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PENENTUAN STRUKTUR SENYAWA

ORGANIK
Bagaimana kita mengetahui:
 Bagaimana atom-atom berhubungan satu sama lain?
 Ikatan mana yang tunggal, rangkap dua, atau rangkap tiga?
 Gugus fungsi apa yang ada di dalam molekul tersebut?
 Apakah memiliki stereoisomer spesifik?

Bidang penentuan struktur senyawa organik
berusaha menjawab pertanyaan di atas.

METODE INSTRUMEN PENENTUAN
STRUKTUR
1. Resonansi Magnet Inti, Nuclear Magnetic Resonance (NMR) – Eksitasi
inti atom melalui penyinaran/pemaparan frekuensi radio. Memberikan
informasi ekstensif tentang struktur molekul dan hubungan atom-atom.
2.

Infrared Spectroscopy (IR) – Memicu vibrasi molekul melalui
penyinaran/pemaparan dengan sinar inframerah. Memberikan informasi
yang lebih banyak tentang ada atau tidak adanya gugus fungsi tertentu.

3.

Mass spectrometry – Pemboman contoh dengan elektron dan
pendeteksian fragmen molekul hasilnya. Memberikan informasi tentang
massa molekul dan hubungan atom.

4.

Ultraviolet spectroscopy (UV) – Promosi elektron ke tingkat energi
yang lebih tinggi melalui penyinaran/pemaparan molekul dengan sinar
ultraviolet. Kebanyakan memberikan informasi tentang adanya sistem
konjugasi dan adanya ikatan rangkap dua dan rangkap tiga.

SPEKTROSKOPI – Studi informasi
spektrum
Rangsangan
secara fisik

Molecule

response

Detecting
instrument

Visual (most common)
representation, or
Spectrum

Upon irradiation with infrared light, certain bonds
respond by vibrating faster. This response can be
detected and translated into a visual representation
called a spectrum.

e. i. Once a spectrum is obtained. the main challenge is to extract the information it contains in abstract. 2. and the interpretation of these patterns in terms of meaningful and logical explanations. . Identify possible meanings. propose explanations. or hidden form. Associate patterns with physical parameters.SPECTRUM INTERPRETATION PROCESS 1. Recognize a pattern. This requires the recognition of certain patterns. the association of these patterns with physical parameters. 3.

In other words.ELECTROMAGNETIC SPECTRUM Most organic spectroscopy uses electromagnetic energy. which consist of helium nuclei. as the physical stimulus. it can be referred to as “pure energy. Electromagnetic energy (such as visible light) has no detectable mass component. have a detectable mass component and therefore cannot be categorized as electromagnetic energy. or radiation. as indicated by the equation below. The important parameters associated with electromagnetic radiation are: • Energy (E): Energy is directly proportional to frequency. and inversely proportional to wavelength. • Frequency ( ) • Wavelength () E = h .” Other types of radiation such as alpha rays.

Jr. Organic Chemistry.G. Pearson Education Inc..EFFECT OF ELECTROMAGNETIC RADIATION ON MOLECULES Graphics source: Wade. L.. 2003 . 5th ed.

000  (cm )  wavenumber   ( m) -1 1    c .An IR Spectrum A plot of % transmittance vs vibrational  frequency in wavenumbers c   (cm-1) λ = wavelength υ = frequency  c = speed of light in a vacuum 10.

10.Wavenumbers  The higher the wavenumber. the shorter the wavelength.000  (cm )  wavenumber   ( m) -1 .

 The frequencies of IR radiation are more conveniently expressed by a wavenumber  (cycles per cm).An IR Spectrum  The wavelength of IR radiation is in the 2. . than by  (cycles per 3.0 x 1010 cm).5-25 micron range (compare to visible light in the 400700 nm range).

.G. 2003 . or atoms. Jr.. Pearson Education Inc. Organic Chemistry. Specific bonds respond to (absorb) specific frequencies Graphics source: Wade. It induces stronger molecular vibrations in covalent bonds.Infrared radiation is largely thermal energy. which can be viewed as springs holding together two masses. L. 5th ed.

Characteristic Vibrational Frequencies of Bonds  Bonds are not rigid but behave like a spring with a mass at either end.  Obey Hooke’s Law: F = -kx  This gives rise to a characteristic frequency for the vibration: 1  2 k reduced mass m1m2   reduced mass  m1  m2 .

12    reduced mass  Where M in amu  The wavenumber is affected by  the masses of the atoms in the bond  the strength of the bond M 1M 2 M1  M 2 .Characteristic wavenumber of Bonds  Characteristic wavenumber for the vibration: 1 k  2c reduced mass K   4.

 The lower the mass.  Stretching frequencies  C≡C > C=C > C-C  C≡N > C=N > C-N  C≡O > C=O > C-O  C(sp)-H > C(sp2)-H > C(sp3)-H . the higher the vibrational frequency. the higher the vibrational frequency.  Stretching frequencies for bonds to carbon: C-H > C-C > C-N > C-O  The stronger the bond.

 Formaldehyde has 6. .  Water has 3 possible vibrational modes.Number of Vibrational Frequencies in a Molecule  There are 3n-6 possible vibrational modes in a nonlinear molecule with no symmetry  Symmetry reduces the number of possible vibrational modes.

VIBRATIONAL MODES
 Covalent bonds can vibrate in several modes, including
stretching, rocking, and scissoring.
 The most useful bands in an infrared spectrum correspond to
stretching frequencies, and those will be the ones we’ll focus on.

Graphics source: Wade, Jr., L.G. Organic Chemistry, 5th ed. Pearson Education Inc., 2003

TRANSMISSION vs. ABSORPTION
When a chemical sample is exposed to the action of IR
LIGHT, it can absorb some frequencies and transmit the
rest. Some of the light can also be reflected back to the
source.
IR
source

Chemical
sample

Transmitted
light

Detector

From all the frequencies it receives, the chemical
sample can absorb (retain) specific frequencies
and allow the rest to pass through it (transmitted
light).
The detector detects the transmitted frequencies, and by doing so also
reveals the values of the absorbed frequencies.

AN IR SPECTRUM IN ABSORPTION MODE
The IR spectrum is basically a plot of transmitted (or absorbed)
frequencies vs. intensity of the transmission (or absorption).
Frequencies appear in the x-axis in units of inverse centimeters
(wavenumbers), and intensities are plotted on the y-axis in
percentage units.

The graph above shows a spectrum in absorption
mode.

This is the most commonly used representation and the one found in most chemistry and spectroscopy books. .AN IR SPECTRUM IN TRANSMISSION MODE The graph above shows a spectrum in transmission mode. Therefore we will use this representation.

A strong band covers most of the y-axis. . or weak (w). depending on their relative intensities in the infrared spectrum.CLASSIFICATION OF IR BANDS IR bands can be classified as strong (s). and a weak band falls to about one third or less of the y-axis. A medium band falls to about half of the y-axis. medium (m).

INFRARED ACTIVE BONDS Not all covalent bonds display bands in the IR spectrum.  Medium polarity bonds and asymmetric bonds produce medium bands. Only polar bonds do so. These are referred to as IR active. .  Weakly polar bond and symmetric bonds produce weak or non observable bands. The intensity of the bands depends on the magnitude of the dipole moment associated with the bond in question:  Strongly polar bonds such as carbonyl groups (C=O) produce strong bands.

as shown below. Narrow bands are thin and pointed. like a dagger. . A typical example of a broad band is that displayed by O-H bonds.INFRARED BAND SHAPES Infrared band shapes come in various forms. Broad bands are wide and smoother. Two of the most common are narrow and broad. such as those found in alcohols and carboxylic acids.

It provides information on molecular fragments. . • IR can provide a molecular fingerprint that can be used when comparing samples.INFORMATION OBTAINED FROM IR SPECTRA • IR is most useful in providing information about the presence or absence of specific functional groups. If two pure samples display the same IR spectrum it can be argued that they are the same compound. • IR does not provide detailed information or proof of molecular formula or structure. specifically functional groups. • Therefore it is very limited in scope. and must be used in conjunction with other techniques to provide a more complete picture of the molecular structure.

The graph shows the regions of the spectrum where the following types of bonds normally absorb. For example a sharp band around 2200-2400 cm-1 would indicate the possible presence of a C-N or a C-C triple bond.IR ABSORPTION RANGE The typical IR absorption range for covalent bonds is 600 ... L. Graphics source: Wade. Organic Chemistry.G. Pearson Education Inc. 2003 . 5th ed. Jr.4000 cm-1.

that is the region to the left of 1400 cm -1. Pearson Prentice Hall Inc. Graphics source: Wade. L. As a student. This is normally a complex area showing many bands. frequently overlapping each other. This is where most stretching frequencies appear.. This complexity limits its use to that of a fingerprint. Organic Chemistry.G.THE FINGERPRINT REGION Although the entire IR spectrum can be used as a fingerprint for the purposes of comparing molecules. 2006 . Fingerprint region: complex and difficult to interpret reliably.. 6th ed. Jr. Focus your analysis on this region. the 600 .1400 cm-1 range is called the fingerprint region. you should focus your analysis on the rest of the spectrum. and should be ignored by beginners when analyzing the spectrum.

v. 735-770 meta-disubst. strong unless marked: m. b. variable. 690-710 and 750-810 (m) para-disubst. broad . moderate. 690-710 and 730-770 ortho-disubst. cm-1 C-H alkanes 2850-2960 and 1350-1470 alkenes 3020-3080 (m) and RCH=CH2 910-920 and 990-1000 R2C=CH2 880-900 cis-RCH=CHR 675-730 (v) trans-RCH=CHR 965-975 aromatic rings 3000-3100 (m) and monosubst. 810-840 (m) alkynes 3300 O-H alcohols or phenols 3200-3640 (b) C=C alkenes 1640-1680 (v) aromatic rings 1500 and 1600 (v) C≡C alkynes 2100-2260 (v) C-O primary alcohols 1050 (b) secondary alcohols 1100 (b) tertiary alcohols 1150 (b) phenols 1230 (b) alkyl ethers 1060-1150 aryl ethers 1200-1275(b)and 1020-1075(m) all abs.Some characteristic infrared absorption frequencies BOND COMPOUND TYPE FREQUENCY RANGE.

.IR SPECTRUM OF ALKANES Alkanes have no functional groups. Pearson Education Inc. Since most organic molecules have such bonds. Organic Chemistry. 5th ed.G. L. which appear around 3000 cm-1.. most organic molecules will display those bands in their spectrum. Jr. 2003 . Graphics source: Wade. Their IR spectrum displays only C-C and C-H bond vibrations. Of these the most useful are the C-H bands.

1385 “ and 1370(s). 1395 (m) .IR spectra of ALKANES C—H bond “saturated” (sp3) 2850-2960 cm-1 + 1350-1470 cm-1 -CH2- + 1430-1470 -CH3 + -CH(CH3)2 -C(CH3)3 “ + and 1375 “ + and 1370.

n-pentane 3000 cm-1 2850-2960 cm-1 sat’d C-H 1470 &1375 cm-1 CH3CH2CH2CH2CH3 .

n-hexane CH3CH2CH2CH2CH2CH3 .

2-methylbutane (isopentane) .

3-dimethylbutane .2.

cyclohexane no 1375 cm-1 no –CH3 .

“unsaturated” vinyl (sp2) 3020-3080 cm-1 + 675-1000 RCH=CH2 R2C=CH2 + + cis-RCH=CHR 910-920 & 990-1000 880-900 + 675-730 (v) trans-RCH=CHR + 965-975 C=C bond 1640-1680 cm-1 (v) .IR of ALKENES =C—H bond.

1-decene unsat’ d C-H 3020 3080 cm-1 C=C 16401680 910-920 & 9901000 RCH=CH2 .

4-methyl-1-pentene 910-920 & 9901000 RCH=CH2 .

2-methyl-1butene 880-900 R2C=CH2 .

3-dimethyl-1-butene 880-900 R2C=CH2 .2.

L.. this band could be obscured by the broader bands appearing around 3000 cm-1 (see next slide) Graphics source: Wade.IR SPECTRUM OF ALKENES Besides the presence of C-H bonds.. Organic Chemistry.G. However. medium bands corresponding to the C=C bond stretching vibration at about 1600-1700 cm-1. 2003 . Pearson Education Inc. appearing around 3080 cm-1 as shown below. Jr. alkenes also show sharp. Some alkenes might also show a band for the =C-H bond stretch. 5th ed.

G. Graphics source: Wade. Organic Chemistry... 2006 . L.IR SPECTRUM OF ALKENES This spectrum shows that the band appearing around 3080 cm-1 can be obscured by the broader bands appearing around 3000 cm-1. 6th ed. Jr. Pearson Prentice Hall Inc.

730-770 ortho-disubstituted + 735-770 meta-disubstituted + 690-710. 750810(m) para-disubstituted + 810-840(m) C=C bond 1500. “unsaturated” “aryl” (sp2) 3000-3100 cm-1 + 690-840 mono-substituted + 690-710.IR spectra BENZENEs =C—H bond. 1600 cm-1 .

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730-770 mono- .ethylbenzene 30003100 cm-1 Unsat’ d C-H 1500 & 1600 Benzene ring 690710.

o-xylene 735770 ortho .

p-xylene 810840(m) para .

750810(m) .m-xylene meta 690-710.

styrene no sat’d CH 1640 C=C 910-920 & 990-1000 RCH=CH2 mono .

2-phenylpropene Sat’d C-H 880900 R2C=CH2 mono .

pmethylstyrene para .

have C-H bonds involving the sp carbon (the carbon that forms part of the triple bond). that is to say those where the triple bond is at the end of a carbon chain. The following slide shows a comparison between an unsymmetrical terminal alkyne (1-octyne) and a symmetrical .IR SPECTRUM OF ALKYNES The most prominent band in alkynes corresponds to the carboncarbon triple bond. In some cases. weak band at about 3300 cm-1 corresponding to the C-H stretch. Terminal alkynes. Internal alkynes. it may not show at all due to the low polarity of the triple bond associated with those alkynes. that is those where the triple bond is in the middle of a carbon chain. It shows as a sharp. Therefore they may also show a sharp. such as in highly symmetrical alkynes. weak band at about 2100 cm-1. do not have C-H bonds to the sp carbon and therefore lack the aforementioned band. The reason it’s weak is because the triple bond is not very polar.

G.IR SPECTRUM OF ALKYNES Graphics source: Wade. 6th ed. Organic Chemistry.. Jr. L. Pearson Prentice Hall Inc.. 2006 .

nitriles show a prominent band around 2250 cm-1 caused by the CN triple bond. but because the CN triple bond is more polar. This band has a sharp. Jr. Organic Chemistry. L. pointed shape just like the alkyne C-C triple bond. 2006 . this band is stronger than in alkynes.IR SPECTRUM OF A NITRILE In a manner very similar to alkynes. Graphics source: Wade..G. Pearson Prentice Hall Inc. 6th ed..

Benzyl isocyanate .

IR spectra ALCOHOLS & ETHERS C—O bond 1050-1275 (b) cm-1 1o ROH 1050 2o ROH 1100 3o ROH 1150 ethers 1060-1150 O—H bond 3200-3640 (b)  .

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1-butanol 3200-3640 (b) O-H C-O 1o CH3CH2CH2CH2-OH .

Jr. broad band covering the range of about 3000 3700 cm-1. and it appears as a strong. Pearson Prentice Hall Inc. 6th ed.IR SPECTRUM OF AN ALCOHOL The most prominent band in alcohols is due to the O-H bond. Organic Chemistry. Graphics source: Wade. The sheer size and broad shape of the band dominate the IR spectrum and make it hard to miss..G. L.. 2006 .

2-butanol O-H C-O 2o .

tert-butyl alcohol O-H C-O 3o .

methyl n-propyl ether no O--H C-O ether .

somewhat broad band (but not as broad as the OH band of alcohols). 2006 . Graphics source: Wade.. Secondary amines have only one NH bond. The spectrum below shows a secondary amine. in the range of about 3200 . resembling a canine tooth.G. tertiary amines have no N-H bonds. and it appears as a weak to medium. and therefore this band is absent from the IR spectrum altogether. which makes them show only one spike. Organic Chemistry.IR SPECTRA OF AMINES The most characteristic band in amines is due to the N-H bond stretch. L. therefore they typically show two spikes that make this band resemble a molar tooth.3600 cm-1. This band is positioned at the left end of the spectrum.. Primary amines have two N-H bonds. 6th ed. Jr. Pearson Prentice Hall Inc. Finally.

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CARBONYL COMPOUNDS Cm-1 1810 1800 1760 1735 1725 1715 1710 1690 Anhydride (band 1) Acid chloride Anhydride (band 2) Ester Aldehyde Ketone Carboxylic acid Amide Factors That Influence the C=O Stretching Vibration Conjugation Effects Lowering of the C=O frequency in a 25-45 cm-1 from the base value .

resulting of the absorption frequency. . Hydrogen-Bonding Effects Hydrogen bonding to a carbonyl group lengthens the C=O bond and lowers the stretching force constant K.Ring Size Effects Substituent Effects The electron-withdrawing effect removes electron from the carbon of the C=O bond. This removal is compensated for by a tightening of the π bond and leads to an increase in the absorption frequency.

they also show a pair of medium strength bands positioned about 2700 and 2800 cm-1. This band is due to the highly polar C=O bond.1720 cm-1 (right in the middle of the spectrum). In aldehydes. and size. whereas in ketones it’s in the middle of the chain. this group is at the end of a carbon chain. shape.IR SPECTRUM OF ALDEHYDES AND KETONES Carbonyl compounds are those that contain the C=O functional group. Because aldehydes also contain a C-H bond to the sp2 carbon of the C=O bond. . it is hard to miss. Because of its position. stake-shaped band around 1710 . the carbon in the C=O bond of aldehydes is also bonded to another carbon and a hydrogen. Aldehydes and ketones show a strong. As a result. Study the similarities and the differences so that you can distinguish between the two. whereas the same carbon in a ketone is bonded to two other carbons. These bands are missing in the spectrum of a ketone because the sp2 carbon of the ketone lacks the C-H bond. prominent. The following slide shows a spectrum of an aldehyde and a ketone.

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G.IR SPECTRUM OF ALDEHYDES AND KETONES Graphics source: Wade. 6th ed. Pearson Prentice Hall Inc.. Jr.. 2006 . L. Organic Chemistry.

2-butanone  C=O ~1700 (s) .

Pearson Prentice Hall Inc. L. At the same time they also show the stake-shaped band in the middle of the spectrum around 1710 cm-1 corresponding to the C=O stretch.. Jr. and around 1320-1210 cm-1 (medium intensity) corresponding to the C-O stretch. 6th ed. 2006 .IR SPECTRUM OF A CARBOXYLIC ACID A carboxylic acid functional group combines the features of alcohols and ketones because it has both the O-H bond and the C=O bond. Graphics source: Wade.G. Therefore carboxylic acids show a very strong and broad band covering a wide range between 2400 and 3400 cm-1 for the O-H stretch. Organic Chemistry..

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ESTERS .

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G. Pearson Prentice Hall Inc.. At the same time they also show the stake-shaped band in the middle of the spectrum around 1710 cm-1 for the C=O stretch. Organic Chemistry.IR SPECTRUM OF AMIDES The amide functional group combines the features of amines and ketones because it has both the N-H bond and the C=O bond. Jr. primary amides show two spikes. As with amines. Therefore amides show a very strong. 2006 . whereas secondary amides show only one spike. somewhat broad band at the left end of the spectrum. 6th ed. in the range between 3100 and 3500 cm-1 for the N-H stretch. L.. Graphics source: Wade.

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Acid Chlorides .

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Anhydrides .

Nitro Compounds .

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Sulfur Compounds Mercaptans R-S-H .

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EXERCISE

C9H12 1500 & 1600 benzene C-H unsat’d & sat’d mono C9H12 – C6H5 = -C3H7 isopropylbenze ne npropylbenzene? .

n-propylbenzene .

isopropylbenzene isopropyl split 1370 + 1385 .

C8 H 6 C-H unsat’d 3300 C-H 1500. 1600 benzene C 8 H 6 – C6 H 5 = C 2 H mono phenylacetylen e .

C4 H 8 Unst’ d 16401680 880900 C=C R2C=CH2 .

Which compound is this? a) 2-pentanone b) 1-pentanol c) 1-bromopentane d) 2-methylpentane 1pentanol .

What is the compound? a) 1-bromopentane b) 1-pentanol c) 2-pentanone d) 2-methylpentane 2-pentanone .

C A biphenyl H2 C C CH2 H E H2 H2 C C 1. do not try to fully analyze each spectrum.In a “matching” problem.2-diphenylethane allylbenzene CH3 CH3 B o-xylene D CH3CH2CH2CH2CH3 n-pentane F CH2CH2CH2CH3 n-butylbenzene . Look for differences in the possible compounds that will show up in an infrared spectrum.

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