Synthesis of the thiophene series 1,3-diselenanes

Direct reaction of propan-1,3-diselenol with thiophene-2-carbaldehydes in trimethylchlorosilane medium is studied. Synthetic procedure for preparation of the previously unknown 1,3-diselenanes of thiophene series is developed. Structure of the newly obtained compounds is established by ¹H, ¹³C, and ⁷⁷Se NMR spectroscopy. Chromatomass spectrometric stidy of the products obtained is carried out. In some cases reaction may be directed to the synthetis of new types of polymers of original structure.     

Efficient Synthesis of 2,3‐Disubstituted‐1,3‐benzoxazines by Chlorotrimethylsilane‐Mediated Aza‐Acetalizations of Aromatic Aldehydes

A series of novel substituted 3,4‐dihydro‐2H‐1,3‐benzoxazines were prepared in moderate to good yields by aza‐acetalizations of aromatic aldehydes with 2‐(N‐substituted aminomethyl)phenols in the presence of chlorotrimethylsilane or SnCl₄. It was found that chlorotrimethylsilane was more effective for the reaction, especially for the reaction of fluorobenzaldehyde, and thereby, an efficient method for the preparation of 3,4‐dihydro‐2H‐1,3‐benzoxazines was developed. The structures of the compounds were determined by FT‐IR, ¹H NMR, ¹³C NMR, MS, and elemental analysis.     

Synthesis and thermal stability of imino-1,3-dithietanes. Influence of structural factors

The reaction of 1,2-dithiol-3-thiones with isonitriles at room temperature affords imino-1,3-dithietanes. The reaction is reversible. According to ¹H NMR spectroscopy, the rise of the temperature shifts the equilibrium to the starting compounds. The structure of one of the imino-1,3-dithietanes was established by X-ray diffraction.     

Synthesis and structure of methyl-substituted 1,3-Dioxa-2-Silacylohexanes

The reaction of dimethyl(diethylthio)silane with 1,3-diols gave methyl-substituted 1,3-dioxa-2-silacyclohexanes.¹H and¹³C NMR spectroscopy were used to study the configuration and predominant conformations of the compounds studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 845–851, June, 1986.     

2-Nitromethyl-2-trichloromethyl-1,3-benzodioxoles and 2-nitromethyl-2-trichloromethyl-1,3-benzoxazolines: Synthesis and structure

A reaction of 1-bromo-3,3,3-trichloro-1-nitropropene with pyrocatechol, o-aminophenol, and their substituted derivatives led to 2-nitromethyl-2-trichloromethyl-1,3-benzodioxoles and 2-nitromethyl-2-trichloromethyl-1,3-benzoxazolines. The structure of the compounds synthesized was established by IR, ¹H and ¹³C NMR spectroscopy with HMQC and HMBC ¹H—¹³C experiments, and X-ray diffraction analysis.     

25,26-Dialkoxycalix[4]arenes. Part 1: 25-Alkoxy-26,27-diacetoxy route

Acetylation of calix[4]arene 1,3-dialkyl ethers yielded the corresponding monoacetates. The ¹H NMR spectral analysis indicated that the products’ alkoxy moieties were ‘rotation restricted’. Acylation of calix[4]arene monoalkyl ethers with acetyl chloride yielded monoacetates and/or 2,3-diacetates in different reaction conditions. A simple recrystallization process was able to isolate 2,3-diacetates in good yield. The ¹H NMR spectra of the diacetylated products indicated that those compounds also possessed the ‘rotation restricted’ alkoxy moieties. In the presence of K₂CO₃ as reaction base, alkylation of 2,3-diacetates produced the acetyl-migrated 1,3-dialkyloxy derivatives. Basic hydrolysis of the acetyl-migrated compounds yielded the known 1,3-dialkoxycalix[4]arenes. In the presence of NaH as reaction base, 2,3-diacetates were alkylated with and without the acetyl-migration. For the highly reactive benzyl bromide and allyl bromide, the majority of alkylation proceeded without acetyl-migration. In the other alkyl halides, the products were the acetyl-migrated 1,3-dialkoxy derivatives along with less than one-fourth the amount of non-migrated 1,2-dialkoxy derivatives.     

手性胍盐离子液体的合成

以1,3-二甲基-2-咪唑啉酮, α-甲基苄胺为原料, 三步合成了手性胍的氯盐, 再经复分解反应, 共合成了14种手性胍离子液体并对其结构性质进行了表征. 该类离子液体有望用于催化不对称Henry 反应、Michael加成反应等.     

A New [5]Ferrocenophane Containing a N–Si–O–Si–N Bridge. Molecular Structure in the Solid State and in Solution

The reaction of 1,1-diaminoferrocene 1 with 1,3-dichloro-1,1,3,3-tetramethyl-1,3-disiloxane in the presence of triethylamine gave the new 1,5,3,2,4-diazaoxadisila[5]ferrocenophane, which was characterized in the solid state by X-ray structural analysis, ¹³C and ²⁹Si MAS NMR spectroscopy, and in solution by [¹H], [¹³C], [¹⁵N], and [²⁹Si]NMR spectroscopy. The ideal ferrocene geometry is slightly distorted, and the cycle containing the heteroelements N, Si, and O is nonplanar. In solution, NMR spectra indicate dynamic processes which may involve both the cyclopentadienyl rings and ring inversion.     

Palladium(II)?NHC complexes containing benzimidazole ligand as a catalyst for C?N bond formation

The reaction of 2‐(2‐bromoethyl)‐1,3‐dioxane with 1‐alkylbenzimidazole derivatives results in the formation of the new benzimidazolium salts (1). The reaction of Pd(OAc)₂ with 1,3‐dialkylbenzimidazolium salts (1a–c) yields palladium N‐heterocyclic carbene (NHC) complexes (2a–c). All synthesized compounds were characterized by ¹H NMR, ¹³ C NMR, IR and elemental analysis techniques which support the proposed structures. As catalysts, these new palladium complexes offer a simple and efficient methodology for the synthesis of triarylamines and secondary amines from anilines and amines and in a single step with potassium tertiary butoxide as a base. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of ruthenium(II) N-heterocyclic carbene complexes and their catalytic activities in transfer hydrogenation of ketones

Three RuCl₂(η⁶-arene, η¹-carbene) and two RuCl₂(NHC)(arene) complexes have been prepared by the reaction of bis(1,3-dialkylperhydrobenzimidazol-2-ylidene) (1) and bis(1,3-dialkyl-4-methylzimidazolin-2-ylidene) (3) with [RuCl₂(arene)]₂ in toluene and characterized by elemental analysis, ¹H NMR, ¹³C NMR and IR spectroscopy. The catalytic activities of these complexes were examined in the transfer hydrogenation of aromatic ketones using 2-propanol as hydrogen source.     

Expedient Approach for the Synthesis of Trispiropyrrolidine Bisoxindoles Through 1,3-Dipolar Cycloaddition Reactions

A series of trispiropyrrolidine bisoxindoles has been achieved via a three-component 1,3-dipolar cycloaddition reaction of 3-aryl-5-arylmethylenespiro[indole-3′,2-[1,3]thiazolane]-2′(1H),4-dione, isatin, and sarcosine in refluxing toluene, which produced the corresponding cycloadducts in good yields (79–88%). Their structures were determined by infrared, ¹H and ¹³C NMR, elementary analysis, and single-crystal x-ray diffraction analysis, and the cycloaddtion reaction was found to be highly regio- and stereoselective.     

Synthesis of New 1,2,3‐Triazole Derivatives Possessing 4H‐Pyran‐4‐one Moiety by 1,3‐Dipolar Cycloaddition Reaction of Azidomethyl Phenylpyrone with Various Alkynes

A series of new 1,2,3‐triazole derivatives were synthesized by 1,3‐dipolar cycloaddition reaction of 2‐(4‐azidomethylphenyl)‐6‐phenyl‐4H‐pyran‐4‐one with different alkynes in 40–71% yields. In the case of terminal alkynes, the reaction was proceeded in the presence of Cu(I) catalyst. The structure of the synthesized compounds were confirmed by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy and elemental analysis.     

α-aminoazoles in synthesis of heterocycles: III. 4-trifluoromethylpyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]pyridines: Synthesis and structure

Cyclocondensation of N-substituted 5-aminopyrazoles with fluorinated 1,3-diketones yielded 4-trifluoromethyl-substituted pyrazolo[3,4-b]pyridines as the only reaction products. The regiostructure of compounds obtained was proved by ¹H and ¹³C NMR homo- and heteronuclear correlation spectroscopy. Characteristic chemical shifts in the ¹³C NMR spectra of regioisomeric pyrazolo[3,4-b]pyridines were established.     

Heterocyclic synthesis using nitrilimines: Part 19. Synthesis of novel 1,3,5-trisubstituted-1,2,4-triazoles

This paper describes the synthesis of a new series of 1,3,5-trisubstituted-1,2,4-triazoles by 1,3-dipolar cycloaddition reaction of C-phenyl-aminocarbonyl-N-arylnitrilimines with guanidine derivatives. The structures of the newly synthesized compounds were elucidated by spectral methods (IR, ¹H NMR, ¹³C NMR and MS spectroscopy) and elemental analysis. The microbial features of the synthesized compounds were studied using well-established methods from the literature.     

An Efficient Synthesis of New Dispiropyrrolidine Derivatives via Three‐Component 1,3‐Dipolar Cycloaddition Reaction

A series of new dispiropyrrolidine derivatives were synthesized via the three‐component 1,3‐dipolar cycloaddition reaction of azomethine ylides generated in situ by the decarboxylative condensation of acenaphthenequinone and sarcosine or l ‐thioproline with 5‐benzylidene‐1,3‐dimethylpyrimidine‐2,4,6‐trione. The structures of the products were identified by IR, ¹H‐NMR, and HRMS spectra.     

Synthesis and structure of phosphorylated nitrocyclohexenes

Diene condensations of 2-nitro-and 2-bromo-2-nitroethenylphosphonates with 2,3-dimethyl-1,3-butadiene, as well as with 2,4-dihydro-and 3-methyl-2,4-dihydrothiophene 1,1-dioxides that generate 1,3-butadiene and isoprene under the reaction conditions were effected. (6-Nitrocyclohex-3-en-1-yl)phosphonates and their dehydrogenation and/or dehydrohalogenation products, namely nitrocyclohexadienyl-and nitrophenylphosphonates were prepared. The structure of the obtained compounds was proved by IR and ¹H and ³¹P NMR spectroscopy, and independent synthesis.     

Synthesis of 1,3-{Di-[N-bis(dimethylamino)methane]}- benzyl-diamide and its Molecular Recognition of Nucleotides in Aqueous Solution

1,3-Di-{N-[bis(dimethylamino)methane]}benzyl-diamide 1 was synthesized by the reaction of isophthaloyl dichloride with 1,1,3,3-tetramethylguanidine (TMG). Its structure was confirmed by IR, ¹H NMR, EI-MS and elemental analysis. ¹H NMR results of the interaction of 1 with phosphate-containing biomolecules showed it has the ability of selective molecular recognition for nucleotides.     

11β-羟基-16β-甲基-16α,17α-环丙烷基-孕甾-1,4-二烯-3,20-二酮的合成

由泼尼松龙(Prednisolone)为原料, 经甲磺酰化、甲基化、脱水、两次1,3-偶极反应以及其后的两次热分解共7步反应, 以23.5%的总收率首次制得了11β-羟基-16β-甲基-16α,17α-环丙烷基-孕甾-1,4-二烯-3,20-二酮这一重要的潜在药物及化学中间体. 实验同时发现, 1,3-偶极反应及其之后的热分解反应具有高度的立体选择性和区域选择性. 这种立体选择性和区域选择性通过¹H NMR数据加以了证明.     

Synthesis of 8,16-diarylacridino[4,3-<Emphasis Type="Italic">c</Emphasis>]acridine-1,9-dione derivatives

A number of new acridino[4,3-c]acridinedione derivatives have been synthesized for the first time by condensation of N¹,N⁵-bis(arylmethylidene)naphthalene-1,5-diamines with cyclic 1,3-diketones (cyclohexane-1,3-dione and dimedone). The product structure has been determined by two-dimensional NMR spectroscopy, and a probable reaction mechanism has been proposed.     

杯[4]芳烃二肟酸-Cu(Ⅰ)配合物的设计与自组装合成

Cu是许多酶中的必须元素[1],Cu与有机配体形成的配合物不仅具有氧化、还原、催化、超分子化合物结构控制等重要作用,而且具有抗菌、抗癌、抗病毒等生物活性.