Bruice_SC_v4.

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O
CH3CH CH2
site of nucleophilic attack
under acidic conditions

site of nucleophilic attack under

basic or neutral conditions

8. Arene oxides can undergo nucleophilic

attack or can rearrange (via an NIH shift)
to form phenols. Arene oxides that form
unstable carbocations are more apt to
undergo nucleophilic attack (10.9).
9. Crown ethers form inclusion compounds
with metal ions based on molecular
recognition. Crown ethers can be used as
phase-transfer catalysts (10.10).
10. Thiols (RSH) are more acidic 1pKa ~102
than alcohols. Thiolate anions react with
alkyl halides to form sulfides (RSR);
sulfides react with alkyl halides to form
sulfonium salts 1R3S # X !2 (10.11).
11. Lithium reacts with alkyl halides to form
alkyllithium compounds; magnesium
reacts with alkyl halides to form Grignard
reagents. These organometallic
compounds are good nucleophiles; they
react as if they were carbanions. For
example, they react with epoxides to form
(after acidification) alcohols. In the
presence of H +, OH, or NH, organometallic
compounds form alkanes (10.12).
12. Gilman reagents 1R 2CuLi2 are formed
from alkyllithium compounds and CuI.
They couple with vinyl, aryl, and alkyl
halides, replacing the halogen. Catalytic
palladium is used to facilitate coupling
reactions with alkenes (Heck), stannanes
(Stille), and organoboranes (Suzuki) and
aryl, benzyl, or vinyl halides (10.13).

Chapter 11
Radicals Reactions of Alkanes

1. Alkanes undergo halogenation with Cl2

or Br2 and heat or light to form alkyl
halides in a chain reaction that has
initiation, propagtion, and termination
steps. The radical formed in the initiation
step is the reactant of the first propagation

2.

3.

4.

5.

6.

step and the product of the second

propagation step (11.2).
Radical stability: 3 7 2 7 1. Relative
rates for chlorination at room temp: 5: 3.8:
1 for 3, 2, 1. Probability and reactivity
factors are used to predict product
distribution (11.3, 11.4).
Relative rates for bromination at 125 C:
1600 : 82 : 1 for 1, 2, 3. A bromine
radical is less reactive and more selective
than a chlorine radical (reactivityselectivity principle (11.5).
When HBr adds to alkenes in the
presence of peroxide, Br is the
electrophile, so it adds to the sp2 carbon
bonded to the most hydrogensopposite
to the regioselectivity of HBr addition
without peroxide (11.6).
If a radical substitution reaction or a
radical addition reaction forms an
asymmetric center, the product will be a
racemic mixture (11.7).
Allylic and benzylic halides are
selectively halogenated at the allylic or
benzylic positions. Bromination of allylic
positions is best carried out with
NBS + peroxide + ; if the resonance
hybrid of the radical intermediate is not
symmetrical, two substitution products
are formed (11.8).

Cosmic
rays

1. An e - beam removes an e - to form a

molecular ion (a radical cation), which
then fragments. A magnetic field focuses
cations toward a detector, giving a mass
spectrum, which plots abundance versus
mass-to-charge (m/z) (12.1).
2. The molecular ion corresponds to the
nominal molecular mass. The base peak is
the highest abundance ion. M+1 peaks can
be used to determine the number of
carbons. For a chlorine-containing compound, the M+2 peak is 1/3 the M peak;
for a compound that contains bromine, the
M+2 peak is equal to the M peak. High
resolution MS can determine the exact
molecular mass. The e - beam is most likely
to dislodge a lone-pair e -. A bond between
carbon and a more electronegative atom
breaks heterolytically; a bond between
carbon and an atom of similar electronegativity breaks homolytically. a-cleavage
(cleavage of the bond a to the heteroatom)
occurs because the positive charge is then
shared by two atoms (12.212.5).
3. Spectroscopy uses electromagnetic
radiation to probe molecular structure.
Frequency 1n2 is directly proportional to
energy 1E = hn2; wavelength 1l2 is
inversely proportional to energy
(E = hc/l; c = speed of light).
IR spectroscopy uses wavenumbers (the
number of waves in 1 cm), which are
directly proportional to energy and have
units of cm-1 (12.6).

1019

1017

g-rays

X-rays

106

104

1015

1010

1013

Ultraviolet Visible
light
light

Infrared
radiation

101

Microwaves

102

0.4 0.8
Wavelength (l) in m

short
wavelength

low
frequency

105
Radio waves
NMR

106

1010
long
wavelength

4. Stretching vibrations involve changes in

bond length and occur at a higher energy
than bending vibrations, which involve
changes in bond angles. Absorption
bands indicate the kind of bonds present
in a compound. Those in the functional
group region 140001400 cm-12 detect
functional groups; those in the fingerprint
region 11400 600 cm-12 are characteristic
of the molecule as a whole (12.7, 12.8).

Chapter 12
Mass Spectrometry, IR Spectroscopy,
and UV/Vis Spectroscopy

Frequency (n) in Hz

high
frequency

Wavelength (m)
2.5 2.6 2.7 2.8 2.9 3

100

3.5

4.5

% Transmittance

5. Amines have poor leaving groups due to

the very strong basicity of -NH 2.
Ammonium ions are weaker acids
1pKa ~102 than hydronium ions 1pKa ~ -22,
so amines are stronger bases and better
nucleophiles than alcohols (10.6).
6. Ethers are cleaved with HI; the reaction is
S N1 (breaking to form the more stable
carbocation) unless the alkyl groups
cannot form a carbocation (primary,
vinyl, aryl); then it is S N2 (with iodide ion
attacking the least sterically hindered
carbon) (10.7).
7. Epoxides react with nucleophiles. Under
acidic conditions, the ring opens to put
the developing positive charge on the
more substituted carbon; under basic
conditions, the nucleophile attacks the
less sterically hindered carbon (10. 8).

5.5

10

OH

CH3CCH2CCH3
CH3

O H
0

4000 3800 3600 3400 3200 3000 2800 2600 2400 2200

C O
2000

1800
1600
Wavenumber (cm1)

1400

1200

1000

5. The greater the change in dipole moment

when a bond vibrates, the more intense
the absorption. The energy required to
stretch a bond depends on the bond
strength and the masses of the bonded
atoms; stronger bonds and lighter atoms
absorb at higher frequencies (Hooks
law); triple bonds are stronger than
double bonds, which are stronger than
single bonds. Electron delocalization can
affect bond order. C-H stretch frequency
depends on the hybridization of C
1sp 7 sp2 7 sp32. Alkene substitution
patterns can be identified in the
fingerprint region (12.912.11).
6. O H (of RCOOH and ROH) and N H
show absorption bands at the same
frequency, but their shapes are different.
The absence of bands can rule out
functional groups. Stretches with no net
change in dipole moment are IR inactive
(12.1212.14).
7. UV/Vis spectroscopy involves excitation
of an e - to a higher energy state: n : p*
and p : p* transitions; the latter are
lower in energy and have greater molar
absorptivities 1e2. The greater the lmax,
the lower the energy: UV radiation
(180400 nm) is of higher energy than
visible light (400780 nm). A chromophore
is the group in the molecule that causes the
absorption. Absorbance depends on the
concentration of the sample, the length of
the light path, and the e of the compound
(Beer-Lambert Law) (12.1512.17).
8. The more conjugated double bonds, the
greater the lmax (due to raised energy of
the HOMO and lowered energy of the