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Aldehydes and Ketones Are Simple Organic Compounds Containing a Carbonyl Group

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Aldehydes and Ketones Are Simple Organic Compounds Containing a Carbonyl Group Aldehydes and Ketones are simple organic compounds containing a carbonyl group. Carbonyl group contains carbon- oxygen double bond. These organic compounds are simple because the carbon atom presents in the carbonyl group lack reactive groups such as OH or Cl. By Dr. Sayed Hasan Mehdi Assistant Professor Department of Chemistry Shia P.G. College, Lucknow Dr. S.Hasan Mehdi 6/13/2020 This is to bring to kind notice that the matter of this e- content is for the B.Sc. IV semester students. It has been taken from the following sources. The students are advised to follow these books as well. •A TEXTBOOK OF ORGANIC CHEMISTRY by Arun Bahl & B.S. Bahl, S. Chand & Company Ltd. Publication. •Graduate Organic Chemistry by M. K. Jain and S.C. Sharma, Vishal Publishing Co. •Pradeep’s Organic Chemistry Vol II by R. N. Dhawan, Pradeep Publication, Jalandhar. Dr. S.Hasan Mehdi 6/13/2020 An aldehyde is one of the classes of carbonyl group- containing alkyl group on one end and hydrogen on the other end. The R and Ar denote alkyl or aryl member respectively. In the condensed form, the aldehyde is written as –CHO. Dr. S.Hasan Mehdi 6/13/2020 Dr. S.Hasan Mehdi 6/13/2020 1. From Alcohols: a. By oxidation of Alcohols: Aldehydes and ketones can be prepared by the controlled oxidation of primary and secondary alcohols using an acidified solution of potassium dichromate or permanganate. Primary alcohol produces aldehydesRef. Last slide. O K Cr O RCH2OH + [O] 2 2 7 + R C H H 10 Alcohol Aldehyde O CH3CH2OH+ [O] K2Cr2O7 + CH3 C H H Ethyl Alcohol Acetaldehyde The aldehydes formed in the above reaction are very easily oxidised to carboxylc acids if allowed to remain in the reaction mixture. O O + [O] K2Cr2O7 C R C H + R OH H Carboxylic acid Dr. S.Hasan Mehdi 6/13/2020 KetonesKetones areare prepared by by the the oxidation oxidation of ofsecondary secondary alcohols. alcohols. OHOH OO R CHCH K2Cr2O7 R ++ [O][O] K2Cr2O7 ++ RR CC R'R' RR'' HH KetoneKetone OHOH OO CHCH K2Cr2O7 CHCH33 ++ [O][O] K2Cr2O7 + CHCH CC CHCH CHCH H+ 3 3 22 33 CHCH22CHCH33 H Ethyl MethylKetone 2-propanol Ethyl MethylKetone 2-propanol Dr. S.Hasan Mehdi 6/13/2020 Ketones are not easily oxidised further and can be obtained in high yield by this methods. Ketones can also be obtained from secondary alcohols by Oppenauer Oxidation. In this process, the appropriate secondary alcohol is refluxed with excess of acetone in the presence of aluminium tertiary- butoxide, AlOC(CH3)3. Note: The mechanism of following reaction has already been discussed in Alcohols. R R CH CH3 3 CHOH + C O AlOC(CH3)3 C O + CHOH Heat R' R' CH3 CH3 2-Propanol 20 Alcohol Acetone Ketone Dr. S.Hasan Mehdi 6/13/2020 Other reagents used for the oxidation of alcohols to aldehydes and ketones are: - A. Alkaline potassium permanganate: KMnO4/OH B. Chromic acid: H2Cr2O7 (CrO3 or Na2Cr2O7 With dil. H2SO4. C. Pyridine chlorochromate (PCC) C5H6NCrO3Cl, in dichloromethane Pyridine chlorochromate (PCC) C5H6NCrO3Cl, in dichloromethane is a special oxidizing agent. It is used to convert primary alcohols to aldehydes. This reagent does not oxidize aldehydes to carboxylic acids. O PCC CH3CH2CH2CH2OH CH3CH2CH2 C H CH2Cl2 10 Alcohol Aldehyde Dr. S.Hasan Mehdi 6/13/2020 b. Catalytic Dehydrogenation of Alcohols: Aldehydes May be Prepared by passing the vapours of primary alcohols over a copper catalyst heated of 0 about 300 C. O Cu RCH2OH R C H 3000C Aldehyde 10 Alcohol O Cu CH3CH2OH CH3 C H 3000C Ethyl Alcohol Acetaldehyde Similarly Ketones are produced from secondary alcohols. OH O Cu R CH R' R C R' + H 3000C 2 Ketone 20 Alcohol OH O Cu CH3 CH CH3 CH3 C CH3 3000C + H2 2 Propanol Acetone Dr. S.Hasan Mehdi 6/13/2020 2. From Acyl halides: A.Rosenmund Reduction B. By Grignard reagents C. By organocadmium compounds D. By Lithium oragano cuprates Dr. S.Hasan Mehdi 6/13/2020 2. From Acyl halides: Rosenmund Reduction: Acid Chlorides can be reduced to Aldehydes when they are hydrogenated in the presence of a catalyst such as palladium deposited on BaSO4. A catalyst poison like Quinoline or Pyridine and sulphur is frequently added to moderate the activity of the catalyst and thus inhibit the further reduction of aldehyde into alcohol. This conversion of COCl into –CHO is known as Rosenmund O reduction. Pd, BaSO4 CH CH CH C Cl + 3 2 2 H2 CH3CH2CH2CH O + HCl Quinoline/Sulphur Butanal Butanoyl chloride O O d, BaSO4 + P CH CH + HCl CH3 C Cl H2 3 Xylene 4-methyl benzoyl chloride 4-methyl benzaldehyde Dr. S.Hasan Mehdi 6/13/2020 Mechanism of Rosenmund reduction: O OH O H Pd, BaSO4 -Cl- R C Cl + H2 R C Cl R C H H O + H + R C H Dr. S.Hasan Mehdi 6/13/2020 b. By Grignard reagents: Grignard reagent reacts with acyl halides under controlled conditions to form ketones. The resulting ketone can otherwise react further with excess grignard reagent to form Mechanism: tertiary alcohol. O CH OM gBr + CH Nucleophilic addition 3 R C 3 M gBr C CH3 Cl Cl Heat CH3 C O Br + Mg CH3 Cl Acetone Dr. S.Hasan Mehdi 6/13/2020 c. By organocadmium compounds. Ketones can be prepared from acid chlorides by the reaction of suitable organocadmium compounds. R2Cd + 2R'COCl 2R'COR+ CdCl2 (R is preferablly a primary alkyl group bur R' cab be alkyl or Aryl group) O O + CdCl2 2NO C (C H )Cd 2NO C 2 + 2 5 2 Cl CH2CH3 p-nitrobenzoyl chloride Diethyl cadmium Ethyl-p-nitrophenylketone Dr. S.Hasan Mehdi 6/13/2020 D. By Lithium organocuprates (for ketones only). Lithium dialkylcuprates react readily with acid chlorides to form ketones in good yields. O O C Cl C R' + R + R'2CuLi R R'Cu + LiCl (R and R' can be alkyl or aryl groups) Lithium dialkylcuprates needed for this purpose are themselves prepared as below: 2R'X 4Li CuX 2R'Li R'2CuLi + LiX -2LiX The advantage of this method is that Lithium dialkylcuprates do not ract with many of the functional group like NO2, CN, COOR etc with which grignard reagents and organolithiums do react. O O Dry ether 2NO2 C (CH3) CuLi 2NO2 C + CH3Cu + LiCl + 2 196K Cl CH3 p-nitrobenzoyl chloride Lithium dimethyl cuprate p-nitroacetophenone Dr. S.Hasan Mehdi 6/13/2020 3. From 1,3 Dithiane: 1, 3-Dithiane is a weak protonic acid and can be converted into its anion by treatment with strong base like n-butyl lithium. The 1,3-Dithane anion being a strong nucleophile reactions with alkyl halide by SN2 mechanism to form alkyl derivatives of 1,3 dithiane which upon subsequent hydrolysis with HgCl2 in methanol or aq. CH3CN gives aldehydes. + + CH3CH2CH2CH3 S S CH3CH2CH2CH2 S S _ Li+ n-Butane H H Li H 1,3-Dithiane RX -LiX O HgCl2, CH3OH.H2O C + S S HS SH Hydrolysis H R H R Aldehyde Thioacetal Dr. S.Hasan Mehdi 6/13/2020 Similary ketones can be eaisly prepared from 1,3-dithiane by first converting it into its disubstitued derivatives, thioketal in two stages followed by hyrdolysis under the similar above conditions. + + CH3CH2CH2CH3 S S CH3CH2CH2CH2 S S _ Li+ n-Butane H H Li H 1,3-Dithiane R-X -LiX O n-butyl lithium HgCl , CH OH.H O 2 3 2 S S -C4H10 S S + C Hydrolysis R'X HS SH R' R R' R H R Thiokettal Thioacetal Ketone Dr. S.Hasan Mehdi 6/13/2020 4. From Carboxylic acids: Reaction of lithium alkyls with carboxylic acids provides a useful route for the synthesis of ketones. For e.g. O O R C OH + + 196 K R' Li R C O Li+ + R'H Dry ether R' = 10, 20, 30 alkyl or aryl group OH O OLi H+/H O - 196 K 2 R C O Li+ + R' Li R C O Li+ R C OH Dry ether Dry ether R' R' The overall reaction may be represented as Unstable O OLi O + 2R'Li H /H2O R C OH R C Li R C R' -R'H Dry ether O R' Ketone R C R' Ketone Dr. S.Hasan Mehdi 6/13/2020 5. From Nitriles: By Reaction with Grignard Reagents or organolithium compounds: Grignard reagents or organolithium compounds add to alkyl or aryl nitriles to form addition products which upon subseqent hydrolysis gives ketones. O Dry ether + R C N + R'MgX R C NMgX+ H /H2O R C R' -NH -Mg(OX)X R' 3, Alkyl or aryl nitrile Ketone Addition product O R C N Dry ether + + + R'Li R C NLi H /H2O R C R' Alkyl or aryl nitrile -NH -LiOH Alkyl or R' 3, aryl Lithium Addition product CH C N + Dry ether H+/H O 3 CH3CH2MgBr CH3 C NMgBr+ 2 -NH3, -Mg(OX)X Acetonitrile ethyl Mag. Bromide CH2CH3 Addition product O CH3 C CH2CH3 Butanone Dr. S.Hasan Mehdi 6/13/2020 6. Oxidation of Alkenes (Ozonolysis): Aldehydes and ketones can be obtained by ozonolysis of alkenes. This involves the treatment of the alkenes with ozone to give ozonides. The ozonides are not isolated because they are explosive often in dry state. They are decomposed with Zn + H2O to form aldehydes and ketones. H H H H 1. O3 CH3CH2C CCH3 + CH3CH2C O O CCH3 2. Zn + H2O 2-Pentene Propanal Acetaldehyde This is not a good method because a mixture of carbonyl compounds is often produced.
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