Tetraethyl 4-(3-nitrophenyl)-2,3,5,6-pyridinetetracarboxylate

Reaction of 3-nitrobenzaldehyde with diethyl oxalacetate in the presence of piperidine acetate and then ammonium acetate/acetic acid gave a moderate yield of tetraethyl 1,4-dihydro-4-(3-nitrophenyl)-2,3,5,6-pyridinetetracarboxylate. This was oxidized with nitric acid to tetraethyl 4-(3-nitrophenyl)-2,3,5,6-pyridinetetracarhoxylate which was hydrolyzed and decarboxylated to give 4-(3-nitrophenyl)pyridine.     

新型荧光试剂5-(4-氯苯偶氮)-8-(4-甲氧基)苯甲醛缩氨基喹啉的合成及荧光性质

近十几年来,有机试剂在荧光分析中的应用日益广泛,有机荧光试剂的合成及应用已是发展荧光分析的重要手段[1].8-氨基喹啉类衍生物是一类较好的荧光试剂和光度试剂[2,3].为了开发新的荧光试剂,我们首次合成了含偶氮基的Schiff碱类化合物5-(4-氯苯偶氮)-8-(4-甲氧基)苯甲醛缩氨基喹啉,通过IR,1H-NMR确证了其结构,并初步测试了其荧光性能.     

Mesomorphic properties of 4-(polyfluoroalkoxycarbonyl)phenyl 4-(4-n-heptoxy-2,3,5,6-tetrafluorophenyl)benzoates

A series of 4-(polyfluoroalkoxycarbonyl)phenyl 4-(4-n-heptoxy-2,3,5,6-tetrafluorophenyl)benzoates were synthesized and observed using DSC and optical polarizing microscopy. The results show that they are not mesogens. Their mesomorphic properties were compared with similar compounds containing no aromatic fluorine substituents.     

Mesomorphic properties of 4-(polyfluoroalkoxycarbonyl)phenyl 4-(4-n-heptoxy-2,3,5,6-tetrafluorophenyl)benzoates

A series of 4-(polyfluoroalkoxycarbonyl)phenyl 4-(4-n-heptoxy-2,3,5,6-tetrafluorophenyl)benzoates were synthesized and observed using DSC and optical polarizing microscopy. The results show that they are not mesogens. Their mesomorphic properties were compared with similar compounds containing no aromatic fluorine substituents.     

4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH): a new chromophoric reagent for quantitative monitoring of solid-phase aldehydes(1-3)

A direct method for quantifying solid-phase aldehydes has been developed, using a new reagent, 4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH). The FmPH reagent was synthesized in three steps (24% overall yield) from commercially available p-hydrazinobenzoic acid. Resin-bound aldehydes reacted quantitatively with FmPH, in the presence of trimethylorthoformate (TMOF) as a dehydrating agent, to form a highly conjugated, immobilized FmPH-hydrazone. Next, mild treatment of the hydrazone with an excess of piperidine-N,N-dimethylformamide (1:1) released the piperidine-dibenzofulvene adduct chromophore (epsilon(301nm) = 7800 M(-1) cm(-1)) from the support. FmPH quantitation of aldehydes proved to be a straightforward, sensitive, and reproducible technique for monitoring resin-bound aldehydes [albeit insufficiently reactive to allow reliable quantification of ketones]. The FmPH aldehyde assay is applicable to a range of solid supports, as demonstrated specifically for poly(ethylene glycol)-polystyrene (PEG-PS), aminomethylpolystyrene (AMP), and cross-linked ethoxylate acrylate resin (CLEAR).     

Synthesis and application of 4-(N,N-dimethylaminosulfonyl)-7-N-methylhydrazino-2,1,3-benzoxadiazole (MDBDH) as a new derivatizing agent for aldehydes

In a five step synthesis, 4-(N,N-dimethylaminosulfonyl)-7-N-methylhydrazino-2,1,3-benzoxadiazole (MDBDH) was prepared in high yields as a stable new derivatizing agent for carbonyl compounds. Reagent and derivatives have not been described in literature before. Major advantage of this substance compared with similar reagents is its improved solubility in polar solvents, e.g. methanol and ethanol. MDBDH reacts with aldehydes in the presence of an acidic catalyst under formation of the corresponding hydrazones. These are separated by means of reversed-phase liquid chromatography and detected UV/vis spectroscopically at wavelengths around 450 nm, depending on the individual hydrazone. MDBDH reacts with oxidizers as nitrogen dioxide and nitrite to only one product, 4-(N,N-dimethylaminosulfonyl)-7-methylamino-2,1,3-benzoxadiazole (MDBDA), which can easily be separated from the hydrazones of lower aldehydes. Due to large molar absorptivities and absorption maxima at wavelengths > 430 nm, limits of detection range from 4 x 10(-8) to 6 x 10(-8) mol.L-1, and limits of quantification range from 1 x 10(-7) to 2 x 10(-7) mol.L-1 for the individual hydrazones. The method was applied to the determination of aldehydes in automobile exhaust.     

Synthesis and application of 4-(N,N-dimethylaminosulfonyl)-7-N-methylhydrazino-2,1,3-benzoxadiazole (MDBDH) as a new derivatizing agent for aldehydes

In a five step synthesis, 4-(N,N-dimethylaminosulfonyl)-7-N-methylhydrazino-2,1,3-benzoxadiazole (MDBDH) was prepared in high yields as a stable new derivatizing agent for carbonyl compounds. Reagent and derivatives have not been described in literature before. Major advantage of this substance compared with similar reagents is its improved solubility in polar solvents, e.g. methanol and ethanol. MDBDH reacts with aldehydes in the presence of an acidic catalyst under formation of the corresponding hydrazones. These are separated by means of reversed-phase liquid chromatography and detected UV/vis spectroscopically at wavelengths around 450 nm, depending on the individual hydrazone. MDBDH reacts with oxidizers as nitrogen dioxide and nitrite to only one product, 4-(N,N-dimethylaminosulfonyl)-7-methylamino-2,1,3-benzoxadiazole (MDBDA), which can easily be separated from the hydrazones of lower aldehydes. Due to large molar absorptivities and absorption maxima at wavelengths > 430 nm, limits of detection range from 4 × 10^–8 to 6 × 10^–8 mol · L^–1, and limits of quantification range from 1 × 10^–7 to 2 × 10^–7 mol · L^–1 for the individual hydrazones. The method was applied to the determination of aldehydes in automobile exhaust. Received: 31 July 2000 / Revised: 9 October 2000 / Accepted: 18 October 2000     

3-(Diethoxyphosphoryloxy)-1,2,3-benzotriazin-4(3H)-one (DEPBT): a new coupling reagent with remarkable resistance to racemization

[formula: see text] The new crystalline phosphate reagent 3-(diethoxyphosphoryloxy)-1,2,3-benzotriazin-4(3H)-one (DEPBT) mediates amide bond formation with a remarkable resistance to racemization. Comparative racemization studies were carried out and DEPBT proved to be superior to typical phosphonium and uronium coupling reagents. DEPBT is easily prepared and is exceedingly stable with a shelf life of months at room temperature. The advantageous properties of DEPBT render it a useful and unique addition to the arsenal of coupling reagents.     

Preparation and use of (S)-O-acetyllactyl chloride (Mosandl's reagent) as a chiral derivatizing agent

(S)-O-Acetyllactyl chloride is used as a versatile chiral derivatizing agent for the chromatographic determination of the enantiomeric excesses of alcohols or amines. However, some precautions must be taken to avoid its racemization during preparation and use. In addition, the racemic counterpart of this reagent can be used to determine the best analytical separation conditions.     

A new facile synthesis of chelate reagent via 2-aminomethylpyridine-Co(III) complex: 2,3,5,6-tetra(2-pyridyl)pyrazine

2-Aminomethylpyridine $\text{(1)}$ readily reacted with Co(II) ion to give a chelate complex which reacted with oxygen to form, presumably, a μ-peroxodicobalt(III) complex or a Co(III)-$\text{(1)}$ complex, and finally it was transformed to 2,3,5,6-tetra(2-pyridyl) pyrazine.     

Spectrofluorimetric determination of aliphatic amines using a new fluorigenic reagent: 2,6-dimethylquinoline-4-(N-succinimidyl)-formate

A new amino fluorescence probe, 2,6-dimethylquinoline-4-(N-succinimidyl) formate (DMQF-OSu) has been synthesized. Based on the selective reaction of DMQF-OSu with primary and secondary aliphatic amines to yield strong fluorescence, a new spectrofluorimetric method for the determination of total aliphatic amines has been developed. At λ_ex/λ_em=324.4/416 nm, the linear calibration range was 6×10⁻⁸-6×10⁻⁶ mol l⁻¹ with the detection limit (3σ) of 1.94×10⁻¹⁰ mol l⁻¹ for the determination of aliphatic amines in weak basic media. The proposed method has been applied to the determination of aliphatic amines in tap water and lake water with the recoveries of 99-104%. Compared with the reported methods, the method presented here is rapid, simple, sensitive and feasible.     

Gas chromatographic separation of optically active anti-inflammatory 2-arylpropionic acids using (+)- or (-)-amphetamine as derivatizing reagent

A method is described for the derivatization of several non-steroidal anti-inflammatory arylalkanoic acids (ibuprofen, ketoprofen, naproxen, fenoprofen, flurbiprofen, pirprofen, cicloprofen, tiaprofenic acid, etodolic acid) with optically active amphetamine. The usefulness of this reagent compared to alpha-methylbenzylamine is described. The enantiomers are separated as diastereoisomers using capillary gas chromatography with nitrogen-phosphorus detection. The procedure is readily applied to the quantification of the enantiomers in urine and plasma samples.     

1-(4-甲基-6-羟基嘧啶)-3-(偶氮苯基)-三氮烯的合成及其与汞的显色反应

合成了新显色剂1-(4-甲基-6-羟基嘧啶)-3-(偶氮苯基)-三氮烯(MHPPAT)并研究了它与汞的显色反应. 在pH 10.0的Na2B4O7-NaOH缓冲溶液中, 壬基酚聚氧乙烯醚 (NP)表面活性剂存在下, 试剂与汞生成4∶1的紫红色配合物. 配合物的最大吸收峰位于520 nm, 表观摩尔吸光系数为2.88×105 Lmol-1cm-1. Hg2+质量浓度在0～4.80×10-4 g/L范围内符合比尔定律.     

Thiophosphoryl bromide: a new reagent for the reduction of sulfoxides to sulfides

Thiophosphoryl bromide (PSBr₃) has been found to be a mild, effective reagent for the reduction of sulfoxides of widely differing structural types to the corresponding sulfides.