Cinnamyl alcohols and methyl esters of fatty acids from Wedelia prostrata callus cultures

Two methyl esters of fatty acids, namely octadecanoic acid methyl ester (methyl stearate) and hexadecanoic acid methyl ester (methyl palmitate), in addition to four cinnamyl alcohol derivatives, sinapyl alcohol, coniferyl alcohol, p-coumaryl alcohol and coniferyl alcohol 4-O-glucoside (coniferin), were isolated from callus cultures of Wedelia prostrata. The structure of coniferin was established by spectroscopic and chemical methods, while the other compounds were identified by gas chromatography-mass spectrometry and thin layer chromatography in comparison with standards.     

钙拮抗剂普拉地平合成的改进

普拉地平 (Pranidipine ,1 ,4 二氢 2 ,6 二甲基 4 (3 硝基苯基 ) 3 ,5 吡啶二羧酸甲酯肉桂醇酯 ,1 ) ,属于 1 ,4 二氢吡啶类钙拮抗剂。化合物 1具有钙通道拮抗作用 ,能缓解抑制钙通道 ,阻滞钙离子内流 ,并能抑制细胞内钙离子的释放 ,起长效降压作用[1 ] 。化合物 1降压作用优于硝苯地平和氨氯地平等钙拮抗剂[2 ] ,处于临床Ⅲ期研究[3] 。专利[4] 报道了 3 氨基 2 丁烯酸甲酯 (2 )和 2 (3 硝基亚苄基 )乙酰乙酸肉桂醇酯 (3 )发生Hantzsch环化反应合成普拉地平 (1 )。本文以双乙烯酮为原料 ,经与肉桂醇酯化制备乙酰乙酸肉桂醇酯 (4…     

Heterotelechelic Polymers by Ring‐Opening Metathesis and Regioselective Chain Transfer

Heterotelechelic polymers were synthesized by a kinetic telechelic ring‐opening metathesis polymerization method relying on the regioselective cross‐metathesis of the propagating Grubbs’ first‐generation catalyst with cinnamyl alcohol derivatives. This procedure allowed the synthesis of hetero‐bis‐end‐functional polymers in a one‐pot setup. The molecular weight of the polymers could be controlled by varying the ratio between cinnamyl alcohol derivatives and monomer. The end functional groups can be changed using different aromatically substituted cinnamyl alcohol derivatives. Different monomers were investigated and the presence of the functional groups was shown by NMR spectroscopy and MALDI‐ToF mass spectrometry. Labeling experiments with dyes were conducted to demonstrate the orthogonal addressability of both chain ends of the heterotelechelic polymers obtained.     

Catalytic Activity of Boron-Beta Zeolite Modified with Indium in the Epoxidation of Cinnamyl Alcohol

Liquid-phase epoxidation of cinnamyl alcohol was carried out with hydrogen peroxide as oxidizing agent using indium-containing boron- and aluminium-beta zeolites. It was proved that InO⁺ ions, created by oxidation of univalent indium cations incorporated into beta zeolite by reductive solid-state ion exchange, play an important role in the activation of hydrogen peroxide. The indium-hydroperoxo complex formed in beta zeolite pores was found to be accessible by the bulky cinnamyl alcohol molecules. Among the applied catalysts In/H[B]-beta (containing 7.6% In₂O₃/g) showed the highest selectivity in cinnamyl alcohol epoxidation.     

N,N-二甲基乙酰胺促进的羧酸肉桂酯的合成及其促进机理

在N,N-二甲基乙酰胺(DMAc)促进下,羧酸(1a～1v)依次与SOCl₂和肉桂醇反应合成了22个羧酸肉桂酯(2a～2v,其中2j, 2k, 2o, 2t和2v为新化合物),其结构经¹H NMR, ¹³C NMR, IR和MS(EI)表征。以巴豆酸肉桂酯(2i)的合成为例,研究了巴豆酸(1i)用量,肉桂醇用量,SOCl₂用量,DMAc用量对2i产率的影响和醇的加入方式对产物组成的影响。结果表明：在最优合成条件(1i 1.0 eq.,肉桂醇1.3 eq., SOCl₂ 1.3 eq., DMAc 2 mL, CH₂Cl₂ 6 mL,酰氯化后加入苄醇)下,2i产率82.2%。采用¹H NMR跟踪反应,确证了DMAc促进反应的机理。     

Highly Efficient Direct Aerobic Oxidative Esterification of Cinnamyl Alcohol with Alkyl Alcohols Catalysed by Gold Nanoparticles Incarcerated in a Nanoporous Polymer Matrix: A Tool for Investigating the Role of the Polymer Host

The selective aerobic oxidation of cinnamyl alcohol to cinnamaldehyde, as well as direct oxidative esterification of this alcohol with primary and secondary aliphatic alcohols, were achieved with high chemoselectivity by using gold nanoparticles supported in a nanoporous semicrystalline multi‐block copolymer matrix, which consisted of syndiotactic polystyrene‐co‐cis‐1,4‐polybutadiene. The cascade reaction that leads to the alkyl cinnamates occurs through two oxidation steps: the selective oxidation of cinnamyl alcohol to cinnamaldehyde, followed by oxidation of the hemiacetal that results from the base‐catalysed reaction of cinnamaldehyde with an aliphatic alcohol. The rate constants for the two steps were evaluated in the temperature range 10–45 °C. The cinnamyl alcohol oxidation is faster than the oxidative esterification of cinnamaldehyde with methanol, ethanol, 2‐propanol, 1‐butanol, 1‐hexanol or 1‐octanol. The rate constants of the latter reaction are pseudo‐zero order with respect to the aliphatic alcohol and decrease as the bulkiness of the alcohol is increased. The activation energy (E_a) for the two oxidation steps was calculated for esterification of cinnamyl alcohol with 1‐butanol (E_a=57.8±11.5 and 62.7±16.7 kJ mol^?1 for the first and second step, respectively). The oxidative esterification of cinnamyl alcohol with 2‐phenylethanol follows pseudo‐first‐order kinetics with respect to 2‐phenylethanol and is faster than observed for other alcohols because of fast diffusion of the aromatic alcohol in the crystalline phase of the support. The kinetic investigation allowed us to assess the role of the polymer support in the determination of both high activity and selectivity in the title reaction.     

Iron‐Catalyzed Allylic Amination Directly from Allylic Alcohols

Allylic amination, directly from alcohols, has been demonstrated without any Lewis acid activators using an efficient and regiospecific molecular iron catalyst. Various amines and alcohols were employed and the reaction proceeded through the oxidation/reduction (redox) pathway. A direct one‐step synthesis of common drugs, such as cinnarizine and nafetifine, was exhibited from cinnamyl alcohol that produced water as side product.     

Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over An Ultrafine Co—B Amorphous Catalyst

A novel Co-B amorphous alloy catalyst in the form of ultrafine particles was prepared by chemical reduction of CoCl2 with aqueous NaBH4, which exhibited excellent activity and selectivity during the hydrogenation of cinnamaldehyde to cinnamyl alcohol in liquid phase. The optimum yield of cinnamyl alcohol was 87.6%, much better than the yield of using Raney Ni, Raney Co and other Co-based catalysts.     

Kinetics of Enzymatic Synthesis of Cinnamyl Butyrate by Immobilized Lipase

This work illustrates the enzymatic synthesis of cinnamyl butyrate by esterification of butyric acid and cinnamyl alcohol. Experiments were performed to study the various operating parameters such as molar ratio, enzyme concentration, temperature, and speed of agitation. Also, the suitable kinetic model for esterification reaction was predicted and the various kinetic parameters were determined. It has been observed that the experimental results agree well with the simulated results obtained by following the ping-pong bi-bi mechanism with dead-end inhibition by both the substrate acid and alcohol. The highest 90% conversion of butyric acid was observed after 12 h at the following reaction conditions: substrate molar ratio 1:2 (butyric acid/cinnamyl alcohol), temperature 50 °C, enzyme loading 2% (with respect to the weight of the substrates), and agitation speed 250 rpm. Diffusional mass transfer limitations between substrate and enzyme surface do not show significant effect on reaction kinetics. Enzyme reusability study reveals that it retains 85% of its catalytic activity after five consecutive cycles.     

Stereoselective synthesis of the styryllactones, 7-epi-goniodiol and leiocarpin A, isolated from Goniothalamus leiocarpus

Two novel styryllactones, 7-epi-goniodiol and leiocarpin A, isolated from Goniothalamus leiocarpus, were stereoselectively synthesized in a short and efficient route from cinnamyl alcohol based on the asymmetric epoxidation and the palladium-catalyzed cross-coupling of vinyl epoxide with vinyltributylstannane.     

超声波辅助Ru-B非晶态合金常压催化肉桂醛加氢制备肉桂醇

采用KBH₄化学还原法制备了超细Ru-B非晶态合金催化剂。Ru-B催化剂在肉桂醇液相常压加氢中显示出较高的肉桂醇选择性。在加氢过程中使用超声辐射能大大提高反应速率而肉桂醇的选择性几乎保持不变。加氢速率随着超声频率或超声时间的增加而增加。通过XRD、XPS、TEM、BET和ICP等各种表征手段，简要研究了超声辐射对Ru-B催化剂结构和电子特征的影响。同时，还讨论了超声对肉桂醛选择性加氢制肉桂醇催化性能的促进作用。     

A concise and stereoselective synthesis of both enantiomers of altholactone and isoaltholactone

A concise and flexible stereoselective route to synthesize both enantiomers of the highly functionalized α,β-unsaturated-δ-lactones, altholactone and isoaltholactone, from readily available cinnamyl alcohol is described. This approach derived its asymmetry from Sharpless catalytic asymmetric epoxidation and Sharpless asymmetric dihydroxylation reactions. The resulting diols were produced in high enantiomeric excess and were cyclized in a stereoselective manner in the presence of a catalytic amount of camphor sulphonic acid.     

Differentiating parts of Cinnamomum cassia using LC‐qTOF‐MS in conjunction with principal component analysis

Cinnamon bark (Rou Gui in Chinese), cinnamon twig (Gui Zhi) and shaved cinnamon bark (Gui Sin) have been widely used as spices and in traditional Chinese medicine since ancient times. On‐going issues related to quality and authenticity necessitate the development of analytical methods capable of providing an objective evaluation of samples. In this study, chemical fingerprints of cinnamon bark, cinnamon twigs and shaved cinnamon bark were established using liquid chromatography quadruple time‐of‐flight mass spectrometry in conjunction with principal component analysis (PCA). From 125 samples of cinnamon, we identified the following eight compounds and their the detection ratios: coumarin, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, 2‐hydroxycinnamaldehyde, 2‐hydroxycinnamic acid, 2‐methoxycinnamaldehyde and 4‐methoxycinnamaldehyde. Of these, 4‐methoxycinnamaldehyde presented the largest variations in detection ratio, making up 64.0, 97.4 and 50.0% in cinnamon bark, cinnamon twig, and shaved cinnamon bark, respectively. The quantities of cinnamyl alcohol, coumarin and cinnamaldehyde also varied between the three parts of the plant. Chemical fingerprints of the three cinnamon samples were established using principal component analysis, the results of which indicate that cinnamon bark and shaved cinnamon bark could be easily differentiated, despite a marked similarity in outward appearance. Cinnamon twig was also shown to depart from the other clusters. The proposed method provides a fast and efficient means of identifying cinnamon herbs for quality control purposes. Copyright © 2016 John Wiley & Sons, Ltd.     

Simultaneous determination of cinnamaldehyde and its metabolite in rat tissues by gas chromatography–mass spectrometry

Cinnamaldehyde (CA), an active ingredient isolated from the traditional Chinese medicine Cortex Cinnamomi, has a wide range of bioactivities. To clarify the distribution characteristics of CA, a selective and sensitive method utilizing gas chromatography–mass spetrometry was initially developed for simultaneously determining the concentration of CA and its metabolite cinnamyl alcohol in rat tissues. Selected ion masses of m/z 131, 105 and 92 were chosen, and separation of the analytes was performed on a DB‐5 ms (30 m × 0.25 mm, 0.25 µm, thickness) capillary column by gas chromatography–mass spectrometry. The calibration curves demonstrated good linearity and reproducibility over the range of 20–2000 and 20–4000 ng/mL for various tissue samples. Recoveries ranged from 86.8 to 107.5%, while intra‐ and interday relative standard deviations were all <11.3%. The analysis method was successfully applied in tissue distribution studies for CA and cinnamyl alcohol. As CA and cinnamyl alcohol may inter‐convert to one another, simultaneous determination of both analytes provides a comparative and accurate data for tissue study. The concentrations of CA and cinnamyl alcohol remaining in spleen were the highest among the main organs, including heart, liver, spleen, lung, kidney and brain. In addition, there was no long‐term accumulation of CA in rat tissues. Copyright © 2014 John Wiley & Sons, Ltd.     

Pt－SPE电极中MnO_2粒子的电催化行为及反应溶剂对肉桂醇电解氧化的影响

讨论了ＭｎＯ２在Ｐｔ／ＳＰＥ电极中的电催化行为，指出与电化学反应相比，化学反应是慢步骤。因此提高后续化学反应的速度对提高反应的电流效率至关重要。并讨论了溶剂对肉桂醇电解氧化的影响，指出在水中溶解度大的溶剂有利于肉桂醇的氧化，当以ＴＨＦ作为溶剂进行电解时，电极电位低，生成肉桂醛的电流效率较高。     

Highly stereoselective synthesis of antitumor agents: both enantiomers of goniothales diol,altholactone, and isoaltholactone

A flexible stereoselective route to synthesize both enantiomers of the highly functionalized substituted tetrahydrofurans and α,β-unsaturated-δ-lactones, goniothales diol, altholactone, and isoaltholactone, from readily available cinnamyl alcohol is described. This approach derived its asymmetry from Sharpless catalytic asymmetric epoxidation and Sharpless asymmetric dihydroxylation reactions. The resulting diols were produced in high enantiomeric excess and were cyclized in a stereoselective manner in the presence of a catalytic amount of camphor sulfonic acid.     

Selective hydrogenation of α,β-unsaturated aldehydes over Pt supported on cerium–zirconium mixed oxide of different composition

Cerium–zirconium mixed oxides with different Ce/Zr ratio were prepared and used as supports for Pt-containing catalysts. The study of the catalysts in the cinnamaldehyde hydrogenation reaction has shown that cinnamaldehyde conversion and cinnamyl alcohol selectivity strongly depend on the CeO₂ content in the support. The highest cinnamyl alcohol yield of 81% was obtained in 105 min at room temperature and atmospheric pressure over the 1%Pt/CeO₂–ZrO₂ catalyst with Ce : Zr atomic ratio equal to 4 : 1.     

Reactions of sodium sulphide—I : With compounds containing hydroxyl groups

Aqueous solutions of sodium sulphide (ca 10%) reagent were reacted at 250° with compounds containing OH groups. This work was part of a programme designed to test the usefulness of the Na₂S solution degradation technique for determining the primary structure of humic acids. The compounds reacted here and the principal products detected (shown in brackets) were: cinnamyl alcohol (benzyl alcohol, benzoic acid, 3-phenylpropan-1-ol, 3-phenylpropionic acid), benzyl alcohol (little reaction), 3-phenylpropan-1-ol (little reaction), 1,2-dihydroxy-1-phenylethane (phenylacetic acid, acetophenone, 1-phenylethanol), catechol and hydroquinone (recovered starting compounds+ polymer products). Sodium hydroxide gave the same products with cinnamyl alcohol, but in different proportions. Possible mechanisms for these reactions are discussed.     

基于纳米镍催化的松香加氢研究--树酯酸组成的研究

松香的主要成份是枞酸型树脂酸,其因共轭双键的存在而易被氧化,大大降低了其附加值。经氢化后的松香具有抗氧性好、脆性小、热稳定性高、颜色浅等特点,因而广泛应用于胶粘剂、合成橡胶、涂料、油黑、造纸、电子、食品等工业部门[1]。采用催化加氢的方法可使枞酸型树脂酸中的共轭双键消除[2]。以枞酸为代表的反应式为:松香催化加氢主要有熔融法[3]和溶剂法[4],所用催化剂主要是Pd和N i。熔融法制氢化松香,当反应温度低于200℃时,枞酸加氢速度较慢,反应不完全。温度升高,氢化松香中枞酸含量显著地减少,但温度高于250℃时,树脂酸脱羧严重,甚至…     

Shoot Multiplication and Callus Induction of Labisia pumila var. alata as Influenced by Different Plant Growth Regulators Treatments and Its Polyphenolic Activities Compared with the Wild Plant

This study aims to investigate whether the in vitro-cultured L. pumila var. alata has higher antioxidant activity than its wild plant. An 8-week-old L. pumila var. alata nodal segment and leaf explants were cultured onto Murashige and Skoog (MS) medium supplemented with various cytokinins (zeatin, kinetin, and 6-benzylaminopurine (BAP)) for shoot multiplication and auxins (2,4-dichlorophenoxyacetic acid (2,4-D) and picloram) for callus induction, respectively. The results showed that 2 mg/L zeatin produced the optimal results for shoot and leaf development, and 0.5 mg/L 2,4-D produced the highest callus induction results (60%). After this, 0.5 mg/L 2,4-D was combined with 0.25 mg/L cytokinins and supplemented to the MS medium. The optimal results for callus induction (100%) with yellowish to greenish and compact texture were obtained using 0.5 mg/L 2,4-D combined with 0.25 mg/L zeatin. Leaves obtained from in vitro plantlets and wild plants as well as callus were extracted and analyzed for their antioxidant activities (DPPH and FRAP methods) and polyphenolic properties (total flavonoid and total phenolic content). When compared with leaf extracts of in vitro plantlets and wild plants of L. pumila var. alata, the callus extract displayed significantly higher antioxidant activities and total phenolic and flavonoid content. Hence, callus culture potentially can be adapted for antioxidant and polyphenolic production to satisfy pharmaceutical and nutraceutical needs while conserving wild L. pumila var. alata.