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放射性同位素碳-14标记氯虫苯甲酰胺的合成与分析

杨征敏 宋明钰 陈沪飞 余志扬 周迪 夏燕婷 郑东敏 薛晓娅

杨征敏, 宋明钰, 陈沪飞, 余志扬, 周迪, 夏燕婷, 郑东敏, 薛晓娅. 放射性同位素碳-14标记氯虫苯甲酰胺的合成与分析[J]. 农药学学报, 2020, 22(1): 19-26. doi: 10.16801/j.issn.1008-7303.2020.0003
引用本文: 杨征敏, 宋明钰, 陈沪飞, 余志扬, 周迪, 夏燕婷, 郑东敏, 薛晓娅. 放射性同位素碳-14标记氯虫苯甲酰胺的合成与分析[J]. 农药学学报, 2020, 22(1): 19-26. doi: 10.16801/j.issn.1008-7303.2020.0003
YANG Zhengmin, SONG Mingyu, CHEN Hufei, YU Zhiyang, ZHOU Di, XIA Yanting, ZHENG Dongmin, XUE Xiaoya. Synthesis and analysis of radioisotope carbon-14 labelled chlorantraniliprole[J]. Chinese Journal of Pesticide Science, 2020, 22(1): 19-26. doi: 10.16801/j.issn.1008-7303.2020.0003
Citation: YANG Zhengmin, SONG Mingyu, CHEN Hufei, YU Zhiyang, ZHOU Di, XIA Yanting, ZHENG Dongmin, XUE Xiaoya. Synthesis and analysis of radioisotope carbon-14 labelled chlorantraniliprole[J]. Chinese Journal of Pesticide Science, 2020, 22(1): 19-26. doi: 10.16801/j.issn.1008-7303.2020.0003

放射性同位素碳-14标记氯虫苯甲酰胺的合成与分析

doi: 10.16801/j.issn.1008-7303.2020.0003
详细信息
    通讯作者:

    杨征敏,通信作者 (Author for correspondence),男,博士,技术总监,主要从事功能化学品的放射性同位素标记合成与代谢研究,E-mail:zmyang@qzisotech.com

  • 中图分类号: O628.21;S482.3

Synthesis and analysis of radioisotope carbon-14 labelled chlorantraniliprole

  • 摘要: 以 [ 14C ] 碳酸钡为放射性同位素原料,通过格氏反应、亲核取代、胺化和缩合等8步放化反应制备了2种放射性同位素碳-14 标记的氯虫苯甲酰胺粗品,经反相高效液相色谱(RP-HPLC)纯化获得标记物纯品14C-氯虫苯甲酰胺 [ 3-溴-N- [ 4-氯-2-甲基-6-( 甲氨基 [ 羰基-14C ] 甲酰基) 苯基 ] -1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺 ( 2 , 55.6 mCi)和3-溴-N- [ 4-氯-2-甲基-6- (甲氨基甲酰基) 苯基 ] -1-(3-氯-2-吡啶基)-1H-吡唑-5- [ 羰基-14C ] 甲酰胺 ( 3 , 58.6 mCi) ] 。以 [ 14C ] 碳酸钡计,两种标记物的总放化收率分别为32%和52%。其结构经核磁共振氢谱、质谱和在线放射性高效液相色谱 (HPLC-FSA) 分析确认。放射性薄层成像分析 (TLC-IIA)、离线放射性高效液相色谱分析(HPLC-LSC)、在线放射性高效液相色谱-二极管阵列检测器/质谱联用 (HPLC-FSA/PDA/MS) 和LSC分析表明,两种14C-氯虫苯甲酰胺的放化纯度分别为99.8%和99.6%,化学纯度分别为99.1%和98.4%,比活度分别为52.45 mCi/mmol和52.30 mCi/mmol。这2种标记物可作为放射性示踪剂,可满足氯虫苯甲酰胺在中国的登记代谢试验研究的需要。
  • 1  氯虫苯甲酰胺 (1) 及其放射性同位素碳-14标记物 ( *表示碳-14标记位点)

    1.  Chlorantraniliprole (1) and its radioisotope carbon-14 labelled counterparts(*indicates carbon-14 labelled sites)

    2  [ 苯甲酰胺羰基-14C] 氯虫苯甲酰胺 (2) 的合成路线 (*表示碳-14标记位点)

    2.  Synthetic route of [benzamide carbonyl-14C]chlorantraniliprole 2 (*indicates carbon-14 labelled sites)

    3  [ 吡唑甲酰胺羰基-14C] 氯虫苯甲酰胺 (3) 的合成路线 (*表示碳-14标记位置)

    3.  Synthetic route of [pyrazolylamide carbonyl-14C]chlorantraniliprole 3 (*indicates carbon-14 labelled sites)

    图  1  碳-14标记氯虫苯甲酰胺 (2) 的离线放射性高效液相色谱图 (HPLC-LSC)

    Figure  1.  Offline radio-chromatogram (HPLC-LSC) of the carbon-14 labelled chlorantraniliprole (2)

    图  2  碳-14标记氯虫苯甲酰胺 (2) 的高效液相色谱图(HPLC-UV)

    Figure  2.  High performance liquid chromatogram of the carbon-14 labelled chlorantraniliprole (2)

    4  丙酯草醚 (15)、氯虫苯甲酰胺 (16) 和环磺酮 (17) 分子中的标记单元

    4.  Radiolabelling units of pyribambenz-propyl (15), chlorantraniliprole (16) and tembotrione (17)

  • [1] 柏亚罗. 氯虫苯甲酰胺将于2021年专利到期[J]. 农药市场信息, 2016(17): 34.

    BAI Y L. The patent of chlorantraniliprole is about to expire in 2021[J]. Pestic. Market News, 2016(17): 34.
    [2] G·P·拉姆, B·J·迈尔斯, T·P·塞尔比, 等. 杀虫的邻氨基苯甲酰胺: CN1419537A[P]. 2003-05-21.

    LAHM G P, MYERS B J, SELBY T P, et al. Insecticidal anthranilamides: CN1419537A[P]. 2003-05-21.
    [3] 农业部种植业管理司. 中华人民共和国农业部公告第2569号: 农药登记资料要求[S/OL]. 2017-09-13. http://www.zzys.moa.gov.cn/gzdt/201712/t20171227_6310271.htm.

    Department of Planting Management, Ministry of Agriculture. Announcement No. 2569 of the Ministry of Agriculture of the People's Republic of China: Data requirements on pesticide registration[S/OL]. 2017-09-13. http://www.zzys.moa.gov.cn/gzdt/201712/t20171227_6310271.htm.
    [4] 农作物中农药代谢试验准则NY/T 3096—2017[S]. 北京: 中华人民共和国农业部. 2017-06-12.

    Guideline for the testing of pesticide metabolism in crops NY/T 3096—2017[S]. Beijing: Ministry of Agriculture of the PRC. 2017-06-12.
    [5] 经济合作与发展组织化学品测试准则编译委员会. 经济合作与发展组织化学品测试准则[M]. 北京: 中国农业出版社, 2013: 1367.

    Compilation and translation committee of OECD guidelines for the testing of chemicals. OECD guidelines for the testing of chemicals[M]. Beijing: China Agriculture Press, 2013: 1367.
    [6] US EPA: Test guidelines for pesticides and toxic substances: series 860-residue chemistry test guidelines[S/OL]. [1996-08].https://www.epa.gov/test-guidelines-pesticides-and-toxic-substances/series-860-residue-chemistry-test-guidelines.
    [7] US EPA: test guidelines for pesticides and toxic substances: series 835-fate, transport and transformation test guidelines[S/OL]. [January 1998]. https://www.epa.gov/test-guidelines-pesticides-and-toxic-substances/series-835-fate-transport-and-transformation-test.
    [8] 贾明宏, 李本昌. 农药学研究的重要手段: 放射性同位素示踪技术[J]. 农药科学与管理, 1996, 17(4): 14-19.

    JIA M H, LI B C. Important method for research pesticide science: radioisotope tracer techniques[J]. Pestic Sci Admin, 1996, 17(4): 14-19.
    [9] GADDAMIDI V, SCOTT M T, SWAIN R S, et al. Metabolism of [14C]chlorantraniliprole in the lactating goat[J]. J Agric Food Chem, 2011, 59(4): 1316-1323. doi: 10.1021/jf103558n
    [10] GADDAMIDI V, ZIMMERMAN W T, PONTE M, et al. Pyrolysis of [14C]-chlorantraniliprole in tobacco[J]. J Agric Food Chem, 2011, 59(17): 9424-9432. doi: 10.1021/jf201995b
    [11] European Food Safety Authority. Conclusion on the peer review of the pesticide risk assessment of the active substance chlorantraniliprole[J]. EFSA Journal, 2013, 11(6): 3143-3250. doi: 10.2903/j.efsa.2013.3143
    [12] ARMAREGO W L F, CHAI C L L. Purification of laboratory chemicals[M]. 7th ed. Boston: Butterworth-Heinemann, 2012.
    [13] MOCHIZUKI M, KORI M, KONO M, et al. Discovery of a 7-arylaminobenzimidazole series as novel CRF1 receptor antagonists[J]. Bioorg Med Chem, 2016, 24(19): 4675-4691. doi: 10.1016/j.bmc.2016.08.005
    [14] SCHAREINA T, ZAPF A, COTTÉ A, et al. A versatile protocol for copper-catalyzed cyanation of aryl and heteroaryl bromides with acetone cyanohydrin[J]. Adv Synth Catal, 2011, 353(5): 777-780. doi: 10.1002/adsc.201000200
    [15] YANG Z M, XU Y J, ZHANG G H, et al. Synthesis of carbon-14 labeled ZJ0712, a novel strobilurin fungicide[J]. J Label Compd Radiopharm, 2018, 61(11): 812-819. doi: 10.1002/jlcr.3646
    [16] 杨征敏, 见才广, 周兵, 等. 两种放射性同位素碳-14标记毒氟磷的合成与分析[J]. 有机化学, 2018, 38(5): 1177-1184.

    YANG Z M, JIAN C G, ZHOU B, et al. Synthesis and analysis of two versions of radioisotope carbon-14 labelled Dufulin[J]. Chin J Org Chem, 2018, 38(5): 1177-1184.
    [17] LAHM G P, STEVENSON T M, SELBY T P, et al. Rynaxypyr: a new insecticidal anthranilic diamide that acts as a potent and selective ryanodine receptor activator[J]. Bioorg Med Chem Lett, 2007, 17(22): 6274-6279. doi: 10.1016/j.bmcl.2007.09.012
    [18] LAHM G P, PASTERIS R J. Arthropodicidal anthranilamides: WO03106427[P]. 2003-02-27.
    [19] 柴宝山, 彭永武, 李慧超, 等. 氯虫酰胺的合成与杀虫活性[J]. 农药, 2009, 48(1): 13-16. doi: 10.3969/j.issn.1008-7303.2009.01.002

    CHAI B S, PENG Y W, LI H C, et al. Synthesis of Chlorantraniliprole and its insecticidal activity[J]. Agrochem, 2009, 48(1): 13-16. doi: 10.3969/j.issn.1008-7303.2009.01.002
    [20] 杨征敏, 叶庆富, 唐庆红, 等. 新型除草剂丙酯草醚A环14C均标记合成和鉴定[J]. 化学学报, 2005, 63(21): 1999-2003. doi: 10.3321/j.issn:0567-7351.2005.21.010

    YANG Z M, YE Q F, TANG Q H, et al. Radiolabeled synthesis and identification of a novel herbicide, propyl 4-[2-(4, 6-dimethoxy-2-pyrimidinyloxy) benzylamino]benzoate with all six benzoic ring carbons labeled by 14C[J]. Acta Chim Sin, 2005, 63(21): 1999-2003. doi: 10.3321/j.issn:0567-7351.2005.21.010
    [21] YANG Z M, YE Q F, LU L. Synthesis of herbicidal ZJ0273 labeled with tritium and carbon-14[J]. J Label Compd Radiopharm, 2008, 51(4): 182-186. doi: 10.1002/jlcr.1498
    [22] YANG Z M, JI Z Q, YE Q F, et al. Synthesis of 6β-([1-14C]propoxy) celangulin V[J]. J Label Compd Radiopharm, 2008, 51(2): 109-112. doi: 10.1002/jlcr.1493
    [23] 杨征敏, 张贵华, 许亚军, 等. 高比活度碳-14标记吡虫啉的合成与分析[J]. 核化学与放射化学, 2018, 40(3): 196-202. doi: 10.7538/hhx.2018.YX.2017055

    YANG Z M, ZHANG G H, XU Y J, et al. Synthesis and analysis of carbon-14 labelled Imidacloprid with high specific activity[J]. J Nucl Radiochem, 2018, 40(3): 196-202. doi: 10.7538/hhx.2018.YX.2017055
    [24] 许亚军, 张贵华, 杨征敏, 等. 高比活度碳-14标记毒氟磷的合成与分析[J]. 农药学学报, 2017, 19(6): 672-678.

    XU Y J, ZHANG G H, YANG Z M, et al. Synthesis and analysis of carbon-14 labelled Dufulin with high specific activity[J]. Chin J Pestic Sci, 2017, 19(6): 672-678.
    [25] Filer C N. Radiolabeled insecticides, herbicides and fungicides[J]. Isot. Phys. Biomed. Sci., 1991, 1(Labelled Compd., Pt. B): 1-44.
    [26] YANG Z M, WANG W, HAN A L, et al. Determination of herbicide ZJ0273 residue in rapeseed by radioisotopic tracing method[J]. Food Chem, 2009, 114(1): 300-305. doi: 10.1016/j.foodchem.2008.08.095
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  • 收稿日期:  2019-05-14
  • 录用日期:  2019-07-02
  • 刊出日期:  2020-02-01

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