Using 2-p-nitrobenzy-loxycarbonylmethoxyimino-3-oxo-butyric acid,sulfuryl chloride as base material,under the certain conditions,(Z or E)-4-chloro-2-p-nitrobenzyloxy-carbonyl-methoxyimino-3-oxo-butyric acid was synthesized.Its chemical structure was characterized by IR and 1H NMR.The better technology has been obtaind as follows ∶the mole ratio of n(2-p-nitrobenzy-loxycarbonylmethoxyimino-3-oxo-butyric acid) ∶n(sulfuryl chloride)=1 ∶1.4,reaction time is 5~ 6 h at 50~55 ℃.After finish reaction system dispose of the technology pH is 6.5±0.1,the separating effect reach over 99%,the yield of the product is 24% and 48%,the purity is all 98%.
Using ethylenediamine,urea,methanal and formic acid as base material,1,3-dimethyl-2-imidazolidinone was prepared via cyclization reaction and methylation.Its structure was characterized by IR and 1H NMR.The effect of solvent,material concentration,material ratio,reaction temperature and reaction time,catalyst on the preparation were studied.The better technology has been obtained:taking water-EG as solvent 2-imidazolidinone was prepared.The molar ratio of the methanal(36%) to the formic acid(85%) is 1 ∶2.8,reaction temperature is 95~100 ℃,reaction time is 16 h,taking cuprous chloride and triethylamine as catalyst,the molar ratio of the cuprous chloride and triethylamin to 2-imidazolidinone is 1.0% while 1,3-DMI was prepared.The yield of 1,3-DMI could reach 71%,the purity of 1,3-DMI is 98.5%.
Reaction of 2,6-dihydroxyacetophenone (1) with benzoyl chloride under phase-transfer catalysis by tetrabutyl ammonium bisulfate formed 5-hydroxyflavone (2) in 65% yield at 60℃ with n (1):n (tetrabutylammoniumbisulfate)=1∶1.3. 1 was synthesized from resorcinol in four steps including cyclization, esterification, rearrangement and ring-opening. The structures of 1 and 2 were identified by IR and 1H NMR. Mechanisms for formation of 1 and 2 were also proposed.
Using citraconic anhydride and hydrazin dihydrochloride as base materials,through three steps 3,6-dichloro-4-pyridazinecarboxylic acid was synthesized.Its structure was analyzed and characterized by IR and 1H NMR.The effects of material,oxidant,dosage of oxidant,reaction temperature and time on the synthesis were studied.The better technology has been obtained:the mole ratio of citraconic anhydride to hydrazin dihydrochloride is 1 ∶1.12 when 3,6-dihydroxy-4-methyl pyridazine was synthesized.The mole ratio of 3,6-dihydroxy-4-methyl pyridazine to phosphorous oxychloride is 1 ∶6 during chloric reaction.Taking nitric acid-chlorate liquor as oxidant,mass ratio of it to 3,6-dichloro-4-methyl pyridazine is 2 ∶ 1,reaction time is 3 h at 35~40 ℃.The yield of 3,6-dichloro-4-pyridazinecarboxylic acid is 52% and purity is over 98%.
Flame-retardant of melamine polyphosphate was synthesized from melamine and polyphosphate as raw materials,the yield was 90.4 %.The structure and performance of product was characterized by IR and DSC.The influence of molar ratio,reaction time and solvent on synthesis process was studied.The results show that the optimum reaction conditions are as follows:n(melamine) ∶n(polyphosphate)=3 ∶1,reaction time 16 h,acetic acid as solvent.
7-Hydroxyflavone(Ⅲ) was obtained by means of phase-transfer catalysis from 2,4-dihydroxyacetophenone and benzoyl chloride using tetrabutylammonium bisulfate as phase transfer catalyst through one-pot reaction.The yield of Ⅲ was 60%.Mechanism for Ⅲ formation was proposed,and mass spectrum of Ⅲ was resolved.2,4-Dihydroxyacetophenone(Ⅱ) was also synthesized from resorcinol(Ⅰ) and acetic acid,the yield of Ⅱ was 70%.
Flame-retardant of pentaerythritol biphosphorate melamine salt was synthesized using pentaerythritol,phosphorous oxychloride,and melamine as raw materials by two steps.The results showed that the optimum synthetic process was:in the first step,n[C(CH2OH)4] ∶n(POCl3)=1 ∶2.2,reaction time 7 h,reaction temperature 80 ℃,the yield 88%;in the second step,n(intermediate) ∶n(C3N6H6)=1 ∶2,reaction time 0.5 h,reaction temperature 80 ℃,the yield 98%.Chemical structure of the product was confirmed by IR and elemental analysis.
Using trinitrotoluene as base material,phloroglucinol was synthesized through oxidation,catalytic hydrogenation,hydrolyzing.Its structure was analysized and authenticed by IR,1H NMR and 13C NMR.The effects of oxidant,dosage of oxidant and catalyst,solvent,reaction temperature on the synthesis were studied.The better technology has been obtained as follows:taking nitric acid-chlorate liquor as oxidant,ratio of dosage of it to trinitrotoluene is 2 ∶1.Taking water-acetone as solvent,the amount of catalyst is 8% of the material,reaction temperature is 60 ℃,reaction time is 2.5 h on the catalytic hydrogenation reaction.At hydrolytic reaction pH is 3~4,reaction time is 16~20 h.The yield of phloroglucinol could reach 60%.The purity of phloroglucinol is 98%.
3,5-Diacetoxystyrene(1) was synthesized from 3,5-dihydroxyacetophenone(4) in a three-step process.3,5-Diacetoxyacetophenone(3) was synthesized from(4) and acetic anhydride with sulfuric acid as catalyst,the yield of(3) was 92%,(3) was identified by 1H NMR;1-(1-hydroxyethyl)-3,5-diacetoxybenzene(2) was obtained by catalytic hydrogenation from(3),the yield of(2) was 98%,(2) was identified by 1H NMR;(1) was obtained from(2) through a solid acid catalytic reaction,the reaction conditions were as follows:m(2) ∶m(solid acid)= 5 ∶1,reflux reaction time was 5 h at 110 ℃,the yield of(1) was 95% and the purity of(1) was 98%.(1) was identified by IR,1H NMR,MS,the results of 1H NMR of(1) and MS of(1) were resolved further.