Qualitative Analysis of Precursor Substances of Phenyl-2-Acetone and 3，4-Methylenedioxyphenyl-2-Acetone

doi:10.12116/j.issn.1004-5619.2024.340701

Abstract

Abstract:

Objective To optimize and establish GC-MS, LC-MS, and infrared spectroscopy （IR） methods for analyzing 1-phenyl-2-propanone （P-2-P） and 3,4-methylenedioxyphenyl-2-propanone （MDP-2-P） precursors. Methods Eleven precursor substances of P-2-P and MDP-2-P were analyzed by GC-MS, LC-MS and IR methods, some key analytical parameters, such as solvent and injection temperature, were optimized. Results Substances such as 3-oxo-2-phenylbutyl methyl ester （MAPA） contain ester bonds in their structures were prone to ester exchange reactions. Therefore, alcohol solvent should be avoided to prevent the esterification. Instead, non-alcohol solvents, such as acetonitrile, were recommended. Substances such as MAPA that may undergo decomposition at the gas phase injection port temperature exceeded 170 ℃. It was recommended to lower the temperature of the injection port to 170 ℃. For substances that did not show peaks during GC-MS analysis, such as 2-methyl-3-phenylglycidic acid sodium salt （BMK sodium glycidylate） and 2-methyl-3-[3,4-（methylenedioxy）phenyl]glycidic acid sodium salt（PMK sodium glycidylate）, it was recommended for IR detection. Conclusion This study established GC-MS, LC-MS and IR methods that can accurately qualitatively analyze eleven P-2-P and MDP-2-P precursors, which can provide technical support for the detection of such substances in related cases.

Key words: forensic medicine, toxicological analysis, 1-phenyl-2-propanone （P-2-P）, 3,4-methylenedioxyphenyl-2-propanone （MDP-2-P）, precursor substances, gas chromatography-mass spectrometry （GC-MS）, liquid chromatography-mass spectrometry （LC-MS）, infrared spectrometry （IR）

CLC Number:

Xue-yan LIU, Wei JIA, Cui-mei LIU, Zhen-dong HUA, Zhen-chuan MA, Zhi-yu LI. Qualitative Analysis of Precursor Substances of Phenyl-2-Acetone and 3，4-Methylenedioxyphenyl-2-Acetone[J]. Journal of Forensic Medicine, 2025, 41(6): 566-573.

Figures/Tables 8

Fig. 1 Chemical structural formulas of P-2-P， MDP-2-P and their 11 precursor substances

Fig. 2 TICs of MAPA， MAMDPA， APAA and EAPA in different solvents （280 ℃）

Fig. 3 Mass spectra of the P-2-P， MDP-2-P and their precursor substances

Fig. 4 Proposed fragmentation pathways of MAPA and EAPA isomers under EI mode

Tab. 1 Peak area percentages of P-2-P and MDP-2-P at different injection port temperatures

物质	P-2-P或MDP-2-P峰面积百分比
物质	280 ℃	210 ℃	190 ℃	180 ℃	170 ℃	160 ℃
BMK methyl glycidate	0.0	0.0	0.0	0.0	0.0	0.0
BMK ethyl glycidate	0.0	0.0	0.0	0.0	0.0	0.0
PMK methyl glycidate	0.0	0.0	0.0	0.0	0.0	0.0
PMK ethyl glycidate	0.0	0.0	0.0	0.0	0.0	0.0
MAPA	7.7	2.4	0.8	0.3	0.0	0.0
APAA	31.2	11.0	10.1	0.0	0.0	0.0
MAMDPA	27.6	10.1	2.8	0.0	0.0	0.0
EAPA	11.4	5.4	3.3	2.6	2.5	2.5
BMK glycidic acid	28.6	14.5	10.5	10.0	5.7	5.6
BMK sodium glycidylate	/	/	/	/	/	/
PMK sodium glycidylate	/	/	/	/	/	/

Fig. 5 TICs of PMK methyl glycidate， PMK ethyl glycidate， BMK methyl glycidate and BMK ethyl glycidate，along with the mass spectra of their cis and trans isomers

Fig. 6 TICs and MS/MS spectra of BMK glycidic acid and PMK glycidic acid

Fig. 7 Infrared spectra of BMK sodium glycidylate and PMK sodium glycidylate

References 14

[1]	International Narcotics Control Board. Precursors and chemicals frequently used in the illicit manufacture of narcotic drugs and psychotropic substances 2022[R/OL]. （2023-03-09）[2024-04-23]. .
[2]	公安部，商务部，国家卫生健康委员会，应急管理部，海关总署，国家药品监督管理局. 关于将3-氧-2-苯基丁酸甲酯、3-氧-2-苯基丁酰胺、2-甲基-3-[3，4-（亚甲二氧基）苯基]缩水甘油酸、2-甲基-3-[3，4-（亚甲二氧基）苯基]缩水甘油酸甲酯、苯乙腈和γ-丁内酯6种物质列入易制毒化学品管理的公告[EB/OL]. （2021-08-16）[2025-03-16]. .
	Ministry of Public Security， Ministry of Commerce， National Health Commission， Ministry of Emergency Management， General Administration of Customs， National Medical Products Administration. Announcement on the inclusion of 3 -oxo-2-phenylbutyl methyl ester， 3-oxo-2-phenylbutyl amide， 2-methyl-3-[3，4-（methylenedioxy）phenyl]glycidic acid， 2-methyl-3-[3，4-（methylenedioxy）phenyl]glycidic acid methyl ester， phenylacetonitrile， and γ-butyrolactone into the management of precursor chemicals[EB/OL]. （2021-08-16）[2025-03-16]. .
	cn:9080/n6557558/c8076986/content.html.
[3]	公安部，商务部，国家卫生健康委员会，应急管理部，海关总署，国家药品监督管理局. 关于将4-（N-苯基氨基）哌啶、1-叔丁氧羰基-4-（N-苯基氨基）哌啶、N-苯基-N-（4-哌啶基）丙酰胺、大麻二酚、2-甲基-3-苯基缩水甘油酸及其酯类、3-氧-2-苯基丁酸及其酯类、2-甲基-3-[3，4-（亚甲二氧基）苯基]缩水甘油酸酯类列入易制毒化学品管理的公告[EB/OL]. （2024-08-02）[2025-03-16]. .
	Ministry of Public Security， Ministry of Commerce， National Health Commission， Ministry of Emergency Management， General Administration of Customs， National Medical Products Administration. Announcement on the inclusion of 4 -（N-phenylamino）piperidine， 1-tert-butoxycarbonyl-4-（N-phenylamino）piperidine， N-phenyl-N-（4-piperidinyl）propanamide， cannabidiol， 2-methyl-3-phenylglycidic acid and its esters， 3-oxo-2-phenylbutyric acid and its esters， and 2-methyl-3-[3，4-（methylenedioxy）phenyl]glycidic acid esters into the management of precursor chemicals[EB/OL]. （2024-08-02）[2025-03-16]. .
[4]	郭建，林小龙，吴升武，等. α-溴代苯丙酮的检验研究[J].刑事技术，2016，41（3）：206-208. doi：10.16467/j.1008-3650.2016.03.009 .
	GUO J， LIN X L， WU S W， et al. Analysis of α- bromopropiophenone[J]. Xingshi Jishu，2016，41（3）：206-208.
[5]	钱振华，徐鹏. GC/MS检验1-苯基-1-丙酮和1-苯基-2-丙酮[J].刑事技术，2012，37（3）：24-26. doi：10.16467/j.1008-3650.2012.03.008 .
	QIAN Z H， XU P. Analysis of 1-phenyl-1-propanone and 1-phenyl-2-propanone by GC/MS[J]. Xingshi Jishu，2012，37（3）：24-26.
[6]	施妍，向平，沈保华，等. 易制毒化学品α-溴代苯丙酮的检测及应用[J].中国司法鉴定，2017（3）：36-39. doi：10.3969/j.issn.1671-2072.2017.03.006 .
	SHI Y， XIANG P， SHEN B H， et al. Detection of α-bromopropiophenone and its application[J]. Zhongguo Sifa Jianding，2017（3）：36-39.
[7]	赵阳，胡羽鹏，常颖，等. MDMA前体PMK methyl glycidate的定性检验[J].刑事技术，2022，47（1）：96-99. doi：10.16467/j.1008-3650.2021.0120 .
	ZHAO Y， HU Y P， CHANG Y， et al. Qualitative identification of PMK methyl glycidate， MDMA’s precursor[J]. Xingshi Jishu，2022，47（1）：96-99.
[8]	周华，翟志平，胡羽鹏，等. 两种苯丙胺类兴奋剂前体化学品的检验与分析[J].中国药物依赖性杂志，2023，32（4）：319-322. doi：10.13936/j.cnki.cjdd1992.2023.04.015 .
	ZHOU H， ZHAI Z P， HU Y P， et al. Inspection and analysis of two kinds of ATS precursor chemicals[J]. Zhongguo Yaowu Yilaixing Zazhi，2023，32（4）：319-322.
[9]	梁未未，林贤文，田源源，等. 新型易制毒化学品α-乙酰基苯乙酸甲酯的结构确认和检验鉴定方法研究[J].刑事技术，2021，46（4）：331-336. doi：10.16467/j.1008-3650.2021.0091 .
	LIANG W W， LIN X W， TIAN Y Y， et al. Structure confirmation and identification of α-acetyl-methyl phenylacetate， a new precursor chemical for designer drug[J]. Xingshi Jishu，2021，46（4）：331-336.
[10]	TSUJIKAWA K， OKADA Y， SEGAWA H， et al. Analysis of potential phenylacetone precursors （ethyl 3-oxo-2-phenylbutyrate， methyl 3-oxo-4-phenylbuty-rate， and ethyl 3-oxo-4-phenylbutyrate） by gas chromatography/mass spectrometry and their conversion to phenylacetone[J]. Drug Test Anal，2022，14（3）：439-449. doi：10.1002/dta.3169 .
[11]	刘翠梅，花镇东，贾薇. 阿米雷司类似物4’-F-4-MAR的结构解析与表征[J].法医学杂志，2020，36（5）：677-681，687. doi：10.12116/j.issn.1004-5619.2020.05.013 .
	LIU C M， HUA Z D， JIA W. Structure analysis and characterization of aminorex analogue 4’-F-4-MAR[J]. Fayixue Zazhi，2020，36（5）：677-681，687.
[12]	孟鑫，花镇东，贾薇，等. 可疑植物制品中合成大麻素5F-EDMB-PICA的鉴定[J].法医学杂志，2021，37（4）：486-492. doi：10.12116/j.issn.1004-5619.2021.310304 .
	MENG X， HUA Z D， JIA W， et al. Identification of synthetic cannabinoid 5F-EDMB-PICA in suspicious herbal products[J]. Fayixue Zazhi，2021，37（4）：486-492.
[13]	刘翠梅，韩煜，贾薇，等. 近红外光谱用于甲基苯丙胺快速定量分析方法研究[J].光谱学与光谱分析，2020，40（9）：2732-2736. doi：10.3964/j.issn.1000-0593（2020）09-2732-05 .
	LIU C M， HAN Y， JIA W， et al. Rapid quantitative analysis of methamphetamine by near infrared spectroscopy[J]. Guangpuxue Yu Guangpu Fenxi，2020，40（9）：2732-2736.
[14]	COLLINS M， HEAGNEY A， CORDARO F， et al. Methyl 3-[3’， 4’-（methylenedioxy）phenyl]-2-methyl glycidate： An ecstasy precursor seized in Sydney， Australia[J]. J Forensic Sci，2007，52（4）：898-903. doi：10.1111/j.1556-4029.2007.00480.x .

[1]	Ya-ning SUN, Dan-yang LI, Qing XIA, Yan GAO, Zong-shi XU, Wen-tao XIA, Hui-ming ZHOU, Xiao-meng HAN, Xiao-ying YU, Yan-liang SHENG. Frontiers and Perspectives of Artificial Intelligence in Forensic Research on CT Imaging Diagnosis of Rib Fractures [J]. Journal of Forensic Medicine, 2025, 41(6): 593-600.
[2]	Yan GAO, Xia LIU, Fang CHEN, Xiao-ping YANG, Ze-yu WANG, Ya-ning SUN, Yan-liang SHENG, Wen-tao XIA. Comparison of NB Chirp ABR and 40 Hz AERP in Normal Hearing Adults [J]. Journal of Forensic Medicine, 2025, 41(6): 559-565.
[3]	Qiong-ying ZHENG, Xue-yi FENG, Hong-xiao DENG, Jia-xin YU, Wen-jia DUAN, Zheng QIAO, Xin WANG, Wei LIU, Ke-ming YUN, Hang CHEN, Ping XIANG. Sources of Uncertainty and Influencing Factors in the Analysis of Volatile Components in Blood Using Headspace Gas Chromatography [J]. Journal of Forensic Medicine, 2025, 41(6): 574-584.
[4]	Hou-ying ZOU, Yin-lei LEI, Ruo-cheng XIA, Yan SHI, Cheng-tao LI. Exploring Microbial Detection of Psychoactive Substances in Wastewater Based on Micobiome Analysis [J]. Journal of Forensic Medicine, 2025, 41(5): 468-476.
[5]	Han ZHANG, Xin HUANG, An-qi CHEN, Ji CHEN, Yan-fang LU, Jian-ye ZENG, Xiang WANG. Skin Microbiome： Expanding Dimensions and Challenges in Forensic Evidence [J]. Journal of Forensic Medicine, 2025, 41(5): 443-455.
[6]	Zhi-yong LIU, Xing-chun ZHAO, Ling CHEN, Ri-ga WU, Mei-qing YUAN, Xiao-hui CHEN, Jian ZHAO, Qu-yi XU, Chang-hui LIU, Hong-yu SUN, Chao LIU. Recommendations for the Standardization of Forensic Microbiological Analysis [J]. Journal of Forensic Medicine, 2025, 41(5): 482-493.
[7]	Yan GAO, Fang CHEN, Wen-tao XIA, Xiao-ping YANG, Ze-yu WANG, Ze-ren YANG, Xia LIU, Yan-liang SHENG. Research Progress of Chirp ABR and Its Application in Forensic Auditory Identification [J]. Journal of Forensic Medicine, 2025, 41(4): 387-393.
[8]	Wen-yan LI, Jin-feng ZHAO, Wei-chen LIU, Shi-jing LÜ, Jia-xin ZHANG, Xu-dong ZHANG, Zhi-wen WEI, Ke-ming YUN, Chao ZHANG. Toxicokinetics of Chlorfenapyr and Its Metabolites in Rats [J]. Journal of Forensic Medicine, 2025, 41(4): 380-387.
[9]	Min SHEN. Practice and Reflection on Forensic Toxicology from the Perspective of Evidence Reliability [J]. Journal of Forensic Medicine, 2025, 41(4): 297-306.
[10]	Li-xia WEI, Bo LIU, Xiao-yuan YANG, Xi ZHANG, Yi-feng LAN, Chao ZHANG, Juan JIA, Dan ZHANG, Zhi-wen WEI, Ke-ming YUN, Zhe CHEN. Detection of Ketamine and Norketamine Using an Aptamer-Functionalized Graphene Oxide Fluorescent Sensor [J]. Journal of Forensic Medicine, 2025, 41(4): 326-339.
[11]	Jia-hao LI, Jiang LING, Zi-hao CAI, Zi-yuan ZHENG, Yan-jun DING. Fluorescent Probe Development for Rapid Detection of Tiletamine Based on Copper Nanozyme and Molecular Imprinting Technology [J]. Journal of Forensic Medicine, 2025, 41(4): 355-363.
[12]	Zi-wen GUO, Tian-yu QIU, Yue CAO. Rapid Identification of Etomidate and Its Structural Analogues Based on Surface-Enhanced Raman Spectroscopy and Machine Learning [J]. Journal of Forensic Medicine, 2025, 41(4): 364-370.
[13]	Tai-shen HE, Zhong-jiang LÜ, Yi-ming SUN, Yu-yang LI, Yi YE, Yao LIN, Lin-chuan LIAO. Rapid Analysis of Cyanide Based on a Ratiometric Fluorescent Probe Using Gold Nanoclusters-Fluorescein [J]. Journal of Forensic Medicine, 2025, 41(4): 340-347.
[14]	Meng-yao TANG, Bo-yu HUANG, Cui-mei LIU, Xue-yan LIU, Wei JIA, Zhen-dong HUA. Rapid Screening of Etomidate and Its Analogues Using a Portable Mass Spectrometer [J]. Journal of Forensic Medicine, 2025, 41(4): 348-354.
[15]	Jing-chun BAO, Jing-jing ZHAO, Jiao-yong LI, Jing-hua MENG, Xiao-long WANG, Xiao-ni ZHAN, Jun YAO, Xu WU. Construction of a Competency Evaluation Model for Forensic Practitioners [J]. Journal of Forensic Medicine, 2025, 41(4): 371-379.