N-(三甲基硅基甲基)酰亚胺 | 18042-62-1

• 物质功能分类: 有机原料 - 氨基化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 中文名称: N-(三甲基硅基甲基)酰亚胺
• 中文别名: 邻苯二甲酰亚氨基甲基-三甲基硅烷；氮-(三甲基硅基甲基)邻苯二甲酰基亚胺；N-(三甲基硅基甲基)邻苯二甲酰亚胺
• 英文名称: N-<(trimethylsilyl)methyl>phthalimide
• 英文别名: N-((trimethylsilyl)methyl)phthalimide；N-(Trimethylsilylmethyl)phthalimide；2-(trimethylsilylmethyl)isoindole-1,3-dione
• CAS: 18042-62-1
• 化学式: C₁₂H₁₅NO₂Si
• mdl: MFCD00042784
• 分子量: 233.342
• InChiKey: FDUSEQGNRUIRAH-UHFFFAOYSA-N

物化性质

• 熔点：
  25-27 °C(lit.)
• 沸点：
  76-77 °C0.01 mm Hg(lit.)
• 密度：
  1.116±0.06 g/cm3(Predicted)
• 闪点：
  >230 °F

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.333
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• WGK Germany：
  3
• 安全说明：
  S22,S24/25

反应信息

• 作为反应物：
  描述：

  N-(三甲基硅基甲基)酰亚胺 以 乙腈 为溶剂， 反应 24.0h， 以81%的产率得到N-甲基邻苯二甲酰亚胺
  参考文献：
  名称：

  Novel and Efficient Azomethine Ylide Forming Photoreactions of N-(Silylmethyl)phthalimides and Related Acid and Alcohol Derivatives

  摘要：

  An investigation of the photochemistry of N-(silylmethyl)phthalimides and related alpha-phthaloylacetic acids and 2-phenylethanol derivatives has uncovered new excited state processes resulting in the formation of azomethine ylide intermediates. Irradiation of N-[(trimethylsilyl)methyl]phthalimide in MeCN promotes C to O silyl transfer to generate the corresponding azomethine ylide which is efficiently trapped by reaction with water to yield the N-methylphthalimide or by dipolar cycloaddition with acetone, methyl acrylate, or acrylonitrile. Cycloadditions with the latter two dipolarophiles are both regioselective and endo-stereoselective. These processes can be triplet photosensitized by use of acetophenone. The related N-[(trimethylsilyl)methyl]-1,8-naphthalimide reacts in a similar manner upon irradiation in MeCN solutions containing the dipolarophiles methyl acrylate and acrylonitrile to produce cycloadducts which undergo spontaneous elimination of TMSOH, yielding alpha,beta-unsaturated ester or nitrile products. The ylide formed by irradiation of the (silylmethyl)phthalimide is trapped in a stereospecific (retention) manner by the dipolarophiles trans-hex-4-en-3-one, dimethyl maleate, and dimethyl fumarate. The effect of aryl ring substitution on the regiochemical course of the photoinduced C to O silyl migration process was probed by use of the 4-methoxy- and 4-carbomethoxyl-N-(silylmethyl)phthalimides. Irradiation of the former substance in an MeCN solution containing acrylonitrile gives rise to a single adduct whose structure suggests that silyl migration to oxygen of the carbonyl meta to the OMe substituent is highly favored. In contrast, the 4-carbomethoxyphthalimide is converted under these conditions to a mixture of regioisomeric adducts. Thus, silyl migration in the excited state of this substance is nonselective. In accord with hints found in earlier observations made by Kanaoka (Chem. Pharm. Bull. 1982, 30, 1263), N-phthalimide derivatives of the alpha-amino acids glycine, alanine, and phenylalanine undergo similar ylide forming photoreactions upon irradiation in MeCN solutions. The azomethine ylides produced by photodecarboxylation of these substances are efficiently trapped by dipolarophiles, and the overall photoreactions starting with the alanine and phenylalanine derivatives are highly stereoselective. Finally, the N-phthalimide derivative of 2-amino-1-phenylethanol also is transformed to a related ylide upon irradiation in MeCN. The nature, regiochemical and stereochemical course, and mechanistic interpretation of these new azomethine ylide forming photoreactions are discussed in this publication.

  DOI：

  10.1021/ja00115a004
• 作为产物：
  描述：

  邻苯二甲酸亚胺 、 氯甲基三甲基硅烷 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以77%的产率得到N-(三甲基硅基甲基)酰亚胺
  参考文献：
  名称：

  曙红Y促进芳香砜的无金属氨基甲基化

  摘要：

  报道了杂环与有机染料的光催化氨甲基化。通过氨基甲基自由基形成的 C-C 键可以一步获得一系列功能化的杂环，而无需过渡金属。

  DOI：

  10.1002/chem.202102124

文献信息

• Activation of aliphatic carbon–carbon bonds of esters and amides by rhodium(II) porphyrin
  作者：Lirong Zhang、Kin Shing Chan

  DOI：10.1016/j.jorganchem.2007.01.012

  日期：2007.4

  Aliphatic carbon–carbon bonds of esters and amides were activated successfully with rhodium(II) porphyrin radical to give rhodium(III) porphyrin alkyls in moderate yields.

  酯和酰胺的脂族碳-碳键已被铑（II）卟啉自由基成功激活，从而以中等收率得到了铑（III）卟啉烷基。
• Nucleophilic Aminomethylation of Aldehydes with α-Amino Alkylsilanes
  作者：Otohiko Tsuge、Junji Tanaka、Shuji Kanemasa

  DOI：10.1246/bcsj.58.1991

  日期：1985.7

  Fluoride-induced desilylation of (α-phthalimido-, α-morpholino-, and α-acetamidobenzyl)silanes and a (phthalimidomethyl)silane generates the corresponding α-amino carbanions which add to a variety of aldehydes. The conversion of phthalimido group of the adducts into amino moiety leads to β-amino alcohols. This simple reaction sequence offers a new and general method of nucleophilic aminomethylation.

  (α-邻苯二甲酰亚胺基-、α-吗啉基-和α-乙酰胺基苄基)硅烷和(邻苯二甲酰亚胺基甲基)硅烷在氟化物诱导下进行脱甲硅烷基化反应，生成相应的α-氨基碳负离子，从而与各种醛加成。加合物的邻苯二甲酰亚胺基团转化为氨基部分产生β-氨基醇。这种简单的反应序列提供了一种新的通用亲核氨甲基化方法。
• Mechanistic Studies of the Azomethine Ylide-Forming Photoreactions of <i>N</i>-(Silylmethyl)phthalimides and <i>N</i>-Phthaloylglycine
  作者：Yasutake Takahashi、Tsutomu Miyashi、Ung Chan Yoon、Sun Wha Oh、Maria Mancheno、Zhuoyi Su、Daniel F. Falvey、Patrick S. Mariano

  DOI：10.1021/ja9841862

  日期：1999.4.1

  spectroscopy have now been employed to investigate the mechanistic details of these novel excited-state processes. The results of this effort show that azomethine ylides are the key reactive intermediates in these processes. In addition, the investigations provide information about the dynamics of several ylide decay pathways and the nature of the excited states responsible for the ylide-forming silyl-migration

  在早期的研究中，我们已经表明，在缺电子烯烃（例如丙烯酸甲酯）存在的情况下，对 N-[（三甲基甲硅烷基）甲基] 邻苯二甲酰亚胺和 N-邻苯二甲酰甘氨酸的 MeCN 溶液进行辐照会产生环加合物。此外，这些物质在 MeCN 水溶液中的辐照会导致 N-甲基邻苯二甲酰亚胺的形成。现在已采用激光闪光光解和荧光光谱来研究这些新型激发态过程的机械细节。这项工作的结果表明，偶氮甲碱叶立德是这些过程中的关键反应中间体。此外，这些研究提供了有关几种内立德衰变途径的动力学以及负责形成内立德的甲硅烷基迁移（单线态和三线态）和脱羧（三线态）反应的激发态性质的信息。N-[(三甲基甲硅烷基)甲基]邻苯二甲酰亚胺 (1) 和 N-邻苯二甲酰甘氨酸 (2) 的 MeCN 溶液的脉冲照射会产生瞬变，其吸收和...
• Azomethine Ylides from Tin-Substituted Cyclic Carbinol Amides:  A New Route to Highly Substituted Pyrrolizidines
  作者：William H. Pearson、Amber Dietz、Patrick Stoy

  DOI：10.1021/ol0499304

  日期：2004.3.1

  text] Addition of organolithium and organomagnesium reagents to N-(tri-n-butylstannylmethyl)phthalimides yields N-(tri-n-butylstannylmethyl) cyclic carbinol amides, which form azomethine ylides upon treatment with HF.pyridine. This novel route to azomethine ylides allows rapid access to highly functionalized pyrrolizidines (1,2,3,9b-tetrahydropyrrolo[2,1-a]isoindol-5-ones).

  [反应：见正文]将有机锂和有机镁试剂添加到N-（三-正丁基锡烷基甲基）邻苯二甲酰亚胺中可得到N-（三正丁基锡烷基甲基）环状甲醇酰胺，经HF。吡啶处理后形成甲亚胺基化物。这种制备偶氮甲亚烷基的新颖途径使得可以快速获得高度官能化的吡咯嗪（1,2,3,9b-四氢吡咯并[2,1-a] isoindol-5-ones）。
• Formation and cycloaddition of nonstabilized N-unsubstituted azomethine ylides from (2-azaallyl)stannanes and (2-azaallyl)silanes
  作者：William H. Pearson、Roger B. Clark

  DOI：10.1016/s0040-4039(99)00744-3

  日期：1999.6

  Protodestannylation or protodesilylation of (2-azaallyl)stannanes or (2-azaallyl)silanes led to the formation of nonstabilized N-unsubstituted azomethine ylides, which underwent cycloadditions with electron-poor alkenes to produce 2-alkyl- or 2,5-dialkylpyrrolidines. 1,3-Disubstituted ylides derived from the stannanes and silanes gave stereochemically complementary results; the stannanes led to trans-2

  （2-氮杂烯丙基）锡烷或（2-氮杂烯丙基）硅烷的原雌烯丙基化或原去甲硅烷基化导致形成未稳定的N-未取代的偶氮甲亚胺基化物，其与贫电子的烯烃进行环加成反应生成2-烷基-或2,5-二烷基吡咯烷酮。衍生自锡烷和硅烷的1，3-二取代的叶立德产生立体化学互补的结果；锡烷导致具有高立体选择性的反式-2,5-二烷基吡咯烷，而硅烷则导致具有中等立体选择性的顺式-2,5-二烷基吡咯烷。