2-氰基-3-(2-氟吡啶-5-基)甲氨基-3-甲硫基氰基丙烯酸酯类化合物的合成及除草活性

设计合成了系列光系统II (PS-II)电子传递抑制剂2-氰基-3-(2-氟吡啶-5-基)甲氨基-3-甲硫基氰基丙烯酸酯类化合物. 其结构经¹H NMR、元素分析确证. 生物活性测定表明: 部分化合物显示出很好的除草活性. 其中活性最好的化合物在150 g/ha, 对阔叶杂草的防效在90%以上. 构效关系研究表明: 氰基丙烯酸酯的3位取代基对它们的活性影响较大. 3位由(2-氟吡啶-5-基)甲氨基取代的氰基丙烯酸酯和相应的氯取代的氰基丙烯酸酯的除草活性相当或稍高.     

Synthesis, Herbicidal Activity, and Structure-Bioactivity Relationship of Pyridyl-Containing 2-Phenyliminothiazolidines

Summary. A series of novel 2-phenyliminothiazolidine derivatives were designed and synthesized. All title compounds were characterized by ¹H NMR and, in some cases, by ¹³C NMR, IR, and HRMS. Their agricultural bioactivities were evaluated and some of these compounds exhibited efficient herbicidal activities against Echinochloa crusgalli, Sorghum vulgare, Digitaria sanguinalis, Eclipta prostrasta, Cucumis sativus, and Brassica campestris at 50 μg/cm³. Analysis of the quantitative structure-activity relationship (QSAR) showed that the electronic parameter was the main factor to affect herbicidal activities.     

Synthesis and Biological Activity of Novel Symmetrical Bis-2-phenyliminothiazolidine Derivatives

A series of novel symmetrical bis-2-phenyliminothiazolidine derivatives were designed and synthesized. The structures of all the title compounds were characterized by ¹H NMR and, in some cases, by ¹³C NMR, IR, and high-resolution mass spectra. Herbicidal activities were examined, and some of these compounds showed selectively herbicidal activity against Triticum aestivum. The type of linker between the two 2-phenyliminothiazolidines was crucial for the biological activities.     

1-(取代吡唑-4-甲酰基)吡唑类化合物的合成及生物活性研究

设计合成了25个新型1-取代吡唑甲酰基吡唑系列衍生物,化合物结构经¹HNMR、元素分析、IR和MS确证.生物活性测试结果表明,该类化合物具有一定除草活性,讨论了其结构与活性的关系.     

Synthesis and Herbicidal Activities of 2-Methylpropan-2-Aminium Methyl 1-(Substituted Phenoxyacetoxy) Alkylphosphonates

Abstract

A series of 2-methylpropan-2-aminium methyl 1-(substituted phenoxyacetoxy) alkylphosphonates were selectively synthesized by reacting the corresponding dimethyl 1-(substitutedphenoxyacetoxy)alkylphosphonates with an excess of 2-methylpropan-2-amine. All the title compounds were identified by IR, ¹H NMR, and ³¹P NMR, some of them were further analyzed by ¹⁹F NMR and ¹³C NMR. Their herbicidal activity was investigated and the results showed that most of the demethylated aminium salts exhibited notable herbicidal activities against Brassica napus L. and Echinochloa crusgalli.

Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text, figures and tables.     

Synthesis and herbicidal activity of (Z)-ethoxyethyl 2-cyano-3-(2-methylthio-5-pyridylmethylamino)acrylates

2-Methylthio-5-pyridinemethylene amine was prepared from 2-chloro-5-methylpyridine. Ethoxyethyl 2-cyano-3,3-dimethylthioacrylate was prepared from ethoxyethyl cyanoacetate, carbon disulfide, and dimethyl sulfate in 86.2% yield. Its reaction with 2-methylthio-5-pyridinemethylene amine yielded (Z)-ethoxyethyl 2-cyano-3-methylthio-3-(2-methylthio-5-pyridylmethylamino)acrylate. Ethoxyethyl (Z+E)-2-cyano-3-ethoxyacrylate was synthesized from ethoxyethyl 2-cyanoacetate and triethyl or- thoacetate in 90.7% yield, and its reaction with 2- methylthio-5-pyridinemethylene amine yielded (Z)-ethoxyethyl 2-cyano-3-methyl-3-(2-methylthio-5-pyri-dylmethylamino)acrylate. The structures of all of the products were confirmed by ¹H NMR, elemental analysis, IR, and mass spectroscopy. The herbicidal activities of the products were evaluated, and the results of bioassay showed that (Z)-ethoxyethyl 2-cyano-3-methyl-3-(2-methylthio-5-pyridylmethylamino)acrylate exhibits good herbicidal activity on rape (Brassica napus) at a dose of 1.5 kg/ha. © 2003 Wiley Periodicals, Inc. 15:67–70, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/.hc10214     

N-(5 -溴-4 -取代嘧啶-2 -基)苯磺酰脲化合物的合成和生物活性

乙酰羟基酸合成酶(Acetohydroxyacid synthase, AHAS, EC 4.1.3.18)是植物和微生物中亮氨酸、异亮氨酸和缬氨酸合成途径的一个关键酶, 以AHAS为靶标的磺酰脲类除草剂具有高效、高选择性和对环境友好的特点. 通过2-氨基-4-甲基嘧啶溴代反应以及进一步的衍生、磺酰基异氰酸酯的胺解, 合成了一系列含有5-溴嘧啶基的新磺酰脲. 其结构经¹H NMR、质谱和元素分析确定. 生物活性测试表明目标化合物在离体水平对大肠杆菌乙酰羟基酸合成酶同工酶AHASII表现出了与市售除草剂苯磺隆相当甚至更优的抑制活性, 而盆栽除草活性低于苯磺隆.     

N-取代芳酰氨基-5-氟代苯基-2-呋喃甲酰硫脲的合成与生物活性测定

从5-氟代苯基-2-呋喃甲酸出发, 经酰化、异硫氰酸酯化, 再与取代芳酰肼反应合成了20个未见文献报道的N-取代芳酰氨基-5-氟代苯基-2-呋喃甲酰硫脲. 目标产物的结构经IR, ¹H NMR和元素分析测定确证. 初步生物活性测试表明, 部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性; 部分目标化合物有较好的除草活性.     

Synthesis and Herbicidal Activity of Acylpyrazole Derivatives Containing 1,2,3‐Thiadiazole Moiety

A series of novel acylpyrazole derivatives containing 1,2,3‐thiadiazole ring 3a – 3m were synthesized by the condensations of 1‐phenyl‐3‐methyl‐4‐(substituted benzal or 4‐methyl‐1,2,3‐thiadiazole‐5‐carbonyl)‐5‐hydroxypyrazole 2 with 4‐methyl‐1,2,3‐thiadiazole‐5‐carbonyl chloride or substituted benzoyl chloride. Their structures were confirmed by IR, ¹H‐NMR, mass spectroscopy, and elemental analyses. The results of preliminary bioassays showed that some of the title compounds 3 exhibited moderate to good herbicidal activities against dicotyledonous plants (Brassica campestris L.) at the concentration of 100 mg/L. For example, compounds 3e , 3f , 3g , and 3k possessed 74.6%, 72.2%, 70.3%, and 84.5% inhibition against B. campestris L., respectively, whereas commercially available herbicide Sulcotrione showed only 35.0% inhibition at the same concentration. Moreover, these compounds displayed higher herbicidal activity against B. campestris L. than Echinochloa crus‐galli. However, these compounds showed weak activities at the concentration of 10 mg/L.     

2-[2-(烷氧羰基苯氧羰基)苯氧基]-4,6-二甲氧基嘧啶类化合物的合成及其除草活性研究

为了寻找高效、安全、经济的除草活性化合物, 设计并合成了9个新的2-[2-(烷氧羰基苯氧羰基)苯氧基]-4,6-二甲氧基嘧啶类化合物, 其化学结构经IR, ¹H NMR, LC/MS和元素分析确证. 初步生物活性测定结果表明, 该类化合物在有效成份2250 g/ha剂量时, 对苘麻(Abutilon theophrasti)、稗草(Echinochloa crus-galli)、狗尾草(Setaria viridis)等都具有良好的除草活性, 抑制率达90％以上. 其中5b, 5e, 5h在187.5 g/ha剂量时, 仍具有良好的除草活性, 抑制率达90％以上.     

Synthesis, Crystal Structure, and Herbicidal Activities of 2-Cyanoacrylates Containing 1,3,4-Thiadiazole Moieties

Three series of novel 2‐cyanoacrylates 7a – 7f , 9a – 9f , 10a – 10f containing 1,3,4‐thiadiazole ring moieties were synthesized as herbicidal inhibitors of photosystem II (PS II) electron transportation. Their structures were clearly verified by ¹H NMR, ¹³C NMR, elemental analysis (or HRMS analysis) and single‐crystal X‐ray diffraction analysis. Bioassay showed that a suitable group at the 3‐position of acrylates was essential for high herbicidal activity. In particular, compound 7e showed the best herbicidal activities and gave 100% inhibitory activity against rape and amaranth pigweed at a dose of 1.5 kg/ha. Introduction of substituent with higher polarity such as sulfinyl or sulfonyl to the 5‐position of 1,3,4‐thiadiazole decreased herbicidal activities.     

Synthesis and Herbicidal Activity of Novel 4‐Acyl‐2,5‐disubstituted‐3‐hydroxypyrazoles and 4‐Arylcarbonyl‐3‐substitutedisoxazol‐5‐ones

Two series of novel 4‐acyl‐2,5‐disubstituted‐3‐hydroxypyrazoles 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h and 4‐arylcarbonyl‐3‐substitutedisoxazol‐5‐ones 7a , 7b , 7c , 7d , 7e , 7f , 7g , 7h , 7i were synthesized by the Scotton–Baumann reaction of 2,5‐disubstituted‐2,4‐dihydro‐pyrazol‐3‐ones 1 or 3‐substituted‐4H‐isoxazol‐5‐ones 6 and various acyl chlorides, followed by the Fries rearrangement in the presence of calcium hydroxide and calcium oxide as the catalyst. Their structures were confirmed by IR, ¹H NMR, mass spectroscopy, and elemental analyses. ¹H NMR indicated that compounds 3 existed in enol forms and compounds 7 in keto configurations. The results of preliminary bioassays showed that some of the title compounds 3 and 7 exhibited moderate to good herbicidal activities against Brassica campestris L. at the concentration of 100 mg/L. Isoxazole compounds 7 showed better herbicidal activity against B. campestris L. than pyrazole compounds 3 did at the concentration of 100 mg/L. Moreover, most of the isoxazole compounds displayed higher herbicidal activity against B. campestris L. than Echinochloa crus‐galli. However, these compounds showed weak herbicidal activities at the concentration of 10 mg/L.     

Design,synthesis and herbicidal activity of novel cyclic phosphonates with diaryl ethers containing pyrimidine

Abstract

Thirteen novel cyclic phosphates were rationally designed and synthesized by introducing diary ethers containing pyrimidine. All the target compounds were characterized by ¹H, ¹³C, ³¹P NMR and HRMS. The test of herbicidal activity indicated that most of the compounds showed good herbicidal activities against Amaranthus retroflexus. The compounds IA-2 (1-(5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)propyl-2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzoate) and IA-3 ((5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)(phenyl)methyl-2-((4,6-dimethoxypyrimidin-2-yl)oxy)benzoate) exhibited remarkable post-emergency herbicidal activity against the tested monocotyledonous weed at the dosage of 112.5?g ai/ha.     

N-取代-6-(3-氯-4-氯甲基-2-氧吡咯烷-1-基)-7-氟-3,4-二氢-2H-1,4-苯并噁嗪-3-酮衍生物的合成与生物活性研究

采用生物活性基团拼接的分子设计方法, 将活性基团2-氧吡咯烷引入到2H-[1,4]苯并噁嗪-3(4H)-酮分子结构的苯环上, 设计并合成了16个未见文献报道的N-取代-6-(3-氯-4-氯甲基-2-氧吡咯烷-1-基)-7-氟-3,4-二氢-2H-1,4-苯并噁嗪-3-酮衍生物6a～6p, 其结构经IR, ¹H NMR, LC/MS和元素分析确证. 初步的生物活性测试结果表明, 部分化合物具有较高的除草和杀虫活性, 如6c～6f等化合物在用量为150 g/hm²时对苘麻(Abutilon theophrasti)、刺苋(Amaranthus spinosus)和藜(Chenopodium album L)等阔叶杂草具有90%以上的抑制率, 6l和6o在500 mg/L浓度下对蚕豆蚜(Aphis fabae)具有90%以上的致死率, 个别化合物还兼具除草及杀虫活性.     

Synthesis and Biological Activity of Ethyl 4‐Alkyl‐2‐(2‐(substituted phenoxy)acetamido)thiazole‐5‐carboxylate

A series of novel ethyl 4‐(methyl or trifluoromethyl)‐2‐(2‐(substituted phenoxy)acetamido)thiazole‐5‐carboxylates 7a , 7b , 7c , 7d , 7e and 8f , 8g , 8h , 8i , 8j , 8k , 8l , 8m , 8n , 8o , 8p , 8q , 8r were synthesized, and their structures were confirmed by IR, ¹H‐NMR, MS spectra and elemental analysis. The results of preliminary bioassays show that some of the title compounds exhibit moderate to good herbicidal activities. Compared with the fluorine free compounds 7a , 7b , and 7e , the compounds bearing fluorine 8g , 8j , and 8q showed higher herbicidal activities with 70–100% inhibition against Capsella bursa‐pastoris, Amaranthus restroflexus, and Eclipta prostrata at the dosage of 150 g/ha, which indicated that the trifluoromethyl on the thiazole ring was beneficial for the herbicidal activity. Furthermore, compounds 8f , 8g , 8h , 8i , 8j , 8k , 8l , 8m , 8n , 8o , 8p , 8q , 8r were tested for fungicidal activity against Pseudoperonospora cubensis at 500 µg/mL. Compounds 8f and 8q showed the best fungicidal activity with more than 80% inhibition.     

2-氰基-3-甲硫基-3-取代甲氨基丙烯酸酯类化合物的合成及其除草活性

A series of 2-cyano-3-methylthio-3-substituted methylaminoacrylates were synthesized as herbicidal inhibitors of photosystem Ⅱ （PSⅡ） electron transport, in order to estimate the effect of fluorine atom, pyridyl group, chirality and ester chain on activity. The important intermediate 2-fluoro-5-aminomethylpyridine was synthesized with high yield. The bioassay results showed that most of rifle compounds had high herbicidal activity in postemergence treatment. The introduction of an a-methyl into the 3-substituted methylamino could improve the activity notably. The replacement of hydrogen by chlorine or fluorine group and phenyl by pyridyl group showed different effects, and at the same time, the ester chain affected the activity too.     

Synthesis and Herbicidal Activity of Novel N‐(2‐Fluoro‐5(3‐methyl‐2,6‐dioxo‐4‐(trifluoromethyl)‐2,3‐dihydro‐pyrimidin‐1(6H)‐yl)phenyl)‐2‐phenoxyacetamide Derivatives

Thirteen novel N‐(2‐fluoro‐5‐(3‐methyl‐2,6‐dioxo‐4‐(trifluoromethyl)‐2,3‐dihydropyrimidin‐1(6H)‐yl)phenyl)‐2‐phenoxy)acetamides were designed and synthesized utilizing 4‐fluoro‐aniline and ethyl 3‐amino‐4,4,4‐trifluoro‐but‐2‐enoate as starting materials. The chemical structures of all compounds were confirmed by ¹H NMR, IR, mass spectrum and elemental analyses. Subsequently, the herbicidal activities of the as‐prepared compounds were evaluated in the greenhouse. Bioassay results indicated that most of compounds had better herbicidal activities against dicotyledonous weeds. Among all the tested compounds, compounds 4a – 4i showed good herbicidal activities at both pre‐emergence and post‐emergence treatment against two or three kinds of dicotyledonous weeds, such as Abutilon theophrasti Medic, Amaranthus ascendens L, and Chenopodium album L at the dosage of 75 g ai/ha.     

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.     

Synthesis and Herbicidal Activity of α-Hydroxy Phosphonate Derivatives Containing Pyrimidine Moiety

A series of α‐hydroxy phosphonate derivatives containing pyrimidine moiety were designed and synthesized. Their structures were characterized by IR, ¹H NMR, MS and elemental analysis. The results of preliminary herbicidal activities (in vitro) showed that some of the title compounds 2 exhibited moderate herbicidal activities against dicotyledonous weeds (Brassica campestris L), and most of compounds 2 showed better activity against dicotyledonous weeds than monocotyledonous weeds (Echinochloa crus‐galli). Further bioassays (in vivo) indicated that some of the title compounds 2 possessed good and selective herbicidal activity against amaranth pigweed (A. retroflexus) in both pre‐ and post‐emergence treatments at the dose of 1.5 kg/ha. For exmple, compounds 2a , 2b and 2e exhibited 100% inhibition against A. retroflexus in pre‐emergence treatment, and 91.7%, 98.8% and 99.5% inhibition in post‐emergence treatment at the dose of 1.5 kg/ha, respectively.     

Synthesis and Herbicidal Activity of Novel Pyrimidinyl Derivatives Containing an α-Amino Phosphonate Moiety

In order to find novel pyrimidinyl carboxylic acid analogs with high activity and low toxicity, a series of novel pyrimidinyl derivatives containing an α-amino phosphonate moiety 5 was synthesized by the condensation of 4-(4,6-dimethoxypyrimidin-2-yloxy)phenoxyacetic 3a or propionic acids 3b with dialkyl α-amino substitutedbenzyl phosphonates 4. Their structures were characterized by spectroscopic data (IR, ¹H NMR, ³¹P NMR, MS) and elemental analyses. The results of preliminary herbicidal activities (in vitro) showed that most of these compounds exhibited higher herbicidal activities against dicotyledonous weeds (Brassica campestris L) than monocotyledonous weeds (Echinochloa crus-galli). Further bioassays (in vivo) indicated that some of compounds 5 possessed selective herbicidal activity against amaranth pigweed (A. retroflexus) in post-emergence treatment.

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.