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Cyclic polyhydroxy ketones. II. xylo-trihydroxycyclohexenediolic acid and keto-inositols

1964; The National Institute of Standards and Technology; Volume: 68A; Issue: 3 Linguagem: Inglês

10.6028/jres.068a.026

2376-5704

Alexander J. Fatiadi, Horace S. Isbell,

Chemical Synthesis and Reactions

A new crystalline compound, Dlrxylo-t rihydro xycycloh exenediolic acid (oL-xylo-pen tah yd rox y-2-cyclohexen-1-on e) (1), has been isola ted from the products of oxidation of myoinositol with nitric acid, and its structme has been establi shed.Compound (1) r educes Tillm a ns reagen t, reacts with iodin e in n eu tral or sli ghtly acidi c solution, produces a blue color with ferric chloride soluti on, and exhibits othe r properti es cha racteri stic of a n en ediolic acid.On catalyt ic reduction , it gives both scyllo-inositol and m yo-inositol.On oxidation, it yields a new t rik eto-inositol, xylo-4,5, 6-trihydroxycyclohexane-1 ,2,3-tri one (II).U nd er acidic cond iti ons, catalytic acetylation of 1 gives two pen taacetates, t he infrared sp ectra of whi ch arc simil a r but n ot id ent ical.One of t hese acetates ex ists in t wo form s, b oth of whi ch , on deacetylation, yield th e pa ren t ac id 1. Th e product form ed by deacetylation of th e othe r pentaacetate has not bee n identifi ed.Benzoylation of I gives a crystallin e p en taben zoate.Unde r basic condition s, acetylation of I proceed s with simultaneous a rom atization, r esultin g in the formation of pentaacetoxybenzene, from whi ch pentah ydrox ybenzene is obtained b y h ydrolys is.xylo-4,5, 6-Trih yd roxycyclohexane-1 ,2,3-trion e (II) gives a crystalline bis(phenylhydrazon e).B y acetylation under basic condi t ion s, it y ields hexaacetoxy ben ze ne.M echanisms are presented for t he a romatization of keto-inositols by en oli zation a nd beta elimin ation-reactions, a nd ce rtain observations reported in t he li teratme a re rationali zed.Infrared and ult raviolet a bso rp t ion spectra a re reported for t he n ew compou nd . 1 This work was supported, in part , by the Division of Air Pollution, Public Health Servicc, U . .D e partm ent of Health, EduCc'l tion , and 'Vel fa re.'Presented, in I)art, before the Division of Carbohyd rate Chemjstry a t th e 141st M eeting of the Ameri can Chemical SOCiety, Washington , D .C., M a rch 26, 1962.Abstracts Papers, Am.Chern.Soc.141,60 (962).Pa per I was published in J. R es.N B S 67A , (Phys.and Chem.)N o.2, 153 (1963) .3 Figures in brackets indicate the li terature references a t tl,e end of tbis paper.4 Tho term j'c ncd iol ic acid" is used here for a,.8-11Jl saiu ratcd, c1 ihydroxy aId£'h ydes and ketones having the SLr ueture R-C = C -C-R '.The cc m-I-IO OlI 1 1 -< JI h r "-K "orr no ""~~ 1 ' "