相转移催化合成11-脱氧甘草次酸-3-位酯类衍生物

以甘草次酸为原料 ,经还原制得 1 1 -脱氧甘草次酸 ,然后在聚苯乙烯固载化聚乙二醇 40 0( PS- PEG- 40 0 )的催化下。合成了七种具有潜在药理活性和应用前景的 1 1 -脱氧甘草次酸 - 3-位酯类衍生物。合成方法简单 ,产率较高 ,后处理方便     

西仑吉肽的固相合成

采用Fmoc固相合成法,选用2-氯三苯甲基氯树脂作为固相载,HBTU/HOBt和HATU/HOBt为缩合剂,合成全保护线性肽.以V(DCM)∶V(THF)＝ 1∶1为溶剂,HATU/HOBt为缩合剂,合成全保护环肽.最后脱除保护基得终产物西仑吉肽.     

生物聚合物单体2,3,4,5-O-四乙基-D-葡萄糖酸-1,6-内酯的简便合成

报道了一种生物聚合物材料的重要单体四乙基-D-葡萄糖酸-1,6-内酯的简便合成方法。室温下以工业原料D-葡萄糖酸-1,5-内酯为起始物,在三苯氯甲烷、吡啶溶液中反应得到三苯甲基保护6-羟基的葡萄糖酸内酯,后者在w(KOH)=30%的甲醇溶液中断裂内酯键,所得葡萄糖酸盐溶于二甲亚砜,0℃时加入氢化钠(12倍摩尔)、溴乙烷(11倍摩尔),25℃搅拌3 h,得6-O-三苯甲基-2,3,4,5-O-四乙基葡萄糖酸乙酯,三步收率40%,后者在V(乙酸)/V(水)=4溶液中70℃反应2 h脱去6-三苯甲基,KOH水溶液中水解除去乙酯键、w(HCl)=5%的盐酸酸化得到重要中间体D-四乙基葡萄糖酸(Ⅵ),最后经双环己基碳化二亚胺(DCC)、4-二甲氨基吡啶(4-DMAP)、4-二甲氨基吡啶盐酸盐(4-DMAP.HCl)脱水成环合成了目标化合物。对上述合成路线进行了优化,羟基的乙基保护反应中,加入过量氢化钠(23倍摩尔),反应结束后加入甲醇和水,所得强碱性溶液断裂乙酯键,产物脱去三苯甲基得到化合物(Ⅵ),实现了羟基保护和羧基脱保护一步法合成,减少了分离提纯步骤。产物结构经核磁共振表征。     

N-(α-苯氧基)十四酰牛磺酸钠的合成

以α-溴代十四酸乙酯、苯酚、牛磺酸为原料,经W illiam son醚化,水解,催化酰化等反应制备了一种芳氧基作疏水基团支链的牛磺酸盐类表面活性剂,即N-(α-苯氧基)十四酰牛磺酸钠(SPTT)。研究了W illiam son醚化制备α-苯氧基十四酸乙酯的反应条件,考察了几种常用酰化方法对于合成N-(α-苯氧基)十四酰牛磺酸钠的可行性。研究结果表明,醚化反应的最佳条件为:n(α-溴代十四酸乙酯)∶n(苯酚)∶n(K2CO3)=1.05∶11∶,DMF为溶剂,用苯回流分水3 h,α-苯氧基十四酸乙酯的收率为78.3%;合成N-(α-苯氧基)十四酰牛磺酸钠(SPTT)的最佳方法是催化酰化法,即在二环己基碳二亚胺(DCC)和N-羟基丁二酰亚胺(NHS)的催化下,α-苯氧基十四酸与牛磺酸及碳酸钠反应,n(α-苯氧基十四酸)∶n(DCC)∶n(NHS)∶n(牛磺酸)∶n(碳酸钠)=1∶1∶1∶1.5∶1.5,收率为72.3%。中间体及产物经FTIR,1HNMR,ESI-MS等表征,符合结构特征。     

4,4,4-三苯基-1-丁烯的合成

以烯丙基溴为原料,在N2保护下,乙醚中与镁反应30 m in制得烯丙基溴化镁的乙醚溶液(Ⅰ)。过滤后,将Ⅰ从45℃逐步加热到65℃,蒸出乙醚。然后快速加入四氢呋喃(THF),65℃搅拌20 m in,制得烯丙基溴化镁的THF溶液(Ⅱ)。在冰浴中向Ⅱ缓慢滴加氯代三苯甲烷的THF溶液,搅拌3 h,制得4,4,4-三苯基-1-丁烯(Ⅲ),收率93%。用红外光谱、核磁共振氢谱和碳谱对产物进行了表征。     

氨噻肟酸的合成

4-氯乙酰乙酸乙酯经亚硝酸异丙酯肟化、硫脲环合一步反应制得去甲氨噻肟酸乙酯。反应条件为:n(4-氯乙酰乙酸乙酯)∶n(亚硝酸异丙酯)=1∶1.05,肟化反应温度为10~12℃,肟化反应、环合反应时间分别为22、3.5h。去甲氨噻肟酸乙酯经甲基化、水解反应后得到氨噻肟酸,总收率46.3%(以4-氯乙酰乙酸乙酯计)。产物经1HMNR表征,符合结构特征。     

活性焦基固体酸的制备及其催化酯化性能

以新疆淖毛湖提质长焰煤与废旧橡胶粉共热解半焦为炭源,经过磷酸-水热耦合活化、磺化两步处理后,制备了固体酸催化剂。以乙醇乙酸酯化反应中乙酸的转化率为催化性能指标,探究了活化条件、磺化条件对所制固体酸催化性能的影响。结果表明,在活化温度448K,质量分数48.73%(下同)磷酸溶液中活化3h得到活性焦,在423 K磺化1 h后得到固体酸催化剂,其酸量达7.2 mmol/g,其中,—SO_3H为1.30 mmol/g;在固体酸催化剂质量分数为9.5%、V(乙醇)∶V(乙酸)=2∶1、反应时间30 min条件下,乙酸转化率达81.98%,催化剂重复使用5次,仍能保持较高催化活性。     

多肽合成中氨基酸活化酯的制备研究

氨基酸活化反应对合成多肽的产率及纯度具有重要影响。以芴甲氧羰基-缬氨酸为研究对象,首次采用反相高效液相色谱法检测活化反应过程,建立了芴甲氧羰基-缬氨酸活化酯的分析方法,优化了氨基酸活化酯的制备条件,并引入了新的用于Fmoc策略合成多肽的溶剂体系——四氢呋喃。结果表明:溶剂和活化试剂对活化酯的产率影响显著;活化酯制备的最佳反应条件为n(Fmoc-Val-OH)∶n(HOBt)∶n(DCC)=1∶1∶1.2,溶剂为THF,反应温度为25℃。     

多氧取代环己基甲醇苯甲酸酯的合成及其表征

以莽草酸为原料,经酯化、丙酮叉保护顺式邻二羟基、叔丁基二甲基硅烷保护羟基、还原、羟基酯化、最后双羟基化反应,得到多氧取代环己基甲醇苯甲酸酯(1),总产率为84.1%,其结构经IR、1H NMR和HR MS确证。对双羟基化反应的条件进行了探索,优化条件为:反应时间为15h,溶剂为THF∶H2O=1∶1(V∶V),配料比为n[(3R,4R,5R)-5-叔丁基二甲基硅氧基-3,4-(丙酮叉二氧)-环己基-1-烯烃-1-甲醇苯甲酸酯(5)]∶n(N-甲基吗啉氮氧化物)∶n(OsO4)∶n(手性配体)=100∶150∶0.5∶1,产率为90.6%,e.e.值为75.1%。     

D-呋喃木糖酯类化合物的合成及其在单料烟中的应用

利用二环己基碳二亚胺(DCC)作缩水剂,4-二甲氨基吡啶(DMAP)为催化剂,以1,2-O-异丙叉基-α-D-呋喃木糖和11种酸为原料,合成了11种具有潜在香味的木糖酯类化合物,结构经1H-NMR、13C-NMR、IR和HRMS图谱检测得到验证,并进行了卷烟加香试验.评吸结果表明,合成的该系列化合物可以提高卷烟烟气的香...     

Synthesis of polylactide/poly(ethylene glycol) diblock copolymers with functional endgroups

Amphiphilic polylactide/poly(ethylene glycol) (PLA–PEG) diblock copolymers with functional groups at the PEG chain ends were synthesized by coupling PLA and PEG homopolymers using different coupling agents. PLA precursors with different endgroups were synthesized by ring‐opening polymerization of l ‐lactide in the presence of different initiators such as octanol, acetic acid or benzoic acid, or water, using non‐toxic zinc lactate as catalyst. The mechanism of the ring‐opening polymerization of lactide initiated by carboxyl groups was investigated and discussed in comparison with the literature. N,N'‐carbonyldiimidazole was used to couple the two hydroxyl groups of PLA and PEG, using 4‐dimethylaminopyridine (DMAP) as catalyst. Dicyclohexylcarbodiimide (DCC) and DMAP were adopted to couple the carboxyl group and the hydroxyl group of PLA and PEG, respectively, while DCC and N‐hydroxysuccinimide were used to connect PLA and PEG by coupling their carboxyl and amine groups. Comparison of different coupling routes shows that the DCC/DMAP one exhibits the highest efficiency. A common tumor targeting ligand, folic acid, was attached to PLA–PEG with hydroxyl endgroups using the DCC/DMAP route. The resulting PLA–PEG copolymers bearing folic acid present great interest for targeted delivery of anti‐cancer drugs. © 2012 Society of Chemical Industry     

Synthesis and characterization of a poly(acrylic acid)‐graft‐methoxy poly(ethylene oxide) comblike copolymer

A methoxy poly(ethylene oxide) (MPEO) grafted poly(acrylic acid) (PAA) comblike copolymer was synthesized by the direct condensation of MPEO onto the PAA backbone in the presence of dicyclohexyl dimethylcarbodiimide (DCC) and 4‐dimethylaminopyridine (DMAP). Its chemical structure was characterized by Fourier transform infrared and ¹H‐NMR spectroscopies. The effects of different catalysts, solvents, reaction temperatures, and reaction times on the grafting degree of the PAA‐g‐MPEO comblike copolymer were investigated. Compared to p‐toluene sulfonic acid, DMAP/DCC as a catalyst markedly increased the grafting degree. The optimum reaction conditions were a tetrahydrofuran/water mixture solvent, a reaction temperature of 50°C, and a reaction time of 168 h. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

亚油酸去氧氟尿苷酯的合成与表征

采用DCC/DMAP催化剂,亚油酸（LA）与去氧氟尿苷（FUdR）酯化合成亚油酸去氧氟尿苷酯。其反应条件为：底物摩尔比n（LA）∶n（FUdR）=1∶1.2,室温反应18 h。用硅胶柱层析分离方法,以V（石油醚）∶V（乙酸乙酯）=3∶1溶剂体系作流动相分离得到目标产物,并用核磁共振及质谱对其表征。结果表明,目标产物为亚油酸去氧氟脲苷酯。     

扶素康的固相化学合成

研究了36肽扶素康的9-芴甲氧羰基(Fmoc)法固相化学合成,包括Fmoc固相逐步化学合成和Fmoc固相片断缩合化学合成。在片段缩合中,研究了多肽片断的分段策略、片断缩合溶剂、片断缩合剂对片断缩合法合成扶素康质量的影响,确立了优化的片段缩合工艺条件为：将扶素康按残基1～10、11～20、21～25、26～36分作4段;以王树脂为固相载体;HATU /HOAt/DIEA为缩合剂(4倍过量);DMF/DCM(1∶1)为反应溶剂;每步加入的全保护肽段为1.5倍过量;缩合及脱保护完成后以DCM为洗涤溶剂洗涤5次,进行固相片段缩合反应。该条件下合成的扶素康,粗品收率达67.31%,按标准曲线定量分析其纯度达38.75%。     

9＇-取代吲哚啉螺噁嗪衍生物的合成与光谱性质

将2个9’－羟基吲哚啉螺萘并噁嗪衍生物（Ia、Ib）,进一步以N,N’－二环己基碳二酰亚胺为脱水剂、4－二甲氨基吡啶为催化剂合成了2个9’－丙烯酰氧基吲哚啉螺萘并噁嗪衍生物（IIIa,IIIb）和2个9’－（α－呋喃丙烯酰氧基）吲哚啉螺萘并噁嗪衍生物（Va,Vb）。通过元素分析、^1HNMR和IR对产物的结构进行了表征。将化合物Ⅲa的乙醇溶液浸渍在脱脂棉上,经太阳光照射由无色变为蓝色;当脱脂棉移至阴暗处后,蓝色慢慢变淡消失。光致变色过程循环50次无异常发生,显示出良好的光致变色性能。     

Direct synthesis of poly(l-lactic acid) in supercritical carbon dioxide with dicyclohexyldimethylcarbodiimide and 4-dimethylaminopyridine

The direct synthesis of poly(l-lactic acid) (PLLA) from an l-lactic acid oligomer has been performed in supercritical carbon dioxide (scCO₂) using an esterification promoting agent, dicyclohexyldimethylcarbodiimide (DCC), and 4-dimethylaminopyridine (DMAP) as a catalyst. PLLA within M_n of 13,500 g/mol was synthesised in 90% yield at 3500 psi and 80 °C after 24 h. The molecular weight distribution of the products was narrower than PLLA prepared with melt-solid phase polymerisation under conventional conditions. Both DCC and DMAP showed high solubility in scCO₂ (DCC: 7.6 wt% (1.63×10⁻² mol/mol CO₂) at 80 °C, 3385 psi, DMAP: 4.5 wt% (1.62×10⁻²mol/mol CO₂) at 80 °C, 3386 psi) and supercritical fluid extraction was found to be effective at removing excess DMAP and DCC after the polymerisation was complete. We show that DCC and DMAP are effective esterification promoting reagents with further applications for condensation polymerisations in scCO₂.     

胸腺素α1的Fmoc固相合成法

本文用Fmoc固相方法合成了胸腺素α1。采用对碱敏感的Fmoc作为α -氨基的保护基 ,并确定与之配套的侧链保护策略。探索出了适宜的接肽方案 ,即前 9步接肽用对称酸酐法 ,后 1 8步用DCC -HOBt缩合法 ,从而保证了每步的高缩合率。试验结果表明各步的缩合率均在 96 2 %以上 ,多数达 99%以上。同时还对合成工艺条件进行了研究。合成粗品的纯度 (胸腺素α1的含量 )为 46 52 % (质量分数 ) ,胸腺素收率为 37 81 %     

胸腺素α1的DIC固相化学合成与鉴定

Thymosin α1 was synthesized manually. The washing condition and the test of the degree of coupling were studied. In addition, the analytical method of crude product was set up. Thymosin α1 was synthesized with the solid-phase method, by using the base-liable Fmoc group to protect the a-amino acid and N,N‘-diisopropylcarbodiimide (DIC) as the coupling regent. The crude product was analyzed by reversed-phase high performance liquid chromatography, SDS-PAGE and liquid chromatography/mass spectroscopy. The synthesis yield was 84.89%. The analytical results indicated that the crude product contained much thymosin α1, and the purity was 50.3%. DIC solid-phase chemical synthesis of thymosin α1 was applicable, and the yield was improved greatly compared to other known methods.     

离子液体中固体酸催化合成四氢呋喃和四氢吡喃衍生物

在固体酸SO4^2-／SnO2—Fe2O3或S2O8^2-／SnO2-Fe2O3或钨磷酸（H3PW12O40）催化下，由离子液体介质中不饱和醇出发，以高收率制得四氢呋喃和四氢吡喃衍生物。讨论了硫酸、对甲基苯磺酸、三氟甲基磺酸、固体酸SO4^2-／SnO2-Fe2O3或S2O8^2-／SnO2-Fe2O3或钨磷酸对反应转化率的影响。结果表明，在固体酸和离子液体催化体系中，利用不饱和醇成功地制得了四氢呋喃和四氢吡喃衍生物，收率达到90％以上，且反应体系可循环使用。