7-hydroxy-5-heptynenitrile | 69285-47-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 7-hydroxy-5-heptynenitrile
• 英文别名: 7-hydroxyhept-5-ynenitrile；6-cyano-hex-2-yn-1-ol；5-Heptynenitrile, 7-hydroxy-
• CAS: 69285-47-8
• 化学式: C₇H₉NO
• 分子量: 123.155
• InChiKey: DPPAXROPUQULFK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  44
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7-hydroxy-5-heptynenitrile 在 吡啶 、 sodium hydroxide 、 三溴化磷 作用下， 以 乙醚 、 水 为溶剂， 反应 9.0h， 生成 7-(1-Methyl-2,5-dioxo-cyclopentyl)hept-5-in-nitril
  参考文献：
  名称：

  Schick, H.; Schwarz, H.; Theil, F., Journal fur praktische Chemie (Leipzig 1954), 1984, vol. 326, # 3, p. 426 - 432

  摘要：

  DOI：
• 作为产物：
  描述：

  5-氯戊炔 在 正丁基锂 、 sodium iodide 作用下， 以 二甲基亚砜 为溶剂， 反应 14.0h， 生成 7-hydroxy-5-heptynenitrile
  参考文献：
  名称：

  Preparation of polyfunctional allenic alcohols by the regioselective addition of functionalized propargylic chromium(III) organometallics to carbonyl compounds

  摘要：

  The reaction of propargylic halides 1 (X = Cl, Br) with an aldehyde or ketone (0.67 equiv) in the presence of CrCl2 (2.0 equiv) and LiI (2 equiv, necessary if X = Cl) affords allenic alcohols 3 with excellent regioselectivities (3-6% of the regioisomeric acetylenic alcohol 4 is formed) and in good yields (68-90%). Interestingly, this method allows the generation of highly functionalized intermediate propargylic chromium organometallics contained an ester, cyano, or chloride functionality. The alpha-alkyl-substituted propargylic bromide 10 reacts with benzaldehyde yielding the acetylenic alcohol 11 as a diastereomeric mixture of only one regioisomer (90% yield).

  DOI：

  10.1021/jo00041a006

文献信息

• Regiocontrolled Cu^I-Catalyzed Borylation of Propargylic-Functionalized Internal Alkynes
  作者：Abraham L. Moure、Ramón Gómez Arrayás、Diego J. Cárdenas、Inés Alonso、Juan C. Carretero

  DOI：10.1021/ja300627s

  日期：2012.5.2

  orbitalic influence from the propargylic group, matched with ligand and substrate size effects, as key factors involved in the high β-selectivity. The vinylboronates allowed the stereoselective synthesis of trisubstituted olefins, while allylic substitution of the SO(2)Py group without affecting the boronate group provided access to formal hydroboration products of unbiased dialkylalkynes.

  在铜（I）催化的二烷基内炔与双（频哪醇）二硼的硼化中已经实现了良好的反应性和区域控制。炔丙基极性基团（OH、OR、SAr、SO(2)Ar 或 NHTs）的存在，与作为配体的 PCy(3) 结合，可以最大限度地提高反应性和位点选择性（β 对炔丙基功能）。DFT 计算表明来自炔丙基的微妙轨道影响与配体和底物尺寸效应相匹配，是高β-选择性的关键因素。乙烯基硼酸酯允许立体选择性合成三取代烯烃，而 SO(2)Py 基团的烯丙基取代而不影响硼酸酯基团提供了获得无偏二烷基炔烃的正式硼氢化产物的途径。
• Diastereoselective Synthesis of an Isoprostane:<b> (</b>±)-8-<i>epi</i>-PGF₂_α Ethyl Ester
  作者：Douglass F. Taber、R. Jason Herr、D. Mark Gleave

  DOI：10.1021/jo9616365

  日期：1997.1.1

  A total synthesis of the isoprostane (+/-)-8-epi-PGF(2)(alpha) ethyl ester (5) is described, based on the diastereoselective cyclization of alpha-diazo ketone 7. This ketone is assembled by aldol condensation between alpha-diazo ketone 8 and aldehyde 9. The sequential alpha-diazo ketone aldol/insertion described here offers a powerful new approach to cycloalkane construction.

  基于α-重氮酮7的非对映选择性环化，描述了异前列腺素（+/-）-8-epi-PGF（2）α乙酯（5）的全合成。该酮通过醛醇缩合组装。在α-重氮酮8和醛9之间。此处描述的顺序α-重氮酮醇醛/插入物为环烷烃的构建提供了一种有力的新方法。
• Cyano Diels−Alder and Cyano Ene Reactions. Applications in a Formal [2 + 2 + 2] Cycloaddition Strategy for the Synthesis of Pyridines
  作者：Takeo Sakai、Rick L. Danheiser

  DOI：10.1021/ja106901u

  日期：2010.9.29

  Two metal-free, formal [2 + 2 + 2] cycloaddition strategies for the construction of polycyclic pyridine derivatives are described that proceed via pericyclic cascade mechanisms featuring the participation of unactivated cyano groups as enophile and dienophile cycloaddition partners.

  描述了用于构建多环吡啶衍生物的两种不含金属的正式 [2 + 2 + 2] 环加成策略，它们通过周环级联机制进行，其特征是未活化的氰基作为亲烯体和亲二烯体环加成伙伴的参与。
• Hybrids of sugars and aromatics: A Pd-catalyzed modular approach to chromans and isochromans
  作者：Markus Leibeling、Dennis C. Koester、Martin Pawliczek、Daniel Kratzert、Birger Dittrich、Daniel B. Werz

  DOI：10.1016/j.bmc.2010.03.004

  日期：2010.6.1

  of our synthetic approach is the annelation of the benzene moiety via a highly efficient Pd-catalyzed domino reaction. This powerful approach led to a small library of highly substituted chromans and isochromans by making use of a variety of different diynes and bromoglycals. We investigated several Pd-catalysts in order to improve the yields and to enlarge the scope of the domino reaction. Furthermore

  在此，我们描述了使用碳水化合物作为起始原料的高度取代的苯并二氢吡喃和异苯并二氢吡喃的合成。我们合成方法的关键步骤是通过高效的Pd催化的多米诺反应使苯部分成环。这种强大的方法通过使用各种不同的二炔和溴代糖，形成了一个高度取代的色团和异色团的小型文库。我们研究了几种钯催化剂，以提高收率并扩大多米诺反应的范围。此外，我们通过同位素标记实验阐明了反应的机理。该反应最有可能通过氧化加成进行，接着是两个碳钯化步骤和最后的环化反应。
• Terminal amino prostaglandin analogues
  申请人：Beecham Group Limited

  公开号：US04315022A1

  公开（公告）日：1982-02-09

  Compounds of the formula (I): ##STR1## having pharmacological activities similar to those of natural prostaglandins wherein: n is 0 to 5; X is CO, CS or CH.sub.2 ; Y is --CH.sub.2 --CH.sub.2 --; or, when n is 1 to 5, --CH.dbd.CH-- or --C.tbd.C--; R.sub.1 is either CH.sub.2 NR.sub.5 R.sub.6, wherein R.sub.5 and R.sub.6 are separately hydrogen or C.sub.1-6 alkyl, or R.sub.5 is hydrogen and R.sub.6 is (CH.sub.2).sub.m CO.sub.2 R.sup.1.sub.9 wherein m is 0 to 4 and R.sup.1.sub.9 is optionally substituted C.sub.1-6 alkyl or benzyl, optionally substituted in the phenyl ring by chlorine or bromine atoms or by nitro or CF.sub.3 groups; or R.sub.5 and R.sub.6 are both the same (CH.sub.2).sub.m CO.sub.2 R.sup.1.sub.9 as hereinbefore defined; or C(NH.sub.2).dbd.NOH; or C(OR.sub.7).dbd.NH.sub.2.sup.+ B.sup.- wherein R.sub.7 is C.sub.1-6 alkyl and B.sup.- is a salting ion; or CH.sub.2 NHR.sub.8, wherein R.sub.8 is SO.sub.2 R.sup.1.sub.9, COR.sup.1.sub.9 or CZNHR.sub.9 and R.sup.1.sub.9 is as hereinbefore defined, R.sub.9 is hydrogen or C.sub.1-6 alkyl and Z is oxygen or sulphur; or CZNH.sub.2 wherein Z is as hereinbefore defined: R.sub.2 is hydrogen or C.sub.1-4 alkyl; R.sub.3 is C.sub.1-9 alkyl, C.sub.5-8 cycloalkyl or C.sub.5-8 cycloalkyl --C.sub.1-6 alkyl; or R.sub.2 and R.sub.3 taken with the carbon atom to which they are joined represent a C.sub.5-8 cycloalkyl group; and R.sub.4 is hydrogen or C.sub.1-6 alkyl; and salts thereof; with the provisos (i) that when X is CH.sub.2 then Y must be --CH.sub.2 --CH.sub.2 --, and (ii) when R.sub.1 is CH.sub.2 NR.sub.5 R.sub.6 or CH.sub.2 NHR.sub.8 then Y must be --CH.sub.2 --CH.sub.2 --, pharmaceutical compositions containing them and processes for their preparation.

  化合物的公式(I): ##STR1## 具有类似于天然前列腺素的药理活性，其中：n为0至5; X为CO，CS或CH.sub.2; Y为--CH.sub.2--CH.sub.2--; 或者，当n为1至5时，为--CH.dbd.CH--或--C.tbd.C--; R.sub.1为CH.sub.2NR.sub.5R.sub.6，其中R.sub.5和R.sub.6分别为氢或C.sub.1-6烷基，或R.sub.5为氢，R.sub.6为(CH.sub.2).sub.mCO.sub.2R.sup.1.sub.9，其中m为0至4，R.sup.1.sub.9为选择性取代的C.sub.1-6烷基或苄基，选择性取代苯环上可以是氯或溴原子或硝基或CF.sub.3基团；或者R.sub.5和R.sub.6均为(CH.sub.2).sub.mCO.sub.2R.sup.1.sub.9，如前所述；或C(NH.sub.2).dbd.NOH; 或C(OR.sub.7).dbd.NH.sub.2.sup.+ B.sup.-，其中R.sub.7为C.sub.1-6烷基，B.sup.-为盐基离子；或CH.sub.2NHR.sub.8，其中R.sub.8为SO.sub.2R.sup.1.sub.9，COR.sup.1.sub.9或CZNHR.sub.9，R.sup.1.sub.9如前所述，R.sub.9为氢或C.sub.1-6烷基，Z为氧或硫；或CZNH.sub.2，其中Z如前所述：R.sub.2为氢或C.sub.1-4烷基；R.sub.3为C.sub.1-9烷基，C.sub.5-8环烷基或C.sub.5-8环烷基--C.sub.1-6烷基；或R.sub.2和R.sub.3与它们连接的碳原子一起表示C.sub.5-8环烷基；R.sub.4为氢或C.sub.1-6烷基；及其盐；但是，当X为CH.sub.2时，Y必须为--CH.sub.2--CH.sub.2--，且当R.sub.1为CH.sub.2NR.sub.5R.sub.6或CH.sub.2NHR.sub.8时，Y必须为--CH.sub.2--CH.sub.2--，包含它们的制药组合物和制备它们的方法。