State the reactions (reagents and conditions) by which aldehydes and ketones can be produced: w Oxidation of primary alcohols using acidified KMnO, or acidified KaCrOy and distilation tp pe aldehydes. (b)the oxidation of secondary alcohols using acidified KMn0, oF acidified KiC10) ang distillation to produce ketones. Describe: (a) the reduction of aldehydes and ketones using NaBH, or LIAL to produce alcchols (tthe Sxidation of aldehydes and ketones with HCN, KCN as catalyst, to Produce hydroxy nitriles by ethant and propanone, Pescribe the mechanism of the nucleophilic addition reactions of HCN with aldehydes and ketones, Describe the use of 2,4-dinitrophenylhydrazine (2,4.DNPH ‘eagent) t0 detect the presence of caren ‘compounds, Deduce the nature (aldehyde and ketones) of an unknown Carbonyl compound from the results of single fests Fehling’s and Tollen's reagents; ease of oxidation). Peduce the presence of a CHiCO-group in an aldehyde or Ketone, CH:CO-R, from its reaction with alaecribe: (a) the restos reaction with reactive: salt, tion by LIAIN, to form a primary alcohol, 8 8 ction with athatls to produce salt and water (¢) the acid-base reaction with carbonates to produce a ter and carton dioxide (a) esterification with alcohols with concentrated NSO as catalyst (6) 19.1 Organic compounds containing the carbonyl functional group are called aldehydes and ketones, metals to produce a salt and Hi(g), (b)neutrattzation ret s recall the rection (reagents and conditions) by which esters can be produced: the condensation reaction petweent an alcohol and a carboxylic acid with concentrated sulphuric acid as catalyst. qo, Describe the hyetrolyis of esters by dilute acid and by dilate athal and heat. ‘Aldehydes Ketones (1) Functional Group Thaldehydes, the C-atom of carbonyl group isdirectly attached to at least one H-atom, in Ketones, the C-atom of carbonyl group is bonded to two carbon atoms called ketonic group. (2) General Formula |The homologous series of aldehydes have | general formula CoH2n0. The homologous series of ketones have general formula CqH0. () Structural Formula Jn aldehyde may be represented by the general formuta structure K ketone may be represented by the general formula structure REA r—t—r () Examples | (i) H-CHO (Formaldehyde) Methanal ° (ii CHs-CHO (Acetaldehyde) Ethanal CH3—C—CcH CHy—¢—CoHs Propanone Butanone (Acetone) (Methyl ethyl ketone)19.2 PREPARATIONS OF ALDEHYDES AND KETONES By the oxidation of Primary and Secondary Alcohols Primary alcohols are oxidized to aldehydes by warming with acidic potassium dichromate solution, while Secondary alcohols are oxidized to ketones. Alcohols are oxidized by acidified KMnO. or acidified K:Cr0; Solutions to give different products, The Teaction of alcohols with acidified K:Cr:0> is characteristic reaction in which solution changes colour from orange to green. \. Primary Alcohol: Aprimary alcohol is first oxidized to an This can be avoi aldehyde, which is further oxidi K,Cr,0;+ HS, CH CH.OH+[o) —2°2 77 M05 50°C CHCHO ey Acetaldehyde K,Cr,0,+ H.50, CHSCHO+ fo] —27 2 Ts CH,cooH aia zcstioadd 2. Secondary Alcohol: . A secondary alcohol is oxidized under similar condition to give a ketone which is not furthe oxidized. KeCre07 + H2SO, —cHOH +0) CHs—C==0 =H.9 CH3—cHOH + (0) are CH ae soe 19.3 REACTIONS OF ALDEHYDES AND KETONES Nucleophilic Addition |- Base Catalysed Nucleophilic Addition Reaction it ic A base catalysed nucleophilic addition reaction takes place with a strong ina a The base reacts with the reagent and generates the nucleophile. The additic iatedeophile on the electrophilic carbon of the carbon, yroup, The general Le ne is as follows: a aoek 7 the reaction f sf ‘ aot mechanis™ f get? SO sbt ye - 4 H—NU Nuv: + HOI oH + Hi (e250) (Reagent) (Nucteophite) (electrophilic carbon) N toe pCi, ———~ Nu —C— 0H 100" eee nadition of hydrogen cyanide roy cyanide adds to aldehydes and ketones to form cyanohydrins, The acid HCN is form fom the reaction of sodium cyanide and HCl. NaCN + HCl ————» HCN + NaCl the reaction is used in the synthesis of a hydroxyl acid that contains one carbon atom more tun the number of carbon atoms in the starting aldehydes or ketones. . H OH Newo + non MHC, TN ae HNN Formaldehyde pes _ ; oe Hy HH Nowo + Hen NaGN/ He! NO He H~ “en Acetaldehyde | Acetaldehyde cyanohydrin oe Hy Hi C=0 + Hen NaCN/ HCl No cry CH“ cn A Acetone: Acetone cyanohydrin c a (OH) gene, i fk follow” 2°"€Fates cyanide ions which act as nucleophile. The mechanism of the reaction petoxide fon "bonyt com ooneh with hydrogen cyanide to produce cyanide ions, which in tum react ind.or \ SN - Nceo + nen Se Sc / 7 Non ~ ee o. OH \ 7 \ 7 NY ey ER me — CN 2. Haloform Reaction (lodoform test) In aldehydes only ethanal or acetaldehyde contain this group. So, this reaction i differentiate ethanal from other aldehydes. Ketones which contain CH3- STOUP direct) attached to carbonyl carbon are called methyl ketones. In ketone only methyl ketone undergo this reaction. Therefore, this reaction is also used to differentiate methyl ketones from other ketones. When iodine solution is added to a small amount of aldehyde of ketone with the addition of sodium hydroxide solution and the mixture is warmed, Appearance of a very pale yellow precipitate of tri-iodomethane called iodoform Shows the presence of CHs-CO- group in the carbonyl compound. S Used ty | Examples: * Inaldehydes only ethanal will give this test positive. ° CH 3—C—H + 31, +4NaoH———» CHI, + HCOONa + 3Nal +3H,0 Ethanal lodoform Sodium methanoate (Yellow pet) * In Ketone only methyl ketones will give this test. cH,—¢ ‘CH3 +312 +4NaOH ———-» CHI, + CH,COONa + 3Nal + 3H, Propanone (falew peg ‘Sodium ethanoate lodoform test is used for distinguishing methyl ketones from other ketones. It is also used to distinguish ethanol from methanol and other primary alcohols. Il- ACID CATALYSED NUCLEOPHILIC ADDITION REACTIONS ker Acid increases the electrophilic character of the carbonyl carbon and the attack of the we! nucleophile on the electrophilic carbon becomes easy.2,4-dinitrophenylhydrazine ct with 2,4-dinitrophenythydrazine (2,4-DNPH) in the presence of ence of an tion with ketones reat yellow or orange precipitate of 2,4- dinitrophenylhydrazone, lyst to form Ry HN Ne tO / Re acatal the identifying test of aldehydes and ketones. ON 2,4-DNPH Yellow / Orange ppt H atom. nd Ketones with hydrides ride (NaBHs) or Lithium aluminum hydride converted to primary or secondary alcohols. (hydride ion). NaBHeis weak reducing agent hyde and y be Alkyl group or ere Re MA) {reductions of Aldehydes a! h as sodium boron hyd ‘when reducing agents suc! (UALHa) is added to aldehydes or ketones, they are he BHsand the ALH4 jon acts as a source. of H ion hile LIALH, is strong, reducing agent. During this reaction Carbonyl group (CO) of aldel etone is converted to CH(OH)- a LiAIH gH y—tow + 2H) H—CH—H Methanal Methanol g i oe eet 2[H] LAH GR eR R ‘secondary Alcohal Ketone cH,cHO+ apy | NSB CH,CH,OH Ethanol Ethanal CH,CocH, + 2(H) Na8Ha, CHgCH(OH)CHs ‘2-Propanol Propanone5. Reaction with hydrogen cyanide Cyanide ion adds to aldehydes or ketones to give a cyanohydrin. * The reaction is usually carried out using NaCN or KCN with HCl. * HCN is a fairly weak acid, but very toxic. HO UCN CI C. ao Ne ° H—c=Sn + r—l oe ee Nucleophilic Addition of Cyanide to an Aldehyde Step 1: The nucleophilic ¢ in the cyanide adds to the electrophilic C in the polar carbonyl electrons from the C=O move to the electronegative 0 creating an intermediate atkoxid; ° sroup ie. Step 2: An acid/base reaction. Protonation of the alkoxide oxygen creates the cyanohydrin product, o Ht ra Heeion + Hyc—t—en H 6. Reaction with Primary Nitrogen Nucleophiles Addition of primary amine to aldehydes or ketones gives imine ° NR" 5 sid R"—NH, + rte —> R— imine R + HO " 7. Oxidation Reactions i. Oxidation of Aldehydes They are also oxidized by strong oxidizing agents such as KxCr207,/ HzSO,, KMnO, / H:SO4, an dilute nitric acid. ° H +0] EGCHOnHSO4 CHj;—C—ox cand if CHj;—C: ‘eotahyse peat KCra07/H,S0, em O° tn it CHy—CH,—C—H + [0] HjsC—CH,—C—oH Propionaldehyde Propionic acidof Ketones ized by strong oxidizing agents such as KaCriO7,/H:SO,, KMnO4/HSO4 and only %! ‘on atom joined to the smaller number of hydrogen atoms {s oxidized. in Ir aga? Spe Cat PON ves only one carbon atom adjacent to the carbonyl group is oxidized are, essen ponte acids is always obtained. Mol Ye of U ‘ HH g K,Cr,0;/H 80, j cy + 10] CH 3% cotone ° CH te + HCOOH ‘cette acid ’ symmetrical ketones, the carbon atom joined to the smaller number of y, inc i of eferentially oxidized and the carbonyl group remains with the smaller alkyl ret toms 5 PI en ato" - K,Cr,07/H SO 4 q i 4, : i GHy—CHs* {0} 27> cH y—t—on + ch,—b—on = bos ‘Acetic acid Hs Gutenone {TESTS USED TO DISTINGUISH ALDEHYDES AND. KETONES 19.4 nts like Tollen’s reagent, Fehling’s solution and Benedict’s solution easily oxidizing ase ‘boxylic acids. Ketones are not oxidised by these weak oxidising agents. tie atdenyaes to car f t1; Fehling Solution Test jest '+ ve solution(a mild oxidising agent)is an alkaline solution of Cu ions and sodium or iin artarate). When Fehling solution is added to an aldehyde, red ppt of Cu0 is formed. assi " his test is not given by ketones. ciclo + 2Cu% + SOH + > CuO + CH;COO% 3H,0 Adetyde oxidise to salt of carboxylic acid and Cu” reduce itself to form Cu". Test 2: Tollen’s Test (Silver mirror test) When Tollens reagent (aqueous Silver nitrate, ammonia and sodium hydroxide) is added.to an aldehyde, ‘silver mirror’ (Ag) is formed. This test is not given by ketones. This test is called ‘iver mirror test. CHOW + ZTAR(NHa)]" (en + OH'aq) . CH:COO'pa) + 2NHs‘eg + 2Agins + 2NHy 19.5 CARBOXYLIC ACIDS pounds which contain carboxyl group (-COOH) functional group in their molecule tben chain ome acids. Aliphatic carboxylic acids have the carboxyl group attached with th hey Carbon atoms. alkyl group. Aromatic carboxylic acids have the carboxylic group "nyl or aryl group. ° Seanic com ® called “May be ° Tepresented by the general formula R—G—oH where R = Hor anyUMMA ke ia etn 19.6 PREPARATION OF CARBOXYLIC Recall that carboxyitc 1. ACIDs acids can be prepared by the following methods, By the Hydrolysis of Nitriles Organic Compounds having a cyanide group are called nitril boiling with Mineral les. Hydrolysis of an rT acid or alkalis yields carboxylic acid, alkyl nitrite g Hel N+ 2H,0 —~—® RcOOH + Ny Cartorytie mid R— HxC—CSSn + ano Nel HCOOH + NH, Artic ac The acid produced by this method Contains one more carbon atom than the Original atkyt hati 2. By the Oxidation of Primary Alcohols Primary alcohol is readily y oxidised to aldehyde, which further Oidises to carboxylic acids in Presence of oxidising agents such 8S potassium dichromate or Potassium Permanganate jn acidic medium. OH O° R—E— nei) Moms RL ‘Oxidation t KMn0,/H,S0, 8 R— bitte joy Know te Roy Oxidation 3. By the Hydrolysis of Esters Esters can be hydrolysed to acid and alcohol dilute acidic or dilute atkali and heat followed acidification. Basic hydrolysis of esters is known as saponification because it leads to the formation of salt of carboxylic acids which is soap. The salt can be converted to carboxylic acidification. cH —t—oc,n, Noor Etiytoootate Concept Assessment Exercise 19,1 How can you convert CHsCl into CHCOOH? 9° cH, —8_ona+ ¢.H,on ‘Sau acetate Ethane a -Ain ene neon eeruleroniC 49.7 REACTIVITY OF CARBOXYLIC ACIDS 9 yt grouP shows the chemistry of both the carbonyl (2) and the hydroxyl of most reactions, the carboxyl group is retained. However, the reactivity of al ‘ oes {s due to the presence of carbonyl group. (Or nol ern 49.8 REACTIONS OF CARBOXYRIC ACIDS 1e following types of reactions. ic acids undergo th " h hydrogen atom -OH group of carboxyl group is involved (salt ot? se reaction i9 whicl 1 gormation)- the reaction in wl 4 The reactions involving carboxyl group as a whole, j reaction involving H-atom of the carboxyl group (Acidic properties ‘i i of carboxylic acid) weaker acids than mineral acids. They produce H’ion when dissolved in nich OH group is replaced by another group. | carboxylic acids are 1} water o ° | H,0 I <4 dy eee! RG O+ H (Carboxylate ion) (Proton) R—C—O a) Reactions with bases t with bases (NaOH, KOH) to form salts arboxylic acids react ; CHjCOOH + NaOH ——————+ CH,COONa + H,0 falcon Sum Aosta b) Reaction with carbonates and bicarbonates (aboxylic acids decompose carbonate and bicarbonates evolving carbon dioxide gas with effervescence. 2CHsCOOH + Na,cCOs; >. 2CHCOONa_ + H20 +CO2 Acetic acid ‘Sodium Acetate CH;COOH +NaHCO, -——————> CH,COONa + H,0 +CO2 Sodium Acetate Acetic acid ©) Reactions with metals atbox 7 outie acids react with active metals such as Na, K, Ca, Mg etc to form their salts with lution of hydrogen gas,2CH,COOH + 2Na —_______..2CH.,coona , cations Sodium Actate q z 2. — Reaction involving the OH group of Carboxylic acid, Reaction with Alcohol (Preparation of Esters) When carboxylic acids are heated with alcohols in the presence Of conc. 1.0, Hs formed, Such a reaction in which two molecules combine with the elimination of smal a like water is called a condensation reaction. 8 coe #90, 9 a—l_ on + Xo r—l_o + Ho cartoxticad . Ese . | i cacti, ° HyC—C—on + H—o—c¢.4, ——— neratero eg #420 | Aceticasid Ethan Emytantze 78? | Mechanism of reaction for Acid Catalyzed Esterification Step 1: Protonation of the carbonyl makes it more electrophilic. CS, cmon yt Hyc—C—on + HY === = H;C—c—on Step 2: The alcohol OH functions as nucleophile attacking the electrophilic C of the C=O group. : 6 —H on H coal Om + CHy—CH,—OH =———= H,C— —ou CHs—CH,—0—_ Step 3: ‘ ‘ In this step, hydrogen ion transfers in the molecule, O—H OH eal =H scot lata CHy—CH,-—9 ae CH,;—cH,—< Step 4: a In this step the elimination of water and H’ ion from the ion takes place.° Te cite oncl Hse ie arr oh OCH, —CH, +H,0 +H", ot W antta 5 tions involving Carboxyl group(—COOH) to Alcohols tio tic acids are reduced to primary alcohols. so oa j ‘ lt of their low reactivity, carboxylic acids can only be reduced by LiALH, to form weal alcohol. fi cH, cooH + 4H] LAs, cH, cH,0H + H,0 = 3 2 fe less reactive to reduction by hydride than aldehydes, ketones or esters. carve acids a : 419.9 HYDROLYSIS OF ESTERS sters can be hydrolysed to acid and alcohol with dilute acid or dilute alkali cal tat © xd peat. ch ysis of esters is known as saponification because it leads to the formation of ia salt of carboxylic acids which is soap. E ° , ° H,0) yt OC,H,—=——= CH s——¢—OH + C,H,OH Ethyle acetate Acetic acid Ethanol ° ° i cH,—¢— 0C,H, => CHj—¢—oNa+ C,H,OH Ethyle acetate: ‘Sodium acetate Bhaicl fgncept Assessment Exercise 19.2 low can you convert? x 1, Ethanoic acid into ethanol 2, Ethanoic acid into ethyl acetate 3, Ethanol into ethanoic acid ; query alcohols can be oxidized to aldehydes (or further to carboxylic acids). tte ondary alcohols can be oxidized to ketones. ; ay alcohols cannot be oxidized (no carbinol C-H). des are prepared by oxidising primary alcohols, ketones by oxidising secondaryalcohols. * The carbonyl group readily undergoes nucleophilic addition, 7 5 followed by the elimination of a molecule of water, resulting in a cone reaction, . eMsati + Aldehydes are generally more reactive than ketones, * Aldehydes can be oxidized to carboxylic acids by a variety of Feagents, Ket not readily oxidized. ones a * Carboxylic acids are the most acidic of the common organic fur * The most important reactions of carboxylic acids convert the: derivatives such as, esters. nctional groups, M into Carboxylic ag References for Further Information * B.Earl and LDR Wilford, Introduction to Advanced Chemistry. * lain Brand and Richard Grime, Chemistry (11-14). + Lawarie Ryan, Chemistry for you. Exercise Choose the correct answer (i) Ketones are prepared by the oxidation of a. Primary alcohol b. Secondary alcohol ¢. Tertiary alcohol d. none of these (ii) Which of the following reagents will react with both aldehydes and ketones? a. Grignard reagent b. Tollen’s reagent ¢. Fehling’s reagent 4d, Benedict’s reagent (ili) Aldehydes are the oxidation product of a. p-alcohols b. s-alcohols c. ter-alcohols d. carboxylic acids ! (iv) Which of the following compounds will not given iodoform test on treatment with h/ NaOH. a. Acetaldehyde b. Acetone cc, Butanone d. 3-pentanone (v) Aldehydes and ketones are carbonyl compounds. Which of them react both wit NaBHs and with Tollen’sreagent. a. Both aldehydes and ketones b. Aldehydes only c. Ketones only d. Neither aldehydes Nor Ketonesy A carboxyl actd contalis finettunal qr OUft) a aA nydroxyl wou Jy, A Carley qe ~ ¢, Hydroxyl and Carbuiyl mroupy A Carbine att alleti yale urvis which reagent {ts used Lo reduce a callineylle all Hert mi c, NaBH, th LAU, ii) carboxylic acids react with metal to fort alte YUH Lhe e7Olitloni OF wi 00, belly ¢.cO de CH esters are formed by the reaction of carboxylle at td vat “ a, alcohols r b. ethers c. aldehydes dd, Alkyl fialiddes When a carboxylic acid reacts with alcohol, It produces a neys clan OF #) compounds. a. ethers by esters c. anhydride d, amide (i) The colour of lodoform is a. White b, Black c. Yellow di, Blue ‘ Give short answer. (i) (ii) (ii) (v) wy) (vi) Wii) (vill) (tx) How can you distinguish ethanol from methanol? Desctibe briefly the nucleophilic addition mechanisin to the carbonyl compound: What is the mechanism of HCN addition to carbonyl compatindst How is ethanol converted to lactic acldi What is Haloform reaction? Which type of alcohols undergo lodoform reactlont What are aliphatic and aromatic carboxylic acts? How are esters produced? How may nitriles be converted Into carboxylic acld? How will you prepare carboxylic acids from? (i) alkyl nitrite (ii) Hydrolysts of esters Give mechanism for reaction for acid catalysed esterification, Whatis thé reactivity of the carbonyl group?Chapter 19: Carbonyl Compounds 10. 12. 13. How formaldehyde reacts with HCN ? Give the following reductions of aldehydes and ketones (i) With NaBH, (ii) Catalytic reduction Examine the mechanisms of carbonyl compounds reactions, What is the minimum number of carbon atoms a ketone may contain, Comm: lent, Write structural formulas of all the carbonyl compounds having molecut; aug CHO. : 3 formy (i) Classify each compound according to the functional group (ii) Give one reaction that can differentiate between them. (iti) Can you use iodoform test to distinguish between them. Give reason, (iv) Write the reactions of these compounds with LiAlH,. (v) What products would you get when these compounds react with HCN, How will you bring about the following conversions. (i) _ Ethanol into ethanoic acid (ii) 2- propanol into propanone (iii) Butanone into acetic acid (iv) Ethanol into acetic acid An organic compound has molecular formula C,H. It has following properties (i) Evolves hydrogen with Na ] (ii) Forms salt with NaOH (iii) Write its structural formula and IUPAC name. (iv) Write its reaction with ethanol in presence of an acid. (v)_ Give one method for its preparation Compound A is an alkene which can be converted into carboxylic acid by the followin route. A —> B —+ C —+ CH,COOH (i) Identify compounds A, B and C (ii) _ Give chemical reactions for each step, (iii) Give IUPAC name of each product. Collect information about the role of carbonyl compounds in flavour and fragrance chemistry. Write an essay on it.tL Define primary and secondary amines and explain their basic properties and reactivity. scondary amines in terms of their structure and chemical Identify the differences between primary and se’ properties. 4. Deseribe the preparation methods of primary and secondary amines including nucleophilic reactions and ‘eduction of nitro compounds. vity of phenylamine and azo compounds, Including their uses as dyes 4. Explain the properties and reacti and pigments. Ieeeresetenen20.1 AMINES replacing one or more hydrogen atoms by alkyl or aryl groups. This means ami of ammonia, Mes are derivatiy to the number of carbon atoms direct attached with nitrogen euBrimagyamines: pth) Secondary amines: pe) Tertiary amines © In primary amines only one alkyl group is linked with nitrogen atom. Th ey have gene formula R-NH: i (© In secondary amines two alkyl groups are linked with nitrogen atom, They have general formula R-NH-R In tertiary amines three alkyl groups are linked with nitrogen atom. They have gener; formula (R)sN CH3 — NH2 CH3 —CH2 — NH2 CH3— CH2 —CH2 —NHp / ‘Methyl amine. Ethyl amine Propyl amine | CH)—-NH—CHy —CHs -CHz—NH—CHy Hs —CH, — NH —CH —CH, Dimethyl amine ‘Methyl ethyl amine Dimethyl amine 20.2 PHYSICAL PROPERTIES OF AMINES: The polar nature of the N-H bond (due to the electronegativity difference of the t atoms) results in the formation of hydrogen bonds with other amine molecules, (Because of hydrogen bonding they have high melting and boiling points compared analogous alkanes and high solubility in water. all stru N Ne sp?-hybrid orbitals while the fourth nor bonding sp?-hybrid carries 4 1 TR a pair of electron. Amines have the ability to donate this electron (un te pair, This makes them a base and a nucleophiles. An amine with three different groups is optically active. Structure amines:y 20.3 PREPARATION OF AMINES (, otic solution of ammonia is heated with an alkyl halide in a sealed tube at 100°C, in ste ter- amines and a quaternary ammonium salt is obtained. ol a CyHs—! + NH3 ———+ C,H,—NH2+ HI 2 ethyl amine CG pH_e—! * Cos —NH,—+ C,H, —N——GHg, + HI. 2 diethyl amino 4h CHa! * Cs N—CrHls ——> (CaHs)N + HI H triethyl amine (CoHs)3N + CoHs| ———> [(CoHs)4N] 7 quatemary ethyl ammonium lodide d of the reaction, addition of strong alkali such as KOH liberates free amines from their - the quaternary salt is unaffected. The three types of amines are separated by fractional a ‘Over alkylation can be avoided by using excess of ammonia but the yield is low. ilatlon- I. en containing functional such as nitriles, amides, and nitro are reduced to amino group yrarious reducing agents. — ziuction of alkyl or aryl nitriles gives primary amines. The reduction may be brought about by ducing agent i.e. LiAlH,, or sodium in ethanol. R—cesn: HAIG, R—cri—-NH, Nitrile Reducing Amine ‘agent irles on reaction with hydrogen gas in the presence of catalysts such as Rh-Al2Os, Pt or Raney ikel gives primary amines CHCN+ 2H, Rh ALS cHcH ANH, Aminoethane Ni ma Phenylethyamine tro . ; 5 Compounds on catalytic or chemical reduction produce primary amines Nitto benzene can Inthe presence of ae be reduced to Aniline (phenyl amine) by using reducing agent as tin /iron concentrated hydrochloric acid or by catalytic hydrogenation (e.g. Hz/Pd)HCl a Ty MN, Aainne CyHyNO,- inetansme “When an amide is treated with reducing agent LIAIH, -CO group g of amide jg and primary amine is formed.(The carbon chain remains intact in this reaction) tog) UAH CHly— 6-H + aH] » CHS CH NH + Hy When an amide is treated with bromine in the presence of KOH, degradation of Place leading to the formation of primary amine. This reaction is known degradation reaction. amide taky as Hoftmay ° chy —U—nn,+ or,-KOH cH NH, + CO,+ HBr 9° CgH~—CH —t—nna+ Br, KOH cH gc NH, + CO.+ HBr et 5 — CH 2 2* COy 20.4 BASICITY OF AMMONIA AND METHYL AMINE because of non-bonding pair of electrons on nitrogen easily be donated to an electron-deficient centre. Consider the following reactions. Neb +H-Cl > NH4? + Cl CHsNH2+H-Cl > CHa-NHt + Cl’ The strength of a base is expressed in terms of phy, for ammonia and methyl amine, the pil values are 4.76 and 3.38 respectively S Since pK ya, > PKenyuni, methyl amine is a stronger base than ammonia. It can be explaing as under: In ammonia, the pair of electrons attracted by s-orbitals of hydrogen atoms whereas CHs—NHb, sp’orbital of carbon push electrons towards nitrogen. Comparison of Basicity of primary and secondary amines. The presence of electron-donating group increases the basicity of amines. Secondary aming stronger base than primary amine, since it has two electron-donating alkyl groups.y eSecondaryamine > primary amine.» 20.5 REACTIONS OF AMINES ine reacts with acid halide, secondary amide is formed. am! eet Il I R——C—Cl + RNH, ———>_ R——C——NHR + HCI CHsCOCL + CHsCH:NH:> CH;CONHCH2CHs + HCL N-Ethyl acetamide St react with alkyl halide to form secondary, tertiary amine and ammonium salt. mines: ni fon ig called alkylation reaction. ', / ™ CaHg—I + Cats —NHz ——® CzHs—N— Cats + HI . oth amine 44 CaHs—I + Cats ——N—CzHs ——> (CoH5)3N + HI tity amine (CoHs)sN + CoHs|_ ——>[(CoHs).N] TF quatemaryethy! ammonium lodide ines react with nitrous acid in the presence of hydrochloric acid, diazonium When amit : is are formed. The reaction mixture must be kept below 10°C. compound! RNH + HNO, +HCI__» R —N ==NCi+2H,0 lazonium on Alkyl diazonium salts are generally too unstable for practical use. When the diazonium group is attached to the benzene ring, the delocalized electron in the ring stabilizes the ion to some extent. Because of this, the benzene diazonium ion is far more stable than the aliphatic diazonium salt of it. Benzene diazonium chloride is a colorless crystalline solid, It is stable below 10°C and decomposes easily above 10 °C. When combined with phenol, itforms an orange-red dye. Phenyl azo compounds are used as dyes and pigments in the textile, cosmetics, paint, and leather industries. Phenyl azo dyes have antibacterial and antifungal properties, CH NH2+ HNO, HCl, ci, -N==Nci+ 2H,0 teams decohm ace* Amines are alkyl or aryl derivatives if ammonia * In primary amines only one alkyl group fs linked with nitrogen atom * In secondary amines two alkyl groups are linked with nitrogen atom’, * Inamines, nitrogen atom is sp3-hybridized and has nearly tetrahedral str, * Amines have the ability to donate electron pair. This makes them neleopr ne * Phenyl azo dyes have antibacterial and antifungal properties, Philes, * Phenyl azo compounds are used as dyes and pigments. References for Further Information * B.Earl and LDR Wilford, Introduction to Advanced Chemistry, * lain Brand and Richard Grime, Chemistry (11-14). + Lawarie Ryan, Chemistry for you. 1. Choose the correct answer (i) General formula for secondary amine is a. RNH, b. RNHR c. NH, d, RCONH, (ii) (ii) General formula for nitriles is a. RNH, b. RNO, c. RCN d. ROH (iii) Which of the following is a reducing agent? a. KMnO, b. K,Cr,0, c. LiAlH, d. NaOH (iv) Which can donate an electron pair? a. RX b, RCOR cc. RCHO d. RNH, 2. Give short answer. (i) What are primary, secondary and tertiary alkyl amines? (ii) | What are the diazonium salt? (iii) Amines are more basic than ammonia. (iv) What are amines?have high melting / boltin amines Ig points as compared to oth er analogous alkanes. why? thylamine isa stronger base than ammonta. Explain ow would you prepare Diazonium salt? vil) Ms s the methods of preparation on amines at are nitriles ? How they can be reduced, tify the differences between different types \ int en ty cal properties. types of amines in terms of their structures yate the importance of diazonium salts in everyday life. iv valt ake a comparison between primary amines and secondary amines.|. Explain the concept of organic synthesis and functional group interconversions, .. Identify organic functional groups using the reactions in this Progression grid, . Predict the properties and the reactions of organic molecules based on functional group presence. |. Devise multistep synthetic route for preparing organic molecules. . Analyze a given synthetic route in terms of type of reaction and reagents used for each step of it, and possible by-products, . Explain the concept of retro-synthesis and its applications in organic synthesis.arch cneists want (0 een New compound, they usually work backwards from the mppound to create # series of reactions, starting with a compound extracted from a oo pvailable raw material. In industry, common starting materials are hydrocarbons ny ‘oil and its refining, and compounds extracted from plants, such as esters from fats dl table oils. You will need some of the skills of a research chemist when tackling ; ae hat involve? jo! es ing the reactions of complex molecules, you have never seen before, containing pret an one functional group. fe a series of reactions to make a given compound from a given starting compound. 0 21.1 IMPORTANT ORGANIC REACTIONS uss’ ing e successful in answering these questions, you will need to be familiar with all the oo ditions ofeach homologous series mentioned inthe syllabus. The flow chart exons 4 is a summary of some of the most useful reactions you need to know, but you / Fa sked about others, so it is a good idea to make your own summary charts for all the pce in oo organic Chapters. t.1.1 Adding Carbon Atoms metimes the starting compound from a raw material does not have enough carbon atoms in molecules to make the desired product. An extra carbon atom can be Med by adding the nitrile functional group, -CN. Remember that these can be made from iy halide, Heating alkyl halide with ethanolic KCN RBr + KCN ————»RCN + HBr x8cama fies HY hie PAM ttedecies cn . tra cntbont alt Bt ts ay ay nO“ fy dilute fie ilen, WON 4 tedwag iy A ty TALL ore Tete ant allyl quan mag i el ir snake aw carinaylie WW Wy Hi make an ariie (oy nedeting | Jali a In ly erie far vip sheet ta a bonzen Wg tof COTnpltig Ct a Priced tong pute “Cty gotul renetlon yhven plan nV We can add att allyl nites, rwac tion, wlle Aes another Uw! for examples ral y CCH, + Ne Cth t CH CHEL AlCl, catalyst a i yabenZene hensene Concept A Name the organic products: assessment Exercise 214 Atod Inthe synth cl add oe tn convent benmene bite betrenediramtun, ta elle route: balan: | GACOOC, Doll vith. Had}, A held 07 1g Mid omen, y | { Devise a Uhressstage synthetic route | chloride, {I How would you convert the benzenediazonturn and Analysis of Reactions Involved in Multi-steg b 1 chloride Inte an orange dye? 21.1.2 Preparation Synthetic Routes of Organi Mol synthesized. from other organic compounds having different es, Following ezarnple Involves the formation of methane ecules. Organle compounds can be functional group via multt-step rout from ethanole acid, To prepare ethanolc acid from methane following steps are involved. ‘Stepi4: Methane to Chloromethane Type of reaction: Free Radical subst{tution. Reagents: Chlorine gas in the presence of UY Light. By Product: HCI CH, + Cl, + CH,Cl + HCl ‘Stepi2: Chloromethane to cyanomethane Type of reaction: Nucleophilic substitution. CH,CL + KCN -» CH,CN + KCL “'Step'3; Cyanomethane to ethanolc aicd Type of reaction: Hydrolysis, CHCN + 2H,0 —-5 CH,COOH + NH,4 Test used for the Identification of Functional Groups. git « gests are used for the fdentification of functional groups. too is used fr the identification of unsaturation (c= ¢ / iste at; Aqueous Bromine, " ation with alkene or alkyne: Redish brown colour of bromine fades away. nse f is used for identifying the halogen present in the given organic compound. js tes nt? ation with Chloro alkane: white ppt of AgCl is formed. pat ‘AgNO, + CH,CH,OH ———> ROCH,CH, + AgCl + HNO; rod €) in an organic compound. ‘Aqueous silver nitrate in ethanol aoservation with Bromo alkane: Cream ppt of AgBr is formed. par + ABNO, + CH,CH,OH ———> ROCH,CH, + AgBr + HNO, ayseration with fodo alkane: yellow ppt of Aal is formed. 1 + ABNO, + CH,CHOH——> —ROCH,CH, + Agl + HNO, qhis test is given by alcohols, aldehydes and ketones. > Inprimary alcohol, only ethanol will give this test positive. > Insecondary alcohol, only those alcohol will give this test where O-H group is attached with carbon no. 2 e.g., CH,CH(OH)- This test is not given by tertiary alcohol. In aldehydes only ethanal will give this test positive. In Ketone only those ketones will give this test in which carbonyl group is at position 2. eg vey ° I CH,—C—R feagent: odie and aqueous sodium hydroxide Gbservation: A yellow ppt of triiodomethane (CHls) is formed. Organic compound + |, + NaOQH——» CHI, + RCOONa+Nal . Yellow ppt This is the identifying test of carbonyl compounds (Aldehydes and ketones). Feagent: 2, 4 - dinitro phenylhydrazine Sbservation: yellow/orange precipitate of dinitro hydrazone is formed. ne+ Qu Sno, - t Nos red pptot 314 Sinttrophenythydrezone ‘This ts tho = 0 group standard test for ~ ‘Test'52jFehling Solution Test This test is given by aldehy yvdes only. This test is used to differentiate aldehydes from ketones. Reagent: Fehling solution (a mild oxidising agent) Fehling’s solution is an alkaline solution of Cu” ions and sodium or potassium tartarate). Observation: Red ppt of Cu,0 is formed with aldehyde not with ketone ionic equation CH,CHO + 2Cu’* + 50H’ + sodium tartarate —» Cu,0 + CH,COO"+ 3H, st This test is given by aldehydes on| ly. This test is used to differentiate aldehydes from ketones. Reagent: Ammonical silver nitrate (Tollens’s reagent) Observation: Silver mirror of Ag is formed with aldehyde not with ketone fonic equation CH,CHO,, + 2[AG(NH)" aq + OH—> CH,COO' a + 2NHp + 2G, +2NHyy Silver mirror Reagent: Potassium dichromate in the presence of concentrated Sulphuric acid Observation with Primary Alcohol: Orange colour solution turns green. With primary alcohols, the initial aldehyde product may be oxidised further to a carboxylic acid, particularly if heated or excess oxidising agent is used. If we want to prepare only aldehyde than condition will be heat the mixture and distilled off. RCH,OH + [0] +RCHO RCHO + [0] + RCOOH Observation with Secondary Alcohol: Orange colour solution turns green. Secondary alcohol oxidised to ketone which gives no colour with Fehling solution. RCH(OH)R + [0] + RcOR Observation with Tertiary Alcohol: No colour change of Potassium dichromate. Tertiary alcohols resist oxidation,identifying test of carboxylic acid, he is sm godium car ee effervescence | Na,CO; ————* CH,COONa + H,0 + CO, Reaction Given by Functional Groups bonate (Na2CO3), oe types of ee dergo Free radical substitution reaction. In this type of reaction, hydrogen of alkane ae wad by free radical i.e Cr. General reaction is given below. te cy Choro alkane + HCL kane * 1 7 diffused sunlight dition* STOTT ho) ‘ocarbons undergo two types of reactions. rsaturated hydr s one of the two bonds in the carbon-carbon double bond is broken and a new these reacti sgle bond is formed from each of the two carbon atoms. x Y I 1 aN + XY — SF —C—C— 7 | | Y ii 6 N c—=c + z—z2 — —e —c — 7 N 1 | it | mi || Figure 21.2: General Equations for Addition Reactions> a with HBr/H20/HOX and b with H,/Br2. In an Addition Reaction a Single Product is always Formed. 1,2-propanediolAlkenes can undergo ozonolysis to form aldehydes and ketones, of Alkene. In this reaction C=C pi bond of alkene is broken and are formed. Alkyne upon ozonolysis yield carboxylic acid, q 1) 03 H ° ~4+ 2) Zn, HCI + A f This is also Oxidation 1 {Wo new carbonyts compan nds H ° H semen 2 —< JN HO (SERERETSRTAP AIG ales Alkyl halides undergo two types of reactions: |n Nucleophilic substitution reaction, the halogen group in alkyl halide (R-X) is dig Placed attacking nucleophiles ©.8 OH”, NH and CN. General reaction is given below. my R-X — OH-/NHs/ cn- R-OH/R-NH,/RCN + Xx- ] In an elimination reaction, hydrogen and halogen are eliminated from alkyl halide, leaving an alkene as the organic product. The reagent used in these elimination Teactions is ethanolic NaOH / KOH, td + alc. KOH —4 tad + KX + H,0 Hx (att natde) (alkene) Alcohol undergoes different types of reactions. Oxidation, Substitution, dehydration, and esterification. Figure 21.3 Fepresents different types of reactions of Alcohol“ a ompounds undergoes different types of reaction such as nucleophilic addition, « categn, and reduction reactions. >In nucleophilic addition hydroxyl nitrile is formed. > Aldehydes oxidised to carboxylic acid while ketone resist > Aldehydes reduce to primary alcohols while ketone reduces to secondary alcohol. ts towards oxidation reaction. (aboxylic acid undergoes acid base reaction and esterification. > Carboxylic acid reacts with base, metal and metal carbonates. These are acid base reactions. "y Reaction of carboxylic acid with alcohol is called esterification. 21.2 KEY REGENTS USED FOR SYNTHESIS kidified potassium dichromate or acidified potassium permanganate. se oxidising agents oxidise primary alcohol to aldehydes and then to carboxylic acid. These ‘idising agents oxidise secondary alcohol to ketones. : ents lowing reducing agents are used. ei: La Reduces a carbonyl group to an alcohol. * Strong reducing agent than NaBHs, it reduces carboxylic acid to alcohol.Hi and Nickel catalyst: Reduces aC = 6 double bond, Tin/HCl: Reduces NO; to NHy A dehydrating agent is one that removes water from a molecule, Common dehydrating agents are ALOs and Concentrating H:50,. Flow chart of Different Reactions of Functional Group Figure 21.4: Organic Functional Group Interconversion Concept Assessment Exercise 21.3 . 1. Compound X, molecular formula C4H8, undergoes the following reactions. Bra aq.NaOH/heat iH > C,H,Br, ———— _ C,H,,0, x Y z H,/Ni C,H, ———> methyipropane x (a) Suggest a synthesis of the starting material i.e C,Hs. (b) What is the formula of compound Z? od 2. Prepare ethanal and propanone starting from 2-methyl but-2-ene. 3. Devise the best synthetic route to prepare 2-hydroxy propandioic acid starting from” ethanal.y 21-9 WEIRUDTNTHETIC ANALYSIS a method of chemleal synthe 5 oth vile Involves vals 192 . Wolias “MecomAnNny! 4 ” yo is readily avatlable, stiple star tity matestals ty aise thes best se wa Hygrercnce between syathesls and retrouyattwests ts that synthuate 1s the licen fen ple reactions to form an organic, Compo, BUL Letivaynithests ts the jor id a card from the LATHE Orgone compound to dea mln any geld am a simple precursor molecule, rintisats, rom a8 wo ynthests for ethyl propanoate 10: pet! retrosynthests for ethyl propanoate, you vall start with the ta ryeh molecule and we yo to Identify Mts precursors, Ethyl propanuate has the following structures yok CH,CH,COOCH,CH, thetic analysis involves breaking down this molecule Into «tmpler fragments that can ie d from known starUng materials or simpler compounds. In thls cae, We can have ; e rt agments CHy-CH,CO and O-CH,CH, qujctt,co you can use CH,CH,COOH (propanote acid) i “ or 0-CH,-CH, you can use HO-CH,-CH, (ethanol) as precursors, oy fe two precursors can be combined to form ethyl propanoate through an esterification in: Ethyl propanoate {s an ester, and It can be synthesized by the reaction of Propanoic ig (carboxylic acid) with ethanol (alcohol) in the presence of sulphuric acid as catalyst a CH,CH,COOH + HO-CH,-CH, £8. CH.CH,COOCH,CH, + HO pe etrosynthetic pathway for ethyl propanoate can be summarized as follows: ftyl propanoate_«~ Propanoic acid + Ethanol Retrosynthesis of cyano propane yano propane contains an alkyl chain (propane) and a cyano group (-CH) attached to one of ts carbon atoms. CH,CH,CH,-CN teak the molecule into its functional groups: Cyano propane can be divided into two simpler lagments: opane backbone CH,CH,CH,- and Cyano group (-CN) iw you need to find simpler motecules that can combine to form the propane backbone and te cyano group. «the propane backbone you will use CH,CH,CH,-Cl cyano group you can use KCN CH,CH,CH,-Cl + KCN > CH,CH,CH,CN + KCIApplication of Retrosynthesis What is the role of retrosynthesis in chemistry? In chemistry, Fetrosynthesis enabl development of multiple reaction pathways or.pathways for a given target compound 5 the various reaction pathways can be more cost-effective, more transparent to the envir, and require fewer reaction steps, NVironment Concept Assessment Exercise 21.4 1. Discuss retrosynthesis of the following compounds (2) CHy-CHy-CH,-Cl (b) CH,-CH,-CH,-OH (C) CHy-CH,-CO-NH-CH, (d) CHy-CH,-COOH (e) CHy-CH,-NH-CH, (f) HCO0C,H, * Recognising the functional groups in a given organic molecule enables us to predict. its. reactions, Knowing the reactions of the different functional groups in organic reactioy to devise synthetic routes to make given compounds. Length of carbon chain can be increased by the hydrolysis of nitriles. Different chemical tests such as bromine water, lodoform, 2,4 DNPH and Fehting sot test are used for the identification of functional group indifferent organte ‘compounds. Organic compounds undergo different types of reactions such as free radi Substitution, electrophilic addition, nucleophilic addition, oxidation, reduction, elimination and nucleophilic Substitution reactions, * Synthesis is a forward Process that combines the building blocks to create molecules. Whereas retrosynthesis is a backward process that breaks down the compl molecule to help chemists understand its origins. Exercise 1. Choose the correct answer ns enables us (i) The product of the reaction between under acidic conditions. What is the a. CHCH(OH)CO,H ¢. (CH;),CHCONH, Propanone and hydrogen cyanide is ydi formula of the final product? b. CHCH,CH,CO;H d. (CH,),C(OH)CO,Hnound X undergoes the following reactions, comP cant NOHlea) Meat 50 SOF Hi(0q)/ heat “ “4,0 only what Is X? a, 1-bromobutane b. 2-bromobutane ¢, tbromo-2-methylpropane d. 2-bromo-2-methylpropane heme outlines the prodi The reaction scl Production of one of the m Te eeimpound X. lonomers of nylon 66 KCN reduction compound X 7 Sihanol” NCCH,CH,CH,CH,CN HANCH NH, Which compound could be X? a. BrCH,CH,CH,CH,Br b. CHy=CHCH=CH, cc. HOCH,CH;CH;CH,0H dd. HO,CCH,CH,CH,CH,CO,H urnt sugar has two functional groups indicated by Q and R. a . R CH: €CHOY When this compound is tested in a laboratory with 2,4-dinitrophenylhydrazine and Fehling’s reagent, which functional groups are responsible for positive tests? a GandR Ronly QandR Gana R only Qonly Rony Ethanal may be converted into a three-carbon acid in a two-step process. Which compound is the intermediate? a. CH,CO;,H b. CH,CN c, CH,CH,CN d. CH,CH(OH)CN Consider the sequence of reactions. step! step It step Ill CH,CH,OH ——® CH,CHO ——® CH,CH(OH)CH,CHO ——® CH,=CHCH=CH, bute-1,3-diene Which term could be used to describe step I? a. condensation b. dehydration ¢. dehydrogenation d. hydrogenation(vil) Which compound reacts with its own oxidation product (an oxid . involves no loss of carbon) to give a sweet-smelling liquid? tion Which a. propanal b. propanoic acid ¢. propanone d. propan-1-ol (Vili) Butanedioic acid may be synthesised in two steps from 1,2-dibromoethane _step1 step 2 BrCH,cH,Br Pt x _Step2 2CCH.CH.CO,1, Which reagents could be used for this synthesis? step 1 step 2 A HCN(g) HCI(aq) B HCO2Na(aq) HCI(aq) c KCN(aq/alcoholic) H2SO,(aq) D NaOH(aq) [icenssineeeaters (ix) Y and Z are two widely-used selective weed killers, HCO. HZCH.OH o* cx cr . cu ¥ z Which reagent will distinguish Y from 22 a. acidified AgNO3(aq) b. Fehling’s solution c.Na d. NaxCO,(aq) (x) Tartaric acid is present in some wines. It may be synthesised in the laboratory in two steps. step 1 step 2 OHCCHO ———-+ intermediate HO.CCH(OH)CH(OH)CO,H tartaric acid Which reagents could be used for this synthesis? = step 1 step 2 A HCI(aq) HCN(g) B HCN, NaCN(aq/aicoholic) H2S0.(aq) c H2SO,(aq) K2Cr207/H2S0.(aq) SD KCN(aq/aicoholic) K2Cr207/H2S0.(aq)ganic compounds have been identified or! in the mandibular foul 2d to this behaviour. The structures of th relal 'ese molecules are glands of ants, and are as follows, ° CHYCH,), Nome Meh . H =C CH.CH,CH.cHcH.o~ : n,cH,0#0H CHYCH,),CcH,cH, Ho ‘ OHHH, No B A cl id a D jne a series of chemical tests, with the observations, to distinguish each compound ot) from the others. les of the following compounds were labelled A to Eas shown, amp! en CH CHOH CH,CH.CHOH)CH, C cHcHo a cH,COCH E CH,CH-cHcH, , ete the table below by inserting the letter (or letters) of the compounds that corespond to each test. reagent observation _|__letter(s) dified potassium Green colour obtained acl iciornate( V1) on boiling cai Ytassium ethanoic acid obtained acidified stecv it) on boiling in the presence SOT im catahyet hydrogen absorbed of a plat atyst | ro | rown-red precipitate Fehling’s reagent obtained on boiling 2,4-dinitrophenylhydrazine orange precipitate =) jt bromine in an inert solution decolourised solvent | 14, Compound G, in which R- represents the rest of the molecule, was Made for use as a tear gas in World War 2. x LA R—cG—cn Br compound G Compound G was made by the following sequence of reactions. ! ii} RH, “80°1 pcu,cr Stage R-CH,cn $1898 R-CHBrCN(vil) Which compound reacts with its own oxidation product involves no loss of carbon) to give a sweet-smelling liquid? (an oxidation Which a. propanal b. propanoic acid ¢. propanone d. propan-1-ol (Vii) Butanedioic acid may be synthesised in two steps from 1,2-dibromoethane. stop 1 step 2 X =" HO;CCH,CHCO. Which reagents could be used for this synthesis? BrCH,CH,8r step 1 step 2 A HCN(g) HCi(aq) B HCO2Na(aq) HCI(aq) © | KCN(aq/alconolic) H2SOx(aq) Dd NaOH(eq) KeCr207/H2S0,(aq) | (ix) Y and Z are two widely-used selective weed killers, COW OCH,CH,OH ‘CH, ‘cr co a Y z Which reagent will distinguish Y from Z? a, acidified AgNOs(aq) b. Fehling’s solution c.Na d, NaxCOs(aq) (x) Tartaric acid is present in some wines. It may be synthesised in the laboratory in two steps. step 1 step2 OHCCHO ————> intermediate ————» HO,CCH(OH)CH(OH)CO.H tartaric acid Which reagents could be used for this synthesis? stop 7 stop 2 A HCi(aq) HCN(g) B | HCN, NaCN(aq/aicohotic) H2S0.(aq) c H2SO.(aq) KCr207/ H2S0.(9q) D KCN(ea/alcohotic) K2Cr2O7/ H2SO.(2q)Po organic compounds have been identified in the mandibular glands of ants, and are ie ed €0 this behaviour. The structures of these molecules are as follows. + ela e 9 | OH cH,cH.CH CH,(CH,),CCH,CH, ac ‘ B CCH. (CH,CH, 4 = i yon A CH,CH,CH,CH,CH,CC N, ° c D tine a series of chemical tests, with the observations, to distinguish each compound (ato p) from the others. samples of the following compounds were labelled A to E as shown. CHjCH,CH,OH B CH,CH,CH(OH)CH, c CH;CHO CH,COCH, E —— CH,CH=CHCH, complete the table below by inserting the letter (or letters) of the compounds that. correspond to each test. reagent ‘observation letters) | Geidified potassium green colour obtained ‘dichromate(V1) on boiling galdified potassium ethanoic acid obtained manganate(VII) on boiling n in the presence es ‘platinum catalyst hydrogen absorbed = brown-red precipitate Fehling’s reagent obtained on boiling | 2,4-dinitrophenylhydrazine orange precipitate | bromine in an inert Sélition decclourt Compound G, in which R- represents the rest of the molecule, was made for use as a tear gas in World War 2. . . H R—C—CN Br compound G Compound G was made by the following sequence of reactions. stage | stage Il AcH, 280°! cror 89°", a cron 229° p_cHBrcN(2) Suggest reagents for each step. (©) Consider the following sequence of reactions. R-cHercn 529° Na cHprco,t 298 R-cHoHco,s4 stage VI FACH,co,4 Suggest reagents for each step from jv to vi. (2) Ethanol may be converted into propanoic acid in a three-stage process which ues ethanol as the only organic compound. C,H,OH Sl eel | stopil C,H,CO,H (© Give the structural formulae of the intermediate compounds K and L, (ii) Suggest reagents for each step. Lactic acid, 2-hydroxypropanoic acid, CHsCH(OHJCOxH, occurs in sour milk. Glycolic acid, 2-hydroxyethanoic acid, HOCH:CO:H, occurs in sugar cane, (@) Lactic acid may be synthesized from propene. Write down the steps involved jn this synthesis. (b) Convert glycoltic acid to ethanoic acid. Outline steps of sequence used to synthesis ethanoic acid from methanol, (2) __ Complete the following reaction scheme which starts with 1-bromobutane, In each empty box, write the structural formula of the organic compound that would be formed. CHaCHCH.CH.Br NaOH(eq)Keatunder heat undo?\N@OH in ethanot w x pune : cone. KMnO, ‘Selangor heat unde’ eho roth = z (b) One of the compounds W, x, Y or Z can be polymerized. Identify this compound by its letter.vesign # chart to sho the following conversion. Write down the nam 8 synthesis also write type of reaction in each case. etre ——> CH,CH(OH)CN r i agents used in the ( cH,cOOH .) CHCH:CHaCHs, ————®CHsCH,CH(Br)CH, ed CHCHIOH)CH, ———CH,CH=CH, @ CH CH=CHs ——> CH,CH(OH)CH,OH o -1-ene, CH: i= : sat nace ntiseonens compare and contrast between synthesis and retrosynthesis. w functional groups interconversion in organic chemistry.