Appendix 4: IR ABSORPTION FREQUENCIES

TABLE 1: GENERAL ABSORPTION RANGES

Abbreviations: (s) = strong, (m) = medium, (v) = variable, (w) = weak

BOND TYPE CH

COMPOUND TYPE Alkanes (aliphatic sp3 CH stretch)

(CH bend)

Alkenes (olefinic sp CH stretch)

2

(CH bend)

Alkynes (acetylenic sp CH stretch)

(CH bend)

Aromatic rings (aryl CH stretch)

(CH bend)

CC C=C CC CC CO C=O OH

NH CN CN NO

Alkanes (CC stretch) Alkenes Alkynes Aromatic rings (in-plane vibrations) Alcohols, ethers, carboxylic acids, esters Aldehydes, ketones, carboxylic acids, esters, amides Monomeric alcohols, phenols H-bonded alcohols, phenols carboxylic acids, water contaminant Amines, Amides Amines Nitriles Nitro compounds (NO stretch) as in CNO2

FREQUENCY RANGE (cm1) 2960-2850 (m-s) 1470-1350 (v) 3080-3020 (m) 1000-675 (v) (See details in Table 2) ~ 3300 (s) ~ 630 (s) 3000-3100 (v) (often weak) 675-870 (See details in Table 3) 1300-1100 (v) (not useful) 1680-1640 (v) 2260-2100 (v) 1500, 1600 (v) (usually 4 peaks, see example p.A-12) 1300-1080 (s) 18001650 (s) (See details given in Table 5.) 3640-3610 (v) 3600-3200 (broad) 3000-2500 (broad) 3710 & 1630 3500-3300 (m) 1360-1180 (v) 2260-2210 (v) 1600-1500 (s) 1400-1300 (s)

TABLE 2: CH BENDING OF ALKENES (in cm-1) 920-910 (s) RCH=CH2 cis-RCH=CHR & 1000-990 (s) R2C=CH2 900-880 (s)

730-675 (v)

trans-RCH=CHR 975-965 (s)

Characteristic Absorptions of Aromatic Compounds There are four regions of absorptions for aromatic compounds. You will be mainly concerned with only Region I this semester. Region I: CH stretch slightly above 3000 cm-1 (Indicative of presence of benzene ring) Region II: Overtones & combination bands at 2000-1670 cm-1 (See Table 4) Region III: C=C in-plane vibrations at 1667-1429 cm-1: four bands at ~1600 (s), 1580 (w, as shoulder), 1500 (s) and 1460 (usually obscured by others). Absence of these bands is fair assurance that there is no aromatic ring in the compound. Region IV: CH bend at 1000-670 cm-1 (See Table 3) A-11

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APPENDIX 4: IR ABSORPTION FREQUENCIES

TABLE 3: For aromatic rings, out-of-plane CH bending (in cm-1) monosubstituted m-disubstituted ~750 (s) (range 770-730) R R & ~700 (s) (range 710-690)
R

~780 (v) (range 810-750)

o-disubstituted
R R

p-disubstituted ~750 (s) (range 770-735)

R R

~830 (v) (range 840-810)

Table 4: IR Absorption Overtones of Substituted Benzenes These are weak absorptions that may not be observed if the sample is not concentrated enough. They are helpful in determining the type of substitution if no interfering absorption is present, such as that of C=O.

IR Spectrum of Propylbenzene (Typical Absorptions of Aromatic Compounds)

Region IV
698 cm-1 743 cm-1 monosubstituted CH bend

Region III
1538 cm-1

1496 & 1453 cm-1

1584 cm-1

Region II aromatic overtones

1941, 1870, 1801, 1604 cm-1 (monosubstituted shown here)

Region I

aryl CH stretch 3100-3050 cm-1

C=C in-plane vibration

APPENDIX 4: IR ABSORPTION FREQUENCIES

A-13

Characteristic IR Absorptions of Carboxylic Acid Derivatives

TABLE 5: IR Absorptions of Carboxylic Acid Derivatives Functional Group ketone acid ester amide Frequency C=O 1710 cm1 C=O 1710 cm1 OH 25003500 cm1 C=O 1735 cm1 C=O 16401680 cm1 NH 32003500 cm1 C=O 1800 cm1 C=O 1800 and 1750 cm1 CN 2200 cm1 Comments lower if conjugated, higher if strained lower if conjugated broad, on top of CH stretch lower if conjugated, higher if strained two peaks for RCONH2 one peak for RCONHR' very high frequency two peaks just above 2200 cm1 (continued on the next page)

acid chloride acid anhydride nitrile