3-溴丙酸叔丁酯 | 13258-68-9

• 物质功能分类: 化学试剂 - 有机试剂 - 酯类
• 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: 3-溴丙酸叔丁酯
• 英文名称: ethynylestradiol diacetate
• 英文别名: 3,17β-diacetoxy-17α-ethinyl-estra-1,3,5(10)-trien；3,17β-diacetoxy-17α-ethynyl-1,3,5[10]-estratriene；17α-ethynylestradiol 3,17β-diacetate；ethylnylestradiol acetate；3,17-diacetoxy-19-nor-17βH-pregna-1,3,5(10)-trien-20-yne；3,17-Diacetoxy-19-nor-17βH-pregna-1,3,5(10)-trien-20-in；Ethynyl Estradiol Diacetate；[(8R,9S,13S,14S,17R)-17-acetyloxy-17-ethynyl-13-methyl-7,8,9,11,12,14,15,16-octahydro-6H-cyclopenta[a]phenanthren-3-yl] acetate
• CAS: 13258-68-9
• 化学式: C₂₄H₂₈O₄
• 分子量: 380.484
• InChiKey: UQWZWQYTKPEDAK-DJCPXJLLSA-N

物化性质

• 溶解度：
  可溶于二氯甲烷、乙酸乙酯、甲醇

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-溴丙酸叔丁酯 在 sodium tetrahydroborate 、 ammonium cerium(IV) nitrate 作用下， 生成 11α-hydroxy-17α-ethynylestradiol 3,17-diacetate
  参考文献：
  名称：

  Formates of stereoisomeric 17α-ethynyl-11-hydroxyestradiols

  摘要：

  DOI：

  10.1007/bf00630384
• 作为产物：
  描述：

  炔雌醇 生成 3-溴丙酸叔丁酯
  参考文献：
  名称：

  WEBER, GISELA;SCHAUMANN, J.;CARL, CONSTANZE;SCHWARZ, S.;LEISNER, ROSEMARI+, J. PAAKT. CHEM., 331,(1989) N, C. 223-230

  摘要：

  DOI：

文献信息

• Process for the manufacture of acetylene derivatives of the cyclopentano-polyhydrophenanthrene series
  申请人：CIBA PHARM PROD INC

  公开号：US02267257A1

  公开（公告）日：1941-12-23

  516,444. Acetylene-cyclopentanophenanthrene compounds. SOC. OF CHEMICAL INDUSTRY IN BASLE. June 27, 1938, Nos. 18992, 18993, 18994 and 18995. Convention dates, June 26, 1937, Aug. 7, 1937, Jan. 18, 1938, and May 12, 1938. [Class 2 (iii)] Acetylene derivatives of the cyclopentanopolyhydrophenanthrene series are-prepared by the reaction of a ketohe of this series with a metal salt of an acetylene or a monosubstituted acetylene in a homogenous liquid phase, and the addition product so produced is hydrolysed or treated with an alkylating or an acylating agent. Parent materials are saturated or unsaturated ketones of the above series, and those specified include the androstanolones such as androsterones or dihydro-testosterones, androstenolones such as dehydroandrosterones, androstane-diones, androstene-diones, oestrone hexahydro-oestrone, equiline, pregnanolones, pregnenolones, pregnane-diones, and pregnenediones. Metal salts of acetylenes or substituted acetylenes includes compounds in which the hydrogen atom of a -C#CH group is replaced by an equivalent of a metal such as sodium potassium, lithium; or copper salts. Substituted acetylenes mentioned include phenylacetylene, acetylene carboxylic acids such as acetylene acetic acid, acetylene propionic acid, acetylene butyric acid, acetylene malonic acid and derivatives of these, such as salts, esters or amides. The reaction may be conducted in the presence of liquid ammonia, an amine such as aniline, an alkylated aniline, pyridine, piperidine, or quinoline, or in the presence of a tertiary alcohol such as tertiary butyl or amyl alcohol. An additional solvent such as an ether or an aromatic hydrocarbon may also be present. Previously prepared solutions of the metal acetylide may be used such as are formed by conducting acetylene into a solution of an alkali metal or alkali amide in anhydrous ammonia, or by introducing an alkali metal or an alkali amide into a solution of acetylene in anhydrous ammonia or in a tertiary alcohol. The addition product which possesses the general formula where R is hydrogen or a substituted or non- substituted hydrocarbon or carboxyl group and Me is a metal hydrolysed by water or acid to the corresponding tertiary alcohol or is reacted with an alkylating agent to produce an ether or with an acylating agent to produce an ester. Alkylating agents mentioned include alkyl or alkylene halides such as methyl iodide, propyl iodide, alkyl bromide, benzyl bromide, chloromethyl ether, triarylmethyl chlorides, and the reactive esters of alcohols such as dialkyl sulphates. Acylating agents mentioned include acid halides such as acetyl-, propionyl-., and benzoyl-chloride, toluene sulpho-chloride, chlorocarbonic acid esters and acid anhydrides. In examples (1) potassium is dissolved in liquid ammonia cooled with acetone and carbonic acid snow. Acetylene is led into the blue solution until it is decolourized, and a benzene solution of trans-dehydroandrosterone is added. Ice is added and the unreacted parent ketone is removed and the residue comprising #<;5>;.<;6>;-17- ethinyl-androstene-diol-3:17 is crystallized. On acetylation with acetic anhydride in pyridine at room temperature the corresponding monoacetate is formed. (2) Trans-androsterone is condensed with acetylene as in example (1) to give 17-ethinyl-androstane-diol-3:17. (3) The #<;5À6>;-17 ethinyl-androstene diol-3:17 prepared in example (1) is acetylated with acetic anhydride in pyridine at raised temperature to form the corresponding diacetate. (4) An ether solution of 1-ethinyl-propionic acid ethyl ester is added to a solution of sodium in liquid ammonia cooled as in example (1). An ether-benzene solution of trans-dehydroandrosterone is now added and the product worked up as in example (1) to give a condensation product of the formula The 1-ethinyl-propionic acid ethyl ester may be made by passing acetylene into a solution of sodium in liquid ammonia, adding benzene, evaporating the ammonia, and treating the product with alphabromopropionic acid ethyl ester. (5) A solution of potassium in tertiary butyl alcohol is added to a solution of acetylene in dry ether at -20‹C., and an ether solution of trans-dehydroandrosterone added. The product is then worked up as before to give #<;5.6>;-17-ethinyl-androstene-diol-3:17. (6) Transandrosterone is reacted with acetylene as in example (5) to give 17-ethinyl-androstane-diol- 3:17. (7) Acetylene is passed into a solution of potassium in liquid ammonia and a solution of oestrone in dioxane added. The product is worked up to give 17-ethinyl-oestradiol-3:17. The corresponding diacetate is prepared by heating with pyridine and acetic anhydride. Specification 468,123 is referred to. The Specification as open to inspection under Sect. 91 includes also as parent materials aetio-cholenyl-17-aldehydes, compounds of the suprannal cortical hormone series, cholestanone, and cholestenone. The metal salts which may be used include also rubidium, caesium and silver salts of acetylene or mono-substituted acetylenes. Moreover the use of previously prepared suspensions of the metal acetylide may be used. 'The derivatives of the compounds formed by the process of the present invention includes also glucosides. This subject-matter does not appear in the Specification as accepted.

  516,444. 乙炔-环戊苯并蒽化合物。巴塞尔化学工业协会。1938年6月27日，编号18992、18993、18994和18995。公约日期，1937年6月26日、1937年8月7日、1938年1月18日和1938年5月12日。[2类(iii)] 环戊苯并蒽系列的乙炔衍生物是通过该系列的酮与乙炔或单取代乙炔的金属盐在均相液相中反应制备的，所产生的加成产物经水解或与烷基化或酰化剂处理。母体材料是上述系列的饱和或不饱和酮，具体包括雄甾酮酮类似物，如雄甾酮或二氢睾酮，雄甾酮类似物，如去氢雄甾酮，雄烷二酮，雄烯二酮，雌酮，六氢雌酮，伊奎林，孕酮酮，孕醇酮，孕烷二酮和孕烯二酮。乙炔或取代乙炔的金属盐包括其中-C#CH基团的氢原子被钠、钾、锂等金属的当量所取代的化合物；或铜盐。提到的取代乙炔包括苯乙炔，乙炔羧酸，如乙炔乙酸，乙炔丙酸，乙炔丁酸，乙炔丙二酸和这些的衍生物，如盐、酯或酰胺。反应可以在液氨、苯胺、烷基化苯胺、吡啶、哌啶或喹啉等存在的情况下进行，或者在三级醇，如叔丁基或戊醇存在的情况下进行。也可以存在额外的溶剂，如醚或芳香烃。事先制备的金属乙炔化物的溶液可以使用，例如通过将乙炔导入无水氨溶液中的碱金属或碱金属酰胺中形成的溶液，或者通过将碱金属或碱金属酰胺引入无水氨或三级醇中的乙炔溶液中形成的溶液。具有一般公式的加成产物，其中R是氢或取代或非取代的碳氢化合物或羧基，Me是被水或酸水解为相应的三级醇或与烷基化剂反应生成醚或与酰化剂反应生成酯的金属。提到的烷基化剂包括甲基碘化物、丙基碘化物、烷基溴化物、苄溴化物、氯甲醚、三芳基甲基氯化物和醇的反应酯，如二烷基硫酸酯。提到的酰化剂包括酸卤，如乙酰氯、丙酰氯和苯甲酰氯，甲苯磺酰氯，氯碳酸酯和酸酐。在示例中(1)中，钾在液氨中与丙酮和二氧化碳雪冷却混合。将乙炔导入蓝色溶液中，直到脱色，然后加入反式去氢雄甾酮的苯溶液。加入冰，去除未反应的母酮，残留物包括#<;5>;.<;6>;-17-乙炔基-雄烯二醇-3:17结晶。在室温下在吡啶中用乙酸酐乙酸化后，形成相应的单乙酸酯。(2)反式雄甾酮与乙炔如示例(1)中凝结，得到17-乙炔基-雄烷二醇-3:17。(3)在示例(1)中制备的#<;5À6>;-17乙炔基-雄烯二醇-3:17在吡啶中升温用乙酸酐乙酸化，形成相应的二乙酸酯。(4)1-乙炔基-丙酸乙酯的醚溶液加入到液氨中钠的溶液中，如示例(1)中冷却。现在加入反式去氢雄甾酮的醚-苯溶液，并像示例(1)中那样处理产物，得到公式的缩合产物。1-乙炔基-丙酸乙酯可以通过将乙炔通入液氨中的钠溶液中，加入苯，蒸发氨，并用α-溴丙酸乙酯处理产物制备。(5)在-20°C下，将钾在三丁醇中的溶液加入到干醚中的乙炔溶液中，然后加入反式去氢雄甾酮的醚溶液。然后像以前一样处理产物，得到#<;5.6>;-17-乙炔基-雄烯二醇-3:17。(6)反式雄甾酮与乙炔反应，如示例(5)中，得到17-乙炔基-雄烷二醇-3:17。(7)将乙炔导入液氨中的钾溶液中，然后加入二氧杂环己酮的二氧六环己酮溶液。处理产物，得到17-乙炔基-雌二醇-3:17。通过与吡啶和乙酸酐加热制备相应的二乙酸酯。参考规范468,123。根据第91条开放检查的规范还包括作为母体材料的aetio-胆甾烯基-17-醛、超肾上腺皮质激素系列化合物、胆甾酮和胆甾烯酮。可以使用的金属盐还包括铷、铯和乙炔或单取代乙炔的银盐。此外，还可以使用事先制备的金属乙炔化物的悬浮液。‘本发明过程形成的化合物的衍生物还包括葡萄糖苷。这一主题在已接受的规范中没有出现。

• 17.beta.-Ethynyl-3,17.alpha.-estradiol and derivatives thereof
  申请人：Ortho Pharmaceutical Corporation

  公开号：US04022892A1

  公开（公告）日：1977-05-10

  17.beta.-ethynyl-3,17.alpha.-estradiol and derivatives thereof are prepared by epimerization of 17-acyl esters of 17.alpha.-ethynyl-3,17.beta.-estradiol 3-ethers. 17.alpha.-ethynyl-3,17.alpha.-estradiol and its derivatives are active as post-coital antifertility agents and inhibit the growth of or reduce the size of the prostate gland and the seminal vesicle.

  17-beta-乙炔基-3,17-alpha-雌二醇及其衍生物是通过将17-乙炔基-3,17-beta-雌二醇3-醚的17-酰基酯进行对映异构化制备的。17-alpha-乙炔基-3,17-alpha-雌二醇及其衍生物作为事后避孕药剂活性，并且能抑制前列腺和精囊的生长或减小其大小。
• Asymmetric Organocatalytic Synthesis of 2,3-Allenamides from Hydrogen-Bond-Stabilized Enynamides
  作者：Zhi-Gang Ma、Jie-Lu Wei、Jun-Bing Lin、Guan-Jun Wang、Jia Zhou、Kai Chen、Chun-An Fan、Shu-Yu Zhang

  DOI：10.1021/acs.orglett.9b00839

  日期：2019.4.5

  Asymmetric catalytic synthesis of 2,3-allenamides from hydrogen-bond-stabilized enynamides in the presence of quinine-based bifunctional squaramide organocatalysts is described. This protocol forms a variety of 2,3-allenamides in high yields and excellent stereoselectivities, in which the elaborated introduction of intramolecular H-bonds within the N,N-bidentate amide group constitutes one of the keys

  描述了在基于奎宁的双功能方酰胺有机催化剂存在下，由氢键稳定的烯酰胺不对称催化合成2，3-烯酰胺。该方案以高收率和优异的立体选择性形成了各种2,3-烯丙酰胺，其中在N，N-双齿酰胺基团中分子内H键的精心引入构成了此高对映选择性转化的关键之一。该反应的合成实用性已通过烯丙酰胺的轴对中心手性转移来提供对映体富集的结构单元而得到证明。
• A facile access to spiro furanone skeleton based on Pd(II)-mediated cyclization–carbonylation of propargylic esters
  作者：Keisuke Kato、Hideaki Nouchi、Keisuke Ishikura、Satoshi Takaishi、Satoshi Motodate、Hikaru Tanaka、Kazuho Okudaira、Tomoyuki Mochida、Ryuichiro Nishigaki、Koki Shigenobu、Hiroyuki Akita

  DOI：10.1016/j.tet.2005.12.033

  日期：2006.3

  mediated by Pd(II) afforded cyclic orthoesters, which were hydrolyzed into γ-acetoxy-β-ketoesters. Based on the NMR experiments, it was presumed that the cyclization reaction was initiated by a nucleophilic attack of carbonyl oxygen to the alkyne carbon coordinated to palladium(II). When the γ-acetoxy-β-ketoesters were treated with a basic condition, Knoevenagel–Claisen type condensation took place, and

  Pd（II）介导的炔丙基酯的氧化环化-羰基化反应生成环状原酸酯，然后将其水解为γ-乙酰氧基-β-酮酸酯。基于NMR实验，推测环化反应是由羰基氧对配位于钯（II）的炔碳的亲核攻击引发的。在碱性条件下处理γ-乙酰氧基-β-酮酸酯时，发生了Knoevenagel–Claisen型缩合反应，并以高收率获得了螺呋喃酮衍生物。我们将这些反应应用于类固醇衍生物，并合成了具有螺呋喃酮片段的类固醇衍生物。其中，螺呋喃酮4j具有血管舒张活性和心动过缓。化合物2i – 4k 对CYP3A有抑制作用。
• Protection of COOH and OH groups in acid, base and salt free reactions
  作者：Xiaotao Zhu、Bo Qian、Rongbiao Wei、Jian-Dong Huang、Hongli Bao

  DOI：10.1039/c8gc00037a

  日期：——

  We report an iron-catalyzed general functional group protection method with inexpensive reagents. This environmentally benign process does not use acids or bases, and does not produce waste products. Further purification beyond filtration and evaporation is, in most cases, unnecessary. Free COOH and OH groups can be protected in a one-pot reaction.

  我们报告了一种廉价的试剂铁催化的一般官能团保护方法。这种对环境无害的过程不会使用酸或碱，也不会产生废品。在大多数情况下，无需进行除过滤和蒸发之外的进一步纯化。一锅反应可保护游离的COOH和OH基团。