(Z)-8-[(tetrahydro-2H-pyran-2-yl)oxy]-5-octen-1-yne | 782485-33-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (Z)-8-[(tetrahydro-2H-pyran-2-yl)oxy]-5-octen-1-yne
• 英文别名: (5Z)-8-[(tetrahydro-2H-2-yl)oxy]-5-octen-1-yne；2-[(Z)-oct-3-en-7-ynoxy]oxane
• CAS: 782485-33-0
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: CDYZOQXAOIGHJC-WAYWQWQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-8-[(tetrahydro-2H-pyran-2-yl)oxy]-5-octen-1-yne 在 正丁基锂 、 对甲苯磺酸 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 2.0h， 生成 (Z)-7-(diphenylphosphinyl)-3,7,8-nonatrien-1-ol
  参考文献：
  名称：

  Base-Catalyzed Endo-Mode Cyclization of Allenes:  Easy Preparation of Five- to Nine-Membered Oxacycles

  摘要：

  A reliable and efficient procedure for constructing five- to eight-membered oxacycles has been developed. Allenes with both a phosphoryl group and a suitable delta-hydroxyalkyl side chain at the Cl-position underwent an endo mode ring-closing reaction to give five- to seven-membered oxacycles. Changing the phosphoryl group to a phosphono functionality facilitated the preparation of eight-membered congeners. Introduction of a cis double bond to the alkyl side chain of the starting allenes made possible the easy formation of medium-sized oxacycles, such as the dihydrooxocin and tetrahydrooxonin frameworks, regardless of the electron-withdrawing group (POPh2, PO(OEt)(2), SOPh, and SO2Ph) at the C-1-position.

  DOI：

  10.1021/jo0488614
• 作为产物：
  描述：

  3-(2-tetrahydropyranyloxy)propyltriphenylphosphonium bromide 在 双(三甲基硅烷基)氨基钾 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 3.58h， 生成 (Z)-8-[(tetrahydro-2H-pyran-2-yl)oxy]-5-octen-1-yne
  参考文献：
  名称：

  Base-Catalyzed Endo-Mode Cyclization of Allenes:  Easy Preparation of Five- to Nine-Membered Oxacycles

  摘要：

  A reliable and efficient procedure for constructing five- to eight-membered oxacycles has been developed. Allenes with both a phosphoryl group and a suitable delta-hydroxyalkyl side chain at the Cl-position underwent an endo mode ring-closing reaction to give five- to seven-membered oxacycles. Changing the phosphoryl group to a phosphono functionality facilitated the preparation of eight-membered congeners. Introduction of a cis double bond to the alkyl side chain of the starting allenes made possible the easy formation of medium-sized oxacycles, such as the dihydrooxocin and tetrahydrooxonin frameworks, regardless of the electron-withdrawing group (POPh2, PO(OEt)(2), SOPh, and SO2Ph) at the C-1-position.

  DOI：

  10.1021/jo0488614

文献信息

• PROCESS FOR PREPARING A 5-ALKEN-1-YNE COMPOUND, (6Z)-1,1-DIALKOXY-6-NONEN-2-YNE COMPOUND, (2E,6Z)-2,6-NONADIENAL AND (2E)-CIS-6,7-EPOXY-2-NONENAL, AND 1,1-DIALKOXY-6-NONEN-2-YNE COMPOUND
  申请人：SHIN-ETSU CHEMICAL CO., LTD.

  公开号：US20200048161A1

  公开（公告）日：2020-02-13

  The object of the present invention is to provide a process for preparing a 5-alken-1-yne compound efficiently at low costs and a process for preparing (2E,6Z)-2,6-nonadienal by making use of the aforesaid process for preparing the 5-alken-1-yne compound. There is provided a process for preparing a 5-alken-1-yne compound of the following formula (4): Y-Z-CR 1 ═CR 2 —(CH 2 ) 2 —C≡CH (4) in which Y in formula (4) represents a hydrogen atom or a hydroxyl group, the process comprising at least steps of: subjecting (i) an alkenylmagnesium halide compound prepared from a haloalkene compound of the following formula (1): Y-Z-CR 1 ═CR 2 —(CH 2 ) 2 -X 1 (1) and (ii) an alkyne compound of the following formula (2): X 2 =C≡C—Si(R 3 )(R 4 )(R 5 ) (2) to a coupling reaction to form a silane compound of the following formula (3): Y-Z-CR 1 ═CR 2 —(CH 2 ) 2 —C≡C—Si(R 3 )(R 4 )(R 5 ) (3); and subjecting the silane compound (3) to a desilylation reaction to form the 5-alken-1-yne compound (4).

  本发明的目的是提供一种以低成本高效制备5-烯-1-炔化合物的方法，以及利用上述制备5-烯-1-炔化合物的方法制备(2E,6Z)-2,6-辛二烯醛的方法。提供了一种制备以下化学式（4）的5-烯-1-炔化合物的方法：Y-Z-CR1═CR2—(CH2)2—C≡CH（4），其中化学式（4）中的Y代表氢原子或羟基，该方法包括至少以下步骤：将（i）由以下化学式（1）的卤代烯烃化合物制备的烯基镁卤化物化合物：Y-Z-CR1═CR2—( )2-X1（1）和（ii）以下化学式（2）的炔烃化合物：X2=C≡C—Si(R3)(R4)(R5)（2）进行偶联反应，形成以下化学式（3）的硅烷化合物：Y-Z-CR1═CR2—( )2—C≡C—Si(R3)(R4)(R5)（3）；并将硅烷化合物（3）进行去硅反应，形成5-烯-1-炔化合物（4）。
• Process for preparing a 5-alken-1-yne compound, (6Z)-1,1-dialkoxy-6-nonen-2-yne compound, (2E,6Z)-2,6-nonadienal and (2E)-cis-6,7-epoxy-2-nonenal, and 1,1-dialkoxy-6-nonen-2-yne compound
  申请人：SHIN-ETSU CHEMICAL CO., LTD.

  公开号：US10781146B2

  公开（公告）日：2020-09-22

  The object of the present invention is to provide a process for preparing a 5-alken-1-yne compound efficiently at low costs and a process for preparing (2E,6Z)-2,6-nonadienal by making use of the aforesaid process for preparing the 5-alken-1-yne compound. There is provided a process for preparing a 5-alken-1-yne compound of the following formula (4): Y—Z—CR1═CR2—(CH2)2—C≡CH (4) in which Y in formula (4) represents a hydrogen atom or a hydroxyl group, the process comprising at least steps of: subjecting (i) an alkenylmagnesium halide compound prepared from a haloalkene compound of the following formula (1): Y—Z—CR1═CR2—(CH2)2—X1 (1) and (ii) an alkyne compound of the following formula (2): X2—C≡C—Si(R3)(R4)(R5) (2) to a coupling reaction to form a silane compound of the following formula (3): Y—Z—CR1═CR2—(CH2)2—C≡C—Si(R3)(R4)(R5) (3); and subjecting the silane compound (3) to a desilylation reaction to form the 5-alken-1-yne compound (4).

  本发明的目的是提供一种低成本高效率地制备 5-烯-1-炔化合物的工艺，以及利用上述制备 5-烯-1-炔化合物的工艺制备 (2E,6Z)-2,6-壬二烯醛的工艺。 本发明提供了一种制备下式（4）的 5-烯-1-炔化合物的工艺：Y-Z-CR1═CR2-(CH2)2-C≡CH(4)，其中式(4)中的Y代表氢原子或羟基，该工艺至少包括以下步骤：使(i)由下式(1)的卤代烃化合物制备的烯基卤化镁化合物：Y-Z-CR1═CR2-( )2-X1(1)和(ii)下式(2)的烷烃化合物：X2-C≡C-Si(R3)(R4)(R5) (2) 进行偶联反应，生成下式(3)的硅烷化合物：Y-Z-CR1═CR2-( )2-C≡C-Si(R3)(R4)(R5) (3)；将硅烷化合物(3)进行脱硅反应，形成 5-烯-1-炔化合物(4)。