1,5-二氮杂双环[3.2.1]辛烷 | 280-28-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂卓
• 中文名称: 1,5-二氮杂双环[3.2.1]辛烷
• 英文名称: 1,5-diazabicyclo[3.2.1]octane
• CAS: 280-28-4
• 化学式: C₆H₁₂N₂
• 分子量: 112.175
• InChiKey: WYQMORNXPLBZBV-UHFFFAOYSA-N

物化性质

• 沸点：
  144.9±8.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tetrafluoroboric acid 、 1,5-二氮杂双环[3.2.1]辛烷 以 甲醇 、 水 为溶剂， 生成 1,5-diazabicyclo[3.2.1]-octonium tetrafluoroborate
  参考文献：
  名称：

  Rational Design of Ceramic-Like Molecular Ferroelectric by Quasi-Spherical Theory

  摘要：

  Molecular ferroelectrics are attracting tremendous interest because of their easy and environmentally friendly processing, light weight, low acoustical impedance, and mechanical flexibility, which are viable alternatives or supplements to conventional ceramic ferroelectrics. However, reports of ceramic-like molecular ferroelectrics that can be applied in the polycrystalline form have been scarce. Here, according to the "quasi-spherical theory", we successfully synthesized a ceramic-like molecular ferroelectric with an m (3) over bar mFmm2 type phase transition at 357 K, 1,5-diazabicyclo[3.2.1]-octonium tetrafluoroborate ([3.2.1-dabco]BF4), which can show excellent ferroelectric performance in the polycrystalline thin-film form at room temperature. On the basis of the reported molecular ferroelectric [2.2.2-dabco]BF4 (2.2.2-dabco = 1,4-diazabicyclo[2.2.2]-octonium) with an Aizu notation of 4/mmmFmm2 and two polar axes, we changed the [2.2.2-dabco](+) cation to the [3.2.1-dabco](+) cation to reduce the molecular symmetry and keep the quasi-spherical shape simultaneously, making the number of polar axes up to six. Moreover, the spontaneous polarization P, gets successfully increased from 4.9 mu C cm(-2) in [2.2.2-dabco]BF4 to 5.5 mu C cm(-2) in [3.2.1-dabco]BF4. This precise molecular design strategy offers an efficient pathway to design ceramic-like molecular ferroelectrics.

  DOI：

  10.1021/jacs.9b11665
• 作为产物：
  描述：

  高哌嗪 、 聚合甲醛 以 水 、 甲苯 为溶剂， 反应 6.0h， 生成 1,5-二氮杂双环[3.2.1]辛烷
  参考文献：
  名称：

  球形分子中的可逆相变和介电异常 [(3,2,1-dabco)2PbBr6]

  摘要：

  摘要 有机-无机杂化材料因其在相变和光电领域的潜在应用而备受关注。在此背景下，球形分子 1, 5-二氮杂双环 [3,2,1] 辛烷 (3,2,1-dabco) 用于与浓 HBr 酸中的 PbBr2 反应，生成离散的有机无机杂化化合物 [( 3,2,1-dabco)2PbBr6] (1)。1 的热力学 DSC 分析和介电测量显示在约 427 K 处明显可逆相变。变温 X 射线单晶衍射表明化合物 1 在室温和高温下经历了从正交系统到立方系统的有序-无序转变。

  DOI：

  10.1016/j.inoche.2020.107932

文献信息

• Using Methanol as a Formaldehyde Surrogate for Sustainable Synthesis of <scp> <i>N</i> ‐Heterocycles </scp> via <scp>Manganese‐Catalyzed</scp> Dehydrogenative Cyclization
  作者：Zhihui Shao、Shanshan Yuan、Yibiao Li、Qiang Liu

  DOI：10.1002/cjoc.202100886

  日期：2022.5.15

  The development of an efficient and sustainable synthetic route for formaldehyde production from renewable feedstock, especially in combination with a subsequent transformation to straightforwardly construct valuable chemicals, is highly desirable. Herein, we report a novel manganese-catalyzed dehydrogenative cyclization of methanol as a formaldehyde surrogate with a variety of dinucleophiles for facile

  开发一种高效且可持续的从可再生原料生产甲醛的合成路线，尤其是结合随后的转化以直接构建有价值的化学品是非常可取的。在此，我们报告了一种新型的锰催化甲醇脱氢环化反应，作为甲醛替代物，其具有多种亲核试剂，可方便地合成N-杂环化合物。通过催化甲醇脱氢原位产生的甲醛可以被多种双亲核试剂选择性地捕获，以避免几种可能的副反应。这种转化的实用性通过其成功应用于合成13 C-标记的N-杂环使用13 CH 3 OH 作为容易获得的13 C-同位素试剂。
• (METH)ACRYLATE MANUFACTURING METHOD
  申请人：TOAGOSEI CO., LTD

  公开号：US20180118658A1

  公开（公告）日：2018-05-03

  The present invention provides a (meth)acrylate manufacturing method characterized in that when manufacturing a (meth) acrylate by an ester exchange reaction between an alcohol and a monofunctional (meth)acrylate using catalyst A and catalyst B together, contact treatment of the ester exchange reaction product with adsorbent C is performed. Catalyst A: One or more kinds of compounds selected from a group consisting of cyclic tertiary amines with an azabicyclo structure and salts or complexes thereof, amidine and salts or complexes thereof, compounds with a pyridine ring and salts or complexes thereof, phosphines and salts or complexes thereof, and compounds with a tertiary diamine structure and salts or complexes thereof. Catalyst B: One or more kinds of compounds selected from a group consisting of compounds comprising zinc. Adsorbent C: One or more kinds of compounds selected from a group consisting of oxides and hydroxides comprising at least one of magnesium, aluminum and silicon.

  本发明提供了一种（甲基）丙烯酸酯制备方法，其特征在于通过在使用催化剂A和催化剂B一起进行醇和单官能基（甲基）丙烯酸酯之间的酯交换反应制备（甲基）丙烯酸酯时，对酯交换反应产物进行与吸附剂C的接触处理。催化剂A：从含有氮杂双环结构的环状三级胺及其盐或络合物、胺嘧啶及其盐或络合物、含有吡啶环的化合物及其盐或络合物、膦及其盐或络合物、以及含有三级二胺结构的化合物及其盐或络合物中选择的一种或多种化合物。催化剂B：从含锌化合物中选择的一种或多种化合物。吸附剂C：从含有镁、铝和硅中至少一种的氧化物和氢氧化物中选择的一种或多种化合物。
• Phosphorus compound
  申请人：——

  公开号：US20030109736A1

  公开（公告）日：2003-06-12

  The phosphorus-containing compound of the present invention is represented by the following formula (I), (II) or (III): 1 wherein Z 1 , Z 2 and Z 3 each represents a cycloalkane, a cycloalkene, a polycyclic aliphatic hydrocarbon or an aromatic hydrocarbon rings which may have a substituent; R represents a halogen atom, a hydroxyl, a carboxyl, a halocarboxyl (haloformyl), an alkyl, an alkoxy, an alkenyl or an aryl groups; A represents a polyvalent group corresponding to an alkane; Y 1 , Y 2 and Y 3 each represents —O—, —S— or —NR 1 —, wherein R 1 represents a hydrogen atom or an alkyl group; k is an integer of to 6; m is an integer of 0 to 2; n is an integer of not less than 1; q is an integer of 0 to 5; r is 0 or 1; and S is an integer of 1 to 4. The phosphorus-containing compound is excellent in heat resistance and is useful as flame retardants, plasticizers, or stabilizers.

  本发明的含磷化合物由以下式(I)、(II)或(III)表示：其中Z1、Z2和Z3分别表示可能具有取代基团的环烷烃、环烯烃、多环脂肪烃或芳香烃环；R表示卤素原子、羟基、羧基、卤代羧基（卤甲酰基）、烷基、烷氧基、烯基或芳基；A表示对应于烷烃的多价基团；Y1、Y2和Y3分别表示—O—、—S—或—NR1—，其中R1表示氢原子或烷基；k为0至6的整数；m为0至2的整数；n为不少于1的整数；q为0至5的整数；r为0或1；S为1至4的整数。这种含磷化合物具有优异的耐热性，可用作阻燃剂、增塑剂或稳定剂。
• MULTIFUNCTIONAL (METH)ACRYLATE MANUFACTURING METHOD
  申请人：TOAGOSEI CO., LTD.

  公开号：US20170204044A1

  公开（公告）日：2017-07-20

  [Problem] The purpose of the present invention is to obtain a multifunctional (meth)acrylate with good yield by an ester exchange reaction of a polyhydric alcohol such as pentaerythritol or dipentaerythritol with a monofunctional (meth)acrylate. [Solution] A multifunctional (meth)acrylate manufacturing method characterized in that when manufacturing a multifunctional (meth)acrylate by an ester exchange reaction of a polyhydric alcohol with a monofunctional (meth)acrylate, catalyst (A) and catalyst (B) are used together. Catalyst (A): One or more kinds of compounds selected from a group consisting of cyclic tertiary amines with an azabicyclo structure or salts or complexes thereof, amidines or salts or complexes thereof, and compounds with a pyridine ring or salts or complexes thereof. Catalyst (B): One or more kinds of compounds selected from a group consisting of zinc-containing compounds.

  [问题] 本发明的目的是通过多元醇（如戊三醇或二戊三醇）与单官能基（甲基）丙烯酸酯的酯交换反应，获得产率高的多功能（甲基）丙烯酸酯。[解决方案] 一种多功能（甲基）丙烯酸酯制备方法，其特征在于，在通过多元醇与单官能基（甲基）丙烯酸酯的酯交换反应制备多功能（甲基）丙烯酸酯时，同时使用催化剂（A）和催化剂（B）。催化剂（A）：选自具有氮杂双环结构的环三胺或其盐或络合物、酰胺或其盐或络合物以及吡啶环或其盐或络合物组成的群中的一种或多种化合物。催化剂（B）：选自含锌化合物组成的群中的一种或多种化合物。
• Process and apparatus for producing ketoisophorone
  申请人：Daicel Chemical Industries,Ltd.

  公开号：US20020055657A1

  公开（公告）日：2002-05-09

  &bgr;-isophorone is formed by isomerizing &agr;-isophorone in the presence of an isomerizing catalyst (an aliphatic C 5-20 polycarboxylic acid) in an isomerizing-reaction unit 1. The &bgr;-isophorone thus formed is oxidized with oxygen in an inert solvent in the presence of an oxidizing catalyst (a complex salt of a transition metal and an N,N′-disalicylidenediamine) in an oxidizing-reaction unit 2, thereby forming ketoisophorone. After removing a low-boiling point component, which is an impurity (non-conjugated cyclic ketone), from the reaction mixture using a distilling unit 3, a high-boiling component (oxidizing catalyst) is separated in a distilling unit 4 , and then ketoisophorone is separated from the solvent in the separation unit 5. Thereafter, the solvent containing 0 to 5,000 ppm (weight basis) of the impurities and substantially free from ketoisophorone is recycled to the oxidizing reaction through a recycling line 6. According to the present invention, the combination of the isomerizing reaction and the oxidizing reaction makes it possible to produce ketoisophorone from &agr;-isophorone while maintaining the activity of the oxidizing catalyst.

  &bgr;-异佛尔酮是通过在异构化反应装置1中，在异构化催化剂（脂肪族C5-20多羧酸）的存在下，将&agr;-异佛尔酮异构化形成的。然后，在氧化反应装置2中，在氧化催化剂（过渡金属的复杂盐和N，N'-二水杨基二胺）的存在下，将&Bgr;-异佛尔酮与氧气在惰性溶剂中氧化，从而形成酮异佛尔酮。使用蒸馏装置3从反应混合物中去除低沸点成分（非共轭环状酮）作为杂质后，使用蒸馏装置4分离高沸点成分（氧化催化剂），然后使用分离装置5从溶剂中分离出酮异佛尔酮。此后，含有0至5,000 ppm（重量基础）杂质且基本不含酮异佛尔酮的溶剂通过回收线6循环到氧化反应中。根据本发明，异构化反应和氧化反应的组合使得能够在保持氧化催化剂活性的同时从&agr;-异佛尔酮中生产酮异佛尔酮。