N,N'-methanediylidenebis(2,2-dimethylpropan-1-amine) | 71054-06-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N'-methanediylidenebis(2,2-dimethylpropan-1-amine)
• 英文别名: bis(2,2-dimethylpropyl)carbodiimide
• CAS: 71054-06-3
• 化学式: C₁₁H₂₂N₂
• mdl: MFCD03413208
• 分子量: 182.309
• InChiKey: PFECYQFYWMDNPE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.909
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N'-methanediylidenebis(2,2-dimethylpropan-1-amine) 在 氯化铵 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以89%的产率得到N,N'-bis(2,2-dimethylpropyl)guanidine
  参考文献：
  名称：

  Iminodiaziridines 的合成和 15N NMR 谱 - 1-Aryl-3-iminodiaziridines 的环扩展为 1H-和 3aH-Benzimidazoles、2H-Indazoles 和 5H-Dibenzo[d,f][1,3]diazepines

  摘要：

  亚氨基二氮丙啶是通过 (i) 用 N-氯胍的叔丁醇钾进行 1,3-脱氯化氢合成的，由 N,N',N"-取代的胍与次氯酸叔丁酯原位生成，以及 (ii) 碱介导的 1 ,3-从 N,N',N"-取代的羟基胍 O-磺酸中消除硫酸。在升高的温度下，（烷基亚氨基）二氮丙啶通过 1,3-移位、[2+1] 环消去反应得到异氰化物和二氮烯，以及开环消除反应得到亚烷基胍。N'-芳基-N-羟基胍O-磺酸提供（N-芳基亚氨基）二氮丙啶，但不提供1-芳基-3-亚氨基二氮丙啶，而是提供重排的异构体。含有全氘化叔丁基的前体得到重排产物，显示完全混乱。这表明 1-芳基-3-亚氨基二氮丙啶是中间体，可进行非常快速的简并价异构化。如果邻芳基位置被取代，则可获得高产率的（芳基亚氨基）二氮丙啶以及 2-亚氨基-2,3-二氢-3aH-苯​​并咪唑。否则，2-氨基-1H-苯并咪唑和强荧光 3-氨基-2H-吲唑，源自难以捉摸的 1-

  DOI：

  10.1002/ejoc.200900350
• 作为产物：
  描述：

  N,N'-bis(2,2-dimethylpropyl)thiourea 在 lead(II) oxide 作用下， 以 水 为溶剂， 反应 3.0h， 以85%的产率得到N,N'-methanediylidenebis(2,2-dimethylpropan-1-amine)
  参考文献：
  名称：

  Iminodiaziridines 的合成和 15N NMR 谱 - 1-Aryl-3-iminodiaziridines 的环扩展为 1H-和 3aH-Benzimidazoles、2H-Indazoles 和 5H-Dibenzo[d,f][1,3]diazepines

  摘要：

  亚氨基二氮丙啶是通过 (i) 用 N-氯胍的叔丁醇钾进行 1,3-脱氯化氢合成的，由 N,N',N"-取代的胍与次氯酸叔丁酯原位生成，以及 (ii) 碱介导的 1 ,3-从 N,N',N"-取代的羟基胍 O-磺酸中消除硫酸。在升高的温度下，（烷基亚氨基）二氮丙啶通过 1,3-移位、[2+1] 环消去反应得到异氰化物和二氮烯，以及开环消除反应得到亚烷基胍。N'-芳基-N-羟基胍O-磺酸提供（N-芳基亚氨基）二氮丙啶，但不提供1-芳基-3-亚氨基二氮丙啶，而是提供重排的异构体。含有全氘化叔丁基的前体得到重排产物，显示完全混乱。这表明 1-芳基-3-亚氨基二氮丙啶是中间体，可进行非常快速的简并价异构化。如果邻芳基位置被取代，则可获得高产率的（芳基亚氨基）二氮丙啶以及 2-亚氨基-2,3-二氢-3aH-苯​​并咪唑。否则，2-氨基-1H-苯并咪唑和强荧光 3-氨基-2H-吲唑，源自难以捉摸的 1-

  DOI：

  10.1002/ejoc.200900350

文献信息

• BORATE-BASED BASE GENERATOR, AND BASE-REACTIVE COMPOSITION COMPRISING SUCH BASE GENERATOR
  申请人：WAKO PURE CHEMICAL INDUSTRIES, LTD.

  公开号：US20160340374A1

  公开（公告）日：2016-11-24

  An object of the present invention is to provide a compound which is capable of attaining a composition having high storage stability without reacting with a base-reactive compound, even in the case of storage for a long period of time in a mixed state with the base-reactive compound, such as an epoxy-based compound, as well as capable of generating a strong base (guanidines, biguanides, phosphazenes or phosphoniums) by irradiation of light (active energy rays) or heating; a base generator comprising the compound; and a base-reactive composition comprising the base generator and the base-reactive compound. The present invention relates to the compound represented by the general formula (A); the base generator comprising the compound; and the base-reactive composition comprising the base generator and the base-reactive compound. (wherein R 1 represents an alkyl group; an arylalkynyl group which may be substituted with a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group; an alkenyl group; a 2-furylethynyl group; a 2-thiophenylethynyl group; or a 2,6-dithianyl group; R 2 to R 4 each independently represent an alkyl group; an arylalkynyl group which may be substituted with a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group; the aryl group which may be substituted with a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group; a furanyl group; a thienyl group; or an N-alkyl-substituted pyrrolyl group; Z + represents an ammonium cation having a guanidinium group, a biguanidium group or a phosphazenium group, or a phosphonium cation.)

  本发明的目的是提供一种化合物，能够在与碱反应性化合物混合状态长时间存储的情况下，仍能获得具有高储存稳定性的组合物，而不与碱反应性化合物发生反应，同时还能通过光照（活性能量射线）或加热产生强碱（胍胺、双胍胺、磷氮烷或磷銨）；包括该化合物的碱发生器；以及包括该碱发生器和碱反应性化合物的碱反应性组合物。本发明涉及由通式（A）表示的化合物；包括该化合物的碱发生器；以及包括该碱发生器和碱反应性化合物的碱反应性组合物。（其中R1代表烷基；可能被卤素原子、烷基、烷氧基或烷硫基取代的芳基炔基；烯基；2-呋喃基炔基；2-噻吩基炔基；或2,6-二硫基基；R2到R4各自独立地代表烷基；可能被卤素原子、烷基、烷氧基或烷硫基取代的芳基炔基；可能被卤素原子、烷基、烷氧基或烷硫基取代的芳基；呋喃基；噻吩基；或N-烷基取代的吡咯基；Z+代表具有胍胺基团、双胍胺基团或磷氮烷基团的铵阳离子，或磷銨阳离子。）
• ACID-RESISTANT BASE AND/OR RADICAL GENERATOR, AND CURABLE RESIN COMPOSITION CONTAINING SAID BASE AND/OR RADICAL GENERATOR
  申请人：WAKO PURE CHEMICAL INDUSTRIES, LTD.

  公开号：US20190002403A1

  公开（公告）日：2019-01-03

  The present invention relates to a compound represented by the general formula (A), a base- and/or radical-generating agent comprising the compound, and so on. In the formula, four pieces of R 1 each independently represents a hydrogen atom or a fluorine atom; four pieces of R 2 each independently represent a fluorine atom or a trifluoromethyl group; R 3 , R 6 , R 7 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R 4 and R 5 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, or R 4 and R 5 are bonded to each other to represent an alkylene group having 2 to 4 carbon atoms; and R 8 and R 9 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms and optionally having a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a halogen atom, and a nitro group, or R 8 and R 9 are bonded to each other to represent an alkylene group having 2 to 4 carbon atoms; provided that two or three of the eight groups R 3 to R 10 are each a hydrogen atom, and, in a case where two of the eight groups are each a hydrogen atom, then three to six of the remaining groups are each an alkyl group having 1 to 12 carbon atoms, and, in a case where three of the eight groups are each a hydrogen atom, then four or five of the remaining groups are each an alkyl group having 1 to 12 carbon atoms.

  本发明涉及一种由通式（A）表示的化合物，包括该化合物的生成碱基和/或基团产生剂等。在该式中，四个R1分别独立表示氢原子或氟原子；四个R2分别独立表示氟原子或三氟甲基基团；R3、R6、R7和R10分别独立表示氢原子或具有1至12个碳原子的烷基基团；R4和R5分别独立表示氢原子或具有1至12个碳原子的烷基基团，或者R4和R5相互连接表示具有2至4个碳原子的亚烷基基团；R8和R9分别独立表示氢原子、具有1至12个碳原子的烷基基团或具有6至14个碳原子且可选地具有选自包括具有1至6个碳原子的烷基基团、具有1至6个碳原子的烷氧基团、具有1至6个碳原子的烷硫基团、具有2至12个碳原子的二烷基氨基团、卤素原子和硝基基团的取代基的芳基团，或者R8和R9相互连接表示具有2至4个碳原子的亚烷基基团；前提是八个基团R3至R10中的两个或三个分别是氢原子，并且在其中两个基团分别是氢原子的情况下，其余基团中的三到六个分别是具有1至12个碳原子的烷基基团，而在其中三个基团分别是氢原子的情况下，其余基团中的四个或五个分别是具有1至12个碳原子的烷基基团。
• Synthetic Access to α-Oxoketene Aminals by the Nucleophilic Addition of Enol Silane-Derived Palladium(II) Enolates to Carbodiimides
  作者：Subba Rao Polimera、Andivelu Ilangovan、Nicholas A. Meanwell、Murugaiah A. M. Subbaiah

  DOI：10.1021/acs.joc.2c02107

  日期：2022.11.4

  Synthetically important α-oxoketene aminal intermediates can now be accessed from readily available and inexpensive carbodiimides as starting materials via the nucleophilic addition of palladium enolates derived from enol silane precursors. This operationally simple method features mild reaction conditions, including open air atmosphere, ligand-free metal catalysis, broad substrate scope, and multi-gram

  现在可以通过亲核加成衍生自烯醇硅烷前体的钯烯醇化物，从现成且廉价的碳二亚胺作为起始材料，获得合成上重要的 α-氧代烯胺中间体。这种操作简单的方法具有温和的反应条件，包括露天气氛、无配体金属催化、广泛的底物范围和多克可扩展性。展示了利用 α-氧代烯胺的烯胺特性并涉及对亲电系统进行 C-亲核加成的选择合成应用，包括 α,β-不饱和酯、偶氮二羧酸酯、芳烷基卤化物和醛。
• Borate-based base generator, and base-reactive composition comprising such base generator
  申请人：FUJIFILM Wako Pure Chemical Corporation

  公开号：US10100070B2

  公开（公告）日：2018-10-16

  A compound capable of providing a composition having high storage stability without reacting with a base-reactive compound, even when stored in a mixed state with the base-reactive compound, as well as capable of generating a strong base by irradiation of light (active energy rays) or heating. A base generator comprises the compound and a base-reactive composition comprises the base generator and the base-reactive compound. The compound is represented by the general formula (A).

  一种化合物，能够提供一种具有高储存稳定性的组合物，即使在与碱反应化合物混合储存的状态下，也不会与碱反应化合物发生反应，并且能够通过光（活性能量射线）照射或加热生成强碱。碱发生器由该化合物组成，碱反应组合物由碱发生器和碱反应化合物组成。该化合物由通式 (A) 表示。
• Acid-resistant base and/or radical generator, and curable resin composition containing said base and/or radical generator
  申请人：FUJIFILM Wako Pure Chemical Corporation

  公开号：US10428015B2

  公开（公告）日：2019-10-01

  The present invention relates to a compound represented by the general formula (A), a base- and/or radical-generating agent comprising the compound, and so on. In the formula, four pieces of R1 each independently represents a hydrogen atom or a fluorine atom; four pieces of R2 each independently represent a fluorine atom or a trifluoromethyl group; R3, R6, R7 and R10 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, or R4 and R5 are bonded to each other to represent an alkylene group having 2 to 4 carbon atoms; and R8 and R9 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms and optionally having a substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, a halogen atom, and a nitro group, or R8 and R9 are bonded to each other to represent an alkylene group having 2 to 4 carbon atoms; provided that two or three of the eight groups R3 to R10 are each a hydrogen atom, and, in a case where two of the eight groups are each a hydrogen atom, then three to six of the remaining groups are each an alkyl group having 1 to 12 carbon atoms, and, in a case where three of the eight groups are each a hydrogen atom, then four or five of the remaining groups are each an alkyl group having 1 to 12 carbon atoms.

  本发明涉及通式（A）代表的化合物、包含该化合物的碱和/或自由基生成剂等。 式中，R1 的四个部分各自独立地代表氢原子或氟原子；R2 的四个部分各自独立地代表氟原子或三氟甲基；R3、R6、R7 和 R10 各自独立地代表氢原子或具有 1 至 12 个碳原子的烷基；R4 和 R5 各自独立地代表氢原子或具有 1 至 12 个碳原子的烷基，或 R4 和 R5 相互键合代表具有 2 至 4 个碳原子的亚烷基；和 R8 和 R9 各自独立地代表一个氢原子、一个具有 1 至 12 个碳原子的烷基或一个具有 6 至 14 个碳原子的芳基，并可选择具有一个取代基，该取代基可选自具有 1 至 6 个碳原子的烷基、具有 1 至 6 个碳原子的烷氧基、具有 1 至 6 个碳原子的烷硫基、具有 2 至 12 个碳原子的二烷基氨基、卤素原子和硝基组成的组，或 R8 和 R9 相互键合代表一个具有 2 至 4 个碳原子的亚烷基；条件是八个基团 R3 至 R10 中的两个或三个基团各自为氢原子，在八个基团中的两个基团各自为氢原子的情况下，其余基团中的三至六个基团各自为具有 1 至 12 个碳原子的烷基，在八个基团中的三个基团各自为氢原子的情况下，其余基团中的四个或五个基团各自为具有 1 至 12 个碳原子的烷基。