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10. Organohalides. Based on McMurry’s Organic Chemistry , 7 th edition. What Is an Organohalide?. An organic compound containing at least one halogen attached to an sp 3 hybridized carbon X (F, Cl, Br, I) replaces H Can contain many C-X bonds Properties and some uses
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10. Organohalides Based on McMurry’s Organic Chemistry, 7th edition
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
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
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
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
10.2 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
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
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.
Relative Reactivity • Based on quantitative analysis of reaction products, relative reactivity is estimated • Order parallels stability of radicals (See Figure 10-2)
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
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
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
10.5 Stability of the Allyl Radical: Resonance Revisited • Three electrons are delocalized over three carbons • Spin density surface shows single electron is dispersed
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
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
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)
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
François Auguste Victor Grignard • Born in Cherbourg, 1871 • PhD, University of Lyon, 1901 • Nobel Prize in Chemistry, 1912
Reactions of Grignard Reagents • Many useful reactions • RMgX behaves as R- (adds to C=O) • RMgX + H3O+yields R-H
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 (1893-1986)
Lithium dialkylcopper reagents react with alkyl halides to give alkanes: