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1
Organic Chemistry
Paula Yurkanis Bruice, 5th Edition
Prepared by Merritt B. Andrus
H
H
H
HC
Methane
H
HH
H
pbond
sbond
C
C
Ethene
C
C
H
H
Ethyne
Chapter 1
Electronic Structure and Bonding
Acids and Bases
1.Atoms consist of protons (p+), neutrons
(n), and electrons
Atomic numberis

the number of p+; mass number is the
sum of p+and n.Isotopes have the same
number of p+with different numbers of n.
The atomic weight of an element is the
average weighted mass of its atoms (1.1).

2. An atomicorbital (s, p, d, f) is the volume
of space around a nucleus where an
electron is most likely to be found. An
electron goes into the lowest energy
orbital available (aufbau principle), with

two in each orbital (Pauli exclusion
principle).An will occupy an empty
degenerate(same energy) orbital before
it will pair up with another (Hund\u2019s
rule). Coreare in filled shells; valence
are used for bonding (1.2).
3. Atoms give up or accept to achieve an
outer shell of eight electrons (octet rule).
Electropositiveelements (on the left of
the periodic table) lose to form cations;
electronegativeelements (on the right)
gain to form anions. Ionic bondsare
formed by electrostatic attraction
between cations and anions.
Electronegativityis a measure of an
atom\u2019s ability to attract
Atoms form
covalent bondsby sharing valence
Nonpolar covalent bondsare formed by
atoms with the same electronegativity;
polar covalent bondsare formed by
atoms with different electronegativities.
A polar bond has adipole with adipole
moment, D(debye). Electrostatic
potential mapsshow how charge is
distributed: red
and blue
(1.3).

4.Lewis structures represent compounds,
showing all bonding and lone pair
The formal charge on an
number of valence minus 1/2 the

bonding minus the lone pair
Carbocationshave a positively charged

carbon;c a r ba n i o n s have a negatively
charged carbon; a carbonradical has a
carbon with an unpaired

Kekul\u00e9
structuresdepict bonds as lines.
Condensed structuresuse subscripts and
few, if any, bonds (1.4).
5. Ans atomic orbital is spherical; the 2s

atomic orbital has a radial node. There are three degenerate, perpendicularp orbitals; each has a node at its nucleus (1.5).

6.Bond length is the distance between
nuclei; bond dissociation energy is

the energy required to break a bond.
Two atomic orbitals combine to form
two molecular orbitals, a bonding MO

( or ) and an antibonding MO(
or ). Asigma
bondis
1s2
p*
s*
p
s
e-.
e-.
e-
e-
atom= the
e\ue000.
1+2
1-2
e-.
e-.
e-
e-e-
e\ue000
e-
e-
e-
e-
1e-2.
#
cylindrically symmetrical. Twop orbitals
overlap side-to-side to form api
bond(1.6).
7. Methane has four identical covalent bonds
formed using fourhybrid
orbitals,
which result from mixing one 2s and three
2p atomic orbitals. It hastetrahedral
(109.5\u00b0) bond angles.Ethane has
carbons and 109.5\u00b0 bond angles.Ethene
(with a double bond) has

carbons and
120\u00b0 bond angles. Ethyne (with a triple
bond) hassp carbons and 180\u00b0 bond

angles. All single bonds are bonds; a
double bondconsists of
bond and
bond; a triple bond consists of
bond
and

bonds. The mores character, the
shorter and stronger the bond and the
larger the bond angle. (1.6\u20131.9, 1.14).

2p
1s
1p
1ss
sp2
sp3
1sp32
1p2
alcohols and water
The equilibrium constant for
an acid-base

When atoms are the same size, the more electronegative the atom to which the hydrogen is attached, the stronger the acid. Relative electroneg- ativities:

When atoms
are very different in size, the strongest
acid will have its hydrogen attached to
the largest atom. For example, acid
strength:

The

stronger the acid, the weaker its
conjugate base. Weak bases are stable
bases. ALewis acid accepts a share in a
pair of

a Lewis base donates a share in
a pair of
Curved arrowsare used to

show electron flow; the arrow begins
where the electrons originate and points
to where they end up (1.16\u20131.26).

Chapter 2
An Introduction to Organic
Compounds
1.Hydrocarbons contain only C and H.
Alkanesare hydrocarbons with only

single bonds. Constitutional isomers
have the same molecular formula but
differ in the way the atoms are connected.

IUPAC (systematic)and common names
are used to name compounds.
methylene group.A primary (1\u00b0) carbon
is bonded to one other C; a secondary (2\u00b0)
carbonis bonded to 2 Cs; a tertiary (3\u00b0)
carbon isbonded to 3 Cs. Substituents
are indicted as prefixes, with theparent
hydrocarbonnumbered in the direction

that puts the lowest number in the name
of the compound. Substituents are listed
alphabetically; di, tri, tetra, are used for
identical alkyl groups, but are not
alphabetized;sec andtert are also not
alphabetized, but iso and cyclo are. In a

cycloalkanewith two substituents, the
first cited substituent gets the lower
number (2.1\u20132.3).
CH2=a
e-.
e-;HI7 HBr7 HCl7 HF.
sp7 sp27sp3.
1productKa2.
reaction=1reactantKa2/
1pKa'152.
1pKa'102;
8. The O and N of water and ammonia are
hybridized;
has 104.5\u00b0 bond
angles;
has 107.3\u00b0 bond angles.
and
are
is
(1.11, 1.12).
9. ABr\ue001nsted aciddonates a proton
a
Br\ue001nsted baseaccepts a proton, forming a
conjugate baseand a conjugate acid,
respectively. The acid dissociation
constant
is a measure of the acidity of
a compound;
the lower
the
the stronger the acid. Protonated
carboxylic acids and protonated
acids
carboxylic
acids
protonated
weak acids
amines= very
1pKa'52;
acids= weak1pKa602;
alcohols= strong
pKa,
pKa= -logKa;
(Ka)
1H+2;
sp3
sp2;C-
C#
C+
NH3
H2O
sp3
CH3CHCH2
CH3
an isobutyl group
CH3CH2CH
CH3
asec-butyl group
CH3CCH3
CH3
atert-butyl group
a secondary carbon a tertiary carbon
a primary carbon
2.Alkyl halides andethers are named as
substituted alkanes;alcohols andamines

are named using a functional group suffix.
Substituents on the nitrogen are preceded
by anN. If a parent chain has a substituent,
the substituent gets the lowest number; if
it has a functional group, the functional
group gets the lowest number; if it has
both a substituent and a functional group,
the functional group gets the lowest
number. Only if the functional group gets
the same number in either direction, is the

2
axial bond
equatorial bond
==
C C
+
+
H
slow
H
a carbocation
intermediate

the electrophile
adds to ansp2
carbon of the
alkene

the nucleophile
adds to the
carbocation

+
CC
fast
Br
Br\u2212
BrH
CC
CH3CHCH
3-methyl-1-butene
3-methyl-1-butanol
CH2
CH3CHCH2CH2OH
1. BH3/THF
2. HO\u2212,H2O2, H2O
CH3
CH3
chain numbered so the substituent gets
the lower number (2.4\u20132.7).

3. Alkyl halides and alcohols are 1\u00b0, 2\u00b0, or 3\u00b0
depending on whether the X or OH is on
a 1\u00b0, 2\u00b0, or 3\u00b0 carbon. Amines are 1\u00b0, 2\u00b0, or
3\u00b0 depending on how many alkyl groups
are bonded to N (2.4, 2.6, 2.7).

4. The stronger the intramolecular forces
holding molecules together, the higher
theboiling point: hydrogen bonds are
stronger thandipole-dipole interactions,
which are stronger than van der Waals
forces, which increase with molecular
weight and decrease with branching (2.9).

5. Polar compounds dissolve in polar
solvents; nonpolar compounds dissolve
in nonpolar solvents. An oxygen can drag
about 3 carbons into water (2.9).

6. Organic compounds exist in various
conformationsdue to bond rotation.
Newman projectionsdepict staggered
(anti and gauche)and higher energy
eclipsed conformations.Cyclopropane
and cyclobutane have significantangle
strain;cyclopentane and cyclohexane are
nearly strain free. Cyclohexane adopts a
chair conformationwith an axialand
equatorial bondon each carbon. Ring-flip

causes one chair conformer to convert into
another chair conformer; bonds that are
axial in one are equatorial in the other. A
substituent is more stable in an equatorial
position. A cis isomer has substituents on
the same side of the ring; a trans isomer
has them on opposite sides (2.10\u20132.14).

2. The

carbons of an alkene and the four
atoms attached to them are in a plane.Cis
isomers have the hydrogens on the same
side of the double bond; intrans isomers
they are on opposite sides. TheE isomer
has the high priority groups (based on
atomic numbers) on opposite sides of the
double bond; theZ isomer has them on
the same side. Proceeding down a
substituent breaks a tie (3.5).

3. The double bond of an alkene is its
functional group(the center of
reactivity). Curved arrows show the
mechanismfor this electrophilic
addition reaction(

is anelectrophile
and the bond is anucleophile; the
carbocation is anelectrophile and

is a
nucleophile) (3.6).
Br-
p
H+
sp2
Chapter 4
The Reactions of Alkenes

1. Hydrogen halides add to alkenes to form alkyl halides.Carbocations are stabilized byhyperconjugation( delocalization by overlap of adjacent bond orbitals

with the emptyp orbital); relative
stabilities:
TheHammond
postulatestates that the transition state is
more similar in structure to the species to
which it is more similar in energy (4.1\u20134.3).
2. Electrophilic addition reactions are
regioselective;the electrophile adds to
the

carbon bonded to the greater
number of hydrogens in order to form
the more stable carbocation (4.4).

3. The addition of water or an alcohol to an
alkene requires an acid catalyst. Addition
of water forms an alcohol; addition of an
alcohol forms an ether (4.5).

4. A carbocation can rearrange to a more
stable carbocation via a1,2-hydride or1,2-
methylshift, or by ring expansion (4.6).
5. Halogens (
and
) add to alkenes to
form vicinal dihalides via a cyclic
bromonium ion intermediate.If the
reaction is carried out in water, a
halohydrinis formed with water adding
to the more substituted

carbon. Since
the intermediate in these reactions is not a
carbocation, carbocation rearrangements
cannot occur (4.7).

6. Alkenes undergooxymercuration-
reductionand alkoxymercuration-
reductionto form alcohols and ethers,

respectively. Carbocations are not formed
as intermediates, so carbocation
rearrangements do not occur (4.8).

7. Alkenes react withperoxyacids

to formepoxides. The reaction
isconcerted (it does not have an
intermediate) (4.9).

8.Hydroboration-oxidation of an alkene
involves the concerted addition of borane
to form a trialkylborane that is
treated with
and

to form an
alcohol. Borane is the electrophile that
adds to the less substituted

carbon;
is the nucleophile that adds to the
other
carbon (4.10).
sp2
H-
sp2
HO-
H2O2
1BH32
1RCO3H2
sp2
Br2
Cl2
sp2
3\u00b07 2\u00b07 1\u00b0.
se-

Chapter 3
Alkenes: An Introduction to
Reactivity. Thermodynamics and

Kinetic

1.Alkenes are hydrocarbons with a double
bond. The total number of bonds and
rings is the degree of unsaturation. The
general molecular formula for a
hydrocarbon is

minus 2
hydrogens for each degree of
unsaturation. The parent hydrocabon is
the longest carbon chain that contains the
double bond, numbered so that the start
of the double bond is given the lowest
possible number.Alkadiene is used for
two double bonds. Vinylic carbons are
double-bonded carbons; allylic carbons
are adjacent to vinylic carbons (3.1\u20133.2).

CnH2n+ 2
p
CH3CHCH2CH CCH2CHCH3
2-bromo-4-ethyl-7-methyl-4-octene
not
7-bromo-5-ethyl-2-methyl-4-octene
because 4 < 5
CH3
CH2CH3
Br
6-bromo-3-chloro-4-methylcyclohexene
not
3-bromo-6-chloro-5-methylcyclohexene
because 4 < 5
Br
Cl
CH3
4. Energy changes are shown by areaction
coordinate diagram.A transition state

has partially broken and partially formed
bonds; anintermediate has fully formed
bonds. The more stable the species, the
lower its energy. The change in Gibbs free

energy
isexergonic
when
forming a more stable species, and
endergonic
when forming a less
stable species.

is related to the
equilibrium constant by
The formation of products with stronger
bonds and greater freedom of movement

causes
to be negative;

If a system at
equilibrium is disturbed, it will adjust to
offset the disturbance (Le Chatlelier\u2019s

principle).The free energy of activation
(
\u2021) is the difference between the free
energy of the transition state and the free
energy of the reactants. The greater
\u2021,
the slower the reaction. Therate-
determining stephas its transition state at

the highest point on the reaction
coordinate. The rate of a reaction is
directly proportional to a rate constant,k;
the smaller the rate constant, the slower
the reaction. The Arrhenius equation
relates the rate constant to the activation

energy
(3.7\u20133.8).
1Ea2
\u00a2G
\u00a2G
\u00a2G\u00b0 = \u00a2H\u00b0 -T\u00a2S\u00b0.
\u00a2G\u00b0
-RTln Keq.
\u00a2G\u00b0
1+2
1-2
1\u00a2G\u00b02
Freeenergy
CH2CH3
Br
+
CH3CH
CH3CHCH2CH3
Progress of the reaction
\u2212\u2206G\u02da
intermediate
Br\u2212
CH3CH CHCH3
HBr

9. Alkenes undergo catalytic (Pd/C, Pt/C,
Ni)hydrogenation to form alkanes. The
most stable alkene has the smallest heat of

hydrogenation.The greater the number
of alkyl substituents attached to the
carbons, the more stable the alkene (4.11).
Chapter 5
Stereochemistry
1.Constitutional isomers differ in the way
their atoms are connected.Stereoisomers
(cis-trans isomersand isomers withsp2
3
a ketone
an aldehyde
H2O, H2SO4
HgSO4
CH3C CH
CH3C CH2
CH3CCH3
OH
O
1. disiamylborane
2. HO\u2212, H2O2, H2OCH3CH CH
CH3CH2CH
OH
O
a.
b.
c.
CH3CH2
CH3
CH3
CH2CH3
Br
H
the two isomers of 2-bromobutane
enantiomers
mirror
Br
H
C
C
(S)-2-bromobutane
(R)-2-bromobutane
C
CH3CH2Br
H
CH3
C
H
Br
CH2CH3
CH3
1
1
2
2
3
3
4
4
asymmetric centers)differ in the way the

atoms are arranged in space. Cis-trans isomers have either a double bond or a cyclic structure (5.1).

2. A molecule ischiral if it is
nonsuperimposable on its mirror image.
A carbon bonded to four different
substituents is an asymmetric center.
A molecule with one asymmetric center is
chiral; it can exist as a pair of

enantiomers(nonsuperimposable mirror
image molecules). Enantiomers have the
same physical and chemical properties
(5.2\u20135.6).

7. In a stereoselective reaction, one
stereoisomer is formed in preference to
another. In a stereospecific reaction,
stereoisomeric (e.g., cis and trans)
reactants form different stereoisomers as
products. When a reactant without an
asymmetric center forms a product with
one asymmetric center, the product will
be a racemic mixture. Electrophilic
addition reactions that form carbocation
intermediates involvesyn andanti

addition.Hydrogenation, epoxidation,

and hydroboration are syn additions; halogenation is an anti addition. CIS- SYN-ERYTHRO or -CIS (5.18, 5.19).

8.Enzymes andreceptors can distinguish
between enantiomers. Enzyme-catalyzed
reactions are completely stereoselective\u2014
only one stereoisomer is formed.
Enzyme-catalyzed reactions are
stereospecific\u2014the enzyme reacts with
only one stereoisomer (5.20, 5.21).

Chapter 6
The Reactions of Alkynes
1.Alkynes are hydrocarbons with a triple

bond. Aterminal alkyne has the triple
bond at the end of a chain; otherwise, it is
an internal alkyne. A compound with a
double and a triple bond is named as an

alkenyne;the double bond has the
greater priority only if there is a tie. OH
and
groups have priority over
double and triple bonds (6.1, 6.2).
2. Electrophiles add to the least substituted
spcarbon. Addition of HCl or HBr forms
a vinyl halide; with excess reagent, a
geminal dihalideis formed. Addition of
or
forms a dihaloalkene; excess
reagent forms a tetrahaloalkane (6.5, 6.6).
3. The acid-catalyzed addition of water to
an alkyne forms anenol, which
tautomerizesto a ketone.
is used
with terminal alkynes (6.7).

4. Borane adds to an alkyne to form a vinyl-
borane, which is oxidized to an enol. An
internal alkyne tautomerizes to aketone: a
terminal alkyne requires disiamylborane
and forms analdehyde (6.8).

HgSO4
Br2
Cl2
NH2
Working from product to reactants, when
designing a synthesis, is called
retrosynthetic analysis(6.10\u20136.12).
Chapter 7
Delocalized Electrons and Their
Effect on Stability, Reactivity, and
1.Delocalized

are shared by three or
more atoms. Benzene has delocalized
all the

bonds have the same length;
the three pairs of
are shared by all
six carbons. Resonance contributors use
localized to approximate the true
structure with delocalized (the
resonance hybrid) (7.1\u20137.3).
e-
e-
pe-
C\u00ac C
e-:
e\ue000
pKa

3. TheR,Ssystem is used to name chiral
compounds by prioritizing the four
substituents attached to the asymmetric
center based on atomic number. When the
lowest priority substituent points to the
rear, an arrow starting at the highest
priority substituent and pointing at the
second highest priority substituent is
clockwise if the compound has theR
configuration, and counterclockwise if it
has theS configuration (5.7).

4. Chiral molecules that rotateplane-
polarized lightto the right are
dextrorotatory

those that rotate it to
the left arelevorotatory
Apolarimeter measures observed

rotation, from which specific rotation
can be calculated. A 50:50 mixture of
enantiomers is an optically inactive
racemic mixture. Enantiomeric
excessis measured by dividing the
observed specific rotation by the specific
rotation of the pure enantiomer (5.8\u20135.10).

5. Stereoisomers that are not mirror images
arediastereomers. Unlike enantiomers,
diastereomers possess different physical
and chemical properties. In compounds
with two asymmetric centers, the
configuration of one of the asymmetric
centers is the same in both diastereomers,
and the configuration of the other is not
the same in both. Compounds with two or
more asymmetric centers that possess a

plane of symmetryare achiral (optically
inactive) meso compounds (5.11\u20135.13).
6. Enantiomers can be separated (resolved)
by chiralchromatography (5.16).
1a=02
[a]
a,
1-2.
1+2;

5. Catalytic hydrogenation of an alkyne
forms an alkane. With Lindlar
catalyst, a cis alkene is formed; with

a trans alkene is
formed via radical anion andvinyl
radicalintermediates (6.9).
6. A terminal alkyne
is
deprotonated with
to form an
acetylide ion,which reacts with a 1\u00b0 alkyl
halide to form a longer-chain alkyne.
NaNH2
1pKa 252
Na1or Li2+ NH3,
2. Rules for drawing resonance contributors:
move only and lone-pair
Move to
a positively charged atom or to an atom
with a bond. Each resonance

contributor has the same net charge. The
greater the predicted stability of the
resonance contributor, the more it
contributes to the hybrid. Destabilizing
features: incomplete octet, positively
charged electronegative atom, charge
separation (7.4, 7.5).

3.Delocalization (resonance) energy is the
gain in stability that results from having
delocalized

The greater the number of
relatively stable resonance contributors,
the greater the delocalization energy.
Relative stabilities:

Allylicand benzyliccations are more
stable than 1\u00b0 alkyl cations because of
delocalization (7.6\u20137.8).
4. Amolecular orbital (MO) results from a
linear combination of atomic orbitals

(LCAO). Two are placed in each MO,
starting from the lowest energy MO. The
number of MOs equals the number of
AOs; a node is added for each ascending
MO. The highest occupied MO (HOMO)
is the highest energy MO that contains

the lowest unoccupied MO (LUMO) is
the lowest energy MO that does not
contain (7.8).
5. Carboxylic acids and phenol have some
delocalization, but their conjugate
bases have more, causing carboxylic
acids
and phenol
to be stronger acids than alcohols
which have no
delocalization. Protonated aniline
is more acidic than protonated
alkylamines

due to an
increase in delocalization energy upon
losing a proton (7.9).

1pKa'102
1pKa'52
e-
1pKa' 152,
1pKa'102
1pKa' 52
e-
e-
e-;
e-
e-
cumulated dienes.
isolated dienes7
conjugated dienes7
e-.
p
e-
e-.
p

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