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1.
This study describes a simple and efficient procedure to synthesize a novel series of fourteen 4-substituted N-(5-pyridinyl-1H-1,2,4-triazol-3-yl)-6-(trifluoromethyl)pyrimidin-2-amines, where the 4-substituents are H, CH3, C6H5, 4-FC6H4, 4-CH3C6H4, 4-CH3OC6H4 and 2-Furyl; from the cyclocondensation reaction of N-[5-(pyridinyl)-1H-1,2,4-triazol-3-yl]guanidines with 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1-trifluoroalk-3-en-2-ones. The reactions were carried out in ethanol under reflux for 18 h and led to 40-68% yields. N-(Pyridyl-triazolyl)guanidine precursors were further obtained from reactions of cyanoguanidine with nicotinic or isonicotinic acid hydrazides and the halogenated enones from trifluoroacetylation of enolethers or acetals.  相似文献   

2.
The tris(trimethylsilyl)amidines RC(NSiMe3)N(SiMe3)2 (R  C6H5, p-CH3C6-H4, p-ClC6H4, p-MeOC6H4, p-Me2NC6H4, p-CF3C6H4, p-C6H5C6H4 and CF3) are prepared by the reaction of the respective nitriles with (Me3Si)2NLi·OEt2 in ether to give intermediates RC(NLi)N(SiMe3)2. Heating these intermediates with ClSiMe3 in toluene affords the products, which are isolated by vacuum distillation, in high yield. With 1,4-dicyanobenzene, two equivalents of reagents affords the per(trimethylsilyl)-1,4-diamidine. Hydrolysis of the intermediates with 6N ethanolic HCl affords the unsubstituted amidine hydrochlorides RC(NH)NH2·HCl (R  C6-H5, p-MeOCh6H4, p-ClC6H4, p-O2NC6H4) in high yield.  相似文献   

3.
Treatment of [BzPh3P][AuCl2] with [Hg(x-C6H4NO2)2] (x = o, m, or p) gives anionic gold(I) complexes of the type [BzPh3P][Au(R)Cl](R = o-, m- or p-C6H4NO2, Bz = C6H5CH2). The chloro ligand in [Au(o-C6H4NO2)Cl]? can be replaced by bromo or iodo ligands by use of NaBr or NaI. The anions [Au(R)Cl]? react with neutral monodentate ligands, L, to give neutral mononuclear complexes [Au(R)L] (R = o-C6H4NO2, L = PPh3, AsPh3; R = m-C6H4NO2, L = PPh3) and with 1,2-bis(diphenylphosphino)ethane (dpe) to give [Au2(R)2(dpe)] (R = o-C6H4NO2). The corresponding [Au(p-C6H4NO2)Cl]? reacts with PPh3 or AsPh3 to give mixtures containing [AuClL]. The anionic ortho-nitrophenylgold(I) complex is much more stable than its meta- or para-nitrophenyl isomers. These are thought to be the first reports of nitrophenylgold(I) complexes.  相似文献   

4.
The first synthesis of a series of 2-aryl(heteroaryl)-4-trifluoromethyl-4,5-dihydro-3H-pyrido[2,3-b][1,4]diazepin-4-ols, where aryl = C6H5, 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-CH3C6H4, 4-OCH3C6H4, 4,4′-biphenyl, 1-naphthyl and heteroaryl = 2-thienyl, 2-furyl obtained from the direct cyclocondensation reaction of 4-methoxy-1,1,1-trifluoroalk-3-en-2-ones with 2,3-diaminopyridine in 54-71% yield, is reported. Another alternative and efficient route for the synthesis of a series of 2-aryl(heteroaryl)-3H-pyrido[2,3-b][1,4]diazepin-4(5H)-ones from the reaction 4-methoxy-1,1,1-trichloroalk-3-en-2-ones with 2,3-diaminopyridine, in 54-70% yield, is also reported.  相似文献   

5.
Solutions of [(C6H5)3P]3CoCH3 (I) in C6H5Cl yield biphenyl, triphenylphosphine, methyldiphenylphosphine and diphenylphosphine. In 4-ClC6H4CH3, 4-methylbiphenyl and 4,4′-bitolyl form as well. Solutions of I in C6H6, C6D6, C6H5CH3, C6H5Br yield only triphenylphosphine and biphenyl, while in 4-FC6H4I 4,4′-difluorobiphenyl is formed but no biphenyl. The cobalt compound is recovered as (Ph3P)nCoX or as CoX2 (XCl, Br, I, n = 3 or 2) from reactions with arylhalides. The results are rationalized in terms of the very strong tendency for I to undergo oxidative addition reactions.  相似文献   

6.
The thermolytic decomposition of Ph4SbSAr in organic solvents are reported. Solvent-derived products from decompositions in CCl4 and cyclohexane confirm the free radical nature of the reactions.Thermal decompositions of Ph3 (p-MeC6H4)SbSC6H4OMe-p, or Ph(p-MeC6H4)3SbSC6H4X(Xp-MeO or H) provide mixed triarylstibines,[Ph3nSb(C6H4Me-p)n (n0, 1, 2 and 3), disulphide (XC6H4SSC6H4X), monosulphides (PhSC6H4X and p-MeC6H4SC6H4X), arenes, (PhH and PhMe) and biaryls (Ph2,PhC6H4Me-p and p-MeC6H4C6H4Me-p).  相似文献   

7.
The cross-polarization magic angle spinning 13C NMR spectra of Hg(SbF6)2 - 2 Arene (Arene = C6HMe5, 1,2,4,5-C6H2Me4, 1,2,3,4-C6H2Me4, or C6H6) have been measured. The spectra of the complexes of C6HMe5 and 1,2,4,5-C6H2Me4 are consistent with static η1-bonding of the mercury to the arene at an unsubstituted carbon atom, while the spectra of the 1,2,3,4-C6H2Me4 and C6H6 complexes show the arene to have time-averaged Cs or C2, and C6 symmetry respectively, at the temperature of measurement (300 K).The reduced temperature 13C NMR spectra of Hg(Arene)n2+ (n = 1 or 2; Arene = 1,3,5-C6H3R3 (R = Me, i-Pr, or t-Bu)) in SO2 solution are also reported and affirm that in these intramolecularly mobile species the mercury bonds in an η1-manner, with unsubstituted aryl carbon atoms being the strongly preferred point of mercury attachment. This site preference is further demonstrated by the solution 13C NMR spectra of Hg(Arene)n2+ (Arene = 1,2,3,4-C6H2-Me4, n = 1 or 2; Arene = 1,4-C6H4R2, R = Me or t-Bu, n = 1). The spectra of the 1,4-C6H4R2 complexes and Hg(p-C6H4-t-BuMe)2+ provide clear evidence for steric influence of the binding site.Like Hg(C6Me6)22+, but unlike most of the complexes of substituted benzenes which have been studied, Hg(1,3,5-C6H3-i-Pr3)22+ exchanges only slowly with excess free ligand.  相似文献   

8.
Three 12-aryl-5H,7H-pyrido[2,3-b:6,5-b??]diindoles (Ar = Ph, 4-BrC6H4, and 4-MeOC6H4) were obtained from appropriate 3-arylidene-2-ethoxyindolenines and hydrazine hydrate.  相似文献   

9.
The regiospecific synthesis of a novel series of nine 4-phenyl- and 3-alkyl(aryl)-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-1-tosylpyrazoles (pyrazolinyl p-tolyl sulfones), as well as their antimicrobial activity against yeast, such as fungi, bacteria, and alga are reported. The 1-p-tosyl-2-pyrazolines were obtained from the cyclocondensation reaction of 3-phenyl- and 4-alkyl(aryl)-1,1,1-trifluoro-4-alkoxy-3-alken-2-ones, [where alkyl = H, Me and aryl are -C6H5, 4-CH3C6H4, 4-OCH3C6H4, 4-FC6H4, 4-ClC6H4, 4-BrC6H4,] with p-tosylhydrazine in a yield of 58-92% when toluene was employed as solvent. The best activity was obtained when the structure possessed a 4-fluorophenyl substituent linked at the carbon-3 of the pyrazoline ring. Subsequently, the dehydration reaction of 3-(4-fluorophenyl) substituted 2-pyrazoline with thionyl chloride/pyridine in benzene as solvent furnished the corresponding 1H-pyrazole in only a moderate yield (49%).  相似文献   

10.
《Polyhedron》1986,5(10):1581-1585
Several new, pentacoordinated, triorganoantimony bis-selenocyanates [R3Sb(SeCN)2 (R = Me, Ph, p-CH3C6H4, p-ClC6H4, p-F-C6H4 or C6F5)], tetraorganostibonium selenocyanates [R3R′Sb(SeCN) (R = R′ = Ph; R = Ph, and R′ = CH2CHCH2)] and μ-oxy-bis(triarylantimony) bis-selenocyanates {[Ar3SbOSbAr3](SeCN)2 (Ar = Ph, p-CH3C6H4, p-ClC6H4 or p-FC6H4)} have been synthesized from potassium selenocyanate and the corresponding organoantimony halide (chloride and/or bromide) in the presence of the phase-transfer catalyst 18-crown-6, and characterized. Spectroscopic evidence suggested an iso structure (Sb—NCSe). The compounds were also obtained in the absence of 18-crown-6 but in lower yields. Some of these compounds were found to exhibit a significant biological activity.  相似文献   

11.
Carbamoyl and alkoxycarbonyl complexes of palladium(II) and platinum(II) of the type M(pnp)(CONHR)Cl (pnp = 2,6-bis(diphenylphosphinomethyl)pyridine; M Pd, R  C6H5, p-CH3C6H4, p-CH3OC6H4, C6H11, t-Bu; M  Pt, R  C6H5), Pd(pnp)[CON(Pr)2]Cl (Pr = propyl), M(pnp)(COOR)Cl (M  Pd, R  C6H5, CH3; M  Pt, R  CH3), Pd(pnp)(COOCH3)2 result from reaction of M(pnp)Cl2 with carbon monoxide and amines or alkoxides at room temperature and atmospheric pressure.The carbamoyl complexes react with bases to give urethane or diphenylurea depending upon the experimental conditions.  相似文献   

12.
Oxidative alkylamination of azinones is a promising method for the preparation of a great variety of alkylaminoazinones. Treatment of 6,8-dimethyl-2-R-pyrimido[4,5-c]pyridazin-3,5,7(2H,6H,8H)-triones 7, 1,3-dimethyl-5-R-pteridin-2,4,6(1H,3H,6H)-triones 8 and 1,3,6-trimethylpyrimido[4,5-d]pyrimidin-2,4,7(1H,3H,6H)-trione 9 with alkylamine/AgPy2MnO4 or alkylamine/KMnO4 has been shown to produce their 4-, 7- and 5-alkylamino derivatives, respectively, in good yields. While 1-methylquinoxalin-2(1H)-one 10 is smoothly alkylaminated under the above conditions giving 3-alkylamino derivatives, quinoxaline itself does not take part in this reaction. Factors influencing oxidative alkylamination of azinones and a regioselectivity of the process are discussed.  相似文献   

13.
The syntheses and properties of the titanium(III) complexes Cp2Tir · R′CN (R = C6H5, o-, m-, p-CH3C6H4, CH2C6H5, C6F5, Cl; R′ = CH3, t-C4H9, C6H5, o-CH3C6H4, 2,6-(CH3)2C6H3) are described. In the complexes the nitrogen atom of the cyanide ligands is coordinated to the metal. The thermal stabilities of the complexes depend markedly on R and R′; on heating they undergo a novel reaction in which two cyanide ligands are coupled by formation of a CC bond, while the metal is oxidized to titanium(IV).  相似文献   

14.
The application of a general synthetic approach to prepare molecular chains is reported. It is based on a step-by-step method each consisting first in a Pd-catalyzed reaction between ArI and HXAr′Br (Ar=aryl, Ar′=arylene) to give ArXAr′Br followed by a Cu-catalyzed replacement of Br by I to give ArXAr′I that can be reacted with HXAr′Br in the following step. The application of this method is here illustrated to prepare phenylene sulfide oligomers (X=S). Starting from RC6H4I-4 (R=H, MeO, NO2, NH2) and HSC6H4Br-x (x=2, 4) it is possible to grow chains in one direction to give X(C6H4S-m)nC6H4R-4 (n=1, X=Br, m=4, R=H, MeO, NO2, NH2, SMe and m=2, R=H, MeO, NO2; n=1, X=I, m=2 or 4, R=H, MeO, NO2; n=2, X=Br, m=2 or 4, R=H, MeO, NO2; n=2, X=I, m=4, R=MeO, NO2; n=3, X=Br, m=4, R=MeO, NO2; n=3, X=I, m=4, R=NO2 and n=4, X=Br or I, m=4, R=NO2). From HSC6H4Br-x and IC6H4I-4 the chains can grow in two directions to give X(C6H4S-4)nC6H4X-4 (n=2 or 4, X=Br or I), 2-XC6H4(SC6H4-4)nSC6H4X-2 (n=3 or 5, X=Br). Using diiodomesitylene the dithioethers C6HMe3-2,4,6-(SC6H4X-4)2-1,3 (X=Br, I) have been prepared. The series of sulfoxides X(C6H4S(O)-4)nC6H4R-4 (X=Br, n=1, R=MeO, n=3, R=NO2, n=4, R=Br; X=R=I, n=2) has been obtained from the corresponding thioethers and PhICl2.  相似文献   

15.
The kinetics of hydrolysis reactions of some chlorodisiloxanes and of the chloropentasiloxanes (Me3) SiO)2Si(Me)OSiAr(Cl)OSiMeAr′ (with Ar = Ph and Ar′ = p-ClC6H4, C6H5 or p-MeC6H4; or Ar′ = Ph and Ar = p-ClC6H4, C6H5 or p-MeC6H4 in dioxane were studied by 1H NMR spectroscopy.Because of their high hydrolysis rate the chlorodisiloxanes can be reacted only with equimolar amounts of H2O. The formal second order rate constants and also the ? value evaluated can be used only in a tentative way.From hydrolysis reactions of the chloropentasiloxanes with an excess of H2O and different amounts of HCl or HClO4 the following results were obtained: hydrolysis is catalysed by HCl and HClO4. The reaction is of first order with respect to chlorosiloxane. With respect to HCl at a tenfold excess of H2O the order is in the range 0.5–0.7. Our results indicate, that there is a “non-catalysed” hydrolysis besides the acid catalysed reaction, ?-Values for the variation of Ar (0.7) and Ar′ (0.3) can be derived from the rate constants of the acid catalysed reactions of chloropentasiloxanes with a tenfold amount of water. The results are interpreted in mechanistic terms.  相似文献   

16.
Ion—molecule reactions occur in the ionization chamber of a mass spectrometer during the combined vaporization of arenechromium tricarbonyls (ArCr(CO)3, Ar = C6H6, C6H5Cl, C6H5N(CH3)2, C4H4S, C4H4Se) and cyclopentadienylmetal carbonyls (C5H4RM(CO)n, M and R = Mn, H;Mn, Cl; Mn, Br; Mn, COCH3; Re, H; V, H) with various aromatic and heterocyclic compounds (L). In all cases secondary ions of sandwich type [ArCrL]+ or [C5H4RML]+ containing a new metalligand bond are formed.  相似文献   

17.
The reactions of the fluorobenzenes, C6F5H, o-C6H2F4, m-C6H2F4, p-C6H2F4, 1,3,5-C6F3H3, 1,2,4-C6F3H3, o-C6F2H4, m-C6F2H4, p-C6F2H4 and C6F5H with thiolate anion nucleophiles RS? (primarily MeS?), have been studied in ethylene glycol/pyridine mixtures as a solvent. Multiple replacement of fluorine atoms was observed in the more highly fluorinated compounds, but in all cases two aromatic fluorine atoms were not replaced. Difluorobenzene and fluorobenzene did not react. The product orientations have been deduced from their NMR spectra. The mass spectra of the isomeric products C6F2H3(SMe), C6F3H2(SMe) and C6F2H2(SMe)2 have been examined.  相似文献   

18.
A series of novel arylantimony derivatives of analogues of demethylcantharimide with the formulae ArnSbL(5−n) and ArnSbL(5−n)(LH=N-hydroxy-demethyldehydrogencantharimide, LH=N-hydroxy-demethylcantharimide, n=3, 4; ArC6H5, 4-CH3C6H4, 3-CH3C6H4, 2-CH3C6H4, 4-ClC6H4, 4-FC6H4) were synthesized and characterized by elemental analysis, IR, 1H NMR and mass spectroscopy. The crystal structures of (C6H5)4SbL, (4-CH3C6H4)3SbL2 and (3-CH3C6H4)3SbL2 were determined by X-ray diffraction. The in vitro antitumor activities of all compounds against six cancer cells are reported.  相似文献   

19.
A series of seven novel f-element bearing hybrid materials have been prepared from either methyl substituted 3,4 and 4,5-pyrazoledicarboxylic acids, or heterocyclic 1,3- diketonate ligands using hydrothermal conditions. Compounds 1, [UO2(C6H4N2O4)2(H2O)], and 3, [Th(C6H4N2O4)4(H2O)5]·H2O feature 1-Methyl-1H-pyrazole-3,4-dicarboxylate ligands (SVI-COOH 3,4), whereas 2, [UO2(C6H4N2O4)2(H2O)], and 4, [Th(C6H5N2O4)(OH)(H2O)6]2·2(C6H5N2O4)·3H2O feature 1-Methyl-1H-pyrazole-4,5-dicarboxylate moieties (SVI-COOH 4,5). Compounds 5, [UO2(C13H15N4O2)2(H2O)]·2H2O and 6, [UO2(C11H11N4O2)2(H2O)]·4.5H2O feature 1,3-bis(4-N1-methyl-pyrazolyl)propane-1,3-dione and 1,3-bis(4-N1,3-dimethyl-pyrazolyl)propane-1,3-dione respectively, whereas the heterometallic 7, [UO2(C11H11N4O2)2(CuCl2)(H2O)]·2H2O is formed by using 6 as a metalloligand starting material. Single crystal X-ray diffraction indicates that all coordination to either [UO2]2+ or Th(IV) metal centers is through O-donation as anticipated. Room temperature, solid-state luminescence studies indicate characteristic uranyl emissive behavior for 1 and 2, whereas those for 5 and 6 are weak and poorly resolved.  相似文献   

20.
Although very bulky ligands e.g.(o-MeC6H4)3E or (μ-C10H7)3E (E = P or As) are inert, the normal photochemical or thermal reaction of tertiary phosphines or arsines, L, with [Mn2(CO)10] is CO substitution with the formation of [Mn2(CO)8(L)2] derivatives (I). At elevated temperatures some triarylarsines, R3As, undergo Lambert's reaction with ligand fragmentation to give [Mn2(CO)8(μ-AsR2)2] complexes (II) (R = Ph, p-MeOC6H4, p-FC6H4, or p-CIC6H4) even though, in the absence of [Mn2(CO)10] R3As are stable under the same conditions. Exceptional behaviour is exhibited by (p-Me2NC6H4)3- As which forms a product of type I; by some HN(C6H4)2AsR which give a product of type II as a result of loss of the non-aryl groups R = PhCH2, cyclo-C6H11, or MeO; and by Ph(α-C10H72P which is the only phosphine to form a product of type II, albeit in trace amounts only. The thermal decomposition of a n-butanol solution of [Mn2(CO)8(AsPh3)2] in a sealed tube gives C6H6 and [Mn2(CO)8(α-AsPh2)2], whilst in an open system in the presence of various tertiary phosphines, L, [Mn(H)(CO)3(L)2] are obtained. It is suggested that Lambert's reaction is a thermal fragmentation of [Mn(CO)4(AsR3]* radicals, the first to be recognised. They lose the radical R* which abstracts hydrogen from the solvent. The resulting [Mn(CO)4(AsR2)] moiety dimerises to [Mn2(CO)8-(α-AsR2)2]. the reaction is facilitated by the stability of the departing radical (e.g. PhCH2 or MeO) and, as the crowding about As is relieved, by its size (e.g. Ph, cyclo-C6H11, o-MeC6H4, or α-C10H7). In general, phosphine-substituted radicals [Mn(CO)4(PR)3]* do not undergo this decomposition, probably because the PC bonds are much stronger than AsC.  相似文献   

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