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1.
Summary White crystalline complexes of general formula Cu2L4X2 (where X = Cl, Br and L = 1, 3-oxazolidine-2-thione, pyrrolidine-2-thione,N-methyl-1,3-imidazolidine-2-thione andN-ethyl-1,3-imidazolidine-2-thione) and CuLX (where L = 1,3-imidazolidine-2-thione) were prepared by reduction of copper(II) halides and studied by i.r. spectroscopy in the 4000–200 cm– range. Evidence for ligand coordination to the metal through sulphur was found in each case. The(CuCI) vibration in all the chloro derivatives falls atca. 240 cm–. 相似文献
2.
N-(1,3-Thiazol-5(4H)-ylidene)amines via 1,3-Dipolar Cycloaddition of Azides and 1,3-Thiazol-5(4H)-thiones Organic azides 5 and 4,4-dimethyl-2-phenyl-1,3-thiazol-5(4H)-thione ( 2 ) in toluene at 90° react to give the corresponding N-(1,3-thiazol-5(4H)-ylidene)amines (= 1,3-thiazol-5(4H)-imines) 6 in good yield (Table). A reaction mechanism for the formation of these scarcely investigated thiazole derivatives is formulated in Scheme 3: 1,3-Dipolar azide cycloaddition onto the C?S group of 2 leads to the 1:1 adduct C . Successive elimination of N2 and S yields 6 , probably via an intermediate thiaziridine E . 相似文献
3.
Simon M. Ametamey Roland Prewo Jost H. Bieri Heinz Heimgartner Jean Pierre Obrecht 《Helvetica chimica acta》1986,69(8):2013-2025
Reaction of 3-(Dimethylamino)-2H-azirines with 1,3-Thiazolidine-2-thione Reaction of 3-(dimethylamino)-2H-azirines 1 and 1,3-thiazolidine-2-thione ( 6 ) in MeCN at room temperature leads to a mixture of perhydroimidazo[4,3-b]thiazole-5-thiones 7 and N-[1-(4,5-dihydro-1,3-thiazol-2-yl)alkyl]-N′,N′-dimethylthioureas 8 (Scheme 2), whereas, in i-PrOH at ca. 60°, 8 is the only product (Scheme 4). It has been shown that, in polar solvents or under Me2NH catalysis, the primarily formed 7 isomerizes to 8 (Scheme 4). The hydrolysis of 7 and 8 leads to the same 2-thiohydantoine 9 (Scheme 3 and 5). The structure of 7a, 8c , and 9b has been established by X-ray crystallography (Chapt. 4). Reaction mechanisms for the formation and the hydrolysis of 7 and 8 are suggested. 相似文献
4.
E. K. Beloglazkina A. A. Chizhevskii V. N. Nuriev R. L. Antipin N. V. Zyk I. V. Chernyshev A. A. Moiseeva K. P. Butin 《Russian Chemical Bulletin》2005,54(12):2757-2770
The reactions of 5-acylpyrimidine-4-thiones with aliphatic diamines in the presence of NiII and CoII salts were studied. New NiII and CoIII complexes with ligands of the pyrimidinethione series were synthesized. The results of the reactions of 5-acetyl-6-methyl-2-phenylpyrimidine-4-thione
and 5-acetyl-2,6-dimethylpyrimidine-4-thione with ethylenediamine or 1,3-diaminopropane in the presence of NiCl2· 6H2O or CoCl2·6H2O depend on (1) the nature of the substituent at position 2 of the pyrimidine ring, (2) the length of the polymethylene bridge
between the nitrogen atoms in the diamine molecule, (3) the nature of complex-forming metal, and (4) the pyrimidinethione:
diamine ratio. The resulting complexes were studied by electrochemical methods. The mechanism of electrooxidation and electro-reduction
of 5-acylpyrimidine-2-thiones and related nickel and cobalt complexes was proposed. The structures of the complexes were investigated
by NMR, UV-Vis spectroscopy, and IR spectroscopy and mass spectrometry. The molecular structure of fac-tris(5-acetyl-2,4-dimethylpyrimidine-6-thiolato)cobalt(III) was established by X-ray diffraction. According to semiempirical
quantum-chemical calculations by the PM3(tm) method, both the highest occupied and lowest unoccupied molecular orbitals in
the molecules of the compounds under study have a π symmetry and are localized predominantly on the ligand fragments.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2666–2678, December, 2005. 相似文献
5.
Subhi A. Al-Jibori Afra S. S. Al-Zaubai Modher Y. Mohammed Talal A. K. Al-Allaf 《Transition Metal Chemistry》2007,32(3):281-286
Palladium(II) and platinum(II) complexes containing the mixed ligands tertiary diphosphines Ph2P(CH2)
n
PPh2, (n = 1–4) and benz-1,3-imidazoline-2-thione, benz-1,3-oxazoline-2-thione or benz-1,3-thiazoline-2-thione have been prepared
and characterized by elemental analysis, magnetic susceptibility, molar conductance and i.r. spectral data. 31P–{1H}-n.m.r. data have been applied to characterize the produced linkage isomers. 相似文献
6.
Anvarhusein A. Isab Abdul R. Al-Arfaj Mohammed Arab Mir M. Hassan 《Transition Metal Chemistry》1994,19(1):87-90
Summary Pd(CN)2 reacts with imidazolidine-2-thione (Imt), 1,3-diazinane-2-thione(Diaz), 1,3-diazipnane-2-thione (Diap) and their derivatives to yield complexes of stoichiometry [PdL2(CN)2] or [PdL(CN)2] (L = Imt, Diaz or Diap and L = Imt having N-Me, Et or Pr substituents), which were characterized by elemental analysis, i.r., 1H and 13C n.m.r. spectroscopy. Both mono- and bis ligand complexes are thought to be square planar with the monoligand binding to metal via sulphur (bridging) and the bis ligand via the monodentate thione group. The 13C enriched Pd(13CN)2 complex was prepared and the 13C n.m.r. recorded. The C-2 resonance of 13C n.m.r. of Imt, Diaz or Diap complexes of the copper(I), silver(I), gold(I) and palladium(II) were compared. 相似文献
7.
M. Sakhawat Hussain M. Latif Hossain Abderehman Al-Arfaj 《Transition Metal Chemistry》1990,15(2):120-125
Summary Novel mixed-ligand complexes of Ag1 and Au1 containing triphenylphosphine (TPP) and heterocyclic thiones, of general formula [TPP–M–L]Cl and [(TPP)2–M–L]Cl, where L=imidazolidine-2-thione (Imt), 1,3-diazinine-2-thione (Diaz) or N-isopropylimidazolidine-2-thione (iPrImt) have been prepared. The spectroscopic data are consistent with S-donation in all complexes. The magnitude of high-field shift in carbon-13 n.m.r. of the thioureide carbon on complexation is interpreted in terms of coordination geometry around the metal atoms. The mixed-ligand complexes are structurally similar to some of the commonly used antiarthritic Au1 drugs and are thus potentially useful in chemotherapy. 相似文献
8.
Nand K. Singh Manoj K. Bharty Surendra K. Kushawaha Ram Dulare Raymond J. Butcher 《Transition Metal Chemistry》2010,35(3):337-344
Three new mixed ligand complexes [Mn(4-pytone)2(bipy)2]bipy (1), [Mn(pot)2(en)2] (2) and [Mn(4-mot)2(en)2] (3) (4-pytone = 5-(4-pyridyl)-1,3,4-oxadiazole-2-thione, pot = 5-phenyl-1,3,4-oxadiazole-2-thione, 4-mot = 5-(4-methoxy-phenyl)-1,3,4-oxadiazole-2-thione)
have been prepared containing bipy/en as coligands. The starting material potassium N-(aryl-carbonyl)-hydrazinecarbodithioates (RCONHNHCSSK) underwent cyclization during complexation in the presence of bipy
or en to give the corresponding 5-aryl-1,3,4-oxadiazole-2-thiones. The complexes have been characterized by physicochemical
techniques and single crystal X-ray structure determination. In all cases, the manganese has a six coordinate octahedral arrangement
coordinated by 4N atoms of two bipy/en and two covalently bonded N atoms of the oxadiazole-2-thione anions. 相似文献
9.
We have obtained 5-(2-pyridyl)[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione for the first time by cycloaddition of 2-ethynylpyridine to 4,5-dihydro-1,3-dithioltrithione (isotrithionedithiol). We have studied this thione, 5-(2-pyridyl)- and 5-(4-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thiones by mass spectroscopy and also IR, UV, 1H and 13C NMR spectra. We have determined the crystal and molecular structure of 5-(2-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 429–434, March, 2005. 相似文献
10.
Additionsreaktion von 1,3-Thiazol-5(4H)-thionen und inaminen; Bildung von Thioamiden und Thioketonen
Addition Reaction of 1,3-Thiazole-5(4H)-thiones and Ynamines; Formation of Thioamides and Thioketones Ynamines and 1,3-thiazole-5(4H)-thiones of type 1 undergo an addition reaction on heating in toluene yielding mainly α,β-unsaturated 2-(4,5-dihydro-1,3-thiazol-5-yliden)thioamides of type 7 (Scheme 2 and Table). In some cases, 1-diethylamino-1-(4,5-dihydro-1,3-thiazol-5-yliden)-2-alkanethiones 8 have been isolated as minor products. In analogy to other reactions of ynamines with C?O and C?S bonds, a [2 + 2] cycloaddition to thiete intermediates, followed by an electrocyclic ring opening is suggested as reaction mechanism. 相似文献
11.
Carbophilic Additions of Organocuprates and 1,3-Thiazole-5(4H)-thiones Organocuprates and 1,3-thiazole-5(4H)-thiones 1 react in THF at 0° via carbophilic addition onto the C? S bond to give 4,5-dihydro-1,3-thiazole-5-thiols 3 (Scheme 3). This observation is in marked contrast to the previously described reaction of organolithium compounds and 1 , which undergo a thiophilic addition onto the exocyclic S-atom. As an exception, treatment of the 1,3-thiazole-5(4H)-thione 1a with tert-butyl cuprate leads to 7a (Scheme 3). 相似文献
12.
Summary Reaction of 1,3-thiazolidine-2-thione and copper(II) chloride and bromide in MeOH yields CuL3X complexes. These react with an excess of copper(II) halide to give CuL2X complexes. From their i.r. spectra, all the complexes seem to be S-bonded to the metal. Thev(CuCl) vibration is identified at 236 cm–1. 相似文献
13.
Anvarhusein A. Isab 《Transition Metal Chemistry》1992,17(5):374-376
The reaction of AgNO3 with imidazolidine-2-thione (Imt), 1,3-diazinane-2-thione (Diaz) and their derivatives yields complexes of stoichiometry
[AgLNO3] (where L=Imt or Diaz and their derivatives). The C-2 resonances of the Diaz complexes were shifted more from the free ligand
positions compared to the Imt complexes, suggesting that the former bind more strongly to Ag1 than the latter.
TMC 2670 相似文献
14.
The photocycloaddition of benzothiazole-2-thiones to electron-rich and aryl-substituted alkenes are described. Irradiation of N-unsubstituted benzothiazole-2-thione ( 1 ) in the presence of alkenes 3 gave 2-(2′-mercaptoalkyl)benzothiazoles 4 , and 2-substituted benzothiazoles 5 and 6 (in the case of 3a and 3h , resp.) through the ring cleavage of an intermediate 2-aminothietane (Schemes 1 and 3 ). The latter was formed by [2+2] cycloaddition of the C?S bond of 1 and the C?C bond of 3 . Irradiation of N-methylbenzothiazole-2-thione ( 2 ) and 2-methylpropene ( 3a ) gave the spiro-1,3-dithiane 8 , 1,2,6-benzodithiazocin-5-one 9 , and disulfide 10 . The structure of 9 was established by X-ray crystal-structure analysis. 相似文献
15.
1,3-Oxathiolanc Synthesis: Spirocyclic 1,3-Oxathiolanes from the Lewis-Acid-Catalyzed Reaction of Cyclic Trithiocarbonates and Oxiranes The cyclic trithiocarbonates 1.3-dithiolane-2-thione ( 4 ) and 1,3-dithiole-2-thione ( 9 ) in 1,2-dichloroethane and MeCN, respectively, react with alkyl- and phenyl-substituted oxiranes 2 in the presence of Lewis acids to give 1-oxa-4,6,9-trithiaspiro[4.4]nonanes 5 and 6 (Scheme 2) and 1-oxa-4,6,9-trithiaspiro[4.4]non-7-enes 10 and 11 (Scheme 3), respectively. The reactions proceed regioselectively yielding 2-alkyl ( 5 , 10 ) and 3-phenyl derivatives ( 6 , 11 ) as the main products. From the reaction of 4 and 2-phenyloxirane ( 2e ) with TiCl4, 2-phenyl-1,4,6,9-tetrathia-spiro[4.4]nonane ( 7 ) is isolated as a minor product. The molecular structures of 5a , 6e , and 7 are established by X-ray crystallography. 相似文献
16.
M. Sakhawat Hussain Abdul Rahman Al-Arfaj M. Latif Hossain 《Transition Metal Chemistry》1990,15(4):264-269
Summary Novel mixed-ligand copper(I) complexes of general formula [TPP–Cu–(L)Cl] or [TPPhos–Cu–(L)Cl], where TPP=triphenylphosphine, TPPhos=triphenylphosphate and L=imidazolidine-2-thione [Imt],N-propylimidazolidice-2-thione [PrImt],N-i-propylimidazolidine-2-thione [iPrImt], and 1,3-diazinine-2-thione [Diaz] and bis coniplexes of formula [(L)2CuCl] where L=[PrImt] and [iPrImt] have been prepared and characterized by electronic, vibrational and n.m.r. spectroscopy. The spectral data are consistent with S-donation of thiones. The magnitude of upfield shift in13Cn.m.r. of the thionreide carbon on complexation has been interpreted in terms of coordination geometry around the metal stoms. X-ray structure analysis agrees with the conclusions from the spectroscopic measurements. The structure of [(PrImt)2CuCl] revealed three-coordinated copper(I) with crystal data:a=14.106(4),b=14.380(2),c=19.024(3) A, =108.8(2)°,z=8 and space group P2/c. 相似文献
17.
Summary Crystalline copper(I) complexes of the general formula [LCuCl] and [L2CuCl] were prepared for imidazolidine-2-thiones and 1,3-diazinane-2-thiones by the reduction of copper(II) halides with an excess of the ligands. The13C n.m.r. and i.r. spectra of these complexes are consistent with thione sulphur (ligand) donation in all cases. The magnitude of the high-field shift in the13C resonance of the thioureide carbon in the complexes as compared with that of the free ligands is interpreted in terms of coordination geometry around the metal atoms. A comparison of the chemical shifts for gold(I), silver(I) and copper(I) revealed a displacement ofca. 6–8 ppm for the mono- and 2–4 ppm for the bis-complexes, respectively. 相似文献
18.
Reactions of 1,3-Thiazole-5(4H)-thiones with Grignard- and Organolithium Compounds: Carbophilic and Thiophilic Additions Organolithium compounds and 1,3-thiazole-5(4H)-thiones 9 reacted via thiophilic addition on the exocyclic S-atom. The intermediate anion E has been trapped by protonation to give 12 and by alkylation to yield 16 , respectively (Schemes 5 and 6). In competition with protonation of E , a fragmentation to benzonitrile and a dithioester 14 was observed (Scheme 5). In some cases, the alkylation of E led to the formation of dithioacetals 17 instead of 16 (Scheme 6). Methyl, ethyl, and isopropyl Grignard reagents and 9 in THF underwent again a thiophilic addition yielding 4,5-dihydro-1,3-thiazoles of type 12 (Scheme 3). In contrast to this result, MeMgI reacted with 9a in Et2O via carbophilic addition to 11 . Again a carbophilic attack at C(5) of 9 was observed with allylmagnesium and 2-propynylmagnesium bromide, respectively, in Et2O. 相似文献
19.
On Chalcogenolates. LXX. Experiments to Prepare Tetrathiooxalates. About Alkylthio-1,3-dithiol-2-thiones Experiments to prepare tetrathiooxalates have been described. The electrolytic reduction of carbon disulfide and the reaction of sodium with CS2 lead to formation of C3S52? ions beside others. The alkylations of C3S52? give alkylthio-l,3-dithiol-2-thiones. The formation of polymeric tetrathiooxalates has not been proved. 相似文献
20.
Grzegorz Mlosto Mireille Petit Anthony Linden Heinz Heimgartner 《Helvetica chimica acta》1994,77(2):435-444
Reaction of Di(tert-butyl)- and Diphenyldiazomethane and 1,3-Thiazole-5(4H)-thiones: Isolation and Crystal Structure of the Primary Cycloadduct Reactions of diazo compounds with C?S bonds proceed via the formation of thiocarbonyl ylides, which, under the reaction conditions, undergo either 1,3-dipolar cycloadditions or electrocyclic ring closer to thiiranes (Scheme 1). With the sterically hindered di(tert-butyl)diazomethane ( 2c ), 1,3-thiazole-5(4H)-thiones 1 react to give spirocyclic 2,5-dihydro-1,3,4-thiadiazoles 3 (Scheme 2). These adducts are stable in solution at ?20°, and they could be isolated in crystalline form. The structure of 3c was established by X-ray crystallography. In CDCl3 solution at room temperature, a cycloreversion occurs, and the adducts of type 3 are in an equilibrium with 1 and 2c . In contrast, the reaction of 1 with diphenyldiazomethane ( 2d ) gave spirocyclic thiiranes 4 as the only product in high yield (Scheme 3). The crystal structure of 4b was also determined by X-ray analysis. The desulfurization of compounds 4 to 4,5-dihydro-5-(diphenylmethylidene)-1,3-thiazoles 5 was achieved by treating 4 with triphenylphosphine in boiling THF. The crystal structure of 5f is shown. 相似文献