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宮原 一元, 工藤 恵子, 熊本 史生, 川崎 敏男
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In connection with a study on the structures of two steroidal compounds, BR-1(XIII) and BR-2(XIV), which were isolated from the rhizomes of an east Himalayan plant Campylandra aurantiaca, an extensive survey for the steroidal constituents of the rhizomes of domestic Rhodea japonica Roth. has been carried out in this laboratory. To date, more than twenty kinds of compounds were obtained, and fourteen of them were characterized. This study concerns the structure elucidations of additional four compounds, R-1(I), R-2(II), R-16(III) and R-23(IV), of R. japonica, and identification of BR-1(XIII) and BR-2(XIV) with I and II, respectively. The structure of I(=XIII) was determined on the basis of chemical and spectral data and unequivocally confirmed by X-ray analysis. III was also assigned the detailed structure with the aid of X-ray crystallography, while II(=XIV) and IV were characterized respectively by correlation with I and III. I(=XIII) and II(XIV) are noted as the spirostane derivatives highly oxygenated in the rings A and B, and III and IV, are, to our knowledge, the first cardenolide glycosides having D-allose attached to the aglycone. It is also worth of note that the C-ring of the aglycone (bipindogenin) of III has the boat conformation.
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岡野 桂樹, 大川 信彦, 村垣 博宣, 池上 晋
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Steroidal glycoside sulfates in the ovary of the starfish Asterias amurensis inhibit the maturation of oocytes and the suppression is overcome by the action of a peptide hormone released from the nervous tissue. We have purified from the ovary fraction B which consists of closely related glycosides and determined the structure of the major two designated B_1 and B_2. The structure of glycoside B_1 is 20α-hydroxy-6α-0-{β-D-quinovopyranosyl-(1'→2')-β-D-glucopyranosyl(1'→4')-[β-D-quinovopyranosyl(1'-2')]-β-D-xylopyranosyl-(1'-3')-β-D-quinovopyranosyl}-3β-sulfo-oxy-5α-cholesta-9(11),24-diene. The structure of glycoside B_2 is 20ξ-hydroxy-6α-0-{β-D-quinovpyranosyl-(1'→2')-β-D-galactopyranosyl(1'→4')-[β-D-quinovopyranosyl(1'→2')]-β-D-xylopyranosyl(1'→3')-β-D-quinovopyranosyl}-3β-sulfo-oxy-5α-cholest-9(11)-en-23-one.
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秋山 敏行, 高木 重和, 三川 潮, 稲荷 昌司, 斎藤 肇
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In order to gain understanding of the hemolytic action of DIG in plasma membrane, a ^2H NMR study was attempted using CHOL-d_6 and SA-d_3 probes together with DIG and its analogs in the multibilayers of egg yolk PC. It was found that DIG changed the ^2H NMR spectra of the former probe more than that of the latter. Thus, CHOL is proved as the target molecule for DIG. As ^2H NMR spectra of CHOL-d_6 in the equimolecular complex gave the quadrupole splitting close to that of solid CHOL-d_6, the complex in the multibilayers of egg yolk PC is characterized by the rigid structure as in the "digitonides" as occurring as precipitates in aqueous ethanol. It was also found that the excess CHOL not directly complexed with DIG (in lower DIG: CHOL ratio) gave rise to ^2H NMR spectra with reduced quadrupole splitting and larger linewidths compared with those of the absence of DIG. Therefore, the alteration of the bilayer structure is not always restricted to the vicinity of CHOL complexed with DIG. It may be concluded that the hemolytic activity of DIG can be explained by the presence of such disordered CHOL and lipids in the bilayers. Furthermore, prosapogenins with reduced number of sugar moiety exhibited quite different behavior. Therefore, configuration of the sugar moiety in DIG plays a crucial role in the interaction with CHOL.
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山田 幸子, 中山 恵子, 高山 浩明, 板井 昭子, 飯高 洋一, 森内 幸子, 鶴木 富紀子, 太田原 洋子
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Dye sensitized photo-oxidation of vitamin D derivatives (1a-f) has been examined. In each cases, the corresponding (6R)- and (6S)-epidioxyvitamin D derivatives (2a-f and 3a-f) have been isolated in 50-60% total yields. The precise structures of the peroxides (2 and 3) were determined based on the X-ray analysis as well as the analysis of the spectral data. Dye sensitized photochemical cis-trans isomerization of the 5,6-double bond has been found to occur concomitantly with the photo-oxidation of vitamin D. Therefore, correctly, the peroxides (2 and 3) were produced from a equilibrated mixture of vitamin D (1) and the corresponding 5,6-transvitamin D (6) in photo-stationary state. The chemical behavior of the peroxides (2 and 3) has been examined in the thermolysis and the reactions with acids, bases and reducing agents. Biological activity of the peroxides (2d and 3d) was tested comparing with that of vitamin D_3 (1d). Significant activity was found in both 2d and 3d.
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釜野 徳明, 井上 益男, G. R. Pettit, 佐藤 久男, 戸澤 満智子
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One of the important component of the toad venom preparation Ch'an Su, cinobufotalin (6) was synthesized from cinobufagin (1) in 4 steps, as shown in Chart 1. The result provided the completion of a new formal total synthesis of cinobufotalitoxin, immediately. By a similar route, the unknown bufadienolide 5β-hydroxybufotalin (18) was synthesized from bufotalin (13) (Chart 2). Also, the new compound (18) was obtained from cinobufotalin (6) in 7 steps, including selective deacetylation besides treatment of the epoxyketone with Cr(OAc)_2 (Chart 3). On the other hand, to determine whether similar stereochemical requirements may be operative in respect to the bufadienolide activity, we undertook the synthesis of bufadienolide stereoisomers. One of them, 5α(H)-cinobufagin (25) was prepared from the corresponding 4-en-3-one 3 by reduction with LiBH_4 in pyridine. Conversion of bufotalin (13) to the 14α-hydroxybufadienolides, 29 and 30 was shown in Chart 4.
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辻 二郎, 清水 功雄, 鈴木 博久, 内藤 洋一郎
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As a new bisannulation reagent, 1,7-octadien-3-one was prepared easily from a butadiene telomer obtained by the palladium catalyzed reaction of butadiene with acetic acid. This reagent is useful for annulation, because it undergoes Michael addition at the enone moiety and then the terminal double bond is oxidized to methyl ketone with PdCl_2/CuCl/O_2 to generate 1,5-diketone system. Tricyclic ketones were prepared from this compound. Also total synthesis of optically active (+)-19-nortestosterone has been carried out.
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佐藤 良博, 園田 よし子
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The effects of lanosterol analogues on cholesterol biosynthesis and their metabolisms were examined. The lanosterol analogues (3), (4), (5), (6), (8), (11), (14). (16), (18) and [24-^3H]-lanosterol (22) were synthesized from lanosteryl acetate (1b) (Scheme 1 and 2). [24-^3H]-Lanosterol (19μM) was incubated in the presence of lanosterol analogues (45 μM) with S-10 from rat liver. It was found that the side chain analogues of lanosterol have the inhibitory activities and that 27-nordihydrolanosterol (4) and 23,24,25,26,27-pentanordihydrolanosterol (14) exhibit high activities (Table II). Furthermore, tritium labeled lanosterol analogues (24 and 25) were synthesized (Scheme 2) and their metabolisms were examined. After the incubation of [24,25-^3H]-27-nordihydrolanosterol (25) with S-10, its nonsaponifiable fraction was chromatographed on t.l.c. plate followed by radioautography (Fig. 1a). The results indicated that (25) was transformed to tritium labeled 27-norcholesterol in the yield of 6.4%. On the other hand, the incubation experiments proved that [22-^3H]-23,24,25,26,27-pentanordihydrolanosterol (24) is not transformed into the corresponding demethylated sterol, 23,24,25,26,27-pentanorcholesterl.
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金子 光, 川村 紀明, 田中 美香子, 三橋 博
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In our detailed experiments on the separation of steroidal alkaloids which accumulate particularly in the illuminated Veratrum plants but not found in the etiolated plants, two new cevanine alkaloids, shinonomenine (1a), (25S)-20-epi-cev-5-enin-3β-ol, which was finally determined by X-ray crystal structure analysis, veraflorizine (2a), (25S)-cev-5-enine-3β,20β-diol, which was synthesized from verticinone, an unique cevanidane alkaloid, procevine (5a), (22R,25S)-cevanid-5-en-3β-ol, which was synthesized from isorubijervine(4a), and a solanidanine alkaloid, isorubijervine (4a) were isolated. The isolation of these alkaloids from the illuminated Veratrum plants suggests the biogenesis of cevanine alkaloid via formation of C-18-N bond from isorubijervine (4a), before C-nor-D-homo rearrangement. In continuation of our works on separation of alkaloids in the illuminated Veratrum plants, hosukinidine (6a), (20R,22R,25S)-veratra-5,12-dien-3β-ol, which was settled by X-ray crystal structure analysis, and epirubijervine (7a), solanid-5-ene-3β,12β-diol, which was synthesized from rubijervine (11), were isolated. The separation of both alkaloids suggests mechanism of C-nor-D-homo rearrangement in the biogenesis of jervanine and veratranine alkaloid.
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橋本 庸平, 石曽根 博之, 小倉 勝
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Investigation of the natural sweetners from the roots of Periandra dulcis Mart. (Leguminosae) afforded three new triterpene-glycosides, periandrin I (PI, 3β-O-[β-D-glucuronopyranosyl-(1→2)-(β-D-glucuronopyranosyl]-25-formyl-olean-18(19)-en-29(or 30)-oic acid), periandrin II (PII, 3β-O-[β-D-glucuronopyranosyl-(1→2)-β-D-glucuronopyranosyl]-25-formyl-olean-12(13)-en-30-oic acid), and periandrin IV (PIV, 3β-O-[β-D-glucuronopyranosyl-(1→2)-β-D-glucuronopyranosyl]-25-hydroxy-olean-12(13)-en-30-oic acid). The structures of PII aglycone (PAII) and PIV aglycone (PAIV) have been elucidated to be 5 and 6, respectively, by correlation with known compound. Evidence for the structures of PII (2) and PIV (3) was obtained by methanolysis of permethylates and NMR spectroscopy. The structure of PI has been proposed to be 1 on the basis of chemical and physicochemical evidence. By taste panel, PI, PII, and PIV have the almost same degree of sweetness as glycyrrhizin.
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古林 祥正, 小川 宗治, 雨谷 栄, 浅田 みや子, 荻原 幸夫
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Summary of new oleanane triterpenoid glycosides from the leaves of Tetrapanax papyriferum and Bupleurum rotundifolium L. are presented. The reaction of oleanane triterpenoid glycosides (1),(6) and (7)with reagent A gave 11-oxo compounds (5) and (8). This fact indicated that this reagent was useful for the oxidation of an allyl alcohol and an allyl ether. On the other hand, the reaction of oleanane triterpenoids (14),(15),(16) and (17) with reagent A gave 16-oxo derivertives (12),(18),(19) and (20), while compounds (21) and (24) with this reagent gave 21-oxo derivertives (26) and (27). Reagent A is also very useful to the selective oxidation of 16- and 21-axial hydroxyl group. Preparation of Reagent A A mixture of CrO_3, pyridine and n-BuOH saturated with water were kept at room temperature for 1 day. The mixture was concentrated under reduced pressure and the residue was washed with water and CHCl_3, and dried under reduced pressure.
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宮本 富美子, 直木 秀夫, 納谷 洋子
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Examination of the secreted wax of a scale insect, Ceroplastes ceriferus has shown the presence of various compounds of considerable biogenetic interest. (a) The sesquiterpenes were enantiomeric with respect to those from C. rubens, which infests the same host tree. Each insect may possess a specific set of C-C cyclases for the formation of sesquiterpenes. (b) Among the identified twelve diterpenes, two of labdane skeletons were the first naturally occurring compounds. (c) The sesterterpenes (1-6)(7-10) having 14-membered monocyclic skeletons were the first naturally occurring compounds being independent of the host tree. Remarkable is the finding of sesterterpenes resulting from different biogenetic cyclization mode from the same species, collected in different districts, or from the different species of the same genus. (d) The "cyclic" wax were the esters consisting of fatty acids (C_<10>-C_<32>) and unusual cyclic alcohols (diterpenes and sesterterpenes). Structures and stereochemistry of nine new sesterterpenes will be discussed on the basis of spectroscopic and chemical methods: Cericerol-I (1), cericerol-II (2), 13-methoxy cericerene (3), 13-ethoxy cericerene (4), α-cericerol-I (5), cericeroic acid (6), 18-dihydro-19-ol cericeroic acid (7), cericera-2(E),6(Z),10(E),15(22), 18-pentene-25-acid (8), cericera-2(E),6(Z),10(E),15(22), 18-pentene-24-acid (9), and cericerene-15,24-diol (10). Possibility of the configurational isomers for the structures (8)and (9) at the position C-24 and C-25 are still remained to be elucidated. Bridged hydrocarbon (16) which was obtained by acid treatment of tosylate of cericerol-I (1) indicated the crown shape (A) for (1).
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野原 稔弘, 富松 利明, 徳渕 信能, 八木 晟, 西岡 五夫, 宮原 一元
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セッションID: 12
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Compound I-XVI were isolated from the water-extractive of Cinnamomi Cortex (Cinnamomum cassia Blume), which exhibits anti-complement activity. Among of them, the structures of I-VIII, XI and XII were clarified on the basis of chemical and spectral evidences. I and II were identified respectively as Cinnzeylanine and Cinnzeylanol, which are unique diterpenoides being highly oxygenated, namely the ones of Ryanodine type. III and IV were proved to be dehydrated compounds resp. of I and II. V and XI were evidenced to be 19-hydroxylated compounds correponding to IV and II, resp. Furthermore, VI and XII were decided to be 19-0-monoglucosides resp. of V and XI. The structure of VII was substantiated by X-ray crystallographic analysis. VII and VIII include eight-membered ring carring two ketone functions in each molecule and seem probably to be derived from XI and II, resp., via glycol fission between C-7 and C-8 in plant.
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原田 宣之, 宇田 尚
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The absolute stereochemistries of clerodane diterpenes, clerodin (3), caryoptin (14), and 3-epicaryoptin (15) previously determined by X-ray and related chemical studies have been reversed on the basis of the exciton chirality circular dichroism and molecular rotation difference data. The 3-epicaryoptin derivative bis(p-chlorobenzoate) (22) previously assigned is antipodal to the model compound of 5α-cholestane-3β,4α,6α-triol 3,6-bis(p-chlorobenzoate) (29) in principal chiral centers. However, comparison of the CD exciton coupling Cotton effects of dibenzoate 22, λ_<ext> 247.5 nm, Δε+17.8/230 nm, Δε-9.2 and 29, λ_<ext>246.2 nm, Δε+27.0/ 231.0 nm, Δε-13.8, has led to the conclusion that the absolute configuration of 3-epicaryoptin should be revised and expressed in the enantiomeric form of 15. The same is true in the case of caryoptin 14. Comparison of the molecular rotation difference data, Δ[φ]_D, of a series of clerodin, caryoptin, 3-epicaryoptin, and clerodendrin A (9) derivatives has confirmed the above assignment, indicating that the absolute configuration of clerodin also should be revised and expressed in the enantiomeric form of 3.
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小嶋 康広, 加藤 夏樹
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セッションID: 14
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Diterpenes which have a neo-clerodane skeleton such as clerodin, clerodendrin A, and caryoptin showed the absolute antifeeding activity for the larvae of insects, and it had been showed that the perhydrofuro[2,3-b]furan ring in their structure was the active center of the activity. In order to elucidate the structure-activity relationship of the absolute antifeeding substances, a clerodin homologue 4 was synthesized via 18 steps using gentisic acid as a starting material. We selected the epoxide derivative 8 as a key intermediate for the synthesis of 4, since the derivation of the oxirane ring to the perhydrofuro[2,3-b]furan ring had been already established by the method which led to the formation of a furan-alcohol derivative by Li di(3-furyl)cuprate. The hemiacetal acetate of 4 was hydrolyzed on silica gel (Kieselgel 60 pF_<254>), and, moreover, 4 gave a ring-opening product, tri-MeOH adduct 28, by the reaction with methanol in a catalytic amount of p-toluenesulfonic acid. These behaviors in 4 agreed with those of the perhydrofuro[2,3-b]furan rings in 1 and 2. It was suggested that C-8 and/or C-9 methyl groups in neo-clerodane diterpenes would considerably contribute to the stability of the perhydrofuro[2,3-b]furan ring.
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和田 弘次郎, 今井 哲弥, 柴田 和憲
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Many researchers focused their attention to the microbial productions of biological active compounds and their analogues from artificial substrates. This paper will report the microbial productions of gibberellins and related compounds from artificial substrates by G. fujikuroi. At first, the substrate specificity of the enzymes operative in the gibberellin biosynthesis was examined and kaurene analogues, (1), (4), (5) and (6) were found to be converted to gibberellin-like compounds by mycelium suspension of G. fujikuroi. Two kaurene analogues, (1)(200 mg) and (4)(500 mg) were then converted to GA-like compounds in the mycelium suspension, in which endogenous biosynthesis of gibberellins was blocked by CCC. The acidic metabolites from (1) were p-bromophenacylated and separated by PTLC and LC. The purified phenacyl esters were dephenacylated and methylated to afford methyl esters of GA-like compounds, A-I and A-II. The alcohol(4) was similarly converted to six GA-like compounds, B-I to B-V and a kaurenoid, B-VI. The acid(7)(600 mg) gave three GA-like compounds, C-I, II, andIII, in the mycelium suspension of G. fujikuroi containing 1-n-decylimidazole. Microbial production of gibberellin-like compounds is now in progress in large scale for tests of their biological activities.
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高野 誠一, 笠原 千義, 小笠原 国郎
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Results of a chiral approach to the gibbane frameworks are presented. Cyclization of the meso triketone(10), obtained through Michael reaction of 2-propargyl-1,3-indandione(14) with methyl vinyl ketone, using L-proline as chiral catalyst gave the chiral enone(8) via the chiral ketol(17). The enone(8) afforded the following gibbane frameworks, 24 by the ene reaction, and 20, 21 and 22 by acid catalyzed aldol type condensation via the acetyl intermediate (19). Similarly, the chiral gibbane frameworks, and 26, 27, and 29, were obtained from the allyl analogue(11) of 10. The propargyl enone(8) was transformed into the gibberic acid framework via the monoketal(36) and the ketenedithioacetal(38) intermediates.
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林 雄二, 松本 武, 西沢 麦夫, 兵野 敏明, 西川 直見, 植村 元一, 戸上 昌紀, 目 武雄
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発行日: 1979/09/20
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Nagilactone F (1), one of the simplest member of the biologically active nor-diterpenoid dilactones of Podocarpus nagi, was first synthesized from (+)-[4S]-podocarpic acid (2). Ozonolysis of a 14-isopropyl-enone 10, derived from (+)-podocarpic acid in several steps, gave a keto-acid 12. The acid 12 was transformed into epimeric (at C-14) enolides, 22 and 23, via reductive lactonization and subsequent dehydrogenation. The two enolides gave the same diene-acid 24 on treatment with KOtBu in DMSO. Stereospecific lactonization of 24 to 14α-isopropyl-8:9-enolide 25 was achieved photochemically under irradiation in ethanol solution. On dehydrogenation with DDQ/BF_3:ether in refluxing dioxane, 25 gave a dienolide 27, which equipped with suitable functional groups and stereochemistry on the ring C necessary for nagilactone F. The dienolide ester 27 was hydrolyzed with conc. H_2SO_4 to form a dienolide acid 28, which was successfully changed to nagilactone F by Pb(OAc)_4 oxidation. Reductive degradation of nagilactone F to the synthetic intermediates, 28, 25 and 24, was also done, starting from nagilactone E, a typical natural dilactone of P. nagi.
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北川 勲, 渋谷 博孝, 藤岡 弘道, 梶原 彰治, 山本 佳男, 高木 昭, 鈴木 賢治, 堀 学
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セッションID: 18
発行日: 1979/09/20
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In the synthetic studies on biologically active taxane-type diterpenes, which possess a characteristic tricarbocyclic skeleton comprising 6-,8-, and 6-membered ring systems, we have first attempted the building-up of the optically active basic skeleton, taxa-4(16),11-diene(2) and its enantiomer(ent-2), according to the anti-synthetic route shown in Fig.1. I. Synthesis of 1,1,2-Trimethylcyclopentane Deriv. In order to prepare the starting compounds for synthesis of segment(A), four 1,1,2-trimethylcyclopentane deriv.(8,10,16,18) have been synthesized from d-camphor(3). II. Ring Enlargement of 1,1,2-Trimethylcyclopentane Deriv. Treatment of a vinyl deriv.(8) with 2,4,4,6-tetrabromocyclohexadienone(TBCO) afforded a desired ring-enlarged product(19), while the TBCO treatment of another vinyl deriv.(16) gave only two 5-membered ring compounds(21,22). In the case of an allyl alcohol (18), the BF_3-etherate treatment brought about the formation of two ring-enlarged products(25,26). Among three ring-enlarged products, 19 was considered to be the most favorable key compound for the synthesis of ent-2. III. Synthesis of ent-Taxa-4(16),11-diene(ent-2) A dithiane deriv.(29) was prepared by reaction of m-dithiane with an epoxide(28), which was derived from 19 via 27. 29 was then converted to a C_<12> compound(32, segment(A)) through 30 and 31. A iodomethyl deriv.(34), prepared from 32 via 33, was then coupled with 1,5-dimethoxy-1,4-cyclohexadiene to furnish a C_<18> compound (35). Derivation of 35 leading to ent-2 through 36 is under study and is discussed.
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野崎 浩, 厚見 和則, 片岡 尚義, 松尾 昭彦, 中山 充, 林 修一
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発行日: 1979/09/20
公開日: 2017/08/18
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In the course of our investigation on terpene constituents of the liverworts, several kinds of enantiomeric sesquiterpenoids consisted of novel carbon skeletons have been isolated. From methanol extracts of the leafy liverworts, P. semidecurrens and P. ovalifolia, belonging to the genus Plagiochila of the Junger-maniales, six new ent-2,3-seco-alloaromadendrane type sesquiterpenoids were isolated by means of combination of column and preparative thin layer chromatography. The structures and absolute configurations of these compounds were, respectively, determined as (+)-ovalifoliene(4), (+)-acetoxy-ovalifoliene(5), (-)-hanegokedial(6), (+)-ovalifilienalone(7), (+)-ovalifolienal(8) and (+)-hanegoketrial(9) based on the chemical and spectral evidence and X-ray analysis. The Unique metabolites, that is, the enantiomeric sesquiterpenoids may be biosynthesized from ent-alloaromadendrane skeleton via oxidative cleavage of the C_2-C_3 bond and followed by formation of cyclic hemiacetal. The main constituents,2, 4 and 8, inhibited the growth of roots of rice at concentration of 50 ppm and 7 did at 100 ppm.
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鈴木 稔, 黒沢 悦郎
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発行日: 1979/09/20
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In connection with our continuing studies of the constituents of the red algae of the genus Laurencia (Rhodomelaceae), a number of halo-chamigrene derivatives were isolated from the Japanese species of Laurencia. We describe herein the structures of several halo-chamigrene derivatives. Halogenated sesquiterpenes, 1,2,3,4,5 and 6, were isolated from L. glandulifera, the structures of which were determined on the basis of the chemical and spectroscopic evidence. The absolute configuration of 1 was established by X-ray crystallographic analysis. The absolute configurations of other compounds, 2,3,5 and 6, were confirmed by the spectral data and the chemical correlation with 1. Furthermore, the structure and the absolute configuration of spirolaurenone (14), possessing a spiro[4.5]decane skeleton, which was isolated from the same alga, were confirmed by the chemical correlation with glanduliferol (2). Halo-chamigrene derivatives, 16 and 17a,were isolated from L. majuscula together with a minor component,21. The structures of these compounds were determined by the chemical and spectral methods. The absolute configuration of 16 was established by X-ray analysis of the acetate (20) of 16. Several known halogenated chamigrene derivatives were also isolated from L. nipponica together with seco-chamigrenes.
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川端 潤, 田原 哲士, 水谷 純也, 古崎 昭雄, 羽柴 宣宏, 松本 毅
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発行日: 1979/09/20
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A novel sesquiterpene lactone was isolated from Chloranthus japonicus Sieb. (Japanese name: Hitori-shizuka) and named shizukanolide (1). The structure of 1 was elucidated by physicochemical properties and X-ray diffraction analysis. The absolute configuration of shizukanolide was determined by chemical correlation with lindenene (4). Chloranthalactone A (2), the dehydro-compound of 1, was also isolated from C. japonicus. The stereochemical structure of 2 was established by correlation between the dihydro-compound of 1 and the tetrahydro-compound of 2. Furthermore, glechomanolid (3) was found in the same source. Chloranthalactone A was ascertained to have a remarkable antifungal activity against fungi of the genus Mucor and Rhizopus.
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小林 正紀, 古山 種俊, 小倉 協三, 瀬戸 秀一
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発行日: 1979/09/20
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The stereospecificity of farnesyl pyrophosphate synthetase was applied to the synthesis and determination of the chiral structure of faranal, an insect trail pheromone. In the presence of the enzyme, E-(12) and Z isomer (15) of 3-methylpent-3-enyl pyrophosphate reacted stereospecifically with (2E,6Z)-3,7-dimethylnona-2,6-dienyl pyrophosphate (34) to give (4S)-(2E,6E,10Z)-3,4,7,11-tetra-methyltrideca-2,6,10-trienyl pyrophosphate (21) and its R isomer(22), respectively. Each of these two enantiomers was also synthesized enzymatically from (Z)-methylpent-2-enyl pyrophosphate (4), isopentenyl pyrophosphate (2), and 12 or 15. Treatment of 21 (or 22) with alkaline phosphatase afforded the free alcohol 41 (or 43), which was then oxidized to the corresponding aldehyde. Reduction of the double bond at C-2 of the aldehydes derived from 12 and 15 was attempted to obtain 4S-faranals (3S,4S+3R,4S) and 4R-faranals (3R,4R+3S,4R), respectively.
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稲山 誠一, 大坂 哲司, シン A. K., 川又 健, 広瀬 忠明, 柴田 徹一, 飯高 洋一
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A novel cyclization-skeletal rearrangement a eudesmanolide, 3-deoxy-4β,5αH-hexahydro-l-α-santonin (1) to an ethanoadamanone, (-)-2,5,9-trimethyltetracyclo[6.3.1.0^<2,6>.0^<5,9>]dodecan-11-one (2) was found in a most unusual reaction of 1 with. hot phosphoryl chloride. Two new tricyclic ketones as the possible intermediates were isolated in the aforementioned reaction. The structure, conformation and absolute configuration of the crystalline ketone was determined mainly on the basis of the X-ray crystallograpic analysis and CD/ORD spectrometry. The structure thus revealed is (+)-1β,3α,6αH,4α,7β,11-trimethyltricyclo[5.4.1^<3,6>.0^<1,7>]dodec-10-en-5-one (3). The structure of the other oily ketone, (+)-4αH,3α,7β,11-trimetyltricyclo[5.4.1^<1,4>.0^<1,7>]dodec-10-en-2-one (4) was deduced from the absolute structure of its crystalline 10α,11α-epoxide (5), which was also established by the same methods as described above. Tricycloeudesmenones (3 and 4) can be regarded as a pair of ring analogs of the cyclopentanone (C) situated on the cyclohexane (B) of the same non-steroid type cis-fused octalin (A/B). A possible reaction pathway for 3 and 4 formed by cyclization from santanolide (1) was proposed. The proposed skeletal rearrangement pathway to ethanoadamantanone (2), starting from the tetracyclic ketone (B) derived from 3 via a tricyclic intermediate (A), was performed through a hypothetical pathway involving intermediates (C and D) by the use of a computer technique for the bond migration by 1,2-shift.
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阿知波 一雄
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Chiral pyrrolidinephosphine-rhodium complexes proved to be very useful for the syntheses of chiral compounds. These asymmetric hydrogenations indicated that α-acetamido-olefins, β,γ-unsaturated acid and α-keto-esters are the most suitable substrates for the asymmetric hydrogenations catalyzed by chiral pyrrolidinephosphine-rhodium complexes to gain the high optical yields. I wish to describe here the another application of this new method to the synthesis of chiral natural terpenoids. For the syntheses of chiral (R)-3,7-dimethyloctanoic acid (R-10) and (R,R)-3,7,11-trimethyldodecanoic acid (R,R-12), two new routes were examined. Synthesis of 11 as a chiral isoprene synthon and it's uses for the syntheses chiral terpenoids gave optically pure R-10 and R,R-12. Further applications of this chiral C_5 unit as a chiral isoprene synthon to the syntheses of chiral natural phytol, vitamins E and K will be also discussed.
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白浜 晴久, 早野 清治, 金元 祥郎, 三角 俊二郎, 大塚 俊一, 羽柴 宣宏, 古崎 昭雄, 松本 毅, 村田 靜昭, 野依 良治
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発行日: 1979/09/20
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Bicyclohumulenone (4), which has recently been isolated from a liverwort, has a stereostructure supposedly derived in vivo from the CC conformer of humulene. On the other hand the marine sesquiterpene, africanol (18) is considered to be biosynthesized from the CT conformer of humulene. Treatment of 9,10-epoxyhumulene (1) with BF_3・OEt_2/Ac_2O/-50°→-20°/1 hr afforded a bicyclohumulerir derivative (2-CC) in 70% yield, through a biogenetic like CC transition state. The product 2-CC was then successfully converted to 4 through 7 steps (2-CC→5→6→7→8→9→10→4) in 41% overall yield. On the contrary cyclization by means of Me_3SiOSO_2CF_3/toluene/-20°→-10°/6 hr led to the formation of tricyclic compounds, 19 and 20, in 80% yield through a CT transition state. Δ^<3,4>-Africene (24), one of the possible biogenetic and chemical synthetic precursors of africanol, was obtained from 20 through 2 steps (20→22→24) in 86% overall yield.
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宮下 正昭, 八浪 哲二, 吉越 昭
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セッションID: 26
発行日: 1979/09/20
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(+)-Nootkatone (1), an eremophilanoid isolated first from the heartwood of Alaska yellow cedar (Chamaecyparis nootkatensis), has been recognized as the key flavor constituent of grapefruit. An highly efficient and stereoselective synthesis of (+)-(1) has been accomplished starting with (+)-nopinone (2) as described below. Although the Michael reaction of silyl enol ether (3) and 3-penten-2-one gave only undesired dione (4) which was culminated in the synthesis of (+)-4-epinootkatone (7), the conjugate addition of methallyltrimethylsilane (11b) to trans-3-ethylidenenopinone (I), which was obtained from (2) on the cross condensation with acetaldehyde followed by acid treatment, afforded an adduct (15a) as the predominant product with the desired stereochemistry. Dione (14), obtained from the adduct on methylation followed by ozonization, afforded nootkatone hydrochloride (17) on treatment with hydrogen chloride. Regioselective dehydrochlorination of the hydrochloride yielded (1). An alternative route in which allyltrimethylsilane (11a) was used has also been studied.
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木村 章彦, 磯江 幸彦
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Warburganal, a potent antifeedant against the army worms S.exempta and S.littoralis was synthesized stsrting from decalone derivatives(1) or (2). Introduction of C-1 unit at C8 of decalone derivative was achieved by the reaction of tosylhydrazone 4 with n-Butyllithium followed by trapping of vinyl anion with DMF. Hydroxy group was introduced at C9 by the treatment of diacetate (6) with selenium dioxide. Triol was successfully oxidized to warburganal by the modified Corey-Kim reaction, in which the counter ion (Cl^-) was replaced by tetrafluoro borate ion. Other synthetic routes to warburganal are also discussed.
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中田 忠, 秋田 弘幸, 大石 武, 内藤 隆信
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発行日: 1979/09/20
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Warburganal (1), isolated from the bark of Warburgia (Canellaceae)(W. stuhlmannii and W. ugandensis), is an extremely effective antifeedant against the African army worms. In addition, it exhibits a number of other activities such as antibiotics, molluscicidal and cytotoxicity (KB test, 0.01μg/ml). We have studied the total syntheses of (+)-warburganal and related compounds. 1) Syntheses of isodrimenin (9) and confertifolin (10) 1-A) (+)-Isodrimenin (9) and (+)-confertifolin (10) have already been synthesized from dehydroabietic acid (6) by the ozonolysis of its phenolic derivatives in our laboratory. 1-B) A large-scale preparation of (+)-(9) and (+)-(10) from β-Ionone (11) has been developed. 2) Synthesis of (+)-warburganal (1) (+)-Isodrimenin (9) was converted into the diol (39) via the triol (31) in eight steps. Moffatt oxidation of 39 gave the α-hydroxy aldehyde (43) in 73% yield, which was hydrolyzed to give (+)-warburganal (1). 3) Synthesis of (+)-cinnamosmolide (5) 4) Synthesis of (+)-cinnamodial (2) (+)-Cinnamosmolide (5) and (+)-cinnamodial (2) were synthesized from the common intermediate (36).
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入江 寛, 水野 行雄, 片川 純一, 伏見 環, 多賀 徹, 大崎 健次
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発行日: 1979/09/20
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Double Michael reaction of 4-methylene-3-methyl-cyclohex-2-enone as a Michael acceptor and dimethyl 3-oxoglutarate as a Michael doner in the presence of potassium fluoride in dimethyl sulphoxide gave 6,8-di(methoxycarbonyl)-2,7-dioxo-9-methyl-cis-decalin stereoselectively. 4-Methylene-3,5-dimethyl-cyclohex-2-enone gave two 6,8-di(methoxycarbonyl)-4,9-dimethyl-2,7-dioxo-cisdecalins in the same manner, the structures of which were confirmed by X-ray crystallographic analysis. Application of the procedure on 4-methylene-2,3-dimethyl-cyclo-hex-2-enone gave 6,8-di(methoxycarbonyl)-1,9-dimethy1-2,7-dioxo-cis-decalin, which was transformed into the key-compound for synthesis of furanoeremophilane, eremophilenolide, and fukinone, providing a formal synthesis of these sesquiterpenes. Next, the synthesis of (±)-occidentalol was completed in a stereoselective manner, starting from one of two stereoisomeric 4,9-dimethyl-cis-decalin mentioned above.
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村井 章夫, 佐藤 慎吾, 正宗 直
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Considerable attention has been paid to the synthesis of natural spirovetivanes, which involve various sesquiterpenes with different stereochemistry; that is, β-vetivone (1), hinesol (2), agarospirol (3), solavetivone (4), oxylubimin (7), and others differ each other in stereochemistry at C-4, C-5, and C-7 of the spirovetivane skeleton. We describe herein a new and efficient process leading to the synthesis of most of the sesquiterpenes. The process is summarized in Scheme 1, which consists of two major steps; (i) the Diels-Alder reaction (Schemes 3 and 6) of substituted dihydroanisoles(Schemes 2 and 6) and methyl acrylate or its equivalents followed by transformation for the second key reaction, and (ii) acid cleavage of the resulting bicyclooctanes and subsequent π-cyclization, giving the spirovetivanes practically in a single step (Scheme 4). The relevant relative stereochemistry between C-4 and C-5 and between C-7 and C-5 could be controlled in the first and second steps, respectively. Examination of reagents and reaction conditions resulted in stereoselective and short-step syntheses of β-vetivone (1), hinesol (2), β-vetispirene, and solavetivone (4).
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栗原 利夫, 児玉 三明, 佐々木 仁子, 伊東 〓
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Synthesis of α- and β-barbatenes (1 and 2) and gymnomitrol 3, novel tricyclic sesquiterpenes isolated from the liverworts, was achieved utilizing cycloaddition reaction of a dihydrobenzene and a cyclopentene derivative and skeletal rearrangement of the resulted bicyclo[2.2.2]octane derivative to the bicyclo[3.2.1]octane ring system. The Diels-Alder adduct 9 obtained by heating 7 and 8 in toluene was converted after demethylation to the sulfide 23 via dimesylate 22. Desulfurization of 23 yielded the common intermediate 26 for both barbatenes and gymnomitrol. Reaction of 26 with HI followed by SiO_2 chromatography afforded the rearranged ketone 35. Methylation and subsequent dehydration gave α- and β-barbatenes. For the synthesis of gymnomitrol, on the other hand, the olefine 26 was oxidized to the epoxide 37, which rearranged smoothly to the ketoalcohol 38 with alumina. Oxidation of 38 afforded the diketone 39, which is identical with the compound derived from natural gymnomitrol. Since the diketone 39, synthesized in completely different strategy, has been converted to gymnomitrol by Coates et al., the present study constitutes formally the second synthesis of natural alcohol.
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上原 忠夫, 大沼 俊雄, 鈴木 赳, 加藤 忠弘, 吉田 利男, 高橋 勝宏
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発行日: 1979/09/20
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From a higher boiling fraction (Bp>100℃/8 Torr) of peppermint oil (Mentha piperia L.) was isolated a white crystalline (mp 59-61℃, 300 mg from 80 g of the fraction) having a molecular formula of C_<15>H_<24>S. The structure of the crystalline was unequivocally determined by X-ray crystallographic analysis and we named it mintsulfide (1)(abbreviated as MS). Ultraviolet irradiation (Pyrex filter) of (-)-germacrene D (2)(abbreviated as GD), one of the major components of the oil, in the presence of sulfur powder afforded the mintsulfide (1), thus demonstrating the absolute configuration of MS. The mintsulfide was converted into the isomer (4). Both 1 and 4 were oxidized to give the products (5〜10), which showed the chemical shifts in the NMR spectra as summarized in table 1 and 2. Table 3 indicates the results of photochemical conversion of GD (2), giving MS (1) and/or β-bourbonene (3) under the various conditions. The evidence in table 3 suggests that activated sulfur (sulfur atom ?) is generated first under the Pyrex filtered irradiation. The activated sulfur reacts with GD, leading the formation of MS (1). This novel photoreaction is substrate specific since presence of caryophyllene (12) or β-bourbonene (3) affects no influence. The preliminary experiments revealed that myrcene (13) and tenmembered diene (14) also react with the photo-activated sulfur.
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山田 泰司, 三條 秀直, 中村 信太郎, 井口 和男
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Thallium(III) salt-induced cyclizations of geraniol (1) and its related derivatives [geranyl acetate (4), ortho-geranylphenol (6) and citral (11)] were investigated. In order to clarify an effect of stereochemistry of double bond on the reaction, the cyclizations of nerol (13), which is a geometrical isomer of geraniol, and ortho-nerylphenol (17) were also examined. Plausible mechanisms for the formation of the products were proposed for each reaction. These cyclization reactions were remarkably characteristic as compared with the cyclization of polyenes induced by acid or other metal salts. It was demonstrated that the present cyclizations were strikingly dependent upon functional groups and the stereo-chemistry of double bond in diene. These cyclizations are noteworthy in connection with the biosynthesis of cyclic monoterpenes. For example, the products (2a) and (2b) obtained by the cyclization of geraniol have already the same carbon skeleton as iridoid. Application of the present cyclization to the synthesis of (+)-iridomyrmecin (24) was also described.
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菅 隆幸, 平田 敏文, 丹下 敬治
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No or negligible incorporation of leucine, isoleucine, and valine into monoterpenoids in higher plants has been reported. We tested the incorporation of radioisotopically labeled leucine, valine, and alanine into linalool in Cinnamomum Camphora and into geraniol and citronellol in Pelargonium roseum. The amino acids were undoubtedly incorporated into these monoterpenoids. In the incorporations, more than 70% of the total radioactivities resided in the DMAPP-derived moiety after uptake of leucine and valine, whereas less than 40% in the DMAPP-derived moiety after uptake of alanine and mevalonic acid. We also examined the effect of inhibition of the IPP isomerase activity on the distribution of radioactivity after uptake of the amino acids. The predominant location of radioactivity in the DMAPP-derived portion was observed when leucine-4,5-^3H_2 had been fed to Cinnamomum Camphora in the presence of iodoacetamide, which is known as the inhibitor. Thus, it was found that leucine and valine may participate in the biosynthesis of monoterpenoids by their conversion to the DMAPP-derived portion of the monoterpenoids through any pathway other than the mevalonoid pathway. On the contrary, alanine is first metabolized to acetyl-CoA, which is converted preferentially to the IPP-derived portion of the monoterpenoids via mevalonic acid.
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佐々木 満, 森 謙治
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Lineatin is an attractant compound isolated from frass produced by female beetle of Trypodendron lineatum(Olivier) boring in Douglas fir. (±)-3,3,7-Trimethyl-2,9-dioxatricyclo[4.2.1.0^<4,7>] nonane 1 and (±)-3,3,7-trimethyl-2,9-dioxatricyclo[3.3.1.0^<4,7>] nonane 2 were synthesized to confirm one or the other of the proposed structures. The key step in the present synthesis was the (2+2) photocycloaddition of vinyl acetate to a cyclopentenone 4. The latter 2 was shown to be (±)-lineatin, the ambrosia beetle pheromone. In order to determine the absolute stereochemistry of the natural pheromone, the both enantiomers of lineatin were also synthesized by another stereo-controlled method. From the CD spectra of both enantiomers of the resolved key intermediate 20 and the ORD of the final product, the absolute configuration of (+)-lineatin was tentatively assigned to be 1S, 4R, 5S, 7S.
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西野 親生, 高柳 久男
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Our discovery of the monoterpenoid sex pheromone mimic, (+)-trans-verbenyl acetate (1'), of the American cockroach (Periplaneta americana L.) stimulated us into elucidating chemical factors important for sex pheromonal activity of this compound. For the purpose, 1' and related analogs (about 100 compounds) having the 6,6-dimethylbicyclo[3.1.1]heptane skeleton were synthesized. In the behavioral assay with the males of the cockroach, the roaches showed the typical sexual display to several compounds (5', 16', 22', 38, 39 and 41'). On the basis of the assay results, the moiety, -O-C=O-R (R=CH_3 or C_2H_5) with α-orientation was revealed to be an important factor when the moiety is at the C-2 of the skeleton. Another key factor may be the methyl group at the C-4. From the stereo-structures of the active compounds and their structurally resemble analogs, a possible shape of the sex pheromone receptor could be seen, although it is incomplete. The EAG responses were recorded using the synthesized compounds. The active compounds were discriminated from inactive ones showing larger M/F ratios in the EAG analysis. This implies that the active compounds are concerned with the sex pheromone receptors.
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高杉 光雄, 長尾 繁光, L. Munoz, 石川 真一, 正宗 直, 白田 昭, 高橋 幸吉
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Phytoalexins are antimicrobial compounds produced newly by plants in response to microbial infection and their production is believed to be an important disease resistance mechanism in higher plants. We describe herein the isolation and structure alucidation of antifungal metabolites isolated from mulberry (Morus alba Linne) infected with Fusarium solani f. sp. mori. and qualified as phytoalexins. The diseased cortex and phloem tissues of shoots, xylem tissues of shoots, and leaves were extracted with acetone. The respective extracts were fractionated sequentially by column and preparative thin-layer chromatography over silica gel, polyamide, and/or Sephadex LH-20, resulting in isolation of twelve new metabolites [moracins A〜L (1〜12)], oxyresveratrol (13) and two new metabolites [4'-prenyloxyresveratrol and moracin M (14 and 15)], and one new unidentified metabolite (16) from the afore-mentioned diseased parts of mulberry, respectively. Healthy epidermis of the plant was also examined in the same manner, and three new antifungal compounds (19〜21) were isolated along with known compounds, kuwanon C (17) and morusin (18). The structure of all these new compounds, except 16, was determined as shown in the formulas on the basis of the spectral and chemical data.
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久保 正良, 高橋 邦夫, 井上 隆夫, 永井 正博
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Previously we reported the structure elucidation of aceroside I (4)(a glucoside of acerogenin A (3)), epirhododendrin (2)(a glucoside of (+)-rhododendrol (1)), and acerogenin B (5) isolated from the bark of Acer nikoense Maxim. Acerogenin A (3) is reportedly the first example of a diphenyl ether type of diarylheptanoids. Further investigation on the ingredients of the plant bark afforded several new glycosides, some of which are now designated as aceroside III (6), IV (7), V (8), and apiosylepirhododendrin (9). Firstly the assignment of chemical shifts of ^<13>C-NMR spectra of 3 and 2 was extensively studied in order to speed up the structure elucidation of their analogous substances. The results are summarized in Table I. Aceroside IV (7) was presumed to be 2-β-D-glucopyranoside of acerogenin C (15)(11-keto derivative of 3) on the basis of its NMR spectrum, which was confirmed by its chemical data. Aceroside V (8) seemed to be 9-hydroxyaceroside IV. On hydrolysis aceroside III (6) and apiosylepirhododendrin (9) afforded acerogenin A (3) and (+)-rhododendrol (1) as aglycone respectively, along with both glucose and apiose as sugar moiety. Partial hydrolysis of aceroside III (6) gave a monoglucoside (19) of 3. On the basis of combination of the chemical shifts in ^<13>C-NMR, PRFT-NMR, and the above chemical evidences, those glycosides (6,9) were elucidated to be β-D-apiofuranosyl (1→6)-β-D-glucopyranosides of acerogenin A (3) and (+)-rhododendrol (1) respectively. Chemical evidences of linkage-sites between apiose, glucose, and aglycones of 6 and 9 were finally obtained from methanolysis of the permethylated apiosylglucosides followed by identification of methylated sugars and aglycones on GLC and/or TLC.
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石井 永, 石川 勉, 村上 佳子, 東條 俊明
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セッションID: 39
発行日: 1979/09/20
公開日: 2017/08/18
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Three new monomeric phenylpropanoids having an isoprene unit in their molecule were isolated from Xanthoxylum (Fagara) plants (Rutaceae) and their structures were well established. Cuspidiol (1): Colourless needles, C_<14>H_<20>O_3, mp 65-67°, was obtained from the bark of X. cuspidatum as a main component. The inspection of spectral data of it and its some derivatives suggested the structure of cuspidiol as the formula (1). Total synthesis of cuspidiol was also performed via condensation of methyl 4-bromotiglate (14) having an E-configuration about the double bond with dihydro-p-coumarylalcohol(7). Boninenal (16) and Methyl Boninenalate (17): These two phenylpropanoids were isolated from X. inerme (Fagara boninensis) as colourless prisms, C_<14>H_<16>O_3, mp 95-97.5° and colourless prisms, C_<15>H_<16>O_4, mp 180° (softened at 107°). Although the isolated amounts of them were so minute that we could measured several spectral data, but taking into account that these substances could be structurally related with cuspidiol, their structures were supposed to be as the formulae (16) and (17). The validity of this assumption was shown by total syntheses of them.
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田口 平八郎, 池谷 幸信, 吉岡 一郎
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セッションID: 40
発行日: 1979/09/20
公開日: 2017/08/18
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Three new dibenzocyclooctadiene lignans, epigomisin O(1), gomisin E(7) and angeloylgomisin Q(26), were isolated from the fruits of Schizandra chinensis BAILL.(Schizandraceae), which are used as an antitussive and a tonic under the names of "Hoku-gomisi" in Japan and "Wu-wei-zi" in China. 1) The structure of epigomisin O(1) was elucidated by correlation with known lignans, gomisins O(2) and N(4). 2) Oxidation of 4 with KMnO_4 in a mixture of 2% NaOH and pyridine gave compounds 3 and 5. Further oxidation of 3 with KMnO_4 gave 5. Reduction of 5 with NaBH_4 afforded deangeloylgomisin B(6). The structure of gomisin E(7) was elucidated by the same reaction to correlate with a known lignan, gomisin D(8). 3) The cleavage of the methylenedioxy group on the aromatic ring with Pb(OAc)_4 in dry benzene into diphenol was studied(19-22→19b-22b). The structure of angeloylgomisin Q(26) was elucidated by the use of the above reaction to correlate with 6.
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山村 庄亮, 丹羽 正武, 寺田 幸正, 西山 敦子, 野々山 幹枝, 井口 正信
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セッションID: 41
発行日: 1979/09/20
公開日: 2017/08/18
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Previously, we isolated the two novel neolignans, asatone (1) and iso-asatone (2), from Asarum taitonense H. growing in Taiwan. In particular, asatone shows antitumor activity toward P388 and Sarcoma 180. We further examined asatone type neolignans in the Japanese species and could isolate seven novel ones (3-9) from Heterotropa takaoi M., and the structures of these neolignans were also determined on the basis of their spectral data coupled with some chemical evidences. In connection with asatone and related neolignans, anodic oxidation of six phenolic compounds has been carried out.
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富岡 清, 石黒 恒男, 水口 英道, 古賀 憲司
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セッションID: 42
発行日: 1979/09/20
公開日: 2017/08/18
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A new mothodology for the chiral synthesis of natural products was developed by the novel approach to use optically active butyrolactone derivative (1), which is easily available from L-glutamic acid, as a chiral synthon. This procedure is cnostituted from the two key steps, the first is the creation of new chiral centers (2) on 1 and the second is the removal of the original chiral center (3) derived from 1. Applying this new mwthodology to the chiral synthesis of pharmacologically active lignan lactones, the key intermediate (S)-11, as well as its antipode (R)-11 were successufully synthesized. (S)- and (R)-11 were shown to be the key intermediates by the conversion into several optically active lignan lactones. The chiral butenolide (18) was also shown to be highly usefull for the synthesis of the chiral lignan lactones, giving the very high selectivity. In addition to the above fundamental methodology, the stereo-selective synthesis of the antitumor burseran (28) and the determination of the stereochemical structure of natural burseran were achived. The novel isomerization reaction of antileukemic steganacin skeleton and the first synthesis of stegane (32), the parent skeleton of steganacin (4), were also achived.
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奥田 拓男, 吉田 隆志, 波多野 力, 新田 博夫
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セッションID: 43
発行日: 1979/09/20
公開日: 2017/08/18
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Geraniin (I) (from Geranium thunbergii and Mallotus japonicus), mallotusinic acid (II) (from M. japonicus) and granatin A (from Punica granatum) were found to be ellagitannins which have dehydro-hexahydroxydiphenoyl (DHHDP) group in their molecules. The CMR signals of these ellagitannins were assigned by comparing them with those of corilagin (IV) for which the CMR signals were assigned by comparisons with those of the derivatives substituted at O-2 or O-4, and also by deuterium-induced differential isotope shifts (DIS). The CMR spectral investigation was then applied to geraniin before and after the equilibration, and also to "phenazine A" which is produced by condensation of geraniin with o-phenylenediamine. The CMR shifts and DIS showed that the equilibration is induced by transformation of a six-membered hemiacetal ring into a five-membered ring. The shielding effect on H-1 in the glucopyranose moiety upon the transformation of "phenazine A" into "phenazine B" indicates that the atropisomerism in the phenylphenazine moiety in "phenazine B" is R, and hence that the absolute configuration at the methine in geraniin is R. The specific rotation of dimethyl hexamethoxydiphenoate produced by methanolysis of nona-O-methylcorilagin (V) indicates that the atropisomerism of hexahydroxydiphenoyl group in geraniin and corilagin is R. The hydrated and equilibrated structure of geraniin is then shown by (Ia)⇄(Ib). Mallotusinic acid and granatin A have analogous hydrated and equilibrated structures. Granatin B was found to be an isomer of geraniin concerning the DHHDP moiety.
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鮫島 正浩, 善本 知孝
原稿種別: 本文
セッションID: 44
発行日: 1979/09/20
公開日: 2017/08/18
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わが国の木材工業においては.伐採時に生する多量の樹皮が.まったく利用きれずに廃棄されている.これらの樹皮の有効利用を考えることは.資源的な立場から,たいへんに有意義なことである.樹皮はその抽出成分量が非常に高いことで知られており,特にタンニン性を有する一群のフェノール化合物においては顕著である。一方,タンニンは古くからなめし剤として利用されてきているが,近年ではフェノール性接着剤原料,あるいはタンパク質との結合性をいかした種々の利用法が考え始められている.また、その徴生物に対する抗菌性や酵素活性の阻害など生理作用も認められている.このようなことから、我々は樹皮利用の基礎として、樹皮タンニンの化学構造、存在量およびその性質について研究を進めている.前報では、スギ内樹皮よりタンニン関連化合物として多量の(+)-catechin (1),(-)-epicatechin(2),dimenic procyanidin B-3(3)すよびB-4(4),きらに3種のtimeric procyanidin異性体を単離し,その構造を同定あるいは推定した,また,さらに重合の進んだhigher oligomeric procyanidin (4量体以上)も内樹皮中に存在することを確認した.今回の報告では,種々の分析法を用いて,スギ内樹皮のhigher oligomeric procyanidinの化学構造の詳細について明らかにした.また,procyanidinの重合度とそのタンニン性について考察を加えた.さらに,日本産針葉樹11種について.その樹皮中に含まれるflavan-3-olおよびproanthocyanidinの化学構造,存在量などを比較した。
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