The Octant Rule

Presented By By:Rahul Sharma M. Pharm ± I (Pharmaceutics) Submitted To To:Dr. G. S. Gadaginmath Department Of Pharmaceutical Chemistry Set¶s College Of Pharmacy (Dharwad)
2/9/2010 1

Contents :‡ ‡ ‡ ‡ ‡ ‡ ‡ Introduction Facts Statement of octant rule Applications with examples Summary Questions References 2 .

Introduction ‡ It is an empirical rule that establishes an absolute configuration or stereochemistry from the sign and intensity of cotton effect 3 .

Facts :‡ Octant rule was developed by Djerrasi and coworkers ‡ It relates the sign and amplitude of cotton effect exhibited by an optically active saturated ketone to the spatial orientation of atoms about the carbonyl function + + 4 - .

Octant rule states that :‡ Substituents lying in the co-ordinate planes comake up no contribution to the rotatory dispersion ‡ Substituents lying the back upper left and back lower right make positive contribution ‡ Substituents in the upper right and back lower left make negative contribution (+) (-) Back Octants (-) (+) 5 .

For a cyclohexane ring:ring:Carbon atom number C1 C2 C3 C4 C5 C6 Total cotton effect 0+0=0 0+(-)= (+)+(+) = + 0+0=0 (-)+(-)= (+)+0= + 6 .

Information: Information ‡ Substituents in nodal planes contribute nothing ‡ Substituents within octant contribute sign of that octant ‡ At a time 4 octants are considered and rest 4 are empty 7 .

6 ± in nodal planes so no contribution ‡ Atoms 3 and 5 cancel each other but the methyl substitution. if axial leads to negative effect and if it is equatorial then the net effect is positive 8 contribution .Example ‡ 3-methyl hexanone ‡ Equatorial confirmation more stable ‡ Atoms 2. 4.

APPLICATIONS 1. Prediction of cotton effect Example : 5 ± cholestan ± 6 ± one 9 .

2.10 ± methyl ± 2 ± decalone 10 . Determination of configuration:configuration: Example: trans .

chloro ± 5 ± methylcyclohexanone 11 .3. Study of conformational mobility:mobility: Example: 2.

cholestanone -94 19. ring C. 15. D Prediction (+)ve 3 ± cholestanone +65 6. D (-)ve 12 .Few back octant projections of some cholestanones Ketone 2 ± cholestanone +121 Octant Diagram 7. ring C. 7. 19. 16 (+)ve 4 .

Summary: Summary:‡ It is an empirical rule that establishes an absolute configuration or stereochemistry from the sign and intensity of cotton effect 13 .

± 616616-623 ‡ Internet (google.3rd William. Palgrave.S. New Delhi. New Age International (p) Ltd.References ::‡ Kemp William.co..279-280 279‡ Kalsi P. Page No. edition ± 1991.S. ³ Organic Spectroscopy ³..in) 14 . ³ Spectroscopy of Organic P. New York. . Compounds´. 6th edition ± 2004. Page No.

15 . ‡ Explain octant rule and its applications with suitable examples .Important Questions ‡ Predict the sign of cotton effect for following compounds using octant rule.

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