Chapter 6:

Reaction Type / Name Reagents & Notes / Observation

Conditions
R–OH + HX → R–X Alcohol → Alkyl halide Conc. HX / SN1 for 3° alcohol,
+ H₂O ZnCl₂ (Lucas SN2 for 1° alcohol.
test)
R–OH + SOCl₂ → Thionyl chloride Pyridine / dry Gaseous by-products
R–Cl + SO₂ + HCl method conditions → easy purification.
3R–OH + PCl₃ → Phosphorus trichloride Room temp Efficient alkyl chloride
3R–Cl + H₃PO₃ reaction formation.
3R–OH + PBr₃ → Phosphorus tribromide Room temp SN2 reaction;
3R–Br + H₃PO₃ reaction stereochemical
inversion occurs.
CH₂=CH₂ + HBr → Hydrohalogenation HBr gas Markovnikov addition.
CH₃–CH₂Br
CH₂=CH₂ + HBr Anti-Markovnikov ROOR / heat Radical mechanism;
(peroxide) → addition Kharasch effect.
CH₂Br–CH₃
R–Cl + NaI Finkelstein reaction Dry acetone NaCl precipitates →
(acetone) → R–I + drives reaction forward.
NaCl
R–Br + AgNO₂ → Nitrite substitution AgNO₂ in O-nitro product
R–NO₂ + AgBr ethanol dominates.
R–Br + KNO₂ → R– Alkyl nitrite formation KNO₂ Produces O-alkyl
ONO + KBr aqueous nitrite.
R–X + KCN → R– Cyanide substitution KCN in Forms nitrile → chain
CN + KX ethanol / heat extension.
R–X + AgCN → R– Iso-cyanide formation AgCN in CN binds via N →
NC + AgX ethanol isocyanide.
R–CH₂–CH₂–X + Dehydrohalogenation Alcoholic KOH Zaitsev product
alc. KOH → R– (E2) / heat favored.
CH=CH₂ + KX +
H₂O
R–X + KOH (aq.) → Hydrolysis of halides Aqueous KOH Nucleophilic
R–OH + KX substitution (SN1/SN2).
R–X + Na (dry Wurtz reaction Dry ether / Na Forms symmetrical
ether) → R–R + metal alkanes.
NaX
R–X + Mg (dry Grignard reagent Anhydrous Highly reactive
ether) → R–MgX formation ether organomagnesium
compound.
R–MgX + H₂O → Hydrolysis of Grignard Water / acid Yields alkane.
RH + Mg(OH)X reagent
C₆H₆ + Cl₂ (FeCl₃) Electrophilic FeCl₃ catalyst Aromatic substitution.
→ C₆H₅Cl + HCl chlorination
C₆H₆ + CH₃Cl Friedel-Crafts AlCl₃ Carbocation
(AlCl₃) → C₆H₅CH₃ alkylation anhydrous intermediate;
+ HCl polyalkylation possible.
C₆H₆ + CH₃COCl Friedel-Crafts AlCl₃ Forms ketone; no
(AlCl₃) → acylation anhydrous polyacylation.
C₆H₅COCH₃ + HCl
C₆H₅Cl + Na (dry Wurtz–Fittig reaction Na metal in Aryl + alkyl/aryl
ether) → C₆H₅– ether coupling.
C₆H₅ + NaCl
2 C₆H₅Cl + 2 Na → Fittig reaction Na in dry ether Diaryl formation.
C₆H₅–C₆H₅ + 2
NaCl
C₆H₅NO₂ + 3H₂ → Nitro reduction H₂ / Ni or Sn + Converts nitrobenzene
C₆H₅NH₂ + 2H₂O HCl → aniline.
C₆H₅NH₂ + NaNO₂ Diazotisation (start) NaNO₂ + HCl Forms diazonium salt
+ HCl (0–5 °C) → cold → key intermediate.
C₆H₅N₂⁺Cl⁻ +
2H₂O

Chapter 7:
Reaction Type / Name Reagents & Notes /
Conditions Observation
R–CH₂–OH → R–CH₃ Reduction of Catalytic H₂ / Ni Converts alcohols
+ H₂O Alcohols or LiAlH₄ / → alkanes.
NaBH₄
R–OH + HX → R–X + Halogenation Conc. HX / ZnCl₂ 3° > 2° > 1°
H₂O (Lucas Test) (catalyst) reactivity; SN₁/SN₂
depends on
substrate.
R–OH + SOCl₂ → R–Cl Thionyl chloride Dry pyridine / Gaseous by-
+ SO₂ + HCl method reflux products; clean
reaction.
3 R–OH + PCl₃ → 3 R– Phosphorus Room temp Used for alkyl
Cl + H₃PO₃ trichloride chlorides.
reaction
3 R–OH + PBr₃ → 3 R– Phosphorus Room temp SN₂ reaction with
Br + H₃PO₃ tribromide inversion of
reaction configuration.
2 R–OH → R–O–R + Dehydration / Conc. H₂SO₄ Intermolecular
H₂O Ether formation (413 K) dehydration; gives
ethers.
R–CH₂–CH₂–OH → R– Dehydration to Conc. H₂SO₄, Intramolecular
CH=CH₂ + H₂O alkene 443 K (heat) elimination (E1);
Zaitsev product
major.
3 C₂H₅OH + 2 CrO₃ → Oxidation Acidified Controlled oxidation
3 CH₃CHO + Cr₂O₃ + 3 (primary alcohol K₂Cr₂O₇ / forms aldehyde.
H₂O → aldehyde) KMnO₄
RCH₂OH → RCOOH Complete Strong oxidant Forms carboxylic
oxidation (K₂Cr₂O₇ / acid.
(primary alcohol) KMnO₄)
R₂CHOH → R₂CO Secondary K₂Cr₂O₇ / Forms ketone.
alcohol oxidation KMnO₄
C₆H₅OH + Br₂(aq) → Bromination of Bromine water White ppt of
2,4,6-tribromophenol + phenol tribromophenol.
3 HBr
C₆H₅OH + CHCl₃ + 3 Reimer–Tiemann CHCl₃ + aq. Forms
NaOH → o- reaction NaOH / warm salicylaldehyde (–
HOC₆H₄CHO + 3 NaCl CHO at ortho).
+ 2 H₂O
C₆H₅OH + CO₂ + Kolbe’s reaction NaOH / CO₂ Salicylic acid formed.
NaOH → o- (400 K, 4–7 atm),
HOC₆H₄COONa → o- then acidify
HOC₆H₄COOH
2 C₆H₅OH + CH₂O → Formaldehyde Conc. H₂SO₄ / Produces ortho- and
HO–C₆H₄–CH₂–C₆H₄– condensation acidic medium para-hydroxymethyl
OH + H₂O phenols.
2 C₆H₅OH + HNO₂ → Nitration / Dil. HNO₃ Forms mono- or di-
C₆H₄(OH)₂ + NO + H₂O oxidation related nitrophenols.
C₆H₅OH → p- Oxidation of Na₂Cr₂O₇ / Forms quinone
benzoquinone phenol H₂SO₄ (yellow solid).
R–O–R′ + HX → R–X + Cleavage of Conc. HX (esp. SN1 or SN2
R′–OH / R′–X + ROH ethers HI), heat depending on R-
group.
CH₃–O–CH₃ + HI → Ether cleavage HI (gas) / 373 K Stepwise formation
CH₃I + CH₃OH example of iodoalkane.
C₂H₅OH → C₂H₄ → Multi-step Dehydration, Illustrates inter-
C₂H₅Br → C₂H₅CN → conversion halogenation, conversion
CH₃CH₂CH₂NH₂ KCN, reduction pathways.

Chapter 8:
Reaction Type / Name Reagents & Notes / Observation
Conditions
R–CH₂OH → R– Oxidation PCC / CrO₃ / Controlled oxidation →
CHO (Primary alcohol K₂Cr₂O₇ aldehyde.
 → Aldehyde)
R₂CHOH → R₂CO Oxidation K₂Cr₂O₇ / Stops at ketone stage.
(Secondary KMnO₄
alcohol →
Ketone)
R–C≡CH + H₂O → Hydration of HgSO₄ / Markovnikov addition; methyl
R–CO–CH₃ Alkyne (Ketone H₂SO₄ / ketone forms.
formation) warm
RCN + 2 H₂O + H⁺ Hydrolysis of Acidic / basic Extends carbon chain.
→ R–COOH + nitrile → Acid or medium
NH₄⁺ Aldehyde
RCOCl + H₂ → R– Rosenmund Pd / BaSO₄ + Acid chloride → aldehyde; no
CHO reduction quinoline further reduction.
RCN + 2 H₂ → R– Stephen SnCl₂ + HCl, Nitrile → imine → aldehyde.
CH₂NH₂ → R– reduction then H₂O
CHO work-up
Benzene + CO + Gattermann Cu / HCl / CO Benzaldehyde formation.
HCl → C₆H₅CHO formylation / AlCl₃
C₆H₆ + CO + HClGattermann–Koch CO + HCl / Alternative formylation of
→ C₆H₅CHO reaction AlCl₃ + CuCl benzene.
catalyst
R–CHO + H₂ → Catalytic H₂ / Ni, Pt, Converts carbonyl →
R–CH₂OH reduction Pd alcohol.
R–CHO + NaBH₄ Reduction of NaBH₄ / Mild reduction to alcohol.
→ R–CH₂OH carbonyl group LiAlH₄
R–CHO → R– Clemmensen Zn–Hg / Removes O; acidic medium.
CH₂OH reduction conc. HCl
R–CO–R → R– Wolff–Kishner NH₂NH₂ / Basic medium;
CH₂–R reduction KOH / heat deoxygenation.
(glycol)
R–CHO + HCN → Cyanohydrin HCN / base Nucleophilic addition; chain
R–CH(OH)–CN formation catalyst extension.
R–CHO + NaHSO₃ Bisulphite NaHSO₃ / Used for purification of
→ R– addition room temp carbonyls.
CH(OH)SO₃Na
2 R–CHO → R– Aldol Dilute NaOH / β-Hydroxy aldehyde forms.
CH(OH)–CH₂– condensation cold
CHO
Aldol → α,β- Dehydration of Heat / acid Forms C=C bond.
unsaturated Aldol
aldehyde + H₂O
Aromatic Cross Aldol Dilute base Mixture of products.
aldehyde + condensation
aliphatic aldehyde
→ mixed aldol
2 Ar–CHO + NaOH Cannizzaro Conc. One molecule oxidised, other
→ Ar–COONa + reaction NaOH / no α- reduced.
Ar–CH₂OH H
R–CO–CH₃ + Br₂ Haloform reaction NaOH + Br₂ / Positive for methyl ketones
+ NaOH → R– warm → yellow ppt of CHBr₃.
COONa + CHBr₃
R–CHO + 2 Tollens’ test Ammoniacal Silver mirror forms; aldehyde
[Ag(NH₃)₂]⁺ + 3 AgNO₃ confirmed.
OH⁻ → R–COO⁻
+ 2 Ag + 4 NH₃ + 2
H₂O
R–CHO + 2 Cu²⁺ + Fehling’s test Fehling Brick-red ppt of Cu₂O.
5 OH⁻ → R– solution (A +
COO⁻ + Cu₂O B) / heat
(red) + 3 H₂O
CH₃COCH₃ + I₂ + Iodoform test NaOH + I₂ Yellow ppt for methyl
NaOH → CHI₃ + ketones.
CH₃COONa + H₂O
R–COOH + PCl₅ Conversion to PCl₅ / Reactive intermediate for
→ R–COCl + acid chloride anhydrous acylation.
POCl₃ + HCl
R–COOH + SOCl₂ Thionyl chloride Dry Gaseous by-products ease
→ R–COCl + SO₂ method conditions / purification.
+ HCl pyridine

⇌ R–COOR +
R–COOH + ROH Esterification Conc. H₂SO₄ Equilibrium; acid catalysed.
(Fischer–Speier) / reflux
H₂O
R–COOR + NaOH Saponification Aq. NaOH / Irreversible base-catalysed
→ R–COONa + (Hydrolysis of heat process.
ROH ester)
R–COOH + NH₃ Amide formation Heat / NH₃ Forms primary amide.
→ R–CONH₂ + excess
H₂O
2 R–COOH → (R– Acid anhydride P₂O₅ / heat Dehydration reaction.
CO)₂O + H₂O formation
R–COOH + LiAlH₄ Reduction of acid LiAlH₄ / ether Strong reduction → alcohol.
→ R–CH₂OH
R–COOH → R– Reduction to HI / Red P / Hunsdiecker/decaboxylative
CH₃ alkane heat type variant.
RCOONa + Br₂ + Hunsdiecker Na salt of Alkyl halide with 1 less C.
NaOH → R–Br + reaction acid + Br₂
Na₂CO₃ + H₂O
RCOONa + NaOH Kolbe electrolysis NaOH + CaO Forms alkane with 1 C less.
→ RH + Na₂CO₃ / Decarboxylation / heat
Ar–CHO + Wolff–Kishner on Base / heat Removes carbonyl oxygen.
NH₂NH₂ → Ar– aromatic
CH=NNH₂ → Ar– aldehydes
CH₃

Chapter 9:
Reaction Type / Name Reagents & Notes /
Conditions Observation
R–X + NH₃ → R–NH₂ Ammonolysis of Alcoholic NH₃ / SN2 reaction;
+ HX Alkyl Halides sealed tube, heat over-alkylation
possible.
R–COCl + NH₃ → R– Acylation (acid Cold NH₃ / Intermediate for
CONH₂ + HCl chloride to amide) anhydrous reduction to amine.
R–CONH₂ + Br₂ + 4 Hofmann Br₂ + NaOH / heat Amide → amine
NaOH → R–NH₂ + Bromamide with one fewer C.
Na₂CO₃ + 2 NaBr + 2 Degradation
H₂O
R–NO₂ + 3 H₂ → R– Reduction of Nitro H₂ / Ni, Sn/HCl or Nitrobenzene →
NH₂ + 2 H₂O Compounds Fe/HCl aniline; universal
prep route.
R–CN + 2 H₂ → R– Catalytic H₂ / Ni, Pd or LiAlH₄ Extends carbon
CH₂NH₂ hydrogenation of chain by 1.
nitriles
R–CONH₂ + LiAlH₄ Reduction of LiAlH₄ / dry ether Primary amine
→ R–CH₂NH₂ amide formed.
R–N₂⁺Cl⁻ + H₃PO₂ Reduction of Hypophosphorous Deamination;
→ R–H + H₃PO₃ + N₂ diazonium salt acid removes –NH₂
group.
C₆H₅NH₂ + CH₃COCl Acetylation of Pyridine / anhydrous Deactivates amine
→ C₆H₅NHCOCH₃ + amine conditions (↓ basicity).
HCl
RNH₂ + HNO₂ → Reaction with NaNO₂ + HCl (in Brisk
ROH + N₂ + H₂O nitrous acid (1° situ, 273–278 K) effervescence
aliphatic amine) (N₂); test for 1°
amine.
R₂NH + HNO₂ → Reaction with 273–278 K Yellow oily
R₂N–NO + H₂O nitrous acid (2° nitrosoamine
amine) forms.
R₃N + HNO₂ → no Tertiary amine — Distinguishes 3°
reaction test amine (no gas, no
oil).
C₆H₅NH₂ + NaNO₂ + Diazotisation 273–278 K, NaNO₂ Forms diazonium
HCl (0–5 °C) → + HCl salt; unstable
C₆H₅N₂⁺Cl⁻ + 2 H₂O above 5 °C.
C₆H₅N₂⁺Cl⁻ + H₃PO₂ Reduction Hypophosphorous Deamination.
→ C₆H₆ + N₂ + (diazonium → acid
H₃PO₃ benzene)
C₆H₅N₂⁺Cl⁻ + H₂O Hydrolysis of Warm water Forms phenol.
→ C₆H₅OH + HCl + diazonium salt
N₂
C₆H₅N₂⁺Cl⁻ + CuCN Sandmeyer CuCN / HCl Diazonium
→ C₆H₅CN + CuCl + Reaction replaced by –CN.
N₂
C₆H₅N₂⁺Cl⁻ + CuCl Sandmeyer CuCl / HCl Forms
→ C₆H₅Cl + CuCl₂ + Reaction (chloro) chlorobenzene.
N₂
C₆H₅N₂⁺Cl⁻ + CuBr Sandmeyer CuBr / HBr Bromobenzene
→ C₆H₅Br + CuBr₂ + Reaction (bromo) formed.
N₂
C₆H₅N₂⁺Cl⁻ + KI → Iodination KI No Cu⁺ needed;
C₆H₅I + KCl + N₂ (Gattermann direct iodination.
variant)
C₆H₅N₂⁺Cl⁻ + HBF₄ Balz–Schiemann HBF₄ then heat Fluorobenzene
→ C₆H₅BF₄ →(Δ)→ Reaction synthesis.
C₆H₅F + BF₃ + N₂
C₆H₅N₂⁺Cl⁻ + Gattermann Cu / HCl Simpler form of
Cu/HCl → C₆H₅Cl + Reaction Sandmeyer.
N₂
C₆H₅N₂⁺Cl⁻ + Azo coupling pH ~ 8 (alkaline) Produces
C₆H₅OH → C₆H₅– reaction orange/yellow azo
N=N–C₆H₄OH dye.
R–NH₂ + CHCl₃ + 3 Carbylamine CHCl₃ + alcoholic Unpleasant odour;
KOH → R–NC + 3 (Isocyanide) KOH test for 1° amines.
KCl + 3 H₂O reaction
RNH₂ + R′–COCl → Acylation Acid chloride / Converts amine →
R–NH–CO–R′ + HCl pyridine amide.
RNH₂ + R′–X → R– Alkylation Alkyl halide / mild Successive
NHR′ / R–NR′₂ heat alkylations
possible.
R₄N⁺OH⁻ (heated) Hofmann Heat quaternary Forms least
elimination ammonium substituted alkene.
→ R′–CH=CH₂ + R₃N hydroxide
+ H₂O
C₆H₅NO₂ + 3 H₂ → Nitrobenzene Sn/HCl or Fe/HCl Common lab prep
C₆H₅NH₂ + 2 H₂O reduction of aniline.
C₆H₅NH₂ + NaNO₂ + Diazotisation Cold conditions Key step in
HCl (0–5 °C) → (again) aromatic
C₆H₅N₂⁺Cl⁻ substitution
chemistry.

PREPARATION:
Compound Preparation Reagents / Notes / Observation
Reaction Conditions
Haloalkanes Alcohol → Alkyl Conc. HX / ZnCl₂ SN1 (3°) or SN2 (1°);
(R–X) halide (Lucas reagent) test for alcohol
classification.
Alcohol → Alkyl SOCl₂ / Pyridine (dry) By-products gaseous
 chloride (SO₂ + HCl).
Alcohol → Alkyl PBr₃ / Room temp Clean SN2
bromide mechanism, inversion
of configuration.
Alcohol → Alkyl Red P + I₂ (HI in situ) Gentle heating.
iodide
Alkene → Alkyl HX / room temp Follows Markovnikov’s
halide rule.
Alkene → Alkyl HBr / ROOR / heat Radical addition
halide (Anti- (Kharasch effect).
Markovnikov)
Alkane → Alkyl X₂ / hv (free-radical Mixture of products,
halide substitution) photochemical.
Carboxylic acid → RCOONa + Br₂ + Decarboxylative
Alkyl halide NaOH → R–Br halogenation.
(Hunsdiecker)
Alkene + Halogen Cl₂ / Br₂ in CCl₄ Anti addition,
→ Dihaloalkane decolorisation test for
unsaturation.
Haloarenes Benzene → Cl₂ / FeCl₃ (cat.) Electrophilic
(Ar–X) Chlorobenzene substitution;
ortho/para directing.
Benzene → Br₂ / FeBr₃ (cat.) Room temperature;
Bromobenzene aromatic substitution.
Aniline → Sandmeyer / Via diazonium salt;
Haloarene Gattermann reactions replaces –N₂⁺Cl⁻ by
halogen.
Alcohols (R– Alkene → Alcohol Dil. H₂SO₄ Markovnikov addition.
OH) (hydration)
Carbonyl NaBH₄ / LiAlH₄ Reduction step.
compound →
Alcohol
Haloalkane → Aq. KOH SN1/SN2 substitution.
Alcohol
Grignard reagent + RMgX + R′CHO / R Primary, secondary,
Carbonyl → ′CO → R′CH(OH)R or tertiary depending
 Alcohol on carbonyl.
Fermentation of Yeast / anaerobic Ethanol + CO₂.
glucose
Phenols (Ar– Chlorobenzene → NaOH (623 K, 300 Dow process.
OH) Phenol atm) → acidify
Benzene → via nitration → Stepwise method.
Phenol reduction →
diazotisation →
hydrolysis
Ethers (R–O–R Alcohol → Ether Conc. H₂SO₄ (413 K) Intermolecular
′) dehydration.
Alkoxide + Alkyl Williamson synthesis SN2; gives
halide → Ether (RONa + R′X) asymmetrical ethers.
Aldehydes (R– Primary alcohol → PCC / CrO₃ Avoid over-oxidation.
CHO) Aldehyde (controlled)
Acid chloride → Rosenmund Selective
Aldehyde reduction (H₂ / Pd- hydrogenation.
BaSO₄)
Nitrile → Aldehyde Stephen reduction Chain extension by
(SnCl₂ + HCl, then one C.
H₂O)
Benzene → Gattermann–Koch or Electrophilic
Benzaldehyde Gattermann (CO + formylation.
HCl / AlCl₃ + CuCl)
Ketones (R– Secondary alcohol K₂Cr₂O₇ / KMnO₄ Controlled oxidation.
CO–R′) → Ketone
Alkyne → Ketone H₂O / H₂SO₄ / Markovnikov
HgSO₄ hydration.
Acid chloride + RCOCl + R′₂CuLi Useful synthetic route.
organocuprate →
Ketone
Carboxylic Primary alcohol / K₂Cr₂O₇ / KMnO₄ Complete oxidation.
acids (R– Aldehyde → Acid
COOH)
Nitrile → Acid Acidic / basic Chain length +1.
 hydrolysis
Grignard reagent + RMgX + CO₂ → Carboxylation.
CO₂ RCOOH (acid work-
up)
Amines (R– Nitro compound → Sn / HCl or Fe / HCl Reduction.
NH₂) Amine or H₂ / Ni
Amide → Amine Hofmann bromamide 1 C shorter.
degradation (Br₂ +
NaOH)
Nitrile → Amine LiAlH₄ / H₂ + Ni 1 C longer.
Alkyl halide → Ammonolysis (NH₃ / SN2; mixture of
Amine heat / sealed tube) amines.
Diazonium salt → Reduction (H₃PO₂ or Deamination or
Amine SnCl₂) regeneration of amine.

CONVERSIONS:

Starting Target Conversion Reagents Reaction Important

Compou Compou Type & Notes
nd nd Condition
s
ALCOHO Alkyl Halogenatio Conc. R-OH + HX → R-X + SN1 for 3°,
LS Halides n HX/ZnCl₂ H₂O SN2 for 1°
(Lucas)
ALCOHO Alkyl Thionyl SOCl₂/ R-OH + SOCl₂ → R-Cl Gaseous by-
LS Chloride chloride Pyridine/ + SO₂ + HCl products
s dry
ALCOHO Alkyl PBr₃ method PBr₃/room 3R-OH + PBr₃ → 3R- SN2 with
LS Bromide temp Br + H₃PO₃ inversion
 s
ALCOHO Alkenes Dehydration Conc. R-CH₂-CH₂-OH → R- Intramolecul
LS H₂SO₄/443 CH=CH₂ + H₂O ar
K elimination
ALCOHO Ethers Dehydration Conc. 2R-OH → R-O-R + Intermolecul
LS H₂SO₄/413 H₂O ar
K
1° Aldehyd Controlled PCC/CrO₃ R-CH₂-OH → R-CHO Avoid over-
ALCOHO es oxidation oxidation
LS
1° Carboxy Strong K₂Cr₂O₇/ R-CH₂-OH → R-COOH Complete
ALCOHO lic acids oxidation KMnO₄ oxidation
LS
2° Ketones Oxidation K₂Cr₂O₇/ R₂CH-OH → R₂C=O Stops at
ALCOHO KMnO₄ ketone stage
LS
ALCOHO Esters Esterificatio RCOOH/ R-OH + R'COOH → Fischer-
LS n H⁺/heat R'COOR + H₂O Speier
method
PHENOL 2,4,6- Bromination Br₂ water C₆H₅OH + 3Br₂ → White
S Tribrom C₆H₂Br₃OH + 3HBr precipitate
ophenol
PHENOL Salicylal Reimer- CHCl₃+NaO C₆H₅OH + CHCl₃ + -CHO at
S dehyde Tiemann H/warm 3NaOH → o- ortho
HOC₆H₄CHO + 3NaCl position
+ 2H₂O
PHENOL Salicylic Kolbe's CO₂+NaOH C₆H₅OH + CO₂ + Ortho-
S acid reaction /heat, then NaOH → o- hydroxybenz
H⁺ HOC₆H₄COONa → o- oic acid
HOC₆H₄COOH
ETHERS Alkyl Cleavage HI/heat R-O-R' + HI → R-I + Stepwise
halides R'-OH reaction
+
 Alcohols
ALKENES Alkyl Hydrohaloge HX/room R-CH=CH₂ + HX → Markovnikov
halides nation temp R-CHX-CH₃ addition
ALKENES Alkyl Anti- HBr/ R-CH=CH₂ + HBr → Radical
halides Markovnikov ROOR/heat R-CH₂-CH₂Br mechanism
ALKENES Alcohols Hydration Dil. H₂SO₄ R-CH=CH₂ + H₂O → Markovnikov
R-CH(OH)-CH₃ addition
ALKYNE Ketones Hydration H₂O/ R-C≡CH + H₂O → R- Markovnikov
S H₂SO₄/ CO-CH₃ addition
HgSO₄
ALKYL Alkenes Dehydrohalo Alc. R-CH₂-CH₂-X → R- Zaitsev
HALIDES genation KOH/heat CH=CH₂ + KX + H₂O product
favored
ALKYL Alkanes Wurtz Na/dry 2R-X + 2Na → R-R + Symmetrical
HALIDES reaction ether 2NaX alkane
ALKYL Nitriles Cyanide KCN/ R-X + KCN → R-CN + Chain
HALIDES substitution ethanol/ KX extension
heat +1C
ALKYL Amines Ammonolysi NH₃/ R-X + NH₃ → R-NH₂ Mixture of
HALIDES s ethanol/ + HX amines
heat
ALKYL Grignar Grignard Mg/dry R-X + Mg → R-MgX Highly
HALIDES d formation ether reactive
reagent
s
ALKYL Alcohols Hydrolysis Aq. KOH R-X + KOH → R-OH SN1/SN2
HALIDES + KX substitution
ALKYL Alkyl Finkelstein NaI/dry R-Cl + NaI → R-I + NaCl
CHLORID iodides acetone NaCl precipitates
ES
BENZEN Chlorob Electrophilic Cl₂/FeCl₃ C₆H₆ + Cl₂ → C₆H₅Cl Ortho/para
E enzene substitution + HCl directing
BENZEN Bromob Electrophilic Br₂/FeBr₃ C₆H₆ + Br₂ → C₆H₅Br Room
E enzene substitution + HBr temperature
BENZEN Toluene Friedel- CH₃Cl/AlCl₃ C₆H₆ + CH₃Cl → Polyalkylatio
E Crafts C₆H₅CH₃ + HCl n possible
alkylation
BENZEN Acetoph Friedel- CH₃COCl/ C₆H₆ + CH₃COCl → No
E enone Crafts AlCl₃ C₆H₅COCH₃ + HCl polyacylation
acylation
BENZEN Benzald Gattermann- CO+HCl/ C₆H₆ + CO + HCl → Formylation
E ehyde Koch AlCl₃+CuCl C₆H₅CHO
NITROBE ANILINE Reduction Sn+HCl or C₆H₅NO₂ + 3H₂ → Universal
NZENE Fe+HCl or C₆H₅NH₂ + 2H₂O method
H₂/Ni
ALDEHY Alcohols Reduction NaBH₄/ R-CHO + 2[H] → R- Mild to
DES LiAlH₄ CH₂OH strong
reduction
ALDEHY Carboxy Oxidation K₂Cr₂O₇/ R-CHO + [O] → R- Complete
DES lic acids KMnO₄ COOH oxidation
ALDEHY Hydroca Clemmense Zn-Hg/ R-CHO + 4[H] → R- Acidic
DES rbons n reduction conc. HCl CH₃ + H₂O deoxygenatio
n
ALDEHY Hydroca Wolff- NH₂NH₂/ R-CHO → R-CH₃ + N₂ Basic
DES rbons Kishner KOH/ deoxygenatio
glycol/heat n
ALDEHY Cyanohy Nucleophilic HCN/base R-CHO + HCN → R- Chain
DES drins addition catalyst CH(OH)-CN extension
ALDEHY Bisulphi Nucleophilic NaHSO₃ R-CHO + NaHSO₃ → Purification
DES te addition R-CH(OH)-SO₃Na method
adduct
ALDEHY Aldols Aldol Dil. 2R-CHO → R- β-Hydroxy
DES condensatio NaOH/cold CH(OH)-CH₂-CHO aldehyde
n
ALDEHY Alcohol Cannizzaro Conc. 2R-CHO + NaOH → Disproportion
DES (no + Acid NaOH R-COONa + R- ation
α-H) salt CH₂OH
KETONE Alcohols Reduction NaBH₄/ R₂C=O + 2[H] → Secondary
S LiAlH₄ R₂CH-OH alcohols
KETONE Hydroca Clemmense Same as R₂C=O → R₂CH₂ Deoxygenati
S rbons n/Wolf- aldehydes on
Kishner
METHYL Carboxy Haloform NaOH+Br₂/ R-CO-CH₃ + 3Br₂ + Chain
KETONE lic acids reaction warm 4NaOH → R-COONa shortening
S + CHBr₃ + 3NaBr + by 1C
3H₂O
ACID Aldehyd Rosenmund H₂/Pd- R-COCl + H₂ → R- Selective
CHLORID es reduction BaSO₄/ CHO + HCl hydrogenatio
ES quinoline n
ACID Esters Esterificatio ROH/ R-COCl + R'OH → R- Acylation
CHLORID n Pyridine COOR' + HCl
ES
ACID Amides Aminolysis NH₃ or R-COCl + 2NH₃ → R- Primary/
CHLORID RNH₂ CONH₂ + NH₄Cl secondary
ES amides
CARBOX Acid Halogenatio SOCl₂/PCl₅ R-COOH + SOCl₂ → Reactive
YLIC chloride n R-COCl + SO₂ + HCl intermediate
ACIDS s s
CARBOX Esters Esterificatio ROH/H⁺/ R-COOH + R'OH → Fischer-
YLIC n heat R-COOR' + H₂O Speier
ACIDS
CARBOX Amides Amidation NH₃/heat R-COOH + NH₃ → R- Primary
YLIC CONH₂ + H₂O amides
ACIDS
CARBOX Alcohols Reduction LiAlH₄/ R-COOH + 4[H] → R- Strong
YLIC ether CH₂OH + H₂O reduction
ACIDS
NITRILES Aldehyd Stephen SnCl₂+HCl, R-CN + 2[H] → R- Imine
es reduction then H₂O CH=NH → R-CHO intermediate
NITRILES Carboxy Hydrolysis Acidic/ R-CN + 2H₂O → R- Chain length
lic acids basic COOH + NH₃ +1
hydrolysis
NITRILES Amines Reduction LiAlH₄ or R-CN + 4[H] → R- Chain
H₂/Ni CH₂-NH₂ extension by
1C
AMIDES Amines Hofmann Br₂+NaOH R-CONH₂ + Br₂ + Chain
degradation 4NaOH → R-NH₂ + SHORTENING
Na₂CO₃ + 2NaBr + by 1C
2H₂O
PRIMAR Isocyani Carbylamine CHCl₃+alc. R-NH₂ + CHCl₃ + Foul smell -
Y des reaction KOH/heat 3KOH → R-NC + identification
AMINES 3KCl + 3H₂O test
ANILINE Diazoni Diazotizatio NaNO₂+HC C₆H₅NH₂ + NaNO₂ + Key
um salt n l/0-5°C 2HCl → C₆H₅N₂⁺Cl⁻ + intermediate
NaCl + 2H₂O
DIAZONI Chlorob Sandmeyer CuCl/HCl C₆H₅N₂⁺Cl⁻ + CuCl → Aromatic
UM SALT enzene reaction C₆H₅Cl + N₂ + CuCl₂ substitution
DIAZONI Bromob Sandmeyer CuBr/HBr C₆H₅N₂⁺Cl⁻ + CuBr → Aromatic
UM SALT enzene reaction C₆H₅Br + N₂ + CuBr₂ substitution
DIAZONI Benzoni Sandmeyer CuCN/KCN C₆H₅N₂⁺Cl⁻ + CuCN -CN group
UM SALT trile reaction → C₆H₅CN + N₂ + introduction
CuCl
DIAZONI Iodoben Iodination KI C₆H₅N₂⁺Cl⁻ + KI → No copper
UM SALT zene C₆H₅I + KCl + N₂ catalyst
needed
DIAZONI Fluorob Balz- HBF₄, then C₆H₅N₂⁺Cl⁻ + HBF₄ → Fluorination
UM SALT enzene Schiemann heat C₆H₅N₂⁺BF₄⁻ → C₆H₅F method
+ BF₃ + N₂
DIAZONI Benzene Reduction H₃PO₂ C₆H₅N₂⁺Cl⁻ + H₃PO₂ Deamination
UM SALT + H₂O → C₆H₆ +
H₃PO₃ + HCl + N₂
DIAZONI Phenol Hydrolysis H₂O/warm C₆H₅N₂⁺Cl⁻ + H₂O → Replacement
UM SALT C₆H₅OH + HCl + N₂ by -OH
DIAZONI Azo dye Coupling Phenol/ C₆H₅N₂⁺Cl⁻ + Colored
UM SALT reaction alkaline pH C₆H₅OH → C₆H₅- compounds
N=N-C₆H₄OH + HCl
AMINES Amides Acylation RCOCl/ R-NH₂ + R'COCl → R- Protection of
Pyridine NH-COR' + HCl amine group
GRIGNA Alcohols Carbonyl R'CHO/ R-MgX + R'CHO → Primary/
RD addition R'COR/ R'-CH(OH)-R secondary/
REAGEN HCHO tertiary
TS alcohols
GRIGNA Carboxy CO₂ addition CO₂, then R-MgX + CO₂ → R- Carboxylatio
RD lic acids H₃O⁺ COOH n
REAGEN
TS
ESTERS Carboxy Hydrolysis H⁺ or R-COOR' + H₂O → R- Acidic or
lic acids OH⁻/heat COOH + R'OH basic
hydrolysis

SPECIAL IDENTIFICATION TESTS SUMMARY

Test For Reagents Positive Reaction
Observation
1°, 2°, 3° Lucas reagent 3°: immediate R-OH + HCl → R-Cl + H₂O
Alcohols (ZnCl₂+[Link]) turbidity, 2°: 5-10
min, 1°: no turbidity
Aldehydes Tollens' reagent Silver mirror R-CHO + 2[Ag(NH₃)₂]⁺ +
 3OH⁻ → R-COO⁻ + 2Ag +
4NH₃ + 2H₂O
Aldehydes Fehling's solution Brick red precipitate R-CHO + 2Cu²⁺ + 5OH⁻ → R-
(aliphatic) COO⁻ + Cu₂O + 3H₂O
Methyl Iodoform test Yellow precipitate of R-CO-CH₃ + 3I₂ + 4NaOH →
ketones CHI₃ R-COONa + CHI₃ + 3NaI +
3H₂O
Phenols Neutral FeCl₃ Violet coloration 6C₆H₅OH + Fe³⁺ →
[Fe(OC₆H₅)₆]³⁻ + 6H⁺ (violet
complex)
Carboxylic NaHCO₃ Effervescence (CO₂) R-COOH + NaHCO₃ → R-
acids COONa + CO₂ + H₂O
Primary Carbylamine Foul smelling R-NH₂ + CHCl₃ + 3KOH → R-
amines reaction isocyanide NC + 3KCl + 3H₂O
Aniline Azo dye test Orange/red dye C₆H₅N₂⁺Cl⁻ + C₆H₅NH₂ →
formation C₆H₅-N=N-C₆H₄NH₂ + HCl
Unsaturati Br₂ in CCl₄ Decolorization R-CH=CH-R + Br₂ → R-CHBr-
on CHBr-R