Organic Chem Reactions

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

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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

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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 Tollen’s Reagent, heat  Ammoniacal silver(I) nitrate o Fehling’s 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 Brady’s Reagent o Brady’s 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 Tollen’s Reagent, heat  Ammoniacal silver(I) nitrate o NOT Fehling’s solution  Reduction o LiAlH4, dissolved in dry ether at room temperature  Condensation reaction with Brady’s Reagent o Brady’s 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/ R2’NH, 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

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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