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ALKYNES
Nomenclature
IUPAC: use the infix -ynyn to show the
presence of a carbon-carbon triple bond.
2-Butyne
1-Buten-3-yne
Dimethylacetylene Vinylacetylene
Cycloalkynes
Cyclooctyne is the smallest cycloalkyne
isolated. (unstable; 155bond angle)
Cyclononyne has high degree angle strain.
It is stable at room temp.
The C-C-C bond angle about the triple bond is
approximately 160 (rather than the optimal
angle of 180), indicating high angle strain.
Cyclononyne
Physical Properties
Similar to alkanes and alkenes of
comparable molecular weight and carbon
skeleton.
Acidity
The pKa of acetylene and terminal alkynes is
approximately 25, which makes them
stronger acids than ammonia (pka 38) but
weaker acids than alcohols (pka ~16)
(Section 4.3).
H bonded to triple bonded C acidic enough to be
removed only by very strong base
Terminal alkynes react with sodium amide to
form alkyne anions.
Acidity
Terminal alkynes can also be converted to alkyne
anions by reaction with sodium hydride or lithium
diisopropylamide (LDA).
CH3CH2CH2CH2CCH
2) CH3CH2CH2CH2Br
CH3CH2CH2CCCH3
B)
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Cl2
DCM
NaNH2, NH3
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Allene
Allene: A compound containing a C=C=C
group
the simplest allene is 1,2-propadiene, commonly
named allene
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Allenes
Most allenes are less stable than their isomeric
alkynes, and are generally only minor products in
alkyne-forming dehydrohalogenation reactions.
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Addition of X2 (electrophilic
addition)
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Addition of X2
Addition of bromine to an alkyne follows much
the same mechanism as that for the bromination
of an alkene, namely formation of a bridged
bromonium ion intermediate, which is then
attacked by bromide ion from the face opposite
that occupied by the positively charged bromine
atom.
Addition of a second mole bromine gives
tetrabromoalkane.
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Addition of X2
What is the major product of the following?
A)
CH2Cl2
CH3CH2CCH + Br2
CH2Cl2
B)
CH3CH2CH2CCH + 2 Cl2
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Electrophilic Addition of HX
Alkynes undergo regioselective (follows
Markovnikovs rule) addition of either 1 or 2
moles of HX, depending on the ratios in
which the alkyne and halogen acid are
mixed.
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Electrophilic Addition of HX
Step 1: Make a new bond between a nucleophile
(a bond) and an electrophileadd a proton.
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Electrophilic Addition of HX
In the addition of the second mole of HX,
Step 1 is reaction of the electron pair of the
remaining pi bond with HBr to form a
carbocation.
Of the two possible carbocations, the resonancestabilized 2carbocation is favored.
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Addition of HX
What is the major product of the following?
A)
B)
+ HBr
CH3CH2CH2CH2CCH + HBr
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Hydroboration
Addition of borane to an internal alkyne
gives a trialkenylborane.
Addition is syn stereoselective.
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Hydroboration
To prevent dihydroboration with terminal alkynes,
it is necessary to use a sterically hindered
dialkylborane, such as (sia)2BH.
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Hydroboration
Treating an alkenylborane with H 2O2 in
aqueous NaOH gives an enol.
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Hydroboration/Oxidation; hydration
Hydroboration/oxidation of an internal alkyne
gives a ketone.
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Hydroboration/oxidation
What alkyne and reagents would give the
following?
A)
B)
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A) CH3CH2CH2CCCH2CH2CH3
B) (CH3)2CHCH2CCCH2CH2CH3
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Reduction
Treatment of an alkyne with H2 in the
presence of a transition metal catalyst, most
commonly Pd, Pt, or Ni, converts the alkyne
to an alkane.
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Hydroboration - Protonolysis
Syn-stereoselective addition of borane to an
internal alkyne gives a trialkenylborane.
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Organic Synthesis
A successful synthesis must
provide the desired product in maximum yield.
have the maximum control of stereochemistry
and regiochemistry.
do minimum damage to the environment (it must
be a green synthesis).
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Organic Synthesis
We analyze a target molecule in the
following ways:
The carbon skeleton: how can we put it
together? Our only method to date for forming a
new C-C bond is the alkylation of alkyne anions
with 1 haloalkanes.
The functional groups: what are they, how can
they be used in forming the carbon-skeleton of
the target molecule, and will they be changed by
the reaction conditions to give the functional
groups of the target molecule?
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Organic Synthesis
We use a method called a retrosynthesis
and an open arrow to symbolize a step in a
retrosynthesis.
target
starting
molecule
materials
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Organic Synthesis
Target molecule: 2-heptanone; starting with
acetylene and haloalkanes.
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Organic Synthesis
Starting materials are acetylene and 1bromopentane.
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