Organic Chem Study-Guide

Basics/Fundamentals

Most important rule of orgo: compounds move towards stability; if it’s unstable it’s more likely to react.
Stability means lower potential energy. Factors that decrease stability: steric strain, localization of
negative or positive charge, charge separation (of opposite charges); factors that increase stability: more
stable conformations, resonance, induction

Bookkeeping: draw out structures, include lone pairs and negative charges, and draw all arrows. It’ll
take more time to draw out everything in detail but you lessen your chances of making a mistake

Acids/Bases: acidity and basicity is relative, can only compare two different compounds together, as
depending on the solution/situation, most compounds can act as both acids and bases. Strength of
acids: look at stability of conjugate base. Strength of bases: look at their stability

Ex: is NH3 or H2O a stronger acid?

NH3 conjugate base is NH2-. H2O conjugate base is -OH. Oxygen is a more electronegative element than
nitrogen and thus holds that lone pair (negative charge) more closely, therefore -OH is more stable.
Nitrogen doesn’t hold the lone pair so closely and thus the lone pair can be donated more easily
compared to -OH. Since H2O has the weaker (more stable) conjugate base, it is the stronger acid
(compounds move towards stability).

Factors to consider ARIO:

 Atom: (Electronegativity and size. Size > electronegativity in the same group)
 resonance (resonance structures stabilize negative and positive charge)
 Induction (partial donation or withdrawal of electron density)
 orbitals (the closer the electrons are to the positive nucleus, the more stable the anion. Ex:
triple-bonded carbon-carbon with a negative charge is more stable than a double bonded
carbon-carbon with a negative charge because sp hybridized orbital is closer to the nucleus vs.
sp2

Ex: which is the more stable anion? I, F, Cl, Br?

I > Br > Cl > F; These are all 7th group elements, and their size increases greatly down a group. They have
the same amount of negative charge. So the atom with the larger size can spread that negative charge,
decreasing the charge density.

Ex: which is the better nucleophile? -OH, -SH,

Both have a negative charge (atoms with negative charge are always better nucleophiles), but S is much
bigger than O, so it’s outer layer of electrons are farther from its nucleus, and thus held less tightly.
Therefore, -SH can donate its electrons more effectively.

Other things: nucleophilicity decreases with more bulky compounds. hydrogen bonding solvents (polar
protic) invert nucleophilicity. In polar protic solvents nucleophilicity increases down the periodic table.
In polar aprotic solvents, it increases up the periodic table.
Alkanes

Branched alkanes have lower boiling points than straight-chained alkanes because branching makes
compounds bulky, disallowing more van der waals interactions to occur.

Branched alkanes are more stable than straight-chained alkanes. The why you probably don’t need to
know as it’s a debated topic, but just in case: branched alkanes can have net stabilizing effect between
1,3 alkyl-alkyl interactions (alkyls that are on the 1st and 3rd carbon, i.e. 2 carbons apart), which lowers
the potential energy of the compound. What you do need to know is that branched alkanes have lower
heats of combustion. Lower heat of combustion means a more stable compound (it’s at a lower
potential energy. Compare 4000 vs 3000 heat released due to combustion. If the compound is releasing
more heat from combustion, the compound must’ve been originally at a higher potential energy level.

Newman Projections and Conformational analysis

Helps us see interactions in the compound and determine its stability.

electrons pairs repel each other. Molecules are most stable when electrons pairs are as far apart from
each other as possible. When electron pairs are closer together, then the molecule is at a higher energy
state and thus more unstable.

Strain is what we call the energy associated with this repulsion of electrons. There is ring strain due to
cyclic structures being forced into specific angles (except in the case of cyclohexane). Steric strain due
to proximity of atoms.

The C—C bond rotates in space. If there are bulky groups on those carbons, then the groups can
interact depending on the angle of rotation (called the torsional or dihedral angle).

 staggered: groups apart, lower energy (vs. eclipsed)

 eclipsed: groups are on top of each other, highest energy
 gauche: steric interaction between two bulky groups—their electron clouds repel each other,
destabilizing the compound.
 anti: groups are 180 degrees apart, lowest energy

Radical Mechanism

Radicals occur from hemolytic bond cleavage shown as two fish-hook arrows (motion of one electron)
breaking a bond:

Geometry of radicals. A CH3+ looks is sp2 hybridized and trigonal planar. A CH3- has a filled sp3 orbital
and is trigonal pyramidal. A CH3● radical has a partial positive on the central carbon and takes on a
“shallow pyramid” structure which can be treated as trigonal planar.
Stability of carbon radicals: Similar to carbocations. Look at surrounding substituents. Electron
donating groups stabilize the partial positive on the central carbon through induction. Resonance also
stabilizes. If you aren’t sure of which structure is more stable, draw them all out and do a pro-con list.
Note that radicals don’t occur on vinylic carbons (directly on the double bond).

All radical mechanisms follow these patterns:

These steps combine to give the initiation, propagation, and termination mechanism.
Cycloalkanes

Cycloalkanes are cyclical alkanes. They have significant angle strain. But larger cycloalkanes can take on
conformations (different 3-D positions) to reduce the strain.

Cyclopropane has the most angle strain. Some strain can be alleviated if its orbitals bend outwards.
However it also has torsional strain (from eclipsing H’s; construct a newman projection)

cyclobutene can adopt a puckered conformation (reduces its angle from 90 to 88, results in less angle
strain)

cyclopentane can also adopt a conformation which makes it much more stable than cyclopropane or
cyclobutene.

Cyclohexane can adopt a chair conformation which is nearly strain free.

Cycli hexane can take on a chair, a boat, or a twist boat conformation.

Draw the newman projections for the chair and boat looking down both carbons on either side of the
left side. For chair you should get something like this:
The newmann projection should give insight into why cyclohexane takes on a chair conformation.

Cyclohexane has 6 axial positions (red) and 6 equatorial positions (blue). Normally these are just the
hydrogens connected to the main 6 carbon ring structure.

Cyclohexane “ring flips” between its two possible chair conformations. Whenever it does so,
substituents on the axial position become equatorial and vice versa.
Stability of the chair conformations: when the two chairs are in equilibrium, the lower energy
conformation is favored (which is the equatorial one, as the substituent points away from the main body
of the ring). In the axial position, the substituent can have unfavorable interactions with other atoms on
the axial positions in what’s called a 1,3-diaxial interaction (interaction between substituents that are
two carbons apart; they are essentially gauche interactions).

Next session

Alkene stability

1. How substituted is the alkene, more substitution means more stability

2. stereochemistry: trans > cis reduces steric strain
3. conjugated alkenes (multiple double bonds spaced one carbon apart to form a pi bond system)
are more stable than isolated alkenes
4. energetics: pi bonds are less stable than sigma bonds, thus in most cases it is more beneficial
for compounds to “give up” their double bond in favor of an extra sigma bondwhy alkenes
undergo addition reactions

Conjugated: C=C-C=C-C=C; isolated: C=C-C-C=C

Pi bonds are sources of electron density and can act as nucleophiles or bases. They are reactive as such.

stereoisomers

enantiomers: use R/S to determine. If you want to double check, can always try to physically overlap
the compounds together. If they can’t be overlapped and they are mirror images, then the compounds
are enantiomers. The compound is meso if there is an internal mirror plane (the two chirality centers of
the compound are mirror images of each other).

Fischer projections: determine R/S as usual, then flip whatever configuration you get (RS). To double
check:
Substitution vs. Elimination

1. what is your leaving group? good or bad?

2. What is your reagent? Base or nucleophile and good or bad?
3. solvents (if relevant)
4. regiochemical and stereochemical consideration
Addition reactions