Page 247 - 精细化工2019年第8期
P. 247
第 8 期 陆婷婷,等: 3-氨基呋咱-4-羧酸的合成 ·1735·
2.42,N:32.63,与 3-氨基呋咱-4-羧酸的理论元素 molecule inhibitors for the β-catenin/T-cellfactor protein-protein
interaction through the optimization of the acylhydrazone moiety[J].
值相似(C:27.92,H;2.34,N:32.55)。Meyer Journal of Medicinal Chemistry, 2015, 46: 113-128.
的元素分析结果为 C:24.15,H;1.62,N:28.25, [4] Sheremeteev A. Chemistry of furazan fused to five-membered rings[J].
Journal of Heterocyclic Chemistry, 1995, 32(2): 371-385.
与 3-氨基呋咱-4-羧酸的理论值相差较大。 [5] Churakov A, Semenov S, Ioffe S, et al. The oxidation of the
Willer 经过 DSC 分析,并进行单晶培养,最终 heterocyclic amines to nitro compounds using dinirogen pentoxide[J].
Mendeleev Communication, 1995, (3): 102-103.
确定了 Sheremetev 的产物为 3-氨基呋咱-4-羧酸,
[6] He Liqin (何黎琴), Gu Hongxia (顾宏霞), Yin Dengke (尹登科),
Meyer 的产物为二(3-氨基呋咱-4-羧酸)钾盐。这 et al. Synthesis and anticancer activity of nitric oxide donorbased
matrine derivatives [J]. Chemical Journal of Chinese Universities (高
两种化合物在酸碱条件下可以互换,如下所示:
等学校化学学报), 2010,31(8): 1541-1547.
[7] Huo Huan (霍欢), Wang Bozhou (王伯周), Wang Xijie (王锡杰),
et al. Research progress in synthesis of furazan energetic compounds
and reaction of their derivatives[J]. Chemical Propellants & Polymeric
Materials (化学推进剂与高分子材料), 2013, 11(3): 15-22.
[8] Li Yanan (李亚南), Zhang Zhizhong (张志忠), Zhou Yanshu: (周
彦水), et al. Synthesis and thermal decomposition mechanism of
虽然 Sheremetev 法可以得到最终产物 3-氨基呋 3,4-bis(3, 5-dinitrobenzene-1-yl) furoxan[J]. Chinese Journal of
Energetic Materials (含能材料), 2011,19(3): 262-268.
咱-4-羧酸,但仔细分析 Sheremetev 法发现其存在一
[9] Zhai Lianjie (翟连杰), Luo Yifen (罗义芬), Li Yanan (李亚南), et
定的缺点:反应温度达到 100 ℃,对于水作为溶剂 al. Synthesis and properties of 3-cyano-4-nitrofuroxan[J]. Chinese
Journal of Energetic Materials (含能材料), 2017, 25(6): 503-507.
的反应较难达到;后处理中要用到有机溶剂乙醚,
[10] Willer R, Storey R, Deschamps J, et al. Synthesis and crystal structure of
乙醚的沸点较低,容易造成危险,而且要对得到的 4,4-(methylenediimino)bis-1,2,5-oxadiazole-3-carboxylic acid and
carboxamide[J]. Journal of Heterocyclic Chemistry, 2013, 50:
化合物进行重结晶,增加了成本;反应收率较低,
949-954.
仅为 64%。 [11] Zhai Lianjie (翟连杰), Wang Bozhou (王伯周), Li Yanan (李亚
本文结合了 Meyer 和 Sheremetev 的合成方法, 南 ), et al. Crystal structure and thermal behavior of 3,4-bis(3-
cyanofurazan-4-oxy) furazan (FOF-12)[J]. Chinese Journal of
先在 KOH 催化下合成二(3-氨基呋咱-4-羧酸)钾 Explosives & Propellants (火炸药学报), 2013, 50: 949-954.
盐,再在一定条件下对钾盐进行酸化,得到产物 3- [12] Michels H,Montgomery J,Christe K, et al. Theoretical prediction of
the structures and stabilities of azidamines[J]. Journal of Physical
氨基呋咱-4-羧酸。目前改进的方法反应温度较低, Chemistry, 1995, A99: 187-194.
其中环化成盐温度为 80 ℃,对比 Sheremetev 法反 [13] Cousins, Poulsen A, Sanders, J. Dynamiccombinatorial libraries of
pseudo-peptide hydrazone macrocycles[J]. Chemistry Communication,
应温度达到 100 ℃,该反应不使用乙醚,环化成盐 1999, 28: 1575-1576.
反应和酸化反应后的总收率 79.73%,产物纯度大于 [14] Poulsen. Direct screening of a dynamic combinatorial library using
mass spectrometry[J]. Journal of American Society Mass Spectrom,
98%,高于 Sheremetev 法报道的收率 64%。 2006, 17: 1074−1080.
[15] Bhat V, Caniard A, Luksch T, et al. Nucleophilic catalysis of
4 结论 acylhydrazone equilibration for protein-directed dynamic covalent
chemistry[J]. Nature Chemistry, 2010, 2(6): 490−497.
[16] Bunyapaiboonsri T, Ramstrom O, Lohmann S, et al. Dynamic
以氰基乙酸甲酯为原料,经过取代、缩合、成 deconvolution of a pre-equilibrated dynamic combinatorial library of
盐、水解制备得到 3-氨基呋咱-4-羧酸,并通过红外、 acetylcholinesterase inhibitors[J]. Chem Bio Chem, 2001, 2(6): 438-444.
[17] Bunyapaiboonsri T, Ramstrom H, Ramstrom O, et al. Generation of
核磁、元素分析对其结构进行了表征。合成中使用 bis-cationicheterocyclic inhibitors of Bacillus subtilis HPr kinase/
先成盐后水解的方法替代了原有合成方法。以 2-氰 phosphatase from a ditopic dynamic combinatorial library[J]. Journal
of Medicinal Chemistry, 2003, 46: 5803−5811.
基-2-肟基乙酸甲酯为原料的前提下,新方法的环化 [18] Eddy W, Brent D, Brian W, et al. Discovery of potent competitive
成盐反应和酸化反应总收率 79.73%,高于 Sheremetev inhibitors of indoleamine 2,3-dioxygenase with in vivo pharmacodynamic
activity and efficacy in a mouse melanomamodel[J]. Journal of
法报道的收率 64%。这将提供一种高效、便捷的 3- Medicinal Chemistry, 2009, 52: 7364-7367.
氨基呋咱-4-羧酸合成方法,以满足新型呋咱类化合 [19] Shen Huaping (沈华平), Lu Yanhua (卢艳华), Cao Yilin (曹一
林 ), et al. Synthesis and characterization of novel insensitive
物设计研发对重要中间体的需求。 energetic plasticizer 3-nitrofurazan-4-monomethyl ether[J]. Chinese
Journal of Energetic Materials (含能材料), 2011, 19(6): 735-738.
参考文献: [20] Sheremetev B, Konkina S, Yudin I, et al. (Pyrrol-1-yl)furazans[J].
Russian Chemical Bulletin, International Edition, 2003, 52(6): 1413-1418.
[1] Zhang Shouzhong (张寿忠), Feng Xiaojing (冯晓晶), Zhu Tianbing
(朱天兵), et al. Research progress in novel energetic materials- [21] Kevin G. Improved synthesis of 3-aminofurazan-4-carboxylic acid[J].
Organic Preparations and Procedures international: The New
furazan-based compounds[J]. Chemical Propellants & Polymeric Journal for Organic Synthesis, 2004, 36(4): 361-362.
Materials (化学推进剂与高分子材料), 2013, 11(2): 1-5. [22] Aleksei B, Nataliya S, Dmitrii E. Synthesis and X-ray study of novel
[2] Rodney L,Robson F, William L, et al. Synthesis and crystal structure azofurazan-annulatedmacrocyclic lactams[J]. Journal of Heterocyclic
of octahydro-5H,12H-4,11-methano-1H,7H-bis[1,2,5]oxadiazolo[3,4-d: Chemistry, 2005, 42: 519-525.
3',4'-j]-[1,7,3,9]dioxadiazacyclododecine[J]. Journal of Heterocyclic [23] Rodney L, Robson F, Mark F, et al. Crystal structures of the "Two"
Chemistry, 2012, 45: 705-709. 4-aminofurazan-3-carboxylic acids[J]. Journal of Heterocyclic
[3] Catrow J, Zhang Y, Zhang M, et al. Discovery of selective small- Chemistry, 2012, 49: 227-231.