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1.
By reaction of N-bromo compounds with iodine among just known ones the following new N-iodo compounds were prepared: N-monoiodocarboxamides [R?CONHJ; R=CH2Cl, CHCl2, CF3, (CH3)3C], hexaiodomelamine and N,N-diiodo-tert.-butylamine · 1/2 J2.  相似文献   

2.
Studies of Polyhalides. 22. On Dimethyldiphenylammoniumpolyiodides (Me2Ph2N)In with n = 3, 13/3, 6, and 8: Preparation and Crystal Structures of a Triiodide (Me2Ph2N)I3, Tridecaiodide (Me2Ph2N)3I13, Dodecaiodide (Me2Ph2N)2I12, and Hexadecaiodide (Me2Ph2N)2I16 The new compounds [(CH3)2(C6H5)2N]I3, [(CH3)2(C6H5)2N]3I13, [(CH3)2(C6H5)2N]2I12 and [(CH3)2(C6H5)2N]2I16 have been prepared by the reaction of dimethyldiphenylammonium iodide [(CH3)2(C6H5)2N]I with iodine I2 in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The structure of the triiodide may be described as a layerlike packing of pairs of nearly linear symmetric anions and tetraedral cations. The tridecaiodide forms zig-zag chains of iodide ions and iodine molecules with the iodide ion also weakly coordinated by two pentaiodide groups. The dodecaiodide is built from two pentaiodide-groups, which are bridged by an iodine molecule and connected with secondary bonds forming double chains. The hexadecaiodide ion forms layers built up from two heptaiodide groups and one iodine molecule. Thus the dimethyldiphenylammonium cation stabilizes a unique series of polyiodides of extraordinary composition and structure.  相似文献   

3.
NEW PHTHALOCYANINE PHOTOSENSITIZERS FOR PHOTODYNAMIC THERAPY   总被引:2,自引:1,他引:2  
Six new aluminum and silicon phthalocyanines have been synthesized and their photocytotoxicity toward V79 cells has been studied. The compounds that have been prepared are: AIPcOSi(CH3)2(CH2),N(CH3)2, I; AIPcOSi(CH3)2(CH2)3N(CH3)3+I?, II; CH3SiPcOSi(CH3)2(CH2)3N(CH3)2, III; HOSiPcOSi(CH3)2(CH2)3N(CH3)2, IV; HOSiPcOSi(CH3)2(CH2)3)3(CH3)3+I?, V; and SiPc[OSi(CH3)2(CH2)3N(CH3)3+I?]2, VI. Relative growth delay values for compounds I-VI and relative cytotoxicity values for compounds I, II, IV, V and VI have been determined. Compounds I and II have been shown to be comparable in photocytotoxicity to what is presumed to be AIPcOH.xH2O, and compound IV has been shown to have greater activity. The classes of compounds to which these six compounds belong appear to have potential for photodynamic therapy.  相似文献   

4.
Perfluoroorgano Tellurium Compounds: New Investigations on the Preparation of Te(Rf)2 and CH3TeRf (Rf = C2F5, C3F7, C6F5) Methyl(perfluoroorgano) tellurium and bis(perfluoroorgano) tellurium compounds are synthesized in high yields from the photochemical or the thermal reactions of (CH3)2 Te with perfluoroorgano iodides in the presence of (C2H5)3N. They are isolated in pure states. Another general method for the preparation of bis(perfluoroorgano) tellurium is the thermal reaction of TeCl4 with bis(perfluoroorgano) mercury. The preparations and properties of the partially new compounds are described.  相似文献   

5.
Hypervalent iodine(III) compounds with tetrazole ligands C6H5I(N4CR)2 (R  CH3, C6H5, 4-CH3C6H4) reacted, in the presence of elemental iodine, with the double bonds in cis-1,4-polyisoprene (polyIP) to afford iodo-tetrazolylated polymers. The alkyl-iodide groups in the products of the polyIP functionalization were utilized as macro chain-transfer agents for the iodine-transfer polymerization of methyl methacrylate, which yielded brush polymers with well-defined poly(methyl methacrylate) side chains. In addition, the iodo-tetrazolylated polymers were reacted with NaN3 in DMF at room temperature, and it was noticed that, in addition to nucleophilic substitution, elimination reactions took place. However, the presence of azide groups was taken advantage of and successful click chemistry-type of grafting-onto reactions were carried out with alkyne-capped poly(ethylene oxide) in the presence of CuBr and N,N,N′,N″,N″-pentamethyldiethylenetriamine. The thermal decomposition of both the iodo-tetrazolylated and the azido-tetrazolylated polymers was exothermic, especially for the latter materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 172–180  相似文献   

6.
The reactions between dichloromethylgallane and the silyl sulfides (CH3)3SiSR (R = CH3, C2H5, n-C3H7, i-C3H7, Ph and CH2Ph) in benzene result in the formation of the hitherto unknown, extremely moisture-sensitive chloro(methyl)(organylthio)gallanes. Reactions of these thiogallanes with the donor compounds N(CH3)3 and O(CH3)2 are reported. Spectra as well as some physical and chemical properties of the new compounds are given.  相似文献   

7.
Trivalent-Pentavalent Phosphorus Compounds/Phosphazenes. IV. Preparation and Properties of New N-silylated Diphosphazenes Phosphazeno-phosphanes, R3P = N? P(OR′) 2 (R = CH3, N(CH3)2; R′ = CH2? CF3) react with trimethylazido silane to give N-silylated diphosphazenes, R3P = N? P(OR′)2 = N? Si(CH3)3 compounds decompose by atmospherical air to phosphazeno-phosphonamidic acid esters, R3 P?N? P(O)(O? CH2? CF3)(NH2). Thermolysis of diphosphazene R3P = N? P(OR′) 2 = N? Si(CH3)3 (R = CH3, R′ = CH2? CF3) produces phosphazenyl-phosphazenes [N?P(N?P(CH3)3)OR′] n. The compounds are characterized by elementary analysis, IR-, 1H-, 29Si-, 31P-n.m.r., and mass spectroscopy.  相似文献   

8.
Summary The equilibrium geometry and barrier to pyramidal inversion of triisopropylamine, N(CH(CH3)2)3, is computed at SCF level of theory. For comparison, results for ammonia NH3 (including a near HF calculation), trimethylamine N(CH3)3 and the three analogous phosphine compounds PH3, P(CH3)3 and P(CH(CH3)2)3 are presented as well.  相似文献   

9.
Different synthetic routes for the preparation of diiodo(methylthio)gallane are given. Some reactions of this compound with Lewis bases, such as O(CH3)2, S(CH3)2, S2(CH3)2, N(CH3)3, P(CH3)3, and other compounds, such as CH3I, CH3OH, C2H5OH, C2H5SH, i-C3H7SH, and C2H5SeH are investigated. Spectra and some physical and chemical properties of the new compounds are reported. The structure of diiodo(methylthio)gallane is discussed in view of some interesting differences of this molecule in solution and in crystal form.  相似文献   

10.
11.
A series of Zr-based UiO-n MOF materials (n=66, 67, 68) have been studied for iodine capture. Gaseous iodine adsorption was collected kinetically from a home-made set-up allowing the continuous measurement of iodine content trapped within UiO-n compounds, with organic functionalities (−H, −CH3, −Cl, −Br, −(OH)2, −NO2, −NH2, (−NH2)2, −CH2 NH2) by in-situ UV-Vis spectroscopy. This study emphasizes the role of the amino groups attached to the aromatic rings of the ligands connecting the {Zr6O4(OH)4} brick. In particular, the preferential interaction of iodine with lone-pair groups, such as amino functions, has been experimentally observed and is also based on DFT calculations. Indeed, higher iodine contents were systematically measured for amino-functionalized UiO-66 or UiO-67, compared to the pristine material (up to 1211 mg/g for UiO-67-(NH2)2). However, DFT calculations revealed the highest computed interaction energies for alkylamine groups (−CH2NH2) in UiO-67 (−128.5 kJ/mol for the octahedral cavity), and pointed out the influence of this specific functionality compared with that of an aromatic amine. The encapsulation of iodine within the pore system of UiO-n materials and their amino-derivatives has been analyzed by UV-Vis and Raman spectroscopy. We showed that a systematic conversion of molecular iodine (I2) species into anionic I ones, stabilized as I⋅⋅⋅I2 or I3 complexes within the MOF cavities, occurs when I2@UiO-n samples are left in ambient light.  相似文献   

12.
Seven R-di-(α-pyridyl) hydroperchlorates (R = (1) CH2, (2) NH, (3) CO, (4) (CH2)2, (5) (CH2)3, (6) (CH2)4 and (7) S-S) were prepared and studied in acetonitrile-d3 solutions by NMR and IR spectroscopy. With the hydroperchlorates of compounds 1 and 4, an equilibrium between non-hydrogen-bonded NH+ groups and intramolecular-bonded NH+ groups is present. With compounds 2, 3 and 5–7, the intramolecular hydrogen bonds are formed quantitatively. In compounds 4–7, the potential wells in these intramolecular structurally symmetrical N+H· N ? N · H+N bonds, are double minima. These hydrogen bonds are easily polarizable. With compounds 1–3, the distance between the N atoms given by the steric conditions of the molecules is smaller than with usual linear hydrogen bonds. Therefore, strong bent intramolecular structurally symmetrical hydrogen bonds are found, with relatively narrow single-minimum potential wells. These bonds cause a band in the region 3000–2500 cm?1 instead of the continuum. Thus they are not easily polarizable.  相似文献   

13.
4-Vinylpyridinium trifluoromethanesulfonate monomers substituted at nitrogen with H, O, CH3, C2H5, C6H13, and C12H25 were synthesized and characterized spectroscopically. Thermal analyses (DSC and TGA) were carried out on all the compounds. The solid monomers (N? H, N? CH3, N? C6H13, and N? C12H25) exhibited endothermic melting followed by exothermic polymerization and exothermic decomposition (>400°C). Liquid N? C2H5 monomer revealed only exothermic polymerization and decomposition. The N? O polymer underwent thermal decomposition below 300°C. The N–C12H25 homopolymer, prepared from monomer in the DSC or in bulk, displayed an unusual thermal transition at 250°C, which has been attributed to a polymer backbone reorientation leading to side-chain ordering of the dodecyl groups.  相似文献   

14.
The vibrational spectra, both i.r. and Raman, of some N-monosubstituted oxamide complexes with Pd(II) and their deuterated derivatives are reported, using ligands which have the general form NH2COCONHR where R = H, CH3, CH2CH3, CH2CH2CH3, NH2, CH2CH2NH2 or CH2CH2OH. The article also reports on the thermal analysis of the compounds, mainly based on thermogravimetric measurements.  相似文献   

15.
Density functional theory method was used to study the heats of formation (HOFs), electronic structure, energetic properties, and thermal stability for a series of bridged ditetrazole derivatives with different linkages and substituent groups. The results show that the ? N3 group and azo bridge (? N?N? ) play a very important role in increasing the HOF values of the ditetrazole derivatives. The effects of the substituents on the HOMO–LUMO gap are combined with those of the bridge groups. The calculated detonation velocities and detonation pressures indicate that the ? NO2, ? NF2, ? N?N? , or ? N(O)?N? group is an effective structural unit for enhancing the detonation performance for the derivatives. An analysis of the bond dissociation energies for several relatively weak bonds suggests that the N? N bond in the ring or outside the ring is the weakest one and the N? N cleavage is possible to happen in thermal decomposition. Overall, the ? CH2? CH2? or ? NH? NH? group is an effective bridge for enhancing the thermal stability of the bridged ditetrazoles. Because of their desirable detonation performance and thermal stability, five compounds may be considered as the potential candidates of high‐energy density materials (HEDMs). These results provide basic information for the molecular design of novel HEDMs. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011  相似文献   

16.
By reaction of primary carboxamides with “dibromoisocyanuric acid” (DBI) N-monobromoamides can be readily obtained as well as the N,N-dibromoamides described in an earlier paper1. Reactions, some of them new, and properties of these compounds are described and compared with those of the N,N-dibromoamides. Like other compounds bearing the NHBr group2, 3 the N-monobromocarboxamides disproportionate at room temperature according to: 2 RCONHBr ? ? RCONH2+RCONBr2. For CH3CONHBr the equilibrium constant was found to beK=0.02. In aqueous solution they behave as weak acids. The dissociation constants of eight compounds [R=?CH3, ?C2H5, ?CH2Cl, ?CHCl2, ?CCl3, ?CF3, ?C(CH3)3 and ?C6H5] were measured: they differ from those of the corresponding carboxylic acids by about three powers of ten.  相似文献   

17.
Thermal decomposition of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW, CL-20) and its oxa-analogs containing four and three nitramine fragments, in the gas phase and in solution predominantly follows the first order kinetics, whereas in the solid phase it proceeds with acceleration. Replacement of the two nitramine groups in the five-membered cycles of the molecule CL-20 by oxa groups practically does not affect the rate of decomposition of oxanitroderivatives in the solid phase. Substitution of the nitro group in one of oxa-nitroderivatives by R = H, NO, COCH3, CH2N(NO2)CH3 differently affects the rate of decomposition. For R = H the rate of decomposition increases; when R = COCH3, CH2N(NO2)CH3, it decreases; for R = NO, the rate of decomposition remains constant. For the studied compounds the activation parameters of thermal decomposition are determined in the solution, the gas phase, and the solid phase. In general, the reactivity of nitramines depends on the length of the weakest bond N-NO2, which is affected by the conformation of the nitro group.  相似文献   

18.
Contributions to the Chemistry of Boron, 134. Adducts of (Dimethylamino)boranes with Aluminium and Gallium Halides2) The (dimethylamino)boranes (CH3)2BN(CH3)2 ( 1 ) and RB[N(CH3)2]2 ( 2, 3 ) form 1 : 1 adducts 1a – c and 2a , b , 3a , b with AlCl3, AlBr3, and GaCl3, respectively, in contrast to B[N(CH3)2]3 ( 4 ) which reacts with GaCl3 to produce a 1:2 adduct 4a . NMR and IR data are in accord with the presence of a simple N – Al or N – Ga coordinative bound for the first two classes of compounds. However, 4a is to be regarded as a tris(dimethylamino)borane-dichlorogallium(1+) tetrachlorogallate containing a bidentate aminoborane component.  相似文献   

19.
Structure and Thermal Decomposition of Bis(triethanolamine)copper(II) Acetate [Cu{N(CH2CH2OH)3}2](CH3COO)2 Bis(triethanolamine)copper(II) acetate [Cu{N · (CH2CH2OH)3}2](CH3COO)2 was prepared using the basic components; the structure was determined by single crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P21/c with a = 9.101 Å, b = 13.136 Å, c = 9.819 Å, β = 111.63°. Details of the synthesis, X-ray data, and the thermal decomposition are reported.  相似文献   

20.
The reactions of the methylhalogenodimethylaminoarsines CH3As-[N(CH3)2]X (X  F, Cl, Br, I) with HY (Y = Cl, Br) yield the methyldihalogenoarsines CH3AsXY. The compounds CH3As[N(CH3)2]X are prepared by the reactions of CH3AsCl2 with HN(CH3)2, CH3As[N(CH3)2]2 with HX (X = Cl, Br) and by exchange reactions between CH3As[N(CH3)2]2 and CH3AsX2 (X = F, Cl, Br, I).  相似文献   

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