一种新型马来酰亚胺的合成研究

研究了Ａｃ２Ｏ／Ｅｔ３Ｎ／ＮｉＳＯ４三元催化体系催化下Ｎ－己基马来酰亚胺的合成，考察了催化剂用量，反应温度，原料配比和反应时间对反应产率的影响，确定了最佳反应条件，所得Ｎ－己基马来酰亚胺产率达８４％，与传统酸催化法相比，该法具有反应条件温和，产率高等优点。     

一种新型马来酰亚胺的合成研究

研究了Ａｃ２Ｏ／Ｅｔ３Ｎ／ＮｉＳＯ４三元催化体系催化下Ｎ－己基马来酰亚胺的合成,考察了催化剂用量,反应温度,原料配比和反应时间对反应产率的影响,确定了最佳反应条件,所得Ｎ－己基马来酰亚胺产率达８４％,与传统酸催化法相比,该法具有反应条件温和,产率高等优点     

N—取代马来酰亚胺在开发新材料中的应用

本文着重介绍了Ｎ－取代马来酰亚胺与异丁烯交替共聚合成新型透明材料、用Ｎ－取代马来酰亚胺改性有玻璃、聚苯乙烯、聚酰亚胺树脂、ＡＢＳ树脂，不饱和聚酯等的研究情况，Ｎ－取代马来酰亚胺可以显著提高上述材料的耐热性，又保持它们优异的力学性能和工艺性。     

某些四乙酸四氮杂环烷烃La^3＋,Gd^3＋络合物的合成

在ＫＯＨ存在下,１,４,７,１０－四氮杂环十二烷与溴乙酸发生Ｎ－羧甲基化反应,得Ｎ,Ｎ’,Ｎ”,Ｎ－四乙酸－１,４,７,１０－四氮杂环十二烷（ＤＯＴＡ,１）,产率８８．１％。在Ｋ２ＣＯ３作用下,１,４,８,１１－四氮杂环＋四烷与溴乙酸苄酯进行反应,得Ｎ－乙酸苄酯衍生物,经Ｐｄ／Ｃ催化氢解生成Ｎ,Ｎ’,Ｎ”,Ｎ－四乙酸－１,４,８,１１－四氮杂环十四烷（ＴＥＴＡ,３）,产率５６．０％。ＤＯＴＡ和ＴＥＴＡ分别与ＬａＣｌ３和ＧｄＣｌ３形成络合物,产率为６４．１％～７４．６％。     

固体超强酸T：O_2／SO_4~(2-)催化合成水杨酸乙酯

研究了以固体超强酸Ｔ：Ｏ＿２／ＳＯ＿４￣（２－）为催化剂，水杨酸和乙醇为原料合成水杨酸乙酯，并考察了醇酸比、催化剂用量、反应时间、反应温度对酯产率的影响。结果表明，在水杨酸用量为０．１ｍｏｌ的情况下用固体超强酸Ｔ：Ｏ＿２／ＳＯ＿４￣（２－）为催化剂，催化剂用量为１．０克，乙醇与水杨酸的摩尔比为３：１或４：１，反应时间为５小时，反应温度９５一１００℃是最适宜的反应条件，酯产率达８９％。并且同硫酸相比，固体超强酸Ｔ：Ｏ＿２／ＳＯ＿４￣（２－）有许多优点：产品容易从催化剂中分离，后处理方便，减少废液，降低动力消耗，具有很好的经济性。     

N—苯基马来酰亚胺的合成

以顺丁烯二酸酐和苯胺为原料，选择二步法合成了Ｎ－苯基马来酰亚胺，无需使用ＤＭＦ溶剂。用正交法优化了工艺条件，产品收率为９２％，质量分数为９７％，溶点８６．８￣８８．０℃。应用试验表明Ｎ－苯基马来酰亚胺是ＰＶＣ塑料有效的热稳定剂。     

1—溴—4—溴甲基苯的简易合成及应用

以 对溴甲苯为原料，Ｎ－溴代丁二酰亚胺为溴化剂，利用光引发的自由基反应合成了１－溴－４－溴甲基苯，产率可达８０％，并利用它制得了一个新的有机合金属前体。     

1－溴－4－溴甲基苯的简易合成及应用

以对溴甲苯为原料，Ｎ－溴代丁二酰亚胺为溴化剂，利用光引发的自由基反应合成了１－溴－４－溴甲基苯，产率可达８０％，并利用它制得了一个新的有机金属前体。     

合成N—丁基马来酰亚胺的新方法

研究了新型的Ａｃ２Ｏ／Ｅｔ３Ｎ／ＮｉＳＯ４三元催化体系催化下Ｎ－丁基马来酰亚胺的合成。考察了催化剂用量,反应温度,原料配比及反应时间对反应收率的影响。确定了优惠反应条件。收率达８８％以上。与传统酸催化法相比,具有反应条件温度,收率高等优点。     

邻苯二甲酰亚胺在K2CO3—Al2O3负载型碱试剂作用下的苄基化反应

邻苯二甲酰亚胺在Ｋ＿２ＣＯ＿３－Ａｌ＿２Ｏ＿３负载型碱试剂作用下的苄基化反应陆文兴，颜朝国（扬州大学师范学院化学化工系，扬州２２５００２）Ｎ－烃基邻苯二甲酰亚胺类化合物是合成脂肪族伯胺和－氨基酸的重要中间体。Ｎ－烃基化反应可使用催化剂或在强碱条件下进...     

羧酸硒醚、二硒醚及相应硒多糖的合成

用NaBH4还原硒粉得Se2-或-SeSe-,然后在碱性水溶液中与氯乙酸、3-氯丙酸和对-溴甲基苯甲酸在室温下反应,制得相应的羧酸硒醚,收率分别为51.9%、62.6%和58.6%,以及丙酸和对甲基苯甲酸二硒醚,收率67.8%和72.1%。用乙酸硒醚分别与邻氨基苯甲酸和水杨酸反应引入其他基团,收率73.6%和69.8%。最后这些合成的化合物通过形成酰氯与麒麟菜多糖中的羟基醚化得到含硒醚或二硒醚结构的新型硒多糖,收率40%~60%。     

Synthesis and Physical Properties of Symmetrical and Non-symmetrical Triacylglycerols Containing Two Palmitic Fatty Acids

A series of symmetrical (ABA) and non-symmetrical (AAB) triacylglycerol (TAG) isomers containing “A,” palmitic (P; 16:0) acid, and “B,” either oleic (O; 9c-18:1), elaidic (E; 9t-18:1), linoleic (L; 9c,12c-18:2) or linolenic (Ln; 9c,12c,15c-18:3) fatty acids were synthesized by esterification of the thermodynamically more-stable 1,3-di- or 1(3)-monoacylglycerols [1,3-DAG or 1(3)-MAG], respectively. 1,3-dipalmitoylglycerol (1,3P-DAG) was esterified with O, L or Ln acid to prepare the symmetrical TAG isomers POP, PLP and PLnP, while the O- E-, L- and Ln-1(3)MAG precursors, synthesized or obtained commercially, were esterified with P acid to prepare the non-symmetrical TAG isomers OPP, EPP, LPP and LnPP, respectively. The drop point(s), solid fat content and melting point values of the synthesized TAG were determined. The 1,3-dipalmitoylglycerol (1,3P-DAG) and 1(3)P-MAG precursors were prepared, in multi-gram quantities, by partial glycerolysis (glycerol/p-toluenesulfonic acid) of tripalmitin. After fractionation by silica gel chromatography, the 1(3)P-MAG and 1,3P-DAG isomers (ca. 80% of total MAG or DAG) were purified (>98%) by crystallization from acetone [silver ion-HPLC was utilized to determine the structural purities of the DAG (or MAG) precursors, and the synthesized TAG]. Esterification of the appropriate, thermodynamically more-stable MAG or DAG precursors was found to be a very versatile method for synthesis (in 80–90% yields) of multi-gram (3–5 g) quantities of symmetrical and non-symmetrical TAG isomers, in chemical and structural purities of >96 and 97–99%, respectively. The 1- and 3- positions on the glycerol backbone of the MAG, DAG and TAG molecules are assumed to be equivalent. Mention of trade names or commercial products in this (publication) is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the US Department of Agriculture.     

两种磺酰胺类染料中间体的合成与表征

合成了两种磺酰胺类染料中间体N (4 氨基苯磺酰基) N′ (3 氨基 4 甲氧基苯磺酰基) 1,4 苯二胺(Ⅴ)和N (4 氨基苯磺酰基) N′ (4 氨基 3 甲基苯磺酰基) 1,4 苯二胺(Ⅸ)。合成步骤如下:(1)乙酰苯胺和氯磺酸反应所得的对乙酰氨基苯磺酰氯与对苯二胺一步胺化得4 氨基 4′ 乙酰氨基苯磺酰苯胺(Ⅰ);(2)邻氨基苯甲醚和邻甲苯胺的氨基保护后与氯磺酸反应得3 乙酰氨基 4 甲氧基 苯磺酰氯(Ⅲ)和3 甲基 4 乙酰氨基 苯磺酰氯(Ⅶ);(3)Ⅰ分别与Ⅲ、Ⅶ在NaOH溶液中进行第二步胺化,所得缩合物水解得产品Ⅴ、Ⅸ。产品均经红外、质谱、核磁、元素分析表征确定了结构。第二步胺化反应优化条件均为:n(Ⅰ)∶n(Ⅲ或Ⅶ)=1∶1 5,反应温度70℃,反应时间4 5h,溶剂为w(NaOH)=3%,n(NaOH)∶n(Ⅰ)=3∶1的溶液,产率分别为91 66%、93 22%。     

4种PEPA衍生物阻燃剂的合成

1-氧基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷(PEPA)与三氯氧磷分别以摩尔比2∶1和3∶1反应,得到二(2,6,7-三氧杂-1-氧基磷杂双环[2.2.2]辛烷-4-亚甲基)磷酰氯(中间体Ⅰ)和三(2,6,7-三氧杂-1-氧基磷杂双环[2.2.2]辛烷-4-亚甲基)磷酸酯(d),产率分别为84.7%和80%。中间体Ⅰ再分别与三溴苯酚、五溴苄基溴及三聚氰胺反应得到另外3种具有笼状结构的磷酸酯化合物(a~c),收率依次为70%,73.5%,81%。用红外、核磁、元素分析等手段对a~d 4种化合物进行了表征,对其合成工艺进行了探讨。热失重数据表明,目标产物均有较好的成炭性和热稳定性,化合物a~d的初始热分解温度分别为285,325,320,337,500℃时残炭质量分数分别达38.4%,26.3%,56.5%,50.0%。     

间甲基苯腈的硝化及产物的结构表征

以浓硝酸为硝化剂硝化间甲基苯腈得到3种硝基间甲基苯腈的异构体。在n(间甲基苯腈)∶n(发烟硝酸)=1∶10,反应时间2 h,反应温度18~20℃的条件下,冰浴中将浓硝酸缓慢滴加到间甲基苯腈中,得3种硝基间甲基苯腈异构体,粗品总收率92%。经柱层析和重结晶,从粗产物中分离出3种纯异构体,分别为3-甲基-4-硝基苯腈、3-甲基-6-硝基苯腈和3-甲基-2-硝基苯腈,以间甲基苯腈计,收率分别为43%、37%和12%。应用核磁共振、红外和气质联用技术,表征了3种纯异构体的结构,对硝化反应的位置选择性进行了初步分析。     

甲烷磺酸的合成研究

先用硫氰化钾（ＫＳＣＮ）和硫酸二甲酯（ＣＨ３）２ＳＯ４合成硫氰酸甲酯（ＣＨ３ＳＣＮ），再由硝酸溶液将其氧化为甲烷磺酸（ＣＨ３ＳＯ３Ｈ），两步的收率分别可达６５％和８３．２％，并采用了两种不同的分离和纯化产品的方法。     

Triacylglycerol structure of an african peanut oil

Triacylglycerols were isolated from an African peanut oil, then fractionated by unsaturation into classes, and the triacylglycerol structure was determined on these classes using pancreatic lipase hydrolysis. Fatty acid analysis of monoacylglycerols and, in some cases, of 1 or 2 classes of diacylglycerols, allowed the proportions of 84 isomers to be calculated. The oil had a high oleic acid content (60.3%) and contained nearly 25% of trioleoylglycerol, the major triacylglycerol. The 4 most abundant isomers together represented more than one-half of the total triacylglycerols. In 30 isomers, the 2-position was occupied by linoleic acid, and in 39 isomers, by oleic acid. The very long-chain saturated fatty acids (20:0, 22:0, 24:0) that formed 5.1% of the fatty acid content of the oil, were not found in the 2-position. In most cases, each was associated with 2 molecules of an unsaturated fatty acid. The placement of fatty acids, respectively, at the 1,3-position and the 2-position was relatively close to a l,3-random-2-random distribution, except for trioleoylglycerol (24.7% instead of 21.7% by the random hypothe-sis). To whom requests should be sent.     

Effect of surfactants on the soil desorption of hexachlorocyclohexane (HCH) isomers and their anaerobic biodegradation

The extensive utilization of hydrophobic organic compounds (HOCs) such as pesticides generates high environmental pollution levels. Due to their hydrophobicity, this type of compound tends to accumulate in soil organic matter and, thus, soil desorption limits their availability for microbial degradation. The use of surfactants may increase the pollutant's desorption from the soil. One of the pesticides with strong sorption characteristics is hexachlorocyclohexane (HCH), a mixture of isomers: α‐, β‐, γ‐ and δ‐HCH. In this work, we evaluated the use of three surfactants, Triton X100, Tween 80 and sodium dodecyl sulfate (SDS), on the HCH desorption from a sandy loam soil. The effects of the addition of these surfactants on anaerobic biodegradation were studied. To attain this purpose, different assays were performed to evaluate both effects. Triton X100 exerted the best desorption of HCH isomers, followed by Tween 80, whereas SDS caused no significant desorption of the isomers. Triton had a strong inhibitory effect on the HCH biodegradation, while Tween 80 did not decrease the degradation rates of the different isomers. Moreover, the degradation rates of β‐ and δ‐HCH were significantly enhanced (around 10%). On the other hand, detrimental effects on the biodegradation rates and yields were due to the ageing of the soil, depending on the period of exposure of the soil to the pollutant. Copyright © 2005 Society of Chemical Industry     

烷基双胍硫酸盐的合成及iNOS抑制活性的测定

二腈二胺在60℃下与硫酸铜反应1 5h得配合物(Ⅰ);然后分2次加入烷基胺(间隔时间为1h)于70℃(对Ⅱa、Ⅱb)或80℃(对Ⅱc～Ⅱe)下反应10h合成了5种烷基双胍硫酸盐(Ⅱa～Ⅱe),Ⅱa、Ⅱb、Ⅱc、Ⅱd、Ⅱe的收率分别为83 75%、84 21%、88 45%、87 62%、86 51%,以元素分析、IR、NMR、UV对化合物Ⅱa～Ⅱe的结构进行了确认。对化合物Ⅱa～Ⅱe及配合物(Ⅰ)的诱生型一氧化氮合酶(iNOS)抑制活性进行了测定,结果表明,化合物Ⅱb及配合物(Ⅰ)有iNOS抑制活性,其中配合物(Ⅰ)的活性强于对照物氨基胍。     

β-氨基酸乙酯盐酸盐的合成与表征

以三种β-苯丙氨酸、二氯亚砜、乙醇为原料分别合成了β-苯丙氨酸乙酯盐酸盐、2F-β-苯丙氨酸乙酯盐酸盐和3F-β-苯丙氨酸乙酯盐酸盐三种稳定的β-氨基酸乙酯盐酸盐,并通过熔点、核磁和质谱对化合物的结构进行了表征。该合成方法操作简单、反应条件温和,收率均在85%以上。