Chemistry - Organic Chemistry Reaction Scheme

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   Zn + H   RH + Zn2+ + X–
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+ K X + H 2 O
H X
2. Dehydration of Alcohols
H H H H
excess conc H2 SO4 , 170  C

H C C H     
or Al2 O3 , 400  C
   H C C H+ H 2O
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+ Z n X 2
X X
Reactions of Alkenes
1. Addition of Hydrogen. Catalytic Hydrogenation
CnH2n   2  Heat
    CnH2n+2
H + Ni, Pd or Pt
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ORGANIC CHEMISTRY REACTION SCHEME – AN OVERVIEW
2. Addition of Halogens [Electrophilic Addition using bromine/ethene]

H H H H
H C C H   dark, room
 temperature
   
X2 /CCl4
H C C H
X X
3. Addition of Aqueous Halogen. Formation of Halohydrin
H H H H
H C C H   X2 /H 2O  H C C H+ H X
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   concH 2HO(g)
  
3 PO 4
H C C H
300C, 60atm
H OH
b) Laboratory Method
H H H H H H
H C C H   conc cold 
H2 SO4
H C C H 
H2 O, heat
(hydrolysis)
→ H C C H+ H 2S O 4
H OS O 3 H H OH
6. Oxidation
a) Cold, alkaline KMnO4 Solution
H H H H
alkaline KMnO4
H C C H  cold
→H C C H
OH OH
b) Hot, acidic KMnO4 Solution
H H H H
−
H C C H →
MnO4 /H2 SO4
H C O + O C H
hot
*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]
NO2

conc. HNO3
conc. H2 SO4
→
55oC
2. Sulphonation
OSO 2H

H2 SO 4 ( l )
reflux
→ + H 2O
3. Halogenation
X
+ X 2

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
+ R C O C l / [(R C O ) 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 + HNX2 + H2O
Or H2/Pd,
ethanol
*Note: This is known as the Clemmensen or Wolff-Kishner Reduction
Reactions of Alkylbenzenes
1. Hydrogenation
R R
+ 3H 2

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
→
w h ite c r y s ta ls
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
NO2
conc HNO3

conc H2 SO4
→ +
o
30 C
NO2
6. Electrophillic Aromatic Friedal-Crafts Alkylation by Electrophillic Addition
R R R
R1

R1X
AlX3
→ +
R1
7. Electrophillic Aromatic Sulphonation by Electrophillic Addition

R R R
OSO 2H

H2 SO4 ( l )
→ +
OSO 2H
8. Electrophillic Aromatic Friedal-Crafts Acylation by Electrophillic Addition
R R R
COR1
+ R 1C O C l / [(R 1C O )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  → R–X + H2O
dry HX, ZnX2 (catalyst)
Reflux
b. Using PX3/PX5 (suitable for 1°, 2° alcohols)

PX3 /PX 5
R–OH  Reflux
→ R–X + POX3 + HX
c. Using SOCl2 (sulphonyl chloride)
SOCl2 , Pyridine(C5H5N)
R–OH  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.
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
Reactions of Halogenoalkanes
1. Alkaline Hydrolysis of Alcohols [Nucleophilic Substitution]
R–X + OH–    reflux   R–OH + X–
aqueous KOH
*Note: Mechanism is SN2 for 1° halogenoalkane and SN1 for 3° halogenoalkane
2. Nitrile Synthesis
R–X + NaCN    reflux
    R–C≡N + NaBr
aqueous ethanol
*Note: Nitriles are useful because they can be used to synthesize 1o amines and carboxylic acids.
Reduction to Amine:
R–C≡N   or 2H
 2 , Ni, heat
   RCH2NH2
LiAlH4 , dry ether
Acidic Hydrolysis:
R–C≡N   reflux
   RCOOH + NH4+
HCl ( aq )
Basic Hydrolysis:
    RCOO–Na+ + NH3
NaOH ( aq )
3. Formation of Amines
δ+ δ–
R–X + excess conc NH3   sealed

  tube  [H3N---R---X]   NH3  RNH2 + NH4+X–
ethanol, reflux
*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–
4. Williamson Synthesis (Formation of Ether)Conc H SO , 140 C 2 4

o
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 + K X + H 2O
H X
Preparation of Halogenoarenes (Aryl Halides)

1. Electrophilic Aromatic Halogenation by Substitution
X
+ X 2

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
→ + N aX + H 2O
-+
O Na OH
+ +

H ( aq )
→ + Na
2. Williamson Synthesis (Formation of Ether)

R–X + ArO–Na+ → R–O–Ar + NaX
Conc H2SO4, 140oC
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+ H 2S O 4
H OS O 3 H H OH
2. Alkaline Hydrolysis of Halogenoalkanes
R–X + OH–  → R–OH + X–
aqueous KOH
reflux
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 + H 2O
HO H
R H
+
C O + 4 [H ] 
or H2 , Ni
→ R C OH
H H
b. Ketones are reduced to their secondary alcohols.

R R
+
C O + 4 [H ] 
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 H 2O 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     Reflux      R–X + H2O
dry HX, ZnX2 (catalyst)
b. Using PX3/PX5 (suitable for 1°, 2° alcohols)

PX3 /PX 5
R–OH   Reflux    R–X + POX3 + HX
c. Using SOCl2 (sulphonyl chloride)
SOCl , Pyridine(C5H5N)
R–OH    2  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.
2. Reaction with Sodium/Potassium

H H
- + 1
H C O H 
Sodium/Potassium
→H C O Na + H 2
2
H H
*Note: Alcohols are too weak to react with hydroxides and carbonates.
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
→ C O
or KMnO4 /H2 SO4
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
→ C O
or KMnO4 /H2 SO4
R1
H R1
c. Tertiary alcohols are not readily oxidized.
4. Dehydration to Alkenes
a. Excess conc H2SO4
H H H H
excess conc H2 SO4 , 170 ° C

H C C H 
or Al2 O3 , 400 ° C
→ H C C H+ H 2O
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

+ H 2O
(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 )
→ CHI3
warm
CH3
a. Step 1: Oxidation of Alcohol to the corresponding carbonyl compound by iodine.
- -
R CH OH + I 2 + 2 HO R C O + 2 H2 O + 2 I
CH3 CH3
b. Step 2: Further oxidation to carboxylate salt and formation of iodoform

- -
R C O + 3 I2 + 4 HO R C O + CHI3 + 3 I + 3 H 2O
-
CH3 O
c. Overall Equation:
H
- -
R C OH + 4 I 2 + 6 HO R C O + CHI3 + 5 I + 5 H 2O
-
CH3 O
Preparations of Phenols
1. Replacement of OH– group in diazonium salts
N O
+ -
NH2 N O S OH OH
O
+

→
NaNO2 , H2 SO 4

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.
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 NO2

conc HNO3
→
NO2
b. With dilute nitric acid
OH OH OH
dil HNO3
 → +
NO2 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
CARBONYL COMPOUNDS
Preparation of Aldehydes
1. Oxidation of Primary Alcohols
R R
OH
C 
K 2 Cr2 O7 /H2 SO4
immediate
→ C O + H 2O
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 + H 2O
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 + NH4Cl
OH OH
Basic Hydrolysis
R R
- +
H C CN 
water, NaOH ( aq )
heat
→ H C COO Na + NH3
OH OH
*Note: Cyanohydrins can undergo reduction.

R R
H C CN →
LiAlH4 in dry ether
or H2 , Ni, heat
H C CH2NH2
OH OH
2. Reaction with 2,4-Dinitrophenylhydrazine (Brady’s Reagent). Condensation Reaction.

R2 R2
C O + H2N NH NO2 C N NH NO2 + 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.
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 SO 4
heat
→
O O
O O
C 
K 2 Cr2 O7 /H2 SO 4
heat
→ C
H OH
R R1
C 
K 2 Cr2 O7 /H2 SO4
→ N o R e a c tio n
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 SO 4
heat
O O
O O
C 
K 2MnO4 /H2 SO 4
→ 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
H
R R1
C 
Fehling's Solution
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
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
d. Oxidation of Aldehydes using Tollen’s Reagent (Silver Mirror Test) (Cont’d)

R R1
C 
Tollen's Reagent
warm
O
*Note: Aldehydes redyce the Ag(I) in Tollen’s reagent to Ag, forming a silver mirror.
RCHO + 2[NH3→Ag←NH3]+ + 3OH–   heat  RCOO– + 2Ag (s) + 4NH3 + 2H2O
4. Reduction Reactions
a. Reduction of Aldehydes to Primary Alcohols
R–CHO + 2[H]   or NaBH 4  ( aq )  R–CH2OH
LiAlH4 in dry ether
R–CHO + H2   heat    R–CH2OH

Ni catalyst
b. Reduction of Ketones to Secondary Alcohols

H
R R1
C
+ H2   LiAlH
 4 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 I 2 + 4 HO  NaOH, warm
→ R C O + CHI3 + 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
→ C O
or KMnO4 /H2 SO4
distillation
H
H H HO
b. Oxidative Cleavage of Alkenes

H H H O O H
C C
C C 
KMnO4 /H2 SO4 , heat
→ +
OH OH
H H
c. Oxidation of an Alkylbenzene (Formation of Benzoic Acid)

O
CH3 C
OH
+ 3 [O ] 
KMnO4/H2 SO 4 , heat
→ + H 2O
2. Hydrolysis
a. Hydrolysis of Nitriles (R–C≡N)
Acidic Hydrolysis
   RCOOH + NH4+
HCl ( aq )
Basic Hydrolysis
    RCOO–Na+ + NH3
NaOH ( aq )
b. Hydrolysis of Esters (RCOOR’)

Acidic Hydrolysis
HCl ( aq ), reflux
RCOOR’ + H2O

conc H2 SO4
RCOOH + R’OH
Basic Hydrolysis
RCOOR’ + H2O   reflux
    RCOO–Na+ + R’OH
NaOH ( aq )
+
RCOO–Na+   reflux
H
  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

+ H 2O
(can use acid or
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]   2. H24 SO4 ( aq )   RCH2OH + H2O
1. LiAlH in dry ether
Preparation of Acyl Chlorides

1. From Carboxylic Acid
RCOOH + PCl5    RCOCl + POCl3 + HCl
3RCOOH + PCl3    3RCOCl + H3PO3
RCOOH + SOCl2    RCOCl + HCl + SO2
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    4     RCHO   H 24SO 4 ( aq )   RCH2OH
LiAlH in dry ether LiAlH in dry ether
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

+ H 2O
(can use acid or
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   reflux
    RCOO–Na+ + R’OH
NaOH ( aq )
2. Reduction to Primary Alcohols

RCOOR’   H 24SO 4 ( aq )   RCH2OH
LiAlH in dry ether
Preparation of Polyesters
1. Condensation Reaction
nHOOCRCOOH + nHOR’OH   reflux  ( OCRCOOR’O )
acid
n + 2nH2O
NITROGEN COMPOUNDS
Preparation of Amines
1. Reaction of Halides with Ammonia or Amines. Ammonolysis
δ+ δ–
R–X + excess conc NH3   sealed

  tube  [H3N---R---X]   NH3  RNH2 + NH4+X–
ethanol, reflux
NH3   RX  RNH2   RX  R2NH   RX  R3N   RX  R4N+X–
2. Reduction
a. Reduction of Amide
RCONH2   H 24/ Ni or Pt   RCH
RNH22NH2
LiAlH in dry ether
b. Reduction of Nitrile
R–C≡N   LiAlH
 4 , dry ether
  
or 2H2 , Ni, heat RCH2NH2
c. Reductive Amination
H H
H
C O + NH3 → 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 NH3 Cl
+ HCl 
→
*Note: Phenylamine is not soluble in water but dissolves in acid.
2. Formation of Amides. Acylation.


R'COCl
→ R'CONHR + HCl
RNH2 ArSO2 Cl
 → ArSO 2NHR + HCl

R''COCl
→ R''CONRR' + HCl
RR'NH ArSO2 Cl
 → ArSO 2NRR' + 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
*Note: To get monosubstituted compounds, react phenylamine with ethanoyl chloride to reduce the ‘strongly
activating’ nature of the amino group to form phenylacetamide.
NH2 NHCOCH3
+ CH3COCl 
→
*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 NO2
conc HNO3
+ conc H SO →
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 ArSO2 Cl
 → ArSO 2NHR + HCl

R''COCl
→ R''CONRR' + HCl
RR'NH ArSO2 Cl
 → ArSO 2NRR' + HCl
Reactions of Amides
1. Acidic Hydrolysis
RCONH2  → R–COOH + NH4+
HCl, H2 O
heat
2. Basic Hydrolysis
RCONH2  → R–COO– + NH3
NaOH, H2 O
heat
Preparations of Amino Acids

1. Hell-Volhard-Zelinsky Reaction
H H H
Br2 , PBr3
C 
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
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
-
------ C C N C ------ 
NaOH ( aq )
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
FeCl3 , cold
 → Cl
+ Cl2 + 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.

Chemistry - Organic Chemistry Reaction Scheme

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Chemistry - Organic Chemistry Reaction Scheme

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ORGANIC CHEMISTRY REACTION SCHEME

2. Reduction of Alkyl Halides

b. Reduction by Metal and Acid

excess conc H2 SO4 , 170  C

3. Dehalogenation of Vicinal Dihalides

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

2. Conversion of side chain

*Note: This is known as the Clemmensen or Wolff-Kishner Reduction

3. Free Radical Aliphatic Halogenation

4. Electrophillic Aromatic Halogenation by Electrophillic Addition

7. Electrophillic Aromatic Sulphonation by Electrophillic Addition

+ R 1C O C l / [(R 1C O )2O ] 

b. Using PX3/PX5 (suitable for 1°, 2° alcohols)

2. Electrophillic Addition to Alkenes

3. Free Radical Substitution of Alkanes

*Note: Mechanism is SN2 for 1° halogenoalkane and SN1 for 3° halogenoalkane

R–X + excess conc NH3   sealed

*Note: NH3 acts as the nucleophile and the base.

4. Williamson Synthesis (Formation of Ether)Conc H SO , 140 C 2 4

R–X + R'O–Na+    R–O–R' + NaX

Preparation of Halogenoarenes (Aryl Halides)

2. Williamson Synthesis (Formation of Ether)

3. Reduction of Carboxylic Acids, Aldehydes and Ketones

b. Ketones are reduced to their secondary alcohols.

b. Using PX3/PX5 (suitable for 1°, 2° alcohols)

2. Reaction with Sodium/Potassium

3. Oxidation to Carbonyl Compounds and Carboxylic Acids

b. Secondary Alcohols are oxidized to ketones.

c. Tertiary alcohols are not readily oxidized.

excess conc H2 SO4 , 170 ° C

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

2. Reaction with NaOH

*Note: Phenols have no reactions with carbonates

6. Reaction with FeCl3(aq)

2. Oxidative Cleavage of Alkenes

Reactions of Carbonyl Compounds

*Note: Cyanohydrins can undergo reduction.

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

C O + H2N NH NO2 C N NH NO2 + H2O

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

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

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

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

R–CHO + H2   heat    R–CH2OH

b. Reduction of Ketones to Secondary Alcohols

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

6. Chlorination using Phosphorus Pentachloride (PCl5)

CARBOXYLIC ACIDS & DERIVATIVES

b. Oxidative Cleavage of Alkenes

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

b. Hydrolysis of Esters (RCOOR’)

Reactions of Carboxylic Acids

3. Conversion into Acyl Chlorides (RCOCl)

Preparation of Acyl Chlorides

Reactions of Acyl Chlorides

2. Ester Formation. Alcoholysis.

3. Amide Formation. Ammonolysis.

4. Reduction to Aldehyde, then Alcohol

2. Reduction to Primary Alcohols

R–X + excess conc NH3   sealed

NH3   RX  RNH2   RX  R2NH   RX  R3N   RX  R4N+X–

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