固相萃取/气相色谱-质谱分析催化裂化柴油中的含氮化合物

采用固相萃取技术分离富集催化裂化柴油中的中性和碱性含氮化合物,优化了洗脱溶剂的种类及用量,并考察了分离方法的回收率和重复性。结果表明,二氯甲烷和丙酮-二氯甲烷可以有效分离富集柴油中的中性和碱性含氮化合物;固相萃取法的回收率高达99. 5%,3次分离实验结果的相对标准偏差均小于4%。分离后的组分采用气相色谱-质谱(GC-MS)定性,数据表明,催化裂化柴油中的中性含氮化合物主要为C0～C3-吲哚及C0～C5-咔唑,碱性含氮化合物主要为C1～C4-苯胺及C0～C2-喹啉。采用气相色谱-氮化学发光检测器对含氮化合物进行定量,发现中性含氮化合物占已定性含氮化合物总量的96. 6%;咔唑类含氮化合物的含量最高,占已定性含氮化合物总量的64. 3%;从化合物结构上看,化合物含量随着甲基取代基数目的增多呈先增加后降低的趋势。该方法可用于催化裂化柴油中含氮化合物的类型分布分析。     

催化柴油中氮化物分布的气相色谱-原子发射光谱分析方法的研究

建立了催化柴油馏分中各种氮化物类型分布的气相色谱-原子发射光谱(GC-AED)分析方法,考察了色谱条件和不同的试剂气压力对各种氮化物分离和检测灵敏度的影响,定性(或归类)了某典型催化柴油中的73个氮化物,计算了程升条件下各种氮化物的保留指数,为不同实验室的定性比较提供了依据。以峰面积对质量浓度作图,氮化物在2.0~600 mg/L浓度范围内,AED检测器对不同氮化物有良好的线性响应,线性相关系数达0.998。几种氮化物(吲哚、1-甲基吲哚、C2-吲哚、咔唑、1-甲基咔唑、1,8-二甲基咔唑)峰面积的相对标     

催化裂化柴油中芳胺类化合物组成分析

采用酸萃取方法分离出催化柴油中的碱性组分,通过色谱-质谱(Gc-Ms)分析其组成。芳胺化合物是催化裂化柴油中碱性氮化物的主要成分,与吡啶类化合物存在共逸出现象,且具有相同的质谱特征,利用胺类化合物能够与乙酸酐发生乙酰化反应的特性,比较乙酰化前后化合物色谱保留时间和质谱图变化研究芳胺类化合物组成。结果表明,催化裂化柴油中的芳胺类氮化物以C0～C4的烷基苯胺类为主,鉴定了苯基苯胺、茚满胺、萘胺、芴胺及菲胺等胺类化合物。     

催化柴油中含氮化合物类型分布的气相色谱分析方法

建立了催化柴油馏分中各种含氮化合物类型分布的气相色谱-氮化学发光检测分析方法,考察了色谱条件对各种含氮化合物分离的影响。采用Al2O3柱富集催化柴油中的含氮化合物,辅以气相色谱-质谱检测器以及部分含氮化合物标准样品对某催化柴油中的80多个含氮化合物进行了定性(或归类)。以N,N-二甲基苯胺、三丁基胺、喹啉、吲哚、咔唑作为标准样品,考察了各种含氮化合物在氮化学发光检测器上的响应,以吲哚为参照,各含氮化合物的相对响应因子为0.97～1.07,表明含氮化合物的响应与其类型无关。氮的质量浓度在1.0～600 mg/L范围内,含氮化合物的峰面积与质量浓度有良好的线性响应,线性相关系数达0.998。催化柴油中几种含氮化合物(吲哚、C2-吲哚、咔唑、1-甲基咔唑、1,8-二甲基咔唑)含量测定值的相对标准偏差均小于8%。当信噪比(S/N)为3时,测得咔唑氮的检出限为1.0 mg/L。苯胺、喹啉、吲哚、咔唑等4种含氮化合物的加标回收率为89.5%～99.8%。该方法可用于不同来源和不同加工工艺的柴油馏分中各种含氮化合物类型分布的研究。     

稀土铬酵母的制备及其铬含量研究

研究了稀土元素La、Nd、Sm、Er的添加浓度分别为50μg·g-1、75μg·g-1、100μg·g-1和125μg·g-1时对富铬酵母中铬含量的影响 研究结果表明,稀土元素能够提高富铬酵母中的总铬和有机铬含量,当添加100μg·g-1Nd时,富铬酵母中的总铬含量和有机铬含量最高,分别为784.24μg·g-1和755.85μg·g-1,是未加稀土的富铬酵母的3倍以上     

重油催化裂化汽油中含氮化合物的分析

利用酸萃取技术浓缩分离重油催化裂化（RFCC）汽油中的氮化物，比较了两种萃取剂和两种油剂比对分离效果的影响，结果发现选用10％（体积分数）HCl作萃取剂，油剂比为10：1（体积比）时，碱性氮化物的提取率较高；浓缩分离出的氮化物用色谱－质谱联用方法对其进行了检测，结果表明RFCC汽油中的氮化物主要是C0－C2苯胺及少量吡啶类、喹啉类碱性氮化物。     

辽河常压渣油中含氮化合物悬浮床加氢过程转化与分布规律研究

采用傅里叶变换红外光谱(FT-IR)、气相色谱-质谱等手段,研究了辽河常压渣油中的含氮化合物在悬浮床加氢反应过程中的转化规律。研究表明,辽河常压渣油轻蜡油(350~400 ℃)中的碱性含氮化合物主要为喹啉类,还有一部分吡啶类及吖啶类,非碱性含氮化合物主要为C_1~5咔唑和吲哚类。重蜡油(400~450 ℃)中含氮化合物主要是吖啶及吡啶类物质。辽河常压渣油加氢反应后的轻蜡油馏分中碱性含氮化合物主要是C_1~7喹啉和苯并喹啉类物质,以及C_1~2吖啶类物质,非碱性含氮化合物主要是C₂、C₃、C₇-吲哚。在反应后的重蜡油馏分中含氮化合物主要为吖啶类和咔唑类物质。喹啉类物质在反应前后常压渣油馏分中的含量随着沸点升高而降低,且加氢反应后常渣中的喹啉类物质浓度高于加氢反应前。在悬浮床加氢反应过程中,含氮杂环化合物减少,部分非碱性含氮化合物向碱性含氮化合物转化。     

极谱法测定锡锭中痕量镉

研究了单扫描示波极谱法直接测定锡锭中痕量镉的条件,在KI-OP底液介质中,于峰电位一0.70V(νS. SCE)处产生一镉灵敏吸附疲,Cd(Ⅱ)含量在0．1～μg/25ml范围内呈线性。测定含镉o．097μg·g-1的样品,相对标准偏差为11％,测出下限为0．05μg·g-1。加标回收平为95%～103％。所拟方法具有较好的选择性,且简便、快速、准确。     

宝明页岩柴油碱性氮化物的梯度富集及GC-MS分析

利用溶剂萃取和柱色谱等技术浓缩分离新疆宝明页岩油柴油馏分中的碱性氮化物。以宝明页岩柴油为原料,经糠醛溶剂精制,初步得到富集碱性氮化物的抽出油。以抽出油为深度富集碱性氮化物的原料,采用柱色谱等分离方法,从抽出油中分离得到碱性氮化物。利用傅立叶变换红外光谱仪(FT-IR)和气相色谱-质谱联用仪(GC-MS)分别对富集的碱性氮化物进行官能团检测和定性、定量分析。结果表明:新疆宝明页岩油柴油馏分中的碱性氮化物经溶剂精制和柱色谱等分离方法梯度富集后,碱性氮化物的质量分数由抽出油的12.08%提高到最终产物的69.48%,并在富集分离的产物中鉴定出60种碱性氮化物,其中主要为苯胺类、喹啉类和吡啶类化合物,各占25.85%,23.56%和16.52%。     

微波消解氢化物发生ICP—AES法测定川山紫中痕量硒

建立了微波消解连续氢化物发生ICP AES法测定川山紫中痕量硒的方法 ,系统地研究了微波消解、氢化物发生的最佳条件 ,方法简便快速 ,检出限为 0 .0 0 38μg·ml- 1,RSD为 1.13% (n =10 ,0 .5 4 7μg·g- 1Se) ,样品加标回收率为 99.2 4 %。     

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.