» across many cases When two or more compounds formula but the study of org: Consist of equal number of like atoms. These compounds have the same molecula differ from each other in physical or chemical properties, and are called Isomers and the enomenon is called Isomerism. Since isomers have the same molecular formula, the difference in properties must be due to different modes of combination or arrangement of atoms within the Blecule. There are two main types of isomerism nic chemistry we com (1) Constitutional Isomerism (2) Stereoisomerism ‘Constitutional Isomerism When the isomerism is due to difference in the arrangement of atoms fn the molecule, without any reference to space, the phenomenon is called Constitutional vrism. In other words, Constitutional isomers are compounds that have the same molecular a but different structural formulas. Constitutional isomerism is of five type (a) Chain Isomerism (b) Position Isomerism (c) Functional Isomerism Metamerism ?) Tautomerism reoisomerism, When isomerism is caused by the different arrangements of atoms or groups , the phenomenon is called Stereoisomerism. The stereoisomers have the same structural s but differ in arrangement of atoms in space. In other words, stereoisomerism is exhibited compounds which have the same structural formula but differ in configuration. (The term ition refers to the three-dimensional arrangement of atoms that characterizes a particular \d). Stereoisomerism is of two types : Geometrical or Cis-Trans Isomerism Optical Isomerism Scanned with CamScanner422 | curren 7 ISOMERS (Same molecular formula) —_——_——_ Constitutional Isomers (Oiferent connectntty among atoms) Different carbon skeletons CH, f CH;CH,CH,CH, and CH,CHCH, Different functional groups CH;CH,OH and CH,OCH, Different position of functional groups : NH, CH;CHCH, and CH,CH,CH,NH,ISOMERISM elpgic 123 Example 2, 2-Methylbutane and 2,2-Dimethylpropane ite CHy—C—CH | CHs 2,2-Dimethylpropane CHy—CH,—GH— CH CHy 2-Methylbutane (2) Position Isomerism Position isomers have the same molecular for group on the carbon chain. Example 1. 1-Bromobutane and 2-Bromobutane mula but differ in the position of a funet Br | CH,CH2CH2CH,Br CHyCHCH,CH3 1-Bromobutane 2-Bromobutane Example 2. _n-Propyl alcohol and Isopropyl alcohol OH CH3—CH,—CH0H CH;—CH—CHg 1-Propyl alcohol Isopropyl alcohol Example 3. |-Butene and 2-Butene CHgCH,CH=CH> CHgCH=CHCHg Example 4, 2-Pentanone and 3-Pentanone 8 ° i (CHg—C—CH,CH2CH3 (CH3CH2—C—CH2CH 2-Pentanone ‘3-Pentanone Example 5. o-Dichlorobenzene and m-Dichlorobenzene cl cl or” o. cl o-Dichlorobenzene m-Dichlorobenzene (3) Functional Isomerism Functional isomers have the same molecular formula but different functional groups. Example 1. Ethyl alcohol and Dimethyl ether CH,CH,OH CHy—O—CHy Ethyl alcoho! Dimethyl ether Example 2, Acetone and Propionaldehyde ei. CHyCH,»—C—H ‘Acetone PropionaldehydeExample 2 Acetic acid and Methyl formate ° H—C—OCH, Methy formate the unequal distribution of carbon atoms on either side of the ¢ same homologous series. H;—O— CH,CH2CHy Methy| propyl ether —NH—CHCH, CH,CH,CH,—NH—CH, Diethyiamine Methylpropylamine 5) Tautomerism It is a special type of functional isomerism in which the isomers are in dynamic equilibrium with cach other. For example, ethyl acetoacetate is an equilibrium mixture of the following two forms, At room temperature, the mixture contains 93% of keto-form plus 6% of the enol-form. ° os tl CH3—C—CH,CO,CH5 = = CH;—C=CH—CO,C>Hs Keto-Form Enol-Form _B< Points to Remember 1. Constitutional isomers are also called structural isomers. 2. Chain isomers have the same molecular formula but different arrangement of carbon atoms. ‘Chain isomers are also called skeletal isomers. 2. fanition isomers have the same molecular formula but differ in the position ofa substituent oree ee Fig.7.1 Rotation about n bond is not Possible because it would break the x bond, ‘This restriction of rotation about the carbon-carbon double bond is responsible for the geometrical isomerism in alkenes, A popular analogy for this situation is based upon two boards and two nails. Driving one nail through two boards will not prevent free rotation of the two boards. But once a second nail is used, the boards cannot be freely rotated. Gb Some rotation Free os not om | is possible Consider the case of 2-butene. It exists in two spacial arrangements : H H H ‘CH, HC CHs HH oo pom and OCS cis-2-Butene trans-2-Butene (bp 4°C) (op 1°C) ‘These two compounds are referred to as geometrical isomers and are distinguished from each, ‘by the terms cis and srans. The cis isomer is one in which two similar groups are on the same of the double bond. The frans isomer is that in which two similar groups are on the opposite ‘of the double bond. Consequently, this type of isomerism is often called cis-trans isomerism, isomers are stereoisomers, because they have the same structural formula but different ‘arrangement of atoms. Scanned with CamScanner126 | cHaPTeR 7 Theérans isomers are more stable than the corresponding cis isomers. This is because, ny cis isomer, the bulky groups are on the same side ofthe double bond. The steric Stain of the groupe makes the cis isomer less stale than the trans isomer in which the bulky groups ate far apart (they we on the opposite sides of the double bond). H ey Ss ek “A a ~ ne mace ‘4 ne eae Fu) HW 4 ne a ‘Steric strain in No steric strain in. cis-2-butene trans-2-butene_ ‘The geometrical isomers have different physical and chemical properties. They can be separated by conventional techniques like fractional distillation, gas chromatography etc, Allalkenes do not show geometrical isomerism, Geometrical isomerism is possible only ‘when each double bonded carbon atom is attached to two different atoms or groups. The following ‘examples illustrate this condition for the existence of geometrical isomers, Example 1. Consider the case of Propene No geometrical isomers are possible for propene (CH;CH=CH,). This is because one ofthe “double bonded carbons has two identical groups (H atoms) attached to it. CHy. a ie | Identical atoms/groups HOON, |__F onthe same carton Propene Example 2. Consider the case of 3-Hexene fe qocomettical isomers are possible for 3-hexene (CHjCHsCH=CHCH. 1s). This is because double bonded carbon atom is attached to two different groups (CH\cth and H). The cis and isomers of 3-hexene are shown below : ‘same side aS xSa ~ * € ee hot tt tt td ea wounm loghitan ‘These isomers differ in physical properties such as melting point, dipole moment, and acidities. ‘The trans-isomer has no dipole, since it is symmetrical, unlike the cis-isomer. The cis-isomer is stronger acid than the ¢rans-isomer, Even chemical properties differ in the butenedioic acids. For ‘example, the cissacid undergoes dehydration at 100°C Hl HN COOH HvpnG I min ll ‘0 + H,0 no c 00H es ~¢ 0 ‘Maleic acid Maleic anhydride However, the trans-acid does not form an anhydride until heated to 240°C. At that temperature there is sufficient thermal energy to break the double bond, so that the cis-acid and the anhydride are formed in succession. ° Il Ho COOH HL COOH An 1 moc, ff ato Si “ 2b. Ay / HoOC~ "~H H7 "COOH neo I ° Fumaric acid (not isolated at Maleic anhydride this temperature) (2) Geometrical Isomerism in Cyclic C Geometrical isomerism is also possible in cyclic compounds. There can be no rotation ‘about carbon-carbon single bonds forming a ring because rotation would break the bonds and break - the ring, For example, 1,2-dimethyleyclopropane exists in two isomeric forms. Ch, CHy CH, H H trans the two methyl groups are on the same side of the ring.$< > OPTICAL ISOMERISM ‘Optical isomerism is a type of stereoisomerism. The outstanding feature of optical isomers i that ~ they have the ability to rotate plane-polarized light. This property is often referred to as optical activity and requires a brief discussion. OPTICAL ACTIVITY - PLANE-POLARIZED LIGHT Light from ordinary electric lamp is composed of waves vibrating in many different planes. ‘When it is passed through Nicol prism (made of calcite, CaCOs) or polaroid lense, light is found to vibrate in only one plane, and is said to be plane-polarized or simply polarized. The diagrams illustrate the vibrations of ordinary and polarized light from a beam propagated perpendicularly to the plane of Paper. Solutions of some organic compounds have the ability to rotate the plane of polarized light. “These compounds are said to be optically active. This property of a compound is called optical activity. @ O Ordinary Light Plane-Polarized Light (Polarized Light) und is detected and measured by means of a Itis indicated by the sig? isreferred to as observed rotation, «., Fig. 7.2 shows he Scanned with CamScannerISOMERISM oreo 129 Nico! sample prism soution rotated rai Polarized polarized light Tight Ordinary _, Le Fig.7.2. A simple polarimeter in operation. © SPECIFIC ROTATION Optically active compounds rotate the plane of polarized light. The degree of rotation depends upon the number of molecules ofthe compound encountered by light along its path It is, therefore. necessary to introduce some standard by which the rotating powers of ‘compared. Specific rotation is defined as the rotation produced by a solution of length 10 centimeters ‘and unit concentration (1 g/ml) for the given wavelength of light at the given temperature. Consider a system in which the plane of polarized light is rotated through o degrees at a temperature 1000 f different compounds may be of @C and using the sodium D-line as the source. The specific rotation [oly isgiven by fo], = a where cris the observed rotation ; 1 is the length of the tube in decimeters ; and cis the number of ‘grams per 100 ml of solution. The specific rotation varies with both the wavelength of light and the ‘temperature. Problem. A 1.20 g sample of cocaine, {ct]p =—16°, was dissolved in 7.50 ml of chloroform and ample tube having a path Iength of 5.0 em. What was the observed rotation ? Is cocaine “de orlevorotatory ? xe a= beerved| rotati¢ degrees _¢ = length of tube (dm) = path length entration of sample (g/ml)130 | cHaPTER 7 An object lacking a plane of symmetry is called Chiral (pronounced as Ki-ral) or Dissymmetr A symmetric object is referred to as Achiral. Ww Plane of symmetry Fig. 7.3. Planes of symmetry. sed on its mirror image. A left hand, for example, does not possess hand but a right hand (Fig. 7.4). The two and on top of the other, A chiral object cannot be superimpo a plane of symmetry, and its mirror image is not another left are not identical, because they cannot be superimposed. If we were to lay one hi 5 and the thumbs would clash. Fig. 7.4. The mirror image relationship of the left and right hands. Notice that right hand is the mirror image of the left hand. CHIRAL (OR ASYMMETRIC) CARBON ATOM ‘A carbon atom which is bonded to four different groups is called a Chiral (or Asymmetric) ‘Carbon Atom. For example, Chiral carbon CH,CHs Chiral carbon CQ3H I | Ce ea Cacia H—C—OH ' Br (CH2OH ‘The term chiral (Greek handedness; pronounced kairal) carbon atom means that a carbon ato™ is bonded to four different groups and that a molecule of this type lacks a plane of symmetry. Such * molecule is also called Asymmetric or Dissymmetrie. OPTICAL ISOMERISM ‘A substance which has the ability to rotate the plane of polarized light is said to be opticall? active and exhibits optical isomerism. Optical isomers are isomers that are identical in all properties ‘except for their effect on plane of polarized light. Scanned with CamScanner' ISOMERISM ol, Joist ‘The isomer which rotates the plane of polarized light to the ight (clockwise direction) isknown as Destrorotatory Isomer or (+)-isomer. The isomer which rotates the plane of polarized light tothe left (anticlockwise direction) is known as the Levorotatory Isomer or (~)-isomer. The optical rotatory of two isomers are equal in magnitude but opposite in sign. An equimolar mixture of the two isomers, therefore, will not rotate the plane of polarized light at all and is said to be Racemic Mixture. Optical isomers have the same physical properties : melting point, boiling point, density, etc. They have the same specific rotation but with opposite signs. OPTICAL ISOMERISM OF LACTIC ACID Lactic acid (2-Hydroxypropanoic acid) isan example of a compound which shows optical isomerism. Itcontains one chiral carbon atom, OH I Lactic acid. The CH,—C—cooH chiral carbon is shown by an asterisk. H ‘Two three dimensional structures are possible for Lactic acid (Fig. 7.5). These structures are not identical because they cannot be superimposed on each other. One is the irror image of the other. Such nonsuperimposable mirror image forms are optical isomers and are ed enantiomers. Thus, three forms of lactic acid are known. Two are optically active and the third optically inactive, 1. (+)-Lactic Acid. It rotates the plane of polarized light to the right (clockwise direction) and called dextrorotatory. 2. (~)-Lactic Acid. Itrotates the plane of polarized light to the left (anticlockwise direction) and. called levorotatory. (~)-Lactic acid is the mirror image of (+)-lactic acid and vice versa. 3, (4)-Lactie Acid. Itdoes not rotate the plane of polarized light. That is an equimolar mixture of (+)-and (~)-forms (racemic mixture).132 | CHAPTER 7 ‘onal molecules on paper, Aly ree-dimensi a .e enantiomers of lactic acid js FISCHER PROJECTIONS ‘of one of th Fischer projections provi xd onto one pl de an easy way to draw th jane. The Fischer projection ‘atoms are proj shown below peor Rice I HO—C—H wo Ons CH3 )-Lactic acid. Fischer projection of (+) ngement aroun 1. The carbon chain of the compound is arranged vertic the top. Or, put the carbon number 7 (as defined by nomencl 2. Represent the chiral carbon(s) at the intersection of crosses show the chiral carbon also. ‘da chiral carbon are as follows: ally, with the most oxidized carbon a Jature rules) at the top. .d lines. Some teachers like to rtical lines are understood to be going back behind the plane of the Groups attached to the ve I lines represent bonds going away from the observer. The chiral paper. That is, the vertical carbon is in the paper plane. 4, Groups attached to the horizontal lines are understood to be coming forward out ofthe paper plane. That is, the horizontal lines represent bonds coming toward the observer. CONDITION FOR OPTICAL ISOMERISM ‘The necessary condition for a molecule to exhibit optical isomerism is that it should be dissymmetric, That is, the molecule should not be superimposable on its mirror image. In simple molecules, the dissymmetry (also called Chirality) results from the presence of a chiral carbon atom. Recall that a chiral carbon is one which is bonded to four different groups.vn FAB. 7.6 shows two three dimension, NWO! a sional mo The i a) os se eenwiils i OF CD and the two cannot be superimposed, If you try to supertmpowe the Four aro attached to achiral carbon aon in form (1) and form (1D, onty two of the four groups coinelde, while the other two are in eonfict, This shows that the two forms represent diferent compounds, carbons but being achiral, do not show optical compounds (sueh as substituted allenes and ip disgymmetric, show optical isomerism OPTICAL ISOMERISM OF TARTARIC ACID isomerism, On the other hand, there are certain henyls) which have no chiral carbons but being ‘Tartaric veld (2,3-Dihydroxybutanedioic acid) contains two chiral carbon atoms, 9H H—C*-COOH Tartaric acid. The two chiral carbons are ne f COOH shown by asterisks, OH Four forms of tartaric acid are known (Fig. 7.7). Two of them are optically active and two are optically inactive. The optically active forms a are related to each other as an object to its mirror image, Thats, they are enantiomers, Mirror i HH c0oH Equimok vixture of HTGTOR “Cand chtorms Hoe —on “HEOK (Racemic mixture) COOH a (-)-Acid meso-Acid (2)-Acid mp = 170°C mp = 143°C. mp = 206°C j Optically active Optically inactive: Fig, 7.7. Isomers of tartaric acid. . ic Acid, It rotates the plane of polarized light to the right (clockwise direction)Mirror Mirror Gs GMs aa § = H—C—Br H—C—Br CH; CH; (B) (C) Fig. 7.8. Four isomers of 3-Bromo-2-butanol. Optical isomers which are not enantiomers (mirror images) such as (A) and (C) or (B) and (D) of the above example, are known as Diastereomers. PROPERTIES OF ENANTIOMERS Optical isomers that are mirror images are called Enantiomers. These always exist as discrete pairs. For example, there are two optical isomers of lactic acid (Fig. 7.9). Notice that (A) is the mirror image of (B). They are a pair of enantiomers. Mirror COOH i COOH HO—C—H H— ie ‘OH bes bis Fig. 7.9. Two isomers of Lactic acid. ‘Enantiomers are stable, isolable compounds that differ from one another in three-dimensional tial arrangements. Enantiomers cannot be interconverted under ordinary conditions. h have identical properties in all respects except in their interaction Basapraneisiesy hay eae pence poneald | i | ISOMERISM obpate rss Notice that (A) is the mirror image of (B) : (C) is the mirror image of (D). Thus the four isomers are two pairs of enantiomers. Now compare (A) with (C), They are neither superimposable nor are they mirror images. They are called diastereomers. (A) and (D) are also diastereomers, as are (B) and (C), and (B) and (D). Stereoisomers that are hot mirror images of each other are called Diastereomers. Mirror Mirror Gs Hs GHs j H—C—OH aa a H—C— OH Br—C—H Pata H—C— Br I CH; CH; CHs (A) (8) (c) Fig. 7.10. Four isomers of 3-Bromo-2-butanol. Diastereomers have different Properties. Two diastereomers will have different melting points, boiling points, and solubilities, They will have different chemical reactivities toward most reagents, PROPERTIES OF MESO COMPOUNDS compound with two or more chiral carbon atoms but also having a plane of symmetry (a mirror Plane) is called the Meso Compound. Fig. 7.11 shows two meso compounds, These molecules have Scanned with CamScannerR,S SYSTEM OF SPECIFYING CONFIGURATIONS The actual three-dimensional arrangement of groups in a chiral molecule is called its Absolute Configuration. We can specify the configuration by using the R.S System. The R.S system is also called the Cahn-Ingold-Prelog System (named after its inventors) In the R,S system, we arrange the four groups attached to the chiral carbon in decreasing ‘order of priority (1, 2, 3, 4) by applying the rules given below. We then view the chiral center with the lowest priority group (4) on the side opposite the observer (group priorities are shown in parentheses) : 1 ga A(t) a i» «4p—c » Neo Q ac. B(2) oe “~~ Anticiockwise = S Left turn = S As seen by the observer Inthe above example, A has the highest priority (1) ; B has the next highest (2) ; Chas the next (3) ; and D has the lowest priority (4). We now go from high to low priority (123). To do so we move in an anticlockwise direction, and therefore we assign to this structure the S Configuration (S = sinister = left). In the structure given below, we go from highest to lowest priority by moving in a clockwise direction. We therefore assign to this structure the R Configuration (R = rectus = right). (me a ye b | a (4p —c: c Qeo ae ee) (@) ee ee ‘Clockwise = R Right tum = R ‘As seen by the observer Scanned with CamScanner«we use the following Sequence Rules : || carbon atom, the one with the hj To establish the group prioritie: N Rule 1, Of the atoms attached directly to the chiral omic number has the highest priority, For example, > Cl> fF > 0 > NizaG gem Lowest he chiral carbon atom are the same, we determine priori n atom. For example, Priority 1 > Highest Rule 2. Ifthe atoms attached tot going to the next atom away from the chiral earbor Cha Ch CHy—C— > CHy—CH— > CH,CH,— > CHy— CHy Highest X«__———— Lowest Ethyl has a higher priority than methyl because the ethyl group has (CHH attached to the firy carbon, whereas the methyl carbon has only hydrogens (HHH), and C has priority over H. Isopropy| is of higher priority than ethyl because it has two carbons attached to the first carbon and ethyl has ‘only one, If there is no difference at the second atom in the chain, we go to the next atom and so forth, Rule 3, A double bond is treated as though each atom of the double bond were bonded to two atoms: 4 H ae yom =I ISOMERISM obpate ts! J, Most errors in designating the configurations of molecules by R.S system come from a failure to point the lowest priority group away from the observer. You can easily assign the wrong, configuration to a molecule if you do not point the lowest priority group away from yourself. 2. The priority sequence for the most common atoms and groups is as follows = /. Points to Remember ° F, —O—C—R, —OR, —OH, —NO2 i NRg, NHR, —NHp, —CCly, —C—Cl, —C—OR, —C—OH i CH, —CN, —CH;OH, GgHs—, CR, —CHR2, — CHa —CHs, —H (Low Priority) Jher projection formula is commonly used to show configuration without going to the invention the chiral center and the 3, The trouble of drawing three-dimensional structure. In this cor bonds to it are represented by crossed vertical and horizontal lines. Itis understood that groups attached by vertical bonds point away from the observer ; those bonded horizontally point toward the observer. Some chemists show chiral earbon also CH CHy cl Br CH, ae Br Fischer Projection tg CHe 7 = Formula H H 4. Inexam you are ordinarily given a Fischer projection formula and asked to specify configuration using the symbols R and S. Itis easy todo sof you follow the following step-by-step method. Consider the following example : (3)CHs «, (Be — = (2c —! (3), s Ce c—Br(1) woes CHy( 5 contain abl) Onler of Priority (1) Br (atomic number 79.9) (Highest) 2) Cl (atomic number 35.5) (3) ClHy C, atomic number 12) (4) Hi (atomic number 1) (Lowest) Determine the priority of groups attached tothe chiral carbon atom. Apply the sequence rules carefully. Inthe above example, the order of priority is: Br > Cl > CH) > 4 this case H) down and avay from the observer. This )2. Position the lowest ‘is done by bonded to the asymmetric carbon, Remember that interchanging in a Fischer projection inverts the configuration. Scanned with CamScannerconfiguration. Thus, the is the original in pairs to avoid a configuration change, o highlight a bond between the rations have been 142 | CHAPTER 7 5 of groups remain two pairs be done Imerchanging must always interchange operation In the above example, a dotted Tine has b chiral carbon and the lowest priority group (1) shown by dotted double-headed curved arrows. lecreasing priority of the three groups (1923). Ignore the roups 1, 2, and 3 are arranged in clockwise fashion, the configuration is R. If the groups occur i anticlockwise fashion, the configuration is 8. In the above example, the configuration is S because the groups 1, 2, and 3 are arranged ckwise fashion (shown by circular arc). een used t |). The interchange Ope! Specify the direction of d Step 3. lowest priority group. If the 8 in anticlo E, Z SYSTEM OF SPECIFYING CONFIGURATIONS ted as cis or trans. If the two identical ‘The configuration of geometrical isomers can be designat e double bond, the isomer is cis ; and if they occur on opposite sides, the isomer is trans, This method does not work when there are no identical groups, as in BrCl CFI (1-Bromo- chloro-2-fluoro-2-iodoethene). The configuration of these and all other geometrical isomers can be specified by using the notations Z and E. To do this, first determine the gen of highest priority on each carbon. If the two high-priority groups are together on the same side, the configuration is Z (German, zusammen = together). If ite si a = . If th configuration is E (German, entgegen = opposite). or ye on op etal groups are on the same side of th High ceo ie Ms J” Priority prionty H he Ve \ 2 aaa c* ey ro High Fac . Priority onan, Cs, of re Priority Scanned with CamScanner