Beruflich Dokumente
Kultur Dokumente
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
400-600 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
H OH
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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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
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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
*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
+
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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H2 SO4 ( l )
+
OSO2H
8. Electrophillic Aromatic Friedal-Crafts Acylation by Electrophillic Addition
R R R
COR1
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.
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
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Reactions of Halogenoalkanes
1. Alkaline Hydrolysis of Alcohols [Nucleophilic Substitution]
R–X + OH–
aqueous KOH
reflux
R–OH + X
–
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
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+
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
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.
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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 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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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.
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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
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
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 CH2NH 2
OH OH
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
O O
O O
C
K 2MnO4 /H2 SO4
C
heat
H OH
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
O O
O O
C
Tollen's Reagent
warm
C + Ag (s)
-
H O
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O
*Note: Aldehydes redyce the Ag(I) in Tollen’s reagent to Ag, forming a silver mirror.
– –
RCHO + 2[NH3AgNH3] + 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
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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
+
Basic Hydrolysis
–
RCOOR’ + H2O RCOO Na + R’OH
NaOH (aq ) +
reflux
RCOO–Na+
+
H
reflux
RCOOH
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
4. Reduction to Alcohols
RCOOH + 4[H]
1. LiAlH4 in dry ether
2. H2SO4 ( aq )
RCH2OH + H2O
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ORG ANIC CHEM IST RY RE ACT ION SCHEM E – AN OVERVIEW
– –
RCOCl + ArO
RCOOAr + Cl
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
+
Reaction of Esters
1. Hydrolysis
a. Acidic Hydrolysis
HCl ( aq ), reflux
RCOOR’ + H2O conc
H2SO
RCOOH + R’OH
4
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
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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
Br Br
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
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 Br COOH COOH
R R H2N R
*Note: The above two equations explains the buffering capability of amino acids.
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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.
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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