6-硫-6-烷硫基-12H-氯代双苯并[d,g][1,3,2]-二氧磷杂八环的合成

通过双- (2 -羟基 -氯代苯基 )甲烷 2与 P4S10 在三乙胺存在下的关环反应 ,得到了6 -硫 - 6巯基 - 12 H-氯代双苯并 [d,g][1,3,2 ]-二氧磷杂八环三乙胺盐 3,后者与卤代烷酯化得到了一系列 6 -硫 - 6 -烷硫基 - 12 H-氯代双苯并 [d,g][1,3,2 ]-二氧磷杂八环 4 ,测试并讨论了它们的1H和31P NMR数据。初步生物试验结果表明化合物 4对黄瓜霜霉病菌具有较好的抑制活性。     

Fungitoxicity of hydroxy- and methoxy-substituted phenyl- and naphthyl-benzofurans,phenylbenzo[b]thiophenes and phenylindoles

The antifungal activities in vitro of 43 methoxy- and hydroxy-substituted aryl-benzofurans, phenylbenzo[b]thiophenes and phenylindoles were compared with those of the unsubstituted compounds. Monohydroxy derivatives were usually the most fungitoxic against Alternaria brassicicola, Botrytis cinerea, Septoria nodorum, Cladosporium cucumerinnum, Fusarium culmorum and Uromyces fahae but the precise effect of substitution upon activity varied with the nature of the parent aryl-hetocyclic compound, with the position in the molecule, and with the presence of other substituents. Fangitoxicity did not correlate significantly with the partitioning properties of the molecuie as measured by reversed-phase thin-layer chromatography.     

6-N-取代的2,4,8,10-四氯-6-硫-12H-双苯并[d,g][1,3,2]-二氧磷杂八环的合成及杀菌活性

通过2,4,6,8,10-五氯-6-硫-12H-双苯并[1,3,2]二氧磷杂八环分别与四氢吡咯、六氢吡啶、吗啉、吡咯、咪唑和1,2,4-三唑反应,得到了6个收率良好的标题新化合物.其结构经1H、13C、31P NMR和元素分析确认.初步杀菌活性测定表明,化合物3c和3d在500 μg/mL浓度下对水稻纹枯病菌Pellicularia sasakii的抑制率为48%～50%,其他化合物对供试菌的活性微弱.     

6-硫-6-烷硫基-12H-氯溴代双苯并[d,g][1,3,2]-二氧磷杂八环的合成

通过双 [2 -羟基 - 3-溴 (氯 ) - 5-氯 (溴 )代苯基 ]甲烷 4 A(4 B)与 P4 S10在三乙胺存在下关环 ,得到中间体 6 -硫 -巯基 - 4 ,8-二溴 (氯 ) - 2 ,10 -二氯 (溴 ) - 12 H -双苯并 [ d,g ][1,3,2 ]-二氧磷杂八环三乙胺盐 5A(5B)。后者与卤代物反应得到了一系列相应的酯 6。测试并讨论了合成的 6的 1H、31P、13 C NMR、MS及抑菌活性。     

Synthesis and in-vitro antifungal activity of 6-trifluoromethylpyrazolo[3,4-d]pyrimidines

Thirty 6-trifluoromethylpyrazolo[3,4-d]pyrimidines were synthesised and tested for antifungal activity in vitro against ten phytopathogenic fungi of different taxonomic classes. Six of the compounds had noteworthy activity against Sclerotinia minor, Corticium solani and Phoma betae. The relationships between structure and activity are discussed on the basis of the present and previous studies.     

Novel 3,3a,5,9b-tetrahydro-2H-furo[3,2-c][2] benzopyran derivatives: synthesis of chiral glycol benzyl ether herbicides

Novel tricyclic 3,3a,5,9b-tetrahydro-2H-furo[3,2-c][2]benzopyran (TFB) derivatives were synthesized, and their herbicidal activities were elucidated. They were synthesized from D-glucose as a natural chiral source. The formation of the TFB skeleton was achieved by a Friedel-Crafts type intramolecular cyclization of methyl 5-deoxy-2,3-O-dibenzyl-5-C-methyl-D-xylofranosides. The intramolecular cyclization was dependent upon the electronic effects of the substituents at the C-2 benzyloxy group of methyl xylofranosides. Some TFBs exhibited a remarkable herbicidal activity to annual paddy weeds, such as Echinochloa sp, without injury to the rice.     

含大体积取代基的吡唑并三嗪酮类化合物的合成及除草活性

以1-(取代)苯基-5-氨基-1H-吡唑-4-甲酸乙酯或1-叔丁基-5-氨基-1H-吡唑-4-甲酰氯和2-甲基-4-炔丙基-6-氨基-7-氟-2H-苯并[b][1,4]-噁嗪-3(4H)-酮为初始原料,分别通过不同的合成路线,得到22个未见文献报道的含大体积取代基的吡唑并三嗪酮类化合物,所有化合物的结构均通过核磁共振氢...     

Synthesis and in-vitro antifungal activity of 6-trifluoromethyipyrazolo[3,4-6d]pyrimidin-4(5H)-thiones

Twelve 6-trifluoromethylpyrazolo[3,4-d]pyrimidin-4(5H)-thiones were prepared by the reaction between 4-thiocarbamoyl-5-aminopyrazoles and trifluoroacetic anhydride. They were tested in vitro for antifungal activity against a series of phytopathogenic fungi of different taxonomic classes. The EC50 and MIC values of four compounds were comparable or inferior to those of reference commercial fungicides in controlling Sclerotinia minor, Corticium solani and Phytium ultimum.     

A new type of plant activator: thieno[2,3-d][1,2,3]thiadiazole-6-carboxylic acid derivatives

A short and efficient synthesis of a series of the title compounds is presented starting with methylenebutanedioic acid and thioacetic acid. Using the Hurd–Mori reaction in the key step, the optimised reaction sequence allows the large-scale preparation of this new type of plant activator in a few steps with a high overall yield. Additional functionalisation of the 5-position via directed ortho-lithiation methodology is also described. © 1998 Society of Chemical Industry     

N-(7-氟-3-氧-3,4-二氢-苯并噁嗪-6-基-)乙酰胺类化合物的合成及除草活性

为了寻找高效、安全的具有除草活性的新化合物,利用2-取代乙酰氯和2H苯并噁嗪-3-酮反应合成了9个N-(7-氟-3-氧-3,4-二氢苯并噁嗪-6-基-)乙酰胺类化合物,其结构经元素分析、IR、1H NMR确证。初步除草活性测试表明:在有效剂量75 g/hm2下,化合物 5d 芽后茎叶处理对刺苋Amaranthus spinosus等4种杂草显示出90%以上的抑制率。     

Metabolism of [2,5-14c]piperazine in barley plants

The shoots of barley plants root-treated with [2,5-¹⁴C]piperazine were analysed 30 days after treatment. Methanol extraction left a solid residue which contained 31.9% of ¹⁴C (all percentages refer to the total of ¹⁴C incorporated into the shoots); further extraction with acidified methanol and dimethyl sulphoxide dissolved respectively 3.2% and 5.8% of ¹⁴C. The initial methanol extract contained radioactive piperazine (16.8%), iminodiacetic acid (8.6%), glycine (15.4%), oxalic acid (7.2%), and un-identified compounds (20.1%). In barley, piperazine is the product of the most advanced metabolism so far identified of the fungicide triforine, 1,4-bis(2,2,2-trichloro-1-formamidoethyl)piperazine; the results obtained here show that piperazine is certainly not the end-product of the metabolism of triforine in barley.     

N-(7-氟-3-氧-3,4-二氢-苯并[b][1,4]口恶嗪-6-基-)乙酰胺类化合物的合成及除草活性

为了寻找高效、安全的具有除草活性的新化合物,利用2-取代乙酰氯和2H苯并[b][1,4]口恶嗪-3-酮反应合成了9个N-(7-氟-3-氧-3,4-二氢苯并[b][1,4]口恶嗪-6-基-)乙酰胺类化合物,其结构经元素分析、IR1、H NMR确证。初步除草活性测试表明:在有效剂量75g/hm2下,化合物5d芽后茎叶处理对刺苋Amaranthus spinosus等4种杂草显示出90%以上的抑制率。     

Studies on pesticides based on coumarin. II. Synthesis and antifungal activity of ten 2-alkyl-7, 8-dihydro-3-hydroxynaphtho[1,2-c]chromen-6-ones

A series of 2-alkyl-7, 8-dihydro-3-hydroxynaphtho[1,2-c]chromen-6-ones was synthesised by the condensation of ethyl 3, 4-dihydro-1-oxonaphthalene-2-carboxylate with substituted phenols in the presence of POCl₃. The compounds were characterised and tested for their toxicity towards the mycelial growth of seven phytopathogenic fungi in culture. Drechslera oryzae, Rhizoctonia solani and Colletotrichum falcatum exhibited maximum sensitivity to these compounds whereas Macro-phomina phaseolina, Fusarium solani, Alternaria alternata and Pythium aphanidermatum were less sensitive. 2-Ethyl-7, 8-dihydro-3-hydroxy-naphtho[1,2-c]chromen-6-ones possessed greatest toxicity with EC₅₀ values ranging from 0.2 to 2.5 μg ml^?1 against all fungi except A. alternata and P. aphanidermatum.     

Excretion,distribution and depletion of [14C]cypermethrin and cis and trans isomers of 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid administered orally to laying hens

Radiolabelled racemic cypermethrin, and the cis and trans isomers of 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (labelled at C-1 of the cyclopropane ring) were each separately administered orally in feed for three consecutive days to White Leghorn laying hens. The amount of individual compound dosed was approximately 7.5 mg per hen per day. Radiocarbon was eliminated very rapidly in excreta. Tissue residues were generally very low with the exception of fat depots, but trace amounts of radiocarbon residues were still detectable in fat, liver and kidney 11 days post-treatment. Residues were detected in the egg albumen of hens treated with cypermethrin and cis isomer of the acid, but none was detected from trans acid. Metabolites identified included products arising from the hydrolysis of the ester bond of cypermethrin, followed by oxidative attack on one or both methyl groups. The rate of oxidative attack on methyl groups was influenced by the geometry of the dichlorovinyl group. On the basis of the metabolites identified a metabolic pathway for cypermethrin in laying hens was proposed which included hydrolysis of the ester bond followed by oxidation of methyl group(s). The data indicate that use of cypermethrin as recommended should not produce residues in eggs and meat of laying hens at levels that are of toxic concern.     

Metabolism of [14C]parathion and [14C]paraoxon in isolated,perfused rat livers

Perfusion of ¹⁴C-(ring)-parathion or ¹⁴C-(ring)-paraoxon with blood through isolated, intact rat livers resulted in the rapid degradation of these insecticides. Degradation was negligible in the absence of rat liver (controls), thus demonstrating the capacity of the liver per se to effectively degrade these compounds. Of the total radiocarbon recovered after liver perfusion with [¹⁴C]parathion, 33 % could be attributed to unchanged [¹⁴C]parathion (similarly distributed between the liver and the blood) while 67.9 % was degraded to water soluble compounds and 2.5% was converted to organic soluble paraoxon and traces of p-nitrophenol. Nearly all of the [¹⁴C]paraoxon, however, was degraded by the intact rat liver, resulting in water soluble products that amounted to 98.5% of the total radiocarbon recovered. Unexplained losses of radiocarbon with the perfusion apparatus used were lower in the presence of rat liver which degraded the insecticides to more water soluble compounds. The water soluble degradation products produced from [¹⁴C]parathion and [¹⁴C]paraoxon were non-toxic to mosquito larvae (Aedes aegypti L.). These ring-labelled products were found to be conjugated p-nito-phenol. Nearly all of the water soluble radiocarbon was located in the perfused blood, while only small amounts (1.8 to 3.0% of recovered) were excreted via the bile or were associated with the liver tissue (1.3 to 1.8 % of recovered).     

Metabolism of carbosulfan [2,3-dihydro-2,2-dimethylbenzofuran-7-yl (di-n-butylaminothio)methylcarbamate] in the rat and house fly

The metabolism of carbosulfan, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl (di-n-butylaminothio)-methylcarbamate, was studied in the rat and house fly. Carbosulfan was metabolized via at least two major pathways in the rat, by initial oxidation of the sulfur atom and by NS bond cleavage. The principal rat metabolites were the conjugated keto-phenol from the ring-labeled carbo-sulfan, carbon dioxide from the carbonyl-labeled carbosulfan, and dibutylamine from the dibutylamino-labeled carbosulfan. In house flies, carbosulfan was converted primarily into carbofuran and related oxidation products. The lower mammalian toxicity of carbosulfan compared to its insecticidal activity is explained on the basis of differences in routes and rates of metabolism of carbosulfan in mammals and insects.     

6-N-取代的2,4,8,10-四氯-6-硫-12H-双苯并 -二氧磷杂八环的合成及杀菌活性

通过2,4,6,8,10-五氯-6-硫-12H-双苯并 二氧磷杂八环分别与四氢吡咯、六氢吡啶、吗啉、吡咯、咪唑和1,2,4-三唑反应,得到了6个收率良好的标题新化合物。其结构经1H、13C、31P NMR和元素分析确认。初步杀菌活性测定表明,化合物 3c和3d 在500 μg/mL浓度下对水稻纹枯病菌Pellicularia sasakii的抑制率为48%~50%,其他化合物对供试菌的活性微弱。     

Residues of clenpirin [2-(3,4-dichiorophenylimino)-l-n-butyl pyrrolidine] in the fatty tissues of steers and in butter fat

A series of trials in which cattle were either treated dermally or dosed orally with clenpirin [2-(3,4-dichlorophenylimino)-l-n-butyl pyrrolidine] was undertaken. Tissue fat from steers and butter fat from milking cattle were sampled and residue levels determined colorimetricaliy. Residues following a single application of clenpirin (9 litres/beast at 0.25% w/v) reached an average maximum of 2.0 mg/kg in body fat and then declined to 0.2 mg/kg after 14 days. Multiple applications (9 litres/beast at 0.25% w/v) resulted in a progressive buildup of residues in body fat to about 30 mg/kg after 4 treatments. When steers were dosed orally with technical clenpirin at 700 mg/beast/day for 15 days the average fat level reached 0.7 mg/kg. In a series of trials with milking cattle a single dermal exposure (0.23-0.3% w/v aqueous emulsion) yielded residues in butter fat ranging from 1 5.5-51 1 mg/kg at the first sampling 5 h after treatment. Six days later these had declined to about 0.8 mg/kg.     

DSC and Raman study on the interaction of DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)-ethane] with liposomal phospholipids

In this paper, a DSC and Raman study of hydrated multilamellar DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) and DMPE (1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine) liposomes in presence of increasing amounts of DDT is reported.The observed changes denote that DDT molecules interact with both phospholipids and that the interaction mainly involves the external part of the bilayer since the deep penetration into the hydrophobic core is prevented by the setting up of polar interactions between the three aliphatic C-Cl bonds of the trichloro group of DDT and the -N⁺(CH₃)₃ of DMPC or the -NH₃⁺ groups of DMPE molecules.This behaviour was particularly evidenced in presence of DMPE, as the insertion of DDT molecules into the central part of the bilayer seems to be completely excluded.Moreover, in DMPE liposomes the overall structure of the bilayer changes to a well defined and structured ‘phase II’ in presence of even small DDT amounts.     

Synthesis and Anthelmintic Activity of 7-Hydroxy- 5-oxo-5H-thieno[3,2-b]pyran-6-carboxanilides and -6-thiocarboxanilides

7-Hydroxy-5-oxo-5H-thieno[3,2-b]pyran-6-carboxanilides and -6-thio-carboxanilides represent a novel series of anthelmintic compounds, with broad-spectrum activity against important parasitic nematodes in sheep and dogs. In particular, an improved efficacy against Trichostrongylus colubriformis in sheep over the related 3-carbamoyl-4-hydroxycoumarins has been noted. New synthetic routes to the key intermediate, 7-hydroxythieno[3,2-b]pyran-5-one, have been developed.