ORGANIC CHEMISTRY TOPIC Reduction, Oxidation & Hydrolysis CONTENTS. Reduction. Oxidation HydrolysisReduction, Oxidation & Hydrolysis (A). REDUCTION At Az @ Introduction Reduction covers both the addition of hydrogen (or deuterium) to a double bond and the replacement of an ‘atom or group by hydrogen (or deuterium). In other words, reduction means hydrogenation or hydrogenolysis. Reduction can be carried out in following ways: Catalytic hydrogenation Metal/proton (acid) reduction Metal hydrides reduction Miscellaneous Reductions Catalytic hydrogenation : Hydrogenation using H,(gas) on metal surface or other suitable catalysts called catalytic hydrogenation. A catalyst provides a new pathway for the reaction that involves lower free energy of activation . Nocatalyst (hypothetical Catalyst present (sua mltstop) aH? =— 120K met Free 50%, >> 46%, co Heterogeneous hydrogenation catalysts typically invotve finely divided platinum, ‘The catalysts used can be divided into two broad classes, (a) Heterogeneous catalysts and (b) Homogeneous catalysts, both of which mainly consist of transition metals and their compounds Heterogeneous catalysts : (catalysts insoluble in the reaction medium) Inheterogeneous catalytic hydrogenation catalysts are used in powdered form. Raney nickel (Ni), Palladium ‘on charcol (Pd/C), Platinum metal or its oxide are common Heterogeneous catalysts. Facts of catalysis: (i) Substrate molecules are assumed to undergo homolysis into atoms at the surface of the catalyst. (i) The substrate is chemisorbed on the surface of the catalyst and hydrogenation takes place. (iii) The process is exothermic, (WH, and D, mixture is used with a Pt catalyst, the two isotopes quickly scramble to produce a random ‘mixture of HD, H, and D,. (No scrambling occurs in the absence of the catalyst.) The product has both D and Hatoms).Catalytic Hydrogenation : [HJPd (C)] Raney nickel (Ni), Palladium on charcol (Pd/C), Platinum metal or ils oxide are commonly used for catalytic hydrogenation, ‘They reduced the organic functional groups as given inthe table. Catalytic Reduction of Functional Groups Using H,/Pd{(C). Ni or Pa R-CH=CH-R+H, R—CH,—CH,—R + heat Substrate Product ROOCI RCH,OH RNO, RNH, RC=CR RCH,CHR RCHO RCH.OH RCH=CHR RCH.CHR RCOR RCHOHR RG=N RGH,NH, Following groups are reduced under drastic conditions RCOOH RCH.OH RCOOR’ RCH,OH + ROH RCONHR’ RCH.NHR, Note: Stereochemistry of catalytic hydrogenation : The above reaction is syn addition (addition takes place from the same face of alkene or alkyne). (i) Homogeneous catalysis : (catalysts soluble in the reaction medium). Ituses reactants and catalyst in the same phase. Both hydrogen atoms usually add from the same side of the molecule. Common ‘example : Use of Wilkinsion catalyst. (ii) Lindlar’s catalyst : [H/Pd (CaCO, quinoline)] itis poisoned palladium catalyst. Itis composed of powdered calcium carbonate coated with palladium and poisoned with quinoline. It carry out partial reduction of alkyne to alkene and acid chloride to aldehyde. Stereochemistry : Syn addition. CH, cH, CH, -CH,—C=C-CH, —Hatindars cast a \ yy (synadition) ame is-alkene (iv) Rosenmund catalyst : [H/Pd (BaSO,, quinoline)] Hydrogenation in presence of H/Pd/BaSO, is called Rosenmund Reduction. It reduces alkyne to alkene and acid halide to aldehyde. Its poisoned palladium catalyst, composed of powdered barium sulphate coated with palladium, poisoned with quinoline or sulphur. Stereochemistry : Syn addition (@) CH,-C-C-CH,_HaPd, BasO..S HON CH, 1, t.Pd. BaSO.S = a) cis-2-butene ° ©) ch, bg) ARPES CH,-CHO Note: Nickel boride Ni,8 (P-2 catalyst) (made from sodium acetate and sodium borohidride) is an excellent alternative catalyst for the conversion of alkyne into alkene. Stereochemistry : Syn addition.AS 0 Gi) Metal/proton (acid) reduction : Reduction by dissolving metals is based on the fact that the metal acts as a source of electrons. Step -1 : Metals give electrons to the electrophilic species and form anion Step-2 : Proton is abstracted from the acidic source. A-B—25 A+B or At+ Bt > A+ B-H A=B—8, :A-B or AB: 5 at BH Birch reduction [Na or Li/NH,(liq.) or (ethyl alcohol)] : Alkyne and Aromatic Compounds are reduced by Na or L/NH,, ‘Alkynes are reduced to trans alkene. R wait, Pag -c=c-R MME “Yo=c: i R-C=C-R DE= CK antiadcition) H Stereochemistry : anti addition, Benzene ring is reduced at 1, 4-position. ‘Typical example of reduction for aromatic system Presence of alkyl, alkoxy, amines reduces the benzene ring at ortho position. (electron releasing group - R, - OR, - NH,) y Nain H Beit iy H Presence of nitro, cyano, carboxylic or aldehyded group reduces the benzene ring at ipso position. (electron withdrawing group Ne =NO,, - COOH, - CHO, - CN) vase ax Bouvealt-Blanc reduction [Na/C,H,OH] : Reduction of aldehydes ketones or esters by means of excess of Na/C,H,OH or n-butanol s called Bouvealt- Blanc reduction reduction. CH.CHO NAIGHOH, cH.cH.oH poetaldenyde Ethanol(ii) Stephen’s Reductions : [SnCi/HCI] When reduction of compounds is carried out with acidified stannous chloride (SnCL/HC!) at room temperature, imine hydrochioride is obtained which on subsequent hydrolysis with boiling water gives aldehyde. This ‘specific type of reduction of nitrile is called stephen’s reduction. LiAIH, or Na/C,H.OH H.NH, ee Rec (Complete Reduction! fone) (i) SMCL, HCI fii) HO. CHO, (Parial Reduction) Ridchyde (iv) Clemmensen’s Reduction : [2n-Hg/Cone. HCI] (Aldehyde and ketones in absence of acid sensitive groups). Itis used to prepane alkanes from carbonyl ‘compounds. Spo Rate, Don, 4 4 5p * (@) R-cHO HREM, RCH 44,0 Oo I ;n-Haeone. ) RGR RISE ROHR +H,O. Clemmensen reduction is not used for compounds which have acid sensitive group. [Like Alcohol, Alkene, Alkyne, Ether, Ester, Amides & Cyanides]. NoteA-4 Metal hydrides reduction Certain complex metal and boron hydrides, are important reagents for reduction. (@) —_LiAIH, (LAH) Lithium aluminium hydride (LiAlH,/ Ether or THF]: LAH is most common and versatile reagent. It is sensitive to protic solvent and therefore used in ether. aw, | UAW, | AM, [LaiNecess[UAMJecess] uAK, | UA, | WAM, | LAM, | LAI, | LAI, Reactant [Aaehyde|ketone [act [rcanyarae [Asaenorae [ecrr _[ovanae ame [socyense [Nao Product [raiconat fe aconar [rracono: —[iraonai _[rravoro [racer [iranne [ramne [anne _[1ranne Note : Alkene, alkyne, benzene rings are not reduced by LiAIH, in ether but itis reported that () double bond can be reduced by LiAIH, / THF in cinnamic system. (LAI “THE Ph-CH=CH—CHO nico > Ph-CH,-CH,-CH,OH Gi) Sodium borohydride [NaBH,/C,H,OH or Ether] : It is more specific than LAH as a reducing agent. It reduces ketones and aldehydes to the corresponding alcohols without affecting other functional groups, reduces acid chlorides to aldehyde. It does not reduce any other derivative of acid. Itis effective even in protic solvent ike alcohol. NaBH, | NaBH, | NaBH, NaBH, Reactant |Aldehyde [Ketone __|Acid chloride Product |1° alcohol |2° alcohol _|Aldehyde 9 ,H Gil) Diisobuty! Aluminium Hydride (DIBAL-H/Inert solvent] : Diisobutyl aluminium hydride is parallel to LAH (Lithium aluminium hydride) as a reducing agent but it is more selective DIBALH | DIBAL-H | DIBALH | DIBALH | DIBAL-HiHiot| DIBAL-H/Coid| DIBAL-HiHydrolysis Reactant [Aldehyde [ketone —_|Acic ctioride [Ester Ester loyanide joduct [1 atconar —|z°atconot freatconor [1° aiconar__|Aicenyde __[ardenyae WAI -THE (a) Ph-CH=CH—cooc,! cr) [ms Ph-CH=CH—CH,OH Ph-CH,-CH,-CH,OH+C,H,OH (e) —_ ByDIBAL at ordinary temperature esters are reduced to alcohols but at low temperature esters are reduced to aldehyde.AS @ Note: Gi) ° 4 DIBAL CHC -OcH, TBaane2se” CHLCH,OH ona sham vo CH.CHO (©) LAH reduce RCN to amine but DIBAL is found to be reduce it to aldehyde. Ny —AlHs-THE CH,-c- 20 [=e psc CH,-CHO Miscellaneous Reductions CH,-CH,-NH, Wolff-kishner reduction [NH,NH,/KOH] Used to prepane alkane from carbonyl compounds N, NH,—NH,/KOH NH.NH,/KOH =F =O ~eing igh boting oH REHO & RCH, L, schon tom aneen ~ b * \Wotf-kishner recluction is not used for compounds which have base sensitive groups used to reduce carbony! & carbony| group. [Halogens, Acid halide, Esters, Anhydride, Cyanide] By Red P & HI: Used to prepare alkane from acid, acid derivatives and carbonyl compounds. Red P &HI| RedP&HI|RedP&HI| RedP&HI | RedP&HI | Red P&H Reactant [Aldehyde |Ketone _|Acid chloride | Acidanhydride [Ester Product [Akane [Alkane [Alkane Jaikane atkane R-Gon REST =EL RH, (yr-c-oSS8P FHL, RCH, fe} t + PH (or-c-o8r —ReSP #4, R_cH, (R-g-n BEE H R_cH j i Red P +H (e)cH,CH=0 _RedPotl CHCH, (0.08, -G~cH, SF" CH,CH,CH, Meerwein-Pondorf-Verley reduction (Reduction by isopropyl alcohol and aluminium isopropoxide) ; tis selective reduction of ketones to alcohol, even in presence of other functional groups using Aluminium isopropoxide in isopropy! alcohol R-G—R'+CH.-GH-CH — Ro GH RF cH 6 Cl . —<—— I OH OH ° on ANOCHMe,), + CH, ~ GH CH, —— + CH. -G-CH, OH °(B). OXIDATION INTRODUCTION 1. oxidations defined as the addition of oxygen (electronegative) element to a substance or removal of hydrogen (electropositive) element from a substance. or 2. Oxidation of an organic molecule usually corresponds to increasing its oxygen content or decreasing its hydrogen content. ° °O RoHOH Hat ROH Il a Faye R-6-0n 3. Oxidation of an organic compound may be more broadly defined as a reaction that increases its content of any element more electronegative than carbon, Replacing hydrogen atoms by chirine atoms is an oxidation OO, ©, _O , Ar—CH, <= AICH, Cl <== AICHE), == AIC, When organic compound is cade someting is the oxidising agent is reduced. When an organic compound is reduced, something else - the reducing agent must be oxidized. OXIDATION OF ALKANES Different products are formed by the use of different oxidising agents or different reaction conditions. Chemical oxidation with KMnO, or K,Cr,O, : Alkanes are usually not affected by oxidising agents like KMnO, or K,Cr,0,. However, alkanes having tertiary hydrogen are oxidised by these oxidising agents to an aleotol ccrycn KO cH con (isobutane) (Tertiary butyl alcohol) OXIDATION OF ALKENES AND ALKYNES Bayer reagent [cold dilute alkaline KMnO, solution] : Bayer Bayer Bayer Reagent | Reagent _| Reagent Reactant |Alkene JAikyne Product |Vicinal diol |Diketone Stereochemistry : syn addition. Both OH groups add from same stereochemical side. Genera Recon C=C + ro, +"0H HO—> G6 — (or 030, 10) ki a (syn etionqi) Gi) Ext Ex.2 Ex3 Ex4 4) Q ee Shee oO oO ‘Osmium tetraoxide in alkaline medium [0s0, /H,0,] : Simitar to Bayer reagent. (Os0, /H,0;| Os0, /H,0, | Os0, /H,0, Reactant |Alkene JAlkyne Product |Vicinal diol |Diketone Stereochemistry : syn addition. O 0804.0. Cyclohexene Cis-Cyclohexane-1,2-diol Oxidation with acidic KMnO, [kMn0/H']: Storeochemistry : syn addition. When alkene & alkyne heated with KMInO, in acidic orn alkaline medium; following changes takes place. KMnOJH" | _KMnOJH" | __KMnOJH™ KMnOJH" | _KMnOJH" | _KMnOJH™ Reactant |=CH. group |=CHRgroup |=CR:R.group | =CH group CR group Product |CO. RCOOH JO=CR.Ragroup [co IRCOOH ICarbon dioxide [Carboxylic acid [Ketone Carbon dioxide [Carboxylic acid RCH= CH, OL, CO, +#,0+RCOOH RC=CH 91, CO, +H,0+RCOOH RC=C-R Il, 2RCOOH Zo KMn0, on on Warn + ORR cone. Ne _Kvtno, Warm * coon 02+ H,0 T er roeExé ExT (iv) ° ° (1) KNnOy, NaOH, t l (Ht cH,-c ~CH,CH, (CHy -C-OH + HO-C-CH,CH3 ° (1) Kn, NaOH, {Kin 4, NAOH, i ae CH.CH,CH, -C-OH + CO,1 +H,0 CH,CH,CH,-C = CH Oxidation with peroxyacids : An alkene is converted to an epoxide by a peroxyacid. [a carboxylic acid that has an extra oxygen atom in a ~ 0 ~ O — (peroxy) linkage] oO ‘0. oO 1 SfN\y 4 General Reaction >C=C<+R- 6 -0-{G}-H—» >é—CC + R-G -0-H (asi Epoxide ‘The epoxidation of an alkene is clearly an oxidation, since in oxidation, an oxygen atom is added, Peroxyacids are highly selective oxidizing agents. Some simple peroxyacids (sometimes called peracids) are shown below: 0 1 : t cH—C—o—!6'— c—o— peroxyacetic acid Peroxy benzoic acid RCOH = Peroxy acid HCO.H = PFA (Performic acid) CH,CO,H = PAA (Peracetic acid) Ph-CO,H = PBA (Per benzoic acid) OH =MCPBA (Metachloro perbenzoic acid) CF,CO,} = TFPAA (Titluoro peracetic acid) Stereochemistry : anti addition in diol formation. I oH 2 wo, bf General Reaction > C=0< +R—C—0oH —» —C—C— HO, _c_¢e t Y J | ay Rect RPO HoH RHO Rc Bon “ OH Ant edton 7 [Aa Power, ou cu ROMO oy by Barren UsH ROR GH Auton HOX. OHPFIH.O. H L_QHOX oH} ch- ROO, ec dak (3) ii) NaOHiA. or HO’ ou tationNote: The more highly substituted olifinc bond is more nucleophilic and therefore reacts faster with the peroxyacid than the less susbstituted double bond. CH, I H, cH,-b¢-cH-cHzcH, OOH, th t “HCO,” CH,-G--CH,—CH = CH, Hs VA. More Less SCH, substituted substituted oH, L (1) RCO,H (1) RCO.H ext /\ ORO HOH 4 enantiomer Ex -ono 4 iH (a. @AO wot on Trans RO Ton oH, cH, (v). Oxidation with ozone (ozonolysis) : Alkene & Alkyne Like permanganate ozone cleaves double bonds to give Ketones and aldehydes. However, ozonolysis is milder, and both Ketones and aldehydes can be recovered without further oxidation. Reductive Ozonolysis Products (0 3/Zn, H20) O,fZn, H,0] OfZn,H,0 | OsZn,H,0 | OyZn,H,O | OJZn,H,0 | Os/Zn,H,0 Reactant |=CH. group ]=CHRgroup |=CR,Regroup |=CHgroup | =CRgroup Product |HCHO JO-= CH Rgroup |0=CR,R_ group [HCOOH IRCOOH Formaldenyce |Aldehyde Ketone Formic acia [Carboxylic acid Oxidative Ozonolysis Products OsH0, | OHO, OsH.0, OJH.02 OHO, OsH;02 Reactant |=CH, group |=CHRagroup |=CR.Regroup |=CHgroup | =CRgroup Product |CO. IRCOOH JO=CR:Ragroup |CO, IRCOOH [Carbon dioxide [Carboxylic acid [Ketone [Carbon dioxide [Carboxylic acid EX16 C,H, (A) —2xt89 , Acid (B) Identity (A) and (B) in the above reaction Sol. (A) (8) ‘COOH Dao] > x17 Acertain hydrocarbon has the formula C,H... Ozonolysis followed by hydrolysis gives CH, (CH,),CO,H and succinic acid as the only product. What is hydrocarbon Sol. DU=4 Molecular structure must be CH,CH,),C=C-CH,-CH,-C-C(CH)-CH,B-4. Oxidation Reaction of Alcohols : on Prodi oan Weak onan ge Song ondsing aon acchotor ecnday acho ine Kane PCC" =(Pyridnium Chlore Chromste) in CHC, (G)+Hic1+c10, _nensas sown oO creo, \ Hq PDC** = Colin's Reagent (2C,H,N.CrO,) X,+NaOH*" = (NaOX sodium hypohalide) Oxidation Product of Alcohor2 Veryery Strong oxiising agent | Copper & heat | Oppenaurs Kino est as oniing agent | oxidation" 4° alcohol ae Carbone aed nieryase | Aldehyde ; Tiare o alcohol or Secondary alcohol Catboxytic acid Ketone Ketone ; Mure of 2° stato! or tetiary alcoho cate Detycatetoakene @ “MnO, (Selectively oxidised allylic and benzylic alcohol into aldehyde and ketone) “Oppenaur's oxidation Base + Ketone (solvent) K(CH,),CO*/{Al(CH,),CO"], + (CH,),CO/ CH,COC,H,/ Cre Selectively oxiised secondary alcohol into ketone. Acidic KMnO, & K,Cr,0, as oxidising agent : Aldehydes are oxidised to carboxyic acid having same number of C atoms as aldehyde. HCHO+[0] —» HCOOH; RCHO+[0] — RCOOH Ketones are oxidised with dificuly. They are oxidised only on heating witha strong oxidising agent Cr,0% +H* OrkMnO +H In case of mixed or unsymmetrical ketones the >C = O group remains with the smaller alkyl group. (Popott's rule) 9 ch, cn, +101 CH,COOH + CO, +H,0 ch,coch,cH, 21, 2cri,coov; cH,coct,cH,ch, —[0l_, cH, cooH + CH, CH, COOHMechanism (with Cr‘* oxidising agents) : Gi) ii) ° il 1) 010, + ,0——H,010, «HO - Gro ° wre t aad on, R- Bo OH seg 04H,00, 6 A 4 unstable 4 a f iy R-6GG Bo a Pp] 2% snd el 160, x i as Gerdiol unstable Remarks : (1) Primary alcohol forms a chromate ester with chromic acid. (2) The chromate ester decomposes in 2 slow step with the elimination of a-hydrogen. So the first oxidation product, an aldehyde is obtained. (3) Inaqueous medium, aldehyde forms a gemdiol (hydrated aldehyde). itis further oxidised to an acid by similar mechanism (4) The following reactivity orders can be explained by this mechanism Rate of Oxidation (a) RCH,OH > R,CHOH > R,C—OH (inert) gH, (b) CH,OH > CH, ~ CH, - OH > CH,- CH - CH.~ OH (Steric factor) (©) R~ CH,OH > R -CD,OH (Bond Energy: C-H<«C-D) (a) RCHO > RCH,OH (€) RCHO > RCDO With Tollen’s reagent : RCHO (aldehydes) can be easly oxidised to RCOOH (except HCHO that can be oxidised to CO.) by weak oxidising agents like ammonical AgNO, (Tollen's reagent) hence they are better reducing agents. ‘Aldehydes reduce Tollen’s reagent toAg and appears inthe form of sliver miroris called silver-mirror test. Itis given by all aldehydes and reducing sugars. RCHO + 2[Ag(NH,)," ]+30H- —*-» RCOO- + 2Ag 4 + 4NH, + 2H,O. With Fehling Solution : Aldehydes (except benzaldehyde) reduce Fehling’s solution (Cu® reduced to Cu‘) which is an alkaline solution of cupric (Cu) ion complexed with tartrate ion RCHO + 2Cu* +30H" —4, RCOO-+ Cuz0} +2H,0 redppt. Aldehydes also reduce Benedict's solution (Cu** complexed with citrate ion) to Cu*B-5 Oxidation reaction of diols (i) HIO, oxidation : (Oxidation by lead acetate is similar to HIO, oxidation) Mechanism RoR Lo if R R R-t6-R p-bod-n bn) (bn Hid. ads sh 2H0, RC 4 CR akon 8 | a “ : Oe 0 Se ow Ne of “ou cycle periodate ester 9 Hi on I-oF aio, ot? OH-| OH No on Remarks (1) HIO, (periodic acid) oxidises vicinal diols (1, 2-diols). (2) Itbrings about oxidative cleavage ot vicinal diol {@) Itcan also oxidise «-hydroxy carbonyl compound, «-dicarbonyl compound and «-hydroxy acid (4) HIO, forms a cyclic periodate ester as an intermediate. So the two - OH groups should have syn- conformation. (6) In cyclic diols only cis-vicinal diols are oxidised. Trans isomers are not oxidised. Ex General reaction R-CHECH TCHR HHO. , HI. , R_ CHO + HCOOH +R - CHO OH OH OH * ex2s (1)(R-oH,-o- R-CH=CH-CH,-O# (Allyfaleohob R-cHo-sR— coon (2) eas (2) __KNnOJIFERCOOH + Mn... (C=C, 1) KCL SQ COOH + Cr*...4C = C, CHC oxidised) at ow © a RCOOH + cr" (C=C, CmC oxicises) (5) C1/Acetoneiwater, RCOOH.....(C = C, C=C not oxidised) (6) Pc) cro,\c#,cL/Pyridine “cto, (7) Guta (300 ~ 350°C) (C=C, CC not oxidised) RHO vm = ©, CHC not oxidised) (dehydrogenation) (8) Oppenauer Oxidation | ——>rost seloctive oxicises aleohol to aldehyde, ©) no, [————>r- CH= cH-cHO 0 CH, =CH,-CH,-OH eo) ca CH, =CH,-CH =O dehydrogenation . (2H) " . 3 CH,-CH-CH, eae dehy ti ~ on fous jas hi ha Ex.22 Write the product of (X). OH, OH= CH GH-c K,C1,0; (1) H,80, Poe. @ x. _Oppenauer oxidation > CH, CH, -OH 1H (%) cH, T onnece- go, yo , on =0H—§ 0H, oko CH, CH = CH- & CH, - CHO @ CxO /aq Tyacetone” CHs #o ch coo I °‘SNo._] Oxidising Agent Reactant Product 1. | Beyer Reagent 1% very dilute, cold and | Alkene Cis-ciol alkaline KMnO, solution | Alkyne 1, 2-Diketones 2. [Jones Reagent | CrO,+H,0 or H.CrO, | 1-Alcohol ag 2: Alcohol Ketones 3. | Golins Reagent | CrOs+Pyridine or “Alcohol ‘Acid Used in (CH,Cl,) | CrOs.2py 2 Alcohol Ketones, Without over- oxidation 4 | Corey-Reagent | NazCr,0; + Pyridine __| Allylic T’Alcohot op Used in (CH,Cl,) | and HCI unsaturated Without over- aldehyde oxidation Allylic 2°Aleohol op unsaturated Ketones, 5. | PCC (Pyridinium | CrO,+6MHCI+ Py or | 4Alcohol ‘Aldehyde Chloro Chromate) _| (pyH" CrOs CI") 2 Alcohol Ketones, 6 MnO, MnO Allylic 1°Aleoho! of cis & trans allylic unsaturated alcohols are oxidized at aldehyde the same rate without | Aliyie 2"Alcohot of isomerisation unsaturated Ketones 7. | Peroxides & Per- | m-chloroperbenzoic__| Alkene Epoxides: acids acid, Peracetic acid, [RAN RiN-O Hydrogen peroxide Ketone Ester Cyciic Ketone Lactones: & | Se0; ‘S80; + HZ0 Electron deficient « carbon | Diketones of aldehyde/ ketones 9. | Lead Tetraacetate | Pb (CHsCOO). Cis diol Cleaves to aldehyde, keone/acid 70._| Per lodate ion or _| 10, or HIOy Cis diol Cleaves to per iodic acid aldehyde, keone/acid 71._| Tollen’s Reagent _ | Ammonical AgNO; ‘Aldehyde Carboxylic, solution acids 72. | Fehling Solution | CuSO, + Sodium- ‘Aldehyde Carboxylic Potassium tartrate acids solution 13. | Benedict Solution | CuSO, +Potassium | Aldehyde Carboxylic, citrate solution acids 74 [cua 7Alcohor Aldehyde 2 Alcohol Ketones ‘3 Alcohol ‘Alkene(C). HYDROLYSIS. ) (i (iv) ™ Introduction : Hydrolysis is a chemical reaction or process in which a molecule splits into two parts by reacting with a molecule of water.(H,0). One of the parts gets OH from the water molecule and the other part gets H' from the water. Such reactions are endothermic. This is distinct from a hydration reaction, in which water molecules are added to a substance, but no {fragmentation of molecule/species occurs Such a process is exothermic. Hydrolysis of an ester : Hydrolysis of an ester involves breaking off an ester link. It can takes place in p *So-k ester linkage (a) Mild acidic medium : Dilute H,SO,, dilute HCl (bp) Strong alkaline medium : Aqueous NaOH or KOH and heat. one hydrolysis product contains a hydroxyl functional group, while the other contains a carboxylic acid functional group. 9 LO, oO a i é R-G iia) + RNG ‘O—R O—H Hydrolysis of an anhydride : The hydrolysis of acid anhydride produces two carboxylic acids. 9 9 O° fe ea we 1 HQ |g HR d eR Nof'sR Non Non Hydrolysis of acid halide : Hydrolysis of an acidhalide results into a carboxylic acid and hydrogenhalide. Only the carboxylic acid product has a hydroxyl group derived from the water, Hydrohalic acid product gains the remaining hydrogen ion. ° R J Hn gy RR +HCI 4 ‘OH Hydrolysis of acid amide : Hydrolysis of an amide results into a carboxylic acid and an amine product or ammonia, only the carboxylic acid product has a hydroxyl group derived from the water. The amine product (or ammonia) gains the remaining hydrogen ion. ° I HON RG RE ann, a“ * ‘oH(vi) Co) (x) (xi) Hydrolysis of cyanides : Cyanides has 3° nitrogen bonded with SP carbon.On hydrolysis C-N bond dissociates to produce ammonia and carboxylc acids. It is carried out in acidic medium. ©. ° tH r-ctn SHH an, OH Hydrolysis of isocyanides IsoCyanides has 4° nitrogen bonded with SP carbon and one ofthe alky/ary! group.On hydrolysis C-N bond dissociates to produce Primary amines and formic acids. is carried out in acidic mecium. °. vg a Ni pongo I Ey on Hydrolysis of Ethers : Ethers has R-O-R group.in strong acidi¢ medium (HI or HBr) in hydrolysis to produce 2 equivalent of alcohols. Hemiacotals and Acetals has R-O-R group. Hemiacetals are unstable and get hydrolysed to aldehyde/ketones even in aq medium. However acetals / Ketals are stable and hydrolyse only in strong acidic medium (HI or HBr) to produce 2 equivalent of alcohols. and one equivalent of aldehyde/ketone. Acetals are often used as protecting groups. Hydrolysis of Alkylhalides : 1° and 2° Alkyl halides in aq basic medium hydrolyses to alcohol and hydrahalic acids.3° alkyl halides are hydrolysed in aq medium only. Hydrolysis of Grignard reagents and metal alkyls : Grignard reagents and metal alkyis are very strong bases and hydrolyse violently even with a trace of water togives hydrocarbons and metal hydroxides.HYDROLYSIS OF COMMON FUNCTIONAL GROUPS meow eee ee ae = R Ci ‘Hydrogen Halides = SL. oe Aes, hse wee = = = ae oe