α-(trimethylsilyl)benzylamine | 100423-11-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: α-(trimethylsilyl)benzylamine
• 英文别名: Phenyl(trimethylsilyl)methanamine
• CAS: 100423-11-8
• 化学式: C₁₀H₁₇NSi
• 分子量: 179.337
• InChiKey: PSOKMHOBNUSHCZ-UHFFFAOYSA-N

物化性质

• 沸点：
  114-117 °C(Press: 19.95 Torr)
• 密度：
  0.917±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.56
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  α-(trimethylsilyl)benzylamine 在 四丁基氟化铵 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 N-<(1,2-Diphenyl-2-hydroxy-ethyl-(1)>-acetamid
  参考文献：
  名称：

  Nucleophilic Aminomethylation of Aldehydes with α-Amino Alkylsilanes

  摘要：

  (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。

  DOI：

  10.1246/bcsj.58.1991
• 作为产物：
  描述：

  (α-phthalimidobenzyl)trimethylsilane 在 一水合肼 作用下， 以 乙醇 为溶剂， 反应 3.0h， 以61%的产率得到α-(trimethylsilyl)benzylamine
  参考文献：
  名称：

  Nucleophilic Aminomethylation of Aldehydes with α-Amino Alkylsilanes

  摘要：

  (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。

  DOI：

  10.1246/bcsj.58.1991

文献信息

• Preparation of enantioenriched α-silyl-benzylcarbamates
  作者：Claude Barberis、Normand Voyer

  DOI：10.1016/s0040-4039(98)01463-4

  日期：1998.9

  enantioselective [1,2] silicon rearrangement are reported. This novel synthetic method lead to the formation of chiral α-substituted benzylamines with an α-silyl group. In the procedure, N-Silyl-protectedN-Boc benzylamines are subjected to enantioselective deprotonation using the chiral complex (−) sparteine. s-BuLi to generate chiral benzyllithium intermediates that undergo a [1,2] silicon shift.

  报告了对映选择性[1,2]硅重排的第一个例子。这种新颖的合成方法导致形成具有α-甲硅烷基的手性α-取代的苄胺。在该方法中，使用手性络合物（-）斯巴丹宁对N-甲硅烷基保护的N -Boc苄基胺进行对映选择性去质子化。s -BuLi生成手性苄基锂中间体，该中间体经历[1,2]硅移位。
• Benzoquinone-Linked Fullerenes with a Pyrrolidine Spacer
  作者：Masahiko Iyoda、Fatema Sultana、Ai Kato、Masato Yoshida、Yoshiyuki Kuwatani、Mitsuo Komatsu、Shigeru Nagase

  DOI：10.1246/cl.1997.63

  日期：1997.1

  The synthesis of 1,4-benzoquinone-linked fullerenes (1 and 2) and an attempted synthesis of 1,2-benzoquinone-linked fullerenes (9 and 10) are described with the interesting redox behavior of these benzoquinone-linked fullerenes.

  1,4-苯醌连接富勒烯（1和2）的合成以及1,2-苯醌连接富勒烯（9和10）的尝试合成，描述了这些苯醌连接富勒烯有趣的氧化还原行为。
• Flavin Chemical Models for Monoamine Oxidase Inactivation by Cyclopropylamines, .alpha.-Silylamines, and Hydrazines
  作者：Jong-Man Kim、Susan E. Hoegy、Patrick S. Mariano

  DOI：10.1021/ja00106a012

  日期：1995.1

  Models for the inactivation of the monoamine oxidase A and B, two closely related flavoenzymes, by cyclopropylamines, alpha-silylamines, and hydrazines have been investigated in order to gain insight into the possible chemical mechanisms for these processes. The activated (i.e. high reduction potential and electrophilicity) flavin, 3-methyl-5-ethyllumiflavinium perchlorate (5), was employed in this effort along with trans-2-phenylcyclopropylamine (1), a host of monosubstituted hydrazines (13-16), and alpha-(trimethylsilyl)benzylamine (9). Admixture of 5 with 1 (25 degrees C, MeCN) results in instantaneous formation of the stable and completely characterized flavin-amine adducts 6 (K-e = 2 x 10(4)) derived by addition of the amine function in 1 to the 4a-position of 5. Reaction of the 4a-adduct 6 with cyclopropylamine 1 (85 degrees C, MeCN) cleanly (80%) produces the aldimine 7 formed by condensation of the initial product, trans-cinnamaldehyde and amine 5. These results demonstrate that 4a-adducts related to 6 are capable of undergoing cyclopropane ring opening reactions by polar pathways to produce electrophilic alpha,beta-unsaturated carbonyl products. Consequently, ring opening reactions proposed for monoamine oxidase inactivation by primary and perhaps secondary cyclopropylamines can occur by polar routes and, thus, are not uniquely attributable to radical mechanistic pathways. In a similar manner, the flavinium salt 5 undergoes rapid reaction with the alpha-silylamine 9 to produce a stable 4a-adduct 10 (K-e = 7 x 10(4)). Reaction of this adduct with 9 (45 degrees C, MeCN) leads to initial production of N-[(alpha-trimethylsilyl)benzyl]benzaldimine (12) which undergoes desilylation to produce N-benzylbenzaldimine (11) under these conditions. Also, 4a-adduct 10 is rapidly converted to aldimine 11 by reaction with TBAF at 25 degrees C in MeCN. These results show that 4a-adducts, generated from activated flavins and alpha-silylamines, participate in fragmentation processes leading to silylation of nucleophiles and production of carbonyl products. This polar mechanistic pathway models the known inactivation reactions of the MAOs by alpha-silylamines previously attributed to SET (radical) routes. Reaction of flavinium salt 5 with phenyl- or benzylhydrazine results in formation of 4a-phenyl or -benzyl flavin adducts. For example, admixture of 5 and PhNHNH(2) in CH3CN at 25 degrees C provides the characterizable 4a-phenyl and 4a-cyanomethyl flavins, 21 (28%) and 22 (55%), and benzene. Benzylhydrazine reacts similarly with 5 to produce only the 4a-benzyl adduct 23 (89%). information about the mechanism for adduct formation in these reactions has come from studies with the hydrazine analogs, NH(2)NHCO(2)CH(2)Ph (15) and NH(2)OCH(2)Ph (16). These substances react rapidly with 5 in MeCN at 25 degrees C to cleanly produce stable 4a-hydrazine adducts, 17. The results suggest that 4a-alkylation or -arylation reactions of the activated flavin 5 with hydrazines probably occur via the intermediacy of 4a-hydrazine flavin adducts related to 17. Thus, a polar mechanistic model is also consistent with the known inactivation reactions of the MAOs with hydrazines which are also reported to generate 4a-flavin alkylated and arylated MAO derivatives.
• Generation and cycloaddition of polymer-supported azomethine imines: traceless synthesis of pyrazole derivatives from α-silylnitrosoamide derivatives bound to resin
  作者：Ken-Ichi Washizuka、Keiko Nagai、Satoshi Minakata、Ilhyong Ryu、Mitsuo Komatsu

  DOI：10.1016/s0040-4039(99)02140-1

  日期：2000.1

  1,3-Dipolar cycloaddition of polymer-supported azomethine imines with dimethyl acetylenedicarboxylate (DMAD) gave pyrazole derivatives in good yields. The azomethine imines were generated from polymer-supported alpha-silylnitrosoamides by a 1,4-silatropic shift. The feature of this reaction is that no cleavage operations are required after the cycloaddition. (C) 2000 Elsevier Science Ltd. All rights reserved.
• TSUGE, OTOHIKO;TANAKA, JUNJI;KANEMASA, SHUJI, BULL. CHEM. SOC. JAP., 1985, 58, N 7, 1991-1999
  作者：TSUGE, OTOHIKO、TANAKA, JUNJI、KANEMASA, SHUJI

  DOI：——

  日期：——