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AN OVERVIEW
ALKANES
Preparation of Alkanes
1. Hydrogenation of Alkenes
CnH2n ⎯⎯⎯⎯⎯⎯
H2 + Ni, Pd or Pt
→ CnH2n+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
400-600C
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
H OH
H ⎯⎯→ H
Zn
H C C C C H + ZnX2
X X
Mr Cheng 1 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
Reactions of Alkenes
1. Addition of Hydrogen. Catalytic Hydrogenation
CnH2n ⎯⎯⎯⎯⎯⎯
H2 + Ni, Pd or Pt
Heat
→ CnH2n+2
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 H3 PO4
→ 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 KMnO4
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
Mr Cheng 2 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
ARENES
Reactions of Benzenes
1. Nitration [Electrophilic Substitution in mononitration of benzene]
NO 2
⎯⎯⎯⎯⎯
conc. HNO3
conc. H2 SO4
→
55oC
2. Sulphonation
OSO 2H
⎯⎯⎯⎯
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
Mr Cheng 3 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
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 2 Cr2 O7
→
white crystals
*Note: Reaction above is only a generic reaction. Actual position of the halogen is dependent on the stability of the carbocation
intermediate.
⎯⎯⎯⎯⎯X2
FeX3 , FeX5
→ +
X
5. Electrophillic Aromatic Nitration by Electrophillic Addition
R R R
NO 2
⎯⎯⎯⎯⎯
conc HNO3
conc H2 SO4
→ +
30oC
NO 2
6. Electrophillic Aromatic Friedal-Crafts Alkylation by Electrophillic Addition
R R R
R1
⎯⎯⎯
R1X
AlX3
→ +
R1
Mr Cheng 4 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
⎯⎯⎯⎯
H2 SO4 ( l )
→ +
OSO 2H
8. Electrophillic Aromatic Friedal-Crafts Acylation by Electrophillic Addition
R R R
COR 1
COR 1
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. SO2 can be bubbled off and HCl, being an acid, will react with pyridine.
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
Mr Cheng 5 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
Reactions of Halogenoalkanes
2. Nitrile Synthesis
R–X + NaCN ⎯⎯⎯⎯⎯⎯
aqueous ethanol
reflux
→ R–C≡N + NaBr
*Note: Nitriles are useful because they can be used to synthesize 1o amines and carboxylic acids.
Reduction to Amine:
R–C≡N ⎯⎯⎯⎯⎯⎯
LiAlH4 , dry ether
or 2H2 , Ni, heat
→ RCH2NH2
Acidic Hydrolysis:
R–C≡N ⎯⎯⎯⎯
HCl ( aq )
reflux
→ RCOOH + NH4+
Basic Hydrolysis:
R–C≡N ⎯⎯⎯⎯⎯
NaOH ( aq )
reflux
→ RCOO–Na+ + NH3
3. Formation of Amines
δ+ δ–
R–X + excess conc NH3 ⎯⎯⎯⎯⎯
ethanol, reflux
sealed tube
→ [H3N---R---X] ⎯⎯⎯
NH3
→ RNH2 + NH4+X–
*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
→ R4N+X–
5. Dehydrohalogenation (Elimination)
H H H H
−
H + OH (aq ) ⎯⎯⎯⎯⎯ → H
alcoholic KOH
H C C reflux C C H + KX + H2O
H 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+
Mr Cheng 6 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
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 /H2 0
or H2 , Ni
→ R C OH
H H
C O + 4[H] ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
1. LiAlH4 (ethoxyethane), reflux 2.H /H2 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. SO2 can be bubbled off and HCl, being an acid, will react with pyridine.
Mr Cheng 7 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
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 /H2 SO4
→ C O
distillation
H
H H HO
*Note: MnO2 is also a milder oxidizing agent.
4. Dehydration to Alkenes
a. Excess conc H2SO4
H H H H
H OH
b. Excess alcohol
140C
R–CH2OH + conc H2SO4 ⎯⎯⎯⎯⎯→
excess alcohol
R–CH2–O– CH2–R
5. Esterification
O
R O R1
C O
conc H2 SO4 C R1
+ heat + H2 O
(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 H2O + 2I
CH3 CH3
Mr Cheng 8 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
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 H2O
-
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
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.
Mr Cheng 9 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
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
O
OH
3+
⎯⎯⎯
Fe
→ Fe
Mr Cheng 10 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
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
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
H C CN ⎯⎯⎯⎯⎯⎯→
LiAlH4 in dry ether
or H2 , Ni, heat
H C CH 2NH 2
OH OH
C O + H2N NH NO 2 C N NH NO 2 + H2O
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.
Mr Cheng 11 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
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 /H2 SO4
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
O O
O O
C ⎯⎯⎯⎯⎯⎯
K 2MnO4 /H2 SO4
→ C
heat
H OH
O O
O
C ⎯⎯⎯⎯⎯⎯
Fehling's Solution
→ No Reaction
warm
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 + 2Cu2+ + 5OH– ⎯⎯→ R–COO– + Cu2O (s) + 3H2O
*Note: Methanal (strongest aldehyde reducing agent) produces metallic copper as well as copper(I) oxide.
HCHO + Cu2O + OH– ⎯⎯→ HCOO– + 2Cu (s) + H2O
O O
O O
C ⎯⎯⎯⎯⎯⎯
Tollen's Reagent
warm
→ C + Ag (s)
-
H O
Mr Cheng 12 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
O
*Note: Aldehydes redyce the Ag(I) in Tollen’s reagent to Ag, forming a silver mirror.
RCHO + 2[NH3→AgNH3]+ + 3OH– ⎯⎯⎯ heat
→ RCOO– + 2Ag (s) + 4NH3 + 2H2O
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
Mr Cheng 13 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
CH3 C
OH
+ 3[O] ⎯⎯⎯⎯⎯⎯⎯
KMnO4/H2 SO4 , heat
→ + H2O
2. Hydrolysis
a. Hydrolysis of Nitriles (R–C≡N)
Acidic Hydrolysis
R–C≡N ⎯⎯⎯⎯
HCl ( aq )
reflux
→ RCOOH + NH4+
Basic Hydrolysis
R–C≡N ⎯⎯⎯⎯
NaOH ( aq )
reflux
⎯→ RCOO–Na+ + NH3
2. Esterification
O
R O R1
C O
conc H2 SO4 C R1
+ heat + H2 O
(can use acid or
alkaline as catalyst) R O
H
OH
4. Reduction to Alcohols
RCOOH + 4[H] ⎯⎯⎯⎯⎯⎯⎯
1. LiAlH4 in dry ether
2. H2 SO4 ( aq )
→ RCH2OH + H2O
Mr Cheng 14 2015
ORGANIC CHEMISTRY REACTION SCHEME – 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.
Preparations of Esters
1. Condensation Reaction of Acid and Alcohol
a. Ethyl Ethanoate
O
R O R1
C O
conc H2 SO4 C R1
+ heat + H2 O
(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 H2 SO4
RCOOH + R’OH
b. Basic Hydrolysis
RCOOR’ + H2O ⎯⎯⎯⎯
NaOH ( aq )
reflux
⎯→ RCOO–Na+ + R’OH
Preparation of Polyesters
1. Condensation Reaction
nHOOCRCOOH + nHOR’OH ⎯⎯⎯
acid
reflux
→ ( OCRCOOR’O ) n + 2nH2O
Mr Cheng 15 2015
ORGANIC CHEMISTRY REACTION SCHEME – 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
RCHRNH
2NH2
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 ⎯⎯
→
Br Br
+ 3Br2 (aq) ⎯⎯
→ (s) + 3HBr
White ppt
Br
Mr Cheng 16 2015
ORGANIC CHEMISTRY REACTION SCHEME – 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
+ CH 3COCl ⎯⎯
→
*Note: NHCOCH3 is also 2,4-directing but moderately activating. Halogenation of ArNHCOCH3 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
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
C ⎯⎯⎯⎯
Br2 , PBr3
heat
→ C ⎯⎯⎯⎯⎯⎯
excess conc NH3
→ C
H COOH COOH COOH
R Br R H2N R
Mr Cheng 17 2015
ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
3. Esterification
HCl
H2N–CH2–COOH + ROH +H
3N–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 + H2O
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.
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.
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.
Mr Cheng 18 2015