Determination of 1-(2-chloroethyl)-3-(trans-4-methylcyclohexyl)-1-nitrosourea by reaction with 2,4-dinitro-β-henylethylamine

A method for the determination of 1-(2-chloroethyl)-3-(trans-4-methylcyclohexyl)-1-nitrosourea (methyl-CCNU) in body fluids is described. After extraction from urine or plasma with diethyl ether, methyl is treated with 2,4-dinitro-β-phenylethylamine to. The urea is separated of the amine and treated with trifluacetic anhydride; the trifluoroacetyl derivative is quantified by gas chromatography. Calibration graphs were linear urine, plasma and aqueous standards of metal-CCNU over the range 0.4–2.0 μg ml. The limits of detection for methyl-CCNU are in urine and 0.08 μg ml^?1 in plasma.     

Transformation of trans-4-aryl-3-chloro-1-(2-chloroethyl)azetidin-2-ones into 3-aryl-2-(ethylamino)propan-1-ols via intermediate 1-(1-aryl-2-chloro-3-hydroxypropyl)aziridines and trans-2-aryl-3-(hydroxymethyl)aziridines

trans-4-Aryl-3-chloro-1-(2-chloroethyl)azetidin-2-ones, prepared through cyclocondensation of chloroketene and the appropriate imines in a diastereoselective way, were unexpectedly transformed into 3-aryl-2-(ethylamino)propan-1-ols using LiAlH(4) in THF under reflux. A stepwise analysis showed that the initially formed 1-(1-aryl-2-chloro-3-hydroxypropyl)aziridines were converted into trans-2-aryl-3-(hydroxymethyl)aziridines, most probably via N-spiro bis-aziridinium intermediates, which were subsequently prone to undergo ring opening by LiAlH(4) to afford 3-aryl-2-(ethylamino)propan-1-ols.     

A study of the OH- -induced beta-elimination reactions of 2-(4-chloroethyl)pyridine, 2-(2-chloroethyl)pyridine, 1-methyl-2-(4-chloroethyl)pyridinium iodide and 1-methyl-2-(2-chloroethyl)pyridinium iodide in acetonitrile/water

Second-order rate constants have been determined for the title reactions in OH(-)/H(2)O and in OH(-)/ (CH(3)CN/H(2)O) [30/70, 60/40, and 85/15 (v/v) mixtures]. A relatively small increase in reactivity is observed for the four substrates upon increasing the percentage of CH(3)CN in the solvent mixture. The methyl activating factors (/) are also slightly affected by the solvent composition. On the other hand, the high acceleration of the reaction by methylation of the pyridine ring amounts to 10(4)-10(6) according to an E1cb mechanism.     

Synthesis of 4-(3-methylpyrazolyl-1)naphthalic anhydride

Heating 4-nitronaphthalic anhydride in an excess of 3(5)-methylpyrazole gives only 4-(3-methylpyrazolyl-1)naphthalic anhydride, which is converted by butylamine into the known N-butylimide of 4-(3-methylpyrazolyl-1)naphthalic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, p. 194, February, 1992.     

Prototropic isomerization of trans-4-benzamido-3-hydroxy-2-(4-carbomethoxybutylidene)thiophan to cis- and trans-4-benza mido-3-oxo-2-(4-carbomethoxybutyl) thiophan

trans-4-Benzamido-3-hydroxy-2-(4-carbomethoxybutylidene)thiophan (I) was prototropically isomerized in the presence of hydrogen chloride. It is shown that the two possible isomers cis- and trans-4-benzamido-3-oxo-2-(4-carbomethoxybutyl)thiophan — are formed in the process.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 2, pp. 175–177, February, 1973.     

Unusual michael reaction of 3-(4-Chlorophenyl)-1-phenylprop-2-en-1-one with 3-amino-N-phenyl-3-thioxopropanamide

3-(4-Chlorophenyl)-1-phenylprop-2-en-1-one reacted with 3-amino-N-phenyl-3-thioxopropanamide under basic conditions in ethanol to give a mixture of 3-(4-chlorophenyl)-2-cyano-5-oxo-N,5-diphenylpentanamide and 3-(4-chlorophenyl)-1,5-diphenylpentane-1,5-dione. The structure of the former was determined by X-ray analysis. The reaction of the same compounds in DMSO in the presence of sodium hydroxide produced 4-(4-chlorophenyl)-N,6-diphenyl-2-thioxo-1,2,3,4-tetrahydropyridine-3-carboxamide.     

Synthesis of potential antineoplastics by condensation of phthalic anhydride with 4-bis(2-chloroethyl)aminophenylacetic acid

Indandione, its enol acetate, and the products of a parallel reaction — a mixture of isomeric acidsE, Z-5, and phthalide — are formed in the reaction of substituted phenylacetic acid with phthalic anhydride in acetic anhydride and triethylamine. 2-Substituted indandione derivatives were obtained.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, 142432 Chernogolovka. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2609–2617, November, 1992.     

顺式和反式-2-氨基-3-氰基-4-苯基-1-(4'-甲基苯基)-2-环戊烯-1-醇的合成和晶体结构

用低价钛试剂(TiCl4-Zn)与4, 4-二氰基-3-苯基-1-(4'-甲基苯基)-1-丁酮反应合成了顺式和反式-2-氨基-3-氰基-4-苯基-1-(4'-甲基苯基)-2-环戊烯-1-醇, 并用X射线衍射分析确定了这两个异构体的构型。     

1-(4-硝基苯基)-3-(2-吡嗪)-三氮烯的合成及与镉(Ⅱ)的显色反应

报道了显色剂1-(4-硝基苯基)-3-(2-吡嗪)-三氮烯化合物的合成及其与镉(Ⅱ)的显色反应。在非离子表面活性剂Triton X-100存在下,pH 10.5的Na2B4O7-NaOH的缓冲介质中,该试剂能与镉(Ⅱ)与发生显色反应,形成摩尔比为4∶1的黄棕色配合物,配合物在波长453 nm处有最大吸收峰,表观摩尔吸光系数ε为6.90×104L.mol-1.cm-1,镉(Ⅱ)质量浓度在0~0.56μg/mL范围内遵守比尔定律。用拟定方法测不同废水中的镉(Ⅱ)。     

Extraction and spectrophotometric determination of titanium(iv) with 3-hydroxy-2-methyl-1-(4-tolyl)-4-pyridone

Titanium(IV) in sulphuric, perchloric and hydrochloric acid media reacts with 3-hydroxy-2-methyl-1-(4-tolyl)-4-pyridone (HY) to give a complex which is extractable into chloroform. The composition of the extractable complex depends on the acidity of the aqueous phase and on which mineral acid is used. The mixed titanium-perchlorate-HY complex which is formed in the presence of excess of perchlorate is the most suitable for the spectrophotometric determination of titanium. The molar absorptivity of the complex is 1.6×10⁴1·mole^–1·cm^–1 at 355 nm. The optimum titanium concentration range is 0.5–6,g/ml. The method has been successfully applied to the determination of titanium in samples of bauxite and alumina refractory.     

Diels-alder reaction of (E)-4-(2-nitroethenyl)-1H-imidazoles and methyl (E)-3-(1-imidazol-4-yl)propenoates

Diels-Alder reaction of methyl (E)-3-(1H-imidazol-4-yl)propenoates 2, 3a-c and (E)4-(2-nitroethenyl)-1H-imidazoles 3d,e with 2,3-dimethyl-1,3-butadiene, cyclopentadiene, and cyclohexa-1,3-diene gave the corresponding cycloadducts 6–9 .