NITROGEN CONTAINING 1. ALIPHATIC AMINES 14.1 INTRODUCTION ‘Amines may be regarded as derivatives of ammonia formed by the replacement of one or more hydrogen atoms by corres ponding number of alkyl groups. NH; snl er | 2R l+ae RNH, R,NH RiN (Primary) (Secondary) (Tertiary) Classification Amines are classified as primary (1°), secondary (2°) or tertiary (3°) depending on the number of alkyl groups attached to nitrogen atom. A primary amine has only one alkyl group directly attached to nitrogen atom, i.e, it has —NH group ‘which is known as amino group. Examples are: CH NH, ; CoHsNH2 5 CslipNH A secondary amine has two alkyl groups directly attached to nitrogen, i.e., it has >NH group which is known as imino group. These are furlierclasified as simple or mixed. When both the alkyl groups are same, i is termed simple secondary amine and in case both the alkyl groups are different, it is called mixed secondary amine. Some examples are: HC, HsCy oe iin > Le Hc Simple Simple fee HsCp o >in >in HC, HyC3 Mixed Mined COMPOUNDS A tertiary amine has three alkyl groups directly attached to nitrogen, £e, ithas S>N group which is known as tertiary nitrogen atom. The three alkyl groups may be same or different. Examples are: HC. Hy, HCN Hs SN HsCy HyCy Simple Mixed Mixed In addition to above amines, tetra-alkyl derivatives similar to ammonium salts also exist which are called quaternary ammonium compounds. NH; RyNT;—(CH)4NT Quaternary “etramethy ammonium iodide ammonium iodide i P f CH or ae x, ae eee R cH; Tes “etrametiyl ammonium corde Structure In amines, nitrogen is sp*-hybridized and the molecules have pyramidal shape like that in NH. Three hybrid orbitals possess one electron each and form sigma bonds either with carbon atoms of the three alkyl groups or with two carbon atoms of two alkyl groups and one hydrogen atom or with one carbon atom of one alkyl group and two hydrogen atoms. One Whe, ip tee, Hoe ae 7 Ba Hye Gry (Primary anne) (Secondary ane) Tota)ining Ce of the hybrid orbitals of nitrogen electron pair and does not take part in bond formation. All bond angles are approximately tetrahedral The amines of the type RiRoRsN (three different alkyl groups attached to chiral N) exist in the form of racemic mixture that cannot be resolved into enantiomers because of rapid inversion of an enantiomer to its mirtor image. This inversion is called amine inversion, flipping. Be name OB ESS ame y RDN erenioe NRA 14.2 NOMENCLATURE Tn common name system, amines are named by naming the alkyl groups attached to nitrogen atom followed by suffix amine. The names are written in one word only. Inthe case of ‘mixed amines, the names of the alkyl groups are written in alphabetical order. When two or three identical alkyl groups are attached to nitrogen atom, the prefix dio ris added to the name of alkyl group. CH3NH; 5 CzHsNH, 5 CHsCH,CHNH ; Metipianine "— Etylanine Propslaie 09 oy 0 CH; 1 HAC HC cry cin, n,n, Isopropytamine HAC HsCz fa Dimetiylamine Dietiyfamine @ ey HC Hy. HyC. xt: HCN ; On; HsC HC HsCy [tiyetivfamioe —Trinetylaine Eyl dneipanine e) oo ) HC HC? Cy thy met propylene e) In another system, amino group is considersd as sub- stituent and amines are named as amino derivatives of alkanes (eminoatkanes). Hy CH;NH) ; CHsNH2 ; cts—ba—nat, ‘Aminomethane Aminoethare 2-Aminopropane Secondary amines are named as alkyl aminoalkanes and tertiary as dialkyl aminoalkanes with highest rank to the aminoalkane (primary amine). HC HC, HC sa; as H3C SN, HC HC: H3C [N-Methy amino- .N-Metylamino- NN -Dimethy amino- ‘methane ‘ethane ‘methane In the IUPAC system, primary amines are named by replacing the final -e of the parent alkane by -amine (alkanamine). A number is added to indicate the position of Hp group. NED { CH3NH, ; CH3CH)NH; CH3—CH—CH3 Methanamine — Ethanaine Propan-2-anine CHsCHaCHaNH; CHs —EH—CH2CHs pan eamine kn Butan-2-amine ‘When two or more amino groups are present, words di-, tri, etc., are used with position numbers. HjNCHp—CH2NH ; HyNCH,CH,CHCH,CHs ‘Bthane1,2-diamine | NH? Peatane 3-iamine Secondary ortertiary amines are named as N-substituted derivatives of primary amines. The largest group attached to nitrogen is taken as the alkyl group of the primary amine, CH (CH3CH,NHCH; ; CH;CH;—N—CHCH,CH3 ‘asimane! i Ei pa eanycrigcnsnot—eia; Cayeath Cin 1 abi as NHCH3 vet ei cle ay Alig Ra — Gee NN-Diethyl-2-methyl pectan--amine Caffeine and coniine are some of the naturally occurring, amines. o Hs Hy ALN CO Jeamersers NH I n op on cH Cafine Conine Cyclic primary, secondary and tertiary amines can be named as, H-N—CpHs om a of Cyciohexanamine __N-Ethyleyslo- N,N: Dicyclopropyl ‘entanartine —_cyopropanamine14.3 ISOMERISM Atmines are represented by a general formula, C,Hq,.3N and exhibit following types of isomerism: 1, Funetional isomerism: This is dueto the presence of different functional groups, Le, NH or >NH or >>N. Molecular formula C3HN represents three functional isomers HyC\_ CH CH CH, NH 5 su; HBC Semyaane ASC eS ‘Primnpi——Etiylmethylamine Trimet (Secondary)2" —_(Tertary)3° 2. Chain isomerism : This is due to difference in the ‘carbon skeleton of the alkyl group attached to the amino group. CH (CHjCH,CH,CHyNH2 ;._CHsCHCH,NH; (C,Hy\N) ‘Bulan-l-amine 2-Methyl propan-I-amine (n-Burylaine) (Geobusylarine) 3. Position isomerism : This is due to the difference in the position of amino group in the carbon chain, CH; CH3CH2CH,NH ; CH3—CH—NH; (C3HyN). ropa -t-amine Propan.?-amine (n-Propylamine) (sopropylamine) 4, Metamerism : This is due to different alkyl groups attached to the same polyvalent functional group. HC HsCy Dw ut cathe By) ASC Methyl propylamine Diethylamine ‘SOME SOLVED EXAMPLES Problem 1. Write the names and strctures of four tso- ‘meric amines having the molecular formula Cy HN, Solution : HC © CHCHCHNE; Gi)" > CHNE, tr Propslanine sc Topeopyanice Hye. Wy) WEN : HsC2 HC “eimai Problem? Write the structures of eight isomericamines having the molecular formula CaHy,N. Solution : CH (@ CH3CH,CH,CH)NH3 ii) CH; —CH—CHNH3; GR. Organic Chemistry for Competitions CHs CHs | Git) Cis E— Na (iv) CH3CH —CH— NH; cay Calls CH,CH,CHs () CoHs—N—H; CH Gia I (vii) CH3—N—H_ (ili) Cs —N—-CHs, 14.4 BASIC NATURE OF AMINES ‘Amines like ammonia are basic in nature. The basic nature is due to the presence of an unshared pair (lone pair) of electrons ‘onnitrogen atom. This lone pair of electrons is available forthe formation of a new bond with a proton or Lewis acids. (vi) CHs—-N—H Hs rin; I | k k ‘Secondary amine (2°) ‘Tertiary amine (3°) ‘Amines are weak bases as they combine partially with the ‘water to form hydroxyl ions R—NH; +H,0 —= R—NH +087 ‘Alky ammonium ion Applying law of mass action, kc, [tN 11087} [R—NH}} (Where, A, is equilibrium constant of the base or basicity constant.) (Concentration of water is considered constant as it is present in large amounts.) The value of Ky describes the relative strength of the bases. Strong bases have higher values of K's while weak bases have low values. ‘A more convenient method of expressing the basic strength of amines isin terms of pK, values (pK, =—log KX). Smaller the value of pp; more isthe basic strength of amine, ‘The K;, and pK, values of some amines are given below:‘Nitrogen Containing Compounds Basicity constants of some amines Ls x10® 1° Amines ‘Methylamine, CH NH: 44xtot 335 Ethylamine, C3HsNHg s.axto* 329 2° Amines Dimethylamine, (CH), NH s4xio* 327 Dithylamine, (C,H)2NH Liao 295. 3 Amines ‘Trimethylamine, (CH,)N 60105 422 ‘Triettylamine, (CoHs)yN 356x104 325 ‘Aromatic amines ‘Asilie, CgHsNHa 42x10 | 938 ‘N-Methylaniline, CgHsNHCHs sox? | 930 NN-Dirmethylanitine, nsx | 892 CHN(CHS) Benzylamine, CH CHNH; 20%105 @ Alkylamines are stronger bases than ammonia: Alkylamines (I°, 2° and 3°) are stronger bases than ammonia. This can be explained in terms of electron releasing inductive effect of alkyl group. As a result, the electron density on the nitrogen atom increases and thus, they can donate the lone pair ‘of electrons more easily than ammonia. nN—n roN—w 2 Amine 3° Amine ‘The electron releasing effect is maximum in tertiary amines and minimum in primary amines (in gas phase). 3° Amine > 2° Amine > 1° Amine > NH However, the actual order of basicity (in aqueous solution) in the case of lower members is found to be as 2° Amine > 1° Amine > 3° Amine >NH3 i.e,(CHs ), NH> CH3NHp > (CH3)3N> NH If, however, the alkyl group is bigger than CH group, ic, ethyl, propyl, ete., there will be some steric hindrance to H-bonding. As a result, the stability due to +! effect predominates over the stability due to H-bonding and hence 3° amines become more basic than 1° amines. In other words, the ‘overall decreasing strength of ethylamine in aqueous medium is . (C2Hs)2NH > (C2Hs)3N> CzHsNH2 p> ee ™ In fact, the basic strength in aqueous solution depends not only upon electron releasing effect but also upon steric effect and hydration effect. (2) Steric effect : The crowding of alkyl groups cover nitrogen atoms from all sides and thus, makes the approach and bonding by a proton relatively difficult which results the ‘maximum steric strain in tertiary amines. The e¥éctrons are there but the path is blocked, resulting the reduced in its basicity. The order of basic nature of various amines has been found to vary with the nature of alkyl groups, Alkyl group Relative strength CHj— — RyNH>RNH,>R3N>NH;~ CaHs— _RyNH> R3N> RNHy > NH3 ‘Note: 1. Aniline is less basic than amunonia, The phenyl group exerts “I inductive) eect, ie, it withdraws electrons. This resus, to the lower availability of letrons on nitrogen for protonation. 2. Ethylamine and acetamide both contain an amino group but scetamide does ot show basic nature. This is because lone pair of electrons on nitrogen is dcocalised by resonance with the carbonyl group which makes it less available for protonation. ‘Not available due to elocalizaton cm Cit, — aj— CoN 4 The compounds with least character (p-tybriied is smosthasic and with mor ‘character (p-hytriized) is east. tric. Examples in decreasing order of basicity are @ cas Nu, > cH; —N—cHce, > Cly—Cm wy Gy ww) (ip CHCH,CHNTE > HjC~CHICH,NI, > HO=CCH,NI, (i) (CHy)aNi> CH,Nit > NH > CogNH Electron withdrawing (CH1s—) groups decreases electron density on nitrogen atom and thereby decreasing basi (i) (Ciy)aNH > CH,NE > CcHGNHCH, > CllsNE, (©) CHSCH,NH, > HO(CH,)gNHy > HO(CH, NB Electron withdrawing indtve effect ofthe OH group ‘decreases the electron density on nitrogen. This effect ‘diminishes with distance from the amino group. (b) Hydration effect: Italso depends upon the stability ofthe conjugated acid formed by accepting « proton from the solution. The hydration effect refers to the stabilization of the protonated amine by water molecules. The water molecules form H-bonding with the protonated amine and release energy (called hydration energy). ‘Now greater the extent of H-bonding in protonated amine, ‘more will be its stabilization, i.e., 1° amine is the most stable since, ithas three H-atoms which can form H-bonds with HO (maximum hydration) and consequently, greater will be the basic strength of the corresponding amine. The 2° amine is lessstable since, it has two H-atoms (less hydration) while that of 3° amines is the least stable since, it has only one H-atomn (least hydration) which can form H-bonds with HO. Therefore, the basic strength of amines in aqueous solution should follow the order. R—NH (1° Amine)> RaNH (2° Amine)> RyN (3° Amine) Hi Ho a: RNR, «Ht = RNA 1 Amine Na tertiary > primary amines Problem 3. Trimethylamine isles basic than dimethyl- ‘amine or methylamine. Explain why itis so? Solution : Methyl groups are electron releasing groups. Although in cimethylamine, te electron density on nitrogen tore in comparison to dimethylamine or methylamine yet itis less basic because crowding of three methyl groups makes it difficult for aprotonto approach the nitrogen inorder to form a bond. Thus, the electrons are therein trimethylamine but the path is blocked 145 GENERAL METHODS OF PREPARATION Methods Yielding Mixture of Amines (Primary, Secondary and Tertiary) 1. Hofmann’s ammonolysis method : A mixture of amines (primary, secondary and tertiary amines) along with GRB. Organic Chemistry for Competitions ‘quatemary compound is formed when alkyl halide is heated with alcoholic ammonia in a sealed tube at 100°C. Osh Calis] + NH; —>C,H NH; —*5 (C2Hs).NH yl iodde (AS) Etylamine Dietiylanine cy @ Coligh CoHigt <2; Colts)sNS (CoHs)4NI Trietine Teracy 3 meron indie ‘This reaction is a typical example of nucleophilic ‘substitution reaction, Mechanism: (@) The mechanism involves the nucleophilic attack of NH3 molecule (through fone pair) on ‘RX. Primary (1°) amine salt is formed which reacts with ammonia to give 1° amines and ammonium halide as follows: cof + aN + RG 28%) ennx- sommes" lly alge Vain st NH; = ant +NHY x iP Amine (b) The primary (1°) amine formed now acts as the nucleophile and reacts with another molecule of R—X to form 2° (ec-) amine. Ox BK, Ryrtty x- "FA at Mi, = R.NH +NH}X~ P hnine (©) The reaction is repeated to form tertiary (3°) and (quatemary ammonium salt as follows. RNn+ RX 22S, away 2hmine 3° amin sal Nil, = BN + NH} X™ oN 3° Amine @ RN +ROY BK, Rt xe sPamine Quseraty amino salt So, the ammonia molecule in the first step and amine auwlovutes iu Ure subsequent steps act as nucleuphies, ‘The primary amine may be obtained in a good yield by using a large excess of ammonia. The process is also termed as ‘ammonolysis of alkyl halides. The amines being basic at once combine with HI produced during reaction to form salts. ‘The reactivity of various halides in this reaction is R-1> R—Br>R—Cland 1° > 2°>3° alkyl halide. Tertiary butyl bromide (3°) on treatment with NH; (base) prefers to undergo elimination rather than substitution.Nitrogen Containing Compounds 2, Ammonolysis of alcohols : A mixture of amines is also obtained when the mixture containing vapours of alcohol ‘and ammonia are passed over heated alumina (Al703 Jor thoria, (THO; ) at 350°C. HOH CyHs0H+ NH —>C,HsNH, >> yl aleobol Amine CHsoH (CHs),NH 5 (CoHs)3N Aine Famine Primary amine may be obtained in a good yletéby using & large excess of ammonia. Methods Yielding Primary Amines 3, Reduction of nitro compounds Primary amines can be obtained by the reduction of nitro alkanes with Sn/HCl; ‘Za/HCI; Ho/Ni; LiAIHin dry ether; Raney Ni or Pt or Pd as catalyst at room temperature. R—NOp +6fH] BO, RN, +240 ZaiBCl or Nr oc LiAlig Cals NO. +e] SCL, CHiN, +2810 ‘Nitoethane oF Pe Etaramine 4. Reduction of nitriles (Mendius reaction) : Primary amines can be prepared by reduction of nitriles. The reduction i. done either catalytically with Hand Raney Ni or with sodium in alcohol or sodium amalgam and alcohol or with LiAIH... H,/Raney Ni Coen + A R—CH,NHy ‘Alkyl nitele Amine [NaiC;H,OH CH;C=N + 4A] ‘Methyl cyanide (Acetonitrile) ‘The start can be made from alcohol or alkyl halide. CH3 —CH)NH Ethanarine soc, x LAM, R-ON—4 RAB, R—CN 5 RCH NH ‘Abobo Aliyl chloride Allyl nile Primary amine This sequence gives an amine containing one more carbon atom than aleohol. 5. By reduction of amides : Primary amines having same number of carbon atoms can be obtained by the reduction of amides by LiAIH, or sodium and absolute alcohol. AIH ether RCONH, + 4) ae ran? * HN GH, OF amide RCH,NH Amine LiAIH, fotber CHCONH, + api) LAM! Oy cHANH ‘Accamide ttylamine 6. By reduction of oximes : Primary amines can be formed by reduction of oximes. The reduction is done by 75. Hz/Ni; sodium and absolute alcohol or LiAlH. The start can ‘be made from an aldehyde or ketone. Ally NOH -——4y RCH;NH2 “Aldoxime H,NOH RCHO 2 RCI Aldehyde CHgCH—NoH + 4] 2 cii,CH,NH + 20 Acetaldoxiine or AIH, Ethylamine R Sc=0+ tno Se NOH R. Ketone Ketoxime R Liat, tT , |—NH, Sea po Amine 7. Hofmann’s bromamide reaction or degradation : By this method, the amide (—CONH, ) group is converted into primary amino (—NH) group. The amide is heated with bromine and concentrated aqueous or ethanolic KOH solution (or potassium hypobromite, KOBr). RCONH2 + Bry + 4KOH Hs RNH +2KBr ‘Amide Wy “amine ¥KCOs +2H,0 For example, CHjCONH; + Bry +4KOH Hy CH3NH +2KBr ‘Acetamide ‘Methylamine +K,CO3 +2H,0 (CH3CHCONH) + Br) + 4KOH 22% CH;CH; NH Propanamide thanamine +2KBr +K;C03 +2H0 This is most convenient laboratory method to give pure amine containing one carbon atom less than amide (For mechanism see Seetion 13.5). 8. Gabriel phthalimide synthesis : This method involves the following three steps: (a) Phthalimide is reacted with ethanolic solution of KOH to form potassium phthalimide. (b) The potassium salt is treated with an alkyl halide. (©) The product N-alkyl phthalimide is put to hydrolysis with dilute hydrochloric acid under pressure when, pure primary amine is formed. CON. Ko O2>« Oe ee OT st, Phthalimide Potassium phthaiide COOH Gk >veas THO, CoHSNHa+ HCl A Betyiamine ‘COOH Ethyl phthalimide Phthalic aidTe ‘When hydrolysis is difficult, the N-alkyl phthalimide can be treated with hydrazine to give the required amine. This is called bydrazinolysis (cleavage by using hydrazine). Clo ho @ Only as pare Gabriel synthesis: Gi) Axiline cannot be prepared by this synthesis because aryl halides (CHCl oF CgHsBs) do not undergo mcleopbilic substitution (ce, the eevage of C—X bood in aloaens is suite dificult) with potassium phbalimide under ordinary conditions to give N-phenyphalimde. 9. By decarboxylation of a-amino acids : Decar- boxylationis done by distilling the amino acid with Ba(OH) rcncoon 2MM2, acH:NH, +BaCO; +H,0 Heat + Amine NH é-Amno aid BxOH), cu,coon 2%, crsni; +BaCOs +130 | Heat “Mettyl- Ni mine t-Aminoceti sid (Giysion) caycucoon 2, cuscuan, «Baca, “1,0 \ Heat Ettylamine NH ce-Atinpropionie acid (Alanna) 10. By. double decomposition between Grignard reagent and chloramine : ‘RMgX +CINH, —4> RNH2 +MgXC1 CoHsMgl+ CINH2 Sots NH sit ae Chloramine 11. By hydrolysis of isocyanides or isocyanates : H ‘oH ©) RNC + 2H,0—Hs ANH, + HCOOH ‘Ol Allyl arine oe C2HsNC_ +2H,0—ECL,¢c,H,NH2 + HCOOH Ethyl isocyanide tyne CH, —Ne +280 cH —NH, + HCOOH Acta jontile Meltazanine H lox (CH; —N=C=0 + 2KOH-> CH; —NH +K;CO3 H'OK Methanaine ‘Meth isbeyanate GRB. Organic Chemistry for Competitions CyHs—NCO +2KOH —+C;Hs—NH +K,C03 thy socyaate thsnamine 12. By Schmidt reaction : Cone. HS0, R—COOH+ N3H ——*—4R—NH, +N2 +CO2 Acid Hydrazote Alkyl acid amine Cone. H,504 (CH CH,COOH + Nj H———*—$.CHCH;NHz+N2+CO2 Propionic acid Eliplanine In this reaction, the acylazide (R—-CON3) and alkyl isocyanate (R —NCO) are formed as an intermediate. (@ R—COOH+N3H—> RCON3 +H;0 ‘Acyazide GeHlgor CHC A Gi) RCON = R—N=C=0+N3 Acylaride Cut EAFAREEMES Ai isocyanate Git) R-N=C=0 + HO —> R—NH3 +COz ‘Alkyl isocyanate ‘Alkyl amie The overall eaton which proceeds bythe eliination of nitrogen from acylazide followed by acidic or alkaline hydrolysis to yield primary amine containing one carbon less, is called Curtius degradation. ‘This method uses acid chloride to prepare primary amine through acylazide. i i Y s00, po 0, pbx, pty Acid Acylazide © a—0—95 % aw ‘Aeylaide ‘The mechanism of Curtius rearrangement is very similar to Hofinann degradation. AGU! Ny = b Schmidt reaction converts R—COOH to. R—NH3; which is a modification of curtis degradation. In this reaction, a carboxylic acid is warmed with sodium azide (Na"N3 and. conc. H S04. The carboxylic acd is direetly converted to the primary amine without the necessity of isolating alkyl azide. ° [NaN + 1,504 (cone) ase I R—C—OH RNH; +Nz +CO2Nitrogen Containing Compounds (NaN; +H)S0, —> N3H+NaHSO,4) ° j Cone #804 crcl, —C—on + any SEE Son scH nt Propanoicasid "tmzsicacid Hest” ptanamine +002 +N2 13, By Ritter reaction : It is a good method for preparing primary amines having a tertiary alkyl group. Thus, tertiary butyl alcohol (or alkene) is treated with hydrocyanic ‘acid (or alkyl cyanide) in the presence of cone. sulphuric acid to give rert. butylamine. (CHs);C—OH + HyS04 + HCN —> (CH3);C—NHy Ter yl lesbo ert. batyamine ‘@* Aco) (i Arn} [acon H,0+ Rct PN, RcN=cH Te eatoction 4.0 _ on HCOO" +8;C—NH, «2! rycNH—CHO 1" Amie H804 on R—Cme N+ (CH;);C—0n 2, Alco noni" R—C—NH—C(CH3)3 > ‘Amide 9 e—tons (CH3)3C—NH 1 Amine 14, Reductive amination of aldehydes and ketones : ‘Aldehyde or ketone when reduced catalytically with nickel, Hp/Raney Ni or NaBH3CN (sodium cyanoborohydride) in presence of excess of ammonia at about 150°C under pressure G00 atm) forms primary amine through the intermediate formation of an imine. oO R—C—H+NH, +H; NISC, g_cH, —NH +120 "Aldeyde 300m primary amine f i X [P60 erat Ben GI Oe Ni Ao Nts | a "nine CH CHO +NH +H, SABES, cHcH Nip + H,0 ‘Acetaldehyde atm pressure Eehylamine O° ie Lc +t BEES ON Ketone i m Loris 82 cc “Acetone (HZ0) Dimethyl ketimine NH HAIN. CH; —CH—CHs ornabien” HSC (sopropytnize ‘This reaction probably takes place through the formation ofan imine (Schif's base). ‘The primary amines can also be converted into secondary or tertiary amines by the following steps: H/Nioe R—CHO+ R'NHy —2 “> RCH)NHR’ NaBHSCN 2° Amine -RNH, + 2H)C—0+ 2HCOOH -> RN(CHs)x+2H,0+ 2CO, 3° Amine 15. By reduetion of azide with NaBHy: NaBH, R—X' +NaN; —> RN; ——*> RNH) Alkyltalide Sodium ——Aky! H20 (1*) Amine (ora) aide aide 16, By Leuckart reaction : Aldehydes or ketones react ‘with ammonium formate or with formamide to give formyl derivative of primary amine. I Scmosniooont —> dean a+2n0 ceed +CO2 +NH3 Oo “1 >C=0+2HCONH, —> >CHNH—C—H+C0, +NH3 Fomeie ‘These formyl derivatives are readily hydrolysed by acid to yield primary amine. R 1 AR Eas HOES, criss +H50+C02 This is called Leuckart reaction, ie., KN 0+ HCOONH, a ‘Am, formate 4 BR 102006 _DCHNH2+H,0+C02 Ketone Primary amive 17. By the action of ammonia on alkenes: Ethylamine is obtained by heating a mixture of ethylene and ammonia at 450°C under 20 atmospheric pressure in presence of cobalt catalyst (commercial preparation). Cobalt catalyst H)C—= CH) +NH3 =", CH3CH)NH> F 50°C, 20 atm718 Methods Yielding Secondary Amines 1, Reaction of primary amines with alkyl halides: A primary amine is heated with calculated quantity of alkyl halide when dialkyl ammonium sat is formed. Itis then treated ‘with NaOH solution to recover free secondary amine. R—NH, +R—X —> R2NH+HX —> R2NH2X RyNH;,X+ NaOH —+ RyNH +H,0+Nax Secondary amine CHy NH +CH31—*>CH3NHCH; +HI Methylamine imethyarine 2. Reduction of N-substituted amides : Reduction of [N-substituted amides with LiAIH, yield secondary amines. Alkyl amino ketones are formed by the action of ketone with formaldehyde and NH 3 (or primary or secondary amines). ‘The product is referred to as Mannich base and the reaction is called Mannich Reaction, CH COCH, + HCHO + RNH2 “5 cHyCOCH,CH,NHR Which can be reduced to alkyl amines. R—connr’ +4(H) 2", ecu. nur’ +H,0 All acid amide Anite 3. Reduction of Isonitrites : Secondary amines are formed when isonitiles ae reduced with hydrogen in presence ‘of Pecatalyst or sodium in presence of alcohol or Raney Ni or Lilly. RN=C_ +4[H]—P!°!_, RNHCH; ylisnide LAI” “D arine CH;CH,N=c+4[e] @™! , cH CH)NHCH; By ineyanide or LiAlH " y-Methyl ethanamine ‘Secondary amine formed by this method always possesses ‘one —CH group linked directly to nitrogen. 4. Reaction of p-nitroso diatky! aniline with strong Pure secondary amine is formed when 2RX, HNO), OM BEO—nn “20x -)—e ee ee oe OHH { Neo ONO) +NRz +H on—{O)—on ‘p-Nitroso-atkyl aniline _-Nitrosophenol + NH Amine This is one of the best methods for preparing -pure secondary amines. GR.B. Organic Chemistry for Competitions 5. Hydrolysis of dialkyl cyanamide : Pure secondary amine may be obtained by the hydrolysis of a dialkyl cyanamide with an acid or alkali. [Can—cN 28208, NaN—CN 2245 RoN—CN] Calcium Sodium Dialkyt cyanamide cyanamide cyanamide R)N—CN+2HOH*, R;NH +CO, +NH3 Dialylanine ‘6. Using Grignard reagent : Grignard reagent on ‘reatment with dichloroamine gives secondary amine. C2HsiMeCl” Cit HsCr it DNHS SNH +2MgCh, CoHsiMgCl Cl Cr Methods Yielding Tertiary Amines 1, Reaction of alkyl halides with ammonia: When an alcoholic solution of ammonia is heated with excess of alkyl halide, a triakyl ammonium salt is formed. This on treatment with dilute NaOH solution gives tertiary amine. 3RK +NH3 —»>RsN +3HX —+ R3NHX Ry NH + NaOH —> R3N+NaX +H,0 2, Reduction of N,N-disubstituted amides : Reduction with LiAIH, is done. X,\-disubsttuted amides on reduction form tertiary amines. The carbonyl group is converted into—CH} group. ,, Lally 5 RCONRS t+ RCH2NR: + H20 3. Decomposition of tetra-ammonium hydroxides : The tetraalkyl ammonium hydroxides are formed when corresponding halides are treated with moist silver oxide. R4Ni + AgOH —> RyNOF + Agl ‘The hydroxides thus formed on heating decompose into tertiary amines. Tetramethy! ammonium hydroxide gives ‘methyl alcohol as one of the products while al other tetra-alkyl ammonium hydroxides give an olefin and water besides tertiary amines, (Cll) ,NOH 484 (CHy)3N + C1011 (C2Hs)4NOH —*+(C,Hs)3N+H,C= CH, +H,0 Tetra ethyl ammonium Famine Ethene hydroxide 4. By reductive amination : This method is suitable for synthesis of both, secondary and tertiary amines. CHyCHO +C,HsNHy +H, —N\> CH;CH,NHC;Hs Acetaldeyde (1°) Amine (2) Amine‘Nitrogen Containing Compounds Ni = N—H+H, iy HyC~ HC 7 ‘Acetone (2) Amine CX DENCH nc | CH G°) Amine ‘Separation of Mixture of Amines (1°, 2° and 3°) ‘When the mixture consists of salts of primary, secondary and tertiary amines along with quaternary salt, it is first distilled with KOH sotution. The mixture of three amines distil cover leaving behind non-volatile quatemary salt in the distillation flask, RNHyHlor RNHy—1+KOH —4s RNH, + KI+H,0 Prinary amine (oat), Disine RyNHHl or RyNHy—I + KOH —*> RyNH+ KI+H,0 RyNHlor RyNi—I + KOH RN+KI+ 10 «Ni (non-volatile tetra-alky! ammonium salt) has no reaction with KOH, however remains as residue. This mixture is separated into primary, secondary and tertiary amines by the application of following methods: 1. Fractional distillation The boiling points of primary, secondary and tertiary amines are quite different, ie., the boiling point of C)HsNH) is 17°C, (C2Hs)2NHis 56°C. and (C2Hs)3N is 95°C and thus, these can be separated by fractional distillation. This method is used satisfactorily in industry. 2. Hofmann’s method : | The mixture of three amines is treated with diethyl oxalate (Hofmann’s reagent), The primary. amine forms a solid dialkyl oxamide, a secondary amine gives ‘while tertiary amine does not react. NHR csujon CONHR ee | CONHR Dialkyl oxamide (Golid) Gowns C00C;Hs Dilly ona eter (Liquid) Primary amine is recovered when solid oxamide is heated with caustic potash solution and collected as distillate on distilling the reaction mixture. Ni IK COOK Diethyl oxalate amine isillate) 779 ‘The liquid (mixture of oxamic ester + tertiary amine) is subjected to fractional distillation when tertiary amine distils over. The remaining liquid is distilled with KOH to recover HOK + Hes, HOK COOK RNH + | yc HHO COOC; Hs Secondary Dialkyl oxamie exter amine” Pot, oxalate 3. Hinsherg’s method : It involves the treatment of the mixture with benzene sulphonyl chloride, ie, Hinsberg’s reagent (CsHsS02C)). The solution is then made alkaline with aqueous alkali to form sodium or potassium salt of ‘monoalkyl benzene sulphonamide (soluble in alkali). CeHsS02Cl_+HNHR ——>CcHsS02NHR S08, Benmene Primary amie All benzene sign ‘sptomaade enone C6HsSO,.NKR Soluble salt ‘The secondary amine forms N,N-dialkyl benzene sulphonamide which docs not form any salt with KOH and remains as insoluble in alkali solution. (CoHs$02Cl + HNRy ——> CoHsS02NR7 SOs ‘Sec. amine -HC! yyy -pialkyt tenzene sulphonamide Noreaction (Insoluble in alkali) Tertiary amine does not react. The above alkaline mixture of the amines is extracted with ether. “Two distinct layers are formed. Lower layer, the aqueous layer consists of potassium salt of Naalkyl benzene sulphonamide (primary amine) and upper layer, the etheral layer consists of N.N-dialkyl benzene sulphonamide (socondary amine) and tertiary amine. “Two layers are separated. The upper layer is fractionally distilled. One fraction obtained is tertiary amine and the other faction is hydrolysed with concentrated HCI to recover secondary amine hydrochloride which gives free secondary amine on distillation with KOH. C¢HsSO2NR, + HCI+ H,0-44C,H;S0,-0H + R2NH-HCI R,NHHC|+KOH—*> R2NH+ KCI+H;0 See. amine ‘The aqueous layer is acidified with dil. HCI and hydrolysed by heating with conc. HCl. The hydrochloride formed is then distilled with KOH when primary amine over and collected. (CeHsSO2N(K)R + HCl —s CgHsS02NHR + KCI (il) “Sulphonamide of primary amine720 ColsSO;NHR + HCl + 30 —+CyHs8070H + NHS HCL one. Primary nine hydrochloride RNH3-HC1+KOH—*+ RNH2 + KCI+H,0 Recently benzene sulphonyl chloride is replaced by p-toluene sulphonyl chloride (tosyl chloride) since, the sub- stituted sulphonamides thus formed are stable solids which can. bbe easily purified by crystallization Physical properties: (i) Lower amines are gases or low boiling point liquids and possess a characteristic ammonia like smell (fishy odour). Higher members are solids. i) The boiling points rise gradually with increase of ‘molecular mass. Amines are polar compounds like NH and have comparatively higher boiling points than non-polar compounds of similar molecular masses. This is due to the presence of intermolecular hydrogen bonding (except tertiary amines). H | HON: R ‘Hydrogen bonding in amines Gi) Amines are soluble in water. This is due to hydrogen bonding between amine and water molecules. Amines are also soluble in benzene and ether. H | |—0:---H—N? I I H R Hydrogen bonding between amine and water molecules Solubility decreases with increase of molecular mass. ‘Chemical properties: The main reactions of amines are ‘due to the presence ofa lone pair of electrons on nitrogen atom. ‘Amines are nucleophilic reagents as the lone pair of electrons, can be donated to electron secking reagents, (ce, electrophiles). (® Salt formation : Amines, being basic in nature, combine with mineral acids to form salts, The amine salts when {treated with NaOH liberates parent amine. R—NHy +1ICI—+ RNIy “HCL or = RNH3C1 “Allylaine (Allyl ammonium chloride) ay -RNHCI+NeOH—> BNE +NaCl+H;0 RyNH +HCI-> RNH,CT MOH, RH + NaCl-+ H30 amine (R,NH2)2S8035 Dialkyl ammonium sulphate R,NH +H,S0,—> Diatkylamine GRB. Organic Chemistry for Competitions RN +HCl> RsNHCI MOH, R,N+NaCl+H30 3° Amine RN +HNO;—> — (R3NH)NOS Trialling “rial ammonium nitrate Further, amine hydrochlorides, on ‘heating undergo dialkylation RsN-HCL—*5 R:NH +RCL ‘riakylamine —Dilkylamine Inydrobloride RyNH- HCI RNHp + RCI RNH2-HCI—*> NH; + RCI (RNH3)2805 (Aly! aromoniur sulphate) With chlorauric acid, chloroplatinic acid and chlorostanic acid, amines form double salts: NH +HAuCly —> RNH3-HAuCly 2RNHy + HpPtClg —> (RNHg)9°HaPIClg 2RNH2 + H2SnClg —+ (RNH2)2° H2SnCly The reaction of diborane (BH )2 with NH3, 1° and 2° amines yield an one compound, H : 2RNI+ >> B< PAmine He ~~ H a 5, . Diane tl : > <4 > i Nx I ><] ty However, 3° amine forms an adduct with diborane. (CH) N+ BH —> (CH) > BH Sanne ‘Addu All the amines are basic and they are stronger bases than ammonia (see Section 14.4. (li) Nature of aqueous solution : Amines combine with water to form alkyl ammonium hydroxides. These ionise to give hydroxide ions in solution, ie, the aqueous solutions of amines are basic in nature, RNH, + HOH == RNHjOH” <= [RNHs]" +OH™ iPAmize RNH + HOH == RyNH2OH” = [R,NHy]* +08" Phmine RN +HOH <== Ry NHOH” == [RjNH]* +OH™ AmineNitrogen Containing Compounds ‘The aqueous solutions of amines behave like NH OH and give precipitates of iron, chromium: and aluminium as hydroxides when their salts are treated with it and also blue solution with copper sulphate. 3RNHOH + FeCly —> Fe(OH)3 +38N11.C1 : Brown ppt (Gi) Reaction with alkyl halides (Alkylation) : The hydrogen atoms of the amino group are suecessively replaced by alkyl groups when amines are treated with alkyl halides. nally, textiay ansine ad vue vivre molecule uf alkyl halide to form a quaternary compound. NH: 24 enue’ 2% r—nes 2% (R—NRD)A Prisamine “AX Sec. amine “FY Ter. amine Quaterary salt (Quaternary ammonium halides on treatment with moist silver oxide (AgOH) or methanolic KOH are converted into their corresponding hydroxides which are strongly basic as NaOH or KOH. [RN] X> +AgOH —> [RyNJ'OH + Agy ‘Quaternary Quaternary amen. halide _amm. hydroxide (iv) Reaction with acid chlorides and acid anhydrides (Acylation or acetylation) : (a) Acid chlorides or acid anhydrides reat with primary amines and form N-substiuted amides. ° ° i -Ha. I (RNH2 + CICCH3 1" Arne Ace storide HG, RNHCCH; Alkyl acetamide ° (CH3CO 7 I NH; + So aSHRCOOH, eC cH, CHO. {N-Alkyl etna ‘Acti anydide (b) Secondary amines react with acid chlorides to form N,N-disubstituted amides. i i RyNH +CI0CH; —ES, —_RyNCOCHs 2 Amine ‘NN -Dialky acetamide (©) Tertiary amines do not react, since they do not have replaceable hydrogen on nitrogen. |” Therefore, all these above reactions are used to distinguish between primary, secondary and tertiary amines. (9) Action of sodium : Primary and secondary mines form sodium salts when heated with sodium. ‘2RNH +2Na —#" 5 2[RNH] Na* +H) 2RyNH-+2Na HS 208 gNT Na’ + Hat (Wi Action of halogens : Primary and secondary ‘amines react with halogens on heating in the presence of alkali solution to form halogeno-amines, 781 x ann 2 5 any NaOH inaloatkylamine xy R.NH 25 R.NX atkyaine “OM loinc (vil) Reaction with Grignard reagents : Primary and secondary amines (tertiary amines have no H-atom) form alkanes with Grignard reagents by providing hydrogen atom of amines to alkyl group of Grignard reagents 3 ANH, +g —> CH +RNH—Mg—1 Alkylamine 1 SH} MgBr —> 2CH, +C2HsN(MgBr)2 RyNH_ +CH3—Mg—I —> CHy +R)N—Mg—I Diatkyamine (vii) Carbylamine reaction : This reaction is shown by only primary amines (1°). Primary amines on heating with chloroform in presence of alcoholic KOH to form isocyanides (or carbylamines) which possess bad smell. This is a test of primary amines and is used to distinguish primary amines from secondary and tertiary amines. RNH2 + CHCl; +3KOH 2 RNC +3KC]+3H30 Alkylamie (19) (Ale) Alkyl isveyanide CH3NH; + CHCI; +3KOH 2 CH, New +3KC1+3H,0 (Gx) Reaction with nitrous acid: (a) Primary amines form alcohols with nitrous acid (NaNO> +H). Nitrogen gas (ith brisk effervescence) is eliminated and a clear solution is obtained (Lab test of primary amine). (NaNOg + HC1—» HNO, +NaCI) RNHy + HNO, SN HO), py mney 22, Diazonium salt (Unstable) R—OH+N27+HC! or RNHy + HONO —+ ROH +N3t +120 1 Amine Nitousacid Alcohol Methylamine is an exception to this reaction. It does not yield methyl alcohol only but can also form methyl nitrite or ‘Simothyl ether, A, CHNH2 +2HONO —+CH,0N=-O +N; +210 Methyl nite 2CHNH +2HONO—> CHOCHs +2N2 +3120 Dimethyl ether (&) Secondary amines form nitrosoamines which are yellow oily liquids insoluble in water. R{NH+HONO—> NNO + H,0 2 Amine N-NitrosoialiglamineSe (On heating with cone. HCI, they give back secondary RyN—NO+ HCl—> R,NH + NOCI {Nitrosoamines on warming with phenol and a few drops of conc, H2S0, give a brown or red colour which soon changes to blue green. The colour changes to red on dilution, and farther changes to blue or violet with alkali. This colour used for the test of secondary amines ] (©) Tertiary amines react with nitrous acid to form nitrite salts which are soluble in water. These salts on heating give alcohols and nitrosoamines. RyN_+HONO—>[R3NHJ"NO3 —Het, > Amine “Tialyl ansnoniam nite R—OH+R,N—N=O ‘Alcohol Nitrosoanine ‘This reaction (nitrous acid test) is used to make distinction between primary, secondary and tertiary amines. (x) Reaction with carbon disulphide : (a) Primary ‘amines react with carbon disulphide to form alkyl derivative of dithiocarbamic acid which is decomposed by mercuric chloride to give alkyl isothiocyanate. This is Hofmann’s ‘mustard oil reaction and is used as a test for primary amines. NHR aN, S234 5-00 anc: eat NSH All isthiceyante PAmine Alkyl dithio- (Mustard oil smell) carbamic acid +HgS+2H101 Black pp. (b) Secondary amines form dialkyl of dithiocarbamic acid which is not decomposed by mercuric chloride. NR ect, Saees — No reaction R NH S=E=S, Son Phmine SH Dial ditio- ‘catbari eld (xi) Reaction with benzene sulphonyl chloride (Galphonylation) : See separation of mixture of amines. (xi) Oxidation : All he three types of amines undergo oxidation. The product depends upon the nature of oxidising agent, class of amine and te nature ofthe alkyl group present. (@) Primary amines are oxidised with potassium permanganate into aldimine of ketimine which on hydrolysis form aldehydes or ketones respectively. rcH,NH, Ly rc =n 22", rerio + NH, 1° Amine KM04 Aldimine Aldehyde or R,cann, —°_, p,c=nn 2°", p,co+NH; Tramine” 5M®0,”” Keinine Ketone Fe mary ani an do wtp onion a oan through the following sequence of reactions. r—xth- Ph g—naon OL ve—Nno f gata 8" Anno, EE But tertiary alkylamine on oxidation with KMnO, gives comesponding nitro compound. 7 KMa0, RyCNHz +0] ——*>_R3C-NOz_ +H20 Amine ‘Ter nitealtane (b) Secondary amines on oxidation with KMnO, form tetra-alkyl hydrazine and with Caro’s acid (H S05) or H;0 form dialkyl hydroxylamine. Ol, R,N—NRy 4 Tetra-alkyl hydrazine RyNH —2l, NOH P Amine H805 " piatky! hydroxylamine (©) Tertiary amines are not oxidised by potassium permanganate but are oxidised by Caro’s acid or HO, or 03 ‘or Fenton’s reagent to amine oxides. R.NH 2 Amine fo), RN H,SOs sN +[0]—2—5> [R3N +0} Amine 4202 Amine N-oxide (ail) Reaction with other electrophilic reagents : (@) Aldehydes and ketones react with primary amines in the presence of trace of an acid as catalyst to form azomethines called Schiff’ base or anils. RNH, + O=HCR' #, Alkylamine — Aldebyde q RN=HCR’ Schiff's base (Aldimine) I + (CHsNH,+ O=C—CH; -,0,HsN = CHCH; ‘Acisehyde —” Etyideneethylamine (* CH HS oHsN= c< CH; Isopropyideneetylamine Aldehydes and ketones that have a-hydrogen atoms react with secondary amines to form stable enamines (a, B-unsaturated tertiary amine). ° © reap gyn Pore ‘Aldehyde or ketone 2” Amine -H;0) NR? eeu —_, (PTS p-Toluene sulphonic acid)Nitrogen Cont ar ‘The double bond in enamines can also be catalytically reduced to corresponding amines. I I (b)2RNH, +Cl—C—CI—“ > RNH—C—NHR +2HC1 Carbonyl Dialkyl rea chloride (Symmetrical) (© RNHH+0=C=N—R’ —45 RNH—C—NHR’ Amine soeyanste Dialkot wea (Cnsymmetic!) . t CeHsNCO +HNC2Hs —*+C.HsNH—C—NHC?Hs Phenyl isoeyanate 1° Amine N-EthyLN “phenyl urea I C6HsNCO+HN(CpHs)2 —*+ CoHsNH—C—N(CpHs)2 > Anne NN -Diethyl-N ‘phenyl urea (@CpHsNHy + NOC > CyHsCl +Nz +H;0 [Nitrsyl ebloride ttyl ehoride (xiv) 2° Amines react with diethyl oxalate to form oxamic ester in liquid state. C00C Hs CoHs | +H < — C00C2 Hs Cals Die oxalate Ditiylamine @ CoH. CON < = | cooc,H,o785 +C,HsOH Onamic ester (xy) Reaction with HCHO and HCOOH (Methylation): Both primary and secondary amines are methylated by heating with formaline solution and excess of formic acid at 100°C, R—NH +CH20 + HCOOH -2°S, RNHCH3 +CO2 +120, RyNH+CH20 + HCOOH 2°; RyN—CH3 +CO2 +120 (xvi) Reaction with metal ions : Lower aliphatic amines form soluble coordination complexes with transition metal ions like Ag* and Cu*, etc. For example, silver chloride dissolves in aqueous solution of methylamine. it AgCl +2CH3NHp ->|CH;—N-> Ag -N—CH) | CI Silver chloride Methylamine | (ivoluble) H 4 ‘Bis rethylamine) Silver (1) chloride (soluble complex) Similarly, ike NH3, lower amines react with Cu”* ions to form a deep blue solution of soluble coordination complex. CuSO, + 4CyHsNHz —> [Co(C3HsNH3)4]**802° ‘Eahylamine ‘Tetrakis (ethylamine) Copper (11) ‘Sulphate (Deep blue colour) (CE.CuCI, + ANH — [CughHs)4 7°?) (vil) Copereaction: Tertiary amine oxides on heating form an alkene and N, N-disubstituted hydroxylamine if and only there is B-hydrogen atom in it. nce Oa 1,0; oo 3 Amine ores 5 g if _CHs om +(CHs)2NOH ¢ "Hy —NC 5 tee (CH2CH2R" (CH2CH2R" #0, RCH,CH2—N_ “0, RN 30 0; CHR CH; Amine vor] CH;CH)R’ R—CH=CH,+N—OH ‘lke cH; Uses: Lower aliphatic amines are used i) _as solvent in laboratory and industry. (ii) as a stabilizer for rubber latex. Gii) in petroleum refining. (iv) in the manufacture of detergents. (v) as reagents in organic synthesis. Tests for Ethylamine (Tests for Primary Amines) * @ Carbylamine test [Note Thi est is also shown by alin. (i) Hofmai’s mustard ofl test ‘Note? Thisteat isnot shown by sulin bt ally primary amines eapond fo thst, il) Nitrous acid test Note: Aniline does not form alcool with nious acid bu W foes benzene diazonium chloride which shows dye test788 G.R.B. Organic Chemistry for Competitions 14.6 DISTINCTION BETWEEN PRIMARY, SECONDARY AND TERTIARY AMINES (Carbylamine test) 2. Action of CS; and HgCly (Mustard oil test) 3. Action of nitrous sci, green colour with phenol and conc. |givesnitrosoamine which responds to Liebermann’s test. 4, Action of acetyl chloride. Acetyl derivative is formed. |Acetyl derivative is formed, JNoaction, 5. Action of Hinsberg’s reagent. |Monoalky! sulphonamide is formed|Dialkyt sulphonamide is finmed|No action. which is soluble in KOH. which is insoluble in KOH, 3 molecules (moles) of CHsLto form|2 moles of CH 0 form quatermary| One mole of CH3Ito form quaternary [quaternary sult with one mole of salt with one mole of secondary|salt with one mole of tertiary amine. [primary amine amine. 6. Action of methyl iodide. 'LUSTRATIONS OF OBJECTIVE QUESTIONS 1. Which of the following would undergo Hofmana’s reaction 7. Which of the following compounds gives secondary amine togiveaprimaryamine? [CET (Karnataka) 2006] onreduction? TDCE 2004] (@) RCONH, (6) RCONHCH (@) Alkyl nitrile (©) RCOCI (@) RCOOR (b) Carbylamine [Ans. (a)} (c) Primary amine 2. Hinsberg’s reagent is used to distinguish between: (d) Secondary nitro compound [PMT (Raj) 2004] fAns. (b)] (a) 1° and 2° amines (b) 2° and 3° amines ‘8. The basicity of compounds I, Il, III and IV (© Gand) (@) none ofthese CHNH:,(CH)2NH, (CHy)5N, CoHlsCHaNH2, tas. 0] t i tt V 3. Which on reduction does not give primary amine? varies in the order: TPMT (Raj 2004] TAMU (Enge.) 2004; AMU (Med) 2010] (@) cHCN ©) GHSNC (@®) 1>m>m>V > T> tv (©) CH,CONH, (@ Allofthese (©) M>1>0>1V @ W>1>n> it Tans. (6) Tans. ()) 4, Primary amine + aldehyde —> X,, what is X? 9. Tertiary alcohol on treatment with cyanide in presence of (a) Nitro () Nitroso cone. HO, gives corresponding primary amine. This () Amino (d) Imino reaction is called as: (ans) (@) Schmidt reaction (6) Curtis degradation ‘5. Complete the following reaction: (©) Leuckart reaction (d) Ritter reaction -RNH + H280, —>? [Ans ()] (@) (RNH]" HS03 (b) [RNHg J} SOF" 10. The end product of the reaction, (0) ANE H, S04 (@ no reaction Bthylamine 22, (4) °O5, (@)KN(0), is Iams. a a a an : (@) propane nitrile (©) triethylamine Eyamine 1d acetamide are distinguished by reacting © diehylamine (@ propylamine (@) Br, water (6) acidic KMnO, tam. (@] (©) ag.NaOH and heat (4) aq. HCl and heat (ans. (©)Nitrogen Containing Compounds 14.7 CONVERSIONS 1. Couversion of methylamine to ethylamine. (Ascent) Lay HNO, CHyNH, "2 cron 72s citst Oy cen EMS, CH cHa NH Metiyl- Methyl Methyl amine alcohol iodide 2. Conversion of ethylamine to methylamine. (Descent) 0) HNO, 25 CH3CH20H. K;07/H80, ” acetaldehyde thanol (CH3CH2NH Ethylamine * 3. Conversion of ethylamine to acetone. Met cyanide cx,cHo (9, cx,coon. Ethylamine soa, Na, 2+ CH3COcI—+ Acetyl «Aloride “Aosticaed By, CH3NH, <—2—CH,CONH? Methylamine HNO, 640. 640, (oH CH gNH, “2, c, 404 22° cHyco 22"? cH ,coon 2%, (cH4C00),Ca H.CH,COCHS Ethylamine Ettyl alcohol 12804 Acetaldehydle 2804 Acetic acid ‘Calcium acetate Acetone ‘4. Conversion of propionic acid to : (a) Ethylamine, (b) n-Butylamine. soc, Nits By (@ cHcH,cooH 2° cH,cH,coct “3, cH,cH,coNH, 825 CHyCH)NH Propionic acid Propionyl chloride Propionamide Ht Ethytamine NH or C;H,coon—" _,c, Hn one 80 ,@ouey 7S? ial a+ CyHsOH © cxictscoon SEs cH cH,CH1,0H cH cHt,CHBr Es CH:CHCHAN Na+ CoH pines ac bro alcohol ropy Gromade Prop evade FLA, (CH3CH,CH)CH2NH2 5. Conversion of ethylene to 1¢-diémino butane. Byfanine LiAlHy Bry H,C=CH, ——? > CH, Br—CH2Br “*8 NccH,CH,CN ——*» NH,CH,CH,CH,CH,NH Bthylene Clg “Ethylene bromide 6. Cyclohexylamine into cyclopentylamine. Ethylene cyanide ei SNO2t BCL on See, thse, KMn0 44") 2 osc 14-Diamizo butane HOOC—(CH2),—COOH ‘Ape acid sf NH NH ° Os AO 300% a 7. Acie acid into glycine. Br NH NH; ceycoon MERE sn sont sc rac Red P+ Bry ‘COONH, ‘COOH Glycine 8. Cyclopentanol into cyclopentylamine. Sand Ny badTie GR.B. Organic Chemistry for Competitions —“——— ebydration to give cycloalkene, (Common name) : g (CH3NC ‘Methyl isocyanide ‘Methyl carbylamine ie 4 (Methyl isonivle) | (Cabylanino methane) (C)HsNC Ethyl isocyanide. Ethyl carbylamine sh, QO (Ghyll) | (Cabyanin eae) cutive. | Propytiscynide | Prop cabylanige 9, n-butylamine into isobutylamine. Propy! isonitrile) ‘(Carbylamino propane) NaNO} + HCL (CH,CH,CH,CHNHy ~~ 2+ CHCHCHCH20H nH, *+CHSFHCHCH — CHsFHCHACHs OH NH2 (Dominant) Isobutylamine 10, n-Propyl cyanide to n-propylamine. Hoe BO AN ZEEN A CONE: 28D aan 2. CYANIDES AND ISOCYANIDES 14.8 INTRODUCTION Hydrogen cyanide is known to exist as a tautomeric mixture. H—C=N = H-N2C Hence, it forms two types of alkyl derivatives which are known as alkyl cyanides and alkyl isocyanides. R—C=N R—N2>C Alkyl cyanide Ally isoeyanide Compounds, having the formula RCN are called alkyl cyanides or as nitriles of the acid which they produce on hydrolysis by the replacement of terminal ‘ic acid” with suffix ‘onitrle’. According to IUPAC system, cyanides are named as Alkane nitrile, ie, in the name of parent hydrocarbon ‘nitrile? is suffixed. In niaming the hydrocarbon part, carbon of the —CN group is also counted. A ‘Ab cyanide Formals (cnn | HAVEAC mame CHACN Methyl eyanide: | Ethane nitrile (Acetonitrile) CqHSCN | Ethyl cyanide Propane nitrile (Propiononitrile) CSH;CN | Propyteyanide | Butane itile (Buryronitrile) C4HigCN | Butyl cyanide Peatane nitrile The compounds having the formula RNC are called ‘isocyanides or isonitriles. The nomenclature of isocyanides is similar to cyanides. In TUPAC system, the isocyanides are also named as alkane isonitrile. CHsNC Methane isonitrile CaHsNC Ethane isonitrile C3HyNC Propane isonitrile 14.9 ALKYL CYANIDES Methods of Preparation 1. From alkyl halides : The alkyl cyanides are prepared by refluxing an alcoholic sotution of an alkyl halide with potassium cyanide at 100°C. The disadvantage of this method is that a mixture of nitrile and isonitrle is formed. RX_+KCN (or NaCn) OC, Alig (Ale) RCN + RNG Nite Iontile halide (Major product) (Minor product) CjHsBr +NaCN (alc) HS C,HsCN +NaBr Ethyl bromide Propanenitile (Major product) ‘This method gives satisfactory results for primary and secondary halides. However, with tertiary halides, a consider- able amount of an alkene is also formed due to elimination of halides. 2, From acid amides : Pure nitriles are obtained by dehydration of primary acid amides with phosphorus pentoxide or thionyl chloride (SOCI2) or POCIs, ete. Amides are distilled with phosphorus pentoxide, P05. » POH, acy “HO Alkyl cyanide cH,conH, 25, cHycN+ 1,0 Acetamide Heat” Methyl cyanide Industrially, alkyl cyanides are prepared by passing a mixture of carboxylic acid and ammonia over alumina at SO0rC. N05, 500°C. RCOOH + NH —> RCOONH, “2° ‘Acid ‘Anarogies’ 20 ‘alt A RcoNi, “2° , ‘Anide ? HQ” Alkyl ejanide‘Nitrogen Containing Compounds 3. From Grignard reagents : Grignard reageats react with eyanogen chloride or cyanogen (CN)2 to form alkyl cyanides. RMpx +CICN BB RCN +m Grignard < reagent ora (Ctts)x0—MeBr + C1CN HH (CH,), C—O MR Tertiry bay Cyanogen Tenia buy CL smogesnenbronide chloe pln 4. From primary amines : Primary amines are de- hydrogenated when passed over copper or nickel at high ‘temperature to form alkyl cyanides. This is also a commercial method. RCH,NH, S228, Ron + 2H Primary amie 500°C” Alkyl cyanide CH;CH)NH, 22%, HCN + 282 Enhytanine 57°C” Mey cyanide 5. From oximes : Aldoximes are converted into alkyl ‘eyanides when distilled with phosphorus pentoxide or acetic anhydride. The dehydration of aldoximes occurs. H 2,0, R—C=NOH—234 R—CN +H,0 ‘Aldoxime “HO” Alkyl eyanide 6. From alkanes : Another industrial method is the ammoxidation of alkanes. 2CH3CHs +2NH3 +30, —S#"_, 2CH,CN +6420 tice 500-600°C” ane nile Physical properties : (i) Alkyl cyanides are neutral substances with pleasant odour, similar to bitter almonds. The anion derived by deprotonation of nitile is resonance stabilized, CH) —CaN Ht + CH) —CmN CH) =C=N] However, the negative charge on anion is shared by C and NY, since nitrogen is not as electro negative as oxygen, hence nitriles are weaker acid than aldehydes and ketones. ) Lower members containing upta 16 eathon atoms are while higher members are solids. i) They are soluble in water. The solubility decreases ‘with the increase in number of carbon atoms in the molecule. (iv) They are soluble in organic solvents. (¥) They are poisonous but less poisonous than HCN. Chemical properties : () Hydrolysis : Alkyl cyan- ‘des are hydrolysed by both acids and alkalies. On partial hydrolysis by using alkaline H20>, amides are formed while ‘on complete hydrolysis carboxylic acids are obtained. lige 7a RCN —2°_, oon, 2°, COOH. +NHs Aligl Alk-H202 "Amide HY Carbonyic acid cyanide cHscn-—2°, cHsconn,™2°, cHiscooH+NHs Methyl AIK-H;02 “Acetamide H* “Acetic acid paid (i) Reduction : When reduced with hydrogen in presence of Pt or Ni, or LiAIH (Lithium aluminium hydride) or sodium and alcohol, alkyl cyanides yield primary amines. RON + 4H) SESE, ecu wy Alkyl eye Primary eine Chemical reduction of alkyl (or aryl) cyanide using LiAIH, or Na/alcobol to form primary amine is named as Mendius reduction. cHON +4) HES, cHycH NH, ne nite mane However, when @ solution of alkyl cyanides in ether is reduced with stannous chloride and hydrochloric acid at room. temperature, imine hydrochloride is obtained which on sub- sequent hydrolysis with boiling water, an aldehyde is formed (Stephen’s reaction). SaCly/HCL -RCH==NH-HCI m0 nine yoctorse RCHO +NH,CI Aldehyde R-C=N R—Conn +2{H] DBA RCHe=NH HOE, so ACES Fai acon wh DA Ov is Wy scketivemeod emis egent ees only —C=N( and bas. effect on any reducing group,_—_ wi Reaction with. Grignard reagents : With Grignard reagent, an alkyl cyanide forms a ketone which further reacts to form a tertiary alcohol. a [ R—C=N + RMX EM, RC NMEY ‘Alkyl cyanide é z 5 | I — =0+ suemr® C=NH. ae R—C=O+NH Ttmay be noted that like Grignard reagents, organo lithium ‘compounds (R—Li), (due to their high reactivity) also react, with cyanides to form ketone. CH;CH,;C=N+ CH;—Li 2, Propane nitrile Methyl lithium Ether CH; Oo <4, HOM (CH3CH, —C=| RO carci, bc, Bulan-2-00e. Tertiary alobol (5°) Gv) Alcoholysis : When an alkyl cyanide is refluxed ‘with an anhydrous alcohol in presence of cone. HzSO4 or dry HCI, an imido ester is formed, which on hydrolysis with water forms ester. Ni RON + ROH + HCL] R—C—or' Jor 2° — |r ‘Alkyl Alcobol cyanide RCOOR' +NH,Cl ‘Eser Hy804 2CH3C=aN +2C2 HOH +2H,0 24, Eiane nitrile Heat i 2CHy —C—OC Hs + (NH4)2805 ny ethaoaie (¥) Addition of dry HCI gas : Imino and amino chlorides are obtained. A R-CmN+HCI—9 RK Iino chloride on R—C=N +2HCI—> R—C: (vi) Addition of hydrogen sulphide = obtained. s R-C=N+H,S atone Thi aid amide (vit) Reaction with ammonia and primary amines : Amidines are obtained. RC +Nily —> RP Nia NH ‘Amidine If amino cyanide (HzN—CN) is taken in place of alkyl cyanide, the product will be guanidine, R—C=N +R'NHp —> R—C—NHR’ ¥ Amine NH Substituted amidine GRB. Organic Chemistry for Competitions Uses: (i) Alkyl cyanides are important intermediates in the laboratory synthesis of a large number of compounds like acids, amides, esters, amines, etc (i) Nitriles are also used in textile industry in the ‘manufacture of nitrile rubber and also as a solvent particularly ‘in perfume industry. 14.10 ALKYL ISOCYANIDES ‘Methods of Preparation 1. From alkyl halides : The isocyanides are prepared by refluxing an alkyl halide solution in alcohol with silver cyanide. The isonitrile is the main product but small amount of nitrile is also formed. HOH. as ROX + RNC + RCN Alkyi halide” (Alc) Heat” Igocyanide "Cyanide (sonisile) (Nitrile) (Main prod) (Minor product) cH + Agen 24%, Hn + CHCN Metiyl chloride (Az) Heat Mey isocyanide (Main prodet) ‘This method is thus, not suitable for preparing isocyanides and CN“ is an ambident nucleophile. 2. From primary amines (Carbylamine reaction) : Alkyl isocyanides may be prepared by heating primary amines with chloroform and alcoholic potash, RNH; + CHCl; +3KOH 8 RNC+ 3KC1+3H20 Primary sine Choroform (Ale) Tsveyanide 3. From Nalkyl formamides : alkyl formamides ‘when dehydrated on heating with POCI; in presence of pyridine give isocyanides. i R-NH—C_H "°3., p_N2C+H,0 1Wealky formamide Pine Physical properties : (i) Alkyl isocyanides are colourless, unpleasant smelling liquids. (i) The boiling points of isonitriles are lower than corresponding alkyl cyanides. (iii) They are insoluble in water but freely soluble in organic solvents (iv) Isonitriles are much more poisonous than isomeric cyanides. ‘Chemical properties : (i) Hydrolysis : Alkyl iso- ceyanides are hydrolysed by dilute mineral acids (but not by alkalies) to form primary amines. : RN2c + 2H,0-# 5 RNHy + HCOOH Alkyl isoeyanide |, Prmryaine Fore acid In alky|isocyanide (R—N=C:), the carbon atom being, negatively charged, initially attracts cleetrophile (i.e, H”) in acidic medium but epels nucleophiles (/e, —O1‘Nitrogen Containing Compounds a result, isocyanides are hydrolysed only by acids but not by. alkalies. (i) Reduction : When reduced with nascent hydrogen ‘or hydrogen in presence of nickel or platinum or Na/aleohol or metal/acid or LiAIH, isocyanides form secondary amines containing methyl as one of the alkyl groups. NaC HOH HON RNHCH Alkyl isocyanide oF Nior Pt Secondary amine CH —N=c + 4H] 52°", cH NHCHs Matt iseyanide Dimetylamine Reduction with Na/C;HsOH is known as Mandius reduction, (if) Action of heat : When heated for sometime at 250°C, a small amount of isonitrile changes into isomeric nitrile. RNC Het, RCN (iv) Addition reaction: Alkyl isocyanide give addition reactions due to presence of unshared electron pair on carbon atom, RINTIiC: or R-N=C The following are some ofthe addition reactions shown by alkyl isocyanides. RNC+ Xz —> RNCX> Alkyl iminocarbonyl halide Cslogeny RNC+S—> RNCS Alkyl isothiocyanate CHNC+S —>CH3Ncs RNC+Hg0 —> NCO +18 isoeyanate CHNC+2Hg0 —+CH; —N=C=0 + Hig,0 CzHsNC_ +03 —> CrHs—N=C=0 iy iocyanide Ely! ineyaate The famous Bhopal tragedy in Dec., 1984 was caused by extremely poisonous, methyl isocyanate (MIC), ‘Methyl isocyanate is industrially prepared by the action of methylamine with phosgene. Hel CHNH; + COC; “HCL (cH; —NH—cocl Est 1, Odour 2, Solubility in| water 789 LBthyl eyanidesCSH4CN.|: Ethyl ineyanide, epmiitien | ES 3. Hydrolysis by] Yields propionic acid] Produces ethylanine acid | CaHsCN > C)HsCOOH | CHsNC—> C,HsNH2 4. Hydrolysis by|Sameasintest3 [No tion alta 5. Retusion [Gives popylamine "| ives ety! (Primary amine) | methylamine (Secondary amie) 6, Hewing al] Noctfot Changes 10 ebyl sore cyan ILLUSTRATIONS OF OBJECTIVE QUESTIONS 11. Which one of the following functiotal groups undergoes hydrolysis with alkali to yield an acid group? [EAMCETT (Engg.)2004] (@ —CHO (&) —CN (©) —COcH, @ —Br (ns. 12. ‘Neethyl formamide on dehydration with POCI; in presence of pyridine gives: (@) ethylamine () thy eyanide (© ethylisocyanide ——_(@)_- methyl isoeyanide FAs. (6) [Min : Cally NCH FOS CH, NC+ HL] 13, Ethyl isocyanide on reduction with sodium and aleohol gives: (@) ethylamine (b) propylamine (©) dimethylamine (@) ethyl methylamine [ans ) 14, Cyanide isan: (9) Zwitter on () ation (©) ambident nucleophile (4) electrophile [As. (0) 1s, ‘Acid hydrolysis of methyl isocyanide gives: @) CHNH, + HCOOH (b) CHjNH, + CH;COOH (©) CoHsNH, + HCOOH (@) CHNH, + CH;CH,COOH [ans (a) 16. Whioh ofthe following reagents oan be wood to prepare athy! carbylamine from ethyl iodide? (@ KCN (©) AgCN (©) Cucn @ HON Tans.) 17. Acetaldoxime reacts with phosphorus pentoxide to give: @) methyl eyanide (©) methyl cyanate (0 st yee (@) none of these Ans.18. Which of the following products is obtained when methyl isocyanide reacts with chlorine? (@) CH;N=CCl (b) CH;NCI—CCly (©) CICH,NC @ C1,CHNC Ans. (9) 14.11 ALKYL NITRITES AND NITROALKANES. ‘Nitrous acid exists in two tautomeric forms. ‘Corresponding to these two forms, nitrous acid gives two types of derivatives, Le, alkyl nitrites and nitro alkanes. RO—N=0 5 RN] Aly tite Oo Nivoutans ‘The most important alkyl nitrite is ethyl nitrite. ETHYL NITRITE, C)H;0N=O. Methods of Preparation 1. It is prepared by adding concentrated hydrochloric acid ‘or sulphuric acid to aqueous solution of sodium nitrite and ely ol at very fw temperature (°C) NaNO; + HCL~—> NaCl+ HINO; CaHjOH+ HNO, > Cp FgONO+ #20 ‘Ethyl nitrite 2. From Ethyl iodide: Calisl_ + KONO —>CaHs0NO+KI Ethyl iodide Pot. nitrite ‘Ethyl nitrite 3; It if also prepared by the action of nitrogen trioxide, 1203, on ethyl aleobol. 2C3Hs0H +N303—»2C3Hs0NO+H30 Properties: Ethyl nitrite isa gas at ordinary conditions. Ithag a characteristic smelof apples is insoluble in water. It is hydrolysed by aqueous alkalies or acids into ethyl alcohol. C2H,ONO+H,0-%08,,c, 11508 + HNO, ‘When reduced with tin and HCI, it produces ethyl alcohol ‘and ammonia. CaH,ONO + 6H—S2-5 Cy HOH + NH +10 Eat nitrite Small amount of hydroxylamine is also formed. (Cy HsONO + 4H —>C;Hj0H + NH;0H It accelerates pulse rate and lowers blood pressure and reduces hypertension and severe pain of angina pictors so itis used as a medicine for the treatinent of asthma and heart diseases. Its 4% solution (alcoholic) commonly known as “sweet spirit of nitre” is used as diuretic. GR.B. Organic Chemistry for Competitions NITRO COMPOUNDS Nitro alkanes are the derivatives of alkanes. They are isomeric to nitrites (esters). They are classified as primary, secondary and tertiary depending on the nature of carbon atom to which nitro group is linked. RR R RCH2NOz ; CHINO: + R>c—NOy Primary itroalkane —R R © Secondary nitroslkane Tertiary strolkane Irmay benoted that —NO, groups ambident group and is capable of getting attached to the carbon chain through nirogen (RN nitroatkan) aswell as trough oxygen (R—O—N=O, alky! nitrite) atom. The chemical properties of nitroalkanes and alkyl nitrites (isomeric compounds) are quite different and nitro compounds are much more stable than alkyl nitrites. Both are alkyl derivatives of nitrous acid (HNO2 ) which exhibits tautomerism as the two forms are in dynamic equilibrium. H—0—N=0 —= tone (iitrous acid) Nitvite form ‘Nite form R—O—N=0 == RNC Ally nitrite Nitroalkane General Methods of Preparation (Nitroalkanes) 1, From alkyl halides: They are prepared by heating. an alkyl halide with aqueous ethanolic solution of silver nitrite. R—X + AgNO, #8, RNO) + AgY (Ale) Nitroalkane CyHsBr_+AgNO> (ale.) 2&5 Cy HsNOz romosthine Silver nitite ‘Nitoediane 10-15%) Some quacity of aly nite is elo firmed ta this reaction. Itcan be removed by fractional distillation since alkyl nitrites have much lower boiling points as compared to nitro alkanes. 2. Nitration : Paraffins (alkanes) after hexane can be nitrated directly with concentrated nitric acid, ‘The nitration in lower members is carried out in liquid phase or with fuming HNO3 in vapour phase at about 400°C. 3. By boiling aqueous solution of sodium nitrite with achalogeno acids. a-nitro substituted acids are first formed which lose CO, to form nitroalkanes.Nitrogen Containing Compounds NaNO, CHyCICOOH ~——3 CH NO2COOH B85 CHyNO2 +COz @-Chorgcatic N°CT” eNivoncetic acid Nivomettane 4. A recent method is by the hydrolysis of «-nitroalkene with water or acid or alkali. . CHs CH;—C4-cHNO, + HoH EOF Oi, 2. Mat -topopene CH; cH, boo + CH3NO2 ‘Acetone Nitromethane Physical properties : Nitroalkanes are colourless pleasant smelling liquids. Their boiling points are much higher ‘than isomeric alkyl nitrites. They are less soluble in water but readily soluble in organic solvents. Chemical properties : () Reduction : Nitroalkanes are reduced to corresponding primary amines with Sn and HCl of iron and HCI or catalytic hydrogenation using nickel as catalyst RNO, +6H-SMHCL, RNH, +2H,0 Nitroalkane Alain However, when reduccd with a acutral reducing agent (zine dust + NH,CI); nitroalkanes form substituted hydro- xylamines. R—NO; 14H 2 NMS, p_NHOH [All onamine (i) Hydrolysis + Primary nitroalkanes on hydrolysis with HCL or 80% 1504 produce hydroxylamine and carboxylic acid. RCHNO; + H,0 —> ROOOH + NH,OH ‘Secondary ntrolkanes on hydrolysis form ketones +120 2R)CHNOz —ECl_ 22,60+N20+H20 Boiling “Ketone (lif) Action of nitrous acid : Nitrous acid reacts with primary, secondary and tertiary nitroalkanes differently. Primary nitro compound forms nitrolie acid which dissolves in alkali to give red solution. “1,0 R—CH, +0=NOH 2% r— oO. [2 Nitros ho, = Prinaty (1) itt aia R—C=NONa NO2 Red colored sodium salt 701 Secondary nitro compounds give pseudo nitrols which are colourless solids and give blue colouration which does not dissolve in alkali -H,0 Ether or, H+ HON=* No Ethers, a +HON 18 Tao” Blve colour NO, ‘NO; Secondary (2°) Peeudo nitro Tertiary nitro alkanes do not react with nitrous acid, ‘The different behaviour of nitrous acid with pri. sec. and tert. nitroalkanes forms the bases of the Vietor Meyer’s Test, for the distinction of pri., sec. and tet. alcohols. (iy) Thermal decomposition : Upon rapid heating, nitroalkanes decompose with great violence, Advantage is taken of this reaction in the commercial use of nitroalkanes as explosives. HNO, HES Np +003 +3 He (¥) Halogenation: Primary and secondary nitroalkanes are readily halogenated in the o.-position by treatment with chlorine or bromine. Chloropicrin is formed when nitro- methane reacts with excess of Clz in presence of NaOH. Chloropicrin is an important insecticide. 34 Cy No; 222-5 cciyNo2 +3NaCI+3H,0 3NSOH Culorupiccin Br Br By I By R—CH2NO,—2>R—CHNO, —2+ R—C—NO) PNitealkane’ NOH” Monobromo” N!OH” | sitoalkane Br Dibromo sitoatkane Br Br | RCH ae R R 2Nitroatkane ———_q-Bromoderivative (vi) Acidic nature of a-hydrogen atoms (action of alkali) : The a-hydrogen atoms in aliphatic primary and secondary nitroalkanes become acidic due to the electron withdrawing nature of nitro group. In strong alkaline medium, they behave as acid and forms salts. Consequently, they are called pseudo acids. The acidic character is explained on the basis of tautomerism. r) 4 0H R—CH,—N = RCH NC Nitto form NQ- Aciform —Q~ ‘The aci form is weak acid and can form salt with strong alkali.792 «0H « 0Na RCHANC "+ NaOH 9 R—CH=N ‘Acifoas Q- Sodamaa Q> ‘Therefore, primary (1°) and secondary (2°) nitroalkanes dissolve in aqueous solution of NaOH or KOH to form salts. ‘The tertiary (3°) nitroalkanes do not have o-H atom and ‘therefore, they do not exhibit tautomerism. The main reasons for acidic nature of nitroalkanes are: () The strong electron-withdrawing inductive effect of NO; group. (ii) The resonance stabilization of the carbanion formed by the treatment with alkali (removal of proton). Nitroalkanes are neutral to litmus, although 1° and 2" nitro- alkanes are weakly acidic as compared to aldchydes and ketones, they are twice as strong. For example, pK, of nitro- ‘methane is 10.2 while that of acetone is 20. Applications : Sodium salts of 1° and 2° nitroalkanes give aldehydes and ketones respectively on acidification with 50% HSO, at room temperature. This reaction is called ‘Nef-Carbonyl synthesis. Distinction between Ethyl GRB. Organic Chemistry for Competitions a ON 2R—CH, —NO, SH, 2R— CH= NS Niatkane "So, salt of nitvonc acid SO 50% H,$0, EAs, 2R CH= 0 +2NaHSO4 +N20+H30 ‘Aldehyde O- Na 28 —CH—NO> Mh 28,0 NS 2P Nitoatkane No- S076 1,604 ee 4, 28) —C=0 + 2NaHISO4 +N2O+H20 ‘tone ‘Aqueous TiCl can also be used to form aldehydes and ketones in better yield Ta, RCH;NO, —“* "3 , p_cHo 1 Nitatkane ‘Aide Tc R,CHNO, “#73 , 2 Nivoatane Uses: Nitroalkanes are used: @ 8 solvents for polar substances such as cellulose acetate, synthetic rubber, et. Gi) as explosives. (ii: for the preparation of amines, hydroxylamines, etc RCO” Ketone 5 Etl alirite, (C1,0NO) ‘itroethane (C3 H=NO2) CHiN + 24,0 RNO; + 6H —> RNH + 28,0 [Not decomposed, i.e, alcohols are not produced. But it may {form soluble sodium salt, because in presence of alkali the nitro form changes into aci form, which dissolves in alkalies to form sodium salt. 1H oN C8, tN OF MOH, eas, cH ™~o ™~o Primary nitroalkanes forms ntroic acid, which dissolve in alkali fo give red solution. Secondary nitroalkanes yields pseudo-nitrol, which dissolves ‘in all to give blue solution.Nitrogen Containing Compounds ILLUSTRATIONS OF OBJECTIVE QUESTIONS 19, Nitroethane on reduction with zine dust and ammonium chloride gives: @) ethanamine (b) Nethy! hydroxyl amine (©) ethyl nitrite (@) nitroso ethane Tans. ()] 20, Hydrolysis of CHyCH;NO? with 85% H,SO, gives! (a) CHsCH)OH (b) CoHe (©) CHyCH=NOH, @ CH;COon Tne 21, 2-Nitropropane on hydrolysis, with boiling concentrated solution of HCI gives: (@) propane (6) propanal (©) propanone (@) propanoie acid Tans. 0] 22. Primary nitro compounds react with nitrous acid to form nitrolic acids which dissolve in sodium hydroxide to give: [CET (Tamil Nadu) 2001] (@) yellow solution (©) colourless solution tans. @] (b) blue solution @ red solution 23, The different behaviour of nitrous acid with 1°, 2° and 3° nitroatkanes forms the bases of: 24, 28, 26. (@) Victor Meyer's test (6) Lucas test (©) Baker-Malliken’s test (4) Nef-Carbonyl synthesis, Tans. (@} Jn Nef-Carbonyl synthesis, primary nitroalkanes on treatment with NaOH followed by acidification with 50% H;S0, gives: (@) aldehydes ©) ketones (c) ketoacids (d) esters Tans. (a) Ethyl nite on reduction with Sn/HCl gives: (@) C,HsNH + HNO; (©) CzH;0H+ NH,OH {Ans. (©) Which of the following isomerism is exhibited in nitroethane? {DCE 2004] (@) Geometrical isomerism (b) Optical isomerism (6) CgHsNH + #120 (@) CoHsOH+ NaNOp (©) Furctional isomerism (4) Space isomerism Tans. ()] . Which ofthe following isnotnitroproduct?__ {DCE 2004), (@) CoHsNO2 (© CHy a (©) CH;CH,ONO (@) C6Hl,(OH)NO; CHy Ans, (6)# ALIPHATIC AMINES . G Amines are derivatives of ammonia in which one or more H ‘atoms have been replaced by corresponding number of alkyl ‘groups. Primary (1°) amines : R—NH;, CH;NH2, CHj;CH.NH2,C;H)NH, Secondary (2°) amines : R,NH,CHaNHCH3, CpHsNHCH3, C,HsNHC)Hs ‘Tertiary (3") amines : R3N, (CHs)3N, (C2Hs)2NCHs, (CH3)2N—C2Hs, O In addition to the above amines, tetra alkyl derivatives similar to ammonium salts also exist which are called quaternary ammonium salts. For example, RAN*X™, ((CH3)¢N*W, CaHs)sN*CHSCI, ((CH3)4N" JOH” Preparation of primary (1°) amines CAmmonolysis of alkyl halides (Hofmann’s method) : By heating an alkyl halide with an excess of aqueous or alcoholic ammonia in a sealed tube at 100°C. DAmmonotysis of alcohol : By passing a mixture of alcohol and excess of ammonia vapours over heated ahumina or thoria at 350°C. Reduction of nitroalkanes : By the reduction of” nitroalkanes with S/HCl or Zn/HC1 or LiAlH, the —NOz ‘group gets reduced into —NH) group. G Reduction of alkane nitrites (Mendius reaction) : When an alkyl cyanide (nitrile) is reduced by Na/C)HsOH or Hp/Raney Ni or LiAIHy (LAH) or catalytically, the —CN group gets reduced to—CHNH2 group. G Reduction of amides: By LiAlH, or Na/alcohol amides give p-amine containing same number of carbon atoms, CReduetion of oximes : By Na/alcohol or LiAIHy or Hz /Ni gives 1° amine. QHofmann’s . bromamide reaction (Hofmann’s degradation of amides) : By this method an amide is converted into p-amine containing one carbon atom less. ‘The amide is heated with Br2 and concentrated aguevus KOH solution. 1 phthalimide reaction: Phthalimide is reacted ethanolic solution of KOH to form potassium phthalimide which on heating with RX gives N-alkyl phthalimide. It is put to hydrolysis with ditute HCI to form pure primary amine, Decarboxylation of c-amino acids : 'Ba(OH)> gives 1° amine. By double decomposition between Grignard reagents and chloramine (CI—NH,). By heating with IMPORTANT POINTS TO REMEMBER (SUMMARY) GR.B. Organic Chemistry for Competitions Q Hydrolysis of isocyanides or isocyanates : By boiling with aqueous solution of KOH or NaOH gives primary amine. G Schmidt reaction: By treating a mixture of carboxylic, acid and hydrazoic acid (N3H) with cold cone. H S04, & primary amine is obtained. Ritter reaction : It is a good method for preparing. pp-amines having a tertiary alkyl group. This reaction occurs ‘between a tertiary alcohol (or alkenc) and alkyl cyanide (or HCN) in presence of cone. H2SO, to form tert. butylamine ‘through the intermediate formation of carbocation. Reductive amination of aldehydes and ketones : ‘Aldehydes or ketones when reduced with Ni or H2/Raney [Ni in presence of excess of NH3 at about 150°C under pressure forms 1° amine through the intermediate formation ofan imine. Leuekart reaction : Aldehydes and ketones react with ammonium formate or with formamide to give formyl derivative of primary amine which are readily hydrolysed by acid to yield primary amine. Preparation of secondary amines Q By heating a primary amine with calculated amount of RX. O By reduction of N-substituted amides with LiAlH. 1 By reduction of alkyl isocyanides (RNC) with H> in presence of Pt catalyst or NaC HsOH or Raney Ni or LiAlH. By heating two moles of alkyl halide with one mole of NH {in a sealed tube. D,By hydrolysis of p-nitroso dialkyl aniline with boiling, "NaOH or KOH solution. By hydrolysis ofa dialkyl cyanamide with an acid oralkali. Preparation of tertiary amines 1G By heating an alcoholic solution of NH with excess of RX. © By reduction of N.N-disubstituted amides with LiAlHa By decomposition of tetra ammonium hydroxide on heating, By heating ketone with secondary amines on reduction in. presence of Ni catalyst (Reductive amination). Methods yielding a mixture of pri., sec. and tert. amines O Tofmann’s ammonolysis method : A mixture of amines, (0°, 2° and 3°) along with quatemary compound is formed ‘when an alkyl halide is heated with alcoholic ammonia in a sealed tube at 100°C. Ammonolysis of alcohols : A mixture of amines is also obtained when the mixture containing vapours of alcohol and ammonia are passed over heated alumina (Al,03) or thoria (THO) at 350°C. Separation of mixture of amines (1°, 2° and 3°) When the mixture having amine salts and Quatemary ammonium compounds is distilled with KOH solution, theNitrogen Containing Compounds mixture of ‘three amines distill over leaving behind non-volatile quaternary salt in the distillation flask. ‘The amine mixture may be separated by the following ‘methods. Oi Fractional distillation : The boiling points of 1°, 2° and. 3° amines are quite different and thus these can be Yébarated by fractional distillation. This method is used satisfactorily in industry. CHofmann’s method : The mixture of three amines is tented with diethyl oxalate The 1° amine farms a dialkyl oxamide, 2° amine gives aliquid oxamic ester and 3° ‘amine does not react. The reaction mixture is subjected to fractional distillation. The 3° amine distlls over and forms the first fraction. This is followed by oxamic ester which forms the second fraction. The solid oxamide remains behind in the distillation flask which on hydrolysis with KOH and then distilled to get pure amine. The oxamic ester is hydrolysed by boiling with KOH solution and distilled when pure 2° amine is obtained. CO Hinsberg’s method : It involves the treatment of the ‘mixture with benzene sulphonyl chloride, ie., Hinsberg’s reagent (CsHsSO2C). The solution is then made alkaline ‘with aqueous KOH solution where 1° amine forms N-alkyl benzene sulphonamide (soluble in KOH). The 2° amine forms .N,N-dialkyl benzene sulphonamide (insoluble in KOH) and 3° amine does not react. The above alkaline ‘mixture of mines is extracted with ether. The 3° amine and ialkyl sulphonamide passes in etheral layer while salt of alkyl benzene sulphonamide remains in aqueous layer. The etheral and aqueous layers are separated. ‘The aqueous layer is acidified with dil. HCl and hydrolysed by heating with conc. HCL The hydrochloride formed is then distilled with KOH when 1° amine distills over and collected. ‘The etheral layer is fractionally distilled when first ether distlls and the other fraction is hydrolysed with conc. HCI followed by distillation with KOH solution gives pure 2° amine. Physical Properties : Amines are polar compounds like NH and have comparatively higher boiling points than ‘non-polar compounds of similar molecular masses. This is due to the presence of intermolecular H-bonding. The boiling points tise gradually with incicase of molecular ‘mass. Lower members are soluble in water. This is because the amines are capable of forming H-bonding with water but the solubility decreases with increase of molecular mass. Chemical properties : The main reactions of amines are due to the presence of a lone pair of electrons on nitrogen atom. Basie nature: Amines form salts with mineral acids (HCI ‘or H2S0,) which on treatment with NaOH liberates parent amine, Amines combine with water to form alkyl ammonium hydroxides which dissociate into ions. Oi Alkylation: When amines are treated with alkyl halides, the H atoms of amino group are successively replaced by alkyl groups. Cl Acylation : Primary (1°) and secondary (2*) amines react with acid chlorides or acid anhydrides to give acyl derivatives (N-substituted amides). Tertiary amines do not react since they do not have replacable H atom. 11 Reaction with sadium «19 and 2° amines form sovtinm salts when heated with sodium. Ci Action of halogens: 1° and 2° amines react with halogens ‘on heating in the presence of alkali to form mono and di halogeno-amines. Reaction with Grignard reagents ; Primary and secondary amines form alkanes with Grignard reagents by providing H-atom of amines to alkyl (R) group of GR. CCarbylamine reaction : Primary amines on heating with CHC! in presence of alcoholic KOH produce isocyanides (Carbylamines) which possess pungent (unpleasant) odour. Itisa test of primary amines only and is used to distinguish 1° amines from 2° and 3° amines. Gi Reaction with nitrous acid (NaNO3 + dil, HCD: Primary amines form alcohols with nitrous acid, HNO, (NaNO) + HCI) and N 2 gasis eliminated. (A distinction between I", 2° and 3° amines). Gi Reaction with carbon disulphide : . Primary amines on warming with CS to form alkyl derivative of NOH). G© Tertiary amines are not oxidised by KMnO4 but are ‘oxidised by Caro’s acid or H302 or Os or Fenton’s reagent to amine oxides. Condensation with aldehyde: Primary amines condense with aldehydes to produce aldimine (Schiff’s base). O Reaction with carbonyl chloride (Phosgene) : Primary amines on heating with carbonyl chloride (COCI2) form, N’-dialkyl urea. Secondary amine forms N.N.N’,N’-tetra alkyl urea. Reaction with alkyl isocyanate: Primary and secondary amines on heating with alkyl isocyanate form corresponding substituted urea.