CLY纳米催化剂催化α-蒎烯合成龙脑

对CLY纳米催化剂催化α 蒎烯酯化-皂化法合成龙脑进行了研究。首先α 蒎烯和无水草酸在CLY纳米催化剂作用下发生酯化反应生成草酸龙脑酯;然后加入氢氧化钠溶液发生皂化反应,水蒸气蒸馏收集龙脑。酯化反应时间为 6h,采用程序升温方式(65℃ 1h, 75℃ 4h, 90℃ 1h),原料最佳配比n(α 蒎烯)∶n(草酸) =1∶0 4。皂化反应并收集龙脑约 1h,n(草酸龙脑酯)∶n(氢氧化钠) =1∶5。在上述反应条件下,当CLY2催化剂质量为α 蒎烯质量的 6%时,龙脑产率 93 3%,m(正龙脑)∶m(异龙脑) =29 1∶62 3;当CLY4催化剂质量为α 蒎烯质量的 2%时,产率为 46 0%,m(正龙脑)∶m(异龙脑) =70 5∶7 3,通过柱层析分离可获得质量分数为 98 9%的正龙脑。催化剂经 5次再生使用,产率仅下降 8 7%,而产品中正龙脑质量分数上升 2 2%,可见催化剂经再生可重复使用。     

天然脑粉二次还原精制右旋龙脑

根据化学平衡理论,提出了还原剂A/无水乙醇体系二次还原精制龙脑的工艺,并且考察了还原剂A用量和溶剂用量对樟脑二次还原的影响.经二次还原,樟脑转化率及龙脑产率都得到了较大提高.在本文的最佳反应条件下,还原剂A/无水乙醇体系二次还原所得的最高樟脑转化率和龙脑产率分别为93%和81%.二次还原法具有反应时间短,反应条件温和,产物收率和产物纯度高,经济效益高,绿色环保等优点.     

固体超强酸SO_4~(2-)/Al_2O_3催化α-蒎烯合成龙脑

对固体超强酸SO24-/Al2O3催化标题化合物作了研究,并对催化剂的制备及龙脑合成反应的最佳条件进行了探索。研究表明:当催化剂的焙烧温度为500℃,焙烧时间为3 h,催化剂的用量为α-蒎烯质量的4%,α-蒎烯与无水草酸的物质的量比为1∶0.2时,产率可达66.93%。产品中正龙脑含量可达85.43%,产品中正、异龙脑的含量比高达12.47∶1。     

固体超强酸SO2-4/Al2O3催化α-蒎烯合成龙脑

对固体超强酸SO2-4/Al2O3催化标题化合物作了研究,并对催化剂的制备及龙脑合成反应的最佳条件进行了探索.研究表明:当催化剂的焙烧温度为500 ℃,焙烧时间为3 h,催化剂的用量为α-蒎烯质量的4%,α-蒎烯与无水草酸的物质的量比为1:0.2时,产率可达66.93%.产品中正龙脑含量可达85.43%,产品中正、异龙脑的含量比高达12.47:1.     

α-蒎烯酯化-皂化法合成龙脑催化剂研究进展

龙脑为重要的香料及医药中间体,工业上主要采用酯化-皂化方法合成,即以α-蒎烯为原料在催化剂硼酐/乙酸酐(或偏硼酸等)作用下,与酯化剂无水草酸反应生成草酸酯再皂化生成龙脑。为了提高合成龙脑产率并降低具有一定副作用的异构体异龙脑含量,国内外从酯化过程中所用催化剂着手展开广泛而深入的研究,催化剂主要集中在含硼类、含钛类、硼钛复合类、固体超强酸类及其他类型如离子液体等。硼酐及偏硼酸是工业上常用催化剂,生产工艺成熟,但催化反应过程剧烈放热,不易控制,产品产率不理想,产品中异龙脑含量较高。偏钛酸催化剂是近年开发且已成功应用于工业生产,性能较平稳,但草酸消耗较大,设备要求高。硼钛复合物和硫酸促进型固体超强酸催化剂,龙脑产率及正龙脑选择性均较好,硼钛复合催化剂结合了硼类及钛类催化剂的优点,效果较好,已进行中试应用;硫酸促进型固体超强酸为绿色催化剂,易于回收再利用,具有较好的应用前景。功能化离子液体、大孔型离子交换树脂和杂多酸等其他新型催化剂的研究也取得进展,在产品产率、选择性、经济性和操作安全可控性等方面各有特点。     

草酸二龙脑酯的合成及其表征

在偏钛酸或者硼酐催化作用下,龙脑和草酸发生酯化反应生成草酸二龙脑酯,探讨了催化剂类型及用量、原料配比、反应温度以及反应时间对酯化反应的影响。结果表明,在50.0 g正己烷溶剂中,m(龙脑)∶m(草酸)∶m(催化剂)=5.0∶12.0∶3.0,于55℃下反应96 h,龙脑的转化率及草酸二龙脑酯的选择性分别为95.8%和99.4%。通过HRMS、IR、1HNMR、13CNMR等对草酸二龙脑酯进行了鉴定与表征。     

五个优选品种樟树样本枝、叶精油的水蒸气提取研究

采集广西南宁苗圃培育的香樟1号、香樟2号、福建芳樟、江西龙脑樟、湖南龙脑樟的新鲜枝、叶,通过水蒸气(水中)蒸馏法提取精油。考察这几种樟树枝、叶出油率和精油主要组分。结果发现,新鲜叶的精油出油率、精油中主成分芳樟醇和龙脑的相对含量均比嫩枝的高。在采集的原料中,江西龙脑樟叶的出油率最高,为2.4%;香樟1号叶精油的芳樟醇相对含量最高,为96.2%;江西龙脑樟叶精油的龙脑相对含量最高,为85.8%。     

大孔吸附树脂纯化右旋龙脑的工艺研究

研究洗脱剂乙醇体积分数、洗脱流速、上样液浓度对D101大孔吸附树脂纯化右旋龙脑效果的影响,确立右旋龙脑纯化工艺。通过单因素考察实验和正交实验,确立的最佳工艺条件为:洗脱剂乙醇体积分数为80%,洗脱流速为3.5 BV/h,上样液浓度为0.55 g/mL。在此条件下,右旋龙脑收率可达81.6%,纯度为98.32%。考察的因素对分离效果的影响程度为:洗脱剂乙醇的体积分数洗脱流速上样液浓度。建立的右旋龙脑精制工艺操作简便、收率高,适合扩大化生产。     

龙脑樟叶脱脑油成分分析

对用挥发油提取器提取得到的龙脑樟叶油进行真空抽滤,获得其脱脑油,再利用气相色谱-质谱联用仪和气相色谱仪对晶体及脱脑油进行了定性和定量分析。试验结果表明,真空抽滤是纯化龙脑樟叶油的可用方法之一;脱脑油中单萜类物质占总量的85.467%(相对质量分数),主要成分为为龙脑(23.813%)、D-苧烯(15.627%)、α-蒎烯(12.593%)、莰烯(6.309%)、β-月桂烯(6.213%)、乙酸龙脑酯(6.153%)和β-蒎烯(4.336%)等,可通过分馏对其加以利用。     

重结晶法纯化右旋龙脑的工艺研究

研究溶剂、固液比、结晶温度、结晶时间对右旋龙脑重结晶效果的影响,确立右旋龙脑重结晶纯化工艺。结果表明,最优重结晶条件是:溶剂为石油醚,结晶温度10℃,固液比1∶3 mg/m L,结晶时间15h。在此工艺条件下,右旋龙脑的收率可达77.06%,纯度可达98.21%。考察的因素对重结晶效果的影响程度为:结晶温度>固液比>结晶时间。     

环己烷捕集水蒸气蒸馏香椿叶挥发油及其成分分析

采用水蒸气蒸馏,环己烷捕集馏出物的方法提取香椿叶挥发油,利用气相色谱-质谱联用技术,分析了香椿叶挥发油的化学组成,分离鉴定出51种化合物,占总组分相对含量的 76.313%,其中主要成分是石竹烯 14.752%,石竹烯氧化物 9.218%,芳樟醇 6.266%,桉-4(14),11-二烯 5.916%,棕榈酸 5.585%,叶绿醇 4.140%,龙脑 3.796%、异龙脑 2.671% 和2-甲基-3-对异丙基苯基丙醛 2.427%。     

Simple Plug-In Synthetic Step for the Synthesis of (−)-Camphor from Renewable Starting Materials

Racemic camphor and isoborneol are readily available as industrial side products, whereas (1R)-camphor is available from natural sources. Optically pure (1S)-camphor, however, is much more difficult to obtain. The synthesis of racemic camphor from α-pinene proceeds via an intermediary racemic isobornyl ester, which is then hydrolyzed and oxidized to give camphor. We reasoned that enantioselective hydrolysis of isobornyl esters would give facile access to optically pure isoborneol and camphor isomers, respectively. While screening of a set of commercial lipases and esterases in the kinetic resolution of racemic monoterpenols did not lead to the identification of any enantioselective enzymes, the cephalosporin Esterase B from Burkholderia gladioli (EstB) and Esterase C (EstC) from Rhodococcus rhodochrous showed outstanding enantioselectivity (E>100) towards the butyryl esters of isoborneol, borneol and fenchol. The enantioselectivity was higher with increasing chain length of the acyl moiety of the substrate. The kinetic resolution of isobornyl butyrate can be easily integrated into the production of camphor from α-pinene and thus allows the facile synthesis of optically pure monoterpenols from a renewable side-product.     

锐钛型介孔偏钛酸催化剂的制备及其催化酯化性能

以工业偏钛浆为原料,通过水洗、碱洗、酸洗处理制备了锐钛型介孔偏钛酸催化剂,将催化剂用于α-蒎烯酯化反应中考察其催化性能,采用FT-IR、XRD、SEM、BET手段对催化剂的晶相结构、形貌、表面积、孔径等结构进行了表征。结果表明,最佳制备条件为：温度30 ℃,碱洗pH=8.5,酸洗pH=4.0;处理后的偏钛酸催化剂基本没有SO42?,且晶型没有发生明显变化,均为锐钛矿相,最佳条件下制备的偏钛酸催化剂孔径分布均匀,晶粒团聚较少,比表面积为334.82 m2/g,平均孔径为3.96 nm,催化α-蒎烯酯化生成草酸龙脑酯含量可达48.59 %,皂化后水蒸气蒸馏收集龙脑,m1（正龙脑）∶m2（异龙脑）=59.27∶37.07。     

Interactions of Borneol with DPPC Phospholipid Membranes: A Molecular Dynamics Simulation Study

Borneol, known as a “guide” drug in traditional Chinese medicine, is widely used as a natural penetration enhancer in modern clinical applications. Despite a large number of experimental studies on borneol’s penetration enhancing effect, the molecular basis of its action on bio-membranes is still unclear. We carried out a series of coarse-grained molecular dynamics simulations with the borneol concentration ranging from 3.31% to 54.59% (v/v, lipid-free basis) to study the interactions of borneol with aDPPC(1,2-dipalmitoylsn-glycero-3-phosphatidylcholine) bilayer membrane, and the temperature effects were also considered. At concentrations below 21.89%, borneol’s presence only caused DPPC bilayer thinning and an increase in fluidity; A rise in temperature could promote the diffusing progress of borneol. When the concentration was 21.89% or above, inverted micelle-like structures were formed within the bilayer interior, which led to increased bilayer thickness, and an optimum temperature was found for the interaction of borneol with the DPPC bilayer membrane. These findings revealed that the choice of optimal concentration and temperature is critical for a given application in which borneol is used as a penetration enhancer. Our results not only clarify some molecular basis for borneol’s penetration enhancing effects, but also provide some guidance for the development and applications of new preparations containing borneol.     

合成樟脑生产中异龙脑洗涤过程的减污生产方式

文章针对高品质合成樟脑生产要求，改进现有生产工艺，增加了异龙脑的热水洗涤和离心操作，并提出了异龙脑洗涤过程中废水减排和产品回收的相关工艺，实现了减污，避免了废水的大幅增加、降低了废水处理难度。     

Effects of Concentrations on the Transdermal Permeation Enhancing Mechanisms of Borneol: A Coarse-Grained Molecular Dynamics Simulation on Mixed-Bilayer Membranes

Borneol is a natural permeation enhancer that is effective in drugs used in traditional clinical practices as well as in modern scientific research. However, its molecular mechanism is not fully understood. In this study, a mixed coarse-grained model of stratum corneum (SC) lipid bilayer comprised of Ceramide-N-sphingosine (CER NS) 24:0, cholesterol (CHOL) and free fatty acids (FFA) 24:0 (2:2:1) was used to examine the permeation enhancing mechanism of borneol on the model drug osthole. We found two different mechanisms that were dependent on concentrations levels of borneol. At low concentrations, the lipid system maintained a bilayer structure. The addition of borneol made the lipid bilayer loosen and improved drug permeation. The “pull” effect of borneol also improved drug permeation. However, for a strongly hydrophobic drug like osthole, the permeation enhancement of borneol was limited. When most borneol molecules permeated into bilayers and were located at the hydrophobic tail region, the spatial competition effect inhibited drug molecules from permeating deeper into the bilayer. At high concentrations, borneol led to the formation of water pores and long-lived reversed micelles. This improved the permeation of osthole and possibly other hydrophobic or hydrophilic drugs through the SC. Our simulation results were supported by Franz diffusion tests and transmission electron microscope (TEM) experiments.     

合成龙脑母液分离新工艺

合成龙脑母液经硼酸酯化反应、分馏回收松油醇、水解硼酸酯回收龙脑的新分离工艺，其龙脑和松油醇回收率分别为８０％和８５％，该工艺安全可行，无污染，可明显提高经济效益。     

气相色谱法测定双料跌打酒中龙脑的含量

目的:建立双料跌打酒中龙脑的含量测定方法。方法:采用气相色谱法,以Rtx-WAX为固定相,载气为N2,柱温起始温度为120℃,以5℃/min的速度升至160℃。结果:龙脑进样量在0.62～4.9mg/mL的范围内与峰面积呈良好的线性关系(r=0.9982),平均回收率为100.4%,RSD为2.22%(n=6)。结论:该方法灵敏,准确,重复性好,可作为双料跌打酒的质量控制方法。     

毛细管柱气相色谱法测定速效救心丸中冰片的含量

目的：改进速效救心丸中冰片的含量的测定方法。方法：以水杨酸甲酯为内标物,乙酸乙酯为溶剂超声提取20min制各供试品溶液;应用SE-54石英毛细管柱（30m×0．25mm,0．33μm）、FID检测器进行分析。结果：在最佳色谱条件下,样品中冰片与内标物能得到很好的分离,冰片在0．2016--2．016mg·mL^-1范围内线性关系良好（r=0．9999,H=6）,加样回收率为99．37％（RSD=0．95％,n=6）。结论：本方法操作简便、准确、重现性好．可用于该制剂中的冰片含量测定。