WOODWARD & FIESER RULES Conjugated bonds

H2C

CH2

Homoannular ring

Heteroannular ring

Exocyclic bonds
CH2

Endocyclic bonds
CH3

Conjugated system Conjugated diene Homoannular ring Heteroannular ring - unsaturated ketones ( if 5 carbon ring is there 202 )

Base value(nm) 217 253 214 215

Cross conjugation do not change max but absorbence will be changed

H2C CH2 H2C H2C CH2

Trans isomer absorb at longer max than cis isomer (Bathochromic) and absorbence will be increased (hyperchromic) Auxocrome will produce Bathochromic as well as hyperchromic shift. Weak acid in Alkaline medium Bathochromic shift Weak base in acidic medium Hypsochromic shift Increase in temperature Bathochromic shift
1

 If addition of methyl substitution cause steric hindrance, then change in max can not be predicted (Usually Hypsochromic & hypochromic )
H3C N CH3 H3C N CH3 CH3

max=251 nm
max * > *> > * Energy required is in reverse direction. * < 200 n * 160260 CH3Cl * 200500 C;C n * 250600 N=N, N=O

max = 243 nm

CC, CH H2O, CH3OH, C=C, C=O, C=N, C=O, C=N,

204nm

260nm

314 nm

Naphthacene 480 nm or Tetracene

Pentacene 580 nm

Rules for 1, 3-Buadiene system (red shift or bathochromic shift )

H2C CH2

Substitution by alkyl group or ring residue shift max by 5 nm towards longer wave length The creation of Exocyclic double bond causes an additional shift of 5 nm If the double bond is Exocyclic to two rings simultaneously then shift is 10 nm Examples:
H2C CH3 H2C H3C CH3 CH2 H3C CH3 CH2 CH3

Base substitution Conj.extension Exocyclic bond TOTAL

217 +5 +0 +0 222 nm

217 +2(5) +0 +0 227 nm

CH2

217 +2(5) +0 +0 227 nm

217 +3(5) +0 +0 232 nm

Base substitution Conj.extension Exocyclic bond TOTAL

217 +2(5) +0 +5 232 nm

217 +4(5) +0 +2(5) 247 nm

217 +4(5) +0 +0 237 nm

3

Rules for alicyclic conjugated system: (red shift or bathochromic shift) Base value: Homoannular ring 253 nm Heteroannular ring214 nm Extension of conjugation by one double bond 30 nm One double bond Exocyclic to one ring 5 nm One double bond Exocyclic to two rings simultaneously 10 nm -R ( alkyl including part of carbocyclic ring ) 5 nm -OR (alkoxy) 6 nm -Cl or -Br 5 nm -SR (R=alkyl) 30 nm -NR2 --> 60 nm solvent correction 0 nm ( solvent has negligible effect on max of transition)

Examples:
CH3 CH3 A A

Base substitution Conj.extension Exocyclic bond TOTAL

214 +3(5) +0 +5 234 nm

CH3

253 +3(5) +0 +5 273 nm

CH3

Assume that A is carboncounted two times 253 +4(5) +30 +2(5) 313 nm
CH2

A=C, counted two times 253 +5(5) +2(30) +3(5) 353 nm

CH2

CH2

H3C

CH3

H3C

CH3

H3C

CH3

H3C

CH3

Base substitution

253 +4(5)

253 +3(5)

214 +2(5)

214 +5
4

Conj.extension Exocyclic bond TOTAL

+0 +0 273 nm

+0 +0 268 nm

+0 +5 229 nm

+0 +0 219 nm

Here base value is 217 nm because the conjugation is not involving all the same ring carbons, while in above case all the ring carbons are involved .

CH2

CH2

H3C

CH3

This compound takes configuration like alicyclik srtucture, so base value is 214, but 5nm of exocyclic bond will not be added

- unsaturated ketones/ aldehyde /esters - unsaturated ketone system

O H2C R O O

OR

OR

CH3

Base value 215 nm - unsaturated ketone system (cycloheptenone)

O
SOLVENT CORRECTION

Base value 202 nm - unsaturated aldehyde system

O H2C O H

Alcohol 0 Hexane +11 Ether +7 Dioxane +5 Choroform +1 Water - 8

Base value 210 nm - unsaturated esters system

O H2C O R

Base value 195 nm It have strong max ( * 230-360 nm due to conjugation) & weak max ( * 315-320 nm due to =C=O group) in alcohol
5

 R band ( *) shows more blue shift when polarity of solvent increase, due to hydrogen bonding K band ( *) shows more red shift because polar * state is stabilized by H-bonding Rules: (red shift or bathochromic shift) alkyl group on carbon 10 nm alkyl group on carbon 12 nm alkyl group on & carbon 18 nm Cl group on carbon 15 nm Cl group on , , or carbon 12 nm Br group on , , or carbon 25 nm -Br group on carbon 30 nm -OH group on carbon 35 nm -OH group on or carbon 30 nm -OH group on carbon 50 nm -OR (alkoxy group) on carbon 35 nm -OR (alkoxy group) on 30 nm -OR (alkoxy group) on 17 nm -OR (alkoxy group) on 31 nm -OCOR (acyloy group) on , , or carbon 6 nm -SR (sulphide group) on carbon 80 nm -NR2 (amino group) on carbon 95 nm One Exocyclic double bond 5 nm One double bond extending the conjugation 30 nm Homodiene componenet Add 39 nm Examples: *) 219 nm ; ( *) 324 nm
O H3C CH2
H3C CH3 O CH3
O CH3 CH3

CH3

CH3

Base Sub. On Sub. On Sub. On - Conj.extension Exocyclic bond TOTAL

CH3 O

215 +10 +12 +0 +0 +0 237 nm

HO

215 +10 +24 +0 +0 +0 249 nm

H3C CH3 O CH3

215 +0 +12 +0 +0 +0 227 nm

O

215 +0 +12 +18 +30 +5 280 nm

O

O
H3C CH2

CH3

Base Sub. On Sub. On Sub. On - Conj.extension Exocyclic bond TOTAL

215 10 12 0 0 0 237 nm
O H3C O

202 +35 +12 +0 +0 +0 249 nm

CH 3
OH

215 +10 +24 +0 +0 +0 249 nm

215 +10 +24 +0 +0 +0 249 nm

CH3 CH3
O

215 +10 +12 +0 +0 +5 242 nm

CH3 CH3

CH3

CH3

Base Sub. On Sub. On Sub. On - Conj.extension Exocyclic bond TOTAL

202 +0 +12 +36 +30 +5 285 nm

O

215 +0 +24 +0 +0 +5 244 nm

O CH 3

215 +10 +24 +0 +0 +10 259 nm

CH 3

215 +0 +12 +18 +36 60 +5 +10 356 nm

CH3

O O O O O

O OH

O CH3 CH3

Base Sub. On Sub. On Sub. On - Conj.extension Exocyclic bond

215 +0 +12 +0 +0 +0

215 +10 +24 +0 +0 +0

215 +0 +24 +0 +0 +5

215 +10 +24 +0 +0 +10

215 +10 +12 +36 +30 +5

7

TOTAL

227 nm

249 nm
CH3

244 nm

259 nm

308 nm

O CH3

Base Sub. On Sub. On Sub. On -

202 +0 +0 +36 (on carbon only)

Conj.extension Exocyclic bond

+30 +5 =273 nm

Rules for substituted benzene ring

O

Parent compound & R=H G= Alkyl or ring residue (Ketone)

G

max 246 nm 250 nm 230 nm

G=H (Aldehyde) G= -OH or O alkyl (carboxylic acid or ester)

Addition for R substituent Alkyl or ring residue -OH, -Oalkyl -Cl -Br -NH2 -NHMe -N(Me)2 Oortho 3 7 0 2 13 0 20 11 meta 3 7 0 2 13 0 20 20 Para 10 25 10 15 58 73 85 78

O Cl

Br 4-bromobenzaldehyde

OH 4-hydroxybenzaldehyde

2-chlorobenzaldehyde

Base value substituent TOTAL

K e to n e stru c tu re
O

250 +15 265 nm

250 +25 275 nm

O OH

250 +0 250 nm
230 +7 +25 +7 269 nm

H3C

HO O OH

OH

M e th o x y

A lk y l

3 ,4 ,5 - tr ih y d ro x y b e n z o ic a c id

Base 246 + o-alkyl 3 + p-methoxy 25 = 274 nm

INTERPRETATION OF IR SPECTRUM
ALKANES :

C-H CH2 CH3 CH2 C-C

sp3 C-H absorption always occurs at frequencies 3000 2840 cm-1 Methylene groups have a characteristic bending absorption of approximately 1375 cm-1 Methyl groups have a characteristic bending absorption of approximately 1375 cm-1 The bending (rocking) motion associated with four or more CH2 groups in an open chain occurs at about 720 cm-1 Many weak peaks

ALKENES :

10

=C-H =C-H C=C

Stretch for sp2 C-H occurs at values 3095 3010 cm-1 Out-of-plane (oop) bending occurs in the range 1000-650 cm-1 Stretch occurs at 1660 1600 cm-1

ALKYNES :

C-H Stretch for sp C-H usually occurs near 3300cm-1 CC Stretch occurs near 2150 cm-1 AROMATIC RINGS :

=C-H =C-H C=C

Stretch for sp2 C-H occurs at values 3050 3010 cm-1 oop bending occurs at 900-690 cm-1 Ring stretch absorption often occur in pairs at 1600 cm-1 and 1475 -1

ALCOHOLS AND PHENOLS :

11

O-H C-O-H C-O

The free O-H stretch is a sharp peak at 3650 3600 cm-1 Bending appears as a broad and weak peak at 1440 1220 cm-1 Stretching vibrations usually occurs in the range of 1260 1000 cm-1

ETHERS :

C-O

The most prominent band is due to C-O stretch, 1300-1000 cm-1

ALDEHYDES :

R-CH=O C=C-CH=O Ar-CH=O Ar-C=CH=O C-H

C=O stretch appears in range 1740-1725 cm-1 for normal aliphatic Aldehydes Conjugation of C=O with C=C; 1700-1680 cm-1 for C=O and 1640 cm-1 for C=C Conjugation of C=O with phenyl; 1700-1660 cm-1 for C=O and 1600-1450 cm-1 for ring Longer conjugated system 1680 cm-1 Stretch, aldehyde hydrogen (-CHO), consists of a pair of weak bands one at 2860 2800 cm-1 and the other at 2760-2700 cm-1

KETONES :

R2-C=O

C=O stretch appears in range 1720 1708 cm-1 for normal aliphatic Ketones 12

C=C-C Ar-C=O-R

Conjugation of C=O with C=C; 1700-1675 cm-1 Conjugation of C=O with phenyl; 1700-1680 cm-1

CARBOXYLIC ACIDS : O-H C=O C-O Stretch usually very broad, occurs at 3400 2400 cm-1 Stretch, broad, occurs at 1730 1700 cm-1 Stretch occurs in the range 1320 1210 cm-1

ESTERS :

R-C=OOR C=C-C=OOR Ar-C=OOR R-C=OO-C=C O-C=O C-O

C=O stretch appears in range 1750-1735 cm-1 1740 1715 cm-1 for C=O and 1640-1625 cm-1 for C=C 1740-1715 cm-1 for C=O and 1600-1450 cm-1 Conjugation of single bonded oxygen atom with C=C or phenyl 1765 1762 cm-1 for C=O Cyclic esters (lactones); C=O frequency increases with decreasing ring size Stretch in two or more bands, one stronger and broader than the other, occurs in the range 1300 1000 cm-1

AMIDES : C=O N-H Stretch occurs approximately 1680 1630 cm-1 Stretch in primary amides (-NH2) gives two bands near 3350 and 13

N-H

3180 cm-1. Secondary amides have one band (-NH) at 3300 cm-1 Bending occurs around 1640 1550 cm-1 for primary and Secondary amides.

ACID CHLORIDES :

C=O C-Cl

Stretch occurs in the range 1810 1775 cm-1 in unconjugated chlorides. Conjugation lowers the frequency to 1780 1760 cm-1 Stretch occurs in the range 730 550 cm-1

ANHYDRIDES :

14

 C=O C-O AMINES :

Stretch always has two bands, 1830 1800 cm-1 and 1775 1740 cm-1 Stretch (multiple bands) occurs in the range 1300 900 cm-1

N-H N-H N-H C-N

Stretch occurs in the range 3500 3000 cm-1 Bend in primary amines results in a broad band in the range 1640-1560 cm-1 oop bending absorption can sometimes be observed near 800 cm-1 Stretch occurs in the range 1350 1000 cm-1

NITRILES :

15

 -CN Stretch is of medium intensity, sharp absorption near 2250 cm-1 ISOCYANATES :

-N=C=S

Stretch in an isocyanate gives a broad, intense absorption near 2270 cm-1

IMINES :

C=N

Stretch in an imine, oxime, and so on gives a variable-intensity absorption in the range 1690-1640 cm-1 16

NITRO COMPOUNDS :

O=N=O

Aliphatic nitro compounds : asymmetric stretch (strong), 1600-1530 cm-1 ; symmetrical stretch (medium), 1390-1300 cm-1 Aromatic nitro compounds (conjugated): asymmetric stretch (strong) 1550 1490 cm-1 ; symmetric stretch (strong), 1355 1315 cm-1

CARBOXYLATE SALTS : O=C=O Assymetric stretch (strong) occurs near 1600 cm-1 ; Symmetrical stretch (strong) occurs near 1400 cm-1

AMINE SALTS : N-H N-H Stretch (broad) occurs at 3300-2600 cm-1 Bend (strong) occurs at 1610 1500 cm-1

AMINO ACIDS : These compounds exist as zwitterions (internal salts) and exhibit spectra that are combinations of carboxylate and primary amine salts. Amino acids show NH3+ stretch (very broad), N-H bend (asymmetric/symmetric), and COO- stretch (asymmetric/symmetric) SULFUR COMPOUNDS : MERCAPTANS : S-H Stretch, one weak band, occurs near 2550 cm-1 and virtually confirms the Presence of this group.

SULPHIDES : 17

R-S-R

Little useful information is obtained from the IR

SULFOXIDES : S=O Stretch, one strong band, occurs near 1050 cm-1

SULFONES : C=O Asymmetric stretch (strong) occurs at 1300 cm-1 Symetric stretch (strong) at 1150 cm-1

SULFONYL CHLORIDES :

S=O

Asymmetric stretch (strong) occurs at 1375 cm-1 Symmetric stretch (strong) at 1185 cm-1

SULFONATES : S=O S-O Asymmetric stretch (strong) occurs at 1350 cm-1, Symmetric stretch (strong) at 1175 cm-1 Stretch, several strong bands, occurs in the range 1000 750 cm-1 18

SULFONAMIDES : S=O N-H Asymmetric stretch (strong) occurs at 1325 cm-1 Symmetric stretch (strong) at 1140 cm-1 Primary stretch occurs at 3350 and 3250 cm-1 Secondary stretch occurs at 3250 cm-1; bend occurs at 1550 cm-1

SULFONIC ACIDS : S=O Asymmetric stretch (strong) occurs at 1325 cm-1 Symmetric stretch (strong) at 1140 cm-1

PHOSPHORUS COMPOUNDS PHOSPHINES P-H PH2 P-H P-CH3 P-CH2 Stretch, one strong, sharp band at 2320 2270 cm-1 Bend, Medium bands, at 1090 1075 cm-1 and 840 810 cm-1 Bend, Medium band, at 990 885 cm-1 Bend, medium bands, at 1450-1395 cm-1 and 1346 1255 cm-1 Bend, medium band, at 1440 1400 cm-1

PHOSPHINE OXIDES P=O Stretch, one very strong band, at 1300 1240 cm-1

PHOSPHATE ESTERS P=O R-O Stretch, one very strong band, at 1300 1240 cm-1 Stretch

ALKYL AND ARYL HALIDES FLUORIDES C-F Stretch (strong) at 1400 1000 cm-1 Aryl fluorides absorb between 1250 and 1100 cm-1

CHLORIDES Stretch (strong) in aliphatic chlorides occurs in the range 785 -540 cm-1 Aryl chlorides absorb between 1100 and 1035 cm-1 CH2 Cl Bend (wagging) at 1300 -1230 cm-1 C-Cl

BROMIDES C-Br CH2-Br Stretch (strong) in aliphatic bromides occurs at 650 510 cm-1 Aryl bromides absorb between 1075 and 1030 cm-1 Bend (wagging) at 1250 1190 cm-1 19

IODIDES C-I CH2-I Stretch (strong) in aliphatic iodides occurs at 600 485 cm-1 Bend (wagging) at 1200 1150 cm-1

Interpretation of mass spectrum

INTRODUCTION: Mass spectroscopy is a powerful analytical technique for identifying the unknown compounds by determining their molecular weights, for qualitative and quantitative determination (bulk, surface and depth analysis) of trace and ultra trace levels of organic compounds and inorganic elements in different matrices and for understanding the physical and chemical properties of different molecules1. Common Fragment Ions and Neutral Fragments Common Small Ions m/z 15 amu 17 18 19 26 27 28 29 30 31 33 34 35(37) 36(38) 39 41 42 43 44 46 56 57 60 composition CH3 OH H2O H3O, F C2H2, CN C2H3 C2H4, CO, H2CN C2H5, CHO CH2NH2 CH3O SH, CH2F H2S Cl HCl C3H3 C3H5, C2H3N C3H6, C2H2O, C2H4N C3H7, CH3CO C2H4O NO2 C4H8 C4H9 CH4CO2 Common Neutral Fragments mass loss 1 amu 15 17 18 19 20 27 28 30 31 32 33 33 35(37) 36(38) 42 43 44 45 55 57 59 60 composition H CH3 OH H2O F HF C2H3, HCN C2H4, CO CH2O CH3O CH4O, S CH3 + H2O, HS H2S Cl HCl C3H6, C2H2O, C2H4N C3H7, CH3CO CO2O, CONH2 C2H5O C4H7 C4H9 C2H3O2 C2H4O2 20

79(81) 80(82) 91 127 128

Br HBr C7H7 I HI

64 79(81) 80(82) 127 128

SO2 Br HBr I HI

MASS SPECTRA OF SOME CHEMICAL CLASSES ALKANES & CYCLOALKANES 1. The alkanes generally require high energy for ionization and the ions so formed undergo random rearrangements. 2. In alkanes, the C C bonds are comparatively weaker than the C H bonds. 3. The molecular ion peak is always present in the straight chain saturated hydrocarbons or n- alkanes. In longer chain compounds the intensity of the peak is low. 4. The greater the branching in the alkane, the less is the probability of the appearance of the molecular ion peak due to rapid and extensive fragmentation. 5. The fragmentation pattern in the mass spectrum of alkanes is characterized by clusters of peaks and the corresponding peaks of each clusters are 14 mass units apart. 6. The largest peak in each cluster represents a Cn H2n+1 fragment and this is accompanied by CnH2n and Cn H2n-1 fragments. 7. The most abundant fragments are at C3 and C4 and the fragments abundances decrease in a smooth curve down to M - C2H5. The M-CH3 peak is characteristically very weak or missing. 8. Each peak is generally accompanied by peaks of mass 1 and 2 units lower, corresponding to the loss of one and two hydrogens respectively. Peaks at m/e 57, 43, 29 in n-pentane are surrounded by clusters of small peaks due to the presence of 13C(M+1)+ and loss of hydrogens (M+1)+ and (M+2)+. 9. A series of peaks separated by 14 mass units due to CH2 group includes CH3+, C2H5+, C3H7+, C4H9+. 10. Compounds containing more than 8 carbon atoms show fairly similar spectra. In such cases, identification can only be made by molecular ion peak. 11. The fission of bonds in alkanes occurs preferentially at the branched carbon atoms, because of the fact that stability of the carboium ions follows the order : Tertiary > Secondary > Primary. 12. A saturated ring in a hydrocarbon increases the relative intensity of the molecular ion peak, and favours cleavage at the bond joining the ring to the rest of the molecule. The fragmentation of the ring is usually characterized by loss of two carbons atoms as C2H4 (28) and C2H5 (29).

21

13. In case of cycloalkanes, the molecular ions are more abundant because the ring structures are more stable. Skeletal fissions occur which involves the fission of atleast two bonds.
+

CH2 CH2

CH2

CH2 CH2

CH2

22

ALKENES 1. The molecular ion peak is generally distinct. The relative abundance of molecular ion peak decreases with increasing molecular mass. 2. The molecular ion of alkene containing one double bond tends to undergo allylic cleavage.

R H2C

HC

+
CH3

H2C

CH2

3. The acyclic olefins are also characterized by clusters of peaks at intervals of 14 mass units as in case of alkenes. 4. If the formation of a six membered cyclic transition state involving hydrogen is possible, a McLafferty rearrangement usually takes place to give two alkenes, the positive charge may reside with either of the alkene. 5. The mass spectra of alkenes containing one double bond are characterized by the presence of peaks at Cn H2n-1 (27, 41, 55, 69) and peaks at CnH2n (28, 42, 56).

6. Because of ready migration of double bond, fragmentation of isomeric alkenes is almost similar.
CH2
+

+
CH2

CH2 CH2

23

7. The peaks at m/e 67 and 69 are the fragments from the cleavage of a biallylic bond.

8. The peak at m/e 93 may be rationalised as a structure of formula C7H9+ formed by isomerization, followed by allylic cleavage.

9. Cycloalkenes usually show a distinct molecular ion peak. The presence of one double bond in the ring introduces a possible pathway involving reversal of Diels-Alder reaction. AROMATIC HYDROCARBONS 1. An aromatic hydrocarbon generally shows a prominent molecular ion peak because of stabilizing effect of ring. 2. The aromatic molecules, characterized by abundant molecular ion which is usually accompanied by small isotopic peaks, (M+1) and (M+2) peaks due to 13C or D. 3. Alkyl substituted aromatic compounds undergo beta cleavage in the side chain and give resonance stabilized benzyl cation or more likely the tropylium ion. A prominent peak (m/e = 91) indicates the presence of an alkyl substituted benzyl ring.

24

H3C C
+

CH2 H

CH3

HC
+

CH
+

4. Aromatic compounds with alkyl groups having a chain of atleast three carbon atoms can undergo a shift of -hydrogen probably according to McLafferty rearrangement. As a result, a prominent peak at m/e = 92 is obtained. 5. In the mass spectrum of napthalene, the molecular ion is also the base peak and the largest fragment peak at m/e = 51 is only 12.5% as intense as the molecular ion peak. 6. Hydrogen migration with the elimination of a neutral olefin molecule accounts for the peak at m/e = 92 observed when the alkyl group is longer than C2.

7. A characteristic cluster of ions due to alpha cleavage and migration fo hydrogen appears at m/e 77 (C6H5+), 78 (C6H6+) and 79 (C6H7+) in monoalkyl benzenes. 8. Alkylated polyphenyls and alkylated polycyclic aromatic hydrocarbons exhibit the same beta cleavage as alkyl benzene compounds. ALCOHOLS 1. The molecular ion peak for primary and secondary alcohols is generally quite small. In case of tertiary alcohols the molecular ion peak is either very weak or absent and is not detectable. Characteristic ions result via fission of the C C bond next to the oxygen atom. 2. The molecular ion is formed as a result of removal of one electron form the lone pair on oxygen atom of the alcohol. R OH + e R O + 2 e 3. Fragmentation mode in alcohols is dependent on the nature of the alcohol. Primary alcohols show a prominent peak at m/e = 31 due to CH2 = OH.

4. Primary alcohols give a distinct and prominent peak at M-18, because of loss of H2O (18 mass units) from the molecular ion. 5. A distinct and sometimes prominent peak can usually be found at M 18 from loss of water. This peak is most noticeable in spectra of primary alcohols. 25

6. The elimination of water, in addition with elimination of olefin form the primary alcohols having a four or more carbon atom chain indicates the presence of peak at M (olefin + water), that is a peak at M-46, M-74 etc. The olefinic ion then decomposes by successive elimination of ethylene.

7. Alcohols also show peaks at M 1, M 2, and M 3 because of successive removal of hydrogen atoms.
CH3 H3C OH CH3 R OH H CH3 R O
+

8. The spectrum in the vicinity of very weak M 2 (R CH = O) and M 3 (R C O+) peaks. 9. Alcohols containing branched methyl groups, frequently show a fairly strong peak at M 33 resulting from the loss of CH3 and H2O. 10. However, the first formed ion of a secondary alcohol can decompose further to give a moderate intense m/e = 31.

26

AROMATIC ALCOHOLS 1. 2. 3. 4. Aromatic alcohols show fairly intense molecular ion peaks. The prominent peaks arise from M 28 and M 29, because of removal of CO and CHO respectively. During fragmentation, benzyl alcohol can lose one, two and three hydrogen atoms. The M H fragment of benzyl alcohol undergoes rearrangement to form hydroxyl tropylium ion.

27

5. Loss of H2O to give a distinct M 18 peak is a common feature, especially in some ortho substituted benzyl alcohols. PHENOLS 1. Phenols generally exhibit strong molecular ion peak and in phenol itself, the molecular ion peak is the base peak, and the M 1 peak is small. The common features of fragmentation are M 28 (loss of CO) and M 29 (loss of CHO) peaks. 2. Phenols with alkyl side chains undergo benzylic fission (loss of H+ and R+) and give hydroxytropylium ion or its variants.

OH

O H H

H
+

OH

H
+

28

ALIPHATIC ETHERS Ether exhibits only a weak or negligible molecular ion peak. The presence of etheral oxygen atom can be ascertained from the strong peaks at m/e = 31, 45, 59, 73. and these represent the fragment RO+ and ROCH2+ . The fragmentation takes place in two important ways. Loss of either of two alkyl groups gives an oxonium ion or the alkyl cation. This cleavage of C O bond generally leads to the most abundant ion in the mass spectrum of aliphatic ethers.The C O bond cleavage with the change remaining on the alkyl fragment can be represented as

Cleavage of the C C bond next to the oxygen atom i.e, alpha cleavage (- bond) may also occur. The ion so produced may undergo fragmentation further to eliminate an alkene. This process is of great importance when alpha carbon is substituted and beta hydrogen is available.

29

The first formed fragment may decompose further by the following process, often to give the base peak; the decomposition is important when the carbon is substituted.

ARYL EHTERS 30

1. The molecular ion peak of aromatic ethers is prominent. Methyl phenyl ether shows two main fragmentation. Primary cleavage occurs at the bond to the ring and first formed ion decomposes further. Loss of CH3 gives the ion (M 15), which further undergoes fission by losing CO to give m/e = 65 peak.

2. The characteristic aromatic peak at m/e =78 and 77 may involve loss of HCHO to give M 30.

ALIPHATIC KETONES 1. The molecular ion peak of ketones is usually quite prominent. The major fragmentation peaks of aliphatic ketones involves the fission of C C bonds adjacent to the oxygen atom. This cleavage gives rise to peak at m/e = 43 or 57 or 71. The base peak is generally obtained from the loss of the larger alkyl group.

31

2. When one of the alkyl chains attached to the C = O group is C3 or longer, cleavage of the C C bond once removed ( ) from the C=O group occurs with migration to give a major peak (McLafferty rearrangement).

3. In long chain ketones the hydrocarbons peaks are not distinguishable from the acyl peaks, because the mass of CO unit (28) is same that of the two methylene units (-CH2) 4. Because the heteroatom can usually stabilize charge more efficiently than the carbon, the charged fragment generally contains the hetero atoms. Hence, for methyl ketones, the acylium ion, CH3C O+ (m/e = 43) is often the base peak, because it is stabilized by resonance.

CYCLIC KETONES 1. The molecular ion peak in cyclic ketones is prominent. Here the primary cleavage is adjacent to the C = O group, but the ions so formed may undergo further cleavage to produce a fragment. The base peak in the spectrum of cyclopentanone and of cyclohexanone is m/e = 55. 32

33

AROMATIC KETONES 1. The molecular ion peak of aromatic ketones is prominent. Cleavage of aryl alkyl ketones takes place at the bond beta to the ring, leaving a characteristic ArC O+ ; fragment which usually accounts for the base peak. Loss of CO from the fragment gives the aryl ion at 77 in the case of acetophenone. 2. The cleavage of the bond adjacent to the ring to form a RC O+ ; fragment is somewhat enhanced by electron withdrawing groups and diminished by electron donating groups in the p position to the phenyl group. 3. As in aliphatic ketones, when the alkyl chain is C3 or longer, Cleavage of the C C bond once removed from the C = O group takes place with migration of hydrogen. This results in elimination of an olefin and formation of resonance stabilized ion. ALIPHATIC ALDEHYDES 1. The molecular ion peak of aldehydes is of low intensity. Cleavage of the C H and C C bonds next to the oxygen atom result in an M 1 peak and in M R peak (m/e = 29, CHO+). 2. In C4 and higher aldehydes (when hydrogen is present), McLafferty rearrangement that is cleavage of the bond occurs to give a major peak at m/e = 44, 58, 72 depending on the substituent. The resonance stabilized ion is formed through the cyclic transition state.

3. In straight chain aldehydes, the other unique peaks are at M 18 (loss of H2O), M 28 (loss of CH2 = CH2), M 43 (loss of CH2 = CH O) and M 44 (loss of CH2 = CH OH). 4. Isomeric aldehydes such as 2- methylbutanal and 3 methyl butanal can be distinguished by the fact that in the case of former, an intense peak at m/e = 58 is obtained, while in latter rearrangement peak occurs at m/e = 44.

34

AROMATIC ALDEHYDES 1. Aromatic aldehydes are characterized by a large molecular ion peak and by a M 1 peak, that is always larger than the molecular ion peak. The atomic hydrogen from the molecular ion is favoured because of stability of Ar C O+ ; ESTERS 1. The molecular ion peak is weak, but generally observable. 2. The most important of the cleavage reactions involves the loss of the alkoxy group from an ester to form the corresponding acylium ion, RCO+.

3. The second useful peak results from the loss of the alkyl group from the acyl portion of the ester molecule, leaving a fragment CH3 O C = O+ that appears m/e = 59. 4. Other fragment ion peaks include the OCH3+ fragment and the R+ fragment from the acyl portion of the ester molecule. These latter ions are much less important than the former two.

ALIPHATIC CARBOXYLIC ACIDS 1. The molecular ion peak of straight chain monocarboxylic acid is weak. The most characteristic peak is m/e = 60 which is due to McLafferty rearrangement. Sometimes it is also the base peak. Branching at the alpha carbon enhances cleavage by McLafferty rearrangement .

2. In small chain acids, peaks at M OH and M COOH are prominent. These are due to cleavage of bonds next to C = O. In long chain acids, the mass spectrum consists of two series of peaks obtained from the fission at each C C bond with the retention of charge either on the oxygen containing fragment (m/e = 45, 59, 73, 87) or on the alkyl fragment (m/e = 29, 43, 57, 71, 85). 3. In addition to McLafferty rearrangement peak, the spectrum of long chain acids resembles the series of the hydrocarbon clusters at interval of 14 mass units. In each cluster however, is a peak at Cn H2n 1O2.

AROMATIC ACIDS 1. The molecular ion peak of aromatic acids is large. The other prominent peaks are formed by the loss of OH (M 17) and of COOH (M 45). 2. If a hydrogen bearing ortho group is available, M 18 peak due to loss of water is also noticed. This is an example of ortho effect noted when the substituents may be in a 6 membered transition state to, facilitate loss of molecules such as H2O, NH3, ROH.

ALIPHATIC AMINES 1. The molecular ion of aliphatic monoamine is an odd number, but it is usually quite weak. The cleavage of the C C bond next to nitrogen is the most characteristic fragmentation pattern of the amines. The fission of this bond is so easy that the molecular ion is difficult to be observed.

2. For primary amines unbranched at the carbon, the base peak is at m/e = 30, which is due to CH2 NH2+. This cleavage of C C bond fission next to nitrogen accounts for the base peak in primary amines and secondary amines which are not branched at the carbon. 3. Primary straight chain amines show a homologus series of peaks of progressively decreasing intensity at m/e = 30, 44, 58, 72, 86, 100. 4. A peak at m/e = 30 is a good but not conclusive evidence for a straight chain amine.

AROMATIC AMINES 1. The molecular ion peak (odd number) of an aromatic monoamine, such as aniline is intense. In aniline the loss of one of the amino H atoms gives an intense M 1 peak. Loss of a neutral molecule such as HCN followed by loss of a hydrogen atom gives prominent and strong peak at m/e = 66 and 65 respectively. 2. When alkyl groups are attached to the nitrogen atom as in the case of arylalkylamines, cleavage of the C C bond next to the nitrogen atom predominates.

ALIPHATIC AMIDES 1. The molecular ion peak of straight chain mono amides is usually discernable. The dominant modes of cleavage depend on the length of the acyl moiety, and on the lengths and number of the alkyl groups attached to the nitrogen atom. 2. The base peak in all straight chain primary amides results from the familiar McLAfferty rearrangement.

3. Primary amides give a strong peak at m/z = 44 from the cleavage of the R CONH2 bond. A moderate peak at m/z 86 results from C C cleavage, possibly accompanied by cyclization.

4. Secondary and tertiary amides with an available hydrogen on the carbon of the acyl moiety and methyl groups on the N atom show the dominant peak resulting from McLafferty rearrangement. 5. When the N-alkyl groups are C2 or longer and the acyl moiety is shorter than C3, another mode of cleavage predominates. This is cleavage of the N alkyl group to the N atom, and cleavage of the carbonyl C N bond with migration of an hydrogen atom of the acyl moiety.

ALIPHATIC NITRILES 1. The molecular ion peak of aliphatic nitriles is very weak or absent. These compounds are usually detected by M 1 peak formed by the loss of an hydrogen atom. This peak is also weak. 2. The base peak of straight chain nitriles (between C4 to C9) is at m/e = 41. This peak is due to ion resulting from hydrogen rearrangement (McLafferty rearrangement) in a 6- membered transition state. This peak, however is not of diagnostic value because of the presence of C3 H5 (m/e = 41) for all molecules containing a hydrocarbon atom. 3. A peak at m/e = 97 is characteristic and intense in straight chain nitriles ( C8 and higher).

ALIPHATIC NITRO COMPOUNDS 1. The molecular ion peak (odd number) of an aliphatic mono-nitro compound is either weak or absent. The main peaks are assignable to the hydrocarbon fragments upto M NO2. The presence of NO2 group is shown by peaks at m/e = 30 (due to NO+) and at m/e = 46 (due to NO2+). AROMATIC NITRO COMPOUNDS 1. The molecular ion peak of aromatic nitro compounds is odd number for one N atom and is strong. Prominent peaks are obtained from the elimination of an NO2 radical ( M 46, the base peak in C6H5NO2), and a neutral NO molecule with rearrangement to form the phenoxy cation (M 30). Both of these peaks are characteristic diagnostic peaks. 2. Loss of HC CH from M 46 ion accounts for a strong peak at M 72. Loss of CO form M 30 ion gives M 58 peak. A characteristic peak results at m/e = 30 form the NO+ ion. 3. Isomeric o-, m-, p- nitroanilines each gives a strong molecular ion peak (even number). They all give characteristic peaks resulting from the following steps 4. The m-, p- compounds give a small peak at m/e = 122 by the loss of an O atom. The o-, compound eliminates OH to give a small peak at m/e = 121 as follows. RULES FOR FRAGMENTATION 1. The relative height of the molecular ion peak is greatest for the straight chain compound and decreases as the degree of branching increases. 2. The relative height of the molecular ion peak usually decreases with increasing molecular weight in a homologous series. 3. Cleavage is favored at alkyl substituted carbon atoms; the more substituted the more likely to cleavage. This is a consequence of the increased stability of a tertiary carbon over a secondary, which in turn is more stable than a primary. 4. Double bonds, cyclic structures and especially aromatic or (heteroaromatic) rings stabilize the molecular ion, and thus increase the probability of its appearance.

5. Double bonds favor allylic cleavage and give the resonance stabilized allylic carbocation. This rule does not hold for simple alkenes because of the ready migration of the double bond, but it does hold the cyclo alkenes.

6. Saturated rings tend to lose alkyl side chains at the alpha bond. This is merely a special case of branching. The positive charge tends to stay with the ring fragment.

Unsaturated rings undergo retro Diels Alder reaction :

7. In alkyl substituted aromatic compounds, cleavage is very probable at the bond beta to the ring, giving the resonance stabilized benzyl ion, more likely the tropylium ion.

8. The C C bonds next to a hetero atom are frequently cleaved, leaving the charge on the fragment containing the heteroatom whose non bonding electrons provide resonance stabilization.

9. Cleavage is often associated with elimination of small stable neutral molecules, such as carbon monoxide, olefins, water, ammonia, hydrogen sulfide, hydrogen cyanide, mercaptans, ketones or alcohol, often with rearrangement.

Interpretation of NMR spectrum:

TYPES OF INFORMATION FROM THE NMR SP ECTRUM
1. Each different type of hydrogen gives a peak or group of peaks (multiplet). 2. The chemical shift ( , in ppm) gives a clue as to the type of hydrogen generating the peak (alkane, alkene, benzene, aldehyde, etc.) 3. The integral gives the relative numbers of each type of hydrogen. 4. Spin-spin splitting gives the number of hydrogens on adjacent carbons. 5. The coupling constant J also gives information about the arrangement of the atoms involved.

Proton Chemical Shift Ranges*

Low Field Regio n

High Field Regio n

* For samples in CDCl3 solution. The scale is relative to TMS at = 0.

SOME REPRESENTATIVE COUPLING CONSTANTS

vicinal trans cis geminal

6 to 8 Hz 11 to 18 Hz 6 to 15 Hz 0 to 5 Hz

three bond three bond three bond two bond

3J

3J

3J 2J

Hax,Hax =8 to 14 Hax,Heq =0 to 7 Heq,Heq =0 to 5 three bond

3J

cis trans

6 to 12 Hz 4 to 8 Hz

three bond

3J

4 to 10 Hz

three bond

3J

0 to 3 Hz

four bond

4J

0 to 3 Hz

four bond

4J

Couplings that occur at distances greater than three bonds are called long-range couplings and they are usually small (< 3 Hz) and frequently nonexistent (0 Hz).

APPROXIMATE 13C CHEMICAL SHIFT RANGES FOR SELECTED TYPES OF CARBON (ppm) R-CH3 R2CH2 R3CH C-I C-Br C-Cl C-N C-O 8 - 30 15 - 55 20 - 60 0 - 40 25 - 65 35 - 80 30 - 65 40 - 80 C C C= C C N 65 - 90 100 - 150 110 - 140 110 - 175 O O R-C-OR R-C-OH O R-C-NH2 O O R-C-H R-C-R

155 - 185 155 - 185 185 - 220