Problem 13.3 2-Chloropropene shows signals for three kinds of protons in its 'H NMR spectrum. Explain. Problem 13.4 The following 'H NMR peaks were recorded on a spectrometer operating at 200 MHz. Convert each into 8 units. (a) CHCly;1454 Hz (b) CHCl; 610 Hz (©) CHOH; 693 Hz = (d) CHCl; 1060 Hz Problem 13.5 When the 'H NMR spectrum of acetone, CH3COCHs, is recorded on an instrument operat- ing at 200 MHz, a single sharp resonance at 2.1 is seen. (@) How many hertz downfield from TMS does the acetone resonance correspond to? (b) if the 'H NMR spectrum of acetone were recorded at 500 MHz, what would the position of the absorption be in 6 units? (c) How many hertz downfield from TMS does this 500 MHz resonance correspond to? Problem 13.14 How many kinds of electronically nonequivalent protons are present in each of the follow- ing compounds, and thus how many NMR absorptions might you expect in each? (a) CH3CH8r (b) CH3OCH2CH(CH3)2_— (¢) CH3CH2CH2NO2 (d) Methylbenzene _(e) 2-Methyl-I-butene __(F) cis-3-Hexene Problem 13.15 How many absorptions would you expect (S)-malate, an intermediate in carbohydrate metabolism, to have in its 'H NMR spectrum? Explain. (S)-MalateProblem 13.18 How many peaks would you expect in the 'H NMR spectrum of 1,4-dimethylbenzene (para- xylene, or p-xylene)? What ratio of peak areas would you expect on integration of the spec trum? Refer to Table 13.3 for approximate chemical shifts, and sketch what the spectrum. would look like. (Remember from Section 2.4 that aromatic rings have two resonance forms.) io Problem 13.19 Predict the splitting patterns you would expect for each proton in the following molecules: (a) CHBr2CHy (b) CHzOCH2CH28r (€) CICH,CH2CH2CI (a) ° (co) 9 0 CHacHCOCHsCHa (CHacHCOcHCHs CHy CH Problem 13.20 Draw structures for compounds that meet the following descriptions: (@) CaHg0; one singlet (b) C3H7Cl; one doublet and one septet (©) CyH3Ciz0; two triplets (d) CaHgO2; one singlet, one triplet, and one quartet Problem 13.21 The integrated 'H NMR spectrum of a compound of formula CqHy9Q is shown in Figure 13.17. Propose a structure. Problem 13.22 3-Bromo-I-phenyl-1-propene shows a complex NMR spectrum in which the vinylic proton at C2is coupled with both the C1 vinylic proton (J = 16 Hz) and the C3 methylene protons (J = 8 Hz). Draw a tree diagram for the C2 proton signal, and account for the fact that a five-line multiplet is observed. H il 3 LCx.2_CHoBr Cc I H 3-Bromo-1-phenyl-1-propene13.24 Into how many peaks would you expect the !H NMR signals of the indicated protons to be split? (Green = Cl.) a (e) Se cd oo 13.25 How many absorptions would you expect the following compound to have in its 'H and !3C NMR spectra? Chemical Shifts and NMR Spectroscopy 13.29 The following 14 NMR absorptions were obtained on a spectrometer operat- ing at 200 MHz and are given in hertz downfield from the TMS standard. Convert the absorptions to 6 units. (a) 436Hz — (b) 956Hz ~— ©) 1804 Hz 13.30 The following ' NMR absorptions were obtained on a spectrometer operat- ing at 300 MHz. Convert the chemical shifts from 8 units to hertz downfield from TMS. @ 215 (b) 3.455 9 6.305 @) 7.70513.45 Propose structures for the two compounds whose HNMR spectra are shown, (@) CaHoBr Chom Rel Shit ae 105 600 197 100 331200 2 2 a ™s: a =| f 8 87 Cr 4 3 2 1 0 ppm Chemical shift (4) (b) CaHtgCle Intensity ‘Chem. ] ‘shift 122150 349 1.00 Intensity | T™s 10 9 8 7 6 5 4 3 2 1 0 ppm Chemical shift (6) Figure 13.17 An integrated 'H NMR spectrum for Problem 132.13.53 The compound whose !H NMR spectrum is shown has the molecular formula C3HgBr2, Propose a structure. i — 5 0 8 8 7 6 5 4 3 2 1 0 ppm Chemical shift (3) 13.54 The compound whose 1H NMR spectrum is shown has the molecular for- mula CyH702Cl and has an infrared absorption peak at 1740 cm™!. Propose a structure, Intensity ™s 0 9 a 7 6 5 4 3 2 1 0 ppm Chemical shift (3)13.58 Propose structures for the three compounds whose 'H NMR spectra are shown, (a) CsH190 z 5 IL T™s i 10 9 8 7 6 5 4 3 2 1 ppm Chemical shift (5) (b) CrHzBr Chem. Rel. shift area 231150 701 100 738100 2 T™sS 0 9 8 7 6 5 4 3 2 1 © ppm Chemical shift (6) (© CgHoBr Chem. Rel. shift area 3.16 1.00 356 100 718100 729 1560 = TMS 10 9 8 7 6 5 4 3 2 1 © ppm Chemical shift (3)