(-)-Adenallene | 114987-18-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: (-)-Adenallene
• 英文别名: 4-(6-aminopurin-9-yl)buta-2,3-dien-1-ol
• CAS: 114987-18-7；121653-99-4；123351-18-8；144071-05-6
• 化学式: C₉H₉N₅O
• 分子量: 203.203
• InChiKey: TYQIYCWCVLIXPH-UHFFFAOYSA-N

物化性质

• 熔点：
  198-200 °C
• 沸点：
  552.7±52.0 °C(Predicted)
• 密度：
  1.45±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.03
• 重原子数：
  15.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  89.85
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (-)-Adenallene 在 吡啶 、 sodium hydride 、 甲基磺酰氯 作用下， 反应 2.17h， 生成 9-乙基腺嘌呤
  参考文献：
  名称：

  Unsaturated phosphonates as acyclic nucleotide analogs. Anomalous Michaelis-Arbuzov and Michaelis-Becker reactions with multiple bond systems

  摘要：

  Reaction of adenallene (4a) with methanesulfonyl chloride in pyridine afforded 4'-chloro-4'-deoxyadenallene (6a). A similar reaction with toluene-4-sulfonyl chloride (NEt3, CH2Cl2) led to elimination of the unsaturated moiety and formation of N9-(4-toluenesulfonyl)adenine (8a). Michaelis-Arbuzov reaction of E- and Z-unsaturated chlorides 13a and 16b with triethyl phosphite afforded phosphonates 14a and 17b. Dealkylation of the latter products, coupled in case of 17b with acid hydrolysis, led to phosphonic acids 15a and 18. By contrast, Michaelis-Arbuzov reaction with butynyl chlorides 19a and 19b led to elimination of unsaturated moiety and alkylation of the released heterocyclic bases to give N9-ethyl derivatives 20a and 20b. In the presence of iodide ion, N9-(2,3-butadien-1-yl)adenine (30a, from 19a) and/or unsaturated diphosphonates 25a and 25b were obtained. The Michaelis-Arbuzov reaction of chloroallene 6a led to 2'-phosphonate 33a which, after dealkylation, afforded phosphonic acid 35a. When iodide ion was present, both 2'- and 4'-phosphonates 33a and 36a were obtained. Compound 36a was also prepared by Michaelis-Becker reaction of chloroallene 6a with sodium diethyl phosphite in THF-HMPA. In DMSO, both phosphonates 33a and 36a were formed. Under similar conditions (DMF), chlorobutyne 19a gave 4'-phosphonate 36a. Dealkylation of 36a furnished phosphonic acid 37a. Adenallene (4a) and diethyl chlorophosphite in pyridine afforded phosphonate 33a whereas butynol 39a afforded only adenine (10a). The probable reaction course of these transformations and spectral properties of the reaction products will be discussed.

  DOI：

  10.1021/jo00034a025
• 作为产物：
  描述：

  腺嘌呤 在 盐酸 、 sodium hydroxide 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 二甲基亚砜 为溶剂， 反应 37.0h， 生成 (-)-Adenallene
  参考文献：
  名称：

  核酸衍生的烯丙醇。具有抗逆转录病毒活性的核苷的不寻常类似物

  摘要：

  L'烷基化加氢碱基puriques ou pyrimidiques par des chloro butynes-2 ou des butyne-2ols Fournit les bases substitueesrespondantes。Une cyclisation en milieu basique se produit et l'on obtient les 组成 dihydro-2,5 furyl-2-B（ou B = 鸟嘌呤、胞嘧啶、腺嘌呤）。L'activite biologique de ces composes est etudiee

  DOI：

  10.1021/ja00197a063

文献信息

• (R)-(-)- and (S)-(+)-Adenallene: synthesis, absolute configuration, enantioselectivity of antiretroviral effect, and enzymic deamination.
  作者：Sreenivasulu Megati、Zafrir Goren、James V. Silverton、Joel Orlina、Hisao Nishimura、Takuma Shirasaki、Hiroaki Mitsuya、Jiri Zemlicka

  DOI：10.1021/jm00100a016

  日期：1992.10

  Synthesis of optically pure (-)- and (+)-adenallene 2 and 3 is described. Racemic adenallene (1a) was subjected to deamination with adenosine deaminase monitored by HPLC using a Chiralcel CA-1 column to give (-)-adenallene (2) and (+)-hypoxallene (4). The latter compound was converted to acetate 5. The reaction of 5 with trifluoromethanesulfonic anhydride and pyridine followed by ammonolysis furnished

  描述了光学纯的（-）-和（+）-腺嘌呤2和3的合成。使用Chiralcel CA-1柱，通过HPLC监测的外消旋腺烯（1a）用腺苷脱氨酶进行脱氨，得到（-）-腺烯（2）和（+）-次氧杂烯（4）。将后一化合物转化为乙酸酯5。5与三氟甲磺酸酐和吡啶反应，然后进行氨解，得到乙酸酯6或（+）-腺嘌呤（3），这取决于在最后步骤中使用的溶剂。乙酸盐5被平滑地转化为6-氯衍生物7，但是尝试进行氨解仅导致外消旋和分解。单晶X射线衍射确定了（-）-对映异构体2的R-构型。后者在晶格中形成具有伪样构象的腺嘌呤部分的伪对称二聚体。烯丙基键的扭转角显示偏离90度（分别为91和97度），并且在二聚体的两个分子中羟甲基的旋转异构偏好不同。R-对映异构体2抑制人免疫缺陷病毒（HIV-1）在ATH8细胞培养中的复制和细胞病变作用，IC50为5.8 microM，而S-对映异构体3活性较低（IC50> 200 microM
• Phosphodiester Amidates of Allenic Nucleoside Analogues:  Anti-HIV Activity and Possible Mechanism of Action
  作者：Holger Winter、Yosuke Maeda、Hiroaki Mitsuya、Jiri Zemlicka

  DOI：10.1021/jm960330n

  日期：1996.1.1

  Lipophilic phosphodiester amidates 2a, 2b, 4a, 4b, and 6 derived from anti-HIV agent adenallene 1a, 3a, inactive hypoxallene 1b, 3b, and 9-(4-hydroxy-2-butyn-1-yl)adenine (5) were synthesized and studied as inhibitors of HIV-1 in ATH8 cell system. All phosphodiester amidates were more biologically active than their parent nonphosphorylated compounds. Analogues 2a and 4a derived from (+/-)-adenallene 1a and (R)-enantiomer 3a are effective anti-HIV agents with EC(50) approximately 0.88 and 0.21 mu M, respectively. Both analogues are 16 and 28 times more effective than parent-compounds 1a and 3a, respectively. Some anti-HIV activity of hypoxallene derivatives 2b and 4b was noted in the range of 0.1-10 mu M but the dose-response relationship was poor. Phosphodiester amidate analogue 6 also exhibited anti-HIV activity in the range of 0.1-100 mu M, but this effect was accompanied by cytotoxicity. Hydrolytic studies performed at pH 9.8 and with pig liver esterase at pH 7.4 have shown that analogue 2a gives adenallene 4'-phosphoralaninate (10a) as the major product. These results can be interpreted in terms of initial hydrolysis of phosphodiester amidates 2a, 2b, 4a, 4b, and 6 catalyzed by intracellular esterase(s) to give stable phosphomonoester amidate intermediates with a free carboxyl group. The results obtained with hypoxallene phosphoramidates 2b and 4b indicate-that the aminosuccinate-fumarate enzyme system responsible for activation of AIDS drug ddIno (didanosine, Videx) can also, albeit less efficiently, activate hypoxallene 4'-phosphate (9b) and the respective (R)-enantiomer released inside the HIV-infected cells.
• XORLIN, A. A.;SMIRNOV, P. P.;KOCHETKOVA, S. V.;TSILEVICH, T. L.;SHCHAVELE+, BIOORGAN. XIMIYA, 15,(1989) N, S. 530-533
  作者：XORLIN, A. A.、SMIRNOV, P. P.、KOCHETKOVA, S. V.、TSILEVICH, T. L.、SHCHAVELE+

  DOI：——

  日期：——
• PHADTARE, SHASHIKANT;KESSEL, DAVID;ZEMLICKA, JIRI, NUCLEOSIDES AND NUCLEOTIDES, 8,(1989) N-6, C. 907-910
  作者：PHADTARE, SHASHIKANT、KESSEL, DAVID、ZEMLICKA, JIRI

  DOI：——

  日期：——
• PHADTARE, SHASHIKANT;ZEMLICKA, JIRI, J. AMER. CHEM. SOC., 111,(1989) N5, C. 1597
  作者：PHADTARE, SHASHIKANT、ZEMLICKA, JIRI

  DOI：——

  日期：——