Gow Hi 2 929 27.4 Hidroxialdehidos e Sec. 27.4 A. Sintesis Hidroxialdehids Lat ioxileion ois or aun dels éereonedioenun ean, dotnet come ter toceno, Earner an Ja reacci6n recibe el nombre de condensacién aciloinica. E] ‘producto ial de la Feacci6n es la sal disédica de un ‘enodiol, que se hidroliza produciendo la aciloina, sclielig +4Na ty O” Nat NN + 1 NaOMe #2, ~ Nat W oH La condensacién aciloinica es un método iil para la sintesis de compuestos siGicos, sobre todo los de tamatio medio (8-13 eslabones) En estos exces, Ip carbonilo del éster produce un intermedio cetilico, La principal reaccion secunda. a &s la condensacién de Claisen (Sece. 185), producida por el ion aleéxido obtenido como producto secundario en la reaccién, J-0s aldehidos aromiticos se convierten en acloinas por accidn del cianuro de joie en ctanol acuoso, Esta reaccién se denomina condensacidn benzoinica, y el ion cianuro es un catalizador especifico, a ‘CHO C—CH. : CT we OC) t wean = dhoraen 2 un grupo ciano y es lo sufcientemente Acido para eliminarse pos una base. A continuacion el carbanién resultante se adiciona a otra molecula dealdehido, obteniéndose un intermedio cianodiol que, por pérdida del ion cianuro, produce la aciloina y regenera el catalizador. i a oH on RCHO 4 CN- = RCHCN 2 RCHCN == RC—CN abe Rogt Fe Pitti TH WC Ae Cm le EC mae REE + ON oe oN cn ‘Aunque las condensaciones aciloinica y benzoinica dan origen al mismo tipo de productos, es de destacar que transcurren a través de mecanismos completamente diferentes. La sintesis més general de f-hidroxialdehidos e hidroxicetonas es la conden- sacin alddlica (Sece, 14,8.C). Recuérdese que los aldehidos simples se condensan produciendo f-hidroxialdehidos cuando se tratan con una base acuosa en frio OH nat Lit 2CHCHO S34 cHCHCHCHO En condiciones més fuertes, como las necesarias para efectuat la condensacion inicial con aldehidos de mas de seis carbonos, el f-hidroxialdehido resultante se deshidrata, obteniéndose el aldehido x,6-insaturado, mle, ae c10 ts RAR a on) . septa 2entlaonenl Las condensaciones aldélicas cruzadas pueden efectuarse convirtiendo una cetona completamente en el enolato de lito, y haciéndolo reaccionar a continua- cién con un aldehido, La hidrolisis del alobxido resultante con agua produce la p- hidroxicetona, en general, con buen rendimiento. a) P Cr fm Tiersen, cuecr, ene no, asx) 4+-hidrox-4eni-2-butanona EJERCICIO 27.6 Las condensaciones aciloinica, benzoinica y aldética se utilizan como métodos de sintesis de dioles. Muéstrese eémo pueden prepararse los dioles siguientes utiizando una de estas condensaciones como etapa clave (a) 1.2-difeniletano-1,2-diol (b) hexano-3.4-diol (© butano-1,3-diol (d) hexano-24-diol Describase el problema estereoquimico que surge en tres de estas sintess, 930963 15, Indiquese cémo utilizar la anelacién de Robinson para obtener cada uno de los “compuestos siguientes Problemas SP COOEt “ os tis 16, El L-feniletenol-t-d, C,H,CHDCH, (B) se ha preparado en forma Spticamente activa Este compuesto es interesante porque su quiralidad se debe a la diferencia isotépica ‘entre el Hy el D. No obstante, su rotacion tiene un valor relativamente alto de [2lp = 06. La configuracién absoluta de B se correlaciona con la configura cién conocida del dcido mandélico mediante los siguientes esquemas de reaccién, oon OH Me Css Mas CH Or AO, Ute CHO eats ‘écido (—)}-mandélico ce Te ti cathy 2 4 p> OF ESO, 6, 44480, Es (HCALCHDCH B Deshizcase la configuracién absoluta de(—}-B y la estructura y configuracion de cada intermedia, C-F, del esquema. Asignese la notacién RS apropiada para cada estructura B-F. 17. Las a-dicetonas experimentan una transposicién interesante cuando se tratan con tuna base fuerte LS se mht a 0, em bcooH ‘ensto | SE oo) La reaccin se denomina transposicién de Acido bencfico, que proviene del nombre ‘vulgar del écido (difenil)-hidro (a) Sugirase un mecanismo para la reaccién, (b) Propéngase un mecanismo para la transformacién andloga siguiente ° A coon x a (o) Esquematizar una transformacién en varios pasos de la ciclohexanona en 1- hidroxiciclopentanona,BENGIL 87 3. Methods of Preparation Benzenesulfony! ebloride ean be prepared by the action of phos- horus pentackloride on henaonosulfonie acid or its salts! by the dotion of phosphors oxychloride upon the salts of benzenesulfonie acid:? by the action of cblorosulfonio acid on benzene® or sodium benzenesulfonate;* and by the aetion of sulfuryl ebloride on benzene in the presence of enhydrous aluminum chloride? BENZIL (CaHCH(OH)COCGH, + (0) ++ CHLCOCOCH, + 10 Submited by. . Cate and BE, Dears. Gheeked by Roose Anus upd Genaia IL. Cours. 1, Procedure Iw a 1241, flask, fitted with « mechanical stirrer and mercury sesl, a rellux condenser and an inlet tube for the introduetion of wir, is placed fa mixture of 4100 g, (18.4 moles) (Note 1) of erystalline copper sul- fate (Note 2), 4000 g. of technical pyridine and 1600 g. of water. "This ig heated on a steam bath with stirring until the eopper sulfate is completely dissolved and then 1696 g. (8 moles) of benzoin (p. 94; ‘unreerystallized material is satisfactory) is added and heating and stirring continued for two hours, ‘The reaction mixture beeomes dark green in color and the melted benzil forms the upper layer. After tooling, the copper sulfate-pyridine solution is decanted and the benzil wwaslied with water and then heated with 2-4 1. of 10 per ent hydro- chlorie acid. After cooling, the benal is filtered, washed with water, dried and recrystallized from carbon tetrachloride (2 1. of solvent por kg. of bensil). By concentration of the mother liquors a certain ‘amount of benzil is always obtained, ‘The total yield is 1450 g, (83 per cent of the theoretical amount) of recrystallized material melting, at 94-95° (Note 3) Gerhardt and Chionaa, Ann. 87, 29 (1853); Vort, Ana. 119, 143 (Footnote) (1861): Otto, Z. Chem. 100 (1886); Barbogln and Kekalé, Der. §, 876 (187295 Bourgeois, Ree, trav, chim. 18, 492 C800); Mobrmsan, Aun. 410, 279 (918); Rosenmiind and Strek, Ber. $4, 430 (1021). Gerhardt and Chance}, Compl, red. 35, 090 (1882). 2 Kip, Z Cheon (1860); Ponumeree, Ver. 42, 102, 2274 (1900; Ulan, Vier. 42, 2057 (1900); Stcshainfsbrie AG, Gee. pat 724886 (Fed 10, 114 ‘ania. “Tlewrsgnn and Rachlin, Ber, 18, 118 (1882). ‘ieacken, Roe, tay, chim. 0, 382 (911),Ao 88 ORGANIC 81 THESES ‘The copper sulfate-pyridine mixture is readily reoxidised by pass ing a current of air through it for thirty-six hours (Note 4). To this resulting solution is now added 200 g, of pyridine and it is then used for oxidising another 1696 g. portion of benzoin. 2, Notes 1. In checking this preparation, runs about 25 per cent of the sine rleseribod were made. The yields were about 3 per cent Tess than in the larger runs, For the reoxidization of the smaller amount of copper sulfate-pyridine solution, air was passed through for fifteen ous. ‘Copper hydroxide (or earbonate) does not dissolve in pytidine. 3. In eomparing the copper sulfate-pyridine method with the nitric ‘acid methiod (Org. Syn, 1, 25) it should be pointed out that the eon- stants on the samples are as follows: etioa ar | ar | ratege tet Grado | rasp | "on leo Compr atte iin sear | ons | Meee Mieadoet co so 3-90 | Positive In other words, by the nitrie acid oxidation it is difficult to obtain ‘8 produet completely free from benzoin, The yiekis by the nitric ‘acid method are generally about 95-96 per eent, whereas with the copper sulfate-pyridine method the yield drops to approximately 85 per cent. ‘The melting temperatures of mixtures of benzil and benzoin show! that the maximum possible depression is 10°. 4. Fifteen hiours was found not long enough to offect » complete oxidation, 3, Methods of Preparation Bensil is readily formed by the oxidation of benzoin with nitric avid? chlorine iodine electrolytically and eatalytically® ‘The pro- janstone, J. Chem. Soe. 98, 600 (1900), 2 inn, Ann. 34, 18 (1940); Adama and Marvel, Org. Syn. 1,25 (1800). Taent, Ann. 17, $1 (180. “Comm itd Meister, J. Aim. Chom, Soe $1, 2998 (1000) James, bid. 21, 598 (1590), ‘Zetucbe nod Za, Helv, Chim. Acts, 9,288 (1820),ENZILIC ACID 89 cedure deseribed is based on the observation? that benzoin reduces Fehling’s solution in the cold. Pyridine was selected because it pre ‘vents precipitation of cuprous oxide, is not so volatile as ammonia, and ‘acts as a partial solvent for benzoin. It has been shown* that copper, pyridine and air oxidize benzoin to benzoic acid. The same oxidation ‘leo takes place in the absence of copper. Bensil can also be prepared from dosoxybensoin with selenium dioxid BENZILIC ACID 3C\I1,CHOHCOC,H, + NaBr0s + SNsOH 3(CaHL.),C(OH)COONa + NaBr-+ 31,0 Submitted by Doseato A, Bauzauo and Wrasse M. Dus Checked by CS. Mavis: and Tax-Taxse Cav. 1, Procedure ‘Taw reaction mixture of bonzoin, propared by the method described on p. 94, is permitted to stand until the next day, when it is filtered, washed with water but is not dried or purified. In a 30-cm. evap- orating dish 500 g, (12.5 moles) of sodium hydroxide and 115 g. (0.76 ‘maole) of sodium bromate (or 125 g. of potassium bromate) are dis- solved in 880 ce. of water. ‘The moist bensoin (450-400 g,) is added in portions to this solution and the mixture is stirred, preferably with ‘8 mechanical stirrer, while hoated on tho steam bath (Note 1). As heating continues the mixture thickens and more water is added from time to time. A total of 750-00 ce. is needed. ‘The heating and stirring are eontinued for about five to six hours or until a test portion is completely or almost completely soluble in water. ‘The mixture is diluted with about 4 1, of water and is permitted to stand overnight. A small quantity of oily or solid impurity (ben- zohydrol) is removed by filtration, and dilute sulfuric acid (about 1300 ce. of a solution of 3 parts of water and 1 part of concentrated sulfurie acid, sp. gr. 1.84) is added to a point short of liberation of bromine, ‘The product is filtered, washed with water and dried. ‘Thus 450-184 g. (§4-90 per cont of tho thooretieal amount based on the enaaldchyde) of benailic acid melting at 149-150° is obtained (Note 2) "Wiech, Aun. 211, 24 (footnote) (1882). * hfchler, Her. Chim, Aeta, 8, 70 (1025). 9 Matt, Pigin, and Hourran, J. Chem, Soc. 1936, 2ollution Prevention and Control Technologies for Plating perations ection 6 - Wastewater Treatment .2. CONVENTIONAL TREATMENT TECHNOLOGIES 2.3 Cyanide Oxidation carly all electroplating shops that generate dilute cyanide bearing wastewaters employ alkaline chlorination treatment. This process, which has cen in commercial use for over 35 years, is suitable for destroying free dissolved hydrogen cyanide and for oxidizing all simple and some ‘omplex inorganic cyanides in aqueous media (ref. 348). If properly designed, maintained and operated (good pH and oxidation reduction ‘tential contre, the process will oxidize cyanides which are amenable to chlorination (i.e. the cyanide that can be oxidized by the alkaline hlorination process), to less than 1.0 mg/l cyanide (ref. 39). Extensive sampling by EPA showed that the average effluent concentration from a ell opcrated cyanide destruction system contains 0.18 mg/l of total CN and 0.06 mg/l of amenable CN. he cyanide in very stable complexes, such as ferrocyanides or ferricyanides, is basically unaffected by chlorination (ref. 243). Cyanide that is ‘ompiexed with copper, nickel and precious metals is amenable to chlorination, but reacts more slowly than free cyanide and therefore requires xxcess chlorine for efficient cyanide destruction. Concentrated cyanide wastes, such as spent plating or stripping solutions, should not be eacted with hypochlorite because the reaction can be violent, with the emission of chlorine gas. These wastes can be batch treated by lectrolytic oxidation and thermal destruction (ref. 242). schematic of an alkaline chlorination process is shown in Exhibit 6-6. Most often the process is operated in two stages, with separate tanks or each stage, A common exception is batch treatment systems, where one tank is typically employed (ref. 38). Destruction of dilute solutions ‘ cyanide by chlorination can be accomplished by direct addition of sodium hypochlorite (NaOC!), or by addition of chlorine gas plus sodium ydroxide (NaOH) to the wastewater. With direct chlorine gas addition, sodium hydroxide reacts with the chlorine to form sodium hypochlorite election between the two methods is based primarily on economics and safety. The chemical costs for chlorine gas treatment are less than half ‘ose of direct hypochlorite addition (see Section 6.3.2), but handling is perceived to be more dangerous and equipment costs are higher (ref. 9), Relative tothe safety issue, one expert source argues that modern gas handling equipment is highly reliable and designed to be relatively ail safe (ref. 38). The results of the Users Survey indicate thet 95% of the respondents with alkaline chlorination processes use sodium yypochlorite and $% use chlorine gas plus sodium hydroxide. The shops that use chlorine was tend to be the same shops that select sulfur joxide for chromium reduction (e.g, PS 025 and PS 093). Generally, these shops have substantial cyanide wastestream flow rates. n the first stage of teatment, hypochlorite oxidizes eyanide to cyanate. This reaction is accomplished most completely and rapidly under Ikaline conditions at pH 10 or higher (prefered range is 11.0 to 11.5) (ref. 38). An oxidation period of 10 to 15 minuies is usually adequate ref 38); however retention times up to 60 minutes are routinely used (ref. 39, 348). An ORP set-point of approximately +325 millivolts is NaCNO +NaCl nd in the second stage, 2NaCNO + 3NaOCI + H20 - > 3NaC1-+N2 + ZNAHCO3 ‘odium hypochlorite consumption is usually estimated to be 25 to 100 percent greater than the stoichiometric requirement (approximately 7 Ibs £C12 or 7.5 Ibs of NaOCl per Ib of CN); where the excess is consumed by oxidation of organics and raising the valences of metals in theastewater (rf. 39), The results of the Users Survey indicate that most shops are using substantially higher dosages (up to five hundred percent more). Higher dosages by respondents may be the result of the formation of metal complexes (¢g., due to inadvertently combining cyanide nd nickel oF iron bearing wastewaters, use of unlined stcel tanks, use of stee] anode baskets and not retrieving fallen pars from tank bottoms) Wor poor pH control during treatment. The latter reason is especially apparent for several shops that operats single stage cyanide destruction rocesses and do not add acid to lower the pH. As a result, the second part ofthe oxidation reaction is slow and operators probably add higher ‘sages of NaOCl to compensate forthe speed ofthe reaction. Shops operating under these conditions include: PS 08, PS 135, PS 204 and PS: {0-It should be noted that acid additions must be made under the correct conditions or a severe safety problem could arise. Dilute acd is ometimes used in place of concentrated acid to reduce the danger of operating this process (ref. 243). Also, some equipment vendors provide a tustic feed capability that is controlled by an independent set-point, usually at a pH of 7.5 (ref. 38). The use of acid in the alkaline chlorination rocess is discussed by Roy (ref. 38). tkaline chlorination systems have generally proven reliable if well maintained. Use of a well-designed ORP control system is highly ecommended, Most problems with the system focus on failures of this element. Exhibit 6-7 shows the response of various electrodes to the {Yanide-to-cyanate reaction end point. The graph shows thatthe gold-plated electrode, although more expensive, gives much better reagent dition control (ref. 39). here are several alternatives to the alkaline chlorination process. These are discussed in the following paragraphs. zone oxidation of eyanide has been practiced asa substitute technology for alkaline chlorination. I is effective in destroying cyanide to the ‘els required by EPA. The advantage of using ozone lies in reduced operating costs. Ozone is generated on-site (typically by the silent lectrical discharge method) and is less expensive than chlorine or sodium hypochlorite. The equipment cost is significantly higher, however, ‘wing to the expense of an ozone generator. Another disadvantage of the process is that it does not oxidize cyanide past the cyanate stage, hess exeess ozone is used. Ozone oxidation requires 1.8 to 2.0 Ibs of ozone per pound of CN to reach the cyanate stage and 4.6 to 5.0 Ibs to each complete oxidation. An advantage of ozone oxidation is the absence of chlorine that ean combine with organics present inthe wastewater produce toxic compounds (ref. 39). Another advantage isthe ability of ozone to destroy zine, copper and nickel cyanide complexes (re. 243). the ozonation process has also been combined with UV radiation forthe treatment of halogenated organics (ref. 348, 386). None of the cespondents to the Users Survey employ ozone oxidation of ey ther alternatives to alkaline chlorination include: alternative chemistries; electrochemical oxidation; thermal oxidation; and precipitation. lemative chemistries include hydrogen peroxide (PS 020 and PS 273) (ref. 386) and calcium hypochlorite (PS 174), lectrochemical oxidation is sometimes used to destroy concentrated cyanide wastes (eg,, >50,000 mg/l CN). A description of the required ‘quipment, including a small commercial unt, is presented in AESF literature (PS 243). thermal treatment of cyanide wastes is performed by two of the respondents to the Users Survey (PS.142 and PS 245). Their equipment is rovided on a rental basis by Cyanide Destruct Systems (Canada). The equipment can be purchased for $40,000 or rented for $600 per week. § 142 also indicated that they required a facility modification/ancillary equipment purchase costing of $700. The equipment is intended for concentrated eyanide wastes (at both shops dilute CN wastes are treated by alkaline chlorination). The rental unit is essentially a heated pressure hhamber (35 gal, 450 t0 470°F, 600 psi) with an agitator. PS 142 used the unit to treat cyanide wastes containing 100,000 mg/l CN to proximately 25 mg/l. Disposal costs for these wastes were previously $800 to $1,000 per $5-gal drum. In operation, CN wastes are fansferred into the vessel and treated on a batch basis for 10 hours and then discharged to conventional treatment. Ammonia gas generated by ‘unit is vented to the atmosphere, PS 142 reported operating costs, excluding labor, of $4,000 pet year and a labor requirement of 750 man- ours, They also indicated that they experienced temperature and pressure control problems due to a seal Teak (N2 and oil seal) atthe point of itator entry into the vessel. PS 142 indicated that the unit had a downtime of $0% and that they have discontinued its use. hemical precipitation of cyanide can be achieved using ferrous sulfate. This process precipitates the cyanide as a ferrocyanide, which can be cemoved in a subsequent sedimentation process (ref. 386), Results of EPA sampling of such a process showed that an average influent ‘oncentration of 2.7 mg/l CN was treated to 0.023 mg/l CN. ext Section/Main Table of Contents|Section 6