RAFFLES INSTITUTION Year 5 H2 CHEMISTRY 2017 Lecture Notes 11 - Alkenes Lecturers: Mrs S20 Lih Sin ‘Mrs Poh Shu-Jia Learning Outcome ‘Students shoud be able to: (2) explain the general reactivity of akenes towards electrophilic reagents /electrophiles. (b) describe the chemistry of alkenes 2s exemplified, where relevant, by the following reactions of ethene: (electrophilic addition of water/steam, hydrogen halides and halogens, ) reduction via catalytic hydrogenation (catalytic addition of hydrogen). (i) oxidation by cold, alkaline solution of manganate VI) ions to form the dil (iv) oxidation by hot, acidified solution of manganate(VIl) ions leading to the rupture ofthe earbon-to-carbon ‘double bond in order to determine the position of alkene linkages in larger molecules (c) describe the mechanism of electrophilic edition in alkenes, using bromine with ethene as an example. (2) apply Markovnikov’s rule to the addition of hydrogen halides to unsymmetrical alkenes, and explain the ‘composition of products in terms of the stability of carbocation intermediates. Lecture Outline ronces & Websites. 1 Introduction 11 Chemistry in Context by G C Hil & J $ Holman 2 Physical properties of alkenes 2 ‘A Level Chomistry by EN Ramsden 3 Preparation of alkenes 3 Principles of Organic Chemisty by Peter RS. 4 Chemical Properties of alkenes Murray 5 Chemical Distinguishing Tests for Alkenes 4. An Introduction to Organic Chemisty by G1. Brown 5 Organic Chemistry David Klein 4 INTRODUCTION ains sre ings + Alkenes form a homologous series of unsaturated aliphatic hydrocarbons with the general formula C,Ha,, where nis an integer greater than or equal to 2. © The carbon-carbon double bond (C- alkene, ) is the distinguishing structural feature of an op bel ott H 120° 4 120° Soo” 4 Na © Ethene, CH, H,, is the first member of the alkene family. H Displayed formula of ethene4.1 BONDING IN AN ETHENE MOLECULI + Each carbon atom in an ethene molecule is sp* hybi ised. ‘+ Two of the three sp? hybrid orbitals of the carbon atom overlap head-on with the 1s orbitals ‘of two hydrogen atoms to form two C-H sigma (a) bonds. + The remaining sp* hybrid orbital overlaps head-on with the sp? hybrid orbital of the neighbouring carbon atom to form a C-C sigma (c) bond + The unhybridised 2p orbital, which is perpendicular to the plane containing the atoms, overlaps side-on with the 2p orbital of the neighbouring carbon atom to form a pi (x) bond. es ead oti The x electron cloud lies above and below the plane containing the atoms. sp hybrid orbital PML i \ 2p otbital bond (not hybrisises) Bonding in an ethene molecule + There are three regions of electron density around each carbon atom in an ethene molecule. To minimise electronic repulsion, these three regions of electron density adopt a trigonal planar geometry such that the H-C-H and H~C-C bond angles are all 120°. 1.2 STRENGTH OF THE 1 BOND ‘Type of bond C-C (ethane) C=C (ethene) Bond Energy / kJ mor 350 610 Bond Length / nm 0.154 0.134 ‘+ Since more energy is required to break a C=C bond, a C=C bond is stronger than a C-C bond. + The energy required to break a C=C bond is less than twice the energy required to break a CC bond. = Ar bond is weaker than a « bond. Side-on overlap of orbitals is less effective than head-on overiap oforbials. Ve yy, fate they 0 CL bod + The C=C bond in an ethene molecule is shorter than the C-C bond in an ethane molecule because the two carbon atoms in ethene are brought closer together upon the formation of © a x bond via the side-on overlap of two unhybridised 2p orbitals.pote ums | 4.3 NOMENCLATURE +The name of an alkene comprises a root and the suffix “-ene”. - The longest continuous carbon chain bearing the carbon-carbon double bond (C=C) determines the root, - Where necessary, the position of the number between the root and the suffix. bond is specified by placing the appropriate Examples: Exercise 4 Structural Formula | IUPAC Name Name the following alkenes. CH=CH, ethene (@) CH;CH=CHCH(CH)CH(CH.). : + wy thy ‘CHsCH=CH, propene Reece CHsCH,CH=CH, but-t-ene hoa a = 405 dinely | heed oe Supe : but-2-ene © on, cms lsO=CHe -methylpropene nea 1a = dey baydape on * Compounds with two C=C bonds are named as dienes by changing the “ane” ending of the parent alkane to the suffix “—adiene”. For example, the IUPAC name of CH.=CH-CH=CH, is buta-1,3-diene, 1.4 CIS-TRANS ISOMERISM IN ALKENES ‘+ The rotation of the carbon-carbon double bond is restricted because it would require the m bond to be broken. At room temperature, there is generally insufficient energy to break the x bond. * If each doubly bonded carbon atom of an aliphatic alkene is joined to two different groups, the hindered rotation of the C=C bond can give rise to cis-trans isomerism. (CH Cis H Ca’ Ne 7 N\ N\ H H a CH cis-but-2-ene trans-but-4 Note: The trigonal planar geometry around each carbon in the C=C bond needs to be clearly shown when drawing the structures of cis- and trans- isomers. The following structures are incorrect when you are asked to draw the structures for cis and trans~ isomers of but-2-ene: Lt et noes | XK Incorrect structures for cis-but-2-ene and trans-but-2-ene Hyco‘+ Cis-trans isomerism is not present in the following alkenes. Reason for the absence of cis-trans isomers Each doubly bonded carbon atom has two identical groups joined to it. The “trans” isomer experiences high ring strain and is hence too unstable to exist. trans-cyciohexene does not exist. ‘cyclohexene only exit the cis-configuration with H. ‘toms on the same side of | H atoms on the double bond in cyclohexene must be on the same the C=C bond, side of the C=C bond so that cyclohexene can only exist in the cis form.* ‘Note: For a cycloalkene to have trans configuration at the double bond, the cyctoalkene needs to have & carbon atoms or more in the ring, Hence, -cyclopropene, cyciobutene, cyclopentene, cyclohexene and cycloheptene do not exhibit ‘cis-trans isomerism as only the cis forms exis for these cycloalkenes: 22 Oo. For cycloalkenes with 8 or more carbor! atoms inthe ring, the configuration of the double bond can be either cis oF trans, eg. eyclooctene exists as both cis-cyclooctene and trans-cyclooctene: Sica cis-eyelooctene trans-cyclooctone 1.4.1 Relative stability of cis-trans isomers + Cis isomers are generally less stable than trans isomers. + This is due to steric strain between two alkyl groups as illustrated in the diagram below. Str sain He Hee anny ae H, trane2-Bxtono cb2Butene madly! grup ay “Uwree evethewa , Las thle Energy / kl mot-* ZL + 60, + The difference in stability can be quantified by comparing the enthalpy change of combustion. AS (91+ 60x19) —> 4C0K9)04H1,00) (AH,"*= -2682 kJ mor ZN G+ 6045) — ac045)4140(0 "= 2686 kJ mor 400+ 440 Hos-vewr mame dup\ cng) eee conduc len 7 ber» ory, 2 PHYSICAL PROPERTIES OF ALKENES ‘The trends of the physical properties of alkenes are essentially the same as those of the alkanes - Alkenes are insoluble in water, but soluble in non-polar solvents e.g. CC/,. - When the number of carbon atoms increases, the boiling point also increases. wed Coho A wed Alkene | Melting point/*€ | Bolling point/°C | 1. | uJ pon canle but-1-ene 185 6 polaned, Py od eHautr —165 30 shy ‘There are some differences in the physical properties of cis-trans isomers. we ¢ ye x H ——— Now cis—but-2-ene trans—but-2-ene ‘Net dipole moment. non-zero (small) zero eo and den bym dt Melting point / °C —139 106 teleshov, bel a u Boiling point / °C 4 1 ce cae P an ~ Cis-but-2-ene is slightly polar while trans-but-2-ene is non-polar. Cis-but-2-ene and trans-but-2-ene form weak instantaneous dipole-induced dipole interactions, Gis-but-2-ene forms some additional permanent dipole-permanent dipole interactions. More energy is needed to overcome the p.c-p.d. interactions. Cis-but-2— ‘ene has a higher bolling point than trans—but-2-ene. —/ shanpar ind - ~ Molecules of trans-but-2-ene pack better in a crystal lattice, so trans-but-2-ene has a higher metting point than cis-but-2-ene. 4, gy, we rpline Vetere wdenlis, © comet yeu w desly.Exercise 2: ‘Arrange the following alkenes in decreasing order of boiling point: ‘2-methylbut-1-ene ‘cis-pent-2-ene trans-pent-2-ene | AW SN “as Highest Lowest Anewres fon spd Lee fen pad Doone a maylhad tne pT he. Tape wh do lat che “a aoe 3____ PREPARATION OF ALKENES. + Alkenes may be synthesised by elimination reactions. | NaOH in alcoho! L_1_ excesscone. S04 | | —c-c— NadHinatcohol fat eae fh X __heatunder refx 170°C AIP halogenoatkane akene 6 3.4 ELIMINATION Of -ROM HALOGENOALKANES : DEHYDROHALOGENATION OF HALOGENOALKANES Helogenoaikane MeOH inaloonolsovent arene + THX} Heat under reflux where X = halogen atom (e.g. Ci, Br) Reagents: NaOH or KOH, ethanol (as a solvent) (izienaol Condition: heat under reflux eee = A hydrogen atom and the halogen atom, -X from adjacent carbon atoms on a halogenoalkane molecule are eliminated as a molecule of hydrogen halide, HX. For example: | NaOH, ethanol lal —C—CH,CH,CH,CH, — CH,CH,CH,CH, + HBr heat under reflux Brotir uh os & Lene bu H obstioch & Ht bow ‘Two points to note: J © okt fe Chek be Be. Am bed fo eet 1. OH acts as a base in the elimination reaction, removing H" from the halogenoalkane. ri wh a beeralytre fom Hou NaOH, ethanol I H—C—=C—CH,CH,CH,CH, + H,0 * Br- How nt f_ooneoricry Cee 1) oH” heat under reflux 2. Reflux is the process of heating a reaction mixture while continuously cooling the vapour via a condenser with running water. On heating, volatile reactants! Reflux setup water products vapourise. The vapour formed condenses ‘when cooled and retums back to the flask as a liquid. Hence, loss of volatile reactants or products is ae minimised. Reflux is commonly used in organic synthesis which involves heating a reaction mixture <— woerin containing volatile reactants/ products for an extended Period of time. The temperature of the reaction can be controlled or maintained using a water bath. » hestty mare. aes L / oy op td an heat rain two lee ohare 100°C 3.2__ ELIMINATION OF H,O FROM ALCOHOLS : DEHYDRATION OF ALCOHOLS Alcohol SES ONE HeSO8 phone + 16 170°C . LL erty day gt _| —F—-E—0 ao, 00% TH OH 1 Oth poy af 150°C ees Reagents: excess concentrated H;SO, Condition: 170°C ‘+ A hydrogen atom and the hydroxyl group, -OH from adjacent carbon atoms on an alcohol ‘molecule are eliminated as a molecule of water. For example: ‘adjacent C atoms V7 meu oy oy 2 on, Ep CHEER + 21,0 170°C I I ‘oe (raion (enon* Other suitable reagents for dehydrating alcohols are: () A405 2t400°C andi) HyPO, at 250°C. 7 3.2.1 SAYTZEFF (ZAITSEV'S) RULE Aan wd mat alky| eobetth wfltle major ‘+ Ifmore than one alkene can be formed by an elimination reaction, the more stable alkene is the major product. An alkene with more alky! substituents is generally more stable. The order of stability of alkenes increases in the order: HOR H eee Rt cmc < Som Nome’ < domeS < Some. ann \, orn an H How Hog H K RK R unsubstituted most substiut Teast stable most stable ‘+ Consider a reaction between butan-2-ol and excess concentrated sulfuric acid at 170 °C. The following products are obtained in this elimination reaction: HoH OH HoH HoH OH leolee) -H.0 ( He HERO“ Ets + HE E=E— Chas tar mes ve I 4 ‘are obtained. But-t-ene But-2-ene (cis & trans) ‘minor product ‘major product (more highly substituted) Exercise 3(a); Draw the structural formulae of the organic products for the following reaction. KOH in ethanol Oo a + Ores ep eat under reflux WW (2 allyl satan) Exercise 3(b) Draw the structural formulae of all alkenes (including stereoisomers) formed when pentan-2-ol is heated with excess concentrated HSO, at 170°C. . Hwan teed Ty H-GU-O-C- rhor gy Hom 2 ally! substite K # hy wy Unie \ Qt - ct eH t , rN 4h “ " Ohh Tee (lallsl pbrttnd) OO -pod-2- ee tans -pod 2 -we4 CHEMICAL PROPERTIES OF ALKENES _ “Students should be able te . | [{@_explain the general reactivity of alkenes towards electrophilic reagents / elecrophiles. | 4.1 CHEMICAL REACTIVITY OF ALKENES. + Alkenes, though generally non-polar, are reactive ny ‘compounds in comparison to alkanes. ‘+The reactivity of alkenes is attributed to the high Ad electron density of the carbon-carbon double bond. The x electron cloud, which lies above and below the plane containing the atoms, attracts reagents known as electrophiles. x Geopemruiiy vested cas Recall: An electrophile s an electron pair acceptor. Electron-deficien, its allracted to regions of negative charge (6) or regions of electron rich sites in a molecule. It usually possesses an empty orbital to accept an electron pai. 7 wasabwabed {his © bond is broken + The C=C bond consists of ag bond andax Re R F ss bond. Reactions of alkenes generally involve ad + ¥ WH { ee the breaking of the weaker x bond. / i : “é ") this x bond is broken. two new o bonds are formed. + Alkenes typically undergo electrophilic addition reactions. 4.2 ELECTROPHILIC ADDITION REACTIONS OF ALKENES A orweth. th Sladenis should be abot: t [1 describe the chemistry of alkenes as exemplified, where relevant, by the flowing reactions of ethene: (electrophilic adcition of water/steam, hydrogen halides and halogens. (reduction via catalytic hydrogenation (catalytic adltion of hydrogen). (ii) oxidation by cold, alkaline solution of manganate( VII) ions to form the dk (iv) oxidation by hot, aciified solution of manganate( VII) ions leading tothe rupture of the carbon-to-carbon double bond in order to determine the poston of alkene linkages in larger molecules. ieee Electrophilic addition reactions of alkenes include: 1. Addition of halogen, e.g. Br,, to form di-substituted halogenoalkanes 2. Addition of hydrogen 4. cold, cone. H_80, halides, e.g. HBr, to form | | 2.H,0, warm \ oy Brinch = | | halogenoalkanes —o-G— bel OG HOw rN “dan Br Br 3. Addition of H,0 to form alcohols Bro (aa)4.2.4 Electrophilic Addition of Xz: lalogenation of Alkenes Toom temperature + —Er > Dihal a XACCl) Eeence of sunight cerns —¢ —c—o— 1 | x x Reagents: X2 (dissolved in an inert solvent e.g. CC/,) where X = Cl or Br Condition: room temperature, in the dark ‘+ The reaction of an alkene with fluorine is highly explosive while the reaction with iodine is, very slow. Hence, only chlorine and bromine are normally used, For example, ethene reacts with bromine at room temperature to form 1,2-dibromoethane. CH=CH + Bre (in CCls) + CHZBrCHBr Observation: Oraye-nd Br, is decolourised. * Useful test to check for unsaturation (ie. the presence of the C=C bond). It can be used to distinguish an alkene from an alkane. ‘Students should be able Wo: [1 describe the mechanism of electrophilic adit in akenes, using bromine with ethene as an example. [ Points to note when describing the mechanism of an organic reaction | 1. Name the type of reaction undergone, e.g. Electrophilic Addition | 2. Show the movement of electrons using curved arrows. Electrons flow from electron donor/electron rich region to electron acceptor/electron deficient region. 3, Show lone pair of electrons on nucleophile, 4. Indicate partial charges, 5+ and ~ (if any), 5. Indicate slow or fast step for each elementary step (if any). } 6. z Shes wat apply # fae ret subetthion Draw the formula of any intermediate. Draw the formula of product, identifying major and minor products (if apy licable), JL 10| Name of mechanism: Electrophilic Addi STEP 1 Addition of electrophile (Br) to the mbond 4. The x bond is broken and the electrons in the: Wher aro molec ponchos | | EEOM ate now shared | ee cons anion] tenon ncacl, the x cton coud || Petwoenthe carbon and | | erat Acwowcaions nn interacts with the approaching bromine atom. itis an extremely reactive ‘molecule and causes the Br-Brbond to | | Adiacent carbon “atom | | eee tang polarised, fo-the bromine Tobe | | 12828 an electron, so a 5 Be_polatad i, te brome molcte || CeTeocationsfoimad. | | 'etéeney to gan an electron pl n 2. The fltheaded arrow S, +Bro represents the flow of two ‘lectrons. from the electron- | [3 When the olactrons flow | wed + shew va ubomedichs. Ter 'Cao' bur io't | | sume x sector aud | mjasoe troctrpi, Br. ‘Aways oom the ucton | "STM sal he » dow po Graw tho. row trom. te | | donsty In the_BI-Sr bord flecromeh source (arow | | shite fo the Br atom ard | rad by shew fone pare fa the elecrordetcnt || rau in ne ec | a Be ‘species (arrow head). fission of the Br-Br bond. A “ tromnids ton is frmed * Inthe first step (i.e. slow or rate-determining step) of the mechanism, heterolytic fission of the Br-Br bond occurs and the x bond of the ethene molecule cleaves. This results in the formation of a bromide ion and a positively charged intermediate. STEP 2 Nucleophilic attack of Br H How ae i i Cee ee Caamiae ar 4H Br Br Br ‘+ Inthe second step (ie. fast step), the negatively charged bromide ion shares a lone pair of electrons with the carbocation intermediate to form the product. Exercise 4 Describe the mechanism for the reaction between cyclohexene and Bra in CC in the dark. elerbephitie odadifion. rane ed wuhsoie | br =p dogs | oo - s j Owe —w 2, Fe Be aoe \s te or a oot 6° —, Ry "14.2.2 Electrophilic Ad ion of HX: Hydrohalogenation of Alkenes Alkene + HXx(g) OOMIEMPCTeIUE Halogenoalkane I H Reagents: HX(g) where X = Ci, Br orl Condition: room temperature + Ethene reacts with hydrogen bromide at room temperature to form bromoethane: CHeCH + HBr—> CH CH.Br 8h 4.2241 Stability of carbocations ‘* A carbocation is an ion with a positively charged carbon atom. It is a Lewis acid which is extremely reactive and it has a strong tendency to gain an electron pair. 4 R “| ot 4 a 4 —_ men calor ‘Secondary (2°) Tertiary (3°) of a charged system is increased by the dispersal of the charge. Any factor Which leads to the spreading out of the positive charge of the electron-deficient carbon over the rest of the ion will stabilise the carbocation. * Consider a substituent, G, bonded to an electron-deficient carbon. Compared to a hydrogen atom, G may either be electron-donating or electron-withdrawing. Rl an electron-donating substituent Ro lan electron-withdrawing | | ., |G will lead to the dispersal of the ., | Substituent G will intensify the SF" | postive charge and stabitise the | C~* | positive charge and dostabilise the Fe | carbocation | carbocation + An alkyl group is electron—donating. b+ For example, in -CHy group, since carbon is slightly more H electronegative than hydrogen, the carbon atom attracts the electron 3+ Ys density ofthe shared electrons towards itself. Carbon thus acquires a 8 H-*C—> charge while H acquires a 3+ charge. This carbon atom can donate the increased electron densiy via o bond through inductive effect. Hence H+ an alkyl group such as CHs-is electron-donating + The greater the number of alkyl groups attached to the carbon bearing the positive charge, the more stable the carbocation. = © stability of carbocations: 3° > 2° > 4°> CH," 124.2.2.2 Markovnikov's rule ‘Students should be able to [1 apply Markovnikov's rule to the addition of hydrogen halides to unsymmetrical alkenes, and explain the composition of products in terms of the stably of carbocation intermediates, * When an asymmetrical alkene undergoes electrophilic addition, the more stable carbocation intermediate is formed. 7 mager prob. + The more stable (ie. more substituted) carbocation is formed by the addition of the electrophile to the less substituted carbon of the C=C bond, i. the carbon containing more hydrogen. ‘+ The orientation of the addition is determined by considering the relative stabil carbocation intermediate. s of the + The more stable a carbocation, the faster it is formed, => stability of carbocations: 3° > 2°> 1° > CH,” = rate of formation of carbocations: 3° > 2° > 1° > CH; Exercise 5: When 2-methylbut-2-ene reacts with dry, gaseous HBr, two products are formed. Write a mechanism to explain why two products are formed. Name of mechanism: Electrophilic Addi Step 1 : Addition of electrophile (*H) to the x bond n CHy Hy Be yo= ‘ cH slow less stable oH ry i Egan + ge fas Hk more stable 13ede aque wedi that pat alloyne, fhe Nh ow be byt He tte (eo we (Ce eqveow midiom Sab alkelre, Hoe our be Brf oe HH, Tage FRE COT Ky 10%, tod heated mony toert qed he or Heo Tw® points to note ‘When 2-methylbut-2-ene reacts with HBr, the H atom bonds to the less substituted carbon, atom to form the more stable 3° carbocation. Since the 3° carbocation is more stable, it is formed faster than the 2° carbocation. Thus, 2-bromo-2-methylbutane is formed faster than 2-bromo~3-methylbutane. Therefore, former is the major product of the addition reaction (consistent with Markovnikov's rule — see below). Alternative presentation showing both step 1 and step 2 hp eer ee a PE 2-bromo->netybutane oe (i oO" Gone cm ph Be ‘bad 2° carocatan os sora, lose sate OR os gages sYekon ar LO on Ld 2bromo2metybutane cx (major) ©) Beran ostey 3° carbocation more stable and formed faster It can be seen from the above example that when an electrophile such as H” adds to one C atom of the C=C bond in an alkene, the other C atom acquires a positive charge. Hence, if the C atoms in the C=C bond are attached to different number of H atoms, a more stable carbocation is formed if the electrophile adds to the C with more H atoms as shown below: Ll dition of H* addition of H* to i—c=C—R Se Cuan besa Cwith more H, asymmetrical alkene primary carbocation, less stable secondary carbocation, more stable ‘One quick way to predict the major product for electrophilic addition of hydrogen halide to ‘an asymmetrical alkene is to use the Markovnikov's rule which states that: “For addition of a hydrogen halide to alkenes, H” from HX adds to the C with the larger number of H atoms.” Hence, the major product of electrophilic addition of HX to an asymmetrical alkene is the ‘one formed by the addition of H’ to the C with more H atoms attached, ‘The reason behind Markovnikov's rule is because the more stable carbocation is formed if H* from HX adds to the C with more H atoms. 14Exercise, ‘Write the structural formulae for the products obtained in the following reactions. Indicate the ‘major and minor products (if applicable). it wb=d—cryors « Hor = (b) + HBr —> Ck (a) 4.2.3. Electrophilic Addition of X,(aq): Formation of Halohydrin Alkene + Xo(aq) —COmMEMPETAIUTE alohydrin —=t— aa a OH X Reagents: Xa(aq) where X Condition: room temperature, in the dark If an alkene reacts with a halogen dissolved in a reactive solvent such as H,O, the product mixture includes a halohydrin For example, i | Bros HeO ‘major Observation: Orange aqueous bromine is decolourised. wren tebe Sion olf Maw + Yo (Coy) 15To explain the formation of all the products; 1° carbocation less stable Step 1: Electrophilic addition of lectrophile to x bond ‘Step 2: Nucleophilic attack Detailed mechanism for the formation of the major product, 1-bromo-propan-2-0l Name of mechanism : Electrophilic Addition ‘Step 1 : Electrophilic addition of electrophile (**Br) to the x bond HoH tye ear eh carbocation testi + The x electron cloud of the alkene interacts with the approaching Br: molecule and causes the Br-Br bond to be polarised. The Br-Br bond cleaves heterolytically. Two carbocation intermediates are formed. The 2° carbocation, being more stable, is formed faster than the 1° carbocation. 16‘Step 2 : Nucleophilic attack of HO which is in excess Ce yaa HH / ir ‘ H (# deen ford: foe soho ea H oe ecu . mee Tm ep pada cece en ‘+ Water is the solvent and is present in great excess. A water molecule competes with the bromide ion (Br) to attack each carbocation intermediate. The oxygen atom of the water molecule shares an electron pair with the carbocation to form an oxonium ion (i.e. the oxygen atom bearing the positive charge). (The reaction of the less stable 1° carbocation with HzO, and the formation of CHsCH(Br)CH.Br from Br attacking the carbocation intermediates, are not shown here) : wt MH 1 a blen «0 re ‘+The oxonium ion loses an H’ ion to form a bromohydrin, 1-bromo-propan-2-ol (major product). At the same time, the H,O molecule shares a lone pair with the H" ion to form the H30" ion. Exercise Give possible products of the reaction between propene and bromine dissolved in concentrated aqueous sodium chloride. Wucduphdes prod > HO, Br ant 0 any ae We-C-C-H HetoH tty kde Wt by Wa by yet a 4 -C-leU-H K 4.2.4 Formation of Alcohols Alkene + 1,9 —————» Alcohol LI L | —e —o—4— lao HOH Ethanol (CHsCH,OH) can be synthesised from ethene in two ways. ‘Method 1 (suitable for school laboratory) 7 toe by Hall aout be an dahoplils Reagents and Conditions: cold, concentrated H:S0, followed by H:O, warm 7Step 1: Electrophilic Addition Ethene reacts with cold, concentrated sulfuric acid to form ethyl hydrogensulfate. Hou 7 Hee cold [ot H-9 0 ——» H-G—c—H AS if H AR H — OSO,H H—o° “o + Electrons flow from the x electron cloud to the electrophile, “H, and the O-H bond cleaves heterolytically. An ethyl hydrogensulfate is formed. Step 2: Hydrolysis When ethyl hydrogensulfate is warmed with water, ethanol is formed. Sulfuric acid is regenerated. The reaction which takes place is hydrolysis. Hydrolysis is a reaction involving breaking a chemical bond using water. be wt H Hq H H A bl Hod | | H,0, warm | | sah wore H—¢C—C—-H Ko ania + HpSO, H — OSO,H HOH jon 1 Gld awe cul, —— = aHmem 4. Uh Method 2 (industrial method, unsuitable for laboratory use) Reagents: H,0(g), HsPO,(0) on celite Condition: 300 °C, 70 atm 4.2.5 Stereochemistry involved in electrophilic addition * The intermediate carbocation is planar. Hence, it can be attacked from either side with equal a likelihood. w3. yp Hoa tH are " 7b ad lene xi Hh ed + Therefore if a new chiral centre is generated (i.e. Ry # Rr # Ry), a racemic mixture of enantiomers is expected.Exercise (a) Describe the mechanism of the reaction between hex-3-ene and HBr. Your account should ‘+ name the type of reaction undergone, * state the conditions of the reaction, ‘+ show the movement of electrons during the reaction, ‘+ include the formulae of the product and any intermediate. Electrophilic Addition, swith” rorm dunpercbing Bt stew Atak tom ep of sane Ve ~y Br ae i ay cance GN 4) CHG ‘CH,CH, ack tam btm of plane on chet SF ono cence a a Nee h (b) Explain why the reaction of either isomer of hex-3-ene with hydrogen bromide gives the same equimolar (1:1) mixture of two isomers of the product. Both cis and trans isomers form the same carbocation where the carbon with positive charge is__ planar Equal probability of attack of carbocation from jolie side A racemic misture is formed with _epial auweunt of yusdinvacs 4.3 Reduction (Catalytic Hydrogenation) * Catalytic hydrogenation is not an electrophilic addition reaction, but it is an addition reaction as well as an example of heterogeneous catalysis (refer to lecture notes on Reaction Kinetics). Method 4 Method 3 Reagent: H,/Ni catalyst Reagent: H,, Pd/C catalyst Condition: 150°C Condition: heat Method 2 Equation: CH,=CH, + H, -» CH;CH; Reagent: H,/Pt catalyst (Le. PtO.) Catalytic hydrogenation is a quantitative Condition: room temperature reaction. The volume of hydrogen gas used is a measure of the number of C: bonds in the alkene. : c 194.4 OXIDATION REACTIONS + Alkenes are prone to oxidation. Edible oils often contain many C=C bonds and when these oils are exposed to atmospheric oxygen, they turn rancid quickly. ‘= Alkenes combust in oxygen completely to form carbon dioxide and water. Catan + 2Ox(@) > mCOxa) + nH-01) | 1_KhnO,(aq), NaQH(aq) \__/ | KMnOs(aq), HeSO4(aq) -o— Caq Fe Sen cold PY O\E heat under refx O=¢ carboxylic diol ie mild oxidation i ‘only x bond in COxg) + H,0() | (C=C bond breaks : strong oxidation : KxCr207(aq), H2Sx(09) heat under reflux No reaction tyme Hed fre Ure readin ttre 4.4.1 Mild Oxidation allane orl Ks brs 95. (mo orddodion !) KMnO,(aq), NaQH(aq) cold Dio! Alkene Reagents: MnO, (aq), NaQH(aq) Condition: cold + For example, ethene reacts with cold alkaline aqueous potassium manganate(VII) to form ethane-1,2-diol. CH=CH, + [0] + HO Ost OND) | CH (OH)CH,OH Observation: Purple KMnO,(aq) is decolourised. ( redid ) ‘A browniblack precipitate of MnO» is observed (useful test for alkenes) + Cold acidic aqueous potassium manganate(Vil) may also be used although it is less ‘common and not preferred. Seg HUM Oy wrdlony op 4 star ward medion > nel pruned oy a at OH 204.4.2, Strong Oxidation 4.4.2.4 Strong o° lation in hot, acidic medium eR’ ally prow, \gue/ fotnouion), HeSOxog) 7° \ “Peat under reflux carboxylic pple Hada ‘oH acid COxXg) + H,0() where R= alkyl Reagents KMnO,{aq), H,S0.(aq) Condition: heat under reflux + Alkenes are oxidised by hot, acidified potassium manganate(V1l) to form products such as carbonyl compounds or carboxylic acids. The carbon-to-carbon double bond is completely ruptured under the strongly oxidising conditions. exidetve. * The oxidation produets formed depend on the type of C=C bond. By analysing the products formed, the positions of the alkene linkages may be determined. Type of reaction: strong oxidation with C=C bond cleavage R R ° . ttn, cut H,S0, = Heat under refx ane oe Jost san Hed RX “ay o duu a R shyt rerdald & -Loot. / Oo carboxylic acid eat under rf ‘\ ‘oH 1 W odhad. for exypnn Kio, dite H,80« don't 7 0, om {Haste 5 CoYa) + HOU) eden H where R= alkyl group > trum + HH, uv owled L to, ad Hoo * Ethene is oxidised by hot, acidified potassium manganate( VII) to form carbon dioxide and water. CH=CH + 6[0] e848. 260, + 24,0 Observations: Purple KMnO, is decolourised. A colourless gas (CO), which forms a white precipitate with Ca(OH)s(aq), is evolved. oH 21 oN toa mu 2. handing wutd dethroned 4 Oy ond Hh‘© Buta-1,3-diene is first oxidised to HCOOH and HOOC-COOH. These two carboxylic acids are further oxidised by hot, acidified potassium manganate(VI) to form CO2 and H.0. H;C=CH-CH=CH, + 110] —MirRe sels, 40; + 3H,0 c=o—— T daw pred of wey De) 4 dle ieee pK © ud deoakl bods : os ply edt cat eled wh 0 oxidised to r i & C4, oH 1 c0,+H,0 Sete © fartueel < Uh, > Os tH further oxidised to ——— 200, + 1,0 i OH Plredlyor- ott TRO, _KednOa(ae), HaSOx(aa) KNinO4(aq), HeSOvaq) Hob bop AO EOD 603+ HO on heat reat Exe ‘rite the structural formulae of the products formed when the following alkenes are subjected to the stated reagents and conditions. () GH KMInO,, H2804(aq) heat under reflux (b) py iV King, H;S0,(2q) uy oh oH ey alter be H—C=C—CHy CCH, Reatunderrefin Yo yy gd ato #WtHO] sch bab, | l wah [hoe 2 (20 po () chy KNinO,, HeSO4(2a) heat under refx 22Exercise 10: Draw the structure of the alkene that forms the following oxidation products. famownsoun. «Gk heat under reflux ~ CH,~C—CHy * CHsCH)~C—OH KWvinO. H, ° 4, HeSOxag) eo heat underreflux — CH;~C—CH,CHy (€) Cry. ——> CH,COOH + HOOCCH,COCH; + CO, + HzO ‘There are 3 oxidation products where one has 2 C=O groups. This indicates presence of 2 C=C, ‘The fragment with 2 C=O group must be in the centre. one e o H wT = OH Ha pradid wath 2 C20 mut be im dhe ordre et od Acfcation step : H” suppl by ‘any aqueous mineral aed euch 32 H:SO(aa) or Haq) \oac/ KéleOule, NaOH(ag) 7“ “heat under retin =f carboxylic: ‘on acid where R= alkyl CO;*(aq) + 1,010) Reagents: KNin0«(aq), NaOH{aq) Condition: heat under reflux 23‘+ When the medium for strong oxidation of alkenes is changed from acidic to alkaline using NaOH(aq), some of the products obtained will change. For example, carboxylate salt, RCOO is obtained instead of carboxylic acid, and carbonate, CO,* is obtained instead of carbon dioxide. ‘+ The carboxylate salt obtained can be easily converted to the carboxylic acid by adding aqueous mineral acids. Hence, carboxylic acids, RCOOH can be obtained from the ini i eee 4 Vigorous oxidation of § using hot alkaline KMnO, followed by acidification. 5____ DISTINGUISHING TESTS FOR ALKENES 5.1 GENERAL NOTES ON DISTINGUISHING TEST (1) Chemical tests to distinguish compounds must result in different observable changes for the compounds involved in the chemical reaction. Examples include Colour change purple MaO,” decolourises) Formation of precipitate (orowrvblack ppt of MnO, formed) © Formation of gas (colouress CO: gas evolved which forms a white ppt wit aq Ca(OH), 4d. Dissolving of a compound due to a chemical reaction...basie sod esolved in acid) etc (2) Simple chemical tests are assumed to be performed in test-tubes, so do not use ‘heat under reflux’ and also do not attempt to measure the pressure of any gas. (@) A possible way of presenting your answers for distinguishing test questions is: + Reagents and conditions : + Test: © Observation: + Equations (if required) Exemplar Desoribe a simple chemical test which would enable you to distinguish between pentane and pent-2-ene. Ay Reagents and conditions : Br, in Cis, at room temperature, in the dark Test: Add Brz in CC to each of the two compounds separately. Observation: orege-Fd colour of Br, is decolourised for pent-2-ene but not for pentane.) Equation: CHsCH=CHCH,CH, + Br2 (CC/,) -> CHsCHBrCHBrCH,CH,, ee 5.2 CHEMICAL DISTINGUISHING TESTS FOR ALKENES + Besides using Bra in CCi, to distinguish alkene from alkane, aqueous Br. also can be Used. Note that the major product is a bromohydrin and if the alkene is assymetrical, the major product is the one formed via the more stable carbocation (predicted using Markovnikov's Rule), + If the alkene is @ gas, the gas is passed through aq Br; and the orange aq Br is decolourised, 245.3. DISTINGUISHING TEST BETWEEN ALKENE WITH TERMINAL C=C BOND FROM ALKENE WITHOUT TERMINAL C=C BOND ‘+ On warming an alkene with acidified aq KMnO., purple KMnO, is decolourised. If the alkene is a terminal alkene (ie the C=C bond is between C1 and C2), besides decolourisation, effervescence of a gas which forms a white precipitate with aq Ca(OH), is also observed. This is due to CO, formed. + Hence a terminal alkene may be distinguished from an alkene which does not contain terminal C=C bond by warming the alkenes separately with acidified KMnO, and passing the gas evolved into aq Ca(OH),. The terminal alkene decolourises KMnO, and gives off a gas that forms white precipitate with aq Ca(OH),. The other alkene decolourises KMnO, and but does not give off a gas that forms white precipitate with aq Ca(OH). Exercise 10: For each of the following pairs of compounds, describe one simple chemical test which would enable you to distinguish between them, Write balanced equations for the reactions involved. (2) Propene and propane (both are gases) Reagent: Ps ® (lly Condition: tnd, ea Henprabre Test: Bulli a sanph ft tue gu Hua br, destred in ClLy in the deck Observation: Graye-rul Bry U dusloced er paper bd tot bv propane hy + By sc Uy By UH, Be () Pentt-ene and pent2ene — ~/N SS Regent: kWa0y Gq) HaS0+ (oy) Condition: Jf Test: Md vtyds ardor: tndeanny Kin Oy 4) ond dle Hse ea Equation: CH, ui = Us Observation: eB dacdlerise. Le kth Og, bid pact [-ene produ mmm TER go UO tafe het paste Nhe Dd” Hh COO), G) Lk pnd emt del aah " LAIN 4 8) AGRE ON XL ow 5 Equatior pobre bod . ON cara, Sh, {mato pideloe _ rt 25SUMMARY OF ALKENES ‘Each earbon atom in an ethene molecule is @p* hybri + Asthe bromine molecule approaches the ethene | molecule, the Br-Brbond | becomes polarised by the x | electron cloud, i + The alkene attacks the "Br electrophile and the | Br-8r bond undergoes Displayed formula of ethene + There are thrae regions of electron density around each carbon atom in an ethene molecule. To minimise electronic repulsion, these three regions of electron density adopt a trigonal planar ‘geometry such that the H-C-H and H-C-C bond angles are all 120" + The rotation of the carbon-carbon double bond is restricted because it would require the ‘bond to be broken, + if'gach doubly bonded carbon atom of an aliphatic alkone is joined to two different groups, heterolytic fission | tng hindaredroltion of the C=C bond can give rise to cfs-trans isomerism, | CHs CHs GH H + This is followed by the i Noe” Noa” formation ofa carbocation | foN S er the bond is broken. | HW H We ‘Cs em t ‘+ The bromide ion shares an electron pair with the | carbocation to give the final! product cis-but-2-ene (left) and trans-but-2-ene (right) immary of Reactions (using propene a¢ an exampl CH,CHBrCH,Br Hi CH.CHCHs MI proc CHsCHBrCHy ae ry HBr(9) NaOH in ethano, CH:CHECH. Heat under rete i KMnO.(aq), | | funny widen rae ie 0 Gem Gang L27 i 4 dire by bot i ae bapa Ft aatdabic a pede Li dine by “a * CHsCH(OH)CH.B: a “ InOaag), sCH(OH)CH,Br vue Sy ettH, call 4249, +2H,0 | CHsCH(OH)CH, BS eat, cone. HaSO4 " uns made *ot9) a it 1 | Ot os or 2. #20, warm ee ps | a Baloo yurdey of wh de Ho i | | GO; + H,0 + CHCOOH CHsCH(OH)CHs 3 Balas H ly aotlip Ho Se aot pada Oy abby Et 5. Wit Hae raped and Cotes 8 Bae arn 26 wedi pol 2 - by ocrbtiel aye Epes bo mel gf Hemel ee a act CALC oth +5 Se OM, coer POR