11/11/2009

Alkenes and Alkynes

Double
C C
bond
N
Names: E di
Ending ane
n ene
n
For example: Ethene, propene, butene, etc.
Rules:
1. Find longest chain wit both Csp2 s in it.
1
2
3

8 6 An oct
octene
ene
7 5 4

2. # Chain with C C close to terminus

1
2
3

8 6 A 3-oct
octene
ene (only the
7 5 4 first of the two Csp2 s
is named by a #)
Lingo: Double bond position

R R
CH2 Terminal
T i l Internal
I t l
R R
3. Name and # substituents, in alphabetical order
4-Ethyl-
Ethyl-3-methyl-
methyl-3-oct
octene
ene

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1
2 1 2
4. Cycloalkenes C C By definition
3
3-Methylcyclohex
Methylcyclohexene
ene
CH3
R
5. Stereoisomers:
cis trans
R R R
Cis/trans used for 1,2-
1,2-disubstituted ethenes.
6. For tri-
tri- and tetrasubstituted alkenes: E, Z
naming. Use R, S priority rules at each sp2-carbon separately
separately,,
to find higher
g priority
p y groups
g p at each end.

1 Opposite sides: E
2 Same side: Z
3

8 6 E-4-ethyl-
ethyl-3methyl-
3methyl-3-oct
octene
ene
7 5 4

2
OH
7. OH ( SH) > ene
3 1
2-Propen-
Propen-1-ol

8.
8 SSubstituents:
b tit t Alk
Alkenyll CH2 CH Ethenyl
E h l (vinyl)
( l)
CH2 CH CH2 2-Propenyl (allyl)

9. Exocyclic alkenes: Alkylidenecycloalkanes

Methylidenecyclohexane
(Methylenecyclohexane)

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 11/11/2009

Structure of Double Bond

“Electron rich”

The
Sigma Bond

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The Pi Bond

Ethene

Orbital
Energies

 Bond is
relatively weak

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How Weak is the  Bond?

Ea = 65 kcal/mol

Bond Strengths (kcal/mol)

Unusually strong because C uses sp2 hybrids

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Acidity:Alkenyl hydrogens C C pKa ~ 44

are relatively “acidic”
H
Cf. CH3CH3 H ~ 50. Therefore, in principle:
R H H
C C + CH3Li RCH C + CH4
H H Li
Problems: Regio
Regio--, stereoselectivity. Better:
H H
CH2 C + Li CH2 C Useful:
Br Li React
R H with
R H
C C carbonyls
+ Mg C C
H Br H MgBr

Why are alkenyl hydrogens acidic?

sp2 Has 33% s character.

C C
In contrast:
H
sp3 has 25% s
character

Net effect: relatively e-withdrawing

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1H NMR C C δ ~ 4.5-
4.5-6 ppm: deshielded!
H

Why? 1. sp2 2. e-Flow of  cloud

Strengthens
H0

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Coupling Constants
Depend on stereochemistry.

H H “Vicinal”
Vicinal coupling:
C C JHH trans= 11-
11-18 Hz; JHH cis= 6-
6-14 Hz
R H
“Geminal” coupling:
JHH geminal ~ 0-
0-3 Hz

For cis/trans isomers: Jtrans always > Jcis.

Double bond “transmits” long range (over 3-
3-4 C)
coupling (1
(1--3 Hz).

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13C NMR Csp 2 deshielded (reasons are complex)

δ = 110 – 150 ppm “left half” of total spectral window
Alkenes Alkanes
H3C 122.8
122 8 CH3 H3C CH3
34.0
C C HC CH
H3C CH3 H3C CH3
18.9 19.2
H H 22.2
22 2
123.7 132.7
C C
H3C CH2CH3 CH3CH2CH2CH2CH3
12.3

20.5 14.0 13.5 34.1

(CH3)4Si

(CH3)4Si

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Vibrations in Molecules:
Infrared (IR) Spectroscopy

Compounds resemble a mechanical frame: they

“rattle”. Rattling is quantized.

Excited state ΔE = hν ~ 11--10 kcal mol-1

E ~
in λ or 1/λ = υ “wave
“ numbers”
b ”
Ground state Range: 600
600--4000 cm-1

A ~ : Determined by Hooke’s Law

B stretching υ
~ f = force constant m = mass
υ = k√ f mA+mB
mAmB (reflects bond strength)
~
υ goes up with larger f, smaller m
Not only stretching: also bending and coupled modes
Complex patterns 600-
600-1500 cm-1 : The fingerprint region

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Infrared Modes

The Infrared Spectrometer

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Fingerprint region

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Most useful: 1. Alkyl ~υC-H = 2900cm-1

~ 2
2. Alkenes υ ~
Csp - H = 3080 cm , υC - C = 1640 cm ,
-1 -1

H R~
C C υ = 970 cm-1
R trans H
3. R O H
3350 cm-1
O (broad)
4. C 1740 cm-1
H

H
Trans-2-hexene

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Degrees of Unsaturation
Molecular formula tells us how many rings and/or
 bonds are present in a molecule. Reference is a
saturated acyclic hydrocarbon: CnH2n+22.
Simple examples:

C6H12, not C6H14. C6H10, not C6H14.

We need to determine the deviation of the

molecular formula from CnH2n+2 (in increments of
2H). Every ring or double bond takes away 2H,
triple bond 4H from CnH2n+2.

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Effect of Presence of Heteroatoms on CnH2n+2

Depends on valency of element:

S, O no effect on count (still CnH2n+2 + Sx or Oy)

C H C O H

Halogen: -1; C H C X

H
Nitrogen: +1
+1;; C H C N R

Steps:

1 Calculate Hsat = 2n C + 2 – nX + nN
1.
n = “number of”

2. Count Hactual in given molecular formula.

formula.

3. Degree of Unsaturation:
Unsaturation: (Hsat – Hactual)/2

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Examples:
C10H16 1. Hsat = (2x10) + 2 = 22
2. Degree of unsaturation: (22-
(22-16)/2 = 3

or etc.

C5H5N 1. Hsat= 10 + 2 + 1 = 13
2. ((13 - 5)/2
) = 4 degrees
g of unsaturation:

Or Or?
N C N
Pyridine

Problem

C3HN: How m
many
y degrees
g of
f unsaturation?

Hsat = 2n C + 2 – nX + nN
Degree of Unsaturation: (Hsat – Hactual)/2

A. 2
B. 3
C. 4

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Relative Stability of Alkenes

Measure heat of hydrogenation ΔHH2 of isomers,
e.g., butene
ΔHH2 (kcal mol-1)
cat.
+ H2 -30.3
cat.
+ H2 -28.6

cat.
+ H2 -27.6

Stability: Internal > terminal , trans > cis

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Why? 1. Hyperconjugation:
H
2. Steric hindrance (strain) C C
C

Cis is less stable than

trans because of
steric hindrance

General order of stability:

CH2 CH2 < RCH CH2 < RCH CHR cis
< RCH CHR trans < tri < tetrasubstituted

Synthesis of Alkenes
E revisited. Best: E2 on RX. Regioselectivity?
CH3 H3C CH3 H2CCH3
base
CH3 CH2 C CH3 C C + C CH2
X H CH3 H3C
more stable less stable

S t
Saytzev-
Saytzev-Rule
R l
Non-bulky base:
Non-
More stable
product.

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Hofmann Rule
Bulky base: Less stable, terminal product is major

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Is elimination stereoselective?
stereoselective?
I.e., will it make preferentially cis or trans
product? Yes, but not completely.
Br +-
Na OCH3
N
+ +
CH3OH
51% 18% 31%

Trans predominates (not much)

S
Stereospecificity?
ifi i ? Yes
Y .
Yes.
E or Z from respective
C* C *
diastereomeric haloalkanes:
H X

Stereospecificity:

Good!
G d! Each
E h
diastereomer
gives only one
stereoisomer of
alkene product

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Alkenes from ROH by

Dehydration:
Often Messy
Rprim OH + H2SO4 conc., goes by E2, requires heat:

+
CH3CH2OH + H
: :

+ H -
CH2 CH2 O + HSO4 CH2 CH2 + H2O

: :
:

H
H + H2SO4

Rsec, Rtert OH : E1 + rearrangements

Acid--Mediated Dehydration of Alcohols

Acid
Acid, Δ
C C C C + HOH
H OH
Relative Reactivity of Alcohols (ROH) in
Dehydration Reactions
R = primary < secondary < tertiary
conc. H2SO4, 170
170°°C
CH3CH2OH CH2 CH2
HOH
HO H
50% H2SO4, 100
100°°C
CH3C CCH3 CH3CH CHCH3
HOH
H H + 80%

CH2 CHCH2CH3 Trace

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CH3
Dilute H2SO4, 50
50°°C
(CH3)3COH H2C C 100%
HOH
CH3

Dehydration
h d with
h Rearrangement
CH3 OH
H3C H
H2SO4, Δ
CH3C CH2 CCH3 C C 54%
HOH
H3C CH2CH3
H H
CH3
+ CH3CCH CHCH3 + other minor isomers

H 8%

33% H2SO4, 1 h, 100

100°°C
+
H2O

OH
Acid-catalyzed
Acid- 15% 9%
α-Terpineol dehydrations give Terpinolene Limonene
mixtures
Terpenes: The scent
of soap
+ + +

28.5% 18.5% 15%

α-Terpinene Isoterpinolene γ-Terpinene

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Reactions of Alkenes

Polyethylene
Tear resistant

Addition Reactions of Alkenes

π Bond is unsaturated
unsaturated.. Reacts
by addition
addition..

C C +A B exothermic
C C
(usually)
A B
We can calculate ΔHº from bond strength
data, using DHºπ-bond = 65 kcal/mol. Note,
however: ΔSº is negative (~ -30 e.u.)

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1. Catalytic Hydrogenation:
Hydrogenation: H2 + catalyst

cat. Heterogeneous
C C +H H C C catalysts

Pd/C, PtO2 (
H2
Pt))
Pt
H H

Why catalysts? Enable a lower Ea mechanism.

Alkenes + H2 Uncatalyzed
no reaction
without catalyst
E pathway

Catalyzed pathway

Mechanism of hydrogenation: Occurs on

surface of catalyst
catalyst.. Involves stereospecific H-
H addition from the same side (syn
(syn)) of double
bond.

H
cat. CH3
+ H2 cis
CH2CH3
H
H
D2 D
R R + SS
cat. H
trans D

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Lipshut
Orbison

Vegetable Oils, Soft Margarine, and Butter:

Hydrogenation “Hardens”

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“Margarine” comes from “oleomargarine”, in turn derived

from : a. Olefins, the original name for alkenes, because
addition reactions of many gaseous alkenes give oils as
products (from oleum facere, Latin, to make oil); b. margaric
acid, one of the constituent fatty acids of margarine,
h t d
heptadecanoici acid
id (f
(forms shiny,
hi “pearly”
“ l ” crystals,
t l Greek,
G k
margaron, pearl)
The fat molecules in butter and hard (stick) margarines are
highly saturated, whereas those in vegetable oils have a high
proportion of cis-alkene functions (more than 90%). Partial
hydrogenation
y g of
f these oils y
yields soft
f ((tub)) margarine.
g
Conditions of hydrogenation also isomerize cis double bonds
to trans. For example, hard margarine: 35% saturated fatty
acids (SFAs), 12% trans fatty acids (TFAs); natural butter
>50% SFAs, 3–4% TFAs. Soft margarine (less hydrgoenation)
~15% SFAs, ~5% TFAs.

TFAs and Health

TFAs not metabolized in same way as cis counterparts;

TFAs in foods greatly affect lipid metabolism;
TFAs accumulate in cell membranes, increase levels of low-
density lipoproteins ((“bad
bad cholesterol”)
cholesterol ) in blood while
reducing high-density lipoprotein levels (good cholesterol);
Increased risk of breast cancer and heart disease.

TFAs are present in fried fast foods (french fries) and many
baked goods (cakes, cookies, crackers, and pastries).
American Heart Association (2005) recommends:
<30% of caloric intake from fat; < 10% trans and saturated
fats.

USDA (1.1.2006) requires all food to list trans fatty acid

content.

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2. Electrophilic Additions
π Bond is e-rich.
rich. Polar reagents + ―B-
reagents A―B
A
add to it.
+ +
Mechanism for A = H: Reverse of E1!
H - H B
+ + :B
C C +H C C C C

+ -
a. Hydrohalogenation H X
- I Reverse of
+ I
+ HI 0ºC
elimination
H H
Br
H
Regioelective: HBr

Cl
+ HCl
Markovnikov’s Rule
H+ (A +) adds to less substituted carbon
Why? Makes the more substituted cation
1838--
1838
1904

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PropeneHCl

Lipshut
Caruso

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+
b. Markovnikov Hydration H2O, H catalyst

H2SO4 CH3
+ H OH OH
H Equilibrium !
solvent

Reversible Hydration of 2-
2-Methylpropene:

H+ consumed H+ regenerated

Consequences of
Reversibility of E1
Alkene isomerization
H+ H+

Equilibration = Thermodynamic control

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Mechanism of Thermodynamic
Control

Step 1

Step 2

Reminder: C C + A B C C
A B
c. Halogenation A = B = X
X X gets polarized during approach
to alkene.
+ Br2 Br
Br
Stereospecific : Anti (not syn)

C C or C C

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Brominations can be “titrated”

Stereospecific 2-Butene Bromination

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- Mechanism:
Br
+
Br Br + - Br
+ Br
C C C C
C C
Br
“Precomplex” anti

Lipshutz
Django

This Is Hot Recent Stuff!!

Bellucci Lenoir,
Bellucci, Lenoir Herges
Herges,
J. Am. Chem. Soc. 1995
Lenoir, Chiappe,
Chem. Eur. J. 2003

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A Chloronium Ion Structure

Kochi, Chem. Commun. 1998

1.92 Å 2.08 Å

Time Out: Alkenes As

Nucleophiles/Bases

Base :

Nucleophile :

General :

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Cylic Halonium Ions : Resonance

Forms vs. Isomerization

Resonance :

Equilibrium :

Halonium ions can be intercepted by other Nu

Br +
Br
OH
+ Br2 + H2O OH2
via
+ H
Cf. O Or X2, ROH Haloethers
+ Nu (all anti and Markovnikov)

H3C CH3OH OCH3

+
+ Cl2 + CH3OH
-H+ Cl
H3C Cl+

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Synthetically useful in
oxymercuration--demercuration
oxymercuration

d. Oxymercuration
Oxymercuration--Demercuration
A Markovnikov hydration
that avoids cations
O
1. Hg(OCCH3)2, H2O CH3
OH
2. NaBH4

O
CH3
Or 1. Hg(OCCH3)2, 2. ROH: Gives OR
ethers

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Goes through rad

3. Hydroboration
Hydroboration--Oxidation
Allows anti
anti--Markovnikov hydration:
hydration:
RCH = CH2 + H2O RCH2CH2OH
Key reaction: B H adds to π-bonds.
Time out: Borane, BH3, exists as dimer to get octet
H
- +
H2B BH2; in THF: H3B O
H
All three B-
B-H bonds react:
H
H
3 C C + B H C C B Alkylborane
H 3

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Hydroboration is regioselective: Steric

control of B-
B-H addition

+ BH3 BR2

less hindered

Why is hydroboration useful?

Oxidation of alkylboranes with H2O2-, OH
gives ROH
ROH [+ B(OH)3]

H2O2
+ BH3 BR2 OH
OH -

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Hydroboration is Stereospecific:
Syn addition of B—
B —H

H3C H H3C H
CH3 H2O2, -OH CH3
+ BH3 B
OH

Negative charge pushes

Look Familiar?

Positive charge pulls

BH3Oxn

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Applications
Think retrosynthetically
retrosynthetically::
H OH H3C H
H3C C C H C C
CH3CH2 CH3 CH3CH2 CH3

CH3
Cl
I OH

4. Electrophilic Carbene Additions

Carbenes, :CR2, are 6-electron

Carbenes 6 electron
species, the parent of which is H
methylene, :CH2. They can be : C
thought of being derived by H
deprotonating carbocations,
CH3+  :CH2 + H+.
M th l
Methylene

Carbenes are electron deficient: electrophilic.

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Synthesis (as reactive intermediates)

a. Methylene from diazomethane CH2N2

b. Dichlorocarbene from chloroform

c. Simmons-
Simmons-Smith reagent Carbenes pick up
the two  electrons
CH2I2 + Zn-Cu  “CH2”
of alkenes to form
cyclopropanes.

a.

Stereospecific !
b.

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c. Simmons-
Simmons-Smith Reagent in Cyclopropane Synthesis

H CH3 CH2
C C Zn Cu, (CH3CH2)2O
+ CH2I2 H C C
H3C -Metal iodide CH3
H
H3C H

Cyclopropanes are made by nature…

H3C (+)- Chrysanthemic acid

(+)-
COOH (used by the flower
H3C
against insects); the
“mother” of the
H3C CH3 Pyrethroids..
Pyrethroids
US market: 1.5 billion $!!

…as drugs:

Antifungal
…for “fun”:
OH
HO

Chiral

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Addition of Six-
Six-electron
Species to the π-Bond

H: H : :H H

:
:

:
B:H C :N: :O: :Br:
H:
X +, , or neutral
:

Oxidation?

5. Electrophilic Oxidation O - +
a. Peroxycarboxylic acids RCO OH

O O O
C C + RCO OH C C + RCO
RCOHH

Commonly used peroxycarboxylic acids:

O O O

CH3COOH, CF3COOH, COOH

Meta-chloroperbenzoic acid
Peracetic Trifluoro-
Trifluoro-
acid peracetic acid “MCPBA”
Cl

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O O
C O OH CHCl3 COH
CO H
+ 90%
+
O
Cl Cl

Stereospecific: Syn
D H O O O
C C + RCOO
RCOOH
H + RCOH
H D 95% D H
H D Aqueous
work up
Trans-2,3-
2,3-di-
di-
deuteriooxa-
deuteriooxa-
cyclopropane

O R
C O R C C
Mech.::
Mech. O C O +
C C O
H O
H
Application:
O HO H
:Nu1 CH3
1.CH3SO2Cl
C C
H3C 2. :Nu2
H3C CH3 Nu1
H
H3C H
H CH3
C C Double nucleophilic syn –
addition to double bond
Nu2 Nu1

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Rates of oxacyclopropanation increase with

alkyl substitution :
O
CHCl3
+ CH3COOH 10ºC
O
1 equiv 86%

Sequence 1. RCO3H, 2. H+, H2O or –OH, H2O

constitutes an anti
anti--dihydroxylation of alkenes.
O
H3C H RCO3H
C C H
H3C
H CH3 CH3
H
HO H
H+, H2O CH3
or –OH, H2O C C meso
H3C
H OH

This is at the forefront !

Sarzi-Amadè et al. J. Org. Chem. Dec. 2002

Good! Not good

Π* -lone pair Non-synchronous

Non-
stabilization concerted

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b. Syn
Syn--dihydroxylation

Reagents : KMnO4, -OH, or better:

O O
OsO4 is reduced to OsVI.
Os
O VIII
O
OH
1. OsO4

2. H2S,, H2O OH
Cis-1,2-
1,2-cyclohexanediol

Gives complementary stereochemistry to

anti--dihydroxylation
anti

Mech.: O
C OVIII O C VI O H O
2
Os Os
C C
O O O O
Six electron TS
Osmate ester
C OH HO O
Can be reoxidized by added
+ VI
Os oxidant, therefore can be
C OH HO O made catalytic in Os

Good because Os is expensive; OsO4, H2S are toxic.

-
O + CH3
Other oxidants: H2O2 ; Fe3+; N
and catalytic OsO4 O

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c. Ozonolysis Complete oxidative cleavage by

1. O3, 2. Reduction of “ozonide”
Ozone generator:

O+
Arc discharge
O2 2-4%- in O2
O O
1. O3
C C
2. Reduction
C O +O C
O O
CH3CH2 CH3 1. O
C C 3
CH3CH2CCH3 + CH3CH
H3C H 2. Zn
Zn,, CH3COOH
90%
Zn2+
CH3 1. O3 O
H
2. H2 , Pt
85%
H2O Ring opening O

H3C H3C O
1. O3
76%
2. (CH3)2S
H (CH3)2SO H Clip off
carbon atom

Ozonolysis

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6. Radical Hydrobromination

Recall: + HBr Markovnikov

Br
RO--OR
RO Anti-
Anti-
But: + HBr Br Markovnikov!
Mechanism different; goes via faster, radical chain.

Popular peroxides :

Compare to radical halogenation of hydrocarbons:

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Does not occur for HCl, HI: One of the

propagation steps endothermic, hence too
slow, and ionic mechanism of Markovnikov
addition wins. But works for RSH, HCX3
anti--Markovnikov additions.
anti

Chloroform Additions
H
ROOR
CH3(CH2)5CH=CH2 + HCCl3 CH3(CH2)5CHCH2CCl3
24%
1,1,1--Trichlorononane
1,1,1
Mechanism:

RO· + CHCl3
CH ROH
RO H + ·CCl3
Chain carrier

N t
Not: RO + Cl
RO· Cl―CHCl
―CHCl
CHCl2 ROCl
RO Cl + ·CHCl
CHCl2

General:
ROOR
RCH=CH2 + A―B RCH―CH2B
A

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Chemistry Nobel Prize 2005

For alkene metathesis:
metathesis: Two alkenes exchange their
doublebonded carbon atoms,

Chauvin, Schrock, Grubbs

7. Alkene Polymerization

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R + R etc.
a. Cationic: C C + H+ H C C
R R
b. Radical: RO + C C RO C C
H H
- C N - C N
c. Anionic: B + C C B C C
Resonance

d.
d Metal (Ti,
(Ti Zr,
Zr lanthanides): Zi l -Natta;
Ziegler-
Ziegler N tt now
Kaminski--Brintzinger. Organometallic mechanism
Kaminski
R R
Insertion CH3 CH3
R Ti CH3 R Ti Ti

a. Acid
Acid--catalyzed Polymerization
Proceeds through carbocations (another
complication), in addition to SN1, E1, and
rearrangements; dominates at high concentrations.

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Controlled Oligomerizations in Nature

Acid--catalyzed Steroid Synthesis: Stepwise
Acid

This one is weird;

makes sec. cation.
True?

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 11/11/2009

b. Radical Polymerization

Not true… stepwise, then concerted :

Corey; Jorgensen;
Hess, J. Am. Chem.
Soc. 1995; 1997; 2002.

Tert-cation first. Would need rearrangement to secondary:

~10 kcal/mol uphill. Necessary? No!

Last two rings :

concerted !
TS

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8. Alkenes in Nature: Pheromones

Sex, war, communication (trail, alarm, defence)

NO2 Termite
defence
O
O Black tail deer (hoof excretion);
recognition and status
O O

OH
“Queen
Queen bee substance
substance”, inhibits ovary development
in workers, attracts–
attracts–excites drones

Limonene: Bee sting, alarm,

aggression

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cis-Tetradecenyl acetate: Sex attractant for

the European
corn borer

SF Chronicle 2003
Male feeds on an azacyclopentane rich diet,
includes this chemical in his sperm, protects
female and eggs. Female senses “chemically-
rich” prospective mating partner!

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The Holy Grail: Human Sex

Pheromones

C&EN, Feb. 2003

Alkynes: The C C Triple

Bond
Names
Like alkenes, but ending -ene turns into –yne.
4
1 3 6
5
4 2 2
HC CH 5 1
3 Br
Eth
Ethyne 1-Pentyne 5-Bromo
B
Bromo--2-hexyne
h

1
Priority: 2

OH 2-Propyn-
Propyn-1-ol
3
-ol > -yne

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When the alkyne contains also double bonds, it

is called an enyne. However, despite being an
“yne”, numbering begins closest to either group:
2
1
3 4
2 6 3

1 5 4
5
3-Hexen-
Hexen-1-yne 6 1-Hepten-
Hepten-4-yne
7

When double and triple bond are equidistant from

each
h terminus: Ene
E first (alphabetical)
( l h l)
2
1
3

4
1-Penten-
Penten-4-yne
5

Substituents:

Ethynyl 1
2 2-Propynyl
(or propargyl)
Rings: Naming follows hydrocarbon rule:
Smaller R is a substituent to larger R (ignore
function)

3-Cyclobutyl-
Cyclobutyl-1-hexyne Ethynylcyclohexane

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Two perpendicular π bonds; sp hybrids

R C C R

Ethyne

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The Triple Bond is

Energetic
DH ° HC CH H2C CH2 H3C CH3
Kcall moll-1 229 173 90

Heat of hydrogenation:
hydrogenation
y g : More than Two Alkene  Bonds
(which would be ~ -60 kcal mol-1)

Acetylene Torch

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- K -
Acidity: RC C H + :B R C C : + HB

pKa ~ 25! cf. CH2 CH2 44, CH3 CH3 50

Why? 5
50% s-
s-charact
characterr

Hydrogens get more acidic (blue)

Synthetic Use of Acidity

+ Li or - + +
Li Li
pKa 25 pKa 50

+ CH3MgBr MgBr + CH4

- -: NaNH2
H H + Na+ :NH2 H
:

1 equiv. +- - +
Na :C C : Na
+ NH3
pKa 33

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1H NMR: RC C H δ = 1.7-
1.7-3.1 !
Recall: RCH CH2 δ = 4.6-
4.6-6 ppm

Why? Cylindrical electron current

shields alkynyl hydrogen
Recall alkene NMR

Alkene
Alk ene hydrogens: Alkyne
Alk yne hydrogens:
deshielded shielded

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Coupling: Long range: H2 C C H J = 2-

RCH
RC 2-4 Hz
RCH
RC CH2 R’ J = 2-
H2 C C CH 2-3 Hz

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13C NMR: δ = 65-

65-85 ppm: Also shielded.

Compare alkenes: HC CCH2CH2CH2CH3

120--150ppm.
120
69 84 14--31
14

IR spectra: diagnostic peaks for triple bond

and its attached H.
strong

~ ~
υ (R
(RC
C CR’) = 2120 cm-1 ;
CR’) υ (RC C H)
H) = 3300 cm-1

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Stability of Alkynes:
Heats of Hydrogenation Revisited

Special
p cat.
HC CH + H2 CH2 CH2 ΔH ° = -44.9
44 9
kcal mol-1

Cat. ΔH ° = -32.7
CH2 CH2 + H2 CH3 CH3
kcal mol-1

First Π bond has more “heat content”, is

also more reactive.
reactive Allows for:
A R2 A B
R1 C C R2 + A B C C + C C
R1 B R1 R2
Stereoselective alkene synthesis

Internal alkynes are more stable than

terminal ones

cat. ΔH ° = -69.9 kcal mol-1

+ H2

+ H2
cat. ΔH ° = -65.1 kcal mol-1

Parallels the behavior of alkenes.

Same reason: hyperconjugation
hyperconjugation..

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Preparation
1. Elimination E2 of Dihaloalkanes

X X
- B: H - B:
C C C C C C
X
H H

NaNH2 H+, H2O

excess workk up
Br NH3 liq.
Br Na 75%

Application in synthesis:

RCH CHR R C C R

Br
Br2 Br
Br
Br
NaNH2
NH3 liq

1,5--Hexadiyne
1,5

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2. Alkylation of Alkynyl Metals

SN2 rules
Li
Li I
THF Δ
90%

Best:: RI, THF, Δ. RBr or RCl need

Best
“coordinating” additives: e.g. H2N NH2 ;
or HMPA. Remember: Grignards don’t work
O
for RX, but O.K. for or carbonyls.

MgBr
+ CH3MgBr OH
CH2 O

O
+ LiNH2 (l equiv) Li OH

O
CH3CH OH HO
+ 2 CH3MgBr BrMg MgBr

O
Li CH3 OH
+ Li

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Reactions
1. Reductions a. Complete hydrogenation
H2, Pt
100%
b. Partial hydrogenation: “Poisoned” Lindlar’s
catalyst:
O Cis!
Pd--CaCO3, Pb(OCCH3)2,
Pd quinoline
N
H2, Lindlar H H
Ci -3-heptene
Cis-
Cis h
100%
c. Na reduction: Trans! Via stepwise 2e transfer
NH3 liq. H
+ Na°
Na° Trans-3-
Trans-
86%
H heptene

Mechanism:
Na dissolves in liquid ammonia, makes “solvated” electrons

Equilibrates between
cis and trans (more stable) Holiday
Lipshutz

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2. Electrophilic additions. Like alkenes.

a. HX:
Internal alkynes + -
R X
R R + H+ C C R Anti to H;
sp 2
H sp pushes R
trans

R X
Resonance with X
-
H+ + X X
C C Markovnikov
RCH
RCH2 C RCH
RCH2CX2R
H R R Geminal dihalide

H HX
HX X
RC CH C C RCX2CH3
R H
Markovnikov twice

Angew. Chem. 2004, 43, 1543.

δ 13C = 202.4 ppm

1.22 Å Linear!
+

~
ν = 1987 cm -1

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Examples:
Br Br
HBr

I I
HI + I I

Cl Cl
HCl

Note:
Br2 NaNH2 HBr
Br
NH3 Br Br
Br
Vicinal Geminal

b. X2: Anti addition,

addition, as for alkenes
Br CH3
Br2
CH3
Br
Br Br
Br2
Br Br

c. Cat. HgSO4, H2O hydration,

hydration, Markovnikov
O
Cat. HgSO4 H R Tautomerization
RC CR H2O C C RCH2CR
H+ or -OH
No NaBH4 R OH catalyzed
needed Unstable

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Mechanism of tautomerization
H R
-
C C H+ or OH catalyzed
R OH

R O
+ R -H+
H+ : RCH2 C RCH2 C + H RCH2CR
OH O

O
- H R H - R +H+
OH : C C - C C RCH2CR
R O R O

cat.HgSO4 HO
O
RC CH C CH2 RCCH3
H2O
R
Methyl
y ketone

d. Radical HBr: Anti

Anti--Markovnikov addition

HBr Br Br

ROOR

HBr Br H Br
+
-Br Mixtures
H

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Haloalkenes
No SN2:

No SN1:

But:

And, metal catalysts couple alkenyl halides to

alkenes in the Heck reaction:

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A variant with alkynes: Sonogashira reaction

R’
R X R
C C + R’C CH C C
H R H R

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e. Hydroboration-
Hydroboration-Oxidation
Use R2BH (R = bulky group) to protect
alkenylborane: R = cyclohexyl

R H H2O2, -OH
RC CH + B-H C C
2 H BR2
Steric control

R H O
Tautomerization
C C RCH2CH
H OH
Aldehyde !

Therefore: 1. HBR2
H
2. H2O2,-OH
O
HgSO4 O
but cat.

H2O

O
1 R2BH
1.
R R RCCH2R
2. H2O2,-OH

R = R : Mixtures

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