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·200· 精细化工 FINE CHEMICALS 第 37 卷

成功合成 D 5 -氯氰菊酯。本法可适用于其他拟除虫菊
酯类化合物的氘标记合成。
（2）对合成关键步骤进行了优化，获得了较好
的工艺条件：当反应时间为 3 h、反应温度为 130 ℃、
催化剂用量为 30 mmol 时，关键标记中间体的收率最
优；解决了关键标记中间体及终产品丰度稀释的技
术难题。以投入的氘代苯酚的物质的量计算，目标
产物 D 5 -氯氰菊酯的总收率为 19.5%。
1
（3）D 5 -氯氰菊酯结构经 HNMR、LC-MS 确
证；HPLC 检测 D 5 -氯氰菊酯的化学纯度超过 98%，
LC-MS 检测氘原子丰度为 98% atom D，同位素丰度
未出现明显稀释。产品可用作稳定同位素稀释质谱
法检测氯氰菊酯残留的内标试剂。

参考文献：
[1] Elliott M, Farnham A W, Janes N F, et al. Synthetic insecticide with a
new order of activity[J]. Nature, 1974, 248(5450): 710-711.
[2] Saxena K K, Seth N. Toxic effects of cypermethrin on certain
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图 4 D 5 -氯氰菊酯的核磁共振氢谱特征峰裂分 Bulletin of Environmental Contamination & Toxicology, 2002, 69(3):
1
Fig. 4 Characteristic peak splitting in HNMR of D 5 -cyper- 364-369.
methrin [3] Qin Wenxiu (秦文秀), Yan Dongyun (颜冬云), Liu Yan (刘艳), et al.
Research advances in toxicology of halogen pyrethroid insecticides
2.3.2 D 5 -氯氰菊酯的质谱解析 [J]. Agrochemicals (农药), 2009, 48(6): 394-398.
[4] Wang Qing (王青), Huang Zheng (黄铮). The study on the
D 5 -氯氰菊酯的液相色谱-质谱图见图 5。其中 development of pretreatment techniques about the detection of
+
m/Z=438 处峰为其加 NH 4 峰，m/Z=440 与 m/Z=442 pyrethroid pesticides residue in the food[J]. Food Research and
+
处两峰与[M+NH 4 ] 峰相比，根据质核比依次差 2 个 [5] Development (食品研究与开发), 2018, 39(11): 186-191.
Li lichun (李丽春), Liu Shugui (刘书贵), Yin Yi (尹怡), et al. Matrix
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442 两峰为 D 5 -氯氰菊酯的 Cl 同位素峰，质谱图与 [6] Sun Mengyuan (孙梦园), Shi Zhihong (石志红), Li Jianxun (李建
化合物结构吻合。 勋), et al. Determination of 7 pyrethroid pesticide residues in tea by
gas chromatography-triple quadrupole mass spectrometry combined

with dispersive solid-phase extraction and dispersive liquid-liquid
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[7] Shen Weijian (沈伟健), Cao Xiaowen (曹孝文), Liu Yijun (刘一军),
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[8] Luo Yong (罗勇), Yang Weicheng (杨维成), Liu Weixia (刘卫霞).
Syntheses of labeled 13C6-crystal violet and 13C6-leucocrystal
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[9] Wang Wei (王伟), Liu Zhanfeng (刘占峰), Du Xiaoning (杜晓宁).

Application of stable isotope in detection of veterinary drug
图 5 D 5 -氯氰菊酯的液相色谱-质谱图 residues[J]. Atomic Energy Science and Technology (原子能科学技
Fig. 5 LC-MS spectrum of D 5 -cypermethrin 术), 2010, 44(7): 813-819.
[10] Zhao Yipeng (赵依芃), Wang Zongyi (王宗义), Sha Fei (沙菲), et al.
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3 结论 isotope dilution gas chromatography-tandem mass spectrometry[J].
Journal of Chinese Institute of Food Science and Technology (中国
（1）以 D 6 -苯酚为原料，经氘氧化钾脱水成盐， 食品学报), 2018, 18(4): 312-317.
[11] Du Xiaoning (杜晓宁), Zhang Pengshuai (张鹏帅), Lei Wen (雷雯),
再与间溴苯甲醛通过优化后的乌尔曼缩合反应成功 et al. Application of stable isotope technique in food safety field[J].
得到关键标记中间体 D 5 -间苯氧基苯甲醛，最后与氰 Journal of Isotopes (同位素), 2019, 32(3): 231-243.

化钠、DV-菊酰氯经过相转移催化（氰醇）一步法 （下转第 216 页）