3-(5,5-二甲基-1,3-二(口恶)烷-2-基)-2-丁烯醛合成研究

以4-乙酰氧基-2-甲基-2-丁烯醛为原料,经醛基保护、酯交换、氧化合成3-(5,5-二甲基-1,3-二(口恶)烷-2-基)-2-丁烯醛.首次采用氯化亚铜协同TEMPO催化氧化2-(3-羟基-1-甲基-1-丙烯基)-5,5-二(口恶)甲基-1,3-二(口恶)烷,合成3-(5,5-二甲基-1,3-二(口恶)烷-2-基)-2-丁烯醛.初步研究了催化氧化反应机理,指明了催化氧化反应研究的方向.氯化亚铜协同TEMPO催化氧化α-烯醇合成α-烯醛,对于现代类胡萝卜素类药物和其他新药开发研究具有重要意义.     

维兰特罗关键手性中间体的合成工艺改进

(5R)-5-(2,2-二甲基-4H-1,3-苯并二氧杂环己烯-6-基)-1,3-唑烷-2-酮(Ⅰ)是合成维兰特罗的关键手性中间体。以2-溴-1-(2,2-二甲基-4H-1,3-苯并二氧杂环己烯-6-基)乙酮(Ⅱ)为原料,通过还原、胺化和成环反应得到目标产物的消旋体Ⅷ,然后再用L-(+)-酒石酸拆分得到目标产物Ⅰ,ee值为90%。产物结构经1HNMR确认。     

噁嗪草酮合成方法述评

总结了文献报道的噁嗪草酮及其中间体的合成工艺路线和具体的合成方法。噁嗪草酮是由关键中间体5-苯基-2,2,6-三甲基-2H,4H-1,3-二氧杂环己烯-4酮或者3-苯基乙酰乙酸乙酯与N-亚甲基-1-甲基-1-(3,5-二氯苯基)乙胺反应制得。主要有2条工艺路线。     

无溶剂超声辐射下琥珀酰亚胺磺酸镧催化合成3-取代吲哚衍生物

该文报道在琥珀酰亚胺磺酸镧催化下,吲哚、芳香醛和2,2-亚戊基-1,3-二口恶烷-4,6-二酮在无溶剂条件下经超声辐射合成了10个5-[(3-吲哚基)-芳甲基]-2,2-亚戊基-1,3-二口恶烷-4,6-二酮衍生物(3-取代吲哚衍生物)。当催化剂用量为3%(即其物质的量与吲哚物质的量的百分数,下同)时,30℃反应20~60 min,收率为82.4%~98.5%。此外,还探讨了琥珀酰亚胺磺酸镧的催化机理。该方法具有反应条件温和、反应时间短、底物普适性好、收率高及对环境友好等优点。催化剂回收利用4次仍然保持很高的催化活性。     

3-((E)- 2-丁烯酰基)- 1,3-(口恶)唑烷- 2-酮的合成

用一种新的方法合成了3-((E)-2-丁烯酰基)-1,3-(口恶)唑烷-2-酮,先用(E)-2-丁烯酸与二氯亚砜反应合成(E)-2-丁烯酰氯,再由(E)-2-丁烯酸与(E)-2-丁烯酰氯反应合成(E)-2-丁烯酸酐,最后把(E)-2-丁烯酸酐加入到三乙胺,无水LiCl,1,3-(口恶)唑烷-2-酮的无水四氢呋喃溶液中,在室温下反应5h,正己烷重结晶得3-((E)-2-丁烯酰基)-1,3-(口恶)唑烷-2-酮,产率80%.并确定了反应的最佳条件反应温度为25℃,反应时间为5h,催化剂无水LiCl与1,3-(口恶)唑烷-2-酮的摩尔比为1:1.     

除草剂氟酮磺隆中间体5-甲氧基-4-甲基-2,4-二氢-1,2,4-三唑-3-酮的合成

5-甲氧基-4-甲基-1,2,4-三唑-3-酮是氟酮磺隆的关键中间体。以硫氰酸钾和氯甲酸甲酯为起始原料,经三步反应得到目的产物。(1)以甲基异丁酮为溶剂,硫氰酸钠和氯甲酸甲酯、甲醇反应制得1,3-二甲基硫代亚胺二羟酸酯;(2)以上产物与水合肼环化制得5-甲氧基-2,4-二氢-3H-1,2,4-三唑-3-酮;(3)经硫酸二甲酯甲基化制得目的产物5-甲氧基-4-甲基-2,4-二氢-3H-1,2,4-三唑-3-酮(MMT)。分别考察了催化剂对1,3-二甲基硫代亚胺二羟酸酯,缚酸剂对5-甲氧基-2,4-二氢-3H-1,2,4-三唑-3-酮和pH值对5-甲氧基-4-甲基2,4-二氢-3H-1,2,4-三唑-3-酮收率的影响。产物总收率55.61%。     

5-烷基-2-(4-氰基苯基)-1,3-二噁烷的合成

对 5 烷基 2 (4 氰基苯基 ) 1,3 二 口恶烷的合成进行了研究 ,以 5 戊基 2 (4 氰基苯基 ) 1,3 二口恶烷的合成为例 ,论述了以溴代烷和丙二酸二乙酯为初始原料 ,采用相转移催化烃基化反应合成了 2 戊基丙二酸二乙酯 ,收率 91 7% ;进而以四氢铝锂和硼氢化钠为还原剂于 0～ 2 0℃在四氢呋喃溶剂中合成了 2 戊基丙二醇 ,收率≥ 80 % ;再与对氰基苯甲醛在催化剂氯化钙存在下反应合成了 5 戊基 2 (4 氰基苯基 ) 1,3 二 口恶烷 ,收率≥ 90 %。并通过核磁共振氢谱和红外光谱证实了其结构     

环状碳酸酯的合成及微波开环聚合研究

以2,2-二甲基-1,3-丙二醇和氯甲酸乙酯为原料合成了环状碳酸酯5,5-二甲基-1,3-二口恶烷-2-酮(DTC),并对DTC在食品添加剂乳酸锌引发下的微波开环聚合进行了研究.结果表明:在170 W的微波辐照下,辐照时间对聚合物的分子量有较大影响,当辐照时间为17 min时,聚合物的分子量达到最大,Mw、 Mn分别达到208 000和127 000.     

DL-3-甲基-1,4-二(口恶)烷-2,5-二酮的合成

聚羟乙酸、聚乳酸和羟乙酸-乳酸共聚物是一类重要的合成生物医用材料,具有良好的生物相容性和生物降解性,广泛用于临床和医药领域。1,4-二(口恶)烷-2,5-二酮1及其甲基同系物是制备这类生物医用高分子材料的单体,如3-甲基-1,4-二(口恶)烷-2,5-二酮2和3,6-二甲基-1,4-二(口恶)烷-2,5-二酮3。2和3因有手性碳原子,故存在对映体。1和3的合成已有许多报道。1一般由羟乙酸在氧化锑存在下脱水,经减压蒸馏而得。类似地,3由乳酸在氧化锌存在下脱水,经减压蒸馏制备。2的合成不同于1和3,迄今只有 Augurt 的专利报道。合成路线如下:     

维兰特罗关键中间体合成新方法

维兰特罗三苯乙酸盐(Vilanterol trifenatate)是由葛兰素史克公司(GSK)开发的长效β2受体激动剂。(R)-5-(2,2-二甲基-4H-1,3-苯并二氧芑-6-基)-1,3-噁唑烷-2-酮是关键中间体,文章基于已有的合成方法,提出一条新的路线。所得的目标化合物都经核磁共振氢谱确定结构,总收率达50%。     

聚醚改性硅油表面性质的研究

对实验室自制聚醚改性硅油(以下简称硅醚)的表面张力及浊点进行测定,并对其表面性质的特征及趋势进行了研究。结果表明,随硅醚质量浓度的增加,硅醚水溶液的表面张力值下降,硅醚质量浓度增至约0.01 g/L后,表面张力值降幅渐缓,其表面张力最低值为29~42 mN/m;随着硅醚侧链聚醚中环氧丙烷链段所占比例增加,其水溶液的浊点略有下降,质量浓度约为0.1 g/L的硅醚以侧链聚醚结构n(EO)∶n(PO)=1∶4的硅醚的浊点最小,为9.5℃;随体系温度上升,质量浓度约为0.01 g/L的硅醚水溶液的表面张力降幅小于同样质量浓度的甲基硅油加乳化剂A25(硬脂醇/脂肪醇醚-25)的水溶液,并求得质量浓度约为0.01 g/L不同环氧乙烷与环氧丙烷摩尔比的硅醚的表面张力随体系温度下降的系数及方程,根据实验建立的方程所得的某温度下表面张力的计算值与实测值之间的平均相对偏差为7%。     

Synthsis and properties of polyvinyl acetate emulsion copolymers by three novel non-ionic functional polyurethane surfactants

Functional polyurethane surfactants (tri-block) were synthesized by addition polymerization of hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI) and 2, 4-toluene diisocyanate (TDI) with poly (propylene oxide) (PPO) and monoallyl-end-capped poly (ethylene oxide) (PEO). The chemical structure of the polyurethane surfactants (PUS) was confirmed by Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopy. Then, a series of polyvinyl acetate (PVAc) latexes were successfully synthesized by the emulsion copolymerization in the presence of different PUS. The particle size, amount of coagulum and surface tension were evaluated. These polymeric surfactants were found to have excellent surface activity. The lowest surface tension of polyurethane surfactant aqueous solutions could be reduced to 41.5 dyn/cm for IPDI. All the polyurethane surfactants synthesized had low critical micelle concentrations and could reduce the surface tension even at very low concentration levels (10^?3–10^?2 molL^?1).     

含疏水侧链聚氨酯表面活性剂的制备及其乳液聚合应用研究

以异佛尔酮二异氰酸酯、二羟甲基丙酸和单硬脂酸甘油酯为主要原料,通过改变原料配比制备一系列含疏水侧链聚氨酯表面活性剂。采用FT-IR和~1H NMR对产物的结构进行了表征。以单体质量5%的聚氨酯表面活性剂制备了固含量(质量分数)为35%的聚甲基丙烯酸甲酯-co-聚丙烯酸丁酯乳液,研究了预聚物n(-NCO)/n(-OH)对表面活性和乳液聚合应用的影响。结果表明,当预聚物n(-NCO)/n(-OH)=1.07时,含疏水侧链聚氨酯表面活性剂水溶液具有最低表面张力值33.24 mN/m。该聚氨酯表面活性剂用于制备聚丙烯酸酯乳液可得到核壳结构乳胶粒子,当预聚物n(-NCO)/n(-OH)=1.11时,制备得到的乳胶粒子最小,直径约为75 nm。     

月桂醇聚醚及其消泡性能研究

以月桂醇为起始剂,在高压反应釜中通过控制加料次序制备了5种不同链段结构的分子量在1 000-1 200的聚醚。分别考察了这5种聚醚的表面张力、浊点与消泡性能之间的关系后发现,随着聚醚浊点温度的降低,其消泡性能基本呈升高趋势,而聚醚的表面张力并不对其消泡性能起决定性作用。     

Synthesis and solution properties of novel nonionic functional polyurethane surfactants

A series of novel nonionic functional polyurethane surfactants were synthesized by the polycondensation of 2,4‐toluene diisocyanate with poly(propylene oxide) (weight‐average molecular weight = 400, 1000, or 2000) and monoallyl‐end‐capped poly(ethylene oxide). The chemical structure of the polyurethane surfactants was determined by Fourier transform infrared and ¹H‐NMR, and the effects of the concentration, salt, rest time, and temperature on the surface tension were investigated. These polymeric surfactants exhibited excellent surface activity. Sample III, which was synthesized with monoallyl‐end‐capped poly(ethylene oxide) (number‐average molecular weight = 1000), poly(propylene oxide) (number‐average molecular weight = 2000), and tolylene diisocyanate, could reduce the surface tension to 37.6 mN/m at a concentration of 0.06 mol/L at 25°C. All polyurethane surfactants synthesized in this study had low critical micelle concentrations (ca. 10^?4 to 10^?5 mol/L) and could reduce the surface tension even at very low concentration levels. Moreover, the surface tension decreased with an increase in the temperature or the concentration of the polyurethane surfactants. The addition of salt resulted in a decrease in the surface tension, and it took some time for the polyurethane surfactants to reach a constant surface tension value. UV spectra were found to be very useful for determining the critical micelle concentration. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2956–2962, 2006     

硅烷偶联剂封端改性水性聚氨酯的研究

以聚醚多元醇(GE210)、异佛尔酮二异氰酸酯(IPDI)和α,α-二羟甲基丙酸(DMPA)为原料合成了基础聚氨酯(PU)预聚体,然后以1,4-丁二醇进一步扩链制得了水性聚氨酯(WPU)乳液,最后以偶联剂γ-氨丙基三甲氧基硅烷对PU分子进行封端,得到了稳定的改性PU乳液。通过对偶联剂的用量和封端条件等研究,确定了适合硅烷改性WPU的方式。实验结果表明,当w(硅烷偶联剂)=4%～5%时(占树脂的质量分数),硅烷偶联剂封端改性WPU乳液具有较低的表面张力,其胶膜的力学性能和耐水耐溶剂性能均相当优异。     

Preparation of water-soluble polyurethane surfactants

A novel series of water-soluble polyurethane surfactants has been prepared by the addition polymerization of 2,4 and 2,6-toluene diisocyanate 80 : 20%, respectively (TDI) to polyethylene glycol (PEG) and/or castor oil and ethylene glycol (EG). These water-soluble polyurethane surfactants have been found to exhibit excellent surface active properties including surface tension, foaming and wetting tendency, and formation of stable emulsions. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1531–1536, 1998     

Synthesis and characterization of cleavable surfactants derived from poly(ethylene glycol) monomethyl ether

A series of noncyclic acetal-linked cleavable surfactants were simply prepared by condensation of aldehydes with poly(ethylene glycol) monomethyl ethers. All of the products were characterized by¹H nuclear magnetic resonance. Their hydrophile-lipophile balance, surface tension, cloud point, critical micelle concentration, and foam height were determined. Hydrolysis kinetic studies, followed by gas chromatography, showed that they had higher hydrolytic reactivity in acidic solution than cyclic acetal-linked cleavable surfactants.     

Guerbet十四醇聚氧乙烯醚硫酸钠的合成与表面活性

以Guerbet十四醇 (C14 GA)为中间体 ,经Williamson反应合成Guerbet十四醇聚氧乙烯醚醇〔C14 GA(EO) nH ,n =1,2 ,4〕 ,再经氯磺酸酯化及NaOH中和 ,得到阴离子表面活性剂Guerbet十四醇聚氧乙烯醚硫酸钠〔C14 GA(EO) nS ,n =1,2 ,4〕。用IR、NMR和元素分析测定了所合成的表面活性剂的结构 ,并利用表面张力法测定了这些表面活性剂水溶液的表面活性。实验结果表明 :所合成的表面活性剂的结构分别为C14 GAEOS (A) ,C14 GA(EO) 2 S(B)和C14 GA(EO) 4 S(C) ;这些表面活性剂其临界胶束浓度CMC(mmol/L) ,在CMC时的表面张力γCMC(mN/m)和Krafft点 (℃ )分别为A :2 5 8mmol/L ,2 7 6mN/m ,5 9℃ ;B :0 80mmol/L ,2 6 4mN/m ,2℃和C :0 12mmol/L ,2 5 3mN/m ,0℃。均比常用的直链阴离子表面活性剂C12 H2 5SO4Na(8.6mmol/L ,4 1 2mN/m ,16℃ )有更低的CMC ,γCMC和Krafft点 ;聚氧乙烯基的引入 ,对降低CMC ,γCMC和Krafft点的效果随氧乙烯基团数目的增多 (由 1增至 4 )而加大。讨论了表面活性剂的结构和表面活性的关系     

Retracted: Synthesis,Characterization, and Surface Activities of Polymeric Cationic Thiol Surfactants in Aqueous Medium

A series of cationic polyurethane surfactants [PQ_8-18] were synthesized by the reaction of alkyl bromoacetate (namely: octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, and octadecyl bromoacetate) as quaternizing agents and modified polyurethane contains tertiary amine species. Modified polyurethane was prepared by the reaction of toluene diisocyanate (TDI) and triethanol amine monomercaptoacetate. The chemical structures of the prepared surfactants were confirmed using elemental analysis, Fourier transform infrared spectroscopy (FTIR), and Proton nuclear magnetic resonance (¹H NMR) spectroscopy. The molecular weight measurements of the prepared polymers showed that the segments of each polymer contain average 10 units of the urethane-triethanol amine mercaptoacetate. The surface activities of the prepared surfactants including: surface tension (γ), effectiveness ( π_cmc), concentration at micelle formation (CMC), efficiency (Pc₂₀), maximum concentration at the interface (Γ_max), and the average area occupied by each surfactant molecule at the interface at equilibrium ( A _min) of surfactants solutions were established at 25°C. The surface tension and the critical micelle concentration values of the prepared surfactants were gradually decreased by the gradual increase of their alkyl chain length. The prepared cationic surfactants showed efficient activity as inhibitors for dissolution of carbon steel in an acidic medium and also as a biocide against the growth of bacteria, fungi, and yeast.