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SECTION

1.1

Introducing Organic Compounds


For hundreds of years, up to and including the 1800s, many influential thinkers believed that an invisible vital energy was a key part of the compounds that make up living organisms. People used the term organic to describe matter that was or that came from living matter, and the term inorganic was used to describe matter that was or that came from non-living matter. This distinction between organic matter and inorganic matter had a powerful influence on the thinking of scientists for several hundred years. Scientists commonly assumed that a different set of scientific laws governed the identity and behaviour of living matter compared to non-living matter. For example, most scientists believed that organic compounds could come only from living organisms. In 1828, however, laboratory evidence showed that this belief was mistaken. A German chemist, Friedrich Whler, was attempting to synthesize ammonium cyanate by reacting one inorganic compound, silver cyanate, with another inorganic compound, ammonium chloride. He was surprised to find that this reaction produced a white, crystalline substance with none of the chemical or physical properties of ammonium cyanate. The properties of this crystalline compound, as well as its molecular formula, were identical to those of a compound that had been isolated from the urine of mammals many years before: urea, shown in Figure 1.1A. At that time, chemists considered (correctly) ammonium cyanate to be inorganic and urea to be organic. Thus, Whlers synthesis demonstrated that organic matter could be synthesized from inorganic matter at that time, a truly amazing discovery. Soon after, other chemists began to synthesize many organic compoundssuch as acetic acid, methane, and ethanolfrom inorganic compounds. By the late 1800s, it was clear to most scientists that all matter, regardless of its source or classification, behaved according to the same scientific laws. Organic matter and inorganic matter, they realized, are not fundamentally different from each other.

Key Terms
organic compound inorganic compound isomer constitutional isomer stereoisomer diastereomer enantiomer

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Figure 1.1 (A) Urea was the first organic compound to be synthesized from inorganic compounds, shattering the belief of scientists at the time that organic compounds could only come from living matter. Today, synthetic urea is used as (B) a fertilizer (due to the nitrogen it contains), in (C) hand creams to re-hydrate skin (because it binds with water), and in (D) instant cold packs (due to its endothermic reaction with ammonium chloride).

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The Modern Definitions of Organic Compounds and Inorganic Compounds


As chemists developed a greater understanding of the organic compounds they were analyzing and synthesizing, they observed that all these compounds contained carbon atoms. The modern definition states that an organic compound is a type of compound in which carbon atoms are nearly always bonded to each other, to hydrogen atoms, and sometimes to atoms of a few specific elements. These elements are usually oxygen, nitrogen, sulfur, or phosphorus, as well as several others. This definition for organic compounds has several exceptions, however. These exceptions are carbonates (CO32-), cyanides (CN), carbides (C22), and oxides of carbon (CO2, CO). Even though these compounds contain carbon, they do not contain any carbon-carbon or carbon-hydrogen bonds. The exceptions, along with all compounds that do not contain carbon atoms, are classified as inorganic compounds.

The Special Nature of the Carbon Atom

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What is the nature of the carbon atom that allows it to form the foundation of all organic compounds and to be the basis of the thousands of molecules found in living organisms? Recall that a carbon atom has four valence electrons. Because it has exactly half of a filled outer shell of electrons and an intermediate electronegativity, a carbon atom is much more likely to share electrons than to gain or lose enough electrons to form ions. Having four valence electrons, a carbon atom can form covalent bonds with four other atoms. This property allows for a wide variety of molecules. When a carbon atom is bonded to four different atoms, the resulting molecule has a specific shape that is often referred to as tetrahedral. Figure 1.2 models this shape for the methane molecule in three common ways. Figure 1.2A is a ball and stick model. The blue lines connecting the hydrogen atoms form a tetrahedron. Figure 1.2B shows an easier way to sketch the shape. In both A and B, the carbon atom and the hydrogen atoms above and to the left of the carbon are in the same plane as the plane of the page. The lowest hydrogen atom is protruding from the page, and the hydrogen atom on the right is behind the page. Figure 1.2C is a space-filling model. When analyzing or drawing two-dimensional structural diagrams of organic compounds, keep the three-dimensional shape in mind, because it is the more accurate shape.
A

Figure 1.2 (A) In a tetrahedron, all of the sides, as well as the base, are identical equilateral triangles. For methane, shown here, the carbon atoms are at the centre of the tetrahedron, and the hydrogen atoms are on the vertices. (B) Notice that a dashed line is used to give the impression that an atom is behind the page, and a wedge is used to show an atom protruding from the page. (C) In this space-filling model of methane, the carbon atom is represented in black and the hydrogen atoms are in white.

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B C

H C H H

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organic compound a type of compound in which carbon atoms are nearly always bonded to each other, to hydrogen atoms, and occasionally to atoms of a few specific elements inorganic compound a type of compound that includes carbonates, cyanides, carbides, and oxides of carbon, along with all compounds that do not contain carbon atoms

Isomers
Carbon atoms can form bonds with each other, often resulting in very long straight or branched chains of carbon atoms. Each carbon atom in a chain is also bonded to hydrogen atoms or atoms of other elements. These structures provide the root for an extremely large number of compounds. For example, consider molecules containing five carbon atoms, all single-bonded to other carbon atoms or hydrogen atoms. Figure 1.3 shows three different structures of molecules that can exhibit this combination of atoms. Notice that, despite being structurally different, these three molecules have the same molecular formula, because they have the same number of atoms of each element. Molecules that have the same molecular formula but with their atoms in a different arrangement are called isomers of each other. There are two main classes of isomers: constitutional isomers and stereoisomers.

constitutional isomers molecules that have the same molecular formula but their atoms are bonded together in a different sequence

H H
Figure 1.3 All of these molecules have the same molecular formula: C5H12. Because their atoms are bonded in a different sequence, they are constitutional isomers of each other. Their physical properties, such as boiling points, vary, as do their shapes. Structural diagrams are shown in (A). Ball and stick models are shown in (B), and space-filling models are shown in (C).

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H C H C H C H C H H C C C H H H H H H H
H H H H C H C C H H H C H H H
B

C H

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

isomers molecules that have the same molecular formula but their atoms are in a different arrangement

Constitutional Isomers The isomers shown in Figure 1.3 are constitutional isomers. Constitutional isomers are molecules that have the same molecular formula, but their atoms are bonded together in a different sequence. Another common term for constitutional isomer is structural isomer. For example, a molecule with 6 carbon atoms and 14 hydrogen atoms can form five constitutional isomers. A molecule with 10 carbon atoms and 22 hydrogen atoms can form 25 constitutional isomers. With 20 carbon atoms and 42 hydrogen atoms, 366 319 constitutional isomers are possible. And these data include only molecules with single bonds!

Figure 1.4 By flipping the molecule or rotating atoms around a single bond, you can see that these three structures are not isomers of the molecules shown in Figure 1.3.

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Now consider the molecules shown in Figure 1.4. Each of these molecules has five carbon atoms and 12 hydrogen atoms, but they are not isomers of the molecules in Figure 1.3. For example, Figure 1.4A is the same molecule as the one shown in Figure 1.3B. To see this, simply flip the image horizontally. Similarly, Figure 1.4B and 1.4C are the same as the molecule in Figure 1.3A, because atoms can freely rotate around a single bond.
A

H H

C H

10 MHR Unit 1 Organic Chemistry

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

In addition to straight or branched chains, carbon atoms also can form rings of three, four, five, six, or more atoms. Figure 1.5 shows all possible ring structures that can be made with five carbon atoms. These molecules are all constitutional isomers of each other, as well as the molecules in Figure 1.3.

H
H H C

H C
H

H C
H H C

H
H H C H H

H
C H

H C
H

C H

H H H H C C H

H H
H C H H H

H H
H H C C C C H C H

C
H

C
C H

C HH

H H

C
C H

H H

H H

Figure 1.5 These five carbon molecules are all constitutional isomers. The coloured portions highlight the ring structures in these molecules. Ring structures are common in organic compounds.

1. Explain how the modern definition of the term organic compound differs from the definition this term had during the 1800s and earlier.

2. Describe the properties of a carbon atom that allow it to be the foundation of all organic compounds.

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H H H C C H
ball-and-stick model

3. Using the modern definitions, explain what determines whether a carbon-containing molecule is classified as organic or inorganic.

Stereoisomers Carbon atoms can form multiple bonds with other carbon atoms. Figure 1.6 shows a structural diagram, a ball and stick model, and a space-filling model of a two-carbon compound with a double bond. An important property of this molecule is the inability of the atoms to rotate around the double bond. Therefore, this molecule is flat and rigid.

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space-lling model

Learning Check

structural diagram

Figure 1.6 Molecules with double bonds are flat and rigid, because their atoms cannot rotate around the double bond.

The rigidity of the structure of atoms around a double bond is one source of another type of isomer called a stereoisomer. Stereoisomers are molecules that have the same molecular formula and their atoms are bonded together in the same sequence. They differ, however, in the three-dimensional orientations of their atoms in space. There are two kinds of stereoisomers: diastereomers and enantiomers.

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4. Why do many organic compounds form a three-dimensional shape instead of a two-dimensional shape? 5. Draw two molecules that could be confused as constitutional isomers but are actually identical. 6. Draw all the constitutional isomers for a molecule with the formula C7H16.
stereoisomers molecules that have the same molecular formula and their atoms are bonded together in the same sequence, but differ in the three-dimensional orientations of their atoms in space

Diastereomers
diastereomer a stereoisomer based on a double bond, in which different atoms or groups are bonded to each carbon in the double bond

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Figure 1.8 Cis (D) and trans (E) isomers can form only when each of the carbon atoms involved in the double bond has two different atoms or groups single bonded to it.

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B

Figure 1.7 The double bonds prevent rotation around the carbon atoms, resulting in two separate orientations in space of the -CH3 groups and H atoms. Thus, these molecules are diastereomers.

CH3 C H C

CH3 H
cis isomer

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B

Stereoisomers based on double bonds are called diastereomers. Diastereomers only form when each carbon atom involved in the double bond has different atoms or groups of atoms bonded to it. Figure 1.7 shows the two diastereomers that can form when the double bond is in the middle of a four-carbon chain. Each carbon atom in the double bond is bonded to two unique atoms or groups: one hydrogen atom and one CH3 group. When two identical atoms or groups are on the same side of the double bond, the structure is called the cis isomer, as shown in Figure 1.7A. When two identical atoms or groups are on the opposite sides of the double bond, the structure is called a trans isomer, as shown in Figure 1.7B. If the double bonds were changed to single bonds, the atoms could rotate around the central C-C bond and the two molecules shown here would be identical. All of the possible isomers containing five carbon atoms and ten hydrogen atoms are shown in Figure 1.8. Notice that structures A, B, and C do not form diastereomers. In each case, one of the carbon atoms involved in the double bond has identical atoms or groups bonded to it. In such cases, structural diagrams are often drawn with the carbon atoms in a straight line. CH3 C H

CH3

trans isomer

H C H

H H C C H

H H

H C

H C

H H

H H

H
E

H C

H C H H H H

H C C H

H C

cis isomer

trans isomer

Figure 1.9 shows structural, ball-and-stick, and space-filling models of molecules in which two carbon compounds are joined with a triple bond. The structure around the triple bond is flat and rigid, like the structure around a double bond. Additionally, the triple bond structure is also linear. Therefore, diastereomers are not possible. However, longer chain molecules with triple bonds can still form constitutional isomers. Figure 1.10 shows the constitutional isomers that can be formed from five carbon atoms and eight hydrogen atoms.

Figure 1.9 The structure around a triple bond is flat, rigid, and linear.

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ball-and-stick model space-filling model

structural diagram

12 MHR Unit 1 Organic Chemistry

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H H C C C C HH H C H H H C H

H H

H H H C H

H H H C C C H
Enantiomers

H C H

H C H H H

H C H C C

H C H

H C H H H

H H C H

C C H

H C C H

A
Br

B
Br

Cl

Cl

Note that enantiomers form only when the carbon atom is bonded to four different atoms or groups. For instance, if the fluorine atoms in the molecules in Figure 1.11 are replaced with hydrogen atoms, the molecules are no longer enantiomers. In fact, as Figure 1.12 shows, they are now identical.
Br Br

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Cl

Mirror

Activity 1.1

Organic Isomers

Unlike many elements, carbon can form branched, double, or triple bonded compounds. In this activity, you will build a variety of molecules in order to become more familiar with carbon compounds and the isomers they form.

Materials

model-building kits

Procedure
1. Build all the possible constitutional isomers for the formula C6H14. Record each structure in a data table.

2. Build all the possible straight-chain isomers (no cyclical or branching structures) for the formula C6H12. Record each structure in your data table. 3. Build the diastereomers, cis and trans, for each of your double-bonded structures. Draw these structures in a data table.

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Cl H

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Figure 1.11 In each molecule, the carbon atom is bonded to a chlorine atom, a fluorine atom, a bromine atom, and a hydrogen atom. Because the hydrogen and fluorine atoms have been exchanged, the molecules are mirror images of each other and are enantiomers.

Figure 1.12 When the fluorine atoms are replaced with hydrogen atoms, the molecules are no longer enantiomers. They are identical.

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Questions

Enantiomers are the second type of stereoisomers. Enantiomers are mirror images of each other around a single carbon atom. To form enantiomers, at least one carbon in the compound must be bonded to four different atoms or groups. Figure 1.11A shows a molecule with atoms of four different elements bonded to one carbon atom. Exchanging the hydrogen atom and the fluorine atom results in the enantiomer of this molecule, shown in Figure 1.11B. These molecules cannot be superimposed on each otherthey are mirror images of each other, just as a persons two hands are mirror images of each other.

Figure 1.10 Although triple bonds do not form diastereomers, there are still three different possible constitutional isomers formed from five carbon atoms and eight hydrogen atoms. Explain why triple bonds do not form diastereomers.

enantiomer a stereoisomer in which molecules are mirror images of each other around a single carbon atom bonded to four different atoms or groups

4. Build, then draw, three possible structures that have the formula C6H10. 5. Build a molecule that has a carbon, a fluorine, and two hydrogen atoms attached to a central carbon atom and build a molecule that has a carbon, fluorine, bromine, and hydrogen attached to the central carbon atom. Build mirror images of these two molecules. Record each structure in a data table.

1. How did building three-dimensional models help you understand more about the different types of isomers carbon compounds can form? 2. Review your models and drawings of molecules for step 5. Identify which two molecules are enantiomers.

Section 1.1 Review

Section Summary
In organic compounds, carbon atoms are almost always bonded to each other, to hydrogen atoms, and occasionally to atoms of a few specific elements. A carbon atom has four valence electrons, allowing it to form covalent bonds with four other atoms. Carbon atoms can bond with each other to produce straight or branched chain molecules that provide the root for a large number of organic compounds. Many organic compounds form isomers. The two main classes of isomers are constitutional isomers and stereoisomers. Diastereomers are stereoisomers in which different atoms or groups are bonded to each carbon involved in a double bond. Enantiomers are stereoisomers in which molecules are mirror images of each other around a single carbon atom bonded to four different atoms or groups.

Review Questions
1.
K/U In the 1800s, the definition of organic compounds such as sugar, fats, and wood required that they came from living organisms. How does this definition compare to the modern definition of organic compounds? 2. A The structure of carbonic acid (H2CO3) is shown below. Explain why it is considered inorganic even though it contains both hydrogen and carbon.

10.

K/U Explain why the molecule shown below is not an example of a cis stereoisomer. H H C H H C C H C H C

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3. A Draw the Lewis structure and a threedimensional shape of CH4. What would be the consequences to living organisms if carbon only formed 90 angles with other atoms? 4. C Draw all the possible constitutional isomers for the following molecules. a. C4H8 b. C2H2Cl2 5.

T/I The following ring structure can also form cis and trans isomers. H H H C H C H C F H C C H H F

K/U Explain why cis and trans isomers normally are not possible around the following bonds. a. a single bond CHEM12_1.355A b. a triple bond

C The terms transnational, transcontinental, and transatlantic all have the same prefix. Explain what makes this prefix appropriate for describing one way of placing different groups around a double bond. 7. A Consider your left hand. If the palm is considered the centre, what are the parts of your left hand that make it a non-superimposable mirror image of your right hand? 8. C Use a Venn diagram to compare and contrast diastereomers and enantiomers. 9. T/I Predict how the physical and chemical properties of a pair of enantiomers would compare.

6.

a. Draw the three-dimensional shape of this molecule, showing both the cis and the trans isomers. b. What makes these structures different from linear cis and trans isomers, and why is this possible? 12. A How would you expect constitutional isomers to compare in terms of their boiling points and their chemical reactivity? Explain your answer. 13. T/I Friedrich Wohlers accidental production of urea from inorganic compounds led to the modern definitions of organic and inorganic compounds. It also was considered the discovery of the existence of isomers. The structure of urea is shown below. Ammonium cyanate is a constitutional isomer of urea. Speculate and draw a possible structure for ammonium cyanate. (Hint: Begin by making a triple bond between the carbon atom and one of the nitrogen atoms.)
O H2N C NH2

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H H H