F.6 Chemistry the | chemistry learning centre in HK Oey | Ne se Topic 11 (Part 5) Chemistry of Carbon Compounds 11.9 Alkanoic Acids / Carboxylic Acids 11.10 Esters and Amides } 11.11 Amines Scanned with CamScannerGeneral formula Alkane RH ic [CoHaneay N22] Haloalkanes RX (X= halogen =, Cl, Br or I) [CoHanaX, m2 1] ca Alkene RCH=CH2 / RCH=CHR / R:C=CHR / RzC=CRp Xf [GHan n> 2] ee Aromatic Ar-H /Ar-R <)> hydrocarbon (ar= benzene ring) [benzene ring] Alcohol R-OH -on ellenot [GHayeiOH, n>} Inydroxyt group] Aldehyde a Jalkanal Bret [CuHznsCHO, n> 0} Ketone q /alkanone fo [CatHamesxCOC Hansa, m and n> 1) [carbonyl / ketone group] Carb id tl {bono cee —ton acl [CaHanexCOOH, n> 0} [carboxyl group] Oo i 1 Ester R—C—O-R" — [CmHzmetCOOC Hansa, M =O and n> 1] [ester group] 1 1 Amide R—C—NH, —C—NH, [CoHaaCONH2, n 2 0] [amide group) ne RNH2 -NH, i [CaHanesNH2, n> 1) [amino group / amine group] Scanned with CamScannerForm6 Topic 11: Chemistry of Carbon Compounds (Part 5] ehemisky Ueaming Contre | 9g 11.9 Alkan 11.9.1 Introduction to carboxylic acids Acids / Carboxylic Acids Carboxylic acids are organic compounds containing carboxyl group —-C—OH « Hic rs from that of alcohols, ketones and aldel B 9 s i] General structural formula of carboxylic acids: R—C—OH where R= H, alkyl ora benzene ring = Examples: | 9 9 I I CHaCH2CHsCOOH H—C—oH methanoic acid butanoic acid ‘CHsCHBrCH,COOH (CHaBrCHBrCH,COOH | a 3-chloropropanoic acid 3-bromobutanoic acid 3,4-dibromobutanoie acid as ao Subeditu ent fi anc Co. cH,COOH = 2 FN, | —OH } Eaaeacian H epcloheranecarbonplicacid cyclohexylethanoic acid (Dien sence acid G.Tsang@Element Scanned with CamScanner=. HO—C—c—ou HO—C—CH,CH,—C—OH J ethangioic acid torhege butarfetioie acid cis-bu@Qebioicacia oR AY tis 14 COOH at “Gis: benzoic acid 1, A-dicarbonyic ack aad Denzoic aci ae 1,4-dicarboxylic acid phenylethanoic Sr iwayle vn ld eat a coon Br cooH a : 4-aminobenzoic acid 2-chlorobenzoic acid 5-bromo-2-chlorobenzoic acid Ez Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner11.9.2 Physical properties of carboxylic acids mop. | bp. | Density at20"C Solubility Alcohols Formula to | ro) (gcm’) (g per 100¢H20) Methanoic acid HCO2H a4 | 101 1.220 ° Ethanoie acid CHsCOH 16.6 | 118 1.049 © Propanoic acid CHsCH:COsH -20.8 | 141 0.992 ° Butanoic acid CHy(CH2):COH | -65 | 164 0.964 ° Pentanoic acid CHy(CH»sCOH | -34.5 | 186 0.939 497 Hexanoic acid cHs(CHyCOH | 15 | 205 0.927 1.08 Heptanoic acid CHyCH)sCOH | -75 | 223 os18 0.24 Octanoic acid chs(cH\eco2H | 16.7 | 240 0.910 0.068 Nonanoic acid CHs(CHaCOH | 125 | 254 0.900 0.028 Decanoic acid CHs(CHaCOoH | 31.6 | 269 0.893, 0.015 Benzoic acid CeHsCO2H 122 | 249 | 1.32 (solid) 0.34 ‘At 25°C and 1 atm, carboxylic acids with no. of Catoms < 10 are bide!" of “) Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerForm6 Topic 11: Chemistry of Carbon Compounds (Part 5) Extensive H-bonds 2 aldehydes Maton anger : Polar, stronger van der Waals’ forces 8 Non-polar, weaker van der Waals’ forces Boiling point (°C) ° 4 3 Number of carbon atoms p.and m.p. than other class of organic compounds (e.8. alkanes, alkenes, haloalkanes, alcohols, ketone and aldehydes) with 4 Due to the formation of extensive intermolecular ‘H-bonds, RCOOH has higher b.f | similar / same no. of C atoms. Chemistry of Carbon Compounds (Part 5) G.Tsang@Element — Scanned with CamScannerTopic 11: Chemistry of Carbon Compounds (Part 5) ‘Chemisty ening Conte Although H-bonds exist between ROH (alcohol) molecules, RCOOH molecules form more extensive intermolecular H-bonds (RCOOH has 1 more electronegative O atom than ROH) => RCOOH has higher b.p. and m.p. than ROH with similar / same no. of C atoms : eee pact 4 pt4 mi lar dispersion fnCe, ar ‘Compounds Relative molecularmass | map. be, CH3sCH2CH2OH, propan-1-ol 60 ale 97 CHsCH(OH)CHs, propan-2-ol 60 “89 82 CH:COOH, ethanoic acid 60 Asno.of Catomsin RCOOH fl => m.p.andb.p. Tt { H-bond TH -bewd +: no. ofCatoms fl => molecular size fl permeleale Per Mrleoe Den 4 mention H-boud | > ven de? Wan ares between molecules Ez Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanneree ee Form6 Topic 11: Chemistry of Carbon Compounds [Part 5) Bercise “rhure Wefoed yer maluwle aren N-> pf deve shan WHS stinger Hobo’ (4) Which one has a higher b.p.(CHsCONH: (3mide) or CHsCOOH? Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanneriN + RCOOH with small no. of C atbms(1 to 6 C atoms) formation of H-bonds with water molecules ies in water J 4 Asthe no, of Catoms in the RCOOH molecules + => _solubil the effect of the non-polar hydrocarbon chain become more and more significant AD sz] + Aromatic carhonylc aids (e.g. benzoic acid / CeHsCOOH) are insoluble in cold water. + All RCOOH are ‘soluble’ in NaOH(aq), Na2CO2(aq) and NaHCOs(aq) due to the formation A | watersoluble RCOONA'. Ai) xt salt csuluble 1M Hd coo 24, C6ONa, “ty (s) t+ WagH&) (NY (ag) + Bote sa 4 AIL RCOOH are soluble in common organic solvents, e.g. alcohols, ethers, Cle and CHCl. Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner| DAM AMM caster — RCOOH tends to form! pure form, in non-polar solvents (e.g. benzene and CCls) and in vapour state, in which two H-bonds are formed between two carboxyl groups. Intermolecular H-bonds between 2 RCOOH molecules = formation of adimer Exercise Given: Relative molecular moss of CHsCOOH = 60.0; Boiling point of CHsCOOH = 120°C Explain why the observed relative molecular masses of CHsCOOH are 120 at 120°C and 60 at 400°C. 4oo°C : l-bewds ate beken, no dimer=7 RAMS muasured RM AY 256 ) zgome ak thes form dimer | Chemistry of Carbon Compounds (Part 5) G.Tsang@Element | Scanned with CamScannerTopic 11: Chemistry of Chemisty Learning Gone 11.9.3 Preparation of carboxylic acids (xT 2°) 1 tion of 1° alcohols and aldehydes} ( \V 7 [Xfou¢ ) + 1 alcohols (NOT 2° and 3° alcohols) and aldehydes can be oxidized to RCOOH by heating under reflux with an oxidizing agent. +4 Mn O21) brow a or, t 4. RH. OH EE a" (00 (1) KMnO«/ H* (or KMnOs/ OH followed by acidification with HCl) fcllowesl by acistication with HC) Common oxidizing agents used: (2) KaCraOr/ H"{or NayCr2O>/ H*) er To kMno/#t f jn pt on Sr gt oy R—C—0H ———* + R—C—o# T reflux i reflux H H ° ° ° i K,Cr,0, / HY i i KMIn0, / HY 1 RCH ET p—c—on RCH RCo reflux reflux = Examples: H ° cto OO oy dt ow sri reflux ? H ° ° 1 _KMnd,/H* i cH C—O# reflux Ei Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner= Form6 Topic 11: Chemistry of Carbon Compounds (Part 5) 2. Hydrolysis of esters ° r oO . i a" i Acid hydrolysis: R—C—O—R’ + H,0 === R—C—OH + ROH : f i Alkaline hydrolysis: R—-C—O—R' + NaOH “heat R—C—ONa + R'OH a > Examples: 7 CHy—C—O—CH,CH, + H,0 === CH,COOH + CH,CH,OH heat i i Sa ao Mona + enon heat % Both acid and alkaline hydrolysis of esters can be carried out to synthesize RCOOH (acidification of RCOO ‘is needed for alkaline hydrolysis). + Alkaline hydrolysis is preferred because the reaction is irreversible and achieves a better yield. Ee Chemistry of Garbon Gompounds (Part 5) G.Tsang@Element Scanned with CamScanner3. Hydrolysis of amides i i ‘Acid hydrolysis: R—C—N—H + H,0 ==== R—C—OH + NH, heat H ‘Acid hydrolysis: R— R—C—OH + R'NH,* heat ° ot i] Alkaline hydrolysis: R—C—N—H + on —PE@L» p—C—o' + NHy 9 heat I R—C—O" + R'NH, Alkaline hydrolysis: R- Both acid and alkaline hydrolysis of amides can be carried out to synthesize RCOOH (acidification of RCOO’ is needed for alkaline hydrolysis). EZ Chemistry of Carbon Gompounds (Part 5) G.Tsang@Element Scanned with CamScannera ee | Form6 ‘Topic 11: Chemistry of Carbon Compounds (Part 5) rent enna 11.9.4 Reactions of carboxylic acids [Reaction with reactive mets]_-= K ~~: Carboxylic acids react with reactive metals such as Na and Mg to form the corresponding metal carboxylates and hydrogen gas. > examples: 2CHCOOH + 2Na —~ 2CH;COONs + He 2CHCOOH + Mg —~ (CH:COO):Mg + Hs same f Cougoen? 33 dee ne COOH + 2Na ——» C)pane +, a \a€ coos + Mg ——> (C)—«0o gh + H, satt 2 2. Reaction with metal oxides, metal hydroxides, carbonates and hydrogencarbonates Carboxylic acids react with common bases to form carboxylate salts and water. = examples: CHSCOOH + NaOH —- CH:COONa + H:0 2CHsCOOH + CalOH]2 —- (CHsCOO),Ca + 21:0 fectscoon + FeO; —~ 2(CH:COO);Fe + 34:0 El Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerForm6 Topic 11: Chemistry of Carbon Compounds (Part 5) Carboxylic acids also react with NazCOs(aq) or NaHCOs(aq) to form sodium carboxylates(aq), carbon diovide and water => tests of RCOOH (gas bubbles formation) ?% Examples: 2CHsCOOH + NaxCO, —= 2CH:COONa + COr + tO HCOOH + NaHCO: —~ CHhCOONa + CO, + H,0 3. Formation of ester / RCOOR’ © Condensation is a reaction in which 2 molecules combine to give a larger one with the elimination of 2 small molecule such as H20, NH» and HCl. Ed DH with R’OH to form esters in the presence of an acid (e.g. cons. H2SO« and nc. H3PO4) thre indensation reaction known as esterification. Cotalyst + Seley drorng ay emt o q O of H20 formed comes 7 Lew = ate ii from RCOOH, not R’OH Contensatiou. : S wramples: (NOT Lely drotion) ql 9 9 cons. H,SO, ll Il CH;—C—OH + CH,OH CH;—C—O—CH, + H,0 reflux methyl ethanoate G.Tsang@Element FEI owning crccncnones Scanned with CamScanneroN 9 I cons. H,S0, I —= —O—CH, CH, C—OH + CH;CH,OH === ICHs + H.0 ethyl benzoate cons. HySO, CH,COOH + CH,OH === CH,COOCH, + H,0 reflux methyl cyclopentylethanoate Vield of the reaction can be + by: [Topic 10} © Common acid catalysts: (1) amount of RCOOH/ R’OH used f . (2) cone. HsSOe (2). cone. HsPO« BL SRS cut ees foe “The ester formed can be isolated from the reaction mixture by | 23 | (1) pouring the reaction mixture into NazCOs(aq) or water, followed by separation in a separating funnel (ester is usually insoluble in water except those with low molecular masses, ester = upper layer in the separating funnel) [Part 7] (2), fractionalgistllation [Part 7) RCCL (wowing NOT required im_DSE) Y — RCOCI (acid chlorides) has the same indensation as RCOO! heat is required for its reaction. Y —RCOG is fibre reactive than RCOOH. It aives| (ci) reaction rates oniiaher vied of reaction OF i 25% ral « reteset ; wt esosble, Ez Chemistry of Carbon Compounds (Part 5) G.Tsang@Element — Scanned with CamScannerForm6 Topic 11: Chemistry of Carbon Compounds (Part 5) Predict the structures of the organic products in the following reactions. Se i + 2H eines ——> Afa plasticizer, DEHP) we DEHP: di(2-ethylhexyl) phthalate Ex Qa Hace HHH Ha CH oe 70-CHs ( Wc) CH-CHe CHa CH» CH f Dnc| Ni 9 (2) chon Cy7HygCOOH conc. H,S0, heat) wt CHa-0- Ge Cn Us ne Colles Va -o- 8 Ce Hs HOH + —Cy7H,COOH C (a lipid molecule) CH,OH CysH3 COOH Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner‘Compounds (Part 5) Chemistry of Carbon 7. Formation of amides (RCONH:, RCONHR and RCONR:) COOH react with Nis or (NHal:COs / 1° amine (RNK:) / 2° amine (R'RNH) to give corresponding carboxylate salts at room temperature. ammonia Galt RCOOH+NH3 —= RCOO'NH«’ (neutralization) ane 5 RCOOH + RNH? (1° amine) —~ RCOO'RNH' (neutralization) RCOOH + R:NH (2° amine) —= RCOO'R:NHD* (neutralization) RCOOH 4{R3N (3° amine) |—~ RCOO'RsNH* (neutralization) ro amide tan Ve Louned 4 Upon heating, these carboxylate salts undergo dehydration to give the corresponding amides. RcoonHs ME RCONH: (1° amide) + M20 (50 [me 2 Bi. RCOO'RNH; HE RCONHR (2° amide) + H20 RCOORNH2* NSE RCONR:(3* amide) + H20 heat RCOO'RSNH* no reaction 2HCI + (NH«)2COs —~ 2NH.CI+CO2+H:0 2RCOOH +(NHs):COs —~ 2RCOONHe + CO2 + H20 i heat I _—C—ON'H, 9'———» R—C—NH, + H,0 i heat I RCNA + H,0 i 1 RRM amine) | 1 R—C—08H ———""»! R—C—ON'H,R'R"———» R—C—NR'R" + HO. NH, or (NH,);CO3 RINH,(1° amine) ‘on i! ) carboxylate salts (can be isolated and purified) tonic | Ohemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerea condensation carboxylic ach Cats) oF ken [Note: 3° amines will NOT react with RCOOH to give amides!!!) a oi N 9 ‘No catalyst (e.9. cone. HaSOs I H needed ent, ——e cry En, + Ho | ord core HPO. is reflux {for amide formation. ethanamide (2°) \/ “Hs ° | + Clit ——> cH, CNC, + 4,0 a enathyeth dee) og ; .eethyethanamide Neethyleyclopentylethanamide (2°) cy ° i G2 1 N,N-dimethylbenzamide (3°) Draw the structure of product A formed from the following reaction. ~. 2ol 4 DSE- heat HANCH,CH,CH,COoH —“—»_ycic product A NS Ne acy, *4 So ¢ Th yen CH, la EY Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner™ Chemistry of Carbon Compounds (Part 5) Form6 Topic chemistry Learning Cente 5. Reduction of carboxylic acids A FENT Why LiAlHs is'a powerful reducing agent which can reduces RCOOH to 1° ROH (NOT 2° and 3° ROH). Dry ether must be used as the solvent to dissolve LiAIHs ~ LiAlHs reacts with water. 9 ge Tl A.tiAlHy dryether pig R—C-0H Sg \ 2.430 i 2° aleohol = Examples: | g 1. AIM, dry ether hia Zs a rye Hye | chy C0 FoF i _ OW TH AOF f i \ Aldehydes (RCHO) CANNOT be formed from the reduction of RCOOH!!! | J RA! oily en aptebew of RU GH «)| (HSASEIE! Wing CoQ] Yt (aistilatten) heniiyaf ron Gonpodr Fat Gtiengetiement Scanned with CamScannerForm6 Topic 1 Chemistry of Carbon Compounds [Part 5) Pa) Exam-type questions: } 1 Thyd ati agen (ate Ay a 1. A compound, reacts with ethanol in the presence of concentrated sulphuric &¢id to form a product with 2 fruity smell. Which of the following statements about this compound is/are correct? fen (1) tt can 1iBerS€carbon dioxide from sodium carbonate solution. \/ (2) Itcan decolorize acidified potassium permanganate solution. X, (8) ts aqueous solutionisanelectroMte. / +5 7 mobile. ions t2 con luet A. Glonly ded tty 8. (1)and (2) only € (1)and (3) only D. (1), (2) and (3) Des answer: KU 2. Which of the following statements concerning propan-1-ol is correct? A. isboiling pointisthe same as that of propan2-ol X C_¢_¢ of Shybor Jp B. tis not a conductor of electricity. ee Be If ; “t lure pe 7 i ._Ithasalowerboltingpointthan that of methanol ¢ Cesanwer B = C-C-C Oper b-p “elegy tr molecular size CRs aqueous solution has a pH value greater than 7. X ~1 ¢qy 3. The following is a series of reactions starting from ethanol: Ds tougar v-dow = sehanot TREE, 5 NACE) 6g, AINOT ter, Ht is a sate ‘cH, COOH CH; (00Na (solrum etheonoate ) of the following correctly describes the nature of reagent A and the product Q? ‘Reagent A Product Q dehydrating agent ethene dehydrating agent y{ ethane oxidizing agent } Gs O77 spftum ethanoate A 8. é D.—_onidizing agent, -fthanole acid CO answer: May JH "Ez Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanneroo ™ ae | Form6 — Topic 11: Chemistry of Carbon Compounds (Part 5) ee Fememicheminiy ovsuiyas Lente) it. Ging emg een 7 eae egucan Qe ~ #4 cHtooH 4. A glass of sweet wine i left on a dining table, After two days, the wine beComes sOur. Which of the ving type of reactions accounts for this change? A oxidation deg 8. hydrolysis substitution D. esterification Ce: answer: BR ‘The compound CHsCH(OH)CH:COOCH; is found in marshmallows. Which of the following statements ‘concerning the compound are correct? (1) Its systematic name ethyl 2-hydroxybutanoate. (2) tthas one chiral carbon. (3) Ittums warm acidified K:Cr:07(aq) from orange to green. A. (1)and (2) only B B. (1) and (3) only © Q)and (3) only D. (1), (2) and (3) Az answer: C 6. Refer to the reaction scheme shown below. yah red ea ery substituhien, Step 1 Step2 CH:CH:CH;cHO —P_, cHycH,cH.cH,oH —""P“_ cHacHacH:cHsBr Which of the following reagents can bring about the reaction indicated? Stept Step2 A LAI: ~ ) Br2(aa) a B.A: | NaBr / cone. H:PO: , —V“o__ 5 efi Xe. aged: Brefaq) Fam) HES) ‘oD. K2Cr202 / H30" NaBr / conc. H2SOs A & answer: h Ea Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerForm6 Topic 11: Chemistry of Carbon Compounds (Part 5) ‘An experimental set-up is shown below. wero reflux condenser ee oar-shaped flask ‘reaction minture sntbuneng Lu ‘Which of the following preparations can this set-up be used for? showld we (1) Preparing ethanal from ethanol, sodium dichromate and dilute sulphuric aci LX! J Uti flatid (2) Preparing bromoethane from ethanol, sodium bromide and concentrated phosphor ‘i acid. 7 (3). Preparing 1,2-dibromoethane from ethene and bromi (2) only (2) only (2) and (3) only {2) and (3) only a 25 Answer: B x Sho hats needed poe EEL Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerg 11.10 Esters and Amides 11,10.1 Introduction to esters and amides Both esters and amides are derivatives of carboxylic acids (can be formed from carboxylic acids). + Functional group of an ester: ° I fest epatees > Examples: ° H HO How HO CH H i] I 1 1 Io Il H—C—o—C—H HOC C—O HOH | i re | Tal 4 Hq HOH H HOH methyl methanoate ethyl ethanoate -methylethy| ethanoate 9 ° | i} C—O—CHy cH, —c—o} gt BOR, ROAM PERE, atehy?e - Phenyl ethanoate > (Cae \with a small no. of C atoms are flammable. + rs leasant, ond fruity smells. ‘The flavours and fragrances of many fruits and flowers are due to a mixture of natural esters. + _ Esters have many uses: (1) Perfumes, cosmetics, many foods and drinks contain esters made by chemists. (2) Esters are good solvents for many organic compounds (e.g. nail varnish remover and whitebo2"¢ marker pens may contain ethyl ethanoate 2s a solvent). istry of Carbon Compo (eer 5) G.Tsang@Element — Scanned with CamScannerFunctional group of an amide: > Examples: tf if wh NH io CH, a namide (_|° ) chloroethanamide ( |? ) 11.10.2 Physical properties of esters and amides There are no H-bonds between ester: mobs (no H atom bonded to electronegative O atom) B => carboxylic acids (RCOOH) have higher b.p. than esters with the same no. of C atoms “presence of intermolecular H-bonds between RCOOH molecules ‘Van der Waals’ force between ester molecules ; a—C—o— R—c—o—#’ | Hdohd per maleate, ‘® _Lamides have higher b.p. than carboxylic acids with the same no. of C atoms ‘5 2 H-bonds per molecule for 1° RCONH: Vs _1H-bond per molecule for RCOOH Scanned with CamScanneroo Relative Name rr Bolling point (°C) pore molecular mass ol Ethanol 0 us (ft anoic acid HCOOH 6 onde Methyl methanoate HCOOCHs 60 32 ne A-yed Ethanamide CHsCONH: 59 rai zy a wales Relative Name Formula Boiling point (°C) molecular mass Propanoic acid CHsCH2COOH 74 44 Ethyl methanoate HCOOCH2CHs 74 at B Methyl ethanoate CHaCOOCHs 74 7 Propanamide CHsCH:CONH: 2B 23 + Esters with small no. of C atoms (e.g. methyl methanoate and ethyl methanoate) can form H-bonds with H20 molecules weep 211) = they are miscible with wate 4 I i—¢ HC, % ‘o—chs 0—CH,CH, 22) Mork eters ate immrdtle with WO Esters with larger no. of C atoms are immiscible with water as the effect of the non-polar hydrocarbon chain become significant > shee imme th weer ng fon wens very important) (£2!!!) Eg Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerCH=CH, compound ally ethavoate VS H2d les polar polar Answer: Compound Xi: @ non-polar compound which con dlssolve ina relatively non-polar organic solvent like ‘ethyl ethanoate. However, water is @ polar solvent. [1M] Or ‘Both compound X and ethyl ethanoate are relatively non-polar compounds. Their molecules are attracted by weak intermolecular forces / van der Waals forces. (1M) Note: In order to dissolve compound X in ethyl ethanoate, the followine esses will occur: (1) Break (absorb energy) eal ay ved. V-3 MW. 7 compound X--- mpound X “AND ‘ethyl ethanoate -. ‘ethyl ethanoate (2) Form (release. ae ebew ethyl ethanoate compound X-~ Energy absorption = Energy release => soluble Inorder to dissolve compound X in water, the following two processes will occur: (1) Break (absorb ee a wae 2004 Uo 4 compound X------ compound X AND —water~—~— water (2), orm (release energy) weal vow compound X------ water Energy absorption > Energy release => insoluble / less soluble BB roricns & Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerhemsirycearing Cente @ 1° amides and 2° amides with small no. of C atoms are soluble in water formation of a large amount of H-bonds with water molecules + 3° amides are only slightly soluble in water “y steric hindrance + absence of H atom attached to an electronegative atom = only form a very small no. of H-bonds with water molecules + Amides with larger no. of C atoms are insoluble in water as the effect of the non-polar hydrocarbon chain become significant Ee Chemistry of Carbon Compounds (Part 5) G.Tsang@Element i — Scanned with CamScanner41.10.3 Preparation of esters and amides RCOOH react with R’OH to form esters in the presence of an acid catalyst (conc. HiSO« / conc. HsPOs) through a condensation reaction => slow, may be low yield condensation q conc.H,S0, ica ae L.@ C reflux 4 RCOCI (acid chloride} more reactive than RCOOH, formed from the reaction between RCOOH and Pls / PCls / SOCh) can be used instead of RCOOH => fastand usuall i ass | edsyse 1 v ro 2 sec asunsotion o a ‘ 2 lg a C® gore adel 4° RCOOH react with NH3 / 1° amine (RNHz) / 2° mine (FRNA) to give corresponding carboxylate salts at room temperature. Upon heating, these carboxylate salts undergo dehydration to give the ardensatio w corresponding amides. a ‘ i noon emits) eto nine at nae + H,0 i jm) poy RR NH|22 amine) neat gO" + H,0 carboxylate salts {can be isolated and purified) ‘Ey Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner——__ RCO react with NHs / 1° amine (RNH:) / 2° amine (R'RNH) to give the corresponding amides at a mild condition and at afasterrate => better xersengrtied) mm, 2SC Gf RINH,(1° amine) I q Rtg SE pce’ eH { ance } ° 9 I cy RBTNH(2® amine) I R—C—NR'R” + HC + HO ° ° Il conc. H,SO, i] OH + HO—CH_CHCH, — C—O—CH,CH,CH, + H,0 eat ° 9 i] ll C)-ta + HO—CH,CH,cHs ————> —o—ci,cH,cH, + HCI Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerForm6 Topic 11: Chemistry of Carbon Compounds (Part 5) ymides at a mild amide Pamide 3° amide CH, + H,0 CH, + HCl ay hi 40 i P= ' I I Be cy, a ay ete ed ee : ' I I : a i] 4 C—Cl + (CH,),NH = —— -C—N(CH3), + HCI Chemistry of Garbon Compounds G.Tsang@Element Scanned with CamScanner11.10.4 Reactions of esters and amides Hydrol of esters (very very important) ++ Esterification is a reversible reaction: 9° esterification hydrolysis R—C—OH + R'-OH > _anester can react with water to form R-COOH and R’'-OH + The reaction between an ester and water is always slow => an acid / an alkali is usually added to speed up the reaction [PF =tatalyst 9 = veaclanly goth 05) => acid hydrolysis 7 alkaline hydrolysis = Sod bydrohisia/ alkaline ly . 1 B NOT aadve bydeelyns ny nee te aloe Catal ot 9 1 > Acid hydrolysis: poe + HO & R oh, Be = Examples: 9! e TT wre: aad \ = .—C—-0—CH, CH: H,0 (CH;COOH + CH;CH,OH CHT EEO as + HO hy icy Oo Oo I Ww I C—O—CH, + 4,0 == C—OH + CH;OH heat ° fe) I Ht Il ‘C—0- *1Oo — ‘—OH + HO: heat Ei Chemistry of Carbon Compounds (Part 5) G.Tsang@Element ] Scanned with CamScannerNement Feperiniy veering corre Cail meter exons MaGill is used TR DE newesinle. | solt( sodium othauente, Alkaline hydrolysis: SS = [sts common ein alkaline hydrolysis: NaOH(aq) and KOH(aq) = Examples: a $naed airs fou =e + HocHacAy Sf O—CH,CH, + NaOH Sart CHy—C—ONa + CH,CH,OH Ds bl 9 ao Lane heat 31 i ‘o> —{ ) + NaOH (phon + wt ) ester call reacted (whew 0 H™= acess? 4 Alkaline hydrolysis always goes to completion as RCOOH formed is immediately removed by reaction with OH" => equilibrium position of the first reaction goes to right [Topic 10] = alkaline hydrolysis is always faster and gives higher yield than acid-catalyzed hydrolysis, OOH + CH,CH,OH i cH; —C—o—CH,CH, + a tea & 4Co0n + ol —* ch,coo + jhe => RCOO’ formed can be converted to RCOOH by acidification using HCl(aq) or HSO.(aq): RCOO' + Ht ——> RCOOH Rodda + HC] > Reo0 Ht NaC | Ey Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner“= Form6 Topic 11: Chemistry of Carbon Compounds (Part 5) ee Fors] spon. Gg @ omen ire Leamalagyeantye R—C—OH + HONH, 9 ql R—C—OH + R’—NH, CNR + H,0 an amide can react with water to form RCOOH and NH; (or an amine) ‘The reaction between an amide and water is always slow => an acid /an alkalis usually added to speed up the reaction | B = cid hydrotyais / alictine hydrofsis_ | Electron diagram of NH \ |. (showing outermost shell Scanned with CamScanner° Ht I i a C—OH + CH;NHy heat Ht i] 4 ees C—OH + HN heat Alkaline hydrolysis: ul we R=C-O + WH; Bi ojH R—CNTH + OF > R—C—0" + NH “OH | H- It heat “ R—C—N—R' + OH ———= R—C—O" + R'—NH, | Alkalis commonly used in alkaline hydrolysis: NaOH(aq) and KOH(aq) = Examples: 9 I heat chy ——wH, + Nao US cHcoone + Ni, ° I _heat chy a eked + OH ———* CH;COO" + CH,CH,NH, 4 EEL Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerForm6 Topic 11: Chemistry of Carbon Compounds (Part 5) t ie f (\ N + Kon (\ + HW 1. Draw the products of alkaline hydrolysis of the following compounds. @) ; ° cH, D0 ot ) 7 ito tt a tance Elna tharda ' Mi to ‘OH i xt an Hs N-Cla-c-0™ Hew CHC -O" YN-CL—S-0° 1 L cH. la, {| 2. Consider the following four-step conversion: | PCle(s) NH,(g) NaOH(aq) HClaq) | AlCHeO,) Sle 8 — Ee ¢ MONG Tom AlCaHe03) 9 r » g cach oy CCC Cet nn, COCO C-G-08 What are the structures of compound A, B, Cand D? | El Chemistry of Carbon Compounds (Part 5) G.Tsang@Element J Scanned with CamScanner4, Anester with an odour of banana has the falo structural emi cecicunen, o q ' “a ie ba, cates ced In which of the following pairs will the substances react together to oa this at A. CHYCHACHCH,COOH+cHOH 8. cH,COOH + ¢H,cH,CHCH,OH x chy . CH;CHCH,COOH + CH;CH,OH D. —CH,COOH + CH,CHCH,CH,OH Gi re CH; Cz answer: CH; B 2... Consider the following three-step conversion: crc 2 conpous AAP comppund s zac compound ¢ CHhgCHEHs pou AT mppund 8 “Cone HiSO,, heat elect, wt-e-tls W-C-C-CH; We, cH Which of the following’ the stluetufeof product cz Y oH Weeet- “0G Hy e A. (CHsCHCOOCHs B. CH;COOCH(CHs), wcdyetyl Vahow et © CHSCHsCHyCOOCHs D. —_CHsCOOCH:CHaCHs Bz answer: g EL ‘Chemistry of Garbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner= (Form6 Topic 11: Chemistry of Carbon Compounds (Part 5) a Tenge Tensmcnenbsiep eamalng-eenize, 9 11.11 Amines 11.11.1 Introduction to amines ‘© According to the number of ally! groups directly bonded to the nitrogen atom, amines can be lassified as 1°, 2° and 3%. secondary amine (2°) tertiary amine (3°) Bamples: 4 RH H # | bo | ae ae am 4 (CHSCH:CH:CHNH: Poe HOH HONK # methanamine (2°) buten-1-amine (2°) butan-2-amine (2°) CH.CANH, NH, NHCH, CHCH,CH,—N—CH,CH, CAG CHC, 4 Neth ine (2°) Neti aerine (2°) H-methyiphenylomine/ ‘A-methylaminebensene (2°) Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner4141.2. Physical properties of amines ‘s pue to the presence of N-H bonds in 1° and 2° amines, H-bonds. amines can form intermolecular intermolecular H-bonds c-Ne amines CANNOT form H-bonds with each other due tothe absence of H bonded to N- 18 and 2° amines (with intermolecular H-bonds) have higher b.p. than alkanes and alkenes (with vany der Waals’ forces only) with the same no. of C atoms. 4 1° amines have lower b.p. than alcohols with the same no. of C atoms. +: Oismore electronegative than N => stronger H-bonds are formed between alcohol molecules bp: RCOOH > ROH > RNHz > alkanes, alkenes EE Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerForm6 Topic oo? Chemistry of Carbon Compounds (Part 5) e ( ? samme Explain the difference in boiling points for the following compounds. ‘Compounds Bolling Point (°C) HCH yw “88 CH3NH2 ) 6 cHhOH { H-bond 65 HCOOH J 100 2 £s solution: ; a! CHsCHs is a non-polar compound. In pure liquid form, Ct1sCHs molecules are held together by weak van der Waals’ forces. However, with H atoms bonded to fighi)) electronegative O and N atoms, CHaNHs, CHOH and HCOOH can form strong intermolecular H-bonds (in addition to van der Waals’ forces). CHsCHs has the lowest boiling point. Qewore $7, theworegt is more electronegative than N / O-H bond is more polarized than N-H bond. CHsOH can form stronger intermolecular H-bonds than CHsNH. Thus, CHsOH has a higher boiling point than CHaNH. Due to the presence of an additional 0 atom, HCOOH can form mor¢ extensive intermolecular H-bonds than CH3OH. Thus, HCOOH has a higher boiling point than CH30H. 7 RH B-U-H A-C~O-H 4 up oh WS Ay ae 7 ‘FD ytend vag! Holand qa ban ay, ees "FREE tents croctesccaranar G.Tsang@Element Scanned with CamScanner‘4 pve to the absence of H-bonds between molecules, 3° amines have lower b.p. than 1° and 2° amines with the same no. of C atoms. Example: id na Y bout Pi on ‘Compound CHaCH2CHaNHs(29) CHsCHaHH|CHs (2°) (CH)3N (3°) Bolling point. 49ec 35°C 3°C ‘amines have lower b.p. than structural isomeric 1° amines ~- (2) 1% amines have 1 more H atom bonded to the Natom => more extensive H-bonds (2) the steric hindrance of an additional alky! group on N atom in 2° amines prevent the formation of more H-bonds /|* amine: were [tutar =p mere ective it formieg W-toud 2 lager sufare oven > Example: Bi _ Compound (CH3CH2CH2CH2NH? (1°) (CH3CH2NHCH2CH (2°) Bolling point 78°C 55°C a N \ 4 Pan eo cee VL “C, Tower 5 t hier one roe volte ethononingr ethonomie? “Coney, 2H ids cc N 4 | | bond ei EE Chemistry of Carbon Compounds (Part 5) G.Tsang@Element PE Eases eS ae ea Scanned with CamScannerChemisty Learning Cente * 1®and 2° amines can form intermolecular H-bonds with water molecules = and 2° amines with small no. of C atoms are very soluble in water Solubility in water: 1° amine > 2° amine > 3° amine (with the same no. of C atoms) «> 2° amine has more N-H bonds => more Hbonds with water. => more soluble | | 0] 3° amine has no N-H bonds => bonds with water => less soluble + All amines are ‘soluble’ in acids ~ formation of water-soluble salts. NH + HCl(aq) —~ NH.*Ct(aq) RNH2 + HCl(aq) —~ RNH;‘CI(aq) RNH + HClaq) —= RiNH‘CtI(aq) RN + HCl{aq) —~ RsNH‘CI(aq) A vey of lower molecular masses have characteristic ‘ammonia’ smell while larger amines have (teeva! 1) \ EE Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScannerForm6 Topic 11: Chemistry of Carbon Compounds (Part 5) suit Reactions of amines cation with water | = 1o ization “e-_Amines with up to 6 Catoms are soluble in water and give an alkaline solution (pH > 7 ¢ ie ee tolaq) +H20(l) = NH'(aq) + OF (aa) \ RNH2(aq)\ H20(l) === RNH3"(aq) + (aq) \ R.NH(aq) + H20(!) === ReNH2"(aq) + OF (aq) OH (aq) & Allamines are ‘soluble’ in acids (e.g, HCI) to give water-soluble salts. Hs + HCl{aq) —~ NHe'CH(aq) RNH2 + HCl(aq) ——~ RNH;"CI(aq) RaNH + HCl(ag) —~ RaNH,*CI(aq) RN + HCl{aq) —~ RaNH*Cr(aq) EL Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner3, Reaction with carboxylic acids / acid chlorides % RCOOH / RCOCI react with NHs / 1° amine (RNHL) / 2° amine (R'RNH) to give amides. N 1 heat( conbeusation ) 9 9 il 1 ~\, 1 R—C—on ——“s tony, Pe —tnn, + H,0 ° Woy INH (2° ami i he 1 R—C—on AMP amined orga Peak pt NaR + H,0 To RR NH(2® ami i i R—C—on SENN amine town wen Pek pone" + 4,0 {ids WE 7 q R-c—al R-C—NH, + HCl) ° ° } i RINH,(1° ami 1 ja RocH RNHa(1° amine) | R—C—NHR' + Hel { we é \ i 'RYNH(2° ami i } aot RRNRP amine) nea + Hel 7 Load Chemistry of Carbon Compounds (Part 5) G.Tsang@Element Scanned with CamScanner(2) How many functional groups are there in X? Name all ofthese functional groups. {b). Write the structures of carbon compounds formed when X is heated with excess sodium hydroxide solution. De solution: {a}. There are 4 functional groups in X: (1) carbon-carbon double bond; (2) amine group; (3) amide group; and (4). ester group. al gle. ee A (b) Q Nona (CHCOONa CHsCHOH NH NH Er Chemistry of Carbon Compounds (Part 5) G.Tsang@Element bE Scanned with CamScanner