appendix four table of characteristic infrared frequencies A. The hydrogen streich region (3600-2500 cm). Absorption in this regi nis associated with the stretching vibration of hydrogen atoms bonded to carbon, oxygen, and nitrogen. Care should be exercised in the interpretation of very weak bands because these may be overtones of strong bands occurring at frequencies one-half the value of the weak absorption, i.e., 1800-1250 cm". Overtones of bands near 1650 cm-1 are particularly common Functional (m=) Group Comments ) 3600-3400 | O—H stretching 3600 cm™ (sharp) unassociated O—H, 3400 Intensity: variable cm (broad) associated O—H; both’ bands frequently present in alcohol spectra; with strongly associated O—H (CO,H or enolized B-dicarbonyl compound) band is very broad (ca, 300 cm with its center at 2900-3000 em, (2) 3400-3200 | N—H stretching 3400 em (sharp) unassociated N—H, 3200 em-" Intensity: medium — | (broad) associated N—H; an NH, group usually appears as a doublet (separation ca. 50 cm”); the N—H of a secondary amine is often very weak, (3) 3300 CH stretching of | The complete absence of absorption in this region (4) 3080-3010 an alkyne strong C=H stretehing of an alkene Intensity: strong to ‘medium (5) 3050 C-H stretching of an aromatic com- pound Intensity: variable; usually medium co weak 3300-3000 em" indicates the absence of hydro- gen atoms bonded to C=C or C=C and usually indicates the lack of unsaturation in the molecule, Because this absorption may be very weak in large molecules, some care should be exercised in this interpretation. (6) 3000-2600 OH strongly hydro- gen-bonded Intensity: medium A very broad band in this region superimposed on the C—H stretching frequencies is charac- teristic of carboxylic acids [see (1) above}.Functional o(em=") Group Comments (7) 2980-2900 | C—H stretching of | Just as in the previous C—H entries [(3)-(9) ‘an aliphatic com- | above), complete absence of absorption in this pound region indicates the absence of hydrogen atoms bonded to tetravalent carbon atoms. The ter~ Intensity: strong tiary C—H absorption is weak. ( 2850-2760 | C—H suetching of | Either one or two bands may be found in this an aldehyde region for a single aldehyde function in the Intensity: weak ‘molecule, B. The triple-bond region (2300-2000 cm"). Absorption in this region is associated with the streiching vibration of triple bonds. Functional oem) Group Comments (1) 2260-2215 | C=N Nitriles conjugated with double bonds absorb at Intensity: strong lower end of frequency range; nonconjugated nitriles appear at upper end of range. (2) 2150-2100 | C: This band will be absent if the alkyne is sym~ Intensity: strong in | metrical and will be very weak or absent if terminal alkynes; | the alkyne is nearly symmetrical. |__ variable in others. ©. The double-bond region (1900-1550 em»). Absorption in this region is usually associated with the stretching vibration of carbon-carbon, carbon-oxygen, and carbon-nitrogen double bonds. Functional o(em=") Group Comments () 1815-1770 | C=O stretching of | Conjugated and nonconjugated carbonyls ab- an acid chloride sorb at the lower and upper ends, respectively, Intensity: strong of the range. (2 1870-1800 | C=O stretching of | Both bands are present. Each band is altered by and an acid anhydride | ring size and conjugation to approximately 1790-1740 | Intensity: strong. thesame extent noted for ketones[see (4) below]. O stretching of — | This band is subject to all of the structural effects an ester or lactone | discussed in entry (4) below. Thus, a conjugated Intensity: very strong | ester absorbs at ea. 1710 em * and a y-lactone absorbs at ca, 1780 em~* (3) 1750-1735 ( 1725-1705 | C=O stretching of | This value refers to the carbonyl absorption an aldehyde or frequency of an acyclic, nonconjugated alde- ketone hyde or ketone in which no electronegative Intensity: very strong | groups, eg, halogens, are near the carbonyl group. Because this frequency is altered in a predictable way by structural alterations, the following generalizations may be drawn.o(em}) Functional Group Comments I. Effect of Conjugation: Conjugation of the carbonyl group with an aryl ring or carbon- carbon double or triple bond lowers the frequency by about 30 em-¥. If the carbonyl group is part of a cross-conjugated system (unsaturation on each side of the carbonyl group), the frequency is lowered by about 50 cm=* Il. Effect of Ring Size: Carbonyl groups in six- membered and larger rings exhibit approxi- mately the same absorption as acyclic ketones; carbonyl groups contained in rings smaller than six absorb at higher frequencies, e.g., a cyclo- pentanone absorbs at ca, 1745 cm? and a cyclobutanone absorbs at about 1780 m=! The effects of conjugation and ring size are addi- tive, eg, a 2-cyclopentenone absorbs at ca. 1710 cm. IIL. Effect of Electronegative Atoms: An electro- negative atom (especially oxygen or halogen) bonded to the a-carbon atom of an aldehyde or ketone may raise the position of the car- bony! absorption frequency by about 20 cm~! (5) 1700 C=0 stretching of an acid Intensity: strong This absorption frequency is lowered by con- jugation as noted under entry (4). (6) 1690-1650 C= stretching of an amide or lactam Intensity: strong This band is lowered in frequency by about 20 em” by conjugation, The frequency of the band is raised about 35 em~ in y-lactams and 70 em~ in B-lactams, 1660-1600 C=C stretching of an alkene Intensity: variable Nonconjugated alkenes appear at upper end of range and absorptions are usually weak; con- jugated alkenes appear ai lower end of range and absorptions are medium to strong. The absorption frequencies of these bands are raised by ring strain but to a lesser extent than noted with carbonyl functions [see (4) above] 1680-1640 CEN stretching Intensity: variable This band is usually weak and difficult to assign.D. The hydrogen bend region (1600-1250 em). Absorption in this region is commonly due to bending vibration of hydrogen atoms attached to carbon and to nitrogen. These bands generally do not provide much useful structural information. In the listing below, the bands that are most useful for structural assignment have been marked with an asterisk. Functional o(em~) Group Comments 1600 —NH, bending ‘This band in conjunction with bands in the 3300 Intensity: strong, cm! region is often used to characterize to medium primary amines and unsubstituted amides. 1540 —NH— bending ‘This band in conjunction with bands in the Intensity: generally 3300 cm- region is often used to characterize weak secondary amines and monosubstituted amines. In the case of secondary amines this band, like the N—H stretching band in the 3300 em-* region, may be very weak. *1520 and | NO, coupled streteh- | This pair of bands is usually very intense. 1350 ing bands Intensity: strong. 1465 —CH,— bending | The intensity of this band varies according to Intensity: variable the number of methylene groups present; the more such groups there are, the more intense the absorption, 1410 —CH,—bending of | This absorption is characteristic of methylene carbonylcontain- | groups adjacent to carbonyl functions; its in- ing component tensity depends on the number of such groups Intensity: variable present in the molecule. +1450 and | —CH, The band of lower frequency (1375 cm) is 1375 Intensity: strong, usually used to characterize a methyl group. If two methyl groups are bonded to one carbon. atom, a characteristic doublet (1385 and 1365 em) will be present, 1325) 1 ‘This band is weak and often unreliable. —CH bending Intensity: weak E. The fingerprint region (1250-600 cm). The fingerprint region of the spectrum is generally rich in detail, with many bands appearing. This region is particularly diag- nostic for determining whether an unknown substance is identical with a known sub- stance, the infrared spectrum of which is available. It is not practical to make assign- ments to all of these bands, because many of them represent combination frequencies land therefore are very sensitive to the total molecular structure; in addition, many single- ‘bond stretching vibrations and a variety of bending vibrations also appear in this region. Suggested structural assignments in this region must be regarded as tentative and generally taken as corroborative evidence in conjunction with assignments of bands at higher fre- quencies.Functional (em) Group Comments 1200 It is not certain whether these strong bands C\- arse fom C0 tering or C—O soehing — vibrations. One or more strong bands is found Intensity: stong in this region of the spectra of alcohols, ethers, and esters. The relationship indicated between 1150 | structure and band location is only approxi- aoe mate and any structural assignment based on this relationship must be regarded as tentative. Intensity: strong Esters often exhibit one or two strong bands i100 | between 1170 and 1270 cm“! —CH—0— Intensity: strong 1050 —cH,-0— Intensity: strong 965 meeHEy This strong band is present in the spectra of So=ct trans-1,2-disubstituted ethylenes. H CHH bending Incgnsity: strong 985 and 910 [HOH The lower-frequency band of these two strong Semel ‘bands is used to characterize a terminal vinyl " group. CHI bending Intensity: strong 590 Ss This strong band, used (o characterize a methylene 2 group, may be raised by 20-80 em”! if the C—Hl bending methylene group is bonded to an electro- Intensity: strong, negative group or atom. 810-840 Hae Very unreliable, this band is not always present, Yeael and frequently seems to be outside this range seal: yuons as substituents are varied. 700 None’ This band, attributable to a cis-1,2-disubstituted wu ethylene, is unreliable because itis frequently obscured by solvent absorption or other bands. Intensity: variable 2. ie 730 and 690 | These bands are of limited value because they a are frequently obscured by solvent absorption ‘or other bands. Their usefulness will be most W Hu important when independent evidence leads 4 to a structural assignment complete except C-H bending for position of aromatic substituents Intensity: strongo(em") Functional Group Comments 750 He HOS OH H C—H bending Intensity: very strong 780 and 700 H. H H H and 1, 2,3 Intensity: very strong 825 H. H it H and 1, 2,4 Intensity: very strong 1400-1000 c-F Intensity: strong 800-600 c-a Intensity: strong 700-500 cC—Br Intensity: strong ca Intensity: strong, The position of these bands is quite sensitive tostructure. They are, therefore, not particularly useful because the presence of halogen is more easily detected by chemical methods. The bands are invariably strong.