(2R,4aS,4bS,6aS,7S,8R,10aS,10bR,12aR)-7-氯-4a,6a,8-三甲基-1,2,3,4,4b,5,6,7,8,9,10,10a,10b,11,12,12a-十六氢屈-2-醇 | 76571-91-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (2R,4aS,4bS,6aS,7S,8R,10aS,10bR,12aR)-7-氯-4a,6a,8-三甲基-1,2,3,4,4b,5,6,7,8,9,10,10a,10b,11,12,12a-十六氢屈-2-醇
• 英文名称: 17α-methyl-17aβ-chloro-D-homo-5β-androstane-3α-ol
• 英文别名: 17α-methyl-17aβ-chloro-D-homo-5β-androstan-3α-ol；17-Mchao；(2R,4aS,4bS,6aS,7S,8R,10aS,10bR,12aR)-7-chloro-4a,6a,8-trimethyl-1,2,3,4,4b,5,6,7,8,9,10,10a,10b,11,12,12a-hexadecahydrochrysen-2-ol
• CAS: 76571-91-0
• 化学式: C₂₁H₃₅ClO
• 分子量: 338.961
• InChiKey: UMWMKSFDTADRMB-YAWPOEEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  4.0
• 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

反应信息

• 作为产物：
  描述：

  孕甾二醇 在 盐酸 、 氢氧化钾 、 三氧化硫吡啶 作用下， 反应 0.5h， 生成 (2R,4aS,4bS,6aS,7S,8R,10aS,10bR,12aR)-7-氯-4a,6a,8-三甲基-1,2,3,4,4b,5,6,7,8,9,10,10a,10b,11,12,12a-十六氢屈-2-醇
  参考文献：
  名称：

  类固醇的临床分析。十二。5β-孕烷3α，20α-二醇二硫酸盐热酸水解过程中发生D-均醛化。

  摘要：

  当将其在3N盐酸中回流时，从5个β-孕烷-3α和20个α-二醇二硫酸盐（II）的水解产物中分离出两种D-类固醇。这些类固醇的结构已阐明为17α-甲基-D-homo-5β-雄烷3α，17aβ-二醇（VI）和17α-甲基-17aβ-氯-D-homo-5β -androstan-3α-ol（VIII）通过仪器分析。前者与通过尿烷二醇重排衍生自5β-孕烯-3α，20β-二醇二硫酸盐（IV）的合成标本相同。获得的主要水解产物是17α-乙基17β-甲基-18-nor-5β-雄甾13-en-3α-醇（V）和5β-孕烷3α，20α-二醇（III ）。

  DOI：

  10.1016/0039-128x(80)90071-9

文献信息

• Isolation and structural elucidation of the degradation products of pregnanediol disulfate obtained by hot acid hydrolysis (Clinical analysis on steroids. XXI).
  作者：ITSUO YOSHIZAWA、RYOKO OHUCHI、KYOKO NAGATA、SHINJI ITOH、NORIO KAWAHARA

  DOI：10.1248/cpb.30.2474

  日期：——

  Besides the main products, 17α-ethyl-17β-methyl-18-nor-5β-androst-13-en-3α-ol (7a), 17α-methyl-D-homo-5β-androstane-3α, 17aβ-diol (8), and 17α-methyl-17aβ-chloro-D-homo-5β-androstan-3α-ol (9), other minor degradation products of pregnanediol 3, 20-disulfate (2) were obtained under reflux in 3 N hydrochloric acid, and were structurally identified by comparison with synthetic specimens. The steroidal mono olefins isolated were 5β-pregn-3-en-20α-ol (10a), 5β-pregn-2-en-20α-ol (11a), 5β-pregn-20-en-3α-ol (12a), and 5β-pregn-17 (20)-en-3α-ol (13a). The Z-isomer of 13a, 5β-pregn-17 (20)-en-3α-ol (14a), was detected by gas chromatography and identified by gas chromatography-mass spectrometric comparison with synthetic compound. Steroidal dienes were obtained as a mixture of Δ2-and Δ3-compounds having partial D-ring structures corresponding to 7a, 12a, and 13a. Although it was a minor product, 5β-pregnane-3α, 20β-diol (16) was also obtained, and its isolation suggests the formation of a C20-carbonium ion in the course of the hydrolysis. The yield of intact steroid, pregnanediol (1), was only 18.4% of the total products obtained.

  除了主要产品17α-乙基-17β-甲基-18-去氢-5β-雄甾-13-烯-3α-醇（7a）、17α-甲基-D-同雄甾-5β-醇（8）和17α-甲基-17β-氯-D-同雄甾-5β-醇（9），在3 N盐酸回流条件下还获得了孕醇-3,20-二硫酸酯（2）的其他少量降解产物，并通过与合成样品的比较对其结构进行了鉴定。分离得到的类固醇单烯包括5β-孕-3-烯-20α-醇（10a）、5β-孕-2-烯-20α-醇（11a）、5β-孕-20-烯-3α-醇（12a）和5β-孕-17（20）-烯-3α-醇（13a）。以气相色谱法检测到的13a的Z异构体为5β-孕-17（20）-烯-3α-醇（14a），并通过与合成化合物的气相色谱-质谱比较进行了鉴定。分离的类固醇二烯作为混合物包括具有部分D环结构的Δ2和Δ3化合物，对应于7a、12a和13a。虽然它是一个少量产物，5β-孕烷-3α、20β-二醇（16）也被获得，其分离表明在水解过程中形成了C20碳正离子。完整类固醇孕醇（1）的产率仅为获得的总产品的18.4%。
• Confirmation of the involvement of C20-carbonium cation during the hot acid hydrolysis of pregnanediol disulfate (Clinical analysis on steroids. XXIII).
  作者：ITSUO YOSHIZAWA、KYOKO NAGATA、SHINJI ITOH

  DOI：10.1248/cpb.30.4325

  日期：——

  The formation of a C20-carbonium cation during the hot acid hydrolysis of pregnanediol disulfate (1b) and the role of this cation in the rearrangement reactions were examined. Hydrolysis of 1b in boiling 3N hydrochloric acid in oxygen-18 water gave 17α-ethyl-17β-methyl-18-nor-5β-androst-13-en-3α-ol (2) as the main product, together with pregnanediol (1a), 17α-methyl-D-homo-5β-androstane-3α, 17aβ-diol (3), 17α-methyl-17aβ-chloro-D-homo-5β-androstan-3α-ol (4), 5β-pregn-20-en-3α-ol (5a), 5β-pregnane-3α, 20β-diol (10), and other minor degradation products. The isotope content of these products was determined by gas chromatography-mass spectrometry. Among then, 3 and 10 were quantitatively labeled with 18O at 17aβ- and 20β-ol, respectively, and 1a was 74% labeled at 20α-ol. No uptake of 18O into 3α-ol of the products was observed. These results confirm the formation of the C20-carbonium cation from 1b. Hydrolysis of 5β-pregn-20-en-3α-ol sulfate (5b), which is considered to be the conjugated base of the C20-cation, gave 2 as the main product accompanied with 1a, 3, 4, 5a, and 10. This result suggests that the C20-carbonium cation plays an important role as an intermediate to D-homosteroids as well as to the Δ15-olefin 2.

  研究了孕二醇二硫酸盐 (1b) 热酸水解过程中 C20-碳鎓阳离子的形成以及该阳离子在重排反应中的作用。 1b 在沸腾的 3N 盐酸中的氧 18 水中水解，得到主要产物 17α-乙基-17β-甲基-18-nor-5β-androst-13-en-3α-ol (2)，以及孕二醇 (1a ), 17α-甲基-D-同-5β-雄甾烷-3α, 17aβ-二醇 (3), 17α-甲基-17aβ-氯-D-同-5β-雄甾烷-3α-醇 (4), 5β-孕- 20-en-3α-ol (5a)、5β-pregnane-3α、20β-二醇 (10) 和其他少量降解产物。这些产物的同位素含量通过气相色谱-质谱法测定。其中，3和10分别在17aβ-和20β-ol处被18O定量标记，1a在20α-ol处被74%标记。没有观察到 18O 被吸收到产物的 3α-ol 中。这些结果证实了 1b 中 C20-碳正离子的形成。 5β-pregn-20-en-3α-ol 硫酸盐 (5b)（被认为是 C20-阳离子的共轭碱）水解，得到主要产物 2 以及 1a、3、4、5a 和 10这一结果表明，C20-碳正离子作为 D-同质类固醇以及 Δ15-烯烃 2 的中间体发挥着重要作用。
• Yoshizawa, Itsuo; Itoh, Shinji; Nagata, Kyoko, Chemical and pharmaceutical bulletin, 1983, vol. 31, # 11, p. 3819 - 3828
  作者：Yoshizawa, Itsuo、Itoh, Shinji、Nagata, Kyoko、Kawahara, Norio

  DOI：——

  日期：——
• Itoh, Shinji; Ichikawa, Harumi; Takagi, Hidetoshi, Chemical and pharmaceutical bulletin, 1988, vol. 36, # 11, p. 4261 - 4268
  作者：Itoh, Shinji、Ichikawa, Harumi、Takagi, Hidetoshi、Yoshizawa, Itsuo

  DOI：——

  日期：——
• ITOH, SHINJI;ICHIKAWA, HARUMI;TAKAGI, HIDETOSHI;YOSHIZAWA, ITSUO, CHEM. AND PHARM. BULL., 36,(1988) N1, C. 4261-4268
  作者：ITOH, SHINJI、ICHIKAWA, HARUMI、TAKAGI, HIDETOSHI、YOSHIZAWA, ITSUO

  DOI：——

  日期：——