M M M MMM MMMM M i MMMMMMMMMM l M I MMMMMMM THE 336 TELYHC a.” -c'r’fzg (15;: SL133 Tm? 2E: BEuZfi»... .5" 5 .. : :ALGEZKZL‘ it MEWS .9 V'. E‘ .. F“:,—,’.- 4. iie-rbsri 2;: 545,2; Na “”4 (w an Na J ‘. ~‘f -. (Erin’s. x.‘ . ugh-J. T 'I mainfi ' ' . 5 : fl 7A.,_I£I :3 r .‘u 4 ’3 i ! 2-3 _ a," “3 Y } I M _ ‘ l r- ‘ _ \ \7.- ‘ '1 <' I n‘ .J '; I .. - 1 -~ 5 > V ~, 5'. H .L: . :1.“ .:~..: ' M 5 ‘ 5': v .‘ . - ! I ,I r ‘ . ~ E 7 ) ~ $9.53,, 4 LL) k '- 1 ) ,. a, M" u- 'v ’u ‘ V! 1) - s'w"""""?¥~‘t‘r‘ '9'" " \‘Pn’u‘ '1" NJ, '1 C THE ELECTROLYTIC REDUCTION OF SUBSTITUTED BENZOIC ACIDS I. HALOBENZOIC ACIDS 3! Herbert Bowers Rickert A THESIS Submitted to the School of areducte Studiee at lichigen Stete College of Agriculture and Applied Science in partial fulfillment of the requiremente for the degree or MASTER OF SCIENCE Department of Chemistry 1952 ABSTRAC The purpoee ct this inveetigction‘eee ee tolloee: To determine the optinnn.eonditionc tor the electrolytic reduction or orthodbromobcneoie ecid end to test the Inltebility of these conditione for the preparation of other eubatituted benzyl elcohole. Forty-nine experimente were cerried out in the following leaner: The electrolytic cell Ia. assembled. the ecid to be reduced.ven pleced in the cetholyte and e current peeeed for e epecitied.period of time. At the end of the experiment the‘beneyl elcohol nee eepereted from eny unreected beneoic ecid end the two compounds purified by conventional methodeo The detailed oonditione need end the reeulte obteined in these experiments are listed in tebulcr form in thie theeie. The meat euiteble conditione for the reduction eppeer to be e leed dioxide cathode, en elcohol-eulfuric ecid cetholyte and e high current density. The porous cup- (which contain the enolyte) ehould be thoroughly cleened before nee in order to remove any iron eelte preeent ee inpuritiee. Electrolytic reduction of the correeponding ecid.eee found to be e deeireble method or preparetion for the mono chloro~ end‘bromo-bensyl elcohole. Thie method of reduction eppeere to be or limited epplicution tor the 4"“ r“ ("'9 , Q I»; , A A 4_ i .j. "“3' a (J; ij ‘ n! preparation of iodc- and dichloro-benzyl alcohole because of the relative incolubility of the corresponding acids in an alcohol-aulfuric acid catholyte. In general, the more eoluble the substituted benzoic acid, the better the yield of the corresponding benzyl alcohol and the greater the current efficiency. Para-bronco, pare-iodo-, and 2,6-dichlorc-henzyl alcohola have been prepared for the first time by electrolytic reduction of the corresponding acide. The latter alcohol (2,6-dichlorobenzyl) ia previouely unren ported in the literature. AC KN OWLED GEME NT The author niches to express his deep appreciation for the help and encouragement of Professor Ralph L. Guile during the course of this investigation. He is also greatly indebted to Professor Dwight Ewing for the use of the Electrochemical Laboratory. Grateful acknouledgement is also due to Professor Bruce Hartsuch for his assistance in the writing of this thesis. leég OF QONTEHTB INTRODUCTIOI 1 HISTORICALrBACKBROUND 8 APPAREIUB 1. Cell Design 10 II. nectredea 18 III. Porous Cups 15 newsman! mocxbunx 1. Preparation of ma. 1! II. Electrolytic Reductions of Aside 18 III. Conditions for Electrolytic Redueticns 19 IV. Purification of Aleohols I? RIBUIEB - 80 ‘DISOUSSIGE 89 CONCLUSIONS 4‘ REFERENCES 46 W Halogen substituted bensyl alcohols are not available commercially, and the synthesis of some of these alcohols. for example the ortho bromo isomer, by the usual organic ‘chemical methods is not too satisfactory. Since many halogen substituted aromatic acids are either commercially available or easily synthesized from available substances. electrolytic reduction of such bensoie acids would be a convenient method for the synthesis of halObensyl alcohols. Fichter (1) lists many examples of aromatic acids which have been successfully reduced to the corresponding alcohols in excellent yields. many of these reductions sore carried out by Mettler (2) (S) (4), but attempts by Wu (5) in this laboratory to prepare o-bromobensyl alcohol by the method of Hettler were not too successful. The purpose of this investigation was as follows: hettler's norkzwith o-bromobensoic acid see to be repeated, different conditions leading to variations in yields of the o-bromobensyl alcohol were to be investigated. and finally other alcohols were to be prepared using the technique developed for the preparation of the o-bromobensyl alcohol. HISTORICAL BACKGROUND The first electrolytic preparation of bensyl alcohol was accomplished, not by the reduction of bensoic acid, but by the reduction of esters of bensoic acid. In 1904- 1905 Hettler reported (6) (7) that by'using a lead cathode and an alcoholic sulfuric acid catholyte ethyl bensoate could be electrolytically reduced to bensyl alcohol. care-cans I 320 ’10 6000335 I SUI] < Chg-OH / 023503 However along‘with.the alcohol bensyl ethyl ether was also formed. lettler obtained similar results with methyl bensoate as well as with esters of o~chloro~ n-chloro-, and mpbromobenzoic acids. Since the yields of the ethers were higher than the yields of the alcohols this was not a very satisfactory method for the preparation of bensyl alcohols. Tafel and Friedrichs (8) also reported that the ethyl and methyl esters of benzoic acid may be reduced to the corresponding bensyl ethers, but they did not mention the production of any bensyl alcohol. They used a lead cathode at a temperature of 12°C. and a current density of 10 amps. per sq. dm. nettler (8) (s) was the first investigator to successfully reduce aromatic acids to the corresponding ‘.aleohels. By working with.a lead cathode and an alcoholic sudfuric acid.cathelyte he was able to bring about the reduction of numerous aromatic acids. ' Jun-coon / em ---o-. menace { age can. of the acids he reduced were bensoie acid. the three acne-chlorobensoic acids. and rebromobensoic acid. rattler reported that the concentration of sulfuric acid had no influence upon the cheuical yield of the alcohol or the current efficiency. It The process was carried out at roos.temperature by cooling sith a water bath. because there was danger of esterification at higher tesperatures. a.cathode area of 1 sq. as. and a current density of 6-12 Ilpl./OQs as. were used. The catholyte was composed of 30 grams of sulfuric acid, 70 grams of alcohol, and so grass of the asid.tc be reduced. It sas possible to replace some alcohol with.water in order to increase the conductivity of the estholyte. settler-found that. in the reduction of benscic acid, it was possible to substitute water for one half of the aleohol in the catholyte. use a temperature of 50~60°G., and add the benscic acid.pcrtionwise. nettler was unable to reduce bensoic acid suspended in cold aqueous sulfuric acid of various concentrations. In the reduction of these aromatic acids Nettler used what is known as a “prepared” lead cathode. This type of electrode is made by Tafel's method, i.e., electrolytic oxidation of the lead in a 20% sulfuric acid solution (9). According to Tafel (10) the surface film of lead dioxide which is formed has a higher overvoltage and is more active than a plain lead cathode. Both Mettler (2) and Tafel (9) found that the porous cups need in electrolytic organic reductions had to be cleaned with Each and HCl in order to remove iron salts which were present as impurities. nettler later reported (6) the reduction of more aromatic acids by the same method. In this article he mentioned that c-bromobensoic acid can be successfully reduced to c-bromobensyl alcohol, and although no yields of specific alcohols were given, he stated that in general yields of 60-85% may be expected. In the reduction of m-iodcbensoic acid, bensyl alcohol is formed along with the expected n-iodobensyl alcohol, and with c-iodobensoic acid only bensyl alcohol is formed. much of the later work on clectroytic reduction of aromatic acids was carried out with bensoic acid. Inoue (ll) repeated Hettler's work with bensoio acid and obtained a 78% yield of bensyl alcohol. Lecane and Dufour (12) carried out the reduction of bensoic acid with a lead cathode, but in contrast to nettler they need boiling aqueous sulfuric acid (60%) as the oatholyte, and added the bensoic acid a little at a time (this minimised esterfication). They found a cathode density of 12-13 ampso/eq. dm. to be Optimwm current density. Besides the bensyl alcohol (75-80%), sons dibensyl ether (cans-cnz)zo (15.20%), ice-hydro- bensoin Cans-63(OH)-CH(OH)-05H5 (1-23). and tar (3%) were obtained. Although bensaldehyde was not detected they believed that the production of ischydrobensoin was evidence of bensaldehyde as an intermediate in the reduction. Baur and Muller (13) carried out the reduction of bensoic acid using a lead cathode. a dilute alcoholic sulfuric acid catholyte. and a low current density (2 amps./eq. dm.). In addition to bensyl alcohol they obtained a product with the empirical formula C6380 which they claimed was AF-cyclohexencne. However comic (is) pointed out that this compound had the properties of the ethyl ester of Al’z’n-dihydrobensoic acid which would be formed by hydrogenation of the ring. Fichter and Stein (15) also repeated Kettler's work and obtained an 80% yield of bensyl alcohol. They believed that hydrogenation of the ring as observed by Baur and luller was due to the very low current density that the latter used. Swann and Lucker (16) studied the reduction of bensoic acid by the liettler method at cathodes of cadmium, tin, lead, mercury, zinc, aluminum, nickel, capper and iron. They reported that good yields of benzyl alcohol were obtained only with lead and cadmium electrodes. According to them the physical structure of the cathode surface was an important factor in controlling the yield. They also found that a lead cathode will lose its activity after prolonged use. This loss of activity was accompanied by excessive formation of lead sulfate on the surface and several days of ”preparation" by the Tafel method would not bring about a resumption in activity of the lead cathode. When using cadmium cathodes they found that the yield of alcohol was dependent upon the ability of the cathode to undergo a macro-etch of its surface, and that the yield of alcohol was proportional to the extent of such etching. Little or no yield resulted when the surface would not undergo an etch. Yields at other common metal.electrodes were not improved by etching the surfaces. Nithack (17) was able to reduce benzoic acid to bensaldehyde by the use of graphite electrodes and 20% sulfuric acids Other investigators have found that the reduction of salicylic acid at mercury electrodes in boric acid solution can be stopped at the aldehyde stage if some method of removing thesalicylaldehyde is used. Wail (18) used para-toluidine to form a Schiff's base with the salicylaldehyde and prevent further reduction. Mottler (19) found that, if benzene were added to the catholyte and the system stirred vigorously, the aldehyde would dissolve in the benzene phase and be protected from further electrolytic action. The best results were obtained by Tech and Lowy (20) who fixed the aldehyde as soon as formed by means of sodium bisulfitc and then recovered the salicylaldehyde by means of acid hydrolysis and distillation. Their best yield was 55%. Hutovskii and Korolev (21) repeated Tech and Lowy's work but obtained yields of only 54%. They also found that cohydroxybenzyl alcohol was the main product when benzene and magnesium butyrate were used in the catholyte. In acid solution at lead electrodes Mottler (19) and Somlo (22) reported that the expected o-hydroxybensyl alcohol was formed. Electrolytic reduction of o-bromobensoic acid'by Wu (5) in this laboratory was not too satisfactory. Five experiments resulted in yields of 40%, 30%, 15%, 0%, and 0% o-bromobensyl alcohol. The conditions used were similar to those described by settler (2) (3) except that a current density of 5nd amps./sq. dm., and a plain lead cathode were used. Olivier (as) attempted to prepare 2,6-dibronobensyl alcohol from 3,6-dibronobenscic acid by the Nettler lethcd. However he found that one bromine aton was . elininated as hydrogen brondde and o-bronobensyl alcohol was for-ed. He stated that the second bromine in position 0 increases the nobility of bromine in position 3.’ On the other hand lettler (2) has successfully reduced 3,5-dibromcsalicylic acid to 5,5;dibroncaelieyl alcohol. a. has also (a) reduced 3.5-diehloroealicylie acid and a,6~diehlore-d-hydrcxybensoicacid to the corresponding alcohols. A.nuiber of other investigators have successfully used the method or lettler for the reduction of aromatic acids. Olivier (24) has prepared p~tolyl carbincl free potoluie acid; Bayer and English (25) have reduced ‘ B-ethylbensoic acid to the corresponding alcohol, and layer, Schafer, and Rosenbaeh (26) have reduced a series of substituted anthranilie acids. Detailed instructions for the reduction of anthranilie acid are given‘by Coleman and Johnson (27) in "Organic Syntheses”. They used essentially the sane conditions as Rattler, the eetholyte being aqueous sulfuric said since anthranilie ‘ acid is fairly soluble in aqueous sulfuric acid. aide chain acids have been successfully reduced at a lead cathode in sulfuric acid solution. filing (28) (89) reports the reduction of ortho, nets, and para tolylaeetic acids to the corresponding ethyl alcohols using these conditions. larie and Marquis (50) were able to Obtain beta-phenylethyl alcohol by the reduction of phenyl acetic acid at lead electrodes. However they found that electrolysis at 60°C., using an alcoholic sulfuric acid catholyte, resulted in the formation of n the ethyl ester of phenylscetic acid. When they used aqueous sulfuric acid (60.70%) some beta-phenylethyl ester was formed along with the beta-phenylethanol, and the yield of alcohol never exceeded 33%. The use of a bensene sulfonic acid catholyte did not increase the yield of alcohol. ' ’ Compounds such as bensene sulfcnic acid are knosn as hydrotropes because, in aqueous solutions, they have a "saltinga-in'l effect on added solutes. boxes and Heard (51) found that sodium benzene sulfonate exhibited hydrotropic properties toward bensyl alcohol. With a saturated sodiue hensenc sulfonate solution as the anolyte they were able to oxidise successfully bensyl alcohol to bensoie acid at nickel electrodes. Aliphatic acids are much more difficult to reduce than aromatic acids. hasuno et a1. (82) found that the best yield of butyl alcohol from butyric acid was 0.55 in 80% sulfuric acid and 17% in dilute sodium hydroxide. 5325:3231 I e 3211 “'1“ Figure l dhows the type of cell used for the first eighteen experiments. The set-up was about the same for all eighteen experiments except for the type of cathode (see following section). Figure 8 illustrates the type of cell used in experiments 19 to 82 inclusive. With a soluble acid, e.g., cabroncbensoie, it was not necessary to have the catholyte stirred, however this eell proved unsuitable for the more insoluble acids where a stirrer was needed to keep the depolariser in contact with the cathode. Figure I shows the type of cell used in experiments 23-d7. in extra wide slot in the cathode next to the stirrer was used to give more rocn.for rotation of the stirrer e '+ \CQAJ HOTO" Ono G j - \“ qua ,3) thss sTirrer CdTher l \fl'er beaker Porous ‘/ c'up H H "N , N \CQ Q As baTh \ a; V E O ' 3 I I ano‘yte (dfho\7Ye Figure 1 -11- + lend - CnThodeSi—ID \Ecld anode \\\ *0.“ form 500 cc. T*‘*-* \\ 13p\ess beaker- “""i x‘ -_ fi _ - J r 3 ‘1 PO 0U CUP h. .4 FL quer b‘Th F'— “‘3er OUT‘Q‘ __l "‘”‘Qho\7*9 t chhcflyTe'W V ; Figure 2 \Ead qnode+ moTov- “Q“ 1... ‘ “\‘ 30° min-beaker W s \ ---L_ porous cvp "‘-‘ 7. Wat'Er bqj'h [— one" OUTIET amo\yTe -......, $ ‘ ‘¢5oss J J—J J ’ sTlrrer CQThO‘YTe Figure 3 ~12- ;_. Electrodes The anode used in all eXperiments was standard quality sheet lead, 7 cm. wide and 20 cm. long. bent to form a hollow cylinder- 7 cm. in circumference finich would fit inside a porous cup. In experiments 1 and 2 the sheet lead cathode shown in Figure 4-A was used. A nickel gauze cathode was used in experiment 3. The sheet lead cathode shown in Figure 4-8 was used in experiments 4.18. This type of cathode was bent part way around the outside of the cup in order to decrease the internal resistance of the cell. Figure d-C shows the type of sheet lead cathode used for experi- ments 19-47. This type of cathode was bent to fit almost completely around the outside of the porous cup and was slotted in order to secure better circulation of the catholyte. The lead cathodes used in experiments 5 and 10-47 were prepared according to the method of Swann (33) by oxidising then in sulfuric acid solution so that a layer of spongy lead dioxide was formed on the surface of the electrode. -13- k 7M. r— Mam—4 Figure 4 -14- T 3:0 i 25c 11. us 0 For the first eighteen experiments the cups were cleaned‘by sucking 80% sodium hydroxide through the'walls until the cup was almost half full, emptying out the warming.‘ and then repeating the process with 20% sulfuric acid. From experiment 19 on the cups were cleaned by allowing them to remain immersed in successive portions of 20% sulfuric acid. This latter treatment is recommended by Swann (33). These dupe were cleaned in order to remove iron impurities which.ware present. In experiment 85 and thereafter the wash sulfuric acid was tested for ferric iron by adding potassium' thiccyanats. If the test was positive the cups were again innersed in sulfuric acid and the treatment continued until a negative test was obtained. - 15 - Labggatggz Procedure 1. :Preparation_g£ Acids The acids used in experiments 8 to 10, 12. 17, 21 to 39, and 42 to_49 were obtained from Eastman Kbdak. All were ”Eastman white Label“ chemicals with the exception of the 3,4ediohlorobenzoic acid which was 'Practical' grade. The ortho-bromobenzoic acid (m.p. 150°C) used in experiments 1 to 7, l5 and 18 was prepared in this laboratory by a Sandmeyer reaction similar to that used by Hodgson and Walker (35). Cuprous chloride used in ' the Sandmeyer reaction was made by the method of Marvel and McElvain (36). The ortho-brcmobensoic acid used in experiments ll, 13 and 16 was made by the same method as above. however, a variation in the purification of the acid was used. Instead of filtering the acidified reaction mixture at once to recover the acid, the system 'was first diluted by adding it slowly (with constant stirring) to three parts of water. The system was then eooled.with an ice-bath and the crude acid filtered off and purified by the usual methods. \ Rare-bromobensoic acid (Hope 251°C) for use in experiment 14 was prepared by the potassiunnpermanganate oxidation of paraebromotoluene. The method was that of Clarke and Taylor (37). This same method was utilized to make the ortho-chlorobcnsoic acid (map. 142°C) used in experiment 19: however. in purifying the acid the usual method was - 15 - changed and the reaction mixture was not concentrated before fin ration. The paraachlorobensoie acid used in experiment 20 was a student preparation obtained from the stockroom. Its method of preparation waslnnknown but it was recrystallised from a 60% alcohol-water medium and had a Imp. of 268°G. ‘ The 2,6-dichlorobensoic acid (mp. 1434-1400) for experiments 40 and 41 was made from 8,6-dichlorotcluene by the method of Lehmstadt and Schrader (ca). .17- II. Electrolytic Reduction Of Acids The porous cup was cleaned, as previously described, filled with the anolyte, and let stand so that the snolyte would permeate the pores of the cup. In the meantime, the cathode and cathclyte were prepared. If alcohol was used in the catholyte it was found best to dissolve the substituted bensoic acid in the alcohol and then cautiously add the sulfuric acid (with cooling) to the alcoholic solution. The apparatus was assembled, the electrodes connected to the switchboard (15 volt line) and the variable resistance adjusted to obtain the desired current. Often when a fairly large current (around 10 amps) was used with an alcoholic catholyte, (with no added water) it was possible to pass only 7 or 8 amps althout excessive heating of the system. However in ten or fifteen minutes the current could often be increased to 10 amps without having the temperature go above 35°C. The reaction was stepped when about three times the theoretical (based on one Faraday per equivalent weight of acid) amount of current had been passed or when increased evolution of hydrogen was noticed. - 13 - III. Conditions For Electrolytic Reductions Forty-nine experiments were carried out using varying conditions of current density, catholyte composition, etc. The conditions used for each experiment are listed in the tables which.follow. These tables are arranged so that acids which behave similarly in electrolytic reductions areiieted together. 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