2-Benzyl-2-(1,1-dimethylethyl)aziridine | 126179-50-8

• 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: 2-Benzyl-2-(1,1-dimethylethyl)aziridine
• 英文别名: 2-benzyl-2-tert-butylaziridine
• CAS: 126179-50-8
• 化学式: C₁₃H₁₉N
• 分子量: 189.301
• InChiKey: ATLFIBFMYHPCCS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  21.9
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-Benzyl-2-(1,1-dimethylethyl)aziridine 在 正丁基锂 作用下， 生成 9-<3,3-dimethyl-2-benzyl-2-(4-tolylsulfonamido)butyl>-9,10-dihydroanthracene
  参考文献：
  名称：

  Nitrogen-sulfur cleavage is faster than homolytic ring opening in single-electron transfer to some N-sulfonylaziridines. Competition between SN2 and SET

  摘要：

  The radical anions of the N-sulfonylaziridines, 1a,b and 3 undergo N-S cleavage in place of homolytic ring opening as is demonstrated by reactions with anthracenide A.- Nucleophilic ring opening of the sulfonylaziridines 1a,b and 3 by the carbanions AH-,X-, and Fl- of dihydroanthracene, xanthene, and fluorene, respectively, proceeds with the expected regioselectivity and is slow enough to allow some competition by a single-electron transfer (SET) initiated N-S cleavage, which provides the desulfonated aziridines and bixanthenyl X-X or bifluorenyl Fl-Fl, respectively. The SET path is favored by light. The competition is in favor of SET to the exclusion of the nucleophilic opening when trityl anion reacts with 1a. The twice-found byproducts 11 and 12 require the azirine intermediate 15, which is, at least formally, generated by elimination of TsH from 1a in a non-SET reaction.

  DOI：

  10.1021/jo00024a028
• 作为产物：
  描述：

  2-benzyl-2-tert-butyl-1-(4-p-tolylsulfonyl)aziridine 在 蒽 、 sodium 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以68%的产率得到2-Benzyl-2-(1,1-dimethylethyl)aziridine
  参考文献：
  名称：

  Nitrogen-sulfur cleavage is faster than homolytic ring opening in single-electron transfer to some N-sulfonylaziridines. Competition between SN2 and SET

  摘要：

  The radical anions of the N-sulfonylaziridines, 1a,b and 3 undergo N-S cleavage in place of homolytic ring opening as is demonstrated by reactions with anthracenide A.- Nucleophilic ring opening of the sulfonylaziridines 1a,b and 3 by the carbanions AH-,X-, and Fl- of dihydroanthracene, xanthene, and fluorene, respectively, proceeds with the expected regioselectivity and is slow enough to allow some competition by a single-electron transfer (SET) initiated N-S cleavage, which provides the desulfonated aziridines and bixanthenyl X-X or bifluorenyl Fl-Fl, respectively. The SET path is favored by light. The competition is in favor of SET to the exclusion of the nucleophilic opening when trityl anion reacts with 1a. The twice-found byproducts 11 and 12 require the azirine intermediate 15, which is, at least formally, generated by elimination of TsH from 1a in a non-SET reaction.

  DOI：

  10.1021/jo00024a028

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
• 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.
• Reactions of a tertiary carbon carrying a tert-butyl Group: Acid-catalyzed alcoholyses of activated aziridines with and without solvent assistance.
  作者：Konstantinos Bellos、Helmut Stamm

  DOI：10.1021/jo00122a057

  日期：1995.9

  Acid-catalyzed ring opening of tosylated and acylated 2-tert-butylaziridines 1 (2-phenyl) and 2 (2-benzyl) generates carbenium ions 18 (from 1) and 19 (from 2) which rearrange by a neopentyl rearrangement to carbenium ions 20 (18 --> 20) and 21 (19 --> 21). Reactions of 18-21 farm the final products: (1) deprotonation yields allylamides, homoallylamides, and enamides; (2) external trapping of 18 or 19 by a solvent molecule yields ethers; (3) internal trapping (only acylated 1 and 2) yields oxazolines and dihydrooxazines. The amount of external trapping with 1a,b depends on the activation: 1a (tosyl activation) yields more methyl ether (75% vs 51%) than 1b (benzoyl), but 1a yields less isopropyl ether (0% vs 25%) than 1b. The latter finding is in accord with an intramolecular interaction of the carbenium center of 18a with one of the tosyl oxygen atoms provided that this interaction distorts the carbenium plane to a pyramid which sterically retards external trapping. The former finding is not observed with 2a and 2b. This points to at least some methanol-assisted ring opening of 1a-H+ that must be supported by a benzylic effect. The required conformation of the phenyl ring is fixed in 1a-H+ (N-protonation and bulky SO2 cis to phenyl) but not in 1b-H+ (O-protonation and planar nitrogen conformation).
• Aziridines, 66 [1]. Arene Hydrides. 12 [2]. Reactions of carbanions with two sterically demanding 1-benzoylaziridines: SET, SN2, carbonyl attack
  作者：Konstantinos Bellos、Helmut Stamm

  DOI：10.1002/prac.19953370157

  日期：——

  Reactions of 2-phenyl (1a) and 2-benzyl (1b) 1-benzoyl-2-butylaziridines with carbanions X(-), AH(-), and Fl(-) of xanthene, dihydroanthracene and fluorene always form N-(2-butylethyl)-benzamides carrying phenyl (9a) or benzyl (9b). This reductive ring opening indicates an SET mechanism with aziridino ketyls 6a, b as intermediates. Nucleophilic ring opening (S(N)s) is found only with the carbanion of the lowest reducing power: Fl(-) --> 5a, b (62 %, 14 %). These two mechanisms cleave different bonds, a finding without precedence in S(N)2/SET competitions. Carbonyl addition resulting in benzoyl transfer to xanthene, dihydroanthracene or fluorene is usually also observed. It is the main reaction with X(-) and 1a. The highest yields of 9a, b are obtained with AH(-) since a special inner-sphere SET is available.
• Stamm, Helmut, Journal fur Praktische Chemie (Weinheim), 1999, vol. 341, # 4, p. 319 - 331
  作者：Stamm, Helmut

  DOI：——

  日期：——