Organic Spectroscopy Workbook

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3 Organic Spectroscopy Workbook

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5 Organic Spectroscopy Workbook TOM FORREST JEAN-PIERRE RABINE MICHEL ROUILLARD A John Wiley & Sons, Ltd., Publication

6 This edition first published John Wiley and Sons Ltd. Registered office John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books. Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold on the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional should be sought. The publisher and the author make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of fitness for a particular purpose. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for every situation. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall be liable for any damages arising herefrom. Print ISBN: epdf ISBN: Typeset in 9.5/11.5pt Times Roman by Laserwords Private Limited, Chennai, India

7 Contents Preface Acknowledgements vii ix Tables of δ for CH 2 Doubly Substituted in α Position 227 Tables of δ for Aromatics 229 Coupling Constants 230 How to Use this Workbook 1 Preliminary Observations 2 Centres of Unsaturation 8 Exercises Infrared Data 210 IR Frequencies: Display of Infrared Database by Frequency 210 IR Groups: Display of Infrared Database by Functional Group H NMR Data 221 General Tables of Functional Groups 221 Comparison of δ of Alkyl Groups Bearing a Substituent in α or β Position 225 Alkyl Groups with an α Substituent 226 Alkyl Groups with a β Substituent C NMR Data 233 General Ranges for CH 3, CH 2, >CH Chemical Shift Ranges for Functional Groups 234 Chemical Shift Estimations 234 Mass Spectrometry Data 240 Main Fragments Observed 240 Atomic Masses 242 Isotopic Abundances in % 243 Internet Resources 254 Glossary of Terms Used in the Exercises 255 Answers 257 Index 261

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9 Preface This workbook arose out of a long standing project for the development of computer based programs to assist students in learning how to deduce the structures of organic compounds from spectroscopic data. The ability to elucidate chemical structures is built largely on implicit heuristics and informal experience accumulated by solving many examples. The accumulation of this experience is greatly facilitated by these computer based programs, However, the knowledge that is so arduously obtained at the computer may evaporate rapidly unless some reinforcement mechanism is in place. This workbook was originally conceived as a way to provide the computer users with a vehicle for making a lasting record of their learning experience. However, we recognized that a similar situation occurs for students who prefer to undertake their study without using computer-based exercises. They could also benefit from a workbook where they could get assistance in solving spectral problems and have a record that could be used for review and reinforcement. The resulting workbook was designed so that it can be used with or without the computer based program. The computer exercises, which are freely available online to any user, provide more detailed explanations and supplementary graphical material for the structural determinations. For each problem in the workbook we provide four spectra together with a detailed analysis of the spectra and an explanation of the derivation of the structure of the compound. The level of detail provided in the solution decreases gradually, until near the end of the set of exercises, very little or no analysis is given. The solutions to all of the exercises are provided, but no structural formulae are shown on the work area of the exercise, so that the student may follow along the analysis and draw the structural components as they are revealed. There are many advanced techniques available in modern spectrometers that may be employed to assist in the solution of more difficult structural problems. In these exercises we have chosen to give low resolution electron impact mass spectra because these spectra are readily available, and are rich in structural information. Modern mass spectrometry employs a multitude of other ionization techniques that can be used in particular circumstances to provide specific information, but these are beyond the scope of an introductory spectral exercise book. In the field of NMR spectroscopy there are numerous sophisticated pulse sequences available that can generate various multidimensional spectra which are used for more difficult structural problems. These techniques are particularly useful for large complex structures, but they are aids that still require the user to have an understanding of the fundamentals of spectroscopic interpretation, which is the goal of these exercises. We hope that students will find that using this workbook will prove to be a pleasant and rewarding experience.

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12 Acknowledgements We have used the resources of our university libraries extensively in preparing this workbook, but have found that we made even more extensive use of the resources available on the internet. We are indebted to the many people who have taken the time to place their data at the disposal of the scientific community in this manner. This easy access to spectral data has been of immense assistance to us in the preparation of this workbook. The availability of such a large amount of primary data allowed us to find very good model compounds which gave more specific support for the assignments than possible from the general correlation tables of secondary publications. It is impossible to list all of the internet sites that we visited during the preparation of the manuscript; however, we would like to specifically acknowledge the providers of those sites that we have found we were consistently using. These are for the most part sites provided by institutions, universities and chemical suppliers: Sigma-Aldrich Corporation, NMR and IR spectra; Acros Organics, IR spectra; University of Wisconsin, Chemistry Department, H. J. Reich, compilation of NMR chemical shifts and coupling constants. We are grateful for the support of: Université de Nice Sophia-Antipolis; Université Numérique Thématique:UNISCIEL (Université des Sciences en Ligne) Dalhousie University NIST, National Institute of Standards and Technology, Chemistry Webbook; National Institute of Advanced Industrial Science and Technology (AIST, Japan), Spectral Database for Organic Compounds;

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14 How to Use this Workbook The exercises give spectral charts and verbal analyses of the spectra, but the structural diagrams that would complete the picture are missing. Although annotated structures would be very helpful in the spectral assignments, they are deliberately omitted to avoid a premature revelation of the answer. You don t want to see the solution before you have had the opportunity to think about the problem. You may want to use a small sheet of paper to cover the conclusion/summary section as you try to solve each structure. There is adequate white space available on the pages to allow you to draw the appropriate structures, and to make notes on the spectral assignments. Complete structural drawings are available in the Answers section of the workbook. Each exercise has a second number in brackets which identifies the number by which the compound can be located in the Answers section, and in the computer-based exercises. The structures are not presented in the same order as the exercises, thus lessening the possibility of an unwanted exposure of the answer to the next exercise. There is no single method that provides the best way to solve these problems. There is usually an abundance of information that allows many paths to the solution. However, it is unlikely that the complete structure will be revealed intact, so the general approach is to derive the partial structures of the molecule and to connect them to form the complete structure. The order of the spectral analysis provided in each exercise is not presented as the best way to approach the problem. Many people do a preliminary scan of the spectra to look for significant features, identify the responsible structural component, then verify its presence using other spectra. For example, a carbonyl group that stands out in the IR spectrum can be verified by the peak at the appropriate chemical shift in the 13 C NMR spectrum. As one moves from spectrum to spectrum like this, it is imperative that an organized approach be maintained and that good notes are preserved. It is recommended that you write down the partial structures as you derive them. You can always erase them if you make a mistake or, better still, simply draw a mark through them, and make notes to ensure that you have them for review and can learn from your mistakes. Take the opportunity to make detailed notes before you leave each exercise. As clear as it will be in your mind at that moment, it is amazing how the details evaporate with time. All the 13 C NMR DEPT spectra are DEPT-135 spectra in which methylene carbons show a negative signal and quaternary carbons show no signal. Methyl and methine carbons show up as normal positive signals. All the mass spectral charts are low-resolution electron impact mass spectra (EIMS). These spectra frequently provide the molecular weight of the compound, and the high degree of fragmentation also offers valuable information to those with knowledge of reactivity of organic compounds. In some examples, the results of high-resolution mass spectra (HRMS) are provided which can be used to obtain the molecular formula directly. The exercises are organized somewhat in the order of complexity of the molecule and level of explanation provided. You will find very simple spectra and detailed explanations at the beginning, and eventually more complex exercises with less in the way of explanation. For the last 20 exercises, only general hints and suggestions are provided. In these exercises the 1 H NMR spectral data is provided in standard text format to show the coupling constants where appropriate. These data should be compared to the spectral pattern, so that you could write such a verbal description of the spectrum. The resource material you require to analyse the spectra is provided in tables and algorithms in separate data sections for each of the spectroscopy types. The exercises presented in this work book are also available in an on-line program, Multispectroscopy, which you may access at spectros.unice.fr. This program provides more detailed explanations, as well as elaborate diagrams and graphics, to help to explain the spectral analysis and structure determination. You may wish to take advantage of this additional resource, while you are using this workbook. Organic Spectroscopy Workbook, First Edition. Tom Forrest, Jean-Pierre Rabine, and Michel Rouillard John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd.

15 Preliminary Observations It is easy to get some information from a quick glance at some spectra. There are some typical shapes that give a good indication of particular structural features. It is essential that these deductions are verified by detailed inspection of the spectrum, and with data from other spectra. Infrared This indicates an alkene. This indicates an alcohol. This indicates an acid. This indicates a terminal alkyne. Organic Spectroscopy Workbook, First Edition. Tom Forrest, Jean-Pierre Rabine, and Michel Rouillard John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd.

16 Preliminary Observations 3 This indicates a nitrile. This indicates an amide R CO NH 2. This indicates a carbonyl. It may be an aldehyde, ketone, acid, ester, amide, urea... This indicates an NH 2. This indicates an aldehyde. This indicates a >NH.

17 4 Organic Spectroscopy Workbook Around 1380 cm 1, this is an isopropyl CH(CH 3 ) 2 or a gem-dimethyl >C(CH 3 ) 2. Around 1380 cm 1, there is a tert-butyl C(CH 3 ) 3. This indicates a propyl group CH 3 CH 2 CH 2 X. This indicates the presence of more than 4 5 CH 2, rocking band near 720cm 1. This indicates an isopropyl group (CH 3 ) 2 CH X. 1 HNMR This indicates an allyl group CH 2 =CH CH 2 X. This indicates an ethyl group CH 3 CH 2 X.

18 Preliminary Observations 5 13 CNMR This indicates a benzene ring with one alkyl substituent, or a benzene symmetrically substituted with alkyl groups. This indicates a quaternary carbon >C<. This indicates a methine >CH. This indicates a benzene para-disubstituted by two different groups (not alkyl groups) which gives an AA XX system. This indicates a methylene CH 2.

19 6 Organic Spectroscopy Workbook M+2 is generally less intense than M+1, but a M+2 that is very intense, perhaps even more intense than M, gives a good indication of the presence of chlorine or bromine. This indicates a methyl group CH 3. By looking at the isotope patterns in the high end of the spectrum, one can usually detect the presence of chlorine and bromine, and even the numbers of these atoms in the molecule. For chlorine, 35 Cl (75%) and 37 Cl (25%), depending on the number of Cl atoms present, one has distinctly different profiles of the isotopic peaks (M, M+2, M+4, M+6, etc.). This indicates an aldehyde. For bromine, 79 Br (50%) and 81 Br (50%), the peak pattern (M, M+2, M+4, M+6, etc.) is quite distinctive, depending on the number of bromine atoms in the molecule. Visually, the pattern looks similar to simple NMR splitting patterns. This indicates a ketone. Mass Spectra The molecular ion peak, M, is not generally the highest mass peak observed in the spectrum. Normally one finds higher mass ions due to isotope peaks: M+1 is normally due to the presence of the 13 C isotope of carbon, 1.1% of M per C, or in the case where silicon is present, it makes a strong contribution to M+1 (5.1% of M per Si). Sulfur also contributes to M+1 but it is easily detected by M+2. For chlorine and bromine in the same molecule, the isotope peak profile is more complex but one can still see distinctive patterns of isotopic peaks (M, M+2, M+4, M+6, etc.).:

20 Preliminary Observations 7 For sulfur, 32 S 100% M, 33 S0,8%M+1, 34 S4,4%M+2. In general, the contribution of sulfur to M+1 is largely masked by the contribution from carbon 13 C (1.1% per carbon). Only the peak M+2 gives a good indication of the number of sulfur atoms, but only in the absence of chlorine or of bromine and only if the peak M is sufficiently intense, so that the intensity of peak M+2 can be read with some precision.

21 Centres of Unsaturation If you have a molecular formula for the compound, don t forget to take the formula into account in all your deductions. The first thing to do is to calculate the number of centres of unsaturation of the compound. If the NCU = 4, this indicates four double bonds, or four rings or one double bond and three rings, or two double bonds and two rings, or three double bonds and one ring (benzene ring). Number of centres of unsaturation Knowing the formula CxHyOzNn, it is possible to determine the number of centres of unsaturation of the compound NCU: NCU = (2x n y)/2 If the formula contains halogens, count them like hydrogens. If the NCU is less than 4, the compound cannot have a benzene ring. If the NCU is 0, the compound cannot have a double bond, or a carbonyl or a ring. You need an NCU of at least 2 to have a compound containing a triple bond. CxHy: no oxygen, no nitrogen The functional group of the compound cannot be alcohol, ketone, aldehyde, phenol, acid, ester, anhydride, amide, amine, nitrile... If the NCU = 0, it is an alkane. If the NCU = 1, this indicates one ring or one double bond (alkene). If the NCU = 2, this indicates two double bond (alkene), or two rings or one double bond and one ring or one triple bond (alkyne). CxHyO: one oxygen, no nitrogen The functional group of the compound cannot be acid, ester, anhydride, amide, amine, nitrile... If the NCU = 0, it is an alcohol or an ether. If the NCU = 1, this indicates one ring or one double bond (>C=C< alkene or >C=O, ketone, aldehyde). If the NCU = 4, this indicates four double bond, or four rings, or one double bond (>C=C< or >C=O) and three rings, or two double bonds (>C=C< or >C=O) and two rings, or three double bonds (>C=C< or >C=O) and one ring (it may be a benzene ring). If the NCU 5, you may have a benzene ring with a double bond (>C=C< or >C=O) or a ring... CxHyO 2 : two oxygens, no nitrogen The functional group of the compound cannot be anhydride, amide, amine, nitrile... If the NCU = 0, it is an alcohol or an ether, or both. If the NCU = 1, this indicates one ring or one double bond (>C=C< or >C=O) or an acid RCOOH or an ester RCOOR. Organic Spectroscopy Workbook, First Edition. Tom Forrest, Jean-Pierre Rabine, and Michel Rouillard John Wiley & Sons, Ltd. Published 2011 by John Wiley & Sons, Ltd.

22 Centres of Unsaturation 9 CxHyO 3 : three oxygens or more, no nitrogen The functional group of the compound cannot be amide, amine, nitrile... If the NCU = 2, it may be an ahydride RCOOCOR. CxHyON: one oxygen, one nitrogen CxHyN: no oxygen, one nitrogen The functional group of the compound cannot be acid, ester, anhydride, amide... If the NCU = 0, it is an amine. If the NCU = 2, it may be a nitrile. The functional group of the compound cannot be acid, ester, anhydride... If the NCU = 1, it may be an amide RCON<

23 Exercises Exercise 001 (001) δ (integration): 1.3 (3), 3.5 (2) δ: 15.19, 65.88

24 Exercises Exercise 001 (001) Preliminary Observation The mass spectrum can be used to get the molecular mass of the compound, to detect the presence of chlorine, bromine or other heteroatoms, and to obtain structural information from the fragmentation pattern. The IR spectrum provides evidence of functional groupsand other structural features. The 13 C NMR spectrum gives the number of different carbon in the molecule, as well as their degree of substitution and functionality. The 1 H NMR spectrum can provide a count of the number of protons and information on their environment. The 1 H coupling patterns give indications of the connectivity of the components of the molecule. Mass Spectrum The isotope patterns give no indication of the presence of chlorine or bromine. The molecular ion (M + ) is usually the highest mass ion (with its associated isotope peaks). An odd-mass molecular ion usually indicates the presence of an odd number of nitrogen atoms. In this spectrum, the highest mass ion 74 (44%) has a 13 C isotope peak at 75 (2%). The natural abundance of 13 C is 1.1%; therefore, each carbon contributes 1.1% to the intensity of the isotope peak. The relative intensity of the M+1 peak in this compound is 4.5% (100 2/44), indicating the presence of four carbons. The most intense peak is known as the base peak and is assigned an intensity of 100%. The ion at 31 (100%) indicates the presence of oxygen in the molecule. The highest mass hydrocarbon in that region is 29 (CH 3 CH 2 + ), but if oxygen is present a peak at 31 (CH 2 OH + ) is possible. The peak at 59 corresponds to M 15, suggesting the presence of a CH 3 group. 13 CNMR The simplest spectrum, the broad band (BB) decoupled spectrum in which all of the C H coupling is removed, shows signals from only two types of carbon. In the off-resonance (OR) spectrum, the size of the direct C H coupling is reduced to make thecoupled spectrum more easily readable. In this exercise, thedirect C H coupling gives a quartet for a methyl group (CH 3 ), and a triplet for a methylene group (CH 2 ). The DEPT spectrum shows inverted signals for CH 2 carbons, and in this example has one such signal. Carbons bearing an odd number of protons show upright signals, and here it shows one such signal, that of the CH 3 group. Quaternary carbons (bearing no H) give no signal in the DEPT spectrum. The chemical shift of the lower field carbon, (66 ppm) is in the range of a methylene carbon bonded to oxygen. The molecule must have an element of symmetry, because the mass spectrum indicates that it has four carbons. 1 HNMR The 1 H NMR spectrum shows only two types of proton, a triplet and a quartet. The small peak at 0.0 ppm is that of the tetramethylsilane reference standard. This simple coupling pattern is easily recognized as that of an ethyl group ( CH 2 CH 3 ), with the methyl protons split by the neighbouring CH 2 protons into a triplet, and the methylene protons being split by the neighbouring CH 3 protons into a quartet. The integration of the spectrum indicates that the two signals have a relative intensity of 2 to 3. A molecule that has no nitrogen or halogen or other odd-valent atom, must have an even number of protons. Thus, there must be an even number of ethyl groups. The low field chemical shift (3.5 ppm) of the CH 2 group indicates that it is attached to an electron-withdrawing group, the oxygen atom in this case. Infrared The band at 1140 cm 1 is a clear indication of C O stretching, most likely that of an ether function. Other than the bands due to the alkyl groups, there are no bands that can be assigned to other functional groups. The IR spectrum can be used very effectively to show that certain functional groups are absent. For instance, in this case one can say with certainty that there is neither a carbonyl group, nor hydroxyl present in the molecule. Summary The 1 Hand 13 C NMR evidence indicates the presence of an ethyl group bonded to oxygen (ethoxy group). The mass spectrum gives a molecular mass of 74, and since an ethoxy group has a mass of 45, another ethyl group (mass 29) is required to complete the structure. The compound is diethyl ether, CH 3 CH 2 O CH 2 CH 3.

25 12 Organic Spectroscopy Workbook Exercise 002 (003) δ (integration): 4.12 (2), 2.04 (3), 1.26 (3) δ: 171.1, 60.4, 21.0, 14.3

26 Exercises Exercise 002 (003) Preliminary Observation In a preliminary scan of the spectra there are several points that stand out. In the IR spectrum, there is a very strong peak in the carbonyl region near 1740 cm 1. The mass spectrum appears to have a peak for the molecular ion, since the highest mass ion has an even mass. The 13 C NMR spectrum can be used to determine the number and type of carbons, and the 1 H NMR spectrum to get the connections between the carbons. The chemical shifts and the IR spectrum will identify the functional group. The mass spectrum can be used to get the molecular weight of the compound. 13 CNMR The broad band spectrum shows that there are four types of carbon in the molecule. The off-resonance spectrum indicates that two of the carbons are methyl groups (quartets, CH 3 ), one is a methylene group (triplet, CH 2 ) and one a quaternary carbon (singlet, no attached hydrogen). The DEPT spectrum shows one inverted signal corresponding to the CH 2 carbon, and the disappearance of a peak at 171 ppm corresponding to the quaternary carbon. There are two different CH 3 groups, one CH 2 group, and a strongly deshielded carbon bearing no hydrogens (quaternary carbon). This spectrum shows that the compound has four carbons and eight protons or a multiple of these. 1 HNMR The 1 H NMR spectrum shows the signals from three different types of proton. The integration of the spectrum shows a relative intensity of 2:3:3 (4.2, 2.0 and 1.3 ppm), for a total of eight protons, which agrees with the 13 C NMR spectrum that indicated a total of eight protons. One CH 3 group is not coupled to any other hydrogen (singlet at 2 ppm), and the other CH 3 (triplet at 1.3 ppm) is coupled to the CH 2 group. Thus, we have an ethyl group and an isolated methyl group. The singlet at 2 ppm is in the chemical shift region of a methyl group attached to an sp 2 carbon, while the CH 2 (4.1 ppm) is in the region of a methylene group attached to an oxygen. As the CH 2 group is coupled to a methyl group, we have a CH 3 CH 2 O group. Infrared This infrared spectrum has two very significant bands of the functional group of the compound. The band at 1740 cm 1 clearly shows the presence of a carbonyl group (C=O), and the band at 1250 cm 1 indicates the presence of a C O single bond. The frequencies of both of these bands are compatible with an ester group (C O C=O). Mass Spectrum The highest even-mass ion in the spectrum is at 88, and is probably that of the molecular ion. The most intense peak (the base peak) is found at 43, which is a fragment most commonly associated with an acylium ion (CH 3 C O + ). This would arise from the loss of the ethoxy radical by α cleavage at the carbonyl group. The ion at 73 comes from the loss of one of the methyl groups. The ion at 70 arises from the loss of a molecule of water, a common rearrangement fragmentation in esters. The majority of the fragment ions have odd masses, which is typical of compounds without nitrogen. These odd-mass ions have an even number of electrons, and are generally more stable than the even-mass fragments, as they consist of the less stable odd-electron radical ions. Even-mass ions are generally formed when a rearrangement creates a stable small molecule, such as, in this case, the loss of water yields the ion at 70. Summary The structural components that have been identified are: an ethyl group, a methyl group and a quaternary carbon, the mass of these adding to 56, which is 32 less than the molar mass of 88 that was found from the mass spectrum. The missing mass is equivalent to two oxygen atoms (2 16), exactly the number required for the ester group that was identified in the IR spectrum. The NMR chemical shifts of the CH 2 group indicate that it is attached directly to the oxygen of the ester. The chemical shifts of the uncoupled methyl group indicate that it is attached to a polarized sp 2 carbon, which would place it on the carbonyl (C=O) carbon. This gives us the complete structure CH 3 (C=O)OCH 2 CH 3, ethyl acetate.

27 14 Organic Spectroscopy Workbook Exercise 003 (010) δ (integration): 3.37 (2), 1.59 (2), 0.93 (3) δ: 72.84, 23.34, 10.60

28 Exercises Exercise 003 (010) Preliminary Observation The infrared spectrum frequently gives the first clue as to the functional group in the molecule. When it is not obvious from the IR, then the chemical shifts in the NMR spectra may give some clues to the functional groups. The NMR spectra give the best information on the substructures within the molecule. The mass spectra may have a lot of information in the fragmentation patterns, but these must be used with caution as they arise from reactions of ions in very high energy states. Mass Spectrum The peak at 102 is a good candidate for the molecular ion. It has an even mass and the spectrum contains many odd-mass fragment ions: at 87 (M 15), at 73 (M 29) and at 59 (M 43). Note the fragment at 31, which usually indicates the presence of oxygen (CH 2 OH + ). The molecule is possibly a mono-oxygenated saturated compound (C 6 H 14 O) or a dioxygenated unsaturated compound (C 5 H 12 O 2 ). Note that there is a peak for the loss of a methyl group (M 15), and for the loss of an ethyl group (M 29), so one might be tempted to conclude that the molecule contains a methyl group and an ethyl group, but this should always be verifiedinthe 1 Hand 13 C NMR spectra. 1 HNMR The spectrum has three signals with an integration ratio of 2:2:3. The coupling pattern of a triplet, sextet and triplet suggests the presence of CH 2 CH 2 CH 3, theterminal CH 2 split by two neighbours, the middle CH 2 split by five neighbours, and the terminal CH 3 split by two neighbours. In view of the chemical shift of the terminal CH 2 group at 3.4 ppm, one would expect this carbon to be attached to an oxygen. The mass spectrum of the compound requires a higher mass than an oxygen and one propyl group. As there are no peaks for other protons, there are probably two equivalent propyl groups in the molecule. spectrum other than the bands from the alkyl chains. There is a doublet of equal intensity near 1380 cm 1 which normally indicates the presence of a gem-dimethyl group. However this pair of peaks is deceptive, as the NMR spectra shows clearly that there is no gem-dimethyl group in the compound. 13 CNMR There are three types of carbon in the compound, two CH 2 (triplets in off-resonance and inverted in DEPT), and one CH 3 (quartet in off-resonance). The chemical shift of the carbon at 73 ppm is in the correct region for a carbon attached to the oxygen of an ether. Summary The molecule has a propyl group attached to oxygen and a molecular mass of 102. The mass of one propyl group (CH 3 CH 2 CH 2 ) is 43, and one oxygen is 16, for a total of 59. This is 43 less than the molecular mass of 102. One more propyl group is needed to complete the structure. The compound is dipropyl ether, CH 3 CH 2 CH 2 O CH 2 CH 2 CH 3. Notice that the peaks of the two triplets in the 1 H NMR spectrum are not symmetrical, particularly that of the methyl group. Each one is distorted, having a larger peak on the side towards the group to which it is coupled. This is typical of systems in which the chemical shift difference is not large compared to the size of the coupling constant. If the spectrum were run in a higher field spectrometer (say, 400 MHz, instead of this one, 60 MHz), one would not expect to see such distortion, as the chemical shift difference in Hertz would be much larger, while the coupling constant would not change. The ratio of the chemical shift to coupling constant becomes much larger, consequently the distortion decreases. Compare the coupling in this compound with that of the compound in Exercise 004. Infrared The strong band at 1120 cm 1 is in the region of C O stretching. As there is no carbonyl band or OH band, this band belongs to an ether. There is little else that one can see in the