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和田 弘次郎, 丸茂 晋吾, 宗像 桂
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A new insecticidal alkaloid, cocculolidine, C_<15>H_<19>O_3N, mp. 146℃, has been isolated from the fresh leaves of Cocculus trilobus DC. through the solvent extractions and subsequent chromatography on alumina (the yield 0.007-0.03%). This report presents evidence which let us assign the structure (I) for cocculolidine. The tertiary nitrogen atom was proved from the ready formation of the methiodide and absence of NH absorption in the infrared spectrum. The spectral data for cocculolidine showed the presence of α,β-unsaturated lactone, a methoxy group and a trisubstituted double bond. The base peak (M-58) in the mass spectrum and the half-height width (24 c.p.s.) of the signal of CH_3O-C-H of (I) suggested the presence of the partial structure (b). Reduction of (I) with NaBH_4 in MeOH gave (II). It was further hydrogenated with PtO_2 in AcOH to the saturated compound (III). Thus, (I) was concluded to be a tetracyclic compound. Oxidation of (II) with KMnO_4 in acetone-H_2O produced γ-lactam (IV). The above data led to the partial structures (b), (c), (d), and (e) for (I). The relationship between the partial structures was elucidated by BrCN reaction. (I) was treated with BrCN to give C-15 cyanamide (VII). The molecular formula, C_<15>H_<14>O_2N_2 and λ^<MeOH>_<max> ; 255mμ (ε=1850), 275mμ, (e=540) of (VII) showed the occurence of the aromatization accompanied by dehydrobromination and loss of methanol during this reaction and the presence of the sterically hindered o-substituted styrene in C-15 cyanamide. From the above data and the n.m.r., C-15 cyanamide was assigned to the structure (VII). Further chemical evidence about the relationship between the cyclohexene ring and the nitrogen in (I) was obtained by the product (VIII) of the acid catalyzed rearrangement. From the above data, cocculolidine was assigned to the structure (I).
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犬伏 康夫, 石井 永, 安井 凡平, 原山 尚, 橋本 真志
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Recently, the constituents of Lycopodium serratum Thunb. var. Thunbergii Makino (Lycopodiaceae) have been examined. The structures of serratenediol (I), a new skeletal triterpenoid contained a seven-membered ring, and several related triterpenoids have been established. Serratinine, a new alkaloid, was found in the basic component of this plant. Serratinine (II), m.p. 244-245°, C_<16>H_<25>O_3N, [α]^8_D-27.8 (C=1.44 in EtOH), IR 3472, 3436, 3185 (OH), 1724 (C=O) and 1424 cm^<-1> (-COCH_2-). Serratinine (II) on acetylation with Ac_2 O-pyridine at 100°gave diacetylserratinine (III) and on a treatment with bonsaldehyde gave benaylidene serratinine (IV). In addition to the above facts, the absence of signals due to vinyl proton and N-methyl group in the NMR spectra of diacetylserratinine (III) suggested that serratinine should be a tetracyclic alkaloid possessing the expanded molecular formula, C_<10>H_<15> (>CH-CH_3)(>CH_2-CO_)(>CH-OH)_2 (-N<). Mass spectroscopy of diacetylserratinine (III) gave the accurate molecular weight, and confirmed that serratinine should be a new skeletal alkaloid, since the fragmentation pattern of (III) was entirely different from those of lycopodium alkaloids reported hitherto. The degradative and spectroscopic evidence led to the conclusion that serratinine could be represented by the structure (II). The stereochemistry including the absolute configuration of serratinine will be discussed and the hypothetical biogenesis from a lycodoline type precursor to serratinine will be also presented.
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萩庭 丈寿, 坂井 進一郎, 久保 陽徳, 浜本 武紀
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The isolation of four tertiary basis from Gardneria nutans Sieb. et Zucc. is described. (Table 1) The Mass spectra of a main alkaloid gardnerine (I) is simlar to that reported for polyneuridine. Also the chemical reactivity of (I) is very close with 21-deoxyajmalol-A (IX) such were shown Fig-1 and 2. Upon oxidation with CrO_3, (I) was transformed into a product (VII). Upon reduction with LiAlH_4, this compound (VII) reverted to gardnerine (I), which a convertion is shown corrected structure of (VII). The both compounds of (VII) and gardnutine were identified by I.R. and Mass spectra. Isolation of 6-oxygenated sarpagine type alkaloid is the first case as natural product. The third alkaloid hydroxygardnutine (XVII) (Fig. 5) is transformed with hydrogenolysis to dihydrogardnutine (XXI), which was obtained from gardnutine (VII) by catalytic reduction. Also it is pointed out C-18 hydroxyl group on (XVII) that NMR spectra of (XX) has shown 5.41τ (doublet J=7 cps, 1H) and 4.57τ (tripled J=7 cps, 2H) as acetoxy-ethylidene group.
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堀井 善一, 花岡 美代次, 山脇 泰彦, 田村 恭光, 斉藤 清一, 重松 暹, 小寺 啓司, 吉川 浩, 佐藤 泰彦, 仲井 英夫, 杉 ...
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The total synthesis of securinine (I), an alkaloid of Securinega suffruticosa Rehd., and its optical antipode, virosecurinine (II), of Securinega virosa Pax. et Hoffm., was accomplished in the following way (Chart-1). 1,4-Dioxaspiro(4,5)decan-6-one (VI) was condensed with pyridyl-lithium to give the pyridyl alcohol (VII). Hydrogenation of VII over platinum oxide gave the piperidyl alcohol (VIII), which on deketalization followed by acetylation afforded two diastereoisomers of the α-ketol, (X) and (XI), after chromatographical separation. Condensation of the α-ketol (X) with lithium ethoxyacetylide and subsequent treatment with dil. sulfuric acid gave a mixture of the lactone (XII) and the hydroxylactone (XIII). Hydroxylation of XII with potassium permanganate followed by dehydration with thionyl chloride gave the butenolide (XV). Alternately, the butenolide (XV) was also obtained as follows; bromination of the α-ketol (X) and dehydrobromination of the resulting bromide (XVI) gave the unsaturated ketone (XVII), which upon reacted with lithium ethoxyacetylide gave XV. The acetyl butenolide (XV) was converted upon hydrolysis and formylation into the formyl derivative (XX), which gave the bromide (XXI) by bromination with NBS. Acidic hydrolysis of XXI and subsequent treatment with potassium carbonate caused the ring closure to give racemic securinine (XXII), which was resolved through d-camphor-10-sulfonates into securinine (I) and virosecurinine (II), identical with the corresponding natural alkaloids, I and II, in all respects.
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富田 真雄, 冨士谷 憲徳, 青柳 良明
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Cycleanine, (O,O-dimethylisochondodendrine), a bisbenzylisoquinoline alkaloid, was first isolated from Cyclea and Stephania genera (Menispermaceae), and the structure of which was elucidated as formula 1. The synthesis of this alkaloid, however, had remained unsuccessful. CuO-catalysed Ullmann condensation of dl-8-bromoarmepavine gave only 4a. Methylation of 4a with diazomethane followed by sodium-liquid ammonia fission gave proof for the structure 4a. In the course of an attempted synthesis of 4a by an alternative route, Bischler-Napieralski cyclization of amide 10 and 8 was effected, and it was found that, in both case, the cyclization proceeds in two directions i.e., ortho and pare positions with respect to the substituted phenoxyl group. Although cyclization products were not differentiated chromatographically, sodium-liquid ammonia treatment of N-methyl-tetrahydroisoquinolines, derived from the cyclization products, gave two phenolic bases 3a and 11. Synthesis of dl-cycleanine was achieved through Bischler-Napieralski reaction of cyclobisamide 22. N-CBZo-carboxylic acid (16) and amino ester (14) were condensed to give an amide (17), which was converted to the corresponding amino acid p-nitrophenyl ester (21). Intramolecular condensation of (21) afforded the cyclobisamide (22) in 17% yield. Bischler-Napieralski cyclization of 22 followed by NaBH_4 reduction and N-methylation gave a mixture of bisbenzylisoquinolines. dl-Cycleanine (A), diastereoisomer of cycleanine (B), and an isomer of cycleanine (C) were isolated in chrystalline state. The structure of the products were confirmed by IR, NMR, and mass spectral comparisons with natural cycleanine. The structure 25 for the isomeric base C was proved further by sodium-liq. ammonia treatment which gave 11 as the sole bisected product.
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塩入 孝之, 山田 俊一
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We have carried out the first synthesis of 1-methy1-16-decarbomethoxy-20-desethylidenevobasine (IV) having the carbon skeleton of the 2-acylindole alkaloids which are represented by vobasine (I). Dimethyl esters (VIIIa, b), which were respectively obtained from N-benzyltryptophan methyl ester (VIIa) and its 1-methyl derivative (VIIb), were subjected to the Dieckmann cyclization reaction to furnish the methyl β-ketoesters (IXa, b). Alcoholysis of IXa, b with benzyl alcohol followed by alkylation with benzyl bromoacetate gave the dibenzyl esters (XIa, b), which were catalytically hydrogenated and decarboxylated to afford the carboxylic acids (XIIa, b). The Huang-Minlon reduction of XIIa, b to XIIIa, b was followed by cyclization with polyphosphoric acid to give the tetracyclic keto lactams (XIVa, b), which were reduced by lithium aluminum hydride to the alcohols (XVa, b), and the latter were oxidized with chromic acid in pyridine to the ketones (XVIa, b). XVIa, b resisted the catalytic debenzylation over palladium-carbon, and only XVIb yielded a small amount of the carbinolamine (XVIIb). Thus XIIIb-1 was debenzylated with sodium in liquid ammonia, and the product (XVIIIb) was successively treated as above with polyphosphoric acid, lithium aluminum hydride and chromic acid to give XVIIb. Finally, methylation of XVIIb with formic acidformalin afforded the desired vobasine derivative (IV).
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伴 義雄, 大石 武, 永井 雅子, 若松 武, 赤木 昌夫, 落合 美和子, 大沼 毅, 岸尾 芳子, 井上 一三, 飯島 郁夫
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I. Studies on the synthesis of iboga alkaloids. In the preliminary experiments for the total synthesis of ibogaine, the Schenker's isoquinuclidine synthesis was followed and modified in this laboratory. Thus, the new stereoisomer (VIb, m.p. 116-117°) was obtained, and its stereochemistry was clarified. The n.m.r. spectral data provided further information about the inversion of the substituent on the trivalent nitrogen of these compounds. Moreover, the epimerization of the compounds (Vb and VIIb) into VIb with a catalytic amount of t-BuOK in t-BaOH was extended to the similar conversion of Va into VIa, which was advantageous for the subsequent Ziegler condensation. And the total synthetis of C_<(21)^->-nor-20-hydroxylbogamine in the form of its racemate was achieved. In connection with this work, anhydrous (98-100) formic acid was found to be an effective catalyst for the Fischer indolization. II. The application of the Meerwein reagent (Et_3O^+BF_4^-) to the organic syntheses. The Meerwein reagent which is effective in preparation of the active iminoethers from the corresponding amides, was successfully applied to the oxindole derivatives. In the preliminary experiments, the steric factors have been shown to be very significant in the reactivities of the iminoethers obtained in this way. Thus, the compound (XIII) through XII was synthesized. This compound could be an important intermediate for syntheses of aspidosperma, iboga and strychnos alkaloids.
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原 昭二, 岡 希太郎
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Salamander alkaloids were found in the toxic secretion from Salamandra maculosa and atra L. by Zalesky in 1866. Samandarine was isolated as a main component of these alkaloids by Gessner and Cramer in 1930. Its structure has been proposed by Schopf and his colleagues through chemical, optical and X-ray crystallographic studies in 1960. The characteristic skeleton of samandarine containing the aza-oxa-bicyclo-octane system is common to four other alkaloids. The synthesis of pentacyclio nucleus of samandarine is described here. 1-Formyl-A-nor-5β-androst-1-en-17β-ol (XIV) was prepared from testosterone by a nine step sequence as described in the previous paper. The benzylamino Schiff base of XIV was reduced with NaBH_4 to give the unsaturated amine(XXVa). The formamide of XXVa was oxygenated with OsO_4 and resulting glycol (XXVI) was cleaved by Pb(OAc)_4 to give the seco-aldehyde (XXVIII). After selective protection of the aldehyde group as the ethylene-acetal (XXIX), carbonyl group at C-1 was reduced with NaBH_4 to give the epimeric amide alcohols (XXXa). Saponification of the formamide led to the epimeric α-amino alcohols (XXXb). Hydrolysis of ethyleneacetal with 75% acetic acid afforded two products in 45 and 38% yields after purification by silica gel 1pc. The former (XXXIa) was bicyclized compound and the latter was intramolecular hemiacetal. Removal of benzyl group of XXXIa with catalytic hydrogenation gave XXXIb, the hydroxyl isomer of samandarine, of which it and nmr spectra are very similar to those of the natural products.
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正宗 直, 高杉 光雄, 村井 章夫, 小林 喜六
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This report describes the results obtained in studies aimed at the total synthesis of jervine (I), a representative compound of C-nor-D-homosteroid alkaloids. This program involves the synthesis of dihydroveratramine (VI) and its transformation into I. The starting substances for preparation of the ring E and the remaining steroid part in VI were XIV and V, respectively, the latter having been derived from hecogenin, a totally synthesized sapogenin. XIV was converted into XVIII (Chart II), and V into VIII (Chart I). Condensation of XIII with an enamine of XVIII produced no satisfactory results from the viewpoint of yield and purity of the products. However, an expected product XXII was obtained from VI and available for further syntheses; treatment of XXII with alkali led to an equilibrium of XXII and its epimer XXIII (3: 1), and the latter was reconverted into VI (Chart III). Reduction of VI with lithium in ethyl amine followed by catalytic hydrogenation gave XXVI, which had been prepared from 11-deoxojervine (III). Oxidation of XXVI followed by alkali treatment and so on has now resulted in the formation of XXXII (Chart IV), which was also derived from III (Chart V). Difficulty was encountered in introduction of an oxygen function to C-11, and attempted oxidations have not completely been successful yet. Nevertheless, an expected oxidation product XXXVI could be derived from I (Chart VI) and used for subsequent reactions. Treatment of a 3-ketone IL, obtained from XXXVI (Chart VI), with DDQ afforded a dienone ILII, which in turn was converted into I (Chart VII). Transformations of I into other naturally occurring jerveratrum alkaloids, veratramine (II), III and verarine (IV), have been established.
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竹内 節男, 米原 弘
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Variotin, an antifungal antibiotic produced by Paecilomyces varioti Bainier var. antibioticus, has the molecular formula of C_<17>H_<25>O_3N. The chemical structure of variotin(I) has been previously reported by the authors. Ozonolysis of acetylvariotin in chloroform followed by oxidative degradation with silver oxide in basic solution gave D(-)-α-hydroxycaproic acid, therefore the configuration at the 8' position is R. Information cocerning the configuration of the 2' and 4' double bonds was obtained from the n.m.r. spectrum. The coupling constants revealed a trans-trans configuration for 2' and 4' double bonds. Relatively ready formation of the adduct by Diels-Alder reaction reconfirmed the presence of trans-trans configuration in the conjugated system. The adduct is white needle crystal; C_<21>H_<27>O_6N, m.p. 137-137.5°. From the physicochemical evidences, the seven membered lactone formation between the 8' hydroxy and a carboxyl of the adduct was confirmed. This fact indicated that the 6' double bond must adapt a cis configuration. In conclusion, the stereochemical structure for variotin is N-(8'-R-hydroxy-6'-methyl-trans-trans-cis-dodeca-2',4',6'-trienoyl)-2-pyrrolidone.
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須原 康次, 前田 謙二, 梅沢 浜夫, 大野 雅二
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Kasugamycin is an antibiotic produced by Streptomyces kasugaensis and exhibits inhibition against various kinds of bacteria. including Pseudomonas and a strong preventive effect against rice blast. The chemical degradation of kasugamycin afforded three main fragments, i.e., d-inositol, methylkasugaminide (II), and kasuganobiosamine (I). The structure of methyl kasugaminide (II) was studied by mainly spectroscopic methods and determined to be methyl 2,3,4,6-tetradeoxy-2,4-diaminohexopyranoside, and it should be mentioned that to the best of our knowledge this is the first isolation from natural products. After structural determination of kasuganobiosamine (I) and kasugamycinic acid (IV), and preparation of each two isomers (V〜VIII) of monoacetyl- and monooxamide-derivatives of kasuganobiosamine (I), kasuganobiosamine (I) was chemically transformed to kasugamycin having an unique amidine structure which attached to 4-amino group of the sugar moiety. The gross structure of kasugamyoin (K) is proposed, since the linking position of d-inositol with kasugamine has been determined by X-ray crystallographic analysis.
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秦 藤樹, 大村 智, 片桐 通子, 小倉 治夫, 伊東 常男, 納谷 恵三, 野田 俊治, 阿部 仁之助, 渡辺 哲夫, 田家 照生
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The structure of a new antibiotic leucomycin A_3 (I) which have been isolated from Streptomyces kitasatoensis Hata are proposed. In the course of chemical degradative and spectroscopic studies on these compounds, interrelations with magnamycins and spiramycins are attempted. I is hydrolyzed in methanol to give VIII and IX, the former is confirmed by analyses of IR, NMR and mass spectra, and the later is treated by concentrated hydrochloric acid to yield XIII which is confirmed with an authentic sample. On the other hand, I is hydrolyzed in a diluted hydrochloric acid to give XV and XVI, the former is methylated to VIII and the later oxygenated to β-hydroxy butylic acid. When I is hydrolyzed after treated with methyl iodide, followed oxidation with sodium periodate to give acetaldehyde in a good yield. From these results, isovaleryl mycarose state to the position 4' of mycaminose, and have the partial structure >C=CH-CH_2-CH.CH_3-O- in I. Hydrogenation of I to yield IV, oxidation of I by an activated manganese dioxide to give VI show the α,β,γ,δ conjugated double bonds and hydroxyl group state in this system. I has an aldehyde from IR and NMR spectra, and from the fact that the data of NMR and UV spectra of III suggested a primary aldehyde, which state on a lactone ring neighboring to mycamino-side, because XXI yielding from XX by oxidation and closed to make a γ-lactone from IR spectrum. Stereochemistry of I are elucidated by IR spectral studies of intramolecular hydrogen bonding and NMR studies of I and related compounds.
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高橋 秀次, 大木 英二
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It was found that azalomycin B (I), which was produced by a species of Streptomyces and showed inhibition against gram-positive bacteria, was a kind of macrolide antibiotics having a composition of C_<52>H_<92>O_<19> as a tentative formula. The sugar component of I was designated as 2-deoxy-l-fucose (VIII). Alkaline degradation of I or its derivative suggested the existence of the carbon chain like XV in the aglycon part of the antibiotic.
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野老山 喬, 神川 忠雄, 西川 隆也, 前田 四郎, 久保田 尚志
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Sclerin, C_<13>H_<14>O_4, m.p. 123°, [α]_D+7.85° is a metabolite of Solerotinia libertiana, which was isolated originally as a lipase formation stimulating factor in the mycelium and later found to have the growth promoting effect for various plants. Sclerolide, C_<12>H_<14>O_4, m.p. 163° is another metabolite of the fungus obtained in minor amount. In this report the structures (3) and (32) are presented respectively for sclerin and sclerolide. The UV and IR data suggested the presence of 3-hydroxyhomophthalic anhydride structure (8) for sclerin and this was substantiated, inter alia, by following transformations. Reduction of sclerin with sodium borohydride gave (9) and (10). The methyl ether methyl ester (12) was degraded to the five-membered imide (19) by Curtius rearrangement and to the γ-lactone (20) by lead tetraacetate decarboxylation. The part structure (8) in conjunction with NMR data led to the expression (3) for sclerin. Final proof for this structure was provided by the synthesis of the nor-acid (23) derived from sclerin through the treatment with aq. 40% potassium hydroxide solution at 180°. The structure (32) for sclerolide was deduced in connection with that of sclerin and justified by the chemical correlation. Upon reduction with sodium amalgam sclerolide was converted to the lactone (20).
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森田 桂, 小林 栄
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Lenthionine, a highly sulfur-containing odorous substance, has been isolated from Lentinus edodes (Berk.) Sing [Shiitake Mushroom]. The compound represents the characteristic odor of the mushroom and the structure was established to be 1,2,3,5,6-pentathiepane (1) by physico-chemical measurements. 1,2,4,6-Tetrathiepane (II) and 1,2,3,4,5,6-hexathiepane (III) were also separated from the mushroom in minor quantities. All these cyclic methylene polysulfides from natural source were synthesized from simple starting materials. A precursor of lenthionine was isolated in a crystalline form. The compound was not stable and gradually decomposed into lenthionine and its analogs after being left standing at room temperature. The structure of this precursor (IV) is proposed on the basis of the conventional and high resolution mass spectral studies. Finally, the mechanisms of formation of lenthionine and its analogs from the precursor is discussed.
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松井 正直, 黄 玉軒
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The compound having the proposed structure for auxin b lactone (III) was synthesized as follows: 2,4-Di-s-butylphenol (IV) which was prepared through several steps from anisol was hydrogenated at high pressure and temperature in the presence of Raney nickel to 2,4-di-s-butylcyclohexanol (V). When the cyclohexanol was oxidized with potassium dichromate in dilute sulfuric acid, 2,4-di-s-butylcyclohexanone (VI) could be obtained in high yield, and the latter compound was further oxidized with ferric chloride to 3,5-di-s-butylcyclohexane-I,2-dione (VII). Reduction of this dione yielded 3,5-di-s-butylcyclohexane-I,2-diol (VIII), which was treated with lead tetraacetate in dry chloroform; and the obtained dialdehyde, without further purification, was immediately cyclized and dehydrated with piperidine acetate in benzene to 3,5-di-s-butyl-I-cyclopentene-aldehyde (IX) in 82% yield. The Reformatsky reaction of IX with ethyl γ-bromo-β-ethoxycrotonate afforded 4-ethoxy-6-(3,5-di-s-butyl-I-cyclopenten-I-yl)-5,6-dihydro-2-pyrone (X). After treating the enol ether with formic acid for 40 hours at room temperature, and purifying the crude acidic portion with column chromatography on silica gel, stereoisomeric mixture of 4-hydroxy-6-(3,5-di-s-butyl-I-cyclopenten-I-yl)-5,6-dihydro-2-pyrone (III), the compound having the proposed structure for auxin b lactone, was obtained as an oil. III was found to be active in Avena coleoptile section test, Avena root growth test, and pea stem section test; but inactive in Avena coleoptile curvature test and slit pea stem curvature test.
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安江 政一, 加藤 義成
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The skeleton of lyoniresinol (1, R=R'=H) was determined as 4-aryltetralin, and the position of the two free phenolic hydroxyl groups were confirmed as the formula (1, R=R'=H). The absolute configuration (2R: 3R: 4S) of lyoniresinol was proved as proposed before by degradation. Lyoniresinol dimethyl ether (1, R=CH_3, R'=H) afforded 2α,3α-dideoxylyoniresinol dimethyl ether (23), m.p. 107.5/111.5-112.5°, [α]^<16,9>_<546>+44.5°(CHCl_3, c 4.825) by reduction with LiAlH_4 after tosylation. The compound (23) was ozonized and the proauct cyclized with acetic anhydride followed by pyrolysis. From the pyrolysate, there was obtained (-)-3,4-dimethylcyclopentanone semicarbazone (24), m.p. 206.9-209°, [α]^<23.2>_<546>-114°(CHCl_3, c 0.11) of which absolute configuration had been determined correlating to that of natural (-)-(S)-2-methylbutanol (29) by B. Carnmalm. (+)-3,4-Dimethylcyclopentanone semicarbazone (27), m.p. 205.5-207.5°, [α]^<22.6>_<546>+81°(CHCl_3, c 0.33) was synthesized for the further comparison from (+)-3,4-dimethyladipic acid (25), m.p. 99.3-100°, [α]^<15.3>_<546>+4.27°(CHCl_3, c 6.43), [α]^<17.3>_<546>+2.98°(H_2O, c 6.165).
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甲斐 勇二, 清水 基弘
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発行日: 1966/09/15
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New phenolic compounds, named sugiresinol (I) and hydroxysugiresinol (II), were isolated from the heart wood of Cryptomeria japonica D. Don. The structure of sugiresinol (I) was established on the following experimental basis: (i) Hydrogenolysis product (VII) of dimethylether (VI) was treated with HIO_4 to give formaldehyde and aldehyde (VIII). (ii) Dimethylether (VI) was oxidized with chromic acid to furnish anisic acid (X), 4,4'-dimethoxychalcone (XI) and α-(p-methoxyphenyl)-Δ^<α,β>-butenolide (XII). In NMR spectrum of triacetate (V), triplet centered at 6.57τ (J=10.5 cps) is assigned to the axial C_6 proton. Both protons at C_3 and C_4 yieled broad signals at 4.65-5.15τ(half-band width 26 cps) and at 6.85-7.25τ(half-band width 20 cps) respectively. This, as it is known, proves the axial position of both C_3-H and C_4-H. Thus, sugiresinol is represented as (XIV). NMR spectra of (XV) and (V) (Table I and II) show that hydroxysugiresinol has the same carbon skeleton as sugiresinol. Trimethylether (XVI) was oxidised with chromic acid to give 4,3,'4'-trimethoxychalcone (XVII). From these results it is evident that hydroxysugiresinol has the structure (II). NMR spectrum of (XV) [C_6-H: 6.58τ,(1H), t. J=10.5 cps; C_3-H: 4.70-5.20τ(1H), br. m. half-band width 26 cps; C_4-H: 6.90-7.30τ (1H), br. m. half-band width 22 cps] bring to light the possibility that the formula (XVIII) represents hydroxysugiresinol.
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中崎 昌雄, 広瀬 良樹, 池松 潔
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From the ethanolic extract of the seeds of Selinum Monnieri L. there were isolated osthol, bergapten, oroselone and a new coumarin compound, O_<21>H_<22>O_7, m.p.144-146°, [α]^<23>_D+106.7°(c 1.71 in benzene), [α]^<25>_D+84.8°(c 1.76 in pyridine) which was however shown identical with edultin (IV)a, m.p.136-142°, [α]^<11>_D+41.5°(c 26.8 in pyridine) recently isolated by Miteuhashi and Ito from the root of Angelica edulis Miyabe. Since (+)-tetrahydrooroselol (V)b, m.p.113.5-114.2°, [α]^<26>_D+68.0°(c 1.11 in chloroform) obtained by hydrogenolysis followed by saponification of edultin was found identical with the one prepared by Schmid et al. upon the same treatment of athamantin(IV)b, the same configuration at C_2, in both compounds was established. The acetate (V)a of (+)-tetrahydrooroselol was converted into (+)-hexahydrooroselone (+)-(VII), [α]^<25>_D+25.4°(c 1.02 in ethanol) by pyrolysis followed by hydrogenation of the resulted unsaturated compound (V1)a. The asymmetric center of (+)-(VII) was correlated with that of the side chain of rotenone as follows. Gattermann's formylation of (-)-(R)-dihydrotubanol (IX) gave the o-aldehyde (X)a. Heating with malonic acid, pyridine and aniline converted the aldehyde into the coumarin carboxylic acid (XI)a, m.p.188°, which was then decarboxylated to give the coumarin (XI)b, m.p.110-111°. (-)-Hexahydrooroselone (-)-(VII), m.p.106°,[α]^<20>_D-72.0°(c 1.23 in ethanol) prepared by catalytic hydrogenation of (XI)b was proved to be enantiomeric with the one obtained from edultin, indicating the(R)-configuration at C_2, in both edultin and athamantin. From its n.m.r. spectrum and thermal stability the cis relation of two hydrogens at C_2' and C_3' was deduced, suggesting the (R)-configuration at C_3, of edultin; probably the same would be true for athamantin.
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福井 憲二, 中山 充, 原野 昭雄, 柘植 八郎
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The reduction of medicagol methyl ether (17) with lithium aluminum hydride in tetrahydrofuran yielded a diol (18) in 60% yield. The removal of water from (18) in boiling diethylene glycol led to the formation of an ether in 56% yield. The identity of this ether with anhydropisatin (3-methoxy-8,9-methylenedioxy-6a,11a-dehydropterocarpan, O-methyl anhydrosophorol) (15) was confirmed by mixed melting point determination and spectral comparisons. Then, (15) was hydrogenated with 10% Pd-C catalyst to a compound in 60% yield. The synthetic compound was identical with (±)-pterocarpin ((±)-maackiain methyl ether) (1) in mixed melting point determination and spectral comparisons. Since the partial synthesis of (±)-pisatin from naturally occurring (-)-pterocarpin had already been carried out by Birch et al., the total synthesis of it was now accomplished. By selective demethylation with aluminum chloride in acetonitrile, 7-hydroxy-2',4',5'-trimethoxyisoflavone (26) gave 2'-hydroxy derivative (27). Sodium borohydride in absolute alcohol-tetrahydrofuran was used to convert (27) into 3-hydroxy-8,9-dimethoxypterocarpan (28). In this procedure (27) was reduced to form an alcohol, and this lost water readily to (28). 3,8,9-Trimethoxy-(25), furano(3',2': 2,3)-8,9-dimethoxy-pterocarpan (34) were obtained by a similar procedure from 7,2',4',5'-tetramethoxy-(30), furano(3",2": 6,7)-2',4',5'-trimethoxy-isoflavone (isoelliptol isoflavone) (32), respectively. (25) was also derived from (28) by methylation. N.M.R. spectra of these pterocarpans were examined.
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森本 浩, 三野 安, 大塩 春治
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Heliangine (I), C_<20>H_<26>O_6; m.p. 227-229°; (α)^<25>_D-110°; λ_<max> 207.5 mμ(ε: 23,800); υ_<max> 3450, 1754, 1660 cm^<-1>, contains three olefinic bonds. When I was hydrogenated over Pd-C, the exocyclic methylene conjugated with γ-lactone was saturated at first, resulting dihydroheliangine (II); 1770 cm^<-1> (γ-lactone); τ8.9 (C-CH_3). I was hydrolysed with Ba(OH)_2 to give tiglic acid and helianginol (IX), C_<15>H_<20>O_5, containing two secondary hydroxyl groups. Hydrolysis of tetrahydroheliangine (III), obtained by hydrogenation of I, afforded α-methylbutyric acid and dihydrohelianginol. The last olefinic bond was hydrogenated over PtO_2 to give two isomeric hexahydroheliangine (IVa, b) and deoxyhexahydroheliangine (V). A pair of two coupled proton signals at τ 3.5 (d, J=11 cps) and τ4.7 (d, J=11 cps) of III is disappeared in either IVa or IVb, and the latter shifted to τ 4.85 (m). The carbon carrying the lactonic oxygen therefore must be neighbored on the last olefinic group. The hydroxyl group of III also neighbored on the olefinic group, for III afforded the α,β-unsaturated ketone (VI); λ_<max> 246 mμ(ε: 5950) by oxidation with CrO_3. As VI was isomerined to hydroxydienone compound (VII); λ_<max> 249.8 mμ(ε: 9430) by treating with acid, the partial structure A was assumed. The dehydrogenation of II or III afforded two azulenic compounds X and XI. It can be therefore concluded reasonably that I contains a germacrane lactone. Now we decided on the basis of a biosynthesis that constitution I is more reasonable for heliangine than another possible constitution XII.
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ヒキノ ヒロシ, 青田 恵太郎, 前林 行雄, 鈴木 範夫, 竹本 常松
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A sesquiterpenic keto-alcohol, cyperolone, C_<15>H_<24>O_2, m.p. 41-42° (monohydrate),[α]_D+31.4°, of a novel skeleton has been isolated from nutgrass (Cyperus rotundus Linne) of Japanese origin and shown to have the stereostructure I. The IR and NMR spectra showed the presence of a secondary hydroxyl, an acetyl, an isopropenyl, and a tertiary methyl group. On hydrogenation, I gave the saturated dihydro-derivative (II). Oxidation of I and II afforded the cyclopentanones (V & VI), respectively. LiAlH_4 reduction of I formed the diol (VII) whose NMR spectrum indicated the acetyl bearing carbon in I to be quarternary. Alkali treatment of VI gave the monoketone (XII) which was synthesized from the known 14-noreudesmanone (IX). β-Configuration of the C-3 hydroxyl was deduced by application of the benzoate rule. β-Configuration of the C-5 acetyl was established by examination of the NMR spectra of I, II, and their acetates (III & IV) and by the positive Cotton curve of the derived ketol acetate (XIV). The cis-relationship of the C-3 and C-5 substituents was confirmed by the presence of an intermolecular hydrogen bond in VII. (+)-α-Cyperone (XV) was reduced to give α-cyperol (XVI) which was oxidized to the epoxy-ketone (VIII) via the epoxy-alcohol (XVII). The epoxide (XVIII) was isomerized with BF_3 to afford the dione (V) which on reduction gave the diol (VII). Partial acetylation of VII followed by oxidation yielded cyperolone acetate (III) which was hydrolyzed to furnish the natural cyperolone (I).
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棚橋 善昭, 和田 正武, 高橋 武美, F. Patil, J.-M. Lehn, G. Ourisson
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A new sesquiterpene, furanoligularenone C_<15>H_<18>O_2, was isolated from roots of a plant which were purchased at Hong-Kong as "Shion (Radix Asteris)", and were later found to be roots of a species of Ligularia genus. Structure (I), including the absolute configuration, was established for furanoligularenone on the basis of the chemical degradations and physico-chemical measurements. One of the main degradations was a conversion of (I) to (V) and (VI), which were found to be isomeric with the known furanoeremophilane (A) and eremophilenolide (B). The absolute configuration was determined by Horeau's method as well as by a transformation of (I) to (XIII), which was identified with the well-established 5,10-dimethyl-3-isopropyl-2-decalone.
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通 和夫
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Recently, Takeda and coworkers have elucidated the structures of linderene (I), which is a sesquiterpenic component of the root of Lindera strychnifolia Vill., and its dihydrogenated products, dihydrolinderene (II) and isodihydrolinderene (III). Here are presented the proton magnetic double and (or) triple resonance studies of I, II, and III in deuteriochloroform and pyridine-d_5 at 100 mc field to make the full interpretation of the spectra of these compounds. The proton spin-decoupling experiments were performed by using a Varian HA-100 spectrometer with two Hewlett-Packard HP-200ABR audio-oscillators and on HP-5212A electronic counter in the frequency sweep and TMS locked mode. As a result, the spectra of I, II, and III were revealed to correspond well to their chemical structures. Particularly, the proton spin-decoupling experiments on II evidently showed the β-configuration of the cyclopropane ring. Several long-range spin couplings in the molecules examined were found also. Incidentally, the spectrum of isolinderoxide (IV), another minor sesquiterpenic component isolated from the same plant, in which the β-configuration of the cyclopropane ring was determined by the degradation, was also studied to show that its structure is correct.
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山田 静之, 高田 進, 中村 司朗, 平田 義正
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Two toxic compounds, anisatin (I) and neoanisatin (II) were isolated from the seeds of Japanese star anise, Illicium Anisatum L. The structure of anisatin was already determined as (I). The properties of two toxic compounds are similar, except that the 1,2-glycol is present in anisatin whereas not in neoanisatin. Correlation of two toxic compounds was investigated: two-step oxidation of neoanisatin (II) gave a ketoacid which is identical with the acid (VII) (its structure and stereochemistry are known) derived from anisatin. Norneoanisatin (VIII), on oxidation with chromic acid in sulfuric acid afforded a lactone-dicarboxylic acid (IX), the formation of which indicates the trans-fusion of two carbocyclic rings. The structure of neoanisatin was deduced as (II) on the basis of the oxidation products mentioned above and the spectral data. Anisatin (I) was isomerized to a lactone-carboxylic acid, anisatinic acid (XI) under basic conditions. The infrared and NMR spectral data show that the carbon atoms marked with asterisks in (I) are involved in the isomerization. The structure (XI) is presented for anisatinic acid. The structure (XII) was assigned to the acetylated product of anisatinic acid. The corresponding isomerization of neoanisatin (II) was also observed. The intramolecular displacement of the β-lactone moiety by the carbanion is the isomerization, leading to formation of a new carbon-carbon bond. The steric compression of the molecule is responsible fbr this unusual transformation.
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岡本 敏彦, 小泉 徹, 首藤 紘一, R. C. Northrop, 染井 正徳, 松山 邦義, 楊田 富子, 夏目 充隆
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In connection with the synthetic studies of C_<20>-gibberellic acids and aconite alkaloids from enmein, the hydroxy acid 5 and the C_<20>-gibberellic acid derivative (34) and its isomer (20) were synthesised. 5 was converted to a cyclopropane derivative (12) and a dihydroxymethyl gibbane derivative (13) by Birch reduction of the dehydrated ester (11). Hemiketal (3) was treated with alkali to give the isomeric hemiketal (14), of which mesylate (17) was rearranged to A/B cis-gibbade derivatives 18 and 19. 34 was derived from the rearranged ketone 21 via the acetal 24, which would be obtained from the Wagner type rearrangement of 23. Attempts to interrelate enmein to garryfoline were partly discussed, and the angular acid azid (47) was synthesized. Eleven diterpenes were isolated from the leaves of Isodon tricocarpus KUDO. The structure of isodonol were proposed as 60 on the basis of chemical and physical data.
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田村 三郎, 高橋 信孝, 室伏 旭, 横田 孝雄, 加藤 次郎, 和田 良雄, 渡辺 英二, 青山 鉄美
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(1) Presence of gibberellin A_3 in immature seeds of morning glory (Pharbitis nil) was established by means of thin layer chromatography after several purification steps. Another active principle in the seeds was isolated in crystalline form as its methyl ester, m.p. 181°, which was tentatively named Pharbitis Gibberellin. Molecular formula, C_<20>H_<26>O_5, was assigned to the methyl ester on the basis of high resolution mass spectrum. Structure IV was established by comparison of NMR spectra measured in CDCl_3 and in pyridine and finally by chemical conversion to tetrahydrogibberellin A_5 methyl ester. (2) Two new gibberellins were isolated in crystalline forms from immature seeds of horse bean (Canavalia gladiata DC), which show typical gibberellin activity to dwarf maize and tentatively named Canavalia Gibberellin-I and -II. Structure V and VI were proposed to Canavalia Gibberellin-I and II respectively, from consideration of high resolution mass spectra and NMR spectra.
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住本 昌之, 近藤 民雄
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The configuration of sciadin, a furanoid diterpene isolated earlier from Sciadopitys verticillata Sieb. et Zucc. has been the subject of the present investigation. N.M.R. spectra of sciadinone(4) and its derivatives clarified the remarkable differences between C-17 H_A and H_B of the series (11). Namely tremendous shifts caused by the different substituents at C-8 were observed only on H_A but not on H_B, and, furthurmore, H_A showed fine splittings (J=1 c.p.s.) due to the coupling with C-1α H whereas H_B did not. (Table 1.). These results were successfully applied to decide to be β-configuration of C-17 H on sciadin.(Table 2). Of the two possible conformations (17 & 18), the latter (=1b) was prefered because of the observation on the large shifts of C-12 H peaks due to C-8-substitution (Table 3.). Configurations of several other sciadin derivatives have also been discussed.
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古森 徹哉, 瀬戸口 信郎, 川崎 敏男
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The unknown, nonsteroidal, nonglycosidal and N-free substance, which had been obtained as crystals from the root tubers of Dioscorea bulbifera L. forma spontanea Makino et Nemoto, was found to be a mixture of at least three compounds. One of them, named bulbiferin C, m.p.255°, (α)_D +17.3°, was isolated only in trace and the structures of major component, bulbiferin B, m.p. 285°, (α)_D+103.0° and minor, bulbiferin A, m.p. 283°, (α)_D +16.2°, were investigated. Bulbiferin B, C_<19>H_<20>O_6, m.w. 344 (mass) has γ-lactone, β-substituted furane and no hydroxyl groups (positive Ehrlich reaction, I.R., U.V. and mass spectra). B is converted to A by hydrolysis with NaOH in pyridine followed by neutralisation and methylation with diazometane. Bulbiferin A,C_<20>H_<24>O_7, m.w. 376 (mass), has hydroxyl, ester, γ-lactone and β-substituted furane functions (Ehrlich reaction, I.R., U.V. and mass spectra). On treatment with NaBH_4 B is unchanged but by catalytic hydrogenation over PtO_2 it gives a hexahydro-compound having tertiary hydroxyl group indicating B (and also A) has an ether oxygen. The hydrogenated B is reduced with LiAlH_4 and the product is subjected to the Se-dehydrogenation to give 1,2,5-trimethyl naphthalene. The N.M.R. spectra of tetrahydro-B and -A indicate the presence of one tertiary methyl group. From these and other experimental data B and A are respectively assigned the partial formulae (a) and (b) of furano-norditerpene type. The results of a further investigation on the location of the functional groups which lead to the tentative structures of B and A are presented.
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藤田 栄一, 藤多 哲朗, 渋谷 雅之
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Five kinds of new diterpenes have been isolated from Isodon trichocarpus Kudo and Isodon japonicus Hara. The structures of isodocarpin and nodosin have been established as shown in the formulas (II) and (III). The spectral features of trichodonin, trichokaurin and oridonin are discussed, and the structures (IV) and (V) are tentatively proposed for trichodonin and trichokaurin, respectively.
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河津 一儀, 三井 哲夫
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A fish-killing component, callicarpone, C_<20>H_<28>O_4, m.p. 111°, [α]^<23°>_D-188°, isolated from the leaf of Callicarpa candicans was proved to be represented by the structure I on the following evidences. The IR, UV and NMR spectral data suggested that I had one tertiary hydroxyl and ene-1,4-dione. Tetraol (IIa), obtained by lithium aluminum hydride reduction of I consisted of two secondary hydroxyls and 1,2-glycol of two tertiary hydroxyls, one of which was involved in α-hydroxy-isopropyl group. This finding, coupled with formation of chlorohydrin (III) showed an oxide ring attached to α-hydroxy-isopropyl group was present in I. It is, therefore, apparent that I is a tetracyclic diterpene. Treatment of I in methanol with sodium carbonate gave a diphenol A (IVa), C_<20>H_<28>O_4 and a smaller amount of diphenol B (Va), C_<17>H_<22>O_3. The structure of this rearranged product (IVa) was established by identifying IVh as 11-methoxy ferruginol methyl ether. As this rearrangement was assumed to be initiated by proton abstraction by base, placement of the oxide ring in 12, 13-position in I was required to explain the formation of IVa. Formation of Va as a minor product was also well explained by aromatization accompanied by liberation of acetone from I.
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丸山 雅雄, 寺原 昭, 中平 靖弘, M. C. Woods, 板垣 又丕, 高木 良子, 中西 香爾
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From the root bark of Ginkgo biloba L. ("icho" in Japanese), a unique fossil tree which has remained unchanged for 1-2 million years, four bitter principles designated ginkgolides A, B, C and M (for "minor") (abbreviated to GA, GB, GC and GM) have been isolated. Early work was greatly hindered by purification problems and polymorphism, but the molecular formulae were finally settled by high resolution MS of GA dimethyl ether (Fig. 1). As shown in Fig. 2, a tert-Bu group is present; these are the first plant products to contain such a group. Establishing the number of lactone groups presented difficulty, but was achieved by titration according to Method B (Fig. 3). The partial structure comprising rings A/B was elucidated from the data summarized in Figs. 5 and 6. NMR analysis of the isolated 4 proton system E-H (Fig. 7) was simplified in GC because of an additional 2°-OH group. The bislactone system containing H_J was clarified (Figs. 8-10) by an NMR analysis of GA-triether utilizing extensively the techniques of solvent shifts and decoupling, and comparison with the triether-d_6 spectrum which resembles the GA spectrum (Fig. 13). An attempt to determine the number of lactone rings was made by measuring the M^+ and isotope peaks of GA dimethyl ether (Fig. 11), the lactone rings of which had been cleaved and recyclized in the presence of H_2O^<18> as depicted in Fig.13-Method B. However, the MS indicated that only two lactones had incorporated O^<18>; presumably, one of the lactones had been cleaved by O-alkyl fission and recyclized by expulsion of O^<18>H. Alkali fusion of GA gave two important bisnor products, but these are not discussed in the Abstract because of limitations of space. Part structures shown in Fig. 12 are proposed for the ginkgolides.
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津田 恭介, 奥田 重信, 野副 重男, 板井 昭子, 山田 充, 中山 勇弥, 飯高 洋一
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The structure of ophiolobin, fungal metabolite from Ophiobolus miyabeanus was established. Subsequently, the structure of zizanin-A and -B, isolated from Helminthosporium zizaniae, were eluoidated by chemical correlation. These compounds, which have O_<25> carbon skeleton were classidied as Sester-terpenoid. On the other hand, we have been engaged the structural studies of helvolic acid which is protolanostan type compound isolated from Cephalosporium caerulans. Recently, this fungus is found to produce new antibiotic named as cephalonio acid which shows weak activity against Staphylococcus aureus. Cephalonic acid, m.p. 139-140°, [α]_D76.2°showed UV absorption maximum at 258 mμ (logε, 4.06). The mass spectrum confirmed the empirical formula C_<25>H_<36>O_4. The IR spectrum indicates the presence of carboxyl group, carbonyl group and olefinic linkage. The n.m.r, showed the presence of five methyls, an olefinic proton at 5.02, a methine proton on the carbon atom bearing hydroxyl group at 5.02, a methine proton at 4.38, and α-proton of αβ-unsaturated carbonyl system at 6.05. The complete structure of cephalonic acid uncluding its absolute configuration was solved by three dimensional X-ray crystallography of the bromoacetyl derivative. The results revealed that the structure of cephalonic acid was as expressed by I. Hydrogenation of methyl cephalonate II with Pt catalyst gave III, IV and V, while with Pd/C afforded Vi as a sole product. The UV spectra of I and VI were identical with those of VIII and VII respectively. The mass spectrometric fragmentation are discussed briefly.
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上田 博之, 岩田 憲治
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発行日: 1966/09/15
公開日: 2017/08/18
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From the leaves of Northern Maidenhair Fern, Adiantum pedatum LINN. collected in Japan, four triterpenoid hydrocarbons, isofernene(I), fernene (II), 7-fernene(III) and filicene(IV), a triterpenoid enal, named filicenal(VI), a nor-triterpenoid ketone, adiantone(VII), and a nor-triterpenoid hemiketal, named adipedatol(VIII) were isolated as shown in Table I. The structure of two new compounds, adipedatol and filicenal, have been established as formulated by VIII and VI, respectively. The NMR spectra (Table II) and Mass analysis of adipedatol (VIII) and its derivatives suggested that VIII has a 30-nor-hopane skelton having oxygen functions at C(28) and C(22). This was confirmed by chemical evidences as shown in Chart 1, especially deriving to 30-nor-21αH-hopane (XV). The structure VI for filicenal was also demonstrated by spectroscopic methods and confirmed by chemical evidence.
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永井 正博, 田中 治, 大沢 富彦, 田中 信寿, 柴田 承二
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発行日: 1966/09/15
公開日: 2017/08/18
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On acid hydrolysis with boiling diI. mineral acid, Ginseng samnins, ginsenoside-Rb_1, -Rb_2, and-Rc, afforded panaxadiol (I), which was also obtained from protopanaxadiol (III) (=12-β-hydroxydammarendiol-I), by the acid treatment, whereas, treatment of these saponins with cold conc. HCl, a chloride (II) was formed. By the action of diethylaniline or silica gel, this chloride gave a mixture of III and isoprotopanaxadiol (IV), while t-BuO^- afforded mostly protopanaxadiol (III). This anomalous orientation of these elimination reactions would be due to the anchimeric assistance of C-20 -OH or O^-. Acid catalyzed epimerization of C-20 OH of betulafolienetriol (VI) (=3-epi-12β-hydroxydammarenediol-II) and betulafolianetriol (VIII) has been examined (see Fig. 2). Conversion of VIII to dihydroprotopanaxadiol (XI) has been achieved, and it has been confirmed that panaxadiol (I) has the same C-20 configuration as that of protopanaxadiol (III). The absolute configuration of C-20 of panaxadiol (I) has been established to be R by correlation with (-)-R-linalool (XIX) as shown in Fig.3. Consequently, it can be now concluded that the absolute configuration of C-20 of dammarenediol-I (XVII) as well as that of protopanaxadiol is represented as R, then that of dammarenediol-II (VII) and betulafolienetriol (VI) and their homologs is S configuration.
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伊東 椒, 児玉 三明, 鴻池 政壽, 荻野 敏夫
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発行日: 1966/09/15
公開日: 2017/08/18
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The mixture of saponins obtained from Camellia japonica L. was hydrolyzed and separated by chromatography into camellia sapogenols, CS-A [C_<30>H_<46>(OH)_4, m. p. 282-283°], CS-B [C_<30>H_<44>(=O)(OH)_4, m. p. 200-205°], and CS-C [C_<30>H_<45>(OH)_5, m. p. 262-263°]. Structural relationships between them were established by the LiAlH_4 reduction of CS-B to CS-C and by the Huang Minion reduction of CS-B to CS-A. The existence of an olean-12-ene carbon skeleton in these compounds was deduced from the spectra of the diene-dione derived from the CS-C diacetonide acetate. The nature and the location of the oxygen functions were shown by close examination of the NMR spectra of the sapogenols and their derivatives and by the result of chemical reactions. On this basis, the sapogenols A, B, and C have been assigned the structures, olean-12-ene-3β, 16α(or β), 22(or 21)α, 27-tetraol, olean-12-ene-3β, 16α(or β), 22(or 21)α, 27-tetraol-23-al, and olean-12-ene-3β, 16α(or β), 22(or 21)α, 23, 27-pentaol, respectively. These three sapogenols have also been isolated from Camellia sinensis (L) O. Kuntse.
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村上 孝夫, 糸川 秀治, 沢田 尚敏
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セッションID: 37
発行日: 1966/09/15
公開日: 2017/08/18
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Camellia sapogenol I,II,III(C. Sg. I,II,III) were produced by hydrolysis of camellia saponin isolated from Camellia japonica L.C. Sg. I, C_<30>H_<50>O_4 was a tetrol. And formation of acetonide suggested that C.Sg.I has a 1,3 -glicol moiety, since the presence of a 1,2-glycol moiety was eliminated the observed stability of C.Sg.I toward perhydroiodic acid. Selenium dioxide oxidation of (V) led to a diene, which on the basis of its characteristic triple ultraviolet absorption maxima could be assigned the heteroannularΔ^<11,13(18)>-formulation, thus showing that C.Sg.I vas a member of the β-amyrin class of triterpenes. By chromium trioxide-acetic acid oxidation of C.Sg.I, camellia trione (VI) was produced, and (VI) was proved to be identical with 28-nor-Δ^<12>-oleanene-3,16,22-trione derived from chichipegenin. So structural formula (4) was presented for C.Sg.I. From the production of (IX) and (X), C-28 carbinol did not concern for acetonide formation. So acetonide must be formed between C-16 and C-22-hydroxyl groups. If C-22 hydroxyl group had β-orientation, it must form acetonide with C-28 carbinol. And C-16(β), C-22(α)-diol type was excluded, because it is same with chichipegenin. Then it was assumed that 16α, 22α-diol type was best. Orientation of hydroxyl group at C-3 was determined as β by lithium aluminum hydride reduction of (X). Hence C.Sg.I can now be given systematic name 3β,16α,22α,28-tetrahydroxyolean-12-ene (I). C.Sg.II, C_<30>H_<48>O_5, having aldehyde group was derived to (I) by Wolff-Kishner reduction and also derived to C.Sg.III, C_<30>H_<50>O_5, by lithium aluminum hydride reduction. C.Sg.III formed diacetonide, and from the observation of NMR spectrum of (XIX), C.Sg.II and III were thus shown to be 23-oxo-3β,16α,22α,28-tetrahydroxyolean-12-ene(III and 3β,16α,22α,23,28-pentahydroxyolean-12-ene(III) respectively.
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吉岡 一郎, 西村 正, 松田 明子, 北川 勲
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セッションID: 38
発行日: 1966/09/15
公開日: 2017/08/18
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The sanogenol mixture obtained by the successive treatment with acid and alkaline of the title saponin has been found consisting mainly of four triterpenic alcohols, designated as theasapogenol A (major)(Ia), C_<30>H_<50>O_6, mp.301-3°;[α]_D+14°(c: 0.5, in pyridine), theasapogenol B (second major)(Ib), C_<30>H_<50>O_5, mp.278-284°;[α]_D+23°(c: 0.5, in pyridine), C, and D, respectively, according to their Rf values from the bottom on TLC. In this report, the chemical studies on theasapogenol A and B leading to the structures: 3β,16α,21β,22α,-23,28-hexahydroxy-olean-12-ene and 3β,16α,21β,22α,28-pentahydroxy-olean-12-ene, are presented. The structure of theasapogenol A was determined by converting it to theasapogenol B through reductive elimination of the 23-hydroxylic function. However, it has been found that anhydro-theasapogenol B (VIb) (3β,22α,28-trihydroxy-16α,21α-epoxy-olean-12-ene) is identical with barringtogenol D, whose structure (XX) has already been proposed as having 22β-OH by Barua et al. The inconsistency of the observation lies on the different configuration of the 22-hydroxyl function. In addition, the identity of theasapogenol B with barringtogenol C (proposed as having 21α,22β-glycol (XXI) by Barua et al.) presents another discrepancy concerning to α-glycolic hydroxyls in ring E. Although the present study favors the 21β,22α-glycol (trans diequatorial) configuration in theasapogenol B and 22α-OH in its anhydro derivative mostly based on the NMR analyses, the further chemical studies on these subjects are important requisite and in progress in this laboratory.
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武田 健一, 岩崎 光隆, 島岡 有昌, 湊 均
原稿種別: 本文
セッションID: 39
発行日: 1966/09/15
公開日: 2017/08/18
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The steroidal constituents of Chionographis iaponica MAXIM. (Japanese name "Shiraitoso") were investigated, and the new compound, chiogralactone (I), C_<23>H_<34>O_4, m.p. 238-240°, [α]_D-113°, was isolated. Its IR spectrum shows absorption bands corresponding to hydroxyl group (3730 and 3540 cm^<-1>), δ-lactone (1733 cm^<-1>) and six-membered ring ketone (1712 cm^<-1>), and NMR spectrum shows the presence of two angular methyl groups (9.22 and 9.21 τ) and one secondary methyl group (8.86 τ, doublet, J=6.5 cps). On the assumption that I has a steroidal skeleton, the physical data of I and its derivatives were examined. ORD curve of Na-salt (V) shows a negative Cotton effect (a=-69). Chemical shift of 19-methyl group in I or IV is in good agreement with the result obtained in laxogenin or β-chlorogenin, respectively. ORD curve of VI shows a negative Cotton effect (a=-220), and the Barbier-Wieland degradation of IV gave the compound assumed to be pregn-16-en-20-one (X). Application of the Hudson-Klyne lactone rule to IV showed that the lactonic oxygen at the 16 position has β-configuration. On these bases, chiogralactone is assumed to have the structure (I). Then, 3β,16β-dihydroxy-6-oxo-24-nor-5α-cholan-23-oic acid lactone (XXIV) was synthesized from diosgenin acetate (XI), and XXIV was identical with chiogralactone by mixed melting point determination and comparison of IR spectra and [α]_D values. Thus, the structure of chiogralactone has been established.
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森 弘, 柴田 健雄, 常田 清, 沢井 政信
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発行日: 1966/09/15
公開日: 2017/08/18
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Synthesis of ecdysone is now in progress in our laboratory. Three key reactions for synthesis of ecdysone were developed. a) The enol form of 2,3-diketone (3) which is easily obtainable from 3-oxo steroid could be reduced by sodium borohydride into 2β,3β-diol (4) as a major product. b) Reaction of the enol acetate of 7-en-6-one (6) with monoperphthalic acid produced 14α-hydroxy-7-en-6-one (7). c) The ethynylation of aldehyde (8), followed by carboxylation gave carboxylic acid (10). This was hydrogenated and hydrolyzed to give the lactone (12), the lactone structure of which could be transformed into 22αF,25-dihydroxy compound by Grignard reaction. Acetonide of 2β,3β-dihydroxy-5α-cholestan-6-one (27) was prepared through two routes (22→23→24→25→27 and 28→29→30→31→32→27) by using the key reaction described above. The hydrolysis of (27) with 10% phosphoric acid yielded 2β,3β-dihydroxy-5α-cholestan-6-one (33a). The stereochemical problem of 2β,3β-dihydroxy-6-ones and their derivatives were examined. The treatment of (33a), (33b), (34a) or (34b) with acid or alkali gave a equilibrium mixture with ratio of 5α: 5β=3: 2. On the other hand, 5α-compound (27) is exclusively stable in acetonide series. A reasonable explanation of this difference was given. Acetonide formation reaction by phosphomolybdic acid is of interest, because reaction was found to be completed only for 10-15 minutes in spite of very weak acidity of the catalyst and any isomerization was not occurred.
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原稿種別: 付録等
p.
App2-
発行日: 1966/09/15
公開日: 2017/08/18
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