Alkyl Halides & Amines · Lecture Lecture · § 1 / 8
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Class XII · Chemistry · Unit 5 · Lecture

Alkyl Halides & Amines

The complete lecture, told through everyday pictures. Scroll down and the live panel keeps pace — a revolving door for substitution, an umbrella turning inside out for the SN2 flip, a leaking fridge for the ozone hole, and a fish market for why amines smell. Press ▶ to let it read and animate itself, section by section.

  • Alkyl halide (haloalkane) — a halogen (X = F, Cl, Br, I) in place of a hydrogen on an alkane: R–X. The C–X bond is polar (C is δ+, X is δ−), so the carbon invites attack.

The defining reaction is nucleophilic substitution: an electron-rich nucleophile (OH⁻, CN⁻, NH₃, OR⁻…) takes the place of the halogen. Picture a revolving door in a busy hotel lobby — as one person pushes in, exactly one person is pushed out. The new group enters, the old halide (the leaving group) departs, and the carbon framework stays put.

The exchangeNu⁻ + R–X → R–Nu + X⁻
The class of the halide — 1°, 2° or 3°, set by how many carbons touch the C–X carbon — decides which route the door turns by, and how fast.
  • SN2 — bimolecular substitution — happens in one step. The nucleophile strikes the carbon from behind the leaving group while the C–X bond breaks at the very same instant.

Hold an umbrella and let a strong gust hit it from behind: the canopy turns inside out, every rib swinging right through to the other side. A carbon does exactly this in SN2 — the three other bonds flip past the carbon as the nucleophile arrives. The product's groups now point the opposite way: inversion of configuration (the Walden inversion).

One concerted stepNu⁻ + R–X → [Nu···C···X] → Nu–R + X⁻
  • Rate = k[RX][Nu] — second order; needs both partners in the slow step.
  • Favoured by 1° (and methyl) halides — an open, uncrowded carbon — plus a strong nucleophile.

Substitution is a swap-partners dance. In SN2 the change-over is instant — old partner out, new partner in, all in one beat. But a crowded 3° carbon dances differently: it uses the SN1 route, letting the old partner leave the floor first.

  • SN1 — unimolecular substitutiontwo steps. Step 1 (slow): the leaving group departs, baring a flat carbocation. Step 2 (fast): the nucleophile cuts in.

Because the floor is now flat and open, a new partner can cut in from either side equally — so you get a 50:50 racemic mixture. Rate = k[RX] (only the halide is in the slow step), and three alkyl groups make the carbocation stable, which is why 3° halides prefer this dance.

A strong base instead of a nucleophile changes the music to elimination (E1/E2): it pulls off a β-hydrogen and a C=C alkene is born — Saytzeff's rule picks the more substituted, more stable alkene.

Why does class flip the mechanism? Think of the carbon as a doorway. A 1° carbon is a wide, empty doorway — the nucleophile walks straight in from behind: fast SN2. A 3° carbon is a doorway jammed with three bulky people — nobody can squeeze past, so backside attack is blocked and the molecule must use the SN1 "leave first" route.

  • Of the halogen (same R): R–I > R–Br > R–Cl > R–F. The weak C–I bond is the best leaving group; C–F is strongest and least reactive.
  • Towards SN2: 1° > 2° > 3° (steric access). Towards SN1: 3° > 2° > 1° (carbocation stability).
BondReactivity
R–Imost reactive (weakest bond)
R–Br
R–Cl / R–Fleast reactive (strongest bond)

The polar, reactive C–X bond makes alkyl halides the workhorses of organic synthesis — intermediates to alcohols, ethers, nitriles, amines and Grignard reagents — and the active part of anaesthetics like chloroform and halothane.

The dark side is the CFC (chlorofluorocarbon) refrigerants such as CCl₂F₂. Picture an old fridge or air-conditioner quietly leaking CFC gas. It drifts up to the stratosphere, where UV light cracks off a chlorine radical (Cl•). Each Cl• then destroys thousands of ozone (O₃) molecules in a chain reaction.

🌍 The ozone hole — this thinning over Antarctica is why the Montreal Protocol phased CFCs out worldwide.
  • Amine — ammonia (NH₃) with one or more H's replaced by R groups. Count carbons on the nitrogen: R–NH₂ is , R₂NH is , R₃N is — the opposite counting to halides.

Walk past a fish market and that sharp smell is free amines (like trimethylamine) escaping from the fish. The reason amines are volatile and reactive is the lone pair on nitrogen — it makes the amine a base. That lone pair reaches out and grabs a passing proton (H⁺), forming an alkylammonium ion; that capture is exactly what basicity means.

As a baseR–NH₂ + H⁺ → R–NH₃⁺  ·  strength: aliphatic amine > NH₃ > aniline

Alkyl groups donate electrons onto N, so the lone pair is more available → aliphatic amines beat ammonia. In aniline the lone pair is pulled into the benzene ring → it is the weakest base.

Three routes to an amine

RoutesR–X + NH₃ → R–NH₂ (ammonolysis)
R–NO₂ →[H]→ R–NH₂ (reduce a nitro)
R–C≡N →[H]→ R–CH₂–NH₂ (reduce a nitrile; adds a C)

Reducing nitrobenzene is the classic factory route to aniline, the parent of countless dyes and medicines. And one famous alkyl halide — chloroform (CHCl₃), once bottled as a surgical anaesthetic — reappears as a reagent for telling amines apart.

  • Carbylamine test — only a 1° amine heated with CHCl₃ + alcoholic KOH gives a foul-smelling isocyanide. A bad smell ⇒ primary amine.
  • Hinsberg's test — with C₆H₅SO₂Cl: 1° → KOH-soluble product, 2° → insoluble solid, 3° → no reaction.
  1. Substitution = revolving door: Nu in, X out; classify R–X by carbons on the C–X carbon.
  2. SN2 — one step, backside attack, inversion (umbrella flip), k[RX][Nu], 1° + strong Nu.
  3. SN1 — two steps via a carbocation, racemisation, k[RX], favoured by 3°.
  4. E1/E2 elimination & Saytzeff's rule; reactivity R–I > R–Br > R–Cl > R–F.
  5. CFCs & the ozone hole; chloroform & halothane anaesthetics.
  6. Amines: classify (carbons on N), prepare, basicity (aliphatic > NH₃ > aniline); carbylamine & Hinsberg tests.
⚛ Live panelAlkyl Halides & Amines
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