CHEMISTRY, SECTION - IT CHAPTER : 13 COMPOUNDS CONTAINING NITROGEN Max. Marks : 4 NEET - 2/3 Que. Marks with opt m6 NITRO COMPOUNDS =- nitoalkanes are considered as the derivatives of alkanes in which one or more hydrogen atoms are replaced by nitro group ( i.e. -NO, group )* Classification of Nitroalkanes : 1. Primary nitroalkanes ( R - CH, - NO, ) : “The nitroalkanes in which NO, group is directly attached to the primary C-atom are called as primary nitroalkanes.” e.g. CH.NO, Nitromethane CHC, NO, Nitroethane 2, Secondary nitroalkanes ( R,CH - NO, ) : “The nitroalkanes in which NO, group is, directly attached to the secondary C-atom are called as secondary nitroalkanes.” e.g. (CH,),CHNO, 2-Nitropropane 3. Tertiary nitroalkanes ( R,C - NO, ) :"The ritroalkanes in which NO, group is directly attached to the tertiary C-atom are called as tertiary nitroalkanes.” eg. (CH,),C-NO, _2-methyl - 2-nitropropane General methods of preparation : 1. By nitration of alkanes : Industrally, nitroalkanes are prepared by direct nitration in two ways ‘a. Vapour phase nitration : The nitration of alkanes is carried out in vapour phase, by heating @ mixture of an alkane and concentrated nitric acid at about 423 to 698K. Methane does not undergo nitration 423K to 698 K R-NO, +0 Nitroalkane m1 yo, 423K to 698 K HO} no, “23K $78 6 cc, -No, + H,0 Nitroethane In case of higher alkanes, a mixture of different nitroalkanes is obtained which involves substitution as well as C - C bond fissions. [> CH, - NO,+ CH, CH, - NO, HO - NO, CH, CH, CH, —————+—_1_» ci, - CH, - CH, - NO, 423K to 698K Propane Pe, ie cH, No, b. Liquid phase nitration : The hydrocarbon is heated with concentrated nitric acid under pressure at 413K. Nitration under these conditions Is always slow and a large number of Polynirto compounds is produced. 2. From alkyl halides : Nitroalkanes are obtained in laboratory by the action of silver nitrite (on primary or secondary alkyl halides. Alkyl iodides and bromides are most satisfactory, alkyl chlorides react too slowly. Reactivity : RI > RBr > RCI R £8r+ AgNO, — R-NO, + Agr Nitroalkanes are also obtained by action of sodium or potassium nitrite on alkyl halides in good yield in presence of solvent dimethyl sulphoxide or N, N - dimethylformamide. vee pe DMSO, Rf Br +NajNo, So k-No, + NaBr 3. From salts of a -halogeno carboxylic acids : Lower nirtoalkanes are obtained by boiling aqueous sodium nitrite with sodium salt of at - halogeno carboxylic acids. ° ° i I io cH, ona + nano, MC | on -cr,-€- ona | M2 cu,-no, + NaHCO, 4. From primary amines : Tertiary Nitroalkanes are prepared by the oxidation of amines with potassium permanganate. BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (1) Scanned with CamScannerR R I KMn0, | Re G- NH + 310] — R= ENO, + #0 R R 5. From a- nitroalkenes : Nitroalkanes are prepared by the hydrolyzing a nitroalkenes in acidic medium. cH cH, re : - .. =... 2 = Methyl - 1 - nitropropene Nitromethane Acetone 6. From oximes : Primary and secondary nitroalkanes are obtained in good yields by oxidizing aldoximes and ketoximes with help of trifluoroperoxyacetic acid. H HO ° \ fivocetoeeee | R-€=N- OH + (0] Aldoxime 1Phitroakane R RO | tsfluoroperonycete acid let R-C=N-OH + [0] Mmuoroperonyeetic BOC R-C=Nt-OH = * R-CH-Nt=O Ketoxime 2 Nitroalkane @ Reactions of nitroatkanes : 1. Reduction :Ntroalcanes are reduced to corresponding primary amines by the action of tin/iron and concentrated hydrochloric acid. This reduction may also be effected by lithium aluminium hydride or catalytic hydrogenation, R-No,+6fH) Scone. HCl ky, + 2H,0 When the reduction is carried out in neutral medium with a metal, nitroalkanes are converted into N-alkylhydroxylamine Zn/NH,Cl R-No,+4th) UTE a NH-on + = 4,0 N-alkylhydroxylamine. 2. Hydrolysis : Primary nitroalkanes on boiling with hydrochloric acid or sulphuric acid undergo hydrolysis to form carboxylic acid and hydroxylamine. ° recH,-no,+Ho Hen + Non Secondary nitroalkanes on boiling with hydrochloric acid form ketones and nitrous acid. R R I He I 2R - CH - NO, “a 2R-C=O0+N,0 + 4,0 Note :- Tertiary nirtoalkanes are generally unaffected by hydrochloric acid. Primary & secondary nitroalkanes, i.e. those containing a-hydrogen atom, exhibit tautomerism. OH = R-CH = Ne \ ce Nitro form Isonitro form (pseudo- acid farm) (aci - form or nitronic acid) The equilibrium lies almost entirely to the nitro form due to resonance stabilization of the nitro group. These nitroalkanes dissolve In aqueous sodium hydroxide to form salts. ° ° ° / // a CHy-N? 40H = CH= NF —- cH,=N > s \o Nef carbonyl synthesis : When the solution of sodium salt of aci -form or nitronic acid is acidified with 50% sulphuric acid at room temperature, an aldehyde (from a primary nitroalkane) or a ketone (from a secondary nitroalkane) is formed. Prof. BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (2) Scanned with CamScannerpres i aR-C + 2HS0, = —-2R=C=0+N,0 + 2NAHSO, + H,0 ‘o aldehydes Rope R aR-c +2450, = —-2R- C=O+N,0 + 2NBHSO, + H,0 ‘o ketones 3. Halogenation : Primary and secondary nitroalkanes are readily halogenated in alkaline medium. The - hydrogens are replaced by chlorine or bromine. Primary nitroalkanes can farm mono-and dihalo derivatives, whereas secondary nitroalkanes form only monohalo derivative. Tertiary nitroalkanes do not react with halogens, H Br i i A - G-No,+ 26,4 2meoH —= A - €-NO, + aNsBr + 21,0 T H Br 1° Nitroaikanes Dibromo derivatives R R I I €-NO,+ Br, + NaOH eRe NO, + NaBr + 24,0 T H Br 2° Nitroalkanes Monobromo derivatives Chloropicrin (trichloronitromethane), an effective insecticide is manufactured by the action of chlorine and sodium hydroxide on nirtomethane. CH,NO, + 3Cl, + 3NAOH —* CCl, - NO, + 3NaCl + 3H,0 4, Reaction with nitrous acid ( Distinguishing test ) + Primary, secondary and tertiary nitroalkanes react differently with nitrous acid. ‘a. Primary nitroalkanes react with nitrous acid to form blue coloured nitroso-nitroalkanes (2ciform) which dissolve in sodium hydroxide to give red solutions. Ho HOO Ii ii R-C-N +HO-N=O—*R-C-N + 2H,0 AN rN HO No oO (nitroform) ut OH Na i LS ce Sa Leek i No ‘or No ‘o (aci form) Blue solution Red solution b. Secondary nitraalkanes react with nitrous acid to form blue coloured nitroso-nitroalkanes, which no more contain «t - hydrogen atom hence are insoluble in sodium hydroxide. Roo Ro I '// Rg sHoNeo—- Re eho H No © (blue solution) ¢. Teriary nitroalkanes do not react with nitrous acid since they have no a-hydrogen atom. 5. Condensation with aldehydes and ketones : Due to the presence of a-hydrogen atom, primary and secondary nitroalkanes undergo condensation with aldehydes or ketones in presence of ethanolic potassium hydroxide. The reaction is quite similar to aldol condensation and proceeds via formation of carbanion. HW W | KOH/C,H,OH | “H,0 GH. C = 0 + CH,NO, Gita E> CH, = NO, ——> GH,» CH = CH = NO Benzaldehyde on B-nitrostyrene |ALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (3) Scanned with CamScannerAMINES ‘Amines constitute an important class of arganic compounds derived by replacing one or more hydrogen atoms of ammonia molecule by alkyl / aryl group(s). In nature, they occur among proteins, vitamins, alkaloids and hormones: Synthetic examples include polymers, dyestuffs and drugs. Two biologic compounds, namely adrenaline and ephedrine, both containing secondary amino group, are ally active Used to increase blood pressure. Novocain, a synthetic arnino compound, is used as an anaesthetic in dentistry. Benadryl, 2 well known antihistaminic drug also contains tertiary amino group. Quaternary ammonium salts are used as surfactants. Diazonium salts are intermediates in the preparation of a variety of aromatic com- pounds including dyes. In this Unit, you will learn about amines and diazonium salts. © INTRODUCTION : “amines are the organic derivatives of ammonia in which one, two or all the three hydrogen atoms attached to nitrogen are replaced by the equivalent number of same or different alkyl and /or aryl group(s)”. 4 H R R i i I I H-N-H R-N-H R-N-H R-N-R NH, RNH, R,NH RN Ammonia 1Amines 2°Amines 3° Amines (Where R = alkyl or aryl group) Like ammonia, in amines the nitrogen undergoes sp3 hybridization. Each of the three sp? hybrid orbitals of nitrogen overlaps with the orbitals of hydrogen or carbon depending upon the class of amines. The remaining fourth sp hybrid orbital of nitrogen, in all amines, contains a lone pair of electrons. Like ammonia, amines have pyramidal geometry. H-N-H, C-N-H or C-N-C bond angle is less than 109°28" In aliphatic amines, the nitrogen is attached to sp? hybridized carbon of alkyl group and in aromatic amines to sp? hybridised carbon of ary! group. © CLASSIFICATION OF AMINES : Depending upon the number of hydrogen atoms replaced by alkyl or aryl groups attached to N in ammonia, molecule, amines are classified as primary (1°), secondary (2°) and tertiary (3°) a. Primary (1°) amines : In primary amines only one hydrogen atom of ammonia is replaced by one alkyl or ary group. The functional group of primary amines is -NH,(amine group). NH es. CH, - NH, Ethylamine ‘Aniline b. Secondary (2°) amines : In secondary amines two hydrogen atoms of ammonia are replaced by two same or different alkyl or aryl groups. The functional group of secondary ‘amines is >NH (imino group). — oe erymmonnvenme = (GYM ¢. Tertiary (3°) amines : In tertiary amines all the three hydrogen atoms from ammonia are replaced by three same or different alkyl or ary! groups. The functional group of tertiary amines is -N - (tertiary nitrogen atom or nitrile group). N(CH), 26 (64 Tretymine (OT bint Secondary and tertiary amines are further classified as a. Simple/ Symmetrical amines: In simple amines same alkyl groups are attached to the nitrogen e.g. C.H,-NH-CH, — Diethylamine (CH),NTrimethyl amine Prof. BHALCHANDRA SURWE’S Perfect Notes of CHEMISTRY. (4) Scanned with CamScannerb. Mixed or unsymmetrical amines: In mixed amines different alkyl groups are attached to the nitrogen. e.g. GH, N-GH, Diethyl methyl amine CH,-NH-C,#, Ethyl methyl amine Af cH, © NOMENCLATURE OF AMINES : 1. Common names : The aliphatic amine are named as alkylamines. The common name of {an aliphatic primary amine is obtained by writing the name of alkyl group followed by the word ‘amine’ In secondary and tertiary amines, the names of alkyl groups are entered in alphabetical order which Is followed by the word ‘amine’ If two oF three alkyl groups are same, the prefix ‘d'or ‘tri’ is added respectively before the name of alkyl group. In arylamines, - NH, group Is directly attached to aromatic nucleus. The simplest example C,H, - NH, is named as aniline. This name is also accepted by IUPAC. Other aromatic amines are named as derivatives of aniline. An aminotoluene is assigned a special name of toluidine. Suffix di, tri should not be considered in alphabetical order of alkyl group. 2. IUPAC names : 1. In this method, aliphatic amines are named as alkanamines. The name of amine is obtained by replacing the suffix ‘e’ from the name of parent alkane by ‘amine’. The position of amino group is indicated by lowest possible number. 2. If more than one amino groups are present at different positions in parent chain, their numbers are indicated by suitable prefix like ‘di, ‘tri’ etc. added before ‘amine’. The letter 'e’ of the suffix of parent alkane is retained. 3. In secondary and tertiary amines, the largest alkyl group is considered as parent alkane and other alkyl groups as N - substituents, 4. In arylamines, the suffix ‘e’ of the arene is replaced by ‘amine’ It should be noted here that, regardless of method of nomenclature, the complex name of amines is always ‘ritten as one word. Table : Common and IUPAC names of some amines benzylamine [common names | 1weacnames | if 1 ! | methylamine | Methanamine \ | ethylamine | ethanamine ' | n-propylamine | Propan -1- amine ai I i ! ft | | I 4.0, OH =n, | sprepyiamine | Propan-2-amine | 5.H.N-CH,+CH,-NH, | ethylenediamine | thane-1,2-diamine | 6.HIN-ICH,-!CH=°CH, | Allylamine | Prop-2-en-1-amine | ! 1 1 1 | | Aniline/phenylamine | Aniline or Benzenamine | | | cH, ' I | | o-toluidine | 2-Aminotoluene { | I 1 1 | ¥elohexylamine | Cyciohexanamine | 1 HM 1 ! i el of, BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (5) Scanned with CamScanner[b. Secondary amine 1. CH,- NH = CH, 2, CH, CH, - NH CH I3.GH-mi- ca = Methyimethanamine = Methylethanamine ~Phenylaniline N-Phenyl benzenamine dimethylamine In ethyimethyamine | N diphenylamine IN |e fe. Tertiary amines N,N - Dimethylmethanamine t 1 i 1 i 7 i i i i 1 1 1 ' i I I 1 ' N,N-Dimethylaniline | N,N Dimethylanilineor 1 | [1 CH-N- CH, | trimethylamine 1 N ! 1 | - | i 12. GH, N= GH, | triethylamine | N,n-Diethylethanamine \ | \ cH ! | i I \ | | | oe ' \ 1 | I | or N,N - Dimethylbenzenamine! I Hy Jo ---- © METHODS OF PREPARATION OF AMINES 1. From alkyl halides : By Hoffmann’s ammonolysis When ethyl bromide is heated with alcoholic ammonia at 373K in sealed copper tube, it gives a mixture of ethylamine, diethylamine and triethylamine along with tetraethyl ammonium bromide. H,- Br - NH, GH, - NH, + HBr (ale) ethylamine A CH.NH, +GH,-Br (GH), NH - HBr diethylamine 4 (GH), NH+ CH= Br = (C,H), N+ HBe triethylamine 4 : (GHD N+ Cy Br ee (GH), N* Br tetraethylammonium bromide aX aX aX. RX Thus, NH, = R- NH,» R,VH = RN» RINX An alkyl halide on reaction with ammonia in alcoholic solution undergoes nucleophilic substitution, in which the halogen atom is replaced by - NH, (amino) group. This process of breaking of C-x bond by ammonia is called ammonolysis. The reaction is also called alkylation of ammonia. ‘The primary amine thus obtained is stronger nucleophile than ammonia and further attacks alkyl halide to give secondary amine. In similar way alkylation continues to form secondary and tertiary amines along with tetraalkyl ammonium halides (quaternary ammonium salts). The order of reactivity of alkyl halides with ammonia RBr [Limitation: 25 ;he method is nat useful for preparation of primary amines because a mixture jof primary, secondary and tertiary amines along with quaternary ammonium salt is obtained |which is difficult to separate. | However, primary amine can be obtained as major product by using excess of ammonia. \Aryl halides do not normally react with ammonia due to low reactivity towards nucleophilic 'substitution reactions. tert - Butylamine cannot be prepared by the reaction of alcoholic ammonia on ten - Duty! bromide, because tertiary alky! halides on treatment with alcoholic base undergo elimination jin preference to substitution. cH, jicohal I Bohol Hy C= CH, + NH Br ' I i I i t= butyl bromide isobutylene Prof, BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (6) anil Scanned with CamScanner2. From alkyl halides: Gabriel phthalimide synthesis (Alkylation of phthalimide) phthalimide reacts with ethanolic potassium hydroxide to give potassium salt of phthalimide. In this step N - H proton is removed to give imide ion. Its then heated with alkyl haligeto give Nally phthalimide, which on akalin hydrolysis give a primary amine, g oe One Ce Cpe Cyr Gh Phihalimide N~ Alkyl p —a "Advantage : Over alkylation is avoided so that secondary or tertiary amin Limitation : Aromatic primary amines cannot be prepared by this method because aryl) ide. 3. From oximes, alkyl cyanides, amides and nilro compounds: By reduction COximes, alkyl cyanides, amides and nitro compounds can be reduced to corresponding primary amines by passing hydrogen gas in presence of catalyst like finely divided nickel, platinum or palladium or by using LiAIM,. ‘Oximes and alkyl cyanides are reduced by using sodium and ethyl alcohol, while nitro compounds are reduced particularly by using tin or iron and concentrated hydrochloric acid. a. From oximes : Aldoximes or ketoximes are reduced by sodium and ethanol to the corresponding primary amines, H I Na/ethanol R-C=N-OH+4{H] = RCH - NH, + H,0 Aldoxime 1° amine R R I Na/ethanol | R-C=N-OH + 4[H] —————= R-CH-NH, + H,0 Ketoxime 1° amine Acetaldoxime reacts with sodium and ethanol to give ethylamine. H | Na/ethanol CH,- C=N-OH + 4[H] —————= __CH,- CH,- NH, + H,0 Acetaldoxime Ethylamine Similarly, cH, cH, L Ne/ethanol 4 c ch-C=N-OH+4[H] = cH,- CH-NH, + H,0 Acetoxime Isopropylamine b. From alkyl cyanides (alkyl nitriles) : Alkyl cyanides on reduction by sodium and ethanol give primary amines. The reaction is called Mendius reduction. Na/ethanol R-C=N + 4[H] aa RCH, NY, Alkyl cyanide Aeamine ‘This reaction Is useful to increase the length of a carbon chain in preparing a primary ‘amine which contains one more carbon atom than the alkyl halide from which alkyl cyanide is obtained. e.g. (i) When acetonitrile is reduced by sodium and ethanol, it gives ethylamine. Na/ethanol CH,- CaN + 4[H) Aelethanel ca, cH NH, Acetonitrile (Ethanenitrile) Ethylamine (Ethanamine) Similarly Na/ethanol ai) (O}-eH,-€ + 4{H] ————+ 1H, - CH, = NH, Phenylacetonitrile B- Phenylethylamine Note : Ary! nitriles can also be reduced to aryl amines. BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (7) Scanned with CamScanner¢. From amides : Acid amides on reduction with lithium aluminium hydride give corresponding amines © 1) UAH ethyl ether n-ne AD Livi fatetiyl ether Se cy, : (ii) HO | Amides 1° Amines e.g. Acetamide on reduction with lithium aluminium hydride gives ethylamine. | ° i) LAI diethyl ether cHy-Hewn, — —OuAN diethylether c= cH, = NH, i HO Acetamide Ethylamine. itro compounds are reduced by tin or iron and concentrated 4. From nitro compounds : HCI to corresponding primary amines, 35n + GHC! — 35nCi, + 6(H) Sn/cone. HCl R=NO,+ 6fH] — SCONE ku, + 24,0 OR Fe & cone, HCl }) Nitrobenzene on reduction by tin and concentrated HCI or by using H,/Pd eg. ethanol gives aniline. NO: ~ NH, (OY +t Saves HoH toy +2H,0 Nivotenzene 3 Aniline Similarly, Sn/conc.HCl ii) CH, - CH, - CH, - NO, + 6[H] —————» cH, - CH, - CH, 1 - Nitropropane ee Propan LIAIH, in ether is also used to reduce - NO, group to - NH, group. UAlH,/ether NH, + 2H,0 amine CH, - CH, - NO, CH, - CH, - NH, Nitroethane Ethanamine . From amides : By Hoffmann bromamide degradation When amide is treated with bromine and aqueous or alcoholic sodium hydroxide, it gives a primary amine. ° "1 R-C-NH,+ Br, + 4NaOH —= R- NH, + Na,CO, + 2NaBr + 2H,0 This reaction is useful for decreasing the length of carbon chain by one carbon atom. It is an example of molecular rearrangement and involves the migration of an alkyl or aryl Group from the carbonyl carbon to the adjacent nitrogen atom. When propanamide is treated with bromine and aqueous or alcoholic sodium hydroxide, it gives ethanamine. ° I } (I) CH,~ CH, C= NH, + Br, + 4NaOH —* CH, CH, = NH, + Na,CO, + 2NaBr + 2H,0 Propanamide thanamine ° il é-ni, Ni, _ oy +B, +4NQOH OF +Na,C0, +2NaBr+211,0 Benzamide Atilne © PHYSICAL PROPERTIES OF AMINES 1. The lower aliphatic amines are colourless gases with fishy odour 2. The primary amines having three or more carbon atoms are liquids and the higher ones are solids. Prof. BHALCHANDRA SURWE’S Perfect Notes of CHEMISTRY. Scanned with CamScannernd other arylamines are colourless liquids when pure but get coloured as they are 3. Aniline 2 very easily oxidized by air, 4, Aryl amines are generally very toxic. 5. Primary, secondary and tertiary amines can form hydrogen bonds with water. As a result, aliphatic amines having up to six carbon atoms are soluble in water. However solubility decreases with increase in molar mass. 6. Amines are soluble in organic solvents like ether, alcohol, benzene etc. 7. The electronegativity of nitrogen is less (3.0) than that of oxygen (3.5). Hence amines are more polar than alkanes but less polar than alcohols. 8. Like alcohols, primary and secondary amines are associated by intermolecular hydrogen bonds 9. The association Is more in primary amines than that in secondary amines as there are two hydrogen atoms on nitrogen 10. Tertiary amines cannot form intermolecular hydrogen bonds due to absence of hydrogen atoms on nitrogen. 411, Thus amines have higher boiling points than alkanes but lower boiling points than alcohols ‘or carboxylic acids. 12. Hence, the order of boiling points of isomeric amines is 1° > 2° > 3°. 19 points of alkane, alcohol and amines of similar molar masses [ Molarmasses 7 6. j | oa @ REACTION OF AMINES : The lone pair of electrons on nitrogen makes amines both basic and nucleophilic. They react with acids to form salts and react with electrophiles in many reactions. With certain reagents, primary, secondary and tertiary amines give different products as nitrogen carries different number of hydrogen atoms. 1. Basic nature of amines : Amines react with aqueous mineral acids to form ammonium, salts. Amines are basic in nature as the lone pair of electrons on nitrogen can be donated. Thus amines are Lewis bases. An amine also acts as Bronsted -Lowry base as it accepts a proton from acid a R-NH+HX ==" R-NHX Ammonium salts when treated with a base like NaOH regenerate the parent amine. These ammonium salts are soluble in water but insoluble in ether. On the basis of these reactions amines can be separated from non-basic organic compounds, which are insoluble in water. R-N)X+NAOH 0 R=NH, + NaX + H,0 €.9. (i) Ethylamine reacts with dilute hydrochloric acid to give ethyl ammonium chloride H,- NH, + HCL = CH, - NHC Ethylamine Ethyl ammonium chloride Similarly, An, 2NH,Cr m OMa= OF aniline Anilinium chloride 2C,H,- NH, +H,SO, ee C,H, NH,*], $0,? Ethylamine Ethyl ammonium sulphate ‘* Write balanced chemical equations for the action of dil. (i) nitric acid on ethyl amine (ji) sulphuric acid on diethyl amine (il) acetic acid on triethyl amine. BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (9) Scanned with CamScanner)) Action of nitric acid on ethyl amine. C,MANH, + HNO, > [C,H,NH",]NO, Ethyl ammonium nitrate Ethyl amine (i) Action of sulphuric acid on diethyl amine } (C\H),NH + H,$0, ==> [(C,H,)NH",],502 Diethyl amine Diethyl ammonium sulphate {Action of acetic acid on triethyl amine (C,H,),N + CH,COOH === [(C,H,) NH") CH,COO ferninesctctog ey “red litmus paper blue. Amines Gi | ' | | | Triethy! amine Triethy! ar “~~ “.qucous solutions of amines are basic, and they turn red dissolve in water and following equilibrium exists, OH ion is stronger base than amines, the equilibrium lies far tothe lft; hence amines are weak bases than alkali NaOH or KOH: Refit H-O-H EER OR=NH, HOH weaker base stronger base ‘ie basic nature of amines can be better understood in terms of their K, and pk, values. [R-NHs J[oH ] [R-Na; [ow] [R-ne][R,0] °* [e-n4] and pk, = - loa K, Higher the value of K, or lower the value of pk,, amine is the stronger base. phase or Kye Tem] ami [Primary alkanamines t T | I Methanamine | 4sxtoe | 338 | \ Ethanamine jedO se soo | | Propan = 2- amine | 4ox10* | 340 | ! Phenyimethanamine | 20x10% | 4.70 i |, Secondary alkanamines: ! I 1 | NWethyietnanarine | Saxa0e | 3.27 | \ N= Ethylethanamine ote = eso | | Tertiary alkanamine: : i ! ' N,N-Dimethylmethanamine | 0.6xi0* | 4.22 | i N,N-Diethylethanamine | 56x10 | 3.25 | | Ammonia We gedose ertzs | | Arylamines: ! i I \ Benzenamine/aniline | 4axioe | 938 | | wetetnniine | 7inio" | 930 | nile LD 30% | 4 Consider the following reactions: 4 4 1 i r Ho Hee Hoo Rome 4 4 4 ‘Ammonia Ammonium ion Alkylamine Alkyl ammonium ion Due to electron releasing inductive effect (+1 effect) of alkyl groups the electron density ‘on nitrogen increases and the lone pair of electrons becomes readily available for protonation. Moreover the alkyl ammonium ion gets stabilized due to the dispersal of positive charge by the +1 effect of alkyl group. Thus, aliphatic amines are stronger bases than ammonia, H 4 R R i I v + HON-H oO R-N-H RN: RI-N-CR NH, RN, 2° Amines 3° Amines Ammonia 1° Amines Prof. BHALCHANDRA SURWE’S Perfect No! of CHEMISTRY. Scanned with CamScanner‘The basic nature of aliphatic amines should increase with the increase in number of alkyl groups. This trend is followed in gaseous phase, The basicity of aliphatic amines in gaseous phase decreases in the order: 3° amines > 2° amines > 1° amines > ammonia. However, in aqueous phase solvation of ammonium lons with water should be considered. The energy of solvation contributes to their stability. Greater the size of ion, lesser is the solvation and lesser is the stability of ion. In secondary and tertiary amines, due to steric hindrance, the alkyl groups decrease the number of water molecules that can approach closely and solvate ion. on, A Ron R i Pam * Row-neon, > SAC Dien-ont, i Rr” “H-on, RY on, : 2 3 Decreasing order of extent of H-bonding in water and order of stability of ions by solvation Thus the order of basicity of aliphatic amines should be 1° amines > 2° amines > 3° ‘amines. To compare the basicity of amines, the inductive effect, solvation effect, steric hindrance etc should be taken into consideration, In aqueous phase the order of basic strength of some alkylamines is as follows. (GH).NH > (GH)N > GHWNH, => ONH, (CH).NH > CHNH, => (CHN > NH, In arylamines, the -NH, group Is attached directly to aromatic nucleus (benzene ring). ‘The lone pair of electrons on nitrogen is in conjugation with benzene ring and is less available for protonation, e.g, Aniline is a resonance hybrid of following five structures. 8-3-6-8-6 5-8-6 © an ‘As, more the number of resonating structures., greater is the stability. Thus, aniline is, more stable than anilinium fon. Hence, aniline or other arylamines accept proton less readily or they are less basic in nature than ammonia, In case of substituted aniline, electron releasing groups like - OCH,, - CH,, - NH, increase the basic strength whereas electron withdrawing groups like - NO,, - C,H, - SO,, ~ COOH, - CN, -X decrease it. 1. Effect of substituent on the basic nature of Amine ‘a. EWG decreases the basic nature of Amine. b. Ortho substituted anilines are weak bases than anilines regardless of the nature of the substituent whether EWG or EDG. This is called as Ortho Effect and it is probably due to combination of steric and electronic factors. rof. BHALCHANDRA SURWI Perfect Notes of CHEMISTRY. Scanned with CamScanner| b. CH, - NH, > CICH, - NH, > ClCH = NH, > CIC-NH, CH, ~ CH, ~ NH, > CHs =f 5 AN NO, «© >O©>e 1 Jn, >©O>@G >@>O I WH, + (> O > T th wc, RNG, HC, a © > © > ” © > © oa 2. Action of nitrous acid : Primary, secondary and tertiary amines react differently with nitrous acid. Since nitrous acid is unstable, it is prepared in situ by the action of cold and dilute hydrochloric acid on sodium nitrite. NaNO, + HCI — Naci + HNO, a. Primary amines except methylamine, aliphatic primary amines react with nitrous acid Prot. BHALCHANDRA SURWE’S Perfect Notes of CHEMISTRY. Scanned with CamScanner‘in cold condition to form unstable aliphatic diazonium salt, which decompose to give alcohol with liberation of nitrogen gas, R-NH, + NaNO, + 2HCI — [R- N,*CI] + NaCl + 2H,0 R-N,Ch + H.0 — R-OH+HCI+ NN, t 2.9, Ethylamine reacts with nitrous acid in cold condition to give ethyl alcohol with liberation of nitrogen gas, Nano, + Hel GH.-NH, Ho, MRO NE cy ont HO +N, 273-278 7 Aromatic primary amines react with nitrous acid in cold conan to give elazonium salt. 7 273-278K } | +NaNo,+2Hc) =~" IP NaCl + 24,0 Aniline Benzene diazonium chloride b. Secondary amines : Secondary amines, both aliphatic and aromatic, react with nitrous acid to give yellow oily N - nitroso amines, NaNo, + HCI Sor RN N=04H0 273K-278K 9: (i) Diethylamine reacts with nitrous acid to give N - nitroso diethylamine. NaNO, + HCI RNH + HO-N (CHy),NH + HO -N (GH)N-N=0+H,0 273-278K Nenitroso diethylamine Similarly, ee oH wa N-N=0, NaNO,+HCl ® tHo =o — MNOMHG +H0 273-278K N= Methylanitine N= Nitroso - N - methylanitine ©. Tertiary amines ; Aliphatic tertiary amines react with nitrous acid to form water soluble nitrite salts; As no visible change is observed, it is said that there is no reaction, NaNO, + HCI RN+HNo, MNO + HC NHI-NO, 27aK278K 49; Triethylamine reacts with nitrous acid to give water soluble triethyl ammonium nitrite NaNO, + KCl (GHAN+ HNO, Freer UGHNHT No, 27aK278K Aromatic tertiary amines undergo electrophilic ring substitution, to give compounds in which a nitroso group is attached to a ring carbon, e.g. N, N- Dimethylaniline reacts with nitrous acid to give 4 - nitroso - N, N - Dimethylaniline NaNO, + HCI (CH), N +HO-N=0 ~ — (CH,),N N=O+H,0 273K-278K N, N-Dimethylaniline 4- Nitroso-N, N-dimethylaniline 3. Acylation of amines : “The replacement of a hydrogen atom attached to nitrogen in fi amines, by acy group (R~ C-) scaled acylation tis nuceopite substation reaction, The reaction Is caries out in presence ofa stronger base then amine like pyridine hich neutralizes HCl produced. The replacement of a hydrogen atom attached to nitrogen amines, by acetyl group is called acetylation Primary and secondary amines react with acetyl cloriée or ace anhydride to glue amides. The amide obtained by acetylation of primary amine is much less basi than omine; further acetylation requires excess of aetyating agent and hightemperature HALCHANDRA SURWE’S Perfect Notes of CHEMISTRY. G3) Scanned with CamScannerTertiary amines do not undergo acetylation as there is no hydrogen atom directly attached to nitrogen. Thus, tertiary amines can be distinguished from primary and secondary amines by acetylation. But primary and secondary amines cannot be distinguished from one another by this reaction. H Oy Hoy LA oe mon eren —] nS En " h h & Amine Acid chloride © byridine cum + ct cr Po uc, + Her etviemine A Nedcetylethyiamine a (N-Ethylethenamide) ° ° u Pyriding \ ay ceryanece,- Ue PEL ny, w cue Het achyerine Wy acetydlethylerine (N- Ethylethanamine) (N,N - diethylethanamide) Similar acetylation takes place with acetic anhydride (ethancic anhydride). a f ridit I chy WH, + H,- 6,0 EEE. Ch, WHC cH, + cH, - OH a ° ° ° Ul Pyridine i I (C,H,),H + (CH,-C-),0 ———= (C,H), N - C- CH, + CH,- C- OH ° ° 9 ul Pyridine u I Gili) CH NH, + (CH,-C-),0 = ———> C,H, - NHC CH, + CH, - C- OH a Aang NN Phenylacetamide Acetanlide) Amines aso react with benzoy chloride 3 ° tl Pyridine ul eg. CH,- NH, + Cl-C- C,H, ———= GH, -N H-C- C,H, + HCI ae N- Ethyibenzamite 4. Alkylation of amines: Hoffmann’s exhaustive alkylatio “The replacement of a hydrogen atom attached to nitrogen in amines, by alkyl group is called alkylation of amines.” Alkylation proceeds by SN? mechanism, so it is not feasible with tertiary alkyl halides because elimination predominates over substitution. When a primary amine is heated with primary alky! halide it gives a mixture of secondary amine, tertiary amine along with tetraalkylammonium halide. Rox RX ee R-NH, 0 RN oe yN RINK “HX “AX “AX. Tetraalky! 1° Amine 2° Amine 3° Amine amm. halide If excess of alkyl halide is used, a mixture of different alkylated products is avoided and tetraalkylammonium halide is obtained. The reaction Is known as exhaustive alkylation of amines. ‘The tetraalkylammonium halides are called quaternary ammonium salts. They are the derivatives of ammonium salts in which all the four hydrogen atoms attached to nitrogen in NH, are replaced by four same or different alkyl groups. Primary, secondary or tertiary amines react with excess alkyl halide to give quaternary ammonium salts. Primary amine consumes three moles, secondary amine consumes two Prof. BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. Scanned with CamScannersean ancon seri ou im presence of mild base NaHCO, to neualize the lrge wg: When methylamine is heated with excess methyl iodide, It gives tevametiviammoniam hl cH, NH, + CH, Se chy nne at A (CH,),NH + CH, 1 = (CH,),N + HI (CH)),N +H, a (CH).NT 5. Hoffmann elimination : When tetraalkylammonium halide is heated with moist silver hydroxide, it gives quaternary ammonium hydroxide. Quaternary ammonium hydroxides are deliquescent crystalline solids, which are strangly basic like NaQH or KOH, Quaternary ammonium hydroxides on strong heating undergo fi - elimination to give alkenes, the reaction is called Hoffmann elimination. In this reaction the major product is, least substituted alkene Ag,0/H,0 eg. Gui, = N* (CH,),1 + AgOH ————+ GH, - N*(CH),OH + Aat Ethyitrimethylammonium iodide A HH, - N° (CH,),OH > Ch, = cH, + (CH,),N + H,0 Ethylene 6. Hoffmann’s carbylamine test/ Isocyanide test : Aliphatic or aromatic primary amines on heating with chloroform and alcoholic potassium hydroxide give foul smelling alkyl isocyanides or carbylamines. Secondary or tertiary amines do not give this test. A R-NH, + CHCl, + 3KOH) —» R-NC + 3KCI+3H,0 A 1) GH, = NH, + CHCI, + 3KOH— C,H, - NC + 3KCI + 3H,0 Ethylamine Ethyl isocyanide Gy, -WH, + cH, + 2kOH + Gy, - Ne + 3K + 34,0 Aine Phenyl sccyaide 7. Reaction with aryisulphonyl chloride: Hinsbera’s test : A. Primary amine + Ethylamine reacts with benzenesulphonyl chloride to give Nethylbenzenesulphony| amide (soluble in alka) ° © CC) trerin- cs, oC Yb ct _ ba Benzene Sulphonylchiorde N= ethylbenzenesulphony! amide The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the Presence of strong electron withdrawing sulphonyl group. Hence it dissolves in aqueous Potassium hydroxide to give clear solution which on acidification regenerates insoluble amide. 8. Secondary amine : Diethylamine reacts with benzenesulphony! chloride to give N,N - diethylbenzenesulphonyl amide ( insoluble in alkali). A A OMeesriy-cn = Ly cn i N, N- diethylbenzenesulphonyl amide Prof. BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (a5) Scanned with CamScannerNN, N- diethylbenzenesulphonyl amide does not contain any hydrogen attached to nitrogen. Hence, it is not acidic and does not dissolve in aqueous potassium hydroxide. It also does not dissolve in acid. ©. Tertiary amine : Tricthylamine does not contain hydrogen attached to nitrogen and hence does not react with benzene-sulphonyl chloride. The unreacted triethylamine does not dissolve in aqueous potassium hydroxide but dissolves in acid. Thus, primary, secondary and tertlary amines can be benzenesulphonyl chloride (Hinsberg’s reagent). However, these days benzenesulphony! chloride is replaced by p-toulenesulphony! chloride. 8. Electrophilic aromatic substitution : Arylamines are bifunctional compounds. They also undergo electrophilic aromatic substitution along with the reactions of amino group. - NH,, - NHR and -NR; groups are ortho and para directing and powerful activating groups. Aniline is a resonance hybrid of five structures and highest electron density is present at ortho and para positions. Thus, aniline undergoes electrophilic aromatic substitution in ortho and para positions, @. Bromination : Aniline reacts with bromine water at room temperature to give a white precipitate of 2,4,6- tribromoaniline. inguished by action of aN be Br CG) em eT He br Aniline 2.4.6: Tbromoanine The - Ni, group is a powerful activating group. Hence, substitution does not stop at Imonobromo stage and brominationogcurs inal ortho and pera postions. To prepare monosubstituted aniline derivatives, the “NH, group Is fist protected by acetylation ane then desired substi seared out The Nh, group i estored by hyaelysie ‘Ths can be achieved, as acetamide group - NHCOCH, Ie lees stonaly activating group than = NH, group because its one poof electrons on nitragen's delocalized by the neighbouring carbony oxygen by resonance. The one pair of electrons on nitrogen isnot easly avalable to donate to benzene rng By resonance and the substitutions limited, 95 9 MEH, — Sweden, Aniline is heated with acetic anhydride to give acetanilide (N - Phenylacetamide). It is then treated with bromine in acetic acid to give p - bromoacetanilide which on acid or alkaline hydrolysis cives» - bromosniine ” xe ya-E-cn, MH — ) ~aathor? = 0) a ee NM Y t t Aatioe esate CC pBromoaaline Nitration Direct nitration of aniline results in the formation of p'- nitroaniline and © - nitroaniline along with dark coloured ‘tars’ due to oxidation. Furthermore, in strongly ‘cidic medium aniline is converted into anilinium ion. The - NH, group is meta directing, hence considerable amount of m - nitroaniline is also obtained. i ‘a vH fim ata eat a Prof. BHALCHANDRA SURWE’S Perfect Notes of CHEMISTRY. Scanned with CamScannerHowever, to get p - nitroaniline as major product, - NH, Is first protected by acetylation, nitration is carried out and then amide is hydrolyzed ° ° NH NH-C-cH, seucono , >) _ cone tv0,tone. 1180, pros a an SO No, p-nitroaniline Aniline ¢. Sulphonation : Aniline reacts with cold concentrated sulphuric acid to give anilinium hydrogen sulphate which on heating with sulphuric acid at 453 - 473K gives p - aminobenzene sulphonic acid (sulphanilic acid) as major product. 1p ~ nitroacetan ee C we O-C [= Explain, aniline does not undergo Friedel Craft’s reaction using aluminium chloride. [Ans. In Friedel Craft's reaction, AIC, is used as catalyst. AIC, is @ Lewis acid and forms a sat |with aniline (aniline is basic in nature). In salt nitrogen atom carries positive charge and it produces strong deactivating effect on the ring and makes it difficult for electrophilic attack IHence, aniline does not undergo Friedel Craft's reaction. © PREPARATION OF DIAZONIUM SALTS : Aliphatic primary amines react with nitrous acid in cold condition to give alkyldiazonium salts which are highly unstable and decompose to give alcohol with liberation of nitrogen gas. Arylamines react with nitrous acid in cold condition to give arenediazonium salts Conversion of primary aromatic amine into diazonium salts is known as diazotization. The arenediazonium salts are stable for a short time and slowly decompose even at low temperatures, hence are used immediately after preparation. ‘The stability of arenediazonium ion can be explained on the basis of resonance. 6-5-G-C-6 Benzenediazonium chloride is prepared by the .action of nitrous acid on aniline at 273 - 278K. Nitrous acid is produced in the reaction by the reaction between sodium nitrite and dilute hydrochloric acid NH, Nor + NaNO, + 2HCI + NaCl + 2,0 Aniline Benzenediazonium chloride Prof, BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (7) Scanned with CamScannerBenzenediazonium chloride Is a colourless crystalline solid. It readily dissolves in water and is stable for a short time at low temperatures. It decomposes easily in dry state. Benzenediazonium fluoroborate is insoluble in water and stable at room temperature. © REACTIONS OF DIAZONIUM SALTS A. Reactions involving replacement of diazonium group : In these reactions, the diazonium group is replaced by nucleophiles such as CI’, Br, T, F, CN, H’, OH" ete. Nitrpgen from diazonium group forms N, gas. (i) Replacement by -Cl, -Br and -CN: Sandmeyer reaction : Freshly prepared solution of diazonium salt is mixed with cuprous chloride or cuprous bromide to give ary! chloride or aryl bromide respectively. To prepare cyanide, diazonium salt is allowed to react with cuprous cyanide. The reaction in which copper (1) salts are used to replace nitrogen in diazonium salt is called Sandmeyer reaction Sct Ar cient are Nyx [SEO Ar areN, t 4 Ar-CN+N,t Alternatively, -Cl or -Br can be introduced in the aromatic ring by treating the diazonium salt solution with corresponding halogen acid and copper powder. The reaction is called Gattermann reaction. But the yield in Sandmeyer reaction is found to be better than Gattermann reaction. ss ar-cl+N, Ar- NX> Leute, ar—Br+N,t (ii) Replacement by -I : When the solution of diazonium salt is heated with potassium iodide aryl iodide is obtained. A Ar-NEX + KI — Ar -T4 NP + KX Replacement by -F : When fluoroboric acid is added to the solution of diazonium salt a precipitate of diazonium fluoroborate is obtained, which is filtered and dried. Dry diazonium fluoroborate on heating decomposes to give aryl fluoride, This reaction is called Balz-Schiemann reaction. HBF, A Ar = NX) Se Ar - Ne BFy = Ar F + BF, +7 (iv) Replacement By -H : Hypophosphorous acid (Phosphinic acid) or ethanol reduces diazonium salts to arenes. This is a reduction of arene diazonium ion. cucl Ar - NX + H,PO, + H,0 Arlt + NT + HPO, + HX Ar = NX’ + CH, CH,-OH——e APH +N, + CH,- CHO + HX (v) Replacement by -OH : The solution of a diazonium salt is slowly added to a large volume of boiling dilute sulphuric acid to get phenols. ilLH,SO, Ar- Nex +H,0 Ar-H + N+ HX (vi) Replacement by -NO, : when benzenediazonium fluoroborste is heated with aqueous solution of sodium nitrite in presence of copper it gives ritro benzene. BF, NaNoy/cu Gye WX GiHy- nor, SNC Cu, -no, + yt + NaBe, B. Reactions involving retention of diazonium group : coupling reaction : Arenediazonium salts react with certain aromatic compounds to give azo compounds having general formula, Ar - N= N - Ar. This reaction is called azo coupling. The azo compounds are often brightly coloured and are used as dyes, ArN’, + ArH Are N= N= Are He ‘The aromatic compound undergoing attack by diazonium ion must contain a powerful electron releasing group like -OH, -NR,, -NHR or -NR,. Substitution usually occurs para to the activating group. These are electrophilic aromatic substitution reactions and the electrophiles are positively charged diazonium ions. Prof. BHALCHANDRA SURWE’S Perfect Notes of CHEMISTRY. Scanned with CamScannerThe azo compounds have an extended conjugated system having both aromatic rings joined through the -N=N- bond, (azo linkage) due to which they absorb in the visible region of electromagnetic spectrum and are coloured. Benzenediazonium chloride reacts with phenol in mild alkaline medium to give p- Hydroxyazobenzene (Orange dye) \ N=N f \ of + Hct Benzenediazonium chloride phenol p-Hydroxyazobenzene Similarly, benzenediazonium chloride reacts with aniline in mild alkaline medium to give Benzenediazonium chloride Aniline-—sp-Aminoazobenzene \ f | € Swencr+ € }- on \_nu, 4 ¢ © IMPORTANCE OF DIAZONIUM SALTS : Arenediazonium salts can be prepared from nearly all primary amines and are helpful in the synthesis of a variety of organic compounds. “Cl, “Br, “I, Arenediazonium salts are very good intermediates to introduce groups like ~ “CN, -NO,, -OH,—H into aromatic ring, Aryl iodides and ary! fluorides cannot be prepared directly by electrophilic aromatic substitution. The cyano group cannot be introduced in an aromatic ring by the nucleophilic substitution of halide group. On the other hand, the halide or cyano group can be easily introduced in aromatic ring through diazonium salts. Thus the compounds which cannot be prepared by direct electrophilic ‘aromatic substitution can be prepared by replacement of diazo group, ‘Azo compounds obtained from diazonium salts are strongly coloured like red, orange, yellow, blue and are used as dyes. oe fof. BHALCHANDRA SURWE'S Perfect Notes of CHEMISTRY. (19) Scanned with CamScanner