N-芳基-N''''-(5-芳基-2-呋喃甲酰基)硫脲衍生物的合成及其生物活性的研究

于固-液相转移条件下,合成了40个未见报道的N-芳基-N'-(5-芳基-2-呋喃甲酰基)硫脲衍生物,用元素分析、UV、IR以及~1H NMR光谱确定了它们的结构.该法具有操作简便、反应条件温和、产率高等优点.初步生物活性试验表明,该类化合物对小麦幼苗生长有明显的促进作用.     

N′-5-四唑基-N-芳甲酰基硫脲的合成及其生物活性研究(I)

为寻找新的高活性农药 ,根据生物等排原理 ,设计合成了 10种未见文献报道的N′ 5 ( 1H 1,2 ,3 ,4 四唑基 ) N 芳甲酰基硫脲类化合物 .它们的结构经IR ,1HNMR和元素分析确证 .初步的生物活性测定结果表明 ,部分化合物具有优良的除草活性或植物生长调节活性 .     

5-(4-羟基苄基)-2,4-咪唑啉二酮酯类化合物合成及生物活性

为了发现高效、低毒、低残留的农药先导化合物,模拟AdSS酶天然抑制剂的活性结构,以L-酪氨酸为起始原料,经过关环和酯化等反应合成了24个新的5-(4-羟基苄基)-2,4-咪唑啉二酮酯系列化合物6a～6x,它们的结构通过IR,1H NMR和元素分析进行了确证。化合物6m经X射线衍射测定: C18H16N2O5,Mr＝340.33,单斜晶系,空间群 P2(1)/c,a＝0.86071(17) nm,b＝1.1167(2) nm,c＝0.93826(2) nm,β＝115.10(3)°,V＝0.8166(3) nm3,Dc＝1.384 g/cm3,Z＝2,F(000)＝356,m(Mo Kα)＝0.103 mm－1,final R＝0.0359,wR＝0.0998。初步生物活性实验结果表明,在200 mg/mL浓度下,部分化合物对小麦和拟南芥的生长有一定的抑制作用,而部分化合物对玉米的生长有促进作用。     

酰氨基硫脲及其相关杂环化合物的研究(Ⅳ)——1-氰乙酰基-4-取代芳酰基硫脲及1,2,4-三唑类化合物的研究

本文合成一系列新的1-氰乙酰基-4-取代芳酰基硫脲化合物(Ⅰ),研究了(Ⅰ)在碱催化条件下环化为1,2,4-三唑类衍生物的反应。初步鉴定了(Ⅰ)类化合物对小麦等植物生长性能的促进作用。     

5-(4-羟基苄基)-2,4-咪唑啉二酮酯类化合物的合成及生物活性

为了发现高效、低毒、低残留的农药先导化合物,模拟AdSS酶天然抑制剂的活性结构,以L-酪氨酸为起始原料,经过关环和酯化等反应合成了24个新的5-(4-羟基苄基)-2,4-咪唑啉二酮酯系列化合物6a～6x,它们的结构通过IR,~1HNMR和元素分析进行了确证.化合物6m经X射线衍射测定:C_(18)H_(16)N_2O_5,M_r=340.33,单斜晶系,空间群P2(1)/c,a=0.86071(17)nm,b=1.1167(2)nm,c=0.93826(2)nm,β=115.10(3)°,V=0.8166(3)nm~3,D_c=1.384 g/cm~3,Z=2,F(000)=356,μ(Mo Kα)=0.103 mm~(-1),final R=0.0359,wR=0.0998.初步生物活性实验结果表明,在200μg/mL浓度下,部分化合物对小麦和拟南芥的生长有一定的抑制作用,而部分化合物对玉米的生长有促进作用.     

2H－1，2，4－噻二唑并[2,3-α]嘧啶衍生物的合成及除草活性研究（Ⅴ）

合成了10个未见文献报道的目标化合物，结构经IR，^1H NMR,MS和元素分析确 证。初步除草活性测定结果表明：目标化合物具有高效、选择除草活性，主要抑制 双子叶植物（如油菜）的生长,而对单子叶植物（如玉米）具有较好的促进生长作 用。     

N'-5-四唑基-N-芳甲酰基硫脲的合成及其生物活性研究(Ⅰ)

为寻找新的高活性农药,根据生物等排原理,设计合成了10种未见文献报道的N'-5-(1H-1,2,3,4-四唑基)-N-芳甲酰基硫脲类化合物.它们的结构经IR,1H NMR和元素分析确证.初步的生物活性测定结果表明,部分化合物具有优良的除草活性或植物生长调节活性.     

N-(香豆素-3-甲酰基)-N -取代硫脲衍生物的合成及生物活性

以香豆素-3-甲酸与亚硫酰氯的反应产物香豆素-3-甲酰氯, 与硫氰酸钾反应, 再与各种杂环胺反应合成了N-(香豆素-3-甲酰基)-N -取代硫脲类衍生物. 其结构由IR, ¹H NMR, 质谱和元素分析所表征, 并初步研究了目标化合物抗菌活性和植物生长促进作用, 发现它们大多数有优良的抑菌活性和较明显的植物生长促进活性.     

吡啶甲酰硫脲嘧啶衍生物的合成及生物活性

酰基硫脲类化合物及其吡啶取代产物不仅是重要的有机合成中间体 ,且有优良的杀虫 ,除草 ,抗病毒 ,及植物生长调节等功效[1 - 3] 。为了寻找高活性的新药物 ,本文采用亚结构连接法 ,将吡啶杂环引入到含取代嘧啶环的酰基硫脲中 ,合成了8个含取代嘧啶环的β (或γ )吡啶甲酰硫脲 4ａ～4ｈ ,结构经ＩＲ、1 ＨＮＭＲ、ＭＳ和元素分析表征。初步生物活性测定结果表明 :目标化合物高效抑制双子叶植物 (如油菜 )的生长 ,而对单子叶植物 (如玉米 )的生长具有一定的促进作用。目标化合物的合成路线为 :表 1　化合物 4ａ～ 4ｈ Ｔａｂ 1　Ｃｏｍｐｏｕ…     

N-[5-(4-三氟甲基苯基)-1,3,4-噻二唑-2-基]-N′-芳酰基脲的合成、结构及其生物活性

通过2-氨基-5-(4-三氟甲基苯基)-1,3,4-噻二唑与芳酰基异氰酸酯反应,合成了14种新的芳酰基脲,它们的结构用红外光谱、核磁共振氢谱和元素分析进行了表征,并且采用X射线单晶衍射分析方法测定了化合物2l的结构.初步的生物活性试验表明,部分标题化合物具有优良的植物生长调节活性.     

双（1—甲酰胺基—3—芳酰基硫脲）的合成及环化

通过草二酰肼与芳酚异硫氰酸酯的加成反应制得一系列新的双(1-甲酰胺基-3-芳酰基硫脲)1。1在碱性溶液中可环化脱水为双(3-基-4-芳甲酰基-1,2,4-三唑啉-5-硫酮)2。所有产物均经元素分析;部分化合物经红外光谱,~1H NMR谱,质谱确定其结构。某些1类化合物具有较强的促进玉米胚芽生长的作用。     

A new spirotryprostatin from the marine isolate of the fungus Aspergillus fumigatus

The new spirocyclic diketopiperazine alkaloid spirotryprostatin F was isolated from the marine isolate of the fungus Aspergillus fumigatus. The structure of the compound was established using on NMR spectroscopy, high-resolution mass spectrometry, and acid hydrolysis. Spirotryprostatin F in low and ultralow doses (10^–6–10^–17 M) exhibited stimulating action on the growth of sprout roots of soy [Glycine max (L.) Merr.], buckwheat (Fagopyrum esculentum Moench), and corn (Zea mays L.). The dose-effect curve had a bimodal character.     

三—（2—甲基氮丙啶）氧化膦异构体的核磁共振和量子化学研究

三-(2-甲基氮丙啶)氧化膦(MAPO)为黄色油状液体,其化学性质活泼,可用作塑料、橡胶及造纸业中高分子化合物的交联剂等。本文对MAPO进行了~1H、~(13)C、~(15)N、~(31)P和~(17)O的核磁共振研究及量子化学计算。结果表明,该化合物存在4种异构体,其中2种为对映体,并得到了这4种异构体的几何构型。     

Development of poly(urethane-ester)amide from corn oil and their anticorrosive studies

Corn oil-based poly(urethane-ester)amide was synthesized from corn oil-based fatty amide diol, camphoric acid, and tolylene 2,4-diisocyanate. The structure of corn polyesteramide and corn poly(urethane-ester)amide (CPEA) was confirmed by Fourier transform infrared, ¹H NMR, and ¹³C NMR spectroscopic techniques. CPUEA coatings were made on mild steel strips and their physicomechanical analysis (scratch hardness, impact test, conical mandrel test, and pencil hardness tests) was performed by standard methods. The surface morphology of coatings was observed by scanning electron microscopy and thermal stability was assessed by thermogravimetric analysis/differential scanning calorimetry. Anticorrosion properties of CPUEA were observed in acidic, saline, and tap water medium at room temperature using potentiodynamic polarization technique. The results of CPUEA coatings exhibit good physicomechanical and anticorrosive properties and can find application up to 175°C.     

Conformation and absolute configuration of nocathiacin I determined by NMR spectroscopy and chiral capillary electrophoresis

Nocathiacin I (BMS-249524) is a highly cross-linked thiazolyl peptide that displays potent activity against Gram-positive bacteria, including a number of antibiotic-resistant strains. This natural product contains 10 chiral centers. NMR studies have been performed to characterize the solution structure of nocathiacin I. A uniformly 13C,15N-labeled sample was used to obtain NMR assignments. Restrained simulated annealing calculations were performed by using accurately determined NOE distance restraints. All of the chiral centers were allowed to float during the simulated annealing protocol. Two clusters of structures were obtained that satisfy the NOE restraints very well and that are reasonably consistent with vicinal J-coupling constants. Within each cluster, all 10 chiral centers are uniquely defined. The two clusters are effectively mirror images of each other: all chiral centers that have the R(S) configuration in one cluster have the S(R) configuration in the other. The single threonine residue in nocathiacin I was subsequently determined to be l-threonine by chiral capillary electrophoresis, allowing the absolute configurations of all 10 chiral centers to be defined.     

Deuterium NMR of the TGBA* phase in chiral liquid crystals

A deuterium NMR (DNMR) study of the TGBA* (twist grain boundary smectic A*) phase in an NMR magnetic field of 9.4 T for the chiral compound 4-[4'-(1-methyl heptyloxy)] biphenyl 4-(10-undecenyloxy) benzoate (11EB1M7) is reported. The deuterium two-dimensional (2D) exchange spectra were observed for the first time in this phase. The present study allows us to learn how the helicoidal structures arrange in an external magnetic field. To derive quantitative kinetic parameters of this novel phase, both 1D and 2D experimental spectra were simulated by means of a jump diffusion model. By comparing the experimental and simulated spectra, an accurate determination of the dynamic parameters in the TGBA* phase was obtained. Furthermore, the twist angle between two neighboring smectic A blocks is found as 26 +/- 10 degrees, which is consistent with the X-ray results for similar chiral liquid crystals. The diffusion constant (D(parallel)) is estimated to be 3.2 x 10(-12) m(2)/s at 379.5 K.     

Distribution and dynamics of hydrogen in the low-temperature phase of Mg(2)NiH(4) studied by solid-state NMR

Distribution and dynamics of hydrogen atoms in the low-temperature phase of Mg(2)NiH(4) have been studied by means of (2)H and (1)H NMR for Mg(2)NiD(4) and Mg(2)NiH(4), respectively. (2)H NMR spectra have been measured in the temperature range between 200 and 340 K, and the line shapes were simulated. The temperature dependence of (2)H NMR spectra was quite well simulated assuming a distorted tetrahedral configuration and a pseudoisotropic rotation of the NiD(4) unit. The estimated jump frequency obeyed Arrhenius relation with a frequency factor of (0.8 +/- 0.6) x 10(13) Hz and an activation energy of 50.1 +/- 1.4 kJ/mol. (1)H NMR spectra were acquired from 240 to 360 K. The observed (1)H second moments were 202 kHz(2) in the rigid lattice (240 K) and 46.6 kHz(2) in a motional state (360 K). The value in the rigid lattice supported the tetrahedron model, and the value in a motional state indicated the isotropic rotation of the NiH(4) unit. Conclusively, the NiH(4) unit has the distorted tetrahedral configuration and undergoes the pseudoisotropic rotation.     

(13)C cell wall enrichment and ionic liquid NMR analysis: progress towards a high-throughput detailed chemical analysis of the whole plant cell wall

The ability to accurately and rapidly measure plant cell wall composition, relative monolignol content and lignin-hemicellulose inter-unit linkage distributions has become essential to efforts centered on reducing the recalcitrance of biomass by genetic engineering. Growing (13)C enriched transgenic plants is a viable route to achieve the high-throughput, detailed chemical analysis of whole plant cell wall before and after pretreatment and microbial or enzymatic utilization by (13)C nuclear magnetic resonance (NMR) in a perdeuterated ionic liquid solvent system not requiring component isolation. 1D (13)C whole cell wall ionic liquid NMR of natural abundant and (13)C enriched corn stover stem samples suggest that a high level of uniform labeling (>97%) can significantly reduce the total NMR experiment times up to ～220 times. Similarly, significant reduction in total NMR experiment time (～39 times) of the (13)C enriched corn stover stem samples for 2D (13)C-(1)H heteronuclear single quantum coherence NMR was found.     

Molecular dynamics of polystyrene solutions in microwave fields

Equilibrium and nonequilibrium molecular dynamics simulation techniques were used to assess the influence of an applied microwave field on the dynamics of methylamine-methanol and methylamine-dimethylformamide (DMF) solutions bound within atactic polystyrene over a range of polymer densities from 35 to 96 wt % polymer. Atomistically detailed systems were studied, ranging from 3000 to 10 644 particles, using previously established potential models. Structural and dynamical properties were determined in the canonical (NVT) ensemble at 298 K. The simulated DMF self-diffusion coefficients in polystyrene solutions were compared with the zero-field experimental results established with pulsed-gradient spin-echo NMR spectrometry. A simulated external microwave field, with a rms electric field intensity of 0.1 VA, was applied to these systems and the simulated dynamical results over field frequencies up to 10(4) GHz were compared with the zero-field values. Simulated evidence of athermal effects on the diffusive characteristics of these mixtures is reported.     

1-取代酰基-4-磷酰基氨基硫脲及其1,3,4-噁二唑杂环衍生物的合成

合成了1-取代酰基-4-磷酰基氨基硫脲(5),以及由(5)衍生的环化产物2-磷酰氨基-5-本基(或氰乙基)-l,3,4-噁二唑(6),它们的结构经~1H NMR,IR和元素分析的证实。初步生测结果表明,部分化合物具有一定的植物生长调节活性和除草活性。