HYDROCARBON-ALKANE

6
Clenmenson Reduction)
CH,-CH, H/Pt, Ni, Pd PREPARATION Zn-HgHCI or
Raney Ni/250°C 200°C NH,NH,/EtO Na' CH,C-R
(wolf kishner reduction)
Sabatie Sanderens Reduction

NaOH+CaO/A
Br CH, CH,
Zn+Dil.HCI
(Sodalimne] -H,c-&-OH
(Decarboxylation)

BrR (1° & 2°)

LiAIH, Kolbes electrolys15H,C Ç-ONa
Et,o CH,
CH,-CH,
NaBH, R-CH,-CH, HI/Red P.
Br R(2° & 3°)
CH,-CH,-CHJ -H--CH,

R"-X HI/Red P.
R,Zn.
(Frankland reaction) H,C -CH,

2Na/Dry ether HI/Red P.

2CH,-Br
Wurtz reaction, HO- -CH
(Not go0d for unsymmetrical Alkane)

R,CuLi R-X(R' 1°, 29 H,0

(Corey house synthesis) .Al,C,
(Good for both syrn. unsyrn. alkane) 4 Al(OH),
 (Good for both sym. unsym. alkane)

CH,-CH,-X X, (FRSR) REACTIONS SO,CI, (FRSR)

F,>Cl,>Br,>l]+ by
hv CH,CH CI
CH,CH.- a, (FRSR)
Cl, Pyrolysis (FRSR)
hv
773K
CH,-CH,+CH,
Br, (FRSR) 573/0,
CH, CH, Br CH, Cu tube +CH, -CH-OH
hv CH,-CH,
R-CH,-CH,
CH,CH,
L/hv (FRSR) CH,-CH,-CH, Mo,0/0, CH, CHO
HIO/HNO,
R-NO,
HNO, (FRSR)
H,SO,/400°C
CH,COO), Mn/O CH-cOOH
H,SO, + SO, Incomplete
RSO,H Combustion C(s)+2H,O ()
(FRSR)

Aromatization : *********
Oxidation at 3° H
Cr,0,/Al,O, CO,+H,O
773K (FRSR) CH,
Isomerization H,C-C-H KMnO4 H,C-C-OH
Cr,0,/Al,O, CH,
773K, 10-20 atm
-CH, Anhy. ACl, CH,
HCI

Reactivity of alkane towards free radical halogenation is Knocking tendency is in the order
cstability of free radical Olefin > cycloalkane > aromatic
CH,-CH,>CH,=CH-CH,CH),CH "Boiling point decrease with increase in number ot sieCHu
>CH,-CH-CH,>CH-CH,>CH,
Reactivity of halogen towards free radical substitution CH,-CH,CH-CH,-CH,>CH, ÇH-CH,-CH,> CH CH
F, > Cl, > Br, > l, CH, neo

Knocking tendency of petroleum as fuel decrease with normal 0SO

increase in side chain. Straight chain > Branched chain

 HYDROCARBON -ALKENE
HSO,/A or
PREPARATION H,/Pd-CaCO, Partial
reduction
RC CH
H,PO,/A or Al,0JA Lindlar Catalyst H,C-cC-CH,
(cis Alkene)

X Alc. KOH Na/Liq. NH,

R-CH,CH, HX Birch Reduction
KCL BpSaytzet Rue (trans Alkene) H,C-C=C-CH
CH,-CH,
Zn dust H,-CH=CH,
R-CHCH R-CH=CH,
R-CH-CH-R

R-CH CH
Zn dust
For Higher Alkene
Pyrolysis
R-o-CH+a
Kolbe electrolysis Elimination Reaction
A
(CHCH),NOH
E' & E
H H
HCCH-CH-CH H,C-HÇH-CH, HCCH, CH-CH
Y Less substituted
more substituted
alkene is major product alkene is major product
Hoffman Rule
Saytzeff Rule
 CH-ÇH-ÇH,
Cold Conc. REACTIONS H-0-C
H,SO, (EAR) (EAR)
+HC-ÇH-CHCI
HÌO,SÎ H OH
X H-X
Os0,/NaHSO. HÌ OH
H,C-H-CH,
(Markownlkovs rule)
HBr, HCI, HI (EAR) or dl. Alk. KMnO, H,C-H-H,
(Bayer's Reagent) (Syn additton)
O-H H+H,0 OH
H,C-CH--CH, V20,/Ag/A H+/H,O19
Intermedlate :carbocaton
(hus rearangemernt occur's)
(EAR) orH,CCO,H H,C-CH-CH H,C-ÇH-H,
Epoxldation 18OH (Anti additton)

0-H Hg(0Ac b CH-CH

CH H,0/Zn
H,c--H+H-H
H,C-CHCH, NaBH, (EAR)
(No rearrangement )
(EAR) H,C-çH CH, H,os H.c--OH+CO.
H OH HO2 B,H/THF LIAIH, H,C-CH,OH + H,C-OH
H,C-CH-CH, NaOH (CH-ÇH-CH,),B4
H (EAR)
H* or ÔH
CH,COOH+CO,
Br KMnO,A
Br
H,C-H-CH, CCI, Br,
CO,+H,O
Br -H,C-CH-CH, (EAR) combustion
H
CI/500°C Çl
0-H Br
+H, CH=CH,
Ani addition of Br,
H,C-H-ÇH,Br cis ’ d,J dibrornide
trans meso dbromide
(FRSR)
Markownikoff Rule (M.R)
Br
NBS
NaCl (FRSR) H, CH=CH,
Hc-CH-ÇH, Br
Br
H,C-H-CH-1 Bt-B
lEAR)
High temp. /Pressure
Catalysts tCH-CH,
H,
HC-H-ÇH, Br
KI
H,C-CH-CH,-N=O+
-N=0 EAR) HBr+R,0,
(Anti-Markonikov's rule)
(FRAR) CH,CH,CH,Br

HBr HBr BrAnt-Markonikov's rule)

(Markonikovsule)Br Peroxide
> RCH,CH,> CH,-CH,
Rate of EAR:R,C=CR, > R,C-CHR > RCH=CHR

(Reverse of stability)
Order of reactivityof olefins for hydrogenation CH,-CH, > R-CH=CH,
Order of reactivityof alkene towards hydration CH-Ç ==CH,> CH,-CH = CH, > CH, = CH,
3
 HYDROCARBON - ALKYNE

Preparation H,0
Br Br () Alc. KOH -CaC2
CH,CH, (i) NaNH,
Elimination
Br
(i) Alc. KOH Electric arc/1200°COC+H.
H,C-CH Berthelots process
Br
() NaNH,
Br Br H-CEC-H
Kolbe's CH-COOK
Zn dust
Br-C-C-Br +R-CEC-H electrolysis CH-COOK
H H
R-CEC-R
Alc. KOH (i) NaNH,or Na -H-C=C-R
H,C=CH-C NaNH2 (0) R-X
&- 8+
6Ag (i) CH,Mgl
2CHL (1) R-X
H-CEC-R
 X H H-X
Reaction Baeyer's reagent R-C-C
(Test of unsaturation)
R- --H-R-Ç= -H (EAR)
X
Markownikoff rule Oxidatio
O,
Hg /d.H,SO, R-C-OH
R--CHR-CH-CH,+ (EAR) H,0
OH

KMnO,/H
OH B,H/THF
A
R-C-OH
R-CH,-C-HR-CH= -H H,O,/ OH
(EAR)
Br Br Combustion
2Br,/CCl, + CO,+H,0
R-C-ÇH H-CEC-H
Br Br
(Test of unsaturatiop
(EAR) R-CEC-H 3n-10.
2

OH R-CEC-R, Na/Liq. NH,

HOCI
HOCI R-CECNa
Hc--CHa, -H,C-=CH-C (EAR) (for terminal Alkyne)

H,/Ni NaNH, R-C=CNS

R-CH, CH, Pd/Pt
(Reduction),
R-c=CAg
(cis) R-CH=CH-R H,/Pd Amm. AgNO (white ppt)
CaCO, Amm. CuCI R-c=CC
(Partial Reduction) H-CEC-H E
(for terminal Alkyne) (Red ppi.)
CuC, NH,C
Na/Liq. NH, H,C-CHCEC-H Þ-
RMgBr
+
(trans) R-CH=CH-R
Birch reduction R-c=CMgBr+RH
(Partial Reduction) (for teminal Alkyne)

C)
Chloroprene
 HYDROCARBON-BENZENE
PREPARATION
MgBr
NaCao CH
HO
ecatooXaON CH,
Red hot Cu tube
NCI
PoRCH,OH: or H.PO.
BENZENE

******w
AO, (500)

REACTONC
Electrophilic Substitution Reactions
E OsPh
HC
Ph--Cl+AICI,

Arenium jon
CH>C,D>C|cHCD=CT
INitrationl
NO, NOS H,/Pt
HNO, + H,SO, Reduction
(Concentration)
(Suphonation)

SO. Na / liq. NH,

or-HSO,SO, Birch Reduction

craft
Friedal
Aliahen
CH, C CI
CH,Cl+AICI, CI,/U.V.
C
C
(BHC)
craft
Friedal CH-&oCH.
+AlCI,
-CH (CH--o Baeyer's
reagent No reactions
Cl+AlCI,
c
Cartoxvation Benzene
ÇOOH CO, ÇHO
AlCl, Zn/H,0
3CHO
Ozonolysis
Sythesis
Mdehyde
Getterman
Kodh

O:c H CO + ICI O/N,,

450°C
AICI, HC
eman
aloehyde
OH
CHO HCN+HCI + ZnCI O,/N,0,
250°C

6Cl,+ Anhyd.AlCI,
oCombustion)
6CO,+ 31,0
CI CI