Raney Ni催化生物基糠醛还原胺化合成糠胺

生物质衍生物糠醛还原胺化是合成糠胺的一种有效方法。本文以糠醛为原料、氨水为氨源,使用商业Raney Ni催化糠醛还原胺化合成糠胺,考察了氢压、温度、n(糠醛)/n(氨水)、溶剂、催化剂用量等条件对反应的影响。实验结果表明：在1,4-二氧六环溶剂中,0.03 g Raney Ni、n(糠醛)/n(氨水)=1/2、130 ℃、2.0 MPa H₂条件下反应3 h,糠醛转化率100%,糠胺选择性96.3%。与传统方法相比,该工艺实现了非贵金属催化剂作用下高选择性反应,具有操作简单、低成本、收率高等优点。      

水杨醛缩糠胺合钴（Ⅲ）配合物的合成,表征与晶体结构

合成了水杨醛缩糠胺合钴（Ⅲ）配合物Co（SF）3[HSF=水杨醛缩糠胺Schiff碱],通过IR和单晶X射线衍射测定了其结构.配合物属三斜晶系,空间群P墿,晶体学参数a=0.900 64（8）nm,b=1.061 13（9）nm,c=1.636 23（14）nm,α=93.989 0（10）°,β=94.886 0（10）°,γ=93.627 0（10）°.分子式C36H30CoN3O6,V=1.550 5（2）nm3,Z=2,Dc=1.413 g/cm3,F（000）=684,R1=0.0350,wR2=0.0958[I〉2sigma（I）],S=1.068.在配合物分子中,Co原子处于三个N原子、三个酚O原子形成的变形八面体场中.     

Asymmetric Synthesis of N-（Diphenylphosphinyl）furfurylamine by the Enantioselective Alkylation of Furfurylimine

Optically active N-（diphenylphosphinyl）furfurylamines 2 with good ee values were obtained by the enantioselective addition of dialkylzincs to furfuryl imine 1 in the presence of chiral aminoalcohol derivatives and oxazolines.     

N-（4-羟基-3-甲氧基苯基亚甲基）糠胺的室温固相合成、晶体结构及二阶非线性光学性质的理论计算

糠胺与香草醛通过室温固相反应合成N-（4-羟基-3-甲氧基苯基亚甲基）糠胺 （C_(13)H_(13)NO_3,M_r = 231.24），用元素分析，IR，~1H NMR和X射线粉末衍 射谱对产物进行了表征，并用X射线单晶衍射法测定了化合物的晶体结构。结果表 明，该晶体属正交晶系，空间群P_2_12_12_1，a = 1.0148(2) nm, b = 1.0806(2) nm, c = 1.0937(2) nm , V = 1.1993(4) nm~3, D_c = 1.281 g/cm~3, Z = 4, F(000) = 488, μ(Mo Kα) = 0.092 mm~(-1), R = 0.0448, wR = 0.1320。用 AM1和INDO-CI方法研究了标题化合物的结构和电子光谱，并在此基础上应用完全态 公式（SOS）采用自编程序计算了二阶非线性光学系数。     

Crystal Structure and Inhibitory Activity against Xanthine Oxidase of Bis（μ2- chloro）-chloro-（μ-N,N＇-（2-pyridylmethylene） Furanmethanoamine Copper（II） Complex

A chloro-bridged dinuclear copper（H） complex with ligand 2-pyridylme-thylene- furfurylamine has been synthesized and characterized by single-crystal X-ray diffraction, and its inhibitory activity on xanthine oxidase （XO） was also evaluated. It crystallizes in the triclinic system, space group P 1 with a = 8.0441（16）, b = 8.5663（17）, c = 10.060（2）A, α = 77.52（3）, β = 72.04（3）, γ = 70.12（3）°, V = 615.3（2）A^3, Z = 1, Dc = 1.731 g/cm^3, F（000） = 322, the final R = 0.0401 and wR = 0.0934 for 1971 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Cu（II） cation is five-coordinated by two N atoms of Schiff base and three Cl anions. The C-H…Cl intermolecular and intramolecular hydrogen bonds connect the molecules to form a three-dimensional network. This copper（II） complex shows more potent inhibitory activity against XO with IC50 = 3.48μM than the standard inhibitor allopurinol.     

Synthesis and thermal properties of a bio‐based polybenzoxazine with curing promoter

A fully bio‐based benzoxazine, 3‐furfuryl‐8‐methoxy‐3,4‐dihydro‐2H‐1,3‐benzoxazine (Bzf), has been prepared using guaiacol, furfurylamine, and paraformaldehyde as raw materials. Its chemical structure has been characterized by 1H and 13C NMR, FTIR, and elemental analysis. The polymerization behavior of Bzf in the presence of methyl p‐toluenesulfonate (PTSM) has been studied by FTIR and DSC, and the thermal stability of the cured resin has been evaluated by thermogravimetric analysis. It was found that PTSM is a good promoter that serves to avoid thermal decomposition of the bio‐based monomer during the curing process at high temperature. In contrast to the situation with neat Bzf, the presence of PTSM (5 mol % for Bzf) significantly improves the polymerization behaviors, including a decrease in the polymerization temperature from 240 to 174 °C, a shortening of the time required to reach the gel point on heating at 200 °C from 47 to 20 min, and an increase in the char yield of the cured resin from 53 to 62%. Moreover, these observed experimental results on the promoting effect of PTSM are interpreted in terms of several possible mechanistic schemes, which involve a catalytic effect on the dissociation of C? O bonds in both the coordination ring‐opening reaction and the rearrangement from a phenoxy structure to a phenolic structure. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Directed molecular recognition: furfurylamine appended ditopic receptor for succinic acid

A furfurylamine appended ditopic receptor (R1) for dicarboxylic acids has been designed and synthesised. The association constants (K_a) between receptors and dicarboxylic acids have been determined using UV–vis and NMR titration techniques. The binding constant (K_a) of succinic acid with R1 was observed maximum, which implies the optimum chain length selectivity for succinic acid. Theoretical calculation and molecular modelling using Gaussian 03 program also support the optimised receptor's cavity for succinic acid.     

The chemical effect of furfuryl amide on the enhanced performance of the diphenolic acid derived bio-polybenzoxazine resin

As a renewable chemical, diphenolic acid (DPA) has attracted immense interest in bio-based polymer science. However, its application for polybenzoxazines is limited due to decarboxylation, that is, the release of CO₂ during the curing reaction of benzoxazine. In this study, the amidation strategy of converting DPA to diphenolic amides (DPAM) was demonstrated to solve this problem while simultaneously improving the thermal properties of polybenzoxazine. DPA was amidated by separately using four amines (hexamine, cyclohexylamine, furfurylamine, and aniline), then reacted with furfurylamine and paraformaldehyde to synthesize their benzoxazine monomers. By using TGA and DMA, all amide-containing polybenzoxazines were found to exhibit excellent thermal stabilities. Among all of the benzoxazine resins, poly(DFA-fa), which was obtained from amidation with furfurylamine, exhibited the highest glass transition temperature (T_g) of 310°C and a decomposition temperature (T_d10) of 406°C. Furthermore, a possible post-curing reaction mechanism was proposed to explain the outstanding thermal performance of poly(DFA-fa) resin. This study proposes an innovative strategy to solve the decarboxylation of DPA-based polymers, which is of significance for high-performance bio-based polymers.     

Post‐functionalization of perfluorophenyl ester‐functional acyclic diene metathesis polymer

The acyclic diene metathesis (ADMET) polymerization was utilized for the design of the ADMET polymer (M_n = 21,200 g/mol, M_w/M_n = 1.74) with pendant perfluorophenyl ester functionality using Grubbs first generation catalysis overnight in bulk at 80 °C. Next, a wide variety of functional groups, like benzyl, octyl, propargyl, allyl, and furfuryl was quantitatively incorporated to the ADMET polymer backbone through various amines using activated ester substitution reaction. The ADMET polymers studied in this work were characterized using ¹H, ¹³C, and ¹⁹F NMR, GPC and DSC and displayed a monomodal distribution and a rather broad polydispersity index in the range of ?1.33 to 1.90. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2593–2598     

两种含杂环的氨基萘醌化合物的合成

以2,3-二氯-1,4-萘醌为主要原料,分别与吗啡啉和糠胺在一定条件下反应生成2种含杂环的氨基萘醌类化合物。2,3-二氯-1,4-萘醌与吗啡啉及2,3-二氯-1,4-萘醌与糠胺物质的量比均为1∶2,反应温度为60℃,溶剂为乙醇。2,3-二氯-1,4-萘醌与吗啡啉反应时间为1 h,产物2-氯-3-吗啡啉基萘-1,4-二酮(a)收率为93.5%;2,3-二氯-1,4-萘醌与糠胺反应时间为4 h,产物N~2,N~3-二(2-呋喃甲基)-1,4-二((2-呋喃甲基)亚胺)-1,4-二氢化萘-2,3-二氯化铵(d)收率为46.7%。对产物进行IR、Uv、MS和H-NMR等分析表征。