Article信州大学文理学部紀要 7: 23-27(1957)departmental bulletin pape

ARAI,  Toshio

English

Shinshu University Institutional Repository

-NaphthoquinoneβElectrolytic Reduction of(Reduction of  Quinones,  II  )By Toshio ARAI Department of Chemistry, Faculty of Liberal  Arts and  Science,  Shinshu University(Received Sept. 30, 1957)   In the previous  paper(') the author has reported the electrolytic reduction of  9,  10-phenanthraquinone. This quinone is considerably stable in spite of its being one of the o-quinone but it is supposed that o-quinone are generally unstable.  P—Naphthoquinone is one of the o-quinone and is unstable compared with p-quinones; that is, in alcoholic acid solution it is decomposed equimolecular  p-naphthohydroquinone and 2-hydroxy-1,  4-naphthoquinone.  (2) It is also transformed into dinaphthyldiquinhydrone slowly in diluted sulfuric acid or rapidly by heating in a sulfuric acid. Therefore, the care must be taken about the treatment of this substance in a acid or alkaline solution.    On the pure chemical reaction  j3-naphthoquinone is easily reduced to  P-naphthohydroquinone with sodium hydrosulfite(3), to 3, 4, 3',  4'-tetrahydroxy-dinaphthyl- (1, 1') by heating with zinc chloride in hydrochloric acid solution, (4) and to 1, 2, 4-triacetylnaphthalene in acetic anhydride in the existence of some sulfuric acid. (5)    In the present experiment the author tried to see how  P-naphthoquinone would act in electrolytic reduction and compare its action with that in the case of pure chemical reaction.    According to the author's experiments, p-naphthoquinone was easily reduced to  p-naphthohydroquinone in 60%  alcohol  .  solution in the existence of some diluted sulfuric acid. In a  sulfuric acid solution, it was easily reduced to dinaphthyldiquinhydrone and this quinhydrone was reduced further to 3, 4,  3',  4'-tetrahydroxydinaphthyl-  (1,  1  ').    Dinaphthyldiquinhydrone and tetrahydroxydinaphthyl obtained in the above experiments, were easily oxidized to  1,  P-dinaphthyl-3, 4, 3', 4'-diquinone by nitric acid or bromine water.    Then, it was recognized that this diquinone was reduced to  tetrahydroxy-dinaphthyl in alcoholic acid solution.    Moreover, in a electrochemical method the author tried to prepare the other reduction products of  p-naphthoquinone, nevertheless other products were not obtained.24 Toshio　ARAI No．　7　　　00ツLrs－Naphthoquinone　　　　　S　oi－iedOHB－Nic　phthohydroquinoneooOH一　　　　　　　OIIDinaphthyldiquinhydrone　ox ooOHLOH　　　　　　　　　OH　　　，　．，　mOI．｛3，　4，　3i　4LTetrahydroxy－dinaphthyl一（1，　1）／　　　　　，．，　o’　3，　4，　3，　4’一Dinaphthyldiquinone工E】x二periment；a1　　　　B－Naphthoquinone　used　in　this　experiment，　was　prepared　in　the　fo11owingmethod（6），　that　is，　orange　II　was　obtained　by　diazotization　of　sulfanilic　acidand　by　its　reduction　1，2－aminonaphthol　was　prepared．　P－Naphthoquinone　wasobtained　with　a　good　yield　by　oxidation　of　1，2－aminonaphthol　with　ferricchloride．　　　（1）　1～eduction　（λf　β一nal》htho（7zainone　to　β一naPhthohニソdro（7uinone．　　　For　this　purpose　electrolysis　was　conducted　under　following　conditions；　　　Cathode：　silver，　copper，　and　nickel　plates，　100　cm2　of　area　respestively．　　　Cathodic　solution：　A　mixture　of　120　inl．　of　60％　alcohol　and　some　5％　　　　　surlfuric　acid，　in　which　2g．　of　P－naphthoquinone　was　suspended．　　　Anode：　Pb　plate　of　cylindrical．　　　Anodic　solution：　5％　sulftu‘ic　acid　solution．　　　Current　density：　2　amp．　Isq．　dm．　．　　　Time　of　electrolysis：2hours．　・　i・Cathodic　and　anodic　solution　were　seperated　by　unglazed　pottery　cylinder　andthe　cathodic　solution　was　stirred　vigorously．　The　electrolytic　chamber　wasimmersed　in　a　water　bath　and　while　solution　was　kept　about　250C　by　runningwater．　　　After　two　hours　electrolysis　the　cathodic　solution　was　poured　into　muchwater，　in　which　sodium　bisulfite　had　been　added　to　the　water　beforehand　inorder　to　prevent　oxidation；　then　it　was　extracted　with　ether　and　the　etherextracts　were　dried　over　anhydrous　sodium　sulfate．　The　ether　was　removedat　room　temperature　and　the　residue　was　about　1．3g．　This　was　recrystallizedtwice　from　the　water　containing　some　sulfur　dioxide　and　leaflet　crystalswere　obtained；　yie1d’ ≠b盾浮煤@O．7g，　m．　p，　57－59‘’C．No．　7 Electrolytic　Reduction　of　P－Naphthoquinone 26　　　　In　order　to　isolate　these　crystals　as　diacetate　they　were　heatecl　withacetyl　chloride　and　recrystallized　from　water　containing　sulfttr　clioxide，　m．　p．102－1030C，　this　corresponds　to　the　diacetate　of　P－naphtl？ohydroquittqne’．’　，　Thishydroquinone　was　easily　oxidized　to　P－naphthoquinone　with　10％　ferrib　chro’ridesolution．　　　（U）　Reduction　of　P－naphthoquinone　to　dinaphthyldiqutnhyarone．　　　　Electrolysis　was　carried　out　under　following　conditions；　　　　Cathode：　nickel　and　silver　（100　cm2　of　area）．　　　Cathodic　solution：　5”／o　sulfuric　acid　and　alcohol．　　Other　conditfions　were　the　same　with　（1）．　As　electrolysis　advanced，’　thecathodic　solution　gradLially　began　to　turn　green－black　from　orange　and　qfterone　hour　it　became　perfectly　green－black．　This　was　dinaphthyldiquinhydrone．　　　Dinaphthyldiquinhydrone　was　obtained・　by　heating　P－naphthbquinon－e．　insulfuric　acid　（1：2）　for　ten　minutes，　but　at　a　low　temperature　it　was　notprepared　fromβ一naphthoquinone　in　5％sulfuric　acid　ill　a　short　ti血e，　therefore，this　is　regarded　as　dinaphthyldiquinhydrone　clue　to　the　combination　betweenreducecl　P－naphthohydroquinone　and　P－naphthoquinone．　　　（III）　1～eductiOn　Oアβ一nα1）h”ZO（luinone　to　tetrah二ydrOX二ydina2：》h”zyl．　　　Electroiysis　was　carried　out　under　following　conditions：　　　Cathode：　nickel　and　lead　plate　（100cm2　of　area）　and　zinc　amalgam　（15．8cm2　　　　　0f　area）．　　　Cathodic　＄olution：　302e（　sulfuric　acid　and　some　alcohol　or　10％　sulfuric　　　　　acid　60’ml．　and　30％　acetic　acid　60　ml．．　　　Curren’t　density：　4・　amp．／sq．dm．　　　Time　of　electrolysis：　1．5　hours．　　　Temperature：　40－450C．　　　Other　conditions　were　the　same　with　〈II）．　As　electrolysis　advanced，　thecathodic　solution　gradually　began　to　turn　greenblack．　ln　that’conditionelectrolysis　was　going　on．　four　hours　the　electrolyte　became　light　pink　colourand　the　electrolysis　was　discontinued．　This　light　pinl〈　color　did　not　disappeareven　electrolysis　was　conducted　several　hours　further．　，　　　Foaming　of　cathodic　solution　in　the　case　of　sulfuric　acid　was　taken　offby　the　acldition　of　alcohol．　ln　a　mixture　of　acetic　acid　ancl　sulfuric　acid，electrolysis　was　favorable　except　that　the　electrolyte　became　deep　colored，therefore　it　was　difficult　to　find　the　formation　bf　quinhydrone　ana　thefinishing　of　electrolysis．　　　The　electrolyte　was　poured　into　a　great　deal　of　water，　in　which　sodium　bi一　’sulfite　had　been　added　to　the　water　beforehand，　the　soiution　w’as　stirredsufficiently，　then　white　crystals　were　depositecl．　The　deposit　was　filtered　offquickly　and　recrystallized　from　30％　acetic　acid　solution　containing　some　sulfurdioxide．26 Toshio　ARAI No．　7Table　1　Electrolytic　conditions　of　quinones　and　reduction　products　Expt．　　　　　　CathodeNo．Catholyten－（234rD678図91011P－NaPhthoquinoneNi，Ag，Cu @16gZ，｛o，．　E．t，gO．H，　i20，i81；Ni，　AgNi，　PbPb’’Cu，　？bZn－Hgi　Pb，　Nii5％，　H，SO，Et－OH30％，　H，SO，E亡一〇H　　　ttglac．　HAc．16N－HCIl細魚・150％　H，SO，Et－OH20％（NH4）2SO4Et－OHDinaf）nthyl　diquinoneCu，　Pb　　ttZn－Hg10％　H，SO，5％，　H，SO4Et－OHsQ％o．　H，SP，glae．　HAc．80　u40’ノ100’ノ20　rt　　tt60’ノ60’ノ100’ノ20’ノ100r／20　tlllO　tr　10　tt120　tt60’ノ60　tt60　tt60　tlTemp．　oCc．　d．　ITimeamp．／dm・21　hrs．2525452525－552560：7025・256e902t4442350444502O．　51．534475335ProductsHyclroquineneQuinhydroneTetrahydroxy－dinaphthyi　　　　　’ノノ’ノ’1’Blue－black　CompoundUiLreducedTetrahydroxy－dinaphthyl！’　　　The　yield　was　1．5g，　m．　p．　170－175　UC．　This　was　tetrahydroxydinaphthyi．This　vLras　added　to　a　mixture　of　acetic　anhydride　and　sodium　acetate　and　themixture　was　heated　a　little　while，　and　acetylated　compounds　was　obtained，m．p．　155－160’；C．　　　Tetrahydroxydinaphthyl　obtained　in　this　experiment　and　acetylateddinaphthyl　had　not　sharp　Melting　point　and　was　not　obtained　，as　clear　crystalsand　the　former　turned　in　coior　to　light　brown　while　it　xKTas　left　alone　and　thecolor　became　beep　brown　gradually．　　　This’　reduction　product　was　easily　oxidized　to　dinaphthyldiquinone，　orangecrystals，　by　heating　with　nitric　acid　or　bromine　water．　　　（IV）1～edzaction　O／dinaP励ッ1吻uinone　to　tetrahydroxydinaP励yl．　　　Dinaphthyldiquinone　obtained　by　the　oxidation　of　reduction　product　inII　and　III　was　used　in　this　reduction．　Electrolysis　was　carried　out　in　amixture　of　acetic　acid　and　some　10％　sulfuric　acid，　in　which　2g．　of　diquinonewas　dissolved　as　diquinone　was　dissolved　easily　in　acetic　acid　solution．Af．．ter．　finishing　the　electrolysis　the　electroyte　was　poured　into　a　great　deal　ofv’a”　ter　’≠獅п@tetrahydroxydinaphthyl　was　deposited．No．　7 Electrolytic　Reduction　of　P－Naphthoquinone 27　　　In　the　case　of　sulfuric　acid　only　as　an　electrolyte　’the　reduction　did　notproceed，　but　by’the　addition　of　alcohol　diquinone　was　reduced　easily　at　a　lowtemperature．　　　（V）　Reduction　of　B－naPhthoquinone　in　zveale　alkaline　solution．　　　Electrolysis　was　cic　rried　out　in　a　mixture　of　20flo（　ammonium　sul’fateand　some　alcohol．　　　Blue－blacl〈　product　was　obtained．　This　substance　was　not　attacked　byheating　with　nitric　acid，　bromine，　and　diluted　sulfuric　acid．　ldentificationof　the　reductipn　product　was　not　investigated　in　this　experiment．　Moredetailed　studies　of　this　subctance　will　be　in　progress．Summary　　　Electrolytic　redgction　of　P－naphthoquinone　was　studied．　lt　was　reducedto　P－naphthohydroquinone　in　acidic　alcohol　solution　at　a　low　temperature　andit　was　also　reduced　to　tetrahydroxydinaphthyl　in　acidic　solution　by　way　ofdinaphthyldiquinhydrone．　　　Dinaphthyldiquinone　obtained　by　the　oxidation　of　tetrahydroxydinaphthylor　dinaphthyldiquinhydrone　was　reduced　easily　to　tetrahydroxydinaphthyl　ina1coholic　acid　solution．　　　Acknowledgment，　　　The　author　expresses　his　sincere　thanl〈s　to　Professor　B，　Sal〈urai，　for　hiskind　guidance　and　encouragement　throughout　this　work，　and　also　to　Mr．T．Oguri，　for　his　assistance　in　this　worl〈．References（1）（2）｛3）（4）（r））（6）ARAI，T．　（1955）　This　fournal　5，　Part　II，　17，FIEsER，　L　and　PETERs，　M．（1931）ノ：∠4m．　C々翻．　Soc．53，793．GRANDMouGIN，　E．　（1906）　Ber．　39，　3563．THrELE，　G・and　WiNTER，　H．　（！902）　Ann．　311，　345．LIEBERMANN，　C・　ancl　YAcoBsoN，　P・　（1882）　Ann．　211，　59．FmsER，　L．　（1937）　Or｛anic　Syntkeses　17，　9，　68．

Electrolytic Reduction of β-Naphthoquinone: Reduction of Quinones. Ⅱ

https://soar-ir.repo.nii.ac.jp/record/17371/files/Bunri07-09.pdf

Electrolytic Reduction of β-Naphthoquinone : Reduction of Quinones. II

Abstract

Similar works

Full text

Available Versions

Shinshu University Institutional Repository