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Br2
It also reacts with 3-methyl-2-pentene to form 2,3-dibromopentane. CH3 A CH3 CHPCCH2CH3 Br CH3 A A CH3CHCCH2CH3 A Br
Br2
Instead of trying to memorize both equations, we can build a general rule that bromine reacts with compounds that contain a CPC double bond to give the product expected from addition across the double bond. This approach to understanding the chemistry of organic compounds presumes that certain atoms or groups of atoms known as functional groups give these compounds their characteristic properties.
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Functional groups focus attention on the important aspects of the structure of a molecule. We dont have to worry about the differences between the structures of 1-butene and 2-methyl-2-hexene, for example, when the compounds react with hydrogen bromide. We can focus on the fact that both compounds are alkenes that add HBr across the CPC double bond in the direction predicted by Markovnikovs rule, introduced in Section O1.8. CH2 P CHCH2CH3 CH3 A CH3C PCHCH2CH2CH3 HBr CH3CHCH2CH3 A Br CH3 A CH3C CH2CH2CH2CH3 A Br
HBr
The CPO group plays a particularly important role in organic chemistry. This group is called a carbonyl, and some of the functional groups based on a carbonyl are shown in Table O2.2.
TABLE 02.2 Functional Groups That Contain a Carbonyl Functional Group O B O COH O B O CO O B O CO Cl O B O COOH O B O COOO O B O CONH2 Name Example
CH3 CHO (acetaldehyde) CH3COCH3 (acetone) CH3COCl (acetyl chloride) CH3CO2H (acetic acid) CH3CO2CH3 (methyl acetate) CH3CONH2 (acetamide)
Exercise O2.1
Root beer hasnt tasted the same since the use of sassafras oil as a food additive was outlawed because sassafras oil is 80% safrole, which has been shown to cause cancer in rats and mice. Identify the functional groups in the structure of safrole. OOCH2 i O
Safrole
CH2 G CHPCH2 Solution Safrole is an aromatic compound because it contains a benzene ring. It is also an alkene because it contains a CPC double bond. The most difficult functional group to recognize in the molecule might be the two ether linkages (OOO).
Exercise O2.2
The following compounds are the active ingredients in over-the-counter drugs used as analgesics (to relieve pain without decreasing sensibility or consciousness), antipyretics (to reduce the body temperature when it is elevated), and/or anti-inflammatory agents (to counteract swelling or inflammation of the joints, skin, and eyes). Identify the functional groups in each molecule. O B C CH3 G D G CH OH
OH O OH M D O C B OOCOCH3
Aspirin (acetylsalicylic acid)
CH3
NH G D C B Tylenol O (acetaminophen)
CH3
Solution All three compounds are aromatic. Aspirin is also a carboxylic acid (OCO2H) and an ester (OCO2CH3). Tylenol is also an alcohol (OOH) and an amide (OCONHO). Ibuprofen contains alkane substituents and a carboxylic acid functional group.
Exercise O2.3
The discovery of penicillin in 1928 marked the beginning of what has been called the golden age of chemotherapy, in which previously life-threatening bacterial infections
were transformed into little more than a source of discomfort. For those who are allergic to penicillin, a variety of antibiotics, including tetracycline, are available. Identify the numerous functional groups in the tetracycline molecule. HO CH3 / N(CH3)2 OH
Tetracycline
OH
B O
Solution The compound contains an aromatic ring fused to three six-membered rings. It is also an alcohol (with five OOH groups), a ketone (with CPO groups at the bottom of the second and fourth rings), an amine [the ON(CH3)2 substituent at the top of the fourth ring], and an amide (the OCONH2 group at the bottom right-hand corner of the fourth ring.)
We can divide the reaction into two half-reactions. One involves the oxidation of sodium metal to form sodium ions. Oxidation Na Na e
The other involves the reduction of an H ion in water to form a neutral hydrogen atom that combines with another hydrogen atom to form an H2 molecule. O D G
O S
Reduction
2H 2H
2H 2 HT
O 2 SO OH Q H2
2e
Once we recognize that water contains an OOH functional group, we can predict what might happen when sodium metal reacts with an alcohol that contains the same functional group. Sodium metal should react with methanol (CH3OH), for example, to give H2 gas and a solution of the Na and CH3O ions dissolved in the alcohol. 2Na(s) 2 CH3OH(l) H2(g) 2 Na (alc) 2 CH3O (alc)
Because they involve the transfer of electrons, the reactions between sodium metal and either water or an alcohol are examples of oxidationreduction reactions. But what about the following reaction, in which hydrogen gas reacts with an alkene in the presence of a transition metal catalyst to form an alkane? H H G D C PC G D H H H H H2
Ni
H C
C H
H H
There is no change in the number of valence electrons on any of the atoms in the reaction. Both before and after the reaction, each carbon atom shares a total of eight valence electrons and each hydrogen atom shares two electrons. Instead of electrons, the reaction involves the transfer of atomsin this case, hydrogen atoms. There are so many atomtransfer reactions that chemists developed the concept of oxidation number (see Chapter 5) to extend the idea of oxidation and reduction to reactions in which electrons arent necessarily gained or lost. Oxidation involves an increase in the oxidation number of an atom. Reduction occurs when the oxidation number of an atom decreases. During the transformation of ethene into ethane, there is a decrease in the oxidation number of the carbon atom. The reaction therefore involves the reduction of ethene to ethane.
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H G D C PC G D H H
H H H2
Ni
H C
3
C H
H H
Reactions in which none of the atoms undergo a change in oxidation number are called metathesis reactions. Consider the reaction between a carboxylic acid and an amine, for example, CH3CO2H CH3NH2 88n CH3CO2 CH3NH3
or the reaction between an alcohol and hydrogen bromide. CH3CH2OH HBr 88n CH3CH2Br H2O
These are metathesis reactions because there is no change in the oxidation number of any atom in either reaction. The oxidation numbers of the carbon atoms in a variety of compounds are given in Table O2.3. The oxidation numbers can be used to classify organic reactions as either oxidationreduction reactions or metathesis reactions.
FUNCTIONAL GROUP CHEMISTRY Typical Oxidation Numbers of Carbon Example CH4 CH3Li H2CPCH2 CH3OH CH3OCH3 CH3Cl CH3NH2 HCqCH H2CO HCO2H CO2 Oxidation Number of the Carbon 4 4 2 2 2 2 2 1 0 2 4
TABLE O2.3
Classes of Compounds Alkane Alkyllithium Alkene Alcohol Ether Alkyl halide Amine Alkyne Aldehyde Carboxylic acid
Exercise O2.4
Classify the following as either oxidationreduction or metathesis reactions. (a) 2 CH3OH H CH3OCH3 H2O 8n O O B B 8n (b) HCOH CH3OH H HCOCH3 (c) CO 2 H2 n CH3OH (d) CH3Br 2 Li n CH3Li LiBr
H2O
Solution (a) This is a metathesis reaction because there is no change in the oxidation number of the carbon atoms when an alcohol is converted to an ether. 2 CH3OH 88n CH3OCH3
2 2
H2O
(b) This is a metathesis reaction because there is no change in the oxidation number of any of the carbon atoms when a carboxylic acid reacts with an alcohol to form an ester. HCO2H
2
H2O
(c) This is an oxidationreduction reaction because the carbon atom is reduced from the 2 to the 2 oxidation state when CO combines with H2 to form methanol. CO
2
2 H2 88n CH3OH
2
(d) This is an oxidationreduction reaction because the carbon atom is reduced from the 2 to the 4 oxidation state when CH3Br reacts with lithium metal to form CH3Li. CH3Br
2
2 Li 88n CH3Li
4
LiBr
Because electrons are neither created nor destroyed, oxidation cant occur in the absence of reduction, and vice versa. It is often useful, however, to focus attention on one component of the reaction and ask, is that substance oxidized or reduced?
Exercise O2.5
Determine whether the following transformations involve the oxidation or the reduction of the carbon atom. H H C H O B H C H O B H C OH O B H C OH OH O B H C H
OPC PO
Solution Each of the transformations involves the oxidation of the carbon atom. The first reaction involves oxidation of the carbon atom from the 2 to the 0 oxidation state. In the second reaction the carbon atom is oxidized to the 2 state, and the third reaction involves oxidation of the carbon atom to the 4 oxidation state.
2
H OH
H C H
0
0 O B H C H
O B H C H
2 O B H C OH 4
O B H C OH
OPCPO
Assigning oxidation numbers to the individual carbon atoms in a complex molecule can be difficult. Fortunately, there is another way to recognize oxidationreduction reactions in organic chemistry: Oxidation occurs when hydrogen atoms are removed from a carbon atom or when an oxygen atom is added to a carbon atom. Reduction occurs when hydrogen atoms are added to a carbon atom or when an oxygen atom is removed from a carbon atom.
The first reaction in Exercise O2.5 involves oxidation of the carbon atom because a hydrogen atom is removed from that atom when the alcohol is oxidized to an aldehyde. O B CH3OH 8n HCH The second reaction in the exercise is an example of oxidation because an oxygen atom is added to the carbon atom when an aldehyde is oxidized to a carboxylic acid. O B HC H O B HCOH
Reduction, on the other hand, occurs when hydrogen atoms are added to a carbon atom or when an oxygen atom is removed from a carbon atom. An alkene is reduced, for example, when it reacts with H2 to form the corresponding alkane. CH2PCHCH3
Ni H2 88n CH3CH2CH3
Figure O2.1 provides a useful guide to the oxidationreduction reactions of organic compounds. Each of the arrows in this figure involves a two-electron oxidation of a carbon atom along the path toward carbon dioxide. A line is drawn through the first arrow because it is impossible to achieve this transformation in a single step. O B HCH
0
CH4
4
CH3OH
2
O B HCOH
+2
CO2
+4
CH2 = CH(CH2)3CH3
CH3(CH2)4CH3
The characteristic red-orange color of bromine disappears the instant this reagent is added to the alkene in the upper left corner as the Br2 molecules add across the CPC double bond in the alkene.
CH2PCH(CH2)3CH3
The other crystallizing dish picks up the characteristic color of a dilute solution of bromine because the reagent doesnt react with alkanes under normal conditions. If the crystallizing dish in the upper right corner is moved into the center of the projector, however, the color of the bromine slowly disappears. This can be explained by noting that alkanes react with halogens at high temperatures or in the presence of light to form alkyl halides, as noted in Section O1.8. Br A Light Br2 88n CH3CH(CH2)3CH3
CH3(CH2)4CH3
HBr
The light source in an overhead projector is intense enough to initiate the reaction, although the reaction is still much slower than the addition of Br2 to an alkene. The reaction between an alkane and one of the halogens (F2, Cl2, Br2, or I2) can be understood by turning to a simpler example. CH4(g) Cl2(g) 88n CH3Cl(g) HCl(g)
It doesnt take place in the dark or at low temperatures. It occurs in the presence of ultraviolet light or at temperatures above 250C. Once the reaction gets started, it continues after the light is turned off. The products of the reaction include CH2Cl2 (dichloromethane), CHCl3 (chloroform), and CCl4 (carbon tetrachloride), as well as CH3Cl (chloromethane). The reaction also produces some C2H6.
These facts are consistent with a chain reaction mechanism that involves three processes: chain initiation, chain propagation, and chain termination.
Chain Initiation
A Cl2 molecule can dissociate into a pair of chlorine atoms by absorbing energy in the form of either ultraviolet light or heat. Cl2 88n 2 Cl H 243.4 kJ/molrxn
The chlorine atom produced in the reaction is an example of a free radicalan atom or molecule that contains one or more unpaired electrons.
Chain Propagation
Free radicals, such as the Cl atom, are extremely reactive. When a chlorine atom collides with a methane molecule, it can remove a hydrogen atom to form HCl and a CH3 radical. CH4 Cl 88n CH3 HCl H 16 kJ/molrxn
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If the CH3 radical then collides with a Cl2 molecule, it can remove a chlorine atom to form CH3Cl and a new Cl radical. CH3 Cl2 88n CH3Cl Cl H 87 kJ/molrxn
Because a Cl atom is generated in the second reaction for every Cl atom consumed in the first, the reaction continues in a chainlike fashion until the radicals involved in the chain propagation steps are destroyed.
Chain Termination
If a pair of the radicals that keep the chain reaction going collide, they combine in a chain terminating step. Chain termination can occur in three ways. 2 Cl 88n Cl2 CH3 Cl 88n CH3Cl 2 CH3 88n CH3CH3 H H H 243.4 kJ/molrxn 330 kJ/molrxn 350 kJ/molrxn
Because the concentration of the radicals is relatively small, the chain termination reactions are relatively infrequent. The chain reaction mechanism for free radical reactions explains the observations listed for the reaction between CH4 and Cl2.
The reaction doesnt occur in the dark or at low temperatures because energy must be absorbed to generate the free radicals that carry the reaction. Cl2 88n 2 Cl H 243.4 kJ/molrxn
The reaction occurs in the presence of ultraviolet light because a UV photon has enough energy to dissociate a Cl2 molecule to a pair of Cl atoms. The reaction occurs at high temperatures because Cl2 molecules can dissociate to form Cl atoms by absorbing thermal energy. The reaction continues after the light has been turned off because light is needed only to generate the Cl atoms that start the reaction. The chain reaction then converts CH4 into CH3Cl without consuming the Cl atoms.
CH4 CH3
The reaction doesnt stop at CH3Cl because the Cl atoms can abstract additional hydrogen atoms to form CH2Cl2, CHCl3, and eventually CCl4. CH3Cl CH2Cl Cl 88n CH2Cl Cl2 88n CH2Cl2 HCl Cl , and so on
The formation of C2H6 is a clear indication that the reaction proceeds through a free radical mechanism. When two CH3 radicals collide, they combine to form an ethane molecule.
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2 CH3 88n CH3CH3 Free radical halogenation of alkanes provides us with another example of the role of atom transfer reactions in organic chemistry. The net effect of the reaction is to oxidize a carbon atom by removing a hydrogen from the atom. CH4
4
Cl2
CH3Cl
2
HCl
The reaction, however, doesnt involve the gain or loss of electrons. It occurs by the transfer of a hydrogen atom in one direction and a chlorine atom in the other.
The systematic nomenclature for alcohols adds the ending -ol to the name of the parent alkane and uses a number to identify the carbon that carries the OOH group. The systematic name for isopropyl alcohol, for example, is 2-propanol. CH3OH CH3CH2OH CH3CHOHCH3 Methanol Ethanol 2-Propanol
Exercise O2.6
More than 50 organic compounds have been isolated from the oil that gives rise to the characteristic odor of a rose. One of the most abundant of the compounds is known by the common name citronellol. Use the systematic nomenclature to name this alcohol, which has the following structure. CH3 A CH D G H2C CH2 A A H2C CH2O OH G CH B C D G CH3 CH3 Solution The longest chain of carbon atoms in the compound contains eight atoms.
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3A
CH3
The longest chain contains the OOH group, which means the compound is named as a derivative of octane. Because it is an alcohol, it would be tempting to name it as an octanol. But it contains a CPC double bond, which means it must be an octenol. We now have to indicate that the OOH group is on one end of the chain and the CPC double bond occurs between the sixth and seventh carbon atoms of the chain, which can be done by considering the compound to be a derivative of 6-octen-1-ol. Finally, we have to indicate the presence of a pair of CH3 groups on the third and seventh carbon atoms. The compound is therefore given the systematic name 3,7-dimethyl-6-octen-1-ol.
Methanol, or methyl alcohol, is also known as wood alcohol because it was originally made by heating wood until a liquid distilled. Methanol is highly toxic, and many people have become blind or have died from drinking it. Ethanol, or ethyl alcohol, is the alcohol associated with alcoholic beverages. It has been made for at least 6000 years by adding yeast to solutions that are rich in either sugars or starches. The yeast cells obtain energy from enzyme-catalyzed reactions that convert sugar or starch to ethanol and CO2. C6H12O6(aq) 88n 2 CH3CH2OH(aq) 2 CO2(g)
When the alcohol reaches a concentration of 10% to 12% by volume, the yeast cells die. Brandy, rum, gin, and the various whiskeys that have a higher concentration of alcohol are prepared by distilling the alcohol produced by the fermentation reaction. Ethanol isnt as toxic as methanol, but it is still dangerous. Most people are intoxicated at blood-alcohol levels of about 0.1 gram per 100 mL. An increase in the level of alcohol in the blood to between 0.4 and 0.6 g/100 mL can lead to coma or death. The method of choice for determining whether an individual is DUIdriving under the influenceor DWIdriving while intoxicatedis the Breathalyzer, for which a patent was issued to R. F. Borkenstein in 1958. The chemistry behind the Breathalyzer is based on the reaction between alcohol in the breath and the chromate or dichromate ion. 3 CH3CH2OH(g) 2 Cr2O72 (aq) 16 H (aq) 88n 3 CH3CO2H(aq)
4 Cr3 (aq)
11 H2O(l)
The instrument contains two ampules that hold small samples of potassium dichromate dissolved in sulfuric acid. One of the ampules is used as a reference. The other is opened and the breath sample to be analyzed is added. If alcohol is present in the breath, it reduces the yellow-orange Cr2O72 ion to the green Cr3 ion. The extent to which the color balance between the two ampules is disturbed is a direct measure of the amount of alcohol in the breath sample. Measurements of the alcohol on the breath are then converted into
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estimates of the concentration of the alcohol in the blood by assuming that 2100 mL of air exhaled from the lungs contains the same amount of alcohol as 1 mL of blood. Measurements taken with the Breathalyzer are reported in units of percent bloodalcohol concentration (BAC). In most states, a BAC of 0.10% is sufficient for a DUI or DWI conviction. (This corresponds to a blood-alcohol concentration of 0.10 gram of alcohol per 100 mL of blood.) Ethanol is oxidized to CO2 and H2O by the alcohol dehydrogenase enzymes in the body. This reaction gives off 30 kilojoules per gram, which makes ethanol a better source of energy than carbohydrates (17 kJ/g), and almost as good a source of energy as fat (38 kJ/g). An ounce of 80-proof liquor can provide as much as 3% of the average daily caloric intake, and drinking alcohol can contribute to obesity. Many alcoholics are malnourished, however, because of the absence of vitamins in the calories they obtain from alcoholic beverages. As a general rule, polar or ionic substances dissolve in polar solvents; nonpolar substances dissolve in nonpolar solvents. As a result, hydrocarbons dont dissolve in water. They are often said to be immiscible (literally, not mixable) in water. Alcohols, as might be expected, have properties between the extremes of hydrocarbons and water. When the hydrocarbon chain is short, the alcohol is soluble in water. There is no limit on the amount of methanol (CH3OH) and ethanol (CH3CH2OH), for example, that can dissolve in a given quantity of water. As the hydrocarbon chain becomes longer, the alcohol becomes less soluble in water, as shown in Table O2.4. One end of the alcohol molecules has so much nonpolar character it is said to be hydrophobic (literally, water-hating). The other end contains an OOH group that can form hydrogen bonds to neighboring water molecules and is therefore said to be hydrophilic (literally, water-loving). As the hydrocarbon chain becomes longer, the hydrophobic character of the molecule increases, and the solubility of the alcohol in water gradually decreases until it becomes essentially insoluble in water.
TABLE O2.4 Formula CH3OH CH3CH2OH CH3(CH2)2OH CH3(CH2)3OH CH3(CH2)4OH CH3(CH2)5OH CH3(CH2)6OH CH3(CH2)7OH CH3(CH2)9OH Solubilities of Alcohols in Water Name Methanol Ethanol Propanol Butanol Pentanol Hexanol Heptanol Octanol Decanol Solubility in Water (g/100 g) Infinitely soluble Infinitely soluble Infinitely soluble 9 2.7 0.6 0.18 0.054 Insoluble in water
Alcohols are classified as either primary (1), secondary (2), or tertiary (3) on the basis of their structures. OH A CH3CHCH3
2
CH3CH2OH
1
OH A CH3CCH3 A CH3
3
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Ethanol is a primary alcohol because there is only one alkyl group attached to the carbon that carries the OOH substituent. The structure of a primary alcohol can be abbreviated as RCH2OH, where R stands for an alkyl group. The isopropyl alcohol found in rubbing alcohol is a secondary alcohol, which has two alkyl groups on the carbon atom with the OOH substituent (R2CHOH). An example of a tertiary alcohol (R3COH) is tert-butyl (or t-butyl) alcohol or 2-methyl-2-propanol. Another class of alcohols are the phenols, in which an OOH group is attached to an aromatic ring, as shown in Figure O2.3. Phenols are potent disinfectants. When antiseptic techniques were first introduced in the 1860s by Joseph Lister, it was phenol (or carbolic acid, as it was then known) that was used. Phenol derivatives, such as o-phenylphenol, are still used in commercial disinfectants such as Lysol. OH OH
Phenol o-Phenylphenol
Water has an unusually high boiling point because of the hydrogen bonds between the H2O molecules. Alcohols can form similar hydrogen bonds, as shown in Figure O2.4. CH3 O H ,, O CH3
FIGURE O2.4 A hydrogen bond between a pair of methanol molecules.
As a result, alcohols have boiling points that are much higher than alkanes with similar molecular weights. The boiling point of ethanol, for example, is 78.5C, whereas propane, with about the same molecular weight, boils at 42.1C. Alcohols are Brnsted acids in aqueous solution. CH3CH2OH(aq) 88n H2O(l) m88 H3O (aq) CH3CH2O (aq)
Alcohols therefore react with sodium metal to produce sodium salts of the corresponding conjugate base, as noted in Section O2.2. 2 Na(s) 2 CH3OH(l) 88n 2 Na (alc) 2 CH3O (alc) H2(g)
[Na ][CH3CH2O ]
Sodium ethoxide
As we saw in Section O1.8, alcohols can be prepared by adding water to an alkene in the presence of a strong acid such as concentrated sulfuric acid. The reaction involves adding an H2O molecule across a CPC double bond. Because the reactions follow Markovnikovs rule, the product of the reaction is often a highly substituted 2 or 3 alcohol.
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CH3CHP CHCH3
H2O
H2SO4
OH A CH3CHCH2CH3
Less substituted 1 alcohols can be prepared by substitution reactions that occur when a primary alkyl halide is allowed to react with the OH ion. CH3CH2CH2Br OH 88n CH3CH2CH2OH Br
Alcohols (ROH) can be thought of as derivatives of water in which one of the hydrogen atoms has been replaced by an alkyl group. If both of the hydrogen atoms are replaced by alkyl groups, we get an ether (ROR). These compounds are named by adding the word ether to the names of the alkyl groups. CH3CH2OCH2CH3
diethyl ether
Diethyl ether, often known by the generic name ether, was once used extensively as an anesthetic. Because mixtures of diethyl ether and air explode in the presence of a spark, ether has been replaced by safer anesthetics. There are important differences between both the physical and chemical properties of alcohols and ethers. Consider diethyl ether and 1-butanol, for example, which are constitutional isomers with the formula C4H10O. CH3CH2OCH2CH3 BP 34.5C density 0.7138 g/mL Insoluble in water CH3CH2CH2CH2OH BP 117.2C density 0.8098 g/mL Soluble in water
The shapes of the molecules are remarkably similar, as shown in Figure O2.5. O OH
The fundamental difference between the compounds is the presence of OOH groups in the alcohol that are missing in the ether. Because hydrogen bonds cant form between the molecules in the ether, the boiling point of the compound is more than 80C lower than that of the corresponding alcohol. Because there are no hydrogen bonds to organize the structure of the liquid, the ether is significantly less dense than the corresponding alcohol. Ethers can act as a hydrogen bond acceptor, as shown in Figure O2.6, but they cant act as hydrogen bond donors. As a result, ethers are less soluble in water than alcohols with the same molecular weight. H O H O CH3
FIGURE O2.6 Water acting as a hydrogen bond donor toward an ether.
CH3
The absence of an OOH group in an ether also has important consequences for its chemical properties. Unlike alcohols, ethers are essentially inert to chemical reactions. They
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dont react with most oxidizing or reducing agents, and they are stable to most acids and bases, except at high temperatures. They are therefore frequently used as solvents for chemical reactions. Compounds that are potential sources of an H ion, or proton, are often described as being protic. Ethanol, for example, is a protic solvent. CH3CH2OH(aq) H2O(l) H3O (aq) CH3CH2O (aq)
Substances that cant act as a source of a proton are said to be aprotic. Because they dont contain an OOH group, ethers are aprotic solvents. Ethers can be synthesized by splitting out a molecule of water between two alcohols in the presence of heat and concentrated sulfuric acid. 2 CH3CH2OH
H
CH3CH2OCH2CH3
They can also be formed by reacting a primary alkyl halide with an alkoxide ion. CH3CH2CH2Br CH3O 88n CH3CH2CH2OCH3 Br
H C
C H
H H
The driving force behind the reaction is the difference between the strengths of the bonds that must be broken and the bonds that form in the reaction. In the course of the hydrogenation reaction, a relatively strong HOH bond (435 kJ/mol) and a moderately strong carboncarbon bond (~270 kJ/mol) are broken, but two strong COH bonds (439 kJ/mol) are formed. The reduction of an alkene to an alkane is therefore an exothermic reaction. What about the addition of an H2 molecule across a CPO double bond? H O B H C C H H H OH H2
Pt
H C
C H
H H
Once again, a significant amount of energy has to be invested in the reaction to break the HOH bond (435 kJ/mol) and the carbonoxygen bond (~375 kJ/mol). The overall reaction is still exothermic, however, because of the strength of the COH bond (439 kJ/mol) and the OOH bond (498 kJ/mol) that are formed. The addition of hydrogen across a CPO double bond raises several important points. First, and perhaps foremost, it shows the connection between the chemistry of primary alcohols and aldehydes. But it also helps us understand the origin of the term aldehyde. If a
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reduction reaction in which H2 is added across a double bond is an example of a hydrogenation reaction, then an oxidation reaction in which an H2 molecule is removed to form a double bond might be called dehydrogenation. Thus, using the symbol [O] to represent an oxidizing agent, we see that the product of the oxidation of a primary alcohol is literally an al-dehyd or aldehyde. It is an alcohol that has been dehydrogenated. O B CH3CH
CH3CH2OH
[O]
The reaction also illustrates the importance of differentiating between primary, secondary, and tertiary alcohols. Consider the oxidation of isopropyl alcohol, or 2-propanol, for example. OH A CH3CHCH3 O B CH3CCH3
[O]
The product of this particular reaction was originally called aketone, although the name was eventually softened to azetone and finally acetone. Thus, it is not surprising that any substance that exhibited chemistry that resembled aketone became known as a ketone. Aldehydes can be formed by oxidizing a primary alcohol; oxidation of a secondary alcohol gives a ketone. What happens when we try to oxidize a tertiary alcohol? The answer is simple: Nothing happens. OH A CH3CCH3 A CH3
[O]
There arent any hydrogen atoms that can be removed from the carbon atom carrying the OOH group in a 3 alcohol. And any oxidizing agent strong enough to insert an oxygen atom into a COC bond would oxidize the alcohol all the way to CO2 and H2O. A variety of oxidizing agents can be used to transform a secondary alcohol to a ketone. A common reagent for the reaction is some form of chromium(VI)chromium in the 6 oxidation statein acidic solution. The reagent can be prepared by adding a salt of the chromate (CrO42 ) or dichromate (Cr2O72 ) ion to sulfuric acid. Or it can be made by adding chromium trioxide (CrO3) to sulfuric acid. Regardless of how it is prepared, the oxidizing agent in the reactions is chromic acid, H2CrO4. OH A CH3CHCH2CH3 O B CH3CCH2CH3
H2CrO4
The choice of oxidizing agents to convert a primary alcohol to an aldehyde is much more limited. Most reagents that can oxidize the alcohol to an aldehyde carry the reaction one step furtherthey oxidize the aldehyde to the corresponding carboxylic acid. O B CH3CH O B CH3COH
CH3CH2OH
H2CrO4
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A weaker oxidizing agent, which is just strong enough to prepare the aldehyde from the primary alcohol, can be obtained by dissolving the complex that forms between CrO3 and pyridine, C6H5N, in a solvent such as dichloromethane that doesnt contain any water.
CrO3 /pyridine CH2Cl2
CH3CH2OH
O B CH3CH
O B HCH
Formaldehyde
O B CH3COH
Acetic acid
O B CH3CH
Acetaldehyde
The systematic names for aldehydes are obtained by adding -al to the name of the parent alkane. O B HCH
Methanal
O B CH3CH
Ethanal
The presence of substituents is indicated by numbering the parent alkane chain from the end of the molecule that carries the OCHO functional group. For example, O B BrCH2CH2CH
3-Bromopropanal
The common name for a ketone is constructed by adding ketone to the names of the two alkyl groups on the carbon of the CPO double bond, listed in alphabetical order. O B CH3CCH2CH3
The systematic name is obtained by adding -one to the name of the parent alkane and using numbers to indicate the location of the CPO group. O B CH3CCH2CH3
2-Butanone
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odor of almonds, vanillin is responsible for the flavor of vanilla, and cinnamaldehyde makes an important contribution to the flavor of cinnamon. O B CH
Benzaldehyde
HO CH3O
Vanillin
O B CH
Cinnamaldehyde
O B CH
We can represent the polar nature of the hybrid by indicating the presence of a slight negative charge on the oxygen ( ) and a slight positive charge ( ) on the carbon of the CPO double bond.
O B C D G Reagents that attack the electron-rich end of the CPO bond are called electrophiles (literally, lovers of electrons). Electrophiles include ions (such as H and Fe3 ) and neutral molecules (such as AlCl3 and BF3) that are Lewis acids, or electron pair acceptors. Reagents that attack the electron-poor end of the bond are nucleophiles (literally, lovers of nuclei). Nucleophiles are Lewis bases (such as NH3 or the OH ion).
O O
Electrophiles O B (H , Fe3 , BF , etc.) 3 C D G Nucleophiles (OH , NH3, etc.) The polarity of the CPO double bond can be used to explain the reactions of carbonyl compounds. Aldehydes and ketones react with a source of the hydride ion (H ) because the H ion is a Lewis base, or nucleophile, that attacks the end of the CPO bond. When this happens, the two valence electrons on the H ion form a covalent bond to the carbon atom. Since carbon is tetravalent, one pair of electrons in the CPO bond is displaced onto the oxygen to form an intermediate with a negative charge on the oxygen atom.
O S
20
O B C D G CH3 CH3 HS
The alkoxide ion can then remove an H ion from water to form an alcohol. O SOS A CH3OC OCH3 A H O SO OH A CH3OC OCH3 A H
O S
H2O
OH
Common sources of the H ion include lithium aluminum hydride (LiAlH4) and sodium borohydride (NaBH4). Both compounds are ionic. LiAlH4: NaBH4: [Li ][AlH4 ] [Na ][BH4 ]
The aluminum hydride (AlH4 ) and borohydride (BH4 ) ions act as if they were complexes between an H ion, acting as a Lewis base, and neutral AlH3 or BH3 molecules, acting as a Lewis acid. H A HOAlOH A H H A AlOH A H
HS
LiAlH4 is such a good source of the H ion that it reacts with the H ions in water or other protic solvents to form H2 gas. The first step in the reduction of a carbonyl with LiAlH4 is therefore carried out using an ether as the solvent. The product of the hydride reduction reaction is then allowed to react with water in a second step to form the corresponding alcohol. O B CH3CH2CH
1. LiAlH4 in ether 2. H2O
CH3CH2CH2OH
NaBH4 is less reactive toward protic solvents, which means that borohydride reductions are usually done in a single step, using an alcohol as the solvent. O OH B A NaBH4 CH3CH2CCH3 CH CH OH CH3CH2CHCH3
3 2
21
O J CH3O C G OH
O J CH3O C G O
The carboxylate ion formed in the reaction is a hybrid of two resonance structures. O J CH3O C G O O D CH3O C M O
Resonance delocalizes the negative charge in the carboxylate ion, which makes the ion more stable than the alkoxide ion formed when an alcohol loses an H ion. By increasing the stability of the conjugate base, resonance increases the acidity of the acid that forms the base. Carboxylic acids are therefore much stronger acids than the analogous alcohols. The Ka value for a typical carboxylic acid is about 10 5, whereas alcohols have Ka values only 10 16. O J CH3C G OH CH3OH O J CH3C G O CH3O H
Ka
1.8
10
Ka
10
16
Carboxylic acids were among the first organic compounds to be discovered. As a result, they have well-established common names that are often derived from the Latin stems of their sources in nature. Formic acid (Latin formica, an ant) and acetic acid (Latin acetum, vinegar) were first obtained by distilling ants and vinegar, respectively. Butyric acid (Latin butyrum, butter) is found in rancid butter, and caproic, caprylic, and capric acids (Latin caper, goat) are all obtained from goat fat. A list of common carboxylic acids is given in Table O2.5. The systematic nomenclature of carboxylic acids is easy to understand. The ending -oic acid is added to the name of the parent alkane to indicate the presence of the OCO2H functional group. HCO2H CH3CO2H CH3CH2CO2H Methanoic acid Ethanoic acid Propanoic acid
Unfortunately, because of the long history of carboxylic acids and their importance in biology and biochemistry, you are more likely to encounter these compounds by their common names. Formic acid and acetic acid have sharp, pungent odors. As the length of the alkyl chain increases, the odor of carboxylic acids becomes more unpleasant. Butyric acid, for example, is found in sweat, and the odor of rancid meat is due to carboxylic acids released as the meat spoils. The solubility data in Table O2.5 show that carboxylic acids also become less soluble in water as the length of the alkyl chain increases. The OCO2H end of the molecule is polar and therefore soluble in water. As the alkyl chain gets longer, the molecule becomes more nonpolar and less soluble in water.
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FUNCTIONAL GROUP CHEMISTRY Common Carboxylic Acids Formula Saturated carboxylic acids and fatty acids Solubility in H2O (g/100 mL)
TABLE O2.5
Common Name
Formic acid Acetic acid Propionic acid Butyric acid Caproic acid Caprylic acid Capric acid Lauric acid Myristic acid Palmitic acid Stearic acid Palmitoleic acid Oleic acid Linoleic acid Linolenic acid
HCO2H CH3CO2H CH3CH2CO2H CH3(CH2)2CO2H CH3(CH2)4CO2H CH3(CH2)6CO2H CH3(CH2)8CO2H CH3(CH2)10CO2H CH3(CH2)12CO2H CH3(CH2)14CO2H CH3(CH2)16CO2H Unsaturated fatty acids CH3(CH2)5CHPCH(CH2)7CO2H CH3(CH2)7CHPCH(CH2)7CO2H CH3(CH2)4CHPCHCH2CHPCH(CH2)7CO2H CH3CH2CHPCHCH2CHPCHCH2CHPCH(CH2)7CO2H
Compounds that contain two OCO2H functional groups are known as dicarboxylic acids. A number of dicarboxylic acids (see Table O2.6) can be isolated from natural sources. Tartaric acid, for example, is a by-product of the fermentation of wine, and succinic, fumaric, malic, and oxaloacetic acids are intermediates in the metabolic pathway used to oxidize sugars to CO2 and H2O.
TABLE 02.6 Common Dicarboxylic Acids Structure HO2CCO2H HO2CCH2CO2H HO2CCH2CH2CO2H HO 2C CO H G D 2 C PC D G H H H HO 2C G D C PC D G H CO2 H Common Name Oxalic acid Malonic acid Succinic acid Maleic acid Structure OH A HO2CCH2CHCO2H OH OH A A HO2CCHCHCO2H O B HO2CCH2CCO2H Common Name
Fumaric acid
Several tricarboxylic acids also play an important role in the metabolism of sugar. The most important example of this class of compounds is the citric acid that gives so many fruit juices their characteristic acidity.
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Citric acid
O2.8 ESTERS
Carboxylic acids (OCO2H) can react with alcohols (ROH) in the presence of either acid or base to form esters (OCO2R). Acetic acid, for example, reacts with ethanol to form ethyl acetate. O B CH3COH O B CH3COCH2CH3
CH3CH2OH
H2O
This isnt an efficient way of preparing an ester, however, because the equilibrium constant for the reaction is relatively small (Kc 3). Chemists therefore tend to synthesize esters from carboxylic acids in a two-step process. They start by reacting the acid with a chlorinating agent such as thionyl chloride (SOCl2) to form the corresponding acyl chloride. O B CH3COH O B CH3CCl
SOCl2
SO2
HCl
They then react the acyl chloride with an alcohol in the presence of base to form the ester. O B CH3CCl O B CH3COCH2CH3
CH3CH2OH
BH Cl
The base absorbs the HCl given off in the reaction, thereby driving it to completion. As might be expected, esters are named as if they were derivatives of a carboxylic acid and an alcohol. The ending -ate or -oate is added to the name of the parent carboxylic acid, and the alcohol is identified using the alkyl alcohol convention. The following ester, for example, can be named as a derivative of acetic acid (CH3CO2H) and ethyl alcohol (CH3CH2OH). O B CH3COCH2CH3
Ethyl acetate
Or it can be named as a derivative of ethanoic acid (CH3CO2H) and ethyl alcohol (CH3CH2OH). O B CH3COCH2CH3
Ethyl ethanoate
The term ester is commonly used to describe the product of the reaction of any strong acid with an alcohol. Sulfuric acid, for example, reacts with methanol to form a diester known as dimethyl sulfate.
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O A HO S OH A O
2 CH3OH
O A CH3O S OCH3 A O
2 H2O
Phosphoric acid reacts with alcohols to form triesters such as trimethyl phosphate. O A HO P OH A OH O A CH3O P OCH3 A OCH3
3 CH3OH
3 H2O
Compounds that contain the OCO2R functional group might therefore best be called carboxylic acid esters, to indicate the acid from which they are formed. Carboxylic acid esters with low molecular weights are colorless, volatile liquids that often have a pleasant odor. They are important components of both natural and synthetic flavors (see Figure O2.8). CH3O C O O CH2 CH3
Methyl salicylate (oil of wintergreen)
FIGURE O2.8 Typical carboxylic acid esters with pleasant odors or flavors.
The systematic names of primary amines are derived from the name of the parent alkane by adding the prefix amino- and a number specifying the carbon that carries the ONH2 group. CHP CH NH2 D G D CH2O CH CH3 G CH3
OH E
CH2 CH2
CH3 CH CH3
CH2
B O
O C
B O
O
B O
CH2 CH2
CH3 CH CH3
(CH3)2CHNH2
Isopropylamine
5-Amino-2-hexene
25
The chemistry of amines mirrors the chemistry of ammonia. Amines are weak bases that pick up a proton to form ammonium salts. Trimethylamine, for example, reacts with acid to form the trimethylammonium ion. CH3 A CH3ONS A CH3 CH3 A CH3ONOH A CH3
The salts are more soluble in water than the corresponding amines, and the reaction can be used to dissolve otherwise insoluble amines in aqueous solution. The difference between amines and their ammonium salts plays an important role in both over-the-counter and illicit drugs. Cocaine, for example, is commonly sold as the hydrochloride salt, which is a white, crystalline solid. By extracting the solid into ether, it is possible to obtain the free base. A glance at the side panel of almost any over-thecounter medicine will provide examples of ammonium salts of amines that are used to ensure that the drug dissolves in water (see Figure O2.9). CH3 CH3O
Dextromethorphan hydrobromide (cough suppressant)
CH3 CH HO CH H CH3
NH2 Cl
Br
Amines that are isolated from natural sources, especially from plants, are known as alkaloids. They include poisons such as nicotine, coniine, and strychnine (shown in Figure O2.10). Nicotine has a pleasant, invigorating effect when taken in minuscule quantities but is extremely toxic in larger amounts. Coniine is the active ingredient in hemlock, a poison that has been used since the time of Socrates. Strychnine is another toxic alkaloid that has been a popular poison in murder mysteries.
N N CH3
Nicotine
N H
Coniine
O N O
Strychnine
FIGURE O2.10 The alkaloids are complex amines that can be isolated from plants.
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The alkaloids also include a number of drugs, such as morphine, quinine, and cocaine. Morphine is obtained from poppies; quinine can be found in the bark of the chinchona tree; and cocaine is isolated from coca leaves. This family of compounds also includes synthetic analogs of naturally occurring alkaloids, such as heroin and LSD (see Figure O2.11). To illustrate the importance of minor changes in the structure of a molecule, three amines with similar structures are shown in Figure O2.12. One of the compounds is caffeine, which is the pleasantly addictive substance that makes a cup of coffee an important part of the day for so many people. Another is theobromine, which is the pleasantly addictive substance that draws so many people to chocolate. The third compound is theophylline, which is a prescription drug used as a bronchodilator for people with asthma. O B CH3COO
Morphine Heroin
HOH
O NOCH3 E HO CH3H N
Cocaine
O
ECH3 N
E CH3CO B O
O
CHPCH2
CO2CH3 HO CH3OH H E CH A N
P O
H OC O
Quinine
O CH3H N O N A CH3
Caffeine
N N
CH3 f
O HH N O N A CH3
CH3 f N N
O CH3H N O N A CH3
Theophylline
H i N N
Theobromine
FIGURE O2.12 The caffeine in coffee, the theobromine in chocolate, and the active ingredient in a common bronchodilator are central nervous system stimulants with very similar structures.
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It is tempting to assume that carboxylic acids will react with amines to form the class of compounds known as amides. In practice, when aqueous solutions of carboxylic acids and amines are mixed all we get is an acidbase reaction. O B CH3COH O B CH3CO CH3NH3
CH3NH2
The best way to prepare an amide is to react the appropriate acyl chloride with an amine. O B CH3CCl O B CH3CNHCH3
2 CH3NH2
CH3NH3 Cl
Excess amine is used to drive the reaction to completion by absorbing the HCl given off in the reaction.
Et O
Because carbon is considerably more electronegative than magnesium, the metalcarbon bond in the product has a significant amount of ionic character. Grignard reagents such as CH3MgBr are best thought of as hybrids of ionic and covalent Lewis structures. CH3OMgOBr [CH3S ][Mg 2 ][Br ]
Grignard reagents are therefore a potential source of carbanions (literally, anions of carbon). The Lewis structure of the CH3 ion suggests that carbanions can be Lewis bases, or electron pair donors. H A HO CS A H
28
Grignard reagents such as methylmagnesium bromide are therefore sources of a nucleophile that can attack the end of the CPO double bond in aldehydes and ketones. CH3 CH3S G CPO D CH3 A CH3O C O O A CH3
CH3
If we treat the product of the reaction with water, we get a tertiary alcohol. CH3 A CH3OC OO A CH3 CH3 A CH3OC OOH A CH3
H2O
OH
If we wanted to make a secondary alcohol, we could add the Grignard reagent to an aldehyde, instead of a ketone. O B CH3CH
1. CH 3MgBr 2. H2O
OH A CH3CHCH3
By reacting a Grignard reagent with formaldehyde we can add a single carbon atom to form a primary alcohol. CH3 A CH3CCH2MgBr A CH3 CH3 A CH3CCH2CH2O A CH3 CH3 A CH3CCH2CH2OH A CH3
H2CPO
H2O
The alcohol can then be oxidized to the corresponding aldehyde. CH3 A CH3CCH2CH2OH A CH3 CH3 O B A CH3CCH2CH A CH3
The Grignard reagent therefore provides us with a way of performing the following overall transformation. CH3 A CH3CCH2MgBr A CH3
1. H2CO 2. H2O 3. CrO3 /pyridine in CH2Cl2
A single carbon atom can also be added if the Grignard reagent is allowed to react with CO2 to form a carboxylic acid. CH3 A CH3CCH2MgBr A CH3 CH3 O A B CH3CCH2CO A CH3
H2O
CO2
OH
Perhaps the most important aspect of the chemistry of Grignard reagents is the ease with which the reaction allows us to couple alkyl chains. Isopropylmagnesium bromide, for
29
example, can be used to graft an isopropyl group onto the hydrocarbon chain of an appropriate ketone, as shown in Figure O2.13.
O
CH3
G ECHMgBr CH3
B CH3CH2CCH3
H2O
FIGURE O2.13 Grignard reagents provide a powerful way to introduce alkyl groups onto a hydrocarbon chain.
Citronellol (3-7-dimethyl6-octen-1-ol)
Garlic, onions, and mustard seed differ from most other sources of essential oils. In each case, the fragrance producing part of the plant must be crushed before the volatile components are released. For more than 100 years, chemists have known that the principal component of the oil that distills from garlic is diallyl disulfide [F. W. Semmler, Archiv der Pharmazie, 230, 434448 (1892)]. CH2PCHCH2 SSCH2CHPCH2
Diallyl disulfide
30
Only recently, however, have chemists explained how the compound is produced when a clove of garlic is crushed [E. Block, Angewandte Chemie, International Edition in English, 31, 11011264 (1992)]. Before garlic is crushed, the intact cell contains S2-propenyl-L-cysteine S-oxideor alliinwhich can be found in the cell cytoplasm. O NH3 B A CH2PCHCH2SCH2CHCO2
Alliin
Within the cell there are vacuoles that contain an enzyme known as alliinase. When the cell is crushed, the enzyme is released. The enzyme transforms the natural product alliin into an intermediate that reacts with itself to form a compound known as allicin. O B CH2PCHCH2SSCH2CHPCH2
Allicin
Allicin has been described as an odoriferous, unstable antibacterial substance that polymerizes easily and must be stored at low temperatures. When heated, it breaks down to give a variety of compounds, including the diallyl disulfide obtained when oil of garlic is distilled from the raw material. An alliinase enzyme can also be found in onions, where it converts an isomer of alliin known as S-(E)-1-propenyl-L-cysteine S-oxide into propanethial S-oxide. CH3CH2CHPS OO
Propanethial S-oxide
The product of the reaction is known as the lacrimator factor of onion because it is the substance primarily responsible for the tears generated when onions are cut. A great deal of progress has been made in recent years in identifying the various organosulfur compounds formed when garlic and onion are cut and in understanding the process by which the compounds are formed. The structures of some of the principal organosulfur compounds associated with garlic are shown in Figure O2.15. In spite of the progress made so far, much still has to be learned about the compounds that can be isolated from extracts of the genus Allium, which includes both garlic and onion.
O S SOH S H O S S S
S S O S S
S O
S S S S S S S S
S S
S S S S S S S
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KEY TERMS
Acyl chloride Alcohol Aldehyde Alkaloid Alkoxide Amide Amine Aprotic Carbanion Carbonyl Carboxylate ion Carboxylic acid Carboxylic acid ester Chain initiation Chain propagation Chain reaction Chain termination Dicarboxylic acid Electrophile Ester Ether Free radical Functional group Grignard reagent Hydrophilic Hydrophobic Ketone Nucleophile Oxidation number Protic
PROBLEMS
Functional Groups
1. Give examples of compounds that contain each of the following functional groups. (a) an alcohol (b) an aldehyde (c) an amine (d) an amide (e) an alkyl halide (f) an alkene (g) an alkyne 2. Describe the difference between the members of each of the following pairs of functional groups. (a) an alcohol and an alkoxide ion (b) an alcohol and an aldehyde (c) an amine and an amide (d) an ether and an ester (e) an aldehyde and a ketone 3. Classify the following compounds as an alcohol, an aldehyde, an ether, or a ketone. O O B B (a) CH3CH2CH (b) CH3CH2OH (c) CH3CH2OCH2CH3 (d) CH3CH2CCH3 4. Classify the following compounds as primary, secondary, or tertiary alcohols. CH3 CH3 OH A A A (a) CH3CH2OH (b) CH3CH2CHOH (c) CH3CH2COH (d) CH3CH2CHCH2CH3 A CH3 5. Cortisone is an adrenocortical steroid that is used as an anti-inflammatory agent. Use the fact that carbon is tetravalent to determine the molecular formula of the compound from the following stick structure. Identify the functional groups present in the molecule. CH2OH A CPO CH3A A O OH
O M CH3 A
J O
32
6. Piperine {(E,E)-1-[5-(1,3-benzodioxol-5-yl)-1-oxo-2,4-pentadienyl]piperidine} can be extracted from black pepper. Identify the functional groups in the structure of the compound. O O N B O
7. PGE2 is a member of the family of compounds known as prostaglandins, which have very significant physiological effects in even small quantities. They can affect blood pressure, heart rate, body temperature, blood clotting, and conception. Some induce inflammation; others relieve it. Aspirin, which is both an anti-inflammatory and an antipyretic (fever-reducing) drug, acts by blocking the synthesis of prostaglandins. Identify the functional groups in the structure of the PGE2 molecule and calculate its molecular formula. O CO2H OH
OH
8. Pseudoephedrine hydrochloride is the active ingredient in a variety of decongestants, including Sudafed. Use the structure of the compound shown in Figure O2.9 to identify the functional groups in the molecule. 9. Cocaine was once used in Coca Cola. Quinine is still added to tonic water. Use the structures of the alkaloids shown in Figure O2.11 to identify the functional groups in the compounds.
OXIDATIONREDUCTION REACTIONS
10. Arrange the following substances in order of increasing oxidation number of the carbon atom. (a) C (b) HCHO (c) HCO2H (d) CO (e) CO2 (f) CH4 (g) CH3OH 11. Classify the following reactions as examples of either metathesis or oxidationreduction reactions. (a) CH4 Cl2 n CH3Cl HCl (b) CH3OH n HCHO (c) HCHO n HCO2H (d) CH3OH HBr n CH3Br H2O (e) (CH3)2CO n (CH3)2CHOH 12. Classify the following transformations as examples of either oxidation or reduction. (a) CH3CH2OH n CH3CHO (b) CH3CHO n CH3CO2H (c) (CH3)2CPO n (CH3)2CHOH (d) CH3CHPCHCH3 n CH3CH2CH2CH3 (e) (CH3)2CHCqCH n (CH3)2CHCH2CH3
33
13. Which of the following compounds can be oxidized to form an aldehyde? (a) CH3CH2OH (b) CH3CHOHCH3 (c) CH3OCH3 (d) (CH3)2CPO 14. Which of the following compounds should be the most difficult to oxidize? (a) CH3CH2OH (b) (CH3)2CHOH (c) (CH3)3COH (d) CH3CHO 15. Which of the following compounds can be prepared by reducing CH3CHO? (a) CH3CH3 (b) CH3CH2OH (c) CH3CO2H (d) CH3CH2CO2H 16. Which of the following compounds can be prepared by oxidizing CH3CHO? (a) CH3CH3 (b) CH3CH2OH (c) CH3CO2H (d) CH3CH2CO2H 17. Predict the product of the oxidation of 2-methyl-3-pentanol. 18. Predict the product of the reduction of 2-methyl-2-pentene with hydrogen gas over a nickel metal catalyst.
Alkyl Halides
19. Use Lewis structures to describe the free radical chain reaction mechanism involved in the bromination of methane to form methyl bromide. Clearly label the chain initiation, chain propagation, and chain termination steps. 20. Use Lewis structures to describe the difference between a CH3 ion, a CH3 radical, and a CH3 ion. Which of these Lewis structures describes a carbanion? Which describes a carbocation? 21. How many different products could be formed by the free radical chlorination of pentane? If attack at the different hydrogen atoms in the compound were more or less random, what would be the relative abundance of the different isomers of chloropentane formed in the reaction? 22. Consider the reaction between a Cl atom and a pentane molecule. Classify the different intermediates that could be produced in the reaction as either primary, secondary, or tertiary free radicals.
34
33. Assign a systematic name to the compound known by the common name menthol.
OH
38. Assign a systematic name to the compound known by the common name geranial.
35
42. Explain the difference between CH3CH2OH and CH3CO2H that makes one of the COOH bonds in the compounds more than 10 orders of magnitude more acidic than the other when values of Ka for the compounds are compared. 43. Use the structures shown in Figure O2.11 to propose a series of reactions that could be used to convert morphine into heroin.
Grignard Reagents
47. Use Lewis structures to decide whether the organic component of a Grignard reagent is a nucleophile (Lewis base) or an electrophile (Lewis acid). Predict which end of a CPO bond this portion of the Grignard reagent will attack. 48. If CH3CH2MgBr can be thought of as containing the CH3CH2 , Mg2 , and Br ions, what would be the product of the reaction between the Grignard reagent and dilute hydrochloric acid? 49. Explain why Grignard reagents are prepared in an aprotic solvent, such as an ether, rather than a protic solvent such as an alcohol. 50. Write a step-by-step mechanism for the reaction between CH3MgBr and H2CPO to form CH3CH2OH. 51. Predict the product of the reaction between (CH3)2CHMgBr and 2-pentanone. O B 52. If CH3CH2CCH3 is used as the starting material, show how a tertiary alcohol can be synthesized by a Grignard reaction. 53. Select from the reagents given below to design a sequence of reactions that would lead to the following compound. OH A CH3CHCHCH3 A CH3 (a) (CH3)2CHMgBr (b) CH3CHO (c) CH3MgBr (d) CH3COCH2CH3 (e) CH3COCH3 (f) CH3CH2MgBr (g) CH3COCH3
36
a way of determining whether a compound is an alcohol or an alkyl halide. a way of determining whether a compound is a carboxylic acid or an amide. a way of determining whether a compound is an alcohol or an amine. a way of determining whether a compound is an aldehyde or ketone.
Integrated Problems
62. Identify the Brnsted acids and the Brnsted bases in the following reaction. CH3CqCH NH2 88n CH3CqC NH3
63. Succinic acid plays an important role in the Krebs cycle, malic acid (apple acid) is found in apples, and tartaric acid ( fruit acid) is found in many fruits. Which of these dicarboxylic acids is chiral? See Table O2.6.