-
Article type: Cover
Pages
Cover1-
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
-
Article type: Appendix
Pages
App1-
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
-
Article type: Index
Pages
I-IV
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
-
Article type: Index
Pages
V-X
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
-
Eiichi Fujita, Kaoru Fuji, Kiyoshi Bessho, Akihisa Sumi, Shigetake Nak ...
Article type: Article
Session ID: 1
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Three new alkaloids, that is, lythranine, lythranidine, and lythramine, were isolated from Lythrum anceps Makino (Lythraceae). Lythranine, C_<28>H_<37>NO_5, was shown to have a secondary hydroxy-, a secondary acetoxy-, a phenolic hydroxy-, an aromatic methoxy-, and an imino-groups, as well as two aromatic rings, on the basis of the spectral investigation. Lythranine, on alkaline hydrolysis, gave lythranidine, C_<26>H_<35>NO_4. Both of lythranine and lythranidine, on acetylation, afforded a same acetate, which confirmed their same skeleton. Lythranine, on treatment with formalin in methanol, gave lythramine, C_<29>H_<37>NO_5, which was subject to hydrolysis and methylation with diazomethane, then reduced with lithium aluminum hydride to give O,N-dimethyllythranidine(VII). O-Methyllythranidine(VI), on oxidation with permanganate, gave 2,2'-dimethoxydiphenyl-5,5'-dicarboxylic acid characterized as the dimethyl ester IX. The double Hofmann degradations of VII-provided that each of the Hofmann degradation was followed by hydrogenation-yielded a neutral alcohol X, C_<27>H_<38>O_4, which was oxidized with the chromic acid-pyridine complex to a completely symmetric diketone XI, C_<27>H_<34>O_4. Lythranine, on dehydrogenation with Pd-black followed by oxidation with permanganate, yielded dipicolinic acid(XII), which confirmea the presence of a piperidine ring in lythranine. The foregoing data and the additional chemical evidence suggested the formulas I, II, and III for lythranidine, lythranine, and lythramine, respectively.
View full abstract
-
Y. Inubushi, T. Harayama, H. Ishii, B. Yasui, R. Nishino, Y. Nakahara, ...
Article type: Article
Session ID: 2
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Recently, the unique structure of serratinine, including its absolute configuration, has been completely established as shown in the formula (I). On the basis of chemical correlation with serratinine, structures of three new alkaloids which were isolated from lycopodium genus plants growing in Japan; 8-deoxyserratinine (II) from Lycopodium serratum Thunb. var. serratum form. intermedium Nakai (Tohogeshiba), serratine (V) and serratinidine (X) from Lycopodium serratum Thunb. var. serratum form. serratum (Hosobatohogeshiba); and two alkaloids which have been reported in the literatures but whose structures have not been settled; fawcettidine (XXII) and fawcettimine (XXV) from Lycopodium fawcettii Lyloid et Underwood growing in Jamaica; were elucidated. The hypothetical biogenetic relationship among these alkaloids was also suggested.
View full abstract
-
Kunisuke Nishikawa, Mieko Miyamura, Yoshimasa Hirata
Article type: Article
Session ID: 3
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Recentry, it was made clear that some Liparis specias of Orchidaceae family contained each one main alkaloid which has similar Rf value and chemical properties. In addition to these main alkaloids, only one or two minor alkaloids were also extracted from each plant in low yield. Being interested in these facts, we developed the structural studies of these Liparis alkaloids in point of view of plant chemotaxonomy. From these results, it is clear that these main alkaloids have something in common among them: all of them consist of following three components; (1) aminoalcohol (2) carboxylic acid (aromatic) (3) sugar. The plants in investigation are descrived below. (I) Liparis nervosa Lindl. (Kokuran) (II) Liparis Krameri Fr. et Sav. (Zigabachiso) (III) Liparis Kumokiri F. Maekawa (Kumokiriso) (IV) Liparis bicallosa Schltr. (Yukokuran) (V) Liparis hachijonensis Kitamura (Shimasasabaran) (VI) Liparis Makinoana Schlechter (Suzumushiso) (VII) Liparis japonica Maxim. (Seitakasuzumushiso)
View full abstract
-
T. Kametani, K. Fukumoto, H. Yagi, I. Noguchi, T. Kikuchi, F. Satoh
Article type: Article
Session ID: 4
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
It has been appreciated for many years that several isoquinoline alkaloids would occur in Nature by phenolic oxidative coupling reactions of coclaurine or its equivalents as precursors. The exhaustive feeding experiments have been made particularly in the morphine and Amaryllidaceae fields and their biogeneses have already been confirmed, but the biogeneses of some isoquinoline alkaloids, especially, cularine type alkaloids, have not been investigated yet. Therefore, we are currently investigating the possibility of such phenolic oxidative coupling reactions in the syntheses of several isoquinoline alkaloids (whether biogenetically likely or not ) and we wish to report the syntheses of cularine type compounds (XIII and XIV), glaucine (XX) and its methopicrate, glaziovine (XXX) and pronuciferine, and homoaporphines (XLIIIa-b and XLV) by the application of phenolic oxidative coupling reaction of the appropriate precursors. It is noteworthy that this phenolic oxidation supplies the useful and important ways for the total syntheses of many isoquinoline alkaloids and it suggests the possible biogenetical pathways in Nature.
View full abstract
-
S. Uyeo, H. Irie, T. Mizutani, T. Shingu, M. Takada, A. Yoshitake, N. ...
Article type: Article
Session ID: 5
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The racemic modification of lycoramine (I), an alkaloid isolable from Lycoris radiata has been synthesized by two routes. Starting from 2-hydroxy-3-ethoxybenzaldehyde the cyano-ketone (XI) was prepared by the standard method and reduced with lithium aluminum hydride to give the hydroxy-aldehyde (XII). The Wittig reaction with the acetate of (XII) afforded the acrylate (XVI) which was transformed to the tetralone (XIX) in the usual manner. Schmidt reaction on the tetralone (XIX) gave two isomeric lactams (XX and XXI) in a ratio of 3:2. The desired lactam (XXI) was selected by snectral data, N-methylated, deacetylated and oxidized, yielding the keto-lactam (XXIV). This compound was obtained from natural lycoramine through a sequence of reactions, including catalytic hydrogenolysis of the furan ring in the ethyl analog (XXVb) of oxolycoraminone (XXVa) in an alkaline solution. Since the keto-lactam (XXIV) was convertible into (+)-lycoramine by a sequence of reactions including bromination, dehydrobromination, demethylation, methylation, and lithium aluminium hydride reduction, the synthesis of (±)-lycoramine was completed. The key intermediate in the second method involved the 1,3-diketone (7), which was obtained by the Claisen condensation of the keto-ester (6). Monoketalization of the diketone (7) followed by lithium aluminum hydride reduction and hydrolysis of the ketal grouping gave the perhydrobenzopyran (10). Hydrolysis of the methoxyl group and cleavage of the pyran ring with constant boiling hydriodic acid and concomitant recyclization afforded the phenol (11). Through a sequence of 7 steps, the phenol (11) was transformed to the tetralone (18) which was subjected to the Schmidt reaction, giving two isomeric lactams (19 and 20). The desired lactam (20) was N-methylated and treated with lithium aluminum hydride to furnish the end product, (±)-lycoramine (XXXI).
View full abstract
-
W. Nagata, S. Hirai, K. Kawata, T. Okumura
Article type: Article
Session ID: 6
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The total synthesis of ibogamine (1b) epiibogamine (1d) and desethylibogamine (1c) was accomplished by applying a new synthetic method for bridged aziridines as well as isoquinuclidines. This new method consists of the oxidation of δ,ε-unsaturated primary amines such as 4 with lead tetraacetate giving the highly strained bridged aziridines 5 which upon treatment with an acylating agent were cleaved mainly to isoquinuclidine derivatives 8. 1-Azatricyclo[3,2,1,0^<2,7>octane 5a obtained by this new method was cleaved readily with indole acetic anhydride in acetone to give the amorphous 13 which upon hydrolysis with aqueous potassium carbonate in methanol afforded the hydroxy derivative 14. The oppenauer oxidation followed by cyclization with 1,2-equiv. p-toluenesulfonic acid in benzene yielded the tosylate 16 which was then treated with sodium methoxide in boiling methanol to give the methoxy lactam 17. This compound on treatment with lithium aluminum hydride unexpectedly gave the enamine 18 which was hydrogenated on palladium to give the methoxy base 19. Finally, reductive elimination of the 18-methoxy group was accomplished smoothly with lithium aluminum hydride yielding desethylibogamine. Likewise, 21 and 22 were transformed to ibogamine (1b) and epiibogamine (1d) respectively.
View full abstract
-
Y. Ban, M. Akagi, I. Iijima, T. Oishi, Y. Sendo, N. Sakabe
Article type: Article
Session ID: 7
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The total syntheses of dl-aspidospermine (Ia) were reported by Stork et al. in 1963 and by Ban et al. in 1964. The key intermediates of the same plane formulas(II and III) in both syntheses were prepared in independent ways, whose physico-chemical properties were quite different. At first, IIa and IIIa were given by Stork to his compounds, and accordingly IIb and IIIb corresponding to the conformation of IIb were preferred by us to our compounds on taking the above assignment into consideration, although the possibility of IIa to our compound was alternatively deduced based on n.m.r. spectral data. For clarification of this point, trans-decahydroquinolone(VI) was synthesized by the method of Grob and derived to VII, whose n.m.r. spectra were compared with the corresponding compounds including II, XI-A and XI-B. In addition, the fact that the intramolecular hydrogen bonding was observed with XIII-B and not with XIII-A, concludes that our intermediates(II and XI-A) are of A/B trans and the Stork's compound(II) and XI-B are of A/B cis. Subsequently, the fused form of C-ring to A- and B- rings in II and III was carefully investigated, and in conclusion IIc and IIIa were given to our intermediates. From IIIa, there were synthesized dl-aspidospermide and the other diastereoisomer of the natural alkaloid, the structure, of the latter was elucidated by X-ray crystallography to be XXVIII, which is compatible with the above assignment to our intermediates.
View full abstract
-
Hiroyuki Inouye, Takashi Yoshida, Yushin Nakamura, Shusaku Tobita
Article type: Article
Session ID: 8
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Besides swertiamarin, gentiopicroside and sweroside, two new strong bitter glucosides (tentatively named substance A and B) were isolated from Swertia japonica Makino. From its degradation reactions and spectral data, substance A, C_<29>H_<30>O_<13>H_2O, m.p. 229〜230°, was assumed to be the ester of 3,5,3'-trihydroxybiphenyl-2-carboxylic acid and sweroside at the C-2' of the glucose moiety of the latter. Substance B, C_<29>H_<30>O_<14>・H_2O, amorphous powder, is considered to be the corresponding ester of swertiamarin. In order to clarify the absolute configuration of the gentianaceous bitter glucosides, an attempt to convert asperuloside, whose absolute configuration is already established, into dihydrosweroside or its stereoisomer by way of the route shown in scheme 1 was undertaken. At the same time, for the purpose of the determining the absolute configuration of loganin, a glucoside of Menyanthes trifoliata L., an intermediate in scheme 1 was treated to transform into the glucoside via the route shown in scheme 2.
View full abstract
-
T. Kamikawa, K. Inoue, N. Ichikawa, T. Kubota
Article type: Article
Session ID: 9
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
A bitter principle, jasminin, C_<26>H_<38>O_<12>, mp.159-161°[α]_D-244.9°, isolated from the leaves of Jasminum primulinum HEMSL. ("unnan sokei." in Japanese) was proved to be represented by the structure (XIII) or (XIV) on the following evidences. The IR, UV and NMR spectral data, and titration suggested that jasminin was a iridoid glucoside having one lactone, one ethylidene, one hydroxyl and two secondary methyl groups. The relation between iridoid and ethylidene double bond was established as in IV by treatment of (5) with Ac_2O-KHSO_4. Further, alkaline fission of jasminin suggested the environment (VI) for jasminin. The system (VI) can be explained by the fact that acidic treatment of jasminin gave aldehydes (7), (8) and diacetate (9), and that nitric acid oxidation of jasminin gave methyl ester E (11). Derivatives from (5) suggested that the hydroxyl A was primary. The NMR spectral data of aldehyde (12) and diacetate (16) showed that the hydroxyl A was included in CH_3CHCH_2OH system. Hydrolysis of jasminin with NaOMe, followed by acetylation gave triacetate (18). The spectral data of anhydride (19) derived from (18) clarified the 1,5-relationship between the hydroxyl A and the hydroxyl B, and the presence of five-membered ring. From the spectra analysis and biogenetic reason, the oxidation products of (16) and (18) can be expressed in (23, R=H) and (17) respectively.
View full abstract
-
T. Sakan, K. Abe
Article type: Article
Session ID: 10
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The stereospecific synthesis of Verbenalol (I), an aglycone of Verbenaline Which is a Glycoside in Verbena officinalis, is repoprted in this papar.
View full abstract
-
F. Micheel
Article type: Article
Session ID: 11
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
-
N. Katsui, A. Murai, M. Takasugi, K. Imaizumi, T. Masamune, K. Tomiyam ...
Article type: Article
Session ID: 12
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
A new antifungal compound, designated as rishitin, has been isolated from tuber tissues of white potatoes (Solanum tuberlosum and S. demissum) infected by an incompatible race of Phytophthora infestans. Rishitin (I) has biological properties qualified as "phytoalexin," and its (planar) structure and the absolute configuration of C-7 have been established as represented by formula I on the basis of chemical and spectral data. The configurations of the remaining three asymmetric centers, C-2, C-3 and C-4, are also discussed from the NMR spectra of I and its dihydrodibromo derivative (V), and formula IA or IB is tentatively proposed. The partial synthesis of I from santonin (VII) has been attempted (Chart I and II) and a compound having the shale R_f value and IR spectrum as I has been obtained.
View full abstract
-
K. Naya, I. Takagi, M. Hayashi, S. Nakamura, M. Kobayashi
Article type: Article
Session ID: 13
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
New two sesquiterpenes, Fukinolide(1A), C_<22>H_<30>O_6 and S-Fukinolide(1B), C_<21>H_<28>O_6S were isolated from the flower stocus of Petasites japonicus Maxim. and their structures were determined. By alkali hydrolysis, (1A) gave a sesquiterpenoid alcohol, Fukinolidol(4), acetic acid and angelic acid, and (1B) gave the same alcohol(4), acetic acid and cis-β-methylthioacrylic acid. The structure(4) was reduced for Fukinolidol on the basis of chemical reactions and the spectroscopic data. Finally, the absolute configuration of Fukinolidol(4) was established by the X-ray diffraction method.
View full abstract
-
N. Abe, R. Onoda, K. Shirahata, T. Kato, M. C. Woods, Y. Kitahara
Article type: Article
Session ID: 14
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Two new sesquiterpenes, Bakkenolide-A, C_<15>H_<22>O_2, m.p. 80-81°and Bakkenolide-B C_<22>H_<30>O_6, m.p. 101-102°, were isolated from the bud of Petasites japonious subsp. giganteus Kitam (Japanese name, AKITABUKI). Structure (5d), including the absolute configuration, was established for Bakkenolide-A (B-A) on the basis of the chemioal degradations (chart I) and their physical measurements (Fig 1 and 2). One of the main degradations was a oonversion of B-A to C_<11>-dioarboxylic acid (2), structure of which was deduced from NMDR technique. The combination of 2 with the new type of spiro laotone (5a) as a partial structure led to the final structure 5C for B-A. The absolute configuration was determined by the transformation of B-A to the known ketone (14). The comparisons of the physical properties of Bakkenolide-B (B-B) with B-A led to the structure 16 for B-B, which will be discussed near future.
View full abstract
-
Shuichi Hayashi, Nanao Hayashi, Tamon Matsuura
Article type: Article
Session ID: 15
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Two new methyl esters of sesquiterpenoid (isosericenine having a furan ring and sericea lactone having a hydroxy α,β-butenolide) were respectively isolated from fractions b.p. 136-139° and 139-148℃ in 5 mmHg of the essential oil collected in the steam distillation of the leaves. When the leaves of the same plant was extracted with n-hexane and chromatographed on a silica gel column with the deep precaution of keeping the treating temperature below 60℃, the third methyl ester, sericenine (V) of sesquiterpenoid which has the carbon skeleton of germacrane was obtained. Isosericenine, [α]_DO, have molecular formula C_<16>H_<20>O_3(high resolution mass spectrometry) and partial structure of CH_2=CH-C, CH_3-C, CH_2 CH_2-O-CH_3, and CH_2=C(COOCH_3)-(on the physical and chemical evidences). On the basis of these evidences the isosericenine must be represented by structure (I) or (II). Since the isosericenine produced ujacazulene in a good yield in the dehydrogenation with selenium, it was concluded the isosericenine have structure (I). Sericea lactone, m.p. 150-151℃, [α]_DO, have molecular formula C_<16>H_<20>O_3 (mass spectrometry and elementary analysis) and CH_2=CH-C, CH_3-C, HO-O-O-CH_3, and CH_2=C(COOCH_3)-. Besides, isosericenine was easily oxidized in the stream of air in the presence of PtO_2 catalyst to produce sericea lactone. Therefore, sericea lactone was represented by structure (III). The structure of the third compound, sericenine, was elucidated by leading it into compound (VI), and its detail will be reported later. Isosericenine and sericea lactone are thought to be derived from sericenine.
View full abstract
-
Fusao Kido, Hisashi Uda, Akira Yoshikoshi
Article type: Article
Session ID: 16
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
A novel sesquiterpene carboxylic acid has been isolated from the essential oil of the vetiver (Vetiveria zizanoides Stapf) cultivated in Japan and was named zizanoic acid. The tricyclic structure (I) has been proposed for this acid from evidence outlined below. Dihydrozizanoic acid (V) was degraded to the norketone (X) through several steps, and it has been established that the ring to which the carboxyl group is attached is five-membered. Ozonolysis of methyl zizanoate (II) afforded the keto ester (XII) whose IR spectrum indicated strainless nature of this cyclic ketone and no existence of methylene adjacent to the keto group. On oxidation with lead tetraacetate followed by Jones' reagent, the diolester (XX) gave the seco-diacid (XXII), being a five-membered ketone. The presence of a gem. dimethyl group on C_2 was indicated by appearance of the most intense peak of m/e 102 (CH_3 CH_3 C=C OH^+ OCH_3) in the mass spectrum of the methylester of XXII and formation of isopropenyl group by photochemical cleavage of the ketoester (XIII). The unsaturated diacid (XXVII) was treated with Ac_2O to yield the anhydride (XXIX), and hydrolysis of the latter regenerated the original diacid (XXVI). Futhermore ditosylate of the diol (XXVIII) underwent ring closure to afford a cyclic ether by treatment with base. These results show that C_9-C_1 bond and the carboxyl group of zizanoic acid is in cis relationship. In addition of the above fact, ORD measurement of some ketone derivatives led to the absolute configuration shown by I for zizanoic acid.
View full abstract
-
Takeshi Matsumoto, Haruhisa Shirahama, Akitami Ichihara, Hyonsobb Shin ...
Article type: Article
Session ID: 17
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The compound XII, which has the unique non-isoprenoid skeleton and characteristic structural features of illudins, has been synthesized. The Michael reaction of IV and X was highly stereo-selective, a single product XI being obtained although eight racemic isomers are possible. The newly formed bond of XI was reasoned to be trans-oriented to the acetoxyl group on the five membered ring. The acetoxyl group at C_4 was introduced by the Pummerer reaction of XI. Treatment of XI with acetic anhydride-pyridine for a week at room temperature gave the expected product XIII. Only a single compound XIII was obtained as a Pummerer reaction product in spite of the possible existence of two stereoisomers. The compound XIII was converted to XIV by reduction with amalgamated aluminum and then to XVI through hydrolysis of the ketal group followed by intramolecular aldol condensation. NMR spectrum of XVI indicated the configurations at C_<3,4,9> as shown in Fig. 2. Attack of the Grignard reagent to XVI was also stereoselective and only one crystalline product was obtained. Total synthesis of illudins through the compounds described above is now under investigation.
View full abstract
-
K. Takase, T. Asao, M. Ando, S. Ibe, S. Kamiya
Article type: Article
Session ID: 18
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Acetylenic nor-sesquiterpene alcohols, dehydrochamaecynenol (I), C_<14>H_<18>O, [α]_D-193.1° and chamaecynenol (II), C_<14>H_<20>O, [α]_D+9.3°, and an acetate of II (III), C_<16>H_<22>O_2, have been isolated from Benihi tree (Chamaecyparis formosesis Matsum.) grown in Taiwan. The IR and NMR spectra of I and II show the prensence of a primaly hydroxyl, a terminal acetylenic linkage and a tertiary methyl group. UV spectrum of I showes the presence of a conjugated double bond. From NMDR and ORD, the structure (E) having a cis-decalin system was proposed for I. The structure (L) was also proposed for II and III from some reactions and NMDR of the derivatives of II. 1-Santonin (XIV) was transformed to cis-decalone carboxylic acid (XVII). Chlorodecarboxylation of XVII, followed by reduction with NaBH_4 and treatment with tBuO^- afforded ethylenic alcohol (XX). Bromination of XX, successive dehydrobromination and oxidation of the alcohol gave acetylenic ketone (XXIII). Bromination of XXIII in AcOH-HBr afforded two kinds of monobromide (XXIV, XXV). Dehydrobromination of XXIV with LiCl-Li_2CO_3 in DMF afforded chamaecynone (XXVI) identical with natural one.
View full abstract
-
Sho Ito, Mitsuaki Kodama, Makoto Sunagawa, Toshio Takahashi, Hiroyuki ...
Article type: Article
Session ID: 19
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
From the seeds of Podocarpus macrophyllus D. DON, a bisnorditerpenoid dilactone, inumakilactone (I), C_<18>H_<20>O_8, m.p. 251-253°(decomp),[α]_D^<±0°, was isolated together with nagilactone C^3. The presence of two secondary hydroxyl groups and a γ-lactone and an α,β-unsaturated-δ-lactone groupings in I was revealed by the acetylation, oxidation, hydrolysis and hydrogenation experiments; two inhert oxygens were concluded to be etheric. The partial structures [A]-[E] established by NMDR of the diacetate II were advanced to [A],[E],[F] and [G]or[G']and then to the planer structure on the basis of close examination of NMR spectra of fourteen derivatives. Stereochemistry of the ring carbons was elucidated by careful analysis of the chemical shifts and the coupling constants of all the hydrogens in these derivatives, particularly by the optical rotation difference between the lactone II and the corresponding hydroxy-ester X and by ORD and CD of the epoxyketones, IX and XII. Configuration at C-15 was determined by the application of the benzoate rule and the Horeau's asymmetric synthesis. The derived structure I has a close similarity with those of totarol, its congeners and nagilactones, which have been isolated from the other Podocarpus species, suggesting their intimate biogenetic relationship.
View full abstract
-
K. Nakanishi, H.-C. Chiang, M. C. Woods, Y. Nakadaira, M. Kurono
Article type: Article
Session ID: 20
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Ten minor constituents (2-11) have been isolated from Taxus Cuspidata Sieb. et ZUCC. in addition to the major constituent taxinine (Table 1). The strucures of 2 (O-cinnamoyltaxicin-I triacetate), 3 (taxinine A or TA), 4 (TH), 5 (TB), 6 (TE) and 7 (TJ) have already been clarified and are indicated in Fig. 1. I Structures of TK (8) and TL (9) and the photochemistry of taxinine. TL corresponds to the acetate of TK. Extensive NMR measurements of TK and TL employing decoupling and solvent shifts clarified the presence of the groupings summarized in Fig. 2; when the groups are fitted into the taxane skeleton it is noticed that C-3 and C-11 both have one unsatisfied valency suggesting that they should be linked. That this indeed is the case was established by the fact that irradiation of TA afforded TK in excellent yield (Fig. 3). Taxinine itself afforded phototaxinine in high yield (Fig. 4), the ease of ring closure obviously being due to the proximity of 3-H to the C_<11>-C_<12> double bond. II Nuclear Overhauser Effect (NOE) It was shown previously that the NOE can be a most powerful method in structural studies of rigid cage molecules; the NOE has also proven to be extremely useful in the taxinine series which have a more mobile ring structure. Protons connected by arrows in Fig. 5 are those exhibiting NOE' s. III Structures of TC (10) and TD (11) Spectroscopic data indicated the presence of the groups summarized in Table 2 and Fig. 6. Comparison of NMR data with the other taxinines and measurements of NOE's lead to two alternative structures 12a and 12b for TC and TD.
View full abstract
-
Tetsuya Komori, Shinro Setoguchi, Toshio Kawasaki
Article type: Article
Session ID: 21
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Diosbulbin B, C_<19>H_<20>O_6, and A, C_<20>H_<24>O_7, (formerly called bulbiferin B and A) are the furano-norditerpenes obtained from the root tubers of Dioscorea bulbifera L. forma spontanea Makino et Nemoto (Nigakashu, in japanese). They had been tentatively assigned the formulas (1) and (2), but a further investigation of the structures, particularly on the site of the ether linkage, has led to revision of the structures as (6) and (7) in which ether oxygen is attached to C-8 and C-12 and tertiary methyl group is located at C-5. The stereochemistry of B, A and their derivatives has been studied and the configurations shown in formulas (6) and (7) have been proposed for B and A, respectively. N.M.R., O.R.D., and Mass spectral data and other experimental results which support the above structures are presented and discussed.
View full abstract
-
A. Tahara, K. Hirao
Article type: Article
Session ID: 22
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
(I). Preferred Conformation of Dehydroabietic Acid(Cis A/B Ring System) Type Compound. Recently there has been an interesting discussion on whether the preferred conformation of a cis ring-fused system is of the steroid or nonsteroid type. In this paper, the conformation of cis 17-norditerpene (15) is discussed in comparison with that of cis 12-methyl compound (24). Analysis of their NMR, IR spectra and reactions leads to conclude that the steroid type conformation of 12-methyl series is preferred to the nonsteroid-type conformation having the 1,3 diaxial nonbonding interaction between the 12- and 1-methyl and, conversely, nonsteroid type conformation is preferred in the 17-nor-compound where the 12-proton is only present. (II). Preferred Conformation of 10 Oxy-podocarpic Acid Type Compound. Conformation of 10β- and 10α-oxy deoxypodocarpic acid derivatives and the corresponding lactones is discussed by their NMR and IR spectrum analysis. The NMR analysis is performed especially on the ABX type proton system as observed between 9-methylene and 10-methine protons.
View full abstract
-
M. Ohashi, M. Tateishi, T. Maruishi, Y. Inouye, H. Kakisawa
Article type: Article
Session ID: 23
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Two novel synthetic methods have been developed for the synthesis of phenolic diterpenoids. One of which is a base catallized condensation of a β-dicarbonyl compound with a β-alkoxyvinyl ketone to give a 2-acylphenol, and the another method involves quaternization of a γ-ketoalkylisoxazole, followed by treatment with aqueous base to yield a 2-acylphenol. Application of the latter method made possible a total synthesis of ferruginol from known decalone (20) via an isoxazole derivative(22) as shown in the figure. Tanshinone-II and Cryptotanshinone, diterpenoid pigments of Salvia miltorrhiza, were synthesized by 16 steps from 1,2,4-trimethoxybenzene. The methoxybenzene was converted by usual methods into the trimethoxydecalone(7), which on condensation with γ-bromocrotonic ester followed by palladium catallized isomerization afforded a naphthylbutyric ester (9). Succesive treatments of the ester (9) with methyl Grignard reagent and sulfuric acid gave a hydrophenanthrene(11) which was converted into the acylphenanthrene derivative (15) by the methods shown in the figure. One of the two methoxy groups in compound (15) was selectively hydrolyzed by BCl_3 to give a acylnaphthol (16), which was converted into the naphthofurane (18) by the usual methods. By heating with excess methyl Grignard reagent, methoxy group in the naphthofurane (18) was hydrolyzed and afforded a unstable furanonaphthol (19), which was oxidized with Fremy's salt to give the Tanshinone-II, identical with the natural compound in all respects.
View full abstract
-
Y. Kitahara, M. Funamizu, T. Kato, N. Ototani, T. Machiguchi, A. Inoue ...
Article type: Article
Session ID: 24
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Total syntheses of tetracyolic diterpenes such as gibberellin and grayanotoxin are one of the big goals for the organic chemists. During the course of the investigations of the structure, total synthesis and some novel reaotions of Hibaene, the authors have found the possibilities to the syntheses of these biologically active diterpenes. In this paper, some approaches to the syntheses of C_<19>-gibberellins and staohenone are desoribed in two separated sections (A and B). A. Approach to the C_<19>-gibberellin A new synthetic route to the gibbane skeleton was established by the B-ring construction from compound 13 which was synthetized from compound 10 following the scheme III. Model experiments for the synthesis of ring A in gibberellin is also desoribed in scheme II. B. Approach to the staohenone Tricyclic intermediate 5a was synthetized by the application of Robinson-Mannich annelation reaction to compound 4, obtained from 4-methyl-cyclohexane-1,3-dione as following saheme IV. Oxidation of allyl group of compound 5a, followed by base catalyzed oyalization led to the potential tetracyclic intermediate 7a, which was converted to the compound 2 (scheme V). Conversion of 9 to stachenone 11 is now being actively investigated.
View full abstract
-
Hideko Ogawa, Shinsaku Natori, Setsuko Sakaki, Kunitoshi Yoshihira
Article type: Article
Session ID: 25
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The distribution of hydroxybenzoquinone derivatives among Myrsinaceae plants growing in Japan has been examined and the presence of embelin (Ia), rapanone (Ib), maesaquinone (IIa), acetylmaesaquinone (IIb), and 2-hydroxy-5-methoxy-3-pentadecenyl(tridecenyl, tridecyl)benzoquinone (Va) and novel type bis(benzoquinonyl)-olefines, designated ardisiaquinones A (V), B (VI), and C (VII), was confirmed. Ardisiaquinones (V-VII), isolated from Ardisia sieboldii in respective yields of 0.02, 0.02, and 0.0005%, showed the similar properties and, from the formation of the derivatives (Chart 1) and from their spectroscopic properties (cf. Table 1), the partial formula (A) was put forward for these compounds. Mass (Table 2), IR and UV spectra suggested the positions of the substituents as shown in the formula (B) and the alkaline hydrogen peroxide oxidation afforded cis-octadec-9-en-1,18-dioic acid. Thus the structure of ardisiaquinones have been established as V, VI and VII. The structure has also been confirmed by the unequivocal synthesis of XIX shown in Chart 2. The biogenesis of the compounds will also be discussed.
View full abstract
-
Z. Horii, T. Momose, H. Hakusui, Y. Tamura
Article type: Article
Session ID: 26
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
η-Pyrromycinone (2) and bisanhydroaklavinone (21), key compounds in the chemistry of the anthracycline antibiotics, were synthesized via the Friedel-Crafts condensations of methyl 2-ethyl-5-hydroxy-1-naphthoate (6) with 3,6-dimethoxyphthalic and 3-methoxyphthalic anhydride, respectively, as shown in Charts 1 and 2. The condensation product, methyl 2-ethyl-5-hydroxy-6-(2-carboxy-3,6-dimethoxybenzoyl)-1-naphthoate (11) or methyl 2 -ethyl-5-hydroxy-6-(2-carboxy-6-methoxybenzoyl)-1-naphthoate (23), was methylated, reduced with zinc powder in boiling aqueous caustic soda and cyclized with polyphosphoric acid to give the naphthacenonecarboxylic acid (16 or 26). The methyl ester of (16) or (26) was oxidized with a large excess of chromium trioxide in glacial acetic acid to the trimethyl ether of (2) or the dimethyl ether of (21), which was demethylated, at room temperature, with boron tribromide in dry methyllene chloride to give η-pyrromycinone (2) or bisanhydroaklavinone (21). The syntheses thus accomplished confirmed unequivocally the structures of η-pyrromycinone and bisanhydroaklavinone. The examination of NMR spectra of several diastereomeric 3,4-disubstituted tetralones and tetralins revealed that the anisotropic deshielding effect of the benzene ring over the C_4-H (quasi-equatorial) in the cis series and the benzylic coupling between the C_4-H (quasi-axial) and the aromatic protons in the trans-series were effective to assign the configuration and the conformation of the tetralones and the tetralins. The result would provide an effective method to assign the configuration and the conformation of substituents on ring A of anthracyclinones.
View full abstract
-
Y. Iida, M. Nagai, O. Tanaka, S. Shibata, T. Ando
Article type: Article
Session ID: 27
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Previously, the sapogenin of ginsenosides-Rb_1, -Rb_2, and -Rc has been reported to be protopanaxadiol(II). However, the finding of the acid catalyzed epimerization of C-20 OH of this type of compounds has prompted the further investigation of C-20 configuration of the genuine sapogenin of these saponins. On Smith's degradation of these saponins, 20-epi-protopanaxadiol(IV) was yielded but formation of II was not observed. Accordingly, it can be now concluded that the genuine sapogens of the above saponins should be represented by IV. Ginsenoside-Rg_1, another saponin of Ginseng, has been purified through its deca-acetate. On hydrolysis with dil. mineral acid, -Rg_1 gave panaxatriol (and its C-20 epimer) (IX) and D-glucose. Treatment of-Rg_1 with conc. HCl followed by dehydrochlorination gave protopanaxatriol(X) as well as its C-20 epimer (XI), whereas Smith's degradation of-Rg_1 yielded XI only. The strucures of X and XI including C-20 configuration have been established as being 6α-bydroxy-protopanaxadiol and 6α-hydroxy-20-epi-protopanaxadiol, respectively. On the basis of the above evidences and other experimental results, -Rg_1 was represented by diglucoside of XI. Methanolysis of permethyl ether of -Rg_1 afforded methyl 2,3,4,6-tri-O-methyl-glucoside. Acid hydrolysis of permethyl ether of hydrogenated -Rg_1 yielded 3,12-di-O-methyl-dihydroprotopanaxatriol(XXII) (or its C-20 epimer). Consequently, -Rg_1 can be formulated as 6,20-di-O-D-glucosyl-20-epi-protopanaxatriol.
View full abstract
-
Kenji MORI, Masanao MATSUI
Article type: Article
Session ID: 28
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Juvabione (Ib=methyl todomatuate) and dehydrojuvabione (IIIb) show strong juvenile hormone activity in the bug, Pyrrhocoris apterus L. (±)-Juvabione (Ib), its stereoisomer (XXIb) and a mixture of (±)-dehydrojuvabione (IIIb) and its stereoisomer (XLIIb) were synthesized in the following manner. (±)-JUVABIONE An acid (IX) was prepared from anisole (V). This was converted to the corresponding dimethylamide (XI). Reduction of (XI) gave an aldehyde (XII) which was treated with isobutyl magnesium bromide to afford (XIII). Birch reduction of (XIII) followed by acid hydrolysis gave (XV). The unsaturated ketone (XV) was reduced to give (XVI) which in turn was acetylated to afford (XVII). The corresponding cyanohydrin (XVIII) was dehydrated to give (XIX). This was hydrolyzed and oxidized to give a mixture of (Ia) and (XXIa) which was separated into (Ia) and (XXIa) via semicarbazones (XXII, crystal; XXIII, oil). The acids were esterified to give (±)-juvabione (Ib) and its stereoisomer (XXIb), respectively. (±)-DEHYDROJUVABIONE A β-keto ester (XXXI), prepared from (X) via (XXIX) and (XXX), was hydrogenated to give (XXXII). This was treated with methyl magnesium iodide to give a diol (XXXIII). Birch reduction of this diol gave (XXXIV). This was treated with acid to give (XXXV) which in turn was hydrogenated and acetylated to give (XXXVII). Addition of hydrogen cyanide to (XXXVII) followed by dehydration gave an unsaturated nitrile (XXXIX). This was hydrolyzed, oxidized and dehydrated to give a mixture of (IIIa) and (XLIIa).This was esterified to give a mixture of (±)-dehydrojuvabione (IIIb) and its stereoisomer (XLIIb).
View full abstract
-
A. Hatanaka, T. Kajiwara, M. Ohno
Article type: Article
Session ID: 29
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
In an earlier work, it was reported that leaf alcohol,when refluxed with metallic sodium, gave a lemone-like flavor, which was assumed as being 3-propyl-nona-3,6-dien-l-ol or 3-propyl-nona-3-en-l-ol. In this report, it was revealed that leaf alcohol resisted catalytic hydrogenation and faded neither KMnO_4 solution nor Br_2, contrary to what was expected from the aliphatic diene. Through chemical and physical means that it was given trimellic acid upon oxidation with KMnO_4 and (VI) was produced from (III-a) by the same condition with leaf alcohol,and then the UV-absorption at 268mμ and IR-absorption bands characteristic (1510, 889,832cm^<-1>) suggesed that it should be resulted a aromatic compound, this structure was deduced as 2-propyl-5-ethyl-benzylalcohol(IV). (IV) was also obtained from each of (I-b-d) and (I-e) under exactly the same reaction conditions. Furthermore, in the extention of this reaction to C_5;(II) and C_4;(III)-a,b), the aromatization was also effected 2-ethyl-5-methyl-(V) and 2-methyl-benzylalcohol(VI). This aromatization reaction originally found with leaf alcohol seemed to be generalized to the aliphatic αβ- and βγ-unsaturated alcohols and aldehyds, and hence was designated as leaf alcohol reaction. This reaction mechanism was proposed on the basis of reaction with (III-b) or (I-e) which on stepweise treatment with weaker bases gave (VI) or (IV) through isolating cyclodiene intermediate, (VIII-a) or (VIII-b). Conclusively, therefore, this mechanism involving dehydrogenation, Michael addition, aldol condensation-cyclization and dehydration, crossed Cannizzarro reaction is preferred to the previously proposed one.
View full abstract
-
A. Ogiso, M. Kurabayashi, H. Mishima, M. C. Woods
Article type: Article
Session ID: 30
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
A crystalline constituent, futoenone; C_<20>H_<20>O_5, m.p. 197°, was isolated from Piper futokadzura and proved to have the structure 1. On the basis of uv spectra of futoenone (1), dihydrofutoenone (3) and the hydroxy compounds (2,4), the presence of a piperonyl and α,β-unsaturated carbonyl moiety were suggested as the chromophores. The structure of diacetate (5), given by the treatment of futoenone with acid in acetic anhydride, was designated as 5 by means of n.m.d.r. and chemical evidences. The result of giving back to futoenone from the diacetate (5) via tosyl-phenol (9) or anisyl-alcohol (10), providing an interesting example of Ar_1-6 participation, strongly supported the spirodienone structure in futoenone. Lemieux oxidation of futoenone and hydrogen peroxide oxidation of demethylfutoenone (13) gave γ-lactone (15) and (16) respectively. This result and the formation of the highly conjugated benzofuran derivative (12) by oxidation of the diacetate (5) with DDQ indicated the presence of a fused tetrahydrofuran ring. N.m.d.r. studies of futoenone (Table 3) deduced a partial structure D for the aromatic ring, E for the saturated carbons and F for the dienone moiety. The three partial structure together account for nineteen carbons, all of the hydrogens and oxygens in futoenone. Since the carbon atom linked with C-5 and C-1 cannot bear any proton and C-11 carbon cannot link any carbon having hydrogen, C-11 carbon must be bonded with an oxygen and C-1, C-5, C-7 and C-11 carbons must all be linked to a spiro carbon to deduce the full structure of futoenone. The stereochemistry was also proposed by the data of n.m.r.
View full abstract
-
K. Nakazawa
Article type: Article
Session ID: 31
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The structure of hinokiflavone was confirmed by synthesis. Permethylated 3-nitrobisapigenyl ether (XVI), the key-intermediate for the synthesis, was prepared by the condensation of 8-hydroxy-4',5,7-trimethoxyflavone (XIV) with 4'-iodo-3'-nitro-5,7-dimethoxyflavone (XV) in DMSO in the presence of K_2CO_3 at 110℃ for 1hr. The nitro ether was reduced by Na_2S_2O_4 in aq. DMF, diazotized and decomposed with 50% H_3PO_2 to give 4'",5,5",7,7"-pentamethoxy-4',8"-bisapigenyl ether (XVIII), different from pentamethyl ether of natural hinokiflavone. An alternative bisflavone with 4',6"-coupling positions has now been synthesized in a similar route described above. 6-hydroxy-4',5,7-trimethoxy flavone (XXVIII) was condensed with 4'-iodo-3' nitroflavone (XV) to 3'-nitro ether (XXIX), which was reduced, diazotized and decomposed to give permethylated ether (XXXI). The latter proved to be identical in m.p., mixed m. ps. and IR spectra with permethyl ether of natural hinokiflavone. The synthesized methyl ether was finally demethylated by means of HI・Ac_2O at 130〜140℃ for 3hrs. to give 4'",5,5",7,7"-pentahydroxy-4',6"-bisapigenyl ether (XX) identical with natural hinokiflavone. 4'-8"-Bisflavone (XVIII) was converted into a bisflavone (XX) identical with natural hinokiflavone, when heated with HI・Ac_2O as above, under conditions which may be expected to bring about the Wessely-Moser rearrangement in flavones, coumarins, xanthones etc.
View full abstract
-
Teruo Matsuura, Hideo Matsushima, Harushige Sakamoto
Article type: Article
Session ID: 32
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
It has been reported that quercetin (Ib) is oxidized to 2-protocatechuoyl phloroglucinol carboxylic acid (II) and carbon monoxide by dioxygenases from Aspergillus species. In view of the resemblance between action of some oxygenases and photosensitized oxygenation, we have carried out photosensitized oxygenation of 3-hydroxyflavones. In a typical run, a solution of quercetin 5,7,3',4'-tetramethyl ether (III) and rose bengal(sensitizer)in pyridine was irradiated with a tungsten lamp or a high-pressure mercury arc lamp under bubbling oxygen. Methylation of the crude products with diazomethane followed by column chromatography afforded depside (IV), its hydrolysed products, carbon dioxide and carbon monoxide. The results are summarized in Table I and II, which show that the presence of a 3-hydroxy group is prerequisite for this oxidation, and a possible reaction mechanism is illustrated in Scheme I. On the other hand, it was found that photoxidation of 3-methoxyflavones caused a quite different type of reaction. Ultraviolet irradiation of 3-methoxyflavone (XXII) under bubbling oxygen yielded the chromono-isocoumarin derivative (XXIII), which has the same carbon skelton as an uncommon flavonoid, distemonanthin (XVIII). This cyclization raises some speculations on the biosynthesis of uncommon flavonoid.
View full abstract
-
B. Shimizu, M. Miyaki
Article type: Article
Session ID: 33
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The alkyl and glycosyl groups of the purine derivatives were found to migrate from N-3 to N-9(N-7) position. The transfer of the glycosyl moiety of the pyrimidine nucleosides to the purine bases was carried out successfully. (Fig. 1) On heating in the presence of HX(X=C1, Br) 3-benzyl-N^6-benzoyl-adenine underwent the benzyl migration giving rise to the 9-benzyl derivative and a small amount of the 7-isomer. γ,γ-Dimethylallyl group of N^6-acyltriacanthine migrated under the same conditions to afford the 9-γ,γ-dimethylallyl derivative, whereas H_gX_2 caused the intramolecular rearrangement to give the 9-α,α-dimethylallyl ismer. (Fig. 2) The glycosyl migration of O,N^6-acyl-3-β-isoadenosine and its 5'-phosphate proceeded milder conditions. The 9-β-ribofuranosyl derivative was predominant in this migration reaction and the amount of α anomer depended on the catalyzer used. (Tab. 3) Similar migrations took place in cases of adenine, N^6,N^6-dimethyladenine and N^2-acetylguanine. (Tab. 1) These migration reactions were applied to the transglycosylation from pyrimidines to purines. When O,N-tetra-acylcytidine or -uridine was heated with N^6-acyladenine in the presence of the catalyzer, the ribosyl moiety of the acylated pyrimidine nucleoside migrated to N^6-acyladenine to yield O,N-tetra-acyladenosine. The derivatives of 3-isoadenosine, N^6,N^6-dimethyladenosine, inosine, guanosine and 7-ribofuranosylguanine were also obtained in good yields. (Tab. 5) Application of the transglycosylation reaction must pay a role in the preparation of purine nucleosides.
View full abstract
-
T. Kitagawa, Y. Sawada, T. Miura, T. Ozasa, H. Taniyama
Article type: Article
Session ID: 34
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The tuberculostatic antibiotic viomycin is a strong basic peptide which shows ultraviolet absorption at 268 mμ(ε 2,3000). Recently A.W. Johnson et al, successively J.R. Dyer et al have presented different structures for viomycin respectively. But on partial hydrolysis of viomycin with dilute hydrochloric acid, we obtained peptide I group (Ia, Ib, Ic), peptide II and peptide III. Finding out of composed amino acid, C-terminal amino acid and N-terminal amino acid of these peptides and viomycin, we could determine the amino acid sequences of viomycin as β-lysyl-seryl-α,β-diaminopropionyl-viomycidyl-seryl-urea. This result shows neither structure for viomycin proposed by Johnson group nor Dyer group are correct even in their amino acid sequences. Treatment of viomycin with diisopropyl fluorophosphates and then methanol gave mono-DIP-methyl viomycin, and the patial structure IX is presented for this. The structure of chromophore group in viomycin is also discussed.
View full abstract
-
H. Ogawara, K. Maeda, G. Koyama, H. Naganawa, H. Umezawa, Y. Iitaka
Article type: Article
Session ID: 35
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Pyridomycin is an antibiotic produced by Streptomyces pyridomyceticus and exhibits strong inhibition against mycobacteria. The structure of pyridomycin has been recently determined by X-ray analysis of the crystal of pyridomycin dihydrobromide (C_<27>H_<32>O_8N_4・2-HBr・H_2O・CH_3CH_2OCOCH_3) as 10-hydroxy-6-(3-hydroxypicolinamide)-5,11-dimethyl-2-(1-methylpropylidene)-9-(3-pyridylmethyl)-8-aza-1,4-dioxa-cyclododecane-3,7,12-trione. On the other hand, structure studies on pyridomycin have been performed by chemical degradation such as ozonolysis and hydrolysis in alkaline and acidic media. The isolation of ethylmethylketone (I) by ozonolysis and α-keto-β-methylvaleric acid (IV) by alkaline hydrolysis verifies the presence of methyl-propylidene group in pyridomycin. Another degradation product from alkaline hydrolysis named pyridomycin acid (III) decomposes in acid into a dehydrated product of 3-hydroxypicolinyl-L-threonine (VI) and 4-amino-3-hydroxy-2-methyl-5-(3-pyridyl) pentanoic acid (IX) along with its dehydration (X) and deamination (VIII) products. The linking position of an unique 12 membered ring containing two ester and one amide bonds is confirmed by spectroscopic methods, pK^1_a values, and finally chromic acid oxidation method. All results obtained by chemical degradations and spectroscopic analysis including n.m.r. spectrum of pyridomycin explain satisfactorily the whole structure of pyridomycin proposed by X-ray crystallographic analysis.
View full abstract
-
T. Endo, H. Yonehara
Article type: Article
Session ID: 36
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Antimycin-A: blastmycin group antibiotics were found as strong fungicides and separated to antimycin A_1, A_2, A_3 (=blastmycin) and A_4. The structures of main components A_1 and A_3 were elucidated as I. Gas-lizuid. chromatographic studies of trimethylsilyl ether or trifluoroacetate of the antibiotics revealed complexity of the components. The degradative products were also investigated by glc to determine each antibiotic structure. Blastmycin could be classified into two components, which differed at acyloxy grous (R'=(CH_3)_2CHCH_2- and R'=C_2H_5(CH_3)CH-) on dilactone ring. Antimycin-A complex have about nine components which are different at alkyl side chains and acyloxy groups. These antibiotics have five asymmetric carbons and two of them are on L-threonine moiety and three of them are contained in neutral γ-lactone (III). Nmr spectrum of III showed coupling constant ca 4 cps for the ring protons. This figure indicates trans-trans configuration comparing with some reported spectra. LiAlH_4 reduction of blastmycin (I-B) or blastmycinone (III-B) gave a triol, which was oxidized to (+)-2-hydroxymethyl-n-caproic acid (XII). Holliday and Polgar depicted L(+)-2-methyl-n-pentanoic acid (XIII) and L(-)-2-methyl-n-pentan-l-ol (XIV) as S configuration. On correlation to XIII and XIV, (+)-2-methyl-n-hexan-l-ol (XVI) derived from authentic (-)-2-hydroxymethyl-n-caproic acid (XV) proved R configuration for the natural (+)-acid (XII). Therefore the configuratin of γ-lactones and original antibiotics were described as XVII and XVIII.
View full abstract
-
K. Isono, K. Kobinata, S. Suzuki
Article type: Article
Session ID: 37
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Polyoxin complex is an antibiotic mixture produced by Streptmyces cacaoi var. asoensis and is active specifically against phytopathogenic fungi. Polyoxins A, B, C, D, E, F, G, H and I were isolated in pure forms out of it. The structure of polyoxin C, the smallest molecule, was elucidated as 1-β-(5'-amino5'-deoxy-D-allofuranuronosyl)-5-hydroxy-methyluracil (I). The position of the amino group was determined spectroscopically and the aminouronic acid moiety was derived into D-allose (IX) after deamination and solvolysis. Polyoxin A was hydrolyzed into four moieties evolving each one mole of NH_3 and CO_2; 5-hydroxymethyluracil, polyoxin C and two amino acids, polyoximic acid (XIII) and polyoxamic acid (XIV). The structure of XIII was proposed as 3-ethylidene-L-azetidine-2-carboxylic acid and XIV was presumed to be α-amino-β,γ,δ-trihydroxyvaleric acid. The structures of the molecular components of polyoxin A were summerized in Fig. 6. The close structural relations of polyoxin A〜I were also discussed.
View full abstract
-
Saburo TAMURA, Akira MURAYAMA, Kengo KAGEI, Kosei HATA
Article type: Article
Session ID: 38
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Fragin (I), C_<13>H_<27>O_3N_3, was isolated by the present autho s from cultured broth of a soil bacterium belonging to Pseudomonas fragi as an inhibitor of the growth of chlorella, fungi and some higher plants. The presence in (I) of an unique N-nitrosohydroxylamino group was deduced from the acidity, colour reactions and spectral data. The formation of caprylic acid on acid hydrolysis together with the IR and NMR spectra of (I) suggested the presence of a secondary caprylamide group in this compound. The NMR spectrum of (IV) clarified the function of the remaining five carbon atoms to be -NHCH_2COCH(CH_3)_2. Further, the series of reactions shown in Fig. 3 established the structure of Fragin as (I). Then, (±)-Fragin was synthesized by the route summarized in Fig. 6. The IR spectrum (in CCl_4) and NMR spectrum (in CDCl_3) of the synthetic Fragin were completely identical with those of natural one. As expected, the synthesized sample showed almost about a half antifungal activity of the natural compound against Asp. niger.
View full abstract
-
T. Irie, M. Izawa, E. Kurosawa
Article type: Article
Session ID: 39
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
A new bromo compound, designated as laureatin-A, has been isolated along with an isomeric bromo compound from Laurencia nipponica YAMADA. Laureatin-A (II), C_<15>H_<20>O_2Br_2, had m.p. 82〜83° and [α]_D+98°and the UV, IR, NMR and mass spectra exhibited the presence of the following groups: -CH_2-CH(trans)=CH-C≡CH, -CH_2-CH_3, 2>CH-Br, 2>CH-O-CH< and 2 -CH_2-. On the basis of chemical and spectral data of the compound and its degradation products, formula II is proposed as the most favorable structure.
View full abstract
-
T. Kikuchi, T Nishinaga, S. Jr. Uyeo
Article type: Article
Session ID: 40
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Pachystermine-A (I) and -B (II), isolated from Pachysandra terminalis SIEB. et ZUCC., are unique in that they carry a β-lactam ring system in the molecule. These alkaloids are now synthesized from epipachysandrine-A (III), a minor alkaloid obtained from the same plant. At first we examined the conversion of pachystermine-diol (IV) to I and II. IV was transformed to the mono-O-acetate (VII) which was then oxidized to the amino acid (VIII). β-Lactam cyclization of this amino acid was successfully performed by the action of DCCD in CH_2Cl_2 to give IX. Subsequent treatment of the latter (IX) with LiAlH_4 under controlled condition afforded pachystermine-B (II), which can be oxidized to pachystermine-A (I) as reported already. Conversion of epipachysandrine-A (III) to a mixture of 3'-epimeric diols (XIII) was easily achieved in essentially reported manner. However, attempts to separate pachysterminediol (IV) from this mixture were unsatisfactory. Eventually N-methylpachystermine-diol (XVA), which could readily be isolated from the 3'-epimeric mixture, was converted to pachystermine-diol (IV) as shown in Chart 2.
View full abstract
-
H. Ageta, K. Iwata, T. Kasama
Article type: Article
Session ID: 41
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
From the leaves of Adiantum monochlamys EATON (Pteridaceae), four triterpenoid mono alcohols, filicenol A (I), filicenol B(VIII), tetrahymanol (XIV) and Isoadiantol B (XVII), were isolated together with hydroxyhopane (XV). Filicenol A was assigned to be filic-3-en-6β-ol (I) by the studies on the IR, NMR and Mass spectra, and the structure was confirmed by the reactions giving the compounds (III), (IV), (V), (VI) and (VII). The structure of filicenol B was also assumed to be filic-3-en-25-ol (VIII) by the physical methods, and the reactions, affording the compounds (X), (IV), (XI), (XII) and (XIII), were carried out. Tetrahymanol (XIV) was the first example of gammaceranes isolated from the plant kingdom, and co-existence with hydroxyhopane (XV) in the same plant was very interesting. Isoadiantol B (XVII) was synthesized from isoadiantone and the configuration at C 22 was assigned as to be XVII by the comparison of optical rotatories with those of 20-hydroxypregnenes. The chemical shifts of the methyl groups of the triterpenoids having the filicane skeleton were shown in Table I.
View full abstract
-
Takahiko Tsuyuki, Yoshihiko Moriyama, Tokiko Hoshino, Yoshiaki Tanahas ...
Article type: Article
Session ID: 42
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
Shionone (I) is a tetracyclic triterpene ketone, C_<30>H_<50>O, isolated from the roots of Aster tataricus L. The partial structure (III) has been deduced for shionone on the basis of chemical degradations. The structure (III) has been extended to (I) by means of biogenetic considerations. In the present report, the nature of rings C and D is clarified and the conversion of friedelin into methyl tetranorshionanoate is described. These evidences lead without the help of biogenetic considerations to the structure (I) for shionone. Shionone (I) was transformed into heptanorshionanone (IV). The IR and ORD data of (IV) indicate that the ring D of (IV) must be a six membered ring with a ring fusion (C/D) of 5 α-cholestan-3-one or -2-one type. The mass spectrum of ethylene ketal of (IV) shows a peak at m/e 99 (fragment ion "a") (base peak) together with a strong peak at m/e 139 ("b"). This means that (IV) must be 20-oxoheptanorshionane (XXII). The NMR studies on the shionone derivatives show that the side-chain bears a 1,3-diaxial relationship to an α-(axial) methyl group at C_<13>. The configuration of the side-chain, therefore, must be α(axial). Structure (I) follows for shionone. The structure (I) was fully demonstrated for shionone by the following transformations: Friedelin (II)→(XXVIII)→(XXIX)→(XXX)→(XXXI)→(XXXII)→norshionene (XXVI)→methyl tetranorshionanoate (XXVII).
View full abstract
-
Itiro Yosioka, Tsutomu Nakanishi, Isao Kitagawa
Article type: Article
Session ID: 43
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The stereochemical studies especially on rings D,E and ring E side chain of zeorin(5), leucotylin(6), and leucotylic acid(7), which were isolated from lichen, Parmelia leucotyliza Nyl., have been performed. It has been found at the beginning that leucotylin possesses an eoimeric hydroxyisopropyl side chain at C_<21> against zeorin, which has been believed to have hopane skeleton. Thus, a monoketone(15) derived from leucotylin has been found identical with a monoketone(24), obtainable from zeorin and being epimeric to it at C_<21>. Furthermore, a hydrocarbon(25) possessing the same carbon skeleton as zeorin has been proved identical with hopane, whereas a hydrocarbon(26) carrying the same carbon framework as leucotylin has been identified with isohopane (≡moretane). Since the fact that the widely co-existed triterpenes, zeorin and leucotylin, in the lichen have the epimeric carbon skeletons at C_<21> seemed quite interesting from the biogenetical view-point and it seemed worthwhile to search for the final proof on their stereostructures, the X-ray analysis of 6-keto-leucotylin-16β-O-p-bromobenzoate (28) has been done. Strikingly, it has been found that leucotylin in fact possesses α quasi-equatorial side chain at C_<21> (as in (6)) and consequently it follows that isohopane should be expressed by (26) with α isopropyl at C_<21> rather than β as believed before and in addition, zeorin and hopane must be formulated by (5) and (25) having β isopropyl side chain at C_<21> rather than α. Leucotylic acid has also been proved as (7) having β-hydroxyisopropyl side chain at C_<21> similarly as in zeorin based on its chemical and physicochemical behaviours.
View full abstract
-
T. Murata, M. Shinohara, T. Hirata, M. Nishikawa, K. Kamiya, M. Miyamo ...
Article type: Article
Session ID: 44
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
The two new triterpenes, named alisol A and alisol B, have been isolated from the rhizomes of Alisma Plantago-aquatica L. var. orientale SAMUELS. (A. orientale JUZEP.), and their structures were elucidated by both chemical and X-ray crystallographic techniques. Alisol A (1) was demonstrated to be a tetracyclic triterpene in which the iso-octyl side chain possesses the glycerol moiety mainly by the chemical evidences that the periodate oxidation of the compound evolved acetone together with the tetranoraldehyde (7), and that acetonization of the compound followed by acetylation afforded the acetonide monoacetate (9). The structure of the ring system was also discussed by physico-chemical measurement. The X-ray analysis on alisol A acetonide monobromoacetate (11) was carried out to establish the structure of alisol A as 1. Alisol B was correlated to alisol A, and was assigned the structure 2. This is the first occurrence of C_<30>-triterpenes having the fusidane-type B/C ring juncture together with a double bond at 13(17) position.
View full abstract
-
G. Kusano, S. Matsumoto, T. Takemoto
Article type: Article
Session ID: 45
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
During the course of work on the constituents of Cimicifuga app., a new triterpenoid xyloside cimicifugoside (I), m.p. 237-238, C_<37>H_<54>O_<11>, has been obtained from the rhizomes of Cimicifuga simplex (Japanese name "sarashina shoma"). I is hydrolyzed with 50% acetic acid, 1% oxalic acid, or sodium periodate giving xylose, cimicifugenin A (III), and others. According to NMR and IR spectra of I and cimicifugoside tetra-acetate (II), which is obtained by complete acetylation of I, it is shown that I has a cyclopropane ring, an acetoxyl group, a double band, and a hemiacetal. The substance III yields the acetate (IV) and the benzoate (V) on acylation, the γ-lactone (VI) on oxidation with pyridine-CrO_3, the methyl ether (VII) on treatment with dil. methanolic HCl, and the deacetyl compound (VIII) on hydrolysis with 5% NaOH. Oxidation of VIII with pyridine-CrO_3 gives the α,β-unsaturated ketone (IX). These chemical properties suggest partial structures A-E for III. The comparison of the data of III with those reported for acetyl acteol (XVIII) shows that III has the same spiroketal structure as the latter (XVIII). On the basis of the above results, the structure III is proposed for cimicifugenin A. Deduction of the structure III for the hydrolyzed product of I, the chemical and physico-chemical properties of I and III, and mechanistic considerations in the transformation from I to III lead to the structure I for cimicifugoside.
View full abstract
-
Article type: Appendix
Pages
App2-
Published: September 25, 1967
Released on J-STAGE: August 18, 2017
CONFERENCE PROCEEDINGS
FREE ACCESS
