Haloalkanes and Haloarenes Reactions PDF
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Rajkiya Pratibha Vikas Vidyalaya, Harinagar
Shobhit Nirwan
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Summary
This document outlines various reactions of haloalkanes and haloarenes, including Finkelstein, Swartz, Sandmeyer, and Wurtz reactions. It also covers Friedel-Crafts alkylation and acylation, as well as Saytzeff's rule for B-elimination.
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NAME REACTIONS OF THIS CHAPTER 4) FinkelsteinReactio (Alkyl halide preparation) R X -...
NAME REACTIONS OF THIS CHAPTER 4) FinkelsteinReactio (Alkyl halide preparation) R X - + Na - I - R - I + Nax [✗ = Cl , Bo ] (this reaction can favoured in forward be direction by precipitating Nax with dry acetone. Acc. to Le chattier 's Principle] (2) Swartz Reaction : R - ✗ + Metallic florid e - R F - + Agx ( ✗ Cl = , Br ) ( AgfSbfz Hgzfz , , Cofz , ) Finkelstein and Swartz Rxh Halogen exchange ox " (3) SandMayer 's Reaction : Cl , Brand CN → can be easily introduced in the benzene. ring of benzene diazonium salt in [v11) ion presence of. Nice ÉÉ + Na " ÉÉ + Ne Benzene diazonium chloride + N2 CUCNIKCN :-) *÷: ↑ K3B= : Diazotization Reaction :( How this Benzene diazonium chloride Ps formed ) Diazonium Gotts Need) is prepared by treating ice cold solution of Aniline in excess dilute HCl with ag Solh. of NaN02 at low temperature. 4h2 HNOZ / HCl or Nice ts (0-52) Aniline Benzene dizonium chloride 141 Wurtz Reaction : R - X + 2N a + X - R ¥É R - R + ZNAX Ñ ey:-(Hz ( Hz Br + 2 Nat Bo [ Hz Ctb ( Hz cuz Ctlz CH } -12 Na Bo - - - - - - - : 2C Hz Na ᵈ% (H } Ig ✗ Ctb 2 Na ✗ - - + 2 - + (5) FPHPG 's Reaction : 2 g + zµa→% + 2Na✗ (6) wuotz - fitting 's Reaction : + 2Na+R-✗ &¥ + 2Na✗ ie egfo CH } - Cd +2 Nat &¥ + 2. Nacl (7) Reaction with metal ( Grignard reagent ) : R R ✗ + My - - mg ✗ - - 1 Grignard reagent) rÉmjÉr i + my µ (8) Friedel-Crafts Reactions : % Cd R ↑ ++AñA→ + [Friedel rafts ,, Alkylation] É products ( major) ' (minor lit -1+r-etA r + ☒ ie lfñedel crafts Acylation] Auto Phenom (mpno , , - r ( major) (9) Saytzaff Rule :( zaitsev rule / B- elimination / dehydro halogenation) Rule : More alkyl group containing alkene is major product. - CHE CH CH 2- ( Hz - Ctb cl - B 9 B CH3-CY-CHz-C.tk : ( Hz G- 1- - KOH.. - - - ( Hz - CH = CH - C Hz - CH}. Br lmajorproduc.tl:2 - alkyl group Note : Now we'll use these Name reactions further in these notes by mentioning only name of the reaction. PREPARATIONS HALO ALKANES ? \ \ \ \ \ \ (1) from Alcohols Luca's test ( Luca's Anny Znllz) reagent cone Hilt → =.. R - OH + Hcd R - Ll + H2O released Darren 's test ( best process as 502 and HCl is as gas) → R OH - + socdz → R Cd - +502-1 till Tnionyichloride → R OH - + Nabs + Hzsoy → R Bo - + Natlsoy 1- H2O → 3R OH- + PX } - 3 R - X 1- H3P0 } / Boric acid] → R - OH É R - ✗ ✗2=882,12 → R - OH + Pcls - R Cl- + Poclzt HCl (2) from Hydrocarbons : → From Alkanes : % RH + ✗2 R - ✗ + HX ( d- CH z [ H2 %) CHICHI Cha ( Hz CH z C Hz CH} 1- ( Hz CH Cl Ctb - - - - - - - - two type of H , so 2 product will be there with Cl on diff position.. → from Alkenes : f) Add Of " Hydrogen Halide :(only Brill , 1) > c=c( + tix _ > c- CC ' H × ( Hz ( H=CHz elf ! + HCl CH } CH ( H2 - - - - - de it E) Add of Halogens " : " H / → - c=c + Boz Boz - CH, - CHZ - Bo / \ H H add " of Bo Pnccdy to alkene give reddish boom fumes help in detach of =/ bonds -. 131 from Halogen Exchange : By Finkelstein and Swartz reaction (mentioned earliest HALOARENES ' \ \ \ \ \ I (1) from hydrocarbons by electrophilic substitution : "" Feo ✗ ☒ * ×, dark + - halo toluene £ (2) From amines p halo toluene by sand Meyer 's Reaction : - NÉX _ NHZ ☒ -H✗ 273 -278k Benzene diazonium halide ( ✗ =ce,Br) Ni" × + Nz Halide Aryl Iii If Iodine , then no cuoeguired : [ Nik - [ # + Nz CHEMICAL REACTIONS HALO ALKANES ? \ \ \ \ " substitution Nucleophilic → Ni - nu - + =,ÉÉ - ¥ - nu + ✗ - → other gins in table 10-4 but main I , É RCN (Nitriles R ✗ /A RCN ( Pso nitrite) -1¥ - R ONO - / Alkyl nitrite) 1¥02 R - N0z(Nitro alkene ) SN ' reaction mechanism : attack fromsides R → Rig # both % , RI , s f- R2 + / Rs Rz sp2 R ! NU R, R / NV (carbocation) ( Racemic mixture) 352° > I → SNZ reaction mechanism : ↑ ↑ ↑ c- ✗ ÷É / no c- × ) ni - - - - - - - HI µ / µ / i > 2° > 3° Walden inversion Transition state (2) Elimination Reaction: ↑ ¥C( I c- B H × g- - - + - + ' B B- / × B- Base , ✗ = leaving group in e-f-IHzc-CHz-ctl-CH-CH3-tlzc-C.tk - Ctb - CH - CH , Hzc- Ctb - Cha - CHE CH ( 81% ) ↓ ( 19%1 (3) Reaction with metals : → Grignard Reagent / both mentioned ] → Wurtz Reaction earlier HALO ARE NES ' \ \ \ \ \ I (d) Nucleophilic substitution : → Chlorobenzene - Phenol ( Dow's Process) 4 % ¥;¥"Em [ This process alternatively add at ten temp very costly Ps , so we IN Oz) so it is affordable. ↓ and Cl And , if we add more No, gaps → temp am easily occurs. ie. Éy ÉT N°2 402 add more Noz : ÉN°2Na÷¥ N°2 Hoz ↓ 02 ↑ NO2 add more N°2 , N°2 No ¥-0m ; N°2 ↓oz Hoa Electrophilic Substitution Ran : major) ' 12 ] ' Call Para products → Halogenation : → ÉÉ + ce. ¥¥s ÉI. ÉI ' " te Nitration : 4¥ → ce el ¥ÉÉI "" + N°2 Sul phonation : sH ÉI - ie ! + friedel ( mentioned earlier) £03M → crafts Rxn ③ Reaction with metals : → Wurtz fiHPg / mentioned earlier) - Fitting PROPERTIES PHYSICAL % They are colourless %) Polar but insoluble in creates %) Soluble in org. solvents F) Polarity ] R - f > R - Cd > R Br - > R - I Molecular wt ✓] Boiling point ✗ - 2. R f < R ce CR Br CR - - - - I vis melting Point ( seen by symmetry) II. < < ¥ [ de