Organic chemistry - chemistry of the compounds of carbon, regardless of origin. - highly organized discipline.

Basic premise: The structure of the compound determines reactivity. Organic chemistry involves the study of the relationship between the structures of molecules and their reactions. Review from Chem 16 1. Hybrid orbitals: a) sp b) sp2 c) sp3 2. Multiple bonds - double bonds or triple bonds. In a multiple bond, only one of the bonds is a sigma bond. The rest are pi bonds. Covalent bond - formed from the overlap of 2 atomic orbitals. 2 modes of overlap: 1. Atomic orbitals may overlap end-on or head-to-head. Electron density is concentrated between the 2 nuclei. Sigma ( ) bond is formed. 2. Lateral or sideways overlap A pi () bond is formed. Electron density is concentrated above and below the 2 nuclei. Properties of a covalent bond: 1. bond length - the distance between the 2 nuclei Generalities: a. The bigger the atom, the longer the bond length. b. The greater the number of bonds/electrons between 2 atoms, the shorter the bond. c. The more s character in the hybrid orbital, the shorter the bond. 2. Bond dissociation energy - the amount of energy required to break a bond - measure of bond strength. The stronger the bond, the more energy is required to break that bond. In general, the shorter the bond, the more energy is required to break that bond. 3. Bond angle - the angle between any 2 bonds to an atom. This angle depends on how the bonding orbitals are oriented about the nucleus of the central atom. - differences based on hybridization of C Lewis structure of a covalent molecule shows all the electrons in the valence shell of each atom; the bonds between atoms are shown as shared pairs of electrons. The total number of electrons in the valence shell of each atom can be determined from its group number in the periodic table. Bonding electrons - shared electrons; may also be represented by a line or lines between two atoms. Nonbonding electrons - valence electrons that are not being shared; they are shown by dots oriented in a square around the symbol for the atom. Formal charge = (number of valence electrons) - (number of nonbonding electrons) - 1/2(number of bonding electrons) The sum of the formal charges on the atoms in an uncharged molecule is zero. For an ion, the sum of the formal charges on different atoms should add up to the charge of the ion. Oxidation number is determined based on two rules: 1. Electrons shared between two like atoms are divided equally between the two like atoms. 2. Electrons shared between two different atoms are counted with the more electronegative atom. Covalent bonds may also be polar or nonpolar. Polarity of the bond depends on the difference in electronegativity between the 2 bonded atoms. Electronegativity - the ability of an atom to attract electrons to itself. If one of the bonded atoms is more electronegative than the other, then a polar bond is formed, since the bonded electrons are more attracted to the more electronegative atom.

Electronegativity: F > O > Cl, N > Br > C, H C-H bond is considered nonpolar. Molecules containing polar bonds may or may not be polar. This will depend on the geometry or shape of the molecule. Intermolecular forces: 1. London forces - forces of attraction between nonpolar molecules 2. Dipole-dipole interaction - forces of attraction between polar molecules 3. H-bonding - a special kind of dipole-dipole attractions - present when H is bonded to a very electronegative atom like F, O and N. Physical properties like melting point, boiling point, and solubility, depend on intermolecular forces. Covalent bonds may be broken in 2 ways: 1. homolytic cleavage - one electron of the covalent bond being broken goes to each of the bonded atoms. - can be represented by a fishhook.

H H(g)

. . H(g) + H(g)
+

H = 107 kcal/mol

2. heterolytic cleavage - both electrons of the covalent bond being broken goes to only one of the bonded atom. - represented by an arrow.

H Cl

+ Cl

Bond breakage requires energy, while bond formation releases energy. Thus the H of the reaction results from the energy released from bond formation minus the energy required to break bonds. Resonance: Resonance contributors - differ only in the arrangement of electrons, not in the positions of the atoms. A double-headed arrow is used between the resonance contributors to indicate their relationship. General Rules for Resonance forms: 1. Individual resonance forms are imaginary, not real. 2. Resonance forms differ only in the placement of their or nonbonding electrons. 3. Different resonance forms of a substance dont have to be equivalent. 4. Resonance forms must be valid Lewis structures and obey normal rules of valency. 5. The resonance hybrid is more stable than any individual resonance forms. Rules for writing resonance structures: (Ege, 1994) 1. Only nonbonding electrons and electrons in multiple bonds change locations from one resonance contributor to another. The electrons in single bonds are not involved. 2. The nuclei of atoms in different resonance contributors are in the same positions. 3. All resonance structures have the same numbers of paired and unpaired electrons. Resonance contributors in which atoms of elements from the 2nd period all have 8 electrons are more important than those in which such atoms have fewer than 8 electrons. Resonance contributors with a greater number of covalent bonds are more important than those with a smaller number. For atoms of elements from periods beyond the 2 nd period, such as S and P, it is possible to write structures with 10 or more electrons around a central atom. 5. Resonance contributors in which there is little or no separation of charge are more important than those with a large separation of charge. Resonance contributors containing like charges on adjacent atoms are not favored. 6. When structures with a separation of charge are written, the more important resonance contributor has the negative charge on the more electronegative atom.

Major contributors to a resonance hybrid would be those resonance structures that have no separation of charge, with the maximum number of covalent bonds, and with octets of electrons around each atom. General reaction: Substrate + reagents products The substrate is the organic compound which is being transformed into the product. Reagents are the compounds necessary to bring about the transformation. Some Types of Organic Reactions: 1. Addition
X C C + XY C C Y

2.

Elimination

X C C
3. X

XY

Y Substitution Y + Y
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