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 condNons Type of reactlon Remarks

excess O(g) + ignition Virtually all organic compounds can undergo
alkanes

1 CH CHP + Oz 4 2COz + H2 Combustion

2 CH3CH3 + C!2
3 High temp (- 500 C) with
H H
4 H C C CHyCHy
source combustion in excess Oz to give COC and HzO
A variety of products is invariably produced.
C/, uv light / high Free Radical
CH3CH C/ + HC/ Substitution Stating uv light as the condition is preferred
temperature
over high temperature.
High temp (- 900 C)
Thermal or Higher M, alkanes are broken down to give
catalytic cracking smaller alkanes, alkenes or H2(g)
catalyst
H(g), Ni, heat The detailed description of this reaction is
+ H, Reduction covered in Reaction Kinetics under
or He(g), Pt, room temp heterogeneous catalysis"
H H

H2O(g) (steam), HPO cat,

heat, high pressure
5 H C C CH,CHy + HCO (industrial conditions)
(i) cold conc HeSO, (ii)
H OH HzO, heat (laboratory Need to be able to predict the major product
conditions) (using knowledge of the mechanism and
Concentrated HBr Markonikovs rule)
HBr(g) generated in
6 H CCCHyCH/ + HBr
situ. NaBr(s) + conc
H Br H2SO Electrophilic
HBr in CC/4 Addition
CC/ is used as an inert solvent, and the reaction
7 H C C CHyCH/ + Bra Bra in CC/4, dark and is carried out in the dark and room
room temp temperature to prevent free radical substitution.
Br Br

Need to be able to predict the major product

8 HC C CHyCHy + B ry(aq) Br2(aq), room temp
(using knowledge of the mechanism)
Br OH
H H H H
KMnO(aq), cold,
9 H C C GH,CH/ + [O] + HCO
H2SO(aq) or
(Mild) Oxidation
OH OH NaOH(aq)

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H2 Chemistry 9729: Organic Chemistry Revision Series - Reactions Copyright @ Yishun Junior College

S/N Reactions Reagente and condltlone Type of reaction Remarks

alkenes
Distinguishing lest for terminal alkenes (double
H C C CHyCH/ + 5[O] COC H,O O C CH/CHy
Oxidation bond between 1" and 2 carbon) : heat with
CH
KMnO4(aq), or acidified KMnO, and test for presence of COC(g).
10 I '
H,C C == C CH, + 3[Oj ----- HzSO4(aq), reflux Oxidative Cleavage If NaOH(aq) is used instead of HMSO,(aq), salt
of carboxylic acid is obtained. CO will react with
OH tO Ohm CO3'
2CO, 2HyO

CONC HNO3* COUc HzSO,

11 H + HNOL + HCO
50 - 60 C Milder conditions may be used when ring
activating groups are present in the benzene ring
C/2. anhydrous FeC/ or (especially -OH and -NH groups)
A/CU or Fe filings, For multiple substitution into the benzene ring,
room temperature need to be able to predict the major product
12 (using knowledge of 2,4-directing and
Brz, anhydrous FeBr3 or 3-directing groups).
Br + HBr
Fe filings, room
temperature
Electrophilic
CHaC/, anhydrous A/CU, Substitution
13 H + CHyC/
room temperature
Friedel-Craft alkylation and acylation reactions.
CHzCOC /, anhydrous A/C/,
14 H + HICCC/
room temperature

As -CH3 group is ring-activating (and 2,4-

Crtg of OWN CH, + H O Conc HNO3, conc directing), the temperature required for the
15
H2SO, 30 C nitration of methylbenzene is lower than that for
benzene (#11).

Cir, uv light / Free Radical The side chain of methylbenzene can also
16 CHP + C/,
high Substitution undergo free radical substitution.
temperature

CHP + 3[O] HCO

KMnO(aq), H2SO(aq), Side-chain oxidation of arenes can occur as long
reflux as the carbon atom bonded to the benzene
H H 0 possesses at least one hydrogen atom (benzylic
17 C OH + CO, HCO Oxidation hydrogen).
In alkaline medium, the benzoate ion is formed
KMnO(aq), NaOH(aq), instead of benzoic acid.
reflux

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S/N Reaalons Ieagente and conditions Type of reaction Remarks

H H H H H H
halogen derivatives
l I l l l l KOH in ethanol, Need to be able to predict the major product
HCC C Crtg + HBr reflux (cannot accept Elimination (using knowledge of Saytzef1s rule -
heat for reactions knowledge of the mechanism is not required).
H Br H H involving RX)
NaOH(aq), reflux Applicable for 1 R-X (Sn2 mechanism). 2 R-X,
CHaCHeBr + OH- 6 CHCHzOH + Br- (cannot accept heat and 3 R-X (Su1 mechanism)
for reactions involving
RX) The relative rate of the reaction between
NaCN in ethanol, reflux halogenoalkane and nucleophile: CHzCH2C/
CH3CHBr + CN" --+ CHCH,CN + Br" (cannot accept heat for
reactions involving RX) <
CHCHzBr < CHCH2
CHyCHyBr + H N H CHyCH N -H + HBr
Nucleophilic due to bond strength: C-C/ > C-Br > C-I
H H Substitution
CHIC HyBr + CH/CH NH CH/CH N CHyCH/ + HBr Halogenobenzene are resistant to nucleophilic
H H
substitutions due to the delocalisation of the lone
NHS in ethanol, heat in pair of electrons on halogen into the benzene
21
CHIC HyBr + CHIC H CH,CH, CHyCH / + HBr sealed tube (with excess ring, leading to the C-X bond to have partial
H CHyCH, RX) double bond character:
CHyCHyBr + CH/CH N CHyCH/ B N{CH,CH,),
CHyCH/ No Reaction

PC/s(s), anhydrous,
CHgCHgOH !PC/s 6 CHzCHgC/ + POC/3 + HC/
room temperature
3cH,cHOH + Pcbs 3CH3CHC/ + H,PO, PC/(/) / PBr(/), PC/sts) and SOClz can be used in distinguishing
3CHCH2OH + PBr3 -+ 3CHCH Br + HPO anhydrous, room test for aliphatic alcohols - white fumes of HC/
temperature Nucleophilic produced, but same observations with carboxylic
22 CH3CHzOH + SOC /z H CHzCH2C/ + 502 HC/ acids
SOC/2( / SOBrz(/), Substitution
CH3CH2OH + SOBr 4 CHzCHzBr + SO + HBr
anhydrous, , room PC/s, PC// are the most effective reagents for the
temperature conversion of alcohols to chloroalkanes.
CHaCHzOH + HC/ 4 CH3CH2C / + H2 Conc HC/. ZnC/ / Conc HBr
CH3CHOH + HBr -' CH3CH2Br + H2 HC/(g) or HBr generated in
situ, NaC/(s) or NaBr(s) + conc
HSO
KMnO cannot be used, as it is too strong an
KtCr2O(aq), HMSO(aq),
23 oxidising agent (will convert the alcohol directly
immediate distillation
H
to the carboxylic acid)

OH 0
n,cc elol ----- H,c c oH + nO Oxidation Can be used as a distinguishing test for tertiary
KMnO(aq), H2SOs(aq),
alcohols and phenols from secondary and
reflux
24 OH O KeCreOz(aq), H2SO(aq),
primary alcohols - no decolourisation of purple
l KMnO or
reflux
HIC C CH, + [O} HIC C CH, HCO n remains orange for KzCr2O, for the
H
tertiary alcohol and phenols

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 H2 Chemistry 9729: Organic Chemistry Revision Series - Copyright @ Yishun Junior College !
Reactions

S/N gea iui Reagents and condltlons Type of reaction Remarks

25 H COH [O] CO + 21- KMnO(aq), Oxidation Distinguishing test for methanol: heat with acidified
1,O
HSO(aq), reflux KMnO, and test for presence of COC(g)
H
H H H Conc H2SO, reflux Need to be able to predict the major product (using
A/zOo, heat Elimination knowledge of Saytzeff s rule knowledge of the
26 H CC C (industrial process) mechanism is not required)
CH,
H Seldom-used distinguishing test for alcohol: sweet
H ON H
O
O
alcohols

27 II smelling liquid formed. Seldom-used due to other

CH CH OH + HOCCH GH3CHOC
conc H2SO, reflux Condensati available distinguishing tests, and because
CH on Or 'sweetness" is subjective. (same reaction as #47)
Nucleophilic
O O
28 CHCOC /, anhydrous, room substitution
(same reaction as #55)
CH/CH OH + C/C CHP Cl-INCH O C CHP temperature
HC/
Dis\inguishin9 test for alcohols or carbonyl
0 Oxidation compounds of the structures:
29 R CCHP + 41, + R C O CHIP + 5T- + 12(aq), NaOH(aq). Of HIC , or HICC - pale yellow ppt
6OH sH,O reflux Oxidative formed
H
Cleavage

Alcohols are such weak acids that they can only

30 CH3CH2OH + Na 4 CH3CH2O-Na + react with very strong bases like Na(s) to produce
H2tg); but not with NaOH(aq) or Na2CO.
/H3 Na(s), room temperature Redox
reaction

Phenols are strong enough acids to react with strong

NaOH(aq) , bases like Na(s) and NaOH(aq); but not with weak
Acid-base Reaction bases like Na2C
room
temperature O
32 OH NaOH
Neutralisation

NaOH(aq) or pyridine Condensation

Phenols are not reactive enough to react with
O followed by Or
phenols

carboxylic acids in conc H,SO to form esters:

CHCOC/, anhydrous Nucleophilic
+ C/CCHP Substitution
condition or cri,cOOH - No Reaction

34
NOT
OH
 dilute HNOL(aq) ,
room -OH group is a strong ring-activating group which
OH * temperature makes phenol undergo electrophilic substitutions
more readily than benzene (milder conditions
Eleclrophilic Substitution required
OH 3HNO, O,N OH
Conc HNOL, Need to be able to predict the major product (using
room knowledge that -OH grou p is 2,4-directing)
3HyO NO,
temperature
 H2 Chemistry 9729: Organic Chemistry Revision Series - Reactions Copyright @ Yishun Junior College

S/N Reactions
-OH group is a strong ring-activating group which
Bre in CC/, makes phenol undergo electrophilic substitutions
room more readily than benzene (milder conditions
or Br
temperature required).

Need to be able to predict the major product

phenols

(using knowledee that -OH group is 2,4-directing)

Br OH + 3 HBr Electrophilic
Bra(aq) , room Distinguishing test for phenol and phenylamine:
Substitution
temperature Bra(aq) - decolourisation of brown Br2taq) with
Br
formation of white ppt.
Br
-OH group is a stronger ring-activating group
36 than -CHP, hence the major product would be
Brz in CC/, 2,4-substituted with respect to -OH group.
room
0 OH temperature The product of the nucleophilic addition of HC N to

37 CH/CH CH HCN, trace of NaOH / NaCN, Nucleophilic a carbonyl compound is a cyanohydrin -

DCN cold Addition an important intermediate prodUCt in
9anic synthesis.

Distin9ishing test for carbonyl compounds (both

2,4-DNPH(aq), room
Condensation aldehydes and kelones) - yellow or orange ppt
temperature
formed.

KMnO,(aq), H2SO(aq), reflux Aldehydes are readily oxidised by strong oxidising

39 HIC C K Cr2A(aq), HzSO(aq), reflux agents to carboxylic acids.
HIC C H + [)] OH

Distinguishing test for methanal: heat with

KMnO(aq), HzSO(aq), reflux
40 acidified KMnO , and test for presence of COz(g).

HIC C O + 2Ag 4 NHS + Tollen's reagent (also known Oxidation Distinguishing test for aldehydes: Tollen's reagent
2HyO as silver(I) diammine
C H 2{ Ag(NHy)y] + - silver mirror formed; and Fehling's solution -
' H,c
3OH OF complex), warm brick red ppt of CuzO is formed.
o 41 O
Fehling's solution is nt strong enough to
O HICC O + ZAg 2 H,O oxidise aromatic aldehydes:
Fehling s solution (also known
HIC C H + 2Ag'
3OH 0 No Reaction

42 II 43 as ex) /
HIC C H + 2C u! + HICC O + CuyO + 3HyO alkalin Cu' in NHS(aq) / [Cu(NHS),]',
POH e Cu'
compl
 Distinguishing test for alcohols or carbonyl
Oxidation Oxidative compounds of the structures:
12(aq), NaOH(aq), heat

Cleavage
HIC C , Or H/C C - pale yellow ppt
formed
H

YJC Chemistry Unit / 2017

 H2 Chemistry 9729: Organic Chemistry Revision Series - Reactions opCyright @ Y hun Junior College

S/N Tteactbris Re"tigent and condkione Type of reaction Remarks

OH

HIC C CHP + 2[H] LiA2Hs in dry ether,

room temperature Ketones and aldehydes are readily reduced to
Na8H in ether, alcohol
form secondary and primary alcohols
44
O OH Ht(g), Ni(s), heal respectively. This process is the opposite to the
II
CH/CH C H + 2[I-I] Hz(g), Pt(s), room Reduction oxidation of primary and secondary alcohols.
temperature

O OH Hz(g), Ni(s) and NaBH are not able to reduce

II I LiA/H in dry ether,
45 CNyCH C OH + 4[H] CH/CH CH+ carboxylic acids to primary alcohols:
room temperature
H,O O
II
H CH CH COH + [H] -- No Reaction
0
Methanoic acid, HCOOH, and ethandioic acid,
HCOH + [O] COC + O (COOH) are the two carboxylic acids that can
46
O O KMnO(aq), HzSO(aq), be oxidized to give CO and HCO
reflux Oxidation
HO C C OH 2(O] 2CO, + Distinguishing test for HCOOH and (COOH) : hea!
HCO with acidified KMnO and test for presence of
co(9)
Seldom-used distinguishing test for carboxylic acids:
O 0 sweet smelling liquid formed - seldom used due to
47 Condensation
other available distinguishing tests, and because
conc H2SO, reux or

HICCOH + HO-CH2C H CC O-CH CH + Nucleophilic sweetness is subjective.

HCO Substitution (same reaction as #27)
O O
48 Na(s), room temperature Redox reaction

O O
NaOH(aq). room Carboxylic acids are strong enough to react
temperature with bases like NaOH(aq), including weak
O O bases like NazCOa / NaHCOz
Acid-base Reaction

2 H,C C OH + NICO, 2 H,C CO Na CO, +

HCO
TO O O

YJC Chemistry Unit / 2017

 N62CO/ (S) Of (aq) / NaHCOo(s) or (aq) ,
room temperature
H2 Chemistry 9729: Organic Chemistry Revision Series - Reactions Copyright @ Yishun Junior College !

S/N
carboxylic acids Readions " Reagents and condl0ons Type of reaction Remarks
0 anhydrous PC/s(s) ,
ld/C C OH + PCI H/C C CJ + POC/, HC/ room temperature

3 HyC C OH + PC/, 3H,CCCI *H,PO, anhydrous PC/z(/) / PBro(

O O , room temperature PC/s(s) and SOC/2 can be used in
3 HIC C OH + PBry 3 HICC Br + N/PO, distinguishing test for carboxylic acids - white
Nucleophilic fumes of HC/ produced, but same observations
Substitution obtained with aliphatic alcohols
anhydrous SOC/2(/) /
o SOBre(/) , room
II j temperature
HICCOH + SOBry H,C C Br * SOC HBr

O O The hydrolysis reaction is reversible when

HC/(aq) / H2SO(aq) / carried out in acidic medium (reverse of
HIC C O CHyCHy + HCO HICCOH + HO -CHECK HNOL(aq), reflux Hydrolysis reaction #47), and it goes to completion in the
O alkaline medium to yield the carboxylate salt.
Nucleophilic
O O Hydrolysis is always the first step in the
NaOH(aq), reflux Substitution
HIC C O-CH/CHy OH' HIC C O + HO -CH/C/ distinguishing test of an ester, and is usually
followed by the identification of the alcohol
formed
Hz(g). Ni(s) or Pt(s) and NaBH are not able to
O OH
II LiA/H in dry ether, reduce esters to primary alcohols:
54 CH/CHy C O CHyCH/ + 4[H] CH,CHy H + H) CACHE Reduction O
room temperature II
CH/CHy C O CHyCH + [H] No Reaction

A very strongly acidic solution is produced

acid chlorides

Hydrolysis due to the HC/ produced

or
H2O(/) , room temperature Nucleophilic Distinguishing test for acid chlorides: AgNO(aq)
Substitution - white ppt of AgC/ produced immediately
(most probably with white fumes of HC/
evolved).
0 O
CHCH2OH, anhydrous
li 11 (same as reaction #28)
condition room
' Condensation
temperature or
56
0 Nucleophilic
NaOH(aq) or pyridine Substitution
HICC f'/ + HO + HC/ followed by (same as reaction #33)
CH3COC/, anhydrous
condition
YJC Chemistry Unit / 2017
 H2 Chemistry 9729: Organic Chemistry Revision Series - Reactions Copyright @ Yishun Junior College

SDN .' ' '') ,.' . /\'. P3 >Po O

acid chlorides I Hi Remarks
conc NHS, room
+ H temperature
Only acid chlorides are reactive enough to react

H,C-Ccf + M-N- HIC C N - H + Condensation

H Sci with NH or amines to form amides, while
conc CH3NH, or
room Nucleophilic carboxylic acids are not:
O 0
57

HICC C7 H - N - CHP HICC N- CHP + temperature No Reaction

substitution
HC/ H,CCOM
N-H +H H-
0 conc (CH)zNH, room (same as reaction #64)
O cn, temperature
HyC CC/ + H- N - CHP HIC C N - CHP +
HCP HC/(aq) / HzSO(aq)
/
58
HICCNN + H 2H,O H,C C OH + HNOL(aq), reflux Hydrolysis Nitriles will undergo hydrolysis in acidic medium
NH, to give a carboxylic acid, and in alkaline medium
o to give a carboxylate salt.
NaOH(aq), reflux
HIC CAN + OH- + HCO QCC O" + NHS
LiA/H in dry ether ,
room temperature NaBH is not able to reduce nitrites to primary
Ht(g), Ni(s), heat amines:
60 Hz(g), Pt(s), /CC CN + [H} No Reaction
room
temperature Reduction
0
Although LiA/H can also reduce nitrobenzene to
phenylamine, it is not usually used, due to the
(i) Sn(s), conc HCI, formation of other products end also to prevent
reflux, the reduction of other functional groups (if any)
(ii) NaOH(aq) that is present.

Distinguishing test for phenylamine and phenol

Electrophilic - decolourisation of brown Bra(aq) with formation
n of white ppt.
62
Bra(aq), room
temperature

H HIC - N -
HIC -N- H H
H
H
amines

?'t, H,C -N-H

H,C- N - H + H H
 HC/(aq) / HeSO(aq) / Acid-base reaction All amines are basic and will react with dilute
63 CH, )H, HNOL(aq), room temperature or acids to form a
M,C-N-CH,+ H --*- H,C-N- neutralisation salt
CH,
H

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H2 C h emistry 972 9 : Org an ie C hemistry Revision Series Reactions Coping h I @ Yishun Junior College

S/N Reactions Reagents and conditions Type of reaction Remarks

amines
H /C N H + r / C CH/ H C N C CH HC /

Condensation or
CH3C OC/, anhydrous
64 Nucleophilic (same as reaction #57)
room temperature
substitution
N H + I/ C CHP

O LiA/H in dry ether, room

temperature NaBH is not able to reduce amides to amines:
CH/CH/ C N H + HCO O
H2(g), Ni(s), heat Reduction
H Hz(g), Pt(s), CH CH/ C NHS + {H] No Reaction
room
O temperature

H,C C < H + H ' + H,O HIC C OH NH,

Dilute acids such as HC/(aq)
66 O / HzSO(aq) / HNO3(aq),
H
reflux
Amides will undergo hydrolysis in acidic medium
H Hydrolysis to give a carboxylic acid, and in alk aline medium
O O to give a carboxylate salt.
HIC C O + NH,
67 O NaOH(aq), reflux
0
H C C N CH + O H H,C C O + H N CHP
amino-acids

H O
HC/(aq) / HzSO(aq) / Acid-Base or
68 HNCCO H H N C C OH
Neutralisation Amino-acids exist as zwitterionic form in aqueous
HNOL(aq) , room
temp sol utions, and can react with an acid (to form the
calionic form, and with a base (to form the anionic
form) . As such, an aqueous solution of amino-
Acid-Base or acids can act as a buffer solution.
69 NaOH(aq) , room temp
Neutralisation

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