(J* j' antibonding e<:) Q>4t (sp3-sp3)

' '
n ➔ a* variab le
n* anti bonding (p-p)
I .. .~
1 n ➔ re*::: 28 0nm
(w eak)

non bonding (p)

1! ➔ re* ::: 180 nm
(strong)
1! bonding ,.,..__ _,. (p-p)
a ➔ a* <1 8 0n m
(strong)
(] bonding -<:X:)e (sp3-sp3-/sp2-sp2/sp-sp)
or
ec:::::::::::o (sp3-s/sp 2-s/sp-s)
Fig. 3.3 Electronic energy levels and electronic transitions.
 oc•CC
00
c<a
C
(a) a ➔ alf< Transition

*
- - - acN

_o_
n
o_ n(sp3)
\ 00
n ➔ er*

0 0
acN

(b) n ➔ ~ Transition

---n*

oO

(c) n➔ 'Tr"" Transition

(fff Transition
Fig. 3.4 Electronic Transitions: (a) a ➔ a* Transition (b) n -
(c) 1C ➔ ~ Transition.
 -0
0
~o
II ( f\ )

..

..

.. n(spJ

Fig. 3.5 ,r-; ,r4 and n -; rr- Transitions or the Carbonyl Group.

1-1 g. 3.6 n -4 ~ Excitation of lb~ carbonyl group.

"T
 Monochromator
f I c:::::;:: I
Beam splitter
I
Attenuators
Sample

Prism
Detector
M

Rotating
Sector
Radiation
Source
1

R
_ ec_o_r_de_r_ ......1
'--I_ _ - . . . . , - - - - '

Electronic
Amplifier
Motor

Electrons

Light - ~ - - + --"
Anode
Dynodes

•
I
J
Radiation - / Photocathode @ e
Multiplication of electrons in a Photocell
photomultiplier tube

.) F·ig. 3.10 Double Beam Ultraviolet Spectrometer

(I Ratt·
IhA_ lation sourcP
 SIJV ,. -

JJ.4 WOODWARD-FIESER RULES FOR CALCULATING ABSORPTION MAXIMA OF

3 UNSATURATED HYDROCARBONS

Calculation of absorption maxima for unsaturated compounds

The absorption maxima for a conjugated or substituted diene can be predicted by
using the data given in the Table 3.6.

Table 3.6 Woodward and Fieser's rules for calculating ultraviolet absorption maxima
of substituted diene (ethanol solution)

(i) Parent acyclic diene 217 nm

(ii) Parent heteroannular diene 214 nm
(iii) Parent hornoannular diene 253 nm
Increments for substituents
(iv) Alkyl group or ring residue +5 nm
(If the alkyl group is attached to
two double bonds, count it twice)
(v) Exocyclic double bond (effect is two- +5 nm
fold if bond is exocyclic to two rings)
(vi) Double bond extending conjugation +30 nm
Substituents on vinyl carbons (for each one)
(vii) Halogen (-Cl, -Br) +5 nm
(viii) O-(alkyl) (-OR) +6 nm
O-(acyl) (-0-COR) +O nm
(ix) S-(alkyl) (S-R) +30 nm
_ (x) N-(alkyl)i (-NRR.,) + 60 nm

Calculat · if ,
°
con · zon Amax (nm) and Emaxfor systems containing more than four
Th ~ugated double bonds
erules dep· t d. . .
upto fo ic e in the table 3.6 holds good for unsaturated compounds conta1n1ng
ur double bonds. However, for conjugated systems containing more than
 e important examples which serve to illustrate the application of these rules
sorn . d d.
•ety of conJugate 1ene systems are depicted as follows ·
wa~n .
Parent acyclic diene = 217 nm

K Substituents 2 x 5

Cale. A max
Obs. Amax
=

=
=
10nm

227nm
226nm

Parent acyclic diene = 217 nm

Substituent or ring residues 2 x 5 = 10nm
Exocyclic double bond 1 x 5 = 5nm

Cale. Amax = 232 nm

Obs. Amax = 237 nm

Parent acyclic diene = 217 nm

Ring residues 4 x 5 = 20nm
Exocyclic doubl e bonds 2 x 5 = 10nm

Cak. A.max = 247nm

Obs. Amax = 247 nm

Base value (heteroannular diene) = 214nm

Substituents or ring residues 3 x 5 = 15 nm
Exocyclic double bond 1 x 5 = 5nm

Cale. A.max = 234nm

Parent heteroannular diene = 214nm

Double bond extending
conjugation I x 30 = 30nm
Ring residues 4 x 5 = 20nm
Exocyclic double bond 2 x 5 = 10nm

Cale. Amax = 274 nm

Parent heteroannular diene = 214nm

Ring residues 3 x 5 = 15 nm
Exocyclic double bond l x 5 = 5 nm
Cale. Ainax = 234nm
Obs. Aimu = 234 nm

Parent heteroannular diene = 214 nm

Ring residues 4 x 5 = 20nm

Exocyclic double bond 2 x 5 = 10nm

Cale. Amax = 244nm