, 342 9,10-dihydro 197 4-oxo-l,2,3,4-tetrahydrophenanthrene, chemical shifts 91 Phenanthroline, spin-spin coupling 309 Phenetole 164 Phenol intermolecular hydrogen bonding in 103 substituted, correlation of chemical shifts with σ~ 66 Phenolates 204 Phenols 203,204,216 Phenylacetylene, correlation of chemical shift with Taft's substituent parameter 67 Phenylcyclohexane, axial and equatorial protons 239 5-Phenyl-l,2,3,4,7,7-hexachlorobicyclo-[2.2.1]hept-2-ene, correlation of che-mical shifts of 5- and 6-protons with Hammett σ-values 66, 69 Phenylhydrazine, N-methyl 178 Phenylmethyl carbanions 265 Phenyl /50-propyl ether 164 Phenyl w-propyl ether 164 Phenyl «0-propyl ketone 164 Phenyl /i-propyl ketone 164 Phosphate esters, chemical shifts 179 Phosphine derivatives chemical shifts 179 spin-spin coupling 300 Phosphorus, spin-spin coupling to protons 353 Phosphorus derivatives 181 chemical shifts 179 Phthalazine, spin-spin coupling 309 Phthalimide, N-methyl 179 Picolines 174 Piperidine 199 452 Index Piperidine (cont.) N-acyl 199 axial and equatorial protons 240 chemical shifts 100 N-methyl 178 Pivalic acid 164 methyl ester 164 Pivalic aldehyde 164 Point dipole approximation for long-range shielding 74 Polyacetylenes, spin-spin coupling 330 Polyenes chemical shifts 170, 187, 225 cyclic, chemical shifts 206 Polynuclear hydrocarbons, chemical shifts 174, 204 Porphin, chemical shifts 97 Porphyrins, chemical shifts 97 Precessional motion of nucleus 3 Propanal, 2-methyl 164 Propane 1 -bromo-3-phenyl 166 chemical shifts 164 1 -chloro-2,2-difluoro 166 1-chloro-l-nitro 166 coupling constants 280 1,1-diphenyl 168 1,3-diphenyl 166 1-nitro 164 2-nitro 164 /jtf-Propanol 164 Λ-Propanol 164 Propene 1 -acetoxy-2-methyl 171 2-acetoxy 171 2-bromo 171 1 -bromo-2-methyl 171 chemical shifts 164 2-chloro 171 2-cyano 171 derivatives 192 derivatives, chemical shifts 170 derivatives, spin-spin coupling 316, 323 2-methyl 171 eis and trans-l-nitro 94 Propiolactam 198 Propiolactone 198 Propionaldehyde 164 Propionamide 164 Propionic acid 164 2-chloro 166 methylester 164 Propionitrile 164 iso-Propy\ acetate 164 Λ-Propyl acetate 164 /so-Propylamine 164 tf-Propylamine 164 iso~Propy\ benzene 164 /z-Propyl benzene 164 wo-Propyl benzoate 164 /z-Propyl benzoate 164 /so-Propyl bromide 164 «-Propyl bromide 164 /so-Propyl chloride 164 /z-Propyl chloride 164 /so-Propyl cyanide 164 «-Propyl cyanide 164 /stf-Propyl derivatives, chemical shifts 164 «-Propyl derivatives, chemical shifts 164 iso-Propyl fluoride 164 «-Propyl fluoride 164 /so-Propyl groups, non-equivalence 375 wö-Propyl iodide 164 «-Propyl iodide 164 /so-Propyl isocyanide 164 «-Propyl isocyanide 164 /so-Propylisothiocyanate 178 /io-Propyl mercaptan 164 « -Propyl mercaptan 164 /so-Propyl thiocyanate 177 /so-Propyl /?-toluenesulphonate 164 «-Propyl/?-toluenesulphonate 164 Propyne chemical shifts 164 solvent effects for 106 Proton exchange, effect on spectrum 17 Pteridines chemical shifts 213 spin-spin coupling 309 Purines 208 chemical shifts 210 spin-spin coupling 309 Pyrane, tetrahydro-, chemical shifts 100 Pyrazines chemical shifts 211 spin-spin coupling 307 Pyrazole derivatives 208 derivatives, chemical shifts 209 derivatives, spin-spin coupling 307 N-methyl 179 methyl derivatives 173 Pyrene chemical shifts 205 2,7-diacetoxy-/ra«5'-15,16-dimethyl-15, 16-dihydro, chemical shifts 97 spin-spin coupling 306 Pyridazines 207 chemical shifts 211 spin-spin coupling 307 Pyridines chemical shifts 207, 211,213 long-range shielding by the lone pair 82 Index 453 Pyridines (cont.) spin-spin coupling 307 a -Pyridones chemical shifts 211 N-methyl 178 4-methyl, protonation 299 Pyrimidines 207 chemical shifts 211 methyl derivatives 174 spin-spin coupling 307 Pyrimidones, chemical shifts 213 y-Pyrone, vicinal spin-spin coupling 304 Pyrone derivatives 172, 189 spin-spin coupling 340 Pyrrole and derivatives 208 derivatives, chemical shifts 209 derivatives, spin-spin coupling 306 N-methyl 179 methyl derivatives 173 Pyrrolidine 199 N-acetyl 199 N-acetyl, derivatives 236 N-methyl 178 Pyrrolidone, N-methyl 178 Pyrrolines N-acetyl 236 methyl derivatives 169 Pyrrolones, tautomerism 383 Pyrylium salts 309 Quadrupole broadening 10, 58, 142, 360 Quaternary ammonium salts 354 Quinazoline 207, 213 derivatives 207, 213 spin-spin coupling 309 Quinolines chemical shifts 207, 211 spin-spin coupling 308 Quinolizidine, methyl derivatives, chemi-cal shifts 82 Quinolizidone, chemical shifts 92 Quinones, stereochemistry from solvent shifts 248 Quinoxalines, spin-spin coupling 309 Radiciol 157 Radiofrequency oscillator 25 Radiofrequency phase 33 Reaction field, contribution to solvent effect 107 References delta (<5) values of 49 internal references for intensity measure-ments 51 Resolution 313 criteria of 31 Restricted rotation 361 Rifomycin B, chemical shifts 97 Ring current in aromatic systems 95 in cyclopropane 98 Ring size, from vicinal spin-spin coupling 303 Ringing patterns 35 Rotation, internal and equivalence 368 Rotsnolone A and B, methyl ethers, chemi-cal shifts in 91 Rotenone, 12-desoxy-6',7'-dihydro, chemi-cal shifts 92 Sample preparation 36. Santonins, stereochemistry from vicinal coupling 295 Satellites 345 Saturation 10 Saturation factor 10, 314 Schiff's bases 172, 226 S^lenophene chemical shifts 209 spin-spin coupling 307 Semicarbazones 336 Sensitivity, enhancement of 41 Shielding constants 182 Shielding effects, additivity of 181, 185 Shikimic acid, stereochemistry from vicinal coupling 296 Shims, current 23 Shoolery's rules 181 Side band modulation 39 Side-chain spin-spin coupling 331 Signal-to-noise ratio 38 Silane derivatives, spin-spin coupling 300 Silicon tetrachloride, solvent effects for 106 Simon's rules 184 Six-membered rings, configuration from spin-spin coupling 288 S-methyl groups 180 Solvent effects 53, 104, 181, 246 and stereochemistry 246 as an aid to analysis of spectra 144 correlation with heats of vaporization 105 Solvents, purification and fast exchange 299 Solvent shifts 246 Spin decoupling (multiple irradiation) 151 analysis of spectra by 145 determination of highly accurate chemical shifts by 155 454 Index Spin decoupling(cont.) determination of relative signs of coup-ling constant by 154 field sweep method 152 frequency sweep method 152 heteronuclear 153 hom*onuclear 153 interrelation of two or more coupled groups of nuclei 157 location of "hidden" absorption by 155 measurement of rate of chemical ex-change by 157 simplification of complex spin multiplets by 153 theory of 151 Spin Hamiltonian 122 Spin-lattice relaxation 6 Spin-lattice relaxation time, 7\ 7 Spinning of sample and hom*ogeneity 23 Spinning side bands 33 Spin numbers 1, 355 Spin-spin coupling 13 applications 269 across 4 single bonds 334 across 5 bonds 333, 342 across 6 bonds 342 allylic 316 and bond-order in aromatic systems 310 and ring size in aromatic systems 310 average over a number of conformations 61 benzytic 330 between 13C and 1H 345 between 19F and XH 348 between nitrogen and protons 354, 383 between 31P and *H 353 between protons and miscellaneous ele-ments 354 constant, / , definition of 17, 116 effect of substituents in aromatic com-pounds 310 geminal 270 across a heteroatom 279 and configuration 275 in exocyclic = CH2 groups 279 in formaldehyde derivatives 277 in unsaturated systems 277 in vinyl derivatives 278 influence of π-bonds 273, 278 influence of H—C—H angle 273 influence of ring size 275 influence of substituents 276 measurement by partial deuteration 143 relative signs 270 small values of 277 solvent effects 277, 279 in X = CH2 groups 277 hom*oallylic 316, 325 inter-ring in aromatic compounds 333 long-range 312 mechanism of 115 of OH, NH and SH groups 298 relative sign of 117, 154 signs in aromatic systems 305 theoretical calculation of 118 vicinal 280 and bond order 303 and conformation 289 and fast exchange 299 axial-equatorial 288 axial-axial 288 equatorial-equatorial 288 gauche and trans 291 in five-membered rings 287 in flexible systems 289 inH—C—X—H 298 II II II in H—C—C—H and H—C—C—H 284 in unsaturated systems 301 in vinyl derivatives 278 influence of dihedral angle 281 influence of ring size in saturated systems 286 influence of substituents in saturated systems 283 of methyl groups 298 relative signs 280, 285 solvent effects 304 Spin-spin multiplet 115 analysis of 122 exact analysis of 123 recognition of 115 Spin-spin relaxation time, T2 8 Spin systems AA'BB' 134 AA'XX' 134 AB 129 AB2 130 A2B2 134 ABC 133 ABX 133 ABXn 134 AMX 132 AX2 130 A2X2 134 classification of 121 miscellaneous 139 Stannic chloride, solvent effects for 106 Stereochemistry cis-trans and vicinal coupling 286, 301 cis-trans from chemical shifts 222 Index 455 Stereochemistry (cont.) from allylic coupling 322 from chemical shifts 219 from solvent shifts 246 Stereoisomers, chemical shifts in meso and dl forms 163 Steroids chemical shifts 92 chemical shifts of angular methyl groups 242 cyano substituted, chemical shifts 94 3a,5a-cyclo, chemical shifts 99 episulphides, chemical shifts 99 epoxides, chemical shifts 99 1 l-keto-5c\-, chemical shifts 91 6Ä- and 6/>-nitro, chemical shifts 94 Δ4-3-οχο, chemical shifts 245 Stilbenes 224 oxides 224 sulphides 224 Strained systems, spin-spin copuling 335 Structure determination, and vicinal coup-ling 300 Styrene derivatives, chemical shifts 170,187,224 a-methyl 171 oxide, spectrum of 126 oxide, spin-spin coupling 272 sulphide, spin-spin coupling 272 Subspectra 123 α-substituents, influence on chemical shifts 165 ß-substituents, influence on chemical shifts 165 Succinic anhydrides 200 chemical shifts 235 Succinimide 200 Sulphides 180 Sulphinamides, non-equivalence 377 Sulphinates 180 non-equivalence377 Sulphites, non-equivalence 377 Sulphonates 180 Sulphones 177, 180 Sulphoxides, non-equivalence 377 Sulphur derivatives 180 Sulphydryl groups averaged spectra 359 spin-spin coupling 298 Symmetry and equivalence 368 if. and fast exchange 221 and rapid inversion 365 Syn-anti isomerism 226 Taft's σ*-constants, correlation with che-mical shifts 66, 70 Tau scale 48 Tautomerism 380 and spin-spin coupling 299 Temperature dependence of spectra 368 Tetrahydrofuran 199 Tetrahydropyran 199 1,2,5,6-Tetrahydropyridine, spectrum of 146 Tetrahydrothiophene 199 dioxide 199 Tetrahydrothiopyran 199 Tetralin 197 a-Tetralone 197 chemical shifts 91 Tetramethylsilane (TMS) as an internal reference 46 Tetrazoles, chemical shifts 213 Thiapyran, tetrahydro-, chemical shifts 100 Thiapyrones, vicinal spin-spin coupling 304 Thiazoles chemical shifts 209 methyl derivatives 173 spin-spin coupling 307 Thienopyr roles chemical shifts 213 spin-spin coupling 309 Thiethane 199 Thiirane, chemical shift 100 Thioacetic acid 177 Thiocyanates 177 Thioethers, chemical shifts 164 Thiols chemical shifts 164, 215 spin-spin coupling of SH groups 298 Thiophens 207, 214 chemical shifts 209 /i3C i H 141 methyl derivatives 173, 175 spin-spin coupling 307 Thiopyrones, vicinal spin-spin coupling 304 Thiosulphites, cyclic, chemical shifts 236 Thiosulphonates 180,220 Tlireo and erythro forms from chemical shifts 163 from spin-spin coupling 291 /?-Thujone, chemical shifts 92 Time-dependent phenomena 17 applications 358 Toluene chemical shifts 164 derivatives, chemical shifts 170 nitro derivatives 175 solvent effects of 112 /7-Toluenesulphonic acid, methyl ester 164 456 Index Transverse relaxation time, T2 see Spin-spin relaxation time Tribromomethane, chemical shift 160 Triazines, chemical shifts 211 Triazoles, chemical shifts 213 1,1,1 -Tr ichloroethane 177 1,1,2-Trichloroethane 166 Trichloromethane, chemical shift 160 Tricyclo[2.2.1.02,6]heptane, chemical shifts 100 Tricyclo[3.1.1.06*7]heptane 99 Tricyclo[2.2.1.02'6]heptan-3-one chemical shifts 100 1,7,7-trimethyl 100 Tricyclo[2.1.1.05'6]hexane, 1-methyl, che-mical shifts 99 Tricyclo[1.1.1.04'5]pentane,l,3-dimethyl, chemical shifts 99 Triethylamine, solvent effects for 106 Trifluoroacetates 179 Trifluoroacetic acid as solvent for amines 359 Trifluoromethane, chemical shift 160 Triiodomethane, chemical shift 160 jS-Triketones, tautomerism 382 Trimethylene oxide 199 2,4,4-Trimethyl-2-pentene 171 Trimethylsilyl ethers 240 Trinitromethane 182 Trioxans 200, 237 Triphenylene, chemical shifts 205 Triphenylmethane 182 Triphenylmethyl anion 263 Triphenylmethyl cation 263 Triptycene 197 Triterpenes 244 chemical shifts 92 Trithians 200 Tropolones 204 spin-spin coupling 309 Tropylium cation 262 UCP non-equivalence, definition 374 Urea derivatives 178 Urethanes 178 Valance-bond tautomerism 362 Valerolactam 198 Valerolactone 198 van der Waal interactions and chemical shifts 105 and solvent effects 71 van der Waals' shifts 204 Variable temperature studies and time-de-pendent phenomena 358 Vicinal spin-spin coupling see Spin-spin coupling, vicinal Vinyl derivatives chemical shifts 187 / 1 3 C .H 141 spin-spin coupling 278 Vinyl ethers, chemical shifts 187 Vinylic protons 184 Virtual coupling 133, 147 Viscosity, effect on spin-lattice relaxation 8 Volume susceptibility, correction for 4 Width at half-height (WH) 288, 314 Wiggle-beats 35,313 W-rule 334 Xylenes 170, 175, 203