3,3-dichloro-4-chloromethyl-1-benzyl-pyrrolidin-2-one | 91989-84-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,3-dichloro-4-chloromethyl-1-benzyl-pyrrolidin-2-one
• 英文别名: 3,3-dichloro-4-chloromethyl-1-benzylpyrrolidin-2-one；N-benzyl-4-chloromethyl-3,3-dichloropyrrolidin-2-one；1-Benzyl-3,3-dichloro-4-(chloromethyl)pyrrolidin-2-one
• CAS: 91989-84-3
• 化学式: C₁₂H₁₂Cl₃NO
• 分子量: 292.592
• InChiKey: WAYUAQGUYZAARY-UHFFFAOYSA-N

物化性质

• 熔点：
  129.3-130.0 °C
• 沸点：
  444.7±45.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  lithium methanolate 、 3,3-dichloro-4-chloromethyl-1-benzyl-pyrrolidin-2-one 以 甲醇 为溶剂， 反应 2.5h， 以62%的产率得到N-benzyl-4-methyl-5,5-dimethoxy-3-pyrrolin-2-one
  参考文献：
  名称：

  Unusual access to 5-methoxy or 5,5-dimethoxy-4-methyl-3-pyrrolin-2-ones from chlorinated 4-methyl-pyrrolidin-2-ones

  摘要：

  The reaction of N-substituted 4-methyl-2-pyrrolidinones, carrying not less than two chlorine atoms on the C(3) and C(6) carbons afforded with alkaline methoxide in methanol, under mild conditions, the corresponding 5-methoxy or 5,5-dimethoxy-4-methyl-3-pyrrolin-2-ones in satisfactory yields. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00792-4
• 作为产物：
  描述：

  N-烯丙基苄胺 在 2,2'-联吡啶 、 copper(l) chloride 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 3,3-dichloro-4-chloromethyl-1-benzyl-pyrrolidin-2-one
  参考文献：
  名称：

  Transition metal-catalyzed radical cyclizations: a low-temperature process for the cyclization of N-protected N-allyltrichloroacetamides to trichlorinated .gamma.-lactams and application to the stereoselective preparation of .beta.,.gamma.-disubstituted .gamma.-lactams

  摘要：

  Cyclizations of N-substituted N-allyltrichloroacetamides, where the substituent is an alkyl, Cbz, Boc, Ts, or Ms group, are catalyzed by a 1:1 mixture of CuCl and bipyridine to give the corresponding beta,gamma-trichlorinated gamma-lactams in high yields. The reactions proceed at temperatures from -78-degrees-C to room temperature. Cyclizations of N-allyltrichloroacetamides of acyclic secondary allylic amines are achieved with good selectivity; the cis/trans ratios of the gamma-lactams formed were dependent on the substituents on the nitrogen atom. The stereochemical outcome is compared with that of free-radical cyclization.

  DOI：

  10.1021/jo00054a034

文献信息

• Catalytic atom-transfer radical cyclization by copper/bipyridine species encapsulated in polysiloxane gel
  作者：Yukihiro Motoyama、Kazuyuki Kamo、Akihiro Yuasa、Hideo Nagashima

  DOI：10.1039/b923213c

  日期：——

  Novel polysiloxane gel, in which CuCl/bipyridine species are immobilized, is prepared by treatment of polymethylhydrosiloxane with 4,4′-bis[(2-propenyl)oxy]-2,2′-bipyridine and 1,5-hexadine in the presence of Karstedt′s catalyst followed by addition of CuCl. This polysiloxane gel acts as a reusable catalyst in the atom-transfer radical cyclization of α-halogenated acetamide derivatives in high turnover numbers without allowing leakage of the metal species.

  一种新型聚硅氧烷凝胶被制备，通过在Karstedt催化剂的存在下，用4,4′-双[(2-丙烯基)氧]-2,2′-联吡啶和1,5-己二烯处理聚甲基氢硅氧烷，然后加入CuCl。这种聚硅氧烷凝胶在α-卤代乙酰胺衍生物的原子转移自由基环化中作为可重复使用的催化剂，表现出高的循环次数且不允许金属物种泄漏。
• Atom transfer radical cyclisations of activated and unactivated N-allylhaloacetamides and N-homoallylhaloacetamides using chiral and non-chiral copper complexes
  作者：Andrew J. Clark、Floryan De Campo、Robert J. Deeth、Robert P. Filik、Sylvain Gatard、Nicola A. Hunt、Dominique Lastécouères、Gerard H. Thomas、Jean-Baptiste Verlhac、Hathaichanuk Wongtap

  DOI：10.1039/a909666c

  日期：——

  Activated N-tosyl-2,2,2-trichloroacetamide 6a, N-benzyl-2,2,2-trichloroacetamide 6d, 2,2-dichloroacetamides 6b–c and 6e–f and 2-monohaloacetamides 11a–g undergo efficient 5-exo atom transfer radical cyclisations at room temperature mediated by CuCl or CuBr in the presence of tris(N,N-dimethylaminoethylene)amine 3 (trien-Me6). The efficiency and stereoselectivity of these cyclisations was found to be greater than existing published atom transfer procedures based upon CuCl(bipyridine), RuCl2(PPh3)3 and CuCl(TMEDA)2. The product distribution for the cyclisation onto alkyne 11g was found to be solvent dependent. Attempts to make larger ring sizes by endo cyclisation of N-tosylacetamides 19a–c led to a competing 5-exoipso aromatic substitution into the N-tosyl group followed by re-aromatisation and loss of SO2 to furnish an amidyl radical. Cyclisation of N-homoallylacetamides 25a–d proceeded smoothly to give δ-lactams with a range of catalysts based upon ligands 2 and 26. The stereoselectivity of cyclisation to give γ lactams could be somewhat influenced by using chiral enantiopure copper complexes 28–30 suggesting that the reactions may involve metal-complexed radicals.

  活化的N-托烯基-2,2,2-三氯乙酰酰胺6a、N-苄基-2,2,2-三氯乙酰酰胺6d、2,2-二氯乙酰酰胺6b–c和6e–f以及2-单卤乙酰酰胺11a–g在室温下通过CuCl或CuBr以及三（N,N-二甲氨基乙烯）胺3（trien-Me6）的介导，经历了高效的5-exo原子转移自由基环化反应。这些环化反应的效率和立体选择性比现有的基于CuCl（联吡啶）、RuCl2（PPh3）3和CuCl（TMEDA）2的原子转移程序更高。环化反应在炔烃11g上的产物分布发现依赖于溶剂。尝试通过N-托烯基乙酰酰胺19a–c的内环化生成更大环的过程，导致N-托烯基基团发生竞争性的5-exo环置换，随后发生再芳香化并失去SO2，生成酰基自由基。N-同烯丙基乙酰酰胺25a–d的环化顺利进行，得到了一系列基于配体2和26的催化剂的δ-内酯。通过使用手性恩路全纯铜复合物28–30，γ-内酯的环化立体选择性受到一定影响，表明反应可能涉及金属配位自由基。
• A novel preparative method for γ-butyrolactams via carbon–carbon bond formation: copper or ruthenium-catalysed cyclization of N-allyl trichloroacetamides
  作者：Hideo Nagashima、Hidetoshi Wakamatsu、Kenji Itoh

  DOI：10.1039/c39840000652

  日期：——

  Trichlorinated γ-butyrolactams are formed by copper or ruthenium-catalysed cyclization of Nallyl tichloroacetamides.

  三氯化γ-丁内酰胺是通过铜或钌催化的N烯丙基三氯乙酰胺的环化反应而形成的。
• Atom-transfer radical reactions catalyzed by a coordinatively unsaturated diruthenium amidinate, [(η5-C5Me5)Ru(μ2-i-PrN C(Me)Ni-Pr)Ru(η5-C5Me5)]+
  作者：Yukihiro Motoyama、Shiori Hanada、Shota Niibayashi、Kazuya Shimamoto、Naoki Takaoka、Hideo Nagashima

  DOI：10.1016/j.tet.2005.08.037

  日期：2005.10

  Atom-transfer radical cyclization (ATRC) and addition (ATRA) catalyzed by a coordinatively unsaturated diruthenium amidinate complex 4, [(η5-C5Me5)Ru(μ2-i-PrNC(Me)Ni-Pr)Ru(η5-C5Me5)]+, are investigated, and their features are compared with those of atom-transfer radical polymerization (ATRP). As an example of ATRC, a cationic diruthenium amidinate 4 is found to exhibit excellent catalytic reactivity

  由配位不饱和二钌催化原子转移自由基环化（ATRC）和加成（ATRA）脒基络合物4，[（η 5 -C 5我5）的Ru（μ 2 -我-PrNC（ME）N我-Pr）的Ru （η 5 -C 5我5）] +，进行了研究，它们的特征与那些原子转移自由基聚合（ATRP）的比较。作为ATRC的一个例子，发现阳离子di胺酸二钌4对N的环化具有极好的催化反应活性。-烯丙基α-卤代乙酰胺，包括环境温度下的生物碱骨架。从卤化物络合物原位产生的催化物种，（η 5 -C 5我5）的Ru（μ 2 -我-PrNC（ME）N我-Pr）的Ru（η 5 -C 5我5）（X）[ X = Cl，Br]和弱配位阴离子如NaPF 6和NaBPh 4的钠盐也显示出高催化活性。这实际上提供了解决作为实用催化剂的不稳定的4的解决方案。原位生成的催化剂种类4在室温下，α-烯烃对α，α，γ-三氯化γ-内酰胺与烯烃的分子间ATRA也有活性，以中等
• A Cationic Diruthenium Amidinate, [(η⁵-C₅Me₅)Ru(μ₂-<i>i</i>-PrN=C(Me)N<i>i</i>-Pr)Ru(η⁵-C₅Me₅)]⁺, as an Efficient Catalyst for the Atom-Transfer Radical Reactions
  作者：Yukihiro Motoyama、Mitsuru Gondo、Satoshi Masuda、Yuya Iwashita、Hideo Nagashima

  DOI：10.1246/cl.2004.442

  日期：2004.4

  A cationic diruthenium amidinate, [(η5-C5Me5)Ru(μ2-i-PrN=C(Me)Ni-Pr)Ru(η5-C5Me5)]+, is generated by treatment of (η5-C5Me5)Ru(μ2-i-PrN=C(Me)Ni-Pr)Ru(Cl)(η5-C5Me5) (3a) with NaPF6 or other metal salts of weakly coordinating anions, which is active towards catalytic atom transfer radical cyclization of N-allyl trichloroacetamides and related reactions.

  通过处理 (η5-C5Me5)Ru(μ2- 生成阳离子二钌脒盐，[(η5-C5Me5)Ru(μ2-i-PrN=C(Me)Ni-Pr)Ru(η5-C5Me5)]+ i-PrN=C(Me)Ni-Pr)Ru(Cl)(η5-C5Me5) (3a) 与 NaPF6 或其他弱配位阴离子的金属盐，对 N-烯丙基三氯乙酰胺的催化原子转移自由基环化具有活性相关反应。