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Science College Price Rs: 500/= Page 1 -—| Hl pon(os 07°) Chapter #01 = Hydrocar! i) Alkane ii) Alkene iii) Alkyne iv) Benzene v) Cyclo alkane PG nal Chapter a 02= v) Ketone’ vi) Crboxylic acid an vii) Amine viii) Diazo comP = Heterocyclic compounds(194 ~ 207) i ine ii) Pyrrole iii) Furane iv) Thiophene Chapter # 05 = Bio molecule (208 — 226)psc paper !V Organic Chemist | Hydrocarbons to other carbon atom and form Ability of an atom| 4 dnd cyclic compound is Called long chain branc Hydrocarbon in which all the carbon atoms are bonded with single covalent Bond Called alkane their general formula is Crane Q# Define Alkene? ining one double There general Hydrocarbon in which carbon atoms contal bond between Carbon Atom called alkenes formula is Cy,H2na enna Qi Define Alkyne? l e bonded with s ar The hydrocarbon in which carbon ston there general one triple covalent Bond Called alky™ formula is CnH2n.2. (2011) Write shorting internal combustion 2.46 low octane number which gent which is tetra ethyl lead, it het but tetra ethyl lead produces s¢it is not good for increase the quality The sharp metallic so engine is called Kn: ocki is improved by ant ki increase the octane Ms te i environmen} of fuel how, decréase the Knocking Octane number is the scale ff of quality of petroleum, the over all eforming of petroleum. It is similar like raight chain of normal octane converts to alkane to increase the quality of fuel which is @s-Maximum octane number and it is 2,2,4- tri methyl CH; CHs | | CHsrC-CHy-CH-CHs CH;had Alkane and their naming by common system Alkane those are saturated hatic hydrocarbon in which all the carbon atoms are bonded with single covalent bond there general formula is CyHane2 The name of first ten all arbon atoms are bonded #1 normal alkane. CH -CH2-CH2-CH2-CH3 n-Pentane Any one carbon atom is directly three carbon atoms called Iso- Alkane. CHs I (CH3-CH-CH2-CH3 H3-CH-CHs Iso- Pentane Iso- Butane Alkane in which any one carbon atom is directly bonded with four carbon atoms called Neo- Alkane. CH3 cts | CH;-C-CH3 CECT | CH3 CH; Neo - Hexane Neo-Pentane Page SQ# Define and explain Homologous series? mber is differ by anges 14 Calleq found in which Series of comp ‘CH2) ie molecul methelene group ( homologous series. All the members oft Series having similar chemi r but there is different PI condition first four me alkanes having five found in Liquid Sta carbons foundvin sollte of members CsHr0.....-- Pentene of alkane is replace by any other atom or sultant group is called alkyl group or alkyl nted by “R” There general formula is CaHanet roup depends on parent alkane by replacement of oe n of “ane”. CH;-Cl Methyl chloride C2Hs-Cl Ethyl chloride cl | CH3-CH-CH; Iso propyl Chloride CH3 I Cec Neo butyl chloride CH; Page 6CHs | CHs-C-CH;-Cl__Neo pentyl chloride | CH3 two alkyl ipSented by secondal atbon similarly if-alp 4 Jeardan i¢ directly bonded ‘compounds called tertiary rtiary carbon represented with thrée/alkyl groups ( t| compounds and such ca C e by3 R-CH,-G CH;-CH2-CH2-Cl Primary con nid Primary propyl chloride CH; \ CH;-CH-Cl Ompound Secondary propyl chloride CH3 | R Aertiary compounds crise ct Tertiary butyl chloride i R CH (2000) Q# Define and Explain different types of hybridization. Process of mixing of two or more than two different energetically and shaped orbitals called hybridization and the orbitals obtained called hybrid orbitals this concept of hybridization was first introduced by linus pauling. Page 7three types OF hybridization are known, a Js following ” cae iii) SP hybridization and “P eyes ! nae! Hybridization ii) SP” hybridization 2 pybridization Acie sdtzation in which one “S” 20 all three “P” orbits The process of hybri ang four sP° hybrid reel is called SP* hybridization’. A hedrally and angle bAw orb The process part in hybridigation and for energy and similar shape i hybrid orbital arrange srigena Example: BFs, C2 The protess of hybridization in whi P 5 of which one “S” and one “P” orbit ear in hybridization and forming two “SP” orbital of Ae acales a similar shape is called SP hybridization. Both SP hybrid orbit oe jiagonally angle b/w orbitals are 180° eg. Becl,, C,H, cos il . » CoH2, CO2. 180°# Explain the shape of following molecules in term of hybrid orbital Model ji) Methane (CH,) =14 2h xbx dey 2P2 (ground state) (excited state) aak et in which ong S # ion iy! nd forms four SP? hybridize orbital fle between orbitals is 109°28'. Out of 6= ak 2 2bx 2by 2Pz (ground state) 74°41 1 2S 2Px 2Py 2Pz | (excited state) ty ) a 4a a)1 in which 0n€ $ and two p Fn three sp” hybridize orbita, ms i 2 in ethene each carbon ei orbitals takes Par those arrangé trig eee sp? hybridize orbital a it is Sl while third form: ER varbon atom .In ethene which is perpendica overlapping forng arbon atom is SP hybridize in which one S and one P é“patt in hybridization and forms two SP hybridize orbitals \nge diagonally and angle between orbitals is 180°. Out of two ze orbitals one forms sigma bond with S orbital of hydrogen while other forms sigma bond with SP hybridize orbital of adjacent carbon | atom. In ethyne each carbon atom having two unhybridize P orbital those are perpendicular to each other these P orbitals by side to side overlapping forms two Pi bonds. tu1 4 i C=6=1S 2S2Px2Py2Pz (ground state) Tey] A) |A 2S 2Px|2Py 2Pz (excited state) Page Ree —_—y ‘ ~O=0-- Preparation of Alkane 4 x (i) From unsaturated h ocarbons (ii) From Alkyl halide (iii) (iv) vy) (i) When unfatyfatt drogen in the by addition of hydrogen a catalytical hydrogena’ 56 convert oil into ghge rese! Be Be btained process is called its industrial importance i 4, ———>_ R-CH,-CH,-R Alkane Ni CH, +H, ————>_ CHs ~ CH: — CHa propane Ni C-R +2H,———_ R-CH- Cha -R Alkyne Alkane (2011) Ni CH; - C= CH + 2H, ———— CH; - CH, — CH3 propane Propyne ii) From Alkyl halide (a) By reduction (b) By reaction wit (c) By reaction wil ith sodium metal ith magnesium metal Page femically hydrogenated oil. number of Pi bonds between NhIdi redui of Alkyl halide Alkyl halides by reduction with re of Zn in HCI then by reduction witl obtained. R-X+[H] Alkyl halide educing agent such as mixture Ih nascent hydrogen Alkane arg Methyl iodide (2017) (ii) isopropyl chlor cl CH; - CH2 - CH3 + HCI le propane | chloride (2- chloro 2- methyl propane) CH;-C-CI+[H] _——> ca +HCl I a CHy-CH-CH, Iso- Butane Is Tertiary butyl chloride {2003,2005,2015) (b) By reaction with sodium metal (Wurtz reacti n When alkyl halide reacts with sodiu dry ether than by coupling reaction im metal in the presence of higher Alkanes are obtained Pagerocess is called wurtz reaction. This method is suitable for having even number of carbon atoms. For preparation alkanes having odd number of carbon atoms two different alkyl halide reacts with sodium metal and it is called mixed wurtz reaction but this method is not suitabje”fo preparation of alkane because by this method mixture of a| k&nie: are obtained. pi preparation of alkane Kee 2 Methyl chidtide (2014,2018) Q# which alkane is obt with sodium mefal (2007) (i) iodo ethane swing compounds reacts eé of anhydrous ether 'CHs —>CH; — CH2 - CH2 —CH; + 2Nal Butane cl CH; - CH -CHs | | ~ CH —CH; — CH; - CH — CH3 + 2NaCl 2H; + 2Na + CHs 2,3 - Dimethyl Butane 50 propyl Chloride (iii) Tertiary butyl chloride ( 2- chloro 2- methyl propane) Hs CH3 CH;CHs I I 1 | CH;-C-Cl + 2 Na+ CH;-C-Cl ———> CH3-C- C- CH; + 2NaCl I ! tol CH; CH;CH3 CH; 2,2,3,3 -tetra methyl- Butane Tertiary butyl chloride Pagechloro Butane a CHs CH: js CHs in i, cH cH + 2NaCl crcl ane 1 ee ? -f CH, CHe i ¢ | CHs cl CH, CHs 2- chloro Butane 3, 4— Dimet e (2012) Ullman feaction i e this‘reaction en alide such as iodo C than by coupling ‘is called Ulmann reaction, coupling o' benzene is heated with cop reaction bi phenyl is ob (2012) Wurtz (Yer +Br—-R+2Na Dry ether «Sr + 2NaBr Page1 (c) By reaction with magnesium metal magnesium metal in the When alkyl halide reacts with presence of anhydrous ether then a highly reactive reagent alkyl magnesium halide is obtained which is called Grignard reagent and it is an example of organo metallic compound. By hydrolysis of Grignard agent alkanes are obtained. C(O) CH; - Cl +M H3IMfgCl + H20 R-X+Mg——>R ——>R- H + MgX( Alkyl! halide ard\reayént we Wy Hs hivfide [Meznane | +MgCl(OH) H3-CH-CH3 Iso- Butane Oxidation Crz0;/H2SO, | f K2Cr20z/H2SO«} Carbonyl compound Carboxylic compound Reduction _| Reduction _} LiAIH, LiAIH, (iii) From Alcohol When Alcoholic compounds reacts which HI in the pres: en red phosphorus then by reduction alkanes are obtained coer Red "P" R-OH+2HI ————> R-H+I,+H,0 Alcohol Alkane PageHOH + 2H! Methanol Aldehyde GH, CHO + [H] NH a (Acetaldehyde) ethanal au oO Il R-CoRA n/Hg, R-CH2-R HCI Keto! Alkane Cc CH, + [H] _Zn/Hg, CH3-CH2-CH3 HCI Acetone Propane (v) From carboxylic compounds re nine by reactions with caustic soda forms in the pre: . decarboxylation forms ec of soda lime (NaOH + CaO) by Pagecao RCOOH + NaQH——> RCOONa + NaQH —* R-H +Na,COs Carboxylic compounds Alkane (2009) CaO CH;COONa+NaOH —A_* CH, +Na2COs Sodium Acetate Methane ving and poor in NO:, “Cl (2010,2011,2018) Define Nucleophild é for example NHs, ‘Cl (2017) Defirle€ ged carbon is called carbonium ion. They are siti: a ry Secondary and tertiary, R-CH,” In tertiary carbonium ion tertiary carbon is directly bonded with three alkyl and in secondary carbonium ion by two alkyl group while in primary carbonium ion it is directly bonded with only one alkyl group. Due to positive inductive effect of alkyl group tertiary carbonium ions are more stable then secondary and they are more stable ten primary carbonium ion Page ee aiex EV > ae i1 + | z Roe ofa | ~ witt , rbonium ion cn i cabonium iol Secondary cal m Tertiary : hy! aornDefine Oxonium | : um 7 is caffed 0x0 oxygens siyecty jth three atoms 1 7 x} c oxyg' ; ol ae a e following Nu eno) Nucleophilicity in Hydro in rder of their stuPated hydrocarbon there for normally it is non givés addition reaction or oxidation by ordinary (ii) Combustion (iii) Thermal decomposition {i) Substitution reaction The chemical reactions in atoms of Alkane are repla which one or more th an one hydrogen ce by any other active atom aE arate Pageof atoms called substitution reactions if this substitution occurs with halogen called Halogenation. Chlorination: The substitution reactions,in which one or more than one hydrogen atoms of Alka! replace by chlorine call chlorination. For example s with chlorine if thé\pkesence-f following s| ted\products are g chloride ( Di chloro methane) CHCI; + HCI Chloro form ( Tri chloro methane) CCl, + HCI Carbon tetra chloride (tetra chloro methane) 002050, 2012,2015,2017 ay e ism for chlorination of methane cha) Mechanism for chlorination of methane is free radical mechanism. Over all this mechanism completes in three steps first step which is called initiation in which chlorine molecule in the presence of sun light by homolysis forms two chlorine free radical. Sun light CEL) |S a Chlorine free radical Page 1aSecond step which is called chain propa enh chlorine free radical attacks on methane art oe methyl free radical which further reacts Me aical which ‘And forms methy! chloride and chlorine res propagate the chain Reaction. radical combj ethane and re e/of oxygen than carbon di ount of heat energy is evolve When Alkane is burns # oxide , water vapors process is called comb of combustion whi nCO, + (n+1)H20 + Heat CO, + 2H20 + Heat Is * 702 > 4CO, + 6H,0 + Heat (iii) Frérmal decomposition (Cracking) The process in which compounds are h i : eated at high temperature and pressure in the absence of oxygen and it salt into smaller molecules is called cracking By fractional distillation of petroleum only 20% petrol is extracted as its i i iti: cracking requirement its additional amount is obtained by Fi Whe 800° hydiFor example When propane is heate 800°C then by cracking mixture of propene, hydrogen is obtained 700-800°C 2C3Hs ———K_CoHs + CHa + CHa + He Propane absence o} ropene ethene metha d in the absence of oxygen at 700 to ethene, methane and h jon atoms ¢£ bond betwe a Atom called @ aia Hc 2 d H2C late iene H, Beta ed diene (2003) Preparation of Alkene ion of Alcohol of by Chugaeff reaction When Vicinal di halo alkane is heated with zinc dust than by removal of one mole of X; alkene is obtained. xX X i Dust R-CH-CH-R #Zn ———* R-CH=CH-R + ZnX, Vic. Dihalo alkane Alkene Page(2009/2014 y2015,2026 Ce _Dust I I CH:-CH2 + zn 2-di chloro ethane cH =CH: + Z0Cle (2015,2018) CHy-CH;-Cl + KO Ethyl chloride in the presence of hot and concentrate than by removal of one mole of H,0 Sac It is a reversible reaction. so occurs with other dehydrating agent such as Conc. H,S04 R- CHy-CH,OH————* R - HC=CH,, + H20 Alcohol 170°C Alkene Al,0,/350-360°C C,Hs0H —————*> CH, + HO 7 HsPO,/Al,03/250°C C,Hs30H ———————*_ C,H, + H20 Pagea H2S0,/170°C CH, -cH- CH; ——————+ CH, - CH=CH, + H,0 2- Propanol Propene (2011,2012) ) (iv) From ethanol by Chugaeff reaction When ethanol reacts sulphide than it co with methyl chlorite convelts t6 methyl xenthé heated at 209° than itdecgnpose to ethene process Chaugaeff re. CH; — H HH + CS. H py CSSNa 1» - O - CSSCH ethyl xenthate = CH, + CH; SH - COS hene ne CH; — CH\- @- CSSNa + CH2e R-HC=CH, Quinoline Alkene H,/Pd + BaSO, CHs- C=CH + He CH; - HC=CH, Propyne Quinoline Propene (2012) vi) Cope Reaction Tertiary amine by oxidation with hydrogen per oxide forms amino oxide those by thermal decomposition at 120 - 150°C forms Alkene process is called Cope reaction. Page i OtH,02z | CHe~ CHa N~ cy, nicHs)e —? CH" ° i Amino gxide \ Propene A halide-by dehydro ha f stgeng alkali forms fp CH; - CH2- CH2- 1- Pentene J Alcoholic CHOCH,-CH; + KOH———> CH;-CH=CH-CH?-CH;, Chioro pentane 2- PentenenN Reactions of alkeme(comparision of reactivity of Alkane and Alkone) zor) Alkene is unsaturated hydro carbon having weak Pi bond between carbon atoms which during reaction broken and proceed the reactions of alkene while alkane those are sat es hydrocarbon so alkane argtess reactive than alkene Oo (208) Q# Arrange the followin stability on whie Since Pi electrons of alkene are nucleophilic in nature hence reaction is initiate by electrophilic attack it shows that addition reactions of alkene are electrophilic addition WF ye Ss —s if ewe | ct a SS — 7 C-E | Ni Nu - lu luc. Pageii) Addit en ili) Addition of Halogen Ih the pres vi) Addition of Hydro hal vii) Addition of Water ion of wate Clz > Brz > Ip x XxX CCl, | | R-CH=CH-R+X,————* R-CH-CH-R Alkene Vic. Di halo Alkane (2014) ci cl CH; —- CH = CH, +Cl, ae t Peas 24h ————+ CH3;~CH-CH, s, obtained the order of reactivity is t types of addition reactions portan' e of inert solvent ce of water igh temperature : ni Spsence of catalyst : n the presence of organic. ° ence of sulphuric act R-CH,-CH2-R Alkane CH, - CH, - CHs propane in the presence of inert solvent acts with halogen in the presence of inert solvent hen by addition of one mole of X2 vic. Di halo 1,2 di chloro propane Pageiii)Addition of Halogen in the presence of water such as chlorine in the ts with halogen When alkene react by addition ‘of one mole presence of water (Chlorine water) then of HOCI chloro alcohols are obtained Cl, +H,0 HOC! + HCI OH Cl 0 1 R-CH chp carbon. Alkenes hi drbon such as propene when reacts with Cl, at hi meratare 450-500°C then instead of addition allyti bs A occurs and chloro propene are obtained . (2014) cl 450-500°C | I, ————» CH,-CH=CH, 1-chloro 2- propene en in the absence of catalyst When alkene reacts with HX such as HBr at room temperature in the absence of catalyst then by addition of one mole of HBr Bromo alkane are obtained product obtained by this reaction are according to Markownikoff;s rule. Br | R-CH=CH-R+HBr ————~> R-CH,-CH-R Alkene Bromo alkane PageBr | (2001,z019,20142018) J ees CH= CH CHs CH, - CH = CH: * HBr 2. Bromo propane Propene (2008,2015,2018) Markownikoffs rule When unsymmetrical a than by addition et product is more Markowniko' te According (CH;-CH=CH, + HCI H-CH; loro propane Propene (Major product according to Markownikoffs rule) | —+ CH3;-CH-CH,” Primary carbonium ion | ——» CH;-CH*- CH: CH, ” ’ ae E__ Secondary carbonium ion E By the addition accordin: irkownikoff': le ition according to Markownikoff's rule intermedi: mediat more stable seconda re stable s ry carbonii the justification of Markownikoff's ne nonoi) Addition of Hydro halogen in the presence of organic per oxide vi When alkene such as propene reacts with HBr in the presence of organic per oxide then by addition of one mole of HBr, 4- Bromo propane are obtained product obtained by this method are according to anti Markownikoff's rule. \ R-CH=CH-R#F Alkene Mechanism ROO! RO +HBr Br+H & ROH + Br More favourable Br 6) : ——> CH; - CH’ - CH2 R +Br__| Secondary free radical Br (More stable) | L—» CH;-CH-CHy Primary free radical (Less stable) Br Br | i} | | CH; — CH - CH, + ROH ——> CH3—CH;—-CHzulphuric acid (2005077 sion of Waterin the resence ofS ‘4 the presence of sulphuri oiled with water in Nutie wen alkene aon ‘of one mole of H20 Caer obtained, ici Shtained by this action are acco! 19 (S\ Markownikoff's rule 7 OH Ny v R-CH=CH7R+ He Alkene (2010) CH; - Cl When alkene such{as propene) dacts with diborane then by ; _ CH,-CH2 + MnO, + KOH Ethylene glycol \p0, itself reduces to brown ppt of MnOz. Alkane) those are saturated hydrocarbon they not 0, it means by reaction with KMn0Q, its violet ais same there for this reaction is used as a test to sh between ethane and ethane ( Alkene and Alkane ) éd and Unsaturated compound)and is called Baeyer test (2006,2009,2012,2016) Distinguish tes 14- pentene OR Ethene OR Alket — Violet colour of KMn' t of saturated and unsaturated hi drocarbons ne OR Unsaturated com + KMnO, 0, changes to Brown ppt of MnO2 ne OR Alkane OR Saturated Comp: + KMnO, 1- pentane OR Etha —+ Violet colur of KMnO, Remains same Page2 +Br2H20) ie urated comP own Colour Change, mp: +Br2t20) ae jomP? “changes Remains sam, ne oR UnSat ted C' e OR oa wn colou ~ eins ag KMnOs then resultant oe sciced to carboxylic acid ah OH OH ( xidation 06cUS I oxic mposition fl by deco! [0] \ OOH rhoxylic aciq I ” 2CH300H Acetic acid kmn0.la' 36) Hot! acidic C (b) ti When alkene are oxi malozonides are obfaii ozonide those on waFruing converts to carbon) we byséarrangement converts to in and water by decomposition ds. Process iS called ozonolysis. H-R —* 2RCHO \/ ity 2 malozonide ozonide Aldehyde CHs-CH=CH-CH; +0;*CHs-Cl z js-CH-CH-CHs> CH5~ nlH,0 I Is ne Cit CH ae 2CH;CHO v 2butene malozonide —_ozonide Ethanal o—o(2007) Polymerization:- When alkene such as ethene is heated the presence of very minute addition polymerization its polymer pol 2008C/ 100atm: On % db nO. HBriROOR ci 2 —p Page C1,/450-500°C | Vw~_ CI,IH20 ast. saa IB,He/Zn+NaOH eee at 200°C and 100atm: in oxygen (0.01-0.02%) than by lyethene is obtained, (-CH,-CHz-)n Poly ethene] 1 CH; - CH- CHs QH OH CH;- CH - CH, Br CH; - CH2 — cH, cl CH, — CH = CH OH Cl I | CH; - CH - CH OH ih | CH; - CH, - CH2SS ——————— OH OH | i | KMino./Alkaline _CH- CH: oyzn+ #20 O14 cHo + HCHO hii CH, - CH = CH2 (2013) Combustion:- When alkene suc! cyclisation forms Addue such reactions Alkeng (diens lover). S|! | Example: When cyclisation Cc} i bonds are Epoxidation 200s,200s) Cyclic ether called epoxy and its i preparation call idati when alkene such as ethane is oxidaised in the ea ae silver then ethylene oxide (Epoxy) are obtained a 2H.C = CH; + O. 0 ill 2 2+ O02 Ag/250°C 2¢Ha~ Che ° — PageAlkyne Q# Define Alkyne? The hydrocarbon in which carbon atoms are bonded wi one triple covalent bond Galled alkyne there general formiukais ‘a halo alkan i in jth H20 tl y hydrolysis ethyne ethod for preparation of ogshation of te 5 When tetr: e is heated with zinc dust than by removal of les dikyne is obtained. xX R R +Zn ———* R-CsC-R+22nX, xx Alkyne Tetra halo alkane (2015) cICl Cah HC-CH +Zn ———* HC=CH+22ZnClh, Ha cic Ethyne 4,1,2,2-tetra chloro ethanekane oholi¢ potash than by e reacts: with Alc jes of HX alkyne is obtaine?- haloal! dehydro. paloge® tion of When di halo alkat removal of WO mol xXx di halo alkane (2014,2018) cicl 4,2- dichly (2000) Q# What happens when i) Tetrabromo ethal cts. dust. )c¢=CH+ Zn Dust H-C=C-H tl Br Br Wal Karehe ; reacts with ozone. HC—CH,-CH = Cl = CH, 2+ 03 HxC-CHy-CH-CH; H3C—CHz-Cl 1 CH CH azn 0’ | lo+d 1- Butene H3C - CH 2 CHO Propan: + HCHO al Formaldehyde Page_ my Il) Tertiary Butyl iodide is treated with sodium metal. CHs CH; CH; CH3 | | It ls —> H3C-C— C-CHs + 2Na H,¢—C —I + 2Na +I-C— lot CHs CH CH3 Tertiary buty! ,2,3,3- tetra p butant (2007,2016) Q# Complete itt) HC=CH ynes are similar as alkene its reactivity is due f two weak Pi bonds between carbon atoms action Pi bonds are broken and precedes the reactions. 4009,2012,2014) w that Alkenes are more reactive than Alkyne. \ \ Since with increase in number of chemical bonds between carbon atoms bond length decreases and bond energy increases which shows that alkynes are less reactive than alkene. Following reaction shows that Alkenes are more reactive then alkyne Page _ _ BTBr Br ie 20 -CH2- CH-CH. a m 2 If 2cH-CH2— CH= CH2* Br? © hadi Oe annie cH t- conten 4-yne oy of reactions ol Alkyne gives following tyP! \ \ \\ \ i) Addition reactio (i)Oxidation re: \ (iii) Polymeriza (iv) Combus on (v) Substit! i aaaifonsaact A dud to presence of ion atom! nerally two moles ertain conditions may be ddftion reactions. sf alkyne reacts with hydrogen in the presence of Nickle at 40°C then by addition of two moles of Hz Alkane is obtained. Ni/300°C Ni R-C=C-R+H,——* R - CH=CH - R +H, R - CHz-CH R Alkyne Alkene Alkane |, \\l He Ni/300°C Ni cs +H, ———> CH=CH, +H, ————* CH3-CHs yl Ethene Ethane _— — PageIf this addition occurs in the presence of Lindler's catalyst which is forms by absorption of Pd on BaSQ, in quinoline then only ‘one mole of H2 is added and reaction stop to alkene Pd/ BaSOx R-C=C-R+H, ——A—_ R-- CHECH- R +H Alkyne Alkene YS )! W Sy \CHECH: +H2 A \ A in in the é of Cl, tetra presence af F chloro alkang cic 1 R +Cl,— REC Cat cicl ‘ghiloro alkene tetra chloro alkane cl cl cl cl FeCl;; | 14 #Cl,—> CH=CH +Cl, ch cH cl cl Ethyne 4,2-dichloroethene 1,1,2,2- tetra chloro ethane If this addition reaction occurs with chlorine in the presence of CS; at 0°C then only one mole of Cl; is added and reaction stop to 1,2 — dichloro alkenegucac-R+ Ch Alkyne HC=CH + Cl2 Ethyne 2014,2017) addition of h cl R - H2C-CHCI, gem. di chloro alkane > R-C=CH + HCl Alkyne én) +HCl —> H,C-CHCl2 Sichloride _1,1- di chloro ethane 5 in the presence of HgCl, then only one ad and reaction stops to chloro alkene HgCl, + HCI —— R - CH=CH-CI Chloro alkene HC=CH + HCI ill HgCle [C=CH + HCl ——> CH,=CH-CI Ethyne vinyl chloride (2003,2017) (d)Addition of Water When alkyne reacts with water in the Presence of HgSO, and HsS0, at 75°C then by addition of one mole of H,0 Ea ‘ quarmediata unstable product alkenol is obtained which by rangement converts to Carbonyl compound. nee emceesHgSO./H2SO4 Rearrangement R-cnG:R#HO or R -HC=C- R———+R - CH,-C-R 75°C | " H-O oO Alkyne alkenol Carbonyl compo! (2004,2008,2009,2011,2016) H 2 Rearrangement HC=CH + H,0 ~ HyC=CH ————> CH Ethyne Bs with HCN In the/p edence of Guprous ul then by addition Acrylonitrile. Resultant p} polymer. R-C=CH + HCN R-HC=CH, Alkyne Cyano alkene (Acrylonitrile) (2017) PCuCINKAC! H,C=CH-CN Vinyl cyanide (Acrylonitrile) by KMnO, then by oxidation di obtained which under hot condition by idized to carboxylic compounds. When ae are oxidised carbonyl compounds are decomposition further oxi KMnO, Hot R-C=C-R+ [0] ———°R- C-C-R+[0] —* 2RCOOH Alkyne ( nll Carboxalic acid oOo Page _Hot = KMnO4 CH3+ [0] — CH, ¢, -c- C-CHs COQ, | CHy-GeC-CHs+10] —*CHs — 7 * ACCHiC aca 2- butyne & A Wi w HC=CH + 4[0] o | Ethyne ¢ ° tc ( (2012,2017) through red hot tube in then by polmerization its Kyne by this reaction forms When alkyne such as et! the presence of organg Ml) ty arty Nickle/500°C CoHe Benzene is burns in the presence of oxygen then carbon water vapors and high amount of heat energy is evolve pro is called Combustion. The heat evolve in this Process temperat ii i vol ure of bout 3000°C so it is used in gas welding. fits flame is CiHz + 5120, ———+ 960, + hO 4H = -312 K.J/mol(2003,2006,2007,2009,2012,2013,2018) (v) Substitution reaction:- ‘Acidic character of Ethyne OR Acetalide formation When 1- Alkyne reacts with active metal then by substitutio there salts acetalides are ktained this reaction shows the| s feaotion is used to predict t ada Sitio) (Note: This reaction nota y triple band i3 on terminal carbo alkyne in whi¢! R- Copper acetalide R - C=CH + CuCl (Red solid) (2011,2017) Q# How would you =CAg + CIl-CH; ———* HC=C-CH3 acetalide Propyne 1- AlkyneEthyne + AgNO; ———> _ White acetalide is obtained (2001) Q# Complete the following. oO ll i) CH;— C—CH, +_Zn/Hg/HG| CH; — CH,— CH3 Acetone n - Propane- mensetay tel og, cH CH= C2 * Hey +Ch | _cH = cle a i on ° Br ne Prope! Lj oth jic compoynd cares By element detection it is fox elements Carbon and Hyd It shows that it is a Hydro formula is CeHs. “6 e/ the general formula of saturated It shows that benzene contain three Pi bonds between carbon atoms. From the above results in 1865 Kekule Proposed the cyclic structure of Benzene. When under certain conditions substitution reactio i ; Ns occurs in benzene it is found that on each carbo! i product is obtained. n only mono substituted It shows that on each ; present. Carbon of benzene only one hydrogen isH I H\ 2. Cc | c cw ‘ «S | H OBJECTION IN amigos NE proposep iy nex Li Kekule observ’ t tasters three diff et types of di substituted-prodi tained called orto) meta para. —> oye KS 2 I B eee Lg According to Kekule structure | and V are similar called ortho structure II and IV called meta while structure Ill called para however an objection is arises that carbon atoms directly linked Pageah single bond and the ed with Sig with doUbIe bo, andl proposed the \ ngie rbitals two between ffbon atom forms a drogen hence er qu a e 12 in which six are in bet ahd maining six are in between carbon and hyd Inbengene each carbon having ndicular to the plane one unhybridize orbital S d : these p orbitals by e § overlapping forms three Pi bonds. tl t fT & 2S 2Px 2Py 2Pz (ground state) t P 42Pz (excited state) oaNomenclature of Benzene containing compounds gi NO, COOH I MOON. 103 hi! Benzene Chloro Kerigé itro benzene aS (CHs)2 \CHi On? Benzald ySp> Ace apfenone Benzenesulp pfopyl benzene (cumene) OH NMG CHACI 5 4 gtid) Aniline Benzyl chloride Oz IH OH 7 S NO, NO, 1,2-dihydroxy benzene (catechol) tro benzene Para dichloro benzene Tri nitro benzene Toulene Pherjo jOH IH (OH ia oc OH ‘OH ou 1,2,3-trihydroxy benzene Resorcinol 1,4-dihydroxy benzene Hydroquinone (Pyrogallol) PagePe _— ae ae OH No, NO>, oH ‘ Oz ie nol P O tro phere ° Gh TM picric ac'4) yy, i pcr phenol) NOz} j (am \) oH ere x TNT) 0 ili COOH Methoxy benze (Anisol) CONH, COOC:H, Styrene Benzamide Ethyl benzoate (1) From aliphatic compounds (2) From aromatic compounds i) From aliphatic compounds (i) From normal hexane (ii) From acetylenei) From normal hexane (Petroleum When normal hexane is heated at 480-550°C under pressure of 150-300 PSi in the presence of catalyst such as oxides of chromium than by cyclization and dehydrogenatio Benzene is obtained. n- heptanes under similar condition fo toluene CoH + 4He Benzene Benzene (ii) is passed through red hot tube in the go nickel at 500°C than by polymerization its is obtained. Organo nickle 3C2H2 > CeHe ne F. rom Aromatic compounds (i) | From Toluene ii) From phenol (iii) From sodium benzoate Page7 , F 65 (2000) m Toluene at 580-760°C in ty, @) ce ate awith nydrogen ® benzeneis -<. When Toluene han by de alkyla’ Ol H presence of 1 Hi WN e n ay reduction + ZnO Phenol Benzene ijl }ONa 0 + NaOQH———> O + Na,CO; Sodium benzoate Benzene (2017) Q# Define resonance energy and explain it with reference to Benzene. | Amount of energy release when one mole of Hp is added in a compound is Called heat of hi i r ydrogenation Hl, {\ j Heat of hydrogenation of cyclo hexene is 28.6 k.cal/mol PageOG +H, ——— CO = - 28.6 k.cal/mol Heat of hydrogenation of cyclo hexa diene is 55.4 k.cal/mol which is about twice then heat of hydrogenation of cyclo he 8 k.cal/mol 49.8 k.cal/mol 36 k.cal/mol (2006,2012) Q # Defin d explain the Aromatic character ounds hibit by aromatic compounds called aromaticity. 4r¢ the criteria of aromatic compounds enzene is a cyclic compound _An compounds each atom is SP hybridize and it favors electrophilic substitution reaction. In benzene each carbon atom is SP? hybridized and it favours electrophilic substitution reaction (iii) Pi bonds must be delocalized Pi elctrons of benzene are delocalized (iv) Compounds having some resonance energy Benzene having 36 K cal / mol resonance energy (v) Pielectron perpendicular to the plane must obey Huckle rule (4n+2)t1 e& Pageto the plane of dicula! electrons PerPery here are Brio Huckle rule Benzene benzene wn'e. Reactions of ance energy } ih reson nig der ordinary Co! hydrogen active atom or gro SindePi electron of = ce reaction initiate by of atoms cal benzene are nucleophili electrophilic attack it & €place by NO," =Nitration NO. NO2 O—o (ii) H* ion is replace by x*( = y X*(Cl*) = Halogenation i —— (iti) H" ion is re v= Sulphonation H lace by *SO,H = s, honati y I O—0= Alkylation or Friedal and (iv) H’ ion is replace by Rt (CHs") Craft alkylation * iopis replace by “COOH = carboxylation ian COOH (2006,2008) (i) Nitration The substitution reactions of benzene in which on one H* ion is replace by NO," ion called Nitration. e or more than Pagemy eT ae wo nae Presencg — e reacts with conc: stitution nitro benzey, ni When Benz at §0-58°C than by sub sulphuric a' Oz obtained. H2SOx, O r Be + letes in three steps le Mechanism of this re ANY Formatio 1% Step e *NO, + HO \e HNOs + 4 oft\Pi ¥fe: Benzene ie ay I Ys Fil The substitution reactions replace by X* ion(Cl’or Br’) called Halogenation. in one or more than one H’ ion are When benzene reacts with Cl, in the presence of FeCl; than by y Substitution Chloro benzene is obtained. cl FeCl, | 0 a eae O +HCIMechanism of this reaction completes in three steps 1% Step Formation of electrophyl Cl, + FeCl; ———_* *Cl + FeCl, {il phyl on Pi electron of Bepzene el cl Gl ‘et wv M2 Ht + y FeCl; + HCI 2" Step Attacking of ele 3" Step Rego rgactions in which H' ion is replace by “SO3H je reacts with SO; in the presence of ated‘sulphuric acid (H2S20,7 oleum) than by substitution e|sulphonic acid is obtained. H,SO, +$03, ———_> Mechanism of this reaction completes in three steps $O3H 1% Step Formation of electrophyl Page _*g0sH + “SOuH electron of Benzene OH § 3H SO3H Jon Pi rn a of electroPhy! H 2n4 Step attacking of © : , A= S i a k i t 503 + H28O% 2001,2004,2006 29972019) iv) Alkylation. Friedel at e in which one or more group (R") called alkylation. methyl chloride (CHCl) in the éubstitution Methyl benzene The substitution reactta than one H ion is (epactby a! When benzene rea¢ presence of A tl (Toluene) is 6 CH; Os AICI, Ly ‘cH ;cL ——* re i: so ‘this reaction completes in three steps 14*\step/ Formation of electrophyl Idi CH;Cl+ AIC; ————*> *CHy + AICI, la 2 Step Attacki p Attacking of electrophyl on Pi electron of Benzene is ie laipey sy) “N. U-E-O | one. Pageeter Sees) (CHO . { HO. a o—O~ ra 3" Step Recovery of catalyst a H* + ZnCly ———+ ZnCl, + HCI {vii) Chloromethylation he substitution reac: ons of i ti f than one H’ ion is fepace by benzene i chen Hs which one or more led Chloromethylation- Page_ When benzene reacts with formaldehyde and HCI in the presence of ZnCl than by substitution in first step benzyl alcohol is obtained which on further reaction with HCI converts to benzyl chloride. \ CHCl ! ZnCl, ‘ —> jetes in threes * + ZnCls Pi tron of Benzene GH.OH CH,0H FH.OH I + fo EO HOH CHCl + HCl — ag H* + ZnCl; ————*> _ ZnCl, + HCI (viii) Carboxylation The substitution reactions of benzene in which one or more than one H’ ion is replace by “COOH called Carboxylation. When benzene reacts with phosgene gas (COCI,) in the presence of AICI; than by substitution in first step benzoyl chloride is obtained which on hydrolysis converts to benzoic acid. Due to highly poisonous nature of phosgene gas thiszoic acid anothe, cooH AICls S Formation of electrophyl i E-N+Cat ———+ “E+ Cat -N" on Step Attacking of electrophyl on Pi electron of Benzeneee 5 6 —G-B 3" Step Recovery of catalyst H* + Cat -A Cat + N-H Addition reactions Benzene (2015,2017) Addition of Chlorirje eal chlorine in the presence of sunlight When benze at 50°C and . addition of three moles of Clz Hexachlero lone ‘ane is obtained. 1 hy, 50°C and 400atm Cl we yc Cl, pnzene of cl cl Hexa chloro cyclo hexane (2013,2015,2017) Hs CH,Cl Sun light +Clz Pageoxidation idized BY ordinary oxidizing agent such a, 8 not ox! or W205 respectively £6, ony § or Syst rh et nzene | | glyoral a edt 7 oxidized by KMn0Os to ‘ie s grouP- \N O + KMnO« action violet ¢ ™ Bind, remain eoor.201020422044" \ (2012) gre CHO (2012,2014,20 Glyoxal sé - 90, ———— La Hoc 400°C ale POT AHO SACO: °o Maleic anhydride Page(2000,2003,2005,2016) Orientation )- nitro phenol P- nitro phenol action shows that subtituent group of position of incoming electrophy! as well as Jehavior is called orientation. On the basis Cons 4 a of incoming electrophy| substituent groups eiclassified into two types. ta director ptho Para director i) Meta director:- The substituent groups of benzene those directs the at meta position called meta director. All electron withdrawing group they decrease e ring hence rate of reaction decreases incoming electrophy! deactivating group. For example NO:, the meta director are the charge density in th so they are called meta COOH , CHO, COCH;, SO3H Page _ - 2 aii jrector:= the inc: ii) Ortho-Para direc e directs ‘OMmin, of benzene thOS' 4 ortho Para directo, The substituent groups OF Ds position C4 onating they increase electrophyl at O' director are electro! of reaction eee \ Mostly Ortho avy in the ng ne ce grouP for examp! jens! tins the chatae ortho pasa al ay ator such Eire due Ou,CHsNH2 However / c nso high negative ind ined called Ortho Wi) there for Ihis easy to PF oi Saup inde a on decreases there for itis ee > ohpHenpl)s easier than benzoic acid, SES pe Ieran ele { donating group it increase the ane hence rate of reaction increases while alectrort withdrawing group it decrease the & ‘ring hence rate of reaction decreases it $f phenol is easier than benzoic acid. (2009,2015) (i) Meta nitro benzoic ci fOOH GOOH AICI, O)-onc OB sino Noe H2S0, 3 QO NO Toluene i Benzoic acid Meta nitro benzoic acid ee ee ace ee(2015) (ii) Ortho Para nitro benzoic acid CH. COOH 102 ‘a 3 ne Kno,” O- alto tohane ©: nto TS CHs coo! | — \\lt | Oz NO2 one P- nitro benzoic acid (2012) (iii) m — di niffo toluene Ni NO2 NO2 CH; NO, Meta nitro benzene _m — di nitro toluene CH; CH; NO2 H2,SO4 Oo NO, Toluene O-Nitro toluene —P- Nitro toluene Page __ — _= 4 i OOH : (ii) Benzoic acid 1504 0OH a — NO2 ° L 0 ™ eta Nitro benzoic acid 7 t (iii) chloro benzene ( (iv) Aceto phenone yor vd, G +HNOs CL NO2 yet meta di nitro benzene (v) Phenal OH OH YNOz 2 H,SO, A_sAINOs | Phenol im (2010) O-Nitro phenol —P- Nitro phenol CH; | GHs p Hs 0 FeCl, cl +c, ———> Toluene r ©-Chioro toluene _P- chloro tole —— Page —Q# Why does benzene gives electrophilic substitution reactions? Since Pi electrons of benzene are nucleophilic in nature hence reaction is initiate by electrophilic attack which shows that benzene gives electrophilic substitution reactions. Q# Define Aromaticity’ aromatic burns with With out Soot. Q# Give two equations (i) Benzene beha a rated hydro carbon. CeHeCle —————*_ OHC-CHO e Behave as Saturated hydro carbon. dH, + KMnO0,——No oxidize Violet colour of KMnO, remains same FeCl; (b) CeH, + Cl, ——> CH Cl + HCI Pagehence Isopropyl benzey, 8 (2018) C(CHs)3 AICI; H)sCCl ——> Ter. Butyl benzene Cyclo alkane G a # What are Alicyclic compounds? Give one method of preparation of Alicyclic compound iii, Wea wr non Benzenoid cyclic compounds in which ring consist om Nic carbon atoms called Alicyclic cot Anta y' mpounds. ob Cyclo Butar ¥ ne Cyclo pentane Cyclo prom oT Page EET BePreparation \t (i) From di halo alkane When Di halo alkane in which halogen atoms are on termina carbon when reacts with ium metal in the presence of anhydrous ether than b} al of X2 cyclo alkane at this reaction is similar eaction z When calcium salt of dica pounds such as calcium adipate on heating cot arbonyl compound which \ by reduction with a édium forms Cyclo alkane (Cyclo Pentane) CH, - Cl Heat Zn/Hg, | ca ——> =O +[H]— c c -CaCO; HCI fe] ladipate Cyclo pentane Vit From unsaturated cyclo alkene When cyclo hexane reacts with Hydrogen in the presence of Nickle then by addition of one mole of H cyclo heane is obtained On —— O Pagene ich cyclo alkane whic! jons of ve! actions In d compoun Reactions o tions ( saturate ids Ring ope" pehave a6 ich cyclo alkane () tions (Reactions in nant penal Lo (2) Substitution eae! ave as $4 ie ; - CH, — CH2 - Br 1-bromo propane Br — CH; - CH2 — CH: - Br 1,3 - di bromo propane cl I Sun light (2011,2014,2015) Stability of ring of c clo alkane (Baeyer’s strain theory) Cyclo alkane are s; is turated h is SP° hybridize 2 ydrocarbons j . than this probable ne? Probable angle is Aaa each carbon angle than there ig an Inter if angle ee Strain in the Pagering which de stablise the ring and is called Baeyer strain theory. For example cyclo propat between orbitals are 60° which is much differ from probable ne its shape is like triangle and angle angle of SP° hybridization so there is maximum internal stré shows that cyclo propane dathe least stable cyclo alkane. square in which angle| Cyclo butane its shapes orbitals are 90° so there Cyclo he orbitals are e is fore stable than Sachse that cyclo yx atoms they internally themselves so cyclo hexane is alkane having 6 or mot reduce their strain and FUsed/ring polycyclic aromatic hydrocarbon Cyclic compounds in which two carbon atoms are common called fused ring aromatic compounds for example Naphthalene. Page - Be MManthracene t! Describe two methods of paration of Naphthalene. 2000 206.2044 i) Hawort! When Benzeg Alcl; than by Succinicanhydride 2nil = HCl fest fail H,S0,ii) From « - methyl Naphthalene (from Petroleum) :- By fractional distillation of Petroleum an organic compound « - methyl Naphthalene obtained which when heated with H2 at 600 then by dealkylation Naphthalen is obtained. ci philic substitution reaction on naphthalene In) not on 2- position(B position) NO,’ attack at positi In 1(a position) \\ql \\ NO, H NO, H. 02 HNO2 Se + + = = > + More stable more stable less stable less stable (Due to complete benzene ring) PageS~show that that more stable afeforms by alpha attack it shows that \fion reaction on naphthalene favours at1- ot on 2- position(B position) philic substitution reactions and substitution favours at NO, H,SO, ele alpha position (2004,2009,2011)ro | +Ch. Heat ihe (2018) Oxidatio (2006,2008,2018) Anthracene When Phthalic anh| fd Bénzene treated in the presence of i} ‘| AICI3 To form Zoyt BenZot€ acid. This on treating with conc. sulphust ites to anthraquinone which on distillation i ynthracene t AICI3 CK & — 0 f Oo oO “O00 @- COD — x Anthracene Page‘Anatom or group © molecule called ; . aN oul alled its functional RR ho eM Ae) | grou) optant types of ful } Alkyl halide SS aloalkane ke) Alkanol GS Alkanal I iii) R-C-H 6 9 . I a RCOR Ketone Alkanone €@H RCOOH Carboxylic acid Alkanoic acid I ii vi) R-C-OR RCOOR Ester (acetate) Alkyl! alkanoate vil) R-NH, Amine A mino alkane viii) AZo com pound CsHeN2CI Benzene di azonium chloride PageQ.7(b)Name the following compounds by I.U.P.A.C System. (2000) i) COOH — CH = CH—CH,— COOH 2 Penten dioic Acid S lip! an |.U.P.A.C Name for. CeHs | i) CH;-CH-OH o - phey! ethanol oO | ii) ch, -d-cH,-cH =CH, 4-—Pentene 2 — one Page SnI 3-OXO Pentanaj SO3H © w) e Sulphonic Aciy >) © CO) een en di) S NHs | ; v) ¢ 4 — chloro CS alene i) Midi! CH, I ami methyl - 2 - Butanol H3C — C — Tr - CH; | OH NH, O GH of ill) _N,N-diethyl Benzamide < ». C-N \ C2Hses down I.U.P.A.c names: for the following Q# Write compounds. Ga CH; \ 4\ iy CHy- CH= C-CHe COOH 3-Methyl 3 —Pentenoic Acid a <_S-cu-¢ CH, 5 — Phenyl 3 — heptanon’ I CHs Re iii) ohh CH, - CHs IS N- Ethyl, ethyl 1 aming ne 00H ve i Fe > 02! a ee it 3,5 — dinitrobenzoic acid af formulas for the following. ol:- ethyl — 2— Penten — 1— CH; OH | | H,C -CH,-CH=C - CH, ii) 3-Keto butanoic Acid:- ° ll H,C - C - CH; - COOH Page _ _AG No Rg, a It correct name is 3,4 di methyl 2 - Hexanone {\ |||| | Q.4(c) Draw the structure of any five of the following compounds. IH i) «-naphthol3 — Bromo — 4 — Methyl Pentanal if u CH; Br i I HG — CH — CH — CH2— CHO iii) 3 — Keto Butanoic Aci oO J I OH |. OH v) A VI) Pyragallot HOOC — CH2 4 {COOH Q# Give I.U,P-A 6 the following compounds. i) = Hz —- COOH 13 ethyl 3 —- Pentenoic Acid — CH, — CH2 — CH2 - CH — NH2 1,4 — diamino Butane iii) OH Cyclohexanol- nitrobenzoic Acid 2,4 di G p oN NO2 OOH : yy _Hooc- CH= Cl eos ae 2-Pentene dioic vi) de 3 ténone amo e following Q#5(d) Write down 1.U.P.. i| GHs Wi i Hl thyl 2- hydroxyl butanoic aciq a— Phenyl Ethanoic acid O° C-CH; Acetophenone Q#8(d) Draw the structure of the followin: c c {i) 2- Chloro pentanoic acid =sinenes cl CH3-CH2-CH,-CH-COOH _ Page(ii) 3- keto Butanoic acid 3- Bromo pyrrole Br f cS CHs-C-CH,-COOH -)Bitanone Propanal Q &.) CH3-C-CH3 Propanone p the structural formulas for the following gompounds Picric acid B - Naphtol OH NO. A, NO2 ~~ OH ie) Oo NO, Page _ ani fF\r 4) Amino benzaldehyde Hl | HO NH,5) N- Phenyl pyrrole Q. Write the s ilae of the fo! y acid RS OH OH 4) 1 - Hydoxy naphthalene « - naphthol Page _anal _g—methy! nen OH OH OH—_— 3) 2,3,4,5,6 — penta hydroxy! Hexanal CH,OH — CH(OH) - CH(OH) — CH(OH) ~ CH(OH) - CHO 4) Oxalic acid HOOC - COOH di oic acid Q# Write IUPAC na he following in Ce IN } on S iW Ore jo aniline Cyclo hexene Br A Br Oo cy Cyclo hexa diene Br Q#6(d) Draw the structure of the following also write their IUPAC Name \ (i) Neopentyl alcohol-OH , _ gimethy! 1" Propanol 2.2- co Diieprartie oO IL Se ‘ (HsChCH z with aromatic ring then called Aryl halide such as chlorobenzene. dil They are classifying into three types. (i) Primary alkyl halide (ii) Secondary alkyl halide (iii) Tertiary alkyl halidei) Primary alkyl halide: Carbon atom ctly linked with halogen atom called alpha carbon if alpha carbon is directly bonded with one alkyl group called primary alkyl halide. Rrimary alkyl! halide (1° WO group \\I If alph directly bonded wi called secon f Ter If alpha carbon js called tertiary alkyl hal 6m alcohol (i) From alkane When alkane suc! presence of sunlight than b! halide) is obtained. R-H+Xp——? R-X + HX has methane reacts with Cl, in the y Substitution chloro methane (Alkyl Page _ I -sunlight cht Ch thal Alkene with HC! ne aa alkene reacts Vt ined. ide, mole of HCI Alkyl chiorit (ii) From Alcohol When alcoholic compo of ZnCl, than Alkyl favorable in tertia cHsc! + HCI n by addition of oe 6 lorg/propane with HCI in the Presence 2 obtained this reaction is more by reaction with PCls, PCl; and R j I R-C-OH +HCl ZnCl, R-¢-Cl PCI;OR PCl; OR SOCI, ——> R - Cl Reactions of alkyl halide Alky! halide gives following types of reactions (i) Reduction (ii) Reactions with sodium (iii) Wurtz fittig reaction (iv) Ullmann Reaction (v) Substitution metal(Wurtz reaction)(vi) Elimination (vil) Reaction with Mg metal i) By reduction of Alkyl halide Alkyl! halides by reduction with reducing agent such as of Zn in HCI then by redué with nascent hydrogen Alkane obtained. R-X+(H] Alky! halide, \\Wt CH;-1 + [H] Methyl iodide (ii) isoprop) H; +[H] ———*> CH3-CH2—-CHs + HCI CH. propyl Chloride propane (iii) Tertiary buty! chloride ( 2- chloro 2- methyl propane) CH3 CHs CH3-C-Cl + [H]_ —— > ' +HCl | CH3-CH-CH; \ Iso- Butane \ CH; Tertiary butyl chloride Page .metal in the presence a alkanes are obtain, yt nallde oupling tion. T ad od non atone "2 urtz rea yen num ot carbon atoms Bot m metal and ti en 8 fo H,C — CHs + 2NaC} ethane ined wen following compounds reacts ftesence of anhydrous ether CH, - CHs—> CH3 — CH, - CH, -CH; + 2Nal Butane cl CH;-CH-CHs I \ J = CH-CH; —> CH; - CH- CH3 +2NaCl propyl Chloride 2,3 - Di methy! Butane 1 iii) Tertiary butyl chloride ( 2- chloro 2- methyl propane) il)! Chs CH; CH;CH,; | \ ch cick +2Na+CH,-C-Cl ———+ CH,-C- a CH; | tol CH3 CH i , 3 CH;CH3 ertiary butyl chloride 2,2,3,3 -tetra methyl- Butanea i] \ (iy) 2- chloro Butane chs Ce Cts CHs ‘ GH CLL aNa Che ere CHa + NaCl i Ch: ¢ chs CH: ; CH; Cl CH; CH; 3, 4— Dime e v4 if de withys oupling reaction alkyl -alled Wurtz fittig reaction alkyl eacts with presente of dry ether.the Stiondé used for coupling of two aryl rin |. When ip are heated with copper powder at 230°c than by g reaction bi phenyls are obtained process is called 230°C Cro OO 08 lodo benzene Bi phenylAttacking 90 :2002,2005,2007,2013,2 (2000; ‘ the difference Give tepinshis step leaving group is depart from alpha carbon and carbonium ion is obtained while second step which is relatively fast in which attacking nucleophyl attack on carbonium ion and forms new product i 1 halidk ativity alkyl | le is neg electron iS Partiay, en atom heneg acquire Partai j attacks and ¥eplace x reactions Sincg ck/henled they ap. présente, ill bad Np sified int, nalog' This mechanism favors in rimary alkyl! halide This mechanism completes in| ingle ste| ee The single step of this “| mechanism is rate determining step in which both process arrival of attacking group and departure of leaving group both process occurs simultaneously and by substitution new product is obtainedibys ae , F | | ‘ Re : 41 neg a w Isa dam | Segoe wih 1 I A R R Y st Guistrate Carbonium ion New product if iy a" [Rate of reaction is fas sin!” | polar medium_ gon polar medi hy Rate of reaction © Rate of reactio concentratio \ \\ Ss R-O-R Ether > R-SH Thiol ley R-CN Alkyl cyanide (nitril) is NaNH, R-NH, Amine } RCOONa RCOOR _ Ester NH3 R-NH2 Amine fh % (2017) i) Q# Starting from ethyl chloride how would you prepare the 5 following? Ethane 7 C2H;Cl + 2[H] ——* CoH + HCI Chloro ethane Ethane Page eemieohOllS yy ceCHs + KCI + Ho thene ) Hi GaHs +2 ae Butane N\ SS H \ 0-H i\+\t20 Ethane Hs - As + Nacl thyether ride S& Hs CN + NaCl ethyl ovanide ends Ethyl amine ‘NH; > _ C2Hs-NH:2 + HCI Ethyl amine L Es 1» NadOCCHs———* GH - OOCCH; + Nac Ethyl acetate dne step wise mechanism of the following reactions? (i) Tertiary butyl chloride with NaCN i| CH; cH CH, I | CN Attacki CHy-4 G 1* step CH; -C* ones vies CN wv Slow | 2" Step an I; leaving gre Substrate Sei ols carbonium ion Tertiary butyl cyanide Pagesd (ii) Ethyl! chloride with sodium cyanide wee Sci NG... CHe Cl NO-CHs ‘i ! 9a re attacking | Zyerwngsroum vs group CH; Ethyl cyan ak) 1.2004 2000) : Show de favors Sy’ while pri aly! ) Q# Show that Tertiary 4 halide favors Sy? ha Since in tertia Je alpha carbon is% ose give hiridrahce with three a nucleop) ga step by\d alogen atom carboniun i ‘obtained thos & relativ) 2 le while in secarfd Step attacking-gro attack\én carbonium ion and by subStitution forms ne} . While in primary alkyl hatide arbon is directly bonded with one alkyl group hindrance for attacking nucleophile there fo echanism in single step in which both process lacking group and departure of leaving group both| rs simultaneously. 2 ie favors SN’ and Primary alkyl tion is much faster if itis done in the polar or polar solvent. e SN’ reaction during reacton carbonium ion is ned which stabilize in polar solvent there for rate of reaction is much faster if it is done in the polar rather ban non polar solvent. (2008,2009) Elimination reaction When alkyl halide reacts with alcoholic potash than halogen atom is eliminated from alpha carbon and hydrogen atom from beta carbon as a result alkene are obtained process is called elimination or beta elimination reaction shortly represented by E- reaction on the basis of mechanism they are classified into two types E; and E2.Hcl atonal “gue ce *KCI+H:0 iB I") KOH alkene —CH- CH * Alkyl halide 20012008 20072019) Q# Explain Ex am Yarbonium ion Alkene g called bi molecular elimination reaction y-alky! halide and completes the mechanism in hich both process removal of halogen atom from a ind hydrogen atom from beta carbon both process s}multaneously and by elimination alkene are obtained. If a (OH...H OH pl a ” I fv CH-CH-Cl ——» CH-CH...Cl_| ——* CH=CH \ \ Alkyl halide re Ss af ene@# Explain the conditions which favours substitution or ( elimination in alkyl halide OR . _ Q# Show that alkyl! halide with aq. Potash gives substitution while with alcoholic potash gives elimination. es SUB size of attacking group i ig\difficult to attack on alpha carbon so it gives elimi 3 rule if size of attacking group is very big tha rule. (2000 ),2017 Q# Cyanid halide produces an Alkene but on ary luces nitriles. OR nature of alkyl halide and size of attacking group. Since in tertiary/alkyl halide « - carbon is directly bonded with 3 alkyl groups there for attacking of attacking reagent is favours on B - carbon hence tertiary Alkyl halide favours B - elimination while in primary Alkyl halide « - carbon is bonded with only one carbon so primary alkyl halide favours substitution reaction therefor cyanide ion on tertiary alkyl halide by elimination form Alkene \ while Primary alkyl halide by substitution forms Alkyl cyanide (Nitrile). Pagei | Hl) (2002,2003,2004, 2009 $007,2015,2018) Saytzeff’s rule and Hofmann dacts with Alcoholic KOH suifferent alkenes are obtained 2) fgvourable called sytzeff’s rule. hydrogen must be eliminated from hydrogen. If size of alcohol is big such anol than product obtained according to alled Hoffmann’s rule which states that § é from carbon having more number of When unsymmetrical than by elimination 10) but which produgt According to this |r carbon havjtig C,HsOH_ CH; — CH = CH — CH; | @H, - CH - CH: 2 3 * KOH 2-Butene (saytzeff rule) {cH CH; - CH, - CH = CH, utene (Hofmann’s rule) (20 ai(2001,2012) Q# Elimination reaction of Br leads CH;-CH= CH-CHs it H,C - CH; - CH - CHs i‘ as major product. According to sytzeff’s rule} - hydrogen favourabily elimi BO hydrogen atoms there from carbon having les: r leads CH3—CH Elimination reaction ot i -CHs i as major product. WW (2003) h Ethanol ee ii) Isop a ropyl chloride st6ai3 oe CH3 Iso propyl chloride fed and eliminated product of ter. Butyl ca Substitution | + 2 NaOHag) ——— cH’ OH | CH; CH; Tertiary butyl chloride Tertiary butyl alcohol CH CH; Elimination ul | CHs-C-Cl +2. NaOH acy” CH;-C CH; CH3 Tertiary butyl chloride 2- methyl 1- propene Page - : :(2002,2008,2007,2017) Reaction with magnesium metal Grignard reagent / Organometallic compound When alkyl halide reacts with magnesium metal in the Prego of anhydrous ether that a highly reactive reagent {3% Magnesium halide is, which is comm s ky grignard reagent wh example of organo culled compound . R-X us ether CH Grignard reageé Ppreparation\g {2004,2005) (i) Alkane R-H + MgX(OH) CH, + Mgl(OH) R-H + MgX(NH.) | CH, + Mgl(NH.) Qy vig R-R + MgX(OH) H3Mgl + CH3OH ———> CH,-CH; + Mgl(OH) (2018) CHsMgBr + C,Hs0H ———+ C,H,- CoH, + MgBr(OH) RMgX +R-NH; ———» R-R+MgX(NH;) (2007,2011) CHsMgl + CHy-NH, ———> CH,-CH; + Mgl(NH;) RMgX+RX ——+> RR+MgX, (2007,2016) CH3MgCl + CH;Cc] ———+ CH3-CH; + MgClz Page _(200.2017) \\\ | Alcohol When Grignard reagent reacts with carbonyl compounds in acidic medium by hydrolysis forms alcoholic compoune ction forms primary alcohol dtbe Formaldehyde by this r Fi aldehydes forms secon; cohol and ketone by re ; forms tertiary alcohol. ¥ ° | H,O/H" —_——_ rf ne eag ‘imal LES sac a 4 RIMgX H-C-H, CH, jcohol Grignard + (2003,2010,2 . OH \ CH;MgBr W,€-H CH3-CH2 Methyl magnesium Formaldehyde Ethanol Bromide \| MgX OH i H0/H* | R-MgX + R+ -CH-R ————> _R-CH-R f 2°Alcohol OMgBr OH | H,0/H* \ “H+ CH3-CH-CH, ———> CH3;-CH-CH3 dm Ethanal 2-Propanol (Acetaldehyde) oO, OMgX OH lI H,O/H* \ R-MgX R-C-R ————> R-C-R ————_* R-C-R I | R R Grignard reagent Ketone Tertiary alcoholqi mg o B \ Wf li| | eoonaoeanre 05 ol ‘a0 cH -CHs fa IL —> CHs“ 2 Hs H, CHs-C-CH: Hs cl 3 Ol Cesta ee Gs Tertiary bu C Bromide amrGarboxwlic acid a =- a =C- Cc R Rylic acid wi BI x > O=C-OH Hi ig! c l is | | onal +O Carbon dig: CH; a lodide Acetic acid Q (2000) «mal when tertiary butyl magnesium a promi be gibon dioxide. En c CH;0 3 c a Il H'/H,0 | CHs 0f/+CH, - C - C - OMg Br CHs-C-COOH a | | CH; CH; ( mote W is 2- Bromo butane prepared from 4- Butanol j|l| | Chi Sllz ClCH OH + H80, Boll CHs ~ CH, CH = CHa HBr ' jutano! Br | CH; - CH,-CH-CH,2 - Butanol OH Br | | CH; - CH, - CH - CHs + ACI ZnCl; CH; — CH -CH - CH, 2- Butanol . ; f (2016) Q# What are alco! ni If one hydrege: Dom ‘Alkane is replace by hydroxyl group called alcohgt/repres by R-OH there general formula is {ifferent types, if they contain one OH group fdric alcohol. ic(comfpounds containing two hydroxyl groups called di a\cohol similarly if they contain three hydroxyl group called fri hydric alcohol if contain more than three hydroxyl group than also called poly hydric alcohol. R-CH2-OH Mono hydric alcohol CH3-CH2-OH_ Ethyl alcohol OH OH OH OH 1 ot 1 | R-CH-CH Di hydric alcohol CH,-CH; 1,2- ethandiol (Ethylene glycol) Page oe aot C2 4,2,3-propan triol (glycerol) (2001 2002,2004,2006,2011) What are Alcohols (& Wrectly bonded with Benzene ring calle uifectly bonded with open chain alkyl group but Zene ring called Aromatic alcohol. 1H H2— OH i Alcohol Phenol Benzyl! alcohol (Aromatic Alcohol) Page | wi2009 (1H Phenols are more acidic as compared to alcohols:~ Effcet of different groups on acidty of phen! Phenols by providing H* ion converts to Phenoxide iopand alcohols forms alkoxide io Gus increase the acidi such as NH2de decrease the'a acidic tl acidity position phenol Dy Phenoxide ion R-o? Alkoxide ion while Alkane not? alcohols are polar substance and water is a polar sol According to general rule of solubility like dissolve like there for alcohols are soluble in water while alkane due to its non polar nature are insoluble in polar solvent water. Q# Show that with increase in number of carbon atoms solubility of alcohols decreases. With increase in number of carbon atoms in alcohol its hydro carbon nature increases those are insoluble in water it shows Pagebility of (© vt which due to, trong” a Ui than corresponding” eZ bo! hydroget ek 9 on alkane tho: e in more ind hydrogen vesence of ZnO and Cr,0; than va t CO +2H2 Methanol Water gas saccharide, In first step starch in the presence of maltose which in the presence of invertase St ney js to glucose. In the presence of Zymase by i fermenjation it converts to ethanol. | (CoHy0Os), _Maltase C1.H».O1, Stach Maltose | Ci2He2044 + H2O Invertase 2CgH120, CoHs205 Zymase ewan 2C. Fermentation ee piningPreparation of alcohols (i) From alkene f (ii) From alkyl halide i (ii) From carbonyl compounds Nl (iv) From Grignard reagent A) 2000) \ i) From alkene y ih X when alkene are c MM acid then by addition 10) Products obtained by fl Markownikot try 3 by, 1a) CH; — CH = CH2 + Propene } 2- Alcohol If addition of alken¢ swith diborane the resultant compound: xidatiop with hydrogen per oxide in basic medium co} Cohiol which is against Markownikoff's Oly ee j2Hg ——> (CH - CH; - CH2)3B im tripropylborane ma OH NaOH | (CH; — CH, — CH2)3B + H202 ——> CH, - CH: - CH, + H3BOs 4- Propanol Tri propyl borane (ii) From alkyl halide When alkyl halide reacts with aqueous potash (KOH) then by substitution alcohols are obtained PageL- | cl +H20 (6 | OH | ( -CH2 om AW IN gud with hydrogen, jn\thi / avts mole/ alcohofg bi Suitable ion forms iS. Aldehyde CH, - OH péimary alcohol R-CH-OH R » R LiAIH, R-CH-OH secondary alcohol Grignard reagent hen_Grignard reagent reacts with carbonyl compounds in acidic medium by hydrolysis forms alcoholic compounds. eo by this reaction forms Primary alcohol other ehydes forms seconda alcoho! i ion forms tertiary alconal ry I and ketone by this reactior a) OMax OH RIMQX Hc ———. Roy, O/H ; R-CH, Grignard reagent Primary alcohol\ lif ° oa i 4 Te . oH Methyl magnesium Formaldehyde eet ano Bromide (2006) i ae H.O0/H* 9 R-MgX + R-C-I sf Z 1 Grignard reagent a R cohol A \ | OMgBr ‘ | oa oe csc ! CHMgB CoH H3-CH-C é seo ao Bromide (Acetaldehyde Fe re IH 0. ) ou R-MgX R-C-R ROR | Grignard reagent e R Tertiary alcohol J OMgBr OH | H,O/H* | CHs-MgBr § —* CH3-C-CH; ———* CH;-C-CH3 Meth’ Acetone | ! i CH; CH; Tertiary butanol Reaetions of Alcohols Reactions of alcohols are mainly classified into two types (i) Cleavage of R-O i H (ii) Cleavage of R + OH (i) Cleavage of R-O +H (Such reactions shows the acidic character of Alcohols)ium matal ion with 80 ith sodium metal a) Bea lic compounds react um alkoxide are" nen alcoho’ fydrogen its $231 character of alcohol. > with the liperereaction shows the acl Oh obtained thi R-ONa pee - Q R-OH+Na ium alkoxt ¥ ‘Apahol ;oNa +1/2H2 YY C,HsOH +Na Ethoxide Ethanol (2006,2009,2010) . b) Esterification a fh acetic acid or acid } . nds ‘fy %A cic I "! Sei tis ore Sulphuric acid forms ester itisa Zalled esterification H2SO.4 R-COO -R+H20 QOH «—— boxylic Acid Ester 1-CO-R = ——— R-OCO-R+HCI Acid chloride Ester C2H;OH +CH;C =— '7HsOH +CH;COOH <——— CH3;COOC-H; +H | Ethanol Acetic Acid Ethyl Acetate "0 (2005) C,HsOH +CH;CH,COOH => CH3CH,COOC,H; +H,0 Ethanol propanoic Acid IPA aie il ili! (2001) ’ Ethyl Propanoate C,H;OH +Cl-COCH; ~——> Ethanol Acid chloride “tenes “wel ieHl (c) Reaction with dilute sulphuric acid Is reacts with dilute sulphuric acid at When alcoholic compound: | hydrogen suphate is obtained . room temperature then alky! R-O-H +HOSO3H ~— R- 0 - SO3H + H:0 (ii)Cleavage of R= reacts with seplace by Cl and is also occu é C2HsOH +HCl Mechanism AI ¥ R-CH,-O-H>R-CH2 Cl>R- CH, - Cl Dxonium ion carbonium ion alkyl halide gnism shows that during mechanism carbonium » ébtained since tertiary carbonium ions are relatively taple there for this reaction is favours in tertiary alcohol f of reactivity is —OH > primary R - OH the Tertiary R—-OH > secondary R This reaction also occurs by reaction with PCls, PCI, or SOCI2 3C2HsOH +PCls —————— 36H,Cl +HsPOs CyH,OH +PCle | ———— > Crs #POChs +HC! C,H,0H+SOCLh 9=——— CHCl +SO, +HClHL ||) gemamgttngim amore" Seo Lacs ne. HCl in the e presence of Zn When Oo roa opal sit ned those are i insoluble in NG \ ‘near. marys secondary and tertian, forms insolul {Ail (brsece ‘ Above test J alcohol is called luca’s te aH Complete the folle (CH3),CH(OH) (2002,2014) Distinguish, CH; - CH2+ A+HCI ZnCl, __ No reaction with out heating °Q Hf fi | | il H— CH +HCI ZnClz, — insoluble layer obtained with in about 5 mine #ropanol (2012,2018) b) Ether formation (Williamsons synthesis’ When excess (Alcohol) ethanol is treated with conc. Sul i h : jphuric acid at 140°C than (Ether) diethyl ether is obtained oR. OH H2S0,(Conc.)/140°C : —— Alcohol Ether R-O-Ratho PageHzS0,(Cone./140°C. C2Hs-O-C2Hs + H20 2C2Hs- OH Di Ethyl Ether Ethanol {c) Dehydration of alcohol When alcohol is heated j at 170°C than OH groug is hydrogen atom from.beta molecule alkene if is an exampl reaction are (2014) resence of conc. sulp R-c f, +H,0 ne \\W (2007) I CHs — CH — CHs Hs - CH= CH, + H20 2- Propanol Propene o (2005,2008) fs CH, — CH= CH- CHy + H20 2 Butene Ip of mechanism show that dehydration of alcohol cidic medium is E, mechanism Mechanism H H R-CH,-CHy-OH +H> R-CH,-CH,-O-H*R-CH-CH2> R-CH=CH, carboniumion alkene Alcohol Oxonium ion Above mechanism shows that during mechanism carbonium ions are obtained those forms in E, mechanism it show that dehydration of alcohol in acidic medium is E, mechanism Page _ =eee er for pe onverts to secondary inated and is called ér 1- butanol by carbonium then beta hyd is ms 2- butene as a major Wegner Mewin rear any ! Mi dehydration in acid Wl) product (20162017) (d) Oxidation s-catporty| compounds. arbbnyl compounds on further oxidation convert to fd. Primary alcohols by this reaction forms | K,Cr,07/H2S0, R-CH,-OH + [0] >. R- CHO + H,O Alcohol Adehyde K2Cr,07,H,SO, RHO + (o] +R. COOH a Carboxylic aci idl] i. aeeruelays K,Cr,071H,80, ylic acid Ethanol |] ————> CH;CHO +H,0 Ethanal Page