H2 Chemistry Organic Chemistry - Reactions

Reactions/ Hydrocarbons

Alkanes CC
Combustion For all hydrocarbons

Alkenes C=C

Arenes Benzene

Arenes Methylbenzene CH3

Combustion Hydrogenation Nitration

Hydrogenation Reagent: H2(g) Condition: 150oC + Ni catalyst or Pt catalyst + r.t. Product: Alkanes *Useful in analysing no. of C=C by measuring amt. of hydrogen absorbed by 1 mol of hydrocarbon Reagent: Br2 in CCl4 Condition: r.t., NO UV light Product: Dibromoalkane Observation: Reddishbrown colour of Br2 is rapidly decolourised * Test for unsaturation

Nitration Reagent: mixture of conc. HNO3 Condition: & conc. H2SO4 + reflux at 60oC Product: Nitrobenzene

Nitration Reagent: mixture of conc. HNO3 Condition: & conc. H2SO4 + 30oC *If temperature is high, further substitution may occur * Methylbenzene more reactive Of side-chain Reagent: Cl2(g) bubbled into boiling methylbenzene Condition: Sunlight/UV light Reagent: Cl2(g) / Br2(l) Condition: halogen-carrier (w/o sunlight)

Halogenation

Reagent: Cl2 (or Br2) in CCl4 Condition: UV light/sunlight Product: Chloroalkanes/ Bromoalkanes

Reagent: Cl2(g) / Br2(l) Condition: halogencarriers + r.t. Product:

1 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions Hydration Industrial Reagent: H2O(g) Condition: H3PO4 catalyst + 300oC + 70 atm Product: Alcohols Laboratory Reagent: conc. H2SO4 + H2O Condition: Product: Alcohols

Hydrohalogenation

Reagent: HX Condition: r.t. Product: Halogenoalkanes Mild Oxidation by cold, dilute, alkaline manganate(VII) ions Condition: OH-/MnO4Product: diols Observation: Purple colour of MnO4- is discharged & brown manganese(IV) oxide is formed *Test for unsaturation Of side-chain Reagent: H+/MnO4Condition: reflux Product: Carboxylic acid Observations: Decolourisation of purple acidified KMnO4 solution. White ppt of benzoic acid *Test to distinguish benzene & methylbenzene * For alkylbenzenes with longer alkyl chains, products include CO2 and H2O too.

Oxidation

By hot, acidified manganate (VII)ions Condition: heat + H+/MnO42 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions Product: Carboxylic acids & Ketones By ozone Reagent: Condition: Product: Carbonyl compounds (aldehydes & ketones) Polymerisation Reagent: Condition: Product: Poly(alkenes)

Others

Friedel-Crafts Reaction Reagent: RX Condition: reflux + AlCl3 Product: Halogenoarenes

Reactions/ Hydrocarbons

Halogenoalkanes

Hydroxy Compounds Hydroxy Compounds Carboxylic Acids - Alcohols Phenols O

H

Hydrolysis Nitration

Hydrolysis Reagent: KOH(aq) / NaOH(aq) Condition: reflux Product: Alcohols

Nitration of benzene ring Reagent: HNO3 (aq) Condition: r.t. Reagent: Mixture of conc. H2SO4 & HNO3 Condition: r.t.

3 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions Halogenation Substitution with HX Reagent: HX (g)* Condition: Reflux Product: R X + H2O *Prepared in situ by mixing NaX or KX with conc. H2SO4 **Involves breakage of C-O bond Of benzene ring Reagent: X2 (aq) [tri] Condition: r.t. Product: tri-bromine Observations: Reddish brown Br is decolourised, white ppt formed & HBr fumes liberated *Chemical test for phenol Reagent: X2 in CCl4 [mono] Condition: r.t. Product: mixture of 2-, 4Observation: Reddish brown Br is decolourised & HBr fumes liberated

Halogenation

Substitution with PX3 Reagent: PX3 Product: R X + H3PO3 Substitution with SOCl2 Reagent: SOCl2 (thionyl chloride) Product: R Cl + SO2 + HCl (g) Substitution with PCl5 Reagent: PCl5 Product: R Cl + POCl3 + HCl (g) Observations: White fumes of HCl evolved *Test for alcohol

Reaction with PCl5 Reagent: PCl5 *No reaction *Breakage of C O bond is very difficult because the p orbital of Oxygen atom overlaps with cloud of benzene ring

4 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions Hydration Deyhydration To Corresponding Alkene Reagent: Excess conc. H2SO4 / Al2O3 Condition: 170oC / 360oC (resp.) Product: Alkenes* *Major product = more substituted alkene = more alkyl group Of Esters Reagent: Alcohol + carboxylic acid Condition: conc. H2SO4 Product: Esters * Breakage of O-H bond is slow & reversible *Suitable for preparing aliphatic esters *Better yield of ester achieved by: 1. Using excess alcohol 2. Removal of ester as it is formed 3. conc. H2SO4 serves to remove water formed Formation

Formation

Of nitriles/cyanides Reagent: alcoholic KCN/NaCN Condition: reflux Product: nitriles/cyanides *Used to lengthen carbon chain

Of Salts Reagent: Bases, carbonates & metals Product: Salts *Vigorous evolution of CO2 with Na2CO3 shows that carboxylic acids are stronger acids than phenol

5 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions Acylation Reagent: Alcohol + acyl chloride Condition: r.t. Product: Esters *Better cos able to carry out in r.t. *Acyl chloride is very reactive thus faster reaction Acylation Reagent: acyl chloride Product: Esters + HCl Reagent: alkaline phenol + benzoyl chloride Product: Esters Of Esters Reagent: Alcohols Condition: reflux + conc. H2SO4 Product: Esters + H2O *Conc. H2SO4 removes the H2O formed, hence increase the yield of ester by shifting the position of equilibrium to the right *Involves braking C O of carboxyl group & O H in alcohol Of Acyl Chlorides Reagent: PCl5 / SOCl2 Condition: r.t. / warm (resp.) Product: Acyl chlorides *Use of SOCl2 is preferred cos both SO2 & HCl are gases, which can escape easily from solution 1o Alcohols; Mild Oxidation Reagent: Acidified K2Cr2O7 Condition: Distil Product: Aldehydes Observations: Orange Cr2O72- turned to green Cr3+ *Further heating with excess H+/ K2Cr2O7 further oxidises aldehyde to carboxylic acids

Of amines Reagent: conc. NH3 (in ethanol) Condition: heat in sealed tube Product: Amines *For higher yield of 1o amine, use excess conc. ammonia Oxidation

Oxidation

6 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions 1o Alcohols; Strong Oxidation Reagent: Acidified K2Cr2O7/ Acidified KMnO4 Condition: Reflux Product: Carboxylic acids Observations: Orange Cr2O72- turned to green Cr3+ / Purple KMnO4 is decolourised 2o Alcohols; Strong Oxidation Reagent: Acidified K2Cr2O7/ Acidified KMnO4 Condition: Reflux Product: Ketones Observations: Orange Cr2O72- turned to green Cr3+ / Purple KMnO4 is decolourised **3o Alcohols resistant to oxidation Elimination Of -HX Reagent: alcoholic KOH or ethanolic KOH/NaOH Condition: Reflux Product: Alkenes

7 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions Others Reaction with Na/Reactive Metal Reagent: Na / reactive metal Product: H2 + alkoxide (R O-) Observation: sodium sinks & bubbles of H2(g) evolved *Reactivity of alcohols with Na decreases as acid strength decreases from primary to tertiary alcohols Iodoform Test Reagent: I2 (aq) / NaOH (aq) Condition: Warm Observations: Yellow ppt/crystal with an antiseptic smell Reaction with Reactive Metal Reagent: Reactive metal Product: H2 gas + phenoxide salt Observation: Sodium sinks & bubbles of H2(g) evolved *Reaction is more vigorous than with ethanol cos phenol is a stronger acid than ethanol Reaction with Base Reagent: NaOH Product: salt + water *Alcohols do not react with base as breakage of O H bond in phenol is easier than in alcohol as phenol is a stronger acid Reaction with Sodium Carbonate Reagent: Na2CO3 *No reaction *Used to distinguish phenol from carboxylic acid

Others

Equation: (for Alcohol) [4, 6, 5, 5]

(for Carbonyl Cmpds) [3, 4, 3, 3]

8 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions

*To identify organic compound with the following structural units

Reactions/ Hydrocarbons

Carbonyl Compounds Aldehydes H/C C=O H

Reagent: 2,4-dinitrophenylhydrazine (Bradys reagent) presence of carbonyl compounds Condition: Warm Observation: orange ppt (NOT YELLOW) Equations: [Aldehyde]

Carbonyl Compounds Ketones R/R C=O R

*Used to detect

Bradys reagent

[Ketone]

9 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions Reagent: I2 (aq) & NaOH (aq) Iodoform test compounds with: Condition: Warm Observations: Yellow ppt/crystal of CHI3 with an antiseptic smell Equations: [Aldehyde]

*Used to detect carbonyl

[Ketone]

Reduction

Reagent: LiAlH4 Condition: In dry ether Equations: [Aldehyde]

[Ketone]

Formation

Of cyanohydrin (Step-up reaction) Reagent: HCN Condition: Trace amt of NaOH (or NaCN) Product: Hydroxynitrile (aka cyanohydrin) Equations: [Aldehyde] 10

R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions

[Ketone]

Oxidation

Reagent: K2Cr2O7/H+ Condition: Warm Observation: Orange Cr2O72- turns green Product: Carboxylic acids Tollens reagent (test for all aldehydes) Reagent: Ag(NH3)2+ (colourless) Observation: Aldehydes give a grey ppt of Ag(s) or silver mirror *Ketones have no reaction Fehlings solution (only for aliphatic aldehydes) Reagent: Alkaline soln of complex copper(II) ions deep blue soln Observation: Aldehydes give a red ppt of Cu2O *Benzaldehyde & ketones have no reaction Acidified aq K2Cr2O7 (for all aldehydes) Condition: Reflux Observation: Orange acidified K2Cr2O7 turns green Acidified aqueous KMnO4 (for all aldehydes) Condition: Reflux Observation: Purple acidified KMnO4 is decolourised 11

Differentiating Tests

R = alkyl/aryl groupX = halogen (F, Cl, Br or I)

H2 Chemistry Organic Chemistry - Reactions

12 R = alkyl/aryl groupX = halogen (F, Cl, Br or I)