Syntheses and Study of a Pyrroline Nitroxide Condensed Phospholene Oxide and a Pyrroline Nitroxide Attached Diphenylphosphine

The reaction of a diene nitroxide precursor with dichlorophenylphosphine in a McCormac procedure afforded 1,1,3,3-tetramethyl-5-phenyl-1,2,3,4,5,6-hexahydrophospholo[3,4-c]pyrrole-5-oxide-2-oxyl. Lithiation of the protected 3-iodo-pyrroline nitroxide followed by treatment with chlorodiphenylphosphine after deprotection afforded (1-oxyl-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrol-3-yl)diphenylphosphine oxide, and after reduction, (1-oxyl-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrol-3-yl)diphenylphosphine was realized, which was also supported by X-ray single crystal diffraction measurements. This pyrroline diphenylphosphine derivative was converted to hexadecylphosphonium salt, which is an analogue of antineoplastic agent, MITO-CP.     

Polynuclear heterocyclic compounds. XIX. Reduction of 3,3,6,6-tetramethyloctahydroacridine-1,8-diones

Reduction in alcohol solution, using hydrogen at atmospheric pressure and platinum oxide catalyst, of 3, 3, -6, 6-tetramethyl-1, 2, 3, 4, 5, 6, 7, 8-octahydroacridine-1, 8-dione and its 9-phenyl derivative gives the corresponding 3, 3, 6, 6-tetramethyl-1, 2, 3, 4, 5, 6, 7, 8, 9, 10-decahydroacridine-1, 8-dione and its 9-phenyl derivative.For part XVIII see [1].     

Oxidation of bis-arylhydrazones of 3,3-dimethylpentane-2,4-dione with silver oxide

Oxidation of the title bis-arylhydrazones 2 with silver oxide gives 1-aryl-5-arylazo-3,4,4,5-tetramethyl-2-pyrazolines 4 in almost quantitative yield. The spectral data of the pyrazolines 4 as well as the reaction mechanism are discussed.     

Reaction of a free organic radical with grignard reagent

Summary The behavior of a free organic radical 2,2,6,6-tetramethyl-4-piperidone oxide of nitrogen in a Grignard reaction was studied. The reaction with the Grignard reagent proceeded without affecting the free valence and led to a new organic radical with a tertiary hydroxyl group.     

Metathesis of alkenylgermanes on a rhenium oxide catalyst

Conclusions Feasibility was demonstrated for the metathesis of dimethyldiallylgermane on a rhenium oxide/alumina catalyst with the formation of dimethylgermacyclopentene and a linear product, 4,4,9,9-tetramethyl-4, 9-digerma-1,6,11-dodecatriene. The metathesis of trimethylallylgermane leads to the quantitative preparation of 2,2,7,7-tetramethyl-2,7-digerma-4-octene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1892–1894, August, 1984.The authors express their gratitude to T. K. Gar for providing authentic samples of 1,1-dimethyl-1-germaeyclopent-3-ene and 2,2,7,7-tetramethy1-2,7-digerma-4-oetene.     

Photochemical degradation of 2,2,5,5-tetramethyl-4-phenyl-3-imidazoline-1-oxyl

The photochemical degradation of 2,2,5,5-tetramethyl-4-phenyl-3-imidazoline-1-oxyl has been studied in solution at room temperature and in glassy matrices at 77 K. Nitrogen(II) oxide is split from the starting radical during the reaction. The quantum yield of the reaction constitutes ～0.2 in a liquid solution at 298 K and ～0.001 in glassy matrices at 77 K. The kinetics of the solid-phase reaction have a stepped character.     

Kinetics of tautomerization of 1,3,4,7-tetramethylisoindole

The kinetics of transformation of 1,3,4,7-tetramethylisoindole(1)to 1,3,4,7-tetramethyl-1H-isoindole(2)in water or in deuterium oxide at various pH or pD at 25℃ were measuredspectrophotometricalty.The results indicated that the transformation of 1 to 2 could be promotedby acid and base.From the solvent isotope effects and the fact that the 1-position of isoindole nucleusis electron-rich,the mechanism of this transformation is suggested.     

四氮杂大环化合物在有机电致发光器件中的应用(英文)

合成了四氮杂大环化合物,Tetraazamacrocycliccompound,6,12,19,25 tetramethyl 7,11:20,24 dinitrilo dibenzo［b,m］［1,4,12,15］tetra azacyclo docosine(TMCD).TMCD作为电子传送材料,探讨了它在有机电致发光器件中的应用.制作了结构为:玻璃基板／ITO阳极／NPD／Alq／TMCD／LiF／Al阴极的器件.评价的结果显示:该有机电致发光器件在538nm的绿色发光来源于Alq层.它的最大外部量子效率为0.84%,视感效率为1.30lm／W.最先提出了四氮杂大环化合物做为电子传送材料,可应用于电致发光领域.     

Polyamidobenzimidazoles as Polymeric Materials for Cold Climate

A frost-resistant polyamidobenzimidazole-based polymer composite is synthesized from 3,3',4,4'-tetraaminodiphenyl oxide, diphenyl adipate or diphenyl sebacate, and hexamethylenediamine or -caprolactam. As stabilizers for the polymers were used 4-phenyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-1-oxyl and carbon black.     

Synthesis of formyl-substituted porphyrins

Syntheses of 1, 4, 5, 8-tetramethyl-2-ethoxycarbonyl-6-formylporphyrin and 1, 4, 5, 8-tetramethyl-2, 3-diethoxycarbonyl-6-formylporphyrin from the copper complexes of 1, 4, 5, 8-tetramethyl-2-ethoxycarbonylporphyrin and 1, 4, 5, 8-tetramethyl-2, 3-diethoxycarbonylporphyrin are described.     

高通量微孔板DAMBO-P~H荧光检测一氧化氮

一氧化氮(NO)是生物体内的一种重要生物信号传导分子,广泛参与生物体内多种生理及病理过程.为建立快速高效、准确检测生物体释放NO的分析方法,本文选用高灵敏度、高选择性的NO特异性荧光探针8-(3,4-diaminophenyl)-2,6-bis(2-carboxyethyl)-4,4-difluoro-1,3,5,7-tetramethyl-4- bora-3a,4a-diaza-s-indacene (DAMBO-P~H),激发波长和发射波长分别为520 nm和535 nm,以高通量微孔板(384孔)作为实验工具载体.该方法荧光强度与NO浓度在8.0×10~(-10)～8.0×10~(-7) mol·~(-1)范围内呈良好线性关系,R=0.9989,检出限为0.18 nmol·~(-1),回收率为98%～102%.该方法应用于多种生物样品中释放NO的分析检测,结果令人满意.     

Solvent extraction of some metals from aqueous solutions

The results for the extractions of divalent (manganese, cobalt, zinc and cadmium) and trivalent (gallium and indium) metals and hexavalent uranium from aqueous solutions by various extractants such as organophosphorus compounds (tributyl phosphate, trioctylphosphine oxide, di-(2-ethylhexyl)phosphoric acid and 2-ethylhexyl 2-ethylhexylphosphonic acid), sulfur-containing compound (dihexyl sulfoxide), high-molecular weight amines (trioctylamine and trioctylmethylammonium chloride) and 7-alkylated hydroxyquinoline (7-(5,5,7,7-tetramethyl-1-octen-3-yl)-8-hydroxyquinoline are discussed in the viewpoint of separation chemistry.     

Boron-containing novolac resins as flame retardant materials

Boron-containing novolac resins were prepared from novolac resins and bis(benzo-1,3,2-dioxaborolanyl)oxide and bis(4,4,5,5-tetramethyl-1,3,2-dioxa-borolanyl)oxide. The reaction of the model compound 2,6-dimethylphenol with these organoborates was complete but when the novolac resin was reacted, the degree of modification was moderate, even when there was an excess of boron compounds. The thermal degradation was investigated by TGA and pyrolysis, collecting volatiles which were investigated by GC-MS analysis, and the various compounds detected at different degradation temperatures were shown. The thermal degradation under air showed that the presence of boron is significant in the residue at high temperature. LOI values were high. Correlations between the high char yields and LOI values mean that the flame retardancy of the novolac resins improves when they are modified with bis(benzo-1,3,2-dioxaborolanyl)oxide.     

Hypervalent iodine oxidation. Synthesis of spin labeled, 1-oxyl-2,2,6,6-tetramethylpiperidine derivatives

Oxidation of 1-oxyl-2,2,6,6-tetramethyl-4-piperidone ( 1 ) with [I,I-bis(acetoxy)iodo]benzene in methanolic potassium hydroxide yields 1-oxyl-4,4-dimethoxy-3-hydroxy-2,2,6,6-tetramethylpiperidine ( 2 ). Treatment of 2,2,6,6-tetramethyl-4-piperidone ( 3 ) with [I,I-bis(acetoxy)iodo]benzene in methanolic potassium hydroxide gave 3-methoxy-2,2,6,6-tetramethyl-4-piperidone ( 4 ) which on oxidation with 30% hydrogen peroxide and catalytic amount of sodium tungstate gave 1-oxyl-3-methoxy-2,2,6,6-tetramethyl-4-piperidone ( 5 ). The esr spectra of 1-oxyl-4,4-dimethoxy-3-hydroxy-2,2,6,6-tetramethylpiperidine ( 2 ) as well as 1-oxyl-3-methoxy-2,2,6,6-tetramethyl-4-piperidone ( 5 ) show three lines.     

Preparation and characterization of a novel star ABC triblock copolymer of styrene,ethylene oxide,and methacrylic acid

The preparation of a star triblock copolymer based on polystyrene, poly(ethylene oxide), and poly(methacrylic acid) blocks (S-St-EO-MAA) is described. The polymer structure was achieved by the following route: the polystyrene macroanion (PS_m) was formed first by a butyllithium-initiated polymerization of styrene and capping with Michler's ketone; the resulting N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethanol (TDDM)-terminated polystyrene was further reacted with metal potassium. The oxo-anion initiated the ring-opening polymerization of ethylene oxide, and the desired ABC triblock copolymer was obtained by precipitation polymerization of methacrylic acid (MAA) initiated with a charge transfer complex (CTC) under UV irradiation using benzene as a solvent. The complex is composed of PS-b-PEO with a TDDM end group (PS-b-PEO_tm) and benzophenone (BP).     

Formation of water-soluble vitamin derivatives from lipophilic vitamins by cultured plant cells

Glycosylation of vitamin E, its homologues, and vitamin A by cultured plant cells of Phytolacca americana and Catharanthus roseus was investigated to produce water-soluble vitamin derivatives. Two new compounds, that is, 2,5,7,8-tetramethyl-2-(4-methylpentyl)chroman-6-yl β-d-glucopyranoside and 2,5,7,8-tetramethyl-2-(4,8-dimethylnonyl)chroman-6-yl β-d-glucopyranoside, together with 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)chroman-6-yl β-d-glucopyranoside were isolated from the cultured cells of P. americana following administration of vitamin E and its homologues, that is, 2,5,7,8-tetramethyl-2-(4-methylpentyl)-6-chromanol, 2,5,7,8-tetramethyl-2-(4,8-dimethylnonyl)-6-chromanol and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-6-chromanol (vitamin E). On the other hand, glycosylation by C. roseus gave two new compounds, that is, 2,5,7,8-tetramethyl-2-(4-methylpentyl)chroman-6-yl 6-O-β-d-glucopyranosyl-β-d-glucopyranoside and 2,5,7,8-tetramethyl-2-(4,8-dimethylnonyl)chroman-6-yl 6-O-β-d-glucopyranosyl-β-d-glucopyranoside, as well. Furthermore, conversion of vitamin A (retinol) by these cultured cells afforded retinyl β-d-glucopyranoside.     

Charge transport and optical properties of MOCVD-derived highly transparent and conductive Mg- and Sn-doped In2O3 thin films

Mg- and Sn-doped In2O3 (MgIn(x)Sn(y)O(z), 6.0 < x < 16.0; 3.0 < y < 8.0) thin films were grown by low-pressure metal-organic chemical vapor deposition using the volatile metal-organic precursors tris(2,2,6,6-tetramethyl-3,5-heptanedionato)indium(III) [In(dpm)3], bis(2,4-pentanedionato)tin(II) [Sn(acac)2], and bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(N,N,N',N'-tetramethylethylenediamine)magnesium(II) [Mg(dpm)2(TMEDA)]. Films in this compositional range retain the cubic In2O3 bixbyite crystal structure. The highest conductivity is found to be approximately 1000 S/cm for an as-grown film with a nominal composition MgIn14.3Sn6.93O(z). Annealing of such films in a vacuum raises the conductivity to approximately 2000 S/cm. The optical transmission window of the present films is significantly wider than that of typical indium tin oxide (ITO) films from 300 to 3300 nm, and the transmittance is also greater than or comparable to that of commercial ITO films.     

Synthesis of substituted 2-arylimino-2,3-dihydro-4H-1,3-thiazines

The synthesis of 3,4,4,6-tetramethyl-2-arylimino-2,3-dihydro-4H-1,3-thiazines, which have a fixed imino structure, was accomplished by two methods: by intramolecular rearrangement of 1,4,6,6-tetramethyl-3-aryl-1,2,3,6-tetrahydropyrimidine-2-thiones and by amination of 3,4,4,6-tetramethyl-2,3-dihydro-4H-1,3-thiazine-2-thione methiodide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 941–943, July, 1972.     

Hydroacridines and related compounds

3,3-Dimethyl-2-oxa-1,2,3,4-tetrahydroacridine and its N-oxide and 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydroacridine N-oxide were synthesized. On heating with acetic anhydride, the N-oxides form, respectively, acetates of 3,3-dimethyl-2-oxa-1,2,3,4-tetrahydro-4-acridinol and 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydro-4-acridinol. Hydrolysis of the acetates gives the alcohols themselves. Oxidation of 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydro-4-acridinol acetate gives the corresponding N-oxide. Oxidation of 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydro-4-acridinol with manganese dioxide gives 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydro-4-acridinone.See [9] for communication VII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1218–1221, September, 1971.