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C) BONDING PRINCIPLES AND HYBRIDIZATION

General assumptions based on valence bonding from general Usually, the shortcut to knowing if an atom has a charge:
chemistry can be drawn: • If its bonds is equal to its expected #bonds = no charge
Element(s) Valence Expected #bonds • If it has more bonds than expected = positive charge (+1)
Electrons • If it has less bonds than expected = negative charge (-1)
Carbon 4 4 (tetravalent)
Nitrogen 5 3 (trivalent) For example, a carbon with 4 bonds has no charge, an oxygen
Oxygen 6 2 (divalent) with 3 bonds has +1 charge, and a nitrogen with two bonds has
a -1 charge.
Halogens 7 1 (monovalent)
Hydrogen 1 1 (monovalent)
Bonds between carbons can have variations due to the shapes
These are the most important elements in organic chemistry.
of their orbitals, namely, sigma and pi. The differences between
these are listed below.
If you see an atom that disobeys the normal amount of bonds
Sigma Pi
stated in the table, they may have a positive or negative charge.
Headways Sideways
overlap/collision overlap/collision
The guide for knowing the charge of an atom is its formal charge
(FC), which is computed by subtracting the total lone electrons Stronger Weaker
and existing bonds to the valence electrons of an atom. Written First bond Anything after sigma
as a formula, Formed by s or Formed by p orbitals
hybridized orbitals
FC = #VE – bonds – lone electrons

Drawing the proper orbital diagram for the valence electrons for carbon would afford you this orientation:

In the excited state, one electron jumps to the p orbital, giving four valence orbitals of carbon ready to form one bond each (totaling to four
bonds, of course).

The problem is that carbon only forms one sigma and three pi bonds based on the above diagram. Organic compounds never do this, and can
form four sigma bonds (ex. ethane), three sigma and one pi (ex. ethene) or two sigma and two pi (ex. ethyne).

Hybridization suggests that the characters of the orbitals can mix or hybridize, giving rise to new orbitals.

(Lifted from organicchemistrytutor.com)

Characteristic sp3 sp2 sp

Orbitals to hybridize One s, three p One s, two p One s, one p
New orbital diagram FOUR sp3 orbitals THREE sp2 orbitals TWO sp orbitals
(1 p orbital unhybridized) (2 p orbitals unhybridized)
Types of bonds formed 4 sigma 3 sigma, 1 pi 2 sigma, 2 pi
Bond angles 109.5 120 180
Shape Tetrahedral Trigonal planar Linear

ORGANIC CHEMISTRY Ser Loisse Mortel, RPh

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D) INTERMOLECULAR FORCES
Chemical bonds are either polar or nonpolar, depending on whether there are charges or not. Once a polar bond exists, the partial
charges between the bonded atoms are called dipoles. Once opposite dipoles from atoms coming from separate bonds interact,
there is an intermolecular force (“inter-“ meaning between or among different things).
The larger the dipole (charge difference), the stronger the force.
The following table summarizes the different intermolecular forces:
Requirement Strength Examples Comments
Van der Waals/ Nothing (universal) Weak Interactions of Exists in practically all
London dispersion hydrocarbons molecules
Dipole-dipole Permanent partial Moderate Carbonyl groups Strength and polarity lies in
charges between VdW and Hbonds
Hydrogen bond H that is covalently Strong OH, NH groups Highly significant in biological
bonded to O, F, or N systems and biochemistry,
such as proteins and DNA
Ion-dipole One partial and one Very strong Inorganic compounds Strongest in this list; not
full charge (with metals) common in organic
compounds

Influence of IMF on polarity

Order of the forces of attraction (in dissolving under water):

Hydrogen bonds (most charge and thus, greatest polarity) > Dipole-dipole > Van der waals

Influence of IMF on melting/boiling point/density

Three factors influence the melting/boiling points/density:
1. Priority consideration: Strength of IMF (stronger means higher MP/BP/densities)
2. Tiebreaker 1: Number of carbons (longer or larger compounds share greater forces, thus higher MP/BP/densities)
3. Tiebreaker 2: Branching (branching among compounds with same #carbons reduces MP/BP/densities)

Observe the following trends:

E) STRAINS AND RESONANCE

As predicted from the hybridizations of carbon, the bond angles are those that conform to tetrahedral, planar, or linear shapes for sp3,
sp2, and sp hybrids, respectively. In addition, general chemistry notes that electrons between different bonds tend to repel each other
(VSEPR), leading to the expected geometries of molecules.

Strains are forces in an organic compound that tend to destabilize it because of certain restraints or arrangements of bonds. The
following table lists those strains.

ORGANIC CHEMISTRY Ser Loisse Mortel, RPh

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Strain Definition
Angle strain/ Ring strain Deviation of bond angles away from the expected angles in a ring
Torsional strain Closing of angles between parallel bonds, drawing atoms closer
Steric effect Competition for space due to bulky groups, pushing bonds away from
expected angles

• Ring strain comparisons (see below, left) show that cyclohexane is the most stable, and deviating from it increases ring strain
• Steric strain also differentiates stability between conformations (see below, right) – the closer the groups, the more the steric strain

On the other hand, there are cases where electrons cooperate with one another. In compounds having consecutive sp2 carbons (such as in
conjugated systems), pi electrons may move around. This effect is called delocalization. This is seen in inorganic compounds like carbonate:

ALL delocalizations stabilize!

Technically speaking, there are three major types of delocalization:
Type Description/ Shortcut Notes
Hyperconjugation Transfer of sigma bond to an adjacent carbon • Weaker than other delocalizations
(sigma bond delocalization) Shortcut: sp3 carbon beside sp2 carbon
Pi delocalization Transfer of pi bonds across atoms • As strong as lone pair resonance
(pi resonance) Shortcut: Conjugated pi bonds • Pi resonance becomes greater if
the area of the compound covered
by it becomes greater
Lone pair delocalization Transfer of lone pairs to an adjacent carbon • As strong as pi resonance
(lone pair resonance) Shortcut: N or O single bonded to an sp2 carbon
Benzene is a very popular model for pi resonance, and the idea of delocalization makes sense to its pi bonds being drawn as a circle:

Inductive Effects
Inductive effects are electron pulls due to differences in electronegativity.

a) Low electronegativity atoms exhibit electron donating inductive effect. Alkyl groups (ex. methyl groups) have this effect. The
more electron donation that exists, the more stable alpha carbons become.

ORGANIC CHEMISTRY Ser Loisse Mortel, RPh

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b) Electronegative atoms exhibit electron withdrawing effect. Halogens and oxygen have this effect. The more electron
withdrawing that exists, the less stable alpha carbons become (ex. F has more withdrawal than Cl, then Br, etc.).
When weak acids have more electron withdrawing effect, their acidity increases (see below, left)
Conversely, more electron donating groups would reduce acidity (see below, acetic acid vs formic acid)

(NOTE: You should already draw from your last term chemistry class that the lower the pKa, the more acidic and vice-versa)

Also note that delocalization sort of “withdraws” electrons from the acidic groups, too. Delocalization/ resonance increases acidity too.
This explains why, for example, carboxylic acids are more acidic than alcohols (see below):

F) ISOMERISM

1) Constitutional Isomers:
a) Structural or Skeletal Isomers – the parent chain length (and thus, degree of branching) is different

b) Positional Isomers – the placement of the functional group differs

c) Functional Isomers – possess different functional groups

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Configuration vs. conformation:

Conformation – temporary spatial differences; NOT FIXED; rotation or twisting of bonds interconverts conformers
Configuration – permanent differences; FIXED; rotation or twisting of bonds impossible

2a) Configurational Isomers - stereoisomers with permanent spatial differences; their placements are FIXED
For R/S and E/Z configurations, please follow the Cahn-Ingold-Prelog (CIP Rules) below:
• Based on atomic number of the first attached atom

Tiebreaker:
o If the first attached atoms are the same, compare all adjacent atoms next
▪ NOTE: If the adjacent atom has a multiple bond
▪ A double bond to a single atom means we will count that atom twice
▪ A triple bond to a single atom means we will count that atom thrice
a) Optical isomers – stereoisomers different in configuration resulting from asymmetry (nonsuperimposable, no
symmetry). Most asymmetric compounds have a carbon that has four distinct groups (called chiral
carbons/stereogenic isomers).
o They are called optical isomers because they usually have optical activity (can rotate plane-polarized light)
o To determine R or S configuration, use the CIP rules to assign priority 1-4, put 4 at the back, then spin from 1 to
3. If the spin is clockwise, assign R. If counterclockwise, assign S (refer to figure below, left)

i. Enantiomers – ALL chiral carbons have been inverted (all R -> S, all S -> R)
ii. Diastereomers – SOME (not all) chiral carbons have been inverted
▪ For a comparison of enantiomers vs diastereomers, refer to examples above, right
iii. Meso compounds – compounds with chiral carbons but have a plane of symmetry; optically inactive.
b) Geometric Isomers – are stereoisomers of a compound having two adjacent carbons with substituents, resulting
from inability to rotate. This happens when either: there is a double bond or when the compound is cyclic.

For double bonds, use cis/trans for compounds whose sp2 carbons have similar substituents (ex. H, methyl, or
halogen on either carbon).

cis -> <- trans

If they don’t have such point of comparison, use E/Z instead.

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2b) Conformational isomers – are stereoisomers of the same compound with temporary differences
Conformations around rotating bonds (“rotamers”) are presented using Newman projections.
• Views the whole structure directly from one end of the alkane.
• Carbon atoms are represented by circles.

• Staggered conformation – substituents at front do not superimpose those at the back; less stable
• Eclipsed conformation - substituents front superimpose those at the back; more stable

For rotamers with a substituents in the front and back carbons, more conformations exist.

Stability rank: anti > gauche > partially eclipsed > totally eclipsed
Additional details:
Conformation Strains that exist Stability Rank (out of all 4)
Totally eclipsed/ Fully eclipsed/ “Syn” High torsional, high steric 4 (most unstable)
Gauche Low torsional, high steric 2
Partially eclipsed/ “Anticlinal” High torsional, low steric 3
Anti Low torsional, low steric 1 (most stable)

TIP: The rankings above suggest a shortcut: any staggered conformation (ex. gauche, anti) is more stable than
any eclipsed conformation (whether partial or full)
In cyclohexane, boat and chair conformations exist. The chair is more stable due to lessened steric effect.

PRACTICE QUESTIONS
1. Name this:
CH3C≡CCH(C2H5)2
A) 1,1-diethyl-2-butyne 3. Name this:
B) 4,4-diethylbut-2-yne
C) 2-ethylhex-4-yne A) pentyl pentanoate
D) 4-ethyl-2-hexyne B) propyl pentanone
E) but-2-ynyldiethane C) propyl pentanoate
D) butyl pentanoate
E) propyl butanoate

4. Which of the following does not describe the pi bond?

A) formed by sideways overlap
B) weaker than sigma
2. Name: C) Present in single bonds
A) 3-chlorobutanal D) two of the above
B) 2-chlorobutan-3-one E) all of the above
C) 3-chlorobutan-2-one
D) B and C are equally acceptable 5. What is the hybridization of central atom in CH2=C=CH2?
A) sp3
B) sp2
C) sp
D) s
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6. What is the total number of sigma bonds found in the A) 2

following compound? B) 3
C) either 2 or 3

A) 8 14. Which of the following has the most stable alpha carbon?
B) 10 A) cyclohexanol
C) 11 B) n-butanol
D) 15 C) benzyl alcohol
D) tert-butyl alcohol
E) Two of the choices
7. What is the bond angle of alkenes?
A) 180 15. When two isomers differ in their branching/ length of
B) 109.5 parent chain, they are called
C) 120 A) conformational isomers
D) 360 B) configurational isomers
C) stereoisomers
D) skeletal isomers
8. Which of the following alkanes would have the highest
boiling point? 16. When two compounds are very similar in name except
they have letters or descriptors to differentiate them from
their isomer, they may be called
A) A) configurational isomers
B) conformers
C) functional isomers
D) skeletal isomers

B)

17. Describe
C) A) cis
B) E
C) S
D) ortho
E) meta
D)
9. Which of the following would have the highest water-
solubility?

18.
A) B) A) cis
B) trans
C) E
D) Z

C) D)
10. Which of the following has the most hydrogen bonds?
A) alkane
B) alkene 19.
C) alcohol A) cis
D) water B) trans
11. Which of the following processes increases the stability C) E
of a carbon? D) Z
A) lack of carbons
B) resonance
C) steric hindrance
D) presence of electronegative atoms
12. Which of the following is the most acidic?
A) 2-methylbenzoic acid 20.
B) 2-chlorobenzoic acid A) R
C) 3-chlorobenzoic acid B) S
D) 3-methylbenzoic acid C) cis
D) trans
13. Which is the more stable atom between carbons 2 and 3
in 3-methyl-2-hexene?

ORGANIC CHEMISTRY Ser Loisse Mortel, RPh

Course Audit 2019-2020
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ANSWERS:
1) D
2) C
3) C
4) C
5) C
6) C
7) C
8) A
9) D
10) D
11) B
12) B
13) B
14) D
15) D
16) A
17) E
18) A
19) C
20) A

ORGANIC CHEMISTRY Ser Loisse Mortel, RPh

Course Audit 2019-2020