中间体6-氯-5-甲氧基吲哚合成工艺研究

以3-氯-4-甲氧基苯胺和水合氯醛、盐酸羟胺为原料,通过Sandmeyer异亚硝基乙酰替苯胺合成法制备得6-氯-5-甲氧基靛红,再由硼氢化钠/三氟化硼乙醚体系还原制备得目标化合物,总收率达49.52%(以3-氯-4-甲氧基苯胺计)。实验考察了酰胺化反应温度和反应时间、成环反应温度、还原体系种类及还原剂用量对反应收率的影响,较佳的酰胺化反应温度和反应时间为90℃回流反应10 min,较优的成环反应温度为80~85℃,选用更加安全的硼氢化钠/三氟化硼乙醚体系作为还原剂,较优的还原剂用量比为n(硼氢化钠)∶n(三氟化硼乙醚)∶n(6-氯-5-甲氧基靛红)=4.0∶2.5∶1.0。所有产物结构均通过~1HNMR、~(13)CNMR和元素分析等进行了表征。     

α-乙酰氧基苯乙酮的合成研究

用三氟化硼乙醚为催化剂,以苯乙酮和乙酸(也是溶剂)为原料,利用碘酰苯为氧化剂"一锅法"合成了α-乙酰氧基苯乙酮。研究了温度和催化剂用量对目标产物的影响,优化的工艺条件为:n(苯乙酮)∶n(三氟化硼乙醚)∶n(碘酰苯)=1∶3∶1.2,反应温度50℃,反应时间6h,此条件下产品收率72%。     

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、¹H NMR和¹³C 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。     

乙二醇二缩水甘油醚的合成及表征

以乙二醇和环氧氯丙烷（ECH）为原料,三氟化硼乙醚络合物为催化剂,合成了乙二醇二缩水甘油醚。通过正交试验的实验方法研究了原料配比、催化剂用量、开环反应温度以及闭环反应时间对产物收率和环氧指数的影响,并且用气相色谱、傅里叶红外光谱和核磁氢谱对产物进行了分析和表征。对正交实验的进一步验证和优化表明,乙二醇二缩水甘油醚的最适宜制备条件为：n(ECH)/n(乙二醇)为2.2,催化剂用量为乙二醇质量的0.5%,开环反应温度为50 ℃,闭环反应时间为1 h。最适宜工艺条件下合成产物的各项技术指标均优于工业生产技术指标。     

硼-10酸的合成

为了开发经济高效的硼-10酸生产路线,文中对于以工业生产得到的三氟化硼-10-乙醚络合物为原料生产硼-10酸的工艺进行了初步研究。首先采用三氟化硼-10-乙醚络合物与甲醇钠反应生成硼-10酸三甲酯,之后水解合成硼-10酸。分别讨论并优化了酯化反应和水解反应的工艺条件。在无水甲醇中,n(甲醇钠)∶n(三氟化硼-10-乙醚络合物)=4.4条件下,于55℃酯化反应32 h,硼-10酸三甲酯收率为87.43%。在n(水)∶n(硼-10酸三甲酯)=7.5条件下,硼-10酸三甲酯于室温下进行水解反应,硼-10酸收率可达97.13%,纯度大于99.0%。     

3-甲基戊酸糠醇酯的合成研究

以3-甲基戊酸为原料,经酰氯化、酯化反应,合成了香料目标化合物。考察了催化剂用量、反应物配比、反应时间、反应温度等对目标化合物收率的影响,结果表明,最佳合成工艺条件为:n(3-甲基戊酰氯)∶n(吡啶)=1∶2,n(糠醇)∶n(3-甲基戊酰氯)=1∶1. 2,反应时间4 h,反应温度50℃,收率达87. 8%。利用IR、1HNMR、13CNMR对目标化合物结构进行确证。     

4′-(6-溴己氧基)联苯-4-甲酸甲酯的合成

4′ 羟基联苯 4 甲酸与甲醇反应,合成了4′ 羟基联苯 4 甲酸甲酯。后者与1,6 二溴己烷反应合成了目标化合物4′ (6 溴己氧基)联苯 4 甲酸甲酯,反应工艺条件为:以无水乙醇为溶剂,n(4′ 羟基联苯 4 甲酸甲酯)∶n(碳酸钾)∶n(1,6 二溴己烷)=1∶1 5∶3,80℃反应8h,收率达60 8%。两步总收率57 6%。目标化合物经IR,1HNMR和元素分析确证了分子结构。     

非离子型水性环氧树脂固化剂的合成与性能研究

采用低相对分子质量的环氧树脂E-51与聚醚-4000反应制备环氧改性聚醚加成物,再与多乙烯多胺进行反应制备胺封端的聚醚-环氧-胺加成物,最后采用单环氧化合物进行封端,合成非离子型水性环氧固化剂,实验表明工艺可行。对环氧E-51改性聚醚-4000合成过程中的各影响因素进行了研究,并对非离子型水性环氧固化剂的固化性能进行了评价。最佳配方与工艺为:n(环氧树脂E-51)∶n(聚醚-4000)2∶1,催化剂选用含三氟化硼(BF3)质量分数2%的乙醚溶液(60℃时加入,加入量为2%)。与现有的市售水性环氧固化剂固化性能相比,非离子型水性环氧固化剂固化的环氧体系的柔韧性和耐冲击性有大幅提高。     

TGDDM环氧树脂的合成研究

以4,4′-二氨基二苯甲烷(DDM)与环氧氯丙烷(ECH)为原料,乙醇为稀释剂进行开环反应,再在碱性条件下进行环化反应,合成TGDDM环氧树脂,并用红外光谱进行表征。结果表明,较优工艺条件为：开环反应温度为60℃,反应时间15 h,n(ECH)∶n(DDM)=4.3∶1,DDM加料温度为50℃,环化反应温度为50℃,反应时间1 h,n(NaOH)∶n(DDM)=4.5∶1,氢氧化钠浓度为30%,此时目标产物TGDDM的收率为94%,环氧值为0.870 mol/100 g,无机氯含量为6.12 mg/kg,易皂化氯含量为114 mg/kg。     

3-甲氧基丙烯酸甲酯的合成工艺研究

以四氯化碳和乙烯基乙醚为原料,在引发剂作用下发生自由基加成反应制备1,1,1,3-四氯-3-乙氧基丙烷(以下简称丙烷化合物),丙烷化合物与甲醇回流得到3,3-二甲氧基丙酸甲酯,然后在裂解催化剂的作用下裂解为3-甲氧基丙烯酸甲酯。优化工艺条件为:催化剂为偶氮二异丁腈/间氯过氧苯甲酸,n(乙烯基乙醚)∶n(四氯化碳)∶n(偶氮二异丁腈)∶n(间氯过氧苯甲酸)=1∶1.6∶0.001 6∶0.001 6,反应温度为68℃,反应时间为6 h;裂解反应所用催化剂为对甲苯磺酸。3步反应总收率为67.7%(以乙烯基乙醚计),含量为98.5%。     

Effect of dihydroxydiphenyl ether on poly(ether ether ketone)

A series of modified poly(ether ether ketone) (PEEK) polymers were synthesized by introduction of addition ether groups from dihydroxydiphenyl ether (DHDE) into the PEEK structure. The inherent viscosity of the DHDE-modified PEEK increased with reaction time at 320 °C. DSC thermograms showed the melting points of the obtained PEEK decreased with the increase of the DHDE content in the backbone. The degradation temperature (T_d) was slightly decreased by the introduction of DHDE. The crystallinity as measured via the X-ray diffraction (XRD) increases with the introduction of DHDE into the modified PEEK. The crystalline structure was identified as an orthorhombic structure with lattice constants a = 7.72 Å, b = 5.86 Å, and c = 10.24 Å. Due to the glass transition temperature (T_g) and the melting temperature (T_m) decreasing with the increase of the DHDE content in the reaction system. the processability of the resultant PEEK could be improved through this DHDE modification.     

—步法合成醇醚混合物的双甲精制新工艺

介绍了双甲精制新工艺的流程及工艺指标等。双甲工艺是一种清洁生产工艺,它已逐步在小氮肥推广。双甲副产物醇醚混合物用于餐馆和家庭,推广这项技术对提高小氮肥技术水平和改善产品结构很有意义。     

The alkyl glycidyl ether as synthetic building blocks

Alkyl glycidyl ether is one of the most useful key materials for industrial applications because the addition reaction of various kinds of nucleophilic reagents to the reactive epoxy bond of the glycidyl ethers has led to glyceryl ether derivatives. Glyceryl ether exhibits many interesting physical and pharmacological properties. The alkyl glycidyl ether can presently be produced at an industrial scale under the phase-transfer catalytic Williamson ether synthesis. We have reviwwed some addition reactions of the alkyl glycidyl ether and possibilities for use as the building blocks for the syntheses of surfactants, pharmaceuticals, etc. that contain glyceryl ether skeletons. Typical examples of alkyl glyceryl ether derivatives include: amino ether as cosmetic material, and isodiglycerin mono- and dialkyl ethers and triglycerin monoalkyl ether as a cosmetic or a pharmacologically useful material, respectively. Another interesting reaction is the rearrangement of the epoxy bond of the alkyl glycidyl ether, which gives alkoxy ketone in a one-pot synthesis.     

Enthalpic relaxation in semi-crystalline PEEK

The effect of crystallisation on the glass transition temperature and enthalpic relaxation in poly(ether ether ketone) (PEEK) has been investigated. The increase in glass transition temperature and the activation enthalpy of ageing is explained in terms of the amorphous phase being constrained by the crystallites. The extent of enthalpic relaxation with time has been analysed in terms of the Cowie-Ferguson model and the β value was found to be dependent on both temperature and the crystalline morphology, changes in the co-operativity of the relaxations are used to explain this observation.     

Synthesis and properties of thio‐containing poly(ether ether ketone)s

A series of thio‐containing poly(ether ether ketone) (PEESK) polymers was synthesized by the introduction of thio groups from 4,4′ thiodiphenol (TDP) into the poly(ether ether ketone) (PEEK) structure via reaction between the phenol and aromatic fluoride groups. The effect of the thio groups on the properties of the PEESK materials was investigated. Differential scanning calorimetry (DSC) analysis and X‐ray diffraction (XRD) patterns show a depression in the crystallinity of the PEESKs with incorporation of the content of thio groups in the backbones. The crystalline structure was identified as an orthorhombic structure with lattice constants of a = 7.52 Å, b = 5.86 Å and c = 10.24 Å for all crystallizable PEESKs. The crystalline structures of the thio‐containing PEEK polymers were the same as that of the neat PEEK, which means the thio‐containing block in the whole thio‐containing PEEK molecule is almost excluded from the crystalline structure and the crystals are completely formed by ‘non‐thio’ blocks only. Due to the glass transition temperature (T_g) and melting temperature (T_m) depression with increase in the TDP content in the reaction system, the processability of the resultant thio‐containing PEEKs could be effectively improved. Copyright © 2004 Society of Chemical Industry     

双套索硫杂冠醚及主链含硫杂冠醚聚酯的合成

从３，１６－二羟基－１－硫杂－５，３，１１，１４－四氧杂环十七烷（二羟基硫杂－１７冠－５）出发，通过醚化反应，合成了双（己氧基），双（十二烷氧基）、双（十六烷氧基），双（苄氧基）和双（烯丙氧基）硫杂－１７－冠－５。单己氧基、单十二烷氧基，单十六烷氧基和单苄氧基硫杂－１７－冠－５作为副产物分离得到。通过二羟基硫杂－１７－冠－５与丁二酰氯缩聚，合成了主链含硫杂冠醚的聚酯。     

两种双取代苯并冠醚的合成

以邻苯二酚为原料,采用不同的方法合成了两种双取代苯并冠醚,并进行了结构表征,确认其组成。     

2-碘乙基甲基醚的合成及工艺改进

以乙二醇单甲醚为原料,经氯化亚砜氯代和碘化钾卤素交换反应得到了2-碘乙基甲基醚,总收率78.9%。     

邻氨基二苯醚的合成工艺研究

本文研究并改进了邻氨基二苯醚的合成方法。以DMSO为溶剂，以氢氧化钾为碱．苯酚和邻硝基氯苯在铜粉催化下高收率的生成邻硝基二苯醚，然后在5％pd／C的催化下。氢化还原硝基得到邻氨基二苯醚，同时对pd／C的回收套用进行试验，探索出一条反应条件温和、收率高、纯度好的较为理想的工业化生产路线。     

氮杂冠醚中间体二氨基芳醚制备的新方法

用５０％水合肼，在ＦｅＣｌ２．６Ｈ２Ｏ及活性炭的催化作用下，还原制得了８个开链冠醚桥连的二氨基芳醚。还原产率７７％～９２％之间。