A Study on Alkyl Polyglycosides of the Starch

The alkyl polyglycosides (APG) is new type the surfactants that is made by regenerationresource of the starch and the grease, since the nineties of 20th century it is energetically exploited ininternational extent. APG not only good in surface activity, but also plenty on bubble, thin greasyand stabilization, there are good decontamination, compatibility, innocuity, not incitation and uniquefunction that organism decomposition of swiftness and downrightness, and so on.APG is to get production that loses one molecule water with half condensation aldehyde hydroxyand sebum alcohol hydroxy under acid catalysis. The production not is one simplicity compound, butis one of sugar polymerization degree, so it is mixture of the alkyl single glucoside, the alkyl twoglucoside and the alkyl three glucoside.Author synthesizes the surfactants of the alkyl polyglycosides, with the oleaster and potato starchand sebum alcohol, that was chosen to use duality system activator of plant acid and p-toluene-sulfoacid for the first time. The adoption way is that the lower alkyl polyglycosides is firstly formed byreaction of lower alcohol with starch then exchanged with high alcohol to obtain APG. The study isto make certain most technics condition, determining capillary tension and the pastern sheafdeepness of critical, calculating HLB value, determining construction by 1R.To synthesize principium:Peroration :[1]Duality system activator of plant acid and p-toluene-sulfo acid is compare idea activator that was the lower alkyl polyglycosides is firstly formed by reaction of lower alcohol with glucose then exchanged with high alcohol to obtain high alkyl polyglycosides. The advantage is that it overcomes agglomeration, there is reaction entirety, high of sugar transform ratio, reaction time short.[2]Most good reaction temperature is 90～ 170℃, the dosage of activator is 0.5%～0.9%, the mated ratio: The APG of glucose basic butane ratio starch is 5:1, the APG of potato starch basic glycol ratio starch is 6:1, the APG of the oleaster starch basic glycol ratio starch is 12:1, the APG of the mealiest starch basic glycol ratio starch is 6:1, the product of complex is good property.[3]The alkyl polyglycosides is the products of surfactant. IR determines the functional group of the products. On the basis of group of the hydrophile and to close on oil, that the feature peak of α-1, 4- glucoside.[4]The capillary tension of the APG is 26.8～31.0mN/m, the HLB value is 16～18, the products is better emulsifying agent of water- solubility. (O/W).     

Synthesis and characterization of a new isocyanato carborane anion [7-OCN-7-CB10H12]; study on its reactivity toward amino containing compounds

The new isocyanato carborane anion, [7-OCN-7-CB₁₀H₁₂]⁻ was prepared by the reaction of 7-H₃N-7-CB₁₀H₁₂ with triphosgene in the presence of triethylamine. The structure of this compound was established by ¹H, ¹¹B and ¹³C NMR as well as IR spectroscopy. The reactivigty of this compound with a series of organic amines was investigated. The resulting ureas were obtained in good to excellent yields. This approach is suitable for development of compounds for use in tumor selective Boron Neutron Capture Therapy (BNCT).     

伯溴代烷的微波快速合成法

198 6年Ｒ .Ｊ.Ｇｉｇｎｅｒｅ[1 ] 和Ｒ .Ｇｅｄｙｅ[2 ] 首次报道将微波用于有机合成反应以来 ,大量实验事实证明[3] 微波不仅能极大地提高某些化学反应速率 ,而且能使一些在常规加热条件下几乎不能进行的反应得以完成、获得满意的收率。用伯醇在溴化氢溶液中微波条件下发生反应制备了伯溴代烷。1　实验部分ＷｈｉｒｌｐｏｏｌＴ1 2 0Ｘ微波炉 (四川大学无线电系改装 ,可连续发射微波 ,功率连续可调 )、ＷＺＳ -Ｉ阿贝折光仪 (未校正 )。工业溴化氢 (Ｃ =40 % ,ｄ =1 38) ,其余试剂均为ＣＰ级。合成通法　将适量的醇、一定量的浓硫酸和过…     

Synthesis of novel derivatives of 2-(azolylimino)thiazoline

Successive alkylation of 5-(3-phenylthioureido)-3H-imidazole-4-carboxamides with alkyl halides and chloroacetone gave (N-oxopropylimidazolyl)isothioureas, which were easily converted into derivatives of purine and imidazopyrazinone. In the case of ethyl 5-(3-phenylthioureido)-3H-imidazole-4-carboxylate, primary alkylation occurs at the N atom of the imidazole ring. Reactions of 5-(3-phenylthioureido)-3H-imidazole-4-carboxamides with haloketones afforded a number of 4-hydroxy-2-imidazolyliminothiazolidines and 2-imidazolylimino-Δ⁴-thiazolines.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2196–2204, October, 2004.     

Synthesis of substituted polymethylenes by radical polymerization of alkyl N,N-dialkylfumaramates and maleamates: Relative reactivity of the isomers

Bulk polymerization of alkyl N,N-dialkylfumaramates (FAE) and maleamates (MAE) was performed in the presence of a radical initiator. It has been found that FAE is more reactive than MAE when the reactivity of the two geometrical isomers was compared for their homo- and copolymerizations. From investigation on the effect of ester and N-substituents of these monomers, it has been found that the isopropyl ester shows a higher reactivity than the methyl ester and that N-ethyl and n-butyl substitution gives polymers with high molecular weight of more than several thousands. The resulting substituted polymethylenes from FAE and MAE were characterized and compared with each other. The isomerization of MAE to FAE with morpholine as an isomerization catalyst and monomer-isomerization radical polymerization were also investigated.     

From crown ethers to zeolites: Reaction of EtAlCl2 with crown ethers

In contrast to aluminum alkyls, alkyl aluminum halides such as EtAlCl₂ react with crown ethers to form cation-anion pairs which exhibit the liquid clathrate effect. Specifically, [12-C-4·AlCl₂][AlCl₃Et] and [18-C-6·AlCl₂][AlCl₃Et] have been isolated and characterized by X-ray diffraction techniques. The cations show aluminum in an octahedral environment made up of four of the oxygen atoms from the crown and two chlorine atoms. The 12-C-4 derivative crystallizes in the monoclinic space group P2₁/c with cell constants of a=7.497(4), b=22.121(8), c=12.339(5) Å, =94.99(3)^o, and Z=4 for =1.43 g cm^–3. Least-squares refinement based on 1413 observed reflections led to a final conventional R value of 0.093. The 18-C-6 complex belongs to the triclinic space group P1 with a=8.414(4), b=12.193(6), c=12.394(6) Å, =73.14(4), =86.07(4), =81.52(4)^o, and Z=2 for =1.45 g cm^–3. Refinement based on 2605 observed reflections led to R=0.063. The complex aluminum-containing species are related to a class of compounds called aluminoxanes.     

气相色谱法测定阳离子表面活性剂合成体系中脂肪烷基二甲基叔胺

选用HP-NINOWax毛细管色谱柱及氢火焰离子化检测器（FID），采用程序升温，建立了4种脂肪烷基二甲基叔胺的分析方法。结果表明，4种脂肪烷基二甲基叔胺质量浓度在0.005~1.0 g/L范围内，其峰面积与质量浓度有良好的线性关系，相关系数（R²）在0.9996以上。检出限（LODs，信噪比为3）在0.001~0.002 g/L之间，定量限（LOQs，信噪比为10）在0.003~0.005 g/L之间，回收率在90%~130%之间，相对标准偏差为1.3%~6.9%（n=6）。方法的线性范围宽、回收率高、选择性好，可用于叔胺的产品质量分析及生产过程控制分析。利用该方法对阳离子表面活性剂合成反应中十六烷基二甲基叔胺进行监测，结果很好地符合双分子亲核取代反应。该方法比滴定分析法更快速、精确，与液相色谱法相比，不需要进行柱前衍生或者使用色谱-质谱联用仪器。     

茂基稀土胺化物与异氰酸正己酯的反应-{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2的合成及表征

茂基稀土胺化物(MeCp)2YbNPh2(THF)与异氰酸正己酯(n-HexylNCO)按11摩尔比反应, 分离出产物{(MeC5H4)2Yb[OC(NPh2)N(n-hexyl)]}2. 产物经元素分析和核磁共振表征, 并测定了其晶体结构. 配合物属三斜晶系, R-3空间群, 晶胞参数为a=2.9533(11) nm, b=2.9533(11) nm, c=1.5873(6) nm, V=11.9896(80) nm3, Z=9, Dc=1.562 mg·m-3, μ=3.536 mm-1 (Mo Kα), F(000)=5670, R=0.034, Rw=0.064. 该化合物具有二个对称氧桥的双分子结构, 并存在着由氮原子向中心金属镱分子内配位而形成的三环骨架, 中心金属镱的配位数是九, 整个分子呈中心对称.     

Theoretical Study on the Reaction Mechanism of Ketene CH2CO with Isocyanate NCO Radical

The bimolecular single collision reaction potential energy surface of an isocyanate NCO radical with a ketene CH2CO molecule was investigated by means of B3LYP and QCISD（T） methods. The computed results indicate that two possible reaction channels exist on the surface. One is an addition-elimination reaction process, in which the CH2CO molecule is attacked by the nitrogen atom at its methylene carbon atom to lead to the formation of the intermediate OCNCH2CO followed by a C-C rupture channel to the products CH2NCO＋CO. The other is a direct hydrogen abstraction channel from CHzCO by the NCO radical to afford the products HCCO＋HNCO. Because of a higher barrier in the hydrogen abstraction reaction than in the addition-elimination reaction, the direct hydrogen abstraction pathway can only be considered as a secondary reaction channel in the reaction kinetics of NCO＋ CH2CO. The predicted results are in good agreement with previous experimental and theoretical investigations.     

Synthesis of Arylidene Derivatives of 1-Aryl-3H-pyrrol-2-ones

The aminolysis of 5-aryl-3-arylidene-3H-furan-2-ones by the action of aromatic amines leads to the formation of substituted amides of 4-oxo acids, the subsequent azacyclization of which in the presence of acetic anhydride leads to the formation of 1,5-diaryl-substituted 3-arylidene-3H-pyrrol-2-ones. The mechanism of the occurring and alternative transformations is discussed.