Chemistry 220A Lectures Th 9/15 and T 9/20/2011 Suggested Problems: 4.23, 4.24, 4.30, 4.31, 4.32, 4.36, 4.

37, 4.40, 4.41, 4.42, 4.43, 4.45, 4.51, 4.53, 4.54, 4.55-4.62 Alkyl halides Know the following common names: isopropyl, isobutyl, sec-butyl, tert-butyl and recognize their use in common names of compounds
Br H 3C CH2 CH2 CH2 Br H 3C CH2 CH CH3

n-butyl bromide
H 3C CH CH3 CH2 Br H 3C

sec-butyl bromide
CH3 C CH3 Br

isobutyl bromide

tert-butyl bromide

Note: primary, secondary and tertiary carbon and hydrogen atoms (a quaternary carbon is present in 2,2-dimethylpropane) Know also the names and structures of methyl chloride, methylene chloride, chloroform and carbon tetrachloride and the corresponding bromides and iodides In IUPAC nomenclature, alkyl halides named as substituted hydrocarbons Polar CX bonds but no hydrogen bonding; alkyl halides not soluble in water Remember that dipole moments depend on bond polarity and bond distance CH3F 1,85D; CH3Cl 1.87D; CH3Br 1.81D; CH3I 1.62D Weak forces go up with number of electrons, polarizability

Alcohols

OH

OH

bp =118

bp =107

OH OH

bp =99

bp =83

In IUPAC nomenclature, named as alcohols Characteristic suffix and OH given primacy in numbering system Boiling points reflect hydrogen bonding Affects of branching hinder maximal hydrogen-bonding Solubility in water n-butyl alcohol vs t-butyl alcohol Acidities similar to that of water Ethanol vs. tert-butyl alcohol as acids importance of solvation Alkoxide ions more strongly solvated than neutral alcohols Bulky t-butoxide ion less well-solvated, stronger base than ethoxide ion

Nucleophilic Substitution Reactions SN1 Mechansim Substitution, Nucleophilic, Unimolecular

H3C H3C C H3C H Nu C CH3 H H C+ CH3 H3C L H3C CH3 C+ CH3 H H C Nu

+ L-

Order vs. Molecularity carbocation formation is slow step of reaction reactivity of 1o << 2o << 3o Alkyl groups are electron donating relative to H disperse positive charge and stabilize carbocation intermediate Induction sp2sp3 orbitals in bond p overlap

Hyperconjugation

Reaction Diagrams plot of E, H, or G vs reaction coordinate Transition states Intermediates Hammonds Postulate for an endothermic step, TS resembles intermediate SN2 Mechanism Substitution, Nucleophilic, Bimolecular

H C L Nu

H L CH3CH2 Nu C

Nu +
CH3CH2

+ L
CH3CH2

Transformations to know 3o ROH to 3o RX with HX for HCl and HBr 1o ROH to 1o RX with HX and heating (slower reaction, different mechanism) thionyl chloride, SOCl2, in pyridine to make 1o and 2o RCl phosphorus tribromide, PBr3, in ether to make 1o and 2o RBr Alkyl Halides from Alkanes (besides combustion, the major reaction of alkanes)
RH + X2 RX + HX

Reactions use relatively expensive halogens and generate HX as biproducts May be useful for making RCl or RBr but never used for making RF or RI Chlorination is not selective except in simple or in special cases. As the relative amount of chlorine is increased, greater amounts of more highly substituted chloralkanes (CH2Cl2, CHCl3 and CCl4) form Energetics of Pathway Initiation step ivolves bond cleavage to input of theral energy (heat) orenergy of a photon required Termination steps are exothermic and have very low activation energies (whenever two radicals collide, they react although they may fly apart again) Propagation steps stronger covalent bonds form when atoms differ more in electronegativity; the smaller the halogen and the more electronegative it is, the shorter and stronger the HX bond Reactions of alkanes with fluorine are too exothermic to control, and the reaction with iodine does not take place for both rate and equilibrium considerations. Halogenation of higher alkanes
n-butane + Cl2 1-clorobutane + 2-chlorobutane + HCl

28% if statistical 60%

72% 40%

relative reactivity in chlorination 3o > 2 o .> 1 o in ratio ~5 : ~4 : 1

Homolytic cleavage of CH bonds more stable radical less energy to cleave bond Stability of alkyl radicals Radicals have electron-deficient carbon atoms Stabilized by electron-donating alkyl groups 3o > 2 o > 1 o Differences in the stability of radicals much less than those of carbocations Bromination far more selective than chlorination of greater synthetic utility than chlorination relative reactivity in bromination 3o > 2 o > 1 o in ratio approximately 1600:80:1 Br less reactive than Cl in hydrogen abstraction step (weaker HX bond forming Higher activation energy so that fewer collinsions have sufficient energy to lead to reaction In general, milder conditions (lower T) give enhanced selectivity Chlorofluorcarbons and ozone-layer depletion CF3Cl + h (UV) CF3 + Cl Cl + O3 ClO + O2 ClO + O Cl + O2 O3 + O O2 + O2 (Net Reaction) Few termination steps available, so propagation steps repeated thousands of times