7种中位—四取代苯基卟啉化合物的合成

卟啉是一类结构与生命物质(如血红素和维生素B_(12))相似的化合物,近年来曾被用于人体肿瘤的光动力学治疗;此外,在电化学、光物理学和光化学、放射医学、微量元素测定、纺织品漂洗等领域中的应用也相当广泛,已受到科技工作者的普遍关注和重视。本文按Rothemond法将相应的取代苯甲醛与新蒸吡咯在丙酸中缩合,制得具有酸性、中性和碱     

丙酮在固体碱催化剂上的缩合反应

随着石油化学工业的发展,丙酮产量不断增加,开展丙酮化学的研究及以丙酮为原料开发精细化工产品具有重要意义。丙酮经缩合反应可得到如异丙叉丙酮、异佛尔酮、甲基异丁基酮等一系列重要化工产品。由于异佛尔酮具有共轭不饱和酮结构,故其双键可进一步反     

微波干法催化芳香醛与绕丹宁及N－苯基绕丹宁的缩合反应

利用微波辐射和固体碱性载体试剂催化绕丹宁及Ｎ－苯基绕丹宁和芳香醛的缩合反应合成了１４个绕丹宁衍生物并研究了影响反应的因素。     

Synthesis of Novel Bis(mesocyclic) polyamines

介绍了带羟基桥连双－（中环多胺）的合成。首先利用Ｎ－对甲苯磺酰基－３－羟基－１，５－二氮杂环庚烷与５种双官能基化合物在Ｎ２气氛下于无水乙腈中反应，得到５种带对甲苯磺酰基的中环多胺，然后利用ＨＢｒ／ＨＯＡｃ脱去保护基团，得到桥连双－（中环多胺）的氢溴酸盐。所有新化合物的结构均经ＩＲ、１ＨＮＭＲ、ＭＳ或元素分析证实。     

Selective synthesis of isobutanol by means of the Guerbet reaction: Part 2. Reaction of methanol/ethanol and methanol/ethanol/n-propanol mixtures over copper based/MeONa catalytic systems

The synthesis of isobutanol via the Guerbet condensation between methanol and ethanol was studied by using sodium methoxide (MeONa) as soluble basic component and copper-based catalysts as heterogeneous dehydrogenating/hydrogenating metal species. The effect of the nature of the catalyst and the relative amount of its individual components with respect to the reacting alcohols as well as of temperature on productivity and selectivity of the process was investigated. The collected data indicated that the copper chromite/MeONa was more active than Cu-Raney/MeONa system. The reaction was shown to proceed with the formation only of n-propanol and isobutanol. Ethanol conversion up to 61% with selectivity to isobutanol up to 98.4% was obtained. The same catalytic systems were also employed in the reaction of the methanol/ethanol/n-propanol ternary mixture. Again copper chromite/MeONa resulted more active than the Cu-Raney/MeONa system. Finally, experiments were carried out on methanol/n-propanol mixtures in the presence of the copper chromite/MeONa catalytic system by recycling both the recovered solid copper component and the liquid reaction mixture for evidencing eventual copper leaching by MeONa. On the basis of the obtained results it was concluded that in the Guerbet reaction copper chromite works as heterogeneous catalyst.     

Condensation reaction of 3-(methacryloxypropyl)-trimethoxysilane and diisobutylsilanediol in non-hydrolytic sol-gel process

The condensation reaction of 3-methacryloxypropyl-trimethoxysilane (MPTS) and diisobutylsilanediol (DIBSD) in a non-hydrolytic sol-gel process was investigated in terms of the reaction time and the catalyst amount for fabrication of inorganic-organic hybrid materials. The degree of condensation, which was characterized by ²⁹Si NMR, ¹H NMR and Abbe refractometry, increases with increased the reaction time and greater catalyst amount. However, a the large catalyst amount breaks the methacryl group during the condensation reaction. Thus, the reaction time and the catalyst amount were optimized to synthesize the condensed methacryl oligosiloxanes.     

在N—甲基吡咯烷酮中聚苯硫醚合成的宏观动力学

研究了无水硫化钠与对二氯苯（以Ｎ－甲基吡咯烷酮为溶剂）合成聚苯硫醚反应的宏观动力学，该反应是一个小分子缩合串联自缩聚的过程，通过测定不同反应聚合体系中氯化钠的徨成率和硫化内的转化率，建立了该反应的宏观动力学方程：１／（１－ＰＮａＣｌ＋ＰＮａ２ｓ）＝Ｃ０Ｋｔ＋１；并计算得到２２０、２５０℃的表观反应速率为４．５×１０＾－４和３．０×１０＾－３ｋｇ／（ｍｏｌ．ｓ），表观活化能为１３４ｋＪ／ｍｏｌ。     

Reaction of ferrocenecarboxylic acid with N,N-disubstituted carbodiimides: synthesis, spectroscopic and X-ray crystallographic analysis of N,N-disubstituted N-ferrocenoylureas and identification of a one-pot coupling reagent for the formation of ferrocenecarboxamides in a non-aqueous solvent

N,N^′-dicyclohexyl-N-ferrocenoylurea 2, N,N^′-diisopropyl-N-ferrocenoylurea 3, N,N^′-di-p-tolyl-N-ferrocenoylurea 4 and N,N^′-di-tert-butyl-N-ferrocenoylurea 5 were obtained by reaction of ferrocenecarboxylic acid 1 with N,N^′-dicyclohexylcarbodiimide (DCC), N,N^′-diisopropylcarbodiimide (DIC), N,N^′-di-p-tolylcarbodiimide 10 and N,N^′-di-tert-butylcarbodiimide 11, respectively. Both N-tert-butyl-N^′-ethyl-N-ferrocenoylurea 6 and N^′-tert-butyl-N-ethyl-N-ferrocenoylurea 7 were obtained by reaction of 1 with N-tert-butyl-N^′-ethylcarbodiimide 12. In all cases a small amount of ferrocenecarboxylic anhydride 8 was formed as a by-product. All compounds were characterized by ¹H NMR, ¹³C NMR, IR and MS. Single crystal X-ray structural analyses were made of 2, 3 and 4. From the consistent results, the reaction products of 1 with carbodiimides appear different from those proposed by some earlier workers. With N-(3-dimethylaminopropyl)-N^′-ethylcarbodiimidehydrochloride 9 ferrocenoylurea was not isolated, but the main product was rather 8. The suitability of 8 as acylation reagent was applied by using 9 to obtain N-(3-triethoxysilyl)-propylferrocenecarboxamide in a one-pot reaction from 1 and 3-(triethoxysilyl)-propylamine.     

Tetrakis(2-fluorophenylamino)silan und sein erstes Kondensationsprodukt N-(2-fluorophenyl)-Si,Si, Si,Si′, Si′, Si′-hexakis(2-fluorophenylamino)-disilazan. Synthesen und Kristallstrukturen

Zusammenfassung Tetrakis(2-fluorophenylamino)silan (1) wurde als Precursor zur Darstellung poröser, nitridischer Festkörper synthetisiert und mit Hilfe der Einkristallröntgenstrukturanalyse charakterisiert (C2/c;a=16.771(7) Å,b=16.827(5) Å,c=16.753(6) Å, ß=111.00(2)°,z=8). Beim Erhitzen mit Ammoniumcarbamat als Katalysator wurde N-(2-fluorophenyl)-Si, Si, Si, Si, Si, Si, -hexakis(2-fluorophenylamino)disilazan (2) als erstes Kondensationsprodukt isoliert ( ;a=9.331(1) Å,b=13.698(5) Å,c=16.164(4) Å, =90.34(2)°, ß=103.03(2), =103.04(3)°, Z=2).

---

Tetrakis(2-fluorophenylamino)silane and its first product of condensation N-(2-fluorophenyl-Si, Si, Si, Si, Si, Si-hexakis(2-fluorophenylamino)disilazane. Syntheses and crystal structures

Summary The synthesis and crystal structure determination of silanetetramine N,N,N,N2-fluorophenyl(C2/c;a=16.771(7) Å,b=16.827(5) Å,c=16.753(6) Å, ß=111.00(2)°, z=8) are reported. In a search for suitable condensation pathways to silicon/nitrogen based porous solids, N-(2-fluorophenyl)-Si,Si,Si,Si,Si,Si-hexakis(2-fluorophenylamino)disilazane (2) has been obtained from the ammonium carbamate catalyzed condensation of the silanetetramine in teflon lined autoclaves. The X-ray crystal structure determination ( ;a=9.331(1) Å,b=13.698(5) Å,c=16.164(4) Å, =90.34(2)°, ß=103.03(2)°, =103.04(3)°, Z=2) shows the disilazane to be a dimer formed by linear condensation from the monomeric silazane.

     

N—乙基—N—苄基苯胺合成方法的改进

以苯胺和乙醇为原料，采用ＲａｎｅｙＮｉ为催化剂，合成了Ｎ－乙基苯胺，再在相转移催化剂作用下，经苄基化反应得到标题化合物，第一步合成方法的收率比通常方法的收率提高约３０％。