CHAPTER 1) ALCOHOLS | 453 Al) Reaction with Active Metals, Ale, 7 jiverale hydrogen and to form metal ek Teact with Li, Na, K, and other active metals to 2CH,OH + ena 2CHONa 4 H, oe Sodium methoxide jCH,OH. se MT —+ (CHCHLOLMg + BE eae 3 Magnesium ethoxide Alkoxide ions are somewhat Stronger bases than hydroxide ion, The following alkoxides are commonly used in organic reactions Tequiring 4 ; 4 strong base in a non aqueous solvent, as, for example, sodium methoxide in methanol and sodi ‘ ' lum ethoxide in ethanol ft > Nat CHO" Nay CHyCH;O-Nat —CH,CO-K* | CH; Sodium methoxide Sodium ethoxide Potassium tert-butoxide Alcohols can also be Converted to salts by reaction with bases stronger than alkoxides. One such base is sodium hydride, NaH. CH3CH,OH + NatH? ——» CH3CH,0° Na* + Ho Ethanol Sodium Sodium ethoxide hydride Reactions of sodium hydride with compounds containing acidic hydrogens are irreversible and driven to completion by the formation of H,, which is given off as a gas. Alcohols do not react with NaOH or KOH. CH3CH,OH + NaQ}H ——> Noreaction Ethanol ‘Sodium metal reacts vigorously with alcohols such as methyl alcohol or ethyl alcohol with the evolution of hydrogen gas (Seen as bubbles). 2) Dehydration of Alcohols using Acids. Dehydration isa B elimination reaction in which the clements of OH and H are removed from the 0, and B carbon atoms, respectively. p | | « eon eat New xbond (an alkene) Elimination of H-OH454 | ADVANCED ORGANIC CHEMISTRY Alcohols undergo dehydration in the presence of strong acids to yield alkenes Typical 9 used for this conversion are H,SO, or p- toluenesulfontc acid (TSOH) CH, ne H,SO, CH;—C—CH, >» GCH,—C=CH, + H,0 | OH H 2-Methyl-2-propano! 2-Methyipropene - cH: CH,CH,—OH, + Br EthanolCHAPTTR 14 ALCOHOLS | 459 Step 2. Nucleophitic atick of Br, geet mony ae EC > Chico +. Hb: ‘ ne Ethyl bromide Fxample 2. Reaction of ten-butyl alcohol with HBr illustrates the $,1 mechanism of a 3° alcohol CH, c CH, ¢ Ol i. iy C ee Hey | ay, Nar + HO ‘3 tert-Buty| alcoho! sig ca MECHANISM. Following steps are involved : Step 1. Protonation of the OH group. CH, cH eae ~ : es — cy —C—bn, + Br CH, CH tert-Butyl alcohol Step 2. Formation of the carbocation, CHg CH Hy PT Oe —* mo + Hb: CHy CH; Carbocation Step 3. Nucleophilic attack of Br. CH; CH. ie c Bat + Br —, Sete CH CH tert-Butyl bromide Because the carbocations are formed in the S,1 reaction of 2° and 3° alcohols with HX, carbocation Tearrangements are possible. The reactivity of hydrogen halides increases with increasing acidity : HCI H-Br Ho Increasing reactivity towards ROH —) Because Cl is a poorer nucleophile than Br or I’, the reaction of 1° alcohols with HCI occurs only when an additional Lewis acid catalyst, usually ZnCl, is added. ZnCl, complexes with the O atom of the alcohol in a Lewis acid-base reaction, making an especially good leaving group and faciitaing the $,2 reaction.460 | Avvanceo ORGANIC CHEMISTRY se “ZnO ROBES OHece “2a, 5 Aer oe ACHE Ol. + Zeca Lewis b; A Leavir ao ‘coho! Lewis acid on "9 Qtoy, _©) Reaction with SOCI,. The treatment of 1° or 2° alcohols with thionyl chloride (SOc) ang Pyridine gives an alkyl chloride, Sulfur dioxide and HC! are formed as by-product. ’ R—OH + SOCl Pueie po} 4 SO, + HC 1° oF 2° Alcohol Alkyl chloride CHsCHa—OH + SOCl, rae CHyCH,—Cl Ethanol Ethyl chloride Ove + ag mm Oo Cyclohexanol Cyclohexyl chloride MECHANISM. Reaction takes place by S,2 mechanism. Following steps are involved - Step 1 and Step 2, Reaction of the alcohol with SOCI, yields an intermediate that loses a prot by reaction with pyridine in Step 2. This two-step process converts OH group into OSOCI, a 2004 leaving group, and also generates the nucleophile (CI’) required for Step 3. cl Fe a Cl i oe e 2 + ae Sa : So ++ rte . Cy S=O apr RO H Good leaving group er) Alcohol ae a « N: sh Step 3, Nucleophilic attack of CI-. o ALS. 3 ante*so = ASC S64 cr cr Alkyl chloride (6) Reaction with PBr,. The treatment of 1° or 2° alcohols with phosphorus tribromide (PBr,) forms an alkyl bromide, R—OH + PBrp ——> R—Br + HOPBr. 1° or 2° Alcohol Alky! bromide | CHsCHp—OH + PBry —» CHCH,—Br Ethanol Ethyl bromide Oaim— On Cyclohexanol Cyclohexyl bromide qws] ADVANCED ORGANIC CHEMISTRY 9 + i eg é WHH 4 or CE OF CHg io ° or CHjCH,—O—Ts 4— _ Good leaving group e: leaving groups, the: Reactions of Tosylates. Because alky! tosylates have good leaving group: Y Undergy ‘ Sate nucleophilic substitution and B elimination, exactly as alky! halides Toanaa alky tosyitee treated with strong nucleophiles and bases, so that the aga iv : ie fon is 82 ae . mechanism of elimination is E2, For example, ethyl tosylate, which has the leaving OUP on : carbon, reacts with NaOCH, to yield ethyl methyl ether, the product of Boilie SUbStitution by an S.2 mechanism, It reacts with KOC(CH,),, a strong sterically hindered base, to yield thy lene e an E2 mechanism, " —— chych, Tors + sek — CHsCHy—OCH3 + Nat -ors Ethyl tosylate Strong nucleophile Substitution H— Soe Sy K* “OC(CHs)3 Strong non-nucleophilic base Elimination H ¢xcH—oTe 2+ CH=CH, + Kt-OTs | This provides us with another two-step method to convert an alcohol to a substitution product : reaction of an alcohol with TsCl and pyridine to forma tosylates, followed by nucleophilic attack on the tosylates. INU TsCl ei R—OH Pyidre” «=~R—-OTs ——> R—Nu + ~OTs Overall process - Nucleophilic substitution er | (8) Reaction with Carboxylic Acids. Alcohols react with carboxylic acids to form esters. Concentrated sulfuric acid is used as a catalyst. The reaction is reversible and can be shifted in the forward direction by removing water as soon as it is formed. f Il . Il ROH + HO-C—R => Ro—C—A + H,0 Alcohol acid Ester ’ ll Ht Il C,HsOH + HO—C—CH, eae CzHsO—C—CH, + H,0 Ethyl alcohol Acetic acid Ethyl acetate| i ALCOHOLS | 463 a ct The reac! ae Picea an alcohol and a carboxylic acid to form an ester is called Esterification (9) Reaction with Acid Halides and Acid Ai i oj anhydrides to form esters, cid Anhydrides, Aloohols react with acid halides and acid 1 ai ll CHs—C—Gl +H—0C,H, —*> cH,—C—OGHs + HC! Acetyl chloride Ethyl alcohol Ethyl acetate = i I CHs—C: +H—0C;H, —“» cH,—C—0C;H, + CHy—C—OH Acetic anhydride Ethyl alcohol Ethyl acetate Acetic acid (10) Reaction with Grignard Reagents. Alcohols react with Grignard reagents (RMgX) to form alkanes. ROH + RMgX —* RH + ROMgX Alcohol Alkane CH3CH,OH + CH;MgBr —» CH, + CH,CH,OMgBr Ethyl alcohol Methane (11) Reduction. Alcohols undergo reduction with concentrated hydriodic acid and red phosphorus to produce alkanes. ROH + 2Hl => RH + |, + HO Alcohol Alkane CHjCH,OH + 2HI > CH,CHs + |p + HO Ethyl alcohol Ethane Uy Oxidation. Oxidation reactions are important and prevalent in organic chemistry. A number of different reagents have been developed to permit selective oxidation — that is, oxidation of one functional group without affecting another susceptible functional group. It is important to gradually develop a feel for the different oxidizing reagents and their strengths. As you will see, most of these Teagents are inorganic compounds, Remember that when any compound (often generically called a substrate) is oxidized, the reagent is reduced (and vice versa). When an organic compound is oxidized, one of two things happens: There is an increase in the ‘oxygen content of the substrate, or there is a decrease in the hydrogen content of the substrate. Families of organic compounds can be placed in ahierarchy of oxidation states, as reflected in Table 13.5. These relationships are important. You can see that the effective laboratory oxidations are those from alcohol (alkanol) to aldehyde (alkanal) to carboxylic acid (alkanoic acid). Note also that only C-H bonds are broken in these oxidations, not C-C bonds. No carbon atoms are removed. ee discuss three oxidation reagents here : (@) Asolution of potassium permanganate (KMn0,). Deep purple in color, such a solution is a j dita Inthe course of reaction, the purple Mn(VI1) is reduced to Mn(IV), which precipitates if ‘as brown manganese dioxide (MnO,). i f 2464 | ADVANCED ORGANIC CHEMISTRY int Structure Ease of Oxidation Highest oxidation Carbon dioxide © O=C=O | state of carbon | | Carboxylic acid ont IER =alkyl, only by combustion (Alkanoic acid) IfR=H, very easy I Very eas! ; Aldehyde R—C+H Very easy (Alkanal) Alcohol (Alkanol) R—-CH,—OH Readily R-CH, Extremely difficult (2) Chromic acid (H,CrO,). A strong oxidant usually used with alcohols, chromic acid can be produced in solution by two methods : (1 ) from sodium dichromate (Na,Cr,O,) and sulfuric acid, or Q) by dissolving chromic anhydride (CrO,) in concentrated sulfuric acid and water (this is called Jones’ reagent). During an oxidation reaction, the orange-colored Cr(VI) in this Teagent forms greenish-blue Cr(II), which remains in solution. (©) Pyridinium chlorochromate (C,H,NCrO,CL, usually abbreviated PCC). Amild oxidizing reagent, PCC is a soluble complex of chromic anhydride (CrO,) and pyridine in dilute HCI. Chemists normally write an organic oxidation reaction showing the reagent used and the organic product(s), but not the inorganic products. Occasionally, they indicate an oxidation process by writing [O] over the reaction arrow, without specifying the actual reagent, In a primary alcohol, two hydrogens can be removed from the carbon being oxidized. The alcohol is oxidized by KMnO, or H,CrO,, initially to an aldehyde, However, it is very difficult to obtain good yields because the aldehyde is more easily oxidized than the alcohol and so is oxidized rapidly to the carboxylic acid. Therefore, the normal product of oxidation of a primary alcohol witha strong oxidant is a carboxylic acid. f 1 NazCr,07 R—CH,—OH eo; R-C—H| ——»+ R—C—OH 1° Alcohol Aldehyde Carboxylic acid For example, oxidation of ethyl alcohol gives acetic acid, and oxidation of isobuty! alcohol yields isobutyric acid. ° NagCr,07 Il Na2Ci I CHsCHOH eS > CHp—C—H Ree CHy—C—OH Ethyl alcohol Acetaldehyde Acetic acid466 | AbvaNcep ORGANIC CHEMISTRY idi with st On this basis, you can see why tertiary alcohols cannot be oxidized, even FONG reagens, th is no hydrogen on the hydroxyl carbon. Rn 3 Jones’ reagent can be used in a qualitative test with alcohols of eh aah lodis ing Primary and secondary alcohols, which will undergo oxidation, from tertiary O18, Which wi erntahe| Ni A positive test result is the change in color from orange Cr(VI) £0 greenish-blue Cr(1l)), idk that the reagent has been reduced and the substrate has been oxidized, \(12)_ Reaction with the Hot Copper ; Dehydrogenation. a types of alcohols give lg Products when their vapors are passed over copper gauze al 300°C. 1 Primary alcohols lose hydrogen and give an aldehyde. ne t i es CH,CH,OH aie CHy—C—H + Hp Ethyl alcohol Acetaldehyde Secondary alcohols lose hydrogen and yield a ketone. c I CHs—CH—CHg =a CH;—C—CHs + Hp lsopropy! alcohol Acetone (2-Propanol) Tertiary alcohols are not dehydrogenated but lose a molecule of water to give alkenes, i rr Cu ne er OH oo” Ore ¢ + HO CH; CH, tert-Butyl alcoho! 2-Methylpropene TESTS FOR -OH GROUP The following three tests may be used to detect the presence of -OH group in organic ‘compounds. For these tests, take the liquid compound or a solution of the solid compound in an inert solvent such as dry ether or benzene. (1) Add to it small pieces of Sodium metal. If bubbles of hydrogen gas are given of, the compound contains an -OH group. 2R—OH + 2Na —* 2R—ONa + Ht 2) Add to it Phosphorus pentachloride. If the mixture becomes warm with evolution of HCI 20s, the given compound contains an -OH group. R—OH + PCl; —» R—Cl + POC, + HCI @)_ Add Acetyl chloride or Benzoyl chloride to the substance. The separation of an oily ae"! the ester and evolution of HCI gas indicates the presence of an-OH group. It may be noted that i the compound was taken in an organic solvent, the oily ester may dissolve in it and thus limiting the tes to the evolution of HCl gas only. HOW TO DISTINGUISH BETWEEN 1°, 2°, AND 3° ALCOHOLS ? The following tests are used to distinguish between primary, secondary, and tertiary alot (1) Latcas Test, In this test, alcohols are treated with a solution of HCI and zine chloride (/4* reagent) to form alkyl halides. Zinc chloride serves as a catalyst.CHAPTER 11 ALCOHOLS | 467 Alcohol Alky| halide The three types of alcohols undergo this reaction at different rates. Tertiary alcobols react with Jwcas reagent very rapidly. Secondary alcohols react somewhat slower. Primary alcobols react with Lucas reagent even more slowly, y In practice, the Lucas test carried out as follows + An alcohol is mixed, al room temperature, with HCl and ZnCl), The alkyl chloride, which is formed, is insoluble in the medium. {t causes to become cloudy before it separates as a distinct layer. (a) With Tertlary alcohols cloudiness appears immediately. (by) With Secondary aleohols cloudiness appears in 5 minutes. (c) With Primary alcohols the solution remains clear, This is because primary alcohols do not pact with Lucas reagent at room temperature. High temperatures are needed. ~ Q) Dichromute Test. This testis based on the fact that different types of alcohols give different ducts on oxidation. The alcohol is treated at room temperature with sodium dichromate in sulfuric (orange solution). Identification of the products gives us information regarding the type of the (a) Primary alcohols give a carboxylic acid containing the same number of carbons. There will change in color of the solution from orange to green. (b) Secondary alcohols give a ketone containing the same number of carbons. There will be a z¢ in color of the solution from orange to green. — (c) Tertiary alcohols do not react under these congitions. Solution will remain orange.CHAR 14 POLYHYDRIC ALCOHOLS | 495 Sep 2. Formation of carbonium ion by loss of water from the protonated diol GHs GHs CH, CHg Seat ote —> CHs—C—C—CH, OH OH, on Protonated diol Carbonium ion Nep&. Rearrangement of carbonium ion by 1,2-shift to give protonated ketone. (GG Gry CHs ~ CHy—C——C—CH, ———» CH;—C—C—CH, cl t ii | ~aQH +OH CH; * Carbonium ion Protonaied ketone Step 4. Formation of ketone by loss of proton from the protonated ketone CH, Ms aegis a —— ayer yet? + HO+ CH, QO CH; ted ketone Pmacoione EnvLeNe GLYCOL, 1.2-Ethanediol, HOCH,CH,OH At ts the simplest and most important member of the class. It 1s often referred to as glycol Preparation (1) Hydroxylation of Ethylene. Ethylene glycol may be prepared by passing ‘ethylene into cold dilute potassium permanganate solution. CH, cos, GHz —OH + O40) wae | bx, "COT ramo” Gra,—on Ethylene Etnyiene gtyco! of Fthylene dibromide, In the laboratory glycol may be obtained by boiling with aqueous sodium carbonate. + NasCO,; +H, ——-* | + 2NaBr CH,OH Ethylene glyco! ee milly by hydrolyzing496 | ADVANCED ORGANIC CHEMISTRY CH, ot que -OH HOO) a> bi, ‘ CH,—Cl Ethylene Ethylene chlorohydnn (4) Hydrolysis of thy lene oxide, By hydrolysis of ethylene oxide with H,0 at 2067 Under Pressure or with dilute H)SO, at 60"C, CH)—CH Hi, CHa—CH, W Jor HyO Fone | OH OH we oxide Ethylene glycol Ethylene oxide is made by passing a mixture of ethylene and oxygen over heated silver Catal CH=CH, + 0, —H» CHy- 70H, 5 ° Ethylene Ethylene oxide Properties. (Physical). Glycol is a colorless viscous liquids, bp 197°C, mp ~ 115°C. sp gl at 20°C. It has a sweet taste, It is miscible with water and ethyl alcohol in all proporions bur insoluble in ether, It is as toxic as methyl! alcohol when taken orally. (Chemical). Ethylene glycol molecule contains two primary -OH groups. Its chemical reactions are, therefore, those of primary alcohols twice over. Generally, one -OH group is attacked completely before the other reacts. More vigorous conditions are sometimes needed for reaction of the second of the two -OH groups. (1) Reaction with Sodium. It reacts with sodium at 50°C to form monoalkoxide and dialkorde when temperature 1s raised, CH,-OH soc CHp—ONa + Na ——»> l | + RH, CH,-OH CH.-OH Ethylene glycol Monoalkoxide CH,-ONa 160°c CHp—ONa —> |. + BH CH,—' CH,-ONa Dialkoxide (2) Reaction with Hydrogen chloride. Hydrogen chloride reacts with ethylene glycol in two steps ; first forming ethylene chlorohydrin at 160°C and then at 200°C to yield ethylene dichloride. CH,—OH CH,—-Cl é +n, SS ip + H,0 CH,—OH CH)~OH e chlor rin Ethylene glyco! oe lie CH,—CI CH,—Cl A + ho So. + 1.0 CH,—OH CH,-Cl 1,2-Dichloroethane loride or phosphorus hi (4) Reaction with Phoyphorus halides. It reacts with phosphorus tric! lie tebromade to form the corresponding dihalides when both the -OH groups are rep ates, :A47 CPOE id RO ATEIIIE ALC EVES at On m CH tr iy ‘ 4 Vn * @ 4 BHM, OHy-OH . dn, tir Ey Uthylana glysat E thoylenvay clarence Mhoyphortie tttlotids, hawever, protien othyhene ditedide which beng anata al ance yields justine anal ethylene: yee on, f ty i \y i _ . » + lp CH OH My) Oy Ethylene giyeot 12. Diindoathane [thyharies (Uivatiabla) (1) Reaction with Carboxylic acids cents with earboryle neldé to give mann ot dieters, depending upan the relative amounoy at ethylene glycol and weld taken CH, OH HOOCEH, Ww GHy OOCCH, ' > i 4 1,0 My OH My OW Ethylene glyool Acetic acid Glygol monoacatate CHy OOCCH, " SHy= OOCCHy * oe + WO Hy OH HOOCCHy My OOCH,CHy Glycol diacetate When esterttied with adibaniy acid i foruin polymers @g. »|nooc-{")-coon + nN HOCH,CH,OH ~~» Torephthalic acid Fihylene glyool ro-t-co-C)-00-oo1010-1-4 + (2n—1)H,0 Torylono (5) Reaction with Aldehydes or Ketones, Hihylene glycol condenses with aldehydes or ketones in the presence of sulfuric acid to yield cyclic acetals or ketuln, ee Cr xX, | mals C: CH,— ~~ «ao se Ethylene glycol Aceluldahyde Cyolle acotul ee ots Ht Tt ieee CH)— ON cH, *” CH—-o~ cH, * HO Ethylene glycol Acotone Cyclic katat ‘The formation of cyclic ketal can be used as u means of protecting carbonyl groups in reactions ‘curried in alkaline solutions, The carbonyl! group can be regenerated hy the action of periodic acid on tho ester, CH,-O. wa Rilo, i i 2H—C—H + R—-C—R moo A Formaldehyde’ 498 | ADVANCID ORGANIC CHEMISTRY ol with nitric weld ylelide a Mber Gf gut, May Johyde and then carhax ytic bt Koy (6) Oxidation. () The oxidation of ethylene gly« at 4S one or both the primary OH groupy may be oxidized [int te Hp, ‘The oxalic acid is obtained as the fil product of oxidation CH,OM | coon Glyoollla acid CH,OH —_-CH,OH CHO, QOOH bH,0H ae cHo COOH COOH Ethylene Glycollic Glyoxylio Oxalio glycol aldohydo acid acid a 9 ee CHO Glyoxal (i) Oxidation of ethylene glycol with acid pomssium permanganate or potassium dichromate results in the formation of formic acid by cleavage of carbon-carbon bond, 0 CH,—OH Il Lt wt, 2H—-C—OH + H,0 CHy—OH Formic acid Ethylene glyco! (iii) When oxidized with lead tetraacetate or periodic acid, ethylene glycol produces formaldehyde. 0 CH,—OH ll ee Os c= CHp—OH Formaldehyde Ethylene glycol (7) Dehydration. (a) When heated with zinc chloride, ethylene glycol gives acetaldehyde. oO CH2—OH ang, ll I art CHy—-C—H 4 H,0 CH,—OH Acetaldehyde Ethylene glycol (b) When heated alone at 500°C, it gives ethylene oxide, qhe--GHe SOUS CH=CH, —» OH OH ‘o +i Ethylene glycol Ethylene oxide (c) Upon heating with concentrated sulfuric acid, it is converted to dioxane which is used as a" industrial solvent,CHAPTER 14. POLYHYDRIC ALCOHOLS | 499 yoo CH,—CH, H—O . a HO p—y 484, 0 Oo + 2H,0 CH)—CH, CH)—CH, Ethylene glycol i (2 Molecti¢s) pyrene (@) When heated with concentrated Phosphoric acid, it gives diethylene glycol. HO—CH,—CH, : HO—CH,—CH, i OH rem! HyPO, O + HO HO—CH,—CH, 1 Ethylene glycol Diethylene glycol Uses. Since glycol forms freezing mixtures with water (60 percent solution freezes at—35°C), itis sold under’ the name Prestone for use as antifreeze for car radiators and as a cooling liquid in aeroplane motors. Itis also used : (i) for Preventing ice formation on aeroplane wings, (ii) in making low-freezing dynamite, (iii) as a preservative, (iv) : as a dielectric in electrical condensers, and (v) as a starting material for numerous valuable compounds : nitroglycol, an explosive; diglycol oleate, a rubber ; glycol stearate, a lubricant for watch Springs; monomethyl ether, a solvent for cellulose, terylene etc. Glyools are polar compounds and dissolve readily in water. They are major components in commercial car-coolants and airplane deicing fluids ETHYLENE CHLOROHYDRIN, 2-Chloroethanol, CICH,—CH,OH Itis made on a large scale by bubbling ethylene into aqueous Solution of hypochlorous acid (chlorine water) H,C=CH, + HOC] ——* HOCH,—CH,CI Ethylene chlorohydrin Itis also obtained by the action of hydrogen chloride on glycol at 100°C. 100°C HOCH,—CH,OH + HCl — HOCH,—CH,CI> 500 | ADVANCED ORGANIC CHEMISTRY lorless liquid, bp 128.8°C. It is miscible with w, ater yieldsethylene oxide, al Properties, Ethylene chlorohydrin is a.col saibtoni proportions. When distilled with concentrated alkali solutt CH,—CHp Distil HOCH,—CH,Cl + NaOH ——* VW + NaCl + 1.0 Ethylene chlorohydrin possesses two different functional groupe ae is useful with Organic synthesis. For example, by heating with aqueous sodium cyanide ie Converted to ethylene cyanohydrin which upon hydrolysis with hydrochloric acid gives 3-hydroxypropanvic acid, —CH,Cl + NaCN ——® HOCH,—CH,CN + NaCI te Ethylene cyanohydnin HCI HOCH,—CH,CN + 2H,0 ——-» HOCH;—CH,COONH, —*» HOCH,—CH,COOH 4 Nic, ‘3-Hydroxypropanoic acia TRIHYDRIC ALCOHOLS (TRIOLS) Alcohols containing three -OH groups are called Trihydric Alcohols ot Triols. The Introduction of the third -OH group in a diol molecule raises the boiling point by about 100°C, Increasing the viscosity. An increase in the number of OH groups also enhances the hydrogen bonding ability ang association, thereby raising the boiling point. 290°C 78°C As Hydrogen Bonding Increases ~ Boiling Points Increase. Chemically, triols give many reactions of the primary and secondary alcoholic groups which they contain. They give the simple reactions of -OH groups in triplicate, The only important member of the class is glycerol or 1,2,3-propanetriol. GLYCEROL, 1,2.3-Propanetniol, HOCH,~CH(OH)-CH;OH % Glycerol 1s the simplest trihydric alcohol (triol), The name glycerol or glycerine was originally derived from the word glycerms, meuning sweet. Its UPAC name is | .2,3-propanetriol since glyce"l sould be considered as trihydroxy derivative of Propane, Manufacture, Glycerol can be prepared industrially by the following methods.(AMR 14 POLYHYORIC ALCOHOLS | 501 (1) From Fats and Oils. Natural oils acids (mainly palmitic, stearic, and oleic glycerol and the salts of the long-chain and fats are triesters of glycerol and long-chain carboxylic acids), On hydrolysis with alkali, the fats and oils produce acids which are called soaps. CH,OOCR tz00 CH,OH GHOOCR + 3NaQqH —* CHOH 4 3ACOONa CH,OOCR . re Soap Fat or Oil Glycerol (1,2,3-Propanetriol) In the above equation, R is 9 to 17 carbons. eat ‘The hydrolysis of futs and oils is carried originally for soap manufacture, and glycerol is obtained as a by-product. This is still a commercial source of glycerol. Glycerol from Soap Manufacture. In Soap manufacture, the fat is hydrolysed by boiling with alkali solution. The carboxylic acids produced by hydrolysis react with the alkali to form solid soap while the glycerol is left in the solution. The soap is filtered out. The filtrate is called Spent Lye. Spent lye “st is Alum To To vacuum pump — vacuum pump Steam NaCl 90% Glycerol Fig. 14.1. Recovery of glycerol from spent lye. Spent lye contains 4 to 6 per cent glycerol, unused alkali, soluble soaps, and suspended impurities. Itis allowed to stand in a tank where most of the suspended impurities settle down. The clear solution is transferred to a new tank where it is first treated with HC! to neutralize excess alkali, It is then treated with alum (aluminium sulphate) and steam (Fig 17.1). The remaining excess alkali is precipitated as aluminium hydroxide and the soluble soaps are converted into insoluble aluminium soaps. These impurities are filtered out. The filtrate is next concentrated under vacuum when most of the sodium chloride separates out. This is filtered and the filtrate is treated with animal charcoal to remove colored impurities. After filtration, it is again subjected to vacuum distillation. The glycerol thus obtained is 90 Percent pure. To obtain pure glycerol, it is redistilled under vacuum until distillate has specific gravity of 1.26, (2) From Propene. Large quantities of glycerol are obtained as a by-product in the manufacture of soap. However, this ‘supply is not sufficient. Today much of glycerol is manufactured from propene obtained by the catalytic cracking of petroleum. Following four steps are involved :_—_ ADVANCED ORGANIC CHEMISTRY 502 a Step L. Propene is treated with Cl; at 600°C to give ally! chloride. °C, CH;—CH=CH, + Cl gon". CICH,—CH=CH, ; Allyl chloride Propene Step 2, Ally! chloride is treated with dil. NaOH to give allyl alcohol. CICH,—CH=CH, + NaOH ——> HOCH,—CH=CH, Allyl chloride Ally! alcohol Step 3. Allyl alcohol is treated with dilute hypochlorous acid to give a chlorohydrin . of HOC] to the carbon-carbon double bond takes place according to the Markoynikoy rule itiog ig i ef HOCH, — CH=CH, + HO—cl —> HOCH CH—cH, - C OH © Allyl alcohol Glycerol a-chlorohydrin Step 4. The chlorohydrin is treated with dil. NaOH to yield glycerol. Ae ae + NaQH —> HOCH: —CH—cH, I OH OH OH cl Glycero} Glycerol a-chlorohydrin Alternative Method. Propene may be oxidized with oxygen (air) in the to give acrolein, Acrolein is then treated with hydrogen peroxide (Hydro: xylati Presence of CuO at 35°¢ ian) followed by reduction to produce glycerol. Il CH;=CH—CH, + 0, 2% CH=CH—C—H ae Propene Acrolein OH O OH | Il Hp | HOCH,—CH—C—H Wiorpt? HOCH,—CH—CH,OH Glycerol Propene required for the In a country like India where petroleum is not found in abundance, n industry. above synthesis may also be obtained from acetone of the wood distillatio ? OH CHy—C—CH, =» — s 3 Bron” CHa—CH—CHy eo» Acetone 2-Propanol Properties (Physical). Glycerol is a colorless, odorless sweet-tasting and syrupy liquid, bp 290°C. Itis nontoxic. Glycerol is soluble in water and ethanol, but insoluble in ether. It is hygroscople. that is, it absorbs moisture from air, (Chemical). Glycerol molecule contains two primary OH groups and one secondary OH group: M undergoes many of the reactions to he expected of these types of alcohols, The carbon atoms in glycerol are indicated as a, B, and a, CH3—CH=CH, Propene| CHAT 4 POLYHYDRIC scons 503 Primary Seconda ry « CH, — Groups group mts On 6 HOH (eee 6 HoH CHE OH a CH, Glycoro! aot Glycerol Feactive than the secondary ~OH group. Some Compounds are modified to a certain extent by In general, the (Wo primary ~0} H groups are C mor of the reactions that are characterist . < ic of Monohydroxy Fecal give disodium glycerolate, The secondary -OH group does not CH,OH CH,ONa GH,ONa Ne GHOH = —*> cHOH Ms Guon CH,OH CH,OH bone Glycerol Monosodium glycerolate Disodium glycerolate Q)_ Reaction with PCL, Glycerol reacts with PCI; to form glyceryl trichloride. All these OH groups are replaced by Cl atoms. treo CH,CI CHOH + 3PCl —+ fuel + 3POCl; + 3HCi CH,OH CH,Cl Glycerol Glyceryl trichloride (1,2,3-Trichloropropane) 3) Reaction with Carboxylic acids, Glycerol reacts with monocarboxylic acids to form mono-, di-, and triesters depending on the amount of acid used, For example, glycerol reacts with a mixture of acetic acid and acetic anhydride to give the following three esters : cman GHLOOCCHs CH,OOCCH, CHOH CHOOCCH, CHOOCCH, G08 CHZOH CH,OOCCH, Glyceryl monoacetate Glyceryl diacetate Glyceryl triacetate (4) Reaction with Hydrogen chloride. When HCI is passed into glycerol at 110°C, both a- and B-glycerol monochlorohydrins are formed. If the reaction is carried for a long time, glycerol ,01-dichlorohydrin and glycerol 0.,-dichlorohydrin are formed. a CH,OH CHCl CH,OH 8 buon + HCl an GHOH + Geil | x’ CH,OH CH,OH CH,OH Glycerol a-Monochlorohydrin f\-Monochlorohydrin ee504 | ADVANCED ORGANIC CHEMISTRY otal (5) Reactioa with Nitric acid. Glycerol reacts with nitric acid in the presence of Sulfuric ag. (catalyst), at 25°C to form glycery| trinitrate, commonly known as Nitroglycerin. Itis a pale yeljoy, ms liquid. It is a powerful explosive which detonates on slight impact. ni CH,OH CH,ONO2 I CHOH + 3HONO, ct» GHOND, + .3th0 I Ni CH,OH mee CH,ONO, Glycerol Glyceryl trinitrate (Nitroglycerine) (6) Reaction with Hydrogen iodide. Glycerol reacts with hydrogen iodide in two ways: (a) When glycerol is warmed with a small amount of hydrogen iodide, jt Bives 1,2,3-triiodopropane. This is unstable and splits out a molecule of iodine to yield allyl iodide CHOH Gt Gp Wi HOF siece” SF Seah) Ct CHT CH.OH CH! CHaI Glycerol (Unstable) Ally! iodide (b) When glycerol is heated with a large amount of hydrogen iodide, allyl iodide first produced as above is reduced to propene. In the presence of excess hydrogen iodide, Propene adds a molecule of hydrogen iodide to give 2-iodopropane (isopropyl iodide). The addition takes Place according to the Markovnikov rule. CH, CH, CH, CH. Mere he aa es iS ane pie = i" ah ie CHI CHI CHa. CHg Allyl iodide (unstable) Propene 2-lodopropane (7) Reaction with Oxalic acid. Glycerol reacts with oxalic acid in two ways : (a) At 110°C glycerol reacts with oxalic acid to form glycerol monoformate. 9° ° ] ] CH,OH” © # HO—C. CH,0—C—H ! no, | TLE —e fe + HO CH,OH CH,OH Glycerol Oxalic acid Glycerol monoformate Glycerol monoformate on hydrolysis gives formic acid and glycerol is regenerated. oO {I ee soe f ae + HO —» CHOH + H—C—OH CH,OH ie OH Formic acid GlycerolCHAPTER 14 POLYHYDRIC ALCOHOLS | 505 (b) AL260°C glycerol renets with oxalic avid to form allyl aleohol, HOH om ol Be, fi ee 1? ot mmo HO Gy, ~260,” Ku | CH,OH CH,OH CH,OH Giyaero) Oxalle acid (unstable) Allyl peat (8) Reaction with Acetyl Chic Rare ian . finn siyooryl ttcetso, cetyl Chloride, Glycerol reacts with acetyl chloride (or acetic anhydride) to io ‘ BROCCH, CH,OOCCH, ) —Y» cHooccH, + SHC! CIOCCH, CH,OOCCH, Glycerol Acetyl chloride Glycerol triacetate (3 molecules) (9) Oxidation, The two primary alcohol groups in glycerol are capable of being oxidized to the aldehyde and then the carboxyl group. The secondary alcohol group can be oxidized to the carbonyl group. Thus glycerol can give rise to a variety of oxidation products depending on the nature of the oxidizing agent (Fig. 14.2), nee GH.OH COH aad — GHOH —+ CHOH CHO CO,H CO;H nor Glyceraldehyde Gilyceric Tartonic HOH acid acid CH,OH CH,OH CO;H Glycerol | | oa — ce CH;OH CO;H Dihydroxy Mesoxalic acetone acid Fig. 14.2, Oxidation products of Glycerol. (@) Oxidation with dilute HNO, gives glyceric acid and tartonic acid. (b) Oxidation with concentrated HNO; gives mainly glyceric acid. (©) Oxidation with bismuth nitrate gives mainly mesoxalic acid. (d) Oxidation with bromine water, sodium hypobromite, or Fenton's reagent (FeSO,+H,0>), gives amixture of glyceraldehyde and dihydroxyacetone. (©) Oxidation with periodic acid gives formaldehyde and formic acid. CH,OH ? Il ll Gon + 2HIO, ——> 2H—-C—H + H—C—OH + 2HIO, + HO CH,OH Glycerol Formaldehyde Formic acid _506 ADVANCED ORGANIC CHEMISTRY (10) Dehydration, When heated alone or with potassium hydrogen sulphate, glycerol} climinat {Wo molecules of water to form acrolein, CH,OH Cte CHOH aes cH + 2H.0 | CH)OH CHO Glycerol Acrolein é This reaction is often used as a qualitative test for the presence of glycerol, since Acrolein jg easily detected on account of its peculiar odor. (1D Formation of Glyptal resins, Glycerol reacts with phthalic anhydride forming Polyesterg Known as glyptals, Each of the three -OH groups in glycerol forms an ester linkage with the anhydride, giving a thermosetting polymer (plastic) used for making synthetic fibers. 0 Il x nC - +a” gehen pi tse aha ——> Cc t OH oO Phihalic anhydride Glycerol 9 ° 1 il ae =O-6 C—O CHp—CH-CHp—O-C. C=O — OW $ oO | Giyptal Uses. Glycerol is nontoxic and an excellent humectant (moisture-retaining agent). It is used in bakery products, hand lotions, vanishing creams, shaving soaps and tooth pastes. Glycerol is used in production of plastics, synthetic fibers, and surface Coatings. Itis used in the manufacture of explosives like Dynamite and Cordite. NITROGLYCERIN, Giycery! trinitrate, CzHs(ONO,), The name ‘nitroglycerin’ assigned to this substance is incorrect, It is atriester of glycerol and nitric acid, and hence the proper name would be glyceryl trinitrate or simply glyceryl nitrate. Preparation. Nitroglycerin is manufactured by adding glycerol slowly to a mixture of nitric acid and sulfuric acid maintained at 20°C, CHa OH CH,-O—NO, H2SO, GOH + 3HO-NO, o> GH-O-No, + 3H0 CH,-OH CH,-O—NO, Glycerol Nitrogiycerin