Leila Section Week 8

Leila Section Week 8 - Chemistry 35: Organic Monofunctional...

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Chemistry 35: Organic Monofunctional Compounds Section 8: November 17, 2008 Prof. Huestis, Fall 2008 TA: Leila Yeh Beach AMINES Part I: Summary of Amine Reactions R = H or alkyl imines R NR 2 2) H 3 O + 1) LiAlH 4 xs R C N R' R' O R' R' N R any carbonyl R' Cl O NH O O 1) base R Br 2) 3) H 3 O + R' OR' O heat R' N H O R OR only 1 O amines and ammonia can be used OR H 2 / Pd R' H N R + HO - , Br 2 R' NH O R H H O R' O forms only 1 O amines NaBH 3 CN H 2 O (pH 2-3) R' O R' any carbonyl R' N R R R' only 2 O amines any carbonyl formaldehyde 1) HCl, ethanol 2) HO - , H 2 O formaldehyde β -ketoamines only 1 O and 2 O amines can be used nitriles forms 2 O or 3 O amides (reaction with ammmonia forms 1 O amides) + enamines Gabriel Amine Synthesis Hofmann rearrangement Mannich reaction R O Cl : electrophile enamines can act as nucleophiles in α -carbon chemistry (as an alternative to enolate formation) NaN 3 , H 2 O, heat the carbonyl carbon is decarboxylated and the amine is transfered to its α -carbon the carbonyl carbon is decarboxylated and the amine being formed is made on its α -carbon. Curtis rearrangement + emitted forms only 1 O amines R' R' HN R amines OR H 2 / Ni CO 2 H 2 O H 2 O H 2 O CO 2 N 2 (1) LiAlH 4 (2) H 3 O + H 2 /Pd OR R NH 2 amines R NH 2 O amides (1) LiAlH 4 (2) H 3 O + R NH 2 amines
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Part II: Preparation of Amines 1] Alkylation of Ammonia (NH 3 ) Overall Reaction Mechanism Alkylation of ammonia to obtain more highly substituted amines will not stop at the primary amine. Why is this? Well, the reaction proceeds because ammonia is a decent nucleophile and can displace the bromine group of an alkyl bromide in an S N 2 reaction. A primary amine, which contains one more alkyl group than ammonia, is an even better nucleophile than ammonia because the extra R group is electron donating and thus increases the partial negative charge on the nitrogen. By the same argument, a tertiary amine is a better nucleophile than a secondary amine which, in turn, is a
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This note was uploaded on 02/13/2009 for the course CHEM 35 taught by Professor Dubois,j during the Fall '07 term at Stanford.

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Leila Section Week 8 - Chemistry 35: Organic Monofunctional...

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