Chapter 1-1 Organic Chemistry

What is it? Why is it a two semester course? Why is it important to careers in health care?

What is Organic Chemistry?

Chem 61

Organic chemistry is essential to the understanding of the intricate details of life The interactions and reactions of organic molecules are what define living systems. One needs to understand bonding, structure, properties, reactions, and synthesis to understand natural systems. CHAPTER 1 INTRODUCTION Organic Chemistry: the study of carbon compounds... organic compounds contain the elements C, H, N, O, S, Cl, Br, etc. Organic compounds were originally thought to come only from living organisms...thus the term organic (until about 1830) Inorganic compounds were all those which came from non-living sources Scientists thought a vital force was necessary to produce organic compounds and that they could not be synthesized in the lab. In 1828 Fredreich Woeller synthesized urea, an organic compound excreted as waste, from ammonium cyanate, and vitalism slowly died out. Organic compounds range from methane , CH4 (natural gas) to DNA, the genetic coding material, and taxol, a plant derived substance which is a potential anticancer agent. Organic chemistry is fundamental to many scientific disciplines...biochemistry, polymer chemistry, microbiology, botany, pharmacy, medicine...since living systems are composed primarily of organic compounds and water.

Chapter 1-2 STRUCTURAL THEORY AND BONDING

Electronic Structure of Carbon

Chem 61

Carbon is intermediate in electronegativity, therefore it neither completely donates or completely accepts electrons. As a result it forms covalent bonds to itself and other atoms. It can bond to itself to form chains and rings...catenation. This allows the formation of a staggering number of organic compounds. 95% of all known compounds are organic.

ATOMIC STRUCTURE
It is important to understand molecular structure to understand reactivity of organic compounds. Molecular structure depends on atomic structure. Atomic structure of carbon C: 1s22s22p2 that is, carbon has 2 electrons in the lowest energy level, the 1s orbital 2 electrons in the next energy level, the 2s orbital 2 electrons in the third energy level, the 2p orbital 1s, 2s, 2p orbitals 1s is spherical with the same phase throughout

1s 2s is spherical with a node node is where ψ2 = 0 2s 2p... three orbitals of equal energy (degenerate)

node

2px

2py

2pz

Chapter 1-3

Rules for Electronic Configuration

Chem 61

Pauli Exclusion Principle: Maximum of two electrons per orbital. Electrons have a spin of +1/2 or -1/2 which gives rise to a small magnetic field since electrons are charged. Repulsion between the electrons is reduced if they have opposite spins and thus opposite magnetic moments. If two electrons occupy the same orbital they must have opposite spins or be paired. Aufbau Principle: orbitals are filled from lower to higher energy 4s 3p 3s 2p 2s 1s __ __ __ __ __ __ __ __ order of filling of atomic orbitals __ __

THUS: Li 1s22s1 Hund's Rule: orbitals of equal energy (degenerate) receive one electron until there is one electron in each orbital: then pairing of electrons begins. THUS: C 1s22s22px12py1

74Å.37Å Atomic radius increases with increasing number of electron shells within an atom and decreases with the increase in the number of protons within an atom Thus atomic radius decreases from left to right within the same row of the periodic table (increasing number of protons in the nucleus) and increases from top to bottom within a group of the periodic table (increasing number of electronic shells) ELECTRONEGATIVITY Electronegativity: a measure of an atom's attraction for outer bonding electrons Electronegativity increases with increasing charge on the nucleus and with decreasing distance between the nucleus and the electrons Thus electronegativity increases from left to right within a row of the periodic table and from bottom to top within a group in the periodic table .Chapter 1-4 ATOMIC RADIUS Atomic Radius and Electronegativity Chem 61 Atomic Radius: distance between the nucleus and the outermost electrons (valence electrons) or one half the bondlength of a diatomic molecule H—H bond length is 0. atomic radius is 0.

. C ..g.one or more electrons is completely transferred from one atom to another creating ions: a cation (positively charged) and an anion (negatively charged). N H ..atoms not having the noble gas configuration tend to form bonds such that each atom may obtain the stable noble gas electronic configuration [OCTET RULE] H H C H H single bond H C::O H double bond 4H + :C: H:C:::C:H triple bond Atoms of the elements of organic compounds can form a fixed number of bonds. O . the ions are held together by electrostatic attractions ionic bonds generally occur between atoms of highly different electronegativies.Chapter 1. .. Nao – e– Clo + e– Nao + Clo Na+ + e– Cl – Na+Cl – Covalent Bond..atomic orbitals merge into shared or molecular orbitals covalent bonds are usually formed between atoms of similar electronegativities since carbon is intermediate in electronegativity it usually forms covalent bonds Generally.....5 CHEMICAL BONDING Chemical Bonding Chem 61 G.N..one or more electrons is shared by atoms. e. Ionic Bond. Lewis put forth the first explanation of the nature of the chemical bond.

Chapter 1. one atom which is part of the covalent bond retains both electrons from the bond Cl+ + Cl – Cl Cl H 3C H H 3C + cation + H– anion ∆H (change in enthalpy) for homolytic cleavage of many covalent bonds has been determined H3C—H H—H Br—Br H—OH 104 kcal/mole 104 kcal/mole 46 kcal/mole 110 kcal/mole CH3—CH3 CH2=CH2 HC≡CH 88 kcal/mole 163 ckal/mole 230 kcal/mole . . Cl Cl H 3C H Cl + Cl .6 COVALENT BONDS Chemical Bonding Chem 61 Bond lengths: the distance between two covalently bonded nuclei Bond angle: the angle formed between two covalent bonds Bond dissociation energy: the energy required for homolytic cleavage of a bond. . two radicals Heterolytic cleavage: cleavage of a bond to give a cation and an anion. H 3C + H .

..Chapter 1-7 POLAR COVALENT BONDS Polar Covalent Bonds Chem 61 covalent bonds between atoms of similar electronegativities are said to be nonpolar bonds since each atom shares the electrons of the bond approximately equally H—H CH3—CH3 if atoms of different electronegativities form a covalent bond. polar covalent bonds cancel each other because of tetrahedral symmetry HCCl3.. CCl4... NH3.very polar δ_ Cl δ Cl δ_ Cl δ_ δ+ dipoles add _ Cl Cl Cl C Cl C δ + δ_ H δ+ H O H δ+ δ_ δ+ dipoles cancel dipoles add .polar H2O.nonpolar. then the molecule is said to be polar. the more electronegative atom will have a stronger attraction for the electrons and polarize the bond giving a polar covalent bond in which one atom is partially negatively (δ–)charged and one atom is partially positively charged (δ+) δ+ δ− H3C—Cl CH3—NH2 δ+ δ− H—Cl δ+ δ− H2C=O δ+ δ− H3C—OH δ+ δ− If any entire molecule has an overall dipole..

N. N.. . Dipole-dipole interactions: permanent dipoles in molecules attract or repel Hydrogen bonding: a specific type of dipole-dipole interaction...not often encountered in organic compounds van der Waals forces: all dipole-dipole forces are both repulsive and attractive. S and a lone pair on O. very strong occur only between a hydrogen atom bonded to an electronegative atom O.Chapter 1-8 ATTRACTIONS BETWEEN MOLECULES Polar Covalent Bonds Chem 61 ion-ion forces: the attraction between oppositely charged ions and repulsion between like charges very strong. the distance at which the repulsive forces are minimized and the attractive forces are maximized is called the van der Waals radius Induced dipole-dipole interactions or London forces: small temporary dipoles occur and induce dipoles in another molecule due to small uneven distribution of electron density. Hydrogen bonds also can influence the shapes of biomolecules by internal hydrogen bonding as well as hydrogen bonding between molecules.. S O H N H :N :O 7 kcal /mole 2 kcal/mole N H O H :N :O 3 kcal/mole 5 kcal/mole Intermolecular hydrogen bonds increase the boiling points of compounds and increase their solubility in water.

...# shared pairs of 3 electrons . number and attachment of atoms..5-4-0 = +1 O1. O3.. 1 .. 2 N.. ..6-4-0 = +2 overall charge (+2) + 4(-1) = -2 C3H7 structural formula empirical formula . draw the molecular skeleton 2..# unshared electrons :O: . .6-1-6 = -1 S. assign charges in the molecule FORMAL CHARGE formal charge on an atom = # valence electrons .. H. O. . draw covalent bonds between all the atoms giving as many as possible an octet (duet for hydrogen) 4.. .6-1-6 = -1 .Chapter 1-9 CHEMICAL FORMULAS Formulas and Formal Charge Chem 61 empirical formula: gives the types and ratios of atoms in a molecule molecular formula: gives the type and actual number of atoms structural formula: gives the type. N:O:H HNO3 Lewis structure: ...the actual structure for example: hexane: C6H14 CH3CH2CH2CH2CH2CH3 molecular formula LEWIS STRUCTURES 1....6-2-4 = 0 ... :O: ... :O:. .1-1 = O H2SO4 Lewis Structure -2 SO4 :O:S:O: . count the number of available valence electrons (be sure to account for any overall charge on the species) 3......6-2-4 = 0 O2... :O: ....

.. C::O .. . H Lewis . each carbon is assumed to have enough additional hydrogens to give each carbon four bonds H H H H C C H H C H C C H C HH H H cyclohexane benzene cyclopropane cyclobutane cyclopentane decalin ..Chapter 1-10 Structural Formulas Formulas and Formal Charge Chem 61 Lewis Structures: as described above using dots for electrons Line-bond formulas: a line is used to represent two electrons forming a bond (a shared pair) Condensed formulas: bonds are not always shown and atoms of the same type bonded to another atom are grouped together H C O H line-bond . ..C::C. H2C=O . . .H H.. . H H Lewis Polygon formulas: polygon formulas are often used to represent cyclic compounds for simplicity.. condensed HC≡CH condensed CH2=CH2 condensed H C C H line-bond H H C C H H line-bond H:C:::C:H Lewis .. . H... ..

HBr Weak acid: only partially dissociated in water: carboxylic acids are weak acid CH3CO2H acid + H2O base CH3CO2conjugate base + H3O+ conjugate acid Acids and Bases Chem 61 amines are weak bases CH3NH2 base + H2O acid CH3NH3+ + conjugate acid HO – conjugate base Generally: strong acids have weak conjugate bases and weak acids have strong conjugate bases that is.g. as acid strength increases. the basicity of the conjugate base decreases Thus the ability of the conjugate base to stabilize a negative charge determines the strength of an acid Conjugate Acids H 2O pKa 15.Chapter 1-11 ACIDS AND BASES Bronsted-Lowry: acid: a proton donor base: a proton acceptor Strong acid: completely ionized or dissociated in water e. H2SO4. HNO3..12 HCl -7 increasing acid strength Conjugate Bases HO – NC – CH3CO2– H2PO4 – C l – decreasing base strength . HCl.75 H3PO4 2.75 HCN 6.37 CH3CO2H 4.

Chapter 1-12
Factors affecting Acidity:

Acids and Bases

Chem 61

the electronegativity and the size of the atom which carries the negative charge influence its ability to stabilize the negative charge size of the atom H—F pKa 3.45 H—Cl -7 H—Br -9 H—I -9.5

increasing size of halogen, increasing acid strength electronegativity pKa (CH3)3C—H 50 (CH3)2N—H 35 CH3O—H 15.5 F—H 3.45

increasing electronegativity of atom, increasing acid strength ACIDITY CONSTANTS, Ka's for acetic acid CH3CO2H + H2O [CH3CO2–] [H+] [CH3CO2H] CH3CO2– + H3O+

Ka =

since stronger acids are more ionized, the larger Ka, the stronger the acid pKa = -logKa, the lower the pKa, the stronger the acid also, the higher the pKa, the weaker the acid or the stronger the base the stronger the acid, the more stable the anion produced by ionization of the acid.

Chapter 1-13
LEWIS ACIDS AND BASES

Lewis Acids and Bases

Chem 61

Lewis acid: electron pair acceptor: any species with an electron deficient atom BBr3, AlCl3, H3C+

Lewis base: electron pair donor; any species with an unshared pair of electrons .. .. H3N:, CH3CH2.. OH, H2C=O:

Chapter 1-14
QUANTUM MECHANICS...Molecular Orbitals

Quantum Mechanics

Chem 61

In 1923 Louis De Broglie postulated that electrons have properties of three dimensional waves Later a wave equation was developed. Solutions (Ψ) to this wave equation give the various electronic states known as atomic orbitals. Ψ = probability of finding an electron in a certain space = electron 2 probability density plots of Ψ give the familiar s,p,d...orbitals
2

WAVE PROPERTIES The amplitude of a wave may be above the resting state (positive) or below (negative)...no charge implied A node is a point at which the amplitude is zero Waves reinforce creating a wave of higher amplitude if they they are in phase.

+ – + + – –

Waves interfere if they are out of phase and create a wave which is of lower amplitude. Complete interference results in the cancelling of one wave by another.

+ –

+ –

+ –

Chapter 1-15 1s... 2s. three orbitals of equal energy (degenerate) node 2px 2py 2pz 4s __ 3p __ __ __ 3s __ 2p __ __ __ order of filling of atomic orbitals 2s __ 1s __ . 2p orbitals 1s is spherical with the same phase throughout + Quantum Mechanics Chem 61 2s is spherical with a node node is where ψ2 = 0 + node 2p.

. . then pair up Pauli Exclusion Principle.. ∆E = 52 kcal/mole if one electron is in the sigma and one in the sigma*...node between nuclei (zero electron density) σ bond is cylindrically symmetrical Aufbau principle.. ..two electrons in the same orbital must have opposite spins .Chapter 1-16 MOLECULAR ORBITALS Molecular orbitals = Linear combination of atomic orbitals Molecular Orbitals Chem 61 2 Atomic Orbitals must produce 2 Molecular Orbitals (the number of molecular orbitals equals the number of atomic orbitals which were combined to form them) the hydrogen molecule σ* H1s ∆E σ Ψ1 bonding Ψ2 Ψ1 + Ψ2 antibonding Ψ1 − Ψ2 >∆E H1s H2 ... the molecule is of higher energy than the two separate atoms because the s* is slightly >∆E higher than the s orbitals while the s is ∆E lower Bonding orbital.. the energy of the hydrogen molecule with two electrons in the sigma orbital is 104 kcal/mole more stable than the separate hydrogen atoms..fill lowest energy orbitals first Hund's Rule.place one electron in each degenerate orbital first.high electron density between nuclei Antibonding orbital.

09Å sp3 Hybridization carbon has electronic configuration 1s22s22p2 2p 2s 1s + 2s + + 3-3p's 96 kcal 2p 2s 1s hybridize sp3 1s 109.5° apart 4-sp3's sp3 orbitals point toward the corners of a tetrahedron.5° apart any carbon bonded to four other atoms is sp3 hybridized. 109.54Å C-H σ bonds require 104 kcal/mol to be broken methane H C H H H bond angles = 109.5° bond lengths = 1. Hybrid orbitals allow for better overlap and a more accurate prediction of molecular structure.Chapter 1-17 MOLECULAR ORBITALS ON CARBON Molecular Orbitals of Carbon Chem 61 Overlap between atomic orbitals in complex molecules often results in electron repulsions which destabilize the molecule.5°. CH4. tetrahedral . Methane CH4 has a central carbon with four equivalent bonds to hydrogen bond angles = 109. e.g. H3CCH3. C—C bond length = 1.

34Å pi (π) bonds are formed by the side by side overlap of two p-orbitals (approx. C=C bond length = 1. one pi C H H H C C H H sigma* orbital H H H C C H C C 120° H sigma orbitalH H E . 68 kcal/mol) pi bonds are above and below the plane where the sigma bond is located pi bonds make the molecule rigid between the two atoms preventing rotation sigma σ* pi π* pi π sigma σ ethylene C=C double bond: one sigma.Chapter 1-18 sp2 Hybridization sp2 Molecular Orbitals of Carbon Chem 61 sp2 hybridized carbons are trigonal planar with atoms 120° apart 2p hybridize 1s sp2 2p 2s 1s 96 kcal 2p 2s 1s ethylene: trigonal planar H H H H H H 2p H C H pi orbital C H H sp2 H C H pi* orbital bond angles = 120°.

bond angles 180° C=C bond length = 1.20Å acetylene has two perpendicular pi bonds and one sigma bond H 2-sp's H H C C H acetylene σ-orbital H H H C C H 2-2p's on each carbon combine to form pi-orbitals C—C σ* C—C π* C—C π C—C σ acetylene π-orbitals E . the remaining two 2p orbitals are 90° to the sp and each other + 1-2p 2-sp's Acetylene: linear.Chapter 1-19 sp Hybridization sp hybridized carbons are linear with atoms 180° apart sp2 Molecular Orbitals of Carbon Chem 61 2p 2p 2s 1s 96 kcal 2p 2s 1s hybridize 1s sp ethylene: trigonal planar + 2s 180° apart.

O CH CH 2 3 CH2CH3 diethyl ether . N H H H .. CH3 H methyl amine N H ammonia .Chapter 1-20 FUNCTIONAL GROUPs CH3CH3 alkanes CH3 OH alcohols CH2 CH2 alkenes CH3 OCH3 ethers O CH3 C CH3 ketones HC CH alkynes CH3 NH2 amines Functional Groups Oxygen: sp3 2p 2s CH3 Br alkyl halides 1s O: 1s22s22p4 hybridize 1s sp3 Chem 61 O CH3 C H aldehydes O CH3 C OH carboxylic acids O CH3 C OCH3 esters . O H H .... ... O sp2 CH3 C CH3 Hybrid orbitals of oxygen and nitrogen Nitrogen: sp3 water acetone 2p 2s 1s N: 1s22s22p3 hybridize 1s sp3 one sp3 orbital already filled with an unshared pair of electrons bonding can occur to three other atoms ... .. O H CH2CH3 ethanol two sp3 orbitals already filled with an unshared pair of electrons bonding can occur to two other atoms sp3 .. . .

Resonance structures exist only on paper.Chapter 1-21 RESONANCE STRUCTURES Chapter 6... Structures with a maximum number of octets is preferred.. 4.282: Resonance Structures Chem 61 Some molecules cannot be accurately represented by one simple line-bond formula: they are "hybrids" of two or more structures – O O C O– O– – O C O– O– – O C O 2/3– O –2/3 O C O –2/3 1. 2.the actual structures are hybrids of all the resonance structures 2... Bruice.not atoms 3. Pages 260 . Minimize charge separation. All resonance structures should have the same number of unpaired electrons Nonequivalent Resonance Structures 1. Charge separation may be enforced by the octet rule (atoms may be charged if they have an octet. Charges should be located on atoms with compatible electronegativity.) . Resonance structures differ only in the position of electron pairs. All structures should be proper Lewis structures (exceptions) 4. 3.

but alkenes and alkynes can react with hydrogen under certain conditions H2. alkenes alkanes contain only C—H and C—C single bonds CnH2n+2. alkynes.Chapter 2-1 CHAPTER 2 Hydrocarbons Chem 61 Hydrocarbons: compounds containing only hydrogen and carbon: alkanes. catalyst CH3 C C CH3 alkyne ISOMERISM Structural Isomers: compounds with the same molecular formula that differ in the order in which the atoms are bonded to one another CH3 C CH3 CH3 CH3 CH3 alkane H3C–H2C CH2–CH3 CH3 H CH3 CH3 C C CH3 H H C5H12 2-methylbutane H H H CH3 C C C CH3 H H H C5H12 n-pentane C5H12 2.2-dimethylpropane . catalyst CH2 CH2 alkene 2H2. alkenes CnH2n contain C— C double bonds and alkynes CnH2n-2 contain C—C triple bonds Alkanes do not react with hydrogen.

etc. special trivial names for branches H CH3 C C CH3 H H isobutyl H CH3 C C CH3 H H sec-butyl – 23 – CH3 C CH3 H isopropyl CH3 C CH3 CH3 tert-butyl .Chapter 2-2 NOMENCLATURE Alkanes are named by the following parent names CH4 CH3CH3 CH3CH2CH3 CH3(CH2)2CH3 CH3(CH2)3CH3 CH3(CH2)4CH3 CH3(CH2)5CH3 CH3(CH2)6CH3 CH3(CH2)7CH3 CH3(CH2)8CH3 methane ethane propane butane pentane hexane heptane octane nonane decane C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 Nomenclature Chem 61 Cyclic alkanes are named the same but with cyclo as a prefix cyclohexane cyclobutane Branched hydrocarbons are named from the parent with a substituent as a prefix hydrocarbon branches are named by dropping ane from the parent and adding -yl thus methane: methyl ethane: ethyl propane: propyl .

Find the longest continuous chain (not necessarily drawn as a straight line) and name the parent 2. Cl—. Attach the number and the name of the branch to the parent name.Chapter 2-3 BASIC RULES OF NOMENCLATURE Nomenclature Chem 61 1. Identify the branch and its position 4. —NO2 -oic acid -al -one -ol -amine -ene -yne prefix substituents – 24 – . C6H5—. Number the parent chain starting at the end nearest the branch 3. Br—.3. therefore methane butane is the parent methyl C CH3 2 1 H 2-methylbutane H CH3 C H 3C H C H CH3H C C CH3 3. H CH3 C 3 4 H CH3 the branch is CH3.5-trimethylhexane CH3H Other Functional Substitutents —CO2H C H O C increasing priority O —OH —NR2 —C=C— —C≡C— R—.

Chapter 2-4 alkenes Nomenclature Chem 61 H CH3 C H C C H C CH3 2.5-dimethyl-2-hexene CH3H CH3 alcohols H CH3 C HO H C H CH3 C H H 2-pentanol carboxylic acids H H C Br H C H H C H COOH 4-bromobutanoic acid aldehydes and ketones H CH3 C H H C CH2CH3 C CHO CH3 H C H O C CH2CH2CH3 C H CH3 CH3H 2-ethyl-3-methylpentanal 4-methyl-3-heptanone – 25 – .

low oxidation level CH2=CH2 CH3CH2OH CH3CH2NH2 CH3CH2Cl HC≡CH CH3CH=O CH3CH=NH CH3CHCl2 high oxidation level CH3CH3 CH3CO2H CH3C≡N CH3CCl3 CO2 CCl4 – 26 – . halogen). >C17 are solids Boiling points increase about 30°C for each additional CH2 unit Alkanes Chem 61 branching lowers the boiling point due to disruption of van der Waals attractions insoluble in water. S. N. soluble in organic solvents like diethyl ether.Chapter 2-5 ALKANES Physical Properties nonpolar compounds C1 to C4 are gases. C5 to C17 are liquids. benzene Chemical Properties very unreactive compounds Halogenation CH3CH3 + Cl2 light CH3CH2Cl + HCl + other products Oxidation of Alkanes Combustion spark CH3CH2CH2CH2CH3 + 8O2 5CO2 + 6H2O oxidation: a reaction that either removes a hydrogen atom from a carbon or adds an electronegative element to the molecule (O.

Ni. H2 Pd.or Pt. H2 heat . Ni. Ni. Ni.Chapter 2-6 "Complete"/"incomplete" oxidation (combustion) of propane CH3CH2CH3 2 CH3CH2CH3 CH3CH2CH3 5O2 7O2 2O2 Oxidation and Reduction Chem 61 3 O=C=O + 4 H2O "complete" combustion 6 CO + 8 H2O 3 C + 4 H2O "incomplete" combustion "incomplete" combustion Heat of Combustion: energy released when a compound is completely oxidized to CO2 and water.or Pt. H2 Pd.or Pt. Ni. Pt H2 CH3CH3 Pd. H2 CH3CH3 CH2=CH2 HC≡CH no reaction (NR) CH3CH3 CH2=CH2 Pd.or Pt. Alkynes reduction: a reaction that either adds H atoms or removes an electronegative atom from the molecule Pd. depends mostly on number of CH2 units: approximately 157 kcal/ methylene unit Reduction of Alkenes.

5 kcal 3.9 kcal anti 60 120 180 240 300 360 H H CH3 CH3 gauche H H H H H CH3 H H HCH3 H H H3CCH3 eclipsed2 H CH3 gauche HCH3 eclipsed3 E eclipsed Ethane staggered 0 60 120 180 240 ∆H = 3 kcal/mole 0 kcal 300 360 .8 kcal gauche 0 0.Chapter 2-7 CONFORMATIONS OF OPEN CHAIN COMPOUNDS Molecular Mechanics Conformations of Acyclic Hydrocarbons Butane Chem 61 E eclipsed Steric Energy: (isolated molecule in gas phase at 0° K): relative energy of a conformation or stereoisomer calculated using classical mechanics (atoms and bonds treated as balls and springs) Stretch (bond length): energy associated with stretching or compressing bonds from their optimal length Bend (bond angle): energy associated with deforming bond angles from their optimal angle Stretch-Bend: energy required to stretch two bonds involved in a severely compressed bond angle dipole-dipole: energy associated with interaction of bond dipoles out of plane: energy required to distort a trigonal center out of planarity torsional strain: destabilization from eclipsing of bonds on adjacent atoms van der waals strain: destabilization from two atoms being too close together dimensional Ethane H H C H H C H staggered H H H H H staggered H H HH eclipsed HH H H Newman projection H H CH3 H H H H CH3 anti H CH3 H HCH3 eclipsed1 H eclipsed methyls 4.

9 793.5° apart cyclopropane bond angles 60° maximum overlap cannot be achieved cyclobutane and cyclopentane H H H H H H puckered cyclobutane H H H H H H H H HH H H envelope cyclopentane puckering allows bond angles to be at or close to the tetrahedral angle and minimizes torsional strain (electron—electron repulsions in eclipsed bonds) between adjacent C—H bonds .4 6.5 0 cyclopropane: bond angles 60°.3 0 total strain energy 27.2 6.5 -∆H per CH2 166.4 strain energy per CH2 9. tetrahedral 109.Chapter 2-8 CYCLIC COMPOUNDS Strain energy Conformations of Cyclic Hydrocarbons Chem 61 -∆H (kcal/mole) cyclopropane cyclobutane cyclopentane cyclohexane 499.6 1.0 158.6 164.6 26.5° sp3 orbitals are 109.5 944.7 157.8 655.

Chapter 2-9 cyclohexane H H H H H chair cyclohexane H H H H H H equatorial bonds H Conformations of Cyclohexane Chem 61 axial bonds half chair boat E twist boat chair 7.1 5.8 kcal 0 60 120 180 240 300 360 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H chair half chair H H H H H H H boat chair twist boat .5 10.

(1.6 kcal/mole more stable H ∆G = -RTlnK ∆G = -(1.3 diaxial interactions in axially substituted cyclohexanes H H H H H H H H H H C H CH3 more stable by 1.8 kcal/mole H H 1.Chapter 2-10 Substituted Cyclohexanes Conformations of Cyclohexane Chem 61 substitutents on cyclohexanes preferntially occupy equatorial positions due to 1.74 kcal/mole for methylcyclohexane .3-diaxial interactions E H H gauche H CH3 C H C H H H H H H H C C H H anti CH3 H axial substitution similar to gauche butane equatorial substitution similar to anti butane H CH3 CH3 H CH3 C H H H H H H C(CH3)3 H 5.98 kcal/mol°)(298)(2.98 kcal/mol°)(298)(ln19) = -1.94) = .

Chapter 3-1 Chapter 3 STEREOCHEMISTRY Geometric isomerism in cyclic compounds Stereochemistry: Geometric Isomers Chem 61 OH H OH OH trans-1.2-cyclohexanediol CH3 OH OH H cis OH H CH3 trans-1.3-dimethylcyclobutane H Br Br cis Geometric Isomerism in alkenes 68 kcal/mole to cleave a carbon-carbon pi bond thus no "free" rotation H C CH3 C H CH3 CH3 H C C CH3 H CH3 Br cis trans-2-butene cis-2-butene H C CH3CH2 C CH3 H H C Cl C H Cl trans-2-pentene cis-1.2-dichloroethene .

not cis or trans CH3 C CH3CH2 C H Cl Cl C Br C I F E entgegen (across) Z zusammen (together) Cahn-Ingold-Prelog Sequence rules 1. if the atoms are different. the atomic numbers of the next atoms are used to assign priority 4. if two isotopes of the same element.Chapter 3-2 Absolute Configuration Chem 61 Stereoisomers: compounds with the same structures differing only in their arrangement of atoms in space. atoms attached by double or triple bonds are given single bond equivalencies O R C R' = (O) R C R' O (C) (C) R O C OH = R (O) C O (C) OH (C) R C CR' = R R' C (C) C (C) (C) R C H C—R' H R H C C (C) H R' . the one with the higher mass gets higher priority 3. if the atoms are the same. highest atomic number gets highest priority 2.

it is achiral. H Cl C* CH3 CH3 H C* Cl CH3 OH C* CH2CH3 CH2CH2CH3 H CH2CH3 CH2CH3 enantiomers Fischer Projections by convention: horizontal bonds come out of the paper vertical bonds go back into the paper CH3 H C OH CH3 H OH CH2CH3 H H C OH H C OH CH3 H H H OH OH CH3 CH2CH3 0000 0000 0000 0000 0000 0000 0000 0000 000 000 000 0000 000 0000 0000 0000 0000 0000 0000 0000 0000 0000 Cl Cl I Br Br H I H 000 000 000 0000 000 0000 0000 0000 000 000 000 000 000 000 000 000 000 000 000 000 Br C* CH3 . mirror plane 0000 0000 0000 Cl Cl Br I I Br H H Stereogenic carbon atom: a carbon with four different groups bonded to it (designated *).Chapter 3-3 CHIRALITY Stereochemistry: Chirality Chem 61 An object or molecule which cannot be superimposed on its mirror image is said to be chiral If an object or molecule can be superimposed on its mirror image. Enantiomers: isomers which are nonsuperimposable mirror images.

interactions with polarized light Polarimeter ordinary light polarized light rotated light lamp polarizer solution of sample if plane polarized light is passed through a solution of a single enantiomer.Chapter 3-4 OPTICAL ROTATION Stereochemistry: Chirality Chem 61 enantiomers have almost all the same physical and chemical properties properties which differ are: 1. interaction with other chiral substances 2. also (+) or d levorotatory: rotates plane polarized light to the left. also (–) or l racemic mixture: a 1:1 (50:50) mixture of two enantiomers does not rotate plane polarized light. the opposite enantiomer will rotate the light in the opposite direction optically active: a compound which rotates plane polarized light optical isomers: enantiomers dextrorotatory: rotates plane polarized light to the right. therefore optically inactive . the light is rotated either to the right or the left.

Project the molecule with the lowest priority group to the rear 3. If the direction of the semicircle is clockwise. assign the configuration as usual and then reverse it 2 Cl 1 Br C CH3 3 3 CH3 2 Cl C H R S 4 S Br 1 H 4 lowest priority group out .Chapter 3-5 Stereochemistry: Absolute Configuration Chem 61 Absolute configuration: the order of arrangement of the four groups around a stereogenic center enantiomers have opposite configurations (R) and (S) Cahn-Ingold-Prelog System R: rectus or right S: sinister or left To assign R and S to an asymmetric atom 1. Rank the four attached groups from 1 (highest) to 4 (lowest) priority based on the Cahn-Ingold -Prelog Sequence rules 2. Draw a semicircle from 1 to 2 to 3 4. configuration is R. if counterclockwise. configuration is S 3 CH3 1 Br C H 4 Cl 2 2 CH3CH2 3 CH3 C H R 4 R OH 1 If lowest priority group is out.

Chapter 3-6
Molecules with Two or more Asymmetric centers

Stereochemistry: Diastereomers

Chem 61

If a molecule has n asymmetric carbon atoms, it contains a maximum of 2n isomers; may not have that many diastereomers CH2OH H H C C OH OH HO HO CH2OH C C H H H HO diastereomers

meso H CH3 H CH3 H CH3

chiral H CH3

HO H meso

OH H

HO H chiral

H OH

CH2OH C C OH H HO H enantiomers

CH2OH C C H OH

mirror plane

mirror plane

CH3 enantiomers

CH3

CH3

CH3

two asymmetric carbons; 4 isomers diastereomers: stereoisomers which are not enantiomers; may have different physical and chemical properties Meso compounds meso compounds contain an internal plane of symmetry and are achiral: that is the mirror image is identical to the original diastereomers meso: identical CH2OH H H C C OH OH HO HO CH2OH C C H H H HO CH2OH C C OH H HO H CH2OH C C H OH

CH2OH

CH2OH

CH2OH enantiomers

CH2OH

superimposable

Chapter 3-7

Stereochemistry: Asymmetric Synthesis, Resolution

Chem 61

Preparation of Enantiomerically Enriched Compounds Generating chiral compounds from achiral compounds Enzymes O O OEt >98% R HO O OEt

yeast

H

Asymmetric Reagents H OH t-BuOOH (+)-diethyl tartrate Ti(i-OPr)4 O OH H >95% one enantiomer Resolution of a Racemic Mixture separated salt converted back to acid (R) R*COOH + (S) R*NH2 + (S) R*COOH racemic (R) R*COO–(S) R*NH3+ + (S) R*COO–(S) R*NH3+ diastereomeric salts (separable) (S) R*COOH

(R) R*COOH

Chapter 4-1
ACIDS AND BASES Bronsted-Lowry: acid: a proton donor base: a proton acceptor Strong acid: completely ionized or dissociated in water e.g., HCl, H2SO4, HNO3, HBr Weak acid: only partially dissociated in water: carboxylic acids are weak acid CH3CO2H acid + H2O base CH3CO2conjugate base + H3O+ conjugate acid

Acids and Bases

Chem 61

amines are weak bases CH3NH2 base + H2O acid CH3NH3+ + conjugate acid HO – conjugate base

Generally: strong acids have weak conjugate bases and weak acids have strong conjugate bases that is, as acid strength increases, the basicity of the conjugate base decreases Thus the ability of the conjugate base to stabilize a negative charge determines the strength of an acid Conjugate Acids H 2O pKa 15.75 HCN 6.37 CH3CO2H 4.75 H3PO4 2.12 HCl -7

increasing acid strength Conjugate Bases HO – NC – CH3CO2– H2PO4 – C l –

decreasing base strength

5 increasing size of halogen. the larger Ka. the more stable the anion produced by ionization of the acid. Ka's for acetic acid CH3CO2H + H2O [CH3CO2–] [H+] [CH3CO2H] CH3CO2– + H3O+ Ka = since stronger acids are more ionized. the higher the pKa. the lower the pKa. increasing acid strength ACIDITY CONSTANTS.45 increasing electronegativity of atom. the weaker the acid or the stronger the base the stronger the acid.45 H—Cl -7 H—Br -9 H—I -9.5 F—H 3. . increasing acid strength electronegativity pKa (CH3)3C—H 50 (CH3)2N—H 35 CH3O—H 15. the stronger the acid pKa = -logKa.Chapter 4-2 Factors affecting Acidity: Acids and Bases Chem 61 the electronegativity and the size of the atom which carries the negative charge influence its ability to stabilize the negative charge size of the atom H—F pKa 3. the stronger the acid also.

. CH3CH2. any species with an unshared pair of electrons . H2C=O: . H3N:.. AlCl3.Chapter 4-3 LEWIS ACIDS AND BASES Lewis Acids and Bases Chem 61 Lewis acid: electron pair acceptor: any species with an electron deficient atom BBr3. . OH.. H3C+ Lewis base: electron pair donor.

34Å pi (π) bonds are formed by the side by side overlap of two p-orbitals (approx.Chapter 5-1 ALKENES Alkene Structure sp2 hybridized carbons are trigonal planar with atoms 120° apart 2p 2s 1s 96 kcal 2p 2s 1s hybridize Alkenes: Structure and Isomerism Chem 61 2p sp2 1s ethylene: trigonal planar H H H H H H 2p H C H pi orbital C H H sp2 H C H pi* orbital bond angles = 120°. C=C bond length = 1. 68 kcal/mol) pi bonds are above and below the plane where the sigma bond is located pi bonds make the molecule rigid between the two atoms preventing rotation H H H C C H C C 120° H sigma orbitalH H C H C C H H H sigma* orbital H E sigma σ* pi π* pi π sigma σ ethylene C=C double bond: one sigma. one pi .

2-dichloroethene Stereoisomers: compounds with the same structures differing only in their arrangement of atoms in space.Chapter 5-2 Geometric Isomerism in alkenes Alkenes: Structure and Isomerism Chem 61 68 kcal/mole to cleave a carbon-carbon pi bond thus no "free" rotation H C CH3 C H CH3 CH3 H C C CH3 H trans-2-butene cis-2-butene H C CH3CH2 C CH3 H H C Cl C H Cl trans-2-pentene cis-1. if two isotopes of the same element. if the atoms are the same. not cis or trans CH3 C CH3CH2 C H Cl Cl C Br C I F E entgegen (across) Cahn-Ingold-Prelog Sequence rules Z zusammen (together) 1. the one with the higher mass gets higher priority 3. atoms attached by double or triple bonds are given single bond equivalencies . the atomic numbers of the next atoms are used to assign priority 4. if the atoms are different. highest atomic number gets highest priority 2.

A mechanism includes the transition states involved in making and breaking bonds and reactive intermediates that are formed along the pathway from reactants to products. I– CH3NH2 H2O Reaction Mechanisms of Electrophilic Addition Reactions reaction mechanism: a detailed description of how a chemical reaction occurs. H Consider Ethylene: The site of reactivity is the pi-bond due to the exposed nature of the pi electrons H H H H H H 2p H C H pi orbital C H H sp 2 H H C H C H Br H H 2p H H H Br– Br H H H H H H H H C C H Br– + CH2—CH2–H H–Br Br H H2C CH2 C C 120° H sigma orbitalH CH2=CH2 H C H pi* orbital C H H H C H C H H sigma* orbital The pi electrons act as a Lewis base (electron pair donor)..Chapter 5-3 Alkenes: Reactivity Alkenes: Electrophilic Addition Reactions Chem 61 The reactivity of alkenes is due to their ability to donate a pair of electrons: their Lewis basicity. These electrons react with electron deficient species (Lewis acids) Alkenes undergo electrophilic additions reactions.. .. Electrophile: an electron deficient ion or molecule H+ Br+ BH3 +CH3 Nucleophile: an electron rich ion or molecule. A roadmap of a reaction.curved arrows show which bonds are formed or broken.

Chapter 6-1 Thermodynamics describes the properties of a system at equilibrium ∆G = – RT ln Keq where Keq = [reactants] [products] R = 1.986 X 10-3 kcal K-1 mol-1 (gas costant) T = temperature in degrees Kelvin ∆Go = ∆Ho – T∆So free energy = enthalpy – T x entropy enthalpy = heat of reaction entropy = state of disorder transition state Thermodynamics Chem 61 Energy Diagram E reactants ∆G ‡ products progress of reaction reactants – ∆G products exergonic + ∆G reactants products endergonic .

transition state slower E reactants progress of reaction first order reaction rate = k[A] rate is proportional to the concentration of one reactant ∆G ‡ E products reactants progress of reaction ∆G ‡ faster transition state products second order reaction rate = k[A] [B] rate is proportional to the concentration of two reactants A two step reaction transition state E ∆G‡ reactants Rate limiting step: is the slowest step (step with the highest energy of activation) transition state ∆G‡ intermediate products . the faster the reaction will be.Chapter 6-2 Kinetics describes the rate of progression of a reaction Kinetics Chem 61 depends on the energy of activation (the stability of the transition state): the lower the transition state energy.

a carbocation. the halogen (A–) is found attached to the most substituted carbon atom of the alkene (Markovnikoff's Rule): . The term regiospecific is used if one product is formed exclusively. I–) X– CH3 CH3 X C CH3 CH3 C CH2 + H—X CH3 + C CH3 CH3 CH3 Reactivity: H—I > H—Br > H—Cl > H—F The reaction is said to be regioselective since an unsymmetrical alkene gives a predominance of one of two possible electrophilic addition products. Br–. C C + Nu: No Reaction However. Cl–. the reagent is E+A– (E+ = electrophile. reacts with A– to yield a product in which E and A have added to the C=C double bond. In these reactions. A– = some anion) C C + E A + – E + C C A A – E C C Note the alkene acts as a Lewis base (or nucleophile) toward the Lewis acid (or electrophile) The intermediate.Chapter 6-3 Electrophilic Addition Reactions Electrophilic Addition: Addition of H–X Chem 61 Nucleophilic addition does not occur with alkenes unless an electron-attracting group is attached to one of the carbon atoms to cause a polarity difference. Addition of HX (E+ = H– A– = F–. in the electrophilic addition reaction.

If a nucleophilic solvent is employed in the electrophilic addition reaction solvent may compete with A – for the intermediate carbocation. + HCl (CH3)2CH CH CH3 (CH3)2CH CH CH2 (CH3)2CH CH CH3 + (CH3)2C Cl CH2 CH3 60% 40% Cl . Since a carbocation intermediate is involved.Chapter 6-4 CH3 C CH2 + H—X + C X– CH3 Electrophilic Addition: Addition of H–X X CH3 C CH3 Chem 61 CH3 CH3 CH3 CH3 R C R CHR + H—X R + C X– CHR R X C R CHR R C R CHR + H—X R 3° carbocation more favored X– + R CH C—R R 2° carbocation less favored H R C R X CHR Thus regioselectivity is explained by the lower Eact leading to the 3° carbocation intermediate. Cl CH CH2 HCl CH3COOH (solvent) CH + CH3 OCOCH3 CH CH3 Note the C=C's of the aromatic ring do not undergo this type of reaction. rearrangement may sometimes occur.

Any structural feature that will disperse a positive charge will stabilize the carbocation. they cannot be observed directly in the reaction mixture since they react as soon as they are formed. Name methyl primary 1° secondary 2° tertiary 3° vinyl allyl secondary allyl tertiary allyl phenyl + benzyl CH2+ secondary benzyl tertiary benzyl diphenylmethyl triphenylmethyl + CHCH3 + C(CH3)2 + CH + C 226 220 215 210 233 Structure CH3+ CH3CH2+ (CH3)2CH+ (CH3)3C+ CH2=CH+ CH2=CH—CH2+ CH2=CH—CH+(CH3) CH2=CH—C+(CH3)2 Hydride Affinity (kcal/mol) 314 274 247 230 287 256 237 225 298 . the more stable the carbocation. The lower the value of the hydride affinity.Chapter 6-5 Carbocation Stability Chem 61 Carbocation stability Carbocations are highly reactive intermediates . This stabilization has been quantitated by so-called hydride H:– affinity measurements (gas phase).

Chapter 6-6 Carbocation Stability Chem 61 Thus the order of carbocation stability is triphenyl methyl > diphenylmethyl > 3° ≈ benzyl ≈ allyl > 2° > 1° >> methyl Carbocation centers can be stabilized by overlap with adjacent pi orbitals (resonance) or adjacent sigma orbitals (hyperconjugation). H + CH3 CH3 p C . .. C H σ H sigma donation adjacent sigma bond donates some electron density to the empty p orbital on the carbocation center more adjacent sigma orbitals result in a more stable carbocation thus 3° > 2° > 1° > methyl + H H p + CH2 pi C C H C H H empty p orbital ovelaps with adjacent pi orbital to disperse the positive charge CH CH2 CH2 CH + CH2 equivalent resonance structures Since the pi orbital is closer in energy to the empty p than the sigma orbital. the pi overlap stabilizes the cation more efficiently.

A– = HOH) use H2SO4. :O H R 2C CH2 R + H3O+ R 2C TS2 Eact + R 2C CH2 R H +O H R 2C CHR R 2C CH2 R O H R 2C CH2 R TS3 Addition of water to alkenes is a reversible reaction and whether the alkene or the alcohol predominates at equilibriuim depends on the reaction conditions... H2O H+ Step 1 R 2C CHR Electrophilic Addition: Addition of H2O Chem 61 + R 2C CH2 R H + :O H . . :OH2 CH2 R TS1 . Step 2 + R 2C H Step 3 H O: + :OH2 CH2 R R 2C CH2 R . Higher temperatures and removal of water favor the alkene.Chapter 6-7 Addition of Water (E+ = H+. Low temperatures and high concentrations of water favor the alcohol..

NaBH4 reduction of the C—Hg bond yields the alcohol in a separate step. O CH3 C O Hg O O C CH3 + CH3 C CH3 CH2 1. NaBH4 C CH3 O Hg O E + O CH3 + – C O C CH3 mercury acetate CH3 C CH3 CH3 CH3 CH2 + +Hg O O C CH3 + CH3 C O CH2 Hg O C CH3 O C CH3 CH3 carbocation or O H2O: CH3 C + Hg O CH2 C CH2 Hg O C CH3 +OH2 CH3 bridged carbocation Since no rearrangement is observed in reactions with +HgOCOCH3 the bridged carbocation is believed to be the true intermediate. ROH 2.Chapter 6-8 Addition of Mercury acetate and Water ( E+ = +HgOCOCH3. Attack by H2O on the more electron deficient carbon opens the bridged cation (backside attack). A– = OH2) Electrophilic Addition: Oxymercuration Chem 61 If alcohol is used as the solvent in this process ethers are obtained as the products. Hg(OCOCH3)2. CH3 CH3 RO To avoid carbocation rearrangements under the conditions used in addition of H2O (H2SO4/H2O) a better system for the addition of water to a C=C has been devised. CH3 CH3 C CH2HgOCOCH3 +OH2 H 2O CH3 CH3 HO C CH2 HgOCOCH3 NaBH4 CH3 CH3 HO C CH3 + Hg° .

Chapter 6-9 Hydroboration (E+ = B. Further reaction of R—CH2–CH2—BH2 with more alkene yields first the dialkyl borane and then the trialkyl borane as the stable product. H R—CH=CH2 + BH3 R H C B C H H H H H R H C B C H H H H ‡ H R C H B C H H H H Note B is the electrophile and H acts as A-. R—CH=CH2 + R—CH2—CH2—BH2 ( R—CH2—CH2)2BH R—CH=CH2 ( R—CH2—CH2)3B Brown discovered that trialkylboranes were easily oxidized by alkaline hydrogen peroxide (H2O2 in HO–). C≡C is termed hydroboration. . The oxidation reaction proceeds as shown.C. The addition of H– and B occur from the same face of the alkene (syn addition). A– = H–) Electrophilic Addition: Hydroboration Chem 61 Discovered by H. Borane is generated by 3 NaBH4 + 4 BF3 2 B2H6 (diborane)+ 3 NaBF4 4 BH3 (borane) Addition of BH3 to C=C. Brown in the 1950's. The reagent BH3 (borane) is used in electrophilic addition reactions.

H3O+ or Hg(OCOCH3)2 then NaBH4 – R—CH2—CH2—OH R—CH=CH2 R—CH—CH3 OH Treatment of a trialkylborane with CH3CO2D yields a monodeuterated alkane CH3CO2D (CH3CH2)3B CH3CH2D . OH Note the reaction is regioselective and yields an alcohol that is isomeric to that obtained by Hg(OCOCH3)2—NaBH4 or H2SO4—H2O. H2O2. BH3 2.Chapter 6-10 Electrophilic Addition: Hydroboration Chem 61 – ( R—CH2)3B OOH RCH2 CH2R B–O OH RCH2 RCH2 RCH2 B O CH2R + —OH OCH2R RCH2 B O CH2R – OOH CH2R RCH2CH2 B–O O OH CH2R – OOH RCH2O OCH2R B O CH2R – OH 3 R—CH2—OH + B(OH)3 The overall reaction is R—CH=CH2 1.

Chapter 6-11 Electrophilic Addition: Hydroboration Chem 61 Treatment of a trialkylborane with CH3CO2D yields a monodeuterated alkane (CH3CH2)3B CH3CO2D CH3CH2D Bromination of a trialkylborane yields the alkyl bromide. Br2 HO– (C6H5CH2CH2)3B C6H5CH2CH2Br Stereochemical Results of Hydroboration Hydroboration is regioselective and stereospecific CH3 H B BH3 H H H2O2 HO– OH H H + H OH H CH3 cis-addition CH3 CH3 enantiomers Thus H and OH add cis to the C=C. .

Nucleophilic opening of the bridged ion by backside attack of Br – at carbon gives overall anti (trans) addition of E+(Br+) and A– (Br–) to the double bond.Chapter 6-12 Stereochemistry of Halogenation Br + C C Br— Electrophilic Addition: Stereochemistry of Halogen Addition Chem 61 Br C C Br C C Alkenes containing alkyl substituents react with Br2 via a bridged bromonium ion intermediate. Some examples: CH3 Br2 H or Cl2 X CH3 C H C CH3 H + X (enantiomers) CH3 H X C C H X CH3 CH3 C H C CH3CO2H (solvent) X CH3 C H C H CH3 Br2 or Cl2 CH3 C H H CH3 meso C X Br2 or Cl2 CCl4 X X H H + X HH X . Chlorination reactions proceed by a similar pathway.

Chapter 6-13 Mixed Addition Electrophilic Addition: Mixed Addition Chem 61 Br— C C Br+ Br+ C C Cl— Br C C Br Br C C Cl Br2 or Cl2 with H2O. HO– present: C C X+ X+ C C HO– X C C OH Mixed Reagents R S+ RS—Cl + C C C C NO C I I—Cl + C C C + RS C C Cl NO C Cl I C C Cl C O=N—Cl + C C + C C .

6 Thus the stability of the three alkenes is Chem 61 CH3 CH3CH=CHCH3. Z > CH3CH2CH=CH2 These comparisons indicate i) increasing alkyl substitution stabilizes an alkene ii) conjugated dienes are more stable than non-conjugated dienes.3 CH3CH=CHCH3. ∆Hh (kcal/mol) CH3CH2CH=CH2 -30. E -27. E > CH3CH=CHCH3.6 CH3CH=CHCH3. H H C CH3CH2 H C CH3 H C CH3 C H Z-CH3CH=CHCH3 E-CH3CH=CHCH3 C CH3 CH3 C H H CH3CH2CH2CH3 + heat CH3CH2CH=CH2 E ∆Hh ∆Hh ∆Hh progress progress progress . Z -28.Chapter 6-14 Hydrogenation of Alkenes addition of H2 is cis (syn) H H2/Pd H CH3 CH3 H2/Pd CH3 H H C C CH3 CH3 Hydrogenation of Alkenes Alkene Heat of Hydrogenation. It is calculated by measuring the amount of heat released in a hydrogenation reaction. iii) trans alkenes are more stable than cis alkenes (steric repulsions in cis) CH3 C C CH3 ii) Heat of Hydrogenation Studies The heat of hydrogenation of an alkene is the energy difference between the starting alkene and the product alkane.

Br . Free radicals are usually encountered as high energy short-lived. CH3 C CH3 combination of any two radicals Br Br H–Br CH2 CH3 H C Br CH2 + Br . . CH3 CH3 CH3 CH3 Stability of Carbon Free Radicals (Which H atom is abstracted?) Stability of carbon free radicals follows the same pattern as carbocations: . . Br C CH2 + Br CH3 Br2 termination CH3 . RO–OR CH3 Br Br C CH2 CH3 2 RO . non-isolable intermediates in certain reactions. . ROOR initiation R C R CHR + H—Br R . C6H5CH2 > (CH3)3C > (CH3)2CH > CH3CH2 > CH3 . H3C . Free Radical: any atom or group of atoms that contains one or more unpaired electrons. A free radical is symbolized as a single dot representing the unpaired electron: Cl . . C Br CHR H R C R Br CHR . propagation R 3° carbocation more favored CH3 CH2 + Br . . . . . etc. CH3 CH3 propagation . allyl benzyl tertiary secondary primary methyl heat or light RO–OR peroxide RO 2 RO . + Br . . . C + H—Br RO–H + Br .Chapter 6-15 Radical Addition Reactions Chem 61 Addition of HBr in the presence of a radical initiator such as peroxides effects so called anti Markovnikov addition of HBr CH3 C CH2 + H—X + C X– CH3 CH3 X C CH3 Reversal of regioselectivity (position of bromine and H addition) results from the inital addition of Br radical rather than H+. CH2=CH—CH2 .

Chapter 7-1
Free Radical Substitution Reactions

Radical Reactions of Alkanes

Chem 61

Free Radical: any atom or group of atoms that contains one or more unpaired electrons A free radical is symbolized as a single dot representing the unpaired electron: Cl , Br , H3C , etc. Free radicals are usually encountered as high energy short-lived, non-isolable intermediates in certain reactions. (Recall that carbocations were seen to be intermediates in certain reactions in Chapter 5). CH3 a) CH3 C Br CH3 CH3
– C+ Br

.

.

.

carbocation intermediate

CH3 double barbed arrows indicate the movement of two electrons CH3 b) CH 3 C CH3 Br CH3 CH3 C

CH3

.

Br.

free radical intermediate

CH3

single barbed arrows indicate the movement of one electron Note that the carbon in a) has lost an electron pair to the bromine atom, thus the carbon has an sp2 configuration and a single "+" charge resulting from the empty p orbital. In b) the carbon atom has lost one electron; the carbon is also in the sp2 configuration with the unpaired electron in the p orbital.

CH3 CH3

C

CH3

(CH3)3C+

CH3 CH3

.
C CH3

(CH3)3C

.

equal probability of electron being in either lobe

Chapter 7-2
Free Radical Substitution Reactions Chlorination of methane in the presence of light is the classic example

Radical Reactions of Alkanes
Hence CH2Cl2, CHCl3, and CCl4 are formed c) Termination of the Chain Reaction

Chem 61

CH4 + Cl2

light

CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl

Any reaction of Cl or of the carbon free radical intermediates (CH3 ,
.

.

.

Reaction mechanism involves three general steps: Initiation, propagation, and termination a) Initiation of the radical chain reaction heat or light

CH2Cl, CHCl2, CCl3) that disrupts the propagation of the chain will

.

.

terminate the reaction. Cl Cl

. .

+ CH3

. .

Cl Cl

2Cl requires 58 kcal/mole two chlorine radicals

.

CH3 + CH3

.

+

.

CH3—Cl CH2Cl2 CH3—CH3 Cl—CH2—CH2—Cl

CH2Cl

.

CH2Cl + CH2Cl

.

b) Propagation (self-perpetuating the chain reaction)

i)

Cl

. .

H H C H

H—Cl + CH3

.

requires 1 kcal/mole a methyl radical

ii)

CH3 + Cl—Cl

CH3—Cl + Cl

.

chlorine radical can now react with more CH4 and propogate the chain Note: Cl has substituted for a H and therefore free radical substitution iii) As the concentration of CH3—Cl increases in the reaction mixture Cl starts to react with both CH4 and CH3Cl. Cl
.

.

+ CH3—Cl

H—Cl +

.

CH2—Cl (chloromethyl radical)

.

CH2—Cl + Cl—Cl

Cl—CH2—Cl + Cl

.

Chapter 7-3
Reactivity of the Halogens F2 Bond Dissociation Energy Cl2 Br2 I2 46 36 kcal/mole
. .

Reactivity of the Halogens

Chem 61

37 58

Thus the energy of activation for formation of F and I is lower than Cl and Br however, the order of reactivity of X. with alkanes is: F2 >> Cl2 > Br2 >> I2 (I2 does not normally react; F2 reacts explosively) Thus the rate determining step is not: X—X 2X.

.

.

Rather, hydrogen atom abstraction is the rate determining step.

X + CH4

.

H—X +

.

CH3

Since chlorination is faster than bromination, Eact for Cl + CH4

.

H—Cl +

.

CH3

must be lower than the Eact for Br + CH4

.

H—Br + CH3

.

[CH3 + HCl +Cl2] E Eact Cl + CH4 CH3Cl + Cl Progress

.

[CH3 + HBr + Br2]

.

.

.

Eact Br + CH4

.

CH3Br + Br

.

H CH3CH2 C CH2Cl CH3 R Br CH3CH2 CH3 C CH2Cl S CH3OH Cl2 Cl CH3CH2 C CH2Cl CH3 S (50:50) OCH3 CH3CH2 C CH2Cl CH3 S CH3CH2 + CH3 R C Cl CH2Cl CH3CH2 + CH3 C R CH2Cl OCH3 (50:50) . C6H5CH2 > (CH3)3C > (CH3)2CH. . racemization will be observed in the products resulting from both intermediates.Chapter 7-4 Stability of Carbon Free Radicals (Which H atom is abstracted?) Reactivity of the Halogens Chem 61 Stability of carbon free radicals follows the same pattern as carbocations: CH2=CH—CH2 . > CH3CH2 > CH3 allyl benzyl tertiary secondary primary methyl . . Unlike carbocations. . CH3 CH3 C CH CH3 CH3 CH3 C CH CH3 + CH3 2° CH3 CH3 C CH CH3 Cl2 CH3 CH3 CH3 C + 3° CH CH3 CH3 CH3 C CH CH3 H 2O OH CH3 . free radicals do not rearrange to a more stable free radical. . CH3 2° CH3Cl Since both carbocations and free radicals involve planar sp2 carbon atoms.

CH3 . light CHCH3 + (56:44) Br CH2CH2Cl a) 1° b) 3° c) allyl e) 2° Br2. . . light Thus intermediates c) and d) should be more stable and should lead to CH3 and Br as products. Br. The transition state in the chlorination reaction is less influenced by the stability of the intermediate free radical. .Chapter 7-5 Selectivity of Hydrogen Atom Abstraction Selectivity of Halogenation Other examples of this are: Cl Chem 61 The more stable free radical should determine the nature of the product CH3 CH2 . thus (CH3)2CH is formed exclusively. CH3 CH2CH3 Cl2. In bromination the more stable free radical intermediate is highly favored. . . CHCH3 100% CH3 Br Chlorination is much less specific than bromination Cl CH3CH2CH3 Cl2 CH3 CH CH3 55% Br CH CH3 100% + CH3CH2CH2Cl 45% CH3CH2CH3 Br2 CH3 The difference in selectivity of H atom abstraction by Cl and Br is explained by the Hammond postulate. CH3 CH3 . thus both (CH3)2CH and CH3CH2CH2 result. d) allyl . . .

. + N≡N C≡N. C≡N. c) alkyl hypochlorites R—O—Cl d) azobisisobutyrylnitrile CH3 CH3 C N N RO + Cl . NBS is used to introduce a Br atom at allylic or benzylic positions. Some of these reagents include: a) dibenzoyl peroxide C6 H5 C O b) hydrogen peroxide H O O H ∆ 2 H O. Clues to Whether a Reaction Involves Free Radicals a) Reaction requires high temperatures (>200°) b) Reaction requires light energy (hν) c) Reaction requires an initiator (a-d above) or oxygen.Chapter 7-6 Bromination with N-Bromosuccinimide (NBS) O CCl4 NBr + O light or peroxide NH + O Br O Halogenations Chem 61 NBS acts as a Br2 source. C≡N. the reaction is initiated by either light or a peroxide (ROOR). O O C O C 6H 5 2 C6 H5 C O O . Other Sources of Free Radicals Although light (hν) and heat (∆) are used for halogenation reactions other reagents are often useful for initiating free radical reactions. CH3 C CH3 2 CH3 CH3 C . .

1° R2CH—X secondary.Chapter 8-1 Nucleophilic Substitution Reactions (SN1. 3° do not easily undergo nucleophilic substitution reactions Examples CH3—I + Na+ – OCH3 CH3CH2CH2—Br + Na+ Cl + Na +– – CH3OH CH3OH CH3—OCH3 + Na+ – I OH CH3CH2CH2—OH + Na+ – Br SH + NaCl SH CH3OH Br + CH3 CH3OH OCH3 + HBr CH3 Anatomy of a nucleophilic substitution reaction SH CH3 CH I CH3 + Na+ – SH CH3OH CH3 CH CH3 + Na+ I – . 2° Nucleophilic Substitution Reactions Chem 61 R3C—X tertiary. SN2) alkyl halides: CH3—X methyl X aryl halide vinyl halide CH2=CH—X RCH2—X primary.

δ+ δ − Nu:– + R—CH2—L electron pair that accompanies L R—CH2—Nu + L:– electron pair for new bond at C . containing the leaving group that is acted on by the nucleophile (here: 2-iodopropane) Solvent: the medium used to dissolve the substrate and the nucleophile (in this case methanol. CH3OH). solvent can sometimes be the nucleophile (solvolysis) Curved arrows are used to indicate the movement of electrons during a nucleophilic substitution reaction.Chapter 8-2 Anatomy of a nucleophilic substitution reaction Nucleophilic Substitution Reactions Chem 61 CH3 CH I CH3 + Na+ – SH CH3OH CH3 CH SH CH3 + Na+ – I (L) Leaving Group: any group that can be displaced from a carbon atom (in this case I—) (Nu) Nucleophile: the species that attacks the carbon atom bearing L and donates the electron pair to form the nucleophile—C bond (in this case —SH) (R—I) Substrate: the molecule. By convention electron movement is written from negative to positive.

. potential energy E CASE 1:SN2 Substitution Nucleophilic 2nd order (bimolecular): sp3 CH3 CH3O – energy of transition state Eact sp2 sp3 CH3 Br δ− CH3O C H partial bonds in transition state H δ− Br CH3O C + Br– CH3 H H reactants products progress of reaction ∆H of reaction H H C Orbital Picture H Nu Nu nonbonding orbital H H Nu C H + L L nonbonding orbital H C L Nu H H C H L H C—L sigma* Nu—C sigma . A mechanism includes the transition states involved in making and breaking bonds and reactive intermediates that are formed along the pathway from reactants to products. A roadmap of a reaction..curved arrows show which bonds are formed or broken.Chapter 8-3 Nucleophilic Substitution Reactions Energetics of SN2 Chem 61 Reaction Mechanisms of Nucleophilic Substitution Reactions reaction mechanism: a detailed description of how a chemical reaction occurs..

thus the reaction is second order Rate = k[substrate][nucleophile] k is the proportionality constant called the rate constant Rate and Eact Under the same reaction conditions. The E increases due to steric hindrance of act nucleophile approach and thus the SN2 rate decreases . the reaction with the lower Eact has a faster rate Reaction 2 below is faster Eact E Eact Rxn 1 Rxn 2 Increasing alkyl group substitution at the carbon atom bonded to the leaving group hinders approach of the nucleophile.Chapter 8-4 Orientation of Nu: and L in SN2: Nucleophile approaches substrate from the backside of L Nucleophilic Substitution Reactions Chem 61 Point of highest energy along the reaction coordinate is the transition state: the O—C bond is partially formed and the C—Br bond is partially broken The Nu is bonded to the carbon on the opposite side of that occupied by the leaving group L: Net inversion of the carbon atom is observed in all SN2 reactions Reaction Rate: the time required for all substrate molecules to be converted to product The rate of an SN2 reaction is proportional to the concentrations of the substrate and the nucleophile.

e. not stepwise. primary carbon.Chapter 8-5 Relationship between Substrate Structure and SN2 Rate Alkyl halide Relative rate of SN2 CH3—X 30 CH3CH2—X 1 CH3CH2CH2—X 0.025 3 2 (CH ) C—X ~0 3 3 Nucleophilic Substitution Reactions Chem 61 Relative SN2 rate CH3—Cl + I – CH3—I + Cl – 93 1 0. no intermediates) Inversion of configuration at the carbon results from backside attack of the nucleophile The rate of SN2 reaction depends on the concentration of the nucleophile and the substrate The rate of SN2 follows the order: CH3—X > CH3CH2—X > CH3CH2CH2—X > (CH) CH—X >> (CH 3C—X 3 2 3) . or secondary carbon. i. The E increases due to steric hindrance of act nucleophile approach and thus the SN2 rate decreases SUMMARY SN2 reactions occur by the attack of a nucleophile on substrates containing the leaving group attached to a methyl.0076 CH3CH2—Cl + I– (CH ) CH—Cl + I– 3 2 CH3CH2—I + Cl– (CH ) CH—I + Cl– 3 2 Increasing alkyl group substitution at the carbon atom bonded to the leaving group hinders approach of the nucleophile.4 (CH ) CH—X 0. SN2 reactions do not occur with tertiary alkyl halides SN2 exhibit a single transition state (concerted reaction.

+ – (CH3)3C Br fast 2 Step 3: deprotonation (loss of proton) (CH3)3C O+ CH3 H Br– Step 1 involves ionization of the alkyl halide to the halide ion and the tertiary carbocation. CH3O—H ...Chapter 8-6 Nucleophilic Substitution Reactions Chem 61 CASE 2: SN1: Substitution Nucleophilic First Order (Unimolecular) Substrates containing the leaving group attached to a tertiary carbon atom react with weakly basic nucleophiles by an alternative nucleophilic substitution reaction mechanism (CH3)3C—Br + CH3OH The process involves three steps: Step 1: ionization (loss of halide ion) (CH3)3C—Br + CH3OH slow 1 Step 2: attack by the nucleophile . ROH) which solvate and thus stabilize the carbocation and the leaving group anion. (CH3)3C O+ CH3 H The transition state is pictured as (CH3)3Cδ+------δ+OCH3 H CH3 The transition state is pictured as (CH3)3C O + H H O CH3 . Step 3 involves acid-base reaction between either Br– or more likely solvent CH3OH in a very rapid reaction fast 3 (CH3)3C O CH3 + HBr (CH3)3C+ + Br – The transition state is pictured as (CH3)3Cδ+ ------Br δ– (CH3)3C—OCH3 + HBr . Ionization is aided by polar solvents (H2O. The step with the highest Eact is the slowest step (rate determining step) in the pathway.

2 X 106 the intermediate carbocation contains an sp2 hybridized carbon atom which is planar Alkyl halide + CH3 CH3 C CH3 CH3—Br CH3CH2—Br (CH3)2CH—Br (CH3)3C—Br Thus attack of CH3OH on the carbocation can occur equally from the top and bottom. tertiary alkyl halides proceed at the faster rate . but depends only on the concentration of the substrate SN1 Rate = k[substrate] The reaction is first order because the rate is proportional to the concentration of only one reactant C CH2CH2CH3 H 2O CH3CH2 CH3 *These observed reaction rates probably proceed through SN2 not SN1 SN1 rates reflect the relative Eact leading to the different carbocations (transition state 1) OH CH3 CH3CH2 C R + CH2CH2CH3 C CH2CH2CH3 (50:50) OH S Since the relative stability of carbocations is 3° > 2° > 1° > methyl.0* 11.0* 1.Chapter 8-7 Stereochemistry of SN1 reaction Nucleophilic Substitution Reactions Chem 61 Relationship Between Substrate Structure and SN1 Rate Relative SN1 rate 1. racemization of the product would be observed Br CH3 CH3CH2 R Reaction Rate of SN1 The rate of the SN1 reaction does not depend on the concentration of the nucleophile. If the carbon atom containing the leaving group were asymmetric.6 1.

Substrate CH3—X CH3CH2—X CH2=CH—CH2—X C6H5—CH2—X Realtive SN1 Rate 1. SN1 reactions occur with substrates that yield stabilized carbocations (allyl.Chapter 8-8 Allyl and benzyl primary halides Nucleophilic Substitution Reactions SUMMARY Chem 61 Allyl and benzyl primary halides are reactive substrates in both SN1 and SN2 type reactions. SN1 reactions lead to racemization. Reactions of Carbocations 1.0 33 380 Relative SN2 Rate 30 1 40 120 SN1 reactions involve an intermediate carbocation which is attacked by the nucleophile to yield the product of nucleophilic substitution. Rearrangement to a more stable carbocation: occurs whenever a more stable carbocation can be formed CH3 + CH H C CH3 CH3 CH3 + CH2 C CH3 CH3—CH=CH2 + H+ CH3 . Elimination of H+ on an adjacent carbon: E1 reactions CH3 + CH CH2 H 3. 3°. benzyl. 2°.0 1. not primary or methyl) SN1 reactions are first order in rate. Reaction with a nucleophile: SN1 reactions R+ + Nu:— or Nu: 2.

Chapter 8-9 Elimination Reactions (E1. E2) Case 1: E1: Elimination First order Elimination Reactions Chem 61 Formation of a carbocation intermediate in a reaction is a first order process. otherwise SN1 reactions are the more likely pathway Since a carbocation is involved. Once formed the carbocation may react with a nucleophile (SN1) or lose a proton from an adjacent carbon to form an alkene (E1) Thus SN1 and E1 reactions are competitive CH3 – C + Br H (CH3)3C – Nu +Br (SN1) (CH3)3C—Br CH3 H C H CH3 C CH3 CH2 + HBr (E1) E1 reactions predominate when the reaction contains only poor nucleophiles. rearangement may occur TS1‡ TS2‡ E Eact R+ R–X alkene .

RO –.Chapter 8-10 CASE 2: E2: Elimination Second Order Elimination Reactions Thus CH3CH2CH2 CHCH3 Br RO– 80°. The E2 reaction does not involve an intermediate as in the E1 reaction E2 reactions are concerted as in the SN2 reaction H RO– H C H H C H Br ROH + H H C C H H + Br– If RO– is bulky (CH3)3CO– vs. ROH Chem 61 CH3CH2CH 69% + CH3CH2CH2CH 31% CH2 CHCH3 Bimolecular elimination results when an alkyl halide is treated with a strong base (HO –. a higher percentage of the less substituted alkene results ROδ− H H H C becoming more sp2 H H ROδ− H H C H C H H Brδ− CH3CH2 CHCH3 Br CH3O – CH3CH CHCH3 + CH3CH2CH 20% + CH3CH2CH 50% CH2 80% (CH3)3CO – CH3CH CHCH3 50% C CH2 Brδ− transition state for E2 Elimination Reaction rate E2 rate = k[base][substrate] halides Direction of Elimination The more substituted (and more stable) product is normally the predominant E2 product CH2=CH2 RCH=CH2 RCH=CHR diR2C=CH2 diR2CH=CHR triR2C=CR2 tetratertiary halides > secondary halides > primary unsubstituted monoincreasing alkene stability . CH3O–. etc) at elevated temperatures (80°-120°).

in E2 reactions the proton and the leaving group must be in an anti orientation.Z alkenes. Relative rates: 3° > 2°. H Ph CH3 C C H Br H rotate Ph C Ph CH3 RO– Ph H Br Ph C CH3 Z C H Ph C In cyclohexane systems the H— and the leaving group must be trans and diaxial Cl D H H D H RO– . This allows for the best overlap of the developing pi orbitals. E2 reactions generally produce the more stable alkene (except with bulky bases or leaving groups).Chapter 8-11 Stereochemistry of E2 Elimination Reactions SUMMARY Chem 61 Generally. E1 reactions are not stereoespecific and yield a mixture of E. E2 reactions result from a concerted reaction and are competitive with SN2 reactions. E2 reactions are stereospecific and give anti elimination of H and L. E1 reactions may be accompanied by carbocation rearrangements. Relative rates: 3° > 2° > 1°. E1 reactions result from carbocation intermediates and are competivive with SN1 reactions. RO– H b c L In order to predict the stereochemistry of the alkene resulting from an E2 reaction: a) rotate the C atoms so that the H to be removed by RO– and the leaving group are in the anti conformation b) the stereochemistry of the alkene resulting from the E2 reaction is as shown a d b C a C d c + ROH + L – E1 reactions generally yield the most substituted (most stable) alkene.

H2SO4. Leaving group attached to tertiary carbon: E2 reaction observed unless Nu: is weak base. . If the solvent has low nucleophilic properties. RO–. – SR) then the reaction will follow SN2 path If the Nu: is HO – or more basic (e.E2 rates. Elimination Reactions Temperature Chem 61 Factors Governing Substitution and Elimination Reactions Structure of Alkyl Halide Leaving group attached to methyl or primary carbon: SN2 reaction observed unless Nu: is a strong base and elevated temperature employed. ROH. E1 reactions Concentration of Nucleophile or Base Increasing the concentration of the nucleophile has no effect on SN1. then the reaction will follow E2 path If the Nu: is a weak nucleophile (e. RC≡C–).Chapter 8-12 Substitution vs. i. – N3. Solvent Highly polar solvents (high dielectric constant) favor SN1. R2N–. then observe E2.g.e. – CN. E1 but increases SN2. H2O.g. H3PO4 then E1 reaction results CH3CH2OH > H2O > CH3CO2H > CF3CH2OH > CF3CO2H increasing solvent nucleophilicity Leaving group attached to secondary carbon: if the nucleophile is less basic than HO – (e. RCO2H) the reaction will follow SN1 path with some E1 The leaving group is attached to an allylic or benzylic carbon: SN1 Increase in temperature increases the rates of all reaction types but has a larger effect on E2 reactions.g. then SN1 observed. Solvent nucleophilicity increases with increasing electron releasing capacity of molecule.

7 9.3 -10.7 vs 6.5 2.7 7.3 3.7 9.8 7. Among neutral nucleophiles while (CH3CH2)3N is more basic than (CH3CH2)3P (pKa 10.7 (CH3OH2) -1.69) the phosphine is 100 times (n = 8.7 8. 5. Also N3– and CH3CO2– are nearly identical in basicity but N3– is 30 times [1.7 9.6 6. 2. (N3–. Nucleophilicity usually increases going down the periodic table (I– > Br– > Cl– > F–.8 8.9 10. Thus CH3O– > PhO– > CH3CO2–> NO3– 4.8 5.7 vs. This order is determined by electronegativity.8 5.69 8.0 1.7 6.9 -7.3 5. Nucleophilicity usually decreases going across a row in the periodic table.6 6. 8.45 4. and PhSe– > PhS– > PhO–) Related to weaker solvation and greater polarizability of the heavier atoms.4 5. 3.7 4.5 6.7 15.9 10.5 pKa of conjugate acid -1.are equivalent nucleophilicity but differ greatly in basicity.5 5.3 4. an(CH3I) = log(knucleophile/kCH3OH) in CH3OH 25°C n = nucleophilic constant . (HO– > F– .7 5. Correlation of nucleophilicity with basicity is better if the attacking atom is the same.74 9.7 15. Br.4 7. PhO–.25 4. Note that nucleophilicity toward CH3I does not correlate directly with basicity.3 6.5 Nucleophilicity General comments Chem 61 1. PhS–> Cl–).8 5.8 6.7) more nucleophilic.Chapter 8-13 NUCLEOPHILICITY Nucleophilic Constants of Various Nucleophiles Nucleophile CH3OH NO3– F– CH3CO2– Cl–≠ (CH2)2S NH3 N3– PhO – Br – CH3O– HO– NH2OH NH2NH2 (CH3CH2)3N NC– I– HOO– (CH3CH2)3P PhS– PhSe– Ph3Sn– n(CH3I)a 0.7 11.5 log units] more nucleophilic).

Chapter 8-14 Examples Nu:– 1° R CH CH2 H hindered strong base heat R L R CH CH2 H Nu Nucleophilicity E1: 3° > 2° > 1° E2: 3° > 2° > 1° SN1: 3° > 2° > 1° SN2: 1° > 2° > 3° Chem 61 SN2 (inversion CH CH2 E2 (anti elimination of HL) 3° NuH C H C L Nu: acts as base C C E2 C C C E1 – C C H C + C C H + C C Nu+ H – H+ –H C C H C Nu S N1 C H S N2 2° H C H C L poor Nu or base H C H C + C SN1 or E1 C E2 Nu: or base: – – C H C C Nu H C C C .

O .. Low molecular weight alcohols are soluble in water Alcohols contain a hydrophobic alkyl group and a hydrophilic hydroxyl group As the alkyl group increases in length and size. . acid CH3CH2O—H + Na0 CH3CH2O– Na+ + H2 . . (CH3)3C O. O . H Alcohols Chem 61 water Alcohols can hydrogen bond thus their boiling points are higher than similar polar compounds which cannot hydrogen bond. ethanol H CH3CH2 . —OH functional group bonded to an sp3 carbon.. with two lone pairs on oxygen H . . . the solubility in water decreases Acidity and Basicity alcohols act as bases in the presence of strong acids CH3CH2 base H H+ acid CH3CH2 H .O . .. H + K+H– base ..Chapter 9-1 Alcohols are similar to water: contain sp3 hybridized oxygen. O ...O+ H and as acids in the presence of strong bases (CH3)3C . .– K+ + H2 ..

. OH . secondary. benzylic CH3OH methyl CH3CH2CH2CH2CH2CH2OH primary 1° CH3CHOHCH3 secondary 2° Alcohols Chem 61 (CH3)3COH tertiary 3° CH2=CHCH2OH allylic CH2OH benzylic REACTIONS OF ALCOHOLS Substitution Reactions: Reaction with Hydrogen Halides (HX) Alcohols do not undergo nucleophilic substitution by X– since HO– is a poor leaving group. is the leaving group.. . H+ R .Chapter 9-2 IUPAC Names For alcohols drop —e from the alkane name and add —ol CH3CH2OH: ethan + ol = ethanol CH3CH2CHOHCH3: butan + ol. tertiary. primary. + O H H X– R R—X + H2O . allylic. Here the alcohol is protonated and H2O. a neutral species.. Alcohols do undergo substitution by X – in acidic solution. —OH on carbon 2: 2-butanol Classification Alcohols are classified as: methyl.

allylic and benzylic react rapidly with HCl 2° and 1° alcohols require the addition of ZnCl2 for rapid reaction with HCl Mechanism of Alcohol Substitutions Methyl and primary alcohols follow the SN2 mechanism Step 1 protonation of the alcohol CH3CH2CH2 OH H+ CH3CH2CH2 + O H H Step 2 SN2 dsiplacement of Water CH3CH2CH2 O+H H Br – S N2 CH3CH2CH2 Br + H2O . Alcohols Chem 61 E + CH3CH2CH2 CH3CH2CH2 OH O H H Reactivity of Alcohols Toward HX CH3CH2CH2 Br progress of reaction methyl primary secondary tertiary allylic and benzylic increasing reactivity of ROH toward HX All alcohols react readily with HBr and HI.Chapter 9-3 Reactivity of Hydrogen Halides The reactivity of hydrogen halides in alcohol substitution reactions is as follows: HF < HCl < HBr < HI pKa 3.45 -7 -9 -9. 3°.5 The reactivity is explained since the acidity of HX increases and the nucleophilicity of X– increases going from HF to HCl to HBr to HI.

Chapter 9-4 Secondary and tertiary alcohols follow the SN1 mechanism Step 1 protonation of the alcohol CH3 CH3 C OH Step 2 loss of water to for the carbocation CH3 CH3 + Alcohols Chem 61 H+ CH2CH3 CH3 + CH3 C OH2 CH2CH3 C OH2 CH2CH3 – H 2O CH3 CH3 C + CH2CH3 Step 3 attack of halide ion on the carbocation CH3 CH3 C + CH2CH3 X– S N1 CH3 CH3 C I CH2CH3 Rearrangement can occur R+ E R–O+H R–OH H R–X .

Chapter 9-5 Conversion of Alcohols to Alkyl Halides Chem 61 Other Reagents for the Conversion of Alcohols to Alkyl Halides R—OH + SOCl2 R—OH + PBr3 R—Cl + HCl + SO2 R—Br + HOPBr2 H CH3CH2 C OH Cl CH3 O S Cl Cl – H O– CH3CH2 C O+ S Cl CH3 Cl H H O Cl H C CH3CH2 CH3 H + CH3CH2 C OSOCl CH3 H R3N: CH3CH2 C O S Cl CH3 + SO2 Esters of Alcohols Reaction of alcohols with carboxylic acids in the presence of acid produces esters of carboxylic acids O CH3CH2CH2 C OH + CH3CH2CH2OH alcohol H+ heat O CH3CH2CH2 ester C OCH2CH2CH3 carboxylic acid .

They are readily prepared form an alcohol and the corresponding sulfonyl chloride. a sulfate ester O P OH O O P OH OH CH3O O S O OCH3 H a diphosphate ester P-toluenesulfonates (tosylates) and methanesulfonates (mesylates) are excellent leaving groups in nucleophilic substitution reactions. O CH3O S O a methanesulfonate (mesylate) CH3 + (CH3CH2)3N+HCl – CH3OH + ClSO2CH3 (CH3CH2)3N O OH + O CH3 S Cl O p-toluenesulfonylchloride (tosyl chloride) O S O CH3 cyclohexyl tosylate Reaction of sulfonates with nucleophiles CH3CH2CH2O– Na+ OTs OCH2CH2CH3 . a nitrate ester ONO2 ONO2 ONO2 H H H H C C C O H H dimethyl sulfate.Chapter 9-6 Inorganic esters Reactions of Alcohols Chem 61 mineral acids such as H2SO4. HNO3 and H3PO4 form esters with alcohols to produce important compounds H H H H C C C H nitroglycerin.

2 shift CH3 + C CH3 CH3 C H OH H+ CH3 CH3 C CH3 CH3 C H CH3 C H CH3 O+H2 OH CH CH3 CH3 H2SO4 heat CH3 CH3 – H 2O – H+ The most stable alkene predominates in dehydration reactions. H2SO4 180° C (CH3)2C=CH2 +H2O CH3CH=CH2 +H2O CH3CH=CH2 +H2O CH3 CH3 C CH3 CH3 + C CH3 – H+ CH3 C C CH3 CH3 CH3 CH3 C C CH3 C H CH3 CH3 1. E ROH2+ ROH R+ alkene progress of reaction . but primary alcohols probably eliminate by an E2 mechanism conc. Rearrangements can occur. H2SO4 (CH3)3COH ease of dehydration (CH3)2CHOH CH3CH2CH2OH Mechanism: H CH3 C CH3 H CH3 C CH3 CH3 C CH3 CH3 C+ CH3 CH3 OH H+ CH3 H C CH3 CH3 C CH3 O+H2 – H 2O CH3 60° C conc.Chapter 9-7 Elimination (Dehydration) of Alcohols Alcohols undergo elimination much like alkyl halides Dehydration of Alcohols Examples: CH2 CHCH2CH3 OH Chem 61 H+ CH CHCH2CH3 Tertiary alcohols readily undergo dehydration by an E1 pathway Secondary alcohols also follow an E1 path. H2SO4 100° C conc.

CH3CH2OCH2CH3 O diethyl ether Preparation of Ethers Williamson Ether Synthesis (SN2 Reaction of an Alkoxide with an Alkyl Halide) tetrahydrofuran CH2 O CH2 ethylene oxide R1O– + R2—X S N2 R1—O—R2 + X– Best results are obtained if the alkyl halide is methyl or primary (2° and 3° give mostly elimination) There are few limitations on the alkoxide CH3CH2CH2O – + (CH3)2CHCH2—Br CH3CH2CH2O—CH2CH(CH3)2 O– + CH3CH2—I OCH2CH3 (CH3)3CO – + CH3—I (CH3)3CO—CH3 . Ethers are less polar than alcohols and water and are not capable of hydrogen bonding to themselves because of the lack of an —OH group.Chapter 9-8 ETHERS. EPOXIDES AND SULFIDES Dehydration of Alcohols Chem 61 Ethers are derivatives of water where both hydrogens have been replaced by an alkyl group. The boiling points of ethers are also much lower than alcohols of comparable molecular weight.

. The orbitals have poor overlap and the bonds are weakened. The C—O bond is also polarized and consequently. Base Catalyzed Cleavage of Epoxides Alkoxides: CH3 C CH3 O C H CH3OH H CH3O – – O H C H OCH3 HOCH3 CH3 HO C H 3C H C H OCH3 CH3 C H 3C CH3O – nucleophile attacks at the least hindered carbon in an SN2 reaction ..Chapter 9-9 Substitution Reactions of Ethers Reactions of Ethers and Epoxides Chem 61 Ethers are relatively unreactive compounds.5°). This is a very similar reaction to the reaction of alcohols with HX Br – CH3CH2CH2—O—CH2CH2CH3 .. but they do undergo substitution reaction when heated with hydrogen halides. epoxides are highly reactive compounds. H—Br + CH3CH2CH2—O—CH2CH2CH3 H HBr CH3CH2CH2—Br + CH3CH2CH2—OH CH3CH2CH2—Br OCH2CH(CH3)2 HI OH + I—CH2CH(CH3)2 unreactive with HI Reactions of Epoxides Epoxides are strained much like cyclopropanes because their bond angles (60°) are far removed from the normal tetrahedral angle (109. particularly HI and HBr.

.Chapter 9-10 Grignard Reagents O C H C H CH3MgBr BrMgO H C H H C H CH3 H+ H Reactions of Epoxides Chem 61 HO C H H C H CH3 H H CH3–MgBr+ Acid Catalyzed Cleavage + CH3 O H H C C H CH3OH CH3 H + O CH3 δ+ C CH3 H C H . CH3OH CH3 C CH3O C H H CH3OH CH3 C C H CH3O + H H – H+ Nucleophile attacks at the most hindered carbon since the carbon is partially positive and the C—O bond is partially broken H + O H OH H H OH trans diaxial opening in cyclohexanes H H 2O . CH3O—H ..

Br HS– SH 12-crown-5 CH3CH2CH2S– I SCH2CH2CH3 Disulfides are formed by the oxidation of thiols and are an important structural feature in some proteins.Chapter 9-11 Crown Ethers Crown Ethers and Thiols Chem 61 Crown ethers are macrocyclic ethers with repeating –OCH2CH2— units. Thiols and thioethers (sulfides) are prepared by substitution reaction in the same way that alcohols and ethers are prepared. Na+ or Li+ O O O O O Na+ O K+ O O O O O 18-crown-6 Thiols and Sulfides The sulfur analog of an alcohol is a thiol. ROH = 16). Thiols are stronger acids than alcohols (pKa = 8. or mercaptan. they effectively chelate alkali metal ions such as K+. RSH I2 or K3Fe(CN)6 RS—SR a disulfide . Depending on the ring size. Thiols form weaker hydrogen bonds than alcohols due to the lower electronegativity of sulfur.

H+ . formaldehyde produces a primary alcohol O C H H 1. the carbon is a strong base and a good nucleophile. diethyl ether CH3CH2δ−—Mgδ+Br HOH CH3CH2—H CH3CH2—Br + Mg Because carbonyl pi bonds are polarized. O– C+ R1 R1 Nu: R1 Oδ− Cδ+ R1 R1 O– C Nu R1 Nucleophilic Addition O– C+ R1 R1 R2 A Grignard reaction with R1 Oδ− Cδ+ R1 R1 O– MgX+ C R2 R1 Nucleophilic Addition Mg-X 1.Chapter 9-12 Grignard Reactions Organometallic Compounds Chem 61 Grignard reagents are organometallic reagents derived from an alkyl halide and magnesium R—X + Mg diethyl ether Rδ−—Mgδ+X Grignard reagent Since the carbon carries a partial negative charge. they can undergo a reaction called nucleophilic addition: the addition of a nucleophile to an electron deficient pi bond. H2O. CH3 Mg-X H OH C CH3 H 2.

2 CH3MgBr 2.Chapter 9-13 Organometallic Compounds Chem 61 2. H CH(CH3)2 4. a ketone produces a tertiary alcohol O C CH3CH2 OH CH3 C CH2CH3 1. ethylene oxide produces a primary alcohol O 1. H+ H OH C CH2CH3 CH(CH3)2 3. H2O. H2O. H+ OH . H2O. H+ CH3 OH C CH3 5. H2O. (CH3)CHMgBr + CH3 2. C6H5MgBr 2. an aldehyde produces a secondary alcohol O C CH3CH2 H 1. (CH3)CHMgBr 2. an ester produces a tertiary alcohol (addition of two molecules of Grignard reagent) O C OCH3 1.

bond angles 180° C=C bond length = 1. the remaining two 2p orbitals are 90° to the sp and each other + 1-2p 2-sp's Acetylene: linear.20Å acetylene has two perpendicular pi bonds and one sigma bond H 2-sp's H H C C H acetylene σ-orbital H H H C C H 2-2p's on each carbon combine to form pi-orbitals C—C σ* C—C π* C—C π C—C σ acetylene π-orbitals E .Chapter 10-1 sp Hybridization sp hybridized carbons are linear with atoms 180° apart Alkynes: Structure and Bonding Chem 61 2p 2p 2s 1s 96 kcal 2p 2s 1s hybridize 1s sp ethylene: trigonal planar – + 2s 180° apart.

Thus: R C C R E+ R + C C E+ E R vinyl carbocation R C C R bridged intermediate secondary vinyl carbocation is about the same stability as a primary carbocation Thus the order of carbocation stability is triphenyl methyl > diphenylmethyl > 3°≈ benzyl ≈ allyl > 2° > 1° ≈ 2° vinyl >> methyl .Chapter 10-2 Reaction of Alkynes with E+A– Reagents Alkynes: Electrophilic Addition Chem 61 Reaction of alkynes with E+A– reagents proceed in the same manner as alkenes except different intermediates are possible R C C R E+ R + C C E+ E R vinyl carbocation R C C R bridged intermediate For H—X the vinyl carbocation is more stable than the bridged intermediate.

Chapter 10-3 For H–X HCl CH3 C C H Cl HCl CH3 C Cl CH3 C C H H Alkynes: Electrophilic Addition Chem 61 CH3 C C CH3 CH3 CH3 C C + H Cl H C CH3 For Hg(OCOCH3)2: Hg(OCOCH3)2 CH3CH2 C CH3CO2 E C CH2CH3 HgOCOCH3 C2H5C≡CC2H5 For Cl2. C6H5—C≡C—C6H5 X2 C X+ C R X C C 6H 5 X C C6 H5 C X X X C C6 H5 + C C 6H 5 C 6H 5 R C C R X X + C C6 H5 Thus the choice of intermediate depends on structure. alkyl groups tend to favor the bridged ion. groups such as phenyl which stabilize the free carbocation tend to proceed via the vinyl carbocation. . Br2: X2 R—C≡C—R R but.

Hg(II) ion is often used.Chapter 10-4 Addition of Water Alkynes: Electrophilic Addition Chem 61 With alkynes this electrophilic addition reaction generates a vinyl alcohol (also called an enol). H2SO4 Hg(II) H 2O OH R—C CH—R enol O R—C CH2—R keto R—C C—R H2O: R—C C—R Hg2+ H +OH R—C C—R Hg2+ H+ H2O: R—C OH C—R H O R—C C—R Hg2+ Hg2+ R—C H OH C—R H O R—C C—R H Hydroboration H R—C C—H BH3 R—C BH2 CH H R—C OH CH enol H O R—C H C–H keto (aldehyde) .

2 . C.7 3. The acetylide ion may be formed by such strong bases as —:NH2 (pKa 33).Chapter 10-5 H C C + base C H pKa = 45 C C H + base C . C H – – Alkynes: Acidity HF + base—H pKa 3.2 H 2O 15. thus the C—H bond is more acidic. The carbon atom is more electronegative in the sp state. RMgX or RLi (pKa 45-50). . increasing base strength R C C H NaNH2 NH3 R C C:– Na+ + NH3 acetylide ion No reaction R CH CH2 NaNH2 NH3 Electronegativities HC≡CH sp > H2C=CH2 sp 2 H3C–CH3 sp3 > Electronegativities acid strength pKa N < O < F NH3 < H2O < HF 36 15..7 HC≡CH 25 NH3 36 H2C=CH2 44 Chem 61 H3C–CH3 50 increasing acid strength + base—H F– HO– HC≡C– NH2– H2C=CH– H3C–CH2– pKa = 25 The relatively high acidity of the alkyne —C≡C—H bond is associated with the large degree of s character in the sp C—H bond (50% compared with 33% in sp2 bonds).

Chapter 10-6 SN2 reaction with acetylide ion NH3 R'—C≡C: Na – + Alkynes: Acetylides Chem 61 + R—CH2—L R—CH2—C≡C—R' R' C C:– MgBr+ + O R' C C—CH2—CH2—O – MgBr+ H+ R' C C—CH2—CH2—OH Nucleophilic addition reaction with acetylide ion. O – MgBr+ H R' C C H+ OH R' C C C H R C H CH3CH2MgBr R' C C—H R O R' C C:– MgBr+ R C O R' C C: MgBr – + + O – MgBr+ C C R' H+ OH C C R' .

Intensity of radiation is proportional to the number of photons. Absorbtion of infrared results in increased amplitudes of vibration of bonded atoms. . Ε= hc λ where c = speed of light.Chapter 12-1 Infrared and Nuclear Magnetic Resonance Spectroscopy Spectroscopy Chem 61 electromagnetic radiation: energy that is transmitted through space in the form of waves wavelength: (λ): the distance from the crest of one wave to the crest of the next wave frequency: (ν): the number of complete cycles per second ν= c λ where c = speed of light Electromagnetic radiation is transmitted in particle-like packets called photons or quanta. h = Planck's constant Ε = hν ultraviolet visible h = Planck's constant infrared radio decreasing energy Absorbtion of ultraviolet light results in the promotion of an electron to a higher energy orbital. The energy is inversely proportional to the wavelength and directly proportional to frequency.

Chapter 12-2 Infrared Spectroscopy Infrared is recorded as %T versus wavelength or frequency Infrared Spectroscopy Chem 61 When a sample absorbs at a particular wavelength or frequency. 100 %T 0 frequency Nuclei of bonded atoms undergo vibrations similar to two balls connected by a spring. Infrared energy is absorbed by molecules resulting in an excited vibrational state. Both stretching and bending vibrations can be observed by infrared. Depending on the particular atoms bonded to each other (and their masses) the frequency of this vibration will vary. O CH3 CH3 stretching O CH3 CH3 bending . %T is reduced and a peak or band is displayed in the spectrum. Infrared is recorded as %T versus wavelength or frequency When a sample absorbs at a particular wavelength or frequency. Vibrations occur in quantized energy levels and thus a particular type of bond will absorb only at certain frequencies. %T is reduced and a peak or band is displayed in the spectrum.

Some common functional groups are shown below. C(O)—OR 1640-1820 cm–1 1640-1820 cm –1 Ethers C—O 1050-1260 strong 2820-2900 and 2700-2780 cm–1 (weak but characteristic) 1640-1820 cm–1 3330-2900 cm–1 1640-1820 cm–1 1100-1300 cm–1 . C(O)—OH Esters C=O . not useful 1600-1700 cm–1 1450-1600 cm–1 2100-2250 cm–1 2800-3000 cm–1 3000-3300 cm–1 3300 cm–1 1360-1385 cm–1 (two peaks) 3500 3000 2500 2000 1500 1000 800 Alcohols and Amines O—H or N—H C—O or C—N 3000-3700 cm–1 900-1300 cm–1 Carbonyls One of the most useful absorbtions in infrared 1640-1820 cm-1 Ketones (saturated) C=O Aldehydes C=O.Chapter 12-3 Interpretation of Infrared Spectra Correlation tables Infrared Spectroscopy C—C and C—H Bonds Chem 61 Infrared spectra of thousands of compounds have been tabulated and general trends are known. OH and NH str CH str C≡N str C=O str C=N str C=C str NH bend C—O str C—N str C—C str CH bend OH bend sp3 C—C sp2 C=C sp2 C—C (aryl) sp C≡C sp3 C—H sp2 C—H sp C—H C(CH3)2 weak. C—H(O) Carboxylic acids C=O.

β Ho α Ho = the external magnetic field ∆E hν β Ho α ∆E Resonance: the flip of the magnetic moment from parallel to antiparallel to the external magnetic field. A proton which resonates at a lower magnetic field is said to be deshielded. these small magnetic moments (of the nuclei) either align with the field (α) or against the field (β). Irradiation at the frequency equal to the energy difference. Different magnetic environments are created by different electron densities in the vicinity of a proton. have a nuclear spin. others) behave as if they are spinning. 13 Nuclear Magnetic Resonance Spectroscopy Chem 61 C. causes resonance.. about 50% with and 50% against the field at any one time.. ∆E depends on the external magnetic field. ∆E. If an external magnetic field is applied. A proton which resonates at a higher field is in a stronger magnetic environment or shielded.they Spinning of a charged particle creates a magnetic moment. Protons (or other nuclei) in different magnetic environments resonate at different field strengths. .Chapter 13-1 Nuclear Magnetic Resonance (NMR) Spectroscopy Some atomic nuclei (1H.

the more electronegative the halogen. the more electronegative the halogen. This is also affected by the inductive effect of the C=O. the greater the field and the greater the shielding. pi electrons in a C=O bond create a field which deshields the proton bonded to the C=O of an aldehyde.7 H3C—I 2. The pi system of benzene creates a magnetic field or ring current which deshields the protons attached to the ring. highly electronegative atoms. Similarly. causing the carbon to be more positive and thus pulling more electrons away from the hydrogen and causing it to be less shielded.0 H3C—Br 2. In methyl halides.1 Pi electron effects Magnetic fields created by pi electrons are directional and said to have an anisotropic effect. Resonances are reported in chemical shifts (δ) downfield from tetramethylsilane (TMS) (CH3)4Si. or the hybridization of the carbon to which the proton is bonded can alter the magnetic environment. This is because F is inductively more electron withdrawing. the more deshielded the protons on the methyl. The more electron density present around the proton.Chapter 13-2 Nuclear Magnetic Resonance Spectroscopy Chem 61 Adjacent electron withdrawing groups. The local electrons create a small electric and magnetic field around a proton and shield it.3 H3C—Cl 3. the more deshielded the pr H3C—F δ 4. δ= distance from TMS in Hz MHz of spectrum ppm In methyl halides. R Ho H C O H H deshielded H deshielded .

Magnetic equivalence is usually the same as chemical equivalence. but not to CH3 protons all six are equivalent equivalent Equivalent protons can be on different carbons. replace one by a different group.Chapter 13-3 Equivalent and Nonequivalent Protons Nuclear Magnetic Resonance Spectroscopy Chem 61 Protons that are in the same magnetic environment are equivalent and have the same chemical shifts. D or Br. Protons in different magnetic fields are nonequivalent and have different chemical shifts. H H C H H C H equivalent. Then replace a different one by the same group and compare the two compounds. If protons are interconverted by rotation about a single bond. the protons are equivalent. e. mirror planes and centers of symmetry Chemically equivalent protons have the same chemical shifts. Diastereotopic hydrogens are chemically nonequivalent and thus give different chemical shifts in the NMR OH H H C H H C H C H Cl H .g. To determine if protons are chemically equivalent. Protons which are homotopic or enantiotopic resonate at the same chemical shift in the NMR. Equivalence can be established by symmetry operations such as rotation. ClH2CCH2Cl anti and gauche forms rapidly interconvert and a single resonance is observed. they will average out on the NMR time scale and a single resonance will be observed. If they are identical. Axial and equatorial hydrogens in cyclohexane average to a single peak because of rapid ring inversion.

Ha will experience two different magnetic fields and two peaks (a doublet) will appear for Ha. Spin-Spin Coupling for example. Ha will appear as a doublet Since in half the molecules. Hb will be in the α state and in half will be in the β state.Chapter 13-4 Intergration Nuclear Magnetic Resonance Spectroscopy Chem 61 The spectrometer can integrate and determine the relative number of hydrogens associated with each resonance in the NMR spectrum by determining the area under the peaks. Ha without an adjacent hydrogen For one adjacent hydrogen α or β Ha with Hb adjacent in theβ state Ha with Hb adjacent in the α state .. 3 CH3CH2OCH3 3 2 TMS If a proton (Ha) is bonded to a carbon which is bonded to a carbon that has one proton (Hb)..

Hc exist: αbαc αbβc βbαc βbβc gives 1:2:1 triplet When both Hb and Hc are α. J. Thus three signals are observed in a 1:2:1 ratio: a so-called triplet For three adjacent protons: ααα ααβ αββ βββ 1:3:3:1 quartet αβα βαβ βαα ββα Thus the splitting pattern of a particular proton or equivalent protons will be a pattern with n+1 lines where n is the number of adjacent equivalent protons. That is. βbαc and αbβc produce the same field and a single signal for Ha is observed with twice the intensity.Chapter 13-5 For two adjacent hydrogens: Hb. When one is α and one is β. a different field is observed than if both are β or one is α and one is β. . the field is the same. Hc Nuclear Magnetic Resonance Spectroscopy Chem 61 At any one time Hb or Hc could be in the α or β state (50:50) thus 4 combinations for Hb. singlet 0 neighboring protons doublet 1 neighboring protons triplet 2 neighboring protons quartet 3 neighboring protons quintet 4 neighboring protons sextet 5 neighboring protons septet 6 neighboring protons The separation of the peaks in a splitting pattern is called the coupling constant.

This is because the intermolecular hydrogen bonding in methanol allows the rapid exchange of the OH proton from one CH3OH molecule to another. the two center lines overlap and a only three lines are observed with the center line twice the height. For a dilute sample at -40° in CCl4 this is the case. since the coupling constant J is the same. Amines and other compounds which can undergo hydrogen bonding can also show this effect. concentration and solvent dependent. Thus the NMR spectra of alcohols. effectively averaging the spin states of the OH proton and resulting in no change in the magnetic field due to the OH. . If the NMR spectrum is run at 25° as a more concentrated sample only two singlets are observed.Chapter 13-6 Splitting Diagrams Nuclear Magnetic Resonance Spectroscopy Chem 61 Splitting patterns for protons can be constructed in diagram form by starting with one line to represent the unsplit proton resonance. Ha without an adjacent hydrogen splitting diagram 1 1 Ha split by one adjacent hydrogen 1 2 1 Ha split by a second adjacent hydrogen Ha split by a third adjacent hydrogen 1 3 3 1 Chemical Exchange and Hydrogen Bonding CH3OH. This can be repeated for additional adjacent protons. If an adjacent proton Hb affects Ha it is split into a doublet. amines and carboxylic acids are temperature. each line of the double will be split into a doublet. methanol would be expected to give an NMR spectrum of a doublet for the CH3 and a quartet for the OH. if another equivalent proton to Hb is present.

2-1.7 6. RCH2Cl Ether.5 1.7 1.9 3.8 3.6 3.4 1.6-1. RNH2 0.0-9.0 2.1-3. RCH2R Tertiary alkyl. ArCH2R Iodoalkane. RCH3 Secondary alkyl. RCH2C(=O)R Aldehyde.3-3.0 (variable) Nuclear Magnetic Resonance Spectroscopy Chem 61 .δ Primary alkyl.3-4.5-5.0 (variable) 0. RC≡C—H Alcoholic hydroxy. R2C=C—CH2R Benzylic.8-1.5-5.6 9.3 3.4-1.1 0. RCH2I Bromoalkane. R2C=CH2 Internal alkene. RCH2OH Ketone.7-3.2-5.2-2.0 1. Ar—H Alkyne. R2C=CHR Aromatic.5-9.6 4.4-3.1-2. RCH2Br Chloroalkane. ROH Amine.5 3.Chapter 13-7 CHEMICAL SHIFTS Functional Group Shift. RCH(O) Terminal alkene. R3CH Allylic. RCH2OR Alcohol.0 5.6-3.6-5.9 2.

A. Show all nonbonding (unshared) electrons and indicate any formal charges . 1. [H2COH]+ 6. trans. Crimmins September 15. 1998 I. M. E. or Z where appropriate. H 3C H C C CH 3 CH 2CH 3 ______________________________ 3. CH(CH3)2 ______________________________ II.CHEMISTRY 61 Exam 1 Dr. cis. Write valid Lewis structures for the following species. CH 3 Name___________________________________________ Pledge: I have neither given nor received aid on this exam. CH 2CH 2CH 2CH 3 CH 2 C H C H CH 2 CH 2 C H CH 3 CH 3 CH 3 ______________________________ 2. (6 points). CH 3 H 4. 1 . IO4 – ______________________________ 7. Signature________________________________________ Nomeclature (12 points) Give the IPUAC name for the following compounds: Indicate R.. 5. Give the hybridization of the indicated atoms in the species below (6 points) O H 3C C O CH 3 H 3C C N: H 3C N CH 2 . S.T.

e. If one is more stable than the other. diastereomers) (8 points) 10. carboxylic acid) (6 points). Draw both chair conformations of trans-1. 9. Draw all the possible stereoisomers of 3-bromo-2-butanol. 12. Draw three structural isomers for C3H6O.2-dimethylcyclohexane. Draw an energy diagram for one 360° rotation about the C3-C4 C–C bond of hexane. circle it.8. (6 points) O H C H Cl Cl B Cl H 3C O H 2 . (6 points) 11. (i. Indicate if they are chiral. Circle the molecule(s) which have a permanent dipole. enantiomers. In those which have a permanent dipole. Also draw a Newman Projection of the most stable conformation. Indicate what type of functional group is represented by each compound (e. show the direction of the overall dipole.g. (8 points). meso or achiral and indicate their relationship to each other.

CH 3 ________________________ Br H H OH ________________________ c. CH3CH3 b. H OH H 3C CH 3 a. cyclopropane c. H2C=O c. Label the species below as Lewis Acids or Lewis Bases (4 points) Br + _____________ H3CO– _____________ 16. CH 3 H 3C CH 3 Br H b. HC≡CH ____________ ______________ ______________ 3 . Indicate the geometry of carbon in the molecules below (e. (4 points) a.g. trigonal bipyramidal). (6 points) a. (9 points). What two effects cause cyclobutane and cyclopropane to be higher in energy than cyclohexane? (3 pts) 15. H CH 3 C C H 3C H H 3C CH 3 C C H H ________________________ 14. enantiomers. In the space to the right. indicate if each of the pairs of molecules below are identical compounds. diastereomers. structural isomers. or conformational isomers. cyclohexane d. cyclobutane 17. cyclopentane b. Circle the following which has the highest heat of combustion per CH2 unit.13.

They do not rotate the plane of polarized light. They have a non-superimposable mirror image.18. Circle the statement(s) which are true of enantiomers. π. (6 points) 20.g. c. They have no asymmetric carbon atoms. π*) results when the pairs of orbitals show below are combined in the indicated manner? (6 pts) + + + a. Draw an energy diagram of the molecular orbitals of the C=C bond of ethylene (H2C=CH2) and label them (e. σ) and indicate their relative energies. b. 4 . What kind of molecular orbital results (σ. b. Indicate the ground state electronic configuration of the C=C electrons. d. σ*. c. They are chiral. 19. (4 points) a.

CH 3CH 2 Name___________________________________________ Pledge: I have neither given nor received aid on this exam. cis. E.CHEMISTRY 61 Exam 1 Dr. A. Write valid Lewis structures for the following species. Signature________________________________________ Nomeclature (12 points) Give the IPUAC name for the following compounds: Indicate R. trans. OH _____________________________ 5.. (6 points). 1999 I. C(CH3)3 CH 3 _____________________________ 3. Show all nonbonding (unshared) electrons and indicate any formal charges . CH2N2 CH3– 6. or Z where appropriate. 1. H 3C CH 2CH 3 C CH 2CH 2CH 3 H _____________________________ 4. M.T. Crimmins September 21. Give the hybridization of the indicated atoms in the species below (6 points) CH 3 H 3C N CH 3 . CH 2CH 2CH 2CH 3 CH 2 C H C H C H CH 2 C H CH 3 CH 3 CH 2CH 3 CH 3 ____________________________ 2. S. H 2C C C(CH3)2 O H 3C C O CH 3 1 .

a cyclic alcohol c. Draw both chair conformations of trans-1.2-dimethylcyclohexane. What intermolecular forces exist between molecules of each of the following. a. enantiomers. CH3CH2OH 9. Write structures for the each of the following having a molecular formula of C4H8O (6 points). meso or achiral and indicate their relationship to each other. a n aldehyde b. O _________________________ _________________________ _________________________ c. (6 points). If one is more stable than the other. (i. diastereomers) (8 points) 10. an ether 8.. Label the following molecules as chiral or achiral.7. OH HO H H OH CH3 CH2OH H C CH2CH3 CH3 ______________ _____________ ______________ 11. (6 points) 2 . Indicate if they are chiral. CH 3 S CH 3 b. CH3CH2CH2CH2CH3 .e.4-dibromohexane. circle it. Draw all the possible stereoisomers of 3. a.

H CH 3 C C H 3C H H 3C CH 3 C C H H ________________________ 15. In the space to the right. Also draw a Newman Projection of the most stable conformation. (8 points).12. In those which have a permanent dipole. CH 3 ________________________ Br H b. show the direction of the overall dipole. indicate if each of the pairs of molecules below are identical compounds. CH 3 H 3C CH 3 H 3C CH 3 H 3C CH 3 CH 3 H 3C CH 3 CH 3 a. structural isomers. or conformational isomers. enantiomers. (9 points). Draw an energy diagram for one 360° rotation about the C2-C3 C–C bond of butane. diastereomers. H OH Br H H OH ________________________ c. (6 points) 14. Circle the molecule(s) which have a permanent dipole. 13. What effect(s) cause cyclobutane and cyclopentane to be non-planar? (3 pts) 3 .

Draw and label the atomic orbitals which combine to form the molecular orbitals of formaldehyde. Indicate the geometry of carbon in the molecules below (e.g. Label the species below as Lewis Acids or Lewis Bases (4 points) H3C+ _____________ H2C=CH2 _____________ 17. c. 4 . σ*. What kind of molecular orbital results (σ. π. b.16. (6 points) CH 3 H 3C C CH 3 H 2C C CH 2 CH 4 ____________ ______________ ______________ 18. . trigonal bipyramidal). (6 points) 19. π*) results when the pairs of orbitals show below are combined (mathematically) in the indicated manner? (6 pts) – + + a. H2C=O.

M.T. H2O 2. 1. H 2C C C H HBr. CH 3 Name___________________________________________ Pledge: I have neither given nor received aid on this exam. H2O 2. 1998 I. NaBH4 1 . H 3C CO 2 CH 3 C C CH 3 Cl2 1 equivalent 7. CH 3 H2. HBr CH 2 peroxide 3. CH 3 1. Hg(OAc)2. -80°C CH 2 H 8. Crimmins October 22. BH3 4.CHEMISTRY 61 Exam 2 Dr. H C H C CH 2CH 3 2. INDICATE STEREOCHEMISTRY AS NEEDED. NaOH H 1. H 3C C C CH 2 + CH 2 H H 3C C C H heat H 3C 6. Pd/C CH 3 5. (4 points each) HI 2. Signature________________________________________ REACTIONS: Predict the major organic products of the following reactions.

What is the stereochemical relationship of the products of the following reaction? H C C H Br2 H 3C a. cis-trans isomers conformational isomers ___15. CH 3 H 3C C c. b.II. Which of the carbocations below is the most stable? a. protonation of the alkene by a strong acid addition of water to a carbocation to form the protonated alcohol loss of a proton from the protonated alcohol to form the alcohol. H 3C H C CH2 d. c. In the addition of HBr to 1. Which of the following free radicals is the most stable? a. ___13. H–CH2CH2OCH3 ___12. CH 2CH 3 diastereomers enantiomers identical (only one stereosiomer of the product is formed). H . d. c. H 3C CH2 CH3 C CH CH3 c. CH 3 H C d. e. a Diels Alder reaction. H 3C C H3C C CH3 H2C CH2 CH3 b. CH 3 H 3C C c. CH3CH=CH2 c. b. Which of the following alkenes would have the lowest heat of hydrogenation? a.3-butadiene the 1.4 product predominates at 40°C.2 product predominates at -80°C while the 1. + CH 2 C d. Multiple Choice: Place the letter in the blank and Circle the best answer (only one). The 1. CH 3 . The rate limiting step for hydration of an alkene with water and acid is a. kinetic control. H H 3C H3C H C CH 3 CH CH H3C CH3 CH C CH 2 ___14. d. H . d. the s-cis diene. H H C+ CH 3 b. ___11. simultaneous addition of H+ and HO – to the alkene. (4 points each) ___9. CH3 C+ CH 3 2 . H C+ CH 3 c. CH3C≡C–H d.4 product is said to result from a. c. Which of the following indicated hydrogens is the most acidic? a. CH3CH2CH3 b. ___10. thermodynamic control. CH 3 H 3C C . b.

___16. Be sure to account for stereochemistry as needed. CH3 C CH2 CH3 X+ Y– CH3 Y X C CH2 CH3 Syntheses: Give reagents to carry out the transformations below. 17. sp3 V. Give a stepwise. O H 3C C C H H 3C C CH 2CH 3 3 . (6 points each) Br2 H3 C H CH3 Br C C CH3 H Br H 18. detailed mechanism with arrows and intermediates for the following reactions. sp2 c. sp d. s Mechanisms. What is the hybridization of the positively charged carbon in the carbocation below? + CH 2 C a. (5 points each) 19. H C H C H H ClCH 2–CH 2Cl 20. H3 C C C H b.

Does G or C form faster from E? _______________ _______________ _______________ _______________ _______________ _______________ _______________ J H N F K 22. Consider the energy diagram below and answer the questions using the letters on the diagram. Draw the HOMO (highest occupied molecular obrital) and the LUMO (lowest unoccupied molecular obrital) of 1. What point(s) in the diagram represent intermediates? c. Is the reaction endergonic or exergonic? f. What is the energy of activation for the reaction? d. What point(s) in the diagram represent transition states? b.21. (10 points). Circle the one which would interact favorably with the ethylene orbital below in a Diels-Alder reaction. (4 points) 4 . What is the free energy change of the reaction? g. What is the rate-limiting step in the reaction? e.3-butadiene and label them. B D C E N E R G Y E M A L G PROGRESS OF REACTION a.

Signature________________________________________ I. HO – H 2O (4 points each) 1 . CH3CH2 C C H NaNH2 CH3CH2Br H2O.REACTIONS: Predict the major organic products of the following reactions. CH3 C C H 3. BH3 2. CH3CH2 C C CH2CH3 H2 poisoned catalyst (Pd/BaSO4) 6. 1999 Dr.T. Crimmins Name___________________________________________ Pledge: I have neither given nor received aid on this exam. INDICATE STEREOCHEMISTRY AS NEEDED. CH3 1. 1. H2O2. CH3 H 5. Hg(OAc)2. H+ CH3 HBr. 2. M. H2 O Br2 C C H CH3 CH2CH3 1. peroxide Br2. H3 C C CH2 H3 C 9. HCl (1 equiv) CH3CH2 4. H3 C C CH2 H3 C 7.CHEMISTRY 61 Exam 2: October 21. NaBH4 2. H C C H 8.

CH3 CH2 d. d2sp3 f. overlap of a filled p orbital with an adjecent σ* antibonding orbital overlap of an empty p orbital with adjacent σ bonding orbitals resonance deduction 17. enantiomers b. c) H3 C C . b. The free energy of reaction is a. sp d. CH3 CH3 c. CH3 b) CH3 . CH3 11. b. diastereomers Br2 13. The carbon -carbon triple bond of an alkyne is composed of_________ a. Which of the following alkenes is the most stable? CH3 a. c. H2C=CHCH2+ b. (CH3)3C+ c. e. In the following reaction what is the relationship of the products formed? H CH3 a. d. What is the hybridization of the positively charged carbon in H3C+ a. CH3CH2+ 12. CH3 CH3 Which of the following is the least stable carbocation? a. s 16. structural isomers d. b. b. the difference in energy between the reactants and an intermediate in the reaction the difference in energy between the reactants and the transition state the difference in energy between the reactants and the products the difference in energy between the transition state and the products the difference in energy between the intermediate and the products 15. c. meso compound c. CH3 CH3 H 2 . d. (3 points each) 10. sp3 e. sp2 c. Multiple Choice: Circle the best answer (only one). Which of the following free radicals is the most stable? a) H3 C C H . two σ bonds and one π bond three σ bonds one σ bond and two π bonds three π bonds 14. d. p b. C6H5(CH3)2C+ d. c. CH3 d) H C . A secondary cation is more stable than a primary carbocation because of a.II.

(4 points each) 19.18. B. Draw an energy diagram for the hypothetical exergonic reaction below where B is an unstable intermediate. Which of the following is not true of H2C=CH2? a) b) c) d) It contains 5 σ bonds. and C on the diagram and indicate the energy of activation on the diagram. It has bond angles of 120°. A slow B fast C 23. It has free rotation about the C=C bond. Syntheses: Give reagents to carry out the transformations below. O HC CCH 2CH3 CH3CH2 C CH3 22. CH 3 C CH2 CH 3 OCH3 CH 3 C CH3 CH3 20. Label the positions for A. (5 points). All the atoms are in the same plane. Draw resonance structures (4 pts each) for a) benzyl cation b) acetate ion (CH3CO2–) 3 . H3 CC C–H CH3CH2CH2CH2CH3 21.

24. H+ CH3 CH3 C CH CH3 OH CH3 25.V. Give a stepwise. H3 C C H3 C CH2 HBr H3 C CH3 C Br CH3 4 . (4 points each) CH3 H3 C C C CH2 H CH3 H2 O. H3 C H C C CH3 Br2 H3 C H Br H H3 C Br H 26. Mechanisms. detailed mechanism with arrows and intermediates for the following reactions.

Which of the following are "concerted" reactions? a. d. SN1 substitution d.T. E2 elimination c. E2 e. c. The rate limiting step for free radical halogenation is a. Reaction of a strong base with a tertiary alkyl halide is most likely to result in: a. b. formation of free radicals b.CHEMISTRY 61 Exam 3 Dr. inversion of stereochemistry ___7. CH 3 OH OH CH 3 OH d. ___5. c. racemization d. Crimmins November 24. 1998 I. a. E1 elimination ___4. Free radical chlorination is more selective than bromination because the transition state is more reactant-like. H2S d. CH 3 b. initiation hydrogen atom abstraction from carbon by the halogen radical attack of carbon radical on molecular halogen termination ___2. CH 2 O H c. NH3 ___6. b. retention of stereochemistry c. Free radical chlorination is more selective than bromination because the transition state is more product-like. H2O 1 . Name___________________________________________ Pledge: I have neither given nor received aid on this exam. Which of the following statements is correct? a. Free radical bromination is more selective than chlorination because the transition state is more reactant-like. d. E1 d. SN1 and E1 f. no reaction b. SN1 reactions lead to a. Which of the folowing species is the most nucleophilic? a. H3P c. Free radical bromination is more selective than chlorination because the transition state is more product-like. SN2 c. SN2 and E2 ___3. Which of the following would undergo the fastest dehydration reaction in the presence of acid? a. (4 points each) ___1. SN1 b. M. Signature________________________________________ Multiple Choice: Place the letter in the blank and Circle the best answer (only one).

NaH 2. CH3I 12. (4 points each) CH 2CH 3 Br2.___8. CH 2 Br NaOH c. II. REACTIONS: Predict the major organic products of the following reactions. H O H NaOH. CH 2 Br NaOH d. CH 3 OH 1. 9. INDICATE STEREOCHEMISTRY AS NEEDED. CH 2Cl NaOH b. H CH(CH3)2 (CH3)3CO–K+ H Br 13. CH 3 CH 2 Br NaOH . Which of the following reactions will proceed the fastest? a. H+ 11. light 10. O C H CH 2 CH 3 CH 2 CH 2 OH. H2 O H C(CH3)3 2 .

(6 points each) CH 3 18.14. Be sure to account for stereochemistry as needed. CH 4 + Br2 heat or light CH 3 Br + HBr 3 . H Br H CH 3 CH3Se– Na+ 15. Give a stepwise. heat CH 3 Mechanisms. Br CH 3 1. H2SO4 V. H H 3C C C C CH 3 CH 3 O H CH 3 16. 17. CH 3 CH 3 OH H3PO4. detailed mechanism with arrows and intermediates for the following reactions. H2C=O 3. Mg CH 3CH 2CH 2Br 2.

Draw the transition state for the reaction of CH3Br with HO–.19. What is the structure of the alkane? (4 points) 23. CH 3 CH 3CH 2 O C CH 3 HI excess CH 3CH 2 I + I CH 3 C CH 3 CH 3 CH 3 Syntheses: Give reagents to carry out the transformations below. O CH 3 O CH 2CH 2CH 3 22. (5 points each) 20. Only one monochlorination product is obtained from an alkane with the molecular formula C5H12. (4 points) 4 . I 21.

CH3 Ph C Br CH CH2 CH3OH –1– . (4 points each) H + H CO2CH3 CO2CH3 1. If more than one product is formed give both and indicate the major product. CH3 H3C C CH2 CH2CH3 H Br2. HBr -80 °C 3. H Br NaI H CH3 5. Indicate stereochemistry where necessary.T. Reactions: Predict the major organic product of the following reactions. M. 1999 Name___________________________________________ Pledge: I have neither given nor received aid on this exam. Crimmins November 23. H 3C H Br CH3 H 2O low temperature 6. Br Ph H CH3 C C Ph H (CH3)3CO K – + 7. light 4.CHEMISTRY 61 Exam 3 Dr. Signature________________________________________ II. heat 2.

(6 points) 1. c. List three criteria for aromaticity. a. Which of the following is the strongest nucleophile? a. CH3NH– b. CH3Se- Which of the following alkyl halides would undergo the fastest SN2 reaction? CH2I b.______________________________________ 2. CH3Od. Diels-Alder reaction c.8.______________________________________ II.______________________________________ 3. e. Indicate if the following compounds are aromatic. diastereomers ___11. 9. CH3CH2CH2CH2—I d. Multiple Choice: Place the letter in the blank and Circle the best answer (only one). CH2Cl b. c. (2 points each) + H + H a. (CH3CH2)2CH—I ___14. CH3CH2CH3 + Cl2 + light → CH3CHClCH3 ___12. enantiomers b. structural isomers d. meso compound c. E1 d. CH3CH2CH3 + F2 + light → CH3CHFCH3 c. Which of the following are "concerted" reactions? a. non-aromatic or anti-aromatic. H 3C Br a. electrophilic addition e. b. d. (3 points each) In the following solvolysis reaction what is the relationship of the products formed? CH2CH3 C CH2CH2CH3 CH3OH ___10. CH3CH2CH3 + Br2 + light → CH3CHBrCH3 b. SN1 b. SN1 and E1 –2– . Which of the following reactions would proceed the fastest? a. Cl___13. CH3CH2CH3 + I2 + light → CH3CHICH3 d.

They may require more than one step. Free radical chlorination is more selective than bromination because the transition state for chlorination is more reactant-like. b. SN1 b. E2 elimination c. Free radical bromination is more selective than chlorination because the rate limiting step for bromination is more exothermic than for chlorination. CH3CH2. → CH3CH2CH2CH3 CH3CH3 + Br. E1 and E2 d.___15. CH3 CH2OH 20. SN1 and E1 Syntheses. Which of the following would be the rate limiting step in a free radical halogenation? a. Free radical bromination is more selective than chlorination because the rate limiting step for bromination is more endothermic than for chlorination. Ionization to give a carbocation and a leaving group is the rate determining step for a. Free radical bromination is more selective than chlorination because the transition state for bromination is more reactant-like. SN1 and SN2 f. d. + HBr ___18. Which of the following statements is correct? a. a. (4 pts each) 19. CH3 CH3 H 3C C CH3 CH CH3 H3 C CH3 CH3 C CH3 C CH2 –3– . c. Br2 → 2 Br. E1 e. ___17. E1 elimination ___16. SN1 substitution d. Give reagents to show how to synthesize the compounds on the right from the compounds on the left. + Br2 → CH3CH2Br + Br. Reaction of a hydroxide ion (HO–) with a primary alkyl halide is most likely to result in: a. SN2 c. 2 CH3CH2. → CH3CH2. d. c. SN2 substitution b.

V. H2C=CH CH=CH2 HBr 40 °C H3 C–CH CH=CH2 Br + H3 C–CH CH–CH2 Br –4– . Give a stepwise. Br OCH3 CH3 CH3OH CH3 + CH3 23. detailed mechanism with arrows and intermediates for the following reactions. (5 points each) 21. light CH 3CH2CH3 CH 3CHBrCH3 22. Br2. Mechanisms.

If D is a charged species and A and B are neutral. what effect will a polar protic solvent have on the rate of reaction?___________________ e. What is the thermodynamically favored product?_________ –5– . C E F E D A +B reaction coordinate G H a.24. What is the rate expression? rate = _______________ d. What is the kinetically favored product?__________ f. What happens to the rate if the concentration of A is doubled? _____________ c. What is the rate determining step?_____________ b. The energy diagram for the hypothetical reaction A + B → D → G + H is shown below. (6pts).

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