15-1 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Chapter 15 Organic Compounds and the Atomic Properties of Carbon

15-2 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Organic Compounds and the Atomic Properties of Carbon 15.1 The Special Nature of Carbon and the Characteristics of Organic Molecules 15.2 The Structures and Classes of Hydrocarbons 15.3 Some Important Classes of Organic Reactions 15.4 Properties and Reactivities of Common Functional Groups 15.5 The Monomer-Polymer Theme I: Synthetic Macromolecules 15.6 The Monomer-Polymer Theme II: Biological Macromolecules

15-3 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.1 The position of carbon in the periodic table.

15-4 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. The Structural Complexity of Organic Molecules Reviewing the atomic structure and properties of carbon, we can get an idea of why organic molecules can be complex. 1. Electron configuration, electronegativity, covalent bonding Contributing factors include: 2. Bond properties, catenation, and molecular shape. catenation - two atoms of the same element bound to each other 3. Molecular stability atomic size and bond strengthavailable orbitals

15-5 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Chemical Diversity Diversity in structure and behavior is due to interrelated factors: 1. Bonding to heteroatoms - See Figure Electron density and reactivity C - C bond  EN = 0; therefore the C-C bond is nonpolar and in general unreactive. C - H bond  EN ~ 0; therefore the C-H bond is nearly nonpolar and fairly unreactive. C - O bond  EN = 1; therefore the C-O bond is polar and reactive. bonds to other heteroatoms are usually large and therefore weak and reactive.

15-6 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.2 The chemical diversity of organic compounds. 4 carbons linked with single bonds, 1 oxygen and needed hydrogens.

15-7 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.2 The chemical diversity of organic compounds continued

15-8 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. HYDROCARBONS Carbon Skeletons and Hydrogen Skins When determining the number of different skeletons, remember that Each C can form a maximum of four single bonds, OR two single and one double bond, OR one single and triple bond. The arrangement of C atoms determines the skeleton, so a straight chain and a bent chain represent the same skeleton. Groups joined by single bonds can rotate, so a branch pointing down is the same as one pointing up.

15-9 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.3 Some five-carbon skeletons CCCCC CCCC C CCC C C CC C CCC CC C C CCCC C CCCC C C CC CC C C C CC CC C CC C C C CC CC C CC CCCC C single bondsdouble bond ring

15-10 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.4 Adding the H-atom skin to the C-atom skeleton A C atom single-bonded to one other atom gets three H atoms. A C atom single-bonded to two other atoms gets two H atoms. A C atom single-bonded to three other atoms gets one H atom. A C atom single-bonded to four other atom is already fully bonded (no H atoms). A double- and single- bonded C atom or a triple-bonded C atom is treated as if it were bonded to three other atoms. A double-bonded C atom is treated as if it were bonded to two other atoms.

15-11 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.1Drawing Hydrocarbons PROBLEM:Draw structures that have different atom arrangements for hydrocarbons with PLAN:Start with the longest chain and then draw shorter chains until you are repeating structures. (a) Six C atoms, no multiple bonds, and no rings (b) Four C atoms, one double bond, and no rings (c) Four C atoms, no multiple bonds, and one ring SOLUTION:(a) Six carbons, no rings

15-12 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.1Drawing Hydrocarbons continued (a) continued (b) Four carbons, one double bond(c) Four carbons, one ring

15-13 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Table 15.1 Numerical Roots for Carbon Chains and Branches Number of C atoms Roots meth- eth- prop- but- hex- pent- hept- oct- non- dec- PREFIX + ROOT + SUFFIX

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15-15 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.5 Ways of depicting formulas and models of an alkane

15-16 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.6 Depicting cycloalkanes cyclopropanecyclobutane

15-17 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.6 continued Depicting cycloalkanes cyclopentanecyclohexane

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15-19 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.7 Boiling points of the first 10 unbranched alkanes

15-20 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.8 An analogy for optical isomers.

15-21 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 15.9 Two chiral molecules. optical isomers of 3-methylhexane optical isomers of alanine

15-22 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The rotation of plane-polarized light by an optically active substance

15-23 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The binding site of an enzyme

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15-25 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure B15.1 The initial chemical event in vision

15-26 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.2Naming Alkanes, Alkenes, and Alkynes PROBLEM:Give the systematic name for each of the following, indicate the chiral center in part (d), and draw two geometric isomers for part (c). PLAN:For (a)-(c), find the longest, continuous chain and give it the base name (root + suffix). Then number the chain so that the branches occur on the lowest numbered carbons and name the branches with the (root + yl). For (d) and (e) the main chain must contain the double bond and the chain must be numbered such that the double bond occurs on the lowest numbered carbon.

15-27 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.2Naming Alkanes, Alkenes, and Alkynes SOLUTION: continued can be numbered in either direction chiral center

15-28 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.2Naming Alkanes, Alkenes, and Alkynes continued

15-29 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure Representations of benzene or

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15-31 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Tools of the Laboratory Nuclear Magnetic Resonance (NMR) Figure B15.2 The basis of proton spin resonance. Figure B15.3 The 1 H-NMR spectrum of acetone. Figure B15.4 The 1 H-NMR spectrum of dimethoxymethane. Figure B15.5 Magnetic resonance imaging (MRI) of a human head.

15-32 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Types of Organic Reactions An addition reaction occurs when an unsaturated reactant becomes a saturated product: Elimination reactions are the opposite of addition; they occur when a more saturated reactant becomes a less saturated product: A substitution reaction occurs when an atom (or group) from an added reagent substitutes for one in the organic reactant:

15-33 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure A color test for C=C bonds

15-34 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.3:Recognizing the Type of Organic Reaction PROBLEM:State whether each reaction is an addition, elimination, or substitution: PLAN:Look for changes in the number of atoms attached to carbon. More atoms bonded to C is an addition. Fewer atoms bonded to C is an elimination. Same number of atoms bonded to C is a substitution.

15-35 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.3: SOLUTION: Recognizing the Type of Organic Reaction continued Elimination: there are fewer bonds to last two carbons. Addition: there are more bonds to the two carbons in the second structure. Substitution: the C-Br bond becomes a C-O bond and the number of bonds to carbon remain the same.

15-36 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure Some molecules with the alcohol functional group

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15-39 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure General structures of amines primary, 1 0, aminesecondary, 2 0, aminetertiary, 3 0, amine the amine functional group

15-40 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure Some biomolecules with the amine functional group. Lysine (1 0 amine) amino acid found in proteins Adenine (1 0 amine) component of nucleic acids Epinephrine (adrenaline; 2 0 amine) neurotransmitter in brain; hormone released during stress Cocaine (3 0 amine) brain stimulant; widely abused drug

15-41 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure Structure of a cationic detergent. benzylcetyldimethyl- ammonium chloride

15-42 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.4:Predicting the Reactions of Alcohols, Alkyl Halides, and Amines PROBLEM:Determine the reaction type and predict the product(s) in the following: PLAN:Check for functional groups and reagents, then for inorganics added. In (a) the -OH will substitute in the alkyl halide; in (b) the amine and alkyl halide will undergo a substitution of amine for halogen; in (c) the inorganics form a strong oxidizing agent resulting in an elimination.

15-43 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.4:Predicting the Reactions of Alcohols, Alkyl Halides, and Amines continued SOLUTION: (a) Substitution - the products are (b) Substitution - the products are (c) Elimination - the product is

15-44 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure Some common aldehydes and ketones. methanal (formaldehyde) used to make resins in plywood, dishware, countertops; biological preservative ethanal (acetaldehyde) narcotic product of ethanol metabolism; used to make perfume, flavors, plastics, other chemicals benzaldehyde artificial almond flavoring 2-propanone (acetone) solvent for fat, rubber, plastic, varnish, lacquer; chemical feedstock 2-butanone (methyl ethyl ketone) important solvent

15-45 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The carbonyl group.

15-46 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.5: SOLUTION: Predicting the Steps in a Reaction Sequence PROBLEM:Fill in the blanks in the following reaction sequence: PLAN:Look at the functional groups and reagents to determine the type of reaction.

15-47 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure Some molecules with the carboxylic acid functional group. methanoic acid (formic acid) an irritating component of ant and bee stings butanoic acid (butyric acid) odor of rancid butter; suspected component of monkey sex attractant octadecanoic acid (stearic acid) found in animal fats; used in making candles and soap benzoic acid calorimetric standard; used in preserving food, dyeing fabric, curing tobacco

15-48 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure Some lipid molecules with the ester functional group cetyl palmitate the most common lipid in whale blubber lecithin phospholipid found in all cell membranes tristearin typical dietary fat used as an energy store in animals

15-49 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. lysergic acid diethylamide (LSD-25) a potent hallucinogen Figure Some molecules with the amide functional group. N,N-dimethylmethanamide (dimethylformamide) major organic solvent; used in production of synthetic fibers acetaminophen active ingredient in nonaspirin pain relievers; used to make dyes and photographic chemicals

15-50 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.6: SOLUTION: Predicting the Reactions of the Carboxylic Acid Family PROBLEM:Predict the product(s) of the following reactions: PLAN:(a) An acid and an alcohol undergo a condensation reaction to form an ester. (b) An amide, in the presence of base and water, is hydrolyzed.

15-51 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The formation of carboxylic, phosphoric, and sulfuric acid anhydrides

15-52 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure An ester and an amide of other nonmetals. glucose-6-phosphate sulfanilamide

15-53 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. SAMPLE PROBLEM 15.7: PROBLEM: SOLUTION: Recognizing Functional Groups Circle and name the functional groups in the following molecules: PLAN:Use Table 15.5 to identify the functional groups. carboxylic acid ester alcohol 2 0 amine ketone alkene haloalkane

15-54 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure Steps in the free-radical polymerization of ethylene.

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15-57 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The formation of nylon-66 interfacial synthesis

15-58 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The structure of glucose in aqueous solution and the formation of a disaccharide.

15-59 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The common amino acids

15-60 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The forces that maintain protein structure

15-61 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure collagen silk fibroin The shapes of fibrous proteins.

15-62 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure mononucleotide of ribonucleic acid (RNA) mononucleotide of deoxyribonucleic acid (DNA) portion of DNA polynucleotide chain Mononucleotide monomers and their linkage

15-63 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The double helix of DNA nm

15-64 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The key stages in protein synthesis.

15-65 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure The key stages of DNA replication.

15-66 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure B15.6 DNA, the genetic material. Figure B15.7 Nucleotide triphosphate monomers.

15-67 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure B15.8 Steps in the Sanger method of DNA sequencing. A. B. C. D.