9.1 INTRODUCTION The replacement of one or more hydrogen atom(s) in a hydrocarbon (aliphatic or aromatic) by corresponding halogen atom(s) (fluorine, chlorine, bromine or iodine) results inthe formation of alkyl halides (haloalkanes) and arylhalides arenes) respectively. (s) attached to sp*-hybridised Both varieties of compounds are health care and medicine. For 0 tetrachloride acts as solvent 1 (chloromycetin) nism is very effective in the Our body produces an iodine roxine, the deficiency of which replacement of onding number 1, Monohalogen derivatives: One halogen stom attached to carbon atom. They are commonly represented by the formula R—X where R is an alkyl radical and halogen atom. r—u =H, rx Alkane ~% "Allyl ba These are termed alkyl halides and the homologous series has the general formula C, Hay." Examples : cH,CI Met chloride Monohalogen derivatives or alkyl halides are clasified as primary (1°), secondary (2°) or tertiary (3°) depending upon ‘whether the halogen atom is attached to primary, secondary ot tertiary carbon atoms CHAI Propyl iodide C,HSBr Ethyl bromide Primary Secondary ae | 7 carbon eX Vv H H primary Alky halide secondary Alby halide RY periacy carbon, Rox Re tertiary Alkyl halide 2. Dichalogen derivatives: The dihalogen derivatives of alkanes are derived by the replacement of two hydrogen atoms by two halogen atoms.2 GRB Organic Chemistry for Competitions (2nd Year Programme) CyHapes ty CHa X2 Alkane 42x Dihalogen derivative ‘The dihalogen derivatives are mainly of three types: () Gem-dihalides: In these derivatives both the halogen atoms are attached to the same carbon atom. These are also called alkylidene (dl) halides. cl cen ; CHj—CBr,—CHy, cl Isopropylidene bromide Ethylidene chloride @.2_Dibromopropane) (1,1 Dichlorosthane) (ii) Vie-dihalides : In these derivatives, the halogen atoms are attached to adjacent (vicinal) carbon atoms. These are also termed as alkylene (di) halides. CH,CICH,C! ; (CHCHCICH,CI Ethylene chloride Propylene chloride (1,2-Dichloroethane) (1.2Dichloropropane) (iii) @-@ halides (terminal dihalides) : In these derivatives, the halogen atoms are attached to terminal carbon atoms. These are also called polyethylene halides. CH,BrCH,CH,Br; CICH,CH,CH,CH,CI Trimethylene bromide Tetramethylene chloride (1,3-Dibromopropane) (14-Dichlorobutane) 3, Tri-halogen derivatives : Tri-halogen derivatives are derived by the replacement of three hydrogen atoms from es by three halogen atoms. They have the general ila C,H,;X3. The tri-halogen derivatives of first CHBry ; Bromoform CHI, Iodofoem ese compounds are termed as haloforms. ‘Tetra-halogen derivatives : The tetra-halogen deriva- derived by the replacement of four hydrogen atoms alkanes by four halogen atoms. All the four halogen Bms are attached to the same carbon atom in derivatives of CBr, Carbon tetrabromide ccl, Carbon tetrachloride Hn other derivatives, the four halogen atoms are attached ferent carbon atoms, ¢.£.. CHC Ila pcetyene tetrachloride or ogous react with halogens to produce IL. Addition products: These compounds are obtaingy by exposing the mixture of aromatic hydrocarbons and the halogens to direct sunlight, .g.. benzene hexachloride (BKC) CH Clo: benzene hexabromide, C,H Bre, ete : 2. Substitution products: “Two types of haloge, substituted products are known (i) Nuclear halogen substitution products (Ary halides) or Haloarenes : In these products, the halogen ig linked directly to the carbon of the benzene nucleus. These products are generally called aryl halides. Chiorobenzene CH : /Br (@-Bromotoluene) O- lodobenzene cl cl 14-Dichlorobenzene (p-Dichlorobenzene) CHs ° 4-Bromotoluene (P-Bromotoluene) (ii) Side-chain halogen substitution products (Aralkyl halides): In these products, the halogen is linked to the carbon atom of the side-chain, 1-Chloro-1- L-Dichloro-l- 1, {-Teichloro-I- phenylmethane —_phenylmethane——_phenylmethane (Benzyl chloride) (Benzal dichloride) (Benzotrichloride) These are also called side-chain aryl halides. They have properties similar to alkyl halides. ‘Arylhalides: According to IUPAC system, ary! halides are named as Haloarenes. If more than one halogen is present, their positions in the ring are indicated by numbers or appropriate prefixes, ortho, meta and para Br CHs CHy a, oo Br 1,3-Dibromobenzene or 2-Chlorotoluene oF (oDibromoberizene) _(o-Chlorotoluene) CHs 2-Chloro-1 4-dimetty! benzene 9.3 CLASSIFICATION OF MONOHALOGEN COMPOUNDS Monohalogen compounds may further be classified according to the nature of C—X bond in haloalkanes and haloalkenes particularly to the hybridization of the carbot ‘atom linked to the halogen.Haloalkanes and Haloarenes (A) Compounds containing C—X bond, where carbon is sp?-hybridized. () Alkyl halides or Haloalkanes: In alkyl halides, the halogen atom is bonded to an alkyl group. The homologous series is represented by Cy Ha,,,.. They are further classified as primary (1"), secondary (2") and tertiary (3°) halides depending upon whether the halogen atom is attached to a primary, secondary o tertiary carbon atom. Examples are: (3 CH)—CH,—CH,—Cl ; }-Chloropropane CH,—CH—cH,; (primary of 1°) 1 2-lodopropane (secondary of chy x CH; Fee Br 2-Bromo-2-methylpropane (ertiary of 3) (i) Allylic halides: In these halides, the halogen atom is, attached to allylic carbon (C=C—C—X), i, carbon atom next to C=C. Examples are: ~ 2” H,C=CH—CH,—I ; H,C=CH—CH—CH, ; 3-lodoprop-Lene (Ally iodide) Br 3-Bromobut-lene thy! bond, (O Arylhatides: In these halides, the halogen a directly attached to the carbon atom ofan aromatic ring. halides are also called haloarenes. Examples are: Chlorobenzene ; Bromobenz: Iodobenzene —;2-Chlorotoluenes 3-Bromotoluene ; 4-Bromotoluene (ii) Vinylic halides: In these halides, the halogen ator is attached to vinylic carbon (C=C—1), Le, one of U carbon atoms of samples are meoci_ ct i Chechens vinta (Rei) tment (©) Compounds containing C—X bond, where carbon cyny In these halides, the halogen atom is attached to one of the carbon atoms ofaC==C. Examples are: HC=C—Br;HyC—C=C—Cl Bromoethyne EChloroprop-1yne (Bromoncetylene) 9.4 NOMENCLATURE (A) Hatoatiaanes (Atky! les) Fo a of hog lerivative Common name — | 1UFAC name CHC [Methyl chloride [Chloromethane CH\CH,Br ety! bromide | Bromoethane CHSCH,CHL n-Propyt iodide |1-1odopropane CH,CHB:CH, lsopropy! bromide |2-Bromopropane CH,CH,CH,CH,Cl_—feBuyl chloride |1-Chlorobutane CH, GU-Ctl Cis fy choi -CHorhtane a cu Isobutyl bromide | -tBromo-2. lropane ethyl tertiary hay 2 -tromer2-methyl [bromide " c—C—ch T propane be CHCH,CH,CH,CH,C1 |n-Pentyl chloride ln-Amyl chloride y= GUC, e-Penyevde a |-Chlotopentane [2-Chloropentane see-Amiyl chloride Hi FICHE open elrde Chowne oF butane cn, Isoamyl chlorideGRB Organic Chemistry for Competitions (2nd Year Programme 4 95 ISOMERISM IN MONOHALOGEN Formula of halogen a ee (SS ; || Eee DERIVATIVES CH Jtert-Pentyl chloride a Higher members of alkyl halides show the following types o oF utane isomerism: CHE CHC “fers Aum cern {@) Chain isomerism: This is due to different arrang q ments of carbon atoms in the alkyl group. For example cH, CyHaCl. INeopentyl chloride |1-Chloro-2,2- CH; cH,—C—CH.CL or |dimethylpropane 5 INeoamy! chloride CH,CH,CH,CH;,Cl_ CH;—CH—CH,CI ca 1-Chlorobutane |-Chloro-2-methylpropane HC, IMetnylene chloride |Dichloromethane Gi) Position isomerism: This is due to differe cl positions of the halogen atom in the molecule. caer Etyidene chloe |1,1-Dishloroetane ¢ cl (CH,CH,CH,CH,CI (CH ,CH,CH—CH. cuc—cuct —_etytene torte |1.2-Dieblorotane Renee ee HCI, |Chloroform ITrichloromethane (ii) Optical isomerism : This is due to the presence o cH; lodoform ltriiodomethane asymmetric carbon atom in secondary butyl halide. cc, carbon tetrachloride Tetrachloromethane H CHCI-CHCL, —_|Acerylene 1.1.22-Terachloo- . . fetachoride __febane CH;—C—CH,CHy Usually, the simple and lower members are called by common names and higher members are given IUPAC names. Halogen derivatives of alkanes are highly reactive as the halogen atoms are easily replaced. These do not occur in ature and are entirely of synthetic origin. These derivatives ‘especially the alkyl halides are widely used in the synthesis of many organic compounds. (B) Haloarenes (Arylhalides) Haloarenes are named by prefixing ‘halo’ (fluoro, chloro, ‘bromo or iodo) to the name of the parent hydrocarbon. If more than one substituent is present, their positions in the ring are indicated by numbers. In the case of disubstituted haloarenes appropriate prefixes, ortho (0), meta (m) and para (p) can be used respectively. cl CH; CH; oo a cl (Garigame, — 2eMaoene —_3-Cionlan eoylchionde) —(e-CHortliene) _(-Chlorotlne) (Monohaloarene) J ee y cl CH, Br ‘Br cl ~12.Dichlorobenzene _3-Bromotoluene 1-Bromo-3-chloro- | (@-Dichlorobenzene) _(m1-Bromotoluene) (Ditsloweng) , ae cl 2-Chlorobutane The total number of isomers in alkyl halides are: Propyl (C3H;—2 ) has two isomers, Butyl (C,Hy—2) has four isomers and Pentyl (CsH,;—X) has eight isomers. (iv) Conformations: Alkyl halides can also. forn conformers due to the free rotation of C—C bond. ~ Se yaa eIRITA00-77107 |e ‘SOME SOLVED EXAMPLES. Example 1. Write structural formula and give thei IUPAC names: (a) see-Butyl chloride (0) tert-Butyl chloride (6) tert-Amyl iodide (g) Neopentyl chloride (i Isopropylidene bromide (&) Croty! bromide (m) 4-Chloro-2-pentene Solution: (a) Cit) —GH—CHCHs a (b) CH; —CH—CH,CI (b) Isobuty! chloride (d) Isopropyl bromide (f) Isopenty! bromide (i) Neohexyl bromide () Allyl iodide (D) Propargyl bromide 2-Chlorobutane 1-Chloro-2-methylpropane HyHaloalkanes and Haloarenes (0 1-Bromo-3-chlorobenzene (g) 2-Chloro-2-phenylbutane ichlorobenzene (hy | () 3-Bromo-1-phenylpro 4-Bromo-|,1-dibromo-1-phenylmethane pene Example 6. Write the possible isomers of aromatic ‘compounds, (a) CeHio. taving molecular formulae (6) CHCl. Solution: (a) Four isomers are possible : Hs o[(O CH (©) ie NZ CHy (i Qhea, CH; “(O CH; (b) Three isomers are possible : Ethylbenzene 1,3-Dimethylbenzene (n-xylene) 1,4-Dimethylbenzene (p-xylene) 1,2-Dichlorobenzene (0-Dichlorobenzene) 1,3-Dichlorobenzene iehlorobenzene) 1,4-Dichlorobenzene (p-Dichlorobenzene) 7 9.6 (A) GENERAL METHODS OF PREPARATION OF MONOHALOGEN DERIVATIVES OR ALKYL HALIDES ‘The following general methods are used for the preparation of alkyl halides. 1. From alkanes : Direct hatogenation of alkanes in presence of sunlight, heat or suitable catalyst yields alkyl halides. Chlorination is fast, bromination is slow while direct iodination is not possible as the reaction is reversible and highly endothermic. (However, iodination can be done in presence of oxidising agents such as HNO, or i HIO3). The reactivity ofthe alkanes follows the following order: tertiary Alkane > secondary Alkane > primary Alkane R—H+N; Ys R—X +HX Alkane Alkyl halide Direct halogenation proceeds through free radical mechanism : Direct halogenation does not form pure monohalogen derivatives but a mixture of polyhalogen derivatives is always obtained. For example, methane reacts ‘with chlorine in presence of diffused sunlight or at 523-673K to form a mixture of methyl chloride, methylene chloride, chloroform and carbon tetrachloride. cH, + cl; > cnc: “2 cH, cl, > cue; CHa rey 7? “Hey is not casy to separate the mixture, However, it is the most important commercial method for obtaining alkyl halides because alkanes are available in large amounts from petroleum and natural gas. If the conditions are well maintained especially the ratio of halogen and alkane, the halogenation may be suppressed beyond monosubstituted product. The displacement of H from hydrocarbon is in the order: Allylic > 3° > 2° > 1° >CHy GH, Light 7H, (exces) +C1, —E*s CHCl + HCL Ethane 1 ay chloride (exjor prod) Light CH CH,CH+Cl; "+ CH, —CHCH, +CH,CH,CH,CI Propane WD? | 1-Chloropropane ch (45%) 2-Chloropropane (55%) Similarly, bromination takes place, but not so vigorous as chlorination. However, iodination can be done by heating, iodine in the presence of oxidising agents such as cone. HNO or HIO, (to oxidise HI formed during the reaction to iodine), and hence, shift the equilibrium in the forward reaction,ea Ri, RE (S14 M10, —> 31, 1 3H,0) ‘The renctivity of halogens decreases in the orer: Fy Cl, > Bry hy. Hromination of alkanes is less _exothern chlorination and so with fuorination, lodine is unig ines is endothermic. “, and above) gives a mixture * racemic mixture (optically than ns ils reaction with al Chlorination of n-alkanes (C. ‘of de and F- optical isomers, 4 inactive). iy (P ch CU,CH,CH,CH, —> H—C—Cl lI netiutane Ww CIRC, CHCHhy dy (hy Racemic ‘Alkane can react with sulphuryl chloride only in presence of light and traces of onganic peroxide, "_, R—Cl +HICL+S0, RU +S0,Cl, Akane Sulphuryl &* PePORHE CHoroalkane chloride 2. From alkenes: Halogen acids (HCI, HBr, 11) react readily with alkenes to form alkyl halides, ‘The order of reactivity of halogen acids is: HL> HBr > HCI> HF 11,C=CH, +r —> CH,CH,Br Br cujci—cu, +11, AM cH) —CH—CH, Propcne 2 tromopropane (Wasyreticl kee) sopropy bromide) “The unsymmetrical alkenes follow Markownikoff's rule during addition forming secondary or tertiary alkyl halides predominantly through the formation of most stable carbo cation. Addition occurs through electrophilic attack. Howeve in presence of light, heat or peroxide (X—O—O—R), such as benzoyl peroxide (C,H,CO—O—O—COC, Hs), the HBr ‘addition follows anti-Markownikof?'s rule (peroxide effect ‘or Kharasch effect) and form primary or normal alkyl bromides. Such an addition follows free radical mechanism. This method is well suited for the industrial preparation of alkyl halides as the lower alkenes are obtained during cracking of petroleum products. x R—CH=CH—R 4X —> R—CHI,—CH—R Symmetrical alkene ‘Alkyl halide GRB Org: janie Chemistry for Competitions (2nd Year Programme Be | CH, ClCH, 1 Br —> CH) —CH-CH, Un 2-lionepropane (hapropyt bromide) Crm — cH jnnnettical alkene cH -Cl= CH, 1B —> Clly ¢ CHCH, Br 2.tbrome-2-methylbutane 3.Methylbut-Lene ‘scan be explained by 1,2-Hydride shift or 12-methyl shift to altain greater stabilily of carbocation. CH,CH,CH=CHCH, + 1Cl— Pent-2-ene anc. CIC, #C1n,CH,CH, CI Hy cl cl 2-Chloropentane (1) 3.Chlorepentane (A) approx. 55%) (approx. 45%) Both haloalkanes (A) and (2) are formed in comparable amounts, Further, since the carbocation (1) leading to the formation of compound (4) is slightly less stable than ‘carbocation (II) leading, to the formation of compound (8), therefore, CHjCHCHICH,CH, — CHyCH,CH,;—CHCH, 0 a iabilised by five hyperconjugation Stabilised by four hyperconjugation St structure (slightly more stable) siructre (slightly less sable) ‘amount of 2-chloropentane (8) will be slightly more than that of 3-chloropentane. CH, —CH=CH, + HBr Peroxide, (44, —CH,—CH)Br Propene (anti:MR ~.prompropane addition) (.Propyl bromide) CH, CH, (CAsCO01 Ci, —C=CH, + HBr neon cHy— eerie 2-Methylpropene Hl Chom i CL i ts It may be noted that the peroxide effect plies to the addition of HBr only and not to the addition of H1CI or Allylic substitution ‘When alkenes are heated with Cl; or Br, at a high temperature of about 773K, the hydrogen atom of the allylicHaloalkanes and Haloarenes carbon (ie. carbon atom next to the double bonds) is substituted with the halogen atom without breaking the double bond (allylic substitution) and forms allyl halide. For example, Hy +¢l; 22K, cicuycH—=cn, + HCL All eloride -Choroprop-tene) The allylic substitution can also be carried out by heating the alkene with N-bromo succinimide (NBS) or sulphuryl chloride (SO;Cl,) at 473K in presence of light and traces of organic peroxides such as benzoyl peroxide. cH,—co, Mn+ | Dyate sat, CH, —Co, 1N throm succinimide (NBS) cHy—cHt pene Cll) —CH: Propene CH,—CO, BrCH,CH=cH, + | >t 3-Bromoprop-l-ene CH, —CO. (allyttomite) Snags Br (Allyl chloride) +80, +HCI can also be selectively halogenated by Br I (Oe, Generally alkyl NBS. Ma Worthy halides are ‘or concentrated sulphuric acids and that of alcohols RON Nt X+RLOn, — RV +H,0 Since, the nucleophilicity (ie., tendency 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, i.e., HI > HBr >HCI (@) Alkyl chlorides are obtained by passing hydrogen chloride (gas) through alcohol in presence of anhydrous zinc chloride (Levis acid). CH,CH,OH + HCK(g) ae CH,CH,CI+ H,0 Ethanol (one) 202 called This mixture (1:1) of cone. HCL and anhyd. ZnCl, Lucas reagent. The yield can be improved when the vapours of alcohol and HCI are passed over alumina at 623K. Itmust be noted that 1° and 2° alkyl chlorides are prepared {om their respective alcohols by using HCI gas and anhydrous ZnCl, (Groove’s process). Tertiary alcohols are very reactive and therefore, they react readily with cone. HCl even in the absence of ZnCl, (CH,);C—OH + Hc} Room, 2-Metiyl-2-propanol —(con::) temp. (ert-Butyl aleohol) (CHy);C—Cl +H,0 2-Chiloro-2- metiypropane (Gert-Buty| chloride) 1° alcohols follow Sy2 path while 2° and 3° alcohols Syt 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 litle concentrated sulphuric acid, These are also ‘obtained when the alcoho! is heated with potassium bromide in presence of conc, HaSO, in excess (Lab method). 1,80, (coe CH,OH+ HBr SO), Cape +H,0 Ethno! Refit promoetiane CrH,OH-+ KBr +H,80, #5 C,11,Br +KHSO, +110 Note: “The mixture of KBrand 1,50, isnot sed in cave of econdany and tertiary alcohols as their dehydration may occur. In case of higher alcohols, there can be 1,2-methyl (CH3—) or 1,2-hydride (H—) shift to form more stable carbocation, me cH, gu CHF CHC, +HCI— Cay —F— Hct CH, OH a 3.3-Dimethyl-2-butanl 2-Chloro-2,3-dimethybutane10 This is due to 12-Methyl shift. , cH, cH, ¢—cH_cH, Ee CH—C—CH-CH, CH, O# cH, 01 1 iodides are prepared by refluxing alcobol with HI (573). These are also obtained when the alcobol is bemed with potassium iodide in presence of phosphoric acd excess 0 C.H.o#-xt-H.P0, = c,d -KH,PO,-H,O edaetace (cs#.0n-Ht BS, c.HA+H.0] (@) Action of phosphorus halides: Action of phospiorss Ealides on alcobols converts them readily into Sip belies 32—OH-PX; —> 3R—X+H,PO; The ally! chlorides are formed by the action of PCI, or POL, cx aleotols. (PBr, and Pl, are not known to exist) “H,OH-PCL; —> 3C,H,CI-H,PO; CH,CH.CH.OH- PCL, —> CH,CH,CH,CI+POCI; bPropacct Pro OPI cy ie case of preparation of alkyl bromides and iodides, 5 required for the reaction is generally produced ‘ction of red phosphorus on bromine or iodine. recction may be depicted as — 2PIs) cx (2P=3Br; —> 2PBr) Ro; d gives cood yield of primary alkyl halides but 7 2nd tertiary alkyl balides because 1s on heating forms alkenes. The g lower alkyl bromides and GRB Organic Chemistry for Competitions (2nd Year Programrne) (ii) Action of thionyl chloride (Darzen’s method) ; Alkyl chlorides are prepared when thionyl chlonde ang alcohols are refluxed in presence of pyridine. R—OH~SOCI, ae, R—C1+S0,1 + HIT c.H,on-soct, 22%) c,H,c1_+s0,7 +H Etaml — Thiomyt (Chloroethane chloride This method is widely used for the preparation of allyt 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 of the fatty acids. This reaction is called Borodine-Hunsdiecker reaction or Hunsdiecker reaction. cay, R—COOAg +Br; SO, R—Br+CO, + AgBr O0Ag + Br, EC *> R—Br +CO; ~ AsBi CH,CH,COOAg + Br, SS, CH,CH,Br +CO, + AgBr Silver propionate Ethyl bromide ° Br HW ARNOs Cy faeer CY ‘This reaction gives the product with one carbon atom less than the fatty acid and the yield of halide is 1° >2°>3°. If R group is 3°, then alkene is produced as major product in this reaction. me ii i HCE — C—O BH c= C—CH, +0. ‘2 Methyipropcl-cne CH, + AgBr But iodine forms ester instead of alkyl halide and is calle Birnbaum-Simonini reaction, 2R—COOAg +1, —> R—COOR +2CO, +2Agh set ‘One useful modification of this reaction is the use of Het or Po(OAc), in place of silver salt to form alkyl halides. Xa/Hi 2n—coon 28, 2R—X +2CO} +HgX, +H0 POOAC): r—coon HOM, 5. By halide exchange method: method for the preparation of alkyl ‘This is a converte’ iodides.Haloalkanes and Haloarenes corresponding alkyl bromides or chlorides are heated with a solution of sodium iodide in acetone or methanol. RCH Nal ASE RL + NaCl . Accione, CNBr Nal Ca + Nabe {ahs bode 8 ety iit This reaction is ealled Binkelstein rea with iodine also results in ignand reagent on reactio the formation of iodoalkane. CH,CH;—MgBr +1; —> CHCHL 4 Mg(BOL Vuh mig. bromide Tovaethane Even alkyl Muorides whieh eannot be prepared by the above methods may be abtained from corresponding chlorides by the action of mercurous fluoride or antimony trifluoride or Asty or Agl, etc., (Swarts reaction), 2CUACL+Hg,Fy —> — 2CH,F + Ug,Cl, Mey Muoride CgHyBr + AgF —> CHF + AgBr Fluoroct 3CH,CCI,CH, +28bF, —> 3CHCF,CH, +28bC1, 6. By Rydons method: An alcohol on heating with halogen in presence of triphenyl phosphate (PhO), PO produces alkyl halides. R—CU,OH + Bry + (CyH,0), POLS R—CHBr +C,HOH + (CHO); POBr 9.6 (B) GENERAL METHODS OF PREPARATION OF HALOARENES 1. (a) By direct halogenation of hydrocarbons : This method is used for the pre cchlorw and bromo derivatives. Halogens react with aromatic hydrocarbons in pre ‘Chorobenze Br Os o* O (minor) p-Dichlorobenzene (mayor) the aro ‘Toluene in pres to form a mixture of o- (minor) and p- (major) chloro or bromotoluenes, respectively. My cHy +l, Any FeCl, Toluene Mixture of o-and p-Chlorotoluene ‘The ortho and para isomers ean be easily separated due to large difference in their melting points. lodo derivatives cannot be obtained by direct reaction with iodine as the reaction is reversible. Cog tly = CyHsl + HI odo di ives can be obtained if the reaction is carried ‘out in presence of an oxidising agent, ¢g., iodie acid or nitric acid, ete. The oxidising agent oxidises HI to iodine and thus. the reaction moves to proceed to the right, @HI+2HNO, —> 2NO, +2H,0 +13) (SHIL+ M10, — 31, +34,0) 1 {0} +, —WL. Aryl fluorides (Aluoroarenes), however, cannot be prepared by direct Muorination of aromatic hydrocarbons because of the high affinity of fluorine for hydrogen and the reaction is very violent +10 lodobenzene Mechanism of Halogenation Halogenation of benzene is an electrophilic substitution reaction, The reaction takes place through the following, steps: Step 1. The electrophile, i«., halonium ion (CI', Br* or 1) is generated by the action of Lewis acid (FeCl, ot anhyd, AICI; ... ete.) on the halogens.2 GRB Organic Chemistry for Competitions (2nd Year Programme) ClI—Cl+FeCl,—> CI + FeCl CH,CHy CHCI-CHs CHy-CH.C (Etectophile) ? vo pate 2, Th eletophil (CI*) attacks the benzene ring Cty. . to form an intermediate known as. ocomplex oa crbcaton “rik” rium ion) which y resonane ich is stabilized by resonance. mw ae as benzene phenyletiane ——_phenylethan (56%) 3) . AH sy se Ce Benzene Chloronium ion Carbocation A H H H cl —| cl —Cho- fe ae Resonance stabilized carbocation The formation of intermediate arenium jon (carbocation) is slow and hence is he rate determining step of the reaction. Step 3. The carbocation loses a proton (H*) o the base FeCl; to give chlorobenzene. At cl Cl +Feti; FA Cr + FeCls+HCl Chlorobenzene This step is fast and hence does not affect the rate of the reaction Side Chain Halogenation Side chain halogenation of toluene takes place when chlorine is passed through boiling toluene in presence of ‘sunlight and absence of halogen carrier. cis onc +c, SS Oo + Hel ‘ive penn ci IfCl, is passed for a longer time, the benzyl chloride so formed reacts further to form first benzal dichloride and then benzotrichloride. CHC! CHCl, CCl; O-« os © a) es oa | wot cample of free radical substitution, fen the side chain (R—) is larger than a methyl group, ‘chain halogenation mainly takes place atthe benzylic ie. carbon atom next to the benzene ring). For Thionyl chloride (SOC!) or sulphuryl chloride (SOCI,) at 475 K in presence of light and traces of peroxide can also be tsed in place of Cl; for benzylic halogenation of arenes, For example, C(H,CH,+S0,C1; 22% C,H.CH;C1+ SO; (Pet0Ude) Benzyl chloride HCIT “Toluene 2. From benzene diazonium salts: Aryl halides can be obtained most satisfactorily by the decomposition of ar diazonium salts in presence of copper halide solution dissolved in the corresponding halogen acid, the diazo erovp js replaced by a halogen atom (Sandmeyer’s reaction). In ths reaction, itis the halogen atom attached to copper which enters the benzene ring. cl cucuncy or Cu3C, Chlorobenzene Br Ae Cupeb NCI oF CuBr a Bromobenzene J I Benzene diazonium | Kltoa) chloride (warm) Todabenzene F BE. Fl LNsBEs + Nz + BF; + NaCl i Oo N2+ BF; Fluorabenzene Jodo compounds may be obtained by boiling th diazonium salt solution with aqueous potassium iodide. Benzene diazonium chloride needed for this purpose obtained by treating aniline dissolved in dil. HC! with 2 aqueous solution of sodium nitrite at low tempers 273-278 K (0-5°C). NaNO, +HCI(dil.)—> Sodium nitrite HNO, +NaCl Nitrous acidHaloalkanes and Haloarenes NH NCI +HONO + Het 2B278K +2H20 Aniline cl Benzenediazonium chloride This reaction is called Diazotisation, Aryl fluorides are prepared by the reaction of corresponding diazonium salt with fluoroboric acid. This feaction produces diazonium fluoroborates which on heating produces fluorobenzene Heat + NBR Gags” —_a Fluoroboric NCD acid Benzene diazonium tetraluoroborate F + BF; +N; Fluorobenzene This reaction is called Balz-Schiemann’s reaction. In Gattermann’s reaction, the catalyst finely divided copper is used to form chlorobenzene or bromobenzene, CcHgN,CI aad CoH Cl+N, powder in presence of corresponding used in place of cuprous halide. +N, Chiorobenzene Br +N 13 Kuen, cqtangcr+Ken 2S, een +Ny + KCI CyHeNC1+ KON —S C,H.CN+N, +KCI Benzene diazonium chloride is obtained from benzene, nitrobenzene or aniline as follows: NO; HNO: Sa H:S0, HCT Benzene Nirobenzene Benzene diazonium conde 3. Hunsdiecker’s reaction: Aryl bromides are obtained by heating the silver salts of aromatic acids (in CCl, or xylene) with bromine. COOAE oy Br or +B, SN +AgBr+CO, Silver benzoate Bromobenzene Note The decomposition ofthe acid is accelerated ifa —NO, group is present in the nucleus. 4, Decarboxylation of halogenated acids: Sodium salts of halogenated acid when heated with soda lime produce aryl halides. Heat cance — > C,H Br +Na,Co, Br Bromobenzene (05m: or pBromabenzoie acid 5. From phenol: Chlorobenzene can be prepared by the action of phosphorus pentachloride on phenol. The yield, is however, very poor because of side reactions giving triphenyl phosphate (TPP), To get better yield alittle of TPP is added in reaction mixture. OH a +PCls +POCI + HCI Phenol Chlorobenzene 6. Laboratory method (Sandmeyer’s reaction) : The most convenient method of preparing chlorobenzene in laboratory is by Sandmeyer’s reaction, in which benzene diazonium chloride obtained from aniline is heated with cuprous chloride in presence of hydrochloric acid,mn GRB Organic Chemistry for Competitions (2nd Year Programm) wc Haloalkane + m-Butyl —Isobutyl — terrBuyy _NaNO¥HCI _CusCh/HCL, bromide bromide bromide T278K Boiling point (K) : 374 364 M6 Benzene 2C,H,C1+2H,0 This method is used composition of the catalyst Germany. The exact nature and still a trade secret, 9.7 PHYSICAL PROPERTIES OF HALOALKANES AND HALOARENES 1. Physical state and smell : ( Haloatkanes: Haloalkanes, the lower members like CH3CLCH,Br,CH,Fand ethyl chloride are colourless {gases at room temperature. The other haloalkanes upto Cig are colourless sweet smelling liquids while higher members are colourless solids. (ii) Haloarenes : Haloarenes are generally colourless liquids with pleasant odour or are crystalline solids with characteristic smell. 2. Boiling Point (®) Haloatkanes ; For the same alkyl group, the boiling, points of haloalkanes decreases in the order RI > RBr RCI. This is because with the increase in the size and ‘of halogen atom, the magnitude of the van der * forces of attraction increases. Thus, : CHyl 2 3184 CH,Br CH;Cl CHyF 2766 248.8 194.6 CHC] CyHsCl CyH;Cl CyH9Cl 248.8 285.5 320.0 351.5 th, branching, ic, primary > Secondary > Teta. branching of the chain makes the pact and therefore, decreases the haloalkanes and so the magnitude of fais’ forces of attraction decreases. It may be noted that haloalkanes have higher boil points as compared to those of corresponding alkane, This is due to their polarity and strong dipole-dipol interactions between haloalkane molecules, Haloarenes: The boiling and melting points of arylhalides are nearly the same as that of haloalkanes containing same number of carbon atoms. The boiling points of moniohalogen derivatives of benzene are in the order: Jodo > Bromo > Chloro > Fluoro For the same halogen atom, the boiling and melting points increase as the size of the aryl group increases, The boiling points of isomeric dihalobenzenes are nearly the same, but their melting points are quite different, Generally, the melting point of the para isomer is always higher than that of ortho or meta isomers. This is due to the reason that the para isomer is more symmetrical and hence its molecules pack closely in the erystal lattice. cl cl a cl ortho meta a para Dope. 453K 446K ask mpi. 256K 249K 325K AS a result, intermolecular forces of attraction are stronger and therefore, greater energy is required to break the para isomer lattice and it melts at higher temperature. solubility : Although haloalkanes are polar in nature (dipole moment 2.05~2.15 D), yet they are insoluble in water. This is because they are not able to form hydrogen bonds with water molecule, However, they are soluble in the organic solvents like benzene, alcohol, ether chloroform and carbon tetrachloride, ete, Aryl halides are insoluble in water but readily miscible with organic solvents. 4. Density : Chloroalkanes are generally lighter than wate whereas bromides and iodides are heavier. Thei densities are in the order RI > R—Br> R—Cl. TheHaloaltanes and Haloarenes is ity increases with increasing nuit nek atic. 9B CHEANOAL PROPERTIES imac cf the halogen REACIVITY OF HACORLIANES Hel, CHE, ert, ; Denlty inky 2 mt Oe ea uo WOME WO AGB a Oh Tertiary * Secendary > Primary (Segp. os on ine 1% Aicanags the primary says kalitien he Aryl halides are heavier than water, Their demities follorws the under WL ACK OL Aryl iodide > Aryl brurmide + Aryl chleride 5. Dipole moment Maloalkanes their polanty depend Dipole moments of halarnet ac tivity Of halogen an the electer ex ate given baler CHCl> CHE OOK re CH by CIT) URED) (168b Dipole moment of fluoro methane is fees then that chloro methane, it is prot fluorine Haloarenes : The dipole mennent of haleateres lies in following sequence yy duc te very seral) ance of Plucrobenzene < Chluraherwene ty oy 1 Bronabrersrene, © Noboheere 11.7004 The lower dipole moment of fluarabenzene 1 pret due to small size of halogen, Resultant dipole. moments of isomeric. dichior teenie (ity Wisaination reactions Band F, reactions| gy resetion | BH OH Ba H H stow, 2 Fast | pce Se meen Re 1 HAY H x " +BOH+X Transition state [As the above reactions involve leaving of X~, the reactivity of alkyl halides (same alkyl group, different halogens) should be limited with CX bond strength. ‘Type of bond c-l c= Br Bond strength (keal/mol) 455 ss 665 ‘Bond siengih increases The breaking of the bond becomes more and more secondary > primary) is due 10 +/ effect of the alkyl groups which increases the polarity of C—X' bond. R R, mene So Rect R R The primary alkyl halides undergo reactions either by S,20r E, mechanisms which involve the formation of sition state, The bulky groups cause steric hindrance in the ation of transition state. Therefore, higher homologues Jess reactive than lower homologues. CH,X >CjHsX >CiH,X, etc, Prorraniciec tien) imnenneaa nee Synthesis as they undergo a large variety of reactions which listed below. © (@ Hydrolysis (Formation of alcohols): Alkyl halides hydrolysed to corresponding alcohols by moist silver oxide ‘or by boiling with aqueous alkali solution (NaOH or GRB Organic Chemistry for Competitions (2nd Year Progrem, CyitBr + AcOH HCHO + ays, Eyl bromide Ett altel [With the help of this reaction an alkene can be conven into alcohol. Alkene is first reacted with HBr to form ai bromide and then hydrolysis is done. njc—cu, HBS cH,cH,Br 44, cH,cH4,01 “Etiylene Et] bromide Fy let (ii) Reaction with alkoxides or dry silver oti (Formation of ethers): Ethers are formed by heatina halides with sodium or potassium» alkoxides or dry si oxide. The attacking nucleophile is OR” (Williamson synthesis). n—x+ Naor’ HE, RoR’ +Nax Sod, alkoxide \eoyin Eber 2R—X +Ag,0 H3 rok -2A0K All halide (659) sym Ether Hea 2C,HBr +Ag,0 “5 C,H,—O—C,H, +2438: Brotoethane (6) Dietiyether Heat C)HBr+ NaocH, — “S$ c,H,—O—CH, = Nab Sodium methoxide Eihytmeiyleter CaHsBr+ NaOC,H, 28S C,H, —O—CHy = NeBr Sodium ethoxide Mechanism : It is a nucleophilic substitution reectic and proceeds via S,,. mechanism, (CH ONa = C,H,O" +Na” Slow CjH,O +C,HsI—“4 c,H,0° mr CoH, ~ Fac, —0—C.H, +! Na’ +1 ==Nal Heat CHy—CH— CCH, +C,HJONa Br CH, 2-Bromo-3-methylbutane CH, CH,CH, ects +CHs = nei OC3Hs 2-Ethoxy-2-methylbutane (rsjor) Mechanism : OC)H, CHs (rioor) CHy—FH—en—cH, Br CH,Haloalkanes and Haloarenes OCH SBF awcH— ec, OCH, CH,CH—F— CH, suit cH, cH, 3° Carbocation (10st sable) There can also be elimination from 2° and 3° carbocation to give an alkene in presence of CH.ONa /C.H,OH. (iii) Reaction with sodium oF potassium hydrogen sulphide (Formation of thioalcohols) : Alkyl halides form thioaleohols with aqueous alcoholic sodium hydrogen sulphide or potassium hydrogen sulphide. The nucleophile is SH. Ro Nasi SHOWN poy Nay Sodium hydrogen a Alkanethiot sslpbide oF Thioaleabot C3H,Br +NaSH —CHOWH.O C\Hs—SH +NeBr Ethyl bromide ttyl thioalcobo! or Ethyl mersaptan A substitution reaction in which the solvent act as ‘nucleophile, is known as solvolysis reaction, (CH),C—Cl +H#—S—— (CH,),C_su = He terrBusl chloride ging tetsu oaleool (iv) Reaction with alcoholic potassium ¢ silver cyanide (Formation of alkane nitriles and isocyanides) + Alkyl eyanides are formed as the major Product when alkyl halides are heated with alcohelic Potassium eyanide (atack occurs through C). The nucleophile mide and RCN | Alkanenitite (Alkyl eyanide) +Ky | Propanenitile (Esty cyanide) many other types of ined by hydrolysis of {C1 or alkalies. R—COOH+NH, Acid CH,COOH + NH, oie acid 17 CONH, Nek so RCL oa con +H,o — cH.CONn, Basan 19 Taro sxom CRCONN Edunnile pharansie (Becton n (6) Primary amines are obtainad by the rafuction of cyanides with nascent hydrogen obtained By action of sodium and ethanol or with LiATH, of with nickel (Mendius reaction). R—CaN = 4H) SHON g_cunn, Alkyl cyanide Primary amine Na Con CHSCH.C=N + sy SE SUCK, CHCH.CH.NK, Propasitaaene (eProp Propansnicile (Edy cyanide) (@) Aldehydes are obtained by partial reduction of eyanides with SnCl, and HCI and then steam distilled (Stephen's reaction). Rca +2 3 0 CH=NH-HC] US Allyl cyanide i) inehyinecttonde x u R—CHO+NUACI Aldshyde When alkyl halides are heated with aqueous cthanolic silver cyanide, alkyl isocyanides (carbylamines) are formed as the major product (attack occurs through N). Isomteric alky | cyanides are also formed in small amounts. Ally isgyamide CoH,Br Bromoethane KCN 43 CHL—N Gk) “i Ett} isocyanide CExhyisarby amine) Ally] isocyanides on reduction with sodium and alcohol gives secondary amines, CH;—N=C 44H Methst isocyanide Na HOW CHy—NH—cH, Dinvty taming fon: The formation of eyanides ot Besvanides from alkyl halides involves nucleophitte sub: N) is a resonance Ni ico Resonating incre Asis evident from the hybrid structure in the ex ani fon Bath the carbon and the nitogen atone Re electrons. Therefore, either the carbon or the ogen atom nucleon hie eet donor to the alkyl hale Suck ucleophilic species which is capable “of attacking the18 molecule through two sites is called ambident nucleophiles. ‘Thus, CN™ ion is an ambident nucleophile. Now alkali metal cyanides (KCN or Nac) are jominantly ionic, Therefore, both carbon and nitrogen es 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 cyanide 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 cyanide group giving alkyl isocyanides as the major product. (9) 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—O is ionic in nature, therefore, negative charge on ‘oxygen serves as attacking site.The nucleophile is —ONO™ Heat R—X +K*—O—N=0" “S R—O—N=0+K—X Haloatkane Aly nitrite Heat GHBr +K—O—N=0 55 c,H,—0_N=0 Ethyl bromide Ethyl nitrite +KBr hanolic solution, nitroalkane is the main product. trite is also obtained. It is because the bond O being covalent.The lone pair on nitrogen acts oO BNO, cotsoning rex < tage ‘0 Nitroalkane 0 CoH 0HH0 ones CNC +AgBr ‘Oo Nitroethane ction with ammonia (Formation of eating with aqueous or alcoholic solution of ed tube at 373K, alkyl halides yield a Heat = C)HsNH, +HBr Edhjlamine (1°) CyH,—NH—CyH, Diethylamine (2°) +HBr GRB Organic Chemistry for Competitions (2nd Year Programme) (Cylig)gNH + Br CH, S82 (C,H,).N_ +e N-Etiyl Tretia (3° canamine (2°) (Calg) N +BrCpHy CE, (C,H) N" Br NNNDiehyl Tetrethylammonium etiaraine (3°) bromide (Quatemary a) This reaction is called Hofmann ammonolysis of alkyl 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™. R—COOAg+X—R ae RCOOR + Agt ster CH,COOAg+BrC,H, 22%, cH,COOC,H, + AgBr Silver acetate Elhyl acetate (vill) Reaction with sodium acetylide (Formation of higher alkynes) : Alkyl halides react with sodium alkynide (R—C=C—Na) to form higher alkynes. The nucleophile is CH= R—X +Na—C=CH —> R—C=CH +Nat Sod. acetylide Aline (higher) CH,CH,Br + NaC==CH —> CHjCH,C=CH +NeBr Bromoethane Butlyne Sodium aliynides are prepared when terminal alkynes rast wih sodamide (or sodium in iguid NH,) at 197 K. Lig. NH 197K Not R-C=CH + NaNH, ROC=C—Na+ NI ‘Terminal alkyne Sod. alkynide / (ix) Reaction 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. CoHSOHMM, Nas “HORE. Sod.sulphide 4 CHSOH/HO cones 2R—X + R—S—R+2NaX Thioether CyH —S — CH, +2NaBr Ethyl thioetane (Cietigl thioether) Thioethers can also be obtained by heating alkyl halides with alcobolic solution of sodium mercaptide (NaSR’), ies ‘metallic derivative of a thioalcohol RX 4Na—Sp’ LMsOUMRO 2C,H,Br +Na,S Bromoethane R—S—R'+ NaN Sodium, “Thioeher mereapide Hgonm CyHBr+ NascH, SOHNE 4, -s_—cHy Sodium metiyt ty ety het rmeeapide (Qty hoes) +NaBrHaloalkanes and Haloarene (9) Renetion with tudes fodidtes): Alkyl chlorides te sodium iodide (in acetone cor alkyl iodide, ‘ormation of alkyl 1 with sodium bromide or methanol) to form alkyl bromide similarly, atkyt bromides react with gudinnn iodide (in acetone oF methanol) 19 form akyL iodides R—CH4 Nabe —Aetane, Nl et ‘Alyt ‘byt cdlorie ile CMB Nat AES Oy, Nabe Vithyt bromide This is called Finkelstein re nation R (i De of alkenes): When alky! halides are boiled with a eoncentiated alcoholic Iydioxide, they undergo dchydrohaloy ) and alkenes sre formed actions are called eth the hydrogen atom of hatoatkane v from a Prearbon (Le, the carbon carries the halogen). h is eliminated comes. fom next to tht which HOV KY ' " OH(ale N—C=C—H ethene +11,0-+ KBr potassium ethoxide Primary (1°) which i 19 Heat CH CHCL + KOT ale.) = » HOCH, Chlorwethane (Py cucy Fihene (onaboanied Nene, Teast able) Heat , Wy H Kotte.) My CCH CH, CM, —CI—Cll, + KOM) resp CHC CH co (ire atte alkenes more stable) 2.C Moropeopane (2°) cy CHC, cl 2.Chloro-2-methylpropane (3°) In the dehydrohalogenation of secondary and tertiary hualoatkanes, when there is a possibility of formation of to isomers, the hydrogen atom is preferentially eliminated from the adjacent carbon atom with lesser number of hydro; ‘atoms, ‘This yenetalization is known as Saytzelf’s rule, ic., the more substituted alkene is more stable. For example, - CH, —CH=CH—CH, But-2ene (70% trans and 10% cise) (Dimethylethylene, mote stable) ‘CHy—CH>—CH=CH Butt -ene (20%) (Ethylethylene, less stable) KOU (ale) I (By, The ease of dchydrohalogenation is in the order: tertiary Aikyl halide > secondary Alkyl halide > primary Alkyl halide and the ease of formation of alkenes is: R,C=CR; > R,C=CHR > R{C=CH, > RCI > RCH=CH, > For different halogens it is in the order: lodide > Bromide > Chloride (sil) Action of heat : Alkyl halides when heated above 573K, tend (0 lose a molecule of hydrogen halide forming alken: r—cuci,x 22%, r—c=cn, +H Alkene Clsbe SBE H,C=CH, + HBr Bromoctane Ethene ‘The decomposition follows the following order: lodide > Bromide > Chloride hen same alkyl group is present) nd Tertiary > Secondary > Primary (When same halogen is present){GRB Organic Chemistry for Competitions (2nd Year Program » ccBareeas Reactions (9) Reaction with magnesium AIL halides fy = a —- Grignard reagents when tated with bry magnesium pygy ip Reduccion (Formation of alkanes): ATMS ae dry ether soon ob int Mado ae PAGAN WEE BAER NYENTA Sremad whan SRY Baas are ; Day ster Sob Sa See EEN AN ROY + Mg ayy) DEES ae ae satin or wT tron Day ether + Mg PES Cn Mone eo) Fini a very la numberof organic compounds. Reactivity onder R—1> 8—Br5R—C1 Reaction with other metals : Orzanometal compounds are formed. (a) When heated with zine powder in ether, alky! hak form dialbyl zine compounds. These are called Frankla reagents. sBr-2Zn == (CH); Zn + ZnBry (b) When heated with lead-sodium alloy, ethyl bron gives tema ethyl lead (TEL) which is used as. antikns compound in pero HBr = 4Pb¢Na) PEP (C.41,), Po = sNaBe =3 TEL () Ali halides form dialky! mercury compounds wt ested with sodium amalgam He > (CsH,),Hg Nebr De Ally halides react wi hiums. (@ Reaction with Lithium : lithium in dry ether to form alkyl lit BS, Rois Liv 721i — CHL = Libr Allyl lithiums are similar in properties with Grigas reagents. These are resctive reagents also and serve as st bases. (e) Corey-House reaction : Alkyl halide reacts wi lithium dialkyl cuprate (R,CuLi) to form unsymmetis alkanes. RyCuLi> RX —s R—R’+R—Cu-Lit Alkane (CH,),CuLi +BrCH.CH, — CH,CH,C Lidium dimetsi Ethyl bromide Propane 7 +CH,Cu + Lib a Ph ] I PhyCati + OC — CO =Ph.cu+ LiClHaloalkanes and Haloarenes Cyne A N [ecHy,CUICuLi + O -(O) HCH CHE (CU, ) Cub CCCI — TCC CHCl, FCLCu Lic alkyl halide on reaction with AyCaLi ive alkenes cH CULCUCI): Cut Lille cu, CH —> ICCC, (ery Cali e—F 2¢Metly}propene Br HCH CuH Lie CH, (xvii) Friedel-Crafts reaction: Alkyl halides react with ‘benzene in presence of anhydrous aluminium halides to form a homologue of benzene, AICI (ony) Coll, + RCI Benzene > Calle—R HCL Aihytbenvene Ali (any. Cally CH — Dr MOY, Cy, ett, stb Benzene Brombethane Tayth ion): Alkyl halides ‘e of sunlight, heat (xviii) Substitution (Iatog undergo further halogenation in pre: __ energy or peroxide. Bi Soc Br x Only CyUBry primary and je with hexamethylene iydrolysis, ive ketone in this reaction. 2 (a) Reactivity for oxidation reaction depends on the numberof hyd jos on alpha (4) carbon of alkyl halides Reactivity « number of e-hyd (b) Reactivity of different halides in decreasing order is as follows Henzyl halides » Allyl halides ~ Alkyl halides (4x) Fsomerisation: —Haloatkanes on heating at S73K or in presence of anhydrous AICI, at low temperature undergo inoleealar rearrangement to form an isomictic haloalkane, For example, cuycnen,cr 28", cn, —cl—cny k a AICI, i EChlotoprapane 4 2-Chhoropropuine CH,CH,CH,CH, Br BE CH, —CH—CH,—CHy Fromobutane SHI AICI | br 2-Hiromobutane 9.9 REACTIVITY OF HALOARENES () Low reactivity for Sy reaction: Aryl halides are less reactive as compared to alkyl halides as the halogen ator in these compounds is firmly attached and cannot be replaced by nucleophiles such as OH", NH3, CN>, ete. In lorobenzene, the electron pair of chlorine atom is in conjugation with m-eleetrons of benzene ring. Thus, lorobenzene is a resonance hybrid of the following structures 1 " ut wv v Low reactivity or inertness of aryl halides has been attributed to the following factors (a) Delocatization of electrons by resonance: The SH, IU and IV inudicate that the C—CL bond in chlorobenzene has partial double bond character. This makes the bond stronger and shorter than pure single bond (de, in alkyl halide). The shortening of bond length imparts stability to alkyl halides and as a result the C—CL bond cleavage becomes difticult which makes aryt halides tess reactive than alkyl halides towards nucleophilic substituti So, aryl halides are stabilized by resonance but alkyl halid are not. Like follows: ryl halides, the vinyl halides show resonance B22 Hite S284! C—¥ bond in vinyl halides like aryl halides is ttle more stronger than in alkyl halides and hence can not be easily broken, (b) Bond energies due to difference in hybridization : In alkyl halides, the carbon holding halogen is sp’-hybridized. In aryl halides, carbon is sp*-hybridized; the carbon-halogen bond is shorter and stronger and the molecule is more stable. This has also been confirmed by the X-ray analysis which shows that the C—CI bond in chlorobenzene is 1.69 A, whereas in methyl chloride it is 1.77 A (177 pm) (©) Polarity of carbon-halogen bond : Another reason for the low reactivity of aryl halides over alkyl halides is their lesser polar character and C—C1 bond in aryl halides is less polar than in alkyl halides. This is supported by the fact that the dipole moment of chlorobenzene is 1.69 D as compared to the dipole moment of haloalkane in the range 1.84-2.22 D. (@) Instability of phenyl (or vinyl) cation : In haloarenes and vinyl halides, the phenyl cation or vinyl cation is not stabilized by resonance (as a result of self ionization) because the sp?-hybridized orbital of carbon having the positive charge is perpendicular to the p-orbitals of the phenyl ring or the vinyl group. Therefore, these cations are not formed hence, haloarenes and vinyl halides do not undergo S,,, reactions. Qu Ove Chlorobenzene Phenyl eation HjC=CH—CIl —x> H,C=CH + Cr Vinyl chloride Vinyl cation us, aryl halides are much less reactive towards eleophilic substitution reactions than haloalkanes. FHowever, under drastic conditions, such as high perature or pressure, etc., the aryl halides can undergo tution reactions. ‘Activation of halogen atom: When a powerful Betron withdrawing group (¢.g.,—NOz, —CN, —SO;H or 1H) is present in the o- or pposition to the halogen the replacement of halogen atom by nucleophile (OH ) is now facilitated. For example, oH a cae +KCl i). ai. cI ro o-and p-aito- pheno! ce NO, and p-ritroaniline 23K 1s “BE CoH, +NH,Cl GRB Organic Chemistry for Competitions (2nd Year Progran, ‘The greater the mumber of electton Within, substituents in benzene nucteus, the easier it Wil hey fut the nucleophilic substitution (S y ) reactions " MK, on aq.) 2. 0,N on" ot Q» NO} . 2.4-Dinitochlorobenzene 24 Dinitophes NO; NO; O,N- —cl+ OH” M8, O;N- On NO: No; 24,6-Teinitrochlorobenzene 2AoeTriitopient (Picvie aid) Further, greater the number of such groups at o- p-positions wer. to the halogen atom, more is the reaciig aryl halides. It may be noted that nitro group at the mera-position to halogen atom has no effect on the reactivity These are the examples of activated nucleoph substitution. (ii) Ullmann reaction : When iodobenzene is hea with copper powder at 473K. in a sealed tube, biphenyl formed. Heat CyHsl +2Cu +1C Hy (ealed tube) Todobenzene Aryl chlorides and bromides usually do not give t reaction unless the halogen vated by. suit substituents (—NO,) in the ortho or para-position. Cots — CH, +00, Diphens! ‘Nucleophilie substitution reactions (i) Reactions of the chlorine atom : The chlorine ato in chlorobenzene is firmly attached to benzene nucleus duc | resonance and cannot be readily replaced by groups Til hydroxy, amino, nitrile, etc. However, by using drs conditions, replacement of chlorine atom by nucleophiles be done, (@) Replacement of —Cl by —OH : When chlorber zene is heated with aqueous solution of sodium hydrosid 623K under 300 atmosphere pressure, sodium phenoxite first formed which upon acidification gives phenol. on G ONa a NaOH(aq) waio, (CO) “BK, TO0amN v Chlorobenzene Sodium phenoxide re This reaction is known as DOW process for ® manufacture of phenol. (b) Replacement by methoxy grou when chlorobenzene is heated with sodium methoxide 4 in presence of copper salts. Ether is orHalogikanes and Haloarenes Oey L won 3 (OT os Crlombenzene — methovnte Atniwste (Merny sean Tete) ut oun treatment witty aloo in prwseise oF NEON) at ester iy fame WEN, wai) el Foon txts YEMEOOC H, Vaiot town (6) Replacement by amine gems When ehlan benzene is treated With aguioony amma: al ATK unntor a pressure of 60 atmosphere in presenioe af eMIPHINS HVE OF cuprous chord, aniline is tonne a nny L 10 e2Nt eco AN 2(C )) setensene Aniline HEWCE MLO Aniline ean also be prepared by th with NaNU/KNU. ng elomwbenzene in Liquid ammonia at ryan fempenatiny, Liquid NUL, CAH CL RNIL, > CQUANUL, ECL EN group: nile in (a) Replacement by benzene is treated with cuprous 473K, phenyl cyanide is tonned. oh “N = Sm Phong evans When chlony fatine oF DME at an be converted into nian) wylamine, benzoic acid, Grignant reagent is ether is sed ay solvent Malte AW) Revtuetion ) Chtawbeavene uintoniaes yestnettan DAN TAM gt NCCAT aon iy NAM sai Na-=NMg AD ge teneene ro \ f yyy Meaty LO} can Mies LO] eet ~ ww FANNY, Unentvanee eon Uh) Waneeditly yeaction ARE bensomes te firmed! when ehhfonabonzene ts tutes witty ATAy hahlos aint owtionn metal ir aley etter 0 \ , tysta , Ol: el (OO) ast Ginoaro rice Ohm, OO Wont (O)-cranerer emavaboaeene 2Nacl Vhis ts Known ats Bitip eenetton, (9) Replacemene hy SU gHonyys Wher ehloasbens cee Is toate vith aaquoots potassionny hystiagen sulpils y presence af eapper sal ALAVAK, pheay Lhiophenol as forest ERUQEL RSH EES Cost RED eahatowane AIK Nahost (0 Resetton with sodiannide fn qukl anunonta (ormation of awithved Wy a mumber at eases ot inicTephilie aromatic substitution, the entering. goon does Hot jocupy the position Vaated by the eypetlet gonap. Re of this fype have boon etl ettessubyttanti tnectianism invalves bo steps (a) Fommation of omayne (1 2atehystonbenrzene) intermediate by a stepwise elimination —Hatkawext by: (by Sopvine adatition &9 henaytne WY Roem the pHMlet A WHieh Position of the nucleophile may be Mifkeveat vo tons ns Vis Nant. NA) NT, TRA wT Ll Ehbrwbemrene Newiyne un ore Anite24 When chlorobenzene is treated with sodamide in liquid ammonia at 196K. the reaction occurs through the intermediate benzyne formation and finally gives aniline (ii) Reactions of benzene ring: The —Cl group in chlorobenzene iso patitvetor and deactivating. However, because of steric hindrance at the o-position, the p-product usually predominates over the o-product, The benzene ring undergoes halogenation, nitration and sulphonation (Electrophilie substitution) reactions. The rate of reactions is bit slower in comparison to benzene, ¢.¢. the nitration off chlorobenzene is 33 times slower than that of benzene, NO; 101) 1-Chloro-4-nitro- benzene (major) a o NSO, (cone) mer Theat, Sulphonation) a SOsH ‘o-Chlorobenzene p-Chlorobenzene sulphonic acid" sulphonic acid (minor) (major) a cl cl ClyFech x (Chiorinationy oie. 4 Tze peDiehlorabenzene HCHO + HCVZnCI ‘nloromethylation) bd o-Chloro- - CHCI enzyl chlorid it benzyl chloride ‘bine benzyl chloride a with chloral: When chlorobenzene is I (trichloroacetaldehydc) in the presence of Spowerful insecticide, DDT (p, roethane) is formed. iH ‘-dichloro- O;N- NO2 Noury ~ThSO, GRB Organic Chemistry for Competitions (2nd Year Program "Oy SHO eye O) : ° {Oya Ls ing Chlorobenzene ~, Oya DDT [2.2-hi( C,H,CH,Cl + POCI, + HCI Benz alcohol Benzyl chloride 3. By heating benzene with formaldehyde solution and HCI in presence of anhydrous zine chloride, benzyl chloride is formed and this reaction is called chloromethylation or Blane reaction, 2aCly +HCl 3, C,H,CH,CI +H,0 CeHy + HCHO Formaldeh Benzyl chloride de Properties: It is a lachrymatory colourless bad smelling liquid. It boils at 452K. Its vapours bring tears from eyes and are irritating. It is insoluble in water but soluble in organic solvents. (@ Nucleophitic substitution reactions : ag. NaOH 2 CH CH,OH (oil) “Benzyl alcohol SERN CyHACHACN eonter (warm) “Benz eyanide Benalchloride | ate. Nu, CH.CH.NH, (warm) ” ‘pezyl amine? CH;COOA, HCOOAE, HsCH,00CCH, Benzyl acetate (i) Wartz reaction : 2CgHsCH,C1+2Na Ether, C,1,CH,—CH. CyHs +2NaCl Benzyl chloride Dibenzyl (ii) Wartz-Fitig reaction : CoHSCH,Cl +2Na+ CIC Hy —3 C.HACH,CyH, Benzyl chloride Chlorobenzene Diphenylmethane +2NaCl (iv) Formation of Grignard reagent : EES CHIC MgCl Benzyl magnesium chloride CoH CH,Cl+ Mg (sy)an (8) Qettatton e When caibeed Wil (lit HHO: Teerveate uit te tinned Ciaran by MCh, alone edie boieate wet awe HO GICLEE Oy - Wow tosttoad awit eupile nltnite or feud aiuate wvidiooa bene nldelivte AH) Heeatettony | Whew sevtucued wrth Ziv Cir capil, Hh ovine totem CQMCH CLOTH Asti) Htectrnphitl C(I COOH HCL ie + 4lly ver eetnnoetle Crh HE sueetiition sh jaye Aistial elec timphiic subetitathon tenctions CHEE rte, pose allivetor Hiletinetton between Chtucubensene and Mengyt Chir ide Uwe cldotatenzene (Nuetent flier cvaryanniay, the Watoygou tone te tne nal Ganiot tne tephiced hy OF, NIL. CN, of, anitor city cvtlitions, while it twueyt eldnide (edtese fae tualowon counpanday, the: hiloent atone ts very’ renetive ant hence cant be: ently aeyhacell by OW NI CN (0 Moncton yttte teat hives white precipitate wil thtorobon zene doe nt eat EQHICHCEE ARNO (alt) 9 White pp of AwCL CgHCL ARNO, (ale,) om No renction AW) Rewethon witty allaline KAINO, 1 HenizyLctloride viliscdl ta beneate cht witty ath, MNO, fa Atocetoutisation ocean andl shot wide chil gives COOH {oe halen atone ths, ellaninnted Chlwabeazene lowe no fone, Ces, tu alocotntaation tikes phic aul the Fualoyon atom fe hit afloctedd by ental ole KM CIACHLCL 210] Aes chloe he AWG) | Honsyl chloride lhe AgNO eutution white CICOOIE HEL Henente oui wth, KMHG ICL > Ne renction Clobenzene (id) Hydtratyater Chlorabeusete cannot Iiydiolysed while beat chloride anid other dleuivatives van easily bo hydrolysed CHLCH CLF ROL (ap) Nehaslehtnide C,IACHCL, ieee hie be evally sldosehila » Gy CHOHL FRCL Weal eel » CALCHO HCL FLO Wiualiehyite HOO, = COI, ¢ ‘HOU HCOOH MCL Henstte weit iene Lae arene odour white Horie in Laeluymatory Iaavieye teint odour, lode Crafts reset | Chlorobenzene dae Crate reaction with benzene «x toluene, while anni Or genie: Chiarnisiry far Cannpves bonis (HA tery Wein ven Friedel Cpalla Feaniean nith eneyl obit wives Fv Ml bene enenics af nndeplvnts BACH, wu Fat ihe nari ANN, Wy OMAN L Me sy TL Har ohh Viphan jatar Wisse 0.1) DIHALOGEH DEMIYAIYES General Methiuds uf Hrepar ation Uy Atliylidene tates car yer Aibeatiden or A diy aihaner 5 The glvens wsmera tcthueds ave vserd tq vegans of pene cities Tap Hy the wetlan of pluvaplinr ns entahatidey Indeleyedes and betwen | Voi buliagen alesis «60 Ls ata tate ashen wenn he wldehibe to Keane wee ete pinapihinis ientababite CUOMO PE, or CNS, A retaliate Ltniddonrathave Wefan eben OM CA Ld Nnableangnenzs Magainifindere CACO, PEL ws Arata Addition of abies eos oa form wenn dilulides. Fer ew tunlecule of un sib yo, Analecttes of leyeens wee ave peaqanved, C4 teil: be ad i Caniverted inte ube Lad and tacw dude Leos ant 9 frat (hy een alleyns Hem CH HCL ae Avetylene CMe NA Mtn i, Lttaen (tere rare CSCI TI mr COLH, Hoye 22: Unedaog onangylniene donde) (i) Allylene hualdes oF viewibatiies or 1,2-dih ines | These may be obtained by talleving meth (ay Hy the addition of halupens to alkenes : Add occurs On the Ho ethan stone Nnked bry w double bend WCC, Ch, CH, CICHLCL {tiene 120i Mennthave (thylereehdenidey > CH CHICH, Hr CHO OF Vin eon Hee 2 oy ‘vet leve shane CHACH CH, Bry apa 124nhn gp (hy thy the wetion of phuspharis nates tdlyenlesGlycolear diya alcohols eact yoth plang Juaides or halogen acids ar SOCL, ta form yie-dihalides Con cH 12NCh, > sapocd, «2 CHOn CHCl Vite 12 Diehlonvethane shyt hijlenw cenitHaloalkanes and Haloarenes ‘Note? Allylidsne or alkylene iodides are prepared by halide exchange ma Physical properties : (i) Dihalogen derivatives of lower alkanes are colourless, sweet smelling liquids. Higher homologues are solids. (ii) They are insoluble in water but soluble in organic solvents. (ili) They are heavier than water. The methylene iodide (CHI; )is 3.32: known (except (iv) They &: melting points show re; Chemical properties are le: le all reactivity as alkyl bal are given ahead in cor = eae (Geman [oo atyietanan iceanacy 7 sai Forma oreo fae ia Ko cae Methyl maloni acid on CH{CHCL, + 2KOH(eg > He | on (esatley HC. on | + 2KOH (2g) cK | (Moogearbonghis acid) H —— cH,—c: CHO) Astaizenee HC on | 2Dishloropropane (este | (propylene ehorde) HC | — c=} FED yc accor | Form atkynes, | Form aynes, cHcucr, KOH), HoH | 1,-Dichloroethane Acetylene | Form alkenes CH,CHCI, ~ Zn HOH, ae tts tidene (4) duct ry one Eagle (4) cN CHEN i cx, TEN no sICH,CHCI, + 2KCN —+ cuca xa 9, as, FEO no i.t-Dictiora ’ CHEN COOH she cH.CO. cHCH tet, cu,CH,CooH Het, § > COOH OP) Propanoic acid cRcooH HO) CHco- Saxe ont (Drcarboagtes sexs) Surin antyernte28 9.12 TRI-HALOGEN DERIVATIVES Chloroform or Trichloromethane (CHCI;) It is an important trihalogen derivative of methane. It was discovered by Liebig in 1831 and its name chloroform was proposed by Dumas as it gave formic acid on hydrolysis. In the ppast, it was extensively used as anaesthetic for surgery but now it is 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. C20Cl,; +H,O —> Ca(OH); +Cly Bleaching powder From alcohol : (i) Alcohol is first oxidised to acetaldehyde by chlorine. (Cl, +H;0 —> 2HC1+0} CH,CH,OH+cl, Seétion, CHACHO +2HCI Ethyl alcohol Acetaldehyde ii) Acetaldehyde then reacts with chlorine to form chloral (trichloro acetaldehyde). CH,CHO +3c1, Hesnation, cetildehyde CCI,CHO loroacetaldchyde ‘ (Chlorad) (So, Cl, acts both as an oxidising (i) and chlorinating agent (Gi) Choral thus formed, i hydrolysed by calcium hydroxide, OHC} CC, +3HCI Hydrolysis JO cul, Chioroform + (HCOO),Ca Calcium formate Hydrolysis ECI,CHO + Ca(OH) —“"*,, 2CHCI, + (HCOO),Ca} (i) Acetone first reacts with chlorine to Clorination “8°, CCI,COCH, +3H1C1 Trichloroacetone jone is then hydrolysed by calcium 2CHCI, Chloroform + (CH;COO),Ca Calcium acetate hloride : Now-a-days, chloro- le by the reduction of carbon Jand water. This method is used GRB Organic Chemistry for Competitions (2nd Year Progranma) feito, Follh;0 cel, +24 CHIC, + HCI This chloroform is not pure and used mainly asa solven, 3. Pure chloroform: [tis obtained by distilling chiogy hydrate with concentrated sodium hydroxide solution CCI,CH(OH)) + NaOH —> CHCl, + HCOONa + 14 Chiral hydrate _ Thloral hydrate Ws a stable compound inspite of the fact that two —OH groups are linked to the same carbon atom. This is due to the fact that intramolecular hydrogen bonding exists in the molecule between chlorine and hydrogen atom of —OH group. Physical properties colourless liquid. (ii) Itis heavy liquid. Its density is 1.485. boi G organ aI cl So a, u-? @ Ww & sweet smeling at 334K. i) It is practically insoluble in water but dissolves it solvents such as alcohol, ether, etc. iv) Itis non-inflammable but its vapours may bum wit green flame. (v) It brings temporary unconsciousness when vapouns are inhaled for sufficient time. Chemical properties : (i) Oxidation : _ When expose to sunlight and air, it slowly decomposes into phosgene (carbonyl chloride) and hydrogen chloride. Cl. cl ch a g N\ eS +10) He, ed cr H andar cr OH Cl. > .C=0+HC cr hore or Might Sunlig 2CHEI, +[0}, TO, , 2COCIy +2HCl Phosgene is extremely poisonous gas. To use chloroform as an anaesthetic agent, it is necessary to prevent the abo reaction. The following two precautions are taken whe chloroform is stored. (a) It is stored in dark blue or brown coloured bot which are filled upto the brim, (b) 1% ethyl alcohol is added, This retards the oxidation” Converts the phosgene formed into harmless ethyl carbonate OC Hs +2HCl OC Hs (Di) Ethyl carbonate COC, +2C,H,0H —5 o= ceHaloalkanes and Haloarenes When rafvoat with zine and HM in presence of ethyl aleohol, it forms cHeI, Cdocoern (ak ory Zenct CHCl, Matteo eons When rafuced with zine dust and water, methane is the rain pooctuct, + HCL ZnO cHeI, oH CH, +3HCI Methane (ii) Chlorination: Chloroform reacts with chlorine in posseace of diffised sunlight or UV light to form carbon cc, + HCL Cderofiem Catv rerachlonde (i) Hydrolysis: Chloroform is hydrolysed when. treated with hot aqueous solution of sodium hydroxide or poussium hydroxide. The final product is sodium ot potassium salt of formic acid, =NYOH(eg.) pou ace ‘3 OH(cq.) —— > | H—CC-OH] —> 7 cio NG = Na OHtag.) “NC on} ‘ortho-for (unable) ,0 0 NOH / HC CHO Sm Sodium formate is chloropicrin or trichloro Iisa liquid, poisonous and ‘gas (Lear 835), CNO,Cl, +H,0 Choropictin y formed high temperature with silver A. HC=CH+6AgCI BAccyene Chloroform 29 a cu. Ze" won HON cuc -o=cC SS >< Cote cH, ene City Acctone 1 leTrishloro-2-nethytpropan-2 (Choretone) Mechanism : ( CUCL, +OH —> iCCI; + H,0 cl; — tech, cry CH CHO Wy De=£6 85, > < cu’ chy CCl cHy z CHA Ou to, aid Set Se cay cet; on” cer, ride : Chloroform when shoxide, ethyl ortho-formate is formed, ESWC, ACs noc€ Ci NrOC.H, —> 4 CoH, - S Gwe ; Ngiinaocstn Eauc) OCH, erin Eyl orhotoviate Gx) Reimer-Tiemann reaction: Chloroform reaets with phenol when heated in presence of sodium hydroxide or potassium hydroxide, The product formed is salicylaldehyde. on Ou -CHO Rsk 7 sy + CUCI+ 3NaOH - or Q O Phenol o-tlydrobenzaldchyde (Salicylaldehyde) + 3NaCl + 21,0 ide test): This lly a test of primary amines. Chloroform, when heated with primary amine in presence of alcohol potassium hydroxide forms a derivative called isoey. (carbylamine) which has @ very otfensive smell, (9) Carbylamine re reaction is act CoHyNHy + HEL, +3KoN M2) Ct, — Nex “ating Chloeoorna Phenyl iseyaie #3KCL+ 31,0 R—NH; +CHCL, +3KOI(ale) A R—-Ne=c +3KCI 1 Amine Carbylaminoatkane {Alkyl isontite) +3110 This reaction is also used for the test of ehlorofonn, (si) G-Elimination reaction: Chloroform undergoes acclimination reaction to give dichlorocarbene (singlet) which ont intermediatecul, ICL, 1 CL HOW EWlorotinmy A Dehn abe Uses: (0) Tis sed ay a solvent for fats, waxes, rubber, resins, iodine, ete Gi) ICs used for the preparation of chloretone (a dig) andl chlonypictin (insecticide), iii) Wis used in laboratory for the test of primary amines, iodides and bromides, Aiv) It can be uscd as anaesthetic but due to huarmfil effects it is not used these days for this purpose. It causes liver damage when inhaled in excess (SO is CCL). Halothane (CACHE is tess toxic than CUCL, but a fo containing anaesthetic agent widely used these days. is isoflurane (I,C—CHCI—O—CHIF,). (8) Temay be used (0 prevent putrefaction ‘materials, cin the preservation of anatomical species. (vi) The major use of chloroform in these days is the ‘manufacture of freon reftigerant R-22, organic Physiological impact : i) On inhaation it depresses the central nervous system, Gi) Us vapours when breathed, eaus fatigue and dizziness ii) Chronic exposure damages liver and kidneys 8 hea Environmental impact : When exposed to sunlight and air, it slowly decomposes, ny! chloride (phosgene) and hydro i Cl ch Deo W cl Chloroform Phosgene or (CHCl, +40, col, +HICI] 42CHCl; +0; —”> 2cocl, +2H1C1 is extremely poisonous To use an angesthetic agent, itis necessary to he! above reaction. The two precautions, (are taken when chloroform is stored. ih dark blue or brown coloured bottles upto the brim. 30 GRD Organkc Chemistry for Competitions (2nd Year Preqrane, Jo + 2Hcy OCH, hy carne COCL, 42C, 10H —r 0 Phosgene Vitunol Vests of chlorofo (cathylamine test), (ii) It forms silver mirror with Tollens' reagent (ili) Pure chloroforin does not give white precipitate y aqueous silver nitrate because C—Cl bond docs not ionie 9.13 IODOFORM OR TRHIODOMETHANE (cH, 1M gives imeyanide lodoform resembles chloroform in the methods of prepara ‘and properties 1 ory preparation : fodoform is prepared in laboratory by heating ethanol or acetone with iodine a alkali, (a) With ethanol: The reactions taking place are: 2NAOW4 1, —> NaOl + Nal + 11,0 Sodium hypoiodite (i) Oxidation H,CH,ON + NaOl > CH,CHO + Nal + 11,0 Eshanol Acetaldehyle (ii) fodination CHACHO + 3NaOl —> C1,CHO+3Na0H foal Gil) Hydrolysis CLCHO NaOH —> CHI, + HCOONa woaeetaldehyde Iodoform — Sodim formate (1) With acetone: () todination CH,COCH, +3NaOl —y C1,COCH, +NaOH Acetone “Triciodoacetone Gil) Hydrolysis CL COC, + NaOH —> CHL, + CH\COONa Todoform — Sodium acetate ‘The complete reaction may be written as: CHCHO1 + 41, +6NaOH 44 CHIL + 11COONs Hh Jodofarm + SNal + SH, Sodium carbonate ean be used in place of KOH or NaOit CH,COCH, +31, +2Na,CO, Ss CHI,, + 3Nal Aectone Todoform + CHjCOONa +200, ‘These reactions are called fodoform reactions. The lodoform test is exhibited by ethyl alcohol acetaldehyde, acetone, those alcohols which posses: —CHOH—CH, group (2-ols) and methyl ketones ete.Haloalkanes and Haloarenes CH, —CH—CH 4-41, 46NA0H 45 CHIL, Todoform on Propa ol + CH,COONa + SNal +5110 " | hGH, + NOt Bs ou b CH, +Nal +110 AFC, #38801 —s kG —Ch, +3800 6 R—C—Cl, + NOH —> R—C—ONa + CHI, § (Yellow ppt) Industrial preparation: Todoform 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 333-343K. KI Ki4r Cathode anode Ki4e7— 5 Ko —S 1, #20 1 K+H,O —> KON+SH, KOI is neutralised by CO, 31 Uses : Iodoform is extensively used as an antiseptic for dressing of wounds; but the antiseptic action is duc to the liberation of free iodine and not duc to iodoform itself. When it comes in contact with organic matter, iodine is liberated which is responsible for antiseptic properties ‘Fests of lodoform 1 Agl. 2, Carbylamine reaction : CHI, on heating with primary amine and alcoholic KOH solution, gives an offensive smell of isocyanide (carbylamine). 3. lodoform reaction : With I, and NaOH or I, and Na,CO,, the iodoform test is mainly given by ethyl alcohol ° AUNO, + CHI, gives a yellow precipitate of (CH,CH,OH), acetaldehyde (CH;—C—H), a-methyl ketone or 2-one (—C—CI), secondary alcohols or 2-ol ou (—CH—CIIy) and secondary alkyl halide at C, I—CH,). Also lactic acid (CH; —CHOH—COOR), pyruvic acid (CH;—C—COOH), methyl phenyl ketone (Cols —C—CH,) and 2-amino alkanes GF give NH, this test. 9.14 CARBON TETRACHLORIDE OR TETRACHLOROMETHANE, (CCI,) It is the most important tetrahalogen derivative of methane. Manufacture From methane : Chlorination of ‘methane with excess of chlorine at 673K yields impure carbon. tetrachloride. cH, + acl, 28; cel, +aHc1 (exce’s) Methane used in this process is obtained from natural gas. (ii) From carbon disulphide: Chlorine reacts with carbon disulphide in presence of catalysts like iron, iodine, aluminium chloride or antimony pentachloride. AICI, oF SbCls CS; +3Cl, ———— CCI, + 8,Cl; (eatalys) Sulphur monochlorideS2CLy farther rovers with CS, t0 form more of carbon tetrachhonite esy ease, > OCH, A 68 Sarton tetrachloride is obtained by thtctional distillation, Was washeat with saat hyatrovie and then distilled to got a FN Sample {8 Broun propane Propane is reacted with ehlorine st about O73K and at a pressttre of 70-100 atmosphere, Meat +91; CC + CC #SHICE Besser” Gan Heaehlono- tesrachloide “ethane guid) Physical properties: i) Iti characteristic smell, (8) Lis non-inflammabte and pois point 350K. il) i solvents, Gy) Trisaneycetlent solvent for Chemical properties + Carbon tetrachloride is. less reactive and inert to mast organic reagents. However, the following reactions are observed. () Reaction with steam — (oxidation): Carbon tetrachloride vapours react with steam above 773K to form phosgene. a poisonaus gas. a colour insoluble in et but soluble in organic Supeticated cer, +H,0 SS, coc, +2Hc1 Phosgene i) Reduction : Carbon tetrachloride is reduced by moist inn filling into chloroform. ‘sean 773K cel, +28 FEE®, cnei, +n (iii) Hydrolysis : On heating with aqueous potassium hydroxide it forms carbon dioxide which combines with Potassium hydroxide to give KCI and potassium carbonate inorganic salts). cel, +4KOH ——> [C(OH),] ——> co, | Carton tetrchloride (ARCH Gensatig) | C210) KOM, k,CO; +11,0 with — phenol (Reimer-Tiemann Carbon tetrachloride combines with phenol in odium hydroxide to form salicylic acid, on COOH 2011 -H4Na01 ‘orllydroxybenzoie acid (Salicylic acid) 4+ ANaCL + 2,0 GRB Organic Chemistry for Competitions (2nd Year Prog (9) Friedel-Crafts reaction: Benzene oy with Cy in presence of anydous AICI, pny ge diphenyl methane which on hydrolysis. form ‘i Ketone (benzophenone). " Aliya. AICI 7 Cig HCCL, ————— (C1, C1, How ener | AOI Dichloro. "2 diphenytmetiane on (CyHs)2C Spor (Coty, Tio} (CoH) \on 1 kt (unstable) Uses + (i) This used asa fire extinguisher under the pyrene, The dense vapours form a protective layer o buming objects and prevent the oxygen or air to co contact with the buming objects, hence the room or wi should be well ventilated, (ii) IL is used as a solvent for fats, oils, waxes and gr resins, iodine, ete, and also in drycleaning ii) WC finds use in medicine as helminthicié elimination of hook worms. Civ) Its used in the manufacture of chloroform as n freon. Phy logical Impact (i) Exposure to carbon tetrachloride causes cant human beings, Gi) ts vapours when breathed cause vomiting, a dizziness, light headedness and it may damage nerve permanently. (iii) On exposure to carbon tetrachloride, a person eye invitation, irregular heart beat also. (iv) On chronic exposure of CCl,, a person may 2 ‘coma and may lead to death. ronmental Impact When vapours of carbon tetrachloride reach 10 Atmosphere, deplets ozone layer, Ozone hole permis ultraviolet radiation to reach on earth. Ultraviolet rai may cause skin cancer, eye disease and disorder: i ' adversely affect our immune system i., defence system”! body. 9.15 SOME MORE IMPORTANT HALOGEN DERIVATIVES DERIVATIVES |. Freons : ‘The chloro fluoro carbon Ag compounds of methane and ethane are called freon the derivatives are: CHE,CI (monochlorodifluorom™*— CECI, (Trichlorofluoromethane or Freon-t!) ch (ichlorogiMuoromethane or Freon!2)._ (chorotrifluoromethane or Freon-13), CaF Cla (FFHaloalkanes and Haloarenes GAC; (Freon-23) and CLF,Cl, (Freon-24) ete, These derivatives are non-inflammable, colourless, non-toxic, low boiling liquids. These are stable upto 823K. The most important and useful derivative is CF;Cl; Freon or freon-12 (CFCl;) is prepared by heating carbon tetrachloride with antimony trifluoride ot 413 K in the presence of antimony pentachloride as a catalyst. It is also called Swarts reaction. 18 SPC, 3CC1,F; +2SbCly (catalyst) Freon-12 Orit can be obtained by reacting carbon tetrachloride with hydrofluoric acid in presence of antimony pentafluoride. 3CCl, +2SbF, cel, +2HF SS, ccl,F, +2HC1 Under ordinary conditions freon isa gas. Its boiling point is 243.2K. It can easily be liquefied. tis chemically inert. It's used in airconditioning and in domestic refigerators for cooling purposes (as refrigerant). Halothane (CF,CHB:C\) and methoxy flurane (CH ,OCF,CHC1,) are used as inhalation anaesthetic. These are also used as propellants in aerosols and foams to spray out deodorants, cleansers, shaving ereams, hair sprays and insecticides. Environmental Impact However, freons are persistent because micro-organisms and other agents that causes biodegradation of natural organic materials are unable to break these stable molecules or can do slowly, Therefore, most freon eventually sphere, freon is able upset the natural refore, their use as anes diluted with catalyst. polar, extremely stable to UV. light It is environment 33 ‘On polymerisation tetrafluoroethylene forms a plastic-like material which is called teflon, Polymerisation 70.1020 K nCF,=CF, CF) —Chy ‘etraioroethylene Teflon Teflon is chemically inert substance. I is not affected by strong acids and even by boiling aqua-regia, Iti stable at high temperatures. It is, thus, used for electrical insulation and preparation of gasket materials. 3. Acetylene tetrachloride (westron)(CHC1;—CHCI;): ‘Acetylene tetrachloride is also known as sym. tetrachloro- ethane. It is prepared by the action of chlorine on acetylene in presence of a catalyst such as ferric chloride, aluminium chloride, iron, quartz or kieselgubr. Chor AICh He Feber A CHCI,—CHCIy (1,1.22-Tetrachloroethane) -CH+2C1, 2 ata) In absence of catalyst, the reaction between chlorine and acetylene is highly explosive producing carbon and HCl. The reaction is less violent in presence of a catalyst. Itisa heavy, non-inflammable liquid. It boils at $19K. It is highly toxic in nature. Its smell is similar to chloroform. It is 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;=CHC1). CHCL,—CHCI, +Ca(OH), —> 2CHCI Westron Westrosal (Trichloroethene) +CaCl, +2H;0 Both westron and westrosol are used as solvents for oils, fats, waxes, resins, varnishes and paints, ete. 4. p.p"Dichlorodiphenyltrichlorocthane (DDT): When chlorobenzene is heated with chloral (trichloro acetaldehyde) in the presence of cone. H,SO,, a powerful insecticide, DDT (p, p’-dichlorodiphenyltrichloroethane) is formed. H Lo. Oretuse, Art cect ccl,c=0+ = Chloral 1O)-cr NOvet DDT (2.2-bis4-chloropneny) Chlorobenzene LL -tichloroethane} Lis a white powder, insoluble in water but soluble in oils. ighly stable and not easily decomposed in the +H,0 Uses : DDT is used as an effective insecticide for mosquitoes, Mies and crop pests. It was also an important antimalarial, since it destroys anopheles mosquitoes which spread malar Many species of insects developed to DDT.34 GRB Orc Environmental Impact The major problem with DDT is its non-biodegradable nature. Its residues accumulate in environment and its long | term effects could be highly dangerous. It is not metabolised by the system and gets deposited on the tissues. This Taises alarming dangers. However, it is highly toxic to fish and its use has been recently banned in several countries. : 5. Benzene hexachloride, (BHC), CoH Cl, : It is Prepared commercially by the addition of chlorine to benzene in presence of sunlight or ultraviolet radiation. Out of nine theoretically possible isomers of benzene ad oH b NS Wo Soe se, GB EE ES +3ClL ———— HC CH Light >A AG | Z\ H H Cl Benzene Benzene hexachloride cl Ch Cl or cl Cl cl (BHC) hexachloride (1,2,3,4,5,6-hexachloroc: isomer is the most important and powerful insecticide under the name of gammexane or 666 or lindane. It is also used extensively as a pesticide in agriculture for killing termite (white ants) from soil. 'yclohexane), the y- effective one. It is used as a nochlorination of 2-methylbutane, the total number compounds is: (IT 2004; AIEEE 2012] (b) 4 (d) 8 b)) The number of monohalogenation products obtained from any alkane depends upon the number of different Be ge ee