This lecture provides a rigorous and systematic breakdown of amine reactivity, essential for mastering the nuances of organic synthesis. It effectively distills complex chemical transformations into a clear, pedagogical framework for the serious student.
Deep Dive
Prerequisite Knowledge
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Deep Dive
Amines part 7Added:
now coming to the chemical properties of amines now amines as it is basic in nature definitely it will react with acid to form salt all right as mines are basic in nature for example c2h5 nh2 when it reacts with hcl it gives you c2h5 and h3 plus and cl minus you can say that similarly this further will react with hcl further we'll react with the minds not hcl c2h5 nh3 plus cl minus plus c2h5 and h2 let us see what we will have you will have c2h5 hold twice you can see two molecules substitute h5 then c2h5 volt wise nh okay here it is nh2 of course nh fine and it will be hcl nh plus cl minus because nitrogen one bond with c two h five a two bonds with c two h five one bond with h plus and you will be getting nothing but that is c l minus so to say so in this way ah that is you will be getting that is uh c2h5 volt twice that is nh uh you will be getting here nh2 here also in h2 so c2h5 volt device let me also write it in this way that will do situation volt device nh2 hold twice c2h5 volt twice so instead of writing c2h5 volt wise i can write it h 2 hold twice plus here 4 hydrogen here this what you can say 5 hydrogen here c 2 h 5 here 2 c 2 h 5 done so here you can see 4 hydrogen here h plus and cl minus now it is ok you can get it in this particular way fine so in this way uh it will further react with c2h5 and h2 h22 form that is nothing but another salt we can say that that is nothing but c 2 h 5 whole ah and c 2 h 5 n whole thrice we can say h plus and c l minus you'll be getting it in this way similarly aniline also reacts with hcl anil also reacts with hcl we can say plus reacts with hcl to form anilinium chloride nh3 plus cl minus anilinium this is your anilinium what i said any lineam chloride let me write the eye properly anilinium chloride we can see that all right it is ethyl ammonium chloride we can say this one is it is diethyl ammonium chloride we can say that clear in this way you will be great now it also reacts with metal ions for example c2h5 and h2 plus a g cl let us see a metal chloride i have taken it a g is here so what will happen is that here here you will be getting c 2 h 5 n 1 a g it will give nitrogen will give a pair of electron to a g then c 2 h 5 and it will be another c 2 h 5 let me write here n that is better when then here it is c 2 h 5 okay so here it is we will see now we'll balance it c2h5 and h2 so two molecules are required so two molecules are said to h5 and h2 now here nh2 of course will be coming c2h5 nh2 here also same thing nh2 c2h5 then plus and outside the bracket i am writing it below that is cl minus it is actually it should be at the side let me write it aside only otherwise you people will get confused plus and cl minus now its okay so in this way you got this particular what you can say salt you will be getting it that is nothing but it is this two two times it is there this bis that is uh ethylamine then silver one chloride we can say that it's a soluble salt it's a bis ethyl amine silver one chloride i should say that clear so in this way you will be getting with the metals also it reacts at this with metal metal chlorides or metal sulphate like copper sulfate it will react to form what you can say tetra methyl ammonium what you can say copper sulphate we can say it is going to form clear so in this way with copper sulphate it will react like ch3 and h2 four molecules four molecules of ch3 and h2 plus coso4 it will be nothing but cu uh nh3 that is cu ch3 and h2 hold uh whole four it will be tetra all right so this nothing but again i repeat cu ch 3 nh2 hold 4 whole 2 plus then so4 2 minus that is what i want to say you in this way see that is cu it that is ch3 and h2 whole 4 2 plus and s of 4 2 minus for that reason what i need to do cuso4 and four molecules of ch3 and h2 four molecules of methyl amine reacts with copper sulfate to give you tetramethyl ammonium copper sulphate we can say that clear you will be getting it or tetracus we can say tetracyclist like it is this here it is tetracus all right then methyl amine ammonium copper to sulphate all right tetra kiss then within bracket it should be methylamine copper two sulfate we can say that clear in this way this also is a soluble salt which is blue in color this is a soluble salt we can say that which is colorless and this is soluble salt which is blue in color so to say so in this way it also reacts with lights all right it also reacts with halides and when it reacts with halides what it forms is that it forms again ah that is exhaustive ah halogenation takes place and it forms a salt we can say that clear so it forms it reacts with halite so to say fine so hence what you find is that it will react with halide so it reacts with allies highlights means for example here it is r and h2 let us say plus rx we can say that clear so what will be getting it is nothing but r n r h this is your 1 degree amide it reacts you form 2 degree amides this h and this h x to form h x we can say that okay i have removed it this this hydrogen actually have removed so i i have showed it here this particular hydrogen don't get confused and again it reacts with rx it will be forming r and r okay and here it is hx we can say that clear again it is going to form again it is going to react with rx to form r4 n plus x minus so in this way exhaustive alkylation takes place like here if you take methyl chlorides exhaustive methylation we can say if you take ethyl chloride you can say exhaustive the thyroid addition we can say that clear so in this way whatever the halides you are taking it whether it is methylchloride or ethyl chloride whatever the highlights you are taking it accordingly respective compounds you'll be getting it accordingly i hope you understood this particular one so this is primary minds it will give you secondary minds and tertiary minds and quarter mirror minds we can say that we'll be getting it now next is this also can be done with the what you can say angelic also it can be done it also can be done with aniline you can say that how see it benzene ring and h2 same thing in place of r will be using that is nothing but ah here that is benzene ring in place of r i have used benzene all right plus rx so to say so what will happen one h will be replaced by r so it is n h and r suppose if r is c is three let me put here something like suppose if i take here ch3cl so what will i get here i will be getting here ch3 and here i will be getting h here finished here hcl will be getting it again it reacts with ch3 cl to form what you will be getting that is nothing but n ch3 pole twice and again here it is minus hcl you will be getting it okay again it will react with ch3cl this will again react with ch3 cl we can say that and what you will be getting it here let me make it shorter this one it will be ch3 whole thrice ch3 volt rise n plus cl minus what i said again it will react with ch3cl this one so you will be getting ch3 whole ah thrice and plus and cl minus you will be getting it finished so this is the different types of anilinium compound you're getting it what i said any linear for example this one is n methyl aniline it is n n dimethyl aniline you can say that clear you will be ah dimethyl aniline then it further reacts to form that is trimethyl got it try with thy anilinium hydrogen chloride trimethyl and elenium white is linear because positive charge is there trying with high anilinium hydrogen chloride so to say okay so in this way we are getting it also you can also say trimethyl ah anilinium chloride i can say that also can be written to be s now next is will come to half man's elimination reaction half mass elimination reaction so to say we will come to so what i said half mass elimination reaction in this particular reaction what we generally do is that for example ch3 ch2 ch2 and here let us say c2h5 here that is your ch3 let us say we'll be having it and here we will be taking another let us say ch3 all right and plus i minus that is we are taking a quaternary salt we have taken a four degree amine i have taken a quaternary amine i have taken it a quaternary salt when it reacts with moist ag2o ag ag2o moist when it reacts with actually moist ag2o means what i've said you earlier also it is nothing but more agoh moist ad2 means ageos then you must be saying why we don't write agues because a g h actually does not exist it exists as much as a moist agent to only because a g o h does not exist so to say so then what will i get it just this uh i minus will be replaced by o h minus so to say this i minus that is ch2 ch2 here it is n here it is ch3 it is ch3 it is ch3 plus oh h minus and here you will be getting it as a gi as a secondary product as a secondary product you'll be getting to be as agi okay now why it is called as hoffmann's elimination reaction because now you see it is substitution no elimination is taking place now you will see the elimination what we'll do is that i'll be heating it to a temperature of around 400 kelvin i'll be heating it all right i'll be heating it to a temperature of around 400 kelvin now when i'll be heating to a temperature of around 400 kelvin what is going to happen here that is the cleavage is going to take place here the cleavage is going to take place here when the cleavage takes place here what you will be getting you will be getting an alkene yeah you will be getting an alkene and here you will be getting tertiary amine we can say that plus water will be released how water because alkene when it is being found means double bond it comes here so from your hydrogen h plus sine this h plus sign reacts without sign to form water again repeat here when i'll be heating at 400 kelvin what happens this cleavage takes place why the cleavage takes place here because this is a bigger alkyl group for that reason i've written it it's a bigger alkyne group so wherever the bigger alkyl group is there definitely the bond will be a weaker bond definitely so hence the cleavage takes place here hence what you will be getting as i said here ch3 ch double bond ch2 so when it forms an alkene h plus ion is released from here h plus ion is released you can see there ch3ch double bond ch2 so here on h plus sine reacts with h minus sign to form what whatever for that reason it's called elimination because a smaller molecule is eliminated all right whenever some smaller molecule like what uh hcl ammonia so2 no2 co2 but these are eliminated they are called as elimination reaction and in case of elimination reaction from single bond it gets converted to double bond from unsaturated it becomes unsaturated see from saturated it gets unsaturated and what more you will be having you will be having ch3 whole thrice and we can say that clear trimethylamine you will be getting it so hence it is called as half max elimination reaction it is said to be s all right now we will see the reaction with ah that is acid chloride clear so this is your half mass elimination reaction you can repeat half max h o f f m a n n apostrophe s half mass elimination reaction next that is nothing but c h three c o c cocl acid chloride reacts with ch3 and h2 all right ch3 cocl reacts with ch3 and h2 what is going to form so here xcl will be released from here 1 h and here 1cl h2 will be released and what is the remaining product remaining product will be ch3 co then nh ch3 nh ch3 plus hc ch3coo and then cs3 said you know from here one hydrogen and here one cl so hcl will be released the cs3 co and then cs3 it is nothing but what is the name n methyl n methyl we can say that clear so you can do this reactionary thylamine also you can do this reaction with the secondary amine also you can do this reaction with tertiary amine also the reaction can be done all right so now with primary amine i have done it uh with methyl and i have done it as i said you can do with ethylmine the same reaction instead of here it is ch3 that is nh2 you will be getting here nhc2 h5 here you can take uh that is secondary amines like uh c2h5 hold twice nh you can take you can also take c2h5 work wise n so this part is going to change you can say that this part is going to change because this part is constant because i have taken phase 3 cocl this part is constant so this part will be the same this part will be the same only this part is going to change when you are taking ethylene then secondary amine touch to your mind this part is going to be changed that's all we can say now this reaction also can be done with the that is nothing but muscle means what it is it is nothing but c6 h5 nh2 that is handling so here also same thing here and whatever you get c6 h5 that's it clear you will be getting c6h5 so it is nothing but known as an acetone light this is known as acetabuli that is n-phenyl it is n-methanol previously same thing it is just this part is changing so it will be dharma might no doubt about it but it is anime thai and phenyl and what you can say ethyl or n-methyl whatever it is this part is changing so it is n-phenyl ethanomide and the common name is acetylide we can say that aceta knee glide acetaminophen we can say that clear in this way here it is ch3 ch3 coca this is acetyl chloride this of course you know that it is acetyl fluoride methanol chloride we can say that clear now ah here also we can change the group we can change it and we will see it let me rub it first so here what will i do instead of acetyl chloride i will take benzoyl chloride i will be taking it what is going to happen benzoyl chloride if c6h5 cocl plus c2h5 and h2 what is going to happen same thing is c6h5co there it was ch3co here it will be c6h5co where to write here i am writing c 6 h 5 c o this will be fixed then it will be nothing but n h and h c 2 h 5 all right plus h c hcl that's it all right so the compound is nothing but n ethyl benzene amide or benzamide n it is here they mean n ethyl benzene because this is your benzoyle chloride this is benzoyl fluoride and this is your ethanol mine it is n ethyl benzamide or benzene we can say that now this reaction is quite slow got it because i said you that arrive basically compounds are quite slow got it it does not undergo nucleophilic substitution reactions readily for that particular purpose i have to take a catalyst here which is nothing but a basic catalyst that is pyridine because this is acidic in nature so hence i will be using a basic catalyst that is pyridine so in presence of pyridine ah you can see the reaction can be carried out we can say that clear so here also what we can do is that i can take here h5 i can take it here so what will i get i will get c6h5 here also so what is the name it will be n phenyl benzamide n phenyl benza amide or we can say benzanilide we can also say benzar nili we can say that either we can say n-phenyl benzamide or we can say benzalide we can say that clear so this is otherwise also called as benzoylation we are doing the reaction with benzoyl chloride so it is also known as benzoylation now here you need to remember that that if i do the reaction with any h instead of pyridine that was an image if i take then this reaction said to be as shortened bowman reaction shorten s-c-h-o-t-d-e-n shorten bound reaction b-a-u-m-a-n-n shorten bowman reaction when it will be listen carefully instead of pyridine if i take aqueous naoh aqueous caustic soda across nmh if i take then it will be called as nothing but shorten bowman reaction s-c-h-o-t-t-e-n shorten bowman reaction okay it is known as now next space is there so what will i do the next is i'll be taking here that is r and h2 plus any uh that is nothing but aldehyde i can take or any ketone i can take it all right r and h two plus aldehydes so aldehyde is nothing but r cho or we can say r dash cho i can take same alkyl group or different alkyl groups why did you write in this way you can see very clearly water is released all right water is released now this reaction is done in presence of a medium which medium acidic medium this reaction is being done in presence of acidic medium now remaining product will write it down r n double bond c here is h and here it is r plus water it is released we cancel that now this is what it is a skips base or anil skips base or animal we can see that not animal animal we can say skips base are anil now we can also do the reaction with ketone we can do the reaction ketones let us say i'll be using another r here this is your ketone okay so hence you'll be getting here it is on so it's also known as skip's base r whether it reacts with aldehyde or ketone it is the skip's base or angle it is honest common name general name because it's not common in general name you can say that the the if you do with idea and ketones and the name is going to vary of course it is going to vary the name is going to vary but otherwise it is known as skip's base or annie we can say that clear so next is uh we can also do this reaction suppose the uh skips based on animal which you will be getting it like let us say i am doing this reaction with uh what will i do that is c2h5 and h2 plus i'm taking it here plus that is ch3cho let us see i am taking it here ch3cha all right i have taken acetaldehyde this one and this is your ethylene i have taken it now what will happen water will be released in presence of h plus water is released so what i got i got c 2 h 5 n then double bond c h then it is here ch3 and water is released we can say that clear now you see what is going to happen now this particular compound if i react with ah random nickel if it doesn't of hydrogen means if i go for reduction this particular compound if i go for reduction for the reduction reduction means what i said you are here you will be using a catalyst that is nickel in presence of hydrogen which nickel i said ran a nickel we can say that a particular kind of catalyst we can say that nickel which contains copper as a another ah substance present in it that is called as rainy nickel so to say clear it is a better catalyst compared to that of nickel we can say that is called randomical so hence what is going to happen here what is going to happen so what what i am going to see it here that is double bond will be broken down it will form a single bond that's it double bond will be broken down it is going to form a single bond clear and hence what i am going to get the product is nothing but c f c 2 h 5 and h and h here it is single bond h then here it will be ch2 already one h is there another ch2 ch3 another h will be added ch2 ch3 and here it will be another hydrogen is added one hydrogen added here one and hydrogen is added here all right so double bond is removed so here you can see the product so you get what you get diameter i sorry diethy am i a secondary amines you're getting it a secondary amine you are getting it we answer that clear in this way now next is we will see the reaction with nitrous acid in the next day we will see that thank you
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