6 \d Techniques a wy ita see See ee pot li ina plane but are directed towards the INTRODUCTION TO ORGANIC ¢ four con aregular tetrahedron, een oer cmon (ii) is because of this reason that van't Hoff was aya cen first Noble prize in chemistry in 1901 Aceordin as been coined from the word "Organism" {o thi definition organic chemistry was defined as the chemistry of compounds found in living beings (Berzelius 1808). Vital Force Theory ey Creanie compounds eannot be synthesized in the laboratory because they require the presence of a mysterious foree (called ‘ital force) which exists only in the living organisms, hler's Syathesis When ammonium eyanate (obtained by doubled ammonium sulphate and potassium well known organic compound is obt ANHSO,~2KCNO —>. lecompasition of reer ate) is hes ned. 2NH,CNO * K,S0, Ammonium esanate H.N-C-NHY i ° Liss J rea a NH,cNo) —st__, (Rearangest The noma ston of alent This synthesis seo i janic molecules = Modern Definition of Organic Chemistry Formation of organi » (We know that 0 [hs branch of chemistry which deals with the study of hydrocarbons and their detiv igure Terahedralrerosenatons of carbon alencies We 4 death blow to vital force theory Figure Tetra nic compounds are earbon compo and carbon atom does not take part as such in bond form, suvesis known as organi chemistry. butts 2vand 2p orbitalts) mix together to form new ork Structure and Shapes of Organic Molecules known as hybrid orbitals and the process in turn isk as hybridization, ndithas urelsctronsin (i) Thetpesofhiytridizatonenesteredin organic compa, Fide pogo involved in: saturated organic compounds contaj only single covalent bonds, eg. methane). sp (Gnvol organic compounds having carbon linked by double bo ethylene) and sp involved in organic compounds h (Wn S74 Sat Holand Le Bel predicted thatthe four bonds __earbon linked by triple bond. ep aversion of carbon in methane and other saturated eompounds doi The bond angles and geometry assocunct with thet Tetracovateney of earbon : (i) The atomic number ofearbon is 6 its valer ‘nee shell. In order to acquire stable inert gas a configuration. it can share its electrons with theelectrons of ‘ther atomy(s)te form four covalent bonds. Thus carbon has a covalency of four or it is tetracovalent. types of hybridization are sunnmarized below Hybridisation | sp? se 9 Angle loss" 120° 180" Geometry | Tetrahedral Trigonal Linear Example | Alkanes, eycloatkanes Aikenes and other compounds | Atkynes and all other and in saturated part containing C=C, C=0, CN compounds containing ofall organie molecules | and C=S double bonds and triple bonds. Bond Fours Three-o. One-s Two-s, Two-r = 25 333 50 P% Ss 66.7 50 lectroncgativi 2 | Elsewonegativity 248 275 oe ® Sigmabona (2) A carbon-carbon o-bond can be formed by ove "050" sp? or sp-hybrized orbitals of caratCHEMISTRY Alkanes anid eyeloalkanes contain only sp3-sp' CC. a-bonds, alkenes contain sp*-sp, C—C o-bonds, while alkynes contain sp—sp, C=C, o-bonds Ina similar way, carbon can form sigma bonds with hydrogen atoms. while alkanes contain only sp" He ce-bonds. alkenes contain sp?-s, C-H, abonds and alkynes contain sp-s, C-H. 6-bonds, ~— Pi-bond: (a) A pr bond is formed by sideways or ki two p-orbitels, Thus, alkities contain 0 C-C.c-bond and ‘bat (b) In alkynes. the carbon atoms are sp-hybridized ‘Therefore. alknesconiain_onesp-sp, C= C t and two x-bonds which are mutually perpendicul cach other The two carbon atoms and two hydrogen atoms of acetylene molecule lie along a line with C —C bon of 80", Thus, aeetylencis a linear molec, Effect of Hyb “strength The bond length and bond strength of any bond depends upon the size of the hybrid orbitals involved. (i) Bond length Since p-orbita is much bigger size than a orbital ofthe same shell, therefore, as we go from sp? + sp? > sp. the pereentage of p-charactr decreases from 75 -> 66.7 — 50% Accordingly, the size of the orbital decreases in the same sp?> sp. orbital forms a longer bond, therefore, C-C_ single bond length decreases inthe order Clsp')- Cisp3) > C (sp")~ Clsp") > Clsp)—Clsp) LS4A 134A 1.20A Bond strength : Shorter the bond, greater is its strength. Thus, the o-bond formed by sp-hybridized carbon is the strongest (i.e. obo “i ir) zation on Bond Length and Bond (i) Organic Chemistry - Some Basic Principles and Techniques ‘maximum bond energy) while that formed by sr" hybridized ext (i.e. minimum bond dissociation cearbon is the we energy), Forexample, Cp) IT Cp?) > Cusp’ 121 keal mol! 106keal mol! 98.6keal mol | Chsp- Clap) > C(sp2)- Clap?) > Clsp)- Cisp') 200 keal mol! —142keal mol | 80-85 keal mol! Since the extent of overlap in sideways overlap is low carbon-carbon m-bond is always weaker than a carbon carbon ¢-bond. A carbon-carbon double bond is, however, stronger than a carbon-carbon single bond since it consists G-bond and a weak x-bond. In a similar way, @ earion carbon triple bond is farther stronger than a carbon carbon double bond. oe 1s-of Carbon and Hydrogen Atoms : ere are four (ypes of carbon atoms : (i) A primary (1°) carbon atom is bonded to one carbon atom. (i) A secondary (2°) carbon atom is bonded to two other carbon atoms. ‘A tertiary (3°) carbon atom is bonded to three other carbon atoms. {A quaternary (4°) carbon atom is bonded to four other carbon atoms. ‘The 1°,2°,3° and 4° cart 9 atoms are illustrated below: the hydrogen attached to them are named correspondingly Ex: (iy wv) ' oy 7 roy CH, CCH, CH CH Ga CLASSIFICATION AND NOMENCLATURE OF ORGANIC COMPOUNDS Classification of Organic Compounds Organic Compounds ‘Open chain or Acyclic or Aliphatic compounds Saturated Unsaturated eg. Alkanes eg. Alkenes & Alkynes Alicyelic Saturated eg. Cyclopropane Ht, Closed chain Cyclic or Ring compounds Homocyclic Benzene ——_, Aromatic Howrocycic eg Pymole Non-benzenoids Unsaturated Benzenoids 8. Cyclopropene344 Organic Chemistry — Some Basic Principles and Techniques (0 Aliphatic or pen chain compounds : {ese Compounds in which fest and las carbon atoms a re onmected with each other. Branched or unbranched rains ae possible in these compounds C c-c-c-¢ oF 1 c kx. Ve (branched) -c ° —_ (unbranched) There are wo varieties in these compounds- arbon: wacent carbons are attached with single @) (b) © Unsaturated hydrocarbons: There will be a double bond or ‘two carbons atoms. CH,=CH-CH, , CH=C-cH, Propene Prone General formula for alkenes and alkynes is CHoy ad C,H,» respectively. fi 7 Alkenes are also called as olefins because they react with halogens to form oily substances olefins (Oleum + fines ie, fa) a triple bond between any (b) © @ 0) Due to presence of m bonds, these are more reactive, Cyelic or closed chain compounds: In these compounds, first and last carbons are, ‘attached with each other. Ex L\ Cyclopropane. These are of two types — Homocyclic compounds : These are the compounds in which complete ing is formed by carbon atoms only. These are also of two types, Alicyelic compounds: These ate the compounds having the Properties like aliphatic compounds, These may be saturated or unsaturated like aliphatic compounds, Ny Cyelopropane (a) (b ffagrant odour and hence, named as aromatic (greek word ‘aroma means sweet smell). oO 8 Toluene Styrene Benzene Heterocyclic compounds : ‘These are cyclic compounds hav ‘more than one kind of atoms, ‘Aromatic heterocyclic compounds ring or rings built up gy @ H Furan Thiophene Pyrrole (®) Aliphatic heterocyclic compounds : Ch —cH, Awe HEN oO Owirne orEpoxyethane gle —7 or Eee and i or Dimethylene oxide ste mans ‘0 Oxo cyclopropane Groups Atom or a group of atoms which itor any'tree valency’ is called a Normal group : Itis represented by '! possesses any ‘charge’ on group. @ (0) Straight chain ofarbon atoms is known as normal group (© Free bond will come ether on Ist carbon atom or on ret carbon atom, n-buyl Cee ie. propyl ~c-¢ Isogroup : (© Wisrepresented by following structure: HyC-CH- ot cH, © When two methyl groups ae attached to the same carbon atom, group is named as iso OQ. = lsopropyt;s (oe Isobutyl; ( aan No © Cece Isopentyt © Secondary group : © ‘Wisrepresented by following structure ~~ c= &- (©) When ethyt 7 eer etl eroupsatschedothe emi earbon atom, group is named RE CrC— secondary butyl c as secondary.coensTRY ow Isomers of few common R. 0 @ 1} (ii) @ i) @ Whoa three alkyl groups (similar or dissimilar) are attached tothe same carbon atom. group is named as tertiary Teatiary butyl 5 ‘Tertiary pentyl Neo group: When a carbon atom is attac ed to other four earbon atoms _eroup is named as neo group. Wis represented by following structure Neopentyl Alkyl group : When a hydrogen is removed from saturated hydrocarbon, then alkyl group is formed. It is represented by R and its general formula is C, Hy,.... A bond is vacant on alkyl group on which any functional group may come. CH, > CH, = Methyl CH,-CH, 47> CH;-CH, —~ Ethyl groups CHL, — has following two isomers ~ Normal propyl CH,-CH,-CH,- CH; ~ CH- | cH, Isopropyl (1-methyl ethyl) C,Hy—has following four isomers n-Buyl H,C-CH, - CH ~ CH, ~ CH, -CH-CH,- I CH; Iso-butyl 2-methyl propy!) Secondary butyl (I-methyl propyl) CH ~CH,~ CH~ cH, ge CHF — CH Tertiary butyl (1, 1-dimethyl ethyl) (iii) CH, has following eight isomers— ‘Organic Chemistry - Some Basic Principles and Techniques 345 « wy nPentyl HyC ~CHy CH, CH=CH, ~ Iso-pentyl 3-methy! butyl) HyC=CU CHL CH= Ie Aetiveamyl (2-methyl butyl) HC-CH, -CH-CH, - He © @ ‘Tertiary pentyl (1. L-dimethy propyl) HC 1 HyC- ome J 0 scondary amyl (I-methyl butyl) HyC-CHl,~ CH, = CH= HC Secondary amyl (1-ethyl propy!) HC~ CH -CH- HC ut ‘Active isosecondary amyl (1,2-dimethyl propyl) H,C-CH-CH- Hye ne () Alkenyl group : Vinyl etheny!) Allyl @-propeny) Propenyl (1-propenyl) Isopropenyl ‘Acetynyl (ethyny!) Ly Propargyl (2-propynyl) CH,-C=C- —_Propynyl(I-propynyl) Nomenclature of Organic Compounds Mainly three systems are adopted for naming of organic compounds, @ Common names or Trivial system Gi) Derived system Gi) TUPAC system or Jeneva system (Common or Trivial System Initially organic compounds were named on the basis of source from which they were obtained:Th © Organic Chemisiry - Same Basie Principles and Techniques an S.No. Organic C Trivial Name ‘huained by destructive distillation of ag 1 CHOW Woo spirit or Methyl spirit ‘Obiained by fermentation of barley | 2 CHO Grain aleohol Obtained from urine eas | ; Me ICONH, Us faa ee aie Hee | Marsh gas (fire day CObiained from acetum " s Ciycoon Vinegar Obiained from oxalis plant | o COOH Oxalicacid Coon sd fiom formicus | : bse | z HCOOH Formic acid fredand | om milk | Rg CH, a ~COOH Lactic acid eee ou - ‘HCOOH, Malic acid Apple (Malu) CH(OH)COOH, ae to, CHCH,CH,COOH Butyrie acid boul Some typical compoundsin which commod and trivial names differ: Compound ‘Trivial Name (CommanName cH, Marsh gas Methane cHOH Wood spirit Methyl alcohol CH;COOH ‘Vinegar Acetic acid Cy -C-cHy, Acetone Dimethyl ketone Acrolein Acryl aldehyde Pyvaldehyde Tertiary valeraldehyde S.No. Compound Name 1 RX Alkythalide z R-OH : Alkyl alcohol 3 R-SH Alkyl thicalcohol 4 Re NH Alkyl amine 5. ae oo Dialkyl ether 7 R-S-R Dialkyl thioether 2 Foren Dialkyl ketone oO g ni a Dialkyl amine 9. | Trialkylamine R 10. R-O-R' i ete Alkyl ally ether i Alkyl alkyl’ ketone oO 2 R-S-R B R-NH-R' Alo Stake i ahioether : sl alkyl amin R-N-R i Alkyl atky RY Salk! alkyl" aminePosition of double b Inan unsaturated hydrocarbon, ithe position of double bond is cot 1 oF last carbo then it perf will bec alpha tis on second carbon its termed ay ff ¢heta) and then y (gamma) and & {dltay. and soon. fe TLC CH Cn cl cc> hutylene He CH CH cH B= ylene MC Cicely «&~ butylene HAC CH Clore © CH=Clly propylene (Both have same position oF double bond) HC = CH, city isobutylene Uy CHy CHE CH CH, CH, y-hexyter CH, CH CH, CIE CIE CTL, CHS-CHy&- vetytene y2oF dihalides: avo same hi fo atoms are al carbon, such compounds ate called g (by Common ines of such compound are alkylidene halides, cl Be cic, bahyhdene chloride No 1 Z cHy=cncn Isobutyidene iodide i “i Hs x men CHS Mathydene halide (wrong Eveepton: CHC Methylene aide (right (6) When nwo same halogen atoms are attached to adjacent carbons, these are called as vieieal dialides. Common names of such compounds are alkyiene halides, cl Be CHs—GHCH Hee CHCl Tae CHy Propylene iodide Isobutylne chloride CH CH, a a Eiylene chide (d) When two same halogen atoms are attached at the twoends. ‘of carbon chain, its common naming will be polymethylene halide. ‘poly’ word indicates the number of -CH,~ groups. CH, 2 Beate Sree Poly ai penta Bx CH=CH) CH 1 1 Trimet lene fodide ti tetra hexa Organic Chemistry~ Some Basic Principles andTechniques 3 GU) CH=CH) CHy CH Br Br Pentamethylene brome Exception: Hs“ dimethylene halide (wrong) CH) Xx Con non naming of d-hydroxy compounds: (a) When two ~ OH groups are attached to adjacent carbons, they are termed as alkylene glycol CH, -CH, CH=CH Bs CHSCs OH OH bu on on cut,-ch, -L-cH-o1 a, Active amylee glycol ‘When two ~ OH groups are attached at the two ends of a carbon chain, these compounds are named as polymethylene ‘glycol. Poly —> Number of CH, groups. by (ily ~CHy~CHy CHa & bu oH ‘Toramethglene glyeo! CH -CH, -CI on Hesamethylene piel CH) -OH diethylene glyco! (wron; Exception: 7 eee cree CH) -OH ethylene glycol (right) | Example 1) Make the structure of following organic compounds. 1. sopropylidene bromide 2. Active amyleneiodide 3. Isobutylene glycol 4.lsobutylene 5. Trimethylene glycol 1 Br 1 Sol. 1. CHO 2. CH) —-C—CH, ier I oy CH.CH, ou B.CHy-C—CH)—OH 4. HC“ E= CH CHy cHy 5.CH —CHa—OH ouChey, °48 Organic Chemistry — Some Basic Principles and Techniques m Common naming ofthe functional groups having carbon: ‘Sufix Functional group] ‘Suffix Functional grouP oO Qo -vic acid ] calaehyde | dl oy 7 amide -ythalide -¢-NH, -oisonitrile -onitite 0 ic anhydride oate -c7 i o No. ofcarbon Prefix e g 1 Carbon om = — E CH; =CH-C-O-CHy CH,~CH=CH—E-9 3Carbon Propion- Melba llaee lates Meth! creme - a Nomenclature of anhydrides formal re ° Iso RCN [> Normal — Roo? ater 250 — i SCarton 5 Ver LO ry g > Tertiary — Rule :- For anhydrides having R = R, add the total nner 3C*(=)doublebond 5 Acryl carbon atoms and divide it by 2, the substract will give yout 4C + double bond Croton number of C- atoms, Now name it according to chart, just give Ex above. oO 0 Total u-boy cH. Bdega ay = Substract= Number of C atom Formaldehyde Acetic Acid Ee ° ° ° r cH, -cn, Ler CH; cu-donn, cx, iy oN a fe b 7 cH ¢ 705 5 =2 (Acetic anhydride) Propionyl chloride Isobutyl amide Acetaldehyde Le Ex i Nomenclature of esters : -C—O—R Zhe group which is attached to oxygen is written as alkyl and the remaining structure is named as given example, Ex ’ CH; -C-0-cH, Methyl acetate Ethy! propionate t g CH; ~C-0~CH, ~CH, H-C-0-cH, Fihy! acetate Meth formate I CHy CH, -C-0-CH, ~cH, =3 (Propionic anhydride) ° il Rc : O.TReRY RicHCHEMISTRY ° a, th cH, -¢ om 0 CH ~CH, Il ° Acetic propionic anhydride (ight) Peopionte acetic anhydride (wrong) Divide it in two parts as above and name it by suffixing ‘ie anhydride’ (alphabetically) t BCH CHn O cH cHy=~cne s- CH=CH, 4 ° Butyrie propionic anhydride Organic Chemistry - Some Basic Principles and Techniques 27 I te CH)-CH-C CHy O- Gt GH-C CH; O Isobutyri secondary valerie anhydride oneorg f Acrylic anhydride (i) Derived System According to this system name of an organic compounds given according to the parent name of the homologous series. This, system is reserved for the following nine homologous series: Sz Namie of iomologues | Derivedname Siracture ot group 1 L Alkane Methane - 2 Alkene Ethylene 3 Alkyne Acetylene 1 4 Alkanol Carbinol 7 ~OH 5 Alkanal Acetaldehyde “CCH 6 Alkanoic acid Acetic acid 4 '-COOH 1. Alkanoyl halide Acetyl halide 1 COX & Alkanamide Acetamide acon 1 | -C-C-C- 9 Alkanone Acetone | § | CH; CH oH Ex.Ci,-C-CH,, CHy-C=C-CH, CH,— ¢-OH cu C=CHO ( cH, cH, Dimethsiacetylene ‘Trimethylearbinol —Trimethylacetaldehyde——————_—_—_= == cn CH Coon cn Types of ethyte csi prmetland ysl P. (©) Semmictrical:Orihe given wo alt lersope one gown vlan the one carbon fethylene and other on the ne catbon 0 Unsymeteicat: When bath the given groups areatahed on the + Symmetrical Lhe 8.0 aks groups are g Nt aan CH. oe ‘and unsymmetrical terms are used only eat om ON, a }tFeal eth methyt ethylene a oN Nair Nw 7a, 5 elt sidechains (comet) ean ee (© Thecarbon which isatached with functional groupmastie Dimethyt acctytent included in the chain selected itrespective ofthe leigh! (ili) U.P.A.C System or Geneva System the chain, (intemational Union of Pure & Applied Chemisty) This system is based on the total ‘number of carbons in the selected carbon chain in any organic compound. Following prefixes are used in this system, G6 Chain Word Chain Word OH OH Length root Length Root 6C-Chain (wrong) 4C-Chain (right) Cc ‘Meth G Hept(a) chy 1 h-CH Cllcu, - c Eth & Oci(a) tr 1CH ~ CHy G Prop & Non(a) LCE CH G But(a) Cio Dec(a) 4C-Chain (correct) C, Pent(a) Ci Undee(a) TGpcas-- ne. 5 CH GH en ; Hex(a) Ci Dodeo(a) Late cH fo Rules for TUPAC nomenclature : CH, CH. (a) Longest chain rule : ae 6a rong According to it, in any: ‘organic compound the longest carbon ‘umbering : Incorrect numbering co cee I c 2-Methyl-4-isopropyl-S-cthytheptane (wr00g) S-Ethyl-2-methyl 4-isopropylheptane (right) (@ Capital word is used for first substitute 12 3 4 5 6 x WyC- CH -CH-CH Ci CH, HC NH, C,H, 3-Amino-4-cthyl-2-methytheEEE “3? Diane Chemisty Some Basi Pingpes TENE er 1 Showving 1 + Nomencl : ‘ 7 "Showing IUPACNames for uni-funetonal groups: NOM all eroupatacheb i OXYBEN rg, Sa, Funetionalgeoup TUPAC names Taesmegen is ncuded andthe TONgest chai Talk, 1 7 eisapace which 0s ain, 3 Axle carbons seested. % [ Alkanamine Be at : Alkane isoitie bu -H,-CHs-O-CH, 5 Alkanal | CH;-CH,-CHs Alkane thiol L-Methowspropane . f ees 6 Alkanone 2. CHy-O- CH) -CH,~CH; 8 ee |More , 2 9 pea CH; -CH-O-CHy Pot Atkancicacd eal § CH 10 7 2-Metbory propane ae Alkanoy chloride ee | rample 4) n, cone Fret TUPACAME OTe COMPO Sth TNH: Atkanamige me Cli; -CH, ~CH-CHy 2 cen Alkane nite ° 13, i ~E-0-R-—Allytatkanoate ° seamed Sol. (2-ethoxybutaney RC. 4 < Nomenclature ofketo group : Regen Alkanoic anhydride The carbon ofa ketone is included in longest chain, It y comes on first ols postions, whereas CH (ain a 8 comes at frst and last position onty (atehe pap is RC eae "CFO Alkanoicalkanoc any BL CH —CH~CH—CH REC veri af ° j - 1 Hy SMBEesthe TUPAC name ofthe compound 3-Methyl-2-pentanone eas : Note: : 3 : i ith hesane cH,CHEMISTRY 9 cH, cu, BMH -Cl ACH, ~CH cH, -CH-CH, CH, -G “NH, 0 Sol. 1. 3-Methyl pentanal 2. 2,2-Dimethyl propanoie acid 3. 3Methylbutanoyl chloride 4._3-Methylpentanamide eee Nomenclature of ester : Alkylalkanoate i Ex. CH, -C-0-CH, [Nomenclature of anhydride Methyl ethanoate ° l Re Do R-C u ° Total C 5 = Substract = number of C atom = Alkanoic anhydride ° i Cs CX 4 CHs-c a 7 Ethanoic Anhydride ° WReR TUPAC name—alkanoic alkanoic' anhydride f O CH-CH,~ C ll 0 Fhanoie propanoie anbydride (Organic Chemistry ~ Some Basic Principles and Tadhniiquss Oo Ih CH - Cy ‘0 CH, -CH CH, OR, a) Tl ‘ames for the compounds having two similar functional iFoups: ‘S.No. Functional group TUPACName I 2-X no., no. - di halo alkane 2 2-0- no, no.,- di alkoxy alkane 3 2-Nih ——_Alkanediamine-no.,n0* 4 2-N2C Alkane di isonitrile-no., no, 5 2-08 ———Altanediol-no.,n0 ‘ 2-H Alkane di thiol -n0,00 1 2-C- Alkane dione-no,no-* é & ae Alkane dial é 9. 2-C-OH Alkane dioic acid {I é 10. 7 oo. Alkane dioyl chloride oO u 2-C-NEy Alkane di amide Il . Oo 12, Alkane di nitrile Rules for TUPAC names forthe comgiound having polyfunetional groups: When an organic compound contains two or more different functional groups one is selected as the principal functional group while other groups are treated as substituents ‘Numbering the principal chain orderis [Principal functional group > double bond > triple bond > substituents] The longest possible chain of carbon atoms containing the functional group and the maximum number of multiple bonds is selected as parent chain,Organic Chemistry - Some Basic Principles and Techniques The priority order of the functional groups is as under Name Formula [_ Functional grou Prefix Suffix Carboxylicacid | (COOH Carboxy oie acid COOH (no count) Carboxylic acid Suphonic acid | soy Sulpho -Sulphonie acid =10)0. 5 Anhydride > i - oie anhydride ~(C) 0 Ester ~(C)OOR a —oate -COOR Alkoxy carbonyl carboxylate Acid halide ~()0X Ls A halide Cox Haloformyl carbonyl halide] Acid amide —(Q)ONH, =e —amide -CONH, Carbamoyl carboxyamide Cyanide -()=N = =nitrile -C=N Cyano carbonitrile Isoeyanide = —isonitrile Carbylamine = Aldehyde Oxo -al formyl carbaldehyde 0 II Ketone +C)- 0x0, keo = one Alcohol OH Hydroxy: -ol Thioalcohol SH Mercapto- thiol Amine NH, Amino- Amine El Note: Example 7 ‘Write the IUPAC name of: (Longest chain is selected on the basis of priority and ‘numbering is also done on priority basis. (ii) Senior groups are never written as substituents whereas juniors are written as substituents. Example 6 Write the IUPAC tame of 304 5 CHis ~CHlp ~CH ~CHty “CH -CHy 2 6 NCH) Sol. (1) The longest chain containing functional group is of 7 carbon atoms. Therefore, the word root is hept and the chain is numbered as shown, (2) There is no tultiple bond init Hence, the primary sufix isane (3) The fmetioal groups is ~CN. Hence. secondary sulfix isnirile (4) Moreover. there is a methyl groups on carbon and ethyl group on carbon 3. (5) The IUPAC hame is therefore, 3-Eihyl5- methylheptanenitrile i “cu,"cHcH, chy sl I cu-ch- eH Br “CHNO, Sol. (1) Primary suffix is ene, due to presence of double bond between C, and Cs. (@) Secondary functional group is aleohol hence secondary suffix iso. (@) Root word is undec. (@) Chain is numbered as shown, (6) 6-Nitro-7-methyi-8-bromo- 0-aminoare prefixes. Arrange them in alphabetical order and give the name: 10-Amino-8-bromo-7-methyl-6-nitroundee-ten-2-0l Nomenclature of Aromatic Compounds (i) Nuclear substituted i.e. those in which the functional group isdirectly atached tothe benzene ring. In the IUPAC system they are named as derivatives of benzene. The positions of the substituents in disubstituted benzenes are indicated either by prefixes or by arabic numerals such as o-ortho) 1, 2-m-(meta) for 1.3-and p-(para) for 1. 4-Organic Chemistry - Some Basic Principles and Techniques (ii). Side-chain substituted : Thosein which the functional group ts present in the side chain of the benzene ring. Both in the ‘common and IUPAC systems, these are usually named as phenyl derivatives of the corresponding aliphatic compounds. The positions of the substituents on the side chain including the benzene ring are indicated by Greek lettersi.e.., By... et, in the common system, and by arabic numerals, i. 1,2, 3... etc. in the IUPAC system, However, ‘many of these compounds are better known by their common names. ‘The IUPAC and common names (given in brackets) ofa few important members of each family are given below. @) Aromatic hydrocarbons (Arenes) : Hydrocarbons which contain aromatic units are called ar (Benzene and alkylbenzenes CH, Benzene Methybenzene ey ‘Toluene (o-Xvlene) cH, cH, y D >CH; S 1 3-Dimethybenzene CH (mvXylene) 1.4-Dimethybenizne (Xylene) CH; CHCHy y HC ACH; 1,3, $Trimethyibenzene ErthyTbenzene (Mesirylene) 123 CHy-CH-CHy 2-Propylbenzene (sopropylbenzene or Cumene) (i) Alkenylbenzenes 12 aH =CHCH, CH=CH, : Een Ibenzene (styrene. vin benzene or penvletyleney |-Propenylbenzene (> Methyltyrene) Bee CH,CH = cry, 3-Proponylienzene (allybinzene) ii) Allynylbenzene =cu thynylbenzene 1-Propynylbene henylaceylene) (®-Methyiphenyaces ten) (Gv) Hydrocarbons containing condensed or fused rings : mE g 9 4 1 2 t 2 ‘ b ‘ S x x w Y ‘Naphthalene aaa 3 4 oe. H 6 y 9 Phenanthrens 7 cH CHS Phenyl Benzyl Banal «Benzo cH, cH, cH, f 7 7 2Toluy 3Toluyl Tost oro-Toliyl "—orm-Tohyl——_aypr~ Touyl () Halogen derivatives : cL fo Ly Tcmene—12-Dibnet o cee ‘0-PichlorabenzeneOrganic Chemistry - Some Basic Principles and cl cl y y a a w eel cl 1 Dichlorohenzene ‘or n-Diehlorobencene 1, 4-Dichlorobencene oF pDichlorobenzene nylehloromethane Phenslnchloromethane lcnzyl chloride) (enaaeihlorade) CHCl O Phony dibloremethane (enzat lore BOM 1-Cho-2-penstthane {Pens elo 3 Ch a i | -tiom-3-pinyopane {o-Pheny prop bromide 1 seiner SChorw-2-ph 3-Bromo-L-phenytpropene (Cinnany bromide) (©) Hydroxy derivatives. The nuclear hydroxy derivativesare called phenols while the side chain substituted hydroxy derivatives are called aromatic alcohols, (Phenols —Monohyat on ou ACH, ; 2-Methyphenol ddl (o-crel) H OH J 1 ieteea crt "msl oy 4 Methyphenl toes ( ddricphenals. HI \ OH 1. 3-Ditydronpbenzene ‘Resorcinol cH Techniques pasta on dW OH 1.4 - Dihydroxybencene (Quinol? IH OH i 1H 1.2.4 -Tribydroxyhenzene (lydroxyquinol) Pyeogaled) Ho® Sou 1,3, 5 ~Telnydroxpbenzene (phloroglucinol) Aromatic aleohols acts cH,oH sCH, ~ CHl,~ OF Phenylnethano! 24 (Benzyl aleohal) enylethanel (B-Phenyletny alcohol) 2 4 (Cis CHO [-Phenylethano! (c-Phenyletiy aleatol @) Aromatic ethers OCH, O-C,Hs Mathoxsbenzene Phenorybenzene (Anisote or Methyipheny ether) (Dipheny ther (©) Aldeliydes CHO CHO cr Benzaldchyde 2Aydroxybenzaldehyde (Salicplaldehyde) a2 4 GH,CHO sf PeCHCHo Phenylethanal 3 -Phenylpropanl (Phenyleetaldey de) ((-PhenylpropionaldehydeyCHEMISTRY Organic Chemistry ~ Some Basic Principles and Techniques 6, Ketones NC Coch, COC\Hs N-Phenylbenzenamine (yphenylamine) Lethenletianone Diphenymetianone ; (Aceupherene oF (lenzopkenane (6 Arallfernlas Metheny ketone) Diphcyl keto a eee H.NH, (GHC NH, COCH,CH, oe henyncthnamine ———2.Phenyedonamine LePhenspopanone (Denzylaine (6-Phenseylamine) (epiphone) a (0) Arenediazonium salts NO; Ho i ner &- NHSO} Denmneaoniam ——_-Bewanedaanum NO; ‘hlonde sydrogensiphse sade | Dien of (0 Cyanidesand isoeyanides: Naroenzene sn-Dinhroberene ony OH ° 1 CH, NNO, gO S Benzntileo Beryl aide No, Phyl vaide Penylctniie aes se sees x -Nitooluene ‘Pipher Hs 7 ON Ze NOn hen isoeanie © P Phenyl eayumie : @ Carboxylic acids : No, COOH ‘OOH 246-Teniropenot 2.46-Tiitotolune 1 erie ai (INT) clts (@) Amines @ Arylamines Benzoie acid -2-Methylbenzoie acid NH, or Benzene cori ald (oobi acid) q COOH COOH NH, on ‘00H ie a i Hy 2Hydoxybenaoie seid Benzene, 2-dkarboxyi aid Benzenamine Samabarinaat (Salielc acid) (Phualicaid) (Aniline) (p-Tobidine) ‘COOH T NCH); ‘00H 3 COOH Benzene-1,2iamine _N.N-Dimethylbenzenamine nS (o-Phenslenediamine) ——_(N_N-Dimethylaniline) a (Terephhalic acid) (Usophthalie acid)rgartc Chemistry ~ Some Basie Principles and Techniques (8) Sulphonie acid: SO. $0;n SO, Beton : sulphonic aid Nu, CH PeAminobenzene Te sulpnic aid Sulphone (Sulphate city ecee Bond-tine notation of organ compounds, in this notation, bonds ae represented by lines and carbon atoms by line ends and intersections, © Iti essumed that required number of H-stoms are presen wherever they are necessary to satisfy tetracovalency of carbon. For example, cH, | CH2=C~CH=CH, is representedas | es 3 2 Methybutane1. 3-diene of Isprcne Some other examples are OH 1 4 Oo 3~6 1 2-Ethenyl3-methyl —3-Ethyl-t-meihythere [3-eyeloheragiene ——hen-2-one Homologous Series When structurally similar organic compounds are aranged in the order of increasing molecular weight, then the series of compounds so obtained is called a homologous series {Ds members of such a series are known as homologous of re another. faracteristics of homologous series : 1, All members ofa homologous series can be represented by only one general formula, 2. The members ofa homologous series differ in their molecular ‘weight by 14 ar its multiple and their molecular formulae’ by CH; or its multiple. 3. Physical properties of the members ofa homologous series normally exhibit a regular gradual change, 4. Themembers ofa: ‘homologous series ‘normally exhibit similar chemical properties. 5. The members of a homologous series can be synthesised by some general methods of preparation, Homologous cannot be isomers due to difference in their molecular formulae, Therefore, two or more than two some can never be included in the same homologous series Series Member General formula Alkane~— CHy. C,H, ete. CyHonsd Jkene ~ CH, CH, ete sig Alkyne - CyHs, CyH, ete ny» Monel CHOH.CHOHee. Chin” “oy AG CHEMIs) cHOde. §— CH, 9 0, CHCHO et. itl He coo! 1, CH,COOH ete. C,H, 6, Ry Alkanal= 1,0) tani te (1r primary ANS) ang Alkylamin secondaryamil onatitute different hor us) aed rallamines rei yi jologous series. ‘y Reactions ar serane reaction is in fact a bond breaking and a ney tong making prose es A-C4B AH Substrate + Attacking reagent — Products, caetion mechanism = eae ittate > Intermediate > Produts (transitory) Type of Bond Fission or Cleavage {Breaking of a Covalent Bond) (i) Homolytic (symimetrical) fission or Homolysis : (@ Ifa covalent bond breaks in such a way that each atom, takes away one electron of the shared pair, itis elgg homolytic or symmetrical fission or homolysis, Aj, Homies aol Free radicals (i) The neural chemical speci (such as A and B) whi contain an odd or unpaired election and which wn produced by homolytic fission of covalent bonds 2 called free radicals. (ii) Favourable conditions ; (©) High temperature) Light of suitable wavelength (©) Non polar solvent (d) Presence of peroxide or oxygen (©) Abily of substrate and attacking reagent to praee free-radicals, Heterolytic (Unsymmetrieal) fission or Heterolysis: {@) When covalent tond joining two atoms A and Bbres in Such a way that both the electrons of the eovlet bond (i.e. shared pair) are taken away by one of he ended atoms, the mode of bond cleavage is ale heterolytic fission or heterolysis, (b) Heterolytic fission is usually indicated by a curved arrow Gi) at Hetervic fission A+ 4. We fission At oR (when Bis more electronegative than A) Heterolytic fission (©) Favourable conditions : f () Low temperature (b) P aia *olar solvent (c) Prese! acid or base catalyst (d) Polar nature of the substrate and attacking reagent,CHEMISTRY Classification of Reagents O/etropiles or electrophilic reagents (E*): is cctron deficient speci (a) They ar {b) They are always in search of electrons. {c) They have a tendency to accept electron pair from another molecule (hence electro electron, phile=love).. Ina reaction, an electrophile attacks the substrate at the point of maximum electron density. Electrophiles may be neutral or positively charged Neutral electrophiles : Central atom has deficiency of electrons. eX. BF, BCly, AICl;, BeCl, FeCl, SO, Charged electrophiles : All the positive ions behave like electrophiles. CU, BE.P.NOYNO" HY, HO". Ni RE, R—C=O.cte wo (©) Flectrophites are generated by heterolysis ofa covalent bond, (Tr Fe} Fe, Ag’ Hg? Ca", ete. (g) All Lewisacids are electrophites (i) Nucleophilic reagents or Nucléophiles (Nu) : (a) They are electron rich species, they have a tendency to donate electron pair. (6) They attack the centre of minimum electron density ina chemical reaction, They are of two types == Charged nucleophiles: All the negative ions qualify as nucleophiles. F,CI.Br-.-,OH-, CN", RCOO™ ROR, R-C=C, NHp, SH, etc. Neutral nucleophiles : Central atom has electron pair. iH, .R- NHR, RN, H,O:,R-O-H, sition metal cations are electrophiles NH;,R— R- 6 -RH,S, 202 Teese R—C—O—H> NH,— a” ot R—Mgx ee ie n Displacement Inductive Effect ‘The permanent displacement of sigma (9) electrons longa carbon chair ina compound due to ' the attachment of a ors clectronegative or more electropositive atom or group ol ‘coms with the terminal carbon of the chain is ‘called inductive effect. ja Na, Wi, » Organic Chemistry ~ Some Basic Principles and Techniques Assunte carbon at the head of a carbon chain is attached to a more electronegativeatom *X" then iss oe" oh Cl CCX (6 more electronegative than carbon) When carbon is attached to less electronegative atom then common electron pairs are push towards carbon chain that produce partialy -ve charge on carbon chain. i550" 85 CoC C OY (bes elestonegtve than erbon) Inductive effect (I-effect) is of two types. ~Leffeet : Atoms or group of atoms which attract the bonded clectrons more strongly than hydrogen atom, are said to have =I effect and are termed as electron attracting (-I groups). Such groups when inked with a carbon chain make it electron poor. (a) e.g, “NR; >~ NO; >-CN>-COOH>-F >-Cl>—Br>-1>-OH >-OR >-C,H,>-H ® +1 Effect : Those atoms or group of atoms which attract the shared electron pair (bond pair) ess strongly than hydrogen ‘atom are said to have +I (electron repelling) effect. Such ‘groups when attached with a carbon chain displace the shared o electrons towards the chain and make it eletron rich, (CH),C-> (CH,),CH-> CH, ~CH,-> CH,~ Inductive effect is represented by an arrow (>) pointing towards the more electronegative element. Inductive effect ofhydrogen is zero, ie. it either attracts nor repels the bond pair between carbon and hydrogen. Applications of inductive effect (@) Reactivity of alkyl halides: ‘Thereactivity order of alkyl halides is— R R>-C>-X > a R R 3 or Tertiary halide (Most reactive) 2 oe Secondary alkyl halide > RACH 3-X> CH, >—X 1 Pi alkylhaide Meth halide (Least reactive) (Acid Strength : Acid strength «« —! FHeffect HCOOH> CH,COOH> CH, ~ CH, -~COOH>360 Organic Chemistry - Some Basic Principles and Techniat CH,- CHCOOH > CH, cn, Acid strength 2 —| effect cH, oF SA E—COOH < Creche leone CH, i) 7 o f < OFC cl Acid strength increases Ka increases, pK decreases w noeen having sronger effect makes an acid stronger Forexample, oF oF I I H> CHC 0-H Fcc Fluoroacetic acid (Strongest acid) BrCl, C9 s ICH, CHy~CH Oy ény-En Lilie, i ; ch B-Chlorabutyr) ‘eChloroburyre aed a « é Hy -COOH bi, C1, -CH FO Or cba cami, lens fendene, (On incr Mary amy, kyl group increases the electry NH the +1 alkyl group increa = nea ‘atom of "NH, group. As a result, the 1 NH, group todonate the electron pair toa pro Increasing order of basic strength of aliphatic pr is ; Nit; < CH;NHy < CH3CH3NHy <(CHy C1) Basiestengh ofaliphatc andaromatic amines varies, NH, Hy > Ar- NH, Electromeric Effect (E-effect) The temporary effect which operates in the organi having multiple bonds ie. double or triple bon influence of n outside attacking species. As aresul, ey electron pair ofthe multiple bond gets completly rans, lo one of the bonded atoms which is usually mer clecronegatve. The eletromeric effects shown ya ans arrow (Cx) representing the electron transfer origina, from the centre of the multiple bond and pointing onan, one ofthe atoms which is more electronegative. The et, can be illustrated by the attack of H’ ion on the molly ¢ '€compaung ids under alkene. Settler Ne ct ZoOWN eoacy H Catoctin Types of clectromeric effect : The electromeric effect is of two types iv ~E-effect. +E-effeet : If the pi- transferred to the aton attached, the effect is a + E-eflect and electron pair of the multiple bond is m to which the attacking reagent gets called +E effect. For example @ CHy>-CHECH, +Ht_, CH, ~ CH-CH: Proper NA toprop aston In this case, CH group has +H (inductive) effec andthe electron shi ft can take place only to the right ~Eceffect: In case thepi-electron Pair of the multiple bondis {ransferred away from the atom which gets linked to the attacking reagent, the effect is known as -E-effect. For “sample attack of CN- ion on formaldehyde,0 en ca W New Fiistamine is more basic than anitine, W hy ? sol, Due toate “Telteet of ethyl y up. le9 CLNH, is tess bayie than methylamine. Why ? sol, Due te Letlectol Cl group and py, _d conjugation (ii) Resonance a) Sometimes. 1015 not possible to assign a single electronic {Lewis}structure toa molecule which ean satistactoniy explain alls properties. In such cases, f has beet Found that the molecule can olen be represented by two oF more Lewis structures, cach one of whieh can exphin most of the propertics but none of them ean eyplam all the properties of the molecule, The real structure of the molecule lies somewhere in between al these electrome structures whieh differ in the positon of position oF atoms. The various Lewis structures are called canonical or resonating structures (b) The real structure of the molecule 1s not represented by’an cofthe eanonteal structures but ts actually a resonanee hybrid of all these Lewis structures. arated by a double headed arrow (6). trons but not an the relative The \nious resonance structures are se} (©) Thus in the light of resonance theory, benzene can be represented as a resonance hybrid of the following two Kekule (Lewis) structures. | and IL. a-o I i Ww Resotfance energy : stable than any of its canonical (hypothetical or imaginary) structures. This stability is due to delocalization of electrons and ismeasured in terms ofresonance energy or delocalization energy. (b) It is defined as the difference in internal energy of the resonance hybrid and the most stable canonical structure, Further, more the number of equivalent resonance structures, treater is the delocalization of electrons, larger is the resonance energy and hence more stable is the compound. 150.62 kJ mol! or 36,0 kcal mol! isthe resonance energy of benzene. ‘Types of resonance : Resonance is of two types. )_AsGvalent resonance : When the different canonical forms of ‘a molecule contain same number of bonds, the resonance is said to be isovalent, For example, a carboxylate ion shows ‘sovalent resonance. {C.Charaeteristics of resonance and resonance hybri Organic Chemistry ~ Some Basi Principles and Techniques 361 (0) Heterovatent reson el When the number of bonds are lifirent in different canonical forms, resonance is sd tobe heterovalent For examph _ cls ssonance in 1, 3-utadiene H=CH Hy © CHy CH=CH CHy ! OCs CHECH GL, WW : Suwueture T hay eleven bonds, while suuctares fl and UL somtain fen bonds each, Conulitions for resonance TH Theatomic arrangement isthesame in all the canonical forms. ii) Same number of paired or unpaired electrons must be present in each canonical form. ii. The canonical forms must possess same or nearly same energy. The molecule must havea planar structure. All the canonical forms do not eontribate equally towards the structure ofa resonance hybrid. A more stable canonical structure contributes more to the resonance hybrid. The conutibution depends upon the following factors (a) Presence of isolated charges or increase in charge separation decreases the stability of a canonical form and hence its contribution in the hybrid structure, (6) Whenall the structures have formal charge. the structure having negative charge on electronegative and positive charge on electropositive element (atom) will be more stable. For example, carbonyl group isa resonance hybrid of the following structures. tiv) w) >C=00>C-06>C-0 1 uw m The polar structure (I) is more stable than (III) because inthis structure negative charge resides on oxygen (more electronegative atom) and +ve charge is present on more electropositive carbon atom, (©) Resonating structure having electron deficient positively charged atoms possess very high energy and hence are unstable, (@) Resonating structures with a greater number of covalent bonds are more stable. @)_ A resonance hybrid is more stable than any ofthe canonical forms. Grecter the number of resonating structures which can be written for a molecule, greater will be its stability Thus, resonance gives extra stability toa molecule and hence decreases its reactivity, Resonance hybrid possesses lesser energy than any of the canonical forms.BGonanee eneray : 1's a measure ofthe stability of a theonanGe hybrid. W may be defined as “the diereec in {he energy of most stable (mn "um contributing) canonical form and the resonance hybyi Resonance Energy ‘Theoretical heat of formation ~ Experimental heat of formation, energy of a molecule, greater is its @) Higher the resonance stability, (Oy ® © Toexpain the aidienatre hydrogen atoms in acetylene molecule, IP ESC-HOHCR CHG iiGacH o fee (© Teexplain the uneactvty othalogen atom sa vinyl halide CU CH Gives Hy ce by a Vig rte () Toexplain the reactivity orhaogen atom in allyl and benzyl halides (CH, =CH-CH,cl = CH, =CH~ CH, +@ t @ Cly-CH=cH, (8) To explain the acidie nature of phenol. Its conjugate base (Phenoxide ion) is resonance stabilize O-n ; One d G Phenol Phenoxide ion w) Toexplain the stability of carboxylate ions, Carboxylate ion Bond order : In the compounds sho wing resonance, bond order may be calculated as follows Organic Chemistry — Same Basic Principles and Techniques number of bonds on eens saber tructne weder = ~~ Number of resonating Bond or be 1» carbon and OxYLeN in carbonate Bond order ae C—Obond distances are equal gy iu (CO,?>) ion = Q Xo — eo f A, ” 2elel_4 Bond order= —S— = 5 1.33 N—Obond order in nitrate (NO5) ion 0 a -n~ —o-n Z —o-n ont 7 \o Bond order between O and N = C—Cbond order in benzene C—C bond order: Bond order in SO, r 2p o “SQ oo ork ai \ ° Bond order between $ and © (@ Mesomeric kftect I involves x-elsctrons and lone pair of electrons in Conjugation with each other Itis a permanent polariz interaction of two x-mo Srbital and one tone pair ofelectrons, The only, Condition for this effect is that the m-bonds ‘should By eation with each other ‘ation caused in a molecule due to cular orbitals or one m-moleculat nes C= CH Nomesomeric effect of ableton oH ae ~CH, 7 CH=CH, Nomesomeric effect nuble bondsOrganic Chemistry ~ Some Basic Pri encarta Conjugated system of (sn Conjugation) nesomcric effect CHy-CH CH- CH, @ CH; ~CH=CH-CH also arises due to %-lone pair conjugation. Mesomeric e For example. in vinyl chloride. © CH, -CH= Cl [+ Meffeet] CHE CH= Cl , Typos Mesomerie effect: ‘yimay be +M or—M fa) *Meeffect : HM effect involves transfer of electrons away from the atom or group and towards the carbon chain, Such groups make the carbon chain electron rich, For example, note the above examples. (b) -Meeffect : -M effect involves the transfor of electrons towards the atom or group. Such groups make the carbon. chain electron deficient, For example : CH-CH=Q © CH)-CH=CH- 6 CMeffect) Acroein ‘Some common atoms or groups which cause +M or -M effect are given below +Meffect : eg. . — Nn, — Nar. —Meffeet \ eg. CHO, 4 yee Hyperconjugation, Baker - Nathan Effect (No Bond Resonance) (2) It involves the delocalization of C—H sigma (a) electrons with electrons of a multiple bond when they are in conjugation. Therefore, itis also called o-7 conjugation. (b)_ Inthe system H-C-C=C, the electrons of C- Hbond are released in the unsaturated carbon chain. This phenomenon is called hyperconjugation @ H H ol eo Wor — -c=C-€ ol Od (co) Thehydrogen atom ofthe H— C bond acquires a +ve charge ‘but remains very close to (a) carbon atom although there is not any bond between the two. Hence, the name no-bond resonance or hyperconjugation. () Greater the number of H-C bonds attached to an unsaturated ‘system, more will be the electron release in the unsaturated CO, — CN. —NO,,— SO,Hlete iples and Techniqu carbon chain, greater will at ch ill be the number of resonating Forexampl n propylene, there arethree HC sigma bonds in conjugation with the bond. So, ce ena Trace ith . So, only three resonating, Propylene contains 3H~Chyperconjugated bond H H | ~ Il - i CH CH, <—» H- C=CH-CH, it In [-butene, there are two a. C ~ H bonds in conjugation with double bond (x-electrons), so only two canonical forms can be written, H ol a Hw cH,—C* CHS CH, <> CH,-C = CH-CHy of an ° H H "-Butee 1 H CH;- é =CH-CH; Hw ‘When an isopropyl group is attached with an olefinic system only one CH bond is hyperconjugated. H + oy H, = CH, -C-CH% CH, <——> CH, -C =CH-CH) be b-€ hn CH CH; {Only one H -C hypercanjgated bond In case a tertiary butyl group is attached with an olefinic system, there is no C —H hyperconjugated bond, hence no hyperconjugation. CH; ol chy CH=CH; CHy [No hyperconjugation, no -electron release because there is no « CH bond]Orpunic Chemistry — Some Basic Frinciples and Techniques Gonance energy : It is a measure of the stability of a Fesonance hybrid, It may'be defined as, “the difference in the energy of most stable (maximum contributing) canonical form and the resonance hybrid! Resonance ‘Theoretical heat of formation @ ~ Experimental heat of formation, Higher the resonance energy of a molecule, greater is its stability, (©) Bond lengths between atoms in a resonance hybrid are tliferent from those in canonical forms. For example in actual benzene molecule the carbon-carbon bond distance between adjacent atoms is equal (1.397 A), while in the Kekule structure, itis 1.54 A.and 1.34 A alternately. \Wpolicatons of resonance: (0) Toesplain the acidic nature ofhydrogen atoms in acetylene molecule, (b) H-C8C-HOHC= CHe Cech ofc 0es/ oy ons” 0 % Bond order between § and O = (0) —Mesomeric Esfect It involves x-eléetrons and lone pair of electrons in Conjugation with each other. : = CH, Cumiative sytem oF double bends Nomesomeric effect CH, H-CH, - CH=CH, Nomesomeric effect bolated system of double bondsOrganic Chemistry - Some Basic Principles and Techniques on rte . eo ) Ciy-cH= CHE CHy © CH; ~CH=CH-CHy Mesomeric effet also arises due to =-one pair conjugation. For example, in vinyl chloride. ry “fin be=M or MI (a) #Meeffect : +M effect involves transfer of electrons away from the atom or group and towards the carbon chain, Such ‘groups make the carbon chain electron rich, For example, note the above examples () -Meffect : -M effect involves the transfer of electrons towards the atom or group. Such groups make the carbon chain electron deficient. For example: n+ - ch, CH-CH=Q © CH;-CH=CH- 6 (-Meffect) Acrolsin Some common atoms or groups which eause #M or -M effect are given below +Meffect: oe. —On.—GR.— Nn,, — Nur, — Nr, — =Meffeet: eg. wo. co. —CN, —NO,,— SOjHete erconjugation, Baker - Nathan Effect (No Bond Resonance) (@)_ It involves the delocalization of C—H sigma (o) electrons with x-electrons of a multiple bond when they are in conjugation. Therefor, itisalso called o- conjugation. (b) Inthe system H-C-C=C, the electrons of C —H bond are released in the unsaturated carbon chain. This phenomenon is called hyperconjugation (s) Thehydrogen atom ofthe H- Cbond acquires a +ve charge ‘but remains very close to (a) carbon atom although there is not any hond between the two. Hence, the name no-bond resonance or hyperconjugation. (d) Greater the number of H-C bonds attached to an unsaturated. system, more wil be the electron release inthe unsaturated carbon chain, greater will be the number of resonating structures. For example :In propylene, there are three H—C sigma bonds in conjugation with the x bond, So, only three resonating forms can be write, 0 © CH= “cH, <> H-C=CH-CH, we | 7 H pyle contains 3H =C hyperconjugated bond i t <> HYC=CH-CH, <> H- C=CH-CH, | we H In I-butene, there are two oC ~ H bonds in conjugation with double bond (n-eletrons), so only two eanonies forms can be written. 7 ° H = cH, a cu ft, CHG = CHC H H 1-Bsene i CH;- C =CH-CH, 7 ‘When an isopropyl group is attached with an olefinic system only one C — H bond is hyperconjugated. tt 4, tka CH, <——> CH, -C =CH-' CH, al ~ i CH CH; {Only oe HC hyperonjugsted bon] In case a tertiary butyl group is attached with an olefinic system, there is no C~ H hyperconjugated bond. hence no hyperconjugation. -G- CHECH, CH [No hyperconjugton, no x-leton release because there is no@ C—H bond]{08 Organic Chemisity Some Basie Principléé and Techniques Thus when the alkyl groups + 1 and CH,~ are atlached with an oletinic bond, their electron releasing tendencies follow the order Chy 1 ‘ts of hyperconjugation Stability of alkenes : Alkylated alkenes are more stable than others. Greater the aikslation ofan alkene (greater the number of allyl groups ‘nan alkene] greater ists stability Thus, the sabilty order ie ROE=C-R> RaC= CHR >RCH= CHR> RR Tetcatkyt ethylene {most stable) (east stable (i Bond lengths : Possibility of hyperconjugation in a ‘molecule results in a change in bond lengths. For example, inpropene, 3 2 4 CHs~CH = CHp the C, ~C, bond distance is observed {0 be more than 1.34 A (expected value while the CC. bond distance is ess than 1.54 A (C-C single band distance) Tis explained by hyperconjugation as follows Ht 2 4 32 HOO™ CHS CH, — H—C=c'H-CH, T U | H H 1 (ili) Stability of alkyl free radicals: The delocalization of C— H c electrons can also take place via the half-flled p-atomic orbital in conjugation. Thus, the relative stabilities of alkyl free radicals are in the order : ser-alkyl> see. alkyl > primary alkyl > methyl radical For examp! > (CH); CH > CH; CH, > CH, Greater the number of hyperconjugative strictures ofan alkyl radical higher isis stability. Ethyl radical may be regarded sa hybrid of following hyperconjugative structures, (CH); € 7 . gfe H 4 Wy, HCH Hu H of alkyl carbocation ) Sia tn : ‘are also conjugated with a dit eration 4 das wen, — Hoc h H The stability of an alkyl carbocation is proportional tothe ber of hyperconjugative structures. ie.. number of {1 -Hbendsinthat carbocation. So. he dsessng by ‘order of alkyl carbocation is: 3°>2°> 1°> CH Ex aH; I «, + + + acs —C* > CH; —CH> CH; — CH > CH CH aC, Meths! (Least sable tecbutyl (Most stable) isopropyl Ethyl (Nine hyperconjugative structures) () Directiveinfluence of groups: Methyl group in toluene is an activating and ortho-para directing group. It can be explained by hyperconjugation, H H H Xu eT we HCH H-C HD -CP+ -O Tohene ~~ 6 1 0 mm Vv Ze flow of electrons takes place towards the benzene ring du to hyperconjugation. Therefore, the electron density increases at both the ortho and para positions, Consequently, the benzene ring is activated and the electrophilic substitution in toluene takes place at ortho and para positions, (Stability of alkyl benzene cH, cH, CHy—CH, CH,—CH-cH, cH,-C-cHl, Oro > O>o Meth 1 tsopropy! ter-utl benzene henzene benzene benzene aC bonds) 3 ocHEMISTRY more acidic than alcohols. Why ? Phenols " R-OH Sol. PhO I ja cw Ph-O" RO Stabe by resonance, No resonance so is more ae ) isless basic than alkyl amine, why ? li Sol, Duc to delocalization of lone pair of electrons on nitrogen in aniline, aniline is less basic. iy) ‘Which is weakest base (0) Coty - CH -NH (b) C,H, CH ~NH-CH, (©)0,N-CH,—NH, l,-NH-CHO. i) (d)CH,-NH=CHO Sol. (4) Duc to delocatisation of one pair of electrons on nitrogen. ‘Which of the following is most stable ? (a) Conjugated alkadiene (CH, = CH-CH=CH,) (b) Isolated alkadiene (CH, =CH-CH,-CH (c) Cumulated alkadiene (CH, =C=CH,) (A)Allare equal Sol. (a) Due to resonance, conjugated alkadiene (a) is most stable. Isolated alkadiene (b) is more stable than cumulated alkadiene (c) due to hyperconjugation. QereRMEDIATES Free Radicals | je fission, oe ye b-x —Homolytic fi _ cx’ | | IPENof C = ENofX (Free radical isan atom or group ofatoms possessing an odd or unpaired electron. It is electrically neutral and shows paramagnetism. (ii) Types of free radicals : CH, CH, CH, (CHy)p CH (CH4),€,CHy=CH- CH, Y ° aly Metyt Hs Bena i) Formation of free radicals : (a) Cly © , Cl-=Cl-[Homolstc fission] Hy (hy CH,CocH, T= CH,~cH,Co>CO+ CH, Organic Chemistry - Some Basic Principles anid Techniques (vii) Stability on the basis of resonane: (©) (CyH,),Pb —> Pb+4€: (d) CH, -N=N-CH, >N, o 0 Salient features : (Free radical reactions proceed in vapour phase or in nonpolar solvents. (i) Free radical reactions are frequently autocataltic. Reactions : (Chlorination of alkanes. (ii) Pyrolysis of alkanes. (i) Wurtz reaction. (iv) Anti-Markownikoff addition (¥) Kolbe electrolytic synthesis. (vi) Polymerisation initiated by free radical Stability of free radicals (reasons): (i)Resonance (ii) Hyperconjugation (sii) Order of stability of free radicals : ter-> see-> pri-alkyl> methyl > methyl ter-butyl > isopropyl> ethy Stability 2 Number of resonating structures Triphenyl methyl fee radical has the maximum number of resonating structures. Hence itis the most stable free radical, ‘The orderis: (@sC'> @,CH'> 6CH,"> CH, [where d= Cts} (@) Resonance in allyl free radical: () Resonance in benzyl free radical Ge CH, $-6-§-4 ‘Geometry, Hybridisation :~ Trigonal planar (sp hybrid) cH, oo 0 Carboniumion or Carbocation,‘Organic Chemistry Same Basie Principles and I cota benzy carbocation: Hetero ON IENOFX > EN orc ( Otganie species containing positively charged carbon atom 's known ay carbocation. The positively charged carbon «atom contains six electrons in its valence shell Gi) A¥pes of carbocations: Git, 4 Eis, erie, eye Maly oe (8) Formation of cartncatoss (2) (CH C~Cl-> (CH), C + CF [Meterlstie fission) 9 CON" CHOH, B25, Cry prownaton) (©) CH CH=CH; chy GH —cHy, [Protonation] (is) Reaetions: © Nucleophilie substitution of Gi) Markownikotaddition, Ikyt halides. (i) Hydrolysis of acetyl chloride. (iv) Dehydration of alcohols, Ex: CyHOH 2 HS08 CH, cH, ‘Hs i = CH, Mechanis CH,—CH,OH CH, ~CH, OH ecccee BS cH CH, 5 crecn, of carbocations : Reasons :(i) Inductive effect (ii) nance (iii) Hyperconjugation 0, (a) Stability of carbocation cc +1 cc 2 2 ® Ctl CH, > CH; > NO,-< CH, +Tgp. Tgp. (b) Stability < No. of resonating structures 2 8 @ (CoHHs)s C >(CgHs)y CH > CgHs CH ° @ > CHy=CH~ CH >3°>2°> 1°> CH Resonance in allyl carbocation : @ H, <> CH,— cucu, Two structures én, rie 2 ; C—O --O Four sretures Obviously benzyl carbocation is more stable as compared tg allyl carbocation. L 1 ‘Amount of charge Stability « Reduction of positive charge on the carbon (o) Stability of charged intermediate 2 R webs Nau RCH, >-CH, R R Explanation Dueto + effect of alkyl group there is dispersal of positive charge of the carbon. g ele Positive charge on carbon Rec is dispersed by three { alkyl groups Is. R Positive charge on carbon R= CHR is dispersed by two alkyl groups * 9 Positive charge on carbon RCH, is dispersed by onealkyl group @ CHy Moreis the dispersal ofthe postive chargemore is the stability of the carbocation ®@ 28 6@ «6 RyC > R,CH> RCH> CH [Stability +1 effet] Electron attractors [— 1 effect] increase the positive charge on carbon and thus reduces the stability of carbocation. 1 ~Teffect J [Stability oc 7 @ Hence, Stability: 0;N—- CH, HC (-I) effect order—NO, > C1cue ch : : satis URN: Ce CH, = Cy enon = ( Helfect oftwo-Clis moreas compared toone Cl ‘nocations: (ui) InteFconversion ofc re eer eevee” Hydride shift 1" —? 2") cH Gh cH, Cc, Alkyl shift [2° 3°] cH cu, cH,— C= GH —CHy—=—* CH, —C —CH—CH, cHy cn (sit) Geometry, Hybridisation : —C® planar (sy?) arhocations are electrophiles, Carbanion IfEN of C> EN of X An organic species containing negatively charged carbon atoms called earbanion, ‘There are eight electrons in the valence shell of negatively charged carbon. Two electrons remain as unshared pair. _()_Fypes of carbanion: CH,CHs ~CH,(CHs)) CH,(CH3)3€ Methyl Ie 2 - (ji) Formation of carbanion : 3 ->—CHO—> CH, ~ CHO +H,0 ane I SH 2 (b) CHO SHE COOC H+ CH:COOCHH +CHOH cH Organic Chemistry - Some Basic ineiples ahd Technigu nee 7 Organometallic compounds act as earbanion Ellon COOEt coon, Peston? MCHC ‘COE & 84 aie R=Li R—Mg Br (ii) Reactions (@ Aldot condensation (i. Claisen condensation (ii) Decarboxylation Example: RCOOH _solalime_, REY oO i : AL Lo aso (jv)_ Stability of carbanion: Reasons : (Inductive effect (i) Resonance (ii s-character in hybridisation Stability ofcarbanion oc-I x Q 2 2 Ex. (i) CHy-Gu, CHCH, > (CH,),CH > (CH3);C Explanation : Stability of alkyl carbanions can be explained by inductive effect. Greater the number of alkyl groups [+1 effect] attached tothe carbon atom bearing negative charge. lesser is its stability ate : 3°<2°< I< Methyl earbanion H CH or HC" > CH — > n> cHy H CH, oy CH, Gi) CH — NO, > CH, —CHO (iv) CH) —CHO > CH; (©) Gy — cH, —NOg > CH, —CH—NO, > (CH CH (vi) F—CH, > CI—CH;CHEMISTRY 308 ‘Organic Chemisity - Some Basic Principles and Techniques ah —fth (sm Resonance exists in CH —C = N hence its stable cearbanion, ato CH, (8) Geometry: Q Electron pair is present in sp? xv hybrid orbital; s- character = 25% | | H H Pyramidal (vi) Carbanions are nucleophiles, Carbenes :¢< - (Biradical) : A short lived divalent carbon with ‘two electrons, ii) Iti electron deficient and contains sx electrons in valence shell. (Itis a powerful electrophile) CH, (Methylene) CCI, (Dichlorocarbene) (ii) Formation of carbenes: CHN, _, :cH,+N, Diazomethane (i) CHy=C=0 —*+ cH, +C0 Ketene Gi) a +0H > H,0+CCh, H CCl —ser + zccl, (Dichtorocaene) fx). Reactions : \i) Hoffmann carbylamine reaction (ii) Riemer Tiemann reaction \n) Formation of eyclopropane from ethene and diazomethane Faample: CHaN, —> $CH, +N, CH, =CH, + #C! cit, (9 Twoforms of Carbene in which both non-bonded Oe rial with oppose spin sp? Angular (b) Triplet ‘Nodilrent orbitals th smespin ‘arbene in which both non-bonded es lie in Itisa neutral intermediate species containing nitrogen atom having one bond pair and two lone pairs. It is an electron deficient nitrogen, Formation ; Amide + bromine + caustic potash CH; —C—NH, +Br,+ 20H I CH 6 Ni: #28,04 2B 3 . Acylitrene . ‘Two forms of nitrene : @ Singlet: —N Singlet TYPES OF ORGANIC REACTIONS ‘The reactions of organic compounds can be classified into four ‘main types. - () Substitution or displacement reactions Q) Addition reactions @) Elimination reactions (4) Rearran, ement reactions ae sabi ‘ution or Displacement Reactions : Substitution or displacement reactions ate those reactions inwhich » Tran oF BF0Up ofatoms attached toa carbon atom in a substrate ‘molecule is replaced by another atom or group of atoms._— cn ry} @ MISTRY Free ralicasubstitation reactions CHC HCI Methane Unde iy CHCH,Be is replaved by chlorine ay KOH CH,CH,O1 KBr Eth akohol nator eto tore om is replaced by hydroxy group MBr——> CHB + HO at Met frome jeplaced by bromine Ahsoaicome) , CyHANOs + 1,0 Bromine wy CHOW Mats! ydhowsl p10 tivd Cyl, + HINO, ten Hydrog is replaced by NO, group He CH, + Cl, 5 CICH,CH= CH, + HCL : As shld «cH Proptene Uylrog, tsi) CH, © Cly 1 need by chlorine CHCL + HCL Chiorobonsene ensene Hyulrogen is replaced by chlorine Mechanism of substitution reactions: These reactions may follow free radical, nucleophilic or electrophilic mechanism. Some typical examples are considered to explain the three types of mechanism. Free radical substitution reactions : Chlorination of methane: The chlorination of methane in int isan example of free radical the presence of ultraviolet substitution (homolysis). CH,+Cl, + CH,CI+HCI ate Methane Methyl chloride The reaction does not stop with the formation of methyl chloride (CH,CI) but the remaining hydrogen atoms are replaced one by one with chlorine atoms to give rise to chain reaction, cH,CI-C, CH.C,-Cl, — CH,CI,+HCI — CHCL,+HCl CHCI,+C, —> CCI,+HC Mechanism : The reaction is initiated by the breaking of chlorine molecule into chlorine—free radicals in presence of Wight 1 Step : Chain initiation a, > cr +er MSeep : Chain propagation The chlorine free radical attacks methane molecule. ci, cr Cn, +H teach ofthe methyl fee radical, in turn reacts with chlorine molecule to form methyl chloride and at the same time Inlorme free radial is produced. ow @ ‘Organic Chemistry Serie Basic Principles and Techniques’ 340 CH Ch —scHyer yer MEStep : Chain termination The chain of reactions initiated and propagated as shown above may be terminated if free radicals combine amongst themselves without giving rise toany new radicals cle Ciel, CHy + ClL—-cH,cr Clly + Cth; 9 cH, = i, Reactivity of the halogen for free radical substitution is in the order Ch, > Bry >I, substitution : Many substitution reactions, especially at the saturated carbon atom in aliphatic compounds such as alkyl halides, are brought about by nucleophilic reagent or nucleophiles. R-X + OW —5R-OH+ X Substate— Nueteopile Leaving group Such substitution reactions are called nucleophilic substitution reactions, i.c., Sy reactions (S stands for substitution and N for nucleophile). The nucleophilic substitution reactions are divided into two classes. Sy2 Reactions : These are bimolecular reactions. When the rate of reaction depends on the concentration of both substrate and the nucleophile, the reaction is said to be $2, ie., 2nd order change. Rate [Sustrate] [Nucleophile] Hytdrolysis of methyl chloride is an example of Sj2 reaction ‘When methyl chloride is attacked by OFF, strong nucleophile from the opposite side ofthe chlorine atom, a transition state (TS) results in which both OH and Cl are partially bonded to carbon atom, MZ sl i x\/ 5 Demo lHo~ 17 al Hoe +r W H H H Methyl aeohol ‘When bromoethane is allowed toreact with sodium hydroxide under conditions where second order kinetics are followed, ethanol is obtained, ‘Transition sate HOW H \ V/s HC — Br—>| yor? HO CH, cH, Bromutiane Transition sate H Z et A cHCHEMISTRY Organic Chemistry ~ Some Basic Principles and Techniques Configuration : Hence, an Sy? reaction proceeds with Step? complete stereochemical inversion. This is also known cn Walden inversion cH; 5 Relative reactivity towards $42 reaction: bcncu +o Fo, CH, -C-CHCH Methl>elhy>isopopy>ter-buyi>aly> benythatdes CH“ “TN on carbocation (il) Sy1 Reactions: SI stands for unimolecular reaction. When clue treatin here 0 BS STZ an the rate of nucleophilic substitution reaction depends only ‘on the concentration ofthe substrate, the reaction is of first order and is represented as Sy 1. Rate [Substrate] The hydrolysis of tert-butyl bromide is an example of Sy reaction. The reaction consists of two steps. ‘Step 1. The substrate undergoes heterolytic fission forming, 4 carbocation. This isa slow process and rate determini step. cH, cH, cn, ft Stow sp, 1 CH; The carbocation is planar as the central positively charged carbon atom is sp? — hybridized. Step 2. The nucleophile (OH") can attack the planar carbocation ion trom either side to form rert-butyl alcohol and the low concentration of OH favours Sy! reaction. cH, CH, A OH Essie, cH, CH, CH, C-OH or Ho-¢-ci, CH, oy In another example, the carbocation formed (in Step 1) can undergo rearrangement to give more stable carbocation, Step t © CH; ci, -¢-cint ee, al cH; CH; : CH; -C-CH, aaa, ci -C*-crcH ii : oo) wy Asa result of Sy inversion, In other wert plus inversion Syl reaetion Hs | slow H-C—Br pry CH, Hs HO-C—H t A; ‘The nucleophilic reagent attacks both the back sideand the front side of the carbocation. Back si ide attack predominates. The two enantiomers constitute the racemic modification, Thus, in Syl reaction, racemization as well as inversion ig observed, while in case of Sy2 complete inversion takes place (where chal carbon exists). Sylteaction is favoured by heavy (bulky) groups on the carbon atom attached to halogens; ie., R\C—X> R,CH—X > RCH,—X >CH; Mattyl Teriary Secondary Primary Electrophilic substitution : Electrophilic substitution involves the attack by an electrophile.Itis represented as S,(S stands for substitution and E stands for electrophile) Ifthe order of reaction i I it is written asS- (unimolecular) andif the order is 2, itis S,? (bimolecular) Spl Reaction Mechanism: Electrophilic substitution in aliphatic compounds (Sl) are very rare. Some ofthe important examples are @) Replacement of the metal atom in an organometalic compound by hydrogen, R—M+H —5R—HeM! CHyCHNa+ Cy, CH, CH; +C,HsNaCHEMIST is and S,1Reaetions 5. Now Factors Sy2 Reactions Tsu Reactions One : _ Two: Ly i Rib+: Nu —9R:Nu+:b | @R:L > Ree (i) R'+ : Nu PBL RE Nu Second order : First order : 2 Reaction rate Rate cc [Substrate][Attacking species] | Rate a [Substrate] or and order Rate = KIRLJ[ : Nu} Rate = K[RL] 3 Molecularity Bimolecular ‘Unimolecular | 4 Reacting 7 a uatiay 7 a of | The nucleophile can attack sidciphie the substrate exclusively from the back} the carbon of the substrate side, both on the back and front sides, although the back side attack predominates. BS Stereochemistry ‘Complete inversion of configuration | Racemisation takes place. takes place 6 Reactivity order Methyl > 1° > 2° > 3° halides 3°>2°> 1° > methyl halides of alkyl halides 5 Ulin aid By electronic factor eae a By steric hindrance stability of R’ determining factor ° =) & Catalysis Not catalysed by any. catalyst (phase | Catalysed by Lewis and Bronsted aly transfer) acids eg, Ag’, AICl,, ZnCl, and strong HA. (0) Isotopic exchange of hydrogen for deuterium or tritium: R—H+D" = R—D+H R-H+T = R-T+H (ii) S_2 Reaction Mechanism: Electrophitic substitution (S,2) is very common in benzene nucleus (aromatic compounds) in which n-clectrons are highly delocalized and an electrophile can attack this region of high electron density. All electrophilic aromatic substitution reactions involves following steps ‘Step 1. The formation of an eleetrophile, E* i.e. E-Nu = E°+Nur e 6 9 «NO. $03 .R®, RCO Step 2. The electrophile attacks the aromatic ring to form carbocation (or arenium ion) which is stabilized by resonance. H. z H. H. z ~ On -O- -O S Resonating structures Step 3. Carbocation loses the proton to form substitution product HE 5 + . O-O" Ex. : The bromination of benzene in the presence of FeBr, is ‘an example of electrophilic substitution. Br COC Mechanism: Step 1. Formation of lectrophile Br—Br+ FeBry—9 Br’ + FeBry- Step 2. The electrophile (Br*) attacks the benzene ring to form a resonance stabilized carbocation. Che doa f Resonating structuresStep 3. Elimination of proton occurs and the substitution Product is formed, Ce or (UW + FeBry—> FeBr, + HBr) Similarly. nteation, sulphonation and Friedel ~Crafts reaction se. in benzene nucleusare other examples of electrophilic stfBstitution, (Z® Addition Reactions : Addition reactions are those in which the attacking reagent adds Up to the substrate molecule, Such reactions are given by those compounds which possess double or triple bonds. In the process, ‘triple bond may be converted into double bond or single bonds and a double bond is converted into single bonds. For each bond of the molecule (wo sigma bonds are formed and the hybridization state of earbon atoms changes fiom sp to sp? and iosp Like substitution reactions, addition reactions are also of three types, dition reactions addition reactions (6) Freeradical addition reactions Some of the exa Pe Ni Hy yi C1 W CHSCH=Hy =aag> CH=CH, Bas CH, -CHy 7 hone nples of addition reactions are Acetylene i) CHy=CI Enhytene Bry —> —CH,Br-CH, Br 1, 2-Dioromeethane (Ethylene bromide) ne ~HCN-——> cH, -< CN Ccyanohyin i Acid ti) CHC=N > HO 75> CHy-C-NH, Aedtamide Mesh cyanide Bs () CH=CH HBr —s CH,=CHBr——> CH,CHBr, a Vinyl bromide 1,1-Dibromocthane (Ethyliine bromide) Mechanism of addition reactions : The addition reactions are the reactions of the double or wiple bonds. These reactions may be initiated by electrophiles, nucleophiles or free radicals. The molecules havin C C = O or \ are readily attacked by nucleophilic reagents, rophilic addition reactions: In electrophilic addition an electrophile approaches the double or triple «lw the first step forms a covalent bond with one of Organic Chemistry ~ Some Basic Principles and Techniques 1s resulting in the formation of carbo the carbon atom DS ‘atagh then takes up a nucleophile to form addition produc, Vs =, 52d renege celta! ctephile lorans-i yolar molecule attacks the double bond of alkene. then = aie tao bond shifts to one of carbon atoms due 10 ectromeric effect. : ‘The aulition of Br on ethylene isan example of electphilic addition. Ethylene is a symmetrical olefin. Br | CH, = CH, + HBr ——> CH, ~CHy H Eiylene Eth brome ‘Mechanism: Step 1. Hydrogen bromide gives a proton and bromide ion. HBr—> H+ Br Etectopile Nockopite ‘Step 2. The electrophile attacks the double bond to form a carbocation. Nat + CH,=CH, +H’ —> H,C-CH, Carboaton ‘Step 3. The nucleophile (Brion) now attacks the carbocation to form the addition product. +e CH;—CH, #3BF —> CH,-CH,Br This clearly indicates that the reaction proceeds in two steps: (a) Formation of carbocation (more stable) and (&) Attack of nucleophile on the carbocation. Stability of carbocation isin order: Benezylic~3°> allylic~2°> 1°> methyl In case, both alkene and the adding reagent are ‘unsymmetrical, two products are expected, [> CH,CH,CH,Br (o-Prepy bromide) CH, ~ CH= CH, + HBr —] Propene : L_s cu, - Ga ck Br sopropst bromide)cHeMisTeY Pca served ha pep Bran the Fameautct Uns cat be explaied om the ants a vane ecTeanien Consider the adie of HE to pene wT es asym nt Tra tle Ise pest pret (Jana bro vind} Hine oe able fos the neband to ive a Step 2. The proton (11) at aL cnc Ci tL Step 4. Phe nucleophile bromide ‘nvcation to rive sopropyl bromide “a a Dec, Ct et Addition of HBr hy L-butene cl, CILCH, (Mowe stale > Cl, Cll, Uy Loss ste acks the more stable (major product) br cy clk cuy cu, Cue Cl EMethy LE buen {" mw chy cu, CH om CH, (2tromo-S-methy butane) Br (Minor produet) CH, I CH, CH CH, CH, Brome I Br (Major pro (major produet) can sment ofthe less stable carbocation by 1,2- Formation of 2-bromo-2-methylbutan be explained on the basis of rearrange 2° carbocation to the more stable 3° hydride shift. cH CH; cu, cH en ants crn la -CH- CH Levi 2° Caboction cH, CHy cnt cu, cH, 2 ch €-CHy- be — 2.tomo-2-metny ane more sable) Organic Chemistry — Hy Some Base Piiplosand Teehniquen 7 Addition reactions on alkali Cinta. a hi lagen a ids, hyclreyren and water, {hea wl 1, 4-adeition products, (Addition of halogens : = e) reacts wih bale amixturcot CBr CHBr CHL Cis 14h ee CH, CH CHC, Be (1, 2aion) hvu BrCl, CH CH CHLBr 1.4 Dio 2-ene (A-addition)| ) Addition acids (HBr or IC): CHCHBr- CH= CH, thon za CH CHL CH CH, # Br: 1, 3-Butadier CH, CH= CH-CH,Br rono-2-butene ta (6) Nucleophilic addition reactions : When the addition reaction ‘occurs on account of the initial attack of nucleophile, the reaction is sai to be « nucleophilic dition reaction, Ducto presence of strongly electronegative oxygen atom, the = leetrons of the carbon-oxyzen double bond in carbonyl group (-C ~ 0) get shifted towards the oxygen atom and thereby such bond is highly polarised. This makes earbon ‘om ofthe carbonyl group electron deficies O+Nu E L_.>de- ‘Theaddition of HCN toacetone (C= O compounds) isan ‘example of nucleophilic addition CH. CHy De=O + HEN — C CH cu’ SCN ‘estone Acetone cyanohyia {on involves following steps The mechanism of the react cyanide Step 1. HCN gives proton (H") and nucleophile jon (CN*) HCN—>H" +N"CHEMISTR 274 Ofanie Chemistry ~ Some Basic Principles and Techniques imination Reactions © levphile (CN attacksthe positively charged (3 Elimination e termed as elimination Sep2. The on reactions are tr™ o sau to rman anion doesn attck the negatively The reverse of addition Fea toms or groups trom charged oxygen as anion is more stable than cation) resetons In these rats in the substrate molecule are wo adjacent carbon atOmS In the process, tg a £0 cnt-5 or NK fonds relost anda new bond Foes, ae “uy sit carbon ato cay CH cH; Sen ae yoridization ofcar¥o? ym chang Step 3. The proton (H™ vombines with anion to form the Sp? tsp. adulition product. Some esamples are: CHs Br Br Ch +! CH OH | + zn BOE H+ Zr, SAO We Nemo oN yy Bi) it ch i cu” Nex TI H a CH CN Ethylene 1.2Ditromeethane _(Dehalogssston) Other examples of nucleophilic addition reations are ° Addition of Grignard reagent to>C= O compounds: Ostet Oy : chy in OMgX 1,0 OH Gi b ethyl eyanide NoB xan Nc iy HE (io) Methyley 7 NR NR H (Dehydration) SGngnaneagsat Addon reduc Alcohol mn (©) Free radical addition reactions : H } " - : 0, 170 40. This type of addition reactions takes place in vapour | Cone, HeSOv WOE ar CH=CH, phase or in non-polar solvents (i.e, Cls. Bry. H.CO, (iti), HC—C—C—H Pirie 2 and CH, ... ete) in presence of sunlight. fy stydeon (i Theadditives are fre radicals andthe rate determin 2 7 step suggests for addition of free radicals. ‘Mechanism of elimination reaction: (ii) For example, the photochemically catalysed addition of An elimination reaction, generally involves loss of atoms or chlorine to ethylene may be shown as follows. ‘groups from adjacent carbon atoms resulting in the formation 7 ofa x-bond between these carbon atoms, so these are reverse HyC=CH,+Cl(@) = sy, Cis of addition reactions. The elimination reactions are divided " : ies Ethylene into two classes = | E2 reactions. E2 stands for bimolecular elimination. El reactions. El stands for unimolecular elimination, © E2reactions : (a) Dehydrohalogenation of alkyl halides, ‘The dehydrohalogenation of the alkyl halides with alcoholic ac Ethylene dichloride (iv) Addition of HBr on unsymmetrie alkene in presence of Peroxide isas follows, CHy-CH=CH,+HBr °°", cy.cH,—CH,—Br alkalis an example of this type It occurs in one step. ‘Mechanism: CH,CH,CH,Br + C,H; > CH;CH= CH, + B+ C)H.OH 1-Bromopropane Peopene Bron Mechanism JO OW Hoss ape R () Chain initiation : 7 vs Sk i 7 } RO*+ HBr —+ ROH+Br* CHO Hoe {Br | cuH0 «a “oe ay (iD Chain propagation : (two steps) nH HOH CH,~CH= CH, +Br-—> CH,~ CH—CH,Br a 2" five radical CH, - CH-CH,Br+ HBr —} CH; ~CH,~CH,Br+ Bre | (iii) Chain termination : ae i c : BC, H Bre~ Bre or 2CH,~ CH-CH,Br = - : r alk \ y CoHGOH+ Br or CH CH -CH,Br+ BreEe Organic Chemistry ~ Some Basic Principles and! Techniques 375 cremesTRY Wn These vecuram WOSIEDS uy eueeetions 7 (a) etdrohalogenation of allyt halides, rhc alky aide foniss to ive the carbocation step 1 cit, cH; Stow I cul ates = cH +X chy CH; CCarbyeaton © step 2. Caboeation loses a proton om the -earbon atom tte base ueleophile) to form alkene ci. Hy cnn on C= CH) +10 cH” Clly @ penydrohalogenation is removal of HX from alkyl halides ‘rthalcoholic KOH of KNI of cr-BuOK (potsssium tertiary putoxide) isan example of \-ciminations. equ CH, —CH,X 8S HyC= CH Bo CH EN a Lane CH, - CH; -CH-CHs x 2+ Halobutane ae (CH,CH=CHCH, ~ CH,CH,CH=CH, (HN) Bigs 2 2 Butene (major) 1-Butene (miner) more stable (according to 2-butene is preferred The more substituted alkene Saytzeffrule). hence the formation o! to 1-butene. 0 Slow Ey — (@ CH;CHCH;CH; CH, CHCH,CHy Br 2-Bromobutane carbocation 27) @ ES CH,CH=CHCH; 2-Butene (ore substtted) (i) CH, CH CH,CH Catbocation Isis another example of elimination orH,PO,areusedas (ii) The proton given (b) Dehydration of alcohol reaction. When acids like cone. H,SO, dehydrating agent the mechanism is Ey by acid is taken up by aleohol. H 1 ww CH, -CH,- 9-H 4H® —>CH,-CH,-Q-H H | * CHs ge 20, CH CH, +H,0 Cubosation The carbocation loses a proton to form alkene. wLouX dys CH= cy Dehalogenation :Itis removal of halogens, ¢.z., CS-CHy + gadis —BUOILIE HyC= CH, Br Br (tn) ylene bromide Blioe Dehydrogenation :Itisremoval ofhydrogen, 2. CH,CH,OH 200°C, CH,CHO CH -CH-CH; "55 cH; -C-CHy I Cn) on 0 Acetone Isopropy alcool Rearrangement Reactions = ‘Te reactions which involve the migration of an atom, group ora multiple bond from one sitetoznother within the molecule (nothing is added from outside and nothing is eliminated) resulting in a new molecular structure are known as {earrangement reaetions. The new compound is actually the structural isomer ofthe original one. ‘Some examples are: ashydons AC, CHCH,CH,CH, > CH CHCH, CH, sr Basane Isobutane [AICI oF AL(SO,)s CH,CH,CH-CH, CH,CH*CHCH, + CH oe CH, 2-Burene 2-Methylropene NH,cNO “> NH, ~CO-NHs ‘Ammonium cyanate Urea AB, _, IL (CH,NH-C—CH, Heat CH,CH,CH,Br -Propyl bromide 1N-Methy!propionamide276 Organic Chemistry = Seine Basic Principles and Techniques ISOMERISM properties a CLASSIFICATION OR TYPES OF ISOMERISM ne molecular formu by Berasias. Compounds possesing the alle isomers and the phenomenon is termed as isomet CHEMIST py aha TEE SSE ho ISOMERISM | tol Td Chain Pesition Functional Metameriamt fen ISOMERISM Structural isomers passes the same molecular form it dflereot Siruetures: however, the term constitutional isomerism in.aimon ‘modern term of structural isomerism, wlifference in the sequence of molecule without ref Wissub-classified into following types W arises bocanise of the ovalently bonded atoms in the to space, (a) Chain Isomerism (Skeleton or Nuclear Isomerism) jresiferent arrangement of carbon atoms ives rseto chain chain Akt Chain isomers possess different lengths of carbon hain (straight or branched), Such isomerism is shone by cach and every family of organic compounds (@ Butane: C,H, CH;~CHy~CHy—CHy CH, —cy ~CHy 1 CH; Buane jsoButne ‘Butane has the chain of four carbons, While isobutane has Hence they are chain isomers, (i) Pentane :C,H,, CHy CHsCH,CH,CH,CH,: CHSCHCH,CH,; CH, -bcu, I | CH Cy Isopentane Neopentane Stereoisomensim | | Contemational Configurational Geomietsieal Optica ‘i Butyl aleohol : C, HOH CH, ~ Clty ~CH,—CH,OH CH; -CH-CH on . I CH, bust aobol tsobuy alco These two butyl alcohols are chain isomers, Ring chain isomerism : They can also be considered as functional isomers, Ex (CH Butene Cyelobutane 13 -Butadiene AD 3-Methyl — Cyelobutene xelopropene () Position lsomerism ; Position isomerism shown by the compounds in which thereis, difference inthe position of func ional group, multiple bond or substituent along the same chain length of carbon atoms ° Bicyclo (1,1, 0) butaneCHEMISTRY b I MNUX~ halogen, NH,.OH.ar OR) ci, Cy Cit cH, CH Ct x x ‘ wb) (¢) ieee In these structures, three carbon atoms form a chain, and X tsyoined at the end in (a), while at the middle carbon in (by, Orgar 'Ganie Chemistry - Some Basic Principles and Techniques (01) Molecular formula: CyHy i ° CH, Clty ~cooanacHy- ¢ -0-CH, Propane acid ea (x) Molecular formu: CHsNO, ° ; Methyl setae esen lay CH, CH, CHOH and CH, CH CHyPesition cH 4 ound CH,-O0-N=0 on methane Mths ite isomers ii) Wt ((d\-Mefamerism : Poopanol ' (by CH,-CHy-CHy Ny and CH, CH CHL Position Muy (i) Molecular formula: C1, CH, Clty CH= Cyand CH, CH= CH CH, 1 Statene (ui) Chloroioutene, C,HCH.)CL exists an three isomeric forms: omtho, meta and para cH, cH cH; © Ad joluens _ m-Chlorotoluene p-Chlorotoluene ; (iy Functional Isomerism + ‘These isomers possess same molecular formula but different (iv) functional groups. Such compounds are called functional isomers. The following pairs of families show this isomerism. —(v) (is Monohydic aleohols and ethers (ii) Aldehydes and ketones (iiiy Acids and esters @ tiv) Cyanides and isocyanides («) Nitroalkanes and allyl nitrites w {vi) Oximes, amides and many more Gai) (sit)Alkenes and cycloalkanes (viii) Alkymes. alkadienes and cycloalkenes By (i) Molecular formula :C3Hg0 CH, - CH, -OHand CH; -O-CH; Ethyl alesbol Dimethyl ether stl (Esher) ii) Molzcular formula: C;H,O 0 ° CH, CH, - C -H and CH, ~ C-CHy Proper) Propanone (Ketone! Aled) ‘This type of isomerism is duc to unequal distribution of substituents on either side of the polyvalent Functional roup. Memibers belong tothe same homologous series. By (i)Diethy! ether and methyl propyl ether CH,CH,OCH,CH, — CHOCH,CH,CH, Deis! eter Methy!peopy eter (i Diethyl amine and methyl propyl amine CH,CH;-NH-CH,CH, CH,CH,CH,~NH-CH Diethyl amine Met! propyl amine Ue) Teuromerism : (i) Tautometism isa special type of functional group isomerism \hich arises duc to the migration of H-atom as proton from a polyvalent atom to other polyvalent atom with reshuflling of ‘bond. ‘Such isomers are directly and readily interconvertible under ‘ordinary conditions, andthe isomers are called tautomers. ‘Tautomersexistin dynamic equilibrium. ‘They have no separate existence under ordinary conditions like other isomers mentioned above. ‘The other names of tautomerism are “desmotroprism’ or ‘prototropy". Keto-enol tautomers ‘When the tautomers exist in the two forms viz keto & enol. Such type of tautomerism is called keto-enol tautomerism. It was discovered by the scientist “Knorr” in 1911 in acetoacetic ester: Ketomeans the compound has keto group > C=O, and the enol form has both double bond and OH (hydroxy) group joined tothe same catbon, HO a -C-C- = i Keto form Eno frm Ee ? ‘ I () CH,-C-H = CH, =C-OH Vinyl alcool ‘Acetaldehyde378 Organic Chemistry Some Basic Principles and Techniques 7 on t ( CHy-C-CH, = CH,=C-cn, Acione Isopropenyt alcoho! ou to i) CH, ~C-CH-Cooc,n, ‘Aeeio aestic esr (AE) Keto foom OH I = CH)-C=CH-cooc,H, B-ttydroxy croton es (0 form) () CH, ~C- Cll CH, = CH = C ~CH, Cs | = CH- © =cH-cH, ‘OH et is l : () CH; -C-CH-COCH, = CH,-C=CH-COcH,, Note: In order for conversion ofa keto form toits enol form it must have an a-hydrogen (ic., hydrogen attached to the carbon adjacent to the carbonyl group), Thus benzaldehyde, mchlorobenzaldehyde (in general, atomatic aldehydes) formaldehyde and trimethylacetaldehyde do not exist as their ‘enolic forms. 9 ° I I a Benzaldchyde m-Chlorobencaldcyde cH, H-¢-H CH,-C-C-H i ri ° CHO Methinal Trimeiylactaldehyde Quantity of enol 2 No. of CO groups « No. of «~H i Ex CH, ~ C-CH,~ C-CH, I 0 ° 4 tl > CH,- C-CH,- C-H > CH,-C-cH, Il ° CHEN > CHy- C-H 0 CCyanile-isoeyanide tautomerism H-caN = CEN-H Nitro-acinitro tautomerism ° ea 2 cH-nS = NS oy STEREOISOMERISM Ce or more compounds which have ths same molecular f iotcsameconctviy ofstoms but ies thre arrangement of their constituent atoms or groups stereoisomers and the phenomenon istered as 5 ‘The branch of chemistry which deals with the study of, structures in three dimensional space is called stereo: Stereoisomerism ——- Conformational Configurational isomerism isomerism Geometrical Optical 1, Configurational Isomerism @) Geometrical isomerism : Tsomerism where the isomers possess the same structural formula containing a double bond and differ only with respect to the arrangement of atoms or groups about the double bond. Geometrical isomerism is shown by (i)Atkenes or their derivatives in which two different atoms oF groups are attached to each carbon containing the double bond. a. b cnn ana cng =CO 7 er wer, Gi) Compounds having C=N bond (e.g. oximes)and pion ee Non \ C=NC oor ZN a (Gii) Compounds having - N= N—bond (e.g. azo compounds) Double bond creates restricted rotation. 00 Q NEN or N= Ear)we cuemnsTey ‘Thecompo aang exhibit geometrical isomerism. ec-b fg-c-b Il |- C-b (cis orm) (rans for) «same groups Tie on {Same grows lis om same sie) apposite sides) ifthe two atoms or groups Linked to same doubly bonded Eivbon are similar a inthe moleculeaaC=Cab, the compound tlesnat show geometrical isomerism. Here the two possible configurations are, in fact the same. a-C-a a-C-a I i b-C-a a-C-b o am Nomenclature of Geometrical Isomerism cisancttrais Cab b-C-a a-C-b o> {I 4 Cab b-C-a— b-C-a Ex. (a) CHy-CH=CH-CH, [2-Butene} HC. CH; HAC, A / Nf \ Wf Now, oO fi A. trane-2-Butene (b)CH (COOH) =" ‘CH(COOH) [Butene-I, 2-dioic acid) K H HOOC, H / \ 7 rN H ‘COOH HOOC Maleie acid (cs) (0) CHy—-CH=CH COOH [2-Butenoie aid] Fume aid (rans) CCrotonie acid (rans) HCI [1,2-Dichloroethene] ad e A H cf Na cr Organic Chemistry 5 5 , ~ Some Basic Prinipl oe ands having the formula abC=Caboccurin vo (i) Cian ion: cis and trans designations for geometrical isomers are suitable ‘when structurally similar or identical groups are Joined to both carbon atoms. However, cis-irans method does not work when there are no similar groups. Ex [BrCIC=CFI] The configuration can be pciedby sing the roatons z (TiepsthtaEZyten : ‘nd out the groups 6f highest priority on each carbon. If two priority groups are on the same side the configuration is Z. (zusammen = together) Ifthe two groups of high priority are on opposite si configuration is E (entegegen = opposite) the (@) Naming of compound is based on priority order (stomic number) Z atomic number T => priority? rity atomicnumber | = pi Ex [>Br>Cl>0>C>H (© _Inisotopes (Use atomic mass) D>H Ex of E, Z-system HAC, cH] HC H Nezc Noa ® By ‘ By (cr) Bui) ran priortyis: Br> CH; . CH;>H Br, F ch F Ted eA Nee @ _ ere C=C cl] L [Bt Y z ( Migher > CH CH,CH, > Higher c=C eZ cu.ces Z.3-Eahyl-2-hexene Higher > C! H eer NL 7 H Br Higher E-1-Bromo-2-chloroethene =N-bond : (iii) Geometrical isomerism due to— Bx. (a) HyN;0, (Hyponitrous acid) N-OH NzoH I | N-OH HO -NOrganic Chemistry: (by Acobenzene (CH, -N He N=D CH 7 (©) CH H Nv N, I Non N-CyH) Cos Co i N a ‘The number of geometrical isomers for alkenes, «) ‘one double bond d. then geometrical isomers are HCC cH cH, Cac cs : HN HoT NH ©) Iratkene has two or more double bonds : {itn structure ifthe terminal groups are non-similar, then we ean use formula, Number of isomers [Whete n= No. of double bond (n = oddeven)] Ex CH;-CH=CH-CH=CH-CH=CH_Br No. of isomers 8 Ui) In structure ifthe terminal groups are similar, then we can use formula, Number of isomers = 2"! 4 2-1 (n= double bond) Ex () HyC-CH=CH-cH=cH. "2 => when m isan even number > when mis an odd number -CH=CH—CH, 2.4. 6-Octatrene 3 n=3 p= Number of isomers 24 I= 44226 (i) HC-cH CH-CH=CH-CH=CH-CH=CHcH, 4 =4. p27 fumber of isomers: diss Optical isomerism ; The g ‘ melting point, boiling point, de hhemical properties 6, 8Decatetraene sepia, pagers differ in physical properties such ‘Some Basic Principles and Techniques i) «ii ‘i Gi) IstRY Aion, vers will have the same chemieat yy, i aall physical propertis me Hone The optical i re heir action ang will beak be distinguished by their action gq rey a at Phispropertyisolen reer Ang Plane the opniay polarized ME Ordinay Nicol prism Pane plana (se ie Ordinary Hh loxaves vibrating io all direc) Pane rotated to the left lane rte he hen certain organic compounds in their solutions ar plage hntepathotapn polarized light, they show dhe remarkae Property ofotating its plane through a certain angle whey imay beeither tothe eo tothe right. I the polarized igh has its vibrations in the plane AB before entering such s Solution, the direction on leaving it will be changed tosay

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