Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 45 , Issue 7
Showing 1-50 articles out of 86 articles from the selected issue
  • Michiya Itoh
    1972 Volume 45 Issue 7 Pages 1947-1950
    Published: 1972
    Released: March 27, 2006
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    The 2-methyltetrahydrofuran solutions of several alkali tetracyanoethylenides (M+, TCNE, where M=Na, K, Rb, and Cs) show strong visible absorption spectra at low temperature which might be considered to be charge-transfer bands between two TCNE anions. Temperature dependence of the electronic absorption and ESR spectra of TCNE in solution yields the monomer-dimer equilibrium of the TCNE anion. The heat of dimer formation of the anion was found to decrease in the order Na+>K+>Rb+>Cs+ with the size of the counter ions. The heat of dimer formation in Na+(TCNE) also depends considerably on the solvent system. The absorption spectra of the solid TCNE anions were found to resemble the spectrum of the TCNE anion dimer (TCNE)2 in solution to a great extent. A comparison of the electronic absorption and ESR spectra of M+(TCNE) in solution and in solid demonstrates that the solid TCNE is almost diamagnetic, and the anion dimer can be the unit of structure in the solid salts.
  • Eiichi Inoue, Hiroshi Kokado, Isamu Shimizu, Hajime Kobayashi, Yohnosu ...
    1972 Volume 45 Issue 7 Pages 1951-1956
    Published: 1972
    Released: March 27, 2006
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    The unstable colorless form (A′) of the reverse photochromic spiran (SP-3) (1,3,3-trimethyl-5-methoxyspiro[indoline-2,2′-benzopyran]-8′-carboxylic acid) was obtained in a stable state by vacuum evaporation (10−5 Torr) on a KBr substrate. It was confirmed by IR spectral analysis that reverse photochromism occurred between the colored (B′; merocyanine-like structure) and the colorless forms (A′; spiropyran). A colorless transient intermediate (X) was observed in the photo-decoloration process of the (SP-3). X was transformed into both A′ and B′. Thus the photo-decoloration efficiency (φB′→A′) depends on the ratio of the conversion from X to A′. State (B′) is stabilized in a polar or proton donative solvent. The life time of X is greatly influenced by the solvent as well as the stability of B′. The photo-decoloration efficiency (φB′→A′) of the spirans is effectively improved by substituting SP-2 with (methoxyl group) at 5-position. Whether X is observable or not depends on the substituent and its position. The reversibility of photochromic cycle of the spirans was restricted by the photobleaching of B′ by UV irradiation. It was observed that the photo-bleaching of B′ is accelerated in a degassed solution.
  • Masaru Ichikawa, Sadao Tanaka, Shuichi Naito, Takahiro Nakamura, Mitsu ...
    1972 Volume 45 Issue 7 Pages 1956-1960
    Published: 1972
    Released: March 27, 2006
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    The mechanisms of the H2–D2 and D2–HZ exchange reactions over 1 : 2 Electron Donor-Acceptor (EDA) complexes of anthracene with sodium, where HZ denotes the EDA complexes, were studied kinetically and spectroscopically in the temperature range 20–90°C. It was found that molecular hydrogen exchanges directly with the hydrogen of the complexes (An2−2Na+ or AnNa+) and also with the monohydroanion complex (AnHNa+), which is formed by the dissociative adsorption of hydrogen. The H2–D2 exchange reaction proceeded via not only the σ-bonded hydrogen of the complexes, but also homolytically dissociated “mobile” hydrogen.
  • Keiichiro Adachi, Hiroshi Suga, Syûzô Seki
    1972 Volume 45 Issue 7 Pages 1960-1972
    Published: 1972
    Released: March 27, 2006
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    The heat capacities of 8 kinds of stable and meta-stable crystalline phases including the glassy crystal of cycloheptanol were measured at temperatures from 13 to 300 K. The crystalline phases have been named crystals I, II, II′, III, III′, III″, Iβ, and glassy crystal. Transition temperatures between crystals II and I, III and II, II′ and II, III′ and III, III″ and III were determined to be 258.45, 227.26, 172.23, 152.30, and 128.2 K, respectively. The melting point and glass transition point of the glassy crystal were determined to be 280.30 and 140 K, respectively. The heats of transition between crystals II and I, III and II, III′ and III and the heat of melting were determined to be 876, 554, 58.1, and 1604Jmol−1, respectively. The residual entropy of the glassy crystal was found to be 0.7 JK−1mol−1 assuming that of crystal III′ to be zero. The stabilization phenomenon in the glassy crystalline state was also studied from the measurements of enthalpy relaxation. The stability of the various phases was determined by calculating their free energies. The degree of freedom which is frozen in the glassy crystalline state was discussed from molecular viewpoints. Classification of various phase transitions found in this material was also made from the viewpoint of thermodynamical stability.
  • Akinori Inoue, Keitaro Yoshihara, Saburo Nagakura
    1972 Volume 45 Issue 7 Pages 1973-1976
    Published: 1972
    Released: March 27, 2006
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    The bimolecular annihilation of singlet excitons in pyrene, perylene, and anthracene crystals was studied by the aid of a nitrogen gas laser. The rate constant, γ, for bimolecular annihilation was estimated at 293°K to be 9×10−15 and 8×10−14 cm3 sec−1 for pyrene and perylene, respectively. The temperature dependence of γ was measured with the result that it increases with the increasing temperature for the pyrene and perylene crystals, while it is almost independent of temperature for anthracene between 77°K and 293°K. The difference in the temperature dependence of γ was attributed to the difference in the mechanism of the exciton migration of the crystals. The method developed by the present authors for studying the exciton migration based on the exciton bimolecular annihilation was compared with that obtained previously by the use of mixed crystals.
  • Yusaku Ikegami, Hidetoshi Watanabe, Shuichi Seto
    1972 Volume 45 Issue 7 Pages 1976-1978
    Published: 1972
    Released: March 27, 2006
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    The ESR spectrum of the tropone anion radical has been examined. The radical was generated from the neutral species by the electrolytic reduction in N,N-dimethylformamide. Splitting constants are satisfactorily explained in terms of the calculated spin densities by the McLachlan procedure, confirming that the unpaired spin orbital belongs to an a2 symmetrical species. The complete delocalization of the π-electrons was assumed for the anion radical.
  • Hiroshi Suzuki, Kinko Koyano, Tosiyasu L. Kunii
    1972 Volume 45 Issue 7 Pages 1979-1988
    Published: 1972
    Released: March 27, 2006
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    Stilbene and some of its alkyl-substituted derivatives were reduced with alkali metals to dianions in 1,2-dimethoxyethane. From comparison of the electronic absorption spectra of these dianions with one another and with the results of semiempirical SCF-MO-CI calculation of the π-electronic state, the geometries of the dianions were inferred to be as follows: (a) the preferred geometry of a sterically unhindered dianion, such as the dianion of stilbene, is probably planar or nearly planar; (b) when alkyl substituents are introduced into the central ethylenic carbon atoms, the steric interference caused by the substituents is relieved chiefly by the rotation about the central ethylenic bond; (c) the steric interference caused by ortho methyl substituents seems to be comparatively small or to be relieved by the rotation about the bonds connecting benzene rings to the ethylenic carbon atoms as well as the ethylenic bond. From the influence of alkali-metal cations on the spectra of the dianions, it was inferred that the dianions exist mainly as contact ion aggregates in which the counter-ions are located near the central ethylenic bond, one probably almost above an ethylenic carbon atom and the other almost below the other ethylenic carbon atom.
  • Takashi Tamaki, Yasuzo Suzuki, Masaki Hasegawa
    1972 Volume 45 Issue 7 Pages 1988-1992
    Published: 1972
    Released: March 27, 2006
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    The effect of the wavelength of an exciting light on four-center-type photopolymerization in the crystalline state has been investigated. 2,5-Distyrylpyrazine (DSP), 1,4-bis[β-pyridyl-(2)vinyl]benzene (P2VB), p-phenylenediacrylic acid (p-PDA) dimethyl ester were converted quantitatively into highly crystalline oligomers (pentamers on the average) on irradiation at the long-wavelength edge of the absorption of the monomer. On subsequent exposure to the light which is absorbed by each oligomer, the oligomer crystals as-polymerized were converted quantitatively into high polymer crystals. The polymer thus obtained was found to be identical with the polymer produced by the light of a xenon or a high-pressure mercury lamp. The quantum yields for the oligomerization and polymerization reactions of DSP and the p-PDA dimethyl ester were found to be between 1 and 2 on the basis of the number of olefinic double bonds consumed to form the cyclobutane ring. These results confirmed that the four-center-type photopolymerization in the crystalline state consists of two kinds of separable, step-by-step addition mechanisms: an oligomerization of the dioleflnic compound and a growth reaction of the terminal group in the growing chain. From the crystallographic information on the DSP oligomer, the oligomerization as well as the polymerization process of DSP were concluded to proceed by a monomer lattice-controlled mechanism.
  • Michinori Oki, Hiroshi Nakanishi
    1972 Volume 45 Issue 7 Pages 1993-1995
    Published: 1972
    Released: March 27, 2006
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    The presence of two or three conformational isomers in monothiocarbonates has been confirmed by nuclear magnetic resonance and infrared spectroscopies and by dipole moment techniques. The data can best be interpreted by assuming that the conformations involving the s-cis conformation are more stable than that of s-trans, s-trans.
  • Yoshio Inoue, Teruhiko Kagawa, Yasuzo Uchida, Harukichi Hashimoto
    1972 Volume 45 Issue 7 Pages 1996-1999
    Published: 1972
    Released: March 27, 2006
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    The cooligomerization of butadiene and ethylene catalyzed by a NiCl2–AlEt3–phosphine system was investigated. The cooligomerization product was 1,cis-4-hexadiene or/and 1,trans-4,9-decatriene. Bidentate ditertiary phosphines had remarkable effects on the reaction. The effects of ditertiary phosphines are also described.
  • Hiroshi Tanida, Tadashi Irie, Kazuo Tori
    1972 Volume 45 Issue 7 Pages 1999-2003
    Published: 1972
    Released: March 27, 2006
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    Transient 8,8-dimethylisobenzofulvene (5) was generated by thermal decomposition of two materials; one is formally an adduct of cyclopentadienone with 9-isopropylidenebenzonorbornadiene (6), and the other an adduct of 3,6-di(2′-pyridyl)-S-tetrazine with 6. The former was prepared by cycloaddition of 6 to tetrachlorodimethoxycyclopentadiene followed by dechlorination giving a ketal, then hydrolysis of the ketal function. Generation without any trapping reagent instantaneously yielded one kind of dimer of a stereospecific structure. In the presence of dimethyl maleate, dimethyl 9-isopropylidenebenzonorbornene-exo,cis-2,3-dicarboxylate and its endo-cis isomer were formed. In the presence of dimethyl fumarate, the trans isomer was obtained. Trapping with tropone led to a 1 : 1 adduct resulting from participation of the exocyclic C2–C8 double bond in 5. All attempts to isolate 5 or prepare a stable metal complex of 5 by conventional means were unsuccessful.
  • Kiyotomi Takao, Hiromichi Azuma, Yuzo Fujiwara, Toshinobu Imanaka, Shi ...
    1972 Volume 45 Issue 7 Pages 2003-2006
    Published: 1972
    Released: March 27, 2006
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    The oxidation of styryl acetate, vinyl acetate, vinyl propionate, methyl acrylate, and methyl cinnamate with RhCl(PPh3)3 catalyst has been studied. The reaction is remarkably affected by the substituent on an olefinic carbon atom. The oxidation mechanism was discussed in connection with decarbonylation.
  • Toshiyuki Shono, Yuko Yamashoji, Koichiro Shinra
    1972 Volume 45 Issue 7 Pages 2007-2009
    Published: 1972
    Released: March 27, 2006
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    Various copper(II) chelates were found to be effective initiators in the polymerization reaction of the methyl methacrylate in the presence of triphenylphosphine. The conversion increases with an increase in the concentration of triphenylphosphine, reaching a constant level at the ratio of 1: 2 between copper chelates and triphenylphosphine. Di-μ-methoxo-bis(ethylacetoacetato)dicopper(II) was the most effective initiator. The dependence of the rate of the polymerization on the square root of the concentration of the complexes suggests that the polymerization by this initiation system proceeds via a radical mechanism. It can be assumed that the copper chelate coordinated the triphenylphosphine and that homolytic fission occurred to give a free ligand radical, accompanied by the reduction of the central copper atom. Stable copper (I) mixed chelates were obtained under conditions similar to those of the polymerization.
  • Takenori Nishino, Masumi Kiyokawa, Yoshiyuki Miichi, Kanji Tokuyama
    1972 Volume 45 Issue 7 Pages 2010-2015
    Published: 1972
    Released: March 27, 2006
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    The reaction of 2-dimethoxymethyl-3-methoxypropionitrile (1) with acetamidine produces pyrimidopyrimidine (8) via the consecutive process of 1→an intermediate→8. The intermediate was not isolated, but two structures have been proposed for it. We have now succeeded in the isolation of the intermediate and determined it to be 2-methyl-4-amino-5-dimethoxymethyl-5,6-dihydropyrimidine (4). Several key intermediates were also successfully isolated. The novel reaction pathway for the title reaction was concluded to be as follows: the elimination of methanol from 1, followed by the addition of acetamidine affords 3-acetamidinopropionitrile (3), the subsequent quick cyclization of which produces the intermediate, 4; the further elimination of methanol from 4, followed by a replacement reaction with acetamidine, gives an acetamidinomethylene compound (6), which is converted into the final product, 8, via an intermediate (7). Some minor pathways will also be presented.
  • Yasuo Ariyoshi, Naotake Sato
    1972 Volume 45 Issue 7 Pages 2015-2018
    Published: 1972
    Released: March 27, 2006
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    The methyl and ethyl esters of α-L-aspartyl-L-phenylalanine (I and II), -L-tyrosine (III and IV), -L-(β-cyclohexyl)alanine (V and VI), and -L-[β-(4-hydroxycyclohexyl)]alanine (VII and VIII) have been found to react with ketones (acetone, methyl ethyl ketone, and cyclohexanone), in the absence of any catalysts, to give the corresponding 4-imidazolidinone derivatives (XVII–XXX). The NMR spectra of the imidazolidinones with an aromatic side chain (XVII–XXVIII) have indicated that these compounds exist in the folded conformation (in which the aromatic ring faces the imidazolidinone ring) in the solution. The imidazolidinones (XVII–XXX) were hydrolyzed with hot water to give the peptide esters (I–VIII), all in their original optical purity. On the other hand, the β-isomers of the peptide esters (IX–XVI) did not react with these ketones under the same conditions. These characteristics were used successfully in the separation of the two structural isomers of these peptide esters.
  • Shigeru Oae, Toshiaki Yoshimura, Naomichi Furukawa
    1972 Volume 45 Issue 7 Pages 2019-2022
    Published: 1972
    Released: March 27, 2006
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    The reactions of diphenyl (I), phenyl benzyl (II), and phenyl methyl N-p-tosylsulfilimines (III) with phenylmagnesium bromide were carried out. (I) gave biphenyl and diphenyl sulfide in high yields. A tracer experiment with diphenyl sulfilimine-1-14C revealed that the reaction proceeds via the initial formation of triphenylsulfonium salt upon which the attack of phenylmagnesium bromide affords the products. “Benzyne” mechanism is ruled out. (II) and (III) gave various compounds, the major products being α-phenylated sulfides which are presumed to be formed by the Pummerer type rearrangement initiated by the abstraction of α-proton by the Grignard reagent.
  • Gen-ichi Tsuchihashi, Katsuyuki Ogura
    1972 Volume 45 Issue 7 Pages 2023-2027
    Published: 1972
    Released: March 27, 2006
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    Ghloromethyl methyl sulfoxide undergoes a Darzens-type reaction with carbonyl compounds in the presence of potassium t-butoxide in t-butanol to afford methylsulfinyloxirane derivatives. The stereochemistry of this reaction has been studied. The reaction with a symmetrical ketone appeared to proceed stereospecifically to give only one isomer. On the other hand, the reaction with unsymmetrical ketones such as pinacolone or acetophenone produced a mixture of two diastereoisomers, in which a thermodynamically unstable isomer was predominant. The reaction with thiobenzophenone gave 1,1-diphenyl-2-methylsulfinylethylene which seems to have been formed from the intermediacy of 2,2-diphenyl-3-methylsulfinylthiirane. Mechanisms of these reactions are also discussed.
  • Juji Yoshimura, Hideo Sakai, Nobuteru Oda, Hironobu Hashimoto
    1972 Volume 45 Issue 7 Pages 2027-2032
    Published: 1972
    Released: March 27, 2006
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    Preparation of 2-acetamido-2-deoxy-D-mannose (2) by epimerization of the corresponding D-glucose was improved by addition of Ni2+ ion to the equilibration system, and several derivatives of (2) were synthesized. N-glycosides were obtained by using ammonium chloride as a catalyst, and p-nitrophenyl glycoside by a fusion method. The composition of four isomers in benzylglycosidation of (2) was determined to be 66% α-pyranoside (6), 11% β-pyranoside, 16% α-furanoside (5) and 7% β-furanoside. Benzylidenation of 6 gave the corresponding 4,6-O-benzylidene derivative which was converted into the 3-O-acetate (8) by acetylation, and to the corresponding 2-amino-2-deoxy derivative by treatment with ethanolic potassium hydroxide. Oxidation of 6 with oxygen in the presence of platinum-charcoal and following esterification gave the corresponding methyl uronate which was derived to the di-O-acetate (11). Periodate oxidation and the following hydrogenation of 5 gave benzyl 2-acetamido-2-deoxy-α-D-lyxofuranoside which was then derived to di-O-acetate (13). Nitromethane condensation of 2 in barium hydroxide solution gave one isomeric 1-C-nitro-1-deoxy-D-heptitol which was converted into methyl 3-acetamido-3-deoxy-D-gaycero-D-galacto-α-heptopyranoside (18). First-order analyses of NMR spectra of 8, 11, 13, and tetra-O-acetate of 18 are described.
  • Minoru Kojima, Hiroshi Minato, Michio Kobayashi
    1972 Volume 45 Issue 7 Pages 2032-2035
    Published: 1972
    Released: March 27, 2006
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    Aryl arylazo sulfones were prepared, and the rates of homolyses in chlorobenzene were determined in the presence of a base for suppression of acid catalysis at 80–118°C. An isokinetic relationship was found to hold between ΔH\ eweq and ΔS\ eweq (β=101.0°C). The substituents on the benzenesulfonyl group influenced the rates very little, whereas the substituents on the phenylazo group decreased the rates (especially the electron-releasing substituents).
  • Ryuki Hisada, Michio Kobayashi, Hiroshi Minato
    1972 Volume 45 Issue 7 Pages 2035-2039
    Published: 1972
    Released: March 27, 2006
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    Reactions of benzoyl p-toluenesulfonyl peroxide (BTP) with several nucleophiles were investigated. The reaction with triphenylphosphine gave benzoyl p-toluenesulfonate and triphenylphosphine oxide, that with diphenyl sulfide gave benzoyl p-toluenesulfonate and diphenyl sulfoxide, and that with p-tolylmagnesium bromide gave p-toluenesulfonate and benzoic acid. In the reaction of BTP[carbonyl-18O] with triphenylphosphine, 88% of carbonyl oxygen-18 was retained as the carbonyl oxygen of the benzoyl p-toluenesulfonate formed, whereas in the reaction of BTP[carbonyl-18O] with diphenyl sulfide only 58% of the label in the starting peroxide was found in the carbonyl oxygen of the benzoyl p-toluenesulfonate formed. In the reaction of BTP[sulfonyl-18O] with p-tolylmagnesium bromide, it was found that the two sulfonyl oxygens of BTP were completely retained in the two sulfonyl oxygens of the p-tolyl p-toluenesulfonate formed. Possible mechanisms of these reactions are discussed.
  • Michio Kobayashi, Sadao Fujii, Hiroshi Minato
    1972 Volume 45 Issue 7 Pages 2039-2042
    Published: 1972
    Released: March 27, 2006
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    Photolysis of phenylazo p-tolyl sulfone and p-chlorophenylazo p′-tolyl sulfone in aromatic solvents at room temperature was investigated. The products were analyzed, and the isomer distribution and partial rate factors in arylation of mono-substituted benzenes were determined. The results indicate that the photolysis involves formation of aryl radicals and p-tolylsulfonyl radicals.
  • Nobumasa Kamigata, Hiroshi Minato, Michio Kobayashi
    1972 Volume 45 Issue 7 Pages 2042-2046
    Published: 1972
    Released: March 27, 2006
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    Anisole-4d, chlorobenzene-4d, chlorobenzene-d5, nitrobenzene-d5, m-dinitrobenzene-d4, and 1,3,5-tri-t-butylbenzene-d3 were phenylated with phenyl radical generated from PhN2BF4–NaNO2, N-nitrosoacetanilide or phenylazotriphenylmethane(PAT), and the isotope effect in these phenylations was determined. The values of kHkD in the phenylations of chlorobenzene and 1,3,5-tri-t-butylbenzene are not so larger than unity, whereas that in the phenylation at the 2-position of m-dinitrobenzene with PAT was very large (∼11).
  • Nobumasa Kamigata, Michio Kobayashi, Hiroshi Minato
    1972 Volume 45 Issue 7 Pages 2047-2050
    Published: 1972
    Released: March 27, 2006
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    The cationic arylation of substituted benzenes was investigated with p-nitrophenyl cation generated from p-nitrobenzenediazonium tetrafluoroborate in acetonitrile and from p-nitrophenylazo p′-tolyl sulfone in the presence of trifluoroacetic acid. The isomer distribution of substituted nitrobiphenyls produced and the partial rate factors indicated electrophilic character of the p-nitrophenyl cation. Selectivity of p-nitrophenyl cation is low compared with those of nitronium or sulfonyl cation, and similar to that of phenyl cation. These facts suggest that the p-nitrophenyl cation functions as a cation diradical with concerted uncoupling of a pair of π-electrons, one of which falls into the vacant sp2 σ-orbital.
  • Tadashi Sasaki, Ken Kanematsu, Akikazu Kakehi, Gin-ichi Ito
    1972 Volume 45 Issue 7 Pages 2050-2052
    Published: 1972
    Released: March 27, 2006
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    The 1,3-dipolar cycloaddition of substituted 1-benzoyliminopyridinium ylides (1, 6, and 9) with dimethyl acetylenedicarboxylate (DAG) produced the corresponding rearrangement compounds (3, 4, 7, 8, and 10). On the other hand, the similar reaction of 11 with DAC in acetonitrile gave 12, accompanied with a Sommelet-type rearrangement compound, 13. The structural elucidation of these products was accomplished by spectral inspections.
  • Ko Taki, Pil Hyon Kim, Susumu Namba
    1972 Volume 45 Issue 7 Pages 2052-2055
    Published: 1972
    Released: March 27, 2006
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    The reactive species, CN radicals, were produced by the irradiation of the focused laser beam on the metal cyanide target. The reaction of CN radicals with low-molecular-weight hydrocarbons gave fragmented hydrocarbons and CN (and NC) compounds, while that with hydrogen gave hydrogen cyanide. From the experimental results, it seems that the products may be formed mainly by the reaction of the reactive species with fragment hydrocarbon radicals which are produced by the collision of the high-temperature reactive species (CN*) with the parent hydrocarbons.
  • Ichiro Hirao, Yasuhiko Kato
    1972 Volume 45 Issue 7 Pages 2055-2057
    Published: 1972
    Released: March 27, 2006
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    In a continuation of our previous papers concerning the syntheses with 5-nitro-2-furonitrile, 2-(5-nitro-2-furyl)vinyl-1,2,4-oxadiazoles and -1,2,3-triazoles were prepared from 3-(5-nitro-2-furyl)acrylonitrile (I). When I was treated with diazomethane in ether, 4-[2-(5-nitro-2-furyl)vinyl]-1,2,3-triazole (II) was obtained. II gave N-acetyl (IIa) and N-morpholinomethyl (IIb) compounds when treated with acetic anhydride and when the Mannich reaction was utilized respectively. 3-(5-Nitro-2-furyl)acrylamide oxime (III) was prepared by the usual method from I and hydroxylamine. The treatment of III with benzaldehyde and acid anhydrides or chlorides afforded 3-[2-(5-nitro-2-furyl)vinyl]-5-phenyl-4,5-dihydro-1,2,4-oxadiazoline (IV) and O-acyl-3-(5-nitro-2-furyl)acrylamide oximes (IIIa—IIIe) respectively. The O-acyl-amide oximes were found to cyclize to 3-[2-(5-nitro-2-furyl)vinyl]-5-alkyl-1,2,4-oxadiazole (V–VII) in their thermal analyses.
  • Takayuki Suga, Nobuo Iwata, Yoshinori Asakawa
    1972 Volume 45 Issue 7 Pages 2058-2060
    Published: 1972
    Released: March 27, 2006
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    The structure of alnustone (1) isolated from the male flower of Alnus pendula Matsum. has been established to be 1,7-diphenyl-1,3-heptadien-5-one. Previously-known compounds, β-phenylethyl cinnamate (6), cinnamaldehyde, benzylacetone, β-phenylethyl alcohol, pinocembrin (7), pinostrobin (8), alpinetin (9), galangin (11), pinosylvin (13), and its monomethyl ether (14), eugenol, chavicol, cinnamic acid, β-phenylpropionic acid, and benzoic acid, were identified along with the above new ketone.
  • Takayuki Suga, Kiyoshi Imamura
    1972 Volume 45 Issue 7 Pages 2060-2064
    Published: 1972
    Released: March 27, 2006
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    The conformations of flexible, cyclic α,β-unsaturated ketones, (−)-p-menth-3-en-5-one (1), (+)-carvone (2), (−)-piperitone (3), (−)-carvenone (4), and (+)-pulegone (5), were examined by means of the temperature-dependent circular dichroism (CD) in the region of the n* transition. In polar solvents, the simultaneous occurrence of the conformational equilibrium and the asymmetric solvation was observed markedly for the compound 1 of these compounds, along with a change in the large rotational strength at lower temperatures.
  • Tetsuo Shiga, Hitoshi Yamaoka, Kazuo Arakawa, Toshio Sugiura
    1972 Volume 45 Issue 7 Pages 2065-2069
    Published: 1972
    Released: March 27, 2006
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    The formation of negative ions and the negative ion-molecule reaction in nitroethylene by electron impact have been studied. The nondissociative resonance electron capture of the nitroethylene molecule led to the formation of the molecular negative ion. The ionization efficiency curves and the appearance potentials of several fragment negative ions and the molecular negative ion were measured. The dimer negative ion of nitroethylene was found to be formed by the ion-molecule reaction between the molecular negative ion and a neutral nitroethylene molecule, and the rate constant of this ion-molecule reaction was estimated to be approximately 3.2×10−13 cc molecule −1sec−1.
  • Juziro Nishijo, Isamu Imanishi, Genzo Hashizume
    1972 Volume 45 Issue 7 Pages 2070-2074
    Published: 1972
    Released: March 27, 2006
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    For the crystallization of aminomalonic acid with several amino acids from an aqueous solution, solid complex formation was studied by means of an X-ray diffractometer. No complex formation of aminomalonic acid with α-alanine, dl-α-amino-n-butyric acid, l-isoleucine, l-leucine, dl-serine, dl-norleucine, α-amino-iso-butyric acid, dl-valine, dl-threonine, or dl-norvaline was observed. However, with β-alanine, the formation of a solid complex with a molar ratio of 1:1 was ascertained. When this solid complex was analyzed by the differential thermogravimetric method in air at a heating rate of 1.4°C/min, a decarboxylation reaction, accompanied by endothermic and exothermic peaks, was observed at 115–133°C. On the other hand, the decarboxylation of aminomalonic acid alone occurred in the temperature range of 112–138°C. The areas of the endothermic peak, which was attributed to the decarboxylation, and the endothermic peak, which was attributed to the crystallization energies of γ-glycine and β-alanine, were, respectively, about 3 and 3/2 times those of the peaks observed in the case of aminomalonic acid. It was also observed that the exothermic process proceeded in two steps. The X-ray analysis of the products of the decarboxylation process suggested that the complex first melted to become amorphous to X-rays, and that it was then decarboxylated to amorphous glycine and amorphous β-alanine with these subsequent crystallization. The two-step exothermic process was explained in terms of a somewhat earlier crystallization of amorphous glycine than in terms of that of the amorphous β-alanine. The activation energy of the solid complex was estimated to 119.2 kcal/mol from the thermogravimetric curve. This large value of the apparent activation energy may be considered to result because the solid complex turns to an amorphous phase much more sensitive to decarboxylation prior to decomposition, and the steep slope of the thermogravimetric curve which results from the rapid decarboxylation of the amorphous gives the large apparent activation energy.
  • Shinji Takahashi
    1972 Volume 45 Issue 7 Pages 2074-2078
    Published: 1972
    Released: March 27, 2006
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    The diffusion coefficients of radioactive methane (CTH3) in normal methane, in carbon dioxide, and in a mixture of normal methane with carbon dioxide (0.522 mol fraction of methane) were measured at the temperatures of 25, 50, and 75°C in the 15–250 atm pressure range. The measurements were made through a plug of porous bronze in the diffusion cell, using the radioactive tracer technique. The diffusion coefficient-density products, Dρ, for the CTH3–normal methane system and the CTH3- the binary mixture system increased slightly with an increase in the density in the lower-density region at 25 and 50°C, but they were nearly constant at 75°C. The Dρ for the CTH3–carbon dioxide system decreased with an increase in the density at each temperature. The Dρ-values at 1 atm, obtained by extrapolation, agreed fairly well with those reported in the literature. The density dependence of the Dρ values at high densities could not be predicted by Enskog-Thorne’s theory.
  • Kanjiro Matsuura, Akira Suzuki, Mitsuomi Itoh
    1972 Volume 45 Issue 7 Pages 2079-2083
    Published: 1972
    Released: March 27, 2006
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    An account was given of the surface acidic properties of a series of BF3-treated aluminum oxides, ranging in their precalcination temperature up to 1000°C. It was concluded that all aluminum oxides dehydrated over 300°C were converted to solid acids with new strong acid centers of H0≤−8.2 by adsorption with BF3. This new acid centers would be certainly of the Brönsted type. Their catalytic activities in some carbonium ion type reactions are well correlated with the n-butylamine acidity in the presence of Hammett’s indicators, and the maximum number of acid centers was observed in catalyst samples precalcined at 450 and 800°C respectively. The present study also suggests that the acid centers developed on the surface of aluminum oxides are somewhat different in nature depending upon their precalcination temperatures. Since there was a good correlation between the amount of the remaining hydroxyl groups and that of the absorbed BF3, the surface hydroxyl groups, in addition to the aluminum atoms serving as the Lewis centers, which are not fully coordinated, were discussed as the most important factors in the formation of such acid centers.
  • Nobuhide Tatsumoto, Takayuki Sano, Norihiko Matsunaga, Eiso Tochigi, T ...
    1972 Volume 45 Issue 7 Pages 2083-2087
    Published: 1972
    Released: March 27, 2006
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    The effect of a solvent on the ultrasonic relaxation of propionic acid has been studied. The relaxation frequency is affected a little in hydrophilic solvents, while in non-hydrophilic solvents it shifts to a higher-frequency side. The activation enthalpy in a reaction from open to cyclic dimers decreases with dilution in the non-hydrophilic solvents; the magnitude of the change in the hydrophilic solvents is less than in the non-hydrophilic solvents. This means that the open dimer is destabilized by non-hydrophilic solvents. The sequence of the magnitude of the solvent effect on the relaxation frequency is consistent not with that estimated from the magnitude of the dielectric constant of the solvent, but with that estimated from the magnitude of the non-hydrophilic strength of the solvent. The stability of an open dimer in a hydrophilic or polar solvent is attributed to the interaction of the free OH group on the open dimer with the solvent.
  • Raj Deo Singh, Ram Gopal
    1972 Volume 45 Issue 7 Pages 2088-2090
    Published: 1972
    Released: March 27, 2006
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    Ion-solvent interaction of the tetraalkylammonium ions (R4N+) in N-methylformamide and N-methylpropionamide has been investigated from the electrical conductance point of view. It appears that the R4N+ ions act as net structure breakers in these solvents as in N-methylacetamide. The appreciable negative deviation of the experimental slope of the Λ vs. \sqrtc curves from the theoretical slope suggests some kind of obstruction to the movement of the R4N+ ions, probably due to their unwieldy size or to some kind of cation-anion association, although the usual kind of association is ruled out in view of the high dielectric constant of these solvents. The cation-anion interaction may be the penetration of the cations by the anions which has been suggested as a possible reason for the negative slope in the apparent molal volume vs. \sqrtc curves, obtained at higher concentrations, to which apparent molal volume measurements usually have to be confined on account of difficulties in accurate density measurements at low concentrations. The smaller alkali metal ions appear to be more solvated than the R4N+ ions, so much so that the λ0+-values of Na+ and K+ ions are lower than the corresponding values of the Me4N+ and Et4N+ ions.
  • Yukiteru Katsube, Tomitake Tsukihara, Nobuo Tanaka, Kazuto Ando, Takas ...
    1972 Volume 45 Issue 7 Pages 2091-2096
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of averufin has been determined by means of the X-ray diffraction method. The space group is P21/a, with a=23.70 Å, b=7.24 Å, c=9.48 Å, and β=105.5°. The structure was solved by the interpretation of the three-dimensional Patterson function and was refined by the least-squares method. The molecular structure is in agreement with that proposed by Roffey and Grandjean. In the crystal, the molecules are linked to form a molecular pair by a OH···O hydrogen bond across the center of symmetry.
  • Kazuo Kan, Yoshio Matsunaga
    1972 Volume 45 Issue 7 Pages 2096-2100
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The electrical resistivities and Seebeck coefficients of 2: 3 iodine complexes of N-methyl- and N-ethyl-phenothiazines were measured. The former complex exhibits a resistivity of 2.0 ohm cm and an activation energy for semiconduction of 0.20 eV at 20°C. Applying the equation of Johnson and Lark-Horowitz for the Seebeck coefficient of an intrinsic semiconductor, the ratio of the electron mobility to the hole mobility in the N-methyl-phenothiazine complex was found to be 2.08 and the electron mobility was estimated as 0.23 cm2/Vsec. The resistivity of the N-ethylphenothiazine complex is 74 ohm cm, and the activation energy 0.15 eV at 20°C. In this complex, the hole appears to be more mobile by a factor of five than the electron. Lichtenecker’s logarithmic rule is observed neither by the resistivity nor by the activation energy of the mixtures of these two complexes.
  • Masayuki Nakagaki, Yoh Sano
    1972 Volume 45 Issue 7 Pages 2100-2107
    Published: 1972
    Released: March 27, 2006
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    The denaturation of bovine serum albumin (BSA) by guanidine hydrochloride (GuHCl) was studied by means of the light-scattering method. The Zimm plots were curved so that apparently imaginary values of the radius of gyration were obtained, but the modified Zimm plots, drawn by applying the correction factor for the optical anisotropy of segments, gave reasonable values of the weight-average molecular weight, the radius of gyration, and the second virial coefficient. The correction factor was calculated by using the experimental values of the scattering ratio at 90° of the scattering angle. The analysis of the intrinsic viscosity showed that the BSA molecules were elongated. According to these results, it has been concluded that the BSA molecules are streched by the denaturation the more as the GuHCl concentration is higher, and that the denatured BSA molecules, at first, form dimers by the side-by-side aggregation of two molecules, but that the intermolecular bindings, too, are broken with the further addition of GuHGl. The length reached at 5M GuHGl was about 1/5 of the fully stretched length. This suggests the possibility that the denatured BSA molecules can keep their local natural conformations.
  • Reiji Tanaka, Sachio Murakami, Ryoichi Fujishiro
    1972 Volume 45 Issue 7 Pages 2107-2110
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    An isothermal displacement calorimeter of the Van Ness type has been constructed. The calorimeter was tested on three systems, benzene+cyclohexane, cyclohexane+n-hexane, and benzene+dichloromethane, at 25°C, and the performance of the calorimeter was discussed in connection with the literature values. The precision of the new calorimeter was within 0.5%; this was equal to, or better than, that of calorimeters of a similar type which have been constructed by several investigators.
  • Makoto Watanabe, Tetsushi Senda
    1972 Volume 45 Issue 7 Pages 2111-2113
    Published: 1972
    Released: March 27, 2006
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    Mono-, di-, or trisodium orthophosphate was heated at 100°C in an equivolume mixture of acetic acid and its anhydride. By X-ray diffractometry and paper chromatography, the products from these three sodium salts of orthophosphate were found to be sodium trimetaphosphate. At the end of the 30-hr reaction period, the purity of the trimetaphosphate was higher than 90%. The ease of formation of the trimetaphosphate ring under various conditions was shown, and the stability of the ring was discussed on the basis of the strain of the bonding angle.
  • Tsuguo Tanaka
    1972 Volume 45 Issue 7 Pages 2113-2120
    Published: 1972
    Released: March 27, 2006
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    In order to study the influence of the side-chain carboxylic acid groups on the formation of the metal chelates, 5-bromo-3-carboxymethyl-, 5-methyl-3-β-carboxyethyl-, and 5-chloro-3-β-carboxyethyl-salicylaldehyde (2a, b c) were synthesized. The green binuclear copper chelates of these aldehydes, di-μ-aquo-bis-(5-bromo-3-carboxymethylsalicylaldehyde)-, di-μ-aquo-bis-(5-methyl-3-β-carboxyethylsalicylaldehyde)-, and di-μ-aquo-bis-(5-chloro-3-β-carboxyethylsalicylaldehyde)-dicopper (11a, b, c) yielded the green binuclear bis-ethylenediimine chelates (12a, b, c), while bis-(5-bromo-3-carboxymethylsalicylaldehyde)-, bis-(5-methyl-3-β-carboxyethylsalicylaldehyde)-, and bis-(5-chloro-3-β-carboxyethylsalicylaldehyde)-ethylenediimine (14a, b, c) gave a brown (13a) and gray-purple (13b, c) mononuclear copper chelates. The reduction of 14a, b, c with sodium borohydride yielded the ihexadentate ligands N,N′-bis-(5-bromo-2-hydroxy-3-carboxymethylbenzyl)-, N,N′,-bis-(5-methyl-2-hydroxy-3-β-carboxyethylbenzyl)-, and N,N′-bis-(5-chloro-2-hydroxy-3-β-carboxyethylbenzyl)-ethylenediamine (15a, b, c), which proved useful for the spectrophotometric determination of the copper (II) ion from solutions containing copper (II) and nickel (II) ions, and the iron (II) ion from solutions containing iron (II) and nickel (II) ions.
  • Akira Ohyoshi, Akinori Jyo, Noriaki Shin
    1972 Volume 45 Issue 7 Pages 2121-2125
    Published: 1972
    Released: March 27, 2006
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    The kinetics of the hydrolysis of pentammineruthenium(III) complexes containing carboxylates and α-substituted acetates (glycolate and glycinate) have been studied. The experiments were carried out in a solution of [H+]=0.025–0.1M, at 40–70°C. For each complex, the rate law was found to be: rate=[complex](kH2O+kH[H+]). The kH2O and kH values for the formato, acetato, propionato, isobutyrato, glycolato, and glycinato complexes are, respectively (at μ=0.10, 59–61°C): kH2O, 5.37×10−5, 11.8×10−5, 14×10−5, 13.7×10−5, 5.7×10−5, and 6.75×10−5sec−1; kH, 3.3×10−3, 2.3×10−3, 2.5×10−3, 1.7×10−3, 0.75×10−3, and 3.1×10−3M−1sec−1. The mechanisms of acid hydrolysis are discussed for the two reaction paths.
  • Hayami Yoneda, Takao Miura
    1972 Volume 45 Issue 7 Pages 2126-2129
    Published: 1972
    Released: March 27, 2006
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    Complete resolution of racemic [M en3]3+ (M=CoIII, CrIII, and RhIII) by means of electrophoresis was achieved in a background solution of sodium d-tartrate and aluminum chloride. Electrophoretic data obtained under various conditions (various compositions, concentrations, and pH values of supporting electrolyte solutions) indicated that the separation of the enantiomers of [M en3]3+ complexes was accomplished not by the d-tartrate anion but by some aluminum d-tartrate complex anion.
  • Fujio Mizukami, Haruko Ito, Junnosuke Fujita, Kazuo Saito
    1972 Volume 45 Issue 7 Pages 2129-2137
    Published: 1972
    Released: March 27, 2006
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    New cobalt(III) complexes containing optically active (RR and SS) and meso(RS) 2,4-pentanediamine (2,4-ptn) have been synthesized. [Co(RR-2,4-ptn)3]3+ gives two diastereoisomers, prismatic crystals with (−)546 rotation and needle-like crystals with (+)546 rotation. The former is produced much more than the latter. The conformations of the RR- (or SS-) and RS-2,4-pentanediamine chelate of the complexes were assigned to λ- (or δ-) twist and chair form, respectively, from comparison of their PMR spectra with those of the corresponding tetra-acetato complexes. [Co(RS-2,4-ptn)3]3+ seems to have fac structure with respect to the coordination of the amino groups adjacent to the R- and S-carbon atoms. The circular dichroism spectra of mono and trans-bis-(RR-2,4-ptn) complexes in the first band region are essentially the same as those of the corresponding R-propylenediamine complexes. The circular dichroism spectra of (+)546- and (−)546-[Co(RR-2,4-ptn)3]3+ and (−)546-[Co(RS-2,4-ptn)3]3+ are very different from those of the triscobalt(III) complexes of R-propylenediamine and trimethylenediamine. Such differences have been discussed with reference to the stereochemistry of six-membered chelate complexes.
  • Ichiro Murase, Kuniko Yamanouchi, Shoichiro Yamada
    1972 Volume 45 Issue 7 Pages 2138-2140
    Published: 1972
    Released: March 27, 2006
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    A new multidentate Schiff base, 1,4-bis(o-salicylideneaminophenyl)-1,4-dioxabutane having six atoms which may be available for bonding with a metal ion was prepared. With this ligand several metal complexes have been synthesized. From their magnetic properties, electronic absorption spectra and X-ray powder diagrams, it has been concluded that the cobalt(II), nickel(II), and zinc(II) complexes are isomorphous, having a five coordinated configuration, in which one of the ethereal oxygen atoms of the ligand is bound with the metal ion. The copper(II) complex with a similar composition has a different configuration.
  • Katsumoto Yamanouchi(Formerly Iwasaki), Shoichiro Yamada
    1972 Volume 45 Issue 7 Pages 2140-2143
    Published: 1972
    Released: March 27, 2006
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    Numerous six-coordinate chromium(III) complexes with N,N′-ethylene-bis(acetylacetoneiminate) (abbreviated as Acen) have been synthesized. The complexes obtained are of the type [Cr(Acen)X2]Y, where X=H2O, NH3, CH3NH2, n-C3H7NH2, and n-C4H9NH2 for Y=Cl and X=CN, NCS, and NO2 for Y=K. The complex [Cr(Acen)(H2O)2]Cl has been obtained by a reaction of anhydrous chromium(III) chloride with N,N′-ethylene-bis(acetylacetoneimine) in tetrahydrofuran. The other complexes have been derived from the diaquo-complex. Infrared spectra show that the nitrite ions in [Cr(NO2)2(Acen)] and the thiocyanate ions in [Cr(NCS)2(Acen)] are bound with the chromium(III) ion through oxygen and nitrogen atoms, respectively. Electronic absorption bands of all these complexes, which arise from internal transitions within the ligand Acen, differ greatly from those of the free ligand, suggesting that the electronic states of the ligand in the complexes differ from those of the free ligand.
  • Masao Mukaida, Terunosuke Nomura, Tatsujiro Ishimori
    1972 Volume 45 Issue 7 Pages 2143-2147
    Published: 1972
    Released: March 27, 2006
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    Complexes with the general formula of [Ru2(RCOO)4X], where R=H, X=Cl, or Br; R=Me, X=Cl, Br, I, SCN, NO3, or MeCOO; R=ph, X=Cl, or Br, were prepared. The magnetic properties, conductivities, polarographic behavior, and infrared spectra of these complexes were investigated. All the complexes show magnetic moments of 2.84–2.96 B.M., and their susceptibilities, at from about 300 to 100°K, can be fitted to the Curie-Weiss law with negative values of the Weiss constant (θ=−30–−60°K). These complexes seem to be isostructural. Monochloroacetato-, and trichloroacetatoruthenium complexes ([Ru2(CH2ClCOO)4Cl]·2H2O and [Ru(OH)(CCl3COO)2(H2O)]) were also prepared.
  • Hiroshi Kobayashi, Tetsuo Hara, Youkoh Kaizu
    1972 Volume 45 Issue 7 Pages 2148-2155
    Published: 1972
    Released: March 27, 2006
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    Cobalt(I) tetraphenylporphin was prepared by reduction of tetraphenylporphinatocobalt(II) with sodium benzophenone ketyl in tetrahydrofuran (THF) and was purely isolated. The compound was identified as Na-[Co(I)TPP]·5THF (tetraphenylporphin is abbreviated to TPP). On the basis of electronic absorption spectrum, magnetic circular dichroism, magnetic susceptibility and NMR spectrum, the complex formed was concluded to be a complex of cobalt(I). Although some part of cobalt electron is migrated into the conjugated system of porphin, an electron furnished by the reducing reagent is mainly trapped by the central cobalt. The compound should be named sodium tetraphenylporphinatocobaltate(I).
  • Ichiro Fujita, Takanori Yazaki, Yasuo Torii, Hiroshi Kobayashi
    1972 Volume 45 Issue 7 Pages 2156-2161
    Published: 1972
    Released: March 27, 2006
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    Electronic absorption spectra of tris(2,2′-bipyridine) complexes of vanadium(II) and chromium(II) were measured. When methyl groups are introduced into the coordinating bipyridine, (d, d*) transitions in the central metal, (π, π*) transitions in the coordinating ligand, and “metal to ligand” charge-transfer transitions show their respective characteristic shifts. Thus the visible and near-infrared bands of tris(2,2′-bipyridine) complexes of vanadium(II) and chromium(II) are assigned to “metal to ligand” charge-transfer transitions as well as the visible bands of tris(2,2′-bipyridine)iron(II). A comparison between the corresponding bands of tris(2,2′-bipyridine) complexes and tris (1,10-phenathroline) complexes also verifies the assignment.
  • Kazuo Konya, Junnosuke Fujita, Hiroaki Kido, Kazuo Saito
    1972 Volume 45 Issue 7 Pages 2161-2165
    Published: 1972
    Released: March 27, 2006
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    Optical inversion of coordinated 2-methyl-2-butene and trans-2-butene in trans(N)-chloro-L-prolinato-olefinplatinum(II), trans(N)-[PtCl(L-prol)(olefin)] (nitrogen of L-prolinate ion is trans to the olefin), i.e. the interconversion between diastereoisomers (Fig. 1), has been kinetically studied in acetone by measuring the decrease in the intensity of circular dichroism (CD) in near ultraviolet region. The rate was measurable only in the presence of olefin, and can be expressed by the relation, Rate=k[complex][olefin]. The Ea and the ΔS\ eweq values for the two complexes are 7.8±1.0 and 9.0±1.0 kcal/mol, and −44 and −39 entropy unit, respectively. The coordinated trans-2-butene is replaced by other olefins, 2,3-dimethyl-2-butene, 2-methyl-2-butene, trans-2-butene (optical inversion), and styrene, under similar conditions to give the same rate formula. The second order rate constant increases in the given order. The inversion seems to take place via bimolecular mechanism with excessive olefin as nucleophile. The corresponding complexes containing styrene and its para derivatives give such an inversion much faster in the absence of excess of olefin. With change of para substituents, the rate increases in the order, methoxy<methyl<hydrogen<chloro<nitro. This seems to be related with their electrondrawing ability.
  • Kenzo Nagase
    1972 Volume 45 Issue 7 Pages 2166-2168
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The thermal decomposition reactions of metal oxalato complexes in the solid state were studied by the TG and DSC methods. The results from TG indicated that the thermal stability of the anhydrous complex decreases approximately with the increase in the electron affinity of the central metal ion. From DSC, the complexes can be divided into two groups, giving endothermic and exothermic peaks on the decomposition of their anhydrous complexes respectively. The two enthalpy changes, ΔH, corresponding to the dehydration and to the decomposition of the anhydrous complexes, are also presented.
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