1α-methyl-androst-4-ene-3,17-dione | 4136-62-3

• 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-methyl-androst-4-ene-3,17-dione
• 英文别名: 1α-methylandrost-4-ene-3,17-dione；1α-methyl-4-androstene-3,17-dione；1α-Methyl-androsten-(4)-dion-(3,17)；4-Androstene-3,17-dione, 1alpha-methyl-；(1S,8R,9S,10R,13S,14S)-1,10,13-trimethyl-2,6,7,8,9,11,12,14,15,16-decahydro-1H-cyclopenta[a]phenanthrene-3,17-dione
• CAS: 4136-62-3
• 化学式: C₂₀H₂₈O₂
• 分子量: 300.441
• InChiKey: OYGFFDKBBBWEGR-WAYFEFRKSA-N

物化性质

• LogP：
  2.65 at 25℃

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1α-methyl-androst-4-ene-3,17-dione 生成 1α-Methyl-5β-androstandion-(3,17)
  参考文献：
  名称：

  Pelc,B.; Hodkova,J., Collection of Czechoslovak Chemical Communications, 1965, vol. 30, p. 3575 - 3578

  摘要：

  DOI：
• 作为产物：
  描述：

  甲氢睾酮 在 chromium(VI) oxide 、 溶剂黄146 作用下， 生成 1α-methyl-androst-4-ene-3,17-dione
  参考文献：
  名称：

  Pelc,B.; Hodkova,J., Collection of Czechoslovak Chemical Communications, 1965, vol. 30, p. 3575 - 3578

  摘要：

  DOI：

文献信息

• 2-iodo-3-keto-.DELTA..sup.4 steroids, process for their production, as
  申请人：Schering Aktiengesellschaft

  公开号：US05391778A1

  公开（公告）日：1995-02-21

  The new intermediate products of general formula I ##STR1## in which R.sup.1 stands for a hydrogen atom or a straight-chain or branched alkyl group with 1 to 4 carbon atoms, R.sup.2 stands for a hydrogen atom or a methyl group, R.sup.3 stands for a hydrogen atom, R.sup.4 stands for an acyloxy group with 1 to 4 carbon atoms in the acyl radical or R.sup.3 and R.sup.4 together stand for a keto-oxygen atom, are suitable in an excellent way for introducing a .DELTA..sup.1 double bond in the steroid skelton with the simultaneous presence of a .DELTA..sup.4 double bond, as well as a saturated carbonyl group, by clevage of hydrogen iodide with a base in an amidic solvent at elevated temperature. If R.sup.2 stands for a hydrogen atom, the A-ring is aromatized after the hydrogen iodide cleavage. For the production of a new intermediate products, special iodization processes, which partially also allow a stereoselective control of the iodization, are used.

  通用公式I的新中间产物为##STR1##其中R.sup.1代表氢原子或具有1至4个碳原子的直链或支链烷基基团，R.sup.2代表氢原子或甲基基团，R.sup.3代表氢原子，R.sup.4代表酰氧基团，该基团中的酰基基团具有1至4个碳原子，或者R.sup.3和R.sup.4一起代表酮氧原子，以极好的方式适用于在类固醇骨架中引入.DELTA..sup.1双键，同时存在.DELTA..sup.4双键以及饱和羰基基团，通过在含有碱的酰胺溶剂中在升高温度下裂解碘化氢。如果R.sup.2代表氢原子，则氢碘酸裂解后A环会芳香化。为了生产新的中间产物，使用特殊的碘化过程，这些过程部分地也允许碘化的立体选择性控制。
• Control of Regioselectivity in the Transition‐Metal‐Catalysed Conjugate Additions of Alkylaluminium Compounds and Methyltitanium Ate Complexes to Androsta‐1,4‐diene‐3,17‐dione
  作者：Jürgen Westermann、Harribert Neh、Klaus Nickisch

  DOI：10.1002/cber.19961290814

  日期：1996.8

  at the sterically hindered C-5. With Me3Al or Me4AlLi in the presence of catalytic amounts of Cu1 salts, a high regioselectivity (up to 97:3) in favour of position 1 is achieved. Application of ate complexes of aluminium and titanium in the presence of Ni(acac)2 as catalyst, however, leads to a reversal of the regioselectivity in favour of position 5 (up to 11:89). Aluminium and titanium ate complexes

  通过改变试剂系统的性质，在交叉偶联的甾族二烯酮1上选择性地在C-1处或在空间受阻的C-5处进行缀合。在催化量的Cu 1盐存在下使用Me 3 Al或Me 4 AlLi，可获得对位置1有利的高区域选择性（高达97：3）。然而，在Ni（acac）2作为催化剂的情况下应用铝和钛的盐配合物会导致区域选择性的逆转，有利于位置5（最高为11:89）。铝和钛酸盐配合物是在Ni（acac）2催化的位阻烯酮加成反应中的有效试剂。
• Methylation or ethylation agent and process for 1,4-addition of a methyl
  申请人：Schering Aktiengesellschaft

  公开号：US05908944A1

  公开（公告）日：1999-06-01

  This invention describes a new methylation or ethylation agent containing trimethyl aluminum or dimethyl zinc or triethyl aluminum as methyl or ethyl source, which additionally contains catalytic amounts of one or more copper(I) and/or copper(II) compounds as well as a process for the 1,4-addition of a methyl or ethyl group to an .alpha.,.beta.-unsaturated or an .alpha.,.beta.-double unsaturated ketone or an .alpha.,.beta.-unsaturated aldehyde using the agent according to the invention. By using only catalytic amounts of copper and a CKW (chlorinatedhydrocarbon)-free reaction medium, the new methylation/ethylation agent/process is distinguished by its environmental compatibility and it is, for example, suitable for the production of initial products for the synthesis of biologically effective compounds.

  这项发明描述了一种新的甲基化或乙基化剂，其中含有三甲基铝或二甲基锌或三乙基铝作为甲基或乙基来源，此外还含有一种或多种铜(I)和/或铜(II)化合物的催化量，以及一种用于将甲基或乙基基团加成到α，β-不饱和或α，β-双不饱和酮或α，β-不饱和醛的过程，使用根据本发明的剂。通过仅使用铜的催化量和无氯化烃的反应介质，这种新的甲基化/乙基化剂/过程以其环境兼容性而著称，例如，适用于生产用于合成生物有效化合物的初级产品。
• Alkylating agent and 1,4-addition process of an alkyl group onto an
  申请人：Schering Aktiengesellschaft

  公开号：US05908945A1

  公开（公告）日：1999-06-01

  Disclosed is an alkylating agent that contains an aluminum reagent Alk.sub.3-m AlL.sub.m, in which Alk means a methyl, ethyl, n- or i-propyl, n-, i- or tert-butyl, pentyl, hexyl, heptyl or octyl group, which all can also be branched, L means an ethoxy group, a chlorine or bromine atom, and m is equal to 1 or 2, as an alkyl source or else zinc dimethyl as a methyl source, which contains in addition catalytic amounts of one or more copper(I) and/or copper(II) compounds and one (or more) silyl reagent(s) of general formula III R.sup.1 R.sup.2 R.sup.3 SiZ (III), in which R.sup.1, R.sup.2 and R.sup.3 are as defined herein, as well as a process for 1,4-addition of an alkyl group to an .alpha.,.beta.-unsaturated ketone or an .alpha.,.beta.-double unsaturated ketone or to an .alpha.,.beta.-unsaturated aldehyde with use of the agent according to the invention. The alkylating agent yields biologically active compounds in excellent yields and the new alkylating agent/process is distinguished by its environmental compatibility based on a CKW (chlorinated hydrocarbon)-free reaction medium.

  本发明揭示了一种烷基化剂，包含铝试剂Alk.sub.3-m AlL.sub.m，其中Alk表示甲基、乙基、正或异丙基、正、异或叔丁基、戊基、己基、庚基或辛基，均可分支，L表示乙氧基、氯或溴原子，m等于1或2，作为烷基来源，或者是锌二甲基作为甲基来源，此外还含有一定催化量的一个或多个铜(I)和/或铜(II)化合物和一个(或多个)通式III R.sup.1 R.sup.2 R.sup.3 SiZ (III)的硅醚试剂，其中R.sup.1，R.sup.2和R.sup.3如本文所定义，以及一种使用本发明所述的试剂进行1,4-加成反应的α，β-不饱和酮或α，β-双不饱和酮或α，β-不饱和醛的过程。该烷基化剂以优异的产率产生生物活性化合物，且新的烷基化剂/过程以其基于无氯烃的反应介质的环境兼容性而著称。
• Synthesis of 6-methylene derivatives of androsta-1,4-diene-3,17-dione
  申请人：Farmitalia Carlo Erba S.r.l.

  公开号：US04970327A1

  公开（公告）日：1990-11-13

  The invention relates to a new process for the preparation of know aromatase inhibitors of the following formula (I) ##STR1## wherein each of R.sub.1 R.sub.3, independently, is hydrogen or C.sub.1 -C.sub.6 alkyl; R.sub.2 is hydrogen, halogen or C.sub.1 -C.sub.6 alkyl; and R.sub.4 is hydrogen or fluorine; the process comprising submitting to Mannich reaction a compound of formula (II) ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are defined above and R is a lower alkyl group, and then dehydrogenating the respective 6-methylene-3-oxo-.DELTA..sup.4 -steroid derivative thus obtained, by methods known per se.

  本发明涉及一种制备以下式(I)的新型芳香化酶抑制剂的方法：##STR1## 其中，R.sub.1 R.sub.3各自独立地为氢或C.sub.1-C.sub.6烷基；R.sub.2为氢、卤素或C.sub.1-C.sub.6烷基；R.sub.4为氢或氟；该方法包括将式(II)的化合物进行Mannich反应：##STR2## 其中，R.sub.1、R.sub.2、R.sub.3和R.sub.4如上定义，R为较低的烷基基团，然后通过已知的方法脱氢得到相应的6-亚甲基-3-酮-.DELTA..sup.4-类固醇衍生物。