y FAST TRACK IPE for SjaStudents. Gr. CHEMISTRY ae PCa ay HALO ALKANES & HALO ARENES Very Short Answer Questions : eens Write the structures of the following compounds 1) 2-chloro-3- methyl pentane . 2) 1-bromo- dsec.butyl- 2 - methylbenzene aD CHy-CH-CH-CH~CH, cl CH, Br CH, 2» CH; -CH-CH, -cH, 2. Write the isomers of the compound having molecular formula C,H,Br. A. Possible isomers for the molecular formula C,H,Br are i) CH,-CH, ~CH, -CH, - ii) CH ~CH, ~CH-CH, Br 2-bromo butane(dextro) Br ili) CH, -CH, ~CH=CH, |, — CH, - CH 2-bromo butane (ieavo) iv) CH,—CH ~CHy= Br CH, 1-bromo-2methyl propane 1D Bo | HO v) H,C- fi —CH; CH, 2-bromo, 2-methyl propane 3. How will you carry, out the following conversions ? i) Ethane to bromoethane ii) Toluene to benzyl alcohol > A. Short Answer Question: i) CH, CH, —Wf CH, ~ CH, ~ Br + HBr cH cH,cl cH,O#, KOH, Chil am Pa & Write the mechanism of dehydrohalogination of 2-bromobutane upon saytzeffrule. Assertion : Saytzeff rule = In dehydro- halogenation Reaction: The preferred product is that alkene- with grater number of alkyl groups attached to the doubly bonded carbon atoms. ~ CH CH CH, Br nate MPO cat, —ct=CH~Ci, +H,0+ KBr pre (CH, -CHy-CH = CH, + KBr +H;0 KOH(ale) What is Wurtz's reaction? Alkyl Halides reacts with sodium metal is presence of dry ether to form Alkane. R-X+2Na+X-R—S2 4R—-R+2NaX * How does PCI, react with the following? a) Water b) C,H,OH ©) CH,COOH d) Ag a) PCI; (cold) +H,0— POCI, +2HC1 PCI, (hot) +4H,0— H,PO, +5HC1 b) CHJOH+ PCI, > CyH.CI+POCI, + HCL ©) CH,COOH + PCI, + CH,COCI + POCI, + HCI 4) PCl, +2Ag—> 2AgCl+ PCI, Explain the mechanism’of nucleophilic uni- molecular substitution (SN!). Reaction with one example. A. In SN! reaction rate depends upon only. the concentration of the alkyl halide and indepen- dent of nucleophile Rate « [RX] 107CH; . CH HyC-C- Br + OH > HyC~C- OH - Br CH, CH; Mechanism : It takes place in two steps itep-I: The alkyl halide Ionises to give arbonium ion and Br-. This is slow step and is ate determining step. CH; CH; slow | H,C-C-Br 22 H,C-Ct +Br° | CH; CH, ate ec [tertiary butyl halide] 3tep-II: In the second step, the carbonium ion sombines with nucleophile to form the final substituted product and it is fast step. Ex: - ie pe Bc-€ +0H _&, HC" 6-08 CH; CH, Explain the mechanism of nucleophilic bimolecular substitution (SN”) reaction with one example? In this rate of reaction depends upon concen- tration of both alkyl halide and nucleophile. Eg: CH,CI reacts with OH" ion to form CH,OH and CI ion CH,Cl+OH™ > CH,OH+CI- nechanism - this takes place in one step. in SN? reaction the nucleophile attacks carbon ‘rom bark side of leaving halogen. During this eaction complete inversion product is formed. Zquation : H OH~ + HinmmyC-Clo fast on Go +cr H Rate « [alkylhalide] [nucleophile] ® Define the following i) Recemic mixture ii) Retention of configuration iii) Enantiomers i) Recemic mixture : It is an equimolar mixture of dextro and laevo forms of an optically active compound Eg: (d, J) 2-chlorobuatane Retention configuration : Retention of configuration is the preservation of the spatial arrangement of bonds to asymmetric centre during a chemical reaction (or) transformation. ii) iii) Enantiomeres: Enantiomeres are stereo- isomers related to each other as non superimpo-sable mirror images. "ALCOHOLS, PHENOLS AND ETHERS Very Short Answer Questions : 1. A. Explain why propanol has higher boiling point than that of hydrocarbon butane The boiling point of propanol is higher than that of butane,. due to’ the presence of strong intermolecular hydrogen bonding. But butane having weak vander waals forces. CH, CH ia ie ae H GH,1, Name 2 reactions ? > oxidation of primary alcohol to carboxyl acid jp oxidation of primary alcohol to aldehyde ») Acid KMn0, j PCC of CO, in anhydrous medium {write the equations for the following reactions ? j) Benzyl alcohol to benzoic acid ji) Bromination of phenol to 2,4,6,-tribromo- phenol CH,OH COOH AKON (e ai SH KC40s Benzyl alcohol Benzoic acid. OH OH Br ae + Bria ii) H,0 Phenol ke 2,4, 6 tribromophenol 4. Identify the reactant needed to form t-butyl alcohol from acetone? A. CH,MgX (methyl megnessium halide) is needed to form t-butyl alcohol from acetone. 0 Il Y H,C-C-CH, +CH;MgBr cH, CHiy:-C-OMgBr— > ' CH (cH;),-C-OH + Mg(OH)Br 5. Give the reagents used for the preparation of Phenol from chlorobenzene? Og S00 atm o- © « Give the equation of reaction ror ration of phenol from cumene? CH; Cts we-a8 Hyc-C-0-0-H O~ Or cumene cumene peroxide oH 4+HC-CO-CHs ‘Acetone Phenol While separating a mixture of ortho and para nitrophenols by steam distillation, name the isomer which will be steam volatile give reason. Ortho nitrophenol is steam 0 © W =~ volatile due to presence of intramolecular hydrogen bond. But P-Nitrophenol is not steam volatile due to presence of inter- molecular hydrogen bond. So it is separated by steam distillation from p-nitrophenol. Ethanol with H,SO, at 443k forms ethene while at 413K forms ethoxy ethane. Explain it? When ethanol is heated with conc.H,SO, at 443k (or) 170°C 1 mole underoges dehydration to form ethene but at 413K 2 moles undergo dehydration to form ether. : con. 380, 2HSOH "ga CH, = CH, +H,0 ones H,S0, 2CH,OH 2H JOH Te GH, ~O-C,H, +H,0 [ASTTRACK IE for Sr. Students a 109om 4, A. Write the products of the following reaction ? OC2Hs i) or +HBr— fi) CH, -CH, -CH, - ‘cone H,80, OC;Hs iti) Oo snes, cone HNO, iv) (CH), C-O-C,H, 15 ‘OC2Hs ny +HBr> + ene 2) CH, -CH, -CH, -O-CH, +HBr—> CH,CH, - CH, - OH + CH,Br CaHs 2 Sao OCHS Calls + 102 N 4) (CH,),C-0-C,H;—* > (CH;),C-1+C,H,OH Explain the products formed by the reduction and oxidation of phenol ? Reduction : a) Phenol on heating with Zn dust to form benzene OH CQ) b) Phenol on reduction in the presence of Ni to form cyclohexanol OH OH Oxidation = Phenol undergo oxidation in the presence of sodium dichromate and acid to form benzoquinone. O-CH, + HBr =. SREMISTRY OH On oO 6, Arragne the following compounds in ier, sing order of their acid strength 2 Propan-1-ol 2,4,6 trinitrophenol, 3-nit 3-S-dinitrophenol, 4-methyl phenol, pheng, ‘A. Propan-1-ol<4-methyl phenol < phenol < 3-nitrophenol<3,5-dinitrophenol< 2,4,6- trinitrophenol. Explain the acidic nature of phenols ang compare with that of alcohols, A. Phenols are acidic in nature because of ther affinity to produce proton and phenoxide ion (conjugate base). So formed phenoxide ion is stabilised by resonance. More is the stability of conjugate base more is the acidic nature of corresponding acid. oe Phenol Phenoxide ion Be ‘The phenoxide is Mhore resonance subi 5 phenol as it does not involve #Y oe Separation in its resonance structures Tesonance is not possible in alkox’ alcohols are weaker acids than phenols ROH>RO- +H" 4 Alkoxide ion ‘4 A ' i) CH,-1 will react faster becau: te any two preparations of phenol? i Vea on reacting with NaOH at 623K and 320atms produces sodium phenoxide on further acidification with HC! produces phenol ONa™ b2-6=6 ii) Aniline on diazotization produces benzene daizonium salt which on further hydrolysis gives phenol Njcr NH OO OH 82, (6) +n, +H ). Explain the acidic nature of phenols and compare with that of alcohol. . Phenols are more acidic than that of alcohols reason C,H,OH = C,H,O" +H* phenol ‘phenoxide ion (HOH —=C,H,0 +H* alcoho! slioride ion Phenoxide ion is stabilized by resonance more the stability of phenoxide ion, more will be the acidic nature of phenol. bd-B-0 But alkoxide ion is not stabilized by resonance. Hence alcohol is less acidic. Which compound in each of the following Pairs will react faster in Sy2 reaction with OH-? (© CH,Br or CHAI. (ii)(CHy)s CC! OF CH,CI se bond dissociation enthalpy of C-1 bond is less than that of C-Br bond. ii) CH,CI will react fas carrying halogen has less, steric hinder fer because carbon ance as __ compared to (CH); CCl Long Answer Questions : Explain the following reactions. a) Kolbe’s reaction: b) Reimer-Tiemann reaction: ¢) Williamson’s Ether synthesis: A. a) Kolbe’s reaction : gu (OOH 1, O Non, (0) 2 Phenol Sodium Phienoxide —_2-hydroxy benzoic acid * Phenol reacts with NaOH to form sodium phenoxide. * This undergoes electrophic substitution with CO, to form 2-hydroxy benzoic acid (or) salicylic acid. b) Reimer-Tiemann reaction: Phenol reacts with chloroform in the presence of NaOH (or) KOH to form salicyladehyde. OH = & = O +CHCI, + 3NaQH—C_, salicylaldehyde ©) Williamson’s Ether synthesis: Alkylhalide reacts with sodium alkoxide to form Ether CyHsONa + CH;I > C,Hs0C;H, + Nal 2. Write the equations of below given reactions, a) Friedel craft’s alkylation of anisole b) Friedel crafts acylation of anisole ©) Nitration of anisole A. a) Friedel crafts alkylation: OCH, @rae —Atiatowwalcy cs, Anisole~~ >) When electron donating groups present in carboxylic acids, they decrease the acidity of sarboxylic acids by destabilising the conjugate vase Hectron donating group destabilises the car- roxylate anion. Write the equations of any aldehyde with Fehling’s reagent. Febling’s reagent is a mixture of two solutions Fehling solution A arid Fehling solution B, Fehling solution A is aqueous copper sulphate and sodium, potassium tartarate (Rochelle salt). These two solutions are mixed in equal amounts to form Fehling’s reagent.On heating an alde- hyde with Fehling’s reagent, a reddish brown precipitate is obtained Aldehyde is oxidised to corresponding carboxylate ion. R-CHO+2Cu? +SOH™ - R~COO" +Cu,0 1 43H,0 What is Tollen’s reagent? Explain its reaction with aldehydes, Ammonical silver nitrate solution is called Tollen’s reagent. On warming an aldehyde with Tollen’s reagent a bright silver mitror is produced due to the formation of silver metal. The aldehydes are oxidsied to corresponding carboxylate ion R-CHO+2[Ag(NH,), | +30H7 > R-COO™ +2Ag 1 +2H,0+4NH, Describe the following, |) Cannizaro reaction _ ii) Acetylation |) Cannizaro reaction : Aldehydes which do 1ot have an o@ hyddogen atom, undergo self. yxidation and reduction (disproportionation) fe es i Long Answer Questions ) a reaction on heating with conce y is called cannizaro reaction ®t Tl 2HCHO + NaOH ~> HCOONa +c ii) Acetylation : The replacement hydrogen of alcohols, phenol benzene with acetyl group (CH. acetylation. It is carried out with or acetic anhydride. 30H OF acting + amines (o, CO) is cay Acetyl chloride C,H,0H +CH,COcI-> CHLCO0C cH (CF -e004 ao, O= Aceto Phenone Describe the following a) Acetylation b) Cannizaro reaction ©) Cross aldol condensation 4) Decarboxylation a) Acetylation: Benzene reacts with ceil chloride in the presence of anhydrous AICI, form acetophenone. OCH; +CH,coc) —Seeaelch © Benzene Acetyl Chloride ‘Aceto phenost b) Cannizaro reaction : Aldehydes which not contain o-hydrogens undergo ‘! oxidation and reduction when heated ¥!! Concentrated alkali (in this reaction molecule of aldehyde is reduced to alcoh? another molecule of aldehyde is oxidized! carboxylic cid) ZHCHO + NaOH ~>CH,OH + HCOON? RieT SE ee aw8. Complete the following conversions. i) Benzoic acid to Benzamide ii) Aniline to p-Bromo Aniline + COOH OONH, — CONH, A. i) NH; A ES G+ SG) s.0 Ni, Nucoce, . ©) (€x4c0),0 oO Bi /CH,COOH ‘Acetanilide. NHCOCH, Ni Hoon, © +cH,COoH Br = pbrome acetanilide" .- prom aiine © ‘Why can’t aromatic primary amines prepared by Gabriel pthalimide synthesis. A. Potassium pthalimide don’t reacts with aryl halides because C-X bond in halo arene is difficult to be cleaved due to the partial double bond character.There fore Aramatic primary amines can’t prepared by this reaction. CON OC ere rt Short Answer Questions : 1. Write the IUPAC names for the following compounds. i) CH, - CH, -NH-CH, -CH, ~CH; ii) PhCH,CN NH CH, - NC o iii) iy) { Br - CH; -N=C+4(H)—S/GHOW CH, —NHCH, (Se SHEMET i) Ne-ethyl,1-propanamine ii) 2-phenyl, ethanenitrile iii) 3-bromo aniline or 3-bromo benzene aming iv) 4-Bromo, phenyl methan carby! amine Account for the following. i) PX» of Aniline is more than that of me thy amine fi) Reduction of alkyl cynide forms 1°-Amine, whereas alkyl isocyanide forms secondary amines. 4) In aniline, the lone pair of Nitrogen atom is involved in conjugation with ring and is less available for protanation than methyl amine PX value of aniline is more than that of methyl amine and aniline is Jess basic ii) When alkyl cyanides are reduced with hydrogen is presence of pt or Ni or LiAlH, gives primary amines. When alkyl iso- cyanide are reduced with H, in presence of ‘Ni or Pt forms secondary amines containing methyl as one of the alkyl groups. CH, -CN + 40) 24H, —CH, NH; How do you prepare the following. i) N,N-Di-methyl propanamine from Ammoni 4) Propanamine from chloroethane, onc i) NH, +C,HCl— C,H, ~NH, E> 3H, -NH-CH, SS" cH, ii) CH; ~CH,CI—8_cH,CH,CN Redon NH: SSS" CH,CH,CH! eee FAST.TRACK IPE for Sr. Stude™®7 ot 9. Explain why the order of basicity for methyl amine, N-N-dimethy! amine, N, N, N- trimethylamine changes in gaseous and aqueous medium. A. 1) The basic nature of aliphatic amines increases with increase in no. of alkyl groups. NH 1°32°>3° -4) As the bulkyness of alkyl group on nitrogen atom increases, basic’ strength decreases. NH, >1°>2°>3° Therefore, by the ciinbination- of above 3 effects basic strength of amines in aqueous solution is 2°>1°>3°> NH, Explain,the following reactions a) Sand meyer reaction b) Gattermann’s reaction ‘A. a) Sandmeyer’s reaction: The nucleophiles like CI", Br-, CN>, are introduced in the benzene ring when bezene diazonium halide reacts with HCI, HBr & KCN in the presence of cuprous ion. cl Cu,Cly/ Het -—— +N: 2° o OMX Br O CuBr, /HBr on N CuCN KCN +N: St. CHEMISTRY] b) Gatterman Reaction: Cl and Br- are introduced in the benzene ring when benzene diazonium chloride reacts with HCI (or) HBr in the presence of copper powder a oe aX cuytici oo +N Cux 6 ) be uy HBr +N: 40ux Long Answer Questions : Explain the following named reactions: i) Iodoform reaction ii) Aldol Condensation iii) Clemmenson’s reduction Carbylamine test “ ¥)-Hell-Volhard Zelinsky reaction vi) Hoffmann Bromamide Reaction vii) Rosenmund Reduction Gatterman — Koach Reaction ix) Wolf-Kishner. rea x) Finkelstein reaction xi) Swart’s Reaction A. i) Todoform reaction: When cthylalcohol is heated with 1, and-alkali (yellow crystalline solid). Iodoform is formed CH,CH,OH + 41,+ 6KOH CHI, + HCOOK + 5KI+5H;0 term ii) Aldol Condensation: Aldehydes and ketones Containing c@—hydrogen atoms undergo aldol condensation. Aldol condensation takes place it Presence of stronybases ke NaOH. Ba\OH): [}-—-_-$- + FAST TRACK IPE for students) aCH; ~CHO+CH, ~ CHo_DOH CH, ~CH=CH-CHO But-2-enal iii) Clemmenson’s reduction: Acetaldehyde on reduction with Zn-amalgam and Cone.HCI gives Ethane CH CHO + 4[H] —2e-Hevticl oy, -CH, +H,0 iv) Carbylamine test: (Isocyanide test) All primary amines give isocyanide test when aniline is treated with chloroform and alk. KOH, phenyl isocyanide is formed. NC 4+3KOH + CHC —e © #3KC1438,0 phenyl isocyanide y) Hell-Volhard Zelinsky reaction: CH,COOH —S2i#_5 CH, -Cl-COOH SHE 5 NH, Aniline CH, -Cl, -COOH—“2/E#_5CCI; - COOH When acetic acid reacts with Cl, in the presence of red phosphorous o1—hydroge are substituted by chlorine atoms vi) Hoffmann Bromamide Reaction: Amide reacts with Bromine and NaOH to form amines R-CONH, + Br, + 4NaOH > R-NH, +2NaBr+Na,CO, +2H,0 vii) Rosenmund Reduction: HO eo) +HCI Benzoyl Chloride Benzaldehyde Benzoyl chloride on reduction with hydrogen in the presence of Lindlar’s catalyst gives Benzaldehyde (Pd/ BaSO, in quinoline) viii) Gatterman - Koach Reaction: Benzene reacts with CO and HCI in the presence of anhydrous AICI, and CuCl to give benzaldehyde. CHO comet Haire TT? Benzaldehyde ix) Wolf-Kishner reaction: Acetaldehyde on reduction with hydrazine in the presence of KOH gives ethane. (CH,CHO+ H,N-NH, >, CH, ~CH, +N, +H,0 x) Finkelstein reaction: Alkylhalides reacts with sodium iodide (Nal) in the presence of dry acetone to give alkyl iodide. CH,Br + Nal —2"""_5 CH, -1+NaBr xi) Swart’s Reaction: Alkyl halides reacts with AgF to to form alkyl fluorides CH; —Br+ AgF > CHF + AgBr xii) Gabriel -Phthalimide Synthesis: [FAST TRACK IPE for Se. Students}—______ rg00Na RNH; + ‘COONa Sodium Salt of Phthalic acid Pthalimide reacts with alkyl halide in the presence of ethanolic KOH to form N- alkylpthlimide. This on reaction with aqueous NaOH to form primary amine, xiii) Wurtz-Fittig reaction: x R alkyl benzene, —BE2 120 ‘Sr. CHEMISTRY Alkyl halide and arylhalide on reaction with sodium metal in the presence of dry ether to form alkyl benzene xiv) Fittig Reaction: x 2 + 2Na SE, (O)-0) +28 Bi Phenyl ‘Aryl halides on reactions with sodium metal in the presence of dry ether gives biphenyl FAST TRACK IPE for Sr. Students