• Title/Summary/Keyword: malononitrile

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A Novel Synthetic Route to Highly Cross-Linked Poly(alkylvinylether)s. Synthesis and Free Radical Polymerization of a Vinyl Ether Monomer Containing Electron Acceptors in Side Chain

  • 이주연;이현주;김무용
    • Bulletin of the Korean Chemical Society
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    • v.17 no.3
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    • pp.257-262
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    • 1996
  • p-(2-Vinyloxyethoxy)benzylidenemalononitrile 2 and methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate 3 was prepared by the condensation of p-(2-vinyloxyethoxy)benzaldehyde 1 with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2 and 3 polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃. The trisubstituted terminal double bond participated in the vinyl polymerization and radical polymerization of 2 and 3 led to swelling polymers 4 and 5 that were not soluble in common solvents due to cross-linking. Under the same polymerization conditions ethylvinyl ether polymerized well with model compounds of p-methoxybenzylidenemalononitrile 6 and methyl p-methoxybenzylidenecyanoacetate 7, respectively, to give 1:1 alternating copolymers 8 and 9 in high yields. Polymers 4 and 5 showed a thermal stability up to 300 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 8 and 9 were soluble in common solvents such as acetone and DMSO, and the inherent viscosities of the polymers were in the range of 0.36-0.74 dL/g. Films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 59-60 ℃.

A Novel Synthetic Route to Highly Cross-Linked Poly(vinyl ethers): Ⅲ. Synthesis and Free Radical Polymerization of Aryloxyethyl Vinyl Ethers Having an Electron Acceptor in ortho- or meta-Position

  • 이주연;김무용;안광덕
    • Bulletin of the Korean Chemical Society
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    • v.18 no.3
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    • pp.318-323
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    • 1997
  • ο-(2-Vinyloxyethoxy)benzylidenemalononitrile (3a) and methyl ο-(2-vinyloxyethoxy)-benzylidenecyanoacetate (3b), m-(2-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl m-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b) were prepared by the condensation of ο-(2-vinyloxyethoxy)benzaldehyde (1) and m-(2-vinyloxyethoxy)benzaldehyde (2) with malononitrile or methyl cyanoacetate, respectively. Bifunctional vinyl ether monomers 3a and 3b polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃, while meta-isomers 4a and 4b gave lower yields of polymers under the same conditions. The polymers 5-6 obtained from the monomers 3-4 were insoluble in common solvents due to cross-linking. Under the same polymerization conditions ethyl vinyl ether polymerized well with model compounds ο-methoxybenzylidenemalononitrile 7a, methyl ο-methoxybenzylidenecyanoacetate 7b, m-methoxybenzylidenemalononitrile 8a, and methyl m-methoxybenzylidenecyanoacetate 8b, respectively, to give 1:1 alternating copolymers 9-10 in high yields. Cross-linked polymers 5-6 showed a thermal stability up to 300 ℃, and showed a double phase degradation pattern in their TGA thermograms. Polymers 5-6 showed broad endothermic bands around 75-110 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 9-10, except copolymer 9b were soluble in common organic solvents. The inherent viscosities of polymer 9-10 were in the range of 0.35-0.62 dL/g. Polymer films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 118-165 ℃.

Synthesis and Characterization of Bis-Thienyl-9,10-anthracenes Containing Electron Withdrawing 2-Cyanoacrylic Acid or 2-Methylenemalononitrile Group

  • Wang, Yuan;Yu, Qu Feng;Park, Hea-Jung;Ryu, Suk-Hwa;Choi, Jung-Hei;Yoon, Ung-Chan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.3081-3089
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    • 2011
  • A series of new bis-thienylanthracene derivatives D1~D5 containing 9,10-antharcene moiety in the center and 2-methylenemalonotitrile or 2-cyanoacrylic acid functional group on the terminal thiophenes were synthesized and characterized by $^1H$-NMR and high-resolution mass spectroscopy. Their optical, electrochemical, and thermal properties were measured. They have absorption ${\lambda}_{max}$ in the range of 437~480 nm and max of $7.4{\times}10^3{\sim}2.0{\times}10^4M^{-1}cm^{-1}$. The substitution of 2-cyanoacrylic acid group allows greater value of ${\varepsilon}_{max}$ than that of 2-methylenemalonotitrile. TGA curves showed that D4 and D5 which have 2-cyanoacrylic acid functional group on the terminal thiophene(s) exhibit good thermal stability and D4 was thermally stable up to $400^{\circ}C$. Their optical properties and LUMO energy levels measured suggest that they can serve as potential candidates for electron donor materials of organic photovoltaic cells (OPVs) or D4 and D5 which contain 2-cyanoacrylic acid group can be used as organic dyes of dye-sensitized solar cells (DSSCs).

Novel Syntheses of 5-Aminothieno[2,3-c]pyridazine, Pyrimido[4',5':4,5]thieno[2,3-c]pyridazine, Pyridazino[4',3':4,5]thieno-[3,2-d][1,2,3]triazine and Phthalazine Derivatives

  • El Gaby, Mohamed S.A.;Kamal El Dean, Adel M.;Gaber, Abd El Aal M.;Eyada, Hassan A.;Al Kamali, Ahmed S.N.
    • Bulletin of the Korean Chemical Society
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    • v.24 no.8
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    • pp.1181-1187
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    • 2003
  • Condensation of 4-cyano-5,6-dimethyl-3-pyridazinone 1 with aromatic aldehydes gave the novel styryl derivatives 2a-c. Refluxing of compound 2a with phosphorus oxychloride furnished 3-chloropyridazine derivative 3. Compound 3 was reacted with thiourea and produced pyridazine-3(2H)thione 4. Thieno[2,3-c]- pyridazines 5a-e were achieved by cycloalkylation of compound 4 with halocompounds in methanol under reflux and in the presence of sodium methoxide. Also, refluxing of compound 4 with N-substituted chloroacetamide in the presence of potassium carbonate afforded thienopyridazines 6a-e. Cyclization of compound 6 with some electrophilic reagents as carbon disulfide and triethyl orthoformate furnished the novel pyrimido[4',5':4,5]thieno[2,3-c]pyridazines 12 and 13a-c, respectively. Diazotisation of compound 6 with sodium nitrite in acetic acid produced the pyridazino[4',3':4,5]thieno[3,2-d][1,2,3]triazines 14a-c. Ternary condensation of compound 1, aromatic aldehydes and malononitrile in ethanol containing piperidine under reflux afforded the novel phthalazines 16a-c. Compound 3 was subjected to some nucleophilic substitution reactions with amines and sodium azide and formed the aminopyridazines 17a, b and tetrazolo[1,5-b]-pyridazine 19, respectively. The structures of the synthesized compounds were established by elemental and spectral analyses.

Synthesis and Characterization of a New Photoconducting Poly(siloxane) Having Pendant Diphenylhydrazone for Photorefractive Applications

  • Lee, Sang-Ho;Jahng, Woong-Sang;Park, Ki-Hong;Kim, Nakjoong;Joo, Won-Jae;Park, Dong-Hoon
    • Macromolecular Research
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    • v.11 no.6
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    • pp.431-436
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    • 2003
  • A new photoconducting polymer, diphenyl hydrazone-substituted polysiloxane, was successfully synthesized by the hydrosilylation method and characterized by FT-IR, $^1$H-NMR, and $^{29}$ Si-NMR spectroscopy. The glass transition temperature (T$_{g}$) of the polysiloxane having pendant diphenyl hydrazone was ca. 62 $^{\circ}C$, which enabled a component of a low-T$_{g}$ photorefractive material to be prepared without the addition of any plasticizers. This polysiloxane, with 1 wt% of $C_{60}$ dopant, showed a high photoconductivity (2.8 ${\times}$ 10$^{-12}$ S/cm at 70 V/${\mu}{\textrm}{m}$) at 633 nm, which is necessary for fast build-up of the space-charge field. A photorefractive composite was prepared by adding a nonlinear optical chromophore, 2-{3-[2-(dibutylamino)-1-ethenyl]-5,5-dimethyl-2-cyclohexenylidene} malononitrile, into the photoconducting polysiloxane together with $C_{60}$ . This composite shows a large orientation birefringence ($\Delta$n = 2.6 ${\times}$ 10$^{-3}$ at 50 V/${\mu}{\textrm}{m}$) and a high diffraction efficiency of 81 % at an electric field of 40 V /${\mu}{\textrm}{m}$.textrm}{m}$.EX>.

The Syntheses of charge transfer dyes and nanofiber formation for recognition and sensing (진단/감응용 전하 이동형 색소의 합성 및 나노 섬유의 제조)

  • Jung, Young-Sun;Park, Joon-Bae;Moon, Hee-Jung;Kim, Sung-Hoon;Bae, Jin-Seok
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2012.03a
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    • pp.48-48
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    • 2012
  • 화학센서는 분석물질과 감응물질간의 화학적 반응을 통해 분석물질을 선택적으로 인지하고 이를 통하여 특정물질을 실시간으로 분석할 수 있는 기술이다. 최근 화학센서로 색소를 이용하여 음이온을 진단/감응하는 기술이 각광 받고 있으며, 더불어 음이온을 선택적으로 인지함에 있어 검출하고자 하는 특정 음이온에 대한 민감도를 높이기 위한 노력이 계속되고 있다. 감응물질로 이용되는 색소는 주로 분자 내 전하 이동형 색소(intramolecular charge transfer dye)로 주위 환경 변화에 민감하게 반응하며, 자극에 따른 변화를 흡수와 발광, 굴절률의 변화 등으로 나타낸다. 또한 다양한 음이온 중 분석물질로써 연구 가치가 큰 음이온에는 플루오린화물(fluoride)이 있다. 이는 플루오린화물이 치아 보호와 골다공증에 중요한 역할을 하는 순기능을 가지는 반면 고농도 상태에서는 불소증(fluorosis)을 비롯한 악영향을 잠재적으로 가지기 때문에 그 양을 인지하는 것이 중요하게 여겨지기 때문이다. 따라서 본 연구에서는 2-(3,5,5-trimethylcyclohex-2-enylidene)-malononitirle과 indole-3-carboxaldehyde를 통하여 분자 내 전하 이동형 색소를 합성하고, $^1H$ NMR, GC-mas, EA로 합성된 색소의 물성을 분석하였다. 우선 반응물인 2-(3,5,5-trimethylcyclohex-2-enylidene)-malononitirle을 합성하기 위해 dimethylfor mamide(DMF) 용매 하에서 isophorone과 malononitrile을 12시간 반응시키고, 얻어진 결과물을 정제한다. 이후 indole-3-carboxaldehyde와 10시간 환류시켜 색소를 얻는다. 합성된 색소는 F 이온 검출에 이용되며, UV-vis 분광법을 이용하여 분석물질에 따른 흡수 정도와 강도 변화를 살펴본다. 연구의 최종적인 목적은 비단 진단/감응 색소의 합성이 아니라 나노 섬유 소재와 색소의 접합을 통해 진단/감응형 나노 섬유를 개발하는 것으로 이를 위해 전기방사법이 이용된다.

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Synthetic method and insecticidal activity of ricinine (Ricinine의 합성법 및 살충활성)

  • Kwon, Oh-Kyung;Lim, Soo-Kil;Choi, Dal-Soon;Kyung, Suk-Hun
    • The Korean Journal of Pesticide Science
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    • v.2 no.1
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    • pp.18-23
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    • 1998
  • In order to obtain leading compound for the development of new pesticide through the organic synthesis of natural products, the synthesis of ricinine, an active compound of Ricinus communis, was established and biological activities of synthetic compounds against insects were examined. The synthetic scheme of ricinine was composed of four steps by the spontaneous condensation of the cyanoacetyl chloride. A modified synthetic process was also estabilshed to enhance the synthetic yield by simple cyclization of ethoxymethylene malononitrile. In the bioassay results of synthetic ricinine and intermediates on four insects, the mortality of ricinine on brown planthopper (BPH, Nilaparvata lugens) and pea weevil(PW, Bruchus rufimanus) was 80% and 75% at the concentration of 1,000 ${\mu}g/ml$ respectively. Chloronorricinine and chlororicinic acid having chloride group in molecular structure gave 60% mortality on two-spotted mite (TSSM, Tetranychus urticae) at the concentration of 500 ${\mu}g/ml$. The mortality of compounds on house mosquito (HM, Culex pipens pallens) was meager at 10 ${\mu}g/ml$ level.

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Non-volatile Molecular Memory using Nano-interfaced Organic Molecules in the Organic Field Effect Transistor

  • Lee, Hyo-Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.31-32
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    • 2010
  • In our previous reports [1-3], electron transport for the switching and memory devices using alkyl thiol-tethered Ru-terpyridine complex compounds with metal-insulator-metal crossbar structure has been presented. On the other hand, among organic memory devices, a memory based on the OFET is attractive because of its nondestructive readout and single transistor applications. Several attempts at nonvolatile organic memories involve electrets, which are chargeable dielectrics. However, these devices still do not sufficiently satisfy the criteria demanded in order to compete with other types of memory devices, and the electrets are generally limited to polymer materials. Until now, there is no report on nonvolatile organic electrets using nano-interfaced organic monomer layer as a dielectric material even though the use of organic monomer materials become important for the development of molecularly interfaced memory and logic elements. Furthermore, to increase a retention time for the nonvolatile organic memory device as well as to understand an intrinsic memory property, a molecular design of the organic materials is also getting important issue. In this presentation, we report on the OFET memory device built on a silicon wafer and based on films of pentacene and a SiO2 gate insulator that are separated by organic molecules which act as a gate dielectric. We proposed push-pull organic molecules (PPOM) containing triarylamine asan electron donating group (EDG), thiophene as a spacer, and malononitrile as an electron withdrawing group (EWG). The PPOM were designed to control charge transport by differences of the dihedral angles induced by a steric hindrance effect of side chainswithin the molecules. Therefore, we expect that these PPOM with potential energy barrier can save the charges which are transported to the nano-interface between the semiconductor and organic molecules used as the dielectrics. Finally, we also expect that the charges can be contributed to the memory capacity of the memory OFET device.[4]

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1,3-bisdicyanovinylindane 색소를 이용한 선택적 $Hg^{2+}$ 감지 특성

  • Kim, Su-Ho;Kim, Young-Sung;Kim, Sung-Hoon;Son, Young-A
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2009.11a
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    • pp.19-20
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    • 2009
  • 최근 화학, 물리, 생명과학, 전기, 전자등의 다양한 분야에 활발하게 연구가 이루어지고 있는 초분자 화학은 선택적 분자인지를 위한 효율적인 골격구조와 나아가 다양한 계에 응용할 수 있다. 초분자 화학의 분자인지 과정의 특징은 일반적으로 수용체 (receptor 혹은 host)가 목표가 되는 기질 (substrate, analyte, 혹은 guest)에 대하여 선택적으로 식별하고 반응하는 것이다. 비공유 결합성 상호작용에 의하여 이루어지는 초분자 화학의 분자 인지 과정의 특징은 일반적으로 수용체 (receptor 혹은 host)가 목표가 되는 기질 (substrate, analyte, 혹은 guest)에 대하여 선택적으로 식별하고 반응하는 것이다. 이는 공유결합을 이용하는 분자화학과는 차별화 된 것이다. 수용체는 간단한 구조의 화합물 및 금속 이온들과 같은 기질과 가역적으로 상호 작용할 수 있는 착물을 형성한다. 최근들어 급격한 산업화가 진행되어 환경문제가 심각하게 대두 되어져 왔고, 그 중에서 특히 수은이나 카드뮴에 의한 질병, 납에 의한 중독 등 중금속에 의한 오염이 크게 나타남에도 불구하고, 현재 그러한 중금속을 검출함에 있어 많은 비용과 시간이 드는 문제점이 있다. 또한 우리에게 이로운 금속은 효율적 분석을 통해 환경계와 의료계에 많은 도움을 줄 것으로 사례되므로 화학센서 기술의 개발은 절실히 요구되어지고 있다. 이에 새로운 1,3-bisdicyanovinylindane 을 통해 $Hg^{2+}$ 금속의 감지 여부 알아보고, 그 특성을 파악하고자 한다. 1,3-indandion (2.18g, 14.9mmol), malononitrile (2.95g, 44.7mmol), ethanol 50ml를 20분간 상온에서 용해시킨다. 후에 sodium trihydrate acetate(3.05g)을 첨가한 후 5시간 동안 환류반응 시킨다. 이 과정에서 얻어진 용액을 필터과정을 통하여 에서 합성 반응 중에 생성된 불순물(1,3-dicyanovinylindane-1-one, monocondensation)을 제거한다. 필터과정을 통해 걸러진 미 반응 물질을 제�G 용반응욕액을 증류수(100ml)를 이용하여 희석시키고 난 후 염산을 이용, 산성화 시켜 고체 생성물을 얻어낸다. 이렇게 생성된 고체 생성물은 다시 필터 및 건조를 통하여 회색의 고체 화합물을 얻어낸다. 1,3-bisdicyanovinylindane과 금속이온에 대한 감응도를 확인하기 위하여 metanol/water(1:2)을 용매로 하여 금속이온의 농도를 변화시켜 발색특성을 살펴보았다. 본 색소화합물과 Hg2+에 대한 UV 흡광도 변화 적정결과와 그 화합물의 상태 살펴본 결과 금속이온이 0.2ml씩 더 참가되면서 색의 변화를 뚜렷하게 나타내었다. 반면 그 밖에 이온($Fe^{3+}$, $Ag^{2+}$, $Pd^{2+}$, $Zn^2$, $Fe^{2+}$, $Cu^{2+}$, $Pb^{2+}$)은 UV 흡광도 변화가 적거나 변화 자체가 없었다. 하지만 과량의 $Fe^{3+}$, $Ag^{2+}$, $Pd^{2+}$는 색상 변화를 나타내었으며,이와 같은 흡광도 변화는 금속에 따라 약간의 차이가 있지만, 420nm를 등흡수점으로 하여, 580nm의 파장 영역에 있는 흡수 밴드의 세기는 감소하는 반면 400nm 파장 영역에 있는 흡수 밴드의 세기가 증가하였다. 1,3-bisdicyanovinylindane 화합물은 다양한 생물계 및 환경계에서 요구되는 micro mol에서 milli mol 농도 영역의 $Hg^{2+}$ 이온의 선택적이고 민감한 검출과 정량적인 분석에 유용하게 사용될 수 있을 것이다.

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Expressions of Laminin-1 in Lung Alveolar Septa after CS gas Exposure in Rats (CS 가스 흡입이 흰쥐의 폐포막내 Laminin-1에 미치는 영향)

  • Chon, Soon-Ho;Paik, Doo-Jin;Lee, Chul Burm;Kim, Hyuck;Chung, Won Sang;Kim, Young Hak;Kang, Jung Ho;Jee, Heng Ok
    • Tuberculosis and Respiratory Diseases
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    • v.59 no.4
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    • pp.397-405
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    • 2005
  • Background : Laminin-1 is known to have regular functions in the development and course of differentiation of the lungs. The morphogenesis and distribution of laminin-1 still remains as a mystery and its distribution and changes in the molecular structure of laminin-1 in the pathogenesis of the lung still is a subject of great controversy. In this study, experiments were done to delineate the distribution and changes in the amount of laminin-1 after inducing inflammation of the lungs by exposing experimental animals to CS gas and especially, to find compositions of laminin-1 within type II pneumocytes. Materials and Methods : The experimental subjects of study were newborn rats and the extracted tissue from the experimental rats were viewed under light microscope and electron microscope after the sections were treated with immunohistochemical methods and immunogold reaction methods using bounded gold particles. Results : 1) Lymphocytes and mononuclear phagocytes invaded the alveolar septa in the 2 day group rats after CS gas exposure and intense interstitial inflammation was seen in the 3 day group. 2) Laminin immunoreactions decreased to a moderate degree in the 2 and 3 day group rats after CS gas exposure and strong laminin immunoreactions were seen again in the 5 and 7 day group rats. 3) Gold particles in basal lamina of the lung blood-air barrier decreased and in the type I pneumocytes decreased in the 2 and 3 day group rats after CS gas exposure. 4) Gold particles were seen only on the surface of the cell membranes of type II pneumocytes of the 1 and 2 day group rats after CS gas exposure. 5) Few gold particles around the lamellar bodies and cytoplasm of type II pneumocytes in the control rat group and at 12 hours after CS gas exposure. Gold particles are seen only on the surface of type II pneumocytes of the 1 and 2 day group rats after CS gas exposure and are evenly distributed in small amounts in the cells of the 3 day group after CS gas exposure. Conclusion : CS gas exposure in the rats caused inflammation of lung alveolar septa and also induced a decrease in laminin-1 in basal lamina and loss of laminin-1 in the cytoplasm of type II pneumonocytes. As the inflammatory cells disappeared, an increase in the distribution of laminin-1 occurred. This reflects tissue regeneration functions of laminin-1 in the pneumocytes of rats and the distribution of laminin-1 in type II pneumocytes can be seen through the electron microscope using immunogold methods.