They provide information about the wavelength of the maximum absorption (symbol λmax) in an ultraviolet-visible (UV) spectrum of a compound. The rules are named after Robert Burns Woodward. He was a professor at Harvard University, which was awarded the Nobel Prize in Chemistry in 1965. The rules are sometimes called Woodward-Fieser rules to honor Louis Fieser. Woodward`s rules are a set of rules about how organic chemical compounds absorb ultraviolet light. When discussing the Woodward-Fieser rules for unsaturated carbonyl compounds, give a negative value for solvent displacement in the polar solvent (for example, -8 nm for water) and a positive solvent change for nonpolar solvents (+7 nm for hexane). About half of the manuals and web resources give the opposite sign for solvent change (usual value: +8 nm for water, -11 nm for hydrocarbon solvents). It may be helpful to check the original literature to ensure that the values are correct. According to Woodward, for carbonyl compounds α,β-unsaturated, the position of the substituent is significant in determining the influence on the wavelength of maximum absorption. The substituents can be on both positions α β. When conjugation is extended to positions γ and δ, substitutions for these positions also play a crucial role in determining the practical λmax. 3] When the conjugation is extended to γ.δ positions to form servant. For example, in such cases, a simple addition of 30 nm to the baseline value of the carbonyl compound α,β-unsaturated provides corresponding estimates of the observed influences.
See Woodward`s rule problem examples page to learn how λmax conjugated carbonyl compounds are calculated. See also the section on Woodward`s rules for dienes and polyenes. Has. Ring-shaped diene homo:– cyclic diene with conjugated double bond in the same ring. As Woodward and Fieser listed, α,β-unsaturated carbonyl compounds have an effect on the λmax of the molecule, depending on: Note: In the case of carbonyl compounds α,β-γ,δ-diene such as those indicated above, the conjugation extended to the α,β-γ,δ positions in the basic value of the nuclear chromophore is considered and does not need to be added separately. However, if there is another substitute for the α.β γ.δ positions, you must add an additional +30 nm for each. In addition, the bond indicated as β-γ is not counted as a β substituent, but as part of the nuclear chromophore and should not be added separately. These rules can be used to predict maximum UV absorption, for example in these two compounds: These sets of papers are intended to show the student how to use these rules to calculate the wavelength of maximum absorption, or λmax, for different systems. The following pages are listed for readers. As we have already seen in the chapter Principle of UV-Vis spectroscopy, the absorption of a certain wavelength of light depends on the π-electron system of the molecule.
The more the π-electron system conjugates in the molecule, the longer the wavelength of light it can absorb. Robert Burns Woodward and Louis Fieser have established a set of rules that empirically calculate the wavelength of the maximum absorption (λmax) of a molecule. These sets of rules for calculating the wavelength of the maximum absorption, or λmax, of a compound in the ultraviolet-visible spectrum have been empirically called Woodward–Fieser rules or Woodward rules. Note: The numerical values of the Woodward-Fieser rules differ slightly from one textbook to another. We tried to compile a long list of numerical values from online resources, textbooks, and journal articles based on the popularity of the number. It is recommended to learn how to apply the values to contributors and then follow the values given in a textbook recommended by your teacher or use our values. We believe that learning to apply the rules is more important than getting the exact answer. The opinions of others may vary. A Woodward-Fieser set of rules for servants is listed in Table 1. A diene is either homoannular with the two double bonds contained in a ring, or heteroannular with two double bonds distributed between two rings. Since carbonyl functional groups have polarity, solvents play an important role in the development of structural electronics.
The rules are simple and straightforward: Table 2: Specifies values of the influence of different chromophores in conjugated carbonyl systems according to Woodward-Fieser rules. The use of these will become clearer in the following examples. Table 3: Influence of substituents on the α position of carbonyl compounds α,β-unsaturated For polyenes with more than 4 conjugated double bonds, the Fieser-Kuhn rules shall be applied.  1. Holzward-Fieser rule for conjugated diene and polyenes. In a particular case where you have α,β-γ,δ diene-carbonyl compound and both double bonds are present in a cyclic system, you get a homoannular or homocyclic cyclohexadiene carbonyl compound. In this case, you need to add an additional 35nm to the system. The rules base the prediction on the type of chromophores present, substituents on chromophores and changes due to the solvent.   Examples are conjugated carbonyl compounds, conjugated dienes, and polyenes.  Hi Thomas, I went through the literature and texts to find information on the reasons for -8nm for water and +7nm for hexane.
It appears that pi->pi* transitions pass through the bathochrome (redshifts or increased wavelengths), while n->pi* transitions undergo hypsochrome (blue shift or wavelength decrease) when the polarity of the solvent is increased. In the case of carbonyl compounds, since an n->ft* junction determines the UV spectrum, you are expected to observe a blue shift (hypsochrome) as the polarity of the solvent increases. Thus, water would give a shift of -8 nm, while hexane would give a shift of +7 nm. Please let me know which books give opposite values and the page so I can check them. 1] The type of carbonyl functionality present. For example, α,β-unsaturated aldehydes contribute to 210 nm, while α,β-unsaturated ketones contribute to 215 nm and α,β-unsaturated esters contribute to 195 nm. In general, exocyclic double bonds add the baseline of +5 nm additional. To identify exocyclic double bonds, we recommend reading the previous chapter on using Woodward–Fieser rules to calculate the λmax of dienes and conjugated polyenes. We explained it in detail there.
The acyclic conjugated diene or ring-shaped heterocyclic conjugated diene has a wavelength of 215 nm. E. Expanding double bond:– if there are more than conjugated double bonds. The Woodward–Fieser rules can be extended to calculate the λmax of α,β-unsaturated carbonyl compounds. Similar to the Woodward rules discussed earlier for dienes, there is a baseline to which substitution effects can be added and the λmax can be calculated with the formula: Woodward`s rules, named after Robert Burns Woodward and also known as Woodward–Fieser rules (for Louis Fieser), are several sets of empirically derived rules that attempt to determine the wavelength of the maximum absorption (λmax) in an ultraviolet-visible spectrum of a given compound. The inputs used in the calculation are the type of chromophores present, auxochromes (substituents on chromophores) and solvents. [ 1]  Examples are conjugated carbonyl compounds,   conjugated dienes, and polyenes.  . Let`s discuss each of the above values and when they should be applied more specifically, using examples: Any alkyl substitution, ring residue or cycle residue: – 5 nm Take the online pharmacist test FREE: CLICK HERE 2. Alkyl substituent or cyclic residue in position α = 10 nm Nice presentation Akul Mehta. Pls, can you show one or more problems with a homocyclic diene component with solution? (III) AROMATIC COMPOUNDS: 1. Basic value: for (a) ArCOR = 246 nm 4) Polar groups: a) –OH, –OCH3, –OAlkyl in o, position m = 7 nm.
For more standard and quality questions, you can join our GPAT, NIPER JEE Test Series Program, Pharmacist Recruitment Exam, Drug Inspector Recruitment Exam, Doctor 1 Pharmacy Entrance Exam. Baseline: a) acyclic α, β unsaturated ketones = 214 nm II) α, β UNSATURATED CARBONYL COMPOUNDS OR KETONES: Check out these great books for analytical chemistry and spectroscopy Your email address will not be published. Required fields are marked with * 2) alkyl group or cyclic residue in ortho- and meta-position = 3 nm. In the compound on the left, the base value is 214 nm (a heteroanne-shaped diene). This group of services has 4 alkyl substituents (labeled with 1,2,3,4) and the double bond in one ring is exocyclic to the other (addition of 5 nm for an exocyclic double bond). In the compound on the right, diene is homoannular with 4 alkyl substituents. The two double bonds in the central ring B are exocyclic to rings A and C. According to the Holzward–Fischer rule, the λmax of the molecule can be calculated with a formula :-.
D. Exocyclic double bond: double bond in which one of the double bond atoms is part of a ring. C. Endocyclic double bond: – Double bond in a ring. e) α, β unsaturated carboxylic acids and esters = 195 nm As we can see in Table 3 below, the action of the different substituents is at the α position. Basic value: – Each type of diene or trian system has a certain fixed value at which absorption takes place, this value is called the base value. 2] When the nucleus is part of a cyclic ring.