unsaturated chemical compound containing at least one carbon-carbon double bond, where rotation...
TRANSCRIPT
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• Unsaturated chemical compound containing at least one carbon-carbon double bond, where rotation about the C=C is very difficult.
• To show the presence of the double bond, the –ane suffix from the alkane name is changed to –ene.
• Also called olefins( fat dissolving)• sp2 atomic orbitals• Trigonal planar, 120o degree
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Geometric Isomerism
• Cis-trans isomerism-isomers that have same order
of atom attachment but a different arrangement of their atoms in space.
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General Formula
CnH2n
• where n is the number of carbon atoms in the molecule
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Physical Properties• Physical state -The first lower
member like ethene, propene and butene are colorless gases.
• Density - lighter than water. • Solubility - insoluble in water and
soluble in nonpolar organic solvents.• more reactive than alkanes due to
their double carbon-carbon bond.
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• Boiling point -The boiling points of alkenes gradually increase with an increase in the molecular mass.
• The cis isomer ( example cis-2-butene, b.p.= 3.7°C) is higher in bpt than its trans isomers (example, trans-2-butene, b.p.= 1°C)
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• Melting point The melting points of alkenes increase with an increase in the molecular mass.
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Natural Sources
• Isolated from petroleum.• Plant material like plant
hormone, like Ethylene – a natural ripening agent and Terpenes – found in essential oil.
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Some Common Alkene Polymers and their Uses
•Ethylene H2C=CH2 Polyethene, Polythene Packaging, cable insulation, films and sheets
•Tetrafluoroethene F2C=CF2 Polytetrafluoroethene, PTFE, Teflon Coatings, gaskets.
•Chloroethene (vinyl chloride) H2C=CHCl Polyvinyl chloride, PVC, Tedlar Insulation, films, pipes
•Styrene H2C=CHC6H5 Polystyrene, Styron Foam for packaging etc.
•Vinyl acetate H2C=CHOCOCH3 poly(vinyl acetate), PVA
•Paints, adhesives.
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Preparations of Alkenes
1. Dehydrohalogenation of Alkyl halides2. Dehydration of Alcohol3. Dehalogenation of Vicinal Halides4. Reduction of Alkynes
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Preparations of alkenes1. Dehydrohalogenation of alkyl halides
C
C
XH
+ KOHalcohol C C
+ KX + H2O
Ease of dehydrohalogenation of alkyl halides
3° > 2° > 1°
Example:
CH3CH2CH2CH2Cl KOHCH3 CH2 HC CH2
n-butyl chloride 1-butene
KOH is an OH- donor use to abstract H
+
CH3CH2CHClCH3KOH
CH3 HC CHCH3 + CH3CH2HC CH2sec - butyl chloride 2 - butene (80%) 1 - butene (20%)
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Dehydrohalogenation of Alkyl Halides
• Is an Elimination reaction. The term "elimination" describes the fact that a small molecule is lost during the process.
Different mechanisms are possible:– Loss of the LG to form a carbocation, removal of
H+ and formation of C=C bond – Simultaneous H+ removal, C=C bond formation
and loss of the LG – Removal of H+ to form a carbanion, loss of the LG
and formation of C=C bond.
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2. Dehydration of alcohol
C C
H OH
acidC C
+ H2O
alkene
Ease of dehydration of alcohols
3° > 2° > 1°
ex.
CH C
H
H
H
H
OH
H2SO4 CH
H
C H
H
+ H2Oethylene
ethyl alcohol
acid serves as H+ donor
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CH3CH2CH2CH2OHH2SO4 CH3CH2HC CH2 CH3 HC CHCH3
n-butyl alcohol 1-butene 2-butene (chief product)
CH3CH2 HC CH3
OH
H2SO4
Al2O2 in
heated tube
CH3 HC CHCH3 + CH3CH2HC CH2
sec-butyl alcohol 2-butene 1-butene (chief product)
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Dehydration of Alcohols
• It is the elimination of water molecule from alcohol to convert into alkene.
• Lost of H and OH from adjacent carbons
• An acid catalyst alkene.
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Mechanism of Alcohol Dehydration
Step 1 : Alcohol unites with a hydrogen ion to form the protonated alcohol
Step 2 : Alcohol associates into water and carbonium ion.
Step 3 : The carbonium ion then loses a hydrogen ion to form alkene.
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3. Dehalogenation of vicinal dihalides (same side)
C
C
X X
+ Zn C
C
+ ZnX2
dihalides
Example:
CH3 HC CH CH3
Br Br
ZnCH3 HC CHCH3 + ZnX2
2,3- Dibromobutane 2- butene
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4. Reduction of alkynes
R C C R
LindlarCatalyst
Pd, NiBr
Na or Li
C C
HH
R R
C C
R
H
H
R
syn (cis)
anti (trans) NH3
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Reduction of Alkynes• Reducing Alkynes to form trans or cis
Alkenes.Using Na/ NH3
Step 1:Sodium transfer an electron to the alkyne giving a radical anion.
Step 2: The radical anion removes a proton from the ammonia in an acid/base reaction
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Step 3: A second atom of sodium transfers
another electron to the alkyne giving an anion.
Step 4 :the anion removes proton from the
ammonia in an acid/base reaction.
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Reactions of Alkene
• Halogenation• Hydration• Hydrogenation• Addition of hydrogen Halides• Addition of sulfuric acid• Addition of Carbenes• Addition of Free Radical
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• Allylic Hydrogenation• Dimerazation• Alkylation• Polymerization• Hydroxylation• Halohydrins formation• Ozonolysis
• Hydroboration-oxidation
• Epoxidation
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C
C
+ X2 C
C
X X
X2 = CL2, Br2
I2 - unreactive with alkane
Reactions of Alkenes
1. Addition of Halogens (X2)
Example.
HCH3C CH2
Br2CH3CHBrCH2Br
propene(propylene) 1,2 dibromopropane (propylene bromide)
CCl4
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Halogenations – Addition of Halogens
• When an alkene is treated at room temperature with a solution of bromine or chlorine in carbon tetrachloride or some other inert solvent, the halogens adds rapidly to the double bond of the alkene to give the corresponding vicinal dihalide ( two halogens attached adjacent carbons
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HCH3C CH2 CH3CH2CH3
H2, Ni
propene(propylene) propane
C C
+ H2
Pt, Pd or NiC
C
H H
2. Addition of Hydrogen (catalytic hydrogenation)
Ex.
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Hydrogenation of Alkenes
• The relationship between reactants and products in addition reactions can be illustrated by the hydrogenation of alkenes yield alkanes.Hydrogenation is the addition of H2 to a multiple bond.
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C
C
+ HX C
C
H X
HX = HCL, HBr, HI
3. Addition of hydrogen halides
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HCH3C CH2HBr
no peroxides
peroxides
H3C C
Br
H
CH3
2 - bromopropane(Isopropyl bromide)
Markovnikov addition.
CH3CH2CH2Br1 - bromopropane
(n - propyl bromide)
anti - Markovnikov addition.
HCH3C CH2HI CH3CHICH3
propene 2 - iodopropane ( isopropyl halides)
Ex.
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Ex.
actual product+ HI H3C CHI CH3H3C CH CH2
HCH3C CH2 + HI H3C CH CH2
H I
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HI CH3CHICl
1-Chloro
-1
-iodoethane
H3CHC=C
CH3
CH3 + HI CCH2CH3
CH3
CH3
I
CH3CH=CHCH3 + HI CH3CHICH2CH3
CH2=CHCl
vinyl chloride
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Addition of hydrogen halides
– In the addition of an acid to the C=C of an alkene, the hydrogen of the acid attaches itself to the carbon that already holds the greater number of hydrogens
– The reactivity of alkene, with halogen acids is in the order;.
HI > HBr > HCl
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C C
+ H2SO4 C
C
H OSO3Halkyl hydrogen sulfates
4. Addition of sulfuric acid
Ex.
HCH3C CH2
propene
80% H2SO4H2O, heat
CHCH3
OSO3H
CH3
CHCH3
OH
CH3
Isopropyl alcohol
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CH2=CH298%H2SO4
CH3CH2OSO3HH2O, heat
CH3CH2OH + H2SO4
CCH3
CH3
CH2
63%H2SO4
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5. Addition of water. HYDRATION
C
C
+ HOH C
C
H OH
H
+
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H3C C
CH3
CH2H2O, H
+
CH3 C
CH3
CH3
OHIsobutylene
tert - butyl alcohol
CH4
Ex.
HCH3C CH2H2O, H
+
propene Isopropyl alcohol (2 - propanol)
CHCH3CH3
OH
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Addition of Water - Hydration
– When heated with water in the presence of an acid catalyst, alkenes yield alcohol ROH.
– The process is called hydration of alkenes because it involves the addition of water across the double bond.
– The addition of the HOH across the double bonded carbon that bears the greater number of hydrogen atoms and the hydroxyl groups goes to the other double-bonded carbon
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C
C
+ X2 + H2O C
C
H OH
+ HX X2 = Cl2, Br2
HCH3C CH2
Cl2, H2OH3C CH CH2
HO Clpropylene(propene)
propylene chlorohydrin
follow Markovnikov rule
6. Halohydrin formation
Ex.
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C
C
HH3C
CH3 H
Cl2, H2O Cl
CH3
H
H OH
CH3cis - 2 - butene
threo (stereospecific)
3 - chloro - 2 - butanol
C
C
CH3H
CH3 H
trans 2 - butene
Cl2, H2O H
CH3
Cl
H OH
CH3
erythro
3 - chloro - 2 - butanol
Sterospecific:
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7. Dimerization (di = two, mer = part, product contains exactly twice the # of C & H atom as the original).
H3C C
CH3
CH2+ H3C C
CH3
CH2H2SO4
H3C C
CH3
CHCH3
C
CH3
CH3+ H3C C
CH3
CH2CH3
C
CH3
CH2isobutylene isobutylene
2,4,4 - trimethyl - 2 - pentene 2,4,4 - trimethyl - 1 - pentene
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Mechanism:
Addition of the tert-butyl cation to iso butylene; the orientation of addition is duch to yield the more stable tertiary cation. Step(2) brings about the union of two : isobutylene units, which is of course necessary for the product.
H3C C
CH3
CH2+ H:Br H3C C
CH3
CH3+
+ : Braddition of a hydrogen ionto isobutylene to formthe carbon
H3C C
CH3
CH3+
+ H3C C
CH3
CH2 H3C C
CH3
CH2
CH3
C
CH3
CH3+H3C C
CH3
CH
CH3
C
CH3
CH3
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8. Alkylation
C
C
+ R Hacid
C C
RHex.
H3C C CH2
CH3
isobutylene+ H3C C H
CH3
CH3
H2SO4 H3C C CH2 C CH3
CH3 CH3
CH3Hisobutane 2, 2, 4 - trimethyl pentane
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mechanism:
H3C C CH2
CH3
+ H3C C
CH3
CH3
+ H3C C CH2 C CH3
CH3 CH3
CH3
+
H3C C CH2 C CH3
CH3
CH3
CH3
++ H C CH3
CH3
CH3
H3C C CH2 C CH3
CH3 CH3
CH3H
+
C CH3
CH3
CH3
+
Addition of a hydrogen ion to form carbocation
Addition of a tert-butyl carbocation to isobutylene
Carbocation abstracts a hydrogen atom with its pair of electrons from a molecule of alkane. This abstraction of hydride ion yields an alkane of 8 carbons and a new carbocation to continue the chain.
H3C C CH2
CH3
+ H:B H3C C CH3
CH3
+ :B+
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A carbocation may:
a.) combine with a negative ion or other basic molecule
b.) rearrange to a more stable cabocation
c.) eliminate a hydrogen ion to form an alkene
d.) add to an alkene to form a larger carbocation
e.) abstract a hydride ion from an alkane
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9. Oxymercuration - demercuration
•Oxymercuration – involves addition to the C=C of OH and HgOAc (mercuric ion)
•Demercuration – the HgOAc is replaced by H
C C + H2O+ Hg(OAc)2 C C
AcOHgHO
NaBH4C C
HHO
oxymercuration demercuration
mercuric acetate
organomercurial cmpd. alcoholMarkovnikov orientation
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Ex. Undergo the process of oxymercuration, involves addition to the carbon – carbon double bond of –OH+ -HgOAc
CH2CH3C CH2
CH3
Hg(OAc)2, H2O NaBH4 CH2CH3C CH3
OH
CH3
2 - methyl - 1 - butene
tert - pentyl alcohol
CH3 CH3
OH
Hg(OAc)2, H2O NaBH4
1 - methylcyclopentene 1 - methylcyclopentanol
H3C C
CH3
CH3
CH CH2 H3C C
CH3
CH3
HC CH3
OH
Hg(OAc)2, H2O NaBH4
3, 3 - dymethyl - 1 - butene 3, 3 - dymethyl - 2 - butanol
H3C(H2C)3HC CH2Hg(OAc)2, H2O NaBH4
1 - hexene2 - hexanol
CH(CH2)3CH3
OH
CH3
Follows Markovnikov addition
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10. Hydroboration – oxidation
With the reagent Diborane, alkenes undergo hydroboration to yield alkylboranes, which on oxidation give alcohols.
(BH3)2 CH3CH2BH2 (CH3CH2)2BH (CH3CH2)3BH2C=CH2 H2C=CH2 H2C=CH2
diborane triethylboron
(CH3CH2)3B + 3H2O2 3CH3CH2OH + B(OH)3
OH-
ethanol boric acid
C C + (BH3)2 C C
H B
C C
H OH
H2O2
OH-
Diborane
Anti - markovnikov orientation
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Mechanism:
Hydroboration involves the addition of the double bond of BH3 w H becoming attach to one doubly bonded carbon and boron to the other. The alkylborane can then undergo oxidation in which the boron is replaced by –OH. Thus, the 2 – stage reaction process of hydroboration oxidation permits the effect. The addition to the carbon – carbon double bond of elements of H-OH.
C C + H - B C C
B
C C
OHhydroboration oxidation
H B = H - BH2, H - BHR, H - BR2
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CH3CH=CH2(BH3)2 H2O2, OH
-CH3CH2CH2OH
n-propyl alcoholpropylene
CH3CH2CH=CH2
(BH3)2 H2O2, OH-
CH3CH2CH2CH2OH
n-propyl alcohol1
-butene
C=CH2CH3
CH3(BH3)2 H2O2, OH
-
CHCH2OH
CH3
CH3
Isobutyl alcoholIsobutylene
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11. Addition of free radicals
C C + Y Z C C
Y Z
peroxides
or light
n - C6H13CH CH2 + BrCCl3 n - C6H13CH
Br
CH2 CCl3peroxide
1 - octane bromotrichloromethane
3 - bromo - 1,1,1 - trichlorononanestability of radical: 3º > 2º > 1º CH3
RCH CH2+ CCl4 RCH CH2 CCl3
Cl
peroxides
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Mechanism:
peroxides rad.
Rad. + Cl:CCl3 Rad:Cl+ .CCl3
.CCl3+ RCH=CH2 RCH - CH2 - CCl3
RC.H - CH2 - CCl3 + Cl:CCl3 RCH - CH2 - CCl3
Cl
+ .CCl3
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Electrophilic addition : Markonikov orientation
HCH3C CH2
HBr
CH3 CH CH3+
2º cation
CH3 CH CH3
Brisopropyl bromide
CH3 CH2 CH2+
1º cation
propylene
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HCH3C CH2
propylene
Br.
CH3 CH CH2Br
2º free radical
CH3 CH2 CH2Br
CH3 CH2 CH2
Br1º free radical
HBr.
.
Free – radical Addition : Anti – Markovnikov orientation
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12. Polymerization of Alkenes
Polymerization – the joining together of many small molecules to form very large molecules.Monomers – the simple compounds form which polymers are made.
Ex.
nCH2 CH2
O2, heat, presH2C CH2 CH2 CH2 CH2 CH2
or
H2C CH2
polythylene(plastic material of packaging film)
•5 processes of polymerization
1. Free - radical polymerization2. Cationic polymerization3. Anionic polymerization4. Condensation polymerization5. Coordination polymerization
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Free – radical polymerization
nCH2 CH
Cl
peroxideH2C CH CH2 CH CH2 CH CH2
Cl Cl Cl
or
H2C CH2
Cl n
poly (vinyl chloride)
Polyvinyl chloride - use to make phonograph, records, plastic pipes, when plasticized with high boiling esters – raincoats, shower curtains and coatings for metal and upholstery fabrics.Peroxide – initiator, required in small amount in polymerization-Free radical initiator
peroxide rad. decomposition of peroxides to form free radical
Mechanism:
Free radical adds to molecule of alkenes which for another free radical
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rad H2C CH
G
radCH2 CH
G
. chain initiating step
This radical adds to another molecule of alkene to generate another free radical. This radical adds to another molecule of alkene to generate a still larger radical
radCH2 CH
G
.+ H2C CH
G
radCH2 CH
G
CH2 CH
G
. chain propagating step
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13. Addition of Carbenes. Cycloadditioncarbenes – derivative of methylene
H2C N N+ -
CH2 N2UV lightphotolysis
diazomethans methylene
H2C C O CH2 COUV light +
ketene methylene
+
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CH2: or H :C. ...
H
H : C....H
Methylene exist into 2 different forms
singlet methylene – unshared electrons are paired, less stable & generated first in photolysis : stereospecific addition
triplet methylene – unshared electrons are not paired, free radical (diradical) : nonstereospecific addition
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HCH3C CHCH3 + CH2N2light
CH2
HCH3C CHCH32 - butene diazomethane
1, 2 - dimethycyclopropane
+ N2
Cycloaddition: addition of the carbon – carbon double bond
Photolysis of diazomethane into in liquid
And in liquid
Sterospecific: (addition of methylene can occur with 2 different kinds of stereochemistry.)
cis - 2 -butene CH2N2 cis 1, 2 - dimethylcyclopropane+
trans 2 -butene CH2N2 trans 1,2 -dimethylcyclopropane+
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CH2: + C C
C C
CH2
C C
CH2Singlet methyleneStereospecificElectrophilic additionElectron deficient and can find electrons at the C-C double bondingle
CH2N2Non – stereospecific: cis/trans2 – butene + both cis and trans 1,2 - dimethylcyclopropane
Triplet methyleneNon - StereospecificFree radical additionff. by addition
CH2 + C C
C C
CH2
C C
CH2
....
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C
H + CH2 C
CH2 H
HCH2C CHCH3 + CHCl3t - BuO
-K
+
HCH3C CHCH3
C
Cl Cl
+ t - BuOH + KCl
2 - butene chloroform
3, 3 - dichloro - 1, 2 - dimethylcyclopropane
Methylene undergoes intersection
Addition of substituted carbenes: 1,1 - elimination
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t - BuO-.. + H..CCl3
..CCl3-
..CCl3-
..CCl2 Cl -+ t - BuO
..H
dichlorocarbene
+
HCH3C CH3CH+ ..CCl2 HCH3C CHCH3
C
Cl Cl
Reaction involves a divalent carbon compound, a derivative of methylene: dichlorocarbene: CU2.Generated in 2 steps, initiated by attack on chloroform by the strong base tert-butoxide ion and then adds to the alkene.
Mechanism:
Because of the presence of halogen atom, the singlet form is the more stable form of dichlorocarbene and is the one adding to the double bond.
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Addition of Carbenes
• Carbenes are intermediates of the general formula CH2:. The derivatives of methylene (CH2) are the carbenes.
• Methylene is formed by the photolysis of either diazomethane, CH2N2 or ketene, CH2=C=O.
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C
C
+ KMnO4 or HCO2OH C
C
OH OH
HCH3C CH2propylene
cold, dil. KMnO4 or HCO2OHH3C CH CH2
OHOH+ 2MnO2
1,2 - propanediol (propylene glycol)
14. Hydroxylation. Glycol formation
Example.
Oxidizing agents that bring about hydroxylation
a. cold alkaline potassium permanganate, KMnO4
b. peroxy acids, such as peroxyformic acid HCO2OH
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KMnO4
OHOH
HCO2OH
OH
OH +OH
OH
syn-hydroxylation
anti-hydroxylation
cis-1,2
-cyclopentanediol
trans-1,2
-cyclopentanediol
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CH
C
C
+ X2heat
CX
C
C
X2 = Cl2, Br2
low conc.
HCH3C CH2propylene
Cl2, 600ºCl - CH2CH CH2
allyl chloride
+ NBS
Br
cychlohexeneN - bromosuccinimide
3 - bromocyclohexene
15. Halogenation. Allylic substitution ( same mechanism with substitution in alkenes)
Ex.
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CH2=CH-CH3
alkene-like site of addition alkane
-like site of substitution
CH2=CH-CH3
heterolytic attack, addition Free-radical attack, substitution
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Can we direct the attack to just one of these sites? Yes, by our choice of rxn. Conditions.
Conditions:1.alkenes undergo substitution by halogen at high temp. or under the influence of UV light, generally in gas phase.2.it can also undergo addition of halogen at low temp. in the absence of light and generally in liquid state(phase).
CH CH2CH3
propylene
Cl2
CH3 CH CH2
Cl Cl
Cl CH2 CH CH2
low T
CCl4 soln
500 - 600ºgas phase
ClH
1,2 - dichloropropane
3 - chloro -1 - propane
heterolytic add'n
free radical subs
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N – bromosuccinimide a reagent used for the specific purpose of brominating alkenes at the allylic position provides a constant low conc. of bromine.
NBS
NC
C
CH2
CH2
O
O
BrHBr +
NC
C
CH2
CH2
O
O
HBr2 +
succinimide
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C
C
C
H
H
H
H
vinylic hydrogen: hard to abstract
allylic hydrogen: easy to abstract.
Ease of abstraction of hydrogen atoms:
Ease of formation of free radicals: allyl > 3º > 2º > 1º > CH3. > vinyl
Vinylic hydrogen- hydrogens attached to C=C
Alylic hydrogen – hydrogens attached to a carbon atom next to a double bond
Allylic >3º > 2º > 1º > CH4 > Vinylic
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Example:
CH3(CH2)3CH2CH2CH=CH2NBS
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16. Ozonolysis (Cleavege rxn)
C
C
+ O3 OO
O
O
O
H2O, ZnC O
+ O C
ozone
ozonide
aldehyde ketone
Cleavage – a rxn in which the double bond is completely broken and the alkene molecules converted into 2 smaller molecule.
Reducing agent (Zn) – prevent formation of hydrogen peroxidewill not react with aldehyde and ketone (aldehyde are often
converted to acid, RCOOH for ease of isolation.)
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CH3CH2CH=CH2O3 H2O, Zn CH3CH2CHO + CH2=O
C=CH2
CH3
CH3O3 H2O, Zn
C=O
CH3
CH3 + CH
H
O
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CH2CH3C
H
O + O C
H
CH2CH3H2O / Zn O3 CH2CH3C
H
C CH2CH3
H
aldehydes 3 - hexene
CH2CH3C
H
O + O C
CH3
CH3H2O / Zn O3 CH2CH3C
H
C CH3
CH3
aldehydes 2 - methyl - 2 - penteneketone
Ozonolysis – is a typical means of degradation
CH3CH2CH2CHO + CH3CHOH2O, Zn O3
CH3CH2CH2CH=CHCH3
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17. Cleavage with periodate ( cleavage with a diol)
C
C
C
C
OH OH
KMnO4
cold, dil.
NaIO4acids, ketones. CO2
RCOOH are generally obtained instead of aldehydes, RCHO a terminal ==CH2 group is oxidized to CO2.
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CH3CH2CH2COOH + CO2KMnO4NaIO4
HCH2CH2CH3C CH2
carboxylic acid carbon dioxide
Example.
CH3COOH + O C
CH3
CH3 CH C
CH3
CH3CH3KMnO4
NaIO4carboxylic acid ketone 2 - methyl - 2 - butene
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Cleavage of cycloalkenes
CH
CH
CH2
CH2
H2C
H2C
O3 H2O, Zn
KMnO4
NaIO4
CHO
CHO
CH2
CH2
H2C
H2C
COOH
COOH
CH2
CH2
H2C
H2C
di - aldehyde
di - acid
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18. Epoxidation of Alkenes
C=C +CHC=C +CH33COOH C C + COOH C C + CH3COHCH3COH O
O O
Alkene Peroxyacetic Acid
Epoxide Carboxylic acid
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H2C=CH(CH2)9CH3 + CH3COOHCH2-CH(CH2)9CH3 + CH3COH
O O
1-Dodecane Peroxyacetic acid 1,2-epoxydodecane
Acetic acid
Example