气相色谱法测定染料产品中喹啉的含量

建立了测定染料产品中喹啉含量的气相色谱(外标法)检测方法。用气相色谱对样品中的喹啉及其他有机组分进行分离,用峰面积外标法进行定量。通过气相色谱-质谱联用仪对喹啉和异喹啉进行了定性。喹啉的检出限为10 mg/kg,样品的加标回收率为70%~130%;喹啉检测的相对标准偏差小于2%。结果显示,该方法线性良好,回收率、精密度好,灵敏度高,符合检测要求。     

可见光促进荧光素催化的氧化偶联反应合成苯并咪唑 [2,1-a]并异喹啉衍生物

苯并咪唑[2,1-a]并异喹啉衍生物广泛应用于生物医药、导电材料以及高分子等领域。开发其绿色的合成新方法具有重要的意义。在室温下以N-丙烯酰胺结构为自由基受体，1,3-二氧戊烷为自由基来源，荧光素为催化剂，可见光驱动下经历自由基加成/环化反应历程制备了苯并咪唑[2,1-a]并异喹啉骨架结构。在最优反应条件下，以48%~78%收率合成了11种具有不同取代基团的苯并咪唑[2,1-a]并异喹啉衍生物，采用1H NMR、13C NMR对终产物进行了结构鉴定。     

异喹啉衍生物的合成研究

报道了以异喹啉为起始原料,通过一步合成了关键中间体5-溴异喹啉,进而由5-溴异喹啉合成了5-溴-8-硝基异喹啉、8-氨基异喹啉、8-溴异喹啉等四个异喹啉的衍生物.产物结构经红外和核磁确定.     

高品质异喹啉生产技术研究

文章简要介绍了目前异喹啉分离精制的工艺研究现状,在此基础上,提出了三步静态熔融结晶加一次精馏的生产方法,即把工业异喹啉经过三步熔融结晶提纯后,再通过精馏的手段对异喹啉产品进行提质,其中:静态熔融结晶工艺过程可将异喹啉提纯到≥98%,结晶工艺收率≥85%;而精馏提质所得异喹啉产品表现为无色透明状或白色结晶,水分含量≤0.05%,金属离子含量(包括钠、钾、铁、钙、镁等)均小于3 ppm,精馏工艺收率≥93%。     

UCST型玫瑰红催化剂的制备与催化合成N-苯基四氢异喹啉类化合物

以甲基丙烯酸甲酯（MMA）和甲基丙烯酰氧乙基三甲基氯化铵（DMC）为原料，合成了聚合物P(MMA-DMC)，通过P(MMA-DMC)对玫瑰红（RB）的吸附作用，制得UCST（高临界溶解温度）型RB催化剂〔P(MMA-DMC)-RB〕。测定了聚合物的相对分子质量、UCST温度以及P(MMA-DMC)-RB在溶液中溶解再析出的稳定性，研究了P(MMA-DMC)-RB在催化N-苯基四氢异喹啉衍生物与硝基甲烷反应的催化活性与稳定性。结果表明，DMC含量为0.5%~2%时(DMC含量以MMA物质的量为基准计算)，UCST温度在35~42℃，P(MMA-1%DMC)-RB经过四次溶解-沉淀实验后，回收量仍可达到首次的93%以上；在N-苯基四氢异喹啉衍生物和硝基甲烷的CDC（交叉脱氢偶联反应）反应中，P(MMA-1%DMC)-RB具有较高的催化活性，催化性能与常规玫瑰红RB相当，在反应温度为45℃，白色1W LED光源下反应8h，产物四氢异喹啉衍生物的收率在80%以上，并且该UCST型RB催化剂具有良好的套用性和稳定性，循环套用8次后，四氢异喹啉衍生物的收率从90.2%降为77.9%。     

从煤焦油洗油中提取喹啉和异喹啉的研究

从煤焦油洗油中提取高纯度喹啉和异喹啉，考察了萃取剂及其质量分数、pH值对提取率的影响，得出最佳条件：萃取剂为硫酸氢铵，硫酸氢铵质量分数为20％，pH值0．8～1．0，喹啉和异喹啉的提取率大于75％。     

从喹啉残液中提取工业异喹啉

异喹啉为无色片状结晶,有吸水性,碱性较喹啉强,能与多种溶剂混合,可溶于稀酸,在有机合成工业中,可作为制造医药、农药和气相色谱固定液等的原料。１原料的预处理生产异喹啉的原料是喹啉残液,即浮选剂II。喹啉残液中的异喹啉含量约为３０％,为此,首先应利用喹啉工段的减压蒸馏装置将喹啉残液进行减压蒸馏,制成异喹啉含量＞５０％的异喹啉原料,其组成见表１。２异喹啉的生产工艺从表１可看出,异喹啉原料中各组分的沸点差较大,故可用蒸馏法制取异喹啉。由于异喹啉原料是分批生产的,故采用间歇精馏较为适宜,年产１０t异喹啉的生…     

取代喹啉、异喹啉非水滴定分析方法研究

研究了取代喹啉、异喹啉非水滴定含量分析方法。以高氯酸标准溶液对氨基和溴取代喹啉、异喹啉的含量进行非水滴定测量,用甲醇钠标准溶液对羟基喹啉、异喹啉的含量进行非水滴定测定,方法容易操作,滴定终点清晰,准确可靠,重复性好,氨基、羟基和溴代喹啉、异喹啉RSD(%)分另为0.27～0.93,0.39～0.93和1.05～1.64。并以气相色谱(GC)、液相色谱(HPLC)对其进行了对比研究,3种方法符合性较好。     

硫酸法制备2-甲基喹啉的工艺研究

2-甲基喹啉是重要的有机化工原料,以异喹啉塔釜油为原料,通过硫酸洗涤使2-甲基喹啉成盐析出,析出的盐与Na OH溶液反应,反应后2-甲基喹啉进入到油相中,经过减压精馏,最终得到2-甲基喹啉产品。实验结果表明,通过硫酸法制备2-甲基喹啉最终可得到含量为93.56%的产品。     

异喹啉-5-磺酸合成及反应机理研究

介绍了一种简单实用的合成异喹啉-5-磺酸的方法,以异喹啉为原料通过成盐、磺化两步反应定向合成了异喹啉-5-磺酸,总收率达到了84.6%,超过了以往文献报道。首次尝试通入氯化氢成盐,避免了浓硫酸成盐造成的对原料的脱水碳化,解决了产品色泽不白的问题,且该法工艺简单,后处理易操作。详细讨论了可能的反应机理,为其定向反应提供了理论依据。     

用精馏法从喹啉残油中提取异喹啉

介绍了用精馏法从喹啉残油中提取纯度98％异喹啉的试验研究。     

Interaction of the quinoline bases of coal tar with sulfonic-acid cationites

The equilibrium distribution of quinoline, isoquinoline, and quinaldine between aqueous solutions and KU-2-4 and KU-2-8 sulfonic-acid ionites of polystyrene type (counterparts of Dowex 50 × 4 and 50 × 8 ion-exchange resins) in the form of copper and iron cations is considered. The distribution coefficients of each base between the two phases (KU-2-4 cationate and the solution) are calculated. The distribution coefficients of the quinoline between the Cu²⁺ form of the ionite and the solution differ by a factor of two from those for quinaldine and isoquinoline. Accordingly, the Cu²⁺ form of KU-2-4 cationite is of interest for the development of ligand-sorptional methods of extracting quinoline from its mixture with isoquinoline and quinaldine, so as to expand the resource base for small-scale chemistry on the basis of coke byproducts.     

一种洗油加工工艺及其产品的应用

介绍从煤焦油的洗油中分离吲哚、甲基萘和喹啉、异喹啉等焦油碱的工艺方法, 以及产品在精细化工领域中的应用。     

Charge-Transfer Complexes Between N-Heteroaromatic Bases and their Salts

Acridine, quinoline and isoquinoline are shown to form 1:1 charge transfer complexes with their protonated or methylated positively charged forms. The complexes exhibit characteristic charge-transfer bands, part of which fall in the region where the components of the complex show no light absorption. The association constant K for mixtures containing acridine, quinoline or isoquinoline and their hydrochlorides or methochlorides in methanol-water was derived from changes in intensity of the apparent charge-transfer band with concentration of the free base. For the above mixtures in water, the association constant as well as the heat of complex formation ΔH were derived. The values of K and ΔH for the complexes formed between each of the three bases and their protonated forms are considerably higher than the analogous values for the complex with the methylated form, presumably due to a hydrogen bond between the coupled base molecules.     

喹啉和异喹啉热解机理的密度泛函理论研究

The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry, including eight reaction paths and a common tautomeric intermediate 1-indene imine. It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products (C6H6, HC C C N, C6H5C N and HC CH) to be the same, and also decides the total disappearance rates of the reactants to be the same, for both original reactants quinoline and isoquinoline during the pyrolysis reaction. The results indicate that the intramolecular hydrogen migration is an important reaction step, which often appears in the paths of the pyrolysis mechanism. The activation energies of the rate determining steps are obtained. The calculated results are in good agreement with the experimental results.     

Hydrodenitrogenation of isoquinoline

To determine the formation and reactivity of addition compounds produced during hydrodenitrogenation (HDN), we investigated the HDN of isoquinoline for a sulfided Ni–Mo/Al₂O₃ catalyst operated under a hydrogen pressure of 12 MPa (cold charge) in the temperature range 300–375°C. The reaction products were classified into five groups of compounds:

1. hydrogenated derivatives of isoquinoline (tetrahydroisoquinolines, decahydroisoquinolines, and their isomers);

2. nitrogen-containing ring-opened products (1-amino-2-(2-methylphenyl)ethane and 1-amino-1-(2-ethylphenyl)methane);

3. denitrogenated products (1-ethyl-2-methylbenzene, 1-ethyl-2-methylcyclohexane, and their isomers);

4. addition products (hydrocarbons with molecular weights of 238, 244, and 250 and nitrogen-containing compounds with molecular weights of 249, 251, and 257); and

5. cracked products (toluene, ethylbenzene, dimethylbenzenes, and their hydrogenated derivatives).

Most of the nitrogen-containing addition compounds appear to be substituted on the nitrogen atom. The HDN of isoquinoline was more than 10 times faster than the HDN of quinoline, whereas the hydrogenation of isoquinoline was difficult compared to the hydrogenation of quinoline. The reaction network for the HDN of isoquinoline is also presented.     

Asymmetric hydrogenation of heteroaromatic compounds

Asymmetric hydrogenation of heteroaromatic compounds has emerged as a promising new route to saturated or partially saturated chiral heterocyclic compounds. In this Account, we outline recent advances in asymmetric hydrogenation of heteroaromatic compounds, including indole, quinoline, isoquinoline, furan, and pyridine derivatives, using chiral organometallic catalysts and organocatalysts.     

PY/GC-MS法研究烟碱热裂解产物

用在线热裂解技术(PY)将烟碱于300、600、650、700、750、800和900℃裂解,用气质联用(GC-MS)对其裂解产物进行了定性和半定量分析,结果表明,烟碱可裂解为麦斯明、可替宁、二烯烟碱、吡啶、喹啉、异喹啉、苯和1,7-菲啰啉等20种物质。在600℃以下烟碱只有少量裂解,在800℃时烟碱完全裂解。在800℃和900℃裂解产物大致一样。根据主要的裂解产物和其相对峰面积百分比的变化,对烟碱的裂解机理进行了初步探讨,归纳为8条裂解途径。为烟碱在卷烟燃烧中的分解过程提供了参考。     

吡啶二甲酸的合成及其应用

在含硫酸铜的酸性水溶液中,用氯酸钠作氧化剂,氧化喹啉得到2,3-吡啶二甲酸,产率为56·4%;以硫酸铜为催化剂,用浓硝酸在高温氧化异喹啉得到3,4-吡啶二甲酸,产率为71·4%,并讨论了影响合成的因素。在钼酸铵存在下,采用固相烘焙法,2,3-吡啶二甲酸和3,4-吡啶二甲酸分别与尿素和氯化亚铜作用得到了氮杂铜酞菁。实验发现,以3,4-吡啶二甲酸合成的氮杂铜酞菁在吡啶中具有较大的溶解度,最大吸收波长为673nm。     

生物碱类化合物的研究进展

生物碱作为一类广泛存在于自然界中的碱性含氮有机化合物,数目众多,结构类型复杂。依据化学结构不同可分为异喹啉类、喹啉类、咪唑类、哌啶类、莨菪烷类、吲哚类、咔唑类、海洋多环胍类、萜类、manzamine型生物碱等。文章就部分生物碱类化合物结构研究进展进行综述。