Several sets of empirical derived rules to estimate the absorption maxima (max) in UV spectrum.

Woodward and Fieser Rule

It depends upon contribution upon substitution like Polyenes, conjugated carbonyl [ketone & aldehyde]. Louis Frederick Fieser (1899 -1977) Synthesis ofVitamin - K

Robert B. Woodward [1917-1979] ,Nobel Prize Winner in Chemistry 1965"for his outstanding achievements in the art of organic synthesis[Synthesis of Vitamin - B12] This work was distilled by Scott in 1964 into an extensive treatise on the Woodward-Fieser rules in combination with comprehensive tables and examples (A.I. Scott, Interpretation of the Ultraviolet Spectra of Natural Products, Pergamon, NY, 1964) A more modern interpretation was compiled by Rao in 1975 (C.N.R. Rao, Ultraviolet and Visible Spectroscopy, 3rd Ed., Butterworths, London, 1975)

Woodward-Fieser Rules for Dienes

Exo-cyclic double bond Exo-cyclic double bond that lies outside a given ring. It may lie within one ring even though it is outside anther ring. Often an exocyclic double bond will be found at a junction point on rings.

Three exocyclic double bond

Woodward-Fieser Rules Cyclic Dienes

Be careful with your assignments three common errors: This compound has three exocyclic double bonds; the indicated bond is exocyclic to two rings This is not a heteroannular diene; you would use the base value for an acyclic diene This is not a homooannular diene; you would use the base value for an acyclic diene

For example:

Worked Problem

Isoprene - acyclic butadiene = 217 nm one alkyl subs. = + 5 nm calculated 222 nm Experimental value 220 nm

Isoprene - acyclic butadiene = 217 nm three alkyl subs. (3X5) = +15 nm calculated 232 nm Experimental value 234 nm

Worked Problem

Where , R=H

Transoid : =214 nm Alkyl group (or) Ring residue : (3X5) = 15 nm Exocyclic double bond = 5 nm --------------Calculated: 234 nm Observed: 235 nm

Find : R = -OCH2CH3, OCOCH3 R=-OCH2CH3 , max = 240nm, R=-OCOCH3 , max = 234nm.

Worked Problem

Cisoid : =253 nm Alkyl group (or) Ring residue : (2X5) = 10 nm --------------Calculated: 263 nm Observed: 256 nm

Cisoid : =253 nm Alkyl group (or) Ring residue : (3X5) = 15 nm --------------Calculated: 268 nm
Cisoid : =253 nm Alkyl group (or) Ring residue : (4X5) = 20 nm Exocyclic double = 5 nm bond --------------Calculated: 278 nm Observed: 275 nm

Worked Problem

Palustric acid Cisoid : =253 nm Alkyl group (or) Ring residue : (4X5) = 20 nm Exocyclic double = 5 nm bond --------------Calculated: Observed: 278 nm 275 nm

Neoabietic acid

Acyclic : =217 nm Alkyl group (or) Ring residue : (5X5)= 25 nm Exocyclic : (2x5) = 10nm Double bond --------------Calculated: 252 nm

Worked Problem

Transoid : =214 nm Alkyl group (or) Ring residue : (3X5) = 15 nm Exocyclic : (1x5) = 05nm Double bond --------------Calculated: 234 nm Transoid : =214 nm Alkyl group (or) Ring residue : (4X5) = 20 nm Exocyclic : (2x5) = 10nm Double bond --------------Calculated: 244 nm Cisoid : =253 nm Alkyl group (or) Ring residue : (4X5) = 20 nm Exocyclic : (2X5) = 10 nm bond --------------Calculated: 283 nm

Home Work Problems

a) Assign the max (275, 239 and 235) of the following steroids ?

(i)

(ii)

(iii)

b) Assign the max (235, 268 and 241) of the following steroids ?

Find the max of the following compound Home work problems [Out of syllabus]

249

284

323

353

Woodward-Fieser Rules for ,-unsaturated carbonyl

a,b-unsaturated corbony compounds or Enol are a conjugated system of an alkene and a ketone.

Woodward-Fieser Rules for ,-unsaturated carbonyl

Group
6-membered ring or acyclic enone 5-membered ring parent enone Acyclic dienone Double bond extending conjugation
Alkyl group or ring residue -OH -OR -OCOR (OAC) -Cl -Br -NR2 Exocyclic double bond Homocyclic diene component , , and higher , , and higher , , , , , , ,

Increment (nm)
215 202 245 30
10, 12, 18 35, 30, 18 35, 30, 17, 31 6 15, 12 25, 30 95 5 39

Worked problems for ,-unsaturated carbonyl compound

Acyclic enone : 2 X Alkyl group (or) Ring residue Exocyclic Double bond Calculated: Observed: = 215 nm : (2X12) = 24 nm : (0) = 0nm --------------239 nm 237 nm : = 215 nm : (1X12) = 12 nm : (1X10) = 10nm --------------237 nm 236 nm = 215 nm : (2X12) = 24 nm : (1X35) = 35nm --------------274 nm 275 nm

Acyclic enone 1 X Alkyl group 1X Alkyl group Calculated: Observed: Cyclicenone (6-member) : 2 X Alkyl group (or) Ring residue OH sub. at Position Calculated: Observed:

Worked problems for ,-unsaturated carbonyl compound

Cyclic enone (6-member) 2 X Alkyl group (or) Ring residue Exocyclic Double bond Calculated: Observed: : = 215 nm

: (2X12) = 24 nm : (0) = 0nm --------------239 nm 238 nm : = 215 nm

Cyclic enone (6-member) 2 X Alkyl group (or) Ring residue Exocyclic Double bond Calculated: Observed:

: (2X12) = 24 nm : (1X5) = 5nm --------------244 nm 241 nm

Cyclic enone (6-member) : = 215 nm 2 X Alkyl group (or) Ring residue : (2X12) = 24 nm 1X Alkyl group : (1X10) = 10nm Exocyclic : (2X5) = 10nm Double bond --------------Calculated: 259 nm 15 Observed: 256 nm

Can these two isomers be discerned by UV-spectrum

Cyclic enone (6-member) : = 215 nm 1 X Alkyl group (or) Ring residue : (1X12) = 12 nm 1X Alkyl group : (1X10) = 10nm Exocyclic : (1X5) = 05nm Double bond --------------Calculated: 242 nm

Cyclic enone (6-member) 1 X Alkyl group (or) Ring residue 0 X Alkyl group Exocyclic Double bond Calculated:

= 215 nm

: (2X12) = 24 nm : (0) = 0nm : (1X5) = 05nm --------------244 nm

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Worked problems for ,-unsaturated carbonyl compound

Cyclic enone (6-member) : = 215 nm 1 X Alkyl group (or) Ring residue : (1X12) = 12 nm 0X Alkyl group : (0) = 0 nm 0X Alkyl group : (0) = 0 nm 1X Alkyl group : (1X18) = 18 nm Exocyclic = bond : (1X5) = 5 nm Extended Double bond : (1X30) = 30 nm --------------Calculated: 280 nm Observed: 277 nm

Cyclic enone (6-member) : = 215 nm 0 X Alkyl group (or) Ring residue : (0) = 0 nm 0X Alkyl group : (0) = 0 nm 1X Alkyl group : (1X18) = 18 nm 1X Alkyl group : (1X18) = 18 nm Exocyclic = bond : (1X5) = 5 nm Extended Double bond : (1X30) = 30 nm --------------Calculated: 286 nm Observed: 290 nm

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Worked problems for ,-unsaturated carbonyl compound

Cyclic enone (5-member) : = 202 nm 1 X Alkyl group (or) Ring residue : (1X12) = 12 nm 0X Alkyl group : (0) = 0 nm 1X Alkyl group : (1X18) = 18 nm 1X Alkyl group : (1X18) = 18 nm Exocyclic = bond : (1X5) = 5 nm Extended Double bond : (1X30) = 30 nm --------------Calculated: 285 nm Observed: 287 nm

Cyclic enone (6-member) 0 X Alkyl group (or) Ring residue 1X Alkyl group 0X Alkyl group 1X Alkyl group Exocyclic = bond Extended Double bond Homoannular conjugated diene Calculated: Observed:

= 215 nm

: (0) = 0 nm : (1X10) = 10 nm : (0) = 0 nm : (1X18) = 18 nm : (1X5) = 5 nm : (1X30) = 30 nm : (39) = 39 nm --------------317 nm 319 nm

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Worked problems for cross- conjugated system:

Cyclic enone (6-member) : = 215 nm 2 X Alkyl group (or) Ring residue : (2X12) = 24 nm 0X Alkyl group : (0X10) = 0nm Exocyclic : (1X5) = 05nm Double bond --------------Calculated: 244 nm

Cyclic enone (6-member) : = 215 nm 1 X Alkyl group (or) Ring residue : (1X12) = 12 nm 0X Alkyl group : (0X10) = 0 nm Exocyclic : (0) = 0 nm Double bond --------------Calculated: 237 nm

Find the max max of the following compounds

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Unsaturated Carboxylic acid: = 195 nm 1X Alkyl group : (1X12) = 12 nm 1X Alkyl group : (1X10) = 1 0 nm Exocyclic = bond : (0) = 0 nm --------------Calculated: 217 nm Observed: 217 nm Unsaturated aldehyde: 1X Alkyl group 1X Alkyl group Exocyclic = bond Calculated: Observed: = 208 nm : (2X12) = 24 nm : (1X10) = 1 0 nm : (0) = 0 nm --------------242 nm 242 nm

Unsaturated aldehyde: = 208 nm 1X Alkyl group : (1X10) = 10 nm 1X Alkyl group : (1X18) = 18 nm Exocyclic = bond : (0) = 0 nm Extended Double bond : (1X30) = 30 nm Homoannular conjugated : (39) = 39 nm diene --------------Calculated: 305 nm Observed: 302 nm

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Application of UV Spectroscopy
Detection of functional group: To dectect the presence and absence of the funtional group (chromophore) like Conjugation, carbonyl (aldehyde, ketone), benzene (Aromatic compounds) and halo compound ( bromo or iodo atom). Extent of conjugation: The extent of conjugation in polyenes can be estimated. An increase in the double bonds shifts the absorption to longer wave length region (Bathochromic shift). it is found that the absorption occurs in the visible region. i.e at about 420 nm, if n=8 in the above polyene. human eye. n=8 and above alkenes appears colored to

Distinction in conjugated and non-conjugated compounds:

The forbidden n=>* band for the carbonyl group in the compound (2) will appear at longer wave-length compared to that for the compound (1).
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Application of UV Spectroscopy
Elucidation of the structure of Vitamins A and K: Due to presence of additional double bond.

Preference over two tautomeric foam:

The spectra of the two compound were found to favour 2-pyridone which is an a,b-unsaturated ketone and the equilibrium shifted towards the right in polar solvents.
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 Identification of a compound in different solvents: some times the structure of the compound changes with the change of the solvents. Eg.Chloral hydrate CCl3.CHO.H2O. In Hexane shows absorption at 290nm In water no absorption observed due to Determination of configuration of Geometrical isomers: Generally trans forms are more stable than cis form.

Application of UV Spectroscopy

UV absorbance for trans-resveratrol UV lambda(max) (EtOH) nm (epsilon) 308 (30 000) and cis-resveratrol UV lambda(max) (EtOH) nm (epsilon) 288 (12 600). Cis form absorbs at lower wave length and trans forms absorbs at higher wave length. http://www.mendeley.com/research/resveratrol-isomeric-molar23 absorptivities-stability/