CHAPTER

Nuclear Magnetic Resonance Spectroscopy

CONTENTS Properties of Important NMR Nuclei Gyromagnetic Ratio of Some Important Nuclei Classication of Important Quadrupolar Nuclei According to Natural Abundance and Magnetic Strength Chemical Shift Ranges of Some Nuclei Reference Standards for Selected Nuclei 1H and 13C Chemical Shifts of Useful Solvents for NMR Measurements Proton NMR Absorption of Major Chemical Families Organic Nitrogen Compounds Some Useful 1H Coupling Constants Additivity Rules in 13C NMR Correlation Tables 13C NMR Absorptions of Major Functional Groups 13C NMR Chemical Shifts of Organic Families 15N Chemical Shifts for Common Standards 15N Chemical Shifts of Major Chemical Families SpinSpin Coupling to 15N 19F Chemical Shift Ranges 19F Chemical Shifts of Some Fluorine-Containing Compounds Fluorine Coupling Constants Residual Peaks Observed in the 1H NMR Spectra of Common Deuterated Organic Solvents

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PROPERTIES OF IMPORTANT NMR NUCLEI The following table lists the magnetic properties required most often for choosing the nuclei to be used in NMR experiments.114 Refer to several excellent texts and the literature for guidelines in nucleus selection.

REFERENCES
1. Silverstein, R.M., Bassler, G.C., and Morrill, T.C., Spectrometric Identication of Organic Compounds, 5th ed., John Wiley & Sons, New York, 1991. 2. Yoder, C.H. and Shaeffer, C.D., Introduction to Multinuclear NMR, Benjamin/Cummings, Menlo Park, CA, 1987. 3. Gordon, A.J. and Ford, R.A., The Chemists Companion, Wiley Interscience, New York, 1971. 4. Silverstein, R.M. and Webster F.X., Spectrometric Identication of Organic Compounds, 6th ed., John Wiley & Sons, New York, 1998. 5. Becker, E.D., High Resolution NMR, Theory and Chemical Applications, 2nd ed., Academic Press, New York, 1980. 6. Gunther, H., NMR Spectroscopy: Basic Principles, Concepts and Applications in Chemistry, John Wiley & Sons, New York, 2003. 7. Rahman, A.-U., Nuclear Magnetic Resonance, Springer-Verlag, New York, 1986. 8. Harris, R.K., NMR and the periodic table, Chem. Soc. Rev., 5, 1, 1976. 9. Kitamaru, R., Nuclear Magnetic Resonance: Principles and Theory, Elsevier Science, Amsterdam, 1990. 10. Lambert, J.B., Holland, L.N., and Mazzola, E.P., Nuclear Magnetic Resonance Spectroscopy: Introduction to Principles, Applications and Experimental Methods, Prentice Hall, Englewood Cliffs, NJ, 2003. 11. Bovey, F.A. and Mirau, P.A., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., Academic Press, New York, 1988. 12. Harris, R.K. and Mann, B.E., NMR and the Periodic Table, Academic Press, London, 1978. 13. Hore, P.J. and Hore, P.J., Nuclear Magnetic Resonance, Oxford University Press, Oxford, 1995. 14. Nelson, J.H., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., John Wiley & Sons, New York, 2003.

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Properties of Important NMR Nuclei Natural Abundance 99.985 0.015 1.108 99.635 0.365 0.037 100 4.70 100 0.76 75.53 50.54 49.46 14.40 Spin Number I 1/2 1 1/2 1/2 1 1/2 5/2 1/2 1/2 1/2 3/2 3/2 3/2 2 1 3/2 3/2 1/2 NMR Frequencya at Indicated Field Strength in kG 14.092 21.139 23.487 51.567 60.0000 9.21037 63.9980 15.0866 4.3343 6.0798 8.134 42.3537 11.9191 24.288 4.6018 7.16 5.8790 6.8956 5.89 15.032 16.204 2.4966 90.0000 13.81555 95.9971 22.6298 6.5014 9.1197 12.201 63.5305 17.8787 36.433 6.9026 10.74 8.8184 10.3434 8.84 22.549 24.305 3.7449 100.0000 15.35061 106.6634 25.1443 7.2238 10.1330 13.557 94.0769 19.8652 40.481 7.6696 11.932 9.7983 11.4927 9.82 25.054 27.006 4.1610 220.0000 33.77134 234.6595 55.3174 15.924 22.2925 29.825 206.9692 43.7035 89.057 16.8731 26.250 21.5562 25.2838 21.60 55.119 59.413 9.1543

Isotope H1 2 1H 3b 1H 13 C 6 14 7N 15 N 7 17 8O 19 F 9 29 14Si 31 P 15 33 16S 35 b S 16 35 17Cl 36 b Cl 17 76 b 35Br 79 Br 35 81 35Br 183 W 74

1

10.000

42.5759 6.53566 45.4129 10.7054 3.0756 4.3142 5.772 40.0541 8.4578 17.235 3.2654 5.08 4.1717 4.8931 4.18 10.667 11.498 1.7716

Isotope H1 H2 3b 1H 13 6C 14 N 7 15 7N 17 O 8 19 9F 29 14Si 31 15P 33 16S 35 b 16S 35 Cl 17 36 b 17Cl 76 b Br 35 79 35Br 81 Br 35 183 74W

1 1 a b c

Field Valuea (kg) at Frequency of 4 MHz 10 MHz 16 MHz 0.940 6.120 0.881 3.736 13.01 9.272 6.93 0.999 4.729 2.321 12.25 7.87 9.588 0.175 9.6 3.750 3.479 22.58 2.349 15.30 2.202 9.341 32.51 23.18 17.3 2.497 11.82 5.802 30.62 19.7 23.97 20.44 24 9.375 8.697 56.45 3.758 24.48 3.523 14.946 52.02 37.09 27.7 3.994 18.92 9.284 49.0 31.5 38.35 32.70 38 15.00 13.92 90.31

Relative Sensitivity Constant H Constant 1.00 9.65 103 1.21 0.0159 1.01 103 1.04 103 0.0291 0.834 7.84 103 0.0665 2.26 103 8.50 103 4.72 103 0.0122 2.52 103 0.0794 0.0994 7.3 105 1.00 0.409 1.07 0.252 0.193 0.101 1.58 0.941 0.199 0.405 0.384 0.597 0.490 0.920 0.26 1.26 1.35 0.042

Magnetic Moment (eh/4Mc) 2.79278 0.85742 2.9789 0.7024 0.4036 0.2831 1.8937 2.6288 0.55477 1.1317 0.6533 1.00 0.82183 1.285 0.548 2.106 2.270 0.117

Electric Quadrupole Momentc (barns) 0.0028 0.01 0.026 0.055 0.04 0.079 0.017 0.25 0.31 0.26

1 kG = 1010 T, the corresponding SI unit. Nucleus is radioactive. 1 b = 1023 m2.

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GYROMAGNETIC RATIO OF SOME IMPORTANT NUCLEI The following table lists the gyromagnetic ratio, , of some important nuclei that are probed in NMR spectroscopy.112 The gyromagnetic ratio is the proportionality constant that correlates the magnetic moment () and the angular momentum, : = .

REFERENCES
1. Carrington, A. and McLaughlin, A., Introduction to Magnetic Resonance, Harper and Row, New York, 1967. 2. Levine, I.M., Molecular Spectroscopy, John Wiley & Sons, New York, 1975. 3. Becker, E.D., High Resolution NMR: Theory and Chemical Applications, Academic Press, New York, 1980. 4. Yoder, C.H. and Shaeffer, C.D., Introduction to Multinuclear NMR, Benjamin/Cummings, Menlo Park, CA, 1987. 5. Silverstein, R.M. and Webster F.X., Spectrometric Identication of Organic Compounds, 6th ed., John Wiley & Sons, New York, 1998. 6. Rahman, A.-U., Nuclear Magnetic Resonance, Springer-Verlag, New York, 1986. 7. Kitamaru, R., Nuclear Magnetic Resonance: Principles and Theory, Elsevier Science, Amsterdam, 1990. 8. Lambert, J.B., Holland, L.N., and Mazzola, E.P., Nuclear Magnetic Resonance Spectroscopy: Introduction to Principles, Applications and Experimental Methods, Prentice Hall, Englewood Cliffs, NJ, 2003. 9. Bovey, F.A. and Mirau, P.A., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., Academic Press, 1988. 10. Hore, P.J. and Hore, P.J., Nuclear Magnetic Resonance, Oxford University Press, Oxford, 1995. 11. Nelson, J.H., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., John Wiley & Sons, New York, 2003. 12. Gunther, H., NMR Spectroscopy: Basic Principles, Concepts and Applications in Chemistry, John Wiley & Sons, New York, 2003.
Gyromagnetic Ratio of Some Important Nuclei Nucleus H1 H2 3 1H 7 3Li 10 B 5 11 5B 13 C 6 14 7N 15 N 7 17 8O 19 F 9 29 14Si 23 Na 11 31 15P 33 16S 35 17Cl 37 Cl 17 39 19K 79 35Br 81 35Br 183 W 74
1 1

5.5856 0.8574 5.9575 2.1707 0.6002 1.7920 1.4044 0.4035 0.5660 0.7572 5.2545 1.1095 1.4774 2.2610 0.4284 0.5473 0.4555 0.2607 1.3993 1.5084 0.2324

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CLASSIFICATION OF IMPORTANT QUADRUPOLAR NUCLEI ACCORDING TO NATURAL ABUNDANCE AND MAGNETIC STRENGTH The following table classies important quadrupolar nuclei according to their natural abundance and relative magnetic strength.1 The magnetic strength, while not a commonly recognized physical parameter, is dened as a matter of convenience for classication of nuclei in NMR. It is dened as follows:
Strong /107 > 2.5 rad T1sec1 Medium 10 rad T1sec1 > 107 > 2.5 rad T1sec1 Weak 107 < 2.5 rad T1sec1

where the ux density in units of tesla (T) and rad refers to 2. In NMR, one can write: 2f = B where f is the resonant frequency, is the gyromagnetic ratio, and B is the ux density. Thus, for the proton, /2 = 43 MHz/T, resulting in a value of /107 = 4.3 rad B1sec1, and therefore medium magnetic strength. The less favorable nuclei for a given element are listed in brackets.

REFERENCES
1. Harris, R.K. and Mass, B.E., NMR and the Periodic Table, Academic Press, London, 1978.
Classication of Important Quadrupolar Nuclei According to Natural Abundance and Magnetic Strength Magnetic Strength Strong Medium
7

High (>90%) Li Be, 23Na, 27Al, 45Sc, 51V, 55Mn, 59Co, 75As, 93Nb, 115In, 127I, 133Cs, 181Ta, 209Bi

Natural Abundance Medium

Low (<10%)

[10B], 11B, 35Cl, 63Cu, 65Cu, [69Ga], 71Ga, [79Br], 81Br, [85Rb], 87Rb, 121Sb, [123Sb], 137Ba, 139La, [185Re], 187Re
25

H, 6Li, 17O, [135Ba]

21

Ne, [113In],

Weak

14

N,

39

189

Mg, 37Cl, 83Kr, Os, 201Hg

95

Mo,

131

Xe,

33

67

S, [41K], 43Ca, 47Ti, 49Ti, 53Cr, Zn, 73Ge, 87Sr, [97Mo]

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CHEMICAL SHIFT RANGES OF SOME NUCLEI The following table gives an approximate chemical shift range (in ppm) for some of the most popular nuclei. The range is established by the shifts recorded for the most common compounds.l11

REFERENCES
1. Yoder, C.H. and Schaeffer, C.D., Jr., Introduction to Multinuclear NMR, Benjamin/Cummings Publishing Co., Menlo Park, CA, 1987. 2. Silverstein, R.M., Bassler, G.C., and Morrill, T.C., Spectrometric Identication of Organic Compounds, 5th ed., John Wiley & Sons, New York, 1991. 3. Harris, R.U. and Mann, B.E., NMR and the Periodic Table, Academic Press, London, 1978. 4. Silverstein, R.M. and Webster F.X., Spectrometric Identication of Organic Compounds, 6th ed., John Wiley & Sons, New York, 1998. 5. Gunther, H., NMR Spectroscopy: Basic Principles, Concepts and Applications in Chemistry, John Wiley & Sons, New York, 2003. 6. Kitamaru, R., Nuclear Magnetic Resonance: Principles and Theory, Elsevier Science, New York, 1990. 7. Lambert, J.B., Holland, L.N., and Mazzola, E.P., Nuclear Magnetic Resonance Spectroscopy: Introduction to Principles, Applications and Experimental Methods, Prentice Hall, Englewood Cliffs, NJ, 2003. 8. Bovey, F.A. and Mirau, P.A., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., Academic Press, New York, 1988. 9. Harris, R.K. and Mann, B.E., NMR and the Periodic Table, Academic Press, London, 1978. 10. Hore, P.J. and Hore, P.J., Nuclear Magnetic Resonance, Oxford University Press, Oxford, 1995. 11. Nelson, J.H., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., John Wiley & Sons, New York, 2003.
Chemical Shift Ranges of Some Nuclei Nucleus
1 7

Chemical Shift Range, ppm 15 10 200 250 930 700 800 15 270

Nucleus
29 31

Chemical Shift Range, ppm 400 700 600 820 60 14,000 2000 150 10,000

H Li 11B 13C 15N 17O 19F 23Na 27Al

Si P 33S 35Cl 39K 59Co 119Sn 133Cs 207Pb

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REFERENCE STANDARDS FOR SELECTED NUCLEI The following table lists the most popular reference standards used when NMR spectra of various nuclei are measured. The standards should be inert, soluble in a variety of solvents, and, preferably, produce one singlet peak that appears close to the lowest-frequency end of the chemical shift range. When NMR data are provided, it is always necessary to specify the reference standard employed.16

REFERENCES
1. Yoder, C.H. and Schaeffer, C.D., Jr., Introduction to Multinuclear NMR, Benjamin/Cummings Publishing Co., Menlo Park, CA, 1987. 2. Duthaler, R.O. and Roberts, J.D., Steric and electronic effects on 15N chemical shifts of piperidine and decahydroquinoline hydrochlorides, J. Am. Chem. Soc., 100, 3889, 1978. 3. Grim, S.O. and Yankowsky, A.W., On the phosphorus-31 chemical shifts of substituted triarylphosphines, Phosphorus Sulfur, 3, 191, 1977. 4. Lambert, J.B., Shurrell, H.F., Verbit, L., Cooks, R.G., and Stout, G.H., Organic Structural Analysis, MacMillan, New York, 1976. 5. Gunther, H., NMR Spectroscopy: Basic Principles, Concepts and Applications in Chemistry, John Wiley & Sons, New York, 2003. 6. Abraham, R.J., Fisher, J., and Loftus, P., Introduction to NMR Spectroscopy, John Wiley & Sons, New York, 1988.
Reference Standards for Selected Nuclei Nucleus
1

Name Tetramethylsilane [TMS] 3-(Trimethylsilyl)-1-propanesulfonic acid, sodium salt [DSS]a 3-(Trimethylsilyl)-propanoic acid, d4, sodium salt [TSP] Deuterated chloroform [chloroform-d] Boric acid Boron triuoride etherate Boron trichloride Tetramethylsilane [TMS] Ammonium nitrate Ammonia Nitromethane Nitric acid Tetramethylammonium chloride Water Trichlorouoromethane [Freon 11, R-11] Hexauorobenzene Trimethylphosphite [methyl phosphite] Phosphoric acid (85%) Sodium chloride Cobalt (III) hexacyanide anion Tetramethyltin Platinum (IV) hexacyanide Dihydrogen platinum (IV) hexachloride Sodium tungstate (external)

Formula (CH3)4Si (CH3)3Si(CH2)3SO3Na (CH3)3Si(CD2)3CO2Na CDCl3 H3BO3 (C2H5)2OBF3 BCl3 (CH3)4Si NH4NO3 NH3 CH3NO2 HNO3 (CH3)4NCl H 2O CCl3F C 6F 6 (CH3O)3P H3PO4 NaCl [Co(CN)6]3 (CH3)4Sn [Pt(CN)6]2 H2PtCl6 Na2WO4

11

H B

13 15

C N

17 19

O F P

31

35

Cl Co 119Sn 195Pt
59 183 a

For aqueous solutions (known also as water-soluble TMS or 2,2-dimethyl-2-silapentane-5sulfonate).

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H AND 13C CHEMICAL SHIFTS OF USEFUL SOLVENTS FOR NMR MEASUREMENTS

The following table lists the expected 1H(H) and 13C(C) chemical shifts for various useful NMR solvents in parts per million (ppm). The table also includes the liquid temperature range (C) and dielectric constants of these solvents. Slight changes may occur with changes in concentration.

REFERENCES
1. Silverstein, R.M., Bassler, G.C., and Morrill, T.C., Spectrometric Identication of Organic Compounds, 5th ed., John Wiley & Sons, New York, 1991. 2. Rahman, A.-U., Nuclear Magnetic Resonance: Basic Principles, Springer-Verlag, New York, 1986. 3. Abraham, R.J., Fisher, J., and Loftus, P., Introduction of NMR Spectroscopy, John Wiley & Sons, Chichester, U.K., 1988.
1

H and

13

C Chemical Shifts of Useful Solvents for NMR Measurements Liquid Temperature Range (C) 95 to 56 44 to 82 6 to 80 112 to 46 23 to 77 64 to 61 6 to 81 95 to 40 140 to 25 60 to 153 19 to 189 12 to 101 7 to 233 98 to 65 6 to 211 29 to 101 42 to 115 44 to 146 108 to 66 17 to 214 111 to 24 154 to 13 15 to 72 0 to 100 Dielectric Constant, 20.7 37.5 2.284 2.641 2.238 4.806 2.023 9.08 Chemical Shifts C (ppm) H (ppm) 2.17 2.00 7.27 7.25 1.43 5.33 2.9, 3.0, 8.0 2.62 3.7 2.60 3.4, 4.8a 8.2, 7.6, 7.5 4.33 7.0, 7.6, 8.6 5.94 1.9, 3.8 7.1, 7.3, 7.4 29.2, 204.1 1.3, 117.7 128.4 192.3 96.0 76.9 27.5 53.6 109.2 31, 36, 132.4 39.6 67.4 36.8 49.3 149, 134, 129, 124 57.3 124, 136, 150 75.5 25.8, 67.9 133.3, 132.8, 130.7, 130.0, 127.6 117.6 126, 117 114.5, 116.5

Solvent Acetone-d6 Acetonitrile-d3 Benzene-d6 Carbon disulde Carbon tetrachloride Chloroform-d3 Cyclohexane-d12 Dichloromethane-d2 Diuorobromochloromethane Dimethylformamide-d7 Dimethylsulfoxide-d6 1,4-Dioxane-d8 HMPA Methanol-d4 Nitrobenzene Nitromethane-d3 Pyridine-d5 1,1,2,2-Tetrachloroethane-d2 Tetrahydrofuran-d8 1,2,4-Trichlorobenzene

Formula (CD3)2CO CD3CN C 6D 6 CS2 CCl4 CDCl3 C6D12 CD2Cl2 CF2BCl DCON(CD3)2 (CD3)2SO C 4D 8O 2 CD3OD C6D5NO2 CD3NO2 C 5D 5N CD2ClCD2Cl C 4D 8O C6D3Cl3 CFCl3 CD2=CDCl CF3COOD D 2O

36.7 46.7 2.209 30.0 32.63 34.8 35.87 123 8.2 7.54 3.9

Trichlorouoromethane Vinyl chloride-d3 Triuoroacetic acid, d Water-d2

a

2.3 8.6 78.5

5.4, 5.5, 6.3 11.3a 4.7

Variable with concentration.

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PROTON NMR ABSORPTION OF MAJOR CHEMICAL FAMILIES The following tables give the region of the expected nuclear magnetic resonance absorptions of major chemical families. These absorptions are reported in the dimensionless units of parts per million (ppm) vs. the standard compound tetramethylsilane (TMS), which is recorded as 0.0 ppm:
CH3 CH3 Si CH3 CH3

The use of this unit of measure makes the chemical shifts independent of the applied magnetic eld strength or the radio frequency. For most proton NMR spectra, the protons in TMS are more shielded than almost all other protons. The chemical shift in this dimensionless unit system is then dened by

s r 10 6 r

where vs and vr are the absorption frequencies of the sample proton and the reference (TMS) protons (12, magnetically equivalent), respectively. In these tables, the protons whose proton NMR shifts are cited are indicated by an underline. For more detail concerning these conventions, refer to the general references below.111

REFERENCES
1. Silverstein, R.M. and Webster, F.X., Spectrometric Identication of Organic Compounds, 6th ed., Wiley, New York, 1998. 2. Rahman, A.-U., Nuclear Magnetic Resonance, Springer-Verlag, New York, 1986. 3. Gordon, A.J. and Ford, R.A., The Chemists Companion, Wiley Interscience, New York, 1971. 4. Becker, E.D., High Resolution NMR, Theory and Chemical Applications, 2nd ed., Academic Press, New York, 1980. 5. Gunther, H., NMR Spectroscopy: Basic Principles, Concepts and Applications in Chemistry, Wiley, New York, 2003. 6. Kitamaru, R., Nuclear Magnetic Resonance: Principles and Theory, Elsevier Science, Amsterdam, 1990. 7. Lambert, J.B., Holland, L.N., and Mazzola, E.P., Nuclear Magnetic Resonance Spectroscopy: Introduction to Principles, Applications and Experimental Methods, Prentice Hall, Englewood Cliffs, NJ, 2003. 8. Bovey, F.A. and Mirau, P.A., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., Academic Press, New York, 1988. 9. Hore, P.J. and Hore, P.J., Nuclear Magnetic Resonance, Oxford University Press, Oxford, 1995. 10. Nelson, J.H., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., Wiley, New York, 2003. 11. Abraham, R.J., Fisher, J., and Loftus, P., Introduction to NMR Spectroscopy, Wiley, New York, 1988.

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Hydrocarbons Family Alkanes of Protons Underlined or Indicated CH3R ~0.8 ppm CH2R ~1.1 ppm >CHR ~1.4 ppm (Cyclopropane, 0.2 ppm) CH3C=C< ~1.6 ppm CH2C=C< ~2.1 ppm >CHC=C< ~2.5 ppm >C=CH 4.26.2 ppm CH3CC ~1.7 ppm CH2CC ~2.2 ppm >CHCC ~2.7 ppm RCCH ~2.4 ppm C6H5G CH3CC=C< ~1.0 ppm CH2CC=C< ~1.4 ppm >CHCC=C< ~1.8 ppm CH3CCC ~1.2 ppm >CH2CCC ~1.5 ppm >CHCCC ~1.8 ppm

Alkenes

Alkynes

Aromatics

G op m-

Range: 8.56.9 ppm

When G=electron withdrawing (e.g., >C=O, NO2, CN), oand p-hydrogens relative to G are closer to 8.5 ppm (more downeld)

When G=electron donating (e.g., NH2, OH, OR, R), o- and phydrogens relative to G are closer to 6.9 ppm (more upeld)

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Organic Oxygen Compounds Family Alcohols Approximate of Protons Underlined or Indicated CH3OH 3.2 ppm RCH2OH 3.4 ppm R2CHOH 3.6 ppm CH3COH 1.2 ppm RCH2COH 1.5 ppm R2CHCOH 1.8 ppm ROH (15 ppm depending on concentration) CH3CHO 2.2 ppm CH3CCHO 1.1 ppm See Organic Nitrogen Compounds CH3C(=O)O 1.8 ppm CH3CC(=O)O 1.2 ppm 3.0 ppm
O C O CH2 C O

Aldehydes

RCH2CHO 2.4 ppm RCH2CCHO 1.6 ppm

R2CHCHO 2.5 ppm

Amides Anhydrides, acyclic

RCH2C(=O)O 2.1 ppm RCH2CC(=O)O 1.8 ppm

R2CHC(=O)O 2.3 ppm R2CHCC(=O)O 2.0 ppm 7.1 ppm

Anhydrides, cyclic

O CH CH C O C O
R2CHCOOH 2.5 ppm R2CHCCOOH 2.0 ppm

CH2

Carboxylic acids

CH3COOH 2.1 ppm CH3CCOOH 1.1 ppm

RCH2COOH 2.3 ppm RCH2CCOOH 1.6 ppm RCOOH 1112 ppm

Cyclic ethers

Oxacyclopropane (oxirane)
2.5 ppm O

Oxacyclobutane (oxetane)

2.7 ppm

O 4.7 ppm

Oxacyclopentane (tetrahydrofuran)

1.9 ppm

3.8 ppm O

Oxacyclohexane (tetrahydropyran)

1.6 ppm 1.6 ppm

3.6 ppm

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Organic Oxygen Compounds (continued) Family 1,4-Dioxane

O 3.6 ppm

Approximate of Protons Underlined or Indicated

1,3-Dioxane
1.7 ppm 3.8 ppm O 4.7 ppm O

Furan
6.3 ppm

7.4 ppm O

Dihydropyran
1.9 ppm 4.5 ppm

6.2 ppm O

Epoxides Esters

See Cyclic Ethers CH3COOR R = alkyl 1.9 ppm R = aryl 2.0 ppm CH3CCOOR 1.1 ppm CH3OOCR 3.6 ppm CH3COOCR 1.3 ppm

RCH2COOR 2.1 ppm 2.2 ppm RCH2CCOOR 1.7 ppm RCH2OOCR 4.1 ppm RCH2COOCR 1.6 ppm
4.4 ppm

R2CHCOOR 2.3 ppm 2.4 ppm R2CHCCOOR 1.9 ppm R2CHOOCR 4.8 ppm R2CHCOOC-R 1.8 ppm
1.6 ppm 1.6 ppm 4.1 ppm

Cyclic
2.1 ppm

2.3 ppm

O 2.3 ppm O O O

Ethers R = alkyl R = aryl R = alkyl R = aryl

CH3OR 3.2 ppm 3.9 ppm CH3COR 1.2 ppm 1.3 ppm

RCH2OR 3.4 ppm 4.1 ppm RCH2COR 1.5 ppm 1.6 ppm

R2CHOR 3.6 ppm 4.5 ppm R2CHCOR 1.8 ppm 2.0 ppm

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Organic Oxygen Compounds (continued) Family Isocyanates Ketones Approximate of Protons Underlined See Nitrogen Compounds CH3C(=O) 1.9 ppm R = alkyl 2.4 ppm R = aryl RCH2C(=O) 2.1 ppm 2.7 ppm R2CHC(=O) 2.3 ppm 3.4 ppm R2CHC(=O) 2.0 ppm 2.1 ppm

CH3C(=O) RCH2C(=O) 1.1 ppm R = alkyl 1.6 ppm 1.2 ppm R = aryl 1.6 ppm Cyclic ketones (n = number of ring carbons) (CH2)n O -hydrogens 2.02.3 ppm (n > 5) 3.0 ppm (n = 4) 1.7 ppm (n = 3) -hydrogens 1.91.5 ppm See Esters, Cyclic See Organic Nitrogen Compounds ArOH 910 ppm (Ar = aryl)

Lactones Nitro compounds Phenols

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ORGANIC NITROGEN COMPOUNDS

Amides of Proton(s) (Underlined) 1. N-substitution RC(=O)NH a. Alpha C(=O)NCH3 C(=O)NCH2 C(=O)NCH b. Beta C(=O)NCCH3 C(=O)NCCH2 C(=O)NCCH 2. C-substitution a. Alpha CH3C(=O)N RCH2C(=O)N R2CHC(=O)N b. Beta CH3CC(=O)N CH2CC(=O)N CHCC(=O)N Amines of Proton(s) (Underlined) 1. Alpha protons >NCH3 >NCH2 >NCH< 2. Beta protons >NCCH3 >NCCH2 >NCCH< Primary RNH2 , ppm ~2.5 ~2.7 ~3.1 Secondary RNHR , ppm 2.33.0 2.63.4 2.93.6 Tertiary RRRN , ppm ~2.2 ~2.4 ~2.8 ~1.1 ~1.4 ~1.7 Primary RC(=O)NH2 , ppm 512 ~1.1 ~1.5 ~1.9 Secondary RC(=O)NHR1 , ppm 512 ~2.9 ~3.4 ~3.8 ~1.1 ~1.5 ~1.9 Tertiary RC(=O)NR1R2 , ppm ~2.9 ~3.4 ~3.8 ~1.1 ~1.5 ~1.9

~1.9 ~2.1 ~2.2 ~1.1 ~1.5 ~1.8

~2.0 ~2.1 ~2.2 ~1.1 ~1.5 ~1.8

~2.1 ~2.1 ~2.2 ~1.1 ~1.5 ~1.8

Cyano Compounds (Nitriles) 1. Alpha hydrogens , ppm CH3CN ~2.1 CH2CN ~2.5 >CHCN ~2.9 Imides 1. Alpha hydrogens , ppm CH3C(=O)NHC(=O) ~2.0 CH2C(=O)NHC(=O) ~2.1 CHC(=O)NHC(=O) ~2.2 Isocyanates Alpha hydrogens , ppm CH3N=C=O ~3.0 CH2N=C=O ~3.3 >CHN=C=O ~3.6 2. Beta hydrogens , ppm CH3C(=O)CNHC(=O) ~1.2 CH2C(=O)CNHC(=O) ~1.3 CHC(=O)CNHC(=O) ~1.4 2. Beta hydrogens , ppm CH3CCN ~1.2 CH2CCN ~1.6 >CHCCN ~2.0

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Isocyanides (Isonitriles) Alpha hydrogens , ppm CH3N=C< ~2.9 CH2N=C< ~3.3 CHN=C< ~4.9

Isothiocyanates Alpha hydrogens , ppm CH3N=C=S ~3.4 CH2N=C=S ~3.7 CHN=C=S ~4.0

Nitriles , ppm CH2ON=O ~4.8

Nitro Compounds , ppm CH3NO2 ~ 4.1 CH3CNO2 ~1.6 CH2NO2 CH2CNO2 ~4.2 ~2.1 CHNO2 ~4.4 CHCNO2 ~2.5

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Organic Sulfur Compounds Family Benzothiopyrans 2H1 4H1 2,3,4H1 Disuldes sp CH ~3.3 ppm sp3 CH ~3.2 ppm sp3 CH 1.92.8 ppm CH3SSR ~2.4 ppm CH2SSR ~2.7 ppm CHSSR ~3.0 ppm CH3N=C=S ~2.4 ppm CH2N=C=S ~2.7 ppm >CHN=C=S ~3.0 ppm CH3SH ~2.1 ppm CH2SH ~2.6 ppm >CHSH ~3.1 ppm + >SCH3 ~3.2 pm (CH3O)2S(=O)2 ~3.4 ppm CH3S 1.82.1 ppm RCH2S 1.92.4 ppm RCHRS 2.83.4 ppm ArCH2S 4.14.2 ppm ArCHRS 3.64.2 ppm Ar2CHS 5.15.2 ppm
3

of Proton(s) Underlined sp2 CH 5.86.4 aromatic ~6.8 sp2 CH 5.96.3 aromatic ~6.9 aromatic ~7.1 CH3CSSR ~1.2 ppm CH2CSSR ~1.6 ppm CHCSSR ~2.0 ppm

Isothiocyanates

Mercaptans (thiols)

CH3CSH ~1.3 ppm CH2CSH ~1.6 ppm >CHCSH ~1.7 ppm

S-methyl salts Sulfates Suldes

CH3CH2S 1.11.2 ppm CH3CHRS 0.81.2 ppm CH3CHArS 1.31.4 ppm CH3CR2S 1.0 ppm ArCH2CHRS 3.03.2 ppm >C=CCH2CHArS 2.42.6 ppm >C=CCH2CAr2S 2.5 ppm R2CHCH2S 2.63.0 ppm Ar2 CHCH2S 4.04.2 ppm >C=CCHRCHArS 2.32.4 ppm >C=CCHRCAr2S 2.83.2 ppm

Sullimines Sulfonamides Sulfonates Sulfones Sulfonic acids Sulfoxides Thiocyanates

Thiols

CH3(R)S=NR2 CH3SO2NH2 CH3SO2OR CH3SO2R2 CH3SO3H CH3S(=O)R CH2S(=O)R CH3SCN CH2SCN CHSCN See Mercaptans

~2.5 ppm ~3.0 ppm ~3.0 ppm ~2.6 ppm ~3.0 ppm ~2.5 ppm ~3.1 ppm ~2.7 ppm ~3.0 ppm ~3.3 ppm

Note: Ar represents aryl.

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SOME USEFUL 1H COUPLING CONSTANTS This section gives the values of some useful proton NMR coupling constants (in Hz). The data are adapted with permission from the work of Dr. C.F. Hammer, Professor Emeritus, Chemistry Department, Georgetown University, Washington, D.C. 20057. The single numbers indicate a typical average, while in some cases the range is provided.
1. Freely rotating chains.
7 68 () 1215

H C C<

H
030

2. Alcohols with no exchange as in DMSO. 1 = triplet 2 = doublet (broad) 3 = singlet Upon addition of TFA, a sharp singlet results. H
5 410

H H 0 >C

OH

3. Alkenes
10

H C C
913

H C C
()

+1.5 to 2.5

H C H

12

H >C C C

H C<

H
03 C 17

1218

C H
311 7

10 612

4. Alkynes () C
12 12 23

5. Aldehydes
8

H >C

H C H >C C C

H C

H C

H C O

H C O

58

H C C

6. Aromatic H
8 13 610

H
0 1 ()

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ADDITIVITY RULES IN

13

C NMR CORRELATION TABLES

The wide chemical shift range (~250 ppm) of 13C NMR is responsible for the considerable change of a chemical shift noted when a slight inductive, mesomeric, or hybridization neighboring change occurs. Following the various empirical correlations in 1H NMR,17 D.W. Brown8 has developed a short set of 13C NMR correlation tables. This section covers a part of those as adopted by Yoder and Schaeffer9 and Clerk et al.10 Refer to reference 8 for some accurate data on more complicated structures and look up the various references included in the literature cited below.117

REFERENCES
1. Shoolery, J.N., Varian Associates Technical Information Bulletin, Vol. 2, No. 3, Palo Alto, CA, 1959. 2. Bell, H.M., Bowles, D.B., and Senese, F., Additive NMR chemical shift parameters for deshielded methine protons, Org. Magn. Reson., 16, 285, 1981. 3. Matter, U.E., Pascual, C., Pretsch, E., Pross, A., Simon, W., and Sternhell, S., Estimation of the chemical shifts of olenic protons using additive increments. II. Compilation of additive increments for 43 functional groups, Tetrahedron, 25, 691, 1969. 4. Matter, U.E., Pascual, C., Pretsch, E., Pross, A., Simon, W., and Sternhell, S., Estimation of the chemical shifts of olenic protons using additive increments. III. Examples of utility in N.M.R. studies and the identication of some structural features responsible for deviations from additivity, Tetrahedron, 25, 2023, 1969. 5. Jeffreys, J.A.D., A rapid method for estimating NMR shifts for protons attached to carbon, J. Chem. Educ., 56, 806, 1979. 6. Mikolajczyk, M., Grzeijszczak, S., and Zatorski, A., Organosulfur compounds IX: NMR and structural assignments in ,-unsaturated sulphoxides using additive increments method, Tetrahedron, 32, 969, 1976. 7. Friedrich, E.C. and Runkle, K.G., Empirical NMR chemical shift correlations for methyl and methylene protons, J. Chem. Educ., 61, 830, 1984. 8. Brown, D.W., A short set of 13C-NMR correlation tables, J. Chem. Educ., 62, 209, 1985. 9. Yoder, C.H. and Schaeffer, C.D., Jr., Introduction to Multinuclear NMR, Benjamin/Cummings Publishing Co., Menlo Park, CA, 1987. 10. Clerk, J.T., Pretsch, E., and Seibl, J., Structural Analysis of Organic Compounds by Combined Application of Spectroscopic Methods, Elsevier, Amsterdam, 1981. 11. Silverstein, R.M. and Webster F.X., Spectrometric Identication of Organic Compounds, 6th ed., John Wiley & Sons, New York, 1998. 12. Gunther, H., NMR Spectroscopy: Basic Principles, Concepts and Applications in Chemistry, John Wiley & Sons, New York, 2003. 13. Kitamaru, R., Nuclear Magnetic Resonance: Principles and Theory, Elsevier Science, Amsterdam, 1990. 14. Lambert, J.B., Holland, L.N., and Mazzola, E.P., Nuclear Magnetic Resonance Spectroscopy: Introduction to Principles, Applications and Experimental Methods, Prentice Hall, Englewood Cliffs, NJ, 2003. 15. Bovey, F.A. and Mirau, P.A., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., Academic Press, New York, 1988. 16. Harris, R.K. and Mann, B.E., NMR and the Periodic Table, Academic Press, London, 1978. 17. Nelson, J.H., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., John Wiley & Sons, New York, 2003.

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Alkanes The chemical shift (in ppm) of Ci can be calculated from the following empirical equation: i = 2.3 + Ai where Ai is the sum of increments allowed for various substituents depending on their positions (, , , ) relative to the 13C in question and (2.3) is the chemical shift for methane relative to tetramethylsilane (TMS).
13

C Chemical Shift Increments for A, the Shielding Term for Alkanes and Substituted Alkanes9,10 Increments Substituent >C (sp3) >C=C< (sp2) CC (sp) C 6H 5 F Cl Br I OH OR CHO COR COOH COO COCl COOR OOCR N< NH3+ [ >N< ]+ ONO NO2 CON< NHCO CN NC S SCO SO SO2Cl SCN C(=S)N C=NOH(syn) C=NOH(anti) R1R2R3Sn R1, R2, and R3 = organic substituents 9.1 19.5 4.4 22.1 70.1 31.0 18.9 7.2 49.0 49.0 29.9 22.5 20.1 24.5 33.1 22.6 5.5 28.3 26.0 30.7 54.3 61.6 22.0 31.3 3.1 31.5 10.6 17.0 31.1 54.5 23.0 33.1 11.7 16.1 5.2 9.4 6.9 5.6 9.3 7.8 10.0 11.0 10.9 10.1 10.1 0.6 3.0 2.0 3.5 2.3 2.0 6.5 11.3 7.5 5.4 6.1 3.1 2.6 8.3 2.4 7.6 11.4 6.5 9.0 3.4 9.7 7.7 0.6 4.3 4.0 2.5 2.1 3.4 2.6 6.8 5.1 3.8 1.5 6.2 6.2 2.7 3.0 2.8 2.5 3.6 2.8 6.0 5.1 4.6 7.2 6.5 4.6 3.2 5.7 3.3 3.0 3.6 3.1 3.5 3.0 3.0 2.5 1.8 1.5 0.3 0.3 0.4 0.6 0.3 0.0 0.5 0.7 0.9 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

0.0 1.4 0.5 1.0 0.4 0.0 0.5 0.0 0.4 0.0 0.0 0.0 0.0 0.6 0.0 0.0 0.0

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Thus, the 13C shift for Ci in 2-pentanol is predicted to be i CH3CH2CH2CH(OH)CH3 i = (2.3) + [9.1 + 9.4 + 9.1 + 9.4 + 10.1] = 44.8 ppm OH Alkenes For a simple olen of the type CCCCi = CCCC i = 122.8 + Ai where A = 10.6, A = 7.2, A = 1.5, A = 7.9, A = 1.8, A = 1.5, and 122.8 is the chemical shift of the sp2 carbon in ethene. If the olen is in the cis conguration, an increment of 1.1 ppm must be added. Thus, the 13C shift for C-3 in cis-3-hexene is predicted to be i CH3CH2CH = CHCH2CH3 i = 122.8 + [10.6 + 7.2 1.5 7.9] + (1.1) = 130.1 ppm () () () () (cis) Alkynes For a simple alkyne of the type CCCi CCC i = 71.9 + Ai where increments A are given in the table below and 71.9 is the chemical shift of the sp carbon in acetylene.9
13

C Chemical Shift Increments for A, the Shielding Term for Alkynes Increments 6.9 7.0 12.0 16.0 11.1 31.4 12.7 10.0 12.0 4.8 5.7 5.7 3.5 3.5 1.9 4.0 6.4 11.0 15.0 2.3

Substituents C (sp3) CH3 CH2CH3 CH(CH3)2 CH2OH COCH3 C6H5 CH=CH2 Cl

Thus, the 13C shift for C1 in 1-phenyl propyne is predicted to be C6H5 C1i C2CH3
1 2

i = 71.9 + 7.0 + 6.4 = 85.3 ppm

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while the 13C shift for C2 in the same compound is predicted to be C6H5C1 C2iCH3
1 2

i = 71.9 + 6.9 + 6.4 = 85.20 ppm

Benzenoid Aromatics For a benzene derivative, C6H5X, where X = substituent, i = 128.5 + Ai where Ai is the sum of increments given below and 128.5 is the chemical shift of benzene.9,10

13

C Chemical Shift Increments for A, the Shielding Term for Benzenoid Aromatics XC6H5, where X = Substituent Substituent X CH3 CH2CH3 CH(CH3)2 C(CH3)3 CH=CH2 CCH C6H5 CHO COCH3 CO2H CO2 CO2R CONH2 CN Cl OH O OCH3 OC6H5 OC(=O)CH3 NH2 NHCH3 N(CH3)2 NO2 SH SCH3 SO3H Ci 9.3 15.89, 15.710 20.39, 20.110 22.49, 22.110 7.6 6.1 13.0 8.69, 9.010 9.19, 9.310 2.19, 2.410 7.6 2.1 5.4 15.49, 16.010 6.29, 6.410 26.9 39.610 31.49, 30.210 29.1 23.0 18.79, 19.210 21.710 22.4 20.09, 19.610 2.2 9.910 15.0 Increments ortho meta 0.8 , 0.6 0.49, 0.610 1.99, 2.010 3.19, 3.410 1.8 3.8 1.1 1.39, 1.210 0.19, 0.210 1.59, 1.610 0.8 1.2 0.3 3.69, 3.510 0.49, 0.210 12.7 8.210 14.49, 14.710 9.5 6.4 12.4 16.210 15.7 4.89, 5.310 0.7 2.010 2.2
9 10

para 2.99, 3.110 2.69, 2.810 2.49, 2.510 2.99, 3.110 3.5 0.2 1.0 5.59, 6.010 4.2 5.19, 4.810 2.8 4.4 5.0 3.99, 4.310 1.99, 2.010 7.3 13.610 7.79, 8.110 5.3 2.3 9.5 11.810 11.8 5.89, 6.010 3.1 3.710 3.8

0.0 0.1 0.19, 0.010 0.29, 0.410 1.8 0.4 0.5 0.69, 1.210 0.09, 0.210 0.09, 0.110 0.0 0.0 0.9 0.69, 0.710 1.39, 10.010 1.4 1.910 1.09, 0.910 0.3 1.3 1.3 0.710 0.8 0.99, 0.810 0.4 0.110 1.3

As an example, the 13C shift for the benzene carbon (C i) carrying the carbonyl in 3,5-dinitroacetophenone, CH3C(=O)(C6H3)(NO2)2, is predicted to be Ci = 128.5 + 9.1 + 2(0.9) = 132.4 ppm

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13

C NMR ABSORPTIONS OF MAJOR FUNCTIONAL GROUPS

The table below lists the 13C chemical shift ranges (in ppm) with the corresponding functional groups in descending order. A number of typical simple compounds for every family is given to illustrate the corresponding range. The shifts for the carbons of interest are given in parentheses for each carbon as it appears either from left to right in the formula or by the underscore.114

REFERENCES
1. Yoder, C.H. and Schaeffer, C.D., Jr., Introduction to Multinuclear NMR: Theory and Application, Benjamin/Cummings Publishing Co., Menlo Park, CA, 1987. 2. Brown, D.W., A short set of 13C-NMR correlation tables, J. Chem. Ed., 62, 209, 1985. 3. Silverstein, R.M. and Webster, F.X., Spectrometric Identication of Organic Compounds, 6th ed., John Wiley & Sons, New York, 1998. 4. Becker, E.D., High Resolution NMR, Theory and Chemical Applications, 2nd ed., Academic Press, New York, 1980. 5. Gunther, H., NMR Spectroscopy: Basic Principles, Concepts and Applications in Chemistry, Wiley, New York, 2003. 6. Kitamaru, R., Nuclear Magnetic Resonance: Principles and Theory, Elsevier Science, Amsterdam, 1990. 7. Lambert, J.B., Holland, L.N., and Mazzola, E.P., Nuclear Magnetic Resonance Spectroscopy: Introduction to Principles, Applications and Experimental Methods, Prentice Hall, Englewood Cliffs, NJ, 2003. 8. Bovey, F.A. and Mirau, P.A., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., Academic Press, New York, 1988. 9. Harris, R.K. and Mann, B.E., NMR and the Periodic Table, Academic Press, London, 1978. 10. Hore, P.J., Nuclear Magnetic Resonance, Oxford University Press, Oxford, 1995. 11. Nelson, J.H., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., Wiley, New York, 2003. 12. Levy, G.C., Lichter, R.L., and Nelson, G.L., Carbon-13 Nuclear Magnetic Resonance Spectroscopy, 2nd ed., Wiley, New York, 1980. 13. Pihlaja, K. and Kleinpeter, E., Carbon-13 NMR Chemical Shifts in Structural and Stereochemical Analysis, VCH, New York, 1994. 14. Aldrich Library of 1H and 13C FT-NMR Spectra, Aldrich Chemical Company, Milwaukee, 1996.

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13

C NMR Absorptions of Major Functional Groups Group >C=O Ketones Aldehydes ,-Unsaturated carbonyls Carboxylic acids Amides Esters Family Example ( of Underlined Carbon) (CH3)2CO (CH3)2CHCOCH3 CH3CHO CH3CH=CHCHO CH2=CHCOCH3 HCO2H CH3CO2H HCONH2 CH3CONH2 CH3CO2CH2CH3 CH2=CHCO2CH3 C 6H 6 CH2=CH2 CH2=CHCH3 CH2=CHCH2Cl CH3CH=CHCH2CH3 CH3CN HCCH CH3CCCH3 CH3OOCCH2CH3 HOCH3 HOCH2CH3 CH3NH2 CH3CH2NH2 C6H5SCH3 CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 CH3CH2CH2CH2CH3 Cyclohexane (206.0) (212.1) (199.7) (192.4) (169.9) (166.0) (178.1) (165.0) (172.7) (170.3) (165.5) (128.5) (123.2) (115.9, 136.2) (117.5, 133.7) (132.7) (117.7) (71.9) (73.9) (57.6, 67.9) (49.0) (57.0) (26.9) (35.9) 15.6 (2.3) (5.7) (15.8, 16.3) (13.4, 25.2) (13.9, 22.8, 34.7) (26.9)

(ppm) 220165

140120

>C=C<

Aromatic Alkenes

125115 8070 7045

CN CC CO CNH2 SCH3 >CH

Nitriles Alkynes Esters Alcohols Amines Suldes (thioethers) Alkanes, cycloalkanes

4020 3015 30(2.3)

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13

C NMR CHEMICAL SHIFTS OF ORGANIC FAMILIES

The following bibliography should give a good set of references for the various organic families. This collection is by no means complete and should be updated regularly.

REFERENCES Adamantanes
Maciel, G.E., Dorn, H.C., Greene, R.L., Kleschick, W.A., Peterson, M.R., Jr., and Wahl, G.H., Jr., 13C chemical shifts of monosubstituted adamantanes, Org. Magn. Reson., 6, 178, 1974.

Amides
Jones, R.G. and Wilkins, J.M., Carbon-13 NMR spectra of a series of parasubstituted N,N-dimethylbenzamides, Org. Magn. Reson., 11, 20, 1978.

Benzazoles
Sohr, P., Manyai, G., Hideg, K., Hankovszky, H., and Lex, L., Benzazoles. XIII. Determination of the E and Z conguration of isomeric 2-(2-benzimidazolyl)-di- and tetra-hydrothiophenes by IR, 1H and 13C NMR spectroscopy, Org. Magn. Reson., 14, 125, 1980.

Carbazoles
Giraud, J. and Marzin, C., Comparative 13C NMR study of deuterated and undeuterated dibenzothiophenes, dibenzofurans, carbazoles, uorenes, and uorenones, Org. Magn. Reson., 12, 647, 1979.

Chlorinated Compounds
Hawkes, G.E., Smith, R.A., and Roberts, J.D., Nuclear magnetic resonance spectroscopy: carbon-13 chemical shifts of chlorinated organic compounds, J. Org. Chem., 39, 1276, 1974. Mark, V. and Weil, E.D., The isomerization and chlorination of decachlorobi-2,4-cyclopentadien-1-yl, J. Org. Chem., 36, 676, 1971.

Diazoles and Diazines

Faure, R., Vincent, E.J., Assef, G., Kister, J., and Metzger, J., Carbon-13 NMR study of substituent effects in the 1,3-diazole and -diazine series, Org. Magn. Reson., 9, 688, 1977.

Disuldes
Bass, S.W. and Evans, S.A., Jr., Carbon-13 nuclear magnetic resonance spectral properties of alkyl disuldes, thiosulnates, and thiosulfonates, J. Org. Chem., 45, 710, 1980. Freeman, F. and Angeletakis, C.N., Carbon-13 nuclear magnetic resonance study of the conformations of disuldes and their oxide derivatives, J. Org. Chem., 47, 4194, 1982. Takata, T., Iida, K., and Oae, S., 13C-NMR chemical shifts and coupling constants JC-H of six membered ring systems containing sulfur-sulfur linkage, Heterocytes, 15, 847, 1981.

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Fluorenes and Fluorenones

Giraud, J. and Marzin, C., Comparative 13C NMR study of deuterated and undeuterated dibenzothiophenes, dibenzofurans, carbazoles, uorenes and uorenones, Org. Magn. Reson., 12, 647, 1979.

Furans
Giraud, H. and Marzin, C., Comparative 13C NMR study of deuterated and undeuterated dibenzothiophenes, dibenzofurans, carbazoles, uorenes and uorenones, Org. Magn. Reson., 12, 647, 1979.

Imines
Allen, M. and Roberts, J.D., Effects of protonation and hydrogen bonding on carbon-13 chemical shifts of compounds containing the >C=N-group, Can. J. Chem., 59, 451, 1981.

Oxathianes
Murray, W.T., Kelly, J.W., and Evans, S.A., Jr., Synthesis of substituted 1,4-oxathianes, mechanistic details of diethoxytriphenylphosphorane and triphenylphosphine/tetra-chloromethane promoted cyclodehydrations and 13C NMR spectroscopy, J. Org. Chem., 52, 525, 1987. Szarek, W.A., Vyas, D.M., Sepulchre, A.M., Gero, S.D., and Lukacs, G., Carbon-13 nuclear magnetic resonance spectra of 1,4-oxathiane derivatives, Can. J. Chem., 52, 2041, 1974.

Oximes
Allen, M. and Roberts, J.D., Effects of protonation and hydrogen bonding on carbon-13 chemical shifts of compounds containing the >C=N-group, Can. J. Chem., 59, 451, 1981.

Polynuclear Aromatics (Naphthalenes, Anthracenes, Pyrenes)

Adcock, W., Aurangzeb, M., Kitching, W., Smith, N., and Doddzell, D., Substituent effects of carbon-13 nuclear magnetic resonance: concerning the -inductive effect, Aust. J. Chem., 27, 1817, 1974. DuVernet, R. and Boekelheide, V., Nuclear magnetic resonance spectroscopy: ring-current effects on carbon13 chemical shifts, Proc. Natl. Acad. Sci. U.S.A., 71, 2961, 1974.

Pyrazoles
Puar, M.S., Rovnyak, G.C., Cohen, A.I., Toeplitz, B., and Gougoutas, J.Z., Orientation of the sulfoxide bond as a stereochemical probe: synthesis and 1H and 13C NMR of substituted thiopyrano[4,3-c]pyrazoles, J. Org. Chem., 44, 2513, 1979.

Suldes
Chauhan, M.S., and Still, I.W.J., 13C nuclear magnetic resonance spectra of organic sulfur compounds: cyclic suldes, sulfoxides, sulfones, and thiones, Can. J. Chem., 53, 2880, 1975. Gokel, G.W., Gerdes, H.M., and Dishong, D.M., Sulfur heterocycles. 3. Heterogenous, phase-transfer, and acid catalyzed potassium permanganate oxidation of suldes to sulfones and a survey of their carbon13 nuclear magnetic resonance spectra, J. Org. Chem., 45, 3634, 1980. Mohraz, M., Jiam-qi, W., Heilbronner, E., Solladie-Cavallo, A., and Matloubi-Moghadam, F., Some comments on the conformation of methyl phenyl suldes, sulfoxides, and sulfones, Helv. Chim. Acta, 64, 97, 1981.

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Srinivasan, C., Perumal, S., Arumugam, N., and Murugan, R., Linear free-energy relationship in naphthalene system-substituent effects on carbon-13 chemical shifts of substituted naphthylmethyl suldes, Ind. J. Chem., 25A, 227, 1986.

Sultes
Buchanan, G.W., Cousineau, C.M.E., and Mundell, T.C., Trimethylene sulte conformations: effects of sterically demanding substituents at C-4,6 on ring geometry as assessed by 1H and 13C nuclear magnetic resonance, Can. J. Chem., 56, 2019, 1978.

Sulfonamides
Chang, C., Floss, H.G., and Peck, G.E., Carbon-13 magnetic resonance spectroscopy of drugs: sulfonamides, J. Med. Chem., 18, 505, 1975.

Sulfones (See Also Other Families for the Corresponding Sulfones)

Balaji, T. and Reddy, D.B., Carbon-13 nuclear magnetic resonance spectra of some new arylcycoproyl sulphones, Ind. J. Chem., 18B, 454, 1979. Fawcett, A.H., Ivin, K.J., and Stewart, C.D., Carbon-13 NMR spectra of monosulphones and disulphones: substitution rules and conformational effects, Org. Magn. Reson., 11, 360, 1978. Gokel, G.W., Gerdes, H.M., and Dishong, D.M., Sulfur heterocycles. 3. Heterogeneous, phase-transfer, and acid catalyzed potassium permanganate oxidation of suldes to sulfones and a survey of their carbon13 nuclear magnetic resonance spectra, J. Org. Chem., 45, 3634, 1980.

Sulfoxides (See Also Other Families for the Corresponding Sulfoxides)

Gatti, G., Levi, A., Lucchini, V., Modena, G., and Scorrano, G., Site of protonation in sulphoxides: carbon13 nuclear magnetic resonance evidence, J. Chem. Soc. Chem. Commun., 251, 1973. Harrison, C.R. and Hodge, P., Determination of the conguration of some penicillin S-oxides by 13C nuclear magnetic resonance spectroscopy, J. Chem. Soc. Perkin Trans., I, 1772, 1976.

Sulfur Ylides
Matsuyama, H., Minato, H., and Kobayashi, M., Electrophilic suldes (II) as a novel catalyst. V. Structure, nucleophilicity, and steric compression of stabilized sulfur ylides as observed by 13C-NMR spectroscopy, Bull. Chem. Soc. Jpn., 50, 3393, 1977.

Thianes
Barbarella, G., Dembech, P., Garbesi, A., and Fara, A., 13C NMR of organosulfur compounds. II. 13C chemical shifts and conformational analysis of methyl substituted thiacyclohexanes, Org. Magn. Reson., 8, 469, 1976. Block, E., Bazzi, A.A., Lambert, J.B., Wharry, S.M., Andersen, K.K., Dittmer, D.C., Patwardhan, B.H., and Smith, J.H., Carbon-13 and oxygen-17 nuclear magnetic resonance studies of organosulfur compounds: the four-membered-ring-sulfone effect, J. Org. Chem., 45, 4807, 1980. Murray, W.T., Kelly, J.W., and Evans, S.A., Jr., Synthesis of substituted 1,4-oxathianes: mechanistic details of diethoxytriphenyl phosphorane and triphenylphosphine/tetrachloromethane promoted cyclodehydrations and 13C NMR spectroscopy, J. Org. Chem., 52, 525, 1987. Rooney, R.P., and Evans, S.A., Jr., Carbon-13 nuclear magnetic resonance spectra of trans-1-thiadecalin, trans1,4-dithiadecalin, trans-1,4-oxathiadecalin, and the corresponding sulfoxides and sulfones, J. Org. Chem., 45, 180, 1980. Willer, R.L. and Eliel, E.L., Conformational analysis. 34. Carbon-13 nuclear magnetic resonance spectra of saturated heterocycles. 6. Methylthianes, J. Am. Chem. Soc., 99, 1925, 1977.

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Thiazines
Fronza, G., Mondelli, R., Scapini, G., Ronsisvalle, G., and Vittorio, F., 13C NMR of N-heterocycles: conformation of phenothiazines and 2,3-diazaphenothiazines, J. Magn. Reson., 23, 437, 1976.

Thiazoles
Chang, G., Floss, H.G., and Peck, G.E., Carbon-13 magnetic resonance spectroscopy of drugs: sulfonamides, J. Med. Chem., 18, 505, 1975. Elguero, J., Faure, R., Lazaro, R., and Vincent, E.J., 13C NMR study of benzothiazole and its nitroderivatives, Bull. Soc. Chim. Belg., 86, 95, 1977. Faure, R., Galy, J.P., Vincent, E.J., and Elguero, J., Study of polyheteroaromatic pentagonal heterocycles by carbon-13 NMR: thiazoles and thiazolo[2,3-e]tetrazoles, Can. J. Chem., 56, 46, 1978. Harrison, C.R. and Hodge, P., Determination of the conguration of some penicillin S-oxides by 13C nuclear magnetic resonance spectroscopy, J. Chem. Soc. Perkin Trans., I, 1772, 1976.

Thiochromanones
Chauhan, M.S. and Still, I.W.J., 13C nuclear magnetic resonance spectra of organic sulfur compounds: cyclic suldes, sulfoxides, sulfones and thiones, Can. J. Chem., 53, 2880, 1975.

Thiones
Chauhan, M.S. and Still, I.W.J., 13C nuclear magnetic resonance spectra of organic sulfur compounds: cyclic suldes, sulfoxides, sulfones and thiones, Can. J. Chem., 53, 2880, 1975.

Thiophenes
Balkau, F., Fuller, M.W., and Heffernan, M.L., Deceptive simplicity in ABMX N.M.R. spectra. I. Dibenzothiophen and 9.9-dicarbazyl, Aust. J. Chem., 24, 2293, 1971. Benassi, R., Folli, U., Iarossi, D., Schenetti, L., and Tadei, F., Conformational analysis of organic carbonyl compounds. Part 3. A 1H and 13C nuclear magnetic resonance study of formyl and acetyl derivatives of benzo[b]thiophen, J. Chem. Soc. Perkin Trans., II, 911, 1983. Clark, P.D., Ewing, D.F., and Scrowston, R.M., NMR studies of sulfur heterocycles: III. 13C spectra of benzo[b]thiophene and the methylbenzo[b]thiophenes, Org. Magn. Reson., 8, 252, 1976. Fujieda, K., Takahashi, K., and Sone, T., The C-13 NMR spectra of thiophenes. II. 2-Substituted thiophenes, Bull. Chem. Soc. Jpn., 58, 1587, 1985. Geneste, P., Olive, J.L., Ung, S.N., El Faghi, M.E.A., Easton, J.W., Beierbeck, H., and Saunders, J.K., Carbon13 nuclear magnetic resonance study of benzo[b]thiophenes and benzo[b]thiophene S-oxides and S,Sdioxides, J. Org. Chem., 44, 2887, 1979. Giraud, J. and Marzin, C., Comparative 13C NMR study of deuterated and undeuterated dibenzothiophenes, dibenzofurans, carbazoles, uorenes and uorenones, Org. Magn. Reson., 12, 647, 1979. Kiezel, L., Liszka, M., and Rutkowski, M., Carbon-13 magnetic resonance spectra of benzothiophene and dibenzothiophene, Spec. Lett., 12, 45, 1979. Osamura, Y., Sayanagi, O., and Nishimoto, K., C-13 NMR chemical shifts and charge densities of substituted thiophenes: the effect of vacant d orbitals, Bull. Chem. Soc. Jpn., 49, 845, 1976. Perjessy, A., Janda, M., and Boykin, D.W., Transmission of substituent effects in thiophenes: infrared and carbon-13 nuclear magnetic resonance studies, J. Org. Chem., 45, 1366, 1980. Satonaka, H. and Watanabe, M., NMR spectra of 2-(2-nitrovinyl) thiophenes, Bull. Chem. Soc. Jpn., 58, 3651, 1985. Stuart, J.G., Quast, M.J., Martin, G.E., Lynch, V.M., Simmonsen, H., Lee, M.L., Castle, R.N., Dallas, J.L., John B.K., and Johnson, L.R.F., Benzannelated analogs of phenanthro [1,2-b]-[2,1-b]thiophene: synthesis and structural characterization by two-dimensional NMR and x-ray techniques, J. Heterocyclic Chem., 23, 1215, 1986.

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Thiopyrans
Senda, Y., Kasahara, A., Izumi, T., and Takeda, T., Carbon-13 NMR spectra of 4-chromanone, 4H-1-benzothiopyran-4-one, 4H-1-benzothiopyran-4-one 1,1-dioxide, and their substituted homologs, Bull. Chem. Soc. Jpn., 50, 2789, 1977.

Thiosulnates and Thiosulfonates

Bass, S.W. and Evans, S.A., Jr., Carbon-13 nuclear magnetic resonance spectral properties of alkyl disuldes, thiosulnates, and thiosulfonates, J. Org. Chem., 45, 710, 1980.

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15

N CHEMICAL SHIFTS FOR COMMON STANDARDS

The following table lists the 15N chemical shifts (in ppm) for common standards. The estimated precision is better than 0.1 ppm. Nitromethane, according to Levy and Lichter,1 is the most suitable primary measurement reference, but has the disadvantage of lying in the low-eld end of the spectrum. Thus, ammonia (which lies in the most upeld region) is the most suitable for routine experimental use.16

REFERENCES
1. Levy, G.C. and Lichter, R.L., Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy, John Wiley & Sons, New York, 1979. 2. Lambert, J.B., Shurvell, H.F., Verbit, L., Cooks, R.G., and Stout, G.H., Organic Structural Analysis, MacMillan, New York, 1976. 3. Witanowski, M., Stefaniak, L., Szymanski, S., and Januszewski, H., External neat nitromethane scale for nitrogen chemical shifts, J. Magn. Reson., 28, 217, 1977. 4. Srinivasan, P.R. and Lichter, R.L., Nitrogen-15 nuclear magnetic resonance spectroscopy: evaluation of chemical shift references, J. Magn. Reson., 28, 227, 1977. 5. Briggs, J.M. and Randall, E.W., Nitrogen-15 chemical shifts in concentrated aqueous solutions of ammonium salts, Mol. Phys., 26, 699, 1973. 6. Becker, E.D., Proposed scale for nitrogen chemical shifts, J. Magn. Reson., 4, 142, 1971.
15

N Chemical Shifts for Common Standards Formula NH3 NH4NO3 NH4Cl (C2H5)4N+Cl Conditions Vapor (0.5 MPa) Liquid (25C), anhydrous Liquid (50C) Aqueous HNO3 Aqueous solution (saturated) 2.9 M (in 1 M HCl) 1.0 M (in 10 M HCl) Aqueous solution (saturated) Aqueous solution (saturated) Chloroform solution (saturated) Aqueous solution (0.3 M ) Aqueous solution (saturated) Chloroform solution (0.075 M ) Neat Neat 1M 2M 9M 10 M 15.7 M Aqueous solution (saturated) Aqueous solution (saturated) 5 M (in 2 M HNO3) 4 M (in 2 M HNO3) 1:1 (v/v) in CDCl3 0.03 M Cr(acac)3 Neat Chemical Shift (ppm) 15.9 0.0 3.37 21.60 20.68 24.93 30.31 27.34 43.54 45.68 63.94 64.39 65.69 62.50 103.81 375.80 367.84 365.86 362.00 348.92 376.53 376.25 375.59 374.68 379.60 380.23

Compound Ammonia

Ammonium nitrate Ammonium chloride

Tetraethylammonium chloride

Tetramethyl urea Dimethylformamide (DMF) Nitric acid (aqueous solution)

[(CH3)2N]2CO (CH3)2NCHO HNO3

Sodium nitrate Ammonium nitrate

NaNO3 NH4NO3 CH3NO2

Nitromethane

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15

N CHEMICAL SHIFTS OF MAJOR CHEMICAL FAMILIES

The following table contains 15N chemical shifts of various organic nitrogen compounds. Chemical shifts are expressed relative to different standards (NH3, NH4Cl, CH3NO2, NH4NO3, HNO3, etc.) and are interconvertible. Chemical shifts are sensitive to hydrogen bonding and are solvent dependent, as seen in the case of pyridine (see table footnote b below). Consequently, the reference as well as the solvent should always accompany chemical shift data. No data are given on peptides and other biochemical compounds. All shifts are relative to ammonia unless otherwise specied. A section of miscellaneous data gives the chemical shift of special compounds relative to unusual standards.115

REFERENCES
1. Levy, G.C. and Lichter, R.L., Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy, John Wiley & Sons, New York, 1979. 2. Yoder, C.H. and Schaeffer, C.D., Jr., Introduction to Multinuclear NMR, Benjamin/Cummings, Menlo Park, CA, 1987. 3. Duthaler, R.O. and Roberts, J.D., Effects of solvent, protonation, and N-alkylation on the 15N chemical shifts of pyridine and related compounds, J. Am. Chem. Soc., 100, 4969, 1978. 4. Duthaler, R.O. and Roberts, J.D., Steric and electronic effects on 15N chemical shifts of saturated aliphatic amines and their hydrochlorides, J. Am. Chem. Soc., 100, 3889, 1978. 5. Kozerski, L. and von Philipsborn, W., 15N chemical shifts as a conformational probe in enaminones: a variable temperature study at natural isotope abundance, Org. Magn. Reson., 17, 306, 1981. 6. Duthaler, R.O. and Roberts, J.D., Steric and electronic effects on 15N chemical shifts of piperidine and decahydroquinoline hydrochlorides, J. Am. Chem. Soc., 100, 3882, 1978. 7. Duthaler, R.O. and Roberts, J.D., Nitrogen-15 nuclear magnetic resonance spectroscopy: solvent effects on the 15N chemical shifts of saturated amines and their hydrochlorides, J. Magn. Reson., 34, 129, 1979. 8. Psota, L., Franzen-Sieveking, M., Turnier, J., and Lichter, R.L., Nitrogen nuclear magnetic resonance spectroscopy: nitrogen-15 and proton chemical shifts of methylanilines and methylanilinium ions, Org. Magn. Reson., 11, 401, 1978. 9. Subramanian, P.K., Chandra Sekara, N., and Ramalingam, K., Steric effects on nitrogen-15 chemical shifts of 4-aminooxanes (tetrahydropyrans), 4-amino-thianes, and the corresponding N,N-dimethyl derivatives: use of nitrogen-15 shifts as an aid in stereochemical analysis of these heterocyclic systems, J. Org. Chem., 47, 1933, 1982. 10. Schuster, I.I. and Roberts, J.D., Proximity effects on nitrogen-15 chemical shifts of 8-substituted 1nitronaphthalenes and 1-naphthylamines, J. Org. Chem., 45, 284, 1980. 11. Kupce, E., Liepins, E., Pudova, O., and Lukevics, E., Indirect nuclear spin-spin coupling constants of nitrogen-15 to silicon-29 in silylamines, J. Chem. Soc. Chem. Commun., 581, 1984. 12. Allen, M. and Roberts, J.D., Effects of protonation and hydrogen bonding on nitrogen-15 chemical shifts of compounds containing the >C=N-group, J. Org. Chem., 45, 130, 1980. 13. Brownlee, R.T.C. and Sadek, M., Natural abundance 15N chemical shifts in substituted benzamides and thiobenzamides, Magn. Reson. Chem., 24, 821, 1986. 14. Dega-Szafran, Z., Szafran, M., Stefaniak, L., Brevard, C., and Bourdonneau, M., Nitrogen-15 nuclear magnetic resonance studies of hydrogen bonding and proton transfer in some pyridine triuoroacetates in dichloromethane, Magn. Reson. Chem., 24, 424, 1986. 15. Lambert, J.B., Shurvell, H.F., Verbit, L., Cooks, R.G., and Stout, G.H., Organic Structural Analysis, Macmillan, New York, 1976.

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15

N Chemical Shifts of Major Chemical Families Family Nitroso compounds Sodium nitrite Azo compounds Nitro compounds Nitric acid (8.57 M ) Nitramines Pyridines Imines (aromatic) Nitrogen (gas) Pyridinium salts Cyanides (nitriles) Pyrroles Isonitriles Thioamides Lactams Amides Sulfonamides Hydrazines Ureas Aminophosphines Aminophosphine oxides Aromatic amines Aliphatic amines Isonitriles Ammonium salts Isocyanates C6H5NO (913, 930) NaNO2 C6H5N=NC6H5 (510) C6H5NO2 (370.3); CH3NO2 (380.2); 4-FC6H4NO2 (368.5); 1,3-(NO2)2C6H4 (365.4) HNO3 CH3NHNO2 (355.6); CH3O2CNHNO2 (334.9) C5H5N (317)b (gas); 4-CH3C5H4N (309.3); 4-NH2C5H4N (271.5); 4-NCC5H4N (327.9) (C6H5)2C=NH (308); C6H5CH=NCH3 (318); C6H5CH=NC6H5 (326) N2 C5H5NH+ (215) CH3CN (239.5, 245); C6H5CN (258.7); KCN 177.8 C4H4NH (158) CH3NC (162) CH3C(=S)NH2 (150.2) HN(CH2)3C=O (ve-membered ring; 114.7) HN(CH2)6C=O (eight-membered ring; 117.7) C6H5CONH2 (100); CH3CONH2 (103.4); CH3CONHCH3 (105.8); CH3CON(CH3)2 (103.8); HCONH2 (108.5) CH3SO2NH2 (95); C6H5SO2NH2 (94.3) C6H5NHNHC6H5 (96) [H2N]2CO (75, 82); [(CH3)2N]2CO (63.5); [C6H5NH]2CO (107.7) C6H5NHP(CH3)2 (71.1) C6H5NHPO(CH3)2 (86.6) C6H5NH2 (55, 59) (322.3)c; C6H5NH3+ (48) (326.4)c, 26.1g; p-O2NC6H4NH2 (70) CH3NH2 (1.3)a (371)c; (CH3)2NH (363.3)c (364.9)d, 6.7a; (CH3)3N (356.9)c (360.7)d, 13.0a CH3NCO (14.1); C6H5NCO (46.5) NH4Cl (26.1)a; CH3NH3Cl (24.5); (CH3)2NH2Cl (26.6); (CH3)3NHCl (33.8); (CH3)4NCl (44.7) CH3NCO (14.1) Example ()

Chemical Shift Range (ppm) <930 608 ~500 380350 367 360325 350300 ~310 310.1 250200 260175 ~160 ~150 120110 110100 12590 ~100 11060 10070 7050 400 5010 6520 ~15

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15

N Chemical Shifts of Major Chemical Families (continued) Family Example () Miscellaneous N-Methylimidazole (111.4, pyridine N; 215.7, pyrrole N)c Piperidinium hydrochloride (344.8); 2-methyl piperidinium hydrochloride (322.1)d trans-Decahydroquinolinium hydrochloride (322.5); cis-decahydroquinolinium hydrochloride (328.5) CH3C(=O)CH=CHNHCH3 [(E)-(294.2); (Z)-(285.9)] 2,6-Diphenyl 4-aminotetrahydropyran (34.5) 2,6-Diphenyl 4-aminotetrahydrothiopyran (33.6) 8-Nitro-1-naphthylamine (313.9) HN[Si(CH3)3]2 (354.2)

Chemical Shift Range (ppm)

130 to 110 and ~212 345 to 310c

Imidazoles Piperidine, hydrochloride salts Decahydroquinolines, hydrochloride salts

293 to 280e 3515f 325 to 310

g

Enaminones 4-Aminotetrahydropyrans 4-Aminotetrahydrothiopyrans 1-Naphthylamines Silylamines

350 to 300h
a

c d e f

g h

Downeld from anhydrous liquid ammonia, 0.2 ppm unless otherwise specied.1 (The indicated superscript numbers refer to the reference list at the beginning of this table.) Varies with solvent, for instance, cyclohexane (315.5), benzene (312.1), chloroform (304.5), methanol (292.1), water (289), 2,2,2-triuoroethanol (277.1). All chemical shifts relative to ammonia.2 Upeld from external HNO3 (1 M ) (CH3OH).4,6,7 Upeld from external HNO3 (1 M ) (cyclohexane).6,7 Relative to external CH315NO2.5 With respect to an external standard of 5 M 15NH4NO3 in 2 M HNO3 (15NH4NO3 = 21.6 ppm relative to anhydrous ammonia).9 In ppm upeld from external 1 M D15NO3 in D2O (DMSO).10 Relative to N(SiH3) (50% in CDCl3).11

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SPINSPIN COUPLING TO

15

The following list gives representative spinspin coupling ranges (JNH in Hz) to 15N.19

REFERENCES
1. Levy, G.C. and Lichter, R.L., Nitrogen-15 Nuclear Magnetic Resonance Spectroscopy, John Wiley & Sons, New York, 1979. 2. DelBene, J.E. and Bartlett, R.J., NN spinspin coupling constants [2hJ(15N-15N)] across N-H: N hydrogen bonds in neutral complexes: to what extent does the bonding at the nitrogens inuence 2hJN-N? communication, J. Am. Chem. Soc., 122, 10480 2000. 3. Del Bene, J.E., Perera, S.A., Bartlett, R.J., Yez, M., M, O., Elguero, J., and Alkorta, I., Two bond 19F14N spin spin coupling constants (2hJ H hydrogen bonds, J. Phys. Chem., 107, F-N) across F-H 3121, 2003. 4. Duthaler, R.O. and Roberts, J.D., Effects of solvent, protonation, and N-alkylation on the 15N chemical shifts of pyridine and related compounds, J. Am. Chem. Soc., 100, 4969, 1978. 5. Duthaler, R.O. and Roberts, J.D., Steric and electronic effects on 15N chemical shifts of saturated aliphatic amines and their hydrochlorides, J. Am. Chem. Soc., 100, 3889, 1978. 6. Kozerski, L. and von Philipsborn, W., 15N chemical shifts as a conformational probe in enaminones: a variable temperature study at natural isotope abundance, Org. Magn. Reson., 17, 306, 1981. 7. Subramanian, P.K., Chandra Sekara, N., and Ramalingam, K., Steric effects on nitrogen-15 chemical shifts of 4-aminooxanes (tetrahydropyrans), 4-amino-thianes, and the corresponding N,N-dimethyl derivatives: use of nitrogen-15 shifts as an aid in stereochemical analysis of these heterocyclic systems, J. Org. Chem., 47, 1933, 1982. 8. Kupce, E., Liepins, E., Pudova, O., and Lukevics, E., Indirect nuclear spinspin coupling constants of nitrogen-15 to silicon-29 in silylamines, J. Chem. Soc. Chem. Commun., 581, 1984. 9. Axenrod, T., Structural effects on the one-bond 15N-H coupling constant, in NMR Spectroscopy of Nuclei Other Than Protons, Axenrod, T. and Webb, G.A., Eds., Wiley Interscience, New York, 1974.

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15

NH Coupling Constants Family Ammonia Amines, aliphatic (1, 2) Ammonium salts Amines, aromatic (1, 2) Sulfonamides Hydrazines Amides (1, 2) Pyrroles Nitriles, salts JNH 61.2 ~ 65 ~ 75 Example NH3 CH3NH2 (64.5) (CH3)2NH (67.0) CH3NH3Cl (75.4) (CH3)2NH2Cl (76.1) C6H5NH3+ (76) C6H5NH2 (78.5) p-CH3OC6H4NH2 (79.4) p-O2NC6H4NH2 (92.6) C6H5SO2NH2 (80.8) C6H5NHNH2 (89.6) HCONH2 (88) (syn); (92) (anti) Pyrrole (96.53) CH3CNH+ (136) CH3NH2 (1.0) (CH3)3N (0.85) C5H5NH+ (3) C4H4NH (4.52) C3H3NS C5H5N (10.76) >C=NOH (syn) >C=NOH (anti) CH3CNH+ (2.8) CH3CONH2 (1.3) C6H5NH2 (1.5, 1.8) C5H5N (0.2) CH3CN (1.7) C5H5NH+ (3.98) C4H4NH (5.39)

Bond Type One bond

78 to 95

~ 80 90 to 100 85 to 95 95 to 100 ~ 135 ~ 1 ~ 3 ~ 5 ~ 10 ~ 10 ~ 15 2.5 to +2.5 ~2 to ~1 to ~1 to ~0 to 1 to ~ 4 ~ 5 4 2 2 1 2

Two bond

Amines Pyridinium salts Pyrroles Thiazoles Pyridines Oximes, syn Oximes, anti

Three bond

Nitriles, salts Amides Anilines Pyridines Nitriles Pyridinium salts Pyrroles

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15

N13C Coupling Constants Family Amines, aliphatic Ammonium salts, aliphatic Ammonium salts, aromatic Pyrroles Amines, aromatic Nitro compounds Nitriles Amides JCH, H2 ~ 4 ~ 5 ~ 9 ~ 10 11 to 15 10 to 15 ~ 17 ~ 14 79 ~3 ~13 Example CH3NH2 (4.5) CH3(CH2)2NH2 (3.9) CH3(CH2)2NH3+ (4.4) C6H5NH3+ (8.9) C4H4NH (10.3) C6H5NH2 (11.43) CH3NO2 (10.5) C6H5NO2 (14.5) CH3CN (17.5) C6H5NHCOCH3 (14.3) (CO); (14.1) (C1) CH3CONH2 (9.5) CH3CN (3.0) C5H5N (2.53) C5H5NH+ (2.01) C5H5NO (1.43) CH3CH2CH2NH2 (1.2) C6H5NO2 (1.67) C6H5NH2 (2.68) C6H5NH3+ (1.5) C4H4NH (3.92) CH2=CHCONH2 (19) CH3(CH2)2NH3+ (1.3) C6H5NH3+ (2.1) C5H5N (2.53) CH3(CH2)2NH2 (1.4) C6H5NH2 (2.68) C6H5NO2 (1.67) C4H4NH (3.92)

Bond Type One bond

Two bond

Amides Nitriles Pyridines and N-derivatives

Amines, aliphatic Nitro compounds, aromatic Amines, aromatic Pyrroles Amides Ammonium salts Pyridines Amines, aliphatic Amines, aromatic Nitro compounds Pyrroles
15

~12 ~ 1 to 2 ~ 1 to 2 ~ 4 9 19 ~3 13 ~ 1 to 3 ~ 2 ~ 4

Three bond

N15N Coupling Constants Family Azocompounds N-Nitrosamines Hydrazones Hydrazines

15

Bond Type

JNN, H2 1225 ~19 ~10 ~7

Example C6H5N=NC(CH3)2C6H5 (17) (anti); (21) (syn) (C6H5CH2)2NN=0 (19) p-O2NC6H4CH=NNHC6H5 (10.7) C6H5NHNH2 (6.7)

N19F Coupling Constants Family Diurodiazines trans cis Fluoropyridines 2-uoro3-uoroFluoroanilines 2-uoro3-uoro4-uoroFluoroanilinium salts 2-uoro3-uoro4-uoroJNF , H2 ~190 ( JNF) ~102 (2JNF) ~203 (1JNF) ~52 (2JNF) 52.5 +3.6 0 0 1.5 1.4 0.2 0 1,2-C6H4F (NH2) 1,3-C6H4F (NH2) 1,4-C6H4F (NH2) 1,2-C6H4F (NH3+) 1,3-C6H4F (NH3+) 1,4-C6H4F (NH3+)
1

Bond Type

Example FN=NF FN=NF FN=NF FN=NF (190) (102) (203) (52)

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19

F CHEMICAL SHIFT RANGES

The following table lists the 19F chemical shift ranges (in ppm) relative to neat CFCl3.14

REFERENCES
1. Yoder, C.H. and Schaeffer, C.D., Jr., Introduction to Multinuclear NMR: Theory and Application, Benjamin/Cummings, Menlo Park, CA, 1987. 2. http://nmrsg1.chem.indiana.edu/NMRguidemisc/19Fshifts.html. 3. Dungan, C.H. and Van Wazer, I.R., Compilation of Reported 19F Chemical Shifts 1951 to Mid 1967, Wiley Interscience, New York, 1970. 4. Emsley, J.W., Phillips, L., and Wray, V., Fluorine Coupling Constants, Pergamon, New York, 1977.

19

F Chemical Shift Ranges Chemical Shift Range (ppm) Relative to Neat CFCl3 70 to 20 +40 to +80 +80 to +140 +140 to +250 +80 to +170

Compound Type FC(=O) CF3 >CF2 >CF ArF Ar = aromatic moiety

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19

F CHEMICAL SHIFTS OF SOME FLUORINE-CONTAINING COMPOUNDS

The following table lists the 19F chemical shifts of some uorine-containing compounds relative to neat CFCl3. All chemical shifts are those of neat samples, and the values pertain to the uorine present in the molecule.13

REFERENCES
1. http://nmrsg1.chem.indiana.edu/NMRguidemisc/19Fshifts.html, 2003. 2. Dungan, C.H. and Van Wazer, I.R., Compilation of Reported 19F Chemical Shifts 1951 to Mid 1967, Wiley Interscience, New York, 1970. 3. Emsley, J.W., Phillips, L., and Wray, V., Fluorine Coupling Constants, Pergamon, New York, 1977.

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19

F Chemical Shifts of Some Fluorine-Containing Compounds Compound CFCl3 CF4 CH3F CF3H CF3R CF2H2 CH3CH2F FCH=CH2 CF2=CH2 CF2=CF2 CF3COOH CF3COOC6H5 CF3COOCH2C6H5 CF3COOCH3 CF3COOCH2CH3 C 6F 6 C 6F 5H p-C6H4F2 C6H5CH2F C6H5CF3 C 4F 8 C5F10 CHF2OR (CF3)2CO F2 CF3Cl ClF3 ClF5 CF2Cl2 CFCl2CFCl2 CFBr3 CF2Br2 IF7 AsF3 AsF5 BF3 (CH3)2O.BF3 (C2H5)2O.BF3 SF6 SO2F SbF5 SeF6 SiF4 TeF6 SF6 XeF2 XeF4 XeF6 NF3 POF3 PF3 Chemical Shift (ppm) 0.00 62.3 271.9 78.6 60 to 70 143.6 231 114 81.3 135 78.5 73.85 75.02 74.21 78.7 164.9 113.5 106.0 207 63.72 135.15 132.9 82 84.6 +422.92 28.6 +116, 4 +247, +412 8 67.8 +7.38 +7 +170 40.6 66 131.3 158.3 153 +57.42 78.5 108 +55 163.3 57 57 +258 +438 +550 +147 90.7 67.5

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FLUORINE COUPLING CONSTANTS The following table gives the most important uorine coupling constants, namely, JFN, JFCF , and JCF , together with some typical examples.19 The coupling constant values vary with the solvent used.3 The book by Emsley et al.1 gives a complete, detailed list of various compounds.

REFERENCES
1. Emsley, J.W., Phillips, L., and Wray, V., Fluorine Coupling Constants, Pergamon Press, Oxford, 1977. 2. Lambert, J.R., Shurvell, H.F., Verbit, L., Cooks, R.G., and Stout, G.H., Organic Structural Analysis, Macmillan, New York, 1976. 3. Yoder, C.H. and Schaeffer, C.D., Jr., Introduction to Multinuclear NMR: Theory and Application, Benjamin/Cummings, Menlo Park, CA, 1987. 4. Schaeffer, T., Marat, K., Peeling, J., and Veregin, R.P., Signs and mechanisms of 13C, 19F spin-spin coupling constants in benzotriuoride and its derivatives, Can. J. Chem., 61, 2779, 1983. 5. Adcock, W. and Kok, G.B., Polar substituent effects on 19F chemical shifts of aryl and vinyl uorides: a uorine-19 nuclear magnetic resonance study of some 1,1-diuoro-2-(4-substituted-bicyclo[2,2,2]oct1-yl)ethenes, J. Org. Chem., 50, 1079, 1985. 6. Newmark, R.A. and Hill, J.R., Carbon-13-uorine-19 coupling constants in benzotriuorides, Org. Magn. Reson., 9, 589, 1977. 7. Adcock, W. and Abeywickrema, A.N., Concerning the origin of substituent-induced uorine-19 chemical shifts in aliphatic uorides: carbon-13 and uorine-19 nuclear magnetic resonance study of 1-uoro-4-phenylbicyclo[2,2,2]octanes substituted in the arene ring, J. Org. Chem., 47, 2945, 1982. 8. Dungan, C.H. and Van Wazer, I.R., Compilation of Reported 19F Chemical Shifts 1951 to Mid 1967, Wiley Interscience, New York, 1970. 9. Emsley, J.W., Phillips, L., and Wray, V., Fluorine Coupling Constants, Pergamon Press, New York, 1977.

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19

FH Coupling Constants JFH Example Two Bond CH3F (45); CH2F2 (50); CHF3 (79); C2H5F (47); CH3CHF2 (57); CH2FCH2F (48); CH2FCHF2 (54); CF3CH2F (45); CF2HCF2CF3 (52) FCl2CH (53); CF2HCl (63); FCHClCHCl2 (49); FCH2CH2Cl (46) FBrCHCH3 (50.5); FH2CCH2Br (46); FBrCHCHFBr (49) FHC=CHF (cis, 71.7; trans, 75.1); CH2=CHF (85); CF2=CHF (70.5); FCH2CH=CH2 (47.5) ClC6H4CH2F (m-47, p-48); FH2CC6H4NO2 (m-47, p48); FH2CC6H4F (m-48, p-48); p-BrC6H4OCF2H (73) FH2COCH3 (74); CF2HCF2OCH3 (46); F2HCOCH(CH3)2 (75) FCH2COCH3 (47); F2HCCOCH3 (54); CH3CH2CHFCOCH3 (50); F2HCCOCH(CF3)2 (54) CH3CH2CHFCHO (51) CFH2CO2CH2CH3 (47); CH3CHFCO2CH2CH3 (48) Three Bond CF2HCH3 (21); (CH3)3CF (20.4); CH3CHFCH2CH2CH3 (23); CF3CH3 (13) CF2HCHCl2 (8); CF2ClCH3 (15) CF2BrCH2Br (22); CF2BrCH3 (16); FC(CH3)2CHBrCH3 (21) CHF=CHF (cis, 19.6; trans, 2.8); CH2=CHF (cis, 19.6; trans, 51.8); CHF=CF2 (cis, 4.2; trans, 12.5); CH2=CF2 (cis, 0.6; trans, 33.8) CF3CH2OH (8); FCH2CH2OH (29); CH3CHFCH2OH (23.6, 23.6); CF3CH(OH)CH3 (7.5); CF3CH(OH)CF3 (6); FC(CH3)2C(OH)(CH3)2 (23) CH3CH2CHFCOCH3 (24); FC(CH3)2COCH3 (21); (CF3)2CHCOCH3 (8); CF2HCOCH(CF3)2 (7) (CH3)2CFCHO (22) CH3CHFCO2CH2CH3 (23); (CH3CH2)2CFCO2CH3 (16.5)

Fluorinated Family

Alkanes

4580

Alkyl chlorides Alkyl bromides Alkenes Aromatics Ethers Ketones Aldehydes Esters

4965 4550 4580 4575 4075 4550 ~50 4570

Alkanes Alkyl chlorides Alkyl bromides Alkenes

225 820 1525 5 to 60 JHCF (cisoid), <20 JHCF (transoid), >20 530

Alcohols

Ketones Aldehydes Esters

525 1025 1025

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F19F Coupling JFCF Examples Two Bond CF3CF2a,bCFHCH3 (Jab = 270); CF2a,bBrCHFSO2F (Jab = 188); CH3OCF2a,bCFHSO2F (Jab = 147); CH3OCF2a,bCFHCl (Jab = 142); CH3SCF2a,bCFHCl (Jab = 222) F2C(CH2)2 (150) (three-membered) F2C(CH2)3 (200) (four-membered) F2C(CH2)4 (240) (ve-membered) F2C(CH2)5 (228) (six-membered) CF2=CH2 (31, 36); CF2=CHF (87); CF2=CBrCl (30); CF2=CHCl (41); CF2=CFBr (75); CF2=NCF3 (82); CF2=CFCN (27); CF2=CFCOF (7); CF2=CFOCH2CF3 (102); CF2=CBrCH2N(CF3)2 (30); CF2=CFCOCF2CF3 (12); CF2=CHC6H5 (33); CF2=CH(CH2)5CH3 (50); CF2=CHAr[Ar=aryl] (50) Three Bond CF3CH2F (16); CF3CF3 (3.5); CF3CHF2 (3); CH2FCH2F (1012); CF2aHCFbHCF2H (Jab = 13); CF2HCF2aCH2F (Jab = 14); CF3aCF2bCFcHCH3 (Jab < l; Jbc = 15); CF3aCFbHCF2cH (Jab = 12; Jbc = 12); CF3aCF2bCCF3 (Jab = 3.3); CF3aCF2bCCCF3 (Jab = 3.3); (CF3a)2CFbCCCl (Jab = 10); CF3CF2COCH2CH3 (1); FCH2CFHCO2C2H5 (11.6); CF3aCF2bCF2cCOOH (Jab < l; Jbc < l); (CF3a)2CFbS(O)OC2H5 (Jab = 8) FCH=CHF (cis, 18.7; trans, 133.5); CF2=CHBr (34.5); CF2=CHCl (41); CF2=CH2 (37)

Carbon

Saturated (sp3)

140250

Cycloalkanes

150240

Unsaturated (sp2)

100

Saturated (sp3)

016

Unsaturated (sp2)

>30

C19F Coupling Fluorinated Family JCF , H2 Examples One Bond CH3F (158); CH2F2 (237); CHF3 (274); CF4 (257); CF3CF3 (281); CF3CH3 (271); (CH3)3CF (167); (CaF3b)2CcF2d (Jab = 285; Jcd = 265) CF2=CD2 (287); CF2=CCl2 (289); CF2=CBr2 (290); ClFC=CHCl (cis, 300; trans, 307); ClFC=CClF (cis, 290; trans, 290) CaF3bCCF (Jab = 259); CF3CCCF3 (256) CFCl3 (337); CF2Cl2 (325); CF3Cl (299); CF3(CCl2)2CF3 (286); CF3CH2Cl (274); CF3CCl=CCl2 (274);CF2=CCl2 (289); CF3CCl3 (283) CFBr3 (372); CF2Br2 (358); CF3Br (324); CF3CH2Br (272); CF2=CBr2 (290) HCOF (369); CH3COF (353) CF3COOH (283); CF2HCO2H (247) CF3CH2OH (278) CF2HCN (244) CF3CO2CH2CH3 (284) CF3COCH3 (289) (CF3)2O (265)

Alkanes Alkenes Alkynes Alkyl chlorides

150290 250300 250260 275350

Alkyl bromides Acyl uorides Carboxylic acids Alcohols Nitriles Esters Ketones Ethers

290375 350370 245290 ~275 ~250 ~285 ~290 ~265

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RESIDUAL PEAKS OBSERVED IN THE 1H NMR SPECTRA OF COMMON DEUTERATED ORGANIC SOLVENTS The following table lists the residual peaks that are observed in the 1H NMR spectra of common deuterated organic solvents. These peaks are generally attributed to the nondeuterated parent compound that serves as an impurity and are marked with an asterisk. In addition, other less signicant peaks often arise due to other impurities. Together with the formula and molecular weight, the table lists the expected chemical shifts, ; multiplicities; and, when possible, the coupling constant, JHD, for every solvent. All spectra are at least 99.5% deuterium pure.15

REFERENCES
1. Yoder, C.H. and Schaeffer, C.D., Jr., Introduction to Multinuclear NMR, Benjamin Cummings, Menlo Park, CA, 1987. 2. Silverstein, R.M. and Webster, F.X., Spectrometric Identication of Organic Compounds, 6th ed., John Wiley & Sons, New York, 1998. 3. Gunther, H., NMR Spectroscopy: Basic Principles, Concepts and Applications in Chemistry, John Wiley & Sons, New York, 2003. 4. Lambert, J.B., Holland, L.N., and Mazzola, E.P., Nuclear Magnetic Resonance Spectroscopy: Introduction to Principles, Applications and Experimental Methods, Prentice Hall, Englewood Cliffs, NJ, 2003. 5. Nelson, J.H., Nuclear Magnetic Resonance Spectroscopy, 2nd ed., John Wiley & Sons, New York, 2003.

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Residual Peaks Observed in the 1H NMR Spectra of Common Deuterated Organic Solvents Solvent Acetic acid-d4 Acetone-d6 Acetonitrile-d3 Benzene-d6 Chloroform-d3 Formula CD3COOD (CD3)2C=O CD3CN C 6D 6 CDCl3 Molecular Weight 64.078 64.117 (mult)a *11.53 (1) *2.03 (5) *2.04 (5) 2.78 (1) 2.82 (1) *1.93 (5) 2.12.15 2.22.4 *7.12 (b) 1.55b 1.60b 7.2 *7.24 (1) *1.38 (b) *4.63 (b)c *4.67 (b)d *3.72 (b) JHD 2 2.2

44.017

2.5

84.153 120.384

Cyclohexane-d12 Deuterium oxide 1,2-Dichloroethane-d4 Dichloromethane-d2 Diethylene glycol dimethylether-d14 Diethylether-d10 Diglyme-d14 N,N-Dimethylformamide-d7 Dimethylsulfoxide-d6 1,2-Diethoxyethane-d10 p-Dioxane-d8 Ethanol-d6 (anhydrous) Glyme-d10 Hexamethylphosphoric triamide-d18 (HMPT-d18) Methanol-d4 Methylene chloride-d2 Nitrobenzene-d5 Nitromethane-d3 2-Propanol-d8 Pyridine-d5

(CD2)6 D20 CD2ClCD2Cl See Methylene chloride-d2 See Diglyme-d14 (CD3CD2)2O CD3O(CD2)2O(CD2)2OCD3 DCON(CD3)2 (CD3)2SO See Glyme-d10 C4H8O2 CD3CD2OD CD2OCD2CD2OCD3 [(CD3)2N]3P=O CD3OH CD2Cl2 C6D5NO2 CD3NO2 (CD3)2CDOD C6D5N

96.236 20.028 102.985

84.185 148.263

80.138

*3.34 (m) *1.07 (m) *3.49 (b) *3.40 (b) *3.22 (5) *8.01 (b) *2.91 (5) *2.74 (5) 3.33.4 *2.49 (5)

1.5

2 2 1.7

96.156 52.106

100.184 197.314 36.067 86.945 128.143

*3.53 *5.19 *3.55 *1.11 *3.40 *3.22 *2.53

(m) (1) (b) (m) (m) (5) (m)

1.6

64.059 68.146

84.133

*4.78 (1) *3.30 (5) *5.32 (3) 1.41.5 (b) *8.11 (b) *7.67 (b) *7.50 (b) *4.33 (5) *5.12 (1) *3.89 (b) *1.10 (b) *8.71 (b) *7.55 (b) *7.19 (b) 4.8b 4.9b

1.7 1

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Residual Peaks Observed in the 1H NMR Spectra of Common Deuterated Organic Solvents (continued) Solvent Tetrahydrofuran-d8 Formula C4D8O Molecular Weight 80.157 (mult)a *3.58 (b) 2.4b 2.3b *1.73 (b) *7.09 (m) *7.00 (b) *6.98 (m) *2.09 (5) *11.50 (1) JHD

Toluene-d8

C6D5CD3

100.191

2.3

Triuorocetic acid-d
a

CF3COOD

115.030

b c

Chemical shift, , in ppm; mult = multiplicity (indicated by a number); b = broad, m = multiplet. Two peaks that may often appear as one broad peak. When DSS, 3-(trimethylsilyl)-1-propane sulfonic acid, sodium salt, is used as a reference standard. When TSP, sodium-3-trimethylpropionate, is used as a reference standard.

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