丁布 | 15893-52-4

• 物质功能分类: 生物化工 - 抑制剂
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 中文名称: 丁布
• 中文别名: 2,4-二羟基-7-甲氧基-2H-1,4-苯并噁嗪-3(4H)-酮
• 英文名称: 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one
• 英文别名: 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3(4H)-one；DIMBOA；2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3-one
• CAS: 15893-52-4
• 化学式: C₉H₉NO₅
• 分子量: 211.174
• InChiKey: GDNZNIJPBQATCZ-UHFFFAOYSA-N

物化性质

• 熔点：
  150-155 °C
• 沸点：
  461.3±55.0 °C(Predicted)
• 密度：
  1.589±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于丙酮（少许）、DMSO（少许）、甲醇（少许）
• 物理描述：
  Solid

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  79.2
• 氢给体数：
  2
• 氢受体数：
  5

安全信息

• 危险性防范说明：
  P261,P280,P301+P312,P302+P352,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  -20°C

制备方法与用途

用途

丁布在农作物中起着抗真菌和抗藻的作用，其结构中的苯并恶嗪酮基团发挥着这些作用。

生物活性

DIMBOA 是一种抗生素，是禾本科植物如玉米、小麦和黑麦的化学防御系统的一部分。研究表明，DIMBOA 对许多已研究的细菌和真菌菌株具有生长抑制特性，例如金黄色葡萄球菌、大肠杆菌以及酿酒酵母。此外，DIMBOA 表现出强大的自由基清除活性，并且在铁 (III) 离子还原活性方面相对较弱，这赋予了其显著的抗氧化性质。

反应信息

• 作为反应物：
  描述：

  丁布 在 (2,2,2-trichloro-ethylidene)-carbamic acid ethyl ester 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以45%的产率得到2,4-dihydroxy-6-methoxybenzoxazolin-2(3H)-one
  参考文献：
  名称：

  天然产物DIMBOA脱水制得的甲酰化剂

  摘要：

  玉米的天然2,4-二羟基-7-甲氧基-2H-1、4-苯并恶嗪-3（4H）-1（DIMBOA，1）经过自然脱水和重排形成3-甲酰基-6-甲氧基苯并恶唑啉-2 （3H）-一（FMBOA，2）与N-乙氧羰基-三氯乙二胺反应。化合物2被证明是针对N-，O-和S-亲核试剂的反应性甲酰基供体，这在生物条件下形成2的情况下可能很重要。

  DOI：

  10.1021/np980515s
• 作为产物：
  描述：

  4-羟基-7-甲氧基-1,4-苯并恶嗪-3-酮 在 四丁基氟化铵 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 10.0h， 生成 丁布
  参考文献：
  名称：

  过氧化物氧化法将环状异羟肟酸进行α-羟基氧化：禾本科化感物质的一种新方法

  摘要：

  天然存在的半缩醛DIBOA和DIMBOA是通过N-羟基内酰胺通过相应的环甲硅烷基烯醇醚的间氯过苯甲酸的第一次α-羟基化反应合成的。

  DOI：

  10.1016/s0040-4039(00)73347-8
• 作为试剂：
  描述：

  阿特拉津 在 丁布 作用下， 以 水 为溶剂， 生成 2-羟基莠去津
  参考文献：
  名称：

  Kinetics of Uptake and Metabolism of Atrazine in Model Plant Systems

  摘要：

  The present work concerns atrazine absorption and metabolism by corn (Zea mays.) seedlings immersed in an aqueous medium in comparison with Acer pseudoplatanus cell cultures. At the point of equilibrium the apparent concentration inside the A. pseudoplatanus cells (with a moderate lipid content: 0.17% of dry weight) was about twice that of the medium. This equilibrium was probably due to a simple partition process; part of the atrazine was dissolved in the cell water and reached the same concentration as in the external medium while the rest was concentrated inside the cellular lipids. The theoretical calculation of the lipid/water partition, taking into account the value of log P measured not with the lipids but with octanol (log P = 2.5), gave a value of 1.5 for concentration inside the plant material. Such an equilibrium, resulting from a partition process between water and lipids, was also obtained in non-living corn seedlings. In living seedlings, an over-concentration of radioactivity due to [C-14]atrazine derivatives was rapidly obtained inside roots and shoots giving concentrations respectively 7- and 12-fold higher than that of atrazine in the external medium. This was due to very rapid chemical transformation of atrazine into its hydroxy derivatives, especially hydroxyatrazine. This hydrolysis of atrazine in corn was due to the presence of high levels of benzoxazinone derivatives in corn seedling cells. The hydroxylated metabolites were able to concentrate in the cells very rapidly and were unable to diffuse freely into the external medium. As a consequence, this process facilitated the penetration of large quantities of atrazine which became rapidly hydroxylated, allowing therefore the passive penetration of atrazine to be further improved, since the concentration C-1 in the receiver compartment was always close to zero. The passive transfer of atrazine, following Fick's law: dq/dt = - Pa (C-0-C-1), was therefore optimized.

  DOI：

  10.1002/(sici)1096-9063(199702)49:2<157::aid-ps517>3.0.co;2-m

文献信息

• Isolation and Synthesis of Allelochemicals from Gramineae:  Benzoxazinones and Related Compounds
  作者：Francisco A. Macías、David Marín、Alberto Oliveros-Bastidas、David Chinchilla、Ana M. Simonet、José M. G. Molinillo

  DOI：10.1021/jf050896x

  日期：2006.2.1

  ongoing research into the potential agronomic utility of these compounds required large amounts of them, which were obtained from natural sources. This paper presents a modified methodology to access DIMBOA from Zea mays cv. Apache and to obtain 2-O-beta-D-glucopyranosyl-2,4-dihydroxy-(2H)-1,4-benzoxazin-3(4H)-one (DIBOA-Glc) and DIBOA from Secale cereale L. New synthetic methodologies were employed for

  自（2H）-1,4-苯并嗪-3（4H）-一骨架的化合物引起了植物化学研究者的关注，因为2,4-二羟基-（2H）-1,4-苯并嗪-3（4H）-一骨架从禾本科（POAceae）家族的植物中分离出（DIBOA）和2，4-二羟基-7-甲氧基-（2H）-1，4-苯并恶嗪-3（4H）-一（DIMBOA）。这些化合物表现出令人感兴趣的生物学特性，例如植物毒性，抗微生物，拒食，抗真菌和杀虫特性。这些化学物质，除了涉及其代谢，解毒机理以及在农作物土壤和其他系统上的降解所涉及的各种相关化合物之外，还引起了人们的极大兴趣，在某些情况下还具有潜在的农学应用价值。除了一些作者对其化学的贡献外，本文还介绍了对合成观察方法的完整综述。正在进行的对这些化合物潜在的农学实用性的研究正在进行的降解和植物毒性实验需要大量的这些化合物，这些都是从自然资源中获得的。本文提出了一种从Zea mays cv访问DIMBOA的改进方法。
• Structure−Activity Relationships (SAR) Studies of Benzoxazinones, Their Degradation Products and Analogues. Phytotoxicity on Standard Target Species (STS)
  作者：Francisco A. Macías、David Marín、Alberto Oliveros-Bastidas、Diego Castellano、Ana M. Simonet、José M. G. Molinillo

  DOI：10.1021/jf0484071

  日期：2005.2.1

  Benzoxazinones 2,4-dihydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (DIMBOA) and 2,4-dihydroxy-(2H)-1,4-benzoxazin-3(4H)-one (DIBOA) have been considered key compounds for understanding allelopathic phenomena in Gramineae crop plants such as corn (Zea mays L.), wheat (Triticum aestivum L.), and rye (Secale cereale L.). The degradation processes in the environment observed for these compounds, in which

  苯并恶嗪酮 2,4-二羟基-7-甲氧基-(2H)-1,4-苯并恶嗪-3(4H)-酮 (DIMBOA) 和 2,4-二羟基-(2H)-1,4-苯并恶嗪-3(4H) )-one (DIBOA) 被认为是了解禾本科作物（例如玉米 (Zea mays L.)、小麦 (Triticum aeSTivum L.) 和黑麦 (Secale Cereale L.)）化感作用现象的关键化合物。在环境中观察到的这些化合物的降解过程（其中土壤微生物直接参与）可能会影响这些植物的潜在化感活性。我们在这项工作中提出了一项完整的结构-活性关系研究，该研究基于观察到的 DIMBOA、DIBOA 及其主要降解产物以及它们的几种合成类似物的植物毒性作用。它们对标准目标物种 (STS) 的影响进行了评估，其中包括作为单子叶植物的 Triticum aeSTivum L.（小麦）和 Allium cepa L.（洋葱）以及 Lepidium
• Reaction of a cyclic hydroxamic acid from gramineae with thiols
  作者：Hermann M. Niemeyer、Luis J. Corcuera、Francisco J. Pérez

  DOI：10.1016/0031-9422(82)85192-3

  日期：1982.1

  Abstract An insect inhibitor isolated from maize extracts, 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA), reacted with cysteine, mercaptoethanol, ethane

  摘要 从玉米提取物中分离的昆虫抑制剂 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA)，与半胱氨酸、巯基乙醇、乙烷反应
• Species-Specific Glucosylation of DIMBOA in Larvae of the Rice Armyworm
  作者：Hiroaki SASAI、Masahiro ISHIDA、Kenjiro MURAKAMI、Naoko TADOKORO、Atsushi ISHIHARA、Ritsuo NISHIDA、Naoki MORI

  DOI：10.1271/bbb.80903

  日期：2009.6.23

  DIMBOA [2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3(4H)-one] is a benzoxazinoid (Bx), part of the chemical defense system of graminaceous plants such as maize, wheat, and rye. When Bombyx mori larvae were fed artificial diets containing DIMBOA, they died in three days. In contrast, Mythimna separata larvae, a serious pest of rice, maize, sorghum, wheat etc., grew well on the same diets. Three kinds of glucosides [1-(2-hydroxy-4-methoxyphenylamino)-1-deoxy-β-glucopyranoside-1,2-carbamate (methoxy glucoside carbamate), 2-O-β-glucopyranosyl-4-hydroxy-7-methoxy-2H-1,4-benzoxazin-3(4H)-one (DIMBOA-2-O-Glc), and 2-O-β-glucopyranosyl-7-methoxy-2H-1,4-benzoxazin-3(4H)-one (HMBOA-2-O-Glc)] were identified by LC-MS and NMR analyses from the frass of M. separata that had been fed on a DIMBOA-containing diet. Furthermore, the incubation of DIMBOA with a midgut tissue suspension of M. separata in the presence of UDP-d-glucose generated DIMBOA-2-O-Glc. These findings strongly suggest that glucosylation by UDP-glucosyltransferase(s) was important for detoxification to circumvent the defenses of host plants against M. separata larvae.

  DIMBOA[2,4-二羟基-7-甲氧基-2H-1,4-苯并恶嗪-3(4H)-酮]是一种苯并恶嗪类化合物（Bx），是玉米、小麦和黑麦等禾本科植物化学防御系统的一部分。当用含有 DIMBOA 的人工饲料喂养蚕蛾幼虫时，它们会在三天内死亡。与此相反，水稻、玉米、高粱、小麦等作物的严重害虫 Mythimna separata 幼虫在同样的饲料中生长良好。三种葡糖苷[1-（2-羟基-4-甲氧基苯基氨基）-1-脱氧-β-吡喃葡萄糖苷-1,2-氨基甲酸酯（甲氧基葡糖苷氨基甲酸酯）、2-O-β-吡喃葡萄糖基-4-羟基-7-甲氧基-2H-1、通过 LC-MS 和 NMR 分析，从喂食了 M. separata 的粪便中鉴定出了 2-O-β-吡喃葡萄糖基-4-羟基-7-甲氧基-2H-1,4-苯并恶嗪-3(4H)-酮（DIMBOA-2-O-Glc）和 2-O-β-吡喃葡萄糖基-7-甲氧基-2H-1,4-苯并恶嗪-3(4H)-酮（HMBOA-2-O-Glc）。通过 LC-MS 和 NMR 分析，确定了以含 DIMBOA 的食物喂养的 M. separata 的粪便中含有 DIMBOA。此外，在有 UDP-d-葡萄糖存在的情况下，DIMBOA 与 M. separata 的中肠组织悬浮液孵育会产生 DIMBOA-2-O-Glc。这些发现有力地表明，UDP-葡萄糖基转移酶的葡萄糖基化作用对于解毒以规避寄主植物对分离贻贝幼虫的防御非常重要。
• Syntheses of 2-hydroxy-4,7-dimethoxy-2H-1,4-benzoxazin-3(4H)-one: A precursor of a bioactive electrophile from Gramineae
  作者：Carlos A. Escobar、Michael Kluge、Dieter Sicker

  DOI：10.1016/s0040-4039(96)02492-6

  日期：1997.2

  2-Hydroxy-4,7-dimethoxy-2H-1,4-benzoxazin-3(4H)-one (8), the hitherto undescribed free hemiacetalic aglycone of a benzoxazinoid acetal glucoside naturally occurring in wheat, has been synthesized following two pathways, independently. This cyclic hydroxamic acid methyl ester proved to be very unstable when in solution. This gives rise to the assumption that HDIBOA naturally released from its acetal

  已经合成了2-羟基-4,7-二甲氧基-2 H -1,4-苯并恶嗪-3（4 H）-one（8），这是小麦中天然存在的迄今未描述的苯并恶嗪样缩醛糖苷的游离半缩醛糖苷。两条途径，独立。证明该环状异羟肟酸甲酯在溶液中时非常不稳定。这引起这样的假设，即从其乙缩醛葡糖苷天然释放的HDIBOA是通过甲醇盐消除而形成多中心亲电试剂的前体，该亲电试剂最近被报道是苯并恶嗪样铅的生物活性成分。

表征谱图