Chapter summaries, must-reads, tips, tricks and reaction patterns for all 5 organic chapters — Haloalkanes to Biomolecules.
| Concept | Key Fact | Example |
|---|---|---|
| Alkyl halide order (SN1) | 3° > 2° > 1° — more substituted = more stable carbocation | (CH₃)₃CBr > (CH₃)₂CHBr > CH₃CH₂Br |
| Alkyl halide order (SN2) | 1° > 2° > 3° — less steric hindrance = easier backside attack | CH₃Br reacts fastest with SN2 |
| Halogen leaving group order | I⁻ > Br⁻ > Cl⁻ > F⁻ — iodide is best leaving group (weakest C–I bond) | RI most reactive; RF least reactive |
| SN1 stereochemistry | Flat carbocation attacked from both sides → racemic mixture (50:50 R:S) | (R)-2-bromobutane → racemic butan-2-ol |
| SN2 stereochemistry | Backside attack → complete inversion of configuration (Walden inversion) | (R) → (S) product exclusively |
| Elimination vs Substitution | High temperature + strong bulky base → E2 elimination (alkene). Low T + strong small nucleophile → SN2 | KOH/alc. → alkene; KOH/aq. → alcohol |
| Haloarenes — less reactive | C–X bond has partial double bond character (resonance). Carbon is sp² (less electron-dense). Ion pair formation (SN1) not favoured. | C₆H₅Cl won't react with KOH (aq.) easily |
| Finkelstein reaction | R–Cl + NaI (dry acetone) → R–I + NaCl↓ (NaCl insoluble drives reaction) | Converts chloroalkane to iodoalkane |
| Swarts reaction | R–Cl + AgF → R–F + AgCl↓ (to make fluoroalkane) | Useful since direct fluorination is explosive |
| SN1 | SN2 | |
|---|---|---|
| Steps | 2 (slow + fast) | 1 (concerted) |
| Rate law | k[RX] | k[RX][Nu⁻] |
| Intermediate | Carbocation | Transition state |
| Substrate | 3° (stable C⁺) | 1° (less hindrance) |
| Stereochem | Racemisation | Inversion (R↔S) |
| Solvent | Polar protic | Polar aprotic |
| Nucleophile | Weak (H₂O) | Strong (CN⁻, OH⁻) |
Finkelstein: NaI/acetone → makes R–I (NaCl precipitates, drives reaction forward)
Swarts: Metal fluorides (AgF, SbF₃) → makes R–F
Wurtz: 2 RX + Na → R–R (chain doubling)
| Concept | Key Fact / Reaction | Example |
|---|---|---|
| Acidic strength | RCOOH (pKa≈5) > PhOH (pKa≈10) > ROH (pKa≈16) > H₂O (pKa≈15.7) | Phenol > ethanol because phenoxide ion is resonance-stabilised |
| Effect of ring substituents on phenol acidity | Electron-withdrawing groups (–NO₂, –Cl) → increase acidity; Electron-donating (+CH₃, +OH) → decrease acidity | 4-nitrophenol is more acidic than phenol |
| Oxidation of 1° alcohol | PCC/CrO₃ → aldehyde (stops here); K₂Cr₂O₇/H⁺ → carboxylic acid (goes further) | CH₃CH₂OH → CH₃CHO (PCC) → CH₃COOH (K₂Cr₂O₇) |
| Oxidation of 2° alcohol | Any oxidising agent → ketone | (CH₃)₂CHOH → CH₃COCH₃ (propan-2-one) |
| 3° alcohol | Resistant to mild oxidation (no α-H on C bearing OH) | (CH₃)₃COH → no reaction with PCC |
| Dehydration of alcohol | Conc. H₂SO₄, 170°C → alkene (intramolecular); 140°C → ether (intermolecular) | CH₃CH₂OH → CH₂=CH₂ (170°C) or CH₃CH₂–O–CH₂CH₃ (140°C) |
| Kolbe's reaction | Sodium phenoxide + CO₂ (300°C, high pressure) → sodium salicylate → salicylic acid (aspirin precursor) | PhONa + CO₂ → o-HOC₆H₄COONa |
| Reimer-Tiemann reaction | Phenol + CHCl₃/NaOH → o-hydroxybenzaldehyde (salicylaldehyde); CHCl₃ forms dichlorocarbene (:CCl₂) which is the electrophile | PhOH + CHCl₃ + NaOH → 2-hydroxybenzaldehyde |
| Williamson synthesis | R'–ONa + R–X (1° alkyl halide) → R'–O–R (ether) | C₂H₅ONa + CH₃I → C₂H₅OCH₃ (methoxyethane) |
| Lucas test | Conc. HCl + ZnCl₂. 3°: turbidity immediately. 2°: 5 min. 1°: no turbidity at RT. | Turbidity = insoluble alkyl chloride formed |
💡 Rule: Anything stabilising the conjugate base (anion) increases acid strength. EWG stabilise, EDG destabilise.
| Reaction / Test | Reagent / Condition | Result |
|---|---|---|
| Tollens test | Ag(NH₃)₂⁺ (silver ammonia solution), warm | Aldehyde → silver mirror on tube wall. Ketone → no reaction. |
| Fehling's test | Cu²⁺ (Fehling A + B), warm | Aliphatic aldehyde → brick red Cu₂O↓. Aromatic aldehyde (PhCHO) → no reaction. Fructose → positive. |
| 2,4-DNP test | 2,4-dinitrophenylhydrazine | Both aldehydes AND ketones → yellow/orange precipitate (2,4-DNP derivative). Identifies C=O. |
| Iodoform test | I₂/NaOH, warm | CH₃CHO, CH₃COR, CH₃CH(OH)R → yellow CHI₃↓ + antiseptic smell. HCHO → no iodoform. |
| HCN addition | HCN + NaCN catalyst | → Cyanohydrin; R–CH(OH)CN. Hydrolyse → α-hydroxy acid. +1 carbon. |
| NaHSO₃ addition | Saturated sodium bisulphite solution | → Crystalline addition product. Used to purify aldehydes and methyl ketones. |
| Grignard addition | R'MgX (dry ether), then H₃O⁺ | HCHO → 1° alcohol; RCHO → 2° alcohol; R₂CO → 3° alcohol |
| Reduction to alcohol | NaBH₄ or LiAlH₄ | C=O → CHOH. NaBH₄ is milder (only C=O); LiAlH₄ reduces all (ester, amide too) |
| Clemmensen reduction | Zn(Hg) + conc. HCl, heat | C=O → –CH₂– (complete deoxygenation). Acid conditions. |
| Wolff-Kishner reduction | NH₂NH₂ + KOH/ethylene glycol, heat | C=O → –CH₂–. Basic conditions. |
| Aldol condensation | Dilute NaOH (α-H required), cold then hot | 2 × RCHO → β-hydroxy aldehyde (cold) → α,β-unsaturated carbonyl (hot) |
| Cannizzaro reaction | Conc. NaOH (no α-H) | 2 HCHO → CH₃OH + HCOONa. Disproportionation. |
| Test | Aldehyde result | Ketone result |
|---|---|---|
| Tollens | Silver mirror ✓ | No reaction ✗ |
| Fehling's | Brick red Cu₂O ppt ✓ (aliphatic only) | No reaction ✗ |
| Schiff's | Pink/red colour ✓ | No reaction ✗ |
| 2,4-DNP | Orange ppt ✓ | Orange ppt ✓ (both give positive) |
| Iodoform (I₂/NaOH) | CH₃CHO → CHI₃↓ ✓ | CH₃COR → CHI₃↓ ✓ (methyl ketone only) |
| Concept | Key Fact | Example |
|---|---|---|
| Basicity — aliphatic | Aqueous: 2° > 1° > 3° > NH₃ (solvation controls 3°). Gas phase: 3° > 2° > 1° > NH₃ | (CH₃)₂NH (pKb 3.27) > CH₃NH₂ (3.38) > (CH₃)₃N (4.22) |
| Basicity — aromatic | Aniline < NH₃ < aliphatic amines (lone pair delocalised into benzene ring → less available) | C₆H₅NH₂ pKb = 9.38 (much less basic) |
| Effect of substituents on aniline | –NO₂ (EWG, para/ortho) → decreases basicity. –CH₃, –OCH₃ (EDG) → increases basicity | 4-NO₂-aniline (pKb 13) < aniline (9.4) < 4-CH₃-aniline (8.9) |
| Gabriel synthesis | Phthalimide + RX (SN2) → N-alkylphthalimide → hydrazine hydrate → 1° amine (pure, no 2°/3°) | Only way to get pure 1° amine without contamination |
| Hoffmann degradation | RCONH₂ + Br₂ + 4NaOH → RNH₂ + Na₂CO₃ + 2NaBr + 2H₂O. Product has one fewer carbon. | CH₃CONH₂ → CH₃NH₂ (one carbon less) |
| Carbylamine test | Primary amine only: R–NH₂ + CHCl₃ + KOH → R–NC (isocyanide, foul smell) | 2° and 3° amines do NOT give this test |
| Diazotisation | Aromatic 1° amine + NaNO₂ + HCl (0–5°C) → diazonium salt Ar–N₂⁺Cl⁻. Aliphatic amines give unstable diazonium → N₂ + alcohol immediately | C₆H₅NH₂ → C₆H₅N₂⁺Cl⁻ (stable at low temp) |
| Sandmeyer reaction | ArN₂⁺Cl⁻ + CuCl → ArCl; + CuBr → ArBr; + CuCN → ArCN | Cu salt needed as catalyst |
| Gattermann reaction | ArN₂⁺Cl⁻ + Cu powder + HCl → ArCl (Cu powder, not CuCl — less efficient Sandmeyer variant) | Used when CuCl unavailable |
| Azo coupling | ArN₂⁺Cl⁻ + phenol/aniline (alkaline) → Ar–N=N–Ar' (azo dye, coloured) | p-hydroxyazobenzene: orange dye |
Starting material: ArN₂⁺Cl⁻
💡 Memory: "Sandmeyer = Cu salts give halides; Balz-Schiemann = fluoride via BF₄⁻ salt". The Cu² → Cu¹ redox is why Cu salt is needed in Sandmeyer.
| Type | Definition | Examples | Key Property |
|---|---|---|---|
| Monosaccharides | Simplest; cannot be hydrolysed further | Glucose, Fructose, Galactose, Ribose | All reducing sugars |
| Disaccharides | 2 monosaccharide units; hydrolysis gives 2 monosaccharides | Sucrose, Maltose, Lactose, Cellobiose | Sucrose = non-reducing; rest are reducing |
| Polysaccharides | Many monosaccharide units; not sweet, insoluble | Starch, Cellulose, Glycogen, Chitin | Non-reducing; structural or storage |
| Starch | α-D-glucose linked by α-1,4 (amylose: linear) and α-1,6 (amylopectin: branched) | Rice, wheat, potato | Energy storage in plants |
| Cellulose | β-D-glucose linked by β-1,4 glycosidic bonds — linear, rigid | Cell walls, cotton, wood | Structural; humans can't digest (no β-glucosidase) |
| Glycogen | Highly branched α-1,4 and α-1,6 (more branching than starch) | Liver, muscle | Energy storage in animals |
| Reducing sugars | Have free –CHO or potential –CHO (open chain); reduce Tollens/Fehling | Glucose, Fructose, Maltose, Lactose | Give positive Fehling's/Tollens |
| Non-reducing sugars | Both anomeric carbons used in glycosidic bond; no free –CHO | Sucrose | Negative Fehling's/Tollens |
| Mutarotation | Change in optical rotation of α or β-D-glucose dissolved in water → equilibrium mixture via open chain. α: +112°, β: +19°, equilibrium: +52.7° | Glucose in water | Open-chain form is the intermediate |
| Level | Structure | Bond / Force | Example |
|---|---|---|---|
| Primary (1°) | Sequence of amino acids in polypeptide chain | Peptide bonds (–CO–NH–), covalent | Insulin: A-chain (21 aa) + B-chain (30 aa) |
| Secondary (2°) | α-helix or β-pleated sheet — regular repeating pattern | H-bonds between C=O and N–H of backbone | Keratin (α-helix); silk fibroin (β-sheet) |
| Tertiary (3°) | 3D folding of secondary structure; overall shape of protein | Disulphide bonds (–S–S–), H-bonds, hydrophobic, van der Waals, ionic | Myoglobin, enzymes |
| Quaternary (4°) | Association of 2 or more polypeptide subunits | Non-covalent interactions between subunits | Haemoglobin (2α + 2β subunits) |
| Denaturation | Loss of 2°/3°/4° structure; 1° (sequence) intact. Loses biological activity. | Broken by heat, acid, organic solvents, urea | Boiling egg white; curdling milk |
| DNA | RNA | |
|---|---|---|
| Strands | Double (anti-parallel) | Single |
| Sugar | 2′-deoxyribose | Ribose |
| Bases | A, G, C, T | A, G, C, U |
| Function | Genetic information storage | Protein synthesis (mRNA, tRNA, rRNA) |
| Location | Nucleus (mainly) | Nucleus + cytoplasm |
| Base pairing | A=T (2 H-bonds), G≡C (3 H-bonds) | A=U, G≡C |
| Vitamin | Type | Deficiency Disease | Source |
|---|---|---|---|
| A (Retinol) | Fat-soluble | Night blindness, Xerophthalmia | Carrots, fish liver oil |
| B₁ (Thiamine) | Water-soluble | Beriberi | Whole grains |
| B₂ (Riboflavin) | Water-soluble | Cheilosis, angular stomatitis | Milk, meat |
| B₁₂ (Cobalamin) | Water-soluble | Pernicious anaemia | Meat, eggs |
| C (Ascorbic acid) | Water-soluble | Scurvy (bleeding gums) | Citrus fruits, amla |
| D (Calciferol) | Fat-soluble | Rickets (children), Osteomalacia (adults) | Sunlight, fish |
| K (Phylloquinone) | Fat-soluble | Poor blood clotting | Green vegetables |