CATHOLIC UNIVERSITY

Development of Complex Curricula for Molecular Bionics and Infobionics Programs within a consortial* framework**

Consortium leader

PETER PAZMANY CATHOLIC UNIVERSITY

Consortium members

SEMMELWEIS UNIVERSITY, DIALOG CAMPUS PUBLISHER

The Project has been realised with the support of the European Union and has been co-financed by the European Social Fund ***

**Molekuláris bionika és Infobionika Szakok tananyagának komplex fejlesztése konzorciumi keretben

CATHOLIC UNIVERSITY

UNIVERSITY

Organic an Biochemistry

Ractions with addition, substitution and elimination

semmelweis-egyetem.hu

(Szerves és Biokémia )

(Addíciós, szubsztitúciós és eliminációs reakciók)

Compiled by dr. Péter Mátyus

with contribution by dr. Gábor Krajsovszky

Formatted by dr. Balázs Balogh

Table of Contents

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1. Substitutions 4 – 7

2. Additions 8 – 8

3. Eliminations 9 – 10

4. The stereochemistry of additions and eliminations 11 – 11

S

1

S

1

Substitution reactions

Organic and Biochemistry: Addition, Substitution, Elimination

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C X a

b c C

a

b c

+ ^X

^{C Nu}

a

b c + ^{Nu C}

a

c b Nu

R C CH

O H

O

R C CH

OH

Br Br

Br

R C CH

OH

Br

R C CH

OH

Br

Br

R C CH

O

Br

+ ^{H Br}

Inversion of configuration S

2

Retention of configuration S

2

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C X a

c b

C a

b c

H

H Y C

a

b c - X

+ Y S

2

C X a

c b

C a

b

c M

H

C Y a

c b + H

S

2

- M

elimináció addíció

C O X

R δ+ δ -

Nu C O

R

X

Nu C O

R Nu

+ X

Cl

NO₂

NO₂

+ Nu

Nu NO₂

NO₂ Cl

NO₂

NO₂ Nu

+ Cl + E

E Hδ+

Eδ+ E

+ H π₁-komplex σ-komplex π₂-komplex

H E

S

Ac

S

Ar

S

Ar

Organic and Biochemistry: Addition, Substitution, Elimination

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addition elimination

π₁-complex σ-complex π₂-complex

O C

C O

Br H₃C H

O C

C O

Br H CH³

δ δ

Br O

C C O

H CH³

H₂C CH CH₂ Nu

gyors H₂C CH CH₂ Nu

H₂C CH CH₂ lassú

- Cl

γ β α

H₂C CH CH₂ Cl

R CH CH CH₂ X Nu R CH CH CH₂ Nu + R CH CH CH₂ Nu

S

' S

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slow fast

C C + X Ad_E

C C

Y

X C C

X

Y

HC CH₂

O₂N + O₂N HC CH₂

Y X

Y O₂N HC CH₂

Y

Ad_N X

XY C C

Y

X

C C + X +

C C

X

X

Ad_R

Ad

Ad

Ad

Addition reactions

Organic and Biochemistry: Addition, Substitution, Elimination

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CH

C

H

C CH

lassú

C Cl H

C

H

C

H

C NaOH

HO

CH

C

CH

H

C

H

lassú CH CH

Br gyors

+ EtO CH

CH

Br

E1

E1cB

Elimination reactions

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slow slow

fast

H CH

CH CH

Br EtOH + H

C CH CH

+ Br EtO

+ X + B H

C C H

C

H

C

C

H

C C H

H

H

C

H

C

X H C

H

B B

C C H

H

C

H

C

X H C

H

E2 Organic and Biochemistry: Addition, Substitution, Elimination

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Stereochemistry of addition and elimination

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R

R

H H Br

Br

Br

Br H H R

R

anti addition

H

Br R R' R

R

R

R

R R' anti elimination

O Mn O

O OK

H R

H R

H

H R

R

syn addition

H

H R

R

syn elimination

6 electrons HO

-H

O -Br

KMnO

H O

H R

H R

H

C O

-CH

COOH