环氧树脂/氨酯丙烯酸酯树脂互穿聚合物网络生成动力学研究

用ＦＴＩＲ跟踪研究了由不同分子量聚氧化丙烯（ＰＰＯ）合成的氨酯丙烯酸酯树脂（ＵＡＲ）／环氧树脂（ｅｐｏｘｙ）同步互穿网络（ＳＩＮ）的生成动力学．结果表明,在聚合反应初期（转化率＜０４）环氧基和不饱和双键的转化率均和反应时间呈近似线性关系,聚合反应主要由单体的扩散控制;由不同分子量ＵＡＲ合成的ｅｐｏｘｙ／ＵＡＲＳＩＮ的生成动力学有较大差异,与ＳＩＮ形成过程中的形态发展有关．通过不同用量的ＡＩＢＮ,可以调节ＵＡＲ网络的形成速度,导致ＳＩＮ中两个网络的生成顺序发生改变．     

含有偶氮染料侧基的聚氨酯（脲）的研究

用扩链法合成了一系列含有偶氮染料的侧基聚氨酯和聚脲。ＴＦ－ＩＲ、ＤＳＣ、ＤＭＡ的研究表明，聚合物有良好的力学性能，样品中软硬段的含量决定材料的物理性能。通过ＵＶ的测定，计算出样品均有较高的三阶非线性光学（ＮＬＯ）系数。     

5，14－二氢－6，8，15，17－四甲基二苯并［b，i］［1，4，8，11］四氮杂［14］轮烯金属配合物的合成和反应性研究

合成了二苯并四氮杂［１４］轮烯金属配合物ＴＭＴＡＡＮｉ（Ⅱ），ＴＭＴＡＡＣｕ（Ⅱ）和ＴＭＴＡＡＶ＝Ｏ，通过ＴＭＴＡＡＭ（Ⅱ）分子中金属离子Ｍ（Ⅱ）对位碳原子上发生酰化反应，获得了十个酰化产物，用元素分析，ＩＲ，ＵＶ，１￣ＨＮＭＲ，（１９）￣ＦＮＭＲ和ＥＰＲ等进行了表征。酰化反应的发生说明了这类金属配合物具有类芳香性，并为改善这类大环金属配合物的光－电性能提供了良好的途径。     

以混合模板剂合成TS—1分子筛及其性能研究

以四丁基溴化铵（ＴＢＡＢｒ）＋四乙基氢氧化铵（ＴＥＡＯＨ，ｎ（ＴＢＡ＾＋）／ｎ（ＴＥＡ＾＋）＝１）或以四丙基溴化铵（ＴＰＡＢｒ）＋ＴＥＡＯＨ为模板剂，钛酸四丁酯和正硅酸乙酯为原料，于１７０℃水热合成出ＴＳ－１分子筛。对合成的ＴＳ－１样品进行了ＸＲＤ，ＦＴ－ＩＲ，ＳＥＭ和ＢＥＴ比表面积分析，证实了样品中钛已进入Ｓｉｌｉｃａｌｉｔｅ－１骨架。选择戊烷氧化为探针反应，考察了ＴＳ－１的催化活性。结果表明以     

IN－SITU FTIR AND UV－VISIBLE－NEAR－IR SPECTROELECTROOHEMICAL STUDIES OF MIXED－VALENCE ISOPOLYANION Mo＿6O＿（19）￣（3－） IN APROTIC MEDIA

ＩＮ－ＳＩＴＵ　ＦＴＩＲ　ＡＮＤ　ＵＶ－ＶＩＳＩＢＬＥ－ＮＥＡＲ－ＩＲ　ＳＰＥＣＴＲＯＥＬＥＣＴＲＯＯＨＥＭＩＣＡＬ　ＳＴＵＤＩＥＳ　ＯＦ　ＭＩＸＥＤ－ＶＡＬＥＮＣＥ　ＩＳＯＰＯＬＹＡＮＩＯＮ　Ｍｏ＿６Ｏ＿（１９）￣（３－）　ＩＮ　ＡＰＲＯＴＩＣ　Ｍ...     

La(ClO4)3-OCBAAP-H2O体系(30℃)溶度及Ln(OCBAAP)4(ClO4)3·nH2O的合成和表征

测定了三元体系Ｌａ（ＣｌＯ４）３－ＯＣＢＡＡＰ－Ｈ２Ｏ在３０℃时的溶解度．结果表明，该体系有一个新固相（不一致溶解化合物）Ｌａ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３·６Ｈ２Ｏ形成．参考该体系溶度图确定合成条件，合成了系列化合物Ｌｎ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３·ｎＨ２Ｏ（Ｌｎ＝Ｌａ，ｎ＝６；Ｌｎ＝Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｙｂ，ｎ＝２）．通过化学分析、元素分析、ＴＧ－ＤＴＧ、ＩＲ和密度对化合物进行了表征，计算了Ｌａ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３热分解过程各阶段的表观活化能．     

DIRECT FORMATION OF TETRAQUINANE SKELETON BY INTRAMOLECULAR ARENE－OLEFIN meta－CYCLOADDITION

ＤＩＲＥＣＴＦＯＲＭＡＴＩＯＮＯＦＴＥＴＲＡＱＵＩＮＡＮＥＳＫＥＬＥＴＯＮＢＹＩＮＴＲＡＭＯＬＥＣＵＬＡＲＡＲＥＮＥ－ＯＬＥＦＩＮｍｅｔａ－ＣＹＣＬＯＡＤＤＩＴＩＯＮ￥ＣｏｎｇＺＨＡＮＧ；ＳｏｎｇＦｕＷＵａｎｄＸｉａｏｃｈｕａｎＧＵＯ（Ｉｎｓｔｉｔｕ...     

IN SITU FT－IR OF SiO_2－SUPPORTED Pt－Mo HETEROBINUCLEAR METAL CARBONYL HYDRIDE CATALYST FOR CO HYDROGENATION

ＩＮＳＩＴＵＦＴ－ＩＲＯＦＳｉＯ_２－ＳＵＰＰＯＲＴＥＤＰｔ－ＭｏＨＥＴＥＲＯＢＩＮＵＣＬＥＡＲＭＥＴＡＬＣＡＲＢＯＮＹＬＨＹＤＲＩＤＥＣＡＴＡＬＹＳＴＦＯＲＣＯＨＹＤＲＯＧＥＮＡＴＩＯＮ￥ＣｈａｎｇＰｉｎｇＳＨＡＯ（ＤＡＬＩＡＮＩｎｓｔｉｔｕｔｅｏ?..     

A CONVENIENT METHOD FOR SYNTHESIZING AND CHARACTERIZATION OF （Z）－ALKENOLS AND THEIR ACETATES

ＡＣＯＮＶＥＮＩＥＮＴＭＥＴＨＯＤＦＯＲＳＹＮＴＨＥＳＩＺＩＮＧＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦ（Ｚ）－ＡＬＫＥＮＯＬＳＡＮＤＴＨＥＩＲＡＣＥＴＡＴＥＳ￥ＧｕＹＵＡＮ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＰｅｋｉｎｇＵｎｉｖｅｒｓｉ...     

FIRST SYNTHESIS OF(±)-3-[(5-HYDROXY)HOMOGERANYL]-△~2-BUTENOLIDE

ＦＩＲＳＴＳＹＮＴＨＥＳＩＳＯＦ（±）－３－［（５－ＨＹＤＲＯＸＹ）ＨＯＭＯＧＥＲＡＮＹＬ］－△￣２－ＢＵＴＥＮＯＬＩＤＥ￥ＪｉｎＱＵ；ＷｅｉＤｏｎｇＬＩ；ＪｉｎｇＬＩ；ＹｕＬｉｎＬＩ（ＳｔａｔｅＫｅｙＬａｂｏｒａｔｏｒｙｏｆＡＰＰｌｉｅｄＯｒｇａｎ...     

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.     

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.     

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.