N′-(取代嘧啶-2-基)-N-菊酰硫脲的合成与生物活性研究

采用活性基团拼接法, 将第一菊酸构型中的最高活性组分(＋)-反式菊酸以及二氯菊酸引入到含取代嘧啶环的酰基硫脲结构中, 合成了5个未见文献报道的N′-(取代嘧啶-2-基)-N-(＋)-反式菊酰硫脲衍生物(3a～3e)和3个均未见文献报道的N′-(取代嘧啶-2-基)-N-二氯菊酰硫脲(3f～3h), 结构经元素分析、IR和¹H NMR得到确证. 初步的生物活性测试结果表明: 大部分化合物具有较好的杀菌活性, 有的化合物兼具除草和杀菌活性, 有的化合物兼具杀虫和杀菌活性.     

Synthesis ofO-methyloximes and nitrones of a series of substituted 4-[2-hydroxy-2-(1H-1,2,4-triazol-1-ylmethyl)cyclohexylidenemethyl]-benzaldehydes and their fungicidal activity

O-Methyloximes and nitrones of a series of substituted 4-[2-hydroxy-2-(1H-1,2,4-triazol-1-ylmethyl)cyclohexylidenemethyl]benzaldehydes have been synthesized, and their fungicidal activity has been assayed. All of them exhibit low fungicidal activity in thein vitro assays and high activity in thein vivo assays; theO-methyl oximes are more active than the corresponding nitrones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2082–2087, December, 1993.     

Chemical properties ofN-(amidomethy)- andN-(imidomethyl)glycine derivatives 2. Reactions at alkoxycarbonyl and carboxyl groups

N-(Aroylarnmomethylfglycine amides were synthesized by reactions ofN-(aroyllminomethyl) glycine esters with ammonia. Alkaline hydrolysis ofN-(amidomethyl)glycine,N-(irnidornethyl)glycine, andN-(amidomethyl)pheriylalariiiie esters afforded the correspondingN-(amidowthyVa-amirio acids- Reactions of the Last-mentioned compounds with ethyl esters of glycine, alanine, and phenylalanine in the presence of dicyclohexylcarbodiimide yielded dipeptides containingNh-amidomethyl substituents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1770–1771, July, 1996.     

Syntheses based on (N,N-difluoroamino)dinitroacetonitrile

High reactivity of the nitrite group in (NN-difluoroamino)dinitroacetonitrile was demonstrated. Based on its reaction with HN₃, a new preparative method for the synthesis of 5-[(N,N-difluoroamino)dinitromethylltetrazole was developed; some derivatives of the latter compound have been obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8. pp. 2056–2058, August, 1996.     

Microwave-promoted solvent-free synthesis of N-(diphenylmethylene)glycine alkyl esters

The efficient synthesis of N-(diphenylmethylene) glycine alkyl esters was achieved for the first microwave irradiation under solvent-free condition, using PEG or quaternary ammonium salts as phase transfer catalysts (PTCs). Under the optimum conditions, N-(diphenylmethylene) glycine alkyl esters were obtained in excellent yields in most cases.     

N-对甲基苯基-N′-（2-吡啶基）脲的低温热容及热分析

通过低温量热和热分析方法,测定了N-对甲基苯基-N′-（2-吡啶基）脲(以下简称NPMPN′2PU)的低温热容和热力学性质.通过对NPMPN′2PU进行低温量热,得到了NPMPN′2PU在80～370 K 温区的热容曲线,热容曲线光滑,没有任何热异常现象,由此实验热容数据计算出NPMPN′2PU在这段温区内的热力学数据.从DSC实验结果发现, NPMPN′2PU熔化峰值出现在173.86 ℃,熔化焓为204.45 kJ•mol－1.紧接熔化峰后NPMPN′2PU开始分解,分解峰只有一个,分解峰值温度为226.11 ℃.TG和DTG的实验结果表明,NPMPN′2PU失重的峰值为227.2 ℃,这些结果与DSC实验结果吻合.     

Synthesis and structures of complexes ofN-2-nitroxyethylpicolinamide and 2-(2-pyridyl)-2-oxazoline with PdCl2

The reaction ofN,N′-bis(2-nitroxyethyl)pyridine-2,6-dicarboxamide with PdCl₂ afforded previously unknowncis-(N-2-nitroxyethylpicolinamide-N,N′)dichloropalladium(II) andcis-[2-(2-pyridyl)-2-oxazoline-N,N′]dichloropalladium(II), which were isolated as a cocrystallizate of the molecular compounds. Its structure was established by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1604–1606, August, 1999.     

3-取代苄氧基-6-取代氨基哒嗪衍生物的合成及其除草活性

通过3-取代苄氧基-6-氟哒嗪在75～80 ℃与二甲胺的绝对无水乙醇溶液封管反应, 或在回流条件下分别与吗啡啉或哌啶反应, 合成一系列新颖的3-取代苄氧基-6-取代氨基哒嗪类化合物, 它们的结构均经IR, ¹H NMR和元素分析确证. 初步的除草活性测定结果表明, 该类化合物具有一定的除草活性, 讨论了它们的结构与除草活性的关系.     

Synthesis ofN-(3-azido-2-nitroxypropyl)-,N-(2,3-diazidopropyl)-, andN-(2-azido-3-methoxypropyl)-N-alkylnitramines

N-(3-Azido-2-nitroxypropyl)-N-alkylnitramines andN-(2,3-diazidopropyl)-N-alkylnitramines were prepared by nitration and azidation ofN-alkyl-N-(2-hydroxy-3-chloropropyl)sulfamates andN-(3-azido-2-hydroxypropyl)-N-alkylsulfamates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 206–208, January, 1999.     

Reactions ofN-nitramines and their trimethylsilyl derivatives withN,N-bis(trimethylsilyloxy)enamines

Trimethylsilyl derivatives of methyl- and ethylnitramine react asN-centered nucleophiles with 2-N,N-bis(trimethylsilyloxy)aminopropene to give trimethylsilyl derivatives of hitherto unknown α-(N-nitro)alkylamino-substituted acetone oximes. As an ambident nucleophile, nonsubstituted methylnitramine reacts with the same enamine to give both a product of N,C-corss-coupling and a product of O,C-cross-coupling,viz., N′-methyl-N-[(2-trimethylsilyloxyimino)propoxy]diazeneN-oxide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2045–2047, October, 1998.     

Regioselective Deprotection of 1,3-Dibenzyl-5-（N,N-dimethylamino）-6-phenylethyluracil

The deprotection of 1,3-dibenzyl-5-（N,N-dimethylamino）-6-phenyl-ethyluracil I was investigated. A practical, regioselective N3 deprotection of compound I was performed with excellent yield using cyclohexene as a hydrogen donor.     

Reactions of hexaorganyldigermoxanes with O-trimethylsilyl carbamates

Hexa-n-butyl- and hexaisopentyldigermoxanes but not hexaphenyldigermoxane react with O-trimethylsilyl N,N-diethylcarbamate and trimethylsilyl piperidinocarboxylate to give O-triorganylgermyl carbamates.     

Peculiarities of electroreduction of trans-2-allyl-6-methyl(allyl,phenyl)-1,2,3,6-tetrahydropyridines

Electrochemical reduction of trans-2-allyl-6-R-1,2,3,6-tetrahydropyridines (R = Me, All, and Ph) on the mercury cathode in anhydrous DMF (with 0.1 M Bu₄NClO₄ as the supporting electrolyte) resulted in catalytic hydrogen evolution, while in the case of anhydrous DMF the electrochemical activity of the endocyclic double bond was dictated by the nature of the R substituent at the carbon atom neighboring the double bond. The electrocatalytic hydrogenation of the piperideines under study on the Ni (Ni_disp/Ni) cathode in 40% aqueous DMF in the presence of a tenfold excess of AcOH yielded the corresponding trans-2-propyl-6-R¹-piperidines (R¹ = Me, Pr, and Ph). Using trans-2,6-diallyl-1,2,3,6-tetrahydropyridine as an example, the conditions (with annealed copper as the cathode) for selective hydrogenation of the double bonds in allyl substituents with preservation of the endocyclic double bond were found.     

(N-methyl-N-alkoxymethylaminomethyl)dialkoxysilanes and bis[N-methyl-N-(dialkoxysilylmethyl)amino]methanes

(N-methyl-N-alkoxymethylaminomethyl)-dialkoxysilanes and bis[N-methyl-N-(dialkoxymethyl)amino]methanes were first obtained by the interaction of (N-methylaminomethyl) dialkoxy-R-silanes with chloromethyl alkyl ethers in yields of 40–67% and 10–25 %, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 382–383, February, 1995.     

3-Cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines in the synthesis of substituted 3-(aminomethyl)pyridines

The reactions of substituted 3-cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines with lithium aluminum hydride in anhydrous diethyl ether afforded the corresponding 3-aminomethyl derivatives, which were used in the synthesis of the corresponding amides.     

DFT Study on Intermolecular Cleavage Reaction of N-（2-Hydroxyphenyl）-phthalamic Acid

The reaction mechanisms of intermolecular cleavage reaction of N-（2-hydroxyphenyl）-phthalamic acid were studied via the density functional theory（DFT）. All geometries of the reactant, transition states, and products were optimized at the B3LYP/6-31G（d, p） level. Vibration analysis was carried out to confirm its identity as transitions＇ structure, and the intrinsic reaction coordinate method（IRC） was used to search the minimum energy path. Two possible reaction channels are reported in this article. The calculated results indicate that O-cyclization reaction channel has the lower activation barrier, and therefore, it occurs more easier than the other.     

Synthesis of 1-(N-alkylnitraminomethyl)-3-nitroureas usingN-alkylsulfamates

1-(N-alkylnitraminomethyl)-3-nitroureas were prepared by nitration of condensation products of urea with formaldehyde andN-alkylsulfamate.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2041–2042, November, 1994.     

Reaction of 2-chloro-3-(4-N,N-dimethylaminoanilino)-1,4-naphthoquinone with cyclic amines (piperidine,morpholine, and pyrrolidine)

It was shown that the reaction of 2-chloro-3-(4-N,N-dimethylaminoanilino)-1,4-naphthoquinone with piperidine in the absence of a solvent gives not only a product of replacement of the chlorine atom by a piperidino group, 3-(4-N,N-dimethylaminoanilino)-2-piperidino-1,4-naphthoquinone, but also 2-(4-N,N-dimethylaminoanilino)-1,4-naphthoquinone and 2-(4-N,N-dimethylaminoanilino-2-piperidino)-1,4-naphthoquinone. The latter compounds are the only reaction products formed in dimethyl sulfoxide. The reaction with morpholine occurs in a similar way, whereas that with pyrrolidine gives only a product of replacement of the chlorine atom by hydrogen.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2451–2454, December, 1995.     

Quantum chemical study of the transformation of 2-(N-alkylamino)-3-(indol-1-yl)-and 2-(N-alkylamino)-3-(indol-3-yl)maleimides by protic acids: Tandem hydride transfer/cyclization mechanism

The geometric parameters, the charge distribution, and the energetics of N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)-and N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimides and their conjugated acids were studied by density functional theory calculations at the B3LYP/6-31G(d) level. The mechanism of the tandem hydride transfer/cyclization sequence, which occurs after protonation of N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)-and N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimides, was analyzed. The investigation of the potential energy surface for the tandem hydride transfer/cyclization of the iminium cation that formed upon protonation revealed that the hydride transfer followed by intramolecular cyclization at position 7 of the indole fragment in N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)maleimide is the preferable process, unlike alternative intramolecular cyclization involving the cationic center at the C(2) atom of the indole fragment and the benzene ring of the N-ethylaniline fragment of the indoleninium cation in N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimide. A study of the key intermediates of the assumed reaction mechanism demonstrated that these intermediates are actually stationary points on the potential energy surface (minima and transition states). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2069–2073, December, 2006.     

Bis(alkoxyethynyl)-substituted silanes,germanes, and stannanes: synthesis and pyrolysis

Previously unknown bis(alkoxyethynyl)-substituted silanes, germanes, and stannanes were synthesized. Pyrolysis of bis(ethoxyethynyl)-substituted silanes and germanes was studied. Depending on the reaction conditions (pyrolysis in a solvent or vacuum pyrolysis without a solvent), the process affects either one ethoxyethynyl group to give (ethoxyethynyl)silyl(-germyl)ketenes or both ethoxyethynyl groups, affording silyl- and germylbisketenes. Pyrolysis of bis(alkoxyethynyl)dimethylstannanes follows another route, resulting in 1,1-bis(alkoxy)-2,2-bis[(alkoxyethynyl)dimethylstannyl]ethenes.