The Octant Rule

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

Contents : Introduction Facts Statement of octant rule Applications with examples Summary Questions References
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Introduction
It is an empirical rule that establishes an absolute configuration or stereochemistry from the sign and intensity of cotton effect

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

+
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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

(-)

(+)
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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= +
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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

Example
3-methyl hexanone Equatorial confirmation more stable Atoms 2, 4, 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

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

2. Determination of configuration:configuration: Example: trans - 10 methyl 2 decalone

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

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Few back octant projections of some cholestanones

Ketone 2 cholestanone +121 Octant Diagram 7, 19, ring C, D Prediction (+)ve

3 cholestanone

+65

6, 7, 15, 16

(+)ve

4 - cholestanone

-94

19, ring C, D

(-)ve

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

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

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

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