Organic Chemistry I - SUNY Morrisville

CHEM 241Organic Chemistry I11:00 – 11:50 am M W F350 Crawford Hall

INSTRUCTOR BIODR. ARTHUR HABER Bristol Myers Frederick Cancer Research Center University of Michigan at Ann-Arbor University of Illinois at Urbana-Champaign Polytechnic Institute of Brooklyn Brooklyn Technical High School Jr. High School 234 P.S. 206 Who’s Who Among American Teachers2006, 2000, 1996

INSTRUCTOR BIOcont’dDR. ARTHUR HABER Father of a SUNY undergrad Yankees fan Socially inept and judgmental, not apeople person Wears the same three golf shirts inrotation all summer long Enjoys being called La Grande Fromage Thinks Glass Plus is better than Windex Would rather be in Florida Loves strong artificial fragrances Has a hording problem Pedagogically sarcastic and cynical

Handouts Tentative Outline And Calendar Useful Information A 60-Second Course in Organic Chemistry Common Functional Groups The Organic Metropolis Other Handouts Available athttp://people.morrisville.edu/ habera/

ORGANICCHEMISTRY10/eFrancis A. CareyRobert M. GiulianoMcGraw Hill2017TEXTBOOK

ORGANICCHEMISTRY9/eFrancis A. CareyRobert M. GiulianoMcGraw Hill2013TEXTBOOK

ORGANIC CHEMISTRYEIGHTH EDITIONF. A. CareyandR. M. GiulianoMcGraw-HillNew York2011TEXTBOOK

ORGANIC CHEMISTRYSEVENTH EDITIONF. A. CareyMcGraw-HillNew York2008TEXTBOOK

HTTP://MOLECULARVISIONS.COM/MOLECULAR MODELS

PHILOSOPHY

YOUR HIGH SCHOOL EDUCATIONMay have been poor preparation forstudying organic chemistry

While general chemistry is a survey ofstoichiometry, physical chemistry, and somedescriptive chemistry, each chapter canusually stand on its own and the order ofpresentation is almost irrelevant.This is not so in organic chemistry.Each chapter in an organic text builds uponwhat came before and the order ofpresentationisthemainfeaturedistinguishing one text from another.

ADVICE FROM YODA Do or do not, there is no try.

THE ORGANIC METROPOLIS Infrastructure Language General Personalities Specific Personalities

THE ORGANIC METROPOLISInfrastructure atomic structure periodic properties hybridized orbitals valence bond orbitals molecular orbitals bond energies (homolytic/heterolytic) thermodynamics kinetics Hammond-Leffler Principle flow of electrons (from electron rich sites to electron poor sites) Frontier Molecular Orbital theory stereochemistry

THE ORGANIC METROPOLISLanguage verbal graphic spectroscopic Lewis StructuresGeneral Personalities oxidizing agent/reducing agent acid/base electrophile/nucleophile carbocation carbon radical carbanion carbene excited state carbon

THE ORGANIC METROPOLISSpecific Personalities functional group approach nomenclature structure physical properties synthesis reactions spectroscopic properties simple chemical tests

ORGANIC CHEMISTRY: A NEW WAY OF THINKING2, , , 8, , 12, , , , 201, , 2, , , 8, , 214, , 23, 34, , , 50, , 72, 81, , , 103, , , 125, 135

SUCCESS IN ORGO COMES FROM WORKINGPROBLEMS

THE GREATEST AMERICANPHILOSOPHER OF EDUCATION

YOGI BERRAWhen you come to afork in the road,

YOGI BERRAWhen you come to afork in the road,take it.

NIKE

NIKEJust do it!

THE EQUALIZERProgress, not perfection.Robert McCall

OTHER COMMENTS There will be no teaching to an exam Learning must be thematic Must read the textbook Solve problems (reading is just not enough) Work hard See Tentative Outline

There will be an assignment for each chapter; an exam afterthree or four chapters.GRADE CALCULATION

urse Grade80 (0.40)(64) (0.60)(80) 73.6% 809075245% 256 102 64400% 245 102 82300888 102 741200 (0.40)(74) (0.60)(82) 78.8

GRADING SCHEMEAAB BBC CCD %65-63%62-60% 60%

History and Definition Compounds originating in living organisms Vital Force Doctrine (Vitalism) 1828 Friedrich WöhlerNH4OCNammonium cyanateinorganic“mineral world”H2NC( O)NH2ureaorganic“living world” ORGANIC CHEMISTRYThe chemistry of carbon containing compounds (except those traditionallybelonging to the mineral world – CO3-2, CN-1, C2-2, OCN-1, etc

BUT

WHAT ABOUT THESE COMPOUNDS? foscarnet, an antiviral agent tetrakis triphenylphosphinepalladium, [(C6H5)3P]4Pd

The answer is that we don’t knowand we don’t care. It is importantthese days to realize that strictboundaries between traditionaldisciplines are undesirable andmeaningless.Organic ChemistryJ. Clayden, N. Greeves, S. Warren, and P. WothersOxford University Press, Inc.2001

Uniqueness of Carbon and General Chemistry PrerequisitesINTRODUCTION

CARBONThere must be something unique aboutcarbon for there to be a whole fielddedicated to its chemistry.

Uniqueness of Carbon Forms strong, short covalent bonds with a wide variety of elements (metalsand non-metals) Bonds to itself extensively in straight chains, branched chains, rings, andendless combinations Carbon readily changes hybridization: sp, sp2, sp3, even sp3d in transitionstates Carbon makes use of a wide range of oxidation numbers:CH4, -4 CO2, 4 and all values between Approximately 12 x 106 synthetic and naturally occurring organic compoundsare documented; the number of such inorganic compounds is much less Extensive system of isomers – different compounds having the samemolecular formula Functional Group Perspective – specific combinations of atoms reacting in acharacteristic way, no matter what the molecular occurrence.

CONSTITUTIONAL ISOMERS C2H6O Ethanol versus Dimethyl Ether

CONSTITUTIONAL ISOMERS 4 Carbons, 1 Oxygen,and the necessary H’s

MOLECULAR MODELSWire FrameBall and StickSpace FillingElectron Density

PRE-REQUISITES TO THE STUDY OF “ORGO” Quantum MechanicsIonic Compounds/Ionic BondsMolecular Compounds/Covalent BondsLewis StructuresValence Bond TheoryMolecular Orbital TheoryIsomersRepresenting Organic MoleculesNon-Bonding Interactions/Intermolecular ForcesFunctional Groups

QUANTUM MECHANICS atomic orbitals electron configuration order of orbital filling and the periodic table quantum number, Pauli Principle, Hund’s Rule periodic propertiesatomic sizeionization energyelectron affinityelectronegativityvalence electrons

IONIC COMPOUNDS/IONIC BONDS metal – nonmetal metal – polyatomic ion aqueous solutions conduct electricity conduct electricity as liquids

MOLECULAR COMPOUNDS/COVALENT BONDS nonmetal – nonmetal non-polar bonds polar bonds electronegativity difference aqueous solutions of polar molecular compounds may conduct electricity

LEWIS STRUCTURES octet rule and exceptions multiple bonds formal charge resonance VSEPR Theory – shapes of molecules molecular dipole moments – polar and non-polar molecules

VSEPR THEORY

Symmetry: A UnifyingConceptI. Hargittai and M. HargittaiShelter Publications, Inc.1994

VALENCE BOND THEORY -C--C -C C tetrahedraltrigonal planarlinearlinearsp3sp2spsps bondingp bondings bonding -O-O -C sp3sp2sp-Nsp3 -C sp-N -C -C sp2spsp

BOND FORMATION

MOLECULAR ORBITAL THEORY bonding orbitals non-bonding orbitals anti-bonding orbitals bond order delocalization/resonance s/p orbitals Frontier Molecular Orbitals (FMO)

ISOMERSConstitutional Isomers, e.g., C2H6O Stereoisomers

REPRESENTING ORGANIC MOLECULES models(wire frame, ball and stick, space filling, electrondensity) formula full Lewis structure condensed Lewis structure bond-line formula

C3H8O orC3H7OH

NON-BONDING INTERACTIONS/INTERMOLECULAR FORCES Ion-dipole dipole-dipole* H-Bond* ion-induced dipole dipole-induced dipole* dispersion (London)*40 – 600 kJ/mol5 - 2510 - 403 - 152 - 100.05 - 40*collectively known as van der Waals forces

Electron Flow in OrganicChemistryP. H. ScudderJohn Wiley & Sons1992FUNCTIONAL GROUPS

CHALLENGES

( )-PROGESTERONE

(-)-TAXOL

MOLECULAR MOTORS

The Nobel Prize in Chemistry 2016 was awarded jointly toJean-Pierre Sauvage,Sir J. Fraser StoddartBernard L. Feringa"for the design and synthesis of molecular machines".THE 2016 NOBEL PRIZE IN CHEMISTRY

OTHER IMPORTANT APPLICATIONS OFORGANIC CHEMISTRY

HYDROCARBONS

MAJOR COMPONENT OF THE TEXTILE INDUSTRY

(ORGANIC) CHEM TIME

THE END

ORGANIC CHEMISTRY 10/e Francis A. Carey Robert M. Giuliano McGraw Hill 2017. TEXTBOOK ORGANIC CHEMISTRY 9/e Francis A. Carey Robert M. Giuliano McGraw Hill 2013. TEXTBOOK ORGANIC CHEMISTRY EIGHTH EDITION F. A. Carey and R. M. Giuliano McGraw-Hill New York 2011. TEXTBOOK ORGANIC CHEMISTRY