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11.
Tetsuji Kametani Shiroshi Shibuya Hideo Sugi Keiichiro Fukumoto 《Journal of heterocyclic chemistry》1973,10(4):451-453
The absolute configuraiton at the C1-position of 1,2,3,4-tetrahydro-1-phenylisoquinolines can be deduced from the CD curves of either the free base or its methiodide. Furthermore, the absolute con figuration of (+)-2-amino-1-(3-hydroxyphenyl)ethanol (V) was revised and found to have R-configuration at the C1 -position. 相似文献
12.
Some molecules with a molecular skeleton similar to that of stilbenes and azobenzenes show orientational disorder in the crystals. If the disorder is dynamic, a conformational interconversion takes place through a pedal motion. In this study X-ray diffraction analyses of (E)-stilbene (1) and azobenzene (2) were carried out at various temperatures. We succeeded in observing thermodynamic nonequilibrium states that were generated by fast freezing of the conformational interconversion at low temperatures. The populations of the two conformers in crystals of 1 at 90 K varied with the cooling rate. Flash cooling of a crystal of 2 from room temperature to 90 K made it possible to observe the minor unstable conformer that does not exist in the equilibrium state at the same temperature. 相似文献
13.
Singlet oxygen was generated by reaction of sodium hypochlorite and hydrogen peroxide in a micro-channel. The two reagent solutions were delivered into the micro-channel by a syringe pump, providing a laminar flow liquid-liquid interface. The chemiluminescence from the singlet oxygen was emitted in the collapse of the interface due to molecular diffusion under laminar flow conditions. The chemiluminescence intensity was observed continuously and stably for each combination of reagents fed into the micro-channel; while, in the normal batch-type reactor the chemiluminescence peaks from singlet oxygen were observed within ca. 5 s. The features of the chemiluminescence emitted under laminar flow conditions were examined by changing the concentrations of sodium hypochlorite and hydrogen peroxide; the concentrations of 2.5 mM sodium hypochlorite and 7.5 mM hydrogen peroxide provided highest chemiluminescence intensities without bubble formation. Also, the effects of beverages, such as green tea, coffee, white wine, red wine, and sake (rice wine), on the chemiluminescence intensity as well as the concentrations of sodium hypochlorite and hydrogen peroxide were examined. The chemiluminescence intensities observed with addition of the beverages to the reagents decreased in the following orders; green tea > coffee > red wine > rice wine > white wine (being added to sodium hypochlorite); coffee > white wine > green tea > red wine > rice wine (being added to hydrogen peroxide). It was found that coffee decreased the chemiluminescence intensity (ca. 33% chemiluminescence decrease) without altering the concentrations of sodium hypochlorite or hydrogen peroxide. The cause of the decrease in chemiluminescence with coffee is discussed. 相似文献
14.
A convenient and one-pot synthetic method of lanthanide thiolate compounds was developed. An excess of metallic samarium, europium, and ytterbium directly reacted with diaryl disulfides in THF to give selectively Ln(II) thiolate complexes, [Ln(SAr)(&mgr;-SAr)(thf)(3)](2) (1, Ln = Sm; 2, Ln = Eu; Ar = 2,4,6-triisopropylphenyl), Yb(SAr)(2)(py)(4) (3, py = pyridine), and [{Ln(hmpa)(3)}(2)(&mgr;-SPh)(3)][SPh] (6, Ln = Sm; 7, Ln = Eu; 8, Ln = Yb; hmpa = hexamethylphosphoric triamide). Reaction of metallic lanthanides with 3 equiv of disulfides afforded Ln(III) thiolate complexes, Ln(SAr)(3)(py)(n)()(thf)(3)(-)(n)() (9a, Ln = Sm, n = 3; 9b, Ln = Sm, n = 2; 10, Ln = Yb, n = 3) and Ln(SPh)(3)(hmpa)(3) (11, Ln = Sm; 12, Ln = Eu; 13, Ln = Yb). Thus, Ln(II) and Ln(III) thiolate complexes were prepared from the same source by controlling the stoichiometry of the reactants. X-ray analysis of 8 revealed that 8 has the first ionic structure composed of triply bridged dinuclear cation and benezenethiolate anion [8, orthorhombic, space group P2(1)2(1)2(1) with a = 21.057(9), b = 25.963(7), c = 16.442(8) ?, V = 8988(5) ?(3), Z = 4, R = 0.040, R(w) = 0.039 for 5848 reflections with I > 3sigma(I) and 865 parameters]. The monomeric structures of 11 and 13 were revealed by X-ray crystallographic studies [11, triclinic, space group P&onemacr; with a = 14.719(3), b = 17.989(2), c = 11.344(2) ?, alpha = 97.91(1), beta = 110.30(2), gamma = 78.40(1) degrees, V = 2751.9(9) ?(3), Z = 2, R = 0.045, R(w) = 0.041 for 7111 reflections with I > 3sigma(I) and 536 parameters; 13, triclinic, space group P&onemacr; with a = 14.565(2), b = 17.961(2), c = 11.302(1) ?, alpha = 97.72(1), beta = 110.49(1), gamma = 78.37(1) degrees, V = 2706.0(7) ?(3), Z = 2, R = 0.031, R(w) = 0.035 for 9837 reflections with I > 3sigma(I) and 536 parameters]. A comparison with the reported mononuclear and dinuclear lanthanide thiolate complexes has been made to indicate that the Ln-S bonds weakened by the coordination of HMPA to lanthanide metals have ionic character. 相似文献
15.
Nobukatsu Nemoto Keiichiro Kakimoto Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(11):1698-1705
This work deals with the cationic ring‐opening polymerization of cyclic thiocarbonates with a norbornene or norbornane moiety, that is, 5,5‐(bicyclo[2.2.1]hept‐2‐ene‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC1 ) or 5,5‐(bicyclo[2.2.1]heptane‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC2 ), respectively. The reaction of TC1 initiated by trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), boron trifluoride etherate (BF3OEt2), or triethyloxonium tetrafluoroborate (Et3OBF4) afforded unidentified products; however, TC1 underwent cationic ring‐opening polymerization with methyl iodide as an initiator to afford polythiocarbonate because the propagating end was stabilized by the covalent‐bonding property. The polymerization of TC2 initiated by TfOH, TfOMe, BF3OEt2, or Et3OBF4 afforded polythiocarbonate with good solubility in common organic solvents and a narrow molecular weight distribution because of the absence of a double‐bond moiety. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1698–1705, 2002 相似文献
16.
Taguchi Y Ohtani H Tsuge S Ishida Y Kimura K Yoshikawa T 《Journal of chromatography. A》2003,993(1-2):137-142
Highly sensitive and specific determination of trace amounts of a polymeric hindered amine light stabilizer (HALS) in polypropylene (PP) materials could be established by improving reactive thermal desorption-gas chromatography (RTD-GC) in the presence of an organic alkali, tetramethylammonium hydroxide. By using nitrogen-phosphorus detection, highly selective detection of the HALS-related components was attained. In addition, the use of a polar poly(ethylene glycol) separation column alleviated the adsorption of minor specific pyrolysis products. This modified RTD-GC method allowed the determination of the polymeric HALS (Mr 1900) in PP even for trace concentrations between 100 and 500 ppm, through observing selectively the characteristic products containing a tetramethylpiperidine moiety, which had been impossible to detect under the previous RTD-GC conditions using a non-polar separation column and conventional flame ionization detection. 相似文献
17.
Kiichiro Matsumura Yuji Atarashi Osamu Fukumoto 《Journal of polymer science. Part A, Polymer chemistry》1969,7(1):311-320
The chemistry of the titanium(III) chloride(AA)–ethylaluminum dichloride–tetrakis-(dimethylamino)silane system for the polymerization of propylene was studied. A complex of ethylaluminum dichloride with tetrakis(dimethylamino)silane was isolated. It was shown that this complex contains ethylaluminum dichloride and tetrakis(dimethylamino)silane in the ratio of 2:1. This complex with titanium(III) chloride is responsible for the polymerization activity. 相似文献
18.
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20.
A stereoselectivity in an intramolecular cycloaddition of the olefinic -quinodimethanes 13 and 23 generated from the thermolysis of optically active 4β-[2-(4-methoxybenzocyclobutenyl)ethyl] -5α-methoxymethyl-3-phenyl-thio-methylenefuran-2-ones 12 and 22, respectively, is studied and a stereoselective synthesis of (+)--4,5-( 4-methoxybenzo) -1β,7aβ-(2α-methoxymethyl-5-oxofuro)hydrindane 1 is also described. 相似文献