Organic Chem Reactions

1. Alkanes
a. Reactions Combustion Free-radical substitution o Steps Initiation Propagation Termination o Conditions Cl2(g)/Br2(l), UV light b. Formation Hydrogenation of Alkenes o H2(g) with Nickel catalyst, at ~150oC, ~5atm o H2(g) with Pt or Pd catalyst, at room temperature Decarboxylation of sodium salt of carboxylic acid o Heating with sodalime

2. Alkenes
a. Reactions Addition of bromine o Br2(l) / Br2 dissolved in CCl4, room temperature Addition of bromine water o Bromine water at room temperature Addition of HBr o HBr(g)/ HBr dissolved in CCl4, room temperature Direct hydration o Steam, H3PO4 catalyst, 300oC, 65 atm Indirect hydration o Cold concentrated H2SO4, followed by heating in the presence of water Addition of Hydrogen o H2(g) with Nickel catalyst, at ~150oC, ~5atm o H2(g) with Pt or Pd catalyst, at room temperature Oxidation o Partial bond cleavage Cold alkali/ cold, dilute acidified KMnO4 o Total bond cleavage Hot, acidified KMnO4 Combustion b. Formation Dehydration of Alcohols o Excess, concentrated H2SO4, 180oC o Al2O3, 400oC Dehydrohalogenation of halogenoalkane Done by Nickolas Teo Jia Ming, CG 12/11

Alcoholic KOH, relfux

3. Benzene
a. Reactions Nitration o Concentrated HNO3, concentrated H2SO4, reflux at less than 60oC Halogenation o Anhydrous AlCl3 / FeCl3/ Fe power, at room temperature Friedel-Crafts Alkylation o Anhydrous AlCl3 / FeCl3/ Fe power, at room temperature Friedel-Crafts Acylation o Anhydrous AlCl3 / FeCl3/ Fe power, at room temperature

4. Alkylbenzene
a. Reactions (side-chain) Halogenation o Cl2(g)/Br2(l), UV light Oxidation o Alkaline/ acidified KMnO4, reflux o Entire side chain is oxidized into CO2H b. Formation Friedel-Crafts Alkylation o Anhydrous AlCl3 / FeCl3/ Fe power, at room temperature

5. Alcohols
a. Reactions Esterification o Concentrated H2SO4, reflux Acylation Halogenation (hydrogen halide) o NaCl(s), concentrated H2SO4, reflux o HX, reflux Halogenation (phosphorus halide) o Cold PCl5 o Red P and Br2, reflux o Red P and I2, reflux Halogenation (Sulfur dichloride oxide) o SOCl2, dissolved in pyridine Dehydration o Excess, concentrated H2SO4, 180oC o Al2O3, 400oC Formation of alkyl hydrogensulfate o Concentrated H2SO4, reflux at 80oC Combustion Oxidation o For aldehyde Acidified K2Cr2O7, heat to distill o For carboxylic acid/ ketone Done by Nickolas Teo Jia Ming, CG 12/11

Acidified K2Cr2O7/ KMnO4 , reflux

b. Formation Alkaline hydrolysis of halogenoalkane o Aqueous KOH, reflux Direct hydration of alkenes o Steam, H3PO4 catalyst, 300oC, 65 atm Indirect hydration of alkenes o Cold concentrated H2SO4, followed by heating in the presence of water Reduction of carbonyl compounds o H2(g) with Ni catalyst at 140oC o LiAlH4, dissolved in dry ether at room temperature c. Test Tri-iodomethane/ Iodoform test o Alkaline I2(aq), heat o Solid I2, NaOH(aq), heat o NaOI(l), heat

6. Phenol
a. Reactions Esterification o Acid chloride and NaOH(aq) Halogenation o Br2 dissolved in CCl4 o Chlorine/ Bromine water at room temperature Nitration o Dilute HNO3, room temperature b. Test Neutral Iron(III) chloride solution at room temperature o Violet coloration Bromine water at room temperature o Decolourisation and white precipitate

7. Aliphatic carbonyl compounds

a. Reactions Oxidation of aldehydes o Acidified K2Cr2O7/ KMnO4 , heat o Alkaline KMnO4 , heat o Tollens Reagent, heat Ammoniacal silver(I) nitrate o Fehlings Solution, heat Alkaline copper(II) tartrate Reduction o H2(g) with Ni catalyst at 140oC o LiAlH4, dissolved in dry ether at room temperature Addition of HCN o Slightly alkaline HCN (aq) at 10-20oC Done by Nickolas Teo Jia Ming, CG 12/11

o HCN (aq), small amount of KCN, 10-20oC Condensation reaction with Bradys Reagent o Bradys Reagent, room temperature. b. Test Tri-iodomethane test o Alkaline I2(aq), heat o Solid I2, NaOH(aq), heat o NaOI(l), heat c. Formation Oxidation of alcohols o Acidified K2Cr2O7/ KMnO4 , heat (to distill for aldehyde)

8. Aromatic carbonyl compounds

a. Reactions Oxidation of aldehydes o Acidified KMnO4 , heat o Alkaline KMnO4 , heat o Tollens Reagent, heat Ammoniacal silver(I) nitrate o NOT Fehlings solution Reduction o LiAlH4, dissolved in dry ether at room temperature Condensation reaction with Bradys Reagent o Bradys Reagent, room temperature. Electrophilic substitution of benzene ring o Fuming HNO, concentrated H2SO4, reflux at 40oC o Cl2 , anhydrous FeCl3, at room temperature b. Test Tri-iodomethane test o Alkaline I2(aq), heat o Solid I2, NaOH(aq), heat o NaOI(l), heat c. Formation For benzaldehyde o Excess Cl2 gas and UV light, followed by reflux with NaOH (aq) For phenylethanone o CH3COCl with anhydrous AlCl3 catalyst, 40oC

9. Carboxylic acid
a. Reactions Metal, metal carbonate, alkali o Room temperature Formation of acyl chloride by a halogen atom o PCl5(s), cold o PCl3(l), cold o SOCl2, dissolved in pyridine Esterification Done by Nickolas Teo Jia Ming, CG 12/11

o Concentrated H2SO4, reflux Reductions o LiAlH4, dry ether, room temperature b. Formation Oxidation of primary alcohol o Acidified K2Cr2O7/ KMnO4 , reflux Oxidation of aldehydes o Acidified K2Cr2O7/ KMnO4 , reflux Oxidation of methyl benzene o Acidified KMnO4 , heat o Alkaline KMnO4 , heat Acid hydrolysis of nitriles o Dilute HCl, reflux Alkali hydrolysis of nitriles o Dilute NaOH, reflux, followed by acidify

10.Carboxylic acid derivatives

a. Reactions Hydrolysis o Ester Dilute H2SO4, reflux o Acyl chloride Water, room temperature o Amide Dilute HCl, reflux React with alcohol/ phenol o Acyl chloride Room temperature Reaction with NH3 o Ester Concentrated alcoholic NH3 o Acyl chloride Room temperature Reduction o Ester LiAlH4, dissolved in dry ether at room temperature o Acyl chloride LiAlH4, dissolved in dry ether at room temperature o Amide LiAlH4, dissolved in dry ether at room temperature b. Formation Acyl chloride o Formation of acyl chloride by a halogen atom Ester o Esterification Done by Nickolas Teo Jia Ming, CG 12/11

 Amide o Acyl chloride, NH3/ RNH2/ R2NH, cold

11. Amine
a. Reactions Alkylation of amine o RX dissolved in ethanol in a sealed tube; Heat Acylation of amine o Acyl chloride; Cold b. Formation Reduction of nitriles o LiAlH4, dry ether, room temperature o H2(g) with Ni catalyst at 140oC o Na and ethanol Reduction of amides o LiAlH4, dry ether, room temperature o H2(g) with Ni catalyst at 140oC o Na and ethanol

12. Phenylamine
a. Reactions Alkylation of amine o RX dissolved in ethanol in a sealed tube; Heat Acylation of amine o Acyl chloride; Cold Halogenation o Br2 dissolved in CCl4 o Chlorine/ Bromine water at room temperature b. Formation Reduction of nitrobenzene o Sn, concentrated HCl, reflux followed by addition of NaOH (aq)

13. Halogenoalkane
a. Reactions Nucleophilic substitution o Alkaline hydrolysis NaOH (aq); Reflux KOH (aq); Reflux o Formation of Nitrile Alcoholic KCN; Reflux o Formation of ether Na in excess alcohol; Reflux o Formation of ester Silver(I) salt of carboxylic acid in alcohol; Reflux o Formation of amine Excess concentrated NH3 in alcohol; Reflux Elimination o Dehalogenation of halogenoalkane Done by Nickolas Teo Jia Ming, CG 12/11

Alcoholic KOH; Reflux Alcoholic CH3O-Na+; Reflux

b. Formation Free radical substitution of alkane Halogenation of alcohols Addition of halogen to alkene

Done by Nickolas Teo Jia Ming, CG 12/11