Organic chemistry

chemistry of carbon compounds

Properties of carbon atom :

-
has 4 valence e-

-
can form 4 covalent bonds

Functional group=
same chem properties

Important for

① A basic by which organic compounds are divided into different classes

8 A basic for naming organic compounds

⑤ A particular functional group will always undergo similar types of chemical reactions

Exercises :

HS : ester
carbo alkoxy
FG :
benzene ring
carbonyl carbonyl
COOCHs carbonyl
↓ Caldehyde (
Hs amide C C
C NH2
:
CH3 CHCHCH 2 -
=

aming
FG : carboxamide hydroxyl amino
NHa " carboxamide
C
C =

amino carboxyl
HS : amine
hydroxyl
FG : Amino

hydroxyl D carbonyl

structural formula

expanded
condensed
-

carbonyl

skeletal
hydroxy
-

C= C
carboxyl
Condensed structure

X show single bonds

show double & triple bond

(HSCH (1) (Hc CH 3

2 .

Skeletal structure
C
H

-
-
show only carbon skeleton I
-

H
-

H atoms are not written

2 it

Exercises
j

1) Il

CH3 CHC CI 3

OH Skeletal

OH
expanded condensed
HHOH
111l I

H -
C -
C -
c -
C -
H CH3CH(OH) C =
0 CH

it of it ↓

Cl
2) .
I

" MHC
H HHH
11
H -
C = c -
c -
c -

C -
C
-

H CH =
=
((C)) C =
0 (He CH (NH2) (He

i " It I
NHL
it

expanded condensed
 3) CHsCH (NH1) ( (OH) (21) H(CH3) -

Skeletal
expanded
NH2

H H OH I
HH
11 OH
H -

C -
C -
C -

C -

C -
H I

itH ' it
"
H-
H

g
4)
CHs- OCHI
.

expanded structural

H O HH
I 1I
8
H -

C -

C -

C -

C -

H II
it
it

Classification of Catoms

① (1 )
%

bonded to
primary >
-

g secondary (20 >

-
bonded to 2

③ tertiary (3 )
%

>
-

bonded to 3

⑦ quarternary (40)
>
-
bonded to 4

Bond Cleavage

Types of covalent bond cleavage

O Homolytic cleavage (symmetry
② Heterolytic clearage

of similar electronegativity
> involving 2 atoms
Homolytic cleavage
-

>
-
a single bond breaks symmetrically into 2 equal parts
-

Formed free radicals

a very reactive species in an unpaired e-

! +

free radicals

##4 primary secondary tertiary radical ?

, ,

E carbon atom

example :

H -

I -
CHaCH
EDG
electron donating group

why tertiary radical is the most stable ?

bes increasing no . of EDG

 HsC- CH ·

CHe
secondary secondary

> occurs in a polar bond

involving unequal sharing of e-pair
cleavage
-
Heterolytic transferred to the electronegative atom
>
-
both the bonding e-are more

cation
polar unsymmetryanion
bond

example :

St 8-
+

H -
Br >
-

H + Br
He Sa
CH + H20 - CH3CHef H
CHz = 2

Catalyst

y H H
4 x 4-
+ + H H
-

I I
11
H-CEC-H + Her
-H
Type of reaction
NuE
M It H
① Addition

electrophilic addition
② substitution

③ Elimination

① Rearrangement

substitution
M <
rearrangement
free radical

Et

Nu-
type of reaction

-
elimination
addition

E NuG

electron-rich & electron-pair donor

species
from Nucleophile (neutral /negatively charged
electron-deficient species & accepting attacking nucleophile
-

e an

Electrophile (neutral/positively charged anior

carbanion
neutral atom (Lewis acids) nucleus negatively neutral atom

atom/ion incomplete octet loving ion lone pair

e-loving
-

the -

Cle
-

expanded octet
+
H -
no lone pair
By : NH3
NOzt BF3 SF4
v Alls
carbocation

Electrophilic site

low electron density around a polar bond

Examples :

S+ 8- 8+ 6-

C =
0 carbonyl C X (naloalhanes (

8+ 8-

C-OH (hydroxy compounds

 SUBSTITUTION
cada uv ,
means free radical

FREE RADICAL SUBSTITUTION ELECTROPHILIC SUBSTITUTION NUCLEOPHILIC SUBSTITUTION tukarje

-

ur/heat S
St a +

CH3 CHCH3 + HBr-

> CHsCHCHs
-reactant +
product H H BL

come from radical

+ Bra >
-
+ HBr
OH HO Br r
H H *

at at CH3 CHCH3 + OH-

H
Step 1 :
initiation step a
+

UV
11 -
21 < 2C1
S

H
Step 2 :
Propagation
H
H H
H

H-c-H H-k-c
Yv

H-
ar

H-
,
He - >

Nut site HH I
H
Hi H
11 1 I I

CH3CHECHCls + Cla >

H -
C -
c -

C -
C -
H - -

C -

C -

C -

C-H

it d i it adi
↑

Termination (Cantumkan balik (

Step 3 :

+
[I CI

+
H

H- it

ADDITION
name of rxn depends on sape yg nk masuk

NUCLEOPHILIC ADDITION NuO site (high density of e-) ELECTROPHILIC ADDITION

① diaxcukusite
Br
EO Nu site
site
CHSCH =
CHCHs + Bra > CH3CHCH (Hs > CH3CHCHCHs
nucleophilic site
8-
O 0 attract E
+
(CH3) OCHe
Br Br
Il I I Br Br
Che -

C -

CHs + CHzOH >

CH3-C-CHe > CH3C- CH3 7

St

OCH3
OH OH
focus ( OHO

electrophilic CH3 CH3 CH3

site I I I

CH3CH = CCH3 + HeO >

CH3CHCCH3 >
CHaCHCCHs

it it bu
a

Nut site
① HQ OHE
C 7

saturated unsaturated
ELIMINATION
>
-

HoSO4
CH3 CHa CH2 OH , CHaCH = CHz + HeO

REARRANGEMENT
C
CH3CHa--CHaCHa-H
H-
= I

C - H
H -
C
Ho
G
ONU BVz
+ >
-

I Il

H "C

2x
H -

-
Br But

H / H
I + Brz >

H & H

substi
M electrophilic
 I somerism

Different structural formula that have the same molecular formula

Type of isomers

Structuralisomers

same molecular formula but differ in order of attachment of atoms

Stererisomers

same molecular formula but different arrangement of atoms in space

STRUCTURAL ISOMERS

1 chain Iskeletal isomerism

2
. Positional isomerism

.
3 Functional group isomerism

/ Skeletal
Chain isoner

-
Isomers differ in the carbon skeleton (diff c chain

same functional group & homologous series

CH 3
-
e .

g
I short >
-

long-
CH3CHCHCHs >
-
CH3CH2CHaCHaCH : CHs
short-
long >
-

CHa

Positional isomer
chain
-
have a substituent grp / functional grp in different positions
positional
-
e .
g (sH = C

functional
CH3CHaCH-Cl CHsCH(C1) CHs
group

I-chloropropane 2-chloropropane
-
alcohol
CH3 CH3 CnHante O -
ether
2
g
-
.
I
I
CH3CH2 CHCH3 CH3CCH2 CH3 OH

CHs
I

CHs H I OH
di
I
2, 3-dimethylbutane 2, 2-dimethylbutane O O O

alkene & cycloalkane

H
I MH
H C= C H C C =
C C C c =
c -

C C
C C C
- - -

CH3
- -
- - - -

2
9 it if i b
-

↓
.

C
CH CH3 I
- V -
-

3 CH3
C =
c -
C

!
-

Functional group isomer ( 3 >

-
can be positional/functional
-

different functional groups & belong to different homologous series in the same general formula

CHaCHzCHaCHzOH CH3CHaCHCH3 CH3CHCH2 OH

g
>
-
e .

OH
CH3 General formula classes of compounds

CnHentzO ; n > 1 alcohol & ether

CH3-O-CHaCHzOHs > CH3CHe-0-CHzCH3 CnHenO ; n33 aldehyde & ketone

X chain / skeletal is owner CnHenOz ; n >, 2 carboxylic acid & ester

CuHan ; n>3 alkene & cycloalkane

j
11
ii
CH3CHzCHaCHaC-H CHaCCHaCHaCHs
e
g
-

.
S

g g
Il positional Il

CHs(Hz CHzC H - > CHz(H2CHcC H -

CHE CH3
 alkene
8 g
-

e .
g Il Il
e
9
.
CsHo [CnHan)
CH3CHcC- OH > CH3C-0- CH3

CHs(H =
CHCH2 (Hs

functional grp C3H6O (CnHanO)

~
CHE
↓
& S
iP
CH3
CH3 H
Ketone
aldehyde

Q2 :
CH3CH =
CHCHz CH2CH3 CsHoOn (CnHznO2)
CH3 COOCHs
CH3 CH = CH =
CH2 g
II
OH
CH3CH =
CHCH CH3 functional :
CH3CH =
CHCH3 g

CH
positional
> :

arid
carboxylic ester
-
LOOH
CH3CH = (H =
CH(H > CH 3

g
Q3 : Il
CcHoO( CnHentz O
CH2CH =
CHCHCH2 C H
H H It
OH OCHzCHa I I

H-
I

H C 0 C 1
r
- -
- -

it H

alcohol ether

carbocation carbo anion

C C
t -

Geometrical isomer >

-

cis-trans isomer

① CH3CH = CHCHs

H H
I I
CH3C =
CCH3

H H Hydrogen at the same side

C =
C

Hs C CH3

cis-isomer

CHE H

C = C

H CH3

trans isomer

② CH3 CHaCH =
CHa

H H
-
I tak boleh bentuk cis-trans isomer)
C =
C
/ I
CH3 (H2 H

CH3
③ I for cycloalkane
CH3
CH3
ada 2 substituents
I
kena
-

H trans isomer
H3C
CH3 H H
I I
-
CH2 (Hs
H CH3
Hz( Hz( CH2CHs

H H
Hydrocarbon
Alkane

In Hant2 straight chain

Cattan cyclic

saturated compound
=
-- sp3 hybridize
>
- all C have 4 Sigma bonds

physical properties- >

boiling point~ intermolecular force (molar mass" IMF ,
B .
PM)
,

IUPAC name

synthesis
chemical reaction

① CH3CH2CHaCHaCHcCHeCHs heptane

CH3

② HHHHHHH
"
FE alphabets
65432 no
7 CH CH3 c * I TF total substituent
&

106 ethyl- 1-methyloctane

-

& 3
-
-

ethyl -

E-methyl octane #
10
& ethyl 4-methyl octane
- -

CH3
③
IHH"CHCHe"CH CHs .

its

2 , 3-dimethylhexane

CH3
&
IHH"CHCHe"CH CHs .

6P43 ,

5-bromo-2 , 3-dimethylhexane

2-bromo-4 , 5-dimethylhexane X

cyclopropane

F fluor

63
3 5412 CHs methyl
5412363
5
CH2 (H3 4

ethyl

& 5-ethyl-1-fluoro-2-methylcyclohexane
- 4-ethyl-2-fluoro -

1-methylcyclohexane
101 -

ethyl-5-fluoro -

4-methylcyclohexane

methyl
CH3
(sbb ada substituent)
> Parent
2
3
, 42

buty
423,
CH2CH2CH = CH3

1-butyl-3-methylcyclobutane
 CH3 Methyl
3

I 2 1-(2-methylbutyl) -

3 - methylcyclobutane

CH CH CHc CHs
↓ (3-methylcyclobutyl) 2-methylbutane -

=
2
I 34

CH3
2 methyl butane
(kalan jadi parent

& Hydrogenation of alkene

Pt Ni
Pd CHaCHcCHa ,
synthesis
X reaction & Combustion >

Alkane (a) in excess O2

,

!
CH3CH CH =
c
Et OH

CH3CH3 + O2 > 2CO2 + HeO

#* I
Synthesis
-

(b) in limited O2

reaction CH3CH3 + O2 > (0 + H20

② Wurt2 Reaction
(a) Identical alkyl halide
ether
> >&
CH3CH2Cl + CHsCHaCI + Na CHsCHa CHeCHs Halogenation >
-

free radical substitution HC

Cl
oR
CHg(CH3
CHaCHCH2 YV
+ Cla > + CH3CHCH2Cl
(b) Different alkylhalide ether
CHsCHzCHcCHs CH3CH2CHs
CH3 cHs zo CHe
CH3(l + CH3CHcCl + Na > CHaCHs + +

double double
H
(major (minor
yg 2nd campur I

yg first H - C -
C -
C tertiary primary
↓ *
-
it

UL
+ Clc > +
-

CH2 H3C Cl CH3

major minor

Alkene
HC H

-
H
12342-methyl-2-butene 111
Cuten H H- C -H
+ x-x + H 4
- -

- -

# H it
Hi it
&
C = C
3-propyl heptene H C H
!
-
-

unsaturated -
6543 is

spa
IUPAC

① CHgCH =
CHCH2CH3
3 2

2-pentene
I
bromo 4
I 2
567
By I
34

② CHe CHCCHCHs
=

methyl
ethyl
methyl
CHe 'HaHs trans-4-ethyl-3-heptene
methyl
1-ethyl -

4-methylbutene
4- bromo-2 , 5-dimethyl-2-heptene
I

CHaH = H =
6

⑥ -

③ CHs H C cis-3-methyl-3-hexene
I -
H
, p
/CH
3-methyl-2 5-hexene C C c = C3
,
X =
2

Hs(32CH3 HEC CH5

v cis-2-chloro-2-butene
4- methyl-1 4-hexene (2H5
,
CHs C H -
-
&
C C c =
C > "trans-3-methyl-3-hexene
cyclopentene
=

H CH H5C" CHS

⑦
6
5 3
CH3 CH2 H trans-2-chloro-2-butene

① HsH = CHCHe
4C =
C3

H 2 CHCH3 methyl
Ha
1 -

cyclohexyl-2-butene trans-2-methyl-3-nexene
 Dehydration of alcohol
+
H H HH H
1, 2-shift
⑦
CH3CHC-H" -C
I
-H20 P
Cha
CH3C-C
>
-
H

Hal CHE H dis H

L V

① Dehydration of alcohol A
- >
saytzeff rule
CH3CCH 3

C most stable alkene CH3( CH

"Ha
HaSOP C =

(CONCS>
=

CH3CH2OH
,

CHc CH2 H2O

CHa
= +
highly substituted
(product sama
M

Synthesis
Elimination Alkene

② R-X
Dehydrohalogenation
KOH
CH3CHaCI > CHc =
CH2 + HC/
reflux

carbonation
DAY AAA 41T bond ,

↑
H
eliminate Ho0 molecule
H H
H H
1 1, 2-shift
go
A .
-
HeO 30 -H 1
+

H30

Ha
-

OH + >
① C -

C -
H

at
-

it
He M

a
H
b I
:
O -
H
-

b A

main S V

agenable
Im " CH2 (Is =
CHCH3
nu
,

ia
i

&
methyl

55 2 substituent

major minor

H I
H CH3 H
H CH3 b CH3
1 100 1 1 2-shift 1 I

CHOC-I
- ,

CH3C- CH CH2 OH >

che
O -
H

b
i
A
~
CHs CH3 CH3
I

CH3) =
C -
CIS CHa C -
=
CH2

CHa CHE
 of alkene & Halogenation in aqueous solution
①Hydrogenation
He
H20
CHu CHa + CH3CHs Bra CH3 CHCH2
=
CH3CH =
CHz + >

unsaturated saturated oh Br
Reaction

Alkene

-
Hydration
CH3CH =
CH + HeO H3Ots CHa CHIHe
L
② Halogenation in inert solvent
HH ↓H
CHsCH = CHz + Bra CHaCl CHs)
1
-C -

Bu Br ⑤ Addition of H2SO4
electrophilic
~
addition CHz(H =
CHc HcSO4(cn s CHCHs >
-
CHsCHCHs
⑥ Hydrohalogenation ,
HBr ,
HI
,
HCI ,
HE ↓ SOsH OH
-

Markonikov rule > H must add to C=

in greater no .
of H
H HH
HH H
CH3CH CHz + HBr CH3CHCH3

H-4-
>

-H
= I 11
= + H-Br <H-CC
Bu it Bri
CH3 CH = CHc + HBr HO CH3 CH2CHB

anti-markonikov

Baeyer's Test

Q Oxidation in OH- , cold KMnO < > ② Oxidation on

O
KMnO4 ,
hot ,
He
Of 11

CH3(H =
CHe + KMn04 > MnOck + CH3CHCHa OH = -

c -
carbonyl
cold
(brown ppt) GHOH 1) H = -

COOH carboxyl
Reaction
2H = CO2 + H20
C =
C O
+ Il
i) H
CHs(1 (12 KMn04 CH3L-OH CO2 H2O
not"
= + + +
ii)

g O
i) KMnO4 ,
He Il Il
CHCH

CHIC
=
Y
CH3CCH3 + CH3C-OH
ii) not
③ Ozonolysis [
O
i

CH3CHECHaH/H30"/H2O
Il
CH3C-H + CHu

#I DA = 0

① oxidation i OH- ,
cold KMnO4 (Baeyer's Test) <
② Unsaturation Test (Brc ,
inert solvent)
Br
CH2Cl2
1. CH3CH =
CH 2
+ KMU04 > MnOct + CHaCHCHa 1 CH3CH =
CHz + Bra >
CH3CHCH2
ofOH
brown cr
precipitate Br
↑ # alkene A reaction
OH- CHack
.
2 CH3CHaCH3 + KMn04 > no reaction Chemical Test 2 CH3CHzCH3 + Bra > no reaction
vold
.

Observation : Observation :

& Purple color KMnOp turn colourless & brown precipitate formed 1 .

Brown color of bromine turns colourless

② color of KMnOp remain .

2 Brown color of bromine remain unchanged
Purple unchanged
 Te

4nf2 =
fre integer

aromaticity
general > O Obey Huckel's rule
CoHo ,

formula ② cyclic
③ planar
ARENE homologous
⑦ completely conjugated (double & single bonds in alternating position
series

grout BENZENE

functional - &
resonance structures

113 < >

aromatic ring & I

dim mechanism cannot lukis

IUPAC I substituent 2 substituents

① benzene ring kalan add I substituent only ①

Br
then no need state no . of position Br
+ 10
-ca
benzene 1
,
2-dibromobenzene or O-dibromobenzene

② prioritize siapa kat atas (jadual

3
NO
②
,

CH3 22

I
3

Br (parent)
methylbenzene >
Ca + 1 ,
3

toluene (nama famous 3-nitrobromobenzene or m-bromonitrobenzene

⑤ OH ③ -
OH
4

I
3

2
COUN

hydroxybenzene C at 1 . 4 (selang dual

4
. hydroxybenzoic acid or p-hydroxybenzoic acid
phenol

-
3 MH 2

NH2
I

aminobenzene IH
aniline

3-aminopheno or m-aminophenol
g g
Il ⑦ Il
C -
H C- CH3

benzaldehyde phenylethanone
acetophenone
⑥
COOH

benzoic acid
3 substituents

I 1
·

1 2 ,
3-triiodobenzene

②
I I
A 2

3 Br

2-bromo-3-chloroiodobenzene

4
③ OH NOz
3 5

COOH

3 -

hydroxy-5-nitrobenzoic acid

④
I OH

4 Z

H3C 3
Br

2-bromo-4-methylphenol
 #8 I reactions

① Halogenation < ③ Friedal Craft Alkylation

FeBVs AICIs -
CHCH3
+ CH3CHaCHaCl ,
+ BVz >
-

CH 3
Br

& Nitration
S
· ① Friedal Craft Acylation
O
j Il
NUc Il C -

CH3
COUC HNOs AlCl3
+ CH3) Cl
. -

>
>

COUC .
HcSO4

ur

Halogenation catalyst

CH3
UV CH2BL free radical substitution
+ BV >

COUN

KMnO4 ,
Ht

Bra
CH 3 > CH3
FeBVs
Br

Br 4f

&
CHcBr

Bu
① - Br
FeBrs
,
+ Brz

Step 1 :
Formation of EQ

Br -

Bri + FeBrs > BrO + FeBryO

Step 2 :
Formation of aremium ion

Br

+ BrQ >
H
①

+
Step 3 : Loss of H

Br - Br A
H
+ FeBryO 7
+ HBr + FeBrs
-Gr

g No -
CONC

COMc
.

.
HNOs

H2SO4
>
A

Step 1 :
Formation of E

↓
HO-NO2 +"H-SOsH < HO-NOL + HaSOpE , NOzO + H2O + HeSOpO
it
-

HNOs H2SO4

Step 2 : Formation of aremium ion

1. No, &

NOc
H

Step 3 : Loss of H +

⑦
HS040
M

+ >
+
H2SO4
NOc

Hr NO2
③
AICIs
+ CH3CH2CH2Cl ,
H

Step 1 :
Formation of EG
1 , 2-shift

CH3CHzCH2Cl + AlCIs ~ CH3CHaHa + AlCIpO- >

①
CHsCHCHa

Step 2 : Formation of aremium ion

+ CH3 CHCHs >

① ⑦

H CHCH3

CH3

Loss of H
+
Step 3 :

+ AlCIG > + HC + AICIs

⑦

H CHCH3
CHCHs
CH3
it

O O
Alls Il

A
Il

+
C -

C 3 C

Step 1 :
Formation of EG /K
C
O O
H N
"G
Il
Al(14G - &
C -

C + AlCIs > +
-

L C
-
i *
2
I I
-
Formation of aremium ion E c -
H
Step 2 :
-
H -
& -

C
O
①
i
Il
O
+ CQ >
Il H
C

k
-

Step 3 :
Loss of H+

① O
Il
C + AICIG >
+ HCl + AICIs
C
H
 <
Methylhalide CHSC)
IUPACS

① CH3CHCH2CHs
<
aryl halide
Bu

2- bromobutane Halo alk ane > 10R-X CHICHcCl

R -

X
Bu
② alphabet hujung kena CnHen +i X > 2
°
R -

X CH3CHCH3
2 dekat in parent
Cl CnHen- , X (cyclic Bu
I

>
3
°
R -

2-bromo-1-chlorocyclopentane Cl

CH3CCH3

③ CHs CH =
CCHcCHs utamakan CH3
kedudukan C= (
By

3-bromo-2-pentene

Synthesis of naloalkene
6
I
5 O hydwhalogenation
2 I Bu & nalogenation in inert solvent
3
③ halogenation in av

Br

3 , 4- dibrumocyclonexene

BV

CH3

2-bromotoluene

o-bromotoluene

⑥
CHICHCHs

1- (2-fluoropropyl) benzene
① Hydrolysis With NaOH (aq) <
③ Reaction with KCN

HeO alcohol
CH3CHCH3 + NaOH > CH3CHCH3 CH3CHCHs + KCN reflux
> CH3CHCH3

Bu OH By CN

Reaction
R -

X
R-MgX
② Reaction with NHS > ① Synthesis of Grignard reagent
ether
CH3CHCH3 NHs CHaCHCHs CH3CHCHs >CHaCHCHs
+
Mg
> +

Bu OH
Br Grignard
(excess) ↑
NH2 R
-

2- MgBr
reagent
3 T12] EBAA ,

synthesis 10R-OH
synthesis alkane
synthesis
,

v
O L
Il
HrO/H + Ho0/HT
CH3CHCHe H -C H CH3CHCH3 CH3 CHCHs CHaCHaCHs
Mg(OH) Br
+
-
> > +

NgBr CH2OH NgBr

H20/H +
CHSCHCH3 CH3CHCHs
i
+ CH3 -H > + Mg(OH) Br
CH3 CHOH
MgBr

Synthesis 30 R -
OH

CHsCHCHs +

CHsCCHa
HcOlHt
~
CHsCHCHs + CHsCHs
My Br
CH3CCH >

Synthesis of carboxylic acid # JULE BY like this

O

H20/Ht Il
CHsCHCH3 + O =
c =
0 > CHsCHCHs HO-C-CHCH3

NgBr Ho
- = 0
CHs
Example

Hydrogenation
Hydration

HsOt Pt
<
H20 + + Ha >

Et OH
HO

CH3
CH3 CH3
+ BVz

CHc(l
V

Br

Bu
CH3