4 Carbony| Compounds + Acetaldehycle and Acetone 4 Other Carbony! Compounds CARBONYL GROUP Introduction Aldehydes and ketones, both have the general formula, C,H,,0 and the common feature of both is carbonyl (C=O) group and, therefore, they ae called carbonyl compounds. Aldehydes and ketones are the first oxidation products of primary and secondary aleohols respectively. Aldehydes are obtained by replacing the two terminal hydrogen atoms of alkanes by the oxygen atom while Ketones are obtained by replacing the two non-terminal hydrogen atoms of alkanes by oxygen. Due to this, aldehyde group becomes chain terminating group and ketonic group occurs within the chain In aldehydes, CHO group may be attached to a hydrogen atom or alkyl group Carbonyl group oF aryl group. is anached with sno: cnc aiom in aldehyde Im ketones, C=O group may be attached to two alkyl groups, two aryl groups cor one alkyl anone aryl group. Ir both the groups are same, they’ are simple Ketones and if they are different, they are mixed ketones, AI Simpte ketones (or) symmetrical Ketones: R-CO-R tg # CHy-CO-CH,, “He, ote Mixed Ketones (or) unsymmet cs | RCO-R Carbonyl group is attached with ‘wo alkyl groups in ketone Aromatic ketones : Ar-CO-R Acetophenone Benzophenone Aldehydes and ketones are wide spread in animal and plant kingdom, Their role in biochemical process of life is very important. They add fragrance and flavour to nature. They are used in many food products and pharmaceuticals. Sor them are used as solvents and as adhesives, paints, resins, perfumes, plastics, fabrics, ete. Three of them are given below Ho (CH=CHCHO. m on OH Vanitlin Cinnamaldehyde —_p-HydroxybenzaldehydeNomenclature WYN Dimethyl ketone is called acetone Ae IUPAC name of saturated aldehyde is alkanal ~~ There are two systems of naming carbonyl compounds, ‘Common system Aldehydes and ketones are often called by their common names. Common names of the aldehydes are derived from the names of the corresponding carboxylic acids by replacing the suffix acid with aldehyde. The location of the substituent in the carbon chain is indicated by letters a, B, ,8, etc, The carbon being the one directly linked to the aldehyde group, B-carbon the next and so on. HCOOH (Formic acid) «LL HCHO (Formaldehyde) CH,COOH (Acetic acid) LLL CH,CHO (Acetaldehyde) The common names of ketones are derived by naming (wo alkyl or aryl groups bonded to the carbonyl group and adding the word ketone. In case of simple ketones, they are named as dialkyl ketones. However, mixed ketones are named by naming the two alkyl groups attached fo the Ketonic group as separate words in alphabetical corder and adding the word ketone. The locations of substituents are indicated by Greek letters, 0,01, B.B’ and so on. Alkyl phenyl ketones are usually named by adding the acyl group as prefix to phenone. CH,-Co-CH, Dimethyl Ketone (Historical name is acetone) CH,-CO-CH, Ethyl methyl ketone cH 4B’ Dichlorodiethyl ketone Methyl phenyl ketone (or) Acetophenone TUPAC system ‘The TUPAC names of open chain aliphatic aldehydes and ketones are derived from the names of the corresponding alkanes by replacing the ending -e with -al and -one respectively. In case of aldehydes, the longest carbon chain is numbered from the carbon of the aldehyde group while in case of ketones, the numbering begins from the end nearer to the carbonyl group. The substituents are prefixed in alphabetical order along with numerals indicating their positions in the carbon chain ‘The name of the simplest aromatic aldehyde carrying the aldehyde group on a benzene ring is benzene carbaldehyde. However, the common name benzaldehyde is also accepted by IUPAC. When three or more aldehyde groups are present in a compound then all the aldehyde groups present in the compound are treated alike and the word carbaldehyde is used, cH—cHo gu-cHo (CH, —CHO ‘The common and IUPAC names of some aldehydes and some ketones are given Propa‘Table 3.1 Common and TUPAC names of some aldehydes and ketones Structure Common name TUPAC name HCHO Formaldehyde ‘Methanal CH,CHO Acetaldehyde Ethanal Isobutyraldehyde 2-Methylpropanal B-Methyl valeraldehyde 3-Methylpentanat CH, = CH - CHO Acrolein 2-Propenal (CH,-CH=CH-CHO ‘Crotonaldehyde 2-Butenal go" Benzaldehyde Benzenecarbaldchyde CHO ‘Cyclohexane carbaldehyde Cyclohexanecarbaldehyde p-Nitrobenzaldehyde 4-Nitrobenzenecarbaldehyde Clone Phihalaldehyde Benzene-I,2-dicarbaldehyde CH,-CO-CH, Acetone Propanone (CH= CH= CO~ CH=CH, T CH, cH, Diisopropyl ketone 2.4-Dimethylpentan3-one CH,-CO-CH,-CH,-CH, Methyl n-propyl Ketone Pentan-2-one 0, 01, .'Trichlorodiethyl ket 2,2,4-Trichloropentan-3-one (CH)).C = CHCOCH, Mesityl oxide 4-Methylpent-3—en-2-one a CH,-CH,-C-CH,-CHO B—Oxopentanal 3-Oxopentanal Ch, Methyl cyclohexanone 2-Methyleyclohexanone om Methyl phenyl ketone Acetophenone oro Dipheny! ketone Benzophenone Ethyl (phenyl)methy! ketone 1-Phenylbutan-2-oneGive the common name and TUPAC name of the compound, CH.=CH-CO-CH=CH,, The common name of CH.=CH-CO-CHECH, is divinyl ketone, TUPAC name is 1 4-pentadien-3-one. Write the structure and common name of 3-phenylpropenal ent of phon popealis (C))—CHCH-CHO Its common name is cinnamaldehyde. Give the structure and IUPAC name of vanillin, cHo ‘Structure of vanillin is Hy on ‘The TUPAC name of vanillin is 4-hydroxy-3-methoxybenzenccarbaldehyde, CHO OH me and common name of ‘The IUPAC name of is 2-hydroxybenzenecarbaldely de (or 2-hydroxybenzaldehyde) ‘Common name of 2-hydroxybenzaldehyde is saicylaldehyde. nn Aldehydes show chain isomerism among themselves and functional isomerism with ketones, cyclic ethers and unsaturated alcohols, They exhibit tautomerism with unsaturated alcohols. Aldehydes with four or more carbon atoms and ketones with five or more carbon atoms show chain isomerism. ‘Aldehyde and Ketones may exhibit metamerism. The formula CnH,,O ean represent structures etone are « pair that have an open chain containing a x bond and a closed chain with out any x, of functional bond (monocyclic). So, alkanals, alkanones, unsaturated aliphatic alcohols, isomers unsaturated alipatic ethers, cycloalkanols, cycloalkylalkanols, alkoxyeycloalkanes, alkoxyalkyleyclo-alkanes and oxacycloalkanes (cyclic ethers) can be isomeric with each other if they have the same number of carbon atoms. Chain isomerism CH, ci -CH-cHo 2-Methylpropanal CH,CH,CH,CHO. Butanal cH, 0 Lo CH,-CH-C-CH, 3-Methylbutanone-2an~ Tautomerism is also called enol-keto ~Ae CHCH,CHO Propanal (aldehyde) cH.cocn, Propanone (ketone) Cycloproponot (saturated alcohol) (unsaturated alcohol) CH, ~CHy i CHCOCH, CH) GH . N\ (CH,CH,CH,CHO. CH,-CH=CH-CH,OH Butanal (aldehyde) But-2-en-1-ol (unsaturated alcohol) Butanone (ketone) Tetrahydrofuran (cyclic ether) ‘Tautomerism : It is also called enol-keto isomerism, ° ° ou CH,-C-CH, == CH,=C-CH, Ethanal Ethenol Propanone Propen-2-ol (carbonyl form) (enol form) (keto form) (enol form) Metamerism : Aldehydes do not exhibit metamerism. Ketones being bivalent, exhibit metamerism, CH,CH,COCH,CH, Diethyl ketone U1 CHy-C-H == CH,=CHOH CH,CH,CH,COCH, Methyl propyl ketone TUPAC names ofthe possible structural isomers of formula, C,H,O. fate the isomers of formula, C,H,O. (Propanaly Gi) CH,COCH, (Propanone) (y) CH,=C-CH, t on (si) CH.=CH-O-CH, (Methoxyethene) (i) CH.=CHCH,OH (Prop-2-en-1-ol) (Propen-2-01) (0) HO-CH=CH-CH, (Propeno!) (oii) CH “CHCH, 1. 2-Epoxypropane) (vil) CH, ~CH,-CH, (L3-Epoxy propane) ©. 0" WON 6) pp 2CHOM cyeroropanad ‘Write the structural formulae and IUPAC names for all the isomeric aldehydes and ketones of ‘molecular formula, C,H 0. With the formula C,H, Possible aldehydes are @ CH, CHyCH,CH,-CHO Pentanal (ai) (CH).CHCH,CHO av) 3-Methylbutanal 2 Possible ketones are () CH,-CH,-CH,-CO-CH, (ii) CH,-CH,-CO-CH,-CH, (iti) (CH,),CHCOCH, 3-MethyIbutanone (0, four allehydes and three ketones are possible. Gi). CHyCH,-CHICH,)CHO, 2-Methytbutanal (cy),ccHo. imethypropanal Pentanone-2 Pentanone-3Structure of carbonyl group aA A hee The bond in carbons group is pol, ith panial postive charge on arom es 3.21 Preparation Both aldehydes and Ketones have carbonyl group as the functional group ‘The carbonyl carbon is sp? hybridised and, thus, it has three sp? hybrid orbitals and ‘one unhybridised p-orbital. It uses sp? hybrid orbitals to form three sigma bonds, one with oxygen atom and remaining two with two other atoms or groups (R or H). The bond angles are approximately 120° as expected of a trigonal coplanar structure ‘The unhybridised p-orbital of carbonyl carbon forms pi bond with oxygen atom by sideway overlapping with half filled p-orbital of oxygen atom. The carbon oxygen double bond is polarised due to higher electronegativity of oxygen relative to carbon. Consequently, oxygen attains a partial negative charge and carbon a partial positive charge making the bond polar. Hence. the carbonyl carbon is an electrophilic (Lewis acid), and carbonyl oxygen, a nucleophilic (Lewis base) centre ‘The high values of dipole moments of carbonyl compounds than the corresponding ethers and the high polarity of the carbonyl group is explained on the basis of resonance involving a neutral and a dipolar structures. Sc-0 —- dé_6 neutral dipolar EXERCISE - 3.1.1 ‘What are aldehydes and ketones? Give the structural differences, . Mention the types of isomerism exhibited by carbonyl compounds. What are symmetrical and unsymmetrical ketones? Give examples. Give the IUPAC names of the following compounds (i) CH,CH,CO(CH,),CH,, (ii) CH,CH(CH,)CH,CH,CHO, (ii) CH,CH,COCH,COCH, and (iv) CH,CH,CH=CHCHO. . Write the names of the isomeric ketones possible for 2,2-dimethyl propanal. ACETALDEHYDE AND ACETON! Pannen nen From alcohols Oxidation : Aldehydes can be prepared by the regulated oxidation of primary alcohols, Oxidation may be carried out by acidified solution of potassium dichromate or potassium permanganate or manganese dioxide. The reaction is controlled by distilling out aldehyde as soon as itis formed as aldehydes are very susceptible to further oxidation to carboxylic acids RCH,OH + (0) —+RCHO + H,0 CH,CH,OH + (0) —4CH,CHO + H,0Seen Ahad Oppenauer method is used for oxidation of secondary alcohol to give ketone Pyridinium chloro chromate (PCC) (C,H, NHC:O,CT>) o Coltin’s reagent (or) Corey's reagent is « good oxidising agent for converting primary alcohols to aldehydes and secondary alcohols o ketones. Collin’s reagent is used in non-aqueous medium, dichloromethane. RCH,OH + Bie 2 RHO +H,0 (CH,CH,OH + (0) 9CH,CHO +H. RCHOHR + (0) —9 RCOR + 1,0 CH,CHOHCH, + (0) — CH,COCH, + H,0 Pyridinium dichromate (PDC), (CsHsNH);Cr,0, can also be used for the oxidation of alcohols to carbonyl compounds. Alcohols containing a double or triple bond can be oxidised to corresponding unsaturated carbonyl compound by Jones’ reagent in acetone medium at 0-20'C. Aqueous chromic acid (CrO, in dil. H,SO,) is called Jones’ reagent. mu r (C,H, -CH-C 2 CH—9G,H,-C-C-2CH oH © 1 (CH, ~CH =CH-CH-C=CH—9CH, ~CH=CH-C-C=CH Collin’s reagent also does not attack double bond and the oxidation stops at aldehyde stage only. oot (Cyeloher-2-en-one MnO, is a fairly selective reagent for oxidation of alcoholic group and is often used {0 oxidise allylic alcohols to a, B unsaturated aldehydes and Ketones, and benzylic alcohols to corresponding carbonyl compounds. “cH = cH-ci,on 2H, cit cH CHO CCrovgl alcohol (allylic) Crotonaldehyde GeO BenzyTalcohol Benraldehyde Oppenauer oxidation : This method is usually employed for the oxidation of secondary alcohols to ketones by aluminium tert. butoxide, [(CH,) CO],Al. The secondary alcohol is oxidised to Ketone at the expense of the reduction of acetone to isopropyl alcohol (or cyclohexanone to cyclohexanol). This method is particularly useful for oxidising unsaturated secondary alcohols because it does not affect carbon-carbon double or triple bond. RAG cHcoch, uuncona, BS : DcHOH +CH,CocH, AH 5S c0+ CH, CHOH CH rv tar RV 5 2 sce.alcohol acetone (excess) ketone isopropyl alecho!Dehydrogenation of 1° alcohol gives aldehyde and 2° alcohol gives ketone Ae Cale om dy disilaton gives ~ CH, ~CH-CH, ~cH=cH, ncaa pene t cn HCH, + eyelohexano pent—4—em—2—one D-L Cyelohex-2-en-I-one Catalytic dehydrogenation : When vapours of a primary or a secondary alcohol are passed over copper or silver catalyst at 300°C, dehydrogenation takes place and an aldehyde or a ketone is formed respectively. R-CH,OH > R-CHO+H; (CH,CH,OH > CH,CHO+H, aT R-CHOH-R’ > R-CO-R’+H. cu.cHoncn, 2-9 cH,cocn, +H, In presence ofthese catayets, if aris present, water i also formed along with carbonyl compouod. The deyrogennion reaction isa beter method of preparaion because there iso risk of further oxidation of aldehyde or Ketone From fatty acids Dry distillation of cacium salts of fatty acids : Aldchydles can be prepared by the dry distillation of equimolar mixture of calcium salt ofa fany acd with calcium formate (RCOO),Ca + (HCOO),Ca —45 2RCHO + 2C:CO, (CH,COO),Ca + (HCOO),Ca 9 2CH,CHO + 2€uCO, The yield is geneally poor due to side reactions. Thus, higher aldehydes are not prepared by this method. Symmetrical ketones may be obtained when calcium salts of fatty acids (ther than formic acid) are heated at 400°C. (RCOO),Ca—2 R-CO-R + CaCO, (CH,CO0),Ca+4CH,CoCH, + CaCO, When vapours of fatty acids mixed with formic acid are pussed over heated thoria at 350°C or manganous oxide at 300°C give aldehydes. RCOOH + HCOOH —> RCHO + 1,0 + CO, CH,COOH + HCOOH — CH,CHO + 11,0 + Co, Under similar conditions, symmetrical ketones are obtained from fatty acidsTeAa Ahad Alkenes in Wacker process give carbonyls we an Alkynes on hydration give carbonyls Wacker process : When an alkene is teated with an acidified agueous solution of palladiara chloride and capric chloride, aldehydes or knloces can be obialaed =CH, + PdCl, + H,O fb (CH,CHO + Pd + 2HCI CH.-CH-CH, + PaCl, + H,0 825 CH,COCH, + Pa + 2HC1 Reductive ozonolysis of alkenes : Alkenes add on ozone to form unstable caonide which when decomposed by passing hydrogen in presence of zine dust and o,adchyde ot ketone r bo ae formed depending upon the stuctre of alkene R-CH=CH-R + 0, 4i >> 2RCHO + H,0 (CH, ~CH=CH CH, + 0, 4-3 2CH CHO + H,0 RR uo.% Rx, wk Rca K pet Ov oO HOCK RH cH AH, DS is 0.2 0H Cy Coy, +08 BABS 2cH,COCH, + H,0 cH From alkynes Addition of water to alkynes in presence of sulphuric acid and mercuric sulphate gives aldehydes or ketones. Acetaldehyde is obtained by passing acetylene gas through an aqueous solution of 40% sulphuric acid and 1% mercuric sulphate at 60°C. An unstable enol vinyl alcohol is formed as intermediate. HC=CH + H,O—> [CH,=CH(OH)]| == CH,CHO. Acetone is obtained by passing propyne into an aqueous solution of 40% sulphuric acid and 1% mercuric sulphate at 60°C. An unstable enol, propenol-2 is formed as intermediate CH,-C=CH + H,0—+[CH,-C(OH)=CH,] —= CH,-CO-cH, Hydroboration-oxidation of alkynes : Aldehydes can be prepared by hydroboration oxidation of terminal alkynes. The overall result san anti Markovnikow addition of water across the triple bond. Aldehydes are formed if the triple bond is located at the end of the chain and in all ther cases, ketones are formed! 3CH,-CecH—#45 (cH,cH=cn-), p Propyne CH=CH =CHOH—CH,CH,CHO propanalWIN Enylidene halide on base hydrolysis gives acetaldehyde WW i n~ Rosenmund’s reduction of acid chlorides give aldehydes Wr Reduction of cyanides foilowed by hydrolysis 10 give aldehydes is called Stephen Ae From gem-dihalides Aldehydes are obtained by alkaline hydrolysis of gem-halides in which two halogen atoms are attached to the terminal carbon atom, (CH,CHC), 2894 5CH,CH(OH), —->CH,CHO Ketones are formed by hydrolysis of gem-halides in which the two halogen ‘atoms are attached to a non-terminal carbon atom, CH ACI axon, CHS OH HS caper cH Soni? cH From Grignard reagent Grignard reagents give aldehydes with hydrogen cyanide and ketones with alkyl eyanides HCO + RMX 91 C-NMX R HeC=N AOE CH,CHO + NHL, + M(OIBr 2L°_y RCHO + NH, + Mg(OH)X RCEN + RMgX—9R-CHNMEX HP R-CHO + NHL, + MeCOHDX R R CH, Con BOMHEY CH, CA04 NH, + M(OHL cHy From acid chlorides Acid chlorides can be reduced into aldehydes with hydrogen over catalyst 1m supported on barium sulphate. ‘This reaction is called Roseamund . Ketones cannot be prepared by this method RCOCI+ H, —pBL—» RCHO + HCI cH.COCT +H, From nitriles and esters An alkyl eyanide is dissolved in ether and reduced with stannous chloride and hydrochloric acid. The iminochloride thus formed gets hydrolysed to give aldehyde HHI E24 RCHO + NH,CL i. This method is for preparing oaly aldehydes. Alernatively, niles are seleaively reduced by d-lobutylalaminium hydride, (DIBAL-H) to imines followed by hydrolysis to aldehydes. cH,cN 88H CH,CHO CH, CH-CH-CH,-CH-CX— MBE CH.cH-CHCH,CH,CHO Similarly, esters are also reduced to aldehydes with DIBAL-H, cu,cooc,n, —288%""4.cH,cH0Process : Aldehydes can be prepared industrially by heating a mixture of the alkene and synthesis gas (CO+H,) under pressure in the presence of octa carbonyl dicobalt as catalyst. This is called hydroformylation or earbonylation. This reaction involves the addition of a hydrogen atom and a formyl group across the carbon- carbon double bond. R-CH=CH, +CO#H, 2M, R-CH-CH, to ‘Alkene bohno Aldehyde The reaction always gives isomeric straight chain and branched aldehyde, straight chain aldehyde is a dominant product. 2CH, CH=CH, + 2CO + 2H, EME cH, CH.CH.cH.cHO + cH, -CH CHO Butanal (Majo) sobutanal (Minor) Some special methods for ketones ‘Treatment of acyl chlorides with dialkyl e: prepared by the reaction of cadmium chloride with Grignard reagent, gives ketones. 2RMgX + CUCL, ——9R,Cd + IMgOOCI 2R-CO-CI + R,Cd—9 2R-CO-R + CaCI, 2CH,COCT + (CH,),Cd —— 2CH,COCH, + CaCl Ketones can be obtained by the reaction of acid chlorides with lithium dialkylcuprate (Gilman reagent), ‘OCH +(CH),CuLt ES or +Licl Cyeloiexane Cyclohexyt ‘carbonyl chloride methyl ketone ‘oc Which ane ies only actos on redacive ornolyss? 2,3-Dimthylbut-2-ene yes only aetne on etive ozonolysis oH oH ct, -C26-ctt+ 0, B25 24, C0 by Which aldehydes are formed by the reductive ozonolysis of penta-1.3~ diene? Formaldehyde, acetaldehyde and glyoxal are formed by the ozonolysis of peata-1,3-diene iL =cH-CH=CH-CH,+0, M2 cH,0-+ OHICCHO + cH,cHO cH cnscrt, 22% x 24> ¥, What are the compounds x’ and"? (Compound X is 2-butanol (C,H,CHOHCH,) and ¥ is butanone (C,H,COCH,).‘Which ofthe vo method (a) Clemmensen’s and (b) Woll-Kichner, re best suitable for conversion of CH_=CH-CH,CHO into CH,=CH -CH.CH. Wolff-Kishner method is the best method asin the other method, double bond gets reduced ‘To get phenylethanal, which compound should be treated with chromy chloride? Give equation. Ethyl benzene on treatment with chromyl chloride, phenylethanal is obtained CHLCH, CH;CHO What products are obtained dry distillalation of a mixture of (CH,COO),Ca and (C,CH,COO).Cx? “The products obtained are CH,COCH, , CH,CH,OCH,CH, and CH,COCH ¢ ‘What combination of Grignand reagent and alkyl nitirle is useful to prepare butanone 9) CHEN 2500 CH.COCHCH, 1») cHCH,cN S48 cH cH,coct, Under what circumstances may an aldehyde be prepared by oxidation of primary alcohol, with acid dichromate? If the aldehyde product is more volatile than the reactant alcohol and H,O, it may be removed from the reaction mixture by distillation as soon as it is formed. Give names ofthe reagents to bring about the following transformations G)_ Pentan-I-ol to pentanal, (i) Ethanaitrile to ethanal, (ii) Allyl alcohol to. propenal, (iv) But-2-ene to ethanal and (v) But -I-yne_ to butanone, Pyridiniumchlorochromate, C,H.NH°CrO,CF (PCC) (iisobuty!) alu sydride (DIBAL -H) Pyridinium chlorochromate (PCC) Ozone, water and zine dust 40% dilute HS, and 1% HgSO, —e ED Physical properties water soluble due to Inydrogen bonding A —— At ordinary temperature, formaldehyde is a gas while next ten members of the aldehyde series are colourless volatile liquids. Ketones upto eleven carbon atoms are also colourless volatile liquids. The higher members of both the series are solids. The lower members of aldehydes and ketones such as formaldehyde, acetaldehyde and acetone are miscible with water in all proportions, because they form hydrogen bond with water. ‘The solubility of these compounds in water decreases with the increase in the size of the alkyl group. It is due to the hydrophobic nature of the alkyl group. All aldehydes and ketones are fairly soluble in organic solvents like benzene, ether, chloroform, eteDipole-dipole interactions are weaker than intermolecular Iydrogen bonding aU Cee Lower aldehydes have unpleasant sharp pungent odours. As the size of the molecule increases, the odour becomes less pungent and more fragrant. M naturally occurring carbonyl compounds are used in the blending of perfumes and flavouring agents, Aldehydes and ketones have relatively high boiling points as compared to hydrocarbons or ethers of comparable molecular masses. It is due to appreciable inter molecular (dipole-dipole) attraction as the aldehydes and ketones are polar molecules. These dipole-dipole interactions are however, weaker than intermolecular hydrogen bonding in alcohols. Consequently, boiling points of aldehydes and ketones are relatively lower than alcohols of comparable molecular masses. The following compounds have almost same molecular mass (58-60). Their boiling points order is: I-propanol (alcohol, 370 K) > propanone (ketone, 329 K) 2 propanal (aldehyde, K) > methoxyethane (ether, 281 K) 2 butane (alkane, 273 K). Arrange the following in the order of increasing boiling points H,CH,OH(B), CH,CH,OCH,CH,(C), CH,CH,CH,CH,CH, (). Molecular masses of compounds A, B, Cand D are almost same (72-74), Compound (B) is an alcohol, associated with extensive inter molecular hydrogen bonding. Hence its boiling point is highest. (A) isan aldehyde. (A) is more polar than (C), which is an ether. (D) isan alkane and possesses only weak van der Waals forces. Hence its boiling point is least Hence the order of boiling points is ;B > A> C>D. — 3.2.3 Chemical properties Sea Aha Carbon atom of carbonyl group is antacked by nucleophile LU eal NN Aldchydes and ketones are highly reactive compounds. Since both possess the same carbonyl functional group. they undergo similar chemical reactions. The characteristic reactions of aldehydes and ketones are nucleophilic addition reactions Nucleophilie addition reactions ‘The carbonyl group is a highly polar group as the m-electrons of the double bond are shifted to the more electronegative oxygen atom. SM >c=0 ‘Thus, the carbonyl group has two active centres which can easily be attacked ‘The positively charged carbon is readily attacked by electron rich nucleophiles. The negatively charged oxygen is attacked by electron deficient electrophiles. However, during addition reaction, nucleophilic attack because the anion produced is more stable than the cation Ne ta —ow_, Se NS c=0+Nu 5 Sc-06 454 >c-on 2 At ar? > Nu Nu In the first step, planar sp? hybridised carbon changes to sp* and a tetrahedral alkoxide intermediate is produced. If nucleophile is weak, the reaction requires an acid cataly:Formaldehyde is most reactive in nucleophilic addition reactions A ain Aromatic aldehydes are less reactive than aliphatic aldehydes 10 nucleophilic addition We > Sc-0 > * Sc cH cH we de cbt > 1 (High I effect) It may be noted that benzaldehyde is less reactive than aliphatic aldehydes. g : R cneben » Gpbar > Oban > OO) (Phenyl group ~ electron releasing resonance effect) HOH ‘Compare the reactivity order of benzaldehyde, p-tolualdehyde, p-nitrobenzaldehyde and acetophenone Order of reactivity : acetophenone < p-tolualdchyde < benzaldehyde < p-nitrobenzaldchyde Due to hyperconjugation, methyl group in p-tolualdehyde is electon releasing because of | ‘which the positive charge on carbonyl carbon decreases. Due to resonance effect (electron ‘withdrawing effect of nitro group) in p-nitrobenzaldehyde, the postive carbon increases. Greater the positive charge on carbonyl carbon, more is the rea Further, it may be noted that ketones are less reactive than aldehydes (a) Addition of hydrogen cyanide Both aldehydes and ketones react with hydrogen eyanide (sodium cyanide and dilute sulphuric acid) to form eyanohydrins. The reaction occurs very slowly with pure hydrogen cyanide. It is catalysed by a base and the generated cyanide ion being a strong nucleophile readily adds on to carbonyl compounds. ln dh 1 1 b+:GN 2 | —¢-0| 2 —C-on eresani Acetone cyanohydrin on hydrolysis gives lactic acid A Carbonyl compounds are purified using NaHSO,, a WT Addition product of aldehyde or etone with Grignard reagent on hydrolysis gives alcohol Ae Aldehydes react with alcohols to form acetals ‘Cyanohydrins are used to prepare O1—hydroxy acids, amino acids, o-amino alcohols and a, B-unsaturated acids. oH on } Hea 1 CH, CH-CN E41, CH-COoH HS CH, =CH COOH +H, hydroxy acid 4, Bunsaturated acid (Lact acid ‘Aerie acid) CH, CH CNS CH, -CH=CH,NH, on on B-amino alcohol on NH; NH, i 1 I CH, HCN CH, -CH-CN—E® 9CH,-CH-COOH camino acid (alanine) Similarly from acetone eyanohydrin, the corresponding compounds can be obtained (b) Addition of sodium bisulphite Crystalline solid derivatives are formed when aldehydes or ketones are shaken With saturated aqueous solution of sodium bisulphite. This reaction is used in the separation of aldehydes and ketones from non-carbony! compounds. Being reversible reaction, the addition compounds can be decomposed by dilute mineral acids oF aqueous alkalies to regenerate the original aldehyde or ketone. This reaction can be used for purification of aldehydes and ketones I | I = 0+ NalISO, === —C—050,H === —C-OS0,Na INa on (6) Addition of Grignard reagent ‘Aldehydes and Ketones react with Grignard reagent to from an adduet which ‘on hydrolysis yield the corresponding alcohols, HCHO + RMex—#2-5 RCH,OH (Primary ateohoty R R-CHO+R’Mex 225, eo SHON (Secondary alcohol) m0 RS R-CO-R'+R'MEX—2 RS COH (re stiary alcohol) ‘The reaction of Grignard reagent with methanal produces a primary alcohol, ‘with other aldehydes, a secondary alcohol and with ketone, a tertiary alcohol (4) Addition of alcohols Aldehydes react with alcohols in the presence of dry HC/ gas to form acetals, In this reaction, the addition of one molecule of alcohol 10 one molecule of aldehyde results in the formation of a hemiacetal, A hemiacetal contains both an ether as well a alcohol functional groups. It is an unstable compound and cannot be isolated. It further reacts with alcohol to form stable acetal. Acetals are dialkoxy compounds (geminal diethers) and have properties similar to ethers.a n~ Acetone reacts with ammonia 10 form diacetonamine ~~ Kn Carbonyls undergo condensation with ammonia derivatives R-CHO > i. apm? R-CH-OR’ + HO or’ Hemiacetal Acetal (one algohol and (Two ether cone ether linkage) linkages) Ketones react with ethylene glycol under similar conditions to form eyelic products known as ethylene glycol ketals Reo g , CHOW crs, RL -O-CH RF on SHO RPS dy, 22 Diallyt-t.3-dioxolane Acetals and ketals are hydrolysed with aqueous mineral acids to corresponding aldehydes and ketones respectively. Ketones do not ordinarily 1 with monohydrie alcohols, (©) Addition of ammonia Ammonia reacts with aldehydes (except formaldehyde) and Ketones to form the products. called imines f m = 0+NH; —4CH,-CH-OH——9CH, -CH=NH Ketones form complex ketonic amines. Acetone reacts with ammonia to form diacetonamine chy TN Yejo+ CH NH ? > See? chy OZ njci,cocH, cH” Scw,cocr, 4-Amino-4-methylpentanone-2 (0) Addition of primary amines Aldehydes and ketones react with primary amines to form Schiff"s bases, which are also known as imines RCHO + H,NR 75> RCHENR (aldimine) R R ROC =OFH;NR— pC =N-R (ketimine) ‘Nucleophilic addition-elimination reactions Reaction with ammonia derivatives : Aldehydes and ketones react with a number of ammonia derivatives to form compounds containing carbon nitrogen double bonds with elimination of water molecule. These reactions are called condensation reactions. ‘The important derivatives of ammonia are Hydroxyl derivative of ammonia is hydroxylamine, Amino derivative of ammonia is hydrazine, Phenyl derivative of hydrazine is phenyl hydrazine, 2.4-Dinitrophenyl derivative of hydrazine is 2,4-dinitrophenyl hydrazine, (Brady's reagent) and Amido derivative of hydrazine is semicarbazide~~ Oximes are condensation products of carbonyls with hydroxylamine In general, if we represent these derivatives by H,N-G, then their reaction with aldehydes and ketones can be represented as follows C=O + H,N-G —» >C=N-G + 1,0 The condensation products of aldehydes or ketones, i) with hydroxylamine are called oxime ii) with hydrazine are called hydrazones, iii) with phenyl hydrazine are called phenyl hydrazones, iv) with 2.4-dinitrophenyl hydrazine are called 2,4-dinitrophenyl hydrazones and ¥) with semicarbazide are called semicarbazones. The various ammonia derivatives and their reaction products with carbonyl compounds are summarized in Table 3.2. For carrying out these reactions, the ‘medium should be slightly acidic, The optimum pH of the medium is around 3.5. It should not be strongly acidic. Reactions of the above type which are basically addition reactions but proceed with the elimination of simple molecules like water ons ives and their produets with carbonyl compounds Formula of the Carbonyl reagent derivative Somecycis Ammonia NH, Imine Amine RNH, Substituted imine (Schift’s base) -o11 Hydroxylamine | NH,OH Oxime -NH, Hydrazine NH. I Hydrazone -NHC,H, Phenythydrazine | NH.NHC,H, y Phenylhydrazone | 24-Diniro | anigat-{)-noy | Deasvn-LO)-so | 24-Dinio- phenythyderine phen lhydrazone NO; ‘Semicarbazide | NH,NHCONH, DC=NNHCONH, | Semicarbazone Beckmann rearrangement Ketomixes when treated with an acid catalyst such as H,SO, are converted to N-subsituted amides. This reaction is called Beckmann rearrangement. The acid catalysts that may be used are H,SO,, HyPO,, P05, PC/, SOCI, and C,H,SO,CT ‘This rearrangement is intramolecular and involves 1,2 - shift : HCY i HAC” Acetoxime N-MethylacetamideCarbonyls form gem-dihalides with PCl, AW an Clemmensen's reduction of acetaldehyde sives ethane and acetone gives propane We Cols. I Se=non seis cya. stat, Benzophenone oxime N-phenylbenzamide Reaction with phosphorus pentachoride or thiol boride : Carbonyl teact with phosphorus pentachloride or thionyl chloride to form geminal halides CH-CHO + PC, —¥CH, CHC), + POC!, + HC! CH,-CO-CH, —4CH,CiCI,)CH, + $0,+ HCI Reaction with primary emines : Aldehydes and ketones react with primary amines to form N-substituted imines, called Sehiff's bases. Schif's hase is pink in colour and it can be decolourised by passing SO, gus. Tis colourtess solution is known as Schff's reagent. These imines give amines on catalytic hydrogenation. CH,CHO + CH,NH, #25CH,CH=NCH, Ey CH.CH,NHCH, ‘Acetaldehyde Methylamine N-Methyl-acetaldimine Ethylmethylamine 0 + CHNH; Ho, (scat a (esc Cyclohexanone Ethylamine N-Ethyleyclo- Cyclohexylethylamine hexanimine TID) Reduction a) Reduction to alcohols ; Aldehydes and ketones on mild reduction give primary and secondary alcohols respectively. This type of reduction is carried out either cataly- tically with hydrogen in presence of Ni, Pt oF Pd or chemically with Fthium aluminium hydride or sodium borohydride or sodium in ethanol. RCHO+H,—"9RCH,OH RCOR +H, 9 RCHOHR CH,CHO + H,—“-9CH,CH,OH cH,cocn, + #, > cH,cHoncH, b) Reduction to hydrocarbons : The catbonyl group can be reduced to methylene {group resulting in the formation of alkanes by any one of the following reagents. Clemmensen's reduetion : Carbonyl compounds are reduced to alkanes by hheuting with zine amalgam and concentrated hydrochloric uci. CH,CHO + 44) 2225 cHL-CH, + H,0 CH,COCH, + 44) 2!" cH,CH,CH, + H,0 Wolff-Kishner reduction : Carbonyl compounds are reduced using hydrazine followed by heating with sodium or potassium hydroxide in high boiling solvent such as ethylene glycol CH,CHO + NH.NH, 22 CH, CH, + HL0#N, CH,COCH, +NH,NH, 22°4CH,CH,CH, + 1,04,WH Two ketone ‘molecules reduce to form pinacolone we ie Tollens reagent, Fehling solution and Benedict solution are mild oxidants Reduction with red phosphorus and HT : Carbonyl compounds are reduced to the corresponding alkanes with red phosphorus and hydroiodic acid at 150°C. CH,CHO + 41" CH,-CH, + H,0 + 21, CH,COCH, + 4HI —!9 CH,CH,CH, + H,0 + 21, Bimolecular reduction : Two molecules of ketones undergo reduction in the presence of Hg/Mg to form pinacol. Upon treatment with mineral acids, pinacol is converted into pinacolone. This transformation involves dehydration and cnt is called pinacol-pinacolone rearrangement, Mets» HCN. ACH _wo Berane C7) NCH: bo VV Mg WA Aci on HT On OH 2, 3-Dimethytbotan -2,3-diol 3, 3-Dimethy! butan-2-one “pinacel) (pinacolone) Meerwein - Ponndorf-Verley (MVP) reduction : Aldehydes and ketones can bbe reduced to corresponding alcohols by heating them with aluminium isopropoxide in excess of isopropyl alcohol. This reaction is highly specific, the other functional ‘groups such as carbon-carbon double bond of nitio group remains uneffected. The co-product, acetone continuously distilled off to drive the equilibrium in favour of the alcohol product. HL oH HL on x WH CHO Xe +CH,COCHS Ket Seon eon stone or To pro cohol acetone ailehyde——"aohot C,H,CH = CHCHO SRESOLA © CH = CHCH,OH + (CH), cHON Cinnamaldehyde CHO ew) ,cHO}AL x —an.air > NO> © -Nitrobenzaldehyde ‘0 -Nitrobenzyl alcohol 1V) Oxidation Oxidation of aldehydes : Aldehydes are easily oxidised and thus act as strong reducing agents. They are oxidised to the corresponding carboxylic acids containing the same number of carbon atoms. The oxidation of aldehydes does not involve the cleavage of carbon-carbon bond. Since aldehyde group is chain-terminating group. it is easily oxidised by even mild oxidising agents like Tollen’s reagent or Febling’s solution or Benedict's solution along with strong oxidising agents like nitric acid or acidified potassium permanganate or potassium dichromate, Oxidation with Tollens reagent : Tollens reagent is ammonical solution of silver nitrate. On warming with this reagent, aldehydes form a silver mirror on the walls of the container. The reaction is also known as silver mirror test for aldehydes. RCHO + Ag,O—+ RCOOH + 2Ag) IRCHO + 2[Ag(NH,),]" OH” — RCO” +2Ag.!+4NH, +2H,0]Aldehyde on heating with reagent gives a red precipitate Oxidation with Fehling solution: Febling solution is an alkaline solution of HO CH COON cupric ion complexed with sodium potassium tartrate |isg Ext COOK Febling solution A is aqueous copper sulphate and Fehling solution B is sodium potassium tartrate. These two solutions are mixed in equal amounts just before test. (On heating an aldehyde with Feling reagent, a reddish brown precipitate is obtained Aromatic aldehydes do not respond to this test RCHO + 2CuO—> RCOOH + Cu,OL [RCHO + 2Cu* + SOF” —> ROO + 31,0 + Cu,04)] Benedict's solution is a mixture of solutions of copper sulphate, sodium citrate (CH,COONS lHo—c—cooNs CH,COON: The reaction of aldehydes with Benedict's solution is same as that with Febling’s solution. Aldehydes reduce Benedict's solution to give reddish brown precipitate Aromatic aldehydes reduce Tollen’s reagent, but not Fehling’s solution or Benedi and sodium carbonate solution. ‘Compound A. C,H,O. forms a phenyl hydrazone, gives negative Tollens and iodoform tests and is reduced to n-pentane. What is the compound, A? ‘Compound A forms hydrazone, so it sa carbonyl compound, Iti a Ketone as it does not reduce ‘ollens reagent. The ketone does not have methy| group ast does no respond to iodoform test. ‘Thus, the compound is pentanone -3. The structure of the compound is CH,CH,COCH,CH,, ‘organic compound (A) with molecular formula C,H,O forms an orange-red precipita heating with iodine in the presence of sodium hydroxide. It nighter reduce Toll Fehling reagent nor does it docolourises bromine water or Baeyer's reagent, On darstic oxidation ‘with chromic acid, it gives a carboxylic acid (By having molecular formula C,H,0,. Identity the ‘compounds (A) and (B) and explain the reactions involved ‘Compound (A) forms 2,4-DNP derivative. Therefore, it isan aldehyde ora ketone. Since it does rot reduce Tollens reagent or Feling solution (A) must be a ketone. (A) responds to iodoform test. Therefore, it should be a methyl ketone ‘The molecular formula of (A) indicates high degree of unsaturation, yet it does not decolourise ‘bromine water of Baeyer’s reagent, indicating the presence of unsaturat aromatic ring, Compound (B), being an oxidation product of a ketone, it should be a carboxylic acid. The ‘molecular formula of (B) indicates ‘Compound (A) should, therefore, be a formula of (A) indicates that it should be pheny! methyl ketone (acetophenone), ° i “Sen HC. + ILNIN, No, eS, CHO coon Ren g " co won on B) cso,‘An alkene, C,H, ,after ozonolysis yielded two products, One ofthese gave a positive iodoform reaction but a negative Tollens test. The other product gave a positive Tollens test but a negative fodoform reaction. What isthe name and structure ofthat alkene? (One product isa methyl ketone as it gives postive iodoform test, bt a negative Tollen’s test ‘The other product is an aldehyde without methyl group attached to carbonyl carbon as it does not respond to iodoform test, Hence, the products of ozonolysis are : CH,COCH, and CH.CH,CHO. cH, i Therefore, the alkene is 2-methylpent-2-ene. Its structure is CHy—C=CHCH,CHs, ‘Two orpanie compounds (A)and (B) with molecular formula, CJH,O, react with HCN in different ‘manner to produce (C) and (D) respectively. On subsequent hydrolysis of (C) and (D) give ‘optically active substances (E) and (F). Both (E) and (F) on decarboxylation give 1 - propanol ‘What are(A),(B),(C)(D), (E) and (F)? (A) is CH,CH,CHO: (B) is CH= CH CH, OH (C) is CH,CH,CH(OH)CN: (D) is CH,-CH(CN}CH,OH ; is CH,CH,CH(OH) COOH and (F) is CH, CH (COOH)CH,OH, (&) and (F) are optically active, Sea aioe Ketoneis difficult 10 oxidise, as it involves the cleavage of the C-C bond ~~ Oxidation of ketones : Ketones are generally oxidised under vigorous conditions, with strong oxidising agents like concentrated nitric acid or acidified potassium permangate or acidified potassium dichromate. Oxidation of ketones involves cleavage of bond between carbonyl carbon and «carbon on either side of keto group giving a mixture of carboxylic acids having lesser number of carbon atoms, CH,-CO-CH, 4+ HCOOH + CH,COOH In case of unsymmettical ketones, the point of cleavage is such that keto group is retained with smaller alkyl group preferentially (Popoff's rule). (CH;CH,CH,+CO4CH, Pentan-2-one @) © CHYCH;COOH + CH,COOH CH,CH.CH.COOH + HCOOH Propanoic acid Ethanoic acid Butanoic acid Methanoie acid Bacyer's Villiger oxidation : Aliphatic ketones are converted to esters when oxidised by Caro's acid, benzoic acid, meta chloroperbenzoic acid, peracetic acid or wifluoroperacetic acid. In the case of unsymmetrical Ketones, oxidation involves insertion of oxygen atom between carbonyl group and alkyl group. The order of preference of alkyl groups is : 3° > 2° > C,H, > CH ° ™ FCO. Cols -C-CHy: it CH)-C=OC Hs (but not CgHy—C-OCH) og cco 8 8Methyl ketones (2-ones) give haloform test a-Hydrogen atoms of carbo nyls are acidie Aldol reaction involves ‘wo carbonyls, atleast one having G.-hydrogen atom ‘Oxidation with sodium hypohalite : Acctaichyde and Kelones having atlas cme methyl group linked tothe carbons carbon atom (methyl ketones) are oxidised by sodiam Rypohalite to sodiuen salts of comespondiag carboxyilc acids having ve eabon ates Les tha that of crbouy] compound, Tho mctyl group Is converted to halofrm. This oxidation does not affect a carbon-carbon double bond, if present in the molecule Noy nce, SOS fi SS No ona + CHC nc nc é Todoform reaction with sodium hypoidite is also used for detection of CH,CO roup oF CH,CH(OH) group which produces CH,CO group on oxidation (Oxidation with selemfum dloxide : Aldehydes and Ketones tat possess methyl ce methylene group adjacent to the carbouyl group are axidlend by selenlum dioxide to give e-dlcarbonyl (1, 2-dicarbony}) compounds. If both methyl and methylene roups ae present adjacent tothe carbonyl group, the former is oxidised preeren- tially, This reaction is known asthe Riley reactlon, i i tl R-C-CH, ~R’+Se0, —9R -C-C-R4Se+H,0 CH,CHO—S%5CHO-CHO | CH,CO CH, *5cH,COcHO. ‘Acetaldchyde lyoxal Acetone Methylelyoxal cH,CocH,CH, S25 cH,CH,COCHO + CH,COCOCH, Butanone Eihyl lyoxal — Dimethylglyoxal (Major) minor) V) Reactions due to c-hydrogen Hydrogen atoms of carbonyl compounds are acidic in nature due to the strong electron withdrawing effect of the carbonyl group and resonance stabilisation of the conjugate base. The aldehydes and ketones undergo a number of reactions ddue to the acidic nature of e-hydrogen 1) Aldol condensation : Two molecules of an aldehyde or a Ketone having at least fone q-hydrogen atom undergo condensation in the presence of dilute alkali such as NaOH, Ba(OH), or K,CO,, ete., to form B-hydroxy aldehydes (aldol) or B~ hydroxy ketones (Ketol) respectively. This is known as Aldol reaction. The aldol and ketol lose water to give o:8-unsaturated carbonyl compounds which are aldol condensation products and the reaction is called aldol condensation, H sunon, i tocH co , 7H,CHO & > CH,-C— CH,CHO Sf CH:-CH=CH-CHO H But-2-enal 3-Hydroxybutanal 2CH,COCH, ESE (CH,),C(OH)-CH,COCH, A1CH,),C=CHCOCH, Diacetone alcohol Mesityl oxideWR In crossed aldot condensation two self and two crossed prod are obtained Ae When acetone is treated with hydrochloric acid, mesityl oxide and phorone are formed. 2CH,COCH, === (CH),C=CHCOCH, (mesityl oxide) 3CH ,COCH, ===? (CH) ,C=CHCOCH=C(CH,), (phorone) Carbonyl compounds which do not contain -hydrogen atom like formaldehyde, benzaldehyde, ete.. do not undergo this reaction Crossed aldol condensation : When aldol condensation is carried out between two different aldehydes or ketones, if both of them contain «hydrogen atoms, a mixture of four different products is formed. Two of them are called crossed aldol. ‘The following reactions take place when acetaldehyde and propionaldehyde condense together. 2CH,CHOCH,-C 2CH,CH,CHO—4CH,-CH,-CH=C(CH,)CHO 2-Methylpent-2-enal CH -CH=CH-CHO+CH,-CH,-CH=C(CH,)CHO But-2-ena 2-Methylpent-2-2na (self aldol) (self aldol) CH,CHO#CH,CH,CHO — + (CH,-CH=C(CH,)CHO + CH,-CH,-CH=CH-CHO 2-Methylbut-2-enal Pent-2-enal {cross aldol) {cross aldol) Acetaldehyde reacts with benzaldehyde in the presence of a base to form an aldol which on heating yields cinnamaldehyde (e:B-uresaturated aldehyde). This reaction is known as Claisen-Schmidt reaction “HCHO + CHCHO 2 C,H, Benzaldehyde Acefaldehyde Cols “CH = CH CHO Although aldehydes ae easily oxidisable, propanal can conveniently be prepared by oxidation ‘of propanol by acidified potassium dichromate, Why? ‘The aldehydes can be conveniently oxidised to their respective acids only if they are not removed from the reaction mixture during preparation. As the boiling point of propanal is low (323K), itis conveniently distilled out during the reaction, This avoids its further oxidation, ‘Aldehydes do not form stable hydrates, yet chloral hydrate is readily formed, why? In chloral, three strong electron withdrawing chlorine atoms are present. As a result, weak nucleophile like water can easily add Besides this, intra molecular hydrogen bonding between chlorine and hydrogen atom of -OH group further stabilises the molecule Chlorination or bromination : One or more ohydrogen atoms present in aldehydes or ketones can be replaced by chlorine or bromine. With chlorine | and acetone gives trichloro acetone,Carbonyl compounds are tested with 2.4-DNP to give orange red precipitates Aliphatic aldehyde restores pink colour of Schiff’s reagent, but not ketone A i Acetylene can he stored in WW CH,CHO + 3C1,9CC1,CHO + 3HC/ CH,COCH, + 3Cl, —4CCI,COCH, + 3HCI Todoform reaction : Compounds containing methyl ketonic group (CH,CO-) undergo iodoform reaction. Both acetaldehyde and acetone respond to iodoform reaction when treated with iodine and alkali CH,CHO + 31, + 4NaOH—+HCOONa + CHI, + 34,0 + 3Nal CH,COCH, + 31, + 4NaOH—+CH,COONs + CHI, + 3H,0 + 3Nal ‘Tests for carbonyl compounds Carbonyl compounds give orange red coloured needle type crystals with 2.4linitrophenyl hydrazine called Borseh reagent, Then aldehydes and ketones are differentiated with other reagents. i) Aldehydes give silver mirror with Tollen’s reagent, but not ketones. ii) Aliphatic aldehydes give red precipitate with Fehling’s solution or with Benedict’s solution, but not ketones ili) Aliphatic aldehydes restore pink colour of aqueous Sehiff’s reagent, but not ketones, Schiff’s reagent is an aqueous solution of p-rosaniline hydrochloride (pink) decolourised by sulphurdioxide. Indigo test : A small amount of o-nitrobenzaldehyde is added to about two millilitres of acetone and is diluted with KOH, a blue colour of indigotin is produced Uses of acetaldehyde Acetaldehyde is used in the preparation of acetic acid, acetic anhydride, ethyl acetate, chloral, 1,3-butadiene, dyes and drugs. Acetaldehyde is used as an antiseptic inhalent in nose troubles and in the preparation of paraldehyde (trimer, a hypnotic drug), metaldehyde (tetramer, a fuel) and acetaldehyde ammonia, Uses of Acetone Acetone is used as a solvent for cellulose acetate, cellulose nitrate, resins, ete., for storing acetylene gas and in the manufacture of cordite a smokeless powder explosive Acetone is used as a nail polish remover, in the preparation of an artificial scent, plexiglass (unbreakable glass) and synthetic rubber. How is acetaldehyde distinguished from acetone ? Acetakdehyde gives silver nitrate on treating with ammonical silver nitrate solution (Tollen's reagard). Acctaldchyde gives a red precipitate on treating with ammonical cuproic sat solution complexed with tartrate (Fehling’s solution) Acetone does not react with Tollen’s reagent and Febling’s solution ‘What are metaldehyde and paraldehyde ?EXERCISE - 3.1.2 1. Write any three methods of preparation of acetaldehyde? 2. How is acetaldehyde prepared separately from CH,CH,OH, CH,CHC/, and CH,=CH,. 3. Write any four properties and two uses of acetaldehyde, 4. Give equations for the formation of acetaldehyde from (i) calcium salts of fatty acids (ii) fatty acids and (ii) acetylene, 5. How does acetaldehyde react with the following : (i) HCN, Gi) HNOH, (ii) C,H,MgBr, H,O and (iv) H,NNHCONH, 6. Give equations for the reaction of acetaldehyde with NH, and with PC 7. Discuss aldol condensation 8. Write three preparations, three properties and three uses of acetone. 9, How acetone is obtained from: (i) CH,CHOHCH, (ii) CH,-C=CH and Gil) CH,COOH. 10. How does acetone react with (i) NaHSO, (ii) 1, + NaOH and (ii) C,H,(NO,),NHNH,.. 11, Explain the similarity in chemical properties of acetaldehyde and acetone. 12. Write any three tests that are useful to differentiate acetaldehyde from acetone. 13, Explain the formation of hemiacetal and acetal from acetone 14, Give the structure and TUPAC name of the product obtained when acetone is treated with barium hydroxide solution Write short notes on Clemmensen reduction and Wolff-kishner reduction. How ethyne and propyne are converted to acetaldehyde and acetone respectively? Give equations for the formation of acetaldehyde and acetone from ethylidene chloride and isopropylidene chloride. Write the reactions between ammonia with (i) CH,CHO and (ii) CH,COCH, How do acetaldehyde and acetone react with Grignard reagent? Write the common and IUPAC names of products obtained when acetone is treated with dry HCI Give the structure and IUPAC name of product obtained when acetone is treated with Ba(OH)y What are the products obtained when acetaldehyde and acetone are treated with separately with cone. H,SO,? Write a note on iodoform reaction Nu, ‘Complete the following reactions: a) CH,CHO 24> and b) CH,CHO MEME Mention the products formed when acetaldehyde reacts with hydrogen in presence Of nickel and acetone reacts with sodium in ethyl alcohol. OTHER CARBONYL COMPOUNDS ——s 3.3.1 Formaldehyde Preparation 1) By the oxidation of methyl alcohol with oxygen in presence of a catalyst like platinised asbestos or by acidified potassium dichromate, formaldehyde is formed, 2CH,OH + 0,285 2HCHO + 2H, : CHOH +) NESE HICHO + 1,0Dehydrogenation of methanol gives ‘methanal Yr Bakelite is a condensation polymer of formaldehyde and phenol We Aldehydes with no o1-H undergo Cannizzaro reaction with cone, alkali Mh ii) Methanal can be obtained by dehydrogenation when vapours of methyl alcohol are passed over copper or silver at 300-400°C. HOH SEAL 4 HCHO + Hy iil) By heating dry calcium formate strongly, methanal is formed, (HCOO),Ca —¥9 HCHO + CaCO, iy) Methanal can be manufactured by controlled oxidation of methane by air in presence of various metallic oxides as catalyst CH, +0, 2" 5 HeHO+H,0 Chemical properties Condensation with phenol ; Formaldehyde condenses with phenol in presence of dilute sodium hydroxide or ammonia at 80-90°C to give a synthetic plastic, bakelite. Bakelite is used for manufacturing electrical insulators, electrical switches, toys, ete to form a plastic like product X H.NCONH, —~CHa, + a DN-CO-N y¥ CHO “CH. c CH Formaldehyde-urea plastic Condensation with ammonia : Like other aldehydes, formaldehyde does not form addition product but gives a crystalline compound, hexamethylene tetramine (urotropine) with ammonia 6 HCHO + 4NH,—9 (CH,), N, + 6H, ‘annizzaro reaction : Aldchydes which do not have an a-hydrogen atom, undergo self oxidation and reduction (disproportionation) reaction on treatment with concentrated alkali In this reaction, one molecule of formaldehyde is reduced to methyl alcohol while another is oxidised to formic acid salt. HCHO + HCHO + KOH —> CH;OH + HCOOK Dero OD. con? OW Furfural Furfuryl alcohol Sodium furoateIsobutyraldehyde undergoes Cannizzaro reaction Isobutyraldehyde, although possesses an alpha hydrogen underegoes Cannizzaro reaction, 2(CH,), CHCHO + NaOH —“2_4(CH, ), CHCH,OH + (CH); CHCOONa Isobuiyraldchyde FRebutylalcohol » sodium isobutyrate Though CI,C-CHO and (C,H,),C ~ CHO have no alpha hydrogen cannot undergo Cannizzaro reaction, Uses of formaldehyde ‘The 40% solution of formaldehyde (formalin) is used as disinfectant, germicide and antiseptic. It is used for the preservation of biological specimens. Formaldehyde is used in the preparation of urotropine as an antiseptic and germicide. It is used in making synthetic plastics like bakelite, urea-formaldehyde resin, ete What products are obtained ina crossed Cannizzaro reaction, involving HCHO and C,H,CHO? “The products obtained are C,H,CH,OH and HOO" . This is because formaldehyde isa good reducing agent and reduces benzaldehyde to benzyl alcohol. ‘An organic compound having molecular formula C,H, 0 exists in two chai isomers, (A) and {B) Isomer (A) undergoes Cannizzaro reaction to BN8 22-dimethy|propanoie ach! and 2 dimethyl propanol-1. Compound (B) in the presence of dilute alkali undergoes aldol jeandensation to form 3-hydroxy-2-propylheptanal. Give the structures of (A) and (B). Isomers have the formula, CJH,CHO. Tsomer(A) undergoes Cannizaro reaction, thus it does not have e-hydrogen. The suructue of (Avis(CH,),CCHO, (CHy,CCHO M5 (CH,),CCOOH + (CH) CCHOH Isomer (B) undergoes aldol condensation as it possesses hydrogen atom. The structure of (B)isCH,CH,CH,CH,CHO. CH.CHLCHCH.CHO + H-CH-CHh CHC, —> cHo (CH Cth CH, CHC EH-CH CHC, on CHO —es 3.3.2 Benzaldehyde aT e~ In Etard reaction, toluene is oxidised to benzaldehyde using CrOCl, Wr Benzaldehyde is the simplest aromatic aldehyde which occurs in bitter almonds, and itis also known as oil of bitter almonds. Preparation ‘Chromyl chloride oxidises toluene to a chromium complex, which on hydrolysis sives benzaldehyde. This reaction is called Etard reaction. Hy CH(OCIOHC!) “HO + COL _ Chromic oxide in acetic anhydride oxidises toluene or substituted toluene to benzylidene diacetate which on hydrolysis with aqueous acid gives benzaldehyde. : CHOCOCH), “HO of + C10, +(CH,C0),0-25 | Mo, Benzal diacetateBenzaldehyde is obtained from benzene in Gattermann-Koch reaction by adding with CO WW Benzaldehyde undergoes Benzoyl chloride on reduction with hydrogen in presence of Lindlar’s catalyst (Rosenmund reduction) gives benzaldehyde ° ° dcr on Oo Ge Side chain chlorination of toluene gives benzal chloride followed by hydrolysis ssives benzaldehyde, This is a commercial method, One, When benzene is treated with carboamonoxide and hydrogen chloride in presence of anhydrous aluminium chloride or cuprous chloride in methylene chloride tives benzaldehyde. This reaction is called Gattermann-Koch reaction, in which formylation of aromatic ring takes place eH 6 HO. When a mixture of calcium benzoate and calcium formate is dry distile, the main product formed is bearaldehyde (C.HyCOO),Ca + (HCOO),Ca 2 2C,H CHO + When phenyl eyanide is reduced partially with stannous chloride and pasing dry HCI gas in eter solution followed by hyrolysis ofthe akdimine stannic chloride ith water, benzaldehyde is formed. This i called Stephen's renction, = 7 “uae 6Y ldehyde synthesis : Benzene is teated with a mixture of HCN and HCT in presence of anhydrous A/C/, to form benzaldiminium tetrachloroaluminate (IID, which is hydrolysed to produce benzaldehyde. This is also called Gattermann formulation HeNHAAICK uo Omens Properties Benzaldehyde undergoes addition reactions with hydrogen eyanide, sodium bisulphite, Grignard reagent, ete. just like acetaldehyde, Benzaldehyde undergoes condensation reactions with hydroxylamine, hydrazine, phenyl hydrazine, semicarbazide, etc., forming the cortesponding condensation products ‘annizzaro reaction : Benzaldehyde undergoes self oxidation reduction (disproportionation) reaction om treatment with concentrated alkali due to lack of hydrogen forming benzyl alcohol and sodium benzoate son OS", GYaan Ahad Cinnamie acid is obtained from benzaldehyde by Perkin’s reaction Ae Tischenko reaction of benzaldehyde gives an ester, Crossed Cannizzaro reaction : In presence of a base, benzaldehyde and formaldehyde condense to form a mixture of benzyl alcohol and sodium benzoate. Cy Hs CHO + HCHO + NaOH E44 C, Hy CHOH + HCOONa Benzoin Condensation ; When benzaldehyde is heated with aqueous ethanolic potassium cyanide, it undergoes bimolecular condensation to form benzoin (2-Hydroxy-1, 2-diphenylethanone). The cyanide ion is specific catalyst for this reaction, © on t Cf” tim OO) Bensoin Witting reaction : Aromatic carbonyl compounds reaet with triphenyl phosphorane (Withing reagent) 10 give an alkene, is known as Wit ction, CyHGCHO+ (C, Hs), P=CH, 29 CH,CH=CH, #(C, 1), P=0 Benzaldchyde Styrene Triphenyl . phosphine oxide Cos, Coty = O4(C, Hs), P=CH; 9 Yo = cH, +(G, Hy), P= cand (Co Hs) oud lo + (Cy Hs), P=O Benzophenone 1,LDiphenylethene Perkin's reaction : An aromatic aldehyde when heated with the anhydride of an aliphatic acid (containing two c-hydrogen atoms) and its sodium salt (base catalysed), condensation takes place and an a, B-unsaturated acid is formed Benzaldehyde with acetic anhydride and sodium acetate yields cinnamie acid. C{H.CHO + (CH,CO),0 822" 6,H,CH=CH-COOH Cross aldol condensation : Benzaldchyde undergoes cross condensation with 4 ketone in dilute alkali, The other important aromatic ketone is benzophenone. eam OO OO 1,3-Diphenylprop-2-en-1-one Electrophilic Substitution : Aromatic aldehydes and Ketones undergo electrophilic substitution at the ring in which the carbonyl group acts as a deactivating and meta-directing, nitration, halogenation and sulphonation, : Tischenko reaction ; On heating benzaldehyde with aluminium ethoxide and alte of anhydrous A/C/, or ZnCl, undergoes intermolecular oxidation and reduction, to produce benzyl benzoate. CHO CH,00C, MOC oOAcetophenone WY Acetophenone is commercially prepared by the oxidation of ethylbenzene AW Acetophenone is prepared by Friedel-Crafts acetylation of benzene Acetophenone the simplest aromatic ketone. It is also called as methylphenyl ketone oF acetyl benzene Preparation i) Acetyl chloride reacts with benzene in presence of anhydrous aluminium chloride to form acetophenone. This is called Friedel-Craft’s acetylation. GH, + CHCOCI 2 C,H,COCH, + HCL ii) Acetophenone is obtained by distillation of @ mixture of calcium benzoate and calcium acetate (C,H,COO),Ca_ + (CH,COO),Ca 2 C,H,COCH, + CaCO, iii) Ethannitrile on treatment with phenyl magnesium bromide followed by hydrolysis gives acetophenone. C,HjMgBr + CH,CN > C= NMgBr—#2 Cy-C =O cHy cH, iv) Phenyl eyanide reacts with CH,Mgl followed by hydrolysis gives acetophenone CH.CX YSIS CH,.COCH, + NH, + MaCORDL ¥)_ Acetophenone can be prepared by the reaction of benzoy! chloride with dimethyl cadmium or by the reaction of benzoic acid with methyl lithium, CH,COCL ASAE C,HCOCH, vi) Commercially acetophenone is prepared by the oxidation of ethylbenzene with air at 126°C under pressure with manganese acetate catalys. C(H,CH,CH, + 0, SM ,4,COCH, +H,0 Properties Acetophenone is chemically similar to acetone, However, it does not form addition compound with sodium bisulphite due to steric hindrance of the phenyl group. Tt gives usual electrophilic substitution reactions of the benzene ring in meta position, Acetyl group in the ring is electron deactivating. Acetophenone does not respond to iodoform test due to tautomerism, Benzaldchyde is treated with acctaldchyde in presence of dilute alkali, What happens? ‘When benzaldehyde reacts with acetaldehyde, first unstable B-hydroxy aldehyde is formed ‘which loses a molecule of water to form cinnamaldehyde, C,H,CHO + CH,CHO 5-9 C,H CHOH)CHL > CH-CH=CHCHO How do you distingush between benzaldehyde and acetophenone? ‘Two reagents are useful to distinguish 4) Tollen’s reagent which react with benzaldehyde, but not acetophenone ») fodoform reaction gives yellow precipitate with acetophenone, but not benzaldchy de Give the structures of the compounds formed when the reaction takes place between ‘benzaldehyde and formaldehyde, What isthe name of that reaction? C,H,CHO HCHO. » HCOONa+C,H,CH,OH “This reaction i called as crossed Cannizzaro reaction.2X arcane YESS Z, uss the sequence and name the compounds X, Y and 7. Compound X is ethylbenzene, C,H,C\H,. The reaction is called Priedel-Craft's ethylation. Y is acetophenone, C,H,COCH,. Oxidation of ethyl benzene at 400 K in the presence of -manganese catalyst gives acetophenone. Z is benzoic acid, C,H,COOH. Aromatic ketones give carboxylic acids in the presence of powerful oxidants How do you prepare acetophenone from benzene? Benzene on reaction with acetylehloride in presence of anhydrous AICI, gives acetophenone, Ga1c1= the rate determining step in Cannizzaro's reaction? m . . and H-C-OH + CH,O—> HCOG'+ CH.OH ‘Transfer of hydride ion on tothe carbonyl carbon is the rate determining step in the Cannizzato's reaction. Solution Predict the products in the following reactions and write their structures. @ Oo + ,4,coci Eg (ond ren, 269 (©)(C,H,CH,),€C4-+2CH,COCL —> coca, o6 ONLO)RCHO at ery Crus Sotution Can (CH, ),CCHO undergo Cannizzaro reaction (CH,,CCHO can undergo Cannizzaro reaction since it does not contain hydrogen. 21H ,CCHO Hy (CH,),CCH,OH + (CH,),CCOONa Cr ms GH CH AS x atte PY ES 2. Discuss and name the compounds X, ¥ and Z. ‘Compound X is ethylbenzene, C,H,C,H,. The reaction is called Friedel-Crafts ethylation, Y is acetophenone, C,H,COCH,, Oxidation of ethyl benzene at 400 K in the presence of ‘manganese acetate catalyst gives acetophenone. Z is benzoic acid, CJH,COOH, Aromatic ketones give carboxylic acids in the presence of powerful oxidantsEXERCISE - 3.1.3 What is Etard reaction? Explain Gattermann-Koch reaction for the formation of benzaldehyde. How benzaldehyde is formed from toluene? How acetophenone is formed by Friedel-Craft’s reaction? Discuss on the Cannizzaro’s reaction. Aldehydes and ketones which contain the common carbonyl functional group are some of the important classes of organic compounds. According to TUPAC nomenclature, aldehydes are called as alkanals and ketones as alkanones. Carbonyl compounds exhibit chain isomerism, functional isomerism, tautomerism and ketones having five or more carbons exhibit metamerism also. Primary alcohols on oxidation or on catalytic dehydrogenation give aldehydes and secondary alcohols on similar conditions yield ketones, Dry distillation of calcium salts of fatty acids along with calcium formate give aldehydes and symmetrical ketones may be obtained when calcium salts of fatty acids alone are heated. Vapours of fatty acids mixed with formic acid when passed over heated thoria or alumina or MaO give aldehydes. Vapours of a fatty acid alone give ketones. Alkenes can be oxidised to carbonyl compounds by Wacker process by using aqueous palladium chloride in presence of cupric chloride catalyst Depending upon the structure of alkene, different carbonyl compounds are obtained by the reductive ozonolysis. Carbonyls are obtained by the hyciration of alkynes or by alkaline hydrolysis of gem halides. Reduction of acid chloride with hydrogen in presence of Lindlar’s catalyst to give aldehydes is called Rosenmund reduction. Ketones cannot be prepared by this method. Reduction of alkyl cyanide with stannous chloride and HC! followed by hydrolysis to give aldehydes is called Stephen reaction. Ketones cannot be prepared by this method. Carbonyl compounds are highly polar and boil at high temperatures than the weakly polar ethers of comparable molar masses. Lower carbonyls are more soluble in water due to hydrogen bonding. Due to larger size of hydrophobic alkyl group, higher carbonyls are insoluble in water.ns of carbonyl compounds are nucleophilic addition reactions. Aldehydes are more reactive than ketones, Aliphatic aldehydes are more reactive than aromatic aldehydes, ‘Ammonia reacts with aldehydes and Ketones to form imines. Formaldehyde forms urotropine swith ammonia. Carbonyl compounds condense with derivatives of ammonia, hydroxylamine, hydrazine, phenyl-hydrazine, 2,4-dinitrophenyl hydrazine, semicarbazide to form the corresponding coximes, hydrazones, phenyl hydrazones, 2,4-dinitrophenyl hydrazones and semicarbazones. ‘Carbonyl compounds react with PCI, or thionyl chloride to give gem dihalides. Aldehydes are reduced to primary alcohols and ketones (0 secondary alcohols with LiATH. NaBH, or by catalytic hydrogenation ‘Carbonyl group is reduced to methylene group, by Clemmensen reduction or by Wolff - Kishner reduction, thereby, carbonyl compounds are reduced to alkanes, Aldehydes are easily oxidised to carboxylic acids by even mild oxidising agents like Tollen’s reagent, Fehling’s reagent and Benedict’s solution. These oxidation reactions are used to distinguish aldehydes from ketones. ‘The hydrogens in carbonyl compounds are acidic. Carbonyl compounds having at least ‘one ct-hydrogen, undergo Aldol condensation, Aldehydes with no a-hydrogen atom on reaction with concentrated alkali undergo Cannizzaro reaction in which aldehyde undergoes disproportionation to give alcohol and salt of carboxylic acid. ‘Compounds containing methyl keto group or which form these on treatment with halogens give haloform reaction, Aromatic carbonyl compounds undergo electrophilic substitution reactions also. Carbonyl ‘group present in aromatic ring is meta directing and deactivating ‘Acetaldehyde undergoes trimerisation or tetramerisation in presence of concentrated sulphuric acid to form paraldehyde and metaldehyde respectively, ‘Condensation polymer of formaldehyde and phenol is Bakelite, Condensation polymer of formaldehyde and urea is formaldehyde-urea, Condensation product of formaldehyde and ammonia is urotro Benzaldehyde can be obtained by the oxidation of toluene with chromyl chloride followed by hydrolysis. This is called Etard reaction Benzaldehyde is prepared from benzene by Gattermann—Koch reaction, ‘Cinnamic acid is obtained from benzaldehyde by Perkin reaction using anhydride of aliphatic acid. Acetophenone is the simplest aromatic ketone, ‘Acetophenone is prepared by the Friedel-Craft’s acetylation on benzene or by the oxidation of ethylbenzene in the presence of manganese acetate.Ethanal to but-2-enal Acetaldehyde to but-2-enoic acid Ethanal to butane-1,3-diol Benzoie acid to benzaldehyde Propanone (© propene Benzaldehyde to benzophenone Ethanol to 3-hydroxybutanal Benzaldehyde to 3-phenylpropan-L-ol Benzaldehyde to o-hydroxyphenyl acetic acid JANSWERS to CONVERSIONS: oH I a 2CH,- CHO OF, CH, -CH-CH, ~CHO p77 CH, - CH = CH - CHO (Aldol) ° 3-hydroxy butanal on i a Tolle 2CH,CHO “CH, -CH-CH, -CHO ig CH, CH=CH~CHO SaaS (Aldol) (Crotanaldehyde) OH t CH, ~cH-CH, -cH 2cH,cHO 44 CH, ~CH-CH, ~CHo SBA ! ' (Aldol) me OH OH €,8,C00H 22 €,1,coc! HABE 5 c,44,CHO (Rosenmund’s reaction) ° on i ! con cu, -C-cn, 2%, cH, -CH-cH, 248250, CH=CH, co coon ma. © a OS) Benzafe acid Benzophenone CH, ~CH, -OH <5 CH,CHO— > CH, -CH-CH, -CHO. Eshanol Eshanal 1 cho ¢H=CH-CHO ABLcu,-cn,on ae Ag NOH HO-CH-CNEXERCISE - 3.2 L. Give the TUPAC names of the following compounds : (CH,)CCH,CHO, CH,CH=CHCHO, (CH,CH,COCH(C,H,)CH,CH,CI and CH,CH(OH)CH,COCH,, Write structures of the compounds : p,p'-dihydroxy benzophenone, cyclopropanone oxime, acetaldehyde dimethylacetal and divinyl ketone. What are the hydrolysis products of gem-halids and vie-halides? |. Give the preparation of acetone from acetyl chloride using dimethyl cadmium, ‘Why oxidation of a ketone gives carboxylic acid(s) with less number of carbon atoms? Why the solubility of carbonyl compounds in water decreases with increase in molecular; weight? |. Why do aldehydes differ in some chemical properties with ketones? Explain the reaction between carbonyl compounds with Grignard reagent. ‘What is the importance of the reaction between carbonyl compounds and DNP? Dry distillation of calcium salt of a dicarboxylic acid gives cyclic ketone, Explain with suitable examples, Predict the order of reactivity of different aldehydes and ketones towards nucleophilic additions. Explain the importance of carbonyl compounds in the preparation of different alcohols using Grignard reagents. Calcium salt of acid “X° on dry distillation gives cyclophentanone, What is “X"? (Ans : Adipic acid) How cinnamic acid is formed by Perkin reaction? Write the mechanism, ‘Write the mechanism of reaction between an aldehyde with any ammonia derivatives. Under what condition, the reaction gives maximum yield? How Clemmenson’s reduction is different from that using lithium aluminium hydride? ‘Write the differences in the mechanism of base catalysed aldol condensation and acid catalysed aldol condensation, How Iodoform reaction is useful in detecting CH,CO- or CH,CH(OH)- groups with sodium hypoiodite? Explain crossed aldol condensation with suitable examples. Explain the condensation reactions of formaldehyde with phenol and with urea, Draw the structures of the condensation products . How benzaldehyde is obtained from benzoyl chloride? HCHO—SMEE 4 HO p EGO 5c. What isthe product ‘C°?. (Ans Discuss the formation of hemiacetal and acetal from ethanol. Write om the following (a) Stephens reaction and (b) Tischenko reaction. ‘Write notes on (i) Rosenmund reduction and (ii) Wolff-Kishner’s reduction,Describe any four methods of preparation of acetophenone? What is the orientation effect of aldehydic and ketonic group when attached to aromatic ring towards electrophilic substitution reactions? What is silver mirror test? Explain its usefulness in the laboratory. ‘Write all the possible aldol products of 6-ketoheptanal Write the products of reactions of ammonia with formaldehyde, acetaldehyde, acetone and benzaldehyde. ‘Oxidation of toluene with CrO, in presence of acetic anhydride is best method for preparation| of benzaldehyde. Justify. Write the sequence of reactions to convert acetylene into acetophenone. (CH,),CCHO does not undergo Cannizzaro’s reaction, Why’ Write the products of the reaction in presence of base between propanal and propanone. CH —CH=CH, +0 + Puch 24 x HCL Y, What is “Y'2 (Ams : Phorone) cucHo HES x Mt, p_Sattne yc Sy pA yp Write the final prouduct “F’ of the given sequence. cu,cHo SEH, 4 20H, p a, ¢ MM, Name the product ‘D’ of the above conversions. (Ans: acetoxime) NeichoH sone. 1.80, CH,CHO —S/GHOH, x ome HSL, y HE 7, What happens when the final product °Z’ is treated with alkali solution? (Ans : gives ethanol) cH,cHo #4 x 825 ¥, what are the functional groups presen in the final product “Y" in the given sequence of reactions (Ans : COOH and -OF) Ci, —Seva BS cy Dy BO op IO gH ‘What is the functional isomer of the product “H’. (Ans : CH,CHO) 0 1.80. K.c.0, com, CH=CH —retiso, > A “artigo? B > C ras > D. ‘Write the final product ‘D’ in the above sequence of reactions? (Ans : CH,COCH,) HHO Heya AER ca DN eH Write the isomer of the product ‘F’