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Study On Functionalization Of Saturated Carbon By Catalytic Oxidation

Posted on:2001-01-18Degree:DoctorType:Dissertation
Country:ChinaCandidate:W T GaoFull Text:PDF
GTID:1101360002452005Subject:Fine chemicals
Abstract/Summary:PDF Full Text Request
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, æ…”-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...
Keywords/Search Tags:Functionalization
PDF Full Text Request
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