Alcohols, Phenols and Ethers

Question 1

H₃O⁺ / H⁺ + H₂O

Answer 1

Acid Hydrolysis - (markovnikov with rearrangement - Carbocation mech.)

R-CH=CH₂ → R-CH(OH)-CH₃

Question 2

1. (CH₃COO)₂Hg
2. NaBH₄/ OH⁻

Answer 2

OMDM - oxymercuration demercuration
(markovnikov with no rearrangement)

R-CH=CH₂ → R-CH(OH)-CH₃

Question 3

1. B₂H₆/THF
2. H₂O₂/ OH⁻

Answer 3

HBO - hydroboration
(Anti-Markovnikov)

R-CH=CH₂ → R-CH₂-CH₂-OH

Question 4

Reducing Agent

Answer 4

Refer the table given in notes

Question 5

Mg / Dry ether

Answer 5

Preparation of GR

R-X + Mg → R-MgX

Question 6

H₂O

Answer 6

Hydrolysis of ester in H⁺ / OH⁻ medium

RCOOR’ → RCOOH + R’OH

Question 7

aq. NaOH / 623K / 300 atm

Answer 7

Dows Process (Benzyne mechanism)

C₆H₅Cl + NaOH → C₆H₅O⁻Na⁺ + H₃O⁺→C₆H₅OH

Question 8

1. O₂
2. H₃O⁺

Answer 8

Cumene process (from Cumene Hydroperoxide)

C₆H₅CH(CH₃)₂ + O₂ →C₆H₅C(CH₃)₂OOH + H⁺ → C₆H₅OH + CH₃COCH₃

To note : Cumene → Phenol

Question 9

1. H₂S₂O₇ (Oleum)
2. NaOH / Δ
3. H₃O⁺

Answer 9

From Benzene Sulphonic acid

C₆H₆ + H₂SO₇ → C₆H₅SO₃H + NaOH / Δ → C₆H₅O⁻Na⁺ → C₆H₅OH

To note : C₆H₅SO₃H + NaOH / Δ → C₆H₅O⁻Na⁺

Question 10

1. conc. H₂SO₄ + conc. HNO₃ / 60°C
2. Sn/HCl
3. NaNO₂ + dil. HCl / 273-278 K
4. H₂O / Δ (or) dil. H₂SO₄ / 100°C

Answer 10

From BDC

C₆H₆ + c.HNO₃+c.H₂SO₄ → C₆H₅NO₂ + Sn/HCl → C₆H₅NH₂ + NaNO₂ + dil. HCl → C₆H₅N₂⁺Cl⁻ →C₆H₅OH

To note:
1. Nitration
2. Reduction
3. Diazotization
4. Hydrolysis

Question 11

1. Br₂/Fe
2. Mg/dry ether
3. O₂ (excess) / H₃O⁺

Answer 11

From GR

C₆H₆ + Br₂/Fe → C₆H₅Br + Mg → C₆H₅MgBr + O₂ + H₃O⁺→ C₆H₅OH

To note:
1. Bromination
2. Prep. of GR
3. GR →Phenol

Question 12

H₂O₂ / HSO₃F (Fluorosulphuric acid)

Answer 12

C₆H₆ + H₂O₂ + HSO₃F → C₆H₅OH

Question 13

O₂ + V₂O₅ / 315°C

Answer 13

C₆H₆ + O₂ + V₂O₅ / 315°C → C₆H₅OH

Question 14

R-OH + M →
R-OH + MH →
R-OH + MOH →

Answer 14

RO⁻M⁺ + H₂
RO⁻M⁺ + H₂
RO⁻M⁺ + H₂O

Question 15

R-OH + R’MgX

Answer 15

R’H + ROMgX

Charge separation and add

Question 16

Esterification

Answer 16

RCOOH + R’OH →RCOOR’ + H₂O

Note :
The Alcohols oxygen stay intact in the ester

one oxygen (O attached to H) from the carboxylic acid is removed as water

Question 17

PCl₅

Answer 17

RCl + POCl₃ + HCl

Question 18

PCl₃

Answer 18

ROH → RCl + H₃PO₃

Question 19

SOCl₂

Answer 19

Darzens process (SN1 - retention)

ROH → RCl + SO₂ + HCl

Both ROH and RCl are either d or l

Question 20

SOCl₂ + Py (Base)

Answer 20

Darzens process (SN2 - inversion)

ROH → Cl-R + SO₂ + HCl

Both of them are different

Question 21

Conc. H₂SO₄ / 443K

Answer 21

Dehydration

ROH → R=R (Alkene)

Carbocation mech. (Rearrangement)

Question 22

Cu + 573K

Answer 22

Dehydrohalogination

α - H elimination
1° ROH → Aldehyde + H₂
2° ROH → Ketone + H₂

β - elimination
3° ROH → Alkene + + H₂O

Question 23

KMnO₄/H⁺
K₂Cr₂O₇/H⁺

Answer 23

Strong Oxidising agent

1° ROH + MOA → aldehyde + MOA/SOA →acid

1° ROH + SOA →acid

2° ROH + M/SOA → ketone + SOA/Δ → mixture of acid

3° ROH + M/SOA →Alkene (Dehydration)

Question 24

FeSO₄/H₂O₂
CrO
MnO₂
PCC (Pyridinium chlorochromate)
PDC (pyridinium dichromate)
CAN (Ceric ammonium nitrate)

Answer 24

Mild Oxidising agent
(selective oxidation - = bond intact)

1° ROH + MOA → aldehyde + MOA/SOA →acid

1° ROH + SOA →acid

2° ROH + M/SOA → ketone + SOA/Δ → mixture of acid

3° ROH + M/SOA →Alkene (Dehydration)

Question 25

Neutral FeCl₃

Answer 25

C₆H₅OH → HCl + (C₆H₅-O-)₃-Fe [Dark violet]

Question 26

CH₃COCl

(CH₃CO)₂O

Answer 26

Acetylation

C₆H₅OH → C₆H₅OCOCH₃ (ester)

Question 27

C₆H₅-CO-Cl

Benzoyl chloride

Answer 27

Schotten Baumann rxn/Benzoylation

C₆H₅OH +C₆H₅-CO-Cl →C₆H₅-OCO-H₅C₆

Question 28

Zn / Δ

Answer 28

C₆H₅OH → C₆H₆

Question 29

Br₂ / H₂O

Answer 29

Bromination

C₆H₅OH → 2,4,6-Tribromophenol (white ppt)

Question 30

Br₂ / CS₂

Answer 30

C₆H₅OH → HO-C₆H₄-Br (o- and p-)

p- is major

Question 31

c.HNO₃ + c.H₂SO₄

Answer 31

C₆H₅OH → Picric acid (TNT)

Question 32

dil.HNO₃

Answer 32

C₆H₅OH →HO-C₆H₄-NO₂ (o- and p-)

o- is major (intramolecular H-bonding)

Question 33

H₂SO₄ + SO₃ / H₂S₂O₇

Answer 33

C₆H₅OH →HO-C₆H₄-SO₃H (p-)

only p- is formed as SO₃ is a neutral electrophile

Question 34

Anhydr. AlCl₃

Answer 34

no FC rxn

salt formation

Question 35

CHCl₃ + KOH/NaOH

Answer 35

Reimer-Teimer rxn

C₆H₅OH →HO-C₆H₄-CHO (o-salicylaldehyde)

Question 36

CCl₄ + KOH/NaOH

Answer 36

Reimer-Teimer rxn (Alteration)

C₆H₅OH →HO-C₆H₄-COOH (o-salicylic acid)

Question 37

CO₂ + NaOH

Answer 37

Kolbe’s electrolysis

C₆H₅OH →HO-C₆H₄-COOH (o-salicylic acid)

Question 38

Rxn of Salicylic acid

Answer 38

1. Acetylation [CH₃COCl / (CH₃CO)₂O]
   HO-C₆H₄-COOH → aspirin/acetylsalicylic acid

2.Benzoylation [C₆H₅
COCl]
HO-C₆H₄-COOH →Benzoyl salicylic acid

3.1 Esterification [CH₃OH/H⁺]
HO-C₆H₄-COOH →methyl salicylate (oil of wintergreen)

3.2 Esterification [C₆H₅OH/H⁺]
HO-C₆H₄-COOH → Phenyl Salicylate (salol - antiseptic)

Question 39

Na₂Cr₂O₇ / H₂SO₄

or any O.A

Answer 39

C₆H₅OH →Benzoquinone (pink)

Question 40

C₆H₅OH + Phthalic anhydride

Answer 40

phenolphthalein

Question 41

CH₄ + O₂ + Cu (573K)

Answer 41

CH₄ + O₂ + Cu (573K) → CH₃OH

Question 42

Water gas / syngas

CO₂ + 2H₂

Answer 42

CO₂ + 2H₂ → CH₃OH

Question 42

Invertase

Zymase

Answer 42

C₁₂H₆O₁₁(Sucrose) + H₂O + Invertase → C₆H₁₂O₆(Glucose) + C₆H₁₂O₆(Fructose)

C₆H₁₂O₆(Glucose) + Zymase → C₂H₅OH + CO₂