HALOGENATED ALIPHATIC Compounds derived from hydrocarbons by the replacement of one ot more hydrogen atoms by the corresponding number of halogen atoms are termed as hhalogen derivatives. The halogen derivatives of aliptiatic hydrocarbons are broadly classified into two classes: (i) Halogen derivatives of alkanes or halo-alkanes. Gi) Halogen derivatives of unsaturated hydrocarbons, ice, derivatives of alkenes and alkynes. 1 HALOGEN DERIVATIVES OF ALKANES OR HALO-ALKANES ‘Compounds derived from alkanes by the replacement of ‘one or more hydrogen atoms by the corresponding ber of halogen atoms (fluorine, chlorine; bromine or iodine) are termed halogen derivatives of alkanes’ or hhalo-alkanes. Depending on the mumber of halogen atoms. present in the halogen derivative, these are termed as mono-, "dix, ti, tetta- and polyhalogen derivatives. -4 -H <4 cH, Ho cH —x Hs cH, x, =H Methane ‘Mono Di cu—x, 45 c_x, tik Tete 1, Monohalogen derivatives: One halogen atom is attached to carbon atom. They are commonly represented by the formula RX where R is an alkyl radical and X is a halogen atom. © RH Ey R—X ‘Alkane ** Aly halide These are terined alky) halides andthe homologous series has the general formula C, Hoy41X. HYDROCARBONS Examples : CHCl CyHsBr CHL ‘Methyl chloride thy! bromide Propyl iodide ‘Monohalogen derivatives or alkyl halides are classified as primary (1°), secondary (2°) or tertiary (3°) depending upon ‘whether the halogen atom is attached to primary, secondary or tertiary carbon atoms. A Primary R’ Secondary |Z eatbon |Z catton RLY R-CLY #H #, Primary alkyl halide Secondary aly! halide R retiary | A catbon ROUX RY Tertiary alkyl halide 2. Di-halogen derivatives: ‘The dihalogen derivatives of alkanes are derived by the replacement of two hydrogen atoms by two-halogen atoms. Cylons SH Cetin, X2 ‘Atkane” —*2X pitalogen derivative ‘The dihalogen derivatives are mainly of three types: @ Gem-dihalides: In these derivatives both the hhalogen atoms are attached to the’same carhon atom. These are also called jene (di) halides. cl cue ch Ethylidene chloride CH,—CBr,—CH, Teopropylidene bromide (@.2:Dibromopropane)Halogenated Aliphatic Hydrocarbons (i) Vie-dihalides : Inv these derivatives, the halogen atoms are attached to adjacent (vicinal) carbon atoms. These are also termed alkylene (di) halides. CH,CICH,CI ; CH,CHCICH,CI Ettyiene chloride Propylene corde (1,2-Dichloroethan) (1.2.Diehioropropane) il) c-« halides (terminal dihalides) : In these derivatives, the halogen atoms are attached to terminal carbon atoms. These are also called polymethylene halides. (CH,BrCH,CH,Br;, CICH,CH,CH;CH,C1 ‘Trimehylene bromide “Tetramethylene chloride (13-Dibromopropane) (14-Dichlorobutane) 3. Tri-halogen derivatives : Tri-halogen derivatives are derived by the replacement of three hydrogen atoms from alkanes by three halogen atoms. They. have the general formula C,H,,-,X;. The tri-halogen derivatives of first alkane (methane) are HCI, ; HBr, cH, Chloroform Bromoform lodoform ‘These compounds are termed as haloforms. 4, Tetra-halogen derivatives : The tetra-halogen deriva- tives are derived by the replacement of four hydrogen atoms from alkanes by four halogen atoms. All the four halogen ‘atoms are attached to the same carbon atom in derivatives of methane, cel, CBr, ‘Carbon ttreshlorids Carbon Kteabromigo In other derivatives, the four halogen atoms are attached to different carbon atoms, €.g., CHCl, CHC!, Similarly, Polyhalogen derivative is: C,Clg Hexachloroethane Acetylene tetrachloride oF 141,22 - tetrachloroethane Classification Monohalogen compounds may further be classified according to the nature of C—X bond in haloalkanes and haaloalkenes particularly to the hybridization of the carbon atom linked to the halogen (A) Compounds containing C—X bond, where carbon 4s sp?-hybridized. (@ Alkyl halides or Haloatkanes: In alkyl halides, the hhalogen atom is bonded to an alkyl group. The homologous series is represented by C,H, 4. They are further classified as primary (I°), secondary (2°) and tertiary (3°) halides depending upon whether the halogen atom is aiached to a primary, secondary or teary carbon atom. Examples ae: CH, —cH, CH, Cl; CH, —CH—CH,; L-oepropane ! or!) eee 2-Fodopropane (cecondary or 2) : CH; Hh—P—CH Br 2-Bromo-2-methylpropane (tertiary 93°) (li) Allylic halides: In these halides, the halogen atom is attached to allylic earbon (C=C—C—X), ie. carbon atom next to C=C, Examples are: H,C=CH—CH,—1 ; H,C=ch—CH—CH, ; $3-lodoprop-I-ene I (Ally Br +} Bromobut-hene [4 cl CH=CH—CHCI 13 2 2Chlorbeyelabeil:ene 3-Chloro--phenyipopI-ene CHy—CH—CH—CHBr (Cinna chris) 1-Bromobut-2-ene Cropt hromide) Allylic halides may be primary, secondary or tertiary. (il) Benzylic halides: In these halides, the halogen atom is attached to a benzylié carbon (CeHsCHy—, CoH CHK of CoHsCS), ie. the carbon atoms of the sidé chain carrying the aryl group. Examples ae: Benzyl chloride; Benzal chloride; Benzo trichloride; B-Phenyl ethyl bromide @) Compounds containing C—X bond, where carbon is sp"-hybridized. (© Arythalides: In these halides, the halogen atom is directly atached tothe carbon atom ofan aromatic ring. These halides are also called haloarenes. Examples are: Chlorobenzene ; Bromobenzene; odobenzene _: 2-Chiorotoluene: 3-Bromotoluene ; 4-Bromotoluene (ii) Vinylic halides: In these halides, the halogen atom is attached to vinylic carbon (C=C—X); ie, one of the carbon atoms of CC. Examples are: H,C=CH—Cl ; Chloroethene (Wing elorde) Aa) 1 -Bromocyclohex-I-ene(C) Compounds containing C—X bond, where carbon is sp-hybridized. Alkynyl halides of Haloalkynes: In these halides, the halogen atomis attached to one ofthe carbon atoms of 2C=C. Examples are: G.RB. Organic Chemistry for Competitions Foro of loge | Common name. | IUPAC same ca, [Gata coe Teboconehas a .DhULhrFrr—C—<“‘ CC;*zsC;sC \Geahionde (ore HO=C—Br 5 HyC—cmc—al Preece coco ame (emma) Nomenclatre Formas ote paap cs a mia tate | comma mame | TUPAC aia ici aoe [clnmaine cae yt trnize [rometae cuycusens ——atroptindde | ndpropne cuycuct, ——iopeytomise fSrnopepe caycnicn,cuc eBuyonde | |-hiobunne Ste - fe etie we DEN atibe fet wente phones ay HC“ Ipropane om, cH —C—cH. [Tertiary butyl fp-Bromo-2-methyl- ioe [Promide [propane be ca\Caycr,crjcr.c frat cioite }-ckaopenine msl re Oe faye eat cipm samy re cri-gx-crc fgets con. eee ae CH, |Isoamy! chloride «at rr py csi 2 horny I or butane Gy i CH;CH; | Tert. amyl chloride ea Ieee | nw 22 CH;—C—CH,C1 or |dimethyipropane i, sony che CHA, . |Methylene chloride |Dichloromethane a CHC fame Deets Secondary alkane > Primary alkane Br or, wha Br a ) A @ AA 1 Br © AN © AY Br R-X +HX on! AN ‘Alkyl halide Direct halogenation proceeds through free radical mechanism : Direct halogenation does not form pure OB sr ann mA ts monohalogen derivatives but a mixture of polyhalogen el i derivatives is always obtained. For example, methane reacts With chlorine in presence of diffused sunlight or at 250-400°C to form a mixture of methyl chloride, methylene chloride, chloroform and carbon tetrachloride, Example 4, Write all the possible structures for the ch molecular formula CyHyBr. Give heir TUPAC names Which CHa * Cla pr? CH,CL Spanc, Ter HC of these are optically active? Solutio : Ch, Gey () CH,CH,CH,CH,CH,Br 1-Bromopentane “ne? ls ‘ (orimary) This method is, thus not used in taborato ry because It naan ees is not easy to separate the individual members from the : mixture. However, it is the most important commercial G)CH,CH,CHCH,CH, 3-Bromopentane method for obiaining alkyl halides because alkanes are i : available in large amounts from petroleum and natural gas. If br Secondary) the conditions are well maintained especially the ratio of : : halogen and alkane, the halogenation may be suppressed OCH CHF —CHLBr-Broma-2-metiytutans beyond monosubstituted product. The displacement of H from CH, mary) hydrocarbon is in the order: () CH,—CH —CH,CH,Br 1-Bromo-3-methylbutane Ae eu I (primary) ca,Halogenated Aliphatic Hydrocarbons. Ligh GH, Gx) +Cl, HHS CH +H Ethane I ty chloride (Majo product cH,cH,CH, +cl, U@, CH,CHCH, +CH,CH,CH,CI Propane ~ I 1c a a3) 68%) Similarly, bromination takes place, but not so vigorous as chlorination. However, iodination can be done by heating with iodine in the presence of oxidising agents such as cone. HN, of HIO, (to oxidise HI formed during the reaction to iodine), and hence, shift the equilibrium in the forward reaction. Heat RH+1, = RIFHI (SHI+HIO, —> 31, +34,0) ‘The reactivity of halogens decreases in the order: F,>C1,>Br,> 1. Bromination of alkanes is less exothermic than chlorination and so with fluorination, Todine is unique as its reaction with alkanes is endothermic. Chlorination of n-alkanes (C, and above) gives a mixture of d- and /- optical isomers, ie, racemic mixture (optically CH,CH,CH,CH, —y H—C—CI Butane * ca.ca, @ © Rackale ‘Alkane can react with sulphuryl chloride only in presence of light and traces of organic peroxide. RH +S0,Cl; —"_4 R—cI +HCI+S0, ‘Akane Sujal PSOE. Choralane ‘chloride 2. From alkenes : Halogen acids (HCI, HBr, HD) react readily with alkenes to form alkyl halides, The order of ity of halogen acids is: HI> HBr>HC.> HE HC=CH, + HBr —> CH,CH,be ‘The unsymmetrical alkenes follow Markownlkof?’s rule uring addition forming secondary ot tertiary alkyl halides predominantly through the formation of most stable carbo- cation. Addition occurs though electrophilic attack. Howevet, in presence of peroxide (R—-O—O—R), such as benzoyl peroxide (C,H,CO—O-—-O—COC,H,), the HBr addition follows anti Markownikof?'s rule (peroxide effet or Kharasch effect) and form primary of normal alkyl bromides. Such an addition follows free radical mechanism. This method is well suited for the instil preparation of alkyl halides as the lower alkenes are oblained during cracking of petroleum products. 393 t R—CH=CH—R + HX —> R—CH,—CH—R ‘Symmetrical alkene Al halide R—CH=CH, +HX —> R Hy ‘Unsymmetricl alkene x Alt hate i CH,—CH=CH, +HBr —> CH,—CH—CH, ‘Unsyrmetical alkene 2-Bromopropane (sopropy! bromide) CH, ie ctf Br — Fc i be tt te 2 heme he ‘This can be explained by 1,2-Hydride shift to attain sreater stability of carbocation. CH; CH, cH ec Con, cry —¢- anc, H H Mebane ee cahoation L2tydie win o CH, a —F-caLc, AE on, -E 1c, i €* Catoctin) a ‘More stable than 2° Cl (CH,—CH=CH, + HBr Pe, CH,—CH,—CH,Br romorone (a-Propyl bromide) cy cH, CH, —C=h, + HBr PH, oH, CH Br 2-Methyl peopene i |-Bromo-2-methyl propane It may be noted that the peroxide effect applies to the addition of HBr only and not to the addition of HCI or HI. Allylic substitution When alkenes are heated with Cl, or Br, at a high ‘temperature of about 500°C, the hydrogen atom of the allylic carbon (ie., carbon atom next to the double bonds) is substituted withthe halogen atom without breaking the double bond (allylic substitution) and forms allyl halide. For example,394 CH,CH=CH, +Cl, 2, Propene CICH,CH=CH, + HCI Ally chloride (@-Chloroprop-t-coe) ‘The allylic substitution can also be carried out by heating the alkene with N-bromo succinimide (NBS) or sulphuryl chloride ($0,Cl,) at 200°C in presence of light and traces of organic peroxides such as benzoyl peroxide. CH) —CH=CH, + Propene 1N -Bromo svecinimide CH, —c0. BrcH,cH=CH + | S>ne Mbenopop.tew | CH; —CO (Ally bromide) ‘Succinimide CH; —CH=CH, +80,Cl,; °C, CICH,CHCH, Propene ‘UV light 3.Chioroprop-I-ene ‘Allyl chloride) +80, +HC1 3. From alcohols : Generally alkyl halides are prepared from alcohols by replacement of —OH by an halogen atom (§ y reaction). R-OH+H—X —+ R—X+H,0 The replacement of —OH group can be done with halogen acids, phosphorus halides or thionyl chloride. (® By the action of halogen acids : Almost quantitative yield of alkyl halides is obtained when alcohols react with halogen acids in presence of a dehydrating agent such as anhydrous zinc chloride or concentrated sulphuric acid. The reactivity of the halogen acids and that of alcohols follow the following orders: HI> HBr> HCI> HF Allyl>3° alcohol >2° alcohol> 1° alcoho! In this Sy reaction, the nucleophile (X°) attacks the protonated aleohol molecule withthe elimination of water (a ‘good leaving group). R—ON+H —s R—ON, fp —> RX +110 Since, the nucleophilicity (ce, tendeney to donate electron pair to the carbon) of halide ions decreases in the order, I” > Br” >CI°”, the order of reactivity of the halogen acids decreases in the Same order, ie. I> HBr >HCL (@) Alkyl chlorides are obtained by passing hydrogen chloride (gas) through alcohol in presence of anhydrous zine chloride (Lewis acid: CH,CH,OH+HC\(g) 8S, (CH,CH,CI+H,0 Ethanol (Cone) 78C2 GR.B. Organic Chemistry for Competitions ‘This mixture (1) of cone. HCLand anhyd. ZnCl, isealled Lucas reagent. ‘The yield can be improved when the vapours of alcohol and HCI are passed over alumina at 350°C. It must be noted that 1° and 2° alkyl chlorides are prepared from their respective alcohols by using HCl gas and anhydrous ZnCl, (Groove's process). Tertiary alcohols are very reactive and therefore, they react readily with cone. HCI even in the absence of ZnCl, (CH,),C—OH + HCL FE (CHHy)xC—C1 + H,0 2-Metiy2-propanol (cone.) T=" (Ger butyl alcoho) 1° alcohols follow Sy2 path while 2° and 3° alcohols Sy path (proceeds through most stable carbocation inter- mediate). (b) Alkyl bromides are obtained in a similar manner by refluxing the alcohol with constant boiling HBr (48%) in presence of a little concentrated sulphuric acid. These are also ‘biained when the alcohol is heated with potassium bromide in presence of conc. HS0, in excess (Lab method). C)H,0n+ HBr SSO), Cope 41,0 ‘Ethanol Reflox " Brotnethane C)H,OH + KBr + H,S0, 4 C,H,Br +KHSO, +H,0 ‘Note? The mistare of KBr and WSO, isnot wedi case of secondary and tertiary alcohols es their dehydration may occu. Tin case of higher alcobols, there can be 1,2-methyl (CH ) or Lhd (i) shit to form mow stable exoeaion " er Cif — FG HC —9 Cif | CH, OH a 3,3-Dimeyl-2-butanol This is due to 1,2-Methy! shift. cH, CH; ofa, eee, CH, On CH, OFF ie He, Ci _ca cus (2° Cabocation) 2 stann ain Gis Gs Gis Gs - I CH,—C—cH—cH, <* cH,—c*—CH—cHy {@° Carbocaton) a ‘More stable han 2°Halogenated Aliphatic Hydrocarbons (©) Alkyl iodides are prepared by refluxing alcohol with excess of HI (57%). These are also obtained when the alcoho! is heated with potassium iodide in presence of phosphoric acid C,H.OH+KI+H,PO, “8% C,H +KH,PO, +H,0 ‘tao Tovoethane Heat [C,H,0H+ HI A, C,H1+11,0) (i) Action of phosphorus halides: Action of phosphorus halides on alcohols converts them readily into alkyl halides 3ROH+PX, —> 3RX +H;PO; The alkyl chlorides are formed by the action of PCl; or PCI, on alcohols. 3C,HjOH +PCl, —> 3C,H.Cl+H,P0, CH,CH,CHOH+ PCL, —> CH,CH,CH,CI+ POCI, 1 Propano} Cheops cy In the case of preparation of alkyl bromides and iodides, PBr, or Pl, required for the reaction is generally produced in situ by the action of red phosphorus on bromine or iodine Thus, the overall reaction may be depicted as: (2P+31, —> 2PI) or (2P+3Br, —> 2PBr5) P+ Br, ron Ft, Ra; ron “3 r—Br 3C,HjOH+ Pl; —> 3C,H5I+H,PO, ‘The method gives good yield of primary alkyl halides but poor yields of secondary and tertiary alkyl halides because secondary and tertiary alcohols on heating forms alkenes. The method is useful for preparing lower alkyl bromides and iodides in the laboratory. Gi) Action of thionyl chloride (Darzen’s method) : Alkyl chlorides are prepared when thionyl chloride and alcobols are refluxed in presence of pyridine. Pyridine Prine, aci+so,t+Hcit ROH+soa,, C,H 0H +socl, 8, Eshnol ‘Thon! shlonide ‘This method is widely used for the preparation of alkyl chlorides only as it has advantage over phosphorus chloride because the byproducts sulphur dioxide and hydrogen chloride are gases which can be easily removed from the reaction mixture. Bromides and iodides are not prepared by this method, because thionyl bromide is unstable and thionyl iodide does not exist 4, From silver salts of fatty acids: Alkyl chlorides or alkyl bromides are prepared by the action of chlorine or bromine in CCl, on silver salt ofthe fatty acids. This reaction is called Borodine-Hunsdiecker reaction or Hunsdiecker reaction. CHCl +80,1 HEI Chioroethane RC60Kg +B, Sy RB 460, +A CH,CH,COOAg+ Br, ©" CH,CH,Br +0, + AgBr Siherpopionte Enh rome This reaction gives the product with one carbon atom less than the fatty acid and the yield of halide is 1° > 2° >3°. But iodine forms ester instead of alkyl halide and is called Birabaun-Simouiu reaction. 2RCOOAR +1, —> ROQOR +260. +2Aal One useful modification of this reaction is the use of HgO ‘or PB(OAC), in place of silver salt to form alkyl halides. XaIHtg0. 2RC00H “Ss 2k —X +200; + Hex, +H,0 coon POM, gy inv 5. By halide exchange method: This is a convenient method for the preparation of alkyl iodides. The corresponding alkyl bromides or chlorides are heated with a solution of sodium iodide in acetone or methanol. RCL+Nal ASE, I+ NaCl Acetone. CH,Br fae? CHI +NaBr hy| bromide Fig nde ‘This reaction is called Finkelstein reaction. Even alkyl fluorides which cannot be prepared by the above methods may be obtained from corresponding chlorides by the action of mercurous fluoride or antimony trifluoride or ASF; or AgF, etc,, (Swarts reaction). +Nal 2CH,CI+Hg,F, —> 2CH,F + Hg Cl, Meth fluoride C.MsBr+AgF —> CHF +AgBr Fluoro ethane 3CH,CCI,CH, +28bF, —+ 3CH,CF,CH, +2SbC1, 6. By Rydons method: An alcohol on heating with hhalogen in presence of triphenyl phosphate (PhO);PO produces alkyl halides. R—CH,OH+ Br, +(C,H,0),P0 85 R—CH;Br +CgH,OH + (CeH,0), POBr 8.4 PROPERTIES OF ALKYL HALIDES Physleal properties : (i) CH,F, CHCl, CH,Br and CyHCl are gases at room temperature, while CHI is a liquid at room temperature. The alky! halides upto Cy, are colourless liquids while higher members are colourless solids. (ii) Alkyl halides are insoluble in water but soluble in organic solvents. i) They burn on copper wire with green edged flame (Beilstein test for halogens).(iv) Alkyl bromides and iodides are heavier than water. Alkyl chlorides and fuories are lighter than water. (©) Alkyl iodides become violet ot brown in colour on exposure as they decompose in ight ori HB, peat, _ (i) Fora given alkyl group, the boiling points of alkyl halides are in the order RI> RBr> RCI > RF and for a given halogen, the boiling points of alky| halides increase wih the increase ofthe size ofthe alkyl group. In a group of isomeric alkyl halides, the order of boiling point is: Primary > Secondary > Testary (viiy Atty! hatides are in general toxic compounds and bring unconsciousness when inhaled in large amounts. Chemical properties : The alkyl halides are highly reactive, the order of reactivity is: Todide > Bromide > Chloride (nature ofthe halogen atom) Tertiary > Secondary > Primary (ype of halogen atom) Amongst the primary alkyl halides the order of reactivity is: CHX > CH > CHK, ee ‘The high reactivity of alkyl halides can be explained in terms ofthe nature of CX bond which is highly polarised covalent bond due to large difference in the electronegativities of carbon and halogen atoms. ‘The halogen is far more electronegative than carbon and tends to pull the electrons way from carbon, Le, halogen acquites'asmall negative charge and carbon a small positive charge. es Cx ‘This polarity gives rise to two types of reactions. @ Nucleophitie substitution : The C* site is susceptible to atack by nucleophiles (an electron rich species) sno + BULEE Nurs x Neen Halidon Rox Se “ R—Nu (8,1 reaction) ., Nov +R—-X SOY) Nu... FAS Nu ‘Tramiton stato R+X- (y2 reaction) In S, reaction, there can be racemization and inversion and ordeof reactivity is: Sy1_ order: Benzyl > allyl > 3° >2°> Sy2 Teactions are concerted reactions and configuration of carbon is changed (Walden Inversion). Sy2 order :Methyl >1° >2°>3° > allyl > benzyl halides. So, tertiary alkyl halides are practically to substitution by Sy2 mechanism because of steri¢ hindrance. (i) Elimination reactions : The positive charge -on carbon is propagated to the neighbouring carbon atoms by 1°>CH,—X GB. Organic Chemistry for Competitions inductive effect. When approached by a strongest base (B), it tends to lose a proton usually from the B-carbon atom. Such reactions are termed elimination reactions. They are also E and Ey reactions. E, reaction : r HOH iia Vl simp ON RC fo HS R—C* cH ES R— | “| t HX H E; reaction : Eiteee als ‘ reese nbhe Ben p=CH HX a& H “Teanstion sate + BMX ‘As the above reactions involve leaving of X~, the reactivity of alkyl halides (same alkyl group, different halogens) should be limited with C—X bond strength “Type of bond cal cam cat Bond strength (kalimal) 45.5 4 66 ‘Bond srength increases ‘The breaking of the bond becomes more and more secondary > primary) is due to + effect of the: alkyl groups which increases the polarity of C—X bond. R R mcs, Sar, R>-CHy +X R R ‘The primary alkyl halides undergo reactions either by Sy2 or Ep mechanisms which involve the formation of transition state, The bulky groups cause steric hindrance in the formation of transition state. Therefore, higher homologues are less reactive than lower homologues. CH X >C,H,X >CH,X, ete, Alkyl halides are extremely important reagents in organic syuulesis ao dicy undergo a large variety uf reactions which are listed below. 1, Nucleophilic Substitution Reactions (@ Hydrolysis Formation of alcohols): Alkyl halides are hydrolysed to corresponding alcohols by moist silver ‘oxide (AgOH) ot by boiling with aqueous alkali solution (NaOH or KOH). The attacking nucleophile is OF Heat RX + AgOH 25 ROH +AgK Alot ie” Mois | Alco RX +KOH(ag.) “5 ROH+KYHalogenated Aliphatic Hydrocarbons C,HyBr +AgoH 2 C,HJOH + AgBr tl bromide ty alcool [With the help ofthis reaction an alkene can be converted into alcohol. Alkene is first reacted with HB#to form alkyl bromide and then hydrolysis is done. H,c—=cH, —#8°5 cn,cu,Br 84, cu,cx,on] Ethylene Ethyl bromide. Ethyl alcohol (ii) Reaction with alkoxides or dry silver oxide (Formation of ethers): Ethers are formed by heating alkyl ‘halides with sodium or potassium alkoxides or dry silver oxide. The altacking nucleophile is OR- (Williamson's synthesis). RX + NaOR’ Sodan ROR’ ‘Unsym. ether Hat, +Nax 2RX' +Ag,0 “5 R—O—R +2AgK Alkyt halide (Dry) Sym ether 2C,HBr +Ag,0 “SS C,H,0C,H, +2AgBr Brooch (Dy) Dieter 2S CyHOCH, +NaBr yt met eer CHsBr+ NeOCHs " C,Hj0C,Hs + NaBr Sodium horide Ditty cher C,HsBr+ NaOCH, Sodium methoxide CH) tC, +C31,0Ne ts Br CH 2-Bromo-3-methyl butane CH | cHyctl,—¢—cH +CH; —CH_—CH—CH, Oc, OCH; CH 2-thoxy-2- mt bane ino) (Majo) Mechanism : , cde CH, Fence cH GHt—torcH, Be Gry oy, Oca Leese CHC, + cH, 2 OS!5 cx, cH, eal cH, cH 3 Cxbocstion (Mos sabe) ‘There can also be elimination from 2° and 3° carbocation to give an alkene, (ili) Reaction with sodium or potassium hydrogen sulphide (Formation of thioalcohols): Alkyl halides form thioalcohols with aqueous alcoholic sodium hydrogen sulphide or potassium hydrogen sulphide, The nucleophile is ae a RX+ Nasi -SAMOWILO, sey + Na Sodivn hydrogen Thoaleobo} sulphide or Alkanethiol HBr +NasH—HOHO, CoH SH +NaBr ty bromide Ey tialeotol oF ligt mereapan Gv) Reaction with alcoholic potassium cvanide and silver cyanide (Formation of alkane nitriles and Isocyanides) : Alkyl cyanides are formed as the major product when alkyl halides are heated with alco potassium cyanide (attack occurs through C). The nucleophile isCN". Rx +KCN Aol, RCN + KX Alkyl halide ‘Alkane nitrile (Ally eyanide) Alcobot C.HsBr +KCN SSM, C.HLCN +KBr Ethyl bromide Propane nitrile (Ethyl eyanide) Alkyl cyanides are used to prepare many other types of ‘compounds, (a) Carboxylic acids are obtained by hydrolysis of cyanides with mineral acids dil. HCI or alkalies. Rc=n —22_, rconH, 2°, RCOOH+ NH Alkyl cyanide Cone, HCI Amide DULEICL™ Acid CH,C=N +2H,0 PLHCL, cH,COOH +NH, thanoic acid (Acetic acid) (b) Amides are obtained -by partial hydrolysis. of cyanides with alk. H,0, or cone, HCI. ‘Alk. HO: ‘or Cone Cone. HCI — (or 0, NaOH RC=N +H,0 Allyl cyanide CHy—C=N + H,0 Ethane nitrile Ethanamide (Acetonitrile) (Acetamide) (©) Primary amiines are obtained by the reduction of ceyanides with nascent hydrogen obtained by action of sodium and ethanol or with TiATH, or with nickel (Mending reaction). RCONH, ‘Acidamide CH,CONH, NalCHj08. NeCAHSOH, RC=N + 4{H] RCH,NH, Aly eyaide Price ene CHCH,C=N + 4H] 3YCHOK, Cy .cH,CH.NH, Propane nile ropa-Lattine Gayl cyanide (rPropyianise) (@ Aldehydes are obtained by partial reduction of ‘cyanides with SnCl, and HCI and then steam distilled (Stephen’s reaction).Sly HO Fa? R—CH== NH Hc! 2, Ime hydrochloride | R—C=N 42H SI, Alkyl eyanide R- SHO+NH,CI Miki When alkyl halides are heated with aqueous ethanolic silver cyanide, alkyl isocyanides (carbylamines) are formed as the major product (attack occurs through N). Isomeric alkyl ‘eyanides are also formed in small amounts. rx eagen As Ro Ae C +A ‘At iocsaide C)HgBr +AgCN 45 CHNes® + Agbr rotate (Ale) ty inseyanide (Eacabyante) Alkyl isoeyanides on reduction with sodium and alcohol gives secondary amines. cHy—N2 Na/CH40H +4H CH,—NH—CH, Mesh! isccyanide Dimethylamine Explanation: The formation of cyanides or ‘isocyanides from alkyl halides involves nucleophili substitution reaction. The cyanide ion (2CN) is a resonance hybrid of the following structures: coe C=N Hybrid sructre As is evident from the hybrid structure inthe cyanide fon, both the carbon and the nitrogen atoms have a pair of electrons. Therefore, either the carbon or the nitrogen atom can act as the electron donor (© the alkyl halide. Such a nucleophilic species which is capable of attacking the molecule through two sites is called ambident nucleophiles. ‘Thus, CN™ ion is an ambident nucteop! Now alkali metal cyanides (KCN or NaCN) are predominantly fonie. ‘Therefore, both carbon and nitrogen atoms are free to donate electron pair. Since C—C bond is relatively stronger than C—N bond, therefore, in this case attack mostly occurs through the carbon atom of the eyanide ‘group and alkyl cyanides are the major product. ‘On the other hand, silver cyanide is predominantly covalent. Consequently only nitrogen electron pair is available for bond formation, and the attack mostly occurs through the nitrogen atom of eyenide group giving allyl fsocyanides as the major product. (¥) Reaction with potassium nitrite or silver nitrite (Formation of alkyl nitrite and nitro alkanes): On heating an alkyl halide with potassium nitrite in an aqueous ‘ethanolic solution, alkyl nitrite is obtained as the main product ‘though some nitroalkane is also formed, It is because the bond between K—0 is ionic in nature, therefore, negative charge ‘on oxygen serves as attacking site.The nucleophile is —ONO™ RX +K*-0—N=0- 4 R—O. Haloalkane ‘Alksnitrite O+KX GRB. Organic Chemistry for Competitions 2H Br Ethyl bromide +K—0—N=0 25 ¢,H,—0—N=0 Baty nite \ +KBr However, wht alkyl halide is heated with silver nitrite in an aqueous ‘ethanolic solution, nitroalkane is the main product, Some alkyl nitrite is also obtained. Its because the bond between Ag—O being covalent.The lone pair on nitrogen acts as aacking site for nucleophilic substitution exHLOWt9 RK +AgNo, HECUAES p NM +Agx alae eat <0 © Catsbe+ Agog SHI carn ae 2 0 Silver nitrite Heat Nitroethane (vi) Reaction with ammonia (Formation of amines): On heating with aqueous ot alcoholic solution of ammonia in a sealed tube at 100°C, alkyl halides yield a mixture of amines and quaternary ammonium salt. The nucleophile is NH3 in the first reaction. CoHsBr+H—Nu, ES ¢,H,NH, +HBr ae)? Bavane iy CyHiNy +B CH, CHOY, cnc, +H at arene) (cation + Brett, BMH, ,ti)yN HBr —o reste) ‘ethanamine (2°) ty oH, SHE, ogi re chee) et ae a This reaction is called Hofmann ammonolysis of alky! halides. (vii) Reaction with silver salts of carboxylic acids (Formation of esters): On heating with silver salts of carboxylic acids in alcoholic solution, alkyl halides yield esters. The nucleophile is R’COO™. HOH, Recooag xn PSH, Recor + Agx CH,COOAR + Br CzHs “HH, CH,COOC,H, + AgBr Silver acetate Ethyl acetate (viii) Reaction with sodium acetylide (Formation of higher alleynes) : Alkyl halides react with sodium alkynide RX +Na—CosCH —> R—C==CH +NaX Sod, aceylide Higher alkyne (CH,CH,Br + NaC=CH —> CH,CH,C=CH+NaBr Beomoethane But-eyneHalogenated Aliphatic Hydrocarbons Note: Sodium allynides are prepared when temninal alignes react ‘With sodamide (or sodium in iguid NH) at 197 K. Roomch + Nant, HENS pcmcia + NH Ee (ix) Reaction with sodium or potassium sulphide (Formation of thioethers): Alkyl halides react with sodium or potassium sulphide in alcoholic solution to form thioethers. The nucleophile is SR. eayousg R-S—R+INeX 2RX+ NaS sobadpite Hea SHOWN 2C HBr +Najs POMS 44, —§ — Cyt +2NaBr Broncethane Ely thethne (Diet toes ‘Thioethers can also be obtained by heating alky! halides with alcoholic solution of sodium mereaptide (NaSR’), Le. tetallic derivative of a thioalcohol. RX + NawSp’ SAEOWTHO, p_ gprs Nay Sodium Heat" “Thioether mercaptide C,HBr + NaSCH, Sodium meityt Heat ‘mereaptide CHOW aS CyHs—S—CH, Edy methyl thioether (Metin thicethane) +NaBr () Reaction with halides (Formation of alkyl fadidos): Allyl chlorides react with sadinm bromide oF sodium iodide (in acetone or methanol) to form alkyl bromide or alkyl iodide. Similarly, alkyl bromides react with sodium iodide (in acetone or methanol) to form alkyl iodides. RCL +NaBr AS, ppp Mp Alot Abst All chloride bromide iodide C)HsBe +Nal “2%, CoH +NaBr iy bromide oie ‘This is called Finkelstein reaction. 2. Elimination Reactions (ai) Dehydrohalogenation (Formation of alkenes): ‘When alkyl halides are boiled with a concentrated alcoholic, potassium hydroxide, they undergo dehydrohalogenation (HX) and alkenes are formed. ‘These reactions are called fretimination reactions bbocause the hydrogen atom of haloalkane which ia eliminated comes from a f-carbon (i.e, the carbon atom next to that which carries the halogen). a WT la *KOH(ale.) —> R-( H (x Haloalkane Piga o-z i aicslean H+K-OH(le.) 225 4 ‘Bromocthane +H,0+ KBr In this reaction, ether is a by-product as potassium, ethoxide is always present in small quantity. C)HsBr+KOCjHy —> Cyl; —O—C)Hy + KBr ‘The reactivity of haloalkanes towards’ elimination reactions is: Tertiary (3°) > Secondary (2°) > Primary (1°) This is due to +f effect of the alkyl groups which increases the polarity of C—X bond. This can also be explained on the basis of the stability of | the alkene formed after dehydrohalogenation of haloalkanes. Tertiary alkyl halides on dehydrohalogenation form more substituted alkenes, which being more stable are formed at faster rate, while primary alkyl halides yield least substituted alkenes, which being less stable are formed at slower rat. teat aa ene (Chloroethane (1° *) a aay Ethene (tna he ae ca —cat-cr, +Kottley iy cyc—ct & ee a chun ipe9 gratis a ah = cy, + Kom) ity cry tc, I HCY >-Methyl propene a (Dimethyl substituted 3-Chloro-2-methyt propane alkene, most stable) 6) In the dehydrohalogenation of secondary and tertiary haloalkanes, when there is a possibility of formation of two isomers, the hydrogen atom is preferentially eliminated from the adjacent carbon atom with lesser number of hydrogen atoms. This generalization is known as Saytzeff's rule, ie, the more substituted alkene is more stable. For example, CHy—CH—=CH—CH, But2-ene (80%) (Dimettyt ethylene, more stable) I=CHy ‘But-l-ene (20%) (Eityleglee, less stable) ‘The ease of dehydrohalogenation isin the order: Tertiary alkyl halide > Secondary alkyl halide > Primary alkyl halide pe rad cmb, OHA Br “cH;—CH;—cH 2-Bromobutane uae and the ease of formation of alkenes R,C=CR, > R,C=CHR > R,C=CH, > RCH=CHR >RCH=CH, > H,C=CH,400 For different halogens itis in the order: Iodide > Bromide > Chloride (sil) Action of heat : Alkyl halides when heated above 300°C, tend to lose a molecule of hydrogen halide forming alkenes. RCH,CH,X 22S, RCH=CH, + HY ‘Alken cote 2S; cmon, +H Eihese ‘The decomposition follows the following order: Todide > Bromide > Chloride (When same alkyt group 1s present) and Tertiary > Secondary > Primary (When same halogen is present. 3. Miscellaneous Reactions (xiil) Reduction (Formation of alkanes): Alkanes are formed when alkyl halides are reduced with nascent hydrogen obiained by Zn/HC! or sodium and alcohol or Zn/Cu couple ‘on alcohol or LiAIH, or palladium carbon or Mg-Hg/water or ‘ributyl tin hydride (Bu SnH) etc. NiorP¢ Mohs Rt Rx +2H SES RH NiorPa CuBr 42H S255 cy, + HBr Ethyl bromide “ethane The reaction is used for the preparation of pure alkanes. ‘Metal catalyst such as Ni, Pd or Pt at 200-250°C, of HI in presence of red phosphorus at 150°C can also be used for the reduction of alkyl halides into comesponding alkanes. ‘Bu,Snl is a selective reducing agent because it reduces ‘only halides (and nitroatkanes) and has no effect on any other functional groups. ‘Among halides, RI> RBr > RCI. Due to this reason, the reagent tributyl tin hydride (Bu,SnH) shows substantial selectivity towards polyhalogenated compounds. cl a Bu;SaHl (Cais) Salt Br NO, | Sal [CH,CH,CHCOOC;H, —=2"" CH,CH,CH,COOC;Hs] (xiv) Wartz reaction : An ether solution of an alkyl halide (preferably bromide or iodide) forms. symmetrical alkanes when heated with metallic sodium. +2Na POSH p_p+2NaX ‘Alkane 2RX All halide CH, PEP, cH, CH, +2Nal Ethane G.RB. Organic Chemistry for Competitions 2C,H,Be +2Ne 2, 1, CuK +2NaBe ae pas 201-1926 2% a-ha CH, 2slodopropane CH, CH, 2,3-Dimethy! butane +2Nal ‘Tertiary hatides do not undergo this reaction. Unsymmetrical alkanes can be conveniently prepared by Corey-House reaction. (xv) Reaction with magnesium : Alkyl halides form Grignard reagents when treated with dry magnesium powder in dry ether. RX +DryMg 22S, p—Mg—x (Powder) Grigaaed reagent cattsbe + Me 22S Cyt aebe yl bromide (Dy) ty ngs romide Grignard reagents are used for making a very large umber of organic compounds. Reactivity order is, RI> RBr > RCI. (vi) Reaction with other metals : Organometallic compounds are formed. (2). When heated with zine powder in ether, alky! halides form dialkyl zine compounds. These are called Frankland reagents. 2C;HyBr +2Zn —EEs (C,H), Zn + ZnBry (b) When heated with lead-sodium alloy, ethyl bromide gives tetra ethyl lead (TEL) which is used as antiknock compound in petro 4C,HsBr + 4Pb(Na) PLS, (C,H) Pb + 4NaBr +3Pb TEL (©) Alkyl halides form diatky! mercury compounds when treated with sodium amalgam. 2C,H,Br +Na—Hg —> (CoHls);Hg +NaBr Brotmelane Die meray (@) Reaction with Lithiam : Alkyl halides react with lithium in dry ether to form alky! lithiums. Rx 421i EM, RL +L C)HsBr +2Li —> CjH,—Li +LiBr Eyl bromide thy iam 2R—Li +Cul —> —LiR,Cu Altar Lithium ay copper Allkyi lithiums are similar in properties with Grignard reagents, These are reactive reagents also and serve as strong bases. ‘Alky/ halide reacts with lithium dialkyl cuprate (RCuLi) to form unsymmetrical alkanes (Corey-House synthesis). RyCaLi+ R'X —s ROR’+R—CatLiX ‘AlkaneHalogenated Aliphatic Hydrocarbons 401 (CH,),CuLi +Br CH,CH, —> CH,CH,CH, (CH,CH,CH,CH,Br —¥°Cr_, cy, CH—CH,—CH Ltn dmeiyl Et bromide Propane Lromabane AB AICS I +CH,Cu + LiBr ee (xvii) Friedel-Crafts reaction : Alkyl halides react with benzene in presence of anhydrous aluminium halides to Uses: (i) Lower members are used as anaesthetic agent, form a homologue of benzene. Call, + Rc MCHC), +I Benzene CHR Ally! benzene Cols + CH Br SES), CoH CH, + HBr Deizebe Dromesthane Eibyt benzene (xviii) Substitution (Halogenation): Alkyl halides ‘undergo further halogenation in presence of sunlight, heat ‘energy or peroxide. By, Be, HBr 2 C)H.Br, $5 CH3Bry (xix) Oxidation reaction: Only primary and secondary alkyl halides undergo oxidation while tertiary alkyl halide does not. Primary (1°) alkyl halides on oxidation with dimethyl sulphoxide, (CH3)SO(DMSO) give aldehydes (Swern oxidation), pera R—CH)X MSO, p_C_u Pade (CHD280" "Aldehyde Onidation can also be done with hexamethylene tetramine, (CH,),N, followed by hydrolysis. Secondary (2°) alkyl halides give ketone in this reaction. soo, A Pe CHe ese eee CHD” Ketone x @HOT 2° Halide DMSO or Ce CHL—X aaa Calls CH Bent tatide OCHO “Benaldchye Oxidation of benzyl halides with (CH) N, is known as Sommelet aldehyde synthesis. (2) Reactivity for oxidation reaction depends on the umber of hydrogen atoms on alpha (a-) carbon of alkyl halides: Reactivity e number of o-hydrogen (b) Reactivity of different halides in decreasing order is as follows: Benzyl halides > Allyl halides > Alkyl halides (xx) Isomerisation: Haloalkanes on heating at 300°C or in presence of anhydrous AICI, at low temperature undergo ‘molecular rearrangement to form an isomeric haloalkane. For example, CH;CH,CH,cl Cor, cH, —cH—cH, [-Chloropropane At AICI, & 2-Chloropropane reffigerant and solvents. (i) Alkyl halides are used as alkylating agents, Le, t0 introduce the alkyl group in a molecule. . (iii) Alkyl halides are starting materials for the preparation of many organic compounds. Ethyl chloride is employed for the manufacture of tetraethyl lead, Pb(C3H)4, used as antiknock in gasoline for running automobiles. 8.5 DI-HALOGEN DERIVATIVES General Methods of Preparation ( Alkylidene halides or gem-dihalides or 1,1-dihalo- alkanes : The given general rhethods are used for the preparation of gem-dihalides: (a) By the action of ‘phosphorus pentahalides on aldehydes and ketones : Two halogen atoms can be added to same carbon atom when aldehydes or ketones are treated with phosphorus pentahalide. CH,CHO +PCl; —+ CH,CHCl, + POCI; ‘Acetaldchyde 1,1-Dichloroethane (iiytidenechirie) CH,COCH.+PCl,—+ _ CHjCCIACH . + POC; ‘Acetone 4 zDichlor opane (sopropyliden. chloride) (b) From alkynes : Additivn of halogen acids to alkynes form gem-dihalides. For each molecule of an alkyne, two molecules of halogen acid are required, ie, triple bond is first converted into double bond and then double bond into single. bond. HC=CH+HCI > H,C=cH—c1+#, H,c—cucl, ‘Acetylene Vinyi eleride| 1.iDiehloroetiane HC=CH+2HBr —+ — CH,CHBr, Acerylene 1.LDibrompethane (Eityldene bromide) CH,C=CH+2HCl—> _CH,CCL,CH, Propyne 22-Diehloropropane (sopropylidee chloride) ue halides or vic-dihalides or 1,2-dihalo- ‘These may be obtained by following metho x the addition of halogens to alkenes :, Addition ‘occurs on the two carbon atoms linked by a double bond. H,C=CH, +Cl, —> CH,CICH,CL liylene 1,2-Dichlorocthane (Gitylene chords) CH,CHCH, + Bry —> CH,CHBrCH,Br 12 Dibromapropane (Propylene bromide) (®) By the action of phosphorus halides on glycols : — Glycols or dihydric alcohols react with phosphorus halides or halogen acids or SOCI to form vic-dihalides,GR.B. Organic Chemistry for Competitions CH,O# CH,CI 42Pcl, >. | +2POCI; +2HCI CH,OH CHC Bttyléne 1,2-Dichloroethane ‘yea! (Ethylene chloride) ‘Note Alkylidene or alkylene iodides ae prepared by halide exchange Physical properties : (i) Dihalogen derivatives of lower alkanes are colourless, sweet smelling liquids. Higher homologues are solids. (i) They are insoluble in water but soluble in organic ts. i) They are heavier than water, The relative density of methylene iodide (CHj1;) is 3.325 which is the heaviest solv regen, liquid known (except mercury). (iv) They have high boiling points, Their boiling and melting points show regular gradation. —. Peiperty ‘Ayden baller (Gombe) [Atlee hates (viable) 1 avers Form lichen or atone, Form deo, |(With ag. KOH) - on ¥ ue + 2KoH(ag) —> CH,CHCI, + 2KOHlag) + CHC Hy cHc—0 cust nt) |. t-Diehloro oH Acetaldeyde 12 eDietdovetie ane tle (Gipe on) WA a Hon cuon c+ KOH Cs) ye HE a ne~ Non wt, | 2 Dieppe ‘Usable 2 tgp cna) (Grob Hic Ll He ‘Aes 2, [pation with sicnotic [Fo ales, Form atynes, kunt wenyaonage cxycuc, EH, omen FR! rowaten, ft 1 Dire ‘spl da a? L2-Delro ssf cone 3. |Reaction’with Zn dust in|Form alkenes, |Form alkenes, methanol cuycuc, +20 4", y,c—cn, ee on ie sien (dy ewe aya ot, ‘erie (Ethylene) Ethylene (Ai) ‘Ethene inte cig) 4.-| Reaction with ale, KEN oN uct cue flowed by hydrobss|cucuic, +2KeN —> cucu +2Kc1 289, xa Ho land heating the product |1,1-Dictloro N HCL CaLCN ome 12 Datlorstane coon H,cooH cca Het, cH,cH,coon i COOH ~©% —Propasoic acid CH,COOH Mette Chemical properties : Chemically, alkylidene halides are less reactive while alkylene halides have nearly the same reactivity as alkyl halides. The important chemical properties are given ahead in comparative form. 8.6 TRI-HALOGEN DERIVATIVES Chloroform or ‘Trichloromethane (CHC1,) It is an important trihalogen derivative of methane. It was discovered by Liebig in 1831 and its name chloroform was eens acide acd Dvecne aciéide (Diarbonyic aid) proposed by Dumas as it gave formic acid on hydrolysis. In the past, it was extensively used as anaesthetic for surgery but now itis rarely used as it causes liver damage. Preparation : 1. Chloroform is prepared both in the laboratory and on large scale by distilling ethyl alcohol or acetone with bleaching powder and water. The yield is about 40%. The available chlorine of bleaching powder serves both as oxidising as well as chlorinating agent.Halogenated Aliphatic Hydrocarbons 403 Ca0Cl, +H,0 —> Ca(OH), +Cl, Bleaching powder From alcohol : (i) Alcohol is first oxidised to acetaldehyde by chlorine. [Cl, +H,0 —>2HCI+0} CH,CH,OH+Cl, xii, CH,CHO +2HCL thy alcohol ‘Actaldeyde (ii) Acetaldehyde then reacts with chlorine to form chloral (trichloro acetaldehyde). Chlorination, Meare, CH,CHO +3C1, CCICHO +3HCI Acetaldebyde Trichloroacetaldehyde (Chioral) So, Cl, acts both as an oxidising () and chlorinating agent Gi] (Gi) Choral thus formed, is hydrolysed by calcium hydroxide, CCh}CHO ORC} CCl, i 1 Ob Hydro pe | Bite crcl Hi—o~Coo—/ H Chloroform + (GHCOO);Ca Calcium formate [2ccl,cHO+caoH), EY, rcHeI, + (HCO0),Cal From acetone: (i) Acctone fist reacts with chlorine to form tichloroacetone. CH,CocH, +3c1, CMetiastin, cy .cocH, +3HC1 Aceone Tichoroucetone {i Trichloroacetone is then hydrolysed by calcium hydroxide, -CChi COC, HSCCO! CCH joie Fates scHcl, Chloroform + (CHsC00),Ca (Cale acetate 2. From carbon tetrachloride: Now-a-days, chloro- form is obtained on a large scale by the reduction of carbon tetrachloride with iron fillings and water. This method is used in countries like USA. cei, +n S82, cuci, +HC1 Heat This chloroform is not pure and used mainly asa solvent. 3. Furecblorotorm: | Wis ubisined by distilling chloral hydrate with concentrated sodium hydroxide solution. CCI,CH(OH), +NaOH —s CHCI, + HCOONa+H,0 ‘Choral hydrate Note Citar iyaiare 5 & sabte compou inspite ofthe fact that two —OH groups gy “5 are linked tothe same carbon stom, This is due to the fact that intramolecular Cl>C—C@HL hydrogen bonding exists in the Cid o rmolecule between chlorine and r hydrogen tom of —OH group. ’ ji) It is a sweet smelling Physical properties : colourless liquid. i) Itis heavy liquid, Its density is 1.485. Itboils at 61°C. (iii) It is practically insoluble in water but dissolves in ‘organic solvents such as alcohol, ether, ete (iv) Itis non-inflammable but its vapours may burn with ‘green flame. (v) It brings temporary unconsciousness when vapours are inhaled for sufficient time. Chemica properties: () Oxidation; | When exposed to sunlight and air, it slowly decomposes. into phosgene and hydrogen chloride Ch Ch cl. cl DeC +101 HAs So (oh H "cr OH ch was e=0 cr — « — [eva,+40, $8 coc, Ha] ‘Sunlight or ACHCI, +3[0], ——="> 4COCI,\+2C1, +2H,0 Phosgene is extremely poisonous gas. To use chloroform 1s on anaesthetic agent, it is necessary to prevent the above reaction. The following two precautions are taken when chloroform is stored {@) It is stored in dark blue or brown coloured boitles which are filled upto the brim. (b) 1% ethyl alcohol is added. This retards the oxidation and converts the phosgene formed into harmless ethyl carbonate 0C,Hs COCI; +2CHJOH —> ome” +2HCL OC;Hs (i Et carbonate (i) Reduction; When reduced with zine _and hydrochloric acid ‘in presence of ethyl alcohol, it forms ‘methylene chloride. cue, +24 HC, cH,cl, +HCL (Chloroform (Ale) Metiylene chloride When reduced with zine dust and water, methane is the main product. cucl, +6 22°, cH, +3HC1 Methane (ii) Chlorination ; _ Chloroform reacts with chlorine in presence of diffused sunlight or UV light to form carbon tetrachloride.cuet, +c, YH, cca, +H Chloroform Carbon tetrachloride (wv) Hydrolysis: Chloroform is hydrolysed when treated with hot aqueous solution of sodium hydroxide or potassium hydroxide, The final product is sodium or potassium salt of formic ac. Cl+NaOH(ag.) on Ho 9 [noon ‘OH. a OH(aq.) CLE Na OH(aq.) (Chloroform Unstable (ortho-forni acid) 0 oO cS BaOH, a4 -H,O oH ona Sotisn mae Forini acid * yrs {S0, CHCL, + 4KOH(aq) 25 HcooK +3KCL+2H,0) (¥) Nitration: The hydrogen of the’ chloroform is replaced by nitro group when itis treated with concentrated nitric acid. The product formed is chloropicrin or trichloro nitro methine or nitro chloroform. Itis aliquid, poisonous and used as an insecticide and a war gas (ter gas). CHCI, + HONO, —> CNO,CI, +1,0 Niticactl—— Choropicrin (oD Heating with silver poder « Acetylene 1s formed when chloroform is heated at high temperature avith silver powder. no Girigar ica 4s women+eager Chlorotem Acetylene (ti) Condensation with acetone: Chloroform condenses with acetone on heating in presence of caustic alkalies. The product formed isa colourless crystalline solid called chloretone and is used as a hypnotic (drug) in medicine. THs roy HO CH; aycaromc€ "808 So ‘CH; €1,C ‘CH, ‘Acetone 1,1, -Trehoro-2smethyl propn-2-01 (Chloretone) Mechanism : (@ CHCI, +0H” —> 2CCy +H,0 Ch; — tc, +c) 20 GRE Organic Chemistry for Competitions. (viii) Reaction with sodium ethoxide: When heated OC pHs ‘OCzHs OC>Hs Ethyl ortho-forate (Gx) Reimer-Tiemann reaction : Chloroform reacts with phenol when heated in presence of sodium hydroxide or potassium hydroxide. The product formed is salicylaldehyde. OH on CHO Oo + CHCI + 3NaoH SS oO Phenol o-Hiydroxy benzaldehyde (Galicylaldetyde) + 3NaCI + 2H,0 (%) Carbylamine reaction (isocyanide test): This reaction is actually a test of primary amines. Chloroform, ‘when heated with primary amine in presence of alcoholic potassium hydroxide forms a derivative called isocyanide (Carbylamine) which has a very offensive smell. CcHsNH, +CHCI, +3KOH —W8™, Cg .NC+3KCL ‘ine Presyl inoeyanide +310 RNH, +CHCI,+3KOH(ala)—"> RNC +3KCI rane Ccatyianioattane| (Alkyl sone +3H,0 ‘This reaction is also used for the tet of chloroform, (xi) o-Ellmination reaction: Chloroform undergoes ‘a-elimination reaction to give dichlorocarbene (singlet) which is a reaction intermediate. Ale, KOH 5 cue; “<8 scot, +c + HOH ‘3 Dihlore- carbene Uses: (i) It is used asa solvent for fats, waxes, rubber, ine, etc. (ii) It is used for the preparation of chloretone (a drug) and chloropicrin (insecticide). (ii) Ils used in laboratory forthe test of primary amines, iodides and bromides. (iv) It can be used as anaesthetic but due to harmful effects itis not used these days for this purpose. It causes liver damage when inhaled in excess (SO is CC,). (v) It may be used to prevent putrefaction of onganic, materials, i. in the preservation of anatomical species. ‘Tests of chloroform = (i) It gives isocyanide test (carbylamine test). (ii) It forms silver mirror with Tollens’ reagent. (ii) Pure chloroform does not give white precipitate with silver nitrate.Halogenated Aliphatic Hydrocarbons 8.7. 1(ODOFORM OR TRHODOMETHANE (CHI) Todoform resembles chloroform in the methods of preparation: and properties. Laboratory preparation; _Todoform is prepared in the laboratory by ‘heating ethanol or acetone with iodine and alkali. (@) With ethanol: The reactions taking place are QNsOH+Is—> NeOl_ +Nal +10 Iypoiodite (i) Oxidation CH,CH,OH + NaOl —> CH,CHO +Nal +H,0 Ethanol Acetaldehyde Todination CH,CHO +3Na0l —> CI,CHO+3Na0H iodal (iii) Hydrolysis CI,CHO — +NaOH —s CHI, + _HOOONa “Wiiodoacetadchyde Todorm »Sodiim formate (b) With acetone : (i) Todination CH,COCH, +3NaOl —> CI,COCH, +NaOH Acetone “riiodoacetone (li) Hydrolysis (CI,COCH, +NaOH —> CHI, +CH,COONa Todoform Sodium acetate The complete reaction may be written as: CH,CH,OH +41, +6Na0H —°5 CHIL +HCOONa tan! Iodoferm +5Nal +5H0 Sodium carbonate cai be used in place 6f KOH or NaOH. CH,COCH, +31, +2Na,00; + CHI,L. +3Nal Aeetone Todatorm +CH,COONs +200, These reactions are called iodoform reactions. The todoform test. is exhibited by ethyl alcohol? acetaldehyde, acetone, those alcohols which possess —CHOH—CH, group (2-ols) and methyl ketones et. city CHGS 41, 480K 25 CHT, +CH,COONe Jodo by _ ecobety Propan-2-0 +5Nal +510 H 2 I R—C—CH, +NaOI—4> R—C—CH, +Nal +0 I on ° R—C—CH, +3Na0l—> Bay -Cl; +3NaOH I 3 R—C—Cl, + NaOH —> R—C—ONa + CHI, (Yellow pt) Industrial preparation : _ Iodoform is prepared on large scale by electrolysis of a solution containing ethanol, sodium carbonate and potassium iodide. The iodine set free, combine with ethanol in presence of alkali to form iodoform. The electrolysis carried out in presence of CO; and the temperature is maintained at 60-70°C. KD Kar es ar cathode Ktet25k 1, 426" 1 K+H,0 —> KOH+51 KOH is neutralised by CO, CsHJOH +41, +3Na,CO, —> CHI, +HCOONa Ethyl aleohot +5Nal +3CO, +2H,0 Properties: (It isa yellow crystalline solid. i) Tthas a pungent characteristic odour. Gil) Te is insoluble in water but soluble in erganic solvents such as alcohol, ether, etc. (iv) Ithhas melting point 119°C. Its steam volatile Reactions of Todoform ——Kot__. cook Hydrolysis potassium formate Rediuetion CHA, : Red POHL Methylene iodide ee | ‘Agpowder Acetylene cur,_{Cututamine action, Crane odotorm{CaNHs+KOH(Ale)” pS aoeyaide | —Hssingalore__. Yodine vapours, ACH; +30)~* 4C0+61;+2H,0 (Less sable than CHC) |__with AgNO: Yetlow precipitate of Agl (This eactions not given by choot) Uses :_Todoform is extensively used as an antiseptic for dressing of wounds; but the antiseptic action is due 1 the liberation offre iodine and not due to iodoform itself. When it comes in contact with organic mater, iodine is liberated ‘which is responsible for antiseptic properties. ‘Tests of Iodoform 1. With AgNO, : Aa 2. Carbylamine reaction : CHI; on heating with primary amine and alcoholic KOH solution, gives an offensive smell of isocyanide (carbylamine) CHI, gives a yellow precipitate of406 ERB, Organic Chemistry for Comperitions 3. Todoform reaction : With I, and NaOH or I and 'Na,CO,, the iodoform testis mainly given by ethyl alcohol ° I (CH,CH,OM), acetaldehyde (CH;—C—), c-methyl 9 ketone or 2-one (—C—CHy), secondary alcohols or 2-0 On (—CH—CH,) and secondary alkyl halide at C, a (—CH—CH,). Also lactic acid (CH; —CHOH—COOH), ° I pyruvic acid (CHy+C—COOH), methyl phenyl ketone 9 (CgHs—C—CH,) and 2-amino alkanes (R—CH—R) give NH, this test 8.8 CARBON TETRACHLORIDE OR TETRACHLOROMETHANE, (CCI,) It is the most important tetrahalozen derivative of methane. ‘Manufacture: (i) From methane: Chlorination of methane with excess of chlorine at 400°C yields impure carbon tetrachloride. 400°C, cH, + 4c, SPS; cer, ran (Gxces) Metliane used in this process is obtained from natural gas. i) From carbon disulphide: Chlorine reacts with ‘carbon disulphide in presence of catalysts like iron, iodine, aluminium chloride or antimony pentachloride. NCra BO Oo. sc, aralys) Sulphur rmonochloride S,Cl, further reacts with CS, to form more of carbon tetrachloride. CS, +3¢1, cs, +28,c1, “SY, ca, +68 Carbon tetrachloride is obtained by fractional distillation. Itis washed with sodium hydroxide and then distilled to get a pure sample. ii) From propane: Propane is reacted with chlorine at about 400°C and at a pressure of 70 ~100 atmosphere. cali, +901, Hs col, + Cel, +881 Propane Tessare Carbon Hexachioro- a, ae ‘gad Sa Physical properties: (i) Itis a colourless liquid having characteristic smell Gi) It is non-inflammable and poisonous. It has boiling point 77°C. ii) It is insoluble in water but soluble in organic solvents. (iv) Itisan excellent solvent for oils, fats, waxes und greases, ‘Chemioal properties : Carbon tetrachloride is less reactive and inert to most organic reagents. However, the following reactions are observed. (@ Reaction with steam (oxidation): Carbon tetrachloride vapours react with steam above 500°C to form, Phosgene, a poisonous,gas. Superheted cl, +H,0 —, ‘Steam 500°C COCI, +2HCI hose * Gi) Reduction + [¢s reduced by moist iron filling into chloroform, ca, +24 4, cc, +AC1 Git) Hydrolysis : On heating with aqueous potassium hydroxide it forms carbon dioxide which combines with potassium hydroxide to give KCI and potassium carbonate (inorganic salts). cot, +4KoH = (c(o),] 28 co, ‘Usable KOH, 00, +H,0 (iv) Reaction with phenol (Reimer-Tiemann reaction) : It combines with phenol in presence of sodium hydroxide to form salicylic acid. on on ‘COOH +408 Oass OF Phe cya a ed {Salicylic acid) + 4NaC+ 2840 (©) Friedel-Crafts reaction: Benzene on treatment with CCl, in presence of anhydrous AICI, gives dichloro- diphenyl methane which on hydrolysis forms dipheny! ketone (benzophenone). ‘Aid. AICIs 2C 6H, +cC1, “MEAS (C,H) cc1, 22% Benzene 4,(2HCD” “Didoro. ” -2HCI) | +KCL+H,0 cH cH, ubylene chore Vinyl chloride Vinyl chloride can also be obtained from ethylene chloride by thermal decomposition st 600-650°C. CHCl CHI — Tene CHCl cH, (i) From ethylene: Free radical chlorination of ethylene at 500°C yields vinyl chloride H,C=CH, +cl, 5 H,c—cuci Ethylene ‘Vinyl eboride (iil) From acetylene : Vinyl chloride is-obtained by controlled addition of HCI on acetylene. Acetylene is passed through dilute hydrochloric acid at about 70°C in presence of gC, as a catalyst to form vinyl chloride. This method is also used for its manufacture. nc=cu+Her S82, ,c—cHet Acetylene WC” Vy cherie Ihisa colourless gas at room temperature. Is boiling point is-13°C. The halogen atom in vinyl chloride is not reactive as in other alkyl halides. However, C=C bond of vinyl chloride aives the usual addition reactions “The non-reactvity of chlorine atom is due to resonance stabilization, The lone pair on chlorine can participate in delocalization (resonance) to give two structures R CHL < HCH 0 @ ‘The following two effects are observed due to resonance stabilization Hy (i) Carbon-chlorine bond in vinyl chloride has some double bond character and is, therefore, stronger than «pure single bond. (ii) Carbon atom is sp*-hybridized and C—CI bond length is shorter (1.69 A) and stronger then in alkyl halides (1.80 A) due to sp* hybridization of the carbon atom, Addition Reactions a (CH,Br—CHBrCI 1,2-Dibromo-1-chlroathane He [> cH —cHBrct 1-Bromo-1-choroethine H,C=CHcl gE : ¢ mt crora) [Povmerion. | coy bay cy, ae Lee Poiyvinyl chloride (PVC) Naot . No reaction The main use of vinyl chloride is in the manufacture of polyvinyl chloride plastic which is employed these days for ‘making synthetic leather goods, rain coats, pipes, floor tiles, gramophone records, packaging materials, etc. 2. Allyl lodide or 3-lodoprop-1-ene (CH ,CH=CH,) It is obtained: (i by heating allyl chloride with. sodium jodide in ‘acetone. Allyl chloride required in the reaction 18 prepared either by chlorination of propene at 500°C or by action of, PCI, on allyl alcohol. cH,cH=cH, +¢1, 2°, cH,—CH=CH, Propene a “Allyl chloride 3th Ceci FC, 28% 3CH,CH—CH,+H,PO, ou a Aly aloha x—CH—ON Aes, iy -cii—cH, a 1 Aly chloride Ay ii “+ NaCl This is halogen-exchange reaction and is called Finkelstein reaction, (i) by heating glycerol with HI HOH cH cua CHOH +341 bn f “HO > G “= cH01 CHI Ch Glycerol 123-Triedo-popane Ally indieIt is a colourless liquid. It boils at 103.1°C. The halogen atom in’allyl iodide is quite reactive. The p-orbital-of the halogen atom does not interact with x-molecular orbital of the double bond because these are separated by a saturated sp’-hybridized carbon atom. Thus, the halogen atom in allyl halides can be easily replaced andthe reactions of allyl halides are similar to the reaction of alkyl halides, Th terms of valence bond approach, the reactivity of halogen atom is due’ to ionisation to yield a carbonium ion which can stabilize by resonance ds shown below. H,C=CH—CH,I —> {H,C=CH—CH, <> H,C—CH=CH,]+1- ‘Substitution Reactions: Nucleophilic _ substitution ns occu 0H, o—cH_cH,0n ; Tanta! EOL, Hjc—cH_cxcn Allyl cyanide H,C=CHCH,I—“®_, H,C=CH—CH,NH, ‘att oat) ‘Allyl amine SBONS, H,C—CH—CH,OCH, ‘Allyl mets eer AeNO: H,C=CH—CH,NO, 2-Nioprop-e ‘Addition Reactions : Electrophilie addition reactions take place in accordance to Markownikoffs rule, H,C=CH—CH,I +Br, —> _ CH,BrCHBrCH,I 1.2-Dibtomo--iodoprepane H—CH,|+HBr —+ _ CH,CHBrCHL 2-Broic-Hiodopropane Allyl iodide is widely used in organic synthesis. 8.10 SOME MORE IMPORTANT HALOGEN DERIVATIVES 1. Freons : The chloro fluoro derivatives of methane and ethane are called freons. Some of the derivatives are: CHF,CI (tonochlorodifluoromethane), CF;Cl, (dichloro- difluoromethane), HCF,CHCl, (1,l-dichloro-2,2-difluoro- ethane) and CF,CI (chlorotrifluoromethane or” freon-11). ‘These derivatives are non-inflammable, colourless, non-toxic, low boiling liquids. These are stable upto 550°C. The most important and useful derivative is CF,Cl,_ which is commonly known as freon and freon-12. Freon or freon-12 (CF,Cl,) is prepared by treating carbon tetrachloride with antimony trifluoride in the presence of antimony pentachloride as a catalyst. HC G.RB. Organic Chemistry for Competitions SbCl 30CI, +280F, E> 3CCLF, +280C, Or it can be obtained by reacting carbon tetrachloride with hydrofluoric acid in presence of antimony pentafluoride. cc, +2HF 8, cci,F, +2HC1 Under ordinary conditions freon is a gas. Its boiling point is -29.8°C. It can easily be liquefied. It is chemically inert. It is used in air-conditioning and in domestic refrigerators for cooling purposes (as refrigerant). Halothane (CF;CHBrCl) and methoxy flurane (CH,OCF,CHC1,) are used as inhalation anaesthetic. 2. Teflon: Itisa plastic like substance produced by the polymerisation of tetrafluoroethylene (F;C—CF;). ‘Tetrafluoroethylene is formed when chloroform is treated ‘with antimony trifluoride and hydrofluoric acid. cucl, 3 cur,ci SES Rc—cr, HET ep. -76°0) On polymerisation tetrafluoroethylene plasticlike material which is called teflon. nCR=CF, —> £CF,—CF, 3; “Tetrafhioroethylene "Teo ‘Teflon is chemically inert substance. It is not affected by strong acids and even by boiling aqua-regia. Itis stable at high temperatures. It is, thus, used for electrical insulation and preparation of gasket materials. 3. Acetylene tetrachloride (westron)(CHCI;—CHCI,): Acetylene tetrachloride is also known as sym. tetrachloro- ethane. It is prepared by the action of chlorine on acetylene in presence of 2 catalyst such as ferric chloride, aluminium chloride, iron, quartz or kieselguhr. FeChor AICI HC=CH+2Cl, ————> CHC, —CHCl, ly (1,1,2,2-Tetachloroethane) In absence of catalyst, the reaction between chlorine and acetylene is highly explosive producing carbon and HCI. The reaction is less violent in presence of a catalyst. Itis a heavy, non-inflammable liquid. It boils at 146°C. It is highly toxic in nature. Its smell is similar to chloroform. Its. insoluble in water but soluble in organic solvents. On further chlorination, it forms penta _ and hexa-chloroethane. On heating with lime (calcium hydroxide), itis converted to a useful product westrosol (CCl,—CHC)). CHCL—CHC!, +Ca(OH), —> 2CHCI—CCI, Weerga Westrosol (Trichtoroetbene) +CaCl, +2H,0 Both westroi and westrosol are used as solvents for ils, fats, waxes, resins, varnishes and pains, et. forms aHalogenated Aliphatic Hydrocarbons 409 ILLUSTRATIONS OF OBJECTIVE QUESTIONS (Ans. ()] fi = (Hine: 23-Dichlorobutane have meso-isomer due to. the 1, On monochlorination of 2-methyl butane, the total mumbe ease of the pane of spemmeny] a ee (T 2004] 5, The compound added to prevent chloroform to form O6 @s phosgene gas (Poisonous gas) is: [PMT (MP) 2004] Qe Ol (@) CH,COOH () CHOH [Hint : The number of monohslogenstion products obtained oe (8 GHSOH any alkane depends upon the number of different Meee tipi i congine Tie. posible 6 Among the halogens, the one which is oxidised by nite ‘monochlorinated products of 2-methy| butane ae acid is: (@) iodine {b) chlorine (©) bromine (@ fluorine fans. (@)] {ilint: 1, +10HNO, > 2H10, + 10NO, + 44,0] toda 7. Which one of the following is excellent substrate for S,.» 4 reaction? —Br (4) and (forms o Oar er i [UPSEAT 2004] (© CH,—0—CH,Br (6) CH —C—CH, Br (@) Ethanol (b) Isopropyl alcohol Tans. @] {© Banal (@) Benzyl alcohol Brine Sg | gy ont om he bon sbi a sition state ofthe S reaction] 43. Which one ofthe following is excellent substate for S,,___8 On treating a mixture of wo alkyl halides with sodium 2 +" metal in dry ether, 2-methyl propane was obtained. The ae alkyl halides are: (@) (CH;);C—Cl (0) (CH, ),CH—CI (a) 1-chloropropane and chloroethane © (CH), NCU, (@) (CI), C—De (0) 2clotopropane and chlorethaue (Ans. ©] (6) 2-chloropropane and chloromethane int: Carbocation of the substrate (¢) is stabilized by (@) L-chloropropane and chloromethane elocalisation} fans. Ol 4. Which of the following will have a meso-isomer also? a Dey ete AIEEE 2006] Bat By EH—CH + Ne Cl, EE (8) 2-Chlorobutane a (b) 2,3-Dichlorobutane (©) 23-Dichloropentene yea + (@) 2-Hydroxy propanoic acid &, Ce ne ETT =ECY oY EY =1“0-1-ToT] 7 ‘SOME SOLVED PROBLEMS. Problem 1. How do alkyl, allyl and vinyl halides differ Problem 2. Give the conimon and IUPAC names for in structure? ‘C,H gBr isomers and classify them as to whether they are\?,2° Solution: The X in an alkyl halide is bonded to sp’- or 3°, hybridized carbon of an alkyl group. Solution : The isomers of C,HyBr are the following CHa; cHcH, ‘with common sid IUPAC names: eee taihnd CH,CH,CH,CH,Br ; CH,CH,CHBrCH, In an allyl halide, there is a CC bonded to the earbon (1-Bromobutane) (2-Bromabutane) ‘Butyl bromide Sec, butyl bromide bearing the X. bom) ia? Bomts) H,C=CHCH,X Allyl halide cH, cH, In vinyl halides, X is bonded to an sp-hybridized carbon I e of an alkene, ee rt H,C=CHX or CH\CH=CXCH, (Brame met propa) ca, | (1° Bromide) (@-Bromo-2-methy propane) ap -bybridied ap hybridized "Trt butyl bromide (G° Bromide)410 Problem 3.: (a) Give simple test 10 distinguish among hexane and CH, —CH=CHCI. (©) Give “simple test 10 distinguish among (CH,—CH—=CHCI, CH,CH,CH,C! and CH,=CH—CH,CI. Solution: (a) Hexane and methyl vinyl chloride are distinguished by adding bromine in CCl, to each. The red brown bromine colour persists in alkane but disappears in methyl vinyl chloride (b) H,C—CH—CH,Cl is an allylic chloride (The Cl is ‘very reactive). This reacts rapidly with AgNO, in the cold to give a white ppt. of AgCl. CH,CH,CH,CI gives white ppt. when warmed with AgNO, as it is comparatively lese reactive, CHy—CH=CHC1 is inert and does not form white ppt. with AgNO, Problem 4. Give reasoris for the following: (@) Potassium cyanide reacts with R-X to give alkyl ‘cyanide, while silver cyanide forms an isocyanide as a major roduct. PG) Silver nivite reacts with R—X to give @ mistre of nitroalkane and alkyl nitrite. (©) ROH does not react with NaBr but on adding H,SO,, it forms RB. (@) Aleohols do not undergo substitution in neutral or alkaline solution. Solution: (a) Potassium cyanide is an ionic compound, K*[{C==N?]” and provide cyanide ions in solution, in which each of carbon and nitrogen carry a lone pair of electrons [CN is an ambident nucleophile (ligand) ‘As lone pair on carbon is more reactive, the carbocation, R® preferentially attacks the carbon atom and thereby forms an aly eyanide predominant RY + [C= —> RCN: Alkyl eyanide (On the other hand, AgCN (being insoluble) is a covalent compound and only nitrogen has the lone pair of electrons. ‘Thus, carbocation attacks through nitrogen and thereby forms an alkyl isocyanide as a major product. Ag—C=Nt+RX —> RNCI+AgK: (b) The nitrite ion hhas two nucleophilic sites, .¢, N and either of the oxygen atoms. The carbocation can attack either N or O, thereby forming a mixture of nitroalkane, R—NO, and alkyl nitrite, R-ONO. (©) Br” ion is a very weak Bronsted base and thus, it ean not displace the strong base —OH™. When H,S0, acid is added, H* are available which form ROH,. Under this condition, Br~ displaces H,O which isa very weak base. ROH, + Br —> R* +H,0+Br” —> RBr+H,0 G.R.B. Organic Chemis for Competitions (@ A leaving group must be a weak base: The leaving —OH group of alcohols in neutral or alkaline solution would be stronger base, hence cannot be removed by weaker bases like CI", Br,” Problem 5. A halide, CsHyyX, on treating with alc. KOH gives only pent-2-ene. What is halide? . Solution : Two possible halides which on elit of HX can form pent-2-ene are: tion (CH,CH,CH,CHXCH,; CH,CH,CHXCH,CH,, o a The (II) structure being symmetrical gives only pent-2-ene on elimination of HX cu,cH,crxcy,cx, 242%, Thus, the halide is 3-halopentane. Note + The sireture () forms a mixture, CH,CH,CH=CHCH, and CH,CH,CH,CH—CH, “oar prey Minor prod) Problem 6. 4 white precipitate was formed slowly when AgNO, is added to a compound (A) with molecular formula (CHHy3Cl. Compound (A) on treatment with hot alcoholic KOH, ‘gave a mixture of two isomeric alkenes (B) and (C) having formula, CgHyy. The mixture of (B) and (C) on ozonolysis “furnished four compounds. (i) CH,CHO, (iil) CH,COCH, What are (4), (B) and (C)? (i).C,H,CHO, ) (CH) ,CHCHO. Solution : Given CgHi,,cl EEO, (B) + (C) ‘The molecular formula of (B) and (C) is CgHy2. Thus, on ‘ozonolysis of each alkene, the two products must have six carbon atoms. ‘One alkene gives CHjCHO and (CH,),CHCHO. Thus, the hydrocarbon should have the structure, (CHyCH—=CHCH(CH, )» @ Other alkene gives C,H CHO and CH,COCH). Thus, the hydrocarbon should have the structure, C;H,CH=C(CH5)2 0 Since (B) and (C) are formed from (A) by dehydro halogenation, the structure of (4) is: empennricrictt, a 3-Chloro-2-methyl pentane Creu cucHCHS AE KOM CHH,CH—=CHCH(CH,), @) a +CH,CH,CH=C(CH,), © As it is 2° halide, it slowly reacts with the AgNO, to form white ppt.Halogenated Aliphatic Hydrocarbons Problem’. How many isomers are possible forCHsF, and give their TUPAC names? Solution: mButane can have two possible gem- diftuoro isomers: F,CHCH;CH,CH, —CH,CF;CH,CH, 1,-Difuorobutane 2,2:Dihuorobutane ‘There are four isomers with two fluorine on different carbon atoms: FCH,CHFCH,CH, _CH,CHFCHFCH, 1,2 Difvorobuane (vie) 2.-Difuorsbutane (ve) PCH,CH,CHFCH, — FCH,CH,CH,CH,F 13-Dimorobuue ‘14 Difliorobutane ‘The ; obutane can have three possible diffuoro isomers: FOR, —PF-Cii, RCH GH-CH, FOR, —Fol-CHF cH, Hy cH, 1,2-Difro-2-nethy 1, Difuoro-2-methy!_1,3-Difloro2-methyl propane(vie) propane (gem) Propane Problem 8. Give the structures of two different alkyl bromides both of which yield the indicated alkene as the exclusive product of E; elimination : (@) CH,CH=CH, (b) (CH),C=CH, (©) BrCH=CBr, Br Sontn: (0 CHCH,CH;Br and CHy CHI, Hs (b) CHy—CH—CH,Br and cee ~CH; & he (©) Br,HC—CHBr, and Bri,C—CBr, SUPPLEMENTARY READING 8.11 ORGANOMETALLIC COMPOUNDS Organic compounds in which a metal atom is directly linked to carbon or organic compounds which contain at least ‘one carbon-metal bond are called organometallic compounds. ‘Some common examples are: CHL 5 (CHs)2Z0 5 (GH), PD Matyi tiie” Diet zine Tevet ead (C,Hs),Sn_ 3 (CyHs).Hg ; CH;Na Teta in Diet! mercury Met! sodiam AGMESK, © CHMaBe 5 RI C=C Ag feria Meth magnesia ilver alkynide CoHsHgCl 3 Phony! mereric chloride Most widely studied and synthetically most useful ‘organometallic compounds are those of magnesium and ithium, Alkyl magnesium halides are termed as Grignard reagents as these were discovered by Grignard in 1900. The Grignard Ait reagents are very reactive and used as synthetic reagents for the synthesis of alkanes, alcohols, aldehydes, ketones, acids, ec. Organometallic compounds are prepared from the respective alkyl ot aryl halides in solvents like ether. These compounds are mostly colourless, mobile liquids having low boiling points and are generally very unstable, A number of these compounds bum violently in air and are readily decomposed by water and alcohol. ignard reagents are prepared by.the action of alkyl halides on dry magnesium tumings in presence of dry alcohol-free diethyl ether. The ether solution of the Grignard reagent is used immediately in the apparatus in which it has been prepared. Dry ether dissolves the Grignard reagent through solvolysis. ieee ee 3) — Ma 208 GH; x GHs Grignard reagents are never isolated in free state on account of their explosive nature ‘Note: (i) Fora givenalkyl radical, the case of formation ofa Grignard reagent i, Todide >" Bromide > Chloride ‘Usually alkyl bromides ae used (ii) For a given halogen, the ease of formation of « Grignard reagent i, CX > GX > GH (ii) Since, tertiary alky iodides eliminate Hi to form an alkene, tertiary alkyl chlorides ar usd in their place. (iv) Grignard reagent cannot be prepared from a compound ‘Which consists in adition to halogen, some reactive group such as —OH because it wil rect rapidly with the GR. ‘The C—Mg bond in Grignard reagent is somewhat covalent but highly polar. Carbon being more electronegative than magnesium acquires partial negative charge and the ‘magnesium has a partial positive charge. ieee x The alkyl group thus acts as a carbanion or nucleophile. ‘The majority of reactions of Grignard reagent fall into two groups: (i Double decomposition with compounds containing active hydrogen atom or reactive halogen atom. RMgX + HOH —> RH + Me(OHDX RMeX +D,0 —> RD+Mg(OD)x RMpX + R’OH — RH + Mg(OR)X RMeX + R/NH, —> RH + Mg(R/NEDX RMgX +R’ —> R—R/+Mgix RMpX + CICH,OR’ —> RCH,OR’ + MgCLYa2 (Gi) Addition reactions with compounds containing the following groups. >c=0, —c=n, >c=s In each case, alkyl group attaches to carbon atom and “MgX part to the oxygen, nitrogen or sulphur atom, Hj OH Donor Rar —>e—0 Max — Do-on ‘The addition products decompose with water or dilute acid. These type of reactions are given by molecules such as 0,,00,, ete. Alkyl lithiums : Organo-tithium compounds are prepared by the action of alkyl halides with lithium metal in dry ether at low temperature in the presence of an inert atmosphere of nitrogen. cH + Li SCHL + Lit ‘Methyl iodide “TOC” pty iti Alkyl iodides and alkyl bromides usually undergo Wurtz reaction. Alkyl chlorides ate visually used and they give good yields. ‘The high reactivity of organo-lithinm compounds over Grignard reagent is due to the greater polar character of C—Li ‘bond in comparison to C—Mg bond. Generally, alkyl lithiums behave like Grignard reagents but are more reactive. They react with compounds containing active hydrogens, aldehydes, Ketones, carbon dioxide, ethylene oxide, etc. : G.RB. Organic Chemistry for Competitions Hy —Li + HOH —+ CH, + LioH cH, Hearst — CH,CH,CH,OLi 88, cH,cH,CH,O# + LiOH | CH,—Li+ Co, —s cH,—C—o—1i , cH,coon +LiOH +H-C=0 —> CH,CH,—O—Li H cH, #8, cH,cH,OH+ LiOH Unlike Grignard reagents, alkyl lithium can add to an alkenic double bond. R-Li + CH,—CH, —+ R—CH,—CH,—Li Diatkyl zines : These were the first organometallic compounds discovered by Frankland, ‘These can be prepared by heating alkyl iodide with zine in an atmosphere of CO>, Heat 2RL+22n HE, 2p 003” alkyl zine iodide Owing to the difficulty in handling and better synthetic reagents are known, their use is restricted to the following preparations: (@) Preparation of quatemary hydrocarbon such as neopentane. (Cli, yCC1+ (CH, p22 —> (CH,),C+CHSZACL > + Fert. butyl ‘Neopentane "lors (i) Preparation. of ketones ; Acid chlorides reacts with dialkyl zine to form ketones. R’COC + RyZn —+ RIGOR + R—Zn—C1 ‘Acid chloride ‘eione4 = IMPORTANT POINTS TO REMEMBER (SUMMARY) === Compounds derived from alkanes by the replacement of ‘one or more H atoms by corresponding number of halogen atoms are termed halogen derivatives of alkanes or hhaloalkanes. They do not oceur in nature. Q Haloalkanes are divided into mono, di, tri, tetra, etc. according to the number of halogen atoms in the molecule. 1 Monohalogen derivatives are called alkyl halides (R—X) and represented by the general formula C,,H,, ,,X. They are further classified as primary (1°), secondary (2°) or tertiary (3°) depending upon whether the halogen atom is, attached to 1°, 2° or 3° carbon atoms. aR a RCH, —X CH-X | RC—X © wv A @ e Q Dihaloatkanes (C,H, Xz) are mainly of three types: Q Gem-dihalides: “In these derivatives, both the halogen atoms are attached to the same carbon atom, Their common name is alkylidene (dijhalides, ¢.., Br CH,CHC!,, CH,CH,CHBr,, CH; —C—CH, ividene _n-Propylidene I (iohlovide (aibromi Be Isopropylidene (dibromide Q Vicinal-dibalides: Both the halogen atoms are attached to adjacent (vicinal) carbon atoms. Their common name is alkylene (dijhalides, e.g, CICH,—CH,Cl , CH,CH(B)CH,Br, Ethylene (dijeloride Propylene (dibromide’ CH,CH(B)CH(BCH, Butylene (ddbromide Q Terminabdihalides (2,0): In them the two halogen atoms are attached to terminal carbon atoms. Their common name is polymethylene (diphalides, e.g. Chl» het, cpt bo ok OG & nay ess “hana (ede C1 Thalolkanes Galatea): Examples ae, CHC!;, CHBr, , CHI, CHF, ee, ae Q Tetrahaloalkanes: Examples are, cc. CBr, CCF, ae” Sila” pisietboce tetrachloride tetabromide methane General methods of preparation of alkyl halides O By direct halogenation of alkanes: In presence of sunlight, heat or catalyst (Free radical halogenation) gives a mixture of mono, di, tri halogen derivatives, etc. Replacement of H' atom from hydrocarbons follows the order: allylic H> 3° H>2° H> I H> CH, O Relative reactivity of 1°, 2°, 3° H atoms for chlorination is in the ratio 1:3.8:5. O Chlorination of n-butane gives a mixture of d- and [- optical isomers, £e., racemic mixture. O From alkenes: By the addition of HX (HI > HBr> HCI > HE), The unsymmetrical alkenes follow Markownikoff’s rule during addition forming 2° or 3° alkyl halides predominantly through the formation of the most stable carbocation. O The less stable intermediate carbocation changes into more stable carbocation by 1,2-hydride or 1,2-methyl or phenyl shift O Addition occurs through electrophilic attack. However, in presence of peroxide (R-O—O—R) the addition of HBr to unsymmetrical alkenes follows anti-Markownikof?’s rule (peroxide effect or Kharasch effect) From alcohols: By nucleophilic substitution (Sw) reactions. Action of halogen acids, HX (HI> HBr>HCI> HF) on alcohols’ in presence of anhydrous ZnCl, yields alkyl halides. The increasing reactivity of alcohols towards HX is: CHOH 2°>3°. O ‘odine forms ester (instead of alkyl hatide) with silver salt and is called Birnbaum-Simonini reaction. O By halide exchange method: R—CI or R—Br on heating with Nal in acetone or methanol sotutjon, forms R—I (This reaction is called Finkelstein reaction). G Alkyl fluorides can be prepared ftom corresponding chlorides by the action of mercurous fluoride (Fg F,) or SbF, (Swarts reaction).a4 Ql Physical properties: Lower members (CH3F,CH,CI, CH,Br,C,H,C) are gases at room temperature while CHI and others are pleasant liquids and higher members are solid. R—Br and R—I are heavier than water while R—F and R—Cl are lighter than water, These are slightly soluble in water but completely soluble in organic solvents. G They bum on copper wire with green edged flame Beilstein test for halogens). Boiling points are in the order RI> RBr > RCI> RF, while in a group of isomeric halides, the order is I°>2°>3°. Boiling points of organo halogen compounds are comparatively higher than the corresponding, ‘hydrocarbons because of strong dipole-dipole and van der Waals’ forces of attraction. Chemical properties: |The high reactivity of RX can be explained in terms of the nature of C—X bond which is highly polarised because the halogen is more electro- negative than carbon and the dipole moment decreases as the electronegativity decreases from F to I. Qi The polarity of C—¥ bond in alkyl halides is responsible for their nucleophilic substitution reactions, elimination reactions and the reaction with metal atoms to form organo metallic compounds. Q Chirality has a profound role in understanding the reaction mechanisms of Sy1.and Sy2 teactions. Sy2 reactions of chiral alkyl halides are characterised by the inversion of configuration while Sy1 reactions by racemisation, 2 Nucleophilic substitution (Sy) reactions of R—X ROX + Nu RNa + G Hydrolysis [action of moist silver oxide (AgOH), ot boiling with aqueous alkali (NaOH or KOH) solution): Formation of alcohols. Action with sodium alkoxide (R—ONa) or dry Ag,0 Formation of ethers with RONa is known as Williamson's synthesis. G Action with aqueous alcoholic NaSH or KSH: Formation of thioaleohols (alkane thiol). Q Action with aqueous alcoholic KCN: Formation of alkyl eyanides (alkane nitrile) as the major product. O Action with aqueous alcoholic AgCN: Formation of alkyl isocyanides (carbylamines or isonitriles) as the major product O Action of aqueous alcoholic KNO,: alkyl nitrite as the major product 1 Action of aqueous alcoholic AgNO,: Formation of nitroalkanes as the major product. G Action of aqueous alcoholic NH,: Formation of a mixture of pri-, sec-, fert- amines along with quaternary ammonium salts. O Action with sitver salt of carboxylic acids: of esters. G Aetion with sodium alkynide (Na—C==C—H): For ‘ation of higher alkynes. Formation of Formation GB. Organic Chemistry for Competitions Action of alcoholic Na,S or K,S or NaSR: Formation of thioethers (alkyl thioalkane), O Action of Nal in acetone or methanol: Formation of alkyl iodides, O Action of alcoholic Na;SO,: Formation of sodium alkyl sulphonate (R—SO;Na). D Action of sodium —_diethyl_—_ malonate NaCH(COOC;H,),: Formation of alkyl malonic ester RCH(COOC;Hs)3.* D Action of sodium —ethy!_—_ acetoacetate, 2 OCH Nac : Formation of alkyl cooc,H, acetoacetic, Oct ester, RCH A COOC;Hs Action of sodium azide NaNy: Formation of alkyl azide, RN. Elimination reactions O Dehydrohatogenation of alkyl halides: On heating with alcoholic KOH, alkenes are formed. This elimination proceeds by Ey or Ey process. Unimolecular elimination (E,): The R-¥ dissociates first to form carbocation and halide ion. CH, —CH—cH, ©" cH, CH—cH, +c 5 Carbocation Ca The ‘strong nucleophile (which is also a strong base) attacks the carbocation to give alkene. oreo —F_, cH,—cH—CH, + HOH OH (as)? Alkene hb QZ, involves the formation of most stable carbocation intermediate due to 1,2-hydride or methyl or phenyl shift giving unexpected products. 1G The order of reactivity of alkyl group is3° > 2° >1° and the most substituted alkene is the Saytzeff product and the less substituted alkene is the Hofinann product. 0 Bimoteclar elimination (Ey. It involves the fomation of itemodiate TS 5 HOH B H aaa Nee ant |e nse Sipe CS | ee Ke 785 BH +H,C—CH,+ G £y climination is stereospecific and follows trans- elimination.Halogenated Aliphatic Hydrocarbons Aetion of heat: Alkyl halides on heating above 300°C loses a molecule of HX to form an alkene. The decomposition follows the order : I> Br>CL. ‘Miscellaneous (some other) Reactions © Reduction: R—¥ on reduction with nascent [H] obtained by Zt/HCI or Na/aleohol or ZnCwC,H,0H or LiAIH, ete. gives alkanes. © Wurtz reaction: An etheral solution of RX (preferably ‘bromides and iodides) forms symmetrical alkanes when heated with metallic sodium. O Tertiary halides do not undergo this reaction Reaction with metals D Alkyl halides form Grignard reagents when treated with ‘Mg powder in dry ether. ete eee (Reactivity order is RI> RBr > RCI). {The CMe bond is conser toe covalent but bighy polar, the Mg—X bond is ionic (R—Mg—X). The Mg-metal is bonded in between X and carbon, hence nature of earbon chain does not alter. Grignard reagents find wide applications as the starting ‘material for the preparation of a very large number of organic compounds, RX on heating with zine powder in ether forms dialkyl ine, These are called Frankland reagents. 2C,HsBr + 2208 (C,H, ), Zn + Z0Br, Ethyl bromide when heated with sodium-lead alloy gives tetracthyl lead (TEL) which is used as anticknock ‘compound in petroleum products. 4C,HBr + 4Na(P6) 2855 (C,H, )_Pb + 4NaBr + 3Pb CLRAX forms dialkyt mercury compounds when treated with Na-Hg. RAY forms alkyl tithiums when treated with lithium in dry ether. GQ R—Xreacts with lithium dialkyl cuprate (Rui) to form alkanes (Corey-House synthesis). RX and ary! halide can react with sodium in presence of ether to form substituted (alkylated) benzene (Wurtz-Fittig reaction). O Friedel-Crafts reaction: R—X reacts with benzene in presence of anhydrous AICI; to form alkyl benzenes. % ant Ales Gy a EN GO) sae a ‘This reaction is named as Friedel-Cralis reaction. This reaction proceeds through the formation of an inter- mediate called o-complex (a resonance stabilized 415 carbocation). Anhydrous AICI, (a Lewis acid) generates, electrophile from the reactant. It is thus Se reaction, Q Halogenation (Substitution) : Alkyl halides undergo further substitution (halogenation) in presence of sunlight, heat, etc, cats Hem G8. © Oxidation reaction: Primary alkyl halides (1°) on oxi ation with dimethyl sulphoxide, (CH, ),S0 (DMSO) gives an aldehyde (Swern oxidation) while 2° halides give ketone. 9 q RCH, x DMSO, pC, r,cHx PMS, r,co Gi) CSO "pigciyde 72) (CHSC Kore Oxidation can also be done with (CH,),N4/HOH, H” ‘oxidising agent.. Benzyl halide on oxidation’ with (CH,).N,/HOH, H* gives benzaldchyde (Sommelet aldehyde synthesis). Methods of preparation of gem-dihalides (Alkylidene halides) O From aldehydes and ketones: By the action of PCI. From alkynes: By addition of two moles of HX (HBr or HC). Methods of preparation of vic-dihalides (Allcylene halides) By the addition of halogens (Cl, or Br,). = By the action of PCI; ot HCI or SOCl,. Chemfcal properties of gem- and vie-dihalides Chemically alkylidene (gem-) dihalides are less reactive while alkylene (vie-) dihalides have nearly the same reactivity as alkyl halides. O Hydrolysis with aqueous KOH: Gem-dihalides give aldehyde or ketones while vic-dihalides give glycols. O Action of ale. KCN followed by hydrolysis and heat: Gem-dihalides give monocarboxylic acid while, vie-dialides give cyclic anhydride. ‘These reactions are distinction tests between gem- and vic-dihalides. G Reaction with Zn dust in methanol: Both gem- and vic-dihalides give alkenes, O Reaction with ale. KOH (Dehydrohalogenation): Both ive alkynes. Reaction with sodamide (NaNH,) on heating: Both give alkynes. ‘Trichloromethane, CHC!, (Chloroform) QQ Preparation: Lab method and large scale preparation. Q From ethanol: By distilling a mixture of alcohol with a suspension of bleaching powder (CaOCI,). The Cly ‘obtained from bleaching powder serves both as oxidising as well as chlorinating agent. Alcohol is first oxidised to416. aldehyde by chlorine. The aldehyde then reacts with chlorine to form trichloro acetaldehyde (chloral) which on hydrolysis with Ca(OH), yields chloroform. O From acetone: Acetone first reacts with chlorine to form trichloro acetone which is then hydrolysed by Ca(OH), to give chloroform. 2 From carbon tetrachloride: with FelH,0. From ehioral hydrate: Pure CHCL, is obtained by distilling chloral hydrate with concentrated NaOH solution. Properties: Chloroform is a sweet smelling liquid, b pt. 61°C, non-inflammable but its. vapour causes By the partial reduction ht and air it slowly decomposes into phosgene (COCI,), a poisonous gas. Such chloroform cannot be used for anaesthetic purpose, 0 itis stored in dark blue or brown coloured bottles filled up to the neck O It is mixed with 1% C,H,OH which retards the oxidation and converts the phosgene into harmless ethyl carbonate. COCl, +2CHyOH—> (C,H,0),CO +2HCI Phosgene Diethyl carbonate Q Reduction: On reduction with Zn/HCI in presence of alcohol, chloroform forms methylene chloride (dichloro- ‘methane). But on reduction with Zn dusvH,O, methane is the main product Q Chlorination: Chloroform reacts with Cl, in presence of diffused sunlight or UV light to form CCl, Hydrolysis with aqueous alkali: It gives Na/K salt of formic acid. Q Nitration: With concentrated HNO,, chloroform forms chloropicrin (nitro chloroform) which is aliquid, poison- ‘ous and used as an insecticide and a war gas (tear gas). Heating with silver powder: Acetylene is formed when chloroform is heated at high temperature. with silver powder. Q Condensation with acetone: Chloroform condenses with acetone on heating in presence of alkali to form chloretone (1,1,1-ttichloro-2-methyl propan-2-ol) which is used as a hypnotic (drug). O Reaction with sodium —ethoxide: On heating chloroform with C,H,ONa, it gives ethyl ortho formate, HC(OC,Hs)s. O Reimer-Tiemann reaction: Chloroform reacts with phenol when heated at 65°C in presence of alkali gives salicylaldehyde (o-hydroxy benzaldehyde) as major product. O Carbylamine reaction (Isoeyanide test): Chloroform con heating with primary (1°) amine in presence of alcoholic KOH forms isocyanide (carbylamine) having very offensive odour (a test of CHCl, and also of primary amine). G.R.B. Organic Chemistry for Competitions Q Tests of chloroform: It gives isocyanide test (pungent smell), Pure CHCl; does not give white precipitate with AgNO,, but with Tollens" reagent, it gives a grey precipitate of silver. On heating with Fehling’s solution, it sives brown precipitate. ‘Triiodomethane, CHI, (Iodoform) O odoform resembles chloroform in methods of preparation and properties. Q It is prepared by heating compounds like ethanol, 2alkanols and methyl ketones with iodine and alkali solution or Na,CO, CH\CH,OH= 41, + 6NaoH 28% cH, + SNal+ HCOONA +5H,0 CAycocHH, +3 +2Na,C0, HA cH, + 3Nat +CH,COONa +200, The reactions producing iodoform are called Lodoform reactions. O Properties: It is a yellow crystalline solid, pungent characteristic odour, m.pt. 119°C and is steam volatile. Itis| used as an antiseptic for dressing wounds. Q Hydrolysis with KOH: lodoform gives HCOOK. Reduction with red P/HI: It gives methylene iodide, CHL, 5 Ol Heating with Ag powder: Acetylene is formed, © Carbylamine reaction: With aniline and KOH gives phenyl isocyanide, C,HNC (an offensive smell) OD Heating alone: It gives 1, vapours. O With AgNO,: It gives a yellow precipitate of Agi difference from CHC). Q Tests of CHIy: Iodoform reaction is mainly given by i CH,CH,OH,CH,CHO, —C—CH, group (methyl ketones), -2-ols Ge} secondary alkyl halides OH (eae: } 5 ete, Lactic acid a [(CH,CH(OF}COOH)] and pyruvic acid ( cH, coon] also gives iodoform reaction. Tetrachloromethane, CCl, (Carbon tetrachloride): Q Preparations—From methane: By chlorination (excess of Cla) at 400°C. Methane used in this method is ‘obtained from natural gas.Halogenated Aliphatic Hydrocarbons From CS,: Chlorine reacts with CS, in presence of catalyst AICI, of SbCl; to form sulphur monochloride (S,Cl,) and then CCl,. Q From propane: By reacting excess of Cl, at 400°C. ‘under atmospheric pressure forms liquid CCly. Ol Properties: It isa liquid, b.pt. 77°C, non-inflammable, hence used as a solvent for fats, oils, waxes and resins, ete. It is used as a fire extinguisher under the name pyren Reaction with steam (oxidation): CCl, reacts with superheated steam at 500°C to form phiosgene, a poisonous as. Reduction: It is reduced by iron filling into chloroform. ‘Hydrolysis with aqueous KOH: It gives CO, and then KCl and K,CO3. Reimer-Tiemann reaction: Phenol combines with CCl, in presence of alkali to form o-hydroxy benzoic acid Galieylic acid). Friedel-Crafts reaction: Benzene on treatment with CCl, in presence of anhydrous AICI, gives dichloro- diphenyl methane which on hydrolysis forms diphenyl ketone (benzophenone). Some important halogen derivatives Chloroftuoro carbons: Freons (CFC’s) Freons are small organic molecules containing C, Cl and F The most common freons ate CF,Cl,, dichlorodifluoro- methane (freon-12) and CF,Cl, chlorotifluoromethane (reon-11). a7 Preparation: Action of HF on CCI, forms freon-12. cel, + 2p SESE, ec, £281 ‘OF SHES, Catalys” Freon.) Freon-12 is widely used as reftigerant and propellant in aerosol sprays of all kinds. Halothane (CF;CHBrC!) is used as inhalation anaesthetic. Action of SbF, on CCl: SbCls A 30C1, + 28bF, 2 3cc1gF +'28bCI, GHE+2s0c1, Hs asbF, + 6HCL Freon isa gas under ordinary condition. Its b.pt. is -29.8°C aind can easily be liquefied. It is chemically inert. GQ. Westron (CHCl; —CHCI,) or acetylene tetrachloride: Feth or CHCl —CHCL, ‘AIC Catalyst ,1,2.2-Tevachloroeiane It is non-inflammable liquid, bpt. is 146°C and highly toxic in nature ‘Westrosol (CHCI=CCl,) or Trichloroethene: HO=CH+2¢1, ‘Aceryene CHCI,—CHCI, + Ca(OH), HS 2cHci—cel, + CaCl, Weston Wesrosat +2H,0 Both westron and westrosol are used as solvents for oils, fats, wanes, resins, pauls aud vaunishics, ct418 G.RB. Organic Chemistry for Competitions Very Short Answer Type 1. Fill in the blanks: (@), The compound prepared by the action of magnesium on dry ethyl bromide in ether is known as. (©) The interaction of clemental sulphur with Grignard reagent gives [ae S+ RMB RMX ES | RH + MOH (6 Pt elm iscsi ty ening... wi aqueous solution of sodium hydroxide (@) Grignard’s reagent has the general formula (©) When acetone is heated with bleaching powder is obtained. (£) A sensitive test of chloroform is based onthe formation of. () The yellow precipitate inthe réaction of acetone with iodine in the presence of alkali is (i) An alkyl halide may be converted into aleohol by... reaction (i) The most reactive alkyl halides are (j) Another name of 1,1,2,2-etrachloroethane is (© The well known’ ‘refrigerant freon has the structure ( Chloropicrin is formed by: the sction of ...... on Chloroform. (am) Carbon tetrachloride is used as fire extinguisher under the name (0) Diethyl ether is obtained from ethyl bromide by treating itwith. .....and thename ofthe reaction is (©) Chloroform when exposed to light and air forms a poisonous gas known as... () Chloroform forms a hypnotic when reacts with. (@ Allyl chloride isa compound while vinyl chloride is inert towards nucleophilic substitution. (© The dihaldes in which halogen atoms are attached to adjacent carbon atoms are termed as (© Alkyl: halides are formed when thionyl chloride and... are refluxed in presence of pyridine. (©) The order of reactivity (ertnry > secondary > primary) isdueto + effect of the alkyl groups which... the polarity of CX bond. (v) The hydrolysis of trialkyl chlorosilane, R, SiC, yields (¥) Bihylene chloride on hydrolysis with aq, KOH forms (w) When chloroform is heated with primary amine and alcoholic KOH, it forms a very offensive smelling compound, the name of the compound is...... and the reaction is known as reaction. _ () Gem dihalides on hydrolysis yield. . (y) Vinyl chloride on reaction with dimethy! copper gives. (2) Both westron and westrosol are used as... for oils, fats and varnishes. . State, whether the following statements are True or False: (@) Alkyl halides follow the reactivity sequence, RI > R—Br > RCL > RF (b) Ally! halides when treated with dry silver oxide form aleohols. (c) Carbon tetrachloride is inflammable. (@) Alkyl halides are soluble in water. (©) Chloroform gives carbylamine reaction with primary (® Westrosol is « very good solvent for fats, oils, waxes, resins, et. (@ Ethyl bromide when heated with silver acetate forms ethyl sleokol. (h) Polytetrafluoro ethylene is commercially known as teflon. (@) Todoform is a yellow coloured antiseptic compound. Cj) Pure chloroform gives precipitate with silver nitrate. ) Todoform when heated with silver nitrate gives yellow precipitate, (), Gene

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