6-羟基-2-乙酰萘的制备

采用6 甲氧基 2 乙酰萘与浓盐酸在缚酸剂三乙胺存在的条件下进行水解反应制得6 羟基 2 乙酰萘。同时通过正交设计研究了反应的优化条件,即 6 甲氧基 2 乙酰萘、浓盐酸、三乙胺与二氯甲烷的比例为:1 g∶90 ml∶0.75 ml∶2.5 ml,反应收率为 79%。反应监控为TLC(展开剂为:正庚烷、二氯甲烷和丙酮=3∶6∶2.5,v/v)。盐酸的用量大幅度降低,产品成本降低36%。     

d-萘普生中间体2-(6’-甲氧基-2’-萘基)丙烯酸合成方法的研究

以丙酮酸乙酯 (Ⅱ )和 2 萘甲醚 (Ⅰ )为原料 ,在AlCl3 催化下反应合成了 2 羟基 2 (6’ 甲氧基 2’ 萘基 )丙酸乙酯 (Ⅲ )。最佳反应条件为 :n(Ⅱ )∶n(Ⅰ ) =1 2∶1 ,反应温度为 0～ 5℃ ,反应时间为 1 5h。Ⅲ经碱催化水解 32h得 2 羟基 2 (6’ 甲氧基 2’ 萘基 )丙酸 (Ⅳ ) ,此两步反应收率为 74 8%。Ⅳ经酸催化脱水得 2 (6’ 甲氧基 2’ 萘基 )丙烯酸 (Ⅴ ) ,收率为 84.6 %。Ⅴ经立体加氢即得d 萘普生 (Ⅵ )。     

煤直接液化条件下萘-四氢萘加氢转化反应行为

以纳米Fe_2O_3为催化剂,在0.5 L高压釜中考察了反应压力19 MPa下,不同反应温度(435℃~465℃)和反应时间(0 min~120 min)对萘-四氢萘体系加氢转化过程及产物分布的影响。根据实验结果和分析,建立了萘-四氢萘体系加氢转化反应机理模型,通过优化算法求解得到各反应的反应速率常数和活化能。结果表明:萘很快达到转化平衡状态,且低温和长停留时间有利于萘的加氢转化;萘的加氢反应速率高于四氢萘的脱氢反应速率,在四氢萘的加氢反应中,以异构化反应为主,主要生成甲基茚满和丁基苯。反应物萘、四氢萘、十氢萘(反)、十氢萘(顺)、1-甲基茚满、正丁基苯和烷基苯的质量分数的实验值和模拟值的相对偏差分别为4.56%,1.35%,9.60%,7.24%,8.29%,10.64%和10.07%。     

1-(支链烷基)萘和1-(支链烷基)萘-4-磺酸钠的合成

采用高效的合成路线制备了支链化的1 烷基萘(Ⅳ)和相应的1 烷基萘 4 磺酸钠(Ⅴ)。合成的6种化合物的结构如下:1 异丁基萘,1 (2 己基)萘,1 丁基萘以及相应的磺酸钠盐。以1 溴代萘为起始原料制备Ⅳ的产率为51 8%,以Ⅳ为原料制备Ⅴ的产率为42%。该方法以1 萘基溴化镁(Ⅰ)和1 丁酮(或1 己酮,或丁醛)回流反应6h,得1 萘基烷醇(Ⅱ),产率80%。Ⅱ与红磷和碘的混合物在冰醋酸溶液反应,回流3h,得到烯烃混合物(Ⅲ),产率95%以上。Ⅲ在室温下用Pd C催化加氢2h,得到Ⅳ,产率90%。Ⅳ用氯磺酸磺化,反应物料比n(Ⅲ)∶n(氯磺酸)=1∶2,以三氯甲烷为溶剂,5℃以下反应5h得到Ⅴ的粗产品,产率70%;粗产品在V(乙醇)∶V(水)=1∶1中重结晶两次,得精产品,收率为60%。用IR,ESI-MS和1HNMR鉴定了Ⅳ和Ⅴ的结构。     

手性离子对HPLC法拆分1-α-萘氧基-3-异丙氨基-2-丙醇对映体

建立了一种在Nova -PakCN HP氰基柱上拆分 1 α 萘氧基 3 异丙氨基 2 丙醇对映体的高效HPLC方法。流动相组成为V(二氯甲烷 )∶V(异丙醇 )∶V(乙酸 ) =98∶1∶1,添加N 苄氧羰基 S 苯基 L 半胱胺酸 (BPC)为手性离子对试剂 ,c(BPC) =3.0mmol/L ,流动相流速为 0 .3mL/min ,检测波长为 2 5 4nm ,1 α 萘氧基 3 异丙氨基 2 丙醇对映体的分离选择性为 1.15 ,分离度为 1.19,线性范围为 0 .1～ 4.5mg/mL ,浓度测定的变异系数为 0 .33 %～ 0 .71%     

2-溴-3-甲基-1,4-二甲氧基萘的合成

以2-甲基萘醌为原料,经过催化氢化、甲醚化和溴化3步反应,合成了维生素K2的重要中间体2-溴-3-甲基-1,4-二甲氧基萘(1)。以钯碳为催化剂加氢还原,得到了2-甲基-1,4-二羟基萘(3),收率98.8%;3在碱性条件下用硫酸二甲酯进行甲氧基保护,生成2-甲基-1,4-二甲氧基萘(4),收率95.1%;4与溴反应可以得到1,收率90.1%。3步反应总收率由传统方法的48.7%提高到84.6%。     

2-甲氧基-6-(2′-萘基)丙酸-(2,″2″-二甲基-3″-溴)丙酯水解反应制备萘普生

用氢氧化钠水溶液水解2-甲氧基-6-(2′-萘基)丙酸-(2,″2″-二甲基-3″-溴)丙酯得到萘普生,以萘普生收率为主要指标,用均匀设计和单因素实验方法,考察了NaOH质量分数,物料摩尔比,水解时间对水解反应的影响。结果表明:在水解温度(110±5)℃,水解反应时间60~90 m in,w(NaOH)=40%,n(氢氧化钠)∶n(原料)=4.4∶1的条件下,萘普生收率可达99.19%。同时确定了高效液相色谱分析萘普生的分析方法。     

1,5-萘二硫醇的合成

硫族元素有机化合物在材料中的应用 ,已成为当今有机化学研究领域的重要课题之一 [1] 。 1 ,5—萘二硫醇是制备半导体材料的重要前体化合物。我们曾经用 Sn Cl2 .2 H2 O[2 ] 、Zn粉及 Zn—Hg[3] 齐为催化剂 ,进行了 1 ,5—萘二硫醇制备研究 ,但收率较低 ,而且 Zn—Hg齐方法有大量汞残杂析出 ,对环境危害很大。因此我们对 1 ,5—萘二硫醇的合成方法进行了改进研究。合成路线如下 :1　实验部分1 .1　仪器与试剂2 4 0 0型元素分析仪 (美国 ) ;V arian MAT2 1 2型快原子轰击质谱仪 (美国 ) ;Jas co FT—IR80 0 0型红外光谱仪 (日本 ) ;J…     

1-(6-甲氧基-2-萘基)乙醇的合成

2 甲氧基萘经1,3 二溴 5,5 二甲基乙内酰脲盐酸催化溴化、Friedel Crafts乙酰化得到5 溴 6 甲氧基 2 乙酰基萘。在KOH、n BuOH和Et3N溶液中、w(Pd)=10%的Pd/C催化下,于60℃和常压下用H2氢化5 溴 6 甲氧基 2 乙酰基萘得1 (6 甲氧基 2 萘基)乙醇,收率98 7%。合成总收率94%(以2 甲氧基萘计)。     

2-萘二硫醚制备新工艺研究

以2-萘磺酰氯为原料,以碘化钾/亚硫酸氢钠/甲酸组成的还原体系制备标题化合物,产物的结构经~1HNMR和~(13)CNMR表征。通过单因素和正交试验,考察反应物物质的量比、反应温度、反应时间等对收率的影响,最终确定合成标题化合物的最优条件为:n(2-萘磺酰氯)∶n(亚硫酸氢钠)=1∶4、n(2-萘磺酰氯)∶n(甲酸)=1∶3. 5、n(2-萘磺酰氯)∶n(碘化钾)=1∶2. 5、水作为溶剂、反应温度为100℃、反应时间2. 5 h,产品收率为69. 7%,纯度可达96%以上。该方法原料易得、操作简单,并实现了对还原剂的部分循环利用,为工业化奠定了基础。     

食品接触材料中正丁醇迁移量的测定

建立了食品接触材料中正丁醇迁移量的顶空-气相色谱质谱联用测定方法。采用水、4%(体积分数)乙酸水溶液、10%(体积分数)乙醇水溶液、50%(体积分数)乙醇水溶液、95%(体积分数)乙醇水溶液和橄榄油作为食品模拟物,不同类型食品接触材料在不同迁移条件下的进行迁移试验。浸泡液在顶空70℃下平衡40 min后进样,采用INNOWAX毛细管柱进行分离。在优化的条件下,橄榄油模拟液中正丁醇在0.01~0.5mg/kg范围内线性良好,曲线相关系数(r)为0.999 5,检出限为0.01 mg/kg,其他5种模拟液中正丁醇在0.01~0.5mg/L线性良好,r均大于0.999 5,检出限为0.01 mg/L。在3个添加水平下,平均回收率在90%~110%之间。方法简单、快速、灵敏,可满足食品接触材料中正丁醇迁移量的检测需求。     

MICROWAVE-ASSISTED EXTRACTION OF GLYCYRRHIZIC ACID FROM LICORICE ROOT-EFFECT OF THE PROPERTY OF SOLUTION ON EXTRACTION OF GA

The property of extraction solution is an important factor influencing the extraction efficiency. In the present work, the effect of the property of solution on extraction of GA was studied, which including the concentration of ethanol, ammonia and cation (M+), pH of extraction solution, different kinds of organic solvent etc. The results show that 50%-60%(v/v) ethanol can reach high percentage extraction of GA. If 1% (v/v) ammonia solution was added into 60%(v/v) ethanol, the percentage extraction can be increased from 2.0% to 2.31%. Without ammonia, 50mmol/L [M+] (M+ = K+, NH4+) was added into 60%(v/v) ethanol, percentage extraction of GA can reach about 2.26%. If pH of solution (60% ethanol) was adjust to pH=4.0, it can reach high percentage extraction. If pH of solution (60% ethanol + 50mmol [M+], pH=6.1) was adjust tO PH=4.0, especially M+ is K+ or NH4+, it can reach almost same extraction efficiency as that of 1% ammonia solution + 60% ethanol, and the operation environment can be greatly improved.     

In situ reactive extraction of lactic acid from fermentation media

Extractive lactic acid fermentation was investigated in the presence of sunflower oil and Alamine‐336 (with oleyl alcohol as the diluent solvent). Lactic acid was produced in various media at 37 °C using Lactobacillus delbrueckii (NRRL‐B 445). First, the effects of oleyl alcohol (33.3%, v/v), immobilisation, and immobilisation in the presence of sunflower oil (5, 10, 15%, v/v) on lactic acid production were investigated. It was found that oleyl alcohol did not affect production while addition of sunflower oil increased lactic acid production from 10.22 to 16.46 gdm^?3. On the other hand, a toxic effect was observed for oleyl alcohol solutions containing 15–50% (v/v) Alamine‐336. A maximum total lactic acid concentration of 25.59 gdm^?3 was obtained when an oleyl alcohol solution containing 15% (v/v) Alamine together with immobilised cells with 15% (v/v) sunflower oil was used. This value was about 2.5 times that obtained from fermentation without organic solutions. © 2001 Society of Chemical Industry     

A new pigment for smart anticorrosive coatings

The purpose of this paper was to evaluate the performance of a modified zeolite as an anticorrosive pigment for paints. A procedure to prepare the pigment was outlined and its anticorrosive properties assessed following the electrochemical behavior of a steel electrode in pigment suspension. In a second stage, alkyd paints were formulated employing different anticorrosive pigments: (1) 30% by volume (v/v) of the modified zeolitic rock, (2) 10% (v/v) of zinc phosphate, and (3) a mixture of 10% (v/v) zinc phosphate plus 20% (v/v) of the modified zeolitic rock. In every case, percentages were referred to the total pigment content. Titanium dioxide, zinc oxide, and barium sulfate were incorporated to complete the pigment formula. The pigment volume concentration/critical pigment volume concentration (PVC/CPVC) ratio was 0.8. The performance of the resulting anticorrosive paints was assessed by accelerated (salt spray and humidity chambers) tests and electrochemical (corrosion potential, ionic resistance, and polarization resistance) essays. It was demonstrated that the modified zeolite is effective in protecting steel from corrosion when it is used in combination with zinc phosphate. There exists a synergism between the modified zeolite and zinc phosphate that allows the zinc phosphate content in anticorrosive paints to be reduced.     

Study on Optimum Extraction Conditions for Olive Leaf Extracts Rich in Polyphenol and Flavonoid

Ultrasound-assisted extraction (UAE) of polyphenols and flavonoids from olive leaves was investigated. The effects of temperature (27?37°C), solvent concentration (10?70% ethanol (EtOH), v/v) and time (30?60 min) were determined by both experimental and Response Surface Methodology (RSM) techniques. Free radical scavenging activity for the antioxidant capacity was tested by 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical. For total phenolic content (TPC), 43.8252 mg-GAE/g dried leaf was predicted at the optimum conditions (34.18°C, 43.61% (v/v) of EtOH, and 59.99 min). In case of total flavonoid content (TFC), 31.9920 mg-CE/g dried leaf was calculated at the optimum conditions (34.44°C, 70% (v/v) of EtOH, and 60 min).     

Development of gas recycling photobioreactor system for microalgal carbon dioxide fixation

A gas recycling photobioreactor was developed to achieve high CO₂ conversion, in whichChlorella vulgaris was cultivated under various light intensities. The light intensity affected the algal growth and the CO₂ concentration in the exit gas. However, the final cell density was independent of light intensity and was limited by nitrate concentration in the medium. In the linear growth phase, the CO₂ concentration in the exit gas ranged 4.6 to 6.0 % (v/v) when 20 % (v/v) CO₂ balanced with 80 % (v/v) N₂ was introduced into the photobioreactor. The gas recycling photobioreactor developed in this work was claimed to be a useful system for microalgal CO₂ fixation.     

Foam fractionation of spent sulphite liquor: Part I: Separation of surfactants

The surface activity of spent sulphite liquor (SSL) and the separation of surface active components by foam fractionation were studied. The maximum activity (lowest surface tension) of SSL was observed at a high pH. The surface tension was found to be 42 mN/m and 38 mN/m at acidic and basic pH values, respectively, and also a maximum foaminess (Σ) of 7 min was observed at pH 10. Foam fractionation reduced the surfactant concentration by 90% at an optimum pH of 10. The surfactants were concentrated in the collapsed foam as shown by the fact that the critical micelle concentrations of the unfractionated SSL and foam were 70% (v/v) and 10% (v/v), respectively. The removed surfactants were concentrated in 20% of the original liquid volume.     

Isolation of Gamma and Delta Tocotrienols from Rice Bran Oil Deodorizer Distillate Using Flash Chromatography

Gamma (γ‐T3) and delta (δ‐T3) tocotrienols are the most potent natural protective agents against harmful effects of radiation exposure and there is substantial interest in advancing these tocols toward Food and Drug Administration approval. However, co‐administration with alpha tocopherol is reported to interfere with the radioprotective properties of the tocotrienols. The objective of this study was to test various flash chromatography conditions for the purification of fractions with a high proportion of γ‐T3 or δ‐T3 and a minimal amount of alpha isomers from tocol extract obtained from rice bran oil deodorizer distillate (RBODD). Load size (0.125, 0.250, 0.500 and 1.000 g), sample cartridge type (pre‐packed silica cartridge, empty cartridge+Celite 545) and mobile phase gradient [varying proportions of hexane–acetic acid (99.1:0.9 v/v) and ethyl acetate–acetic acid (99.1:0.9 v/v)] were evaluated. Peak resolution was best with a load size of ~1 % column capacity and a 5‐g silica sample cartridge coupled with a 12‐g silica column. A linear gradient of 0.8 % ethyl acetate–acetic acid (99.1:0.9 v/v) to hexane–acetic acid (99.1:0.9 v/v) (50 min) → 100 % ethyl acetate–acetic acid (99.1:0.9 v/v) (5 min) resulted in the best separation of tocols. The method developed was used to isolate tocols from samples of crude RBODD, tocol concentrate and tocol‐rich extract. The use of these conditions with a tocol‐rich extract resulted in several fractions containing 100 % purities of both γ‐T3 and δ‐T3.     

Surface tension and contact angle of herbicide solutions affected by surfactants

Contact angle and surface tension were measured for distilled and hard water solutions of adjuvants, Ortho X-77, Span-20, Sterox-NJ. Surfactant-WK, Triton B-1956, Triton X-114, Tween-20, and Sun Oil 11E. The same parameters were measured for suspensions of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] and ametryne [2-(ethylamino)-4-(isopropylamino)-6-(methylthio)-s-triazine] with and without each adjuvant. All adjuvants reduced surface tension and contact angle of distilled water; Surfactant-WK was most effective and Tween-20 was least effective. Increasing concentration of surfactants from 0 to 0.1% (v/v) gave progressive reduction in surface tension and contact angle while higher concentrations, 0.1 to 2.0% (v/v), had no further effect. Surfactant-WK at 0.1% (v/v) in distilled water reduced the surfact tension from 72.8 dynes/cm to 27 dynes/cm and contact angle from 110° to 41°. An additional increase in Surfactant-WK concentration from 0.1% (v/v) to 2% (v/v) did not further reduce surface tension and contact angle. Sun Oil 11E was identical in behavior except that it was less effective than the surfactants. Water hardness up to 1,000 ppm as Ca ions did not affect surface tension and contact angle in surfactant solutions. An aqueous solution of atrazine had a higher surface tension and contact angle than ametryne in the absence of surfactants. However, these differences were not observed when surfactants were added to either herbicide.