NAlkanes

interpretedintermsof4vibrations:
stretchingandbendingofCHandCCbonds
CCbends:ca.500cm1(outofspectralwindow)
CCstretches:1200800cm1,weakbands

notofvalueforinterpretation(fingerprint)
morecharacteristic
CHstretches:occursfrom30002840cm1
CH3: 2962cm1,asymmetricalstretch
2872cm1,symmetricalstretch
CH2:

2926cm1,asymmetricalstretch
2853cm1,symmetricalstretch
Noteprecision!

nalkanes

CH2(s)1467cm1
scissor

CH
Stretches

CH3(as)1450cm1

CH3(as)2964cm1
CH2(as)2924cm

CH3(s)1375cm1

CH3(s)2872cm1
CH2(s)2853cm1

CH
Bends

C12H25

CH2(s)720cm1
Rock
Alkanesof7or
morecarbons

Fingerprinting

C10H22

C12H26

Similar
ButNot
Identical

UnconjugatedAlkenes
linearalkenes:
C=Cstretch:moderatetoweakabsorptionat16671640cm1

H
H
H

H
H

1640 cm1 , moderate

1650 cm1 , moderate

H
1670 cm1

weak

C=CH:
stretch:3000cm1

moderate
weak

UnconjugatedAlkenes

Overtoneof910cm1
Absorption
(1820cm1)

CH2rock
720cm1

CHstretch
3049cm1
C=Cstretch
1642cm1

OutofplaneC=CHbends
991,910cm1

1decene

IRtutor

http://members.aol.com/charlieabr/downloads.html

cyclicalkenes:
C=Cstretch:sensitivetoringstrain
CH3
1650 cm1

1566 cm1

1641 cm1

1640 cm1

1650 cm1

1781 cm1

cumulatedalkenes:
C=C=Cstretch(asymmetric):20001900cm1
conjugatedalkenes:
thealkenebondstretchingvibrationsinalkenesw/oacenterof
symmetrygiverisetotwoC=Cstretches

forsymmetricalmolecules,e.g.butadiene,onlytheasymmetric
stretchisobserved
Me

1650 cm1 (as)

1600 cm1 (s)

1600 cm1 (as)

ConjugatedDoubleBonds

Symmetrical
C=Cstretch
1640cm1
(weak)

CHstretch
3090cm1

Asymmetrical
C=Cstretch
1598cm1(strong)

Outofplane
C=CHbends
990,892cm1

Alkynes
1
C C
stretch:weakabsorptionat22602100cm

notobservedforsymmetricalalkynes(v.weakforpseudo
symmetricalkynes
terminalalkynes(RCCH)absorptionsarestrongerthan
internal(RCCR)absorptions

CCHstretch:
33333267cm1

strong,narrow(ascomparedtoOHorNH)

CCHbend:
700610cm1:broad,strongabsorption

14001220cm1,overtoneofabove

TerminalAlkynes

Alkyne
CCstretch
2119cm1

Alkyne
CHbendovertone
1260cm1

Alkyne
CHstretch
3310cm1

Alkyne
CHbend
630cm1

MononuclearAromaticHydrocarbons(benzene)
OutofplanebendingofaromaticCHbonds:mostinformative

900675cm1
intensebands,stronglycoupledtoadjacenthydrogensonthering
positionandnumberofbandsgivesinformationaboutthe
substitutionpattern(particularlyusefulforalkylsubstituted
aromatics.Substitutionofpolargroupscangiverisetoexceptions)

C=CHstretch:31003000cm1
CCstretch:16001585;15001400cm1
CCoutofplaneringbending:600420cm1

MononuclearAromatics

Overtonebands
20001650cm1
Aromatic
CHStretches
3087,3062,
3026cm1

AromaticCHinplanebends
13001000cm1

AromaticCCStretches
16001585;15001400cm1

Aromatic
CHoutof
Planebends
728cm1

outof
plane
ring
bending
428cm1

694cm1

CH3

CH3

795cm1

CH3

CH3

768cm1

CH3

CH3

742cm

691cm1

AlcoholsandPhenols
Stronglydependentonhydrogenbonding
nonhydrogenbondedOHgroupsabsorbstronglyinthe37003584
cm1range.
vaporphase;dilute,nonpolarsolvent;veryhindered
OH

not H-bonded
even when 'neat'
too hindered

Intermolecularhydrogenbondingoccursasconc.increases;
accompaniedbyashifttolowerfreq.(35503200cm1),atthe
expenseofthefreeOHband
PronouncedforintramolecularHbonding
O

CH3

H
O

CH3

OH
3600 cm 1 in dilute CCl 4
3100 cm 1 neat

3077cm1 in dilute CCl4

regardless of concentration

COstretchingVibrations
Alcohols(12601000cm1)

Phenols(18001260cm1)

primaryalcohol:10501085cm1

secondaryalcohol:108511251
tertiaryalcohol:11251200cm1

OH
1073cm1

OH
1110cm1

OH

1202cm1

Ethers
COCstretchingbandsaremostcharacteristicbands
strongbecauseofstrongdipolemoment
aliphaticethers:strongbandduetoasymmetricalstretching,

11501085cm1(usually1125cm1)
weakbandduetosymmetricalstretching(lowerfreq)
Alkylarylethers:asymmetricalstretchat12751200cm1

symmetricalstretchat10751020cm1
Vinylalkylethers:asymmetricalstretchat12251200cm1

symmetricalstretchat10751020cm1

O+
_

Carbonyls
C=Ostretcheasilyrecognized,intenseband
Ketones,aldehydes,acids,esters,lactones,acidhalides,
anhydrides,amidesandlactamsallshowC=Ostretching
intheregion18701540cm1.
Positionisdeterminedby(1)physicalstate(2)electronicand
massofneighboringgroups(3)conjugation(4)hydrogenbonding
(5)ringstrain

Ketones
aliphatic:normalpositionofaneataliphaticketoneis1715cm1
competingeffects
O

O
G
inductive: increases

O
Cl

F
1869

18151785
O

O
OH
1760 (monomer)

O
G+

resonance: decreases

Br
1812
OR
1750-1735
O

NH2

SR

1695-1650

1720-1690

Ketones
conjugation:shiftspositiontolowerfrequency
alkeneorphenylgroupcausesabsorptioninthe16851666cm1

region.Forunsaturatedcarbonyls,2absorptionsmaybe
observed

O
CH3

3350cm1
OvertoneofC=Ostretch

1685 cm 1

1685cm1

Forunsaturatedcarbonyls,2absorptionsmaybeobserved
O

CH3
CH3

s-trans
1685 cm

s-cis

1699 cm 1

1,3Diketones
O
R

O
R

enol
16401580 cm1

keto

hydrogen bonding
broadens and shifts
the carbonyl absorption
to shorter

OHstretching

H3C

CH3

1725cm1

H3C

1630cm1

CH3

CyclicKetones
ThebondangleinfluencestheabsorptionfrequencyoftheC=O
O
C

Instrainedrings,interactionwiththeadjacent
CCbondsincreasesthefrequencyofC=Ostretching

1715 cm 1

1751 cm 1

1775 cm 1

Aldehydes
C=Ostretch
Aliphaticaldehydes:C=Ostretchat17401720cm1
Electronwithdrawinggroupsshifttohigherfrequency
Conjugativegroupsshifttolowerfrequency(17101685cm1)
O
H3C

1730 cm

O
H

Cl3C

1768 cm 1

1678 cm 1

1703 cm 1

1666 cm 1

CHstretch
28302695cm1Often,twobandsareobserved(theotheris
aresultofanovertoneoftheCHbendofthealdehyde)

CarboxylicAcids
OHstretch
freeOH(ca.3520cm1)isobservedonlyinthevaporphase
orinverydilute(<0.01M)solutioninanonpolarsolvent
Otherwise,acidsexistasdimers
R

H O

O H

Intense,OHstretchinginthe33002500cm1region
centerednear3000cm1

C=Ostretch
monomer:1760cm1foraliphaticacids
dimer:Hydrogenbondingreducesthefrequencyofthe
asymmetricC=Ostretch,especiallywhenintramolecular
alkyl

O
O H

H O
O

alkyl

cm-1
17201706

aryl

O
O H

H O
O

aryl

1710-1680 cm -1

H
O

H
1665 cm -1
O

Esters
C=Ostretch
saturatedaliphaticesters:C=O:17501735cm1

formates,unsaturated,andbenzoateesters:17301715cm1

phenylorvinylesters:17701780cm1
COstretches(strongabsorptions;asymmetricalcoupledvibrations)
saturatedaliphaticesters(exceptacetates):CO:12101163cm1

acetates:1240cm1
unsaturatedesters:13001160cm1
benzoateesters:13101250cm1

O
1749cm1
C=O

OCH2CH3

1243cm1CO

1763cm1
C=O

1199,1164,1145cm1CO

O
O

1730cm1
C=O

O
O

1770cm1
C=O

O
H3C

1823cm1
C=O

AcidHalides
O

O
R

Cl

Cl

18151785 cm1

18001770 cm1

Anhydrides
Twocarbonylstretches(symmetricalandasymmetrical)
O
alkyl

O
O

alkyl

1818; 1750 cm 1

1775; 1720 cm

1865; 1782 cm 1

Amides

NHstretching:
O
R

NH2

Twobands
3520(as),3400(s)cm1(dilute)
3350(as),3180(s)cm1(conc)

O
R

N
H

35003400cm1(dilute)
33303060(s)cm1,multiplebandsduetoHbonding(conc)

C=Ostretching(AmideIband):
O

NH2
O

N
H

1690cm1(dilute)
1650cm1(conc)(exceptCH3CONH2,whichabsorbsat1694cm1)
16801700cm1(dilute)
1640cm1(conc)

O
R

N
R

16801630cm1(Hbondingnotpossible,unlessinproticsolvent)

Amides

NHBending(AmideIIband):
O
R

NH2

16201590cm1(dilute)separatefromamideI
16551620cm1(conc)overlapwiththeamideIband

O
R

N
H

15501510cm1(dilute)
15701515(s)cm1(conc)

Lactams
O

O
NH

O
NH

17501700cm1

1650cm1

NH
17601730cm1

SecondarylactamsdonothaveanNHbendingband(AmidebandII)near1550cm1.Thisisa
Characteristicofstranslactams.

HN H
Et
Et
N
H H

1662

(II)
1662cm1(I)

O
H3C

N
H

CH3
1
1565cm
(II)
1
1655cm (I)

Amines
NHstretching
indilutesolution,primaryamines(RNH2)display
2bands,near3500and3400cm1.Theserepresent
freeasymmetricalandsymmetricalstretches.
indilutesoln,secondaryamines(R2NH)displayoneband
near33503310cm1.
weakerandsharperthanOH
neatprimaryaliphaticamines(alkylNH2)absorb
at34003300and33303250cm1.ArylNH2absorbat
slightlyhigherfrequencies.

Nitriles
alkyl C N

22602240cm1

C N

22402222cm1

Nitrocompounds
2bandsfromtheasymmetricalandsymmetricalstretchingof
N O
thebond
alkylNO 2

NO2

1550 cm -1 and 1372 cm -1

1550-1500 cm -1 and 1360-1290 cm -1

1523(as)

1347(s)

Vinylalkylethers:C=Cstretchat16601610cm1

oftenadoublet
R

O+

trans:~1620cm1

R
_

cis:~1640cm1

vinyletherswaggingshiftedtolowerfrequency
R

terminal wag: 813 cm 1

trans CH wag: 960 cm -1

alkyl

terminal wag: 909 cm 1

trans CH wag: 1000 cm -1