William L Masterton Cecile N.

Hurley
http://academic.cengage.com/chemistry/masterton

General, Organic, and Biochemistry, 8e

Bettelheim, Brown, Campbell, & Farrell

Organic Chemistry
Edward J. Neth University of Connecticut

Organic Chemistry
Organic chemistry: the study of the compounds of carbon. Organic compounds are made up of carbon and only a few other elements. chief among these are hydrogen, oxygen, and nitrogen also present are sulfur, phosphorus, and halogens (fluorine, chlorine, bromine, or iodine)

Organic Chemistry
Why is organic chemistry a separate discipline within chemistry? Historical: scientists at one time believed that a vital force present in living organisms was necessary to produce an organic compound. The experiment of Whler in 1828 was the first in a series of experiments that led to the demise of the vital force theory. O
NH4 Cl + AgNCO Ammonium Silver ch loride cyan ate heat H2 N-C-NH2 + AgCl Urea Silver chloride

Organic Chemistry
The sheer number of organic compounds Chemists have discovered or made over 10 million organic compounds and an estimated 100,000 new ones are discovered or made each year. By comparison, chemists have discovered or made an estimated 1.7 million inorganic compounds. Thus, approximately 85% of all known compounds are organic.

Some organic chemicals

DNA

Medicines
Active Pharmaceutical Ingredients Excipients

Fuels

Materials

Essential oils

Pigments

Organic Chemistry
The link to biochemistry Carbohydrates, lipids, proteins, enzymes, nucleic acids, hormones, vitamins, and almost all other chemicals in living systems are organic compounds.

Organic Chemistry
Organic chemistry deals with compounds of carbon, of which there are millions Over 90% of all known compounds contain carbon Carbon atoms bond to each other to a greater extent than atoms of any other element Chains and rings may form

Common Elements in Organic Chemistry

1. Organic compounds are molecular rather than ionic 2. Each carbon atom ordinarily forms four covalent bonds 3. Carbon atoms may bond to atoms of other elements, most often hydrogen, a halogen, oxygen, nitrogen and sulfur

Organic Chemistry
a comparison of organic and inorganic compounds
Organi c Comp ound s Bond ing is almost entirel y co val ent May be g ases, li quid s, o r so li ds w ith l ow melti ng po ints (l ess than 360C) Mo st are i nsol ubl e in w ater Mo st are so lu ble i n o rg an ic so lv en ts such as d iethy l ether, to luene, and dichl orometh ane Aqu eo us so lutio ns do n ot condu ct el ectrici ty Al most all burn Reacti ons are usuall y sl ow Ino rg an ic Co mpou nds M ost have i oni c bo nds M ost are sol id s w ith h ig h melting po in ts M any are so lu ble i n w ater A lmo st al l are i nso lubl e in o rgani c so lvents A queous sol uti ons cond uct electrici ty V ery f ew burn Reactio ns are o ften very fast

Considerations in this Chapter

Hydrocarbons Carbon and hydrogen only Organic compounds containing N or O Structural formulas Isomerism Organic Reaction

Saturated Hydrocarbons: Alkanes

Formula: CnH2n+2 Simple alkanes (n = 1, 2, 3)

Carbons surrounded by four single bonds sp3 hybrid orbitals Bond angles approximately 109.5

n 1 2 3 4

Molecular Formula

Structural formula
H H C H H H H H C C H H H H H H H C C C H H H H H H H H H C C C C H H H H H

Name methane ethane

Condensed structural formula

CH4 C2H6 C3H8 C4H10

CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 CH3CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH3

propane

butane

5
6

C5H
C6H

H H H H H 12 H C C C C C H H H H H H H H H H H H 14 H C C C C C C H H H H H H H

pentane

hexane

Further members of the series

Heptane Octane CH3CH2CH2CH2CH2CH2CH3 CH3CH2CH2CH2CH2CH2CH2CH3

Nonane
Decane

CH3CH2CH2CH2CH2CH2CH2CH2CH3
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3

Undecane
Dodecane Etc., etc.

CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3

Table 22.1 Nomenclature of Alkanes

Structural Isomers of Butane

Two different alkanes with the formula C4H10

Molecular view of alkanes Figure 22.1

Figure 22.2 - Molecular Structures of Butane Isomers

Nomenclature
IUPAC naming schema For straight chains, the name is based on a single word For branched chains, the name is derived from the longest straight chain, with additions for branch points
Suffix is based on the longest chain Prefix is numbered for the carbon where the branch is located

IUPAC Names for Isomers of Pentane

Sources and Uses of Alkanes

Natural gas 80-90% methane Remainder is C2H6, C3H3, and C4H10 Bottled gas Compressed such that the gas inside is liquefied Petroleum Crude oil is the source of other hydrocarbons Distillation separates the components
Gasoline Diesel fuel Asphalt

Figure 22.3 Bottled Gas

Figure 22.4 Refining Petroleum

Gasoline
Straight chain and branched isomers Branched isomers burn more smoothly

Anti-knock compounds Tetraethyl lead (C2H5)4Pb

Not used in the US in decades

Ethyl alcohol (C2H5OH)

Currently widely used in gasoline

Cycloalkanes
Alkanes can form rings rather than straight chains These are called cycloalkanes Contain two fewer hydrogens than chain alkanes

Figure 22.5 - Molecular Structure of Cycloalkanes

Unsaturated Hydrocarbons: Alkenes and Alkynes Unsaturated compounds contain at least one multiple bond Alkenes contain double bond(s)
Each double bond replaces a pair of hydrogens General formula is CnH2n

Alkynes contain triple bond(s)

Each triple bond replaces two pairs of hydrogens General formula is CnH2n-2

Structures of Alkenes and Alkynes

Alkene

Alkyne

Example 22.3

Alkenes
The simplest alkene: ethene (common name, ethylene)

A double bond consists of a sigma and a pi bond There is no rotation about the bond The ideal bond angles are 120 Ethene is produced commercially in vast quantity Used as a starting material for polyethylene Also a plant hormone that ripens fruit

Naming Alkenes
Alkenes are named as alkanes, with two exceptions -ane is replaced by ene Where necessary, the number used to designate the carbon of the double bond is made as small as possible

Example 22.4

Alkynes
The name of an alkyne is derived from that of an alkane, with the suffix changed from ane to yne Acetylene, C2H2, is the most common alkyne (systematic name: ethyne)

Acetylene
Acetylene is used as a welding gas
C2H2 (g) + O2 (g) CO2 (g) + H2O (l) H = -1300 kJ

Acetylene is thermodynamically unstable with respect to decomposition into its elements

C2H2 (g) 2C (g) + H2 (g) G = -209.2 kJ at 25 C Because of the instability, acetylene is stored in a cylinder packed with porous material as a solution in acetone

Aromatic Hydrocarbons and Derivatives

Aromatic hydrocarbons (also called arenes) Derived from benzene (C6H6) Highly unsaturated
Differ in properties from alkenes Each carbon forms three sigma bonds, one to a hydrogen atom and two to carbon atoms The remaining electron pairs are spread over the molecule

Condensed Ring Structures

Fusion of benzene rings results in polycyclic compounds

Functional Groups
Many organic molecules contain functional groups Functional group: an atom or group of atoms within a molecule that shows a characteristic set of predictable physical and chemical properties. Nonmetal atom Small group of atoms

Functional Groups
Functional groups are important because They undergo the same types of chemical reactions no matter in which molecule they are found. To a large measure they determine the chemical and physical properties of a molecule. They are the units by which we divide organic compounds into families. They provide the basis on which we derive names for organic compounds.

Table 22.2

Alcohols
Alcohols, R-OH R is the alkyl group -OH is the functional group

Ethers
Ethers have the general structure R-O-R The R groups may be the same or different CH3-O-CH3, dimethyl ether CH3-O-CH2CH3, methyl ethyl ether

Alcohols and Ethers

Properties of alcohols and ethers Alcohols have higher boiling points than ethers of comparable molar mass
The hydrogen bond strengthens the interaction of alcohol molecules Ethers cannot hydrogen bond

Alcohols of low molar mass are generally watersoluble

Again, the hydrogen bond accounts for the solubility

Table 22.3 Physical Properties

Commercial Alcohols and Ethers

Methanol is prepared from synthesis gas
ZnO, Cr2O3

CO (g) + H2O (l)

250 atm, 350 C

CH3OH

Ethanol is formed from fermentation of sugar Common name: grain alcohol CH3CH2OH

Commercial Alcohols and Ethers, (Contd)

Alcohols with more than one OH group

Diethyl ether C3CH2OCH2CH3 Ethers react with oxygen in air to form peroxides, which are potent explosives

Aldehydes and Ketones

The carbonyl group

In a ketone, there are alkyl groups on either side of the carbonyl group In an aldehyde, there is a hydrogen on one side (at the end of the chain) Properties of aldehydes are different from those of ketones

Common Aldehydes and Ketones

Acetone Water soluble Common solvent Used in fingernail polish remover Formaldehyde Used in a water solution as formalin Preservative Carcinogenic

Aromatic Aldehydes
Aromatic aldehydes are used as flavoring agents and as odorants

Example 22.6

Carboxylic Acids and Esters

Carboxylic acid

Common carboxylic acids

Acidity of Carboxylic Acids

RCOOH (aq) H+ (aq) + RCOO- (aq) Strength varies from weak to strong Trichloroacetic acid has Ka = 0.20
Strong acid Used to remove warts

Treatment of carboxylic acids with alkali metal hydroxide (strong base) results in a sodium salt of the acid For long-chain acids, these are soaps

Esters
Reaction between a carboxylic acid and an alcohol results in an ester

The reaction between acetic acid and methyl alcohol is typical of these reactions Product is methyl acetate

Table 22.4 - Properties of Esters

Amines
Amines have the structure R-NH2 Primary amines have one alkyl group CH3NH2, methylamine, is the simplest amine
Flammable gas Unpleasant, fishy odor Weak base (Kb = 4 X 10-4) Reacts with strong acid
CH3NH2 (aq) + H+ (aq) CH3NH3+ (aq)

Other amines have foul odors

Isomerism in Organic Compounds

Isomers are distinctly different compounds, with the same molecular formula Have different chemical and physical properties

Chain Structural Isomers

Consider the structural isomers of C5H12 One is linear and the other two are branched

Position Structural Isomers

Consider the structure C4H8 Look at the position or location of the double bond

Structural Isomers with Functional Groups

Consider the structural isomers of C3H8O Two are alcohols; the third is an ether

Example 22.9

Stereoisomers
Types of stereoisomers Conformational, Geometric and Optical
I som ers s ame dif f erent connectivi ty connectivi ty Stereoi som ers without with s tereocenters s tereocenters A chiral Cis-Tra ns I som ers C hiral Enantiom ers Dias tereomers C ons titutional I s omers

Geometric Isomers: cis-trans

Geometric isomerism arises where alkenes are concerned There is no free rotation about the double bond Consider C4H8
One pair of isomers is geometric cis when groups are on same side of double bond; trans when on opposite sides

Example 22.10

Optical Isomers
Optical isomers are possible when at least one carbon is bonded to four different atoms or groups Non-superimposable mirror images Consider your right and left hands
They are mirror images They are not superimposable on each other

Figure 22.11 Optical Isomers

Terminology
A carbon with four different atoms or groups bonded to it is called chiral The two different forms are called enantiomers The carbon atom is the chiral center Molecules may contain more than one chiral center, and there are more than two enantiomers as a result

Example 22.11

Two Stereocenters
For a molecule with n stereocenters, the maximum number of possible stereoisomers is 2n. We have already verified that, for a molecule with one stereocenter, 21 = 2 stereoisomers (one pair of enantiomers) are possible. For a molecule with two stereocenters, a maximum of 22 = 4 stereoisomers (two pair of enantiomers) are possible. For a molecule with three stereocenters, a maximum of 23 = 8 stereoisomers (four pairs of enantiomers) are possible. and so forth

Interaction of Enantiomers with Light

When plane polarized light is passed through a sample of an enantiomer, the plane is rotated from its original position Optical isomerism
One isomer rotates right One isomer rotates left

Figure 22.13

Optical Activity
Dextrorotatory: clockwise rotation of the plane of plane-polarized light. Levorotatory: counterclockwise rotation of the plane of plane-polarized light. Specific rotation: the observed rotation of an optically active substance at a concentration of 1 g/mL in a sample tube 10 cm long.
COOH H H3 C OH (S)-(+)-Lactic acid
21 [] D = +2.6

COOH H C CH3 HO (R)-(-)-Lactatic acid

21 [] D = -2.6

Optical Inactivity
If both isomers are present in equal amounts, the mixture is called racemic
Offsets cancel and there is no net rotation

Mesocompounds- when there is internal mirror image, optical rotation will cancel out

Organic Reactions
Organic reactions Usually between molecules, not ions Solvents are often nonpolar Four general types Addition Elimination Condensation Substitution

Polymers
Polymers are large molecules Made up of smaller units called monomers Chain of monomers can be thousands of units long Synthetic organic polymers Joined by addition or condensation Make up tires, cups, plates, fabrics Natural polymers Cellulose, a polymeric carbohydrate Proteins

Table 23.1 - Synthetic Addition Polymers