Alkaloids

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 What are they

• Plant origin basic organic compounds

• At least one nitrogen in heterocylic ring

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Examples

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 General properties

• Colorless and crystalline non-volatile solids

• Water insoluble, soluble in organic solvents

• Exceptions -water soluble liquids; eg. Nicotine

• Bitter taste
• Optical activity

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 Classification
• Based on chemical substructures
• Phenylethylamine group
• Pyrrolidine group
• Pyridine and Piperidine group
• Quinoline group
• Isoquinoline group
• Phenanthrene group
• Indole group
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Hofman’s exhaustive methylation

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Exceptions

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Emde modification

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 Von Braun’s method
• Tertiary amines

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`

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 Methods for structure determination
• Combustion analysis of pure sample

• If oxygen present -

test for hydroxyl group

moles of acetic anhydride consumed

• FeCl3 test – phenolic OH

• Ready solubility in sodium carbonate – COOH

• Precipitate with 2,4-DNP – carbonyl group

• Reaction with bromine water and KMnO4-unsaturation

• Oxidative degradation into simpler molecules

• Methoxy group-treatment with boiling HI-formation of MeI-precipitated by alc. AgNO3 to AgI

and weighed 16
 Nature of nitrogen present
• No reaction with Acetic anhydride, nitrous acid- tertiary
nitrogen
• Positive reaction with hydrogen peroxide – formation of
N-oxide – tertiary nitrogen
• Alkaloid distillation with KOH- formation of
dimethylamine, methylamine, trimethyl amine, evolution
of ammonia – original nature of nitrogen present
indicated
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 Phenylethylamine group
• Ephedrine – structure determination

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Synthesis

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Mescaline

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Synthesis

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Adrenaline

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Synthesis

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Tobacco alkaloids-Nicotine

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Synthesis

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Solanaceous alkaloids-Atropine

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Synthesis – Tropic acid

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Synthesis

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