3-氨基呋咱-4-羧酸的合成及表征
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摘要
以氰乙酰胺为起始原料,经亚硝化、加成、环化得到标题化合物,并利用红外光谱、核磁共振、质谱、元素分析等鉴定了产物结构。初步探讨了环化反应过程,确定反应的最适宜条件为:采用冰醋酸为亚硝化反应的最佳催化剂,产率高达96%;加成反应中最佳投料比为n(2-肟基氰乙酰胺)∶n(盐酸羟胺)=1∶3,产率可达95%;环化反应反应时间为4 h,反应温度为65~70℃,产率为62%。研究表明,该方法具有能耗低、操作简便、收率高的优点。
The title compound was synthesized from 2-cyanoacetamide via nitrosation,addition and cyclization. The molecular structure was confirmed by IR,1 HNMR,13 CNMR,MS and elemental analysis. The cyclic reaction process was preliminarily discussed,and the optimum conditions were determined: glacial acetic acid was used as the best catalyst for nitrosation,with a yield of up to 96%.In addition reaction,the optimal feeding ratio was n( 2-oxime cyanoacetamide) ∶n( hydroxylamine hydrochloride) = 1∶3,and the yield can reach 95%. Cyclization reaction time was 4 h,the reaction temperature was 65 ~ 70 ℃,and the yield was62%.The results showed that this method had the advantages of low energy consumption,simple operation and high yield.
The title compound was synthesized from 2-cyanoacetamide via nitrosation,addition and cyclization. The molecular structure was confirmed by IR,1 HNMR,13 CNMR,MS and elemental analysis. The cyclic reaction process was preliminarily discussed,and the optimum conditions were determined: glacial acetic acid was used as the best catalyst for nitrosation,with a yield of up to 96%.In addition reaction,the optimal feeding ratio was n( 2-oxime cyanoacetamide) ∶n( hydroxylamine hydrochloride) = 1∶3,and the yield can reach 95%. Cyclization reaction time was 4 h,the reaction temperature was 65 ~ 70 ℃,and the yield was62%.The results showed that this method had the advantages of low energy consumption,simple operation and high yield.
引文
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[2]周彦水,王伯周,周诚,等.3,4-双(4'-叠氮基呋咱-3'-基)氧化呋咱合成、表征与晶体结构研究[J].有机化学,2010,30(7):1 044-1 050.
[3]王军.3,3'-二(3-氨基呋咱基氧化呋咱-4-基)-4,4'-偶氮呋咱的合成与表征[J].含能材料,2008,16(2):238-241.
[4]马姣丽,李成凤,周立超,等.过渡金属催化芳香偶氮化合物的合成研究进展[J].化学试剂,2018,40(8):750-754.
[5]周彦水,李建康,黄新萍,等.3,4-双(4'-氨基呋咱基-3')氧化呋咱的合成及性能[J].火炸药学报,2007,30(1):54-56.
[6]PHILIP W L,COLIN J P,DAVID E C,et al.3,6-Bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,4,2,5-dioxadiazene(BNDD):a powerful sensitive explosive[J]. Synlett,2011,(14):2 097-2 099.
[7]LIM C H,KIM T K,KIM K H,et al.Synthesis and characterization of bisnitrofurazanofuroxan[J]. Bull. Korean Chem.Soc.,2010,31(5):1 400-1 402.
[8]李战雄,唐松青.氧化呋咱衍生物的合成研究进展[J].含能材料,2006,14(1):77-79.
[9]李云路,薛梅,王建龙,等.多硝基呋咱类含能化合物的合成研究进展[J].有机化学,2016,36:1 528-1 538.
[10]王乃兴,李纪生,张来新.苯并氧化呋咱化合物研究概述[J].合成化学,1995,3(4):309-313.
[11]TOSHIMASA T,KAZUHIRO I.New fluorogenic reagent having halogenobenzofurazan structure for thiols:4-(Aminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole[J].Anal.Chem.,1984,56(13):2 461-2 464.
[12]李战雄,唐松青,欧育湘,等.呋咱含能衍生物合成研究进展[J].含能材料,2002,10(2):59-65.
[13]范艳洁,王伯周,来蔚鹏,等.3,3'-二氰基二呋咱基醚(FOF-2)的合成、表征及量子化学研究[J].有机化学,2009,29(4):614-620.
[14]姬月萍,李普瑞,汪伟,等.含能增塑剂的研究现状及发展[J].火炸药学报,2005,28(4):47-51.
[15]MICHAEL D C. Picrylamino-substituted heterocycles[J].J.Heterocylic Chem.,1986,5:83-87.
[16]沈华平,卢艳华,曹一林,等.新型钝感含能增塑剂3-硝基呋咱-4-甲醚的合成与性能研究[J].含能材料,2011,19(6):735-738.