5，11-二乙基吲哚[3，2-b]咔唑的合成及光谱特性

以苯肼为原料,与1,4-环己二酮反应,制得环己胺-1,4-二酮一二苯腙,再在硫酸、醋酸强酸性环境下闭环制得吲哚[3,2-b]咔唑,经N-烷基化反应制得乙基取代基的吲哚[3,2-b]咔唑衍生物．本文合成方法使其产率由参考文献的64％提升到80％,其结构经’HNMR表征,并初步研究了该化合物的光谱性质．     

1-苯基氨基脲的合成研究

以盐酸苯肼和尿素为原料,用水作溶剂,在浓硫酸催化下合成1-苯基氨基脲。研究了原料摩尔比、浓硫酸和溶剂量、反应时间、催化剂用量对产品质量和收率的影响,确定了最佳工艺反应条件:n(盐酸苯肼)∶n(尿素)∶n(浓硫酸)∶V(水)=1∶1.2∶0.2∶500 mL,盐酸苯肼与催化剂的比例为1∶10(mol/g),反应时间10 h。放大实验的收率达到92%以上。     

Phenylhydrazine rearrangement revisited over modified ZSM-5 catalysts

The rearrangement of phenylhydrazine too- andp-phenylenediamines was carried out over ZSM-5 and its modified catalysts. Sm and V showed the promoting effect. In presence of ammonia flow Ga and Cr modified ZSM-5 catalysts gave good yields ofo- andp-phenylenediamines. The better temperature and WHSV for this reaction are found to be 400°C and 0.25 h^–1 respectively. The SiO₂/Al₂O₃ catalyst showed very low ortho-para selectivity when compared with zeolite catalysts.IICT Communication No. 3372.     

Determination of genotoxic phenylhydrazine agaritine in mushrooms using liquid chromatography-electrospray ionization tandem mass spectrometry

A new method with good sensitivity and specificity for detecting and quantifying genotoxic hydrazines, agaritine and 4-(hydroxymethyl)phenylhydrazine (HMPH), was developed using liquid chromatography-electrospray tandem mass spectrometry (MS). Synthetic agaritine and HMPH were structurally assigned by ¹H-, ¹³C- and two-dimensional nuclear magnetic resonance (NMR) analysis (HMBC and HMQC), high-resolution fast-atom bombardment (HR-FAB) MS and time of flight (TOF) MS. The polar molecule agaritine was separated on an ODS column using 0.01% AcOH-MeOH (99:1, v/v) as an eluent with a simple solid-phase extraction cleanup. There were no interference peaks for any of the mushrooms. Agaricus spp. contained 1247 and 2017 µg g^-1 agaritine. Other species of mushroom had no agaritine. Recoveries of agaritine from spiked mushroom samples were 60.3-114%. Intra-day precision values were 5.5 and 4.2%, and the inter-day precision values were acceptable (15.0 and 23.0%), as agaritine is unstable. The limit of quantification was 0.003 µg g^-1. Even a trace amount of agaritine in mushrooms can, therefore, be determined using this method. We also directly analysed HMPH, an active free hydrazine form of genotoxic agaritine, and obtained direct evidence of its absence from mushrooms. A precursor ion scan confirmed that agaritine derivatives, which could exert similar toxicity, were absent. The results indicate that this specific and sensitive analytical method for detecting and quantifying agaritine and its derivatives could help evaluate the risk of mushroom hydrazines to humans.     

高纯度苯肼的合成

通过对苯肼的合成工艺进行改进 ,高收率地合成了高纯度苯肼 ,产品纯度为 99% (GC)以上 ,联苯胺浓度小于 0 0 0 1 5 % (HPLC) ,苯胺小于 0 1 % (HPLC) ,苯酚小于 0 0 5 % (HPLC) ,总收率由 70 %提高到 75 %。     

高效液相色谱法测定工业废水中盐酸苯肼

通过实验建立了工业废水中盐酸苯肼的高效液相色谱分析方法。色谱条件为:Kromasil-C18(150 mm×4.6 mm,5μm)色谱柱,流速1 mL/min,柱温30℃,进样体积10μL,流动相为V(甲醇)∶V(8 mmol/L KH2PO4+4 mmol/LK2HPO4)=35∶65,测定波长235 nm。测定结果表明,线性范围为0.1～100 mg/L,平均加标回收率为98.2%,相对标准偏差为1.06%。该方法操作简单,分析快速、准确。     

盐酸苯肼废水的治理研究

盐酸苯肼是生产农药、医药等的中间体，在其生产过程中产生的废水成分复杂，毒性大，采用树脂吸附和Fenton氧化法综合处理后其可生化性大大提高。     

吡唑嘌呤席夫碱的合成

以苯肼、盐酸氨基脲为起始物,经缩合、Vilsmeier-Haak 试剂(DMF/POCl_3)环化、再缩合消除合成了2种吡唑嘌呤席夫碱:1,2-二甲基-2-{2-{6-氯-2[(3-苯基-1H-吡唑-4基)亚甲氨基]-9H-嘌呤-9-基}乙基}丙二酸和二甲基-2-{2-{6-氯-2[(5-氯-3甲基-1-苯基-1H-吡唑-4基)亚甲氨基]-9H-嘌呤-9-基}乙基}丙二酸。其中吡唑酮环化反应的最佳反应条件为:反应温度70℃,反应时间5 h,收率在80%以上。目标产物总收率分别为79.7%和71.8%,通过熔点测定、红外光谱、核磁共振光谱对目标物化学结构进行了表征。     

2-(3,4-二氯苯基)-2,4-二氢-5-甲基-3H-吡唑啉-3-酮的合成及表征

本文以3,4-二氯苯胺为原科合成了3,4-二氯苯肼盐酸盐,再与乙酰乙酸乙酯环化,合成2-(3,4-二氯苯基)-2,4-二氢-5-甲基-3H-吡唑啉-3-酮.用红外光谱、熔点仪、高效液相色谱和核磁共振对产品进行了表征和检测.考察了盐酸用量、还原剂、反应温度、溶剂和后处理对转化率和纯度的影响.结果表明:选用氯化亚锡作还原剂,在低温和盐酸过量下有利于提高3,4-二氯苯肼盐酸盐的收率.选用V(乙醇)∶V(水)=6∶1为溶剂,75℃下反应4小时,以碳酸钠调节pH =7,2-(3,4-二氯苯基)-2,4-二氢-5-甲基-3H-吡唑啉-3-酮转化率为82.6％,熔点163～164℃,纯度述96％.     

苯肼下游产品的合成及应用

介绍了苯肼作为一种重要的有机合成中间体,与羰基化合物、烯醇化合物发生成环反应,合成吲哚、吲唑、吡唑、吡唑啉、嘧啶、哒嗪、色胺及其衍生物,对反应发生的条件及苯肼的上述衍生物的应用做了简单概述。