UST FACULTY OF PHARMACY

Organic Chemistry Lecture

Monthly Exams Reviewer
Earl Mantes 7/10/2012

This reviewer covers topics on atomic structure, hybridization, formal charge, electronegativity, definition of acids and bases according to Bronsted-Lowry and Lewis, structural effects, acidity and/or basicity of organic compounds, and isomers.

Atomic Structure
An ATOM is about 2 x 10-10 m or 200 picometers in diameter. A. Nucleus dense, positively charged; 10-14 to 10-15 m in diameter; contains almost all of the atoms mass a. Protons positive subatomic particle b. Neutrons neutral subatomic particles B. Electrons negatively charged; surround the nucleus at a relatively large distance (10-10 m) ATOMIC NUMBER (Z) number of protons/electrons MASS NUMBER (A) number of protons + neutrons ISOTOPES atoms having the same atomic number but different mass numbers ORBITAL region around the nucleus where the electron is most likely to be found; arranged into different layers called energy shells A. s orbital spherical with the nucleus at the center B. p orbital dumbbell shaped and can be oriented according to three mutually perpendicular directions: px, py and pz

Electron Configuration
a listing of orbitals that the atoms electrons occupy

SOME PROPERTIES OF CARBON:

Always at excited state fourbonding capability Can bond with itself, forming longer chains Has the ability to form an immense diversity of compounds

Formal Charge
FORMAL CHARGE = # valence (# bonding/2) - # non-bonding Example: FCO1 = 6 (2/2) 6 = -1 FCO2 = 6 (4/2) 4 = 0 FCN = 5 (8/2) 0 = +1 Therefore, Nitrogen is partially positive while the oxygen in the single bond is partially negative.

Bonds
A. IONIC transfer of electrons; electronegativity = 2.0 and above B. COVALENT sharing of electrons a. POLAR unequal sharing; electronegativity = 0.5-1.99 b. NON-POLAR equal sharing; electronegativity = 0-0.4

Electronegativity
Intrinsic ability of an atom to attract the shared electrons in a covalent bond

Always indicate which atom is partially positive and partially negative. Also, add a crossed arrow towards the more electronegative atom. Ex.: + C- N (2.5 3.0) --REMEMBER THIS: FONBrICH (F > O > N > Br > I > C > H) Flourine is the most electronegative among the 7 atoms.

Trends in the Periodic Table

LEFT to RIGHT increasing electronegativity UP to BOTTOM decreasing electronegativity

MOST ELECTRONEGATIVE ATOMS: N, O, F, Cl, Br

Characteristics of a Covalent Bond

BOND STRENGTH energy required to form/break the bond BOND LENGTH center-to-center nuclei of their maximum distance for them to form the bond; the optimum distance that enables two atoms to attract each other BOND BOND STRENGTH BOND LENGTH BOND ANGLE SHAPE (GEOMETRICAL) Tetrahedral Trigonal planar

Single-bonded C Double-bonded C

340 kJ/mole 610 kJ/mole

154 pm 133 pm

109.5o 120o

Triple-bonded C H-H NH3 H2O

830 kJ/mole 436 kJ/mole 449 kJ/mole 498 kJ/mole

120 pm 74 pm 100.8 pm 95.8 pm

180o

Linear

107.3o 104.5o

Hybridization
Bonds
1. Sigma Bond head-on overlap of hybridized orbitals 2. Pi bond sideways overlap of unhybridized p orbitals

Orbitals
1. sp orbital greatest s character (50% s, 50% p); triple-bonded C; 1 sigma bond, 2 pi bonds

2. sp2 orbital double-bonded C; 1 sigma bond and 1 pi bond

3. sp3 orbital least s character (25% s; 75% p); single-bonded C; 1 sigma bond

Acids and Bases

Bronsted-Lowry
1. ACID H+ donor 2. BASE H+ acceptor Ex.: HCl (acid) + H2O (base) Cl- (conjugate acid) + H3O (conjugate base)

Lewis
1. ACID accepting pair of electrons 2. BASE donating pair of electrons Ex.: Al03Br + :O(CH3)2 Al-Br3O+(CH3)2

Structural Effects
A. RESONANCE (pi electron delocalization) pi electron of sp2 atom displaces to a neutral atom (double bond), hence a lone pair of another atom displaces to the sp2 atom, thus the charge and placement of double bond change

B. CH HYPERCONJUGATION (sigma electron release) attributed to sp3 s character of molecule adjacent to sp2 atom; releases H+ to elicit acidic property C. LONE PAIR DELOCALIZATION lone pair delocalized to adjacent sp2 atom

D. INDUCTIVE EFFECT a. Electron Withdrawing positive and partially positive ions, highly polarizable ions (I-), high orbital electronegativity (triple-bonded C, C triple-bonded to N), high electronegativity (F-, Cl-, Br-) b. Electron Donating negative and partially negative ions, CH3 < C-CH3 (primary) < C-(CH3)2 (secondary) < C-(CH3)3 (tertiary) E. H BONDING H bonded to a more electronegative ion, making H partially positive and the other ion partially negative F. VAN DER WAALS distance, proximity and orientation of electron cloud a. Dipole-Dipole polar attraction with polar b. Dipole-Induced Dipole polar attraction with non-polar c. Induced Dipole-Induced Dipole non-polar attraction with non-polar G. STERIC EFFECT twisting from normal angle because of congestion due to presence of bulky groups; no more lone pair delocalization

Acidity of Organic Compounds

1. 2. 3. 4.

The higher the e- withdrawing effect, the more acidic The nearer the e- withdrawing atom, the more acidic C > primary C > secondary C > tertiary C Steric effect, less acidic.

Basicity of Organic Compounds

1. 2. 3. 4. C < Primary < Secondary < Tertiary 2 groups, more basic Lone pair delocalization, less basic Steric effect, least basic

Higher Ka = stronger acid = higher acidity = lower pKa = lower pH

Isomers
A. CONSTITUTIONAL differ in atom connectivity a. Skeletal b. Positional change in position of functional group

c.

Functional change in functional group

B. CONFORMATIONAL differ in arrangement of atoms due to rotation around a single bond a. Sawhorse

b. Newman

Torsional Strain due to congestion C. STEREOISOMERS same in connectivity of atoms but differ in 3D orientation a. Cis/Trans of Alkanes i. Cis on the same plane ii. Trans on different planes

b. Cis/Trans of Cyclic Structure

c.

E,Z Rule i. Entgegen opposite sides (E = enemy, therefore theyre on opposite sides) ii. Zusammen same sides (Z = Zee Zame Zides [the same sides])

To learn more about the E,Z Rule, please read the article found in the following linked website: http://www.chemguide.co.uk/basicorg/isomerism/ez.html