CHAPTER 7 ULTRAVIOLET SPECTROSCOPY ost organic molecules and Functional groups are transparent in the portions ofthe electro- Me ‘spectrum that ve call the ultraviolet (UY) and visible (VES) regions—that is, the regions where wavelengths range from 190 nm to 800 nm. Consequently, absorption spec. Lwoscopy is of limited uttty in this range of wavelengths. However, in some cases we can derive use- fal information from these regions of the spectrum. ‘That information, when combined with the detail provided by infrared.and nuclear magnetic resonance (NMR) spectra, can lead to valuable structural proposals (C1 7.1 THE NATURE OF ELECTRONIC EXCITATIONS ‘When continous radiation passes through & transparent materia, a portion ofthe radiation may be absorbed. I tht occurs, che residual radiation, when itis passed through a prism, yields a spect with gaps in it called an absorption spectrum. As a result of energy absorption, atom or mole, cules pass from a slate of low energy (the initial, or ground state) tow state of higher energy (the excited state). Figure 7.1 depits this excitation process, which is quantized. The electromagnetic, radiation that is absorbed has energy exactly equal to the energy difference between the excited and ground states. Tn the case of ultraviolet and visible spectroscopy, the transitions that result in he absorption of clectromagnetic radiation inthis region of the spectrum are transitions between electronic enctey levels. As a molecule absorbs energy, an electron is promoted from an occupied orbital to ay \wvoceupied orbital of greater potential energy. Generally, the most probable transition is from the highest occupied motecular orbital (HOMO) to the lowest ymoceupied molecular orbital (LUMO). The energy dltferonces between electronic levels in most molecales vary from 125 to £650 idole (kilojoules per mote). For most molecules the lowest-energy occupied! molecular orbitals are the e orbitals, which correspond to @ bonds. The 7 orbitals lie at somewhat higher energy levels, and orbitals that hold dashed pairs, dhe nonbonding (a) orbitals, lie at even higher encrpies. The umaccupied, or antibonding orbitals (7 * and o*), are the orbitals of highest energy. Figure 7.24 shows a typical progression of electronic energy levels lexcitoc) AE= (excites) — Egroure eho FIGURE 7.1 Theescitation process tground) 381382, ‘Ultraviolet Spectroscopy ot Eneicy| f Occupied levels w FIGURE 7,2 Blecronic energy levels and transitions Jn all compounds other than alkanes, the electrons may undergo several possible transitions of different energies. Some of the most important transitions are o—+o* Inalkanes o> In earbony! compounds nm In alkenes, carbonyl compounds, alkynes, Increasing energy azo compounds, and so on n— ot In oxygen, nitrogen, sulfur, and Dalogen compounds ar In earbonyl compounds Figure. 7.2b illustrates these transitions. Blectronic energy levels in aromatic molecules are more: complicated than the oncs depicted here. Section 7.14 will describe the electronic transitions of ‘aromatic compounds. Clearly, the energy required to bring about transitions from the highest occupied energy Tevel (HOMO) in the ground state tothe lowest unoccupied energy level (LUMO) is less than the energy required to bring about a transition from a lower occupied energy evel. Thus, in Figure 7.20 an n= a transition would have 8 lower energy than a. —* zc transition. For many purposes, the transition of lowest energy isthe most important Not all of the transitions that at first sight appear possible aro observed. Certain restrictions, called selection rues, must be considered. One important selection rule states that transitions, that involve a change in the spin quantum number of an clectron during the transition are not allowed to take place; they are called “forbidden” transitions. Other selection rules deal with the numbers of electrons that may be excited at one time, with symmetty properties of the mol- ‘cule and of the electronic states, and with other factors that need not be discussed here. “Transitions that are formally forbidden by the selection rules are often not observed. However, theoretical treatments are rather approximate, and in certain cases forbidden transitions are ob- served, although the intensity of the absorption tends to be much lower than for transitions that are allowed by the selection rules. The n—* * transition i the most common type of forbidden transition.723 Principles of Absorption Spectroscopy 383 (7.2 THE ORIGIN OF UV BAND STRUCTURE For an atom that absorbs inthe ultraviolet, the absorption spectrum sometimes consiss of very shat lines, a5 would be expected fora quantized process occuring between two diserete energy {evels. For molecules, however, the UV absorption usually ozeus over a wide range of wavetengthe because molecules (as opposed to atoms) normally have many excited modes of vibration and rota, {ion at room temperature. In fact, the vibration of molecules cannot be completely “irozen out” oven tabsolite zo. Consequently, a collection of molecules generally has its memibers in many states of vibrational and rotational excitation, The energy levels fr these states are quite closely spaced, Corresponding to energy differences considerably smaller than those of electronic levels, The rotational and vibrational levels are ths “superimposed” on the elecronic levels. A molecule may therefore undergo electronic and vibrational-rotational excitation simultaneously, as shown ix Figure 7.3. Because there ae so many possible transitions, each differing from the others by only a slight umount, each electronic transition consists of a vast number of lines spaced so closely that the spectrophotometer cannot resolve them. Rather, the instrument traces an “envelope” over the entire Pattern. What is obscrved from these types of combined transitions is thatthe UV spectrum of a ‘molecale usually consists of a broad band of absorption centered near the wavelength of tie mejor transition, (7.3 PRINCIPLES OF ABSORPTION SPECTROSCOPY ‘The greater the nuraber of molecules capable of absorbing light of a given wavelength, the greater the extent of light absorption. Furthermore, the more effectively a molecule absorbs light ofa given wavelength, the greater the extent of light absorption. From these guiding ideas, the following empirical expression, known as the Beer-Lambert Lavy, may be formulated. Ff os ee ea eft EEE ‘Vibrational levels b. ELECTRONIC GROUND STATE FIGURE 7.3 Electronic transitions with vibrational trasitions supesimposed. (Rotational levels ‘hich are very losely paced within the vibrational tevels, ae omitted for elarity.)384 Uttraviolet Spectroscopy A=log(lo/P) A= absorbance 1 for a given wavelength Equation 7.1 Jp= intensity of light incident upon sample cell = intensity of light leaving sample cell ¢= molar concentration of solute 1 length of sample cell (em) e= molar absomptivity ‘The tem log lis also known asthe absorbance (ore optical density in older teratae) and may be represented by A. The molar absorptivity (formerly known as the molar extinction coefficient) s 4 propery of the molecule undergoing an electronic transition and is not a function of the variable ‘parameters involved in preparing a soloion, The sizeof the absorbing system and the probability that the electronic transition wil take place contol the absorptivity, which ranges from O to 10%. Values above 10" are termed high-intensity absorptions, while values below 10" arc low-intensity absorp Sons, Forbiddon transitions (see Section 7.1) have ubsorptivities inthe range feom 0 to 1000. ‘The Beer-Lambert Law is rigorously obeyed when a single species gives rise to the observed sorption. The law may not be obeyed, however, when different forms of the absorbing molecule ‘rein equilibrium, when solute and solvent form complexes though some sort of association, when thermal equilibrium exists between the ground clectonic state and a low-lying excited rate, cr wen Muorescent compounds or compounds changed by imadiation are preset (7.4 INSTRUMENTATION ‘The typical ultaviolet—visible spectrophotometer consists of a light source, a monochromator, ‘und a detector. The light source is usually a deuterium lamp, which emits electromagnetic radiation in the ultraviolet region of the spectrum. A second light source, a tungsten lamp, is used for wave lengths in the visible region of the spectrum. The monochromator isa diffraction grating; its role is to spread the beam of light into its component wavelengths, A system of slits focuses the desired wavelength on the sample cell. The light that passes through the sample cell reaches the detector, Which records the intensity of the transmitted light /. The detector is genenally a photomultiplier tube, although in modem instruments photodiodes are also used. In a typical double-beam instrit- ment, the light emanating from the light source is split into two beams, the sampie beam and the reference beam, When there is no sample cell in the reference beam, the detected light is taken to be equal to the intensity of light entering the sample Jy ‘The sample cell must be constructed of a material that is transparent tothe electromagnetic rad ation being used in the experiment, For spectra in the visible range of the spectrum, cells composed of glass or plastic are generally suitable. For measurements in the ultraviolet region of the spectruna, however, glass and plastic cannot be used because they absorb ultraviolet radiation, Instead, cells ‘made of quartz: must be used since quartz does not absorb cadiation in this region, ‘The instrument design just described is quite suitable for meesurement at only one wavelength, If a complete spectrum is desired, this type of instrument has some deficiencies. A mechanical system is required (0 rotate the monochromator and provide u scan of all desired wavelengths. This type of system operates slowly, and therefore cousiderable time is required to record a spectrunn A modem improvement on the traditional spectrophotometer is the diode-array spectro- photometer. A diode array consists of u series of photodiode detectors positioned side by side on a silloon crystal. Bach diode is designed to record a narrow band of the spectrum, ‘The diodes are con- ected so thatthe entre spectrum is recorded at once. This type of detector has no moving parts and i i a7.5 Presentation of Spectra 385 can record spectia very quickly, Furthermore, its output can be passed to a computer, which ean process the information and provide a variety of useful ousput formats, Since the number of photo Odes is limited, the speed andl convenience described here are obtained at some small cost in resol i tion. For many applications, however, the advantages of tis type of insteument outweigh the loss of resolution (1 7.5 PRESENTATION OF SPECTRA The ultraviolet-visible spectrum is generally recorded as a plot of absorbance versus wavelength. Ie is customary to then replot the data with either € or log ¢ plotted on the ordinate and wavelength plotted on the abscissa, Figure 7.4, the spectrum of benzoic avi is typical of the manner in whiel spectra are displayed. However, very few electronic spectra are reproduced in the scientific liter ture; most are described by indications of the wavelength maxima and absorptivties ofthe principal absorption peaks, For benzoic acid, a typical description might be Aygg = 230 01 log e=4.2 mm a1 282 29 igure 7.4 is the actual spectrum that corresponds to these data : He 45] : Benzois acid YOM 200 Solvent: eystohexane 4 _| g 33 | \ 2a 0h — 22 — 2 Eee 20) \ 200024 Zea B89 B00 Hao Wavelength (nm) FIGURE 7.4 Utravioletspectnum of benzpic acid in cyclohexane. (From Friedl, R.A..and M. Orci, Uteravioler Spectra of Avematic Compounds, Sok Wiley and Sons, New York, 1951. Reprinted by permission)386 Ultraviolet Spectroscopy (1 7.6 sowvenrs ‘The choice of the solvent to be used in ultraviolet spectroscopy is quite important. The first cvterion for a good sotvent is that it should not absorb ultraviolet radiation in the same region as the sub © stance whose spectrum is being determined. Usually solvents that.do not contain conjugated sys- 3 fems are most suitable for this purpose, although they vary regarding the shortest wavelength at which they remain transparent to ultraviolet radiation, Table 7.1 lists some common ultraviolet spectroscopy solvents and their cutoff points or minimum regions of transparency. Of the solvents listed in Table 7.1, water, 95% ethanol, and hexane are most commonly used, Bach is transparent in the regions of the ultraviolet spectrum in which interesting absonption peaks from sample molecules are likely to occur. A second criterion for @ good solvent is its effect on the fine structure of an absorption band. Figure 7.5 illustrates the effects of polar and nonpolar solvents on an absorption band, A not plac solvent does not hydrogen bond with the solute, and the spectrum of the solute closely approximates the spectrm that would be produced in the gaseous state, in which fine structure is often observed. Ina polar solvent, the hydrogen bonding forms a solute-solvent complex, and the fine structure may disappear: TABLE 7.1 SOLVENT CUTOFFS eee eee Ee ee Eee Eee Pee EEE ei Acetonittle 190mm n-Hexane 201 nm, Chloroform 240 Methanol 205 Cyclohexane 195 Tsonceane 195 I4Diowme 215, Water 190 9596 Ethanol 205 ‘Trimethyl phosphate 210 Wavelength (nm) FIGURE 7.8 Ulvavioles spectra of phenol in ethanol and in isooctane. (From Coggeshall, N.D.- and E.M, Lang, Jounal af the American Chemical Soviets. 70 (1948), 3288, Reprinted by persion.)77 What is a Chromophore? 387 TABLE 7.2 SOLVENT SHIFTS ON THE n—> 1 TRANSITION OF ACETONE Solvent 0 CHOH CHLOH CHC, Cy Fromm) — 264.5270 m a7 2 +> A third criterion for 2 good solvent is its ability that will be absorbed via stabilization of either the g ‘form hydrogen bonds as readily with the exeited sates, and these polar solvents increase the energi solvents shift transitions of the n> x type to leases the excited states may form stron, to influence the wavelength of ultraviolet light ound or the excited state. Polar solvents do not states of polar molecules as with their ground es of electronic transitions in the molecules. Polar shorter wavelengths. On the other hand, in some iger hydrogen bonds than the corresponding ground states, 1h Such a ease, a polar solvent shifts an absorption to longer wavelength since the eneruy of the «* type, ‘These transitions are of such a high energy that they absorb ultraviolet energy at very short wore. lenaths—shorter than the wavelengths tht re experimentally accessible using typical apectropho. tomteters. Figure 7.6 illustrates this type of transition. The exeitation of the czbondling electron to the 6-antibonding orbital is depicted at the right. Alcohols, Ethers, Amines, and Sulfur Com, !pounds. In saturated molecules that contain atoms bear- ing nonbonding pairs of eleettons, transitions Of the > 6° type become important, They are also c% asd q ‘ C i G Je Seacasg83 FIGURE 7.6 oF 0% casiion388 Ultraviolet Spectrascopy ‘5 (sp?) eeu FIGURE 7,7 n— 0° transition rather high-energy transitions, but they do absorb radiation that ies within an experimentally accessible ‘range. Alcohols and amines absorb in the range from 175 t0:200 nim, while organie thiols and sulfides absorb between 200 and 220:nm. Most of the ahscrptions are below the extoff points for the common solvents, so they are not observed in solution spectra. Figure 7.7 illustrates an. > o* transition for an amine. The excitation of the nonbonding electron to the antibonding orbital is shown atthe tight. Alkenes and Alkynes. With unsaturated molecules, —> * transitions become possible. These transitions are of rather high energy as well, but their positions are sensitive to the presence of sub- stitution, as will be clear later: Alkenes absorb around 175 nm, and alkynes absorb around 170 nen. Figure 7.8 shows this type of transition, Carbonyl Compounds. Unsaturated molecules that contain atoms such as oxygen or nitrogen may also undergo n— 1* transitions. These are perhaps the most interesting and most studied transi- tions, particularly among carbonyl compounds. These transitions are also rather sensitive (© sub- stitution on the chromophoric structure. The typical carbonyl compound undergoes ann —> x ‘transition around 280 t0 290 nm (e~ 15). Most n— 2* transitions ate forbidden and hence are of low intensity. Carbonyl compounds also have a z—* x* wansition at about 188 nm (e= 900), Figure 7.9 shows the n+ * and a * transitions of the earbonyl group. FIGURE 7.8 5+ x* transition * Contry to what yon might expect from simple theory, the oxygen atom of the carbonyl exp is at 5p" hybridize. Spectroscopist have shows that shhong the carbon atom is sp* hyde, the hybridiation ofthe eayen alow mare closely appeximaes sp.7.7 Whatis a Chromophore? 389. Pano %a aie " ay ee, 7a & 0) ‘o— a0. ater) FIGURE 7.9 Blecironic wansitions ofthe carbonyl soup. ‘Table 7.3 lists typical absorptions of simple isolated chromophores. You may notice that these simple chromophores neasy al absorb a approximately the same wavelength (160 to 210 nm) ‘The attachment of substituent groups in place of hydrogen on a basi chromophore structure changes the position and intensity of an absorption band of the chromophore. The substityent -Foups may not give rise to the absorption ofthe ultraviolet radiation themselves, but their presence ‘modifies the absorption of the principal chromophore. Substituents tht increase the intensity ofthe absorption, and possibly the wavelength, arc called auxochromes, Typical auxochromes include ‘methyl, hydroxyl, alkoxy, halogen, and atmino groups. Other substituents may have any of four kinds of effeets om the absorption: 4, Bathochromic shift (ced shift)—a shift to lower energy or longer wavelength 2. Hypsochromie shift (biue shitt)—a shift to higher energy or shorter wavelength, 3. Hyperchromic effect—an increase in intensity 4, Hypochromic effect—a decrease in intensity390 Ultraviolet Spectroscopy TABLE 7.3 ‘TYPICAL ABSORPTIONS OF SIMPLE ISOLATED CHROMOPHORES lass Transition Anas (nm) loge _Class__Transition aya (nm) log € R-OW not 180-25 RAND, net 1 R-O-R = not 180, 3.5 RCH ew? 19020 RON no 19035, noe 29010 ROSH nvo* 2103.0 RO 13030 ROR eee S30 none BOS RCC-R rte 1103.0 -RCOOH ss mtx* 05S RCN none 160 <0 RCOOR’ nt 05S RNNER ontm® MO <10-RCONH) nt? 20045 (1 7.8 THE EFFECT OF CONJUGATION (One of the best ways fo bring about a bathochromic shift is to increase the extent of conjugation in a double-bonced system. In the presence of conjugated double bonds, the electronic energy levels ofa chromophore move closer together. As a result, the energy required to produce a transition from an occupied electronic energy level to an unoccupied level decreases, and the wavelength of the light absorbed becomes longer. Figure 7.10 illustrates the bathochromic shift that is observed in a series of conjugated polyenes as the length of the conjugated chain is increased. Conjugation of twa chromophores not only results in a bathochromic shift but incresses the intensity of the absorption. These two effects are of prime importance in the use and interpretation of electronic spectra of organic molecnles because conjagation shifts the selective light absorption of isolated chromophores from a region of the spectrum that is not readily accessible toa region that loce Wavelengtn, am FIGURE 7.10. Cliy(CH=CH),~CHyultayiolet spectrs of dimesty}polyenes. (2) n= 3; (o) n= 4: (e)n=5. (From Nayler Band MC. Whiting, Joursal ofthe Chemical Society (1955): 3042.)394 Ultraviolet Spectroscopy tL Mp “system and its auxochrome. ‘of resonance system In similar fashion, methyl groups also produce a bathochromie shift. However, as methyl groups do not have unshared electrons, the interaction is thought to result from overtap of the ing orbitals with the zsystem as fallows: “This type of interaction is often called hyperconjuugation Its net effets an extension of the a system. CO] 7.10 THE WoopWaRD-FESER RULES FOR DIENES 1h butadiene, two possible — i* ansitions can occur: ya ys and ys—> y;2. We have ale realy discussed the easily observable ys > ys* transition (See Fig. 7.12), The yo —> yy" transition {snot often obsetved, for two reasons. First, if lies near 175 nim for butadiene: sccand, itis a forbid. den transition for the s-rrans conformation of double bonds in butadiene, 175 oniten) 3" 50 am Gal Ws a Onn Gowen rans Wx HO 2 fut conformation ry740 The Wootward-Fieser Rules for Dienes 395 A transition at 175 nm lies below the cutoff points of the common solvents used to determine UV spectra (Table 7.1) and therefore is not easily detectable. Furthermore, the s-trune conformation is mote favorable for butadiene than is the s-cis conformation, Therefore, the 175-nm band is not usually detected, In general, conjugated dienes exhibit an intense band (¢ = 20,000 to 26,000) in the region from 217 to 245 nm, owing to a x» 2* transition. The position of this band appears to be quite insensi- tive to the nature of the solvent. Butadiene and many simple conjugated dienes exist in a planar s-trans conformation, 2s noted, Generally, alkyl substitution produces bathochromic shifts and hyperchromic effects, However, ‘with certain patterns of alkyl substitution, the wavelength increases but the intensity decreases. The Sedialkylbutadicnes possess too much crowding between alkyl groups to permit them (0 exist in the s-trans conformation, They convert, by rotation around the single boud, to an s-cis conforma- tion, which absorbs at longer wavelengths but with lower intensity than the corresponding s-trans conformation \ C H ah Sen Bh OO ea 1H J a . In cyclic dienes, where the central bond is a part of the ring system, the diene chromophore is, usually held rigidly in either the s-crans (transoid) or the s-cis (cisoid) orientation. Typical absorp- tion specira follow the expected pattern: oe =6hle Homoannular diene (cisoid or s-cis) Heteroanmular diene (transoid or s Less intense, € = 5,000-15,000 More intense, ¢ = 12,000-28,000 longer (273 nm) A shorter (234 nm) By studying a vast number of dienes of each type, Woodward and Fieser devised an empirical correlation of structural variations that enables us to predict the wavelength at which « conjugated iene will absorb, Table 7.5 summarizes the rules, Following are a few sample applications of these rules. Notice that the pertinent parts of the structures are shown in bold face.42 C1 7.16 VISIBLE SPECTRA: COLOR IN COMPOUNDS Ultraviolet Spectroscopy The portion of the electromagnetic spectrum lying between about 400 snd 750 nm is the visible region. Light waves with wavelengths between these limits appear colored to the human eye. As anyone who has seen light diffracted by a prism or the diffraction effect of a rainbow knows, one nd ofthe visible spectrum is violet, andthe other is ved. Light with wavelengths near 400 nm is viol, while that with wavelengths near 750 ni is red The phenomenon of color in compownds, however, is not as straightforward as the preceding discussion would suggest. Ifa substance absorbs visible light, it appears to have a color if not, it appears white, However, compounds that absomb light in the visible regiow of the spectrum do not possess the calor cocresponding tothe wavelength of the absorbed light. Rather, there is an inverse relationship between the observed color and the color absorbed. ‘When we observe light emitied from a source, as from a lamp or an emission spectrum, we ob- serve the calor corresponding 10 the wavelength of the light being emited. A light source emitting violet light emits light at the high-energy end of the visible spectrum, A light source emiting red Tight emits light atthe low-energy end of the spectrum, However, when we observe the color of a particular object or substance, we do not observe that ‘objector substance emitting light. (Certainly, the substance,daes nor glow in the dark.) Rether, we ‘observe the light that is being reflected. ‘The color that our eye perceives is not de color cortespond- {ng to the wavelength of the light absorbed but its complement. When white light falls on an object, light of a particular wavelength is absorbed. The remainder ofthe light is reflected. The eye and brain register all of the veflected light as the color complementary tothe calor that was absorbed. Jn the case of transparent objects or solutions, the eye receives the light that is transmitted, ‘Again, light ofa particular wavelength is absorbed, and the remaining light passes through to reach the eye. As befor, the eye rexisters this transmitted light as the color complementary tothe color that was absorbed. Table 7.13 ilustrates the relationship between the wavelength of light absorbed by a substance and the color perceived by an observer Some familiar compounds may serve to underscore these relaionships between the absorption spectrum and the observed color, The structural formulas of these examples are shown, Notice that ach of these substances bas a highly extonded conjugate system of electrons. Such extensive con- iugation shifts their electronic spectra to sueh long wavelengths that they absorb visible light and appear colored. TABLE 7.13 RELATIONSHIP BETWEEN THE COLOR OF LIGHT ABSORBED BY A COMPOUND AND THE OBSERVED COLOR OF THE COMPOUND. Color of Light Wavelength of Light Observed Absorbed Absorbed (nm) Color Violet 400 Yellow Blue 450 Orange Blue-green 300 Red Yeilow-green 530 Redviolet Yellow 550 Viele ‘Orange-red 60 Blue-green Red 700 GreenSeen | ‘TAT What (© Look for in an Ultraviolet Spectram: A Practical Guide 413 B-Carotene (piginent from carrots) Anus = 452.000, orange Cyonidin (blue pigment of corntiower: Jo Malachite green (a triphenylethane dye) Cus cH F-Carotene (a carotenoid, which isa class of plant pigments) Ane = 452 un on ‘OH ‘oH on ‘Cyanidin chloride (an anthocyania, another class of plant pigments) Anan = 545 cH, CH nN Malachite green (atriphenylmetiane dye) Ans, = 617 am 7.17 WHAT To Look FoR IN AN ULTRAVIOLET SPECTRUM: A PRACTICAL GUIDE is often difficult to extract a great deal of information from a UV: lear by now that @ UV spectrum is most useful whien at least a ‘own; in this way, the vavious empirical rules can be applied, Nevertheless, ‘spectrum used by itsett. It should be414 Ultraviolet Spectrascopy setve to guide our use of UV data. These generalizations are a good deal more meaningful when oo, bined with infrared and NMR date—which can, for instance, definitely identify carbonyl soups, dow ble bonds, aromatic systems, nitro groups, nitriles, enones, and other important chromophores. Inthe: absence of infiared or NMR data, the following observations should be taken only as guidelines: 1. A single band of tow-to-medivan intensity (€= 100 to 10,000) at wavelengths tess than 220 mm vovelly indicates ann —r a wansiton. Amines, alcohols, ethers, and thiols are possbilifes Provided the nonbonded electrons are no inched in conjugated sytem. An exception to his ‘generalization is thatthe n — 2e* transition of oyano groups (—C=N : ) appears in this vegion, = However, ths is a weak tansition (€ < 100), and the cyano group is easly identified inthe in. = frared. Do not neglect to look for NH, OH, C—O, and $—H bands inthe infrared spectrum. 2. A single band of low intensity (€ = 10 10 100) in the region 250 to 360 rm, with no major absorption at shorter wavelengihs (200 t0 250 nm), usualy indicates an n ~* re transition, Since the absorption dees not occur at long wavelength, a simple, or uneonjugated, chro. ‘ophore is indicated, generally one that contains an O, N, ot $ atom Examples of this may include C=O, C=N, N=N, “NO, ~COOR, ~COOH, ot ~CONH,. Once again, infised and NMR spectra should help a great deal 3. Tio bends of medion intensity (¢ = 1,000 to 10,000), Bote with Anas above 200 nm, gener ally indicate the presence of un aromatic system. If an atomatie system is present, there may be @ good deal of fine structure in the longer-wavelength band (in nonpolar solvents only). Substitution on the aromatic rings increases the molar absomptvity above 10,000, paticu. larly ifthe substituent increases the length ofthe conjugated system, Jn polynuctear aromatic substances, a third band appears ear 200 nm, a band that in sim- pler aromiatics occurs below 200 nim, where i¢ cannot be obscrved. Most polynuclear aro- maties (and heterocyslic compounds) have very charicteristic intensity and band-shape (Gine- structure) patterns, and they may often be identified via comparison to spect that are available in the literature, The textbooks by Jaffé and Orehin and by Scott, which are listed inthe references atthe ond ofthis chapret, are good sources of spectra 4. Bands of hig intensity (€ = 10,000 t0 20,000) that appear above 210 nm generally represent cither an a,p-unsaturated ketone (check the infrared spectrum), a diene, or a polyene. The _geater the length of the conjugated system, the longer the observed wavelength, For dienes, the Ags may be calculated using the Woodward-Fieser Rules (Section 7.10). 5. Simple ketones, acids, esters, amides, and other compouncis containing both m systems and unshared electron pairs show two absorptions: am n—> r* transition at longer wavelengths (300 nm, low intensity) and a 2 —* * transition at shorter wavelengths (<250 nm, high intensity). With conjugation (enoves), the Zyx of the x —* * band moves to longer wave= Jongths and can be predicted by Woodward's Rules (Section 7.12). The # value usually rises above 10,000 with conjugation, and as it is very intense, it may obscure at bury the weaker n> a transition, For 0,B-unsaturated esters and acids, Nielsen's Rules (Section 7.13) may be used to predict the position of Ayas with inereasing conjugation and substitution, 6. Compounds that ave highly colored (have absorption in the visible region) are likely to contain ‘long-chain conjugated system ot a polycyclic aromatic chromophore, Benzenoid compounds may be colored if they ave enough conjugating substituents, For nonaromatie systems, usu ally a mininuam of four to five conjugated chromophores are reyuired to produce absorption in the visible region, However, some simple nitro, a20, nitroso, a-diketo, polybromo, and polyiodo compounds may also exhibit color, as may many compounds with qinoid structures, <>