FPP Wd eee 1. CLASSIFICATON, ISOMERISM, PHYSICAL & CHEMICAL PROPERT AND NOMENCLATURE. Preparation: 1, From alcohols (Replacement of OH by X) Examples: ROH—SSR-X Hye OH otc Pease I, ROH+PCI, > RCI+POCI, +HCI ROH+SOCI; + RCI+SO, +HCI 2. Halogenation of Hydrocarbons: R-H—S>R-X+H-X — SYNOPSIS aS ries STRUCTURE ces CHy ‘Example: es By, Saar a HC. HC 'CHy Hy Hy +HyC cH, ‘Bric regents. The typical reaction of alkyl halides her boiling points than ‘group, the boiling point increas wit hhas the lowest boiling, and iodide bas are insoluble in water, probably because of soluble in typical organic solvents: have considerably higan ith of IVE CHEMISTAY 116 | Sj MECHANISMS & ARYL HALIDES PREPARATION ‘METHODS TS of slow step i) RX REX” carbonium ion _, RY+ Nu” > RNu or ii) RY +Nu—> Nu” at = K{RX] (Ist order) HAC. we HC 5 X —(HyC),-C* R:X+Nuv > RNu+X™ or R:X+Nu->RNu? +X” = K[RX][:NU] (2nd order) ‘effect on rate — Effect of nucleophile ‘Catalysis Competitive reaction ARYL HALIDES Inversion and racimization Unimolecular 3°>2°>1°> CH, Stability of R* RI>RBr> RCI > RF Rate increases in polar solvent Tieewis acid Eg: Ag, AICL,, ZnCl, Elimination rearrangement (E,) Inversion (backside attack) Biomolecular CH, > 19> 2?> 3° Steric hindrance in R. group RI> RBr >RC1> RF With Nu there is a large rate increase in polar aprotic solvents rate depends on nuclephilicity I> Br > Ch; RS“> RO- None Elimination (E,) Aryl halides are the compounds in which halogen atom is directly attached to the benzene ring.(Sandmeyer reaction) MISCELLANEOUS REACTIONS) eophilie substintion reaction. this er to the carbon-chlorine bond, vand hence chlorobenzene #* moreIECTIVE CHEMISTRY. 1B Benzyne is a symmetrical intermediate and can be attacked by nucleophile at both the positions. Cl, \.NH *e +O -ol . NH Isotopic labeling confirmed that there is an equal chance of abstraction from both carbons. An aryl halide which does not contain alpha hydrogen with respect to halogen does not undergo this reac- tion. In the reaction involving Benzyne intermediates, two factors affect the position of incoming group, the first one is direction of aryne formation. When there are groups ortho or para to the Teaving group, then the following intermediates should be formed. Zz 7 z: Zz a a a} Ny aoe When a meta group is present, aryne can from in two ways, in such cases Zz Zz Zz Os0-O e ‘More acidic hydrogen is removed, ‘gen while an electron donating .. an electron attracting °Z' favours removal of ortho hydro- favours removal of para hydrogen, ent sas sae 344 EXERCISEH bie (Preparation, Physical & Chemical Properties of Alky! halides) _Stralght Objective Type Questions ons, the product is 1-cllorobutane| [ALA AM ‘AND ARYL HALIDES P>>—— —HOBJECTIVE CHEMISTRY Ii Which of the following reagents is the best for preparation of alky! chord a 1 pure fo Dre, 8 Soc, PC), 4) Chlorine & Red P 4 In which of the following reaction, alkyl ehloride is not formed a) ROH + PCI, DT ROH + NaCl c) ROH + SOCl, 6) Ethane + SO, S$, The Vield of alkyl bromide obtained as a result of heating the dry silver salt of bromine in CCI, 1s 2) 1° > 3" > 2 bromides sl? > 2 > 3° bromides ) 3° > 2? > 1° bromides d) 3° > 1° > 2? bromides 6. The reaction of SOCI, on alkanols to form alkyl chlorides gives good yields becaw 44) Alkyl chlorides are immscible with SOCl, 27 The other products of the reaction are gases and escape out ©) Alcohol and SOC, are soluble in water 4) The reaction does not occurs via intermediate formation of an alkyl chloro sulphite See oe OO “hy i : Br 8 The alkyl halide which possess highest dipole moment is a) CHF rCHel ©) CH,Br a)CHL % The products of reaction of alcoholic AgNO, with ethyl bromide are a) Ethane b) Ethyl nitrite A Nitrocthane d) Ethyl alcohot 10. The inajor product formed tn the feaction is «) Bt-§-CH, -CHOH)CH, « bt § CH-cH-en, CH, -cH«cnycH, AT §-cHCH cH,on @) Et- §-cH, ch cn, AM Wdent fy the set of feSgentifredttion ebidltions *X* aod “Y* in the followihg set of transformaton CH, - CH, - CH, $+ Predict cH, CH-CH,/ inactive more stable ‘more stable than trans-compound 1g isvare polar aprotic solvents b) CH,SOCH, (DMSO) ) bc ralfowing reactions depict the nucleophilic substitution of C,H,Br _BeG NOH CH, + HBr + C:H,SCHs+NaBr D) C)HsBr NC+AgBr @) CyHyBr+KOH + CH,OH + KBr aC derivatives, on further chlorination ean yield only three dichloro ¢) Chlorobenzene 4) Chloroeyelohex vith ethyl bromide, would yield diethyl ther © the i _b) 2-Chloropropane reagents, on reaction ‘p) Alcobolic KOH ¢) Silver oxides _-—«) Sodium etboride 30, WE a) CH- CH, - Br _ wot, x] + 04). (Xd and [YT d CH; » ‘OH 6, a On @) products among the following.ARYL HALIDES ‘of the following react with CH,l, ee OO Oe 12, What is the product of the given reaction? Br De Benen Jvc one OH 16. 4 CH CH; ws Ai ) ue ¢ OH y z ata faster rate under Sy2 condi onat =ALKYL AND ARYL HALIDES Cy Cills HL ft Cc a) PS Pa we °) he 4) None is correct Hs CH cae — CH,- Mgl, H,0*, (ii) H,S0,, ia HBr, R,O, >) @ CH,- Mgl, H,0°*, (ii) H,SO,, A. (iii) HBr CH,- Mgl, H,0*, (ii) HBr HBr, R,O,, (ii) CH, Mgl, H,0* More than One correct answer Type Questions -reaction, which of the following statements are truc: poireaction is independent of the concentration of the nucleophile altacks the C-atom on the side ofthe molecule opposite to the group being displaced ily than (CH,), CHI for §,2 reactions. fe readily than CH,-CH,-CH,-Br for S,. reaction. Pmore readily then (CH,),C-CH,-Br for S,2 reactions than NO,-C,H,-CH,Br for S,2 reaction > cH.CH,CH-CN CH, above reaction’? don of carbocationjut will obtained. aN ARTI AR an only inverted prod! c) Spa” Tn which of following react a) Syl b) Sy hate by Cone of substrate ppt i) Nate of vole © OOOO ‘The shown order is-a correct order during the rate oft 21. Ami 2) Sq! mechanism 6) E? mechanism €) mechanism 4) Sy! mechanism ax 24, Consider the reaction given below. Des ‘CBs x ~ cl 2 L + NaCN(oq)— 22> N (LO equivalent) 4x ‘The correct statement(s) applicable to the above reaction isfare a) Cl is substituted predominantly b) Cl is a better leaving group aT -c) substitution of f in the above reaction required greater activation energy than for Cl 1 aa 29. MC reactions is 1>Il>IM —b) Reactivity for §,2 reactions is 1> I> Il mi I<smon 4)IVel>l>m Matrlx Matching Type Questions the leaving group the energy of the product, driving the equilibrium ‘Column-I P) Nucleophiti-aromatie substitution reaction ) Elimination reaction 1) Sy! reaction 5) S,2 reactionBr B) aca ° ‘oe D)H,C-1 CH; CH, CHs a 6) wel H) ao? CHs give Sy2 reaction with measurable rate is °x". What 's ne stereosiomers in the following reaction? ‘Number of compounds that 49, Identify the total number of S, and E, products including , — CH = CH, reacts with Cl, at 500°C. Find out no, of possible products. (includinga ct OE a Bi 3. Chlorination of toluene in the presence of light and heat followed by treatment with 1: NaOH ey a) oeresol ») p-cresol ©) 2A-dihydroxytoluene dy Benzoie acid 4, Which of the following is likely to have highest melting point AY ae Pe een a ca oO, Oo : ») °) ca EO ‘same mop. as they are isomers q following compounds in order of increasing dipole moment M1) medichlorobenzene Ill) o-dichlorobenzene IV) p-dichlorobenzene —F* WhS Ufw»fOBJECTIVE CHEMISTRY IB} CH; i Ao ¢qy Ut 9 (B) ater? (C(O! LC Ne Hy 24. CH, g CH,OH CHOH—CH,0H CH,—CH,OH CH,—CH; 25 2 More than One correct answer Type Questions 18. Benzyl chloride (C,H,CH,CI) can be prepared from toluene by chlorination with: AySo,Cl, ») socl, ey Clshy 4) NaOCl ¥ 19, Oresnic halide that posses a functional group that react with R-MgX cannot themselve form a nt. Indicate which of the following chlorides need to have its other functional group sgrignard reag protected in order to generate R-MgCl cl cl lee oH i) 4 0 » LO OU Grignard reagent? b) H)N-CH,CH,CI Br es HO’ BEL resonance structure, of th: Be onclesphiey species formed in the nucleophilic oe 10) tated product Z~_On CH,CL co —— ‘ haitanyi ICON Student HOt £0 10 completion to give theof the following statements are not correct? Srobenzene is more reactive than benzene tow: = Cl bond in chlorobenzene is Jess polar than in £) Chlorobenzene is less reactive than Ci d) In ards electrophilic substitution reactions. CHC HCI towards nucleophilic substitution reactions further substitution take place at meta position ich of the following reactions result in a Product with more number of carbon atoms tt ing compound? b) Gattermann reaction d) Balz-Shiemenn reaction Welds diphenyl methane on reaction with __ in the presence of anhydrous AICI, ‘The items can be ‘ (Oyen ©) CHCl, 4 (O)-crce ‘of the following aryl halides will react with sodamide/liquid ammonia leading to substitution yne mechanism ™pe Questions>+[ALKYL AND ARYL HALIDES} srent products formed in mononitration of 1, 3 ~ dibromo benzene including minor et of substitution products formed whe metabromo anisole is treated with KNH,/NH, is compounds do not react with NaOH. Sh x CH, —Br ; ¢) CH,-I jd) uc/" SS ;AURYL AND ARYL HALIDES XERCISE-IV 3 : (Mixed Problems) 1 whet of the fol a a cl cr a) a) ») ole A F tel pa nr 0 ‘ ee CH, cH cH Hy BT Hy HCl ci--+H -D H+-p Hp y Hp }-Br » Ht 1-H aa =D HD np tp 9. Hy cH cHy Hy dee of ucloophiticity in p a) 1 >Br® >cl® >F° b) FP >cl® >Br® >1° ) B® >1%>Br® >ci” d) 9 >Cl® > Br? >F* ' {ferent b toms towards NaSH in Ba 10 a. Oo fh )Q>S>P>R 4)P>S>Q>R a ° me il CH,-C-o a avy their leaving group ability in nculeop o)IV>1>i>m dIV>M>M>I SERIES for St Chaftanya Sr. CON Students) {OBJECTIVE CHEMISTRY Ra 2 CTH Which (eure F a) Reac ©) Both Selec ait The a) CHY a) Al HO Step abCTIVE CHEN * TACEYE AND ARYL HALIDE For the compounts CH,C1. Cyt, CHL see CHU tive corset attier of teresting C-halingen bond Aerygth ACHE < CHC conor een by) CHP < CHB < CHE < CH) SV CHE < CH\I « CH\tir< CHC 4) CHCl < CH,Br < CHP < CHS Tthy! alcohol reacts at a faster rate swith ML than sith HCH in forming. the comenponding etry! batiden tundor identical conditions mainly because a) HL, being 4 stronger acid, protonates ethyl alcohol at oxygen much betuer and helps substinution: ') the bond lengul in HI is mitch shorter than that in HCI ©) F is a much better leaving group 4) Fis a much better micleophile than Cl- Which of the following ix Yeast reactive in a nucleophilic substitution reaction? a) CH, = CHCI b) CH,CH,CI ©) CH, =CHCH,Cl 4) (CHY,C - Cl Which of the following hus highest dipole moment? a) CHCl ») CHE ©) CH,Br 4) CHI |. 1.3-Dibromopropane reacts with metallic zine to form a) propene b) cyclopropane ©) propane 4) hexane - CH, Ma x SS oy vis a) CH,CH,CN b) NC -CH, - CH, - CN ©) Br— CH, ~CH,CN 4) Br~ CH = CHCN A primary atky! iodide on treatment with dry silver oxide gives a) Diethyl ether 'b) Ethyl methyl ether c) An uleohol d) An ether HOH ; Te pod formed in te action 3 + SOC, + ws More than One correct answer ‘The less reactive alkyl halide towards teaction than ethyl chloride soc, ———&) SOC, Which of the following. does/lo pl-— sar li ring. une formation of FodoForm fr ‘¢) Hodination 17 Which of the following pwocosse a) Oxidation fb) Redwetion 1X Whick af the following statennen 1) Alky! chlorides are lighter than water 1) Tetrachloromethane is heavier than waler «<) Alky chlorides undergo nucleophilic substitution mors easily than alky! bromides canneet” reaction 4) Floonsdenzene can be prepared by Sandmeyer’s © Which of the following compounds would yield chloroform on warming walt bleaching pow, poste a) IsPropanol b) Propanone c) Ethanol d) Propanal 20. Winch of the following spbstrate(s) upon treating with a base at higher temperature will yieye predominantly Hoffmann’s product CHHCHCHCHCH: HCH: CHCHCH, Cie CH;-CH-CH-cy, x b) EY 1 7% a mh Be In the given reaction ac{ =i [Xs EX] will be H( weCrmet) << HO a 22. CH=! i CH= CH; 42" 5 (X) major Br ie fs . a ‘ CH;-C-CH=CH; ») CH — 7 CH=CH, cH a i h-C-CH=| 4 co of oyMatri> MeALIDES >” 28. Match the following reactions with the corresponding: Column-L A) CF,-CHCI, He KoWls , CF, = CC p) CH, =CH- CH, 2S CH, = CH~CH,CI ©) CH, -CH, pr —2KOW/s_, CH, = CH, D) (CH),C~ Br H+ (CH3),6 = CH The number of structural isomers possible for C,H, Br is in an alkyl chloride to exhibit optical activity is of following reaction, Mininum number of carbon atom ii Find the maximum numberof ehlorine atom which {s present in major products obtained during the reaction. . Find the total number of possible monobrominate product CH=CH) NBS Ween ncaa) HC Ota Se onan Bp 'C PCly ‘D> > e ‘The number of 7¢ bonds in *D’ are - CHC], A “A 80,5501, +G!. The no. of oxygen atoms in ‘G’ are - How many primary halides (excluding stereo isomers) are possible for the molecular formula C,H, Br?Arrange the following in increasing order of reactivity in an S.2 reaction with KI in acetone solvent. i (renner Oe O-ye Ons CH «ay ai c P) Swi Pat iv we a me CH, OH 8) 0 +s0ci, nat, ee @ Se ® (Ss) ° aya Bese aor > D S¢ CH; aN fe a hs oe + ” wes wa cat Sa ie Column-T Column-Il (Substrate) (Relative rate of solvolysis in 50% in ‘aqueous ethanol at 45°C) a a p) 7700 B ~~p> Br a) Bey EOL (X) products » Zoe se Kot (yy Br CH > iy 4 ony} sO 5p ‘Br Br CH; Sum of X+Y+Z+P= 6. If 1,)-dichloropropane is reacted with aqueous NaNO, solution, only one of the chlorine undergo nucleophilic substitution (S,2) reaction. How many mono-substitution products would be formed? (including stereomers) | How many of the following are stereo specific? 18x 2)Sya )E, 4B, 3) Exe 6) Additions of Bayers reagent 7) Pinacole-Pinacolone rearrangement, How many of the following compounds encourages ‘S,z' mechanism? CHy=Br CH; -Br CH;-Br CH; -Br ce “ oO D) NO; COOH OCH, CH, -Br CH; - Br ) o) : : fi Hy How many of the following give more amount of r-mixture in an S,; reaction, when compared toWhich of the following compounds will show faster Ar Sy e a Br : » » 2 4 No; No; NO; Correct reactivity order for Aromatic nucleophilic substitution (AiS,,) reaction for the following is: ci cl he al ON. ANO; ON A a ; ofl i YU » UO » NO; NO, NO2 NO, a)i>ii> ili>iy b)ii>i>iv> iii oii >iv> iii >i 4) iii >ii>iv>i Which one of the following compound will be most readily hydrolyzed in aqueous alkali 1 ca 1 a NO; NO; a) » °) 4) 0; ow’ NO NO} Br dey cher (E130) The product Z in the given reaction is : 2 + 2Na So te (E40) 674+ 2NaBr i nO -OO .ae Arrange the following compounds in‘decreasing order of rate of solvolysis reaction. i) (Oct —Br ii) HC Oc: CHa iii) CHs—CH, ~(O)-etis-Br iw CH CH, a) ii>iv>ii>i b) iv>ili>ii >i 9) iv>i *)i>ii>ili>iv Which of the following is most reactive towards the reaction with EtONa? Br a » 9 o NO; NO; NO; 2correct answer T)Linked Comprehension Type Questions eel: ‘Aliphatic nucelophilic substitution mainly place by twa mechanisms (ie) Sys & Spar Primary halides mainly undergo by Syx mechanism and are favourable in polar aprotic solvents. Sixt reactions takes place mainly By tertiary halide and are more favourable in polar protic solvents. In case of tertiary halides, E, comes competetion to Sy1 reaction. Keeping in view of these general points, answer the following questions. fod. Which of the following ractions, the reactions takes place by S,y) mechanism mainly. CHBr CH,CH,CI a a) cy b) cr °) cy d) CH,CH,CH,Br |. (4)CJH,CH(CH Cl» (4)C,H,CH(OH)CH, in which of the following solvents, the above reaction is most favourable a) 7S% water + 25% CH,OH b) 25% water + 75% methanol ©) 100% methanol d) 10% water + 90% methanol rassage-IT = ‘Aryl halides are tess reactive than alkyl halides due to the presence partial double character of €-X bond in aryl halides. Arly halides undergo nuclephilic substitution reactions, if electron withdrawing groups are introduced in ortho & para-positions in aryl halides. The reaction mechanism involves two steps. Keeping these points in view answer the following questions. 166. Which of the following is the correct order of reactivity of the aryl halides with a given ruclephile? FP C1 Br I D Cr 1) oy m Iv) ajI>I>lI>Iv b)IV>M >>I o) l=-M=M-=IV d) I>>=M=1V 27, Which compound undergo nucleophilic substitution under mild conditions? a cl NOx CO Ge » ° NO; No; NO; Matrix Matching Type Questions Column-I Column-! cl A) el a. p) Friedel-Crafts reaction q) Electrophilie substitution35. How many of the following will give 3° alkyl halides up on reaction with Bryhy. io VW of) oC iomie © 4 exercise. jit (Mixed Problems) nt Objective Type Questions 1. Reactivity onder with respect to alkyl group of Hunsicker reaction is i . a) I> 2°>3° b) 38> 2°> 1° 6) 99275 1° dP =2)>3 CH,CH,CH,c| Mester, 4 SiON By 50: Ba Care a) CH,CH,CH,CH,, CH,CH,CH, b) CH,CH,CH,OCH,. CH,CH,CH,D ©) CH,CH,CH,, CH,CH,CH,D ) CH,CH,CH,, CH,CH,CH,OD CCI, does not give a precipitate with AgNO, because: 4) it forms a complex with AgNO, €) precipitate is soluble in CCI, b) it does not ionise to give Cl- ions 4) AgNO, does not give Ag* ions. 4. Which ane of the following compounds most readily undergoes substitution by Sy2 mechanism? CH, ne 1 HC... Cis a) HC eee ° wel 4) ‘3H, H3C cl cf Mos stable carbocation formed from (CH,),C ~ Br, (C,H9),CBr, (C,H),CHBr and C,H,CH,Br would be ® . % 5 a) CH,CH, 'b) (CH,),C ©) (Ces), ¢ 4) (CgHs), CH 6. The Order of decreasing nucleophiticity of the following is a) H,0 > OH” > CH,COO- > CH,0- ©) CH,COO- > CH,O-> OH-> H,0 7. Consider the following anions. ») CH,O-> OH- > CH,COO- > H,0 4) HO- > CH,O- > CH,COO->H,0 o oO ie 1. 3 CBE Gits-S-0 or I a 4 CH, —C_ 9 @ (hy, (ny, (Iv) ‘When attached to sp?-hybridized carbon, their leaving g ability in nucleophilic substitution reactions decreases in the order, ie! : a)I>1>M>1v byl >>IVomr SIV>Io1>m‘More than One correct answer Type Questions 16 Identify the alkyl halide(s) that produce a terminal alkene as major product on treatment with ‘alcoholic NaOH or KOH a a F ( a aes si 3 ol: 4 Sea H 4 ef H 17. Consider the following reaction: cl Cha +H —> x When a pure enantiomer of X is taken in the above:reastion, correct completion reagarding the reaction is/are a) Four (stereo) different dichlorocyclohexane are formed as significant products b) a pair of enantiomers is formed ¢) two pairs of diastereomers are formed 4) product mixture has zero specific rotation 18. Which is/are true statement(s): 4) Protonation increases electrophilic nature of carbonyl group b) CR,SOsis better leaving group than CH,SO5 is stabilized by resonance ¢) Benzyl carbonium i OH d) cacn< is stable, due to H-Bonding Linked Comprehension Type. Questions Passage-I The nucleophilic substitution reaction taking place in aromatic system are designated as SyAr. In fact aryl halides do not easily undergo nucleophilic substitution under ‘ordinary conditions. ‘However, introduction of electron-withdrawing groups in 0, p-positions makes the reaction to g0 faster. Keeping these general points in view answer the following questions. ir 2. ON oO product. The solution is tealed with aqueous [AgNO, solution. Which of the following CH; is correct? _ a) A white precipitate of AgCl is formed ; b) A pale yellow precipitate of AgBr is formed ~ ¢) No precipitate of any kind is ¥ 4) A mixture of AgCl + AgBr formed oo20. Which of the following struetures is correct in the ™ cl cL NH, cl >>» aL AN A IE] Passage-IH ‘These problems differ from thoxe in earlier chapters in that core material rather than using a descriptive passage (0 exten idens. The number of factors that contribute to nucleophilic sui The really major ones, though, are few and readily applied to specific mechanism to guide your analysis. 23. Which compound undegoes substitution by the S,i mechanism at the fastest rate? Bi pA ayes Bly Br they direetly test your knowledge of id the material or introduce mew stitution can be daunting. by using the Sy and Sys PHy H——Br J 7 PAs ie. a > What is the major product of the reaction shown’ CHCH CH) Hy "Hy CH, f CN nc—}-H H CN NCH a) HAC. H ») Hjc—+—4 ou CH, 4 - CH, CH.CH, CHSCHy CHACHy HCH, Matrix Matching Type Questions 25. Column-f Column-Il A)E,cb p_ Fist order B) Sy 4) No rearrangement OE, 1) Rearrangemnt D) Sy 8) Strong nucleophile 1) Inversion of configuration Numerical / Integer Type Questions 26. Identify the substrate those can give Sy andS,q reaction both. CH, ons Br (\-« -Br. etc. ex f i) , PS CH, Hy Br Ph HC ay @ G) 4 ) bm co) ay Br or cr OG. © o 6 oyALKYL AND ARYL HALIDES