10-(4-联苯基)-2-异丙基噻吨酮硫鎓六氟磷酸的合成与表征

以2-异丙基硫杂蒽酮为原料,乙腈为溶剂经硝酸铈铵氧化得到中间体2-异丙基硫杂蒽酮亚砜,在硫酸存在的条件下,再与联苯反应得到锍盐中间体,最后以醇类和水为混合溶剂,锍盐中间体与六氟磷酸钾进行离子交换得到10- (4-联苯基)-2-异丙基噻吨酮硫鎓六氟磷酸,通过紫外光谱、红外光谱和核磁共振测定,对产物进行了结构确证。     

2-Benzopyrylium salts. 29. A new approach to the synthesis of the natural alkaloid salsolidine using 2-benzopyrylium salts

The reaction of 6,7-dimethoxy-1-methyl-2-benzopyrylium salt with ammonia forms the corresponding isoquinoline, and its reaction with methylamine and benzylamine forms mixtures of the corresponding isoquinolinium salts and naphthylamines. The reduction of 2-benzyl-1-methyl-6,7-dimethoxyisoquinolinium perchlorate with sodium tetrahydroborate has given the corresponding tetrahydroisoquinoline, the hydrogenolysis of which has led to salsolidine. The products have been characterized by elementary analyses and IR and PMR spectroscopy.     

The taming of CN7(-): the azidotetrazolate 2-oxide anion

The highly sensitive 5-azidotetrazolate anion was oxidized to its corresponding N-oxide by aqueous oxidation in a buffered oxone solution to the azidotetrazolate 2-oxide anion. After acidic extraction and neutralization with ammonia, the ammonium salt was isolated. Several energetic salts of this novel anion were prepared from the ammonium salt, and in all cases were found to be of lower sensitivity than the corresponding 5-azidotetrazolate salt while still being highly sensitive towards mechanical stimuli. Explosive performances (detonation velocity, detonation pressure) of applicable salts were also found to be higher than the non-N-oxide variants. Preparation of the free acid 2-hydroxy-5-azidotetrazole was achieved by protonation of the anion and identified by NMR spectroscopy, whereas the majority of the azidotetrazolate 2-oxide salts have unequivocal crystallographic proof.     

Catalytic enantioselective [2+2]-cycloaddition reaction of 2-methoxycarbonyl-2-cyclopenten-1-one by chiral copper catalyst

A new catalytic system for enantioselective [2+2]-cycloaddition reaction of 2-methoxycarbonyl-2-cyclopenten-1-one with thioacetylene derivatives is described. The use of a catalytic amount (20-30 mol%) of copper(II) salt with chiral bis-pyridine ligand was found to be effective in promoting the [2+2]-cycloaddition reaction, furnishing the corresponding bicyclic compound in good yield and good enantioselectivity.     

氯化二甲基-3,3-二氯-2-丙烯基锍的制备和反应

以二甲硫醚和1,1,3-三氯-1-丙烯反应合成了锍盐2, 经碱处理形成 叶立德1;1不经分离能顺利地对羰基加成, 制得带偏二氯乙烯基的环氧衍生物3-9, 与α,β-不饱和酮反应生成相应的环丙烷衍生物10、11。     

Nucleophilic chain substitution on perfluoroketene dithioacetals by ethyl 2-trimethysilyl acetate. Application to the synthesis of 2-trifluoromethyl succinic acid derivatives

A highly efficient substitution of the vinyl fluoride of perfluoroketene dithioacetals was achieved using trimethylsilylacetate to give 2-perfluoroalkyl succinic acid derivatives and 2-trifluoromethyl succinimides. This chain process was initiated by a catalytic amount of fluoride salt, whereas reaction failed with the corresponding lithium enolate.     

P-N compounds. 25. Phosphaminimides. 1. Synthesis and bioevaluation of a derivative of tetrahydro-2H-1,3,4,2-oxadiazaphosphorinium inner salt

2-Phenoxy-4,4-dimethyltetrahydro-2H-1,3,4,2-oxadiazaphosphorinium 2-oxide inner salt, the first known cyclic phosphaminimide, was synthesized by dehydroiodination of its hydrazinium salt. The corresponding 2-phenyl derivative was unstable and not isolated. The 2-phenoxy and 2-phenylphosphorinium iodides and their precursors produced weak inhibition of sympathetic ganglionic transmission. The phosphaminimide caused a slight potentiation and was also found to be less toxic than its corresponding hydrazinium iodide precusor.     

One‐Pot Synthesis of 3,5‐Disubstituted Pyridin‐2‐ones by Annulation of β‐Keto‐amides with 2‐Dimethylaminomethylene‐1,3‐bis(dimethylimonio)propane Diperchlorate

β‐Keto‐amides react with 2‐dimethylaminomethylene‐1,3‐bis(dimethylimonio)propane diperchlorate salt to give the corresponding 3‐acetyl‐5‐formylpyridin‐2‐ones. The annulation reactions proceed with excellent yields.     

Na+, K+//Cl-, B4O2-7-H2O四元体系273 K介稳相平衡

采用等温蒸发法研究了四元体系Na+, K+//Cl-, B4O2-7-H2O 273 K时的介稳相平衡与相图. 测定了该体系273 K平衡液相中各组分的溶解度及平衡液相的密度; 绘制了该体系的介稳相图. 该四元体系273 K相图由5条溶解度单变量线、4个结晶区及2个共饱和点组成. 体系无复盐或固溶体形成. 四个结晶区分别对应单盐NaCl、KCl、K2B4O7·4H2O 和Na2B4O7·10H2O. 共饱点E1处KCl、NaCl及Na2B4O7·10H2O三盐共饱和,所对应的平衡液相组成为w(Cl-)=29.15%, w(B4O2-7)=0.64%, w(K+)=5.97%, w(Na+)=15.55%; 共饱和点E2处盐KCl、Na2B4O7·10H2O和K2B4O7·4H2O的三盐共饱和, 所对应的平衡液相组成为w(Cl-)=22.84%, w(B4O2-7)=10.98%, w(K+)=28.01%, w(Na+)=1.53%. 同体系298 K时的稳定相图相比, 273 K时硼酸钠的结晶区变大, 而硼酸钾、氯化钠结晶区变小.     

Conversion of 3,7-Dialkoxy-4H,8H-benzo[l,2-c:4,5-c']diisoxazole-4,8-dione into new heterocyclic systems

Treatment of 1a or 1b with concentrated acids yielded the acid 3 , with alkali hydrogen carbonates the sodium salt 7 and the potassium salt 8 ; by reacting with phosphorus pentachloride the vinylogous acid chloride 9 was isolated. Reactions of 9 with amines such as N-nucleophiles led to the corresponding amides 10, 11, 14, 15 , and with alcohols such as O-nucleophiles to the corresponding alkoxyderivatives 16a, 16b , which are isomeric compounds to 1a, 1b and 2a, 2b.     

The benzoin condensation catalysis by bis(azolin-2-ylidene)s and bis(azolidin-2-ylidene)s and its interpretation within the context of nucleophilic carbene chemistry

The preparation of bis(thiazolin-2-ylidene)s by passing a methanol solution of the corresponding thiazolium salt through an ion exchange column (basic form) is reported and the use of these “dimers” as benzoin condensation catalysts is studied. The “dimers” show better catalytic activity than the corresponding thiazolium salt plus base. A general discussion of the benzoin condensation catalysis within the framework of nucleophilic carbene chemistry is carried out and as a result of it the important role played by the “dimers” is emphasized. Mechanistic suggestions related with this fact are put forward.     

2-Benzopyrylium salts. 29. A new approach to the synthesis of the natural alkaloid salsolidine using 2-benzopyrylium salts

The reaction of 6,7-dimethoxy-1-methyl-2-benzopyrylium salt with ammonia forms the corresponding isoquinoline, and its reaction with methylamine and benzylamine forms mixtures of the corresponding isoquinolinium salts and naphthylamines. The reduction of 2-benzyl-1-methyl-6,7-dimethoxyisoquinolinium perchlorate with sodium tetrahydroborate has given the corresponding tetrahydroisoquinoline, the hydrogenolysis of which has led to salsolidine. The products have been characterized by elementary analyses and IR and PMR spectroscopy.For communication 28 see [1].Scientific-Research Institute of Physical and Organic Chemistry, M. A. Suslov Rostov State University. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 815–818, November–December, 1985.     

Study of the mechanism of formation of heterocyclic disulfonium dications from 1,3-benzothiazole-2-thiol and 1-iodopropan-2-one

The potential energy surface for the formation of heterocyclic disulfonium dications from 1,3-benzothiazole-2-thiol and 1-iodopropan-2-one has been analyzed at the DFT B3LYP level of theory. The reaction involves oxidation of 1,3-benzothiazole-2-thiol to the corresponding disulfide, followed by alkylation of the exocyclic sulfur atoms. Stabilization of the salt with iodide anion is initiated by thermodynamically controlled reaction with molecular iodine, leading to the formation of stable structure with triiodide anion.     

Synthesis of 4-diphosphocytidyl-2-C-methyl-D-erythritol and 2-C-methyl-D-erythritol-4-phosphate

2-C-Methyl-D-erythritol 4-phosphate (MEP, 2) and 4-diphosphocytidyl-2-C-methyl-D-erythritol (CDPME, 3) are metabolites in the MEP pathway for biosynthesis of isoprenoid compounds in bacteria, plant chloroplasts, and algae. The free phosphoacid of 2 was prepared from benzyloxyacetone in five steps with an overall yield of 27% and an enantiomeric ratio (er) of 75:25. Following titration to the corresponding tributylammonium salt, 2 was coupled to cytidine 5'-monophosphate using a protocol originally developed for synthesis of base-sensitive nucleoside diphosphate sugars to give 3 in 40% yield, following purification by size exclusion chromatography.     

Direct C–H amination for indole synthesis from N-Ts-2-Styrylaniline derivatives catalyzed by copper salt

A direct C–H amination reaction of N-Ts-2-Styrylaniline derivatives to realize the synthesis of indole derivatives was developed in the presence of copper salt. A variety of N-Ts-2-Styrylaniline derivatives were transformed into the corresponding indole products in good to excellent yield under mild conditions with the oxidation of potassium persulfate.     

N-丁基-2-乙氧基硫代吖啶酮的光化学反应机理

采用荧光光谱研究了N-丁基-2-乙氧基硫代吖啶酮的光化学反应机理.结果表明:在Xe灯光照下,N-丁基-2-乙氧基硫代吖啶酮转变成了相应的吖啶酮,用紫外-可见光谱和质谱证实了吖啶酮的存在;生成的吖啶酮可被二苯基碘NFDA1 盐猝灭,它们之间的荧光猝灭遵循电子转移的反应机理.实验又证明了由硫代吖啶酮、二苯基碘NFDA1 盐和硫代水杨酸三者组成的光聚合引发体系的引发效果最好.     

Reactions of arenediazonium tetrafluoroborates with 3-chloro-2-methylpropene in the presence of potassium chloride,bromide, and thiocyanate

Arenediazonium tetrafluoroborates reacted with 3-chloro-2-methylpropene in the presence of potassium chloride, bromide, and thiocyanate to give the corresponding 1-aryl-3-chloro-2-halo(thiocyanato)-2-methylpropanes. The presence of a copper salt is a necessary condition for the reaction to occur. The yields of the corresponding 1-aryl-3-chloro-2-halo-2-methylpropanes in the Meerwein reaction were approximately twice as low. Introduction of a methyl group to C2 in the 3-chloropropene molecule does not change the reaction regioselectivity.     

Synthesis and reactivity of 2-(benzothiazol-2-yl)-1-bromo-1,2-ethanedione-1-arylhydrazones

The novel, highly versatile 2-(benzothiazol-2-yl)-1-bromo-1,2-ethanedione-1-arylhydrazones 3 were prepared and their behavior toward some nucleophiles was investigated. Thus, reaction of 3 with the sodium salt of malononitrile afforded the aminopyrazolecarbonitriles 5 that undergo cyclocondensation with hydrazine, formic acid, and formamide to give the corresponding pyrazolo[3,4-d]pyridazine 6, pyrazolo[3,4-d]pyrimidinone 7, and pyrazolo[3,4-d]pyrimidine 8 derivatives, respectively. Similarly, reactions of 3 with each of acetylacetone, dibenzoylmethane, and benzoylacetonitrile afforded the corresponding pyrazole derivatives 9, 10, and 11, respectively. The latter products undergo cyclocondensation with hydrazine to afford the corresponding pyrazolo[3,4-d]pyridazines 12, 13, and 14, respectively. © 1997 John Wiley & Sons, Inc.     

Synthesis of modified pyrimidine nucleosides via Vorbrüggen-type N-glycosylation catalyzed by 2-methyl-5-phenylbenzoxazolium perchlorate

Several acidic azolium salts prepared from oxazole, thiazole, and imidazole derivatives were investigated as catalysts in N-glycosylation reaction using a silylated modified pyrimidine and an acylated ribose or glucose to afford the corresponding pyrimidine nucleoside. Among the salts, 2-methyl-5-phenylbenzoxazolium perchlorate showed the highest catalytic activity. This salt is a nonhygroscopic crystalline compound that shows higher activity than the frequently used trimethylsilyl triflate. Reactions with this salt can be conducted in gram scales.     

Reaction of 2-Propynyl Phenylcarbamate with Benzaldehyde Oximes in the Presence of N-Chlorobenzenesulfonamide Sodium Salt

2-Propynyl phenylcarbamate reacts with substituted benzaldehyde oximes on heating in ethanol in the presence of N-chlorobenzenesulfonamide sodium salt, yielding the corresponding 3-aryl-5-(phenylcarbamoyloxymethyl)isoxazoles.