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Based on McMurry’s Organic Chemistry, 7th edition

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1 Based on McMurry’s Organic Chemistry, 7th edition
10. Organohalides Based on McMurry’s Organic Chemistry, 7th edition

2 What Is an Organohalide?
An organic compound containing at least one halogen attached to an sp3 hybridized carbon X (F, Cl, Br, I) replaces H Can contain many C-X bonds Properties and some uses Fire-resistant solvents Refrigerants Pharmaceuticals and precursors


4 Epibatidine (200X more effective than morphine!)

5 Vancomycin (antibiotic from amycolatopsis orientalis):

6 10.1 Naming Alkyl Halides Name is based on longest carbon chain
(Contains double or triple bond if present) Number from end nearest any substituent (alkyl or halogen) Halogens have same priority as alkyl groups


8 Naming with Multiple Halides
If more than one of the same kind of halogen is present, use prefix di, tri, tetra If there are several different halogens, number them and list them in alphabetical order

9 Naming if Two Halides or Alkyl Are Equally Distant from Ends of Chain
Begin at the end nearer the substituent whose name comes first in the alphabet

10 Many Alkyl Halides That Are Widely Used Have Common Names

11 10.2 Structure of Alkyl Halides
C-X bond is longer as you go down periodic table C-X bond is weaker as you go down periodic table C-X bond is polarized with slight positive on carbon and slight negative on halogen

12 Properties of the Halomethanes


14 10.3: Radical Halogenation
Alkane + Cl2 or Br2, initiated by heat or light; replaces C-H with C-X Hard to control for monosubstitution Reacts via a free radical mechanism See mechanism in Figure 10-1 It is usually not a good idea to plan a synthesis that uses this method


16 Multiple Substitution

17 Radical Halogenation of Alkanes
If there is more than one type of hydrogen in an alkane, the reaction favors replacing the hydrogen at the most highly substituted carbons: 3o>2o>1o The number of available hydrogens is a factor Methyl hydrogens, for example, often outnumber 2o or 3o hydrogens.

18 Chlorination is unselective:

19 Relative Reactivity Based on quantitative analysis of reaction products, relative reactivity is estimated Order parallels stability of radicals (See Figure 10-2)



22 Bromination is much more selective than chlorination:

23 10.4 Preparing Alkyl Halides
Alkyl halide is formed by the addition of HCl, HBr, HI to alkenes to give the Markovnikov product (see Alkenes chapter) Alkyl geminal dihalide from anti addition of bromine or chlorine

24 10.5 Allylic Bromination of Alkenes
N-bromosuccinimide (NBS) selectively brominates allylic positions Requires light for activation: a source of bromine atoms at very low concentrations

25 Allylic Bromination of Alkenes


27 Allylic Stabilization

28 Allylic Stabilization
Allyl radical is delocalized More stable than typical alkyl radical by 40 kJ/mol (9 kcal/mol Allylic radical is more stable than tertiary alkyl radical

29 10.5 Stability of the Allyl Radical: Resonance Revisited
Three electrons are delocalized over three carbons Spin density surface shows single electron is dispersed

30 Allylic Resonance:

31 Allylic Radicals as Reaction Intermediates:

32 Use of Allylic Bromination
Allylic bromination with NBS creates an allylic bromide Reaction of an allylic bromide with base produces a conjugated diene, useful in synthesis of complex molecules

33 Practice Problem 10.1: Products?

34 Problem 10.5: Draw resonance forms

35 Problem 10.5

36 Problem 10.6: Explain?

37 Problem 10.6: mechanism

38 10.6 Preparing Alkyl Halides from Alcohols
Reaction of tertiary C-OH with HX is fast and effective Add HCl or HBr gas into ether solution of tertiary alcohol Primary and secondary alcohols react very slowly and often rearrange, so alternative methods are used

39 Reactivity of Alcohols with HX

40 Preparation of Alkyl Halides from Primary and Secondary Alcohols
Specific reagents avoid acid and rearrangements of carbon skeleton Thionyl chloride converts alcohols into alkyl chlorides (SOCl2 : ROH to RCl) Phosphorus tribromide converts alcohols into alkyl bromides (PBr3: ROH to RBr)


42 Problem 10.23: Products?

43 Prob. 10.8: Synthesize from alcohols?

44 10.7 Reactions of Alkyl Halides: Grignard Reagents
Reaction of RX with Mg in ether or THF Product is RMgX – an organometallic compound (alkyl-metal bond) R is alkyl 1°, 2°, 3°, aryl, alkenyl X = Cl, Br, I

45 François Auguste Victor Grignard
Born in Cherbourg, 1871 PhD, University of Lyon, 1901 Nobel Prize in Chemistry, 1912

46 Grignard Carbon as Nucleophile:

47 Reactions of Grignard Reagents
Many useful reactions RMgX behaves as R- (adds to C=O) RMgX + H3O+ yields R-H

48 10.8 Organometallic Coupling Reactions
Alkyllithium (RLi) forms from RBr and Li metal RLi reacts with copper iodide to give lithium dialkylcopper (Gilman reagents) Henry Gilman ( )


50 Lithium dialkylcopper reagents react with alkyl halides to give alkanes:

51 Problem (continued):

52 Utility of Organometallic Coupling in Synthesis
Coupling of two organometallic molecules produces larger molecules of defined structure Aryl and vinyl organometallics also effective Coupling of lithium dialkylcopper molecules proceeds through trialkylcopper intermediate

53 10.9 Oxidation and Reduction in Organic Chemistry
In organic chemistry, oxidation occurs when a carbon or hydrogen that is connected to a carbon atom in a structure is replaced by oxygen, nitrogen, or halogen Not easily recognizable as loss of electrons by an atom as in inorganic chemistry Oxidation is a reaction that results in loss of electron density at carbon (as more electronegative atoms replace hydrogen or carbon) Oxidation: loss of H, and/or gain of O, N, X

54 Reduction: gain of H and/or loss of O, N, X
Reduction Reactions Organic reduction is the opposite of oxidation Results in gain of electron density at carbon (replacement of electronegative atoms by hydrogen or carbon) Reduction: gain of H and/or loss of O, N, X



57 Oxidation Levels Functional groups are associated with specific oxidation levels

58 Practice Problem 10.2: Rank in order of increasing oxidation level

59 Problem 10.13: oxidation or reduction?

60 Problem 10.33: oxidation or reduction?

61 Problem 10.39: Identify reagents

62 Problem 10.39 a = BH3/THF followed by H2O2/OH-1 (hydroboration/oxidation) b = PBr3/ether c = (CH3)2CuLi/ether

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