Hydrocarbons

Preparation of Alkanes
Pt P Pd Roomtemp
R CH v12 or R CECH Ruth Ni Requires higher
T ppa Temp Pressure
syn addition

cnet.iiiie.ndki es.tn trans

HE cis
mess
In
Addition
Pairof
enantiomers

R Effie R H
in 14 Norm
RedP HI 3 RX l Alkene

r i r rear
Be carefulaboutacid a base
sensitive groups on the carbonyl

ragx abstracts acidic

R
La ÉÑgx R H
proton from the molecule

R R Hz Nazco Soda lime Decarboxylation

U_04
alkanes with even no of C
Th
ver
R R R R Filterent
2 Int r gives mix ofalkanes

EEgtntde
R WOH r coo.it

g
Ea.tt
R CH COOH KOH R cn cn
R de coom
Toga r.­EE

18 g.R
c c r

Kolbe's Electrolysis
Reactions
of Alkanes
F 42 Br Is
R
Reality
R H 3 2 1
1 Chy
4 Br Free radical Mechanism

542 4924 0154 413 Fast Reactive

43 412 41 121 1
4
1
43 CH Ut Br Chz up CH slow a selective
11 Bg

attack on 4 unique Be careful aboutgeneration of

p positions
chiral centre in product
Fluorination is tooviolent to be controlled
sodination is reversible we add ox agent like HNO or 4103
Chy I F 433theftagent 1103 541 312 3H20

Controlled oxidation Isomerisation Aromatisation

4 1 110005
2H14 0 201304

an on s auto no

24134 302 50M 2uecoon

7H 7 0H

NCERT
Preparation of Alkenes
Palladised charcoal partially
R CEC R
h t Y C deactivated with poisons like
Sulphur or quinoline

i
SET mechanism
m Ci BIRCH Reduction

medium
7 4 dehydration in acidic

ff
2 OH
elimination with Base
eg ale KOH t BuOK
β R I R Br R A
Rell Reality
Rhole 3 20 1

Pyn s
ah
Pk EI
E2
favored by weak Base
11 1
strong Base

were
i
RX 2nBVz
RY Br

Hofmann Elimination Giver less substituted alkene as majorproduct

Quaternary Amm salts

titi Major minor

Poor Lia like

very bulky base

f

No intermediate no rearrangement

Cope Elimination 3 amine oxide when heated give alkene

syn elimination intramolecular

RIFFE Rx x one
 Reactions
of Alkenes Px
Eaton in tn tmmore
substituted carbon

4 43 r
gu
R a a

YE r ui Br r ut clear AntiMarkomikov
product

s allylic or benzylic bromination

Peroxide effect is not observed with HCl or H1 as one the chain propagating
their vxn
of
steps is strongly endothermic for

ar i
us r Teir ef a
r cy ae a.ie i
ushmr
y.it 1er ugugi tmr qq.it­
BH3THF
Merceriniumioonymer
ndemer
rearrangements on­.no
541 9h No carbocation
Antiaddition water across C C
of
12 more steps

2 42 B on syn
addition
of 120
41,42 regulate anti markovnikovaddition
No rearrangements
Trialkylborane
 1
at u cT asa o 0
3

coo
syn
dihydroxylation pedalk
kM
c Reductiveozonolysis
use o
with Zn or DMS
Clue
413 4
be 10H

Is ox
Nu Na

it
1,2 Addition 1,4 Addition
Kinetic Product Product
Thermodynamic

favored at lowT falored at RT or HighTemp

R ue ue
911 R
45,9s

mr E
r ceut
jyfr F.lu ue

ÉÉ
R CEC R
191h r r

a cook R cook
Emporiii
minal alkynes
Enolysis

R CECH LET RECAP

Ppt
Preparation Reactions
of Benzene

II It EI
34 9
EYE

If E Reactivity 5 42 Bra 2

B
1 free radical mechanism

EI EI but
II k ornor Para
nitration
o
H Picricacid
Poor
yield

EI EY EL t.IE 45
Lotwer 1
BP HigherBP

II 1s Éf
03k
Picricacid GoodYield

EI conchason H2o

1
FC Reactions R AlUu
R U Ad

EI Tg II run r E

u.­gg
an map my map
Generating Electrophile

Drawbacks
ofF 1 Alkylation

Vinyl and aryl halidesdon't react

Rearrangements are common
Multiple alkylations
Poor
yield with EWG

eg NO2 ÑR3 COOH COOR COR CFz 5034 NHz

EINER
rice
Et Eg more

Phenol andaniline have highly activated benzene

ring for SEAR
monobromination

2112µs Tribromination

ICH NHz
TH

5
Acetanilide
I
El
Kajor
 us
E 4130010
If

E 642
18s Hexachlorobenzene

E 3H
I
Benzene Hexachloride
k BHC or Lindane

i Éf Ej
snafina
Evita

is Éi II II
HaNi
let 1 Ian Eino

É IT IT IT
 Nucleophilic Aromatic substitution

Addition Elimination In presence ofstrong EWG at 0 p positions

Elimination Addition No EWG are present needs strong base
Benzyne

sej.eei Eita
reactivity
Eto Ed _Egg

EI EI II
I It
Benzyne II t.LI
Nitrobenzene

FEE
Éi Éj y
mulliken x
man
Azobenzene

Ag
Blackppt Barker's test
ph NH NH Ph
MHz Electrolytic p g Hydrazobenzene

101 Redn
Langice
angidic
medium
be weaklyacidic
medium
Diazotisation

Ñ NCe0
Efi Eaten.sc
no

Ef.pt no Phy
amine R1
Ef N Nitroso N alkyl aniline
2 Yellow oil

ph if r
s
p nitroso N N dialkylaniline
3amine

i
Ar NH s _Ñ n Phenol
0 5C stable Benzine
s
Felled
IcuPowder ph x Sandmeyer RM
Ar NO 1 Gatterman Rxn
ph x
EYED PHI
4 ph F Schiemann RX

GS Ph CN
Coupling Rx of Avenediazonium salts Ar ÑN weak electrophile

Attacked
by phenoll arylamines to
give azo compounds

Ph Ñ Nx̅ H
EY 2 N N
E 2

Z OH NR Azo Compound

slightly Slightly
acidic

E N N
E OH
9H
Ph N N
orange solid phnice

E N N
E NHz
If
Yellow solid
Ph
pen n

I red dye jn methylorange

Phenylazo p naphthol

an
FINE
00
1 p MethylRed
Haloalkanes Alcohol Ethers

is 2 R OH HCl IR R U
Betty HI HBr tell
3 R OH HQ R G 3 20710

2nA is added b'coz C is weaker Nuc than Br P I

3 R OH 3 R Br POH
2s

R OH 2s RU Poll tell

82s R U so g HU Ig

Isocyffines R U so g HU 19

R Nat R I Nax Finklestein RM SN2

Cl Br

RX R F Agx 492 2 Swarts Reaction

p
R 612 NF
R cg NH s
unstable j.fr azole
 Sn2 Reaction

1
A
Ng
Nu shEsion
Na
Gigo
TransitionState

strong nus req eg CN SH I etc

10 2 3
Reactivity R
G
at x chyx allyl benzyl

Singlestepmechanism no intermediates no rearrangement

dextro laevo Not necessarily

stereospecific in
Favored
by polar aprotic
solvents
eg DMSO DMS DMF acetone DMA etc

SNI E1 Major Minor

Retention Inversion
2s

define
8 Alkene
weak nuci base required eg H2O ROH etc

Reactivity α stability of carbocation

Snl El go hand in beriand

E2 Reaction
Singlestepconcerted mechanism
Base I favored strong Base
µ by

wifi.im e
creativity 3072071

H LG should be anti coplanar

stereospecific
Baseused Alc KOH t BuOK
NaOEt NANH
 abuson
us a
Usag emo
process
T
Chat 420 co 3H
sm 41304 Indutrial synthesis of
Methanol

pE n rallies r Hir

R OH M room'gx R H

EYE.fi E ir
iE­2 igr
r

ce OR NH2 Ocollt3

E le
R
La RUH

RER pÉr
R COOH 9 R CHOH

LY NO R

R Éfor s R CHOH R 0H

R É I s R Cho R CHOH

R R ir aF chs
41,13 Y.gs Ryuts
unstable

R E OR a CHO R ER me corresponding Alcohol

Hydrolysis of Ester

R If r NaOH R Onat Rote saponification of Ester

R'OH RCOOH R E OR
Reality Chgote Clean 4154504 1 OH

HOOH Chzcook CHz2CH COOH

UK
on the use 2 or 3 alcohol is avoided asthey
now of
Tg give alkene

RFI R o r Williamson Ethersynthesis

keep the RX compact 1 preferably

N Alkoxymercuration Demercu nition

R Ago x R R O R 2Agx

EI dn ED E2 elimination

100 1 2 20 Ht kMnoulHt Cro

1.1291 f R CHO PCC or PDC

r R Ain't carbonylcompounds

3 alcohol s Allane
3 alcohol NO RX

m
ACHO
Tydogentions
ANOH
Mmo2 is specific for oxidising allylic or
Ph OH s ph up benzylic alcohol
Pinacol
i i t.to F It It
Pinacolone

my 44
NANO

IT this
413 0 UH Us cease Utter

ago Eu us arson I Irs

die

attack on more substitutedcarbon

T s
a
on protonated epoxiii.de

In Is It attack on lesshindered
carbon in basic medium
Phenol reacts with Naoh but not with Nancy
Crivel violet coloration with neutral

11
Felly
Also known as carbolic acid

1 Labpreparation

Ence
E me
E 10 E on

2 Industrial Preparation

EI 1 If
Dow Process

EFinat.gg jonatIsE1
3 From Camene hydroperoxide Most
of the worldwide production of phenol is based
on this method
on

E a
Eft It
Cumene hydroperoxide

011120 Ph
4581 Ph
use rn
IF
Phenol Acetone

4 Cleavage ethers
of alkylaryl
Ph O R Is ph jR s Ph OH R I
Kolbe's Reaction

i Eye D EI said
Claisen Rearrangement Heating allyl phenyl ether to 200C causes an
intramolecular rearrangement to generate o allylphenol

Eto t.fi fine

IF Effe H
It 3
If
Fries Rearrangement
1 01

II
Reimer Tiemann Rx
II
Ei m
EI Itdo É
EI Ejo f e
m
Major
EI.ca
Cook
Minor
Aldehydes Ketones CarboxylicAcids

price R H Rosenmund Red

R CEN R CH NH s R CH 0 NHz

r E or r
uo

TEFow4
lte­.EE

gE1
g 1011040442 15 140
EI 54 1
EI EI Gatterman Koch Rxn

R ENRFR cq.MY sr E H­

2RMgx ldU Raid 1 R R call

RNOH Rna 0

RYOH RYO
Aldehydes and ketones undergo nucleophilic addition

R
É ff Rita Nuc Addition

pffes 2
p
OH Cl OR NHz
no Nuc substitution
 Aldehyde is more reactivethan ketone

Reactivity rice R r R le RIR

R or RINH ROO

no
m
iii.in
are Iii
IR Butan 2 of

i ni
rm
21 in addition

re
Recep 1,4 Addition

IT Eination I
nu BasT
abstracts
the α H
To
t.tt aon
E
 k cyanohydrin

Llets H
Hydrate favouredby ENG

IF NR Imine

WE JNR
Enamine

Lex Hemiacetal
ik
Acetal

70 7Nt
H2N Z

H Ammonia NH Imine

R Amine NR substituted Imine

Schitt's Base
OH Hydroxylamine N 0H Oxime

Nity Hydrazine N NH Hydrazone

Nfp Phenylhydrazine N Nlp Phenylhydrazone

NH_É N BiliYehydrazine N NH no 2,4 dinitrophenyl

hydrazone

NH E NH Semicarbazide N NH CONH Semicarbazone

 more
Wiou
at E 9 Evous

s
out ion
Acetal as protecting group
Not attackedby basic groups
hydrolysed back to 7 0 in acidicmedium

Preparation R COOH
of
RUTOH R WO
RMgx 102
Carboxylic
got
a c or r Ea r I NH Acid
R CEN r Éo I r
EIR
Reactions
of R COOH

R E a Polls HU

R E OH 3 R a HPO

ne
R E a 5029 He
 hydrolysis a COOH

R R Coor

R E 4 a on

Good Fi

may
R EH Rosenmund Reduction

hr rÉ r Cd4

R CHOH

1H R NH Hoffmann Bromamide
Degradation
E
Ho
R
NH R chintz

R CEN

Hell VolhardZelinsky RM HVZ

L a halogenationofaliphaticacids in presenceof P

CH COOH COOH
Chy cuz COOH
Hook
043 142 2004 Reactive
as ago
ChscBy cook selective
n
Arndt Eistert Reaction

R COOH
R cha cook
H2O Ag Tydrolysis
R a c o
RIT 44 Ketene

I F Nz
HQ
On passing acid vapours over MMO at 300C we getketone

2 R COOH
e R E R 02 H2O

CHOH co s 4130011 CHICHOH

4 4
aera

on

WOH
Ñ 0
78 9 1
d

YET cooks Methylsalicylate

oil of wintergreen

cooph
1s phenylsalicylate
Salol mildantiseptic

To detect the presence of aldehydes ketones

2,4 DNP Test orange yellowcrystals

sodium Bisulphite test
 Aldehyde Ketone
orcign pincco.us
ff.it
Tollen's Test
I ii
Red 420
o
Green Blue colour
can
X

Sodium nitropresside test Red colouration