REDUCTION 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 hycrogenoWysis. Reduction can be carried out in following ways: () Catalytic hydrogenation (Wi) Metaliproton (acid) reduction (il) Metal hydrides reduction () Miscellaneous Reductions 1. Catalytic hydrogenation : Hydrogenation using H(gas) on metal surface or other suitable catalyst is called catalytic hydrogenation. A catalyst provides a new pathway for the reaction that involves lower free energy of activation. No catayet (ryote) Catalyst present (Cssalymutistep) Lacs, at =~ 120k) mot” a f >> 06%, Heterogeneous hydrogenation catalysts typically involve 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 i) Heterogeneous catalysts : (catalysts insoluble in the reaction medium) In heterogeneous 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 catalysi (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. ‘ii) The process is exothermic, lote: (If H, 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 he absence ofthe catalyst.) The product has both D and Hatoms).Catalytic Reduction of Functional Groups Using H/Pd(C) or H,/Pt or HJNI R-CH=CH-R +H, MOPS; R—cH,-CH,-R-+ heat Substrate . RNH, RCH.CHR RCH,OH RCHCHR, RCHOHR RCH,NH, Note: (i) Generally RCOOH, RCOOR, RCONH, groups are not reduced by catalytic hydrogenation (ii) i) (iv) (ii) Stereochemistry of catalytic hydrogenation : The above reaction is syn addition (addition takes place from the same face of alkene or alkyne) Homogeneous catalysis : (catalysts soluble in the reaction medium). It uses reactants and catalyst in the same phase. Both hydrogen atoms usually add from the same side of the molecule. ‘Common example : Use of Wikinsion catalyst Rh [(C,H,),PI,CI. Lindlar's catayst : [HJPd, CaCO,, quinoline] [tis poisoned patiacium cafalyst. tis composed of powdered calcium carbonate coated with palladium and poisoned with quinoline, It is used to carry out partial reduction of alkyne to alkene and acid chior ide aldehyde. Stereachemistry : Syn addition. CH cH, CH,-CH,-CxC-CH, —tathsarscrinet “ g (syn addition) C one 4 ‘cis-alkene Quinoline Rosenmund catalyst : [H/Pd, BaSO,, quinoline] Hydrogenation in presence of H/PdIBaS04 called Rosenmund Reduction. it reduces alkyne to alkene and acid halide to aldehyde, itis poisoned palladium catalyst, composed of powdered berium sulphate coated with palladium, poisoned with inoline orsuiphur Stereochemistry : Syn adsttion. (a) CH-Cec-cH,_HiP0. 8050, NA, -CH NY cis-2-butere H.Pd, BaSO, , 9 © on-bo CH, - CHO Note: Nickel boride Ni, (P-2 catalyst) (mace from Nickel acetate and sodium borchidre) isan excellent atom ative 2 catalyst for the conversion of alkyne into alkene. Stereochemistry- Syn addition, Ni(ococH,), + ni.,8. eaHgoH Metal/proton (acid) reduction : Reduction by dissolving metals is based on the fact that the metal acts as @ 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 84 A+B orate 5 A+ B-H =p 8, Spore 8 oe A=B 2, :A-B' of A'-B: "5 BHi) Birch reduction (Na or LUNH,(\ig.) or (ethyl alcohol)] : Alkyne and Aromatic Compounds are reduced by Na or LUNH,. Alkynes are reduced to trans alkene. Stereochemisty : anti addition. R yt R-c=0-R MM» =o (anti adi : yo a etaton Benzone ring is reduced at 1, 4-position. ‘Typical example of reduction for aromatic system Presence of alkyl, akory, amines reduces the benzene ring at ortho position (electron releasing group G -R,~OR, —NH,) H Nery H W Presence of nitro, cyano, carboxylic or aldehyded group reduces the benzene ring at ipso position. (electron withdrawing group H =NO,, - COOH, - CHO, ~ CN) vanity co ii) Bouvealt-Blane reduction [Na/C,H,OH) : Reduction of aldehydes, ketones, esters or cyanide by means of excess of Na/C,H,OH or n-butanol s called ‘Bouvealt-Bianc reduction reduction. CH,CHO NaCHOH, cH.cHoH Acalaldehyde Ethano! ) Stephen's Reductions : [SnCIJHCI] ‘When reduction of cyanide is cartied out with acidified stannous chloride (SnCL/HC) at room temperature, imine hydrochloride is obtained. Which on subsequent hydrolysis with boling water gives aldehyde. This ‘specific type of reduction of nitriles called stephen’s reduction UAH, oF NalG.H.OH Po eae R- CHAN, (Gomplets Reduction! (yong) R-CeN. Sn, HCI) HO “PartarReduction HEN iv) Clemmensen’s Reduction : [2n-Hg/Cone. HC Itisused to prepare alkanes from carbonyl compounds (Aldehyde and ketones in absence of acid ‘sensitive groups). Zn=HIHCL, Soy, t ® ° i Hylooe (ay R- CHO 2HBMSEE HC, ROH, + HO (by R-C-R’ ESE, RCH R+H,O Note : Clemmensen reduction is not used for compounds which have acid sensitive group. {Like Alcohol, Alkene, Alkyne, Ether].3. Metal hydrides reduction Certain complex metal and boron hydrides, are important reagents for reduction. (@—_LIATH, (LAH) Lithium aluminium hydride [LiAlH,/ Ether or THF] : LAH ismost common and versatile reagent. Itis sensitive to protic solvent and therefore used in ether. Reagent] LAM, | LAK, [UAMVEscom|UAKVEscem] LAK, | LINK, | LIAM, | LIAM | LIAR, | LADY Reacant|Acahyae etre [aca TAcideriyrion [Act cianae [Eater [Cyanide [amide [severe [wwe Proavet [acon [Paschal [Patch [reece [wacom [racona [vance [ranme [ranne [arine Note : Alkene, alkyne, benzene rings are not reduced by LiAIH, in ether but itis reported that ii) (ii) (") double bond can be reduced by LiAIH, / THF in few cases like Ph-cH=t (UA THE CH-CHO yuo PR-CH;-CH,-CH,OH Sodium borohydride [NaBH,)C,H,OH or Ether]: Itis more specific than LAH as a reducing agent. It reduces Ketones and aldehydes to the correspond ing alcohols without affecting other functional groups, reduces acid chiorides to 1° alcohols. It does not reduce any other derwvative of acid. tis effective even in protic solvent ike alcohol Reagent | NaBt, | NaBH, NaBH, Reactant |Aldehyde |ketone [Acid chloride Product [1° alcoho! [2° alcohol [1° alcohol ° ed Diisobutyl Aluminium Hydride [DIBAL-H inert solvent]: Diisobuty aluminium hycride is parallel to LAH (Lithium aluminium hydride) as a reducing agent butit is more selective Reagent | DIBAL-H/Cold| DIBAL-HiHydrolysis Reactant [Ester Cyanide Product Aldehyde [Aldehyde f@) ©) Pr-cHscHt_co0c H, AMT PrcH-CH-CHLOH+ HOH [osu Ph-CH=CH—CH.OH By DIBAL at ordinary temperature esters are reduced to alcohols but atlow temperature esters are: reduced to aldehyde. ° ot ne ree C.H.CHO(c) LAH reduce RCN to amine but DIBAL is found to be reduce it to aldehyde. CH, CoN —HAML=THE CCH. NH, i pieaL poe CH,-CHO Miscellaneous Reduction: By Red P & HI Used to prepare alkane from acid, acid derivatives and carbonyl compounds. Red P &HI| Red P&HI|RedP&HI| RedP&HI | RedP&HI | Red P&HI Reactant [Aldehyde [Ketone [Acid chloride [Acidanhydride [Ester Product [Alkane [Alkane [Alkane JAikane latkane RedP + Hl (a) R-GoH REST RH () R-¢- ci ROSE eH, R-CH, j ci RedP + Hi (eyR-G-o8t REST EL, RCH, (R-c-R RCE R-CH,- ° ° + Red Pr Hl (e)CH,CH=O Echt, CH,CH, (90H, -G- CH, 7 CHSCHLCH, ° Meerwein-Pondorf-Verley reduction (Reduction by isopropyl alcohol and aluminium isopropoxide) : Itis selective reduction of ketones to alcohol, even in presence of other functional groups using Aluminium isopropoxide in isopropyl alcohol. AOCHMe,), . RG RCH GH cn, MOE sR fe R'+ CH, — v cH, OH ° A\(OCHNe,), —— “OO ogo : ea: G-om j Wolff-kishner reduction [NH,NH, / KOH] : Used to prepane alkane from carbonyl compounds NH.—NH,/KOH NH,NH, / KOH 9 =O “Ting gn baling SCH, + RCHO a Ren, fy seventtebalene aves Y Not Wolff-kishner reduction is not used for compounds which have base sensitive groups used to reduce carbonyl | & carbonyl group. [Halogens, Acid halide, Esters, Anhydride]@ @ OXIDATION Introduction 1. 2. ‘oxidation is defined as the addition of oxygen (electronegative) element to a substance or removal of hydrogen (electropositive) element from a substance. or . ‘Oxidation of an organic molecule usually corresponds to increasing its oxygen content or decreasing its hydrogen content. ° 2, to, f ROHOH ay R-CH E> R_C-OH 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 chlorine atoms is an oxidation (0) (0) ©) Ar=CH, oo arc, cl arcHcl, = arcel, a aa) ® When organic compound is oxidised, oxidising agent used is reduced. When an organic compound is reduced, the reducing agent used must be oxidized. Oxidation of Alkanes Different products are formed by the use of different oxidising agents or different reaction conditions. Chemica! oxidation with KMnO, or K,Cr,0, : Alkanes are usually not affected by oxidising agents like KNnO, or K,Cr,©,, However, alkanes having tertiary hydrogen are oxidised by these oxidising agents to an alcohol (CHy),cH MRO. (cH,),c0H (isobutane) (Tertiary butyl alcohol) ‘Oxidation of alkenes and alkynes Baeyer reagent (cold dilute alkaline KMinO, solution] : Baeyer | Baeyer | Baeyer Reagent | Reagent | Reagent i [Reactant [akone [aye [ Product |Vicinal diol [Diketone Stereochemistry : syn addition. Both-OH groups add from same stereochemical side. \ Scece + Gonoral Reaction = > C=C + Kino, + “OH, HO —C~C— (or 0s0,, H.0,) bu bn (yn edaiton) Stereochemistry : syn addition. 6 o -on uno. + << _ Sy es sR Mino, 4 + H,0 ud ‘OH Mn se SO eo cis-diolOsmium tetraoxide in alkaline medium [050,/H,0,): ‘Similar to Baeyer reagent 080, /H,0,| O50, /H,0; | O80, /H,0,, Reactant |Aikene JAikyne Product |Vicinal diol |Diketone Oo, Om 050,.H,0, Cx oH Cyclohexene cis-Cyclohexane-1,2-diol Oxidation with peroxyacids An alkene is converted to an epoxide by a peroxyacid. [a carboxylic acid that has an extra oxygen atom in a ~O — 0 ~ (peroxy) linkage} oO f° Oo sence i - N 2 l General Reaction = C=C <+R-C -0-[9}-H—> > CK + REC -O-H (acid) Epoxide ‘Some simple peroxyacids (sometimes called peracids) are shown below ° il os I y CHC —0—f6}— © c—o—i8!—n peroxyacetic acid Peroxy benzoic acid ° I + c—0—iG!—H i () H-~C—O—10;— © Peroxyformic acid G1 Metachloro perbenzoie acid (MCPBA) OH u I — io, bd | | ox (anti addition) 2 General Reaction > © = CC +R—c—00H —* — ° Stereochemistry : anti addition in diol formation. 00H HO" ‘OH Cyclohexene trans- Cyclohexane-1,2-diol 1) RCO.H vt JP DESO HOt 4 Enantiomer as SHO yo fy cH,cH, x rv (ROOM, 1 on, tans QMO Toy cH, Meso Note: The more highly substituted olfinic bond is more nucleophilic and therefore reacts faster with the peroxyacids than the less susbstituted double bond, CH, Hy OME 5G - CHL CHE CH, EO g G— CH, - CH= CH, 4 t =HCO,H” CH, © \,- CH= CH, More Less substituted substituted Oxidation with acidic KMnO, [kMn0,H1] : Stereochemistry : syn addition. When alkene & alkyne heated with KMnO, in acidic or in alkaline medium; following changes takes place KMnOJH’ | KMnO,/H* KMnOJH" KMnOJH” KMnOJH” KMnOJH" Reactant | = CH, group =CHRgroup |=CR,Rogroup | =CH group =CRgroup | Product |CO, IRCOOH }O = CRiRz group |CO, |RCOOH: Carbon doxce [Carbonyic aad [Ketone carbon dioxde |Carboxye 2c | Ex. RCH=CH, IL, Co, +H,0 + RCOOH Ex. RCH IO, CO, +H,0+RCOOH Ex, RC=C-R —I21, 2RCOOH 7 i I Smarr an (CH -C-OH + HO-C-CH,CHy ° () Kino, NaOH, a, I CH,CH2CH, ~C-OH + CO,1 +H,0 a Ex. CH,-C=C-CH,CH, Ex. CH,CH,CH,-C=CH‘Oxidation with ozone (ozonolysis) : Alkene & Alkyne Like permanganate ozone cleaves double bonds to give Ketones and aldehydes. However, ozonotysis is milder, and both Ketones and aldehydes can be recovered without further oxidation. Reductive Ozonolysis Products (0 3/ Zn, H 0} Oy Zn, H,0] Oy Zn,H,0 | OyZn,H,O | O,/Zn,H,0 | 0,/Zn, H,0 | 9229, 410 Reactant |=CH.group |=CHRgroup |=CR,Rzgroup |=CHgroup | =CRgroup Product [HCHO l= CH Raroup [O=CR,R, group |(-keto aldehyde | diketone [Formaidenyae [Aldehyde Ketone Formic acid | diketone Oxidative Ozonolysis Products O90; | Ot; O3iHOy OsOz Os0s CFO: Reactant | = CH, group =CHRgroup |=CR,R2group | = CH group = CRgroup Product |CO2 IRCOOH }O=CRiRz group |COz |RCOOHK |Carbon dioxide |Carboxylic acid |Ketone |Carbon dioxide |Carboxylic acid ©X! C,H,, (A) Out? _, C,H,0, Acid (B), Identify (A) and (B) in the above reaction Sol: (A) [vos ~<] ® [e001 ‘®X: 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=0-CH,-CH,-CxC(CH,),-CH, Oxidation Reaction of Alcohols Oxidation Product of Alconoht Weak oxidising agent “Strong exidieing agent * inert medium | OO! W8TT Kwon? | K:Cr:OrH" pees | ppe~ | croyiinent medi er Wcron | KMnoUH | KsersO4/H = sieohol ‘Aldehyde Carboxylic #cid ‘or Primary alconol ny v icenel or Sesendary alconel| Ketone Ketone ¥ alcohol or tertiary alcohol Not oxidised Not oxidised (@) Pyridinium Chloro Chromate (PCC ) Oo +HCI+ Gro, __Non aquous sowvent oO cr.cro, N 4 \ 4 (©) Pyriinium dichromate (POC) = (2,H,N.CrO,) (©) Colin's Reagent = diute chromic acid + acetone (d) Jones reagent = C0, + pyridine (e) MnO, = Its Selectively oxidised reagent & oxidised allylic and benzylic alcohol into aldehyde and ketone.(Oxidation Product of Alcohoh? Very-Very Strong oxidising agent | Copper & heat KMnO,/H+/Heat a8 oxidising agent Palconol oe Carbonic aod ‘Aldehyde : econo! or Secondary sicahor a ‘one 2 alcohol or tortay alcohol oattaae Dehyate tens allytic/benzylic alcohol CH,-CH,-CH,+OH Cus, cH, -CH,-CH= 0 (dehydrogenation) (-2H) cus ti oH, HCH, CoH CHS G-CH, (dehydrogenation oH cH, cH, i ula I on}E— oH, Hoy CH E=CH, [dehydration (Reduced Product] ‘OH Opponaur's oxidation (i) This reaction invotves the oxidation of a secondary aloohol wth ketone and base tothe corresponding ketone, (i) Commonly used bases are aluminium tert-butoxide, AiOCHo), R.CHOH + (CH),CO === R,CO + CH.CHIOHICH, Alcohol Acetone Ketone Alcohol Rate of Oxidation (a) RCH,OH > R,CHOH > R,C— OH (inert) (b) RCHO > RCH,OH Write the product of following reactions. CH, - CH= CH ~ CH -CH,— CH, - OH on ~ ° Kor oy, d ~ OH + HOOC- G -CH,- § - OH ()H,SO, g § Pos. x—~@ 7 CH-C CH- G-CH,—CHO 3 x —_OPpenauer oxidation oy iy CH= CH- @ ~ CH, CHO @ 10, /eq, . Taceione” CH,~ CH= CH— ¢ CH, COOH ° MnO, x “> CH, ~CH= CH~C~CH, ~CH, -OH © il °Acidic KMnO, & K,Cr,O, as oxidising agent : Aldehydes are oxidised to carboxylic acid having same number of C atoms as aldehyde HCHO +{0] —-» HCOOH; RCHO + [0] ——> RCOOH Ketones are oxidised with difficulty. They are oxidised only on heating with a strong oxiéising agent Cr,OF +H" ‘orKMnO, +H® In case of mixed or unsymmetrical ketones the >C = O group remains with the smaller alkyl group. (Popoff’s rule) i CH, - CCH, + [0] CH,COOH + CO, + H,0 cx,coct.ch, I 2cH,c00H; ci,coch,cr,cl, [91 cl,cooH + cH, cH, COOH Mechanism (with Cr°* oxidising agents) : I () C10, + Ho ——>H,c10, [ref ow Loo 4 9 4 Pe i T -H,0 , R- = on rds (iy R-G CHEESE fon BE + Ox Sf OH RG = O+H,c10, H H H TanstabTe chromate ester , Hi con gg Beale Fo) 20. .n Bo Ah on 28 Reg 0 4 NH Gemdiot Reid unstable Romark: (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) In aqueous medium, aldehyde forms a gemdiol (hydrated aldehyde). It is further oxidised to an acid by similar mechanism. (4) The following reactivity orders can be explained by this mechanism Rate of Oxidation (@) R-CH,OH > R-CD,OH (Bond Energy: C-H RCDO With Tollen’s reagent : RCHO (aldehydes) can be easily oxidised to RCOOH (except HCHO that can be oxidised to CO,) by weak oxidising agents ike ammonical AgNO, (Tollen’s reagent) hence they are better reducing agents. ‘Aldehydes reduce Tollen’s reagentto Ag and appears in the form of silver mirror is called silver-mirror test. Itis given by all aldehydes and reducing sugars. , RCHO + 2(Ag(NH,),*] + 30H —4-> RCOO- + 2Ag 1 + 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 RGHO + 2Cu* + 30H —4-+ RCOO-+ Cu; a +2H,O Pr ‘Aldehydes also reduce Benedict's solution (Cu complexed with citrate ion) to Cu@ (ii) Oxidation reaction of diols HIO, oxidation (Oxidation by lead acetate is similar to HIO, oxid: Mechanism Re if RoR R-G—G-R wo, [PTS Tah, a dy be bn on Xp ay Sb of \p cyclic periodate estor Remarks (1) HIO, (periodic acid) oxidises vicinal dois (1, 2-diol). {Q)Itbrings about oxidative cleavage of vicinal dol @)tcan also oxidise a-hydroxy carbony\ compound, c-dicarbonyl compound and a-hydroxy acid (4) HIO, forms a cycic periodate ester as an intermediate, Sothe wo -OH groups should have syn-confo rm (8) In cyclic diols only cis-vicinal diols are oxidised. Trans isomers are not oxidised General reaction R-GHt cH tor tO. , _HIO._, CHO + HCOOH + R-CHO OH OH OH on CH=O0 Hi0. Aw. HYDROLYSIS 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 ofan ester involves breaking off an este lnk. It can takes place in é He “po-a| esterinkage (8) Mild acidic medium : Dilute H,SO,, dilute HCl (b) 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. ° OW, 0 P wr. A Ro HOM, a + RON Souk Sonn” ROSHHydrolysis of an anhydride : roe sarin cfs 0. fo f Ho HoH, go I af fl Eg ofS OR don Hydrolysis of acid halide : Hydrolysis of an acid halide 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 jon Beg uces R—C+-Cl ———> R—C—OH + HCI Hydrolysis of acid amide : Hydrolysis of an amide results into a carboxylic acid and an amine product or ammonia, only the carboxylic ‘acid producthas a hydroxyl group derived from the water. The amine product (or ammonia) gains the remaining hydrogen ion Bla, OH —Ernk, AS R— Con +, Hydrolysis of cyanides : Cyanide on hydrolysis produce ammonia and carboxylic acids.It is carried out in acidic medium. °. NH ie Rohn SHOWS Doe ny, Hydrolysis of isocyanides : Isocyanides on hydrolysis produce Primary amines and formic acids.|t is carried out in acidic medium. L ON, . r-ndo 3H H, H n— don + ent, Alkylisocyanide does not hydrolyse in basic medium, Hydrolysis of Ethers : Ethers has R-O-R group.in strong acidie medium (Hi or HB) in hydrolysis to produce 2 equivalent of alcohols. Hydrolysis of Hemiacetals and Acetals : Hemiacetals 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 onl in strong acidic medium (HI or HBr) to produce 2 equivalent of alcohols. and one equivalentof aldehyde/ketone. Acetals are often used as protecting groups. HOH OR HMO, MOH ~, a ~N —> 4] —c=0 oR > RO! ou am HOH! Unstable