Haloalkanes & Haloarenes: Named Reactions & Conditions

Bond Energy and Length Data

$\text{C-F: } \ell = 135 \text{ pm}, \quad E = 485 \text{ kJ/mol}$ $\text{C-Cl: } \ell = 177 \text{ pm}, \quad E = 339 \text{ kJ/mol}$ $\text{C-Br: } \ell = 193 \text{ pm}, \quad E = 285 \text{ kJ/mol}$ $\text{C-I: } \ell = 214 \text{ pm}, \quad E = 213 \text{ kJ/mol}$

Named Reactions — Complete Reference

Named Reaction	Equation	Reagent	Key Condition	Driving Force	Product
Finkelstein	RCl + NaI → RI + NaCl↓	NaI	Acetone solvent	NaCl insoluble in acetone → precipitates (Le Chatelier)	Iodoalkane (RI)
Swarts	RBr + AgF → RF + AgBr↓	AgF	Neat or anhydrous	AgBr insoluble → precipitates	Fluoroalkane (RF)
Dow Process	$C_{6}H_{5}Cl$ + NaOH → $C_{6}H_{5}OH$ + NaCl	NaOH	623 K, 300 atm	Harsh conditions overcome resonance-strengthened C-Cl	Phenol (ArOH)
Grignard Prep	R-X + Mg → R-MgX	Mg metal	Dry ether (anhydrous)	—	Organomagnesium (Grignard)
Williamson Ether	R-X + R' $O^{-}$ → R-O-R'	NaOR' (alkoxide)	Anhydrous, SN2 conditions	—	Ether (R-O-R')

Reaction Conditions Summary

$\text{SN1: 3° substrate + polar protic + weak Nu} \rightarrow \text{ROH (racemic)}$ $\text{SN2: 1° substrate + polar aprotic + strong Nu} \rightarrow \text{ROH (Walden inversion)}$ $\text{E1: 3° substrate + protic + high T} \rightarrow \text{Alkene (Saytzeff) + SN1 competition}$ $\text{E2: bulky base (t-BuO}^-\text{) + 2°/3° substrate} \rightarrow \text{Alkene (Saytzeff/Hofmann)}$

Phosgene Formation

$2\text{CHCl}_3 + \text{O}_2 \xrightarrow{\text{light/air}} 2\text{COCl}_2 + 2\text{HCl}$

CFC Ozone Depletion

$\text{CF}_2\text{Cl}_2 \xrightarrow{\text{UV}} \text{CF}_2\text{Cl}^{\bullet} + \text{Cl}^{\bullet}$ $\text{Cl}^{\bullet} + \text{O}_3 \rightarrow \text{ClO}^{\bullet} + \text{O}_2$ $\text{ClO}^{\bullet} + \text{O}^{\bullet} \rightarrow \text{Cl}^{\bullet} + \text{O}_2 \quad \text{(Cl regenerated — catalytic)}$