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------=_NextPart_01C81F22.6E41BC10 Content-Location: file:///C:/932A4E74/ch11ppt_files/master05.xml Content-Transfer-Encoding: quoted-printable Content-Type: text/xml; charset="utf-8" ------=_NextPart_01C81F22.6E41BC10 Content-Location: file:///C:/932A4E74/ch11ppt_files/pres.xml Content-Transfer-Encoding: quoted-printable Content-Type: text/xml; charset="utf-8" ------=_NextPart_01C81F22.6E41BC10 Content-Location: file:///C:/932A4E74/ch11ppt_files/slide0001.htm Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset="us-ascii" Chapter 11: Reactions of Alkyl Halides: Nucleophilic Substitutions a= nd Eliminations
Chapter 11: Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations
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R0lGODlhGQIKAHcAMSH+GlNvZnR3YXJlOiBNaWNyb3NvZnQgT2ZmaWNlACH5BAEAAAAALAAAAQAX AgcAgwAAAJmZuZycu5qauaGhvqGhv7q61L+/2K2tybS0zqamw7i40qysyMPD3MXF3cDA2QT/sMlJ Jbg46827B1UojtNnnmi6kWypfk4szzT93vhZ73Xu/0AYzxEsGo9IjWHJbDqf0Kh0Sq1aoUnVdXvl HL7gsHhMLo+zHrN6zT7j2m0UvD2sD9F4o312Qfj/gIGCg4SFhoeIiYqLjI2OjQmRkpOTHZSXmJma m5ydnp+goaKjpJ4Pp6ipqqusra6qeTivs68mBLe4ubq7vL2+v8DBwsPExbg4CsnKyrFHy8/Q0dLT 1NE+1djZ2tvcKQvf4OHi4+Tl5ufo6err7ObNAAHx8vP09fb3+Pn6+wHv/v8AA2YRQLCgwYMIEypU KBAAg4cQI0qcSLGixYsYM2rcyPFhw48gJkOKHEmypEkgBVKqXMmypcuXMFmahHmyps2bOHPq3MlT 5ICfACIAADs= ------=_NextPart_01C81F22.6E41BC10 Content-Location: file:///C:/932A4E74/ch11ppt_files/slide0003.htm Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset="us-ascii" Chapter 11: Reactions of Alkyl Halides: Nucleophilic Substitutions a= nd Eliminations
Goals
3D=After this chapter, you should be able to:
=3D"*"Determine the stereochemistry of SN2 reactions
=3D"*"Determine Products of SN2 vs SN1 reactions
=3D"*"Determine whether SN2, SN1, E1 or E2 will occur
3D"*"
3D"*"
3D"*"
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What is an SN2 Reaction?
3D"*"SN2 mechanism; S for substitution, N for nucleophilic and 2 because two molecules collide in the rate determining step of the reaction.
------=_NextPart_01C81F22.6E41BC10 Content-Location: file:///C:/932A4E74/ch11ppt_files/slide0038.htm Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset="us-ascii" Chapter 11: Reactions of Alkyl Halides: Nucleophilic Substitutions a= nd Eliminations
An SN2 Reaction
<= span class=3DBB>3D"*"Substitution of Bromine
<= span class=3DBB>3D"*"Nucleophile is –OCH3
3D"*"2 Molecule collision controls reaction rate
3D"*"http://fp.academic.venturacollege.edu/doliver/ochemreact= ions/reactions/Reaction05.htm
•
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Another
SN2 Reaction
3D=Substitution of Bromine
3D=Nucleophile is –:CΞN:
3D=2 Molecule collision controls reaction rate
3D"=http://fp.academic.venturacollege.edu/doliver/ochemreaction= s/reactions/Reaction06.htm
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Eliminations
Walden Inversion
•
3D"*"
P. Walden, Ber. 28,1287, 2766 (1895).
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Stereochemistry of Inversion
3D"*"If the nucleophile and the lea= ving group are both high in the R/S priority order, this means that an R alkyl halide gives an S product, and <= i>vice-versa
•
------=_NextPart_01C81F22.6E41BC10 Content-Location: file:///C:/932A4E74/ch11ppt_files/slide0006.htm Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset="us-ascii" Chapter 11: Reactions of Alkyl Halides: Nucleophilic Substitutions a= nd Eliminations
Energy of Inversion
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Energy of Inversion
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With SN2, Size of Substituent Groups Matters
Relative React= ivity Toward SN2= 3;
tertiary < secondary < primary < methyl
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------=_NextPart_01C81F22.6E41BC10 Content-Location: file:///C:/932A4E74/ch11ppt_files/slide0008.htm Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset="us-ascii" Chapter 11: Reactions of Alkyl Halides: Nucleophilic Substitutions a= nd Eliminations
Kinetics of Nucleophilic Substitution
3D=Rate =3D k[RBr][Nu-]
=3D"*"Rate depends on the concentration of both
3D=Second order kinetics
=3D"*"Two molecules collide
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Effect of Bond Strength of the Leaving Group on SN2 Reactivity
3D"*"Since the carbon-halogen bo= nd strength increases up the periodic table the relative SN2 reactivity of the alkyl halide is:
• R-F < R-Cl < R-Br < R-I = ;
•TosO- is a better leaving group than I-
•OH-, NH2-, and RO- are worse than F-
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Nucleophilicity:
 CH3CO2 (-) < Cl(-) &= lt; Br(-) &= lt; N3(-) &= lt; CH3O(-) < CN(-) &= lt; I(-) &= lt; SCN(-) &= lt; CH3S(-) 
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Nucleophilicity
3D=Parallels basicity
=3D"*"H2<= /span>O < C2H3O2- < OH-
3D=Increases down the periodic table
=3D"*"I-<= /span> < Cl- < F-
3D"*"Anions are more nucleophilic than neutral compounds
3D=The solvent matters!
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Solvent Effects
•Consider KBr as a nucleophile source&= #13;
3D=Protic solvents with –OH, -NH slow SN2 rxn
3D"*"These solvents cluster around the nucleoph= ile lowering the effective nucleophilicity
3D=Polar aprotic solvents speed SN2
3D"=These solvents cluster around the metal ion of the salt freeing the nucleophile to be nucleophilic.
3D"*"
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Characteristics of SN<= /span>2 Reactions
= 3D"*"Single Step Mechanism
= 3D"*"Inversion of configuration
SN2 rea= ctions are generally reliable only when the alkyl halide is primary
= 3D"*"Halogen is generally Cl or Br since
3D"*"C-F bond is too strong
3D"*"C-I bond is weak and compounds are unstable
------=_NextPart_01C81F22.6E41BC10 Content-Location: file:///C:/932A4E74/ch11ppt_files/slide0039.htm Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset="us-ascii" Chapter 11: Reactions of Alkyl Halides: Nucleophilic Substitutions a= nd Eliminations