Organic Chemistry

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

Resources of organic compounds: petroleum and coal

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

Classification of Organic compounds: functional groups

In organic chemistry functional groups are submolecular structural motifs, characterized by specific elemental composition and connectivity, that confer reactivity upon the molecule that contains them.

O rg anic co mpo und s

Hyd ro ca rb on s

Hyd rocar rbon de rivative s

Aliph atic

Aro matic

Alka nes Alke nes Alkyn es c-c C C C C

Haloa lka ne s R X

Alco ho l R OH

Ether O

Amin e Ald eh yd es Keton es O O R NH 2 C CH

Car bo xylic acids

Ester

Amid e

RCOO H

RCO OR RCO NH2

Functional groups

Structural formula and nomenclature

 Structural Theory
Central Premises
Valency: atoms in organic compounds form a fixed number of bonds

Carbon can form one or more bonds to other carbons

 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

Different Kinds of Carbons & Hydrogens

Naming of Alkanes, Alkenes & Alkynes

 Alkanes are hydrogen carbons containing only single bonds

General formula: CnH2n+2

Naming straight-chain alkanes

Number of Carbons 1 2 3 4 5 6 Prefix Methane Ethane Propane Butane Pentane Hexane Structure CH4 CH3CH3 CH3CH2CH3 CH3(CH2)2CH3 CH3(CH2)3CH3 CH3(CH2)4CH3

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

CH3CHCH2CH2CH3 CH3 2-methylpentane

CH3CH2CH2CHCH2CH2CH2CH3 CHCH3 CH3 4-isopropyloctane

CH3 CH3CHCH2CH2CH3 common name: isohexane systematic name: 2-methylpentane

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

(substituents are listed in alphabetical order)

4. Assign the lowest possible numbers to all of the substituents

CH3 CH3
CH3CH2CHCH2CHCH3 CH3 CH3
CH2CH3 CH3

CH3CH2CH2C

CCH2CH3

CH3CH2CHCH2CH2CHCHCH2CH2CH3 CH2CH3 CH2CH3

CH3 CH3 3,3,4,4-tetramethylheptane

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

CH3CH2CHCHCH2CHCH2CH3 CH3 6-ethyl-3,4-dimethyloctane not 3-ethyl-5,6-dimethyloctane because 4<5

2,2,4-trimethylpentane not 2,4,4-trimethylpentane because 2<4

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

CH3CH2CHCH2CH2CH3 CHCH3 CH3 3-isopropylhexane (one substituent)

3-ethyl-2-methylhexane (two substituents)

8. Certain common nomenclatures are used in the IUPAC system

CH3CH2CH2CH2CHCH2CH2CH3 CHCH3 CH3 4-isopropyloctane or 4-(1-methylethyl)octane
CH3CH2CH2CH2CHCH2CH2CH2CH2CH3 CH2CHCH3 CH3 5-isobutyldecane or 5-(2-methylpropyl)decane

Nomenclature of Alkyl Substituents

Nomenclature of Cycloalkanes
1. No number is needed for a single substituent on a ring
CH2CH3

CH2CH2CH2CH2CH3

CH3

methylcyclopentane

ethylcyclohexane

1-cyclobutylpentane

2. Name the two substituents in alphabetical order

CH3
H3CH2C
H3C CH2CH2CH3 1-methyl-2-propylcyclopentane

CH3

CH3
1-ethyl-3-methylcyclopentane

1,3-dimethylcyclohexane

3. If there are more than two substituents,

CH3CH2CH2

CH3 CH3

H3C

CH2CH3

CH3 1,1,2-trimethylcyclopentane not 1,2,2-trimethylcyclopentane because1<2 not 1,1,5-trimethylcyclopentane because 2<5

4-ethyl-2-methyl-1-propylcyclohexane not 1-ethyl-3-methyl-4-propylcyclohexane because2<3 not 5-ethyl-1-methyl-2-propylcyclohexane because 4<5

Nomenclature of Alkenes

Alkenes
Hydrocarbons containing double bonds

double bond the functional group center of reactivity

Molecular Formula of Alkene

Noncyclic alkene: CnH2n
CH3CH2=CH2

Cyclic alkene: CnH2n2

Systematic Nomenclature of Alkenes

Longest continuous chain containing the functional group
A B C

Cite the substituents in alphabetical order

Name with the lowest functional group number and then the lowest substituent numbers

5-methyl-2-propyl-2-hexene

No numbering of the functional group is needed in a cyclic alkene

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

A substituent receives the lowest number if there is no functional group suffix,

Cl Br CH3CHCHC CCH2CH2CH3
1 2 3 4 5 6 7 8

3-bromo-2-chloro-4-octyne not 6-bromo-7-chloro-4-octyne because 2 < 6

or if the same number for the functional group suffix is obtained in both directions
CH3 CH3CHC
6 5 4

CCH2CH2Br
3 2 1

1-bromo-5-methyl-3-hexyne not 6-bromo-2-methyl-3-hexyne because 1 < 2

Physical Properties of Alkynes

The physical properties of alkynes are similar to those of alkanes and alkenes.

Structure and Bonding in Alkynes: sp Hybridization

Structure
linear geometry for acetylene
H

120 pm C C

106 pm

106 pm

CH3

121 pm C C

146 pm

106 pm

Nomenclature of Alkyl Halides

CH3Cl chloromethane CH3CH2F fluoroethane CH3CHI CH3 2-iodopropane CH3CH2CHBr CH3 2-bromobutane

In the IUPAC system, alkyl halides are named as substituted alkanes

CH3 CH3CH2CHCH2CH2CH2CH3 Br 2-bromo-5-methylheptane

CH3 CH3CH2CHCH2CH2CH2Cl CH3 1-chloro-5,5-dimethylhexane

Br

CH2CH3

Cl
1-ethyl-2-iodocyclopentane

CH3 4-bromo-2-chloro-1-methylcyclohexane

Different Kinds of Alkyl Halides

 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

1 curve arrow = 1 pair e-

 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

All structures must be proper Lewis structures

 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

Reaction Building Paradigms

1. Additions => bimolecular reactions if linear; unimolecular if cyclization occurs
(a) linear

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

=> involves re-organization of skeletal arrangement of molecule

=> term applied to substrate structure re-organization or to intermediate structure re-organization => usually are unimolecular

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

Mechanisms of Organic Reactions

A detailed description of the changes in structure and bonding that take place in the course of a reaction, and the sequence of such events is called the reaction mechanism. A reaction mechanism should include a representation of plausible electron reorganization, as well as the identification of any intermediate species that may be formed as the reaction progresses.

The Arrow Notation in Mechanisms

two kinds of curved arrows are used in drawing mechanisms:
A full head on the arrow indicates the movement or shift of an electron pair:

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

The following equations illustrate the proper use of these symbols:

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