Organic Chemistry

Youll Need to Know

the properties of organic compounds and how they are different from non-organic compounds how to draw condensed formulas how to draw and name various hydrocarbon compounds including: alkanes alkenes alkynes cyclic hydrocarbons how to draw and name various ring (aromatic) compounds how to draw and name compounds containing various functional groups including: alcohols carboxylic acids amides amines aldehydes ketones esters ethers how to draw and name various isomers including: structural chain positional functional stereisomerism geometric optical

Organic Chemistry

Properties of Organic Compounds

Organic compounds are any of a large class of chemical compounds whose molecules contain carbon, with the exception of carbides (i.e., SiC), carbonates (i.e., CaCO3), and carbon oxides (i.e., CO2). Organic compounds are generally covalently bonded and allow for unique structures such as long carbon chains and rings. The reason carbon is excellent at forming unique structures and that there are so many carbon compounds is that carbon atoms form very stable covalent bonds with one another (catenation). Some general properties of organic compounds include: 1. They usually have low melting points. In contrast to most inorganic materials, organic compounds typically melt, boil, sublime or decompose below 300C. 2. They usually are non-polar (unless they contain functional groups). Neutral organic compounds tend to be less soluble in water compared to many inorganic salts, with the exception of certain compounds such as low molecular weight alcohols and carboxylic acids where hydrogen bonding occurs. 3. They are usually nonconductors of electricity. 4. They can exist in solid, liquid, and gaseous form. Compounds with: 14 carbons tend to be gases at room temperature; butane and propane are among the lightest hydrocarbons and are used for fuel. 510 carbons tend to be in the liquid state at room temperature; compounds that fall in this size range are used to make gasoline and solvents. 1218 carbons make up jet fuels and kerosene. More than 18 carbons tend to be solids at room temperature. Organic compounds can exist as polymers, in which many repeating units called monomers, make up a larger molecule. Amino acids are monomers of proteins when amino acids are bonded in a chain and make a polypeptide or protein. Starches are polymers of the monomer glucose. Plastics are polymers of organic molecules extracted from crude oil. Some common examples include:

Polyethylenemany ethenes (ethylenes) strung together with covalent bonds. Example: shopping bags and plastic bottles. Polypropylenemany propenes strung together. Example: glues and carpets. Polystyrenea clear, hard, brittle polymer used in CD cases; if you blow carbon dioxide into it during manufacture you get the soft, opaque, foamy polymer used in coffee cups.

Condensed Formulas
Structures are condensed by leaving off the lone pairs and grouping the hydrogens with the carbon they are bonded to. Oxygens are also grouped with the carbon they are bonded to. For example, COH implies an alcohol group, whereas CHO implies an aldehyde. A very condensed structure might consist only of lines representing carboncarbon bonds. A carbon is assumed at every point where the line segments join. If that does not make four bonds around the carbon, it is also assumed that carbonhydrogen bonds make up the missing bonds. The hydrogens are not written.

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Examples
Q. How many hydrogen and carbon atoms are in each of the following structures?

CH3

HO A. B. C.

A. (a) 8 carbons, 18 hydrogens.

H

H C H

H C H

H C H

H C H

H C H

H C H

H C H

H C H H

(b) 3 carbons, 8 hydrogens.

H

OH H C H C H O

H C H

H C H H

(c) 7 carbons, 14 hydrogens.

H C H H C H C H H C H H H C H H C C H H

Hydrocarbons
A hydrocarbon is any chemical compound that consists only of the elements carbon and hydrogen. Aliphatic hydrocarbons do not contain a benzene ring whereas aromatic hydrocarbons do. All hydrocarbons contain a carbon backbone, called a carbon skeleton, and have hydrogen atoms attached to that backbone. Most hydrocarbons are combustible. There are essentially three types of hydrocarbons: (1) aromatic hydrocarbons, which have at least one benzene ring; (2) saturated hydrocarbons, also known as alkanes, which do not have double, triple, or aromatic bonds; and (3) unsaturated hydrocarbons, which have one or more double or triple bonds between carbon atoms and can be further divided into alkenes and alkynes.

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Alkanes
Alkanes are also known as saturated hydrocarbons (ending in ane). The saturated open-chain hydrocarbons form a homologous series called the alkane, or paraffin, series. The composition of each of the members of the series corresponds to the formula CnH2n +2, where n is the number of carbon atoms in the molecule. Among the members of the series are methane, CH4; ethane, C2H6; propane, C3H8; and butane, C4H10. All the members of the series are unreactive; that is, they do not react readily at ordinary temperatures with such reagents as acids, alkalis, or oxidizers; however, they are combustible at high enough temperatures. The first four members of the series are gases at ordinary temperature and pressure; intermediate members are liquids; and the heavier members are semi-solids or solids. Petroleum contains a great variety of saturated hydrocarbons, and such petroleum products as gasoline, heavy fuel oil, lubricating oils, and paraffin consist principally of mixtures of paraffin hydrocarbons, which range from the lighter liquid members to the solid members. CnH2n+2

Root Word and Number of Carbons meth- (1) hex- (6) eth- (2) hept- (7) prop- (3) oct- (8) but- (4) non- (9) pent- (5) dec- (10)

Examples methane H H C H CH4 H H ethane H C H H C H H H H C2H6 C H propane H C C H H H H H H H C4H10 H H H C butane H C H C H C H H H H C C C H C4H10 C H H isobutane H H H H

C3H8

Common Alkyl Groups methyl ethyl n-propyl n-butyl isopropyl CH3 CH2CH3 CH2CH2CH3 CH2CH2CH2CH3 H3C H3C t-butyl CH3 C CH3 CH3 CH

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Common Functional Groups amino fluoro chloro bromo iodo nitro vinyl NH2 F Cl Br I NO2 CH=CH2

Example
Q. Draw all of the structural isomers of C6H14 and name each. A. H H H H H H
H C H C H C H C H C H C H H

n-hexane H H H H C H H C H H C H H C H C H C H H H H H C H C H H C C H H C H C H H H

H 2-methylpentane H H H H C H H C H H C C C H H C H H H H

H 2, 3-dimethylbutane

H C H

H C H H

H C

H C H

H C H H

H 2, 2-dimethylbutane

H 3-methylpentane

Alkenes
Ending in ene, the alkene, or olefin series of chain hydrocarbons are those in which a double bond exists between two carbon atoms. The general formula for the series is CnH2n, where n is the number of carbon atoms. As in the alkane

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series, the lower members are gases, intermediate compounds are liquids, and the higher members of the series are solids. The alkene series compounds are more active chemically than the saturated compounds. They easily react with substances such as halogens, adding atoms at the double bonds. They are found to some extent in natural products, and are produced in the destructive distillation of complex natural substances, such as coal, and are formed in large amounts in petroleum-refining. CnH2n
Examples ethylene or ethene H H C C H H H C H C3H6 C H propene H C H H

C2H4

Example
Q. Draw all isomers of pentene, C5H10, and label them. A. CH2
CHCH2CH2CH3 1-pentene H C H C CH2CH2CH3 H CH3 H CH3CH CHCH2CH3

2-pentene CH2CH3 H cis-2-pentene CH3 H H C C CH2CH3

trans-2-pentene

Alkynes
The members of the alkyne series contain a triple bond between two carbon atoms in the molecule. They are very active chemically and are not found free in nature. They form a series analogous to the alkene series. The first and most important member of the series is ethyne, C2H2. CnH2n2
Examples C2H2 C3H4 Name ethyne propyne H Structural Formula H C H C H C4H6 butyne H H C H H C H 1-butyne C C H H H C H 2-butyne C C H C H H C C H C H

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Example
Q. Draw all of the structural isomers of pentyne and name each. A. H H H
H C C C H C H C H H H C C H C H C H H C H H C H H 3-methyl-1-butyne H H

1-pentyne H H C H C C H C H 2-pentyne

Cyclic Hydrocarbons
A cyclic compound is one in which a series of carbon atoms are connected together to form a loop or ring. The simplest of the saturated cyclic hydrocarbons, or cycloalkanes, is cyclopropane, C3H6; the molecules of which are made up of three carbon atoms to each of which two hydrogen atoms, are attached. Cyclopropane is somewhat more reactive than the corresponding open-chain alkane, propane, C3H8. CnH2n

Examples

Name

Structural Formula H H C H H C C CH2 CH2 H C H H H

C3H6

cyclopropane

H2C C4H8 cyclobutane H2C

C5H10

cyclopentane

H H

H C C H C C H H H H

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Ring (Aromatic) Compounds

All aromatic compounds are based on benzene, C6H6, which has a ring of six carbon atoms and has the symbol:

Each corner of the hexagon has a carbon atom with a hydrogen attached. A phenyl group, C6H5, is formed by removing a hydrogen from a benzene ring. There are three ways in which a pair of substituents can be placed on an aromatic ring. In the ortho (o) isomer, the substituents are in adjacent positions on the ring. In the meta (m) isomer, they are separated by one carbon atom. In the para (p) isomer, they are on opposite ends of the ring. The three isomers of dimethylbenzene, or xylene, are shown below.
CH3 CH3 CH3 CH3

CH3 ortho meta

CH3 para

Examples Cl NO2 CH3 CH2Cl COOH

chlorobenzene

nitrobenzene

methylbenzene

chloromethylbenzene O

benzoic acid

O NH2 CH CH2 C CH3

CH3

C O OH

phenylamine

phenylethene

phenylethanone

phenylethanoate

phenol

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CH3 CH3 Cl CH3

Cl 2-chloromethylbenzene 3-chloromethylbenzene

Cl 4-chloromethylbenzene

derivatives of methylbenzene OH Cl Cl COOCH3

COOH OH

Cl 2-hydroxybenzoic acid 2, 4, 6-trichlorophenol

NO2 methyl-3-nitrobenzoate

Example
Q. Name each of the following compounds. (a)
H3C CH2 CH CH CH3 CH2 CH3

(b)
H3C CH CH CH CH2 CH2 CH2 CH3

(c)
H2C CH CH2 CH CH2 CH2 CH3

CH3 CH3

A. (a) 3-methyl-4-phenylhexane; (b) 2-phenyl-3-octene; (c) 4-ethyl-2-phenylheptane

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Functional Groups
Alcohols
The hydroxyl group (OH) found in alcohols makes alcohols more soluble in polar solvents than the hydrocarbon from which they were derived and also increases the boiling point due to hydrogen bonding formed between the alcohol molecules. When naming alcohols, remove the ending of the hydrocarbon and replace with ol; e.g., ethane becomes ethanol.
OH

Examples methanol H H H CH3OH C O H H ethanol H C H H C H OH H H C H propanol H C H H C H OH

C2H5OH

1-propanol 2-propanol (isopropyl alcohol or isopropanol) H H C H C H C H

H OH H C3H7OH

Example
Q. Name the following alcohols.
OH H3C CH CH2 CH3 OH H2C CH CH3 CH3 H3C CH2 CH2 CH CH2 CH2 OH

CH2 CH3

A. (a) 2-butanol; (b) 2-methyl-1-propanol; (c) 3-ethyl-1-hexanol

Organic (Carboxylic) Acids

The functional group of an organic acid is known as a carboxyl group (COOH). Carboxylic acids are weak acids. To name organic acids, replace the ending with oic acid.
O C OH

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Examples methanoic (formic) acid O H C OH HCOOH H ethanoic (acetic) acid H C H C OH O H propanoic acid H C H C H C H OH O

CH3COOH

CH3CH2COOH

Amides
Amides are commonly formed from the reaction of a carboxylic acid with an amine which forms peptide bonds between amino acids. Amides can participate in hydrogen bonding as hydrogen bond acceptors and donors, but do not ionize in aqueous solution. Amide formation plays a role in the synthesis of some condensation polymers, such as nylon and Kevlar. For amides with an NH2 group, name the parent carboxylic acid, drop the oic acid and add amide. For amides with a substituted nitrogen, name the alkyl groups attached to the nitrogen, then name the parent acid, drop the oic acid and add amide.
O R1 C N R2 R3

Name acetamide or ethanamide

Structural Formula

O CH3CONH2 H3C C NH2

Amines
Amines are organic bases. The R groups can be hydrogen atoms or hydrocarbon groups. To name an amine, use the name of the hydrocarbon group followed by amine all written as a single word.
N R2

R1

R3

Examples methylamine H N H H C H H CH3NH2 H

H methylethylamine H diethylamine H H H N C C H H H H C C H H H

N C
H H

C C H

H H

H H

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Example
Q. Name the following amines.
CH3 CH2 a) H3C CH2 N CH2 CH3

b) H3C

CH2 CH2

NH

CH2 CH2 CH2 CH3

CH3 c) H2N CH CH3

A. (a) triethylamine (b) n-butyl-n-propylamine (c) isopropylamine

Aldehydes
Aldehydes contain a carbonyl group (C = O) to which at least one hydrogen is attached and the carbonyl group must be attached to the last carbon of the chain. To name an aldehyde, add the suffix -al.
O C R H

Examples methanal (formaldehyde) O C H CH2O H H3C ethanal (acetaldehyde) O C H CH3 propanal (propionaldehyde) H C H CH3CH2CHO O C H

CH3CHO

Ketones
Ketones have a carbonyl group (C=O) attached to an interior carbon atom. Ketones are commonly used as organic solvents due to their polarity. To name ketones, replace the ending of the molecule with the suffix -one and use a number to indicate the position of the carbonyl group in the molecule.
O C R1 R2

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Examples propanone (acetone) O C H3C CH3 H3C 2-butanone (methyl ethyl ketone) O C CH2 CH3COC2H5 CH3 C8H8O C6H10O acetophenone H3C C O O cyclohexanone

CH3COCH3

Esters
Esters are commonly formed as the product of a condensation reaction between an acid (usually an organic acid) and an alcohol (or phenol compound). Condensation reactions occur when two molecules are joined together and eliminate a small molecule, e.g., H2O. A condensation reaction to form an ester is called esterification. To name esters, use the name of the group derived from the alcohol followed by the name of the group derived from the acid, end with -oate.
O C R1 OR2

Examples methyl methanoate (methyl formate) O H O methyl ethanoate (methyl acetate or acetic acid methyl ester) O O C3H6O2 ethyl ethanoate (ethyl acetate) O O C4H8O2

HCOOCH3

Ethers
Ethers are formed by the condensation reaction between two alcohols. To name ethers, place the names (in alphabetical order) of the two R groups before the word ether. R1OR2

Examples dimethyl ether H H C H O H C H H H ethyl methyl ether H C H H C H C2H5OCH3 O H O C H H C2H5OC2H5 diethyl ether

CH3OCH3

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Isomers
Isomers are compounds with the same formula but different properties that result from different structures. There are two broad classes of isomers: structural isomers and stereoisomers.
Chain Structural Positional Functional Isomerism

Geometrical Stereo Optical

Structural Isomerism
Structural isomerism occurs when two or more organic compounds have the same molecular formula, but different structures. These differences tend to give the molecules different chemical and physical properties. Structural isomers have the same molecular formula but different molecular structures (different connectivities or different numbers and kinds of chemical bonds). Organic examples of structural isomers: CH3OCH3 (dimethyl ether) and CH3CH2OH (ethyl alcohol). There are three types of structural isomerism: chain isomerism, positional isomerism, and functional isomerism.

Chain Isomerism
Chain isomerism, also called nuclear isomerism, occurs when the way carbon atoms are linked together is different from compound to compound. There are three chain isomers of C5H12 shown below. Note that these isomers have the same molecular formula as pentane, but different conformations.

pentane H H C H H C H H C H H C H H C H H

2-methylbutane H H C H H C H H C H C H H H C H H

2,2-dimethylpropane H H H H C H H C H C C H H C H H H

Positional Isomerism
Positional isomerism occurs when functional groups are in different positions on the same carbon chain. Positional isomers of alcohols, alkenes, and aromatics are common. Below are models of the positional isomers of butanol:

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1-butanol H H C H H C H H C H H C H OH H

2-butanol H C H H C H C H C H

H OH H

Functional Isomerism
Functional isomerism occurs when substances have the same molecular formula but different functional groups. This means that functional isomers belong to different homologous series. There are two functional group isomers of which you need to be aware of:

alcohols and ethers aldehydes and ketones

Below are models of the functional isomers ethanol and methoxymethane.

ethanol (alcohol) H H C H H C H OH

methoxymethane (ether) H H C H O H C H H

Alcohols have the hydroxyl group OH.

Ethers have the functional group ROR.

Below are the models of the functional isomers propanal and propanone both of which have 3 carbons, 6 hydrogens, and 1 oxygen.

propanal (aldehyde)
H CH3 C H O C H

propanone (ketone) O C H3C CH3 O C

O C R1 H R1 Aldehydes have this funtional group

R2

whereas ketones have this functional group

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Stereisomerism
When the atoms in a molecule can have different arrangements in space, stereisomerism occurs. There are two types of stereoisomerism: geometrical isomerism and optical isomerism.

Geometric Isomerism
Geometric isomerism occurs when substances have the same molecular formula, but a different arrangement of their atoms in space. When like groups are on the same side of the double bond, we call it a cis isomer; when they are on opposite sides it is called a trans isomer.
cis-2-butene
1

trans-2-butene
4

H3C
2 3

CH3 C C H

H
2 3

CH3 C C H

H3C
1

Optical Isomerism
Optical isomerism occurs when substances have the same molecular and structural formula, but one cannot be superimposed on the other; i.e., mirror images of each other. No matter how hard you try, the molecule on the left will not turn into the molecule on the right. Molecules like this are said to be chiral (pronounced ky-ral), and the different forms are called enantiomers.

Optical isomers can occur when there is an asymmetric carbon atom. An asymmetric carbon atom is one which is bonded to four different groups; there must be four groups, and they must be different. Optical isomers can rotate the plane of polarization of plane-polarized light: one enantiomer rotates the polarized light clockwise (to the right) and is the (+) enantiomer and the other rotates the polarized light counterclockwise (to the left) and is called the () enantiomer. A mixture containing equal concentrations of the (+) and () enantiomers is not optically activei.e., will not rotate polarized light and is called a racemic mixture. Below are models of the optical isomers of 2-hydroxypropanoic acid (lactic acid). Lactic acid is a fairly common and simple example of optical isomerism. The (+) enantiomer of lactic acid is found in muscles. Sour milk contains a racemic mixture of the two enantiomers.

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(+) lactic acid COOH HO C CH3 H

() lactic acid COOH H C CH3 OH

See Chapter 16 for organic reactions.

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