Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 37

Chap. 12 Structure Determination: MS and IR 12.1-11.2 Mass Spectrometry a) Basics

b) Mass spectrum

c) High-Resolution MS

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 38

12.2-12.4 Fragmentation patterns (skipped) 12.5 Spectroscopy a) Definition: the study of interactions between electromagnetic radiation and molecules.

b) Principles

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 39

12.6-12.7 IR Spectroscopy a) Position of absorption b) Intensity

c) Four regions

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 40

12.8 IR spectra of some common functional groups a) Hydrocarbons

Backbone of most organic compounds, only C-H and C-C C-H C-C Alkane (C-C) 28502960 cm-1 (8001300 cm-1) Alkene (C=C) 30203100 cm-1 16401680 cm-1 Alkyne (CC-H) 3300 cm-1 21002260 cm-1 Internal CC none weak or none

b) Oxygen-containing compounds

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 41

Chap. 13 Structure Determination: NMR 13.1-13.3 NMR spectroscopy a) Basics:

b) Chemical shift

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 42

c) Timescale d) Operational issues 13.4-13.7 13C NMR a) Position of absorption

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 43

b) Intensities of the signals c) DEPT

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 44

d) Applications 13.8-13.10 1H NMR a) Position of absorption b) Equivalence test: replacement of two Hs with X, respectively

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 45

c) Chemical Shifts

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 46

c) Intensities

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C5H12O (1:3)

C8H10 (2:3)

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C6H12O (1:3)

C6H12O (1:1)

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 47

13.11-13.12 Spin-spin splitting (Multiplicity)

# of Hs on adjacent C # of peaks in multiplet Area ratio 0 1 2 3 4 5 6

1 (singlet) 2 (doublet) 3 (triplet) 4 (quartet) 5 (quintet) 6 (sextet) 7 (septet)

1 1 1

1 2 1 1 3 3 1

1 4 6 4 1 1 5 10 10 5 1

1 6 15 20 15 6 1 Give examples of OCH3, OCH2CH3, OCH(CH3)2, and OC(CH3)3

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Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 48

13.11-13.12 Solving structures using 1H NMR

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Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 49

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Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 50

Chap. 6 An Overview of Organic Reactions 6.1 Four basic types of Organic Reactions

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 51

6.2-6.3 Radical Mechanisms a) Mechanism

Half-headed curved arrows (fishhook) show movement of ONE electron (radical reactions)

Full-headed curved arrows show movement of ONE PAIR of electrons (polar reactions)

b) Radical reactions

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 52

6.4-6.6 Polar Mechanisms a) Polarity vs Polarizability b) Polar reactions (remember to follow the flow of electrons) (The 3rd most important concept in organic chemistry)

E+ or E+ = electrophile or electron sink (Lewis acid), loves electrons (must have empty orbitals for electrons)

Nu- or Nu = nucleophile or electron source (Lewis base), loves nucleus (positive charge), rich in electrons

Electrons always go from Nu (electron source) to E (electron sink)

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 53

6.7-6.10 Thermodynamic and Kinetics

a) Thermodynamics

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 54

b) Calculation of H using Bond dissociation energy (BDE)

CH3H 438 kJ/mol HCl 432 kJ/mol CH3Cl 351 kJ/mol ClCl 243 kJ/mol HBr 366 kJ/mol CH3Br 293 kJ/mol BrBr 193 kJ/mol HI 298 kJ/mol CH3I 234 kJ/mol II 151 kJ/mol

c) Reaction rate theory d) Reaction energy diagrams

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 55

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 56

Chap. 7 Alkenes: Structure and Reactivity 7.1-7.2 Unsaturated compounds Alkane (sp3) Alkene (sp2) Alkyne (sp)

Degree of unsaturation: CaHbOcNdXe

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 57

7.3-7.5 Nomenclature a) Rules for alkenes

Longest chain containing C=C Number the chain to give lowest number to C=C Number and name other substituents Assign (E) or (Z) prefix as needed

E = entgegen = opposite Z = zusammen = together = ze zame side the same side Priority: higher atomic number (if tie, count next atom) If double (or triple) bond, count twice (or three times)

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 58

7.6 Stability of alkenes a) Equilibrium

b) Heat of hydrogenation

c) General trend

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 59

7.7-6.10 Electrophilic Addition of HX a) Electrophilic addition reaction b) Markovnikovs rule

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 60

c) Carbocations (planar, sp2 hybridization) 7.10 Hammond Postulate

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 61

7.11 Carbocation Rearrangement

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 62

Chap. 8 Alkenes: Reactions and Synthesis 8.1 Addition/Elimination a) Dehydrohalogenation (-HX): Remove H and X on adjacent carbons only b) Dehydration of alcohols (-H2O): Remove H and OH on adjacent carbons only

8.2-8.4 Addition reactions a) General

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 63

b) Addition of halogens c) Halohydrin formation

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 64

d) Addition of water

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 65

8.5-8.6 More Addition reactions a) Hydroboration

b) Reduction/hydrogenation

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 66

8.7-8.8 Oxidation a) Epoxide b) OsO4 (osmium tetroxide)

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 67

c) Ozonolysis 8.9 Addition of carbenes

Chem 331 Organic Chemistry Iowa State University

Notes for Organic Chemistry, John McMurry, 8th Ed., 2015 Yan Zhao 68

8.10 Brief introduction of polymer 8.12-8.13 Stereochemistry of reactions

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