Beruflich Dokumente
Kultur Dokumente
Choice of solvents
Rules for dienes and trienes absorption Rules for , unsaturated aldehydes and ketones
affected by substitution and WOODWARD (1942) found that the position of the absorption maximum depends on their number and type of dienes.
As a result WOODWARD developed a set of
empirical rules (later modified by fieser,1948) for calculating max from the molecular structure of the compound.
wavelength of absorption.
With the increase in the length of
coloured to the naked eye if there are more than five double bonds are in conjugation and absorption occurs around or above 400nm.
The presence of alkyl group on the double bond
Spectroscopy
It is a measurement and interpretation of EMR.
Absorbance
The difference between the intensity of incident light and intensity of transmitted light.
Chromophore
The group which is responsible for absorption of the U.V radiation and may or may not impart the colour to the compound.
SOLVENTS WAVELENGTH Ethanol 210nm Hexane 210nm Methanol 210nm Cyclohexane 210nm Diethyl ether 210nm Water 205nm Benzene 280nm Chloroform 245nm Tetrahydrofuran 220nm Carbon tetra chloride 265nm
217nm
245nm 253nm
215nm
Increment for each substituteAlkyl substituent or ring residue Exocyclic double bond Double bond extending conjugation 5nm 5nm 30nm
Auxochrome
-OR - SR - Cl*, - Br* - NR2 -OCOCH3 + 6nm + 30nm + 5nm + 60nm 0nm
Homoannular diene
Heteroannular diene
CH2
Acyclic diene
H2C
H2C
H3C
CH3
2.
H3C
CH3
H3C
H3C
CH3
Calculate the max for the following compounds.
2.
H3C
H3C
CH3
Observed max 235 Calculated max Base value 214 3-alkyj substituent s 15 1-exocyclic double bond - 05 234
Woodward and fieser framed certain emrpical rules for estimating the
These rules were later modified by Scott and are as follows The basic value , - unsaturated ketone is taken as 215 nm.
The , - unsaturated ketone may be a cyclic or six membered. For a compound, = CH COX, basic value is taken as 215nm If X = alkyl group then the basic value is 215nm If X = H, then the basic value is 207nm If X = OH, then the basic value is 193nm membered ring (cyclopentanone), then for such an , - unsaturated ketone, the basic value becomes 202 nm (The Emax for such compounds are generally above 10,000)
If the double bond and the carbonyl group are contained in a five
For each exocyclic double bond + 5nm For each double bond endocyclic in 5 or 7 membered Ring except cyclo-pent-2 enone + 5nm For each alkyl substituent or ring residue at the position + 10nm position + 12nm or position + 18nm For each double bond extending conjugation + 30nm For a Homoannular conjugated diene + 39nm
Chromophore
carbonyl
-OH -OAc
+ 35 +6 + 15 + 25 + 35
-Cl
-Br -OR
-SR
-NR2
+ 85
+ 95
HO
Observed max 247 Calculated base value 202 1- substituent 10 -OH 35 247
O
O CH3
215 12 10 247
CH3 CH3
Calculate the max for following structures
CH3
Examples: 1
H3C O CH3 OH
H3C
CH3
H3C
CH3
Observed max 270 nm Calculated max base value R--alkyl substituent(-OH)215 14 35 274
Example 2
OH
R-C6H4-COG
Parent chromophore
G-Alkyl or Ring residue G=H G=OH or OR
Addition for R
Alkyl or ring residue -OH or Ome ,-O-Alkyl -O
R-C6H4-COG -Cl
-Br
O,M -2 nm P 15 nm
-NH2
P 58 nm O,M -13 nm
-NHAC
O,M -20 nm
P 45 nm
-NHMe O,M -20 nm P 45 nm -NHMe2 O,M 20 nm P 85 nm
Examples: 1.
Observed max 276 nm Calculated max parent value - 246 para-methoxyl - 25 ortho-ring residue 03 274
CH3
2.
H3C
H3C O
system of 4 double bonds or less conjugated polyenes having more than 4 double bonds the fisher-kuhn rules are used.
chemical analysis , Himalaya publishing house, 5th edition ,2008. B.K.sharma,Instrumental methods of chemical analysis , Goe publication, 23rd Edition. www.bing.com www.google.com