Alkenes, Reactions. NR some NR Acids Bases Metals Oxidation Reduction Halogens R-H R-X...
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Transcript of Alkenes, Reactions. NR some NR Acids Bases Metals Oxidation Reduction Halogens R-H R-X...
Alkenes, Reactions
NR NR
NR some NR NR
NR NR NR
NR NR NR
NR NR NR
NR NR NR NR
Acids
Bases
Metals
Oxidation
Reduction
Halogens
R-H R-X R-OH R-O-R Alkenes
Alkenes, reactions.
Addition
ionic
free radical
Reduction
Oxidation
Substitution
Reactions, alkenes:
1. Addition of hydrogen (reduction).
2. Addition of halogens.
3. Addition of hydrogen halides.
4. Addition of sulfuric acid.
5. Addition of water (hydration).
6. Addition of aqueous halogens (halohydrin formation).
7. Dimerization.
8. Alkylation.
9. Oxymercuration-demercuration.
10. Hydroboration-oxidation.
11. Addition of free radicals.
12. Polymerization.
13. Addition of carbenes.
14. Epoxidation.
15. Hydroxylation.
16. Allylic halogenation
17. Ozonolysis.
18. Vigorous oxidation.
1. Addition of hydrogen (reduction).
| | | |— C = C — + H2 + Ni, Pt, or Pd — C — C —
| | H Ha) Requires catalyst.b) #1 synthesis of alkanes
CH3CH=CHCH3 + H2, Ni CH3CH2CH2CH3
2-butene n-butane
Alkanes
Nomenclature
Syntheses
1. addition of hydrogen to an alkene
2. reduction of an alkyl halide
a) hydrolysis of a Grignard reagent
b) with an active metal and acid
3. Corey-House Synthesis
Reactions
1. halogenation
2. combustion (oxidation)
3. pyrolysis (cracking)
heat of hydrogenation:
CH3CH=CH2 + H2, Pt CH3CH2CH3 + ~ 30 Kcal/mole
ethylene 32.8
propylene 30.1
cis-2-butene 28.6
trans-2-butene 27.6
isobutylene 28.4
fats & oils: triglycerides
OCH2—O—CCH2CH2CH2CH2CH2CH2CH2CH2CH3
| O CH—O—CCH2CH2CH2CH2CH2CH2CH2CH2CH3
| OCH2—O—CCH2CH2CH2CH2CH2CH2CH3
“saturated” fat
OCH2—O—CCH2CH2CH2CH2CH=CH2CH2CH2CH3
| O CH—O—CCH2CH2CH2CH2CH=CH2CH2CH2CH3
| OCH2—O—CCH2CH2CH=CHCH2CH2CH3
Ω - 3 “unsaturated” oil
Saturated triglycerides are solids at room temperature and are called “fats”.
butter fat, lard, vegetable shortening, beef tallow, etc.
Unsaturated triglycerides have lower mp’s than saturated triglycerides. Those that are liquids at room temperature are called “oils”. (All double bonds are cis-.)
corn oil, peanut oil, Canola oil, cottonseed oil, etc.
polyunsaturated oils + H2, Ni saturated fats
liquid at RT solid at RT
oleomargarine
butter substitute
(dyed yellow)
Trans-fatty acids formed in the synthesis of margarine have been implicated in the formation of “bad” cholesterol, hardening of the arteries and heart disease.
2) Addition of halogens.
| | | |— C = C — + X2 — C — C —
| | X X
a) X2 = Br2 or Cl2
b) test for unsaturation with Br2
CH3CH2CH=CH2 + Br2/CCl4 CH3CH2CHCH2
Br Br 1-butene 1,2-dibromobutane
3. Addition of hydrogen halides. | | | |— C = C — + HX — C — C —
| | H Xa) HX = HI, HBr, HClb) Markovnikov orientation
CH3CH=CH2 + HI CH3CHCH3
I
CH3 CH3
CH2C=CH2 + HBr CH3CCH3
Br
Markovnikov’s Rule:
In der Hinzufügung einer Säure zu einem alkene wird der Wasserstoff zum Vinylkohlenstoff gehen, der schon den größeren Anzahl Wasserstoffe hat.
In the addition of an acid to an alkene the hydrogen will go to the vinyl carbon that already has the greater number of hydrogens.
Regla de Markovnikov:
En la adición iónica de un ácido al doble enlace de un alqueno, el hidrógeno de aquél se une al átomo de carbono que ya tiene el mayor número de hidrógenos.
“Al que tiene, le será dado.”
“El que tiene, recibirá.”
Dans l'addition d'un acide à un alcène l'hydrogène ira au carbone de vinyle qui a déjà le nombre plus grand de hydrogène.
알켄에 산의 추가안에 수소는 이미 수소의 더 중대한 수가 있는 비닐 탄소에는에 갈 것이다 .
アルケンへの酸の付加で水素はビニールカーボンにへ行く既に水素の大きい数がある。
В дополнении кислоты к алкен водород будет идти в углерод винила, который уже имеет больший номер(число) водорода.
CH3CH2CH=CH2 + HCl CH3CH2CHCH3
Cl
CH3 CH3
CH3CH=CCH3 + HBr CH3CH2CCH3
Br
CH3CH=CHCH3 + HI CH3CH2CHCH3
I
An exception to Markovikov’s Rule:
CH3CH=CH2 + HBr, peroxides CH3CH2CH2Br
CH3 CH3
CH3C=CH2 + HBr, peroxides CH3CHCH2Br
“anti-Markovnikov” orientation
note: this is only for HBr.
Markovnikov doesn’t always correctly predict the product!
CH3 CH3
CH2=CHCHCH3 + HI CH3CH2CCH3 I
Rearrangement!
Ionic electrophilic addition mechanism
1) C C + YZRDS
C C
Y
+ Z
2) C C + Z C C
YZY
mechanism for addition of HX
1) C C + HXRDS
C C
H
+ X
2) C C + X C C
HXH
why Markovinkov?
CH3CH=CH2 + HBr CH3CHCH2 1o carbocation
| H
or? CH3CHCH2 2o carbocation | more stable H
+ Br- CH3CHCH3
| Br
In ionic electrophilic addition to an alkene, the electrophile always adds to the carbon-carbon double bond so as to form the more stable carbocation.
4. Addition of sulfuric acid.
| | | |— C = C — + H2SO4 — C — C — | |
H OSO3H
alkyl hydrogen sulfate
Markovnikov orientation.
CH3CH=CH2 + H2SO4 CH3CHCH3
O O-S-O OH
5. Addition of water.
| | | |— C = C — + H2O, H+ — C — C —
| | H OHa) requires acidb) Markovnikov orientationc) low yield
CH3CH2CH=CH2 + H2O, H+ CH3CH2CHCH3
OH
Mechanism for addition of water
1)
2) C C
H OH2
C C
H
3)
C C H
C C
H OH
+ H
+
C C
H
+ H2O
C C
H OH2
RDS
| | H+ | |— C = C — + H2O — C — C — | | OH H
Mechanism for addition of water to an alkene to form an alcohol is the exact reverse of the mechanism (E1) for the dehydration of an alcohol to form an alkene.
Mechanism for dehydration of an alcohol = E1
C C
H OH
+ H C C
H OH2
1)
2) C C
H OH2
RDSC C
H
+ H2O
C C
H
3) C C + H
mechanism for addition of X2
1) C C + X--XRDS
C C
X
+ X
2) C C + X C C
XXX
How do we know that the mechanism isn’t this way?
One step, concerted, no carbocation
C C
X X
RDS
C C
X X
CH3CH=CH2 + Br2 + H2O + NaCl
CH3CHCH2 + CH3CHCH2 + CH3CHCH2
Br Br OH Br Cl Br
CH3CH=CH2 + Br--Br CHCHCH2
Br
Br H2O Cl
Some evidence suggests that the intermediate is not a normal carbocation but a “halonium” ion:
| | — C — C —
Br
The addition of X2 to an alkene is an anti-addition.
6. Addition of halogens + water (halohydrin formation):
| | | |— C = C — + X2, H2O — C — C — + HX | | OH X
a) X2 = Br2, Cl2
b) Br2 = electrophile
CH3CH=CH2 + Br2(aq.) CH3CHCH2 + HBr OH Br
mechanism for addition of X2 + H2O
1) C C + X--XRDS
C C
X
+ X
2) C CH2O + C C
XH2OX
C C
XH2O
3) C C
XHO
- H
7. Dimerization:
CH3 CH3 CH3
CH3C=CH2 + H2SO4, 80oC CH3C-CH=CCH3
CH3
+ CH3 CH3
CH3C-CH2C=CH2
CH3
CH3C=CH2
CH3
+ H CH3CCH3
CH3
CH3C
CH3
CH3
+ CH2=CCH3
CH3
CH3C
CH3
CH3
CH2CCH3
CH3
CH3C
CH3
CH3
CH2CCH3
CH3 - HCH3C
CH3
CH3
CH=CCH3
CH3
+ CH3C
CH3
CH3
CH2C=CH2
CH3
carbocation as electrophile
8. Alkylation:
CH3 CH3
CH3C=CH2 + CH3CHCH3 + HF, 0oC
CH3 CH3
CH3C-CH2CHCH3
CH3
2,2,4-trimethylpentane ( “isooctane” )
Used to increase gasoline yield from petroleum and to improve
fuel performance.
CH3C=CH2
CH3
+ H CH3CCH3
CH3
CH3C
CH2
CH3
+ CH2=CCH3
CH3
CH3C
CH3
CH3
CH2CCH3
CH3
CH3C
CH3
CH3
CH2CCH3
CH3
+ CH3CCH3
CH3
H
CH3C
CH3
CH3
CH2CCH3
CH3
H
CH3CCH3
CH3
+
intermolecular hydride (H:-) transfer
Internal combustion engine (four-stroke).
Also called an Otto engine.
1. Intake stroke: air/fuel mixture is drawn into the cylinder.
2. Compression stroke: air/fuel mixture is compressed.
Ignition of air/fuel mixture by spark at approximately 0o top dead center.
3. Power stroke: expanding gases push piston down driving crank shaft around.
4. Exhaust stroke: CO2 + H2O are pushed out of the cylinder.
<http://www.k-wz.de/vmotor/v_omotore.html>
Compression is the key to building a more powerful four-stroke engine. The more the air/fuel mixture is compressed prior to ignition, the more efficient is the conversion of heat energy into mechanical motion. Increasing the compression ratio =>
1. More powerful engine.
2. Lighter engine (greater power to weight ratio).
3. Greater fuel economy.
But, compression of the air/fuel mixture above a certain point causes “knocking”.
PV = nRT
T P
If, during compression of an air/fuel mixture, the temperature goes high enough, the mixture may explode prematurely.
A knocking sound is produced by an internal combustion engine when fuel ignites spontaneously and prematurely (pre-ignition) during the compression cycle in an engine’s combustion chamber. Consequently, the piston will be forced down when it should be traveling upwards on its compression stroke.
At best, knocking reduces the performance of the engine; at worst, it can damage the engine’s moving parts.
Fuel for four-stroke internal combustion engines:
Gasoline ( historically a waste product from the production of kerosene ).
Gasoline is a complex mixture of hydrocarbons distilled from petroleum. It is mixed with air to form an explosive mixture.
Gasoline + (xs) O2, spark CO2 + H2O + heat
The fuel limits how high the compression ratio can be before the engine knocks.
CH3CH2CH2CH2CH2CH2CH3 knocks like crazy at
n-heptane low compression.
CH3 CH3
CH3CCH2CHCH3 resists knocking CH3
2,2,4-trimethylpentane ( “isooctane” )
Octane rating: a measure of the resistance of a fuel to knock in an internal combustion engine at high compression ratios. Determined by comparing the fuel to mixtures of:
n-heptane (octane number = 0)
and
2,2,4-trimethylpentane (octane number = 100)
in a test engine.
Tetraethyl lead, (CH3CH2)4Pb, was discovered to increase the octane rating of gasoline.
Lead is extremely toxic, especially in small children where exposure leads to nerve damage.
All gasoline in the US is now “lead free”.
Tetraethyl lead has been replaced by “alkylates” and catalytically reformed hydrocarbons.
Compression vs. Octane Number
5:1 72
6:1 81
7:1 87
8:1 92
9:1 96
10:1 100
11:1 104
12:1 108
Use the octane rating recommended by your car maker! Using a higher octane gasoline only puts more of your money into the fuel company’s pockets.
9. Oxymercuration-demercuration.
| | | |— C = C — + H2O, Hg(OAc)2 — C — C — + acetic | | acid OH HgOAc
| | | |— C — C — + NaBH4 — C — C — | | | | OH HgOAc OH H
alcohol
oxymercuration-demercuration:
a) #1 synthesis of alcohols.
b) Markovnikov orientation.
c) 100% yields.
d) no rearrangements
CH3CH2CH=CH2 + H2O, Hg(OAc)2; then NaBH4
CH3CH2CHCH3
OH
With alcohol instead of water:
alkoxymercuration-demercuration:
| | | |— C =C — + ROH, Hg(TFA)2 — C — C — | | OR HgTFA
| | | |— C — C — + NaBH4 — C — C — | | | | OR HgTFA OR H
ether
alkoxymercuration-demercuration:
a) #2 synthesis of ethers.
b) Markovnikov orientation.
c) 100% yields.
d) no rearrangements
CH3CH=CH2 + CH3CHCH3, Hg(TFA)2; then NaBH4 OH
CH3 CH3
CH3CH-O-CHCH3
diisopropyl ether Avoids the elimination with 2o/3o RX in Williamson Synthesis.
Ethers
nomenclature
syntheses
1. Williamson Synthesis
2. alkoxymercuration-demercuration
reactions
1. acid cleavage
10. Hydroboration-oxidation.
| | | |— C = C — + (BH3)2 — C — C — | | diborane H B — |
| | | |— C — C — + H2O2, NaOH — C — C — | | | | H B — H OH |
alcohol
hydroboration-oxidation:
a) #2 synthesis of alcohols.
b) Anti-Markovnikov orientation.
c) 100% yields.
d) no rearrangements
CH3CH2CH=CH2 + (BH3)2; then H2O2, NaOH
CH3CH2CH2CH2-OH
CH3
CH3C=CH2 + H2O, Hg(OAc)2; then NaBH4
CH3
Markovnikov CH3CCH3
OH CH3
CH3C=CH2 + (BH3)2; then H2O2, NaOH
CH3
anti-Markovnikov CH3CHCH2
OH
Alcohols:
nomenclature
syntheses
1. oxymercuration-demercuration
2. hydroboration-oxidation
3.
4. hydrolysis of a 1o / CH3 alcohol
5.
6.
8.
11. Addition of free radicals.
| | | |— C = C — + HBr, peroxides — C — C — | |
H X
a) anti-Markovnikov orientation.b) free radical addition
CH3CH=CH2 + HBr, peroxides CH3CH2CH2-Br
Mechanism for free radical addition of HBr:
Initiating steps:
1) peroxide 2 radical•
2) radical• + HBr radical:H + Br• (Br• electrophile)
Propagating steps:
3) Br• + CH3CH=CH2 CH3CHCH2-Br (2o free radical) •4) CH3CHCH2-Br + HBr CH3CH2CH2-Br + Br• •
3), 4), 3), 4)…
Terminating steps:
5) Br• + Br• Br2
Etc.
In a free radical addition to an alkene, the electrophilic free radical adds to the vinyl carbon with the greater number of hydrogens to form the more stable free radical.
In the case of HBr/peroxides, the electrophile is the bromine free radical (Br•).
CH3CH=CH2 + HBr, peroxides CH3CH2CH2-Br
12. Polymerization.
CH2=CH2 + heat, pressure -(CH2CH2)-n n = 10,000+
polyethylene
CH3CH=CH2 polymerization -(CH2CH)-n
CH3
polypropylene
CH2=CHCl poly… -(CH2CH)-n
Clpolyvinyl chloride (PVC)
Plastics: man-made polymers that at some time in their manufacture are soft and pliable.
Thermoplastics: plastics that soften when heated.
Free radical polymerization.
| | | | | |R• + — C = C — R — C — C • + — C = C — | |
13. Addition of carbenes.
| | | |— C = C — + CH2CO or CH2N2 , hν — C — C
—
CH2
•CH2• “carbene” adds across the double bond | |— C = C — •CH2•
| | | |— C = C — + CHCl3, t-BuOK — C— C —
CCl2
-HCl
•CCl2• dichlorocarbene
| |— C = C — •CCl2•
CH3CH=CH2 + CH2N2
hv HC CH2
CH2
H3C
CHCl3, t-BuOK HC CH2
CCl2
H3C
14. Epoxidation.
| | C6H5CO3H | |
— C = C — + (peroxybenzoic acid) — C— C —
O epoxideFree radical addition of oxygen diradical. | |— C = C — •O•
2-butene
H3C CH
CH
CH3 + C6H5CO3HHC
HC
OCH3H3C
peroxybenzoic acid
15. Hydroxylation. (mild oxidation)
| | | |— C = C — + KMnO4 — C — C — syn | | OH OH
OH | | | |— C = C — + HCO3H — C — C — anti peroxyformic acid | | OH
glycol
CH3CH=CHCH3 + KMnO4 CH3CH-CHCH3
OH OH 2,3-butanediol
test for unsaturation purple KMnO4 brown MnO2
CH2=CH2 + KMnO4 CH2CH2
OH OH ethylene glycol
“anti-freeze”
16. Allylic halogenation.
| | | | | |— C = C — C — + X2, heat — C = C — C — + HX | | H allyl X
CH2=CHCH3 + Br2, 350oC CH2=CHCH2Br + HBr
a) X2 = Cl2 or Br2
b) or N-bromosuccinimide (NBS)
CH2=CHCH3 + Br2 CH2CHCH3
Br Braddition
CH2=CHCH3 + Br2, heat CH2=CHCH2-Br + HBr
allylic substitution
17. Ozonolysis.
| | | |— C = C — + O3; then Zn, H2O — C = O + O = C —
used for identification of alkenes
CH3
CH3CH2CH=CCH3 + O3; then Zn, H2O
CH3
CH3CH2CH=O + O=CCH3
18. Vigorous oxidation.
=CH2 + KMnO4, heat CO2
=CHR + KMnO4, heat RCOOH carboxylic acid
=CR2 + KMnO4, heat O=CR2 ketone
CH3CH2CH2CH=CH2 + KMnO4, heat
CH3CH2CH2COOH + CO2
CH3 CH3
CH3C=CHCH3 + KMnO4, heat CH3C=O + HOOCCH3
CH3CH=CHCH3 + KMnO4 CH3CHCHCH3
OHOHmild oxidation glycol
CH3CH=CHCH3 + hot KMnO4 2 CH3COOH
vigorous oxidation
Reactions, alkenes:
1. Addition of hydrogen
2. Addition of halogens
3. Addition of hydrogen halides
4. Addition of sulfuric acid
5. Addition of water/acid
6. Addition of halogens & water (halohydrin formation)
7. Dimerization
8. Alkylation
9. Oxymercuration-demercuration
10. Hydroboration-oxidation
11. Addition of free radicals
12. Polymerization
13. Addition of carbenes
14. Epoxidation
15. Hydroxylation
16. Allylic halogenation
17. Ozonolysis
18. Vigorous oxidation
CH3 CH3
CH3C=CH2 + H2, Pt CH3CHCH3
isobutylene CH3
“ + Br2/CCl4 CH3C-CH2
Br Br
CH3
“ + HBr CH3CCH3
Br
CH3
“ + H2SO4 CH3CCH3
O SO3H
CH3 CH3
CH3C=CH2 + H2O, H+ CH3CCH3
isobutylene OH
CH3
“ + Br2(aq.) CH3C-CH2Br OH
CH3 CH3 CH3
CH3C=CH2 + H2SO4, 80oC CH3C-CH=CCH3
(dimeriz.) CH3
CH3 CH3 + CH3C-CH2C=CH2
CH3
CH3 CH3
CH3C=CH2 + CH3CHCH3 + HF, 0oC
CH3 CH3
CH3C-CH2CHCH3
CH3
CH3 CH3
CH3C=CH2 + H2O,Hg(OAc)2; then NaBH4 CH3CCH3
OH
CH3
“ + (BH3)2; then H2O2, OH- CH3CHCH2
OH
CH3 CH3
CH3C=CH2 + HBr, peroxides CH3CHCH2
isobutylene Br CH3
“ + polym. -(CH2C)-n
CH3
CH3
“ + CH2CO, hv CH3C–CH2
CH2
CH3
“ + PBA CH3C–CH2
O
CH3 CH3
CH3C=CH2 + KMnO4 CH3C–CH2
isobutylene OH OH
CH3
“ + Br2, heat CH2C=CH2 + HBr Br
CH3
“ + O3; then Zn/H2O CH3C=O + O=CH2
CH3
“ + KMnO4, heat CH3C=O + CO2