α-[二(烷氧羰基)甲基]查尔酮的制备及其在多取代环丙烷衍生物合成中的应用

doi:10.6023/cjoc202408023

摘要/Abstract

研究了α-[二(烷氧羰基)甲基]查尔酮的合成和环丙烷化反应. 2-芳甲酰甲亚基丙二酸酯与芳甲基对甲基苯基砜在氢化钠作用下反应, 经共轭加成/消除过程得到α-[二(烷氧羰基)甲基]查尔酮. α-[二(烷氧羰基)甲基]查尔酮与三甲基碘化亚砜在氢化钠作用下反应, 经共轭加成/环丙烷化过程得到多取代环丙烷衍生物2-(1-芳甲酰基-2-芳基环丙基)丙二酸酯. 初步研究表明所得环丙烷衍生物可在无催化剂条件下与乌洛托品或1,3,5-三苯基-1,3,5-三嗪烷发生环缩合反应, 生成结构新颖的杂环产物.

关键词: 合成, 共轭加成, 查尔酮, 环丙烷化

The synthesis and cyclopropanation of α-(di(alkoxycarbonyl)methyl)chalcones were studied. In the presence of sodium hydride, 2-aroylmethylenemalonates reacted with arylmethyl p-tolyl sulfone to give α-(di(alkoxycarbonyl)methyl)- chalcones via a conjugate addition/elimination sequence. Under the promotion of sodium hydride, the reaction of α-(di(alkoxy- carbonyl)methyl)chalcones with trimethylsulfoxonium iodide proceeded via a conjugate addition/cyclopropanation sequence to give multisubstituted cyclopropane of 2-(1-aroyl-2-arylcyclopropyl)malonates. In a preliminary study, these cyclopropanes showed good reactivity in the cyclocondensation reactions with urotropin or 1,3,5-triphenyl-1,3,5-triazinane to provide structurally novel heterocyclic products under catalyst-free conditions.

Key words: synthesis, conjugate addition, chalcone, cyclopropanation

引用此文

焦俊强, 杨高升. α-[二(烷氧羰基)甲基]查尔酮的制备及其在多取代环丙烷衍生物合成中的应用[J]. 有机化学, 2025, 45(7): 2586-2599.

Junqiang Jiao, Gaosheng Yang. Preparation of α-(Di(alkoxycarbonyl)methyl)chalcones and Their Application in the Synthesis of Multisubstituted Cyclopropanes[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2586-2599.

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图/表 7

图式1. α-[二(烷氧羰基)甲基]查尔酮的合成

Scheme 1. Synthesis of α-(di(alkoxycarbonyl)methyl)chalcones

Entry	TsBn/equiv.	NaH/equiv.	Solvent	Temperature/℃	Time^b/h	Yield^c/% of 3aa
1	1.5	2.5	DMF	25	12	NR
2	1.5	2.5	DMF	40	10	66
3	1.5	2.5	DMF	60	6	84
4	1.5	2.5	DMF	80	3	67
5	1.5	2.0	DMF	60	24	58
6	1.5	3.0	DMF	60	5	62^d
7	1.5	2.5	THF	60	6	78
8	1.5	2.5	DMSO	60	12	90
9	1.1	2.5	DMSO	60	14	85

表1. 苄基对甲基苯基砜(1a)与2-苯甲酰基甲亚基丙二酸二乙酯(2a)反应条件的优化a

Table 1. Optimization of reaction conditions for 2-benzoylmethylenemalonate (2a) with benzyl p-tolyl sulfone (1a)

表2. α-[二(烷氧羰基)甲基]查尔酮(3)的制备a,b

Table 2. Preparation of α-(di(alkoxycarbonyl)methyl)chalcones (3)

Entry	OS^＋(CH₃)₃I⁻/equiv.	NaH/equiv.	Solvent	Temperature/℃	Time^b/h	Yield^c/% of 4a	dr^d
1	2.0	3.0	DMF	40	96	78	96∶4
2	2.0	3.0	DMF	50	48	88	94∶6
3	2.0	3.0	DMF	60	37	80	87∶13
4	1.5	3.0	DMF	50	52	40	75∶25
5	2.5	3.0	DMF	50	72	45	90∶10
6	2.0	2.5	DMF	50	96	42	91∶9
7	2.0	3.5	DMF	50	30	75	80∶20
8	2.0	3.0	DMSO	50	48	82	89∶11
9	2.0	3.0	THF	50	78	63	88∶12

表3. 三甲基碘化亚砜与3aa反应条件的优化a

Table 3. Optimization of reaction conditions for 3aa with trimethylsulfoxonium iodide

表4. 多取代环丙烷衍生物4的合成a,b

Table 4. Synthesis of the multisubstituted cyclopropanes 4

图式2. α-[二(烷氧羰基)甲基]查尔酮(3)的制备及其环丙烷化反应的可能机理

Scheme 2. Possible mechanism for the preparation and cyclopropanation of α-(di(alkoxycarbonyl)methyl)chalcone (3)

图式3. 环丙烷4a与乌洛托品或1,3,5-三苯基-1,3,5-三嗪烷的反应

Scheme 3. Reactions of cyclopropane 4a with urotropin or 1,3,5-triphenyl-1,3,5-triazine

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