Subject Index

Subject Index

Downloaded by EASTERN KENTUCKY UNIV on March 20, 2013 | http://pubs.acs.org Publication Date (Web): March 19, 2013 | doi: 10.1021/bk-2013-1128.ix002

A

77Se/31P

hyperfine splittings, 175 square planar dppeNiCysEt+ cation and JCP splitting patterns, 177f TpMBH4 in CD2Cl2, 11B NMR spectrum, 183f Tp'Rh(cod) in protio-THF, 13C NMR spectrum, 179f unconventional hyperfine splittings, 13C NMR spectroscopy, 177 various heteronuclei accessible to modern FT-NMR instruments, 170t

Aldol reactions Claisen-Schmidt reaction, 92 aldol condensation of 2'-hydroxyacetophenone with benzaldehyde, 93s crossed aldol condensation and Michael addition, 93s crossed aldol condensation of acetophenone with benzaldehyde, 92s conclusions, 101 discussion 2'-hydroxyacetophenone, aldol reaction, 95 2-pyridinecarboxaldehyde, tandem Aldol-Michael reactions, 99 investigate products, using NMR, 91 (APT). See attached proton test (APT) Attached proton test (APT), 17

C Correlation spectroscopy (COSY), 3, 32 COSY. See correlated spectroscopy (COSY); correlation spectroscopy (COSY)

D B Beyond ordinary undergraduate experiences routine measurements with heteronuclear, heterogeneous, and aramagnetic samples 27Al NMR spectroscopy, collaborative dye experiment, 180 11B NMR chemical shifts, 182f 11B NMR spectra, schematic representations, 176f cis/trans geometric isomers, 31P NMR resolution, 173 conclusions, 184 experimental methods, 171 introduction, 169 KTp' supported on polystyrene synthesis beads, 13C NMR spectrum, 181f [PPh4][Tp'Mo(CO)3], 13C NMR spectrum, 178f resin-supported ligands, 13C NMR spectroscopy, 180 routine paramagnetic 11B NMR spectroscopy, 182 scorpionates, 11B NMR specotrscopy, 175

DEPT. See distortionless enhancement by polarization transfer (DEPT) Distortionless enhancement by polarization transfer (DEPT), 18 D2O shake test, 50

E Eugenol hydrogenation, 84s

F Friedel-Crafts acylation reactions p-methyl anisole with propionyl chloride, 108, 108f potential products, 109f reaction of p-cymene with acetyl chloride 13C NMR spectrum, 118f 1H NMR spectrum, 119f spectral data (1H, 13C, and HSQC) and partial peak assignments, 119t two isomeric products, 120f two possible isomers, 117f

341 In NMR Spectroscopy in the Undergraduate Curriculum; Soulsby, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


reaction product of p-methyl anisole aromatic methyl group, 2- and 3-bond HMBC cross peaks, 113t, 114t 13C NMR spectrum, 109f chemical shift values, 111t chemical shift values and their assignment to atoms, 115t 1H NMR spectrum, 110f HMBC spectrum, 112f HSQC spectrum, 110f structure, 116f reaction products of p-cymene with acetyl chloride, 117 HMBC spectrum, 120f HSQC spectrum, 118f spectral data (1H, 13C, HSQC, and HMBC) and complete peak assignments, 121t structure with chemical shifts of atoms, 122f

I INADEQUATE. See incredible natural abundance double quantum transition (INADEQUATE) Incredible natural abundance double quantum transition (INADEQUATE), 19

K

G

Keto-enol equilibria, effect of substituents comparison of keto-enol equilibrium constants Kc with Hammett substituent constants, 208t conclusions, 209 experimental methods, 206 introduction, 205 NMR shift assignments, peak integrations, and experimentally determined values, 207t 2,4-pentanedione derivative, tautomeric equilibrium, 206s

Gated 13C experiment, 15 Geometric isomers, heteronuclear coupling, 155

L

H H2BC. See heteronuclear 2 bond correlation (H2BC) HETCOR. See heteronuclear chemical-shift correlation (HETCOR) Heteronuclear 2 bond correlation (H2BC), 29 Heteronuclear chemical-shift correlation (HETCOR), 27 Heteronuclear correlation through multiple quantum coherence (HMQC), 27 Heteronuclear multiple bond correlation (HMBC), 29 Heteronuclear single quantum coherence (HSQC), 3 Heteronuclear single quantum correlation (HSQC), 27 HMBC. See heteronuclear multiple bond correlation (HMBC) HMQC. See heteronuclear correlation through multiple quantum coherence (HMQC) HSQC. See heteronuclear single quantum coherence (HSQC); heteronuclear single quantum correlation (HSQC)

Less common NMR experiments, one- or two-dimensional experiments, 39t Less common one-dimensional 13C NMR experiments, summary, 38t Lipid membranes' phase behavior 1H NMR MAS investigations 1:1 DMPC:cholesterol mixture, 1H NMR MAS spectra, 254f chemical shift assignment, 252f DMPC spectral assignment, 252 effect of rotor spinning frequency, 253 further studies, 256 1H MAS NMR experiments, 251 1H NMR MAS spectra, temperature dependence, 255f introduction, 245 lipid phases, 246 magic-angle spinning, 250 normalized (CH2)n intensity for DMPC and DMPC, 255f phase transition temperature, determination, 253 preparation of DMPC, cholesterol samples, 251



M Modern NMR experiments benzene-containing C9H12 structural isomers, 11 butyl 2-phenylbutyrate, COSY spectrum, 32f camphor in DMSO-d6, partial INADEQUATE spectrum, 31f conclusions, 36 2D INADEQUATE experiment, 30 2D NMR experiments, introduction, 27 2D NOESY experiment, 34 2D TOCSY experiment, 35 1H-13C HMQC spectrum, 28f HETCOR, HMQC, and HSQC experiments, 27 HH-COSY experiment, 32 HMBC and H2BC experiments, 29 9-hydroxyphenalenone, expanded HMBC spectrum, 30f one-dimensional 13C NMR experiments, introduction, 8 α- and β-anomers of glucose, 12f 5% solution of sodium borohydride, 1H NMR spectrum, 26f 13C attached proton test, 17 carboxylic acid resonance, proton-coupled 13C NMR, 16f (C6H5)2CHOCH(C6H5)2, APT spectrum, 17f cyclohexanone mixture, percentages, 14t 1D INADEQUATE experiment, 19 1D NOESY experiment, 20 1D TOCSY experiment, 22 DEPT experiment, 18 19F spectra, 24f gated 13C experiment, 15 inorganic cobalt complex, 25 inverse-gated 13C experiment, 13 inversion recovery 13C experiment, 12 isobenzofuranone Diels-Alder product, 22f off-resonance 13C decoupling, 16 one-dimensional 1H NMR experiment, 19 other nuclides, 1D NMR experiments, 23 31P NMR spectroscopy, 25 partial 1H NMR and NOE difference spectrum, 21f partial 1H NMR spectra, 20f proton broadband decoupled 13C experiment, 10

various liquid sample experiments, non-theoretical explanations, 8 verbenone, HH-COSY spectrum, 33f Most common NMR experiments, summary, 37t

N National Science Foundation, research and curriculum programs, 321 NMR. See nuclear magnetic resonance (NMR) NMR data acquisition and processing, collaboratory conclusions, 304 Oregon NMR Consortium member institutions, overview, 295t program design activities, 298 common NMR spectroscopy experiments, 299t Consortium network configuration for users, 297f curriculum, 298 equipment, 296 overview, 296 sample transport and analysis at remote locations, 299 project assessment overview, 300 remote access to operate NMR spectrometer, 302 student cohorts in organic chemistry, assessment scores, 303t using modern chemical technology, assessment of confidence, 302 using remote access, assessment scores of student attitudes, 302t NMR spectrometers categories, 8 signal-to-noise ratios, 11 writing more competitive grant proposals NMR spectroscopy conclusions, 5 development, 2 future directions, 4 high-field magnets, 5 impact, 2 instruments, 4 introduction, 1 National Science Foundation (NSF) encouragement, 4 overview, 2 undergraduate curriculum, 3



NMR technology, 3 NOE. See nuclear Overhauser effect (NOE) NOESY. See nuclear overhauser effect spectroscopy (NOESY) Nondeuterated solvents (No-D NMR) advantages, 71 common NMR solvents, cost, 72t conclusions, 80 FT-NMR spectrometers, 70 1H NMR spectroscopy, deuterated solvents, 70 instrument setup and shimming, 73 introduction, 69 4-methoxyphenethylamine, NMR spectrum, 71f 2-methyl-3-buten-2-ol, 1H-NMR spectrum, 75 solvent selection and sample preparation, 72 anhydrous grade solvents, 73 sample, 73 spectral snalysis, 74 undergraduate organic laboratory, applications, 75 esterification, product purity, 77 product from esterification of propanoic acid and ethanol, 13C-NMR spectrum, 77f progress of esterification of 4-hydroxybenzoic acid with ethanol, 1H NMR spectrum, 78f pyranochalcone synthesis, 79s reaction mixture, 1H NMR spectra, 80 synthetic projects, monitoring reactions, 79 unknowns identification, 76 Wittig reaction, 78 Nuclear magnetic resonance (NMR), 1 Nuclear Overhauser effect (NOE), 10 Nuclear Overhauser effect spectroscopy (NOESY), 20

O Oregon NMR Consortium, 293 Organic chemistry introducing NMR, 45 conclusions, 53 N,N-dimethylformamide (DMF), 47s proton exchange at C-2 position, 51s proton exchange reaction, 51s Organic chemistry lab overcoming problems incorporating NMR

benzylic methylene, splitting patterns, 87 conclusions, 89 continuous-flow reactors, 84 Delta™ software, 83 1H NMR (CDCl3) spectra of eugenol, 88f introduction, 83 partial expanded 1H NMR (CDCl3) spectrum of eugenol, 88f version of iNMR, 86 Organometallic complexes characterization conclusions, 166 further experiments, 165 introduction, 155 NMR nuclei, 156 NMR nuclides, selected properties, 156t P(mes)3, 13C NMR spectrum, 162f 195Pt and 31P NMR, 155 [Pt(μ-Cl)]2 31P NMR spectrum, 165f partial 1H NMR spectrum, 164f [Pt(PhCN)2Cl2] 13C NMR spectrum, 163 1H NMR spectrum, 163 [Pt(PhCN)2Cl2] and [Pt(μ-Cl)]2, 195Pt NMR spectra, 162f relative receptivity, 156 synthesis data acquisition, 160 heteronuclear coupling, 160 [Pt(μ-Cl)]2, 159 [Pt(PhCN)2Cl2], 158 selected NMR data summary, 161t tunable broadband probe, 157

P Physical chemistry laboratory projects DFT-B3LYP-GIAO method, theoretical calculations, 231 NMR and DFT-B3LYP calculations Bruker Spectrospin 400 NMR, 231 conclusions, 241 Dalton’s law of partial pressures, 236 dimerization for methanol vapor, determination of enthalpy, 235 dimer-monomer equilibrium of methanol, determination of ΔH and ΔS, 237f experimental, 230 impurity peaks, 231 mass susceptibility and magnetic moment of O2, 234



measured and calculated chemical shifts for methanol, comparison, 233t methanol in dilute solutions, 238 methanol molecules, dimers, and trimers, minimized structures, 233f methanol neat liquid and vapor in air, NMR spectra, 232f methanol–acetone activity coefficients at infinite dilution, 240 methanol–solvent interaction energies, 239 molar susceptibility and magnetic moment for oxygen, 235t OH chemical shift, effect of hydrogen bonding, 232 OH chemical shift as function of mole fraction methanol, 238f OH chemical shifts and hydrogen bond energy for methanol, 240t

S Sophomore organic chemistry lab use of HSQC, HMBC, and COSY background, 104 conclusions, 127 experimental, 107 fisher esterification and COSY spectra, 123 Structure-reactivity relationships in carbonyl reduction carbonyl reduction using borohydride reagents, 264 carbonyl substrates, structural differences, 271 conclusions, 272 electron-withdrawing groups, 271 examined trends, 266t expansion of NMR spectroscopy in curriculum, 263 experiment, results and discussion, 268 experimental procedure development, 267 performance evaluation, 272 reduction of acetone, reaction orders, 269f reduction of acetone by NBu4BH4 in CD2Cl2, 1H NMR spectra, 269f reduction of carbonyl compounds by borohydride reagents, 265s reduction reactions, rate constants, 269t sophomore experience and senior capstone experience, 273

vertical integration, 262 vertically integrate NMR spectroscopy, 263 Substituent interactions in aromatic rings background, 190 C4 and C6 nuclei, 13C chemical shift differences, 199t 13C nucleus in benzene, gas-phase isotropic shielding, 194t 13C shifts relative to TMS, 196t chemical shift values, 191 electronic structure calculations, 193 conclusion, 202 conventions, terminology, and values for 13C chemical shifts, 192f curious case of 2-nitroaniline, 194 experimental and calculated 13C chemical shifts relative to TMS, 196t experimental 13C chemical shifts [ppm] of aniline, nitrobenzene, and 2-nitroaniline, 196f 1H-coupled 13C NMR spectra, 199 hydrocarbon systems, 2,2,4-trimethyl1,3-pentanediol, 202f indanes, 5-substituted indane, 201f magnetic field, different energy levels, 191 5-methyl-2-nitroaniline, 200f 1H-coupled 13C spectrum, selected region, 201f nuclear spin JCH couplings, 200t 2-nitroaniline in CDCl3, 2-D CH-COSY spectrum, 197f practical considerations, 202 shielding tensor [ppm], calculated components, 198t WebMO interface, 202

T Teaching of NMR spectroscopy 13C NMR spectrum of cholesterol, 310f ChemSpider record, 308f conclusions, 317 data quality, 309 database, 308 future work, 317 integrating NMR data to other RSC platforms ChemSpider SyntheticPages, 312 example reaction, screenshot, 314f learn chemistry wiki, 310, 311f SpectraSchool, integrated data for teaching spectral interpretation, 312



SpectraSchool website, infrared spectrum for butyric acid, 313f NMR spectral data, programmatic access final level of game offers five structures, 315f large solvent peaks, 316 spectral data identifiers, 316 spectral game, 314 spectral data, 309 TOCSY. See total correlation spectroscopy (TOCSY) Total correlation spectroscopy (TOCSY), 22

U Undergraduate chemistry laboratories NMR-based kinetic experiments approximate completion times, 217t arrhenius analysis using VT-NMR, 221 conclusion, 228 dehydration kinetics and establishing reaction order, 217 1,1-diphenylpropan-1-ol, monitoring dehydration, 212 Undergraduate curriculum at University of Notre Dame Avance III 400 MHz NMR console, 276f Bruker Avance III NMR, 277f conclusions, 287 IconNMR sample entry screen, screen shot, 277f NMR spectrometer use in majors courses chemical principles laboratory, introduction, 279 chemistry across periodic table laboratory, 283 dicyclopentadiene cracking cyclopentadiene distillation experiment, 282f H2-tetraphenylporphyrin, 1H NMR spectrum, 284f mixture of (Z)- and (E)-2-bromo-1-phenylethene, 1H NMR spectrum, 281f organic reactions and applications laboratory, 282 organic structure and reactivity laboratory, 279 paramagnetic cobalt tetraphenylporphyrin, 1H NMR spectrum, 284f

saccharin alkylation experiment, results, 280f 119Sn NMR spectrum of Tin (IV) Iodide in DMSO-d6, 283f NMR spectroscopy, 275 non-majors introductory and advanced-level courses, NMR spectrometer use anomeric proton signals of lactose, 286f biochemistry laboratory, 287 HSQC NMR spectrum of methyl-α-glucose, 286f organic reactions and applications laboratory, 285 Notre Dame chemistry courses, 278 Notre Dame facilities, 276 trouble-shooting sample preparation, 287 Undergraduate inorganic curriculum conclusions, 151 inorganic and organic curricula, comparison of NMR spectroscopy topics, 151t inorganic chemistry I magnetic inequivalence, N3P3F6 structure, 143f monitoring reactions, 138 31P NMR spectroscopy, introduction, 136 inorganic chemistry II NMR active nuclei, 146 NMR active nuclei, magnetic inequivalence, 149 student insights, 132 Undergraduate organic laboratory courses promote active learning, using NMR spectroscopy 1 M t-butyl bromide solvolysis alkene mixture, 1H NMR spectrum, 62f analyses of mixtures, 1H NMR spectroscopy, 61 aromatic tertiary alcohols synthesis, 59 atom equivalency and 13C NMR spectroscopy, 58 C6H12 alkene isomers, 58f conclusions, 67 cyclopentadiene, dimerization, 66f 3-methyl-2-phenyl-2-butanol, 1H NMR spectrum, 60f reaction kinetics, 65 teach experimental design, 63 tertiary alcohol syntheses, unknown ketones used, 59f


use of unknowns, engage student learning, 59

V

Writing more competitive grant proposals NMR spectrometers conclusions, 331 MRI and TUES proposals, project description section, 322 TUES program focus, 321


Vertical integration of NMR in chemistry curriculum, 261

W


Subject Index

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