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Organic Chemistry by Solomons and Frayle
Spectroscopy and Structure of Organic Molecules (First Long Examination) II. Alkenes and Alkynes-Part II: Addition Reactions and Synthesis III. Reactions Involving Radicals IV. Ethers and Alcohols (Second Long Examination) V. Oxidation, Reduction and Organometallic Compounds: Reactions Involving Alcohols and Carbonyl Compounds VI. Aldehydes and Ketones : Nucleophilic Addition Reactions of the Carbonyl Group (Third Long Examination) VII. Reactions Involving Aromatic Compounds VIII. Carboxylic Acids and Related Functional Groups: Nucleophlic AdditionElimination the Acyl Carbon IX. Amines: Properties, Synthesis and Biochemical Relevance (Fourth Long Examination)
CHEM 36 ORGANIC CHEMISTRY II I. Spectroscopy and Structure of Organic Compounds
Reference: Organic Chemistry. Solomons and Fryhle. 8th Edition
Chem. 36 Ch1.
Spectroscopy: the study of the interaction of quantized energy (electromagnetic energy) with matter
• Energy applied to matter can be absorbed, emitted, cause a chemical change, or be transmitted. • In organic chemistry, we typically deal with molecular spectroscopy particularly absorption spectroscopy.
Chem. 36 Ch1.
MMUy 03 . IR is useful for identifying functional groups in a molecule. Examples of Spectroscopy • Ultraviolet Spectroscopy Absorption of ultraviolet energy results to electronic transitions in molecules. carbonyl and aromatic systems. • Infrared (IR) Spectroscopy Infrared energy causes bonds to stretch and bend. conjugated systems. UV spectroscopy indicates the presence of chromophores in a molecule particularly unsaturation. 36 Ch1. Chem.
The resulting mixture of ions is sorted by mass/charge (m/z) ratio. hydrogen and carbon nuclei). 36 Ch1. MMUy 04 . Molecular weight and chemical formula may be derived from the M+ and M+1 ions. Molecular structure may be deduced from the distribution of fragment ions. Mass Spectrometry (MS) Molecules are converted to ions by one of several methods (including bombardment by a beam of electrons). M+). The ions formed may remain intact (as molecular ions. Nuclear Magnetic Resonance (NMR) Spectroscopy • Energy applied in the presence of a strong magnetic field causes absorption by the nuclei of some elements (most importantly. or they may fragment. • NMR is used to identify connectivity of atoms in a molecule. and detected. Chem.
MMUy 05 . 36 Ch1.• Schematic absorption spectrum: wavelength frequency change in energy An absorption band is characterized primarily by two parameters: (a) the wavelength λ at which maximum absorption occurs (b) the intensity of absorption at this wavelength compared to baseline or background absorption Chem.
MMUy 06 . 36 Ch1. Chem.• Spectroscopic transition: takes a molecule from one state to a state of a higher energy and its change in energy is given by ∆E: where h = Planck’s constant The energy gap of a transition is a molecular property and is a characteristic of a molecular structure.
MMUy 07 .The Electromagnetic Spectrum Electromagnetic radiation has the characteristics of both waves and particles. • The wave nature of electromagnetic radiation is described by wavelength (λ) or frequency (ν). • The relationship between wavelength (or frequency) and energy (E) is well defined. Chem. 36 Ch1.
• The higher the frequency.• Wavelength and frequency are inversely proportional (ν= c/λ). the greater the energy of the wave. the greater the energy of the wave. MMUy 08 . Chem. • The shorter the wavelength. 36 Ch1.
36 Ch1.Chem. MMUy 09 .
MMUy 10 .Chem. 36 Ch1.
36 Ch1. MMUy 11 . Chem. An extensive region at wavelengths shorter than ~200 nm (“vacuum UV”) also corresponds to electronic transitions but this region is not accessible with standard instruments. Ultraviolet Spectroscopy generally refers to electronic transitions occurring in the ultraviolet (λ range 200-380 nm) region of the electromagnetic spectrum Electronic transitions are also responsible in the visible region (λ range 380-800 nm) which is easily accessible instrumentally but are of less importance in the solution of structural problems since most organic compounds are colorless.I.
36 Ch1. types of electronic transitions: n to π* σ to π* π to π* n to σ* the transitions are brought about by the presence of chromophores in the molecule ( a part of the molecule which can be a functional group or a single atom or group of atoms in a molecule which may not be associated with chemical functionality) Chem. MMUy 12 .
MMUy 13 .Basic Instrumentation Chem. 36 Ch1.
36 Ch1. hexane. For UV measurements. water or dioxan are usually chosen as solvents. double-beam instruments are used where the absorption of a reference cell. the cells and optical components are typically made of quartz and ethanol. In practice. containing only solvent. the materials from which the dispersing device and detector are constructed must be appropriate for the range of wavelength scanned as transparent as possible to the radiation. MMUy 14 . The energy source. is subtracted from the absorption of the sample cell. Chem.
e.. MMUy 15 . in terms of Absorbance A: Chem.Quantitative Aspects The y-axis of a UV spectrum may be calibrated in terms of the intensity of transmitted light (% transmission or absorption) or on a logarithmic scale i. 36 Ch1.
36 Ch1. The presence of small amounts of strongly absorbing impurities may lead to errors in the interpretation of UV data. MMUy 16 . Beer’Lambert law: Absorbance is proportional to the concentration and path length. intensity is usually expressed as molar absorbance or molar extinction coefficient ε: Where M = molecular weight C = concentration (g/L) l = path length (cm) UV absorption bands are characterized by the wavelength of maximum absorption (λmax) and ε. Chem. • The values of ε vary from 10 and 105 and are conveniently tabulated as log10(ε).
Classification of UV Bands UV absorption bands have fine structures due to the presence of vibrational sub-levels but are rarely observed in solution due to collisional broadening. MMUy 17 . As transitions are associated with changes of electron orbitals. 36 Ch1. they are often described in terms of the orbitals involved or by another classification method: Chem.
36 Ch1. Chem. UV spectra typically contain far fewer features than IR. MMUy 18 . A molecule may give rise to more than one band because it contains more than one chromophore or because more than one transition of a single chromophore is observed. NMR or MS spectra and thus have a lower information content.
-halogen) bathochromic shift: shift of absorption maximum to longer wavelength hypsochromic shift: shift of absorption maximum to shorter wavelength • Hyperchromic effect: an increase in absorption intensity • Hypochromic effect: a decrease in absorption intensity Chem. but which often have significant effects on the absorption (both λmax and ε) of a chromophore to which they are attached.Special Terms in UV Spectroscopy Auxochromes (auxillary chromophores): groups which have little UV absorption by themselves. -NR2. are atoms with one or more lone pairs ( -OH. 36 Ch1. MMUy 19 . -OR.
Important UV Chromophores Most of the reliable and useful data is due to relatively strongly absorbing chromophores (ε > 200) which are mainly indicative of conjugated or aromatic systems. 36 Ch1. MMUy 20 . Chem. (1) Dienes and Polyenes Extension of conjugation in C chain is always associated with a pronounced shift towards longer wavelength (bathochromic shift) and towards greater intensity (hyperchromic shift).
36 Ch1. MMUy 21 .Bicyclic diene Chem.
Empirical rules (Woodward Rules) of good predictive value are available to estimate the positions of λmax in conjugated polyenes and conjugated carbonyl compounds. the absorption maximum of polyenes is such that they absorb light strongly in the visible region. 36 Ch1. MMUy 22 .Table 1. The Effect of Conjugation on UV Absorption When there are more than 8 conjugated double bonds. Chem.
... +6 X.... 36 Ch1...(Sulfide Group) ..(Alkyl Group) ..(Cl. +60 Further π -Conjugation C=C (Double Bond) .(Amino Group) . +30 R2N... +10 RCO2...or Br-) . +5 nm RO. +60 MMUy 23 Cyclohexadiene* 260 nm Chem.(Acyl Group) ...(Alkoxy Group) .. 0 RS. +30 C6H5 (Phenyl Group) ..Woodward-Fieser Rules for Calculating the λmax of Conjugated Dienes and Polyenes Core Chromophore Transoid Diene 215 nm Substituent and Influence R.....
36 Ch1. there are two exo-double bond components: one to ring A and the other to ring B. λmax (calculated) = Base (215 or 260) + Substituent Contributions Chem. a base value of 260 nm should be chosen.(i) Each exocyclic double bond adds 5 nm. This includes the ring substituents. * When a homoannular (same ring) cyclohexadiene chromophore is present. MMUy 24 . In the example on the right. (ii) Solvent effects are minor. Rings of other size have a lesser influence.
Chem. 36 Ch1. MMUy 25 .
MMUy 26 .Chem. 36 Ch1.
MMUy 27 . 36 Ch1. Chem.(2) Carbonyl compounds All carbonyl derivatives exhibit weak (ε < 100) absorption between 250 and 350 nm. and this is only of marginal use in determining structure. Conjugated carbonyl derivatives always exhibit strong absorption.
MMUy 28 . UV Absorption Bands in Common Carbonyl Compounds Chem.Table 2. 36 Ch1.
(Acyl Group) +6 Chem.(Hydroxyl Group) +35 RO.(Chloro Group) +25 HO. 36 Ch1.Substituent R.(Alkyl Group) +10 nm Cl.(Alkoxyl Group) +35 RCO2.(Chloro Group) +15 Br. MMUy 29 .Woodward-Fieser Rules for Calculating the π __> π* λmax of Conjugated Carbonyl Compounds Core Chromophore R = Alkyl 215 nm R = H 210 nm R = OR' 195 nm Cyclopentenone 202 nm Substituent and Influence α.
(Acyl Group) +6 RS.Substituent R.(Sulfide Group) +85 R2N.(Chloro Group) +30 HO. +30 C6H5 (Phenyl Group) ..(Alkyl Group) +18 nm (both γ & δ) HO.β. 36 Ch1.(Alkoxyl Group) +30 nm (γ) Further π -Conjugation C=C (Double Bond) ...(Hydroxyl Group) +50 nm (γ) RO.(Chloro Group) +12 Br.(Hydroxyl Group) +30 RO.(Alkyl Group) +12 nm Cl..(Alkoxyl Group) +30 RCO2. MMUy 30 . +60 Chem.Substituents R.(Amino Group) +95 γ & δ.
MMUy 31 . 36 Ch1. there are two exo-double bond components: one to ring A and the other to ring B.(i) Each exocyclic double bond adds 5 nm. In the example on the right. (ii) Homoannular cyclohexadiene component adds +35 nm (ring atoms must be counted separately as substituents) (iii) Solvent Correction: water = –8. ether = +7. hexane/cyclohexane = +11 λmax (calculated) = Base + Substituent Contributions and Corrections Chem. methanol/ethanol = 0.
36 Ch1.Chem. MMUy 32 .
MMUy 33 . 36 Ch1.Chem.
-OCH3 Groups which increase conjugation: -CH=CH2.(3) Benzene derivatives exhibit medium to strong absorption with bands having characteristic fine structure and the intensity of the absorption being strongly influenced by substituents: Weak auxochromes: -CH3. -NO2 Auxochromes whose absorption is pH dependent: -NH2 and -OH Chem. -C(=O)-R. MMUy 34 . 36 Ch1. -Cl.
MMUy 35 . UV Absorption Bands in Common Benzene Derivatives Chem.Table 3. 36 Ch1.
Table 3. MMUy 36 . Chem. cont. 36 Ch1.
The added conjugation in naphthalene. Chem. anthracene and tetracene causes bathochromic shifts of these absorption bands. 36 Ch1. MMUy 37 .
• The bonds behave like tiny springs connecting the atoms. The bonds can absorb energy and vibrate faster only when the added energy is of a particular resonant frequency. • The frequencies of absorption are very characteristic of the type of bonds contained in the sample molecule. • Energy is absorbed by the bonds in the molecule and they vibrate faster.II. Infrared Spectroscopy: An Instrumental Method For Detecting Functional Groups Electromagnetic radiation in the infrared (IR) frequency range is absorbed by a molecule at certain characteristic frequencies. Chem. MMUy 38 . 36 Ch1.
Infrared Spectrometer • An infrared spectrometer detects the frequencies absorbed by the sample molecule. MMUy 39 .• The type of bonds present are directly related to the functional groups present. Chem. 36 Ch1. • The absorption frequencies are specified as wavenumbers in units of reciprocal centimeters (cm-1). • A plot of these absorbed frequencies is called an IR spectrum. • Light of all the various IR frequencies is transmitted to the molecule and the frequencies absorbed are recorded.
36 Ch1.• Alternatively the wavelength (λ) in units of microns (µm) can be specified. Chem. • The spectrum is a plot of frequency on the horizontal axis versus strength of absorption on the vertical axis. MMUy 40 .
MMUy 41 .• There are different types of stretching and bending vibrations induced by the absorption of infrared energy: Chem. 36 Ch1.
36 Ch1. MMUy 42 . Triple bonds (which are stiffer and stronger) vibrate at higher frequencies than double bonds: Double bonds in turn vibrate at higher frequencies than single bonds. Chem. The actual relative frequency of vibration can be predicted: Bonds with lighter atoms vibrate faster than those with heavier atoms.
The IR is a “fingerprint” of the molecule because of the unique and large number of peaks seen for a particular molecule. 36 Ch1. Chem. These peaks are due to the various types of vibrations available to each of the different bonds. MMUy 43 . Additional peaks result from overtone (harmonic) peaks which are weaker and of lower frequency.• The IR spectrum of a molecule usually contains many peaks.
Chem. 36 Ch1. MMUy 44 .
36 Ch1.Chem. MMUy 45 .
Chem. MMUy 46 . • Those peaks that are large and above 1400 cm-1 are most valuable. Hydrocarbons • The C-H stretching regions from 2800-3300 cm-1 is characteristic of the type of carbon the hydrogen is attached to.Interpreting IR Spectra Generally only certain peaks are interpreted in the IR. stronger and stiffer and thus vibrate at higher frequency. 36 Ch1. • C-H bonds where the carbon has more s character are shorter.
C-H bonds at sp centers appear at 3000-3100 cm-1 C-H bonds at sp2 centers appear at about 3080 cm-1 C-H bonds at sp3 centers appear at about 2800-3000 cm-1 • C-C bond stretching frequencies are only useful for multiple bonds: C-C double bonds give peaks at 1620-1680 cm-1 C-C triple bonds give peaks at 2100-2260 cm-1 These peaks are absent in symmetrical double and triple bonds. MMUy 47 . Chem. 36 Ch1.
• Example: octane Chem. MMUy 48 . 36 Ch1.
MMUy 49 . 36 Ch1.• Example: 1.hexyne Chem.
Alkenes • The C-H bending vibration peaks located at 600-1000 cm-1 can be used to determine the substitution pattern of the double bond: Chem. MMUy 50 . 36 Ch1.
36 Ch1.• Example: 1-hexene Chem. MMUy 51 .
MMUy 52 . Aromatic Compounds • The C-C bond stretching gives a set of characteristic sharp peaks between 1450-1600 cm -1 • Example: Methyl benzene Chem. 36 Ch1.
Other Functional Groups Carbonyl Functional Groups • Generally the carbonyl group gives a strong peak which occurs at 1630-1780 cm-1. The exact location depends on the actual functional group present: Chem. MMUy 53 . 36 Ch1.
MMUy 54 . A phenol has a hydroxyl group directly bonded to an aromatic ring. In more concentrated solutions. Alcohols and Phenols • The O-H stretching absorption is very characteristic: In very dilute solutions. the hydroxyl groups hydrogen bond to each other and a very broad and large peak occurs at 3200-3550 cm-1. hydrogen bonding is absent and there is a very sharp peak at 3590-3650 cm-1. 36 Ch1. Chem.
36 Ch1. MMUy 55 . Carboxylic Acids • The carbonyl peak at 1710-1780 cm-1 is very characteristic • The presence of both carbonyl and O-H stretching peaks is a good proof of the presence of a carboxylic acid • Example: propanoic acid Chem.
• Amides have amine N-H stretching peaks and a carbonyl peak. MMUy 56 . 1o amines give two peaks and 2o amines give one peak. 36 Ch1. Chem. 3o have no N-H bonds and do not absorb in this region. Amines • Very dilute solution of 1o and 2o amines give sharp peaks at 3300-3500 cm-1 for the N-H stretching. • More concentrated solutions of amines have broader peaks.
• The nuclei of protons (1H) and carbon-13 (13C). MMUy 57 . NMR spectrometers are used to measure these absorptions. behave as if they were tiny bar magnets. • When placed in a magnetic field and irradiated with radio frequency energy. 36 Ch1. Chem. and certain other elements and isotopes. these nuclei absorb energy at frequencies based on their chemical environments.Nuclear Magnetic Resonance Spectroscopy NMR involves absorption of energy in the radiofrequency range of the electromagnetic spectrum.
Continuous-Wave (CW) NMR Spectrometers • the oldest type of NMR spectrometer • The magnetic field is varied as the electromagnetic radiation is kept at a constant frequency. MMUy 58 . Chem. 36 Ch1. • Different nuclei absorb the electromagnetic energy based on their chemical environment and produce peaks in different regions of the spectrum.
superconducting magnets used in FT-NMR spectrometers lead to greater sensitivity and much higher resolution than continuous wave instruments. • The sample is irradiated with a short pulse of radio frequency energy that excites nuclei in different environments all at once. Fourier Transform (FT) NMR Spectrometers • The sample is placed in a constant (and usually very strong) magnetic field. which leads to enhancement of real spectral signals versus noise. • The strong. • This signal is converted to a spectrum by a Fourier transformation. 36 Ch1. • The resulting signal contains information about all of the absorbing nuclei at once. MMUy 59 . • FT-NMR allows signal-averaging. Chem.
36 Ch1. MMUy 60 .Diagram of a FT NMR Spectrometer Chem.
Chemical Shift: Peak Position in an NMR Spectrum • Nuclei in different chemical environments in a molecule will absorb at slightly different frequencies. 36 Ch1. • The position of the signals in the spectrum is called the “chemical shift”. • There are two reasons for differences in the magnetic environment for a proton: 1) The magnetic field generated by electrons circulating around the nucleus giving the signal 2) Local magnetic fields generated by electrons elsewhere in the molecule Chem. MMUy 61 .
these absorptions are said to be downfield. MMUy 62 . 36 Ch1.• Example: 1. Lower frequency is to the left in the spectrum. Chem.4-dimethylbenzene The spectrum is measured on a delta (δ) scale in units of parts per million (ppm).
The small signal at δ 0 corresponds to an internal standard called tetramethylsilane (TMS) used to calibrate the chemical shift scale.4-dimethylbenzene Higher frequency is to the right in the spectrum: these absorptions are said to be upfield. 36 Ch1. Chem. MMUy 63 .• Example: 1.
1. MMUy 64 .4-dimethylbenzene The number of signals in the spectrum corresponds to the number of unique sets of protons. 36 Ch1.4-dimethylbenzene has protons in two unique environments and so shows two signals.• Example: 1. Chem.
MMUy 65 . The height of each step in the integral curve is proportional to the area of the signal underneath the step.2-trichloroethane Chem. 36 Ch1.1. The Integral Curve The area under each signal corresponds to the relative number of hydrogen atoms in each unique environment within a molecule.• Integration of Peak Areas. 1.
36 Ch1. Characteristic peak patterns result from signal splitting that are related to the number of protons on adjacent carbons.• Signal Splitting The signal from a given proton will be split by the effect of magnetic fields associated with protons on adjacent carbons. 1.2-trichloroethane Chem.1. MMUy 66 .
Nuclei with I = 0 do not have spin (12C and 16O) and do not respond to an external magnetic field. 19F and 31P and these also respond to an external magnetic field. MMUy 67 .Nuclear Spin: The Origin of the Signal The nuclei of certain elements and isotopes have spin states that are quantized. Other nuclei with I = 1/2 are 13C. Chem. 1H has a spin quantum number I = 1/2 and has allowed spin states of +1/2 or -1/2. 36 Ch1.
Nuclear Spin: The Origin of the Signal The nuclei of NMR-active nuclei behave like tiny bar magnets. In the absence of an external magnetic field these bar magnets are randomly orientated (a). In an external magnetic field they orient either with (α spin state) or against (β spin state) the magnetic field (b). 36 Ch1. MMUy 68 . Chem.
• Nuclei aligned with the magnetic field are lower in energy than those aligned against the field. MMUy 69 . Chem. • The amount of energy required depends on the strength of the external magnetic field: The stronger the external magnetic field. the higher the radio frequency energy required to flip the nuclear spin. • The nuclei aligned with the magnetic field can be flipped to align against it if the right amount of energy is added (∆E). 36 Ch1.
At (c) the external magnetic field is 7. At (a) there is no external magnetic field and therefore no energy difference between the two states. At (b) the external magnetic field is 1.04 Tesla energy corresponding to a frequency of about 300MHz is needed to flip between the spin states. 36 Ch1.41 Tesla and energy corresponding to a frequency of about 60MHz is needed to flip between the spin states. Chem. MMUy 70 .
MMUy 71 . 36 Ch1.Shielding and Deshielding of Protons Protons in an external magnetic field absorb at different frequencies depending on the electron density around that proton. Chem.
High electron density around a nucleus shields the nucleus from the external magnetic field. 36 Ch1. • Shielding causes absorption of energy at higher frequencies (more energy is required for this nucleus to flip between spin states) . MMUy 72 .the signals are upfield in the NMR spectrum. Chem.
36 Ch1. Lower electron density around a nucleus deshields the nucleus from the external magnetic field. MMUy 73 . Chem. • Deshielding causes absorption of energy at lower frequencies (less energy is required for this nucleus to flip between spin states) .the signals are downfield in the NMR spectrum.
causing deshielding or shielding. Chem.• Electronegative atoms draw electron density away from nearby protons and therefore deshield them. Alkene and aromatic ring hydrogens are deshielded by the circulation of π electrons. MMUy 74 . A terminal alkyne hydrogen is shielded by the circulation of π electrons. • Circulation of π electrons leads to a local induced magnetic field: The induced field can reinforce or diminish the external field sensed by a proton (depending on the location of the proton). respectively. 36 Ch1.
Chemical Shift Chemical shifts are measured in relation to the internal reference tetramethylsilane (TMS). • The protons of TMS are highly shielded because of the strong electron donating capability of silicon. The δ scale for chemical shifts is independent of the magnetic field strength of the instrument (whereas the absolute frequency depends on field strength). MMUy 75 . Chem. 36 Ch1. • The signal for TMS is well away from most other proton absorptions.
Thus. the chemical shift in δ units for protons on benzene is the same whether a 60 MHz or 300 MHz instrument is used. MMUy 76 . 36 Ch1. Chem.
MMUy 77 . 36 Ch1.Chem.
36 Ch1.Chem. MMUy 78 .
Chemical Shift Equivalent and Nonequivalent Protons
To predict the number of signals to expect in an NMR spectrum it is necessary to determine how many sets of protons are in unique environments. Chemically equivalent protons are in the same environment and will produce only one signal.
Chem. 36 Ch1.
• Hydrogens are chemically equivalent or homotopic if replacing each one in turn by the same group would lead to an identical compound.
Chem. 36 Ch1.
Enantiotopic and Diastereotopic Hydrogen Atoms
• If replacement of each of two hydrogens by some group leads to enantiomers, those hydrogens are enantiotopic.
In the absence of a chiral influence, enantiotopic hydrogens have the same chemical shift and appear in the same signal.
Chem. 36 Ch1.
36 Ch1.• If replacement of each of two hydrogens by some group leads to diastereomers. MMUy 82 . Chem. Diastereotopic hydrogens have different chemical shifts and will give different signals. the hydrogens are diastereotopic.
Chem. 36 Ch1. Characteristic peak patterns result from signal splitting that are related to the number of protons on adjacent carbons. MMUy 83 .Signal Splitting: Spin-spin Coupling The signal from a given proton will be split by the effect of magnetic fields associated with protons on adjacent carbons. • The effect of signal splitting is greatest between atoms separated by 3 or fewer σ bonds.
• Signal splitting is not observed between homotopic or enantiotopic protons. Signal splitting occurs only when two sets of protons have different chemical shifts (i. MMUy 84 . are not chemical shift equivalent).e.. 36 Ch1. Chem.
The magnetic field sensed by a proton (Ha) being observed is affected by the magnetic moment of an adjacent proton (Hb): • A proton (Hb) can be aligned with the magnetic field or against the magnetic field. • The observed proton (Ha) senses the two different magnetic moments of Hb as a slight change in the magnetic field. 36 Ch1. MMUy 85 . Chem. one magnetic moment reinforces the external field and one substracts from it. resulting in two energy states for Hb.
36 Ch1. Chem. MMUy 86 .• The signal for Ha is split into a doublet with a 1:1 ratio of peak areas. • The magnitude of the splitting is called the coupling constant Jab and is measured in Hertz (Hz).
• Ha is split into a triplet having a 1:2:1 ratio of signal areas. • One combination of magnetic moments reinforces and another subtracts from the applied magnetic field. 36 Ch1. When two adjacent protons Hb are coupled to Ha. Chem. causing no net displacement of signal. MMUy 87 . there are four possible combinations of the magnetic moments for the two Hbs: • Two of these combinations involve pairings of magnetic moments that cancel each other.
36 Ch1. MMUy 88 .Chem.
36 Ch1. When three adjacent protons are coupled to Ha. there are 10 possible combinations of the magnetic moments for the Hbs: • Four unique orientations exist and so Ha is split into a quartet with intensities 1:4:4:1. MMUy 89 . Chem.
MMUy 90 . 36 Ch1.Chem.
The general rule for splitting is that if there are n equivalent protons on adjacent atoms. • Spin-spin coupling can be long-range (i. • Comparison of coupling constants can help with the analysis of complex spectra. more than 3 bonds). MMUy 91 . Chem. Several factors complicate analysis of NMR spectra: • Peaks may overlap..e. Coupled peaks have the same coupling constants J. these will split a signal into n + 1 peaks. 36 Ch1.
MMUy 92 . Splitting patterns in aromatic groups can be confusing: • A monosubstituted aromatic ring can appear as an apparent singlet or a complex pattern of peaks. Chem. 36 Ch1.
Much more complex splitting can occur when two sets of adjacent protons split a particular set of protons. Chem. • The spectrum of 1-nitropropane shows splitting of Hb into only 6 peaks. 36 Ch1. In the system below. Hb is split by two different sets of hydrogens : Ha and Hc • Theortically Hb could be split into a triplet of quartets (12 peaks) but this complexity is rarely seen. MMUy 93 .
MMUy 94 .Chem. 36 Ch1.
• Impure ethanol contains acid and base impurities which catalyze the exchange of hydroxyl protons. only an average of the changes will be seen. the hydroxyl proton is split into a triplet by the two adjacent hydrogens.. • This process is called spin decoupling. MMUy 95 . When a 1H NMR spectrum of very pure ethanol is taken. Chem.e. • This rapid exchange is so fast that coupling to the adjacent CH2 is not observed. i. When an 1H NMR of regular ethanol is taken the hydroxyl proton is a singlet. The NMR spectrometer will observe rapid processes as if they were a blur.Proton NMR and Rate Processes An NMR spectrometer is like a camera with a slow shutter speed. 36 Ch1.
Spin decoupling is typical in the 1H NMR spectra of alcohols. MMUy 96 . amines and carboxylic acids. • The proton attached to the oxygen or nitrogen normally appears as a singlet because of rapid exchange processes. 36 Ch1. Chem.
Carbon-13 NMR Spectroscopy
accounts for only 1.1% of naturally occurring carbon:
has no magnetic spin and produces no NMR signal.
One Peak for Each Unique Carbon Atom:
• Since the 13C isotope of carbon is present in only 1.1% natural abundance, there is only a 1 in 10,000 chance that two 13C atoms will occur next to each other in a molecule. • The low probability of adjacent 13C atoms leads to no detectable carbon-carbon splitting.
Chem. 36 Ch1.
and 13C do split each other, but this splitting is usually eliminated by adjusting the NMR spectrophotometer accordingly.
• The process of removing the coupling of 1H to an attached carbon is called broadband (BB) proton decoupling.
Most 13C NMR, therefore, consist of a single peak for each unique carbon.
Chem. 36 Ch1.
• Just as in 1H NMR spectroscopy, chemical shifts in 13C NMR depend on the electron density around the carbon nucleus: Decreased electron density causes the signal to move downfield (desheilding). Increased electron density causes the signal to move upfield (sheilding).
• Because of the wide range of chemical shifts, it is rare to have two 13C peaks coincidentally overlap.
A group of 3 peaks at δ 77 comes from the common NMR solvent deuteriochloroform and can be ignored.
Chem. 36 Ch1.
Chem. 36 Ch1. MMUy 100 .
36 Ch1. MMUy 101 .Chem.
MMUy 102 . Off-Resonance Decoupled Spectra • Broad-band decoupling removes all information about the number of hydrogens attached to each carbon. • Use of off-resonance decoupled spectra has been replaced by use of DEPT 13C NMR. 36 Ch1. Chem. • Off-resonance decoupling removes some of the coupling of carbons to hydrogens so that the coupled peaks will not overlap.
CH. 36 Ch1. the broadband decoupled spectrum is annotated with the results of the DEPT experiments using the labels C. CH. • The final DEPT spectra explicitly show C. • To simplify the presentation of DEPT data. CH2 and CH3 above the appropriate peaks . DEPT 13C NMR • DEPT (Distortionless Enhanced Polarization Transfer) spectra are created by mathematically combining several individual spectra taken under special conditions. MMUy 103 . Chem. CH2 . and CH3 carbons.
MMUy 104 . and CH3 signals Chem. 36 Ch1. CH2.• Example: 1-chloro-2-propanol (a) The broadband decoupled spectrum and (b) a set of DEPT spectra showing the separate CH.
Chem. The x-axis of a mass spectrum represents the masses of ions produced.Introduction to Mass Spectrometry (MS) A mass spectrometer produces a spectrum of masses based on the structure of a molecule. 36 Ch1. The y-axis represents the relative abundance of each ion produced. The pattern of ions obtained and their abundance is characteristic of the structure of a particular molecule. MMUy 105 . A mass spectrum is a plot of the distribution of ion masses corresponding to the formula weight of a molecule and/or fragments derived from it.
MMUy 106 . 36 Ch1.Chem.
The Mass Spectrometer • One common type is the Electron Impact Mass Spectrometer (EI MS). Chem. • An electron may be dislodged from the molecule by the impact.) because it has the same molecular weight as the analyte. 36 Ch1. Ionization (the formation of ions) • A molecule is bombarded with a beam of high energy electrons. This initial ion is called the molecular ion (M+. leaving a positively charged ion with an unpaired electron (a radical cation). MMUy 107 .
36 Ch1. MMUy 108 .this causes fragmentation. Fragmentation • Excess vibrational energy is imparted to the molecular ion by collision with the electron beam . The fragmentation pattern is highly characteristic of the structure of the molecule. Chem.
Chem. MMUy 109 . 36 Ch1. where z = +1). (m/z). • Most of the fragments detected have charge +1. the net effect is sorting of the ions by mass (m/z. • The charged molecular ion (M+) and fragments pass through an analyzer that sorts the ions according to m/z. Ion Sorting • The fragments are sorted according to their mass to charge ratio.
as the magnetic field is varied.• One method of sorting involves directing the ions through a curved tube that passes through a magnetic field. MMUy 110 . Chem. 36 Ch1. ions of different m/z values successfully traverse the tube and reach the detector.
36 Ch1. MMUy 111 .The Mass Spectrum After ion sorting the results are plotted as a spectrum with m/z on the horizontal axis and relative abundance of each ion on the vertical axis. The masses are based on rounding of atom masses to the nearest whole number (in low resolution mass spectroscopy). Chem. Data from a mass spectrometer can be represented as a graph or table. The most abundant (intense) peak in the spectrum is called the base peak and is assigned a normalized intensity of 100%.
The data and fragmentation patterns for ammonia are as follows: The base peak for ammonia is the molecular ion. 36 Ch1. Chem. MMUy 112 . but this is often not the case.
The small peak at m/z 18 comes from the small amount of 15N1H3 because of the small natural abundance of 15N compared to 14N. MMUy 113 . This peak is called an M+1 peak. 36 Ch1. Chem.
36 Ch1.Chem. MMUy 114 .
Determination of Molecular Formulas and Molecular Weights The Molecular Ion and Isotopic Peaks • The presence of heavier isotopes one or two mass units above the common isotope yields small peaks at M+. 36 Ch1.+1 and M+. Chem. MMUy 115 .+1 and M+.+2. • The intensity of the M+.+2 peaks relative to the M peak can be used to confirm a molecular formula.
Predicted ratios of molecular ions for compounds containing various ratios of chlorine and bromine. MMUy 116 . 36 Ch1. based on natural isotopic abundance. Chem.
MMUy 117 .016% natural abundance of 2H: Chem. 36 Ch1.+1 peak of 1.11% natural abundance of 13C and a 0.17% based on a 1.• Example: In the spectrum of methane one expects an M+.
High-Resolution Mass Spectrometry
Low-resolution mass spectrometers measure m/z values to the nearest whole number. High-resolution mass spectrometers measure m/z values to three or four decimal places. The high accuracy of the molecular weight calculation allows accurate determination of the molecular formula of a fragment.
Example: One can accurately pick the molecular formula of a fragment with a nominal molecular weight of 32 using highresolution MS:
Chem. 36 Ch1.
The exact mass of certain nuclides is shown below:
Chem. 36 Ch1.
In EI mass spectrometry the molecular ion is highly energetic and can break apart (fragment). Fragmentation pathways are predictable and can be used to determine the structure of a molecule. The processes that cause fragmentation are unimolecular. The relative ion abundance is extremely important in predicting structures of fragments.
Chem. 36 Ch1.
In the spectrum of propane the peak at 29 is the base peak (most abundant) 100% and the peak at 15 is 5. Fragmentation by Cleavage at a Single Bond • Cleavage of a radical cation occurs to give a radical and a cation but only the cation is observable by MS.6%: Chem. • In general the fragmentation proceeds to give mainly the most stable carbocation. 36 Ch1. MMUy 121 .
resides). 36 Ch1. Chem. Ion is formed by loss of one of its most loosely held electrons . the location of the lone electron cannot be predicted and the formula is written to reflect this using brackets. Fragmentation Equations • The M+. If nonbonding electron pairs or pi electrons are present. • In molecules with only C-C and C-H bonds. and π electrons in double bonds are common locations for an electron to be lost (i.e. MMUy 122 . Loosely held nonbonding electrons on nitrogen and oxygen.. an electron from one of these locations is usually lost by electron impact to form M+. where the remaining unshared electron in M+.
MMUy 123 . 36 Ch1.• Example: The spectrum of hexane Chem.
36 Ch1. Chem.• Example: spectrum of neopentane Fragmentation of neopentane shows the propensity of cleavage to occur at a branch point leading to a relatively stable carbocation. MMUy 124 . The formation of the 3o carbocation is so favored that almost no molecular ion is detected.
Alkenes fragment to give resonance-stabilized allylic carbocations. • Carbon-carbon bonds next to an atom with an unshared electron pair break readily to yield a resonance stabilized carbocation.• Carbocations stabilized by resonance are also formed preferentially. Chem. MMUy 125 . 36 Ch1.
MMUy 126 . Chem.• Carbon-carbon bonds next to carbonyl groups fragment readily to yield resonance stabilized acylium ions. 36 Ch1.
36 Ch1.• Alkyl substituted benzenes often lose a hydrogen or alkyl group to yield the relatively stable tropylium ion. Chem. MMUy 127 .
Chem. MMUy 128 .• Other substituted benzenes usually lose their substitutents to yield a phenyl cation. 36 Ch1.
-18 peak from loss of water. MMUy 129 . Chem. Fragmentation by Cleavage of 2 Bonds • The products are a new radical cation and a neutral molecule. 36 Ch1. • Alcohols usually show an M+.
Chem. H. 36 Ch1. OH. OR etc. MMUy 130 . • Carbonyl compounds can undergo a McLafferty Rearrangement: where Y may be R.• Cycloalkenes can undergo a retro-Diels Alder reaction to yield an alkadienyl radical cation.
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