1,7,7-三甲基双环[2.2.1]庚烷-2-醇 | 405197-74-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: 1,7,7-三甲基双环[2.2.1]庚烷-2-醇
• 英文名称: borneol
• 英文别名: Sumatra camphor；(1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol
• CAS: 405197-74-2
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: DTGKSKDOIYIVQL-SHTILUHOSA-N

物化性质

• 物理描述：
  Borneol appears as a white colored lump-solid with a sharp camphor-like odor. Burns readily. Slightly denser than water and insoluble in water. Used to make perfumes.
• 颜色/状态：
  White to off-white crystals
• 气味：
  Piney, camphor-like odor
• 味道：
  Burning taste somewhat reminiscent of mint
• 沸点：
  212 °C
• 熔点：
  202 °C
• 闪点：
  150 °F (60 °C) /closed cup/
• 溶解度：
  In water, 738 mg/L at 25 °C
• 蒸汽压力：
  5.02X10-2 mm Hg at 25 °C

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  11
• 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：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

ADMET

毒理性

• 毒性总结

识别和使用：冰片是一种固体。它被用作香料，并作为药物使用，包括传统中医。人类暴露和毒性：冰片不会引起皮肤过敏。其毒性实质上与樟脑相似。人类外周血淋巴细胞在DMSO中暴露于不同浓度的l-冰片，浓度高达600微克/毫升，持续4小时，有和无代谢激活以及24小时无代谢激活。在研究的条件下，l-冰片被认为不具有致裂变性。动物研究：与樟脑类似，实验室动物对冰片的毒性似乎比人类要小得多。冰片增加了大鼠口服处理7天后CYP2D的活性。冰片在小鼠中已被评估其镇痛和抗炎活性。冰片在爪子舔舐的早期和晚期显著减少了痛觉行为，并减少了小鼠的扭动反射。当进行热板测试时，高剂量的冰片产生了痛觉行为的抑制。此外，冰片处理的小鼠减少了角叉菜胶诱导的白细胞迁移到腹腔。冰片的致突变潜力在Ames试验中通过使用鼠伤寒沙门氏菌TA1535、TA1537、TA1538、TA98和TA100菌株，在存在和不存在代谢激活的情况下，用冰片以高达5000微克/平板的浓度处理进行了评估。其他研究证实了在鼠伤寒沙门氏菌TA98和TA100菌株中缺乏致突变潜力。在研究的条件下，冰片被认为在细菌中不具有致突变性。

IDENTIFICATION AND USE: Borneol is a solid. It is used as a flavoring, and as a medication, including traditional Chinese medicine. HUMAN EXPOSURE AND TOXICITY: Borneol does not present a concern for skin sensitization. Toxicity is essentially indistinguishable from that of camphor. Human peripheral blood lymphocytes were exposed to varying concentrations of l-borneol in DMSO up to 600 ug/mL for 4 hr, with and without metabolic activation and 24 hr without metabolic activation. Under the conditions of the study, l-borneol was considered non-clastogenic. ANIMAL STUDIES: As with camphor, laboratory animals appear to be much less susceptible to borneol toxicity than man. Borneol increased the activity of CYP2D in rats orally treated by borneol for 7 days. Borneol has been evaluated for antinociceptive and anti-inflammatory activities in mice. Borneol produced a significant reduction of the nociceptive behavior at the early and late phases of paw licking and reduced the writhing reflex in mice. When the hot plate test was conducted, borneol (in higher dose) produced an inhibition of the nociceptive behavior. Additionally, borneol-treated mice had reduced the carrageenan-induced leukocytes migration to the peritoneal cavity. The mutagenic potential of borneol was assessed in an Ames test with Salmonella typhimurium strains TA1535, TA1537, TA1538, TA98 and TA100 treated with borneol at concentrations up to 5000 ug/ plate in the presence and absence of metabolic activation. Other studies confirming a lack of mutagenic potential in S. typhimurium strains TA98 and TA100 have been published. Under the conditions of the study, borneol is considered not mutagenic in bacteria.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 副作用

神经毒素 - 其他中枢神经系统神经毒素

Neurotoxin - Other CNS neurotoxin

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

毒理性

• 相互作用

为了研究冰片对具有不同亲水性和分子大小的化合物经角膜透过性的增强效果。选择了六种化合物作为模型药物，分别是罗丹明B、荧光素钠、异硫氰酸荧光素（FITC）葡聚糖4、10、20和40 kDa。透过性研究使用兔眼角膜摘除，通过Franz型扩散装置进行。冰片的安全性评估基于角膜水合水平和Draize眼刺激性试验。将0.2%冰片应用于角膜，使罗丹明B、荧光素钠、4和10 kDa FITC-葡聚糖的表观透过系数分别增加了1.82倍（p<0.05）、2.49倍（p<0.05）、4.18倍（p<0.05）和1.11倍（无统计学意义）。与对照组相比，10、20和40 kDa FITC-葡聚糖与冰片混合并未发现显著的透过性增强。0.2%冰片增强的透过系数与模型药物的分子量呈线性相关（R(2)=0.9976）。应用0.05%、0.1%和0.2%冰片后，角膜水合值小于83%，Draize评分小于4。冰片可能在不引起毒性反应的情况下，改善亲水和疏水化合物的经角膜渗透，尤其是亲水性化合物。此外，0.2%冰片可以增强分子量小于或等于4 kDa的亲水性化合物的透过性。因此，冰片可以被认为是一种安全有效的眼部给药渗透增强剂。

To investigate the enhancing effect of borneol on transcorneal permeation of compounds with different hydrophilicities and molecular sizes. Six compounds, namely rhodamine B, sodium-fluorescein, fluorescein isothiocyanate (FITC) dextrans of 4, 10, 20 and 40 kDa were selected as model drugs. Permeation studies were performed using excised cornea of rabbits by a Franz-type diffusion apparatus. The safety of borneol was assessed on the basis of corneal hydration level and Draize eye test. The application of 0.2% borneol to the cornea increased the apparent permeability coefficient by 1.82-(p<0.05), 2.49-(p<0.05), 4.18-(p<0.05), and 1.11-fold (not significant) for rhodamine B, sodium-fluorescein, FITC-dextrans of 4 and 10 kDa, respectively. No significant permeability enhancement of FITC dextrans of 10, 20 and 40 kDa with borneol was found compared to control. The permeability coefficient enhanced by 0.2% borneol was linear correlated to the molecular weight of model drugs (R(2)=0.9976). With the 0.05%, 0.1% and 0.2% borneol application, the corneal hydration values were <83% and Draize scores were <4. Borneol may improve the transcorneal penetration of both hydrophilic and lipophilic compounds without causing toxic reactions, especially hydrophilic ones. Furthermore, 0.2% borneol can enhance the permeation of hydrophilic compounds with molecular weight </= 4 kDa. Hence, borneol can be considered as a safe and effective penetration enhancer for ocular drug administration.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 相互作用

这项研究旨在通过MTT实验、流式细胞术和Western印迹法调查自然冰片/姜黄素（NB/Cur）对A375人类黑色素瘤细胞系生长和凋亡的协同效应。我们的结果显示，NB有效地与Cur协同作用，增强了对A375人类黑色素瘤细胞的抗增殖活性，通过诱导凋亡，表现为亚G1细胞群体增加、DNA断裂、PARP裂解和caspase活化。进一步的机制研究通过Western印迹法显示，细胞经NB/Cur处理后，磷酸化JNK表达水平上调和磷酸化ERK和Akt表达水平下调，促使A375细胞凋亡。此外，NB还增强了Cur触发细胞内ROS过度产生和DNA损伤的能力，并上调了磷酸化ATM、磷酸化Brca1和磷酸化p53的表达水平。结果表明，NB和Cur联合应用在癌症治疗中具有潜在的应用价值。

This study was to investigate the synergistic effect of natural borneol/curcumin (NB/Cur) on growth and apoptosis in A375 human melanoma cell line by MTT assay, flow cytometry and Western blotting. Our results demonstrated that NB effectively synergized with Cur to enhance its antiproliferative activity on A375 human melanoma cells by induction of apoptosis, as evidenced by an increase in sub-G1 cell population, DNA fragmentation, PARP cleavage, and caspase activation. Further mechanistic studies by Western blotting showed that after treatment of the cells with NB/Cur, up-regulation of the expression level of phosphorylated JNK and down-regulation of the expression level of phosphorylated ERK and Akt contributed to A375 cells apoptosis. Moreover, NB also potentiated Cur to trigger intracellular ROS overproduction and the DNA damage with up-regulation of the expression level of phosphorylated ATM, phosphorylated Brca1 and phosphorylated p53. The results indicate the combinational application potential of NB and Cur in treatments of cancers.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

立即急救：确保已经进行了充分去污。如果患者停止呼吸，开始人工呼吸，最好使用需求阀复苏器、气囊面罩装置或口袋面罩，按训练进行操作。根据需要执行心肺复苏。立即用缓慢流动的水冲洗受污染的眼睛。不要催吐。如果发生呕吐，让患者前倾或置于左侧（如果可能的话，头部向下）以保持呼吸道畅通，防止吸入。保持患者安静，维持正常体温。寻求医疗帮助。/樟脑及其相关化合物/

Immediate First Aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Camphor and related compounds/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

为了开发一种气相色谱-火焰离子化检测法（GC-FID）来测定冰片在小鼠组织中的浓度，并研究静脉注射和鼻腔给药后冰片的组织分布，收集了在给药后1、3、5、10、20、30、60、90、120分钟的冰片30.0 mg/kg剂量下的小鼠大脑、心脏、肝脏、脾脏、肺和肾脏。用乙酸乙酯提取组织中的药物，以十八烷为内标，通过气相色谱检测冰片的浓度。校准曲线显示出良好的线性关系。提取回收率、日间和日内精密度以及稳定性均符合生物样本分析的要求。冰片主要分布在大多数组织中，心脏、大脑和肾脏中较多，肝脏、脾脏和肺中较少。建立的GC-FID方法适用于组织中冰片含量的测定。在小鼠静脉注射和鼻腔给药后，冰片主要分布在血液供应丰富的组织中。在鼻腔给药后，大脑组织中显示出最高的目标系数和目标效果。

To develop a GC-FID method to determine borneol's concentration in mouse tissues, and to investigate the tissue distribution after intravenous and intranasal administrations of borneol, mouse brains, hearts, livers, spleens, lungs and kidneys were collected at 1, 3, 5, 10, 20, 30, 60, 90, 120 min after administration of borneol with the dose of 30.0 mg/kg. The drug in tissues was extracted with ethyl acetate, and borneol's concentration detected by GC, with octadecane as the internal standard. The calibration curve showed a good linear relationship. Extraction recoveries, inter-day and intra-day precisions and stability were in conformity with the analytical requirements of biological samples. Borneol was mainly distributed in most tissues, more in heart, brain and kidney, and less in liver, spleen and lung. The established GC-FID method is applicable for content determination of borneol in tissues. After intravenous and intranasal administrations in mice, borneol is mainly distributed in abundant blood-supply tissues. After intranasal administration, brain tissues showed the highest target coefficient and target effectiveness.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

为了理解静脉注射、鼻腔给药或口服给药后血液和大脑的药物动力学，并探讨鼻腔给药的优越性和可行性，开发了一种带有火焰离子化检测（FID）的简单气相色谱（GC）方法，用于定量测定冰片。在给小鼠静脉注射、鼻腔给药或口服给药30.0 mg/kg冰片后，分别于1、3、5、10、20、30、60、90和120分钟收集血液样本和大脑。样品前处理是通过使用辛烷内标溶液的液-液萃取来进行的。药代动力学参数是通过计算机软件计算得出的。血浆和大脑中冰片的校准曲线分别在0.11-84.24 ug/mL和0.16-63.18 ug/g范围内呈线性。方法回收率和提取回收率均在85%-115%范围内。血浆和大脑样本的日内和日间变异性均小于或等于5.00%相对标准偏差（RSD）。鼻腔给药和口服给药的绝对生物利用度F分别为90.68%和42.99%。鼻腔给药和口服给药的相对脑靶向系数Re分别为68.37%和38.40%。所开发的GC-FID方法可用于测定和药代动力学研究。注射给药的冰片分布和代谢速度快，没有吸收过程。口服给药的冰片分布较慢，绝对生物利用度最低。冰片的鼻腔给药能迅速吸收进入血液和大脑，使用方便，安全性高于注射，这使得它值得作为治疗脑病的给药途径进一步开发。

... In order to understand the blood and brain pharmacokinetics after intravenous, intranasal, or oral administration and to investigate the superiority and feasibility of intranasal administration, a simple gas chromatographic (GC) method with flame ionization detection (FID) was developed for the quantification of borneol. Blood samples and brain were collected from mice at 1, 3, 5, 10, 20, 30, 60, 90, and 120 min after intravenous, intranasal, or oral administration of borneol at a dosage of 30.0 mg/kg. Sample preparations were carried out by liquid-liquid extraction with an internal standard solution of octadecane. The pharmacokinetic parameters were calculated /using computer software/. The calibration curves were linear in the range of 0.11-84.24 ug/mL and 0.16-63.18 ug/g for borneol in plasma and brain, respectively. The methodological and extraction recoveries were both in the range of 85%-115%. The intra-day and inter-day variabilities for plasma and brain samples were </= 5.00% relative standard deviation (RSD). The absolute bioavailabilities F of intranasal and oral administrations were 90.68% and 42.99%. The relative brain targeted coefficients Re of intranasal and oral administrations were 68.37% and 38.40%. The GC-FID method developed could be applied to determination and pharmacokinetic study. The borneol from injection was distributed and metabolized fast without absorption process. The borneol from oral administration was distributed more slowly and had the lowest absolute bioavailability. Nasal administration of borneol was quickly absorbed into the blood and brain, was easy to use and had a greater safety than infection, which makes it worthy of further development as an administration route for encephalopathy treatment.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

这项工作的目的是研究冰片的原位和活体鼻腔吸收。应用了一种新颖的单次通过原位鼻腔灌注技术来检查大鼠鼻腔吸收冰片的速率和程度。研究了灌注速率、pH值和药物浓度等实验条件。原位实验显示，冰片的鼻腔吸收不依赖于药物浓度，并且符合一级过程。吸收速率常数Ka随着灌注速度的增加而变化。在鼻咽腔的生理条件下，冰片在pH值范围内被很好地吸收。在大鼠中进行了冰片吸收的活体研究，并比较了鼻腔内给药（in）与静脉给药（iv）的药代动力学参数。冰片的生物利用度为90.82%，达到峰浓度的时间Tmax为10分钟。平均驻留时间MRT分别为262.55 +/- 67.35分钟和204.22 +/- 14.50分钟，分别对应于鼻腔内给药和静脉给药。结果表明，冰片可以通过大鼠鼻腔内给药被迅速且彻底吸收。

The aim of this work was to study the in situ and in vivo nasal absorption of borneol. A novel single pass in situ nasal perfusion technique was applied to examine the rate and extent of nasal absorption of borneol by rats. Experimental conditions, such as perfusion rate, pH and drug concentration, were investigated. The in situ experiments showed that the nasal absorption of borneol was not dependent on drug concentration, and fitted a first order process. The absorption rate constant, Ka, influenced with an increase in perfusion speed. The borneol was well absorbed in the conditions of the nasal cavity within the pH range and pH value of physiological conditions. In vivo studies of borneol absorption were carried out in rats and the pharmacokinetics parameters of intranasal (in) was compared with intravenous (iv) administration. The bioavailabilities of borneol was 90.82% for i.n. while Tmax values were 10 min. MRT (Mean Residence Time) were 262.55 +/- 67.35 min and 204.22 +/- 14.50 min for in and iv methods, respectively. The results demonstrate that borneol could be absorbed promptly and thoroughly by in administration in rats.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

先前的研究表明，冰片对中枢神经系统（CNS）具有双重作用，但机制尚不清楚。本研究的目的是阐明兴奋比率[兴奋性氨基酸（AAs）含量与抑制性氨基酸含量之比]与单次口服剂量后天然冰片含量的关系。小鼠通过口服摄入给予1.2 g/kg剂量的天然冰片（含98% D: -冰片）。在给药前和给药后0.083、0.167、0.25、0.333、0.5、0.75、1、1.5、2、2.5、3、4和5小时收集脑样本。通过GC-MS和HPLC-FLU分别测定小鼠脑中天然冰片的浓度和AA神经递质的含量。口服给药后，天然冰片迅速被吸收进入大脑，并在给药后5分钟可检测到。给药后1小时达到最大脑浓度（86.52微克/克）。天然冰片能够影响小鼠脑中AA神经递质的含量：L: -门冬氨酸在给药后0.083至1小时显著增加，L: -谷氨酸在给药后0.333小时显著增加并在1.5至5小时降低，γ-氨基丁酸在给药后0.167至5小时显著增加，而甘氨酸不受影响。兴奋比率是兴奋性AAs含量与抑制性AAs含量之比，反映了机体的兴奋或抑制状态。兴奋比率在给药后0.5小时暂时升高然后下降；在给药后1.5-5小时与给药前有显著差异。本研究表明，天然冰片能够影响AA神经递质的含量，兴奋比率的改变导致冰片对CNS的双重作用。

Previous studies have indicated that borneol has double side effects on the central nervous system (CNS), but the mechanism is unknown. The aim of this study was to clarify the relationship between excitation ratio [contents of excitatory amino acids (AAs) versus that of inhibitory] and the content of natural borneol after a single oral dose. Mice were administered a 1.2 g/kg dose of natural borneol (containing 98% D: -borneol) by oral ingestion. Brain samples were collected before administration and at 0.083, 0.167, 0.25, 0.333, 0.5, 0.75, 1, 1.5, 2, 2.5, 3, 4, and 5 hr after administration. The brain concentration of natural borneol and contents of AA neurotransmitters in mice brain were determined by GC-MS and HPLC-FLU, respectively. After per oral application, natural borneol was absorbed rapidly into the brain and could be determined 5 min after dosing. The maximal brain concentration (86.52 ug/g) was reached after 1 hr post-dosing. Natural borneol could affect the contents of AA neurotransmitters in mice brain: L: -aspartic acid increased significantly from 0.083 to 1 hr after administration, L: -glutamic acid increased significantly at 0.333 hr and decreased from 1.5 to 5 hr, gamma-amino-N-butyric acid increased significantly from 0.167 to 5 hr, whereas glycine was not affected. The excitation ratio is the contents of excitatory AAs versus that of inhibitory AAs, which reflects the excitatory or inhibitory state of the body. The excitation ratio elevated transitorily and then declined 0.5 hr post-dosing; there were significant differences between 1.5-5 hr post-dose compared with pre-dose. The present study indicated that natural borneol could affect the contents of AA neurotransmitters, and the change in excitatory ratio led to borneol's double side effects on the CNS.

来源:Hazardous Substances Data Bank (HSDB)

反应信息

• 作为反应物：
  描述：

  1,7,7-三甲基双环[2.2.1]庚烷-2-醇 在 potassium carbonate 作用下， 以 水 为溶剂， 以86%的产率得到白樟油
  参考文献：
  名称：

  负载在聚合物离子液体官能化磁性二氧化硅上的铂纳米粒子：有效和可重复使用的非均相催化剂，用于水中酒精的选择性氧化†

  摘要：

  在这项研究中，描述了核壳磁性二氧化硅纳米结构的合成，该结构通过聚合物离子液体的作用和铂纳米颗粒的固定化。首先，通过一步法使用含胺的有机硅烷合成并改性了磁性二氧化硅纳米粒子。通过将吡啶鎓离子液体和甲基丙烯酸甲酯单体分别合成和聚合到它们的表面上，使合成的纳米结构官能化。铂纳米颗粒固定在功能化的纳米颗粒上。所获得的官能化的纳米结构已用于在水性介质中的选择性和有氧氧化伯脂肪族和受阻仲脂肪族醇的氧化，并在温和的温度下表现出高活性。

  DOI：

  10.1039/c6ra16851e
• 作为产物：
  描述：

  白樟油 在 异丙醇 作用下， 反应 5.0h， 生成 1,7,7-三甲基双环[2.2.1]庚烷-2-醇
  参考文献：
  名称：

  阮内镍催化不饱和单萜类化合物的简单无氢加氢

  摘要：

  使用PriOH /阮内镍系统在82或150°C下将一系列单萜类化合物（柠檬酸，香芹酮，薄荷酮，樟脑）以及环己酮和6-5-烯-2-酮进行转移氢化。在单萜类化合物中，柠檬醛和香芹酮在5小时内于82°C进行了完全转化。

  DOI：

  10.1016/j.mencom.2019.07.006

文献信息

• Modified Hydroborate Agent: (2,2′-Bipyridyl)(tetrahydroborato)zinc Complex, [Zn(BH₄)₂(bpy)], as a New, Stable, Efficient Ligand-Metal Hydroborate and Chemoselective Reducing Agent
  作者：Behzad Zeynizadeh

  DOI：10.1246/bcsj.76.317

  日期：2003.2

  rato)zinc complex, [Zn(BH4)2(bpy)], is a new white stable compound which has been used for efficient reduction of variety of carbonyl compounds such as aldehydes, ketones, acyloins, α-diketones and α,β-unsaturated carbonyl compounds (1,2-reduction) to their corresponding alcohols in acetonitrile at room temperature. Excellent chemoselectivity was also observed for the reduction of aldehydes over ketones

  (2,2'-联吡啶基)(四氢硼酸根)锌配合物，[Zn(BH4)2(bpy)]，是一种新型白色稳定化合物，已用于有效还原各种羰基化合物，如醛、酮、酰基化合物, α-二酮和 α,β-不饱和羰基化合物（1,2-还原）在乙腈中在室温下转化为相应的醇。还观察到使用这种还原剂还原醛而不是酮具有优异的化学选择性。
• ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis
  作者：Peter W. Moore、Christopher D. G. Read、Paul V. Bernhardt、Craig M. Williams

  DOI：10.1002/chem.201800531

  日期：2018.3.26

  commercial catalyst supply. However, the mild instability of TPAP creates preparation, storage, and reaction reproducibility issues, due to unpreventable slow decomposition. In search of attributes conducive to catalyst longevity an extensive range of novel perruthenate salts were prepared. Subsequent evaluation unearthed a set of readily synthesized, bench stable, phosphonium perruthenates (ATP3 and

  该魔网格里菲斯四ñ丙基过钌酸铵（TPAP）催化剂已被合成界广泛采用，主要用于将醇氧化为醛和酮，还用于多种其他合成转化（例如二醇裂解，异构化，亚胺形成和杂环合成）。在广泛的反应范围，官能团耐受性，温和条件和商业催化剂供应上已经锻造了这种受欢迎度。但是，由于无法防止的缓慢分解，TPAP的轻度不稳定会导致制备，储存和反应重现性问题。为了寻找有利于催化剂寿命的属性，制备了多种新颖的过硼酸盐。随后的评估发现了一组易于合成，稳定的台式过氧化磷鎓（ATP3和MTP3），它们反映了TPAP的反应活性，
• Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols
  作者：Wen Zhang、Keith L. Carpenter、Song Lin

  DOI：10.1002/anie.201910300

  日期：2020.1.2

  context of alcohol oxidation. However, to date, the scope of this catalytic methodology has been limited to benzyl alcohols. In this work, mechanistic understanding of flavin-catalyzed oxidation reactions, in either the absence or presence of thiourea as a cocatalyst, was obtained. The mechanistic insights enabled development of an electrochemically driven photochemical oxidation of primary and secondary

  核黄素衍生的光催化剂在酒精氧化方面已得到广泛研究。然而，迄今为止，这种催化方法的范围仅限于苯甲醇。在这项工作中，获得了在不存在或存在硫脲作为助催化剂的情况下黄素催化氧化反应的机理。这些机理见解使得能够使用一对黄素和二烷基硫脲催化剂开发电化学驱动的伯醇和仲脂肪醇的光化学氧化。电化学可以避免使用 O2 和氧化剂并生成 H2 O2 作为副产物，这两种副产物都会在反应条件下氧化降解硫脲。这种修饰开启了一种新的机制途径，其中未活化醇的氧化是通过硫基介导的氢原子提取来实现的。
• Flat and Efficient H<i>CNN</i>and<i>CNN</i>Pincer Ruthenium Catalysts for Carbonyl Compound Reduction
  作者：Steven Giboulot、Salvatore Baldino、Maurizio Ballico、Rosario Figliolia、Alexander Pöthig、Shuanming Zhang、Daniele Zuccaccia、Walter Baratta

  DOI：10.1021/acs.organomet.8b00919

  日期：2019.3.11

  was isolated from 1 by reaction with NEt3. The monocarbonyl complexes trans-[RuCl2(HCNN)(PPh3)(CO)] (5–7) were synthesized from [RuCl2(dmf)(PPh3)2(CO)] and HCNN ligands, while the diacetate trans-[Ru(OAc)2(HCNN)(PPh3)(CO)] (8) was obtained from [Ru(OAc)2(PPh3)2(CO)]. Carbonylation of cis-[RuCl(CNN)(PPh3)2] with CO afforded the pincer derivatives [RuCl(CNN)(PPh3)(CO)] (9–11). Treatment of 9 with Na[BArf]4

  二齿ħ CNN二羰基钌络合物的反式，顺式-将[RuCl 2（H CNN）（CO）2 ]（1 - 3）和反式，顺式-将[RuCl 2（AMPY）（CO）2 ]（1A）通过制备将[RuCl的反应2（CO）2 ] ñ与1- [6-（4'-甲基苯基）吡啶-2-基]甲胺，苯并[ ħ ]喹啉（HC NN），和2-（氨基甲基）吡啶（AMPY ）配体。可替代地，衍生物1 - 3由水合RuCl 3与HCO 2 H和HC NN的反应得到。钳CNN顺-将[RuCl（CNN）（CO）2 ]（4）从分离1通过与净反应3。的单羰基配合物的反式-将[RuCl 2（H CNN）（PPH 3）（CO）]（5 - 7）从将[RuCl合成2（DMF）（PPH 3）2（CO）]和H CNN配体，而双乙酸酯反式-[Ru（OAc）从[Ru（OAc）2（PPh 3）2（CO）]获得2（HC NN）（PPh 3）（CO）]（8）。的羰基化的顺式-将[RuCl（C
• 一种化合物的纯化方法
  申请人：浙江华贝药业有限责任公司

  公开号：CN111410599A

  公开（公告）日：2020-07-14

  本发明公开了一种化合物的纯化方法，即(R,R)‑2,5‑二(4‑氟苯基)‑1,7,7‑三甲基双环[2,2,1]‑2,5‑庚二烯的纯化方法：以2‑甲基四氢呋喃和水为反应溶剂，反应结束后，静置分层，有机相减压浓缩至干得到粗品，粗品用醇和水精制，静置分层，有机相浓缩至干成品。由于2‑甲基四氢呋喃具有一定的疏水性，反应结束后可直接静置分层，有机相减压浓缩得到粗品，无需向反应液另加有机溶剂萃取产物，简化了工艺操作，减少了溶剂使用。粗品采用醇水精制，相比于原工艺的粗品采用过柱纯化的方法，可顺利进行放大生产。该纯化工艺制造成本低，操作简便，生产效率高，三废排放少，环境友好，适合工业化大生产。