Oxidation with or Solution, And Reduction with (lithium aluminium hydride) in

Nucleophilic addition of ALDEHYDE AND KETONE In the presence of

Reaction Or in the presence of (alkali) with Reaction

Oxidation with Fehlings of Benedicts solution Reagents : contain complexed ions in an Solution Why Cu ions are complexed? - to prevent precipitation of Cu(OH)2
2+

Oxidation with Tollens Reagent (silver mirror test) Reagents : contain diamminesilver(I) ions, How to make? Add silver(I) nitrate solution and dilute ammonia

Steps : A few drops of the aldehyde or ketone are Steps: A few drops of the aldehyde or ketone are added added to the reagent. The mixture is warmed gently. to the reagent. The mixture is warmed gently. Results: Results : Ketone : No change in the colourless solution Ketone : No change in the blue solution Aldehyde : produce silver mirror on the test tube Aldehyde : A red brown precipitate of copper (I) oxide Half-equations: Half-equations: Overall equation: Overall equation:

Oxidation with acidified potassium dichromate (VI) solution Reagents : dilute sulfuric acid and potassium dichromate (VI) solution Steps: Half-equations:

Results: Overall equation: Ketone : No change in the orange solution Aldehyde : orange solution turns green

Reduction Reducing agents : (NaBH4) in ethanol in dry ether (ethoxyethane) or sodium tetrahydridoborate Conditions: room temperature

LiAlH4 : more reactive can reduce esters, amides and carboxylic acids : reacts violently with water and alcohol. (reaction must be in dry condition) Aldehyde : Reduced into 10 alcohol Equation : + 2[H] Ketone: Reduced into 20 Equation: + 2[H]

*CANNOT REDUCED C=C BOND. Reducing agent for C=C BOND : H2 with nickel or platinum catalyst Nucleophilic addition Reagents : HCN (Hydrogen cyanide) in the presence of KCN in cold alkaline condition Nucleophile attacks the + Carbon atom Why must have KCN? To produce sufficient CN- ion Equation : Mechanism : 1) with ethanal: produce 2-hydroxypropanenitrile 2) with propanone : produce 2-hydroxy-2-methylpropanenitrile

Stereochemistry in nucleophilic addition Eg : Ethanal -ethanal is a planar molecule - cyanide ion has equal chance of attacking plane of the molecule either from above or below Mechanism

SN1 nucleophilic substitution in halogenoalkane -Form a planar intermediate - nucleophile has equal chance of attacking the planar intermediate either from above or below

Mechanism

- Form racemic mixture (equal amount of enantiomer) no effect on plane of polarization of the plane-polarised monochromatic light - optical isomerism : form molecule with asymmetric carbon atom that has chiral centre (carbon atom that has 4 different groups bonding with it)

Condensation reaction with Bradys reagent (2,4-dinitrophenylhydrazine) -to test compound containing carbonyl group such as aldehyde and ketone Reaction : condensation (a reaction in which two molecules join together to form one big molecule with the loss of small molecule such as water) Mechanism : nucleophilic addition-elimination reaction Equation :

Results : A yellow precipitate The derivative can be removed by and purified by

Each 2,4-dinitrophenylhydrazine derivatives have characteristic melting temperatures which can be compared with values given in data books. Reaction with Iodine in the presence of alkali (NaOH) - Name : iodoform reaction - To identify the presence of CH3CO group in aldehydes and ketones or CH3CH(OH) group in alcohols - Compound which gives positive results : ethanol. Ethanol. Propan-2-ol, butanone *Equation : Results : precipitate of triiodomethane (CHI3) which has smell

Filtration and Recrystallisation

Determine Melting Point

Preparation 1. Reagents : Conditions : Reflux Results : Orange solution turns green (chromium (VI) Compound is reduced to chromium (III) ) Equation: 2. Equation: of a nitrile by boiling with a dilute acid of primary alcohols or aldehydes

Diagram of Reflux

Making ester (reflux) - Reactions with in the presence of an Carboxylic Acid

Reduction with (lithium aluminium hydride) in Dry ether

Neutralization to produce salts -with reactive metal, eg zinc -with metal hydroxides - with carbonates and hydrogencarbonates - with ammonia

Making acid chloride - Reagent : Phosphorus (V) chloride or phosphorus pentachloride - test OH group

Making Acid Chloride Reagent : Solid phosphorus (V) chloride Results : Steamy acidic fumes of , phosphorus trichloride oxide (phosphorus oxychloride) POCl3, acyl chloride (separated by fractional filtration_ Equation: - must be dry condition : acyl chlorides react readily with water vapour Equation :

Making Ester Reagent : carboxylic acid, alcohol and strong acid catalyst : H2SO4 (equilibrium reaction) Name : (condensation) Equation : Alternative : use more reactive acyl chloride or acid anhydride Equation :

Neutralisation Eg Q : to determine the amount of citric acid in fruit

Water Equation : Alcohol Reaction : Esterification - Vigorous reaction Results : steamy fumes of HCl *Acid chloride need to be kept dry (water vapour in air will react with it) - non-reversible reaction, higher yield of ester - take place without heating Equation :

Acyl chloride

Concentrated Ammonia
- Take place without heating

Amines Results : Produce a substituted amide Equation :

- Produce amide Equation :

Additional Reaction : (Unit 5) 1. Phenol Equation : CH3COCl + C6H5OH CH3COOC6H5 + HCl

Product : Phenyl ethanoate - less vigorous as that between alcohols and ethanol chloride - reactivity of the OH group is modified by the benzene ring - to manufacture aspirin (2-hydroxybenzoic acid) 2. Friedel-Crafts acylation Product : Ketone Reagent : benzene, acid chloride and aluminium chloride (AlCl3) (catalyst) Equation : C6H6 + CH3COCl Benzene Mechanism : ethanoyl chloride phenylethanoate + HCL

Hydrolysis with Acid Equation : - reversible, small yield

Transesterification 1. reaction of vegetable oils (triglyceride or ester) with methanol or ethanol Reagent : sodium hydroxide (catalyst)

Hydrolysis with Base Equation :

Product: methyl ester (biodiesel-greener fuel) - very efficient (yield of 98%) - low temperatures (50C) and atmospheric pressure

- saponification (using KOH) - non-reversible, higher yield

-cheap and readily available catalyst Equation:

2. reaction of an ester with an acid (manufacture margarine) Ester Adv : produce fewer trans fats compared with hydrogenation (nickel catalyst)

Condensation polymerization (form polyester) Eg : 1. Benzene-1,4-dicarboxylic acid and ethane-1,2-diol = - making plastic bottles alternative : diacyl chlorides, diacid anhydrides 2. Nylon: make at room temperature, non-biodegradable Equation : 2. react

Combustion Observation : Equation : (Benzene) 2C6H6 + 15O2 CO2 + H2O CO2 + H2O yellow flame (incomplete combustion)

(Addition reaction) hydrogenation Reagent: Raney nickel catalyst (finely divided with a very large surface area and very high catalytic activity) Temperature : 150C Equation : (Benzene) Benzene or methylbenzene (Methylbenzene) + 3H2

(Methylbenzene) C6H5CH3 + 9O2

Halogenation 1. Addition reaction (only for benzene) = free radical reaction Condition : UV light Equation : (benzene) + 3Cl2 uv, heat Product : 1,2,3,4,5,6-hexachlorocyclohexane

2. electrophilic substitution Condition : catalyst of iron (III) bromide or iron filings (halogen carrier) Temperature : room temperature Equation for catalyst : 2Fe + 3Cl2 rt Equation : 2FeCl3

Nitration (Benzene) Reagent : concn nitric acid and concn sulfuric acid (catalyst) [nitrating mixture] Temperature : 55C - Both H2SO4 and HNO3 are corrosive -HNO3 is powerful oxidant - Electrophile is nitronium ion, NO2+ - Equation for electrophile : HNO3 + 2H2SO4 - nitric acid acts as a base and accepts protons from the sulfuric acid Product:nitrobenzene* use to produce phenylamine (C6H5NH2) for diazonium dye (Methylbenzene or toluene) : use same reagent but at lower temperature

WHY? Temperature : - above 55C further substitution HOW? - Use cold water and slow dropwise addition of benzene to the mixture to maintain temperature -exothermic reaction : acid react and give out heat

Benzene or methylbenzene(toluene) Friedel Crafts reaction (electrophilic substitution) 1. Alkylation 2. Acylation

Sulphonation (replace with SO3H) -Reagent : fuming sulfuric acid ( concn H2SO4 contains sulfur trioxide) - Electrophile: sulfur trioxide - Temperature : room temperature Equation : + H2SO4 C6H6 + H2SO4 ____ + H2O Product : acid

- Reflux benzene with a halogenoalkane/ acyl chloride - halogen carrier catalyst :AlCl3 Product : alkylbenzene/ ketone

Methylbenzene is more reactive as methyl group donate electron density to the ring making it more susceptible for electrophilic attack.

Mechanism of Electrophilic substitution reactions Halogenation Nitration

Alkylation (Friedel-Crafts reaction)

Acylation (Friedel-Crafts reaction)

Phenol - oxygen atom on hydroxyl group of a phenol has two lone pairs electrons - one of the lone pairs on oxygen atom donate electron density into its benzene ring, making it more susceptible to electrophilic attack. - make phenol more acidic than alcohol -its a weak acid it is fairly insoluble in water reacts with NaOH produces sodium phenoxide (colourless solution) doesnt react with Na2CO3 or hydrogencarbonate solutions (very weakly acidic) reacts with Na to produce sodium phenoxide and hydrogen gas Reaction with bromine water - without heating and catalyst Results : 1. bromine water is decolourised 2. white precipitate of 2,4,6-tribromophenol 3. smell of antiseptic Equation : Reaction with dilute nitric acid - reagent: dilute nitric acid Results : white precipitate of 2,4,6-trinitrophenol Equation :

Coupling reactions of diazonium ions : making azo dye Condition : ice cold alkaline solution (NaOH) of phenol and benzenediazonium chloride solution * Benzenediazonium ion carries a positive charge and is a strong electrophile * coupling : joing two aromatic rings together - no N2 gas is produced Equation :

Smell :fishy or smell of decay Alkaline nature : - methyl amine > ammonia > phenyl amine - It has a lone pair on nitrogen atom Equations: 1. bases (amine) (phenylamine) 2. form salts (amine) (phenylamine)

Solubility : 1,2 & 3 can form hydrogen bonds with H2O

Complex ion formation with copper (II) ions (ligand exchange) Results: blue precipitate dissolves to form a deep blue solution Equation:

Boiling point: 1>2 > 3 - no H bonding in 3 amine

Treatment with ethanoyl chloride (Ethanoylation) and halogenoalkanes (condensation) - amine acts as _____, product : amide (ethanoylation)
2& 3Amine (condensation)

Eg: making paracetamol using 4-nitrophenol with tin and HCl (reduction) Equation :

Reaction of phenylamine with nitrous acid to form _________ 1. Prepare nitrous acid, HNO3 in situ, HNO3 unstable ( Equation : NaNO3 + ______ at room temperature) : Reagent: _____NaNO3,

Condition : ice-water mixture, temp: below___

If tempt above ___, it will produce _______. If tempt below ___, it will produce ____ Equation for tempt> 5C : Equation for tempt< 5C :

Displacement structure

Laboratory Preparation of benzenediazonium compound Reagent : Temperature : Steps:

- a strong electrophile due to the positive charge on one nitrogen atom

Condition :Ice bath

Benzenediazonium ions - very unstable

Diazonium compound stable, unreactive - dye ~ can form hydrogen bonds with groups in cotton and wool - coloured dye ~ extensive delocalized electron system that spread across the entire molecule through N N coupling

Coupling reaction with phenol in cold NaOH to form a dye Equation :

Preparation : (Name : ethanoylation : replacement of a Hydrogen atom attached to a nitrogen or oxygen atom by CH3CO- using ethanoyl chloride or ethanoic anhydride) Amide 1. Reaction of an amine with ethanoyl chloride Equation : 2. Reaction of an ammonia with an acid chloride Equation :

Manufacture of Paracetamol Steps : Advantage : no chiral centre in paracetamol molecule - 100% atom economy - manufacturing process easier (no filtration)

POLYMERIZATION
1. Condensation polymerization i) Polyesters : Terylene (PET) Equation : ii) Polyamides : a) Nylon : - used in stockings add durability (tough) Equation : b) Kevlar: make bulletproof vest Equation :

2. Addition polymerization : DISADVANTAGE : very resistant to a range of chemicals (non-biodegradable) i) Poly(propenamide) Equation : Equation: ii) Poly(ethenol) : -hydrogen bonding soluble laundry bags or liquid detergent capsules (liquitabs)

Manufacturing of Poly(ethenol)

AMINO ACIDS Effect of aqueous solutions on plane polarized monochromatic light Acidity :

Acidity and Basicity and the formation of zwitterions Zwitterion Stuctural formula

Basicity - solid in room temperature Reason :

Separation and identification by chromatography

Formation of peptide groups in proteins by condensation polymerization

Reaction with Ninhydrin

Diagram for preparation of phenylamine