3Β,6Z-9,10-断胆甾基-5(10),6,8-三烯甘油酯-3 | 1173-13-3

• 物质功能分类: 分析化学 - 标准品 - 药典标准品和杂质标准品
• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 中文名称: 3Β,6Z-9,10-断胆甾基-5(10),6,8-三烯甘油酯-3
• 中文别名: 前钙化醇；3Β,6Z-9,1-断胆甾基-5(1),6,8-三烯甘油酯-3
• 英文名称: previtamin D3
• 英文别名: previtamin D；Praevitamin D₃；(1S)-3-[(Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(2R)-6-methylheptan-2-yl]-1,2,3,3a,6,7-hexahydroinden-4-yl]ethenyl]-4-methylcyclohex-3-en-1-ol
• CAS: 1173-13-3
• 化学式: C₂₇H₄₄O
• 分子量: 384.646
• InChiKey: YUGCAAVRZWBXEQ-WHTXLNIXSA-N

物化性质

• 沸点：
  496.0±24.0 °C(Predicted)
• 密度：
  1.017±0.06 g/cm3(Predicted)
• 溶解度：
  二甲基亚砜：10mM

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

安全信息

• 海关编码：
  29362900

制备方法与用途

生物活性方面， previtamin D3 是合成胆骨化醇（维生素D3）的中间体。

反应信息

• 作为反应物：
  描述：

  3Β,6Z-9,10-断胆甾基-5(10),6,8-三烯甘油酯-3 在 咪唑 、 aluminium hydride 、 氢氧化钾 、 四丁基氟化铵 、 CrO₃-3.5-dimethylpyrazole 、 丁酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 51.03h， 生成 阿法骨化醇
  参考文献：
  名称：

  A stereocontrolled partial synthesis of 1α-hydroxy vitamin D3

  摘要：

  DOI：

  10.1016/s0040-4039(00)87003-3
• 作为产物：
  描述：

  4-[[(1,1-二甲基乙基)二苯基甲硅烷基]氧基]-环己酮 在 Lindlar's catalyst 、 bispalladium(II) acetate 喹啉 、 copper(l) iodide 、 正丁基锂 、 四丁基氟化铵 、 氢气 、 sodium hydride 、 magnesium sulfate 、 对甲苯磺酸 、 二乙胺 、 三苯基膦 、 mercury dichloride 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 乙腈 、 paraffin 、 苯 为溶剂， 反应 18.92h， 生成 3Β,6Z-9,10-断胆甾基-5(10),6,8-三烯甘油酯-3
  参考文献：
  名称：

  Studies of vitamin D (calciferol) and its analogs. 44. Thermal [1,7]-sigmatropic shift of previtamin D3 to vitamin D3: synthesis and study of pentadeuterio derivatives

  摘要：

  Specifically pentadeuteriated previtamin D3 11 has been synthesized to impart thermal stability to the otherwise labile material. A 12-step synthesis of the trideuteriated A-ring 14b from p-methoxyphenol was developed and employed the addition of (methyl-d3)magnesium iodide to either the keto thiomethylene intermediate 23 or the keto dioxane 27. The enantiomerically pure trideuterio A-ring (-)-14b was then coupled with the deuteriated CD fragment 13b followed by hydrogenation to afford pentadeuteriated previtamin D3 11. A primary deuterium kinetic isotope effect (KIE) study of the [1,7]-sigmatropic hydrogen migration in the conversion of previtamin D3 to vitamin D3 indicated a more ''normal'' primary deuterium isotope effect (as compared to a previously reported literature value of approximately 45). At 80-degrees-C, a k(H)/k(D) for the previtamin D3 to vitamin D3 isomerization was determined to be approximately 6.2. At 25-degrees-C, this [1,7]-sigmatropic hydrogen migration proceeds with a k(H)/k(D) Of approximately 11.4. The reversible, first-order [1,7]-sigmatropic hydrogen shift of previtamin D3 to D3, determined over the temperature range 60.1-85.5-degrees-C is characterized by the following activation parameters: log A(H) = 8.8 and E(a)H = 19.6 kcal/mol. Deuteriated pre-D3, which rearranges over this temperature range, is characterized by the activation parameters log A(D) = 9.5 and E(a)D = 21.9 kcal/mol.

  DOI：

  10.1021/jo00055a011
• 作为试剂：
  描述：

  (22E)-5,7,22-ergostatriene-1α,3β,25-triol 、 potassium nitrate 在 汞 、 水 、 氮气 、 3Β,6Z-9,10-断胆甾基-5(10),6,8-三烯甘油酯-3 、 乙醇 作用下， 以 乙醚 、 四氢呋喃 为溶剂， 反应 1.05h， 以to give 22 mg of the title compound (IIa) which的产率得到25-二羟基维生素D2
  参考文献：
  名称：

  Process for the preparation of 1.alpha.,25-dihydroxyvitamin D.sub.2 and

  摘要：

  (22E)-5,7,22-Ergostatriene-1.alpha.,3.beta.,25-triol及其24-表异构体是合成1.alpha.，25-二羟基维生素D.sub.2及其24-表异构体的新中间体。还描述了一种制备1.alpha.，25-二羟基维生素D.sub.2及其24-表异构体的新工艺，该工艺包括对(22E)-5,7,22-ergostatriene-1.alpha.，3.beta.，25-triol或其24-表异构体进行辐照，然后进行异构化。

  公开号：

  US05087709A1

文献信息

• Ultraviolet irradiation apparatus for photochemical reaction and preparation process of vitamin D derivative making use of the same
  申请人：CHUGAI SEIYAKU KABUSHIKI KAISHA

  公开号：US20040108198A1

  公开（公告）日：2004-06-10

  Disclosed herein are an ultraviolet irradiation apparatus for photochemical reactions which can irradiate the photo-reactive solution with ultraviolet rays having a specific wavelength suitable for the intended photochemical reaction at a high efficiency, and a process by which a provitamin D derivative can be converted into a provitamin D derivative at a high efficiency by means of a photochemical reaction by one-step process of light irradiation, thereby preparing a vitamin D derivative at a high efficiency. The ultraviolet irradiation apparatus irradiates the photo-reactive solution with the ultraviolet rays having the specific wavelength through a quartz rod. Specifically, the apparatus is constructed by an electric discharge lamp, a condensing and reflecting mirror and a plane mirror both having wavelength selective property, an optical filter which transmits the ultraviolet rays having the specific wavelength, and a quartz rod on which the ultraviolet rays having the specific wavelength are struck. The photo-reactive solution is irradiated with the ultraviolet rays from the quartz rod. The quartz rod is immersed in the photo-reactive solution, or a reaction vessel is irradiated with the ultraviolet rays from the quartz rod. In the preparation process of the vitamin D derivative, an ultraviolet irradiation apparatus for photochemical reactions having an ultraviolet radiation-emitting lamp, an optical system having wavelength selective property and a quartz rod on which the ultraviolet rays having the specific wavelength from the optical system are struck is used, and a solution of a provitamin D derivative is irradiated with the ultraviolet rays having the specific wavelength emitted from the quartz rod to cause a photochemical reaction of the provitamin D derivative solution, thereby forming a previtamin D derivative. The previtamin D derivative is further subjected to a thermal isomerization reaction to prepare the vitamin D derivative.

  本文披露了一种用于光化学反应的紫外辐射装置，该装置可以以高效率照射具有特定波长的紫外线的光敏反应溶液，适用于预期的光化学反应，并通过光照的一步法将一种类维生素D衍生物转化为高效率的类维生素D衍生物的过程，从而高效率地制备维生素D衍生物。紫外辐射装置通过石英棒以特定波长的紫外线照射光敏反应溶液。具体而言，该装置由电放电灯、具有波长选择性的聚焦和反射镜和平面镜、透射具有特定波长的紫外线的光学滤波器以及被特定波长的紫外线击中的石英棒构成。光敏反应溶液从石英棒处照射出紫外线。石英棒浸泡在光敏反应溶液中，或者光敏反应溶液从石英棒处照射到反应容器中。在维生素D衍生物的制备过程中，使用一种用于光化学反应的紫外辐射装置，该装置具有紫外辐射发射灯、具有波长选择性的光学系统和石英棒，光学系统发出具有特定波长的紫外线，用于照射类维生素D衍生物溶液，从而引发类维生素D衍生物溶液的光化学反应，形成前维生素D衍生物。进一步对前维生素D衍生物进行热异构化反应，制备维生素D衍生物。
• lα-hydroxy previtamin D3, and its selective formation from 1-keto previtamin D3
  作者：L.J. Vanmaele、P.J. De Clercq、M. Vandewalle、S.J. Halkes、W.R.M. Overbeek

  DOI：10.1016/s0040-4020(01)99323-8

  日期：1984.1

  An efficient method for the preparation of crystalline α-hydroxy previtamin D3 is described. Also the stereoselective reduction of 1-keto previtamin is discussed; it was observed that with aluminum hydride is the most abundant product. This stands in contrast with previously reported LiAlH4 and NaBH4 mediated reductions.

  描述了制备结晶的α-羟基维生素原D 3的有效方法。还讨论了1-酮前维生素的立体选择性还原。观察到氢化铝是最丰富的产物。这与先前报道的LiAlH 4和NaBH 4介导的还原形成对比。
• Calciferol and its relatives. Part XVI. Total synthesis of precalciferol3 2
  作者：T. M. Dawson、J. Dixon、P. S. Littlewood、B. Lythgoe、A. K. Saksena

  DOI：10.1039/j39710002960

  日期：——

  The total synthesis of precalciferol3 has been effected without the use of photochemical methods. 9α-Chloro-des-AB-cholestan-8-one 5α-chloro-1β-[(1R)-1,5-dimethylhexyl]-7aβ-methyl-trans-perhydroindan-4-one}(1; X =α-Cl) and (1S)-3-ethynyl-4-methylcyclohex-3-en-1-ol (2; R = H) were combined to give the chlorohydrin (3; X =α-Cl), which was transformed, first into the dienyne (4) and then, by semihydrogenation

  钙化固醇3的总合成无需使用光化学方法即可完成。9α-Chloro- des- AB -cholestan-8-one 5α-chloro-1β-[（1 R）-1,5-methyldimethylhexyl]-7aβ-methyl- trans - perhydroindan -4-one}（1; X =将（α-Cl）和（1 S）-3-乙炔基-4-甲基环己-3-烯-1-醇（2; R = H）合并得到氯醇（3; X =α-Cl），首先转化为二烯炔（4），然后通过乙炔键的半氢化反应转化为前钙化甾醇3（5）。描述了与维生素原和相关途径有关的模型实验。
• Effects of wavelength and conformation on the photochemistry of vitamin D and related conjugated trienes
  作者：H.J.C. Jacobs、J.W.J. Gielen、E. Havinga

  DOI：10.1016/s0040-4039(01)82052-9

  日期：1981.1

  Irradiation experiments under various conditions establish that the photoreactions of conjugated trienes are governed by the ground state conformational equilibrium and the NEER principle, as well as by the wavelength dependent relaxation behaviour of the excited species.

  在各种条件下的辐照实验确定，共轭三烯的光反应受基态构象平衡和NEER原理以及受激发物质的波长依赖性弛豫行为的控制。
• Mechanism of error caused by isotope-labeled internal standard: accurate method for simultaneous measurement of vitamin D and pre-vitamin D by liquid chromatography/tandem mass spectrometry
  作者：Min Huang、Amy B. Cadwallader、Rebecca Heltsley

  DOI：10.1002/rcm.6987

  日期：2014.10.15

  to 25% has been observed for vitamin D3 and D2 samples exposed to heating during sample preparation, even when isotope‐labeled internal standards are used. The goals of this study were to identify the mechanism of the positive bias observed in measuring vitamin D3 and D2 by liquid chromatography/tandem mass spectrometry (LC/MS/MS) and determine a way to eliminate the error source.

  即使在使用同位素标记的内标的情况下，在样品制备过程中暴露于加热的维生素D 3和D 2样品也观察到高达25％的偏差。这项研究的目的是确定通过液相色谱/串联质谱法（LC / MS / MS）测定维生素D 3和D 2时观察到的正偏差的机理，并确定消除误差源的方法。