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  • 1995-1999  (1,922)
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  • Inorganic Chemistry  (10,139)
  • Heterocycles
  • Phosphorus
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Mycorrhiza 9 (1999), S. 97-101 
    ISSN: 1432-1890
    Keywords: Key words Glomus mosseae ; Lipid ; Phosphorus ; Protein ; Seed ; Triticum durum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Root colonization by arbuscular mycorrhizal fungi (AMF) may affect protein and lipid composition of plants by altering P nutrition or by eliciting other metabolic responses in the host plant. This study was conducted to determine the effects of an AMF and soil P on seed protein and lipid contents and yield of two genotypes of durum wheat (Triticum durum L.). Plants were grown in a greenhouse using soil: sand mixes with different levels of P, and with or without the AMF Glomus mosseae [(Nicol. and Gerd.) Gerd. and Trappe]. Percentage AMF root colonization decreased as P added to soil increased. The wheat genotype CR057 had higher AMF root colonization but lower seed P and protein concentrations than CR006. Without added soil P, protein concentration was significantly lower and lipid concentration and seed dry weight higher in arbuscular mycorrhizal (AM) than in nonAM plants. Seed lipid and protein contents were highly correlated with P content of plants. In nonAM plants, seed lipid and protein contents were low with no added soil P and did not differ with added soil P. Seed protein/lipid (Pro/L) concentration ratios of AM plants were higher than those of nonAM plants only when no P was added to the soil. The data indicate different patterns of seed P accumulation and different relationships between seed P and protein and lipid in AM and nonAM plants. Thus, both the presence and degree of AMF root colonization affected seed lipid metabolism in these durum wheat genotypes.
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  • 2
    ISSN: 1432-1890
    Keywords: Key words Arbuscular mycorrhizae ; Lythrumsalicaria ; Phosphorus ; Wetland ; Emergent aquatic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The relationship between nutrient availability and mycorrhizal status has been well studied for terrestrial plant species, but has been examined rarely in aquatic and emergent aquatic species. The purpose of this study was to determine the effect of phosphorus availability on the arbuscular mycorrhizal (AM) status of an emergent aquatic, Lythrum salicaria L. L. salicaria was grown in hydroponic sand culture at five phosphorus concentrations (0, 100, 1000, 10 000, and 47 500 μg PO4/l nutrient solution) for 49 days with or without mycorrhizal inoculum obtained from wetland soil. Inoculated plants at the lowest three phosphorus concentrations were colonized by AM, whereas there was no colonization of plants grown at the highest two phosphorus concentrations. Colonization by AM fungi occurred in conjunction with symptoms of phosphorus deficiency in L. salicaria under experimental conditions: plants at the lowest three phosphorus concentrations had lower biomass and higher root: shoot weight ratios than plants at the highest two concentrations. However, total biomass and internal phosphorus concentration did not differ between inoculated and control plants. Further studies are needed under conditions more closely mimicking natural dynamics.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1432-1890
    Keywords: Key words Competition ; Ectomycorrhiza ; External hyphae ; Phosphorus ; Pisolithus arhizus ; Uptake kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Our objective was to evaluate the ability of an ectomycorrhizal fungus to alter the competitive interaction of pine seedlings growing with grass, and to determine whether the interaction was modified by soil-phosphorus (P) concentration. Slash pine (Pinus elliottii), inoculated with the ectomycorrhizal fungus Pisolithus arhizus or fortuitously colonized by Thelephora terrestris, and a native grass (Panicum chamaelonche) were grown in a greenhouse at three P levels (0.32, 3.22, 32.26 μM H3PO4). Pine inoculated with P. arhizus took up more P when competing with the nonmycorrhizal grass than when competing with another pine (irrespective of pine mycorrhizal status). Phosphorus uptake kinetics (Cmin, the minimum concentration at which P can be absorbed from a solution; Imax, the maximum uptake rate) for pine and grass were also determined under hydroponic conditions. Pine had a higher Imax than grass but grass had a lower Cmin, suggesting that pine is more competitive at higher nutrient concentrations while grass is more competitive at lower nutrient concentrations. The controlled conditions used in these experiments allowed us to evaluate specific parameters (P uptake and absorbing surface area) affecting plant competition.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 28 (1999), S. 204-211 
    ISSN: 1432-0789
    Keywords: Key words Alley cropping ; Calcium ; Magnesium ; Nitrogen ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  Balances between nutrients applied or mineralized and nutrients removed in maize grain and stover were calculated in a hedgerow intercropping experiment in which Leucaena leucocephala and L. pallida prunings and cattle manure were applied. Hedgerow intercropping (also called alley cropping) is an agroforestry system in which trees are grown in dense hedges between alleys where short-cycle crops are grown. The hedges are pruned periodically during the cropping period and the prunings are added to the soil as green manure. In control treatments, nutrient depletion per season was in the order of 7–19 kg N ha–1, 4–12 kg P ha–1, 10–26 kg K ha–1, 0–2 kg Ca ha–1 and 3–6 kg Mg ha–1. N fertilizer reversed the depletion of N, but it accelerated the depletion of the other nutrients. Manure and at least two applications of leucaena prunings resulted in net positive balances of N, K, and Ca between amounts applied or mineralized and amounts removed by maize. The amounts of P and Mg applied with, or mineralized from, prunings or manure were insufficient to offset the negative balances of these nutrients.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 28 (1999), S. 182-195 
    ISSN: 1432-0789
    Keywords: Key words Alley cropping ; Calcium ; Magnesium ; Nitrogen ; Phosphorus ; Intercropping
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  A litter bag technique was used to study the decomposition and release of N, P, K, Ca, and Mg from Leucaena leucocephala and L. pallida prunings and cattle manure in a hedgerow intercropping trial conducted in the Ethiopian highlands. Hedgerow intercropping (also called alley cropping or alley farming) is an agroforestry system in which trees are grown in dense hedges between alleys where short-cycle crops are grown. The hedges are pruned periodically during the cropping period and the prunings are added to the soil as green manure. Manure was the most resistant to decomposition, losing only 15% of its dry matter (DM) in 15 weeks, compared to 41–57% lost by leucaena prunings. Large quantities of K (up to 104 kg ha–1) were mineralized from prunings and manure, but Ca and Mg were mostly immobilized. More N and P were released from prunings than from manure, which resulted in net immobilization of these nutrients in the initial stages of decomposition and net mineralization in later stages. Between the leucaenas more N was mineralized and less Ca and Mg were immobilized when L. leucocephala prunings were applied than when L. pallida prunings were applied. Fertilizer N increased DM decomposition and N mineralization. Mineralization of the nutrients was constrained by lignin and polyphenol contents. It is concluded that leucaena mulch and cattle manure may be significant sources of N and K for crop growth, but external sources of P, Ca and Mg may be required, particularly in acid soils which have low contents of these nutrients. However, this fertility effect has to be evaluated against the competition effect of trees to predict crop response.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1432-0789
    Keywords: Key words Alley cropping ; Calcium ; Magnesium ; Nitrogen ; Phosphorus ; Leaf pruning
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  The effects of Leucaena leucocephala and L. pallida prunings and cattle manure on maize nutrient uptake and yield were investigated in a hedgerow intercropping trial in the Ethiopian highlands. Hedgerow intercropping (also called alley cropping) is an agroforestry system in which trees are grown in dense hedges between alleys where short-cycle crops are grown. The hedges are pruned periodically during the cropping period and the prunings are added to the soil as green manure. For each leucaena species, the experiment had 16 treatments resulting from a factorial combination of four levels of leucaena leaf prunings (no prunings applied; first prunings applied; first and second prunings applied; first, second and third prunings applied), two levels of air-dried cattle manure (0 and 3 t dry matter ha–1) and two levels of N fertilizer (0 and 40 kg N ha–1 as urea). Uptake of N, P and K increased significantly with application of the three nutrient sources, but uptake of Ca and Mg either did not respond or decreased with application of prunings and manure. All the three factors increased maize grain and stover yields significantly, usually with no significant interactions between the factors. At least two applications of prunings were required to significantly increase nutrient uptake and maize yield. Maize in the row closest to the hedge did not respond to these nutrient inputs. It is concluded that hedgerow intercropping, with or without manure application, can increase crop yields moderately (to 2–3 t ha–1 maize grain yields) in the highlands, but P, Ca and Mg may have to be supplied from external sources if they are deficient in the soil. Additional N is still required for higher yields (〉4 t ha–1 maize grain yields). However, quantification of the competition effects of the trees is also required to confirm these results.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 30 (1999), S. 7-13 
    ISSN: 1432-0789
    Keywords: Key words Earthworm ; Surface casts ; Rainfall events ; Soil erosion ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  We investigated whether, under a temperate climate and in a maize crop, earthworm casts could contribute to soil erosion and further favour the exportation of phosphorus by runoff waters. Recording of casts was made in compacted (wheel-tracks) and non-compacted inter-rows, for a 2-month period in spring. To assess the rainfall impact on cast evolution, half of the observation sites were protected against rain splash by a nylon mesh placed above the soil surface. The water runoff was collected and analysed for sediment contents and phosphorus concentration. The mean annual production of surface casts was calculated to be 34 kg (dry weight) year–1 kg–1 earthworm (fresh weight). Synchronization between cast erosion and rainfall events was shown under natural conditions (unprotected sites). The erosion rate was 4 times greater over rainy periods than dry ones, reaching 80% of cast numbers. It appeared that not the runoff effect but the splash effect, due to the kinetics of the drops, disrupted casts. Newly formed casts disappeared first, with the erosion rate decreasing twofold for casts more than 10 days old. Cast erosion and runoff, as well as worm casting activity, were greater under compacted sites than under non-compacted sites, indicating an influence of earthworms on soil erosion from compacted soils. The total phosphorus content was similar in casts and uningested soil (0.80 mg phosphorus g–1). Potential phosphorus losses from cast erosion was calculated to reach 25–49 mg phosphorus m–2 per rainfall event depending on soil compaction. The amounts of particulate phosphorus recovered in water runoff after each rainfall event varied from 1 mg to 11 mg phosphorus. These results are compared and discussed.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Oecologia 119 (1999), S. 247-255 
    ISSN: 1432-1939
    Keywords: Key words Nitrogen ; Phosphorus ; Nutrient spiraling ; Uptake rate and length ; Stream nutrient cycling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Nitrate and phosphate solutions were released into two reaches of two central Idaho streams to determine within- and between-stream variability in uptake lengths, uptake rates, and mass transfer coefficients. Physical and biotic stream characteristics and periphyton nitrate-uptake rates in recirculating chambers were measured to determine their influence on nutrient dynamics. Phosphate uptake length did not differ among the four reaches. There were no within-stream differences in nitrate uptake lengths but they did differ between the two streams. Long nitrate uptake lengths likely were due to instream concentrations above saturation but also may have been influenced by differences in active surface area and algal abundance. Nitrate and phosphate uptake lengths were longer, and uptake rates higher, than most other published values. However, mass transfer coefficients were comparable to measurements in other streams. Mass transfer coefficients may be a better parameter for temporal and spatial comparisons of instream nutrient dynamics, and for determining the underlying causes of variability in uptake length.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Coral reefs 18 (1999), S. 263-271 
    ISSN: 1432-0975
    Keywords: Key words Syringodium isoetifolium ; Cyanobacteria ; Stable isotopes ; Nitrogen ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract  The natural carbon and nitrogen stable isotope ratios (δ13C, δ15N) of various autotrophs and heterotrophs were measured in a Syringodium isoetifolium-dominated seagrass bed at Dravuni Island, Fiji to define carbon and nitrogen sources for heterotrophic organisms in a system where few animals graze directly on seagrass leaves. The organic carbon, nitrogen, and phosphorus content of organisms was also determined. The δ13C and δ15N data suggest that herbivorous heterotrophs in this seagrass bed depend significantly on epiphytic cyanobacteria rather than seagrass leaves and its detritus. This can be attributed to relative differences in nitrogen content of those organic materials. The cyanobacteria nitrogen content (3.6–4.8% of DW) is nearly half that of heterotrophs (7.0–8.6% N of DW) while that of S. isoetifolium origin (0.6–1.1% N of DW) is less than one third of the cyanobacteria nitrogen content. Phosphorus content was similar among cyanobacteria (0.8–1.1 mg g-1) and S. isoetifolium (0.4–1.4 mg g-1). These results suggest that cyanobacteria are important food sources for heterotrophs at the study site, and that inorganic nitrogen released through breakdown of cyanobacteria by heterotrophs may support the continued production of S. isoetifolium.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Hydrobiologia 410 (1999), S. 123-130 
    ISSN: 1573-5117
    Keywords: Nitrogen ; Phosphorus ; rivers ; modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In many European rivers, including the major streams of the Rhine and Elbe basins, the nutrient load (N and P) still exceeds target levels. In this paper, a model is presented that describes the river nutrient load as a function of nutrient sources, runoff and lithology in the upstream basin. The model was tested with independent data on nutrient sources (input) and nutrient river load (output) for 130 specific combinations of sub-basins and 5 year periods. A wide range of river systems within the Rhine and Elbe basins were included and the analysis covers a period of 25 years from 1970 to 1995. Most of the observed spatial and temporal variation in the average annual river nutrient load was successfully described by the model. It is therefore concluded that the model can be used to predict the effect of changes in nutrient sources (e.g. reduction of livestock numbers, further improvement of waste water treatment plants etc.) on the average annual nutrient loads of the rivers Rhine, Elbe and their main tributaries.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 1173-1183 
    ISSN: 1434-193X
    Keywords: Marine alkaloids ; Pyrroloquinoline ; Total synthesis ; Heterocycles ; Alkaloids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Batzellines A and B (1a, b) and isobatzellines A and B (2a, b) are 1,3,4,5-tetrahydropyrrolo[4,3,2-de]quinoline-containing marine alkaloids characterized by the presence of a methylthio substituent at C-2 of the tricyclic system. We describe here the total synthesis of these natural compounds following the synthetic strategy that we have used previously for the synthesis of damirones A and B, batzelline C, isobatzelline C, discorhabdin C, and makaluvamines A, B, C, and D. The introduction of the methylthio group by electrophilic substitution of a pyrrolo[4,3,2-de]quinoline, appropriately substituted and in a suitable oxidation state, is the key step in the success of these syntheses.
    Additional Material: 2 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 1213-1221 
    ISSN: 1434-193X
    Keywords: Diazo compounds ; Carbenes ; Carbenoids ; Silicon ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Copper(I) triflate catalyzes the transformation of α-[(2-alkynyl)oxy]silyl-α-diazoacetates 1a-g into 1,2-bis(2,5-dihydro-1,2-oxasilol-4-yl)ethenes 2 and/or 2H-1,2-oxasilines 3. With rhodium(II) perfluorobutyrate as catalyst, 1a-e furnish only 3 but no 2. Bicyclic 2-methoxyfurans 6 are formed when 1a,c,e (containing terminal alkyne functions) are treated with catalytic amounts of copper(I) chloride. The experimental observations are explained in terms of metal-mediated intramolecular cyclopropenation and subsequent metal-assisted ring-opening of the strained bicyclic cyclopropene leading to vinylcarbene-metal complexes. An unusual autoxidation of 2H-1,2-oxasilines 3a,c,e is also described.
    Additional Material: 1 Ill.
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  • 13
    ISSN: 1434-193X
    Keywords: Homogenous catalysis ; Palladium ; Cross-coupling ; Heterocycles ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 5-acceptor-substituted 2,3-dibromofurans 1 and 2 underwent a regioselective Pd0-catalyzed coupling reaction at the C-2 carbon atom. With alkynes the corresponding 2-alkynylfurans 4 and 5 were accessible (49-97% yield). Alkyl-, aryl-, and alkenylzinc reagents gave the 2-substituted furans 8 starting from compound 2 (66-84% yield). The 2-allylfurans 8e and 8f were obtained by a regioselective Stille coupling in 79% and 73% yield. The latter reaction was also applied to the parent 2,3-dibromofuran (27) and yielded the substitution product 28 (60% yield). Subsequent Pd0-catalyzed reactions to introduce a methyl group in 3-position by a methyldebromination were successfully conducted for 2-alkynyl-3-bromofurans with MeZnCl and PdCl2(PPh3)2 as the catalyst in THF (reflux) to yield compounds 13-16 and 24 (67-76%) and with SnMe4 and PdCl2[P(o-Tol)3]2 as the catalyst in DMA (90 °C) for the 2-allyl-3-bromofuran 8e to yield 18 (70%). The more facile reaction of the 2-alkynylfurans relative to those of furans bearing an sp3-carbon atom at C-2 appears to be due to steric reasons. Studies on the 2-alkyl-3-bromofuran 20 supported this notion. With the regioselective coupling methodology the terpene rosefuran (22) was prepared in four steps starting from furan 2 (35% yield overall). The F5 furan fatty acid (26) was synthesized from furan 1 in five steps (29% yield overall).
    Additional Material: 4 Tab.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 2965-2967 
    ISSN: 1434-193X
    Keywords: Amino alcohol ; Asymmetric synthesis ; Cell signaling ; Dihydroxylations ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cytoxazone [(4R,5R)-(-)-5-hydroxymethyl-4-(4-methoxyphenyl)-2-oxazolidinone, 1], a new immunosuppressant, was synthesized by starting from p-methoxycinnamyl alcohol (2) employing the Sharpless asymmetric dihydroxylation as the key reaction in 26% overall yield (7 steps).
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  • 15
    ISSN: 1434-1948
    Keywords: Metallaoxirane ; HBR2 addition ; (Formaldehyde)zirconocene ; (Butadiene)zirconocene ; Heterocycles ; Boron ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (η2-Formaldehyde)zirconocene dimer (8) cleanly adds one or two molar equivalents of the borane HB(C6F5)2 by insertion of the H-[B] unit into the zirconium-carbon bond of the metallaoxirane moieties to form the mono- and bis-insertion products 16 and 17, respectively. These systems contain five-membered heterocyclic rings that are built up by connecting five different elements, namely H, B, C, O, and Zr. The bis(borane) insertion product 17 was characterized by an X-ray crystal structure analysis. (Butadiene)zirconocene reacts with HB(C6F5)2 in a similar way by insertion of the H-[B] unit into the (butadiene)C4-Zr linkage to form the metallacycle 18.
    Additional Material: 1 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1659-1664 
    ISSN: 1434-1948
    Keywords: Phosphorus ; Iminophosphorane ; Staudinger reaction ; Heterocycles ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Staudinger-model reaction H3P (1) + HN3 (2) → H3P=NH (5) + N2 (6) has been investigated at the CCSD(T)/6-31G**//MP2(Full)/6-31G* level. Primary products formed in this reaction are the phosphazides H3P=N-N=NH (3) which exist as trans and cis isomers. In contrast to some previous assumptions, cis -3is 8.2 kcal mol-1 more stable than trans -3 but decomposes rather easily into the expected products H3P=NH and N2. This decomposition can be effectively hampered by intramolecular donor-acceptor interactions as shown by calculations on model compounds as well as by experiments. Thus the reaction of a methylene-σ3,λ3-phosphanyl-σ5,λ5-phosphorane with PhN3 led to a new four-membered heterocycle containing a thermally remarkable stable cis-phosphazide moiety.
    Additional Material: 4 Ill.
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  • 17
    ISSN: 1434-1948
    Keywords: Aluminium ; Amides ; Calcium ; Metallacycles ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of calcium bis[bis(trimethylsilyl)amide] with two equivalents of tris(trimethylsilylmethyl)alane yields (Me3SiCH2)2Al-N(SiMe3)2 (1) and the dimer [(Me3Si)2N-Ca(μ-CH2SiMe3)2Al(CH2SiMe3)2]2 (2). The five-coordinate bridging carbon atoms show Ca-C bond lengths of 264 and 268 pm. A similar reaction with calcium bis[bis(trimethylsilyl)phosphanide] gives the dimer [(Me3SiCH2)2Al-P(SiMe3)2]2 (3) with crystallographic C2 symmetry. A calcium-containing species is not isolable, however, in the presence of DME - ether cleavage reactions and the formation of the centrosymmetric dimer [(Me3SiCH2)2Al-OCH2CH2OMe]2 (4) are observed. The central moiety is an Al2O2 cycle with fivefold coordinated aluminium centers.
    Additional Material: 4 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2215-2220 
    ISSN: 1434-1948
    Keywords: Magnesium ; Metalation ; Phosphorus ; Polyhedra ; X-ray structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The magnesiation of triisopropylsilylphosphane with dibutylmagnesium in toluene yields the octanuclear complex [Mg8(PSiiPr3)6{P(H)SiiPr3}4] (1) which consists of MgPSiiPr3 units forming a hexagonal Mg6P6 prism, with two opposite Mg2P2 moieties capped by additional Mg[P(H)SiiPr3]2 groups. If a small amount of THF is present during the metalation reaction [(THF)4Mg6(PSiiPr3)6] (2) also containing a hexagonal Mg6P6 prism can be isolated. The magnesiation of H2P-SiiPr3 in tetrahydrofuran leads to the formation of the tetrameric complex [(THF)MgPSiiPr3]4(3) with a slightly distorted Mg4P4 cubane-like structure.The structures depend strongly on the steric strain caused by the trialkylsilyl substituents and the neutral coligands at the magnesium center. The highest steric strain, which is induced by coordination to every magnesium atom, leads to the smallest MgnPn polyhedron - the central Mg4P4 heterocubane moiety. In compounds 1 and 2 the hexagonal Mg6P6 prism is formed, however, with reduced steric strain as observed for 2 where the Mg-P bond lengths become more similar.
    Additional Material: 4 Ill.
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  • 19
    ISSN: 1434-1948
    Keywords: Metallacycles ; Solid-state structures ; Heterocycles ; Oxidations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Direct oxidation of PhC(O)NHPPh2, H2NC(S)NHPPh2, (C5H4N)C(S)NHPPh2 with O2, S8, or Se gives [PhC(O)NHP(O)Ph2] (1), [H2NC(S)NHP(S)Ph2] (2), [H2NC(O)NHP-(S)Ph2] (3), [PhC(O)NHP(S)Ph2] (4), [(C5H4N)C(S)NHP(S)Ph2] (5), and [H2NC(S)NHP(Se)Ph2] (6). Deprotonation of 1, 2, 4-6 with potassium tert-butoxide gives K[PhC(O)NP(O)Ph2] (7), K[H2NC(S)NP(S)Ph2] (8), K[PhC(O)NP(S)Ph2] (9), K[(C5H4N)C(S)NP(S)Ph2] (10), and K[H2NC(S)NP(Se)Ph2] (11). Reaction of 4with KOBu and [Cu(Ph3P)2][NO3] gives [Cu(Ph3P)(PhC(O)NP(S)Ph2)] (12) which is the first crystallographically characterised example of a non-ionic six-membered “true” heterocycle (i.e. a ring in which every heterocatom is different). 9 and 10 were treated with [PdCl2(COD)] to give [Pd{PhC(O)NP(S)Ph2}2] (13) and [Pd{(C5H4N)C(O)NP(S)Ph2}2] (14), respectively The anion of 8 coordinates to zinc forming [Zn{H2NC(S)NP(S)Ph2}2] (15). Treatment of 2 or 8 with [PtCl2(COD)] gives [Pt{H2NC(S)NP(S)Ph2}{H2NC(S)NHP(S)Ph2}]+Cl- (16) and [Pt{H2NC(S)NP(S)Ph2}2] (17), respectively. The X-ray structures of 12, 15-17are reported.
    Additional Material: 5 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 393-398 
    ISSN: 1434-1948
    Keywords: Boranes ; Bipyridine ; Crystal structures ; Donor-acceptor interaction ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 6,6′-Bis(diethylboryl)-2,2′-bipyridine (1a) was obtained in low yield by in situ deprotonation of 2,2′-bipyridine in the presence of diethyl(methoxy)borane. 6,6′-Dilithio-2,2′-bipyridine reacts with various alkoxyboranes leading to bipyridinediborates 2 in good yields. The derivatives 2b and 2c allow the formation of the free diborylbipyridines 1b and 1c. The coordination properties of the diboryl-bipyridines as tetrafunctional donor-acceptor compounds have been used for the formation of the copper complex 4 and of the adduct 5 which is built from diborylbipyridine and a dihydroxydiboroxan derivative. The composition of the products follows from spectroscopic data and from X-ray structure analyses for 2f, 4, and 5.
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  • 21
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 491-497 
    ISSN: 1434-1948
    Keywords: Boron ; Diazaboroles ; Hydrides ; Tin ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Di-tert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (4a) and 1,3-bis(2,6-dimethylphenyl)-2,3-dihydro-1H-1,3,2-diazaborole (4b) were formed by the reaction of the corresponding 2-bromo or 2-iodo derivatives 1a and 2b with LiAlH4. Treatment of 1a with n-butyllithium afforded 2-n-butyl-1,3-di-tert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (5a), whereas 1,3-di-tert-butyl-2-cyano-2,3-dihydro-1H-1,3,2-diazaborole (3a) was converted into the 2-tert-butyl derivative 6a or the 2-ethynyl-1,3,2-diazaborole 7a by means of tert-butyllithium or by the ethylenediamine adduct of lithium acetylide. Similarly, 1,3-di-tert-butyl-2-trimethylstannyl-2,3-dihydro-1H-1,3,2-diazaborole (8a) and 1,3-bis(2,6-dimethylphenyl)-2-trimethylstannyl-2,3-dihydro-1H-1,3,2-diazaborole (8b) were accessible from 1a or 2b and trimethylstannyllithium. In the complex 9a the compound 3a serves as an η1 ligand towards the [Cr(CO)5] unit via the cyano group. These novel compounds were characterized by 1H-, 11B-, 13C-, and 119Sn-NMR spectroscopy, as well as by X-ray structure analyses of 4b, 8a, and 9a.
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  • 22
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 499-504 
    ISSN: 1434-1948
    Keywords: Alkynes ; Heterocycles ; Cyclizations ; Cobalt ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following monocyclic and bicyclic 14-membered diynes were treated with [CpCo(cod)]: 1-oxacyclotetradeca-4,11-diyne (2), 1,8-dioxacyclotetradeca-4,11-diyne (3), cyclotetradeca-4,11-diynone (4), cyclotetradeca-4,11-diyne-1,8-dione (5), 1,1,8,8-tetramethyl-1,8-disilacyclotetradeca-4,11-diyne (6), 1-allyl-1-azacyclotetradeca-4,11diyne (7), 1,8-dipropyl-1,8-diazacyclotetradeca-1,11-diyne (8), 1,8-diallyl-1,8-diazacyclotetradeca-4,11-diyne (9), 1,8-diazabicyclo[6.6.4]octadeca-4,11-diyne (10), 1,8-diazabicyclo[6.6.6]eicosa-4,11-diyne (11), 1,10-diazabicyclo[8.6.6]docosa-13,19-diyne (12) and 1,12-diazabicyclo[10.6.6]tetracosa-15,21-diyne (13). In all cases we obtained an intramolecular cyclobutadiene complex stabilized with a CpCo fragment (15-26). For 3 we could isolate, besides the cyclobutadiene complex 16, the trimerization product 28. In the cases of 15, 16, 18, 20, 23, 25, and 26 the structure of the cylobutadiene complexes could be confirmed by X-ray studies. Common to all structures is a boat-like conformation of the tricyclic unit containing the cyclobutadiene ring. The two cycloheptene units adopt a chair conformation in which the heteroatom is removed from the metal center.
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  • 23
    ISSN: 1434-1948
    Keywords: Phosphorus ; Ferrocenes ; Phosphorylated iminophosphoranes ; Dendrimers ; Cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several R3P=N-P(X)R′2 and Fe[C5H4Ph2P=N-P(X)R′2]2 derivatives (X = S, O) are readily obtained from Staudinger reactions between phosphanes and N3-P(X)R′2. The P=N-P=X groups are easily alkylated on the × atom with methyl or isopropyl triflates. The alkylation induces a lengthening of the P-X bond, as shown by X-ray diffraction studies. This corresponds to a weakening of the P-X bond which can be cleaved with P(NMe2)3 to yield [P=N-P:] linkages. The presence of tricoordinated phosphorus atoms opens the way to a versatile reactivity, including the reaction with alkyl iodides and functionalized azides. These molecules are good models for screening which types of reagents and reactions could be used with macromolecules possessing also P=N-P=X linkages, such as dendrimers.
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  • 24
    ISSN: 1434-1948
    Keywords: Arsenic ; Barium ; Calcium ; Metalations ; NMR spectroscopy ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metalation of triisopropylsilylphosphane with bis(tetrahydrofuran-O)calcium bis[bis(trimethylsilyl)amide] in tetrahydropyran (thp) in a molar ratio of 3:2 yields (Me3Si)2NCa[μ-P(H)SiiPr3]3Ca(thp)3 (1) containing a trigonal-bipyramidal Ca2P3 core, the metal atoms occupying apical positions. Reaction of two equivalents of triisopropylsilylphosphane or -arsane with bis(tetrahydrofuran-O)barium bis[bis(trimethylsilyl)amide] in tetrahydrofuran gives the corresponding bis(phosphanide) 2 and bis(arsanide) 3, compounds of the type (thf)3Ba[μ-E(H)SiiPr3]Ba(thf)2E(H)SiiPr3 with E = P, As. The equimolar reaction of (tri-tert-butylsilyl)phosphane with (thf)2Ba[N(SiMe3)2]2 in toluene yields heteroleptic dimeric (thf)2Ba[N(SiMe3)2][P(H)SitBu3] (4). Addition of a further equivalent of H2PSitBu3 leads to the formation of homoleptic (thf)nBa[P(H)SitBu3]2 (5). Dissolution of the latter in aromatic hydrocarbons leads to the elimination of H2PSitBu3, yielding dimeric (thf)Ba3(PSitBu3)2[P(H)SitBu3]2 (6). The inner core of 6 consists of the tetramer (BaPSitBu3)4 based on a Ba4P4 heterocubane unit, two opposite faces being capped with (thf)Ba[P(H)SitBu3]2 molecules.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2233-2241 
    ISSN: 1434-1948
    Keywords: Phosphorus ; Heterocycles ; Phosphinines ; Gold ; Cycloadditions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination behaviour of 2,6-disilyl-substituted phosphinines towards gold(I) has been examined. The reaction of the bis(trimethylsilyl)phosphinine 1 with [AuCl(SMe2)] gives the corresponding AuCl derivative 2. X-ray crystal structure analysis reveals that the aromaticity of the phosphinine ring is slightly reduced as a result of the poor π-back bonding ability of the AuCl fragment. The same phenomenon is observed in the cationic complex [Au(1)2][GaCl4] (3) which was readily prepared by reaction of two equivalents of 1 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. Reaction of 2,6-bis(phenylethynyldimethylsilyl)phosphinine (4) with the same precursor leads similarly to the complex [AuCl(4)] (5). Interestingly, this complex dimerizes upon crystallization to give the bis(phosphabarrelene) complex 6, also structurally characterized. The formation of 6 results from a [4 + 2] cycloaddition between one alkynyl group of each phosphinine with the other phosphinine subunit. The formation of the cationic complex [Au(4)][GaCl4] (8) occurs under classical conditions but it disproportionates to give the cationic complex [Au(4)2][GaCl4] (9) and colloidal gold deposition. The formation of 9 has been ascertained by treating 8 with one equivalent of ligand 4. Additionally, 9 can also be obtained in a straightforward fashion by treating two equivalents of 4 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. The structure of 9 has been elucidated. Despite a particular arrangement of the alkyne groups which encapsulate the gold coordination sphere, no gold-alkyne interactions are visible.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2295-2299 
    ISSN: 1434-1948
    Keywords: Lewis acids ; Bismuth ; Aluminum ; Phosphorus ; Tin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dilithium salts of N-methyl-N′,N′′-bis(diisopropyl)- and -(trimethylsilyl)-diethylenetriamine 1a,b react with SnCl2 affording the corresponding stannylenes 2a,b in 60 and 80% yield, respectively. Compound 1b also reacts with BiCl3 to give the bismuth chloride 5 (90% yield). Derivatives 2b and 5 have a symmetrical bicyclic structure and are monomeric both in solution and in the solid state. When 2b is treated with BiCl3 or PCl3, an oxidation reaction leads to the hypercoordinated tin(IV) dichloride 3 (58% yield), or a transmetallation gives rise to the oniophosphane 4 (95% yield), respectively. Transmetalation reactions also occurred when 5 was treated with AlCl3, GaCl3 or SnCl2 affording the corresponding aluminum chloride 6 (81% yield), gallium chloride 7 (38% yield) or tin dichloride 3 (38% yield). The observed reactivity for 2 and 5 is compared to that reported for Veith's stannylene or bismuth chloride.
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  • 27
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 887-898 
    ISSN: 1434-1948
    Keywords: Tin ; Phosphorus ; Intramolecular coordination ; O ligands ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New intramolecularly coordinated organotin compounds containing the monoanionic O,C,O-coordinating ligand {4-tert-Bu-2,6-[P(O)(OEt)2]2C6H2}- have been synthesized by substitution reactions starting from organotin halides. In view of the enhanced reactivity of the intramolecularly coordinated compounds {4-tert-Bu-2,6-[P(O)(OEt)2]2C6H2}SnR2R′ (2, R = Ph, R′ = CH2SiMe3; 3, R = R′ = Ph; 6, R = R′ = Cl), cationic tin species are suggested to occur as intermediates in the formation of the heterocyclic compounds [1(Sn),3(P)-Ph2SnOP(O)(OEt)-5-tert-Bu-7-P(O)(OEt)2]C6H2 (8), [1(Sn), 3(P)-Ph(Me3SiCH2)SnOP(O)(OEt)-5-tert-Bu-7-P(O)(OEt)2]C6H2 (15), and {[1(Sn),3(P)-Cl2SnOP(O)(OEt)-5-tert-Bu-7-P(O)(OEt)]C6H2}2 (16). The latter compounds are formed by intramolecular cyclizations of pentacoordinate cationic tin species under elimination of ethyl halide. Furthermore, the synthesis of [1(Sn),3(P)-Ph2SnOP(O)(OH)-5-tert-Bu-7-P(O)(OH)2]C6H2 (13) is described. Reaction of 8 with an excess of Me3SiBr leads to the unexpected formation of {2-[P(O)(OEt)(OSiMe3)]-4-tert-Bu-6-[P(O)(OEt)2]C6H2}SnPhBr2 (9) as a result of an O-Sn bond cleavage initiated by Me3SiBr and subsequent reaction of the intermediate with further Me3SiBr under Sn-C bond cleavage. The high donor capacity and the rigidity of the new ligand {4-tert-Bu-2,6-[P(O)(OEt)2]2C6H2}- are demonstrated by X-ray diffraction analyses of the tetraorganotin compound 2 and the monoorganotin trichloride 6. Furthermore, the molecular structures of the 2,3,1-oxaphosphastannoles 8 and 16 are discussed.
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  • 28
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 7-9 
    ISSN: 1434-1948
    Keywords: Boranes ; Diazaboroles ; Heterocycles ; Ketiminoboranes ; Crystal Structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclocondensation reaction of benzil-bis(trimethylsilylimin) (3) and Cl2B-NiPr2 via silicon-boron exchangeresults in the solvent-dependent formation of the 1,3,2-diazaborole 1a or the 1,3,6,8,2,7-tetraazadiborecin 2a. Using the more rigid 9,10-bis(trimethylsilylimino)phenanthrene instead of 3 only the five-membered heterocycle 4,5-biphenylene-2-diisopropylamino-1,3,2-diazaborole (1b) is formed. The cyclic ketiminoboranes are characterized by NMR and X-ray diffraction data. The 1,3,2-diazaborole ring is almost planar, while the conformation of the 1,3,6,8,2,7-tetraazadiborecin has the shape of a figure-eight loop.
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  • 29
    ISSN: 1434-1948
    Keywords: Phosphorus ; Rhenium ; 31P-NMR spectroscopy ; Tripodal polyphosphanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of white phosphorus with [(triphos)Re(CO)2(OTf)] (1) in dichloromethane affords the new tetraphosphorus complex [(triphos)Re(CO)2(η1-P4)](OTf) (2) [triphos = MeC(CH2PPh2)3; OTf = OSO2CF3]. Compound 2 reacts with a second equivalent of 1 to give the binuclear complex [{(triphos)Re(CO)2}2(μ,η1,η1-P4)](OTf)2 (3) in which a tetrahedro-P4 ligand behaves as tethering unit between two [(triphos)Re(CO)2]+ moieties. Complexes 2 and 3 represent the first soluble metal complexes of the tetraphosphorus molecule where the P4 ligand has not undergone any major modification.
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  • 30
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 945-949 
    ISSN: 1434-1948
    Keywords: Phosphorus ; Pn ; C5H3(SiMe3)2 ligands ; Cobalt ; Coordination chemistry ; Crystallography ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal or photochemical reaction of [Cp′′Co(CO)2] (1) [Cp′′ = C5H3(SiMe3)2-1,3] with white phosphorus (P4) gives [{Cp′′Co}2(P5-P5){CoCp′′}2] (2) and [{Cp′′Co}3P4(μ-CO)] (3) as well as [{Cp′′Co}2(μ-η2:η2-P2)2] (4). Cobalt complexes 2, 3, and 4 have been characterized by an X-ray crystal-structure determination.
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  • 31
    ISSN: 1434-1948
    Keywords: Cyclotriphosphazenes ; Oxypyridine ; Carbonyltungsten compounds ; NMR spectroscopy ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of [N3P3(dobp)2Cl2] and [N3P3(dobp)Cl4] with a mixture of HOC5H4N-4 and K2CO3 in acetone give the cyclotriphosphazenes [N3P3(dobp)2(OC5H4N-4)2] and [N3P3(dobp)(OC5H4N-4)4], respectively. These compounds react with [W(MeOH)(CO)5] in methanol to give mixtures of the polymetallic complexes [N3P3(dobp)2(OC5H4N-4)2{W(CO)5}x] (x = 1, 2) and [N3P3(dobp)(OC5H4N-4)4{W(CO)5}x] (x = 1-4), which are unstable in solution, slowly undergoing loss of the pentacarbonyl moiety. A complete characterization by multinuclear 1H, 15N, 31P, 183W magnetic resonance has revealed that the complexation of the N atom of one 4-oxypyridine ligand by the W(CO)5 fragment has a measurable effect on other parts of the phosphazene molecule very far away from the coordination site. The changes observed in δ183W have been used to identify the components in mixtures of compounds incorporating different numbers of tungsten atoms in the molecule. The characterization of less sensitive nuclei has been accomplished by means of indirect detection methods.
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  • 32
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2327-2333 
    ISSN: 1434-1948
    Keywords: Heterocycles ; Organo-phosphorus compounds ; Dithiadiphosphetane disulfides ; Phosphonates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New salts of thionated (naphthalene-1,8-diyl)bis(phosphonic) acid monoanhydrides [PPh4+]2[C10H6PS2(μ-S)PS22-] (2) and [K+]2[C10H6PS2(μ-S)POS2-]·H2O (3) both containing the C3P2S ring, were prepared in high yields by the reaction of 2,4-(naphthalene-1,8-diyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide (1) with NaHS and PPh4Cl, or KOH, respectively, in water. The derivative 3, containing a P=O terminal bond as well as P-S-P bridge, undergoes, in acid conditions, a rearrangement reaction leading to the O,S-symmetrically substituted derivative [K+]2[C10H6PS2(μ-O)PS22-] (4) containing a C3P2O heterocycle. Dipotassium salt 4 was converted into the bis(tetraphenylphosphonium) salt 5 by the treating with PPh4Cl. Hydrolysis of [PyH+][C10H6P(S)(NHMe)(μ-S)PS22-] (15) led to [CH3NH3+][PyH+][C10H6POS(μ-O)POS2-]·1.5 Py (6). New compounds were characterised by 31P{1H}-, 1H- and 13C{1H}-NMR, FT-IR, ES-MS and in the cases 2-6 by X-ray structure determination. The 31P{1H}-NMR spectra of these mixed O,S-derivatives are briefly discussed.
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  • 33
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1193-1198 
    ISSN: 1434-1948
    Keywords: Boron ; Triazaboroles ; Heterocycles ; Halogens ; Cyanides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3,4-Dihydro-2,4-diphenyl-2H-1,2,4,3-triazaboroles 3a, 3b, and 4 were synthesized by cyclocondensation of N1,N3-diphenylformamidrazone (1) with dibromophenylborane, dibromomethylborane, and boron trichloride. 3-Chloro-3,4-dihydro-2,4-diphenyl-2H-1,2,4,3-triazaborole (4) was converted into 3,4-dihydro-2,4-diphenyl-2H-1,2,4,3-triazaborole (5) by treatment with LiAlH4. The corresponding 3-cyanato and 3-cyano derivatives 6 and 7 resulted from the reaction of 4 with AgOCN and AgCN, respectively. Compound 7 was transformed into the bis(1,2,4,3-triazaborolyl)oxane 8 by silver oxide. Compounds 1-8 were characterized by elemental analyses and spectroscopic methods (1H, 11B, and 13C NMR; IR; MS). The molecular structure of 8 was established by single-crystal X-ray diffraction analysis.
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  • 34
    ISSN: 1434-193X
    Keywords: Amino acids ; Lactams ; Schiff bases ; Nitrogen heterocycles ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several derivatives of homopipecolic acid are prepared by α-amino alkylation of malonic acid with cyclic imines 6 and 7. These are prepared on a large scale and with different substitution patterns. The β-amino acids 8 and 9 were formed in high yield and with remarkable diastereoselectivity if chiral imines are used as starting materials. The diastereoselectivity of the amino alkylation leading to homopipecolic acid analogues is compared to those of thiazolidineacetic acids by epimerisation experiments. A method for resolution of the obtained racemic β-amino acids by diastereomeric salt formation is described. The β-amino acids 9 and 15 were converted into their corresponding carbacepham analogues 14 and isopenam 16. The isopenam endo-16 was selectively epimerised by mild basic treatment of the N/S-acetal to give an exo-configured precursor of isopenicillin G.
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  • 35
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Heterocycles ; Palladium ; Alkylations ; Allyl complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A convenient synthesis of racemic tetrahydropyridine 1 was developed. Pd-catalyzed allylic alkylation of 1 with malonate and dimethylacetoxymalonate as nucleophiles with the phosphanylcarboxylic acid L1 and the dihydrooxazol L2 as ligands, were carried out and gave enantiomeric excesses of up to 98%. Absolute configurations were determined for all compounds described. From the alkylation products (+)- and (-)-2a, and (+)- and (-)-2b a variety of versatile, nonracemic chiral intermediates were prepared.
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  • 36
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 789-793 
    ISSN: 1434-1948
    Keywords: Boranes ; Carbenes ; Heterocycles ; Imidazoles ; X-ray structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nucleophilic carbene 3-borane-1,4,5-trimethylimidazol-2-ylidene anion (1-) reacts with the electrophiles CH3I, (CH3)3SiCl, (CH3)3SnCl, and the bromodiazaboroline 7 to form the 2-substituted imidazoles 4, 5, 6, and 8. With triethylborane, the anionic carbene borane adduct 9- is obtained. An unexpected result was achieved when chlorodimethoxyborane and HBCl2 · S(CH3)2 were used as electrophiles. In both cases only the imidazabole 14a could be isolated. Imidazole 5, the imidazole borane adduct 3a and the imidazabole 14a were characterized by X-ray structure analyses.
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  • 37
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1095-1102 
    ISSN: 1434-1948
    Keywords: Silanorbornenes ; Silanorbornanes ; Silicon-functionalized olefins ; Silacyclobutanes ; Hydrogenations ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Catalytic hydrogenation of olefins containing functionalized silicon groups affords the saturated products in good yields. Chloro and alkoxy substituents at the silicon atom remain unaffected and, in the case of heterocyclic compounds, the cyclic or bicyclic moieties remain intact. The 2-silanorbornanes 4, 5, and 6 were synthesized from the corresponding 2-silanorbornenes 1, 2, and 3, and organosilanes 13 and 14 possessing the cyclopentyl group, were prepared from the cyclopentenyl-substituted precursors 10 and 12. The 3-vinyl-substituted silacyclobutanes 15, 17, and 18 were also hydrogenated in a simple apparatus with diethyl ether or THF as solvent, and Pd/C as a recoverable catalyst system. A basic organosilicon compound, trichloro(vinyl)silane, is hydrogenated in a nearly quantitative yield to form the saturated trichloro(ethyl)silane; this emphasizes the general applicability of this method.
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  • 38
    ISSN: 1434-193X
    Keywords: Carboxylic acid amides ; Chitinase ; Chitobiose ; Heterocycles ; Enzyme inhibitors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-(Dimethylamino)oxazoline-4-carboxylic acids 5 were prepared by condensation of binucleophilic amino acids 4and O-ethyl-N,N-dimethylisourea 3. New heterocyclic N-acetylglucosaminyl amides and chitobiosyl amides 8 were obtained by the coupling of tetraacetylglucosamine 6a or heptaacetylchitobiosylamine 6b with acid chlorides of heterocyclic carboxylic acids 2 or 5a and subsequent deacetylation. Based on their substitution patterns, compounds 8were expected to have inhibitory activity towards chitinases. Enzyme assays showed that glycosyl amides 8 indeed were moderate inhibitors of chitinases, the diacetylchitobiosyl amides 8d-f generally having higher inhibitory activities than the N-acetylglucosaminyl amide derivatives 8a-c. Inhibitory activities depended on the chitinase tested.
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  • 39
    ISSN: 1434-193X
    Keywords: Heterocycles ; Thiazoles ; Pyrido[3,4-c]thiazoles ; Triflates ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The readily available 2-substituted 5-acetyl-4-thiazolyl triflates 2are useful building blocks for the preparation of functionalised thiazoles by means of palladium-catalysed cross-coupling reactions with organometallic reagents and alkoxycarbonylation and deoxygenation reactions. The combination of palladium-catalysed coupling of 2 together with 1-alkynes/6-endo-dig annulation reactions in the presence of ammonia leads to functionalised pyrido[3,4-c]thiazoles in satisfactory yields. The utilisation of uncatalysed displacement reactions of the triflate group represents a very simple method for the synthesis of 4-N-,4-O-, and 4-S-substituted thiazoles.
    Additional Material: 2 Tab.
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  • 40
    ISSN: 1434-193X
    Keywords: Diazo compounds ; Carbenes ; Carbenoids ; Silicon ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photolysis of (ethoxy)silyl-, (propyloxy)silyl-, and (isopro-pyloxy)silyl-substituted diazoacetates 1a-c leads to tetrahydro-1,2-oxasiloles 2a-c by intramolecular C-H insertion of a carbene intermediate. Photochemical or catalytic decomposition of (allyloxysilyl)diazoacetates 3a-e results in intramolecular cyclopropanation which provides 3-oxa-2-silabicyclo[3.1.0]hexane systems 5a-e. In contrast, the thermal reaction of 3b-d gives rise to 2,5-dihydro-1,2-oxasiloles 4b-d, which are likely to be formed on a pyrazoline rather than a carbene route. For (3-butenyloxysilyl)diazoacetate 3f, all modes of decomposition generate the 3-oxa-2-silabicyclo[4.1.0]heptane system 7. Fluoride-induced cleavage of the bicyclic systems 5b-d provides trans-2-hydroxyalkyl-1-cyclopropanecarboxylates 9 diastereospecifically.
    Additional Material: 1 Tab.
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  • 41
    ISSN: 1434-193X
    Keywords: Amino acids ; Azaspiropentanes ; Heterocycles ; Peptides ; Strained molecules ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Azaspiropentanecarboxamides 10 and 12 are formed with remarkable ease in two steps in a one-pot operation from methyl 2-chloro-2-cyclopropylideneacetate (4) by addition of a primary amine in tetrahydrofuran and subsequent treatment with sodium hydride/triethylamine in the presence of another equivalent of a primary amine or ammonia. Achievable yields of the amides 10, 12 were moderate to good (27-59%, 12-48%), while the corresponding esters 9 could only be obtained in poor yields (4-14%). The new α-amino acid amides are surprisingly stable, and they can be incorporated into small peptides as demonstrated with the preparation of the glycine 13e and the spirocyclopro-paneoxazoline derivative 14e.
    Additional Material: 2 Ill.
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  • 42
    ISSN: 1434-193X
    Keywords: Amino acids ; α-Amino acid phenylhydrazides ; Heterocycles ; Cyclization reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ring forming condensation between some natural α-amino acid phenylhydrazides (1) and aqueous formaldehyde (2) has opened a novel synthetic route to hexahydro-1,2,4-triazin-6-one derivatives (3). Polycyclic systems were obtained from the same reaction carried out with L-aspartic acid 1,4-bis(2-phenylhydrazide) (1d), L-histidine phenylhydrazide (1e) and L-tryptophan phenylhydrazide (1f) which gave perhydro-4,6-dioxo-2,8-diphenyl[1,2,4]triazino[4,5-d][1,2,4]triazepine (5) perhydro-1-oxo-3-phenylimidazo[5,4-d][1,2,4]triazino[4,5-a]pyridine (7) and 1,2,3-H-3-(2-phenylcarbazoyl)-β-carboline (8), respectively. Substrates 1 were conveniently obtained by direct reaction of phenylhydrazine with L-α-amino acid esters retaining the original chirality.
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  • 43
    ISSN: 1434-193X
    Keywords: Heterocycles ; Alkaloids ; Castanospermine ; Metathesis ; Azasugars ; Manzamine A ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The application of the ring-closing metathesis (RCM) reaction to the construction of a wide variety of nitrogen-containing ring systems is described. The examples include pyrrolizidine, indolizidine, and quinolizidine derivatives related to azasugars. A formal total synthesis of castanospermine (5) is presented. The utilisation of two RCM steps in the synthetic sequence leading to the multicyclic ABCDE nucleus 7 of the complex alkaloid manzamine A (6) is discussed.
    Additional Material: 3 Ill.
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  • 44
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 1455-1458 
    ISSN: 1434-193X
    Keywords: Nucleoside analogues ; 1,3-Oxathiolanes ; Chiral sulfoxides ; Heterocycles ; Antiviral agents ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -A ready asymmetric synthesis of 3′-oxathionucleosides has been accomplished in three main steps from benzoyloxyethanal. The synthesis is characterized by high overall yield and considerable enantiomeric excesses. It represents a general synthetic path to prepare a wide range of heterosubstituted sulfur-containing nucleoside analogues.
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  • 45
    ISSN: 1434-193X
    Keywords: Carbohydrates ; Heterocycles ; Electrostatic interactions ; Glycosylation ; Glycosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two pairs of novel stereoisomeric, cyclic glycosyl donors exhibit different behaviors in glycosylation processes. In the pair of α-gluco (1) and β-manno (2), the former exhibits reversability with its glycoside product whereas the latter does not. In the α-gluco (3) and β-manno (4) set, the former undergoes glycosyl transfer via an isolable intermediate whereas the latter does not. The differing anomeric effects exerted in the ground states are proposed as the force which explains the differences in behavior.
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  • 46
    ISSN: 1434-193X
    Keywords: Acetals ; Heterocycles ; Mouse ; Mus musculus/ Pheromones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two components [2-sec-butyl-4,5-dihydrothiazole (1) and 3,4-dehydro-exo-brevicomin (2)] of a male-produced pheromone of the mouse Musmusculus have been synthesized in optically active forms. The enantiomers of 1 were obtained with an enantiomeric purity of ca. 92% ee and were found to be readily racemizable. Asymmetric dihydroxylation was employed as the key reaction (15→16) allowing the preparation of (1R,5S,7R)-2 with ca. 94% ee.
    Additional Material: 1 Tab.
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  • 47
    ISSN: 1434-193X
    Keywords: Lithium ; Lithium trimethylsilyldiazomethane ; Heterocycles ; Uracil derivatives ; Pyrazolo[4,3-d]pyrimidindiones ; Pyrazolo[4,3-d]pyrimidindiones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nucleophilic addition of TMSC(Li)N2 at the low reactive C-5 position of the uracil ring of C-6 substituted uracil derivatives is reported. The ratio of C-5 versus C-6 nucleophilic addition of TMSC(Li)N2 dramatically depends on the stereoelectronic properties of the C-6 substituent. In particular, substituents characterized both by sterically bulky and/or electron-withdrawing (EWG) effects appear to direct the nucleophile mainly (methyl, chloromethyl or halogen) or completely (isopropyl) toward the C-5 position. The fine-tuned substituent selectivity found in the nucleophilic addition of TMSC(Li)N2 to C-6 substituted uracils plays a leading role in the synthesis of new trimethylsilyl-1H-[4,3-d]pyrimidin-5,7-dione derivatives, which can in turn be easily modified through known silicon chemistry.
    Additional Material: 1 Ill.
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  • 48
    ISSN: 1432-1890
    Keywords: Key words Arbuscular mycorrhiza ; Iron ; Peanut ; Phosphorus ; Sorghum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The influence of an arbuscular mycorrhizal (AM) fungus on phosphorus (P) and iron (Fe) uptake of peanut (Arachis hypogea L.) and sorghum (Sorghum bicolor L.) plants was studied in a pot experiment under controlled environmental conditions. The plants were grown for 10 weeks in pots containing sterilised calcareous soil with two levels of Fe supply. The soil was inoculated with rhizosphere microorganisms only or with rhizosphere microorganisms together with an AM fungus (Glomus mosseae [Nicol. & Gerd.] Gerdemann & Trappe). An additional small soil compartment accessible to hyphae but not roots was added to each pot after 6 weeks of plant growth. Radiolabelled P and Fe were supplied to the hyphae compartment 2 weeks after addition of this compartment. After a further 2 weeks, plants were harvested and shoots were analysed for radiolabelled elements. In both plant species, P uptake from the labelled soil increased significantly more in shoots of mycorrhizal plants than non-mycorrhizal plants, thus confirming the well-known activity of the fungus in P uptake. Mycorrhizal inoculation had no significant influence on the concentration of labelled Fe in shoots of peanut plants. In contrast, 59Fe increased in shoots of mycorrhizal sorghum plants. The uptake of Fe from labelled soil by sorghum was particularly high under conditions producing a low Fe nutritional status of the plants. These results are preliminary evidence that hyphae of an arbuscular mycorrhizal fungus can mobilise and/or take up Fe from soil and translocate it to the plant.
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  • 49
    ISSN: 1432-1890
    Keywords: Key words Allium cepa ; Appressorium ; Arbuscular mycorrhiza ; Root colonisation ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The effect of root exudates from P-deficient onion on root colonisation by an arbuscular mycorrhizal fungus was examined. Onions (Allium cepa L.) were grown in solution culture at phosphorus concentrations of 0 (P0) and 2 (P2) mg P l–1. Root exudates were collected and fractionated with Amberlite XAD-4 resin to give EtOH and water soluble fractions. Onions inoculated with the arbuscular mycorrhizal fungus Gigaspora margarita Becker & Hall were grown with or without (control) root exudates and exudate fractions in a growth chamber. After 24 days, arbuscular mycorrhiza levels and appressoria formation had increased in plants treated with P0-root exudate or the P0-EtOH fraction when compared to corresponding P2 treatments or control plants. P0 and P2 water-soluble fractions did not significantly affect either aspect of fungal development. These results suggest that hydrophobic compounds found in root exudates from P-deficient onion increase appressorium formation and, therefore, enhance mycorrhiza development.
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  • 50
    ISSN: 1432-1890
    Keywords: Key words Acaulospora ; Hyacinthoides non-scripta ; Bluebell ; Disturbance ; Glomus ; Fine endophytes ; Phosphorus ; Scutellospora
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Early-season colonisation of new roots of Hyacinthoides non-scripta (L.) Chouard ex Rothm. was investigated to determine how arbuscular mycorrhizal symbiosis is re-established after the annual root system is shed. During the rootless phase in summer, colonies of bulbs were removed and replanted after the soil around and below the bulb had been mixed (major disturbance) so as to disrupt the external mycelium of arbuscular mycorrhizal (AM) fungi. As a minor disturbance treatment, top soil was removed, bulbs were turned or not in their growth position with as little other disturbance as possible, and the top soil replaced. Control plants were left undisturbed. Half of the plants were harvested 3–4 weeks after the onset of root emergence. Populations of all AM fungi in roots were greatly reduced by major disturbance, whilst those in other treatments and controls were unaffected. At the second harvest, in spring, when shoots had emerged, root colonisation by fine endophytes and Scutellospora morphotypes developed in all treatments, whereas that of Acaulospora morphotypes remained low after major disturbance. Disturbance treatments delayed the appearance, at the second harvest, of mycorrhizas with degenerate arbuscules. Leaf phosphorus concentration was unaffected by soil disturbance, possibly due to partial recovery of AM fungal populations or buffering by resources stored in the bulb.
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  • 51
    ISSN: 1432-1890
    Keywords: Key words Winter wheat ; Mycorrhiza ; Phosphorus ; Dryland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  A field experiment was conducted to determine the seasonal patterns of arbuscular mycorrhiza (AM) in a dryland winter wheat (Triticum aestivum L.) system and to determine wheat growth and P uptake responses to inoculation with mycorrhizal fungus. Broadcast-incorporated treatments included (1) no inoculation with mycorrhizal fungus, with and without P fertilizer, and (2) mycorrhizal fungal inoculation at a rate of 5000 spores of Glomus intraradices (Schenck and Smith), per 30 cm in each row, with and without fertilizer P. Winter wheat was seeded within a day after treatments were imposed, and roots were sampled at five growth stages to quantify AM. Shoot samples were also taken for determination of dry matter, grain yield and yield components, and N and P uptake. No AM infection was evident during the fall months following seeding, which was characterized by low soil temperature, while during the spring, the AM increased gradually. Increases in wheat grain yields by enhanced AM were of similar magnitude to the response obtained from P fertilization. However, responses differed at intermediate growth stages. At the tillering stage, P uptake was mainly increased by P fertilization but not by fungal inoculation. At harvest, enhanced AM increased P uptake regardless of whether or not fertilizer P was added. The AM symbiosis increased with rising soil temperatures in the spring, in time to enhance late-season P accumulation and grain production.
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  • 52
    ISSN: 1432-1890
    Keywords: Key words Peas ; Aphanomyces euteiches ; Phosphorus ; PAGE ; Isozymes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The effects of inorganic phosphate levels and the presence of arbuscular mycorrhiza on disease severity of Aphanomyces euteiches in pea roots were studied. Disease severity on roots and epicotyl as well as the oospore number within infected root tissue were correlated with the phosphorus (P) level in the growth medium. The arbuscular mycorrhizal fungus Glomus intraradices increased P uptake and the P concentration in the plant but reduced disease development in peas. Polyacrylamide gel electrophoresis followed by densitometry of glucose-6-phosphate dehydrogenase specific to A.euteiches was used to measure the activity of the pathogen in roots. The enzyme activity increased with disease severity and disease incidence, except in plants supplemented with P at the highest level, where a peak in activity was seen 12 days after inoculation with the pathogen, followed by a decrease in activity. The epicotyl of mycorrhizal plants showed a reduction in disease severity although this part of the plants was not mycorrhizal. Thus, an induced systemic factor may be responsible for increased resistance in mycorrhizal plants.
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  • 53
    ISSN: 1432-0789
    Keywords: Key words Rhizobia ; Cowpea ; Antibiotic resistance ; Phosphorus ; Aluminium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  A large collection of cowpea rhizobia strains was obtained from soil samples collected from either a semi-arid or a tropical rain forest area located at about the same latitude in the north-eastern region of Brazil and evaluated for their intrinsic antibiotic resistance to eight commercial antibiotics. The aim of this study was to correlate antibiotic resistance of native rhizobia strains to edaphic-climatic factors as a way to establish suitable inoculants for specific areas. A large diversity regarding intrinsic antibiotic resistance was found, and 17 clusters were identified as varying from sensitive to gradually resistant up to 500 μg·ml–1 of the antibiotics tested. Clustering analysis did not show any pattern related to the geographic region where isolates have been obtained. On the other hand, an increase in the antibiotic-resistant rhizobia population was associated with an increase in soil P and Al contents. lsolates which were sensitive to spectinomycin, ampicillin, streptomycin, chloramphenicol and tetracycline were present at higher rates in soils devoid of Al. Rhizobia bacteria producing mucus type I (fluid and capable of spreading over the solid media) were found preferentially in soil with Al concentrations up to 36 mg·kg–1, diminishing quickly at higher levels.
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  • 54
    ISSN: 1432-1939
    Keywords: Key words Mangrove species zonation ; Sulfate reduction ; Pyrite formation ; Phosphorus ; Decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We examined soil porewater concentrations of sulfate, alkalinity, phosphorus, nitrogen, and dissolved organic carbon and solid phase concentrations of pyrite in relation to mangrove species distributions along a 3.1-km-long transect that traversed a 47.1-km2 mangrove forest in the Dominican Republic. Iron, phosphorus, and sulfur dynamics are closely coupled to the activity of sulfate-reducing bacteria, the primary decomposers in anoxic soils of mangrove ecosystems. Patterns in the chemistry data suggested that sulfate reduction rates and storage of reduced sulfur were greater in the inland basin forest dominated by Laguncularia racemosa than the Rhizophora mangle dominated forest of the lower tidal region. The distribution of Laguncularia was significantly correlated with concentrations of total phosphorus (r= 0.99) and dissolved organic carbon (r= 0.86), alkalinity (r= 0.60), and the extent of sulfate depletion (r= 0.77) in the soil porewater and soil pyrite concentrations (r= 0.72) across the tidal gradient. Leaf tissue chemistry of Laguncularia was characterized by lower C:N and C:P ratios that could fuel the higher rates of decomposition in the Laguncularia-dominated forest. We suggest that a plant-soil-microbial feedback contributes to the spatial patterning of vegetation and soil variables across the intertidal zone of many mangrove forest communities.
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  • 55
    ISSN: 1432-1939
    Keywords: Key words Dinitrogen fixation ; Plant functional types ; legumes ; Nutrient limitation ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Plant nutrient responses to 4 years of CO2 enrichment were investigated in situ in calcareous grassland. Beginning in year 2, plant aboveground C:N ratios were increased by 9% to 22% at elevated CO2 (P 〈 0.01), depending on year. Total amounts of N removed in biomass harvests during the first 4 years were not affected by elevated CO2 (19.9 ± 1.3 and 21.1 ± 1.3 g N m−2 at ambient and elevated CO2), indicating that the observed plant biomass increases were solely attained by dilution of nutrients. Total aboveground P and tissue N:P ratios also were not altered by CO2 enrichment (12.5 ± 2 g N g−1 P in both treatments). In contrast to non-legumes (〉98% of community aboveground biomass), legume C/N was not reduced at elevated CO2 and legume N:P was slightly increased. We attribute the less reduced N concentration in legumes at elevated CO2 to the fact that virtually all legume N originated from symbiotic N2 fixation (%Ndfa ≈ 90%), and thus legume growth was not limited by soil N. While total plant N was not affected by elevated CO2, microbial N pools increased by +18% under CO2 enrichment (P = 0.04) and plant available soil N decreased. Hence, there was a net increase in the overall biotic N pool, largely due increases in the microbial N pool. In order to assess the effects of legumes for ecosystem CO2 responses and to estimate the degree to which plant growth was P-limited, two greenhouse experiments were conducted, using firstly undisturbed grassland monoliths from the field site, and secondly designed `microcosm' communities on natural soil. Half the microcosms were planted with legumes and half were planted without. Both monoliths and microcosms were exposed to elevated CO2 and P fertilization in a factored design. After two seasons, plant N pools in both unfertilized monoliths and microcosm communities were unaffected by CO2 enrichment, similar to what was found in the field. However, when P was added total plant N pools increased at elevated CO2. This community-level effect originated almost solely from legume stimulation. The results suggest a complex interaction between atmospheric CO2 concentrations, N and P supply. Overall ecosystem productivity is N-limited, whereas CO2 effects on legume growth and their N2 fixation are limited by P.
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  • 56
    Electronic Resource
    Electronic Resource
    Springer
    Journal of computer-aided materials design 5 (1998), S. 81-88 
    ISSN: 1573-4900
    Keywords: Aggregation ; Arsenic ; Diffusion ; Lattice Monte Carlo ; Phosphorus ; Silicon ; Vacancy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In this work, we show that lattice Monte Carlo simulations can be used to span the time and distance scales between underlying atomistic processes and macroscopic diffusion behavior. We use ab- initio calculations of binding energies versus configuration to calculate hopping rates of vacancies for use in lattice Monte Carlo (LMC) simulations of diffusion and aggregation in silicon. The LMC simulations consider the biased nature of vacancy hop frequencies in the neighborhood of dopants, with interactions up to sixth-nearest- neighbor distances included. We use these simulations to investigate the expected macroscopic diffusion behavior, as well as the process by which dopant/defect aggregation occurs. Specific phenomena investigated include collective behavior leading to greatly enhanced diffusivity at high doping levels, the time dependence of effective diffusivity due to the formation of dopant/vacancy clusters, and dopant fluxes in the presence of a vacancy gradient.
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  • 57
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 97 (1998), S. 777-783 
    ISSN: 1432-2242
    Keywords: Key words Rice ; QTL ; Phosphorus ; Use efficiency ; Deficiency tolerance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Phosphorus (P) deficiency of soils is a major yield-limiting factor in rice production. Increasing the P-deficiency tolerance of rice cultivars may represent a more cost-effective solution than relying on fertilizer application. The objective of this study was to identify putative QTLs for P-deficiency tolerance in rice, using 98 backcross inbred lines derived from a japonica×indica cross and genotyped at 245 RFLP marker loci. Lines were grown on P-deficient soil and P uptake, internal P-use efficiency, dry weight, and tiller number were determined. Three QTLs were identified for dry weight and four QTLs for P uptake, together explaining 45.4% and 54.5% of the variation for the respective traits. Peaks for both traits were in good agreement which was to be expected considering the tight correlation of r=0.96 between dry weight and P uptake. For both traits the QTL linked to marker C443 on chromosome 12 had a major effect. Two of the three QTLs detected for internal P-use efficiency, including the major one on chromosome 12, coincided with QTLs for P uptake; however, whereas indica alleles increased P uptake they reduced P-use efficiency. We concluded that this was not due to the tight linkage of two genes in repulsion but rather due to an indirect effect of P uptake on P-use efficiency. Most lines with high use efficiency were characterized by very low P uptake and dry weight and apparently experienced extreme P-deficiency stress. Their higher P-use efficiency was thus the result of highly sub-optimal tissue-P concentrations and did not represent a positive adaptation to low P availability. The number of tillers produced under P deficiency is viewed as an indirect indicator of P-deficiency tolerance in rice. In addition to the major QTL on chromosome 12 already identified for all other traits, two QTLs on chromosome 4 and 12 were identified for tiller number. Their position, however, coincided with QTLs for tiller number reported elsewhere under P-sufficient conditions and therefore appear to be not related to P-deficiency tolerance. In this study P-deficiency tolerance was mainly caused by differences in P uptake and not in P-use efficiency. Using a trait indirectly related to P-deficiency tolerance such as tiller number, we detected a major QTL but none of the minor QTLs detected for P uptake or dry weight.
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  • 58
    ISSN: 1432-0878
    Keywords: Key words Calvaria ; Mineralization ; Calcium ; Phosphorus ; Apatite ; Atomic-force microscopy ; Transmission electron microscopy ; Rat (Sprague Dawley)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  The application of transmission electron microscopy (TEM) and atomic-force microscopy (AFM) aid the acquisition of detailed structural information on the process of hard tissue formation. The sutural mineralization of rat calvaria is taken as a model for a collagen-related mineralization system. After cryofixation or chemical fixation an anhydrous tissue preparation technique with no staining procedures is used. The atomic-force microscope and the transmission electron microscope are used for structural analysis of the mineralizing region of the sutural tissue. With the application of AFM the collagen macroperiod is shown to be well represented in the unmineralized sutural tissue. At the mineralization front the collagen fibrils are found to be thickened and to change to a characteristic stacked platelet structure. Using TEM the macroperiod is faintly visible before mineral crystallites have formed and is more prominent after the apatite crystallization has started in the fibrils. In this step a needle-like structure of the newly formed apatitic crystals is visible.
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  • 59
    ISSN: 1573-143X
    Keywords: Cage culture ; Dietary lipid ; Dietary water ; Feeding frequency ; Moist diets ; Nitrogen ; Phosphorus ; Rainbow trout (Oncorhynchus mykiss)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The nutrient losses into the water from rainbow trout (Oncorhynchus mykiss) cage culture using locally caught low-fat Baltic herring, herring-based moist diets and fishmeal-based dry diets were estimated. Feeding with herring led to nitrogen and phosphorus losses into the water twice as high as those feeding with dry pellets (78–162 versus 37–39 g N and 15–39 versus 7–18 g P per kg growth). This was supported by direct measurements of ammonia and phosphate excretion. Increasing feeding frequencies resulted in increased nutrient losses irrespective of diet. Increasing dietary lipid level had a more pronounced effect in reducing the expected nutrient losses in dry pellets than herring. The reduction within the herring was approximately 18% on average for nitrogen and 25% for phosphorus losses. Dietary water content did not affect the nutrient losses. © Rapid Science Ltd. 1998
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  • 60
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 407-414 
    ISSN: 1434-1948
    Keywords: Ruthenium ; Phosphorus ; Triphos complexes ; Fluxionality ; Arm-off dissociation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structural fluxionality is apparent in the 1H- and 31P-NMR spectra of compounds of the type [Ru(L)(MeCN)(triphos)](CF3SO3), 2-5, at 25°C, where L represents a diorganyldithiocarbamate or a heterocyclic κ2N,S coordinating thioamide. In contrast, complexes [Ru(Et2NCS2)(Y)(triphos)]n+ (6, n = 1, Y = CO; 7, n = 0, Y = CN-; 8, n = 0, Y = H-) are stereochemically rigid in solution at this temperature, indicating that MeCN dissociation must occur for the crowded octahedral coordination spheres of 2-5. Reaction of [Ru(MeCN)3(triphos)](CF3SO3)2, 1, with Na(Et2NCS2) at a 1:2 molar ratio yields [Ru(Et2NCS2-κ2S)(Et2NCS2-κS)(triphos)], 9, which slowly converts to [Ru(Et2NCS2-κ2S)2(triphosO-κ2P)], 10, on recrystallization from ethanol/acetone under air [triphosO is O=P(Ph)2CH2C(CH3)(CH2PPh2)2]. A similar κ3P→κ2P arm-off dissociation leads to the formation of [Ru(mpy-κ2N,S)2(triphosO-κ2P)] (13) and [Ru(mmim-κ2N,S)2(triphosO-κ2P)] (14) (Hmpy = 2-mercaptopyridine, Hmmim = 2-mercapto-1-methylimidazole). Crystal structures are reported for [Ru(mbt-κ2N,S)(MeCN)(triphos-κ3P)](CF3SO3) (4) (Hmbt = 2-mercaptobenzothiazole), [Ru(mpym-κ2N,S)(mpym-κS)(triphos-κ3P)] (11) (Hmpym = 2-mercaptopyrimidine) and 14, the latter of which is present as the OC-6-13 isomer.
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  • 61
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    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 745-749 
    ISSN: 1434-1948
    Keywords: Gallium ; Silicon ; Heterocycles ; Main group elements ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of Ga2X4· 2 dioxane with four equivalents of (Me3Si)3SiLi(thf)3 (= hypersilyllithium) affords for X = Br a 1,3,2,4-disiladigalletane together with tetrahedral hypersilylgallium(I). For X = Cl an anionic 1,2,3,4-silatrigalletanate, a four-membered heterocycle with a Ga3 unit, is isolated. These primary examples of gallium/group-14 heterocycles have been investigated by NMR spectroscopy as well as by X-ray single-crystal structure analysis. In addition, the synthesis and structure of bis(hypersilyl)gallium chloride is described. This monomeric molecule has a nearly T-shaped Si2GaCl framework.
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  • 62
    ISSN: 1434-1948
    Keywords: Silicon ; Phosphorus ; Oligophosphides and -phosphanes ; NMR spectra ; X-ray structure analysis ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The violet THF adduct (tBu3Si)2P3Na(THF)4 (1a) of the triphosphide (tBu3Si)2P3Na (1) is prepared, (i) by protolysis of the tetraphosphide (tBu3Si)2P4Na2 (2) with an equimolar amount of CF3CO2H in THF (transformation of 2 into 1), (ii) by the reaction of tBu3SiNa and the oligophosphane (tBu3SiP3)n in THF (building-down of Pn), and (iii) by the action of tBu3SiNa on PCl3 in THF (building-up of Pn). According to X-ray structural analysis, the SiPPPSi skeleton of the anionic part [tBu3SiPPPSitBu3]- of 1a is W-shaped with two P-P 11/2 bonds; in addition, 1a contains a planar deltoid P3Na backbone with the 4 THF molecules coordinated to Na. The protolysis of 1a leads to cyclotriphosphane (tBu3Si)2P3H (11), and the oxidation of 1a leads to 1,1′-bicyclotriphosphane (tBu3Si)2P3-P3(SitBu3)2 (12) as the main product and bicyclo[3.1.0]hexaphosphane (tBu3Si)4P6 (13) as an isomer of 12. The structures of 11, 12, and 13 as well as the structure of 1a have been unambiguously determined by 31P-NMR studies. Ab initio structure and energy calculations show that the acyclic P3H2- with allylic conjugation and P-P 11/2 bonds is thermodynamically more stable than the cyclic isomer whereas, in contrast, the neutral compound P3H3 prefers the cyclic form. The exceptional downfield shift of the NMR signal of the central phosphorus in 1a is in agreement with DFT NMR calculations for a model compound [H3SiPPPSiH3]Na with P-P 11/2 bonds.
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  • 63
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    Liebigs Annalen 1998 (1998), S. 1517-1520 
    ISSN: 1434-193X
    Keywords: Nucleophilic carbenes ; Heterocycles ; Decarboxylation ; Photochemistry ; Matrix isolation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Irradiation of imidazole-2-carboxylic acid (3) - matrix-isolated in argon at 10 K - with a wavelength of 254 nm leads to decarboxylation and the formation of a complex between 2,3-dihydroimidazol-2-ylidene and carbon dioxide (1·CO2). Upon irradiation of 2,3-dihydroimidazol-2-ylidene (1) with λ = 254, 193, and 185 nm no imidazole can be detected. On the other hand flash vacuum pyrolysis of imidazole-2-carboxylic acid (3) produces imidazole and carbon dioxide. 2,3-Dihydroimidazol-2-ylidene (1) - the possible intermediate - cannot be trapped under these conditions.
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  • 64
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    Liebigs Annalen 1998 (1998), S. 1919-1922 
    ISSN: 1434-193X
    Keywords: Heterocycles ; Carbocations ; Dienes ; Cycloadditions ; Kinetics ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the [2+ + 4] cycloadditions of 1,3-dithian-2-ylium ions (1) with 1,3-dienes was investigated photometrically in dichloromethane. The second-order rate constants determined for the reactions of 1 with 2,3-dimethyl-1,3-butadiene (2a) and isoprene (2b) were identical to those calculated for the first step of a stepwise cycloaddition pathway by the correlation lg k = s (E + N). Though a concerted cycloaddition pathway is not excluded by this finding, it is obvious that the transition states of these reactions are not noticeably stabilized by the simultaneous formation of two new σ bonds.
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  • 65
    ISSN: 1434-193X
    Keywords: Sultones ; Intramolecular Diels-Alder reaction ; Desulfurization ; Heterocycles ; Actic acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A highly stereoselective and flexible sultone route to actic acids, the monomeric subunits of the macrotetrolides, has been developed and exemplified for nonactic acid (2a). Due to the extensive application of tandem transformations, only six steps were needed to secure methyl nonactate (20) from furan.
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  • 66
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    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1145-1152 
    ISSN: 1434-1948
    Keywords: Boron ; Diazaboroles ; Halogens ; Isocyanides ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of differently substituted 2-chloro-, 2-fluoro- and 2-iodo-2,3-dihydro-1H-1,3,2-diazaboroles have been prepared by various methods. 1,3-Di-tert-butyl-2-fluoro-2,3-dihydro-1H-1,3,2-diazaborole (3a), 1,3-di-tert-butyl-2-chloro-2,3-dihydro-1H-1,3,2-diazaborole (5a), 1,3-bis(2,6-dimethyl-phenyl)-2-chloro-2,3-dihydro-1H-1,3,2-diazaborole (5b), 2-chloro-4,5-dimethyl-1,3-dineopentyl-2,3-dihydro-1H-1,3,2-diazaborole (5c), and 1,3-di-tert-butyl-2-iodo-2,3-dihydro-1H-1,3,2-diazaborole (6a) were formed from the corresponding lithiated Z-1,2-diaminoethenes, by treatment with BF3·OEt2, BCl3, or BI3 in n-hexane. Compounds 3a, 5a, and 5b are also available by sodium amalgam reduction of the adduct (tBu)(BF3)N=CH-CH=N(BF3)(tBu) (2a), and the borolium salts [RNa=CH-CH=Nb(R)BCl2]X (Na-B) (4a: R = tBu, X = BCl4 and 4b: R = 2,6-Me2C6H2, X = Cl) respectively. The iodo derivative (2,6-Me2C6H2)-Na-CH=CH-Nb(2,6-Me2C6H2)BI (Na-B) (6b) was synthesized in a redox reaction between the 1,4-diazabutadiene 1b and BI3. The novel compounds were characterized by 1H-, 11B- and 13C-NMR spectroscopy, as well as by an X-ray structure analysis of 6b.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1998/98047_s.pdf or from the author.
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  • 67
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    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1163-1168 
    ISSN: 1434-1948
    Keywords: Chelates ; P,N ligands ; Phosphaferrocene ; Catalysis ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new pyridyl-substituted phosphaferrocene ligands 3 and 6 are prepared by addition of lithiated pyridine or α-picoline to 2-formyl-3,4-dimethylphosphaferrocene (1). The ligands 3 and 6 react with [Cp*RuCl]4 in THF to give the P,N-chelate complexes [Cp*RuCl·3] (9) and [Cp*RuCl·6] (10) with high diastereoselectivity. Addition of monodentate ligands like CO or PPh3 to the complexes leads by displacement of the Ru-bound pyridyl group to the respective carbonyl or phosphane complexes with monodentate P-coordinated phospha-ferrocene ligands. Reaction of the ligand 6 with [(C3H5)PdCl]2 and NH4PF6 gives the seven-membered chelate complex [(C3H5)Pd·6]PF6 (13) which was characterized by X-ray diffraction. The ligands 3 and 6 were tested in the palladium-catalyzed asymmetric alkylation of 1,3-diphenylallyl acetate.
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  • 68
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    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 305-310 
    ISSN: 1434-1948
    Keywords: Ab initio calculations ; Carbene homologues ; Boron ; Isoelectronic analogues ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: While Arduengo-type carbenes are now well established for the Group IVa elements carbon, silicon and germanium, they are experimentally unknown for the isoelectronic anions with the Group IIIa elements boron, aluminum, gallium, and indium. In the present quantum chemical investigations, the bonding features of this class of compounds are explored. As a result, they are predicted to be stable species with sizeable singlet-triplet energy separations and electron affinities. Hence, they may be considered as valid targets for experimental investigations. An analysis of the electron density distribution in the case of boron and aluminum reveals a strongly polar B-N bond for the former, and a half Al-N bond with positive charge at the aluminum, emphasizing the donor-acceptor formulation for the latter.
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  • 69
    ISSN: 1434-1948
    Keywords: Phosphorus ; Phosphonic anhydrides ; Oligophosphonic acids ; Peptide synthesis ; Solid-state structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By reaction of RP(O)Cl2 with RP(O)(OSiMe3)2, phosphonic anhydrides (RPO2)3 (R = tBu, 2-methylphenyl, 2,4,6-trimethylphenyl) 1a-c are conveniently obtained. In contrast to 1b and 1c, compound 1a is remarkably stable against protolysis. Intermediates of hydrolysis of 1a, namely tris(tert-butyl)triphosphonic acid (2) and bis(tert-butyl)diphosphonic acid (3), can also be isolated in good yield. The structures of 1-3 were determined mainly by NMR spectroscopy (1 H, 13C, 31P). Assuming an energetic preference for the chair conformations in solution, and considering the steric requirements of the bulky substituents R, configurations Ia (point group Cs, two R in equatorial positions) for 1a and b, and IIa (point group C3v, all R equatorial) for 1c are suggested. - Reaction of 1a with N-benzyloxycarbonylglycine (4) in methanol affords strong evidence that in the first step of peptide synthesis with (RPO2)3, a mixed anhydride of triphosphonic acid and the N-protected amino acid is formed. - The crystal structure of 1a (monoclinic, space group P21/n) widely corresponds to the suggested configuration Ia, but reveals an envelope conformation for the six-membered ring with a P3O2 plane in the crystal. In the crystal structure of the octahydrate of the disodium salt of 2 (monoclinic, space group P21/c), it can be seen that the polar end groups of the anions [tBu3P3O7]2- together with the water molecules and the Na+ cations, form hydrogen-bonded double-layers, strictly separated from each other by the non-polar tert-butyl groups of the anions.
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  • 70
    ISSN: 1434-1948
    Keywords: Bis(silyl)phosphanes ; Magnesium ; NMR spectroscopy ; Oligomers ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metathesis reaction of (dme)LiPH2 and chlorodiisopropylsilane yields HP(SiHiPr2)2 (1) and P(SiHiPr2)3 (2). The metalation of 1 by n/sec-dibutylmagnesium in heptane leads to the formation of dimeric magnesium bis[bis(diisopropylsilyl)phosphanide] [(3)2]. A toluene solution of magnesium bis[bis(trimethylsilyl)phosphanide] (4) shows a dimer-trimer equilibrium in the 31P{1H}-NMR spectrum at -40°C with an increasing amount of the dimer with increasing temperature. A molecular mass determination by freezing-point depression in benzene yields a value of 516 g·mol-1, which lies between a monomeric and a dimeric molecule. Cooling of the toluene solution to -30°C leads to the precipitation of single crystals of monoclinic {(Me3Si)2P-Mg[μ-P(SiMe3)2]2}2Mg [(4)3].
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  • 71
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    Liebigs Annalen 1998 (1998), S. 1615-1623 
    ISSN: 1434-193X
    Keywords: Homoconjugation ; Cyclovoltammetry ; ESR spectroscopy ; Diketones ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclovoltammetric investigations have been carried out on 3,3,6,6-tetramethylcyclohexane-1,2,4,5-tetrone (4), bicyclo-[3.2.2]nonane-6,7,8,9-tetrone (5), and several of their congeners, such as 6,13-dihydro-6,6,13,13-tetramethylquin-oxalino[2.3-b]phenazine (13), 5,10-dihydro-5,5,10,10-tetra-methylpyrazino[2,3-g]quinoxaline (17), and 6,13-dihydro-6,13-propanoquinoxalino[2,3-b]phenazine (20). For 5 and 20 a large difference (ΔE° ≥400 mV) between the first and second reduction potentials was found. The ESR results of the radical anion 20•- are in support of a strong homoconjugation. ESR studies of 4•-, 13•-, and 17•- also reveal a symmetrical displacement of the unpaired electron over both acceptor groups on the ESR time scale which, however, based on the small potential difference ΔE° ≤ 200 mV can be most likely described to a fast electron exchange.
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  • 72
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    Liebigs Annalen 1998 (1998), S. 1997-2001 
    ISSN: 1434-193X
    Keywords: Alkaloids ; Acetylcholine receptor ; Palladium ; C-C coupling ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Epibatidine (1) is a recently discovered trace alkaloid found in the skin of a Latin-American poisonous frog. Its remarkably high analgetic activity is accompanied by high toxicity. Therefore, in order to tune its biological activity, a convergent and efficient synthetic pathway was sought to synthesize epibatidine derivatives with different (het)aryl substituents. The hydro(het)arylation of the key intermediate 7-azabicycloheptene (10) represents such an approach. The synthesis of 10 by a Diels-Alder reaction of an N-activated pyrrole (7) with ethynyl p-tolyl sulfone (6) and subsequent steps has been optimized. The crucial last step, the reductive cleavage of the vinyl sulfone 9, has been replaced by a high-yield fluoride-induced degradation of the β-silylated sulfone 12 to give 10. A number of structurally different racemic epibatidine analogs (16b-e) can be prepared by palladium-catalyzed hydro(het)arylation of 10 with iodo(het)arenes 15b-e in good yields.
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  • 73
    ISSN: 1434-1948
    Keywords: Carbene complexes ; Tungsten ; Phosphorus ; 2H-Azaphosphirene complexes ; Cyclization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first syntheses of pentacarbonyl[2-(pentamethyl-2,4-cyclopentadien-1-yl)-2H-azaphosphirene]tungsten complexes are reported, using a one-pot reaction of dichloro(pentamethyl-2,4-cyclopentadien-1-yl)phosphane (Cp*PCl2) with triethylamine and {[amino(aryl)carbene]pentcarbonyltungsten(0)}. [Pentamethyl-2,4-cyclopentadien-1-yl]phosphanediyl-bridged dinuclear carbene complexes are formed as long-lived intermediates, which, by elimination and rearrangement reactions, led to the final products. If traces of water were present, then by-products were formed; in one case, a dinuclear carbene complex with a P(Cp*)-O-P(Cp*) bridging unit was isolated. Under ordinary reaction conditions 2H-azaphosphirene complexes are slowly transformed into {pentacarbonyl[chloro(pentamethyl-2,4-cyclopentadien-1-yl)phosphane]tungsten(0)}. NMR-spectroscopic and single-crystal X-ray structural data of some dinuclear carbene complexes and 2-(pentamethyl-2,4-cyclopentadien-1-yl)-2H-azaphosphirene complexes are presented.
    Additional Material: 6 Ill.
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  • 74
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    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 843-849 
    ISSN: 1434-1948
    Keywords: Boranes ; Carbenes ; Carbene complexes ; Heterocycles ; Imidazoles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of the Lewis acids BH3 and BEt3 with trimethylimidazole (1) lead to the borane adducts 2a and 2b. Deprotonation of 2a with n-butyllithium results in the formation of the novel N-borane-substituted imidazol-2-ylidene anion 3a- whereas deprotonated 2b rearranges unexpectedly to the anionic compound 3b-. This can be transformed into the carbene-borane adduct 4 by methylation. The reaction of 3a- with [Mn(CO)5Br] yields the carbene complex 5. Surprisingly, 3a- attacks Fe(CO)5 at a carbon atom which leads to the iron acyl complex anion 6-. The compositions of the products follow from spectroscopic and analytical data and from X-ray structure analyses for Li(thp)+3a-, Li(thf)2+3b- and Li(thp)3+6-.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 951-955 
    ISSN: 1434-1948
    Keywords: Ab initio calculations ; Phosphorus ; Strained molecules ; Substituent effects ; Pericyclic reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: According to quantum chemical calculations at an ab initio level parent 1,2-diphosphete is slightly more stable than its corresponding 1,4-diphosphabutadiene structural isomer. The quantum chemical calculations indicate that substituents at phosphorus and to a much less extent at carbon exert strong influences on the equilibrium geometries of 1,2-diphosphete structures: π donors at phosphorus strongly elongate the P-P bond while electronegative substituents at phosphorus increase the interflap angle of the four-membered ring systems, bringing an envelope conformation to the fore. The lengthening of the P-P bond gives rise to a Möbius-type delocalization within the ring moiety.
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  • 76
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    Liebigs Annalen 1998 (1998), S. 847-851 
    ISSN: 1434-193X
    Keywords: Fluorescent dyes ; Perylenes ; Heterocycles ; Carboxylic acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and properties of perylene-bisimides 4 with one carboxylic acid anchor group are described. The properties of 4 are strongly influenced by the spacer between the carboxylic acid group and the imide moeity. Dyes with aliphatic (4d-4g) and aromatic (4a-4c) spacers have been prepared.
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  • 77
    ISSN: 1434-193X
    Keywords: Diazo compounds ; Carbenes ; Heterocycles ; Enaminones ; Indoles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copper-catalyzed decomposition of alkyl diazoacetates in the presence of semicyclic enaminones 1a-o leads primarily to enamino esters 2 which constitute formal products of C-C insertion of the carbene unit. In the case of N-methyl (1a-e) and N-benzyl (1f-i) enaminones, 2a-i are accompanied by 2,3,5,6-tetrahydroindoles 3a-i, in which two carbene moieties are incorporated. At 250 °C, compounds 2b-e, which could not be isolated in pure form, undergo cyclocondensation to form 1,2,3,5-tetrahydrocyclopenta-[b]pyrroles 4b-e. In contrast, 2f-i can be isolated as Z,E mixtures and are transformed thermally into 4f-i only in the presence of silica gel. Carbene transfer to N-phenyl enaminones 1j-m and N-methyl enamino esters 1n,o leads only to the 1:1 adducts, enamino esters 2j-o, which do not undergo the cyclocondensation reaction under the previous conditions. Dehydrogenation of tetrahydroindoles 3c-e with tetrachloro-p-benzoquinone can be controlled to give either 1,2-dihydroindole-6,7-dicarboxylates 5 or indole-6,7-dicarboxylates 6.
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  • 78
    ISSN: 1434-193X
    Keywords: 1,3,4-Thiadiazoles ; Pyridines ; Cyclizations ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of 6,8-diaroyl-6,7-dihydro-5H-1,3,4-thiadiazolo[3,2-a]pyridines 4a-e was prepared by the reaction of 5-ethylthio-1,3,4-thiadiazole-2-amine (1) and p-substituted 3-(dimethylamino)propiophenones 2a-e in pyridine. The unexpected cyclization process was established by NMR and X-ray diffraction measurements.
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  • 79
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    Liebigs Annalen 1998 (1998), S. 1353-1360 
    ISSN: 1434-193X
    Keywords: Heterocycles ; Substitution ; Carbohydrates ; Anomeric O-hetarylation ; Glycosylation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Anomeric O-hetarylation of tetra-O-benzyl- and tetra-O-acetylglucose (1a, b) can be directly performed with electron-deficient heteroaromatic/heterocyclic systems 2-14, which contain imide halide moieties. The reactions were carried out in the presence of a base and led, through an exchange of the halide by the glucopyranosyloxy moiety, to the products 2a-14a, 7b-14b. Predominantly or exclusively β-products were obtained. Systems bearing more than one imide halide moiety, such as cyanuric fluoride (15) or 5-chloro-2,4,6-trifluoropyrimidine (16), can be employed for successive anomeric O-hetarylations. Investigation of the glycosyl donor properties of O-glucosyl heteroaromatic imidates with 6-O- and 4-O-unprotected glucose derivatives 18 and 19 as acceptors and comparison of the results obtained with data for the corresponding β-trichloroacetimidates 17aβ and 17bβ, reveals that 2,3,5,6-tetrafluoropyridin-4-yl glucopyranosides 14aβ and 14bβ exhibit similar properties. For specific tasks, for instance α-glucopyranoside formation, 14aβ may even be advantageous.
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  • 80
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    Liebigs Annalen 1998 (1998), S. 2775-2784 
    ISSN: 1434-193X
    Keywords: Heterocycles ; Cycloadditions ; Diatomic carbon ; Sulfones ; Alkenes ; Polycycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Chloro-1,4-benzodithiin 1,1,4,4-tetraoxide 11 is a reactive dienophile that forms Diels-Alder adducts with a number of dienes. Adducts 17a-j undergo facile dehydrochlorination to give 2,3-substituted 1,4-benzodithiin tetraoxides 18a-j, which react further with another molecule of diene (the same or a different one) affording the “double” adducts 19-23. Upon reductive desulfonylation with sodium amalgam, the latter are transformed to tetrasubstituted polycyclic olefins 24-27. These olefins correspond to the cycloadducts that would theoretically have been formed by the cycloaddition of diatomic carbon with two molecules of diene, reacting in a Diels-Alder fashion.
    Additional Material: 4 Ill.
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  • 81
    ISSN: 1434-193X
    Keywords: Isoquinolinium N-arylimides ; Azomethine imines ; Cycloadditions ; Heterocycles ; 1,3-Dipoles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The red isoquinolinium N-arylimides 19-23 are azomethine imines of which the C=N bond is part of an aromatic ring. The N-(4-nitrophenyl)imide 22 and the N-(2-pyridyl)imide 23 were obtained crystalline; in solution the latter equilibrates with the hexahydrotetrazine 24 as its dimer. The N-phenylimide 19 is not stable; an isolated solid appears to be a tetramer. Generated by deprotonation of 11-13, the N-arylimides 19-21 undergo in situ cycloadditions to carbon disulfide, phenyl isocyanate, phenyl isothiocyanate, and diphenylketene. The storable CS2 adduct 29 offers a neutral source of theN-phenylimide 19, since a cycloreversion equilibrium is established in solution.
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  • 82
    ISSN: 1434-193X
    Keywords: Cycloaddition ; Elimination ; Heterocycles ; 1,2,4-Thiadiazolidines ; 1,2,4-Dithiazolidines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 5-Imino-1,2,4-thiadiazolidin-3-ones 1 react with compounds containing electron-rich double bonds such as enamines and ester enolates to afford the 2-iminothiazolidines 3, 4, and 10 in cycloaddition-elimination reactions. The less reactive 5-imino-1,2,4-dithiazolidin-3-ones 2 only give the 2-iminothiazolidines 3 or 4 with enamines; with ester enolates the 5-alkylidene-1,2,4-dithiazolidines 12 are formed. The reaction products with enamines undergo hydrolysis and elimination to form the corresponding hydroxy compounds 5, 6 or the unsaturated compounds 7, 8, depending on the size of the fused ring.
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  • 83
    ISSN: 1434-193X
    Keywords: Heterocycles ; Lipases ; Oxidations ; Pheromones ; Stegobinone ; Stegobium paniceum ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crystalline (-)-stegobinone [(2S,3R,1′R)]-2,3-dihydro-2,3,5-trimethyl-6-(1′-methyl-2′-oxobutyl)-4H-pyran-4-one (1)], the major component of the female-produced sex pheromone of the drugstore beetle (Stegobium paniceum L.), was synthesized by oxidation of crystalline and the minor component (-)-stegobiol [(2S,3R,1′S,2′S)-2,3-dihydro-2,3,5-trimethyl-6-(2′-hydroxy-1′-methylbutyl)-4H-pyran-4-one (2)] under the appropriate conditions using Jones's chromic acid, Dess-Martin's periodinane or Ley's ruthenium reagent. The latter (2) was synthesized by employing lipase and the Sharpless epoxidation for the introduction of the proper chiral centers. The streostructure of 1 was comfirmed by X-ray analysis.
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  • 84
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 1391-1395 
    ISSN: 1434-193X
    Keywords: Heterocycles ; Nitrones ; 1,3-Dipolar cycloadditions ; β-Carbolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal isomerization of the 1,3-dipolar cycloadducts of 3,4-dihydro-β-carboline 2-oxide is studied using 1H-NMR spectroscopy. Stereoisomerizations of the cis or syn cycloadducts with dipolarophiles such as methyl crotonate, methyl cinnamate, and methyl methacrylate into the trans or anti cycloadducts are observed. On the other hand, regioisomerization of the 1-substituted cycloadduct with nitroethylene into the 2-substituted cycloadduct is also observed.
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  • 85
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 593-594 
    ISSN: 1434-193X
    Keywords: Heterocycles ; NBS bromination ; Selective bromination ; Polybrominated thiazole ; Structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical bromination of 4,5-dimethylthiazole (1) was carried out using different stoichiometries of N-bromosuccinimide in the presence of 2,2′-azobisisobutyronitrile. Mono-, tri- and tetrabromo compounds 2, 5, and 6 were obtained in good yields with regioselectivity while the dibromo derivatives 3 and 4 were formed without any selectivity. Substitution at the thiazole ring occurred in the presence of silica gel or in the perfluoro ether FC-77 (C8F16O), affording the 2-bromothiazole 7. The order of reactivity observed was 5-Me 〉 4-Me 〉 C-2. Structural assignment of compounds 2-7 was made by chemical correlations and NMR spectroscopy.
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  • 86
    ISSN: 1434-193X
    Keywords: Ambident dianions ; Regioselectivity ; Heterocycles ; C-C coupling ; Oxalyl dielectrophiles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Y-Shaped ambident dianions 1-6 were reacted with dielectrophilic oxalic acid-bis(imidoyl)dichlorides 7 providing a convenient access to novel N-heterocycles 8-13 containing a heteroanalogous oxalic acid unit. The cyclization reactions generally proceeded with good regioselectivity which is controlled by the heteroatoms of the dianion reagents.
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  • 87
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 1471-1477 
    ISSN: 1434-193X
    Keywords: Cyclophanes ; Dilution principle ; Heterocycles ; Medium membered rings ; Ring strain ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The N-protected 1,10-diaza[2.2]metacyclo- and 1,10-diaza-[2]metacyclo[2](2,6)-pyridinophanes 4 and 5 have been synthesized for the first time using high dilution conditions. The free secondary diamine 7 was obtained from 4 by alkaline hydrolysis. - Quantum chemical calculations support the hypothesis that 7 is one of the most strained anti-hetera[2.2]metacyclophanes known. This is also evident from the 1H-NMR spectrum of 7, which shows one of the strongest high field shifts for the intraannular protons in comparison to other anti-[2.2]metacyclophanes.
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  • 88
    ISSN: 1434-193X
    Keywords: Azomethine ylides ; Difluorocarbene ; Cycloadditions ; Heterocycles ; Oxazolidines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Iminiodifluoromethanides generated by the reaction of difluorocarbene with benzaldehyde and benzophenone imines undergo regioselective 1,3-dipolar cycloaddition to aldehydes to give oxazolidine derivatives.
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  • 89
    ISSN: 1434-193X
    Keywords: Antibiotics ; Dipeptides ; Heterocycles ; β-Amino acid ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: TAN-1057 (1a, b) - a new natural dipeptide antibiotic active against methicillin resistant strains of Staphylococcus aureus - was synthesized starting from Nα, Nδ, Nω-tri-Z-L-arginine 20b via the corresponding diazoketone 21b. This upon photolysis rearranged to the ketene which was trapped by (±)-2,4,5,6-tetrahydro-5-methylamino-2-ureidopyrimidin-4-one (3) to yield the fully protected dipeptide 23 (30%). The latter was deprotected by hydrogenolysis to give the final compound as a mixture of two epimers - TAN-1057A, B - isolated previously from a strain of Flexibacter sp. PK-74. The intermediate 3 was prepared from 3-amino-2-(N-Z-N-methylamino)propionic acid methyl ester hydrochloride (16) and 2-methyl-2-thiopseudobiuret hydroiodide (18) in one step in 35% yield.
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  • 90
    ISSN: 1432-1890
    Keywords: Key words Glomus clarum NT4 ; Lentil ; Wheat ; Indigenous AMF ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The growth responses of lentil (Lens esculenta L. cv. Laird) and two wheat cultivars (Triticum aestivum L. cv. Laura and Neepawa) to Glomus clarum NT4 in soil containing indigenous arbuscular mycorrhizal fungi (AMF) and fertilized with phosphorus at different (0, 5, 10, 20 ppm) levels was studied in a growth chamber. Soil was inoculated with a monospecific culture of G. clarum NT4 to provide an inoculant:indigenous AMF ratio of ca. 1 : 100. The shoot and root growth, and AMF colonization levels of NT4-inoculated lentil were significantly (P≤0.05) greater than the appropriate control plants in the unfertilized soil at 48 days after planting (DAP). At 95 DAP, NT4 inoculation had significantly increased the shoot dry weight (P≤0.08) and AMF colonization (P≤0.05) of lentil plants receiving 5 mg P kg–1 soil, whereas 20 mg P kg–1 soil reduced the shoot growth of NT4-inoculated plants. The NT4 inoculant had no effect (P≤0.05) on shoot P content, but increased (P≤0.08) the P-use efficiency of lentil plants receiving 5 mg P kg–1 soil. In contrast to the inoculant's effect on lentil, NT4 generally had no positive effect on any of the parameters assessed for wheat cv. Laura at any P level at 48 or 95 DAP. Similarly, there was no positive effect of NT4 on shoot or root growth, or AMF colonization of wheat cv. Neepawa plants at any P level at 48 DAP. However, NT4 inoculation increased the grain yield of Neepawa by 20% (P≤0.05) when fertilized with 20 mg P kg–1 soil. This yield increase was associated with a significant (P≤0.05) reduction in root biomass and a significant (P≤0.05) increase in the grain P content of inoculated plants. Thus, NT4 appears to have a preference for the Neepawa cultivar. Our results show that lentil was more dependent on mycorrhizae than wheat and responded to an AMF inoculant even in soil containing high levels of indigenous AMF. It might, therefore, be possible to develop mixed inoculants containing rhizobia and AMF for field production of legumes.
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  • 91
    ISSN: 1432-1890
    Keywords: Key words AM ; Drought resistance ; Genotype ; Phosphorus ; Triticum durum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The effects of an arbuscular mycorrhizal (AM) fungus and drought stress on the growth, phosphorus, and micronutrient uptake of two wheat genotypes exhibiting differences in drought resistance were investigated. Plants were grown on a low P (4 mg kg–1 soil) silty clay (Typic Xerochrept) soil-sand mix. Mycorrhizal infection was higher under well-watered than under dry soil conditions and the drought-resistant genotype CR057 had a higher mycorrhizal colonization than the drought-sensitive genotype CR006. Total and root dry matter yields and total root length were higher in mycorrhizal than in nonmycorrhizal plants of both genotypes. CR057 had higher total dry matter but not root dry matter than CR006 plants. The enhancement in total dry matter due to AM inoculation was 42 and 39% under well-watered and 35 and 45% under water-stressed for CR057 and and CR006, respectively. For both genotypes, the contents of P, Zn, Cu, Mn, and Fe were higher in mycorrhizal than in nonmycorrhizal plants and higher under well-watered than under dry soil conditions. The enhancement of P, Zn, Cu, Mn, and Fe uptake due to AM inoculation was more pronounced in CR006 than in CR057, particularly under water-stressed conditions. Thus CR006 benefitted from AM infection more than the CR057 under dry soil conditions, despite the fact that CR057 roots were highly infected. It appears that CR006 is more dependent on AM symbiosis than CR057.
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  • 92
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 24 (1997), S. 1-12 
    ISSN: 1432-0789
    Keywords: Phosphorus ; Isotope techniques ; Forest P immobilization ; Soil-plant system ; Root activity Nutrient cycling ; Organic P sources
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A sound understanding of nutrient dynamics in ecosystems is required in order to manage these systems on a sustainable basis. A valuable approach to studying phosphorus (P) dynamics in soil-plant systems has been the use of P isotope techniques. Isotope techniques used for studying P cycling in agricultural and forest soils are reviewed in this paper with particular reference to advances made in the part 15 years. A brief discussion of the properties of P isotopes and their measurements is included together with techniques for measuring exchangeable P in the soil, dissolution and decomposition rates of inorganic and organic P sources applied to the soil, rates of organic P immobilization and mineralization, rates of P release and retention in the soil, root activity and lifter decomposition rates in forest soils, and gene probing and hybridization. Basic principles, assumptions, procedures, limitations and merits of methods are discussed. These techniques have served as or have the potential to be valuable tools for advancing our understanding of P dynamics in soil-plant systems, and for studying the molecular characteristics of microbial communities in relation to the cycling of nutrients in the soil.
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  • 93
    Electronic Resource
    Electronic Resource
    Springer
    Biology and fertility of soils 24 (1997), S. 183-187 
    ISSN: 1432-0789
    Keywords: Key words Enzyme ; Hydrolysis ; Ion association ; complex ; Phosphorus ; Soil solution ; Podzol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Phosphate in solutions of model esters and polyphosphates (glucose phosphate, inositol hexaphosphate, pyrophosphate, ribonucleic acid, tripolyphosphate and trimetaphosphate) was quantitatively released in 〈6 h by acid phosphatase or phytase at pH 5.0. Interference from insoluble, ion association complexes formed between protein in the enzymes and the phosphomolybdenum blue during the colorimetric determination of the molybdate reactive phosphorus released was removed by adding dimethyl sulphoxide. Filtered (0.45 μm) soil solution from a peaty soil contained 590 μg dm–3 total dissolved phosphorus (TDP), of which 13% was molybdate reactive phosphorus (MRP), 26% dissolved organic phosphorus (DOP) and 61% dissolved condensed phosphorus (DCP). When acid phosphatase was added to the soil solution under the conditions used to hydrolyse the model compounds, MRP increased to 54% of the TDP in about 10 h and then remained constant. From a mass balance, at least 25% of the DCP was hydrolysed. Incubation of the soil solution at 35°C without enzyme increased MRP to 44% of the TDP, reflecting native enzyme activity. Soil solution containing a higher concentration of TDP (1.27 mg dm–3) was also obtained. The distribution of MRP, DOP and DCP fractions was similar but acid phosphatase hydrolysed a greater proportion of the P and MRP increased to 64% of the TDP and at least 40% of the DCP was hydrolysed. The results of hydrolysis with phytase were similar to those with acid phosphatase. The protection of part of the DOP or DCP fraction from hydrolysis was likely caused by occlusion within colloids or the existence of P compounds unlike those of the model substrates.
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  • 94
    ISSN: 1432-0789
    Keywords: Key words Acidic forest soil ; Phosphorus ; Coal combustion by-product ; Carbon cycling ; Cellulose ; Microbial biomass ; Liming
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Phosphate rock (PR), limestone, coal combustion by-product (CCBP) high in Ca and high organic manures are potential amendments for increasing agricultural production in the acidic soils of the Appalachian region. The objective of this study was to examine effects of PR, CCBP and cellulose addition on soil microbial biomass in an acidic soil based on the measurement of soil microbial biomass P (P mic) and on the mineralization of organic matter. Application of PR alone or in combination with CCBP increased P mic. The P mic was far less when the soil received PR in combination with limestone than with PR application alone or PR in combination with CCBP. Either CCBP or limestone application alone considerably decreased P mic in the soil due to reduced P solubility. Cellulose addition alone did not increase P mic, but P mic was significantly increased when the soil was amended with cellulose in combination with PR. The decomposition of added cellulose was very slow in the soil without PR amendment. However, mineralization of both native organic matter and added cellulose was enhanced by PR application. Mineralization of organic matter was less when the soil was amended with PR in combination with high rates of CCBP (〉 2.5%) because PR dissolution varied inversely with amount of CCBP addition. Overall, CCBP had no detrimental effect on soil microbial biomass at low application rates, although, like limestone, CCBP at a high rate may decrease P mic in P-deficient soils through its influence on increased soil pH and decreased P bioavailability in the soil. Application of PR to an acidic soil considerably enhanced the microbial activity, thereby promoting the cycling of carbon and other nutrients.
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  • 95
    ISSN: 1432-1939
    Keywords: Key words Grasslands ; Mineral nutrition ; Allocation ; Phosphorus ; Adaptations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Waterlogging frequently reduces plant biomass allocation to roots. This response may result in a variety of alterations in mineral nutrition, which range from a proportional lowering of whole-plant nutrient concentration as a result of unchanged uptake per unit of root biomass, to a maintenance of nutrient concentration by means of an increase in uptake per unit of root biomass. The first objective of this paper was to test these two alternative hypothetical responses. In a pot experiment, we evaluated how plant P concentration of Paspalum dilatatum, (a waterlogging-tolerant grass from the Flooding Pampa, Argentina) was affected by waterlogging and P supply and how this related to changes in root-shoot ratio. Under both soil P levels waterlogging reduced root-shoot ratios, but did not reduce P concentration. Thus, uptake of P per unit of root biomass increased under waterlogging. Our second objective was to test three non-exclusive hypotheses about potential mechanisms for this increase in P uptake. We hypothesized that the greater P uptake per unit of root biomass was a consequence of: (1) an increase in soil P availability induced by waterlogging; (2) a change in root morphology, and/or (3) an increase in the intrinsic uptake capacity of each unit of root biomass. To test these hypotheses we evaluated (1) changes in P availability induced by waterlogging; (2) specific root length of waterlogged and control plants, and (3) P uptake kinetics in excised roots from waterlogged and control plants. The results supported the three hypotheses. Soil P avail-ability was higher during waterlogging periods, roots of waterlogged plants showed a morphology more favorable to nutrient uptake (finer roots) and these roots showed a higher physiological capacity to absorb P. The results suggest that both soil and plant mechanisms contributed to compensate, in terms of P nutrition, for the reduction in allocation to root growth. The rapid transformation of the P uptake system is likely an advantage for plants inhabiting frequently flooded environments with low P fertility, like the Flooding Pampa. This advantage would be one of the reasons for the increased relative abundance of P. dilatatum in the community after waterlogging periods.
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  • 96
    ISSN: 1573-5052
    Keywords: Deciduous ; Evergreen ; Leaf nutrient levels ; Nitrogen ; Phosphorus ; Quercus ; Soil fertility
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Leaf and soil nutrient levels interact with and may each influence the other. We hypothesize that to the extent soil fertility influences the nutritional state of trees, soil fertility should correlate with summer leaf nutrient levels, whereas to the extent that trees influence soil nutrient levels, the quality of leaf litterfall should correlate with soil fertility. We examined these correlations for five sympatric oak species (genus Quercus) in central coastal California. Soil fertility, including both nitrogen and especially phosphorus, correlated significantly with summer leaf nutrient levels. In contrast, phosphorus, but not nitrogen, in the leaf litterfall correlated positively with soil nutrients. These results suggest that soil nitrogen and phosphorus influence tree nutrient levels and that leaf phosphorus, but not leaf nitrogen, influence soil fertility under the trees. Feedback between the soil and the tree for phosphorus, but not nitrogen, is apparently significant and caused by species-specific differences in leaf quality and not by litterfall quality differences within a species. We also compared functional differences between the evergreen and deciduous oak species at our study site. There were no differences in soil nitrogen and only small differences for soil phosphorus between the phenological types. Differences in leaf nutrient concentration were much more pronounced, with the evergreen species having substantially lower levels of both nitrogen and phosphorus. Evergreen species conserved more phosphorus, but not more nitrogen, than the deciduous species, but there was no consistent relationship between retranslocation and either soil nitrogen or phosphorus. These results do not support the hypothesis that evergreenness is an adaptation to low soil fertility in this system.
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  • 97
    Electronic Resource
    Electronic Resource
    Springer
    Plant ecology 130 (1997), S. 143-153 
    ISSN: 1573-5052
    Keywords: Community boundaries ; Fynbos ; Nitrogen ; Phosphorus ; Soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The relationship between changes in soil nutrient characteristics and fynbos community boundaries was investigated near Cape Agulhas, South Africa. Soil characteristics relating to total nutrient content (pH, total N and total P, organic carbon, and various cations) were assessed at sites along three transects crossing the boundaries between five plant communities. Dynamics of available N and P in soils of three communities were studied in the field over one year, using ion-exchange resins. There was a wide range in the degree of change in soil nutrient content across different community boundaries. The characteristics that varied most were pH, total N, Ca and total P. Differences in available nutrients among soils indicated that the communities in this landscape were associated with a mosaic of N and P availability. It is proposed that spatial variation in soil nutrient availability rather than total soil nutrient contents may be important in explaining landscape-level species distributions and community composition in nutrient-poor mediterranean-climate ecosystems.
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  • 98
    Electronic Resource
    Electronic Resource
    Springer
    Water, air & soil pollution 99 (1997), S. 283-295 
    ISSN: 1573-2932
    Keywords: Sedimentation ; Iron ; Aluminum ; Fractionation ; Organic material ; Phosphorus ; Humic lakes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The sedimentation of organic, amorphous oxides, crystalline oxides and crystalline silicate species of Fe and Al was investigated in humic Lake Örträsket. The covariation with C, N and P sedimentation also was studied. The results showed a strong temporal variation in the occurrence of different Fe species. During high discharge, such as in spring, Fe mostly occurred as crystalline Fe-silicate species, while the amorphous form dominated at other times of the year. Al generally sedimented as crystalline Al-silicate species (95%). Amorphous Fe species showed a strong relation with organic C and N, suggesting an association between organic material and amorphous Fe oxides. P was not as strongly related to amorphous Fe, probably as a result of apatite or clay bound-P species sedimentation.
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  • 99
    Electronic Resource
    Electronic Resource
    Springer
    Water, air & soil pollution 99 (1997), S. 283-295 
    ISSN: 1573-2932
    Keywords: Sedimentation ; Iron ; Aluminum ; Fractionation ; Organic material ; Phosphorus ; Humic lakes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The sedimentation of organic, amorphous oxides, crystalline oxides and crystalline silicate species of Fe and Al was investigated in humic Lake Örträsket. The covariation with C, N and P sedimentation also was studied. The results showed a strong temporal variation in the occurrence of different Fe species. During high discharge, such as in spring. Fe mostly occurred as crystalline Fe-silicate species, while the amorphous form dominated at other times of the year. Al generally sedimented as crystalline AI-silicate species (95%). Amorphous Fe species showed a strong relation with organic C and N, suggesting an association between organic material and amorphous Fe oxides. P was not as strongly related to amorphous Fe, probably as a result of apatite or clay bound-P species sedimentation.
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  • 100
    ISSN: 0009-2940
    Keywords: Alkoxopalladium(II) ; Conformational analysis ; Hydrogen bonding ; Two-dimensional and cage structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of palladium acetate with two equivalents of di- and triethanolamines RN(CH2CH2OH)2 in the presence of a base affords the new chelate-stabilized alkoxo Pd(II) complexes [Pd(OCH2CH2N(R)CH2CH2OH)2] [R = Me (1), Et (2), n-Bu (3), benzyl (4) or CH2CH2OH (5)]. These N,O-ligated complexes are isolated in high yield as yellow, crystalline solids and are thermally stable despite the presence of several β-hydrogen atoms in the ligand system. Both complexes possess a square-planar palladium coordination geometry with the two oxygen atoms positioned mutually trans. The most notable difference in the molecular structures is that 1 forms a two dimensional network of intermolecular O-H≡O hydrogen bonds, whereas 5 forms intramolecular O-H⃛O hydrogen bonds, which cage the palladium center. In solution 1-4 exist as a diastereoisomeric mixture (a racemic enantiomeric pair SNSN, RNRN and a mesomeric form RNSN) in a 1:1 molar ratio, and this ratio is independent of temperature in nonalcoholic solvents, When complexes 1-4 are dissolved in protic solvents (e.g. MeOH) the diastereomeric excess is temperature-dependent due to an exchange process between the meso diastereoisomer and the (racemic) enantiomeric pair. Thermodynamic parameters for this process in a mixture of MeOH-toluene have been determined with NMR and show this process to be influenced by the steric nature of the alkyl substituent (R) on nitrogen. A conformational analysis based on 1H-NMR coupling constants within the N,O-chelate ring of complexes 1-4 provides details on the solution structure of the ring in both diastereoisomers.
    Additional Material: 9 Ill.
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