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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  .

ten ten-- membered carbon ring is the smallest that can contain the alkyne function without excessive strain. . u  u  m ¦ [ecause of its linear configuration.

] 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 .

¦ The suffix Œ  is used in the paren hydrocarbon name to denote an alkyne. . Nomenclature ¦ Akynes are named by general rules similar to those used for alkanes and alkenes. 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. | | | | ||| |  [    .

    |    .

 .

triple bonds are called  . .   ¦ Compounds containing both double and .

¦ Ifthere is a choice in numbering. whether double or triple.¦ Numbering of the hydrocarbon chain starts from the end nearer the first multiple bond. double bonds receive lower numbers than triple bonds. u u  u u u u u u  u u u u u u u  3 3   u    . For example.

       .

2 (1. Preparation of Alkynes ¦ Alkynes are generally prepared by * ºehydrohalogenation of either geminal (1.2--)alkyl dihalides (usually [r or Cl).1--) or vicinal (1. using a strong base. ¦ Thesereactions are typically E2 reactions and occur via an alkenyl halide. halide. usually NaNH2. .1 (1.

| |     | |  . halides.* The reaction of metal acetylides with primary alkyl halides.

2-dibromohexane c) 1.2- 1.1-dibromooctane d) 2.2- 2.3--dibromohexane .1- 1.] m ¦ §hat is the alkyne product from the reactions of the following with NaNH2: a) 2.3 2.2-dibromopropane b) 1.

¦ The 22ü ü bonds are produced by the —R —R   —R . Structure and Reactivity ¦ The alkyne functional group consists of two  hybridised C atoms bonded to each other via one ı and two ü bonds.

of the two pairs of .

¦ The diagram shows the heats of hydrogenation of 2- 2-butyne (in the slide: blue in units of kcal/mole) kcal/mole) .-orbitals not utilised in the hybrids.

¦ The "extra" ü bond in an alkyne is weaker that an alkene ü bond: 2 x 28.4 kcal .¦ It indicates that alkynes are thermodynamically less stable than alkenes to a greater degree than alkenes are less stable than alkanes.3 (C=C) ± 65 (C (CŁ ŁC)= 8.

ı ü ı Two separate perpendicular .¦ The 2 C of the || and the 2 atoms attached directly to the || are R  so they cannot exist as R— R—/ — — isomers.

molecular orbitals .

¦ The ü bonds are a region of high electron density. alkynes are typically  . so it allows an acetylinic carbon density to have a greater amount of electronegative character.. ]As a result. character.

.  .R—.

R— ] Terminal alkynes. . are quite acidic (pKa = 26). R- R-|Î|-H.

sodium amide. -butyllithium or a Grignard reagent. sodium amide.¦ Reacting with a strong base such as sodium.. a terminal alkyne gives the anion of the terminal alkyne (a ©  ):    ): | | |. reagent.

 |.

 | | |.

 |.

 .

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

is a good |-nucleophile and can undergo nucleophilic substitution reactions (usually SN2) with 1o or 2o alkyl halides (Cl. Alkylation of Alkynes  ¦ The acetylide carbanion. . RCŁC . [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 carbanion reacts The with the electrophilic carbon in the alkyl halide with loss of the leaving group.      ¦  The amide ion acts as a The base removing the acidic terminal H to generate the acetylide ion. a carbon nucleophile. . forming a new || bond.

] ×× !" ¦ §   .

  .

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     ¦          ¦  .

     ¦ .

       ! .

 .

and . ). 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 || ||).

 stability of any intermediates (for example. we might expect addition reactions of alkynes to be more exothermic and relatively faster than equivalent reactions of the alkenes. . ¦ Since alkynes are thermodynamically less stable than alkenes. carbocations).

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

¦ 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.

. ¦ Hydrogen halide reactivity order : #$%$|$& (paralleling acidity order). å       ¦ §hen treated with HX alkynes form vinyl halides. 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. .

¦ Notstereoselective since reaction proceeds via planar carbocation (CH3C=CH2 & CH3C[rCH3).¦ Reactionproceeds via protonation to give the more stable carbocation intermediate. .

] m ¦ §hat would be the product from the reaction of 2- 2-butyne with excess H[r ? .

in the presence of radicals %. (compounds such as peroxides) the radical addition occurs with .¦ For%.

.

—R rR R—: rR R—: ] m §hy does this reaction have the opposite regiochemistry ? .

|() * *'|() 2° 1°-Allyl 1° 1°-[enzyl 3° .¦ |!  ! |'() * ||()+ |()* ||() Dethyl 1°-Vinyl 1° 1° 1° 2°-Vinyl < |()* |||()+ *| +||.

    ¦ Alkynes can be hydrated to form enols that immediately  R— to ketones. most commonly H2S`4. . acid. ¦ Reagents Reagents:: aq. 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 -||-). CH2Cl2. ¦ Reagent: normally the halogen ( Reagent: ( r [r2) in an inert solvent like methylene chloride.

bonds form in separate steps one from X2.¦ Reaction proceeds via cyclic halonium ion. . ¦ Stereoselectivity :  R since the two |. the other X-.

 ¦ `zonolysis implies that ozone causes the alkyne to break (- (-—R— —R— . Ú      ¦ `verall transformation : || to 2 x |.

work ¦ Note that each of the || bonds in the |/| becomes a |.¦ Reagents : ozone followed by aqueous work--up. . bond.

3 2.1- 1.3--dibromohexane .2-dibromopropane b) 1.2- 1.2- 2.1-dibromooctane d) 2. ×    ¦ 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-dibromohexane c) 1.

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     (from the slide 20)   (from           .

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