ALKYL HALIDE CHARACTERISTICS @) &) © @ © oO ® ‘These are the organic compound in which halogen is directly linked with carbon atom. ‘These are also called as Haloalkane. Their general formula is C,H,.X,(X =F, Br, Cl. 1). In these compounds, hybridisation state of carbon is sp?. In these compounds, geometry of carbon is tetrahedral. Central carbon atom has a bond angle of 109° 28". (On the basis of no. ofhalogen atom, these are of following types — @ — Monohalide © - —Theyppossess single halogen atom. eg. CH, -Cl, CH, - CH,Br (@) —Ditalide ~=— = These areofthree types eg. gem dihalide, vicinal dihalide and a, cahalide Tiitnide — - They possesthree halogen atoms. eg. CHCl, CHI, (v) Terahalide — —_Theyppossess fourhalogen atoms. ¢g-CCl, (vi) Polyfulide © — ~—-Theypossess more than fourhalogen atoms. (h) Ally! halide shows chain and position isomerism. Iunsyrfimetrical or chiral carbon is present then it shows optical isomerism also. METHODS OF PREPARATION OF ALKYL HALIDES ® By Halogenation of Alkanes Halogenation of alkanes takes place by free radical mechanism. R-H+X-X —™4 R-X+H-X R-H+CI-SO,-Cl P=, R-C1+SO, +H-CI From Alkene ( Hydrohalogenation ) :— HH HH pede +H-X —> nH XH Note: From alkyne we cannot obtain monoalkythalide. From Alcohol :— (a) UsingdryH-X:- Aahytrows nC R-OH + H-x Soe R-X+H,0 (dry)Note: @ ‘The reactivity order of HX in the above reaction is— HI>HBr> HCl @ _ The reactivity order of alcohols in the above reaction is- 3°>2°>1°>McOH ‘The above reaction is called as ‘Grove's Process’. :~3ROH +PCl, —+ 3R-CI+H,PO, ROH+PCI, —+ R-Cl+HCI+POCI, Important Note: = Bromine or lodine derivatives can not be obtained from the above reaction because duc to larger size of Bromine or lodine, PBr, or Pl, are unstable. (@) _Darzen’s Process: - isthe best method for preparation of alky! halide. ROH +SOCI, #*+RCI+HCIT +sO,t From Silver Salt of Carboxylic Acid : ‘The reaction is called as ‘Borodiene - Hunsdiecker" reaction. It is alsoa good method for obtaining, alkyl halide, but from this reaction we obtain only bromo derivatives because reaction is based upon Ronee Bebe SS» R-Br + CO;T AgBr Note: — @ _ Inthe above reaction the reactivity of alkyl group is : 1°>2°>3° @ _htisatsoan example of decarboxylation. From Alkyl Halide : Finkelstein Reaction : R-BrorR-Cl+KI —“**> R-1+KCI In his reaction only exchange takes place and the reaction is called as Halogen exchange reaction or ‘Finkelstein Reaction’. Swarts reaction rn R-BrorR-Cl Sieg? R-F ‘This reaction is called as'Swarts reaction’ PHYSICAL PROPERTIES (a) Alkyl halides are colourless with swect smell or pleasant smell oily iquid, whereas CH,F, CHCl, CH, - CH, - F, CH, - CH, - Cl are gaseous in nature. () _Alkyt halides having 18-carbon or more than it ae solid in nature.© @ © @) Although carbon - halogen bond is polar in nature but alkyl halides are insoluble in H,O because they cannot form bond with HO. ‘These are completely soluble in organic solvents. M.P& B.P. x molecular weight. For same alkyl group the order of B.P. is RI>RBr> RC1> RF Polarity order is RF> RC1>RBr> RI Reactivity orderis RI> RBr>RC1>RF For same halide group reactivity orderis 3° halide > 2° halide > I halide Fluorides and Chlorides are lighter than water where as bromides and iodides are heavier than H,0 due to more density of bromine than oxygen. CH,t, is heavicr liquid after Hg. CHEMICAL PROPERTIES Onxidation reaction @ —_Onlyprimary and secondary alky! halides undergo oxidation. Tertiary alkyl halide does not undergo eae @ __ Primary alkyl halides give aldchyde where as secondary alkyl halides give ketone in thisreaction. (ii) Oxidising agentiscither: (3) Dimethy! sulphoxideor (b) Reaction with (CH,),N, followed by hydrolysis. () Reactivity <-number of a-hydfogens. R-CH,-x —28224 R-C-H (Crt gg HOW? x ° | u mtn ieee nt 00H CAHCH,-X SAAN oH —C-H Note: (1) Oxidation of Benzy! halides by (CH,),N, is known as sommelet aldehyde synthesis. (2) Oxidation of alky! halide with DMSO is known as swern oxidation. Reduction : Haloalkanes on reduction produces alkanes frequently, reduction is done as follows. R-X +2H = —+ R-H+HX@ —_ ByNascent hydrogen liberated from Na/C,H,OH or Sn/ HCl or Zn/ HCl or Zn-Cu couple! C,H,OH ete. R-X+2H = —+ R-H+HX @ _Byhydrideion (:}1®) liberated from LiAIH , or NaBH, Itis completed by nucleophilic substitution reaction. R-X+:H® —, R-H+:x® (@—_Bycatalytic hydrogenation of haloalkane - R-xX+H, MMP, RH HX @) _Byreduction of RI with HI in presence of red P. R-X+Hl S298", R-H+], Reaction with KOH : (3) Withaqueous KOH : - R-X +KOH(aq) —+ R-OH+K-X ® With alcoholic KOH : - Dehydrohalogenation takes place and alkenes are formed. R-CH - CH,- X+KOH(ale.) —+ R-CH =CH; Reaction with KCN: R-X+KCN/—+ R-C®N+KX Alkane nitrile Alkane nitrile is an important compound which gives following products. @R-C=N et RG -O-H+NH, @® R-cen- o> Reg @ — R-Can oem, R_CH,-NH, Reaction with AgCN : R-X+AgCN —+ R-N=C+AgX R-N=C —"28*_, R-NH, + HCOOH 4 R-N=C hee RACH 2 amine Reaction with KNO, = -N=0 —> R-O-N=O alkyl nitriteR-X+Ag-O-N=-0 —> R-ngo nitro alkane Reaction wi R-X+K-SH——> R-SH alkane thiol Reaction with Na,S :— 2R-X + Na,S——> R-S-R dialkyl sulphide Reaction with Na,SO, : R-X+ Na,SO, ———> RSO,Na + NaX alkyl sodium sulphonate Reaction is know as “Strecker reaction”. Reaction with NaOR: R-X + NaOR——> R-O-R + NaX ‘The above reaction is called as “Williamson ether synthesis”. Reaction with Ag,O: (@)—_UsingdryAg,0: 2R-X+Ag,0 —+R-O-R+2AgX (b) — Usingmoist Ag,O: 2R-X +Ag,0+H,0 =, R=OH + 2AgX Reaction with Silver Acetate: R-X #/Ag20=C“CHy —°R-0-C-CH, 4 I ° ° ester The reaction is called as ‘Esterification’. Coupling Reactions (A) By Watrz Reaction : An alkane having even number of carbon atoms can be obtained by Wurtz @) Reaction. R-X +2Na+X-R —Ors_, R-R+2NaX ‘Alkane having odd number of carbon atoms can be obtained by mixed Wurtz Reaction. R-X+X-R' Hs RR+R-R'+R'R? CH-1+ H,-CH-1 PLES CH,-CHL$ CH-CH,-CH,+ CH,-CHL-CH,-CH, By Wurtz-Fitting Reaction R-I+2Na+-Ar —ve=_, R-Ar+ 2Nal CHy-1+2Na+-C,H, 22", CH,-C,H, + 2NalReaction with metals: (0) With Na: (Wurtz reaction) R-X+2Na+X-R —SveOr_,R_R+2NaX (&) _WithMg:~ (Grignard reaction) R-X+Mg —Sreihet_, R_Mg-x (©) With Zndust :~ (Frankland reaction) R-X+2Zn+X-R —+ R-Zn-R+ZnX, dialkyl zinc Dialkyl zinc is known as “Frankland - Reagent’. @ =~ WahLi:- R-ci+2Li OVS, RLI+ LIC alky! lithium Note: Alkyl lithium is more reactive than Grignard reagent. (©) With Na-leadalloy:— 4CHy-CH, + 4Na—Pb —+(CH,-CH, ),Pb + 4NaCl TEL (tetracthyl lead), Note : Tetra ethyl lead is used as antiknocking agent. Reaction with Benzene : 4 x oO +RX > (OC) +H-x ‘The reaction is calledas ‘Friedel-craft Reaction’ Important Note :~ Alkyl halide shows electrophilic substitution reaction in the above reaction, which is exception in alky! halide Uses of Alkyl Halides © Alkyl halides are used as weak refrigerants, but more suitable freons are now being used in place of alkyt halides. (Synthesis of detergents is carried out from alkyl halides by Streckcr’s reaction. (i) Synthesis of antiknock compounds. (iv) Alkyt halides, especially alkyl bromides and alkyl iodides are used for the synthesis of other organic compounds of almost all classes, in laboratory and in industry. () Alkyl halides are generally used as starting substances for the manufacture of alcohols, ethers and esters. (vil) Synthesis of important organometallic compounds, like Grignard’s reagents. Frankland’s reagents, etc., is carried out from alkyl halides.TYPES OF DIHALIDES Dihalides are of two types :— (3) Gem dihalide : These are the halides in which two identical halogen ators arc attached on same carbon, (b) Vicinal dihalide:: In these halides two identical halogen atoms are attached on adjacent carbon atoms. METHODS OF PREPARATION OF GEM DIHALIDES ()__ FromAlkyne (Byhydrohalogenation) :— x R-CmC-H+HX —+ RgagH ts Repos XH x (&) —_ Fromcarbonyl compounds :— R, C1 RCHO+PCl, x +POCK, 7 ch (terminal dihalide) Note : If ketone is taken internal dihalide is formed. METHODS OF PREPARATION OF VICINAL DIHALIDES (2) FromAlkene (By halogenation) R-CH=CH, +l, —> neg (b) From Vicinal glycol:— R-CHOH 5 PCls Riel +2HCI+ 2POCI, dH-on Pol, Cyl PHYSICAL PROPERTIES OF DIHALIDES (a) _Dihalides are colourless with pleasant smnell liquid, Insoluble in water, soluble in onganic solvent. (6) Melting point and boiling points are directly proportional to molecular mass but boiling point of vicinal dihalides arc more than gem dihalides. Also, reactivity of vicinal dinalideis more than gemdihalide, but these are less reactive than monohalide. CHEMICAL PROPERTIES OF DIHALIDES (a) Reaction with aqueous KOH : — R x R, OH SS R a7 Ny KOH) Xn ag aRox +kOH(aq.) I +10-+H,0 R R CH-LHOH + Noo! ——e CH,-6=0 + Nal + HO 2Hydrony 2° atoohot R R cr -be0 + stiao1 —» 4-4-0 + aNaoH Amettyl ketone ‘Triodo derivative R R 1-420 + Neo —» crt, + donaTETRAHALIDE ‘PYRENE’ General method of preparation : FromCs, :— C8, +3C1-Cl 28+ CCI,+S,Cl, sulphur monochloride 2S,Cl, + CS, ———+ CCI, + 684 ‘The reaction is used for industrial production of CC,. FromCH,: CH, +Cl,—> CH,Cl _&_, CHCl, —&_, CHCl; —& _, CCl, From CHC); : CHCI, +Ct-Cl_wenesmige_, CCI, +HCI Physical Properties : (@) _Itiscolourless liquid with specific smell. Itis insoluble in water and Soluble in organic solvent. (b) _Itisthe only organic solvent which is non-combustible. So used as firé-extinguisher called as. *Pyrene’. Chemical Properties: (@) _Itreacts with hot HO of With water vapour and forms poisonous gas ‘Phosgene’. CCI,+ H,O(g) =4_, COCI, + 2HCI. (b) _Itreacts with aqueous or alcoholic KOH and forms inorganic salt potassium carbonate. CCI, + 4KOH (aq.) a+ C(OH), —ayp > CO, —72-+ K,CO,+ 1,0 (unstable) (©) Itreacts with phenol and forms salicylic acid. ou oO +CCI, —2aXOu_, ‘The reaction is called as ‘Riemer-Tieman Carboxylation’. (4) Reaction with benzene. on coonFREONS ‘These are poly chlorofluoro derivative of alkane. Preparation of freons: CCl +HF 825, CChF+HCI C,Clg+2HF 8, C)F,Cly + 2HCI hexachlorocthane —_freons-112 Nomenclature of Freons = ‘The common name of freons is Freon - cba or freon C - 1, H +1, F, where ¢=no. of carbon atom 1, b=no. hydrogen atom + 1, a= total no. of atoms of fluorine cg. CFCI; C-1=0,H+1=1,F =1 Freon-11 Properties & uses of freons :— (@) _Freonsarecolourless, odouriess, unreactive & non-combustible liquids. (©) Having very low boiling points (c.g CF,Cl, =- 29.8°C). They easily converted from gaseous state to liquid state, therefore they are used as a coolant in A.C. & Refrigerator. (©) Usedasaacrosole propellant in aeroplane & rockets. (@)— Alsousedasasolvent. ‘Note : CFC is the main cause of Ozone layer decay (CFC - chlorofluoro carbon)GRIGNARD REAGENTS ‘Organomagnesium halides were discovered by French chemist Vietor Grignard in 1900. PREPARATION OF GRIGNARD REAGENTS GR_ are prepared by the reaction of organic halide (RX) with Mg in dry either solvent. RX+Mg —""="> RMgX ArX+Mg "2+ ArMgx The order of reactivity of halides with M RI>RBr>RCI GR forma complex with ether solvent and formation of this complex imparts stability to GR. RA 9 Rex * 9 R7 oR ‘The method (which can be used for I*, 2? and 3* alcohols) is little used in practice, since an alkyl halide canbe converted into the cotresponding alcohols. REACTIONS OF GRIGNARD REAGENTS 1. Reaction with carbonyl compounds : GR react with carbonyl compounds to give I°, 2° and 3°alcohols. (a) GR. react with formaldehyde (methanal, HCHO) to gives I° alcohol. ‘ Hy 4 " nag! b, His 1-§ 9 ax HO no +Me. R 1* Alcohol ou(©) GR. react with ketones to give 3° alcohols. Reaction with ester : ‘Twomoles of GR. reacts with esters to give 3° alcohols. One mole of GR. reacts with esters to form ketones. Ketones are more reactive towards GR. than esters. Therefore, as soon as amolecule of the ketone is formed in the mixture, itreacts with a second molecule of GR. After hydrolysis, the product is 3*alcohol, with two same alkyl groups that correspond to the alkyl portion of the GR. Nyro itt Penne fat] of eX nail pict ” bane a * ORES cn,-c-on (i) HO" Le aatcaghtel Reaction with dialkyl carbonate: Preparation of 3* alcohol containing three identical alkyl groups This maybe prepared by the reaction between 3 malofGR. with | molof dehy erbonae. necnore-o] For example SEMgBr + EOL-O gg Ethylmagnesium —Ethylmagnesium —ESt> - OH ‘bromide ‘bromide hovel Reaction with alkanoy! halide: ° I ‘Two moles of GR. reacts with acid halids \R -C- XJ to give 3° alcohols.° i] (One mole of GR. reacts with acid halids \R —C—X J to form ketones. Ketones are more reactive than acid halides. Therefore, as soon as a molecule of ketone is formed in the mixture, it reacts with a second molecule of GR. After hydrolysis, the product is 3° alcohol, with two same alkyl groups that correspond. tothealkyl portion of the GR. : ® Nog on ttt fae 4o™ ways [D2] ne xy h alt aga ue wlio R ¥*Akobol rere: cH, @t -0-c1+ "oe any 1c on Co mms a ‘carl chloride 3-Mathytpetan-3-o1 i] ‘Twomoles6f GR, reacts with formyl halides or methanoyl halides \H-C-X.) to give 2°alcohols, with ewo same alkyl groups that comesponds to the alkyl portion of the GR. Ya” rio ‘On sete [y fo] Aa, taal poe For example: ° cn nea + CCH Mewe aan con Medan ni . ch, Foamy chloride mm (2 alcobol) (Pemtan-3-ol)9 Reaction of dialkyl cadmium (R,C4) or dialkyl lithium cuprate with acid halides (R -C-X) gives I ketones and with formythalides \H-C-X) gives aldehydes. oO | (y2n-€-xerca THEA, apr cax, i Tura, I (yH-c-x+rca HEA coe Reaction with anhydride: Oo QO ‘Two moles of GR. reacts with acid anhydride Lokal to give 3*alcohol. Acid anhydrides react in the same way as ester, and acid halides react with RMgX. Reaction of RMgX (GR.) with oxirans (epoxides) and other cyelic ethers : RMgX reacts with oxiranes orcyclic ethers via SN? mechanism. The R® (nucleophile) of RMgX attacks the pantally changed C atom of oxirane ring. Since itis highly strained, the ring opens and forms asaltof I°Calcohol, which gives alcohol on acidification.2-Methyt ‘oxetane Reaction with O,: GR_ react with O, to give I* alcohol TReMx + 0-0» R-0-0-Mgx MEX, 2-0 HO’, 2Ron + Mg ZX ‘ou For example: HW Non Reaction With ackds: RMgX gives alkane (R-H) on reaction with acids R-MgX + H-X—>R-H+Mgx, 2CHMgbr +0, TEs sc Hort Me LO: “Ethanol R-MgX + HO R-H+ Mg mecy Reaction with R-CN : RMgX gives ketone on reaction with R-CN R R 1 . I we-cfye Ralex Connex Ho 6 e-c-0 Ketone on further reaction with RMgX gives 3° alcohol. ® © ® Ns Ben fo Ss font on P&S OPT St N ‘Re Mex ®