Studies on the Syntheses of the Pyrethrin Analogues and their Biological Activities

Some new allethronyl esters of cyclopropanecarboxylic acids were prepared, and their insecticidal activities were tested against common housefly. Allethronyl esters of cyclopropanecarboxylic acids having 3,4-methylenedioxyphenyl group on the cyclopropane ring were more or less toxic. Among them, allethronyl 2,2-dimethyl-3-(3′,4′-methylenedioxyphenyl)-cycloopropane-l-carboxylate was found to be more toxic than α-dl-trans-allethrin, and the calculated relative effectiveness were 1.48 and 1.21 on the mortality and knock-down activity respectively as compared with α-dl-trans-allethrin.     

Syntheses of Alarm Pheromone Analogues of the Mold Mite,Tyrophagus putrescentiae,and Their Biological Activities

Against the mold mite, Tyrophagus putrescentiae, 3,7-dimethyl-(Z)-2-octenyl formate (II) is the most active compound as an alarm pheromone besides the natural pheromone, neryl formate (I), and this activity is equal to I (1-10 ppm). In order to elucidate the structural requisites for inducing alarm pheromone activity, a total of 16 analogues of I were prepared by modifying the structure of II. For preparation of 3-methyl- and 3-ethyl-(Z)-2-alkenyl formates, the Wittig reaction of ethoxy- or methoxy-carbonylmethylene triphenyl phosphorane with 2-alkanone or 3-alkanone was used. The reaction with 2-alkanone gave a mixture of (Z)-2-alkenoate (ca. 40%) and (E)-2-alkenoate (ca. 60%) in an average 60% yield. The reaction with 3-alkanone gave a mixture of (Z)-2-alkenoate (56%) and (E)-2-alkenonate (44%).

Alarm pheromone activities were demonstrated on 14 compounds of (Z)-2-alkenyl formates. The presence of the (Z)-allylic primary alcohol formate moiety in a molecule was clarified as the key to induce pheromone activity, and no necessity for an acyclic monoterpene carbon skeleton was demonstrated.     

Syntheses and Biological Activities of Isonitrile Dipeptides

We investigated GroEL substrates from Bacillus subtilis 168 using the single-ring mutant of B. subtilis GroEL. We identified 28 candidates for GroEL substrates, of which Spo0B, Ald, Eno, SpoIIP, and FbaA were involved in spore formation, and Rnc, Tuf, Eno, Tsf, and FbaA were essential for B. subtilis growth. As observed at the protein level, the amount of SpoIIP interaction with GroEL increased at 3 h after initiation of sporulation.     

Syntheses and Biological Activities of Danicalipin A Derivatives

Synthesis of three derivatives of danicalipin A, tetrachloride, trisulfate and a fluorescent probe was achieved through Wittig reaction strategy. Toxicity of the derivatives against brine shrimp (Artemia salina) as also investigated to provide useful information for the biological activity; i) less chloride derivative showed similar toxicity to danicalipin A, ii) the amphiphilic property, a characteristic feature of danicalipin A, was crucial because trisulfate considerably decreased the toxicity and iii) fluorescent derivative kept brine shrimp toxicity of danicalipin A.     

Syntheses and Biological Activities of Analogs of Abscisic Acid

Selenium dioxide oxidation of methyl α-ionylideneacetate (IIb) in ethanol afforded methyl 1′-and 4′-hydroxy-α-ionylideneacetate (IIIb and IV), methyl 3′-hydroxy-β-ionylideneacetate (V) and crude dihydroxy-ionylideneacetate (VI). The latter was oxidized with active manganese dioxide to give methyl abscisate (Ib). The growth and germination-inhibitory activity of compounds related to abscisic acid on Azuki bean seedlings and some species of seeds were examined.     

Syntheses and Biological Activities of Dihydro-5,6-dehydrokawain Derivatives

The syntheses and biological activities of dihydro-5,6-dehydrokawain derivatives against plant pathogenic fungi and termites were investigated. Dihydro-5,6-dehydrokawain was isolated by a simple method without chromatography from the leaves of Alpinia speciosa K. Schum. The white crystalline compound obtained was identified as dihydro-5,6-dehydrokawain (1) by instrumental analyses. 4-Hydroxy-6-(2-phenylethyl)-2H-pyran-2-one (3) was prepared by hydrolyzing dihydro-5,6-dehydrokawain. Three dihydro-5,6-dehydrokawain derivatives were synthesized by reacting 3 with phosphoric agents.

Among the synthesized compounds, dimethyl [6-(2-phenylethyl)-2-oxo-2H-pyran-4-yl] phosphorothionate (4) had the strongest antifungal activity of 91% at 100 ppm against Corticium rolfsii.     

Syntheses of Female Sex Pheromone Analogues of the German Cockroach and Their Biological Activity

Several analogues of 3,1l-dimethyl-2-nonacosanone, one component of the sex pheromone of the German cockroach, were synthesized. Their activity for the male to raise his wings was assayed and summerized in Tables I and II.     

Syntheses and Biological Activities of 1-O-Glucopyranosyl Fatty Acid Esters

1-O-Palmitoyl-d-glucopyranose was prepared by the selective 1-O-acylation of 4,6-O-benzylideneglucose followed by hydrogenolysis of the protecting group. 1-O-Oleoyl-d-glucopyranose was synthesized from the corresponding benzylidene derivative by selective hydrolysis in acetic acid. This procedure constitutes a useful method for the synthesis of 1-O-acyl-d-glucopyranoses containing unsaturated carboxylic acids. However, 4,6-O-benzylidene-l-O-linolenoyl-d-glucopyranose was converted to 3-O-linolenoyl-d-glucopyranose by the acidic hydrolysis due to acyl migration.

Synthesized glucosyl esters were inactive in the bean second-internode bioassay. However, it was found that 3-O-linolenoyl-d-glucopyranose had a promoting activity on germination of pollen and growth of pollen tube.     

悬钩子属植物生物学作用研究进展

悬钩子属（Rubus）植物是蔷薇科（Rosaceae）中的一个大属,全世界已知有750余种,我国约有210多种,分布广泛,但以长江以南及西北地区多见。本属植物中有些种类果实柔嫩多汁,营养丰富;有些种类的果实、种子、根及叶可入药,药用价值较高,具活血化瘀,祛风祛湿,清热解毒,止血止痛,固肾涩精等功效。20世纪80年代以来,我国覆盆子研究利用引起了人们的关注。就近年来悬钩子属植物生物学作用研究情况作一总结。     

Role of Adenosine Kinase in the Biological (Antiviral and Anticellular) Activities of Adenosine Analogues

Abstract

A paired adenosine kinase-positive/adenosine kinase-negative cell system is proposed to distinguish those adenosine analogues that need to be phosphorylated to exert their biological effects from those that are mainly targeted at S-adenosyl-L-homocysteine hydrolase.     

Biological Activities of Analogues of Ser-Val-Gly-Glu (AS-I), a Toxin Pathogenic to Sunflower

The tetrapeptides Ser-Val-Glu-Gly, Hse-Val-Gly-Glu, Thr-Val-Gly-Glu, Val-Ser-Gly-Glu and Ser-Val-Glu-Gly, analogues of the AS-1 toxin which is pathogenic to sunflower, were examined for biological activity on sunflower and eight other plant species. These peptides were synthesized in solution or on a solid phase. Of the species studied by leaf inoculation, sunflower and zucchini were the most susceptible and cotton the most resistant to ail of the toxins tested. The effect of Ser-Val-Glu-Gly was similar to that reported for AS-I, whereas the tetrapeptide Thr-Val-Gly-Glu was the most toxic.     

Syntheses of Several Compounds Related to Helminthosporol and their Plant Growth-regulating Activities

Several compounds related to helminthosporol (I), a natural plant-growth promoter, were prepared from I and their plant-growth regulating activities were examined together with those of the derivatives reported in the previous paper, using rice and lettuce seedlings. Among the compounds tested, helminthosporic acid (III) exhibited marked elongation effect to the shoot growth of rice and lettuce seedlings, whereas the effect of I was specific to the former. Results of the biological test are reported in details.     

鸡蛋花中化学成分及生物活性研究进展

本文对鸡蛋花植物的化学成分和生物活性进行综述,为该植物的进一步开发和利用提供科学依据。     

Syntheses of New Quarternary Ammonium Iodides as Plant Growth Retardants and Their Biological Activities

Twelve new quarternary ammonium compounds were synthesized and their plant growth retarding activities were examined. Among the candidates, N,N,N-trimethyl-l-methyl-3-(3′,3′5′-trimethylcyclohexyl)- and N,N,N-trimethyl-l-methyl-3-(3′,3′,5′,5′-tetramethylcyclohexyl)-2-propenylammonium iodides were the most effective to suppress the growth of rice and cucumber seedlings, and their activities were far stronger than those of any growth retardants hitherto known.     

Syntheses and Biological Activities of New Plant Growth Inhibitors Structurally Related to Abscisic Acid

Several analogs of abscisic acid (ABA) were prepared and their biological activities were assayed. Among the compounds tested, 5-(l, 2-epoxy-2, 6, 6-trimethyl-l-cyclohexyl)-, 5-(l-hydroxy-2, 6, 6-trimethyl-2-cyclohexen-l-yl)- and 5-(l-hydroxy-2-methylene-6, 6-dimethyl-l-cyclohexyl)-3-methyl-cis, trans-2, 4-pentadienoic esters (V, IX, XXIII and XXV) were found to be potent plant growth inhibitors. Their activities were superior or comparable to that of ABA.     

Syntheses of 14C-Labeled Pyrethrin I,Allethrin, Phthalthrin,and Dimethrin on a Submillimole Scale

Studies on the metabolic fate and degradation chemistry of pyrethroid insecticide chemicals are greatly facilitated by the use of compounds radiolabeled, in separate preparations, in the acid and alcohol moieties. Acid-labeled preparations were made by converting d-trans-chrysanthemic acid-1-¹⁴C (88 mg, 1.3 mCi/mm) into d-trans-d-pyrethrin-1-¹⁴C (68 mg, 1.3 mCi/mm), d-trans-d-allethrin-¹⁴C (43 mg, 1.3 mCi/mm), d-trans-dimethrin-¹⁴C (54 mg, 0.294 mCi/mm), and d-trans-phthalthrin-¹⁴C (47 mg, 0.294 mCi/mm), incorporating approximately 81% of the starting radiocarbon into the four pyrethroid preparations. Alcohol-labeled preparations were made by converting acetone-1,3-¹⁴C into d-trans-dl-ailethrin-¹⁴C (146 mg, 0.162 mCi/mm) and formaldehyde-¹⁴C into d-trans-phthalthrin-¹⁴C (299 mg, 0.276 mCi/mm). Each labeled compound had a high stereochemical purity and a radiochemical purity of greater than 99%. Detailed procedures were worked out for all conversions which took place in high yields except in one case: the synthesis of allethrin labeled in the alcohol moiety.     

莲藕的化学成分与生物活性研究进展

对莲藕(Nelumbo nucifera Gaertn)不同组织(莲藕、荷花、荷叶、莲梗、莲子、莲心、莲蓬)的有效化学成分(类黄酮、酚类、生物碱、三萜、多糖、SOD、膳食纤维、挥发油)作了简要的综述,并对其主要的生物活性进行了归纳,以期对莲藕资源的综合利用提供理论依据。     

Biological Activities of p-Ethylphenyl and p-Acetylphenyl Phosphates and their Thiono Analogs

Sixteen phosphate or phosphorothioate esters related to neurotoxic tri-p-ethylphenyl phosphate and its active metabolites were synthesized and their biological activities including inhibitory activity against cholinesterases, insecticidal activity, toxicity to mammals and neurotoxicity were examined. Dialkyl p-ethylphenyl phoshates, p-acetylphenyl phosphates and their thiono analogs showed insecticidal activity, but did not show the ataxic sign by any sublethal doses in hens. When a methyl group was introduced on p-acetylphenyl ring, the biological activity changed remarkably by its position. The introduction of a methyl group into o-position made the ester inactive, while the introduction into m-position made it active to insects selectively.