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2010

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Nomenclature
Preparation
Structure
Chemical reactions
 a



¦  are hydrocarbons that have at

least one triple bond,
bond, |Ł| with the
formula | .

¦ ºisubstituted alkynes, R-
R-|Ł|-R', are
"R
 "
described as "R " alkynes;
¦ Donosubstituted alkynes, R-
R-|Ł|-H,
are described as "
R
"
R "
" alkynes.
 


u

u u


u u


u
u

m
m m 
mmm  m




u


u

 m

¦ [ecause of its linear configuration, ten

ten--
membered carbon ring is the smallest that
can contain the alkyne function without
excessive strain.
] m
¦ Classify each of the following as an internal or
a terminal alkyne:
a) 1-
1-hexyne b) 3-
3-octyne
c) cyclooctyne d) propyne
 Nomenclature

¦ Akynes are named by general rules similar

to those used for alkanes and alkenes.
¦ The suffix Œ
 is used in the paren
hydrocarbon name to denote an alkyne,
and the position of the triple bond is
indicated by its number in the chain.
¦ Numbering begin at the chain end near the
triple bond so that the triple bond as low a
number as possible.
|
| | | ||| |
[
 


    
 
|

  


 


¦ Compounds containing both double and

.
triple bonds are called 

.
¦ Numbering of the hydrocarbon chain starts
from the end nearer the first multiple
bond, whether double or triple.
¦ Ifthere is a choice in numbering, double
bonds receive lower numbers than triple
bonds. For example,
u

u




u
 u u u



u u





u
 u u u u



u u

3 3

u 
       
 Preparation of Alkynes

¦ Alkynes are generally prepared by

* ºehydrohalogenation of either geminal
(1,1--) or vicinal (1,2
(1,1 (1,2--)alkyl dihalides
(usually [r or Cl), using a strong base,
usually NaNH2.
¦ Thesereactions are typically E2 reactions
and occur via an alkenyl halide.
halide.
* The reaction of metal acetylides with
primary alkyl halides.
halides.

| |
    | | 
] m
¦ §hat is the alkyne product from the reactions
of the following with NaNH2:

a) 2,2-
2,2-dibromopropane
b) 1,2-
1,2-dibromohexane
c) 1,1-
1,1-dibromooctane
d) 2,3
2,3--dibromohexane
 Structure and Reactivity
¦ The alkyne functional group consists of two
 hybridised C atoms bonded to each other
via one ı and two ü bonds.
¦ The 22ü
ü bonds are produced by the —R
—R



—R
 of the two pairs of -orbitals
not utilised in the hybrids.
¦ The diagram shows the heats of hydrogenation
of 2-
2-butyne (in the slide: blue in units of kcal/mole)
kcal/mole)
¦ It indicates that alkynes are thermodynamically
less stable than alkenes
to a greater degree than
alkenes are less stable
than alkanes.

¦ The "extra" ü bond in an alkyne is weaker that

an alkene ü bond:
2 x 28.3 (C=C) ± 65 (C
(CŁ
ŁC)= 8.4 kcal
¦ The 2 C of the || and the 2 atoms
attached directly to the || are R  so
they cannot exist as R—
R—/
 —
— isomers.

ı ü

ı
Two separate perpendicular  molecular orbitals
¦ The ü bonds are a region of high electron
density;; so it allows an acetylinic carbon
density
to have a greater amount of
electronegative character.
character.
]As a result, alkynes are typically
 R—..
 R—
] Terminal alkynes, R-
R-|Î|-H, are quite
acidic (pKa = 26).
¦ Reacting with a strong base such as
sodium,, sodium amide,
sodium amide, -butyllithium or a
Grignard reagent,
reagent, a terminal alkyne gives
the anion of the terminal alkyne (a ©

):
  
):

|
| |

|
 |
|
|

|

The acetylide ion is a good nucleophile and
can be alkylated to give higher alkynes.
 Like alkenes (||
(||),), the alkyne ||
undergoes a variety of addition reactions in
which one or both of the ü bonds are
converted to new ı bonds.
 Alkylation of Alkynes


¦ The acetylide carbanion, RCŁC , is a good
|-nucleophile and can undergo
nucleophilic substitution reactions (usually
SN2) with 1o or 2o alkyl halides (Cl, [r or I)
to produce an internal alkyne.
¦ `neor both of the terminal H atoms in
ethyne (acetylene) H-
H-|Ł|-H can be
susbtituted providing monosubstituted (R-
(R-
|Ł|-H) and symmetrical (R=R') or
unsymmetrical (R  R') disubstituted
alkynes R-
R-|Ł
|Ł |-R'
D 
  

 
 

¦  The amide ion acts as a

The
base removing the acidic terminal
H to generate the acetylide ion,
a carbon nucleophile.
¦  The carbanion reacts
The
with the electrophilic carbon in the
alkyl halide with loss of the leaving
group, forming a new || bond.
] ×
× !"

¦ §
 
  
  Œ
 
     
¦
   

 
 


¦ 

   


¦   
    !

 Addition Reactions of Alkynes

¦ lkynesundergo addition reactions in an

analogous fashion to those of alkenes.
¦ Two factors influence the relative
reactivity of alkynes compared to alkenes:
 increased nucleophilicity of the starting ü
system (|
(|Ł| vs ||
||), ), and
 stability of any intermediates
(for example, carbocations).

¦ Since alkynes are thermodynamically less

stable than alkenes, we might expect
addition reactions of alkynes to be more
exothermic and relatively faster than
equivalent reactions of the alkenes.
 3 

   

¦ Alkynes can be partially reduced to R—

R—--
alkenes with H2 in the presence of poisoned
catalysts,
] er Pd / CaC`3/ quinoline which is also
known as
R 's
's catalyst.
¦ Alkynes can be reduced to alkanes with H2
in the presence of catalysts (Pt,
(Pt, Pd, Ni etc.)
¦ Thereaction is —
 —RR
giving only the —
addition

addition
product since the new C-
C-H ı
bonds is formed simultaneously
from H atoms absorbed onto the
metal surface.
   D

  
   

¦ Thereaction of Na in NH3(l) with alkynes

occurs —
 —RR giving only the

 —
—alkene via an 
R-

R-addition
addition..
¦ The reaction proceeds via single
electron transfer from the Na with
H coming from the NH3.

¦ These reaction conditions do not

reduce alkenes.
 å 

    


¦ §hen treated with HX alkynes form vinyl

halides.

¦ Hydrogen halide reactivity order :

#$%$|$&
(paralleling acidity order).
order).
¦ Inthe presence of excess HX, a second
addition can occur to the product alkene
giving a geminal dihalide.

¦ Regioselectivity
predicted by
Darkovnikov's rule with the H adding to
the C with the most H already present.
¦ Reactionproceeds via protonation to give
the more stable carbocation intermediate.

¦ Notstereoselective since reaction

proceeds via planar carbocation
(CH3C=CH2 & CH3C[rCH3).
] m
¦ §hat would be the product from the
reaction of 2-
2-butyne with excess H[r ?
¦ For%, in the presence of radicals
%,
(compounds such as peroxides) the
radical addition occurs with  —R


rR R—
:
rR R—
:

] m
§hy does this reaction have the

opposite regiochemistry ?
¦ |
! 
 
!

|'() * ||()+ |()* ||()

Dethyl 1°-Vinyl
1° 1°
1° 2°-Vinyl

< |()* |||()+

*| +||,|() *
*'|()
2° 1°-Allyl 1°
1°-[enzyl 3°



   

¦ Alkynes
can be hydrated to form enols that
immediately

R— to ketones.

¦ Reagents
Reagents::
aq. acid, most commonly
H2S`4, with a mercury salt.
¦ Regioselectivity predicted by
D  R —

¦ Reactionproceeds via protonation to give
the more stable carbocation intermediate.
|'|| ? |'||
¦ Not stereoselective since reactions proceeds
via planar carbocation.
 à 


   

¦ `verall transformation: || to --||

||---
(and potentially to -||-).

¦ Reagent: normally the halogen (

Reagent: ( r [r2) in an
inert solvent like methylene chloride, CH2Cl2.
¦ Reaction proceeds via cyclic
halonium ion.
¦ Stereoselectivity : 
R since
the two |- bonds form in
separate steps one from X2,
the other X-.
 Ú     

¦ `verall transformation : || to 2 x |.

¦ `zonolysis implies that ozone causes the
alkyne to break (-
(-—R—
—R—
¦ Reagents : ozone followed by aqueous
work--up.
work
¦ Note
that each of the || bonds in the |/|
becomes a |. bond.
 ×
 


¦ Classify each of the following as an internal or a terminal
alkyne (from the slide 4)
a) 1-
1-hexyne b) 3-
3-octyne
c) cyclooctyne d) propyne

¦ §hat is the alkyne product from the reactions of the

following with NaNH2: (from the slide 10)
a) 2,2-
2,2-dibromopropane
b) 1,2-
1,2-dibromohexane
c) 1,1-
1,1-dibromooctane
d) 2,3
2,3--dibromohexane
¦ §
 
  
  Π 

      (from the slide 20)
  (from

   

 
 




   


  
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