3-oxabicyclo<4.4.0>dec-5-en-4-one | 6051-18-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 3-oxabicyclo<4.4.0>dec-5-en-4-one
• 英文别名: 3-Oxabicyclo<4.4.0>dec-5-en-3-on；1,5,6,7,8,8a-hexahydro-isochromen-3-one；(+/-)-1,5,6,7,8,8A-hexahydro-isochromen-3-on；1,5,6,7,8,8a-Hexahydroisochromen-3-one
• CAS: 6051-18-9
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: RCGZMGWNUYIXAA-UHFFFAOYSA-N

物化性质

• 熔点：
  59-60 °C(Solv: ethyl ether (60-29-7); hexane (110-54-3))
• 沸点：
  158-160 °C(Press: 12 Torr)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-oxabicyclo<4.4.0>dec-5-en-4-one 在 乙醇 、 镍 作用下， 80.0 ℃ 、9.81 MPa 条件下， 生成 trans-2,3-tetramethylene-δ-valerolactone
  参考文献：
  名称：

  α-羟基亚烷基-内酰胺-IX-合成d，l-iridomyrmecins和verwandter bicyclischer内酯

  摘要：

  据报道，普遍适用的合成方法可导致d，1- iridomyrmecin以及相关的双环γ和δ-内酯。

  DOI：

  10.1016/0040-4020(59)80002-8
• 作为产物：
  描述：

  2-(羟基甲基)环己酮 在 potassium hydride 、 三乙胺 作用下， 以 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 3-oxabicyclo<4.4.0>dec-5-en-4-one
  参考文献：
  名称：

  Synthesis of Erythrina and Related Alkaloids. XXVIII. Studies toward Total Synthesis of Non-aromatic Erythrina Alkaloids. (1). Synthesis and Isomerization of Unsaturated Bicyclic .DELTA.-Lactones.

  摘要：

  作为红细胞素C/D环系统的模型，合成了环状不饱和δ-内酯，并研究了它们在酸、碱（DBU，1, 8-二氮双环[5.4.0]十一烯）和氢氧化钠存在下的异构化反应。在内酯形式中，6-烯（3）是最不稳定的，并异构化为5-烯（1），然后再转变为1(6)-烯（2）。后两种内酯在DBU的存在下达到了大约3:2的1和2的平衡。相反，在打开状态下（氢氧化钠），内酯1是最不稳定的，异构化为2和3。1(10)-烯（4）在所有检查的条件下都表现惰性。

  DOI：

  10.1248/cpb.39.2797

文献信息

• SYNTHESIS IN THE FIELD OF THE ERYTHRINA ALKALOIDS: PART II. APPROACHES TO THE RING SYSTEM OF β-ERYTHROIDINE
  作者：B. Belleau

  DOI：10.1139/v57-095

  日期：1957.7.1

  The newly developed method for the elaboration of the ring system of the aromatic class of Erylhrina alkaloids has been successfully extended to the synthesis of 1,2,3,4-tetrahydroerythrinane (VI), a non-aromatic analogue. The key step in this synthesis involves ring closure of ketoamide (IV) itself, obtained from hexahydroindole and cyclohexenylacetic acid. Attempts to further extend this sequence

  新开发的用于合成 Eryhrina 生物碱芳香类环系的方法已成功扩展到 1,2,3,4-四氢赤藓烷 (VI)，一种非芳香类似物的合成。该合成中的关键步骤涉及从六氢吲哚和环己烯基乙酸中获得的酮酰胺 (IV) 本身的闭环。尝试将该顺序进一步扩展到使用 2H-5,6-二氢吡喃乙酸作为起始材料在后者的制备阶段遇到了失败。对图 III 所示的一种新的且不相关的逐步方法进行了研究，但在最终步骤中失败了。还简要描述了其他不成功的方法。
• Synthesis of Erythrina and Related Alkaloids. XXVIII. Studies toward Total Synthesis of Non-aromatic Erythrina Alkaloids. (1). Synthesis and Isomerization of Unsaturated Bicyclic .DELTA.-Lactones.
  作者：Yoshisuke TSUDA、Akiko ISHIURA、Saho TAKAMURA、Shinzo HOSOI、Kimiaki ISOBE、Kunihiko MOHRI

  DOI：10.1248/cpb.39.2797

  日期：——

  As a model of the C/D ring system of erythroidines, bicyclic unsaturated δ-lactones were synthesized in a regio-selective manner, and their isomerization reaction in the presence of acid, base (DBU, 1, 8-diazabicyclo[5.4.0]undec-7-ene), and NaOH were studied. In the lactone form, the 6-ene (3) was the most unstable and isomerized to the 5-ene (1) then to the 1(6)-ene (2). The latter two lactones equilibrate to give ca. 3 : 2 mixture of 1 and 2 in the presence of DBU. On the contrary, in the opened form (NaOH), the lactone 1 was the most unstable and isomerized to 2 and 3. The 1(10)-ene (4) was inert under all of the conditions examined.

  作为红细胞素C/D环系统的模型，合成了环状不饱和δ-内酯，并研究了它们在酸、碱（DBU，1, 8-二氮双环[5.4.0]十一烯）和氢氧化钠存在下的异构化反应。在内酯形式中，6-烯（3）是最不稳定的，并异构化为5-烯（1），然后再转变为1(6)-烯（2）。后两种内酯在DBU的存在下达到了大约3:2的1和2的平衡。相反，在打开状态下（氢氧化钠），内酯1是最不稳定的，异构化为2和3。1(10)-烯（4）在所有检查的条件下都表现惰性。
• Method of repelling insects
  申请人：COULSTON INTERNATIONAL CORPORATION

  公开号：EP0167265A1

  公开（公告）日：1986-01-08

  Compositions containing certain bicyclic lactones and having insect repellent properties are disclosed. Such compositions comprise a compound of the formula: or the corresponding unsaturated compound thereof having the formula: wherein R, R', R" and R''' each are lower alkyl or hydrogen; wherein y is an integer from 1-3, and x and z each are 0 or 1, with the proviso that y is 1 or 2 when x is 1; and a carrier. A method of using such a repellent composition to repel an insect from a situs comprises applying to such situs an effective amount of the composition, with or without the carrier, and thereby repelling the insect from the situs.

  本发明公开了含有某些双环内酯并具有昆虫驱避特性的组合物。 这种组合物包括式中的化合物：或其相应的不饱和化合物，其式为： 其中R、R'、R "和R'''各自为低级烷基或氢；其中y为1-3的整数，x和z各自为0或1，但当x为1时，y为1或2；以及载体。 使用这种驱避组合物来驱赶昆虫的方法包括将有效量的组合物（含或不含载体）施用于该部位，从而将昆虫从该部位驱赶出去。
• Insect repellent composition and method of repelling insects
  申请人：ANGUS CHEMICAL COMPANY

  公开号：EP0167266A1

  公开（公告）日：1986-01-08

  Potentiated insect repellent compositions comprising Deet and certain bicyclic lactones having insect repellent properties are disclosed. The lactones comprise compounds of the formula: or the corresponding unsaturated compounds thereof having the formula: wherein R, R' and R" and R'" each are lower alkyl or hydrogen; wherein y is an integer from 1-3, and x and z each are 0 or 1, with the proviso that y is 1 or 2 when x is 1. Preferably, R, R', R" and R'" each are hydrogen or methyl. Such compositions preferably further include a carrier. A method of using such a potentiated composition to repel an insect from a situs comprises applying to such situs an effective amount of the composition, with or without the carrier, and thereby repelling the insect from the situs.

  本发明公开了由 Deet 和某些具有驱虫特性的双环内酯组成的增效驱虫组合物。这些内酯包括式中的化合物： 或其相应的不饱和化合物，其式为 其中R、R'和R "和R'"各自为低级烷基或氢；其中y为1-3的整数，x和z各自为0或1，但x为1时y为1或2。这种组合物最好还包括一种载体。使用这种增效组合物驱赶昆虫的方法包括将有效量的组合物（无论是否含有载体）施用到该部位，从而将昆虫从该部位驱赶出去。
• Method for preparation of lactones
  申请人：COULSTON INTERNATIONAL CORPORATION

  公开号：EP0219199A1

  公开（公告）日：1987-04-22

  A method for synthesizing a wide variety of bicyclic lactones, as represented generally by the following structures (la) and (lb) wherein A= represents the group, which has had an additional hydrogen atom removed from a ring-carbon to form a carbon-oxygen bond between said ring-carbon and the oxygen atom in the lactone ring; and wherein each of R1, R3, R4, R5, R6, and R8 are independently selected from the group consisting of-H and-CH3; R2 is selected from the group consisting of -H,-CH3, and -C2H5; R7 is hydrogen; or with respect to structure (la), R7 together with R3, or if R2 and R3 are both groups other than hydrogen, together with R8 may represent a carbon-carbon bond; and wherein m is an integer from 1 to 5; o is 0,1,2, or3; and p is 0, 1, or2; providedthatthe sum of m+o+p is an integer from 3 to 5. When the desired lactone is represented by formula (Ib) above, the method of the present invention comprises heating under aqueous acidic conditions a beta, gamma-unsaturated cyclic nitrile having the formula (II), wherein R2, R3, R4, R5, R6, R8, m, o and p are as defined above, to form the desired bicyclic lactone. When the desired lactone is represented by Formula la above, an aldehyde having the formula (III), wherein R, is as defined above, is employed as an additional reactant.

  一种合成各种双环内酯的方法，一般由以下结构（la）和（lb）表示 其中 A= 代表以下基团 其中 R1、R3、R4、R5、R6 和 R8 各自独立地选自由-H 和-CH3 组成的组；R2 选自由-H、-CH3 和-C2H5 组成的组；R7 是氢；或者对于结构 (la)，R7 与 R3 一起，或者如果 R2 和 R3 都是氢以外的基团，则 R7 与 R8 一起可代表碳-碳键；其中 m 是 1 至 5 的整数；o 是 0、1、2 或 3；p 是 0、1 或 2；条件是 m+o+p 之和是 3 至 5 的整数。 当所需内酯由上式（Ib）表示时，本发明的方法包括在酸性水溶液条件下加热具有 式（II）的β、γ-不饱和环腈、 其中 R2、R3、R4、R5、R6、R8、m、o 和 p 如上定义，以形成所需的双环内酯。当所需内酯由上式 la 表示时，可使用具有式（III）的醛、 其中 R 如上文所定义，用作额外的反应物。