22.7 Reactions of Amines: A Review and a Preview

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1 22.7 Reactions of Amines: A Review and a Preview

2 Preparation of Amines Two questions to answer: 1) How is the C N C N bond to be formed? 2) How do we obtain the correct oxidation state of nitrogen (and carbon)?

3 Methods for C N C N Bond Formation Nucleophilic substitution by azide ion (N 3 ) (Section 8.1, 8.13) Nitration of arenes (Section 12.3) Nucleophilic ring opening of epoxides by ammonia (Section 16.12) Nucleophilic addition of amines to aldehydes and ketones (Sections 17.10, 17.11) Nucleophilic substitution by ammonia on a-halo a acids (Section 19.16) Nucleophilic acyl substitution (Sections 20.3, 20.5, and 20.11) Hofmann rearrangement (Section 20.17)

4 22.8 Preparation of Amines by Alkylation of Ammonia

5 Desired reaction is: Alkylation of Ammonia 2 NH 3 + R X R NH 2 + NH 4 X

6 Desired reaction is: Alkylation of Ammonia 2 NH 3 + R X R NH 2 + NH 4 X via: H 3 N X + X + R H 3 N R + then: H H 3 N + H + N R + H 3 N H + N H R H H

7 Alkylation of Ammonia But the method doesn't work well in practice. Usually gives a mixture of primary, secondary, and tertiary amines, plus the quaternary salt. NH 3 RX RNH 2 RX R 2 NH R 4 N + X RX R 3 N RX

8 Example CH 3 (CH 2 ) 6 CH 2 Br NH 3 CH 3 (CH 2 ) 6 CH 2 NH 2 As octylamine is formed, it competes with ammonia for the remaining 1-bromooctane. 1 Reaction of octylamine with 1-bromooctane 1 gives N,N-dioctylamine.

9 Example CH 3 (CH 2 ) 6 CH 2 Br NH 3 CH 3 (CH 2 ) 6 CH 2 NH 2 (45%) + CH 3 (CH 2 ) 6 CH 2 NHCH 2 (CH 2 ) 6 CH 3 (43%) As octylamine is formed, it competes with ammonia for the remaining 1-bromooctane. 1 Reaction of octylamine with 1-bromooctane 1 gives N,N-dioctylamine.

10 22.9 The Gabriel Synthesis of Primary Alkylamines

11 Gabriel Synthesis gives primary amines without formation of secondary, etc. amines as byproducts uses an S N 2 reaction on an alkyl halide to form the C N C N bond the nitrogen-containing nucleophile is N-potassiophthalimide

12 Gabriel Synthesis gives primary amines without formation of secondary, etc. amines as byproducts uses an S N 2 reaction on an alkyl halide to form the C N C N bond the nitrogen-containing nucleophile is N-potassiophthalimide N K +

13 N-Potassiophthalimide the pka p a of phthalimide is 8.3 N-potassiophthalimide is easily prepared by the reaction of phthalimide with KH NH KH N K +

14 N-Potassiophthalimide as a nucleophile N + R X S N 2 N R + X

15 Cleavage of Alkylated Phthalimide N R + H 2 acid or base C 2 H C 2 H + imide hydrolysis is nucleophilic acyl substitution H 2 N R

16 Cleavage of Alkylated Phthalimide hydrazinolysis is an alternative method of releasing the amine from its phthalimide derivative N R H 2 NNH 2 NH NH + H 2 N R

17 Example N K + + C 6 H 5 CH 2 Cl DMF

18 Example N K + + C 6 H 5 CH 2 Cl DMF N CH 2 C 6 H 5 (74%)

19 Example NH NH + C 6 H 5 CH 2 NH 2 H 2 NNH 2 (97%) N CH 2 C 6 H 5

20 22.10 Preparation of Amines by Reduction

21 Preparation of Amines by Reduction almost any nitrogen-containing compound can be reduced to an amine, including: azides nitriles nitro-substituted benzene derivatives amides

22 Synthesis of Amines via Azides S N 2 reaction, followed by reduction, gives a primary alkylamine. CH 2 CH 2 Br NaN 3 CH 2 CH 2 N 3 (74%) 1. LiAlH 4 2. H 2 CH 2 CH 2 NH 2 (89%)

23 Synthesis of Amines via Azides S N 2 reaction, followed by reduction, gives a primary alkylamine. CH 2 CH 2 Br NaN 3 CH 2 CH 2 N 3 azides may also be reduced by catalytic hydrogenation (74%) 1. LiAlH 4 2. H 2 CH 2 CH 2 NH 2 (89%)

24 Synthesis of Amines via Nitriles S N 2 reaction, followed by reduction, gives a primary alkylamine. CH 3 CH 2 CH 2 CH 2 Br NaCN CH 3 CH 2 CH 2 CH 2 CN (69%) H 2 (100 atm), Ni CH 3 CH 2 CH 2 CH 2 CH 2 NH 2 (56%)

25 Synthesis of Amines via Nitriles S N 2 reaction, followed by reduction, gives a primary alkylamine. CH 3 CH 2 CH 2 CH 2 Br NaCN CH 3 CH 2 CH 2 CH 2 CN nitriles may also be reduced by lithium aluminum hydride (69%) H 2 (100 atm), Ni CH 3 CH 2 CH 2 CH 2 CH 2 NH 2 (56%)

26 Synthesis of Amines via Nitriles S N 2 reaction, followed by reduction, gives a primary alkylamine. CH 3 CH 2 CH 2 CH 2 Br NaCN CH 3 CH 2 CH 2 CH 2 CN the reduction also works with cyanohydrins (69%) H 2 (100 atm), Ni CH 3 CH 2 CH 2 CH 2 CH 2 NH 2 (56%)

27 Synthesis of Amines via Nitroarenes Cl HN 3 H 2 S 4 Cl N 2 (88-95%) 1. Fe, HCl 2. NaH Cl NH 2 (95%)

28 Synthesis of Amines via Nitroarenes Cl HN 3 H 2 S 4 Cl N 2 nitro groups may also be reduced with tin (Sn) + HCl or by catalytic hydrogenation (88-95%) 1. Fe, HCl 2. NaH Cl NH 2 (95%)

29 Synthesis of Amines via Amides CH 1. SCl 2 2. (CH 3 ) 2 NH (86-89%) 89%) CN(CH 3 ) 2 1. LiAlH 4 2. H 2 CH 2 N(CH 3 ) 2 (88%)

30 Synthesis of Amines via Amides CH only LiAlH 4 is an appropriate reducing agent for this reaction 1. SCl 2 2. (CH 3 ) 2 NH (86-89%) 89%) 1. LiAlH 4 2. H 2 CN(CH 3 ) 2 CH 2 N(CH 3 ) 2 (88%)

31 22.11 Reductive Amination

32 Synthesis of Amines via Reductive Amination In reductive amination, an aldehyde or ketone is subjected to catalytic hydrogenation in the presence of ammonia or an amine. R fast R C + NH 3 C NH + H 2 R' R' The aldehyde or ketone equilibrates with the imine faster than hydrogenation occurs.

33 Synthesis of Amines via Reductive Amination The imine undergoes hydrogenation faster than the aldehyde or ketone. An amine is the product. R fast R C + NH 3 C NH + H 2 R' R' R C NH 2 R' H 2, Ni H

34 Example: Ammonia gives a primary amine. + NH 3 H 2, Ni ethanol H NH 2 (80%) via: NH

35 Example: Primary amines give secondary amines CH 3 (CH 2 ) 5 CH + H 2 N H 2, Ni ethanol CH 3 (CH 2 ) 5 CH 2 NH (65%)

36 Example: Primary amines give secondary amines CH 3 (CH 2 ) 5 CH + H 2 N H 2, Ni ethanol CH 3 (CH 2 ) 5 CH 2 NH (65%) via: CH 3 (CH 2 ) 5 CH N

37 Example: Secondary amines give tertiary amines CH 3 CH 2 CH 2 CH H 2, Ni, ethanol + N H N CH 2 CH 2 CH 2 CH 3 (93%)

38 Example: Secondary amines give tertiary amines possible intermediates include: H N CHCH 2 CH 2 CH 3 N+ CHCH 2 CH 2 CH 3 N CH CHCH 2 CH 3

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