Design,Synthesis and Herbicidal Activity of Novel Sulfonylureas Containing Tetrahydrophthalimide Substructure

To develop novel sulfonylurea herbicides, a series of chlorsulfuron derivatives was designed and synthesized through introducing tetrahydrophthalimide substructure taken from protoporphyrinogen IX oxidase(PPO) inhibitors onto the critical 5-position of the classical benzene ring. The structures of title compounds were confirmed by infrared spectroscopy, ultraviolet spectroscopy, ¹H and ¹³C NMR spectrometry, mass spectrometry and elemental analysis. In addition, the crystal structure of compound II-5 was further determined by X-ray diffraction analysis. Bioassay results showed that individual compounds exhibited good herbicidal activities, especially compound II-8, which displayed 100% inhibition rate against Echinochloa crusgalli at 150 g/ha(1 ha=10⁴ m²) with the method of foliage spray in the pot experiment.     

Synthesis and Herbicidal Activities of Novel Uracil Derivatives Containing Pyrimidinyl Moiety

In order to find novel protoporphyrinogen oxidase inhibitors with high efficacy, broad-spectrum activity, and safety to crops, nine title compounds（4a-4i） were designed and synthesized by introducing pyrimidine moiety into the uracil skeleton with commercially herbicide butafenacil as the lead compound. Their structures were con- firmed by 1H NMR, IR, mass spectroscopy and elemental analysis. The bioassay results indicate that most of com- pounds 4 tested exhibit good to excellent herbicidal activities against B. campestris, A. retroflexus, E. crusgalli and D. sanguinalis in pre-emergence treatment at a dose of 1.5 kg/ha（1 ha=10^4 m^2）, for example, compound 4i showed 100% inhibition against the four plants tested in pre-emergence treatment at a dose of 1.5 kg/ha. So, this type of skeleton can be used as a valuable lead compound for the further development of a pre-emergent herbicide.     

Synthesis and biological activity of novel N-(3-furan-2-yl-1-phenyl-1H-pyrazol-5-yl) amides derivatives

A series of novel N-(3-furan-2-yl-1-phenyl-1H-pyrazol-5-yl) amides derivatives were designed and synthesized. Their structures were confirmed by ¹H NMR, ¹³C NMR and HRMS. All title compounds were evaluated for their herbicidal and antifungal activities. Preliminary bioassay results indicated that the title compounds showed good to moderate herbicidal activity at 1000 mg/L. Compound 6q presented the best activity against Digitaria sanguinalis (L) Scop., Amaranthus retroflexus L. and Arabidopsis thaliana with an inhibition degree of five. Compound 6d also showed an inhibition degree of five against D. sanguinalis. In addition, at 50 mg/L, most compounds exhibited good in vitro antifungal activity against Sclerotinia sclerotiorum, with compound 6c showing over 90% antifungal activity against S. sclerotiorum and Pellicularia sasakii.     

含有单取代嘧啶的新型磺酰脲类化合物的设计、合成及除草活性

为了寻找高效的磺酰脲类除草剂, 以商品化磺酰脲类除草剂为基础, 将单取代嘧啶结构引入到分子中, 合成了一系列新型磺酰脲类化合物, 并通过¹H NMR和高分辨质谱确定了其结构. 采用盆栽法和平皿法测试了所有化合物的除草活性以及部分化合物对油菜的IC₅₀值. 结果表明, 一些化合物具有一定的除草活性, 其中化合物7b和7d对油菜和反枝苋具有较好的抑制活性.     

Synthesis and Herbicidal Activities of 2-Methylpropan-2-aminium O-Methyl 1-（Substituted Phenoxyacetoxy）alkylphosphonates

A series of 2-methylpropan-2-aminium O-methyl 1-（substituted phenoxyacetoxy）alkylphosphonates （5a-5o） was selectively synthesized by reacting the corresponding O,O-dimethyl l-（substituted phenoxyacetoxy）-alkylphosphonates with an excess of 2-methylpropan-2-amine.The results of preliminary bioassays show that the title compounds exhibit moderate to good herbicidal activities against Brassica napus and Echinochloa crusgalli.Furthermore,compounds 5a-5j,which show much higher activities than compounds 5k-5o,were selected to further evaluate their post-emergence herbicidal activity at a dosage of 150 g/ha（l ha=10000 m2）.Especially,2-methylpropan-2-aminium O-methyl 1-[2-（4-chloro-2-methylphenoxy）acetoxy]butylphosphonate（5h） shows 100％ inhibitory effect on the growth of Brassica juncea and Amaranthus retroflexus,which is comparable with the commercial herbicide 2,4-dichlorophenoxy acetic acid（2,4-D）.     

Synthesis,structural characterization and solubility of 2-(1-substituted-1,11-undecylidene)-5-arylimino-△~3 -1,3,4-thiadiazolines

A series of novel 2-(1-substituted-1,11-undecylidene)-5-arylimino-△~3-1,3,4-thiadiazolines(4) were synthesized and their structure was characterized by ~1H NMR,~(13)C NMR and elemental analysis.Their solubility in both polar and non-polar solvents is significantly improved owing to the introduction of ethyl or methylthio group at cyclododecyl ring as compared with parent compounds[1,2-(1,11-undecylidene)-5-arylimino-△~3-1,3,4-miadiazolines].However,their fungicidal activity against Rhizoctonia solani is ...     

1,3,2-Diazastanna-[3]ferrocenophanes bearing alkyn-1-yl groups at tin and their 1,1-organoboration with triethylborane—molecular structure of a novel spirotin compound

2,2-Dichloro-1,3-bis(trimethylsilyl)-1,3,2-diazastanna-[3]ferrocenophane (3) reacts with lithium alkynides LiCCR¹ to give the corresponding di(alkyn-1-yl)tin derivatives 4a (R¹=^tBu) and 4b (R¹=SiMe₃). 1,1-Organoboration of 4 with triethylborane affords the spirotin compounds 5 which contain both a ferrocenophane and a stannacyclopentadiene ring. The crystal structure of 5b was determined by X-ray analysis. The compounds 4 and 5 were characterised in solution by multinuclear magnetic resonance (¹H-, ¹¹B-, ¹³C-, ¹⁵N-, ²⁹Si-, ¹¹⁹Sn-NMR), using pulsed field gradients in HMBC experiments for the ¹H detected ¹⁵N- and ¹¹⁹Sn-NMR signals. The compound 5b was also studied by solid-state ¹³C, ²⁹Si and ¹¹⁹Sn MAS NMR in order to correlate liquid and solid-state NMR data with the structural evidence.     

Synthesis and insecticidal evaluation of tetrahydroimidazo[1,2-a]pyridin-5(1H)-one derivatives

A series of novel tetrahydroimidazo[1,2-a]pyridine-5(1H)-one derivatives containing a electronegative pharmacophore(=CNO₂) were synthesized via practical aza-ene reaction and characterized by ¹H NMR, ¹³C NMR, ¹⁹F NMR and HRMS. Preliminary bioassays showed that some of the target compounds exhibited good insecticidal activity against brown planthopper(Nilaparvata lugens) and cowpea aphids(Aphis craccivora) at 500 mg L^-1. Among them, compound 11h was active against brown planthopper at 100 mg L^-1. The insecticidal activities varied significantly depending on the types and patterns of the substituents, which provided guidance for further investigation on structure modifications.     

含芳氧乙酰基和间-三氟甲基苯基的双酰胺化合物的合成及其除草活性

通过组合不同除草作用机制的活性基团,采用芳氧乙酸为酸组分的Ugi四组分反应合成了一系列芳氧乙酰基和间三氟甲基苯基片段的双酰胺化合物3a~3v,采用IR、¹H NMR、EI-MS和元素分析等技术手段对其结构进行了表征。 温室盆栽测试结果表明,部分目标化合物对油菜、反枝苋、稗草和马唐表现出中等至良好的除草活性,如化合物3r在温室盆栽时,在1.5 kg/ha剂量下,在苗前处理时对反枝苋和马唐显示出100%的抑制活性;在苗后处理时对马唐显示出100%的抑制活性。 初步探讨了目标化合物的构效关系。     

Synthesis and Herbicidal Activity of 3-Acetyl-4-hydroxy-2,1-benzothiazine Derivatives

In order to develop a novel herbicide containing the 2,1-benzothiazine motif, a series of 3-acetyl-4- hydroxy-2,1-benzothiazine derivatives was synthesized. All the target compounds were confirmed by 1H NMR,13C NMR, and high-resolution mass spectrometry(HRMS).In addition,the crystal structure of compoimd T27 was detemiined by single crystal X-ray diflraction. The bioassay results showed that some of the 3-acetyl-4-hydroxy- 2,1-benzothiazine derivatives(T13, T15, T22, and T24) showed good herbicidal activity at a dosage of 100 pg/mL. Among them,compounds T22 and T24 showed promising post-emergent herbicidal activities against Brassica campestris and Amaranthus retroflexus even at a dosage of 375 g/ha(1ha=104 m^2) in the greeiiliouse test. Studies on the structure-activity relationship demonstrated that the type of acetyl group played an important role in the herbicidal activity, and that the introduction of a phenoxyacetyl group at the 3-position of 2,1-beiizothiazine was beneficial in improving the herbicidal activity. The present study also indicated that 3-phenoxyacetyl-4-hydroxy-2,1-benzothiazine could be a potential lead compound for fiirther development of novel 2,1 -benzothiazine-containing herbicides.     

芳香寡聚磺酸酯桥联大环化合物的合成和紫外光谱

以芳香二磺酰氯和芳香二酚为原料,三乙胺作缚酸剂,二氯甲烷作溶剂,采取一步成环法合成了一系列新型的、芳环单元不同的芳香寡聚磺酸酯桥联大环化合物。 合成产物的结构用IR、¹H NMR、¹³C NMR和MALDI-TOF等技术手段进行了确认。 并对合成方法、紫外光谱和变温核磁结构研究进行了有价值的探讨。 化合物3~5的DMF溶液的最大紫外吸收峰在266 nm处,化合物6在267 nm处,摩尔吸光系数分别是4.65×10⁴、5.61×10⁴、5.09×10⁴和9.98×10⁴ L/(mol·cm);检出限分别是2.15×10^-7、1.78×10^-7、1.96×10^-7和1.00×10^-7 mol/L。 变温核磁数据证明,苯环上连有支链有利于固定构象,可以通过这种方法合成结构固定的杯芳烃。     

The Synthesis and Structure of Herbicidal Mononuclear Cobalt (Ⅱ) Sulfonylurea Complex CoL2 (L=Sulfometuron-methyl Anion)

A number of sulfonylureas are commercialized ALS-inhibiting herbicides to control broad-spectrum weeds in various crops when applied at very low dosage (5-50 g/ha)^[l]. But little sulfonylurea complex is investigated in the literature. Previously we reported the preparation and herbicidal activity of (Chlorsulfuron)₂Cu(OAc)₂^[2]. Herein we report the preparation and structure study of the following novel sulfonylurea cobalt (Ⅱ) complex to study its herbicidal activity:     

新三取代嘧啶苯磺酰脲衍生物的合成与生物活性

设计合成了22个具有4,5,6-三取代嘧啶磺酰脲衍生物, 其结构经1H NMR, MS和元素分析确证. 经盆栽试验测定了化合物的除草活性, 结果表明, 嘧啶环5位取代基的引入对分子除草活性有一定的影响.     

Vibrational (FT-IR and FT-Raman) and NMR studies on selected metal (Ca, Mn, Zn) complexes with ortho-, meta-, and para-iodobenzoic acids

The vibrational (FT-IR and FT-Raman) and NMR (¹H and ¹³C) spectra of Ca, Mn, and Zn complexes with ortho-, meta-, and para-iodobenzoic acids have been studied. The solid state samples of all complexes have been measured within the range 4000–400 cm⁻¹, while water solutions of ortho-iodobenzoates within the range 4000–800 cm⁻¹. Based on previous experimental data and normal mode calculations for simpler complexes the assignment of bands observed in vibrational spectra of studied compounds has been done. Some significant differences in vibrational structure (frequency and intensity of selected bands) have been observed and discussed. The effect of metal on ring vibrations and carboxylic anion stretching and deformation has been investigated. Also, influence of iodine substitution on the aromatic ring and carboxylic anion, depending on iodine ring position, has been discussed. In case of soluble compounds, wavenumbers of characteristic bands of water solution samples have been compared with wavenumbers of corresponding bands of solid state samples.     

Novel phosphorus-silicon synergistic flame retardants:Synthesis and characterization

Three novel flame retardants containing both phosphorus and silicon elements in their structures,including[（1,1,3,3- tetramethyl-1,3-disiloxanediyl）di-2,1-ethanediyl]bis（diphenylphosphine oxide）（FR-1）,[（2,4,6,8-tetramethylcyclotetra-siloxane -2,4,6,8-tetrayl）tetra-2,1-ethanediyl]tetrakis[diphenylphosphine oxide]（FR-2） and 1,3,5,7,9,11,13,15-octakis（di-phenylphosphine oxide-2,1-ethanediyl）pentacyclo[9.5.1.1^3,9.l^5,15.1^7,13]octasiloxane（FR-3） were synthesized by a convenient pathway from the reaction of diphenylphosphine oxide（DPPO） and vinyl-terminated siloxanes under the catalysis of triethylborane. The chemical structures of the target compounds were confirmed by nuclear magnetic resonance(¹H NMR,¹³C NMR,²⁹Si NMR and ³¹P NMR),matrix-assisted laser desorption/ionization time-of-flight mass spectrometry（MALDI-TOF-MS） and Fourier transform infrared（FT IR） measurements.Thermogravimetric analysis（TGA） results indicated that the new flame retardants possessed good thermal stability both in nitrogen and in air.FR-3 containing polyhedral oligosilsesquioxanes（POSS） moiety exhibited the best thermal properties with a 10%weight loss temperature>400℃ and a residual weight ratio>39%at 700℃ .     

芳香寡聚磺酸酯桥联大环化合物的合成及其对Sn2+和Bi3+的识别作用

以4,6-二烷氧基-1,3-苯二磺酰氯和芳香二酚为原料,三乙胺作缚酸剂,二氯甲烷作溶剂,采取一步成环法合成了3种磺酸酯桥联大环化合物。合成产物的结构用IR、¹H NMR、¹³C NMR和MALDI-TOF等技术手段进行了确认。利用紫外光谱分析的方法研究了4,6,16,18-四正戊氧基-11,23-二甲基-1,3,13,15-四磺酸酯间苯芳香大环(5)对Ca²⁺、Pb²⁺及部分过渡金属等20种金属离子的识别。结果发现,其对Sn²⁺显示出一定的选择性,由于Sn²⁺和Bi³⁺协同作用的影响,在化合物5-Sn²⁺的体系中加入Bi³⁺,紫外吸收光谱在325 nm左右的吸收增强了许多,这说明化合物5对Bi³⁺显示出优于Sn²⁺的较好选择性。     

Design and Synthesis of 1-Glycosyl-4-{N-[(2'-morpholinethoxy)-phenyl]aminomethyl}-1H-1,2,3-triazoles as Calcium Activators

A series of novel 1-glycosyl-4-{N-[(2'-morpholinethoxy)phenyl]aminomethyl}-1H-1,2,3-triazoles was designed and synthesized through a simple and efficient multistep synthetic method in good yields. The 1,2,3-triazole moiety acted as a single disubstituted ring and a linker between carbohydrates(D-glucose, D-galactose, maltose and lactose) and morpholine. The compounds were characterized by ¹H NMR, ¹³C NMR and mass spectra(MS). Two different deprotection methods were discussed. The effects of compounds 5a, 5c and 6e on the intracellular calcium ion concentration([Ca²⁺]_i) in the central neurons of S. exigua were well investigated by calcium imaging technique. The results demonstrated that compound 6e could elevate the calcium concentration in the glial cells, not in the neurons.     

NMR conformational studies of (1,2-bis(diarylphosphino) ethane) -(diorgano sulfide) ruthenium complexes

Some (η⁵-cyclopentadienyl)(1,2-bis(diarylphosphino)ethane)(diorganosulfide)ruthenium complexes, [Ru(η⁵-C₅H₅)(Ar₂PCH₂CH₂-PAr₂)(R¹R ²S)]BF₄ (Ar = Ph, p-Tol; R¹, R² = Ph, Et) were prepared. Variable temperature NMR spectra of these complexes showed the existence of two fluxional processes; inversion at the sulfur atom and δ-λ interconversion of the chelate ring. The former process was slower, and its barriers in these complexes were calculated as ca. 7 kcal mol⁻¹. The spectral features of ethyl phenyl sulfide complexes suggested that substantiation of the new chiral center at sulfur induces a significant conformational rigidity at the chelate ring.     

手性膦酸二酯类化合物的合成与结构

手性呋喃酮1a1b与亚磷酸三酯2a2b通过串联的不对称Michael加成/分子内Michalis-Arbazov重排反应,得到含磷官能团的新手性化合物5-(S)-(1S)-冰片氧基-4-膦酸二酯基-3-卤素-2(5H)-呋喃酮(3a～3d).该反应具有条件温和,产率高(69%～93%),光学纯度单一(d.e.≥98%)等特点.通过元素分析,IR,UV¹HNMR¹³CNMR,MS,[α]_D²⁰等分析数据以及X射线四圆衍射确定了它们的化学结构和绝对构型.     

不同pH条件下典型有机磷核磁图谱差异性解析

液相磷-31核磁共振波谱技术(31PNMR)是当前国内外土壤有机磷(Po)分子形态表征的主流分析技术,其主要利用乙二胺四乙酸-NaOH溶液提取,然后在高pH值(pH=13)条件下采集谱图.然而,高pH值条件下P.可能水解,同时鉴于实际土壤pH值通常在6～8范围内,因此有必要探究pH值对P.核磁谱图的影响.对D-葡萄糖-...