• Title/Summary/Keyword: alkyl aluminum

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Chiral Molecular Recognition by Alkoxy-amine-aluminum Derivatives (Alkoxy-amine-aluminum 유도체에 의한 키랄 분자 인식)

  • Kim, Jong-Mi
    • Journal of the Korean Society of Industry Convergence
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    • v.12 no.3
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    • pp.143-147
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    • 2009
  • The enantioselective reduction of representative prochiral alkyl-aryl ketones with a new chiral alkoxy-amine-aluminum derivatives from aluminum hydride and ${\alpha},{\alpha}$-diphenyl-${\beta}$-amino alcohols, such as (S)-(-)-2-amino-3-methyl-1,1-diphenylbutan-1-ol(AMDPB) and (S)-(-)-2-(diphenylhydroxy-methyl)pyrrolidine(DPHMP), in THF at $0^{\circ}C$ was studied. In the reduction of alkoxy-amine-aluminum derivatives, acetophenone, propiophenone, isopropiophenone, and butyrophenone are reduced to corresponding aromatic secoundary alcohols with 34~60 % enantiomeric excess of (S)-isomers. For such ketones, the optical induction was enhanced by increasing a size of alkyl groups.

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Synthesis of Organic Carbonates with Alkyl/aryl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylates and ROH/AlCl3 under Ambient Condition

  • Sung, Gi Hyeon;Kim, Bo Ram;Ryu, Ki Eun;Kim, Jeum-Jong;Yoon, Yong-Jin
    • Bulletin of the Korean Chemical Society
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    • v.35 no.9
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    • pp.2758-2764
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    • 2014
  • We demonstrated the synthesis of organic carbonates using alkyl/aryl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylates and alcohol in the presence of aluminum chloride. Alkyl/aryl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylates were reacted with alcohol in the presence of $AlCl_3$ in toluene at room temperature to afford the corresponding unsymmetric and symmetric organic carbonates in good to excellent yields. These are efficient and convenient processes. Alkyl/aryl 4,5-dichloro-6-oxopyridazine-1(6H)-carboxylates are solid, stable and non-toxic $CO_2/CO_2R$(Ar) source. It is noteworthy that the reaction is carry out under an ambient and acidic conditions, the easy-to prepare and readily available starting materials and the quantitative isolation of reusable 4,5-dichloropyridazin-3(2H)-one.

Proposals for Revising the Occupational Exposure Limits for Aluminum in Korea (국내 알루미늄 노출실태 및 노출기준 개정 제안)

  • Seung Won Kim;Young Gyu Phee;Yong-Joon Baek;Taejin Chung;Hye-Sil Lee
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.34 no.1
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    • pp.85-97
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    • 2024
  • Objectives: This study was intended to investigate the revision status of the occupational exposure standards for aluminum at home and abroad; to investigate worker exposure at domestic aluminum manufacturing and handling workplaces; to conduct social and economic evaluation for the revision of domestic aluminum exposure limits. Methods: We investigated the current status of occupational exposure limits for aluminum at home and abroad, and analyzed supporting data. An exposure survey was conducted targeting domestic aluminum manufacturing and handling workplaces. Based on these, revised aluminum occupational exposure limits were proposed. Results: The major aluminum exposure limits at home and abroad show a notable difference. The toxicity of aluminum, which was revealed through animal experiments and epidemiological investigations. The average concentration of aluminum in the air at 12 workplaces was 0.016 mg/m3, and the maximum was 0.0776 mg/m3. When total dust and respiratory dust were measured side by side and simultaneously for the same process, 12.1% of the total mass concentration of aluminum dust was respiratory dust. As a result of measuring and comparing the size distribution of dust with an optical particle counter in real time, 48.1% of the total dust in the form of welding fume and pyro-powder was respiratory dust. Based on the literature review and workplace survey, three proposals for changing the aluminum exposure limit were proposed. Proposal (1): For all types, 10 mg/m3 is unified as the exposure limit except for soluble salts and alkyls. Proposal (2): 1(R) mg/m3 as the exposure limit for all forms except soluble salts and alkyl. Proposal (3): 1(R) mg/m3 for pyro-powder and welding fume, and 10 mg/m3 for metal dust, aluminum oxide, and insoluble compounds as exposure standards. A pyro-powder was defined as dry aluminum powder of 200 mesh size (74 ㎛) or smaller (larger size classified as metal dust). Reason for setting: In the workplace survey, the ratio of respiratory dust to total dust was analyzed to be about 1:10, so it was judged that the domestic standard and the ACGIH standard were compatible. Conclusions: In all scenarios according to the revision of the exposure standard, the B/C ratio was greater than 1 or only benefits existed, so it was evaluated as sufficiently reasonable as a result of the socio-economic evaluation.

Reaction of Sodium Diethyldihydroaluminate with Selected Organic Compounds Containing Representative Functional Groups

  • Yoon Nung Min;Shon Young Seok;Ahn Jin Hee
    • Bulletin of the Korean Chemical Society
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    • v.13 no.2
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    • pp.199-207
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    • 1992
  • The approximate rates and stoichiometry of the reaction of excess sodium diethyldihydroaluminate (SDDA) with 68 selected organic compounds containing representative functional groups were examined under standard conditions (THF-toluene, $0^{\circ}C$ in order to compare its reducing characteristics with lithium aluminum hydride (LAH), aluminum hydride, and diisobutylaluminum hydride (DIBAH) previously examined, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, thiols and amines evolve hydrogen rapidly and quantitatively. Aldehydes and ketones of diverse structure are reduced rapidly to the corresponding alcohols. Reduction of norcamphor gives 11% exo-and 89% endo-norborneol. Conjugated aldehydes such as cinnamaldehyde are rapidly and cleanly reduced to the corresponding allylic alcohols. p-Benzoquinone is mainly reduced to hydroquinone. Hexanoic acid and benzoic acid liberate hydrogen rapidly and quantitatively, however reduction proceeds very slowly. Acid chlorides and esters tested are all reduced rapidly to the corresponding alcohols. However cyclic acid anhydrides such as succinic anhydride are reduced to the lactone stage rapidly, but very slowly thereafter. Although alkyl chlorides are reduced very slowly alkyl bromides, alkyl iodides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced very slowly; however, tertiary amides take up 1 equiv of hydride rapidly. Tertiary amides could be reduced to the corresponding aldehydes in very good yield ( > 90%) by reacting with equimolar SDDA at room temperature. Hexanenitrile is reduced moderately accompanying 0.6 equiv of hydrogen evolution, however the reduction of benzonitrile proceeds rapidly to the imine stage and very slowly thereafter. Benzonitrile was reduced to give 90% yield of benzaldehyde by reaction with 1.1 equiv of hydride. Nitro compounds, azobenzene and azoxybenzene are reduced moderately at $0^{\circ}C$, but nitrobenzene is rapidly reduced to hydrazobenzene stage at room temperature. Cyclohexanone oxime is reduced to the hydroxylamine stage in 12 h and no further reaction is apparent. Pyridine is reduced sluggishly at $0^{\circ}C$, but moderately at room temperature to 1,2-dihydropyridine stage in 6 h; however further reaction is very slow. Disulfides and sulfoxides are reduced rapidly, whereas sulfide, sulfone, sulfonic acid and sulfonate are inert under these reaction conditions.

A Study on the Control of Microstructures of Polyalphaolefins via Cationic Polymerization (양이온 중합을 이용한 폴리알파올레핀의 미세구조 조절에 관한 연구)

  • Ko, Young Soo;Kwon, Wan-Seop;No, Myoung-Han;Yim, Jin-Heong
    • Polymer(Korea)
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    • v.39 no.2
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    • pp.346-352
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    • 2015
  • Polyalphaolefin (PAO) is a synthetic lubricant that is superior to mineral-based lubricants in the terms of physical and chemical characteristics such as low pour point, high viscosity index (VI), and thermal and oxidation stability. Several kinds of PAOs have been synthesized by using 1-pentene, 1-hexene, 1-octene, or 1-dodecene as monomer with three kinds of aluminum-based Lewis acid catalysts via cationic polymerization. The control of the catalytic performance and physical properties of PAO such like molecular weight, kinematic viscosity, pour point, and viscosity index was done by changing polymerization parameters. The alkyl aluminum halide-based catalysts show better catalytic activity than that of the conventional $AlCl_3$ catalyst. The microstructure of PAO was investigated by means of TOF-MS (time of flightmass spectroscopy) analysis in order to elucidate the correlation between the performances of the lubricant (VI, pour point) and the molecular structure of PAO. The VI of PAO increases with increases in the carbon number of ${\alpha}$-olefin. In other words, the performances of PAO as a lubricant strongly depended on the branch length of PAO.

Fluorophotometric Determination of Basic Drugs with Lumogallion, Superchrome Garnet Y and Their Alkyl Derivatives (루모갈리온, 슈퍼크롬 가넷 와이 및 그 알킬 유도체에 의한 염기성 의약품의 형광정량)

  • 송만영;김동오;이은엽;안문규
    • YAKHAK HOEJI
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    • v.37 no.3
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    • pp.209-215
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    • 1993
  • Basic drugs could be extracted as ion-paired complexes with Lumogallion, Superchrome Garnet Y and their alkyl derivatives from aqueous acid solution, and then determined fluoro-metrically after addition of aluminum ion. The analysis was carried out as follows; To a 1 ml portion of basic drugs (10$^{-9}$~2$\times$0$^{-8}$mole/ml), 1ml of 0.01w/v% fluorescent reagent solution, and 10ml of dichloroethane are added. The mixture is stirred for 1 minute. After standing for a few minutes, the dichloroethane layer is transfered to 1 ml of 0.1w/v% Al(NO$_{3}$)$_{3}$ ethanol solution. After mixing, and standing for 30 minutes at room temperature, the fluorescence intensity is measured with each maximum excitation and emission wavelength. The reagent blank is run through the whole procedure. From the degree of enhancement of fluorescence intensity, hexyl and dodecyl lumogallion and Superchrome Garnet Y were judged to be the useful one of fluorescent reagent for basic drugs analysis.

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Preparation of (n-BuCp)2ZrCl2 Catalyst Supported on SiO2/MgCl2 Binary Support and its Ethylene-1-hexene Copolymerization (SiO2/MgCl2 이원 담체에 담지된 (n-BuCp)2ZrCl2 합성과 에틸렌-1-헥센 공중합)

  • Carino, Ann Charise;Park, Sang Jun;Ko, Young Soo
    • Applied Chemistry for Engineering
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    • v.29 no.4
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    • pp.461-467
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    • 2018
  • In this study, $(n-BuCp)_2ZrCl_2$, was supported on $SiO_2/MgCl_2$ binary support. Before supporting the catalyst, the $SiO_2/MgCl_2$ binary support was surface treated with three different alkyl aluminum compound, namely trimethylaluminum, triethylaluminum, and ethylaluminum sesquichloride. The synthesized surface-treated $SiO_2/MgCl_2$ supported metallocene catalysts were used for the copolymerization of ethylene and 1-hexene. Their catalytic properties and performances were analyzed through BET, XPS analysis, ICP-AES analysis, and FE-SEM. While the resulting copolymers were analyzed through DSC analysis, GPC analysis, 13C-NMR analysis, and FE-SEM. The analysis of synthesized surface-treated $SiO_2/MgCl_2$ supported metallocene catalysts showed that the Zr content of these catalysts is relatively lower compared to that of the catalyst supported on $SiO_2$. This could be attributed to the reduction in the surface area of $SiO_2$ due to the presence of recrystallized $MgCl_2$ and alkyl aluminum. Furthermore, they exhibited a better copolymerization activity compared to that of $SiO_2$ supported catalyst, particularly the EASC-surface treated binary support, which has the highest activity of 1.9 kg PE/($mmol-Zr^*hr$) because EASC acts as a strong Lewis acid. It could also be observed that the larger the ligand of alkyl aluminum used, the rougher the particle surface of the resulting polymer.

Growth of Aluminum Nitride Thin Films by Atomic Layer Deposition and Their Applications: A Review (원자층 증착법을 이용한 AlN 박막의 성장 및 응용 동향)

  • Yun, Hee Ju;Kim, Hogyoung;Choi, Byung Joon
    • Korean Journal of Materials Research
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    • v.29 no.9
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    • pp.567-577
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    • 2019
  • Aluminum nitride (AlN) has versatile and intriguing properties, such as wide direct bandgap, high thermal conductivity, good thermal and chemical stability, and various functionalities. Due to these properties, AlN thin films have been applied in various fields. However, AlN thin films are usually deposited by high temperature processes like chemical vapor deposition. To further enlarge the application of AlN films, atomic layer deposition (ALD) has been studied as a method of AlN thin film deposition at low temperature. In this mini review paper, we summarize the results of recent studies on AlN film grown by thermal and plasma enhanced ALD in terms of processing temperature, precursor type, reactant gas, and plasma source. Thermal ALD can grow AlN thin films at a wafer temperature of $150{\sim}550^{\circ}C$ with alkyl/amine or chloride precursors. Due to the low reactivity with $NH_3$ reactant gas, relatively high growth temperature and narrow window are reported. On the other hand, PEALD has an advantage of low temperature process, while crystallinity and defect level in the film are dependent on the plasma source. Lastly, we also introduce examples of application of ALD-grown AlN films in electronics.

Reaction of Lithium Gallium Hydride with Selected Organic Compounds Containing Representative Functional Groups

  • Choe, Jeong Hun;Yun, Mun Yeong;Yun, Jong Hun;Jeong, Dong Won
    • Bulletin of the Korean Chemical Society
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    • v.16 no.5
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    • pp.416-421
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    • 1995
  • The approximate rates and stoichiometry of the reaction of excess lithium gallium hydride with selected organic compounds containing representative functional groups were examined under the standard conditions (diethyl ether, 0 $^{\circ}C)$ in order to compare its reducing characteristics with lithium aluminum hydride and lithium borohydride previously reported, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, and amines evolve hydrogen rapidly and quantitatively. However lithium gallium hydride reacts with only one active hydrogen of primary amine. Aldehydes and ketones of diverse structure are rapidly reduced to the corresponding alcohols. Conjugated aldehyde and ketone such as cinnamaldehyde and methyl vinyl ketone are rapidly reduced to the corresponding saturated alcohols. p-Benzoquinone is mainly reduces to hydroquinone. Caproic acid and benzoic acid liberate hydrogen rapidly and quantitatively, but reduction proceeds slowly. The acid chlorides and esters tested are all rapidly reduced to the corresponding alcohols. Alkyl halides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced slowly. Benzonitrile consumes 2.0 equiv of hydride rapidly, whereas capronitrile is reduced slowly. Nitro compounds consumed 2.9 equiv of hydride, of which 1.9 equiv is for reduction, whereas azobenzene, and azoxybenzene are inert toward this reagent. Cyclohexanone oxime is reduced consuming 2.0 equiv of hydride for reduction at a moderate rate. Pyridine is inert toward this reagent. Disulfides and sulfoxides are reduced slowly, whereas sulfide, sulfone, and sulfonate are inert under these reaction conditions. Sulfonic acid evolves 1 equiv of hydrogen instantly, but reduction is not proceeded.