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    CHAPTER 21 Halogen Containing Organic Compounds

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    Animesh Srivastava

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    Vidyamandir Classes Halogen Containing Organic Compounds ALKYL HALIDES : [RX] Section - 1 Preparation of Alkyl Halide: In the ‘Hydrocarbons’ chapter, you have observed that hydrocarbons react with halogens to form Organic Halide. ‘These compounds are called halogen derivatives of hydrocarbons, Here, the halogen atom (X) acts asa functional group and is attached to the carbon atom by a covalent bond, These organic halides are of two types: ky! Halids (aliphatic) and. “Aryl talides (aromatic). ‘The alkyl halides are classified into three categories based on type of carbon atom to which the halogen atom is attached. Primazy (1°) Halide : RCH, Secondary (2°) Halides:R,CHX Tertiary (3°) Halide :R,CX (R: alkyl radical, X:F,CLBr,D) ‘The Organic Halides are further classified as monobalides, dihelides and tihalides depending upon number of halogen atoms, vichaloderivative of CH, are known as HALOFORM, Fully halogenated hydrocarbons are also called pethalohydrocarbons. (C,X,,.-2).For Example :Perfluoroethane C.F, Halogenation (a) From Alkanes: Halogenation of alkanes is carried out in the presence of heat or light, Chlorination is fast, bromination is. slow while directiodination isnot possible as the reaction is reversible Direct halogenation does not form pure mono-halogen derivatives since a mixture of polyhalogen derivatives is always ‘obtained, For example, in chlorination of Methane we get amixture of products. cH, —2__, cuca + cul, s+ cH, + cy, Methane hv or 520-670K ” Chloromethane _Dichloromethane Trichioromethane ‘Tetrachloromethane (chiorform) In case of higher alkanes, even mono-halogenation gives a mixture ofall the possible isomeric haloalkanes. cH,cH,cH, 2 ,cH,-cH, -CH,-cl + CH,-CH(C)-CH, Propane” 288K .chioropropane(@o%) _-2-Ciloropropane(55%) CH,CH,CH,CH, 92", CH,CH,CH,CH,C] + CH,CH, -CH(C)-CH, 298K 1 chlorobutane 28%) 2 Chlorobutane (72%) In general, the ease of substitution of various hydrogens follows the sequence | > 2° > 1" > CW Jodinntion is reversible, butt may be carried out inthe presence of an oxidising agent, such as, HIO,, HNO, , HgO, etc. which oxidises HI sit is formed. CH+1, BS cHi+u ; sHl+H10, —31,+38,0 ‘Plourination The best way to prepare alkyl fluorides is by halogen exchange. An alkyl chloride or bromide is heated in the presence of a metallic fluoride, such as Ag. Hg,F,, CoF or SbF, to give alkyl fluorides. Set Stuy Course or TEE with One Suppor 1 Organic Halides CHBr +AgF —> CHF + Agbr Bromomethane Fiuoromethane 2CH,CH, ~ Cl + Hg,Kj —> 2CH,CH, -F+ Hg,Cl, Choroetnane Fluoroethane This reaction is called Swarts reaction, When the organic halide contains two or three halogen atoms on the same carbon, CoF, or the more easily available SbE, is used. For example, 3CH,~ CCl ~ CH, + 2SbF, —s 3CH,-CK,-CH, + 28bCl, 2,2-Dichloropropane 2,2-Diflusrepropane (b) From Alkenes Alkenes react with halogen acids to form haloalkanes. The order of reactivity is : HI> HBr> HC1> HF. CH, +HX —> RCH-CH, I x The unsymmetrical alkenes follows Markovnikov’s rule during addition forming secondary or tertiary alkyl halides predominantly. Notes In presence of peroxides, the addition of HBr only (not HCI or Hl) to unsymmetrical alkenes takes place via Anti Markovnikov's rule forming primary alkyl bromides. Thisis known as yo video//eesor Kharasch effect HBr CH,-CH-CH, (Markomitov'sadition) CH,CH=CH,— hae Peroxide) (Anti-Markownikov's addition) (c)_ Allylic halogenation : When alkenes (except Ethylene) are heated with Cl, or Br, ata high temperature of about 773 K, the hydrogen atom at the allylic carbon (ie., carbon next to the double bond) is substituted by a halogen atom. For example ci, -cH=ct, +c, 2% cic, cen, 3-Chloroprop-t-ene (Ally chloride) However, a more specific reagent for allylic bromination is N-bromosuccinimide (NBS). ,c0 cH,-cH=cH, + Sear Be cnco 2 “H = CH, (Ally bromide) Allylic chlorination ean also be carried out with sulphuryl chloride. 415K, by CH, -CH=CH, +S0,C, SEER ClCH, ~CH=CH, + HCl +0, 2 EEE, sere stucy course for 112£€ with Ontine Support Ric eu ee Organic Halides 2. From Alcohols : Generally alkyl halides are prepared from alcohols by ceplacement of -OH group by an hhslogen ion. This is usually achieved by using HX or PCI, (a) By the action of Halogen acids : Catalyst R-OH+HK >R-X+H,0 ‘Note: () The order of reactivity for halogen acids is : HI > HBr > HC1 and for alcohol is : 3° alcohol > 2° alcohol > 1° alcohol. (i) The catalyst used is generally a dehydrating agent such as ZnCl, or cone. H,SO, (Using He1 CH,CH,OH + HC) Rb CH,CH,C1+H,0 CH, -CH-CH, + HC1(e) BH CH, —CH-CH, + H,0 1 wt 1 on a Anhysdrous ZnCl, helps in the cleavage of C- 0 bond. Being a Lewis acid, it co-ordinates with the oxygen atom of the alcohol. As a result, C 0 bond weakens and ultimately breaks to form carbocations (C"), whieh form chlorides (CH,),-C-OH + Hel ISS (Cl), -C-C1 + H,0 (cone) ° . ‘The yield can be improved when the vi outs of alcoho! and HCL ae passed over alumina a 350°C (il) Using HBr: Alkyl bromides are obtined by reftning the alcohol with constant boiling in HBr (40%) in presence of litle cone #80, CH,CH, - O11 + Br SCF S08 CH,CH,-Br+H,0 C,H,OH + KBr+H,80, —> C,H,Br+KHSO, +1,0 Note: The mixture of KBr and H,SO, is not used in case of secondary and tertiary alcobols as their dehydration may occur, to give alkenes, (ii) Using HI Reflux CH, -CH, - OH + HT » CH,CH, -1+H,0 cron +Kr+1h20, 25 cH. +KHL20, +110 (b) By the action of Phosphorus Halides : Phosphorus halides react with alcohols to form haloslkanes in excellent yield (80% or above), ROMs PX, —> R-X+ POX, +X ere X can be either chlorine or bromine ot iodine. 3ROH +PCI, —> 3R-C1+H,PO, Self Study Course for IITJEE with Online Support 3 Organic Halides Ric Sores Since PBr, and PI, ate not very stable compounds, these are generally prepared in stu by the action of red phosphorus on bromine and iodine respectively. Py + 6Xp —> 4PX3 R-oH ~**2,R-pr ; R-on +2, R-1 ‘This method gives good yield of primary alkyl halides but poor yields of secondary and tertiary alkyl halides. ‘The method is useful for preparing lower alkyl bromides and iodides inthe laboratory. {@) By the action of Thionyl chloride : (Darzen’s method) Chloroalkanes are conveniently prepared by refluxing aleohol with thionyl chloride (SOCI,) in presence of pyridine (C4H.N). R-OH + Socl, Pailin’, C14 $0, T+HCIT Reflux Thionyl chloride method is preferred over hydrogen chloride or phosphorus chloride method for the preparation of Chloroalkanes since both the by-products (SO, and HCI in this reaction being gases escape, leaving behind chloroalkanes in almost pure state ‘Note: Bromides and iodides are not prepared by this method, because thionyl bromide is unstable and thionyl iodide does not exist 3. From Silver salt of fatty acid: cu,cH,cooag + te, SSH RE oH. oH, Be 4C0, ABBE This reaction is called as Bovodinne Hunsdiecker reaction and is a free radical reaction. This reaction gives the product with one carbon atom less than the fatty acid, The yield of the alkyl halide formation with this reaction is primary > secondary > tertiary, Chloroalkanes can also be prepared by this method by using Cl, instead of Br, butthe yields are poor. With I, silver salts sive esters instead of iodoalkanes. 2RCOOAR-+I, —> RCOOR+CO, +2Azh ‘Note: This method is very popularin the formation of aromatic bromides as the yield is very high. Halogen exchange reaction odoalkanes can be easily prepared from the corresponding chloroalkanes or bromoalkanes by heating with sodium iodide in acetone or methanal. RX+Nal ASP RI Na X=ClorBr ‘This reaction is called Finkelsrein Reaction Its a halide exchange reaction which involves a substitution of CUBr by I. The reaction was specially designed to prepare indo-alkanes which were not easily prepared using simple halogenation method. (Due to the reversibility of Todination) R-X+Nal AS", R-1+Naxl x 4 Self Study Course for IITJEE with Online Support ‘Lor Br ‘Note: Fluoro alkanes are di Nie eucUr ume Organic Halides Reaction is believed to be based on the principle of greater solubility of Nal in acetone as compared to NaCl or NaBr because of greater covalent character in Nal. That is why despite of being a weaker reagent than CBI, Fstll substitutes them and the NaC/NaBr formed precipitates out driving the equilibrium in forward direction jcult to prepare as all the hydrogen atoms are replaced by fluorine. The monofluoro alkanes are prepared by heating alkyl halides with KF in diethyl glycol KE. RX (CHO), RF +KX Physical Properties : Physical state, colour, odour, ete : Alkyl halides are colourless when pure, but bromides and particularly iodides develop colour when exposed (o light, Methyl chloride, Methyl bromide, Ethyl chloride and some Chlorofluoromethanes and Chlorofuloroethanes are gases atroom temperature, Other chloro, bromo, iodo compounds are ether liquids or solids. Many volatile halogen compounds have sweet smell 2. Melting points and boiling points : The melting points and boiling points of haloalkanes are several degrees higher than those of parent alkanes mainly due to greater magnitude of van der Waals forces of attraction, For the same alkyl group, the boiling points of haloalkanes decrease in the order : RI> RBr> RCI> RF. This is because with the inerease in the size and mass of the halogen, the magnitude of the van der Waal’s forces of attraction increases. For isomeric alky1 halides, the boiling points decrease with branching, because with branching the surface ares ofthe alkyl halide decreases and hence the magnitude of the van der Waal’s forces of attraction decreases. ‘Tae boiling points of chloro, bromo and iodo compounds inerease as the number of halogen atoms increases. 3. Solubility : Even though haloalkanes (dipole moment, 2.05 — 2.15 D) are polar molecules still they are insoluble in water, This is due to the reason that haloalkanes can neither form hydrogen bonds with water nor can they break the Bydrogen bonds already existing between water molecules. However, they are quite soluble in organic solvents of low polarity such as petroleum ether, benzene, ether chloroform, carbon tetrachloride ete 4, Density Their relati Alkyl fluorides and chlorides are generally lighter than water whereas alkyl bromies and iodides are heavier, densities follow the order: RI> RBr> RCI. "The density increases with increasing number and atomic mass of the halogen, CHCl, < CHL, < CC, 5. Stability : Since the stength of the C—X bond decreases in the order : C-F>C—Cl > C-Br> CI, therefore stability of the haloalkanes having same alkyl group is in the order: R-F>R-C1>R-Br>R-L. ‘Thatis why alkyl iodides, on standing become violet or brown because of their decomposition in presence of light to give iodine. ap-1 HEM, RR +I, 6. Dipole moment: CH, ~ Cl> CH, —F > CH ~ Br> CH, ~ set study Course for IEE with Ontne Support 5 Organic H Reactions of Alkyl halides : The alkyl halides are highly reactive compounds due to the polavty of C - X. The order of reactivity is With respect to halogen atom: #1 = RB: RCI 5 With respect to alkyl groups: 3 >2)> 1 1. Nucleophilic Substituti be In alkyl halides, C— X bond is highly polar, so nucleophile (Nur) attacks electrophilic carbon atom easily. Hence alkyl n Reai ons : halides give Nucleophilic Substitution Reactions readily, The halogen atom is replaced by a wide range of nucleophiles to give almost all important organic families. R-X + No R-No eX Nucleophile Leaving group Note: > Nucleophile isa species which is seeking to attack electrophilic region ie, carbon with a +ve charge or 6+ charge. Itis| able to share its rich electron cloud with electrophilic species, Some important electron rich nucleophiles are OH CN ,RO",RCOO” and HS ions, > The mechanism of nucleophilic substitution reaction will be discussed in next chapt Organie Concepts! (i) Substitution by aq. KOH : Rev x+ Ko! By ReHon +x {i) Substitution by moist Silver oxide (AgOH) : Ago 2°, sgon RCH,X+Ag0H —> RCH,OI+AX (lil) Substitution by Sodium alkoxides (RONa) : CHO" act as strong nucleophile and atacks on alk halides to produce eters. cur ec Nat 85 cH,-0- crn +a The above reaction is called as Williamson's synthesis of ethers. Note: (i) 2° and 3” alkyl halides, however prefer to give alkenes as elimination products. )) The ethers are also prepared by use of Ag,0. 2RI + Ag,0 —Y ROR + 2Agi tary (lu) Substitution by Hydro sulphide group : (Formation of Thioalcohols). RX + Nasi R-SH + NaX Thigaleohel 6 QUETCUNNNNNNNNNIIA,. ser stay course for rs with ontne Support HOH 11,0 SaHSOH/ QO, a Organic Halides (v) Substitution by Mercaptice group : (Formation of Thioethers) {a) By heating an alkyl halide with Sodium or Potassium mercaptide : RX + NaS’) ———> R-S—R’ + Natx™ Thioether ium sulphide : (b) By heating an alkyl halide with Sodium or Pota 2R-X +Na,S ———> R -S-R 42NaX ‘Thioether (vi) Substitution by Amino group : (Formation of Amines) Haloalkanes when heated with an ethanolic solution of ammonia ina sealed tube at 373 K, form amixture of 1°,2° and 3° amines along with quaternary ammonium salts, next) BOS i eae Pane ‘Note Ifalkyl halide is in excess, then 2° and 3° amines and even quaternary salts are also formed. rx rn, BX a XS pw BK Ry Sac "Amine ZAmine 3°Amine (Quaternary salt) This reaction is called Mojjnann's ammonolysis of alkyl halides. (i substitution by Cyanides bo) Racy EAROWHEO 5 Roy 4 KX ACCNisanionc compounding Ces mulepie mies Tote is resco ali ali Xen) ead of waa lininaton occasion lio (ON wg atase apn bales) 1,0 Wore: R-C=N "25 RooOML NUE (b) RX FAgCN CoHSOHIO | RNC 4 AgX “ Isocyanides (AgCNis covalent compound giving = C, an ambident nucleophile) (vili) Substitution by salts of Carboxylic acids : ° i eBr+8 COA EBM, ROH — ON Age Ses (i) Substitution by Acetylides : (Formation of higher alkynes) RX + R)-C=C-Na—> RO“ C-R + NX Sodium Alkynide Higher alkynes Note In this reaction also, if alkyl halide, RX is tertiary (3°), instead of substitution, elimination occurs to give an alkene. Self Stuy Course or IEE with One Suppor 7 Organic Halides ‘Sodium alkynides are themselves prepared by the action of sodamide (or Na in lig. NH, st 196 K) on terminal alkynes. Lig. NHy R-C=CH + NaNH, 5 R-€ CNa + NH, (Substitution by AgNO, and KNO, CyHOH/H,0 RX+KO-N-0 >» R-O-N-0 +KX ‘ Alkyl nitrite © 0 CyHsOH/H0 RX+Ag-O-N=0 —SHBOBMDO | gy so +agx Nitvoalkane (xi) Substitution by N,- (Azide ion) RX+N7—3 RN + X Alkyl azides 2. Elimination reaction with ale. KOH/NaOH : (Dehydrohalogenation) RCH,CH,X —=_, RCH=CH, + KX +H,0 KOH. plkenes Ifthe structure of the alkyl halide is such that it can undergo climination in two different ways, duc to availability of different types of B-hydrogen, then the more highly substituted alkene is the major product of dehydrohalogenstion. This is known asSayteeff’s rue, Boa 8 ale, RCH, -CH-CH, <> RcI i KOH CHCH, + RCH,CH=CH, + KX +H,0 Major Minor x The reaction is also referred to as B-elimination (1,2-elimination), as f-His lost. In general the ease of dehydrohalogenstion for a given alkyl group decreases in the order : 3° > 2° > 1” and for a given halogen, the order decreases as: R-I>R-Br>R-Cl ‘Note + ‘Theabove elimination also achieved using alkoxide (RO /ROH), as discussed in "Organic Concept 3. Action of Heat: ‘Al halide whe ested above 300°, tendo lotamolecale a yon forming alkenes rence °C, pen cuy, sim ‘The decomposition follows the order With respect to alkyl group :3°>2°> 1° and With respect 5 CUETETUNEEENNIINIIIA,.—serstacy course for se with ontine support halogens : R-I>R-Br>R-C1 Ai eueuumecs Organic Halides 4, Wartz Reaction: - 2RI+2Na #5 R-R + 2Nal br Ne oat +c cl + Reaction usually gives 7 oe mixture of products This is referred to as “intramolecular wurtz reaction”, 5. Formation of Grignard Reagent RX+Mg —“ 5 R-Mp-x ‘Alkyl magnesium halides ‘heal magnesium halides known at Grignard Reagent. The chemist Grignard Reagentsdiscase sections & Reaction with ther active metals cuore + 241 P25 cca + ibe Alkyl lishiums are similar in properties with Grignard reagents. These are highly reactive reagents. 4CH,CH,Br + 4Pb/Na = —P2_5 (CH,CH,), Pb + 4NaBr + 3Pb y ether Ethyl bromide Sod. lead alloy Tetraethyilead (TEL) Tetraethyl lead (TEL) is used as an «i-Anocking agent in gasoline used for running automobiles. 2C,HyBr + Na—He = —> (C)H), He + NaBr Sodium amalgam Diethyimercury Esher 2C,HsBr= 22 BME 5 (C,H), Zn + ZnB, Dialkyl zine compounds are called Frankland reagents 7. Redu (Formation of alkanes) () Hydrogen in the pretence ofa metal eaalyst such as Ni or Pd or Pt exe, 4 pat ux 7 (i) Hydronic acid in the presence of red phosphorus Red HCH, -1+ Ht S225 cH - crt + i) Nascent hydrogen produced by the action of zinc or tin on hydrochloric acid or by the action of zine-copp. ‘on aleohol Zn + HCL cu,cH,cl —_1 #el_ ‘oF ZaCu + alcohol » CH, -CH, + HCI (iv) Substitution by hydride fon : 11 from LiAll1, acts as a Nucleophile (8 ay te no R x SSP Roux (Grom iA) LAI, + 4Rx 22 ether Self Study Course for IITJEE with Online Support 9 AR-H+AIX, +LiX (R 43° alkyl group as 3° RX prefer elimination) Organic Halides Tertiary alkyl halides, however, undergo dehydrohalogenation to give alkenes. On the other hand sodium borohydride whereas tri-phenyl tin hydride (Ph, Snl) reduces (NaBH, reduces secondary and tertiary alky1 halides but not primary all the three types of alkyl halides. 8 |somerisation + When a haloalkane is heated to 573 K or at a lower temperature in presence of anhydrous AICI, (Lewis aca) itundergoes isomerisaton, a i - « sx cit, cit, cl SBR ct, Ce ifehdbal Identify the compounds A, B, in the following reaction setup. cot, NBS 4_HBfPeroside , y Nether KN, pt AKO, pt »E SOLUTION : CH SEGA Wisalz allie substation in alkenes) Hence CH, is an alkene (Note that C,H, also represents cyclopropane) cxycr cH, S25 cH, cc, ZEB cH, cH, cH “| eee LoL tantieMarkovnitow’s addition a a ) ch ; ons Nether © sol Su (Major) CH, (Minor ‘Wurtz Reaction cyecherone _eylopronane HO" KCN, cH, —CH=CH, > CH, —CH=CH, swceopite | | Substtaton CN) coon wecion Ho © wen —"2_, rcoom cH, — Coon +(Co,+,0) < © __] Terie © Coot Malone acid ‘Note: Heating effect on Di-carboxylic acids and fi-Keto ack OxalicAcid: (COOH, —+ H,0+C0+C0, Malonic Acid: CH(COOH), + Co, + CH,COOH, A CH- COL cH,CH,- coo” —*> | « Succinie Acid: HOOC. 1, CO~ B-Keto acid: CH,~C-CH,-COOH —*> cH, cH +CO, oT ° io) WRECTUITRN say cours foritsze with onine Support “dentfy (A) to (Gin the following series of reactions. Also identify the major product among F and G. alcKOH NBS Br, Gyelopentane Fei» A ROT, gp ES. be agKOH Ne > F sowie a, pr KOH, [Ny vas, FY BE iinnt (A) @B) Br Leet, Son Ss ons utes SS = xa — S| S (©) Br e) ®) oO «@) were foscceonens)—bethven reac 2 oie some ene Note : (i) Diene (ie. elimination product) will be majorhere, since conjugated diene is highly stable. Usually cycloalkyl bromide (29 prefer elimination over substitution with RO™ (ii) OFF (ag) acts as a nucleophile whereas OHT (alcoholic) acts asa base, UESESSUEST identify P, Q, R, .... in the following reaction set up. Wy p NBS, NBD. Cen ar ah ° ‘ a ale) ) HBr, g 1b 7M ou ARES, y set, yO, cl, ‘MeOH ce QO mn OQ . cer TaD, (Q) Br D (Reduction using Das Nu) tu, _NBs_, 7 “ean caer “ca,” fA corey vows synthesis (Allylic bromination is preferred at 3° carbon) / ™ ¢ Cyclohexanone [More stable: Saytzeff's Rule] Self Study Course for IITJEE with Online Support cr SOLUTION : Organic Halides IN-CHAPTER EXERCISE - A 1 MentifyA,B. C, 0) Cty gare esis o HCH Br A> CoHgCH,COOH 2 Mentify (A), (B), (Ch... in each of the following, )—— cHcH,cH,on PEs (4) AEKOM_, (py Br, (ce) ARN, (py oy (City), cx1cr AKON, (4) MNO (py 800%, (cy tact) © cHycH,cH = cH, SE (4) Ale KOH (7) #5 (c) CH (CH,), Mer HOH, (4) P25 (py BONE, (6) 5 (D) Ere | Bonnwon Choose the correct alternative. Only one choice is correct. °3. Which reagent cannot be used to prepare an alky! halide from an alcohol ? ()Het+Zncl, Nac © Pel, © soct, “A mixture of wo organic chlorine compounds was treated with sodium metal in ether solution. Isobutane was obtained 4s one ofthe product. The two chlorides are (A) Methyl chloride and propyl chloride (B) Methyl chloride and ethyl chloride (©) Isopropyl chloride and methyl chloride (0) Isopropyl chloride and ethyl chloride 5. Amalkyl Bromide (X) reacts with Na to form 4, $-diethyloctane, Compound X is () CHYCH,,Br ©) CH\CH),Br (© CH\CH) cH BrcH, (D)— CHKCH),CH.BrCH,CH, *6. Inwhich one ofthe following conversions phosphorus pentackloride is used as a reagent? () -HyC=cH, — cH CHC @) -HC-0-cH, — cH, © chron — crn ©) HC=cH— cH,=cHe 7 CH,Brcan be prepared by (A) CH,COOAg+ Br, 45 (B) CH,+NBS —> (©) Bothare correct D) None is correct 8. Increasing order of rate of nucleophilic substitution is (| RFeRCIsier onsets atio aniline Benzene diazonium chloride ‘The formation of benzene diazonium chloride is known as Diazotisation. (a) Sandmeyer Reaction : recut BS fore nel cucl ca: Nyer+ Cur Br Note that Fluorides and Iodides are not formed in this manner, (b) For iodides : (Oy eres 2 (Orono Note that itis not Sandmeyer reaction, (0) For fluorides Hydroboro ‘Note Haloarenes particularly chloro and bromo arenes can also be prepared by Gailey mann reacvion, lis amodification of the Sondimeyer reaction. In this reaction, a mixture of freshly prepared copper powder in the presence of corresponding ‘halogen acid (HCI or HBr) is used instead of cuprous halide as used in Sandmeyer reaction. The yield of this reaction is around 40%, Self sty Cours or IEE with One Suppor 3 Organic Halides 3. From Silver salt of carboxylic acids : (For bromides only). ca,cooAg + By SEL Cat, — Be + C0, + Aer ‘The above reaction is known as “unvicker Reaction”. By this method mainly aromatic bromides are formed asthe yield incase of liphatic romidesis oot RcooAg +Br, £5 RBr+00,+ Abe i +Br, ), + AgBs 4. Commercial preparation of chlorobenzene : act, 1216140, SH neater 28,0 Physical Properties : Physical properties of aryl halide imilar to alky! halide, ‘The boiling points of isomeric dihelobenzenes are very nearly the same but the melting points ofthe para isomers are higher than the ortho and meta isomers. Being more symmetrical, the para isomer fits better inthe erystal lattice of the solid form, than the ortho or meta isomers. Boilingpoint 0>p>m Meltingpoint — p>o>m Reactions of Aryl Halides : Arylhalides are relatively un-reactive towards nucleophilic substitution under conditions which are used for alkyl halides since the lone pair of electrons over halogen atom is involved in resonan + with benzene ring. ca ‘i (iy “Ww “ Resonating Structures of CHorabennene Resonance Hybrid Asa result of resonance, a-C oftring loses its cleetrophillic character, so Nu fails to attack a-C in aryl halides. Duc to resonance, C—Cl bond acquires partial double bond character (CCl), which is difficult to break by Nu". For example, lorobenze e doesnot react with ag, NaOH. It does not give a precipitate of AgCl with alcoholic AgNO,, However, Aryl halides show nucleophilic substitution reaction under dvastic conditions 0 along with use ofcopper salts. high temperature and pressure 350°, 200 atm Clls - C1 + NaH 2 CcHs -OH + NaCl ‘This reaction is referred to as Dow's process for the manufacture of phenol. 200°C, 50 atm Colts Cl + 28H; AREA tig Nitty + NACL This reaction is known as [Dow's reaction. 250°C CgHs Cl + CuCN EE CH, CN ia) RESET 50 ours or sc wit Onie Support ies Organic Halides [Note () The presence of @ deactivating group (strong electron withdrawing group) such as nitro, cyano in ‘o" or “p* position ‘makes nucleophillic substitution possible. This results in an increase in electrophillic character of o-Carbon atom (which otherwise is lost due to resonance). cl on NO, 1g. NaH1CO,/400 K No so ae (went Br ocH, +CHON’. —> No, NO, p-Nitrobrome benzene ptroanisole (i) Wit strong bass like NaNH, or KNH,, aryl halides react easily to form aniline Br NH, ig. NH, +knu, “M4, +KBr — 38 (iil) Chlorobenzene reacts with methyl cyanide in presence of NaNH, al room temperature to give benzyl eyanide. cater +cr.ey 225 cgucrycn + He 2. (a) Wurtz -Fittig reaction : C,-BrstNa seis Ps 048,-CH + 2NaBe 3. Ullmann reaction : Heat 2 14200 ape »2Cut Host ane-{O)-H204 ae 4¢-{O){O)- er e200 prlodotoluene Self Study Course for IITJEE with Online Support 15, Halides CT CUGUC LUE Orgar 4. Reduction eat -Bs H+ Hor es ‘NaOH, 4 & cu, cu, Atty . aH, A Hel & p-trthere 5. Reaction with Metals: Cay t+ Me 61, Mel (orgnard Reagent Gig -1+ 211 8s CLs LL ta ny 6. Formation of DDT: ‘Two moles of Chlorobenzene reacts with chloral in H,SO, to give 1, 1, 1-Trichloro-2, 2-di(p-chlorophenyl) ethane, «an inseeticide commonly known as DDT. cl cl 180, 2 +cc,cHo Pe CH-cCcl, (007) hi {Dichioro Dipheny/ Trichoro ethane) al 7. Electrophillic substitution reaction (involving benzene ring) : alogens are weakly deactivating group because of their strong electron withdrawing tendeney, but due to ~M effect, they are weakly ‘o’ and ‘p’direeting Na ‘Resonance hybrid . ‘Observe that incoming electrophile, €° can substitute Sate Niomae aa paton eave a6 WREST, study course or with onine Support Wiens Organic Halides HNOyH,S0, Br Br,eidark © Q Q QQ . ® . O LEY fa wtiyanconen (2) Bromobenzene to styrene in steps) (>) Bromobenzene to Benzyl alcohol (in 3 steps) SOLUTION: Br Br Br Br 7 cul CHCH, _Nas CHCH, a CH=CH, act sive be ROH FC. Alkylation cu-ci, | Niar__| Reduction styrene NaOH, & Br coou HoH . 10", Prrigine LiAIN, ther Altematively = cucr, 2+ c,a,coon — Anisole can be prepared by either of following methods. Which of the two methods is the correct ? Method: (O)-om+ ct Method (Oya | ciyoxa —> Set Study Coure fo IIEE with Online Support ” Organic Halides SOLUTION : Arylhalides donot givenucleophilic substitution reection under normal conditions (whereas alkyl halides give this reaction). tis due to resonance in these compounds, C—X bond snot polaras in alkyl halides and due to partial double bond character (Resonance), itisnoteasly broken. 5. a * Hence Method - is not comet ¥ > Clearly Method - Lis the correct choice forthe formation of anisole as itis a simple nucleophilic substitution in CHCl by Phenoxide, as nucleophile. Hence for preparing aromatic ethers, we should always prefer Method - In general. LSE OUST Mentify A, B,C .... in the following reaction set up. cat NO, 4 HCL, PHCHRCL, , _NBS_, y_KoHOD , p Hae =sG 4 as” ® Nate sowuttow: cain NSO 4 misisltsaton ean hence is tne sa Ne A or ence Ns Ali ‘NH; NO. cr cc) Cl (Sand Rei “ Fae so” Fas a es ‘meyer Reaction) aT acne | Nae,9 . rt Fig Rsctn teat Or IN-CHAPTER EXERCISE - B L Identify A, B,C, oy Gat, A eg wy Gate A seunscoon ‘ i) eager 28 wor) Gs) oBromoben! bromide E> A wo o-Bromobenzyl bromide 1. Mg /ether (excess) 21,0 od CaHtgar ERP (a+ wy) HON Ce + Dy 7504 (cone so ETTOUESNNNNNNNNINIA, +s crs orm thon ipo Nic uur ace Organic Halides POLYHALOGEN DERIVATIVES Section - 3 Di-Halides ‘These compounds are divided into two categories : Geminal dibalides and Vicinal-(1, 2)-dibalides. Geminal dihalides (or Gem- CH,X-CHX CH =CH+2HX —> CH,CHX, cH, i, C= CH4+2HX —— CH,-CX,-CH, 2. By the action of Phosphorus pentachloride (PCI,) : cH,OH cHci i vr | cH,0H cH, iyo! cial dale CH,CHO + PCI, —> CH,CHCI, + POCI, Aldenyde Gem aihalide inal - (2, 2) -dihalides {or alkylene dibalides) R-CH-CH, iol x x Vieeinal dihalide Geminal dihalide Geminal dihalide 4+ POCI, + 2HCI CH,COCH, + PC, —> CH, -CCl, -CH, + POCI, Ketone Gem ihaide Reactions of Di-halogen derivatives : 1. Action of alcoholic KOH : (Dehydrohalogenation) xeu,ci,x 2&5 ca=cH Vicinal KOH cH,cHxX, 5 cH=cH MEX: om 2. Action of Zinc dust (Dehalogenation) XCH,CHX —425 CH=CH, CH, - CH, 2&5 CH=CH, vinyl halide) Vr KOHL [Neva x Xx 8 CH=CH 1g ia stronger base than ae. KON (ale: alcoholic medium) Selfstudy Course for IDEE wih Onine Support TTT 15 Organic Halides Ric) GucUm core 3. Action of aq. KOM : (Alkaline hydrolysis) XCH,CH,X + 2KOH (ag) —> CH, - CH, (vein) ion Ethylene glycol OH OH ‘viene ey CH,CHXCH,X + 2KOH(ag) —> CH,-CH - cH, (vicinal) 11 * @ropan-t, 2-¢i0l) OH OH CHCHX, +2KOH(ag) —> CH,CH(OH), — > cH,CHO (Gem) (Unstable) BO” acetaldehyde CH,CX,CH, + 2KOH(eq) — CH, -C(OH), ~CH, ———> CH, -CO-CH, (gem) (Unstable) “HQ0 acetone Note: > The above reaction is used to distinguish between gem and vicinal dibalides. > Gem diols are unstable and loses H,O to form carbonyl compounds. 4, Reactions of alc. KCN: 1,0 cs » (CH,COOH), (succinic aca) X=CH, ~CH,-x + 2KeN —“& NC-CH, -CH, -© cucnx, + 2Kew 2s cnc1cex), 22s e14en1(coow, A+ cx4cH,coon (a-methyimalonicacid) —* Note: Malonic acid and its a-alkyl derivatives loses CO, on heating to give corresponding monocarboxylic acid, Tri-Halogen Derivatives: ‘Trihaloderivative of methane is called as haloform. cucl, cHBr, cHI, Chloroform Bromoform lodoform (Liquid) Ligaid (Yellow solid) Haloforms are prepared by haloform reaction. Any organic compound having CH, -CH-R or CHy—C-R typeof 1 1 on ° structure undergoes haloform reaction on treatment with halogen and alkali or with hypohalite salt (NOX). CH, CHR or CH, -C-R 5 HX, +RCOO™ 1 W or OH ° R=H, alkyl, phenyl CH; ~CH(OH)-R-+4X, + 6NsOH —> CHX, + RCOONa + 5NaX +5H,O (CHCOR +3X, +4NaOH — CHX, + RCOONa+3NaX +3H,0 20 CE Self Study Course for IITJEE with Online Support Wiener Organic Halides Mechanism of Haloform Reaction : x, (Oxidation: CH, -CH-R_» —2__, cH, -C-R+2HX C Oadaion ¢ on ° 0) ognton cr -E-R =e R-oLeH ASS Rect x Hy R= cH ° on 1D ° Similarly remaining 1 stom undergoes halogenation to frm t-haloketone t Cy Xp oth, -x BR -6-eox ox on —>. | - i) RCo 0X, OH > R-C-cX, ——» R-C-O-H Ex, ——> R-C- al 1V i “0 © ° ° Chloroform : [ CHCI,] Itisa sickly sweet smelling liquid with b.p. as 61°C. Itis sparingly soluble in HO but readily soluble in ethanol and ether. Itis used in surgery as an anaesthetic. It is non-inflammable but its vapours may burn with green flame Preparation of Chloroform : L._ By distilling ethanol with a suspension of bleaching powder in water : (Laboratory method) C201, + HO —> Cl, + Ca(OH), (Bleaching powder) Here chlorine acts both as an oxidising as well as a chlorinating agent. Oxidation CH,CH,OH+Cl, —> CH,CHO+2HCI Chlorination: CH,CHO +3Cl, —> ccl,cHo “Trichiore acetaldehyde (Choral) cworn,s2cc,cn0 22 acxict, + gic00,ce Chto cal fomate Note: (i) Inplace of C20Cl,, we can use NaOH/CI,. NsoHt+ci, —>Nsocl+HC1 Nao — (01 +38C1 Pure Chloroform can be prepared by the action of sodium hydroxide solution on chloral hydrate. CCLCH(OH), or CClCHO.H,0 + NtOH —> CHCl, + HCOONa + H,0 Chloralhydrate Chloroform Sod. formate 1.140 CCL,CH(OHD, isstable due to H-bonding: CI— © — CH CLO, Self stuy Course for IDEE with Onine Support TTT 2, Organic Halides CUCU Sore 2 ‘Note 3. 4 From Acetone CH,COCH, +3Cl, —> CCI,COCH, ‘Wichioroacetone 2CC1,COCH, + Ca(OH), — CHC, + (CH,COO),Cs Acetone is preferred to Ethyl alcobol, asthe yield is better. From Carbon tetrachloride : cl, + 2[H) ee, CHC, + HCL From chlorination of Methane at 370°C : 310°C Hy 30h, diffuse sunlight CHCI, + 3HCI Reactions of Chloroform : 1. Oxidation : Chloroform in presence of sun light and air (O,) undergoes slow oxidation to form a highly poisonous gas, Phosgene, COCI, acnct, +0, #, acoct, + 2He1 Phosgene ‘Note Chloroform is stored in brown bottles to cut off light and filled upto brim to stop the above decomposition, 1% ethanol is also added which destroys the trace of phosgene that may be formed on storage 2C,H,OH + COCl, —(CH3), CO, + 2HCL Diethy! carbonate (Non - toxic} 2 Reduction: CHCl, + 2p] HCL, cy,c1, + Hel CHC, + 6[H) 222, cH, asHel 3. Heating with Silver powder : (Dehalogenation) 4. Nitration : CHC), + HNO, —> CCLNO, + H,0 Chloropcrn CChloropicrin isa poisonous liquid and used as insecticide and in chemical warfare. 5. Condensation with Ketones : on I ‘Visualise nucleophilic addition of (CH), -c-0 + H-cc, 4, (cH,), -C-cel, sualise nucleophilic addition of o*) Acetone Chloretone ° Chloretone is a colourless crystalline solid and is used as a hypnotic (sleep inducing drug). 2 Set sty Course for ITIEE wit Ontine Support Organic Halides 6. Carbylamine reaction + Both aliphatic and aromatic 1° amine react with chloroform to give isocyanides. RNH, + CHCL,+3KOH 5 RNC + 31,043.KCI (aliphatic 1° amine) Alkyl Isocyanige Isocyanides (carbylamines) have a very disagreeable smell, so the above reaction is used as a test (under the name Carbylamine Test) of chloroform and test of both aliphatic and aromatic primary amines. , owas, 6 -O (major CHO (Salicylaléehyde) (Minor 7. Reimer - Tiemann reaction : OH ‘Note : You will study the details of Reimer-Tiemann reaction later in Chapter on Phenols. oH Ko# 8. Hydrolysis: CHCl, *3KOH(eq) gq +He HOOD, ++ NC lodoform : [CHI, ] Todoform resembles chloroform in the methods of preparation. Preparation of lodoform : 1, With Ethyl alcohol : C)HjOH +4, + 6NaOH —> CHI, + HCOONa + SNal + 5H,O todoform (ellow sole} C\HOH + 41, +3Na,CO, —> CHI, | +5Nal + HCOONa +3CO, +2H,0 2. With Acetone : CH,COCH,+31,+4NUOH —» Cl) + 3Nal+CH,COONa+ 34,0 Note: This reaction is known as Iodoform reaction or lodoloim (en. Since the iodoform is a yellow coloured solid, so the iodoform reaction is used to test ethyl alcohol, acetaldehyde, secondary alcohols of type R(CH,)CHOH (methyl alkyl carbinol) and methyl ketones (RCOCH,), because all these form iodoform, The side product of the iodoform reaction, sodium carboxylate is acidified to produce carboxylic acid (RCOOH), Todoform is apale yellow solid, with m.p. 392 K, having characteristic odour, [Lis insoluble in water but dissolves readily in ethyl alcohol and ether. Itis used as an antiseptic for dressing wounds. self study Course for IEE with Onne Support _ UTR 25 Organic Halides CTE UC RCo Reactions of lodoform : Kou Heating in ie (0,) Hydra HCOOK co~ +H,0 ledine vapours 5 Reduction . cu, | -Reseaen CHL, cH, ‘with AgNO, Ag] (yellow ppt) fc Carhylamsine Reaction Heating CH=CH x ‘Ag powder GHNH, +KOHGe) HEN Tetra - Halogen Derivatives : Carbon Tetrachloride : CCI, Preparation of Carbon tetrachloride : 1. From Methane : w cH, +4ch 5 coy + 4H. 4 ACR CoC impute) ‘Methane used here is obtained from natural gas. 2. From Carbon disulphide : AICI, C5, +3 GREE Ch, + 83C 8,Cl, is separated by fractional distillation, Itis then treated with more CS, to give CCL, CCl, is washed with NaOH and distilled to obtain pure CCl. 28,Cl, +8; —+CCL, +65 (Pure) 3. From Propane : 400°C CH,CH,CH, + 9¢1, AOC CCl, + CCl, + SHCL (Uiquiey (Sot) (Note: CCI, isa colourless and poisonous liguid which is insoluble in HO. Itis a good solvent for grease and oils. CCI, is used in fire extinguisher esp. electzc fites) as Pyrene. Itis also an insecticide for hookworms. ‘Organic halogen compounds are less inflammable than the hydrocarbons, The inflammability decreases with increasing halogen content, Because they are good solvents for fats and oils and do not catch fire easily, polychloro compounds (ei and tetrachloro ethylenes) are widely used as solvents fordry cleaning, carbon teta-chloride is used in fire extinguishers ‘and calledaas pyrene. 1, 1,2-Trichloroethylene calledas westrosol. Reactions of Carbon tetrachloride : 1. Oxidation: cc + #0 2S, coc, + axe (steam) Phosgene 2. Reduction: CCiy + 2[11] 22°, cue, + He 2a) NRE I i Sy Corso wih ine apport ieee Organic Halides 3, Hydrolysis: CCl, + 4KOH (aq) 2-5 CCH), — > co, XH, K,co, + H,0 RCT astabie) 2° Sos 4, Action of HF: CCl, + 4HF SE, cee, + 2HC1 Freon12 5. Action of SbF, 2c, + 2805 S55 scents + SHC ‘Note: Freon is widely used as a refrigerant cooling agent in refrigerators and air conditioners. It is also used as a propellant in aerosols and foams. Recently, itis discovered that Freon depletes ozone layer. So, its uses have been banned in many countries 6. Reimer -Tiemann reaction : ou ou . coon oO 4 cet, + nso 2° Oo + 4Nacl +284, Pal sane a Some other Important Halides : Vinyl Chloride : [CHp=CHCI —; vinyl group CH, =CH-] Preparation of Vinyl chloride : 1. From Acetylene CH= CH+He! HEC cH, = CHI 2. From Ethylene Chloride : (Viccinal dihalides) c1c#,- cH,61 gree CH= CHC! + HCI 3. From ethylene: CH=CH +c °° cn, =cuter+ ner Properties of Vinyl chloride Vinyl ehloride is colourless gas at room temperature, with bp. a8 13°C. The halogen atom in vinyl chloride is not reactive as in other alkyl halides. However, ~ chloride in aucleophillic substitution reactions is due to resonance in it -C- bond of vinyl chloride gives the usual addition reactions. The non-resctivity of viny! Kc cu=cH SS Ea Tr WEEE WR OS EE ‘| -—+ CH, -CH=C1 Organic Halides Reactions of Vinyl chloride : Itgives same reactions as given by alkenes. Br, senel ay cH,Br—CH(BAC Reduction Red Pi CH, CH, “ Jc, KOH ako cus cine oc NaN, (1.0 €@) Polymerisetion q q Peroxide ~CH,~CH-CH, CH evo * Allyl Chloride : [CH, = CHCH,Cl] Preparation of Allyl chloride : 1. From Propene : cmt, =creay, sc, 2°89 on), crease ner Propene Ally chloride 2. By the action of Phosphorus halides on allyl alcohol : CH, = CHCH,OH + Pcl, —\—> CH, =CHCH,CI + POC) + HCI Aly alcoho! 3CH, Br-CH,-CH@&)-CH,CL (CH, = CH-CH,Cl+ HBr —> CH,CH(B)-CH,CL 2-Bromo-1-Chloropropane Note : The addition follows Markovnikov's tule, However in presence of peroxides, 1,3-Dibromopropane is formed, HBr. (CH, = CH-CHyBr IG? CH ~CHy~ CHB Br 2c WUETTEINNNNNNI, ser ty course for st with Ont Support Winn Organic Halides 2. Nucleophillic Substitution Reactions Since in allyl chloride, there is no resonance (unlike in vinyl chloride), nueleophillic substitution reactions take place with cease, For example CH,=CH-CH,Cl + KOH(@a) — cH, CH,-CH-CH,CI + NH, — CH, HCH,OH +KCI 1H-CH,NH, + HCL CH, =CHCH,CI + KCN —> CH, =CH-CH,CN + KCI cHyecuceyct + Mg YE cH, « cHCH, Mec (Allylic Grignard Reagent) CH, =CH-CH,CI+CHONa —> CH, =CH-CH,-0-CH, (ally methyl ether) Benzyl Chloride : [ C,H,CH,Cl ] Preparation of Benzy| chloride = 2. By heating benzene with formaldehyde : (O) stieto ser Es cuci+ner 3. By the action of PCI, on benzyl alcohol : Note: Benzyl bromide is prepared by action of NBS/CCI, on toluene (Allylic bromination). Opn Orn Reactions and Properties of Benzyl Chloride : 1. From Toluene : Itis acolourless bad smelling liquid, with b.p. st 179°C. ts vapours bring teats from eyes and are irritating. Iti insoluble in water but soluble in organic solvent ‘The main reactions of benzyl chloride and bromide ate like those of Alkyl halides. Nucleophillic substitution reactions occur with ‘case unlike in case of aryl halides (due fo resonance in aryl halides), Self study Course for IEE with Onine Support TTT 27 Organic Halides COU RCE 1. Nucleophilic Substitution Reactions : Kolliag) egi,cn,on1 + Ket Benzyl alcohol KeN CU,CH,CN + KCL “ Benzyl cyanide Nib CH.CH,NH, “ Benzyl amine CH,COOAg _ SEEESSE . c,CH,00CCH, Na 28 (Oy auen-{O) + axaci Dipheny! ethane 2. Wurtz Reaction : Ors 3. Wurtz - Fittig reaction : (O)-ausers2%+e-{O) 8 (O)-an-{O) same Diphenyl methane 5. Reduction : CHSCH,Cl + 2[1] a CgHSCH, +HC1 Toluene (a) cH,cHo POS, 42 KOH, p MBH, c(t) + D(as) (b) CHCl, (A) SRO, p_NOOH/D 5) + D(ag.) SOLUTION enone 24 excrc, 82, cxreno em dinaide —~"#° —pcetaldehyde ® o i ch,ciio a CHC + H—C—ONa (aq) chloroform Sod. formate © fos 2a) NREDEIEEE I 5 yon trrice with tine Suppor Rie eeu Umer Organic Halides ) CMe, SEO, p MOH, 6%) + Diag) (a) nh Since 8) gives iodoform tes, s0 13) is either a2" alcobol of type CH, —CH —R orametby! ketone of type CH, —C—R fl on 0 Now (13) is obtained by hydrolysis of a dihalide \). Amust be gem-cdihalide, as viccinal dihalide gives glycols on hydrolysis. Now (\) can be terminal gem- CH,CH,CH,CHO | a or (Cit), HCH cl ger» (CH), CH—cHo a Sel study Course for IDEE wih Onine Support TTT 25 Organic Hali les CGIUCUCUMo cnr (©). The possible structures of B and their reduction products with Zn — Hg/lCl (Clemmenson’s reduction) are: ° i zn He cH, —C—cH,cH, SE cHcHcH.cH, Hg cuycu,cH,cHo + cn,ci,cH,cr, cH, ex co at cH, — cH cH, I cH, cH An organic compound (A), C,H,Br reacts with ag. KOH solution to give another compound (B), CyH,0. The compound (B) upon treatment of alkaline solution of iodine gives a yellow precipitate. The filtrate on acidification gives a white solid (C), CHO, Give structures of A, B, C and explain the reactions involved. SOLUTION: CyHoBr —8KH, cy4,0 MOB cut, J a B) 2” Yellow ppt Since (4) is hydrolysed, Br is not attached to ring ic, it is attached to the side chain. () could be (Opener 8 (Oren an, br i iS Op pres 2 (O)- prom te ou Seo sot “ (O)- ere, SHES (Oe, COON) Cts | 1 = yellow bu 8 (Op co0%s = (O)- coor © An alkene (A) C,,#1,.0n ozonolysis gives only one product (B) C,H,0. Compound (B) on reaction with NaOHIL, yields sodium benzoate. Compound (B) reacts with Zn-HglHCl yielding a hydrocarbon (C) C,Hyy Write the structures of compounds (B) and (C). Based on this information two isometric structures can be proposed for alkene (A), Write their structures and identify the isomer which on catalytic hydrogenation (H.JPd ~ C) gives a racemic mixture. 20 ETTETIENININNINII,. 4st cor rite wit onine Spor ieee Organic Halides CyB ——* Coy > COONa + (D) (s) Clearly the compound (9)isiodoform ; CHI, (a ®B) * po ©) CHo A I ; ro (A) must be a symmetric alkene asit gives only one compound, C,H,0. Me Me © A) Qi y\ / Me is form transform vor), BAPE, Racemicmintwe Recall that hydrogenation is ‘syn” addition, th. ph ph pe | | H, Me—C—H H—C—Me 1 | + | {oh phen, Me: meth c. an adin H—C—Me Me—C—H Me ph i I ph pa trons (Racemic mixture} h h Me pI ph c h u—t— me ll 2 (Meso compound) A ont fe rh “Me ph Setfstudy Courts for LEE wth Once Support A/T 5, MIC CIuGU Cee IN-CHAPTER EXERCISE - C L. What isthe final product in each reaction ? HNO, ) cuct, Rs,» (0) CH NH, FP 9 OH 2. Whar happens when ? Give equations only (2) Chlorine reacts with CS, in presence of anhydrous aluminium chloride (©) Chlorine is passed through ethyl alcohol (©) Chloral is treated with aqueous sodium hydroxide (3) Chloroform is boiled with agucous potassium hydroxide 3. Identify the products (A), (B) and (©) br drole NagCOs Colt, EE (A) ED (8) ES (0) 4. Explain the following (a) Carbon tetrachloride is used as fire extinguisher ()) Todoform gives precipitate with AgNO, on heating while chloroform does not. (©) Alkyl iodides become darken on sanding in presence of light While preparing alkyl halides form alkanes, dry goscous halogen acids are used instead oftheir aqueous solutions. 5. Match the following () Carbon tetrachloride 1 Antiseptic: (B) Chioretone I. Refrigerant (©) Westrosot UW. Chloroform (D) Freon WV. Polymer © Iodoferm V. Hypnotic: © Teflon Vi Pyrene (©) Carbylamine reaction VI. Solvent Choose the correct option. Only one choice is correct. Questions marked with ‘*' may have more than one correct option. 6. Which of the following reactions leads to the formation of chloretone ? () Enel, + cH,cocn, (B) CCl, + Acetone (©) CHCI,+KOH () CHCl, +HNO, ©. Todoform is formed on warming I, and NaOH with () HOH 3) CHOH (© CHOOH =) CHCHO 8. When chloroform is treated with cone. HINO, it gives chloropicrin, Its formula is (\) CHINO, —(B) CCN, ()_—CHCL,HINO,-—(D)_—_ None of these 9. When chloroform is treated with excess oxygen it forms: () COCLFHCE (B) — COCL+ CAH CO — COC, AC, + 0 D)_—_No product will be formed 10, Todoform on heating with KOH gives (\) CHCHO(B)—CH,COOK.—()—HCOOK (HCHO LL, Chloroform with zine dustin water gives : cH, (B)— Chloropierin (©) CCl, Oo cH, 32 ESTED, sete study course for i3Ee with ontine Support Vidyamandir Classes Organic Halides THE CHEMISTRY OF GRIGNARD REAGENT Section - 4 Introduction : Organo-magnesium halides popularly known as Grignard reagents were discovered by French chemist Victor Grignard. ‘The organic part may be detived from various types of hydrocarbons. The most important type is alkyl magnesium halide. Itis represented as RMeX (X: CL, BrorD) Generally Grignard Reagent is prepared by eating an organic halide with magnesium metal in ether as solvent. sedluxin RX + Mg Senex. Alkyl magnesium halide Reflux is a technique, allowing one to boil the contents ofa vessel over an extended period, 'R’ may be primary (1°), secondary (2°) or tertiary (3°) alkyl, may be replaced by cycloalkyl, alkenyl, aryl or alkynyl group. The halide ions are Cl, Br or I. Fluorides are least reactive, so they are not considered. The reactivity of halides follows the order : > Br> C1>F. Alkyl halides are more reactive than aryl and vinyl halides. Azyl and vinyl halides ate best prepared by using THF (Tetrahydrofuran) instead of ether as solvent. THE CH, = CHCL+ Mg THES cu, — CHMgCL Sere ea ‘Note In the preparation of Grignard reagents, ether asa solvent is must. The Grignard reagent are unstable in aqueous medium so avoid aqueous medium, Properties : Grignard Reagent, RMgX is avery strong base because of polarisation of R-Mg bond = RMX. Itabstracts a proton from species containing acidic hydrogen such as water (—O—H), 1°, 2° and 3° alcohols (—O—H),1° and 2° amines (CNH, terminal alkynes (C= C -H). Inthe reactions with these species, a protons transferred tothe negatively polarised carbon atom of the Grignard Reagent to give a hydrocarbon Grignard Reagent, RMgX is not only a strong base, but also a strong niicleophile de,, it shows a strong tendency to donate the electron cloud to the species seeking electrons (#lectrophiles). Reactions As Base Grignard reagent asa base reacts with compounds such as acids, water, primary alcohols, primary amines, secondary amine and. terminal alkynes, all containing active Hydrogen atom (H) to give alkanes. “This reaction is also used to determine active hydrogen atoms in the onganic compound” os 3 & -Mgl + HO -~ H —> RH + Mg(@OH)I ce R—-Mgl + R’-O-H —> RH + Mg(OR’)I soe Mg] +R’ NH ~H —> RH + Mg(NHR’)I xs R-Mgl + R'- C= C-H —> RH+R’-C=C-Mgl Sel Study Course for IEE with Onne Support APTI 35 Orgar Halides CT CIUCUT Eee Reactions As Nucleophile : Grignard reagent acts asa strong nucleophile and shows nucleophilic addition reactions to give various products. Alkyl group, being electron rich (carbanian) acts as a nucleophile in Grignard reagent and reacts with carbonyl compounds, esters, acid halides, eyanides ete ree i= MgX = E-MgX 1. With carbonyl group : so nO | ol “oMex + 56-0 — -¢-0-max “ ~C-0H = Me(OH)X - k k GrararReagert eee a akon Tshuceopile, “subsete (2) With aldehydes : ° OMel I () HOCH + CMe > H-c-4 22 cu,cH,0n + Mg(OHDT I ¥ aleohot cy ° oMet i ig (0) RCH + eMgI— R-C-H FRO, RCHOH (alcohol I a I R R ° oat i Lino CH, -C-H + C.Mgl — cH,—C-1 B22, cH, CHO (eon) I uw I cH cH, {lsopropyl alcohol) (bo) With ketones : R R I 1 RoC =0# Mg —9R- C - omer 1224 R- C-OH (rakechob HY R” Re e (CH,),C=0 + CH,Mgl —> (CH,),C- Mgt 122.5 (cH), -C-on 1 {tert butyl alcohol) Deore ent Bs eo erst Cyclohexanone cH, Fy Sy Ce for TEE WA Gis Bappot Vidyaman Organic Halides 2. With acid chloride : ° oMe'ct i 1 CH,C-CE + CHMgCl —s CH, -C-cl —> CH, C=0 + MgCl, (aceey elorde) én, oy, ‘Note Ketones (¢g., acetone) formed above further reacts with Grignard reagent to form 3° alcohols if one uses excess of Grignard reagent. However with 1: I mole ratio of acd halides and Grignard reagent, one can prepare only ketones. 3. With Esters : “OMe'Br ° & a GQ 1 SSigpr + bon 2 bon 2 2-6 + maior ye maiaagen Cee | carbon ‘ceanar Reagent Hetroprie R ™ ssNucleophle suber comou (2) With formates : "0 Mg'Br ° HCOOR + |), MgBr —» H— COR —+ 01), -C-H = Mg(OR)Br (Formates) by an aldehyde Note: The akdchyides react further with CH,MeBrto give 2° alcohol, ifitis present in excess, But with I: | moleratio of reactants will certainly give aldehydes only (b) With carboxylates Cy Me's ° CH,COOR + Cli MgBr ——+ CH,— COR ——+ CH, -C~ CH, + Mg(OR)Br ‘acetate by aketone Note: The ketones react further with CH,Mgl to give 3° alcohol if tis present in excess, But 1:1 mole ratio of reactants will certainly give ketones only. (c)_ With Lactones (cyclic esters) a} + [one Lege [ee tt [ —° MgB | on! Lactone (a cycic ether) ‘Note : Ifan organic compound has both ester and keto group, the Grignard regent prefers to attack keto group (keto group has higher electrophilic character than ester group). NT as ic Halides (keto group) (ester group) . ° Oe Me He om 4, With cyanides : + NH} ~ Mg(OH)1 ° ° ° if i i eapt + €=0 —> x-G-ongt 22, Con + agcomt ‘dryice " Carboxylic acid 6. With Oxygen Ho RMgl +$0, —— Rome! 27> RH + Melon) 7. With ethylene oxide (oxiranes) : so™ HO PML HRSA —+ B-CHLCH, OME G+ RCHCH,OH + Me(OHDT 0% an alcohol oxiane ‘Note: Allthe above reactions can also be visualised by taking phenyl group (ph : C,H, instead of R (AlkyD to get corresponding aromatic compounds. 8. With inorganic halides : (Formation of Organometallics) 4CHsMgBr + 2PbCl —> (CgH1s),Pb +Pb=4MgBu(C) Tetraethy! lead (2) 2RMgBr + CdCl; —> (R),Cd + 2MgBr(Ch Dialkyicadmium 36 i Ss Cure Yor TEE Wil Orie SoppaR Organic Halides Ai CUS ere CELI entity compounds A, B, C.. Ope 1 Opn »- in the following reaction setup. Ho, oe 20/H,0 © 1» Oem B = p c—“__.g Ou eee memati 2 HOTA 2 HOTA [ a | SOLUTION: " o, cuca, cH cH, =e HO + HCHO i a Zain, cH on “ ® On OrO* OD o Observe that (D) has a conjugated system hence it is more stable. oO) em) (Miner) (Major) ‘The formation major and minor products during the dehydration of alcohols will be discussed more extensively in ‘upcoming modules. EY saentity componds A, B, C, .. in the following reaction setup. ee one g boa, 80, me 2.10 a 21,00 a Tae y Leth. p TSG Se souman © 1. MeMgBr Ox Rt Oo Sie Oro tit OK Oem (ketone) (3° alcohol) “ "= Congas gn "Qn “ Me trans-2-methycyleherano| Self Study Course for IITJEE with Online Support AU Ey, Organic Halides CCUCUC Soe on (yon rc Ove _CH,COCH, one) HS, e< ) 2 MgiELO oy a oT CH cH, @ SEND’ sensity the final product in the given sequence of reactions. 2 MgELO (Xo eR OMe wa (Nove Cx OH es > SOLUTION : @ 1. PB, 2. Mpether no. wore wo | ES ave-o | — < ne Me o Sot Formation of (©) from (13) is referred to as “intramolecular nucleophilic addition". (SEL saentify att he possible products in the given reaction. One or more options may be correct. CHy-C=CH + Mec— Br Xa, (A) Me,-C-C=C-Me @B) (©) MeC-CH,-C=cH o SOLUTION : cH, -ca Cu "82, cy, ce Na Terminal alkyne Propynide anion Acie Hydrogen Propynide anion can set as nucleophile and also as a base Me, —C—Br (tert. butyl bromide) isa tertiary (3°) halide, which prefers elimination over substitution ci, ch

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