【作者】 高文涛；

【导师】 杨锦宗； 张淑芬；

【作者基本信息】 大连理工大学 ， 精细化工， 2000， 博士

【摘要】 本文在全面综述金属卟啉和金属酞菁类模拟细胞色素P-450酶催化剂催化氧化饱和碳原子功能化的基础上，选择由4-硝基甲苯-2-磺酸制取4,4’-二硝基二苯乙烯-2,2’-二磺酸和由4,4’-二（二甲胺基-二苯基）苯基甲烷制取4,4’-二（二甲胺基-二苯基）苯基甲醇两个反应体系进行饱和碳原子碳功能化和氧功能化的具体研究。 采用改进的烘焙法合成了β-CuPc、α-CuPc、α-CoPc和α-FePc四个金属酞菁类模拟酶催化剂，用X-射线衍射对它们的结构和晶型进行了表征。 首次以金属酞菁络合物为模拟酶催化剂，在碱性水溶液中，于温和条件下，研究了4-硝基甲苯-2-磺酸催化氧化制取4,4’-二硝基二苯乙烯-2,2’-二磺酸的方法和工艺。采用红外光谱、核磁共振谱、紫外光谱和高压液相色谱对主产物进行了鉴定。采用紫外光谱和高压液相色谱对原料的转化率、主产物的选择性和纯度进行了测定，分析结果表明原料转化率达100％，主产物的纯度为96.78％，大于工业品的纯度（87.93％）。 本文重点研究了催化剂种类及其用量、碱种类及碱浓度C_a、原料初始浓度C_NTS、反应时间t和反应温度T对氧气液相催化氧化4-硝基甲苯-2-磺酸制取4,4’-二硝基二苯乙烯-2,2’-二磺酸的影响。发现金属酞菁催化剂，特别是合成的α-CuPc和经活化处理的工业品α-CuPc具有较好的催化活性，考虑到工业化要求价廉易得，选择催化活性高、效果好的金属酞菁XPc作为反应体系的催化剂，且其最佳用量为原料的1％（W/W）。在确定了合适的催化剂种类及用量和碱剂（NaOH）后，采用正交实验设计考察了各因素的相互影响，发现碱浓度C_a、原料初始浓度C_NTS、反应时间t和反应温度T四个因素对主产物收率的影响显著性顺序为T＞C_NTS＞C_a＞t，同时得出制备4,4’-二硝基二苯乙烯-2,2’-二磺酸的最佳工艺条件为T=68℃、C_NTS=0.375mol/L、C_a=1.0mol/L和t=18h。在此条件下产物的收率为81.8％，远远大于现行工艺的收率（70～75％）。 X-射线衍射分析表明催化剂在反应前后的结构和晶型没有发生变化，因而催化剂可循环使用，同时避免了现行工艺中因为使用铁盐而造成的红色 ·2·大这理工大舍q十q依伦大 废水污染，使得该工艺为环境友好工艺。 探讨了在温和条件下于碱的水溶液中氧气液相氧化个硝基甲苯．2－磺酸 制取4，4’－二硝基二苯乙烯｛了－二磺酸的反应机理，发现个硝基甲苯－2－磺酸 在碱作用下发生离于化生成个硝基－2－磺酸基卡基阴离于，然后被活化的分 于氧氧化成个硝基－2－磺酸基卡基自山基是反应的关键步骤。金属酞青催化 剂的作用是活化分子氧并促使个硝基－2－磺酸基书基阴离子氧化成个硝基．2． 磺酸基苇基自山基和催化个硝基－2．磺酸基苦基氢过氧化物分解生成个硝基－ 2－磺酸基卡基自山基，最终生成4，4’－二硝基二苯乙烯－2，2－二磺酸。 首次采用紫外光谱和高压液相色谱初步研究了4，4’－二硝基二苯乙烯－ 2，2－二磺酸稀溶液中的光致顺反异构现象。结果表明在光照条件下4，4’－二 硝基二苯乙烯－2，2’－二磺酸的稀溶液中的确存在着顺、反异构体之间的转换。 溶液的浓度越稀，光照的时间越长，反式异构体转化成顺式异构体越快、越 多。 研究了余属酞普和金属盐等催化剂对氧气液相催化氧化孔雀绿隐色体制 耿孔雀绿醇色体的影响。发现金属酞菩催化剂在此反应体系中催化效果不 佳，而合适的催化剂是MX，且其最佳用量是原料用量的3石4％。 探讨了冰乙酸及其用量、四氯苯酮及其用量对氧气液相催化氧化孔雀绿 隐色体制取孔雀绿醇色体的影响，发现二者对醇色体的收率和纯度均有很大 影响。没有冰乙酸，醇色体的收率仅为20％；没有四氯苯酿，醇色体的收 率几乎为零。在一定的范围内，醇色体的收率随着二者用量的增加而增加， 超出这个范围，收率呈逐渐下降的趋势。 考察了乙醇等一系列溶剂对氧气液相催化氧化孔雀绿隐色体制取孔雀绿 醇色体的影响，发现乙醇和甲醇是反应最合适的溶剂。考虑到溶剂的毒性和 叫收率，乙醇是更佳的选择。 采用小交实验考察了反应时间t、反应温度T、溶剂加量V和催化剂加 量W对氧气液相催化氧化孔雀绿隐色体制取孔雀绿醇色体的影响，发现它 们对其收率影响的程度为T＞w＞1＞V。最佳工艺条件为F10h、＊－50℃、 V－25ml、W叫。在最佳条件下醇色体的收率为82石％，高出现行工艺 的收率 15二％；纯度为 76．3％，低于工业品的纯度 8．9％。但其染色效果不受 影晌，而且》［艺具有反应条件温和、无污染的优点，先全适合工业化。更多还原

【Abstract】 Based on reviewing of functionalization of saturated carbon by catalytic oxidation with metalloporphyrins and metal phthalocyanines as a mimic of the enzyme cytochrome P-450, two reaction systems of which one was the preparation of 4,4?dinitrostilbene-2,2 ?disulfonic acid(DNS) from 4-nitrotoluene- 2-sulfonic acid(NTS) and the other was the preparation of 4,4?bis(dimethylamino -diphenyl)phenylmethanol(TAML) from 4,4?-bis(dimethylamino-diphenyl)phenyl methane(TAMD), were specifically studied as carfunctionalization and oxy- functionalization of saturated carbon. Four metal phthalocyanine type simulated catalysts(3-CuPc,c-CuPc,c~- CoPc,ci~-FePc) were synthesized by improved method. Their structures and crystalline form were characterized by XRD. The novel process of preparation of DNS by means of dioxygen liquid-phase oxidation of NTS with synthesized metal phthalocyanine complex catalyst in alkali(NaOH) solution under mild condition were systematically investigated for the first time. The structure of main product was confirmed by IR, 慔-NMR, UV and HPLC. The purity and selectivity of main product and the conversion of reactant were determined by HPLC and UV. The analytic results showed that the conversion was 100% and the purity of main product exceeded 96.78%, which was 8.85% higher than that of industrial product. The effect of type and amount of catalyst, the type of alkali and alkali concentration(Ca), initial concentration of NTS(CNTS), reaction time(t) and reaction temperature(T) on the preparation of DNS by means of dioxygen liquid- phase oxidation of NTS was emphatically studied, and the results showed that the metal phthalocyanines, especially the synthesized c-CuPc and the activated industrial product o-CuPc had better catalytic activities. As the industrialization was considered, the activated industrial product XPc was selected as catalyst in the reaction system. Based on these results, 1 .0% catalyst (w/w) was selected as optimum. The mutual effects of C, C NTS, and T on the yield of DNS were studied by the orthogonal experimental design after the prefered catalyst and its amount was determined. The order of the significance to affect the yields of DNS was T>CNT ~>C a>t, and the optimum process parameters were T=68 0C CNTS=0.37Smol/L, Ca=1.Omol/L and t=18h. The yield of DNS was 8 1.8% under the optimum condition which was 6.8%-A 1.8% higher than present technology. XRD of catalyst showed that its structure and crystalline form did not change after the reaction, so the catalyst could he recycled. At the same time, the pollution of red water caused by FeSQ4 in existent technology could be avoided. The mechanism of dioxygen oxidation of NTS to DNS in alkali solution under mild condition was inquired into. The result showed that the key step in the preparation of DNS from NTS was the formation of 4-nitro-2-sulfobenzyl anion as a result ionization of NTS in strong alkali and then oxidization to 4-nitro-2- sulfobenzyl radical by activated dioxygen. The action of metal phthalocyanine catalyst was to activate dioxygen and to promote reactions of NTS and 4-nitro-2- sulfobenzyl anion with activated dioxygen, and to catalyze the decomposition of 4-nitro-2-sulfobenzy hydrogen peroxide to 4-nitro-2-sulfobenzyl radical and the ultimate product, DNS. UV and HPLC were used for the first time to study the photo-cis-trans isomerism in dilute DNS solution. The result showed the existence of更多还原