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Chapter 1,2,3

by: dsenat2013

Chapter 1,2,3 chm2210

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Class notes for chapters 1,2 and three pick out the thing s that are required and those that are not for your course.
Organic Chemistry 1
Salvatore Lepore
Class Notes
Organic Chemistry, Molecular Orbital Theory, IUPAC naming, Octet Rule




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This 34 page Class Notes was uploaded by dsenat2013 on Monday September 12, 2016. The Class Notes belongs to chm2210 at Florida Atlantic University taught by Salvatore Lepore in Fall 2016. Since its upload, it has received 271 views. For similar materials see Organic Chemistry 1 in Organic Chemistry at Florida Atlantic University.


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Date Created: 09/12/16
1 CHAPTERS 1-3 STUDY GUIDE Aliphatic—straight/branched chain organic compounds Cyclic—organic compounds in ring form Heterocyclic—cyclic compounds with an atom other than carbon in the ring Alkanes—organic molecules with all single bonds, general formula C n 2n+2 Alkenes—organic molecules with a double bonds, general formula C Hn 2n Alkynes—organic molecules with a triple bonds, general formula C n 2n-2 Hydrocarbons—organic molecules with hydrogen and carbon only Isomers Constitutional Isomers Ionic/Covalent Electronegativity Resonance Lewis Acid/base Aromatics Olefin Saturated/Unsaturated Functional Group Polarity Dipole Moment Substitution/Addition/Elimination/Rearrangement Heterolysis/Homolysis Carbocations Carbanions Solubility Hybridization Inductive Effect Solvation Protic/Aprotic Solvents Sterics Leveling effect Alkoxide ion 2 HISTORY/CHAPTER 1 History of life—air-sea-soup-nucleics(sugar, pyrimidines, purines)-DNA-cells-life-humans Organic chemicals around for years—Egyptians(alizarin, indigo), Phoenicians(royal purple) Today—ceramics, plastics, synthetics, fibers, paints, food, drink, fuel…. Vitalism—vital force; all organic compounds must be made from other organic compo unds Wohler and the synthesis of urea NH4CNO NH 2ONH 2 Lavoisier, Leibig, Berzelius, Dumas, Cannizaro, Kekule, Couper, Butlerov—qual/quant/ef/mf/structure Organic vs synthetic Organic vs. Inorganic—flammable, mp, bp, solubility, bonding, complexity, reactivity Organics—drugs, medicine, plastics, polymers, ceramics, superconductors, fabrics, cloths, synthetics, foods, drinks, cleansers, detergents, plants/animals/humans…. Polyester/nylons…cheap clothing, easy to make…allergic reactions, waste Adhesives/sealants…makes building cheaper easier…waste, fumes Polymers, plastics…convenience, cost, multiple uses…non biodegradable Herbicides, pesticides, insecticides…helps prevent illness, increases productivity…environmental BHA, BHT, MSG…flavor enhancer, preservative…allergies Saccharin…sugar substitute…cancer causing Antibiotics, Sulfa, Steroids…saves millions of lives…side effects, can be abused CFC’s…cheap, nonflammable, saved lives and money…harmful to the ozone layer STRUCTURE OF ORGANIC COMPOUNDS Organic compounds contain covalent bonds. You need to know Lewis Struct ures, Fomal Charge and Resonance theories to draw correct structures(see handout). Carbon—always 4 bonds Nitrogen—always 3 bonds Oxygen—always 2 bonds Hydrogen, halogens—always 1 bond Carbon-carbon connections can be single, double or triple bonds. 3 Isomers—connectivity/structure EF vs MF vs Structural Formula Van’t Hoff/Le Bel 4 bond arrangement is a tetrahedral Lewis/Kossel—ionic vs covalent bonding, octet rule… Linus Pauling—electronegativity Linus Pauling won 2 nobel prizes. One for chemistry and a peace prize. His chemistry prize was for his groundbreaking work on the bonding of chemicals(esp. orbital ov erlap, sigma, pi… bonds) Who else won 2? Lewis Structure Exceptions to the octet Rule—all molecules can violate by having less than 8, 3 period can violate by having more than 8, d-orbitals Formal Charge = valence e – bonds – nonbonding e Carbon with 3 bonds is positive—carbocation Carbon with 3 bonds and lone pair is negative—carbanion Nitrogen with 4 bonds is positive, with 2 bonds(and 2 lone pairs) is negative Oxygen with 3 bonds is positive, with 1 bond(and 3 lone pairs) is nega tive RESONANCE Curved arrow notation Electrons move from (-) to (+) Can only move electrons(lone pairs or double/triple bonds) Can not break or violate octet rules unless allowed by d-orbitals Use correct reaction arrows to indicate resonance Know Rules pages 16-18 4 Rules for Resonance Structures 1. Only move electrons(lone pairs or double bonds). 2. Electrons can move only from element to bond or vice versa. 3. Move electrons from electron dense(negative…) to electron poo r(positive) region. 4. When moving a pair of electrons if a violation of the octet occurs by having more than 8 electrons on a period 1 or 2 element, that is an ill egal resonance structure. 5. When a pair of electrons moves into a bond and creates a violation of the octet rule, other electrons must be moved away to stabilize the structu re. 6. All elements can violate the octet rule by having less than 8 electrons. 7. Benzene structures have resonances by rotating the 3 double bonds inside. 8. Resonances with all closed shells and no charges are the best. 9. Charge separation lowers the stability. 10. Negative charges on less electronegative atoms and positive charges on more electronegative atoms destabilize the resonance structure. 11. Open octets are the most destabilizing factor. Rules for Orbital Diagrams. 1. Replace each double bonded(sp2) element with a pi-orbital. 2. Replace each triple bonded element with 2 pi-orbitals at 90 degrees to each other. 3. Connect double and triple bonded elements with 2 lines(one from top lobe and one from bottom lobe). 4. Leave all single bonds as is. 5 O O N N O O N N O O N N O O N N 6 O O CH3 CH 3 N N O O N N N N Rank = 2 CH O 3 O CH3 N O N O N N N N Rank = 2 O CH3 O CH 3 N O N O N N N N Rank = 1 O O CH3 CH 3 N N O O N N N N Rank = 2 7 MOLECULAR/ATOMIC ORBIT THEORY MO theory is helpful for understanding the physics behind bonding of org anic molecules and some of their reactivity. Don’t get bogged down in theory though. You can know everything you need to know abou t organic chemistry without understanding orbital theory. Quantum mechanics—Schrodinger—wave mechanics, wave equations, wave functions The graph of the solutions for Schrodinger’s wave functions(squared) lead to a region of space where electrons have the highest probability of being found in relation to the nucleus(zero, zero, zero). This plot gives us the orbital shapes for s, p, d, f. Remember orbital repres ent d graph of space where it is likely to find electrons. There is NOT a physical shell around the elec trons. Recall, the Aufbau principle along with Hund’s Rule and Pauli’s Pr inciple allow us to create a very simple easily understood model of the electron density around the nucleus. As two atoms approach each other, atomic orbitals of each combine to for m molecular orbitals. # of atomic orbitals = # of molecular orbitals. Bonding molecular orbits are always lower than atomic orbitals(in Energ y). They represent a positive interference, when the two atomic orbitals enter together in phase and r einforce each other, representing a large probability that electrons will be found in that region of space b etween the two nuclei. Electrons found here increase or stabilize the newly formed covalent bond. Nonbonding molecular orbitals are always higher than atomic orbitals(in Energy). They represent a negative interference, when the two atomic orbitals enter together out o f phase and cancel each other, representing a small probability that electrons will be found in that region of space between t he two nuclei. Electrons found here destabilize the bond strength of the new c ovalent bond. HOMO—highest occupied molecular orbital LUMO—lowest unoccupied molecular orbital Hybridization of orbitals—In organic chemistry orbitals are often hybridized. 3 For ex, singly bonded carbons exhibit sp hybridization. The 2s and the three 2p orbitals mix to form 4 new(s + p + p + p) sp orbitals that exhibit characteristics of both. These new orbitals are 25% s and 75% p in character. Tetrahedral geometry. Angles = 109.5 o 8 Double-bonded carbons exhibit sp hybridization. The 2s and two of the three 2p orbitals mix to form 3 2 new(s + p + p) sp orbitals that exhibit characteristics of both. These new orbitals are 33% s and 67% p in character. This leaves one p orbital unhybridized. This unhybridize d p orbital make the “double” bond. Trigonal planar geometry. Angles = 120 o Triple-bonded carbons exhibit sp hybridization. The 2s and one of the three 2p orbitals mix to form 2 new(s + p) sporbitals that exhibit characteristics of both. These new orbitals are 5 0% s and 50% p in character. This leaves two p orbital unhybridized. These unhybridized p orbitals make the “triple” bond. Linear geometry. Angles = 180 o 2 3 s-orbitals(and sp, sp and sp ) make single “sigma” bonds. p-orbitals make double/triple “pi” bonds. A double bond consists of a sigma and a pi bond. A triple bond consists of a sigma and 2 pi bonds. The more s in a bond the shorter the bond. I.E. the shortest bonds are sp, the longest are s p. 3 Or in other words, triple bonds are shortest, single bonds are the longe st and double bonds are in between in size. sp orbitals make sigma(single) bonds. They are the longest and have a tetrahedral geometry. 2 sp orbitals make sigma(single) bonds. They are middle in length and hav e a trigonal planar geometry. sp orbitals make sigma(single) bonds. They are the shortest and have a linear geometry. p orbitals make pi(double/triple) bonds. The double bonds are trigonal planar, the triple are linear . Single bonds can rotate. Double bonds can not rotate. Double bonds can exist as cis/trans isomer s. Cis isomers have the groups on same side of double bond. Trans have the m on opposite sides. Know summary 36-38. VSEPR—tetrahedral geometry includes trigonal pyramidal(ammonia) and angular( water) Structural Formulas—dash, condensed, bond line 9 Molecular Orbital Theory H H H H π H H H C C C C σ C H H H H H H π H O H H H H H H H H H H H C H 4 10 CH 3H 2H 2H 3 H C C C C H 2 4 1 3 H H H H MF Condensed Dash Bond Line O O Br 10 CH CH 3 3 (CH 3 2HCHBrCH(CH )C3CH 2 CH CH CH 2 H3C CH C H Br CH 3 CH 3 CH CH CH2 H3C CH C H Br H2 H H2 CH CH 3H 2H(OH)CHCHCH CCH 2 C C C H3C CH C C H OH H2 H H 2 C C C H3C CH C C CH H OH CH3 H H2 H CH C C C H3C C C C C H H Br OH 2 H 3 CH 3 Br O H (CH3 2CHC(CH 3 2HCHCH CB2CHCH OH 2 11 O H2C C C C C C OH H H 2 O H C C C C C C OH 2 H H 2 O H2C C C CH 2 2 C OH H O H2C C C CH 2 2 C OH H sp2 O Br H C C CH CH HC C C C H 2 HC CH C sp H 2 3 sp sp sp3 O Br 12 EXTRA PRACTICE: Draw at least 2 resonance structures for each and indicate the best resonance structures of the ones you drew. O O N O H O O N 13 CH 3 H 2 H 2 C CH H C H C C C CH 3 H 3 2 CH 3 O H H 2 C O C H 2 C C CH 3 H2 H2 CH CH CH 3 3 3 H 2 CH C CH C H 3 C C C CH 3 H H 2 H3C CH 3 14 O O O N H O 15 O O O O . 16 CHAPTER 2 methane CH 4 ethane propane butane pentane hexane heptane octane nonane decane 17 cyclopropane cyclobutane cyclopentane cyclohexane cycloheptane cyclooctane Benzene—Know the Kekule Structure According to first 2 pictures there should be alternating double and single bonds. But in reality all 6 bonds are of the same length(1.39A). This can be explained by resonan ce and Molecular Orbital Theory. What is meant by delocalization? The electrons are dispersed between multiple bonds. In benzene the electrons are delocalized through the 6 pi orbitals of th e 6 carbons in the ring structure. These electrons are able to move freely from carbon to carbon. Know polarity/electronegativity. Be able to identify polar bonds and indicate dipole moments and/or partial charges. Polar covalent bonds/dipole moments are responsible fo r all reactions/mechanism 18 P o la r b o n d s , n o n e t d ip o le P o l a r b o n d s , n e t d ip o le N o p o la r b o n d s o r d ip o le H O C H O C O 2 4 N H C l C l 3 C 5H 1 2 C C l C l C l C l C H C l C 8H 1 8 B r C l C l C H H B r C l H C H H C l C l FUNCTIONAL GROUPS Alkyl functional groups—methyl, ethyl, propyl, butyl…isopropyl allyl ISOBUTYL sec-Butyl ISOPROPYL 4 4 3 vinyl 5 2 3 3 2 2 3 2 1 1 1 1 4 neopent yl 1 1 1 1 2 1 3 2 2 2 METHYL 4 ETHYL 3 3 tert-Butyl or t-butyl 4 PROPYL BUTYL 19 Phenyl C H Ph- φ− 6 5 Benzyl H2C H2C C H CH - Bn- 6 5 2 Alcohol/halides—F, Cl, Br, I, OH Need to know difference between 1 , 2 and 3 alkyl halide or alcohols. 2o 3 0 Br Cl HO OH F Cl 1o 3o 2o 2o Ethers—COC O O 20 Amines—NR , i3 R= 3 H’s, it is ammonia; if R = 2H’s, it is a primary amine; if R = 1 H, it is a secondary amine; if R = 0 H’s, it is a tertiary amine. + NH 4 Ammonium ion NH 3 Ammonia 2o NH 2 o NHCH 2H 3 1 o 3 (H3C)2N N(CH2CH 2H C2 )3 2 3o NHCH 3 2o Carbonyl—C double bonded to an Oxygen Aldehyde—carbonyl withH attached directly to carbon Ketone—carbonyl with two alkyl groups attached to carbon Carboxylic acid—carbonyl with OH attached to carbon Ester—carbonyl with alkoxy group(OR) attached to carbon Amide—carbonyl with amine attached to carbon Nitrile—carbon triple bonded to nitrogen Imine—nitrogen double bonded to carbon 21 O O K etone aldehyd e H N H O imine acid OH O ester O CH3 C N O nitrile CN ester O O O amide o 2 am ide N H2 N HC H3 O o O 1 amide 3 amide NH 2 N(C H3 2 PHYSICAL PROPERTIES Melting/Boiling points Melting/boiling points are determined by intermolecular forces. Ion-ion, dipole-dipole forces, hydrogen bonding In general, the larger the MW the larger the melting and boiling points. The more the branching the lower the mp/bp. Increasing the branching decreases the Van der Waal Fo rce’s which decreases mp/bp. Increasing MW increases Van der Waal Force’s which increases mp/fp. In general, the higher the polarity the larger the melting point. Hydrogen bonding increases the melting point. Symmetry increases the melting point. 1-4 Carbons—gas; 5-17 Carbons—liquids;18 and above—solids Solubility Hydrophilic/hydrophobic/lipophilicity 22 In the following pictures, identify the indicated functional groups. A H NHCH3 O O OH O 1 N O F NH E OH O Br OH NH 2 G NH D 3H C B 2 3 H Cl NH 2 N(CH2CH3 2 O O 6 5 4 I J A B C D E F G H I J In the above drawings identify as primary, secondary and tertiary the indicated groups(alcohols, halogens, amines and amides). 1 2 3 4 5 6 23 CHAPTER 3 Know differences between substitutions/addition/elimination and rearrang ement reactions. Substitutions—1 functional group replaces another Addition—double or triple bond replaced by functional group Elimination—functional group replaced by double or triple bond Rearrangement—internal structure of molecule rearranges Homolysis/Heterolysis—most reactions go through heterolysis. Homolysis is used in radical forming reactions. In general, the more polarized the bond the easier it will b e for the bond to undergo heterolysis. ACID/BASE Bronsted-Lowry vs. Lewis definitions Conjugate acid/conjugate base In organic chemistry both forms of acid/base chemistry is important. Bronsted-Lowry—many different situations in the upcoming chapters will involve protonation/deprotonation reactions. Lewis—also we will see acid/base reactions that involve electron pairs and ope n orbitals. One of the main types of Lewis Acids we will see is group three halides. Boron trifluoride, al uminum trichloride…these have open p orbital which acts as electron pair acc eptor. F B NH 3 F F Carbocations(carbons with positive charge and open p orbital) are also good Lewis Acids. Carbanions(carbons with negative charge) are good Lewis Bases. Electrophile/Nucleophile pKa, pKb… 24 The larger the pKa the stronger the base will be that is generated from that substance. The lower the pKa means the substance is a stronger acid. Low pKa strong acid, high pKa weak acid. Increasing base strength is due to the instability of the conjugate base of an acid. The more stable the conjugate base is of an acid, the stronger it will b e as an acid. The less stable the conjugate base is of an acid, the weaker it will be as an acid. A stable base is a weak base. An unstable base is a strong base. Insoluble acids can be made soluble in water by adding a stronger base t o it. In general, acidity increases as you go down a column; i.e., HI is strongest of halogen acids. In general, basicity increases as you go up a column. In general, acidity increases left to right across periodic table and ba sicity decreases left to right. The more s character of a bond the more stable the conjugate base will be; therefore, it will be a weaker base. Therefore, alkynes have most s-character and are the best acids and the weakest conjugate base. Alkanes have the least s-character and are the worst acids and the strongest conjugate bases. The more stable a base is the weaker it is(and conversely it is a stron ger acid). Stability to a base is increased by the inductive effect and by resonanc e delocalization of negative charge. Electron withdrawing groups close to the negative charge will pull the negative charge towards them through the bonds. Inducing the negative charge to move. The more(or any) resonance hybrids that can be drawn the more stable t he base. The easier it is to ionize(deprotonate) an acid the stronger that acid will be and the weaker its conjugate base will be. The more stable the conjugate base the stronger the acid. 25 Solvent effects Acids are much stronger in solvent than in gas phase. Solutions can also help stabilize the conjugate base anion. Protic solvents are hydrogen bondable and very good at stabilizing conjugate base. Aprotic solvents can not hydrogen bond and do not stabilize the conjugat e base. Neutral organic bases Alcohols can protonate to form alklyoxonium ions. Ethers can also do th is. Carbonyls can also protonate(or esp. act as Lewis Base). Nitrogen compounds can do this as well. Double/Triple bonds have the ability to protonate. They have large pi e lectron density in double bond that acts as Lewis base. - + Leveling effect—In water there can not be a stronger base than OH or a stronger acid than H O 3 If you need a stronger base you must use a non-water solvent. Sodium amide is often used in liquid ammonia. Hexane and ether bases are often used also. MECHANISM NOTATION Curved arrows are used to show the movement of electrons. Arrows are always drawn from nucleophile(electron pair, negative charge ) to the electrophile(positive charge, carbocation, lewis acid…). H B r H B r B r 26 Label the acid, base, conjugate acid and conjugate base in the reaction below. Does the reaction go forwards, backwards or is it at equilibrium? Why? O H O H + NH 3 + N H 4 NH 3 NH 2 FO RW A RDS OR B AC KW AR DS OR E QU IL IBR IUM W HY? + -2 H P3 (aq4 + H O2aq) H 3 (aq) + H P2 (aq4 Circle the better base from the two below and explain why it is better. C C E x plain F F H H A F O R H H O N E x plain H B O R H 2 H 2 O R H2 F 2 O H O H C C C C F 3 C O H H3C C O H O R H 2 H 2 E x p lain: C H3 O O C H3 Ex p la in: 27 In each pair below, circle the compound that is a stronger acid and expl ain why it is a stronger acid. H2 H2 H F OH OH C C OR 2 2 F C C OH C C 3 H H3C C OH OR 2 H2 Explain: Due tothe inductiveeffect, this molecule CH3 O OCH3 isa much stronger acid. The anionis stabilized by theelectronwithdrawingeffectxplain: of the twofluorines adjacent tothe negaThis one isstronger due to resonance charge. stabilization. The3H can not contribute tothe resonance hybridlike thecarbonylcan - O O Negativecharge canbedelocalized tothe oxygen of thecarbony. Theothermolecule can not accomplish this. - O OCH3 O OCH3 28 Using the pKa chart predict and draw the product of this Bronsted acid/base reaction. For each hydrogen indicated by an arrow, list the pKa of that hydrogen. 1 OH O 1 equivalent Br 2 OH NH3 H 2 + C CH 3 Br 4 5 NH2 O O 3 If you use excess NH 3 list the hydrogens(using 1, 2, 3, 4, 5) that will deprotonate. If you use excess CH 3H O2list the hydrogens(using 1, 2, 3, 4, 5) that will deprotonate. 10.0 1 OH O 4.2 OH O + + NH 2 1equivalent 4 Br Br - OH NH O + 3 H H 2 2 C CH 3 C CH3 Br 5 Br 4 9.4 9.2 19 NH O O NH2 O O 2 3 36 If you use excess NH 3 list the hydrogens(using 1, 2, 3, 4, 5) that will deprotonate. 2 and 4 - If youuse excess CH C3 O 2ist the hydrogens(using 1, 2, 3, 4, 5) that will deprotonate. 1, 2 and 4 29 Part I: Connectivity Worksheet—Page 12—bottom of page B, D, G, I, J Worksheet Page 4—Draw 3-D orbital pictures for methyl cyanate and methyl isocyanate Page 5—Draw a resonance form for this cation that has all closed shell atoms Page 7 (page 26) b(i) Page 8 (page 27) A (a,c) Page 11 (page 30) a, b Part II: For the molecule below, list all the functional groups. On the atoms identifiedowito ao arrow, indicate if the functional groups are primary, secondary or tertiary (1 , 2 , 3 ). 30 Fill in the C’s and H’s for the following: OH OH Br F Cl 31 32 PAGE 5 H H H C H H C H C C C C C C C C H H N H N H H H 33 34 CH 3 H2C CH 3 H H2 CH C CH C H3C CH C CH CH 3 H H2C CH 3 CH 3 CH3 CH 3 H H C CH C C2 H2C C C C CH 2 OH CH H C CH OH 3 2 3 CH 3 Br CH 3 F H CH CH CH C H 3 CH CH C CH 3 H Cl CH H3C CH 2 CH3


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