Bene Raffles Institution Year 6 H2 Chemistry 2018 Lecture Notes 16 — Carbonyl Compounds. Lecturers: Ms Jacinta Lim & ‘Mrs Goh Juan Juan Learning Objectives Candidates should be able to (@) describe the formation of aldehydes and ketones from, and their reduction to, primary and secondary alcohols respectively. (b) describe the mechanism of the nucleophilic addition reactions of hydrogen cyanide with aldehydes and ketones. (c) Explain the difference in reactivity between carbonyl compounds and alkenes towards nucleophilic reagents such as lithium aluminium hydride and hydrogen cyanide. (d) describe the use of 2,4-dinitrophenylhydrazine (2,4-DNPH) to detect the presence of carbonyl compounds. (e) deduce the nature (aldehyde or ketone) of an unknown carbonyl compound from the results of simple tests (i.e, Fehling’s and Tollens’ reagents; ease of oxidation). (f) Deduce the presence of a CHsCO- group in a carbonyl compound from its reaction with alkaline ‘aqueous iodine to form tr-iodomethane References Understanding Advanced Organic and Analytical Chemistry by Kim Seng Chan & Jeanne Tan. Chemistry in Context by G. C. Hill & J. S. Holman ‘A Level Chemistry by E. N. Ramsden Organic Chemistry by John McMurry Contents 4. Introduction 2 2. Nomenclature... 3 3. Physical properties 4 3.1 Melting and boiling points. 4 3.2 Solubility 4 4. Preparation methods for carbonyl compounds... 5 4.1 Oxidation of alcohols. 8 4.2 Oxidation of alkenes... 6 4.3 Electrophilic substitution of benzene. 6 5. Chemical properties of carbonyl compounds ... 7 5.1 Relative reactivities of carbonyl compounds towards nucleophilic attack. 8 5.2 Formation of cyanohydrins — Nucleophilic additon........ : 8 5.2.1 Nucleophilic addition mechanism... a 9 5.2.2 Stereochemistry of addition products. 12 5.2.3 Difference in react between carbonyl compounds and alkenes towards nucleophiles 2 5.3 Hydrolysis and reduction of cyanohydrins. 5.4 Formation of alcohols - Reduction 5.5 Condensation reaction 5.6 Formation of carboxylic acids -Oxidation 5.7 Formation of carboxylate salts using Tollens’ Reagent 5.8 Formation of carboxylate salts using Fehiing’s Soiution....... 5.9 Formation of tr-iodomethane (iodoform)... Reactivity of aromatic carbonyl compounds... = Summary of reactions with oxidising and reducing agents in Organic Chemistry ‘Summary of distinguishing tests. cara ‘i ‘Summary of reactions. 6. 7. 8. 9. Page 1 of 224 Introduction 44 Examples of Naturally Occurring Carbonyl Compounds Ow! Oxy, HCHCHO cts on : cinnamaldehyde [Link] benzaldehyde vantin (oeweramondovertac) ——qvantfavourngy OT PeMAropenal__ (cooked mses) ‘ih cinnamon) 42 Carbonyl Compounds — Aldehydes & Ketones \ C=O Carbonyl Functional Group aldehyde ketone % Compounds with the general & Compounds with the generat formula RCHO where -CHO is formyla RCOR’. R and R’may termed the aldehyde group. R may be analkyl or aryl group Be Hi elky! of any! group, Have two alkyl or aryl aroups Aliphatic aldehyde - R is an alkyl attached to the carbonyl group; Aromatic aldehyde — R is an carbon atom, aryl group. © Have at least one H atom attached to the carbonyl carbon atom. Page 2 of 222 Nomenclature [ For aliphatic aldehydes, Q__ the longest chain carrying the -CHO group is considered the parent structure and is named by replacing the —e of the corresponding alkane by —al. a the position of a substituent is indicated by a number, the carbonyl carbon being considered as carbon-1. ‘Structural Formula IUPAC Name Common Name HCHO. methanal formaldehyde CHsCHO: ethanal acetaldehyde (CH3CH2CHO: propanal (CHa(CH:)CHO butanal fe Oprencne HO 3-phenylpropanal 3B] For aromatic aldehydes, - Ho foul dnaly 6 © <) Q the parent structure is named as a benzaldehyde. Q the carbon on the benzene ring bearing the carbonyl functional group is considered carbon- 1, and the position of a substituent on the benzene ring takes reference from this carbon- 1 ‘Structural Formula IUPAC Name Common Name Ope benzaldehyde benzenecarbaldehyde eC) cr 4-bromobenzaldehyde ; [” For ketones, Q___ the names obtained by replacing the final -e of the name of the corresponding alkane with ~one. Othe chain is numbered such that the carbonyl carbon atom has the lower possible number, and this number is used to designate its position. 2 ‘Structural Formula IUPAC Name Common Name 3 [Link] propanone acetone : = CHsCH2COCH butanone [Link],COCHs pentan-2-one (CHsCH2COCH,CH3 pentan—3—one Ce cyclohexanone a Exercise: Name the following compounds t ft Ah a Se No Hy 3-methylbutanal ‘3-phenylbutanone Page 3 of 223 Physical Properties 3.1 Melting and boiling points As polar compounds, aldehydes and ketones have higher boiling points than alkanes of similar electron cloud size. Example: Table 1 Pentane _Butanal Butan-t-ol cnc TTT SE moet formula HEE Cet He tt —on = hahaa i HAA cae 36.0 76.0 1172 Butan-1-ol has the highest boiling point as the hydrogen bonds are stronger and require more energy to break compared to permanent dipole-permanent dipole forces between butanal molecules and instantaneous dipole-induced dipole forces between pentane molecules. Butanal has a higher boiling point than pentane as the permanent dipole-permanent dipole forces are stronger and require more energy to break than the instantaneous dipole-induced dipole forces between Pentane molecules. Hdd and teow west form A bord vith thenuelrer os H-atom bendd 4. Ce tat pate 3.2 Solubility + The lone pair of electrons on the carbonyl oxygen atom allows carbonyl compounds to form hydrogen bonds with the H atom of water molecule. + This ability to form hydrogen bonds accounts for the appreciable solubility of short-chain carbonyl ‘compounds in water. * As the length of the carbon chain increases, solubility in water decreases due to the increasing size of the hydrophobic alkyl chain + As the carbon chain length becomes longer (more than 5 carbons), the molecule becomes essentially more non-polar, the instantaneous dipole-induced dipole interactions become the predominant intermolecular forces. * Carbonyl compounds have good solubility in non-polar solvents. In fact, propanone, also known as acetone, itself is widely used as an organic solvent for cleaning apparatus in laboratories and is the active ingredient in nail polish remover. © 65 atoms aptly ol eT TOM GSAS Ue Heaglh P 3 akbly a wake Page 4 of 224 Preparation Methods for Carbonyl Compounds 44 Oxidation of alcohols © Candidates should be able to describe the formation of aldehydes and ketones from primary and secondary alcohols respectively, The type of oxidation products obtained depends on the type of alcohol and the strength of the oxidising agent. Distilation set-up For example: = Acidifed KoCroO7 Oxidation of primary aleohol to form aldehyde A ae OH ° 120 out I i K.620,.1450, Bavat +10) SERS RCH + HO 4 iets Seaton Reagents: K2Cr20;(aq), H2SO,(aq) Conditions: Heat with immediate distillation aleohol Observations: _Orange solution turns green Heatiog mantle The oxidising agent is added slowly to the alcohol so that the alcohol is aways in excess. aldehyde a KMnO« is too strong an oxidising agent to be used for this purpose. a The reaction mixture is kept at a temperature below-the boiling point of the alcohol and above that c the aldehyde so that the aldehyde is distilled off the reaction mixture as it is formed, © Immediate distillation of the aldehyde from the reaction will prevent further oxidation by the potassiu dichromate(VI) in the flask. This is possible as the aldehyde has a lower boiling point than the alcohe Reason: Aldehydes have weaker permanent dipole-permanent dipole forces between their molecules as compared to the hydrogen bonds between the alcohol molecules. Thus, less energy is required to break the permanent dipole-permanent dipole forces between the aldehyde molecules resulting in a lower boiling point of the aldehyde. Oxidation of secondary alcohol to form ketone Heat with reflux set-up OH ° . AGH + [01 nee, pba Ho stare a Reagent and conditions: KeCr207(aq), H2SO«(aq), heat with reflux Options: KMnO«(aq), HSO.(aq), heat with reflux ‘Observations: Orange solution turns green (for acidified KzCra0;) wun Purple solution decolourises (for acidified KMnO.) Q: Why is there no need to distil out the ketone immediately? A‘ Ketones are not further oxidised by KzCr.O; hence need not be distilled out immediately. Page 5 of 22he debe Jord ot alkenes atl cave 4.2 Oxidation of alkenes - ana bbe lays R R R Ncac™ 2(0} 51 5 Scio = + tS 7 \ a 7 R Reagents and conditions: KMnO«(aq),HzSO.(aq). heat, , dau md oxTds Observations: Purple solution decolourises allan G awat wor HAO 4.3. Electrophilic substitution of benzene (Friedel-Crafts acylation) g g C + R-CHCl —> oO Roo+ HCl Reagents and conditions: RCOCI, AICh Exercise 4 Which of the following is correct? ew Reagent and conditions Product KCr2O;, dilute HsSOx, heat with 9 CS! boy immediate distiation ay 4 KIMnO, dilute H_SO,, heat with reflux 9 ‘C—CH, i C—CH OF 8 = @ lin (CO)-tore H = HY _ZH3 — KMnO« dilute H:S0,, heat with reflux 49 c=c¢ Chi, H-G-C-H 7 Ho H Sto uy 7 Page 6 of 225 Chemical Properties of Carbonyl Compounds Structure and bonding + The carbonyl carbon is sp? hybridised. + The three sp? hybrid orbitals of this carbon form « bonds with three other atoms. +c bonds are 120° apart (trigonal planar), + The remaining p-orbital of C overlaps with a p-orbital of O to form a x-bond. The carbon and oxygen atoms are thus joined by a double bond Heo H*o H L lt Lot H— T ‘C—H Ween H H H Aldehyde Ketone = Carbony! compounds undergo nucleophilic addition reactions. © A typical nucleophilic addition reaction is the addition of HCN molecule to the carbonyl functional group. (refer to section 5.2) Why do carbonyl compounds attract Why do carbonyl compounds undergo an “nucleophiles? : addition reactions? | © The C atom, of the -C=O group, ie. the| + There is a C=O bond that is unsaturated | carbonyl carbon bears the partial positive charge as it is bonded to a more electonegative oxygen atom. © Asa result, electron rich nucleophiles are attracted to this electron-deficient site. Page 7 of 225.1 Relative reactivity of carbonyl compounds towards nucleop! The susceptibility of the carbonyl carbon to nucleophilic attack is affected by the following factors: (1) Electronic factor Electron-releasing alkyl or aryl groups reduce the magnitude of the partial positive charge on the carbonyl carbon, and hence decrease attraction for nucleophiles and the susceptibility of the carbonyl carbon to nucleophilic attack. R c - - Tis sobetaontin cocron Bt 8 | Auingriweatenpcabon en Rr ~ ‘ Where alkyl groups release electrons by inductive effect, aryl groups do so by resonance. AP LP KA NA KAY — Ao bb. Bulky hydrocarbon groups increase steric hindrance about the carbonyl carbon, hinder the approach of the attacking nucleophile and contribute to a reduction in reactivity. (2) Steric factor Important Conclusion. From the two factors above, we can conclude that aldehydes are generally more reactive than ketones. This is because: «the carbonyl carbon in aldehydes is more electron deficient as it has only one electron donating R group while ketone has two such groups; and «there is less steric hindrance around the carbonyl carbon in aldehydes as it is only bonded to one R group. 5.2 Formation of cyanohydrins — Nucleophilic Addition ° cN Ba. FE i R-C-H + HON ———> RC OH > readin, j R = alkyl group or clait i ° nN R—C—R + HCN > R—C -OH R Reagents and conditions: HEN, a trace amount of KCN as catalyst Or HCN, a trace amount of KOH as catalyst or KCN(aq), H:SOs (aq) Page 8 of 22HM Candidates should be able to describe the mechanism of the nucleophilic addition reactions of hydrogen cyanide with aldehydes and ketones. 5.241 Nucleophilic Addition : a ‘Worked example: N2007/3/4 & Cyanohydrins are useful intermediates in organic synthesis. They can be made by reacting aldehydes and ketones with a solution of HCN to which a small amount of NaCN has been added. In a series of experiments, the reaction was carried out with different concentrations of the three reagents and the following relative initial rates were obtained. Experiment no. [CHsCHO] | [HCN] [NaCN] Relative initial rate/ Jmol do Imot dm? | __smol dm" mol dm”? s* i 0.040 0.040 0.008 4.00 2 (0.050 “0.040 0.008 1.25 ~ 3 (0.040 0.040 0.008 0.75 _ 4 0.050 0.050 0.006, 0.94 } (2) Use these data to deduce the order of reaction with respect to each of the three reagents, showing how you arrive at your answers. Hence, write a rate equation for the reaction. oopay epured Var s, when INN) ns vubued by om 9-008 fs 9.00b, the nbaim ath wake deseaved by Ae foe 0 te OTF wal ot onde wrt NAN I company oped Vand, wha LOL Ut) wa ancoad by 4 hon 0.040 te 0.0TD mal dee, the rele iota vate Grama lyf fore LOD te LT dds ork vt UHL cempartg ptitocd 3 aad Vy sha tH) mew rene by AF ben 92 0° OFD wll? Cty OD vas Corns by bom BAY oe 0.97 nal, ride bat de Kure | ae ben 015 4. 29 2 Ode wit HU O- ade = CULO T TNA tN] Page 9 of 22Fe eg et ede rere cee we vary ee (b) Describe a mechanism that is consistent with your rate equation and indicate which step in the mechanism is the rate determining step. Name of mechanism: Nucleophilic Addition Reagents and conditions: HCN with trace amount of KCN catalyst ", Arne wed db Hatt /Kaly Guana f raleg de Acton nat HOL+ OH > NT +H Ke yt NT (HG oH > act HD) oe EN) (8 Step 1 (Slow): Nucloplck ethuks dedyan - defied og when te fom ta ontoare tnlurmadiade - Step 2: (c) Explain if propanone would react ata faster rate as compared to ethanal. Be cng) when & HO 4 tame alba defrind (84) tow Had f CHS). Oo He athe bv om additamel elbow 1 goog. Ta, opanore urdirgser ruboplidie oddidm tus vy Bed te ety Le wm cite y Jedd & ru alls} geups ont anpre tore Stare bone oy simgard + te J whe a eee el a beded te ly me allyl gray - Theche , propanme ee ne nk (d) State the roles of HCN and NaCN in the mechanism of this reaction. tar cna Nain porly He Orta (N- coy fry the nuclyephitic aac om the xd | olin. Hols) sh te the setond ty ay 0 (Brot) and to prdnrk te enioae bemadhste. Page 10 of 22From kinetics studies of the nucleophilic addition of ethanal, the experimentally derived rate equation is: rate = Iebad]le This is consistent with the mechanism shown above whereby _ ow _sthanel molecule collides with ene _(N” ion in the slow step. However, HCN is a weak acid (K. HCN (aq) === H" (aq) + CN (aq) Since reaction rate is dependent on Ley) , a low [u"] means a slow reaction. x 10 mol dm) and only dissociates partially to give CN” To increase the reaction rate, [¢N"] can be increased through the following ways: (1) Add a small amount of strong base such as NaOH(aq) or KOH(aq). + When a base such as OH”is added, the H’ jons are consumed to form water: OH-+ Ht —> H20 ‘+ ByLe Chatelier’s Principle, the equilibrium position of HCN=H" + CN- will shift to the right, resulting in an increase in the concentration of__. Hence the reaction rate increases. + The above reactions can be simplified to: HCN + OH" > HO + :CN" (2) Add a strong electrolyte containing CN~ such as NaCN(aq) or KCN(aq). The complete ionisation of the electrolyte provides sufficient _to start the reaction NaCN(s) +aq —> Na*(aq) + CN-(aq) The following energy profile diagram depicts the nucleophilic addition mechanism: fa, > Ee, Potential Energy Progress of reaction Page 11 of 225.2.2. Stereochemistry of addition products jonal planar, the nucleophile can to form a racemic mixture (or Since the geometry around,he spi hybridiged carbonyl carbon alom ist Tacemate) containing equal amounts of enantiomers. cN attals fom ghee * chiral carbon cit tacks fom ol es. wee Land Il are mirror images, 1007 Noy, Utd Serta Ho ee r non-superimposable, a 7 H H. HxCitr,, a ar aly Foe? (" e elas He plore cN I Candidates should be able to explain the difference in reactivity between carbonyl compounds and ‘alkenes towards nucleophilic reagents such as lithium aluminium hydride and hydrogen cyanide. 5.2.3 Difference in reactivity between carbonyl compounds and alkenes towards nucleophiles Why do carbonyl compounds undergo nucleophilic addition reactions but not alkenes? «The sp? hybridised C atom, of the ~C=O group, i.e. the carbonyl carbon bears the partial positive charge as it is bonded to a more electonegative oxygen atom. © Asa result, electron rich nucleophiles, such as CN” are attracted to this electron-deficient site. ‘The sp? hybridised C atoms, of the C=C group in alkenes do not have a partial positive charae, and hence do not attract nucleophiles. Page 12 of 225.3 Hydrolysis and reduction of cyanohydrins Cyanohydrins are known also as 2-hydroxynitriles. Just like nitriles, cyanohydrins are useful reagents in organic synthesis as their formation extends the lenath of the carbon chain by one C atom. The difference is that there is an additional OH group in the molecule. In addition, they serve as an intermediate in the synthesis of other organic compounds such as carboxylic acids and amines. Cyanohydrins can undergo acidic hydrolysis to form 2-hydroxycarboxylic acids. CN COOH lays race ee vat mada R—¢—oH + HCl + 2H,0 > REO +” NHC! H H Reagents and conditions: Dilute HCT (aq), heat Or. Dilute H2SO, (aq), heat + Cyanohydrins can undergo reduction, using different reagents, to form amines: 7 SNH Rearend wie het Nell by) br ton ya — Ah anc hydeyas t | H H > yysnralyphns oe toned ba nt CH,NH, - | comport | ni, as0sc | waft, Ot R—¢-0H + 2th ABE Bc —om H Reagents and conditions: LIAIH,, dry ether Or: ‘Ha, Ni, heat He Pt one Exercise 2: J2003/1/30 The product of the reaction between propanone and hydrogen cyanide is hydrolysed under acidic conditions. What is the formula of the final product? A ‘CHsCH(OH)CO2H c CH3CH2CH2CO2H_ 8 CH;CH:CH(OH)CO.H LB (CHs)-C(OHCO.H ° oH w t aH Uses > = dy a6 =U, 1 1 w ow Page 13 of 22Exercise 3 Fill in the blanks for the reaction scheme below. Hen Kn 4(29), HeS04(aq) 4 heat 54 Formation of alcohols — Reduction | {@ Candidates should be able to describe the reduction of aldehydes and ketones to primary and | |___ secondary alcohols respectively. | Aldehydes are reduced to primary alcohols whereas ketones are reduced to secondary alcohols. NoBl: speube Fev vedas qi NaBH oH aldehyde ave, A a Pat eden". H ° Nast, =| 9H R-C—-R + 2H] ————> R-C—R . | H Reagents and conditions: ~ NaBH; (specific for carbonyls) Or: LiAIHs in dry ether or 7 HLINi, heat Any of the three reagents can be used to reduce the carbonyl compounds. The selection of a particular method over the others should factor in the reactivity, if any, of other functional groups present in the intended compound. For instance, if an organic compound contains both the aldehyde group and alkene functional groups, the use of Ha with Ni is not feasible unless the objective is to reduce both groups. If you only want to reduce the aldehyde group, use NaBH, instead. Q: Can LiAIHs and NaBH, be used for reducing alkenes? A’ No. The reductions using LiA/H, and NaBH, involve the H~ nucleophile. Since the carbon atom of the ‘C=C group in alkenes do not have a partial positive charge, it will be unable to attract the H~ nucleophile, hence reduction will not occur. (refer to Section 5.2.3) Page 14 of 225.5 Condensat n reaction (Addition-elimination reaction) i Candidates should be able to describe the use of 2,4—dinitrophenylhydrazine (2,4-DNPH) to detect the presence of carbonyl compounds. ‘Aldehydes and ketones react with the -NH2 group of 2,4-dinitrophenylhydrazine (2,4-DNPH) to form 2,4— dinitrophenylhydrazones with the elimination of water. Dissolving solid 2,4-dinitrophenylhydrazine in methanol and some concentrated sulfuric acid gives Brady's reagent, which is used in the detection of carbonyl groups. NO, NO; HoH hy \ ii \\ C=O + HNN ( Y)-No, + 4,0 a S=/ yl) 2,4-dinitrophenylhydrazine 2 2-dinitrophenylhydrazone fet ube ae = The 2,4-dinitrophenylhydrazones formed are orange crystalline solids with characteris points. + Useful for detection of aldehydes and ketones. Such reactions are termed condensation reactions (or addition-elimination reactions). A condensation reaction is one in which two molecules combine together with the elimination of a small molecule such as water. melting Exercise 4 Draw the structure of the product formed when CcHsCOCH reacts with 2,4-dinitrophenylhydrazine. In general, when ‘X' represents an alkyl or aryl group, the compound is known as a primary amine. Its reaction with a carbonyl compound results in the formation of a carbon-nitrogen double bond (~C=N-). R Page 15 of 225.6 _ Formation of carboxylic acid — Oxidation (for aldehydes only) Candidates should be able to deduce the nature (aldehyde or ketone) of an unknown carbonyl! compound from the results of simple tests (.e. Fehling’s and Tollens’ reagents; ease of oxidation) O° ° R = alkyl group or il ; R—C—H + fo) —SSee 5 R—C—OH heat Reagents and conditons: K:Cr20,(aq), H2SO«(aq), heat Or: KMnO.(aq), H2SO«(aq), heat Observations: ‘Orange KxCr207 turns green (using acidified K2Cr207) Purple KMnO« turns colourless (using acidified KMnO.) «Aldehydes are easily oxidised to carboxylic acids; ketones are not ‘An aldehyde has a hydrogen atom attached to the carbonyl carbon, but not for ketones. ‘Apparently, this hydrogen is abstracted in oxidation, either as a proton or an atom, and the ‘analogous reaction for a ketone ~ abstraction of an alkyl or aryl group — does not take place. + This reaction can be used to distinguish aldehydes from ketone. 5.7 Formation of carboxylate salts using Tollens’ Reagent ~ Oxidation (for aldehydes only) ° 9° i Heat i R—C—H + 2IAg(NH,)]* + 30H” ——> R—C—O" + 2Ag + ANH, + 2H,0 silver mirror — R = alkyl group or Reagents Follens reagent, [Ag(NHaa eae Conditions: Heat Alternative name:__Alkaline diamminesilver(|) ions Observations: A silver mirror is formed. « Toliens’ reagent: Alkaline solution of diamminesilver(|) ions, [Ag(NHs)2]" «Aldehydes (both aromatic and aliphatic) reduce the Ag(i) in Tollens’ reagent to Ag. Under ‘carefully controlled conditions, the silver will deposit on the walls of the reaction vessel as @ mirror. * Can be used to distinguish aldehydes from ketones since ketones do not react with Tollens’ reagent 4 rated ty ovidabyn . Page 16 of 2258 n of carboxylate salts using Fehling’s Solution — Oxidation of aliphatic aldehydes ° 9 1 Heat i R—C—H + 2Cu% + SOH” ———> R—C—O™ + Cu,0 + 3H,0 R = alkyl group only reddish-brown precipitate Reagents and conditions: ~ Fehling’s solution copper(I!) complex, heat Options: Alkaline copper (II) citrate (Benedict's solution) Observations: A reddish-brown ppt of Cuz0 is formed. * Fehling’s solution: Alkaline solution of Cu* ion complexed with tartrate ion. U0 wt indy wkd © Aliphatic aldehydes reduce the copper(ti) in Fehling's solution to the reddish-brown copper(!) 4 ya. 5, oxide, whichis precipitates, peru rolled, amt be erie. «Aromatic aldehydes and ketones do not react with Fehling’s solution. As such, this reaction can be used to tell apart an aliphatic aldehyde from the aromatic aldehydes and ketones compounds. Exercise 5 Determine the identity of liquids A, B and C, given that these are propanal, propanone and benzaldehyde but not necessary in the order. HOH How — 0 i toad y rl H—C—C—C—H Sai cae C+ H HOH H H S/ Propanal Propanone Benzaldehyde Since there are three colourless unknown compounds, at least two different tests need to be carried out to correctly identify them as shown below: ‘Observations recorded for: A Bo c “Jest 1: Add Toliens’ reagent to a sample of iver Miey Silvey mumor Aly sey ivy each compound and heat Test 2: Add Fehling’s solution to a fresh Wah brew eel Tim Ne eda Torn thd ao rr vi sample of each compound and heat “Deductions made: _ (i, LeI) Tegan (CAiphohe) Bera dekgde Chramshi) Page 17 of 22YU dbyh oo W rom er Ty reaped, YY Ud, 0 thw, XU Uy UH. 2 ou Ot, tort ( Grsuery HY wy Exercise 6: Noaiang SALA He pred of Le HY.) ‘The compound CHyBr undergoes a sequence of reactions as follows: OH- (aq), Acidified KoCr20y Tollens' reagent, C.H;8r eX ecomemt o eG seme oo silver mirror 1° alede ald weap ad What could be the formulae for X, Y and Z? x Y z A CHsCH2CH-OH CHsCH2CO2H CH3CH,CHO B » CHsCH=CH2 CHsCH(OH)CH:0H (CHsCH2CO2H 7 ‘[Link] CHsCH2CHO (CHsCH2CO2H D CHsCH(OH)CHs ‘CHsCOCHs ‘CHsCO2H 5.9 Formation of tridodomethane (iodoform) — Oxidation (for carbonyl cpds with CHsCO-) (refer to hydroxyl compounds lecture notes on compounds with —CH(OH)CHs) TH Candidates should be able to describe the reaction of CH3CO- compounds with alkaline aqueous iodine to give triiodomethane. Only carbonyl compounds containing the following structure can undergo this oxidation reaction. This group of compounds consists of ethanal and all methyl ketones, 9 R here must be either a H atom or iL another C atom. R—C—CH When such carbonyl compounds are heated with alkaline lx{aq), a carboxylate salt will be obtained along with yellow crystals of tri-iodomethane, CHls: 9 ° R-C—CH, + 3I, + 40H ———> R-—C—O" + CHI, + 3 + 3H,0 oo Reagents and conditions: _12(aq) with NaOH(aq), heat Or. 12,(aq) with KOH(aq), heat ‘Observatioi Yellow ppt of CHls, ———_———————EEEE In general, alcohols, aldehydes and ketones with the following structures give positive results for tri- iodomethane test. (Refer to Hydroxy Compound lecture notes) ee ee RoG—CHs Rog Chal R-G—CHIz R-G-Cls H H H H oO oO i i i it ROC—CH; R-C—CHzI R-C-CHlz_ R—-C-Chy where Ris a carbon or hydrogen atom Page 18 of 22, fe. &cas oy be af ° r exorcise 7 7 thy enn tbe toe mt tb, How many structural isomers, with the molecular formula CéH;2O can give yellow crystals of tri- iodomethane with hot aqueous alkaline iodine and orange precipitate with 2,4-dinitrophenylhydrazine? Aq B 2 cs wa Svat le alhyde olde Since orange ppt is obtained with 2,4 DNPH and yellow crystals is obtained with hot aqueous alkaline iodine, the isomers must have a methyl carbonyl group: CHsCOC COz, carboxylic acid or ketone (oxidative Alkylbenzenes—benzoic acid 1 alcohols + carboxylic acid 2° alcohols ~+ ketone. Aldehydes -» carboxylic acid + Alkenes — alkane * Aldehydes — 1° alcohol * Ketones — 2° alcohol = Nitrile: Ri _| benzoate salt = TP alcohols > aldehyde {immediate distillation) ‘+ 2°alcohols —+ ketone Aldehydes —-carboxylic acid ‘Ailaidehydes — carboxylate or af | Aliphatic aldehydes — +} carboxylate salt * Aldehydes — 1° alcohol Ketones —+ 2° aleohol Nitrile: RC=N —+ RCH2NH2 Carboxylic acids—+ 1° alcohol Amides —> amine (refer to Organic Nitrogen Compounds) ‘Aldehydes — 1° alcohol Ketones — 2° alcohol 8 Summary of distingui To distinguish: Reagents and Conditions Expected Observation Carbonyl compounds from other functional groups 2,4-dinitrophenyihydrazine (2,4-DNPH) Carbonyl compounds will give an orange ppt. Between aldehydes and ketones KMnO.(aq) / dil H2SO, and heat Aldehydes will decolourise the purple KMnOx. K2Cr20;(aq) J dil. H2SO« and heat Aldehydes will change the solution from orange to green. Tollens' reagent, heat ‘Aldehydes will give a silver mirror. Fehling's solution, heat Aldehydes will give reddish-brown ppt of CuO. (only for aliphatic aldehydes) Between aliphatic and aromatic aldehydes Fehling’s solution, heat Aliphatic aldehydes will give reddish- brown ppt of Cuz. Methyl carbonyl compounds Alkaline aqueous kz, heat Methyl carbonyl compounds will give yellow ppt of CHis. Page 20 of 22Preparation of reagents (self-read for planning) 1. 2,4 -dinitrophenylhydrazine Dissolving solid 2,4-dinitrophenylhydrazine in methanol and some concentrated sulfuric acid gives Brady's reagent, which is used in the detection of aldehydes and ketones. 2. Tollens' Reagent Tollens’ reagent contains diamminesilver(|) ions, [Ag(NHs)2]*. It is unstable and should always be freshly prepared, One drop of dilute NaOH(aq) is added to about 2 cm? of AgNO.(aq) to produce a grey precipitate of AgzO. Dilute NHs(aq) is then added dropwise until the brown precipitate first formed just redissolves. The solution contains [Ag(NHs)2I" ions. 3. Fehling's Solution Fehling’s solution is an alkaline solution of copper(ll) tartrate. As the reagent deteriorates on storing, it is usually prepared in two parts which are added together when a test is carried out. It is a reagent commonly used to test for aldehydes. It consists of * Fehling’s solution A (CuSO, solution) and + Fehling’s solution B (sodium potassium tartrate + excess NaOH) which are mixed just before use. ‘A deep blue solution is obtained on mixing the two solutions owing to the formation of a copper(ll) tartrate. The tartrate ions (2,3-dihydroxybutandioate ions) present prevent the precipitation of Cu(OH)2 by complexing with the copper(ll) ions. 4. Triiodomethane test ‘+ Dissolve about 50 mg of the compound in 1 om? of water. = [Link]® of 10% sodium hydroxide solution is added to 1 cm? of the organic compound ‘© Aqueous Iz is added with shaking until the colour of iodine persists and the mixture warmed. Page 21 of 22Raffles Institution Year 6 H2 Chemistry 2018 Lecture Notes 16 - Carbonyl Compounds Nucleophillic addition mechanism 1. Using HCN, trace KCN as catalyst Generation of nucleophile: 2. Using HCN, small amount of NaOH Generation of nucleophile: Please note the KCN ——~ K+ + :cN OH +HCN ——+ H,0 + :CN- | difference in this step Step 1: Step 1: ° #. ° It CHy—C—ON a er ee | CHS OH | H H anionic intermediate anionic intermediate Step 2: i ro " f Nasty CHy—G—ON + CN’ |CH.—C—CN + HCsn —ty mime. + CN" H H H H cyanohydrin cyanohydrin * If H20 is used to protonate the intermediate in step 2: Ov OH T Q fe 1 osbeon Y\Sy — CHe-G-CN + OH 4 4 OH: + HCN + CN- + H20 (regeneration of CN- nucleophile)