4-羟基-7-甲氧基-1,4-苯并恶嗪-3-酮 | 69884-05-5

• 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: 4-羟基-7-甲氧基-1,4-苯并恶嗪-3-酮
• 英文名称: 4-hydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one
• 英文别名: 4-hydroxy-7-methoxy-3,4-dihydro-2H-1,4-benzoxazin-3-one；4-hydroxy-7-methoxy-1,4-benzoxazin-3-one
• CAS: 69884-05-5
• 化学式: C₉H₉NO₄
• 分子量: 195.175
• InChiKey: AFMLVQPDSTZQOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  14
• 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：
  59
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-羟基-7-甲氧基-1,4-苯并恶嗪-3-酮 在 potassium carbonate 作用下， 以 乙醚 为溶剂， 反应 0.75h， 生成 4-(2-hydroxy-5-methoxyphenyl)-7-methoxy-2H-1,4-benzoxazin-3(4H)-one
  参考文献：
  名称：

  由独特的生物活性环状异羟肟酸4-羟基-7-甲氧基-2H-1,4-苯并恶嗪-3（4H）-形成的多中心亲电试剂

  摘要：

  4-羟基-7-甲氧基-2H-1,4-苯并恶嗪-3（4H）-1（HMBOA）由于其药理，农药和抗微生物特性而备受关注。HMBOA的可能的生物活性代谢物是4-乙酰氧基-7-甲氧基-2H-1,4-苯并恶嗪-3（4H）-one（AMBOA）。研究了AMBOA与苯酚，苯胺，硫醇，杂芳族化合物，氨基酸衍生物和核酸的亲电反应，以及该化合物引起的生物学效应的化学机理。结果表明，HMBOA在代谢O-酰化后充当蛋白质和核酸的烷基化剂。

  DOI：

  10.1016/s0040-4020(01)96098-3
• 作为产物：
  描述：

  3-甲氧基苯酚 在 palladium on activated charcoal sodium tetrahydroborate 、 硝酸 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 水 、 溶剂黄146 、 丙酮 为溶剂， 生成 4-羟基-7-甲氧基-1,4-苯并恶嗪-3-酮
  参考文献：
  名称：

  Analogs of the cyclic hydroxamic acid 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3-one (DIMBOA): decomposition to benzoxazolinones and reaction with .beta.-mercaptoethanol

  摘要：

  Analogues of the aglucones of naturally occurring cyclic hydroxamic acids (2,4-dihydroxy-1,4-benzoxazin-3-ones) from Gramineae (Poaceae) have been synthesized by the reductive cyclization of the ring-substituted methyl alpha-(o-nitrophenoxy)-alpha-methoxyacetates, followed by demethylation of the C-2 methoxy group with BBr3 or BCl3 to reveal the 2-hydroxy group. A structure-activity series was produced by varying the substituent at C-7 on the aromatic ring [R = MeO (1), t-Bu (6), Me (7), H (8), Cl (9), F (10), CO2Me (11a)]. The pK(a) values for the hydroxamic acid and the phenol moieties were determined for each member of the C-7 series. They correlated well with sigma in a linear free energy relationship (LFER) yielding values of rho = 0.71 (with sigma-p) for pK(a1) (the hydroxamic acid) and rho = 1.6 (with sigma-m) for pK(a2) (the phenol). A LFER also existed between the rate constants for the unimolecular decomposition of these hydroxamic acids to benzoxazolinones and sigma+ (rho = 1.1). The rates of hydroxamic acid reduction to lactams by beta-mercaptoethanol were also investigated. It was found that only compounds with electron-rich aromatic rings and specifically an oxa functionality para to the hydroxamic acid nitrogen atom (compounds 1 and 3-5) had measurable rates of reduction. H-1 NMR spectra recorded during this reaction in D2O buffers (pD9), however, showed that compounds 1, 2, 6-9 (the only ones investigated) formed a hemithioacetal at C-2 even though only 1 has a measurable rate of reduction by the same thiol. The remarkable rate enhancement provided by an oxa functionality suggests that reduction occurs by direct attack of thiolate on the hydroxamic nitrogen of a resonance-stabilized ion pair.

  DOI：

  10.1021/jo00005a025

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
• New Herbicide Models from Benzoxazinones:  Aromatic Ring Functionalization Effects
  作者：Francisco A. Macías、João M. De Siqueira、Nuria Chinchilla、David Marín、Rosa M. Varela、José M. G. Molinillo

  DOI：10.1021/jf062709g

  日期：2006.12.1

  electronic molecular parameters, the resulting molecular volume (V) and dipole moment (mu) being the most influential ones. Halogenations at C-6 and fluorination at C-7 were the most successful modifications. Compounds 6-fluoro-(2H)-1,4-benzoxazin-3(4H)-one (6F-D-DIBOA), 7-fluoro-(2H)-1,4-benzoxazin-3(4H)-one (7F-D-DIBOA), and 6-chloro-(2H)-1,4-benzoxazin-3(4H)-one (6Cl-D-DIBOA) had the highest phytotoxic

  苯并恶嗪酮及其一些合成衍生物在寻找除草剂模型开发的新线索中的用途已被广泛讨论。由于苯并恶嗪酮骨架包含三个不同的潜在官能化区域（C-2，N-4和芳族质子H-5，H-6，H-7和H-8），并且前两个已经进行了优化，这项工作的主要目的是将芳香族质子替换为不同的取代基类型，并研究所制备的化学品对所选标准目标物种（STS）和杂草的影响。因此，在不同位置引入了芳族取代基的不同组合，包括甲氧基，甲氧基羰基，氟，氯和三氟甲基。植物毒性结果已成功与空间和电子分子参数相关联，最有影响的分子体积（V）和偶极矩（mu）。最成功的修饰是C-6处的卤代和C-7处的氟化。化合物6-氟-（2H）-1,4-苯并恶嗪-3（4H）-一（6F-D-DIBOA），7-氟-（2H）-1,4-苯并恶嗪-3（4H）-一（ 7F-D-DIBOA）和6-氯-（2H）-1,4-苯并恶嗪-3（4H）-一（6Cl-D-DIBOA）具有最高的植物毒
• Rearrangement of 4-acetoxy-2H-1,4-benzoxazin-3(4H)-one.
  作者：YUICHI HASHIMOTO、TAKAYOSHI ISHIZAKI、KOICHI SHUDO、TOSHIHIKO OKAMOTO

  DOI：10.1248/cpb.31.3891

  日期：——

  4-Acetoxy-2H-1, 4-benzoxazin-3 (4H)-one (3) undergoes rearrangement or nucleophilic attack to give 2-, 5-, 6-, and 7-substituted derivatives of the benzoxazinone according to the reaction conditions. The formation of 5- and 7-substituted products was interpreted in terms of nucleophilic attack on the cation (14) formed by the heterolysis of the N-O bond of 3. For the formation of 6-substituted derivatives of the benzoxazinone, participation of the oxygen atom at position 1 of the benzoxazinone (that is, formation of an oxonium ion, 18) is important. A possible mechanism for the formation of 2-substituted products also involves an oxonium ion (19). These novel aspects of acetoxybenzoxazinone chemistry may contribute to an understanding of the mechanism of the actions of the prohibitins in cereal plants.

  4-乙酰氧基-2H-1, 4-苯并恶嗪-3 (4H)-酮(3)根据反应条件进行重排或亲核攻击，得到苯并恶嗪酮的2-、5-、6-和7-取代衍生物。 5-和7-取代产物的形成被解释为对由3的N-O键杂解形成的阳离子(14)的亲核攻击。对于苯并恶嗪酮的6-取代衍生物的形成，氧的参与苯并恶嗪酮 1 位原子（即形成氧鎓离子 18）很重要。形成 2-取代产物的一个可能机制还涉及氧鎓离子 (19)。乙酰氧基苯并嗪酮化学的这些新颖方面可能有助于理解谷类植物中抑制素的作用机制。
• α-Hydroxylation of cyclic hydroxamic acids by peroxide oxidation : A novel approach to allelochemicals from Gramineae
  作者：Holger Hartenstein、Dieter Sicker

  DOI：10.1016/s0040-4039(00)73347-8

  日期：1994.6

  Naturally occurring hemiacetals DIBOA and DIMBOA were synthesized by the first α-hydroxylation of N-hydroxylactams via m-chloroperbenzoic acid oxidation of corresponding cyclosilyl enol ethers.

  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。