ALKANES

Reagent Functions
1. Hydrogenation [H2/Ni, Pt, Pd] • π Bond dks H, H ls rksM+ks
=
CH 2 CH 2 →
H2
Ni
CH 3 − CH 3

2. From Alkyl halide [Zn + dil. HCl]

• X gVkvks, H yxkvks
CH 3 − Cl →
Zn
CH 4
3. Wurtz Reaction [Na + dry ether] dil HCl

• R – X bond dks F.R. rksM+ks 2R° dks tksMk+ s

Br

Na + dry ether

4. Decarboxylation [NaOH + CaO sodalime] • COOH gVkvks H yxkvks COONa gVkvks H yxkvks

CH 3 − COOH 
NaOH
→ CH 4
5. Kolbe's Electrolysis(e−) CaO
• •
(Same as wurtz Reaction) • C––COOH C+ C → C − C even number
• Cl
6. Frankland Reaction [Zn, dry ether] Zn •
• dry ether •
•

7. Corey-house synthesis- • X gVkvks Gilman dk R yxkvks

• Gilman's Reagent (R–Cu + R Li ) or R2CuLi
 +
CH 3 − Cl →
Et CuLi
CH 3 − Et

8. Halogenation [X2 /hv] • 'H' gVkvks 'X' yxkvks

R − H →
X2
hν
R−X
Cr2O3
9. Aromatisation [ Cr2 O3 / V2 O5 / Mo 2 O3 ] 773 K, •
V2O6, Mo2O3
10-20 atm Anhyd.
•
AlCl3
10. Isomerisation [Anhydrous AlCl3]
∆
• CH 4 + 2O 2  → CO 2 + 2H 2 O [∆H = –ve]
11. Combustion
• 2CH 4 + O 2 → 2CH 3OH
Cu /523 K

CH 4 + O 2 →
Mo 2 O3
HCHO + H 2 O
12. Controlled oxidation
2CH 3CH 3 + 3O 2 
(CH3COO)2
Mn
→ 2CH 3COOH + 2H 2 O
13. Reaction with steam • CH 4 + H 2 O 
Ni
∆
→ CO + H 2

14. Pyrolysis C6H12+H2

773K
• C6H14 C4H8 + C2H6

C3H6+ C2H4+CH4

[1]
 ALKENES
Reagent Functions
1. Hydrogenation of Alkynes H H R R'
H2+
[H2 + Pd/C, H2, + Pd/BaSO4] Lindlar's Catalyst R – C = C– R' C =C Cis
Pd/C
Or H2/Ni2B • H H

H H R H
Na+
2. Birch reduction [Na + Liq.NH3/Li + Liq.NH3] R – C≡ C – R' C =C Trans
liq.NH3 R'
For Non-terminal alkynes H
Zn =
3. Dehalogenation [Zn/CH3COOH] • C C C C
CH3COOH
X Zn X
4. Dehydration of alcohols (E1) +
H Removal +
[H+/∆ (443 K), Conc.H2SO4, H3PO4] R–OH protonation R–O–H of H O
2
R + H2O
H Rearran. if poss.
• Alkene
H
5. Dehydrohalogenation β α
Alc. KOH
[Alc.KOH/Alc.NaOH/NaNH2] • –C–C– –C=C (Anti-elimination)
[RO−/ROH] X
X
X2
6. Halogenation • R–CH=CH2 CCl4
R–CH–CH2
• X2 in non-polar solvent (CCl4, CS2) X
• Interhalogen (BrCl, ICl, IBr) Br
• X2 In polar solvent + – Br2
R–CH=CH2 R–CH–CH2
(X2 + H2O → HOX) H2 O
(X ≠ F) OH
(Bromohydrin)
– + H
+ –
X
7. Addition of HX [HCl, HBr, HI] • R–CH=CH2 R–CH–CH3 R–CH–CH3
(rearran. if poss.) X
+
Markovnikov's Rule [HX] HX
–

• CH3–CH=CH2 CH3–CH–CH3
–ve part of reagent → Less hydrogen atom
X
+
+ + + – + ⊕ H 2O/–H
8. Addition of water [dil.H2SO4/H , H2O/H3O ] R–CH=CH2
H
R–CH–CH3 R–CH–CH3

• OH
+ – + +
H + H 2O/–H
R–CH=CH2 R–CH–CH3 R–CH–CH3
OH
BH3
• 3RCH=CH2 B(CH2CH2R)3
9. Hydroboration oxidaion (HBO) + –
H OH
 B2 H 6 / THF , H 2 O 2 / OH  RCH
(RCH2CH2CH
R–CH=CH2)3B
22 R–CH2–CH2–OH +H3BO3
Antimark.

(Anti-Markovnikov addition of H2O)

+ –
H OH
10. Oxymercuration Demercuration (OMDM) • R–CH=CH2 R–CH–CH3
N.A.R.
[ Hg(OAc)2 / H 2 O, NaBH 4 ] OH
δ+ δ–
HBr
11. Addition of HBr/ Peroxide R–CH=CH2 R–CH2–CH2–Br
peroxide [2]
(Free radical addition) Anti-Markovnikov addition of HBr •
 Reagent Functions
+
12. Addition of sulphuric acid • H
R–CH = CH2 R–CH–CH3 [Rearran. if poss.]
[H2SO4, H+/HSO4–] –
OSO3H
R–CH–CH3
|
OSO3H
13 Oxidation [dil. Alk. KMnO4]
dil. /Alk addition
syn
Baeyer's reagent C=C C– C
KMnO 4
OH OH
14. Ozonolysis
vicinal dial
(1) Reductive ozonolysis •
O3+CCl4 O3 +CCl4 O3 O3 O
� , , Zn,H 0 , Zn + HCl � O3
Z𝑛𝑛 Me2 S 2
• C=C C C Ozonide
(2) Oxidative ozonolysis
O3+CCl4 O3 +CCl4 O O
� or � ZnO
H2 𝑂𝑂 H2 O2
* Strong oxidizing reagents C C
Hot KMnO4 /K 2 Cr2 O7
� �
Acidic KMnO4 /K 2 Cr2 O7 O O
(aldehyde, ketone)

R R R R
C=C C=O+O=C
H R R
• HO
(Carboxylic acids) (ketones)

CH3 OH
• H CH3
C=C C=O+O=C CO2
H H OH OH
Acetic acid Carbonic acid
15. Allylic substitution t − buOCl
• Ph − CH3 
• → Ph − CH 2 Cl
Chlorination C=C–C Cl
Br
Bromination C

Cl2/hv Br2/hv • NBS

Br
t-buOCl t-buOCl
Cl2/500°C Br2/500°C
NCS NBS

[3]
 ALKYNES
Reagent Functions
1. From Carbides- H3O +
• CaC2 → Ca(OH) 2 + CH ≡ CH
∆ C H 2O
CaCO3  → CaO + CO 2 → Acetylene
H O
CaC2 
2 → CH ≡ CH
H H
| |
2. From Dehydrohalogenation- Alc. KOH
• – C– C – –C≡C –
[Alc.KOH/alc.KOH, NaNH2/NaNH2] | | NaNH2
X X
Br Br
3. Test for unsaturation- | |
[Br2/CCl4] Br2
• R – C ≡ C – R' R – C – C – R’
CCl4 | |
Br Br
(Colorless)
4. Kucherov Reaction
+ – 2+
Hg /H2O
[Addition of H2O hydration] • R – C ≡ CH R – C = CH2 R – C – CH3
H2 SO4
dil H 2SO 4 , +  HgSO4
| ||
  OH O
dil HgSO 4 or  tautomerism
 2+  X
 Hg / H 2 O  |
2HX
5. Hydrohalogenation (RX) • R–C≡CH R–C– CH3 Gemi nal dihalide
|
X
6. Coupling reaction- Cu2Cl2
2CH≡CH CH=CH2 CH2 = CH – C ≡ CH
a) Linear [Cu2Cl2/NH4Cl] NH4Cl |
Vinyl ac etylene
b) Cyclic [Red hot tube] • Cl≡CH
C

c) Oxidative [O2] R.H.T.

• 3CH≡CH
or Fe tube
O
• 2R − C ≡ C − CH →
2 R −C≡C−C≡C−R
7. Silver nitrate test [Tollen's Reagent] • AgNO
R − C ≡ C − H 
3
→ R − C ≡ CAg (white ppt)
NH 4OH
[AgNO3 + NH4OH] Ammoniacal silver nitrate
Cu Cl
8. Cuprous chloride test • R − C ≡ C − H 
2 2 → R − C ≡ CCu (Red ppt)
NH OH 4
[Cu2Cl2 + NH4OH] Ammonical cuprous chloride OH OH O O
dil./Al K | | || ||
9. Baeyer's reagent [dil. alk. KMnO4] • R–C≡C–H R – C – C –H R – C – C –H
KMnO4 | | [O]
OH OH
O O
|| ||
R – C – C – OH

10. Ozonolysis- OO
O3 + CCl4
1) Reductive ozonolysis [O3 + CCl4/Zn] • R–C≡C–R’ R–C–C–R’
Zn
2) Oxidative ozonolysis [O3 + CCl4/H2O] OO O
O3 + CCl4 || || ||
• R–C≡C–H R–C–C–OH R–C–OH + H2CO3
H2 O
11. Lower to higher alkynes
H2O + CO2
[Na/∆, NaNH2]
Na/ ∆
• R − C ≡ C − H 
or NaNH
→ R − C ≡ C − Na + or
2

R '− X

1° /2°
→R − C ≡ C − R '
[4]
 Reagent Functions
+ Cl– –AsCl2 β
CH CH –Cl β-Chlorovinyl dichloro
12. Lewisite Formation ||| ||
– arsine
aren es (Lewisite)
[AsCl3 Anhydrous AlCl3] CH CH–AsCl2
• α
13. Internal to Terminal NaNH2
• CH3–C≡C–CH3 CH3–CH2 −C≡CH
Na + liq NH3

14. Terminal to Internal

• CH3 − CH 2 − C ≡ CH →
Alc
KOH

CH3 − C ≡ C − CH3

[5]