1.

9
(a)

Synthesizing Organic Compounds

There are many reasons why chemists create new organic substances. They may be synthesized as part of research or to demonstrate a new type of reaction. Others are synthesized if a compound is needed with specific chemical and physical properties. Large amounts of some synthetic compounds are routinely produced industrially (Figure 1). Chemical engineers can design and create synthetic replicas of naturally produced compounds by adding or removing key functional groups to or from available molecules. For example, there is a large market demand for caffeine as a stimulant for use in non-coffee beverages such as soft drinks and in solid foods. Caffeine is a cyclic compound containing nitrogen, and is extracted from coffee beans and tea leaves. To meet the large demand, a compound called theobromine is obtained from cocoa fruits and modified chemically to produce caffeine; the structures differ by the presence of a single methyl group, which is added to the theobromine. In recent years, however, the popularity of decaffeinated coffee has resulted in the increased availability of natural caffeine, removed from coffee in the decaffeination process. O H CH3 C C N C H N O CH3 N C O C N C C CH3 N C H N

O C O OH O C C H
ASA (b)

H H

H H H N C N H
urea

N C

C N

O O

CH3
theobromine

CH3
caffeine

Figure 1 (a) More than ten million kilograms of Aspirin, or acetylsalicylic acid (ASA), are produced in North America annually. Because of this compounds ability to reduce pain and inflammation, it is the most widely used medicine in our society. (b) Urea, the organic compound first synthesized by Whler in 1828, is produced in even larger quantities than ASA. Urea is used primarily as plant fertilizer and as an animal feed additive.

Throughout our study of organic families, we have focused on the transformation of functional groups. Let us take our knowledge of these reactions and devise a method of preparing a more complex molecule from simpler ones. Lets say that we have been assigned the task of preparing an ester with a pineapple flavour, to be used in candies. We have available a number of short-chain alkanes and alkenes as starting materials. What substance will we make, which starting materials should we use, and what steps should we take in the synthesis?

Pineapple Flavouring: Ethyl Butanoate

When planning a synthesis pathway for any substance, we have a couple of options. One approach is to look at the available compounds and examine the transformations they can undergo. For example, what products can we obtain from short-chain alkanes and alkenes? We can then look at the possible products of these transformations and proceed further. Because there are many possible reactions and products, however, this approach presents several pathways to consider, many of which are ultimately unproductive. Another approach is to start with the compound we want to prepareethyl butanoateand think backwards. Ethyl butanoate is, like all synthetic esters, derived from an acid and an alcohol. Having identified the acid and the alcohol, we then identify a reaction that would produce each of them from our choice of short-chain alkanes and alkenes. This approach limits the possible reactions and is a more efficient method of selecting a synthesis pathway.

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O CH3CH2CH2C O CH2CH3
ethyl butanoate

Let us apply the backwards approach to the synthesis of ethyl butanoate, the ester with a pineapple flavour. As the name and structure show, this ester is formed from a reaction between ethanol and butanoic acid. The steps in our multi-step procedure are shown in the sample problem below. Of course, there is more than one possible synthesis pathway for any product; when selecting a procedure, industrial chemists always pay attention to the availability and cost of starting materials, as well as safety and environmental concerns.

Designing Synthesis Pathways

Write a series of equations to illustrate the synthesis of ethyl butanoate from an alkene and an alcohol from simpler molecules. First, plan a pathway for the production of ethyl butanoate. To make the ethyl portion of the ester, we will need to synthesize the necessary alcohol, ethanol. Ethanol can be prepared by the addition reaction of water to ethene, a hydration reaction. We will select ethene and water as the starting materials for this alcohol. Next, we will need to prepare butanoic acid. Recall that acids can be prepared from the controlled oxidation of aldehydes, which, in turn, are prepared from the controlled oxidation of alcohols. We need to determine which alcohol to use for this sequence. 1-butanol will produce butanal, which will produce butanoic acid. However, being a primary alcohol, 1-butanol is difficult to prepare from the reactions we have studied so far. The addition reaction of H2O to either 1-butene or 2-butene would produce predominantly 2-butanol, as predicted by Markovnikovs rule.
CH2 CHCH2CH3 H 2O
H2SO4

SAMPLE problem

CH3CHCH2CH3 OH

CH2CH

CHCH3

H 2O

H2SO4

CH3CHCH2CH3 OH

Other reagents and reactions are available for preparing primary alcohols, as you may learn in future chemistry courses. For this synthesis, we will use 1-butanol as our starting material to prepare butanoic acid. Our pathway is now complete.

ethyl butanoate (an ester)

ethanol (alcohol)

ethene (alkene) water

butanoic acid (carboxylic acid)

butanal (aldehyde) (O) (O)

1-butanol (alcohol)

The equations are

1. CH3CH2CH2CH2OH 1-butanol 2. CH3CH2CH2CHO butanal (O) CH3CH2CH2CHO butanal (O) CH3CH2CH2COOH butanoic acid H2O

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Organic Compounds

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3. CH2 CH2 ethene

H2O CH3CH2OH ethanol

4. CH3CH2CH2COOH butanoic acid

CH3CH2OH CH3CH2CH2COOCH2CH3 ethanol ethyl butanoate

Example
Write a series of equations for the synthesis of propanone, starting with an alkene.

Solution
1. CH3CH

CH2

H2O

CH3CH(OH)CH3

ACTIVITY 1.9.1
Building Molecular Models to Illustrate Reactions (p. 90) What do molecules really look like, and how does one substance turn into another? This activity helps you visualize, using molecular models, how reactions happen.
2.

propene

2-propanol
O

CH3CH(OH)CH3
2-propanol

(O)

CH3CCH3
propanone

Practice
Understanding Concepts
1. A food additive that is named as a single ingredient is often a mixture of many

ACTIVITY 1.9.2
Preparation of an Ester Aspirin (p. 90) The reaction between salicylic acid and acetic anhydride produces a well-known pharmaceutical product.

compounds. For example, a typical artificial strawberry flavour found in a milkshake may contain up to 50 different compounds. A few of these are listed below. For each, write a structural formula and an equation or a series of equations for a method of synthesis from the suggested reactants. (a) 2-pentyl butanoate from pentene and butanal (b) phenyl 2-methylpropanoate from phenol and an appropriate alcohol (c) 4-heptanone from an alcohol (d) ethyl ethanoate from ethene

Section 1.9 Questions

Understanding Concepts
1. For each product, write a structural formula and an equa-

Applying Inquiry Skills

3. In artificial apple flavour, the main ingredient is ethyl

tion or a series of equations for a method of synthesis from other compounds. (a) pentyl ethanoate from ethene and an alcohol (b) phenyl ethanoate from an alkene and an alcohol (c) 3-octanone from a simpler compound (d) methyl benzoate from two alcohols (e) sodium salt of butanoic acid from an ester (f) trimethylamine from ammonia and alkanes (g) N-ethylethanamide from an alkane and ammonia
2. The smell of freshly cut grass can be simulated by the addi-

2-methylbutanoate. (a) Draw a flow chart to show the synthesis of this compound, starting with simpler compounds. (b) Describe the steps in the procedure for this synthesis. Include experimental conditions and safety precautions in the handling and disposal of materials. Making Connections
4. The flavour of almonds is obtained from phenyl methanal,

tion of hexanal to substances such as air-fresheners. Describe how hexanal can be made from an alcohol.

also called benzaldehyde. Natural almond flavour is extracted from the pit of peaches and apricots, and may contains traces of the poison hydrogen cyanide. (a) Write a structural diagram for benzaldehyde. (b) Write equations for a series of reactions in the synthesis of benzaldehyde from an ester.

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(c) Research and describe the toxicity of the reactants listed in (b), and compare the toxicity to that of hydrogen cyanide. In your opinion, do your findings substantiate consumer perception that natural products are always healthier than their artificial counterparts?

6. If you were told that a neighbour was starting a new career

in organic products, why might there be some confusion about what the new job involves?
7. Look at the product labels on foods, pharmaceuticals, and

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5. Quinine is a fairly effective treatment for malaria, a mainly

tropical disease that kills or incapacitates millions of people every year. Quinine has a bitter taste and was mixed with lemon or lime to make it palatable; it was later included as a component of a beverage called tonic water. (a) Tonic water contains approximately 20 mg quinine per 375-mL can; the dosage required for the treatment of malaria is approximately six 300-mg tablets per day. In your opinion, would drinking tonic water be an effective approach to the treatment of malaria? Explain. (b) Refer to the structural diagram of quinine (Figure 2), and explain why quinine is soluble in water. (c) Research the effectiveness of quinine as an antimalarial agent from the early 1800s to the present.

dietary supplements in a supermarket or drugstore. In particular, look for the terms organic, natural, and chemical. What is the purpose of using these terms on the packaging? Do they always mean the same thing? Do they have a positive or negative connotation? Write a short opinion piece on the use of these three terms, and what these terms mean to consumers.

CH=CH2 N H CH2OH N
Figure 2 Structure of quinine

HO

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SUMMARY

Flow Chart of Organic Reactions

alkenes addition

+ H2
substitution alkanes

+ HX
alkyl halides

+ H2O + H2O
1 alcohol (O)* aldehydes alcohols 2 alcohol (O)* ketones dehydration

+ X2

+ NH3
amines *(O) indicates controlled oxidation with KMnO4 or Cr2O72, in H2SO4 amine

(H2SO4)
ethers

(O)*
carboxylic acids alcohol condensation amides esters

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Organic Compounds

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