• 제목/요약/키워드: Aziridine Ring

검색결과 12건 처리시간 0.019초

Substituents Effect on Aziridine Chemistry: N-Inversion Energy, Reactivity and Regioselectivity of Nucleophilic Ring-opening

  • Park, Gyoo-Soon;Kim, Seok-Chan;Kang, Han-Young
    • Bulletin of the Korean Chemical Society
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    • 제26권9호
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    • pp.1339-1343
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    • 2005

  • The N-inversion energies and nucleophilic ring-opening reactions of N-substituted aziridine compounds are investigated using B3LYP/6-31+$G^*$ methods, where substituents (R) on the nitrogen atom has been H (1), Me (2), Ph (3), Bn (4), CHMePh (5), $CO_2Me$ (6), COPh (7) and $SO_2Ph$ (8). The N-inversion energy with X group are decreased as the following order: R = CHMePh (17.06 kcal/mol) $\gt$ Me (16.97) $\gt$ Bn (16.70) $\gt$ H (16.64) $\gt$ $SO_2Ph$ (12.18) $\gt$ Ph (8.91) $\gt$ COPh (5.75) $\gt$ $CO_2Me$ (5.48). For reactivity of the ring opening toward cyanide ion, the aziridine 6 (R=$CO_2Me$) is shown to be the most reactive one. During the ring opening of aziridine 6 by CN$^{\ominus}$, the torsional OCNC angle becomes near to $180^{\circ}$, where the geometry allows for the effective incorporation of electrons of the nitrogen atom to the C=O bond. It would be a possible driving force for nucleophilic ring opening reaction as well as decreasing the N-inversion energy barrier. Regarding to the regioselectivity, the orientation of nucleophile in ring opening reaction appears to be different in the case of 9 and 10. The results are discussed in terms of steric/electronic effect of the $C_2$-substituents.

  • https://doi.org/10.5012/bkcs.2005.26.9.1339 인용 PDF KSCI

Semiempirical MO Calculation of Hetero Atom Three-Membered Ring Compounds (I) : N-Nitroso-aziridine, -oxaziridine, and -dioxaziridine

  • Hwang, Ki-Woon
    • Bulletin of the Korean Chemical Society
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    • 제11권5호
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    • pp.422-426
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    • 1990

  • Fully optimized MNDO molecular orbital calculations are described for N-nitroso-aziridine (I), -oxaziridine (II), and -dioxaziridine (III). The ground state geometries show the nonplanar configuration around the imino nitrogen. The nitroso group rotational energy barriers are 3.25, 0.43 and 1.18 kcal/mol for I, II and III, respectively. Also the calculated aziridine ring inversion barriers are 3.98, 15.61 and 27.46 kcal/mol for I, II and III, respectively.

  • https://doi.org/10.5012/bkcs.1990.11.5.422 인용 PDF

Bicyclic Derivatives of Aziridine - Materials for New Indicators of Radiation

  • Chebanov, V.A.;Zbruyev, A.I.;Desenko, S.M.;Doroshenko, A.O.;Vaschenko, V.V.
    • Journal of Radiation Protection and Research
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    • 제30권1호
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    • pp.31-34
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    • 2005

  • The article is devoted to the study of some hi-and tricyclic derivatives of aziridine as materials lot newindicators of ionizing radiation. To create high sensitive materials some aspects of photo induced ring opening processes in aziridine derivatives in ethanol solutions and in polymeric matrix were studied and two steps character of the processes investigated was established. Two types of radioindicators were suggested and preliminary tested. The new way of synthesis of radiochromic derivatives of aziridine was developed and series of target compounds synthesized.

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Silyl-Tranfer Photoreactions of Trimethylsilylmethyl Substituted Acyclic N-Sulfonylbenzamides

  • Oh, Sun-Wha
    • Journal of Photoscience
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    • 제12권2호
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    • pp.63-66
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    • 2005

  • The azomethine ylide forming photoreaction has been explored by probing the excited state chemistry of several N-trimethylsilylmethyl substituted cyclic and acyclic imides and amide analogs. N-[(Trimethylsilyl)methyl]-N-mesylbenzamide (5) undergoes the excited state C to O silyl migration reaction to produce azomethine ylide intermediate 13. This ylide undergoes electrocyclization to form transient aziridine intermediate 14 which react further by ring opening to generate N-phenacylamine product 10. On the other hand, photolysis of N-[N-mesyl-N-(trimethylsilyl)methyl]aminoethyl-N-mesylbenzamide (8) brings about desilylation resulting in the production of dimer 17.

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아지리딘 N-옥시드의 酸性化 자리옮김 反應에 關한 硏究 (Studies on the Oxidative Rearrangement of Aziridine N-Oxides)

  • 최세천;장향동
    • 대한화학회지
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    • 제27권1호
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    • pp.38-45
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    • 1983

  • 아지리딘 유도체들은 저온에서 아지리딘 N-옥시드 화합물들을 생성하는데 쓰여졌으며, 이 N-옥시드 화합물들은 수소이온이 첨가된 아지리딘처럼 실온에서 쉽게 분해하거나 또는 자리 옮김 반응을 일으켰다. N-옥시드 화합물이 분해하여 생성되는 니트로소 3차 부탄 화합물은 푸른색을 띄므로 쉽게 알 수 있다. 이 화합물은 아지리딘 고리의 탄소원자에 알킬기가 치환되지 않고, 아지리딘의 질소원자에 3차 부틸기와 같이 N-옥시드 자리옮김 반응이 불가능할 경우에 주요생성물임을 밝혔다. 그러나 알킬기로 치환되었을 경우 메틸기일 때는 대부분의 아지리딘이 시그마트로픽 자리옮김 반응이 일어나 올레핀 화합물이 생성되었다. 이때 아지리딘 고리의 질소에는 3차 부틸기가 치환된 때이다. 만일 질소에 3차 부틸기를 에틸기로 치환하면 아지리딘 고리에 자리옮김 반응이 일어나지 않고 에틸기가 에틸렌으로 제거 반응이 일어나서 N-히드록시 아지리딘 화합물이 생성되었다.

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2,2-gem-Diphenylaziridine의 開環反應 (Ring-Opening Reaction of 2,2-gem-Diphenylaziridine)

  • 한치선;남궁하일;강용익
    • 대한화학회지
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    • 제13권3호
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    • pp.229-232
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    • 1969

  • 2,2-gem-dephenylaziridine의 醋酸에 의한 開環反應에서 反應生成物은1,1-diphenyl-2-amino-ethyl acetate 임을 알았다. 또한 이 開環反應은 aziridine環 안에 있는 窒素原子와 tertiary炭素原子사이의 結合이 切斷되어 中間體로서 carbonium이온이 形成되는 過程을 거쳐서 進行됨을 알았다.

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