• Title/Summary/Keyword: 자리옮김

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Beckmann Rearrangement of Ring A Steroidal Oxime Using the Carbon tetrachloride-triphenylphosphine (사염화탄소와 트리페닐포스핀을 사용한 스테로이드 링 A 옥심의 벡크만 자리옮김반응)

  • Kim Jack C.;Choi Soon-Kyu;Park Won-Woo;Lee Yong-Tae
    • Journal of the Korean Chemical Society
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    • v.23 no.1
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    • pp.42-45
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    • 1979
  • The experimental procedures of Beckmann rearrangement mostly involve the use of vigorous conditions such as strongly acidic reagents (conc. HCl, $H_2SO_4$, $PCl_5$, etc.) or elevated temperatures, which frequently cause isomerization of ketooximes prior to rearrangement.We have effected the Beckmann rearrangement on $5{\alpha}$-cholestan-3-one oxime using the carbon tetrachloride-triphenylphosphine reagent under mild, neutral conditions to give 3-aza-A-homo-$5{\alpha}$-cholestan-4-one. This new, mild, facile and rapid general method of Beckmann rearrangement is presented, and compared with the classical (more conventional) Beckmann reagent of polyphosphoric acid.

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Synthesis of Quinoxaline Derivatives from Benzofuroxan (Part I) (Benzofuroxan으로부터 Quinoxaline 유도체의 합성(제1보))

  • Kim, Ho-Sik;Hur, Jae-Hyuck
    • Journal of the Korean Chemical Society
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    • v.48 no.4
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    • pp.385-393
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    • 2004
  • 2-Ethoxycarbonyl-3-methylquinoxaline 1,4-dioxide (8) was synthesized from benzofuroxan and ethyl acetoacetate. The reaction of compound 8 with hydrazine hydrate or selenium dioxide gave 2-hydrazinocarbonyl-3-methylquinoxaline 1,4-dioxide (9) or 2-ethoxycarbonyl-3-formylquinoxaline 1,4-dioxide (10), respectively. The reaction of compound 9 with alkanoyl chlorides, benzoyl chlorides, heteroacyl chlorides, and benzenesulfonyl chlorides afforded 3-methyl-2-(substituted hydrazinocarbonyl)quinoxaline 1,4-dioxides (11-14), respectively. The reaction of compound 9 with sodium azide gave 2-azidocarbonyl-3-methylquinoxaline 1,4-dioxide (15), and then its refluxing in dioxane/alcohols resulted in the Curtius rearrangement to give N-(3-methyl-1,4-dioxoquinoxalin-2-yl)-alkyl carbamates (16). The reaction of compound 15 with substituted anilines afforded 2-(3-substituted phenylureido)-3-methylquinoxaline 1,4-dioxides (17). The reaction of compound 10 with benzoic hydrazide or substituted anilines provided quinoxaline 1,4-di-oxides (18, 19), respectively. The herbicidal and fungicidal activities of the synthesized compounds were investigated.

Rotation-invariant Object Categorization using Bag-of-features with Angular Pyramid (각도 피라미드를 이용한 Bag-of-features 를 통한 회전에 강한 물체 인식)

  • Kwon, Bojun;Kim, Seona;Lee, Kyong Joon;Yun, Il Dong;Lee, Sang Uk
    • Proceedings of the Korean Society of Broadcast Engineers Conference
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    • 2011.07a
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    • pp.449-450
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    • 2011
  • 본 논문에서는 영상에서의 물체 인식에 주로 사용되었던 공간 피라미드를 변형시킨 각도 피라미드를 이용한 bag-of-features 방법으로 회전 변화에도 강한 물체 인식에도 적용할 수 있도록 한다. 기존의 공간 피라미드에서 수직의 격자 모양으로 영상을 나누었던 것에 비해 각도 피라미드는 영상의 중심을 기준으로 동일한 각도로 영상을 분할하여 피라미드로 만든다. 각 영역 안에서 특징들의 히스토그램으로 영상을 표현하고 영상간의 유사도는 각도 피라미드를 단계별로 순환적 자리옮김을 통해 회전시켜가며 히스토그램 교집합을 구하여 측정한다. 이 방법을 Caltech-101 데이터베이스에 적용해본 결과 회전 변환을 준 테스트 영상에 대해 기존의 공간 피라미드를 사용한 방법에 비해 높은 성능을 보이는 것을 확인하였다. 따라서 이 방법을 통하여 다양한 상황의 일반적인 물체 분류할 수 있을 것으로 기대한다.

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Synthesis of Pyrimidines and Heteroannulated Pyrimidine Ring Systems (Pyrimidines과 pyrimidine의 헤테로고리의 합성)

  • Mohammed, F.K.;Badrey, M.G.
    • Journal of the Korean Chemical Society
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    • v.55 no.2
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    • pp.218-229
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    • 2011
  • We have involved the imine compound 1 in condensations with various nitrogenous reagents including hydrazine hydrate to construct differently substituted pyrimidines. One of the pyrimidines so obtained was further subjected to interactions with different reagents such as propionic acid, formic acid, ethyl chloroformate, acdetic anhydride, carbon disulphide, cyanogene bromide, triflauroacetic acid and ethyl chloroacetate which resulted in the formation of annulated heterocyclic systems as pairs of isomers in most cases as a result of Dimroth-type rearrangement.

Reactions of Iron Alkynyl(Ethoxy)Carbene Complexes with Amines (철 알킨일(에톡시)카르벤 착물 유도체와 아민의 반응)

  • Park, Jaiwook;Kim, Jinkyung;Jung, Hyunmin
    • Journal of the Korean Chemical Society
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    • v.40 no.8
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    • pp.571-578
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    • 1996
  • Iron alkynyl(amino)carbene complexes, (${\beta}$-aminovinyl)carbene complexes, ${\eta}^3$-(2-(alkylcarbonyl)vinyl)carbene complexes, and a 3-aminoallenylidene complex were formed in the reactions of iron alkynyl(ethoxy)carbene complexes with amines. The ratio of the products, which were formed by substitution reaction, the Michael addition of amines, rearrangements after the addition reaction, and the addition followed by the elimination of the ethoxy group, respectively, was dependent on reaction temperature, the substituent of the alkynyl moiety, and employed amines.

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Substituent Effects on the Wallach Rearrangement of 4'-Halogenated Azoxybenzenes in Conc. Sulfuric Acid : Reaction Mechanism and Linear Free Energy Relationship (황산 수용액내에서 4'-Halogenated Azoxybenzenes의 Wallach Rearrangement 반응에 대한 치환체효과 : 반응메카니즘과 Linear Free Energy Relationship)

  • Keum Sam-Rok;Lee Hyo-Il
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.148-153
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    • 1993
  • The Wallach rearrangement of 4'-halogenated azoxybenzenes in strong sulfuric acid was reinvestigated by UV-Vis spectrophotometric method. Interestingly an excellent linearity $(logk_{obs}=-0.61\;{\sigma}_R{^+} -3.29,\;{\gamma = 0.998)$ was obtained on plotting log (rate) vs. substituent constant, ${\sigma}_R{^+}$, which is known as the Pi delocalization parameter. Thus B-H mechanism via a charged intermediate $(DC^{++})$, which can be largely stabilized by resonance, is far more favored for the Wallach rearrangement.

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Ozone Oxidation of Trans-3-hexene with/without Pyridine (Pyridine 존재여부에 따른 Trans-3-hexene의 오존 산화 반응)

  • Kim, Chul G.;Hong, Won P.
    • Applied Chemistry for Engineering
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    • v.3 no.4
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    • pp.579-587
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    • 1992
  • It was explored, whether the usual course of the ozonolysis of olefins can be modified with the help of pyridine. In the First step, the ozone oxidation of trans-3-hexene was performed with and without pyridine in the inert solvents n-pentane and dichloromethane. In addition, base catalyzed decompositions of monomeric and polymeric ozonides were also examined to identify the reaction mechanism. The reaction products were identified by modern analytical tools. The results of this work showed that reactions of ozone with olefins in the absence of pyridine in aprotic solvents gave, one hand, dominantly peroxidic products, namely monomeric and polymeric ozonides. The other hand, they in the presence of pyridine gave only the non-peroxidic products, namely propionaldehyde and rearranged propionic acid without peroxidic products. It seems, also, that the pyridine-catalyzed isomerization of the Criegee zwitterion of trans-3-hexene to give propionic acid takes place in the ozone oxidation of trans-3-hexene.

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Studies on the Desulfurization of 1,3,4-Oxathiazol-2-one and 1,2,4-Dithiazol-3-one with Trivalent Phosphorus Compounds (1,3,4-옥사티아졸-2-온과 1,2,4-디티아졸-3-온의 3가인 화합물과의 탈황반응에 관한 연구)

  • Dong Young Oh;Chung Ryeol Kim
    • Journal of the Korean Chemical Society
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    • v.27 no.5
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    • pp.368-375
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    • 1983
  • The reactions of various 5-aryl-1,3,4-oxathiazol-2-ones with triethylphosphite resulted in the formation of the corresponding benzonitriles and ethylphosphorothioate by desulfurization reaction in 66∼94% yields. 5-(4-Nitrophenyl)-1,3,4-oxathiazol-2-one was also reacted with trimethylphosphite, triethylphosphine, and triphenylphosphine to give 4-nitrobenzonitrile. But it did not react with triphenylphosphate. The reactions of 5-(4-bromophenyl)-1,2,4-dithiazol-3-one with triphenylphosphine resulted in the formation of 4-bromothiobenzoyl isocyanate and triphenylphosphine thioxide. The thioacyl isocyanate was fragmented into nitrile in ether but was stable in chloroform. This desulfurization reaction observed in each reaction may proceed by the intramolecular rearrangement after insertion of the phosphorus compound into the ring. The stable thioacyl isocyanate in chloroform reacted with imine to give 1,3,5-thiadiazin-4-one via 1,4-cycloaddition reaction.

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