Woodward's rules

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Woodward's rules are a set of rules which give information about the wavelength of the absorption maximum (symbol λmax ) in an ultraviolet-visible (UV) spectrum of a compound. The rules are named after Robert Burns Woodward. He was a Harvard University chemistry professor who won the Nobel Prize in chemistry. The rules are sometimes called the Woodward-Fieser rules, to also honor Louis Fieser. The rules build the prediction on the type of chromophores present, the substituents on the chromophores, and changes due to the solvent.[1][2] Examples are conjugated carbonyl compounds[3][4] conjugated dienes,[5] and polyenes.[4]

Implementation[change | change source]

One set of Woodward-Fieser rules for dienes is shown in table one. A diene is either homoannular with both double bonds contained in one ring or heteroannular with two double bonds distributed between two rings.

Base value for heteroannular diene 214
Base value for homoannular diene 253
Double bond extending conjugation + 30
Alkyl substituent or ring residue + 5
Exocyclic double bond + 5
acetate group + 0
Ether group + 6
Thioether group + 30
bromine, chlorine + 5
secondary amine group + 60
Table 1. Rules for wavelength of maximum
diene absorption (in nanometers) [6]

These rules predict the UV absorption maximum of compounds. Here are two examples:[7]

Example of Woodward-Fieser rules

In the compound on the left the base value is 214 nm (a heteroannular diene). This diene group has 4 alkyl substituents (labeled 1,2,3,4) and the double bond in one ring is exocyclic to the other (adding 5 nm for an exocyclic double bond). In the compound on the right, the diene is homoannular with 4 alkyl substituents. Both double bonds in the central B ring are exocyclic with respect to rings A and C.

References[change | change source]

  1. Woodward, Robert Burns (1941). "Structure and the Absorption Spectra of α,β-Unsaturated Ketones". J. Am. Chem. Soc. 63: 1123. doi:10.1021/ja01849a066 .
  2. Louis F. Fieser, Mary Fieser, Srinivasa Rajagopalan (1948). "Absorption Spectroscopy and the Structures of the Diosterols". J. Org. Chem. 13: 800. doi:10.1021/jo01164a003 . PMID 18106021 .
  3. Neil Glagovich (2007-07-19). "Woodward's Rules for Conjugated Carbonyl Compounds". Central Connecticut State University. http://www.chemistry.ccsu.edu/glagovich/teaching/316/uvvis/conjugated.html. Retrieved 2008-05-05.
  4. 4.0 4.1 William Reusch. "UV-Visible Spectroscopy". VirtualText of Organic Chemistry. Michigan State University. http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/UV-Vis/uvspec.htm.
  5. Neil Glagovich (2007-07-19). "Woodward-Fieser Rules for Dienes". Central Connecticut State University. http://www.chemistry.ccsu.edu/glagovich/teaching/316/uvvis/diene.html. Retrieved 2008-05-05.
  6. Spectroscopic Determination of Organic Compounds, 5th Edition, Silverstein, Bassler, Morrill 1991
  7. Organic spectroscopy William Kemp