Ti－Si沸石的催化氧化性能Ⅱ．环己醇的氧化及环己酮的肟化

Ｔｉ－Ｓｉ沸石的催化氧化性能Ⅱ．环己醇的氧化及环己酮的肟化夏清华，王公慰，应慕良，郑禄彬（中国科学院大连化学物理研究所，大连１１６０１２）关键词Ｔｉ－Ｓｉ沸石催化剂，Ｈ_２Ｏ_２氧化剂，环己醇氧化，环己酮肟化．１．前言环己酮肟是生产ε－己内酰胺的关键中...     

Enthalpies of dilution of aqueous solutions of amides and alcohols

Enthalpies of dilution of aqueous systems containing formamide, dimethyl-formamide, the mixture of these amides, and each amide separately with mannitol, inositol, and cyclohexanol have been determined at 25°C. The data have been treated in terms of the Savage-Wood additivity principle and in combination with literature data. New values for the methylene-amide, carbinol-amide, and amide-amide group interaction enthalpies are presented. These may be used with data on a wider variety of solute systems to obtain interaction enthalpies for new groups.     

Structural Studies on Host + Guest Recognition Sensory Systems

Rhodamine B-ethylenediamine--cyclodextrins (RhB--CDen) and rhodamine B--cyclodextrins (RhB--CD) can form inclusive complexes with many guest molecules, a reaction which can be used as a nucleic acid probe. In this paper, the most stable conformations of RhB--CDen and RhB--CD have been determined by fluorescence experiments and analyzed by molecular modeling simulation. The interaction between RhB--CDen and two guest molecules, 1-borneol and cyclohexanol, has also been investigated. The results showed that RhB--CDen has a stronger interaction with 1-borneol than with cyclohexanol. Borneol could push the three aromatic-rings of rhodamine B out of the CD cavity, while the cyclohexanol could not. The interactive sites of host and guest are also presented.     

离子液体相转移催化环己醇氧化制备环己酮

以不同种类的离子液体作为相转移催化剂,用双氧水作为氧化剂,Na2WO4·2H2O为催化剂,在适当的反应条件下,能有效进行相转移催化环己醇氧化制备环己酮.实验结果表明,采用酸性离子液体[C16mim]HSO4和[C14mim]HSO4相转移催化合成环己酮,可提高环己酮的产率,具有反应条件温和、操作简便、需用时间短、相转移催化剂可以循环使用等优点.在反应温度为90℃,反应时间为50min条件下,环己醇的转化率高达100%,选择性99%以上.     

Alternate Method for the Synthesis of Six-Membered Carbocycles with Five Stereocenters: 1,2,3,4,6-Pentasubstituted-4-hydroxy-cyclohexanes

A series of novel 1,2,3,4,6-pentasubstituted-4-hydroxy-cyclohexanes (3a–u) were synthesized from the reaction of aromatic ketones with aromatic aldehydes under mild reaction conditions in good yields. The stereochemistry of the synthesized compounds was established using 1D and 2D-NMR spectra.     

应用正交试验确定环已醇最佳工艺条件

应用正交试验确定环已醇最佳工艺条件．本文采用正交试验的方法，对锦西化工总厂环已酮车间利用环已醇脱氢生产环已酮的生产工艺过程进行了正交试验设计，应用方差分析方法得出了最佳生产工艺条件，同时给出了经济效益分析评价     

A structural study of (1RS,2SR,3RS,4SR,5RS)‐2,4‐dibenzoyl‐1,3,5‐triphenylcyclohexan‐1‐ol chloroform hemisolvate and (1RS,2SR,3RS,4SR,5RS)‐2,4‐dibenzoyl‐1‐phenyl‐3,5‐bis(2‐methoxyphenyl)cyclohexan‐1‐ol

(1RS,2SR,3RS,4SR,5RS)‐2,4‐Dibenzoyl‐1,3,5‐triphenylcyclohexan‐1‐ol or (4‐hydroxy‐2,4,6‐triphenylcyclohexane‐1,3‐diyl)bis(phenylmethanone), C₃₈H₃₂O₃, (1), is formed as a by‐product in the NaOH‐catalyzed synthesis of 1,3,5‐triphenylpentane‐1,5‐dione from acetophenone and benzaldehyde. Single crystals of the chloroform hemisolvate, C₃₈H₃₂O₃·0.5CHCl₃, were grown from chloroform. The structure has triclinic (P) symmetry. One diastereomer [as a pair of (1RS,2SR,3RS,4SR,5RS)‐enantiomers] of (1) has been found in the crystal structure and confirmed by NMR studies. The dichoromethane hemisolvate has been reported previously [Zhang et al. (2007). Acta Cryst. E 63 , o4652]. (1RS,2SR,3RS,4SR,5RS)‐2,4‐Dibenzoyl‐3,5‐bis(2‐methoxyphenyl)‐1‐phenylcyclohexan‐1‐ol or [4‐hydroxy‐2,6‐bis(2‐methoxyphenyl)‐4‐phenylcyclohexane‐1,3‐diyl]bis(phenylmethanone), C₄₀H₃₆O₅, (2), is also formed as a by‐product, under the same conditions, from acetophenone and 2‐methoxybenzaldehyde. Crystals of (2) have been grown from chloroform. The structure has orthorhombic (Pca2₁) symmetry. A diastereomer of (2) possesses the same configuration as (1). In both structures, the cyclohexane ring adopts a chair conformation with all bulky groups (benzoyl, phenyl and 2‐methoxyphenyl) in equatorial positions. The molecules of (1) and (2) both display one intramolecular O—H...O hydrogen bond.     

十聚钨酸盐催化环己醇制备环己酮工艺研究

合成新型N-甲基吗啉十聚钨酸盐[Mor1,2]4W10O32,对其进行提纯、表征和催化性能研究。催化体系是以[Mor1,2]4W10O32为催化剂,30%H2O2为氧化剂,催化氧化环己醇制备环己酮。考察催化剂用量、氧化剂用量、反应温度变化和反应时间变化对环己酮产率的影响,确定最佳反应条件为:反应温度80℃、环己醇用量5mmol、催化剂用量30μmol、氧化剂H2O2用量12.5 mmol,反应时间6小时,此时环己酮产率可达到96%。     

Effect of carriers and additives on the activity and stability of copper-based catalysts for the dehydrogenation of cyclohexanol

A continuous process for the dehydrogenation of cyclohexanol to cyclohexanone on copper-based catalysts was described. The catalysts were characterized by XRD, XPS and TPR, and Cu⁰ was found to be the active site for the copper-based catalysts studied. The two carrier catalysts were proved to be more active than the single carrier ones, and the Cr additive, which mainly existed as the CuCr₂O₄ phase on the catalyst’s surface, was found to have a significant effect on the activity and stability of the Cu-Cr-Mg-Al catalyst.