O-乙基-N-异丙基(取代硫脲基)硫代磷酰胺酯类衍生物杀菌作用的构效关系研究

研究了一系列O-乙基-N-异丙基(取代硫脲基)硫代磷酰胺酯类化合物的杀菌活性,发现分子的活性中心在硫脲基上,其氮原子上所连的取代基对活性有重要影响。采用取代基物理参数及化合物对多种植物病菌的抑制活性,进行了结构与活性定量关系的研究。建立了较好的结构与活性的相关式,预测出更高活性的化合物并得到实验证实。     

O-乙基O-芳基N-异丙基硫代磷酰胺脂结构与活性定量关系中芳基邻位取代效应的影响

利用π、Σσ、F、Verloop的STERIMOL参数及邻位取代基形成氢键的指示变量、定量地分析了39个O-乙基O-芳基N-异丙胺基硫代磷酰胺酯类化合物结构与除草活性的关系,进一步讨论了芳基邻位取代基团对分子除草活性的贡献。     

O-烷基,O-芳基硫代磷酰取代硫脲和O-烷基硫代磷酰-双-取代硫脲的研究(Ⅱ)

用硫氰酸钾与硫代磷酰氯制备了硫代磷酰异硫氰基酯和二异硫氰基酯,并以其与不同胺反应,合成了硫代磷酰取代硫脲和硫代磷酰-双-取代硫脲两系列20个新的有机磷化合物,经1HNMR、IR及元素分析确定了它们的化学结构,测定了它们的生物活性。结果表明只有O-异丙基,O-(4-甲基-2-硝基苯基)-N''-萘基硫代磷酰硫脲(PD-1)具有较好的杀菌活性。     

O-乙基-N-烷基(取代硫脲基)硫代磷酰胺酯的合成及其生物活性

采用O-乙基-N-烷基(异硫氰基)硫代磷酰胺酯与不同胺的加成反应,合成了一系列新型的O-乙基-N-烷基(取代硫脲基)硫代磷酰胺酯,其结构经元素分析、IR及¹HNMR证实.生物活性初步测定表明,这类化合物均具有一定的广谱杀菌及除草活性.     

新型O-取代苯磺酰羟胺化合物的合成及其热性能

以O-取代苯磺酰氯和乙酰羟肟酸乙酯为原料，经消除、水解反应合成了6个新型的O-取代苯磺酰羟胺化合物：O-2-硝基苯磺酰羟胺、O-3-硝基苯磺酰羟胺、O-2,4-二硝基苯磺酰羟胺、O-2,4-二甲基苯磺酰羟胺、O-2,4,6-三甲基苯磺酰羟胺和O-2,4,6-三异丙基苯磺酰羟胺，其结构经¹H NMR, ¹³C NMR, IR和元素分析表征。并初步探讨了可能的反应机理。利用差示扫描量热分析(DSC)研究了化合物的热性能。结果表明：苯环上取代基供电子能力越强，化合物的热稳定性越好。     

O,O-二乙基亚磷酰基异氰酸酯与亚苄基苯胺的反应研究

O,O-二乙基亚磷酰基异氰酸酯与亚苄基苯胺反应,当亚苄基苯胺分子中苯环上具有邻位取代基时,产物不是稳定的1,3,4-二氮磷杂环戊烷衍生物,却是α-(O,O-二乙基)膦酰基苄基苯胺.这可能是由于邻位取代基的立体效应阻碍了环加成反应,且中间体水解之故.所得化合物均经元素分析、IR、H、N、AF及MS谱证实.     

S-[N-取代氨基甲酰甲基]-O,O-二烷基二硫代磷酸酯类化合物的合成及其对植物的抑制活性

用O,O-二烷基二硫代磷酸酯与α-卤代乙酰胺在丙酮或氯仿/水体系中反应,合成了40余种标题化合物,确定其结构;研究了酰胺分子中不同取代基对反应的影响.测定它们对植物的抑制活性发现,引入磷酰基可保持原来卤代酰胺的生物活性,但选择性却有明显提高,初步讨论了这类化合物结构与活性的规律。     

硫代磷酰胺酯类化合物的合成及其结构与除草活性的定量关系

O-乙基O-芳基N-异丙基硫代磷酰胺酯(Ⅰ)具有除草活性,为了研究这类化合物的结构与活性的定量关系,用O-乙基O-芳基硫代磷酰氯与异丙胺在40％NaOH存在下于0℃反应,制得了30余个化合物Ⅰ,收率及纯度均较理想。并发现化合物的活性大小与苯环上取代基密切相关。根据Hansch方程,发现化合物Ⅰ抑制稗草生长的活性与其苯环上取代基的亲脂性参数π,空间效应参数E_s,电子效应参数σ及场效应参数F密切相关。分别用实验测得的△R_m及△δ_p代替π及σ和F进行回归分析,亦可得较好的相关关系。文中讨论了该两项实验参数在结构与活性定量关系研究中的实用意义。     

季铵化N,O-(2-羧乙基)壳聚糖的制备及其抑菌性能

以缩水甘油基三甲基氯化铵(GTMA)、缩水甘油基三乙基氯化铵(GTEA)、缩水甘油基三丙基氯化铵(GTPA)、缩水甘油基三丁基氯化铵(GTBA)和缩水甘油基二甲基苄基氯化铵(GDMBA)等活性季铵盐为季铵化试剂,对N,O-2-羧乙基壳聚糖(N,O-2-CEC)进行了化学改性,得到了系列季铵化N,O-2-CEC(QCEC...     

O-氯丙基和O-氰丙基间苯二酚杯芳烃的合成，晶体结构和电化学性质

四烃基和四二茂铁基间苯二酚杯芳烃在丙酮回流条件和碳酸钾存在下用1-溴-3-氯丙烷或4-氯丁腈进行烃基化反应分别生成全取代的O-氯丙基和O-氰丙基间苯二酚杯芳烃,晶体结构测定表明烷基间苯二酚杯芳烃倾向于以全顺式构型存在,而芳基间苯二酚杯芳烃倾向于以顺-反-反式构型存在。本文还已经了四二茂铁基间苯二酚杯芳烃的电化学性质。     

S-烷基O-芳基硫代磷酸衍生物的合成及其杀虫活性的研究

研究了O,O-二烷基O-芳基硫代磷酸酯与三氧氧磷的异构化氯化反应。由此生成的S-烷基O-芳基硫代磷酰再与亲核试剂(醇,酚,硫醇,硫酚,伯胺或氨)在缚酸剂存在下反应,合成了42种化合物,其中34种未见文献报道。本文还研究了这类化合物的杀虫活性。     

Potassium Fluoride on Alumina: Synthesis of O-Aryl N,N-Dimethylthiocarbamates and their Rearrangement into S-Aryl N,N-Dimethyl-Thiocarbamates Under Microwave Irradiation

A series of O-aryl N,N-dimethyl thiocarbamates have been prepared by the reaction of dimethylthiocarbamoyl chloride with phenols absorbed on potassium fluoride on alumina. The rearrangement of O-aryl N,N-dimethylthiocarbamate into S-aryl N,N-dimethyl thiocarbamate under microwave irradiation was also studied. The use of conductive support like graphite or silicon carbide allow these rearrangements although the O-aryl N,N-dimethylthiocarbamates have very low dielectric lost.     

Substituent Effects on 31P NMR Chemical Shifts and 1JP–Se of triarylselenophosphates

The effect of electron-withdrawing (EW) and electron-releasing (ER) substituents on the ³¹P NMR chemical shifts and the structural parameters of a series of tris-(p-X-aryl)selenophosphates is reported in this article. Similarly to O-aryl phosphates and O-aryl thiophosphates, EW groups attached to aromatic rings induce a shielding effect on the ³¹P NMR signal. After a detailed experimental and theoretical analysis, we confirmed that the selenium atom is the main part responsible for the charge density transfer toward phosphorus through a back-bonding effect. The obtained ¹J_P-Se values for the complete series agree with this observation.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

A mild thermal and acid-catalyzed rearrangement of O-aryl ethers into ortho-hydroxy arenes

[reaction: see text] An unusual rearrangement of an O-aryl ether to an ortho-hydroxyaryl system was discovered during our studies on the synthesis of diazonamide A. We discuss the exploration of this rearrangement under mild thermal and both Br?nsted and Lewis acid-catalyzed conditions.     

O-乙基O-取代芳基N-异丙基硫代磷酰胺酯类化合物急性毒性与结构的相关性

通过测定O-乙基O-取代芳基N-异丙基硫代磷酰胺酯类化合物的急性毒性、疏水性、电性、水解性,对这类化合物的急性毒性与化学结构进行了定量构-效相关(QSAR)分析。表明该类药物的急性毒性与电偶极矩μ显著相关,提示药物分子与受体的作用可能含有偶极成分。根据实验所得的QSAR方程,证明该类药物分子当电偶极矩小(苯环对位有推电子基团)、亲水性高时,其急性毒性较低。     

Curved Hammett plot in alkaline hydrolysis of O-aryl thionobenzoates: change in rate-determining step versus ground-state stabilization

Second-order rate constants have been measured for alkaline hydrolysis of O-aryl thionobenzoates (X-C(6)H(4)-CS-OC(6)H(4)-Y) in 80 mol % H(2)O-20 mol % DMSO at 25.0 +/- 0.1 degrees C. The Hammett plot for the reaction of O-4-nitrophenyl X-substituted thionobenzoates (X-C(6)H(4)-CS-OC(6)H(4)-NO(2), 1a-e) exhibits a downward curvature. However, a possible traditional explanation in terms of a change in the rate-determining step (RDS) has been considered but rejected. The proposed explanation involves stabilization of the ground-state (GS) through-resonance interaction between the electron-donating substituent X and the thionocarbonyl functionality on the basis of the linear Yukawa-Tsuno plot obtained for the same reaction. The Br?nsted-type plot for the reaction of O-aryl thionobenzoates (C(6)H(5)-CS-OC(6)H(4)-Y, 2a-i) is linear but exhibits many scattered points with a small beta(lg) (-0.35). The Hammett plot for the same reaction shows rather poor correlation with sigma(-) constants but much better correlation with sigma(o) constants. The alkaline hydrolysis of O-aryl thionobenzoates (1a-e and 2a-i) has been proposed to proceed through an addition intermediate in which bond formation is the RDS.     

Enantiomer separation and preparation of five organophosphorus compounds and their biological activities

Summary The direct enantiomeric resolution of five O-aryl O-alkyl N-alkyl-phosphoramidothioates was carried out and their pure enantiomers were prepared on a commercially available Pirkle model chiral column (OA-4700). Absolute configurations of the enantiomers were determined by circular dichroism (CD) spectroscopy. S-enantiomers were the first compounds to elute chromatographically and the chromatographic elution order was in accordance with the results of computer simulating calculation. The biological activity test suggested that all the S-enantiomers were more active than R-enantiomers in killing barnyard grass.     

Synthesis of thiopyrano[4,3-b]benzofurans

Representatives of a new heterocyclic system — thiopyrano[4,3-b]benzofuran — were synthesized by cyclization of the O-aryl ethers of tetrahydro-4-thiopyrone and 4-thiochromanone oximes in acid media.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 762–764, June, 1971.     

Copper-catalyzed arylation of beta-amino alcohols

[reaction: see text] Methods for synthesizing N-aryl beta-amino alcohols and O-aryl beta-amino alcohols are described. The presence of a neighboring hydroxyl or amino group, respectively, is thought to activate beta-amino alcohols toward these transformations. These protocols significantly increase access to a variety of arylated beta-amino alcohols.