The Stable-isotope Labeling And Application Of Triazine Herbicides

Because of its harm to human and animal health seriously,environmental hormones received extensive attention of the whole society.The two kinds of environmental hormones which are widely distributed are triazine herbicides and biphenyl compounds. The content of biphenyl compounds and triazine compounds in the environment are low. So the special detection method are needed for testing of them. The four carbon-13 labeled triazine compounds were synthesized and applied to detect the content of these four triazines in the soil. Meanwhile, the method of preparing deuterium labeled triazines were explored. For biphenyl compounds, the important intermediate of benzene-d6 were synthesized to provide technical support for further localization of standard substance.Triazine herbicides for simetryne, prometryne, terbuthylazine, terbutyrn belong to the environmental hormone and mainly affect the endocrine system, which have potential carcinogenic effects. In order to scientifically and accurately inspect the content of melamine in food and the pollution situation of triazine herbicides including simetryne, prometryne, terbuthylazine, terbutyrn in environment, for the first time this paper used the labeled urea as raw material and the content of the above triazine herbicides of ten provinces in soil in China was determined by isotope dilution mass spectrometry after the high temperature ring, chlorination, amination, methylthiolation for simetryne-13C3, prometryne-13C3, terbuthylazine-13C3, terbutyrn-13C3, at the same time the use of simetryne-13C3, prometryne-13C3, terbuthylazine-13C3, terbutyrn-13C3 as internal standard. All the LOQs were less than 0.2ug,RSDS were less than 10% and R2>0.999.For the actual test samples,prometryne was detected only in Beijing and Ningxia’soil, respectively 0.021 mg and 0.056 mg, which were lower than the maximum residue limits.of EU and Japan. Experiment results show that the use of these four kinds of C-13 labeled triazines as internal standard to detect the content of triazine herbicides in soil, could effectively correct the error caused by the instrument instability and pretreatment, eliminated matrix effect and improved the accuracy of the method. Moreover, the method can also be applied to the detection of triazine herbicides in other matrices.S-triazine is an important chemical intermediate. Melamine belongs to s-triazine, which has been widely used as an additive in the food industry. For the purpose of study the stable isotope labeling method of heterocyclic triazine compounds and its application, this study presents one step for the synthesis of melamine-d6 with a yield of 30%( calculate in ND4OD), which starts from ND4 OD, by the reacted with cyanuric chloride. According to the exchange mechanism of H/D, we discussed the feasibility and the necessary conditions for applying deuterium labeled in isotope dilution mass spectrometry method.The new method for synthesis of Benzene-d6 was discovered. In this process, Pt-black was used as the catalyst at H/D exchange reaction between benzene and deuterium oxide. The prepared method was in an overall yield of 20% and chemical purity of 99.7%. The product contained stable isotopes at 98% enrichment. The MS spectra, 13 C NMR, IR between benzene and benzene-d6 were discussed.