cis-1-benzoyl-2-benzyl-3-phenylaziridine | 98943-70-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: cis-1-benzoyl-2-benzyl-3-phenylaziridine
• 英文别名: cis-1-benzoyl-2-benzyl-2-phenylaziridine；[(2S,3R)-2-benzyl-3-phenylaziridin-1-yl]-phenylmethanone
• CAS: 98943-70-5
• 化学式: C₂₂H₁₉NO
• 分子量: 313.399
• InChiKey: FECGXYHGMSIABD-ZOAFEQKISA-N

物化性质

• 沸点：
  488.2±34.0 °C(Predicted)
• 密度：
  1.187±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  20.08
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  cis-1-benzoyl-2-benzyl-3-phenylaziridine 在 silica gel 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以91%的产率得到erythro-N-(1-benzyl-2-hydroxy-2-phenethyl)benzamide
  参考文献：
  名称：

  N-苯甲酰基氮丙啶光化学的物理方面：甲亚胺盐化物和相关光中间体的表征

  摘要：

  Results of a time-resolved study based on nanosecond laser flash photolysis are presented for phototransients derived from three N-benzoylaziridines in fluid solutions. The major transients, best assigned as azomethine ylides, are characterized by two maxima (380-440 and 560-610 nm) in the absorption spectrum in the visible region and by microsecond lifetimes at room temperature (tau(Y) = 0.2-31-mu-s); these are sluggish in their reactivity toward dimethyl acetylenedicarboxylate (k(q)Y less-than-or-equal-to 2 x 10(4) M-1 s-1 in benzene). Relatively short-lived triplets (tau(T) = 1-90 ns in benzene), 'quenchable by biphenyl and 2,5-dimethyl-2,4-hexadiene, act as precursors for the ylides. Between trans-1-benzoyl-2,3-diphenylaziridine (1a) and its cis isomer (1b), tau(T) is considerably shorter for the former (1 ns for 1a vs 40 ns for 1b, on the basis of the assumption that the rate constant for triplet quenching by 2,5-dimethyl-2,4-hexadiene is 2 x 10(9) M-1 s-1 in benzene); this is explainable in terms of efficient intramolecular quenching of the benzamide-type triplet by a beta-phenyl group in 1a while this interaction is less favorable in the most stable conformer of 1b (wherein the benzoyl moiety protrudes away from the cis phenyl groups). Steady-state photolysis and product analysis studies have provided evidence for photocleavage of both C-N and C-C bonds of the aziridine ring.

  DOI：

  10.1021/j100182a046
• 作为产物：
  描述：

  9,10-二氢蒽 、 alkaline earth salt of/the/ methylsulfuric acid 在 正丁基锂 作用下， 反应 0.42h， 生成 cis-1-benzoyl-2-benzyl-3-phenylaziridine
  参考文献：
  名称：

  Reactions with aziridines. 33. Arene hydrides. Part 1. Highly regioselective ring cleavage of N-acylaziridines by "anthracene hydride" (anion of 9,10-dihydroanthracene). Intermediacy of a carbonyl adduct. Influence of nitrogen inversion on the ring opening

  摘要：

  DOI：

  10.1021/jo00224a060

文献信息

• Homolytic aziridine opening (aza variant of cyclopropylcarbinyl-homoallyl rearrangement) by addition of tributyltin radical to N-acylaziridines. Factors contributing to the regioselectivity
  作者：Jürgen Werrya、Helmut Stamm、Pen-Yuan Lin、Reinhard Falkenstein、Stefan Gries、Hermann Irngartinger

  DOI：10.1016/s0040-4020(01)81081-4

  日期：1989.1

  fell drastically with steric hindrance of the addition of Bu3Sn. to the acyl oxygen of 1. They depended to some extent on the experimental conditions for hydrogen capturing when aziridine homolysis provided a primary radical 3 or 6. The regioselectivity of (probably reversible) ring homolysis can be understood in terms of the stability of the arising radical (3, 6), of stereoelectronic control (e.g. 1i

  AIBN在回流的苯中引发N-酰基丙啶1与Bu 3 SnH的反应，提供了还原性开环的产物5和8。由于添加了Bu 3 Sn的位阻，产率（大多数情况下是定量的）急剧下降。到1的酰基氧。他们在一定程度上取决于当氮丙啶均质分解提供伯自由基3或6时捕获氢的实验条件。的（可能是可逆的）环均裂区域选择性可以的产生自由基（稳定性的观点出发可以理解3，6），立体声电子控制（例如1i与1h相比）和边界轨道相互作用（1j）。从1j形成一级自由基的解释中，键长可能存在差异，但从N-甲苯磺酰基-2-甲基-氮丙啶11的X射线结构分析中未发现支持。异构体产物仅获得两次（1i，1j），比率5j：8j取决于Bu 3 SnH的浓度和氢同位素。没有发现比例为5:14的这种依赖关系（环化和无环化时减少3）由N-肉桂酰基氮丙啶11得到的吡咯烷酮。该比率（1：9为11和1：3为1N）必须反映在EZ异构体3。所观察到的由2形成E-3的偏
• Friedel-Crafts-Reaktion einigerN-Acylaziridine: Oxazoline als Zwischenstufen
  作者：Thomas Mall、Berthold Buchholz、Helmut Stamm

  DOI：10.1002/ardp.19943270606

  日期：——

  2‐Diphenylethylamine), die teilweise zu 1,1,2,2‐Tetraphenyläthan (5) weiterreagierten. Daneben wurden die Oxazoline 6a,b und 7b gefunden. Anhand des 2,4,5‐Triphenyloxazolins 6b wird gezeigt, daß die Oxazoline Zwischenstufen für 3, 4 und 5 sind. Die ungewöhnliche heterolytische Ringöffnung dieser speziellen Oxazoline wird diskutiert.

  3-取代的 1-酰基-2-苯基氮丙啶 1a、b 和 2b 出人意料地在苯中用 AlCl3 生成了 Friedel-Crafts 产物 3a、b 和 4b（酰化的 1-取代的 2,2-二苯乙胺），而无需加热，其中一些反应进一步到 1,1,2,2-四苯基乙烷 (5)。此外，还发现了恶唑啉 6a、b 和 7b。2,4,5-三苯基恶唑啉6b表明恶唑啉是3、4和5的中间体。讨论了这些特定恶唑啉不寻常的异裂开环。
• Aziridines. 69. Reactions of N-Acylaziridines with Sodium Metal and Sodium Naphthalenide. Elimination of olefines
  作者：Pen-Yuan Lin、Konstantinos Bellos、J�rgen Werry、Petros Assithianakis、Rainer Wei�、Thomas Mall、Gunther Bentz、H. Stamm

  DOI：10.1002/prac.19963380153

  日期：——

  Reactions of N-acylaziridines 1a-g (N-benzoyl except 1d) with sodium or naphthalenide N-.- in THF provide a variety of products that usually arise via the aziridino ketyls 2. Homolytic ring opening of 2 generates the amidatoalkyl radicals 3. Only with a very short reaction time were small amounts of benzil or benzoylnaphthalenes obtained indicating a reversible trapping of 2 by dimerization or coupling with N-.-. Homolysis of 2 produced always the more stable 3 apart from reactions of monomethylaziridines 1c,d where the primary radical i-3c,d is kinetically favoured. The amides R(1)CONHCHR(4)CHR(2)R(3) (9: isopropylamides i-9c,d from 1c,d) were usually the main products. 9 arise from 3 either by H atom abstraction from THF (probably in sodium metal runs) or by reduction of 3 to carbanions 5 that abstract a proton from THF (N-.- runs). Addition of 5a (R(2-4) = H) to 1a gives finally the ketone 8a. Self reaction of primary radical 3a is dimerization. Self reaction of tertiary or secondary radicals is disproportionation when an allylamide arises. This isomerizes to an enamide unless it is conjugated.R(2)R(3)C=CHR(4) and R(1)CONH(2) arise (probably) always. The mechanism, possibly a cyclic process of anion 6, is not clear.
• Mall, Thomas; Stamm, Helmut, Chemische Berichte, 1988, vol. 121, p. 1349 - 1352
  作者：Mall, Thomas、Stamm, Helmut

  DOI：——

  日期：——
• Single electron transfer versus nucleophilic ring opening in reactions of cis-trans pairs of activated 2-phenylaziridines. Strong influence of nitrogen pyramid for N-benzoylaziridines
  作者：Reinhard Falkenstein、Thomas Mall、Dieter Speth、Helmut Stamm

  DOI：10.1021/jo00078a014

  日期：1993.12

  Activated 2-phenylaziridines with a second substituent R in position 3 were made to react with xanthyl anion X-. Nucleophilic ring opening ia the only reaction that occurs with sulfonyl activation. The analogous N-benzoylaziridines 1 undergo this type of ring opening when the two substituents Ph and R are trans. The cis isomers (cis-1, Ph and R cis) react in this manner to a negligible extent if any. The (nearly) exclusive ring cleavage reaction of cis-1 is C-N homolysis of an intermediate ketyl formed by single electron transfer (SET) from X-. This cis-trans phenomenon is in accordance with the hypothesis that the two competing reactions depend in an opposite manner on the steepness of the nitrogen pyramid. A predominant or exclusive final result of SET is reductive aziridine opening and dimerization of the xanthyl radical X.. Formation of both diastereomers of the[GRAPHICS]amidoethylated xanthene in one case (R = Me) is evidence for a cross combination of X. with the radical formed by homolytic ring opening. Cross combination is also a likely path for R = H (no cis-trans isomerism), in addition to reductive ring opening. cis-Aziridines with dimethylcarbamoyl on nitrogen do not react via SET since the ketyl is not stabilized and therefore difficult to generate. Carbonyl attack on both types of acylaziridines competes more or less successfully with the two ring cleavage reactions.