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2015-1436

Learning ObjectivesLearning ObjectivesChapter three discusses the following topics which have to be understood and memorized :

The structure, hybridization and Bonding in alkynes

Common and IUPAC naming of alkynes

Physical properties of alkynes

Preparation of alkynes

Reactions of alkynes: addition reactions and acidity

Alkynes: Molecular And Structural

Formulae The alkynes comprise a series of carbon- and hydrogen-

based compounds that contain at least one triple bond. This group of compounds is a homologous series with the general molecular formula of Cn H2n—2

The alkyne triple bond is composed of one σ and two 2 covalent bonds, the triple bond can be terminal or internal.

The simplest alkyne, ethyne (also known as acetylene), has two carbon atoms and the molecular formula of C2H2. The structural formula for ethyne is: CH CH3

sp Hybridization Of Alkynessp Hybridization Of Alkynes This involves the mixing of one s- and one p-orbital forming two sp-hybrid orbitals of equivalent energy. The two sp-hybrid orbitals are oriented in a linear arrangement and bond angle is 180° to minimize the repulsion between them. The remaining two p orbitals (py and Pz) are unaltered

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CH CH

Molecular formula of ethyne is C2H2. In ethyne, each carbon atom is sp-hybridized. In this way, four sp-orbitals are generated. One sp- orbital of each carbon atom by overlapping forms a

sigma bond between carbon atoms. Remaining one sp-orbital of each carbon atom overlap with

1s-orbital of a hydrogen atom to produce two sigma bonds. Py-orbital and Pz-orbitals of each carbon by parallel

overlapping form two pi-bonds between the two carbon atoms.

Geometry (shape) of ethyne molecule is linear in which bond angles are 180o.

The length of CΞC is 1.20 A°5

Orbital Overlap IN EthyneOrbital Overlap IN Ethyne

2s2 2p2 2s1 2p3 2 x sp 2p

sspp HYBRIDISATION OF ORBITALS in ALKYNES HYBRIDISATION OF ORBITALS in ALKYNES

The electronic configuration of a carbon atom is 1s22s22p2

promotion hybridization

Carbon in ground state

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SummarySummary

spsp hybridization occurs when a C has 2 sigma hybridization occurs when a C has 2 sigma bonds onlybonds only

spsp hybridized orbital has 50% s and 50% p hybridized orbital has 50% s and 50% p character character

The 2 The 2 spsp hybrids point in opposite directions at hybrids point in opposite directions at 180180oo to each other to each other

Each Each spsp hybrid is involved in a(hybrid is involved in a(σσ)sigma bond )sigma bond The remainingThe remaining p p orbitals form the 2pi bonds orbitals form the 2pi bonds The triple bond is one (The triple bond is one (σσ)bond and two pi ()bond and two pi (∏∏) bonds) bonds.

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Find the longest chain containing both atoms of the triple bond; Find the longest chain containing both atoms of the triple bond; this gives the root name. this gives the root name.

Add the ending Add the ending ––yneyne to the root nameto the root name.. Number the chain, starting at the end closest to the triple bond. Number the chain, starting at the end closest to the triple bond. Give branches or other substituents names and numbers to locate Give branches or other substituents names and numbers to locate

their positions.their positions. Indicate the number of identical groups by prefixes di, tri, tetra, Indicate the number of identical groups by prefixes di, tri, tetra,

etc.etc. Place the position numbers and names of the substituent groups Place the position numbers and names of the substituent groups

in alphabetical order, before the root name. In alphabetizing in alphabetical order, before the root name. In alphabetizing ignore prefixes like ignore prefixes like terttert., di, tri, etc. but include iso and cyclo.., di, tri, etc. but include iso and cyclo.

DoubleDouble and and tripletriple bonds are considered to bonds are considered to have equal priorityhave equal priority: thus : thus in a molecule with both a double and triple bond, whichever is in a molecule with both a double and triple bond, whichever is close to the end of the chain determines the direction of close to the end of the chain determines the direction of numbering.numbering.

In case where double and triple bonds would have the In case where double and triple bonds would have the same same position numberposition number, the , the double bond takes the lower numberdouble bond takes the lower number..

In writing the final name In writing the final name ‘’ene’’ comes before ‘’yne’’‘’ene’’ comes before ‘’yne’’ regardless regardless which takes the lower number (i.e. alphabetical order).which takes the lower number (i.e. alphabetical order).

IUPAC Nomenclature of AlkynesIUPAC Nomenclature of Alkynes

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ExamplesIUPAC Names Of

Alkynes

C CHHC

CH3

CH

F

F

4,4-Difluoro-3-methyl-1-butyne

C CH-CH2-CH3

H

CHC

Hex-3-en-1-yne(triple bond closer to the end of chain)Note: An''e'' is dropped from ''ene''

due to it is followed by a vowel

HC C CH2 CH CH2

Pent-1-en-4-ynedouble and triple bonds have have the same position number

thus ene take lower number

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2345

6-Ethyl-4-nonyne

C C

Br

H3C

5-Bromo-2-pentyneNot 1-Bromo-3-pentyne

1 2 34

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1 2

3 4 5

7

8

9

1

5

1 2 3 4 5 6

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Common Nomenclature Of AlkynesCommon Nomenclature Of Alkynes The simplest alkyne its common name is The simplest alkyne its common name is acetyleneacetylene Therefore the common names of alkynes are derived from Therefore the common names of alkynes are derived from

acetyleneacetylene

( e.g. Methyl acetylene( e.g. Methyl acetylene)

Examples:CH3 C CH CH3 CH

CH3

CH2 C C CH

CH3

CH3

C CH3C

Common : IsobutyisopropylacetyleneCommon : Methyl acetylene

Common: Isopropylmethylacetylene

ExerciseExercise 1) Give the IUPAC and common names of the

following compounds:

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C CH

C CH2

CH2

C HC C C(CH3)3

a) b)

c) d) -

Physical PropertiesPhysical PropertiesNonpolar, insoluble in water.Nonpolar, insoluble in water.Soluble in most organic solvents.Soluble in most organic solvents.Terminal alkynesTerminal alkynes, R-C, R-CC-H, are C-H, are

more more acidicacidic than other hydrocarbons. than other hydrocarbons.For example: alkynes b and d have For example: alkynes b and d have

acidic hydrogen while a and b don’t acidic hydrogen while a and b don’t

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C CH

C CH2

CH2

C HC C C(CH3)3

a) b)

c) d) -

Preparation of alkynesPreparation of alkynes1.1. By dehydrohalogenation of geminal and vicinal dihaloalkanes By dehydrohalogenation of geminal and vicinal dihaloalkanes

(- 2 HX) (- 2 HX)

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C C

XX

Strong base

- 2 HXC C

Br

Br

1,2-dihaloalkane

Excess NaNH2

- 2HBr

Br

Br

Br

KOH/ alcohol

heat

NaNH2

heat

Preparation of alkynesPreparation of alkynes2.2. From reaction of sodium Acetylide with Primary Alkyl Halides From reaction of sodium Acetylide with Primary Alkyl Halides (Alkylation of acetylide with primary alkyl halide)(Alkylation of acetylide with primary alkyl halide)

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C CHR + Na liq NH3 C C

- Na

+R + H21/2

C C- Na

+R + R' X C CR R' + NaX

Sodium acetylide

For Terminal CC (use only Acetylene H-CC-H)

For Non Terminal CC (use Monosub. R-CC-H)

Na

NaNH2/ NH3 CH3Br

- NaBr

Reactions of alkynesReactions of alkynes11. Addition of hydrogen ( Hydrogenation. Addition of hydrogen ( Hydrogenation))

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Alkynes can be reduced to trans-alkenes using Na or Li in liquid NH3

Alkynes can be partially reduced Alkynes can be partially reduced to to ciscis-alkenes -alkenes with with HH22 in the presence of in the presence of poisoned poisoned

catalysts. (Landlar catalyst)catalysts. (Landlar catalyst)

HH

+ H2C C

Pd(BaSO4) or (NiB)

Cis- alkene

H

H

+ H2C C

Na or Li / liq. NH3

Trans -alkene

2. Addition of halogen Addition of halogen (Halogenation) (Halogenation)

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C C C C

X

X

+ X2 + X2 C C

X X

XX

Tetrahalide(X= Br or Cl)

• If we used only one mole of X2, (alkene) will be produced

• If two two mole of X2, an alkane will be produce

+ Br2

Br

Br

+ Br2

Br

Br

Br

Br

33 .Addition of hydrogen halideAddition of hydrogen halide

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HC CR + HX HHC=CX R + HX HHHC – CXXR

+ HBr

Br

+ HBr

Br

Br

C C C C

H X

+ HX + C C

H X

XH

A gem dihalide(X= Br , Cl, I)

HX

A haloalkene

44 . .Addition of water: Addition of water: HydrationHydration

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HO-HH2SO4 / HgSO4C C +

O

H

an enol unstable

O

H

carbonyl more stable

H

Hketo-enol tautomerism

H C

Acetylene

Specific example:

C H/ H2SO4, HgSO4 H-OH H

H

Acetaldehyde(a stable carbonyl compound)

HH

C

H

Vinyl alcohol(an unstable enol)

C

H

O HC

O

CH

HC

Propyne (an unstable enol)

C CH3

/ H2SO4, HgSO4 H-OH

Acetone(a stable carbonyl compound)

H

C

H

C

CH3

O HCH3C

O

CH3

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1. An alkyne’s name ends with(a) –ane (b) -ene(c) –yne (d) diene

2. An alkyne function has …….. pi bond(s).(a) one (b) two(c) three (d) four

3. Alkynes react with HCl by a mechanism called(a) elimination (b) Markovnikov addition(c) (d) substitution

4. Alkynes react with water in the presence of a catalyst to give(a) a dialcohol (diol) (b) an alkane(c) an enol (d) a dibromide

5. The conversion of alkynes to alkanes is an example of(a) oxidation (b) reduction(c) chlorination (d) dehydration

Practice problems:

Questions?