• Title/Summary/Keyword: ene-reaction

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Theoretical Studies on the Gas-Phase Pyrolysis of 2-Alkoxypyrimidines, 2-Alkoxypyrazines, 4-Ethoxypyrimidine and 3-Ethoxypyridazine

  • Kim, Chang-Kon;Lee, Bon-Su;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.32-36
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    • 1992
  • The gas-phase pyrolysis reactions of 2-alkoxypyrimidines(II), 2-alkoxypyrazines(III), 4-ethoxypyrimidine(IV) and 3-ethoxypyridazine(V) are investigated theoretically using the AM1 MO method. These compounds pyrolyze in a concerted retro-ene process with a six-membered cyclic transition state (TS). The relative order of reactivity if (IV)>(II)>(III)>(V), which can be rationalized by the two effects arising from electron-withdrawing power of the aza-substituent: (ⅰ) Electron withdrawal from the C-O bond accelerates the rate and (ⅱ) electron withdrawal from the $N^1$-atom, that is participating in the six-membered TS, deactivates the reaction. We are unable to explain the experimental result of the greatest reactivity for pyridazine, (V), with our AM1 results. The reactivity increase accompanied by successive methylation of the ethoxy group, ethoxytert-butoxy, is due to a release of steric crowding in the activation process.

Synthesis of Alternating Head-to-Head Copolymer of Methyl $\alpha$-cyanoacrylate and 2,3-Dihydrofuran. Ring-Opening Polymerization of 3-Methoxy-4-cyano-2,9-dioxabicyclo[4.3.0]non-3-ene

  • Lee, Ju-Yeon;Cho, I-Whan
    • Bulletin of the Korean Chemical Society
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    • v.9 no.3
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    • pp.176-179
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    • 1988
  • 3-Methoxy-4-cyano-2,9-dioxabicyclo[4.3.0]non-3-e ne (1) was prepared by (4 + 2) cycloaddition reaction of methyl ${\alpha}$-cyanoacrylate with 2,3-dihydrofuran. Compound 1 was ring-open polymerized by cationic catalyst such as boron trifluoride etherate to obtain alternating head-to-head (H-H) copolymer (2) of methyl $\alpha$ -cyanoacrylate and 2,3-dihydrofuran. For comparison, head-to-tail (H-T) copolymer (3) was also prepared by free radical copolymerization of the corresponding monomers. The H-H copolymer exhibited minor differences in its $^1H$-NMR and IR spectra, but in the $^{13}C$-NMR spectra significant differences were observed between the H-H and H-T copolymers. All of the H-H and H-T copolymers were soluble in common solvents and the inherent viscosities were in the range 0.2-0.3 dl/g.

Soluble Polyimide Binder for Silicon Electrodes in Lithium Secondary Batteries (리튬이차전지 실리콘 전극용 용해성 폴리이미드 바인더)

  • Song, Danoh;Lee, Seung Hyun;Kim, Kyuman;Ryou, Myung-Hyun;Park, Won Ho;Lee, Yong Min
    • Applied Chemistry for Engineering
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    • v.26 no.6
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    • pp.674-680
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    • 2015
  • A solvent-soluble polyimide (PI) polymeric binder was synthesized by a two-step reaction for silicon (Si) anodes for lithium-ion batteries. Polyamic acid was first prepared through ring opening between two monomers, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCDA) and 4,4-oxydianiline (ODA), followed by condensation reaction. Using the synthesized PI polymeric binder (molecular weight = ~10,945), the coating slurry was then prepared and Si anode was fabricated. For the control system, Si anode based on polyvinylidene fluoride (PVDF, molecular weight = ~350,000) having the same constituent ratio was prepared. During precycling, PI polymeric binder revealed much improved discharge capacity ($2,167mAh\;g^{-1}$) compared to that of using PVDF polymeric binder ($1,740mAh\;g^{-1}$), while the Coulombic efficiency of two systems were similar. PI polymeric binder improved the cycle retention ability during cycles compared to that of using PVDF, which is attributed to an improved adhesion property inside Si anode diminishing the dimensional stress during Si volume changes. The adhesion property of each polymeric binder in Si anode was confirmed by surface and interfacial cutting analysis system (SAICAS) (Si anode based on PI polymeric binder = $0.217kN\;m^{-1}$ and Si anode based on PVDF polymeric binder = $0.185kN\;m^{-1}$).

Addition Polymerization of 5-Norbornene-2-carboxylic Acid Esters Using Palladium Catalyst System: Synthesis of Monomers, Effect of Their Stereochemistry on Polymerization Behavior (Palladium 촉매를 이용한 5-Norbornene-2-carboxylic Acid Esters의 부가 중합: 단량체의 합성, 단량체의 Stereochemistry(Endo-, Exo-이성질체)가 고분자의 중합 거동에 미치는 영향)

  • Chung, Hae-Kang;Shim, Hyoug-Sub;Jeon, Seung-Ho;Kim, Ji-Heung;Nam, Sung Woo;Jeon, Boong Soo;Kim, Young Jun
    • Polymer(Korea)
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    • v.39 no.3
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    • pp.487-492
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    • 2015
  • The effects of chemical structure of alkyl groups of norbornene carboxylic alkyl esters(methyl, octyl, 4-chlorobenzyl) and endo/exo ratios of norbornene monomers on activity of palladium catalyst and polymerization behavior were investigated. Norbornene ester monomers were synthesized from the reaction of 5-norborene-2-carboxylic acid and various alcohols. Polymerization catalyst, di-${\mu}$-chloro-bis(-methoxybicyclo[2,2,1]-hept-2-ene)palladium(II) (DCBMP), was synthesized according to the literature procedure and silver hexafluoroantimonate ($AgSbF_6$) was used as a conjugate anion source. Gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) were the principal techniques for polymer characterization and $^1H$ NMR spectroscopy was used for chemical structures determination of monomers and polymers. For all of the norbonene alkyl esters GPC data showed that when the amounts of endo isomers exceeded those of exo isomers decreased molecular weight polymers were obtained probably due to the decreased catalyst activity. Polymerizations were conducted by varying the monomer/catalyst mole ratios (100:1, 200:1, 300:1). When 300:1 monomer/catalyst ratio was employed it was possible to synthesize high molecular weight ($M_n=27500g/mol$), film forming polymer from exo-norbornene carboxylic acid octyl ester.

A Study on the Bio-Based Polyurethane (바이오 폴리우레탄에 관한 연구)

  • Ko, Jong-Sung;Lee, Jin-Hui;Sung, Ki-Chun
    • Journal of the Korean Applied Science and Technology
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    • v.29 no.3
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    • pp.531-542
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    • 2012
  • The thesis covers the trend of research on bio-based polyurethane which is made from polyols derived mainly from plant oils and isocyanates. Castor oil is a triglyceride of ricinoleic acid containing hydroxyl group. Hydroxylation is done on the unsaturated bonds of the oils by the reactions of epoxidation/ring opening, hydroformylation/hydrogenation, ozonolysis/hydrogenation, and thiol-ene reaction. Polyols from hyperbranch, primary alcohol, polysaccharide have been studied to control the reactivity of the polyol and morphology of the microdomains. Besides, researches cover biodegradable polylactic acid polyol for medical use, fatty acid dimer polyol for the prevention of hydrolysis, and polyol with ionic group for water-borne polyurethane. Bio-based polyurethanes are being used in flexible and rigid foams, coatings, sealants, and elastomers.

Ring-Opening Metathesis Polymerization and Hydrogenation of Ethyl-substituted Tetracyclododecene

  • Kwon, Oh-Joon;Vo, Huyen Thanh;Lee, Sul-Bee;Kim, Tae-Kyung;Kim, Hoon-Sik;Lee, Hyun-Joo
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2737-2742
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    • 2011
  • Ring-opening metathesis polymerization (ROMP) of an ethyl-substituted tetracyclododecene (8-ethyltetracyclo[$4.4.0.1^{2,5}.1^{7,10}$] dodec-3-ene, Et-TCD) was carried out in the presence of a ternary catalyst system consisting of $WCl_6$, triisobutyl aluminium (iso$Bu_3Al$), and ethanol. The optimal molar ratio of Et-TCD/$WCl_3$/iso-$Bu_3Al$/ethanol was found as 500/1/3/2 at which the yield of ring-opened polymer was 100%. 1-Hexene was shown to be an effective molecular weight controlling agent for ROMP reaction of Et-TCD. The hydrogenation of the ring opened polymer (p-Et-TCD) was conducted successfully using Pd(5 wt %)/${\gamma}$-$Al_2O_3$ at $80^{\circ}C$ for 1 h. Chemical structures of p-Et-TCD and its hydrogenated product($H_2$-p-Et-TCD) were characterized using 2D NMR techniques ($^1H-^1H$ COSY and $^1H-^{13}C$ HSQC). The changes of physical properties such as thermal stability, glass transition temperature and light transmittance after the hydrogenation were also investigated using TGA, DSC, and UV.

Synthesis of Protoberberine Derivatives and Their Biological Activities (Protoberberine의 고급지방산 유도체합성 및 활성연구(V))

  • Kim, Sin-Kyu;Kwon, Chang-Ho;Yook, Chang-Soo;Rho, Young-Soo;Seo, Seong-Hoon;Choung, Se-Young;Chung, Sung-Hyun;Kim, Dong-Hyun;Hwang, Soon-Ho
    • YAKHAK HOEJI
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    • v.36 no.1
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    • pp.1-6
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    • 1992
  • Irradiation of phenolbetaine in a stream of nitrogen produced 8,14-cycioberbine[1]. Compound[1] was treated with 10% HCl solution to give the 8-hydroxycycloberbine[2] in 67.7% yield. Subsequently addition of ethylchloroformate to the compound[2] gave rise to the 8-hydroxy-7-ethylcarboxy-9, 10-dimethoxy-2, 3-methylenelioxy-13-oxo-norochotensane[3] in 78% yield. Treatment of the compound[3] with bis-(2-chloroethyl)amine then lead to the 7-bis(2-chloroethyl)carbamyl-norochoteneare[4]. On the other hand the compound[5], which is the 8-methoxynorochotensane, was derived when compound[1] was treated with methanol in a few drops of BF. Treatment of the compound[6], and the compound[7], 7-bis(2-chloroethyl)-carbanyl-8-methoxy-norocheyensane, was then synthesized by reaction of the compound[6] with bis(2-chloroethyl) amine. In the other synthetic pathway when compound[5] was treated with $POCl_3$ in dried benzene, 13-chloro-6-ene-norochetensane[8] with 42% yield was formed. Finally the 13-bis-(2-chloroethyl) amino-8-methoxy-norochotensane[9] was produced when we treated the compound[8] with bis-(2-chloroethyl) amine. In another pathway, reaction between phenolbetaine which is the precursor of the compound[1] and benzoylchloride in dried chloroform gave us the 5,6,7 trihydro-2, 3-methylene-dioxy-9-chloromethyl-10, 11-dimethoxyphenylisoquinoline-8-benzoate[10] in 73% yield. The results of biological activities for these compounds are also presented in Table I and II.

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Developmental Stage-Specific Expression Patterns of c-rn yc and myn Proto-Oncogenes and a Possible Role of myn in Preimplantation Mouse Embryo Development (착상선 생쥐 초기배아에서 c-myc과 myn유전자의 발현 기능에 관한 연구)

  • 이상구;이성호;김경진
    • The Korean Journal of Zoology
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    • v.39 no.4
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    • pp.352-361
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    • 1996
  • The c-myc proto-onco9ene, one of the immediately early genes, is involved in ceflular proliferation and differentiation, and its biologleal function is regulated hy dimerization with a heterodimeric partner, myn. In the present study, gene expression patterns of c-myc and myn during mouse preimplantation embryo development were examined using a semi-quantitative reverse transcription-poiymerase chain reaction (RT-PCR). Myn transcripts were rather constitutively expressed throughout embryonic stages with a slight increase only at biastocyst stage. in contrast, expression of c-myc transcripts wm developmental stage-'pedfic. The c-myc transcripts were detected at 1-cell stage, declined abruptly at 2-cell stage and then increased gradually at blastocyst stage. To examine the possible role of myn during preimpiantation mouse embryo development, two myn antisense oligonucleotides spanning the tail of zipper dognain (myn2; 20-mer) and the second helix domain (myn3; 20-mer) were microinjected into the fertilized 1-cellembryos. Microinjection of myn2 and myn3 resulted in developmental tion at morula/biastocyst transition stage, leading to the fiagentation of embryos. Talien together, these results suggest that c-myc and its heterodimeric partner, myn, are differentially expressed In a developmental stage-dependent manner, and myn may play an important role in mouse preimpiantation embryo development.

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Polydiacetylene-Based Chemo-/Biosensor of Label Free System with Various Sensing Tools (다양한 감지 방법을 갖고 있는 폴리디아세틸렌 기반 비표지 화학/바이오센서)

  • Park, Hyun-Kyu;Park, Hyun-Gyu;Chung, Bong-Hyun
    • KSBB Journal
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    • v.22 no.6
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    • pp.409-413
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    • 2007
  • Polydiacetylene(PDA)-based sensors possess a number of properties that can be successfully applied for label-free detection system. PDA is one of the most attractive color-generating materials, with growing applications as sensors. Here we introduce various PDA-based devices, used as biosensor, chemosensor, thermosensor, and optoelectronics sensor. In general, PDA liposomes and films are closely packed and properly designed for polymerization via 1,4-addition reaction to form an ene-yne alternating polymer chain. PDA-based two/three dimensional structures have been used for colorimetric or fluorescent devices, sensing biological as well as chemical components. This color-generating material also present a very high charge carrier mobility, allowing its application as field-effect transistor (FET). The immobilized PDA structures or films have distinct advantages for the detection of low concentration target molecules over the aqueous solution-based detection systems. In the present review, reported detection methods by using various PDA structures are summarized with updated references.

The embryological studies on the interspecific hybrid of ginseng plant (Panax ginseng x P. Quiuquefolium) with special references to the seed abortion (인삼의 종간잡종 Panax ginseng x P Quinquefoilium의 발생학적 연구 특히 결실불능의 원인에 관하여)

  • Jong-Kyu Hwang
    • KOREAN JOURNAL OF CROP SCIENCE
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    • v.5 no.1
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    • pp.69-86
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    • 1969
  • On the growing of the interspecific hybrid ginseng plant, the phenomena of hybrid vigoures are observed in the root, stem, and leaf, but it can not produce seeds favorably since the ovary is abortive in most cases in interspecific hybrid plants. The present investigation was undertaken in an attempt to elucidate the embryological dses of the seed failure in the interspecific hybrid of ginseng (Panax Ginseng ${\times}$ P. Quinque folium). And the results obtained may be summarized as follows. 1). The vegetative growth of the interspecific hybrid ginseng plant is normal or rather vigorous, but the generative growth is extremely obstructed. 2). Even though the generative growth is interrupted the normal development of ovary tissue of flower can be shown until the stage prior to meiosis. 3). The division of the male gameto-genetic cell and the female gameto-genetic cell are exceedingly irregular and some of them are constricted prior to meiosis. 4). At meiosis in the microspore mother cell of the interspecific hybrid, abnormal division is observed in that the univalent chromosome and chromosome bridge occure. And in most cases, metaphasic configuration is principally presented as 23 II+2I, though rarely 22II+4I is also found. 5). Through the process of microspore and pollen formation of F1, the various developmental phases occur even in an anther loclus. 6). Macro, micro and empty pollen grains occur and the functional pollen is very rare. 7). After the megaspore mother cell stage, the rate of ovule development is, on the whole, delayed but the ovary wall enlargement is nearly normal. 8). Degenerating phenomena of ovules occur from the megaspore mother cell stage to 8-nucleate embryo sac stage, and their beginning time of constricting shape is variously different. 9). The megaspore arrangement in the parent is principally of the linear type, though rarely the intermediate type is also observed, whereas various types, viz, linear, intermediate, Tshape, and I shape can be observed in hybrid. 10). After meiosis, three or five megaspore are some times counted. 11). Charazal end megaspore is generally functional in the parents, whereas, in F1, very rarely one of the center megaspores (the second of the third megaspore) grows as an embryo sac mother cell. 12). In accordance with the extent of irregularity or abnormality in meiosis, division of embryo sac nuclei and embryo sac formation cause more nucellus tissue to remain within th, embryo sac. 13). Even if one reached the stage of embryo sac formation, the embryo sac nuclei are always precarious and they can not be disposed to theil proper, respective position. 14). Within the embryo sac, which is lacking the endospermcell, the 4-celled proembryo, linear arrangement, is observed. 15). Through the above respects, the cause of sterile or seed failure of interspecific hybrid would be presumably as follows, By interspecific crossing gene reassortments takes place and the gene system influences the metabolism by the interference of certain enzyme as media. In the F1 plant, the quantity and quality of chemicals produced by the enzyme system and reaction system are entirely different from the case of the parents. Generally, in order to grow, form, and develop naw parts it is necessary to change the materials and energy with reasonable balance, whereas in the F1 plant the metabolic process becomes abnormal or irregular because of the breakdown of the balancing. Thus the changing of the gene-reaction system causes the alteration of the environmental condition of the gameto-genetic cells in the anther and ovule; the produced chemicals cause changes of oxidatio-reduction potential, PH value, protein denaturation and the polarity, etc. Then, the abnormal tissue growing in the ovule and emdryo sac, inhibition of normal development and storage of some chemicals, especially inhibitor, finally lead to sterility or seed failure. Inconclusion, we may presume that the first cause of sterile or seed abortion in interspecific hybrids is the gene reassortment, and the second is the irregularity of the metabolic system, storage of chemicals, especially inhibitor, the growth of abnormal tissue and the change of the polarity etc, and they finally lead to sexual defect, sterility and seed failure.

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