普瑞巴林中间体的合成

以异戊醛和氰基乙酸乙酯为原料,经Knoevenagel缩合、氰基加成、高温脱羧3步反应合成了普瑞巴林中间体异丁基丁二腈(Ⅲ),其中第1步和第2步反应产物分别为5-甲基-2-氰基-2-己烯酸乙酯(Ⅰ)和5-甲基-2,3-二氰基己酸乙酯(Ⅱ)。通过对原料配比、反应温度、反应时间等反应条件的考察和优化,得到最优反应条件下化合物Ⅰ、Ⅱ、Ⅲ的收率分别达到92.3%、93.6%和94.2%,总收率为81.4%。各反应产物的结构通过1HNMR、IR及MS进行了表征和确认。     

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。     

一水硫酸氢钠催化合成乙二醇单甲醚乙酸酯

以一水硫酸氢钠为催化剂,由乙二醇单甲醚和冰乙酸合成了乙二醇单甲醚乙酸酯。考察了乙二醇单甲醚和冰乙酸摩尔比及催化剂用量对酯化率的影响。适宜反应条件为:乙二醇单甲醚∶冰乙酸∶一水硫酸氢钠=1∶1.75∶0.036(摩尔比),苯作带水剂,回流分水60min,酯化率达90.0%。产品经元素分析和红外光谱表征。     

Mass Spectrometric Confirmation of γ-Linolenic Acid Ester-Linked Ceramide 1 in the Epidermis of Borage Oil Fed Guinea Pigs

Ceramide 1 (Cer1), a Cer species with eicosasphingenine (d20:1) amide‐linked to two different ω‐hydroxy fatty acids (C30wh:0:C32wh:1), which are, in turn, ester‐linked to linoleic acid (LNA; 18:2n‐6), plays a critical role in maintaining the structural integrity of the epidermal barrier. Prompted by the recovery of a disrupted epidermal barrier with dietary borage oil [BO: 36.5 % LNA and 23.5 % γ‐linolenic acid (GLA; 18:3n‐6)], in essential fatty acid (EFA)‐deficient guinea pigs, we further investigated the effects of BO on the substitution of ester‐linked GLA for LNA in these two epidermal Cer1 species by LC–MS in positive and negative modes. Dietary supplementation of BO for 2 weeks in EFA‐deficient guinea pigs increased LNA ester‐linked to C32wh:1/d20:1 and C30wh:0/d20:1 of Cer1. Moreover, GLA ester‐linked to C32wh:1/d20:1, but not to C30wh:0/d20:1, of Cer1 was detected, which was further confirmed by the product ions of m/z 277.2 for ester‐linked GLA and m/z 802.3 for the deprotonated C32wh:1/d20:1. C20‐Metabolized fatty acids of LNA or GLA were not ester‐linked to these Cer1 species. Dietary BO induced GLA ester‐linked to C32wh:1/d20:1 of epidermal Cer1.     

2-甲基-4-甲醛肟基苯甲酸甲酯的合成

以2-甲基-4-溴苯甲酸为起始原料,经酰化和酯化反应制得2-甲基-4-溴苯甲酸甲酯,2-甲基-4-溴苯甲酸甲酯与氰化亚铜在DMF中发生取代反应得到2-甲基-4-氰基苯甲酸甲酯,接着与盐酸羟胺在碳酸钠存在下反应得到标题化合物,总收率为61%,纯度为99.2%。化合物的结构经IR、MS、~1HNMR和~(13)CNMR等确证。该路线中目标产物肟经由氰基直接一步反应制得,工艺简单可靠、产品收率高。该方法为肟的合成提供了良好的实验基础。     

5—降冰片烯—2,3—二羧酸单甲酯的合成

由双环戊二烯热解制得的环戊二烯与顺丁烯二酸酐反应得５－降冰片烯－２,３－二酸酐（ＮＡ）,再单甲酯化制得５－降冰片烯－２,３－二羧酸单甲酯（ＮＥ）,产品收率可达５．６２％,左右,纯度≥９７％。     

3-脲基-2-氰基-2-丙烯酸乙酯的合成研究

在二甲苯中以氰乙酸乙酯、原甲酸三乙酯和尿素合成3-脲基-2-氰基-2-丙烯酸乙酯.产物用乙酸乙酯重结晶,通过1H NMR对产物结构进行了表征.并对合成工艺进行了优化,得到较适宜的工艺条件:n(氰乙酸乙酯):n(原甲酸三乙酯):n(尿素)=1.0:1.12:1.1,反应时间10 h,收率73.65 %.     

(E)-4-吗啉-2-丁烯酸盐酸盐的合成

以吗啉为起始原料,与溴丁烯酸甲酯反应,得到4-吗啉-2-丁烯酸甲酯,然后在二氧六环中用浓盐酸水解,得到目标产物,总收率为49.65%,产物结构经过1H NMR确证。     

甲基丙烯酸十六酯的合成

以甲苯为携水剂,采用溶液聚合法合成甲基丙烯酸十六酯,对甲基丙烯酸十六酯的多种合成条件进行探讨,应用酯化物酸值测定法确定反应酯化程度。改进提纯分离方法,提高甲基丙烯酸十六酯的纯度。结果表明,在反应温度110℃,酸醇摩尔比为1.2∶1,催化剂用量为2.0%,反应时间为5 h时为最佳反应条件,酯化率可达92%。     

5-溴-2-羟基-3-(1-丙酰基)苯甲酸甲酯合成工艺的研究

以水杨酸为原料合成5-溴-2-羟基3-(1-丙酰基)苯甲酸甲酯,从催化剂的用量、物料配比等方面研究了水杨酸甲酯化反应,以及从反应溶剂、加料方式和原料配比等方面研究了C-酰化反应,并利用IR、GC-MS确认产品结构。最佳工艺条件为:m(离子交换树脂催化剂):m(水杨酸)为1:100,n(甲醇):n(水杨酸)=7:1,氯仿为溶剂,加料方式为将酯滴加到氯化铝的氯仿溶液中,n(氯化铝):n(5-溴水杨酸甲酯):n(丙酸酐)=2:1:1,反应物总收率为74.52%。     

双月桂酰酒石酸酯的合成

利用酒石酸与月桂酰氯反应合成一种新型双子表面活性剂双月桂酰酒石酸酯,探讨了物料配比、反应时间等因素对产品收率的影响,结果表明合成反应的最佳条件为n(月桂酰氯):n(酒石酸)为2．2:1,反应时间为3．0h,产品收率可达86％．产品具有良好的表面活性,与月桂酸钠相比具有更低的临界胶束浓度．     

减压条件下催化酯化合成聚乙二醇单甲醚丙烯酸酯

聚乙二醇单甲醚丙烯酸酯是合成梳形分散剂的重要单体。以聚乙二醇单甲醚和丙烯酸为原料,对甲苯磺酸为催化剂,减压条件下直接酯化合成聚乙二醇单甲醚丙烯酸酯,采用傅立叶红外光谱表征产物结构。对反应条件进行了优化,结果表明,在温度90 ℃、压力0.06 MPa、催化剂用量为反应物总质量的2.0%、阻聚剂用量为丙烯酸质量的1.5%、丙烯酸与聚乙二醇单甲醚物质的量比3∶1和反应时间5 h条件下,酯化率可达92.6%。高效液相色谱分析证明,用饱和食盐水和乙酸乙酯萃取后的产物纯度为99.2%。     

Separation of yttrium from europium using a hollow fiber-supported liquid membrane with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester as an extractant

The separation of Y(III) from Eu(III) using a hollow fiber-supported liquid membrane with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (EHPNA) as an extractant was studied. The effects of HCl and metal concentrations in the feed solution, the EHPNA concentration in the membrane, and the HCl concentration in the stripping solution on the initial fluxes of the two metals and the separation factor were investigated. The optimum conditions for selective recovery of Y(III) from an equimolar solution of Y(III) and Eu(III) chlorides (0.001?mol?L^?1 each) were as follows: HCl concentration in the feed solution, 0.1?mol?L^?1; EHPNA dimer concentration in the organic phase in the membrane, 0.1?mol?L^?1; and HCl concentration in the stripping solution, 4?mol?L^?1. Under these conditions, complete Y(III) extraction was achieved after 1 ks of operation, and the Y(III) purity in the stripping solution was 84%.     

β-Ketophosphonates with Pentalenofuran Scaffolds Linked to the Ketone Group for the Synthesis of Prostaglandin Analogs

β-Ketophosphonates with pentalenofurane fragments linked to the keto group were synthesized. The bulky pentalenofurane skeleton is expected to introduce more hindrance in the prostaglandin analogues of type III, greater than that obtained with the bicyclo[3.3.0]oct(a)ene fragments of prostaglandin analogues I and II, to slow down (retard) the inactivation of the prostaglandin analogues by oxidation of 15α-OH to the 15-keto group via the 15-PGDH pathway. Their synthesis was performed by a sequence of three high yield reactions, starting from the pentalenofurane alcohols 2, oxidation of alcohols to acids 3, esterification of acids 3 to methyl esters 4 and reaction of the esters 4 with lithium salt of dimethyl methanephosphonate at low temperature. The secondary compounds 6b and 6c were formed in small amounts in the oxidation reactions of 2b and 2c, and the NMR spectroscopy showed that their structure is that of an ester of the acid with the starting alcohol. Their molecular structures were confirmed by single crystal X-ray determination method for 6c and XRPD powder method for 6b.     

Properties of β-fructosidases (invertases and inulinases) of Fusarium oxysporum grown on an aqueous extract of Cichorium intybus roots

Four different forms of invertase and inulinase named as Invertase, I, II, III, IV and inulinase I, II, III, IV were purified from a culture filtrate of Fusarium oxysporum, grown on a fructan containing medium, by ammonium sulphate fractionation, gel permeation and ion exchange chromatography. Invertases had a higher optimum temperature (55–60°C) as compared to that of inulinases (35–45°C). Of sucrose, raffinose, stachyose and inulin, sucrose was the best substrate for all the four invertases and none of the invertases showed activity with inulin. Inulinases showed maximum activity with inulin. The optimum pH of invertase I and II was 5.5 whereas invertase III and IV showed a maximum activity at pH 4.0. Inulinases I, II, III and IV had an optimum pH of 5.5, 5.5, 6.0 and 6.5, respectively. The thermal stability of invertases was in the order of invertase III > IV > II > I. Inulinase II was more stable than inulinase I whereas inulinase III and IV were the least stable. Inulinases showed a low K_m in the range of 10–95 μmol dm^?3 of inulin, thereby showing their high affinity for inulin. K_m for invertases varied from 2 mmol dm^?3 to 4 mmol dm^?3 of sucrose. HgCl₂ and CuSO₄ were found to be strong inhibitors for both invertases and inulinases.     

丙烯海松酸聚乙二醇酯的合成及聚集行为

以松香和丙烯酸为单体合成了丙烯海松酸,利用气相色谱-质谱联用技术（GC-MS）对合成的丙烯海松酸进行了表征。以丙烯海松酸和聚乙二醇2000为单体采用条件温和的steglich酯化法合成了两亲性的丙烯海松酸聚乙二醇酯,并应用红外（FT-IR）、凝胶渗透色谱（GPC）和热重（TG）研究了该物质的结构和性能。结果表明：丙烯海松酸聚乙二醇酯数均相对分子质量为4 700,多分散系数为1.2,分解温度在308~410℃范围内。采用表面张力和芘稳态荧光法测定了该物质的临界胶束质量浓度（CMC）,其CMC为1 g/L。用共振光散射（RLS）、动态光散射（DLS）和扫描电镜（SEM）法研究了丙烯海松酸聚乙二醇酯水溶液的聚集行为,结果表明：1 g/L的丙烯海松酸聚乙二醇酯水溶液在高于聚集温度74℃时胶束聚集,随着溶液的质量浓度由1 g/L增加到1.5 g/L时,聚集温度由74℃降低到65℃;1 g/L丙烯海松酸聚乙二醇酯水溶液的温度由25℃升高到85℃时,水合粒子平均直径（D_h）由295 nm增加到1 056 nm。     

制备绿色润滑剂三羟甲基丙烷酯的催化酯化新工艺

以油酸和三羟甲基丙烷(TMP)为原料,用SnCl2.2H2O作催化剂,通过减压酯化的方法合成了三羟甲基丙烷油酸酯。反应的优化条件如下:n(油酸)n∶(TMP)=3.11∶,催化剂用量4%,反应温度170℃,反应时间4h,真空度0.09MPa。优化条件下TMP的酯化率达到94%。产物结构经IR光谱证实。     

脱氢枞酸(β-丙烯酰氧基乙基)酯的合成和表征

以脱氢枞酸为原料,以草酰氯为酰基化试剂(摩尔比1∶1),先合成脱氢枞酸酰氯,然后再与丙烯酸-β-羟基乙基酯酯化(摩尔比1∶1),合成脱氢枞酸(β-丙烯酰氧基乙基)酯,得率75%,质量分数98.5%。用FTIR、GC-MS、13CNMR和DSC对其结构和性能进行了表征。结果表明,脱氢枞酸(β-丙烯酰氧基乙基)酯是一种熔点为59~61℃的白色晶体,在引发剂的存在下,可以发生聚合反应,均聚物玻璃化转变温度约为54.2℃。     

共轭亚油酸乙酯的合成

采用间歇式反应 ,以硫酸、磷酸、对甲苯磺酸为催化剂对共轭亚油酸乙酯进行了合成 ,并采用正交实验设计研究了物料比、反应温度、反应时间、催化剂用量对产品收率和品质的影响。硫酸、对甲苯磺酸催化活性佳 ,磷酸催化活性差。得到了如下合成工艺条件 :硫酸催化 ;n(共轭亚油酸 )∶n(无水乙醇 ) =1∶6;酯化反应温度 76℃ ;反应时间 1h ;催化剂用量为共轭亚油酸质量的 2 5 % ,收率可达 75 % ,产品w(共轭亚油酸乙酯 ) =77%～ 82 %。     

Synthesis and Highly Stereoselective Hydrogenation of the Statin Precursor Ethyl (5S)‐5,6‐Isopropylidenedioxy‐3‐oxohexanoate

A search for the large‐scale preparation of (5S)‐5,6‐(isopropylidenedioxy)‐3‐oxohexanoates ( 2 ) – a key intermediate in the synthesis of pharmacologially important statins – starting from (S)‐malic acid is described. The synthesis of the required initial compound methyl (3S)‐3,4‐(isopropylidenedioxy)butanoate ( 1 ) by Moriwake’s reduction of dimethyl (S)‐malate ( 3 ) has been improved. Direct 2‐C chain elongation of ester 1 using the lithium enolate of tert‐butyl acetate has been shown to be successful at a 3‐ to 5‐fold excess of the enolate. Unfortunately, the product, tert‐butyl (5S)‐5,6‐(isopropylidenedioxy)‐3‐oxohexanoate ( 2a ) is unstable during distillation. Ethyl (5S)‐5,6‐(isopropylidenedioxy)‐3‐oxohexanoate ( 2b ) was prepared alternatively on a multigram scale from (3S)‐3,4‐(isopropylidenedioxy)butanoic acid ( 7 ) by activation with N,N′‐carbonyldiimidazole and subsequent reaction with Mg(OOCCH₂COOEt)₂. A convenient pathway for the in situ preparation of the latter is also described. Ethyl ester ( 2b ) can be advantageously purified by distillation. The stereochemistry of the catalytic hydrogenation of β‐keto ester ( 2b ) to ethyl (5S)‐5,6‐(isopropylidenedioxy)‐3‐hydrohyhexanoate (syn‐ 6 and anti‐ 6 ) has been studied using a number of homogeneous achiral and chiral Rh(I) and Ru(II) complexes with phosphine ligands. A comparison of Rh(I) and Ru(II) catalysts with (S)‐ and (R)‐BINAP as chiral ligands revealed opposite activity in dependence on the polarity of the solvent. No influence of the chiral backbone of substrate 2b on the enantioselectivity was noted. A ratio of syn‐ 6 /anti‐ 6 =2.3 was observed with an achiral (Ph₃P)₃RuCl₂ catalyst. Ru[(R)‐Tol‐BINAP]Cl₂ neutralized with one equivalent of AcONa afforded the most efficient catalytic system for the production of optically pure syn‐(5S)‐5,6‐isopropylidenedioxy‐3‐hydroxyhexanoate (syn‐ 6 ) at a preparative substrate/catalyst ratio of 1000:1.