 triple bonds

 unsaturated hydrocarbons
 CnH2n-2
 non-polar
 has a linear structure (molecules are more closely packed)
 weak intermolecular forces
 higher alkyne = greater boiling and melting point
 have higher boiling points than alkanes and alkenes because of its ability to stack
 at room temperature, the first 3 members (ethyne, propyne, butyne) are gaseous, the next
8 members are liquid, the greater rates are solid
 hydrophobic
 colorless
 Ethyne has an odor of garlic smell
 weakly polar in nature
 lighter than water, immiscible with water, soluble in organic solvents (petroleum ether,
benzene, carbon tetrachloride)
 1 pair sigma bonds, 2 pairs pi bonds

 CnH2n-4
 Cyclooctyne is the smallest possible cycloalykne capable of being isolated and stored as
a stable compound (decomposes upon standing on room temperature)

 cycloalkynes with small rings are unstable

 carbon chain must be long enough to connect the two ends of the triple bond without
introducing too much strain

PREPARATION OF ALKYNES

1. from CALCIUM CARBIDE

 Acetylene is prepared in the laboratory as well as an industrial scale by the
action of water in calcium carbide.
 Obtained by heating calcium oxide (from limestone) and coke in an electric
furnace at 2275 K.

2. from VICINAL DIHALIDES

 Undergo dehydrohalogenation (1 molecule of hydrogen halides is eliminated to
form alkenyl halide)
 Treatment with sodamide will produce alkynes
 REAGENTS FOR ELIMINATION

1. Molten or Alcoholic KOH (potassium hydroxide)

 at 200 C favors an internal alkyne

2. NaNH2 (sodium amide)

 at 150 C and followed by water favors a terminal alkyne

INTERNAL TERMINAL (acetylenic hydrogen)

The triple bond is between 2 carbons The triple bond is between a hydrogen and carbon
more stable than terminal alkynes

REACTION OF ALKYNES

Addition Reactions
 pi bonds become 2 sigma bonds
 usually exothermic
 1 or 2 molecules may be added

1. Addition of dihydrogen
 alkynes react with hydrogen in the presence of Ni, Pt, Pd as catalysts
i. Add lots of H2 with catalyst to reduce alkyne to alkane (completely
saturated)
ii. Use Lindar’s catalyst to convert an alkyne to cis-alkene
iii. React to sodium in liquid ammonia to form a trans-alkene

2. Addition of Halogens
 used as a test for unsaturation (bromine water test)
 Cl and Br are added to alkynes to form a vinyl dihalide
 may add syn or anti so product is a mixture of cis and trans isomers

3. Addition of Hydrogen Halides

 1 molecule of hydrogen halides = vinyl halides
 2 molecules of hydrogen halides = geminal dihalides
 2 halogens are attached to the same carbon atom
 for terminal alkynes, Markovnikov product is formed

4. Addition of Water
 react with water in the presence of mercuric sulphate (HgSO4) and sulphuric
acid at 337 K
 the product is carbonyl compounds (aldehydes and ketones)
 H-OH to one pi bond with a Markovnikov = vinyl alcohol (enol) that rearranges
to a ketone
 H-OH with an anti-Markovnikov = aldehyde
 belong to a homologous series of organic compounds
similar to alkanes and alkenes
 contains the functional group -OH (hydroxyl group)
 Molecular formula: C2H5OH
 Condensed Structural Formula: CH3CH2OH
 General Formula: CnH2n+1OH

CLASSIFICATION OF ALCOHOLS

PHYSICAL PROPERTIES OF ALCOHOLS

Physical States
 aliphatic alcohols and lower aromatic alcohols = liquids at room temperature
 highly branched alcohols and alcohols with 12+ carbon atoms = solids

Boiling Points
 higher than alkanes and chloroalkanes of similar relative molecular mass because of
intermolecular hydrogen bonds

Solubility in Water
 alcohols with short carbon chains dissolve in water and hydrogen bonds are formed
 higher alcohols are insoluble in water
 contains a polar end (-OH group) “hydrophillic” and a non-polar end (alkyl group) “hydrophobic”
 solubility decreases as length of carbon chain increases
 polyhydroxy alcohols are more soluble than monohydroxy alcohols
(polyhydroxy can form more hydrogen bonds with water molecule)
 USES OF ALCOHOLS

ETHANOL
 solvent for varnishes, perfumes, flavorings, medium for chemical reactions, and recrystallization
 an important raw material for synthesis
 classified as hypnotic (sleep producer)
 less toxic than other alcohols
 the alcohol of alcoholic beverages
 prepared by HYDRATION OF ETHYLENE and FERMENTATION OF SUGARS

REACTION OF ALCOHOLS

1. Reaction with sodium

 Alcohols react with sodium (Na) at room temperature to form salts and hydrogen
 Reactivity of alcohols with sodium in order: 1 > 2 > 3
2. Oxidation
3. Esterification
4. Halogenation and Haloform Reactions
 Reactivity of hydrogen halides in order: HI > HBr > HCl
 Reactivity of alcohols with hydrogen halides in order: 3 > 2 > 1
5. Dehydration
 Dehydration of alcohols will form alkenes.
 The products will follow Saytzeff Rules - a reaction that produces an alkene
would favor the alkene that has the greatest number of substituents attached to
the C=C group.
6. Formation of Ether (Williamson Ether Synthesis)

LABORATORY TESTS FOR ALCOHOLS

1. Lucas Test
 The alcohol is shaken with Lucas reagent (a solution of ZnCl2 in concentrated HCl)
PRIMARY - no cloudiness/reaction at room temperature
SECONDARY - turns cloudy within about 5 minutes
TERTIARY - immediate cloudiness due to the formation of alkyl chloride

2. Oxidation of Alcohols
 Only primary and secondary alcohols are oxidized by hot acidified KMnO4 or K2Cr2O7
KMnO4 purple color disappears
K2Cr2O7 orange color changes to green

HALOFORM TEST TO IDENTIFY METHYL ALCOHOL GROUP

1. Iodoform Test
 Ethanol and Secondary Alcohols containing methyl ethyl group reacts with
alkaline solutions of iodine to form triiodomethane (iodoform, CHl3)
TRIIODOMETHANE - a pale yellow solid with a characteristic smell
 Can distinguish ethanol from methanol

tertiary alcohols do
 Can distinguish 2-propanol from 1-propanol not give a positive
iodoform test