通过Gabriel反应合成经典化学发光试剂鲁米诺
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摘要
以3-硝基邻苯二甲酸为起始原料,先通过"一锅煮"的方法,连续实现酐交换、开环和闭环3步反应得到关键中间体N-甲基-3-硝基邻苯二甲酰亚胺。在40%水合肼溶液中,该中间体在100℃条件下发生Gabriel反应生成环酰肼,同时,中间体苯环上的硝基在自制催化剂Fe OOH作用下被水合肼还原为氨基。两个反应同步完成,极大的缩短了生产周期、反应温度较低、合成方法及操作简单、成本低、收率高、污染小,适用于工业化生产。在优化条件下,以83. 4%的总产率得到了超过现有技术标准的目标化合物。
In"one-pot"reaction with three continuous steps as anhydride exchange,ring-open and cyclization,the initial material of 3-nitro-phthalic acid was effectively converted to the key intermediate named N-methyl-3-nitro-phthalimide. In 40% hydrazine hydrate solution,ring hydrazide was formed via Gabriel reaction at 100 ℃,meanwhile,the nitro group on the benzene ring was reduced to amino group under the catalysis of home-made Fe OOH catalyst. The two-step reactions were completed simultaneously with low reaction temperature,simple method,convenient operation,low cost,high yield and decrease pollution,all of which merits were benefit for the industrial production process. Under the optimization conditions,the total yield of the product reaches up to83. 4%,higher than the existing technical standard.
In"one-pot"reaction with three continuous steps as anhydride exchange,ring-open and cyclization,the initial material of 3-nitro-phthalic acid was effectively converted to the key intermediate named N-methyl-3-nitro-phthalimide. In 40% hydrazine hydrate solution,ring hydrazide was formed via Gabriel reaction at 100 ℃,meanwhile,the nitro group on the benzene ring was reduced to amino group under the catalysis of home-made Fe OOH catalyst. The two-step reactions were completed simultaneously with low reaction temperature,simple method,convenient operation,low cost,high yield and decrease pollution,all of which merits were benefit for the industrial production process. Under the optimization conditions,the total yield of the product reaches up to83. 4%,higher than the existing technical standard.
引文
[1]庞彬彬,孙海鹰,徐云根.化学发光试剂的研究新进展[J].化学试剂,2017,39(9):942-948.
[2]HUNTRESS E H,STANLEY L N,PARKER A S,et al.The oxidation of 3-aminophthalhydrazide(“Luminol”)as a lecture demonstration of chemiluminescence[J]. J.Chem.Educ.,1934,11(3):142-145.
[3]DREW H D K,PEARMAN F H.Chemiluminescent organic compounds. PartⅡ. The eflect of substituents on the closure of phthalhydraxides to 5-and 6-membered rings[J].J.Chem.Soc.,1937,26(1):26-33.
[4]HUNTRESS E H,STANLEY L N,PARKER A S. The preparation of 3-aminophthalhydrazide for use in the demonstration of chemiluminescence[J]. J. Am. Chem. Soc.,1934,56(1):241-242.
[5]REDEMANN C T,REDEMANN C E. 5-Amino-2,3-dihydro-1,4-phthalazinedione[J]. Org. Synth.,1949,29:8-10.
[6]龙韬,刘相国,邹增龙.一种以邻苯二甲酰肼为原料制备异鲁米诺的方法:105 348 202A[P].2016-02-24.
[7]王中喜,王安琪,熊飞,等.一种利用一锅法合成鲁米诺或异鲁米诺的方法:106 810 501A[P].2017-06-09.
[8]刘维岩,杨瑜涛,李雪,等.反应型荧光探针在肼检测中的应用[J].化学试剂,2018,40(6):507-512.
[9]CASWELL L R,CAVASOS G.Cyclic imides.16.Hydroxy and methoxy derivatives of aminophthalimide and phthalhydrazide[J]. J. Heterocyclic Chem.,1995,32(3):907-914.
[10]袁雪生,张书胜.一种高产率异鲁米诺发光试剂的制备方法:106 083 732A[P].2016-11-09.
[11]LAUWINER M,RYS P,WISSMANN J.Reduction of aromatic nitro compounds with hydrazine hydrate in the presence of an iron oxide hydroxide catalyst.Ⅰ. The reduction of monosubstituted nitrobenzenes with hydrazine hydrate in the presence of ferrihydrite[J].Appl.Catal.AGen.,1998,172(1):141-148.
[12]蔡可迎.氢氧化氧铁催化剂制备及其催化活性[J].精细石油化工进展,2010,11(7):26-28.
[2]HUNTRESS E H,STANLEY L N,PARKER A S,et al.The oxidation of 3-aminophthalhydrazide(“Luminol”)as a lecture demonstration of chemiluminescence[J]. J.Chem.Educ.,1934,11(3):142-145.
[3]DREW H D K,PEARMAN F H.Chemiluminescent organic compounds. PartⅡ. The eflect of substituents on the closure of phthalhydraxides to 5-and 6-membered rings[J].J.Chem.Soc.,1937,26(1):26-33.
[4]HUNTRESS E H,STANLEY L N,PARKER A S. The preparation of 3-aminophthalhydrazide for use in the demonstration of chemiluminescence[J]. J. Am. Chem. Soc.,1934,56(1):241-242.
[5]REDEMANN C T,REDEMANN C E. 5-Amino-2,3-dihydro-1,4-phthalazinedione[J]. Org. Synth.,1949,29:8-10.
[6]龙韬,刘相国,邹增龙.一种以邻苯二甲酰肼为原料制备异鲁米诺的方法:105 348 202A[P].2016-02-24.
[7]王中喜,王安琪,熊飞,等.一种利用一锅法合成鲁米诺或异鲁米诺的方法:106 810 501A[P].2017-06-09.
[8]刘维岩,杨瑜涛,李雪,等.反应型荧光探针在肼检测中的应用[J].化学试剂,2018,40(6):507-512.
[9]CASWELL L R,CAVASOS G.Cyclic imides.16.Hydroxy and methoxy derivatives of aminophthalimide and phthalhydrazide[J]. J. Heterocyclic Chem.,1995,32(3):907-914.
[10]袁雪生,张书胜.一种高产率异鲁米诺发光试剂的制备方法:106 083 732A[P].2016-11-09.
[11]LAUWINER M,RYS P,WISSMANN J.Reduction of aromatic nitro compounds with hydrazine hydrate in the presence of an iron oxide hydroxide catalyst.Ⅰ. The reduction of monosubstituted nitrobenzenes with hydrazine hydrate in the presence of ferrihydrite[J].Appl.Catal.AGen.,1998,172(1):141-148.
[12]蔡可迎.氢氧化氧铁催化剂制备及其催化活性[J].精细石油化工进展,2010,11(7):26-28.