STRUCTURAL ISOM ISOMERISM INTRODUCTION @ @ Gi) @ ‘The compound which have the same molecular formulabut differ in physical and chemical properties are called as Isomer and the phenomenon is called Isomerism., ‘The term ‘isomer’ was given by Berzellius. ‘The isomer was derived from Greek word meaning ‘equal or like part’ (isos= equal, meros= parts) Isomerism Structural Isomerism Stereoisomerism (Chain isomerism -—___ Position isomerism © id _ ee i oie ‘onfigurational ‘onformati Functional ieomerism ee Geometrical Optical Tastes Teomerism Isomerism STRUCTURAL ISOMERISM / CONSTITUTIONAL ISOMERISM ‘Structural isomers possess the same molecular formula but different connectivity of atoms, The term constitutional isomerism isa more modem term of structural isomerism. Itis sub-classified into following types. (Chain Isomerism : ‘The different arrangement of carbon atoms gives rise to chain isomerism, Chain isomers possess different Iengths of carbon chains (straight or branched). Such isomerism is shown by each and every family of organic compounds, Butane : C,H yg CH,- CH,-CH,-CH, n-butane CH HCH iso butane CHy n-butane has the chain of four carbon while isobutane has three in carbon chain. Hence they are chain isomers. Butyl alcohol : C,H,OH CH,-CH,-CH,-CH,OH n-Butyl alcohol CHy-CH-CH,OH Isobutyl alesho! CHy ‘These two butyl alcohols are chain isomers. Scanned with CamScannerSTRUCTURAL ISOME! i) dil) wy Position Isomerism Position isomerism is shown by the compounds in which there is difference in the position of functional group, multiple bond or substituent along the same chain length of carbon atoms. ‘To show position isomerism following conditions must be followed G) The same molecular formula ii) The same length of carbon chain ii) The same functional group, Example: (a) CHy~CH,~CH,CI_ and CHs-CH-CHy cl 1- Chloropropane 2- Chloropropane (b) (CH,—CH, - CH,OH and Hs GHCHy OH 1 -propanol 2-Propanol Ring chain isomerism Such isomerism arises because of the difference of carbon-chain or ring. For example : o L\ cneren, Cyclopropane —_Propene Cyclopropane and propene are ring chain isomers, @) — CH,-CH,-CH=CH, [| Cyclobutane Cyclobutane is the ring-chain isomer of I-butene, Note: Acyclic Alkanes do not exhibit ring-chain isomerism. Functional group isomerism Compounds with the same molecular formula but differing in the type of functional group they possess are classed as functional isomers and isomerism between them is known as functional isomerism. For example: CH,-CH,-OH and CH,-O-CH, Ethyl alcohol Dimethyl ether (Alcohol) (Ether) i Cis C-0-CHy Methyl acetate (Ester) Scanned with CamScannerWw) STRUCTURAL ISOMERISM 5-6 Alcohal CH,CH.NH, , — (CH,),NH, (CH,)N (1°—amine) (2-aminey (G*-amine) ef CHCH.CHECNH, — . CH,-CH-C-NH* CH,- C-N-CH, (1 amide) (amide) | (amide) cH, CH,CN , CH,NC (Cyanide) (socyanide) 1°, 2°, 3°—alcohols never considered asdifTerent functional group isomers but 1°, 2°, amine and 1°, 2°, 3°amides are considered as functional group isomers, Metamers : This type of Isomerism arises due to unequal distribution of alkyl substituents around a polyvalent functional group, ‘Some example of Polyvalent functional groups. -O- (Ether) —C- (Ketone) il oO =N-= (tert.amine) =S- (Thioether) | ? “FT ~ (Thioketone) =C-0- (Ester) s oO ih _* (acid anhydride) oT ® CH; ~C-CHl,—CH; CH; a4 CH, ~CHl~¢-CH, —CHs oO oO (2=Pentanone} (3-Pentanone) i)_Diethyl ether and methyl propyl ether CH,CH,OCH,CH, (Diethyl ether); CH,OCH,CH,CH,(Methyl propyl ether) Scanned with CamScannerSTRUCTURAL ISOMERISM Gi) Diethyl amine and methyl propylamine ‘CH,CH,- NH - CH,CH, (Diethyl amin ‘CH, CH,CH,-NH-CH,(Methyl propyl amine) 9 9 OH w) Oon-u eC) sro weer (vi) Tautomerism : (@ —_Tautomerism is a special type of functional group isomerism which arises due to the transfer of hydrogen atom as proton from a polyvalent atom to other polyvalent atom. (Such isomers are directly and readily inter convertible under ordinary conditions, and the isomers are called tautomers. (ii) Tawtomers exist in dynamic equilibrium. Gv) The other names of tautomerism are “desmotroprism’ or ‘prototropy’. () — Tautomerism is thus the property shown by certain compounds exhibiting different properties, as if they posses different structures and these constitutional isomers are called tautomers. (i) TF the hydrogen atom oscillates between two polyvalent atoms linked together, the system is called as Diad. H-C=N = C=N-H Hydrocyanic acid ‘isocyanicacid (i) Hydrogen atom oscillates in between first and third atoms ina chain, the system is called as triad, H-O-C=N = O=C=N-H (a) Keto-Enol Tautomerism - @ ‘When the tautomers exist in the two forms keto & enol then, such type of tautomerism is called keto-Enol tautomerism’. @ It was discovered by the scientist ‘Knorr’ in 1911 in acetoacetic ester. (ii) ‘The Keto means the compound has a Keto group > C = Q, and the enol form has both double bond and OH (hydroxy) group Joined to the same carbon. HO OH la ee — “— Keto forms Enol forms Conditions for tautomerism @ Presence of groups like >C = 0, -N =O ,>C =N- & a-H with respect to these groups In order for conversion of a keto form to its enol form it must have an a-hydrogen (i.¢., hydrogen attached to the carbon adjacent to the carbonyl group). Thus benzaldehyde, m-chlorobenzaldehyde (in general, aromatic aldehydes) formaldehyde, trimethylacetal dehycle do ‘not exist as their enol forms. i ? co Cul CO Y a Benzaldehyde m-Chlorobenraldehyde Scanned with CamScannerSTRUCTURAL ISOMERISM re cnt es cH CH; O Methanal ‘Trimethyl-acetaldehyde Keto enol tautomerism can occurs both in and basic medi Example of Keto enol tautomerism i t i 4) CHy=C-OH == CH-CH Vinyl alcohol “Acctaldehytle Keto form Enol form ? e qi) CH;-C-CH; <== CH,=C-CH; Acetone Isopropenyl alcahol Keto form Enol form Enol— Contents: Itis the % amount of enoL in ketacnoL. system usually ketocontent is generally more than Enol. contents. Enolcontents: Stability of enol aromaticinenol «« conjugation in enol « Hydrogenbondinginenol « Acid strength of a-H of keto form Presence of electron withdrawing group ‘Nonmnally Enol content of cyclic syste ondis easicrin cyclic system. -A.8 p Ap opel s greater than corresponding acyclic system as insertion of x- Scanned with CamScannerOH (Aromatic enol) STRUCTURAL ISOMERISM Scanned with CamScannerSTRUCTURAL ISOMERISM Qi (ay &) (oy (dd (ec) oO Q2 Q3 o4 ‘Mention thespecific type of isomerism exhibited by each of the following pairs: 1,2-dichloro ethane and 1,1-dichloro ethane Propanoic acid and methyl acetate Methyl acetate and ethyl formate o-Nitrophenol and P-nitrophenol Anisole and o-cresol Phenol and Cyelohexa-2,4-diea-1-one Incach of the following pairs which is more stable : Oa” Aaey oo fous w Incach of the following pairs which will have lessenol content ° i oly and (b) off OH, ° oT CT (©) CH, -CHO and CH, —CHO 1 a Incach of the. tneriee ‘pairs which will have lessenol content : poets polls (a a 2% we mo and Co. it ut Scanned with CamScannerSTRUCTURAL ISOMERISM as Qu In each of the following sets of compounds write the decreasing order of % enol content. © = Cy a ay a ay an wy) Ineach of the following sets of compounds write the decreasing order of % enol content, ° ° g 0 9 9 Ao~ JU AK SJL aw WV u cu tl A An we a Pu cHy Naa of eo, cy “cH; ® ay ay Among these give ease of enolization. 6 Ra Ra oH on + JM. iol wee A +d ae A” (ino) (Oe ad (Major) (Minor) Explain the observation, Decreasing order of enol content of the following. (along with proper explanation). a 2 9 © @ XK w AK, © us one aN we Assign the priority order nurmber tothe following atoms or groups, (a) -CHO, -CH,OH, -CH, , -OH (&) = -Ph,-CH(Me),,—H, -NH, (ce) -COOH,-Ph , -CHO, -CH= CH, (a) -CH(Me),,-CH=CH,,-C=CH, -Ph () — =CH,, -CH,Br,-CH,OH,-CH,CI @® — =H,=N (Me),, -Me, -OMe (@) -CH=CH,,-Me,~Ph,-Et (hb) -CH,-CH,-Br,-Cl,-CH,-CH,-CH,-Br, (Me),CH- @ = -Cl-Br-1,-NH, @ —_NH,.NO,, CH,NH, , C2N ‘Minimum number of carbon atoms required for an alkane toshow any kind of isomerism, Scanned with CamScannerSTRUCTURAL ISOMERISM “EXERCISE-2 (Objective Questions) Q4 Q6 Q7 [SINGLE CORRECT CHOICE TYPE] The number of primary, secondary and tertiary amines possible with the molecular formula C,H,N respectively. (A) 1.2.2 (B)1,21 (21,1 (D)3,0,1 C,H,Cl shows how many benzenoid aromatic isomers? (aya (B)3 (c)5 (D)6 ‘OOH HH & functionalisomer OMe Ot oro & metamers ‘Me CH,-CH,- OH ‘CH, O-CH, Oo ‘oO “ Me-N-Me & functionalisomers (A) TFTF (B)FTTF (C)TTFT (D)TEFT How many structural isomeric primary amines are possible for the formula C,H, yN? (a2 (B)3 4 (D)s How many structural isomers of C,H, are possible. (10 (ay ©i2 (D) 13 How many structural isomer are possible when onc of the hydrogenis replaced by a chlorine atom in anthracene? {A)3 (B)7 «4 (D)6 ‘Tautomer in followingis Diad system : 9 (A) CH,COCH, (B)CH,CH,NO, (C) (D) HCN Among the following the compounds having the highest enol content : (A) CH,COOCH, «B) CH,COCH, (© cH, -¢~cH,cHo (®) CH,-CO-CH,-CO,CH, Scanned with CamScannerSTRUCTURAL ISOMERISH Qo Q10 Qu Q2 Q13 Qua Qs Q6 it 10", cH,-C-CH—Ph 2 ay o ) isomerizes to (II) on addition on small amount of base structure of (II) is OH OH 9 ou (Ay cH, —-CH— CHP nen, -ci- Ph © A CB-CHRR ©) CH,-E—C-Ph OH O 00 Decreasing order of enol content of the following eompoundsin liquid phase HOW ate a) 2) @ @ (AJ2>1>3>4 (BYL>2>3>4 (C)4>3>2>1 — (D)3>1>2>4 ‘Which of the following cannot be written in an isomeric form? (A)CH,-CH(OH}-CH,-CH, (B) CH,-CHO (©)CH,=CH-Cl (D)C-CH,CH,-Cl “Thenumber of isomers of dibromaderivative of an alkene (molarmass 186 g mol~!) is (ay (B)3 4 (D)6 ‘The compounds C,H,OC;H, and CH,OCH,CH,CH, are (A)chainisomers (B) geometrical isomers: (C) metamers (D) conformational isomers ‘Which of the following have zerodipole moment?” (A) benzene 1,4-diol (B) trans-1,2-dichloro ethene (C)cis-1,2-dichloro ethene {D) 1, 1-dichioro ethene Br ,coon ILO) =} 8) nooé “Br (A) Positional (B)Chain, {C) Geometrical (D) Functional: ‘Molecular formulaC,H,,O canhave: (A)6-Aldehyde, 4-Ketone (B) 5-Aldehyde, 3-Ketone (C)4-Aldehyde, 3-Ketone (D) 5-Aldehyde, 2-Ketone Scanned with CamScannerSTRUCTURAL ISOMERISM Quiz Qs Qi9 Q.20 Q2r Q.22 Q.23 ‘Molecular formula C,H,Br., can have structures of (A) Twogem dibromide (B) Two vic dibromide (©) Twotcr-dibromo alkane (D) Noncof these ‘Only twoisomeric monochloro derivatives are possible for (excluding stereo) (A) butane (B) 2, 2-dimethylpentane (©) benzene (D) neopentane ‘Thenumber of structural isomers of C;HBryis (aya (B)3 os (D)7 On chiorination of propane number of products of the formula C,H,Cl, is (Only structural isomers) {A)3 (B)4 «C)5 (D)6 [MULTIPLE CORRECT CHOICE TYPE] ‘Which compound show tautomerism: f N OH (A) Oo (B) O «© QO (D) None of these ‘Which of the following compounds havehigher enolic content than Keto content; im (A) CH, -C-C-CH, B) ° “Lf oS In which of the fallowing pairs first will have higher enol content than secand : COO Et Q (ay THE and coon a Ne, (7000 Bt A By) HR an coos en “ent pat g c . 0 Saf nf on of wh A «D) id i A ons AA me No tH Scanned with CamScannerSTRUCTURAL ISOMERISM 0.24 25 Q26 qr Q28 ‘What statement is correct for Keto-enol tautomerism ? (A) Tautomersimis catalysed by acid and base. (B) Tautomers are present in dynamic equilibrium state, (C) Generally keto form is more stable than enol form in mono Ketones. (D) Atomic arrangements are same in tautomerism ‘Tautomer of following compounds: Oper y wOppery-O ou Oo OH On ° OH Which compound show tautomerism ‘ N-OH (A) Ph-NO B®) (Q (D) HCHO Enolic form of acetyl acetone is stabilised dueto: (A) resonance asa result of conjugation (B)intramolecularkydrogen bonding (©) vander waals foree (D)dipole-dipolerepulsion What is relation between (1), (ID) and (IM) ? 9 1H J a gs HN’ i 3 BRA o a) (um) I Pye, Malian Moibe (A) Tand Il are tautomers (B)ITTis conjugate base of I (C) lis resonance structure of 1 (Dyno relationexists Scanned with CamScannerSTRUCTURAL ISOMERISM Q29 Q30 Q3t Which of the fallowing is/are correct matchings ? ° Il (A) CH,—C—OH and H—C—OCH, Ti (B) CH—CH.—C = CH and CH—C = C—CH, = (C) CH,CH,CH.NH, and CH,—CH— NH, (D) CH,CH,OH and (CH,),0 - ‘Which compound cannot show tautomerism? 0 wah ok © 0 H Metamers Position isomers ‘Tautomers: Functional isomer [MATCH THE COLUMN] Match Column Iwith Column Il: Column I oO oO 4 I (a) CH3-C-O-CyH, & BI-C= cy CH, oy & 9 CHy IH ©L, * wl oo noon (D) CH,-CH-O-CH, & CH,-CH,-CH,-O-CH, I O-Et cn, cu, Column It ()— Chainisomer (Q) Positional isomers (R)— Metamers (8) Tautomers Scanned with CamScannerSoa mJ (JEE ADVANCED Previous Year's Questions) Q.1 Write structural formulae for all the isomeric alcohols having the molecular formula C,H ,O, [EE 1984] Q2 TrueorFalse: m-chlorobromobenzeneis anisomer of m-bromochlorabenzene. UEE 1985] Q.3. Thebondl energy (in keal mol) of a C-C single bond is approximately [EE 2010 (al «B) 10 (©) 100 (D) 1000 Scanned with CamScannerSTRUCTURAL ISOMERISM [SINGLE CORRECT CHOICE TYPE] Q.1 Which of the following has incorrect relation Me Pr a or «CL identical Me Me: Et ®) or & Cx positional isomers fr be Fo «) Cr & oO positional isomers Pe Me E ©) Cx & CS homologues Pr Q.2 Given compound shows which typeof isomerism 9 t Oro = OF-@ 8 b (A) Chain isomerism (B) Positional isomerism (C)Metamerism (D) Funetional group isomerism. oO PREP Q.3 0 Ph =— (P) final product is ? Cc: Woy a ®) py YN Db D 9 0 © a . ANP Scanned with CamScannerSTRUCTURAL ISOMERISM a4 Qs Q7 Decreasing oriler of enol content af the following compound in liquid phase oO ° °o Il IL IL i @) CH, -C-CH,-C-O-Et (b) CH,-C-CH,-C-CH, 0 tf cr (© Ph-C-CH,-C-Ph w || (Aja>b>e>d — (B)e>b>a>d — (C)e>b>d>a — (D) b> e> ard a{6)-bo cl H cH, a “es H” NcH, He Shouts which type ofisomerism (A) Functional groupisomexism (B) Geometrical isomerism (©)Meiamerism (D) Position isomerism [MULTIPLE CORRECT CHOICE TYPE] Identify the positionisomer. “w “YY try ®) ox &/™,, cN NC © ‘OCH, aN o Vf A OCH, ‘Which of the following can tautomerise. i 0 (4) €D,-C-Ph ot) “CLO ©) 8 H ‘Which of the following compounds show tautomerism ? q i (A) NH.—C-NH, (8) NH,—C—NH, 9 ll © wo-( Vw 0 (Db) CH,—C—cHh, Scanned with CamScannerQs Ql0 Qu Qi2 Q3 Qi4 STRUCTURAL ISOM [MATRIX TYPE] Match the column Column I Column Tt 9 OH “~ O OQ (P) — Tamtomers 9 OH ® O O (Q) Structural isomers HOH © O (R) Position isomers Oo CH. (Dd) Ch (S}__ Atleast one of the two structures is enol ‘OH [SUBJECTIVE TYPE] How many benzenoid isomer are possible for cresol. Find out the total number of cyclicstructural isomers of CgH,.. Calculate the total number of structural isomers of 3*-amines for the molecular formula CH, .N are? How many cyelopentane sinuctures (excluding sterea isomer) are possible for CyH,,. 20) Find out total number of structures of X. Scanned with CamScannerSTRUCTURAL ISOMERISM Qs Qi6 Quit Incachof the following pairs which is more stable : on oO) Sy ¥ (ib vou O10 Say FS Ineach of the following sets of compounds write the decreasing order of % enol content, io) os cr A Le QO oO CH a oO fe () ~N , H H 0 wy ay ayy 3% enol content of acetylacctane in following solvents is found as > Solvent “% enol content H,0 15 Liquid state 16 hexane 92 gas phase 92 Explainthe observation. Scanned with CamScannerSTRUCTURAL ISOMERISM Ql Q2 Qs Q6 a) ) © @ © Q10 Ql Qs Qis Q.22 Q29 ANSWER KEY EXERCISE-1 (a)Positional (b) Functional (c) Mctamerism (d) Positional (¢) Functional (f)Tautomerim (a) 2; (b) 2; (c) 15, (4) 2; (e) 1 Q3 (a) 2; (b) 1; (c) 25 (4) 15 (ep (a) 2; (b)2 Q5 (a) 3>1>2; (b) d>2>1>3 3>2>4>1 Q7 3l>2 o oO pia Non > Me Me (@ fe) p o 0 oO tS » AD ys @) ® Me > Me (b) (© I Keto formis less stable due torepulsion between — C = © groups so that this exist in enol farm. Enol a formisalso stable due toH-bonding Active 'H' atom / Aci molecular H-bonding)> atom so has more enolic content (enol stabilise by resonance & Intra Enolic contents decreases with introduction af e“ donator group which causes repulsion in enolic form . Due to ester group acidic structure of active H decreases & C=C of enol undengoese cross resosnace > Lowest enolic content because C=O is more stable than C=C Bond (a) 4,1,2,3 (b) 4,1,2,3 Co) 1,3,24 (A) 4,3,2,1 (©) 24,3,1 (9 4,2,3,1 (2) 314.2 (h) 2.4,1,3 (03.214 G)2, 14,3 4 EXERCISE-2 c Q2 A Q3 ¢ aac Qs c Qc Qi0 BO Qn Qu2 A Q16 B QI7 A QI8 A Qs BD Q23 AC Q.24 ABC Q.25 ACD Q.26 BD O30 B Q3I (A)R,(B)QKC)S,D)Q O6 A a7 D Qs c¢ Qi B Q20 B Q2zl ac Q27 AB Q28 AC oe Scanned with CamScannerSTRUCTURAL ISOMERISM EXERCISE-3 Qi B Q2 ¢ Q3 C Q4 B Qs oc Qe BC Q7 ABC Q8 ABCD Q9 (A)P.OS;(B) QS; (C) QRS; (2) OS Q10 5 Qu 12 Qiz 7 Qi3 4 Qi 7 QS (a) 156) 1; PG) (ey Q16 (a) 4>1>3>2; — (b)3>1>4>2 Scanned with CamScanner