Professional Documents
Culture Documents
1. addition of HBr
H2SO4 alcohol
OH OH goes to more subst side
carbocation mechanism (rearrangements)
H2O
4. oxymercuration-reduction
5. hydroboration-oxidation
1. BH3-THF alcohol
OH goes to more less side
2. H2O2, NaOH no rearrangements
OH
6. addition of X2
X2 vicinal dihalide
X a halogen goes to both sides
X
(no regioselectivity!)
X2 halohydrin
OH OH goes to more subst side
H2O X
8. catalytic hydrogenation
H2 alkane
H goes to both sides
Pd/C reduction
LG Ch 12 p 3
9. hydroxylation
PhCO3H epoxide
O same O bonded to both sides
oxidation
11. cyclopropanation
cyclopropane
12. polymerization same O bonded to both sides
H2SO4 polymer
C=C's attach to each other
end to end
So, what new compounds can we make from alkenes using addition reactions? Which of
these are the most useful?
alkyl halides - can be used in SN2 rxns
alcohols - very useful!
vicinal dihalides - not commonly needed
halohydrins - might be useful
alkanes - only way so far to make
vicinal diols - can be useful
epoxides - can be used to make other things
cyclopropanes - not very common, but this is the only way (in this class) to make
them
polymers - plastics $$$
LG Ch 12 p 4
Catalytic hydrogenation of alkenes
During catalytic hydrogenation, what gets added to the double bond? two H's
note relationship on
What kind of catalyst is needed? metal such as Pd, Pt, Rh, or Ni Periodic Table;
finely divided, precipitated on C often called noble
metals
How do these catalysts need to be handled? very carefully - pyrophoric!
What do we call it when the catalyst is a different state of matter than the reaction?
heterogeneous catalysis
H2 H
added
H
H Pd/C
H
Do we need to worry about regioselectivity? nope - both H's are the same
Parr shaker - H2 tank, glass reaction bottle, motor to shake it show image
no Nu or E
no rearrangements - no C+
H2 and pi bond form weak bonds to metal surface, then to each other show diagram
How many alkenes with the formula C9H16 could be used as the starting material to make
1-methyl-2-propylcyclopentane?
H2
11! (9 constitutional isomers
Pd/C + 2 stereoisomers)
LG Ch 12 p 5
Hydroxylation of Alkenes
What is added to the C=C in a hydroxylation reaction? OH to both sides
Which reagent would you used with the following starting materials? Write a reaction.
OsO4 OH
enantiomerically pure
OsO4 compound - don't want to
H2O, H2O2
lose any
OH
OH
Why would KMnO4 make a good chemical test, while OsO4 would not?
KMnO4 gives a visible color change - purple to brown color - easy to see, also it is
cheap, not too toxic
OsO4 is too dangerous and difficult to work with, plus it gets regenerated
How reactive are they, and why? much more reactive than normal ethers - ring strain
How can you make a peroxyacid? react a carboxylic acid with hydrogen peroxide
O H2O2 O
H O
O O H
CH3CO3H
O + CH3CO2H
Why are peroxyacids a good reagent to use when there are other functional groups in
the molecule?
it only reacts with C=C
LG Ch 12 p 7
Give the solubility and any other special properties of the peroxyacids below.
O
O
O
O O H
O H
peroxyacidic acid
peroxybenzoic acid
simplest stable peroxyacid soluble in low polarity solvents
soluble in water, alcohols
O
O O
O
O H O
O
O H H O
Cl O
O
Mg+2
O O
m-chloroperoxybenzoic acid (MCPBA)
magnesium monoperoxyphthalate (MMPP)
soluble in low polarity solvents soluble in water, alcohols
product crystallizes out of solution crystalline
somewhat shock sensitive stable
What type of mechanism does this reaction have?
CH3CO3H O 1.0
+ CH3CO2H
CH3CO3H O
+ CH3CO2H 22 faster
CH3CO3H O
+ CH3CO2H 296
What happens when an alkene reacts with a carbene? a cyclopropane ring is formed
What is a carbene?
H
C reactive intermediate
H no charge, lone pair, empty orbital
heat
CH2N2 = H2C N N CH2 + N N
or light
CH2N2
1
light
What two chemists discovered a reagent that gives better yields and isn't explosive?
CH2I2
2
Zn, CuCl
LG Ch 12 p 9
What happens when chloroform or bromoform react with potassium tert-butoxide?
alpha elimination - very rare
O K
Cl Cl Cl Cl Cl
C OH
Cl H Cl
C + C + K Cl
Cl
carbene
Give the product of the reaction shown below.
CH2N2
cyclopropane rings don't have an O
light
MMPP
O
Addition of X2 to alkenes
Br
Br2
vicinal dihalide
Br
Br2 works
most commonly used
Cl2 works
I2 can be used, but the products decompose easily (why? sterics - I is huge)
Cl2
etc substitution rxn
hv or heat Cl radical goes to any 2o spot
Is it always written? no
Cl2 Cl
Cl
Cl2
same thing!
CH2Cl2
solvent - don't freak out!
If you had two test tubes, one with cyclohexane and one with cyclohexene, how could you
tell them apart?
both clear liquids
they smell different (if you had a labeled bottle, you could use this)
IR - look for C=C band, C-H on C=C band
NMR - look for peaks at 4.5-6.5
chemical test - add Br2 solution show demonstration in 2 test tubes
Br
Br2
clear stays red - rxn is slow
red
Br
Br2
clear goes clear - rxn is fast
red Br
LG Ch 12 p 11
What happens first in the mechanism of this reaction?
alkene attacks a Br, pushes the other one off, Br attaches to the other C
Br Br
Nu Br Br
Br
E
doesn't stop here this is about the only time
you'll ever see a halogen with
What happens next? a + charge
Br no rearrangments occur, so no C+ is
Br formed
Br
Br
Br2 OH
H2O Br
it takes the place of the bromide ion - there are more water molecules around
O
H H Br
Br
O
Br + H3O+
O
H H H H OH
Why does the water attack the more substituted side of the ring?
OH Br
Br2
+
H2O Br OH
LG Ch 12 p 12
Polymerization of alkenes
H2SO4 1 2
2 2
1 1 2 1 2
1
Polymers molecules
are usually hundreds
or thousands of
carbons long. 2 1 2 1 2
1
How would the polymer be different if the alkenes below were used?
1
2 H2SO4 polypropylene
1 1
2 1 2 2
1 H2SO4 each of these polymers would
2 2 2 have different properties
1 1 1
2
H2SO4
polyethylene
1 1
2 1 2 2
Cl Cl Cl
1 H2SO4
Cl polyvinylchloride PVC
2
What problems can this reaction cause when storing alkenes or taking a boiling point?
Polystyrene is a clear, brittle plastic used in drinking cups, CD cases, etc, and in making
styrofoam. How can it be formed using an organic peroxide?
light
H3CO OCH3 2 CH3O + 1 2 H3CO 1 2 + 1
or heat 2
1 1 1 1 1
2 2 2 2 2
we usually don't worry H3CO
about the piece on the
end left by the initiator
H2SO4 OH
H2O
C+ forms, reacts with water
H2SO4
C+ forms, nothing to
react with but the alkene
LG Ch 12 p 14
II. Stereochemistry of Alkene Reactions
yes - E/Z, but not a chiral one; at least not the C=C atoms
Y-Z Y Y
if Y=Z and there is a plane
+
of symmetry, meso
Z Z
Y-Z Y Y
even if Y=Z, there will be no
+ plane of symmetry - 2
Z Z enantiomers
3) nonselective addition - new substituents are added to the same and opposite sides
Y-Z Y Y Y Y
+ + +
Z Z Z Z
hydroboration-oxidation
hydrogenation
hydroxylation
epoxidation
cyclopropanation
H's added from the same face - the side that is toward the surface of the catalyst
LG Ch 12 p 16
Hydroxylation
meso? NO! (use models
both O's attach at the same time if you don't see it
OH
O O O O H2O2
+ Os Os
O O O O
OH
H H
H2O2
+ notice that the
B BH2
H H NaOH OH focus is on the
new substituents,
H H2O2 not the ones
already there!
BH2
NaOH OH
Epoxidation
CH2N2
+
heat 2 enantiomers
note that a pre-existing
H H stereocenter is not changed!
CH2I2
+ 2 diastereomers
Zn-Cu stereoselective - chiral
H H starting material
LG Ch 12 p 17
What reactions give anti addition?
addition of X2
addition of X2 with H2O
Why? bromide ion (or water) must attack from behind the ring
Addition of X2
enantiomers
Br Br Br Br
Br
Br + Br +
Br Br
Cl Cl Cl Cl Cl
*
H2O +
* OH OH OH
+
constitutuional OH OH
isomers * OH
+
* Cl Cl Cl
Oxymercuration-reduction
Hg(OAc)2 OH NaBH4 OH
* * all four
H2O * HgOAc * H
this step is actually anti but this step is random, so the connection is destroyed
LG Ch 12 p 18
Addition of HX
H can come from the top or bottom of the alkene; Cl can come from top or bottom of
the carbocation - both are trigonal planar
HCl
Cl Cl
H Cl
Cl Cl
NOT!!
H
Addition of HBr with peroxide
Br radical can attack C=C from top or bottom, H can attack radical
from the top or bottom
Br
HBr
CH3OOCH3 Br
H H Br
Br
H
Br
Acid-catalyzed hydration
HO
H3PO4
H2O
all four
What steps should you follow when writing out the products with stereochemistry?
1. Draw all products without stereochemistry (watch for constitutional isomers).
2. Identify the stereocenters in the product.
Give all stereoisomers of the following reactions. doesn't matter that it's syn addition - the
other C isn't a stereocenter
H2, Pd/C +
*
OH OH OH
* OH OH OH
OsO4
* +
H2O, H2O2
syn addition, 2 enantiomers
H
CH2N2 *
meso don't forget
heat bridgehead carbons!
* H
1. Hg(OAc)2, H2O OH OH OH
2. NaBH4 *
H H
achiral
OH
OH
O O O
+
H2O2 O
OH
don't have to memorize ketone
this structure COOH
not an addition rxn!
LG Ch 12 p 20
What happens if dimethyl sulfide is present? C's are oxidized to aldehydes and/or ketones
O3
+ O
(CH3)2S O
H
What happens if hydrogen peroxide is present? C's are oxidized to ketones and/or
carboxylic acids
O3 O
+
O
H2O2 OH
O3 OH OH
+
H2O2 O H O
2 O
3 1 O3
6 7
H
4 1 2 3
6 7 (CH3)2S 4 5
5 O
O 4 2
H 1 2 3 5 1
OH 3
O O
O 5 4
it helps to number cyclic ones
OH
O
O O
H
could be cis or trans
only one product =
symmetrical
Reaction Reagents Product Mechanism? Rearrangements? Regioselectivity Stereoselectivity
addition of HX 1) HI, HBr, or HCl alkyl halide yes yes X on more nonselective
substituted C
2) HBr/ROOR alkyl bromide yes no Br on least nonselective
substituted C
addition of X2 1) I2, Br2, or Cl2 vicinal dihalide yes no none anti addition
2) I2, Br2, or Cl2 and H2O halohydrin yes no OH on more anti addition
substituted C