1β-benzoyloxy-7aβ-methyl-5,6,7,7a-tetrahydroindan-5-one | 41878-37-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1β-benzoyloxy-7aβ-methyl-5,6,7,7a-tetrahydroindan-5-one
• 英文别名: [(1S,7aS)-7a-methyl-5-oxo-2,3,6,7-tetrahydro-1H-inden-1-yl] benzoate
• CAS: 41878-37-9
• 化学式: C₁₇H₁₈O₃
• 分子量: 270.328
• InChiKey: JYQRKKRFLJUJIV-RDJZCZTQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1β-benzoyloxy-7aβ-methyl-5,6,7,7a-tetrahydroindan-5-one 在 manganese(IV) oxide 、 硼烷四氢呋喃络合物 、 碘 、 双(三甲基硅烷基)氨基钾 、 caesium carbonate 、 pyridinium chlorochromate 、 三氟乙酸 、 锌 作用下， 以 四氢呋喃 、 乙酸乙酯 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 97.33h， 生成 (+)-methyl 17β-benzoyloxy-14β-hydroxy-3β-isopropenyl-1,7-dioxo-5β-androstan-19-oate
  参考文献：
  名称：

  Stereocontrolled synthesis of optically active 14β-hydroxy steroids and other steroid derivatives

  摘要：

  报道了通过碱催化反应合成具有光学活性的14β-羟基类固醇。

  DOI：

  10.1139/v92-243
• 作为产物：
  描述：

  (1S,7aS)-1-hydroxy-7a-methyl-2,3,7,7a-tetrahydro-1H-inden-5(6H)-one 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 26.0h， 生成 1β-benzoyloxy-7aβ-methyl-5,6,7,7a-tetrahydroindan-5-one
  参考文献：
  名称：

  Synthesis and photochemical rearrangement of (1(R),7a(S))-1-(tert-butyldiphenylsiloxy)-7a-methyl-5(7aH)-indanone

  摘要：

  Reaction of (1S,7aS)-1-hydroxy-7a-methyl-7,7a-dihydro-5(6H)-indanone (5a) with benzoic acid under the usual conditions of the Mitsunobu reaction gave a low yield of a 1:1 mixture of the benzoate derivatives 6b and 5b resulting from inversion and retention of configuration, respectively, at C-1. Under conditions in which the benzoic acid concentration was kept low, only the inversion product 6b was obtained but the extent of conversion of the alcohol to the ester was low. The substitution of p-nitrobenzoic acid for benzoic led to a significant improvement in the yield of the inversion product 6c. Several other methods of obtaining alpha-oxy derivatives of the type 6b-e were explored but with little or no success. The reaction of the tosyloxy enone 5d with azide ion and cyanide anion gave enones of the type 12 resulting from retention of configuration at C-1 largely or exclusively. The (p-nitrobenzoyl)oxy derivative 6c was converted into the corresponding cross-conjugated cyclohexadienone, (1R,7aS)-l-(tert-butyldiphenylsiloxy)-7a-methyl-5(7aH)-indanone (4a), which was irradiated in glacial and in aqueous acetic acid. In the former solvent, the dienone system underwent photochemical rearrangement to give the 5/6-fused acetoxyl enone 14 and a 2:1 mixture of the tricyclic cyclopropyl ketone 15 and 16 in 25% and 17% yields, respectively, but in aqueous acetic acid phenolic products 18 and 20, obtained by thermal cleavage of the 1,7a carbon-carbon bond, were obtained almost exclusively. In contrast, under the same photolysis conditions, the dienone 1a, the C-1beta epimer of 4a, gave a mixture of photoproducts composed of the 5/6-fused hydroxy ketone 21, the 5/6-fused acetoxy ketone 2a, and the tricyclic conjugated cyclopropyl ketone 22 in 47%, 5%, and 15% yields, respectively.

  DOI：

  10.1021/jo00050a040

文献信息

• Process for the preparation of bicycloalkane derivatives
  申请人：Schering Aktiengesellschaft

  公开号：US04017545A1

  公开（公告）日：1977-04-12

  Bicycloalkanes useful as intermediates in the total synthesis of steroids of the formula ##STR1## WHEREIN N IS THE INTEGER 1 OR 2; R.sub.1 is lower-alkyl; X is free or ketalized carbonyl or free, esterified or etherified hydroxymethylene; and Y is --SO.sub.2 --R.sub.2 or --C(Z)(R.sub.3)--R.sub.4 wherein R.sub.2 is alkyl, aryl or aralkyl R.sub.3 is H or lower-alkyl, R.sub.4 is alkoxycarbonyl or acyl and Z is lower-alkoxycarbonyl, lower acyl, lower alkylsulfinyl or lower-alkylsulfonyl, are produced by the steps of hydrogenating a compound of the formula ##STR2## AND CONDENSING THE THUS-PRODUCED RING SATURATED COMPOUND WITH A SALT OF THE FORMULA C(Z)(R.sub.3)R.sub.4 .sup.-Me.sup.+ wherein n, X, R.sub.1, R.sub.2, R.sub.3, R.sub.4 and Z have the values given above.

  环脂肪烷可以作为合成类固醇的中间体，在总合成中有用，其化学式为##STR1## 其中N是整数1或2；R.sub.1是较低的烷基；X是自由的或缩醛化的羰基或自由的、酯化的或醚化的羟甲基；Y是--SO.sub.2 --R.sub.2或--C(Z)(R.sub.3)--R.sub.4，其中R.sub.2是烷基、芳基或芳基烷基，R.sub.3是H或较低的烷基，R.sub.4是烷氧羰基或酰基，Z是较低的烷氧羰基、较低的酰基、较低的烷基磺酰基或较低的烷基磺基，通过将化合物氢化为##STR2## 并将因此产生的饱和环化合物与C(Z)(R.sub.3)R.sub.4的盐进行缩聚制备，其中n、X、R.sub.1、R.sub.2、R.sub.3、R.sub.4和Z具有上述给定的值。
• Synthesis of an optically active 13β-methyl 14β-hydroxy steroid via base-catalyzed reactions
  作者：Réjean Ruel、Pierre Deslongchamps

  DOI：10.1016/s0040-4039(00)94472-1

  日期：1990.1
• Synthesis and photochemical rearrangements of bicyclic cross-conjugated cyclohexadienones containing .delta.-oxy substituents
  作者：Drury Caine、Pravin L. Kotian、Melisa D. McGuiness

  DOI：10.1021/jo00022a018

  日期：1991.10

  Several 6/5-fused cross-conjugated cyclohexadienones containing delta-oxy substituents on the B ring including the benzoyl, SEM, and TBDPS hydroxyl-protected systems 12b, 12f, and 12g were prepared from the corresponding enones by the phenylselenenylation-selenoxide elimination procedure. Attempted preparation of dienones 12a, 12c, and 12d containing tert-butyl, methyl, and trimethylsilyl hydroxyl-protecting groups failed. Instead, the phenolic aldehyde 13 was obtained after workup or column chromatography on silica gel. The THP-protected dienone 12e could be purified and characterized, but it gave aldehyde 13 on standing in acetic acid at room temperature. Irradiations of dienones 12b, 12f, and 12g in glacial acetic acid using a high-pressure mercury lamp housed in a Pyrex probe gave mixtures containing several photoproducts. The corresponding 5/6-fused acetoxy ketones 22a, 22c, and 22b were the major products in each case. The 5/6-fused hydroxy ketone 23 was also obtained from dienone 22a. Mixtures of tricyclic ketones of the type 27 and 28 resulting from rare examples of trapping of Zimmerman-Schuster cyclopropyl carbocation intermediates, i.e., 26, by the solvent were also obtained from all three dienones. Dienones 12g and 12f also gave tricyclic acetoxy ketones 31a and 31b, which presumably arose via a 1,4-sigmatropic rearrangement of an excited-state precursor of 26.
• Tietze, Lutz F.; Beifuss, Uwe; Loekoes, Magdolna, Angewandte Chemie, 1990, vol. 102, # 5, p. 545 - 547
  作者：Tietze, Lutz F.、Beifuss, Uwe、Loekoes, Magdolna、Rischer, Matthias、Goehrt, Axel、Sheldrick, George M.

  DOI：——

  日期：——
• TIETZE, LUTZ F.;BEIFUSS. , UWE;LOKOS, MAGDOLNA;RISCHER, MATTHIAS;GOHRT, A+, ANGEW. CHEM., 102,(1990) N, C. 545-547
  作者：TIETZE, LUTZ F.、BEIFUSS. , UWE、LOKOS, MAGDOLNA、RISCHER, MATTHIAS、GOHRT, A+

  DOI：——

  日期：——