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p. 445
Chapter 12: Organohalides
12.5 – 12.15 : Substitution and Elimination Reactions12.4 : The Grignard Reagent12.1-12.3 : Preparation of Alkyl Halides
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Fig. 12-2, p. 455
The Walden Inversion Cycle (1896)
(+)-Maleic Acid[]D = +2.3
(-)-Maleic Acid[]D = -2.3
(+)-chlorosuccinic acid
(-)-chlorosuccinic acid
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Fig. 12-5, p. 459
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Characteristics of the SN2 reaction
1.Rate equation
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Characteristics of the SN2 reaction
1.Rate equation
2.Molecular factors effecting SN2 reaction rate
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Fig. 12-6, p. 460
The Effect of Reactant and Transition Structure Energies on Reaction Rate
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p. 461
Effect of ELECTROPHILIC CARBON on SN2 rate
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Fig. 12-7, p. 461
Effect of ELECTROPHILIC CARBON on SN2 rate
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The sterics around the electrophilic carbon alters the SN2 rate by changing…
0%
0% A. The ground state energy of the starting materials.
B. The energy of the transition state.
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Effect of ELECTROPHILIC CARBONon SN2 rate
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p. 463
Effect of LEAVING GROUP on SN2 rate
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The leaving group alters the SN2 rate by changing…
0%
0% A. The ground state energy of the starting materials.
B. The energy of the transition state.
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Effect of LEAVING GROUP on SN2 rate
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Table 12-2, p. 462
Effect of NUCLEOPHILE on SN2 rate
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The nucleophile alters the SN2 rate by changing…
52%
48% A. The ground state energy of the starting materials.
B. The energy of the transition state.
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Effect of NUCLEOPHILE on SN2 rate
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p. 465
Effect of Solvent on SN2 rate
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Poorly solvated anion(increased nucleophilicity)
O
CNH
CH3
CH3
+
-
OC
N
H
CH3
H3C
O
CN H
H3C
CH3
O CN
H
H3C
CH3
++
+-
-
-X-
Well solvated anion(reduced nucleophilicity)
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The solvent alters the SN2 rate by changing…
20%
80% A. The ground state energy of the starting materials.
B. The energy of the transition state.
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O
CNH
CH3
CH3
+
-
OC
N
H
CH3
H3C
O
CN H
H3C
CH3
O CN
H
H3C
CH3
++
+-
-
-X-
Solvent effects on SN2 rate
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Fig. 12-8, p. 466
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Characteristics of the SN1 reaction
1.Rate equation
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Characteristics of the SN1 reaction
1.Rate equation
2.Molecular factors effecting SN1 reaction rate
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p. 467
Effect of electrophilic carbon on SN1 rate
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Fig. 12-11, p. 469
Stereochemical effects of the SN1 mechanism
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Fig. 12-12, p. 470
Stereochemical effects of the SN1 mechanism
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p. 472
Effect of electrophilic carbon on SN1 rate:
Carbocation Stability
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Fig. 12-13, p. 471
Effect of electrophilic carbon on SN1 rate:
Resonance in Carbocations
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p. 472
Bond Disassociation Energies and Carbocation Stability
<
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p. 472
Effect of LEAVING GROUP on SN2 rate
Effect of LEAVING GROUP on SN1 rate
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Fig. 12-15, p. 474
Effect of Solvent on SN1 rate
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p. 474
Effect of Solvent on SN1 rate
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SN2 vs. SN1
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What is the mechanism for the reaction below?
50%
50% A. SN1
B. SN2
Cl NaI
DMF
I
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What is the mechanism for the reaction below?
50%
50% A. SN1
B. SN2
CH3
OHCH3
ClHClH2O
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What is the mechanism for the reaction below?
50%
50% A. SN1
B. SN2
OHHBr
BrCH3CO2H
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What is the mechanism for the reaction below?
50%
50% A. SN1
B. SN2
BrCH3ONa
OCH3CH3OH
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Elimination Reactions
1.Intro: Eliminations vs. Substitutions
The E2 Mechanism
1.Rate
2.Molecular factors effecting the E2 mechanism
Stereochemistry
Zaitzev’s Rule
Barton’s Experiments
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Fig. 12-19, p. 482
Stereochemistry of the E2 mechanism
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Elimination Reactions : The E1 Mechanism
1.Rate
2.E1 and SN1
3.Molecular factors effecting the E2 mechanism
Stereochemistry
Zaitzev’s Rule
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Summing it all up : SN1, SN2, E1 and E2
1. Primary Alkyl Halides
2. Secondary Alkyl Halide
3. Tertiary Alkyl Halides
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Table 12-1, p. 446
Properties of Alkyl Halides
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p. 447
Properties of Alkyl Halides
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p. 453
The Grignard Reagent
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p. 227
Synthesis of alkyl halides : review1. Addition of HX to an alkene (section 7.6)
a. Obeys Markovnikov’s Rule (section 7.7)
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p. 239
Synthesis of alkyl halides : review1. Addition of HX to an alkene (section 7.6)
a. Obeys Markovnikov’s Rule (section 7.7)b. Carbocations that can rearrange, will rearrange (section 7.10)
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p. 255
Synthesis of alkyl halides : review2. Addition of X2 to an alkene (section 8.2)
Anti addition
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p. 255
Synthesis of alkyl halides : review3. Radical Halogenation (section 6.3)
CH3
CC
CH3
HH
H H
+Cl2
CH3
CC
H2C
HH
H HClCH3
CC
CH3
HH
H Clheator
light
Statistical
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Synthesis of alkyl halides : New
1. From alkynes
Allylic bromination with N-Bromo
Succinimide
2. From Alcohols
a. Using strong acid
b. Via Tosylates
c. Using SOCl2 and PBr3
N
O
O
Br
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Fig. 12-1, p. 449
The Allyl Radical
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End