2-溴-3-甲基-1,4-二甲氧基萘的合成新方法研究

以2-甲基萘醌(2)为原料,经过催化氢化、甲醚化和溴代三步反应,合成了维生素K2的重要中间体2-溴-3-甲基-1,4-二甲氧基萘(1)。(2)催化加氢还原得到2-甲基-1,4-二羟基萘(3)。(3与硫酸二甲酯反应生成2-甲基-1,4-二甲氧基萘(4),甲醚化反应通过正交实验可使产物收率达到95.1%;(4)与溴反应,经单因素实验在较佳的反应工艺条件下得到目标产物(1),收率90.1%。三步反应总收率达到84.6%。     

3,6-二溴-9-(4-溴苯基)-9H-咔唑的合成

以咔唑为原料,经两步反应和一锅法分别合成目标产物3,6-二溴-9-(4-溴苯基)-9H-咔唑。N-芳基化反应和N-溴代丁二酰亚胺(NBS)的亲电取代反应均采用N,N-二甲基甲酰胺做溶剂,并使用将反应母液加入甲醇的方法,以69.6%的收率得到目标产物3,6-二溴-9-(4-溴苯基)-9H-咔唑。     

2-(2-羟基-4-溴苯基)-5,6-二硝基苯并咪唑的合成

以4,5-二硝基邻苯二胺和5-溴水杨醛反应,控制不同条件,可分别得到单Schiff碱化合物5-溴水杨醛缩4,5-二硝基邻苯二胺和苯并咪唑衍生物2-(2-羟基-4-溴苯基)-5,6-二硝基苯并咪唑,前者在一定的条件下能够关环转化为后者,对它们的结构进行了UV-Vis、IR、1HNMR、MS表征,对构形转化的反应机理进行了研究.     

2-(2′-乙酰氧基-5′-溴甲基苯基)-2H-苯并三唑的合成

2-(2′-羟基-5′-甲基苯基)-2H-苯并三唑(UV-P)经过羟基乙酰化、N-溴代丁二酰亚胺(NBS)溴代,合成了具有高反应活性的2-(2′-乙酰氧基-5′-溴甲基苯基)-2H-苯并三唑。为提高目标产物产率和反应效率,分别对溶剂、引发剂、反应温度、反应时间、反应物投料比和反应底物浓度进行了研究。得出较优合成条件为:氮气保护下,四氯化碳为溶剂,偶氮二异丁腈(AIBN)引发,NBS与2-(2′-乙酰氧基-5′-甲基苯基)-2H-苯并三唑摩尔比1∶1,回流反应1h。在上述条件下,2-(2′-乙酰氧基-5′-溴甲基苯基)-2H-苯并三唑产率为60%。产物经过IR、1HNMR、MS分析证明结构正确。     

3,5-二甲基-4-溴碘苯和2,6-二甲基-4-溴碘苯的合成

二甲基对溴碘代苯是带有两种不同卤素基团的芳香族有机合成中间体。2,6-二甲基苯胺在过碳酸钠作用下,于45~50℃与碘反应1 h,得到2,6-二甲基-4-碘苯胺,收率42.5%。2,6-二甲基-4-碘苯胺在-5~0℃下进行重氮化,进一步与溴化亚铜发生Sandm eyer反应,得到3,5-二甲基-4-溴碘苯,收率31.5%。2,6-二甲基苯胺室温下与六亚甲基四胺溴络合物反应30 m in,得到2,6-二甲基-4-溴苯胺,收率62.0%。2,6-二甲基-4-溴苯胺在-5~0℃进行重氮化,与K I反应,得到2,6-二甲基-4-溴碘苯,收率33.1%。通过熔点、红外光谱和核磁共振氢谱对中间体2,6-二甲基-4-碘苯胺、2,6-二甲基-4-溴苯胺以及最终产物3,5-二甲基-4-溴碘苯和2,6-二甲基-4-溴碘苯进行了表征。     

托尼卟吩结构模型中D环结构单元的合成

由乙酰乙酸乙酯(1)为原料经过肟化、还原缩合成环等反应首先合成knorr吡咯(4),然后再由knorr吡咯经氧化反应得到2,4-二乙氧羰基-3-甲基-5-甲酰基吡咯(5),5经皂化反应得到2-羧基-3-甲基-4-乙氧羰基-5-甲酰基吡咯(6),6再经溴化反应得到2-溴-3-甲基-4-乙氧羰基-5-甲酰基吡咯(7),最后,7通过皂化及脱羧得到托尼卟吩结构模型的重要中间体D环结构单元2-溴-3-甲基-5-甲酰基吡咯(Ⅴ)。合成产物的结构都通过1HNMR、IR和GC-MS或MS得到了表征。同时对第二步中氧化反应中的氧化剂以及第四步溴化反应中的溶剂进行了研究。结果表明,氧化反应中的最佳氧化剂为硝酸铈铵,产率达到91.5%,溴化反应中的最佳溶剂为甲醇,反应产率达到58%。     

超声波促进3-(4-苯磺酰基-3-甲基-2-丁烯基)-4,5,6-三甲氧基-2-甲基苯基苄基醚的合成

以3,4,5-三甲氧基甲苯(Ⅰ)为原料,经过Vilsmeier-Haack反应合成了6-甲基-2,3,4-三甲氧基苯甲醛(Ⅱ),收率94.1,Ⅱ经过Dakin反应得到2,3,4-三甲氧基-6-甲基苯酚(Ⅲ),收率96.2,用溴化苄对Ⅲ进行酚羟基保护得到2,3,4-三甲氧基-6-甲基苯基苄基醚(Ⅳ),收率95.0,Ⅳ在有机碱作用下发生溴代反应,得到6-甲基-5-溴-2,3,4-三甲氧基苯基苄基醚(Ⅴ),收率92.2,Ⅴ在超声波作用下制成格氏试剂(Ⅵ),再与4-溴-2-甲基-1-苯磺酰基-2-丁烯发生格氏偶联反应得到辅酶Q10的关键中间体3-(4-苯磺酰基-3-甲基-2-丁烯基)-4,5,6-三甲氧基-2-甲基苯基苄基醚(Ⅶ),收率72.0,五步反应总收率为57.1,产物经FTIR和1H NMR确定结构。     

4-溴-2-(溴甲基)苯甲醛的合成研究

4-溴-2-(溴甲基)苯甲醛是合成1, 2-二氢酞嗪化合物的重要中间体。以4-溴-2-甲基苯腈为原料,通过溴代、还原得两步反应得到目标化合物4-溴-2-(溴甲基)苯甲醛。确定了溴代反应最佳条件:N-溴代丁二酰亚胺(24.0 mmol)、过氧苯甲酰(4.0 mmol),反应体系在CCl_4中回流反应8 h。还原反应最佳条件:二异丁基氢化铝(DIBAL-H)(12.0 mmol),反应溶剂二氯甲烷,室温反应3 h。两步反应总收率85.4%,产物及中间体结构通过~1H NMR、~(13)C NMR和电喷雾电离质谱(ESI-MS)进行了表征。     

可光固化单体2,7-二溴-9,9-双[4′-(1″,4″-戊二烯-3″-氧基酰基戊基氧基)苯基]芴的合成

以芴为原料,经溴代、氧化反应首先合成了2,7-二溴芴酮,再与苯酚反应合成2,7-二溴-9,9-双(4′-羟基苯基)芴.利用2,7-二溴-9,9-双(4′-羟基苯基)芴与1,4-戊二烯-3-醇-6′-溴己酸酯经醚化反应合成了用于发光聚合物制备的可光固化单体标题化合物.反应总收率66％.中间产物和目标产物结构经1HNMR、13CNMR和元素分析表征.     

一种紫外线吸收剂的合成新方法

采用新方法合成了紫外线吸收剂苯基-(3,5-二叔丁基-4-羟基苄基)丙二酸二(1,2,2,6,6-五甲基-4-哌啶)酯。苯基丙二酸二乙酯和N-甲基-2,2,6,6-四甲基-4-哌啶醇在甲苯中微纳米碳酸钾催化下反应,得到苯基丙二酸二(1,2,2,6,6-五甲基哌啶醇)酯,然后在乙醇中与 4-羟基-3,5-二叔丁基苄基氯反应,得到目标产物,总收率为80%。化合物的结构通过1H NMR和13C NMR进行了表征。     

溴化聚苯乙烯阻燃剂的合成及性能研究

以聚苯乙烯 (PS)、溴素为原料 ,在 40℃ ,2 5 %催化剂 (相对于PS的质量 ) ,溶剂CH2 Cl2 用量 1mL/ 0 1gPS ,时间 3h的反应条件下合成了溴化聚苯乙烯 (BPS)阻燃剂 ,溴的质量分数为6 0 % ,并用红外光谱和X射线光电子能谱表征了其基本结构。对于不同阻燃剂质量分数的高抗冲聚苯乙烯 (HIPS)体系进行了阻燃性能、力学性能和流变性能的初步研究 ,结果表明 :随阻燃剂质量分数的增加 ,阻燃性能逐渐提高 ,但力学性能和流变性能均有所降低。当在共混物中添加质量分数为 3%的BPS阻燃剂时 ,复合材料的水平燃烧速率为 33mm/min ,满足了我国关于家用电器的阻燃法规 (<40mm/min) ,而且此时体系的综合性能也较好。     

The relative physical and thermal properties of polyurethane elastomers. Effect of chain extenders derived from dihydroxynaphthalene

Polyurethane elastomers were synthesized based on polyols such as poly(caprolactonediol) and poly(tetramethylene glycol), diisocyanates such as diphenylmethane-4,4′-diisocyanate (MDI) and dicyclohexylmethane-4,4′-diisocyanate (HMDI), and two dihydroxynaphthalenes (DHNs) and their brominated derivatives used as chain extenders. The effects of the chemical structures of the chain extenders on the physical and thermal properties of the polyurethanes were investigated. Because of the higher degree of phase mixing of the 1,5-DHN unit, the 1,5-DHN-based polyurethanes have higher T_g values and higher dynamic properties than 2,7-DHN-based polyurethanes. Introduction of bromine atoms increased the flame retardance. However, the large free volume of bromine atoms restricted the rotation of DHNs, thus, directly decreasing the degree of phase-mixing and crystallinity of the polyurethanes. Introducing bromine atoms also decreased the mechanical and dynamic properties and increased the solubility of the polyurethanes.     

溴化环氧树脂合成的研究

本文主要介绍了由环氧氯丙烷(ECH)与不同比例的四溴双酚A(TBBPA)和双酚A(BPA)混合物合成溴化环氧树脂。也可以根据溴含量和分子量的不同要求,先合成液态双酚A型环氧树脂或不同溴含量的液态溴化环氧树脂,再与TBBPA或BPA,或BPA和TBBPA的混合物反应,合成不同活性、不同溴含量的溴比环氧树脂即二步法。     

5-溴乙酰基水杨酰胺的制备

5-溴乙酰基水杨酰胺是一种非常重要的医药与农药中间体。选择溴在乙酸溶剂中,5-乙酰基水杨酰胺溴化。当反应物n(5-乙酰基水杨酰胺)∶n(溴)=1∶1.05,5℃反应12h,可高选择性得到5-溴乙酰基水杨酰胺,收率93.2%。     

Novel strategies for the synthesis of hydroxylated and carboxylated polystyrenes

Hydroxylated and carboxylated polystyrenes (PHMSt and PCSt, respectively) were synthesized using facile strategies. For this purpose, PSt was synthesized through atom transfer radical polymerization (ATRP) approach and then brominated at the para-position of the aromatic rings to produce PBrSt. The bromination efficiency was calculated to be 37 and 68%, even though there was a degradation of the polymer chains, using 60 or 100 mol% of bromine relative to the PSt, respectively. The brominated polymer was converted into Grignard reagent (PSt-magnesium-Br), and then reacted with anhydrous formaldehyde and solid carbon dioxide (Dry Ice) to afford PHMSt and PCSt, respectively. The chemical structures of all synthesized polymers were characterized using Fourier transform infrared (FTIR) as well as proton nuclear magnetic resonance (¹H NMR) spectroscopies. Furthermore, the thermal behavior of the synthesized PHMSt and PCSt were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).     

4-[2-（1-苯乙烯基）]-N,N-二（4-溴苯基）苯胺的合成研究

苯乙烯基三苯胺化合物被认为是很有开发前景和实用价值的一类空穴传输发光材料,它具有较为优异的综合性能,如良好的成膜性,较好的热稳定性等。以三苯胺为原料,经维尔斯迈尔反应,溴化,维蒂希反应合成一种新颖的三苯胺类芳香共轭体系分子即4-[2-（1-苯乙烯基）]-N,N-二（4-溴苯基）苯胺。苯乙烯基的加入,使分子共轭效应增强,电子传输能力更强。溴原子的取代会使其溶解性得到改善,同时增强材料的热稳定性,得到一种非常有潜力,光电性能好的三苯胺衍生物。     

Synthesis and properties of 4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonates and effects of their flame retardance on impact polystyrene

p-Cresol was converted into 2,3,5,6-tetrabromocresol by AlCl₃ catalyst bromination, and then further brominated to 4-hydroxy-2,3,5,6-tetrabromobenzyl bromide (HTBBB) in benzene by light. HTBBB reacted easily with trialkyl phosphite to produce 4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonates (HTBBPs) in solvents. Although the reaction of HTBBB with triaryl phosphite was slower than that with trialkyl phosphite, it does produce corresponding phosphonate with ease. Except for DMF, DMAc, chloroform, and tetrahydrofuran, HTBBP was difficult to dissolve in ordinary organic solvents. Of all the synthesized HTBBP, dimethyl hydroxy-2,3,5,6-tetrabromobenzyl phosphonate showed the poorest solubility. With the addition of these new compounds containing bromine and phosphorus atoms to HIPS as flame retardants, the results of oxygen index measurement showed that the flame resistance of these compounds was greater than the additive effect of the two corresponding individual brominated compound and phosphorus-containing compound. It means that these new compounds seem to act synergistically as flame retardants in HIPS. Simultaneous addition of bominated compound and phosphorus-containing compound to HIPS ends up with a similar effect as mentioned above, but the new compounds can prevent the exclusion of phosphorus-containing compound from polymer matrix.     

Isolation of brominated long-chain fatty acids from the phospholipids of the tropical marine spongeAmphimedon terpenensis

Preliminary investigation of the phospholipid fatty acid composition of the tropical marine spongeAmphimedon terpenensis by gas chromatography/mass spectrometry revealed the presence of some novel brominated fatty acids. Two new brominated fatty acids, (5E, 9Z)-6-bromo-5,9-tetracosadienoic acid (2a) and (5E, 9Z)-6-bromo-5,9-pentacosadienoic acid (3a) were subsequently isolated from a chloroform/methanol (3∶1, vol/vol) extract of the sponge and characterized as their methyl esters 2b and 3b. The known brominated fatty acid (5E, 9Z)-6-bromo-5,9-hexacosadienoic acid (4a) was also isolated. The new fatty acid methyl esters were confirmed as brominated δ5,9 acid derivatives by chemical ionization mass spectrometry. The position of the bromine substituent was determined to be C-6 by nuclear magnetic resonance techniques while the stereochemistry of the two double bonds was deduced by nuclear Overhauser enhancement difference spectroscopy. The biosynthetic implications of the co-occurrence of the three brominated acids are discussed.     

The efficiency of reaction between reactive fluorescent whitening agents and wool

Potential fluorescent whitening agents (FWAs) containing halogen atoms which intramolecularly quench fluorescence have been synthesised and applied to wool in a number of ways. Application by cold pad-batch methods revealed that the complete displacement of all halogen atoms by nucleophilic groups in wool did not take place. Treatment of these materials with morpholine, sodium carbonate or water was necessary to develop the full potential fluorescence yield of the FWA on the fabric. The fluorescence of FWAs can be quenched by the heavy atom effect, as shown by the fact that no fluorescence was observed when commercial FWAs were applied to brominated wool. If the FWA-treated brominated fabrics were subjected to a reduction treatment then the bromine atoms were removed and the fluorescence of the FWA was restored. Application of the potential FWAs by exhaustion, with thioureadioxide present in the liquor, at high temperatures always led to strongly fluorescent fabrics, implying that the halogen atoms were completely displaced using this application method, but the question remains as to how much of the displacement leads to covalent bonds between the fabric and the FWA.     

高分子阻燃剂溴化聚苯乙烯阻燃PA6的研究

采用原子转移自由基聚合(ATRP)法合成低相对分子质量、相对分子质量分布较窄的聚苯乙烯(PS),以PS、Br2为原料,AlCl3作催化剂,CH2Cl2为溶剂,低温反应5～6h合成低相对分子质量溴化聚苯乙烯(BPS),用于对PA6进行阻燃。考察了反应条件对聚合过程及产物性能的影响,并研究了阻燃PA6的流变性能、力学性能、阻燃性能。结果表明,随着阻燃剂含量的增加,PA6的阻燃性能和流变性能均有较大提高,力学性能下降较少,当在PA6中添加质量分数为19%的BPS和Sb2O3复合阻燃剂时,阻燃PA6能够达到UL94V-0级,满足家用电器的阻燃法规,而且此时体系的综合性能也较好。