Reaction of Acetoacetamide (I) with α, β-unsaturated ketone (II) and aldehyde (XV) is described. Reaction of I with 3-buten-2-one (IIa) gives rise to 3-carbamoyl-2, 6-heptanedione (IIIa), 2-carbamoyl-5-hydroxy-5-methylcyclohexanone (IVa), 6-carbamoyl-3-methyl-2-cyclohexanone (Va), 3-acetyl-6-methyl-3, 4-dihydro-2 (1H)-pyridone (VIa), and 3, 9-dimethyl-2-azaspiro [5, 5] undeca-3, 8-diene-1, 7-dione (VII). Reaction conditions such as catalyst and reaction temperature influence the product formed. Similarly, reactions of I with 3-penten-2-one (IIb), 4-methyl-3-penten-2-one (IIc), 4-phenyl-3-buten-2-one (IId), and 2-benzylideneacetophenone (IIe) afford the corresponding cyclohexanone derivatives (Vb, c, d, e) besides the dihydropyridone derivatives (VIb, d, e). α, β-Unsaturated aldehyde such as crotonaldehyde (XVa) reacts with I to give 3-acetyl-6-hydroxy-4-methyl-2-piperidone (XVIa), 3-acetyl-4-methyl-3, 4-dihydro-2 (1H)-pyridone (XVIIa), and 3-acetyl-6-ethoxy-4-methyl-2-piperidone (XVIIa). Similar reaction of cinnamaldehyde (XVb) with I gives rise to the adduct (XVIb), dihydropyridone derivative (XVIIb), and piperidone derivative (XVIIIb).

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Chemical structures of the minor components obtained from the culture filtrate of Streptomyces rochei var. volubilis, lankacyclinol A and iso-lankacidinol, and the anti microbially active metabolites, lankacyclinol, were proposed by chemical degradation studies and spectral analyses. Lankacyclinol A and lankacyclinol were the decarboxylated compounds of lankacidinol A and lankacidinol, respectively. Iso-lankacidinol was assumed to be 16-epimer of lankacidinol. These compounds are belong to lankacidin-group (T-2636) antibiotics whose chemical structures are shown in Chart 1.

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Continuing our study on new types of non-narcotic analgesics, we synthesized 1, 2, 3, 4, 5, 6-hexahydro-8-methoxy-6, 6-dimethyl-3-benzazocine (XI) from 2-(2-cyano-1, 1-dimethylethyl)-4-methoxybenzoic acid, through 3-(2-cyanomethyl-5-methoxyphenyl)-3-methyl-butyronitrile (X). The reductive ring closure reaction of X was particularly investigated to obtain XI and the pathway of this reductive ring closure reaction was estimated from the reactivity of the by-products, 3-[2-(2-aminoethyl)-5-methoxyphenyl]-3-methylbutyronitrile and 3-[2-(2-aminoethyl)-5-methoxyphenyl]-3-methylbutylamine.

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An attempt was made to use liposomes as a carrier intended for prolonged intramuscular absorption of highly water-soluble drugs. ¹³¹I-Insulin, ¹⁴C-sucrose, ¹⁴C-inulin, and ¹⁴C-cefazolin sodium, a new derivative of cepharosporin antibiotics, were chosen as model compounds. These model drugs were dissolved in pH 7.0 buffer solution and entrapped in liposomes composed of various ratios of phosphatidyl choline, cholesterol, and dicetylphosphate. After injection in the form of such liposomal suspensions, clearance of model drugs from the intramuscular injection site was delayed to a considerable extent in comparison with the control aqueous buffer injections. It was observed that the larger the amount of cholesterol incorporation into liposomes were, the slower the drug absorption became. Although the intramuscular absorption of the drugs from the rat thigh muscle was delayed by their entrapment in liposomes, extent of the prolongation was less than that expected from their in vitro release characteristics determined by dialysis experiments. Physical stability of liposomes containing ¹⁴C-cefazolin sodium was tested in the presence of serum and muscle homogenate. It appears that liposomes are gradually hydrolysed or affected by serum thereby losing their integrity and releasing the entrapped drugs.

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The preparation of 10-(4-methylpiperazino) dibenzo [b, f] thiepin (16a) and related Compounds is described. The reduction of 16a in an acidic medium yield the dihydro derivative (21) which was pharmacologically a valuable compound. Many of the compounds in this series showed marked neuroleptic effects similary to octoclotepine (2).

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To prevent metastasis along the lymph pathways, it is greatly necessary to create a selectively high concentration of anticancer agent in the lymphatic system. The enhancement of lymphatic transport of Mitomycin C (MMC) was accomplished by the injection of fat emulsion to tissue spaces. A comparison of concentration of MMC in thoracic duct lymph and plasma after intraperitoneal and intramuscular injection showed that W/O emulsion was the most effective and followed by O/W emulsion and aqueous solution. In O/W emulsion, the one emulsified by gelatin observed to facillitate the lymphatic transport whereas the one emulsified by polysorbate 80 had little effect. This difference appears to depend upon the binding to oil droplets, because MMC was bound to oil only in the emulsion by gelatin. A measuring of oil in thoracic duct lymph and lymph nodes indicated that MMC did not always accompany with oil in the lymphatic system.

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Investigations on the preparative methods and some chemical modifications of the previously reported potent diuretic, 1, 4-dimorpholino-7-phenylpyrido [3, 4-d] pyridazine (1 : DS-511) were undertaken, producing a variety of derivatives shown in Table I. Comparison of the reactivity between the two chloro groups in 1, 4-dichloropyrido [3, 4-d] pyridazine showed that the 4-chloro group is more reactive toward nucleophilic substitution than the 1-chloro group. Some reaction of 1, e. g. acid hydrolysis, reduction and Grignard addition reaction were also carried out. Significance of the ring nitrogen at the 6-position in 1 for diuretic activity is discussed.

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Ethyl N-(2-pyridyl) formimidate (Va) reacted with diketene to give 3-acetyl-4H-pyrido [1, 2-a] pyrimidin-4-one (VIIa) and ethyl 2-(2-pyridylaminomethylene) acetoacetate (VIIIa). Reaction of diketene with ethyl N-(2-pyridyl) acetimidate (Vb) and ethyl N-(2-pyridyl) propionimidate (Vc) afforded 4H-pyrido [1, 2-a] pyrimidine derivatives (VIIb and VIIc), respectively. Similarly 2-benzylideneaminopyridine (VIa) reacted with diketene to give 3-acetyl-4-hydroxy-2-phenyl-4H-pyrido-[1, 2-a] pyrimidine (XI). On the other hand, reaction of trimethylsilyl isocyanate with Va, Vb, and Vc gave rise to 4H-pyrido [1, 2-a]-sym-triazin-4-one derivatives (XIXa, XIXb, and XIXc), respectively. Reaction of phenyl isocyanate with VIa afforded 2, 3-diphenyl-4H-pyrido [1, 2-a]-sym-2, 3-dihydrotrazin-4-one (XX).

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Three types of condensation reaction shown in Chart (Scheme 1-3) were carried out. Scheme (1) shows a condensation of the protected mononucleotide with the protected nucleoside to give UpU. Scheme (2) shows a condensation of the mononucleotides and Scheme (3) involves a reaction of the dinucleotide blocks obtained in reaction (1) and (2). Reagents used for the first reaction were : dicyclohexylcarbodiimide, DCC ; triphenylphosphine-2, 2'-dipyridyldisulfide, Ph₃P-(PyS-)₂ ; diphenylphosphoryl azide, DPPA ; diethylphosphoryl cyanide, DEPC ; 2-isobutoxy-1-isobutoxycarbonyl-1, 2-dihydroquinoline, iBiBDQ : 2, 4, 6-triisopropylbenzenesulfonyl chloride, TPS ; p-toluenesulfonic anhydride, Ts₂O. DCC, TPS and Ph₃P-(PyS-)₂ gave almost quantitative yield to form the dinucleoside monophosphate. For the second and the third reactions above three activating reagents were used. These experiments showed that DCC seemed to be suitable for the synthesis of the dinucleotide using aromatic phosphoramidates as protection of the terminal phosphate and TPS for block condensation involving the protected UpU and UpUp to yield the tetranucleotide, UpUpUpU.

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Carroll reaction of 1, 1-diphenyl-2-propynyl acetoacetate results in the formation of 3, 5-hexadien-2-one derivative (IIIc) besides 2, 4-hexadienoic acid derivatives (IV and IV'). IV and IV'are proved to be geometrically isomers by the comparison of their nuclear magnetic resonance data. Other reactions are explained.

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On the basis of chemical and physicochemical evidence, two major saponins named Mi-saponin A and Mi-saponin B, which were isolated previously from the seed kernels of Madhuca longifolia (L.) MACBRIDE (syn. Bassia longifolia L.), have been elucidated to be expressed respectively as 3-O-β-D-glucopyranosyl-28-O-[α-L-rhamnopyranosyl (1→3)-β-D-xylopyranosyl (1→4)-α-L-rhamnopyranosyl (1→2)-α-L-arabinopyranosyl]-protobassic acid (9) and 3-O-β-D-glucopyranosyl-28-O-{3-O-β-D-apio-D-furanosyl-4-O-[α-L-rhamnopyranosyl (1→3)-β-D-xylopyranosyl]-α-L-rhamnopyranosyl (1→2)-α-L-arabinopyranosyl}-protobassic acid (10).

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The structure of thalictine (1), isolated from the stems and leaves of Thalictrum thunbergii DC., has been established as 1, by nuclear magnetic resonance spectral data and chemical degradation.

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Quinoline 1-oxide (Ia) reacted with potassium cyanate and tosyl chloride in ethanol at -10°to give ethyl N-(2-quinolyl) carbamate (IIa) in 70% yield. The reaction under reflux caused decrease of the yield of Ia (11%) and additional formation of 2-ethoxyquinoline (IIIa) (54%) and carbostyril (IV) (29%). Unless ethanol was used, no definite product was isolated. Reactions of some derivatives of Ia as well as that of isoquinoline 2-oxide were also examined under the same conditions.

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Parathion (O, O-diethyl-O-p-nitrophenyl phosphorothioate) was reduced to hydroxylaminoparathion and aminoparathion by heated spinach chloroplasts with an artificial electron donor system in the light. Spinach ferredoxin was not required for this reaction, the rate of which increased as the heating time of chloroplasts became longer, at least up to 3 min at 50°. In these respects, the present photoreduction of parathion is very different from the ferredoxin-dependent one by unheated chloroplasts. It is presumed that parathion directly accepts electrons from the primary electron acceptor of photosystem I in heated chloroplasts.

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The reaction of various nucleosides (III) with trichloromethylphosphonic acid dichloride in triethyl phosphate or m-cresol afforded nucleoside 5'-trichloromethylphosphonates (IV). The intramolecular cyclization of IV with potassium t-butoxide in dimethyl sulfoxide or N, N-dimethylformamide led to the synthesis of nucleoside 3', 5'-cyclic phosphates (I) in high yields by fission of the C-P bond of the phosphonate (IV).

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The docosapeptide corresponding to positions 18 to 39 of the revised amino acid sequence of porcine ACTH (porcine ACTH-like intermediate lobe peptide, CLIP) was synthesized and its radioimmunoassay was conducted. It was shown that its mode of the cross reaction with the ACTH antiserum (prepared from porcine ACTH) was parallel, like synthetic human and bovine type CLIPs, to that of porcine ACTH, when ¹²⁵I-synthetic human CLIP was used as a tracer.

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A new synthetic route to 1, 4-dimorpholino-7-phenylpyrido [3, 4-d] pyridazine (1), a potent diuretic, has been investigated. Chlorination and the subsequent dechlorination by catalytic hydrogenation of ethyl 3-cyano-2-oxo-6-phenyl-4 (1H)-pyridinecarboxylate (2) gave ethyl 3-cyano-6-phenyl-4-pyridinecarboxylate (6), which was also obtained by desulfurization of ethyl 3-cyano-6-phenyl-2-thioxo-4 (1H)-pyridinecarboxylate (3). 6 was led to 7-phenylpyrido [3, 4-d] pyridazine-1, 4 (2H, 3H)-dione (12), a key intermediate in the synthesis of 1, by way of cyclic imide (10) or anhydride (11). Several homologs of 1 could also be prepared by employing these procedures. Reactivity of the three chloro groups in 1, 4, 5-trichloro-7-phenylpyrido [3, 4-d] pyridazine (18) towards nucleophilic substitution with morpholine is discussed.

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Stereochemistry of the hydroxy diacid (III), which was obtained by the benzilic acid rearrangement of the dioxo ester (II) derived from l-abietic acid (I), was determined uneqivocally. Moreover, the rearranged compounds (III and IX) were concluded to have a nonsteroidal form.

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A-ring substitution of hydrofluorene compound derived from l-abietic acid (I) was accomplished and several hydrofluorenes with A-ring substituent were synthesized.

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d-Kaurene (XXXVI) and d-phyllocladene (XXXVII) were synthesized from l-abietic acid (I) via intramolecular carbenoid reaction of diazoketones and subsequent cleavage of the resulting cyclopropyl ring with Li-liq. NH₃. Methyl dehydroabietate (XVI) and dehydroabietane (V) introduced from I were used as the starting materials. The improved synthesis of V was also described.

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The protected tetradecapeptide corresponding to positions 9 through 22 of porcine motilin, Z (OMe)-Glu (OBzl)-Leu-Gln-Arg (Tos)-Met-Gln-Glu (OBzl)-Lys (Z)-Glu (OBzl)-Arg-(Tos)-Asn-Lys(Z)-Gly-Gln-OH, was synthesized to serve as a starting material for the total synthesis of this gastric motor activity stimulating polypeptide.

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Synthesis of the docosapeptide corresponding to the newly revised sequence of porcine motilin, a gastric motor activity stimulating polypeptide, was accomplished. Synthetic peptide exhibited characteristic contractile activity patterns of the stomach and the duodenum in dogs, which were quite similar to those of the burst activity of these organs.

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General 3, 3-dichloro-2-azetidinone formation in good yield has now been realized by a new reaction of trichloroacetic anhydride with Schiff bases. Process of the reaction is characterized by the formation of carbon dioxide and carbon tetrachloride, mechanistically involving chlorine cation extraction from trichloroacetyl group by trichloromethyl anion.

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In order to clarify the stereochemistry of hydrogen loss from C-4 during the enzymatic dehydrogenation the stereospecifically labeled 4-d₁-5α-androstane-3, 17-diones (III, VI) were synthesized. Each substrate was incubated with the cell-free extract of Nocardia restrictus and the biotransformation products, androst-4-ene-3, 17-dione and androsta-1, 4-diene-3, 17-dione, were separated. Inspection of their mass and nuclear magnetic resonance spectra revealed that elimination of hydrogen from C-4 in the △⁴ unsaturation process is stereoselectively β.

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The addition of both native and boiled 105000 g supernatant from rat liver to dopamine β-hydroxylase assay system caused marked decreases in dopamine β-hydroxylase activity, and the degrees of these inhibitions were dose-dependent. When the boiled supernatant was fractionated by using chromatography on a Sephadex G-25 superfine, at least two inhibitory peaks were observed by the addition of each column fraction. The second inhibitory peak (fraction 26) was estimated to have a molecular weight of about 1000-1300. This inhibition was non-competitive with substrate, tyramine and co-substrate, ascorbic acid and completely reversed by the addition of sulfhydryl reactive agents such as N-ethylmaleimide. The second inhibitory peak coincided to the peak of the stimulation of adenyl cyclase of rat brain synaptosomes by the addition of column effluent of a Sephadex G-25 superfine.

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Human liver alkaline phosphatase (E. C. 3. 1. 3. 1) has been purified by butanol extraction, acetone precipitation, and a combination of diethylaminoethyl (DEAE)-cellulose, carboxymethyl (CM)-cellulose, Sephadex G-200 gel chromatography. The homogeneity of purified enzyme was demonstrated by disc electrophoresis and micro-Ouchterlony. The heat activation for hydrolysis of p-nitrophenyl phosphate was calculated as 21000 cal/mole and liver alkaline phosphatase was inhibited by homoarginine. A molecular weight of 180000 was obtained by gel filtration and isoelectric point of pI 4.7 was determined by isoelectric focusing. The optimum pH for the hydrolysis of p-nitrophenyl phosphate was 10.6 and optimum temperature was 40°in the standard assay system and other enzyme properties were also examined.

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A highly sensitive method for the determination of trace amounts of Mn (II) is based on the catalytic effect of Mn (II) on the autoxidation of 3-ethyl-2-thiohydantoin (ETH). Under given conditions of concentrations of reactants, temperature and reaction time, the coloration due to the oxidation of ETH in alkaline solution is proportional to the concentration of Mn (II) present. Mn (II) is determined by measuring the absorbance of the colored sample solution at 500 nm. Concentrations in the range of 2 to 16 ng of Mn (II) may be determined. The present method was applied to the analysis of natural water.

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Quaternization of 9a-cyanomethyl- and 9a-ethoxycarbonylmethyl-octahydroquinolizine (VI and XI) with methyl iodide afforded cis (VIIa and XIIa) and trans methiodides (VIIb and XIIb), respectively. On treatment with lithium in liquid ammonia, the methiodides (VIIa, XIIa, and XXIV) gave the ten-membered ring amines (VIII, XIII, and XXV), respectively, in moderate yields, however, the methiodide (XXIX) gave only the demethylated product (XXVIII). And the methiodide (VIIa) yielded also the decyanated amines (IX and X) as the by-products. The formation of the ten-membered ring amines (VIII, XIII, and XXV) was proved to proceed as shown in Chart 5 via the unsaturated ten-membered ring amines (XVII, XVIII, and XXX), which were actually derived from the methiodides (VIIa, XIIa, and XXIV), respectively. On the other hand, treatment of VIIa and XIIa with sodium ethoxide afforded the endocyclic olefinic ring amines (XV and XVI), which were shown to be obtained by isomerization of the initially formed exocyclic olefinic ring amines (XVII and XVIII), respectively.

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2-Bis (methylthio) methylenebenzothiophen-3 (2H)-one, which was prepared by the reaction of benzothiophen-3 (2H)-one with carbon disulfide in the presence of sodium hydroxide in dimethyl sulfoxide, reacted with nucleophilic reagents such as amines or active methylenes to give the corresponding the replacement products of one or two methylthio groups in good yields.

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Two new polyoxypregnane derivatives, tomentin (12β-O-, 20-O-diacetyltomentogenin) and dehydrotomentin (12β-O, 20-O-diacetylutendin), were isolated from the stem of Marsdenia tomentosa. Dehydrotomentin is a diester possessing the utendin skeleton to be isolated from the Asclepiadaceae plants for the first time. Very characteristic fragment pattern for tomentogenin derivatives was observed in the mass spectrum of tomentin.

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A facile one step synthesis of hypoxanthine and 1-alkylhypoxanthines from 2-cyano-2-phenylazoacetamide and its N-alkyl analogs has been achieved by means of catalytic reduction in ammonia-formamide system at elevated temperature. Mechanistic investigation has revealed a pathway involving pyrimidine ring-closure followed by imidazole ring-closure for this reaction.

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The octadecapeptide corresponding to the entire amino acid sequence of equine β-melanocyte-stimulating hormone (MSH) was synthesized by assembling 4 subunits ; Z (OMe)-Asp (OBzl)-Glu (OBzl)-Gly-OH (I), Z (OMe)-Pro-Tyr-Lys (Z)-Met-NHNH₂ (II), Z (OMe)-Glu (OBzl)-His-Phe-Arg (Tos)-Trp-Gly-OH (III), Z (OMe)-Ser-Pro-Arg (Tos)-Lys(Z)-Asp (OBzl)₂ (IV), followed by deblocking of all protecting groups with hydrogen fluoride. The in vivo MSH activity of synthetic equine β-MSH was found equivalent to that of synthetic human β-MSH (in vitro activity, 6.2×10⁹ MSH unit/g).

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N, N-Dibromo-o-carbomethoxybenzenesulfonamide (1) was allowed to react with cyclohexene and styrene to give trans-2-bromo-1-o-carbomethoxybenzenesulfonamidocyclohexane (2) and 1-phenyl-1-o-carbomethoxybenzenesulfonamido-2-bromoethane (5), respectively. Compound 2 was converted to its aziridine derivative (3). It was found that the hydrolysis of 2 with 10% HCl-AcOH gave β-chloroamine which was converted to benzene-sulfonyl derivative 4. When 5 was treated under the same condition, formation of corresponding β-chloroamine, which was identified as its benzenesulfonamide 6, was observed. On the other hand, the treatment of 5 with base followed by the hydrolysis gave the amino alcohol 8, whose substitution pattern was different from that of 6, by way of the aziridine 7.

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γ-Induced addition reactions of thiols to methyl oleate were investigated and the corresponding sulfides were prepared in yield of 94-97%. The adducts consisted of approximately equal amount of C-9-adduct and C-10-adduct. The effects of concentration of ethanethiol, dose and solvent were examined. Diethyl disulfide and sulfide also afforded the ethanethiol adducts in lower yield.

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The calcium-binding activity in the soluble fraction of a normal rat liver was studied. Calcium binding in the supernatant depends on the competition between a cation-exchange resin and a soluble calcium-binding substance for added calcium. The calcium concentration found in the supernatant of the test system was approximately 12-fold of that of calcium contained in the soluble fraction of a normal rat liver. The binding of calcium in the supernatant of the test system using the heat-treated soluble fraction increased linearly up to 0.75 mM calcium and was saturated 1.0 mM calcium. When the radiocalciumbinding activity was expressed as S/R net, the radiocalcium-binding activity existed in soluble fraction, and it increased approximately 4-fold by the heat treatment. These results suggest that the calcium-binding factor exists in the soluble fraction of a normal rat liver.

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In the chromic acid oxidation of 2-aminomethyl-5-chloro-1-methyl-3-phenylindole (1) to 7-chloro-1, 3-dihydro-1-methyl-5-phenyl-2H-1, 4-benzodiazepin-2-one (2), 1 reacts rapidly with chromic acid to form an oxidation intermediate A, which on acetylation with acetic anhydride gives 2-acetamido-2'-benzoyl-4'-chloro-N-methylacetanilide (3). The rate for formation of 2 from A has been determined by following the change of the quantities of 2 and 3 obtained by periodical sampling followed by quenching with acetic anhydride. The rate is first order with respect to the concentration of A.

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The treatment of 6-anilinouracils with a mixture of nitric acid and 4-phenylurazole (which is virtually a mixture of nitrous acid and 4-phenyl-1, 2, 4-triazoline-3, 5-dione (PTAD)) in dioxane gave the corresponding alloxazine 5-oxides exclusively. This reaction involves the nitrosative cyclization of 6-anilinouracils by nitrous acid, followed by the dehydrogenation of the hydroxylamine intermediates with PTAD. 6-Anilinouracils react with PTAD to give the corresponding Michael-type adducts, 6-anilino-5-(4-phenylurazol-1-yl) uracils.

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En partant des chloro-5 ou bromo-5 salicylaldehydes, nous avons synthetise quatre acyl-3 halogeno-5 benzofurannes : acetyl-3 chloro-5-(1), benzoyl-3 chloro-5-(2), acetyl-3 bromo-5-(3) et benzoyl-3 bromo-5-(4) ethyl-2 benzofurannes. Ces acyl-3 benzofurannes halogenes peuvent etre transformes en (halogeno-5 hydroxy-2 phenyl)-5 pyrimidines, par la guanidine, la thiouree, l'acetamidine et la cyanoguanidine, mais pas par l'uree. On peut classer les aptitudes des reactifs diamines a donner des pyrimidines avec les acyl-3 halogeno-5 benzofurannes dans le meme ordre que celui que nous avions deja releve pour les benzofurannes non-halogenes : guanidine>thiouree>acetamidine»uree.

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The induced paramagnetic shifts between Eu (DPM)₃ and aliphatic amines or alcohols were measured to the stoichiometry, etc., with the following results. 1) The continuous variation and molar ratio methods showed a 1 : 1 stoichiometry between Lewis base and Eu (DPM)₃ complex in CCl₄ solution. 2) The shift parameters S_0.01 and S_1.0 corresponded well with each other, and the chemical shifts of equimolar mixtures were of the same magnitudes as S_1.0. 3) The chemical shift differences of the 1 : 1 mixture and free base at infinite dilution afforded linear relations between the slope 0.8 and S_0.01. 4) The induced paramagnetic shift parameters S_0.01 do not represent the so-called bound chemical shift △B, but are measures of the equilibrium binding constants K_b of the 1 : 1 complex formed between Lewis base and Eu (DPM)₃.

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The feasibility of gas chromatographic estimation is reported for iron in air-borne particulates. The particulate is ashed, in an electric furnace, and digested with HNO₃. The acidic digest is neutralized with NaOH, and bufferized with acetate buffer at pH 4.5, and then treated with 0.5% trifluoro-acetylacetone (TFA)-benzene solution to extract iron as Fe TFA chelate. The extracted chelate is submitted to gas chromatography. Some observations have been made on the gas chromatographic conditions.

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Fusarenon-X, neosolaniol and T-2 toxin, 12, 13-epoxytrichothecene mycotoxins of Fusarium spp. cause in vitro an inactivation of SH-enzymes such as creatine phosphokinase, lactate dehydrogenase and alcohol dehydrogenase when the enzyme molecules were preincubated with the mycotoxins in the absence of substrates, and the supplement of dithiothreitol prevents this inactivation. Gel-filtration of a mixture containing alcohol dehydrogenase and ³H-labelled fusarenon-X revealed the formation of a complex [³H-fusarenon-X-alcohol dehydrogenase] with a molecular ratio of 4 : 1, and dithiothreitol prevented the complex formation. These results indicate that the epoxytrichothecenes bind with the thiol residues of SH-enzyme protein.

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Essential oils of the methylchavicol type Magnolia salicifolia MAXIM. were examined. The yields of oils were 0.78-1.06% of fresh shoots, 1.42% of fresh leaves, 0.51% of branchlets, 3.80% of fresh flower buds, and 0.92% of fresh flowers. The shoot oil contained 69.1-84.1% of methylchavicol and the leaf oil contained as high as 91.4% of methylchavicol, but the oil from branchlets contained 23.8% of 1, 8-cineole, 19.7% of citral-b, and 30.2% of citral-a, and the oils from buds and flowers also contained 22.6-24.2% of citral-b and 38.1-43.3% of citral-a, as in the case of the anethole type, and the methylchavicol, safrole, and methylengenol type M. salicifolia. The oil of Magnolia kobus DC. examined by Asahina, et al. was not the oil of a true Magnolia kobus but was an oil of this methylchavicol type Magnolia salicifolia.

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In order to obtain an useful derivative for radioimmunoassay, The Tyr residue was attached at the N-terminus of somatostatin. N¹-Tyr-somatostatin prepared by the conventional method was found active as synthetic somatostatin. It was confirmed that des-[Ala¹-Gly²]-somatostatin is an active compound.

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A new isoflavone, 6, 4'-dihydroxy-7-methoxy-isoflavone, was isolated from Chinese Pueraria flowers.

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The reaction of 2-acetoxymethyl-3-acetylquinolines (V, VI) with sodium hydride gave 2-hydroxymethyl-3-quinolinecarboxylic acid lactones (IX, X), presumably formed with the migration of acetyl group. On the other hand, the fact that the reaction of 3-acetyl-2-benzoyloxymethylquinoline (VIII) with sodium hydride gave a lactone (IX) and acetophenone would strongly support for the mechanism of the lactone formation with the acyl migration.

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Sulfur-containing carbamates, which are used in a number of pesticides and herbicides, were examined for their reductive cleavage with Raney nickel. Three types of the carbamates, S-p-chlorobenzyl N, N-diethylthiolocarbamate (I), S-benzyl N, N-diethyldithiocarbamate (II), and methyl N-phenylthiocarbamate (III), were respectively reacted with Raney nickel in ethanol to afford the corresponding reduction products as follows : I→N, N-diethylformamide, toluene, and hydrogen chloride ; II→N, N-diethylmethylamine and toluene ; III→N-ethylcyclohexylamine, N-methyl-N-ethylcyclohexylamine, and N, N-diethylcyclohexylamine. Formation of some of the reduction products indicated an effective participation of ethanol in the process of reduction of the carbamates. Most of the products were adsorbed more or less on Raney nickel, resulting in their unstisfactory recovery.

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The mechanism by which dosage of ethinamate elevates falsely the values for the urinary 17-ketosteroids has been investigated. A specimen of urine collected following oral administration of ethinamate to man was hydrolyzed with sulfuric acid and then extracted with dichloromethane. From the urinary extract two non-steroidal chromogens responsible for the Zimmermann reaction were isolated. The spectral and chromatographic properties indicated that these chromogens would be 1-acetylcyclohex-1-en-4-ol and 1-acetylcyclohex-1-en-5-ol. Their structures were unequivocally characterized by comparison with the synthetic samples. It has been disclosed that during the acid-catalyzed hydrolysis of the conjugates in the process of 17-ketosteroids determination the 4- and 3-hydroxylated metabolites formed from ethinamate are converted artificially into the ketones which give a typical color for the 17-ketosteroids in the Zimmermann reaction.

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An alkaloid from Streptomyces sp. NA-337, whose structure was assigned previously as (E, E)-4-methyl-2-pentadienyl-1-pyrroline, is re-investigated and revised as (E, E)-2-pentadienyl-3, 4, 5, 6-tetrahydropyridine.

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A papaverine-like active compound named paragracine was isolated from Parazoanthus gracilis (Lwowsky). The structure of paragracine was determined to be 1 from its chemical and spectral properties and by X-ray crystallographic analysis of paragracine dihydrobromide trihydrate.

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Thermal elimination of β-ketosulfoxides prepared from esters of m-methoxyphenyl-butyric acid and sulfoxides in the presence of methylcyclopentanedione gave easily a trione and a dione, key intermediates in the Smith's synthesis of estrone.

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