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

• Synthesis and Properties of Thiamethoxam and Related Compounds
  作者：Peter Maienfisch

  DOI：10.1515/znb-2006-0401

  日期：2006.4.1

  The neonicotinoids are the most successful chemical class of insecticides reaching sales of more than $1 billion in 2003, mainly due to the excellent market performance of imidacloprid and thiamethoxam. This paper describes the discovery, the synthesis and the insecticidal activity of thiamethoxam and related compounds and reports the hydrolytic stability and the degradation pathways of thiamethoxam together with the synthesis of the degradation products

  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。
• 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.
• 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
  作者：E. L. Metelkina

  DOI：10.1134/s1070428007100041

  日期：2007.10

  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.