-. First Edition April 2014. » = Second Edition =. March 2015 CAREER ENDEAVOUR PUBLICATIONS has taken due care in collecting the data and providing the solutions, before ‘publishing this book. Inspite ofthis, i'any inaccuracy or printing errots are there, CAREER ENDEAVOUR PUBLICATIONS owos No responsibil, CAREER ENDEAVOUR PUBLICATIONS wil be grateful f you could point out any such emor, Your suggestions willbe highly appreciated, All right reserved by CAREER ENDEAVOUR PUBLICATIONS, No par! of this book may be reproduced or | utilized in any form without the written permission from the publisher. CAREER ENDEAVOUR Publications}PREFACE TO THE SECOND EDITION The book “Organic Reaction Mechanism & Named Reactions” is written with the objvctiv of providing description of principles involved in organic Chemistry including their application at a level suitable for graduate and post-graduate students of Chemistry in different universities. Starting with glimpse of general organic chemistry, the book deals with stereochemistry followed by basic principles of reaction mechanism. Later part of this book focuses on important name reaction and rearrangement reactions. Chemistry of synthetically important heterocyclic compounds is also discussed along with some challenging problems This book will be highly useful for the candidates preparing for various competitive examinations at national and state levels such as CSIR-UGC-NET, GATE, SLET, etc. In all the competitive examinations such as CSIR-UGC-NET/IRE, GATE, SLET, ete, the section ef Organic Reaction Mechanism & Named Reactions carry approximately 10-12 percent weightage of total marks. + Inevery year CSIR-UGC-NETIIRF includes at least 25 to 30 marks from this section out of 200 marks + In every year GATE paper includes at least 10 to 12 marks from this section out of 100 marks. Apart from NET, GATE, PSUs this book will also be very useful to candidates appearing ‘or various Ph.D. entrance examinations. ‘The book is designed and prepared in such a way that it provides the required information regarding almost all important topics. Students preparing for competitive examinations are advised to go through every topic for their understanding and conceptual clarity and then get into solving the problems. For more practice students are also advised to go through our classroom assignments, Much care has been taken to minimize the typographical errors, yet if any noticed, then your suggestions are invited with a view to improve the book in future editions. ‘We would like to thank our respected faculty members for their valuable inputs in the book. Thanks to Mr. Ramashish Paul & Mr. Raj Pandey for their constructive support in doing corrections and proofreading. A note of thanks also to Mohammad Firoz fo: formatting, designing and type-setting the book.Page Nos, Chapter -2 ‘Chapter -4 Kian Chapter -6 Chapter -8 Heterocyclic Chemistry 268-316 eee oaCHAPTER General Organic Chemistry Ll Electron Displacement Effects: Effect occuring due to displacement of electron in organic compound is called Electron Displacement Effect or Electron Delocalisation Effect. Electron displacement effect is of mainly two types. Electron Displacement Effect >— Permanent effect ‘Temporary effect Polarization effect) (Polarizabilty effect) Inductive Hyper Resonance Mesomeric Inductomeric Electromeric effect conjugation effect effect effect Other Effect: (@) Steric inhibition of resonance _(b) Ortho effect. (1) Inductive effects: Ina covalent bond between two different atoms, the electrons in the —bond are not shared equally. The electrons are attracted towards the most electronegative atom. An arrow drawn above the line representing the covalently bonded electrons shifts towards higher electronegative atom can show this. Electrons arepulled in the direction ofthe arrow. When the wom 0 is mace When the atom (Biss electronegative than carton electronegative than carbon electrons attracted toX electrons attracted to carbon +> =<- XO \ —c-x —-z 7/4 7 4 egative inductive positive inductive effect (effect) fect (+ effet) I groups +I groups aGeneral Organie Chemistry X=Br, Cl, NO;, OH, OR, SH, ‘SR, NH, NHR, NRo, CN, COH, CHO, COR, ‘The more electronegative the atom(X), the stronger the I effect Z=R(alkyl or aryl), metals (eg. Li or Mg) The more electropositive the atom (Z.), the stronger the +1 effect. Pauling electronegativity scale The inductive effect ofthe atom rapidly diminishes as the chain fength increase kook Teas the chain fength increases C=23 0 Br=28 N=30 = 3.0 0-35 -F = 40 Higher the value, more electronegative will be atom + 88+ B+ BE HeG—CH— CHa CHa ~ch experiences a negligible ~i effect experiences a strong -I effect ‘The overall polarity ofa molecule is determined by the individual bond polarities, formal charges and lone pair contributions, and this can be measured by the dipole moment (1). Higher the dipole moment (measured in debyes (D)), more polar will be compound. (2) Hyperconjugation: Ao —bond can stabilise a neighbouring carbocation (or positively charged carbon) by donating electrons to the vacant p-orbital. The positive charge is delocalised or ‘spread out’, and this i stabilising effect is known as “no-bond resonance”. TAY CH the electrons in the o-bond e-bond spend time in the vacant p-orbital vacant p-orbital ‘Points te Remember : ‘Number of « hydrogen oc number of hyperconjugating structure o: stability 1 1 «——___________ « Polarity « dipole moment «& — Heat of hydrogenation bond length Problem : The correct order for the stability among following compound is ® ® Hee, Hee, CH;CH, — CHyCH,CH, cH ey Hye SoG, Hye’ tod @ ay qa avy) @IPU>U> IV (E> M>IV>M @IV>M>0>1 @Iv>m>I> 0 Soln, Number of er hydrogen oc stability. Ths, © a a ay ® Hac, HaC, CH;CH, — CH;CH,CH, No Sh yooh Z Hee we ‘Number of a hydrogen 3 Zz 1 0 Stability, [> 11> I> iV Hence, option (a) is correct. isGeneral Organic Chemistry @ Problem : Which is more stable methyl o -D glucopyranoside or methyl f -D glucopyranoside. fi ys OCHs cXH orbital Methyl a-D glucopyranoside Methyl B-D glucopyranoside ‘There is stabilising interaction i.e. hyperconjugation between the unshared pair on the hetero atomand co" orbital for the axial C-X bond in the case of a anomer. thus itis more stable as compared to its @ analogue in which there is no such interaction, Note : Ifoxygenis replaced by carbon, there is no such stability interactionas like as above. Thus, stability can only be decided on steric ground. Thus stability order for such species will be (Stability) OMe (3) Mesomeric effects: Whilst inductive effects pull electrons through the o bond framework, electrons. can also move through the —bond network. A —bond can stabilise a negative charge, a positive charge alone pairof electrons or an adjacent bond by resonance (ie. delocalisation or ‘spreading out’ ofthe elec- trons). Curly arrows are used to represent the movement of = or non-bonding electrons to give different resonance forms. Itis only the electrons, not the nuclei, that move in the resonance forms and a double-headed arrow is used to show their relationship. (a) Positive mesomeric effect: * When a r-system donates electrons, the 7 -system has a positive mesomeric effect (#M effect). \Omnd, \.-_ 8 - mor <~_— aati donates electrons: “4M group + When a lone pair of electrons is donated, the gorup donating the electrons has a positive mesomeris effect. of ® Ne oy 7 donates electrons: 4M group (b) Negative mesomeric effect: + Whena 7~system accepts electrons, the ~system has a negative mesomeric effect (-M efiect). 2 8 Shon <—> Some Se fou 7H Accept electrons: ‘M groupLe General Org: ie Chemistry “The actual structures of the cations or anions lie somewhere between the two resonace forms. All resonance forms must have the same overall charge and obey the same rules of valency. ‘groups generally contain an electronegative atom(s) and/or a n-bond(s): CHO, C(0)R, CO,H, CO,Me, NO,, aromatics groups, alkenes ef, +M groups gererlly contain atleast a fone pair of electrons or am -bondts) In neutral compounds, thete will always be a+M and —M groups(s): ‘One group donates (+M) the electrons and the other sour) accepts the electrons(—M). nivel > ROH CHG +M group —M group Allresonance forms are not of the same energy. In phenol, for example, the resonance form which theintact aromatic benzene ring is expected to predominate, Ger =b bd Asarule of thumb, the more resonance structures an anion, cation or neutral —system can have, the more stableitis, aromatic 2M group ring is intact Inductive versus mesomeric effects: Mesomeric effects are generally stronger than inductive effects. A+M group is likely co stabilise an anion more effectively than a +I group. ‘Mesomerie effects can be effective over much longer distances than inductive effects, provided that conjugation is present (ie. alternating single and double bonds). Whereas inductive effects are determined by distance, mesomeric effects are determined by the relative positions of +M and -M groupsina molecule. Application of inductive effect, hyperconjugation and mesomeric effect: Acidity and basicity: Acids: An acid is a substance that donates a proton (Bronsted-Lowry). Acidic compounds have low pK- values and are good proton donors, as the anions (or conjugate bases), formed on the deprotonation, are relatively stable. Tnwater: os Ke e ° HA + HO === M0 tere, i acidity constant Acid Base Conjugate Acid Conjugate Base The more stable the conjugate base the stronger the acid fees As H,0 is in excess PK, = logo ‘The higher the value of K,, the lower the pK, value and.the more acidic is HAGeneral Organic Chemistry 5) The pK,-value equals the pH of the acid when it is half dissociated. At pH above the pK, the acid exists predominantly as the conjugate base in water, At pH below the pK, it exists predominantly as HA. pH = 0 (strongly acidic) pH =7 (neutral) pH =14 (strongly basic) ‘The pK -values are influenced by the solvent, Polar solvents will stabilise cations and/or anions by solvation. in which the charge is delocalised over the solvent (e.g, by hydrogen-bonding in water) 4 B® @ & & lo 8 HO-HunAuiH—OH, HOM ORIOH, oN HO SH ‘The more electronegative the atom bearing the negative charge, the more stable the conjugate base (which is negatively charged). pK, 3 16 3 48 Mostacidic HF > HO > NH, > CH, increasing electronegativity ‘Therefore, 1 is more stable than H,C®. ‘The conjugate base can also be stabilised by 1 and -M groups which can delocalise the negative charge. (The more spread out the negative charge, the more stable it is) ‘and —M groups therefore lower the pK, , wl +Land +M groups raise the pK, (a) Inductive effects and carboxylic acids: The carboxylate anion is formed on deprotonation of carboxylic acids, The anion is stabilised by resonance (ie. the charge is spread over both oxygen atoms) but can also be stablised by the R group if thishas a—I elect O 0 8 pP. Base ¢ Roce Gas R-Cy <——_ Roo ‘on Basel) ‘Od Ny The greater the effect, the more stable the carboxylate anion and the more acidic is carboxylic aia ~+ + Oc ae, “Sen (b) Inductomeric Effect 5 + Temporary effect. “Takes place in sigma bonded system. + In presence of attacking reagent, transition of'a electron cloud takes place more readily. Example: © ROH + Bo Inpresence ofbase B, movement of sigma electron takes place faster. ) Other Enfect : (a) Effect of inertia/steric inhibition of resonance: Resonance ability ofan atoms lost ifit looses planarity with the other part ofthe system due tosteric crowding bybuiky group in adjacent positions NH, NH. HC. CHs HyC’ ‘CHs NO2 NOz @) @) iqThe above two compounds A and B have everything identical except position of the two methyl group. Itis expected that A should be stronger base than B due to closeness of two electron donating methyl group ‘0 — NH, The fact is opposite to this. In compound B -NO, is surrounded by two bulky methyl group and they sterically sepel the -NO, group. In order to minimize the steric repulsion by the two adjacent methyl group, the nitro group loses planarity with the benzene ring. So, now -NO, due to lack of planarity weigh ring, not able to resonate. This is known as steric inhibition ofresonance, Thus in B ,-NO, is not decreasing basic strength by resonance, InA —NO, lies in the plane of the ring, itis in resonance with the ring, decreases basic strength of -NH, by resonance, hence weaker base. Similarly we can explain the acidic strength of Cand D COOK COOH HC. CH3 HC” ‘CHs NO2 NO» oO @) Cis stronger acid inspite of closeness of two electron donating methyl group to ~COOH, (b) Ortho effect: Ifany group present on ortho position ofthe benzoic acid. It always increases acidic nature of acid because this group decreases outer resonance of the ring toward acidic nature. Similarly ffany group present on ortho position of aniline, it decreases basic nature. This effect is known as ortho effect. Problem : The correct order of acidity among the following compound I-IV is Or OL 'NO2 No, @O ap ay (iv) @U>M>IV>1 ()IV>I>II>1 (I> IV>m>1 (@IV>mI> > 1 Because of ortho effect o-nitro benzoic acid is most acidic followed by para and meta. Thus order willbe it > IV > III> 1. Hence, option (¢) is correct. Keynotes in Organic Chemistry: + I£-M groupsare introduced at 2-,4- and/or 6-positions, the anion can be further stabilised by debcalisation through the system , as the negative charge can be spread onto the-M group. We can use double- headed curly arrows to show this process. + If-M groupsare introduced at the 3- and/or 5-positions, the anion can not be stabilised by delocalsation, as the negative charge cannot be spread onto the-M group. There is no way of using curly arrows to delocalise the charge onto the-M groups. + If-1 groupsare introduced on the benzene rng, the effect will depend on their distance from the negative charge. The closer the I group isto the negative charge, the greater the stabilising effect willbe. The order of-Istabilisationis therefore 2-position >3-position>4-position, + The—Meffects are much stronger than I effects, eq =General Organic Chemistry Example: The NO, group is strongly electron- withdrawing; —I and —M. HO OH On oo Nop ‘NO 4 pK 99 84 Least acidic ss 0-Lor-M The NOpcnonystbilse froupson he rng theanion ndacve'y “The NO, can only stabilise the anion induetively and ar NO; NOz 40 Moet acidic as both NO, groups in stabilise the anion induetvely and by rexonance Bases: A base isa substance that accepts proton (Bronsted-Lowry). Basic compounds have high pK.- values and are good proton acceptors, as the cations (or conjugate acids), formed on protonation, are relatively stable, In water: es Kk ® ° Bo + HO === BH + HO Base Acid Conjugate Conjugate Acid Base ‘here, Ky is basicity constant ‘The strength of bases are usually described by the K,-and pKa-values of the conjugate acid. Ky ® @ BH + H,0 B + H;,0 (a][2,0"] Pee [ ® [a5 #,0 isin exces] where K, is acidity constant. ® + IfBisastrong base, then BH will be relatively stable and not easily deprotonated. BH will therefore | have ahigh pK, -vahie ® © + [fBisaweak base, thenBH willbe relatively unstable and easily deprotonated, BH will therefore have alow pK -value, ‘The cation can be stabilised by +I and +M groups, which can delocalise the positive charge. (The more ‘spread out’ the positive charge, the more stable itis). on Inductive effects and aliphatic (or alkyl) amines: On protonation of amines, ammonium salts are < © © Ro ea RNHs X | &General Organic Chemistry ‘The greater the HI effect ofthe R group, the greater the electron density at nitrogen and the more basic the amine. The greater the +1 effect, the more stable the ammonium cation and the more basic the amine, He Be NES HON-H ERONGH BRON—H EP -N—H / / / / H H H Hf pK, 93 10.7 10.9 10.9 ‘The pK,-values should increase steadily as more + alkyl groups are introduced on nitrogen, Howeves, the pK,-values are determined in water, and the more hydrogen atoms on the positively charged nitrogen, the ‘greater the extent of hydrogen-bonding between water and the cation. This solvation leads to the stabilisation ofthe cations containing N-H bonds. Inorganic solvents (which can not solvate the cation), the order of pK sis expected to beas follows: R,N > R,NH > RNH, > NH, (R= +I alkyl group) st base les bse ‘The presence of -I and /or ~M groups on nitrogen reduces the basicity, and hence, for example, amides are poor bases. Ethanamide has a pK, of -0.5, qG ni ‘The C=O group stabilises the lone pa on aitogen by CRS, ~~ —* -_Cx® resonance. Ths reduces the HsC7 [WH HgC7 “Sip Geeton densiy on nitogen Mt (@) Mesomeric effects and aryl (or aromatic) amines: ‘The lone pair of electrons on the nitrogen atom of aminobenzene (or aniline) can be stabilised by the delocalisation ofthe electrons onto the 2-, 4-and 6-positions of the benzene ring. Aromatic amines are therefore less basic than aliphatic amines. @ ® © NH, NH, Ny Cf bbb. * GS + If-Mgroupsare introduced at the 2-, 4-and/or 6-positions (but not at the 3- or 5-position), the anion can be further stabilised by delocalisation, as the negative charge can be spread onto the-M group. This reduces the basicity of the amine. + f-L.groupsare introduced on the benzene ring, the order of I stabilisation is 2-position > 3-position> 4- position, This reduces the basicity ofthe amine. Ni, HAN i, NO2 NO2 pK, * 46 245 028 Most basic 28 no-T or-M ‘The NOp group can stabilise the __—_—LaBst basic: The NOp group can stabilise groups on the cing lone pair inductively the lone pair inductively and by resonanceGeneral Organic Chemistry + If+M group (e.g. OMe) are introduced at the 2-, 4- or 6-position of aminobenzene, then the basicity is increased. This is because the +M group donates electron density to the carbon atom bearing the amine ‘group. Hohl NH, Holi OMe ‘OMe Meo pK, 42 45 5.3 ‘Most basic: The OMe group can donate electron density tothe nitrogen and it has a weak I effect (aswell. apart from the nitrogen) Least basic: ‘The OMe group cannot donate electron density t the carbon atom bearing the nitrongen The OMe group can donate electron density tothe nittogen but ithas a strong effect as itis in the 2-position Curly arrows canbe used to show the delocalisation of electrons onto the carbon atombearing the nitrogen, iit, iit, iin, lO eleton density — a ‘sicentoue alpen eres ewe ‘OMe @0me @OMe (©) Lewis acids and base: + A Lewis acids any substance that accepts an electron pair in forming a coordinate bond. Examples inelnde HBF, AICI, TiCl,, ZnCl, and SnCl,. They have unfilled valence shells and hence can accept electron pairs. + A Lewis base is any substance that donates an electron pair in forming a coordinate bond. Examples include H,O, ROH, RCHO, R,CO, RN and R,S, They all have a lone pair(s) of electrons on the hetero atom (0, NorS) (0 Basicity and hybridisation: ‘The greater the ‘s’ character ofan orbital, the lower is energy the electrons and the more tightly the electrons are held to the nucleus, The electrons in an sp-orbital are therefore less available for protonation than those in an sp?- or sp'-hydrid orbital and hence the compounds ate less basi. most basic: R;N > RC? least basic © most basic: RC > RC sp sp? least basic sp (25%) @3%s) 60%)CHAPTER Aromaticity Introduction Aromaticity isa chemical property of organic compound, aromatic compound have following characteristies @_Ithashigh degree of stability (i) It shows electrophilic substitution reaction rather than electrophilic addition reaction. Itmeans it does not, decolourise bromine water solution. (i) Aromatic compound follow Hilckel rule. According to which A cyclic planar conjugated species having (4n+2)r electrons (where n=0, 1, 2,3, ...) is aromatic in nature. () Theresa diamagnetic ring current. (¥) Each carbon mast be sp*-hybridized or sp-hybridized. (vd) Ithas high degree stability due to filed bonding molecular orbital. Oo 400 4142-60, 4x0#2-28 4x142-6n 4x1+2=6n (Aromatic) (Aromatic) (Aromatic) (Aromatic) Forexample: igh Degree of stability: High degree of stability is associated with resonance energy. The compound which ‘have more resonance energy is more stable. The compound which have more potential energyyis least stable. 1 Aromatcity ce Resonance energy (R-E) ac Stability c: ‘Potential Energy(PE) Greater the resonance energy higher willbe the stability of compound, Resonance energy ofsome aromatic systemare given below as 2O000 21 keal/mol 29 kcal/mol 16 kcal/mol 36 kcal/mol 32 keal/metAromaticity (3) Presence of diamagnetic ring current: Aromatic compounds show diamagnetic ring current due to paired electron. | Facog (60) HH, where, Hy ~extemat magnetic felé i Fane = HAH , ~induced magnetic field A, Clockwise direction in electron present for aromatic compound. Deshielding region (igh 5 value) ae oy 47 deshielding region (down field) t a 11 shielding region (up field) % Aniacomatc comping ——_ —— > Deshiclding region Shielding region #765 4327 0 5 value—sp*> sp > sp? (decreasing order) due to anisotropic effect. + Molecule in which outer protons are deshielded and inner protons are shielded is known as diatropic molecule, These type of molecules are always aromatic in nature. Similarly, molecule in which inner protons are shielded and outer protons are deshileded are known as paratropic molecule. Paratropic molecule is aromatic in nature. ‘Antiaromatic compounds show paramagnetic ring current due to unpaired electron. Q oS \ == ‘ N \) H. H Il Pa HNC _| ! 4 H LY "\ t N | —~ Highly shielded proton a ¢ = (low 5 value) oO oO” OdAromaticity 3 Hiickel Rule: This is a very popular and useful rule to identify aromaticity in monocyclic conjugated com- pound, According to which a planar monocyclic conjugated system having (4n +2) delocalised (where, n= 0, 1,2, .».) electrons are known as aromatic compound . For example: Benzene, Naphthalene, Furan, Pyrroie ete. ne (4x0 +2) we (421+2)z6" =6ne n=2 (4%242)me" =10e~ n=3 (4x342)ne" =14ne" n=4 (4342) ne" =1876" + Craig's Rule: This rule is applicable for polyelic non-benzenoid compounds. If molecule contain C;-axis then count total number of double bonds (N) and calculate value of N-1 which decide aromaticity in compound, (Jf N-1=0dd, compound is non-aromatic (2) fN— 1 even, compound is aromatic. eg. Azulene resonating N-1 =4n bond (aromatic) + Insystem C,-axis must be present Cyaxis 1 — —CD—-C> (non-aromatic) — N=4 , odd. Hence, compounds non-aromatic. O-CO-OO (eptatene) (non-aromatic compound) N=6 =5, odd. Hence compound is non-aromatic. + Pentalene and heptalene is a non-aromatic compound, Since it does not follow craig’s rule + The organic compound which show aromaticity are aromatic in nature or diatropic in nature and th (outside the rings) signal always exist away from the TMS (these protons are dishielded protons) + Identification of aromatic, anti-aromatic and non-aromatic compounds.Aromaticity ‘Organic Compound (1)AromaticCompound —_(2) Anti-aromatic compound (3) Non-aromatic compound (a) Huckel rule 4n ne” delocalized restriction of delocalization me" (i) Monocyclic system n=1,2,3,4,5, (i) Polycyclic benzenoid Ane (b) Craig’srule n=2= 8ne Polycyelicnon-benzenoid. = n= 3 = 12 ne system planar (sp and sp*-hybridized) (system conjugated) sp? non-planar structure sp? hybdridized carbon atom insert sp’ restiction of ne~ ‘conjugation —> XY? COT (Cyclooctatetraene) Tub shaped (aon-aromatic) + Order of stability and order of resonance energy: Aromatic>Non-aromatie> Anti-aromatic. Calculation of x-electrons: During -electron count double bond count 27: electron and triple bond count 2m electron. Also, lone pair in conjugation is also counted. meal {3 3 oO Lép2e 6ne(4ne + | lp) Gne" (4ne +1 lp) 6ne~ (4ne +1 lp) species in which lone pair is not in conjugation can not be counted: Z Les | Ce : Se hybrid eg. S ASA yp hybridized ~~ sp? hybridized N Lone pair which participate in conjugation system and follow Hiickel's rule ae called Hiickel one pair while which lone pair does not participate in conjugation are known as non-Hiickel lone pair. Non-idekel 1) entte bon —— (Non-Hackellone-pair because bond 2 alcoon Semon i osen| Jone pair of nitrogen is not present (non-Hiickel (cabana) eer at pecipbery. double bond) ana Resonance Structure qiAromaticity [Non-Huckel double bond i 14x elton (Aromatic) 4 carbon = 14 election (Aromatic compound) Resonance Structure + Energy level of aromatic and anti-aromatic compounds can be shown by using frost circle or diagram. Energy levels of regular planar polygonic molecules with an even number of atoms form a symmetrical pattern as shown below. { Antibonding energy level ane { Bonding energy level Ifall bonding energy levels are filled then itis aromatic [Hiickel criterion also required] — — w1.80p — — «0456 — — ap — — att258 — «tp — asap 8 9 — «2p — — 1808 — = wt41p = : a eS =" aiossp — — att4ip — = atl s3p — _ai2p — —at2p Figure : HMO energies for conjugated planar ring systems of three to nine carbon atoms.Aromaticity te Anti-bond Do -- 0A oe 2n electron ‘Non-bonding sp? “me ; ‘energy level 7 Co \ Ay~ Ao AoA ‘4r electron oo 7 (Anti aromatic) eaicctaee level Frost Diagarm for Cyclopropenyl system + Anti-aromatic compound behaves as a biradical + Inanti-aromatic compounds two unpaired electron are present which are all paired. + Oxygen also behave as biradical and triplet state. + Carbene-triplet state are biradical ‘Types of Aromatic Compounds (A) 2n-electron system. (i)It follow (4n +2) ne” system. (ii) electron delocalised then compound is aromatic. (iii) Ifelectrons not delocalised then compound is non-aromatic iv) Compound will never be antiaromatic. Examples: ® g Q ° o&=A wfe = Jo 2 OO oA=A “Avnatic Aromatic Anti-aromatic Anti-aromatic ® ® OO OO weet (anti-aromatic) 2 OH o, 9 hy) | o ‘oH o ‘0 G A R @ (Aromatic compound) Displacement of electrons takes place towards higher electeonegative atom.Aromaticity (B) 4n-electronic system: (@Belongsto 4n xe” system doesnot follow Hiickel rule. (ii) [felectron is delocalised then compound is antiaromnatic. (ii) Ifelectron does not delocalised then compound never antiaromatic (iv) Ifelectron does not delocalised then compound is non-aromatic. ° @ O oA © of] (} A.a- “.. Anti-aromatic ss KA AA + (©)6r ebectron system: Examples: (i Belongs to (4n +2) ne" system. (ii) Helectronis delocalised then compound willbe aromatic. ii) Ifelectron does not delocalise then compound must be non-aromatic For example CH, AH OSes Or LOO CH, 6 e [G}-Fe(co), —> re O —Fe_,. ie = lo A A 6m e° system A (D) 8r electronic system : (Belongs (4n) ne" rule (ii) Ifelectronis delocalised the compound must be anti-aromatic (i) electron does not delocalise then compound is non-aromatic. W ca Tub shaped ‘Non-aromatic Anti-aromaticAromaticity (B) 10x electronic system: () Belongs (4n +2) me” system. (i) Ifelectron delocalised then compound aromatic in nature. (ii) Ifelectron does not delocalise then compound will be non-aromatic. (iv) Compound never be anti-aromatic. A 7 (Repuision between H-hydrogen atoms, causes the compound Lt J tobe non plana. So, compound is no-aromate) (Non-aromatic) We" system Cycisation Bridging Dehydrogenation > ‘Aromatic XC,N,O Aromatic os LN, 10ne" system somatic CD — CO- OD (10m €° system) * Azulene’is the isomer of Naphthalene + Aaulene is less stable than naphthalene + Azulene gives electrophilic substitution reaction + Five membered ring gives substitution reaction (because small siz, electronegativity) 3 oH oh : oH a like (same) charge must be at maximum distance and opposite charge must be at minimum distance for stability resonance structure, (F) 12 % electronic system: (i)Belongs to (4n) re" system (i) Ifelectron is delocalise then compound is anti-aromatic (il) Ifelectron does not delocalization then compound will be non-aromatic, (iv) Compound never be aromatic aqAromaticity cavity size small > repulsion ron-planar > non-aromatic 12ne a S OS (AL ci N,O AA 12ne” system-(non-planar) #5" aromatic, ae ] \ 2K aromatic S (G) 14x electronic system: (i Belongs to (4n+2)zte” system (ii) Ifdelocalize electron then the compound is aromatic (iif) electron does not delecalised then the compound non-aromatic (iv) It never be antiaromatic. Aromatic Aromatic Aromatic ANF a S nonaromatic pheneline Phenelone ion a (aromatic)6. Aromaticity Phenelene is acidic in nature why? Proton (H") remove from the phenaline and acidic in mature and system gain aromaticity. S-F {14 electron system) (BH) 167 electronic system: (i) Belongs to 4nre™ rule, (i) Ifelectron is delocalised then compound is anti-aromatic. (iii) Ifelectron does not delocalised then compound will be non-aromatic (iv) Itnever be aromatic. Dishielded (6-value high) \6re(Anti-aromatic) (1) 18 7 electronic system: (6 proton highly shielded) H | (double bond) Jo“s 4 [18] annutene 18ne" (aromatic) Completely conjugated monocyclic system called annuilene + 18 Annulene contain 3 cis close bond. coca Other Aromatic System: Fased ring aromatic. triafulvalene calicene qAromaticity + Such type of systems is aromatic or non-aromatic but never be anti-aromatic + Ifsuch type of system is aromatic then both ring must be aromatic after displacement of camman double bond. Otherwise both ring will not be aromatic p<] PR a | Pd PM pe pe AA A A ‘overall system nan-aromatic ‘overall system aromatic ‘overall system — non-aromatic Resonance energy of some aromatic system: OOOO 29 kcalimol 16 keal/mol 36 keal/mol 32 kcal/mol 21 tat Pyrrole is called as super aromatic compound 00 8 36- Smt g 67! forC-atomenerey. (tai C-atom) 5 1.2 per C-atom According to electron density at per C-stom, pyrrole is electronically rich. So, pyrrole gives electrophilic substitution reaction more easily than benzene. Electrophilic substitution reaction oc —————1____ resonance energy (aromaticity) ‘Quasi Aromatic Compound: These are generally ionic aromatic compound OH + Clog cS OF : ENa Nu + HCIO, ——> ‘Quasi aromatic compoundAcomaticity cl + NOS F a + AgNO; ——» + AgCl A + SbF; —> A (Quasi aomatic compound) Allotrops of Carbon: (Diamond (i) Graphite (ii) Fullerene Allotrops of earbon a Diamond Graphite Fullerene se hb { = a | Non-aromatic aromatic gives Aromatic gives addition reaction addition reaction Unstable (stable) (non aromatic) 22+ Aromatic) honge Dicimond >Graphite AH =-ve Hate + Tyiamond, AH =+ve (Stable) 242-5 (Unstable) Organometallic aromatic compound: Ferrocence —_Dibenzene chromium Fe Cr + Mesoionie Compound: Sydonsis the first meso-ionic compound which show aromaticity + Meso-ionic compound gives electrophilic substitution reaction + Meso-ionic compound also known as internal salt. & Jr i @ | \, _-0 (Sydons) + Homo-aromatic compound : Compound that contain one or more sp'-hybridized C-atomina conjugate cycle but sp’-hybridized carbon atomare force to lie almost vertically above the plane of the aromatic system known ashomoaromatic compounds. Ha H He + HS, ——> nl ). He " Hd lomrpylim Homotopslivm ——ormoopylimy cationAromaticity ava NaN CHCl GHsOH™ K Bu HM HOM a bb Na -—~| B>C. Which of the following compound is more stable, ® eo Oe) OQ @3 Soin, Soln, Which ofthe fotiowing compound is more anti-aromatic e 2 oA @ GO ° @ A (More anti-aromatic because more planar) The anti-arornatic compound have tandeney to adopt the non-planar structure to maximize its stability Which ofthe following compound gives H,-gas with metal. @| & O (both O--©) 10m electron system O-8=O 10" (planar) H acidic | Acide + Yel H OK SS (Cyclopentadienyl) ‘Aromatic (eyelopentadienyl anion) NA. Cyclopentadiene is acidic in nature due to aromatic character of cyclopentadienyl anion. Which of the compound have more dipole moment. Ae —K A aq ‘Maxiraum charge separation— maximum dipole moment because = qd, where, q=amount of charge, d = distance between two poles. (QD have more dipole moment than (11) ‘Which of the following reaction takes place. ot OO (Non-aromatic) —_(Anti-romatic) {Reaction is not possible because stability decrease} SN! > +L Ye because 2° carbocation form. (non-aromatic) (aromatic)Aromaticity 7. Which ofthe following compound gives geometrical isomerism. For geometric isomerism: At this carbon for both group must be different and C-C bond rotation must be restricted. 0 tio ects «iy bo C-Crotation possible Non-aromatic. 8. Which ofthe following compound is best hydride donor. OC. Q wh we Me le @ “Oe QO the the 9. Which ofthe following compound gives ppt. with AgNO,, Br Br ; “aD eA Soln. (and (i) Br + AgBr ——e Ol QO + AgNO; > O + AgNOs} LA) . ow (Quasi aromatic compound) 10, Arrange these molecules in correct order of deprotonation. D> O-—-De Soin. (ii)>Gi)>Aromaticity Soln. More acidic: ° ° ° ° H ase . H tase 5 H H ° 0 0 ‘O Stable de to resonance Mate the following Column-I Li @) ®) re ° of] 2 of 1O A-(), (iv); BH), (iv), Ci), D-(i)) ‘Match the folloiwng Column-L 4 A ar ie COHN tn | H Stable due to resonance ‘Column-It (Aromatic ii) Anti-aromatic (ii) Non-aromatic (iv) (4n +2) ne" Colamn-it (Aromatic il) Non-aromatic Gi Anti-aromatic (iv) HeterocyclicAromaticity eL | Soln, A-(i), (iv); B+), (iv); C-G), (iv); D-Gi); E-Gii) | HOSO;F 13. SoPs, SO;CIF CO;CHy _agee Inthe above reaction, Ais (@)Antiaromatic —-—(b) Homoaromatic__(c) Non-aromatic Soln. (b) (@) AntiaromaticCHAPTER Stereochemistry Stereochemistry : Tt involves the study ofthe relative spatial arrangement offatoms within the molecules Dynamic stereochemistry: Dynamic stereochemistry is the study ofthe effect of stereochemistry on the raie ofachemical reaction. First Stereochemist — Louis Pasteur (1849 Significance of stereochemistry: One of the most infamous demonstration of the significance of stere- ochemistry was the Thalidomide disaster. Thalidomide is a drug was first prepared in 1957 in Germany, prescribed for treating morning Sickness in pregnant women. It was discovered that one optical isomer Le, R- Jsomer of the drug was safe whereas the S-isomer had teratogenic effect, causing serious genetic damage to early embryonic growth and development. o Q ul / 0 Os i ° S-isomer Reisomer Drug for morning sickness in pregnant women, Teratogenic effect (Remark: In human body, Thalidomide undergoes racemization: even if only one of the two stereoisomers is ingested, the other one is produced } Now we have another example - Propanolol. R-Propanstt (contraceptive) $-Propanotol (ansibyperensive}Stereocheristry SOME TERMINOLOGY Optical activity: The term optical activity derived from the interaction of chiral materials with polarized light. Scalemic: Any non-racemic chiral substance is called Sealemic. + A cchiral substance is enantio pure or homochiral when only one of two possible enantiomer is present. + Acchiral substance is enantio enriched or heterochiral when an excess of one enantiomer is preset b the exclusion of the other. Three terms are used f0 designate a carbon atom bonded tetrahedrally to four different substituents i eh molecule, (a) Asymmetric atom (LeBell & Vant Hoff for an atom attached with different groups). (b) Chiral centre (©) Stereocentre. Asymmetric atom: ‘Compounds with one such atom are truly asymmetric as they lack symmetry. For example Asymmetic atom CH" Noclement of symmetry SAL isprseat inthe motel Sea oa % However, there are molecules which also have atoms with four different substituents and whiehialza bave various symmetry element including plane of symmetry as in mesotartaric acid. COOH Asymmetric centre fon —+ Plane of symmetry =} on Asymmetiecente-—~ QOH ‘Two asymmetric center but also plane of symmetry. Chirality is a geometric property which influences and affects all parts ofa chiral molecule. Stereogenic centre or Stereocentre: A stereogenic centre or in short a stereocentre isanatom having groups of such nature that an interchange of any two groups will produce a stereocentre, f 2 > OH Ho faeces ond-t owen Hon Da ; Hie HOH Ig 3. CHOH S.form Reform + Acarbonatom that is a stereocentre is also called a stereogenic carbon. Conformation: Structures that can be interconverted simply by rotation about single bonds are conform- tion of the same molecule. For example: 4 HH Kesh QW 1H H Hey HH Staggered conformation __‘Eclipsed conformation Note: These two are the conformation of ethane arises due to rational possibilites across C-<-c single bond. Configuration: Structures that can be interconverted only by breaking one or more bonds have different configuration and they are stereoisomers specifically known as configurational isomers. SStereochemistry Isomers Constitute same Stseoiomers > Chain isomerism Position Tsmerisn os > Metameris t Conformational omer Configurations Isomers > Taos + Valence Isomers r ae Ae vero single bond cots 9 es HA Teac 0 ae (or Umbrella inversion) iN i Conformational Isomer (conformers) ‘Configurational Isomers Contigurational Configurational Enantiomers Diastereomers Conformational Isomers - Conformational Conformational ‘enantiomers diastereomers \ nciomer: ast “These Wb ae eationers These to are diastereomers 4 4 H 7 4 " CH Hye H CH CHs @ s So, (A) and (S) are mirror image of each other as shown below H i 4 4 wot ow H om Eye 4 CHs CHy So, these two are conformational enantiomers‘Stereochemistry L 2 Gh, H Now, H. H ‘er H 4 wNtA.ci, CH Hs I stg Since, Iand I are not mirror image to each other so these two aré conformational diasteromers. Ss SS . a XS Conformational diastereomers Structures that are not superimpossible on their mirror image, and can therefore exist as two enantiomers are called chiral. Essential criteria for a molecule to be chiral. There is no any single criterion. There must be lack of element of symmetry. Note: [t isnot necessary and sufficient condition because there are some set of molecules which have some element of symmetry still they are optically active. For example, re Hck Q au a Ck Cz Optically active but having C,-symmetry, ‘The carbon in the molecule should be attacked to four different groups. Itis not a necessary and sufficient condition also because we have an example in which carbon have four different groups but iis still optically inactive. For example: coo ‘Two asymmetric centre but still optically in active owing to plane of symmetry. ‘On the other hand we have also an example in which there is not any chiral centre but still moleculeis optically active. For example: Properly substituted allene Br Br We re cnStereochemistry ‘Not any chiral cenise but stilliis optically active Remral This compound is optically active not due to chiral centre but due to chiral axis, ‘There should be an absence of plane of symmetry. SYMMETRY ELEMENT Asymmetry element is a geometrical entity such as a line, a plane, of a point with respect fo Whichone or more symmetry operations may be carried out. Symmetry Operation: Asymmetry operation is the movement ofa molecule about the symmetry element in sucha manner thatthe resulting configuration ofthe molecule sindistinguishable Srom the original molecule. The molecule may assume.an equivalent configuration or an identical configuration. Group Theory: Mathematical study of symmetry is called group theory. Symmetry element Symbol ‘Symmetry operation Axis ofsymmetry c, do C, Alternating axisofsymmetry S, dos, Plane of symmetry o doo Point ofsymmetry or centre of syinmetry i doi Tdentity E doing nothing, Various types of elements of symmetry are explained below as: (A) Axis of symmetry: An imaginary axis passing through the molecule, rotation on which by 9° gives an equivalent orientation of molecute, tis denoted by ‘n’. Where,n=1,2,3,4, Orientation: Orientation is three dimensional distribution of atoms and groups of molecule. For example: i\ aN wy a ore aes Initial orientation, Equivalent orientation Adentical orientation 360° So, the order of axis Cy = gis? ie. C, (pronounced as C-two) ‘Two things do an axis of symmetry. ee Axis of symmetry ——] L_y Interchange For example in H,0.Sereochemistry is of syeumetry Principal axis Subsidiary axis axis Axis other than Axis of highest Drineipal axis, ‘order Let us consider another example of NH. Vv Neu cs Nonny 7 Nils —— yr yin ‘These two ate identical ‘configuration ‘configuration . N., ys <2 a We HO, Hy Let us consider an example of BE, In BF, one C,-axis is passing through B-atom which s perpendicular to the molecular plane F fy F F, ito! ge Po \ a B B. os, N FL Fy F/ Fy FL Fo Identical Configuration BF, molecule has also 3C, axis. (1) Passing through B—F, bond and interchanging F /F, (2) Passing through B—F, bond and interchanging F/F,. (3) Passing through B—F, bond and interchanging F These three C,-axis can be represented as Fy \ CBF) B. rf FaStereacemisty (B) Plane of synumetry: Imaginary plane passing through a molecule which can bisect the molecule into two mirror image halves. Bisect ‘There ace two functions of a plane — L Reflect For example: () bisecting oxygen ator and reflecting H/H, (i Bisecting all three atoms. O, 9, Og 47D yp HH, (ii) Ammonia have three plane of symmetry. (1) Bisecting H,-N bond and reflecting H/H,. (2) Bisecting H.-N bond and reflecting H/H,, (3) Bisecting H,-N bond and reflecting H,/H,, ym ottisN) Neorg, GB) HY a Hg Hy Hp (iv) BR, is four plane of symmetry. (1) Passing through F,-B bond and reflecting F/F, (2) Passing through F,~B bond and reflecting F /F, (3) Passing through F,~B bond and reflecting F/F, (4) Biseoting all the four atoms viz F, F,,F,and B. (C) Centre of symmetry: A centre of symmetry is a point from which lines, when drawn on one side and produced an equaldistance on the other side, wil meet identical point in the molecule. For example: 2, 4-dimethylcyclobutane-1, 3-dicarboxylic acid Centre of symmetry) CHy Centre of symmetry ‘Now, we want to discuss symametry element of cyclopropane for the purpose of optical activity. Cyclopropane have one C, axis and three C, axis and four plane of symmetry,Stereochemistry Gs axis is passing through centre of triangle and perpendicular to all the three C,-axis, f Cyraxis Hy Ik Hy He 3C axis, 3 2 He Hs (a) Passing through, and interchanging C/C, or H/H, H/H, and HH, (b) Passing through C, and interchanging C/C, of H/H,,H/i3,, Hi, (©) Passing through C, and interchanging C/C, or H/H,, HH, and H/H,. 4 plane of symmetry. (a) Bisecting H, —Cy—Hg and reflecting C,/C,, H,/H, and H/H,, (b) Bisecting H;—c,—H, and reflecting C/C,, H/H,, H/H,, {© Biseoting Hy —Ca—n, and reflecting C /C,, 11/11, HJ, (@) Bisecting C,, C, and C, and reflecting H/H,, H,/H, and H/H, Now, we want to make cyclopropane molecule chiral for this we will have to remove all plane of symmetry from cyclopropane molecule. Because for & molecule to be chiral, plane of syrametry should not be present. Case J Mono substituted cyclopropane a a XK He/IN He Hs. Hs, Ithas plane of symmetry bisecting CILC-H, and reflecting H/H,and Hl, So, this molecules optically ~hyi Case IT: Homodisubstituted cyclopropane S a aia \/ MA “4 H Plane ofsymmetry — Plane of symmetry >No prea > Achiral ~>Achiral ~ But Cy-symmetryis present > Optically inactive > Optically inactive ~ Chiral molecule + Optically ative. Case IIE: Heterodisubtituted cyclopropane Hy Y. =k Br. a. a Bs, a a iy H « oer HM 7 = EN Sw NA jr : H 4 ~ Plane of syrimetry is present , > Noplane of symmetry >No plane of symmetry > Achiral > Noaxis of symmetry —>Noaxis of symmetry > Optically inactive Chiral Chiral > Optically active => Optically activeStereochemistry Case - II: Trisubstituted cyclopropane, cl cl a a Br 4 4 Br 4 ~+Plane ofsymmetry present. Plane of symmetry present > Achiral —Achiral > Optically inactive. + Optically inactive H @ 7 Br Br “fe H a Br i a > Plane of symmetry present > Noplane ofsyrmmetty > Noaxis ofsymmetry Chiral > Achiral > Opticaity active Problem: Find out which of the following molecule is optically active. Br ~ &, F cy, wT N70 ‘Symmetry properties of cyclobutane. Hy be : 2 He 7 h, . 3 He Hy Cyclopropane have one C,-axis and 4Cy's axis, 4o,'s and one o,. C,-axis passing through centre of square and perpendicular to Cy! s axis, Cr—Cp {-[ Cy—C 4C;s axis, (a) Passing through C, and C,, and interchanging C/C,, Hi /H, H/H,, H/H,, H/H,. (0) Passing through C, and C, and interchanging C, and C, H/H,, H/H, Hi /H,, AJ, (c) Passing through C,-C, and C,-C, and interchanging #1/H,, H/H., H/H,, HJ, (@ Passing through C,-C, and C,-C, and interchanging, H/H,, H1/H,, H,/H,, H/H,, 40,8 () Bisecting H,-CH, and H,-C, and reflecting H/H,, H/H, (b) Bisecting H,-C;, and HCH, and reflecting Hi /H, HL/H,,Stereochemistry (© Bisecting CC, and C.-C, bond length and reflecting HW, W/W, W/E, H/H,. (@ Bisecting C,-C, and C,-C, bond length and reflecting H/H,, H/H,, H/H, HH, (© Bisecting C,, C,, C, &C, and reflecting H /H, H/H,, H/H, and H/H,, Now, let us consider a case of substituted cyclobutane ~+ Plane of symmetry, -Achiral + Optically inactive, ci cle oO > Noplane ofsymmetry > Chiral > Optically active ci Me No plane of symmetry + Optically active cl a Plane of symmetry > Optically inactive COOH ~> Plane of symmetry ~> Optically inactive H cl cr 1. cea H + Plane ofsymmetry + Achiral > Optiacally inact 4 cl cr u By A H ow 4 —+Noplane of symmetry > Chiral + Optically active o + Plane ofsymmetry > Optically inactive + Achiral molecule, cl <1 of Bw > Plane of symmetry = Optically inactive Colts, COOH CHS “00H No plane of symmetry = Optically ative S Chiral molecule.Stereochemistry CH Hy HyC' CH 3c" “Hy COOH Hee ae Coon Plane of symmetry No plane of symmetry ~ Achiral molecule > Chiral motecule ~ Optically inactive. > Optically active Problem-2: Find out which molecules are/is optically active. os eo cf “ey ae 4 1 2 3 Br [%, BA “el Be Br Br Specification of configuration R/S : Then is absofute configuration of chiral centre Proposed byR.S. Chan, Sir Christopher Ingold, V, Prelog. Sequence rule: Priority to the four atoms or groups of atoms attached to the chiral centre can be deter- mined in accordance with sequence rule which are as follows. Rule 1: Ifthe four atoms attached to the chiral centre are al different, priority depends on atomic number, with the atom ofhigh atomic number getting higher priority. Rule 2: In case of isotope, the atom ofhigher mass number has the higher priority. For example among Br, C, D, H priority order is Br>C>D>H. 2 4 oe aha oe H—G—SogH H3C—C—Br 4 D3 Rule 3: [f the relative priority of two groups cannot be decided by rule mentioned above, then look for nextStereochemistry Rule 4: Where there isa double bond or triple bond, both atoms are considered to be duplicated or tripli cated. Ac I | —C—A 14 aac cH \ —c=cHy—> —C—C-C H If H (1) Assign the priority sequence by above mentioned method. (2) Find out position of the 4th group. 3) Connect 12-93 making a circle. : Hffourth group is below the plane, ‘LP. C LP Low priority group. C a HP — High priority group. HP. se y a LP. Clockwise + R Anticlockwise > S ‘Note: In this case 4th group'H' is below the plane and rotation is elockwise so, it is"R’ am 3 a CH, ey — HP. LP. HoH,c~\ %, 1 4 ‘Movement is clockwise So, itis R. Case 2: If fourth group is above the plane, rw BP. LP. Clockwise movement->$ Anticlockwise movement -> R. For example: 4 Zar oly . \Z Note: In this case 4th group is above the plane, c, So, clockwise movement gives 'S'. a” Case III: Ifthe fourth group is on the plane then do double interchange in such a way that the 4 group ‘undergoes below the plane.‘Stereochemistry For example: a 2 . js Qulchtacy In this case 4" group is on the plane. 1H” Yon, 3 Double interchange can be done as SOLVED PROBLEMS 2 cooH 1 4 1 : 3 CuwliMe i 2 (yn NH 2 fesdnooon neocX™,,, 1 2 Pw it s 3 OH “ s MY mm S-Methyl dopa I I 4 COOH 3 ICH,Br HO Br 2 i Note: In this case fourth group is onthe plane. So, we will have to do double interchange as shown below 3CHBr COOH CH,Br I Fint ' Second Comgoon PNA terchange™ AQ COM nergy HO! Br Ho "er 1. 20HL PROBLEMS Find R/S of the following compounds HAN, CoH ‘B/S Nomenclature in Fischer projection. ge Horizontal Line Nm eet eyee Intersection of these two lines represent C-atom. Vertical Line > away from the viewer. Horizontal Line ~> Towards the viewer, yea ‘Towards the viewer ‘Away from the viewer” For R/S nomenclature, Assign priority sequence, Case i If fourth group is present on the top or bottom of vertical line then t\ HP. LP, — Clockwise +R LP. HP. —» Anticlockwise > S1 NH 2 wos Loa Hye: COOH pe COOK aoe mae R NH H 1 4 CN a RR. Le. LP. AP. Clockwise > S Antclockvise +R For example: 2 3 oy, 3 chy Ph 1 200H 4 1 ‘NH; Cote H3C- ‘OH maw 7 ats 5 1 4 ; “ COOH 3CH, S OH CoHs $2 si 3 For example: 3 Ph ut 4 |s J 1 3 Hon Ho CH a z H3C’ Et H- Cos 4 Ss 4 Ss 3 CHO. Br 1 1 Conversion of Fisher -> Wedge. GHOH HOH. HOH;C. 40H CH Hac Cl HO—-H 5 fry a =) a, A ‘a Ona ltae “on fH ~0H ly Hy H L Bt” “ou Ho® ‘et Hs Ho por He cH, HOH Oe How" iy HOH H a y a Ho“, % oH “ou #0" Zo ts Note: Inall conversion, the configuration (R/S) should not be chang«CH He ph Hon on, H—--OH H Cols Cots, Conversion of fischer to sawhorse, FowW CH _ Ind carbon H OH ‘Note: Consider at first carbon shape like H: ‘OH (Pronounced 'Y') rah carbon H, (OH H. (OH oa eG Sts ; and then combine these two by a straight line like Hs oH Ht ‘ou oe H ‘OH Gis ‘Note: Since Fischer projection is represented in eclipsed form so the resulting sawhorse should also be in eclipsed formif we have need of staggered form we can obtain it by simple rotation. OTs For example: PL “Es Staggered form is suitable for elimination reaction since, for a form Ey elimination, the two departing group should be trans. H H Me, Me Me, ph s+ HOH + OTs wd Dd H Ph Tat Conversion of Fischer to Newmann: 2nd carbon, Me Ho, Reis Me an Ho, oes Ho. CoHs oh = — Staggered t—Catts eclipsed form — CHs oH form Me Me Me. Me Ist Carbon. | eclipsed form