(3-(tert-butyl)-4,5-dihydroisoxazol-5-yl)methanol | 191676-58-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: (3-(tert-butyl)-4,5-dihydroisoxazol-5-yl)methanol
• 英文别名: (3-Tert-butyl-4,5-dihydro-1,2-oxazol-5-YL)methanol
• CAS: 191676-58-1
• 化学式: C₈H₁₅NO₂
• 分子量: 157.213
• InChiKey: QKZPPUZEXMEYMU-UHFFFAOYSA-N

物化性质

• 沸点：
  228.3±32.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  41.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3-(tert-butyl)-4,5-dihydroisoxazol-5-yl)methanol 在 草酰氯 、 氢气 、 硼酸 、 镍 、 二甲基亚砜 、 三乙胺 作用下， 以 甲醇 、 水 为溶剂， 反应 2.0h， 生成 syn-5,6-dihydroxy-2,2-dimethyloctan-3-one
  参考文献：
  名称：

  Nucleophilic additions to and reductiosn of 5-formyl-and 5-acyl-2-isoxazolines (4,5-dihydeoisoxazoles): a stereoselective route to β,γ-dihydroxy ketones

  摘要：

  Reductions of readily available 5-acyl-2-isoxazolines with L-Selectride follow the Felkin-Anh model and produce syn-5-hydroxyalkyl-2-isoxazolines with excellent (> 95:5) selectivities. Swern oxidation of 5-hydroxymethyl-2-isoxazolines, followed by direct addition of a Grignard reagent to the intermediate 5-formyl-2-isoxazolines, also follows the Felkin-Anh model and produces anti-5-hydroxyalkyl-2-isoxazolines with modest (80:20) to excellent (> 95:5) selectivity. In contrast, additions of Grignard reagents to 5-acyl-2-isoxazolines follow the chelation model, and give syn or anti products (depending on choice of acyl substituent and Grignard reagent) with good (90:10) to excellent selectivity. These selectivities are almost always far superior to those that can be obtained by direct nitrile oxide cycloaddition to a chiral allylic alcohol or ether. The resulting products are readily reduced to syn- or anti-beta,gamma-dihydroxy ketones. A speculative model to explain this surprising reversal in selectivity between formyl and acyl isoxazolines is proposed.

  DOI：

  10.1039/p19910002613
• 作为产物：
  描述：

  (1Z)-N-hydroxy-2,2-dimethylpropanimidoyl chloride 在 氟化氢吡啶 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 25.0h， 生成 (3-(tert-butyl)-4,5-dihydroisoxazol-5-yl)methanol
  参考文献：
  名称：

  A strategic alternative to solid phase synthesis: Preparation of a small isoxazoline library by “fluorous synthesis”

  摘要：

  The preparation of a highly fluorinated silyl group and its use as a ''fluorous label'' are described. Allyl and propargyl alcohols are rendered fluorous upon attachment to the fluorous label. Cycloaddition of the fluorous dipolarophiles to nitrite oxides provides the corresponding isoxazol(in)es which are purified by simple liquid-liquid extractions. After detachment of the label and renewed extraction, the organic isoxazol(in)es are obtained. This new fluorous methodology allows the preparation of isoxazol(in)es in high purities without using chromatography. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00224-x

文献信息

• Manganese-Promoted Oxidative Cyclization of Unsaturated Oximes Using Molecular Oxygen in Air under Ambient Conditions
  作者：Daisuke Yamamoto、Takuto Oguro、Yuuki Tashiro、Masayuki Soga、Kazuhito Miyashita、Yoshiaki Aso、Kazuishi Makino

  DOI：10.1002/ejoc.201600998

  日期：2016.11

  A highly efficient manganese-promoted oxidative cyclization of unsaturated oximes to afford the corresponding 4,5-dihydroisoxazoline alcohols was developed. A very low loading (generally 0.1–0.2 mol-%) of Mn(acac)3 (acac = acetylacetonate) promoted the oxidative cyclization through the direct incorporation of molecular oxygen present in air (open flask) at room temperature.

  开发了一种高效的锰促进的不饱和肟氧化环化，以提供相应的 4,5-二氢异恶唑啉醇。Mn(acac)3（acac = 乙酰丙酮化物）的负载非常低（通常为 0.1–0.2 mol-%）通过在室温下直接掺入空气（开口烧瓶）中存在的分子氧来促进氧化环化。
• Cobalt-catalyzed aerobic oxidative cyclization of β,γ-unsaturated oximes
  作者：Weifei Li、Pingjing Jia、Bing Han、Dianjun Li、Wei Yu

  DOI：10.1016/j.tet.2013.02.032

  日期：2013.4

  Cobalt complex Co(nmp)2 can efficiently catalyze the aerobic oxidative 5-exo cyclization of β,γ-unsaturated oximes to afford isoxazolines. The key cyclization step involves the generation of carbon-centred radicals. The products are largely dependent on the reaction conditions. The oxidative termination products 2 were produced predominantly when the reaction was carried out in i-PrOH, whereas the

  钴配合物Co（nmp）2可以有效催化β，γ-不饱和肟的有氧氧化5-外切环化反应，得到异恶唑啉。关键的环化步骤涉及碳中心自由基的产生。产物在很大程度上取决于反应条件。当在i -PrOH中进行反应时，主要产生氧化终止产物2，而在环己-1,4-二烯存在下，在甲苯中选择性地获得还原终止产物3。
• Isoxazolines as antiinflammatory agents
  申请人：Pfizer Inc.

  公开号：US05552424A1

  公开（公告）日：1996-09-03

  Certain novel isoxazoline compounds having the ability to inhibit the 5-lipoxygenase enzyme and having formula (I), ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.4 alkyl or --NR.sub.3 R.sub.4 ; R.sub.3 and R.sub.4 are each independently H or C.sub.1 -C.sub.4 alkyl; M is H or a pharmaceutically acceptable cation; A is C.sub.1 -C.sub.6 alkylene, C.sub.2 -C.sub.6 alkenylene or C.sub.2 -C.sub.6 alkynylene; Ar is phenylene or mono-, di- or tri-substituted phenylene wherein the substituents are each independently selected from halogen, C.sub.1 -C.sub.4 alkyl and C.sub.1 -C.sub.4 alkoxy; n is an integer of 0 or 1; Y is H or C.sub.1 -C.sub.4 alkyl; R.sub.2 is C.sub.1 -C.sub.10 alkyl, C.sub.1 -C.sub.4 arylalkyl or C.sub.2 -C.sub.4 arylalkenyl; and said aryl and each aryl moiety in said arylalkyl and arylalkenyl may be substituted by from one to three substituents independently selected from halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, halosubstituted C.sub.1 -C.sub.4 alkyl, halosubstituted C.sub.1 -C.sub.4 alkoxy, aryl-C.sub.1 -C.sub.4 alkoxy, phenoxy and mono-, di- and tri-substituted phenoxy wherein the substituents are each independently selected from halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy and halosubstituted C.sub.1 -C.sub.4 alkyl. These compounds are useful in the treatment or alleviation of inflammatory diseases, allergy and cardiovascular diseases in mammals and as the active ingredient in pharmaceutical compositions for treating such conditions.

  某些新型异噁唑啉化合物具有抑制5-脂氧合酶酶的能力，其化学式为(I)，其中R.sub.1为C.sub.1-C.sub.4烷基或--NR.sub.3 R.sub.4; R.sub.3和R.sub.4分别为H或C.sub.1-C.sub.4烷基; M为H或药用可接受的阳离子; A为C.sub.1-C.sub.6烷基，C.sub.2-C.sub.6烯基或C.sub.2-C.sub.6炔基; Ar为苯基或单、二或三取代苯基，其中取代基分别独立地选自卤素、C.sub.1-C.sub.4烷基和C.sub.1-C.sub.4烷氧基; n为0或1的整数; Y为H或C.sub.1-C.sub.4烷基; R.sub.2为C.sub.1-C.sub.10烷基，C.sub.1-C.sub.4芳基烷基或C.sub.2-C.sub.4芳基烯基; 而且，在所述芳基和所述芳基烷基和芳基烯基中的每个芳基基团可以被从一个到三个取代基独立地选自卤素、C.sub.1-C.sub.6烷基、C.sub.1-C.sub.6烷氧基、卤代C.sub.1-C.sub.4烷基、卤代C.sub.1-C.sub.4烷氧基、芳基-C.sub.1-C.sub.4烷氧基、苯氧基和单、二和三取代苯氧基，其中所述取代基独立地选自卤素、C.sub.1-C.sub.4烷基、C.sub.1-C.sub.4烷氧基和卤代C.sub.1-C.sub.4烷基。这些化合物在哺乳动物中治疗或缓解炎症性疾病、过敏和心血管疾病，并作为制备用于治疗此类疾病的药物组合物的活性成分。
• Process for preparing isoxazolines
  申请人：von Oppolzer, Wolfgang Wilhelm R.E.J.

  公开号：EP0453189A1

  公开（公告）日：1991-10-23

  Chiral oxazolines having the general formula: wherein R is C₁ to C₁₀ alkyl or phenyl and the R¹ groups are independently hydrogen or C₁ to C₄ alkyl are prepared in substatially optically pure form by a process comprising the steps of (1) reacting a nitrile oxide of formula R-C=N-O with an acryloyl derivative of formula Z-COCH=C(R¹)₂ where Z is a moiety derived from a chiral sultam and    (2) reacting the product of step (1) with a hydrogenating agent to produce the oxazoline and a chiral sultam of formula ZH. The chiral oxalines described are useful as intermediates in e.g. the pharmaceutical or agrochemical industries.

  具有通式的手性噁唑啉： 其中 R 为 C₁ 至 C₁₀ 烷基或苯基，R¹ 基团独立地为氢或 C₁ 至 C₄ 烷基，通过以下步骤制备亚光学纯形式的手性噁唑啉。 O 与式 Z-COCH=C(R¹)₂ 的丙烯酰衍生物反应，其中 Z 是衍生自手性苏坦的分子；(2) 将步骤 (1) 的产物与氢化剂反应，生成草唑啉和式 ZH 的手性苏坦。 所述手性噁唑啉可用作医药或农用化学品等行业的中间体。
• FLUOROUS REACTION AND SEPARATION SYSTEMS
  申请人：UNIVERSITY OF PITTSBURGH

  公开号：EP0907625A1

  公开（公告）日：1999-04-14