/ CHAPTER 2 ; TABLES OF CHARACTERISTIC FREQUENCIES I 2.1. POSITION OF ABSORPTION BANDS Unless otherwise stated the bands usually appear within £10 cm"? of the position shown. The data are mostly for compounds measured as dilute solutions in nonpolar solvents, and the external and internal factors such as solvation, inter- or intra+ molecular hydrogen-bonding, electric effects of nearby groups, steric strain, and other ste effects will shift the bands from their normal positions. Bands that are not practically useful are written in italics. Some have been completely omitted, e.g., skeletal vibration in the finger-print region. 2.2. INTENSITY The infrared absorption intensities still cannot be expressed in terms of a uni~ versal constant, because the band width is of the same order as the slit width, which causes the measured optical density to be influenced strongly by the slit width. ‘Therefore, in qualitative organic chemistry the intensity is usually expressed as vs (very strong), s (strong), m (medium), w (weak), etc. However, these notations, which are merely given subjectively to a band by glancing at the spectrum in question, do not represent the true intensity of a band. In the following tables the apparent molecular coefficient <* has been given whenever possible, besides the conventional notations. It is defined as: 1 Ty 4 onal), : apparent molecular absorption coefficient €: concentration, moles per liter 1: cell thickness, cm Tp and T: intensity of entering and transmitted light, Measurements are not made under strictly monochromatic conditions because of the slit width, Accordingly, logy (To/T). is the apparent optical density obtained when the instrument is set to awave- number of », and it is not the true absorptivity involved in the Beer-Lampert rule. The apparent integrated area is defined as: B=2.303f 7Methods for converting apparent intensities into true molecular absorption coefficients and integrated areas (A) are described in reference (1). The = values given in the tables give only a rongh idea of the intensities sine the values vary according to the instrument, slit widtis, and other experimental condi tions, and the difference between ¢ and = is also variable (¢ is larger than « by 0 ~20%). Even under identical instrumental conditions the « values may vary as much as 10% according to the sample concentration. An example has also been reported in which the « was 1430 with a sodium ebloride prism whereas it was 1890 with a calcium fluoride prism. "The © values are hence still in quite an unsatisfactory state but conventional notations are even more inconsistent. 2.3. ASSIGNMENTS A molecule of n atoms has 3n degrees of freedom, three of which are assigned to translational, another three to rotational (two in linear molecules such as acetylene), and the remaining 32-6 (3-5 if linear) to vibrational motions. ‘These various vibr tions (fundamental vibrations) absorb, respectively, the infrared beam at characteristic frequencies and give rise to absorption bands. However the number of absorption, bands does not coincide exactly with the number of fundamental vibrations. Thus, if the vibration dees not induce any change in the polarity of the entire molecule, the vibra- tion will not absorb the infrared energy and the number of infrared peaks will be de- creased accordingly. For example, the vibration of the central C=C bond of the ethylene molecule will not absorb infrared energy (infrared inactive). Fundamental vibration bands can be divided into those caused by stretching vibrations and those caused by deformation vibrations. Vibrations of the methylene group are shown as an example: : Ne ee ane er hs Pot ee A [ IP asymmetric symmetric stissoring. wagging twisting, rocking vasCHe »sCHs CH, Biretching vibsation ‘bending (or deformation) vibration Vibrations of the methylene group. (the + and —signs denote vibrations in the direction perpendicular to the paper). Note: Particular asymmetric stretching vibrations in which two bonds move in the opposite direction, such as the asymmetric stretching of the methylene group, are also called antisymmetric stretching vibrations. Other groups having similar arrangements of atoms, eg, HL 0 0 : n€ sot ke AG Ko & } amino nitro: carboxylate also possess fundamental vibrations corresponding to those of the methylene group. In certain cases, vibrations other than the normal ones will appear. 18+ Tables of characteristic frequenciesOvertone: Overtones having twice the frequency of the normal vibration will occa- sionally be observed as weak bands. For instance, the overtone of the carbonyl 1715 cm™ absorption may appear around 3430.cm~', and may be confused with the hydroxyl absorption, ‘Combination tone: ‘These are weak bands occasionally appearing at frequencies that are the sum or difference of two or more fundamental bands. Thus, fundamental bands at x and y em“ may give rise to weak bands at (x+y) or (r—y) em" ‘The following phenomena also occur in the spectra, ‘Coupling: Very often a 1:1 correspondence between a bond vibration and an ab- sorption band cannot be assumed. This coupling phenomenon occurs when two bonds of the same symmetry are closely located within the molecule, the respective bands are strong, and the absorptions oceur in the same region. It must be borne in mind that the coupling will cause bands to shift outside the characteristic frequency range. However, there are cases in which the coupled bands themselves constitute useful characteristic absorption bands, such as is encountered in acids and amides. Fermi resonance: When an overtone or combination band is located near a fundamental frequency, the band intensity of the former may be anomalously enhanced or bands may be split (w-butyl vinyl ether, @). ‘This coupling between an overtone or com= bination band and a fundamental band is called the Fermi resonance; the two levels also have to be of the same symmeti Reference [1] RN. Jonesand C. Sandorfy, “ Chemical Applications of Spectroscopy,” p. 271, (1956) Interscience. latsui, ‘* IR Spectra” Vol. 3, p. 151 (1958). . Kuratani and R. Mineyasu, ibid. Vol. §, p. 1 (1959) K. S. Sheshadri and R. N. Jones, “‘The Shapes and Intensities of Infrared Absorption Bands A Review,” Specirochimica Acta, in press (2] GD. Mealtins and R. J. Moss, J. Chem. Soe. 993 (1959). Abbreviations aliph, aliphatic H-bonding: hydrogen-bonding arom. aromatic , primary assoc. associated resp. respectively 7 asym. asymmetric 5 secondary conj. conjugation sad. saturated corresp. corresponding sym symmetric freq. frequency of Frequencies a tertiary unsatd, unsaturated Tables of characteristic frequencies ~ 19| Band TABLE 1 ALKANES: eo Assignment Remarks Figs 2960) | s 70 | ye CH | 70 | m 30 [og CH, — | 28902815 (er _35~75) in -OMelll, | | “lacking in -OEt. ! 2730~ 289) (28 1321) in ~> 2 | | (lacking in. -NEc oe 1 | 2820~2710 in methylenediony. (3 a 4460 | mis — | dy CH, ® 1380 | sas | a CH, — | Doublee in gem- \@ : | | 8+7). See also (11)~(13). | p-cH, | 27% |oy cH, | ‘i 2 45 1 CH: \ m 8 ‘CH scissor) 1445 in eyclopentanes, 1450 in cyslo- | | | “hasanen See also (14)~(15). | i s 3 | (CH),rock| Sometimes doublet in solid state. | | Present when w=4._ Higher with j smaller 9, Pr 743~734; Et 790~ | @ 790. “CH, also has wag and twist | ! i band at ca. 1300 (2* 1). Solid stare | ‘spectra of long chain with terminal | polar group (acids, esters, amides) @ | Show “regular series of bands at | i 1380~1180 (CEE wag). | D 6-4 | 2890 | w » CH ‘OF no practical use. 1 : | 1400 | jacH ‘Of no practical use, 4) 4CH)-0-| 742~734 | CH, rock | Corresponds to 720 band of (2) gi; 5) CH, 1170 | 8 Weaker | skeletal |. Doubletat 1380suggestszem-dimethyl |) CH than the group; indentifcation ofthis rou | cHy 1380, (e* thea made by skeletal ‘vibration oe 13) dou- 6)~). | blee pa 43 145 band is shoulder on 1170 band. | 1255 [8 Position more constant than 1210 band. m0 |e» | Absorption also at 930~925. | 1215 so Position of 1195 band more constant: |, @ aay band forms shoulder on 1195 uss |e» x | 8) CHAS) 3030 | m [ima CH, | Lecting when zing carkene CH, [@ 9E——CC | ygg¢m1005 | m 20~80 | skeletal Often obseured by other strong bands | (hydroxyl, ether, ete.) %) Code 000, 20~60 | » CH of Shifted to 3040~ 3030 if ring strain of |@ r€—Cefi)| methine | epoxy increased, e.g., fused to eyelopentanes(l, i AesTable 0) /uisgggg 30 | vas CH; of | | | methylene: : 10) NH 3050 ater, : 20 - Table 1 AtkanesSome characteristic CH bending frequencies around 1400 em~! it) O-CO-CH, | 1989~ 1368 | Characterized by high intensity. Upon aeetylaton, the 1380 [i @ 7 | Ran usually becomes sven that 1460 band. Same’ with | | snol and phenol acetates. Ocassionally doublet, 32) -CO-CH, | 13601358 | Lower than ordinary CH, bending (1380)- strong and aap. (@ @ | Ssmmetric lending it usual position (1460), but lower 10" | | terpenes (14200142 13) -COOCH,!) | 1440~ 1435 | a CH, Bands also at 1133, 1155, 790~760. 1365~1356 | 3, CH, | between ordinary 1465 and 1380 bending bands. Same with | | -CHySO,-, etc, Tnteurated intensity may give number of | @.@ 44) -CHy-CO: | 1440~ 1400 | Bending of all setive methylenes appear as strong sharp bands | @,@ | setive encthylene. | 35) ~CH-C-C | 1445~1430 | Not so-strong. Double bond can be aromatic. Lowered further |@y “CHE EE. it “Cliye between two multiple bonds. 8 16) -CHEN*Pl | 1440~1400 | ~CH,- adjacent to the clectron-attracting Nis alga shifted lower |, | ‘as in (14) and (18). [fnew band appears in this region upon conversion of amine to its salt, -CHy-N- group is presents : References [1] HB. Henbest, G. D. Meakins, B. Nicholls and A. A, Wagland, J. Chen. Soc, 1462 (1937), [2] B.D. Hills and GD, Meakins, J. Chem. Soc, 760 (1958); J. T. Braunholtz, E. A.V. Ebsworth, F.G, Mann and N. Sheppara, ibid. 2780 (1958) [3] L. 1. Briggs and L. D. Colebrook, Anal. Cheon. 29, 904 (1957), [4] JM. Martin, R. W. B. Johnston, and M. J. O'Neal, Spectrochim. Acta 12, 12 (1958). [5] CfS.A. Liebman and B. J. Gudzinowiez, Anal. Chem. 33, 931 (1961), [6] H.B. Henbest, G. D. Meakin, B. Nicholls, and K. J. Taylor, J. Chem. Soe. 1459 (1987), [7] Ju. Scheinker, E. M, Peresteni, and G, T. Bras, J. Phys. Chem. Moscow 29, 518 (1955) (see DMS. card No. 649 and. 650). ‘[8] A. R.H. Cole and D. W. Thornton, J. Chem. Soe. 1007 (1956). [9] K, Nakonishi, T, Goto and M. Ohashi, Bull, Chem. Soe. Japan 30,403 (1957). ABSORPTIONS OF ALKANES Since organic compounds often contain methylene and methyl groups most IR spectra have bands at 2950~2850 cm"! (CH, usually two with the resolution obe tained by NaCl prism), ca. 1465 em"! (CH of methylene and methyl), and 138 emt (3CH of methyl). ‘The spectrum of paraffin oil (nujol) shows these bands quite typically (Pig. 1.5). Absorption in 3000.cm- Region Alkane groups have their CH stretching at frequencies lower than 3000 cm~, whereas alkenes and aromatics have them higher than 3000 cm-1; the eyelopropane methylene and ~CH,chalogen also absorb at 305:cm-!, Thus the shape of absorption around 3000 em! gives a rough idea of the groups present. ‘The region is better re~ solved with quartz, lithium Huoride, or calcium fluoride prisms or with a grating in- strument. The spectrum of polystyrene (Fig. 1. #) shows a deep cut between the arising from the saturated and unsaturated portion of the palymer. Table } Athanes - 21gem-Dimethy! Groups (‘Table 1, 5~7) The asymmetric CH, bending at 1380 em’ is split into a doublet. However, if the weight of the gem-dimethyl group is small, as in steroids containing the side-chain isopropyl group, it will not be easy to detect with sodium chloride optics, Calcium fluoride prisms or grating instruments should be used in these cases. Bands due to groups other than alkanes might appear in the same region to form an apparent doublet. The next step is to characterize the gem-dimethyl groups from the 1150~1250 em~! bands, However, since the band intensities are not so great, and since many other vibrations have absorptions in this a molecule is rather simple. , characterization is possible only when the Groups Having Characteristic Absorption Around 1400.cm (‘Table 1, 11~16) As exemplified by the nujol spectrum (Fig. 1. 5), organic compounds usually have bands at 1460 cm~ and 1380 cm™, the former being the stronger. Reversed in= tensity relations would suggest an acetoxyl; a rather sharp band on the lower frequency side of the 1380cm band would suggest a methyl ketone or a methoxycarbonyl ; and a band near 1410.cm“? between the two usual absorptions would suggest -CH,-CO-, ~CH,-N*-, and the like, to be present. It is better to employ a calcium chloride prism or a grating instrument, and to measure solid samples as KBr disks or carbon tetra- chloride solutions. The extensive studies on steroids by Jones and coworkers are typical! Other Absorptions Alkane groups show absorptions in the 1300~1100.cm~! region besides the bands at 3000em"*, 1400 cm, and 720 cm™ (methylene chain). These are caused by CH, wagging, CH, twisting, and CH, rocking, but they are usually weak; more- over, C-C stretching and other skeletal vibrations appear in this region. ‘These 1300 ~1100 cm-! bands are therefore not used in qualitative organic chemistry excepting those associated with the gem-dimethyl groups (Table 1, 5~7). molecule contains 2 polar group they are sometimes unusua cases the strongest in the spectrum. However, when the strong, in certain [1] R.N, Jones and ALR. H. Cole, f Am. Chem, Soc. 74, 5648 (1952); R.N.Jones, A. LHL. Cole and B. Nolin, ibid, p. 3662. 22» Table 1 AtkanesTABLE 2 ALKENES CH streching frequencies (2* in parentheses) 4) CH 3080, m (34) | Yay CH [2975 m | ws CH, “2 -CH- 2 i (cH, m7 Bands higher than 3000 suggest presence of unsaturan Ikenes, aromatics). nd overlaps with alkane absorption. | Overtone of Ty SCH west é ofeplane) | Figs mo [cae | Bc wets | Pen 3) R-CH-CH. 18601800 | 1685, m (40) | 120, | 980.2 50), and 210» (110); m'(10~20) | vibration of three > | Sten teplon | Fiton of nen-cenal | | sete 11 moving im opponts | | 1300, maw | : DR 1800~1750 1653, m (35) 1415, | 890, = (100~150) lae oot m (30) | | 00~20) Phe two H's vibrate in | | Same region| epporite diesetion. (term. methylene) | | scin'Table', a “ tere i 3 R. R’ 1660, am (10) | 1415, 730-65 m (40), butambi- | @.@ So-edg m (10~20) | ““guous in. certain cases. Tey compound several bands of equal (i) intensity (e" 50~ 100) are found in 00~650, but | ssslznment is not clear. | : ® ® H 7675, w (2) 965, s (100) wo'<_ vibente ath ection. 7 R Re 1670, w=m 840-900, = (40), eyelic Sack 2,2 [08 R: H parrof bands at 850~ (tri-substd,) 0, 8 \7670, | [No out-ef-plane bending eae Ips (ef aeent, Bue ‘ ay it bon ced | >e-6-CH: may be (cerra-substd, bere | daa rental | | reiabent yeh Conjugated double bonds Group 2e-C | 4 CH (out-of-plane) Figs. 9) Diene 1650 and 1600 Position not affected much by conjugation. |@ ‘The trans 965 band ss sometimes shifted 10.990. ‘The cit band is usually found at | | 720, occasionally as a group of bands. | 1) ‘Triene: 1630 and 1600; sometimes only | trans-cis-trans and ejstvans-trans systems @ ‘ane band; sometimes addi- tional shoulder on 1650 band, 11) Patyene | Broad bond at 1650~ 1580. a4 - Table 2 Athens have bands at 990's, 960 m, and 720. 990~970 if sras-double band presentABSORPTION OF ALKENES ‘As described already, unsaturated compounds can be detected by virtue of the bands higher than 3000 cm”! if they are not hidden by the stronger main band below 3000 cm-1, It is advantageous to use calcuim fluoride or lithium fluoride prisms or grating instruments. Presence of the double bond is further checked by looking for the C-€ stretching frequency in the 1650cm~ region, and the mode of substitution is identified by the C-H out-of-plane bending bands. Overtones and C-H in-plane bending bands also may be of assistance. ‘The tetrasubstituted double bond usually cannot be detected unless an oxygen or nitrogen atom is directly attached to it. It is advisable to check the original assignments of the characteristic frequencies of alkenes by chemical reactions. For example, if a compound having the isopropenyl group is reduced, its characteristic frequencies should disappear and instead, characteristic frequencies of the isopropyl group should appear; this would provide strong support CH, CH, Nc. \ — .CH- cH,” cH : for the preliminary assumption. Ultraviolet spectra undoubtedly are more suited for dealing with conjugated systems. The 990~970 cm” band arising from the trans double bond in conjugated systems, however, is quite strong and is useful for its detec- tion. Table 2 Alkenes - 25TABLE 3. AROMATICS Phenyls (naphthalenes, phenanthrene etc., are similar) Position Intensity, Remarks 1) ~3030, several | less than 60 | ¥CH and | With NaCl prisms, the bands frequent--@.@ | ‘combination | ly app sa weak shoulder on | the main »CH sliph. band. In cer- | tain arom. compounds, the main absorption appears below 3000 em=* 2) 2000~1660,1 | w, ~5 ‘Gvertone of | Group of 2 to 6 bands characteristic |}@.@ Several bands SCH (out-of- | of substitution pattern ; identified by (Fig. 2. 1) plane) and | comparison with standard curves, combination | e.g. alkylbenzenes. Hidden by strong bands due to C-O, ec. Sample concentration should be more than ten times that of normal. 3) 1600, (1580), | em variable but usu- | Phenyl Variable intensity, 1500 u 1500, (1450) ally less than 100. ‘nucleus er than 1600. In principle, 1380 ‘The 1600 ern"! band bband only appears when phens? is, sometinies stoner conjugated ‘with unsatd. groups oF than CC band. groups having lone pair electrons Conj. intensifies all 3 peaks but posi | tions nok affected. 1430 cm“! peak verlaps with CH, band. Condensed | Systeme absorb. at 1630~1600 (1600), 1525 —1850 (tuo) ens ps | dines similar to phenyl group. In-plane bending (1225~950 cm-! region) One to several absorptions appear according to the number of hydrogen atoms on phenyl group ; weak but sharp. However, polar substituents may intensify them considerably. In-plane bands have only supplementary significance because C-C, ~C-O and other single bonds absorb in the same region. They are not affected much by conjugation. \ 4) e214, DD 1275 ~1175, 1175 ~ 1425 (only with 1:2:4-substitution), | B,@ T070~ 1000 (two} | 8) Wy Usd 1223, 12325 | 8175—~1125, 1110~ 1070 (absent with 1: 3: S~substitution). | 1070~ 1000 6) 122, 1000~960 { Out-of-plane bending (below 900 cm™) They are usually the strongest band below 900cm-. They can be con- veniently divided according to the number of adjacent hydrogen atoms on the phenyl group. Results shown in the following Table also hold for condensed systems'*) and pyridines, In pyridines, quinolines, etc., the hetero-atom is treated as a ring substituent. Electron-attracting groups such as NO, increase the wave-number to the extent of 30m", Very intense (* 100~500) ; bands due to isolated H (900~860em~) are weaker than others, and the positions also may be shifted down to 300.em~ (cf. 1, 3, S-substituted phenyl, Fig. 2. 1). 26 - Table 3 Aromatics7) Five adjacent H| 770~730 | | (710~690) | Appears also in 1:3-, 1:3: 5-, ia iieiced ce (“henyls: assignment is unknown since theoretically only | ‘one out-of-plane bending band is expected. } §) Four 5, | 70~735 1@e 9%) Three ., ., | 310~730 \@ 10) Two 4. | 860~800- | Frequently appears at $20~800 emo, aa 11) Isolated H | 900~8#0 | May be shifted to ea, 800 em” |oo References : 1 no-20° j — aoe 5 (1] CW. Young, R.B. DuVall and N. Wright, Amat. Chem. 23, 2 709 (1932) [2] M.P, Gronewege, Spectrochim, Acta Proc. of Coli, Spectro~ sit scop. International VI, p. 579 (1957), p. 163, [3] HL. Shindo, “IR Spectra,” Vol. 3, p.163 (1958) ABSORPTION OF AROMATICS “The presence of an aromatic group is shown by the 3030 and 1600~1500em~? bands, and substitution pattern is identified by strong absorption below 900 em". ‘The overtone and combination tone bands at 2000~ 1600 cm- are also employed sometimes. 1225~950em- bands are of secondary importance. ‘The strong CH out- of-plane bending bands and the 5~6 « pattern associated with various types of benzene substitution are shown in Fig. 2. 1. a10~130 9) ria ~690.5 re 49810 a 78-10 123 W515 | a . ae eee ~nid eal 730-278 25-105 : Lad B85 —879 12a4- 10-800 N\d Sa \/ 1248+ 1235+ 50-0 re sn a0 ow 20 16a? Fig. 2-1, Shape of 5~6c band (redrawn from rel. 1) and ous-ofsplane bending band. Table 3 Aromaties - 27TABLE 4 X Y, z Groups The strong absorptions at 2300~2000 cm-tand the weak absorptions at ca. 1350cm~! of the cumulenes are due to XYZ antisymmetric stretching and symmetric stretching, respectively. roup | Remarks 1) Acetylene, terminal position H appears sharply at 3300 | 2140~2100 emt e100, 2C-H also shows bend ing at700~ 600, | and occasionally its over- | | | tone at 1300~1200 em", || central: — 2260~2190 1 | Completely absent when symmetry i high, 2260~2210 “The lower wave-number te- | ion indicated is observed when conjugated to other unsatd. groups or when contained in cyanamide | (N-CN) group, | 3) Diaeoniurs salt, 2260.20 [i 4) Diazoketone, {5,6 -CO-CHN, 3100~2090 2O=O appease 16451630 -CO-CRN, | 2070~2060 meee oe eee | | = : pt 5) Allene, C=C=C 1950 Split when at terminal posi- ie at oe ee | trop-attracting groups.c.8 | , COR. | 850 (terminal allene Stronger than 1950 cit | only, # CH) ‘Overtone also at 1700.6"! ‘but unpraetical. | 6) Isocyanate, 22752250 1300~2000 | Extremely strong, position |8,9'g) eS erated Brean | 1350 No practical value becouse | | | “ottweak intensity and over- || lapping with Cl, peak. | aliphatic: 2140~2130 | 1340~1580 | Extremely hich intensity, | 10 @ stranger than carbonyl (2 | 600). past aromatic: 2145 138001680 | Values of 3} measurements. | | 2s 4~ 1560 [iso 8) Azide, Ny 2160-~2120 a 1340~0180 | 9) Thiocrange | {aliohaie: 2140 | Integrated intensity has been 12, ~S-CaN || aromatic: 2175~2160 Stronger | measured. ja3,| Tsothiocyanate, | faliphatie: 2140~1990 | than | Somewhat broad, frequent- | SN=C28 | Laromatic : 2130—2080 | Oevanates |TV" solic “or accompanies shoulders. Other bands: | | aliph. 1090(s); arorn, 1280 | (Gu) and 930 ems (2.121 | | \ 28 - Table 4 XzV, X=Vaz| for calibration of spectro | photometer. Group [Bane Cem 10) Kerene, C0 | ~ 2150 | =1120 | 11) Ketenimine, | ~2000 | li oa a [| 12) Carbon dioxide 2349.3 | Strong, antisym. stretching, 0 fine structure, | | 720.3 | | 67.3 Fine structure, all thee used | References [1] R.A. Nyquist and W. J. Potts, Spectrochim. Acta 16, 419 (1960). [2] RLE. Kitson and N. E. Grifith, Anal. Chem. 24, 334 (1952); M. W. Skinner and H.W. ‘Thompson, J: Chen. Soc. 87 (1955); D. G. I. Felton and 8. F.D. Orr, ibid. 2170 (19 Sensi and G. G. Gallo, Gazz, chim. itat. 85, 224, 235 (1955). [3] 1-P. Jesson and H.W. Thompson, Spectrochim. Aeta 13, 217 (1958). Aroney, Le Fevere and Werner J. Chem, Soc. 276 (1953): Whetsel, Hawkins and Johnson, J. Am. Cherm, Soc. 87, 3360 (1956). [5] P. Yates, B. L. Shapiro, N. Yoda and J. Fugger, J. Aun. Chen. Soe. 79, 9756 (1987). [6] E. Fahr, Ann, 617, 11 (1958), [7] J. H. Wotiz and D. E. Mancuso, J. Org. Chem. 22, 207 (1957). [8] H. Hoyer, Ber. 89, 2677 (1956). [9] G, L, Caldow and H, W, Thompson, Spectrochim. Acta 13, 212 (1958), [10] G. D. Meakins and R. J. Moss, J. Chem. Soc. 993 (1957). [11] L. J. Bellamy, “Infrared Spectes of Complex Molecules,” p. 263, Methuen, London (1958). [12] of E, Lieber, C.N.R. Rao and J. Ramachandran, Spectrochim. Acta 13, 296 (1959). [13] N.S. Ham and J. B. Willis, Spectrochim. Acta¥®, 279, 393 (1960). [14] PB. B. Butler, D. R. Eaton and H.W. Thomeon, Spectecehim. Acta 13, 223 (1958). [15] C.L, Stevens and J. ©, French, J. Ant, Chem, Soe, 75, 657 (1953). [16] CG. L. Stevens and R. J. Gasser, rid. 79, 6057 (1957), THE 2200cm™ REGION Absorptions appearing in this region originate from groups of the type X=Y, X-¥-Z. Although interpretations are easy since no other groups absorb strongly in this region, due consideration should be given to the fact that carbon dioxide absorbs strongly at 2350.cm~1. ‘Thus, the carbon dioxide peak is seen in all infrared spectra measured with single beam instruments; it also appears as small troughs or peaks when measured with double beam instruments in which the sample and reference light paths are not correctly compensated. Furthermore, peaks of nitrile and other groups may become smeared or blanked out under high carbon dioxide concentration. In order to avoid this, the room should be well-ventilated or a carbon dioxide absorbant should be placed within the instrument With terminal acetylenic groups =C-H, the »CH band appears sharply at a characteristic position and the «C=C band is also present. Central C=C bonds, on the other hand, will not appear if the symmetry is good, and thus, absence of the stretching hand will not necessarily mean absence of the group. Although “immonium bands" (2200~1800 cm~!, ‘Table 7d) also appear in this region, they are always accompanied by broad “ ammonium bands” (2500~2300 em") and therefore can be distinguished from cumulene bonds. Table 4 XSY,X=YV=uZz-TABLE 5 ALCOHOLS AND PHENOLS. Table 5a O-H Stretching vibration State of OH | Shape | Remarks Free (monometric) | 36403610 | 30~100 | sharp | Data measured in so-called mon- eee ee | polar (CCl, CHCIy, ete.*) dilute pon aoa | 70 olations g er Water absorption at 3710em" when » OH 3630 60~ 30 nk is damp. j OH 620 45 phenolic OH 3610 Intermol. H-bond ‘aay hidden in polymeric band me fe infra) unless polymer Form- 2) dimeric 3600~3500 cee ation is hindered by steric bind- ance. Absorptions arising ftom H-bond with polar solvents such as ethers, ketones, and amines also appear in this region, | e 3) polymeric $400~3200 | strong | broad | With solids and liquids, this broad | @.@ absorption 3 the only one ob- served; in dilute solutions, ac- | companied by monomer band, Free. and into NEL GF mines ‘and amides slso appear at 3300~ | Sg cats REY grees or uC-O (6a, 1720cm“) also ape pears at 3300~3400em~*, but can | i be differentiated because of low intensity, et<10. Water of crystallization: also at 3600~3100 em", but not so strong and somewhat narrowe: also weak band at 1640~1615 em"! (H-O-H bending vibra- tion), ® Intramol. H-bond 4) Pores ‘alcohols | 360 ~3500 | $0~100 | sharper | eS T,2-diels) shan dimerie band 5) = H-bond 3600 ~3300 ‘Many data since 19571~11, 6) chelation (intramol. | 3200~2500 broad | Lower the freq., stronger the in- | bond with C-O, cramolecular H-bond. May be | + 616.) | overlooked even when not over= | i @ } | lapping with »CH, because oc- | | casionally broa | | | may appear as and weak, and /-separated band | | | aroups. * Intensity of free -OH underwent temperature variation when methanol was measured in CCI, under dilute conditions in which no intermolecular H-bond was present. This was regarded as being due to the presence of a weak H-bond between the OH and the solvent C-Cl, and it was inferred that even CCI is not an “inert solvent: U. Liddel, nn. N. ¥. Acad. Sei. 69, 70(1957). 30 - Table § Alcohols and PhenolsTable $b C-O Stretching vibration® Standard position te. a=200) | Shift p-OH | a-branching: -15 em" OH a-unsaturation : -30 em"! Pea Bel ‘OH ring formation between a, a’: =S0em-* further than 3- |.® unsaturation and a’-branching : -90 em-t | Pesition has. ne Se sab erates ase ¢ Seaeae ifect. Additional ee and @’-unsaturations: -0.cm™ af and @” branches also lowers by 15 1 3 * Deduced empirically from ref. §, standard cards, and other data. Relation between C-O peak posi tion and various factors affecting the position is quite variable. ‘The Table has been made only to give a rough guide to approximate positions. ae, a=, and a”-unsaturations : ~140.cm™* phenolic OH: 1200em~ Table 5c O-H Bending vibration (no practical value) | Free OH | Associates OH | Figs. 1500~ 1300, broad, frequently two, m. Shifted tw higher |@ frequencies with stronger H-bond. ineplane | 1250 cm", m Soeaiplase | (~228em-1? | 650, broad, m. Higher frequencies with stronger H-bonds. References : [1] A.W. Baker and A. T. Shulgin, J. dm. Chem. Soe. 80, 5358 (1938), {2] 1. M. Goldman and R. ©. Crisler, J. Org. Cliens, 23, 751 (1958). {3] D.‘T. Trifan, J. L. Weinmann and L. P. Kuhn, J. Am. Chem. Soc. 79, 6566 (1957). a [4]. P. von R. Schleyer, D. $. Trifan and R. Bacsissi, J. Am. Chem. See. 80, 6691 (1958) [5] West, J. Arm, Chem. Soc. $1, 1616 (1959), [6] P. von R. Schleyer, G. Winter, D. S. Trifan and R. Bacskai, Tetrahedron Letters No, 14, 1 (1959). (7] M. Oki and H. Iwamura, Bull. Chem, Soe. Japan 34, 1595 (1961), and previous papers. [8] HH. Zeiss and M. Tsutsui, J. Ain. Chem, Soc. 75, 897 (1953). [9] A.V. Sard and G. B. B. M. Sutheriand, J. Chem. Phys. 24, 559 (1956). a Table 5 Alcohols and Phenols - 31ABSORPTIONS OF HYDROXYL GROUPS The hydroxy! absorptions were the subject of early IR inve and have been measured since the end of the 19th century. All of the characteristic frequencies are intimately related with hydrogen-bond formation. Usually the most important is the LOH band in the 3300 cm-! region, the position of which is subtly affected by concentration, state of measurement, and temperature. Furthermore, measurements in the 3000cm-! region of all prism instruments are quite sensitive to temperature vati- ation, and accordingly, the wavelength should be accurately calibrated for rigorous discussions. It is also advisable to use LiF or CaF , prisms or grating instruments for better resolution. Because the ~3600cm-* band of the free hydroxyl is sharp and appears at a position well-separated from other absorptions®, it is effective for the identi- fication of hydroxyl groups; moreover, accurate measurements (comparison with models) may identify the type of hydroxyl group and give information on its conforma- tion. ‘The intermolecular hydrogen-bond peak is intensified with increase in coneentra- tion, but the intramolecular hydrogen-bond is unaffected by concentration. The same relation holds for partners of the hydrogen-bonds, e.g. C-O, NO,. For instance, i 1, 2-diols, the intensity ratio of the free OH and the intramolecularly bonded OH is constant under low concentrations in which no hydrogen-bond occurs (usually CCl, solutions of concentrations less than 0.005 mole per liter). When the concentration is increased, only the free OH band is weakened, and is replaced by a band arising from intermolecular hydrogen-bonds at 3500em-! or lower, i., at frequencies lower than the intramolecular hydrogen-bond peak (3600~3500 cm-). The -OH band simply appears as a monomeric or dimeric band if association of the hydroxyl group is sterically prevented or hindered. This can be observed in the following data of hindered phenols measured in nujol: 2--butyl-+-methylphenol: 3380.cm-» (API 924) 2-methyl-4, 6-di-tbutylphenol: 3570.cm-' (shoulder at 3462 cm-*) (API 928) 2, 6-di-t-butyl-4methylphenol: 3510 em™} (API 926) 2, 6-di-t-butyl-4-ethylphenol: 3570 em-? (API 927) 2, 6-di-t-butyl--cyelohexylphenol: 3530 cm~! (API 928) The »C-O band is stronger than the -OH band, but it should be kept in mind that other absorptions also appear in the 1200~1000 cm"! region, Furthermore, the -OH band also appears with moist samples, or samples containing water of crystallization or alcohol. Presence of the hydroxyl group can be ascertained if upon acetylation, the OH band disappears and is replaced by acetate bands; disappearance of the alcoholic C—O band cannot be used as a diagnosis for ester formation, because acetoxyl groups also have two absorptions at 1300~ 1050 em~? besides the 1735 em-1+C-O band. Phenols'! naturally give rise to aromatic absorptions in addition to the above-mentioned hydroxyl absorption, Bending vibrations given in Table 5c are only of complementary signi fiance and have no practical value with complex molecules. * Overtones of carbonyl peaks may also appear in the O-H stretching region. Thus, the avertone of & 1715 cm~4 C=O band may be present as a medium intensity broad band at ea, 3430 cm", [1] IR of alkyl phenols: D. D. Shrewsbury, Spectrochim. Acta, 16, 1294 (1960). 32- Table 3 Alcohols and PhenalsTABLE 6 ETHERS AND RELATED GROUPS : s of »C-O bands are usually greater than 200. Band (sm=") Remarks | Figs. Group 1) Ethers, | aliph. and ring | 1150~1070 | C-O-C antisym. steetching. Common with other | @ general | C-O-Citl C-O bands. Effeet af a-branehing unclear. arom.and vingl | 1273~1200” | Antisym. sttiching. Common with other -C-0. 39-4 caries ‘So-called “1280 em band”. uC-C of vinyl ethers intensified. 1073~1020_| Sym. stretching. Weaker than 1230 cm“ band. | | Methoxy! group has following bands in addition. ian Zinn | Cy wm. mecching, Ung OGH, The] ) -ocre! (e250) asym. stretching is at 2990-2970 (present in | | a | “OG.H1)y but position i non-ehanterstc. | | arom. a) CH, sym. stretching. Following bands also | @ | cecaiad ‘resent, but position non-characteristic: 3000. 2950, 2515 (the 3 appear as triplets), 1460 and 1340 G Cit), 1250 (-C-O-C antisym, stretch ing), 1180 ‘and 1125 (methyl rocking and arom. ?),1080~1020(«C-O-Csym. stretching 2) Methylenedioxy(3) 2780 CH, som. stretching. 1@ °. 925 Most useful, probably related to C-O stretching. af 720 Frequently 28 shoulder on other strong bands. | ce Following peaks also observed: 3010, 2950, 0. 2910 (other »CH), 1480 (@CH,), 7400 and 1360 (sometimes lacking), 1250" (-C-O-C, sometimes branched), 1130 (sometimes lack- ing), 1040 (=C-O-C). 3) Ketals, acetals 1200~1040_ | Group of + to 5 bands. C0-C-0-ci eyelic €0-€-0-681 49) Spiroketal of steroidal 1350~ 650 | Many characteristic sharp bands, ‘sapogenins(! 3) Epoxy [Sere {t.r91] 3000 (e# 40) | Epoxy methine group of chain compounds and | @ Soe Derainless tings. 3040 (07 20) | Epoxy methine group of strained rings. 3030 (c? 30) | Methylene group of terminal epoxy rings. 1250 | So-called "8 y band "5 950~ 810 | So-called “11 y band sym. stretching of ring. asym. stretching of ring. HO~ 750 | So-called “12 yx band”. | Steroidal 900~ $00 | Either band appears according ta position of epoxyll0l oF, ‘epoxy fing. Above-mentioned 1250 cm! 1000~1035 | band was abseni 6) Peroxidesttt) €-0-0-C, aliph, | 990~820 | Both weak and difficult to detect. arom, 1000 | ~O-O-H at 3450 em~*. Aliph. -CO-O-0-CO- at 1820~1810 and 1800~1780 em (2 bands), | and arom, ~CO-O-O-CO= at 1805~1780 and 1785~1755 em"! (two bands). 7) Ozonidesttit 1060~ 1040 ‘36 - Table 6 Ethers, etc,References [11]. Review of natural products containing these bonds: A. Fujino and M. Yamaguchi, “TR Spectra,”” Vol. 3, p. 101 (1958). [2] HB, Henbest, G.D, Meakins, B, Nicholls and A. A. Wagland, J. Chem, Soc. 1462 (1957). [3] L.H, Briggs, L. D. Colebrook, H. M. Fales and W. C, Widman, Anal. Chem, 29, 904 (1937). [4] B.D. Bergmann and S. Pinchas, Rev. trae. cline. 71, 161 (1952). [3] H.Tschamler and R. Leutner, Monatsh, 83, 1502 (1952), [6] R.N. Jones, E. Katzenellenbogen and K. Dobriner, J. dm. Chim. Soe. 75, 158 (1953). C.R. Eddy, M. E, Wall and M. K. Seott. Anal. Chem. 28, 266 (1953). [7] J. Bomstein, Anat, Chem, 30, S44 (1958), [8] HB. Henbest, G. D. Meakins, B. Nicholls and K. J. Taylor, J. Chem. Soc. 1459 (1957). [9] W. A. Patterson, Aual. Chen. 26, 823 (1954). [10] Hs, H, Gtinthard, H. Heasser and A, Part, Hele. 36, 1900 (1953), [11] L. J. Bellamy, “ Infra-red Spectra of Complex Molecules," Methuen, London, (1958). ABSORPTION OF ETHERS ‘The mass of the oxygen atom and the strength of C-O bonds do not differ much from those of the carbon atom, and hence the positions of ether absorptions are not characteristic. However, the intensities are large because the change in dipole mo- ment accompanying C-O vibrations is larger than that of C-C, Identification of ether groups from the infrared is not easy because organic compounds frequently contain other C-O bonds, e.g., alcohols, esters, acids. In summary, a peak at =1100cm™ or = 1250 cm™ only infers the presence of a C-O bond or a =C-O bond, respectively. Band intensities are usually strong with an ¢* larger than 200, but quantitative measure- ments have not been carried out, Of the two ethereal C-O-C symmetrical and anti- symmetrical stretching vibrations, only the latter is infrared active. Table 6 Ethers, ete. - 37TABLE 7 AMINES AND AMMONIUM SALTS Table 7a Stretching vibrations Amino group sm Intensity Remarks | Pigs Free | | : Amine R-NHe and ArH, [Phe two correspond to vs and 3, |B, B #~30 in ANH, | _ tesp, : wave wumber relation: 2.5 345.532 0.876 salt. 2) wAmine RENH-R | 3350~3310 7 Especially weak in Neheterocyctic | compounds, eis piperidine, | | | | Acne | aso | at s0~ 40 Pyrrotes, indotes,| 1690 | 4 150~300 | Position and intensity both charac | ete.) | teristic. See Table 10-2, cexn | 3400~3300 bC=N band at 1690~1640 em Association: ‘The shift from the free position is less than 100cm7}, and is generally smaller than the case of hydroxyl groups, but a shift down to 3100 em™ i sometimes observed. Hydrogen-bonding, change of dielectric constants and/or inter- action between adjacent molecules in. solids, liquids, and concentrated solutions are responsible for the shifts. ‘The position of the lower frequency band is fairly constant when the hydroxyl group is participating in hydrogen-bonding, and the intensity also in- ereases with concentration; when it is not involved in hydrogen-bonds, its position is continuously shifted towards lower wave-numbers with increasing concentration, Table 7b N-H Bending vibrations (lacking in f-amines) Bs. Gan [one | laveny | Remarks | e 3) C=NH* group can be easily identified because in addition to the sNH* band of the tertiary amine type, an “immonium band ” appears at =2000 cm (tertiary amine salts lack the = 2000em-1 absorption). ‘The fact that the C=N absorption is shifted to higher frequencies upon salt formation is also of practical importance (Table 74~12), Substituted guanidines can be detected by the guanidinium bands of their hydrochlorides. ‘The 2800~2700 cm-! bands shown in Table 7e are characteristic for the N- methyl group but they are somewhat confusing because transq other groups (‘Table 7e) also absorb in this area. Quaternary ammonium compounds lack characteristic frequencies. It has been jnoted that carbon disulfide is unsuited as a solvent for amines because of the rapid reac- tion with primary and secondary amines to give alkyldithiocarbamates (R. N. Jones and C, Sandorfy, * Chemical Applications of Spectroscopy,” p. 511, 1956). lizidine rings and Table 7 Amines, ete. = 41TABLE 8 CARBONYL GROUPS (Bold figures denote »C-O) The standard uC-O position (of saturated aliphatic compounds) and other characteristic frequencies are given first, and these are followed: by conjugated unsaturated groups and others, Unless otherwise stated, the values the »C=O of refer to dilute solutions in non-polar solvents such as CCI, and CS., Deviations from given value are usually within £10cm~. When intramolecular hydrogen-bonds are formed, bands may be shifted lower by 50cm~ according to H-bond strength. Group Band (em) Remarks | Firs, 1 Ketone iis & 300~600, Values of CHCIs solutions |B “CO- and solids, lower by 19~20 em", Values 1b) Ar-CO- Le) Ar€O-Ar 1 BCO-R 1k) achalo- 1m) -CO-co- I 42.- Table 8 Carbony! groups 1a) a, f-unsatd. 16) ay f-7, d-unsatd, 1d) a,6-o/,#/-unsatd 1g) 7memb. and larger 1h) 6-membered 1 i) Ssmembered 1 j) 4-membered 1690, 1665 1695 1705 wis 174s 1780 shift of O~ 425 | suteor ns 1720 of gares, +20 em™\. Occasionally over- | tone at ca. 3400 em"*, ' = 30-150. Caused by C-C-C bending | and C-C stretching af -C-(CO}-C~ | CAC shows clearly at 1650~1600 em"; in s-cis forms, may be shifted below , 1600 cm-" and intensity becomes com- parable to that of » C-O. | Affected by [, M, and sterie effects of substituents. Conj. em ith eyclopropane lowers by ca, 20 Same as standard valus. Shift caused by conj. with unsatd. groups is same wit aliph. ketones. caused by conj.with unsatd. groups is same with aliph. ketones. Shift to higher freq. is larger the smaller the angle between CxO and C-X. No shift when angle exceeds 90°," Follow- ing values apply to satd. aliph. and | eyelie ketones: | One 25; ~Br. Ow +20: O~ +10 cm-* Effect of single halogen substitution ap- pears additively. Shift of #45 em™ results when Cl on both sides of C=O are in same plane with €-O, Co-exist- ence of several conformers give rise 10 each corresp. band, the relative intensi- ties of which are dependent upon state of measurement. (Caused by antisym. stretching of the two ‘C20 (a); sym. stretching is 1Reinactive. When C0 groupsare fixed in secis form {b), 26-0 fs at 1760 and 1730 em! in 6 membered rings, and 1775 and’ 1760, em" in 5 membered rings oe orto fa) (b) seisRemarks Figs 2 CrC at 1630 em, strong. | on 10) -Co-cH-Co- =1720 Occasionally doublet. | tL 1p) -C-C-Co- 1650 (free) GH (or NEA) 1615 (when intra. | »C=C appears at 1605 em™* with same | mol, T-bonded) | intensity'as 9 C- 14) -C-C-co 1640 OR 1 #) ortho-CO-C,H OH 1630 Influenced by J, M, and steric effects of | @ | or NH ‘substieuene. z |1 3) 1, 4-quinone 1675 Affected by M effect of substituent. Ske- | @ bidaien} | Meets C2 acca 1600'cm=" When | peri-OH is present, strong band is Shown at 1630cm-!, and 1675 em™ bband becomes much weaker. 10) extended quinone 1645 1 u) ropone 1650 1600 cm! in. intramolecularly H-bonded tropolones. 2 Aldehyde 2820, 2720 | » CH of CHO, and overtone or eombina- | “GHD tion tone, 17s Several bands also at #400~1000cm"), ‘but not practical. \ . 2a) @, P-unattd. 1685 2b) a,f-7.d-unsatd. 1675 [26 arcHo 1700. aa a| ‘Acid Data are mostly for dimers because | @,@ ‘bonding power is unusually strong, 2nd -COOH they exist also in gas state. 3000~ 2500 Very characteristic. Group of small bands. 3a) C+C-COOH and Ar-COOIH 3b) arhalo~ 1760 (monomer) 1710 (dienes) 420 1300~1200 1720 (monomer) 1690 (dimer) Shift of $10~20.em! Band at highest freq. 1s due to » OH, and others axe combinations. 3550 cm | in monomers. jepasis stronger than ketonie +C=O. | ev up to 1500. ‘Two bands may be ob- served with gases or solutions. O-H bending and C-O stretching of |e due to coupling between in-plane dimer. ee OR GP | | Broad, medium intensity. Q-H out-of plane bending of dimer. Values for a-Br and a-Cl. Larger for | a-F, ca, +50 em. | Table $ Carbony? groups @ -43Group Band (em) | Remarks + Carboxytate 1610~1550 and~ | C-O antisym, and sym. stretching, resp... -CO0- 1400 « Z of ce ‘When an acid is converted into its inor= ganic salt, the five characteristic req. are replaced by these two. Instead of Being | converted to inargani¢ salts, they ean Figs. &, be changed to ammonium saits by add: | © ing few drops of EtN to CHCl, solu- ton; cusbomlate itt are nct formed in CCI, while sdalzion of NH, orp-amines | sve! confusing NH, and N*fi, bands | that overlap with -COO- band. 173s Intensity intestuediary between ketone | @, ‘nd carboxyl, (e300 ~ 1000) jee | wo at 1300~1050 | Asym. and sym. stretching, resp..of ester | ] C-O-6. “The asym. stretching (* ester | i usually steonger thin.» =O | {ale oceationally split. This Haher > 0-0 ‘band! icy constant according to type of exter: H-CO-OR, Tagen é | 1240 em @ | 190 em" | R-CO-OCH,, 1165 em" 6 $3) ~C-C-C0-0- 320 ‘Shift couped by conjognted vossruration | relatively small.» C-O at 13001250 | (Gs) and'1200~i080.em~ (6). 5b) Ar-CO-0- 4720 Cat £300~1280 (vs) and 1180~1100 | @ 5 6) -CO-0-C=C- 1760 » CoC at 1690~1650 (8) (may shife up to | @ 3715 em"I0, In CH,-CO-O-C-C Grol and phinol acstatea), one of the vG-O appears at 1210 cm"! (wo). 5d) achalo- shift of Shife dependent on electronegativity and $10~+40cm- | number of avhalo atoms; dependent flvo on angle between C-X and C-O as ‘with ketones. $6) ArCO-O-Ar 173s 5.1) eckero exter a5 5g) Beketo exter keto: 1735 | The f-keto group (VC-0, 1750em") | @ Goes not affect exter » C ensl: 1650 | Broad C-€ at ea. 1630 em (vs). 0 sm Co 1735 Same as with aliph. esters. 0 so 0 1720 Same 28 with aliph. esters. j 0 Isa ° 1760 Same as with aliph. eaters. 2C+C at 1685 re ang sy & 0 Table 10-4 | @-Pyrones, See Table 10-5 for y-pyrones. | @ sof yo | om i 44 - Table 8 Carbonyl groupeBand (cm7!) ea) ce Acid anhydride =CO-0-CO 1750 when a-H is present: 1785 and 1755 (doublet) 1770 1880 1820 and 1760 1300~1050 In non-polar solvents (CCl, CS;1, the higher band is stronger, while in polar solvents (CHCl,, CH,CN, CH,OH) or Liquids and solids, the lower band is strongeri. yC=C is weak. Around 1780 in non-polar solvents, and | @ ‘ca. 1760in polar ealvente; affected by polarity of solvents, Influenced by MT and other effects of substituent’ on arom. ring. ‘The band is not split, contrary toa, Unsatd.-y-lnetones. | C=C at 1660 em? (6. Relative intensity of two bands variable. | & Band separation usually ca, 60 .em™", but this may difer from 38 to 90 cme! according to typed; lower band absorbs near sC+O of corresp. ester OF lactone, "Htnber. ‘and lower, band, resp., i stronger in acyclic and cyclic aniydridesttl a 122 strong bands arising from, C-O-C portion. Acid halide satd. 1800 ® : Vas ana 1725 6b) 6-membered 1800 and 1750 ACO, 80-70 em=* 131. 6 ¢) @, Pruncaid, 1780 and 1738 | 4C=O, 45 em when double bond isendo | @ ‘6-membered (75 cm=t when exo). 6d) S-membered 4868 and 1785 | 4C-O, 80 emo™1, ® 6 e} maleic 1850 and 1790 4C«0, 60 em™. 1790 cm band is split i God behaves similary to 5 mb 6 6) phihalic | 1850 ana 1770 | 1770em-* band is split and behaves simi- | gp | wil Tardy to 5 mi Peroxide l ~C0-0-0-6O alkyl 1815 and 1790 argt 1990 and 170 | | = | Value for-COCI, small band also at 1750~ | gj 1700 exn' 1690 1650 ~CO-X tensat © 1780~ 1750 ee cher, | | COBY and COT, lower. | Carbonate satd.: 1750 Absarptions also at 1250 5) and 10900 (vr) l@ | ~0-CO-0- unsatd.: 1770 | Absorptions also at 1250 (s) and 1160 (m) | 9 Amide Free | Assoc. | Complicated but extensively studied. In- } fluenced by state of measurement as | -CO-N with -COOH, Data for both free and | | tssoe, states are given. | | primary Jrweo at: leeveral: | anit \® -CONH; 3500, 3400 3050 ~3200 | #C-0, “Amide 1 band.” Table 8 Carbonyl groups - 45Remarks Fig Band (crv toe | tet ants aH, “Amie L band" Shifted | iaher upon association. Solid spectra | af ~CORT, show twe strong bands at 1650~ 1640: but “I band "is stronger. | | Th concentrated solutions, all four bands | | arising from free and sosoc, states may | eyestt secondary 340 | 3900. | uNHH, 3300 cmt band considered to be is : 79, | duc to trans assoc. form (structure 1 in sae 5070, | ‘Beare shown). Origin of 3070 cm" Bind unkown Tnvoyelic lactams, 3440 when free, and | 3I73 (dimeric, stnucture 11) and’3070 | emt when assoe. (3300 lacking). 1680 | 1685 | Amide I band” 1530 1330. Mainly 6NH, mixed with vC-N, “Amide | TI band.”"” As with primary amides, | tually Amide band baonges 1260 1300, Mainly »C-N, mixed with NH, “Amide itt bana | Shift in positions of free and assoc. yNH and“ Amide T~TIT bands” is consis- tent with assignment. ‘Thus contribu- tion of limiting structure Ib is enhanced. upon association. Deanne (a) «Ib) dimeric lactam (IT) Solid IR of amides are, however, especi ally sensitive to crystal orientation. | Effect of substituents may thus not be | exerted correctly, and a slight complica- tion in structure may prevent the shife of “1” and IE" Bands to lower fre- quencies in the solid state. In concentrated solutions the assoc. and : free absorptions both appear. tertiary 1650 1650 ‘Since H-bonding with NH is absent, posi- tion is only slightly higher in the free CONE state (similar to other C=O groups). | | 9 8) ReCO-N-C+C shift of ea. +15 em" Goeraw Gono aa ae pirelectrons both C=C and C=O. 9b) C-C-CO-N shift of ca.+15 emo!) Extent of resonance within amide group | ce ees | C=C operates (7), The state of C-O becomes simi ® 9c) C-C-CO-N-C-€ of ca.— 18 cm’ F to oF- dinary carbonyl groups because N is already in eonj. with C-C; thus +Af effect of the other CC is exerted. | 9 4) -CO-NH-X 1708 (free) |X: halogen: | [9 9) achalo 4+5~-+50 | Depends upon eectroncgatvity and num | | | ber of ashalo atoms; -+-50.¢m™ shift is | observed in CF,CO-N, 46 = Table 8 Carbonyt groupsBand (em!) Remarks Figs 1670 (free) Amide II band is present in 9. mem! lactams." Shifted slightly to higher | freq. when @,6-unsatd, 1640 (free) +20"! when «,f-unsatd, Shifted | hhigher in N-bridged systems. ~1700 (free) ||Shifted higher in N-bridged systems. In general, the steric inhibition of conj. between N and C=O is expected t6 increase 2C=O, ~ 1745 (free) 9 9) cyclic imide 6 membered 1710 and 1700 «, é-unsatd, 1730 and 1670 baa Usually lower band stronger. 5 membered 1770 and 1700 «, feunsatd, 1790 and 1710 ‘S'membered 9k) R-NH-CO-NHR 1660 9 1) cyclic ureide 6 membered 1640 5 membered 1720 9m) urethane 1740~1690 in mono and di-sub- | @ R-0-CO-N 2, et, 1700 em! in non-substituted compounds. “Amide TI band” | Non- and mono-substituted compounds ibsorb, resp., in the “Amide 1 region of p- and s- amides. | 2NH Non- and mono- substituted compounds | absorb in usual NH region. -CO-SHH 1720 | R-CO-SR'5) 1690 et. Chap. 4 “Ar-CO-SRDI 1665 | 7 | R-CO-S-artl) 1710 | ~ Ar-CO-S-A: 1685 ; 1 | Othersis | | References [1] NJ. Leonard and F. H. Owens, J. Amr. Cihem., Soc. 80, 6039 (1958). [2] RN. Jones, CL. Angell, T. Ioand R. J.D. Smith, Can. J. Chom. 37, 2007 (1959). [3] Re G, Cook, Chem. and dnd, 142 (1955) [4] W. G. Dauben and W. J. Potts, Speetreciim, Acta 514 (1959), [5] R.A. Nyquist and W. J. Potts, Spectrochim. Acta 314 (1959), [6] ef. Following reviews for complex C=O compounds ‘Oxygen: A. Fujino and M. Yamaguchi, “IR Spectra,” Vol. 3, p. 101 (1958). fur: M. Yamaguchi, ibid. Vol. 4, p. 85 (1958), Nitrogen: A. Fujino and M. Yamaguchi, ibid. Wal. 6, p. 61 (1958). [7] IR of Me, Ety2- and f-Pry n- and /-Bu esters: A.R, Katriteky, J, M, Lagowski, and J. A. T. Beard, Spectrochin. sleta 16, 984, 964 (1960). Fable & Carbonyl groups - 47ABSORPTION OF CARBONYL COMPOUNDS The C=O stretching vibrations of various carbonyl groups absorb in the region 1900~1600cm-2; a more specific range is defined by the type of carbonyl (e.g., ketanes, esters), and the position is further affected in a subtle manner by a variety of effects (cf. _ Chap. 5 and Table 8). Thus, the absorption will give information on various effects as well as the type of carbonyl group. ‘This is why the region has a tendency to be over emphasized by organic chemists. ‘The type of carbonyl group is identified by taking into account vibrations other than the C=O stretching. Rigorous discussions should be avoided unless the measurement is made in dilute non-polar solvents. It should be noted that chloroform contains ethanol as a stabilizer, and this may conspicuously affect the C=O position by interacting selectively with the solute molecule. In certain cases, valuable information can be obtained by changing the method of sample measurement. 48- Table 8 Carbonyl groupsTABLE 9 NITRO, NITROSO, ete. -NOs P e = = ‘0 ° vas 1650~1500 em? vg 1370~1250 em Group Band Remarks | Figs Nitro a 1) C-NO, 1560 and 1350 | Very sirong, In nitrobenzénesll] (1527 and 148em-? for |G,@ CH,NO, in CHCI,) the vas is affected by J- and M- effects (1550~1515 €m™), whereas > is affected by plan= arity of nitro group and phenyl ring (1385~1345 cm~'). 870 (GUN stretching. In arom. nitro compounds, the out-of | | plane 6CH may be shifted higher and in addition this S70 cm band i present: thus care should be taken in identifying substitution pattem. 610 | CNO bending 2) Nitrate 1640~1620 | Other bands: 870~855 (O-N stretching); 760~755 (out- | | ONO, 1285~1270 of-plane bending) ; 710~695 (NO, bendingyi® | | 3) Niramine 1630~1580 | | N-NO, 1300~1250 -N=0 Nitroso 4) CMO eons ease & Te Seer Moser” group... Acoma nitroso at ca. 1500, taliph, nitroso at oa. 1580 em“ | 5) Nitrite 1680~1610 | vN-O. Two bands, the higher one assigned to tranr and O-N-O (twa) | Tower to ei, resp. In t-nitrites trans form content in- | exaiees, and bene intensity dnenonecs conascquently. 815~ 750 | .O-N 6H~ 620) | O-N-O bending of cis and trans forms, resp. os sua) | eof - 6) Nitrosamine | 1300~1630 | »N-O. Lower than other N-O strething, thus indicating | anes increased contribution of limiting structure, N°«N-O". | -N-o- TD) Oxime 3650~3500 | vOH; value for free OH. Shifted lower by H-bonding. | (C«N-OH | | 1685~1650 | ¥C-! Position influenced by as c-O} |" Gexclopentanone oxene, 1684 ern. 960~ 99012 vN-0. In quinone mona-oximes shifted to 1075~97S | em74i3] because of contribution of ~C-N-O*H. 50 - Table 9. Nitro, Nitroso, ete.Group Bind | Remarks | Figs. 8) N-oxide | sliphtt | “NO 970~980 | N-O stretching, very intense. 8 | arom. (5 | 1500~1200 | N-O stretching, very intense. Higher than aliph, because | of contribution of structure (b). Addition of methanol to organic solvents lowers it by 20- | bind to appear ot ca, 2360 cart; this fs cxplained by ar- sociated form (c) and is useful for oxide identification 9) Azoxy N-N~O | 1310~1250 | N-O stretching, strong, tons (ef. Table 13 for inorganie nitrates) 10) Organic nitrate -NO,- 1410~1340 | NO,” stetching b0- 00,| OD peste) References [1] T. Kinugasa and R. Nakajima, Nippon Kagaku Zasshi 82, 1473 (1961), [2] A. Palm and H. Werbin, Cam. J. Chem. 32, 858 (1954). [3] D. Hadi, J. Chen, Soc. 2725 (1956). {4] RB. Mathis-Noel, R. Wolf and F. Gallis, Compt. rend. 242, 1873 (1956). [S] H. Shindo, Pharm. Bull. 7, 407, 791 (1959). [6] R.A. G, Carrington, Spectrochim. Acta 16, 1279 (1960). Table 9 Nitro, Nitraso, etc. - 5!TABLE 10 HETEROCYCLIC COMPOUNDS Remarks Fig 3168~3125 | Higher than 3000 cm-as with other arom. +CH. | ~1565. and | YC=C of nucleus, variable intensity. |@ ~1500 10301018 Benzoluans)| ggs__ 379 | Shagp and most characteristic. 800~ 740 | Width and region both wide, sometimes split. 2) Pyrzoles 3490 vNH, Rather sharp and characteristic.’ Lower by ea. 90 ® em“? upon H-bonding. | } s1a5.~ LCH. er thae alltane 2CH. x “S00tw H we | {lndoles 1300(ewo} | Oe sia) 3) Thiophenes | 3125~3050 | vCH. Position characteristic, clearer than pyrrole »CHL es ~1820.and | xC-C, Becomes clear when conjugated with other groups ‘ ~1040 | “Gower band stonaer. Mostly absent when not eonjugat- 750~ 690 | Strongest of thiophene bands, shifted to higher freq. by ‘lectron-attracting groups 4) a@-Pyronesi | 1740~1720 | Frequently aplit; higher band stronger in non-polar sol- | @ 6 vente (CC1,CS,), and lower band stronger in polar salvents ° (CHCl, CH,CN) on as liquid or solid(l. Reason for this | not well-known. Considerably shifted by substituents, Coumsring, but cannot be explained consistently, (aeegmiros) | 16801620 Nee urease : co ar | iszo~is40 [PC“C: Uretl for supporting preenes of pyron rings 5) 7-Pyronest5l | 1680~1650 | Position not affected much by substituents, and splicing | @ also rare (change in intensity of ewo bands when splieit &_ 0 game as with a-pyrones(0l ‘Chromones 1650~1600 \xCuC. Intensity variable, useful in supporting presence of “Frilar) | 1500~1560 |} pyrone rin ©) «-Pyridones | 3200~240017] Complex shape, broad. Stretching of assce. NHL | NH (3400: free) | Sharp monomer band at 3400 cm~* in CCl, solutions less <_e than 0.025 mole per liter, iecocanlas 1690~165018] vC+O. Shifted slightly to lower freq. upon association similar) 7) 7-Pyridones | 1650~163008] Shifted slightly to lower freq. upon association — | @ aN 0 (cee) 8) r-Thiapyrones! 161011 | Overlapping of xC+O and vC=C Very broad and intense. | a i = 1. - 52 - Table 10 Heterocycles(i) Q1 [3] tt] 15) (6) 7 [8] (91 f10] References ‘M, Yamaguchi, Japan Analyst 4, 210 (1958), A. Fujino and M. Yamaguchi, * IR Spectra,” Vol. 3, p. 101 (1958). A. Fujin, M. Yamaguchi, ibid. Vol. 6, 61 (1959). (M. Yamaguchi, ikid. Vol. 4, p. 85 (1958), K, Yamada, ibid. Vol. 7, p- 106 (1959). R.N. Jones, C. L. Angell, T. Ito and R. J.D. Smi H, Shindo, Chem. and Pharm, Bull. 7, 407 (1959). 5. F. Mason, J. Chem. Soc. 4874 (1957). D. $. Tarbell and P. Holland, J. 4m. Chem. Soc. 16, 2451 (1954). References of various heterocyclic compounds are given by R, N. Jones and C. Sandorfy, Chemical Applications of Spectroscopy," pp. 534, 547 (Interscience, New York, 1956). 1» Can. J. Chem. 37, 2007 (1959). Table 10 Heterocycles + 53TABLE 11 SULFUR GROUPS!) Bonds between S, C, H San [ee = Trin 1) -SH | ssw | 2SEL Weaker than OH band. Shift to lower freq. upon | | 2600~25500 | Et Gonding ia not so large. \® Peers Oe re ee a os | $00~ dod | »C-S. Common to C-S of mercaptancs, sulfoxides, ere. | a Ss | sam atte | SC | OO=PI ph tag lower tan corp. C-CH, bande | j na 3 Sch, |__ 715250 | Considerably lower than CH of C-CH, ®) C8 1200~1050s | Influenced by J and M-effects of oubstituente, ring strain, ete, as with »C-O, 7) Thioureide | ~3400(s01n {thiolzetam: | ~3150(sotid) > \~ 1460 vs| Corresp, to “Amide II” band, { | 1300~1100s | CaS. Cortesp. to "Amide 1” band. ~ 1300 Corresp. to “Amide IIT" band. | 1H. Bonds between S, O -S Heccaan es All are intense. When C-S (above-mentioned) and C-O 4490-1310] (€% 1000 cm, s) bonds are present in the sulfur-contain- vSO, {1230-1120} *™E 87 uPs, the corresponding bands appear in addition. 1) Sulfinate R-SO-OR’ Group | Bena | Remarks Figs 8} Sulfoxide | 1060~1040 | Shifted lower by 19~20 cmt upon conj, and H-bonding ; | @ Eo. | a 2500 shifted higher when bonded to halogens or oxygen. | 9) Sulfinie acid | ~10%s | SO R-SO-OH | | | 11) Sulfurous acid | ~1200s | »S=O, Higher than (8) ~ (10) because two O-atoms are bonded to S-O, R-0-80-0-8 | 12) Sulfose | 1380~1310, | | te2s0~600 | #50) In solids shifted lower by 10~20 om", and fre- | @ Bsonn | eo | sienty slit into band groups. Neither affected [BBS | 80, | ASR ECan ner an 13) Suifonamide | 1370~1520 | Lower by 10-20 em" in solids. @ 11801160 | Same position in solids. ‘The fact that the two SO-bands RSOrNC | “are higher than in sulfones is contrary to relation between | Ketones and amides, | WH Sulonie we | aaiwti@e | m0 R-SO,OH | 1080~1010s | »SO, } Similar absorption range in salts. | 700~ 600 | »s-0 S4- Table 11 Sulfur groupsGroup Band (cm"1) Remarks Figs 15) Sulfonate 1420~1330s | »4:50, R-SO,OR’ | 1200~11458 | SO. 16) Sulfate 14401350 R-O-S0,-OR) 1230~1150 17) Saeco | 1370~ 1365 R-SO-xm | 1190~1170 Higher than (14) of (15) because of attachment of two oxygens to SO, References [1] Various $ bonds have been described by M. Yamaguchi, “IR Spectra,” Vol. 4, p. 85 (1958). [2] N. Sheppard, Trans. Far. Soc. 51, 1465 (1935). [3] A. Simon and H. Kriegemann, Chem. Ber. 1883, 1990 (1956); R. N. Haszeldine and J. M. Kidd, + Je Chen, Soc, 2901 (1955). Table 11 Sulfur groups ~ 55PH | 2s40~2350 TABLE 12 PHOSPHORUS GROUPS ‘The following bands assigned to respective bonds appear additively. \ Sharp, medium intensity PC | 750~ 650 P-O-Cyyy | 1950~1030 | 20-0, very intense. _In additions sharp but weak band is | shown at 1189 em"? by P-O-CH, and at 116em"? by | P-O-C.H, (2P-02). i P-0-Cuyi 1240~1190 | 4-0, very strong. 1160 | Sharp but weak, »P-O? 1: P.O 1300~1250 | Strong ; 1 PS 300~ 050 | Weak PO-P | 970~ 910 | Somewhat broad, Present in pyrophosphates:; it is in the | region of absorption of other P bonds t 2700~2560 | Assos. vOH, free OH band at ca, 3600 cmt does nat ap- pear upon dilution, LG 1240~1180 | uPsO, stronger than P+O absorption of (5). Organic, | | | phosphates | ally 1180~1150 | Substienss | aggy | |} P-O-C bond, absorption range identical with (3) | aryl 1090~ 1040, | ‘substituents I | = Table 12 Phosphorus groupe» 2 a 4 3) o 7 % 10) i) 12) 13) 14y 15) 19) 7 don, (1958). 8) NC TABLE 13 HALOGENS AND INORGANIC SALTSU-231 cr 1400~1000 vs ct. ca 800~ 600s (C-Br 600~ 5002 ~ 300s 1450~1410 (vs), $80~860 (m) 1130~1080 (vs), 680~610 (m~w) 1380~1350 (vs), 840~815 (m) 1250~1230 (vs), $40~800 (ww); also: at 1380~132014) 3300—-3030 (vs), 1430~1390 (s) | 1100~1000%s) } 2200~2000(s) cates, 1100~900 (=) Various Various oxysalts of phosphorus.(5) References 1] L. J. Bellamy, “ The Infra-red Spectra of Complex Molecules,” pp. 329 and 344, Methuen, Lon- |] FA. Miller and C. H. Wilkins, Anal. Chem. 24, 1253 (1952). |] Charseteristic frequencies for 20 ions in the 700~300 em region: F. A. Miller, G. L. Carlson, F, B. Bentley, and W. H, Jones, Spectrochim. Acta 16, 135 (1960). ||P. Tarte, Ann. Soc. Sci. Bruxelies, 70, 244 (1956); H. G. Hafele, Z. Phivk. 148, 262 (1937). ] D.E.C. Corbridge and E. J. Lowe, J. Chem. Soc. 4555 (1954). D.E, C. Corbridge, J. Appl. Chem, 6, 456 (1956). Table 13 Halogens and inorganic salts - 57