Synthesis of 1-benzyl-3,6-diazahomoadamantane

By condensation of 4-phenylbutan-2-one with tetramethylenediethylenetetramine 1-benzyl-3,6-diazahomoadamantan-9-one was synthesized. Further nitration of 1-benzyl-3,6-diazahomoadamantan-9-one yielded 1-(4-nitrobenzyl)-3,6-dia?ahomoadamantan-9-one. The modification of the nitro and carbonyl groups resulted in the formation of 1-benzyl-3,6-diazahomoadamantane and its derivatives with functional groups in the benzene ring and at the bridge carbon atom C⁹.     

Synthesis of 3,6-diazahomoadamantane

Condensation of 1-phenylsulfanylpropan-2-one with 1,3,6,8-tetraazatricyclo[4.4.1.1^3,8]dodecane gave 1-phenylsulfanyl-3,6-diazahomoadamantan-9-one which was reduced to 1-phenylsulfanyl-3,6-diazahomoadamantane, and the latter was subjected to desulfurization over Raney nickel to obtain previously unknown 3,6-diazahomoadamantane. Heating of 9-phenyl-3,6-diazahomoadamantan-9-ols with Raney nickel resulted in reduction of the hydroxy group with formation of 9-phenyl-3,6-diazahomoadamantanes.     

Synthesis of 1-(pyridin-4-yl)-3,6-diazahomoadamantane and its derivatives

Condensation of 1-(pyridin-4-yl)propan-2-one with 1,3,6,8-tetraazatricyclo[4.4.1.1^3,8]dodecane gave 1-( pyridin-4-yl)-3,6-diazahomoadamantan-9-one as intermediate product in the synthesis of 1-(pyridin-4-yl)-3,6-diazahomoadamantane and its derivatives having functional substituents at the bridging carbon atom in the homoadamantane skeleton.     

Synthesis of 1-methyl-8-(pyridin-2-yl)-3,6-diazahomoadamantane and its derivatives

Condensation of 1-(pyridin-2-yl)butan-2-one with 1,3,6,8-tetraazatricyclo[4.4.1.13, 8]dodecane gave 1-methyl-8-(pyridin-2-yl)-3,6-diazahomoadamantan-9-one as intermediate product in the synthesis of 1-methyl-8-(pyridin-2-yl)-3,6-diazahomoadamantane and its derivatives with various functional groups at the bridging carbon atom.     

Heteroadamantanes and their derivatives. 21. Synthesis of thioureas of the 3,6-diazahomoadamantane series

Unsubstituted and phenyl-substituted thioureas were obtained by the action of benzoyl isothiocyanate and phenyl isothiocyanate on amino-substituted diazahomoadamantanes.For Communication 20 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 814–817, June, 1993.     

Heteroadamantanes and their derivatives. 23. Reduction of nitroaryl derivatives of 3,6-diazahomoadamantane

It has been found that nitroaryl derivatives of diazahomoadamantane can be reduced selectively by hydrazine. New data are presented on the noncatalytic reduction of p-nitrophenyldiazahomoadamantane by hydrazine hydrate.For Communication 22 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1405–1408, October, 1993.     

1-(2,6-二甲苯基)-1-苯乙酰基-4-丁基氨基脲的合成与表征

１－（２，６－二甲苯基）－１－苯乙酰基－４－丁基氨基脲的合成与表征刘长令李宗成张少铭龚葆青（化工部沈阳化工研究院１１００２１）杀菌剂甲霜灵和酰胺分别由瑞士汽巴－嘉基公司及山道士公司于７０年代后期开发的、主要应用于防治藻菌纲病原菌特别是卵菌亚纲病原菌...     

New Stereoselective Synthesis of 4-Butyl-α-agarofuran

A potent anxiolytic 4-butyl-α-agarofuran (AF-5) was synthesized from ( )dihydrocarvone. Acid catalyzed hydration of ( )dihydrocarvone and interconversion with β-O-ketone 8 and the key intermediate α,β-unsaturated ketone 5 made this synthesis more practical.     

Synthesis of 1-(pyridylalkyl)-1-aza-3,6-diphosphacycloheptanes

Reactions of 1,2-bis[(hydroxymethyl)(phenyl)phosphino]ethane with primary pyridylalkylamines gave earlier unknown 1-aza-3,6-diphosphacycloheptanes containing the pyridyl group in the exocyclic substituent. The reactions were found to be stereoselective, preferentially yielding the racemate with the RR/SS-configuration of the P atoms. A mixture of diastereomers of 3,6-diphenyl-1-[2-(2-pyridyl)ethyl]-1-aza-3,6-diphosphacycloheptane reacted with dichloro(cycloocta-1,5-diene)platinum(II) to give cis-P,P-chelate complexes from the meso-isomer and bridged oligomeric complexes from the racemate.     

Synthesis of Cellulose Long-Chain Esters in 1-Butyl-3-methylimidazolium Acetate: Structure-Property Relations

In this study, we prepared cellulose long-chain esters homogeneously in 1-butyl-3-methylimidazolium acetate, using cotton linter as the raw material, long-chain fatty acid as the esterification agent and paratoluensulfonyl chloride as the co-reactant. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction were used to characterize the product. The maximum degree of substitution was found to be 1.53 when the molar ratio of cellulose, lauric acid and paratoluensulfonyl chloride was 1 : 6 : 6, provided that the reaction temperature was 60°C and the reaction time was 24 h. The mechanical property of the free-film made of cellulose laurate was also tested. It was found that the toughness of cellulose laurate was much better than that of cellulose acetate.     

1-丁基-3-甲基咪唑氯化锌离子液体的合成、表征及催化性能

本文合成了1-丁基-3-甲基咪唑氯化锌([BMIM][Zn2Cl5])离子液体,通过红外光谱、TGA、DSC以及1H-NMR等方法对[BMIM][Zn2Cl5]进行了结构表征,实现了对于[BMIM][Zn2Cl5]的定性分析。以尿素醇解合成碳酸二乙酯反应为探针,考查了[BMIM][Zn2Cl5]离子液体的催化性能,结果显示,[BMIM][Zn2Cl5]表现出较好的催化活性及重复利用性能,碳酸二乙酯的收率接近30%。     

3,6-二氨基-N-异丁基邻苯二甲酰亚胺的合成

以3-硝基邻苯二甲酸为原料,经脱水成酐、氨解、还原酰化、硝化、水解、还原等六步反应合成了一种新型的环芳酰胺的构筑单元对苯二胺衍生物——3,6-二氨基-N-异丁基邻苯二甲酰亚胺,总收率16.4％,其结构经1H NMR,13C NMR和ESI-MS表征.     

Correlation of the Solubilizing Abilities of 1-Butyl-1-methylpiperidinium Bis(trifluoromethylsulfonyl)imide and 1-Butyl-1-methylpyrrolidinium Tetracyanoborate

Chromatographic retention data were measured for a wide range of organic solutes on 1-butyl-1-methylpyrrolidinium tetracyanoborate ([BMPyrr]⁺[B(CN)₄]^?) and 1-butyl-1-methyl-piperidinium bis(trifluoromethylsulfonyl)imide ([BMPip]⁺[Tf₂N]^?) stationary phases at 323 K and 353 K. The measured retention factors were combined with published infinite dilution activity coefficient and gas-to-water partition coefficient data to yield gas-to-anhydrous ionic liquid (IL) and water-to-anhydrous IL partition coefficients. Both sets of partition coefficients were analyzed using the Abraham model. The derived Abraham model correlations describe the observed gas-to-IL (log₁₀ K) and water-to-IL (log₁₀ P) partition coefficient data to within average standard deviations of about 0.10 and 0.15 log₁₀ units, respectively.     

One-Pot Synthesis of 2-Arylthiazolines with 1-Butyl-3-Methylimidazolium Tribromide as a Catalytic Reagent

Abstract

A simple, inexpensive, and efficient one-pot synthesis of 2-arylthiazoline derivatives under solvent-free conditions using a catalytic amount of 1-butyl-3-methylimidazolium tribromide with excellent product yields is reported. This methodology provides easy, quantitative access to various 2-arylthiazoline derivatives, using environmentally benign 1-butyl-3-methylimidazolium tribromide as a catalyst.     

Pressure-Induced Solidification of 1-Butyl-3-methylimidazolium Tetrafluoroborate

We have used Raman spectroscopy to investigate the high-pressure phase behavior of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), a representative ionic liquid, at pressures up to ~7.5 GPa. We have also studied how increasing pressure leads to conformational changes in the [bmim]⁺ cation. We have found that liquid [bmim][BF₄] undergoes pressure-induced solidification (freezing) into a superpressed (metastable) state at 2.5 GPa; another structural change probably occurs at ~6 GPa. Remarkably, conformational changes in the [bmim]⁺ cation between trans and gauche conformers are concordant with the metastable structural changes of [bmim][BF₄]. As the pressure is increased from ambient, the fraction of gauche conformers increases, but the gauche fraction decreases above the solidification pressure (2.5 GPa), and slope of the gauche/trans ratio changes again above 6 GPa. We interpret these results in terms of the fragility of the ionic liquid.     

2,7-二甲氧基-3,6-二苯氧基萘的合成

以3,6-二溴-2,7-二羟基萘为起始原料,与硫酸二甲酯经甲醚化反应得3,6-二溴-2,7-二甲氧基萘(2);2与苯酚在碘化亚铜催化下经取代反应合成了新化合物——2,7-二甲氧基-3,6-二苯氧基萘,总收率82.5%,其结构经1H NMR,13C NMR,ESI-MS和元素分析表征。