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Organic Chemistry
Organic compounds are compounds containing carbon Carbon neither readily gives up nor readily accepts electrons
Carbon shares electrons with other carbon atoms as well as with several different kinds of atoms such as H, O, N, S, X etc. A simple molecule: CH4 A complex molecule: polymer
Organic products
Petroleum and its products Natural gases Coal Synthetic resins and plastics Adhesives Pharmaceutical Cosmetics Soap and detergents Synthetic organic chemicals Sugar and sweeteners Textiles Dye Pigments and paint
Some examples
O CH3 Cl CH CCl3 DDT O S N CO2H H3C O CH3 N Cl O COOH aspirin H N O O penisilin
N N CH3 caffein
n Cl PVC
N N methyl orange
SO3Na
Hyd ro ca rb on s
Aliph atic
Aro matic
Haloa lka ne s R X
Alco ho l R OH
Ether O
Ester
Amid e
RCOO H
Functional groups
Structural Theory
Central Premises
Valency: atoms in organic compounds form a fixed number of bonds
Isomers
Isomers are different molecules with the same molecular formula Many types of isomers exist Example Consider two compounds with molecular formula C 2H 6O These compounds cannot be distinguished based on molecular formula; however they have different structures The two compounds differ in the connectivity of their atoms
Constitutional Isomers
Constitutional isomers are one type of isomer They are different compounds that have the same molecular formula but different connectivity of atoms They often differ in physical properties (e.g. boiling point, melting point, density) and chemical properties
Constitutional isomers have the same molecular formula, but their atoms are linked differently
7
8 9 10 11 12
Heptane
Octane Nonane Decane Undecane Dodecane
CH3(CH2)5CH3
CH3(CH2)6CH3 CH3(CH2)7CH3 CH3(CH2)8CH3 CH3(CH2)9CH3 CH3(CH2)10CH3
Nomenclature of Alkanes
1. Determine the number of carbons in the parent hydrocarbon
8 7 6 5 4 3 2 1
CH3CH2CH2CH2CHCH2CH2CH3 CH3
CH3CH2CH2CH2CHCH2CH3 CH2CH2CH3
3 2 1
CH3CH2CH2CHCH2CH2CH3 CH2CH2CH2CH3
5 6 7 8
2. Number the chain so that the substituent gets the lowest possible number
1 2 3 4 5
1 2 3 4 5 6 7 8
3. Number the substituents to yield the lowest possible number in the number of the compound
CH3CH2CHCH2CHCH2CH2CH3 CH3 CH2CH3 5-ehtyl-3-methyloctane not 4-ethyl-6-methyloctane because 3<4
CH3CH2CH2C
CCH2CH3
2,4-dimethylhexane
3,3,6-triethyl-7-methyldecane
5. When both directions lead to the same lowest number for one of the substituents, the direction is chosen that gives the lowest possible number to one of the remaining substituents
CH3 CH3CHCH2CHCH3 CH3 CH3
CH3 CH2CH3
6. If the same number is obtained in both directions, the first group receives the lowest number
Cl CH3CH2CHCH3 Br 2-bromo-3-chlorobutane not 3-bromo-2-chlorobutane
CH2CH3 CH3CH2CHCH2CHCH2CH3 CH3 3-ethyl-5-methylheptane not 5-ethyl-3-methylheptane
7. In the case of two hydrocarbon chains with the same number of carbons, choose the one with the most substituents
3 4 5 6
1 2 3 4 5 6
CH3CH2CHCH2CH2CH3
2 CHCH3 1 CH3
Nomenclature of Cycloalkanes
1. No number is needed for a single substituent on a ring
CH2CH3
CH2CH2CH2CH2CH3
CH3
methylcyclopentane
ethylcyclohexane
1-cyclobutylpentane
CH3
CH3
1-ethyl-3-methylcyclopentane
1,3-dimethylcyclohexane
CH3CH2CH2
CH3 CH3
H3C
CH2CH3
Nomenclature of Alkenes
Alkenes
Hydrocarbons containing double bonds
Name with the lowest functional group number and then the lowest substituent numbers
5-methyl-2-propyl-2-hexene
Isomers of Alkene
Nomenclature of Alkynes
Alkynes are hydrocarbons that contain a carboncarbon triple bond General formula: CnH2n2 (acyclic); CnH2n4 (cyclic)
Nomenclature
In common nomenclature, alkynes are named as substituted acetylenes
or if the same number for the functional group suffix is obtained in both directions
CH3 CH3CHC
6 5 4
CCH2CH2Br
3 2 1
Structure
linear geometry for acetylene
H
120 pm C C
106 pm
106 pm
CH3
121 pm C C
146 pm
106 pm
CH2CH3
Cl
1-ethyl-2-iodocyclopentane
CH3 4-bromo-2-chloro-1-methylcyclohexane
Resonance
Often a single Lewis structure does not accurately represent the true structure of a molecule The real carbonate ion is not represented by any of the structures 1,2 or 3
Experimentally carbonate is known not to have two carbonoxygen single bonds and one double bond; all bonds are equal in length and the charge is spread equally over all three oxygens
The real carbonate ion can be represented by a drawing in which partial double bonds to the oxygens are shown and partial negative charge exists on each oxygen The real structure is a resonance hybrid or mixture of all three Lewis structures Double headed arrows are used to show that the three Lewis structures are resonance contributors to the true structure The use of equilibrium arrows is incorrect since the three structures do not equilibrate; the true structure is a hybrid (average) of all three Lewis structures
One resonance contributor is converted to another by the use of curved arrows which show the movement of electrons The use of these arrows serves as a bookkeeping device to assure all structures differ only in position of electrons
A calculated electrostatic potential map of carbonate clearly shows the electron density is spread equally among the three oxygens Areas which are red are more negatively charged; areas of blue have relatively less electron density
Rules for Resonance: Individual resonance structures exist only on paper The real molecule is a hybrid (average) of all contributing forms Resonance forms are indicated by the use of double-headed arrows Only electrons are allowed to move between resonance structures The position of nuclei must remain the same Only electrons in multiple bonds and nonbonding electrons can be moved Example: 3 is not a resonance form because an atom has moved
Rules to Assign Relative Importance of Resonance Forms A resonance form with more covalent bonds is more important than one with less Example: 6 is more stable and more important because it has more total covalent bonds
Resonance forms in which all atoms have a complete valence shell of electrons are more important Example: 10 is more important because all atoms (except hydrogen) have complete octets
Resonance forms with separation of charge are less important Separation of charge cost energy and results in a less stable resonance contributor Example: 12 is less important because it has charge separation
Forms with negative charge on highly electronegative atoms are more important Those with positive charge on less electronegative atoms are also more important
Example The nitrate ion is known to have all three nitrogen-oxygen bond lengths the same and the negative charge spread over all three atoms equally
Resonance theory can be used to produce three equivalent resonance forms Curved arrows show the movement of electrons between forms When these forms are hybridized (averaged) the true structure of the nitrate ion is obtained
Type of reactions
2. Condensations => involves loss of small hydroxylic molecule such as water or alcohols => bimolecular reactions if linear; unimolecular if cyclization occurs
3. Couplings => usually reserved for synthesis of new carbon-carbon bonds => may be an addition with no elimination products (see 1(a) and 1(b)), or an addition with elimination products (i.e., a substitution (see 6) or a condensation (see 2(a) and 2(b)). => bimolecular reactions if linear; unimolecular if cyclization occurs
4. Cyclizations => rings are formed => may be bimolecular or unimolecular (a) See 1(b) (b) See 2(b)
(d) special reactions involving rings: ring expansions (usually by one atom unit); ring contractions (usually by one atom unit)
5. Rearrangements
6. Substitutions => part of substrate molecule is replaced by another group => rate determining step is bimolecular if concerted => rate determining step is unimolecular if rate determining cleavage occurs first followed by capture of intermediate by incoming group
7. Oxidation with respect to substrate => substrate loses Hs, gains Os, and/or loses electrons => oxidizing agents are necessarily reduced
8. Reduction with respect to substrate => substrate gains Hs, loses Os, and/or gains electrons => reducing agents are necessarily oxidized
9. Fragmentations => cleavage of original structure into at least two fragments => may be coupled with reduction or oxidation process => usually are unimolecular
10. Eliminations => cleavage of original structure into two fragments, one of which has a new pi-bond => rate determining step is bimolecular if concerted => rate determining step is unimolecular if rate determining cleavage occurs first followed by creation of new pi-bond
A partial head (fishhook) on the arrow indicates the shift of a single electron:
If a covalent single bond is broken so that one electron of the shared pair remains with each fragment, as in the first example, this bondbreaking is called homolysis. If the bond breaks with both electrons of the shared pair remaining with one fragment, as in the second and third examples, this is called heterolysis.
Bond-Breaking Bond-Making
Chemists also use arrow symbols for other purposes, and it is essential to use them correctly.
The Reaction Arrow The Equilibrium Arrow The Resonance Arrow
Reactive Intermediates
The products of bond breaking, shown above, are not stable in the usual sense, and cannot be isolated for prolonged study. Such species are referred to as reactive intermediates, and are believed to be transient intermediates in many reactions.
ENDS