Chapter 13

Alkenes, Alkynes, and Aromatic Compounds


Chapter 13 suggested problems: 23, 24, 25, 26, 27, 28, 29, 34, 36, 38, 40, 44, 48, 50, 58, 60, 84, 86, 88, 90

Interesting Links:

    Class Notes

  1. Alkenes and alkynes: general information
    1. Unsaturated hydrocarbons that contain one or more carbon-carbon double bonds
      1. Saturated hydrocarbons: every carbon atom is bonded to the maximum number of hydrogen atoms
      2. Unsaturated hydrocarbons: one or more carbon atoms is not bonded to the maximum number of hydrogen atoms due to the presence of, for example, carbon-carbon double or triple bonds
    2. General formulas and the index of hydrogen deficiency
      1. Alkenes: same as for a cycloalkanes: CnH2n
      2. Alkynes: same as for dienes CnH2n - 2
      3. General: the molecular formula provides information about the numbers and types of atoms in a compound
      4. It also provides information about the index of hydrogen deficiency, i.e., the number of pairs of hydrogen atoms the compound is missing due either to the presence of double bonds, triple bonds, and rings
        1. This index of hydrogen deficiency is also known as double bond equivalence
        2. Index = # carbons (tetravalent atoms) - (monovalent atoms/2) + (trivalent atoms/2) + 1
          1. Tetravalent atoms: C, Si
          2. Monovalent atoms: H, halogens
          3. Divalent atoms: O, S
          4. Trivalent atoms: N, P
        3. The Octet Rule must be obeyed when drawing the Lewis structures that correspond to predicted structures, i.e., every atom in the structure must have an octet regardless of any resulting formal charges
        4. Examples
          1. Hexane C6H14 I = 6 - 14/2 + 1 = 0
          2. 1-hexene C6H12 I = 6 - 12/2 + 1 = 1
          3. 1-hexyne C6H10 I = 6 - 10/2 + 1 = 2
          4. 1,3-hexadiene C6H10 I = 6 - 6/2 + 1 = 2
          5. 1,3,5-hexatriene C6H8 I = 6 - 8/2 + 1 = 3
          6. Cyclohexane C6H12 I = 6 - 12/2 + 1 = 1
          7. Cyclohexene C6H10 I = 6 - 10/2 + 1 = 2
          8. Benzene C6H6 I = 6 - 6/2 + 1 = 4
    3. Sources: most commonly obtained from the cracking of petroleum, although there are many naturally occurring and biologically important alkenes; alkynes are less common biologically
    4. Similar physical properties to those of alkanes
      1. The predominant intermolecular bonding forces are dispersion forces, as is the case with alkanes
      2. Nonpolar and insoluble in water
      3. Flammable
      4. Low toxicity
      5. Much more reactive than alkanes, pi bonds serve as the focal point for reactions
    5. Bonding in alkenes and alkynes: hybridization, sigma bonds, and pi bonds
      1. Carbon atoms that form sigma bonds use hybridized orbitals
      2. A double bond is made up of one sigma bond and one pi bond, a triple bond of one sigma bond and two pi bonds
      3. Using ethylene as an example, the four C-H bonds are formed by the overlap of the H's 1s orbital and a hybrid orbital of a carbon atom
      4. The orbitals of the remaining unhybridized p electrons overlap out of the plane of the bonding atoms to form the pi bond
      5. Pi bonds are about 50-75% as strong as sigma bonds - due to being out of plane? slightly electron repulsion?
      6. sp2 hybridization explains the 120° angles and molecular flatness observed in the carbons involved in the double bond (trigonal planar geometry)
      7. Using acetylene as an example, the two C-H bonds are formed by the overlap of the H's 1s orbital and a hybrid orbital of a carbon atom
      8. sp hybridization explains the 180° angles and molecular linearity observed in the carbons involved in the triple bond (linear geometry)
  2. Constitutional isomers of alkenes
    1. Alkenes have more possible constitutional isomers for a given number of carbon atoms than alkanes due to variations both in the backbone arrangement and in the placement of the functional group
    2. Ethene - 1 isomer
    3. Propene - 1 isomer
    4. Butene - 4 isomers: 1-butene, cis-2-butene, trans-2-butene, 2-methyl-1-propene
    5. Pentene - 6 isomers
  3. Naming alkenes and alkynes
    1. Simple alkenes and alkene side chains
      C2H4
      ethene
      CH2=CH-
      vinyl
      C3H6
      propene
      CH2=CHCH2-
      allyl
      C4H8
      1-butene
      CH2=CCH3
      isopropenyl
      C5H10
      1-pentene
      -CH2=CHCH2CH3
      butenyl 
      C6H12
      1-hexene
       
       
      C7H14
      1-heptene
       
       
      C8H16
      1-octene
       
       
      C9H18
      1-nonene
       
       
      C10H10
      1-decene
       
       
    2. Identify the longest chain
    3. Number the chain so that the position of the double bond is as low as possible
    4. Carbon-carbon double bonds take precedence over alkyl groups and halogen atoms in determining the chain length and the direction of numbering
      3-methyl-1-butene
      6-bromo-3-propyl-1-hexene
    5. Hydroxyl groups outrank the double bond
    6. Dienes and trienes - two and three C=C respectively, indicated with suffixes "adiene" or "atriene" rather than "ene"
      (3E)-hexa-1,3-diene
      (3E, 5E)-1,3,5-nonatriene
    7. Cycloalkenes - use "cyclo" prefix
      cyclohexene
      1,3,5-cycloheptatriene
  4. The structure of alkenes: cis-trans isomerism
    1. Rotation around carbon-carbon double bonds is restricted (i.e. does not occur under normal circumstances), as is also the case with rotation around rings
    2. This means that compounds with the same molecular formulas and the same groups attached to the same carbons (i.e. the same configurations) but on different sides of a double bond will have different physical and chemical properties
      cis-2-butene
      trans-2-butene
    3. Cis-tran isomerization is only possible when each of the two carbons in the double bond have two different substituents
      1. Used when the groups on either end of the double bond are the same or are structurally similar (Carey: 173)
      2. Cis - Latin: "on this side
      3. Trans - Latin: "across"
      4. Examples of compounds that are cis-tran isomers include oleic acid (cis-CH3(CH2)6CH2CH=CHCH2(CH2)6COOH) and cinnamaldehyde (trans-C6H5CH=CHCHO)
      5. Examples of compounds that are not geometric isomers
        2-methyl-1-propene
        1,1-dichloropropene
        1-chloro-2-ethyl-1-butene
        1,1-dibromo-2-chloro-2-iodoethylene
    4. Z and E are also used in lieu of cis and trans when groups of various sizes or weights are involved or when it is not obvious when substituents are similar
      1. The Z-E system is an unambiguous system based on the atomic numbers of atoms bonding to the double-bonded carbon atoms
      2. Z - zusammen: "together;" atoms or groups of highest rank (based on atomic numbers) on same side of double bond
      3. E - entgegen: "opposite;" atoms or groups of highest rank (based on atomic numbers) on opposite sides of double bond
      4. First the atomic numbers of the atoms bonding to the double-bonded carbon atoms is examined, and then the atomic numbers of the atoms bonded to those atoms is checked, and so on until a classification is determined

      5. Z-3-methyl-2-pentene
        E-3-methyl-2-pentene
        Z-1-bromo-2-chloro-1-iodoethylene
        E-1-bromo-2-chloro-1-iodoethylene
        (2Z)-3-methyl-2-propylhexyl-2-en-1-ol (2E)-3-methyl-2-propylhexyl-2-en-1-ol
  5. Addition reactions: the pi bond(s) in alkenes and alkynes results in their being much more reactive than alkanes
    1. Lewis acid-base chemistry and reactions in organic chemistry
      1. Acid-base theories
        1. Arrhenius theory
        2. Bronsted-Lowry theory
        3. Lewis theory
      2. Nucleophile - shares an electron pair with another atom to form a new covalent bond: a Lewis base
      3. Electrophile - gains an electron pair from another atom to form a new covalent bond: a Lewis acid
    2. Addition reactions - general information
      1. A reaction in which two molecules combine to yield a single product molecule; the reagent is simply added to the substrate molecule; resulting in the breaking of a pi bond and the formation of two sigma bonds
      2. Pi electrons are not held as tightly, serve as electron source (nucleophilic)
      3. Alkenes/alkynes can be attacked by electrophiles or free radicals
    3. Addition of symmetric substances (H2, halogens)
      1. Hydrogenation
        1. A hydrogen molecule is broken into hydrogen atoms which add to the carbon atoms involved in the double bond
        2. Takes place at room temperature but requires a catalyst (Pt or Ni), so the process is sometimes called catalytic hydrogenation
        3. An alkane forms as a result
        4. Ex: the addition of hydrogen to 2-butene and 1-hexene
      2. Halogenation
        1. A halogen molecule is broken into halogen atoms which add to the carbon atoms involved in the double bond
        2. Takes place at room temperature
        3. A vicinal dihalide is formed as a result
        4. Ex: the addition of hydrogen to 2-butene and 1-hexene
    4. Addition of asymmetric substances (hydrohalides, water)
      1. Markovnikov's Rule
        1. Hydrogen preferentially - but not exclusively - adds to the carbon atom with the most hydrogen atoms bonded to it
        2. This results in the formation of major (more abundant) and minor (less abundant) products
        3. Carbocation stabilization and the inductive effect: 3° > 2° > 1°
        4. Ex: the addition of HBr to ethylene and to 1-butene
      2. Hydrohalogenation
        1. A molecule is broken into a hydrogen atom and a halogen atom which add to the carbon atoms involved in the double bond
        2. An alkyl halide is formed as a result
        3. Ex: the addition of hydrogen to 2-butene and 1-hexene
      3. Hydration
        1. A water molecule is broken into a hydrogen atom and a hydroxide ion which add to the carbon atoms involved in the double bond
        2. Requires a acid catalyst
        3. An alcohol is formed as a result
        4. Ex: the addition of hydrogen to 2-butene and 1-hexene
  6. Oxidation of alkenes and alkynes
    1. Alkenes undergo combustion reactions, in which every carbon and hydrogen atom is oxidized to its highest oxidation state
      1. The concept of oxidation numbers: a brief review
      2. Oxidation of an organic compound involves forming bonds between carbon and oxygen and breaking C-C and/or C-H bonds
      3. The greater the oxidation state of the carbon the more C-O bonds exist
      4. Maximum oxidation number of carbon is +4 (CO2)
      5. All carbon atoms are completely oxidized
    2. Selective oxidation of carbon atoms involved in C-C double bonds and colorimetric functional group analysis
      1. Ozone: cleaves both the sigma and the pi bond, forming two new compounds, either aldehydes or ketones
      2. Potassium permanganate: results depend on conditions - can either add a hydroxyl group to both of the participating carbon atoms and form a vicinal diol, or it may form aldehydes or carboxylic acids: purple solution turns brown (M&B: 220f, March: 732f)
      3. Potassium dichromate: orange solution turns green, behaves similarly to permanganate solutions with respect to its effects on the double bond
  7. Alkene polymers
    1. Polymers are molecular chains
      1. The basic building blocks of polymers are monomers
      2. The monomers used to build the polymer are reflected in the name of the polymer
        1. There are hundreds of polymers, both natural and synthetic
        2. Natural: proteins, nucleic acids, rubber, cellulose, starch, etc.,
        3. Recyclable polymers
          code
          polymer resin
          description
          products
          1
          PETE: polyethylene-
          terephthalate
          usually clear or green; sinks (more dense) than water soft drink, salad dressing, and peanut butter bottles
          2
          HDPE semi-glossy, crinkly toys, liquid detergent bottles, motor oil bottles, plastic bags, milk - water - juice containers
          3
          PVC semi-rigid, glossy, sinks in water clear food wrap, blister packaging, shampoo and vegetable oil bottles
          4
          LDPE flexible, not crinkly frozen-food bags, grocery bags, shrink-wrap, bread bags, garment bags
          5
          PP semi-rigid, low gloss most bottle caps, yogurt and margarine containers, medicine containers
          6
          PS often brittle, glossy insulated cups, containers, and trays, video cassette jackets and jewel cases
          7
          other
          (multi-layer plastics)
          squeezable squeezable food delivery devices
    2. Many important monomers are alkenes, includes ethylene, propylene, styrene, tetrafluoroethylene, vinyl chloride, acrylonitrile (vinyl cyanide), and methyl methacrylate)
    3. In addition polymerizations, the monomers add one to another to form polymers that can range from dozens to thousands of monomers in size
    4. Addition polymerization requires a catalyst
    5. Addition polymerization will not take place in the presence of things that add to a double bond (hydrogen, halogens, hydrohalogens, water, sulfuric acid)
  8. Aromatic compounds
    1. Aliphatic versus aromatic hydrocarbons
    2. Benzene - the basic building block of aromatic compounds
      1. Structure results a high degree of stability, relatively low degree of reactivity
        1. 6 co-planar sp2 hybridized carbon atoms
        2. Overlap of the p orbitals results in the formation of 3 pi bonds
        3. Benzene's actual structure is a combination of resonance structures
        4. Resonance structures indicate electron delocalization, which results in stabilization of the compound
        5. Due to resonance stability, benzene is about 152 kJ/mol more stable than 1,3,5-cyclohexatriene
        6. Combustion experiments corroborate that benzene is lower in energy than similar alkenes
        7. This results in the representation of benzene rings as benzene
      2. Reactivity notes
        1. Halogens, hydrogen halides, water, and sulfuric acid do not add to the double bonds of the ring under any condition
        2. Substitution of functionalities for ring hydrogens can occur (electrophilic aromatic substitution)
  9. Isomers and names of aromatic compounds
    1. Monosubstituted benzenes
      1. Many are named by placing the substituent name in front of "benzene"
        1. Chlorobenzene, bromobenzene, iodobenzene
        2. Nitrobenzene
      2. Common names and systematic names
        1. Toluene - methylbenzene
        2. Phenol - benzenol
        3. Aniline - benzenamine
        4. Benzoic acid - benzenecarboxylic acid
        5. Styrene - vinyl benzene
        6. Anisole - methoxybenzene
        7. Benzaldehyde - benzenecarbaldehyde
    2. Disubstituted benzenes
      1. The constitutional isomers of xylene (dimethyl benzene)
        1. 1,2-xylene or o-xylene
        2. 1,3-xylene or m-xylene
        3. 1,4-xylene or p-xylene
      2. The o, m, p prefixes may be used in two circumstances
        1. When a disubstituted substance is named as a benzene derivative
          1. o-dichlorobenzene
        2. When there are two substituents and one of them is responsible for giving benzene a common name
          1. m-nitrotoluene
          2. p-chloroanisole
    3. Trisubstituted benzenes and beyond
      1. Numbers must be used for trisubstituted and beyond (substituents are named alphabetically)
        1. 2,4,6-trinitrotoluene
        2. 2,4-dichloro-1-nitrobenzene
        3. 3-ethyl-2-methylaniline
    4. Benzene as a substituent
      1. Benzene rings as substituents are called phenyl groups
        1. 2-phenylethanol
        2. 1-phenylnonane
        3. 1-phenyl-2-propanone
    5. Chlorinated aromatic compounds
      1. Commonly found in a wide variety of products
      2. 2,4-D and 2,4,5-T; 2,4-D is 3rd most widely used herbicide in world; over 1500 products contain it (Wikipedia); Agent Orange
        2,4-D 2,4,5-T
      3. Two phenyl groups joined by a sigma bond are called biphenyl
      4. Polychlorinated biphenyls: 209 congeners (structurally related compounds), used as insulating oils, etc.
        pcb-decachlorobiphenyl
        1. See "The Chemistry of Polychlorinated Biphenyls: PCB, The Manmade Chemicals That Won't Go Away" at http://environmentalchemistry.com/yogi/chemistry/pcb.html
        2. See "Polychlorinated Biphenyls (PCBs): Uses and Environmental Releases" at http://www.chem.unep.ch/pops/POPs_Inc/proceedings/bangkok/FIEDLER1.html
      5. Polybrominated diphenyl ethers: 209 congeners, used in flame retardants, etc; questions about toxicity and bioaccumulation in breast milk, fatty tissues, etc.
        PDBE
      6. Hexachlorophene: antibacterial
        hexachlorophene
      7. DDT: insecticide
        DDT
      8. Dioxins: 210 related compounds, 75 polychlorinated dibenzodioxins (PCDD) and 135 polychlorinated dibenzofurans (PCDF); acutely toxic, carcinogenic, teratogenic, bioaccumulative
        PCDFPCDD
        1. Times Beach, MO; Love Canal, NY; Seveso, IT
        2. "Dioxin" at http://en.wikipedia.org/wiki/Dioxin
        3. "the number and position of the chlorine atoms determine the toxicity of the PCDD, and the most toxic among them is 2,3,7,8-tetrachlorodibenzo-p-dioxin (commonly referred to as "dioxin").

          "In humans and other vertebrates dioxins have been shown to be risk factors for cancer; immune deficiency; reproductive and developmental abnormalities; central nervous system and peripheral nervous system pathology; endocrine disruption, including [diabetes] and thyroid disorders; decreased pulmonary functions and bronchitis; altered serum testosterone level; eyelid pathology, including meibomian gland hypersecretion and hyperpigmented conjunctivae; gum pigmentation; nausea; vomiting; loss of appetite; skin rashes, including, rarely, chloracne or acne caused by chlorine-containing organic chemicals; hypertrichosis; liver damage; elevated serum cholesterol and triglycerides; and enamel hypomineralization of permanent first molars in children. An increased risk of mortality was associated with high levels of occupational exposure to dioxins with acute ischemic cardiovascular events. Transient acute health effects including headache, pruritus, fatigue, irritability, inability to have erections or ejaculations, personality changes, pain in the abdomen or extremities, diarrhea, and insomnia have been reported, especially following industrial exposures." ("Seveso disaster." Wikipedia, The Free Encyclopedia. 24 Apr 2007, 02:23 UTC. Wikimedia Foundation, Inc. 5 May 2007)

    6. Polyaromatic hydrocarbons
      1. Two or more fused benzene rings are called polyaromatic hydrocarbons
        1. Naphthalenenaphthalene
        2. Anthraceneanthracene
        3. Phenanthrene phenanthrene
        4. Chrysenechrysene
        5. 1,2-benzanthracene1,2-benzanthracene
        6. Benzo[a]pyrene (BAP)benzo[a]pyrene
        7. Chrysene, 1,2-benzanthracene, and benzo[a]pyrene are carcinogens
  10. Reactions of aromatic compounds
    1. Electrophilic aromatic substitution - the replacement of a ring hydrogen by another substituent often require a metal halide or sulfuric acid as a catalyst
      1. Halogenationthe halogenation of benzene
      2. Alkylationthe alkylation of benzene
      3. Nitrationthe nitration of benzene
      4. Sulfonationthe sulfonation of benzene
    2. Oxidation
      1. Alkylbenzenes undergo oxidation under moderately strong oxidizing conditions, such as hot potassium permanganate or potassium dichromate
      2. The benzene ring is untouched while the aliphatic moiety is oxidized completely to carbon dioxide and water
      3. The carbon attached to the ring is oxidized to a carboxylic acid
    3. Combustion - aromatics do undergo complete oxidation in combustion reactions, but need a good oxygen source for complete combustion

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