Alcohols, Phenols and Ethers Flashcards
H₃O⁺ / H⁺ + H₂O
Acid Hydrolysis - (markovnikov with rearrangement - Carbocation mech.)
R-CH=CH₂ → R-CH(OH)-CH₃
- (CH₃COO)₂Hg
- NaBH₄/ OH⁻
OMDM - oxymercuration demercuration
(markovnikov with no rearrangement)
R-CH=CH₂ → R-CH(OH)-CH₃
- B₂H₆/THF
- H₂O₂/ OH⁻
HBO - hydroboration Oxidation
(Anti-Markovnikov)
R-CH=CH₂ → R-CH₂-CH₂-OH
Reducing Agent
Refer the table given in notes
Mg / Dry ether
Preparation of GR
R-X + Mg → R-MgX
H₂O
Hydrolysis of ester in H⁺ / OH⁻ medium
RCOOR’ → RCOOH + R’OH
aq. NaOH / 623K / 300 atm
Dows Process (Benzyne mechanism)
C₆H₅Cl + NaOH → C₆H₅O⁻Na⁺ + H₃O⁺→C₆H₅OH
- O₂
- H₃O⁺
Cumene process (from Cumene Hydroperoxide)
C₆H₅CH(CH₃)₂ + O₂ →C₆H₅C(CH₃)₂OOH + H⁺ → C₆H₅OH + CH₃COCH₃
To note : Cumene → Phenol
- H₂S₂O₇ (Oleum)
- NaOH / Δ
- H₃O⁺
From Benzene Sulphonic acid
C₆H₆ + H₂SO₇ → C₆H₅SO₃H + NaOH / Δ → C₆H₅O⁻Na⁺ → C₆H₅OH
To note : C₆H₅SO₃H + NaOH / Δ → C₆H₅O⁻Na⁺
- conc. H₂SO₄ + conc. HNO₃ / 60°C
- Sn/HCl
- NaNO₂ + dil. HCl / 273-278 K
- H₂O / Δ (or) dil. H₂SO₄ / 100°C
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
- Br₂/Fe
- Mg/dry ether
- O₂ (excess) / H₃O⁺
From GR
C₆H₆ + Br₂/Fe → C₆H₅Br + Mg → C₆H₅MgBr + O₂ + H₃O⁺→ C₆H₅OH
To note:
1. Bromination
2. Prep. of GR
3. GR →Phenol
H₂O₂ / HSO₃F (Fluorosulphuric acid)
C₆H₆ + H₂O₂ + HSO₃F → C₆H₅OH
O₂ + V₂O₅ / 315°C
C₆H₆ + O₂ + V₂O₅ / 315°C → C₆H₅OH
R-OH + M →
R-OH + MH →
R-OH + MOH →
RO⁻M⁺ + H₂
RO⁻M⁺ + H₂
RO⁻M⁺ + H₂O
R-OH + R’MgX
R’H + ROMgX
Charge separation and add
Esterification
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
PCl₅
RCl + POCl₃ + HCl
PCl₃
ROH → RCl + H₃PO₃
SOCl₂
Darzens process (SN1 - retention)
ROH → RCl + SO₂ + HCl
Both ROH and RCl are either d or l
SOCl₂ + Py (Base)
Darzens process (SN2 - inversion)
R-OH → Cl-R + SO₂ + HCl
Conc. H₂SO₄ / 443K
Dehydration
ROH → R=R (Alkene)
Carbocation mech. (Rearrangement)
Cu + 573K
Dehydrohalogination
α - H elimination
1° ROH → Aldehyde + H₂
2° ROH → Ketone + H₂
β - elimination
3° ROH → Alkene + + H₂O
KMnO₄/H⁺
K₂Cr₂O₇/H⁺
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)
FeSO₄/H₂O₂
CrO
MnO₂
PCC (Pyridinium chlorochromate)
PDC (pyridinium dichromate)
CAN (Ceric ammonium nitrate)
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)
Neutral FeCl₃
C₆H₅OH → HCl + (C₆H₅-O-)₃-Fe [Dark violet]
CH₃COCl
(CH₃CO)₂O
Acetylation
C₆H₅OH → C₆H₅OCOCH₃ (ester)
C₆H₅-CO-Cl
Benzoyl chloride
Schotten Baumann rxn/Benzoylation
C₆H₅OH +C₆H₅-CO-Cl →C₆H₅-OCO-H₅C₆
Zn / Δ
C₆H₅OH → C₆H₆
Br₂ / H₂O
Bromination
C₆H₅OH → 2,4,6-Tribromophenol (white ppt)
Br₂ / CS₂
C₆H₅OH → HO-C₆H₄-Br (o- and p-)
p- is major
c.HNO₃ + c.H₂SO₄
C₆H₅OH → Picric acid
dil.HNO₃
C₆H₅OH →HO-C₆H₄-NO₂ (o- and p-)
o- is major (intramolecular H-bonding)
H₂SO₄ + SO₃ / H₂S₂O₇
C₆H₅OH →HO-C₆H₄-SO₃H (p-)
only p- is formed as SO₃ is a neutral electrophile
Anhydr. AlCl₃
no FC rxn
salt formation
CHCl₃ + KOH/NaOH
Reimer-Teimer rxn
C₆H₅OH →HO-C₆H₄-CHO (o-salicylaldehyde)
CCl₄ + KOH/NaOH
Reimer-Teimer rxn (Alteration)
C₆H₅OH →HO-C₆H₄-COOH (o-salicylic acid)
CO₂ + NaOH
Kolbe’s electrolysis
C₆H₅OH →HO-C₆H₄-COOH (o-salicylic acid)
Rxn of Salicylic acid
- 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)
Na₂Cr₂O₇ / H₂SO₄
or any O.A
C₆H₅OH →Benzoquinone (pink)
C₆H₅OH + Phthalic anhydride
phenolphthalein
CH₄ + O₂ + Cu (573K)
CH₄ + O₂ + Cu (573K) → CH₃OH
Water gas / syngas
CO₂ + 2H₂
CO₂ + 2H₂ → CH₃OH
Invertase
Zymase
C₁₂H₆O₁₁(Sucrose) + H₂O + Invertase → C₆H₁₂O₆(Glucose) + C₆H₁₂O₆(Fructose)
C₆H₁₂O₆(Glucose) + Zymase → C₂H₅OH + CO₂
Glycerol + 3HNO₃
CH₂(OH)-CH(OH)-CH₂(OH) + 3HNO₃ → Tri Nitro Glycerine
Nitro Glycerine + Kieselguhr → Dynamite
conc. H₂SO₄ / 413 K
ROH → ROR + H₂O
Glycerol + HI (excess)
Glycerol + HI (excess) → CH₃-CHI-CH₃
ROH + CH₂N₂
ROH + CH₂N₂ → CH₃-O-R + N₂
RX + NaOR’
Williamson ether synthesis (SN2)
RX + NaOR’ → ROR + NaX
If R is less bulky = SN2 and form ether
If R is more bulky = E2 and form alkene
R’ can be bulky
RX + Ag₂O
RX + Ag₂O → ROR + AgX
ROR + [O]
Oxidation of ether
ROR + [O]→RO(O)R (peroxy ether)
ROR’ + HX
Refer notes
SN2 - if 1°, 2°, methyl (Less bulky)
SN1 - if 3°, allyl, benzyl (Stable CC)
C₆H₅OCH₃ - anisole
o- , p- directing group
note : C₆H₅OCH₂CH₃ - phenetole
Epoxides
Refer notes
Victor Meyer Test
1° Alcohol - Red (Blood)
2° Alcohol - Blue
3° Alcohol - Colorless (White)
Hint : RBC
