Organic Chemistry M R NaimiJamal Faculty of Chemistry

Organic Chemistry M. R. Naimi-Jamal Faculty of Chemistry Iran University of Science & Technology

Chapter 1. Continue Polar Covalent Bonds Acids and Bases Based on: Mc. Murry’s Fundamental of Organic Chemistry, 4 th edition, Chapter 1

Polar Covalent Bonds: Electronegativity n n Covalent bonds can have ionic character These are polar covalent bonds n n Bonding electrons attracted more strongly by one atom than by the other Electron distribution between atoms in not symmetrical 3

Bond Polarity and Electronegativity n n Electronegativity (EN): intrinsic ability of an atom to attract the shared electrons in a covalent bond Differences in EN produce bond polarity Arbitrary scale. As shown in next figure, electronegativities are based on an arbitrary scale F is most electronegative (EN = 4. 0), Cs is least (EN = 0. 7) 4

The Periodic Table and Electronegativity 5

Bond Polarity and Electronegativity n n n Metals on left side of periodic table attract electrons weakly: lower electronegativities Halogens and other reactive nonmetals on right side of periodic table attract electrons strongly: higher electronegativities Electronegativity of C = 2. 5 6

Bond Polarity and Inductive Effect n n Nonpolar Covalent Bonds: atoms with similar electronegativities Polar Covalent Bonds: Difference in EN of atoms < 2 Ionic Bonds: Difference in electronegativities > 2 (approximately). Other factors (solvation, lattice energy, etc) are important in ionic character. 7

Bond Polarity and Inductive Effect n Bonding electrons are pulled toward the more electronegative atom in the bond n n n Electropositive atom acquires partial positive charge, + Electronegative atom acquires partial negative charge, - Inductive effect: shifting of electrons in a bond in response to the electronegativities of nearby atoms 8

Electrostatic Potential Maps n n Electrostatic potential maps show calculated charge distributions Colors indicate electron-rich (red) and electron-poor (blue) regions 9

Polar Covalent Bonds: Dipole Moments n Molecules as a whole are often polar, from vector summation of individual bond polarities and lonepair contributions 10

Polar Covalent Bonds: Dipole Moments n n Dipole moment - Net molecular polarity, due to difference in summed charges - magnitude of charge Q at end of molecular dipole times distance r between charges n n = Q r, in debyes (D) 1 D = 3. 34 10 30 coulomb meter 11

Dipole Moments in Water and Ammonia n Large dipole moments n Electronegativities of O and N > H n Both O and N have lone-pair electrons oriented away from all nuclei 12

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Practice: Suggest an explanation Ammonia (NH 3) has a dipole moment of 1. 46 D, while the dipole moment of NF 3 is only 0. 24 D. Why? 14

Absence of Dipole Moments n n In symmetrical molecules, the dipole moments of each bond has one in the opposite direction The effects of the local dipoles cancel each other 15

Cis- & trans-1, 2 -dichloroethylenes: 16

Formal Charges n n Sometimes it is necessary to have structures with formal charges on individual atoms We compare the bonding of the atom in the molecule to the valence electron structure If the atom has one more electron in the molecule, it is shown with a “-” charge If the atom has one less electron, it is shown with a “+” charge 17

Formal Charges 18

Nitromethane: 19

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Formal Charges 21

Resonance n n n Some molecules have structures that cannot be shown with a single Lewis representation In these cases we draw Lewis structures that contribute to the final structure but which differ in the position of the bond(s) or lone pair(s) Such a structure is delocalized and is represented by resonance forms 22

Resonance n The resonance forms are connected by a doubleheaded arrow 23

Resonance Hybrids n n n A structure with resonance forms does not alternate between the forms Instead, it is a hybrid of the two resonance forms, so the structure is called a resonance hybrid For example, benzene (C 6 H 6) has two resonance forms with alternating double and single bonds n In the resonance hybrid, the actual structure, all of the C-C bonds are equivalent, midway between double and single bonds 24

Resonance Hybrids 25

Resonance Hybrids 26

Rules for Resonance Forms n n n Individual resonance forms are imaginary - the real structure is a hybrid (only by knowing the contributors can you visualize the actual structure) Resonance forms differ only in the placement of their or nonbonding electrons Different resonance forms of a substance don’t have to be equivalent Resonance forms must be valid Lewis structures: the octet rule usually applies The resonance hybrid is more stable than any individual resonance form would be 27

Curved Arrows and Resonance Forms n n We can imagine that electrons move in pairs to convert from one resonance form to another A curved arrow shows that a pair of electrons moves from the atom or bond at the tail of the arrow to the atom or bond at the head of the arrow 28

Curved Arrows and Resonance Forms 29

Drawing Resonance Forms Any three-atom grouping with a multiple bond has two resonance forms 30

Different Atoms in Resonance Forms n Sometimes resonance forms involve different atom types as well as locations n The resulting resonance hybrid has properties associated with both types of contributors n The types may contribute unequally 31

Resonance in the acetone enolate The “enolate” derived from acetone is a good illustration, with delocalization between carbon and oxygen. 32

2, 4 -Pentanedione n The anion derived from 2, 4 -pentanedione n n Lone pair of electrons and a formal negative charge on the central carbon atom, next to a C=O bond on the left and on the right Three resonance structures result 33

Practice: Draw three resonance forms: 34

Solution: 35

Practice: Draw three resonance forms: 36

Solution: 37

Solution: 38

Acids and Bases: The Brønsted–Lowry Definition n n Brønsted–Lowry theory defines acids and bases by their role in reactions that transfer protons (H+) between donors and acceptors. “proton” is a synonym for H+ - loss of an electron from H leaving the bare nucleus - a proton. Protons are always covalently bonded to another atom. 39

Brønsted Acids and Bases n n n “Brønsted-Lowry” is usually shortened to “Brønsted” A Brønsted acid is a substance that donates a hydrogen ion, or “proton” (H+): a proton donor A Brønsted base is a substance that accepts the H+: a proton acceptor 40

The Reaction of HCl with H 2 O n n n When HCl gas dissolves in water, a Brønsted acid– base reaction occurs HCl donates a proton to water molecule, yielding hydronium ion (H 3 O+) and Cl The reverse is also a Brønsted acid–base reaction of the conjugate acid and conjugate base 41

The Reaction of HCl with H 2 O 42

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Quantitative Measures of Acid Strength n n n The equilibrium constant (Keq) for the reaction of an acid (HA) with water to form hydronium ion and the conjugate base (A-) is a measure related to the strength of the acid Stronger acids have larger Keq Note that brackets [ ] indicate concentration, moles per liter, M. 44

Ka – the Acidity Constant n n n The concentration of water as a solvent does not change significantly when it is protonated in dilute solution. The acidity constant, Ka for HA equals Keq times 55. 6 M (leaving [water] out of the expression) Ka ranges from 1015 for the strongest acids to very small values (10 -60) for the weakest 45

Ka – the Acidity Constant 46

Acid and Base Strength n n n The ability of a Brønsted acid to donate a proton to is sometimes referred to as the strength of the acid. The strength of the acid can only be measured with respect to the Brønsted base that receives the proton Water is used as a common base for the purpose of creating a scale of Brønsted acid strength 47

p. Ka – the Acid Strength Scale n n n p. Ka = -log Ka (in the same way that p. H = -log [H+] The free energy in an equilibrium is related to –log of Keq (DG = -RT log Keq) A larger value of p. Ka indicates a stronger acid and is proportional to the energy difference between products and reactants 48

p. Ka – the Acid Strength Scale The p. Ka of water is 15. 74 49

p. Ka values for some acids: 50

Predicting Acid–Base Reactions from p. Ka Values n n p. Ka values are related as logarithms to equilibrium constants The difference in two p. Ka values is the log of the ratio of equilibrium constants, and can be used to calculate the extent of transfer 51

Predicting Acid–Base Reactions from p. Ka Values 52

Predicting Acid–Base Reactions from p. Ka Values 53

Organic Acids and Organic Bases n n The reaction patterns of organic compounds often are acid-base combinations The transfer of a proton from a strong Brønsted acid to a Brønsted base, for example, is a very fast process and will always occur along with other reactions 54

Organic Acids n n Those that lose a proton from O–H, such as methanol (CH 3 OH) and acetic acid (CH 3 COOH) Those that lose a proton from C–H, usually from a carbon atom next to a C=O double bond (O=C– C– H) 55

Organic Acids 56

Organic Acids: 57

Carboxylic Acids: 58

Conjugate Bases: 59

Organic Bases n Have an atom with a lone pair of electrons that can bond to H+ n Nitrogen-containing compounds derived from ammonia are the most common organic bases n Oxygen-containing compounds can react as bases when with a strong acid or as acids with strong bases 60

Organic Bases 61

Acids and Bases: The Lewis Definition n n Lewis acids are electron pair acceptors; Lewis bases are electron pair donors The Lewis definition leads to a general description of many reaction patterns but there is no quantitatve scale of strengths as in the Brønsted definition of p. Ka 62

Lewis Acids and the Curved Arrow Formalism n The Lewis definition of acidity includes metal cations, such as Mg 2+ n n n They accept a pair of electrons when they form a bond to a base Group 3 A elements, such as BF 3 and Al. Cl 3, are Lewis acids because they have unfilled valence orbitals and can accept electron pairs from Lewis bases Transition-metal compounds, such as Ti. Cl 4, Fe. Cl 3, Zn. Cl 2, and Sn. Cl 4, are Lewis acids 63

Lewis Acids and the Curved Arrow Formalism n n Organic compounds that undergo addition reactions with Lewis bases (discussed later) are called electrophiles and therefore Lewis Acids The combination of a Lewis acid and a Lewis base can shown with a curved arrow from base to acid 64

Illustration of Curved Arrows in Following Lewis Acid-Base Reactions 65

Some Lewis Acids: 66

Lewis Bases n n n Lewis bases can accept protons as well as other Lewis acids, therefore the definition encompasses that for Brønsted bases Most oxygen- and nitrogen-containing organic compounds are Lewis bases because they have lone pairs of electrons Some compounds can act as either acids or bases, depending on the reaction 67

Some Lewis Bases 68

Lewis Acid-Base Reactions 69

Imidazole: 70

Drawing Chemical Structures n n Condensed structures: C-H and C-C and single bonds aren't shown but understood n If C has 3 H’s bonded to it, write CH 3 n If C has 2 H’s bonded to it, write CH 2; and so on. Horizontal bonds between carbons aren't shown in condensed structures - the CH 3, CH 2, and CH units are assumed to be connected horizontally by single bonds, but vertical bonds are added for clarity 71

2 -methylbutane Structures 72

Skeletal Structures n n Minimum amount of visual information but unambiguous C’s not shown, but assumed to be at each intersection of two lines (bonds) and at end of each line H’s bonded to C’s aren't shown – whatever number is needed will be there to fill out the four bonds to each carbon. All atoms other than C and H are shown 73

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Practice: How many H’s on each carbon? 75

Solution: 76

Problem: How many H’s on each carbon? 77

Molecular Models n n n We often need to visualize the shape or connections of a molecule in three dimensions Molecular models are three dimensional objects, on a human scale, that represent the aspects of interest of the molecule’s structure (computer models also are possible) Drawings on paper and screens are limited in what they can present to you 78

Molecular Models n Framework models (ball-and-stick) are essential for seeing the relationships within and between molecules – you should own a set n Space-filling models are better for examining the crowding within a molecule Framework Space-filling 79

Summary n n Organic molecules often have polar covalent bonds as a result of unsymmetrical electron sharing caused by differences in the electronegativity of atoms The polarity of a molecule is measured by its dipole moment, . (+) and ( ) indicate formal charges on atoms in molecules to keep track of valence electrons around an atom Some substances must be shown as a resonance hybrid of two or more resonance forms that differ by the location of electrons. 80

Summary n A Brønsted(–Lowry) acid donates a proton n A Brønsted(–Lowry) base accepts a proton n The strength Brønsted acid is related to the -1 times the logarithm of the acidity constant, p. Ka. Weaker acids have higher p. Ka’s A Lewis acid has an empty orbital that can accept an electron pair A Lewis base can donate an unshared electron pair 81

Summary n n n In condensed structures C-C and C-H are implied Skeletal structures show bonds and not C or H (C is shown as a junction of two lines) – other atoms are shown Molecular models are useful for representing structures for study 82

Chapter 1 -2, Questions 42, 43, 44, 46, 47, 50, 54, 55, 57 83