• 제목/요약/키워드: Triethylsilane

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광분해 반응에 의한 Phenylsilylene의 생성과 그 반응성에 관한 연구 (Photochemical Generation of Phenylsilylene and Its Chemistry)

  • 이도남;신한섭;김장환;이명의
    • 대한화학회지
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    • 제37권8호
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    • pp.757-764
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    • 1993
  • Phenylsilylene(PhHSi:)의 광분해 전구체인, 1,1,1,3,3,3-hexamethyl-2-phenyltrisilane(2)과 2,3-dicarbomethoxy-1,4,5,6,7-pentaphenyl-7-silanorbornadiene(5)을 10%와 73%의 수율로 각각 합성하였다. 전구체 2를 254 nm의 빛을 조사시켜 광분해 실험시킨 결과 triethylsilane 존재하에서는 phenylsilylene이 Si-H 결합에 삽입된 생성물인 1,1,1-triethyl-2-phenyldisilane (6)이 44%의 수율로 얻어졌고, diphenylacetylene 존재하에서는 phenylsilylene이 삼중결합에 첨가된 후 diphenylacetylene과 [2+2] 첨가반응이 일어나 얻어진 생성물, 1-phenyl-1-silacyclopenta-2,4-diene(4)과 phenyl-silylene이 삼중결합에 첨가된 다음 곧 이합체화되어진 화합물인 1,2-diphenyl-1,2-disilacyclohexa-2,5-diene(10)이 각각 68% 와 26%의 수율로 얻어졌다. Neat 광반응에서는 생성된 phenylsilylene이 분자간 C-H 삽입반응을 하여 생성된 화합물, 1,5-dihydrosilanthren(11)과 전구체 2가 Si-H 결합에 삽입된 화합물, 1,2-diphenyltrisilane(12)이 5%와 7%의 수율로 각각 얻어졌다. 같은 조건에서 화합물 5를 triethylsilane과 methanol 존재하에서 광분해시킨 결과 phenylsilylene은 생성되지 않고 분자내 1,5-sigmatropic 자리옮김에 의한 silylenolether가 생성됨을 확인하였다.

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Radical Additions of Arenethiols to Ynamides for the Selective Synthesis of N-[(Z)-2-(Arylsulfanyl)-1-alkenyl]amides

  • Sato, Akinori;Yorimitsu, Hideki;Oshima, Koichiro
    • Bulletin of the Korean Chemical Society
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    • 제31권3호
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    • pp.570-576
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    • 2010
  • A variety of ynamides undergo highly regio- and stereoselective radical addition of arenethiols with the aid of triethylborane as a radical initiator. The products, N-[(Z)-2-arylsulfanyl-1-alkenyl]amides, can be reduced with triethylsilane in trifluoroacetic acid to yield N-[2-(arylsulfanyl)alkyl]amides.

A Direct Transformation of Aryl Aldehydes to Benzyl Iodides Via Reductive Iodination

  • Ruso, Jayaraman Sembian;Rajendiran, Nagappan;Kumaran, Rajendran Senthil
    • 대한화학회지
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    • 제58권1호
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    • pp.39-43
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    • 2014
  • A facile transformation of aryl aldehydes to benzyl iodides through one-pot reductive iodination is reported. This protocol displays remarkable functional group tolerance and the title compound was obtained in good to excellent yield.

(S)-5-요오드 -2-아미노인단.염산염의 합성 (Synthesis of (S)-5-iodo-2-aminoindan.HCI)

  • 마은숙
    • 약학회지
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    • 제45권6호
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    • pp.582-587
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    • 2001
  • (S)-5-iodo-2-aminoindan.HCI (7) was synthesized for developing a serotonergic agent. (S)- Phenylalanine was protected with trifuoroacetyl group and compound 2 was prepared by direct iodination in acetic acid and in the presence of I$_2$, KIO$_4$, and sulfuric acid. Compound 3 was cyclized by Friedel-Crafts reaction and reduced with NaBH$_4$ to form 5-iodo-2-(N-trifluoroacetyl)aminoindan-1-ol (4) . This compound was reduced to indan derivative 5 using the triethylsilane and BF$_3$ . Et$_2$O. It was basified with $K_2$CO$_3$ solution and treated with saturated HCl in ethyl ether to isolate compound 7.

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Interaction of Hydrosilanes with the Surface of Rhodium

  • Boo Bong Hyun;Hong Seung Ki;Lee Sun Sook;Kim Hyun Sook
    • Bulletin of the Korean Chemical Society
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    • 제15권12호
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    • pp.1103-1107
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    • 1994
  • Interaction of triethylsilane and diphenylsilane ($Ph_2$$SiH_2$, $Ph_2$$SiD_2$) with the surfaces of rhodium has been examined by trapping the reaction intermediates with 2,3-dimethyl-l,3-butadiene. 1,4-Hydrosilylation of the diene is predominantly observed to occur under mild condition over the rhodium catalyst. It is inferred from the product analyses that silylene and silyl radicals bonded to rhodium surfaces are the intermediates for addition of silylene to the diene, and for 1,4-hydrosilylation, respectively.

Determination of Relative Reactivities of Free Hydroxyl Groups in β-Cyclodextrin, Amylose, and Cellulose by Reductive-Cleavage Method

  • 이창규;김은주;전중호
    • Bulletin of the Korean Chemical Society
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    • 제20권10호
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    • pp.1153-1158
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    • 1999
  • β-Cyclodextrin, amylose, and cellulose were partially methylated and acetylated in order to examine the relative reactivities of 2-, 3-, and 6-OH groups to alkylation and acylation. The partially methylated samples of the polysaccharides were treated with excess of ethyl iodide and sodium hydroxide in dimethyl sulfoxide to convert all of the free hydroxyl groups to ethyl ether groups. The partially O-ethylated and O-methylated polysaccharides were reductively cleaved with triethylsilane in the presence of trimethylsilyl methanesulfonate and borontrifluoride etherate (5 : 1 by mole) and the resulting 4-OH group was acetylated and benzoylated to form mixtures of eight 4-O-acyl-1,5-anhydroalditols. The relative ratio of the alditol esters were analyzed by gas chromatography to determine the degree of substitution at each position. A similar sequence of reactions was carried out with partially acetylated polysaccharides. The results indicated that the order of relative reactivities for methylation are 2-OH > 6-OH > 3-OH and for acylation are 6-OH > 2-OH > 3-OH regardless of the anomeric configuration.