1α,2α-epoxy-22-tetrahydropyranyloxy-23,24-dinorchola-4,6-dien-3-one | 66875-16-9

• 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
• 英文名称: 1α,2α-epoxy-22-tetrahydropyranyloxy-23,24-dinorchola-4,6-dien-3-one
• 英文别名: 1α,2α-epoxy-24-tetrahydropyranyloxy-22,23-dinorchola-4,6-dien-3-one；(20S)-1α,2α-Epoxy-20-methyl-21-(tetrahydro-2H-pyran-2-yl)oxy-4,6-pregnadien-3-on；(20S)-1α,2α-epoxy-20-methyl-21-tetrahydropyranyloxypregna-4,6-dien-3-one；(20S)-1alpha,2alpha-epoxy-20-methyl-21-tetrahydropyranyloxy-pregna-4,6-dien-3-one；(1S,2R,3R,5R,11S,12S,15R,16S)-2,16-dimethyl-15-[(2S)-1-(oxan-2-yloxy)propan-2-yl]-4-oxapentacyclo[9.7.0.02,8.03,5.012,16]octadeca-7,9-dien-6-one
• CAS: 66875-16-9
• 化学式: C₂₇H₃₈O₄
• 分子量: 426.596
• InChiKey: YWNZVURZZOMEDS-PCGWCGNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  48.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1α,2α-epoxy-22-tetrahydropyranyloxy-23,24-dinorchola-4,6-dien-3-one 在 lithium 、 氯化铵 作用下， 生成 (20S)-20-Methyl-21-(tetrahydro-2H-pyran-2-yl)oxy-5-pregnen-1α,3β-diol
  参考文献：
  名称：

  EINE ergiebige Herstellung冯1α，3β二羟基Δ 5 -steroiden第三人以Reduktion冯1α，2α环氧-4,6-二烯-3- onen MIT锂在Ammoniak †

  摘要：

  用于制备1α，3β二羟基Δ的有效程序5个由1α还原，-steroids2α环氧-4,6-二烯-3-酮与锂在氨

  DOI：

  10.1002/hlca.19810640621
• 作为产物：
  描述：

  (20S)-(20-Methyl-5-pregnen-3β,21-diol)-21-acetat 在 甲醇 、 sodium hydroxide 、 双氧水 、 对甲苯磺酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醇 、 苯 为溶剂， 反应 27.0h， 生成 1α,2α-epoxy-22-tetrahydropyranyloxy-23,24-dinorchola-4,6-dien-3-one
  参考文献：
  名称：

  EINE ergiebige Herstellung冯1α，3β二羟基Δ 5 -steroiden第三人以Reduktion冯1α，2α环氧-4,6-二烯-3- onen MIT锂在Ammoniak †

  摘要：

  用于制备1α，3β二羟基Δ的有效程序5个由1α还原，-steroids2α环氧-4,6-二烯-3-酮与锂在氨

  DOI：

  10.1002/hlca.19810640621

文献信息

• Pregnane derivatives
  申请人：Hoffmann-La Roche Inc.

  公开号：US04193921A1

  公开（公告）日：1980-03-18

  The present invention relates to pregnane derivatives of the formula ##STR1## wherein R.sup.1 and R.sup.3 are hydroxyl groups or readily cleavable etherified or esterified hydroxyl groups and R.sup.20 is hydroxymethyl or readily cleavable etherified or esterified hydroxy methyl, formyl, carboxyl or carbalkoxy useful as intermediates for the preparation of 1.alpha.-hydroxycholecalciferols. The present invention also relates to processes for the preparation of the pregnane derivatives and the intermediates thereof.

  本发明涉及公式为##STR1##的孕烷衍生物，其中R.sup.1和R.sup.3是羟基或易于水解的醚化或酯化羟基，R.sup.20是羟甲基或易于水解的醚化或酯化羟甲基，甲酰基，羧基或羧酸酯，用作1α-羟基胆钙化醇的中间体。本发明还涉及制备孕烷衍生物及其中间体的方法。
• Process for 1.alpha.,3.beta.-dihydroxy-.DELTA..sup.5 -steroids
  申请人：Hoffmann-La Roche Inc.

  公开号：US04305881A1

  公开（公告）日：1981-12-15

  A process for the synthesis of 1.alpha.,3.beta.-dihydroxy-.DELTA..sup.5 -steroids from steroids such as 1.alpha.,2.alpha.-epoxy-cholesta-4,6-dien-3-one, which is reacted with lithium in liquid ammonia in the absence of a proton donator and subsequently reduced by repeated alternative additions of a proton donator, said additions being followed in each case by an equivalent amount of lithium. The final product, a 1.alpha.,3.beta.-dihydorxy-.DELTA..sup.5 -steroid, is useful in the synthesis of derivatives of cholecalciferol.

  一种从类固醇合成1α,3β-二羟基-Δ^5-类固醇的方法，其中类固醇如1α,2α-环氧胆甾-4,6-二烯-3-酮与液氨中的锂在无质子给体的情况下反应，并通过重复交替添加质子给体的方式进行还原，每次添加后紧接着相等量的锂。最终产物为1α,3β-二羟基-Δ^5-类固醇，可用于合成胆钙醇衍生物。
• Synthesis and biological activity of (22E,24R)- and (22E,24S)-1.ALPHA.,24-dihydroxy-22-dehydrovitamin D3.
  作者：HIROSHI SAI、SUGURU TAKATSUTO、NOBUO IKEKAWA、YOKO TANAKA、CONNIE SMITH、HECTOR F. DELUCA

  DOI：10.1248/cpb.32.3866

  日期：——

  Chemical synthesis of (22E, 24R)- and (22E, 24S)-1, 24-dihydroxy-Δ22-vitamin D3 has been achieved starting with the commercially available dinorcholenic acid acetate. Synthesis involved introduction of the 1-hydroxy group by a reduction of the 1, 2-epoxide generated by epoxidation of the 1, 4, 6-trien-3-one. The side chain on the steroid was then constructed by means of a Wittig reaction followed by introduction of the Δ7 bond by standard methods and its protection with 1-phenyl-1, 2, 4-triazoline-3, 5-dione. Subsequent reduction of the hydroxy groups in the steroid side chain followed by reduction of the Diels-Alder addition products yielded the both 24-isomers. The 5, 7-dienes were irradiated and the corresponding vitamin D compounds isolated. Nuclear magnetic resonance was used to identify individual isomers. The (22E, 24S)-1, 24-hydroxyvitamin D3 compound bound equally well to the chick intestinal cytosol receptor as 1, 25-dihydroxyvitamin D3, while the 24R-isomer was approximately ten times less active. In vivo, both isomers were less active than 1, 25-dihydroxyvitamin D3 ; however, the 24S-isomer was considerably more active than the 24R-isomer approaching the activity of 1, 25-dihydroxyvitamin D3.

  (22E, 24R)- 和 (22E, 24S)-1，24-二羟基-Δ22-维生素 D3 的化学合成是从市售的二去甲胆烯酸乙酸酯开始的。合成过程包括通过还原 1，4，6-三烯-3-酮环氧化反应生成的 1，2-环氧化物来引入 1-羟基。然后通过维蒂希反应构建类固醇的侧链，再通过标准方法引入 Δ7 键，并用 1-苯基-1，2，4-三唑啉-3，5-二酮对其进行保护。随后还原类固醇侧链中的羟基，再还原 Diels-Alder 加成产物，就得到了 24-异构体。对 5，7-二烯进行辐照，分离出相应的维生素 D 化合物。核磁共振被用来鉴定单个异构体。(22E, 24S)-1，24-羟基维生素 D3 复合物与 1，25-二羟基维生素 D3 一样能很好地与小鸡肠道细胞质受体结合，而 24R 异构体的活性大约低十倍。在体内，两种异构体的活性都低于 1, 25-二羟基维生素 D3；但是，24S-异构体的活性大大高于 24R-异构体，接近 1, 25-二羟基维生素 D3 的活性。
• Synthesis of 1.ALPHA.,25-dihydroxy-26,27-dimethylvitamin D3, a highly active analogue of 1.ALPHA.,25-dihydroxyvitamin D3.
  作者：Hiroshi Sai、Suguru Takatsuto、Noriyuki Hara、Nobuo Ikekawa

  DOI：10.1248/cpb.33.878

  日期：——

  1α, 25-Dihydroxy-26, 27-dimethylvitamin D3 (5) was synthesized from 1α, 2α-epoxy-24-tetrahydropyranyloxy-22, 23-dinorchola-4, 6-dien-3-one (7) and was found to be more active than 1α, 25-dihydroxyvitamin D3 (1).

  1α, 25-二羟基-26, 27-二甲基维生素D3 (5) 由1α, 2α-环氧-24-四氢吡喃氧基-22, 23-二去甲胆甾-4, 6-二烯-3-酮 (7) 合成，活性高于1α, 25-二羟基维生素D3 (1)。
• DELUCA, HECTOR F.;IKEKAWA, NOBUO;TANAKA, YOKO
  作者：DELUCA, HECTOR F.、IKEKAWA, NOBUO、TANAKA, YOKO

  DOI：——

  日期：——