- Synthesis method of ethylene sulfate
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The invention discloses a synthesis method of ethylene sulfate. The synthesis method comprises the following steps: mixing ethylene sulfite, a first organic solvent, an oxidant calcium hypochlorite solid and a catalyst ruthenium trichloride, adding the mixture into a reaction kettle, and cooling the reaction system to -15 DEG C to 10 DEG C; slowly dropwise adding a certain amount of cold water in a violent stirring state, continuously reacting for 6-10h at the temperature of -10 DEG C to -5 DEG C after dropwise adding is finished, carrying out suction filtration, separating filtrate, washing an organic phase twice by using a small amount of ice water, adding a molecular sieve, performing drying to remove water, performing filtering, performing concentrating, and performing recrystallizing and centrifugal drying to obtain an ethylene sulfate finished product. According to the invention, the synthesis yield of ethylene sulfite is improved; because the common oxidant sodium hypochlorite solution is easy to decompose after being stored at normal temperature, the calcium hypochlorite solid is convenient to store and can be used immediately after being prepared, and the catalyst is less in dosage and low in cost in the oxidation process of ethylene sulfate.
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Paragraph 0027-0032
(2021/04/21)
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- Synthesis process of ethylene sulfate
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The invention discloses a synthesis process of ethylene sulfate. The synthesis process comprises the following steps: dissolving ethylene glycol in an organic solvent, dropwisely adding thionyl chloride, reacting at 5-10 DEG C for 1-1.5 hours while keeping the temperature, adding a sodium carbonate solution to regulate the pH value to 7-8, and standing to stratify to obtain an ethylene sulfite-containing mixed solution; adding a catalyst into the mixed solution containing ethylene sulfite, dropwise adding a 70% tert-butyl hydroperoxide aqueous solution for 0.5-1 hour, reacting at 30-40 DEG C for 1-3 hours after dropwise adding, then adding a sodium sulfite solution, standing for layering, carrying out aqueous phase extraction, combining organic phases, carrying out reduced pressure concentration, and recrystallizing to obtain ethylene sulfate. The mixed solution containing the ethylene sulfite is directly subjected to oxidation reaction, so that the technological process is simplified;70% tert-butyl hydroperoxide aqueous solution and copper chloride are adopted, so that the cost is further reduced; and the obtained ethylene sulfate has high yield and purity.
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Paragraph 0019-0020; 0022-0023; 0025-0026; 0028-0029; 0031
(2021/02/20)
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- Process for preparation of ethylene sulphate
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The present invention relates to a process for preparation of ethylene sulfate, the process comprises the following steps: (1) providing a mixture of an oxidizing agent and an organic solvent, whereinthe oxidizing agent comprises calcium hypochlorite; and (2) adding ethylene sulfite to the mixture to form the ethylene sulfate. According to the method for preparing the ethylene sulfate, a water system heterogeneous oxidation reaction mode adopted in the prior art is avoided. According to the method, the reaction is directly carried out in an organic solvent, so that the practical problem thatthe ethylene sulfate is decomposed in water is solved from the source, the moisture residue and the free acid residue in the product are remarkably reduced, the reaction yield of the ethylene sulfateis improved, and the purity of the product is improved.
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Paragraph 0074-0077; 0081-0084; 0088-0091; 0095-0098
(2020/11/05)
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- Synthesis method of ethylene sulfate
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The invention discloses a synthesis method of ethylene sulfate. The synthesis method comprises the following steps: adding ethylene glycol into a reaction kettle, and cooling the kettle to 35 DEG C orbelow; adding thionyl chloride into the reaction kettle; raising the temperature of the kettle to 45-60 DEG C, and continuously keeping the temperature for 1-3 hours; when the kettle temperature is 30 to 60 DEG C, vacuumizing to -0.05 MPa to-0.1 MPa; recovering the kettle pressure to the normal pressure, dropwise adding alkali liquor into the reaction kettle when the kettle temperature is 10-40 DEG C, and adjusting the pH value of the kettle liquid to 7.5-8; separating out a lower-layer solution to obtain a finished product of ethylene sulfite; adding a sodium hypochlorite solution into the reaction kettle; dissolving the ethylene sulfate crude product in an organic solvent, and adding ice water into the solution; adding a dehydrating agent into the ethylene sulfate organic solution; concentrating and crystallizing the obtained ethylene sulfate organic solution, and drying the obtained solid; dissolving the primary crystal substance in the organic solvent again, and filtering to obtain a white filter cake. The synthesis method has the advantages of high product yield and high product purity.
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Paragraph 0047-0048; 0050-0051; 0053-0054; 0056-0057
(2020/11/25)
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- Synthesis of Cyclic Sulfite Diesters and their Evaluation as Sulfur Dioxide (SO2) Donors
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Although sulfur dioxide (SO2) finds widespread use in the food industry as its hydrated sulfite form, a number of aspects of SO2 biology remain to be completely understood. Of the tools available for intracellular enhancement of SO2 levels, most suffer from poor cell permeability and a lack of control over SO2 release. We report 1,2-cyclic sulfite diesters as a new class of reliable SO2 donors that dissociate in buffer through nucleophilic displacement to produce SO2 with tunable release profiles. We provide data in support of the suitability of these SO2 donors to enhance intracellular SO2 levels more efficiently than sodium bisulfite, the most commonly used SO2 donor for cellular studies.
- Malwal, Satish R.,Pardeshi, Kundansingh A.,Chakrapani, Harinath
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p. 1201 - 1205
(2020/02/04)
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- Synthetic method of battery-grade ethylene sulfate
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The invention relates to a synthetic method of battery-grade ethylene sulfate and belongs to the technical field of lithium battery materials. The synthetic method is characterized by comprising the following steps: mixing glycol with an organic solvent, adding sulfoxide chloride, and adding a deacidification agent; continuing to react at the room temperature, filtering, and distilling, so as to obtain vinyl sulfite; mixing vinyl sulfite with an organic peroxide, and adding an initiator for reaction; and carrying out distillation, suction filtration and recrystallization, so as to obtain battery-grade ethylene sulfate. The synthetic method has the beneficial effects that the conditions are mild, the side reaction is avoided, the craft process is simple, the requirements on equipment and environmental protection are low, the product is easily separated and extracted, the contents of moisture and impurities are low, and the prepared product is high in product.
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Paragraph 0016; 0017; 0018; 0019; 0020; 0021
(2019/04/14)
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- Profiling the oxidative activation of DMSO-F6 by pulse radiolysis and translational potential for radical C-H trifluoromethylation
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The oxidative activation of the perfluorinated analogue of dimethyl sulfoxide, DMSO-F6, by hydroxyl radicals efficiently produces trifluoromethyl radicals based on pulse radiolysis, laboratory scale experiments, and comparison of rates of reaction for analogous radical systems. In comparison to commercially available precursors, DMSO-F6 proved to be more stable, easier to handle and overall more convenient than leading F3C-reagents and may therefore be an ideal surrogate to study F3C radicals for time-resolved kinetics studies. In addition, we present an improved protocol for the preparation of this largely unexplored reagent.
- Santschi, Nico,Jelier, Benson J.,St?helin, Samuel,Nauser, Thomas
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supporting information
p. 9734 - 9742
(2019/12/02)
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- Preparation method of cyclic sulfite
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The invention relates to a preparation method of cyclic sulfite. Cyclic sulfite is shown as a general formula (I), wherein R1, R2, R3, R4, R5 and R6 can be identical or different and respectively refer to hydrogen, halogen atom substituted or unsubstituted C1-4 alkyl or halogen atom substituted or unsubstituted C2-4 alkenyl, and n is 0, 1 or 2. The preparation method includes: using diol shown asa general formula (II) (wherein, R1, R2, R3, R4, R5, R6 and n are identical with the above definition) and thionyl halide as raw materials, and allowing the raw materials to sequentially pass two reaction temperature areas for continuous reaction, wherein temperature of the first reaction temperature area is set within a range of 25-45 DEG C, and temperature of the second reaction temperature areais set within a range of 50-100 DEG C. The preparation method is high in industrialization feasibility, safe, environment-friendly, catalyst-free, low in raw material cost and capable of preparing high-purity cyclic sulfite with high yield.
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Paragraph 0068-0095
(2019/04/06)
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- Method for preparing ethylene sulfate
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The invention relates to a method for preparing ethylene sulfate. According to the technical scheme, the method comprises the following steps: firstly, taking sulfoxide chloride and ethylene glycol asreactive raw materials to carry out a substitution reaction; secondly, adding a catalyst and a buffer agent into the reaction product, and oxidizing with sodium hypochlorite; and thirdly, centrifuging the reactant in the previous step, re-crystallizing, filtering, refining, and drying, thereby obtaining the finished product. The method disclosed by the invention has the beneficial effects that the method has the characteristics of being readily available in reactive raw materials, low in preparation cost, high in molar yield, high in purity of the prepared product and low in moisture content,the reaction can be rapidly and efficiently carried out by the catalyst adopted in the invention, the oxidation time is reduced, and hydrolysis of the ethylene sulfate is reduced. In addition, the mixed aqueous solution of ammonium di-hydrogen phosphate and borax is adopted as a buffer agent needed by oxidation, the oxidative pH value can be effectively controlled to be 6-7, and stable oxidationis promoted. Moreover, by taking magnesium sulfate as a water removal agent, the moisture of the product is controlled to be 50ppm or less.
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Paragraph 0019; 0020; 0021
(2019/04/09)
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- Synthetic method for ethylene sulfite derivative
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The invention relates to a synthetic method for an ethylene sulfite derivative, and belongs to the field of fine chemical synthesis. The synthetic method comprises the following steps: with titanate as a catalyst, carrying out ester exchange on dimethyl sulfite and corresponding glycol to synthesize the target compound, wherein the using amount of the catalyst is 0.01% to 2% of total weight of reactants, and the mole ratio of the used glycol to the used dimethyl sulfite is 1 to 1.2; reacting at the temperature of 80 to 150 DEG C, gradually carrying out fractionation to remove generated methylalcohol, and stopping the reaction when the methyl alcohol is not fractionated any longer; and carrying out vacuum distillation on the reaction product, and collecting the target substance. The methodhas the advantages of no corrosion, high raw material conversion rate, high yield and the like.
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Paragraph 0023-0026
(2018/06/13)
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- Sulfuric acid preparation of vinyl method (by machine translation)
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The invention disclosed sulfuric acid preparation of vinyl method, preparation steps are as follows: (1) the substitution reaction: to thionyl chloride and ethylene glycol as the raw material for the substitution reaction, then the use of deionized water the reaction liquid washing to neutral, then standing, layered separating the sulfurous acid vinyl ester; (2) oxidation reaction: to the sulfurous acid vinyl ester is added in methylene chloride and ferric sulfate solution, then cooling to 0 - 5 °C, then dropwise sodium percarbonate solution, the aqueous phase and the organic phase may be coexistence of the reaction liquid, the reaction fluid settlement, layered separating the aqueous phase, then the organic subtracted pressure distillation, get sulfuric acid ethylene the ester is thick product; (3) refining: sulfuric acid ethylene the ester is thick using dichloromethane to recrystallize the product, to obtain high purity sulfuric acid vinyl ester. The above preparation method has the high molar yield, the product has high purity, low water content, low acid value, preparation and low cost, wherein: molar yield can reach 85% or more, can achieve the purity of 99% or more, the water content ≤ 60 ppm, acid value ≤ 60 ppm. (by machine translation)
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Paragraph 0016
(2017/01/17)
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- Lewis Acid Catalyzed Synthesis of α-Trifluoromethyl Esters and Lactones by Electrophilic Trifluoromethylation
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An electrophilic trifluoromethylation of ketene silyl acetals (KSAs) by hypervalent iodine reagents 1 and 2 has been developed. The reaction proceeds under very mild conditions in the presence of a catalytic amount of trimethylsilyl bis(trifluoromethanesulfonyl)imide (up to 2.5 mol %) as a Lewis acid providing a direct access to a variety of secondary, tertiary, and quaternary α-trifluoromethyl esters and lactones in high yield (up to 98%).
- Katayev, Dmitry,Matou?ek, Václav,Koller, Raffael,Togni, Antonio
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supporting information
p. 5898 - 5901
(2015/12/11)
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- Potent ketoamide inhibitors of HCV NS3 protease derived from quaternized P1 groups
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Blood borne hepatitis C infections are the primary cause for liver cirrhosis and hepatocellular carcinoma. HCV NS3 protease, a pivotal enzyme in the replication cycle of HCV virus has been the primary target for development of new drug candidates. Boceprevir and telaprevir are two novel ketoamide derived inhibitors that are currently undergoing phase-III clinical trials. These inhibitors include ketoamide functionality as serine trap and have an acidic alpha-ketoamide center that undergoes epimerization under physiological conditions. Our initial attempts to arrest this epimerization by introducing quaternary amino acids at P1 had resulted in significantly diminished activity. In this manuscript we describe alpha quaternized P1 group that result in potent inhibitors in the enzyme assay and demonstrate cellular activity comparable to boceprevir.
- Venkatraman, Srikanth,Velazquez, Francisco,Wu, Wanli,Blackman, Melissa,Madison, Vincent,Njoroge, F. George
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scheme or table
p. 2151 - 2155
(2010/06/19)
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- Synthesis of hydroxy sulfonate surfactants
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The selective synthesis of sulfonate surfactants with side chains containing ether- and hydroxy groups was carried out using cyclic sulfates as epoxide analogues. The main chain was elaborated from 1,2-dodecane sulfate by the addition of various hydroxy/alkoxysulfonates. Ethyleneoxy- and 1,2-propyleneoxy- groups were introduced using ethylene sulfate and 1,2-propylene sulfate, respectively.
- Rist, ystein,Carlsen, Per H. J.
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p. 1169 - 1178
(2007/10/03)
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- High yield synthesis of cyclic phosphites, phosphates, sulphites and sulphates of catechol and glycol mediated by hypervalent silicon centres
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Room temperature reactions of both tris(catecholato)silicate, M2[Si(o-C6H4O2)3] {M=Na, Et3NH} and glycolato silicate, K2[Si2(O2C2H4)5] with PCl3, POCl3, SOCl2 and SO2Cl2 proceed exothermally and afford easy isolation of the corresponding cyclic derivatives of catechol/glycol (1-8) in high yield, exemplifying the merit of hypervalent silicon centres in synthesis. (Et3NH)2[Si(o-C6H4O2)3] afford near quantitative conversions.
- Kingston,Sudheendra Rao
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p. 4841 - 4844
(2007/10/03)
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- Reaction of diethylaminosulfur trifluoride with diols
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Diethylaminosulfur trifluoride (DAST) reacts with dialcohols to give difluorides, sulfite esters or cyclic ethers depending on the number of carbons separating the two alcohol groups.Vicinal and 1,3-diols give large amounts of sulfite ester products while butane-1,4-diol gives almost exclusively the cyclic ether tetrahydrofuran.Terminal dialcohols longer than four carbons give primarily difluoride products.Semiempirical calculations indicate a preference for cyclic intermediates when four or less carbons separate the two alcohol moieties.These cyclic intermediates lead directly to the cyclic ethers and sulfite ester products.
- Shellhamer, Dale F.,Anstine, D. Timothy,Gallego, Kelly M.,Ganesh, Brian R.,Hanson, Aaron A.,et al.
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p. 861 - 866
(2007/10/02)
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- The stereospecific synthesis of (2S,3R) 3-carboxyproline and (2S,3R) 3-aminoproline
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Stereospecific syntheses of (2S,3R) 3-carboxyproline and (2S,3R) 3-aminoproline are reported which make use of the stereospecific alkylation of (4S)-N-(t-butyldimethylsilyl)azetidin-2-one 4-carboxylic acid with the cyclic sulfate derived from ethylene glycol.
- Baldwin, Jack E.,Adlington, Robert M.,Gollins, David W.,Godfrey, Christopher R. A.
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p. 5169 - 5180
(2007/10/02)
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- Reactions of N-sulfinylfluoroalkanesulfonyl amines with nucleophiles containing reactive hydrogen
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The reactions of N-sulfinylfluoroalkanesulfonyl amines, RfSO2NSO (1), with malonate or dialkyl phosphite gave 1:1 adducts RfSO2NHS(O)Nu , and with alcohols or phenols formed RfSO2NH2 and the sulfites O=S(OR)2 by double addition .Trans-sulfinylation occurred during the reaction of 1 with anilines (C6H5NH2, 4-FC6H4NH2 and C6F5NH2).
- Li, Ai-Wen,Xu, Bin,Wang, Chao-Xian,Zhu, Shi-Zheng
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- Kinetic resolutions concentrate the minor enantiomer and aid measurement of high enantiomeric purity
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Although many methods can measure enantiomeric purity, only a few can measure high enantiomeric purity, >98% ee, because in most methods the signal for the major enantiomer overwhelms the signal for the minor enantiomer. We use a kinetic resolution to concentrate the minor enantiomer into the product and thereby extend the ability of all existing techniques to measure high enantiomeric purity. The original enantiomeric purity is calculated using the enantioselectivity of the kinetic resolution and the extent of conversion. We verified this method with samples of (1S)-menthol using an acetylation with vinyl acetate catalyzed by lipase from Candida rugosa. The enantiomeric purities determined by capillary gas chromatography directly and after kinetic resolution agreed for samples with 90-99.9% ee. Error analysis suggests that the usual accuracies for conversion and enantiomeric ratio are sufficient for accurate determination of enantiomeric purity with this method. In another example, we used a kinetic resolution followed by a simple optical rotation measurement to accurately quantify 98.5% ee for a commercial sample of (S)-(+)-6-methoxy-α-methyl-2-naphthaleneacetic acid (naproxen). Thus, this kinetic resolution method allows simple techniques such as optical rotation to measure high enantiomeric purity.
- Caron,Tseng,Kazlauskas
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- REACTION OF HYDROXY AND CARBONYL COMPOUNDS WITH SULFUR TETRAFLUORIDE IX. REACTIONS OF GLYCOLS WITH SULFUR TETRAFLUORIDE
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Selective substitution of one of the hydroxyl groups by a fluorine atom occurs in the reactions of 1,2-, 1,3-, and 1,4-glycols with sulfur tetrafluoride under mild conditions.The regioselectivity of substitution in the case of unsymmetrical glycols depends on the electronic nature of the groups present in the molecules of the initial compounds.
- Hassanein, Salah Mohamed,Burmakov, A. I.,Bloshchitsa, F. A.,Yagupol'skii, L. M.
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p. 1473 - 1477
(2007/10/02)
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- COORDINATION AND CATALYTIC REACTIONS OF UNSATURATED COMPOUNDS: IV.* INTERPRETATION OF THE MECHANISM OF EPOXIDATION OF ETHYLENE BY SULFUR DIOXIDE
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Sulfur dioxide reacts with ethylene (but not with higher 1-alkenes) under conditions of heterogeneous catalysis at 300-400 deg C to form ethylene oxide and sulfur together with other products.The epoxidation evidently results from complex formation between the ethylene, sulfur dioxide, and catalyst with subsequent colligation of the C-S bonds, ring enlargement through insertion of an oxygen atom at one of these bonds, and elimination of SO from the unstable cyclic sulfinate.Elemental sulfur is formed in all the secondary transformations (during the decomposition of SO and the reduction of SO2 by the oxirane).
- Devekki, A. V.,Koshelev, Yu. V.,Malov, Yu. I.
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p. 829 - 834
(2007/10/02)
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