Preparation and fungitoxicity of 3,6-dichloro-and 3,6-dibromo-8-quinolinols

Summary 3,6-Dichloro- and 3,6-dibromo-8-quinolinols were prepared by direct halogenation of 8-nitroquinoline by N-halosuccinimide in acetic acid or by halogenation of the corresponding 6-halo-8-nitroquinoline prepared via aSkraup reaction. The nitro group was reduced to amino and the amine was hydrolyzed to the phenol in 70% sulfuric acid at 220°C. The fungitoxicity of 3,6-dichloro- and 3,6-dibromo-8-quinolinols, as well as intermediates in their preparation, againstAspergillus niger, Aspergillus oryzae, Myrothecium verrucaria, Trichoderma viride, andMucor cirinelloides was determined. 3,6-dichloro-8-quinolinol is the most fungitoxic analogue of this class of compounds observed to date.

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Herstellung und Fungitoxizität von 3,6-Dichlor- und 3,6-Dibrom-8-chinolinen

Zusammenfassung 3,6-Dichlor- und 3,6-Dibrom-8-chinoline wurden durch direkte Halogenierung von 8-Nitrochinolin mit N-Halogensuccinimid in Essigsäure oder durch Halogenierung der entsprechenden nachSkraup synthetisierten 6-Halogen-8-nitrochinoline hergestellt. Die Nitrogruppe wurde zum Amin reduziert und die Aminofunktion in 70% iger Schwefelsäure bei 220°C zum Phenol hydrolysiert. Die Fungitoxizität der 3,6-Dichlor- und 3,6-Dibrom-8-chinoline und jene der bei ihrer Herstellung auftretenden Zwischenstufen gegenAspergillus niger, Aspergillus oryzae, Myrothecium verrucaria, Trichoderma viride undMucor cirinelloides wurde bestimmt. 3,6-Dichlor-8-chinolin ist der derzeit stärkste bekannte fungitoxische Vertreter dieser Substanzklasse.

     

Spektroskopische Eigenschaften von Di(phthalocyaninato)metallaten(III) der Seltenen Erden. Teil 2: Die Multikern(1H-, 13C-, 15N-, 17O- und 31P)-NMR-Spektren und Nachweis komplexgebundenen Wassers

Spectroscopical Properties of Di(phthalocyaninato)metalates(III) of the Rare Earth Elements. Part 2: The Multinuclear (¹H, ¹³C, ¹⁵N, ¹⁷O, and ³¹P) NMR Spectra and Determination of Complex Bound Water The ¹H, ¹³C, ¹⁵N, ¹⁷O and ³¹P NMR spectra of (PNP)[Ln(Pc^2?)₂] and (TDOA)[Ln(Pc^2?)₂] (Ln = La …? (—Pm) …? Lu); PNP: di(triphenylphosphine)-iminium; TDOA: Tri(n-dodecyl)n-octylammonium dissolved in CD₂Cl₂ are reported. With the exception of the nitrogen atoms of the cations all light atoms of both homologues complex salt rows have been detected and assigned. Proof of the presence of additional water contained in the (solid) complex salts has been given unambigously. The otherwise strong Fermi contact interactions diminuish rapidly with growing distance from the paramagnetic centre favouring dipolar (pseudo-contact) interactions. As a consequence the mostly element independent paramagnetic shifts of the atoms situated on the periphery of the anion as well as those of the cations and water are determined by the distance factor. Therefore a first glance of the structure of the ion-pair present in solution emerges, in which the water molecule seems to play an important role.     

3, 6-二取代-均三唑并[3, 4-b]-1, 3, 4-噻二唑的合成

研究了2-苯基-1, 2, 3-三唑-4-羧酸(1)与3-烷基/芳基-4-氨基-5-巯基-1, 2, 4-三唑(2a～o)在POCl~3催化下, 脱水缩合得到15个新的3-烷基/芳基-6-(2'-苯基-1', 2', 3'-三唑-4'-基)均三唑并[3,4-b]-1, 3, 4-噻二唑类化合物(3a～o)。     

CCSD(T) expectation value calculations of first-order properties

An expectation value approach to calculations of first-order properties using the non-iterative, triple-excitation amplitudes in the coupled cluster wave function is exploited. Three methods are suggested and analysed using the many body perturbation theory (MBPT) expansion arguments. The first method, in which non-iterative triple-excitation amplitudes are used in the expression for the expectation values, makes the wave function accurate through the second order of MBPT. In the second method, which is an extension of the first, effects of triple-excitation amplitudes are coupled with single- and double-excitation amplitudes. The correlated density matrix equivalent through the fourth order to that obtained when CCSDT-la amplitudes are used is employed in the third method. The suggested methods are tested on dipole moment and polarizability calculations for several diatomic closed-shell molecules and are compared to other related approaches. Received: 15 May 1997 / Accepted: 5 June 1997     

高分子路易斯酸催化剂—阳离子交换树脂四氯化锡复合物

大孔强酸性聚苯乙烯系阳离子交换树脂与SnCl_4在CS_2中反应可生成一种稳定的高分子路易斯酸催化剂.其制备简单、易分离.这种催化剂不怕水,对酯化、缩醛、缩酮、醚化及付氏烷基化反应具有较好的催化作用,且催化性能稳定,至少可重复使用10次.     

Metal complexes in catalytic transformations of olefins. 6. Mechanism of formation and characteristics of the precursors of active centers of ethylene dimerization to butene-1 in the Ti(O-n-Bu)4-AlEt3 system in ethers

Reaction of Ti(O-n-Bu)₄ (TBT) with AlR₃ (R = Me, Et,i-Bu) in solvents such as R₂O, Py, and Et₃N, reduces Ti(IV) to Ti(III), Ti(II), or Ti(I). The organotitanium compounds formed by the reaction of TBT with organoaluminum compounds (OAC) undergo homolytic decomposition at the bond in Ti-C. Isotopic exchange analysis using C₂D₄ suggested the formation of particles containing Ti-CH₂CH₂-Ti, Al-CH₂CH₂-Al, Al-CH₂CH₂-Ti, M=CHCH₃, and MMCHCH₃ (M, M = Al or Ti) fragments. An ESR spectral analysis established that reaction of TBT with TEA in R₂O, Py, and Et₃N environments produced two types of paramagnetic complexes, precursors of active centers of ethylene dimerization. The influence of various factors on the kinetics of accumulation and consumption of these complexes was investigated and their structures are suggested.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1516–1525, July, 1992.     

Gould-Jacobs reaction of 6-amino-2,3-diphenylquinoxaline

Summary Catalytic hydrogenation of 2,3-diphenyl-6-nitroquinoxaline led to the corresponding amine1 which in turn afforded products3a-i on reaction with alkoxymethylene derivatives2a-i. Thermal cyclization of3b and3f yielded substituted pyrazinoquinolones5b and5f, respectively. Optimal conditions for the successful hydrolysis of ester5b were found. The structures of all products were deduced from their IR, UV,¹H, and¹³C NMR spectroscopic data.Dedicated to Prof.F. Sauter on the occasion of his 65th birthday     

Redox Transformation of Adducts from Cycloaddition of Diazoacetic Ester to β-Arylacryloyloxiranes

It was established that, in addition to ethyl 4-aryl-3-(2,3-epoxyalkanoyl)-4,5-dihydro-1H-pyrazole-5-carboxylates, the reaction of diazoacetic ester with β-arylacryloyloxiranes also gives ethyl 4-aryl-3(5)-(3-hydroxy-2-methylalkanoyl)-1H-pyrazole-5(3)-carboxylates. The latter are formed from the tautomeric ethyl 4-aryl-5-(2,3-epoxyalkanoyl)-4,5-dihydro-1H-pyrazole-3-carboxylates as a result of intramolecular oxidative-reductive disproportionation. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, 1150–1160, August, 2005.     

[1‐Allylpyridinium][Cu2Cl3]: Synthesis,X‐ray Structure and the Regularity of Crystal Architecture of 1‐Allyl/(amino)‐pyridinium Copper(I) Chloride π‐Complexes

By alternating‐current electrochemical technique crystals of copper(I) π‐complex with 1‐allylpyridinium chloride of [C₅H₅N(C₃H₅)][Cu₂Cl₃] ( 1 ) composition have been obtained and structurally investigated. Compound 1 crystallizes in monoclinic system, space group C2/c a = 24.035(1) Å, b = 11.4870(9) Å, c = 7.8170(5) Å, β = 95.010(5)°, V = 2150.0(2) ų (at 100 K), Z = 8, R = 0.028, for 4836 independent reflections. In the structure 1 trigonal‐pyramidal environment of π‐coordinated copper(I) atom is formed by a lengthened to 1.376(2) Å C=C bond of allyl group and by three chlorine atoms. Other two copper atoms are tetrahedrally surrounded by chlorine atoms only. The coordination polyhedra are combined into an original infinite (Cu₄Cl₆^2—)_n fragment. Structural comparison of 1 and the recently studied copper(I) chloride π‐complexes with 3‐amino‐, 2‐amino‐, 4‐amino‐1‐allylpyridinium chlorides of respective [LCu₂Cl₃] ( 2 ), [L₂Cu₂Cl₄] ( 3 ), and [LCuCl₂] ( 4 ) compositions allowed us to reveal the trend of the inorganic fragment complication which depends on pKa (base) value of the corresponding initial heterocycle.     

双－（3－烷基／芳基）－7H－1，2，4－三唑并[3,4-b]-1,3,4-噻二嗪类化合物的合成及波谱性质

利用1，4－二溴丁二酮（1）分别与3－烷基／芳基－4－氨基－5－巯基－1， 2，4－三唑（2a-2n）反应，合成了14种新的双－（3－烷基／芳基）－7H－1，2， 4－三唑并[3,4-b]－1，3，3-噻二嗪类化合物（3a-3n），并利用EA、IR，~1H NMR和MS确定了其结构。