Alkene Addition Reaction Type 1 Catalytic Hydrogenation (+H2)

H H H H

Pt/ Pd, 25'C, 1 atm Ni, 150'C, 5 atm

H H H H H H

The Catalyst is usually in powder formed, so as to increase the Contact Surface Area for Reaction. Type 2 Halogenation (+X2)

1. F2 : too reaction, may explode, and break the double bond Cl2/Br2 : moderate reaction I2 : too unreactive, give poor yield 2. Different solvent different product Organic Water NaNO3 NaCl solvent
X X X OH X
NO3

X Cl

3. Decolorization By Red Orange Br2 in CCl4 Alkane: under sunlight; substitution, give white fumes (HBr) Alkene: X light; Addition, which become colorless By Purple Acidified diluted KMnO4 Purple to colorless, give Diol

Type 3 Hydrohalogenation (+HX)

Markovnikovs Rule In addition of Unsymmetrical Reagent to C=C of alkene, The hydrogen of HA attach itself to Carbon holding greater no. of H Give the more stable intermediate Carbocation

Haloalkane Substitution Reaction

R can only be Alkyl group, but not aromatic ring Medium Leaving Group (affect the rate) Apparatus Usually Ethanol R-I > R-Br > R-Cl bond length --- bond Strength/Energy R-F: usually unreactive, since the bond is so strong Heating under Reflux

(prevent the loss of reaction mixture) State the procedure how to compare the Br, Cl and I in alkane NaOH and Ethanol (Substitution) AgNO3/ HNO3 (Precipitation) What would happened if there is no HNO3 addition after NaOH? (Ag2O)

Alcohol 1. Categorized by the no. of Alkyl gp. Attached Primary Alcohol Secondary Alcohol

Tertiary Alcohol

Substitution Reaction
R OH + HX R X

H2O

Reactivity-- Tertiary> Secondary> Primary -- HI> HBr > HCl (xHF) By Lucas Reagent (HCl + ZnCl2) Catalyst: ZnCl2

Indeed, it is a test to examine the alcohol structure Heating under reflux

By NaCl(Br)/H2SO4 or NaBr or NaI/ H3PO4 NaX+ H2SO4 HX+ NaHSO4, NaX+ H3PO4 HX+ NaH2PO4 ROH RX Sulphuric Acid is used because HCl is not a Strong RA But for NaI, since HI is strong RA, so HI+ H2SO4 H2S + I2 Heating Under Reflux

By Phosphorus Halide (PX3) 3 ROH + PBr3 3 RBr + H3PO3 Heating Under Reflux

By SOCl2 ROH + SOCl2 RCl + HCl + SO2 Only for RCl Heating under Reflux Convenient since the latter 2 are gases

Phosphorus prepared and used rapidly Since PX3 is volatile Water Bath is used Prevent boiling by Exo Reaction

NaOH be used No water enter

Elimination Reaction Dehydration of Alcohol (-H2O)

Reactivity: -- Tertiary> Secondary> Primary (Stability of intermediate) Condition: Conc. H2SO4, at 180C (if 140C give ether) Dehydrating Agent: Primary Conc. H2SO4 (at 180C), Al2O3 (at 300C) Secondary 85% H3PO4 (at 165-170C) Tertiary 20% H2SO4 (at 85C)
H H3C H CH3 OH CH3 H3C H H CH2 CH3

H H3C

CH3 CH3

Which one is major?

Oxidation Reaction (by KMnO4/H+ or KCr2O7/H+ + Reflux) For primary Alcohol, To limit the oxidation to aldehyde - at room temp + X excess OA - Distill the aldehyde immediately - use KCr2O7/H+

Aldehyde and Ketone Reduction (by LiAlH4/ Dry Ether, H3O+

or NaBH4, Ethanol )

Sodium Borohydride is a milder RA, so aqueous solvent can be used as medium Lithium Aluminum hydride is a Strong RA, it would react violently with water It is Explosive and Corrosive in Aqueous condition, so anhydrous condition is needed These two RA would not react with the C=C bond but C=O bond

Carboxylic Acid Esterification (Catalyzed by Acid )

O R OH

H O R'

Conc. H2SO4

O R

OR' + H OH

Type of Condensation (reaction in which two or more molecules react together to form a larger molecule with elimination of a small molecules) Reversible Reaction Role of Conc. H2SO4: 1. Catalyst 2. Dehydrating Agent ( to remove water, so eqm. Shift to Right) Where is the oxygen atom come from? Ester Pleasant Smell, Insoluble in Water, but Organic Solvent lower Bp. Than corresponding Alkanol/ Alkanoic Acid Uss: Perfume, Artificial Flavor, Solvent for Organic Compound Experimental Procedure of Ester Preparation

i) What would be the observed if the A is Cold Water?

ii) What would be the observed if the A is Sodium Carbonate?

Hydrolysis of Ester (Reflux with Catalyst)

Acidic Medium - Reversible Reaction(incomplete) - Yield - Alcohol + Carboxylic Acid

Alkaline Medium - Irreversible Reaction(Complete) - Yield - Alcohol + Salt of Carboxylic Acid - Rate of Hydrolysis: Alkaline> Acidic > neutral Experimental Procedure of Ester Preparation 1. Add NaOH/NaHCO3 1. Add Ether (react with RCOOH) (Remove NaOH, 2. Add Ether Carboxylate) (Remove NaOH, 2. Add Anhydrous CaCl2 Carboxylate) (Remove Water) 3. Add Anhydrous CaCl2 3. Filtration (Remove Water) 4. Distillation 4. Filtration (To collect Alcohol) 5. Distillation (Bp. Alkanoic Acid> Alcohol> Ester) Can I collect the Carboxylic Acid from the Alkaline Medium?

Reduction (by LiAlH4)

Lithium Aluminum Hydride should be separated from Water/Alcohol It is explosive and corrosive
H

H2O

H2

+ OH-

Amide Formation (by NH3 + Heating or (NH4)2CO3 + Heating ) By Ammonia

O R OH

Neutralization NH3 R

O O NH4
+

Heat (Dehydration) O R NH2

OH

By Ammonium Carbonate
O 2R OH

Neutralization
(NH4 )2CO3

O 2R
O NH 4 +

CO2 + H2 O

Heat (Dehydration) O 2R
NH2

2 H2 O

- Add Excess Alkanoic Acid shift the eqm to Right, increase the yield - Distillate at 170C to remove Alkanoic Acid and Water Amide (white Crystalline Solid) - The least reactive in Acid Derivatives Hydrolysis of Amide

In Acid Medium O R NH + 2
H2O

Reflux

O R OH

+ NH4

In Basic Medium O R
NH2+ OH

Reflux R

O O

+ NH3

- both are irreversible reaction, unlike the acidic hydrolysis of ester

Organic Synthesis Percentage Yield = [Actual Yield (grams) / Theoretical Yield (grams) ] X 100 %

1. Amide P are generally prepared by reacting equimolar amount of an Amine (A) and an Acid Halide(B), as the equation shown below
H NH2 H H H A H H O H H H B Cl H H H H H Amide P O N H H H H H H H

Calculate the Mass (in g) of A required to react with 4.0 g of B, then calculated the percentage yield of the same reaction if 4.0 g of the Amide P is obtained (given Relative Atomic Mass H:1.0, C: 12, N:14, O: 16 and Cl: 35.5 )

2. In an experiment to prepare 1-bromobutane, a mixture of butan-1-ol, potassium bromide and concentrated sulphuric(VI) acid was heated under reflux for 30 minutes. i) Draw a labeled diagram of the set-up used.

ii) Suggest how to isolate 1-bromobutane from the reaction mixture.

3. In an experiment to prepare propanal from propan-1-ol,

a side-product N (C6H12O2) was formed. What is N ? Suggest how N is formed.

4. In an attempt to prepare 1-methylcyclopentene, 1methylcyclopentanol was allowed to react with phosphoric(V) acid. The reaction mixture was then subjected to simple distillation. i. Draw a labelled diagram to show the set-up of apparatus used in a simple distillation.

ii. Suggest a chemical test, giving the expected observation, to show the presence of an alkene in the distillate.

iii. The distillate was known to contain a small amount of unreacted 1-methylcyclopentanol. Suggest a method to separate it from the desirable product.

iv. Is 1-methylcyclopentene the only compound obtained after the suggested separation method in (iii)? Explain.

5. 3-Methyl-1-butyl Ethanoate, commonly known as isoamyl acetate, is a naturally occurring compound having a distinctive pleasant banana odor and is used in food flavoring. In an experiment to prepare the compound, 5.0 cm3 of isoamyl alcohol is allowed to react with 15.0 cm3 of Glacial Acetic Acid in the presence of a reagent L.

i. Suggest what reagent l may be and give the reaction conditions for this reaction.

ii. Calculate the mole ratio of isoamyl alcohol to Glacial Acetic Acid used in this preparation. (Given density of isoamyl alcohol is 0.81 gcm-1 and that of Glacial Acetic Acid is 1.05 gcm-1)

iii. What are the major compounds in the resulting mixture at the end of this preparation?

iv. outline the procedure to isolate isoamyl acetate from the resulting mixture. (it is known that isoamyl acetate cant be effectively separated from the resulting mixture by fractional distillation)

v. suggest why isoamyl alcohol is not used in excess in this preparation