N-（2-氯吡啶-3-基）羰基-2＇-取代芳基磺酰胺的合成及除草活性

通过2-氯吡啶-3-甲酸与2-取代芳基磺酰胺的缩合反应合成了6个N-（2-氯吡啶-3-基）羰基-2＇-取代芳基磺酰胺化合物，其结构经元素分析、^1HNMR、IR确证。初步室内除草活性试验表明，化合物对根、茎的生长均有一定的抑制作用。     

2009年公开的农药专利集锦(二)

具有杀虫活性的N-苯基-3-取代氨基吡唑类化合物;具杀虫活性的含氮杂环二氯烯丙醚类化合物;4-乙酰氨基-3-（4-芳基噻唑-2-氨基）苯甲酸酯及其制备方法与应用;制备3-甲基氨基-1-（2-噻吩基）-1-丙醇化合物的方法;具有杀虫活性的邻氨基N-氧基苯甲酰胺类化合物;丝孢类真菌杀螨制剂;     

β-芳基-δ-氨基酸衍生物的新合成方法

为高效构建β-芳基-δ-氨基酸衍生物,以易制备的5-邻苯二甲酰亚胺基-2-戊烯酸甲酯和芳基硼酸为原料,通过（1,5-环辛二烯）氯化铑（I）二聚体〔[Rh(COD)Cl]2〕催化的Michael加成反应,以95%以上的产率获得了9种5-邻苯二甲酰亚胺基-3-芳基戊酸甲酯 （Ⅲ）。利用1HNMR、13CNMR 和HRMS对合成产物的结构进行了确证。合成5-邻苯二甲酰亚胺基-3-芳基戊酸甲酯最佳的反应条件为：5-邻苯二甲酰亚胺基-2-戊烯酸甲酯 0.2 mmol,芳基硼酸 0.4 mmol,KOH水溶液（0.1 mL,1.0 mol/L）,[Rh(COD)Cl]2 0.005 mmol,溶剂为1.0 mL 1,4-二氧六环,反应温度100℃,反应时间10 h。此外,以5-邻苯二甲酰亚胺基-3-对氯苯基戊酸甲酯（Ⅲb）为原料,实现盐酸高巴氯芬的快速制备。     

1，3-双-（3-N-乙酰基-2-芳基-1，3，4-噁唑啉-5-基）苯化合物的合成与表征

以间苯二甲酸二甲酯为起始原料,设计合成了8个新型的1,3-双-（3-N-乙酰基-2-芳基-1,3,4-噁唑啉-5-基）苯化合物,其结构经元素分析、IR、^1HNMR和MS表征,并对其质谱裂解途径进行了探讨。     

N-(2-氯吡啶-3-基)羰基-2′-取代芳基磺酰胺的合成及除草活性

通过2-氯吡啶-3-甲酸与2-取代芳基磺酰胺的缩合反应合成了6个N-(2-氯吡啶-3-基)羰基-2′-取代芳基磺酰胺化合物,其结构经元素分析1、HNMRI、R确证。初步室内除草活性试验表明,化合物对根、茎的生长均有一定的抑制作用。     

以3,5-二芳基取代吡唑为Cap的新型选择性HDAC6抑制剂:设计、合成及抑酶活性评价

为发现新型组蛋白去乙酰化酶抑制剂（Histone deacetylase inhibitors, HDACis）,基于现有代表性选择性HDAC6抑制剂的结构特征,采用构象限制型的3,5-二芳基取代吡唑为Cap单元构建目标分子,经Claisen-Schmidt反应、环合、亲核取代、水解、缩合、羟胺解反应合成了9个化合物,并通过氢谱和质谱对其进行结构确证。抑酶活性测试结果显示,化合物4-((3,5-二（4-氯苯基）-1H-吡唑-1-基)甲基)-N-羟基苯甲酰胺（5a）对HDAC6具有良好的抑制活性(IC₅₀=0.25μmol/L)和一定的亚型选择性。     

3-巯基-5-芳香基-4-芳基亚甲胺基-4H-1．2．4-三唑的合成及波谱研究

3，6-二取代5，6-二氢-1，2，4-三唑并噻二唑类化合物有广泛的生物活性，其同分异构体3-巯基-5-取代基-4-芳基亚甲胺基-1，2，4-芳基亚甲胺基-4H—1．2，4-三唑是近年来才引起人们注意的杂环类化合物，作为农药具有除草、杀菌、促进作物生长等作用，有很好的应用前景，本文报道3-巯基-5-芳香基-4-芳基亚甲胺基-4H-1，2，4三唑(3a～3d)合成，结构表征(Eq．1)。为了改进其水溶性，又由于葡萄糖基在生物体中强的亲合性质，     

N-(2-氯吡啶-3-基)羰基-2''''-取代芳基磺酰胺的合成及除草活性

通过2-氯吡啶-3-甲酸与2-取代芳基磺酰胺的缩合反应合成了6个N-(2-氯吡啶-3-基)羰基-2'-取代芳基磺酰胺化合物,其结构经元素分析、1HNMR、IR确证.初步室内除草活性试验表明,化合物对根、茎的生长均有一定的抑制作用.     

4-甲基-2-芳基(杂环基)-1,3-噻唑-5-甲酸乙酯的合成及抑菌活性研究

以硫代芳基(杂环基)甲酰胺和2-氯乙酰乙酸乙酯为原料合成了4-甲基-2-芳基(杂环基)-1,3-噻唑-5-甲酸乙酯。于甲醇溶剂中,55℃至回流条件下,由腈与17%硫化铵溶液反应4~5 h制得硫代芳基(杂环基)甲酰胺中间产物。所合成的硫代酰胺及目标产物经IR、1HNMR、MS表征,其中4-甲基-2-(苯酞-5-基)-1,3-噻唑-5-甲酸乙酯尚未见报道,并分别测试了上述化合物对大肠杆菌(Escherichia coli)和枯草芽孢杆菌(Bacillus subtilis)的抑菌活性,结果表明部分化合物具有一定的抑菌活性。     

新型噻唑-腙类化合物的合成及抗肿瘤活性的研究

通过芳基硫脲1a~g与3-氯-2,4-戊二酮2环合得到2-芳氨基-4-甲基-5-乙酰基噻唑3a~g,再与肼基甲酸甲酯4进行缩合反应得到目标产物。以5e为例,分别对反应时间、催化剂种类及物质的量比进行了试验,最佳的缩合反应条件是:反应时间6h,催化剂用浓盐酸,物质的量比1∶1.1,收率70.9%。合成得到7个目标产物2-[1-(2-芳氨基-4-甲基噻唑-5)-乙缩醛]肼基甲酸甲酯5a~g,目标化合物结构经IR、1 H NMR、MS和元素分析确证。采用MTT法对MCF-7和SMMC-7721人肿瘤细胞株进行体外抗肿瘤活性测试,结果发现此类化合物活性较弱,化合物5f有一定的抗肿瘤活性。     

Investigations on Structural and Electrochemical Properties of Some Disulfides Prepared by Schiff Base Reactions

Four different disulfides, [2,2′‐dithiobis‐(2‐mercaptoacetophenone)]‐4‐triphenylmethylthiosemicarbazone ( 1 ), [5,5′‐dithiobis‐(4‐formyl‐3‐methyl‐1‐phenylpyrazole)]‐4‐triphenylmethylthiosemicarbazone ( 2 ), bis[1‐(2‐mercaptophenyl)‐2‐(4‐(1‐phenyl‐3‐methyl)pyrazole)‐azaethene]di‐sulfide ( 3 ) and bis[1‐phenyl‐2‐(4‐(1‐phenyl‐3‐methyl‐5‐mercapto) pyrazole)‐azaethene]disulfide ( 4 ) were synthesized by Schiff base reactions. Their electrochemical behaviour was examined by cyclic voltammetry. The results show low potentials for the disulfide reduction so that these compounds are suitable for the syntheses of tridentate thiolate ligands from disulfides by electrochemical cleavage. In addition compounds 2 and 4 were characterized by X‐ray structure determination. The structures show significant differences of the S—S bonds and angles as compared to other disulfides without bulky substituents.     

Thiophosphoryl disulfides as crosslinking agents for chloroprene rubber

The objective of this investigation was the determination of a suitable substitute for ethylene thiourea (ETU), a well‐known vulcanizing agent for polychloroprene rubber (CR). Unfortunately, ETU is a potent carcinogenic compound, and so its replacement is needed. The efficacy of several thiophosphoryl disulfides as crosslinking agents for CR, either alone or in combination with other compounds, was examined. It was shown that bis(diisopropyl)thiophosphoryl disulfide (DIPDIS) and bis(dicyclohexyl)thiophosphoryl disulfide (DCHDIS), being ecofriendly, could be replacements. Additionally, these thiophosphoryl compounds were shown to provide significant antioxidant protection. CR vulcanizates containing DIPDIS or DCHDIS exhibited higher tensile strengths than those containing ETU. Bis(3‐ethoxysilylpropyl) tetrasulfide imparted to CR vulcanizates a notable modulus, which was comparable to that obtained with ETU‐cured products. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1913–1919, 2004     

Homolytic cleavage and aggregation processes in cyclopentadienylchromium chemistry

The reactivity of the cyclopentadienylchromium tricarbonyl dimer [CpCr(CO)3]2 (Cp = C5H5, 1) toward several classes of organo-P-, -S- and -N-compounds will be described. The organic substrates include the following: (i) bis(diphenylthiophosphinyl)disulfane, R2P(S)SSP(S)R2; (ii) bis(thiophosphoryl)disulfane, (RO)2P(S)SSP(S)(OR)2; (iii) tetraalkylthiuram disulfides, R2NC(S)SSC(S)NR2; (iv) tetraalkyldiphosphine disulfides, R2P(S)P(S)R2; (v) dibenzothiazolyl disulfide, (C6H4NSC)2; and (vi) Lawesson's reagent, (CH3OC6H4)2P2S4. The primary products, namely, the complexes CpCr(CO)2(SPR2), CpCr(CO)2)(S2CNR2), CpCr(CO)2(SCSN(C6H4)), and CpCr(CO)2(SPC6H4OCH3), containing the thiophosphinito, dithiocarbamate, 2-mercaptobenzothiazole, and dithiophosphorane ligands, respectively, arise from facile cleavage of the S-S, P-P, and P-S bonds in the organic substrates. Further treatment of these complexes with 1 under thermal activation results in cleavage of C-X (X = N, S), P-S, and Cr-E (E = C, N, P, S) bonds, accompanied by C-C and P-P bond formation in some cases, generating a variety of organometallic compounds belonging to the phosphido, phosphinidene, thiocarbenoid, dithiooxamide, aminocarbyne, aminoalkenylacyl, and cuboidal types.     

Mechanisms of antioxidant action: Tellurium dithiocarbamates as antioxidants for polypropylene

The tetrakis (dialkyldithiocarbamato)tellurium(IV) complexes are highly effective thermal antioxidants and melt stabilizers for polypropylene and the evidence suggests that they are converted to the bis(dialkyldithiocarbamato)tellurium(II) complexes and the corresponding dithiocarbamoyl disulfides during processing. The Te(IV) complexes are also effective photoantioxidants and their activity increases with increasing processing time. The bischelates are in general less effective when used alone.     

Iron‐Promoted Electrophilic Annulation of Aryl Enynes with Disulfides or Diselenides Leading to Polysubstituted Naphthalenes

An iron‐promoted electrophilic annulation of aryl enynes with disulfides or diselenides has been developed. In the presence of iron(III) chloride (FeCl₃) and iodine (I₂,), a variety of trifluoromethyl‐containing aryl enynes underwent electrophilic annulation with various disulfides or diselenides successfully to afford the corresponding polysubstituted naphthalenes in moderate to excellent yields.

     

Cure synergism in XNBR vulcanization in presence of thiophosphoryl disulfides and amine disulfide/thiazole accelerators

The study deals with the vulcanization of carboxylated nitrile butadiene rubber (XNBR) having synergistic combinations of accelerators comprising thiophosphoryl disulfide as one of the components. Other constituent accelerators employed in the present investigation are 2-mercaptobenzothiazole (MBT), 2-mercaptobenzothiazyl disulfide (MBTS), bis(N-oxydiethylene)disulfide (ODDS), N-oxydiethylene 2-benzothiazole sulfenamide (OBTS), etc. The binary combinations of thiophosphoryl disulfides with OBTS exhibited the highest mutual activity in the respective areas, so far as the physical properties are concerned. Structural characterization of different thiophosphoryl disulfide-accelerated XNBR vulcanizates, including those formed from the synergistic combinations with OBTS, were studied using a methyl iodide probe. It was found that the amount of sulfidic crosslinks arising from the reaction between  COOH groups of XNBR and thiophosphoryl disulfides, actually controls the network structure as wellas the physical properties of the vulcanizates. © 1996 John Wiley & Sons, Inc.     

Synthesis and properties of new poly(amide‐imide)s based on 1,3‐bis[4,4'‐(trimellitimido) phenoxy] propane and aromatic diamines

Six new poly(amide‐imide)s 8a–f containing trimethylene moiety in the main chain were synthesized by the polycondensation reactions of 1,3‐bis[4,4'‐(trimellitimido) phenoxy] propane 6 with six different aromatic diamines 7a–f in a medium constituting N‐methyl‐2‐pyrrolidone, triphenylphosphite, CaCl₂, and pyridine as condensing agents. The polycondensation reaction produced a series of novel poly(amide‐imide)s 8a–f in high yields with inherent viscosities between 0.35 and 0.63 dL/g. The resulting poly(amide‐imide)s were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis (TGA and DTG), solubility tests, and FTIR spectroscopy. 1,3‐Bis[4,4'‐(trimellitimido) phenoxy] propane 6 as a new monomer containing trimethylene moiety was synthesized using a three‐step reaction. At first 1,3‐bis[4,4'‐nitrophenoxy] propane 3 was prepared by the reaction of 4‐nitrophenol 1 with 1,3‐dibromo propane 2 in DMF solution . Then, dinitro 3 was reduced to 1,3‐bis[4,4'‐aminophenoxy] propane 4 by using a solution of sodium sulfite in ethanol. Finally, 1,3‐bis[4,4'‐(trimellitimido) phenoxy] propane 6 was prepared by the reaction of one equivalent diamine 4 with two equivalents of trimellitic anhydride 5 in a mixture of acetic acid‐pyridine (3 : 2). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Light‐colored fluorinated polyimides based on 2,5‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl and various aromatic dianhydrides

A novel trifluoromethyl‐containing aromatic diamine monomer, 2,5‐bis (4‐amino‐2‐trifluoromethylphenoxy)biphenyl (2), was prepared through the nucleophilic substitution reaction of 2‐chloro‐5‐nitrobenzotrifluoride and phenylhydroquinone in the presence of potassium carbonate to yield the intermediate dinitro compound (1), followed by catalytic reduction with hydrazine and Pd/C. A series of fluorinated polyimides (code 5a–f) were synthesized from diamine (2) with six commercially available aromatic dianhydrides using a standard two‐stage process with thermal or chemical imidization of poly(amic acid). Most of fluorinated polyimides showed good solubility at a concentration of 5–10 wt % and even in pyridine and dioxane. For improving solubility of 5c, copolyimides (5c/a–f) were also prepared from 2 and a pair of dianhydrides (3c/a–f), which were mixed in the molar ratio 1:1. All the polyimide films had a tensile strength in the range from 73 to 112 MPa, an elongation at break within a range of 9–23%, and an initial modulus in the range of 1.6–2.2 GPa. These polyimides exhibited glass transition temperatures of 220–267°C and showed no significant decomposition below 500°C under either nitrogen or air atmosphere. In comparison with the analogous nonfluorinated polyimides based on 2,5‐bis (4‐aminophenoxy) biphenyl (2′), the fluorinated polyimides showed better solubility as well as reduced color intensity, lower dielectric constant, and moisture absorption. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4101–4110, 2006     

Organosoluble and light‐colored fluorinated polyimides based on 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane and aromatic dianhydrides

A novel fluorinated diamine monomer, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane (2), was prepared through the nucleophilic substitution reaction of 2‐chloro‐5‐nitrobenzotrifluoride with 2,2‐bis(4‐hydroxyphenyl)propane in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C. Polyimides were synthesized from diamine 2 and various aromatic dianhydrides 3a–f via thermal imidization. These polymers had inherent viscosities ranging from 0.73 to 1.29 dL/g. Polyimides 5a–f were soluble in amide polar solvents and even in less polar solvents. These films had tensile strengths of 87–100 MPa, elongations to break of 8–29%, and initial moduli of 1.7–2.2 GPa. The glass transition temperatures (T_g) of 5a–f were in the range of 222–271°C, and the 10% weight loss temperatures (T₁₀) of them were all above 493°C. Compared with polyimides 6 series based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane (BAPP) and polyimides 7 based on 2,2‐Bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane (6FBAPP), the 5 series showed better solubility and lower color intensity, dielectric constant, and lower moisture absorption. Their films had cutoff wavelengths between 363 and 404 nm, b* values ranging from 8 to 62, dielectric constants of 2.68–3.16 (1 MHz), and moisture absorptions in the range of 0.04–0.35 wt %. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 922–935, 2005     

Bis(diisopropyl)thiophosphoryl sulfides in vulcanization reactions

A synergistic combination of bis(diisopropyl)thiophosphoryl disulfide, dimorpholyl disulfide, and sulfur is used to produce an efficient vulcanizing system for a range of rubbers. This produces vulcanizates with the exceptional thermal and thermal-oxidative stability characteristic of sulfur donor vulcanizates and the rapid and extensive crosslinking reaction normally associated with a conventional sulfur–accelerator combination. A pronounced induction period is noted. The crosslinks initially produced in cis-1,4-polyisoprene rubbers are predominantly polysulfide but reduce to mono- and disulfides at optimum and extended cures. The crosslinks of the ethylene–propylene terpolymer and the styrene–butadiene vulcanizates are initially mainly disulfide but are rapidly reduced to monosulfides at the high curing temperatures (180°C) used. A comparison with vulcanization systems based on tetramethylthiuram disulfide and bis(diisopropyl)thiophosphoryl tri-and tetrasulfides as sulfur donors and with a conventional cyclohexylbenthazyl-2-sulfenamide–sulfur combination, respectively, shows it to have distinct advantages.