Reagen 2. Ag,0 Silver Oxide Silver oxide is used in the Tollens’ reagent for oxidizing aldehydes to carboxylic acids: HO no HO? + As Like other aldehydes, aldoses(For Example Glucose) react with Tollens’ reagent giving the positive test. Avo. 7 Wo WO. 9 non aia Woasorntton—-H—|—oH. on: ee le rot on e Oe Hyp aed Meee cao u—|——on ou on + ketose (for example fructose) can also give tollen’s test. Because in basic medium it will converted into aldose. + Reducing sugars -Sugars that give positive tests with Tollens’ or Benedict's or Fehling’s solutions are known as reducing sugars 2. AlCl Aluminura Chloride + Anhyd. AlCl, (or AlBr, ) isa strong Lewis acid + used as a catalyst in Friedel- Crafts Reaction and other Electrophilic Aromatic Substitution reaction Alkylation seen CHES “Ratparous AICI In this reaction Carbocation intermediate is formed (please do remember to rearrange if possible) Acylation O26 NO rearrangement because acylium cation is stabilized by back bonding (a special cease of resonance) 3. BH,(B,H,) Borane (diborane) Reo, ‘Aniyows AICI, It is used in the hydroboration-oxidation reactions of alkenes and alkynes. 1. In Alkenes Alkeneform Alcohol by anti-Markovnikov addition of water on. NOH “cH, OM, HC SCH: ito;Kon” HC 2. In Alkynes Alkyne fornk“Carbonyl Compound by anti-Markovnikov addition of water followed by tautomerization. os 2 ce? ne San ae be We can also use diborane with THF (Tetra Hydrofuran solvent).The vole of THE is used to break dimer BH, To prevent addition of BH, to the second x bond of the alkyne, dialkylboranes (R,BH) such as 9-BBN or isoamylborane are used. 4. Br, Bromine 1. With Alkenes Olt is an anti-addition reaction:1.In solvent like CCl, , CHCl, ete Orc Vicinal dibromide formation : 2.In solvent like HO Br be Wo , “on Halohydrin formation Olt is a regioselective reaction OThe nucleophilic attack of the water occurs at the more substituted carbon atom. 2. With Alkynes Olt is an anti-addition reaction: Br a near ste ney Bene ™ Tetrabromide formation 3. With Aromatic Compounds Br Br, FeBr, 4. Photo halogenation of alkanes Hc” cH Hye CH Major 5. Alpha Bromination of carbonyl conpounds : : ee Hye” oH, Acetioacid H,0° Br ©. Oxidation of Monosaccharides 1.Bromine water is a mild oxidizing agent 2.selectively oxidizes the aldehyde group (for example CHO group) to a carboxylic acid 7. Haloform Reaction converts methyl ketones to Haloform (CHX,(X = Cl, Br, 1) and salt of carboxylic acids. 8. The Hoffmann Bromamide degradation It converts primary amide to a primary amine with one less carbon ator. Hy Br, Huo Me Be te 8 NaOH 9. Hell—Volhard—Zelinski (or HVZ) reaction gD REAP Br © x i 2Ho MC on oH Ss. CN™ Cyanide lon (Nitrile Group) 1. Conversion. of Nitriles to a Primary Amine he 2. Conversion of Nitriles to Aldehydes peach Hc OH 3. Reaction of Nitriles with Grignard reagent ° 4. CH MgCl Hye a Tine” cH 4. Hydrolysis of Nitriles to Carboxylic Acids ° . ato Hye6. CrO, Chromium trioxide + The mixture of chromium trioxide and sulfuric acid dissolved in @ mixture of acetone and water is called Jones reagent. + In aqueous acidic solutions, CrO, forms chromic acid (H,CrO,) which acts, as a strong oxidizing agent. + It is also used to prepare Pyridinium chlorochromate (PCC) (Pyridine + CrO, + HCI) which is a mild oxidizing agent. Function — Mild oxidizing agent | Strong oxidizing agent 1. converts 1. converts primary primary alcohols to alcohols to Aldehydes carboxylic acids 2. secondary 2. secondary alcohols to alcohols to ketones. ketones. 3. NO oxidation of |3. NO oxidation of tertiary alcohols| tertiary alcohols on _ 0°05 Hye A80, De Pcc. © on 4 a ue chs wei we Pec chs fee ee et on ° We can also use chromic acid H,CrO, + Chromic acid is a strong oxidizing agent + Converts primary alcohols to carboxylic acids, and secondary alcohols to ketones. + It is prepared by mixing a variety of compounds with aqueous acidic solution. + Some common examples are CrO,/H.0", Na,Cr,0,/H,0", K,Cr,0,/H,0", NaCrO,/ H,0", and K,CrO,/ H,0". 7. Cuprous Halides (Cu,X,) 1. Used in the reactions of arene diazonium a O, cu,ciJHe Cu,8r/HBr cular ~eucNHeN™ 7 Sandmeyer’s Reaction Cu,Cl,/HCl Cu,Br,/HBr CuCN/HCN Gatterman’s Reaction cu/Hel Cu/HBr 2. Itisalsoused for preparing organccuprates (Gilttaw’ reagents) which is useful in Corey house synthesis ui or (CH,),CuLi CH —Br We can also use CuCl or Cul 8. DMS Dimethyl sulfide 2. used in the reductive ozonolysis of alkenes 2. Carbonyl compounds are formed a tiem 2. AL “S28. aHCHOch He 72H 0.2604 = CH,CHOFCHO Hl osccn, 3 "— mes o 6 @. CHANa, Diazomethane 1. Methyl-esterification of carboxylic acids 0 CHN, ° we ne’ on oor 2. Cyclopropanation of alkenes Hye Sc, Bm Hye 3. Insertion of methylene into OH bond of phenol H oH G ae O 10. DIBAL-H Di-isobutyl aluminum Hydride Reduction of Esters to Aldehydes Pee 4.DiBAL-H O-Cry 20 va ee et Reduction of Nitriles to Aldehydes 9 ne To ne 11. Fe tron oa eee of nitrobenzene into aniline Oy remot We can also use Sn /HCI , in ethanol 2. electrophilic reactions. OQ _Bafe H, + Nit Pd aromatic substitution 12. Hy Hydrogen Hydrogen with metal catalysts such as Pd, Pt, Ni is used for the reduction of alkenes, alkynes and other functional groups containing bonds. 1. Reduction of Alkenes and alkynes to alkanes Dihydrogen gas adds to alkenes and alkynes in the presence of finely divided catalysts like platinum, palladiara or nickel to form alkanes. This process is called hydrogenation. H,Mi orto Pa Hye cH Hye, s ior PLor Pa. ye Son 2 neo Reduction of Alkynes to alkenes 2 Cis Alkene TN a ~or Beso,” CezHoxene Partially deactivated palladised charcoal is known as Lindlar’s catalyst. O Trans Alkene alkynes on reduction with sodium in liquid anamonia fori trans alkenes. INatLia NH Soh ye NALIN Trans:2-Hoxone 3. Reduction of7a Cyanide to Amine ONit¥iles’ on reduction with catalytic hydrogenation produce primary araines OThis reaction is used for ascent of amine series, i.e., for preparation of arnines containing one carbon atom more than the starting amine. nc HNP 4. Catalytic Hydrogenation of Benzene Under vigorous conditions, ie., at high temperature and/ or pressure in the presence ofnickel catalyst, hydrogenation of benzene gives cyclohexane. oJ NH, neo13. H,0° Acidic Hydrolysis 1. Hydrolysis of Cyanide Wy “ wo’ 2. Hydrolysis of Acid Derivatives O Hydrolysis of Acid Chloride ‘i © O Hydrolysis of Anhydride wh, gen ene © Hydrolysis of Ester we bee ee ye Font enca O Hydrolysis of Amide 3. Hydrolysis of isocyanide Ho" cynic 2 cy nn) + HoOoH we 14. HX Hydrohalic acid (X = Cl, Br, t) 1. used in the addition reactions of alkenes and alkynes Q Reaction of HX with Alkene In this reaction carbocation is formed , check the possibility of rearrangements like hydride shift , methyl shift ring expansion and ving contraction wee aun wean, Ee won i TT Habe Reaction of HX with Alkyne is Hs 2h ct At BH A e Br Q Reaction of HBr/peroxide with Alkene Addition of HBr takes place according to anti~raarkovnikov's Rule Peroxide effect or Kharasch effect is applicable to HBr only Hs ets He Hye aE hype 2. used in the substitution reactions of primary, secondary, and tertiary alcohols. In this reaction carbocation is formed , check the possibility of rearrangements like hydride shift , methyl shift ving aaa and ring contraction ere ye GeO 15, Hg(OAc), Oxymercuration- Meveuvic di-acetate Demercuration veaction of alkenes +\s used in the + Alkenes into alcohols following the Markovnikov’s rule. oH He Hg(OAc),/H,0 = NaBH, Ha(OAc) /H,0 Mel NaBH, "8° i o Hye So+ Is used in the Alkoxymercuration- Demercuration reaction of alkenes + Alkenes into Ethers Markovnikov's rule. weary, HOLA) MEOH, i NaBH, following the cH, _Hg(OAc),/MeOH CH ne a Hye" 's 16. HgSO, Mercurie Sulfate + It is used in conversion of alkynes to ketones. Hg dil. Hg80, “aLAS0, > gon Sh 980, ny 27. HIO, Periodic acid + used for the oxidative cleavage of Cis-1,2- diols (vieinal diols) forming aldehydes and ketones. A + used for the oxidation of a-Hydroxy ketones forming carbonyl compound and carboxylic acid AL + Be 4 7 oon + used for the oxidation of a-diketones forming carboxylic acids. vse eee + ok re an Hee. CHs 10, —t> ne OH OH Hat. ctr Io, te he on oO 18. HNO, Nitric Acid used primarily for the nitration of aromatic compounds + Nitration of Aromatic Compounds Ox 4-0” Sy’ 19. HsPO, Phosphoric acid + used mainly in the elimination reactions of alcohols chy We on b Ct Hee Eye ‘conc.HsPO, Major Minor + More stable alkene is the major product + In this reaction carbocation is formed , check the possibility’oPrearrangement like hydride shift, methyl shift, ring expansion, ring contraction-cte. + We can also use conc. sulfuric acid in this reaction 20. KMnO, Potassium permanganate + It is a strong oxidizing agent + used for the oxidation of alcohols, benzylic carbons, oxidative cleavage of alkenes and alkynes, and syn dihydroxylation of alkenes. 1. Oxidation of Primary Alcohols to Carboxylic Acids on _KMno, pp Hye sea erase Huerta2. Oxidation of Secondary Alcohols to Ketones on _KMnO, Oo He Ya ean: CHy CHS 3. Oxidation of the Benzylic Position to a Carboxylic Acid Ox oH Hs KMnO, HF 4. Oxidative Cleavage of Alkenes Same as oxidative ozonolysis Kno, ne Fo, A 9 ne Ho + He i¢ HO 5. Oxidative Cleavage of Alkynes Like in the ozonolysis of internal alkynes, carboxylic acids are produced: KMn0, Z SMO Hye Fs HF fo) 0 + Hef In the case of terminal alkynes carboxylic acid , CO, and H,0 are produced KMnO, Hye Son ee Hye. +CO, + H,0 ete + Syn Dihydroxylation of Alkenes Baeyers reagent is used. A cold solution is a must here otherwise oxidative cleavage will oceur. iH KMno, il. & alk. "OH 21. ‘Buk Potassium tert-butoxide + It Is.a strong, sterically hindered base used for E2 elimination reactions. + The steric nature makes it a suitable base for predominating the Hofmann product. ee tBu0k ioe Cty ——— ye Hae Minor chy + He Mejor He 2 Hee, ao) tBuOk oc) 22. LiAIH, Lithiurn Aluminum Hydride + Lithiunn Aluminum Hydride (LAH) is ‘one of the strongest and most common reducing agent + Capable of reducing aldehydes, ketones, carboxylic acids, esters, acid chlorides, araides and anhydrides etc. 1. Reduction of Aldehydes to Primary Alcohols He" 2. Réduction of Ketones to Secondary Alcohols 3. Reduction of Carboxylic Acids to Primary Alcohols 4. Reduction of Acid Chlorides to Primary Alcohols LAI, ou cre Hye ‘OH5. Reduction of Anhydride to Primary Alcohols wh A, 6. Reduction of Esters to Primary Alcohols Ce et 7. Reduction of Amides to Amines ; eet 8. Reduction of Epoxides to Secondary Alcohols Hye. aa ‘Cth —— ac ‘oH AIH, LAH, bh ete SZ Lia, Hie! ‘0 9. Reduction of Nitriles to Primary Amines LAH, He CH chy 25. LiAIH(Ot-Bu), Lithium tri tert-butoxy aluminum hydride + It is a bulky reducing agent + Not as reactive as LiAIH, + It is used for reduction of acid chlorides and ester to aldehydes. Reduction of Acid Chloride to Aldehyde He ocaaanaeee ce 4 24. MCPBA m-chloroperoxybenzoic acid 2. It is an oxidizing agent most commonly used for the epoxidation of Alkene ie e McPBA ed Anti-Dihydroxylation of Alkenes with MCPBA oH 2. In the Baeyer-Villiger reaction. McPBA 1,0" convertion of aldehydes and ketones to carboxylic acids and esters respectively oh =orx 25. Na/liq.NHy Sodium 1. Sodium is a very reactive metal that works as an electron donor and thus a reducing agent. 2. It is used in Birch reduction. O Reduction of internal alkynes to trans alkenes oly Naga, CH HC Hye OQ Reduction of benzene O09 + Reduction of Substituted benzene with Electron Donating Groups 9—CHy o—CHy ae + Reduction of Substituted benzene with Electron withdrawing Groups Ox LOH Ox LOH & Na/Lig. NH, &26. NaBH, Sodium borohydride 4. NaBH, is mild reducing agent. 2. it is not so reactive and can be used to reduce aldehydes, ketones and acid halides OReduction of Aldehyde into primary alcohol : H ° Reduction of Ketone into secondary alcohol Ke Q Reduction of Acid Chloride into Primary alcohol © NaBH, isalsoused inthe Oxymercuration— Demercuration reaction 27. NaNH, Sodium amide 1. It is a very strong base most often used for preparing and deprotonating alkynes 2. It isalso used in the nucleophilic aromatic substitution for generating the benzyne intermediate. Preparation of Alkynes from alkyl dihalides cl CHy CH. 2NaNH, se Cs HyC’ ee eS a © Deprotonation of terminal Alkynes i tH ae OAnilines from Aryl Halides oad When +I group is present Na + NH Nite Ny Nant, Tent, CH Hy CH Minor Major When -I group is present ¢ Nia NH san Tom, O-cH O—cH, Oc, Major Minor 28. NaOEt Sodium Ethoxide 1. It is a gthengy unhindered base and a good,Aucleophile used for E2 and Sy2 and inueleophilic addition elimination feattions, 2. In nucleophilic substitution reactions Williamson ether synthesis ci NaOEt yew ye OT", 2. In Elimination reactions Dehydrohalogenation 7 ee EtOH3. For converting acid chlorides to esters oe a NaQeEt HC’ ‘cH 24. NaOH Sodiurn Hydroxide It isthe most common base and the nucleophile used in many instances predominantly for SN2, E2 and nucleophilic addition elimination reactions. 2. In nucleophilic substitution reactions NaOH Hye Se ye 0H 2. In elimination reactions ots oi cl . AKG Nao c Hy ee SF cy Major Che Het R Hye ‘Cy Minor 3. In nucleophilic addition-elimination reactions 2 i NaH ‘CHa ‘CH 4. In hydrolysis of esters ot wo’ tne mor Hy ‘Cs NaOH Hye. 30. NBS N-Bromosuccinimide It is used for allylic and benzylic bromination, formation of bronmohydrins. 1. Allylic Bromination sc, NBS PN cu, HyC’ 2. Benzylic Bromination 6-6 3. Bromohydrin formation OO 31. NH,OH Hydroxylaraine 4. It is a good nucleophile 2. Reacted with carbonyl compounds for preparation of oximes 1. Oximes from aldehydes AZ NH,OH Hac! ae ne’ An 2. Oximes from ketones 0 NH,OH wey? MH oH 32. NHy Ammonia a ~y 4. Ammonia is a base and a nucleophile most commonly used in the preparation of primary araines and avnides. 2. It can also be used as solvent for the reactions of Na, K, Li)sodium amide and other similar bases. 1. Preparation of Primary Amines from Alkyl Halides AN, He" ae ne’ ee 2. Preparation of Primary Amides from Acid Chlorides aE ‘Hs ‘os 3. In the Reduction of an Alkyne to a Trans Alkene Trans alkenes are prepared by reducing internal alkynes by dissolving Na or Li in NH,, LiorNa, M6, Nee Ne je _——==—cn, cH33. NHNH,, Hydrazine 1. It is a good nucleophile and a reducing agent 2. used in the Wolff-Kishner reaction for conversion of Carbonyl compounds to alkanes. Q In the Wolff-Kishner reaction ° NH Oe O ‘ethylene glycol 34. Ni,B Nickel boride 1. Nickel boride, a P-2 catalyst, is a reducing agent similar to the Lindlar’s catalyst 2. used for converting alkynes to cis alkenes. 35.05 Ozone 1. It is an oxidizing agent used in the ozonolysis of alkenes and alkynes. 2. The ozonolysis of alkenes produces aldehydes or ketones when dimethyl sulfide or Zn is used (Reductive ozonolysis) 3. The ozonolysis of alkenes produces Carboxylic acid when water or Hydrogen peroxide is used. (Oxidative ozonolysis) 4. The ozonolysis of alkynes produces alpha dicarbonyl compounds when dimethyl sulfide or Zn is used (Reductive ozonolysis) 5. The ozonolysis of alkynes produces carboxylic acids when water or Hydrogen peroxide is used. (Oxidative ozonolysis) O Reductive Ozonolysis of Alkenes Zot O40), e He" Zn orMe,S" nee ee 2 Oxidative Ozonolysis of Alkenes 7 0. p Ce ee H,0 or H,0, OH on O Reductive Ozonolysis of Alkynes He 9 occ, Zn oF Me,” g < 2 Oxidative Ozonolysis of internal Alkynes ALrcn, 280% Hye" * "H,0 or H,0, HO wef ‘ K& ‘OH HyC o 2 Oxidative Ozonolysis of terminal Alkynes Soy 228 OC, Hye" ‘CH HO or HO, He ‘on + COntH,O 36. PBrs Phosphorus tri bromide tt is used for converting alcohols to alkyl bromides and carboxylic acids to acid broraides. 2 Conversion of alcohols to alkyl bromides " ae HyC" 2 carboxylic acide ae ° kp — be yeh BT. P305 Phosphus pentoxide AME i$ a dehydrating agent 2. used for converting carboxylic acids to anhydrides, and amides to nitriles respectively. OConversion of carboxylic acids to anhydrides " A, ee IO Hygc™ “OH ~~ Hye” 0 cH 2 Conversion of amides to nitriles 9 i fai a Hg" H3C-3a. PCC Pyridiniunn chlorochromate 1. It is a mild oxidizing agent 2. converting primary alcohols to aldehydes and secondary alcohols to ketones. OConversion of primary alcohols to aldehydes Pcc yc” OH ———* Hc“ S0 alcohols to Conversion secondary ketones ‘ Hyo7 OH Pcc He 34. POCI, Phosphorus oxychloride 1. Is a dehydrating agent 2. used for converting alcohols to alkenes and amides to nitriles. Alcohols to alkenes by POCl, OO 2 Amides to Nitriles by POCI, 9 A roo, Hc Nt a 40. PhP Triphenylphosphine It is used for preparing Wittig reagent PPh, CHL Further it is used to prepare alkene ° Hc ~cHs ye Sy 41. R,CuLi Organocuprates 1. Organocuprate reagents, also known as Gilman reagents 2. Used for preparation of alkanes and conjugate (1, 4-) addition to a, B-unsaturated carbonyls 2 Corey house synthesis - Preparation of Alkanes Rew rt 1 2S» R-R'+ RCu + LiCl Cl must be 1 Halide fr beter ya 2 Conjugate Addition to a, B-unsaturated carbonyl compounds . vol, apa en ECHL ye A IL EIOH ‘ 42. Ra-Ni Raney Nickel 4. It is a reducing agent that is used most commonly for converting thio acetals to alkanes. 2. a good way of converting aldehydes and ketones to alkanes. 2 Carbonyl to alkane alkene to Alkane i Hye Sette Rar Hye Hs 43. S05 ‘Sulfur trioxide 1. Itisused for the sulphonation of aromatic compounds OC Oleum2. The sulfonylation is reversible process i.e. the SOH can be removed if treated used for blocking the with acid. position It is 44. SOCI, Thionyl chloride 1.I¢ is a chlorinating agent used for converting alcohols to alkyl chlorides and carboxylic acids to acid chlorides. 2 Conversion of alcohols to alkyl chlorides cH CH soci, ae 7 *pyriame om ‘SN? ls CH CHs soci, —- ‘SN’ CH Conversion of carboxylic acids to acid chlorides 45. Sn Tin 1. It is a reducing agent used, in the presence of an acid Conversion of amine nitro group into an Oxyr0 a 46. TsCl p-Toluenesulfony| chlovide 1. It is used for converting alcohols into alkyl sulfonates called tosylates (OTS) which is a good leaving group 2. Tosylates can then be used in substitution and elimination reactions Q Substitution Reaction OH ee ae TsCl bs Ha CHLOH hc Hg 2 Elimination Reaction Hc: Tcl a Hs wt ae Srl at, Na’) ICH,OH aa g Note that the stereochemistry of the alcohol is retained in the tosylating step, but it will change in an 5,2. reaction.47. TsOH p-Toluenesulfonic acid 1. [tis a strong acid 2. used for the dehydration of alcohols (E1 Elimination ) ‘OH TsOH Heat We can also use H,SO, » HsPO, and KHSO, 48. Zn Zine 1. It is used as an alloy with mercury for the Clemmensen reduction of Carbonyl compounds to alkanes st ae Hye “8 ConeHCl 2. It is also used in the Simmons—Smith reaction Olt is a stereospecific reaction and depending on the configuration of the alkene, cis or trans product is obtained: He, pry CHa Hy —/ an, cue a Ha, CH, wy v6 ead aw ,