Organic Chemistry Revision Reactions

One of the most basic principles in Organic Chemistry is the concept of a functional group, which is a specific atom or group of atoms within an organic molecule
that is responsible for its characteristic chemical properties. Therefore a good knowledge of the reagent(s) and conditions necessary for the conversion of a
compound having a particular functional group into another is quite basic and important.
For these frequently encountered reactions, you are expected to know: (i) reagents and conditions, (ii) identity of the major products, (iii) balanced equation, and
(iv) type of reaction that has occurred.

S/N Reactions Reagents and conditions Type of reaction Remarks

excess O2(g) + ignition Virtually all organic compounds can undergo
1 CH3CH3 + O2 2CO2 + H2O source
Combustion
combustion in excess O2 to give CO2 and H2O
A variety of products is invariably produced.
Cl2, uv light / high
alkanes

Free Radical
2 CH3CH3 + Cl2 CH3CH2Cl + HCl
temperature Substitution Stating uv light as the condition is preferred over
high temperature.
High temp (~ 900 C)
Thermal or Higher Mr alkanes are broken down to give
3 C10H22 C3H6 + C3H8 + C4H8 High temp (~ 500 C) with
catalytic cracking smaller alkanes, alkenes or H2(g)
catalyst
H H H H
The detailed description of this reaction is
H C C CH 2CH 3 + H2 H C C CH 2CH 3
H2(g), Ni, heat
4 reduction covered in Reaction Kinetics under
or H2(g), Pt, room temp
H H
heterogeneous catalysis

H H H H H2O(g) (steam), H3PO4 cat,

300C, 60 atm (industrial
5 H C C CH 2CH 3 + H2O H C C CH 2CH 3 conditions)
(i) cold conc H2SO4, (ii) H2O, Need to be able to predict the major product
H OH
heat (laboratory conditions) (using knowledge of the mechanism and
alkenes

H H H H Concentrated HBr Markonikovs rule)

H C C CH 2CH 3 + HBr H C C CH 2CH 3
HBr(g) generated in situ,
6
NaBr(s) + conc H2SO4
H Br HBr in CCl4 Electrophilic
Addition
H H H H
CCl4 is used as an inert solvent, and the reaction
H C C CH 2CH 3 + Br2
Br2 in CCl4, dark and room
7 H C C CH 2CH 3 is carried out in the dark and room temperature to
temp
Br Br prevent free radical substitution.
H H H H
Need to be able to predict the major product
8 H C C CH 2CH 3 + Br2(aq) H C C CH 2CH 3 Br2(aq), room temp
(using knowledge of the mechanism)
Br OH

YJC / 2016 Pg 1 of 10
 Chemistry: Organic Chemistry Revision Series Reactions Copyright @ Yishun Junior College

S/N Reactions Reagents and conditions Type of reaction Remarks

H H H H

H C C CH 2CH 3 + [O] + H2O

KMnO4(aq), cold,
9 H C C CH 2CH 3 (Mild) oxidation -
H2SO4(aq) or NaOH(aq)
OH OH
H H OH

H C C CH2CH3 + 5[O] CO2 + H2O + O C CH2CH3 Distinguishing test for terminal alkenes (double
st nd
bond between 1 and 2 carbon): heat with
alkenes

CH3 H CH3 OH Oxidation or acidified KMnO4, and test for presence of CO2(g).
KMnO4(aq),
10 Oxidative cleavage
H3C C C CH3 + 3[O] H3C C O+ O C CH3 H2SO4(aq), reflux
If NaOH(aq) is used instead of H2SO4(aq), salt of
H H
carboxylic acid is obtained. CO2 will react with
- 2-
OH to form CO3 .
H C C H + 6[O] 2CO2 + 2H2O

Conc HNO3, conc H2SO4,

11 H + HNO3 NO2 + H2O
50 60C Milder conditions may be used when ring
activating groups are present in the benzene ring
Cl2, anhydrous FeCl3 or (especially OH and NH2 groups)
H + Cl2 Cl + HCl AlCl3 or Fe filings, room For multiple substitution into the benzene ring,
temperature need to be able to predict the major product
12 (using knowledge of 2,4-directing and
H + Br2
Br2, anhydrous FeBr3 or Fe Electrophilic 3-directing groups)
Br + HBr
filings, room temperature Substitution

,
CH3Cl, anhydrous AlCl3 ,
13 H + CH3Cl CH3 + HCl
room temperature
arenes

Friedel-Craft alkylation and acylation reactions

O are not specifically mentioned in your syllabus
O
CH3COCl, anhydrous AlCl3,
14 H + H 3C C Cl C CH 3 + HCl
, room temperature

Cl2, uv light / high Free Radical The side chain of methylbenzene can also
15 CH3 + Cl2 CH2Cl + HCl
temperature Substitution undergo free radical substitution

O Side-chain oxidation of arenes can occur as long

CH3 + 3[O] C OH + H2O as the carbon atom bonded to the benzene
KMnO4(aq), H2SO4(aq), posseses at least one hydrogen atom (benzylic
16 oxidation hydrogen)
H H O reflux
C C H + 5[O] C OH + CO2 + H2O In alkaline medium, the benzoate ion is formed
instead of benzoic acid.

YJC / 2016 Pg 2 of 10
 Chemistry: Organic Chemistry Revision Series Reactions Copyright @ Yishun Junior College

S/N Reactions Reagents and conditions Type of reaction Remarks

O
KMnO4(aq), NaOH(aq),
CH3 + 3[O] + OH- C O + 2H2O
reflux

H H H H H H
KOH in ethanol, reflux Need to be able to predict the major product
17 H C C C CH 3 H C C C CH 3 + HBr (cannot accept heat for Elimination (using knowledge of Saytzeffs rule knowledge
H Br H H
reactions involving RX) of the mechanism is not required)

NaOH(aq), reflux
Applicable for 1 R-X (SN2 mechanism), 2 R-X,
18 CH3CH2Br + OH CH3CH2OH + Br (cannot accept heat for
reactions involving RX) and 3 R-X (SN1 mechanism)
halogen derivatives

NaCN in ethanol, reflux The relative rate of the reaction of

19 CH3CH2Br + CN CH3CH2CN + Br (cannot accept heat for halogenoalkane with nucleophile: CH3CH2Cl <
reactions involving RX) CH3CH2Br < CH3CH2I
CH 3CH 2Br + H N H CH 3CH 2 N H + HBr due to bond strength: C-Cl > C-Br > C-I
H H Nucleophilic
Halogenobenzene are resistant to nucleophilic
CH 3CH 2Br + CH 3CH 2 N H CH 3CH 2 N CH 2CH 3 + HBr Substitution
substitutions due to the delocalisation of the lone
H H pair of electrons on halogen into the benzene
CH 3CH 2Br + CH 3CH 2 N CH 2CH 3 CH 3CH 2 N CH 2CH 3 + HBr NH3 in ethanol, heat in ring, forming partial double bond character for the
20
H CH 2CH 3
sealed tube (with excess RX) C-X bond:

Br + :Nu No Reaction

PCl5(s), anhydrous, room

CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl
temperature
3CH3CH2OH + PCl3 3CH3CH2Cl + H3PO3 PCl3(l) / PBr3(l), anhydrous,
3CH3CH2OH + PBr3 3CH3CH2Br + H3PO3 room temperature
PCl5(s) and SOCl2 can be used in distinguishing
SOCl2(l) / SOBr2(l), test for aliphatic alcohols white fumes of HCl
CH3CH2OH + SOCl2 CH3CH2Cl + SO2 + HCl
alcohols

anhydrous, , room produced, but same observations with carboxylic

CH3CH2OH + SOBr2 CH3CH2Br + SO2 + HBr Nucleophilic
21 temperature acids
Substitution
Conc HCl, ZnCl2 / Conc HBr
PCl5, PCl3 are the most effective reagents for the
HCl(g) or HBr generated in situ,
NaCl(s) or NaBr(s) + conc
conversion of alcohols to halogenoalkanes.
CH3CH2OH + HCl CH3CH2Cl + H2O
H2SO4
CH3CH2OH + HBr CH3CH2Br + H2O

YJC / 2016 Pg 3 of 10
 Chemistry: Organic Chemistry Revision Series Reactions Copyright @ Yishun Junior College

S/N Reactions Reagents and conditions Type of reaction Remarks

OH O
KMnO4 cannot be used, as it is too strong an
H3C C H + H2O
K2Cr2O7(aq), H2SO4(aq),
22 H3C C H + [O] oxidizing agent (will convert the alcohol directly to
immediate distillation
H
the carboxylic acid)

OH O

H3C C H + 2[O] H3C C OH + H2O Can be used as a distinguishing test for tertiary
KMnO4(aq), H2SO4(aq),
alcohols and phenols from secondary and primary
H reflux
23 Oxidation alcohols no decolourisation of purple KMnO4 or
OH O K2Cr2O7(aq), H2SO4(aq),
solution remains orange for K2Cr2O7 for the
CH3 + H2O
reflux
H3C C CH3 + [O] H3C C tertiary alcohol and phenols
H
H

H C OH + [O] CO2 + 2H2O KMnO4(aq), H2SO4(aq), Distinguishing test for methanol: heat with
24
reflux acidified KMnO4, and test for presence of CO2(g)
H
H H H H H H
Conc H2SO4, 170C Need to be able to predict the major product
o
25 H C C C CH 3 H C C C CH 3 + H2O Al2O3, 350 C (industrial Elimination (using knowledge of Saytzeffs rule knowledge
H OH H process) of the mechanism is not required)
H

O O Seldom-used distinguishing test for alcohol: sweet

smelling liquid formed seldom used due to other
26 CH3CH2 OH + HO C CH3 CH3CH2 O C CH3 + H2O
conc H2SO4, reflux
Condensation or available distinguishing tests, and because
Nucleophilic sweetness is subjective. (same reaction as 43)
O O substitution
CH3COCl, anhydrous, room
(same reaction as 55)
alcohols

27
CH3CH2 OH + Cl C CH3 CH3CH2 O C CH3 + HCl temperature
Distinguishing test for alcohols or carbonyl
compounds of the structures:
OH O
OH O H3C C , or H3C C pale yellow ppt
Oxidation or formed
28 R C CH 3 + 4I2 + 6OH- R C O + CHI3 + 5I + 5H2O
- I2(aq), NaOH(aq), reflux H
Oxidative cleavage
H

YJC / 2016 Pg 4 of 10
 Chemistry: Organic Chemistry Revision Series Reactions Copyright @ Yishun Junior College

S/N Reactions Reagents and conditions Type of reaction Remarks

Alcohols are such weak acids that they can only

+
29 CH3CH2OH + Na CH3CH2O Na + H2 react with very strong bases like Na(s) to produce
H2(g); but not with NaOH(aq) or Na2CO3.
Na(s), room temperature Redox reaction

30 OH + Na O Na+ + 1/2H2
Phenols are strong enough acids to react with
strong bases like Na(s) and NaOH(aq); but not
NaOH(aq) , room Acid-base reaction with weak bases like Na2CO3.
31 OH + NaOH O Na+ + H2O
temperature or neutralisation

NaOH (aq) or pyridine Phenols are not reactive enough to react with
O O
followed by CH3COCl, Condensation or carboxylic acids in conc H2SO4 to form esters:
phenols

32 OH + Cl C CH3 O C CH3 + HCl anhydrous condition Nucleophilic

substitution OH + CH3COOH No Reaction

dilute HNO3(aq) , room OH group is a strong ring-activating group which

temperature makes phenol undergo electrophilic substitutions
Electrophilic more readily than benzene (milder conditions
33 NO2 required
Substitution
OH + 3HNO3 O2N OH + 3H2O
Conc HNO3, room Need to be able to predict the major product
temperature (using knowledge that OH group is 2,4-directing)
NO2

OH group is a strong ring-activating group which

Br2 in CCl4, room makes phenol undergo electrophilic substitutions
temperature more readily than benzene (milder conditions
required
34 Br Need to be able to predict the major product
(using knowledge that OH group is 2,4-directing)
phenols

OH + 3Br2 Br OH + 3HBr Br2(aq) , room temperature Electrophilic

Substitution Distinguishing test for phenol and phenylamine:
Br2(aq) decolourisation of brown Br2(aq) with
Br
formation of white ppt
Br
OH group is a stronger ring-activating group
Br2 in CCl4, room
35 H 3C OH + Br2 HC 3 OH + HBr
than CH3, hence the major product would be
temperature
2,4-substituted with respect to OH group

YJC / 2016 Pg 5 of 10
 Chemistry: Organic Chemistry Revision Series Reactions Copyright @ Yishun Junior College

S/N Reactions Reagents and conditions Type of reaction Remarks

O OH The product of the nucleophilic addition of HCN to
CH3CH2 C H + HCN
HCN, trace of NaOH / NaCN, Nucleophilic a carbonyl compound is a cyanohydrin an
36 CH3CH2 C H
10C 20C Addition important intermediate product in organic
CN synthesis
H H H
H 3C H 3C
Distinguishing test for carbonyl compounds (both
C O + H N N NO2 C N N NO2 + H 2O 2,4-DNPH(aq), room Condensation
37 aldehydes and ketones) yellow or orange ppt
H 3C H 3C temperature Reaction
O2N O2N
formed

KMnO4(aq), H2SO4(aq),
O O
reflux Aldehydes are readily oxidized by strong oxidizing
carbonyl compounds

38
H 3C C H + [O] H 3C C OH K2Cr2O7(aq), H2SO4(aq), agents to carboxylic acids
reflux
O
KMnO4(aq), H2SO4(aq), Distinguishing test for methanal: heat with
39
H C H + [O] CO2 + H2O reflux acidified KMnO4, and test for presence of CO2(g)
O O Tollens reagent (also known
H 3C C H + 2[Ag(NH3)2 + ]+ 3OH-
as silver(I) diammine
H 3C C O + 2Ag + 4NH3 + 2H2O
complex), warm Oxidation Distinguishing test for aldehydes: Tollens reagent
40 silver mirror formed; and Fehlings solution
or brick red ppt of Cu2O is formed
Fehlings solution is not strong enough to oxidise
RCHO + 2 Ag + 3OH + - -
RCO2 + 2Ag + 2H2O aromatic aldehydes:
O
Fehlings solution (also C H + 2Cu2+ + 5OH- No Reaction
O O 2+
known as alkaline Cu
41 2+
H3C C H + 2Cu2+ + 5OH- H 3C C O + Cu2O + 3H2O complex) / Cu in NH3(aq) /
2+
[Cu(NH3)4] , warm

Distinguishing test for alcohols or carbonyl

compounds of the structures:
O O
Oxidation or OH O
42 I2(aq), NaOH(aq), heat
carbonyl compounds

R C CH3 + 3I2 + 4OH- R C O + CHI3 + 3I- + 3H2O Oxidative cleavage

H3C C , or H3C C pale yellow ppt
formed
H
O OH

H 3C C CH 3 + 2[H] H3C C CH 3
LiAlH4 in dry ether, room
temperature Ketones and aldehydes are readily reduced to
H NaBH4 in ether, alcohol form secondary and primary alcohols
43 Reduction
O OH H2(g), Ni(s), heat respectively. This process is the opposite to the
CH3CH2 C H + 2[H] CH3CH2 C H
H2(g), Pt(s), room oxidation of primary and secondary alcohols.
temperature
H

YJC / 2016 Pg 6 of 10
 Chemistry: Organic Chemistry Revision Series Reactions Copyright @ Yishun Junior College

S/N Reactions Reagents and conditions Type of reaction Remarks

H2(g), Ni(s) and NaBH4 are not able to reduce
LiAlH4 in dry ether, room carboxylic acids to primary alcohols:
O OH temperature
O
44 CH3CH2 C OH + 4[H] CH3CH2 C H + H2O
CH 3CH 2 C OH + [H] No Reaction
H

O Methanoic acid, HCOOH, and ethandioic acid,

H C OH + [O] CO2 + H2O
(COOH)2, are the two carboxylic acids that can be
KMnO4(aq), H2SO4(aq), oxidized to give CO2 and H2O
45 Oxidation
O O reflux Distinguishing test for HCOOH and (COOH)2:
carboxylic acids

HO C C OH + 2[O] 2CO2 + H2O heat with acidified KMnO4, and test for presence
of CO2(g)
Seldom-used distinguishing test for carboxylic
Condensation or acids: sweet smelling liquid formed seldom
46 conc H2SO4, reflux Nucleophilic used due to other available distinguishing tests,
substitution and because sweetness is subjective.
(same reaction as 26)
O O
47 Na(s), room temperature Redox reaction
H3C C OH + Na H3C C O Na+ + 1/2H2

O O
NaOH(aq), room
48 Carboxylic acids are strong enough to react with
H3C C OH + NaOH H3C C O Na+ + H2O temperature
bases like NaOH(aq), including weak bases like
O O Na2CO3 / NaHCO3
Acid-base reaction
2 H3C C OH + Na2CO3 2 H3C C O Na+ + CO2 + H2O Na2CO3 (s) or (aq) /
49 O O
NaHCO3(s) or (aq) , room
temperature
H3C C OH + NaHCO3 H3C C O Na+ + CO2 + H2O

O O
anhydrous PCl5(s) , room
carboxylic acids

H3C C OH + PCl5 H3C C Cl + POCl3 + HCl temperature Nucleophilic

Substitution
O O PCl5(s) and SOCl2 can be used in distinguishing
50 test for carboxylic acids white fumes of HCl
3 H3C C OH + PCl3 3 H3C C Cl + H3PO3 anhydrous PCl3(l) / PBr3(l) , produced, but same observations obtained with
O O room temperature aliphatic alcohols
3 H3C C OH + PBr3 3 H3C C Br + H3PO3

YJC / 2016 Pg 7 of 10
 Chemistry: Organic Chemistry Revision Series Reactions Copyright @ Yishun Junior College

S/N Reactions Reagents and conditions Type of reaction Remarks

O O
H3C C OH + SOCl2 H3C C Cl + SO2 + HCl anhydrous SOCl2(l) /
O O SOBr2(l) , room temperature Nucleophilic
H3C C OH + SOBr2 H3C C Br + SO2 + HBr
Substitution

O O The hydrolysis reaction is reversible when carried

HCl(aq) / H2SO4(aq) / out in acidic medium (reverse of reaction 46), and
51
H3C C O CH3CH2 + H2O H3C C OH + HO CH3CH2 HNO3(aq), reflux Hydrolysis or it goes to completion in the alkaline medium to
Nucleophilic yield the carboxylate salt
O O Substitution Hydrolysis is always the first step in the
esters

52 NaOH(aq), reflux distinguishing test of an ester, and is usually

H3C C O CH3CH2 + OH- H3C C O + HO CH3CH2
followed by the identification of the alcohol formed
O OH H2(g), Ni(s) or Pt(s) and NaBH4 are not able to
LiAlH4 in dry ether, room reduce esters to primary alcohols:
53 CH3CH2 C O CH2CH3 + 4[H] CH3CH2 C H + HO CH2CH3 Reduction O
temperature
H CH 3CH 2 C O CH 2CH 3 + [H] No Reaction

A very strongly acidic solution is produced due to

O the HCl produced
O
Hydrolysis or
54 H2O(l) , room temperature Distinguishing test for acid chlorides: AgNO3(aq)
H3C C Cl + H2O H3C C OH + HCl Nucleophilic
Substitution white ppt of AgCl produced immediately (most
acid chlorides

probably with white fumes of HCl evolved)

CH3CH2OH, anhydrous
(same as reaction 27)
condition, room temperature
Condensation or
55 Nucleophilic
O O NaOH(aq) or pyridine
substitution
followed by CH3COCl,
H3C C Cl + HO H3C C O + HCl (same as reaction 32)
anhydrous condition

O O H
H
conc NH3, room temperature Only acid chlorides are reactive enough to react
acid chlorides

H 3C C Cl + H N H H 3C C N H + HCl
with NH3 or amines to form amides, while
O O Condensation or carboxylic acids are not:
H H conc CH3NH3, room
56 Nucleophilic O
H 3C C Cl + H N CH 3 H 3C C N CH 3 + HCl temperature H
substitution
H 3C C OH + H N H No Reaction
O O
CH 3 CH 3 conc (CH3)2NH, room (same as reaction 63)
H 3C C Cl + H N CH 3 H 3C C N CH 3 + HCl temperature

YJC / 2016 Pg 8 of 10
 Chemistry: Organic Chemistry Revision Series Reactions Copyright @ Yishun Junior College

S/N Reactions Reagents and conditions Type of reaction Remarks

O
HCl(aq) / H2SO4(aq) /
57 H 3C C N + H+ + 2H2O H 3C C OH + NH4+ HNO3(aq), reflux Nitriles will undergo hydrolysis in acidic medium
Hydrolysis to give a carboxylic acid, and in alkaline medium
O
to give a carboxylate salt
58 H 3C C N + OH- + H2O
NaOH(aq), reflux
H 3C C O + NH3

LiAlH4 in dry ether , room

nitrogen compounds

H H
temperature NaBH4 is not able to reduce nitriles to primary
59 H 3C C N + 4[H] H 3C C N H H2(g), Ni(s), heat amines:
H H2(g), Pt(s), room H3C C N + [H] No Reaction
temperature
Reduction
Although LiAlH4 can also reduce nitrobenzene to
phenylamine, it is not usually used, due to the
(i) Sn(s), conc HCl, reflux,
60 NO2 + 6[H] NH2 + 2H2O formation of other products and also to prevent
(ii) NaOH(aq)
the reduction of other functional groups (if any)
that is present
Br
Distinguishing test for phenylamine and phenol
Electrophilic
61 NH 2 + 3Br2 Br NH 2 + 3HBr Br2(aq), room temperature decolourisation of brown Br2(aq) with formation of
Substitution
white ppt
Br
H H
+
H3C N H + H+ H3C N H
H
CH3 CH3
+
H3C N H + H+ H3C N H
amines

H HCl(aq) / H2SO4(aq) / Acid-base reaction All amines are basic and will react with dilute
62 CH 3 CH 3
+ HNO3(aq), room temperature or neutralisation acids to form a salt
H 3C N CH 3 + H+ H 3C N CH 3
H
H H
+
N H + H+ N H
H

O H O
H
H 3C N H + Cl C CH 3 H 3C N C CH 3 + HCl
O CH 3O
amines

CH 3 Condensation or
CH3COCl, anhydrous
63 H 3C N H + Cl C CH 3 H 3C N C CH 3 + HCl Nucleophilic (same as reaction 56)
condition, room temperature
O O substitution
H H
N H + Cl C CH 3 N C CH 3 + HCl

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S/N Reactions Reagents and conditions Type of reaction Remarks

H
LiAlH4 in dry ether, room NaBH4 is not able to reduce primary amides to
O H H temperature primary amines:
64 CH3CH2 C N H + 4[H] CH3CH2 C N H + H2O H2(g), Ni(s), heat Reduction O
H H2(g), Pt(s), room CH 3CH 2 C NH 2 + [H] No Reaction
temperature
O H O

H3C C N H + H+ + H2O H3C C OH + NH4+ Dilute acids such as HCl(aq)

amides

65 O H O H / H2SO4(aq) / HNO3(aq),
H 3C C N CH 3 + H+ + H2O H 3C C OH + H N CH 3
+ reflux
Amides will undergo hydrolysis in acidic medium
H Hydrolysis to give a carboxylic acid, and in alkaline medium
O H O to give a carboxylate salt
H 3C C N H + OH- H 3C C O + NH3
66 O O
NaOH(aq), reflux
H H
H 3C C N CH 3 + OH- H 3C C O + H N CH 3

H H O H O
H
+
+ H+
+ HCl(aq) / H2SO4(aq) / Acid-Base or Amino-acids exist as zwitterionic form in aqueous
amino-acids

67 H N C C O H N C C OH
HNO3(aq) , room temp Neutralisation solutions, and can react with an acid (to form the
H R H R
cationic form, and with a base (to form the anionic
H H O
H H O form)
+ Acid-Base or As such, an aqueous solution of amino-acids can
68 H N C C O + OH- H N C C O + H2O NaOH(aq) , room temp act as a buffer solution
Neutralisation
H R R

YJC / 2016 Pg 10 of 10