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Aldehyde and ketone

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Preparation and reaction of aldehyde and ketone, electromeric effect, aldol condensation, cannizarro reaction, perkin condensation, benzoin condensation, nucleophilic addition reaction and uses of aldehyde and ketone

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Aldehyde and ketone

  1. 1. Aldehyde and ketone Mr. Mote G.D. ADCBP, Ashta Dist: Sangli Maharashtra
  2. 2. Method of preparation of aldehyde and ketone 1. Oxidation of alcohol 2. Catalytic dehydrogenation of alcohol 3. Oxidation of alkene 4. Hydration of alkynes 5. Hydrolysis of gem- dihalides 6. Reduction of acid chlorides 7. From nitriles using Grignard reagents 8. Oxo process 9. Pyrolysis of calcium salt of acid 10. Catalytic decomposition of acids. 2Mr. Mote G.D
  3. 3. 1. Oxidation of alcohol • Alkyl halide undergo reduction with nascent hydrogen in presence of reducing agent like Zn/HCl to form alkanes. 3Mr. Mote G.D CH3 H C H OH O K2Cr2O7 CH3 C H O H2O ethanol acetaldehyde
  4. 4. 2. Catalytic dehydrogenation of alcohol • Alkyl halide undergo reduction with nascent hydrogen in presence of reducing agent like Zn/HCl to form alkanes. 4Mr. Mote G.D CH3 H C H OH Cu 300°C CH3 C H O H2 ethanol acetaldehyde
  5. 5. 3. Oxidation of alkene • Alkyl halide undergo reduction with nascent hydrogen in presence of reducing agent like Zn/HCl to form alkanes. 5Mr. Mote G.D C H C H CH3 O3 Zn/ H2O CH3 C H O 2 - pentene acetaldehyde H2 CH3C ZnO H3C H2 C C O H Propionaldehyde
  6. 6. 4. Hydration of alkynes. • Alkyl halide undergo reduction with nascent hydrogen in presence of reducing agent like Zn/HCl to form alkanes. 6Mr. Mote G.D CH CH H OH HC C H H OH 2HC C H H O ethyne ethanal
  7. 7. 5. Hydrolysis of gem dihalides • Alkyl halide undergo reduction with nascent hydrogen in presence of reducing agent like Zn/HCl to form alkanes. 7Mr. Mote G.D H3C CH H OH H2C C H H OH H2C C H H O ethanal Cl Cl OH -H2O 1,1-dichloroethane 2
  8. 8. 6. Reduction of acid chlorides • Aldehydes can be prepared by the hydrogenation of acid chlorides in the presence of palladium supported over barium sulphate. 8Mr. Mote G.D R C O Cl H2 R C O H HCl H3C C O Cl H2 H3C C O H HCl acetyl chloride acetaldehyde Pd/BaSO4 Pd/BaSO4
  9. 9. 7. From nitriles using Grignard reagents. • A Grignard reagent attacks to nitrile to give the magnesium salt of an imines. • Acid hydrolysis of the imines leads to ketone 9Mr. Mote G.D CH3 CH2 C N CH3MgCl CH3 CH2 C N CH3 MgCl H+ CH3 CH2 C N CH3 H H2O CH3 CH2 C O CH3 NH3 butan-2-one propiononitrile methylmagnesium chloride butan-2-imine
  10. 10. 8. Oxo process. • Alkene react with hydrogen and carbon dioxide to form aldehyde 10Mr. Mote G.D CH3 C H CH2 CH3 H C CH2 C CO2 H2+ O H Hprop-1-ene butyraldehyde
  11. 11. 9. Pyrolysis of calcium salt of acid. • Pyrolysis of calcium salt of dicarboxylic acid to give ketone 11Mr. Mote G.D R C O O R C O O Ca R C O R CaCO3  H3C C O O H3C C O O Ca H3C C O CH3 CaCO3  Calcium salt of dicarboxylic acid acetone
  12. 12. 10. Catalytic decomposition. • When carboxylic acid treated with manganese oxide at 300°C to form ketone. 12Mr. Mote G.D R C O OH R C O OH R C O R CO2 MnO H3C C O OH H3C C O OH H3C C O CH3 CO2 MnO acetone H2O 300°C H2O acetic acid 300°C
  13. 13. Electromeric effect • The complete transfer of shared pairs of π electrons of a double bond or multiple bond to one of the bonded atoms under the influence of the attacking reagent is known as electromeric effect. • Since the effect involves complete transference of electrons, it lead to the development of full positive charge (+) and negative charges (-) within the molecule. Electromeric effect is a temporary effect and operates in presence of attacking reagent. • If a proton (H+) adds to C=C bond, the π bond will break and the electron pair will be transferred completely to one of the C atoms. • When the displacement of an electron pair is away from the atom or group, it is called + E effect. • When the displacement of an electron pair is towards the atom or group, it is called + E effect 13Mr. Mote G.D C O- HH + + C O- HH CN H++ HC OH H CN- C O- HH + + E Effect - E Effect
  14. 14. Reactions of aldehyde and ketones A) Nucleophilic addition reaction 1. Addition of water 2. Addition of alcohol 3. Addition of hydrogen cyanide B) Addition- elimination reaction 1. Reaction with ammonia 2. Reaction with hydroxyl amine 3. Reaction with hydrazine 4. Reaction with phenyl hydrazine 5. Reaction with 2,4 dinitrophenyl hydrazine C) Reduction of aldehyde and ketone D) Oxidation of aldehyde and ketone E) Reaction involving alpha hydrogen 1. Aldol condensation 2. Perkin condensation 3. Benzoin condensation 4. Canizzaro reaction 14Mr. Mote G.D
  15. 15. A. Nucleophilic addition reaction • Positively charged carbon is readily attacked by electron rich nucleophile and negatively charged oxygen is attacked by electrophile. 15Mr. Mote G.D C O- + + Nu C O- Nu H+ C OH Nu Addition product Base catalysed reaction Nu-H + B- Nu- + BH Acid catlysed addition HC O H H++ HC OH H HC OH H Nu Nu- strongweak
  16. 16. 1. Addition of water • Water can add to a carbonyl group to form a 1,1 diol called as gem- diol or hydrate. 16Mr. Mote G.D R C O R H2O+ R C OH R OH Hydrate ketone H3C C O CH3 H2O+ H3C C OH CH3 OHacetone propane-2,2-diol
  17. 17. 2. Addition of alcohol • Addition of alcohol to carbonyl group of aldehyde in presence of strong acid to form hemiacetal and acetal. • Addition of alcohol to carbonyl group of ketone in presence of strong acid to form hemiketal and ketal. 17Mr. Mote G.D R C O H R-OH+ R C OH H OR hemiacetal ketone H+ R-OH R C OR H OR + H2O Acetal Mechanism R C O H H+ + R C OH H R-OH R C OH H O R H -H+ R C OH H O R H+ R C O H O R H H -H2O R C H O R ROH R C H O R O R H -H+ R C H O R O R Acetal Hemiacetal
  18. 18. 3. Addition hydrogen cyanide • Hydrogen cyanide can add to the carbonyl group of an aldehyde or ketone to form cyanohydrins. 18Mr. Mote G.D R C O H HCN+ R C OH H CN CN- HCN + OH- CN- + H+ CN- + R C O H CN HCN R C OH H CN + CN-
  19. 19. 4. Addition of Grignard reagents • Aldehydes and ketones react with Grignard reagents to give an addition product which can be hydrolyzed to give alcohol. 19Mr. Mote G.D CH3 C O H + CH3MgI acetaldehyde CH3 C O H MgI CH3 H2O CH3 C O H H CH3 propan-2-oliodo(isopropoxy)magnesium
  20. 20. B. Addition- elimination reactions • Nucleophilic addition to carbonyl group followed by elination of water to form product containing a double bond. 20Mr. Mote G.D R C O R + R C OH R NuH addition H-NuH -H2O R C R Nu
  21. 21. 5. Reaction with ammonia • Ammonia is a nucleophile that can attack a carbonyl group of an aldehyde or ketone and product is imine. 21Mr. Mote G.D R C O R + R C OH R NH2 addition H-NH2 -H2O R C R NH R C O R + R C OH R NHR addition R-NH2 -H2O R C R NR H3C C O CH3 + H3C C OH CH3 NHCH3 addition CH3-NH2 -H2O H3C C CH3 NCH3 acetone imine
  22. 22. 6. Reaction with hydroxy amine • Aldehydes and ketones react with hydroxylamine to form oximes. 22Mr. Mote G.D + H2N-OHC H OH3C C H NOHH3C acetaldehyde oxime + H2O
  23. 23. 7. Reaction with hydrazine • Aldehydes and ketones react with hydrazine (NH2-NH2) to form hydrazones. 23Mr. Mote G.D + H2N-NH2C H OH3C C H N-NH2H3C acetaldehyde hydrazone + H2O
  24. 24. 8. Reaction with phenyl hydrazine • Aldehydes and ketones react with phenylhydrazine to form phenyl hydrazones. 24Mr. Mote G.D + H2N-NHC H OH3C C H N-NHH3C acetaldehyde Phenylhydrazone + H2O C6H5 C6H5
  25. 25. 9. Reaction 2,4 dinitro phenyl hydrazine • Aldehydes and ketones react with 2,4 dinitrophenyl hydrazine to form 2,4 dinitrophenyl hydrozones. 25Mr. Mote G.D + H2N-NHC H OH3C C H N-NHH3C acetaldehyde 2,4 dinitrophenylhydrazone + H2O NO2 NO2 NO2 NO2
  26. 26. 10 . Reduction of aldehyde and ketone • Reduction of aldehyde and ketone to form alcohol and alkane. 26Mr. Mote G.D Catalytic hydrogentation CH3 C O H + H2 Pt CH3CH2OH ethanol acetaldehyde Reduction with lithium aluminium hydride or sodium borohydride CH3 CH2 C O CH3 LiAlH4 NaBH4 H3C CH2 C H OH CH3 H3C CH2 C H OH CH3 butan-2 -olbutan-2 -ol Clemmensen reduction- Carbonyl group(C=O) converted into CH2 CH3 CH2 H2 C C O CH3 CH3 CH2 H2 C H2 C CH3 Zn/Hg HCl pentan-2 -one pentane
  27. 27. 11. Oxidation of aldehyde and ketone • Aldehydes undergoes oxidation in presence of sodium dichromate to form carboxylic acid • Aldehydes and ketone oxidized by Fehling's or benedicts or tollens reagent to form acid and gives red ppt 27Mr. Mote G.D oxidation of aldehydes CH3 C O H + H2 Na2Cr2O7 acetaldehyde oxidation of ketone CH3 CH2 C O CH3 HNO3 H3C CH2 C O OH H2SO4 CH3 C O OH acetic acid + CH3 C OH acetic acid propanoic acid2- butanone O
  28. 28. 12. Aldol condensation • The reaction of an aldehyde or ketone with dilute base or acid to form a beta-hydroxycarbonyl product. 28Mr. Mote G.D RCH 2 C O H2 OH - or H + RCH 2 C H OH CH R C O H RCH 2 C O H +R' C O H OH - or H + R' C OH H CH R C O H
  29. 29. CH3CH=O dil. NaOH CH3CHCH2CH O OH acetaldehyde 3-hydroxybutanal OH CH2CH=O CH3CH+ O CH3CHCH2CH O O + H2O + H2O nucleophilic addition by enolate ion.
  30. 30. H3C C CH3 O OH H3C C CH2 O H3C C CH3 O H3C C O C H2 C O CH3 CH3 + H2O + H2O H3C C O C H2 C OH CH3 CH3 dil. NaOH
  31. 31. 12. Crossed aldol condensation • If you react two aldehydes or ketones together in an aldol condensation, you will get four products. However, if one of the reactants doesn’t have any alpha hydrogens it can be condensed with another compound that does have alpha hydrogens to give only one organic product in a “crossed” aldol.. 31Mr. Mote G.D CH3CH2CH + H2C OO CH3CHCH2 OH CH O
  32. 32. A crossed aldol can also be done between an aldehyde and a ketone to yield one product. The enolate carbanion from the ketone adds to the more reactive aldehyde. C CH3 O acetophenone + CH3CH=O acetaldehyde dil OH- CCH2 O C H OH CH3
  33. 33. 13. Perkin condensation • Benzaldehyde react with acetic anhydride in presence of sodium acetate to form cinnamic acid. 33Mr. Mote G.D CH=O + (CH3CO)2O CH3COONa CH=CHCOOH H2C C O O CCH3 O CH OH CH2 C O O CCH3 O + H2O H C C H C O O CCH3 O hydrolysis of anhydride + CH3COOH
  34. 34. 14. Benzoin condensation • The Benzoin Condensation is a coupling reaction between two aldehydes that allows the preparation of α-hydroxyketones. 34Mr. Mote G.D C O H 2 KCN/ C2H5OH C O OH Benzaldehyde Benzoin
  35. 35. 14. Benzoin condensation 35Mr. Mote G.D
  36. 36. 15. Canizzaro reaction • Aldehyde are treated with sodium hydroxide to form alcohol and sodium salt of acid. 36Mr. Mote G.D
  37. 37. 15. Mechanism of Canizzaro reaction 37Mr. Mote G.D H C O H OH- H C O H OH H C O H OH H C O H H C O OH H C O OH CH3OH H C O O H C O O Na+ H C O ONa CH3O- CH3O-
  38. 38. 15. Crossed canizzaro reaction • When the mixture of formaldehyde and non enolizable aldehydes are treated with NaOH to form alcohol and formic acid is converted into formic acid called as crossed cannizaro reaction. • E.g. Benzaldehyde and formaldehyde is treated with strong base to form benzyl alcohol and formic acid. 38Mr. Mote G.D C O H Benzaldehyde H C H O C OH H Benzyl alcohol H HCOOH NaOH
  39. 39. 16. Reformatsky reaction • Alkyl halide undergo reduction with nascent hydrogen in presence of reducing agent like Zn/HCl to form alkanes. 39Mr. Mote G.D R C O R + Br CH 2 C O OR' Zn benzene/1. 2. R C O H + Br CH 2 C O OR' Zn benzene/1. 2. OH C OR' O CCH 2 H R OH C OR' O CCH 2R R H3O + H3O +
  40. 40. Identification test for aldehyde and ketone Sr. No Name of test Aldehyde Ketone 1 DNP test DNP solution: phenyl hydrazine in 5M hydrochloric acid . Red or orange ppt Red or orange ppt 2 Tollen’s test :dissolve *1 gm of silver nitrate in 10 ml of water] ( solution A ) and [1 gm of NaOH in 10 ml of water] (solution B ) when the reagent is required mix equal volumes 1 ml from A & B in a clean test tube and add dilute ammonia solution drop by drop until the silver oxide is just dissolve Red ppt on heating of sample solution with Tollen’s reagent Red ppt heating of sample solution with Tollen’s reagent 3 Fehling’s reagent Fehling Reagent A: Copper sulphate and sulphuric acid in water. Fehling reagent B: Sodium hydroxide and Sodium potassium tartarate in water Red ppt with Fehling reagent A and B by heating Red ppt with Fehling reagent A and B by heating 4 Sodium nitroprusside no red color with sodium nitropruside Red color with sodium nitropruside
  41. 41. Sr. No Name of compound Uses structure 1. Formaldehyde Strong smelling gas, Building construction materials, in automobile for light material and durable compounds 2. Paraldehyde Anticonvulsant, alcoholism, hypnotics, sedatives 3. Acetone Solvent, cleaning tool, polyester resins, volatile components for paints, varnishes 4. Benzaldehyde Flavoring agents, Preparation cinnamic acid, Benzoin for throat infection, cinnamaldehyde, mandelic acid 5. Chloral hydrate Sedative, hypnotics, 6. Hexamine In preparations of phenolic resin, used as binders, e.g. in brake and clutch linings, abrasive products, non-woven textiles, formed parts produced by moulding processes, and fireproof materials 7. cinnamaldehyde It is also used in some perfumes of natural, sweet, flavouring in chewing gum, ice cream, candy and beveragesinducer of apoptosis, protect mice against obesity and hyperglycemia 8. Vanilin food flavouring, It is also used in cleaning products, tobacco, and toothpaste, Vanillin is also used in perfumes, to mask unpleasant odors, or tastes in medicine H C O H formaldehyde O O O CH3 CH3H3C H3C C O CH3 C O H CCl Cl C H Cl OH OH

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