Beruflich Dokumente
Kultur Dokumente
Generally the reaction is exothermic because one p and one s bond are converted to two s bonds.
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In addition reactions the alkene changes from a nucleophile in the first step to an electrophile in the second
Slow, RDS
Step I
Step II
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Electrophilic Addition of HX
The reaction has a highly endergonic first step (rate determining) and a highly exergonic second step
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The Step I is slow & it largely or entirely controls the overall rate of addition, thus it is RDS. It involves attack by an acidic , e- seeking reagent (electrophile) thus called Electrophilic Addition. The electrophile can be Bronsted acid or any e- deficient molecule a Lewis acid.
CH3 + Cl CH3
+ Cl
OSO3H
CH3 + CH3
OH2
The proposed mechanism is consistent with: 1. The orientation of addition 2. The relative reactivities of alkenes
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CH3
H3C
CH3 C H C CH3
2 cation
CH3 I
3-iodo-2,2-dimethylbutane
CH3 H3C
o
H C CH3
CH3
H3C
3 cation
2-iodo-2,3-dimethylbutene
The formation of rearranged product proves that the electrophilic addition occurs via carbocation intermediate.
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2o cation
H3C
CH
CH2
Cl isopropyl chloride H2 C
propylene
H3 C
H2 C
CH2
Cl
H3 C
CH2 Cl
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1o cation
3o cation
H3C
H3C
H C
C H
2o cation
Orientation in addition is determined by the relative rates of the two competing reactions : formation of one carbocation or the other.
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+ H:Z
C H
+ :Z
Reactants
Transition state
Products
Can we relate the rate of formation of carbocation in the Addition reaction with its stability ???
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Eact
PE
H3 C
H2 C
2o cation +:Z
Progress of reaction
Progress of reaction
The rate of addition of a proton to double bond depends upon the stability of the carbotaion being formed.
This factor determines not only the orientation of addition to a single alkene, but also relative reactivities of differ alkenes.
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>
H3C
CH
H C
CH3 H2C
>
H3C CH2
H2 C
CH C H
CH2 Cl
>
>
>
H2C
A 3o carbocation is formed faster than a 2o cation thus isobutyelene is more reactive than 2-butene The e- release by alkyl groups disperse the positive Charge & stabilizes a carbocation. The e- withdrawal by halogens intensifies positive charge & destabilizes a carbocation. Thus vinyl chloride is less reactive than ethylene.
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isobutylene CH H C CH3 + H: Z
H3C
2-butene H2 CH C 1-butene
H3C
CH2 + H: Z
H3C
CH3 + : Z
2o cation H C
+ H: Z
H3C
CH3
+ :Z
2o cation H3 C
o
+ H: Z
CH2
+ :Z
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ethylene
1 cation
Note: Alkanes do not react with bromine in the dark. 31 Above reaction used as test for alkenes.
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1. Alkenes show the same order of reactivity toward halogens as toward the acids.
Support: e- relaing groups activate alkenes whereas, ewithdrawing groups deactivate them. 2. Halonium ion intermediate is formed during reaction, which can react with other added nucleophiles (negative ion or basic molecule) to give other products. Experimental support:
if ethylene is bubbled into aq. solution of bromine & NaCl, then products obtained are Dibromo compound & Bromoalcohol.
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Br
Cl
NO3
H2O
Br H2C CH2
36 OH 2-bromoethanol
Stereospecific Reactions
A reaction is stereospecific if a particular stereoisomeric form of the starting material reacts in such a way that it gives a specific stereoisomeric form of the product Example: cis- and trans-2-butene give stereoisomeric products when halogenated
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Halohydrin Formation
Addition of Hypohalous acids
H3C CH CH2 Br2 H2O H3C Br H C CH2
propylene
H2C
CH2
Cl2 H2O
ethylene
Halohydrins are not formed by direct addition of preformed Hypohalous acid (HOX), but by the successive addition of 38 Halogen and water according to the mechanism.
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Step I
CH2 CH2
X X2 H2C CH2 + :X
OH Halohydrin
For unsymmetrical alkenes orientation follows Markonikov,s Rule: the positive halogen going to the same carbon that the hydrogen of a protic acid would go. For Propylene, Bromine attached to the terminal carbon.
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CH3 H2 C C CH3 CH3 CH3 H2 Ni H3C C H H2 C CH3 C CH3 2,4,4-trimethylpentane (isooctane) CH3
2,4,4-trimethyl-1-pentene
isobutylene
CH3 2,4,4-trimethyl-2-pentene
The alkene produced contain exactly twice the number of carbon & hydogen atoms as the isobutylene, this reaction called Dimerization. Other alkenes undergoes analogous reaction by treatment 41 with sulfuric or phosphoric acid.
Step I
isobutylene
Step II
H3C
CH3 C H2 C
Addition of isobutylene to carbocation to yield another 3o carbocation. Which may undergo similar addition to one more isobutylene to give larger molecule or may loose a proton to give dimer alkene products.
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CH3
Step III
CH3 H3 C C H2 C
H2 C
2,4,4-trimethyl-1-pentene
CH3 H3C C C H
CH3 C CH3
CH3 2,4,4-trimethyl-2-pentene
Indeed in the given case it looses a proton to give dimer alkene products. Since the proton can be lost from either side of the positively charged carbon, two alkenes should be formed. 43
isobutylene
CH3 isobutane
CH3 2,2,4-trimethylpentane
isooctane
CH3 H3C C CH2 +
Step I
H:B H3C
CH3 C CH3 + :B
isobutylene
3o cation
Step II
H3C
CH3 C H2 C
Step III
CH3 H3C C H2 C CH3 C CH3 CH3 + H CH3 C CH3 H3C
CH3 C H H2 C
CH3 isobutane
The carbocation abstracts a hydride ion ( :H- ) from alkane. This step yields an alkane and a new carbocation to continue the chain. This reaction is an example of intermolecular hydride shift and shows that carbocation is extremely strong acid (Lewis acid).
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Oxymercuration-Demercuration:
We can make Alcohols from Alkenes : Markovnikov Addition
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Oxymercuration-Demercuration
CH3 Hg(OAc)2 / THF-H2O H3CH2C C CH2 2-methyl-1-butene NaBH4, OH CH3
H3CH2C
CH3
OH tert-pentyl alcohol
H C OH
CH3
1-hexene H3C
1-methylcyclopentene
49 1-methylcyclopentanol
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CH3CH2BH2
(CH3CH2)3B triethylboron
3 H2O2 / OH
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H3C
C H
CH2
(BH3)2
H2O2 / OH
H3C
H2 C
H2 C
OH
n-proyl alcohol
H3CH2C
H2 C
H2 C
OH
H2O2 / OH
OH 3-methyl-2-butenol
H2O2 / OH H3C
H2 C
H2 C
OH
In practice, a borane complex with the solvent (THF) tetrahydrofuran is often used
Mechanism of Hydroboration
Step I
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Boron becomes attached to the least substituted carbon of the double bond. The bulky boron group can approach the least sterically hindered carbon more easily This orientation also allows a + charge in the transition state to reside at the most substituted carbon
This orientation leads to anti-Markovnikov product Reaction is highly regioselective. The boron and hydride add with syn stereochemistry
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Step I
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Step I
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Step II : Oxidation and Hydrolysis of Alkylboranes Oxidation and hydrolysis to the alcohol takes place with retention of stereochemistry at the carbon bonded to boron
Step II
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Step II
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Hydroboration of methylcyclopentene gives the anti-Markovnikov product with syn addition of the elements of water
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