ALKUNA

Fithria Dyah Ayu S., M.Sc., style Click to edit Master subtitleApt. Prodi Farmasi-Fakultas MIPA UII

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Alkynes

Hydrocarbons that contain carboncarbon triple bonds, the triple bond may be between the terminal carbon atoms of the chain, or may be between internal carbon atoms in the chain. General formula is CnH2n-2 Some reactions are like alkenes: addition and oxidation.
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Acetylene, the simplest alkyne is

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Why this chapter?

We will use alkyne chemistry to begin looking at general strategies used in organic synthesis

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8.1 Naming Alkynes

General hydrocarbon rules apply with -yne as a suffix indicating an alkyne Numbering of chain with triple bond is set so that the smallest number possible for the first carbon of the triple bond Multiple triple bonds are: diynes, triynes, etc Double and triple bonds are: enynes

Number nearest a multiple bond (either double or triple) If you have a choice, double bond lower number than triple
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Name these:
CH3 C CH
propyne

CH3

C C CH2

CH2

Br

5-bromo-2-pentyne

CH3 CH3 CH CH2

CH3 C C CH CH3

2,6-dimethyl-3-heptyne
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Additional Functional Groups

All other functional groups, except ethers and halides have a higher priority than alkynes. For a complete list of naming priorities, look inside the back cover of your text. =>
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Examples
CH3 CH2 CH CH2 CH C CH
3-methyl-5-hexen-1-yne

OH CH3 C C CH2 CH CH3

4-hexyn-2-ol =>
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Physical Properties

Nonpolar, insoluble in water. Soluble in most organic solvents. Boiling points similar to alkane of same size. Less dense than water. Up to 4 carbons, gas at room temperature.
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Electronic Structure

The sigma bond is sp-sp overlap.

The two pi bonds are unhybridized p overlaps at 90, which blend into a cylindrical shape.

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Bond Lengths

More s character, so shorter length. Three bonding overlaps, so shorter.

Bond angle is 180, so linear geometry. 3/4/12 Chapter 9 1010

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Acidity of Alkynes

Terminal alkynes, R-CC-H, are more acidic than other hydrocarbons. More s character, so pair of electrons in anion is held more closely to the nucleus. Less charge separation, so more stable. The high electron density of the p bonds makes them nucleophilic.
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Acidity Table

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1. Catalytic Hydrogenation
The usual Pt and Pd hydrogenation catalysts are so effective in promoting addition of hydrogen to both double and triple carbon-carbon bonds that the alkene intermediate formed by hydrogen addition to an alkyne cannot be isolated.

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Step 1: Hydrogen gets absorbed onto the metal surface.

Step 2: Alkyne approaches the H atoms absorbed on the metal surface. Step 3: CC reacts with the H atoms on the surface forming the two new C-H s bonds generating the alkene. 3/4/12

2. Addition by Electrophilic Reagents The initial interaction

between an electrophile and an alkene or alkyne is the formation of a picomplex, in which the electrophile accepts electrons from and becomes weakly bonded to the multiple bond. Such complexes are formed reversibly and may then reorganize to a reactive intermediate (e.g. a carbocation or a halonium cation) in a slower, ratedetermining step. Subsequent reaction then leads to addition products. The following diagram shows the role of a picomplex in reactions of alkenes with Brnsted 3/4/12 acids and halogens. Polar

2. Addition by Electrophilic Reagents

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2. Addition by Electrophilic Reagents

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Why are the reactions of alkynes with electrophilic reagents more sluggish than the corresponding reactions of alkenes? Two factors are significant in explaining this apparent paradox:
although there are more -electrons associated with the triple bond, the sphybridized carbons exert a strong attraction for these -electrons, which 3/4/12 are consequently bound more tightly to

Keto-enol Tautomerisme
Reaksi adisi air thd alkuna membutuhkan adanya asam kuat seperti asam sulfat, dan diperlukan adanya katalis HgSO4. adisi tsb menghasilkan suatu keton, tetapi pada awalnya adisi tsb menghasilkan suatu enol, yaitu senyawa yang memiliki substituen hidroksil pada ikatan rangkap C=C, kemudian scr cepat mengalami penataan ulang mjd tautomer keton yang lebih stabil.

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Keto-enol Tautomerisme

Tautomer didefinisikan sbg perubahan yang berlangsung cepat pd isomer konstitusional, bisa tjd akibat perbedaan letak dari ikatan atom hidrogen yang labil dan perbedaan letak ikatan rangkap. 2 faktor yang mempengaruhi tautomerisme:
Perbedaan energi potensial di antara 2 bentuk tautomer faktor penentu pd 3/4/12