1.

4
organic halide a compound of carbon and hydrogen in which one or more hydrogen atoms have been replaced by halogen atoms

Organic Halides
Organic halides are a group of compounds that includes many common products such as Freons (chlorofluorocarbons, CFCs) used in refrigerators and air conditioners, and Teflon (polytetrafluoroethene), the nonstick coating used in cookware and labware. While we use some organic halides in our everyday lives, many others are toxic and some are also carcinogenic, so their benefits must be balanced against potential hazards. Two such compounds, the insecticide DDT (dichlorodiphenyltrichloroethane) and the PCBs (polychlorinated biphenyls) used in electrical transformers, have been banned because of public concern about toxicity. In Section 1.3 you learned that when H atoms in an alkane are replaced by halogen atoms, the resulting organic halide is more specifically referred to as an alkyl halide.

Naming Organic Halides

When naming organic halides, consider the halogen atom as an attachment on the parent hydrocarbon. The halogen name is shortened to fluoro-, chloro-, bromo-, or iodo-. For example, the structure shown below is 1,2-dichloroethane, indicating an ethane molecule substituted with a chlorine atom on carbon 1 and a chlorine atom on carbon 2. Cl H C H Cl C H H

1,2-dichloroethane

SAMPLE problem

Drawing and Naming Organic Halides

Draw a structural diagram for 2,2,5-tribromo-5-methylhexane. First, draw and number the parent alkane chain, the hexane:

C
1

C
2

C
3

C
4

C
5

C
6

Next, add two Br atoms to carbon 2, one Br atom to carbon 5, and a methyl group to carbon 5.

Br C
1

Br C
3

C
2

C
4

C
5

C
6

Br Br
1 2 3 4

CH3 Br
5 6

CH3CCH2CH2CCH3 Br CH3

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Section 1.4

Finally, complete the bonding by adding H atoms to the C atoms.

Example 1
Write the IUPAC name for CH3CH2CH2CH(Cl)CH2CH(Br)CH3.

Solution
This compound is 2-bromo-4-chloroheptane.

Example 2
Draw a structural diagram of 1,2-dichlorobenzene.

Solution

Cl Cl

Practice
Understanding Concepts
1. Draw structural diagrams for each of the following alkyl halides:

(a) (b) (c) (d)

1,2-dichloroethane (solvent for rubber) tetrafluoroethene (used in the manufacture of Teflon) 1,2-dichloro-1,1,2,2-tetrafluoroethane (refrigerant) 1,4-dichlorobenzene (moth repellent)

2. Write IUPAC names for each of the formulas given.

(a) CHI3 (antiseptic) C CH2 Cl (b) CH2 CH3 (insecticide) (c) CH2Cl2 (paint remover) (d) CH2Br CHBr CH2Br (soil fumigant)

Properties of Organic Halides

The presence of the halogen atom on a hydrocarbon chain or ring renders the molecule more polar. This is because halogens are more electronegative than C and H atoms, and so carbon halogen bonds are more polar than C H bonds. The increased polarity of alkyl halides increases the strength of the intermolecular forces. Thus alkyl halides have higher boiling points than the corresponding hydrocarbons. Because like dissolves like, the increased polarity also makes them more soluble in polar solvents than hydrocarbons of similar size. When organic halides are formed from halogenation of hydrocarbons, the product obtained is often a mixture of halogenated compounds. These compounds may contain 1, 2, 3, or more halogens per molecule, reflecting intermediate compounds that can be further halogenated. The molecules that contain more halogen atoms are usually

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more polar than the less halogenated molecules, and thus have higher boiling points (Table 1). This difference in boiling points conveniently enables us to separate the components of a mixture by procedures such as fractional distillation.
Table 1 Boiling Points of Some Hydrocarbons and Corresponding Organic Halides Hydrocarbon CH4 C2H6 C3H8 C4H10 Boiling point (C) 164 89 42 0.5 Alkyl halide CH3Cl C2H5Cl C3H7Cl C4H9Cl Boiling point (C) 24 12 46 78

The Cost of Air Conditioning

The cost of a new car with air conditioning includes the price of the unit plus an additional air-conditioner tax. On top of that, there is another, less obvious, cost: possible environmental damage. Let us take a look at how organic chemistry can be used to solve some problems, and how sometimes new problems are created along the way. In the late 1800s, refrigerators were cooled using toxic gases such as ammonia, methyl chloride, and sulfur dioxide. When several fatal accidents occurred in the 1920s as a result of leaked coolant, the search began for a safer refrigerant. In 1930 the DuPont company manufactured Freon, a chlorofluorocarbon, CF2Cl2(g), also called CFC-12. (Industrial chemists sometimes name Freons using a non-SI system.) As it was inert, it was considered very safe and its use spread to aerosol sprays, paints, and many other applications. In the 1970s, large ozone holes were detected in the upper atmosphere, particularly over the polar regions. It appears that although CFCs are inert in the lower atmosphere, they are reactive in the upper atmosphere. In the presence of UV light, CFC moleculesincluding Freon decompose, releasing highly reactive chlorine atoms. The chlorine destroys the ozone molecules in the stratosphere, leaving us unprotected from harmful UV radiation (Figure 1). You may have learned about these reactions in a previous chemistry course. Automobile air conditioners use over one-third of the total amount of Freon in Canada, and about 10% of this total is released into the atmosphere each year. Hence the search is on again to find a new chemical to meet the demand for inexpensive airconditioning systems, and to minimize environmental damage. Two types of chemicals have been developed as substitute refrigerants: the hydrochlorofluorocarbons (HCFCs), and the hydrofluorocarbons (HFCs). These molecules differ from CFCs in that they contain hydrogen atoms in addition to carbon and halogen atoms. The H atoms react with hydroxyl groups in the atmosphere, decomposing the molecules. Since the HCFCs and HFCs readily decompose, they have less time to cause damage to the ozone layer. Note that HCFCs still contain chlorine, the culprit in ozone depletion; HFCs contain no chlorine and so are the preferred substitute for CFCs. These molecules are more readily decomposed in the lower atmosphere and thus have less time to cause damage. However, they do release carbon dioxide, a major greenhouse gas, upon decomposition. The most commonly used coolant now is HFC-134a. Since 1995, it has been used in all new automobile air conditioners. In 2001, the Ontario government introduced legislation requiring that all old units, when refilling is needed, be adapted to use one of the new alternative refrigerants.
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Figure 1 An ozone hole (blue) forms over the Antarctic every spring (September and October).

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Chapter 1

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Practice
Understanding Concepts
3. Create a flow chart outlining the effects of an accidental leak of refrigerant from a

cars air conditioner. Include chemical equations wherever possible.

4. Draw a time line showing the use and effects of various refrigerants over the last 150

years.
5. (a) Write chemical equations predicting the decomposition of HCFCs and HFCs.

(b) Why might HCFCs and HFCs decompose more quickly than CFCs? (c) Why might this make them less damaging than CFCs?

EXPLORE an issue

Decision-Making Skills Define the Issue Analyze the Issue Identify Alternatives Defend the Position Research Evaluate

Role Play: Can We Afford Air Conditioning?

When a car manufacturer is planning to develop a new model, all aspects of the vehicle are reconsidered. Government regulations prohibit the manufacture of new vehicles with air-conditioning units that use CFCs. Alternative coolants have been developed, and now most manufacturers use HFC-134a. However, HFCs are greenhouses gases and so, if released, are likely to be contributors to global warming. Imagine that a committee is set up to decide whether the next new model should have air conditioning using HFC-134a, or no air-conditioning unit at all. Committee members include: a union representative for the production-line workers; the local MP; an environmentalist; a reporter from a drivers magazine; a physician; a representative from the Canadian Automobile Association; an advertising executive; shareholders in the car company. (a) Costs can be measured in many ways: financial, social, environmental, political, etc. Choose one way of

assessing cost and collect and sort information to help you decide whether the costs of automobile air conditioners are justified. (b) Select a role for yourselfsomeone who would be concerned about the kinds of costs that you have researched. Consider how this person might feel about the issue of air conditioning. (c) Role-play the meeting, with everyone taking a turn to put forward his/her position on whether the new car model should have air conditioning. (d) After the meeting, discuss and summarize the most important points made. If possible, come to a consensus about the issue.

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Preparing Organic Halides

Alkyl halides are produced in halogenation reactions with hydrocarbons, as we learned in Section 1.3. Alkenes and alkynes readily add halogens or hydrogen halides to their double and triple bonds. Recall also that Markovnikovs rule of the rich get richer applies when hydrogen halides are reactants, and must be considered in designing the synthesis of specific alkyl halides. These alkyl halides can then be transformed into other organic compounds. An example of the halogenation of an alkyne is shown below for a review of the reactions that produce alkyl halides. These reactions readily take place at room temperature. (a) H C C H + Br Br + bromine H Br C
ethyne

Br C H

1,2-dibromoethene

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LEARNING

TIP

(b) H

Br C

Br C H + Br Br H

Br C Br

Br C Br H

Learning Tip
Several letter symbols are commonly used in general formulas to represent constituents of organic compounds: R represents any alkyl group R , R , etc. (R-prime, R-double prime) represent any alkyl group different from other Rs X represents any halogen atom represents a phenyl group

1,2-dibromoethene + bromine

1,1,2,2-tetrabromoethane

If we wanted to produce a halide of a benzene ring, we would need to arrange a substitution reaction with a halogen. The following example illustrates the chlorination of benzene in the presence of a catalyst. Further substitution can occur in the benzene ring until all hydrogen atoms are replaced by halogen atoms. Cl Cl
benzene

Cl

FeCl3 chlorobenzene

Cl

chlorine

hydrogen chloride

Preparing Alkenes from Alkyl Halides: Elimination Reactions

elimination reaction a type of organic reaction that results in the loss of a small molecule from a larger molecule; e.g., the removal of H2 from an alkane

Alkyl halides can eliminate a hydrogen and a halide ion from adjacent carbon atoms, forming a double bond in their place, thereby becoming an alkene. The presence of a hydroxide ion is required, as shown in the example below. This type of reaction, in which atoms or ions are removed from a molecule, is called an elimination reaction. Elimination reactions of alkyl halides are the most commonly used method of preparing alkenes. H H C Br H C H
+ hydroxide ion

DID YOU

KNOW

C H

H + OH

Mustard Gas Mustard gas is a toxic alkyl halide that was used as a chemical weapon in World War I. When this compound is inhaled, it reacts rapidly with water molecules in the lungs, releasing HCl. The high concentrations of hydrochloric acid destroy lung tissue, leading to death. Mustard gas was banned in the 1980s as a result of international treaties, but nevertheless has been used since.

2-bromopropane

H H C

H C

H C H H + H O + Br H
+ water + bromide ion

propene

ClCH2

CH2

CH2

CH2Cl

SUMMARY
Preparation:

Organic Halides

Functional group: RX alkenes and alkynes organic halides addition reactions with halogens or hydrogen halides alkanes and aromatics organic halides substitution reactions with halogens or hydrogen halides Pathway to other groups: alkyl halides alkenes elimination reactions, removing hydrogen and halide ions
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Practice
Understanding Concepts
6. Classify the following as substitution or addition reactions. Predict all possible prod-

ucts for the initial reaction only. Complete the word equation and the structural diagram equation in each case. You need not balance the equations. (a) trichloromethane chlorine (b) propene bromine (c) ethylene hydrogen iodide (d) ethane chlorine (e) Cl C C Cl F F (excess) H H H H (f)

C Cl Cl

C H

C H Cl

Cl

(g)

Extension
7. Why are some organic halides toxic while others are not? And why are some organ-

isms affected more than others? Use the Internet to find out, using the following key words in your search: bioaccumulation; fat soluble; food chain. Report on your findings in a short article for a popular science magazine or web site.

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Section 1.4 Questions

Understanding Concepts
1.

Draw structural diagrams to represent the elimination reaction of 2-chloropentane to form an alkene. Include reactants, reaction conditions, and all possible products and their IUPAC names. lowing organic reactions: (a) propane chlorine 1-chloropropane 2-chloropropane hydrogen chloride (b) propene bromine 1,2-dibromopropane (c) benzene iodine iodobenzene hydrogen iodide

write a report or present one such case study. Examples of topics include: leaded and unleaded gasoline, use of solvents in dry cleaning, use of aerosol propellants, and use of pesticides and fertilizers.
5. Why was mustard gas such an effective weapon, both

2. Classify and write structural formula equations for the fol-

during World War 1 and more recently? Research its properties and effects, and what defences have been developed against it.

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6. Shortly after the connection was made between the hole

Applying Inquiry Skills

3. The synthesis of an organic compound typically involves a

series of reactions, for example, some substitutions and some additions. (a) Plan a reaction beginning with a hydrocarbon to prepare 1,1,2-trichloroethane. (b) What experimental complications might arise in attempting the reactions suggested in part (a)? Making Connections
4. Research examples of the use of organic chemistry to

in the ozone layer and the release of chlorofluorocarbons, many manufacturers stopped using CFCs as propellants in aerosol cans. (a) Research what alternatives were developed, and the effectiveness of each in the marketplace. Are the alternatives still in use? Have any of them been found to cause problems? (b) Design a product (one that must be sprayed under pressure) and its packaging. Plan a marketing strategy that highlights the way in which your product is sprayed from the container.

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address health, safety, or environmental problems, and

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