• 제목/요약/키워드: n-$Bu_3$SnH

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Redistribution/Dehydrocoupling of Tertiary Alkylstannane $n-Bu_3 SnH$ Catalyzed by Group 4 and 6 transition Metal Complexes

  • 우희권;송선정;김보혜
    • Bulletin of the Korean Chemical Society
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    • 제19권11호
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    • pp.1161-1164
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    • 1998
  • The catalytic transformation of sterically bulky tertiary stannane n-Bu3SnH by the Cp2MCl2/Red-Al (M=Ti, Zr, Hf) and M(CO)6 (M=Cr, Mo, W) catalysts yielded two kinds of catenated products: one is a cross-linked polystannane as minor product, and the other is hexabutyldistannane (n-Bu3Sn)2 as major product. The distannane was produced by simple dehydrocoupling of n-Bu3SnH, whereas the cross-linked polystannane could be obtained via redistribution/dehydrocoupling combination process of n-Bu3SnH. The redistribution/dehydrocoupling combination process may initially produce a low-molecular-weight oligostannane with partial backbone Sn-H bonds which could then undergo an extensive cross-linking reaction of backbone Sn-H bonds, resulting in the formation of an insoluble polystannane.

1-[(아릴)(페닐셀레노)메틸]벤조트리아졸과 셀렌화 6-아릴-6-(벤조트리아졸-1-일)-1-헥센일 페닐의 삼부틸틴 수소화물과의 반응메카니즘에 관한 연구 (Mechanistic Studies on the Reactions of 1-[(Aryl)(phenylseleno)methyl]benzotriazoles and 6-Aryl-6-(benzotriazol-1-yl)-1-hexenyl Phenyl Selenides with Tributyltin Hydride)

  • 강윤호;김경태
    • 대한화학회지
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    • 제43권1호
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    • pp.74-84
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    • 1999
  • 벤조트리아졸을 보조체로 사용하는 유기합성법은 거의 대부분 이온성 반응 메카니즘으로 설명되며 라디칼 반응을 이용한 벤조트리아졸의 응용은 거의 없었다. 벤조트리아졸의 N-1의 ${\alpha}$위치 탄소 원자에 라디칼 중심을 만든 후 벤조트리아졸의 다섯고리를 형성하는 질소 원자중에서 질소 분자가 빠져나감으로서 생성되는 페닐 라디칼의 반응을 연구하기위해 1[(aryl)(phenylseleno)methyl]benzotriazole, AIBN, 그리고 $Bu_3$SnH을 벤젠에 용해시키고 환류시켜 주었다. 이 반응 혼합물로 부터 2-aminodiphenyl selenide (16∼29%), 2-aminobiphenyl (9∼15%), diphenyl diselenide (30∼93%), 1-(arylmethyl)benzotriazole (9∼39%), 그리고 tributyltinphenyl selenide (10∼36%)을 얻었으며, AIBN없이 과량의 $Bu_3$SnH 존재하에 같은 조건하에서 반응시키는 경우,diphenyl diselenide (53∼100%), benzotriazole (27∼35%) 그리고 1-(arylmethyl)-benzotriazole (16∼33%)와 함께 arylmethylidenaniline이 과량의 $Bu_3S_nH$에 의해 환원된 N-(arylmethyl)anilines (44∼66%)이 생성되었다. 같은 조건 하에서 6-aryl-6-(benzotriazol-1-yl)-1-hexenyl phenyl selenides, AIBN, 그리고 $Bu_3$SnH의 반응으로부터 6-aryl-6-phenylamino-1-hexene(9∼31%)과 1-aryl-1-oxo-5-pentene (15∼44%)을 얻었다. 이들 생성물의 생성 메카니즘을 제시하였으며 벤조트리아졸이 합성 보조체로 이용된 경우 $Bu_3$SnH에 의해 벤조트리아졸의 세개의 질소 원자를 포함하는 다섯원자고리로 부터 라디칼 반응에 의해 질소 분자가 빠져나가는 것을 보여준 새로운 예이다.

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Redistribution/Dehydrocoupling of Endocrine n-$Bu_3SnH$ to Polystannanes Catalyzed by Group 4 Metallocene Complexes

  • Park, Jaeyoung;Kim, Seongsim;Lee, Beomgi;Cheong, Hyeonsook;Noh, Ji Eun;Woo, Hee-Gweon
    • 통합자연과학논문집
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    • 제5권2호
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    • pp.79-83
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    • 2012
  • Trialkyltin n-$Bu_3SnH$, an endocrine disruptor, was slowly converted by the catalytic action of group 4 $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) to produce two phases of products: one is an insoluble cross-linked solid, polystannane in 7-23% yield as minor product via redistribution/dehydrocoupling combination process, and the other is an oil, hexabutyldistannane in 69-90% yield as major product via simple dehydrocoupling process. Redistribution/dehydrocoupling process first produced a low-molecular-weight oligostannane possessing partial backbone Sn-H bonds which then underwent an extensive cross-linking reaction of backbone Sn-H bonds, leading to an insoluble polystannane. This is the first exciting example of redistribution/dehydrocoupling of a tertiary hydrostannane catalyzed by early transition metallocenes.

Radical Polymerization of Vinyl Monomers to Poly(vinyl)s having nBu3Sn end Groups with Biological Activity

  • Park, Jaeyoung;Lee, Beomgi;Kim, Seongsim;Cheong, Hyeonsook;Gwak, Gyeongja;Lee, Ki Bok;Woo, Hee-Gweon
    • 통합자연과학논문집
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    • 제6권2호
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    • pp.71-75
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    • 2013
  • $Bu_3Sn$-endded poly(vinyl)s with biological activity were obtained by the radical polymerization of vinyl monomers using thianthrene cation radical/$^nBu_3H$. Thianthrene cation and stannyl radicals promoted the homopolymerization and copolymerization of styrene and ethyl vinyl ether having number average molecular weights of 2000-3100. Tributyltin hydride functions as a chain transfer agent. Such polymereization by cationic thianthrene and stannyl radicals could provide some clues for the biological reaction in living animals. Plausible polymerization mechanisms were suggested.

칸나(Canna generalis)의 뿌리로부터 지질화합물의 분리.동정 (Isolation and Identification of Lipids from the Roots of Canna generalis)

  • 방면호;송명종;이대영;양혜정;한민우;백남인;이윤형
    • Applied Biological Chemistry
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    • 제49권4호
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    • pp.339-342
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    • 2006
  • 칸나의 뿌리를 80% MeOH용액으로 추출하고, 얻어진 추출물을 EtOAc, n-BuOH 및 물로 용매 분획 하였다. 이 중 EtOAc 분획과 n-BuOH 분획으로부터 silica gel과 octadecyl silica gel(ODS) column chromatography로 정제하여 4종의 화합물을 분리하였다. 각 화합물의 화학구조는 NHR, MS 및 IR 등의 스펙트럼 데이터를 해석하여, $\beta$-sitosterol(1), linoleic aicd methyl ester(2), monoglycosyldiglyceride(3), daucosterol(4)으로 동정하였다. 이 화합물들은 칸나에서 처음으로 분리되었다.

스파티필름(Spathiphyllum cannifolium) 지상부로부터 지질화합물의 분리 (Isolation of Lipids from the Aerial Parts of Spathiphyllum cannifolium)

  • 이대영;박지해;유종수;송명종;백남인;이윤형
    • Applied Biological Chemistry
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    • 제51권1호
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    • pp.60-64
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    • 2008
  • 스파티필름 지상부를 80% MeOH 용액으로 추출하고, 얻어진 추출물을 EtOAc, n-BuOH 및 $H_2O$로 용매 분획 하였다. 이 중 EtOAc 분획으로부터 silica gel, ODS 및 Sephadex LH-20 column chromatography로 정제하여 3종의 지질화합물을 분리 하였다. 각 화합물의 화학구조는 NMR, MS, 및 IR 등의 스펙트럼 데이터를 해석하여 stigmasterol (1), $(2S)1-O-linolenoyl-2-O-myristoyl-3-O-{\beta}-D-galactopyranosyl-sn-glycerol$ (2), stigmasterol glucoside (3)으로 동정하였다. 이 화합물들은 스파티필름에서 처음으로 분리 및 동정 되었다.

Disproportionation/Dehydrocoupling of Endocrine Disruptor, Tributyltin Hydride to Polystannanes Using Cp2TiCl2/N-Selectride (Cp' = Cp' = C5H5, Cp; Me-C5H4, Me-Cp; Me5C5, Cp*) Catalyst

  • Park, Jaeyoung;Kim, Seongsim;Lee, Beomgi;Cheong, Hyeonsook;Lee, Ki Bok;Woo, Hee-Gweon
    • 통합자연과학논문집
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    • 제6권1호
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    • pp.34-38
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    • 2013
  • Tributyltin hydride ($n-Bu_3SnH$), an endocrine disruptor, was slowly polymerized by the group 4 ${Cp^{\prime}}_2TiCl_2/N$-selectride (Cp' = $C_5H_5$, Cp; $Me-C_5H_4$, Me-Cp; $Me_5C_5$, $Cp^*$) catalyst combination to give two phases of products: one is an insoluble cross-linked solid, polystannane in 3-25% yield as minor product via disproportionation/dehydrocoupling combination process, and the other is an oil, hexabutyldistannane in 65-90% yield as major product via simple dehydrocoupling process. Disproportionation/dehydrocoupling process first produced a low-molecular-weight oligostannane possessing partial backbone Sn-H bonds which then underwent an extensive cross-linking reaction of backbone Sn-H bonds, resulting in the formation of an insoluble polystannane. The disproportionation/dehydrocoupling of a tertiary hydrostannane mediated by early transition metallocene/inorganic hydride is quite unusual and applicable.