An Introduction to Organic Chemistry

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An Introduction to Organic Chemistry
Dr. Pete Wilson Department of Chemistry Simon
Fraser University
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The Periodic Table of the Elements

• The Building Blocks of Matter

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CARBON - Diamond, Graphite and Soot
Diamond
Graphite
Buckminsterfullerene ( C60 )
The Allotropes of Elemental Carbon
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ORGANIC CHEMISTRY (Carbon-based Molecules)
Methane Oxygen
Carbon dioxide Water
Octane ( C8H18 )
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The Organic Chemistry of Life - DNA
The Double Helix of DNA Side (left) and top view
(right)
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The Glue That Holds It Altogether - Base Pairs
Single strand DNA
A-T base pair
Base pairs in DNA double helix
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The Organic Chemistry of Life - PROTEINS
a - Amino acids
Tryptophan
Proteins
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Enzymes, Receptors and Structural Proteins
Triose phosphate isomerase ( ribbon model of an
enzyme )
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Pharmaceuticals (Top Three in 1997)
Omeprazol Simvastatin
Fluoxetin
Losec (Astra) Zocor (Merck Co)
Prozac (Lilly)
3.8 billion 2.8 billion 2.4 billion
Stomach ulcers Hypercholesterolemia
Depression
Drug Development 8-15 years, 300-500 million
(1 drug per 10,000 substances)
H.-J. Quadbeck-Seeger (Ed.), R. Faust, G. Knaus,
U. Siemeling (translated by W. E. Russey) World
Records in Chemistry Wiley-VCH, 1999, pp. 199
and 207
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Cancer Chemotherapy
Taxol
10-Deacetylbaccatin III
Source Taxus brevifolia (Pacific Yew tree )
extracted from the bark
Source Taxus baccata (European Yew tree )
extracted from the needles and twigs
Total Syntheses K. C. Nicolaou, E. J.
Sorensen Classics in Total Synthesis VCH,
Weinheim, 1996, pp. 655-672 and references cited
therein
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HIV and AIDS
Azidothymidine (AZT)
Lamivudine (3TC)
Glaxo Wellcome Inc.
BioChem Pharma ( Montréal ) Glaxo Wellcome Inc.

Anti-retroviral agents Effective against
HIV-1, the causative agent of AIDS
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VIAGRA
Sildenafil citrate (Viagra)
Selective inhibitor of cyclic guanosine
monophosphate (cGMP)-specific phosphodiesterase
type 5 (PDE5) smooth muscle relaxant
http//www.pfizer.com
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A Balanced Diet - Vitamins
Vitamins A, E and C
Pigment (Vision)
Anti-oxidant (Aging) Stimulates
Immune System
(prevents
scurvy)
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Some Like it Hot !
Capsaicin
Resiniferatoxin
10,000 x hotter !
Source Chili peppers
Source Euphorbia poisonii (plant)
C. S. J. Walpole et al. J. Med. Chem. 1993, 36,
2362 A. Szallasi, P. M. Blumberg Neuroscience
1989, 30, 515
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For Those with a Sweet Tooth ...
Sucrose Saccharin
Sucronic acid
300 x sweeter
200,000 x sweeter !
T. H. Grenby in Advances in Sweeteners,
Blackie, London, 1991
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Something for the Palette ...
1-p-menthen-8-thiol
Wine lactone
Lowest Taste Threshold 2 x 10-5 ppb in water(2
mg in 100,000-ton tanker)
Lowest Aroma Threshold 1 x 10-14 g L-1 in
air(coconut, sweet, slightly woody)
Source Grapefruit
Source Wine
E. Demole et al. Helv. Chim. Acta 1982, 65,
1785 and H. Guth ibid. 1996, 79, 1559
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Sending a Message and Making Your Mark
Methyl-4-methyl pyrrole-2-carboxylate
Dimethyldisulfide
Source Atta texana (ant)
pheromone
Source Female hamsters pheromone
2 ng turns on a male hamster
3 ng per day to mark track 1 mg would go 3 x
around the Earth !
A. G. Singer et al. Science 1976, 191, 948 B.
Hölldobler, E. O. Wilson The Ants, Springer,
Heidelberg, 1990, pp. 246
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Was that you?
Allicin
Sulfur-containing compounds
Source Allium sativum (garlic)
Source Mephitis mephitis (skunk)
R. Rawls Chem. Eng. News September 23, 1996,
pp. 53-60 K. K. Andersen, D. T. Bernstein J.
Chem. Ecol. 1975, 1, 493
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Poisonous Molecules
Strychnine LD50 750 mg Kg-1 (cat)
Dioxin LD50 22 mg Kg-1 (rat)
Source Strychnos nux-vomica (nut)
Source Synthetic
Total Synthesis R. B. Woodward et al. J.
Am. Chem. Soc. 1954, 76, 4749
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Most Toxic Low Molecular Weight Toxins
Botulinum toxin - Source Clostridium botulinum
(bacterium) Protein (bio-polymer)
Molecular Weight 150,000 g mol-1 LD50
0.0003 mg Kg-1 (mouse)
Batrachotoxin (MW 539) LD50 2 mg Kg-1 (mouse)
Tetrodotoxin (MW 319) LD50 10 mg Kg-1 (mouse)
Source Colombian arrow-poison frog
Source Fuga pufferfish
T. Tokuyama et al. J. Am. Chem. Soc. 1969, 91,
3931 C. Y. Kao, F. A. Fuhrmann J. Pharmacol.
Exp. Ther. 1963, 140, 31
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The Most Toxic and Complex Natural Product
and the waters that were in the river were
turned to blood. And the fish that were in the
river died and the river stank and the Egyptians
could not drink of the water of the river
Exodus 720-21
Maitotoxin LD50 0.050 mg Kg-1 (mouse)
Source dinoflagellum Gambierdiscus toxicus
(phytoplankton - red tides)
M. Murata et al. J. Am. Chem. Soc. 1994, 116,
7098
22
Most Complex Natural Product Synthesized
Palytoxin LD50 0.45 mg Kg-1 (mouse)
64 stereocentres ( 264 1.8 x 1019
stereoisomers ! )
Source Palythoa toxica (coral species)
E. M. Suh, Y. Kishi J. Am. Chem. Soc. 1994,
116, 11205 and references cited therein
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Explosives and Rocket Propellants
TNT RDX CL20
For CL20, the shock wave travels at 21,000 mph !
c.f. Sound in air (675 mph)
H.-J. Quadbeck-Seeger (Ed.), R. Faust, G. Knaus,
U. Siemeling (translated by W. E. Russey) World
Records in Chemistry Wiley-VCH, 1999, pp. 151-153
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Molecules of Theoretical Interest
Cubane ( C8H8 )
Octanitrocubane
( C8N8O16 ? 8 x CO2 4
x N2 BOOM ! )
P. E. Eaton, T. W. Cole, Jr. J. Am. Chem. Soc.
1964, 86, 962 The New York Times January 25,
2000
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Dodecahedrane (The Organic Chemists Dodecahedron)
Dodecahedrane ( C20H20 )
Systematic Chemical Name Undecacyclo9.9.9.02,
9.03,7.04,20.03,15.06,16.08,15.010,14.012,19.013,1
7eicosane
L. A. Paquette Chem. Rev. 1989, 89, 1051
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Organic Crystals
Adamantane-tetra-carboxylic acid
Hydrogen-bonded diamond-like lattice
Benzoic acid Hydrogen-bonded dimer
O. Ermer J. Am. Chem. Soc. 1988, 110, 3747
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2 x Triquinacene ? Dodecahedrane ?
2 x C10H10 ? C20H20 ?
Triquinacene ( C10H10 )
P. D. Wilson, J. A. Cadieux unpublished results