Aimi, Hironori

Hamada, Noriaki

Kagehi, Koji

Umezu, Masahiro

Yamamoto, Jiro

Tottori University Research Result Repository

The Wanach Rearrangement of´一Nitroazoxybenzenesand the Reaction with Chlorosulfonic AcidJiro YAMAMOTO*1,Koji K▲GEHI*2,HttOnori AIMI*1,Noriaki HAMADA*3 and WIasahiro l」MEZU*(Received October 20,197のSu■1】maryThe Wallach rearrangement of α― d,9ψ―nitroazoxybenzenes using concen―trated sulfuric acid was exanlined in detall in comparison with the previousrePorts, In addition to 4-hydroxy-4′―nicroazobenzene already known as a mainprOduct, 2■hydroxy-4′―nitroazobenzene and´―nitrOazobenzene were isolated asby―Products, The formation of 2■hydroxy-4r_nitroazobenzene from α=´―nitro―azoxybenzene is interpreted by an interconversion between α― and β=´―nitrO_azoxybenzene which are formed froェl their onop tonated form.The reactionof α―and β=´―nitroazoxybenzene with chlorosulfonic acid was also broughtabout with the same results concerning the reaction products although highortho―Para ratio of hydroxyazo compounds was obtained in comparison withthe Wallach rearrangement using sulfuric acid.l lntroductionSince Wallach et,al.よ)obtained´―hydroxyazobenzene by treatinent of azoxybenzenewith concentrated sulfuric acid and Bambergerワ)found that ο―hydFOXyaZobenzenewas formed silnultaneously as a by―pr duct in the same condition,  the generalityof the Wallach rearrangement was recognized for many azoxybenzene derivatives,3)α―(1)and βψ―nitroazoxybenらene(2)were Synthesized by Angelli et.al.4)and theyreported the different behavior in the reaction、vith nitric acid (speCifiC gravity ;1.48)and irradiation of UV ray on both compounds. In addition, they obtained 4-hydroxy-4′―nitroazobenzene(3)by warrling both compounds with suifuric acid butits yield and material balance in this reaction are not clearly decided, GoreS)indiとatedthat the reaction rate of (2)was faSter than that of(1)and β一―→α cOnversiOn oc‐cured in the reactiom process with 98%sulfuric acid for 23 hrs, at 20°C. The e og‐nization inethod for β――→α cOnVerSion by Gore6)waS Visual observation of the colorchange of recovered少一nitroazoxybenzene in concentrated stllfuric acid, but this me‐thod is not adaptable if α――→β COnversion occurs to a small extent. We authors*l The Faculty of Engineering,Tottori University*2 0saka Prefecture(graduated at 197の*e Taki Kagaku Co.Ltd.,(graduated at 197のReports oC the Faculty c: Engineering, Tottori University,Voユ. 6           65studied theヽVallach rearrangement of(1)and(2)in order to know whether this re‐action is the best synthetic method for obtaining (3)and alSO α,β一inte c nversionoccurs in the process, by bringing under notice material balance and by―productsformation,We will report iater in detail α,β―interconversion on azoxybenzene deriva‐tives. IIigh yield of (3)was obtained as 、vell as 2-hydroxy-4′一nitroazobenze (4)and―´nitroazobenzene(5)as the results of this examination.のドNO配α―form(1) HO-8-N=N-6-N02+ON=ざ舎剛2QttN-6-N叫 ON一NO配β―form(2)The monocationic state of(2)seemed tO exist as a co■llnon in ermediate because(4)was fOrmed as the ortho isomer in the Wallach rearrangement of (1) and (2).Peal et. al,7)indicated that ―´hydroxyazobenzene was produced by treatment withanllnonium hydroxide solution after the reaction of azoxybenzene and c1310rOSulfonicacid (6). There is little investigation on the reaction of azoxybenzene derivativesand (6)except α二沙―m thylazoxybenzene8). The same results were also obtained inthe reaction of(1)and (2)with (6), as the case with the Wallach rearrangement.2 Experimental2.l Synthesis of α―(1)and β「―´nitroazoxybenzene(2)Crude(4)was synthesized by nitration using giacial acetic acid―nitric acid。)。After it 、vas extracted with acetone, red crystal was obtained by recrystalizationusing ethanol, m,p. 136.0～137.0°C (Literature,10)139,0°C).(2)was led by oxidationof(5)with hydrogen peroxide in glacial acetic acid, 1コ.p.146.5～147.0°C (Lit rature,10)152.0°C)and(1)Was led from(2)by treatment with chromium trioxide in glacialacetic acid,m.p., 1開.5°C,(LiteratureiO),152.0°C)。2.2 The Wallach rearrangement of α―(1) d βi″―nitrOazoxybenzene(2)1.Og (41×10~4 Mol,) Of´―nitroazoxyⅢeazene and 15ml sulfuric acid were pouredinto 100 ■1l round bottomed flask. After lbri at 80°C, th  reaction products wereseparated by the method as indicated in Fig. 1.(3)(5)(4)H2S0466 JirO Yamamoto,Koti Kagehi,Hironori Aimi,Noriaki Hamada and MasahirO Umezu:TheWallach Rearrangement of´―NitrOazoxybenzenes and the Reaction with Ch10rosulだ。nic AcidPour into ice water|extracted with eherextracted Mh 3%NaOH soln.acidined ?h Hci|extracted tth eher|dried|evaporatedSeparated by colui chrOmatography(benzene―s licagel G)dried,cvaplratedseparated by colutlnlchromatographyFig。l separatiOn of products in the Wallach rearrangement of α―and β=―´nitroazoxybenz e2.3 The reaction of α―(1)and β=沙―nitroazoxybenzene(2) with Ch10rosulfonic acid(6)2.Og (3.2x10~4 Mol。) Of 一´nitroazoxybemzene was put into lCICl nぅl four―neckedflask and the nlixture was stirred for 40 min. at 40°C.  The reaction ■〕ix ure w sgradually poured into ice―water form the precipitate.  The precipitate 、vasallowed tO stand over―night in concentrated aminonium とydroxide solution and theresultant red crystal was dissolved in benzene. The separation of the productswas carried out by the method indicated in Fig, 1.Identification of the products ,(3)agreed With authentic sample synthesized bystandard method, mop. 214.0～215,0°C (Literature,4) 213.0°C), Rf value in TLC(WakOgel G―benzene)and IR spectra。 (4) also agreed with authentic sample bythe synthetic method above, Rf v91ue in TLC (WakOgelG―benzene)and IR spectra,and in addition, IR spectra of complex of(4)with Cuprous acetate agreed with thatof the complex of authentic sample.´―NIIP,niline(7)has the same IR speOtra帯ith authentic sample t∞14).(benzene―silicagel G)ρぃnitroazobenzene4-hydroxy-44nitrO~azObenzeneRcPOrtS Or the_FaCulty of■4gineeirng,Tottori University,Vol. 63  Results and DiscussiOnTracing on the products yield iIJ treatment of(1)and (2) with Sulfuric acid invarious concentration, the material balances over 90ラか 、vere obtained in all cases.In the case of(2)with 92%sulfuric acid, 33%of(3), 5。2% of(ム)and 8 4%of(5)were respectively obtained withOut recovered(2)。 AlFX30S the sam  results werealso obtained in the case of(2). The Wallach rearrangement of both ―´nitroazoxy‐benzenes seemed to be the best method for preparation of(3)becauSe Of easinesson separation of(3)from Other products, Noticing the disappearance of´―nitrOazoxy‐benzene and the formation of(3)as indiCated in Fig. 2 and Fig。 3, the r arrange‐ment rate of (1)seems tO be later than that of (2)as Gore5)haS Once reported.Sulfuric acid concentrajon(%)Fig。2 The sulfuric acid cOncentration dependance on the prOduct ratioin the Wallach rearrangement Of α_ ―´nitroazoxybenzene (つReaction conditionReaction temperature;80。C,Reaction time ,lhr.,錦継♂基譜4絲.m ate畑;.Og e工Xlo-3Md.)一o―;4-Hydroxy-4JttitroazObenzene(の―o一12-Eydroxyttrnitroazobenzene(4)一⑬― ; ―´NitroazObenzenec5)―o―‐;Recovered αψ―nitroazoxybenzenecI)The reaction rate became larger rernarkably as concentration of sulfuric acid ap‐proaches nearly to 90ラ歩. The result is in accordance with the kinetic study reportedby Buncel et.al。15)that a 10t Of dications are formed with increasing sulfuric acidconcentration and the reactiOn rate becomes large rapidly so as to effect smoothlynJcleophilic attack on the dications by water molecule. The dication was pointed100（????68 Jiro Yamamoao,Koji Kュgehi,Hitonori Aini,Noriaki Hamada and MasahirO Umezu:TheWVallach Rearrangement of´―Nitroazoxybenzenes and the Reaction with Chlorosulfonic AcidSulFuric acid concentraion(%)Fig,3 The sulfuric acid concentration dependance o4 the product ratioin the Wallach rearrangement of βi ―´nitroazoxybenzene(2)Reaction conditionReaction temperature ;80°C, Reaction time ;ihr,Amounts ot starting materal,1.Og c4ユx10-3 MO .)Sulfuric acid ; 15ml.一o―;4-HydToxy-4′―nitroazobenzeneC3)_o_,2-Hydroxy望′―nitroazobenzenec4)ЧD一; ―´Nitroazobenzene(5)一o―;Recovered αψmitrOazoxybensene(1)out to be an intermediate in the process of the Wallach rearrangement by Oae et.al.16)and recently has been detected by Olah et,al.17)uSing NMR in SbF6~HF-302system at-78°C. The Wallach rearrangement to ortho position seemed to proceedvia intramolecular rearrangement toward remote phenyl ring from monocationicstate 16)。f aZoxyoxygen as sbown by Oae et. al.16)Since (1)and (2)forコa 4 as an Ortho isomer, these ―´nitroazoxybenzenes areinterchanged to each other in lronocationic state, and on the other hand,(4)seemsto be produced fronl monocationic state of(2)via intermolecular rearrangement,The presence of monocation was also recognized by Olah et, al.17)uSing NMR inF S03H―S02 System at-78°C. The monocationi。)V)of(1)and(2)are interchangedto one another, and on the other hand, they are transformed into dication15)!6)17)f。1_owed by nucleophilic attack by 、vater molecule. The reason Vヽhy rearrangementrate of(2)was faSter tlaan that of(1)seems to be due to the more rapid formationrate of dication, since diprotonated (2) is dehydrated more easily than the sameform of(1)beCause of the stronger effect of nitro group. The reason for the forma‐tion of(5)as by―product seems to be due to two electron reduction of dication15),6)17)RcPortS OE the Faculty ot Engineering, Tottori University,Vol.6              69although it was not clear where electrons were produced. The possible reactionmechanism is as follows,OH2 OH2④N=NONQ翠生ひ↓百】∫《邑汚N02島:OttN-6-m2姪雲と営一N-8-配HO④N一N-6-配(7)was fOrmed as an other by―produc  as much as 4.7ヮぢin 95琵チ ulfuric acid onlywith (2)。 The results of the reaction of(1) and (2) with (6) were indicated inTable l.Table l  The Reaction of α―(1)and β■´―Nitroazoxybenzene C2)with Ch】。rosulfonic acid (の?? (3)(%)???④ ド‐NoN01(5)(%)樹蟄名??舎卜↓ひ∝(2)-10知61J80HSOaCl ③a)HSOsCl t6Ja)HSOaC1 0)a)HSOaC]0)])80%H2SOF)95%H2604b)62.447.410.08035202410.514 80000752011XO,1∞0,11000m331.560 卜Nitroanittinerormed 4.2%G↓卦X》I??????HSOaC1 0B)80%H,S04b)95%H2S04b)76442.080620097?????00お0 30お ReaCtion tine i 40min,Starting material,208$2x10~3M。1ぅ,(6):10g゛,7x10=Molうb)Reactおn tinlせ,l hr.,Starting materiaI,10g e工×io~3MoI).H2S04'15ni70 JirO Yanamoto,Koti Kagehi,HirOnori Aimi,Noriaki Hamada and Masahiro Umezu:TheWallach Rearrangement of´―NitrOazoxybenzenes and the Reaction with Chlorosulfonic AcidAfter thc optimum reaction condition on temperature was investigated f9r the re―action of(2)and(6), thiS reaction condition was also applied to the case of(1)。「rhedata of the Wallacb rearrangement、ve  added in comparison with the reaction (1)and (2)with (6)in Table l. The higher ortho―para ratio were fenerally obtained inthe case (6)than that of the Wallach rearrangement, the reason being the weakernucleophilic character of chlorosulfonic anion in comparison with sulfonic anion, 4-nitro-4′―chlorosulfonyl azobenzene formed in the reaction of (1)and (2) with (6)was detected by the method indicated in the literature8).We authors are greatly ユndebt d to professor M. Tanaka in this university for hiscontribution to complete this paper.Literaturel)O・Wallach,L.Belli,働¢".β修″.,13,525o880)り E.Bamberger,C力珍解.β珍″。33,3192(190り3)P.H.Gore,G.K.Hughes,Af7st″αJ122工Sじす。買¢S¢, 力々,4A,185c951)4)A.Angdi,B.Valori,4.五.L.,21,I.729c19■)iC力¢務・スうS″.,6,2747(191りの P.H.Gore,I濾.g働効.,1959,1916)Po Ho Gore,G.K.Hughes,4″,AC″筋.4¢杉.,5,537o951)つ I.A.Pearl,A.Ro Ronzo,ユOrFo C物9″・,12,785(194つ8)Jiro Yamamoto,Kenti Furuya,ユげ 勲″.0管.C″し吻.31,605c197の9)A,Werner,E.Stiasny,鋭効.膨″.,32,3257(189りとの A.Angeli,K.Alesandri,4.4.L.,20,896(1911),C力効・ 4うSサ′.,5,3405 ■)11)L.Gattermarn,H.Wieland,“Dic Praxis des Organischen Chemikers"P.262(1961)Walterde Cruyter Cot,1りM.Elkins,L.Hunter,J.C´¢解,Sοθ.,1935,19581のD.K.Drew,J.K.Landquist,チ Cカワ脇.Sο,.,1985 252lo I R D C Card,Infrared Band Data Committee of JaPan(T,Shimanouchi)NankodolのE.Buncel,B.To Lawton,Ct7″.ェC力¢″.,43,862(196め1のS,Oae,T.Fukumoto,M.Yanagami,B″.助♂物。肋σ.」砂r72,36,601o96の17)G.A.Olah,K.Dunne,D.P,Kelly,Y.K.Mo,ュん″″.C力勢 。Sο♂.,94,7438(197り

The Wallach Rearrangement of p-Nitroazoxybenzenes and the Reaction with Chlorosulfonic Acid

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The Wallach Rearrangement of p-Nitroazoxybenzenes and the Reaction with Chlorosulfonic Acid

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