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The thermolysis of the isomerized products derived from norbornadiene-coordinated carbonyl iron complexes gave two sorts of the thermolytic products based on different substituents on the olefin ligands. One is the corresponding diiron dimer complex, and the other is the complex in which the C-C bond of the cycloolefin ligand is broken.

以降冰片二烯三羰基铁络合物衍生出来铁卡宾络合物的异构化产物的热解,随着烯烃配体上取代基的不同,而分别得到了络合物发生二聚和烯烃配体发生碳碳键断裂的两类热解产物。

The dissertation mainly consists of two parts:1. The Reaction Chemistry of Alkynes under Palladium Catalysis Part 1 studies the reaction α,β-unsaturated carbonyl compounds with alkenylpalladium intermediate generated by nucleopalladation, and discovered 1 the Pd-catalyzed tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls,2 the four-component tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls, 3 the tandem intramolecular oxypalladation-conjugate additionreaction of alkynoic acids with α,β-enals. These new reactions provide notonly efficient highly stereoselective methods for the synthesis of γ,δ-unsaturated,polyunsaturated carbonyl compounds and γ-lactonic aldehydes, but also thebasic transformations for a number of C-C bond formation reactions which can be usedto design synthesis of many acyclic, cyclic or polycyclic compounds.

本论文的主要工作分为两个部分:一、钯催化下炔烃的反应化学在本小组前人工作的基础上,我们详细研究了炔烃亲核钯化产生的烯基钯中间体与α,β-不饱和羰基化合物的反应,发现两价钯催化下卤离子-炔烃-α,β-不饱和醛酮的串联加成反应、卤离子-炔烃-α,β-不饱和醛酮的西组分串联加成及炔酸分子内氧钯化-串联Michael型加成反应;由此发展了γ,δ-不饱和醛酮、多不饱和羰基化合物和带有醛酮基侧链的γ-丁内酯衍生物的高立体选择性合成方法,这一过量卤离子存在下的烯基钯对α,β-不饱和羰基化合物共轭加成反应的发现,为大量碳-碳键形成反应的实现提供了基础,使我们能够从这一基本反应出发,设计和开发多种分子内、分子间的碳碳成键反应,以好的立体、区域选择性组建开链、环状及多环类型的化合物。

The results showed that myristic acid(14∶0) and linoleic acid (18∶2) were significantly increased,and positively correlated with the levels of TC, TG, LDLC and apoB;while the levels of docosahexaenoic acid (DHA,22∶6),arachidonic acid (20∶4) and docosatetraenoic acid (22∶4) an...

结果表明:患者肉豆蔻酸(140)和亚油酸(182)明显增高,与总胆固醇、甘油三酯、低密度脂蛋白-胆固醇和载脂蛋白B水平呈正相关;而二十二碳六烯酸(DHA,226)、二十碳四烯酸(AA,204)和二十二碳四烯酸(224)以及硬脂酸(180)明显降低,与TC、TG、LDL-C和apoB水平呈负相关。

Unsaturated fatty acids including linoleic acid、γ-linolenic acid、 dihomo-γ-linolenic acid、 arachidonic acid and eicosapentaenoic acid have played important roles in prevention and treatment of heart disease and high blood pressure、 in the inflammatory area (for example, treatment of asthma、 arthritis and psoriasis) and for some cancer treatment Natural sources of UFAs are animal and plant, such as EPA in fish oils, arachidonic acid in porcine liver and y -linolenic acid in Oenothera biennis L..

不饱和脂肪酸包括亚油酸、γ-亚麻酸、双高γ-亚麻酸、花生四烯酸和二十碳五烯酸等在内对心脏疾病、高血压、炎症(如哮喘、关节炎和牛皮藓)和某些癌症的预防和治疗均有显著效果。不饱和脂肪酸的自然来源主要是动植物,如二十碳五烯酸存在于深海鱼油,花生四烯酸存在于猪肝而γ-亚麻酸多来源于月见草等植物种籽。

For TRO there are a little surfacatants whose effect are not good.In this paper,content of sulfonates and composition of alkyl are decided through right design ;under control reaction conditions different alkylbenzene sulfonates are synthesized;Polyreaction catalyst is developed .non-straight high carbon olefine are made through C9-C12 Polyreaction technolgy;clear composition alkylkenzene is sulfanated in falling-film reactor by SO,product can be adjusted,recipe of the surfacate can be used for super-low interfacialtension with Daqing oil -10-3-10-4mN/m,and stablity is good too.According to method issued by Daqing Develop and Explore Research institute,EOR is over 20% in natural core .

本文研究通过烷基苯磺酸盐组成的正确设计,确定了磺酸盐的当量范围和烷基碳数组成和分布;通过对烷基化条件控制,设计合成了不同碳数的直链和支链烷基苯及烷基二甲苯,并用于制备了相应的烷基苯磺酸盐;研制出了新型的烯烃叠合络合催化剂,采用C_9、C_(12)支链烯烃叠合工艺合成了更高碳数的支链烯烃,并进一步合成出相应的烷基苯和烷基二甲苯;以SO_3为磺化剂,通过对磺化条件的选择和控制,采用已知组成的烷基苯混合物进行膜式磺化反应,使合成工艺得以简化;所得磺酸盐组成确定并且可控,最终配方可与大庆原油形成超低界面张力,达10~3~10~(-4)mN/m数量级,且稳定性良好;以合成的烷基苯磺酸盐为主体形成了三元复合驱配方,室内驱油模拟实验表明,按照大庆研究院对复合驱体系活性剂的评价方法,在天然岩芯上的驱油效率在20%以上。

The electron impact mass spectra of the chemical products modified by 2-amino-2-methylpropanol of the fatty acids in sunflower oil were analyzed; the allocation rule for the carbon double bonds in olefinic acids was discussed and the location of the carbon double bonds of the fatty acids in sunflower oil was confirmed.

解析了葵子油脂肪酸2-氨基-2-甲基-丙醇化学修饰产物的EI质谱图,讨论了烯酸中碳碳双键的定位规则,确定了葵子油脂肪酸中碳碳双键的位置鉴定出葵子油6种脂肪酸,不饱和脂肪酸相对含量为89.41%,其中人体必需脂肪酸9,12-十八碳二烯酸含量占65.30%。

The geometric optimization of C_(59)Sm and C_(60)Sm shows that the replacement of a C atom with a Sm in C_(60) yields a stable substitutionally doped fullerene C_(59)Sm, and among the five possible optimized geometries for C_(60)Sm, the most favorable exohedral sites are above the center of a hexagon and a pentagon ring.

替代掺杂富勒烯C_(59)Sm与外掺杂富勒烯C_(60)Sm几何结构与电子结构分析表明,以Sm原子取代C_(60)分子中的一个碳原子后碳笼仍保持稳定的替代结构,而对五种可能的C_(60)Sm结构,Sm原子倾向于栖息在六碳环与五碳环的空洞上方。

Results Eleven compounds were obtained and identified as sarcodonin A, scabronine B, 3β-hydroxy-5α, 8a-epidioxyergosta-6, 22-dien,(22E, 24R)-ergosta-7, 22-diene-3β, 5α, 6β-triol,(22E, 24R)-ergosta-7, 22-diene-3β-ol, benzoic acid, 4-hydroxylben-zaldehyde, 4-monopropanoylbenzenediol, ethy1-β-D-glucopyranoside, thioacetic anhydride,(2S, 2'R, 3S, 4R)-2-(2-hydroxyoctadecanoylamino) docosane-1, 3, 4-triol.

结果共分离鉴定了11个化合物,分别是:sarcodonin A、scabronine B、3β羟-5α,5α-过氧麦角甾-6,22-二烯-3β-醇、(22E,24R)-麦角甾-7,22-二烯-3β,5α,6β三醇、(22E,24R)-麦角甾-7,22-二烯-3β-醇、苯甲酸、对羟基苯甲醛、对羟基苯甲酸乙酯、乙基-β-D-吡喃葡萄糖苷、硫代乙酸酐、(25,2'R,3S,4R)-2-(2-羟基-十八碳酰胺)二十二碳烷-l,3,4-三醇。

Molybdophopsphoric Acid Catalysis in the Oxidative Cleavage of Olefins by the Hydrogen Peroxide Oxidative cleavage of the double bond could be catalyzed by H_3PMo_(12)O_(40) using H_2O_2 as oxidant, various trisubstituted olefins were oxidized to aldehydes or ketones in high yields. The system was not satisfied for electron-deficient olefins such as trans-(2-nitrovinyl) benzol or chalcone. The reaction of aliphatic olefins did not occur under the same conditions.

二、磷钼酸催化过氧化氢对烯烃的氧化断裂反应用过氧化氢(30%)作为氧化剂,磷钼酸可以催化氧化碳碳双键的断裂反应,三取代的烯烃被氧化生成醛或酮,产率较高;此体系对于缺电子烯烃如查尔酮,不饱和硝基化合物的断裂反应效果较差,脂肪族烯烃在此体系下的氧化并不发生。

The study of natural fullerenes is a new area of across fullerene science and geological science. So far natural fullerenes have been found in shungite, fulgurite, carbonaceous conglomerates in impact crater, E/K boundary carbonrich clay rock layer, T/P boundary layer, dinosaur eggshell, coal, heavy crude oil, solid bitumen and socalled seminatural fullerenes in common soots, Chinese ink sticks, commercial char, et al., only with low concentrations.

天然富勒烯研究是富勒烯科学和地质科学相交叉的一个新兴研究领域,迄今为止已在桑加岩、闪电熔岩、陨石撞击坑中的含碳质角砾岩、古近系/白垩系地层界线的含碳粘土岩、三叠系/二叠系界线岩石、恐龙蛋壳、煤、重质油、固体沥青以及半天然的烟灰、木炭、书墨等物质中检测到富勒烯的存在,但含量很低。

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