Haloatkanes and Haloarenes 53 ‘= Points to remember ¥ Halogen derivatives of alkanes t + Monohalogen derivatives Polyhalogen derivatives One hydrogen atom of an alkane is More than one hydrogen substituted by one halogen atom. atom of alkanes are General formula CyHayiaX substituted by correspo- [nis an integer} nding number of halogen R-X[X=F, CL Br, Land lun R= alkyl group] Bg, CH, ~ CH, ~ Br Ethyl bromide (Bromoethane) Dihalogen derivatives Trihalogen derivatives ‘Tetrahalogen derivatives Two hydrogen atoms of an || ‘Three hydrogen atoms of an || Four hydrogen atoms of an alkane are substituted by ]| alkane are substituted by || alkane are substituted by two halogen atoms, three halogen atoms, four halogen atoms. General formula :C,HagX2 | | General formula :CyHsy4Xq_| | General formula: C,Hey 2X. IX=F, Cl, Br,land‘nvisan | [X=F,C)Brlandnisan || |X=F,Cl Br, landnisan integer] integer. | integer.] eg. CHI, eg. CCl, Todoform Caron tetrachloride Geminal dihalides Vicinal dihalides Both the halogen atoms are Both the halogen atoms are attatliel ty saute Caton attached to adjacent (vicinal) °g. H Catom, I e . IkC —C— Dr BHCC ! Br Br Ethylene dibromide (1 LDibromoethane) 2 Dibromoethane) Primary alkyl halide (1 Secondary alkyl halide (2 Halide group is attached to | | Halide group is attached to primary carbon atom of an | | secondary carbon atom of an alkyl group, alkyl group. eg, CH,CH,CH,Br °g cH, n-Propyl bromide I ‘-Bromopropane HyC—¢— Be H Isopropyl bromide @-Bromopropane)5a MHT-CET - Part II Std. 12) 1 Markownikoft’s rule and Anti-Markowniff’s rule: H.C— CH=CH, Propene HYC— CH=CH, Propene Hor CHy—CH—CH, + HyC— Crh —CHBr Markownitts > Tf H,C— Cl, — CHB: = Br 1-Rromopropane DeRenmopepane (Minor product) ‘Major produch Hbrperoxide - SC —crk—CH,— Br + .C— CH cH, “Ant Markowniffs i rule “romopmone 1 (Major produc) sen pune (Minor product)Haloatkanes and Haloarenes . (Haloalkanes ) H.C— cH, Ethane HyC= UM, Ethane Halethane accl Preparation of alkyl halids : {Chy suntight inv) ‘Or UV light Br, ‘Anhydrous ATBr, L HIU,/ HNO, HgU ail) HCI ft HCL Rahydrous ZnCl, HBr (Walir + cone: H,S0p, Reflux cone HI oF GHX L__,| Hiatoethane DCI, BriReactions of alkyl halids : (Haloatkanes) Hydrolysis under pressure Na-O-CHy AlcKOH [X=CL Br, I] Diy ether MHT-CET - Part II Std. 12) Ag. KOH boil AgOH Moist Agi GCN Ethanenitrile GCN Carbylaminoethane (Ethyl isocyanide) (hj CH, NH Ethanamine HyC,-O-CHy, Methoxyethane ° W CH,-0 0 -GH, Fthyipenpannate (ethyl propioanate) Ethyl magnesium hHaloatkanes and Haloarenes © Substitution Rection An atom or a group is replaced by another atom or group without the change in structure. Unimolecular nucleophilic substituion (SN') 1 2 3. 10. u ‘They are unimolecular. Nucleophile may attack from any side. Inversion in configuration may or may not take place. Recemisation occurs. Favoured by polar solvents Order of reactivity of alkyl halides tert > sec> pri> CH,X Fission of C - Br bond is followed by the formation of C- OH bond, A free carbonium ion is formed. Obeys Ist order kinetics Rate depends only on the concentration of alkyl halide. Involves two steps. Kinetic Expression ; Rate = k [ter - butyl bromide] seen 10. "1 _ Bimolecular Nucleophilic Substitution (SN*) ‘They are bimolecular. Nucleophile attacks only from back side, Inversion in configuration takes place. Favoured by non- polar solvents, Order of reactivity of alkyl halies CHX > pri > sec > ter Fission of C - Br bond and formation C—OH bond take place simultaneously, A free carbonium ion is not formed. It obeys 2nd order kinetics. rate depends on the concentrations of both, alkyl halide and nuclecophile (OH) It involves a single step. Kinetic Expression : Rate = k [ CH, Brl[OH] Classification of halogen derivatives of arenes : Halogen d Eg. Monohaloarenes One hydrogen atom Of benzenering is Substituted by one Halogen atom. Br Bromobenzene Dihaloarenes Two hydrogen Atoms| lof benzene ring are pubatitutedby two halogen atoms Eg, Br Br Dibromobenzrne Tetrahaloarenes Four hydrogen atom of benzenering is Sub- stituted by four Halogen atom Es. a a ca a Tetrachlorobenzene| Preparation of haloarenes : OO FelFeCh, dark Br FeBr,, dark Benzene ab x 10} , dark NH, Haloarene (X= CI, Br, 1). Aniline Important formula : For a given optically active compound ; Number of possible stereoisomers = 2" (where n = number of asymmetric C - atoms (¢) precent in the molecule of that particular compound). OH NaOH. 1 SN aR Phevol x pressure Nuelonphile cN iy Substitution X=Cl__ reactions Halosrene ~ (X=, Br, D Cyanobenzene NB, Cus0 NH 473K, pressureMaster Key MHT- CET Part (Std. 12) Reactions of Haloarenes : a a a cl Clp, anhydrous Fe A SS (Minor product) (Oajor product cd cl oO HNU, AF A cone HSU, ~ = NO, 1Chtnntnthonsone (hajor produc) cl cone. H,SO, a j ‘ SO sos 2Chlorobenzene Sulphonic acid 2Chorohensen Suphonte acd ‘Minor product) ‘hajr product a cl cH, It CHC! a il ~ xe aaa =) ~ Ww HalSsvene = cH, KeG Br) 1.Chloro-t-methgthenrone IChlam-2-mehythenzene Gy ether (Minor product (Major produc) a sg cl cay cHcoct ca ZA ae C cl 2.Chtoroacetophenone & (Minor produc) e of cu, a 4Chioroacetophenone (Major product) Na CHI « Nacl dry ether Methyl oluene) (@y product) 2Na L__2Ni_,, + 2NaxBinlogen derivatives of Alkanes and arenes MHT-CET- Part Il (Sta. 199 Pn en my EVALUATION PAPER - HALOGEN DERIVATIVES OF ALKANES AND ARENES: Time : 30 Min. Marks : 25 a @) (@) a) 6) 6) (7) (8) proto oo oe eee ee = == The following reaction is known as C\H,OH + s0c1, P85 C,H,Cl4 SO, + HCT (a) Kharasch effect (b)Darzen’s procedure (c) Williamson's synthesis (d) Hunsdiecker synthesis reaction Which of the following halide is 2°? (a) Isopropyl chloride (b)Isobutyl chloride (0 n-propyl chloride (a) n-butyl chloride In the following sequence of reactions CH,CH,CH,Br 5a) (5) Mes 5(€), The product (C) is (a) propan-2-0l (b)_propan-1-ol (ce) propyne (a) propene An alkyl bromide (X) reacts with Na to form 4,5-diethyloctane. Compound X is (a) CH/CH,),Br (b) CH(CH,) Br (©) CHCH,),CH-Br.CH, (a) CHCH,),CH.Br.CH,CH, When but 3-en-Z-ol reacts with aq. HBr, the product formed 1s (2) 3-bromobut-1-ene (v) 1-bromobut-2-ene (©) a mixture of both (a) and (b) (4) 2-bromobut- Which of the following halogen-exchange reactions is possible ? (a) R-1+ Nach —> (bo) R-F+KCI—> (©) CUE + Agb: <> (a) RCI+ Nat 5 Identify Z, in the following series. Cg 8", x yy yz (a) CH,CH,CN ) (©) BrCH, - CH,CN «@ Reaction of Cbutyl bromide with sudiuin methoxide produces (a) isobutane () isobutylene () sodium t-butoxide (dé) t-butyl methyl ether aHaloatkanes and Haloarenes 61 PT ey, 1 (9) Ethyl chloride on heating with silver cyanide forms a compound X (major). 1 ! ‘The functional isomer of X is ! t (a) GHC (b) C,H CN t (©) H,C-NH-CH, (4) CH,NH, (10) Which of the following is the correct formula of dichlorodiphenyl trichloroethane ? Ho » OL a (a) i (c) @ a cC—c—ca ad ad (11) Most readily hydrolysed halide is (a) CHCl (b) (C,H,),CHCI (ce) CjH,CH,Cr (d) (C,H,)sCCE (12) Aryl fluoride may be prepared from diazonium chloride using (a) HBF,/NaNO, . Cu. & (bo) HBE,/A (©) CuF/HF (@) Cu/HF NH --- eee tMHT-CET- Part Il (Sta. 12) (14) (15) (16) which is not the Wurtz-Fittig reaction > (a) (0) enc vcna > » (ee. (6)-0= (©) (O) erent (d) None of the above ‘The conversion of benzene diazonium chloride to bromobenzene can be accomplished by (a) Gattermann reaction (b) Azo coupling reaction (c) Friedal-Crafts reaction (a) Riemer-tiemann reaction Match the following, List - I List - A) C,H,CI 1) Williamson synthesis B) Mg = dry ether 2) Wurtz reaction ©) C,H,CI + C,H,ONa 3) Anaesthetic D) Na + dry ether 4) Antiseptic 5) Grignard reagent ‘The correct match is c (a) (b) (c) (da) wou aseuw BYNNG Which of the following alkyl halides would be most likely to give a rearranged product under SN? condition ? @) me wo Ader Br Br © MY (a) a, NeeHaloatkanes and Haloarenes 63 Pn ny (17) Chlorobenzene on heating with aqueous NH, under pressure in the presence off cuprous chloride gives (a) Benzamide (b) Nitrobenzene () - (4) Chloroaminobenzene (18) Out of CHC Ch Cl O Q a seeee a NO, I u a Vv which undergo SN reaciton easily ? (a) Allexcept IIT (b) All except II, IV (©) All except I, 111 (d) All except IV (19) Chtorobenzene reacts with Mg in dry ether to give a compound (A) which further reacts with ethanol to give (a) phenol (b) benzene (©) ethyl benzene (4) phenyl ether (20. Friedel-Craft’s reaction of bromobenzene with methyl iodide gives (a) o-bromotoluene (>) p-bromotoluene (©) o-and p-bromotoluene (d)_ m-bromotoluene (21) Which of the following statement is incorrect (a) GHr reacts with ale. KOH to form GH,OH (b) C,H,Br when treated with metallic sodium gives ethane (©) C,H,Br when treated with sodium ethoxide forms diethyl ether (@) Both a and b (22) 2, 6-Dimethylheptane on monochlorination produces derivatives fa) 5 (bo) 6 () 3 (a) 4 (23) In the following sequence of reactions CH,- OH 2, A mitten, B In this reaction, product B is -- = = dO cha ‘alle. — 0). CHAO _ _ Md) CH=64 MHT-CET - Part II Std. 12) Pe my (24) In which case formatiuon of butane nitrile is possible ' (a) GHDi+KCN ()) C,H,Br+HCN ( CH,OH+KCN (4) C,H,OH + KCN I missing item is I 1 I 1 I (25) Chlorobenzene when heated with .... in the presence of conc.H,SO, gives D.D.T. The ! I (a) Acetone () Ethanal (c) Chloroform (a) Chloral Nee eee ee et