addition, stereochemistry, and delocalizationocw.snu.ac.kr/sites/default/files/note/9952.pdfpart 2...
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PART 2
Addition, Stereochemistry,and Delocalization
Chapter 3. Alkenes4. Reactions of alkenes5. Stereochemistry6. Alkynes7. Electron delocalization
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Chapter 3
Alkenes
Structure and nomenclatureReactivityThermodynamics and kinetics
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Alkenes HC containing a C=C (double bond) common name ~ olefin [oil-forming] alkane ~ paraffin [little affinity]
unsaturated, CnH2n
alkane ~ saturated, CnH2n+2
degree of unsaturation [DU]
1 DU per 1 π bond or 1 ring (– 2 H) DU = (max # of H - # of H)/2
– 2 H
– 2 H
– 2 H
DU = 0 DU = 1 DU = 1 DU = 2
Ch 3 #3
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isomers of C8H14
DU = (18 – 14)/2 = 2
Do Prob 3c p122.
Having fun? Draw all the constitutional isomers of C5H8.
Ch 3 #4
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Nomenclature of alkenes similar to alkanes
common and systematic
butylene, pentylene,---?
vinyl and allyl group isobutylene
ethenyl propenylvinyl allyl allyl from allene
CH2=C=CH2hybridization?orbital structure?
allyl carbon
Ch 3 #5
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Systematic nomenclature of alkenes1. Find longest chain with =. Number to give = the lowest.
2. -ene for 1 =, -diene for 2 =‘s, -triene for 3 =‘s, ---
3. Give lowest # to =, not to subs.
hex-2-ene (more formal)
cycloocta-1,3,5,7-tetraene1,3,5,7-cyclooctatetraene
Ch 3 #6
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4. Alphabetize subs
5. (Lowest # for =, then) lowest # for subs.
6. No need to number = in cyclic alkene (always 1=2).Number subs to give lowest #.
7. If the same # for =, number subs to give lowest #.
even though 1+6 > 2+3
Ch 3 #7
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cis and trans isomers of alkenes isomers constitutional isomers ~ different connectivity Chapter 2
stereoisomers ~ different spatial arrangement geometric isomers ~ cis-trans or Z-E ~ around = or ring
enantiomers [optical isomers] ~ around chiral carbon Chapter 5
cis- and trans-2-butene
different conformation? configuration?
Ch 3 #8
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cis- and trans-2-butene two different compound
cis-isomer is of higher energy steric strain
cis-2-butene trans-2-butene
cis = ‘on the side’ trans = ‘across’
28.6 kcal/mol 27.6 kcal/mol
Ch 3 #9
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Z-E designation cis-trans designation for 1,2-disubstituted alkenes only
for tri- or tetrasubstituted ~ Z-E designation
Cl BrCl
BrBr
Cl
Br
Cl
Z isomerzusammen [‘together’]
E isomerentgegen [‘opposite’]
Ch 3 #10
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rules for priority Cahn-Ingold-Prelog sequence rule
Rule 1. higher priority for higher atomic number
Rule 2. higher atomic number at the first point of difference
Rule 3. Divide-duplicate multiple bond
C H H
Cl H H O H H
C C H
O H H C H H
C C C C
C
C
C
C
C C C
C C H
C C C C
CC
Ch 3 #11
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Prob 12(a) Draw E, Z isomers of
Box p132 isomers of
(E)-3-methylpent-2-enetrans-3-methylpent-2-ene
(Z)-2-pentenecis-2-pentene
(E)-pent-2-enetrans-2-pentene
Ch 3 #12
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Reaction mechanism mechanism ~ how the reaction proceeds
Organic reactions are interaction betw e-deficient ande-rich atoms or molecules.
functional group ~ where the reaction takes place; either electrophile ~ e-deficient ft’nal grp looks for electron (pair)
with (partial or full) positive charge, or
with incomplete octet [empty orbital]
nucleophile ~ e-rich ft’nal grp looks for electrophile
with e pair (to share with electrophile), or
with π electrons
org rxn ~ ‘A Nucleophile reacts with an electrophile.’
C = C C ≡ C
Ch 3 #13
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electrophilic addition reaction of alkenes
2-step reaction
‘substrate’
curved arrow ~e movement2 e’s to form and/or break bond
Ch 3 #14
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Drawing curved arrows Box p136
arrows follow e flow (from – to +)
arrows not for atom movement
Ch 3 #15
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arrows point to atom or bond (not to space)
arrows start at e source (e pair not atom)
For more, Study guide pp103-115
Ch 3 #16
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Thermodynamics and kinetics
reaction coordinate diagram
A----B----Ctransition state
Ch 3 #17
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Thermodynamics
∆G° = – RT ln K ∆G° = G°(products) – G°(reactants)
∆G° < 0 ~ exergonic K > 1 ~ products favored
∆G° > 0 ~ endergonic K < 1 ~ reactants favored
Table 3.1 p139 for ∆G°, K, and %product
Ch 3 #18
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∆G° = ∆H° – T ∆S°
∆S° ~ change in degree freedom change in volume, # of molecules, ---
∆H° ~ change in heat heat IN – heat OUT
Σ bond dissociation energy – Σ bond formation energy
∆H° < 0, exothermic; ∆H° > 0, endothermic
determines the direction of reaction when T∆S° is not large
Ch 3 #19
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Kinetics ∆Gǂ determines the rate of reaction. ∆Gǂ ~ free energy of activation
∆G° determines the direction.
conc’n of reactants
catalyst may help
Temperature
∆Gǂ
Ch 3 #20
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rate law 1st-order reaction ~ rate = k [A]
2nd-order reaction ~ rate = k [A][B] or k [A]2
k ~ rate constant
k = A exp [–Ea/RT] A ~ (collision) frequency factor
Ea ~ activation energy
rate and equilibrium
True activation energy is Gǂ∆Gǂ = ∆Hǂ – T∆SǂEa = ∆Hǂ + RTEa is an approximate ∆Gǂ,
and lowered by catalyst.
Ch 3 #21
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Transition state and intermediate transition state ~ [TS]ǂ
bonds partially broken or formed
unstable ~ cannot be isolated
intermediate metastable ~ may be isolated
betw steps of multi-step reactions
1st step
2nd step
RDS
Ch 3 #22