-
Takashi Matsumoto, Tetsuaki Okabe, Kenji Fukui
1973 Volume 2 Issue 8 Pages
773-776
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The absolute configurations of latifolic acid (IVa) and its stereoisomers (IVb, Va, and Vb) have been elucidated. (
S)(+)-3-Methoxycarbonyl-2-methyl-cis-3-pentenoic acid (VIIIa), correlated to (
S)(−)-2-methyl-1,4-butanediol (XII), was converted to latifolic acid (IVa: 2
S,3
S,4
R) and Va (2
S,3
R,4
S). Similarly, the enantiomer (VIIb) was also converted to IVb (2
R,3
R,4
S) and Vb (2
R,3
S,4
R). The CD spectra of these butyrolactones were also examined.
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Masatsugu Kajitani, Junko Okada, Tetsuya Ueda, Akira Sugimori, Yoshiyu ...
1973 Volume 2 Issue 8 Pages
777-780
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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A new method of activation of ppt-Ni by refluxing with alcohols is described. The ppt-Ni activated in this way (U–Ni–N) exhibits high catalytic activity corresponding to U–Ni–A. The catalyst performs selective reactions in the hycrogenation of 1-octene (low isomerization) and of cyclcolefins.
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Hidemasa Takaya, Masashi Yamakawa, Ryoji Noyori
1973 Volume 2 Issue 8 Pages
781-782
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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In the presence of nickel(0) complexes
cis-9,10-dicarbomethoxypentacyclo[4.4.0.0
2,5.0
3,8.0
4,7]decane isomerizes cleanly to give a mixture of
endo- and
exo-
cis-9,10-dicarbomethoxytricyclo[4.2.2.0
2,5]deca-3,7-dienes.
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Akinobu Sasane, Tomoyoshi Tanaka, Akira Toba, Yoshio Kume, Daiyu Nakam ...
1973 Volume 2 Issue 8 Pages
783-786
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The nuclear quadrupole resonance of chlorine in MptCl
6–6H
2O (M(II) = Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba) was observed between 77 and 450 K. Copper(II) hexachloroplatinate(IV) hexahydrate shows a phase transition at 137 K. This complex and barium hexachloroplatinate(IV) hexahydrate yield resonance lines showing a positive temperature coefficient capable of being interpreted in terms of hydrogen bond formation.
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Susumu Tsuchiya, Yoshiaki Saito, Tsugio Murakami, Hideaki Iwata, Tsuto ...
1973 Volume 2 Issue 8 Pages
787-788
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The alkylation of toluene with propylene takes place over the electron donor–acceptor complexes of anthracene, chrysene, benzoquinone, and
p-chloranil with sodium, and two types of the alkylation, the side-chain- and the nuclear-alkylation, have been suggested by the reaction products, butylbenzenes and cymenes.
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Takashi Suzuki, Norio Sugita, Mitsuko Asai
1973 Volume 2 Issue 8 Pages
789-792
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Absolute configurations of neutral sugar of antibiotic B-58941 and two methyl glycosides of its dihydro-sugar are assumed as 2,3,6-trideoxy-
L-hexopyranos-4-ulose and methyl 2,3,6-trideoxy-(α or β)-
L-erythro-hexopyranoside, respectively. Methyl glycoside of a basic sugar of B-58941-B is identified as methyl
D-mycaminoside.
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Takashi Suzuki, Eiji Mizuta, Norio Sugita
1973 Volume 2 Issue 8 Pages
793-798
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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A new condensate (macrocyclic lactone) is obtained by refluxing depoxy B-58941-B, prepared by depoxidation of antibiotic B-58941, with sulfonic acid-type resin in methanol. The structure of the condensate is assumed as 3,5-dihydroxy-4,8,12,14-tetramethyl-9-oxo-6,8-(1-methoxyethano)-10,12-heptadecadien-15-olide.
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Takashi Suzuki
1973 Volume 2 Issue 8 Pages
799-804
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Structure of new compound derived by reaction of diacetate of antibiotic B-58941 with sodium methoxide in methanol is assumed as 2′-
O-acetyl-2,3-anhydro-13-hydroxy-12-methoxy-depoxy B-58941. It is also assumed that in antibiotic B-58941,
D-mycaminose and 4-ulose sugar are bound to C-5-O of the aglycone (by β-linkage) and to C-4′-O of
D-mycaminose (by α-linkage), respectively.
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Tetsuo Aida, Naomichi Furukawa, Shigeru Oae
1973 Volume 2 Issue 8 Pages
805-808
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The reaction of benzyl phenyl or methyl phenyl
N-
p-tosylsulfilimine with trivalent phosphorus compounds in DMF gave the original sulfide. From, the kinetic study the reaction mechanism is proposed to proceed via the initial nucleophilic attack by phosphine to sulfinyl sulfur atom. Meanwhile, the addition of water to the solvent changed both the products and kinetic results.
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Matsuji Takebayaski, Toshinobu Kashiwada, Masashi Hamaguchi, Toshikazu ...
1973 Volume 2 Issue 8 Pages
809-812
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The copper chelate-catalyzed reaction of α-diazoacetophenones with substituted diphenyl sulfoxides gave two types of products, diaryl sulfides (V) and oxosulfonium ylides (VI), of which ratios depended on the substituents of α-diazoacetophenones and of diaryl sulfoxides. The oxosulfonium ylides exhibit a novel reaction with phenylglyoxal affording oxosulfonium glyoxalylphenacylides (VII) in the presence of copper acetylacetonate. When copper-phthalocyanine was employed as a catalyst, the reaction gave a lactone (X) besides (V).
View full abstract
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Hidemasa Takaya, Nobuaki Hayashi, Tatsuzo Ishigami, Ryoji Noyori
1973 Volume 2 Issue 8 Pages
813-816
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Methylenecyclopropane under the influence of nickel catalysts dimerizes to give 2-vinylmethylenecyclopentane. The intervention of butadiene intermediate has been determined on the basis of the isotope incorporation into the product and the asymmetric transformation.
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Shin-ichi Ohno
1973 Volume 2 Issue 8 Pages
817-820
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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An
ab initio calculation of the primary radiolysis yields was examined. The method is based on the classical theory developed by Thomas in 1927 for the collision between two free moving electrons. The results of applying it to the irradiation of He with 100 keV-electrons are: G
ion = 2.42, G
ex(n
1p) = 0.91, and G
ex(n
3S, n
3P) = 0.13.
View full abstract
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Hiroo Morimoto, Tadashi Furukawa, Kyoko Miyazima, Oyo Mitsunobu
1973 Volume 2 Issue 8 Pages
821-824
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The reaction of
N-benzyloxycarbonylcarboxamides with alkyl sulfonates or halides gave N-alkylated and O-alkylated products. On treatment with HBr-AcOH, the
N-alkyl-
N-benzyloxycarbonylcarboxamides were converted to
N-alkylcarboxamides. When
N-benzyloxycarbonylbenzamide was allowed to react with (
S)-(−)-ethyl lactate, triphenylphosphine and diethyl azodicarboxylate, followed by treatment with HBr-AcOH, (
R)-(−)-
N-benzoylalanine ethyl ester was obtained with high optical purity.
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Tsutomu Sakai, Yoshio Hirose
1973 Volume 2 Issue 8 Pages
825-828
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Three new sesquiterpenes related to pseudotsugona and todomatuic acid, named dihydropseudotsugonol, dihydropseudotsugonol, and ar-todomatuic acid, have been isolated from the volatile wood oil of Douglas fir. The structures and stereochemistry of these compounds have been established.
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Yoshiaki Konishi, Hiroshi Saijo
1973 Volume 2 Issue 8 Pages
829-832
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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When the thermal stabilities of a number of metal maleates in solid state were studied by means of TGA and DTA, they exhibited a remarkable exothermic process at a temperature characteristic of each metal salt. It was found that this process corresponds to the polymerization reaction of the metal maleate. In the cases of Na and Pb(II) salts, the polymer in the form of methyl esters was a brown amorphous solid ( DP \doteqdot 3 ).
View full abstract
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Kazuo Soga, Masahiro Akiyoshi, Tsutomu Kagiya
1973 Volume 2 Issue 8 Pages
833-836
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Various transition metal compounds were supported on magnesium hydroxide and propylene polymerization was carried out by using them as catalyst. The isotacticity of polypropylene was remarkably increased in comparison with that obtained with the use of carrier free catalyst, from which it has been concluded that the stereoregulation of polymer is mainly based on the crystalline structure of the catalyst not on the transition metal compound.
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Shoichi Matsumoto, Masahiro Kawamoto, Tomomichi Tsukada
1973 Volume 2 Issue 8 Pages
837-842
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Conductivity effects on the cut-off frequency f
c of the electrohydrodynamic instability were studied, using nematic liquids doped with an organic electrolyte in different concentrations. The values of f
c were obtained from the optical observation. It was found that f
c is proportional to the conductivity (ρ
−1) of the nematic liquids, just as f
c = Kρ
−1; K = 1.25×10
12Ωcm/sec. This relation supports that the space charge is responsible for the electrohydrodynamic instability.
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Shigeo Miyata, Teruhiko Kumura
1973 Volume 2 Issue 8 Pages
843-848
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The new hydrotalcite-like compounds which consist of divalent metal, trivalent metal and inorganic or organic anion were synthesized and it was found that they have many characteristic properties such as the formation of solid solutions, anion exchange and molecular sieving. Some of them were capable of separating the mixture of air and hydrogen into N
2, O
2 and H
2.
View full abstract
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Shin-ichi Tadokoro, Shizuo Fujiwara, Yoshihiro Ichihara
1973 Volume 2 Issue 8 Pages
849-852
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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C-13 NMR spectra were measured for poly-
L-methionine in CDCl
3-trifluoroacetic acid mixtures. The α- and carbonyl carbons showed upfield displacements of 2.3 and 3.4 ppm, respectively, due to the helix-coil transition of the compound. The clearly split peaks assigned to each side-chain carbon of PLM in the α -helix and the random-coil form were observed in the range of the helix-coil transition.
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Michio Hirota, Yasuo Koike, Hidehiro Ishizuka, Akira Yamasaki, Shizuo ...
1973 Volume 2 Issue 8 Pages
853-854
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Carbon-13 chemical shifts were measured for 15 cyanometallate complexes in aqueous solution with Fourier-Transform NMR spectroscopy. The chemical shift values are distributed between −50.3
3 ppm (from external benzene standard) for Fe(CN)
64− and +2.6
6 ppm for Pt(CN)
42−. The coupling constant
1J
C-Co was found to be 126 ± 4 Hz for Co(CN)
63−.
View full abstract
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Shigeo Nishimura, Hiroshi Sakamoto, Tsuyoshi Ozawa
1973 Volume 2 Issue 8 Pages
855-858
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The stereoselectivity of the platinum metals in the catalytic hydrogenation of 1,2- and 1,6-dimethylcyclohexene, 1-methyl-2-methylenecyclohexane and 6-ethoxy-1-methylcyclohexene has been studied. The formation of trans isomer increased in the order Ir < Os < Pt,Ru,Rh << Pd. This order in stereoselectivity has been related to the olefin isomerization activities of the metals.
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Tsujiaki Hata, Takashi Kurihara
1973 Volume 2 Issue 8 Pages
859-862
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Useful intermediates in the syntheses of polynucleotides, such as 3′-
O-acetyl
N4 -benzoyldeoxycytidine 5′-phosphate, 2′,3′-
O-diacetyl
N4-benzoylcytidine 5′-phosphate,
N4-benzoyldeoxycytidine and
N4-benzoylcytidine, were prepared conveniently in high yields by the use of a new mild benzoylating reagent, 2-chloromethyl-4-nitrophenyl benzoate.
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Yoshio Ueno, Makoto Okawara
1973 Volume 2 Issue 8 Pages
863-866
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The protonation of benzylidenebis(
N,
N-dialkyldithiocarbamates) with 70% perchloric acid or conc. sulfuric acid produced new four-membered heteronium salts; 2-dialkylamino-4-aryl-1,3-dithietan-2-ylium salts in high yields. A possible mechanism for the formation and the structural elucidation of 1,3-dithietan-2-ylium salts were described.
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Kazuhisa Hiratani, Hiroyuki Shiono, Makoto Okawara
1973 Volume 2 Issue 8 Pages
867-870
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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A new and useful synthetic route to 1,3-dithiolium salts involving neighboring group participation of dithiocarbamate group as a key step is described. 4-Bromo-2-dialkylamino-1,3-dithiolan-2-ylium bromide was obtained in high yield by the addition of equimolar bromine to
S-vinyl-
N,
N-dialkyldithiocarbamate, and then, pyrolysis of the salt under reduced pressure gave 1,3-dithiolium salt in excellent yield. 4-Substituted-1,3-dithiolium salts were also obtained in the same way.
View full abstract
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Norio Kunieda, Junzo Nokami, Masayoshi Kinoshita
1973 Volume 2 Issue 8 Pages
871-874
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Sulfinic esters react with methylsulfinylcarbanion to give the corresponding α-methylsulfinylmethyl sulfoxides(I) in good yields. The per cent ratio of meso form to dl form of the product obtained is about 60 : 40. When (−)-menthyl (−)-(
S)-
p-toluenesulfinate is treated with methylsulfinylcarbanion, dextrorotatory α-methylsulfinylmethyl
p-tolyl sulfoxide(IIa) is obtained. Recrystallization of (IIa) yields the diastereomerically pure (+)-(
S)-α-methylsulfinyl-(
R)-methyl
p-tolyl sulfoxide(IIb). Based on these observations, the stereochemistry of the reaction is discussed.
View full abstract
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Yoshihiro Mori, Tetsuo Ooyasu, Hiroyuki Matsuda
1973 Volume 2 Issue 8 Pages
875-876
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The translation of Na
+ with an eluent on strong electrolyte cation exchanger column is larger than that of K
+, but with electromigration smaller than that of K
+. An effective separation of Na
+ and K
+ may be expected with a simultaneous use of ion-exchange and electromigration. When an electric field[150 v(between electrodes), 3.3 mA] was applied on a strong electrolyte cation exchanger(Diaion PK-228) column(height; 10 cm, diameter; 1 cm) with parallel but reverse direction to the eluent(0.1 N NH
4Cl) flow, Na and K(each 0.5 meq) have been separated perfectly by the elution.
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Kiyonori Shinoda
1973 Volume 2 Issue 8 Pages
877-878
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The copyrolysis of 1,1,2-trichloroethane (TCE) and methanol on activated alumina was carried out at 250∼400°C. 1,1-dichloroethylene (VDC) to 1,2-dichloroethylene (DE) ratio amounted to several times of the ordinary pyrolysis. This reaction proceeded as follows.
CH
2ClCHCl
2 + CH
3OH → CH
2:CCl
2 + CH
3Cl + H
2O
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Kenji Yoshihara, Takanobu Shiokawa, Kogoro Maeda, Yosaku Nakai, Kazuyo ...
1973 Volume 2 Issue 8 Pages
879-880
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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X-ray photoelectron spectroscopy of some indium compounds was studied. Chemical shifts were found among the InM
4 or M
5 electrons emitted from metallic indium, indium oxide, indium EDTA·OH and indium EDTA. It was shown that the simple charge-binding energy relationship did not always hold good for the complex compounds studied.
View full abstract
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Manabu Ishizuka, Ken-ichi Aika, Atsumu Ozaki
1973 Volume 2 Issue 8 Pages
881-882
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Coconut carbon adsorbed with sodium or potassium vapor gives an ESR band at g=2.004 or 2.007 which diminishes on introduction of hydrogen, and catalyzes the H
2-D
2 exchange reaction, whereas the coconut carbon itself gives no such ESR and the catalytic activity.
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Hiroshi Fujita, Rokuro Endo, Keisuke Murayama
1973 Volume 2 Issue 8 Pages
883-886
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Reactions of
N,
N′-disubstituted phenylpropiolamidines with triethylammonium
N-substituted dithiocarbamates at room temperature afforded corresponding β-mercaptocinnamamidines and isothiocyanates in good yields, respectively. This constitutes a convenient route to isothiocyanates from dithiocarbamates.
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Teruo Matsuura, Akio Horinaka, Ruka Nakashima
1973 Volume 2 Issue 8 Pages
887-890
Published: August 05, 1973
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The relative reactivities of various cyclic olefins toward singlet oxygen generated by photosensitized oxygenation were determined. The differences in reactivity are mainly rationalized in term of the conformational requirements of olefins for the concerted “ene” mechanism.
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Tokio Iizuka
1973 Volume 2 Issue 8 Pages
891-892
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The generation of 2,2′- and 4,4′-dipyridyl anion radicals by adsorption on magnesium oxide was confirmed by means of electron spin resonance and visible spectroscopies. When the adsorbed species were exposed to air, the dipyridyl anion radical faded away and the ESR spectrum which was attributed to the oxygen molecule anion radical was observed.
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Yoshiya Harada, Kazuhiko Seki, Akira Suzuki, Hiroo Inokuchi
1973 Volume 2 Issue 8 Pages
893-896
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The photoelectron spectrum of vinylcyclopropane has been measured by using the 21.22 eV helium resonance lines. Eleven ionization potentials have been observed. The values of the first two ionization potentials have been explained by the conjugative interaction between the σ-orbitals of the cyclopropane ring and the bonding π-orbital of the vinyl group.
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Kiyonori Shinoda
1973 Volume 2 Issue 8 Pages
897-900
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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The chlorination of trans-1,4-dichloro-2-butene (tr-DCB-2) in chlorinated hydrocarbon solvents yielded solid and liquid isomers. When methylene chloride (
I) was used as a solvent, the solid isomer was obtained in high yield. The ionic pathway dominated in
I and was an exclusive trans-addition process.
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Tetsuo Suami, Seiichiro Ogawa, Shuichi Oki
1973 Volume 2 Issue 8 Pages
901-906
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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All eleven stereoisomers of dianhydroinositols (
1–
11), except 1,4-anhydro derivatives, have been synthesized from inositol disulfonates and their structures were established by PMR spectra together with a reaction mechanism. A migration of oxirane ring caused by participation of neighboring hydroxyl group induced an isomerization of the epoxide in an alkaline medium.
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Taro Tachibana, Toshiaki Takamatsu, Eiichi Fukada
1973 Volume 2 Issue 8 Pages
907-910
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Thermally stimulated current curves were determined for two samples of smectic liquid crystals; diethyl azoxybenzene-4, 4′-dicarboxylate and ethyl
p-(
p-ethoxybenzylidene) aminocinnamate. The curves showed peaks or kinks at phase transition points. The form of the curves was interpreted in terms of the release of impurity ions accompanying the phase transition.
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Kei Tanemoto, Tetsuro Nakamura, Toshiyuki Sata
1973 Volume 2 Issue 8 Pages
911-914
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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Magnetic susceptibilities of chloride systems containing paramagnetic ions Mn
2+(3d
5), Co
2+(3d
7) and Ni
2+(3d
8) were measured with increasing temperatures from their solid states to molten states. The susceptibility of each system obeyed the Curie–Weiss law in the both states and jumped at the melting temperature. The magnetic moments increased on melting in the systems of Co
2+ and Ni
2+ (L≠0).
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Heitaro Obara, Jun-ichi Onodera, Fumitada Yamamoto
1973 Volume 2 Issue 8 Pages
915-916
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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4′,5,6,7- and 4′,5,7,8-Tetrahydroxyflavanone (
II and
III) have been synthesized by the isomerization of 2′ ,3′ ,4,4′,6′ -pentahydroxychalcone (
I), and the structures of carthamidin and isocarthamidin were corrected by the comparison with these synthetic flavanones.
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Toshio Fuchigami, Keijiro Odo
1973 Volume 2 Issue 8 Pages
917-918
Published: August 05, 1973
Released on J-STAGE: March 27, 2006
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2-lmidoyl-3-imino-5-methylthio-Δ
4-1,2,4-thiadiazolines [
I] were easily prepared by the reaction of
N-chloroamidines [
II] with potassium methyl cyanoiminodithiocarbonate [
III]. By reduction, [
I] was readily cleft at the N–S link and was recyclized to two kinds of s-triazines, and by alkaline hydrolysis, [
I] was converted into 2-amino-4-hydroxy-s-triazine.
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Toshikazu Nagai, Kaoru Katayama, Niichiro Tokura
1973 Volume 2 Issue 8 Pages
919-922
Published: August 05, 1973
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Epr spectra were obtained from solutions of amines in liq·SO
2 due to the radical cations of the amines which might be the first observation of the electron transfer from organic molecules to liq·SO
2.
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