1559T.ch02.18-3710/22/051:11Page18 EQA 2 Structure and Reactivity:Acids and Bases, Polar and Nonpolar Molecules Then we proceed bases,which wo purposes:It provides uswith good exampe of h applie to reactions rates a proces tha ted to m ganic compounds,the chapter tums to aconsideration of the simplest of those classes,the nonpolar alkanes. (4)applications of kinetics and thermodynamics to changes in molecular shape.In Chapter3we cover chemi- cal reactions of alkanes. Outline of the Chapter 2-1 Kinetics and Thermodynamics The energetic factors that govern the transformations of molecules chapters to come.Also,a first look at the notation used to describe how organic reactions take place 23feceadlCesP2amlnlkstaeeataseeiyooa 2-5 Nomenclature The first of a group of rules used to unambiguously name any organic compound 2-6 Physical Properties A topic that is usually not emphasized very much but that does reveal several useful,generalizable points about molecules. 2-7 and 2-8 Conformations A discussion of the spatial arrangements that are possible for atoms in alkanes and the energy changes associated with their interconversions. 18
18 2 Structure and Reactivity: Acids and Bases, Polar and Nonpolar Molecules Organic chemistry is largely a study of chemical reactions involving organic molecules. The textbook chapter therefore begins with a review of the principles of kinetics and thermodynamics, which apply to all reactions. Then we proceed to discuss acids and bases, which serves two purposes: It provides us with good examples of thermodynamics as applied to reactions, and it illustrates a process that is actually closely related to most of the reactions of polar organic molecules. After an introduction to functional groups and the classes of organic compounds, the chapter turns to a consideration of the simplest of those classes, the nonpolar alkanes. These sections cover (1) how to name organic molecules (nomenclature), (2) the relation of the physical properties of molecules to their molecular structure, (3) flexibility and shape of molecules (conformation), and (4) applications of kinetics and thermodynamics to changes in molecular shape. In Chapter 3 we cover chemical reactions of alkanes. Outline of the Chapter 2-1 Kinetics and Thermodynamics The energetic factors that govern the transformations of molecules. 2-2 Acids and Bases; Electrophiles and Nucleophiles Reviewing chemistry that you’ve seen before, with an eye to chemistry you will see a lot of in the chapters to come. Also, a first look at the notation used to describe how organic reactions take place. 2-3 Functional Groups The “business ends” of molecules: where reactions are likely to occur. 2-4 Straight-Chain and Branched Alkanes Alkanes of various structures. Isomers. 2-5 Nomenclature The first of a group of rules used to unambiguously name any organic compound. 2-6 Physical Properties A topic that is usually not emphasized very much but that does reveal several useful, generalizable points about molecules. 2-7 and 2-8 Conformations A discussion of the spatial arrangements that are possible for atoms in alkanes and the energy changes associated with their interconversions. 1559T_ch02_18-37 10/22/05 1:11 Page 18
1559T_ch02_18-3710/22/051:11Page19 ⊕ EQA Keys to the Chapler·19 Keys to the Chapter amics changes in or nic chemistry.Even though some of the orientation purpose this co conc s later on get rid of some of its energy somehow.So.relatively speaking.high-energy species are generally unstable. Heat and e ergyare also related,so high-energy species will hav a tendency to undergo processes that give and the two are very different.Energetically favorable processes can take placc at st rate or in some cases.hardly seem to take vooden match in th happens at ro om.of theeaction sw:The umber bum and continues until the whole thing has bumed up.The reaction of most organic molecules with oxyger ven tho net en rgy anter the rea on ha Some partial breaking of old bonds has to take place before anything else,and that re quires an input of ener gy.Onc this proc rted,it can leac ew bo s.and the re of reactions ides nlied apiction.The problemsillive youhances tousethm. Acids and Bases;Electrophiles and Nucleophiles and are govemed by the ions of equilibria of the general sort stronger acid+stronger base=weaker acid+weaker base△G°<0， whe terms strong and weak.In other words,a compound that acts as the strong acid in one such equation may be scale.Water is the most familiar of substances to show such varied behavior. Water acts as a weak acid (the way we normally think of it):
Keys to the Chapter • 19 Keys to the Chapter 2-1. Kinetics and Thermodynamics This section introduces ideas associated with energy changes in organic chemistry. Even though some of the terminology may be somewhat familiar to you from freshman chemistry, a few comments may be useful for orientation purposes. In this course you are going to encounter a lot of discussion concerning the energy content of molecules or other species. This term will refer in general to what is called potential energy in physics: energy that is stored in some way and can potentially be released in some process later on. Discussions involving energy will often refer to the stability or instability of various substances or systems. Energy and stability are related in the following way: A species with high-energy content will tend to want to get rid of some of its energy somehow. So, relatively speaking, high-energy species are generally unstable. Heat and energy are also related, so high-energy species will have a tendency to undergo processes that give off lots of heat. However, that a substance is capable of doing such a thing doesn’t necessarily mean that it will do it quickly. The point here is that the rate of a process is the subject of kinetics, whereas the energetic favorability is one of thermodynamics, and the two are very different. Energetically favorable processes can take place at fast rates, slow rates, or in some cases, hardly seem to take place at all. A wooden match in the presence of air is a good chemical example of the latter. The reactions with oxygen of the compounds in the wood as well as on the head of the match are all extremely energetically favorable (thermodynamics), but nothing perceptible happens at room temperature. Why not? The rate of the reaction is too low: The number of molecules actually reacting with the oxygen at room temperature is so small that nothing seems to be happening at all (kinetics). However, when we strike the match—heat the match head with friction—it starts to burn and continues until the whole thing has burned up. The reaction of most organic molecules with oxygen requires energy input to get started even though it ultimately results in net energy output after the reaction has finished. The reason is as follows: In most reactions, old bonds are broken and new ones are formed, but not exactly simultaneously. Some partial breaking of old bonds has to take place before anything else, and that requires an input of energy. Once this process has started, it can lead to the formation of new bonds, and the release of energy—enough to make more old bonds break plus extra in the form of the flame and heat of burning. This initial energy input is the activation energy of the reaction, and it is a key factor governing kinetics: rates of reactions. This section provides a brief mathematical description of each of the main concepts involved in thermodynamics and kinetics as applied to organic chemistry. The equations are generally fairly straightforward in their application. The problems will give you several chances to use them. 2-2. Acids and Bases; Electrophiles and Nucleophiles The beginning of this text section covers the material you are most likely to have encountered in freshman chemistry: the mechanics of acid-base chemistry. The guiding principle is that such processes are reversible and are governed by thermodynamics. Notions of strong and weak acids and bases are based upon the positions of equilibria of the general sort stronger acid stronger base weaker acid weaker base G° 0, where the thermodynamic driving force favors conversion of the stronger acid and stronger base into the weaker ones. While this concept may be familiar to you, you may not be quite as used to the relative nature of the terms strong and weak. In other words, a compound that acts as the strong acid in one such equation may be the weak partner in another, or may even play the role of a base. After all, the range of known acid strengths covers sixty orders of magnitude, and in organic chemistry we will encounter examples from every part of the scale. Water is the most familiar of substances to show such varied behavior. Water acts as a weak acid (the way we normally think of it): 1559T_ch02_18-37 10/22/05 1:11 Page 19
1559rch0218-3710/22/051:11Page20 EQA 20.chapter 2 STRUCTURE AND REACTIVITY HCI NaOH C8 But water may act as the strong acid (and conversely,hydroxide as the weak base!) H2O NaNH2 stronge And finally,water acts as a base when it encounters a strong enough acid: weaker weake base acid In describing acid-base reactions.we define a very simple relationship:the one between an acid and its con and its conjugate acid)Th ougn this re with which we are more familiar.We use the notion that.speaking.strong acids have weak coniu p.we may use an s of either component of a c base:increased size and increased of the negatively charged atom,and any effects that dis e or weake This text secu n also revie s of cids and base andcompares them with sess panial or full electrical charges and,as a result,are places w e iccd-base action ucleophilic tion is of thes ize thecurd rwnotation that west presented in Chaper I when we dicu rs t ver.we use the arro nt t ofapolar o reaction pay os attention to the details here:Wewill be retuming to thes to memorize. 2-3.Functiongl Gr One look at the 16 classes of organic compounds in Table 2-3(and these are only some of the most common may have emed that the H and A in H-A relate versely to its ach as t he hy in th e th eare very ier
HCl NaOH NaCl H2O stronger stronger weaker weaker acid base base acid But water may act as the strong acid (and conversely, hydroxide as the weak base!): H2O NaNH2 NaOH NH3 stronger stronger weaker weaker acid base base acid And finally, water acts as a base when it encounters a strong enough acid: HCl H2O Cl H3O stronger stronger weaker weaker acid base base acid In describing acid-base reactions, we define a very simple relationship: the one between an acid and its conjugate base (or, conversely, a base and its conjugate acid). Through this relationship it is possible to estimate the strength of acids and bases that we’ve never seen before by making structural comparisons with species with which we are more familiar. We use the notion that, relatively speaking, strong acids have weak conjugate bases, and vice versa. Through this relationship, we may use an analysis of either component of a conjugate acid-base pair to find the strengths of both, relative to other acids and bases. The most common application is to determine the strength of an acid by evaluating effects that stabilize (and make weaker) its conjugate base: increased size and increased electronegativity of the negatively charged atom, and any effects that disperse negative charge away from the negatively charged atom, such as resonance.* By comparing the degree to which these properties are present in each of a pair of conjugate bases, you can usually tell which of the corresponding conjugate acids is stronger or weaker. This text section also reviews the definitions of Lewis acids and bases and compares them with their analogs in organic chemistry: electrophiles and nucleophiles. The latter are the two terms that we use to describe electron-poor and electron-rich atoms in molecules, respectively. Such atoms possess partial or full electrical charges and, as a result, are places where chemical reactivity is usually high. Many of the functional groups are characterized by the presence of electrophilic or nucleophilic carbon atoms, for example. The analogy between a simple inorganic acid-base reaction and an organic nucleophilic substitution is illustrative of these principles. It also utilizes the “curved arrow” notation that we first presented in Chapter 1 when we discussed the shifting of electron pairs to interconvert resonance forms. Here, however, we use the arrows to show the electron movement that takes place when bonds break or form in the course of a chemical reaction. As your first example of a polar organic reaction, pay close attention to the details here: We will be returning to these principles repeatedly. The curved arrow convention is an especially powerful tool to help you understand how and why chemical reactions of organic compounds take place. The more you understand, the less you will have to memorize. 2-3. Functional Groups One look at the 16 classes of organic compounds in Table 2-3 (and these are only some of the most common ones!) will immediately tell you how complicated organic chemistry can become. At the same time, however, closer inspection reveals features of these categories that can greatly simplify learning in this course. Each 20 • Chapter 2 STRUCTURE AND REACTIVITY * You may have learned in freshman chemistry that the bond strength between H and A in H–A relates inversely to its acid strength. This correlation is not as general as you may have been led to believe: It holds only when the acids being compared are all from the same column of the periodic table, such as the hydrogen halides. It fails, for instance, in the series CH4, NH3, H2O, HF, where the acid strength increases as the bond strength goes up! The reason? Acidity relates to heterolytic bond cleavage to give ions, whereas bond strength relates to homolytic bond cleavage to give uncharged species. The two processes are very different. Differences in atomic electronegativity affect heterolytic bond cleavage (and therefore acidity) much more. 1559T_ch02_18-37 10/22/05 1:11 Page 20
1559T_ch02_18-3710/22/051:11Page21 EQA Keys to the Chapler·21 und class is char only carbon,hydrogen,and oxygen.Knowledge of the characteristics of these atoms and the bonds betweer hem,as w s the prop almembers of compounds,for instan.have certain common physical and chemica lting from the presence lizable,qualitativ nized.and.above all.logical wav structured,orga polarizedor charged ar the parts of molecules that most often take part in chemical re actions of those molecules.They are the"centers of reactivity"of molecules- -where the a ion is. any. of functional goupAkon'have 2-4and2-5. Structures and Names for Alkanes of c r half a million wo se possible xist in nature or been pared heless.o 80 mil any of these materials to communicate about them in a clear and sensible wav The text presents b ief descriptions of the problems with naming compounds before the systemai PAC ped.I tnen s on to single nds hol the atoms together.Only four rules are needed at this stage: oups attached to this chain as nchain)in the molecule and name it. 3.Nur r the arbon atoms o the parent chain from the end that gives the one containing the first 4.Assemble the name,using the proper format. ahteehc Example】 3CH3 Proper numbering CHCH2CH3+Chain"b"(Proper parent stem) Name:CH,CH2CHaCHCH2CH2CH3-Chain" 765 321 Improper numbering st chain so this is a h Ho re two ways to ider s specify that,in case of a tie fo
Keys to the Chapter • 21 compound class is characterized by a specific atomic grouping called a functional group. Notice that only nine different elements are represented: C, H, S, N, O, and the four halogens. In fact, 11 of these classes contain only carbon, hydrogen, and oxygen. Knowledge of the characteristics of these atoms and the bonds between them, as we will see, will tell us the properties of the functional groups in which they appear. The functional groups will, in turn, provide the key to understanding the chemistry of all the members of the category. Thus, all members of the “alcohol” class of compounds, for instance, have certain common physical and chemical properties, resulting from the presence of the OH group in all of them. This kind of generalizable, qualitative similarity among compounds in any given class allows organic chemistry to be learned in a structured, organized, and, above all, logical way. Functional groups consist either of polarized bonds, whose atoms can attract other polarized or charged species, thereby leading to reactions, or of multiple (double or triple) bonds that also show reactivity for reasons we’ll explore later. Functional groups are the parts of molecules that most often take part in chemical reactions of those molecules. They are the “centers of reactivity” of molecules—where the action is. The most fundamental feature of alkanes relates to this concept of functional groups: Alkanes don’t have any. We’ll see the consequences of this in the next chapter. 2-4 and 2-5. Structures and Names for Alkanes There are a lot of organic compounds. Table 2-4 lists the numbers of isomers of just alkanes, and only goes up to 20 carbons, and already over half a million structures are possible! Imagine how many more structures can be manufactured when functional groups are present, or when the molecules get larger. Obviously not all these possible structures exist in nature or have been prepared in laboratories. Nonetheless, over 80 million different compounds are known at present, and nomenclature is the language that allows anyone interested in any of these materials to communicate about them in a clear and sensible way. The text presents brief descriptions of the problems associated with naming compounds before the systematic procedures of the IUPAC were developed. It then goes on to introduce just the rules necessary for naming simple alkanes: molecules containing only carbon and hydrogen atoms and having only single bonds holding the atoms together. Only four rules are needed at this stage: 1. Identify the longest carbon chain (the parent chain) in the molecule and name it. 2. Name all groups attached to this chain as substituents. 3. Number the carbon atoms of the parent chain from the end that gives the one containing the first substituents the lowest possible number. 4. Assemble the name, using the proper format. Although examples are given in the text and there are lots of problems for you to practice on, here are four additional worked-out examples to further clarify some fine points of the procedure. Example 1. Analysis: The longest chain contains seven carbons, so this is a heptane. However, there are two ways to identify a seven-carbon chain (see numbering). Which one is the parent? The rules specify that, in case of a tie for longest chain, the one with the most substituents is chosen as the parent. The seven-carbon chain labeled “a” CH3CH2CH2CHCH2CH2CH3 CHCH2CH3 CH3 Name: 7 6 5 4 3 2 1 3 2 1 Chain “b” (Proper parent stem) Improper numbering Chain “a” Proper numbering 1559T_ch02_18-37 10/22/05 1:11 Page 21
1559rch0218-3710/22/051:11Page22 EQA 22.chapter 2 STRUCTURE AND REACTIVITY has one substitu propylheptan Example 2. CH3 Name:CH.CHCH.CH.CH.CHCH.CCHC-CHCHCH.CH CHs CH3 CHsCHs Analysis:The main chain he e is unamb and 14carbons ong the numbers if we number right-to-left.But that is not the criterion for determining which way to number the chain.The rule says in the direction t t gives the carbon containing the first t the lo So left-to ctand the molccule's name is6.10-dicthl28810.11.12-hexamethyltetradecane Ever though the name that comes from numbering the other way has mostly low numbers.(59-diethyl-3.4.5.7.7.13- methyltetradecane).it is wrong-its lowest number is a3."and the correct name's lowest number is Example3. CH3 CH3 CHaCH3 Name:CH3-CH-CH-C-CH-CHs h Analysis:A hexane.Numbering left-to-right gives 2.3,4,4.5-pentamethylhexane:right-to-left gives 2.3.3.4.5- pentamethylhexane.The choice is made by comparing substituent numbers from lowest to highest.The name with the lower number at the first point of difference is the winner.So 2.3.3.4.5 is preferred over 2.3.4.4.5. Example 4. 133456780 ←Main numbe Name: CH.CH.CH.CH.CHCH.CH.CH.CH, CH 2CH thon 5 Rule 3 illus The substituent has three carbons.so it has a name based on propyl.Then add appropriate numbe nd name for groups attached to th opy Is t of th 5-(1-rmcthypropyonan.Note punctuation.snot hard but analysis
has one substituent (a sec-butyl group on carbon 4). The seven-carbon chain labeled “b” has two substituents (a methyl on carbon 3 and a propyl on carbon 4), so it wins. The molecule is called 3-methyl-4-propylheptane. Example 2. Analysis: The main chain here is unambiguous and 14 carbons long—the parent is tetradecane. Which is the correct numbering direction, however? Most of the groups are close to the right-hand end and will have low numbers if we number right-to-left. But that is not the criterion for determining which way to number the chain. The rule says to number in the direction that gives the carbon containing the first substituent the lowest possible number. If we number from right-to-left, the first substituted carbon is C3; if left-to-right, it is C2. So, left-to-right is correct, and the molecule’s name is 6,10-diethyl-2,8,8,10,11,12-hexamethyltetradecane. Even though the name that comes from numbering the other way has mostly low numbers, (5,9-diethyl-3,4,5,7,7,13- hexamethyltetradecane), it is wrong—its lowest number is a “3,” and the correct name’s lowest number is a “2.” Example 3. Analysis: A hexane. Numbering left-to-right gives 2,3,4,4,5-pentamethylhexane; right-to-left gives 2,3,3,4,5- pentamethylhexane. The choice is made by comparing substituent numbers from lowest to highest. The name with the lower number at the first point of difference is the winner. So 2,3,3,4,5 is preferred over 2,3,4,4,5. Example 4. Analysis: A nonane with a complicated substituent on carbon 5. Rule 3 illustrates what to do. Number the substituent carbons from the point of attachment to the main chain, outward along the substituent’s longest chain. The substituent has three carbons, so it has a name based on propyl. Then add appropriate numbers and names for groups attached to the substituent chain. So, 1,1,2-trimethylpropyl is the complete name of the substituent. Now, attach the substituent’s name to the name of the main chain to get the name of the whole molecule: 5-(1,1,2-trimethylpropyl)nonane. Note punctuation. It’s not hard, but it does take some careful analysis. CH3 CH CH3 CH3 CH3 CH3 CH3CH3 Name: CH C CH CH3CHCH2CH2CH2CHCH2CCH2C CH3 CH3 CH3 CH3 CH3 CH3 CH3CH2 CH2 CH3 Name: CHCHCH2CH3 1 2 3 1 2 22 • Chapter 2 STRUCTURE AND REACTIVITY 1559T_ch02_18-37 10/22/05 1:11 Page 22