Organometallic synthesis in the furazan series 1. Functionalization of 3-methyl-4-R-furazans

The possibility of synthesizing functionally substituted furazans by alkylation of lithium derivatives of 3-methyl-4-R-furazans was investigated. It was shown that one or both methyl groups of 3,4-dimethylfurazan could be lithiated and alkylated. A series of previously unknown furazan derivatives was obtained.For previous communication, see [1].N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 365–371, February, 1992.     

C~6~0, C~7~0的烷基化

本文利用低价稀土化物(S~mI~2或YbI~2)与C~6~0、C~7~0及卤代烃(烯丙基溴、氯苄)的混合溶液反应,制得烯丙基化、苄基化的富勒烯。发现与C~6~0相接的苄基数可以从1到14,验证了Krusic等人的结果。此外,还发现C~6~0可以进行烯丙基化,得到(CH~2=CHCH~2)~nC~6~0(n=1-10),C~7~0可以进行苄基化,C~7~0上至少可以接13个苄基,实验证明这类反应是对富勒烯进行烷基化的一种简便、有效的方法。     

Alkylation of catechol with methanol to guaiacol over sulphate-modified zirconia solid acid catalysts

A series of sulphate-promoted ZrO₂ solid acid catalysts with different contents of SO₄ ²⁻ were calcined at 450°C in air for 4 h and tested for the liquid-phase alkylation of catechol to guaiacol in a fixed-bed down-flow reactor. The 5 wt.% SO₄ ²⁻ on ZrO₂ showed the best conversion (82%) and selectivity for guaiacol (84%) at 200°C and 1 bar pressure. A smooth correlation was observed between the catalytical activity and surface acidity of sulphated zirconia. Based on our results, a surface mechanism is proposed.     

Synthesis and properties of methyl hydropyrimidineacetates

The alkylation of 1-aryl-substituted dihydro-2,4(1H,3H)-pyrimidinediones with methyl 2-bromoacetate has been studied followed by hydrolysis and condensation of the products with o-phenylenediamine. The compounds have been identified by NMR, and IR spectrometry and mass spectrometry. Structural characteristics in the ¹H and ¹³C NMR spectra of the synthesized are discussed. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, 1095–1105, July, 2007.     

Acidity effects of Hβ zeolite on olefin alkylation of thiophenic sulfur in gasoline

Olefin alkylation of thiophenic sulfur process was carried out in model gasoline, using Hβ zeolites with different Si/Al2 ratios as catalysts. In particular, the influence of acid properties of Hβ zeolites on its catalytic ability for the thiophene alkylation, xylene alkylation and hexene oligomerization was investigated. The results showed that the acidity of the Hβ zeolite was increased with the decrease of Si/Al2 ratio, but its catalytic ability was not always increased. In fact, it reached the maximal catalytic ability at Si/Al2 ratio of 66, and under the reaction conditions of 60 ℃, 1.5 MPa, WHSV 3.0 h^-1 and time on stream 2 h. At the ratio, the conversion of thiophene, xylene, and oligomerized hexene were 96.6%, 2.7% and 2.8%, respectively. An optimal Si/Al2 ratio exists for the catalytic performance of Hβ zeolite. By investigating the coke deposition of the used Hβ zeolite catalysts, it has been found that the optimal Si/Al2 ratio is attributed to the combined effect of the carbocation activation capability and the hydrogen transformation capability of the Hβ zeolite catalyst.     

三氟甲基磺酸锌催化选择性合成2-苄基-4-氯苯酚

在温和条件下,Zn(OTf)2能有效催化氯化苄对对氯苯酚的C-苄基化反应,选择性合成杀菌剂2-苄基-4-氯苯酚（BCP）,合成的优化条件为n(对氯苯酚):n(氯化苄)=1.2:1,催化剂Zn(OTf)2对氯化苄摩尔分数为5%,60 ℃下反应6 h,用硝基甲烷为溶剂,氯化苄转化率和产物BCP的产率分别＞99%和94%。     

以苯为模块自组装合成碳纳米片

在300 ℃苯溶剂中, 以无水三氯化铝为催化剂, 以苯和六氯乙烷为碳源, 基于傅克烷基化反应生成三氯乙烯苯, 并以之为模块自组装合成了具有叠层结构的碳微米颗粒, 其层片厚度为300～500 nm. 进而在反应体系和反应条件不变的情况下, 通过引入铝粉颗粒作为基底成功地诱导出厚度为30～50 nm的碳纳米片. 实验结果表明, 所得碳材料由纳米石墨微晶和非晶碳组成. 文中探讨了叠层结构的台阶长大机制, 以及碳纳米片在铝粉表面的异质形核机制.     

侧链含8-羟基喹啉铝配合物的聚苯乙烯的合成与发光性能研究

通过高分子反应法研究制备了高分子化的8-羟基喹啉铝发光材料.首先使用自制的氯甲基化试剂1,4-二氯甲氧基丁烷(BCMB),制备了5-氯甲基-8-羟基喹啉(CHQ);通过聚苯乙烯(PS)与CHQ之间的Friedel-Crafts烷基化反应,制得侧链键合有8-羟基喹啉(HQ)的改性聚苯乙烯HQ-PS;再使HQ-PS与二配体...     

金属氧化物和硅沉积改性 ZnO/SiO2/ZSM-5的甲醇择形芳构化反应催化研究

采用真空浸渍法对ZSM-5分子筛进行硅沉积和负载金属修饰,制备了复合改性的ZnO/SiO₂/ZSM-5催化剂,并将它应用于甲醇择形芳构化反应中。采用XRD、BET、NH₃-TPD、SEM、TEM等方法对制备的催化剂进行了物化表征。考察硅沉积次数和ZnO负载量对甲醇芳构化反应(MTA)中对二甲苯(PX)的选择性和收率的影响。结果表明,两次硅沉积改性并负载2.0%金属ZnO的ZSM-5分子筛具有较高的PX收率,在优化的反应温度420 ℃、反应压力0.2 MPa、甲醇空速WHSV为1.25 h^-1下,PX收率在28%以上。