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Isomerism Typ Notes

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Isomerism Typ Notes

Best notes on isomerism for jee

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Harsh bajaj
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ISOMERISM INTRODUCTION (The compound which have the same molecular formula but differ in physical and chemical properties are called as Isomer and the phenomenon is called Isomerism. @ —_Theterm ‘isomer’ was given by Berzellius. (a) Theisomer was derived from Greck word meaning ‘equal or like part’ (isos equal; meros = parts) Isomerism Structural Isomerism ‘Stereoisomerism |_— cain isoeneriem |— Position isomerism ; , | Sing ei ram Configurational Conformational | Functional isomerism [_ Metamerism Geometrical Optical — Tautomenism Isomensm is (1) STRUCTURAL ISOMERISM / CONSTITUTIONAL ISOMERISM ‘Structural isomérs possess the samemolecular formula but different connectivity of atoms. The term constititional isomerism isa more modem term of structural isomerism. Itis sub-classified into following types. @ — Chain tsomerism: ‘The different arrangement of carbon atoms gives rise to chain isomerism. Chain isomers possess different lengths of carbon chains (straight or branched). Such isomerism is shown by each and every family of organic Butane : C,Hig CH,-CH,-CH,-CH, n-butane CHiy-CH-CHy iso butane buy ‘butane has the chain of four carbon while isobutane has three in carbon chain. Hence they are chain isomers. Butyl alcohol : CH,OH CH, - CH,- CH,-CH,OH ‘Butyl alcohol HOH Isobutyl alcohol These two butyl alcohols are chain isomers. Gi, 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 (@ The same molecular formula (ii) The same length of carbon chain Gi) The same functional group. Example: @ CH,-CH,-CH,CI and cy GH-cHy a 1-Chloropropane _—_-2- Chloropropane © CH,-CH, - CH,OH and Ceca 11-propanol 2-Propanel Ring chain isomerism ‘Such isomerism arises because of the difference of carbon-chain or ring. For example : 0 L\ CH,CH*CH, Cyclopropané\. 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 ample: CH,-CH,-OH and CH,-O-CH, Ethyl alcoho! Dimethyl cther (Alcohol) (Ether) ° CH,-CH, CHty-E-0-cH, Propanoie acid Methyl acetate (Acid) (Ester) ” Phenol ‘Alcohol CH,CH,NH, , cH CH,),NH , (°=amine) (2-amine) CHCH-C-NH, , CH,-CH-C-NH > (I amide) (2 amide) | an, CH,CN , ‘CH,NC (Cyanide) ((socyanide) (CH,CH,),N (@%amine) CH,-CH,-C-N-CH, (3*amide) 1°, 2,3°—alcobols never considered as different functional group isomers but 1°, 2”, 3°-amine and I°, 2,3" amides are considered as functional group isomers. Metamers : This type of Isomerism arises due to unequal distribution of ally] substituents around a polyvalent group. ‘Some example of Polyvalent functional groups. —O- (Ether) + (tertamine) 0 CHy-C-CH,-CH, CH, and oO (2—Pentanone) -C-— (Ketone) I CH,-CH;-¢-CH,-CH, (3—Pentanone) (ii) Diethyl amine and methyl propylamine CH,CH, — NH-CH,CH, (Diethyl amine); CH, CH,CH,-NH-CH,(Methyl propyl amine) @ Co Lory Naa ™oleg are metamers (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. (i) Such isomers are directly and readily inter convertible under ordinary conditions, and the isomers are called tautomers. Gi) —_Tautomers exist in dynamic equilibrium. (iv) The other names of tautomerism are ‘desmotroprism’ or ‘prototropy’. (¥) Tautromerism 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) If the hydrogen atom oscillates between two polyvalent atoms linked together, the system is called 2 as Diad. H-C=N = C=N-i Hydrocyanic acid isocyanic acid! (ii) Hydrogen atom oscillates in between first and third atoms in athain, the Systert is called as triad. H-O-C=N <= QAC=N-H (a) Keto-Enol Tautomerism- (When the tautomers exist in tH€’two forins keto & enol then, such type of tautomerism is called keto-Enof tautomerism’. It was dise6vered, by the. scientist ‘Knorr’ in 1911 in acetoacetic ester. ‘The Ketomeans the compound has a Keto group > C= O, and the enol form has both double bond and OH (hydroxy) group Joined to the same carbon. he u CC = To | Keto forms Enol forms Conditions for tautomerism (@ Presence of groups like >C = O, -N = 0 , >C = N- & a-H with respect to these groups. (i Inorder for conversion of a keto form to its enol form it must have an a-hydrogen (i.e, hydrogen attached to the carbon adjacent to the carbonyl group). Thus benzaldehyde, m-chlorobenzaldehyde (in general, aromatic aldehydes) formaldehyde, trimethylacetaldchyde do not exist as their enol forms. CH; ent CHs-¢—CH ° cH, 0 ‘Methanal Trimethyl-acetaldehyde Gi) Keto enol tautomerism can occurs both in acidic and basic medium. Example of Keto enol tautomerism :~ H 0 cHy-C-on = cit Vinyl alcohol Acetaldehyde Keto form Enol form ° Ht @ CHyC-CH; — = CHyCCH; Acetone Isopropenyl alcohol Keto form Enol form. Enol— Contents : Itisthe % amount of enoL in keto enoL system dstfally keto contéft is generally more than Enol. contents. Enol contents: « Stability of enok, & aromatic in enol ‘e€onjugation ittenol alHydrogen bonding in enol « Acid strength of a-H of keto form x Presence of electron withdrawing group Normally Enol content of cyclic system is greater than corresponding a cyclic system as insertion of n- bond is easier in cyclic system. «Ad th at SL ° ALA, 0.0:0 BA» Bt wh Ka Hedtocf OH (Aromatic enol) MC Qu Q CH,CH,CH,-Cl and cx, -cH-CH, shows which type isomerism 1 a (A) Chain isomers (B)Position isomers (C) Functional isomers (D) Metamers CH,CH,CH,-OH and CH, -CH-CH, shows which type of isomerism OH (A) Chain isomers (B) Position isomers (C) Functional isomers (D) Metamers CH,CH,OH and CH,-O-CH, express which type of isomerism (A)Functional isomers (B)Chain isomers (C) Metamers (D)Position isomers Qa Qi Qs Qs Q10 Qu Q12 CH,-CH,-CH,-CH, and CH, ~CH-CH, shows which type of isomerism I CH, (A)Chainisomer _(B) Position isomer (C) Functional isomer (D)Metamers Alcohol and ether express which type of Isomerism (A)Position isomers (B)Chainisomers (C) Metamers (D) Functional isomers How many position isomers are shown by CH, -CH = CH-CH, (a)2 (B)3 4 (D)5 How many pasion isomers are shown by Hy eft -CH,-NH, (ays (D)2 re Gane (A)Position isomers (B)Chainisomers _(C) Functional isomers (D)Metamers How many Ring chain isomers are possible for Cyl. (a)2 (B)3 ©4 (D)s CH,—CHy=CH=CH, and [ ~] express which ype isomerism. (A) Ring chain isomers (B) Metamers (©Positionisomers _(D) Chainisomers cH, -cuscryana L egetichopeotiemetin (A)Ringchainisomers (B)Chainisomer (C)Positionisomers (D)Mctamers CH,CH,CH,NH,,CH,CH,NHCH, and CH, - N-CH, express which of lomerism I CH, (A) Functional Isomers (B) Chain Isomers (C) Metamers (D) Position isomers g (CH,CH,COOH and CH, ~C-O-CH, express which of isomerism (A)Position isomers (B) Chain Isomers (C) Metamers (D) Functional Isomers. Alkynes and Alkadienes express which type of isomerism (A)Position isomers (B) Chain isomers (C)Metamers (D) Functional isomers. Q17 Q.18 Quis Q20 Q2 Q22 Q3 Qu CH,-CH,-O-CH,CH, and CH,-O CH, CH, CH, express which type of Isomerism (A)Metamers (B) Functional isomers (C)Tautomerism (D) Functional isomers a, cH, CH,-C-CHCH, and CH, -C-CH,CH, express which pe tomers 0 (A)Meumers (8) Tautomers (©) Functional isomers (D) Position isomers Rae oO oO and express which type of isomers (A)Meamers —_(B)Tautomers (©) Functional Isomers (D) Chain Isomers Diethyl amine and methyl propyl amine express which type of Isomers. (A) Functional isomers (B) Position isomers (C)Mctamers (D)Chain isomers The molecules which exhibit metamerism are {A)C,H,,0 (ethers) (B)C,H,(alkene) —_ (C) C,H, (ketone) (D) C,H, (amine) Which molecule does not express Tautomerism. {A)(CH,),CCHO — (B)CH,CHO (©, CH, -C-cH, (D)CH,-CH,CHO ° Which form ig more stable for CH, -C-CH, ll (A)enol-form (B)keto form (C) both form are equally stable (D) keto and enol form does not exist ‘Which molecule has higher enol content CH,-C-CH. CH,-C-C-CH ap ® ri? ° 00 (©) CH -C-CHl,-€-CH, oct ° o Which molecule has higher keto-contents (ay Cit, -C-CH, (B)H-C-CH,-C-H 0 9 ° ° (D) CH, ~C-CH,-C-CH, g Which ofthe following compounds can exhibit tautomerism : wl oF of : ‘CH= CH-OH @) Q.26 Thenumber of structural isomer shown by C,H,, (Ayo Bs ary (D)8 Q.27 How many chain isomers are shown by C,H,g- (A)3 (B)2 « (Ds Q.28 How many chain isomers are shown by C,H,OH (A)2 @®)3 oa (ys Q.29 Number of structural of isomers shown by C,H,,: (a4 Bs (8 (D)6 “ANSWERS Qi B Q2 B Q3 A Q4 A QS Di Q6 A Q7 D QB A Q9 A QO Al QU A “Quiz a Q13 D QI4 D QUIS D O16 A, Q47 A Qu A Q19 C — Q.20 A,C.DQ21 A Q22°B O23 C OM B Q25A,B,C.DQ26B Q27 B 9 Q2 A Q29 B (11) STEREOISOMERISM / SPACE ISOMERISM Compounds having same molecular formula, same connectivity and structural formula but differ due to spatial arrangement of group or atom are said to be sterco isomers and phenomenon is termed as stereoisomerism. [tis divided into two parts : (1) Configuration isomerism (2) Conformational isomerism L Configuration isomerism : Stereoisomers which are not interconvertible at room temperature are known as configurational isomers Configurational isomerism is further divided into two parts (A) Geometrical isomerism (B) Optical isomerism GEOMETRICAL ISOMERISM It is type of configurational isomerism which arises duc to restricted rotation of atoms or groups around a double bonded system or cyclic system. Forexample: ™~ al x UY @ =¢ ) c= x7 Ny yr “x Not showing G.L Showing Gl. (Because same group X and Y present on each carbon) Geometrical isomers are [Link] (a)cis-trans isomers (b)EandZisomers — (c)Syn-anti isomers (a) Cis-trans isomers. When like atoms or groups attached at the same side of double bonded (C-atom-called as cis. isomers. When like atoms or groups are on the opposite sides of doubly bonded carbon, are called. trans isomers. an “4 a > per oNp poor, cis isomers trans isomers. a UA CK, Ln c-€ cae um OM wm “a cis isomer trans isomer HOOC.. COOH HOOCL LH c= oC. 17 O™ ~~ coon Maleic acid Fumaric acid (cis isomer) (trans isomer) () EandZisomers, 0 ‘The above system is used for derivatives of alkenes in which all the four substituents should be different a Sdened @ Following stofrles( Cate = Ingold-Prelog rules) the substituents on a double bbond are assigned priorities. (The double bond is assigned the configuration E (From entgegen, the german word for opposite) ifthe two groups of higher priority are on the opposite sides of the double bond. 1 7 pency, * form Wool goercX, Zform Priority rule : cahn, ingold & prelog proposed a sequence rule. Rale-1 Role-2 Rale-3 Rules ‘When atom or group of atom which are directly attach to the stereogenic centre have higher atomic number will have higher proirity. Example Q), 2) Feet NH NO; 7 Bray Fo NCH M 3 (2) Z-form E-form ‘When the atomic number will be same, priority assigned on basis of atomic weight. (NH HQ) Q)cHy-cH, "Sp E-form When both atomic number and atomié weight are same then proirity will be decided by the next joining atom. chy crc cy) =cf CH; -CH,-CH, “ CH, -CHy eg a) ay (E-form) (2) CH, CH; cu, ! ISCL Ci; - CH-CHy @) ch, °C ch 2 Sara, ay () OH CH; (Z-form) If multiple bonded group attach to the double bonded carbon, then they are considered in following manner. 7 eno > EG Crane -G-pe a, © Ex.1 Qcr-cHy _ ecu=0") aha SCH; -OH (2) (E-form) Qc _-cH=-cH,? Ex? cng 7 ca ay 6 form) ‘Syn-anti isomers This type of isomerism exhibit by oximes and Azo compound. Oximes are the compounds formed by the reactions of aldehydes or ketones with hydroxyl amine. The products obtained have all the necessary conditions for Geometrical isomerism. i.e. restricted rotation they can be represented by the general formula N-OH— Oxime of aldehyde x and oxime of 7 C=N~-OH *) Ketone also show Oxime _\Geometrical Isomerism Aldoximes Cin ol Cy ll Ml NN on Ho7™ Syn form ‘Anti form ‘When -OH group and H atom is same side, then it is syn form otherwise anti form CHs S77 CH2-CH2 CH, - CH, \,7CHS Non Non Syn form Anti form In unsymmetrical Ketoxime, if-OH and the alphabetically alkyl present on the same side of double bond, then it is called as syn form and other isomer is anti form Geometrical Isomerism in Azo compound : Ea. Ph-N=N-Ph ay” ~™R Yr t i _— a | Geometrical Isomerism in cyclo alkane : In cyclic compound the rotation about C - C single bond is not free because of the rigidity caused by the presence of other carbon of the ring which keep them tightly held, thus a disubstituted cyclic ‘compound (having the two substitution atthe separate carbon) will also show Gcometrical Isomerism. ‘The substituents on the same side are cis-isomers while the substituents on opposite sides represent trans-isomers. 4 WNW IN A A W a a a a a Hu 1 Trans form ‘Trans form Cis form Cis form No. of geometrical Isomers in polyenes : Case-1 In case of unsymmetric alkene. If R, # R, (R, - CH = CH #CH = CH) R,) [Link]| 2" n+ number of double bond showing geometrical isomerism Ex- CH, - CH = CH+ CH = CH~CH, - CH, N= 2" = 4. Case-2 [Link] of symmetric alkene. If R, = R, (R, - CH = CH - CH = CH-R,) [Link] GL=2""'42"1 ifn is even no. then , P = 5 if n is odd no. then, P= °2* Ex. CH, - CH = CH-CH = CH-CH=CH-CH, as3 Bat my here N=2+2'=6 MCQ Q.1._ Which of the following compounds exhibits geometrical isomers - (A) GH,Br (B)(CH)(COOH), (C) CH,CHO (D) (CH,)(COOH), Q3 > Malcic and fumaric acids are: (A) Geometrical isomer (B)Tautomers (C)Optical isomers (D) Metamers Q4 Which of the following can exhibit cis-trans isomerism - (A) HC = CH (B) CICH = CHCI (C)CH,.CHCLCOOH (D) CICH, - CH,CI QS Geometrical isomerism is possible in case of: (A) Pent-2-ene (B)Butane (C)2-Butene (D) Ethene Q6 Give the E-Z designation of the following compound - Colts 1 cane" (NE (B)Z (EZ (D) E-E Q.7 Which of the following compounds will exhibit trans (geometrical) isomerism? (A) 2-butene (B)2-butyne (C)2-butanol (D)butanal "ANSWERS Qt B Q2 D Q3 A Q4 B .Q5 AC Q6 A Q7 A OPTICAL ISOMERISM Configurational isomers which are differ in their optical activity. Optical Activity : The ability of optically active substances to cause rotation in the plane of oscillations of polarized light is called optical activity. The substances which do not have any interaction with plane polarized light are called optically inactive substances. Following experiment was conducted to determine the optical activity of a substance (a) _Undcrordinary conditions, the light waves oscillate in infinite number of planes passing through the line of propagation at right angle. (b) Plane polarized light isa light whose vibrations take place in only onc of these possible planes. (© Ordinary light can be turned into plane polarized light by passing it through Nicol prism (made up of calcite, a special crystalline form of (® When plane polarize light i passed through the liquid or dissolved state of such substances. (© Theplane of oscillation gets rotated through some angle towards left or right of the original plane of oscillations. The substances which rotate the plane of polarized light are called optically active substances. (9) Thesubstances which rotate the plane of polarized light in the clockwise direction, ic., towards right are called dextrorotatory substances (Latin : dextro means right). This is indicated by putting abettcrd or (+) sign before the name of the substances. (© _Thesubstances which rotate the plane of polarized light in the anticlockwise direction, ic. towards let are called leavorotatory substances (Latin; laevus means left). This is indicated by putting letter ‘I* or (sign before the name of the substance. @ ®) © (i) The amount of rotation caused by an optical active compound depends on various factors (a) Wavelength of ightbeam (b) Temperature (©) Density or concentration (d) Length of the solution through which light beam has been passed. ‘Specific Rotation : The specific rotation of optically active compound can be defined as the amount of optical rotation observed when plane polarised light is passed through a solution of 1 gm per ml ‘concentration solution ina I dm long tube. a Specific rotation = [a], = = Cause of optical activity: Inorder to exhibit optical activity, an object or molecule must be chiral. ‘Any molecule or object is said to be chiral if does not have any clement of symmetry ic. plane of ‘symmetry or acentre of symmetry. Plane of symmetry:= A ‘Plane’ of symmetry is a plane which divides an object in such a way that the part of iton one side ofthe plane is the mirror image of that on the other side for eg. a ball is symmetrical while a hand i$ asymmetric A chiral molecule or object is non-super impossible on its mirror images. Hence, chiral objects or molecules are also called dissymmetric objects or molecules the word chiral in fact is derived from the Greek word cheir, meaning hard. Chiral centre:- (i) Acarbon atom bonded to four different atoms / groups in the molecule is called Chiral centre. (i) The chiral centre in the molecule is represented by asterisk (*). For example, the sccond carbon in lactic acid is chiral centre because it is bonded to four different groups (-H,-CH,, -OH and - COOH). qd) Chiral centre H ly cx,-¢- COOH on ii) Somme more examples of molecules having one chiral centre are cH,-CH-cH, cH,-CH-CsH, CH,[Link],-CH-C.H, Br OH cH, 2-Bromobutane 2-Butanol 3-Methythexane ‘Compounds which are mirror images of each other and are not superimposable are termed enantiomers and the phenomenon is described as enantiomerism. Enantlomers : Enantiomers are molecules which are mirror images of each other ic. they should be non-superimposable. e ‘a ‘Characteristics of Enatiomers : 0 @ @ @) ‘Some of the important characteristic$ ofenantiomers arc as given below : Enantiomers have identical physical properties such as melting point, boiling point, density, refractive index etcs Enantiomers are optically active substances. They rotate the plane of polarized light in opposite directions but to the equal Extent. Enantiomers have identical chemical properties. This means that they form same products as a result ‘ofchemical combination. However, their reactivity ic. rates of reaction with other optically active substances are different. Enantiomers have different biological propcrties. For example (+) -sugar plays significant role in animal metabolism. On the other (~)-sugar does not play any role in metabolism. Representation of Enantiomers : @® (a) Wedge and dash formulae (b) Fischer Projection Formulae Wedge and dash formulae : G) In this method, the four groups bonded to the chiral centre are represented by different means. Gi)Anormal line represents the bond lying in the plane of paper. Gi) A broken line represents the bond going behind the plane of the paper and a solid wedge represents the bond projected out towards the viewer. bow thle in the plane (@) Fischer Projection Formulae (i) Emily Fischer devised a most simple and convenient method to represent the three dimensional arrangement of groups bonded to chiral centre. (ii) He used the point of intersection of two perpendicular lines to represent the chiral centre. (iii) Horizontal lines represent the bonds projected out of the plane of the paper towards viewer. (iv) Vertical lines on the other hand, represented the bonds projected back from the plane of the paper away from the viewer. (v) The Fischer projection formulac of enantiomers of 2-butanol and lactic acid are as under ‘Chiral centre cH, CH, CH, cH, OH H HOH OH wo aH, CH, (00H COOH Enantiomers of 2-butanol Enantiomers of lactic acid Important Points About Fischer Projection Formula : (1) Fischerprojection ofa stereoisomier must not be lifted from the plane of the paper and tumed over. ‘Such an operation would result into an arrangement which is enantiomer of the original stereoisomer. w w — — x Y Y (A) Enantiomer of A (2) Fischer's projection can be rotated in the plane of the paper about the chiral centre through 180° or its whole number multiple. Such an operation produces the same arrangement Ww Y + Sa la (A) (Same as A) @ @ @ ww) Keeping on rou as steady, the othe groups in the Fischer projection can be road clockwise o anticlockwise simultancously. Such operation would give same arrangement as the original. W) Fixed Ww [Pe geen y—}—x Ne (A) (Same as A) Diastercomers : ‘The stereoisomers which are non-superimposable and donot bear mirror image relationship are called diastereomers. For Example, a compound having two asymmetric carbon atoms can have four stereoisomers as shown below in the case of tartaric acid: COOH COOH n—lon } Ho —H X- on | Ho——# a ; cH, (is mirror image of (II), similarly (II) and (TV) aré mirror in isomers are two pairs of enantiomers. Now compare (I) with nor they are mirror images. They are called diastereomers. (I) and (IV) are also diastereomers, as are (II) and (III) and (Il) and (IV): Characteristics of Diastereomers are: ‘They show similar but not identical chemical properties. The rates of reactions are different. ‘They have different physical properties, such as melting points, boiling points, densities, solubilities, refractive indices, etc. ‘They canbe easily separated through fractional crystallization, fractional distillation, chromatography, ete. Diastereomers are also encountered in the case of geometrical isomers: HO CH, WC C= Cac “a u~ cn, Cis Trans MESO COMPOUND (a) The: containing two or more chiral centres but sing achiral molecular structure o © @ © CH,CH, (2S, 4R) Meso Compound Plane of symmetry is represented by dotted line Meso compounds do not rotate the plane of polarized light in any direction, ie. they are optically inactive. Thisis bocausc of achiral nature of their molecules. Because ofthe present of plane of symmetry the optical rotation caused by half of the molecule is compensated by the rotation caused by the other half This cancellation of rotation within the molecule is referred to 2s internal compensation. Inshort, the meso compounds are optically inactive due to intemal compensation. CONFIGURATION 0 @ Ww ‘Three dimensional arrangement of groups abott the chiral Centre is called configuration ‘There are two methods for assigning configuration to amolecule : (@) Relative method (b) Absolute method. Relative method of configuration (D, L System): (a) ItusesD-Glyceraldchyde and L-Glyceraldchyde asthe basis for the configuration determination. (b) The stereochemical descriptor D refers to the arrangement in which - OH group attached to the chiral centre is on the right side of Fischer projection, whereas descriptor L refers to arrangement in which ~ OH group is on the left side ofthe Fischer projection of glyceraldchyde. cHO. wefon —— wo—tcn, CHOH CHOH o wo (@) This method was found suitable for the study of optically active sugars as the sugars are defined as poly hydroxy aldehydes and ketones. (€) Glyceraldchyde also contains hydroxy and aldchyde groups but this method cannot be used for those molecules which do not process hydroxy aldehyde groups like CFC1 Bel. (0) Iftwo or more than two ~OH groups are present then D, L configuration is decided on basis of -OH ‘group of lowest chiral in the Golden rule following fischer projection Examples: o iy 1H ‘COOH COOH ‘OH ‘OH H ‘OH oH H Hi, D-form D-form L-form R-S system (Absolute configuration) R-+ Rectus (Right) S~ Sinister (Left) R-S nomenclature is assigned as follow : Step-I :- By the sct of sequence rule, we give the priority order of atom or group connected through the chiral carbon. Step-II :- If atom/group of minimum priority present on the vertical line, then Movement of eyes in clockwise direction = R Movement of eyes in anticlockwise = S Movement of eyes taken from 1 -+ 2+ 3 through Low mole¢ular weight group (if needed) Optical Isomerism in compound containing no chiral carbon atom \Various types of compounds belonging to this group are allenes, alkylidene cycloalkanes, spiro ‘compounds (spiranes) and properly substituted biphenyls. @ _Allenes These are the organic compounds ofthe following general formula. >C=C=C< Allenes containing even number of double bonds exhibit optical isomerism provided the two groups attached to each terminal carbon atom are a a a x NS 4 S 2 C=C=C0 oor C=C=C ob “ob bo Sy @ __Alkylidenc, cyclosikanes and spiro compounds : When one or both of the double bonds in allencs are replaced by one and two rings, the resulting systems are respectively known as alkylidene cycloalkanes and spiranes. HC. vt or a AnH a C Cc ww NY vw coo o” \cu,% Now \p 1-Methyl cyclo hexylidene-4-acetie acid (Alkylidene cycloalkane) ‘Spiranes @ _Bipheny!s :Suitably substituted diphenyl compounds are also deVoid of individual chiral carbon atom, but the molecules are chiral due to restricted rotation around the single bond between the two ‘benzene nuclei and hence they must exist in two nOn-superimposable mirror images of cach other. coon 63 Noo ( ee! ) Q—D — 4? Number of optical isomers : Case -1 When the molecule is unsymmetrical. (It cannot be divided into two halves) Number of d and / isomers = 2* Number of meso form = 0 Total number of optical isomers = 2* Where n is the number of chiral carbon atoms. For eg. 2, 3+ Pentane diol d and | isomers = 2? = 4 Case - 2 When the molecule is unsymmetrical, number of chiral carbon = even number Number of d and I forms =2°- Number of meso form =22- 0 Total number = addition of the above amete ot For eg.: Tartaric acid 1H u—C—on u—€_on 4 Number of d and | forms = 20? - =2 Number of meso form = 222-"=2°= 1 Total optical isomers = 3 Case- 3. ‘When the molecule is symmetrical. number of d and / form = 2-1) - 2 «92-0 Number of meso form = 262 - *9) Total number of isomers = 2" RACEMIC MIXTURE @ b) () @ ‘An cquimolecular mixture ofa pair of enantiomers is called racemic mixture of Taccmic modification. ‘Aracemic mixture is optically inactive. This is because ofthe fact that in equimolecular mixture of ‘enantiomeric pairs, the rotation caused by the molecules of 6né enantiomer is Cancelled by the rotation caused by the molecules of other enantiomer. This type of compensation of optical rotation inaracemic mixture is referred toas external compensation. Thus, raccmic mixture becomes optically inactive because of extemal compensation. Representation of Racemic mixturé: The racemic mixture of a particular sample is indicated by using the prefix (d,1) or (+). For example, racemic mixture of lactic acid is represented as (4) lactic acid, RACEMIZATION Iisa process of conversion of an optically active compound into the racemic modification. Both (+) and (-) forms ofthe compound are capable of racemizations under the influence of heat, light or chemical reagents. RESOLUTION ‘The process of separation of constituent enantiomeric forms from the racemic mixture is known as resolution. (Chemical method : This is probably the best method of resolution. The racemic mixture is to combine with another optically active compound and the resulting products (salt - formation) differ in properties, particularly in solubility in various solvents. By fractional crystallization from a suitable solvent, they can be separated. Mechanical method : Ifthed and /-forms of a substance exist in well defined crystalline forms, the separation can be done by hand picking with the help of magnifying lens anda pair of tweezers. Qa Qs MC A Fischer projection of (2R, 3S)-2,3-butanediol is : - s ty ale Hy at HB) 1M oro cH, m7 Hy ay ‘The correct statement about the compound A, B and C. cooct cooH coon H Hi u—t—on H——on i ‘OH H Ou HO———H coon coocn, coocH, ww ® © (A)‘A’and°B' are identical (B) ‘A’ and “B’ are diastereomers (C)‘A’and °C’ are enantiomers. (D)*A’and ‘B" are enantiomers ‘The correct statement about the compounds I, II and III " u 4 coon o q H a coon, im am (A) land are identical (B)1 and Il are diastereomers (C) land I are enantiomers (D) land Tare enantiomers ‘The number of optically active isomer possible for CH; -CH-CH-CH-CH,OH is OH OH OH (ay (B)4 «os (Ds (10 Which of the following compounds is chiral? Be (A) BrCH,CH,CH,CH,CH, (8) CH,CH,CHCH,CH, (€) H,C=C~cHcH, (D) BrCH = CHCH,CH,CH, Br (E)None of these Q6 — Thefollowing hydrocarbon can exhibit. HC ‘CH=CH, CH,CH, (A) Geometrical isomerism (B) Optical isomerism (©)Both geometrical and optical isomerism (D) Tautomerism Q8 The compound whose stereochemical formula is written below exhibits x geometrical isomers and y optical isomers. CH oH - I ca cH, cH, €- cH, H ‘The values of x and y are (A)4and4 (B)2and2 (©)2and4 (D)4.and2 ANSWERS QI A Q2 B Q3 A Q4 D QS E106 B Q7 Bo Q8 B 2. CONFORMATIONAL STEREOISOMERISMS Differeit non-identical arrangement of atoms or group in a molecule that result by the rotation about a sifigle bond and that can easily be reconverted at room temperature are known as conformational stcrio isomers of conformers. ‘Conformation isomerism : The different arrangement of atoms is space that result from the free rotation of group about C-C bond axis are called conformers, and this phenomenon is called conformation isomerism. The basic structure of the molecule various bond length and bond angle remain the same. There arc infinite no. of conformers of any molecule two out of them are defined as staggered and eclipsed. Condition of conformation : ‘There should be three o-bond present in a molecule. Projection of Tetrahedral Carbon Atom : Newman projection : In this method the molecule is observed along the central carbon-carbon bond. a circle is drawn and centre of the circle represents the front carbon. the bonds of the front carbon are drawn from the centre of the circle while the bonds at the hack carbon are drawn from the periphery. ‘Saw horse projection : In this method, central carbon-carbon bond of the molecule is represented by a straight line written in bond of the molecule is represented by a straight line written in slightly tilted manner and the molecule is observed from the right side. cot Nu Wu Dihedral angle :- Angle between valencies of two adjacent atoms Conformation in ethane (CH,-CH,) H HoH 4 H Saw horse formula : ¥ Hye, att H Eclipsed ‘Straggered Hy H oP H: H ‘Newman's projection formula > H Ectipsed form : When H-atoms of onc carbon are directly behind the other is called eclipsed form. ‘Staggered form : The hydrogen of two atoms are maximum distance with respect to one another. ‘Skew form : The different forms which exist between 0° to 60°. Stability : The eclipsed form is less stable than staggered due to Vander Waal repulsion and torsional ‘strain, Eclipsed < Skew < Staggered ‘Vander Waal repulsion : Repulsion between atoms or group of atoms. ‘Torsional strain : Bond pair-bond pair repulsion in eclipsed form. Potential energy curve: E,,- E,=3Keal/mole or 125kJ/mole Conformation in propane : H Hew, cH, " a we, A H H, u i 7 xu Wi > Staggered Eclipsed Eclipsed E,,-E,= 13.8kJ/mole 60" 130 | 180" Staggered Ecipeed Supgered Rotation ‘Conformation in n-butane : Loo. 3 4 ‘ CH, -CH, -CH, ~CH, (C;-C, bond rotation) Hy Hy CHic, 1 Hen, H ' Q CH, H H Hl CH, Fully Eclipsed (onan sazecred Partially Eclipsed Fully staggered or Anti form CH, Hy cl H ' H H ci, Partially Eclipsed Partially staggered (Gauche form) Stability order: Anti form> Gauche> Partial eclipse> fully eclipsed Exercise: _n-pentane (about C,-C,) @ —_3-methy! pentane (about C,—C,) ‘Some important example: aH, Edytenegyeat: ‘0-H Gauche form is most stable duc to intramolecular H-bonding. eee Z-CH;-CH, Z=-OH, -NH,, -F, -CHO' -COOH, OCH, bu Gauche in all cases due to H-bonding. Gauche effect : In a lone pair containing compound bulkier group should be placed in Gauche (60°) from|[Link] Lp. has minimum steric repulsion. CH, cH, H cH Hy aS 1s 1 Draw most stable conformation of following compound. @ pentane (C,-C,) bond rotation. Hy tt ae 4 @) ” 2 c-cyyc-c-c 3-methyl pentane (C,-C,) CH, H cee’ H Ht 3,3-dimethyl hexane (C,-C,): CH; CH, or a 22,3.4.5S-hexamethyl hexane (C,-C,): id Write stable conformer for Z-CH,- CH,~ Z in Newman's projection. If tyuaioq = 1.0 D and mole fraction of anti form = 0.82, find Hoste [JEE 2005} Meaune™ 5.55 D Zz z i, H H Z wt ‘H H Zz H (Antiy (Gauche) ‘Mole fraction of anti form = 0.82 ‘Mole fraction of Gauche form = 0.18 Hep, = 1 Ayaan * 0.82 + Hayes * 0-18 Haaiy = 0 T= Hecate 1 Hewacte = O18 Conformation in cyclo alkane: Bacyer's strain theory : According to Baeyer's strain theory, the amount of the strain is directly proportional 10 the angle through which a valency bond has deviated from its normal position. i.c. «0.18 =5.55D 1 ‘Amount of deviation d= > (109° 28'— Valency angle) 1 in cyclopropane d= > (109° 28'- 60°) = 24°44" 1 ‘in cyclobutane d= 2 (109° 28'- 90°) = 9°44" in cyclopentane d= 4 (109° 28"— 108°) = 0°44" 1 incyclohexane d= > (109° 28'- 120°)=-5°16" Heat of combustion : Cyclohexane > Cyclopentane> Cyclobutane > cyclopropane Heat of combustion per—CH,- CCyclopropane > Cyclobutane > Cyclopentane > Cyclohexane Orbital picture of angle strain : cao In cyclopropane however, the C-C-C bond angle cannot be 109° 28" but instead must be 60°. As a result the C-atom cannot be located to permit their sp? orbitals to point toward each other. there is less overlap and the bond is weaker than the usual C-C bond. Conformation of cyclobexane : Cyclohexane exist in different form, such on chair form, boat form twist boat form, half chair form. Stability order : Chair form> boat form (Chair form of cyclohexane: Ha i H Newman's projection There are two type of hydrogen in cyclohexane: Me je He- He He " a BL ie fs . axes Equatorial bond Incyclohexane all carbon maintain tetrahedral geometry so that cyclohexane is most stable cycloalkane. At room temperature one chair form flips to another chair form during flippitig axial bonds converts to ‘equatorial & equatorial bonds converts to axial. _ # ey W.. He K=1 Both chaie form are equally stable. Conformation of mono substituted cyclohexane : Hy 3b Methyl cyclohexane rN A os Mh f K>1 (1.3-1,Sintraction) ‘When methy! groups add axial position than their willbe more I 3— 1.5 intraction so that this conformation will be least stable. By ring flipping methyl group occupied equatorial position so that new reverse chair forma will be more stable. Write the orders of equitibrium constant for following equilibrium. Hy ° rN a An GHs \ ° ao WAL order K, b>d>a (B)cdd>a (D)c>d=d>a ‘Which form is more stable in the shown case- Kaw ts7 al yn (=m (yu>t Increasing order of stability among the three main conformation (.c. eclipse, anti, gauche) of ethylene gheolis: (A) Eclipse, gauche, anti (B) Gauche, eclipse, anti (©)Eclipse, anti, gauche (D)Anti, gauche, eclipse The correct stability order ofthe following species is H 4 Me Zar "Me Me @ Hoy # (A)e

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