4-nitroimino-1,3,5-oxadiazinane | 123019-22-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-nitroimino-1,3,5-oxadiazinane
• 英文别名: 4-nitriminotetrahydro-1,3,5-oxadiazine；4-nitroimino-1,3,5-oxadiazinan；N-Nitro-3,6-dihydro-2H-1,3,5-oxadiazin-4-amine；N-(1,3,5-oxadiazinan-4-ylidene)nitramide
• CAS: 123019-22-7
• 化学式: C₃H₆N₄O₃
• 分子量: 146.106
• InChiKey: WHDVTHIOPKCRGZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  91.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-nitroimino-1,3,5-oxadiazinane 在 硝酸 、 乙酸酐 作用下， 以 水 为溶剂， 反应 1.0h， 以56%的产率得到4-nitrimino-3,5-dinitrotetrahydro-1,3,5-oxadiazine
  参考文献：
  名称：

  2-nitroguanidine derivatives: X. Synthesis and nitration of 4-nitriminotetrahydro-1,3,5-oxadiazine and 2-nitriminohexahydro-1,3,5-triazine and their substituted derivatives

  摘要：

  A new synthetic procedure was developed to obtain 1-hydroxymethyl-2- nitroguanidine from 2-nitroguanidine and formaldehyde without catalyst. Reactions of 2-nitroguanidine and its 1-methyl- and 1-phenylsubstituted derivatives with formaldehyde and urotropin under acid catalysis resulted in 4-nitriminotetrahydro1,3,5-oxadiazine and 2-nitriminohexahydro-1,3,5-triazine and their methyl- and phenyl-substituted derivatives, whose nitration with concn. HNO3 in the presence of acetic anhydride and concn. H2SO4 depending on the temperature conditions led to the formation of 4-nitrimino-3,5-dinitrotetrahydro-1,3,5-oxadiazine, 3-methyl-4-nitrimino5-nitrotetrahydro-1,3,5-oxadiazine, 2-nitrimino-5-nitrohexahydro-1,3,5-triazine, and 1,3,5-trinitro-hexahydro-1,3,5-triazine-2-one.

  DOI：

  10.1134/s1070428007100041
• 作为产物：
  描述：

  聚合甲醛 、 硝基胍 在 甲酸 作用下， 生成 4-nitroimino-1,3,5-oxadiazinane
  参考文献：
  名称：

  Synthesis and Properties of Thiamethoxam and Related Compounds

  摘要：

  新烟碱类杀虫剂是最成功的化学类杀虫剂之一，其销售额在2003年达到了10亿美元以上，主要是由于咪唑烟碱和噻虫嗪的市场表现优异。本文描述了噻虫嗪及其相关化合物的发现、合成和杀虫活性，并报告了噻虫嗪的水解稳定性和降解途径，以及降解产物的合成。

  DOI：

  10.1515/znb-2006-0401

文献信息

• Azido-Neonicotinoids as Candidate Photoaffinity Probes for Insect Nicotinic Acetylcholine Receptors [1]
  作者：Peter Maienfisch、Joerg Haettenschwiler、Alfred Rindlisbacher、Arnaud Decock、Henning Wellmann、Hartmut Kayser

  DOI：10.2533/000942903777678605

  日期：——

  The neonicotinoids are the most successful chemical class of insecticides reaching sales of more than 630 Mio $ in 2001, mainly due to the excellent market performance of imidacloprid and thiamethoxam. The insect nicotinic acetylcholine receptors (nAChRs) are the targets for these compounds, which are highly effective against a variety of sucking and chewing insects. Compared with the other neonicotinoid sales products, thiamethoxam binds in a different way, possibly to a different site of nAChRs in aphids. To gain further insight into the different modes of binding, a research program applying the photoaffinity labeling technique was started. A series of novel candidate photoaffinity probes containing a 5-azido-6-chloropyridin-3-ylmethyl group were prepared from 5-azido-6-chloropyridin-3-ylmethyl chloride, which was obtained in three steps from 6-chloropyridin-3-ylmethyl chloride. These probes showed good to excellent contact/feeding and systemic activity against Myzus persicae, however, they were at least 4- to 16-fold less effective against Aphis craccivora, Nilaparvata lugens, Spodoptera littoralis, and Diabrotica balteata than the neonicotinoid sales products. In general, the introduction of an azide group at C(5) of the 6-chloropyridin-3-ylmethyl substituent resulted in reduced potency as well as in a narrower pest spectrum. In competition binding assays with [3H]imidacloprid, analogues of imidacloprid, clothianidin, thiacloprid and thiamethoxam containing a 5-azido-6-chloropyridin-3-ylmethyl group showed high displacing potency with nAChRs from Aphis and Myzus (Ki values: 2 to 27 nM) suggesting that these compounds are valuable candidate photoaffinity probes. Taking into account the biological screening activity as well as the receptor binding potency, 1-(5-azido-6-chloropyridin-3-ylmethyl)-2-nitroimino-imidazolidine, N-(5-azido-6-chloropyridin-3-ylmethyl)-N?-methyl-N?-nitroguanidine and 3-(5-azido-6-chloropyridin-3-ylmethyl)-2-cyanoimino-thiazolidine were identified as the preferred candidate neonicotinoid photoaffinity probes to study the imidacloprid binding site.

  新烟碱类杀虫剂是最成功的化学类杀虫剂之一，2001年销售额超过6.3亿美元，主要归功于良好的市场表现，如吡虫啉和噻虫嗪。这些化合物的靶点是昆虫的尼古丁乙酰胆碱受体（nAChRs），对多种吸食和咀嚼昆虫具有高效作用。与其他新烟碱类杀虫剂销售产品相比，噻虫嗪以不同的方式结合，可能是与蚜虫的nAChRs上的不同位点结合。为了进一步了解不同的结合模式，开始了一个应用光致亲和标记技术的研究项目。从6-氯吡啶-3-甲基氯化物中经过三步制备了一系列新型候选光致亲和探针，其中包含5-叠氮-6-氯吡啶-3-基甲基基团。这些探针对桃蚜具有良好至优异的接触/摄食和系统活性，但对黑豆蚜、褐飞虱、棉铃虫和斜纹夜蛾至少比新烟碱类杀虫剂销售产品低4至16倍。总的来说，在6-氯吡啶-3-甲基取代基的C（5）位置引入叠氮基团导致了活性降低以及害虫谱变窄。在与[3H]吡虫啉竞争结合实验中，含有5-叠氮-6-氯吡啶-3-基甲基基团的吡虫啉、克虫啉、噻虫啉和噻虫嗪类似物在蚜虫和桃蚜的nAChRs上显示出高位移能力（Ki值：2至27 nM），表明这些化合物是有价值的候选光致亲和探针。考虑到生物筛选活性和受体结合效力，1-（5-叠氮-6-氯吡啶-3-基甲基）-2-硝基亚咪唑啉、N-（5-叠氮-6-氯吡啶-3-基甲基）-N？-甲基-N？-硝基胍和3-（5-叠氮-6-氯吡啶-3-基甲基）-2-氰基亚噻唑啉被确定为首选的候选新烟碱类光致亲和探针，用于研究吡虫啉结合位点。
• 一种3-乙酰基-4-硝基亚氨基-1,3,5-恶二嗪 的合成方法
  申请人：南通天泽化工有限公司

  公开号：CN107245060B

  公开（公告）日：2020-08-04

  本发明涉及一种3‑乙酰基‑4‑硝基亚氨基‑1,3,5‑恶二嗪的合成方法,(1)在反应釜A加入含水量为25％的硝基胍和多聚甲醛，然后滴加质量百分浓度为40％的甲酸，并升温至70‑80℃反应，反应完成后加碳酸钾中和PH＝7‑8，降温过滤洗涤烘干，得到4‑硝基亚胺基‑1,3，5‑恶二嗪；(2)在反应釜B中依次加入甲苯和4‑硝基亚胺基‑1,3，5‑恶二嗪，形成混合液，然后滴加溶有乙酰氯的甲苯溶液，并加热至100‑110℃反应5‑6h，降温过滤，用甲苯洗滤饼，烘干得到产品3‑乙酰基‑4‑硝基亚氨基‑1,3,5‑恶二嗪。本发明的优点在于：严格控制各反应中各原料的摩尔比以及各工艺参数条件，可大大提高产品收率，且大大保证产品的含量。
• The discovery of thiamethoxam: a second-generation neonicotinoid
  作者：Peter Maienfisch、Hanspeter Huerlimann、Alfred Rindlisbacher、Laurenz Gsell、Hansruedi Dettwiler、Joerg Haettenschwiler、Evelyne Sieger、Markus Walti

  DOI：10.1002/1526-4998(200102)57:2<165::aid-ps289>3.0.co;2-g

  日期：2001.2

  Neonicotinoids represent a novel and distinct chemical class of insecticides with remarkable chemical and biological properties. In 1985, a research programme was started in this field, in which novel nitroimino heterocycles were designed, prepared and assayed for insecticidal activity. The methodology for the synthesis of 2-nitroimino-hexahydro-1,3,5-triazines, 4-nitroimino-1,3,5-oxadiazinanes and 4-nitroimino-1,3,5-thiadiazinanes is outlined. Bioassays demonstrated that 3-(6-chloropyridin-3-ylmethyl)-4-nitroimino-1,3,5-oxadiazinane exhibited better insecticidal activity than the corresponding 2-nitroimino-hexahydro-1,3,5-triazine and 4-nitroimino-1,3,5-thiadiazinane. In most tests, this compound was equally or only slightly less active than imidacloprid. A series of structural modifications on this lead structure revealed that replacement of the 6-chloro-3-pyridyl group by a 2-chloro-5-thiazolyl moiety resulted in a strong increase of activity against chewing insects, whereas the introduction of a methyl group as pharmacophore substituent increased activity against sucking pests. The combination of these two favourable modifications led to thiamethoxam (CGA 293 343).Thiamethoxam is the first commercially available second-generation neonicotinoid and belongs to the thianicotinyi sub-class. It is marketed under the trademarks Actara(R) for foliar and soil treatment and Cruiser(R) for seed treatment. The compound has broad-spectrum insecticidal activity and offers excellent control of a wide variety of commercially important pests in many crops. Low use rates, flexible application methods, excellent efficacy and the favourable safety profile make this new insecticide well-suited for modern integrated pest management programmes in many cropping systems. (C) 2001 Society of Chemical Industry.