(E)-叔丁基(1-碘基-1-戊烯基-3-氧代)二甲基硅烷的合成

以(R)苯甲基环氧丙醇((S)环氧丙醇苄基化作用得到)为原料,经格氏反应、TBS羟基保护、脱苄基、缩合、碘仿反应,其中,考察了格氏反应的萃灭方法,萃取溶剂的选择:饱和氯化氨溶液萃灭,二乙醚作为萃取溶剂。也考察了TBS羟基保护反应中的溶剂筛选:采用二氯甲烷作为溶剂,产物收率较高。同时讨论了超低温缩合反应体系中,氮气保护是体系确保收率的关键控制点,最后分析合成化合物f中影响收率关键点:催化剂的用量和滴加化合物e的四氢呋喃溶液温度(2℃)。经过以上合成步骤,得到目标产物,总收率为28.25%,产物结构经过1H NMR确证,合成路线尚未见文献报道。     

6-(4-苯磺酰基-3-甲基-2-丁烯)-基-2,3-二甲氧基-5-甲基氢醌双苄醚的合成

以异戊二烯为原料,经与苯磺酰氯加成、水解乙酰化、皂化3步反应,制得末端羟基取代的异戊二烯短侧链——(E)-1-苯磺酰基-2-甲基-4-羟基-2-丁烯(简称产物A),并用乙酸乙酯-乙醚混合溶剂对产物A进行提纯精制。以还原型辅酶Q0(氢醌)为母环,杂多酸为催化剂,与产物A进行偶联反应,然后采用溴化苄对母环羟基进行保护,用乙醚-异丙醚的混合溶剂进行提纯精制,选择性结晶得到了侧链延长法合成辅酶Q10的关键中间体辅酶Q1前体,即6-(4-苯磺酰基-3-甲基-2-丁烯)-基-2,3-二甲氧基-5-甲基氢醌双苄醚(简称产物B)。探讨了各主要影响因素对合成反应过程及结果的影响,目标产物B收率达75%(以产物A为基准)。产物A与目标产物B经测熔点、1H NMR分析和FTIR分析鉴定,确证其为(E)-异构体。     

4-羟基吡啶合成研究

以4-氨基吡啶为原料,在适量的15%(质量分数)硫酸溶液中,采用过量的10%(质量分数)的亚硝酸钠为重氮化剂,在30～50°C左右进行重氮化反应,重氮液在NaOH溶液中水解后合成4-羟基吡啶,采用连续逆流萃取得到提纯产物,产物的收率可达93%左右。     

9,10-二羟基环十六内酯的合成

紫胶桐酸是一种具有生物活性的长链羟基烷酸,可用于大环内酯的合成。以紫胶桐酸多羟基作为起始原料,利用高度稀释的合成策略,通过缩醛选择性保护邻二醇、直链前体内酯化环合及酸催化环缩醛脱保护三步反应制备得到了目标产物9,10-二羟基-环十六内酯,总收率为31%,所得产物经红外光谱(IR)、核磁共振氢谱和碳谱(1 H NMR和13C NMR)、电喷雾质谱(ESI-MS)表征得以证实。实验均在室温下进行,反应条件温和,简洁有效。     

炔草酯的合成工艺研究

研究了以R-(+)-2-(4-羟基苯氧基)丙酸、氯丙炔、2,3-二氟-5-氯吡啶为原料,经由R-(+)-2-(4-羟基苯氧基)丙酸炔丙酯制备炔草酯的合成工艺,并讨论了溶剂、反应时间、反应温度对合成目标产物的影响。结果表明,以DMF为溶剂,碳酸钾为缚酸剂,在80℃左右条件下,R-(+)-2-(4-羟基苯氧基)丙酸与氯丙炔反应6 h,再升温到95℃左右,滴加2,3-二氟-5-氯吡啶反应10 h,过滤、重结晶得到炔草酯,收率达到89%,光学纯度为99%。     

聚乙烯亚胺-松香改性聚羟基酸酯类超分散剂的研发

以松香和12-羟基月桂酸为原料合成溶剂化部分。12-羟基月桂酸在160℃-180℃时用二甲苯为溶剂,在催化剂和氮气保护下反应18小时,生成N=6聚羟基酸酯链。树脂酸与聚羟基酸酯的酯化反应温度为200℃～205℃,氧化二丁基锡作催化剂生成松香改性溶剂化链;再与高分支聚乙烯亚胺(分子量1200)反应合成标题化合物。此分散剂应用于高固体颜料浓缩物(颜料含量40%-60%)在有机溶剂中的分散取得了很好的效果。     

碳基固体酸催化合成月桂醇聚氧乙烯醚(7)异辛基磺基琥珀酸混合双酯钠

采用碳基固体酸为酯化反应催化剂,合成了月桂醇聚氧乙烯醚(7)异辛基磺基琥珀酸混合双酯钠,对各步反应进行考察,得到最佳工艺条件为:单酯化反应:n(顺酐)∶n(聚醚7)=1.10∶1.00,ω(碳基固体酸)=1%(以顺酐质量计),反应温度130℃,反应时间2.5 h,在此条件下得到产率为98.16%的单酯化产物;双酯化反应:n(顺酐)∶n(异辛醇)=1.00∶2.00,反应温度200℃,反应时间5.0 h,在此条件下得到产率为93.94%的双酯化产物。测定了产物的表面性能和应用性能,并与对甲苯磺酸作催化剂进行了比较。结果表明:碳基固体酸做催化剂时异辛醇用量少了一半;产物性能一致。     

高选择性合成羟基对苯二甲酸单酯的反应规律及其应用

为满足羟基有序改性高聚物的需要,研究了制备AB型新单体所需关键中间体--羟基对苯二甲酸单甲酯的合成方法。探讨了不同位置酯化和双酯单水解的理论和反应规律,建立了一种通用于非对称取代对苯二甲酸单酯的合成和分离纯化技术。结果表明:以羟基对苯二甲酸(HTA)为起始原料,先经氯化亚砜作用下的甲醇双酯化,再经碱性水溶液中的单水解反应,高选择性地合成了2-羟基-4-羧基苯甲酸甲酯(α-MHT),总收率76%以上;而HTA硫酸催化甲醇直接单酯化则制得3-羟基-4-羧基苯甲酸甲酯(β-MHT),收率近70%。 同时在2,6-二羟基对苯二甲酸(DHTA)单酯化合物α-单甲酯(α-MDHT)和β-单甲酯(β-MDHT)的合成中得到应用。     

均匀沉淀法制备锡酸锌与锡酸锌包覆纳米碳酸钙的研究

以均匀沉淀法制备了羟基锡酸锌和羟基锡酸锌包覆纳米碳酸钙,利用超声分散和共沸蒸馏对所得产物处理后,经高温煅烧得锡酸锌包覆纳米碳酸钙粉体.采用XRD,TG-DTA对羟基锡酸锌及羟基锡酸锌包覆纳米碳酸钙的煅烧产物进行分析,确定合成锡酸锌和锡酸锌包覆纳米碳酸钙的最佳煅烧温度为500 ℃,最佳煅烧时间为3 h.X射线光电子能谱(XPS)分析表明,锡酸锌已包覆在纳米碳酸钙表面,透射电子显微镜(TEM)结果表明,锡酸锌包覆纳米碳酸钙的粒径在40～60 nm.     

聚醚-砜单体4,4’-双(4-羟基苯磺酰)联苯的合成工艺研究

4,4’-双(4-氯苯磺酰)联苯和4,4’-双(4-羟基苯磺酰)联苯是聚醚-砜等重要的单体。以四氯化碳为溶剂,氯苯用氯磺酸磺化、氯化得到对氯苯磺酰氯,在无水氯化铁的催化下,对氯苯磺酰氯与联苯反应得到4,4’-双(4-氯苯磺酰)联苯,然后在氢氧化钠溶液中水解得到4,4’-双(4-羟基苯磺酰)联苯。总收率为55.6%。     

我国脂肪酸的生产和应用

简要介绍脂肪酸的分类、原料来源、生产工艺、品种以及用途。并对我国脂肪酸的生产现状进行了分析。重点介绍了脂肪酸在我国橡胶工业中、塑料助剂等领域的应用,脂肪酸甲酯作为表面活性剂在不同领域的广泛应用,最后还简述了癸二酸和改性醇酸树脂应用。     

酸液体系的研究现状分析和现场应用

酸化解堵与压裂改造相比,它具有施工相对简单和成本相对较低等特点,所以酸化解堵是一项各油田广泛使用的油气田增产技术。酸化解堵技术已有将近100历史,现已研制出具有不同特点的酸液体系,如乳化酸、泡沫酸、固体酸、多氢酸等,基本能满足复杂地质条件对酸液的要求。     

油酸的精制研究

油酸酰胺是一种很好的塑料添加剂 ,可用作塑料加工成型时的脱膜剂、润滑剂。油酸的原料来源很广 ,牛油、羊油、猪油等动物油油脂以及大豆油、花生油、棕榈油等植物油脂中都含有大量的油酸。由于油酸的来源和生产方法多种多样 ,因此其所含的脂肪酸种类及含量都不尽相同。除油酸外 ,还有亚油酸、亚麻酸等高不饱和脂肪酸。针对油酸中因含有大量的多不饱和组分如亚油酸、亚麻酸而容易产生氧化泛黄的问题 ,采取了尿素络合法对原料油酸进行精制 ,以减少原料中亚油酸、亚麻酸组分的含量。经气相色谱验证 ,产品达到了应用指标 ,提高了产品的抗氧性。     

The Growth‐Inhibiting Effects of Beef Fatty Acids on MCF‐7 Cells Are Influenced Mostly by the Depot Location and Inconsistently by the Biohydrogenation Intermediate Content

Biohydrogenation intermediates (BHI) including conjugated linoleic acid (CLA) isomers are formed during ruminal biohydrogenation of polyunsaturated fatty acids (PUFA) in ruminants. Although many studies have examined the anticarcinogenic effects of CLA, few studies have reported the anticarcinogenic properties of BHI in their natural form found in dairy and beef fats. The present study compared the growth‐inhibitory effects of fatty acids from beef perirenal fat (PRF) or subcutaneous fat (SCF) with low or high levels of BHI in MCF‐7 human breast cancer cells. Cells were exposed for 72 h to media containing increasing doses (50 to 400 μM) of different beef fat treatments. Fatty‐acid analysis showed that BHI were readily incorporated into cell phospholipids (PL) in a treatment‐dependent manner, but higher BHI in PL did not consistently inhibit growth. Culturing with low‐BHI PRF or high‐BHI PRF did not lead to growth inhibition, but low‐BHI SCF inhibited growth, and inhibition was further increased by high‐BHI SCF. Other classes of fatty acids may, therefore, be interacting with BHI resulting in differential effects on growth inhibition in human breast cancer cells.     

磷钼杂多酸的合成研究

介绍了磷钼杂多酸的合成。通过正交试验探讨了反应物料量比、三氧化钼浓度、反应温度和反应时间对产物产率的影响。结果表明,最适宜的反应条件为:反应物量比n(三氧化钼)∶n(磷酸)=12∶1.0、反应温度t=70℃、反应时间7 h、三氧化钼与水的质量比1∶8。经红外光谱分析及熔点测定确定所得产品为磷钼杂多酸化合物。并以磷钼杂多酸取代硫酸作催化剂制备乙酸乙醋来研究其催化活性,并与硫酸做催化剂进行对比实验收率为70.75%,超过硫酸催化剂水平。     

Quality of Sunflower Oil Obtained in the Main Producing Region of Brazil: Adherence to the Codex Alimentarius

The objective of this work was to evaluate the quality of the oil extracted from sunflower achenes grown in Campo Novo de Parecis, the main producing region of Brazil, to optimize its use by the processing and food industries. In addition, the fatty acid profiles of the oil were checked for their adherence to the CODEX STAN 210–1999. Traditional and high-oleic genotypes were grown between 2014 and 2017 during trials with a randomized complete block experimental design with four replications. The contents of oleic, linoleic, palmitic, and stearic acids were determined using gas chromatography. The fatty acid profiles of traditional genotypes were observed to be outside the ranges established by the CODEX, with an oleic acid content above 39.4% and linoleic, palmitic, and stearic acid values lower than 48.3%, 2.7%, and 5.0%, respectively, as well as high-oleic sunflower oil with a stearic acid content of less than 2.6%. The availability of this information can, on the one hand, positively impact industries and encourage the use of better quality raw materials that are more technologically and nutritionally adequate. On the other hand, the commercialization of sunflower oil with a fatty acid profile outside the ranges established by CODEX can be difficult, because the contents are out of specification due to the climatic conditions in the cropping region.     

Fatty Acid Profiles of Oil Obtained from Mid-Oleic Sunflowers Grown in Tropical Region

This study aimed to verify whether the fatty acid profiles of mid-oleic genotypes grown in the tropical region of Brazil fit the Codex Alimentarius and to examine the possibility of using traditional inbred lines to produce high-oleic hybrids. For this purpose, we assessed the fatty acid profile of six mid-oleic hybrids grown in environments with different minimum temperatures during oil formation in the achenes. The tests were conducted between 2015 and 2017 in an experimentally randomized complete block design with four replications. The oleic, linoleic, palmitic, and stearic acid contents were determined using gas chromatography. The mid-oleic hybrids presented varying levels of fatty acids, with oleic acid ranging between 43.6% and 84.6%, linoleic acid between 8.5% and 45.6%, palmitic acid between 3.9% and 5.7%, and stearic acid between 2.2% and 6.2%. Some of the fatty acid values were outside the ranges established by the CODEX STAN 210-1999 and were characteristic of high-oleic type sunflowers. This finding shows that we can take advantage of the potential of combining traditional inbred lines to produce high-oleic hybrids for faster and more economical breeding programs in these environments.     

Fatty Acid Profiles in Sunflower Grains During Storage in Different Environments

This study aimed to evaluate the fatty acid profiles of sunflower oil extracted from hybrid grains produced and stored in different environments. The trials were conducted in Teresina (Piauí), Vilhena (Rondônia), and Jaguariúna (São Paulo) in randomized complete block design with 4 replicates. After harvesting, grains from 1 high oleic and 3 traditional hybrids were packed in kraft paper bags and stored in a covered shed and in a cold chamber up to 12 months. The fatty acid profiles were determined by gas chromatography after 0, 4, 8, and 12 months of storage. Analyses of variance were conducted in a split‐plot design, with hybrids being considered as whole plots and storage times as subplots. Tukey's test was performed to compare hybrids and regression analyses for storage times. The initial fatty acid profile of the grains of the same hybrid varied depending on the production location. The grain storage of high oleic and traditional sunflower hybrids during 12 months in covered shed and in cold chamber resulted in little changes in oil fatty acid profiles, regardless of the initial contents. These changes occurred only for linoleic and palmitic acids.     

质子酸催化合成α-氯代十二酸工艺研究

采用廉价的浓硫酸为催化剂,氧气为自由基捕集剂,以十二酸为原料,经氯化合成α-氯代十二酸。系统考察了反应温度、催化剂用量、氯气流量、氧氯比、反应时间等因素的影响,得到最佳工艺条件:十二酸20 g,在反应温度135℃、催化剂10%、氯气流量50 mL·min-1、vO2/vCl2=1∶2、反应时间3 h,可实现十二酸基本完全转化,目标产物α-氯代十二酸选择性达到94.5%。     

草酸作助剂磷钨酸催化H2O2氧化环己醇合成己二酸

在无有机溶剂、无相转移催化剂条件下,以草酸作助剂,采用磷钨酸催化过氧化氢氧化环己醇的方法来制备己二酸。考察了磷钨酸用量、反应时间、反应温度、过氧化氢用量及草酸用量对己二酸的分离产率的影响,得到最佳工艺条件,即环己醇10.51 mL、磷钨酸0.6 mmol/L、草酸1.0 mmol/L,H2O2(30%)70 mL,温度85℃、时间8 h,己二酸的最大分离产率为77.83%,纯度为99.9%。