Studies On Syntheses And Activities Of Ketals And Oxime Carboxylates Of 2,4-Dichloroacetophenone And Its α-Substituted Derivatives

1 Syntheses of fungicides l-[2-(24-dichlorophenyl)-4-R(H)-l3-dioxolan-2-yl]-lH-l24-triazoleTriazole fungicides l-[2-(24-dichlorophenyl)-4-R(H)-l3~dioxolan-2-yl] -1H-1,2,4-triazole include azaconazolemetaconazole etaconazole and propiconazoledifenoconazole is similar in structure. There are some varieties of tens of triazole fungicideseach of them has more than 100 million dollars sales a yearhave exceeded or will exceed their patent time limits. Propiconazloe is one of themits total sale per year surpasses 200 million dollarsthe value of development and application is tremendous. This series of compounds have strong bioactivity against moulds such as AspergillusnigerTrichoderma viridefungi such as Chaetomium globosum Trychophyton mentagrophytesand yeasts such as Candida albicans. Their syntheses can be achieved by several routesbut no reference data has expounded which is necessary in industrial production. So study and contrast of different routes and reaction factors should be our research purpose.Azaconazolemetaconazole and propiconazloe were synthesized by three routes of bromization chloridization and later cyclization. The chloridization route' s total yield was 30% or soand product purity was low. The bromization route' s total yield was about 40%and high quality' s product was yielded. And in later cyclization routetarget compounds's total yield was only about 20%product purity was 25~45%and further purification was difficult. The synthetic products were confirmed by infrared spectrographyGC/MS and 'H NMR spectrography.There were many factors which would affect the synthesis of 1-[2-(24-dichlorophenyl)-4-R(H)-l3-dioxolan-2-yl]-lH-l24-triazole. Differe catalysts in cyclization could change the ketal yields for example4% HXAmade the yield increased to above 95%. Dehydrolysis time of cyclization reaction were important on synthetic yield . And the suitable temperature and time of condensation were 130癈 and 16h or sorespectively. Moreoversolvent1 could make the content of a -bromic-24-dichloroacetophenone raised to more than 85%. Additive stabilizer could avoid the decomposition of ketal. And the preparation of nitrate improved the quality of propiconazole greatly to 97%.2 Study on industry production technique of propiconazoleThe technological process of industry production of propiconazole was designed on the base of research about bromization routeand the analytical method of propiconnazole was established. The result of three running experiments indicated that the production process was reasonablethe rules of operation and safety were feasible. The produced propiconnazole crude oil appeared brownthe average purity and yield were 68.77% and 66.78%respectively. The propiconnazole nitrate appeared pale yellow solidand its further reaction with NaOH gave pale yellow refined oilits average purity and yield were 97% and 53. 83%respectively. Preliminary accounting indicated that 1.5 million yuans(RMB) fixed assets investment and 2 million yuans circulating capital for 100 tons propiconnazole crude oil produced a year were necessaryand the total investment were about 3.5 million yuans. The total sale costwas 32.429 millions yuansand the profit and tax was about 12.456 million yuans a year.The toxicity of propiconnazole refined oil and its nitrate was determined in laboratoryand the values of EC5() to Gibberella zeaeRhizoctonia cereal isFussrium monili formePyricularia griseaColletotrichum orbiculare and Botrytis cinera were compared to those of Propiconnazole sample from Ciba-Geigy Limited Company. The fungicidal activity of refined oil was better than CK sample except Fussrium moniliformeand nitrate was not as good as refined oil to pathogenic fungibut it would match CK sample if its molcular weight component is considered.3 Preliminary study on preparationseparation and analysis of optically active isomers and cis- and trans-isomers of propiconazolePropiconazole structure contains four enantiomers including cis-recemate and trans-racematethe cis-recemate contains the pa...