Hydrocarbon: Reagent - Function: Notes

Major Test-02 (05-03-2023)_NEET Dropper Hindi_Phase-04
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
3. Wurtz Reaction [Na + dry ether]
CH 3 − Cl →
Zn
dil HCl
CH 4
4. Decarboxylation [NaOH + CaO sodalime] • R – X bond dks F.R. rksM+ks 2R° dks tksM+ks
Br
Na + dry ether
5. Kolbe's Electrolysis/(e−)
(Same as wurtz Reaction) • COOH gVkvks H yxkvks COONa gVkvks H yxkvks
CH 3 − COOH 
NaOH
CaO
→ CH 4
6. Frankland Reaction [Zn, dry ether]
• •
• C––COOH C+ C → C − C even number
7. Corey-house synthesis- • Cl
• Gilman's Reagent (R–Cu + RLi+) Zn •
R2CuLi • dry ether •
•
8. Halogenation [X2 /hv] • X gVkvks Gilman dk R yxkvks

CH 3 − Cl →
Et CuLi
CH 3 − Et
9. Aromatisation [ Cr2 O3 / V2 O6 / Mo 2 O3 ] 773 K,
10-20 atm • 'H' gVkvks 'X' yxkvks
R − H →
X2
hν
R−X
10. Isomerisation [Anhydrous AlCl3]
Cr2O3
•
11. Combustion V2O6, Mo2O3
Anhyd.
12. Controlled oxidation •
AlCl3
13. Reaction with steam ∆

• CH 4 + 2O 2  → CO 2 + 2H 2 O [∆H = –ve]
• 2CH 4 + O 2 
Cu /523 K
→ 2CH 3OH
14. Pyrolysis
CH 4 + O 2 →
Mo 2 O3
HCHO + H 2 O
2CH 3CH 3 + 3O 2 
(CH3COO)2
Mn
→ 2CH 3COOH + 2H 2 O
• CH 4 + H 2 O 
Ni
∆
→ CO + H 2
C6H12+H2
773K
• C6H14 C4H8 + C2H6
C3H6+ C2H4+CH4
Aryabhatta Tower, A-51(A), Road No. 3, Behind City Mall, Indraprastha Industrial Area, Kota, Rajasthan 324005, Mo. No. +917019243492 [1]
Reagent Functions
1. Hydrogenation of Alkynes H H R R'
H2+
[H2 + Pd/C, H2, + Pd/BaSO4] Lindlar's Catalyst R – CºC – R' C =C Cis
Pd/C H
↑ • H
Or H2/Ni2B H H R H
Na+
R – C≡ C – R' C =C Trans
liq.NH3 R'
2. Birch reduction [Na + Liq.NH3/Li + Liq.NH3]
•
H
For Non-terminal alkeynes
Zn =
• C C C C
3. Dehalogenation [Zn/CH3COOH] CH3COOH
X Zn X
4. Dehydration of alcohols (E1)
+
H Removal
[H+/∆ (443 K), Conc.H2SO4, H3PO4] R–OH R–O–
+
R + H2O
• protonation of H2 O
H Rearran. if poss.
Alkene
5. Dehydrohalogenation
H
[Alc.KOH/Alc.NaOH/NaNH2] β α Alc. KOH
[RO−/ROH] • –C–C– –C=C
X
6. Halogenation X
X2
• In non-polar solvent (CCl4, CS2) • R–CH=CH2 R–CH–CH2
CCl4
• X2 Interhalogen (BrCl, ICl, IBr) X
• X2 In polar solvent Br
(X2 + H2O → HOX) + – Br
• R–CH=CH2 H O R–CH–CH2
(X ≠ F) 2
OH
(Bromohydrin)
7. Addition of HX [HCl, HBr, HI] – –
+ H
+
X
• R–CH=CH2 R–CH–CH3 R–CH–CH3
8. Markovnikov's Rule [HX] (rearran. if poss.) X
–ve → Less hydrogen atom + –
HX
• CH3–CH=CH2 CH3–CH–CH3
+ +
9. Addition of water [dil.H2SO4/H , H2O/H3O ] X
+
+ – +
H ⊕ H 2O/–H
10. Hydroboration oxidaion (HBO) R–CH=CH2 R–CH–CH3 R–CH–CH3
 B2 H 6 / THF , H 2 O 2 / OH  • OH
+ – + +
H H2O/–H
R–CH=CH2 R–CH–CH3 R–CH–CH3
12. Oxymercuration Demercuration (OMDM)
OH
[ Hg(OAc)2 / H 2 O, NaBH 4 ] BH3
• 3RCH=CH2 B(CH2CH2R)3
+ –
13. Addition of HBr/ Peroxide H OH
RCH2CH22
R–CH=CH R–CH2–CH2–OH +H3BO3
Antimark.
•
(Anti-Markovnikov addition of H2O)
+ –
H OH
• R–CH=CH2 R–CH–CH3
N.A.R.
OH
δ+ δ–
HBr
R–CH=CH2 R–CH2–CH2–Br
peroxide
•
(Free radical addition) Anti-Markovnikov addition of HB6
Aryabhatta Tower, A-51(A), Road No. 3, Behind City Mall, Indraprastha Industrial Area, Kota, Rajasthan 324005, Mo. No. +917019243492 [
Reagent Functions
+
14. Addition of sulphuric acid • H
R–CH = CH2 R–CH–CH3 [Rearran. if poss.]
[H2SO4, H+/HSO4–] –
OSO3H
R–CH–CH3
15 Oxidation [dil. Alk. KMnO4]
|
Baeyer's reagent
OSO3H
dil. /Alk addition
syn
16. Ozonolysis [O3, H2O, go] C=C C– C
KMnO 4
(1) Reductive ozonolysis
O3+CCl4 O3 +CCl4 O O OH OH
�
Z𝑛𝑛
, Me2 S
, Zn,H3 0 , Zn +3HCl �
2 vicinal dial
•
(2) Oxidative ozonolysis O
O3+CCl4 O3 +CCl4 O3
� or � • C=C C C Ozonide
H2 𝑂𝑂 H2 O2
* Strong oxidizing & rgenty O O
Hot KMnO4 /K2 Cr2 O7 ZnO
� �
Acidic KMnO4 /K2 Cr2 O7
C C
17. Allylic substitution O O

Chlorination C=C–C (aldehyde, lcetore)
Bromination C R R R R
C=C C=O+O=C
Cl2/hv Br2/hv H R R
t-buOCl t-buOCl • HO
Cl2/500°C Br2/500°C (ketones) (Carboxylic acids)
NCS NBS OH
• CH3 H CH3
C=C C=O+O=C CO2
H H OH OH
Acetic acid Carbonic acid
t − buOCl
• Ph − CH3 
• → Ph − CH 2 Cl
Cl
Br
• NBS
Br
ALKYNES
1. From Carbides-
∆ C
CaCO3  → CaO + CO 2 → ALKYNES
H 2O
CaC2 
→ CH ≡ CH H3O +
• CaC2 → Ca(OH) 2 + CH ≡ CH
H 2O Acetylene
2. From Dehydrohalogenation- H H
[Alc.KOH/alc.KOH, NaNH2/NaNH2] | |
Alc. KOH
• – C– C – –C≡C –
3. Test for unsaturation- | | NaNH2
[Br2/CCl4] X X
Br Br
4. Kucherov Reaction | |
Br2
[Addition of H2O hydration] • R – C ≡ C – R' R – C – C – R’
CCl4
dil H 2SO 4 , +  | |
  Br Br
dil HgSO 4 or  (Colorless)
 2+  + –
 Hg / H 2 O 
2+
Hg /H2O
• R – C ≡ CH R – C = CH2 R – C – CH3
H2 SO4 | ||
HgSO4 OH O
tautomerism
• Terminal allane Methyllcfrne
Reagent Functions
5. Hydrohalogenation (RX) X
2HX |
• R–C≡CH R–C– CH3 Gemi nal dihalide
|
6. Coupling reaction- X
a) Linear [Cu2Cl2/NH4Cl] Cu2Cl2
• 2CH≡CH CH=CH2 CH2 = CH – C ≡ CH
b) Cyclic [Red hot tube] NH4Cl |
Vinyl acetylene
c) Oxidative [O2] Cl≡CH
R.H.T.
• 3CH≡CH
or Fe tube
7. Silver nitrate test [Tollen's Reagent]
[AgNO3 + NH4OH]
O
Ammoniacal silver nitrate • 2R − C ≡ C − CH →
2 R −C≡C−C≡C−R
• R − C ≡ C − H  3 AgNO
→ R − C ≡ CAg (white ppt)
NH OH 4
8. Cuprous chloride test
Cv ,Cl
[Cu2Cl2 + NH4OH] • R − C ≡ C − H 
2 2 → R − C ≡ CCu (Red ppt)
NH OH 4
Ammonical cuprous chloride OH OH O O
dil./Al K | | || ||
• R–C≡C–H R – C – C –H R – C – C –H
KMnO4 | |
9. Baeyer's reagent [dil. alk. KMnO4] [O]
OH OH
O O
|| ||
10. Ozonolysis- R – C – C – OH
OO
1) Reductive ozonolysis [O3 + CCl4/Zn]
O3 + CCl4
2) Oxidative ozonolysis [O3 + CCl4/H2O] • R–C≡C–R’ R–C–C–R’
Zn
OO O
O3 + CCl4 || || ||
11. Lower to higher alkynes • R–C≡C–H R–C–C–OH R–C–OH + H2CO3
H2 O
[Na/∆, NaNH2]
H2O + CO2
Na/ ∆
12. Lewisite Formation • → R − C ≡ C − Na + or
R − C ≡ C − H 
NaNH 2
[AsCl3 Anhydrous AlCl3] R '− X

1° /2°
→R − C ≡ C − R '
14. Internal to Terminal + Cl– –AsCl2 β

CH CH –Cl β-Chlorovinyl dichloro
||| || arsine
aren es (Lewisite)
–
CH CH–AsCl2
15. Terminal to Internal • α
Alc NaNH2
CH3 − CH 2 − C ≡ CH 
KOH
→ • CH3–C≡C–CH3 CH3–CH2 −C≡CH
Na + liq NH3
• CH3 − C ≡ C − CH3
Reagent Functions
Method of preparation of Benzene-
2CH3≡CH ; CH3–C≡CH
1. Cyclic coupling of Alkyne
2. From phenol (Zn dust)

CH3 –C≡C–CH3
3. Decarboxylation (NaOH/CaO/∆)
•
* Properties of Benzene- Zn
→
• Ph–OH dust Ph–H
1. E.S.R
E.A.R
StAr/ArSt COOH H COONa H
• Nitration • ,
Reagent
(1) Conc. HNO3 + Conc. H2SO4 H E
(2) NO2+ BF4–
(3) N2O5(NO2+ NO3–)
E+ + H⊕
•
• Halogenaion
• H2SO4 → H+ + HSO4–
Reagent
(1) X2 + anhy. FeX3(Cl, Br) H+ ⊕
HO NO2 H2O NO2
(2) X––X, Br––Cl
Polar ⊕
NO2 (Nitroniu m ion)
• Fridel craft alkylation

Reagent
FeX3
•
–
(1) R–X + anhy. AlX3 X X X + FeX4
+ (Halonium ion)
(2) R–CH=CH2 + H R–CH–CH3
(3) R–OH + H+ → R+
AlX3 ⊕
• Fridel craft Acylation • R+ X– R + AlX4–
(Rearran. if poss.)
Reagent
O O
|| O
(1) R – C – X + Anhy. AlX 3 Anhy. +
•
– –
R C X R C + AlX4
O O AlCl3
No
–
+
R C O–C–R+ AlX3
COOR rearrang.
(2)
• H2SO4  SO3 +H2O
• Sulphonation
Reagent
(1) Conc. H2SO4
(2) Oleum (H2S2O7 – SO3 + H2SO4)
(3) SO3
Generation of electrophile
Reagent Electrophile
(1) Conc.HNO3 + Conc.H2SO4 NO2+
(2) X2 + Anhy. FeX3 X+
(3) R–X + Anhy.AlX3 R+
O O
(4) R–C–X + Anhy. AlX3 R–C
(5) Oleum (H2S2O7) SO3
Formation of Carbocation
⊕ ⊕ H
E
E+ 3
sp Resonance Resonance hybrid
E
Aromatic Non-aromatic
Wheland Intermediate
Removal of proton
⊕ H
E
–H+
E
N.A. Aromatic
Carbocation
Directive influences of the group

+M o, p +M +M
E⊕ E
+  1 
 ROR ∝ + M ∝ − M 
 
E
–M m –M
E⊕
Addition of reaction
Cl
Cl Cl
Cl2 (excess)
hν
Cl Cl
Cl
Benzene hexachloride
(BHC)
Gammaxane
Gammaxene
Lindane
Hydrogenation
Highly exothermic
3H2+ Ni2 CH3 COOH
HighTemp. Hot alk.
Pressure
Cyclohex ane KMnO4
HYDROCARBONS
REAGENT FUNCTIONS
1. Hydrogenation [H2/Ni, Pt, Pd] • π Bond dks H, H ls rksM+ks
=
CH 2 CH 2 →
H2
Ni
CH3 − CH3
2. From Alkyl halide [Zn + dil. HCl] • X gVkvks, H yxkvks
CH 3 − Cl →
Zn
dil HCl
CH 4
3. Wurtz Reaction [Na + dry ether] • R – X bond dks F.R. rksM+ks 2R° dks tksM+ks
Intra. Br
Na + dry ether
4. Decarboxylation [NaOH + CaO • COOH gVkvks H yxkvks COONa gVkvks H yxkvks

sodalime] CH3 − COOH 
NaOH
→ CH 4
CaO
5. Kolbe's Electrolysis/HCOOH • •
• C––COOH C+ C → C − C even number
(Same as wurtz Reaction)
6. • Cl
Frankland Reaction [Zn, dry ether] •
•
Zn
• •
dry ether
7. Corey-house synthesis-
• Gilman's Reagent (R–Cu + RLi+) • X gVkvks Gilman dk R yxkvks
R2CuLi CH 3 − Cl →
Et CuLi
CH 3 − Et
8. Halogenation [X2 /hv] • 'H' gVkvks 'X' yxkvks
R − H →
X2
hν
R−X
9. Aromatisation [Cr2O3 / V2 O6 / Mo2 O3 ] Cr2O3
773 K, • V2O6, Mo2O3
10-20 atm
10. Isomerisation [Anhydride AlCl3] Anhyd.
• AlCl3
11. Combustion • CH 4 + 2O 2 
→ CO 2 + 2H 2 O [∆H = –ve]
12. Controlled oxidation • 2CH 4 + O 2 
Cu /523 K
→ 2CH 3OH
CH 4 + O 2 →
Mo 2 O3
HCHO + H 2 O
2CH3CH 3 + 3O 2 
(CH3COO)2
Mn
→ 2CH 3COOH + 2H 2 O
13. Reaction with steam • CH 4 + H 2 O  → CO + H 2
Ni
∆
14. Pyrolysis C6H12+H2

773K
• C6H14 C4H8 + C2H6
C3H6+ C2H4+CH4
REAGENT FUNCTIONS
1. Hydrogenation of Alkynes H H R R'
H 2+
[H2 + Pd/C, H2, + Pd/BaSO4] Lindlar's R – C ≡ C – R' C =C Cis
Pd/C H H
Reagant •
↑
Rosenmund
Cl – CHO
2. Birch reduction [Na + Liq.NH3/Li + Liq.NH3] H H R H
Na+
Terminal X • R – C ≡ C – R' C =C Trans
liq.NH3 H R'
3. Dehalogenation [Zn/CH3COOH] Zn
C C =
• C C
CH3COOH
X Zn X
4. Dehydration of alcohols (E1) H

+
Removal +
R–OH R–O– R + H2O
[H+/∆ (443 K), Conc.H2SO4, H3PO4] • protonation of H2 O
H Rearran. if poss.
(Ether, 413 K) Alkene
5. Dehydrohalogenation H
β α Alc. KOH
[Alc.KOH/Alc.NaOH/NaNH2] –C–C– –C=C
•
X
6. Halogenation X
• In non-polar solvent (CCl4, CS2) • R–CH=CH2
X2
R–CH–CH2
CCl4
Interhalogen (BrCl, ICl, IBr)
X
• In polar solvent Br
(X2 + H2O → HOX) + – Br
R–CH=CH2 H O R–CH–CH2
• 2
OH
(Bromohydrin)
7. Addition of HX [HCl, HBr, HI] – + + –
X
H
(rearran. if poss.) X
+
8. Markovnikov's Rule [HX] HX
–
CH3–CH=CH2 CH3–CH–CH3
–ve → Less hydrogen atom •
X
9. Addition of water [dil.H2SO4/H2, H2O/H3O+] + –
H
+
H2O/–H
+

•
OH
10. Hydroboration oxidaion (HBO) BH3
3RCH=CH2 B(CH2CH2R)3
 B2 H 6 / THF , H 2 O 2 / OH  •
+ –
11. Oxidation [H2O2] H OH
• R–CH=CH2 R–CH2–CH2–OH
Antimark.
+ –
12. Oxymercuration Demercuration (OMDM) H OH
R–CH=CH2 R–CH–CH3
[ Hg(OAc)2 / H 2 O, NaBH 4 ] • N.A.R.
OH
13. Addition of HBr/ Peroxide δ+
HBr
δ–
[HBr/ Peroxide] Anti markovnikov's R–CH=CH2 R–CH2–CH2–Br

peroxide
•
+
14. Addition of sulphuric acid H
R–CH = CH2 R–CH–CH3 [Rearran. if poss.]
–
OSO3H
[H2SO4, H+/HSO4–]
• R–CH–CH3
|
OSO3H
15. Oxidation [dil. Alk. KMnO4]
Baeyer's reagent
16. Ozonolysis [O, O, go]

(1) Reductive ozonolysis • dil./Alk
C=C C– C syn
O3+CCl4 O3 +CCl4 O3 O3
� , , Zn , Zn + HCl� KMnO4
Z𝑛𝑛 Me2 S
OH OH
vicinal dial
(2) Oxidative ozonolysis •
O3+CCl4 O3+CCl4
C=C C=O+O=C
� or �
H2 𝑂𝑂 H2 O2
Ketone 
Aldehyde 
* Other reagent • CH3 H CH3 OH
Hot KMnO4 /K 2 Cr2 O7 C=C C=O+O=C CO2
� � H H OH OH
Acidic KMnO4 /K2 Cr2 O7
Acetic acid Carbonic acid
17. Allylic substitution • O

O3
Chlorination C=C–C C=C C C Ozonide
Bromination C O O
ZnO
Cl2/hv Br2/hv
C C
t-buOCl t-buOCl
Cl2/500°C Br2/500°C O O
NCS NBS • t − buOCl
Ph − CH3 
• → Ph − CH 2 Cl
Cl
Br
•
NBS
Br
ALKYNES
REAGENT FUNCTIONS
1. From Carbides- • H O+
CaC2 →
3
Ca(OH) 2 + CH ≡ CH
∆ C H 2O
CaCO3 
→ CaO + CO 2 → Acetylene
H O
CaC2 
2 → CH ≡ CH
2. From Dehydrohalogenation- • H H
[Alc.KOH/alc.KOH NaNH2/NaNH2] | |
Alc. KOH
– C– C – –C≡C –
| | NaNH2
X X
3. Test for unsaturation- • Br Br
[Br2/CCl4] | |
Br2
R – C ≡ C – R' R – C – C – R’
CCl4 | |
Br Br
4. Kucherov Reaction + – 2+
• R – C ≡ CH
Hg /H2O
R – C = CH2 R – C – CH3
[Addition of H2O hydration] H2 SO4 | ||
HgSO4 OH O
dil H 2SO 4 , + 
  tautomerism
dil HgSO 4 
 2+ 
 Hg / H 2 O 
5. Hydrohalogenation (RX) • X
2HX |
R–C≡CH R–C– CH3 Gemi nal dihalide
|
X
6. Coupling reaction- • Cu2Cl2
2CH≡CH CH=CH2 CH2 = CH – C ≡ CH
NH4Cl |
a) Linear [Cu2Cl2/NH4Cl] acetylene
Cl≡CH Vinyl
b) Cyclic [Red hot tube] • R.H.T.

3CH≡CH
or Fe tube
c) Oxidative [O2] • 2R − C ≡ C − CH →
2 O
R −C≡C−C≡C−R
7. Silver nitrate test [Tollen's Reagent] • R − C ≡ C − H 
AgNO
3
→ R − C ≡ CAg (white ppt)
NH OH 4
[AgNO3 + NH4OH]
Ammoniacal silver nitrate
8. Cuprous chloride test • R − C ≡ C − H 

Cu,Cl2
→ R − C ≡ CCu (Red ppt)
NH OH 4
[Cu2Cl2 + NH4OH]
Ammonical cuprous chloride
9. Baeyer's reagent [dil. alk. KMnO4] OH OH O O

• dil./Al K | | || ||
R–C≡C–H R – C – C –H R – C – C –H
KMnO4 | | [O]
OH OH
O O
|| ||
R – C – C – OH
10. Ozonolysis-
1) Reductive ozonolysis [O3 + CCl4/Zn] • OO
O3 + CCl4
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
H2O + CO2
Na/ ∆
11. Lower to higher alkynes • R − C ≡ C − H 
NaNH
→ R − C ≡ C − Na +
2
[Na/∆, NaNH2]
R '− X '
→ R − C ≡ C − R '
12. Lewisite Formation • Cl– –AsCl2 β

+
CH CH–Cl β-Chlorovinyl dichloro
[AsCl3 Anhydrous AlCl3] ||| || arenes (Lewisite)
–
CH CH–AsCl2
α
13. British antilewisite • CH–Cl
|| Cl HS CHCl
CH–As || S
BAL Sn OH Cl HS CHAs
Sn S
HO
HO
14. Internal to Terminal • CH –C≡C–CH NaNH CH –CH −C≡CH
3 3
2
3 2
Na + liq NH3
Na +
15. Terminal to Internal • → CN3CH 2 C ≡ C− Na +
CH3 − CH 2 − C ≡ CH 
liq.NH3
Alc
CH3 − CH 2 − C ≡ CH →
KOH
CH3 − C ≡ C − CH3
REAGENT FUNCTIONS
Method of preparation of Benzene- •
1. Cyclic coupling of Alkyne •
2CH3≡CH CH3 –C≡CH
CH3 –C≡C–CH3
2. From phenol (Zn dust) • Zn

→
Ph–OH dust Ph–H
3. Decarboxylation (NaOH/CaO/∆) • COOH H COONa H
* Properties of Benzene- •
1. E.S.R • H E
E.A.R
+ H⊕
StAr/ArSt
• Nitration • • H2SO4 → H+ + HSO4–
Reagent
H+ ⊕
(1) Conc. HNO3 + Conc. H2SO4 HO NO2 H2O NO2
(2) NO2 + BF4– ⊕
(3) N2O5(NO2+ NO3–) NO2 (Nitroniu m ion)
• Halogenaion •
FeX3 –
Reagent X X X + FeX4
(1) X2 + anhy. FeX3(Cl, Br) (Halonium ion)
(2) X––X, Br––Cl
Polar
• Fridel craft alkylation • AlX3 ⊕
R+ X– R + AlX4–
Reagent (Rearran. if poss.)
(1) R–X + anhy. AlX3
(2)
+
R–CH=CH2 + H R–CH–CH3
(3) R–OH + H → R++
• Fridel craft Acylation • O O

Reagent – Anhy. + –
R C X R C + AlX4
AlCl3
O No
|| rearrang.
(1) R – C – X + Anhy. AlX 3
O
+
(2) R C COOR + AlX3
• Sulphonation
Reagent
(1) Conc. H2SO4
(2) Oleum (H2S2O7 – SO3 +
H2SO4)
(3) SO3
Generation of electrophile
Reagent Electrophile
(1) Conc.HNO3 + Conc.H2SO4 NO2+
(2) X2 + Anhy. FeX3 X+
(3) R–X + Anhy.AlX3 R+
O O
(4) R–C–X + Anhy. AlX3 R–C
(5) Oleum (H2S2O7) SO3
Formation of Carbocation
⊕ ⊕
H
E Resonance Resonance hybrid
E 3
E
sp
Wheland Intermediate
Aromatic Non-aromatic
Removal of proton
⊕ H
E
E
N.A. Aromatic
Carbocation
Directive influences of the group

+M o, p +M +M
E⊕ E
+  1 
 ROR ∝ + M ∝ − M 
 
E
–M m –M
E⊕
Addition of reaction
Cl
Cl Cl
Cl2 (excess)
hν
Cl Cl
Cl
Benzene hexachloride
(BHC)
Gammaxane
Lindane
Hydrogenation
Highly exothermic
3H2+ Ni2 CH3 COOH
HighTemp. Hot alk.
Pressure
Cyclohex ane KMnO4
HALOALKANE AND HALOARENES
REAGENT FUNCTIONS
1. From alcohol
• from HX [HX → H+ + X– ] •
+
H X–
: :
R–OH R–OH2 R R–X
• Reaction with PX3 , PX5, SOX2 •

(i) PX3 / Red P + X2 • 3R–O–H + PX3 3RX + H3 PO3
(ii) PX5 • R–O –H

R–X + POX3 + HX
X– OX3 –X
(iii) SOX2 • R–O –H
R–X + SO32 + HX
X– SO3–X
* Darzen's Reaction : - • R – OH
SOCl2
R–Cl+ SO2 + HCl
Best method of R–Cl
2. From Halogenation of alkanes:- • R–H
X2
R–X
HV
3. Halogenation of alkeanes :- • X
X2
R–CH=CH2 R–CH–CH2
CCl4
X2 + CCl4
X
X2 + H2O • X
X 2+ H 2O
R –C H= C H 2 R –C H –C H 2
HO ⊝ X ⊝
OH
4. From Hydrohalogenation of alkenes :- • H X

⊕
X
–

X
5. From halogen exchange:- • R–X R–F
AgF
(a) From swartz reaction (Preparation of alkyl
fluorides). X gVkvksa F yxkvksa
Reagent : Inorganic fluorides.
AgFf+, Hg2Ff2, COFf2, SbFf3, etc.
6. (b) Frinkelstein reaction (Preparation of alkyl • R–X NaI R–I
DMSO
iodide)
X gVkvksa I yxkvksa
Reagent :- NaI acetone =O
DMSO (Dimethyl sulphoxide) S=O
MOP of Haloarenes :- • X
X2
(1) Electrophilic substitution reaction Fe/FeX3
X2/Fe/FeX3
(2) From aniline • −
NH2 N2++ClCl
Diazotization (NaNO2 + HCl/HNO2) HNO2
0 – 5°C NaNO 2+HCl
0–5°C
BDC = Benzene diazonium chloride
Diazotization
(a) Sandmeyer reaction [Cu2Cl2/HCl] for Cl and • PhN + Cl– Cu2Cl2/HCl Ph–Cl
2 /
Br. (Cv2Br2/HBr) CuCN + –
PhN2 Cl Ph–CN
NaCl
HCN
–
• N2 + Cl Br
Cu2Br/H
B2/HBr
2O
•
+ –
(b) Gattermann reaction [Cu/HCl] N2 Cl Cl
Cu/HCl
–
•
+
(c) Balz–Schiemann's reaction [NaBF4] + – H BF4 –
PhN2 Cl PhN2 + BF4 pHF
Fluoro Bromo NaBF 4
BF3 + F⊝ replace
•
+ –
(d) Aryl iodide [KI] PhN2 Cl
+ – H I pH–I
NaBF 4
Halogenation [I2 + OA] • Ph–H

I2
Ph–I
O.A
HIO3, NIO4, HNO3
Important reaction :- • Ph–NO2

Sn+HCl
pH–NH2(Aniline)
Fe+HCl
1. Sn + HCl / Fe + HCl
2. Benzonitrile 
H3O +
→ Benzoic acid • OH O
+
H3 O
Ph–C≡N Ph – C – OH P – C – OH
Benzoic acid
OH
Nucleophilic substitrution reaction (NSR) • Nu
R–X R – Nu + X
* SN1 → 2 step C+, • SN1 – Racemic

* SN2 → 1 step, backside, attack • SN2– Inversion
1
ROR ∝
SN
Elimination Reactions :- • Br
E2 → Alc.KOH/ NaNH2 Alc.KOH
NaNH 2
+
Major
• E
1 1
* E Elimination :-
Br H2 O
∆
S N1
Br H2 O OH
* E1cb (Elimination via conjugate base): •

* Alkyl Fluorides Br F
– – – –
AgF Alc
F < Cl < Br < I KOH
Worst Transition Alc
L.G. KOH
* E1cb and E2 → Same reagent Alc. KOH
•
2 Br
9. Bulky Base in E
–
ter butoxide
O tert-butoxide tbuok
(3º alkoxide)
* Less hindered alkene is the major-Product.
Reaction with Metals: •
1. WURTZ Reaction (Na/dry ether) • 2R – X
Na
R–R [alkyl halide]
dry ether
R+R
2. Fittig Reaction (Na/dry ether) • 2Ph–X
Na
Ph–Ph [aryl halide]
dry ether
3. WURTZ Fittig Reaction (Na/dry ether) • Ph–X + R–X

Na
Ph–R
dry ether
4. Ullmann Reaction (Cu) (Same as fittig) • 2Ph–I

Cu
Ph–Ph
5. Grignard Reaction • Mg R–MgX 50% covalent

R–X dry ether
R–MgX
R–MgX 50% ionic
* Properties of Haloarenes •
1. NSR in Aryl halide (ArSN ) 2
• X 2
sp
NO
X [Reasons]
2. Dow's process: • Cl OH
Na+OH (H.T-625 k)
(H.P-300atm) NaOH NaOH
H temp H.P
* EWG - nitrohalobenzene
* Carbanion, ROR-stability of C– ONa OH
* ROR ∝ nitro group
acidic
+
H
Meisenheimer Complex: • Cl
HO
Cl
NO2 NO2
OH
Meisenhei mer complex

3. ESR - •
2X O/P X X
+ F
F
F
Major
a. Chlorination- Cl2/Fe/FeCl3 • X X X
Cl
Cl2
Fe/FeCl3
Cl
b. Nitration - conc. HNO3, conc. H2SO4 • X X X
NO2
NO2
Major
c. Sulphonation - H2S2O4/Oleum/SO3 • X X X
SO3H
SO3H
Major
d. Friedal Craft Alkylation- • X X X
anhy. AlCl3/R–CH–CH2/HF/R–OH/H+ R
R–X
anh. AlCl 3
R
e. Friedel craft Acylation • X
O X O X
O C–R
R–C–X
R–C–X, Anhy. AlX5 anh. AlCl 3
R–C=O, Acylation cation

Acylivm cation O=C–R
ALCOHOL PHENOLS AND ETHER

Reagent Function
(1) MOP of alcohol:-
1. From alkenes (dil H2SO4/H+ H2O/H3O+) • dil H2SO4
rearrangement
Markovnikov addition OH if POS
2. HBO Hydroboration oxidation • HBO OH

OH )
−
(B2H 6/TnF, H2O2/OH)
THF
Antimarko vniko v
3. OMDM (Hg(OAC)2 / H 2 O, NaBH 4 ) OH
↓
Markovnikov
• OHOM
* Reduction reaction:-
1. Reduction of carbonyl compound. • π ca/k dks H, H ls rksM+ nksa
O OH
LaH
LiAlH4(LAH)
xenone
NaBH4 (SBH)
CHO CH2OH
H2
H2/Catalyst
N1
Aldehyde
2. By reduction of carboxylic acid and ester. • COOH gVkvksa CH2OH yxkvksa

LiAlH4 – strong
O
LiAlH4
R–C–OH R–CH2OH
* NaBH4 → mild reducing agent • H 2 / catalyst → good yield.

Only with carbonyl
↓
Carboxylic and ester
ester
O O +
R'OH HH
2+Ca
2/Pt
R–C–OR
H R–C–OR' R–CH2–OH+R'OH
3. By grignard reagent • PhMgBr

Ester – grignard → 3° H
+
O Ph
OH
(2) MOP of Phenol:-
(1) Dow’s process Cl OH
• (i) NaOH
(ii) H+
623K 300 atm
(2) Benzene sulphonic acid SO3H OH
conc. NaOH
•
H2SO4 H+
(3) Diazonium salt
(4) Frome cumene

OH
O
•
(i) O2 /hv
+
(ii) H+
Isopropyl
Benzene
(3) MOP of ether:-
(1) Dehydration of alcohol H+/O
ROH + HOR ROR
• Hydrocarbon – 413K (con H2SO4
OH
H3PO4) → alkene • conc. H2SO4
O
413K
(2) Williamson ether synthesis C2H5O–NAI

CH3–Cl CH3–OC2H5
NiSN 2 (i) Rx • SN2
(1°)
Alc.KOH
(2°,3°) → C2
↓ NaOH CH3O–H+
Alc.KOH, NaOH
Br (2°
E2 and 3°)
Properties of alcohol:-
1. Acidic Nature:- * ROH + Na / O → RO − Na + + H 2

→ RO − + H +
ROH ←
 * ROH + Al → RO − ( ) 3
Al3+ + H 2
* ROH + Na + H − → RO − Na + + H 2
* ROH − + Na + NH 2 − → R − ONa + NH3
 ROH + NaOH → R − ONa + + H 2O 
 − ⊗
 ROH + NaHCO3 → CO NaI + H 2CO3
2. Esterification:- • O
R–C–OH+H OR`
Remove
O O
H+
R–C–OH+R`OH R–C–OR'
3. Lucas test:- • R–OH

H+ +
R–OH2 R
+ Cl–
R–Cl
(Turbidity)
Conc.HCl anhy ZnCl2.
ROR :- 3° > 2° > 1°
* to distinguish b/w 1, 2°, 3° ROH
In Sec. Min. No turbidity
In resonance c+
1°,2°,3° - Turbidity in sec.
4. Dehydration:- •
OH H+/∆ rearrangement
(1) VIA E1
Conc H2SO4/H+∆
(2) VIA E2 • OH
Dehydrating agent :- P2O5/∆ +
P2O5/∆
POCl3/∆
Major
Al2O3/∆
(3) VIA E1cb • + –
ThO2/∆ Thorium oxide ThO2 /∆
Major
Minor carbanion
OH 1º more
stable
5. DARZEN'S REATION •
a) VIA SN1 (Intramolecular) • ROH
SOCl2
R−Cl +SO2 ↑+ HCl↑
* Retention. [Retention]
b) VIA SN2 • ROH
SOCl2
R−Cl [Inversion]
• Pyridine + SOCl2
• Inversion N
6. With PX3 • ROH

PCl3
R−Cl
PCl5
R−Cl
7. Oxidation: [MOA] [SOA]
[HOA] → PCC, POC, CrO3 + • Ion → Aldehyde • Ion → Acid
Acetone, • RCH2OH → R– • R–CH2OH → R–
CHO COOH
• 2º → Ketone • 2º → Ketone
Collin's • R–CH2–OH → • R–CH2–OH →
reagent O O
R–C–R R–C–R
CrO3+2 , Cu/36ºC
N
β
[SOA] → KMnO4/H+, HO + KMnO4, 3° Cu/Ag Cu/300°C
* 300° C α OH
K2Cr2O7/H+, E2
Cr2 O3 + H 2SO 4 * For allylic or Benzylic alcohol (MnO2)
H2Cr2O4
Jone's reagent
• R–CH =CH–CH2OH 
MnO2
→ R–CH=CH–
CHO
• ph–CH2OH 
MnO2
→ ph–CHO
OH
• ×
Properties of Phenol
1. NITRATION:-
(1) With dil HNO3 [Low temperature 298K OH OH OH
O/P] NO2
dil.HNO3
* Steam distillation • + +
NO2
(Intra H bond) NO2
(Inter H bond)
* B. Point P >O
* Volatility P<O
(2) With Conc. HNO3 [Picric acid] OH OH

yield → Poor NO2 NO2
Conc. HNO3
• +
NO2
NO2
(Picric acid )
* Now days H2S2O7 → SO3H OH OH
(1) Sulphonation from SO3 H
H2S2 O7
nitrodisulphide •
Conc. H2SO4
Conc. HNO3
+
NO2
(Phenol)
SO3H
OH
NO2 NO2
NO2
2. HALOGENATION: OH OH OH
(1) Mono bromination Br
Br2,CO2
Br2, CS2, CHCl3, CCl4 • +
CHCl3
Solvent — low polarity CCl4
Br
(Major)
(2) Tri bromination OH OH
Br2, H2O (Bromine water) Br Br
Br2
•
H2O
+ M power white pp t.
Br
OHCO−
3. ACIDIC NATURE: • Na / ∆
phOH  → phO− Na+ +H2
phOH  phO + H – +
• phOH 
NaH
→ phO−Na+ +H2
• phOH 
NaNH 2
→ phONa+ + NH3
• phOH 
NaOH
→ phONa+ +H2
• phOH 
NaHOOH
→ phO−Na+ + H2 CO3 ×
more acidic
4. ESTERI FICATION: O O
• R–C–OH + H–Oph → R–C–O–ph
O O
• R–C–Cl + H–Oph → R–C–O–ph + HCl
O O
• R–C–OCOR + H–Oph → R–C–O–ph + RCOOH
an hydride
5. ASPIRIN FORMATION: COOH COOH O

* Acetylation of salicylic acid - aspirin OH O O−C−CH3
+
O + CH3−C−OCOR H + RCOOH
[CH3–C] acetyl •
Salicylic acid o-acetyl salicylic acid
o-hydoxy benzoic acid
[Aspirin]
6. KOLBE'S REACTION: OH– O−Na+
OH OH
COOH
•
+ –
+ Na OH + H2 O
i) NaOH
ii) CO2 phenoxide
iii) H+
H gVkvksa → vkWFkksZ COOH yxkvksa O
–
O− O O OH
C–O– COO–
O=C=O

•
H+
OH
COOH
o-salicylic acid
7. REIMOR TIEMANN REACTION: • OH OH OH
Intermediate → Benzal chloride CHO
CCl3
+
KOH (minor)
(phenol) (major)
CHO
Important: • OH OH
phOH + CCl3/HOH → salicylic aldehyde CHO
+ CCl3 /KOH
phOH + CCl4/HOH → salicylic acid • OH OH

COOH
CCl4
KOH
8. Oxidation of phenol with Zn dust • Zn ph–H

ph–O–H dust
9. Oxidation of phenol • OH O
Na2 Cr2 O7
H2SO4
O
Parabenzoquinone
10. Test of Phenol:
(i) FeCl8 Test • 6 phOH

FeCl3 +3 3–
[Fe/(Oph)6 ] + 3HCl + 3H
[Voilet]
(ii) Br water test • OH OH
Br Br
Br2
H2 O
White ppt.
Br
•
2+ –
11. Coupling reaction OH N Cl OH
ESR. [p-hydroxy azo benzene]
ESR
Couple bangs +
N (p-hydroxy
(orange dye)
azobenzene)
N
12. Elb's reaction • OH OH

H2S2O6/HOH hydroxyquinol
K2S2O7
KOH
(hydroxyquinol)
OH
PROPERTIES OF ETHER
1. Reaction with HX • X–
R–O–R' R–X + R'OH
1º and 2º alkyl – SN2 SN2
H
Nucleophilic attack
on less hindered alkyl
3º and Reso – SN1 • ph–CH2–O–CH3

Conc.HI
ph–CH2 –I + CH3 –OH
SN1
Anhydrous Hx – SN2
Ion HX – SN1
2. Hydrolysis of ether • +
H3O
+
O OH HO
• H3O+
O HO OH
3. Electrophilic substitution reaction:
(i) Halogenation [X2/Fe]-para major •

OCH3 OCH3 OCH3
always
X
X2
Fe +
X
(major)
(ii) Friedel craft reaction: • OCH3 OCH3 OCH3
• Alkylation (RCl/AlCl3)
R
RCl
AlCl 3 +
• Acylation • OCH OCH O OCH
3 3 3
O O C–R R
(R–C–Cl/Anhy. AlCl3) R–C–Cl
anhy.AlCl 3 +
R O=C–R
• Nitration (Conc. HNO3/H2SO4) • OCH3 OCH3 OCH3
NO2
conc. HNO 3
+
conc. H2SO4
NO2
4. Reaction with PCl5 • CH3–O–C2H5 
→ CH3Cl + POCl3 + C2H5Cl
PCl5
5. Reaction with cyclic ether • H

+
OCH3 OH–
O OH
• – Nu
Nu
(Anisole)
O
1. VIA E1cb
ThO2/∆ Thorium oxide
5. DARZEN'S REATION
a) VIA SN1 (Intramolecular)
* Retention.
b) VIA SN2
• Pyridine + SOCl2
• Inversion
6. With PX3
7. Oxidation:
[HOA] → PCC, POC, CrO3 + Acetone,
Collin's
reagent
CrO3+2 , Cu/36ºC
N
[SOA] → KMnO4/H+, HO + KMnO4, K2Cr2O7/H+,
Cr2 O3 + H 2SO 4
H2Cr2O4
Jone's reagent
Properties of Phenol
1. NITRATION:-
(1) With dil HNO3 [Low temperature 298K O/P]
* Steam distillation
(2) With Conc. HNO3 [Picric acid]
yield → Poor
* Now days H2S2O7 → SO3H
(1) Sulphonation from nitrodisulphide
Function:
+ –
ThO2 /∆
• Minor
Major
carbanion
OH 1º more
stable
SOCl2
• ROH R−Cl +SO2 ↑+ HCl↑
[Retention]
SOCl2
• ROH R−Cl [Inversion]
N
PCl3
• ROH R−Cl
PCl5
R−Cl
[MOA]
• Ion → Aldehyde
• RCH2OH → R–CHO
• 2º → Ketone
O
• R–CH2–OH → R–C–R
[SOA]
• Ion → Acid
• R–CH2OH → R–COOH
• 2º → Ketone
O
• R–CH2–OH → R–C–R
Cu/Ag β Cu/300°C
* 3° α OH
300° C
E2
* For allylic or Benzylic alcohol (MnO2)
• R–CH =CH–CH2OH 
MnO 2
→ R–CH=CH–CHO
• ph–CH2OH 
MnO 2
→ ph–CHO
OH
• ×
OH OH OH
NO2
dil.HNO3
+ +
NO2
(Intra H bond) NO2
(Inter H bond)
* B. Point P >O
* Volatility P<O
OH OH
NO2 NO2
Conc. HNO3
+
NO2
NO2
(Picric acid )
OH OH
SO3 H
H2S2 O7
Conc. H2SO4
Conc. HNO3
+
NO2
(Phenol)
SO3H
OH
NO2 NO2
NO2
2. HALOGENATION:
(1) Mono bromination
Br2, CS2, CHCl3, CCl4
Solvent — low polarity
(2) Tri bromination
Br2, H2O (Bromine water)
3. ACIDIC NATURE:
phOH  phO– + H+
4. ESTERI FICATION:
5. ASPIRIN FORMATION:
* Acetylation of salicylic acid - aspirin
O
[CH3–C] acetyl
6. KOLBE'S REACTION:
OH OH
COOH
i) NaOH
ii) CO2
iii) H+
H gVkvksa → vkWFkksZ COOH yxkvksa
7. REIMOR TIEMANN REACTION:

Intermediate → Benzal chloride
Important:
phOH + CCl3/HOH → salicylic aldehyde
phOH + CCl4/HOH → salicylic acid
OH OH OH
Br
Br2,CO2
+
CHCl3
CCl4
Br
(Major)
OH OH
Br Br
Br2
H2O
+ M power white pp t.
Br
OHCO−
• Na / ∆
phOH  → phO− Na+ +H2
• phOH 
NaH
→ phO−Na+ +H2
• phOH 
NaNH 2
→ phONa+ + NH3
• phOH 
NaOH
→ phONa+ +H2
• phOH 
NaHOOH
→ phO−Na+ + H2 CO3 ×
more acidic
O O
• R–C–OH + H–Oph → R–C–O–ph
O O
• R–C–Cl + H–Oph → R–C–O–ph + HCl
O O
• R–C–OCOR + H–Oph → R–C–O–ph + RCOOH
an hydride
COOH COOH O
OH O O−C−CH3
•
+
+ CH3−C−OCOR H + RCOOH
Salicylic acid o-acetyl salicylic acid

o-hydoxy benzoic acid
[Aspirin]
OH– O−Na+
•
+ –
+ Na OH + H2 O
phenoxide
O
–
−
O O O OH
C–O– COO–
•
O=C=O

H+
OH
COOH
o-salicylic acid
OH OH OH
CHO
CCl3
• +
KOH (minor)
(phenol) (major)
CHO
OH OH
CHO
• + CCl3 /KOH
OH OH
COOH
CCl4
•
KOH
Reactant
Oxidation of phenol with Zn dust
9. Oxidation of phenol
10. Test of Phenol:
(i) FeCl8 Test
(ii) Br water test
11. Coupling reaction
ESR. [p-hydroxy azo benzene]
Couple bangs
12. Elb's reaction
H2S2O6/HOH hydroxyquinol
PROPERTIES OF ETHER
(1) Reaction with HX
1º and 2º alkyl – SN2
Nucleophilic attack
on less hindered alkyl
3º and Reso – SN1
Anhydrous Hx – SN2
Ion HX – SN1
(2) Hydrolysis of ether
(3) Electrophilic substitution reaction:
(i) Halogenation [X2/Fe]-para major always
(ii) Friedel craft reaction:
• Alkylation (RCl/AlCl3)
O
• Acylation (R–C–Cl/Anhy. AlCl3)
• Nitration (Conc. HNO3/H2SO4)
(4) Reaction with PCl5
(5) Reaction with cyclic ether
OCH3
(Anisole)
Functions
Zn ph–H
ph–O–H dust
OH O
Na2 Cr2 O7
•
H2SO4
O
Parabenzoquinone
FeCl3 +3
•
3–
6 phOH [Fe/(Oph)6 ] + 3HCl + 3H
[Voilet]
OH OH
Br Br
Br2
• H2 O
White ppt.
Br
2+ –
OH N Cl OH
• +
ESR
N (p-hydroxy
(orange dye)
azobenzene)
N
OH OH
K2S2O7
• KOH
(hydroxyquinol)
OH
X–
• R–O–R'
SN2
R–X + R'OH
H
Conc.HI
ph–CH2–O–CH3 ph–CH2 –I + CH3 –OH
• SN1
•
+
H3O
+
O OH HO
+
H 3O
•
O HO OH
OCH3 OCH3 OCH3

X
X2
• Fe +
X
(major)
OCH3 OCH3 OCH3

R
RCl
• AlCl 3 +
R
OCH3 OCH3 O OCH3
O C–R R
• R–C–Cl
+
anhy.AlCl 3
R O=C–R
OCH3 OCH3 OCH3
NO2
conc. HNO 3
• +
conc. H2SO4
NO2
• CH3–O–C2H5 
→ CH3Cl + POCl3 + C2H5Cl
PCl5
+
H
• OH–
O OH
Nu
– Nu
•
O
Organic Chemistry
REAGENT FUNCTION
MOP of Carbonyl Compound • 1° R–CH2–OH 
MOA
→ R–CHO (aldehyde)
1. By oxidation of alcohols: •
2° R–CH–R 
MOA
→ R–C–R (ketone)
MOA  PCC, PDC, Cu, O3 O , 2Py OH O
R
Cu/Ag 300°C
* Allylic benzylic → MnO4 • 3° R–C–R 
MOA
→ No oxidation
OH
2. By dehydrogenation of alcohols:-
Cu/Ag 300°C
• • OH →
Cu /Ag
300° C
Alkene
3. Form hydrocarbons:-
(a) ozonolysis (Reductive):-
O + CCl
O3 + CCl4/Zn/Me2S • 
3 4
Zn H O / MeS
→ O+O
2
(b) Kucherov reaction:- O O
Hg2+/H2O/dil. HgSO4/dil. H2SO4
2+
• R–C≡CH 
Hg
H2O
→ R–C=CH → R–C–CH3
MOP of Aldehydes 2
1. Rosenmund reaction:- OH O
Tautomerism
H2+Pd/BaSO4
O O
H 2 + Pd
2. Stephen's reduction:- • R–C–Cl →
BaSO4 R–C–H
SnCl2 + HCl/Steam/H3O+ H H
* DM – Cl hatao, – OH lagao.
3. DIBAL-H:-
* di isobutyl aluminium hydride/H3O+ H H H +2
R R′
* mild reducing agent. • Alkynes R–C≡C–R′ 
Pd/C
→ C = C cis
H H
4. From hydrocarbons:- H H
(1) Etard reaction:- • R–C≡N →
H2
R–CH=NH
CrO2Cl2/Cs2 or CCl4 imime
(2) Side chain oxidation:- OH
2Cl2/hν – aq. HOH(SN2) × 2 times 
→ R–CH + NH3
OH
1Cl2 → alcohol 
  R–CHO + NH3
 2Cl2 → aldehyde 
 3Cl2 → acid  + +
H H
R–C≡N
–
(3) Alternate of Etard:- • R–C=N R–CH=NH
O
H
CH3–C–OCOCH2/C2O3 R–CHO
(4) Gatterman Koch reaction
CO + HCl/Anhy. AlCl3 • Ester → Aldehyde
O
MOP OF KETONES R–C–OR′ → R – CHO + R ′ OH
1. From acyl chloride

+O
Cadmium Chloride (CdCl2)
•
C r O Cl
Ph – CH3 →
2 2 2
Cs / CCl
Ph CH[OCs(OH)Cl2 ]2
2 4
Chromium complex
2. Grignard reagent
Reaction with cyanide OH
→ Ph–CH PhCHO
3. Friedel Crafts acylation OH OH
+4
+ HO–CH–Cl
Cl
Properties of Carbonyl compound OH
CH3 CHCl2 CH
1.( Nuclophilic addition reactions:- OH
1 • 2Cl2 aq. KOH
Reactivity:- ROR ∝ hν
S·H 2HCN SN2
Benzal
ROR ∝ Electrophilicity, – M, – I Chloride
1 1
Aldehyde > ketones ∝ ,
+M +I CH3 CH(OCOCH3 )
O
CHO
Eg of NAR:- CH3 –C–OCH3
1. Addition of hydrogen cycnide (HCN):- • CrO3
O OH Benzal
diacetate
DM:- CH3–C–H CH3–C–H Racemic mix
CN
λ and L • CO + HCl 
AlCl3
→ CHO
2. Addition of sodium hydrogen sulphide (NaHSO3) O

O
R–C–Cl R
• Cd R–C–R
O R ketone
R–C–Cl
RMgX
• R'–C≡Ν +
R'–C=O
H3O
R
O C–R
R–C–Cl
• B·B (no compound)
Anhy AlCl 3
Nu Nu
•
– +
Nu – H
C=O C=O C–OH
sp
2 alkoxide
3
(sp )
CN +
CN
• C=O
NaCN
C=O
– H
C–OH
H2 O cyanohydrin
+
• R – CN 
H 3O
→ R – COOH
HSO3 Na OH
• C=O C
SO3 Na
R–C–CH3
All aldehyde + methyl ketone
O
(Section-I) ORGANIC CHEMISTRY
REAGENT FUNCTION
1. Addition of Alcohol 1. Reaction with 1 mole ROH
+ – +
C = O ROH
+
C– OH
(ROH) H
OR
Aldehyde – hemi acetal
Direct method: R + – ROH+ R OH
C=O C
H Hemi acetal
H OR
2 mole ROH Ketone — Hemi ketal

H OR H+ OR
R R OH Hemi ketal
C=O C C=O C
H OR OR
R R OR
2C2 H5 OH Ph OC2 H5
* Ph–C–H C acetal
H OC2 H5 2. Reaction with 2 mole ROH
R– OH+ C–OH HOC C–OR
C=O
H+ H+
OR OR
Aldehyde hemi acetal acetal

Ketone hemi ketal ketal
4. Hydrolysis of hemi acetal, acetal, ketal, hemi acetal R OH H3O

+ R
• C C=O
All will become carbonyl again. H OR H
Hemi acetal Carbonyl

5. Addition of ammonia and its derivatives.
O
C = O + H2N–Z C=N–Z • NH2NH2 CH3
CH3–C–CH3 C = N–NH2
CH3
hydrazone
Reduction Reactions LAH
H
H
• O OH
1. Reduction by LAH, SBH and Catalytic
hydrogenation. SBH
• Ph – CHO  → Ph – CH2OH
O OH
H2 + Pd
•
2. Clemmenson’s Reduction •
[Zn(Hg)con HCl] acidic zinc amulgum. Zn(Hg)
C=O CH2 alkane
Conc. HCl
O
• Zn(Hg)
conc HCl
HO Cl
reaction
3. Wolff-Kishner reduction OH
OH (i)NH 2 OH
OH
NH2–NH2 glycol ( basic medium) O CH2 (alkene)
OH (ii) OH
•
O + H2N – NH2 C=N–NH2 CH2

hydrazine hydrazine
Oxidation Reaction •
O O
+
Ag
Ph/R–C–H Ag + R–C–O –
OA
1. TOLLEN’S TEST: slivery white ppt
* Aliphatic and aromatic aldehyde
AgNO3 + NH4OH (Ammoniacal silver nitrate) • O 2+
O
Cu
2. FEHLING TEST: R–C–H Cu2O + R–C–O –
OA
* Aliphatic aldehyde: Reddish
Brown PPT
Fehling A Fehling B:
aq CuSO4 NaI (sodium K tartals)
•
(Rochell’s salt) OA +1
–
RCHO R–COO + Cu2O
3. BENDICT’S TEST: + Reddish brown
* Aliphatic aldehyde: Cu2+
aq CuSO4 + Sodium nitrate

CH3COONa alkaline hydrolysis
HO–C–COONa NaOH
R–C–CH3 R–C–CX 3 R–COONa
CH2COONa +
O O
CHX3
4. HALOFORM TEST: Haloform
(i) X2 + OH (NaOH/HOH) • 2º Alcohol → ketone
MOA
(ii) NaOX or HOX R–CH–CH3 R–C–CH 3
Mild O.A.
OH O
• Carbanion intermediate
• 1º Alcohol → Acetal dehyde
• ROR ∝ stability of e– HOA → CH CHO
CH3CH2–OH  3
• ROR Cl2 ≈ Br2 ≈ I2 ethanol acetaldehyde
5. POPOFF’S RULE:
• KMnO4
CH3–CH2–OH + CH3COOH
∆
Oxidation of ketone KMnO4/∆hightra O
CH3COOH
• 2º alcohol 
→ ketone
• Ketone 
→ carboxylic acid
(Section-I) PHYSICS
REAGENT FUNCTION
6. STRONG OXIDISING REAGENT 1º → Acid, 2º → Ketone
3º → reaction.
OH
• →
Cr2O3
H SO
2 4
1º COOH
CH2OH → COOH reaction
2º
• →
H 2CO 4
OH O
ALDOL CONDENSATION β α
1. Aldol Condensation :- 2CH3CHO  →
dil
1. CH –CH–CH 2–CHO
* Carbonyl Compounds having αH NaOH 3
|
* Reagent → dil NaOH/HOH or Na2CO3/H2CO3 OH
β-hydroxycarbonyl
Carbonyl compound 
dil
NaOH
→ β hydroxycarbonyl
αH CH3
C=O+H–CH2 CHO  →
dil
compound • NaOH
H
• β hydroxy Carbonyl Compound → α, β, ∆
unsaturated carbonyl compound CH3 OH

H
H CH2 HO
2. 2CH3CHO → CH3–CH=CH–CHO
Crotonaldehyde
2. Cross-aldol condensation:-
* 2self + 2 ions = 4 CH3 H
∆
• C=O + CH–CHO 
dil Ba
→
H H
CH3
C=CH–CHO
H
3. Intramolecular aldol condensation crotonaldehyde
O O
|| || O
CH3–C–CH2–CH2–C–H ||
CH3–CHO + CH3 –C–CH3
• Acetaldehyde acetone 
dil. OH
∆
→
* 6 > 5 > 7 > 4 ring
NAR Ald > Ket. Total no of structural product (4)
* 2 self
4. Cannizzaro Reaction :- CH3 H CH3
* Opp. of aldol C=O CH–CHO → C=CH–CHO
* Req. – Aldenyde (not having αH) H H H
Ketone – Hydride Shift
Reagent → conc.KOH/NaOH
50% KOH/NaOH
* 2 ions
5. Cross Cannizzaro: - O
O
Conc KOH. CH3 H ||
CH3 ||
C=O CH–C–CH3 → C=OH–C–CH3
H H H
H H H
C=O H CH C=CH
6. Intramolecular Cannizzaro: -
CH2 C=O CH2 C=O
CH2 CH2
H – CHO  → H – COOH

50%
KOH
7. Electrophilic Substitution Reaction :-
* Aromatic aldehyle and ketone. H – CHO  → H – CH2OH
50%
KOH
• H − CHO + ph CHO 

conc. KOH
→
↓
always
CARBOXYLIC ACID oxidise
Method of preparation of carboxylic acid H-COOR + pH CH2OH
CHO 50% COOH

• |  → |
CHO KOH CH2OH
COONa
1. From oxide of OH, aldehyde, Ketones COOH
• 
50%
NaOH
→
SOA: - KMnO4/H+, not KMnO4/H2Cr2O7/H+/Cr2O3 + COOH CH2OH
H2SO4 O O
|| ||
C–OH C
CrO3 + H2O → H2 Cr2O4 /con HNO3. + +
→
H
acidity
→
H O
CH2OH CH2
CHO
CHO
2. From oxidation of alkylated benzene:
• 
conc. HNO3
→
* Atleast 1 Benzylic H. con. H SO
2 4
NO2
Alc KMnO 4 KMnO 4 − KOH –M

* Reagent meta di n e
H+ H+
• 1º alcohol → Acid
• Ald. → Acid
COOH
• Ketone → Acid (popoa)
• → Terephthalic acid OH COOH

alk + KMnO4
•  + →
H
COOH
OH
COOH H
AgNO3 +
•  →
NH OH H +
• → Phthalic acid 4
Tollen 's Test
O O
COOH
Salt → Acid 
 H+ 
CH3 COOH
→
alk KMnO4
+
H
COOH
• Isophthalic acid
COOH
COOH 
KMnO4
→
H+
COOH COOH O
||
• COOH COOH Helithelic acid • R–C≡N 
Partially
hydroly
→ R–C–NH2 (electron)
H + OH − amide
COOH COOH +
• R–C≡N 
H3O
→ RCOOH (acid)
3. From hydrolysis of acid derivatives:-
O O
(a) Nitrile || + ||
• R–C–Cl 
H3O
→ R–C–OH
(b) Acid chloride
O O O O
(c) Anhydride || || ||
H3O+
||
• R–C–O–C–R → R–C–OH + R′–C–OH
S. Reagent Functions
No.
d) Ester O O
H3O +
e) Amides • R – C – OR R – C – OH + R'OH
O +
O
H3O
• R – C – NH2 R – C – OH
Acidic
* Compound +
RCOOH
H3O
Alkaline
OH−/H 2O
R−COO
9. From Grignard reagent :- O
R MgX O=C=O
R – C – O MgX → RCOOH
Properties of Carboxylic acid
1) Acidic Strength : COOH COOH COOH
• Acidic Strength : * 1>2>3

1 1 +I
∝ −M ∝ −I ∝ ∝
+M +I +M > +I
2) Reaction with PCl3, PCl5, SOCl2 :- OH SOCl2 Cl
−OH → Cl O O
3) Anhydride formation:- O O O
P2O5 /
P2O5/conc. H2SO4 R – C – OH R – C – O−C – R
conc. H 2SO4
4) Esterification :- O O
H+
R – C – OH R – C – OR' + H2O
+
HOR'
5) Reaction with Ammonia :- O O
R – C – OH + NH3 R – C – O NH4
∆ H2O
O
R – C – NH2
DM : - OH hatao, NH2 lagao
O O
R – C – OH + H – NH2 R – C – NH2
6) HVz Reaction :- Red P – X2/H2O (1) Red P–X2
R – CH2 – COOH R – CH – COOH
(2) H2O
Hell volhard zeheinskey. X
Acid having α-H DM : - H hatao, X lagao.
7) Kolbe's Electrolysis :- enetro R
R – COOH R R–R
+
8) Decarboxylation :- NaOH
R – COOH R–H
CaO
NaOH, CaO NaOH +
R – COONa R–H
CaO
9) ESR :- COOH COOH
NO2
Conc. HNO3, conc H2SO4 conc. HNO3
–M conc. H 2SO4
meta NO2
REAGENT LAH / B2H6

REDUCTION:-
HUNSDIECHER REACTION :-
Br2 / CCl4
DM− COOAg hatao, Br lagao
FUNCTION
SIMONINI REACTION :-
LAH
R – C – OH R – CH2 – OH
O B2H6
O
I2 , R— C— OAg
H OH
SCHOTTEN BAUMAN REACTION:- LAH
O O OH OH
Py (Basic)
N
B2H6
HEATING EFFECT :-
H
β−keto acid OH
O
Dicarboxylic acid.
O
COOH Br2
General formula (CH ) 2 n R – C – OAg R – Br
COOH CCl 4
O
O O
n= 0 1 2 3 4 5 I2 R – C – Ag
R – C – O Ag R–I R – C – OR + AgI
O O
O M S G A p Py
Oxalic Malic Succinic Glutamic PhOH + Cl – C Ph – O – C
Adipic acid pamelic acid + HCl
N
COOH COOH
CH2
COOH COOH
CH2 COOH CH2 COOH COOH
CH2 (CH2)4
CH2 COOH CH2 COOH COOH N Cl
COOH O H
(CH2)5 O O
COOH
R – C – CH2 – C – OH Warm R – C – CH3
COOH
n = 0 CO, CO2, H2O CO + CO2 + H2O
COOH
n = 1 CO2 COOH
CH2 CH3 – COOH+ CO2
n = 2,3 H2O COOH
n = 4,5 CO2 , H2O O
OH
O
OH
NO2 NH2
Sn /HCl
Fe /HCl
H2 +Pd / ^OH
MOP Of AMINES:-
NO2 hatao, NH2 lagao.
(1) Reduction of nitro compounds:
R −X
Sn/HCl or Fe/HCl NH3 R-NH2 R − X R2NH
H2 +Pd/OH 1°
SN2 R−X
+ − R −X
(2) Ammonolysis of alkyl halide:- R4 NX R3N
LAH
R −C N R − CH2 − NH2
(3) Reduction of nitrile:-
Na(Ag)+ EtOH
LAH/| Na(Ag) + EtOH /H2 + Ni H2 + Ni
CN hatoa, CH2 NH2 lagao
(4) Reduction of amide:-
O
LAH
LAH R −C − NH2 R − CH2 − NH2
(5) GABRIEL PHTHALIMIDE SYNTHESIS:- C = O hatao, CH2 lagao
• Aliphatic iamine O
COOH
(6) HOFFMAN BROMAMIDE DEGRADATION
1) HOH
REACTION:- N−H + R−NH3
2) R - X(1°)SN2
O  O 3) HOH COOH
[Br2/HOH]  ||  chupa do Salt of
C  phthalimide phthalic acid
 
4 mole HOH R-X R - NH2
X hatao NH 2 Lagao
PROPERTIES OF AMINES:-
(1) Basic strength :- O
Br2
R −C = NH2 R−NH2
Availability of l.p. on N ↑ S1B −BS ↓ 1° and 0 KOH
1 S1B −BS ↑ 2° and 3° O

B.S ∝ + M ∝
− I, − M R −C = NH2 + Br2 + 4HON R NH2 + 2HBr
+ H2CO3 + 2H2O
(2) Alkylation:-
(3) Acylation:- only time
Py – to neutralize HCl
SNAt
Alternate pattern:-
O O
R − C − N− − Br R −C = N R − N − Br
NITRENE
− N : + H+
+
−N H
NH2 > NH2 B.S
RX
NH3 R−NH2 RX R−NH −RRX
RX
R4 N+ X R−N −R
R
O O
Py
R − NH2 + R' −C − Cl R − NH − C−R'
acid cloride O
R' −C − Cl
No reaction
O
R − NH −H − Cl −C−R
4. Carbyl amine test

Isocyanide test
Aliphatic and 1° aromatic amine
Reimer tiemann reaction
intermediate CCl2 (dcc)
Reaction with nitrous acid
1° aromatic amine (diazotionsation)
2° aromatic amine / Aliphatic O O
3° aromatic R–C–
' ⊖ R–C–NHR + HCl
N
+Cl
NaNO2 + HCl + – –N2 H–N–H NHCl
R–NH2 R–N2 Cl R⊕ R–OH
HNO2 reagent
1° aliphatic H
unstable if pos.
O O
Aliphatic 3°:- +
RNH –H R–C–Cl R–C–NHR
' + HCl
⊕
NO +
O O
R3 N R3 N –NO
+
RNH –H R–C–OCOR R–C–NHR + RCOOH
CHCl3
5. Hinsberg test R–NH2 HOH
R–NC
O amine isocyanide
Ph–S–Cl Hingberg’s Reagent 2HOH
O NaNO 2 + HCl 
→ HNO 2 + NaCl
Benzene sulphonyl chloride
NaNO 2+HCl + –
Ph–NH2 PhN2 Cl
HNO 2
6. ESR
H
(i) Bromination ⊕ ⊕
NO ⊕
Ph2 –NH Ph–N–N=O Ph–N–N=O
Br2 + Cs2 – Tribromo
Ph Ph
Br2 +H2O – Tribromo Nitrosomonas
Phenol – monobromo R R R R
N N
Phenol-Tribromo
⊕
NO
ESR
NO
+M
O/P directing
1° amine
O O
R–NH2 R–NH–S–ph R–N–S–ph
O aq KOH
O O
Cl–S–ph (N-alkyl sulphoamide) (soluble)
2° amine
O
R2 NH R–N–S–ph aq KOH No reaction
O (insoluble)
RO
Cl–S–ph
(N–N dialkyl sulphoamide)
O
3° amine → No reaction
NH2 NH2
Br Br
Tribromo
Br
NH2 NH2
Br Br
Tribromo
Br
Nitration :- NO2+
To get monobromide in aniline:-
Case I :- for monobromination:-

O
CH3–C–Cl, Br+,H3O+
NH2 NH2
Br
Case II :- For mononitration
O
CH3–C–Cl, NO2+,H3O+
NH2 NH2
NO2
3. Sulphonation :-
* H2SO4, Acid Base — Zooithrtion / Bipolanion.
NH2 NH3
SO3–
* MOP of Diazonium salt :-
Ph − NH 2  → PhN 2 + HSO 4 −

NaNO
2
H SO 2 4
* Reducing Reaction:-
aq H3PO2 /
* OH
* alcohol — aldehyde.
H OH
[O] –H2O
OH OH O
Formation of nitrobenzene:-
NaBF4 / NaNO2 / Cu∆
NH2 NH2 NH2 NH2

+ NO2
NO2
+ +
NO2
NO2
2% 47%
51%
O O
NH2 O NH–C–Cl NH–C–CH3 NH2
CH3–C–Cl + +
Br H3O
acid chloride
Acetamilide Bulky so para Br
O O
NH2 NH–C–Cl NH–C–CH3
O
CH3–C–Cl NO2+
NO2
H3O+
NH2
NO2
+
NH2 NHHSO4– NH2 Base NH3
H2SO4
453-473K
SO3H Acid SO3–
Zwitor ion/ Bipolar
NaNO + HCl
* Ph – NH 2  2
0 − 5° C
→ Ph − N +2 Cl−
BDC
N +2 Cl−
Cu 2 Cl2 / HCl
* Ph – → Ph − Cl
PhN +2 Cl− 
Cu Br / HBr
* 2 2
→ Ph − Br
* PhN 2+ Cl− 
CuCN / HCN
→ Ph − CN
PhN 2+ Cl− 
Cu / H O
* 2
→ PhOH
* PhN 2+ Cl− 
Cu / HBr
→ PhBr
* PhN +2 Cl− → PhI
HI
* PhN +2 Cl− 

Cu / HCl
→ Ph − Cl
HBF4
PhN2+Cl– +
phN 2BF4
–
∆
Ph–F
PhN+2Cl– aq.H3PO2
H3PO3 + pH–H+N2
H+
OH
Ph–N+2Cl– O + ph–H+N2
NaBF4 NaNO2–
PhN+2Cl– PhN+2+BF4–
Cu/∆
Ph–NO2+N2+NaF+BF3
PhN+2Cl− + Η OH
(1)
Ph − N = N
p-hydroxyoxobenzene
(orange red)
(2)
PhN+2Cl − + Η NH2 Ph − N =N NH2

p-amino
(yellow dyl)

Hydrocarbon: Reagent - Function: Notes

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8. Halogenation [X2 /hv] • X gVkvks Gilman dk R yxkvks

13. Reaction with steam ∆

17. Allylic substitution O O

14. Internal to Terminal + Cl– –AsCl2 β

2. From phenol (Zn dust)

• Fridel craft alkylation

Directive influences of the group

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

14. Pyrolysis C6H12+H2

4. Dehydration of alcohols (E1) H

R–CH=CH2 R–CH–CH3 R–CH–CH3

[HBr/ Peroxide] Anti markovnikov's R–CH=CH2 R–CH2–CH2–Br

16. Ozonolysis [O, O, go]

17. Allylic substitution • O

b) Cyclic [Red hot tube] • R.H.T.

8. Cuprous chloride test • R − C ≡ C − H 

9. Baeyer's reagent [dil. alk. KMnO4] OH OH O O

12. Lewisite Formation • Cl– –AsCl2 β

2. From phenol (Zn dust) • Zn

• Fridel craft Acylation • O O

Directive influences of the group

• Reaction with PX3 , PX5, SOX2 •

(ii) PX5 • R–O –H

4. From Hydrohalogenation of alkenes :- • H X

R–CH=CH2 R–CH–CH3 R–CH–CH3

DMSO (Dimethyl sulphoxide) S=O

Halogenation [I2 + OA] • Ph–H

Important reaction :- • Ph–NO2

* SN1 → 2 step C+, • SN1 – Racemic

* E1cb (Elimination via conjugate base): •

3. WURTZ Fittig Reaction (Na/dry ether) • Ph–X + R–X

4. Ullmann Reaction (Cu) (Same as fittig) • 2Ph–I

5. Grignard Reaction • Mg R–MgX 50% covalent

Meisenhei mer complex

R–C=O, Acylation cation

ALCOHOL PHENOLS AND ETHER

2. HBO Hydroboration oxidation • HBO OH

2. By reduction of carboxylic acid and ester. • COOH gVkvksa CH2OH yxkvksa

* NaBH4 → mild reducing agent • H 2 / catalyst → good yield.

3. By grignard reagent • PhMgBr

(3) Diazonium salt

(4) Frome cumene

(2) Williamson ether synthesis C2H5O–NAI

3. Lucas test:- • R–OH

6. With PX3 • ROH

(2) With Conc. HNO3 [Picric acid] OH OH

5. ASPIRIN FORMATION: COOH COOH O

phOH + CCl4/HOH → salicylic acid • OH OH

8. Oxidation of phenol with Zn dust • Zn ph–H

(i) FeCl8 Test • 6 phOH

12. Elb's reaction • OH OH

3º and Reso – SN1 • ph–CH2–O–CH3

(i) Halogenation [X2/Fe]-para major •

5. Reaction with cyclic ether • H

7. REIMOR TIEMANN REACTION:

Salicylic acid o-acetyl salicylic acid

OCH3 OCH3 OCH3

OCH3 OCH3 OCH3

1. From acyl chloride

2. Addition of sodium hydrogen sulphide (NaHSO3) O

2 mole ROH Ketone — Hemi ketal