One-pot synthesis of 2,5-bis(hydroxymethyl)furan from biomass derived 5-(chloromethyl)furfural in high yield

5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.

(Z)-2-(2-甲氧亚胺基)呋喃乙酸合成工艺研究

以2-乙酰呋喃为起始原料合成了(Z)-2-(2-甲氧亚胺基)呋喃乙酸,收率达86%,最佳肟化反应工艺条件:甲氧胺盐酸盐为1.8 eq,反应体系pH为3.0,温度为10℃,时间10 h,转化率99.13%,Z构型选择性92.63%。(Z)-2-(2-甲氧亚胺基)呋喃乙酸降解符合一级反应动力学,pH越低,降解越快。

Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts

The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.

Synthesis of 2-aryl-5-alkyl-7-methoxylbenzo[b]furan derivatives

A series of 2-aryl-5-alkyl-7-methoxylbenzo[b]furan derivatives have been synthesized by utilizing the coupling of methyl 3- methoxy-4hydroxy-5-bromocinnamate with cuprous phenylacetylide as the key step. The structures of the new compounds were confirmed by 1H NMR, IR and MS. The structure of compound 14 was further confirmed by single crystal X-ray. Compound 17 showed cytotoxic activity against human lung carcinoma A549.

2-FURFURYLKETONES FROM 2-(CHLOROMETHYL)FURAN AND LITHIUM TRIALKYLALKYNYLBORATES

2-(Chloromethyl)furan as an electrophile attacks lithium trialkylalkynylborates,followed by the oxidation with H_2O_2 under basic conditions to afford 2-furfurylketones in good yields.

2-苯基苯并[b]呋喃类化合物的Pin1抑制活性研究

本文选取了8个2-苯基苯并[b]呋喃类化合物,以糜蛋白偶联方法检测化合物对Pin1的抑制能力,在50 μmol/L浓度下8个化合物对Pin1酶均有一定的抑制作用,其中化合物b6、b7的抑制作用显著强于阳性对照胡桃醌,IC50值分别达0.658 μmol/L和0.800 μmol/L。以MTT法检测化合物b6、b7对肝癌细胞SK-Hep-1与SNU-423生长抑制活性,化合物b6的IC50值分别为70.40 μmol/L、90.35 μmol/L,化合物b7的IC50值分别为79.83 μmol/L、57.48 μmol/L。本研究获得一些具有较好Pin1抑制活性的2-苯基苯并[b]呋喃类化合物,可为抗肿瘤先导药物的研究提供参考。

Synthetic Studies of Naphtho[2,3-b]furan Moiety Present in Diverse Bioactive Natural Products

The preparation of several functionalized furan derivatives and attempts to transform them into a derivative containing 6H-furo[3,4-b]furanone skeleton towards the construction of naphtho[2,3-b] furan are described. Attempted Pummerer reaction of a furan sulfoxide derivative produced four interesting furan derivatives. Base promoted annulation between methyl 2-(phenylsulfinylmethyl)-3-furoate and 2-cyclohexenone proceeded to give dihydro naphtho[2,3-b]furanone derivative in a regiospecific manner.

Synthesis, Characterization and Bioactivity of 1,1-bis(2-Carbamoylguanidino)furan-2-ylmethane

This study reports the synthesis of 1,1-bis(2-Carbamoylguanidino)furan-2-ylmethane, characterisation and bioactivities on selected microorganism. The first step involves the coupling of furfural with urea to obtain 1-((2-carbamoylguanidino)(furan-2-ylmethyl)urea, which was subsequently refluxed with more urea in ethanol for 1 hour to afford the product. Both intermediate and product were characterized by GC-MS, IR, 1H-NMR, 13C-NMR. The synthesized compound1,1-bis(2-carbamoylguanidino)furan-2-ylmethane was bioactive on Escherichia coli, Salmomellatyphi and Bacillus subtilis to different extent and is inactive on Staphylococcus aureus. The presences of bioactive moieties and pharmacological activities have proved the potency of furfural derivatives in the development of novel drug in future.

Synthesis and Bioactivity of 1-((2-Carbamoylguanidino) (furan-2-ylmethyl)urea

1-((2-Carbamoylguanidino)(furan-2-ylmethyl)urea was synthesised by coupling purified furfural with urea. The compound was characterized by GC-MS, FTIR, and 1H-NMR. The pathogens, Escherichia coli, Salmonella typhi, Staphylococcus aureus and Bacillus subtilis were isolated and screened with different concentrations of 1-((2-carbamoylguanidino)(furan-2-ylmethyl)urea. All the pathogens were susceptible to the synthesized compound except Bacillus subtilis. Due to this broad spectrum of activity, 1-((2-Carbamoylguanidino)(furan-2-ylmethyl))urea) can be use for various medicinal purposes and is therefore encouraged for the development of a novel drug in future.

4-[(Furan-2-ylmethylene)-amino]-1,5-dimethyl-1,2-dihyl-1,2-dihydo-pyrazol-3-one

The title compound （C16H15N3O2, Mr= 281.31） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the C=N double bond. It crystallizes in the monoclinic system, space group P2 1/c with a = 11.150（3）, b = 9.906（3）, c = 13.624（4） A, β = 106.360（4）°, V= 1443.9（7） ,A^3, Z = 4, Dc = 1.294 g/cm^3, F（000） = 592,μ（MoKa） = 0.088 mm ^-1, R = 0.0577 and wR = 0.1214. Of the 5766 total reflections, 2540 were unique. In the molecule there exist two different planes of pyrazoline and O（2）-C（10） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0026 A） with the dihedral angle between them of 6.3°.

2-氨基乙基呋喃的合成

2-氨基乙基呋喃是一种重要的医药中间体。以糠醛和硝基甲烷为起始原料,经过缩合、双键加成及还原反应制备了2-氨基乙基呋喃,GC纯度大于99%,总收率为62.2%,其化学结构经MS、^(1)H NMR和^(13)C NMR确证。探讨了缩合反应中硝基甲烷的用量对化合物3收率的影响,当n(硝基甲烷)∶n(糠醛)=1∶1时,产物收率最高,达到82.6%。考察了硼氢化钠的用量对化合物4收率的影响,当n(硼氢化钠)∶n(化合物3)=2∶1时,产物收率最高,达到88.6%。考察了甲酸铵的用量对目标产物收率的影响,当n(甲酸铵)∶n(化合物4)=4∶1时,还原反应收率最佳,达到85.0%。实验结果表明此方法操作简单、反应条件温和、适用于工业化生产。

2-取代芳基苯并[b]呋喃类化合物的合成

以4-取代苯乙炔化亚铜与3-甲氧基-4-羟基-5-溴肉桂酸甲酯为原料进行缩合反应得到2-取代芳基并[b]呋喃,并将其衍生化,得到14个2-芳基-5-烷基-7-甲氧基苯并[b]呋喃化合物,并确证了其结构.

2,5-呋喃二甲酸的合成

以糠酸为原料,经过酯化、氯甲基化、水解、氧化得到2,5-呋喃二甲酸,并对各步反应中的工艺参数进行了优化。优化结果:酯化反应时间为10 h,氯甲基化反应温度为35～40℃,水解反应原料摩尔比为n(氢氧化钠)∶n(5-氯甲基-2-呋喃甲酸甲酯)=2.1∶1,氧化反应体系pH=7～8,反应总收率47.5%。按该工艺顺利完成了3次20 L扩试反应,平均收率可达47.3%,产品HPLC纯度大于99.4%。

2-取代芳基苯并呋喃类化合物生物活性及合成研究进展

综述了近十几年来报道的具有良好生物活性的 2-芳基苯并呋喃类化合物, 以及这一类化合物结构骨架的构建与合成方法.

糠醛气相催化加氢合成2-甲基呋喃的研究

采用所研制的ＦＳ－９０型Ｃｕ－Ｃｒ／Ａｌ２Ｏ３催化剂进行糠醛加氢合成２－甲基呋喃。研究了反应温度、压力、空速、氢／醛摩尔比对２－甲基呋喃收率的影响。２－甲基呋喃收率达９６．６％，经６００ｈ寿命试验，２－甲基呋喃收率在９０％以上，与常用的Ｃｕ－Ａｌ合金催化剂相比具有收率高、稳定、寿命长的特点。电镜测试结果表明，催化剂表面呈层状分布，有助于活性组份在层状结构上分布均匀；活性组份颗粒粒径呈窄分布，有助于提高选择性、稳定性和产品收率。

N-[5-(2-氯苯基)-2-呋喃甲酰氨基硫羰基]-L-α-氨基酸乙酯的合成与生物活性测定

设计并合成了9种未见文献报道的N-(5-邻氯苯基-2-呋喃甲酰氨基硫羰基)-L-α-氨基酸乙酯衍生物,其结构经IR,1HNMR,MS和元素分析测试确证.MTT法测试结果表明大部分目标化合物对白血病K562细胞系的增殖具有明显的抑制作用.

5-烷氧基-3,4-二卤-2(5H)-呋喃酮与α,ω-二胺的串联反应

在三乙胺作用下,亲核试剂α,ω-二胺与5-烷氧基-3,4-二卤-2(5H)-呋喃酮在室温下发生串联的迈克尔加成-消除反应,合成了16个新化合物.通过旋光度,UV-Vis,IR,HNMR,CNMR,MS,元素分析和X射线单晶衍射等表征方法,113确定了目标化合物的化学结构和绝对构型.

微波辐射下2-取代-5-(2-苯并呋喃)-1,3,4-噁二唑类化合物的合成与表征

在微波辐射条件下,以2-氯亚甲基-5-苯并呋喃-1,3,4-噁二唑为中间体,合成了一系列新的1,3,4-噁二唑类化合物.用元素分析,IR及1H NMR确证了其结构.

高锰酸钾法制备2,5-呋喃二甲酸

探索了以5-羟甲基糠醛为原料,用高锰酸钾法氧化制备标题化合物。以126 mg(1 mmol)5-羟甲基糠醛为定量,考察了高锰酸钾用量、碱溶液的浓度和反应时间对反应的影响。当高锰酸钾用量为379.2 mg(2.4 mmol),碱溶液的浓度为2.2 mol/L,反应时间为10 min时,得到标题化合物收率为76.3%。研究结果表明,高锰酸钾法制备标题化合物,是一种不用贵金属催化剂,在室温下就可反应的简便方法。

糠醛常压气相加氢制2-甲基呋喃催化剂的研究

在Φ2 5mm× 1 .5mm× 40 0mm的不锈钢固定床积分反应器中对Cu Cr/γ Al2 O3 催化剂进行活性测试 .研究反应温度、催化剂中Cu/Cr摩尔比、H2 /糠醛摩尔比对 2 甲基呋喃收率的影响 .当Cu/Cr摩尔比为 2 .4∶1、H2 /糠醛摩尔比为 4.61∶1、反应温度为 1 85～ 1 90℃时 ,糠醛转化率几乎达 1 0 0 % ,2 甲基呋喃选择性达 91 .83 % .对催化剂的X 射线衍射分析表明 ,催化剂的活性组份是Cu。,Cr与Cu相互作用形成CuCrO4,有助于提高活性组份Cu。 的分散程度 ,提高糠醛转化率及 2 甲基呋喃的选择性 .