香粉叶挥发性成分提取和分析

采用水蒸汽蒸馏法提取香粉叶的挥发组分,用乙醚萃取蒸馏溶液的挥发性成份,利用气相色谱-质谱联用仪分别定性定量分析了它们的化学成分。 结果表明,挥发油的提取率为0.75%(质量百分数,以下同),主要成分有：1,8-桉叶素28.94%、α-甲基香豆酮15.75%、4-松油醇5.13%、α-松油醇11.22%、2-羟基肉桂酸7.97%、愈创木醇2.87%。 水层乙醚萃取物得率为0.25%,主要成分有：2-甲基苯并呋喃8.47%、2H-1-苯并吡喃-2-酮24.13%、2H-1-苯并吡喃-3-醇-3,4-二氢乙酸酯18.07%、p-羟甲苯基缩水甘油醚2.09%、1-苯基苯乙基-3,3-二乙酯4.50%、丙三醇二乙酸酯17.19%、乙酸金合欢酯11.80%。     

煤液化重质产物压力流体萃取过程的研究 Ⅰ.萃取物料和溶剂的选择

实验室研究结果表明,压力流体萃取是从煤液中分离矿物质和回收低挥发度煤衍生液体产物的有效技术。在萃取氢-煤法减压蒸馏釜液或水力旋风分离器底流物时,这些重质物料可分离成灰分在0.05%以下的低灰液体产品和灰分达60%以上的富灰残渣。以溶剂精炼煤法所得的滤料作为萃取原料时,也得到了良好的结果。分别采用正壬烷、甲苯,乙苯、对二甲苯、四氢呋喃、对甲酚和吡啶作为压力流体萃取用的溶剂,在100大气压和350℃条件下萃取时,上述溶剂中芳香烃是适宜的溶剂。用甲苯、乙苯或对二甲苯萃取时,萃取物收率均非常接近于用吡啶的萃取物收率,而且比用相应溶剂在索氏萃取器中所得为高。可以设想,在压力流体萃取过程中,有一部分甲苯不溶物转化成甲苯可溶物。     

粮谷中灭草松残留量检测的GC及GC-MS/MS研究

试验证明GC-ECD及GC-MS／MS两种方法均能用于粮谷中残留除草剂灭草松的测定。GC-MS／MS法可同时进行定性和定量分析,测定结果的可靠性较高。GC-ECD法具有较高的灵敏度,用于定量分析的效果较好。提出一种可与上述两种方法接用的试样预处理方法。10 g试样用甲醇提取其中的测定组分,再用正己烷萃取除去脂肪。用稀盐酸调节水相的酸度至pH≤3, 用二氯甲烷将灭草松萃取至有机相。在45℃减压干燥除去溶剂,所得浓缩的残渣溶于0．2 mL甲醇中并进行甲烷化和纯化(用固相萃取法),所得残留灭草松溶于1 mL正己烷中供GC-ECD或 GC-MS／MS测定。用两种方法进行粮谷试样的分析,测定结果的RSD值依次为2．3％-4．7％和 3．5％-6．7％。用标准加入法测得两方法的回收率依次为77％-98％和80％-102％,方法的检出限为0．01 mg·kg-1。     

Separation and analysis of the degradation products of two coals in aqueous NaOC1 solution

两种煤于温和条件下在次氯酸钠水溶液中进行降解,所得水溶液经酸化后,水溶物依次用乙醚、CS2、石油醚、乙酸乙酯和苯进行分级萃取,萃取物经重氮甲烷酯化后用GC/MS分析.结果发现氯代物、脂肪酸和芳酸是煤的NaOCl水溶液降解的典型化合物,不同极性溶剂分级萃取可以实现产物的初步族组分分离.通过该研究建立煤的次氯酸钠氧化反应混合物有效分离和分析的方法,为煤的高附加值利用提供有效的途径.     

核桃楸树皮乙醇提取物的成分分析

采用常规提取法浸提核桃楸树皮的活性成分,采用GC-MS联用技术对核桃楸树皮乙醇提取物中氯仿萃取物和乙酸乙酯萃取物的化学组成和各成分进行分析. 结果表明,核桃楸树皮乙醇提取物中氯仿萃取物的主要活性成分分别为:5-羟基-1,4-萘醌(胡桃醌,质量分数36.65%),4-羟基-2-甲氧基肉桂醛,2,3-二氢苯并呋喃,香草醛,2-甲氧基-4-乙烯基苯酚. 核桃楸树皮乙醇提取物中乙酸乙酯萃取物的主要活性成分分别为:1,2,3-苯三醇(质量分数42.31%),5-羟基-1,4-萘醌(胡桃醌,质量分数12.33%),7-甲氧基-1-四氢萘酮(质量分数11.26%),5-羟甲基-2-呋喃醛,3,4-二氢-6,7-二羟基-1(2H)-萘酮,4-羟基-2-甲氧基肉桂醛,D-阿洛糖.     

两种煤的次氯酸钠水溶液降解产物的分离与分析

两种煤于温和条件下在次氯酸钠水溶液中进行降解,所得水溶液经酸化后,水溶物依次用乙醚、CS2、石油醚、乙酸乙酯和苯进行分级萃取,萃取物经重氮甲烷酯化后用GC/MS分析。结果发现氯代物、脂肪酸和芳酸是煤的NaOCl水溶液降解的典型化合物,不同极性溶剂分级萃取可以实现产物的初步族组分分离。通过该研究建立煤的次氯酸钠氧化反应混合物有效分离和分析的方法,为煤的高附加值利用提供有效的途径。     

小叶女贞花挥发性成分分析

采用水蒸汽蒸馏法,分别以正己烷和乙醚为萃取剂从小叶女贞花中提取挥发性成分,结合气相色谱-质谱(GC-MS)法,运用峰面积归一化法计算各化学成分在挥发油中的相对含量.在正己烷萃取的挥发油中鉴定了45种组分,在乙醚萃取的挥发油中鉴定了58种组分.研究了不同极性溶剂作萃取剂对小叶女贞花挥发性成分的影响.     

大兴安岭地区细叶杜香挥发性成分的研究

1　实验部分1.1　仪器与样品　　固相微萃取(SPME)手柄及100μm聚二甲基硅氧烷(PDMS)萃取头(美国Supelco),恒温磁力搅拌装置,GC 17A QP5050GC/MS仪(日本Shimadzu)。　　细叶杜香2002年8月采于内蒙古大兴安岭,在避光处将其自然晾干后,将其嫩枝和叶剪成细末,待用。1.2　杜香挥发性成分的提取　　水蒸气蒸馏:取细叶杜香样品100g,按常规方法进行水蒸气蒸馏,提取6h,水层用氯化钠饱和后,用乙醚萃取,回收乙醚,得棕黄色透明油状物0 6g,将其用乙醚稀释后用于气相色谱 质谱(GC/MS)分析。　　SPME:将SPME纤维在GC/MS仪进样口250℃下老化2…     

在线萃取流动注射分光光度法测定二羟基苯磺酸钙中微量对苯二酚

用在线萃取-流动注射分光光度法(FISP)测定了作为杂质与2,5-二羟基苯磺酸钙共存的对苯二酚。专门设计并制作了与流动注射分光光度测定单元组合在一起的在线萃取流路,对苯二酚用乙醚萃取进入有机相并在此相中于其吸收峰297.5 nm波长处测定其吸光度,通过萃取基体成分,即2,5-二羟基苯磺酸钙的干扰,由于其在乙醚中不溶解而得以消除。对苯二酚的吸光度与其相应浓度在3.5×10-6~5.0×10-4mol.L-1之间呈线性关系,相关系数达0.999 4。该方法的检出限为2.53×10-6mol.L-1。应用此方法分析了来自不同批次的3个试样,所得结果的RSD在0.69%~1.65%之间,且其值与药典法所测得结果相符。     

DNS光度法测定风味鱿鱼中淀粉、还原糖和蔗糖的含量

为测定风味鱿鱼中淀粉、还原糖和蔗糖的含量,取2份样品(每份3～5g),一份样品经水溶解及在盐酸溶液的水解作用下分成供测定原含还原糖和由蔗糖水解产生的还原糖在内的总还原糖测定的两部分试样溶液;另一份样品经乙醚萃取除去脂肪和用水溶解分离蔗糖后,将留下的不溶物通过在盐酸溶液中回流等操作将其中淀粉水解产生单糖,经过滤后取其滤液作为测定淀粉的试样溶液。从上述3份试样溶液中各分取2.0mL溶液,用DNS光度法测定其中还原糖的含量并换算成上述3组分的含量。用葡萄糖标准溶液制作工作曲线。在测定淀粉试液的制备中,对除去蔗糖的处理进行改进,在加水溶解的操作中增加了3～5次的重复操作,使样品的不溶解部分中残留的可溶性糖大大降低,例如未进行改进时测定得到的不溶物中糖含量分别为27.0,62.2mg·g-1的两份样品,对方法进行改进后,不溶物中糖含量依次降为0.32,0.63 mg·g-1,分别降低了98.8%,99.0%,保证了淀粉测定结果的准确性。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.