Amines Name Reactions PDF

 NAME REACTIONS OF THIS CHAPTER 4) Diazotisation Reaction : Nice -...

 NAME REACTIONS OF THIS CHAPTER 4) Diazotisation Reaction : Nice - " ☒ %¥ ② Hoffman Bromide Reaction : for both aliphatic and aromatics I.ami ° → es R - G - N Hz -11382 + 4 KOH - R N Hz - -12k Bo + Kzc 03+21420 0 (one C less in product) ③ Gabriel Pthalamiode Synthesis :( I formed) → Only for Aliphatic jn%-→ 0 → in # 0 Phthalamide 17%-0 Na N-alkylphthadami.de/,Na0H(Hz0) ¥g- ONA + R N H2 - (I amine ) Reaction : 14 ] Coupling - Hee 5°C -N=N-- 0° - > OH ☒ OH / NaOH → hydroxy azobenzene Grange ) - P- -N=N - ce - 8- 5°C - HCl , -N=N--NH2 Ntk / HCl P - amino azobenzene ( yellow) ⑤ Carbylamine Reaction / Isocyanide test : R/ Ar - N Hz 1- CHI } -13 KOH - R Ar / NC +3kcal -1-31120 - Hint smell ) ↳ to differentiate b/w 1° amine 243? use from  PREPARATIONS 4) Reduction of Nitro compounds : N°2 " "2 I, H Ethanol " "2 N°2 % SIE 00 Fe + HCl , F- Reduction with iron scrap and Hee Ps preferred because Fella formed gets hydrolysedsmall to release Hee. to initiate reaction - only amount of tell is required. SB ② Am Monty of Alkyl halidesC- : The process of cdevage of ✗ bond by ammonia molecule Ps Ammo no lysis s Ry Ni - R N Hz - R2 NH sR3H ammonium salt Quaternary R - NH%X⊖ -1 NaOH - R N Hz - + H2O + Not G mixture of 5,273° and 4° salt Disadvantage : It yields. tips major product by taking large excess of ammonia. Order of Reactivity R-2 > R Br > Red - of halides with Amine ③ Reduction of Nitrites : → I amine produced → This reaction is used for ascent of amine series i. e- preparation of amines containing one carbon atom more than starting amine. R CEN - É R- CHz - N Hz Nat H g) / Ca Hs OH 08 LPALHY 141 Reduction of Amides : R - É - N H2 Ñ H2O R- CH 2- NH 2 (5) Gabriel Phthalamide Synthesisdo: Aromatic I amines cannot be prepared by this method because aryl halides not undergo nucleophile substance with anion formed by phthalamide. ⑥ Hoffman Bromide degradation Reaction : lone carbon less in product)  CHEMICAL REACTIONS ☆ Amines behave as nucleophile. 4) Basic character of Amines : with salt They are basic in nature , react Acid → R N Hz - + HX R - Nz salt F- H2 Nj%cI ¥ ☒ + HCl Ammonium chloride → Amine salts are soluble Pn H2O and not Pnoog. Sol Like ether.. salt + base - parent amine RNH%✗⊖ +0% - R - NII + H2O + → This reaction is basis for separation of amines from non - basic 00g. Compounds insoluble in water. plkb) of.pl/2b)---logkbf&Kbordpkb - ammonia = 4- 75 strong → base Aliphatic amines strong base due to +I → are ↳ pkb btw 3-4.22. pkb Of aniline is high aromatic amine pkb < ammonia. → Structure - basicity related to Amines : basicity depends on of form of cation " ease by accepting a proton from the acid. More stable cation, more basic amine → Acylation H Ghs - I N + ( Hz É- - Cd É Cz Hs - 00 1N - C - C Hz -1 H - Cd , ↳ Hs Cztls Colts § CH } O CH } CH> COOH § H CH} + Cots § N + - - - - - - - - - is Benzanamine Ethan 0Pa anhydride Acetanilide  [ HzNHz + ( 614510cal - CH3NHCO( Hs + Hcl chloride Benzoyl reaction carbylamine Reaction with nitrous acid } at last in easy way Reaction with aoyesulphonyechbn.de Ms " 'd ce % - Hinsberg 's reagent : ☒ ≈ (2) Electrophilic substitution : (a) Boom Pnation '" "° + 313oz É + 3 HBO É ¥80 NHZ H d- CH, 4112 H CH} %÷i¥ ¥1 4- 4- - - - ¥¥:s Acetanilide Bo Bo ( major) (b) Nitration : acidic medium aniline is protonated tofoomaniliumion which In strongly , is meta directing. N 2 ,H2 "" ☒ HÉ + + µ, V02 147%1 12%7 151%1 → By acetylation reaction with acetic anhydride reaction can be controlled and P can obtain major product ¥÷:÷÷÷iÉÉ NHCOCH} 4ᵗʰ Nfl COCH } Nba to Sul phonation : , (C) MHz ni-j-HS.iq Nite 4%3 EH = ☒É Anioliniom state ski hydrogen sulphate svlphanalic acid zwilterion  Diazonium Salts i \ I \ \ \ \ PREPARATIONS : diazonium The conversion primary of aromatic amines into salts is → known as diazotisation Nice '. H2 ✗ + Na NO , + 2 HCl ¥-283K [ + Nacd + 21420 PHYSICAL PROPERTIES : Benzene diazonium chloride colourless solid - crystalline It is readily soluble →. stable Pn cold but reacts with water when warmed →. in decomposes state easily dry →. Benzene diazonium Floro borate Ps water insoluble and stable at. room temp. CHEMICAL REACTIONS : Reactions involving displacement of Nitrogen - t. Replacement by halide or cyanide Pon. Sand 's t reactions aka Mayer → É Arcd Na + , Ao NII - ÉÉ Ar Bo + Nz Ar CN + N2 → OR , Br or Cl can be introduced by halogen acid in presence of Cu powder, this is called Ga Herman reaction. And + Net ax Nix - Ar %7r Bo + Nz + Cut sand Mayer is better than Ga Herman 2. Replacement by iodide Pon : Iodine not introduced Pn benzene ring directly , but when easily diazonium salt solution is treated with potassium Iodide Todobenzene , is formed. Ar Nic d- + KI - Ar I t-KC.lt Nz  3. Replacement by fluoride Pon : Ar NÉCÑ + HBFY - Ar - NBF → Ar F - + BF> + Nz 4. Replacement by H As NÉ( d- + Hzpoz + H2O → Art + Nz -1 113 Post HCl ↓ ↓ hypo phosphorous acid/ Phosphorus acid acid Phosphine AoÑz(d- t-ctlzCHZOH-AJH-Nz-ctb.CH 0 + HCl 5- Replacement by Hydroxyl group : Temp ↑ then 283k Phenol form get -. Arnold + H2O - Aron + Nz + HCl 6. Replacement by Noa group : NO 2 42 Bfy ☒ + HBFY - 1¥02 + Nz + Na Bfy diazo B. Reactions involving retention of gop. coupling reaction → IMPORTANCE : Diazonium salts are good intermediate for intro of F. Cd , Br , I , NO ≥ CN , OH , gop. Help in forming compound which cannot substitute directly.  3 TESTS : 1) Carbylamine Reaction / Isocyanide Test Cdifferentiate from other) to → Aliphatic / Asom i amine on heating with chloroform and ethanol potassium hydroxide forms isocyanide or carbylamine , foul in smell. → distinguish famine from 2° and 3° R / Ar - N Hz -1 CH clog + 3 KOH - R Ar/ - NC + 3kV -1 3h20 ☒ v1 smell ) 2) Reaction with Nitrous acid ( test 2) (diff. btw aliphatic & aromatic from Ponty ) B P aliphatic amine R N Hz - + ( Na NO, + HCl) - R OH- + Nz t NaCl 08 I HNOZ Produced %) 1° aromatic amine Ar N Hst- HNOZ 05¥ Ar - Ñzcé 273 -278k diazonium chloride Hinsberg Reagent ( HR) → 3) Reaction with Arylsvlphonyl chloride test (separates 172%39 alkali IT soluble -§-NH Ph I R § Y R - - - - - O ④acids 's e * r p 2° R NI Ph not soluble § H.. + H - - R - - - N - R ( because H absent) ↑ 3° H.R. + R - N - R - no reaction H - absent