(1R,5S)-6,6-二甲基-3-氮杂双环[3.1.0]己烷-2-酮 | 159172-92-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 中文名称: (1R,5S)-6,6-二甲基-3-氮杂双环[3.1.0]己烷-2-酮
• 英文名称: (1R,5S)-6,6-dimethyl-3-azabicyclo[3.1.0]hexan-2-one
• 英文别名: (1R-cis)-6,6-dimethyl-3-azabicyclo[3.1.0]hexan-2-one
• CAS: 159172-92-6
• 化学式: C₇H₁₁NO
• 分子量: 125.17
• InChiKey: NOEANOXILSYOIN-WHFBIAKZSA-N

物化性质

• 沸点：
  254.9±9.0 °C(Predicted)
• 密度：
  1.057±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R,5S)-6,6-二甲基-3-氮杂双环[3.1.0]己烷-2-酮 在 lithium aluminium tetrahydride 作用下， 以80 %的产率得到6,6-dimethyl-3-azabicyclo[3.1.0]hexane
  参考文献：
  名称：

  Ru(II)催化分子内环丙烷化合成6,6-二甲基-3-氮杂双环[3.1.0]己烷

  摘要：

  6,6-二甲基-3-氮杂双环[3.1.0]己烷 (6,6-DMABH) 是多种抗病毒药物的重要成分，例如 boceprevir 和 pf-07321332。为了更有效地合成 6,6-DMABH，我们开发了一种创新方法，通过Ru (II) 催化和 Gabriel 合成利用 α-重氮乙酸酯的分子内环丙烷化。由 3-甲基-2-丁烯醇合成 6,6-DMABH 的克级合成通过七个不同的步骤实现，总产率为 28%。

  DOI：

  10.1007/s00044-023-03158-z
• 作为产物：
  描述：

  methyl (1R,3S)-2,2-dimethyl-3-[(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)methyl]cyclopropanecarboxylate 在 肼 作用下， 以 甲醇 为溶剂， 反应 25.0h， 以100%的产率得到(1R,5S)-6,6-二甲基-3-氮杂双环[3.1.0]己烷-2-酮
  参考文献：
  名称：

  EP2014647

  摘要：

  公开号：

文献信息

• Production Method of Polycyclic Lactams
  申请人：Hirata Norihiko

  公开号：US20090118519A1

  公开（公告）日：2009-05-07

  A process for producing lactams of formula (1) below, including the step of reacting lactones of formula (2) below with imides of any of formulae (3a), (3b) and (3c) to thereby obtain corresponding carboxylic acids (step A); the step of esterifying the carboxylic acids into corresponding esters (step B); and the step of reacting the esters with amines to thereby obtain lactams of the formula (1) (step C). In the formulae (1)-(2) and (3a)-(3c), when R 3 and R 4 are simultaneously hydrogen atoms, R is a substituted methylene or optionally substituted polymethylene; when at least one of R 3 and R 4 is a substituent other than hydrogen atom, R is an optionally substituted methylene or polymethylene; each of R 3 , R 4 , R 5 and R 6 independently is a hydrogen atom, a halogen atom, cyano, etc.; each of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 independently is a hydrogen atom, a halogen atom, nitro, etc.; and M is a hydrogen atom or an alkali metal atom.

  以下为制备式（1）内的内酰胺的方法，包括将制备式（2）的内酯与制备式（3a）、（3b）或（3c）的亚酰胺反应，从而得到相应的羧酸（步骤A）；酯化羧酸以得到相应的酯（步骤B）；将酯与胺反应以得到制备式（1）的内酰胺（步骤C）。在制备式（1）-（2）和（3a）-（3c）中，当R3和R4同时为氢原子时，R为取代亚甲基或可选的取代聚亚甲基；当R3和R4中至少有一个是除氢原子以外的取代基时，R为可选的取代亚甲基或聚亚甲基；R3、R4、R5和R6中的每一个独立地是氢原子、卤素原子、氰基等；A1、A2、A3、A4、A5、A6、A7、A8、A9和A10中的每一个独立地是氢原子、卤素原子、硝基等；M为氢原子或碱金属原子。
• N-Tert-Butoxycarbonyl-2-Pyrrolidinones and Production Method Thereof
  申请人：Hirata Norihiko

  公开号：US20100280259A1

  公开（公告）日：2010-11-04

  N-tert-butoxycarbonyl-2-pyrrolidinones represented by the following formula (1). In the formula (1), R1, R2, R3, R4, R5 and R6 independently represent a hydrogen atom, a halogen atom, a cyano group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, which may have a substituent, a linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms, which may have a substituent, or the like, R1 and R2 may be linked to form a >C═O group along with the carbon atom to which both are attached, R3 and R4 may be linked to form a >C═O group along with the carbon atom to which both are attached, R5 and R6 may be linked to form a >C═O group along with the carbon atom to which both are attached, or any two among R1, R2, R3, R4, R5 and R6 may be linked to form a polymethylene group having 1 to 4 carbon atoms which may have a substituent.

  以下公式（1）表示N-tert-丁氧羰基-2-吡咯酮。在公式（1）中，R1，R2，R3，R4，R5和R6独立地表示氢原子，卤素原子，氰基，具有1到10个碳原子的线性，支链或环状烷基，可以具有取代基，具有2到10个碳原子的线性，支链或环状烯基，可以具有取代基，或类似物，R1和R2可以连接形成>C═O基团，同时与它们附着的碳原子，R3和R4可以连接形成>C═O基团，同时与它们附着的碳原子，R5和R6可以连接形成>C═O基团，同时与它们附着的碳原子，或者R1，R2，R3，R4，R5和R6中的任意两个可以连接形成具有1到4个碳原子的聚亚甲基基团，可以具有取代基。
• N-TERT-BUTOXYCARBONYL-2-PYRROLIDINONES AND PRODUCTION METHOD THEREOF
  申请人：Hirata Norihiko

  公开号：US20090163722A1

  公开（公告）日：2009-06-25

  N-tert-butoxycarbonyl-2-pyrrolidinones represented by the following formula (1). In the formula (1), R1, R2, R3, R4, R5 and R6 independently represent a hydrogen atom, a halogen atom, a cyano group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, which may have a substituent, a linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms, which may have a substituent, or the like, R1 and R2 may be linked to form a >C═O group along with the carbon atom to which both are attached, R3 and R4 may be linked to form a >C═O group along with the carbon atom to which both are attached, R5 and R6 may be linked to form a >C═O group along with the carbon atom to which both are attached, or any two among R1, R2, R3, R4, R5 and R6 may be linked to form a polymethylene group having 1 to 4 carbon atoms which may have a substituent.

  下列化学式（1）代表的是N-叔丁氧羰基-2-吡咯酮。 在化学式（1）中，R1、R2、R3、R4、R5和R6各自独立地代表氢原子、卤素原子、氰基、具有1到10个碳原子的直链、支链或环状烷基，可能具有取代基，具有2到10个碳原子的直链、支链或环状烯基，可能具有取代基，或者类似物。R1和R2可以连接形成>C═O基团，同时与两者连接的碳原子相连。R3和R4可以连接形成>C═O基团，同时与两者连接的碳原子相连。R5和R6可以连接形成>C═O基团，同时与两者连接的碳原子相连。或者，在R1、R2、R3、R4、R5和R6中的任意两个可以连接形成具有1到4个碳原子的聚亚甲基基团，可能具有取代基。
• PRODUCTION METHOD OF POLYCYCLIC LACTAMS
  申请人：HIRATA Norihiko

  公开号：US20100324305A1

  公开（公告）日：2010-12-23

  A process for producing lactams of formula (1) below, including the step of reacting lactones of formula (2) below with imides of any of formulae (3a), (3b) and (3c) below to thereby obtain corresponding carboxylic acids (step A); the step of esterifying the carboxylic acids into corresponding esters (step B); and the step of reacting the esters with amines to thereby obtain lactams of the formula (1) (step C). In the formulae (1)-(2) and (3a)-(3c), when R 3 and R 4 are simultaneously hydrogen atoms, R is a substituted methylene or optionally substituted polymethylene; when at least one of R 3 and R 4 is a substituent other than hydrogen atom, R is an optionally substituted methylene or polymethylene; each of R 3 , R 4 , R 5 and R 6 independently is a hydrogen atom, a halogen atom, cyano, etc.; each of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 independently is a hydrogen atom, a halogen atom, nitro, etc.; and M is a hydrogen atom or an alkali metal atom.

  以下是制备式（1）内酰胺的过程，包括将式（2）内酯与式（3a）、（3b）和（3c）内酰亚胺反应以得到相应的羧酸（步骤A）；将羧酸酯化成相应的酯（步骤B）；将酯与胺反应以得到式（1）内酰胺（步骤C）。在式（1）-（2）和（3a）-（3c）中，当R3和R4同时为氢原子时，R是取代基甲基或可选取代聚甲基；当R3和R4中至少有一个是非氢原子取代基时，R是可选取代的甲基或聚甲基；每个R3、R4、R5和R6独立地是氢原子、卤素原子、氰基等；每个A1、A2、A3、A4、A5、A6、A7、A8、A9和A10独立地是氢原子、卤素原子、硝基等；M是氢原子或碱金属原子。
• N-TERT-BUTOXYCARBONYL-2-PYRROLIDINONES AND PROCESS FOR PRODUCING THE SAME
  申请人：Sumitomo Chemical Company, Limited

  公开号：EP2008999A1

  公开（公告）日：2008-12-31

  N-tert-butoxycarbonyl-2-pyrrolidinones of the following formula (1): [wherein, R1, R2, R3, R4, R5 and R6 represent each independently a hydrogen atom, halogen atom, cyano group, optionally substituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, optionally substituted linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms, optionally substituted aryl group having 6 to 20 carbon atoms, optionally substituted amino group, -ORa group, or -SRb group, Ra and Rb represent each independently a hydrogen atom, alkylcarbonyl group having 2 to 10 carbon atoms, arylcarbonyl group having 7 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkoxyalkyl group having 2 to 10 carbon atoms, trialkylsilyl group having 3 to 10 carbon atoms, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, alternatively, R1 and R2 may be connected to form a >C=O group together with a carbon atom to which they are connected, R3 and R4 may be connected to form a >C=O group together with a carbon atom to which they are connected, R5 and R6 may be connected to form a >C=O group together with a carbon atom to which they are connected, any two of R1, R2, R3, R4, R5 and R6 may be connected to form an optionally substituted polymethylene group having 1 to 4 carbon atoms, one or no-mutually-adjacent two methylene groups constituting the polymethylene group may be substituted by an oxygen atom, one or two ethylene groups constituting the polymethylene group may be substituted by a vinylene group, no-mutually-adjacent two methylene groups constituting the polymethylene group may be mutually connected via an oxygen atom, methylene group, ethylene group or vinylene group.].

  下式(1)的 N-叔丁氧羰基-2-吡咯烷酮： [其中，R1、R2、R3、R4、R5 和 R6 各自独立地代表氢原子、卤素原子、氰基、任选取代的具有 1 至 10 个碳原子的直链、支链或环状烷基、任选取代的具有 2 至 10 个碳原子的直链、支链或环状烯基、任选取代的具有 6 至 20 个碳原子的芳基、任选取代的氨基、-Ra和 Rb 各自独立地代表氢原子、具有 2 至 10 个碳原子的烷基羰基、具有 7 至 20 个碳原子的芳基羰基、具有 7 至 20 个碳原子的芳烷基、具有 2 至 10 个碳原子的烷氧基烷基、具有 3 至 10 个碳原子的三烷基硅基、具有 1 至 10 个碳原子的烷基、具有 6 至 20 个碳原子的芳基、 或者，R1 和 R2 连接在一起，形成一个 >C=O 基团，R3 和 R4 连接在一起，形成一个 >C=O 基团，R5 和 R6 连接在一起，形成一个 >C=O 基团，R7 和 R8 连接在一起，形成一个 >C=O 基团，R8 和 R9 连接在一起，形成一个 >C=O 基团，R1 和 R2 连接在一起，形成一个 >C=O 基团，R3 和 R4 连接在一起，形成一个 >C=O 基团，R5 和 R6 连接在一起，形成一个 >C=O 基团、 R1、R2、R3、R4、R5 和 R6 中的任意两个可连接成具有 1 至 4 个碳原子的任选取代的聚亚甲基，构成聚亚甲基的一个或不相邻的两个亚甲基可被一个氧原子取代、构成聚亚甲基的一个或两个亚乙基基团可被亚乙烯基团取代，构成聚亚甲基的不相邻的两个亚甲基基团可通过氧原子、亚甲基基团、亚乙基基团或亚乙烯基团相互连接。].