• 제목/요약/키워드: 1,4-Diketones

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Palladium Catalyzed Carbonylative Vinylation of Aryl Halides with Olefins and Carbon Monoxide

  • Kim, Jin-Il;Ryu, Cheol-Mo
    • Bulletin of the Korean Chemical Society
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    • 제8권4호
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    • pp.246-250
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    • 1987
  • The reaction of aryl iodides or bromides with olefins in the presence of 1 mol % of $PdCl_2(PPh_3)_2$ and 3 equiv. of $n-Bu_3N\; at\; 100^{\circ}C$ in carbon monoxide atmosphere gave the corresponding aryl vinyl ketones in good yields with small amount of vinylated 1-aryl olefins. But, when the reaction was proceeded under the 10 atm of carbon monoxide, aryl vinyl ${\alpha}$-diketones and aryl vinyl ketones were obtained in moderate to good yields. The reaction was tolerant of a wide variety of functional groups on either the aryl halides or olefin compounds. Reactivity of aryl halide decrease in the order; aryl iodide > aryl bromide ${\gg}$aryl chloride. In general, the reaction proceeded well and gave good yields of aryl vinyl ketones and aryl vinyl ${\alpha}$-diketones when reactants are substituted with electron withdrawing groups.

전이금속촉매-일산화탄소-물계에 의한 카르보닐화합물의 이중 히드로히드록시메틸화 반응 (Transition Metal Catalyzed the Double Hydrohydroxymethylation of Carbonyl Compounds by a Carbon Monoxide-Water System)

  • 심상철;민경은;허근태
    • 대한화학회지
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    • 제30권1호
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    • pp.101-104
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    • 1986
  • 아디파알데히드, 구르타르알데히드 및 숙신알데히드와 같은 디알데히드는 물-에톡시에탄올 및 에탄올내에 촉매량의 육로듐 십육카르보닐 또는 오카르보닐철의 존재하, 70기압, 일산화탄소, 180$^{\circ}C$, 4시간동안 반응시켜 쉽게 환원되어 대응하는 1,6-헥산디올 및 1,5-펜탄디올 및 1,4-부탄디올이 좋은 수득율로 얻어졌다. 같은 조건하에서 2,5-헥산디온, 2,4-펜탄디온도 대응하는 디올이 보통 수득율로 얻어졌다. 디알데히드의 이중 히드로히드록시메틸화 반응에 대해서는 금속카르보닐 촉매가 다른 촉매보다 더욱 활성적이다. 특히 벤조퀴논은 정량적으로 히드로퀴논을 주었다.

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Efficient One-Pot Synthesis of Acridinediones by Indium(III) Triflate-Catalyzed Reactions of β-Enaminones, Aldehydes, and Cyclic 1,3-Dicarbonyls

  • To, Quang Huy;Lee, Yong-Rok;Kim, Sung-Hong
    • Bulletin of the Korean Chemical Society
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    • 제33권4호
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    • pp.1170-1176
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    • 2012
  • An efficient one-pot synthesis of acridinediones by $In(OTf)_3$-catalyzed reactions was developed starting from ${\beta}$-enaminones, aldehydes, and cyclic 1,3-diketones. The key strategies of these reactions involve domino Knoevenagel condensation/Michael addition/cyclodehydration reaction.

Study on the Development of CVD Precursors I-Synthesis and Properties of New Titanium β-Diketonates

  • 홍성택;임종태;이중철;Ming Xue;이익모
    • Bulletin of the Korean Chemical Society
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    • 제17권7호
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    • pp.637-642
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    • 1996
  • Preparation and properties of potential CVD (Chemical Vapor Deposition) precursors for the TiO2, a major component of the perovskite materials such as PT, PLT, PZT, and PLZT were investigated. Reactions between β-diketones and TiMe3, formed in situ failed to produce stable Ti(β-diketonate)3 complexes but a stable purple solid, characterized as (OTi(BPP)2)2 (BPP=1,3-biphenyl-1,3-propanedione) was obtained when BPP was used. Several new Ti(Oi-Pr)2(β-diketonate)2 complexes with aromatic or ring substituents were synthesized by the substitution reaction of Ti(OiPr)4by β-diketones and characterized with 1H NMR, IR, ICP, and TGA. Solid complexes such as Ti(Oi-Pr)2(BAC)2 (BAC=1.-phenyl-2,4-pentanedione), Ti(Oi-Pr)2(BPP)2, Ti(Oi-Pr)2(1-HAN)2 (1-HAN=2-hydroxy-1-acetonaphthone), Ti(Oi-Pr)2(2-HAN)2 (2-HAN=1-hydroxy-2-acetonaphthone), Ti(Oi-Pr)2(ACCP)2 (ACCP=2-acetylcyclopentanone), and Ti(Oi-Pr)2(HBP)2 (HBP=2-hydroxybenzophenone) were found to be stable toward moisture and air. Ti(Oi-Pr)2(ACCP)2 and Ti(Oi-Pr)2(HBP)2 were proved to have lower melting points and higher decomposition temperatures. However, these complexes are thermally stable and pyrolysis under an inert atmosphere resulted in incomplete decomposition. Ti(Oi-Pr)2(DPM)2 (DPM=dipivaloylmethane) and Ti(Oi-Pr)2(HFAA)2 (HFAA=hexafluoroacetylacetone) were sublimed substantially during the thermal decomposition. Pyrolysis mechanism of these complexes are dependent on type of β-diketone but removal of Oi-Pr ligands occurs before the decomposition of β-diketonate ligands.

Novel Conversion of 2-(4-Dimethylaminoaryl)-1,4-diphenylbutane-l,4-diones into 3-(4- Dimethylaminoaryl)-l-phenylpropenones via Debenzoylation and Oxidation

  • Kim, Sung-Sik;Chang, Ji-Ae;Kim, Ae-Rhan;Cho, Kyung-Won;Park, Sang-Kyu
    • Journal of Photoscience
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    • 제12권2호
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    • pp.109-111
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    • 2005
  • It was found that 1,4-diketones such as 1,4-diphenyl-l,4-butanediones containing N,N-dimethylaminophenyl (pDPB) and N,N-dimethylaminonaphthyl (nDPB) at C2 are converted into 3-(4-dimethylaminoaryl)-1-phenylpropan-lones (pPPA and nPPA) by treatment with $Ca(OH)_2$ in methanol, which was easily oxidized to enone, i.e., 3-(4-dimethylaminophenyl)-l-phenylpropenones (pPPE and nPPE), when treated with 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ) in dichloromethane.

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Photoaddtion Reactions of ο-Benzoquinones to Some Olefins and Alkynes

  • Kim, Sung-Sik
    • Journal of Photoscience
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    • 제5권4호
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    • pp.143-148
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    • 1998
  • Photoaddition reactions of ο-benzoquinones to some organic molecules were ivestigated to yield three types of photoadducts. Irradiation (350nm UV light) of a dichloromethane solution of tetrahal-1, 2- benzoquinones and 1, 4-diphenylbutadiene yielded 1, 3-dienes, which was found to be used to synthesize 1-phenylphenanthrenes. The 1, 3-dienes were also produced, when irradiated tetrahalo--1, 2-benzoquinones and 1,4-dipenylbut-1-en-3-yne in the similar conditions, which was applied to get 9-phenylphenanthrenes. An enolic compound come from the tautomerization of dibenzoylmethane was found to add to ο-benzoquinones to give, 1, 4-dioxenes and 1, 5-diketones as the major products. Although depenylbutadiyne did not add to ο-benzoquinones, diphenylacetylene added to ο-benzoquinones to give $\rho$-quinomethanes as well as two isomeric $\rho$-quinomethanes. One-way photoisomerism was observed for two isomeric $\rho$-quinomethanes.

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Synthetic Studies on Fused Nitrogen-heterocycles from N-Amino-N,N $^\prime$-dihydrodiazinediones (I). Condensation of N-Amino-N,N $^\prime$-dihydrodiazinediones with 1,3-Dicarbonyl Compounds

  • Shin, Sung-Chul;Lee, Youn-Young
    • Bulletin of the Korean Chemical Society
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    • 제9권6호
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    • pp.359-362
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    • 1988
  • The condensation of 1-amino-1,2-dihydro-3,6-pyridazinedione (1) and 2-amino-2,3-dihydro-1,4-phthalazinedione (2) with 1,3-diketones or 1,3-dialdehydes in polyphosphoric acid gave 6,9-dihydro-6,9-dioxopyridazino [1,2-a][1,2,3]triazines (3-6) and 6,11-dihydro-6,11-dioxo[1,2,3]triazino[1,2-b]phtha lazines (7-10), respectively. The condensation of 2 with 2,4-pentanedione in acetic acid gave N-alkylidene intermediate (11), which was cyclized to 9 by treatment with polyphosphoric acid.

Synthesis of Some New 4H-(Pyrano and/or Piperidino)[3,2-d] Pyazoles and Pyrazolo[5,4-d] Thiopyrans

  • Etman, H.A.;El-Ahl, A.S.;Metwally, M.A.
    • Archives of Pharmacal Research
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    • 제17권4호
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    • pp.278-280
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    • 1994
  • 1,5-diketones(3) undewent cyclization to 4H-pyrano[3,2-d]pyrazoles (4a-d),4H-piperidino[3, 2-d]pyrazole (5) and pyrazolo[5,4-d]thiopyran (6) upon treatment with P/sub 2/O/sub 5/, CH/sub 3/COONH/sub 4/ and /or P/sub 2/S/sub 5/. Moreover, treatment of (4) with CH/sub 3/COONH/sub 4/ and/or P/sub 2/S/sub 5/ afforded (5) and (6). The structures of the hitherto unknown ring systems have been confirmed by analytical and spectral data.

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Selective Monobromination of 1,3-Diones with N-Bromosaccharin/Mg(ClO4)2 System in Solution and under Solvent-Free Conditions

  • Alinezhad, Heshmatollah;Tajbakhsh, Mahmood;Tehrani, Shahram Shahriari
    • Bulletin of the Korean Chemical Society
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    • 제32권5호
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    • pp.1543-1546
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    • 2011
  • N-Bromosaccharin/$Mg(ClO_4)_2$ is an effective and regioselective system for ${\alpha}$-monobromination of 1,3-dicarbonyl compounds. A wide variety of ${\beta}$-keto esters and 1,3-diketones in reaction with this system afforded a regioselectively ${\alpha}$-monobrominated products. The bromination reaction can be conducted at 0-5 $^{\circ}C$ either in solution or under solvent-free conditions.