Name: Class: A-level Chemistry Revision Pack ¢ Nomenclature and isomerism e Carbonyl compounds e Aromatic chemistry (eet Se ALDEHYDES | KETONES carboxylic acids x x §-s BALA 1: wba, halides amices CHe Vad ed i area’ Kensington Aldridge AcademyEa B Level srlences 25 Nomenclature and isomerism AQA Chemistry Checklist Nomenclature and isomerism : ss = 3.3.4 Can you describe how IUPAC rules are used for naming organic j | c ed fe | | compounds? aor Can you describe what type of molecules show optical isomerism? 337 Can you state what a racemate is? 33.7 Can you describe how a racemate is formed by synthesis? © Oxford University Press 2016 www.oxfordsecondary.co.ukacknowiedgements| ‘This resource sheet may have been changed from the original 12} ORGANIC NOMENCLATURE 3 homelogow sees | functinatorup | pete! sti, ee stan LL | ate ne a eee ct ci Ieee i aod Se raatanee | —Leswae [PM sae | LTT tetera Fi ii cre alderydes ae ieseeties thant ee on Seis eee ee ee ec ee toe ae ee be cn | suf? = amine tid ane ome | bw [Suet ELL rem peste wus ff retlteed ot, ety otancte ovo ff | see am i. pana comin | L [amrstom | TD mote ectenmato | 1h | oat seamen) EES ET cmc ame | i (© www.CHEMSHEETS.co.uk 16-Jul-12 Chemsheets A2 010» a) b) a 4) °) 9 2) a) ») ° 4 °) » 9% » Draw the structural formula of each of the foloing compounds. 2.chlorobutane Smethylpent2-ene butanal 2,3-cimethylbutan-2-c1 pontan-2-one butanoic acid propanamide Name the following organic compounds. rr CHy—cH- Gt cr CHLCHC(CHY,CH.CHS (CHypo=oF Cy — GHC Crh CH OH oy decor Os Cry, cyto iy bub ° i coh t oo hy ethylamine 1) propyl ethanoate J) Shydroxybutanenitrle )_ethanoy! chloride |) propancic anhydride 1m) 3-chloro-S-ethyt-hydroxy-4-methyipentt-ene fn} Nemethylethanamide ™) n) ° P) rir Cho Groce, CHACHLCH.CH(OH)CHs CH:CHLCH.CHCHO Hs GH: o CH CH CHO —H CCHACH(CHW)CH:CH.COOH CH:CH.COOCH.CH.CHCH: Cy Cy C—O hak —c—a (© www.CHEMSHEETS.co.uk 16-Jul-12 Chemsheats A2 010a . NAMING AROMATIC.COMPOUNDS ‘Aromatic compounds are oflen named as derivatives of benzene, so benzene forms the root of the name, Some aromatic ‘compounds have old non-systematic names — some of these are shown undemeath in brackets. Chemisis are sometimes less systematic in naming aromatic compounds than other organic compounds. b q hos ‘mathybronzono chlorobenzene itrobenzane bonzanacarboxyle aold (otene) (eerzoie ac) If two oF more substituents are present on the benzene ing, their postions must be indicated by the use of numbers. This should be done to give the lowest possible numbers to the substituents. When two or more different substitients are resent, they are listed in alphabetical order. 7 » za ie ol Oo * . (mexlene} ‘ad ‘eld ‘The benzene ring can be regarded as a substituent on another moleculo, ike alkyl groups are. The CaHs- group is known as ‘he phenyl group. We y Oba a—ot Ne phenyiamine pheryethene 2-phenylbutane phonylethanone (aniine} j RN, oan. phenyl thanoate ‘meth! benzenscarboryate Nephenylotnanamie (rnaty! benzoato) ‘There are some other compounds to be awere of, such es phenol. oS & & oF (© ww CHEMSHEETS.co.uk 25Alay2016 CChemshoets a2 1024or on Noy Ny Oo Chomsheets A2 1024 25-May-2016 © wwra.CHEMSHEETS co.uk‘ISOMERISM OVERVIEW | | Structural isomers = Molecules with the same molecular formula but a different structural formula Staraolsomers = Wclecules with the same molecular and structural formulae but a diferent arrangement ofthe atoms in space ‘Structural isomerism a) Chain isomerism ‘The carbon chain of molecules with the same molecular formulae cen vary causing isomerism: ie 03 Cia Gran ch oh eG atone rrybeepane ) Position isomerism Functional groups can be in diferent postions on the carbon chain resulting In Isomar: oa a i ea CoHOM yeas orders ropan-tt ropan-204 ©) Functional jrlam Some compounds with the same molecular formulae can contain ciflerent functional groups. i g ohydes eros i e ouortn aon es coo propane rowan cetoeye cols Bests z a g om-at-ton — ced-onay HE -0- ato a0 cto ay abaraia eenioenaesie Stereoisomerism ae + Would heve to break the O=C double bond to rotate around it. ‘+ If both C of the C=C have two different groups attached, the molecule has E-Z CHs, H \X/ ieee cP +E engegan gest pony oppose) es H CH, 2 zusammen (highest priorly together) 13+ Gahn-Ingold Provity (CIP) rules assignod priority of groups attached to C=C ~ the biigher the atomic number of the group attached to the C's, the higher the priority (if {hey are the samo, look atthe atoms attached to those atoms) oF oy 6 ow chet a.8 ie Naty, oad yak ea No o ow oy i TASK1 Decide which of the following alkenes exhibit geometric isomerism. For those that do, sketch the two | stereoeomet to shout tho isomerism coal methyropene -—«Zemelhypent--ene ——«Smetiypent-2ene—3.4cdinethyhexd-ene | ‘-chloopropene —-_2sthypen-tene buttene 2bromne-d-chorobut2-ene | © www.CHEMSHEETS.co.uk 2-June-2016 Chemsheets AS 1047do isomerism ‘+All molecules have a mirror image but often the mirror image Is the same molecule. However, sometimes the mirror image isa different molecule. Molecules have optical isomers i their mitror images are non-supetimposable. ‘+ Molecules containing 2 C with four different groups attached to it exhibit optical isomerism, A carbon atom that has four diferent groups attached is called a chiral (asymmetric) carbon atom. og (pects acta (oot acid TASK2 Decide which of the following elkenes oxhibit goometic isomerism. For those that do, sketch the two stereoisomers fo show the isomerism clearly propan-2-o1 2chlorobutane 4-chiorobutane S.methyhexane butanone 2methybutancie acid ——_butan-2-01 ‘-chloro-3-methylpentane ‘+ Two compounds that are optical isomers of each other are called enantiomers. ‘+ A mbxure containing 2 5050 mixture of the two isomers (enantiomers) is descrbed as being a racemate or racemic mixture, + Many naturally oceutting molecules contain chiral C atoms, but are usually found in nature as a pure enantiomer. * Opal isomers nave ie eae chomicl and phyla propria a aah cher, excep for he elect on Pane parsed it ‘+ Light is @ form of electromagnetic radiation and so consists of waves that vibrate in many directions perpendicular to the direction of travel, Some substances have the ablity to remove from normal light all the light waves except those vibrating in @ single plane - producing plane-polarised fight (in the diagrams below, the arrows show the plane in which the light waves are vibrating, with the ight waves coming out of the plane of the paper). ® O WY soca sorppoures ig ar (wove uenseresen) (Sen nenyonn arin) ‘Sabana osten ‘+ Optical isomers can rotate the plane of polarised light (and so these compounds are said to optically active). ‘+ One enantiomer rotates It in one diaction and the othor enantiomer rotates it by the same amount in the opposite direction. ‘+ Different systems of nomenclature are Is existence for optical Isomers. D/L or +/- are commonly used, but both have baen superseded by the mote useful anc informative RIS system. ‘+ A racemate will have no effect on the plane of the light - itis optically Inactive (each enantiomer cancels out the effect of the othe), Gheretone (oyun once nny (aerate (ost tac) + Many naturally oceurting compounds contain chiral C stoms and occur as one pure enantiomer only. + Many érugs contain chiral G atoms and occur as enantiomers, Often, only one ofthe enantiomers has the desired effect (in the seme way a left hand nly fits a left handed glove), With some drugs, the opposite enantiomer can have an Unwanted effect and so tha drug must be produced as one enantiomer only (© www.CHEMSHEETS.co.uk 2-June-2016 Chemsheets AS 1047Ca A Level Sciences 25.2 Optical isomerism AQA Chemistry Calculations Optical and cis-trans isomerism, and 3-D diagrams Specification reference «337 Learning outcomes After completing this worksheet, you should be able to: ‘+ draw 3-D representations of the optical isomers of transition metal complexes draw 3-D representations of the cis-trans isomers of transition metal complexes identify the number of chiral carbons in an organic compound when given the skeletal formula draw the optical isomers of simple carbon compounds; for example, amino acids. Introduction ‘There will be at least one question in the exam on chirality and optical isomerism. You need to practise drawing 3-D representations of simple optically active molecules, showing both optical isomers (enantiomers) in the same drawing. You do not have to be artistically gifted to draw these 3-D molecules. Just follow some set rules and you can create diagrams that perfectly represent the enantiomers (optical isomers). For example, consider the molecule CHsCH(Br)Cl. This molecule has a chiral carbon because it is bonded to four different groups or atoms. if you draw the molecules in 3-D, you end up with the following representations: ‘The solid wedge represents a bond which is coming out of the paper. <_— The solid lines show 2 bonds “5 in the plane of the paper The line down the middle represents a ‘mirror The dashed wedge shows a bond Sing me the paper Note that the drawings are mirror images of each other, This worksheet will allow you to practise this skill, and will also give you the ‘opportunity to identify chiral carbons in organic molecules (© Oxtord University Press 2017 http:/hvww.oxdordeecondary,co.uk/acknowledgements This resource sheet may have beon changed from the oginat 1Cz A Level Sciences 25.2 Optical isomerism AQA Chemistry Calculations Worked examples Question 1 a Explain why the amino acid alanine, CHsCH(NH,)COOH, has optical isomers. b_ Draw both enantiomers showing the 3-D tetrahedral arrangement around the central carbon. Answer a Work out the central atom. In this case it is the one marked with an asterisk: CHsC*H(NH2)COOH. This molecule has enantiomers because it has a chiral carbon; that is, itis attached to four different atoms or groups of atoms. b_ Draw both enantiomers (optical isomers). we Note: There are two bonds in the plane of the Cooney | Hane paper; of the other two bonds one is coming Hooe’” YH nu” coos out of the paper, and one going behind. Both isomers are mirror images of each other. 2 Draw the two cis-trans isomers of the square planar complex, platin PH(NH).Ch. Step 1 ‘Once again you must give some idea of a 3-D compound. Remember, cis-trans implies ‘together-opposite’. Step 2 Non, go Ns May, oat me * on ow eo Nw spain transplan 3 Draw asterisks to locate the chiral carbons in the molecule shown below: OH H 3 76 54 When you are presented with a skeletal formula and asked to identify chiral carbons, you need to look for carbons bonded to four different groups. Carbon 1 obviously falls under this category. Carbons 3, 6 and 7 are also bonded to four different groups or atoms, but this is not immediately obvious because the fourth atom is a hydrogen atom which, as you know, is not shown on skeletal formulae. So remember to look for carbons which appear to have only three different groups attached, ‘© Oxford University Press 2017 hitpuswuu.ovfordsecondary.co.uW/acknowledgements This resource sheet may have been changed ftom te originalEa ALevel Sciences - 25.2 Optical isomerism AQA Chemistry Calculations | Remember that you must look at the rest of the molecule to see if your carbon is a chiral carbon. If you go clockwise from carbon 1, the arrangement of atoms is different to the arrangement if you go anti-clockwise. OH 4 4. Draw the optical isomers of the complex ion, [Cr(HaNCH2CH:NHz)3)*. The ligand, HNCH,CH,NHz, can be represented by the below diagram where the curved line represents the hydrocarbon chain. C) NOON This is a more difficult task, but it can be done. on , w No A 8 Draw A first. When you draw B you place the Cr** at the same level/height on the page as the other Cr°* ion, and then you draw the ligands as mirror images of the ones in A. Questions In the following questions, en = H,NCH,CH,NHb, and in the complexes it can be drawn as: NOON 1 Draw the cis-trans isomers of the following transition metal complexes. a [Cu(NHs)«(H20)2)* © Oxford University Press 2017 httod Mwy oxtordsecondary.co.uklacknowledgements “This resource shoot may have beon changed fem the original 3Ez) A Level Sciences 25.2 Optical isomerism AQA Chemistry Calculations b [Co(en),Ch]* 2 Draw the optical isomers of the following transition metal complexes. a_ [Nilen):I** b [Co(en).ChI* sw (3 marks) 3. Using asterisks, identify the chiral carbons in the following molecules: a on on (1 mark) (1 mark) on (1 mark) © Oxford University Press 2017 httod isecondary.co.uklacknowledgements “This escurce sheet may hava bean changed fom the original 4Ez A Level Sciences 25.2 Optical isomerism AQA Chemistry Calculations Ho" (1 mark) (1 mark) b i The amino acid, threonine, CH;CH(OH)CH(NH2)COOK, has two chiral carbons. Draw its skeletal formula and identify the chiral carbons. . (2 marks) ji The diagram below shows one of the four different spatial arrangements of the molecule. Draw the three sets of optical isomers. (© Oxford University Press 2017 http:/Avww,oxfordsecondary.co.uk/acknowedgements, “his resource set may have beer changed fom the original 5Ez] A Level Sciences 25.2 Optical isomerism AQA Chemistry Calculations ; “Onn Hoc” Nie ¢ i The amino acid, isoleucine, CzHs(CHs)CHCH(NH2)COOH, has two chiral carbons. Draw its skeletal formula and identify the chiral carbons. .. (2 marks) Draw the three sets of optical isomers. .. (6 marks) Maths skills links to other areas Drawing molecules in 3-D is a necessary skill to describe the shapes of molecules covered at AS level, ‘© Oxford University Press 2017 htto:/iwway oxtordsecondary.co.uk/acknowledgements ‘This resource sheet may have been changed fom the originalEa A Level Sciences AQA Chemistry 26 Compounds containing the carbonyl group Checklist Compounds containing the carbonyl group 3.3.8 Can you desoribe aldehydes and ketones? oO 33.8 Can you state how aldehydes and ketones are named? O aaa Can you describe the mechanism of nucleophilic addition reactions of oO carbonyl compounds? aaa Can you describe how these compounds react when oxidised or oO} reduced? | aaa Can you describe carboxylic acids and esters? oO. ory Can you state how they are named? i) 33.9 Can you describe how carboxylic acids react? Oo aa Can you state how esters are formed from carboxylic acids? oO aa9 Can you describe how esters are hydrolysed? oO 33.8 Can you describe how esters are used? oO 33.9 | Can you describe acylation reactions? oO aa Can you explain the nucleophilic addition-elimination mechanism for Oo | acylation reactions? © Oxford University Press 2016 www.oxfordsecondary.co.uklacknowledgements ‘This r2ource shost may Reve boon changed from the eign |(} REACTIONS OF ALDEHYDES & KETONES Aldehydes can be oxidised by mild oxidising agents to carboxylic acids, but ketones ate not oxidised by these oxidising agents as a C-C would have to be broken. Aldehydes and ketones can both be reduced to alcohols (primary alcohols to aldehydes, ketones to secondary alcohols). OXIDATION & iden ‘dation | REDUCTION 1 alcohol <———?_ aldehyde ———» carboxylic acid | eduction | idan eu 2" alcohol <———* ketone Tecicion K,01401+ W580 (roux) 9H Ki0n01+ Ha804 Ks0n07+ H:S0s fi | (heat & disti off product) Il heat or refx) cH > > con ——— : | Nana or Tollen’s reagent (heal) " ‘or Fohling’s sohiton (heat) 1 alcohol aldehyde carboxylic acid 9x Ks0n01+ Hs80 | heat rei ——H Fe Jeera I NaBH (ag) 2 alcohol ketone Important notes about the reactions KiCriOy & H280¢ Tollen’s reagent Fehling’s solution + Orange 6120; ons (Cr +8) are themselves reduced fo areen C1 lons (Cr +3) as they oxidise the ‘leohel/aldohyde + Ifyou wish fo oxidise a primary alcoho! and prevent oxidation ofthe aldehyde toa carboxylic acd, the aldehyde Is removed by dstilaton as it is formed (the aldohyde has a lower Boling point than {he alcohel a it does not have hydrogen Bonding) ‘+ Totlon’s reagent contalns [Ag(WHs)" ions (Ag +1) which are reduced toa sllver mirror (Ag 0) as it ‘ouidses the aldehyde toa carboxye acid ‘This ronction Is used as a skmple test to distinguish aldehydes from ketones ‘+ Fehling’s solution, which Js a blue solution, contains Cu" jons (Cu #2) which are reduced to a brick-red precipitate of Cuz0 (Cu +1) as itoxicises the aldohyde to a carboxylic acid. + This reaction is used as a simple test to distinguish aldehydes from kotones (© www. CHEUSHEETS co.uk 20-0ctober2016 CChemsheets a2 1048,OXIDATION equations 1 alcohol > aldehyde aldehyde > carboxylic acid 1 alcohol -» carboxylic acid 2 alcohol -> ketone * (0) + 0 REDUCTION equations aldehyde -> 1” alcohol asta + 21H} ——> ena H v ketone > 2” alcohol + 2|K} ——> Seer TASK Write balanced equations for the folowing reactions. Always draw structural formulas of organic compounds and name the organic product. Write no reaction ifthere is no reactant » propanal + NaBHs 2) propan-t-ol + HsSOc/ K:Cr0y dstling off the product 3) butanal + Tollen’s reagent with heating 4) propanone + Febhing’s solution with heating 5) butanone + NaBHy 6) mothyipropan-2-0] + H:SOx / KeCreOr refluxing 7 methyipropan-t-ol + H:SOq/ K.Cr0y refluxing 8) Semethyoutanal + HaSOx / KeCrO7 refluxing (© wwrw.CHENSHEETS.couk 2-0ctober2016 ‘Chomshoots A2 1048, |NUCLEOPHILIC ‘The three atoms joined to the C of the C=O group are ADDITION ‘The C=0 is polar with the C being 5+ (due to O being much more electronegative than C). This means that the C is susceplible to attack by nucleophiles (electron pair donors), arranged in a trigonal planar shape, and so the C, O and the other two atoms joined to the C are in the same plane. As there is a double bond, reagents can add across the double bond. NUCLEOPHILIC ADDITION 1 — reduction Reagent NaBH, Conditions aqueous What happens | Two H atoms add onto the C=O double bond, one onto the C and one onto the O Products Primary alcohols (from aldehydes) ‘Secondary alcohols {from ketones) Overallequation | O oe Mechanism Note Example 4 eg, ethanal + NaBHe | ‘nucleophilic addition I | 4 Example 2 6.9, propanone + NaBH, (© waw.CHEMSHEETS.couk 20-0ctober-2016, Chemsheets AZ 1048NUCLEOPHILIC ADDITION 2 — addition of HCN Reagent KCN followed by dilute acid Conditions aqueous What happens | CN adds onto the C of the C=O; H adds onto the O of the C=o Products Hydroxynitriles Overall equation Mechanism Note “The CN fons come from the KON, The acid provides the H+ fons. You will not do this in the lab as the KCN (and HCN that may be formed) are very toxic. For many aldehydes and ketones, the hydroxynitrile produced will be formed as a mixture of enantiomers as most contain chiral Catoms. ‘Due to the planar nature of the C=O group, the CN’ Ion has an equal chance of attaching the 5+ C from above or below and so a racemic mixture (50/50 mixture of the two enantiomers) would be formed. Example 3 @.. propanone + KCN then acid g qn CHy=C—cH, + Hon —e CH. F—CHy on ‘nucleophilic addition ae <— coternyaryas «+ If ester hydrolysis is carried out in the prasance of alkall then the carboxyile acid formed reacts with the alkall to form a carboxylate salt, and the reaction is known 2s saponification. 1+ The reaction is stow so the ester and alkali are normally bolled together. ° soon ——e Roto + ROH carboxylate on soto TASK.4; Write equations forthe following saponification reections fa) propyl ethanoate + potassium hydroxide > ) mettylethyl methanoate + sodium hydroxide —» = Fats and oils ‘+ Fats and oils (lipids) are naturally occuring esters ofthe alcohol glycerol, which has three -OH groups, and thres ‘carboxylic acids (known as fatty acids). The three fatty acids do not have lo be the same. CO CC CO Ce LCCC CHCl CEH 2 ! + - a a Crea CHE CHC CHS CHC O CeCe ron Sabot ses sade (ty ac) yet i Ob Otc Ct Cl OO Ot CO Otek ce Oe i CC he HOH CHC OCH COLO —omO-tH + SHO i C4 -Ob Oyr h-Crs EH Ch lO Che Oe HCHO Oe Si (te ani) (© WWW.CHEMSHEETS.co.uk 16-Jul-12 Chemsheets A2 014‘+ Inva saturated fat, the fatty acid part of tho molecule Contains no C=C bonds. + Ina polyunsaturated fal, each fatty acid part of the chroRehai-ctarsy-oRanoKnc-aicORE OG HEA ‘molecule contains several C=C bonds. i «The more unsaturated tho fat, the lowor its meting SS@rH-eRsr Oink amar cH oR orRAOH-A oI EC point, Saturated fats are solids at room temperature, i hile polyunsaturated fats are liquids at room ch-crc+ai-awemoraganarotatn temperature ‘+ Fats that are liquids at room temperature are called oils ‘+ Margarine Is made by reacting polyunsaturated fals (8.9. sunflower of) with hydrogen over a nickel catalyst to form solid saturated fats. pobjunssturated fet + Esters are hydrolysed by alkalls to form glyoorol and carboxylic acid salts, In the case of fats and ols, this forms ‘lycerol and fatty acc sats, Soap is faty acid salts and is made by boling fats and oils with potassium hydroxide. i OO Ol Oh Or HO CCH Cy Oi CHer Cr CHeI— OOM i Ce Ch he HCH CHh he i OC Choy Cyc —o—« + akon > i CCH CCH hr C-Chee br CH CHC cheer CREOLE ‘9d (lsd is) Moe ARG Ol Clr Oy Ob CH Ce Gol OH aha aratiroti-ck— ok! HoH, CRORE OH Or Ob-Oe-Op-aimc-o0 K+ Homa Gere eee cx tats ens Biodiese! + Bee & made tom vege als by reactn wit meal nd seu hyo, In fhe UK, rapeseod ob thomas connor gatas te amon i vet bot. sn Bb sho bimon bok ‘© In affect, the vegetable oll s hydrolysed by the sodium hydroxide to form the fatty acid salt which is then converted Into the methyl ester by roaction with sodium hyéroxide. ‘+The methyH estar ofthe fatty acid formed can be used in most diesel engines in place of diesel derived from crude ll +The advantages of biodiesel over diesel are that its renewable and carbon neutral, but massive amounts of farm land are needed to meke the vegetable al, ‘TASK 2: The lipid containing thres fatty acids units of palmelototic ol CHa(CHs)sCH=CH(CH_};COOH can be (a) ‘reacted with potasslum hydroxide to make soap and (b) methanol / sodium hydroxide to make biodiesel, White equations for these reactions. (© www.CHEMSHEETS.co-uk 16-Jul-12 Chemsheets A2 01426 Compounds containing the | Oxford | PLAVETSplences) carbonyl group AQA Chemistry Application Carbonyl compounds Specification references + 9.3.8,3.3.9 Introduction As well as practising generating IUPAC names for carbonyl containing compounds, this worksheet will give you a greater appreciation of how the structure of carbonyl compounds affects the reactions that they can undertake. Learning outcomes After completing this worksheet you should be able to: * name carbonyl compounds represent carbonyl compounds using molecular, skeletal, and structural formulae * describe reactions involving carbonyl compounds using arrow pushing * explain how the structure of a carbonyl compound affects the reactions it can undertake. Background The carbonyl functional group is C=O. When this group is on a terminal carbon atom, an aldehyde is formed. This can undergo oxidation to make another carbonyl- containing species known as a carboxylic acid. Aldehydes can also be reduced to make primary alcohols. When the carbonyl group is not on the terminal carbon atom, a ketone is formed. Ketones cannot be oxidised but can be reduced to form secondary alcohols, Carboxylic acids can be identified by observing effervescence with reactive metals or carbonates. They can also be identified by checking the pH with a pH probe or universal indicator. Ketones and aldehydes can be differentiated by using Tollens’ reagent, Fehling’s solution, or acidified potassium dichromate. These reagents are oxidisers, and therefore a change is observed only with the aldehyde, which is being oxidised to a carboxylic acid, Questions 1 Ketones and aldehydes contain carbonyl functional groups, They can be identified using simple laboratory tests. a State the observations of Tollens’ reagent when added to an aldehyde. smenmeninnen (2 marks) ‘© Onford University Press 2017 httos/www.oxfordsecondan..co.ul/adknowledgements This resource sheet may have boon changed fom the eiginal 126 Compounds containing the EERE 4 ove! sciences carbonyl group AQA Chemistry Application b Describe the observations of Fehling’s solution when it is added to an aldehyde and warmed. (2 marks) © State and explain the observation of a ketone with acidified potassium dichromate. (2 marks) 2 Complete this table for different aromatic compounds. “tsi | ra OR CH,C(O)H ‘2-methylpropanal | CHsO CiHCO Of [me pe 4 rage bao (11 marks) 3. Carbonyl compounds can react with nucleophiles such as the cyanide ion. a Explain why NaCN is used in organic synthesis rather than HCN. (2 marks) (© Oxford University Press 2017 http:/iwww,oxfordsecondary.co.ub/acknomledgoments ‘This resource shest may have been changed ftom the erignat 226 Compounds containing the KEY 4 Lever sciences carbonyl group AQA Chemistry Application b Draw a mechanism for the reaction between propanone and sodium cyanide. State the name of the organic product. (4 marks) ¢ Write a balanced chemical equation for the reaction between ethanal and sodium cyanide and name the product. (2 marks) d_ Explain why all aldehydes except for methanal will produce enantiomers when they react with the cyanide ion. (4 marks) 4 Aldehydes and ketones can be reduced to make alcohols. ‘a State the reagents and conditions for this reaction. (3 marks) b_ Draw a mechanism for the reduction of propanone and state the name of the organic product. (4 marks) © Oxford University Press 2017 hithulwnv.oxfordsecondary.co,uklacknowledgements ‘This rosouree chest may have been changed fom the oignal 3» : 26 Compounds containing the cz Above sciences: carbonyl group AQA Chemistry Application ¢ Write a balanced chemical equation for the reduction of 2-methylpropanal and name the product. (2 marks) 5 Carboxylic acids contain the functional group ~COOH. a Write @ balanced chemical equation for ethanoic acid reacting with sodium and name the salt formed. (2 marks) b Write a balanced chemical equation for ethanoic acid reacting with sodium carbonate and describe any observations. | (3 marks) ¢ Write @ balanced chemical equation for ethanoic acid reacting with ethanol. Name the organic product produced and the practical conditions required to obtain a suitable yield. (3 marks) © Oxford University Press 2017 hito:!vwu.oxfordsecondary.co.uklacknowledgements, ‘This resource sheet may have been changed frm the orignal 426 Compounds containing the 7 carbonyl group AQA Chemistry Stretch and challenge Carbonyl reactions Specification references + 338 + 33.9 Introduction The carbonyl functional group Is C=O and has a permanent dipole due to the difference in electronegativity between C and O. This means that the carbon atom is susceptible to nucleophilic altack. The group is present in aldehydes and ketones. Aldehydes and ketones can be distinguished with Tollens’ reagent, Fehiing’s solution, or acidified potassium dichromate. With ketones there will be no reaction, but aldehydes will oxidise to a carboxylic acid and therefore produce a visual change. Carbonyls can be reduced with NaBH, via a nucleophilic addition reaction to produce an alcohol, When a carbonyl in an aldehyde is reduced, a primary alcohol is formed, where the -OH group is on a terminal carbon. When a carbonyl in a ketone is reduced, a secondary alcohol is formed, where the -OH group is attached to a carbon atom within the hydrocarbon chain. Carbonyl compounds can also react with the cyanide ion to make a hydroxynitrile compound. With the exception of methanal, this reaction produces enantiomer products with aldehydes, and with unsymmetrical ketones enantiomers are also produced. Learning outcomes After completing this worksheet you will be able to: © explain the difference between aldehydes and ketones + use arrow pushing mechanism and prose to explain the nucleophilic addition to an aldehyde or a ketone + predict ang justify enantiomers forming Background Reaction mechanisms are a model to help explain a chemical reaction and predict the product. Curly arrows are used to show the movement of electrons in reaction mechanisms. They should start from the electron(s) moving and point to where they are going. Each arrow head represents one electron, so a double-headed arrow shows two electrons moving. In reaction mechanisms, to simplify the diagrams often the structural formula of a molecule is used. But the area of the molecule that is involved in the reaction is drawn as a displayed section showing all the individual atoms, bonds, lone pairs of electrons, and dipoles. ‘© Oxford Universi Press 2017 hitpufimwy.enfordsecondary.co.uk/acknowledaements ‘This resource shoot may have been changed from the orignal 1; 26 Compounds containing the | oxford ELaNel Beleneps carbonyl group AQA Chemistry Stretch and challenge Task Read Topic 26.1 Introduction to aldehydes and ketones and 26.2 Reactions of the carbonyl group in aldehydes and ketones from the Student book. Then create a spider diagram summarising the difference between aldehydes and ketones as well as their nucleophilic addition reactions. Your spider should include answers to the questions that follow. Questions 41 Depending on the position of the carbonyl functional group, either an aldehyde or a ketone is shown. Describe the test to distinguish between an aldehyde and a ketone using a. Tollens’ reagent (3 marks) b_ Fehling’s solution (3marks) ¢ acidified potassium dichromate. (3 marks) © Oxford University Press 2017 hito:/iwwn,oxfordsecondary.co.ublacknowieduements, ‘This resource shoot may have been changed fm the orignal 2Ena «i a 26 Compounds containing the carbonyl group AQA Chemistry Stretch and challenge 2. Drawa reaction mechanism for the reaction between NaBH, and: a propanal (4 marks) b_ propanone. (4 marks) 3 Draw a reaction mechanism for the reaction between potassium cyanide and: a propanal (3 marks) b_propanone. (3 marks) 4 The cyanide ion is a nucleophile which can attack @ carbonyl and produce a hydroxynitrile product. a Explain why potassium cyanide is often used rather than hydrogen cyanide. (1 mark) ‘© Oxlord University Press 2017 hiipyiivww.oxfordsecondary.co.uklacknowledgements ‘This resource sheet may have been changed trom the orignal 3ae 26 Compounds containing the EEE + tever sciences eles | AQA Chemistry Stretch and challenge b_ Explain how the product with propanal can produce enantiomers but the product of propanone will not. (5 marks) I | © Oxford University Press 2017 htip:/hww.oxtordsecondery.co.uklacknowledaements ‘This resource sheet may have been changed fom the orignat 4Ezz] A Level Sciences AQA Chemistry 27 Aromatic chemistry Checklist Aromatic chemistry 3.3.10 Can you explain why the a ring is a planar hexagon? Oo 33.40 Can you ae why the carbon-carbon bonds i of equal length? Oo 3.3.10 Can you describe how substituted arenes are named? ll o| | 3.3.10 Can you state how the arene ring affects reactivity? f O 3.3.40 Can you explain why arenes react by electrophilic substitution? Oo 3.3.10 Can you describe the mechanism of nitration? Oo 3.3.10 Can you describe the mechanism of acylation? Oo ‘© Oxford University Press 2016 vrww.oxfordsecondary.co.uklacknowledgements ‘This recoureo sheet may have been changed ftom the orignal ‘‘+ Benzene has the formula Cet “+ Its basie structure Is six atoms in a hexagonal ring, with one H atom bonded to each C atom + The moloculeis planar, and the six C-C bonds are the same length — intermediate between single and double. + Each © atom is bonded to two other C atoms and one H atom by single covalent o-bonds, + This leaves one unused electron on each C atom in a p orbital, perpendicular tothe plane ofthe ring. + Each p orbital overlaps with the neighbouring p orbitals to form a s-bond. +The averall result is a ring of negative charge (‘electron cloud”) above and below the plane ofthe rng, the &x pores before ‘vertap ‘+ The electrons in the = system do not belong to any particular C atom (orto a bond between two C atoms) - they are free to move throughout the whole x system - they are delocalised, + Dus to ths, the structure of benzone is represented by: + There are some key places of evidence fa support this structure, In particular how they fit this structure and not a structure with three C=C bonds and three C-C bonds, that ofa "tiene" 1,3,5.cyclohexatilena, 1) CC bond tenath * All the C-C bonds are the same length — and this length Is in-between the length of C-C single and C=C double bonds. + Ifbenzeno was a tone we would expect three longer C-C single bonds and three shorted C=C double bonds. 2)_Addition reactions ‘= Benzene does not readily undergo addition reactions (2. benzene does nat decolourise bromine water) + If benzone was a tiene, we would expect it to readily undergo additon reactions 3)_Enthalpy of hydrogenation cen iret + We would expect a trione to react vith 3 He to form cyclohexane roleasing 360 kuimol of energy (3 x 120). only releases 208 kil of ‘energy showing that benzene is 152 kuimol more stable than the trione. 1 This extra stability is due to the delocalisation of electrons and is known as the delocalisation stabil. (© www.CHEMSHEETS.co.uk 16-Jul-12 Chemsheets A2 017‘+The acyl group is aoe + Acyiation isthe ingertion ofan acyl group into a compound. +The acyl group ofton comes from acyl chlorides or acid anhydrides. ‘+The acyl group replaces the H on the O of an alcoholwater or the N of an amine/ammonia, +The other products an acid, With amines/ammonia, this acid reacts with @ second molecule ofthe aminefammoni to form an ammonium satt ofthe aci 8.,g. acylation ofan alcohol (using an acy chloride) i Rota to 89. seylation ofan amine (using an acyl chlor) > ll gpa vo then THINK, a) Replace an H on the O/N to give the main product. b) Fusing an amine/ammonia, the acid by-product donates H" to another molecule of aminelammonia 1) water + propanoyl chloride 2) ammonia + othanoyl chloride 3) propan-2-ol + ethanoyl chloride 4) othylamine + propanoie enhyride 5) propylamine + butanoy! chloride 6) propan-t-ol + ethanolic anhydride 7) water + butanote anhyctide 8) ammonia + propanoic anhydride 16-Jul-12 Chemsheets A2 016ACYLATION of ALCOHOLS /-AMINES NUCLEOPHILIC ADDITION-ELIMINATION — acylation Reagent | acyi chioride (RCOCI) or acid anhycride (REOOCOR) Conditions What ¢ happons |. The acylgrouvis nf ‘= Acylation is the insertion of an acy! group into @ compound. ‘+ The Hon the 0 of an aleoholiwater is replaced by an acyl group, ‘+ The Hon the N of an aminefammonla is replaced by an acyl group. ‘+ The other product is an acid. With amineslammonia, this acid reacts with @ second molecule of the aminelammonia to form an ammonium salt of the acid. OVERALL a) Replace an H on the OIN to give the maln product. ») Hf using an aminelammonia, the scld by-praduct donates H to another molecule of amine/ammonia Products | Carboxylic acid (from water) Ester (rom alcohols) Amide ((rom ammonia) Nesubsttuted amide (Irom amines) Overall equation 6. acylation of an alcohol (using an acy chore) , Q. og — LL. « ‘2. acylation of an amine (using an acy! chloride) then (© wan-CHEMSHEETS.co.uk Sune 2016 ‘Chemsheets A2 1054 { |Example 1 [ea ebro! popanoy chietae I I Hp oH Lal + HOCH ACH, —e CHs-CH. NO;" + 2HSO; + H,0* + HL NOs NO Reaction of 2 electrophile - with benzene — noe Example 4 ‘2, mothybonzone + conc HNO, & cone H-SO, at 50°C to make 2-nitrometnyibenzene Hs is GH, v0 | + HNO, ——> + HO HNO, + 2H;S0,-> NO;* + 2HSO; + HO" chs electrophilic te yf ‘substitution | oH #7 No, Nos © www.CHEMSHEETS. co.uk wealay2016 (Chemnsheets a2 1025,Example 2 ‘eg. mathylbenzene + conc HNO» & conc H,S0, at 50°C to make 4-nitromethylbenzene Example 3 4, 1.3-dimethylberzene + conc HNOs & cone HeSO, at 60°C to meke 2-nitro-,8-dimethybenzene, (© woew.CHEMSHEETS co.uk sotlay-2016 (Chomshoots A2 1025ELECTROPHILIC SUBSTITUTION 2 — Friedel-Crafts acylation Reagent Acyl chloride or acid anhydride & AlCl; Conditions ‘Anhydrous (to prevent reaction of AlCl, What happens | H atom on ring is replaced by RCO (acy!) group Products ‘Aromatic ketones — this reaction is extremely useful for adding C atoms to aromatic rings and ‘ny reaction that adds C atoms onto the aromatic ring is very valuable In organic synthesis, Overall equation Ox eR with an acyl 8 chloride oO eer eee chal Og UR So: with an acid g 8 e mnere oO + abola — + ation Mechanism =| (acyl chloride) electrophile = RCO" (acylium ion) Generation of ‘lectrophil, a R—CHcl + A, ——e ROC, + A © © i Ok Reaction of ! WR electrophile Pare 1 | with benzene a — — | | Regeneration oy 4 yy a | agenoration Agu +H’ > AlCl + HCl | Mechanism (acid anhydride) | Goneration of | electrophite i i wl Reaction of tl cloctrophile Rete Z with benzene cau 7 ° Regeneration il fl ofeatalyst. §— [CLAR-O—C—R| +H} ——= AG, + HOC ‘© wwew.CHEMSHEETS cok ao-ay2016 ‘Chomshoots A2 1025,Example 4 ‘8g. methylbenzone wit ethanoie anhydride and AlCl fo make 2-methyiphenylethanone th a) e 6 A ° + He ob on, oH yo ton eo 9 hoo i i Hye—-C—~0—c—cH, + AK, ——e HOC, + [apr-ot en hy chs He J i 1 pot Tn electrophilic ‘substitution u i pelle ee Example 5 ° e.g. methylbenzene with propanoy chloride and AICI to make Hac O ‘© won. CHEMSHEETS.co.uk May. 2016Example 6 No, 2.9. nitrobanzene with ethanoyl chloride and AICI to make Hs i Example 7 mp e.g. 1,3-dimethylbenzene with ethanole anhycride and AICI: to make be cH (© wirw.CHEMSHEETS co.uk ay 2016 Chomsheets A2 1025,