Brain Map(aldehyde and ketones)Aldehydes and ketones(ALIPHATIC COMPOUNDS)Methods of preparationsA- From alcohols1. By oxidationa. Aldehydes(oxygen with copper at 200`C)b. Ketones(oxygen with copper at 200`C)2. By catalytic dehydrogenation of alcoholsa. Aldehydes(Cu at 532K)b. Ketones(Cu at 532K)B- From carboxylic acids1- By dry distillation of calcium salts of carboxylic acids.a- Aldehydes(heat the contents)b- Symmetrical ketones(heat the contents)c- Unsymmetrical ketones(heat the contents)2- By catalytic decomposition of carboxylic acids a- Aldehydes(MnO at 543 K)b- Symmetrical ketones(MnO at 543 K)C- From acid chloridesa- Aldehydes(Rosenmunds reaction)Condition add H2 to acid chloride in presence of Pd/BaSO4,S and boiling xylene.b- Ketone(Rosenmund not applicable)D- Form Grignard Reagentsa- Aldehydes(HCN)(dry either followed by hydrolysis)b- Ketones(RCN) (dry either followed by hydrolysis)E- From alkenesa- Aldehydes(reductive ozonolysis)(Zn + water)b- Ketone(reductive ozonolysis)(Zn + water)F- From gem dihalidesa- Aldehydes(starting substance 1,1-dicholoroethane)(hydrolysis in acid medium)b- Ketone(starting substance 2,2-dibromopropane)(hydrolysis in acid medium)G- Form alkynesStarting product any alkyne(1%HgSO4, Hg2+ in presence of dil.H2SO4)(markownikoff)AROMATIC ALDEHYDESa- By oxidation of alkyl benzenes1. Oxidation of CrO3 in acetic anhydride(starting substance toluene)2. Oxidation of CrO3 in CCl4(starting substance toluene)Also called Etard Synthesis(it only attacks the terminal carbon)b- By Reimer-Tiemann reaction(used for prepn of phenolic acids)Condition phenol with CHCl3 + NaOH at 340Kc- By Gattermann-Koch reaction(for benzylic aldehydes)Condition-benzene+CO,HCl in presence of AlCl3 or CuCl

PREPARATION OF AROMATIC KETONES By Freidal-Crafts reactionBenzene+ acid chloride in presence of anhydrous AlCl3 gives aromatic ketonesButIf benzoyl chloride is taken, final product will be diphenyl ketoneSome Important nucleophillic addition reaction of aldehydes and ketones1. By addition of sodium bisulphite(starting substance aldehyde or ketone2. Addition of hydrogen cyanide(very important cyanohydrins)a. Synthesis of alpha-hydroxy carboxylic acids and alpha, beta-unsaturated acids(lactic acid formation )(condition- hydrolyse cyanohydrin in acidic medium resulting in the formation of lactic acid then followed by heating it in presence of conc. sulphuric acid and then loss of water takes place as a result of dehydration reaction and the final product an alpha,beta- unsaturated acid is formed)b. Synthesis of amino acids(Streckers Synthesis) (treat cyanohydrin with ammonia followed by the hydrolysis in acidic medium results into the formation of Alamine or alpha-aminopropanoic acid)c. Synthesis of beta-aminoalcohols(treat cyanohydrin with lithium aluminum hydride and so 3-aminopropan-2-ol is formed)3. Addition of Grignard Reagenta. Aldehyde(1` alcohol is formed)b. Ketone(2`alcohol is formed)4. Addition of alcohols(presence of dry HCl and then treated with alcohol)alcoholsa. To aldehyde when it is added first hemiacetal is formed then acetal is formed b. To ketone it does not react under normal conditions Dihydric alcoholsa. Aldehydes forms cyclic acetalsb. Ketones form cyclic ketalsdate---1/8/2013