Spectroscopy Data Tables

Infrared Tables (short summary of common absorption frequencies) The values given in the tables that follow are typical values. Specific bands may fall over a range of wavenumbers, cm-1. Specific substituents may cause variations in absorption frequencies. Absorption intensities may be stronger or weaker than expected, often depending on dipole moments. Additional bands may confuse the interpretation. In very symmetrical compounds there may be fewer than the expected number of absorption bands (it is even possible that all bands of a functional group may disappear, i.e. a symmetrically substituted alkyne!). Infrared spectra are generally informative about what functional groups are present, but not always. The 1H and 13C NMRs are often just as informative about functional groups, and sometimes even more so in this regard. Information obtained from one spectroscopic technique should be verified or expanded by consulting the other spectroscopic techniques. IR Summary - All numerical values in the tables below are given in wavenumbers, cm-1 Bonds to Carbon (stretching wave numbers)
sp3 C-X single bonds
C C C N C O C C C N

sp2 C-X single bonds

C O

not used sp2 C-X double bonds

1000-1350 not very useful

1050-1150 alkoxy C-O

not very useful sp C-X triple bonds

1250

1100-1350 acyl and phenyl C-O

C C C C N

1600-1680

1640-1690

1640-1810 expanded table on next page

2100-2250

2240-2260

Stronger dipoles produce more intense IR bands and weaker dipoles produce less intense IR bands (sometimes none).

Bonds to Hydrogen (stretching wave numbers)

C C H H C C H

O C H

2850-3000 sp3 C-H

H C N H C

3000-3100 sp3 C-H (see sp2 C-H bend patterns below)

3300 sp3 C-H (sp C-H bend 620)

O

2700-2760 2800-2860 aldehyde C-H (two bands)

N H

3100-3500 primary NH2 (two bands)

3100-3500 secondary N-H (one band)

3200-3400 alcohol O-H

2500-3400 acid O-H

2550 -2620 (very weak) thiol S-H

amides = strong, amines = weak

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Spectroscopy Data Tables

Carbonyl Highlights (stretching wave numbers)

Aldehydes
O C R H R

Ketones
O C R R

Esters
O C O

Acids
O

R'
R

C O

saturated = 1725 conjugated = 1690 aromatic = 1700

saturated = 1715 conjugated = 1680 aromatic = 1690 6 atom ring = 1715 5 atom ring = 1745 4 atom ring = 1780 3 atom ring = 1850 Anhydrides
O C O

saturated = 1735 conjugated = 1720 aromatic = 1720 6 atom ring = 1735 5 atom ring = 1775 4 atom ring = 1840 Acid Chlorides
O

saturated = 1715 conjugated = 1690 aromatic = 1690

Amides
O C R NR2 R

nitro
O

C O R R Cl

N O

saturated = 1650 conjugated = 1660 aromatic = 1660 6 atom ring = 1670 5 atom ring = 1700 4 atom ring = 1745 3 atom ring = 1850

saturated = 1760, 1820 conjugated = 1725, 1785 aromatic = 1725, 1785 6 atom ring = 1750, 1800 5 atom ring = 1785, 1865

saturated = 1800 conjugated = 1770 aromatic = 1770

asymmetric = 1500-1600 symmetric = 1300-1390

Very often there is a very weak C=O overtone at approximately 2 x (3400 cm-1). Sometimes this is mistaken for an OH or NH peak.,
sp2 C-H bend patterns for aromatics aromatic substitution pattern descriptive aromatic term absorption frequencies (cm-1) due to sp2 CH bend 690-710 730-770

sp2 C-H bend patterns for alkenes alkene substitution pattern

R C H R C H R C H R C R R C R R C R C R C H R C H R C R H C H H C H R H

descriptive alkene term

absorption frequencies (cm-1) due to sp2 CH bend 985-1000 900-920

monosubstituted alkene

monosubstituted aromatic

cis disubstituted alkene

675-730 (broad)
X

ortho disubstituted aromatic

735-770

trans disubstituted alkene

960-990

geminal disubstituted alkene

880-900

meta disubstituted aromatic

680-725 750-810 880-900 (sometimes)

trisubstituted alkene

790-840

para disubstituted aromatic

790-840

tetrasubstituted alkene

none

Aromatic compounds have characteristic weak overtone bands that show up between 1650-2000 cm-1). Some books provide pictures for comparison (not here). A strong C=O peak will cover up most of this region.

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Spectroscopy Data Tables

units = cm-1 4000 3500 3000 2500 2000 1700

3
1500 1400 1300 1200 1100 1000 900 800 700 alkene sp2 C-H bend mono trans acyl C-O phenol C-O alkoxy C-O C=C stretch aromatic aromatic sp2 C-H bend mono ortho nitro nitro meta para geminal tri cis 600 500

sp C-H stretch

sp3 C-H stretch thiol S-H stretch

C C

C=O stretch

sp C-H bend

sp2 C-H stretch aldehyde C-H stretch alcohol O-H stretch carboxylic acid O-H stretch 1o N-H2 stretch 2o N-H stretch 4000 3500 3000

C N

C=N stretch

C=C stretch alkene

N-H bend

2500

2000

1700

1500 1400 1300 1200 1100 1000 900

800 700

600 500

1000 mono trans

900

expansion of alkene & aromatic sp2 C-H bend region (units = cm-1) 700 600 800

500

mono cis geminal tri

alkene sp2 C-H bend

mono ortho meta para meta

mono

meta

aromatic sp2 C-H bend

1800

1750

expansion of carbonyl (C=O) stretch region (units = cm-1) 1700

1650

1600

Saturated C=O lies at higher cm-1 C=O in samll rings lies at higher cm-1

carboxylic acid C=O (also acid "OH") ester C=O (also acyl C-O and alkoxy C-O) aldehyde C=O (also aldehyde C-H) ketone C=O (nothing special)

Conjugated C=O lies at lower cm-1

acid chloride C=O (high C=O, 1 peak) anhydride C=O anhydride C=O (high C=O, 2 peaks)

amide C=O (low C=O, amide N-H)

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Spectroscopy Data Tables

IR Flowchart to determine functional groups in a compound (all values in cm-1). IR Spectrum does not have C=O band
C C C N

has C=O band (1650-1800 cm-1) very strong aldehydes

O

1725-1740 (saturated) 1660-1700 (unsaturated) C sometimes lost 2860-2800 in sp3 CH peaks 2760-2700 aldehyde C-H (both weak) ketones
O C

nitriles
C N

2250 sharp, stronger than alkynes, a little lower when conjugated

alkanes sp3 C-H stretch sp3 C-H bend

C C

2850-3000 1460 & 1380 not useful 3000-3100 650-1000 (see table for spectral patterns) 1600-1660 weak or not present 3050-3150 690-900 (see table), overtone patterns between 1660-2000 1600 & 1480 can be weak

alkenes sp2 C-H stretch sp2 C-H bend

C C

alkynes 1710-1720 (saturated) 1680-1700 (unsaturated) 1715-1810 (rings: higher in small rings) 1735-1750 (saturated) 1715-1740 (unsaturated) 1735-1820 (higher in small rings) 2150 (variable intensity) not present or weak when symmetrically substituted, a little lower when conjugated
C C

esters - rule of 3
O C

sp C-H stretch sp C-H bend

3300 sharp, strong 620

aromatics sp2 C-H stretch sp2 C-H bend

C C

acyl
C C

alkoxy

1150-1350 (acyl, strong) (1000-1150, alkoxy, medium)

O O C

acids 1700-1730 (saturated) 1715-1740 (unsaturated) 1680-1700 (higher in small rings)

O

acyl
C

1210-1320 (acyl, strong) 2400-3400, very broad (overlaps C-H stretch)

All IR values are approximate and have a range of possibilities depending on the molecular environment in which the functional group resides. Resonance often modifies a peak's position because of electron delocalization (C=O lower, acyl C-O higher, etc.). IR peaks are not 100% reliable. Peaks tend to be stronger (more intense) when there is a large dipole associated with a vibration in the functional group and weaker in less polar bonds (to the point of disappearing in some completely symmetrical bonds).

alcohols alcohol
O H

3600-3500 1000-1260 (3o > 2o > 1o) 2550 (weak) (easy to overlook) 3300 - 3500, two bands for 1o amines, one band o H for 2 amines, weaker than in amides,

alkoxy
C O

acid
O H

thiols thiol Alkene sp C-H bending patterns monosubstituted alkene (985-1000, 900-920) geminal disubstituted (960-990) cis disubstituted (675-730) trans disubstituted (880-900) trisubstituted (790-840) tetrasubstituted (none, no sp2 C-H)
2

H H

amides
O C H N

amines 1630-1680 (saturated) 1745 (in 4 atom ring) 3350 & 3180, two bands for 1o amides, one band for 2o amides, H stronger than in amines, extra overtone sometimes at 3100
N

1o
N N

N H H C

2o

N H

N-H bend, 1550-1640, stronger in amides than amines 1000-1350 (uncertain) 1120 (alphatic) 1040 & 1250 (aromatic)

2o

Aromatic sp2 C-H bending patterns monosubstituted (730-770, 690-710) ortho disubstituted (735-770) meta disubstituted (880-900,sometimes, 750-810, 680-725) para disubstituted (790-840) There are also weak overtone bands between 1660 and 2000, but are not shown here. You can consult pictures of typical patterns in other reference books. If there is a strong C=O band, they may be partially covered up.

N-H bend, 1550-1640, stronger in amides than amines 1800 (saturated) 1770 (unsaturated) Inductive pull of Cl increases the electron density between C and O. 1760 & 1820 (saturated) 1725-1785 (unsaturated) two strong bands

ethers alkoxy
C O

acid chlorides
O C

nitro compounds
O N O

1500-1600, asymmetric (strong) 1300-1390, symmetric (medium)

anhydrides
O C

carbon-halogen bonds

acyl
C O

usually not very useful

1150-1350 (acyl, strong) X = F, Cl, Br, I

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Spectroscopy Data Tables

deshielding side = less electron rich (inductive & resonance) typical proton chemical shifts Carbon and/or heteroatoms without hydrogen do not appear here, but influence on any nearby protons may be seen in the chemical shifts of the protons. 5
amide N-H alcohol O H

5
Typical 1H and 13C NMR chemical shift values.
shielding side = more electron rich (inductive & resonance)
amine N-H

1 1 1

6
S C H thiols, sulfides

2.5
N C H amines

2.0

X C H X = F,Cl,Br,I

3.0 3 2.5

2.3
allylic C-H 1.5 thiol SH 1.5 1.3

5
alkene C-H carboxylic acid O-H

benzylic C-H carbonyl alpha C-H

7+ 10
H O C

3+
epoxide C-H

2 2.5
C H

12

3.5
alcohols ethers esters

aldehyde C-H

aromatic C-H

simple sp3 C-H CH > CH2 > CH3

10 12 11 10

9 9

8+ 8 7 PPM

6 6

5+ 5 4

3.3 3 3

2 2

2 1

0.5 0

typical carbon-13 chemical shifts

halogen

with & without H O R C ketones no H R 95

F 80-95 Cl 45-70 Br 35-65 I 15-45 15 N C amines, amides with & without H

220+

180

O C X N C no H 125 110 O C C C with & without H 90

+

50 O epoxides with & without H 60

-

30

carboxylic acids anhydrides esters amides acid chlorides no H 180 O R C H C 160

40 S C

70

thiols, sulfides with & without H alcohols, ethers, esters 40 20

with & without H C C 80

+

50

aldehydes with H 210 180 160+

with & without H 10060+

simple sp3 carbon C > CH > CH2 > CH3 with & without H 0

240

220

200

180

160

140 PPM 120

100

80

60

40

20

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Spectroscopy Data Tables

Calculation of chemical shifts for protons at sp3 carbons H C C C

Estimation of sp3 C-H chemical shifts with multiple substituent parameters for protons within 3 C's of consideration. = directly attached substituent, use these values when the hydrogen and substituent are attached to the same carbon = once removed substituent, use these values when the hydrogen and substituent are on adjacent (vicinal) carbons = twice removed substituent, use these values when the hydrogen and substituent have a 1,3 substitution pattern 0.0 0.8 0.9 1.4 3.2 2.2 2.1 2.0 2.3 2.1 1.5 2.5 2.8 2.8 3.1 2.8 1.5 2.1 3.2 1.3 1.3 1.1 1.2 1.7 1.1 1.1 1.0 1.8 1.1 1.6 1.8 0.0 0.2 0.3 0.4 0.5 0.5 0.7 0.9 0.3 0.3 0.4 0.4 0.5 0.5 0.5 0.4 0.2 0.3 0.8 0.4 0.4 0.4 0.3 0.3 0.3 0.3 0.3 0.4 0.4 0.5 0.5 0.0 0.1 0.1 0.1 0.2 0.2 0.2 0.1 0.1 0.1 0.1 0.2 0.3 0.1 0.2 0.0 0.1 0.1 0.1 0.1 0.1 0.1 0.0 0.1 0.1 0.1 0.1 0.1 0.2 0.3 0.3 Starting value and equations for CH3's CH3 = 0.9 + H3C

X = substituent R- (alkyl) R2C=CR- (alkenyl) RCC- (alkynyl) Ar- (aromatic) F- (fluoro) Cl- (chloro) Br- (bromo) I- (iodo) HO- (alcohol) RO- (ether) epoxide R2C=CRO- (alkenyl ether) ArO- (aromatic ether) RCO2- (ester, oxygen side) ArCO2- (aromatic ester, oxygen side) ArSO3- (aromatic sulfonate, oxygen) H2N- (amine nitrogen) RCONH- (amide nitrogen) O2N- (nitro) HS- (thiol, sulfur) RS- (sulfide, sulfur) OHC- (aldehyde) RCO- (ketone) ArCO- (aromatic ketone) HO2C- (carboxylic acid) RO2C- (ester, carbon side) H2NOC- (amide, carbon side) ClOC- (acid chloride) NC- (nitrile) RSO- (sulfoxide) RSO2- (sulfone)

CH3 = 0.9 + ( + )

H3C C C

is the summation symbol for all substituents considered Starting value and equation for CH2's In a similar manner we can calculate chemical shifts for methylenes (CH2) using the following formula CH2 = 1.2 + ( + + ) H H C C C is the summation symbol for all substituents considered Starting value and equation for CH's In a similar manner we can calculate chemical shifts for methines (CH) using the following formula CH = 1.5 + ( + + ) H C C C is the summation symbol for all substituents considered

a. methine b. methylene CH2 CH3 HO N CH O H c. methyl Calculations are generally close to actual chemical shifts for a single substituent, but are less reliable as the number of substituent factors goes up. Multiple substituent factors tend to overestimate an actual chemical shift.

d. methyl H3C H2C H2C

e. methylene f. methylene a. methine = 1.5 + (1.4) + (2.3) + (0.2) = 5.4 ppm actual = 5.2 b. methylene = 1.2 + (1.5) + (0.4) + (0.3) = 3.4 ppm actual = 3.0 and 3.2 c. methyl = 0.9 + (1.5) = 2.4 ppm actual = 2.6

d. methyl = 0.9 + (0.1) = 1.0 ppm actual = 1.0 e. methylene = 1.2 + (0.3) = 1.5 ppm actual = 1.7 f. methylene = 1.2. + (1.7) = 2.9 ppm actual = 2.9

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Spectroscopy Data Tables Estimated chemical shifts for protons at alkene sp2 carbons

Substituent HHydrogen RAlkyl C6H5CH 2Benzyl X-CH2Halomethyl (H)/ROCH2alkoxymethyl (H)2/R2NCH2aminomethyl RCOCH2-keto NCCH2-cyano R2C=CRAlkenyl C6H5Phenyl FFluoro ClChloro BrBromo IIodo ROakoxy (ether) RCO2O-ester (H)2/R2NN-amino RCONHN-amide O2NNitro RSThiol OHCAldehyde ROCKetone HO2CC-acid RO2CC-ester H2NOCC-amide NCNitrile

geminal 0.0 0.5 0.7 0.7 0.6 0.6 0.7 0.7 1.2 1.4 1.5 1.1 1.1 1.1 1.2 2.1 0.8 2.1 1.9 1.1 1.0 1.1 0.8 0.8 0.4 0.3

cis 0.0 -0.2 -0.2 0.1 0.0 -0.1 -0.1 -0.1 0.0 0.4 -0.4 0.2 0.4 0.8 -1.1 -0.4 -1.3 -0.6 1.3 -0.3 1.0 0.9 1.0. 1.0 1.0 0.8

trans 0.0 -0.3 -0.2 0.0 0.0 -0.1 -0.1 -0.1 0.0 -0.1 -1.0 0.1 0.6 0.9 -1.2 -0.6 -1.2 -0.7 0.6 -0.1 1.2 0.7 03 0.5 0.5 0.6

Substitution relative to calculated "H" cis H C C trans gem (ppm) = 5.2 + gem + cis + trans Example Calculation gem H C CH3O C H cis H trans

gem = 5.2 + 1.4 = 6.6 actual = 6.6 trans = 5.2 - 0.1 = 5.1 actual = 5.1 cis = 5.2 + 0.4 = 5.7 actual = 5.6 c d H H C C O C O e H C Hf

bH C aH

a = 5.2 + (-0.4) = 4.8 actual = 4.9 (J = 14, 1.6 Hz) b = 5.2 + (-0.6) = 4.6 actual = 4.6 (J = 6, 1.6 Hz) c = 5.2 + 2.1 = 7.3 actual = 7.4 (J = 14, 6 Hz) d = 5.2 + 0.8 = 6.0 actual = 6.2 (J = 18, 11 Hz) e = 5.2 + 0.5 = 5.7 actual = 5.8 (J = 11, 1.4 Hz) f = 5.2 + 1.0 = 6.2 actual = 6.4 (J = 18, 1.4 Hz)

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Spectroscopy Data Tables Estimated chemical shifts for protons at aromatic sp2 carbons

Substituent HHydrogen CH3Methyl ClCH2Cholromethyl Cl3CHalomethyl HOCH 2Hydroxymethyl R2C=CRAlkenyl C6H5Phenyl FFluoro ClChloro BrBromo IIodo HOHydroxy ROAlkoxy RCO 2O-ester (H)2/R2NN-amino RCONHN-amide O 2NNitro RSthiol/sulfide OHCAldehyde ROCKetone HO2CC-acid RO2CC-ester H 2NOCC-amide NCNitrile

ortho 0.0 -0.2 0.0 0.6 -0.1 0.1 1.4 -0.3 0.0 0.2 0.4 -0.6 -0.5 -0.3 -0.8 0.1 1.0 -0.1 0.6 0.6 0.9 0.7 0.6 0.4

meta 0.0 -0.1 0.0 0.1 -0.1 0.0 0.4 0.0 0.0 -0.1 -0.2 -0.1 -0.1 0.0 -0.2 -0.1 0.3 -0.1 0.2 0.1 0.2 0.1 0.1 0.2

para 0.0 -0.2 0.0 0.1 -0.1 -0.1 -0.1 -0.2 -0.1 0.0 0.9 -0.5 -0.4 -0.1 -0.7 -0.3 0.4 -0.2 0.3 0.2 0.3 0.2 0.2 0.3

Substitution relative to calculated "H" meta para meta ortho ortho H

(ppm) = 7.3 + ortho + meta + para

Example Calculation 1 CH3O 2H H 3 2 H H

3 H

5 H 6 H 7

CH2 4

1. (CH3) = 0.9 + 2.8 = 3.7 actual = 3.8 2. (2) = 7.3 + (-0.5) ortho + (-0.1) para = 6.7 actual = 6.8 3. (3) = 7.3 + (-0.2) ortho + (-0.4) para = 6.7 actual = 7.1 4. (CH 2) = 1.2 + (0.8) + (1.4) = 3.4 actual = 3.3 5. (5) = 5.2 + (0.7) gem = 5.9 actual = 5.9 6. (6) = 5.2 + (-0.2) trans = 5.0 actual = 5.1 7. (7) = 5.2 + (-0.2) cis = 5.0 actual = 5.1

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Spectroscopy Data Tables Real Examples of Combination Effects on Chemical Shifts bond anisotropy bond example too 0.8 shielded (CH 2)

0.8, shielded H CH2 2.6 H electronegativity and bond O C H 9.5 C O H electronegative substituent and distance from protons O CH2CH 2CH2CH2CH 3 3.6 1.5 1.3 1.3 0.9 multiple substituents CH4 0.2 = 2.8 CH3 Cl 3.0 CH 3Cl 3.0 = 2.3 CH3CH 2 Cl 1.3 CH3CH2CH 2 Cl 1.0 CH2Cl2 5.3 = 1.9 O Ph H 3C C 2.6 6.4 3.7 H 2C H 3C 1.3 O O 7.2 deshielded 10-12 H O C hydrogen bonding H 3C H 1.5 O C

shielding cone from bond

H C H

O C

15, hydrogen bonded enol CH3

CH3CH 2CH 2CH2 Cl CH3CH 2 R 0.9 CHCl3 7.2 O H 3CH2C C 3.0 4.2 H 3C 2.1 O C O C H 7.3 C H 4.6 H =? 0.9 CCl4 ? (oops) O Ph (H3C)2CH C 3.5 4.9 Ph

substituents at methyl (CH3), methylene (CH2) and methine (CH) CH3Cl 3.0 CH3CH 2Cl (CH 3)2CHCl 3.5 4.1

alkene substituent resonance and inductive effects 0.9 1.4 2.0 O 3.8 H H CH CH CH H 5.0 CH O C 3 2 2 3 C C C C C H H H H H 5.8 4.9 5.3 6.1 aromatic resonance and inductive effects 6.6 H H 7.3 7.1 H H 6.7 H H H 2N H

H C

O C C

H 5.8

H 6.5 8.2 H

H 4.0 7.5 H 7.7 H

H H 2N

H O H O

H O N

H H

H H H H H H bond anisotropy produces deshielding Extra electron density via resonance produces shielding effect on aromatic protons, especially effect on aromatic at ortho/para positions. protons. sp C-H H C C H R C Ar 2.4 C H 1.9 C C H 3.0 RO ArO RS ArO H H H H

O H H H H Withdrawal of electron density via resonance produces deshielding effect on aromatic protons, especially at ortho/para positions.

R2N H amine H = 1-5 enol H = 10-17 H O alcohol H = 1-5 C C phenol H = 4-10 O O amide H = 5-8 thiol H = 1-2.5 R C R C aromatic thiol H = 3-4 NH2 O H acid H = 10-13

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Spectroscopy Data Tables

H1 observed proton C

1. One nearest neighbor proton Ha C one neighbor proton = Ha

10
increasing increasing E ( , Bo) perturbation(s) by neighbor proton(s) the ratio of these two populations is about 50/50 (or 1:1) H1 J1a 1 1 H1 C C C Protons in this environment have a small additional increment added to the external magnetic field, Bo, and produce a higher energy transition by that tiny amount. N + 1 rule (N = # neighbors) J (Hz) # peaks = N + 1 = 1 + 1 = 2 peaks

Eto flip proton Bo Protons in this environment have a small cancellation of the external magnetic field, Bo, and produce a smaller energy transition by that tiny amount. J = coupling constant small difference in energy due to differing neighbor's spin (in Hz) E1 (observed)

E2 (observed)

H1 C

(ppm) 2. Two nearest neighbor protons (both on same carbon or one each on separate carbons) two neighbor Ha protons C Hb Eto flip proton Bo H1 C C two neighbor protons are like two small magnets that can be arranged four possible ways (similar to flipping a coin twice) two equal energy populations here 1 E1 E 2 E 3 J1b the ratio of these four populations is about 1:2:1 H1 J1a J1b

H1 observed proton C

N + 1 rule (N = # neighbors) J (Hz) J (Hz) # peaks = N + 1 = 2 + 1 = 3 peaks

(ppm) 3. Three nearest neighbor protons (on same carbon, or two on one and one on another, or one each on separate carbons) H1 observed proton three neighbor Ha protons Hb Eto flip proton Bo H1 C C three neighbor protons are like three small magnets that can be arranged eight possible ways (similar to flipping a coin thrice) E1 E2 Hc the ratio of these eight populations is about 1:3:3:1 H1 E3 J1a E4 J1b J1c J1c J1b J1c

C C

three equal energy populations at each of middle transitions

N + 1 rule (N = # neighbors) J (Hz) J (Hz) J (Hz) # peaks = N + 1 = 3 + 1 = 4 peaks

(ppm)

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Spectroscopy Data Tables

11

Splitting patterns when the N+1 rule works (common, but not always true)
= group without any coupled proton(s) N=0 H C N=1 H C H C

N=2 H C H2 C t, J=7 I=1H N=2

H C CH CH

N=3 H C CH3

H H C CH CH2 CH C CH q, J=7 I=1H N=3 CH

s, J=none I=1H N=0

d, J=7 I=1H N=1

= calc or exp N=4 H C CH CH3

= calc or exp

= calc or exp N=5

= calc or exp H H CH C CH CH3 CH H C CH2 CH2

H C CH2 qnt, J=7 I=1H N=4 CH2 CH

H C CH CH2

C CH2

CH3

sex, J=7 I=1H N=5

= calc or exp N=6 H C CH3 sep, J=7 I=1H N=6 CH3 CH H C H2 C CH3 H2C H C CH2 CH2 CH N=7 H C CH3 CH3

= calc or exp

H H2 C oct, J=7 I=1H N=7 C CH2 CH3

= calc or exp N=8 H2C H C CH3 non, J=7 I=1H N=8 CH3 s = singlet d = doublet t = triplet q = quartet qnt = quintet sex = sextet = calc or exp sep = septet o = octet 1 1 7 1 1 6 5 1 4 1 1 1 3 6 2 3 4 1 1 1 1 1

= calc or exp

Pascal's triangle = coefficients of variable terms in binomial expansion (x + y)n, n = integer

Multiplets when the N + 1 rule works (all J values are equal). 1 peak = 100% 1 peak = 50% 1 peak = 25% 1 peak = 12% 1 peak = 6% 1 peak = 3% 1 peak = 1.5% 1 peak = 0.8% relative sizes of peaks in multiplets (% edge peak shown)

10 10 5

15 20 15 6 1 21 35 35 21 7 1

Combinations or these are possible. dd = doublet of doublets; ddd = doublet of doublet of doublets; dddd = doublet of doublet of doublet of doublets; dt = doublet of triplets td = triplet of doublets; etc.

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Spectroscopy Data Tables

12
Range Typical 14 Hz Ha C C C Hb Range 0-3 Hz Typical 1 Hz

Typical Coupling Constants

Ha 0-30 Hz

Hb geminal protons - can have different chemical shifts and split one another if they are diastereotopic Range Ha Hb C C 6-8 Hz Typical

cis / allylic coupling, notice through 4 bonds Range Ha 7 Hz C C C Hb 0-3 Hz 1 Hz Typical

vicinal protons are on adjacent atoms, when freely rotating coupling averages out to about 7 Hz Ha Hb C C H = dihedral angle Range H 0-12 Hz Typical

trans / allylic coupling, notice through 4 bonds Range C 7 Hz Ha C C Hb C 9-13 Hz 10 Hz Typical

depends on dihedral angle, see plot of Karplus equation Range Typical 0 Hz

sp2 vicinal coupling (different bonds) Range Ha C C O Hb 1-3 Hz Typical 2 Hz

Ha C

Hb C C

0-1 Hz

protons rarely couple through 4 chemical bonds unless in a special, rigid shapes (i.e. W coupling) Range Ha C C Hb sp2 geminal coupling Range Ha C C Hb 5-11 Hz Typical 10 Hz 0-3 Hz Typical 2 Hz

sp3 vicinal aldehyde coupling Range Ha C C

2

Typical 6 Hz

Hb C O

5-8 Hz

sp vicinal aldehyde coupling Range Ha C C C Hb 2-3 Hz Typical 2 Hz

sp2 cis (acylic) coupling (always smaller than the trans isomer) Ha C C Hb sp2 trans coupling (always larger than the cis isomer) Ha C C C Hb Range 4-10 Hz Range 11-19 Hz Typical 17 Hz

sp / propargylic coupling notice through 4 bonds Range Ha C C C Hb C 2-3 Hz Typical 3 Hz

bis-propargylic coupling notice through 5 bonds Typical ortho, meta and para coupling to 7 Hz this proton H H ortho H meta Range ortho 6-10 Hz meta 2-3 Hz para 0-1 Hz Typical 9 Hz 2 Hz 0 Hz

sp2 / sp3 vicinal coupling

Hpara

When J values are less than 1 Hz, it is often difficult to resolve them and a peak may merely appear wider and shorter.

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Spectroscopy Data Tables

13

Similar chemical shift information presented in a different format. Remember, proton decoupled carbons appear as singlets. When carbons are coupled to their hydrogens, carbons follow the N+1 rule. Methyls = q, methylenes = t, methines = d, and carbons without hydrogen appear as singlets = s. DEPT provides the same information. Carbon chemical shifts are spread out over a larger range than proton chemical shifts (they are more dispersed), so it is less likely that two different carbon shifts will fall on top of one another. The relative positions of various types of proton and carbon shifts have many parallel trends (shielded protons tend to be on shielded carbons, etc.) CH3 d 0 - 30 ppm (q) CH3 O d 50 - 60 ppm (q) sp3 carbon next to nitrogen CH3 N d 10 - 50 ppm (q) sp3 carbon next to bromine or chlorine (X = Cl, Br) CH2 X d 25 - 50 ppm (t) d d d d CH2 20 - 40 ppm (t) CH2 O 55 - 80 ppm (t) CH2 N 35 - 55 ppm (t) d d d CH 30 - 50 ppm (d) CH O 60 - 80 ppm d (d) CH N 50 - 70 ppm d (d) CH X 60 - 80 ppm (d) d d C 30 - 60 ppm (s) C O 70 - 90 ppm (s) C N 50 - 70 ppm (s) C X

Simple alkane carbons

sp3 carbon next to oxygen

60 - 80 ppm (s) C N 110 - 125 ppm C X

sp carbon (alkynes) sp2 carbon (alkenes and aromatics)

sp carbon (nitriles)

70 - 90 ppm

100 - 140 ppm

simple sp2 carbon resonance donation moves lower, resonance withdrawal moves higher O C X 160 - 180 ppm carboxyl carbons (acids, esters, amides) (s) C H O

140 - 160+ ppm sp carbon attached to an electronegative atom (X = oxygen, nitrogen, halogen) or C carbon conjugated with a carbonyl group
2

O C R 180 - 220 ppm ketone carbons, lower values when conjugated (s)

180 - 210 ppm aldehyde carbons, lower values when conjugated (d)

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Spectroscopy Data Tables

Calculations of alkane 13C chemical shifts not listed above. sp3 Carbon Chemical Shift Calculations

14

Calculations for sp3 carbon 13C chemical shifts of functionalized carbon skeletons can be performed starting from the actual shifts found in the corresponding alkane skeleton, and introducing corrections factors based on the functionality present in the molecule. This assumes that the alkane 13C shifts are available, which is why several examples are provided below. Examples of Cn alkanes as possible starting points for calculation 13C shifts in ppm.
Steric Corrections for sp3 carbon chemical shift calculations
The attached C carbons are: The calculated carbon atom is: primary primary secondary tertiary quaternary 0 0 0 -1.5 secondary 0 0 -3.7 -8.4 tertiary -1.1 -2.5 -9.5 -15.0 quaternary -3.4 -7.5 -15.0 -25.0 1 6 2 3 4 5 C1 = -2 + 9(1+3) - 2(2) + (-3) = 29 (actual = 28.3) (actual = 34.0) (actual = 47.9) C2 = -2 + 9(4+2) - 2(2) + [3x(-1.5)+(-15.0)] = 28 C3 = -2 + 9(3+5) - 0(2) + [(-9.5)+(-15.0)] = 45 C4 = -2 + 9(3+2) - 3(2) + (-9.5) = 27 C5 = -2 + 9(1+2) - 2(2) + (-1) = 20 C6 = -2 + 9(1+2) - 5(2) + (-1) = 14

Approximate 13C shift calculation from scratch. C = -(2) + 9x(# + #) - 2x(# ) + steric corrections

(actual = 27.2) (actual = 19.5) (actual = 8.5)

13

C shifts for various carbon alkane skeletons - useful starting points for calculating sp3 carbon chemical shifts
C2 C3

CH4

16.3 15.8

C4

25.0 13.8 11.5

25.4 25.0

C5

22.3 22.6 34.4 30.2 31.9 11.8 32.0 29.7 32.0

-2.3 C6

5.9

14.1

22.9 32.9

22.7 27.9 20.6 14.4

29.0 18.8 19.2 30.4 36.5

29.8 48.3 33.4 14.7

8.9 33.9

19.5

14.1

41.5 22.7

36.3

29.3

15.0 18.1 31.8 40.6 26.9 12.0

C7 14.1 22.9

22.9 32.1

29.3

11.4 29.9 14.1 23.1 29.7 34.4 39.2

20.3
17.5

28.1
27.0 9.1 35.3 36.4

39.0

14.5

48.9

27.0

25.6

11.0 25.2 42.3

37.2 38.0

17.9

C8 22.9 14.1 C9 22.8 14.1 32.1 29.6 29.8 14.2 32.1 29.5 22.7 27.2 28.1 39.2 C10 32.3 22.8 14.1 11.5 29.6 34.6 36.5 29.7 19.3 14.1

14.5 20.3

39.6 32.4 19.7 10.9 25.6 40.3 35.4 20.1 14.6

22.9 32.2

29.6 29.9

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Spectroscopy Data Tables

X

15

X is attached to a terminal carbon atom (ppm) Substituent = X

CH3 CH2CH3 CH(CH3)2 C(CH3)3 C H C CH2 CH

X is attached to an internal carbon atom (ppm) C correction C correction 6 9 14 20 15 2 8 6 3 1 5 6 C correction -2 -2 -2 -2 -1 -4

C correction C correction 9 18 26 32 20 5 9 7 4 2 6 5

C correction -2 -2 -2 -2 -1 -4

23

-2

17

-2

X is attached to a terminal carbon atom (ppm) Substituent = X

OH OR O O C R NH2 NH(CH3) N(CH3)2 O H N C R NO2

X is attached to an internal carbon atom (ppm) C correction C correction 44 57 7 5 C correction -4 -6

C correction C correction 48 60 10 7

C correction -6 -6

51

-6

49

-6

28 38 45

10 8 5

-5 -5 -5

24 32 37

8 5 3

-5 -4 -4

26

-5

21

-5

62

-5

58

-5

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Spectroscopy Data Tables

16

X is attached to a terminal carbon atom (ppm) Substituent = X

F Cl Br I O C H O C CH3 O C OH

X is attached to an internal carbon atom (ppm) C correction C correction 67 36 28 7 5 8 10 11 C correction -7 -5 -4 -2

C correction C correction 70 31 20 -7 8 10 10 11

C correction -7 -5 -4 -2

30

-3

24

-1

-3

31

-3

26

-3

22

-3

18

-3

X is attached to a terminal carbon atom (ppm) Substituent = X

O C OCH3 O C NH2 C O C Cl SH SR N

X is attached to an internal carbon atom (ppm) C correction C correction C correction

C correction C correction

C correction

20

-3

16

-3

25

-3

19

-3

-3

-3

33

-3

30

-3

11 22

10 8

-3 -3

12 20

8 6

-3 -3

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Spectroscopy Data Tables

Additional starting point for calculating 13C chemical shifts (ppm) of substituted benzene rings (just a few possibilities) Substituent 128 ppm starting point for benzene carbon 4 3 Substituent -H -CH3 -CH2CH3 -CH2CH2CH3 -CH2CH2CH2CH3 -CH(CH3)2 -C(CH3)3 -CH2F -CH2Cl -CH2Br -CH2I -CH2OH -CH2NH2 -CH2NO2 -CH2CN -CH2SH -CH2CHO -CH2COCH3 -CH2CO2H -CH2=CH2 -CCH -C6H5 -F -Cl -Br -I Z1 0 9 12 10 11 20 19 8 9 9 11 12 15 2 2 12 7 6 6 13 -6 8 34 5 -5 -31 Z2 0 1 -1 0 0 -2 -3 -1 0 1 -1 -1 -1 2 0 -1 1 1 1 -3 4 -1 -13 0 3 9 Z3 0 0 0 0 0 0 0 0 0 0 0 0 0 1 -1 0 0 0 0 0 0 0 2 1 2 2 Z4 0 -3 -3 -3 -3 -3 -3 0 0 0 -1 -1 -2 1 -1 -2 -1 -2 -1 -1 0 -1 -4 2 -1 -1 Substituent -OH -OCH3 -OC6H5 -NH2 -NHCOCH3 -NHOH -NHNH2 -N=N-R -NO -NO2 -SH -SCH3 -S(O)CH3 -SO2CH3 -SO2Cl -CN -CHO -COCH3 -CO2H -CO2CH3 -CONH2 -COCl -Li -MgBr Z1 29 34 28 18 10 22 23 22 37 20 4 10 18 12 16 -16 8 9 2 2 5 11 -43 -36 Z2 -13 -14 -11 -13 -8 -13 -16 -6 -8 -5 1 -2 -5 -1 -2 3 1 0 2 1 -1 0 -13 -11 Z3 1 1 0 1 0 -2 1 0 1 1 0 0 1 1 1 1 0 0 0 0 0 0 2 3 Z4 -7 -8 -7 -10 -4 -5 -10 -3 7 6 -3 -4 2 5 7 4 6 4 5 4 3 -3 3 4 1 2 Use correction term for carbon atom in relative position to the substituent. Start with 128 ppm.

17

Starting points for other common ring systems. (ppm). No correction terms included for substituents. 128 126 134

naphathalene 136 124 150 108 pyrrole N H 118 110 furan O 143 126 thiophene S 125 pyridine

Additional starting point for calculating 13C chemical shifts (ppm) of substituted alkenes (just a few possibilities) 123 ppm starting point for alkene carbon C C C C C ' C ' C ' C C 2 C 1 Z Effect of substituents on alkene 13C shifts (ppm) Substituent -H -CH3 -CH2CH3 -CH2CH2CH3 -CH(CH3)2 -C(CH3)3 -CH2Cl -CH2Br -CH2I -CH2OH -CH=CH2 -CCH -C6H5 Z1 0 13 17 16 23 26 10 11 14 14 14 -6 12 Z2 0 -7 -10 -9 -12 -15 -6 -5 -4 -8 -7 6 -11 Substituent -F -Cl -Br -I -OCH3 -O2CCH3 -N(CH3 )2 -NO2 -CN -SCH2CH3 -CHO -COCH3 -CO2H -COCl Z1 24 3 -9 -38 29 18 28 22 -15 9 15 14 5 8 Z2 -34 -6 -1 7 -39 -27 -32 -1 14 -13 14 5 10 14

123 + correction factors increments for directly attached carbon atoms ' = -8 = 11 ' = -2 =5 '= 2 = -2 steric corrections for each pair of cis-, ' substituents for each pair of geminal-, substituents for each pair of geminal-, 'substituents if one or more sutstituents are present -1 -5 3 2

C = 123 ppm + Zi

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Common fragmentation patterns in mass spectroscopy

1. Branch next to a bond

R C C C C C C C C C Characteristic carboncation stability also applies. 3o R > 2o R > 1o R > CH3

radical cation bond of an alkene or an aromatic

Pi electrons partially fill in loss of electrons at carbocation site via resonance. This is common fragmentation for alkenes and aromatics

2. Branch next to an atom with a lone pair of electrons

R X C radical cation X C X C

X lone pair electrons partially fill in loss of electrons at carbocation site via resonance. This is a common fragmentation for any atom that has a lone pair of electrons (oxygen = alcohol, ether, ester; nitrogen = amine, amide, sulfur = thiol or sulfide, etc.). Alcohols often lose water (M-18) and primary amines can lose ammonia (M-17).

3. Branch next to a carbonyl (C=O) bondand possible subsequent loss of carbon monoxide, CO
O R1 C R2 R2 C O R2 C O R1 C O R1 C O loss of C O R2 subsequent loss of CO is possible after fragmentation so not only can you see loss of an branch you can see the mass of an branch. R1

radical cation R1 or R2 can be lost from aldehydes, ketones, acids, esters, amides...etc.

An oxygen lone pair partially fill in the loss of electrons at the carbocation site via resonance. This is a common fragmentation pattern for any carbonyl compound and can occur from either side, though some are more common than others.

4. McLafferty Rearrangement
O R1 C H C C C R1 H C C C Positive charge can be on either fragment, which typically have an even mass. = alpha position = beta position = gama position

O C

lost neutral still a radical fragment cation This is another common fragmentation pattern for carbonyl compounds (and other pi systems as well: alkenes, aromatics, alkynes, nitriles, etc.). If the pi bond has at least 3 additional nonhydrogen atoms attached and a hydrogen on the "gama" atom, the branch can curve around to a comfortable 6 atom arrangement and the pi bond can pick up a hydrogen atom and cut off a fragment between the C and C positions. The positive charge can be seen on either fragment and usually the fragments have an even mass (unless there is an odd number of nitrogen atoms). radical cation

Knowing these few fragmentation patterns will allow you to make many useful predictions and interpretations. Loss of small molecules, via elimination is common: H2O = 18, H2S = 34, CH3OH = 32, C2H5OH = 46, NH3 = 17, CH3CO2H = 62, HF = 20, HCl = 36/38, HBr = 80/82, etc.
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Spectroscopy Data Tables

A sampling of unusual and/or miscellaneous peaks that are commonly seen, (even when they don't make sense).
R

19

CH3 = 15 CH3CH2 = 29 C3H7 = 43 C4H9 = 57 C5H11 = 71 C6H13 = 85

R C H

mass = 39 (R = H) 53 (R = CH3) 67 (R= CH2CH3) also works for

R H CH2

mass = 41 (R = H) 55 (R = CH3) 69 (R= CH2CH3)

mass = 65 (R = H) 79 (R = CH3) 93 (R= CH2CH3)

mass = 91 (R = H) 105 (R = CH3) 119 (R= CH2CH3)

H2N

O C H2

mass = 44
H

mass = 27

mass = 77

RO

mass = 45 (R = H) 59 (R = CH3) 73 (R= CH2CH3) Loss of small molecules via elimination reactions. H2 O mass = 18 H2 S 34 CH3OH 32 C2H5OH 46 NH3 CH3CO2H 62 17 HF HCl HBr 80 20 36 82 38
H H O R2 R1 R C H2 O

mass = 29 (R = H) 43 (R = CH3) mass = 42 (R = H) 57 (R= CH2CH3) 56 (R = CH3) 71 (R = C3H7) 70 (R= CH2CH3) 105 (R = C6H5)

McLafferty Possibilities
R

Notice! even masses

R

McLafferty
C CH2

R2 R1

HC

=
CH2

mass = 44 (R = H) 58 (R = CH3) 72 (R= CH2CH3) 86 (R = C3H7)

variable mass, (can sometimes see cation on this side too)

mass = 28 (R = H) 42 (R = CH3) 56 (R= CH2CH3) 70 (R = C3H7)

Similar Patterns
H CH2 R2 R1 R C H2 C H2 H R2 R1 C H2 H H C R2 R1 C H2 N H R2 R1

H H2C C R CH2 R2 R1 R

H H R2 R1

H C C

H R2 R1 CH2 N C

H R2 R1 CH2

mass = 42 (R = H) 56 (R = CH3) 70 (R= CH2CH3) 84 (R = C3H7)

mass = 92 (R = H) 106 (R = CH3) 120 (R= CH2CH3) 134 (R = C3H7)

mass = 40 (R = H) 54 (R = CH3) 68 (R= CH2CH3) 82 (R = C3H7)

mass = 41 (R = H) 55 (R = CH3) 69 (R= CH2CH3) 83 (R = C3H7)

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