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Symmetrical and unsymmetrical (E,E)-1,4-diaryl-1,3-butadienes can be prepared in high yields from (E)-2-arylethenesulfonyl chlorides by treating with vinylarenes in the presence of ruthenium(II) phosphine complex in benzene.

Reactions of dimethylmethylthiosulfonium fluoroborate with phenyl phosphite, pyridine, 4-cyanopyridine, N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, thiophenol or sodium thiophenolate are almost instantaneous at room temperature, while the reactions with phenols and anisole proceed slowly at 60°C. Products are determined, and the mechanisms are discussed.

The accelerated transport of the blood neutral amino acids into the brain in encephalopathic patients with fulminant hepatitis and advanced liver cirrhosis was demonstrated not only by determining the cerebrospinal fluid (CSF) aminogram but also by calculating the predicted velocity of the amino acid transport through the blood-brain barrier. Significant elevation in CSF aromatic amino acid (AAA) and methionine levels was observed in the encephalopathic patients. Arousal from hepatic encephalopathy by drip infusion of a branched chain amino acid (BCAA)-enriched solution was obtained coincidentally with the elevated BCAA levels and diminished concentrations of AAA and methionine in CSF. These clinical observations were confirmed experimentally in rats treated with carbon tetrachloride (CCl4) and D-galactosamine by obtaining the elevation of neutral amino acid contents in the brain and the slight increase in the brain uptake index (BUI) of a radiolabeled amino acid.

The heptafluoropropylations of several substituted thiophenes with bis(heptafluorobutyryl) peroxide were studied. The orientations of the heptafluoropropylation were examined and compared with those of usual electrophilic substitution. The method for the preparation of 3-heptafluoropropylthiophene was also explored.

S-Phenyl thioacetate (1) quantitatively reacted with 1/2 mole of bromine (or chlorine), yielding acetyl bromide (or chloride) and phenyl disulfide. With iodine, 1 formed a complex, which reacted with an alcohol (MeOH, Me3CCH2OH, PhCH2OH), forming the corresponding ester; a catalytic amount of iodine was sufficient for this transesterification. 1 reacted quantitatively with 1-chlorobenzotriazole. The reaction of 1 with t-butyl hypochlorite yielded t-butyl acetate (70%) and acetyl chloride(30%).

Enantiomerically pure, stable 4-(methoxycarbonyl)phenyl 2,4,6-tri-isopropylphenyl selenoxide (–)-(3) was isolated by fractional recrystallization of diastereoisomeric 4-[(–)-menthyloxycarbonyl]phenyl 2,4,6-tri-isopropylphenyl selenoxide dia.-(1) followed by removal of the chiral source. The absolute configuration around the selenium atom was determined by X-ray crystallographic analysis of diastereomerically pure selenoxide (–)Se-(1).

Aryltriethylgermanes and diethyldiphenylgermane were found to split easily to generate germyl radicals by irradiation with a medium-pressure mercury lamp in hexane or cyclohexane. The germyl free radicals produced reacted with hydrocarbon radicals generated from the solvent by hydrogen abstraction either by recombination or by disproportionation.

過去12年間に経験した食道静脈瘤合併肝癌の治療経験を検討した.この著しく治療困難な疾病の治療方針に関しては,まだ多くの解決すべき問題点があるが,現時点での我々の見解は以下の通りである.(1) 食道静脈瘤合併肝癌でも,肝癌を早期に診断できれば小範囲肝切除で満足すべき成績をおさめうる.この際,吐血の既往を有する静脈瘤あるいはGradeの高い静脈瘤に対しては同時に静脈瘤手術を併施しうる.(2) 40%以上の硬変肝切除を行なうと,約40%の門脈圧上昇を来すので,特にGradeの高い食道静脈瘤では症例に応じて静脈瘤手術を考慮すべきである.術式としては,手術時間,肝癌再発によるシャントの閉塞の可能性などを考えた場合,遠位脾腎静脈吻合術が好ましいと考える.(3) 肝癌が切除されない症例での静脈瘤手術は必ずしも吐血を防止しえず,今後,検討されるべき課題である.

An effective synthesis of selenoxides by the oxidation of selenides with t-butyl hypochlorite in the presence of methanol and pyridine followed by hydrolysis is descrived. This oxidation method is particularly effective for the oxidation of selenides which possess electron-withdrawing groups. A synthesis of partially optically active selenoxide with bulky substituents can be achieved using a novel oxidation method.

過酸化ペルフルオロブチリル[1]の分解反応の詳細を研究した。[1]は対応する非フッ素化過酸化ジアシルにくらべラジカル分解を起こしやすいこと,また種々の求核剤の攻撃により容易に誘発分解を受けることを見いだした。

SummaryThe dietary induction of liver G6PD was found to be markedly impaired in the acute hepatic injury of rat caused by thioacetamide intoxication. The level of cyclic AMP in the injured liver was increased and could not be reduced by glucose-containing diets. The results indicated that the suppressed dietary inducibility of G6PD in hepatic injury is accounted for at least by the dietary unresponsive increase in cyclic AMP level in the injured liver.

Acid-catalyzed oxygen exchange of C-, N-, and O-nitroso compounds with 18O-enriched water is investigated. The rates of exchange increase in the order of C-, N-, and O-nitroso compounds, and nitrite esters exchange their oxygens with those of H218O fairly rapidly.

Assessment of cellular immunity was performed in 41 patients with squamous cell carcinoma of the esophagus to clarify factors associated with immune deficiency. Four parameters, total lymphocytes, numbers of T cell and B cell, lymphocyte blastogenesis in response to phytohemagglutinin and the purified protein derivative skin reaction were measured on admission, after preoperative radiation therapy, and 4 as well as 8 weeks after surgery. The assessment indicated that immune depression clearly existed in esophageal cancer patients on admission. Of the factors of age, dysphagia and stage of cancer, all were associated with immune depression. The effect of treatment for cancer on the immune status was also assessed. The parameters of cellular immunity were markedly depressed by surgery either with or without preoperative radiation therapy. Thus, these results indicate that treatment including surgery and radiation, dysphagia, stage of cancer and age, especially the treatment, are critical factors associated with immune deficiency in esophageal cancer patients.

Electronic absorption spectra of methylene blue layers adsorbed on glass plates have been measured. Higher aggregates of this dye, up to the tetramer, are shown to exist by an analysis of the aggregate spectra on the basis of a three-dimensional PPP calculation and a diagrammatic exciton-splitting model. A shoulder, located around the monomer peak, observed in the spectrum of the adsorbed methylene blue layer is tentatively assigned to the tetramer. The observed spectral behaviour on aggregation is reproduced by the PPP calculation in which a sandwich type structure is assumed for the aggregates. The band splitting patterns in the methylene blue aggregates are explained diagrammatically in terms of the interactions of the transition moments of the monomer sub-units in an aggregate.

La reaction des chlorures de styrenesulfonyle, propene-1 sulfonyle et d'ethylenesulfonyle avec des derives du styrene, conduit a des diaryl-1,4 butadienes-1,3 via des (alcene-1yl [aryl-2 chloro-2] ethyl) sulfones

The enhancing or inhibitory action of the hepatotoxic agents, carbon tetrachloride (CCl4) and azathioprine (AZP), on the evolution of hyperplastic liver nodule (HN) and hepatocellular carcinoma (HCC) in diethylnitrosamine (DEN)- and N-2-fluorenylacetamide (FAA)-treated rats (control group) was tested. The area of gamma-glutamyl transpeptidase(gamma-GTP)-positive HN and/or foci in the eighth week was remarkably small in rats fed on a diet containing FAA and AZP (the AZP group), but was quite large in rats fed a diet containing FAA in addition to repeated CCl4 injections (the CCl4 group). HCC was first detected in the 21st week and the incidence of HCC within the 36 weeks of the experiment was very high in the CCl4 group. However, no tumor, including HCC, was detected in the AZP group during this observation period. No essential differences in the biochemical characteristics of HCC between the control group and the CCl4 group were observed with respect to several enzyme activities. The increased activity of liver aniline hydroxylase observed 12 hr after the administration of FAA, AZP, or DEN decreased when AZP was administered simultaneously with FAA to rats treated with DEN in advance. The mechanisms of the enhancing of inhibitory effect observed are discussed with special reference to the drug-drug interactions.

The photochemical reaction of a series of 2-aryl-1,2-benzisothiazol-3(2H)-ones (1) under deaerated conditions was found to give dibenzo[b,f][1,4]thiazepin-11(10H)-ones (2). A mechanism through a biradical species is proposed for the photoreaction. When the photolysis of 1 was carried out in the presence of oxygen, 2-aryl-1,2-benzisothiazol-3(2H)-one 1-oxides (11) were formed together with compounds 2.

Cathepsin B and L activities in cancerous and noncancerous mucosal tissues from 29 patients with gastric cancer were determined with a small amount of tissue homogenate. Both enzyme activities were significantly higher in cancerous tissues than in noncancerous tissues. The cathepsin B activity was higher with decreasing differentiation of the cancerous tissues, and also with increasing depth of invasion and metastasis to regional lymph nodes. Significantly high cathepsin B activity was observed in specimens of poorly differentiated adenocarcinomas, as well as in specimens from patients with extensive metastasis to n2 or n3 lymph nodes. These results suggest that high cathepsin B activity is characteristic of gastric cancer which invades and metastasizes. Therefore, in cases of marked elevation of cathepsin B activity in cancerous tissues, relatively extensive resection may be necessary to obtain a cure.

カロリー病の1例を報告する.症例は22歳,男性で腹痛を主訴に来院した.腹部エコー,腹部CTにて多発性嚢状性肝内胆管拡張を末梢性優位に認めたことからカロリー病と診断し,確認のため胆道シンチグラフィー,ERCPを施行した.胆道シンチグラフィーでは拡張胆管に一致する不均一な取りこみ像および十二指腸,小腸への排泄遅延を認めた.またERCPでは総胆管,2次肝管に異常なく,末梢性優位の多発性嚢状性肝内胆管拡張を両葉にび漫性に認め,典型的なカロリー病と思われた.腎病変としては腹部エコー,腹部CTより嚢胞腎の合併が考えられた.入院中施行しえた腹腔鏡検査では,肝は硬度が増強し,肝表面に幅広い白色紋理が肝小葉構造を規則正しく取り囲んでいたため,肝はしもふり様を呈していた.組織学的には門脈周囲に著明な線維化を認めるも,肝実質細胞,肝小葉構造に異常を認めず,先天性肝線維症の合併を認めた.

The nematic-isotropic transition temperature of 4-cyano-4′-pentylbiphenyl (host) has been elevated by admixture of 1,5-di-(p-n-butylanilino)-anthraquinone (guest), the elevation being as much as 2.1 °C for 1 mol% guest concentration (β=−0.689). This phenomenon has been considered to be attributable to the guest-host interaction which must be at least attractive and, in addition, of “many-body” type.

1H-and 13C-CIDNP spectra were obtained during the thermal decomposition of several arylazo aryl sulfones (Ar–N=N–SO2–Ar′) in tetrachloroethylene or 1,1,2,2-tetrachloroethane at 100 °C. An enhanced absorption from the C1 of the starting material, azo sulfone, was observed; this indicates that the decomposition of azo sulfone proceeds by means of one-bond fission. The formation of sulfones (ArSO2Ar′) and sulfinic esters (ArO(SO)Ar′) as recombination products in a solvent cage was established from the signs of polarization (enhanced absorption or emission).

Plasma amino acid, plasma pancreatic glucagon and serum insulin levels were simultaneously measured in cirrhotic patients with (drinkers) and without a history of alcohol drinking (non-drinkers), as compared to those in alcoholics without liver disease. Clinical characteristics in drinkers and non-drinkers, such as the extent of liver dysfunction, which may affect plasma amino acid levels, were strictly matched. Plasma pancreatic glucagon levels in the drinker group were much higher than those in the non-drinker group. In the former group, the elevated plasma pancreatic glucagon levels were correlated (p less than 0.05) to total amino acid levels (the sum of 20 kinds of L-amino acid concentrations) and, elevated AAA concentrations leading to a diminished BCAA/AAA ratio. Drinkers with histories of hepatic encephalopathy presented grossly elevated glucagon levels and severely abnormal aminograms similar to those observed in hepatic insufficiency.

Nutritional assessment was performed in 41 patients with squamous cell carcinoma of the esophagus to clarify factors associated with nutritional deficiency. Six parameters, i.e., body weight, triceps skin fold, arm muscle circumference, creatinine/height index, serum albumin and serum transferrin were measured on admission, after preoperative radiation therapy, and at four as well as eight weeks after surgery. The assessment indicated that, on admission, nutritional deficiency clearly existed in esophageal cancer patients. Out of factors including age, dysphagia, stage of cancer and cellular immunity in patients on admission, dysphagia and stage of cancer were associated with nutritional deficiency. The effect of treatments for cancer on nutritional status was also assessed. The parameters of nutrition were markedly depressed by the surgery with or without preoperative radiation therapy. These results indicate that treatments including surgery and radiation, dysphagia and stage of cancer, especially the former two, are critical factors associated with nutritional deficiency in esophageal cancer patients.

Serum alpha-fetoprotein (AFP) concentrations were estimated postoperatively at weekly intervals with the radioimmunoassay in eight adult patients. Seven patients underwent partial hepatectomies of up to 80% of the liver. Surgical drainage was carried out in one individual who had a huge pyogenic abscess in the right hepatic lobe. Despite evidence of clinical and biochemical recovery associated with normal liver regeneration, none of the sera were positive for AFP during the period 4-12 weeks after operation. This study does not support the hypothesis that the elevation of serum AFP in benign liver diseases reflects the extent of liver regeneration.

Polarized ATR spectra have been measured for the dye layers adsorbed on stacked, thin glass plates. For the adsorbed Crystal Violet (CV) layer, the metachromasy band in the || polarized ATR spectrum is blue-shifted and intensified in comparison with that in the ⊥ polarized ATR spectrum. This is in marked contrast to the observation for the adsorbed Methylene Blue (MB) layer that the || polarized ATR spectrum is similar in shape and position to the ⊥ polarized ATR spectrum. The blue shift and the enhancement of the metachromasy band in the || polarized ATR spectrum for the adsorbed CV layer is ascribed to an optical property characteristic of the adsorbed CV layer; the adsorbed CV layer exhibits an extra electronic transition band located at the high-energy side of the metachromasy band and polarized normal to the glass plane. Two possible explanations for the occurrence of this extra band are presented.

Arylthiodimethylsulfonium perchlorates (1) are prepared from arenesulfenyl chloride, methyl sulfide and silver perchlorate. The reactions of 1 with benzyl methyl sulfide, sodium methoxide, anisole, and 2,6-di-t-butylphenol are investigated, and all these nucleophiles attack 1 at its sulfide sulfur atom. The reactivity of 1 is compared with those of anilinosulfonium ion and phenoxysulfonium ion.

Aliphatic thiols ( 1 ) can be prepared under the mildest conditions presently available by desilylation of the appropriate α-trimethylsiloxy sulfide ( 3 ). Sulfides 3 are generated by either alkylation of the corresponding alkyl halide or by standard literature methods.

Arylazo p-tolyl sulfones(I) were thermolyzed or photolyzed in the presence of trapping agents such as α,N-diphenyl nitrone(II), α-phenyl N-t-butyl nitrone(III) and 2-methyl-2-nitrosopropane(X). ESR studies showed that phenyl radical or p-methoxy phenyl radical is produced from the decomposition of I and adds to II or III. The adduct of phenyl radical to II and that of p-methoxyphenyl radiacl to III were synthesized for comparison by separate pathways. The photolysis of phenyl p-tolylazo sulfone(Ia) in the presence of III yielded benzhydryl t-butyl nitroxide, benzoyl t-butyl nitroxide and t-butyl p-toluenesulfonyl nitroxide(XVI) radicals. The photolysis of la in the presence of X gave di-t-butyl nitroxide(XII) and XVI. The photolysis of phenylazotriphenylmethane in the presence of X yielded XII and t-butyl nitroxide radical. The mechanisms of the formation of these radicals are discussed. The formation of arenesulfonyl radicals from the decomposition of I has been proved indirectly (analyses of the product...

Intra and extracellular localization of alpha-fetoprotein (AFP) has been studied by an indirect peroxidase labeled antibody method using 12 cases of human hepatocellular carcinoma (HCC). With light microscopic observation, positive immuno-staining for AFP was observed in 6 out of 12 cases and demonstrated as granular or diffuse deposits in the cytoplasm of neoplastic hepatocytes. In electron microscopic studies, 8 cases showed the positive immuno-staining for AFP in the neoplastic hepatocytes. Intracellular antigen was well circumscribed within certain cell organelles with the positive immuno-staining for AFP being observed in perinuclear space, cisternae of rough endoplasmic reticulum (RER), Golgi complexes, and secretory vesicles. In addition, the positive immuno-staining for AFP was observed in bile canaliculus-like space in most cases with increased levels of serum AFP and in some cases which showed normal levels of serum AFP. Furthermore, the positive immuno-staining for AFP was also observed in intercellular, Disse's-like and sinusoid-like spaces, and micropinocytotic and lysosome-like vesicles in the endothelial cells in a few cases which showed excessively high value of serum AFP. ACTA PATHOL. JPN. 37:915–928, 1987.

Methyl sulfide was very rapidly t-butylated by di-t-butylmethylsulfonium ion, forming t-butyldimethylsulfonium ion. Benzylation of methyl sulfide with dibenzylmethylsulfonium ion was a little slower, and i-propylation with methyldi-i-propylsulfonium ion was not observed. A mechanism presented involves the formation of a tetracovalent sulfur intermediate.

Benzoyl peroxide (BPO) was decomposed in benzene in the presence of trifluoroacetic acid. The thermal reaction is first order in BPO, and the activation energy and activation entropy are 18.7 kcal/mol and −26.3 e. u., respectively. The isomer distributions in the phenylation and benzoyloxylation of substituted benzenes determined indicate that the phenylation and benzoyloxylation are electrophilic substitution reactions. The reaction mechanisms are discussed.

The electronic absorption spectrum of diphenylhexatriyne has been divided into two components polarized along the long and the short molecular axes by means of dichroism analysis using the stretched-polymer-film technique; i.e., a reduced polarization spectrum has been obtained. This reduced polarization spectrum can be explained by a modified PPP calculation including the interaction between mutually perpendicular π and π′ systems in the conjugated system. It has been clarified that the relative intensities of the first and second bands of diphenylhexatriyne reflect the magnitude of interaction between mutually perpendicular π and π′ systems, which is quite great. The magnitude of the electron-repulsion integral between π and π′ electrons is estimated to be about 20–30 per cent of that between ordinary π (or π′) electrons.

In hexamethylphophoramide, 18O-labelled nitrite ion readily exchanged with the nitro group of p-dinitrobenzene at 30°C, whereas the formation of p-nitrophenol by the O-attack of nitrite ion is much slower. p-Nitrochlorobenzene is quickly converted to p-dinitrobenzene by the N-attack of nitrite ion, and p-nitrophenol is the final product. The nitro group of p-nitrobenzonitrile is slowly exchanged with nitrite ion.

The effects of 5-fluorouracil (5-FU) on regenerating liver were studied after two thirds hepatectomy in rats. In Group I, 68% hepatectomy was performed. In Group II, 5-FU in a dose of 20 mg/kg was administered intravenously immediately after, 24 and 48 hours after the same hepatectomy. In Group III, the same amount of 5-FU was given after sham-operation. The mortality rates were 4.5% in Group I, 28.0% in Group II, and 0% in Group III. The treatment with 5-FU following hepatectomy caused not only suppression but delay of liver cell division. Histologic changes such as cellular degeneration, liver steatosis and dilatation of the sinusoidal space were marked and prolonged in the hepatectomy-5-FU group. The metabolic abnormalities in albumin, cholesterol, triglycedides, and phospholipids were further more profound in Group II compared to those in Group I. In Group III, moderate derangements in albumin, triglycerides and phospholipids were observed. The results may indicate that adjuvant chemotherapy with 5-FU or similar drugs immediately after partial hepatectomy in hepatoma patients should be performed with great care if necessary. Otherwise, it should not be carried out until hepatic regneration is almost completed.

Several N-benzylideneanilines were synthesized which possess anilino benzene rings rotated out of the Ar–C=N plane by various degrees due to steric hindrance. Their 13C-NMR spectra indicated that the N lone pair electrons are delocalized to ring A especially in the compounds in which ring A is forced to rotate out of the molecular plane.

Extremely high concentrations of hepatic acetaldehyde were induced in rats by the intragastric administration of ethanol and cyanamide, an aldehyde dehydrogenase inhibitor; and these high levels were maintained for 4 weeks. Liver function tests, including mitochondrial ornithine carbamoyltransferase (OCT) and GOT activities, were within normal limits, and no increase in either hepatic triglyceride or collagen contents was observed. These results suggest that hepatotoxic effects of ethanol are not derived from the high acetaldehyde levels in the liver.

2-Alkyl-3-cyclopentenones were prepared in moderate yields starting from tetrahydrothiopyran-4-one by the one-pot Ramberg–Backlund reaction of 6-alkyl-1,4-dioxa-8-thiaspiro[4.5]decane 8,8-dioxides, followed by acid catalyzed de-dioxolanation.