国内C9石油树脂生产现状与发展研究

介绍了C9石油树脂的原料组成及C9石油树脂合成机理。对C9石油树脂的合成工艺进行了介绍,阐述了合成工艺的选择原则并对几种C9石油树脂的合成工艺进行了比较分析。重点介绍了C9石油树脂合成工艺的发展状况,指出了C9石油树脂加氢技术研发要解决的关键技术及发展方向。     

阿奇霉素及其关键中间体的合成研究进展

以红霉素A为原料经肟化反应、贝克曼(Beckman)重排反应、还原反应和N-甲基化还原反应制备大环内酯类药物阿奇霉素是一条合理的合成技术路线.本文着重评述了阿奇霉素和关键中间体红霉素A(E)肟、红霉素A6,9-亚胺醚、9-脱氧-a-氮杂-9a-类红霉素A的合成方法,提出今后阿奇霉素及其关键中间体合成工艺研究方向和需解决的关键问题.     

Investigation of the mechanism of formation of BaTi<Subscript>4</Subscript>O<Subscript>9</Subscript> from initial mixtures of different dispersion

The mechanism of solid-phase interaction in synthesis of BaTi₄O₉ is investigated using initial mixtures characterized by different degrees of dispersion and prepared by three methods: (i) mechanical mixing and grinding of initial components, (ii) coprecipitation from aqueous solutions of salts, and (iii) the citrate-nitrate sol-gel technique. The use of initial mixtures consisting of nanoparticles in the synthesis makes it possible to decrease the sintering temperature by 100–300°C, which ensures the preparation of single-phase samples, and to reduce several times the heat treatment time. Dilatometric investigations of the sintering process in the synthesis of BaTi₄O₉ from the initial mixtures under study indicate that the maximum change in the linear sizes of samples occurs in the temperature range 1000–1250°C. It is shown that, in this temperature range, the concurrently formed impurity phases undergo decomposition and the growth rate of BaTi₄O₉ crystals increases. The optimum conditions for synthesis of BaTi₄O₉ in the form of a powder with a particle size of approximately 77 nm and in the form of a ceramic material are determined, which is necessary for use of this compound as different functional materials.     

1800kt／a甲醇装置合成催化剂运行总结

结合神华包头煤化工分公司煤制甲醇合成工艺，介绍Katalc051-9型甲醇合成催化剂升温还原、生产运行、钝化等各个阶段的情况，并指出其在运行等阶段存在的问题及解决措施。     

Effect of L-triiodothyronine on Δ9 desaturase activity in liver microsomes of male rats

Male rats injected with a single saturating dose of L-triiodothyronine (T₃) showed, after a lag time of approximately eight hr, a sharp rise in Δ9 desaturase activity. Desaturase activity reached a plateau which was 1–1.2 times above the base line levels of rats which were not hormone-treated. The plateau was maintained for five days in animals which were kept on daily hormone-treatment. The increase in Δ9 desaturase activity by T₃ required ongoing protein synthesis, because the increase in enzymatic activity due to hormone treatment was completely abolished in the presence of cycloheximide. These findings suggest that cycloheximide may block the induction of Δ9 desaturase by T₃ and/or inhibit the synthesis of protein(s) essential to the desaturation-response to T₃. Modifications observed in liver microsomal fatty acid composition in T₃ treated rats were independent of the effect on desaturation. It is suggested that other factors, such as diet, membrane lipid synthesis and degradation, as well as fatty acid turnover and oxidation, could be involved in affecting the fatty acid composition of thyroid hormone-treated rats.     

Synthesis of civetone from palm oil products

Metathesis of ethyl oleate, catalyzed by WCl₆ and SnMe₄, provided diethyl 9-octadecenedioate (the desired starting material for the synthesis of civetone) in 99% yield. Dieckmann condensation of diethyl 9-octadecenedioate gave 2-ethoxycarbonyl-9-cycloheptadecenone (63% yield), the hydrolysis-decarboxylation reaction of which yielded civetone (93%). Identification of all products was by¹H nuclear magnetic resonance, infrared and mass spectroscopic data. This is the first report of the synthesis of civetone from palm oil-derived products.     

Hydrogenation of Carbon Oxides over Perovskite-Type Oxides

Transition metals, metal oxides and metal-containing mixed oxides have been extensively used for Fischer-Tropsch hydrocarbon synthesis (1-9) and their ability to yield oxygenated compounds. During the last two decades, an extensive search has been carried out in examining the mechanism of catalytic hydrogenation of co and CO, which produced hydrocarbons and oxygenate compounds. The catalytic models for hydrocarbon synthesis have already been reviewed by Vannice (lo), which gives detailed information and discusses the data which were obtained during their development. As a broad product distribution is obtained during the FT synthesis, the mechanisms are extremely complicated and not clearly understood: therefore this topic is beyond the objective of this chapter and hence no further attention will be paid.     

Template synthesis of rotaxanes with carbamate-linked axles

Proceeding from diisocyanates 4 and 10 – 13 , (4-hydroxyphenyl)triphenylmethane 14 and tetralactame macrocycles 1 , 2 and 9 the threading synthesis of rotaxanes 16 – 21 containing carbamate units in the axle is described. In addition to aromatic diisocyanates aliphatic ones are firstly introduced as building blocks in rotaxane chemistry. The template synthesis of the new tetralactame macrocycle 9 with a pyridine unit is presented. It is used as wheel in a rotaxane synthesis towards the carbamate-linked rotaxane 21 .     

盐酸沙拉沙星的合成

以2,4-二氯氟苯乙酮为原料,在制取了7-氯-6-氟-1-对氟苯基-1,4-二氢-4-氧代喹啉-3-羧酸后,再与哌嗪缩合,并成盐制得盐酸沙拉沙星。     

Synthesis of Substituted Quinolizidines via a Gold‐Catalyzed Double Cyclization Cascade

A novel synthesis of quinolizidines by a cationic gold‐catalyzed double cyclization cascade has been developed. The reaction was initiated by the gold‐catalyzed 6‐exo‐dig cyclization of ynamides, which was followed by a second cyclization of an enamide intermediate to provide the corresponding quinolizidine derivatives. The utility of this reaction was demonstrated by application to the synthesis of multi‐substituted quinolizidines and by the total synthesis of a quinolizidine alkaloid, (±)‐lupinine.

     

Hydrogenation of Carbon Oxides over Perovskite-Type Oxides

Transition metals, metal oxides and metal-containing mixed oxides have been extensively used for Fischer-Tropsch hydrocarbon synthesis (1–9) and their ability to yield oxygenated compounds. During the last two decades, an extensive search has been carried out in examining the mechanism of catalytic hydrogenation of co and CO, which produced hydrocarbons and oxygenate compounds. The catalytic models for hydrocarbon synthesis have already been reviewed by Vannice (lo), which gives detailed information and discusses the data which were obtained during their development. As a broad product distribution is obtained during the FT synthesis, the mechanisms are extremely complicated and not clearly understood: therefore this topic is beyond the objective of this chapter and hence no further attention will be paid.     

The Anionic [1,3]‐H‐Shift Applied in Synthesis: A Novel Access to (+)‐Citreoviral

In this paper we present a highly stereoselective and concise synthesis of the tetrahydrofuran derivative 3 and thus, a formal synthesis of the mycotoxin metabolite (+)‐citreoviral ( 2 ). In our route we made use of a novel anionic [1,3]‐H‐shift to convert the homoallylic alcohol 9 into the allylic benzyl ether 10 . Another key step was the regio‐ and stereocontrolled cyclization of epoxide 18b to tetrahydrofuran 19b , which was then converted into ester 3 .     

Stable iron-incorporated mesoporous silica materials (MFS-9) prepared in strong acidic media

Iron-incorporated mesoporous silica materials (MFS-9) have been successfully prepared in strong acidic media by a two-step synthesis procedure, which has an hexagonal structure with uniform mesopores and exhibits superior hydrothermal stability and high catalytic activities for the hydroxylation of phenol and also of bulky trimethylphenol. X-ray diffraction data show that mesoporous ferrisilicate (MFS-9) can retain its mesoporous structure in boiling water up to 100 h. Characterization of MFS-9 by a variety of spectroscopic techniques, including electron spin resonance, UV–vis and UV–Raman spectroscopies, suggests that Fe species in the framework of MFS-9 are mainly tetrahedrally coordinated even after calcination at 823 K.     

3-羟基-6-O-甲基红霉素A9-肟的合成

从克拉霉素的前体 6 O 甲基 2′, 4″ 二 (三甲基硅 ) 红霉素A 9 ( 1 异丙氧基环己基 )肟出发,在φ(C2H5OH) =50%的乙醇水溶液中加入甲酸,加热回流 2h脱去保护得到 6 O 甲基红霉素A9 肟,将它悬浮于水中,在w(HCl) =1%的盐酸水溶液作用下水解去除 3 克拉定糖得到目标化合物 3 羟基 6 O 甲基红霉素A9 肟,它是合成对耐药菌有优良活性的第三代红霉素酮内酯和酰内酯的重要中间体, 收率为 73 3%。为了简化反应步骤,试探了在脱保护一步不分离产物而在w(C2H5OH) =95%的乙醇和w(HCl) =2%的盐酸水溶液反应体系中直接水解脱糖的方法,得到了目标化合物,总收率为 69 0%。通过1HNMR、13CNMR和MR确定了目标化合物的结构。     

两个Galaxamide类似物的固相合成及抗肿瘤活性研究

以N-芴甲氧羰基-L-亮氨酸(Fmoc-Leu-OH)和N-芴甲氧羰基脯氨酸(Fmoc-Pro-OH)为原料,采用经典的Fmoc固相合成法,通过对氨基酸N端的保护及脱保护、氨基酸的甲基化、缩合等步骤合成线性五肽,以缩合试剂六氟磷酸苯并三唑-1-基氧基三吡咯烷基磷(Py \BOP)关环,分别以59.5%和41.1%的环合收率得到了两个新的环五肽化合物G_1和G_2,结构通过~1HNMR、~(13)CNMR、ESI-MS进行确认。采用MTT法对目标化合物G_1和G_2进行了体外抗肿瘤活性的研究。结果表明:含有脯氨酸片段的Galaxamide类似物G_2具有良好的活性,尤其对人乳腺癌细胞株(MCF-7)具有较好的细胞毒性,其IC_(50)值为5.85 mg/L。     

以6-氯嘌呤为原料合成2-氟腺嘌呤的新方法

医药中间体2-氟腺嘌呤的合成主要存在3个问题：①使用易爆炸的重氮化反应;②原料成本高;③总收率不高,规模化难度大。这些问题限制了2-氟腺嘌呤的进一步广泛应用。为了解决以上问题,本文以廉价的6-氯嘌呤为原料,先用四氢吡喃基保护6-氯嘌呤9位NH;然后以二氯甲烷为溶剂,在三氟乙酸酐和四丁基硝酸铵体系作用下,以85%的收率得到6-氯-2-硝基-9-吡喃基嘌呤;继而以DMF为溶剂,和NH₄F反应,以83%的收率得到2-氟-6-氯嘌呤;最后在饱和的NH₃/CH₃OH溶液中氨解,得到2-氟腺嘌呤。共4步,总收率58%,产物及中间体的分离纯化不需要柱层析。同时考察了保护基团和反应规模对收率的影响。本方法原料廉价易得,避免使用高毒和剧毒试剂,操作安全简便,有较好的实际应用价值。     

泰利霉素重要中间体3-氧代-6-O-甲基红霉素的合成

由克拉霉素的前体6-O-甲基-2′,4″-二(三甲基硅)-红霉素A9-(1-异丙氧基环己基)肟(Ⅰ)出发,常温下以φ(HC l)=10%的盐酸催化水解得3-羟基-6-O-甲基红霉素A9肟(Ⅱ);然后一锅煮进行化合物Ⅱ的2′-羟基乙酰化、3-羟基氧化,得2′-乙酰基-3-氧代-6-O-甲基红霉素A9-(O-乙酰基)肟(Ⅳ);最后脱乙酰基、还原9-肟基再次应用一锅煮法合成,得到目的化合物3-氧代-6-O-甲基红霉素(Ⅵ),总收率为57.0%,经HPLC测定w(Ⅵ)=98.5%。通过1HNMR1、3CNMR和MS,表征了各中间体及目标化合物的结构。     

Olefin Metathesis of Vinylgermanium Derivatives as Method for the Synthesis of Functionalized Cubic and Double‐Decker Germasilsesquioxanes

For the first time, olefin cross metathesis has been developed for vinylgermanium compounds. This paper also marks the first case of transition metal‐catalyzed functionalization of heterosilsesquioxanes, which in our case are cubic vinylgermasilsesquioxanes and newly synthesized di(vinylgermyl)substituted double‐decker silsesquioxane. These processes lead to a series of new molecular, unsaturated mono‐ and divinyl‐substituted germasilsesquioxanes, which can be potentially applied as precursors for optoelectronics and for the synthesis of new advanced materials. Additionally, preliminary tests of metathetic copolymerization of divinylsubstituted double‐decker digermasilsesquioxanes (DDSQ‐2ViGe) with selected diolefins proved to be very promising and resulted in the synthesis of novel stereoregular trans‐germasilsesquioxyl‐vinylene‐phenylene macromolecular derivatives. All newly obtained compounds were isolated and characterized by mass and spectroscopic methods.

     

枯草芽孢杆菌联产纳豆激酶和g-聚谷氨酸

利用实验室保存的纳豆激酶生产菌Bacillus subtilis Natto NLSSe进行了g-聚谷氨酸合成研究,在不添加谷氨酸的培养基中合成了分子量在200~300 万Da的g-聚谷氨酸,表明该菌是谷氨酸非依赖型菌. 合成纳豆激酶的合适碳、氮源分别是蔗糖和大豆蛋白胨,合成g-聚谷氨酸的合适碳、氮源分别是柠檬酸和NH4C1. 通过正交实验研究了碳、氮源对纳豆激酶和g-聚谷氨酸联产的影响,结果表明,增加培养基中大豆蛋白胨及柠檬酸的浓度能分别促进纳豆激酶和g-聚谷氨酸的合成,而不抑制另一产物的合成,有利于纳豆激酶和g-聚谷氨酸的联产. 在大豆蛋白胨10 g/L, NH4C1 9 g/L,柠檬酸15 g/L时,纳豆激酶酶活为121.2 U/mL,g-聚谷氨酸产量为1.1 g/L,均达到了单独合成时的水平.     

昆布氨酸清洁化合成研究

昆布氨酸是昆布中一种具有降压活性的非蛋白质氨基酸,但是由于含量极少,大都采用仿生合成的方法制备.本文中采用L-赖氨酸为原料,仿生合成了具有降压活性的昆布氨酸,产率可达37.6%,纯度可达97.2%.并研究了昆布氨酸的若干物理和化学性质,结构分析表明,准分子离子峰[M H] m/z 207,HNMR质子位移信号δ=3.6288ppm,单重峰,9H,红外光谱在1480cm-1、2945cm-1和2863cm-1的吸收峰都说明在赖氨酸ε-氨基的N上引入了甲基,形成了季铵盐侧链,与昆布氨酸的结构相符合.