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ORGANIC CHEMISTRY REACTION SCHEME

AN OVERVIEW

ALKANES
Preparation of Alkanes
1. Hydrogenation of Alkenes
CnH2n 
H2 + Ni, Pd or Pt
 CnH2n+2

2. Reduction of Alkyl Halides


a. Hydrolysis of Grignard Reagent
RX + Mg 
dry ethyl ether
 RMgX 
water
 RH + Mg(OH)X
*Note: RMgX is the Grignard reagent, alkylmagnesium halide. The alkyl group is covalently bonded to magnesium;
+ –
and magnesium-halogen bond is ionic ie. [R:Mg] [X] . In the second step of the reaction, it is a displacement
reaction in which water (the stronger acid) displacing the weaker acid (R–H) from its salt (RMgX).

b. Reduction by Metal and Acid


+ –
RX   RH + Zn + X
Zn + H 2+

Reactions of Alkanes
1. Halogenation [Free Radical Substitution]
CnH2n+1H + X2  heat, or UV
 CnH2n+1X + HX
2. Combustion
CnH2n+2 + excess O2  heat
 nCO2 + (n+1)H2O
3. Pyrolysis Cracking
400-600 C
alkane 
with or w/o catalyst
 H2 + smaller alkanes + alkenes

ALKENES
Preparation of Alkenes
1. Dehydrohalogenation of Alkyl Halides
H H H H

H C C H  OH 
alcoholic KOH
reflux
 H C C H+ KX + H2O

H X

2. Dehydration of Alcohols
H H H H

excess conc H2SO 4 , 170 C


H C C H 
or Al2 O3 , 400 C
 H C C H + H2O
or H3PO4 , 200-250 C

H OH

3. Dehalogenation of Vicinal Dihalides


H H H H

H  H
Zn
H C C C C H + ZnX2

X X

Reactions of Alkenes
1. Addition of Hydrogen. Catalytic Hydrogenation
CnH2n 
H2 + Ni, Pd or Pt
Heat
 CnH2n+2

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2. Addition of Halogens [Electrophilic Addition using bromine/ethene]


H H H H

H C C H  X2 /CCl4
dark, room temperature
 H C C H

X X
3. Addition of Aqueous Halogen. Formation of Halohydrin
H H H H

H C C H 
X2 /H2 O
 H C C H + HX
Dark, room temp
X OH
4. Addition of Hydrogen Halides
H H H H

H   H
HX
H C C C C H

X H
5. Addition of Water. Hydration
a) Industrial Method
H H H H

H C C H 
H2 O(g)
conc H3PO4
 H C C H
300C, 60atm

H OH
b) Laboratory Method
H H H H H H

H C C H 
conc H2 SO4
cold
 H C C H 
H2 O, heat
(hydrolysis)
 H C C H + H2SO4

H OSO3H H OH
6. Oxidation
a) Cold, alkaline KMnO4 Solution
H H H H

H C C H 
alkaline KMnO 4
cold
H C C H

OH OH
b) Hot, acidic KMnO4 Solution
H H H H

H C C H 
MnO4 /H2 SO4
hot
H C O + O C H
*Note: Terminal carbons will be oxidized into carbon dioxide.
*Note: Under such oxidizing conditions, the aldehydes will be oxidized to carboxylic acid very quickly. To extract the
aldehyde only, we must use immediate distillation.

7. Combustion

ARENES
Reactions of Benzenes
1. Nitration [Electrophilic Substitution in mononitration of benzene]
NO 2


conc. HNO3
conc. H2 SO4

o
55 C

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2. Sulphonation
OSO2H


H2 SO4 ( l )
reflux
 + H2O

3. Halogenation
X

+ X2 
cold, dark
FeX3 , or AlX3
 + HX

Or Fe

4. Friedel-Crafts Alkylation
R

+ RX 
FeX3 , or AlX3
Lewis Acid
 + HX

5. Friedel-Crafts Acylation
COR
Note: acyl group
O
+ RCOCl / [(RCO) 2O] 
FeX3 , or AlX3
+ HX
R C

6. Hydrogenation

+ 3H 2 
Ni
150C

Preparation of Alkylbenzenes
1. Attachment of Alkyl Group. Friedal-Crafts Alkylation
R

+ RX 
FeX3 , or AlX3
Lewis Acid
 + HX

2. Conversion of side chain


R H
H
C C
O

Zn(Hg), HCl, heat
or N2H4 , base, heat
 R + HX
N2 + H2O
Or H2/Pd,
ethanol
*Note: This is known as the Clemmensen or Wolff-Kishner Reduction

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Reactions of Alkylbenzenes
1. Hydrogenation
R R

+ 3H2 
Ni, Pt, Pd
150C

2. Oxidation
a. Mild Oxidation
R CHO


MnO2
oxidation

b. Strong Oxidation
R COOH


MnO4 /H2 SO4
or acidified K 2Cr2O7

white crystals

3. Free Radical Aliphatic Halogenation


RCH3 RCH2X

 X2
UV, light or heat

*Note: Reaction above is only a generic reaction. Actual position of the halogen is dependent on the stability of the
carbocation intermediate.

4. Electrophillic Aromatic Halogenation by Electrophillic Addition


R R R
X

X2
FeX3 , FeX5
 +

X
5. Electrophillic Aromatic Nitration by Electrophillic Addition
R R R
NO 2


conc HNO3
conc H2 SO4
 +
o
30 C

NO 2
6. Electrophillic Aromatic Friedal-Crafts Alkylation by Electrophillic Addition
R R R
R1


R1X
AlX3
 +

R1

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7. Electrophillic Aromatic Sulphonation by Electrophillic Addition


R R R
OSO2H


H2 SO4 ( l )
 +

OSO2H
8. Electrophillic Aromatic Friedal-Crafts Acylation by Electrophillic Addition
R R R

COR1

+ R1COCl / [(R1CO)2O] 


FeX3 , or AlX3
 +

COR1

Alkylbenzenes clearly offers two main areas to attack by halogens: the ring and the side chain. We can
control the position of the attack simply by choosing the proper reaction conditions. Refer to Appendix for
more details.

HALOGEN DERIVATIVES
Preparation of Halogenoalkanes
1. Substitution in Alcohols
a. Using HX (suitable for 3° alcohols)
R–OH 
dry HX, ZnX2 (catalyst)
Reflux
 R–X + H2O
b. Using PX3/PX5 (suitable for 1°, 2° alcohols)
R–OH  PX3 /PX 5
Reflux
 R–X + POX3 + HX
c. Using SOCl2 (sulphonyl chloride)
R–OH 
SOCl2 , Pyridine(C5H5N)
Reflux
 R–Cl + SO2 + HCl
*Note: This is the best method because it is very clean. SO 2 can be bubbled off and HCl, being an acid, will react
with pyridine.

2. Electrophillic Addition to Alkenes


a) Addition of Hydrogen Halides
H H H H

H   H
HX
H C C C C H

X H
b) Addition of Halogens
H H H H

H C C H  X2 /CCl4
dark, room temperature
 H C C H

X X

3. Free Radical Substitution of Alkanes


CnH2n+1H + X2 
heat, or UV
 CnH2n+1X + HX

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Reactions of Halogenoalkanes
1. Alkaline Hydrolysis of Alcohols [Nucleophilic Substitution]
R–X + OH– 
aqueous KOH
reflux
 R–OH + X

*Note: Mechanism is S N2 for 1° halogenoalkane and S N1 for 3° halogenoalkane

2. Nitrile Synthesis
R–X + NaCN 
aqueous ethanol
reflux
 R–C≡N + NaBr
o
*Note: Nitriles are useful because they can be used to synthesize 1 amines and carboxylic acids.
Reduction to Amine:
R–C≡N 
LiAlH4 , dry ether
or 2H2 , Ni, heat
 RCH2NH2
Acidic Hydrolysis:
R–C≡N   RCOOH + NH4
HCl ( aq ) +
reflux

Basic Hydrolysis:
R–C≡N 

 RCOO Na + NH3
NaOH ( aq ) +
reflux

3. Formation of Amines
δ+ δ–

R–X + excess conc NH3   [H3N---R---X]   RNH2 + NH4 X
ethanol, reflux NH3 +
sealed tube
*Note: NH3 acts as the nucleophile and the base.
*Note: In the presence of excess RX, there will be polyalkylation of the halogenoalkane and 1°, 2°, 3° and even 4° ammonium
salt will be formed.
+ –
NH3 
RX
 RNH2 
RX
 R2NH 
RX
 R3N 
RX
 R4 N X

4. Williamson Synthesis (Formation of Ether) Conc H2SO4, 140oC


R–X + R'O–Na+   R–O–R' + NaX
*Note: The sodium or potassium alkoxide (anion of alcohol) is prepared by dissolving sodium and potassium in appropriate

alcohol. ROH + Na   RO Na + ½H2
+

5. Dehydrohalogenation (Elimination)
H H H H

H  OH (aq )   H
alcoholic KOH
H C C reflux C C H + KX + H2O

H X

Preparation of Halogenoarenes (Aryl Halides)


1. Electrophilic Aromatic Halogenation by Substitution
X

+ X2 
cold, dark
FeX3 , or AlX3
 + HX

Reactions of Halogenoarenes
1. Industrial Hydrolysis (Replacement of Halogen Atom, difficult due to strong C–X bond)
- +
X O Na


2NaOH
350C, 150atm
 + NaX + H2O

-+
O Na OH


H ( aq )
 + Na+

2. Williamson Synthesis (Formation of Ether)



R–X + ArO Na   R–O–Ar + NaX
+

o
Conc H2SO4, 140 C

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HYDROXY COMPOUNDS
Preparation of Alcohols
1. Alkene Hydration. Addition of Water.
H H H H H H

H C C H 
conc H2 SO4
cold
 H C C H 
H2 O, heat
(hydrolysis)
 H C C H + H2SO4

H OSO3H H OH
2. Alkaline Hydrolysis of Halogenoalkanes
– –
R–X + OH 
aqueous KOH
reflux
 R–OH + X
3. Reduction of Carboxylic Acids, Aldehydes and Ketones
a. Carboxylic Acids and Aldehydes are reduced to their primary alcohols.
R H
+

C O + 4[H] 
1. LiAlH4 (ethoxyethane), reflux 2.H /H2 0
or H2 , Ni
 R C OH + H2O

HO H
R H
+

C O + 4[H] 
1. LiAlH4 (ethoxyethane), reflux 2.H /H 2 0
or H2 , Ni
 R C OH

H H

b. Ketones are reduced to their secondary alcohols.


R R
+

C O + 4[H] 
1. LiAlH4 (ethoxyethane), reflux 2.H /H 2 0
or H2 , Ni
 R1 C OH

R1 H
*Note: Lithium aluminium hydride (or Lithium tetrahydridoaluminate(III)), LiAlH4, is one of the few reagents that can
reduce an acid to an alcohol; the initial product is an alkoxide which the alcohol is liberated by hydrolysis.

The H ion acts as a nucleophile, and can attack the carbon atom of the carbonyl group. The intermediate then
reacts with water to give the alcohol.
-
R O OH
H3C H2O H3C
C O C C
– H H
H H H H
Carboxylic Acid: 4RCOOH + 3LiAlH4 
 4H2 + 2LiAlO2 + (RCH2O)4AlLi 
H2O
 4RCH2OH
Ketones: 4R2C=O + LiAlH4 
 (R2CHO)4AlLi 
H2O
 4R2CHOH + LiOH + Al(OH)3

Reactions of Alcohols
1. Substitution in Alcohols
a. Using HX (suitable for 3° alcohols)
R–OH  dry HX, ZnX2 (catalyst)
Reflux
 R–X + H2O
b. Using PX3/PX5 (suitable for 1°, 2° alcohols)
R–OH  PX3 /PX 5
Reflux
 R–X + POX3 + HX
c. Using SOCl2 (sulphonyl chloride)
R–OH 
SOCl2 , Pyridine(C5H5N)
Reflux
 R–Cl + SO2 + HCl
*Note: This is the best method because it is very clean. SO 2 can be bubbled off and HCl, being an acid, will react
with pyridine.

2. Reaction with Sodium/Potassium


H H
- + 1
H C O H 
Sodium/Potassium
H C O Na + H2
2
H H
*Note: Alcohols are too weak to react with hydroxides and carbonates.

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3. Oxidation to Carbonyl Compounds and Carboxylic Acids


a. Primary Alcohols are oxidized to aldehydes first, then carboxylic acids.
R R R
OH
C 
K 2 Cr2 O7 /H2 SO4
immediate
 C O 
K 2 Cr2 O7 /H2 SO4
or KMnO4 /H2SO4
 C O
distillation
H
H H HO
*Note: MnO2 is also a milder oxidizing agent.

b. Secondary Alcohols are oxidized to ketones.


R R
OH
C 
K 2 Cr2 O7 /H2 SO4
or KMnO4 /H2SO4
 C O
R1
H R1

c. Tertiary alcohols are not readily oxidized.

4. Dehydration to Alkenes
a. Excess conc H2SO4
H H H H

excess conc H2SO 4 , 170 C


H C C H 
or Al2 O3 , 400 C
 H C C H + H2O
or H3PO4 , 200-250 C

H OH

b. Excess alcohol
140C
R–CH2OH + conc H2SO4 
excess alcohol
R–CH2–O– CH2–R

5. Esterification
O
R O R1
C conc H2 SO4 C R1
+ O     heat
   
 + H2O
(can use acid or
alkaline as catalyst) R O
H
OH

6. Acylation
a. Acid Chloride Note: acyl group
O
R C Cl + R1 OH 
room temperature R C O R1 + HCl
R C
O O
H

b. Acid Anhydride
R C O C R + R1 OH 
room temperature
 R C O R1 + R C OH

O O O O
H
7. Tri-Iodomethane (Iodoform) Formation
*Note: Reaction is only positive for alcohol containing a methyl group and a hydrogen atom attached to the carbon at H C OH
which the hydroxyl group is also attached.
H CH3

R C OH 
I2 , NaOH ( aq )
 CHI 3
warm

CH3
a. Step 1: Oxidation of Alcohol to the corresponding carbonyl compound by iodine.
- -
R CH OH + I2 + 2 HO R C O + 2 H2 O + 2I
CH3 CH3

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b. Step 2: Further oxidation to carboxylate salt and formation of iodoform


- -
R C O + 3 I2 + 4HO R C O + CHI 3 + 3 I + 3 H2 O
-
CH3 O

c. Overall Equation:
H
- -
R C OH + 4 I2 + 6HO R C O + CHI 3 + 5 I + 5 H2O
-
CH3 O

Preparations of Phenols

1. Replacement of OH group in diazonium salts
N O

+ -
NH2 N O S OH OH

O



NaNO2 , H2 SO4

water, H , heat

Reactions of Phenols
1. Reaction with Reactive Metals (e.g. Na or Mg)
- +
OH O Na
1
+ Na + H
2 2

2. Reaction with NaOH


- +
OH O Na
1
+ NaOH + H O
2 2

*Note: Phenols have no reactions with carbonates

3. Esterifications
- +
OH O Na O O
C

NaOH
 
RCOCl

*Note: Phenols do not react with carboxylic acids but their acid chlorides to form phenyl esters.
*Note: Esterification is particularly effective in NaOH(aq) as the alkali first reacts with phenol to form phenoxide ion which is a
stronger nucleophile than phenol.

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4. Halogenation
a. With bromine(aq)
OH
OH
Br Br

+ 3HBr

3Br2 ( aq )

Br
*Note: 2,4,6-tribromophenol is a white ppt.

b. With bromine(CCl4)
OH OH OH


Br2 (CCl4 )
 +

Br Br

5. Nitration
a. With conc nitric acid
OH
OH
O 2N NO 2


conc HNO3

NO 2
b. With dilute nitric acid
OH OH OH


dil HNO3
 +

NO 2 O 2N

6. Reaction with FeCl3(aq)


*Note: This is a test for phenol. Violet complex upon adding iron(III) chloride will confirm presence of phenol. Colour may vary
depending on the substitution on the ring.
3--

O
OH
3+

Fe
 Fe

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CARBONYL COMPOUNDS
Preparation of Aldehydes
1. Oxidation of Primary Alcohols
R R
OH
C 
K 2 Cr2 O7 /H2 SO4
immediate
 C O + H2 O
distillation
H
H H

Preparations of Ketones
1. Oxidation of Secondary Alcohols
R R
OH
C 
K 2 Cr2 O7 /H2 SO4
or KMnO4 /H2 SO4
 C O + H2O
R1
H R1

2. Oxidative Cleavage of Alkenes


R2 R3 R2 R3

C C 
MnO4 /H2 SO4
+
hot C C
R1 R4 R1 O O R4

Reactions of Carbonyl Compounds


1. Addition of Cyanide. Cyanohydrin formation.
[Nucleophilic Addition of Hydrogen Cyanide to Aldehyde and Ketone]
H
H H
C -
+ CN 
HCN, small amount of base
 H C CN
O
OH
*Note: Cyanohydrins can be hydrolysed to form 2-hydroxy acids.
Acidic Hydrolysis
R R

H C CN 
water, HCl (aq)
heat
 H C COOH + NH 4Cl

OH OH
Basic Hydrolysis
R R
- +
H C CN 
water, NaOH ( aq )
heat
 H C COO Na + NH 3

OH OH

*Note: Cyanohydrins can undergo reduction.


R R

H C CN 
LiAlH4 in dry ether
or H2 , Ni, heat
H C CH2NH 2

OH OH

2. Reaction with 2,4-Dinitrophenylhydrazine (Brady’s Reagent). Condensation Reaction.


R2 R2

C O + H2N NH NO 2 C N NH NO 2 + H2 O

R1 R1

O 2N O 2N
*Note: 2,4-dinitrophenylhydrazones formed are orange or yellow crystalline solids with characteristic melting points. They are
useful for identifying individual aldehydes and ketones.

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3. Oxidation Reactions
*Note: Aldehydes are easily oxidized to carboxylic acids. Ketone are not.
a. Oxidation of Aldehydes using hot, acidified potassium dichromate(VI)
*Note: K2Cr2O7 turned from orange to green if test is positive.
R H R OH
C C

K 2 Cr2 O7 /H2SO4
heat

O O
O O

C 
K 2 Cr2 O7 /H2 SO4
heat
 C

H OH
R R1
C 
K 2 Cr2 O7 /H2 SO4
 No Reaction
heat

b. Oxidation of Aldehydes using hot, acidified potassium manganate(VII)


*Note: KMnO4 turned from purple to colourless if test is positive.
R H R OH
C C


K 2MnO4 /H2 SO4
heat

O O
O O

C 
K 2MnO4 /H2 SO4
 C
heat

H OH

c. Oxidation of Aliphatic Aldehydes using Fehling’s Solution (Fehling’s Test)


-
R H R O
C 
Fehling's Solution
 C + Cu2O (s)
warm

O O
O

C 
Fehling's Solution
warm
 No Reaction
H
R R1
C 
Fehling's Solution
 No Reaction
warm

O
*Note: Aliphatic aldehydes reduce the copper(II) in Fehling’s solution to the reddish-brown copper(I) oxide.
– –
R–CHO + 2Cu + 5OH   R–COO + Cu2O (s) + 3H2O
2+

*Note: Methanal (strongest aldehyde reducing agent) produces metallic copper as well as copper( I) oxide.
– –
HCHO + Cu2O + OH   HCOO + 2Cu (s) + H2O

d. Oxidation of Aldehydes using Tollen’s Reagent (Silver Mirror Test)


-
R H R O
C 
Tollen's Reagent
 C + Ag (s)
warm

O O
O O

C 
Tollen's Reagent
warm
 C + Ag (s)
-
H O

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ORG ANIC CHEM IST RY RE ACT ION SCHEM E – AN OVERVIEW

d. Oxidation of Aldehydes using Tollen’s Reagent (Silver Mirror Test) (Cont’d)


R R1
C 
Tollen's Reagent
 No Reaction
warm

O
*Note: Aldehydes redyce the Ag(I) in Tollen’s reagent to Ag, forming a silver mirror.
– –
RCHO + 2[NH3AgNH3] + 3OH   RCOO + 2Ag (s) + 4NH3 + 2H2 O
+ heat

4. Reduction Reactions
a. Reduction of Aldehydes to Primary Alcohols
R–CHO + 2[H] 
LiAlH4 in dry ether
or NaBH4 ( aq )
R–CH2OH
R–CHO + H2  Ni catalyst
heat
 R–CH2OH
b. Reduction of Ketones to Secondary Alcohols
H
R R1
C
+ H2 
LiAlH4 in dry ether
or NaBH4 ( aq )
R C R1
O OH
H
R R1
C R C R1
+ H2 
Ni catalyst
heat

O OH

5. Reaction with Alkaline Aqueous Iodine (Tri-Iodomethane (Iodoform) Formation) H C O


*Note: Reaction is only positive for alcohol containing a methyl group attached to the carbon at which the carbonyl group CH3
is also attached i.e. methyl carbonyl compounds. For aldehydes, only ethanal will form iodoform. All methyl ketones will
form iodoform.
- -
R C O + 3 I2 + 4HO  NaOH, warm
 R C O + CHI 3 + 3I + 3H2O
-
CH3 O

6. Chlorination using Phosphorus Pentachloride (PCl5)


*Note: Aldehydes and ketones react with phosphorus pentachloride to give geminal-dichloro (cf. vicinal) compounds. The
oxygen atom in the carbonyl group is replaced by two chlorine atoms.
CH3CHO + PCl5 
 CH3CHCl2 + POCl3
CH3COCH3 + PCl5 
 CH3CCl2CH3 + POCl3

CARBOXYLIC ACIDS & DERIVATIVES


Preparation of Carboxylic Acids
1. Oxidation
a. Oxidation of Primary Alcohols and Aldehydes
R R R
OH
C 
K 2 Cr2 O7 /H2 SO4
immediate
 C O 
K 2 Cr2 O7 /H2 SO4
or KMnO4 /H2SO4
 C O
distillation
H
H H HO

b. Oxidative Cleavage of Alkenes


H H H O O H
C C
C C 
KMnO4 /H2 SO4 , heat
 +
H H OH OH

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ORG ANIC CHEM IST RY RE ACT ION SCHEM E – AN OVERVIEW

c. Oxidation of an Alkylbenzene (Formation of Benzoic Acid)


O

CH3 C
OH
+ 3[O] 
KMnO4/H2SO4 , heat
 + H2O

2. Hydrolysis
a. Hydrolysis of Nitriles (R–C≡N)
Acidic Hydrolysis
R–C≡N   RCOOH + NH4
HCl ( aq ) +
reflux
Basic Hydrolysis

R–C≡N 
NaOH ( aq )
reflux
 RCOO Na + NH3
+

b. Hydrolysis of Esters (RCOOR’)


Acidic Hydrolysis
HCl ( aq ), reflux
RCOOR’ + H2O   conc
  H2SO
   RCOOH + R’OH
4

Basic Hydrolysis

RCOOR’ + H2O    RCOO Na + R’OH
NaOH (aq ) +
reflux

RCOO–Na+ 
+
H
reflux
 RCOOH

Reactions of Carboxylic Acids


1. Salt Formation
a. Reaction with Metal

RCOOH + Na  RCOO Na + ½H2
+

b. Reaction with Bases



RCOOH + NaOH  RCOO Na + H2O
+

c. Reaction with Carbonates



2RCOOH + Na2CO3 
 2RCOO Na + H2O + CO2
+

2. Esterification
O
R O R1
C conc H2 SO4 C R1
+ O     heat
   
 + H2O
(can use acid or
alkaline as catalyst) R O
H
OH

3. Conversion into Acyl Chlorides (RCOCl)


RCOOH + PCl5   RCOCl + POCl3 + HCl
3RCOOH + PCl3  3RCOCl + H3PO3
RCOOH + SOCl2   RCOCl + HCl + SO2

4. Reduction to Alcohols
RCOOH + 4[H] 
1. LiAlH4 in dry ether
2. H2SO4 ( aq )
 RCH2OH + H2O

Preparation of Acyl Chlorides


1. From Carboxylic Acid
RCOOH + PCl5  RCOCl + POCl3 + HCl
3RCOOH + PCl3  3RCOCl + H3PO3
RCOOH + SOCl2  RCOCl + HCl + SO2

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ORG ANIC CHEM IST RY RE ACT ION SCHEM E – AN OVERVIEW

Reactions of Acyl Chlorides


1. Conversion into Acid. Hydrolysis
RCOCl + H2O  RCOOH + HCl
ArCOCl + H2O  ArCOOH + HCl
*Note: Benzoyl chloride reacts much slower than acyl chlorides because of the reduce in the positive nature of the carbonyl
carbon caused by resonance.

2. Ester Formation. Alcoholysis.


RCOCl + R’OH 
room temperature
 RCOOR’ + HCl
*Note: Reaction is slow when phenol is directly reacted with acyl chloride.
RCOCl + ArOH  slow
 RCOOAr + HCl
*Note: Because phenol is a weaker nucleophile (lone pair of electron delocalizes into the ring), it is converted to phenoxide to
increase nucleophilic strength.

ArOH + NaOH   ArO Na + H2O
+

– –
RCOCl + ArO 
 RCOOAr + Cl

3. Amide Formation. Ammonolysis.


RCOCl + NH3   RCONH2 + HCl
RCOCl + R’NH2  RCONHR’ + HCl
RCOCl + R’R’’NH 
 RCONR’R’’ + HCl

4. Reduction to Aldehyde, then Alcohol


RCOCl 
LiAlH4 in dry ether
RCHO 
LiAlH4 in dry ether
H2SO4 ( aq )
RCH2OH

Preparations of Esters
1. Condensation Reaction of Acid and Alcohol
a. Ethyl Ethanoate
O
R O R1
C conc H2 SO4 C R1
+ O     heat
   
 + H2O
(can use acid or
alkaline as catalyst) R O
H
OH

b. Phenyl Benzoate

ArOH + NaOH   ArO Na + H2O
+

ArCOCl + ArO–Na+  ArCOOAr + NaCl

Reaction of Esters
1. Hydrolysis
a. Acidic Hydrolysis
HCl ( aq ), reflux
RCOOR’ + H2O   conc
  H2SO
   RCOOH + R’OH
4

b. Basic Hydrolysis

RCOOR’ + H2O  
NaOH (aq )
reflux
 RCOO Na + R’OH
+

2. Reduction to Primary Alcohols


RCOOR’ 
LiAlH4 in dry ether
H2SO4 ( aq )
RCH2OH

Preparation of Polyesters
1. Condensation Reaction
nHOOCRCOOH + nHOR’OH 
acid
reflux
 ( OCRCOOR’O ) n + 2nH2O

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ORG ANIC CHEM IST RY RE ACT ION SCHEM E – AN OVERVIEW

NITROGEN COMPOUNDS
Preparation of Amines
1. Reaction of Halides with Ammonia or Amines. Ammonolysis
δ+ δ–
+ –
R–X + excess conc NH3 
ethanol, reflux
sealed tube
 [H3N---R---X] 
NH3
 RNH2 + NH4 X
+ –
NH3 
RX
 RNH2 
RX
 R2NH 
RX
 R3N 
RX
 R4N X

2. Reduction
a. Reduction of Amide
RCONH2 
LiAlH4 in dry ether
H2 / Ni or Pt
RNH
RCH22NH2
b. Reduction of Nitrile
R–C≡N 
LiAlH , dry ether
4
or 2H , Ni, heat
2
 RCH2NH2
c. Reductive Amination
H H
H
C O + NH 3  C NH 
H2 , Ni
or NaBH3 CN
H C NH2
H imine
H H
Reactions of Amines
1. Salt Formation

RNH2 + HCl 
 RNH3 Cl
+

+–
RNH2 + R’COOH 
 RNH3 OOCR’
+ -
NH2 NH 3 Cl

+ HCl 

*Note: Phenylamine is not soluble in water but dissolves in acid.

2. Formation of Amides. Acylation.



R'COCl
 R'CONHR + HCl
RNH2

ArSO2Cl
 ArSO2NHR + HCl

R''COCl
 R''CONRR'  HCl
RR'NH

ArSO2 Cl
 ArSO2NRR'  HCl

R'''COCl
 no reaction
RR'R''N

ArSO2 Cl
 no reaction
*Note: Since HCl is formed, some of the ammonia/amine will be protonated and cannot act as a nucleophile. Hence, at least
double the amount of ammonia / amine must be used.
*Note: Acylation of 1° and 2° amines leads to the formation of substituted amides. 3° do not undergo acylation because they
do not have any replaceable H atoms.
CH3CH2NH2 + CH2COCl   CH3CH2NHCOCH3 + HCl
ArNH2 + Ar’COCl 
 ArNHCOAr’ + HCl
ArNH2 +RCOCl 
 ArNHCOR + HCl

3. Ring Substitution Reactions of Aromatic Amines


a. Halogenation
NH2 NH2

Br Br

+ 3Br2 (aq)  (s) + 3HBr

White ppt
Br

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ORG ANIC CHEM IST RY RE ACT ION SCHEM E – AN OVERVIEW

*Note: To get monosubstituted compounds, react phenylamine with ethanoyl chloride to reduce the ‘strongly
activating’ nature of the amino group to form phenylacetamide.
NH2 NHCOCH 3

+ CH3COCl 

*Note: NHCOCH3 is also 2,4-directing but moderately activating. Halogenation of ArNHCOCH 3 will give N-(2-
bromophenyl)acetamide or N-(4-bromophenyl)acetamide. Reacting this with aqueous NaOH and heating will give
2-bromophenylamine or 4-bromophenylamine.

b. Nitration
NH2 NH2

O 2N NO 2
conc HNO
+ conc H SO3 
2 4

NO 2
*Note: The same steps as above can be taken if we want monosubstituted nitrophenylamine.

Preparations of Amides
1. Ammonolysis of Acid Derivatives
RCOCl + NH3  RCONH2 + HCl
RCOCl + R’NH2  RCONHR’ + HCl
RCOCl + R’R’’NH 
 RCONR’R’’ + HCl

2. Reaction between Amine and Acid Chloride



R'COCl
 R'CONHR + HCl
RNH2

ArSO2Cl
 ArSO2NHR + HCl

R''COCl
 R''CONRR'  HCl
RR'NH

ArSO2 Cl
 ArSO2NRR'  HCl

Reactions of Amides
1. Acidic Hydrolysis
RCONH2 
HCl, H2 O
heat
 R–COOH + NH4+
2. Basic Hydrolysis
RCONH2 
NaOH, H2 O
heat
 R–COO– + NH3

Preparations of Amino Acids


1. Hell-Volhard-Zelinsky Reaction
H H H

C 
Br2 , PBr3
heat
 C 
excess conc NH3
 C
H COOH Br COOH COOH
R R H2N R

Reactions of Amino Acids


1. Salt Formation
+
a. Reaction with H . Cationic
+
H3N–CH2–COO–(aq) + H+(aq) 
 H3N–CH2–COOH (aq)
+

b. Reaction with OH . Anionic
– – –
H3N–CH2–COO (aq) + OH (aq)   H2N–CH2–COO (aq) + H2O(l)
+

*Note: The above two equations explains the buffering capability of amino acids.

2. Acylation (Formation of Amides)


CH3COCl + H2N–CH2–COOH 
 CH3–CO–NH–CH2COOH + HCl

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ORG ANIC CHEM IST RY RE ACT ION SCHEM E – AN OVERVIEW

3. Esterification
HCl +
H2N–CH2–COOH + ROH     H3N–CH2–COOR + H2O

4. Peptide Formation
*Note: A peptide is any polymer of amino acids linked by amide bonds between the amino grup of each amino acid and the
carboxyl group of the neighbouring amino acid. The –CO–NH– (amide) linkage between the amino acids is known as a
peptide bond.
H2N CH C OH + H2N CH C OH H2N CH C N CH C OH + H2 O
R O R1 O R O H R1 O

5. Hydrolysis of Peptides
a. Acidic Hydrolysis
H O H H O H
+
------ C C N C ------ 
H2 SO4 ( aq )
heat
 ------ C C OH + H3N C ------

R H R1 R R1

b. Basic Hydrolysis
H O H H O H
-
------   ------ +
NaOH ( aq )
------ C C N C heat C C O H2N C ------

R H R1 R R1
*Note: A peptide bond can be cleaved by hydrolysis in the presence of a suitable enzyme (trypsin, pepsin etc) or by
heating in acidic or alkaline medium.

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ORG ANIC CHEM IST RY RE ACT ION SCHEM E – AN OVERVIEW

APPENDIX
Halogenation of Alkylbenzenes: Ring vs Side chain

Alkylbenzenes clearly offer two main areas to attack by halogens: the ring and the side chain. We can
control the position of attack simply by choosing the proper reaction conditions.

Halogenation of alkanes requires conditions under which halogen atoms are formed, that is, high
temperature or light. Halogenation of benzene, on the other hand, involves transfer of positive halogen,
which is promoted by acid catalysts like ferric chloride (FeCl3).
CH4 + Cl2  heat or light
 CH3Cl + HCl
Cl

+ Cl2 
FeCl3 , cold
 + HCl

We might expect, then, that the position of attack in, for example, methylbenzene would be governed by
which the attack particle is involved, and therefore by the conditions employed. This is so: if chlorine is
bubbled into boiling methylbenzene that is exposed to ultraviolet light, substitution occurs almost exclusively
in the side chain; in the absence of light and in the presence of ferric chloride, substitution occurs mostly in
the ring.

CH3 Cl● Atom: Attacks side chain

Cl+ Ion: Attacks ring

Markovnikov’s Rule
In the ionic addition of an acid to the carbon-carbon double bond of an alkene, the hydrogen of the acid
attaches itself to the carbon atom that already holds the greater number of hydrogens.

Saytzeff’s Rule
For elimination reactions, the preferred product is the alkene with the most alkyl groups attached to the
doubly bonded carbon atoms i.e. the most substituted product.

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