松香基琥珀酸双酯磺酸钠的合成及性质

以松香性产品歧化松香醇聚氧乙烯醚（RP）为原料合成了非离子表面活性剂歧化松香醇聚氧乙烯醚琥珀酸双酯磺酸钠（RPS）,研究了影响RP与马来酸酐（MA）的酯化反应及酯与NaHSO,磺化反应的各种因素,得出比较适宜的反应条件：酯化反应以对-甲苯磺酸作催化剂,其用量为RP质量用量的0．3％,反应温度130-140℃,n（RP）n（MA）=2：1,反应时间4h;磺化反应温度120-130℃,n（NaHSO3）：n（双酯）=1．1：1,反应时间4h。研究了合成产物的表面物理化学性质,结果表明：随着环氧乙烷（EO）聚合度（n）的增加,表面张力、钙皂分散力、乳化力先逐渐提高,临界胶束浓度和润湿力先逐渐减小,然后趋于平衡;RPS和RP相比,乳化力,泡沫性能及润湿力均有明显提高。     

腰果基表面活性剂的合成及其表面性质

以腰果酚为起始原料,合成了中间体腰果酚聚氧乙烯醚(CPE),进而在NaOH的催化作用下,由CPE和氯乙酸合成了系列腰果酚聚氧乙烯醚羧酸盐(CPEC)。采用红外光谱和元素分析技术对产物的结构进行了表征,用表面张力法研究了CPEC的表面性能。结果表明,该表面活性剂水溶液的临界胶束浓度(CMC)为9.30、8.50、8.10和7.71mmol/L,相应的临界表面张力为28.38、28.60、30.40和30.00mN/m。根据Gibbs公式得出表面活性剂在溶液表面的最大吸附量为0.7087、0.7350、0.7195和0.7346μmol/m2,表面活性剂的最小分子截面积为2.3439、2.2600、2.3087和2.2613nm2。     

腰果基表面活性剂的合成与表面性质

以腰果酚为起始原料,合成了中间体腰果酚聚氧乙烯醚（CPE）,进而在NaOH的催化作用下,由CPE和氯乙酸合成了系列腰果酚聚氧乙烯醚羧酸盐（CPEC）。 采用红外光谱和元素分析技术对产物的结构进行了表征,用表面张力法研究了CPEC的表面性能。 结果表明,该表面活性剂水溶液的临界胶束浓度(CMC）为9.30、8.50、8.10和7.71 mmol/L,相应的临界表面张力为28.38、28.60、30.40和30.00 mN/m。 根据Gibbs公式得出表面活性剂在溶液表面的最大吸附量为0.7087、0.7350、0.7195和0.7346 μmol/m²,表面活性剂的最小分子截面积为2.3439、2.2600、2.3087和2.2613 nm²。     

单一及复合表面活性剂对联苯菊酯微乳液的影响

通过对单一及复合型表面活性剂水溶液临界胶束浓度(CMC)和表面张力(γcmc)的测定分析,研究了表面活性剂对以水为介质、环己酮为溶剂形成的联苯菊酯质量分数为2.5%微乳液相行为及稳定性的影响.结果表明,在几种单一非离子表面活性剂中,苯乙烯基苯酚聚氧乙烯聚氧丙烯醚嵌段型非离子表面活性剂EPE的γcmc最低,为28.18 mN/m;按m(EPE):m(SDBS)=2∶1形成的复合型表面活性剂水溶液的γcmc更低,为27.60 mN/m,有利于O/W型微乳液的形成,当其质量分数为10%时,配制联苯菊酯质量分数为2.5%微乳液的有效成分热贮分解率为2.35%.     

阴离子孪连表面活性剂的合成及其表/界面活性研究

合成了疏水链长度不同和连接基长度不同的7种系列阴离子孪连表面活性剂,研究了它们的表/界面活性。结果表明,它们有较低的表面张力和临界胶束浓度(CMC),有很好的表面活性。它们的CMC都在10-5~10-6mol/L之间,表面张力在26·5~34mN/m之间。它们有非常好的抗一价、二价盐的能力。除了C16-C2-C16在高于5%的NaCl溶液中会产生析出外,其余孪连表面活性剂都能耐盐20%以上。随着盐浓度的增加,孪连表面活性剂与烷烃间的界面张力逐渐降低,能达到10-3mN/m。与中原油田原油间的界面张力能降低到10-3~10-4mN/m,表明它们可应用于特高矿化度油藏提高采收率。     

微乳液中脂肪酶和含明胶的微乳液凝胶中固定化脂肪酶的催化特性

在双2-乙基己基琥珀酸酯磺酸钠(AOT)油包水微乳液中Calytical脂肪酶催化月桂酸和戊醇的酯化反应动力学研究表明,反应符合乒乓(BiBi)机制.表观速率常数k_m酸=0.13518mol/L,k_m醇=0.22423mol/L,最大反应速度v_max=1.3873×10^-5mol/(L·min·mg).将该脂肪酶固定于含明胶的微乳液凝胶(MBGs)中,制得固定化脂肪酶,含酶MBGs在非极性溶剂中可作为固相催化剂,并研究了其在辛烷中催化酯化的性能.所制得的含酶MBGs物理稳定性好,重复利用10次以上,其转化率仍达初始转化率的90%.     

NPES/AOT反胶束增溶体系及性质研究

该文以壬基酚聚氧乙烯醚硫酸钠(NPES)与琥珀酸二(2-乙基己基)酯磺酸钠(AOT)复配体系为主表面活性剂,正丁醇为助表面活性剂,以柴油为油相,研究了反胶束增溶体系的粘度和电导率等物理化学性质;利用脉冲核磁共振图谱中水的T2弛豫时间分布曲线,研究了反胶束溶液中水的结合状态和分布,采用正规溶液理论计算了NPES/AOT的相互作用参数β值(-7.78),研究结果表明二者存在较强的协同效应,从理论上解释了二者在反胶束溶液中的最佳比例和协同增效作用.     

高分子表面活性剂P(AM-co-OPMA)的合成与表征

辛基酚聚氧乙烯醚(10)(OP-10)与马来酸酐在95℃下反应,合成了辛基酚聚氧乙烯醚马来酸单酯(OPMA);并在水溶液中与丙烯酰胺(AM)单体进行共聚合,获得了高分子表面活性剂P(AM-co-OPMA);考察了引发剂用量、单体组成、单体总浓度及反应温度对共聚物特性粘数与阴离子度的影响.通过红外光谱、紫外光谱、荧光发射光谱和电导滴定对共聚物结构和组成进行了表征;利用视频光学接触角测量仪分别测定了共聚物表面和界面张力.结果表明,在聚丙烯酰胺分子主链上引入OPMA链节后,不仅保持了PAM优良的增稠能力(特性粘数达764.31 mL/g),且赋予了共聚物较高的表面活性(浓度为1.5 g/L共聚物水溶液的表面和界面张力分别可达53.94 mN/m和5.41 mN/m).     

光-碱双重可降解阳离子表面活性剂的合成与性能

以香草醛、溴代十二烷、硝酸等为原料,通过O-烷基化、硝化、还原、酯化、成盐五步反应,合成了一种含邻硝基苄酯的可光-碱双重降解的吡啶盐阳离子表面活性剂.中间体与目标产物都进行了1H NMR结构表征;所得阳离子表面活性剂的临界胶束浓度(CMC)值约为0.3 mol·L-1.以该表面活性剂为乳化剂,进行苯乙烯乳液聚合可以得到稳定的乳液,表明该表面活性剂具有良好的乳化性能.将乳液进行紫外光照2h,可明显观察到乳液破乳并变色.经光降解测试证实该表面活性剂可在光作用下降解;发泡测试表明该表面活性剂具备一定的发泡性能;pH降解测试表明表面活性剂可在pH为7～9下实现碱降解.     

新型非离子性嵌段型聚氨酯表面活性剂的合成及其表面活性研究

本文以异佛尔酮二异氰酸酯、聚醚为主要原料,通过逐步聚合得到新型非离子性两、三嵌段型聚氨酯表面活性剂(Di/Tri-PUn),使用红外光谱及1HNMR对其结构进行了表征,并用表面张力仪对其表面活性进行了测定。实验结果表明,所制备出的六种非离子性两、三嵌段型聚氨酯表面活性剂均具有较低的临界胶束浓度(其中Di-PUn系列临界胶束浓度数量级可达10-6),产物Di-PU34水溶液在室温下的表面张力最低可达33.7mN/m,并且在浓度很低时仍具备较好的降低表面张力的能力。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.