Nanyang Technological University School of Physical and Mathematical Sciences, Division of Chemistry and Biological Chemistry

CBC DATABOOK

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CONTENTS
Relative Atomic Masses of the Elements Units, Symbols and Constants The International System of Units (SI) Recommended Values of Physical Constants Selected Spectroscopic Data Infrared Characteristic Wavenumbers of Absorptions of Organic Functional Groups Anions and Cations Coordination Compounds Nuclear Magnetic Resonance Properties of Selected NMR-Active Nuclides Chemical Shifts of Common Functional Groups 13 C nuclei 1 H nuclei attached to saturated linkages 1 H nuclei attached to unsaturated linkages 1 H nuclei attached to heteroatoms Additivity Table for 1H Chemical Shifts of Methylene Groups SpinSpin Coupling Constants: 1H1H Ultraviolet and Visible Absorption Maxima of Substituted Benzene Rings WoodwardFieser Rules for the Prediction of max Values Electronic Absorption Characteristics of Transition Metal Complexes Spectrochemical and Trans-Effect Series Mass Spectrometry Common Fragmentations and Fragment Ions Symbols and Abbreviations Commonly Encountered in Organic Chemistry The Proteinogenic Amino Acids Group Theory Symmetry Point Group Flow Diagram Character Tables Physical Definitions and Formulae Mathematical Definitions and Formulae The Greek Alphabet The Periodic Table 2 4 7

8 11 11 12 13 14 15 15 15 16 17 18 19 19 20 21 22 23 24 27 28 31 32

RELATIVE ATOMIC MASSES Ar(E) ('ATOMIC WEIGHTS') OF THE ELEMENTS

(Scaled to Ar(12C) = 12) The atomic weights of many elements are not invariant but depend on the origin and treatment of the material. The footnote to this Table elaborates the types of variation to be expected for individual elements. The values of Ar(E) given here apply to elements as they exist naturally on Earth. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
a

Hydrogen Helium Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon Potassium Calcium

H He Li Be B C N O F Ne Na Al Si P S Cl Ar K Ca

1.00794 4.002602 6.941 9.01218 10.811 12.011 14.00674 15.9994 18.9984032 20.1797 22.989768 24.3050 26.98154 29.0855 30.973762 32.066 35.4527 39.948 39.0983 40.078

a,b,c a,c a,b,c a,b,c c a,c a,c a,b

21 22 23 24 25 26 27 28 29 30 31 32 33

Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton Rubidium Strontium Yttrium Zirconium

Sc Yi V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr

44.955910 47.88 50.9415 51.9961 54.93805 55.847 58.93320 58.69 63.546 65.39 69.723 72.61 74.9216 78.96 79.904 83.80 85.4678 87.62 88.90585 91.224 a a,b a a,c c

c c a,c a

34 35 36 37 38 39 40

J. Emsley. The Elements, 3rd Edition, OUP, 1998. Geologically exceptional specimens are known in which the element has an isotopic composition outside the limits for normal material. The difference between the atomic weight of the element in such specimens and that given in the Table may exceed considerably the implied uncertainty. Modified isotopic compositions may be found in commercially available material because it has been subjected to an undisclosed or inadvertent isotopic separation. Substantial deviations in atomic weight of the element from that given in the Table can occur. Range in isotopic composition of normal terrestrial material prevents a more precise Ar(E) being given; tabulated Ar(E) value should be applicable to any normal material.

41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72
d e *

Niobium Molybdenum Technetium* Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium* Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium

Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf

92.90638 95.94 98.9062 101.07 102.90550 106.42 107.8682 112.411 114.82 118.710 121.75 127.60 126.90447 131.29 132.9054 137.327 138.9055 140.115 140.90765 144.24 145 150.36 151.965 157.25 158.92534 162.50 164.93032 167.26 168.93421 173.04 174.967 178.49 a a a a a d a a a a a a a,b a a a e a

73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium* Astatine* Radon* Francium* Radium Actinium* Thorium* Protactinium* Uranium* Neptinium* Plutonium* Americium* Curium* Berkelium* Californium* Eisteinium* Fermium* Mendelevium* Nobelium* Lawrencium*

Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Fr Ra Ax Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

180.9479 183.85 186.207 190.2 192.22 195.08 196.96654 200.59 204.3833 207.2 208.9804 209 210 222 223 226.0254 227 232.0381 231.03588 238.0289 237.0482 244 243 247 247 251 254 257 258 259 260 d d d d d d d d d d d d d d d d a,c,e e a,b,e a,c a

Radioactive element that lacks a characteristic terrestrial isotopic composition. An element, without stable nuclide(s), exhibiting a range of characteristic terrestrial compositions of long-lived radio-nuclide(s) such that a meaningful atomic weight can be given. Element has no stable nuclides.

UNITS and CONSTANTS

The International System of Units (SI) Physical Quantity Name of Unit SI base units length mass time electric current thermodynamic temperature amount of substance metre kilogram second ampere kelvin mole SI derived units energy, work, heat force pressure, stress power electric charge electric potential electric resistance electric conductance electric capacitance magnetic flux inductance magnetic flux density frequency Celsius temperature () plane angle solid angle joule newton pascal watt coulomb volt ohm siemens farad weber henry tesla hertz degree Celsius radian steradian J N Pa W C V S F Wb H T Hz

Symbol

Expression in terms of SI base units

m kg s A K mol

m2 kg s2 m kg s2 = J m1 m1 kg s2 = N m2 = J m3 m2 kg s3 = J s1 sA m2 kg s3 A1 = J A1 s1 m2 kg s3 A2 = V A1 m2 kg1 s3 A2 = 1 m2 kg1 s4 A2 = A s V1 m2 kg s2 A1 = V s m2 kg s2 A2 = V s A1 kg s2 A1 = V s m2 s1 / (T/K 273.15)

rad sr

SI Prefixes Fraction 101 102 10 10

3 6

Prefix deci centi milli micro nano pico femto atto

Symbol d c m n p f

Multiple 10 102 10 10
3 6

Prefix deca hecto kilo mega giga tera peta exa

Symbol da h k M G T P E

109 1012 1015 1018

109 1012 1015 1018

Decimal Fractions and Multiples of SI Units Having Special Names Physical Quantity length area volume force pressure energy kinematic viscosity (dynamic) viscosity magnetic flux magnetic flux density concentration Name of Unit ngstrm barn litre dyne bar erg stokes poise maxwell gauss Symbol b l dyn bar erg St P Mx G M Definition 1010 m = 101 nm = 100 pm 1028 m2 1203 m3 = 1 dm3 = 1000 cm3 105 N 105 Pa 107 J 104 m2 s1 101 N s m2 108 Wb 104 T 103 mol m3 = mol dm3

Units Defined Exactly in Terms of the SI Units Physical Quantity length mass time time plane angle force pressure pressure pressure pressure pressure energy energy electric dipole moment
a b

Name of Unit inch pound minute hour degree kilogram-force standard atmosphere conventional millimetre of mercuryb torr bar pounds per square inch kilowatt hour thermochemical calorie debye

Symbol in lb min h kgf atm mmHg Torr bar psi kW h calth D

Definitiona 0.0254 m 0.453 592 37 kg 60 s 3600 s (/180) rad 9.806 65 N 101 325 Pa 13.5951 9.806 65 Pa = 133.322 Pa (101 523/760) Pa = 133.322 Pa 105 Pa 6894.757 Pa 3.6 106 J 4.184 J 3.335 64 1030 C m

These definitions are exact. The difference between 1 mmHg and 1 Torr is less than 2 107 Torr.

Recommended Values of Fundamental Constants Fundamental Constant Avogadro constant gas constant Boltzmann constant Faraday constant at T = 298.15 K elementary charge electron volt Planck constant speed of light in vacuuma permeability of a vacuuma permittivity of a vacuuma rest mass of electron rest mass of proton Hartree energy Bohr radius Bohr magneton nuclear magneton Rydberg constant unified atom mass unit gravitational constant standard acceleration due to gravitya
a

Symbol L, NA R k, kB F ( RT/F ) e eV LeV = FV h h = h/2 c o o me mp Eh a0 B = eh/4 me = eh/4 mp R u G g

Value 6.022 1367 1023 mol1 8.314 510 J K1 mol1 1.380 658 1023 J K1 9.648 5309 104 C mol1 0.025 693 V 1.602 177 33 1019 C 1.602 18 1019 J 9.648 547 104 J mol1 6.626 0755 1034 J s 1.054 5726 1034 J s 2.997 924 58 108 m s1 4 107 A2 8.854 187 816 1012 F m1 9.109 3897 1031 kg 1.672 6231 1027 kg 4.359 7482 1018 J 5.291 772 49 1011 m 9.274 0154 1024 J T1 5.050 7866 1027 J T1 109 737.315 34 cm1 1.660 54 1027 kg 6.67259 1011 m3 kg1 9.806 55 m s2

These values are exact.

SPECTROSCOPIC DATA
INFRARED

~ Characteristic Wavenumbers, , of Fundamental Absorptions of Organic Functional Groups

~ /cm1
1. OH stretching free intramolecular hydrogen-bonded single bridges (excluding chelates) intermolecular hydrogen bonded polymeric associations intermolecular chelates and carboxylic acids 2. NH stretching (hydrogen bonding lowers as in OH stretching) primary amides primary amines secondary amides secondary amines 3. CH stretching alkynes alkenes and aryls methyls and methylenes aldehydes 4. CX stretching nitriles alkynes 5. X=Y=Z stretching allenes C=C=C azides RN=N+=N carbon dioxide O=C=O 6. (a) C=O stretching Aldehydes saturated aryl ,-unsaturated 17401720 17001650 17051680 table continued on next page antisymmetric ~1950 21602120 2349 22602220 22602100 two or three bands 3300 30403010 29602850 29002700 two bands two bands ~3500 and 3400 35003300 34603400 34503300 sharp sharp broad broad 36503590 36003450 34003200 32002500

~ Characteristic wavenumbers, , of fundamental absorptions of organic functional groups (continued)

C=O stretching continued (b) Ketones four ring five ring saturated acyclic, alicyclic six-ring and larger, and ,-unsaturated five ring aryl ,-unsaturated (c) Carboxylic acids saturated ,-unsaturated aryl most carboxylate anions (d) Esters and lactones esters of phenols or enols five-ring lactones ,-unsaturated five-ring lactones saturated esters and six-ring and larger lactones esters of aromatic or ,-unsaturated acids (e) Amides and lactams primary amides primary amides (solid phase) secondary amides secondary amides (solid phase) tertiary amides four-ring lactams five-ring lactams six ring and large lactams (f) Anhydrides saturated aryl and ,-unsaturated (g) Acid chlorides saturated aryl and ,-unsaturated 7. C=N stretching imines and oximes variable and of little diagnostic value ~16901640 table continued on next page 18151790 17901750 two bands two bands 18501800 and 17901740 18301780 and 17701710 two bands two bands two bands two bands ~1690 and 1600 1650 and 1640 17001670 and 15501510 16801630 and 15701515 16701630 ~1745 ~1700 ~1670 18001750 17801760 17701740 17501735 17301715 17251700 17151690 17001680 16101550 ~1780 17501740 17251705 17001680 16851660

~ /cm1

10

~ Characteristic wavenumbers, , of fundamental absorptions of organic functional groups (continued)

~ /cm1
8. C=C stretching isolated conjugated aromatic aromatic 9. N=O stretching Nitro compounds asymmetric symmetric 10. Carbonhalogen stretching CF CCl CBr CI 11. CH deformations i-propyl 13851380 13701365 11751165 11701140 t-butyl 13951385 1365 14001000 800 600 600500 500 15551540 13851350 variable one or two bands two bands weak or absent when ring is not further conjugated 16801620 16501590 ~1600 and 1500 1580

12551245 12501200 RCH=CH2 RCH=CHR (trans) R2C=CH R2C=CHR RCH=CHR (cis) RCCH 12. NH bend primary amines and amides 13. PX stretching PH PPh POR P=O 14. BH stretching terminal BH bridging BH 26502450 20901600 24402350 1440 12401030 13001250 16501560 995985 915905

970960 895885 840790 ~690 ~630

11

~ Characteristic Wavenumbers, , of Fundamental Absorptions of Anions and Cations

~ /cm1
ammonium cyanide thiocyanate acetate acetate carbonate nitrate perchlorate sulfate phosphate chromate N-bonded thiocyanate S-bonded thiocyanate [NH4] + [CN]

33003030 14301390 22002000 CN stretch COO antisymmetric stretch COO symmetric stretch

[SCN] [CH3CO2] [CH3CO2] [CO3]

2

21502050 15801550 14301410 14901410 13801350 11701050 11301080 11001000 885

[NO3] [ClO4] [SO4]

2

[PO4] 3 [CrO4]
2

CS stretch CS stretch

860780 720690

~ Characteristic Wavenumbers, , of Fundamental Absorptions in Coordination Compounds ~ /cm1

Transition metal carbonyls: Wavenumber ranges of these CO stretching vibrations apply only to unsubstituted, neutral species. Actual values depend also on the compound and the nature of other ligands attached to the metal. terminal CO bridging CO triply bridging or capping CO MetalX stretching modes MH M=O MF MCl MBr MI 22501700 1050950 750500 400200 300200 200100 21501900 19001750 18001600

12

NUCLEAR MAGNETIC RESONANCE Properties of Selected NMR-Active Nuclides

Nuclide Natural Abundance C I

/ 107 rad T1 s1

Relative Receptivity values for I= nuclei are 3C 1.00 1.45 106 3.93 103 0.133 1.76 104 1.00 103 3.85 106 1.08 105 0.834 9.27 102 0.207 3.69 104 0.067 5.30 104 3.16 105 3.48 105 4.92 105 3.49 103 4.51 103 5.69 103 1.06 105 3.39 103 9.82 104

1 2

99.985% 0.015% 19.58% 80.42% 1.108% 99.63% 0.37% 0.037% 100% 100% 100% 4.70% 100% 7.58% 100% 51.82% 48.18% 7.61% 8.58% 26.44% 14.40% 33.8% 16.84%

1/2 1 3 3/2 1 1 1/2 5/2 1/2 3/2 5/2 1/2 1/2 1/2 1/2 1/2 1/2 1/2 1/2 1/2 1/2 1/2 1/2

26.75 4.11 2.87 8.58 6.73 1.93 2.71 3.63 25.18 7.08 6.98 5.32 10.84 5.12 0.85 1.09 1.25 9.58 10.02 7.44 1.12 5.77 4.82

H, D
10 11 13 14 15 17

B B C

N N O F

19 23

Na Al Si P

27

29

31 77

Se Rh

103 107 109

Ag Ag Sn Sn

117 119 129

Xe W Pt

183

195 199

Hg

13

Chemical Shifts of Common Functional Groups Positions of 1H- and 13C-NMR signals in the following tables are given as chemical shifts, , expressed as parts per million, ppm, relative to tetramethylsilane, TMS. Usual ranges of values for 1H-NMR are 015, except that most MH shifts are < 0. For 1H-NMR, values are usually within 0.2 of those quoted unless inductive, anisotropic or steric effects associated with functional groups operate. Chemical shifts for 13C-NMR are usually 0250.

Chemical Shifts of 13C Nuclei in Common Functional Groups Alkanes Cyclopropanes Cycloalkanes RCH3 RCH2R R2CHR R3CR 08 525 525 2245 3058 2850 160177 162183 185205 190220 525 538 3962 3575 110133 100143 7595 Other Heteroatoms RCH2S Halogens CH3X RCH2X R2CHX R3CX RCH2P ArP ArN ArO RCN 2242 1025 120130 130138 130150 118123 Amines CH3N Carbonyls RCOOR RCOOH RCHO RCOR RCH2N R2CH2N R3CN 1045 4555 5070 6075 Ethers CH3O RCH2O R2CHO R3CO 4560 4270 6577 7083

Unsaturated Compounds Aromatics Alkenes Alkynes

14 Chemical Shifts of Methyl, Methylene and Methine Protons Attached to Saturated Linkages
Methyl CH3C CH3CC=C CH3CO CH3C=C CH3CONR CH3C=CCO CH3COOR CH3S CH3COR CH3I CH3CHO CH3Ar CH3N CH3COOAr 0.9 1.1 1.4 1.6 2.0 2.0 2.0 2.1 2.2 2.2 2.2 2.3 2.3 2.4 CH2COOR CH2CONR CH2CHO CH2C=C CH2CN CH2COR CH2S CH2C=CCO CH2N CH3COAr CH3Br 2.6 2.6 >CHCOR >CHCN >CHN CH3NCOR CH3NAr CH3Cl CH3OR CH3N
+

Methylene

Methine

CH2C CH2CC=C CH2CO

1.4 1.7 1.9

>CHC >CHCO

1.5

2.2 2.2 2.2 2.2 2.3 2.4 2.4 2.4 2.5 2.6 2.7 2.7 2.8 >CHCHO 2.4

CH2Ar

2.9 3.0 3.0 CH2I 3.3 3.3 3.4 CH2OR CH2Br CH2Cl CH2OH 3.4 3.5 3.6 3.6 >CHOR >CHOH >CHCl CH2OCOR CH2OAr 4.1 4.3 >CHOCOR 4.8 >CHBr >CHI 3.7 3.9 4.0 4.1 4.2 3.2 >CHAr >CHS >CHCOAr 3.0 3.2 3.3

CH3OH

CH3OCOR CH3OAr CH3OC=C

3.7 3.8 3.8

Chemical Shift Ranges of Protons Attached to Unsaturated Linkages

Proton CCH CH=CN CH=C=O C=CH C=CHN C=CHCO 1.83.1 3.75.0 4.05.0 4.56.0 5.78.0 5.86.7 Proton C=CHO Aromatic protons CH=CCO HCOO, HCON RCHO, ArCHO 6.08.1 6.09.0 6.57.8 8.08.2 9.410.5

Chemical Shift Ranges of MH, OH and NH Protons Group MH (M = Transition metal) ROH RNH2 RNHR' ArNH2, ArNHR' RCONH2 RCONHCOR' RCO2H Range 300 210 25 3.56 or larger 58.5 9ca. 12 10ca. 13 Often very broad (sometimes unobservable) Often very broad Diagnostic of metal hydride H-bonded enols usually in range 1116 Position depends strongly on solvent

Additivity Table for Estimation of the 1H Chemical Shifts of Methylene Groups (CH2X1X2) = 1.25 + X1 + X2 substituent alkyl vinyl alkynyl phenyl OH OR OPh Xn 0.0 0.8 0.9 1.3 1.7 1.5 2.3 substituent OCOR NH2, NR2 NO2 F Cl Br I Xn 2.7 1.0 3.0 2.1 2.0 1.9 1.4 sustituent SH, SR SO2R -CHO -COR -CO2H -CO2R -CN Xn 1.0 1.7 1.2 1.2 0.8 0.7 1.2

16

H1H SpinSpin Coupling Constants J / Hz J / Hz

H C H

8 to 18a

CH

CH

03

CH

CH

68b 68b

CH

CH

13

H 3C

CH2

CH

CH

46

H3C CH H3C

68b

CH

CH

02

Ha

aa
Heq Heq

813 26

ortho meta
H

69 13 01

ae ee

Ha

26
H H

para

CH

CH

411

cis

512

H
C CH CH C

613
H H

trans

1218

CH

CH

58
H

gem

3 to +3a

The sign of J is unimportant for first-order spectra. Assumes free rotation.

17

ULTRAVIOLET and VISIBLE Absorption band intensities are expressed in terms of the molar absorption coefficient =

A cl

where A = dimensionless absorbance, c = molar concentration, and l = path length of the absorbing species. Units of may therefore be mol1 dm3 cm1 or 103 cm2 mol1. Absorption bands with maxima, max, below 215 nm are observable only as end absorption. Compounds containing unconjugated -bands show only end absorption. Saturated aldehydes and ketones do, however, show a low-intensity band with max = 1030 mol1 dm3 cm1 in the range 275295 nm.

Absorption Maxima of Substituted Benzenes PhR solvent: H2O or MeOH R max

/ nm / mol1 dm3 cm1

max

max
/ nm

/ mol1 dm3 cm1

max

max / nm

/ mol1 dm3 cm1

max

H NH3 Me Cl, Br OH OMe SO2NH2 CN CO2

+

203 203 206 210 210 217 217 224 224 230 230 235 238 248 268 273

7400 7500 7000 7700 6200 6400 9700 13000 8700 11600 8600 9400 10500 1400 7800 21000

254 254 261 262 270 269 264 271 268 273 280 287 282

204 160 225 190 1450 1480 740 1000 560 970 1430 2600 750 291 500

CO2H NH2 O

NHAc CH=CH2 NO2 (E)-CH=CHCO2H

18 WoodwardFieser Rules for the Prediction of max Values for * Transitions of Dienes, Polyenes and ,-Unsaturated Aldehydes, Ketones and Acids
Basic Chromophore: Diene Diene max (EtOH) / nm 214 Increment / nm Each additional double bond extending the conjugation Each homoannular diene
a b

30 39 5 5

The exocyclic nature of any double bond Each alkyl group or ring residue Each auxochrome:

OAcyl OAlkyl SAlkyl Cl, Br NAlkyl2

0 6 30 5 60 max (EtOH) / nm 215 202 209 197 Increment / nm

Basic Chromophore: , -unsaturated Aldehydes, Ketones and Acids Six-ring or acyclic ,-unsaturated ketone Five-ring ,-unsaturated ketone ,-unsaturated aldehyde ,-unsaturated acid

Each additional double bond extending the conjugation Each homoannular diene
a b

30 39 5 10 12 18 35 30 50 6 35 30 17 31 85 15 12 25 30 95
b

The exocyclic nature of any double bond Each alkyl group or ring residue

for aldehydes and ketones only Each auxochrome: OH

OAcyl OAlkyl

, ,

SAlkyl Cl Br NAlkyl2
a

Exocyclic double bond:

Homoannular diene:

19

Typical Electronic Absorption Intensities of Transition Metal Complexes Type of Transition Spin-forbidden, Laporte forbidden Spin-allowed, Laporte forbidden Spin-allowed, Laporte forbidden, but with dp mixing (Td symmetry) and/or intensity stealing Spin-allowed, Laporte allowed; charge transfer max / mol1 dm3 cm1 0.011.0 1.0100 1001000 > 1000

Spectrochemical Series Common Ligands I < Br <Cl < S2~ SCN <F < OH < O2 ~ H2O < NCS < py < NH3 < ethylenediamine (en) < bipyridine (bipy), PR3 < CH3 < CN CO Metal Ions Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Cr3+ < V3+ < Co3+ < Mn4+ < Mo3+ < Rh3+ < Ru3+ < Pd4+ < Ir3+ < Re4+ < Pt4+ o values for metals of the first transition series are typically in the ranges M2+: 700016000 cm1 and M3+: 1300026000 cm1 for all but the strongest ligands. In any group o increases with atomic mass of the metal, i.e. 3d < 4d < 5d. For tetrahedral complexes, t
4 9

o .

3 (3+ ion) 2 (2+ ion) for isoelectronic ions.

The Trans-Effect Series CN , CO > PR3, H > CH3 > C6H5 > NO2 , I > Br > Cl > py, NH3 > OH > H2O

20

MASS SPECTROMETRY Common Fragmentations and Fragment Ions in Mass Spectrometry Common Fragmentations m/z
M 3 to M 14 M 15 M 17 CH3 OH NH3 M 18 M 26 H2O C2H2 CN M 31 M 35 or M 37 M 43 M 58 M 77 M 79 or M 81 M 91 M 105 M 127 CH3O Cl CH3CO nitrile, odd molecular weight methyl ester or ether a molecular ion consisting of two peaks of intensity 3:1, two mass units apart, indicates a monochloro compound methyl ketone alcohol or carboxylic acid primary amine, odd molecular weight alcohol, aldehyde, ketone

Fragment Lost

Inference
highest mass peak observed is itself a fragment and not a molecular ion

CH2=C(OH)CH3 McLafferty rearrangement, methyl ketone with -hydrogen C6H5 Br C7H7 C6H5CO I monosubstituted a molecular ion consisting of two peaks of equal intensity, two mass units apart, indicates a monobromo compound benzylic aromatic ketone or ester

Fragment Ions m/z

18 28 30 31 57 58 65 77 91

Fragment
H2O+ CO+, C2H4+, N2+ CH2NH2+ CH2OH+ C4H9
+

Inference

primary amine, odd molecular weight primary alcohol tert-butyl group

CH2=C(OH)CH3 methyl ketone C5H5+ C6H5 C7H7

+ +

secondary fragment from tropylium ion monsubstituted aromatic tropylium ion, usually the base peak

SYMBOLS AND ABBREVIATIONS COMMONLY ENCOUNTERED IN ORGANIC CHEMISTRY Groups

R Me Et Pr i-Pr Bu, n-Bu i-Bu s-Bu, sec-Bu t-Bu, tert-Bu Ar Ph () Ac Bn Boc, BOC or t-Boc Bz Ms Tf Ts TMS TBDPS TBS THP Z alkyl methyl ethyl propyl isopropyl butyl isobutyl sec-butyl tert-butyl aryl phenyl acetyl (ethanoyl) benzyl t-butoxycarbonyl benzoyl mesyl (methanesulfonyl) triflyl (trifluoromethanesulfonyl) tosyl (toluenesulfonyl) trimethylsilyl (or tetramethylsilane in NMR) tert-butyldiphenylsilyl tert-butyldimethylsilyl (also seen as TBDMS) tetrahydropyranyl benzyloxycarbonyl or Cbz C6H5CH2OCO generalised alkyl group CH3 CH2CH3 CH2CH2CH3 CH(CH3) 2 CH2CH2CH2CH3 CH2CH(CH3) 2 CH(CH3)CH2CH3 C(CH3)3 generalised aromatic ring C6H5 COCH3 CH2C6H5 COOC(CH3)3 COC6H5 SO2CH3 SO2CF3 SO2C6H4CH3 (para) Si(CH3)3 SiPh2C(CH3)3 Si(CH3)2C(CH3)3

Reagents, Solvents and Others

aq. n-BuLi or nBuLi cat. D DIBAL DMAP DMF DMSO DCM Et2O EI FAB aqueous n-butyllithium catalyst or catalytic deuterium diisobutylaluminium hydride 4-dimethylaminopyridine N,N-dimethylformamide dimethyl sulfoxide dichloromethane diethyl ether electron impact (ionisation) fast-atom bombardment HMPA h IR LDA mCPBA NMR PCC PDC TBAF TFA THF hexamethylphosphoramide light infrared lithium diisopropylamide meta-chloroperoxybenzoic acid nuclear magnetic resonance pyridinium chlorochromate pyridinium dichromate tetra-n-butylammonium fluoride trifluoroacetic acid tetrahydrofuran heat

THE PROTEINOGENIC AMINO ACIDS

R H R H or in zwitterionic form H3N CO2

For the generalised L-amino acid structure:

H2N

CO2H

All have S absolute configuration except cysteine which is R

Amino Acid
Glycine (Gly or G) Alanine (Ala or A)

R
HCH3H3C CH3

Amino Acid
Cysteine (Cys or C) Methionine (Met or M)

R
HS

H3CS
HN

Valine (Val or V)

Histidine (His or H)

CH3

Leucine (Leu or L)

H3C

Lysine (Lys or K)
CH3 H

H2N
H N NH

Isoleucine (Ile or I)

H3C

Arginine (Arg or R)

H2N

Phenylalanine (Phe or F)
HN

Aspartic acid (Asp or D)

HO2C

Tryptophan (Trp or W)

Glutamic acid (Glu or E)

HO2C

HO

Serine (Ser or S)
CH3 OH

Asparagine (Asn or N)

H2N

Threonine (Thr or T)

H
HO

H2N

Glutamine (Gln or Q)

Tyrosine (Tyr or Y)

L-Proline: Proline (Pro or P):

N H H CO2 H or N H2 H CO2

23

24

GROUP THEORY
Character Tables CS = Ch A' A" E 1 1 h 1 1 x, y, Rz z, Rx, Ry x2, y2, z2, xy yz, xz

C2v A1 A2 B1 B2

E 1 1 1 1

C2 1 1 1 1

v(xz) 1 1 1 1

'v(yz) 1 1 1 1 z Rz x, Ry y, Rx x2 , y2 , z2 xy xz yz

C3v A1 A2 E

E 1 1 2

2C3 1 1 1

3v 1 1 0 z Rz (x, y), (Rx, Ry) (x2 y2, xy) (xz, yz) x2 + y 2 , z2

C4v A1 A2 B1 B2 E

E 1 1 1 1 2

2C4 1 1 1 1 0

C2 1 1 1 1 2

2v 1 1 1 1 0

2d 1 1 1 1 0 (x, y), (Rx, Ry) z Rz x2 y2 xy (xz, yz) x2 + y 2 , z2

C5v A1 A2 E1 E2

E 1 1 2 2

2C5 1 1

2C52 1 1

5v 1 1 0 0 z Rz (x, y), (Rx, Ry) (xz, yz) (x2 y2, 2xy) x2 + y 2 , z2

2 cos 72 2 cos 144 2 cos 144 2 cos 72

25

D2h Ag B1g B2g B3g Au B1u B2u B3u

E 1 1 1 1 1 1 1 1

C2(z) 1 1 1 1 1 1 1 1

C2(y) 1 1 1 1 1 1 1 1

C2(x) 1 1 1 1 1 1 1 1

i 1 1 1 1 1 1 1 1

v(xy) 1 1 1 1 1 1 1 1

v(xz) 1 1 1 1 1 1 1 1

v(yz) 1 1 1 1 1 1 1 1 z y x Rz Ry Rx x2 , y2 , z2 xy xz yz

D3h A'1 A'2 E' A"1 A"2 E"

E 1 1 2 1 1 2

2C3 1 1 1 1 1 1

3C2 1 1 0 1 1 0

h 1 1 2 1 1 2

2S3 1 1 1 1 1 1

3v 1 1 0 1 1 0 z (Rx, Ry) (xz, yz) Rz (x, y) (x2 y2 , 2xy) x2 + y2 , z2

D4h A1g A2g B1g B2g Eg A1u A2u B1u B2u Eu

E 1 1 1 1 2 1 1 1 1 2

2C4 C 2 1 1 1 1 0 1 1 1 1 0 1 1 1 1 2 1 1 1 1 2

2C'2 2C"2 1 1 1 1 0 1 1 1 1 0 1 1 1 1 0 1 1 1 1 0

i 1 1 1 1 2 1 1 1 1 2

2S4 1 1 1 1 0 1 1 1 1 0

h 1 1 1 1 2 1 1 1 1 2

2v 1 1 1 1 0 1 1 1 1 0

2d 1 1 1 1 0 1 1 1 1 0 (x, y) z (Rx, Ry) Rz x2 y2 xy (xz, yz) x2 + y 2 , z2

26

D2d = Vd A1 A2 B1 B2 E

E 1 1 1 1 2

2S4 1 1 1 1 0

C2 1 1 1 1 2

2C'2 1 1 1 1 0

2d 1 1 1 1 0 z (x, y), (Rx, Ry) Rz x2 y2 xy (xz, yz) x2 + y 2 , z2

Cv A1 + A2 E1 E2 E3

E 1 1 2 2 2

C2 1 1 2 2 2

2C 1 1

v 1 0 0 0 z Rz (x, y), (Rx, Ry) (xz, yz) (x2 y2, xy) x2 + y2 , z2 1

2 cos 2 cos 2 2 cos 3

Dh g
+

E 1 1 2 2

2C 1 1
2 cos

v 1 0 0 1 0 0 1

i 1 1 2 2 1 1 2 2

2S 1 1

C2 1 Rz (Rx, Ry) (xz, yz) (x2 y2, 2xy) z (x, y) 0 0 1 0 0 x2 + y 2 , z2 1

g g g u u
+

2 cos 2 cos 2

2 cos 2

1 1 2 2

1 1
2 cos

1 1
2 cos

u u

2 cos 2

2 cos 2

27

PHYSICAL DEFINITIONS AND FORMULAE

Classical Mechanics

F =m a W =F x
p=m v

Newtons Second Law

F = force, m = mass, a = acceleration W = work done, F = force, x = distance moved p = momentum, m = mass, v = velocity

T = 1 m v2 = 2
P= P= F A

p2 2m

T = kinetic energy, m = mass, v = velocity, p = momentum P = pressure, F = force, A = area P = pressure, m = mass, g = acceleration due to gravity, A = area = density, m = mass, V = volume P = pressure exerted by a column of density and height h where g = acceleration due to gravity, A = area, V = volume Electrical Energy

mg A m V

= P=

mg V g = =gh A A

V =I R
E =V I t =
W=

Ohms Law

V = electrical potential I = current, R = resistance E = energy, V = electrical potential I = current, t = time, R = resistance W = power, E = energy, t = time Electrostatics

V2t 2 = I Rt R
E t

V=
F=

q1 q2 4 0 r
q1 q2 4 0 r 2

Coulombs Law

V = potential energy of two charges q1 and q2 separated by r, for a medium of permittivity, 0

F = force acting between two charges q1 and q2 separated by r, for a medium of permittivity, 0





 

   
   




   
  
  



        
         
             
         
        

      

      


 
       
 



  

  

              
 
                  
  
  
 

     



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32

PERIODIC TABLE OF THE ELEMENTS

1 2

H
3 4 5 6 7 8 9

He
10

Li Be
11 12

B
13 21 22 23 24 25 26 27 28 29 30 31

C
14 32

N
15

O
16 17

F Ne
18

Na Mg
19 20

Al Si
33 39 40 41 42 43 44 45 46 47 48 49 50 51

P
34 52

Cl Ar
35 36 53 54

K Ca Sc Ti
37 38

V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr I
85

Rb Sr
55 56 87 88

Y
57 89

Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te
72 73 74 75 76 77 78 79 80 81 82 83 84 104 105 106 107 108 109

Xe
86

Cs Ba La Hf Ta W Re Os Ir Fr Ra Ac Rf Db Sg Bh Hs Mt
58 59 60 61 62 63

Pt Au Hg Tl Pb Bi Po At Rn

64

65

66

67

68

69

70

71

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 96 97 98 99 100 101 102 103

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr