Page 1
Chemistry 506 Dr. Hunter’s Class Chapter 11.1
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Chemistry 506: Allied Health Chemistry 2
Chapter 11: Alkenes, Alkynes, and Aromatic Compounds
Hydrocarbons with Multiple Bonds
Introduction to General, Organic & Biochemistry, 5th Edition byBettelheim and March: Chapter 11, Pages 353-390
Outline Notes by Dr. Allen D. Hunter, YSU Department ofChemistry, 2000.
Outline
11A SECTION(S) 11.1/2/4 INTRODUCTION AND NOMENCLATURE OF ALKENES ...................................................... 2
11B SECTION(S) 11.3 ππ -BONDS ................................................................................................................................................... 4
11C SECTION(S) 11.5 PHYSICAL PROPERTIES ..................................................................................................................... 5
11D SECTION(S) 11.6 CHEMICAL PROPERTIES: ADDITION REACTIONS................................................................... 6
11E SECTION(S) 11.7 ADDITION POLYMERS ........................................................................................................................ 8
11F SECTION(S) 11.8 ALKYNES ............................................................................................................................................... 13
11G SECTION(S)11.9/10 AROMATIC HYDROCARBONS ................................................................................................... 17
11H SECTION(S)18.2 AMINO ACIDS HAVING SIMPLE AROMATIC SIDE CHAINS .................................................. 22
11I SECTION(S) 11.11 AROMATIC REACTIONS ................................................................................................................. 23
11J SECTION(S) 11.12 FUSED RING AROMATICS .............................................................................................................. 25
11K SECTION(S)11.13 HETEROCYCLICS (NOT COVERED IN DETAIL)....................................................................... 26
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Chemistry 506 Dr. Hunter’s Class Chapter 11.2
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11A Section(s) 11.1/2/4 Introduction and Nomenclature of Alkenes
Ø Ethene = (Ethylene), CH2=CH2
Ø IUPAC Rules
Ø Start numbering from the end that gives the double bond the
lowest number.
Ø Indicate position of double bond(s) by numbers.
Ø Use the ene ending
Ø Indicated number of double bonds by prefixes (ene, diene,
triene, tetraene, etc.)
Ø Examples
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Chemistry 506 Dr. Hunter’s Class Chapter 11.3
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Geometric Isomers
Ø No free rotation (π-bonds)
Ø Experimental observations
Ø cis isomers vs. trans isomers
Ø Examples
Page 4
Chemistry 506 Dr. Hunter’s Class Chapter 11.4
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11B Section(s) 11.3 π-Bonds
Ø Bonding: sp2 hybridization for 3 σ-bonds to the three atoms
bonded to each carbon
Ø pz orbital for π-bond
Ø Typical C=C bond distance (i.e., 1.34
Å) shorter than C-C bond distance (i.e., 1.54 Å)
Ø slightly shorter C-H distance than alkanes
Page 5
Chemistry 506 Dr. Hunter’s Class Chapter 11.5
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11C Section(s) 11.5 Physical Properties
Ø Almost identical to Alkanes of same MW
Ø Van der Waals forces
Ø Slightly higher Mp and Bp
Ø Smell (turpentine like)
Ø Density
Ø Solubility
Page 6
Chemistry 506 Dr. Hunter’s Class Chapter 11.6
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11D Section(s) 11.6 Chemical Properties: Addition Reactions
Ø Addition reaction (generic)
Ø π-bonds weaker than σ-bonds
Ø Hydrogenation: Addition of H2 or D2 (Pt catalyst)
Ø Addition of Cl2 or Br2 (X2)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.7
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Addition of HX ((HF) HCl, HBr (HI))
Ø Halide Influences
Ø Markovnikov Addition
Ø Addition of Water (Hydration)
Ø H+ Catalyst
Ø Markovnikov
Page 8
Chemistry 506 Dr. Hunter’s Class Chapter 11.8
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11E Section(s) 11.7 Addition Polymers
Ø Definition of Addition Polymers
Ø No loss of mass
Ø Rapid chain growth
Ø π-bond opening
Ø “Generic” Synthesis Reaction
Ø typical monomers are CH2=CH-R
Ø Role of Catalysts
Ø Speed reaction but aren’t themselves consumed
Ø Highly reactive species
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Chemistry 506 Dr. Hunter’s Class Chapter 11.9
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Reversibility of Reactions
Ø Polymerization under low temperatures/high pressures
Ø i.e., monomer (liquids or gasses) -> polymer (solids)
Ø Depolymerizations (unraveling) at high temperatures
Ø i.e., polymer -> monomer
Ø Molecular Weights and Molecular Weight Distributions
Ø High average Molecular Weights
Ø Distributions rather than discrete weights
Ø Linear Chains vs. Branched Chains
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Chemistry 506 Dr. Hunter’s Class Chapter 11.10
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Examples
Ø Polyethylene, PE, Synthesis
Ø CH2=CH2, R = H
Ø Poly(vinyl chloride), PVC, Synthesis
Ø CH2=CH-Cl, R = Cl
Page 11
Chemistry 506 Dr. Hunter’s Class Chapter 11.11
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Polypropylene, PP, Synthesis
Ø CH2=CH-CH3, R = CH3
Ø Polystyrene, PS, Synthesis
Ø CH2=CH-C6H5, R = C6H5
Ø Poly(methyl methacrylate), PMMA, Synthesis
Ø CH2=C(CH3)(CO2CH3)
Page 12
Chemistry 506 Dr. Hunter’s Class Chapter 11.12
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Teflon Synthesis
Ø CF2=CF2
Ø Rubber (Polyisoprene) Synthesis
Ø CH2=CH-CH=CH2
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Chemistry 506 Dr. Hunter’s Class Chapter 11.13
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11F Section(s) 11.8 Alkynes
Ø Carbon-Carbon Triple Bonds
Ø sp hybridized
Ø Very Short C≡C Bond distance (i.e., 1.20 Å ), much shorter
than the C=C distance (i.e., 1.34 Å) and the C-C distance
(i.e., 1.20 Å)
Ø Bonding: 1 σ-bond and 2 π-bonds (px and py)
Ø slightly shorter C-H distance than alkanes or even alkanes
Ø Ethyne = Acetylene, H-C≡C-H
Ø Physical Properties
Ø Almost identical to Alkanes/Alkenes of same MW
Ø Van der Waals forces
Ø Slightly higher Mp and Bp
Ø Density
Ø Solubility
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Chemistry 506 Dr. Hunter’s Class Chapter 11.14
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Nomenclature
Ø yne ending
Ø yne > ene in priority of naming
Ø Examples
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Chemistry 506 Dr. Hunter’s Class Chapter 11.15
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Alkyne Reactions
Ø Generic Reaction
Ø Very like Alkenes
Ø Normally Double Addition
Ø Hydrogenation: Addition of H2 or D2 (Pt catalyst)
Ø Addition of X2 (Cl2 or Br2)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.16
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Addition of HX (most commonly HCl and HBr)
Ø Markovnikov Addition
Ø Addition of H2O (H+ catalyst)
Ø Markovnikov Addition
Ø Secondary elimination of water from diol
Ø gives carbonyl group (aldehyde or ketone)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.17
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11G Section(s) 11.9/10 Aromatic Hydrocarbons
Ø Sources
Ø Coal Tar
Ø Coke production
Ø Direct separation
Ø Start of industrial chemistry
Ø Petroleum
Ø multiple processing steps
Ø Uses
Ø Octane enhancers in gasoline
Ø Plastics
Ø Pigments/Dyes
Ø Pharmaceuticals
Ø Aromatic: Properties, Reactivity, C/H Ratios (cf.
Alkane/Alkenes/Alkynes)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.18
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Substitution Reactions not Addition Reactions (i.e., not like
alkenes)
Ø Bonding / Resonance Stabilization
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Chemistry 506 Dr. Hunter’s Class Chapter 11.19
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Nomenclature
Ø IUPAC Names
Ø Halobenzenes (X = F, Cl, Br, I)
Ø Nitrobenzene (Z = NO2)
Ø Alkylbenzenes (phenylalkanes)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.20
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Common Names (IUPAC)
Ø Phenol (Z = OH)
Ø Aniline (Z = NH2)
Ø Toluene (Z = CH3, methylbenzene)
Ø Benzoic Acid (Z = CO2H)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.21
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Multiply Substituted Arenes
Ø Numbering Ring Positions
Ø Ortho, Meta, Para, Ipso
Ø As Side Chains (phenyl groups)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.22
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11H Section(s) 18.2 Amino Acids having Simple Aromatic Side
Chains
Ø Generic AA = H2N-CHR-CO2H
Ø Phenyl Alanine (non-polar)
Ø R = CH2C6H5
Ø PKU
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Chemistry 506 Dr. Hunter’s Class Chapter 11.23
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11I Section(s) 11.11 Aromatic Reactions
Ø Substitution Reactions
Ø Require catalyst
Ø "Generic"
Ø Z+ Electrophiles
Ø Nitration (Z = NO2, HNO3/H2SO4, TNT)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.24
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Ø Sulfonation (Z = SO3H, H2SO4/SO3)
Ø Halogenation (X = Cl or Br, Cl2/Fe or Br2/Fe)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.25
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11J Section(s) 11.12 Fused Ring Aromatics
Ø Polycyclic Aromatic Hydrocarbons, PAHs
Ø Toxicity
Ø Naphthalene (C10H8)
Ø Anthracene (C14H10)
Ø Phenanthrene (C14H10)
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Chemistry 506 Dr. Hunter’s Class Chapter 11.26
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
11K Section(s) 11.13 Heterocyclics (Not covered in detail)
Ø Replace C-H by Heteroatom Groups such as: N, O, S, etc.
Ø Important in Biomolecules
Ø Pyridine (C5H5N)
Problems: All up to 11.50
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Chemistry 506 Dr. Hunter’s Class Chapter 11.27
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Index of Topics and Vocabulary
1
1.20 Å................................................................................ 13
1.34 Å............................................................................ 4, 13
1.54 Å 4
A
Acetylene .......................................................................... 13Addition ............................................................................ 15Addition of HX................................................................... 7Addition of Water ............................................................... 7Addition Polymers.............................................................. 8Addition reaction................................................................. 6Addition Reactions............................................................ 18aldehyde ............................................................................ 16alkanes ................................................................................. 4alkenes ............................................................................... 18Alkenes.............................................................................. 15Alkylbenzenes................................................................... 19Alkyne Reactions.............................................................. 15Alkynes ............................................................................. 13Amino Acids having Simple Aromatic Side Chains......... 22Aniline............................................................................... 20Anthracene ........................................................................ 25Arenes ............................................................................... 21Aromatic............................................................................ 17Aromatic Hydrocarbons.................................................... 17Aromatic Reactions........................................................... 23
B
Benzoic Acid..................................................................... 20Biomolecules ..................................................................... 26Bonding................................................................... 4, 13, 18Bp ................................................................................. 5, 13Br2 ................................................................................. 6, 15Br2/Fe................................................................................ 24Branched Chains ................................................................. 9
C
C≡C Bond distance ........................................................... 13C/H Ratios......................................................................... 17C=C bond distance.............................................................. 4C=C distance..................................................................... 13C10H8 ................................................................................. 25C14H10................................................................................ 25C5H5N ............................................................................... 26Carbon-Carbon Triple Bonds............................................ 13carbonyl group .................................................................. 16catalyst .............................................................................. 23Catalysts.............................................................................. 8C-C distance...................................................................... 13CF2=CF2............................................................................ 12C-H distance.................................................................. 4, 13CH2=C(CH3)(CO2CH3)..................................................... 11CH2=CH2 ...................................................................... 2, 10
CH2=CH-C6H5 .................................................................. 11CH2=CH-CH=CH2............................................................ 12CH2=CH-CH3 ................................................................... 11CH2=CH-Cl....................................................................... 10CH2=CH-R.......................................................................... 8chain growth........................................................................ 8Chemical Properties: Addition Reactions.......................... 6cis isomers........................................................................... 3Cl2 ................................................................................. 6, 15Cl2/Fe................................................................................. 24Coal Tar............................................................................. 17Coke .................................................................................. 17Common Names ................................................................ 20
D
D2 ................................................................................. 6, 15Density .......................................................................... 5, 13Depolymerizations.............................................................. 9diene .................................................................................... 2diol..................................................................................... 16Double Addition................................................................ 15Dyes .................................................................................. 17
E
Electrophiles...................................................................... 23ene ................................................................................. 2, 14ene ending............................................................................ 2Ethene.................................................................................. 2Ethylene .............................................................................. 2Ethyne............................................................................... 13
F
free rotation......................................................................... 3Fused Ring Aromatics ....................................................... 25
G
gasoline.............................................................................. 17Geometric Isomers .............................................................. 3
H
H+ catalyst......................................................................... 16H+ Catalyst.......................................................................... 7H2 ................................................................................. 6, 15H2O ................................................................................... 16H2SO4/SO3......................................................................... 24Halide Influences................................................................. 7Halobenzenes .................................................................... 19Halogenation ..................................................................... 24HBr................................................................................ 7, 16H-C≡C-H .......................................................................... 13HCl................................................................................ 7, 16Heteroatom Groups........................................................... 26Heterocyclics..................................................................... 26HF ....................................................................................... 7HI ....................................................................................... 7HNO3/H2SO4..................................................................... 23HX................................................................................. 7, 16
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Chemistry 506 Dr. Hunter’s Class Chapter 11.28
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University
Hydration ............................................................................ 7Hydrogenation............................................................... 6, 15
I
industrial chemistry .......................................................... 17Ipso ................................................................................... 21IUPAC Names .................................................................. 19IUPAC Rules ...................................................................... 2
K
ketone................................................................................ 16
L
Linear Chains ...................................................................... 9
M
Markovnikov....................................................................... 7Markovnikov Addition ................................................. 7, 16Meta .................................................................................. 21methylbenzene .................................................................. 20Molecular Weight Distributions ......................................... 9Molecular Weights.............................................................. 9monomer.............................................................................. 9monomers............................................................................ 8Mp................................................................................. 5, 13
N
Naphthalene....................................................................... 25Nitration............................................................................ 23Nitrobenzene..................................................................... 19Nomenclature .............................................................. 14, 19
O
Octane ............................................................................... 17Ortho................................................................................. 21
P
PAH .................................................................................. 25Para.................................................................................... 21PE ..................................................................................... 10Petroleum .......................................................................... 17Pharmaceuticals................................................................. 17Phenanthrene..................................................................... 25Phenol................................................................................ 20Phenyl Alanine.................................................................. 22phenyl groups.................................................................... 21phenylalkanes .................................................................... 19Physical Properties........................................................ 5, 13Pigments............................................................................ 17PKU .................................................................................. 22Plastics .............................................................................. 17PMMA.............................................................................. 11Poly(methyl methacrylate)................................................ 11Poly(vinyl chloride)........................................................... 10Polycyclic Aromatic Hydrocarbons.................................. 25Polyethylene...................................................................... 10Polyisoprene...................................................................... 12Polymerization.................................................................... 9Polymers ............................................................................. 8Polypropylene ................................................................... 10Polystyrene........................................................................ 11PP ..................................................................................... 10
Problems............................................................................ 26Properties .......................................................................... 17PS ..................................................................................... 11Pt catalyst...................................................................... 6, 15PVC ................................................................................... 10px ..................................................................................... 13py ..................................................................................... 13Pyridine............................................................................. 26pz ....................................................................................... 4
R
Resonance Stabilization .................................................... 18Reversibility of Reactions................................................... 9Ring Positions ................................................................... 21Rubber............................................................................... 12
S
Secondary elimination of water ........................................ 16Smell.................................................................................... 5Solubility....................................................................... 5, 13sp hybridized..................................................................... 13sp2 hybridization ................................................................. 4Substitution Reactions ................................................ 18, 23Sulfonation ........................................................................ 24
T
Teflon................................................................................ 12tetraene................................................................................ 2TNT................................................................................... 23Toluene.............................................................................. 20trans isomers ....................................................................... 3triene.................................................................................... 2
V
Van der Waals forces .................................................... 5, 13
X
X2 ................................................................................. 6, 15
Y
yne ending......................................................................... 14
Z
Z+ ..................................................................................... 23
C-CC-C
C-C bond distance ............................................................... 4
ππ
π-bond ................................................................................. 4π-bond opening.................................................................... 8π-bonds.......................................................................... 3, 13π-Bonds............................................................................... 4π-bonds weaker than σ-bonds............................................. 6
σσ
σ-bond ............................................................................... 13σ-bonds................................................................................ 4
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Chemistry 506 Dr. Hunter’s Class Chapter 11.29
2000, Dr. Allen D. Hunter, Department of Chemistry, Youngstown State University