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Preparation method for alpha-cyanoamine

A technology of cyanoamine and cyanoacetic acid, which is applied in the preparation of organic compounds, the preparation of carboxylic acid nitrile, chemical instruments and methods, etc., can solve problems such as affecting experimental safety, low atomic utilization, environmental pollution, etc. Good activity, good for purification and simple post-processing

Active Publication Date: 2016-01-13
SUZHOU UNIV
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  • Abstract
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  • Application Information

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Problems solved by technology

[0003] Murahashi et al. reported that in RuCl 3 , O 2 , Synthesis of α-cyanoamine under the NaCN system, in which highly toxic NaCN is used, which seriously affects the safety of the experiment (see: Murahashi, S.-I; Komiya, N.; Terai, H.; Nakae, T.J.Am.Chem. Soc.2003,125,15312); Ofial et al reported FeCl 2 Catalyzed, using TMSCN as the synthesis method of α-cyanoamine as the cyanogen source, the transition metal used in it has great pollution to the environment, and the atom utilization rate of the reaction is not high (see: Han, W.; Ofial, A.R. Chem.Commun.2009, 5024); StephensonC.R.J. et al. reported the α-cyanation reaction of N-aryl tetrahydroisoquinoline guided by visible light, in which NaCN was used as the cyanide source and expensive transition metals such as Ru and Ir were used Catalysts (See: Freeman, D.B.; Frust, L.; Condie, A.G.; Stephenson, C.R.J. Org. Lett. 2012, 14, 94)

Method used

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  • Preparation method for alpha-cyanoamine
  • Preparation method for alpha-cyanoamine
  • Preparation method for alpha-cyanoamine

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027]

[0028] The reaction bottle was loaded with TBAI (0.3mmol, 111mg) sequentially, and the compound 1a (2mmol, 214mg), compound 2 (4mmol, 341mg), NaOAc (4mmol, 164mg), TBHP (0.6mL), water (4.0mL), tetrahydrofuran (4.0mL). Then the system was heated in the air at 80°C for about 12 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40mL×3), adsorbed on silica gel, and the product was obtained by simple column chromatography 3a , the yield is 84%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0029] 1 HNMR (400MHz, CDCl 3 )δ7.32–7.28(m,2H),6.93–6.84(m,3H),4.12(s,2H),2.97(s,3H); 13 CNMR (100MHz, CDCl 3 )δ147.7, 129.4, 120.1, 115.5, 114.8, 42.1, 39.1; MS (ESI-quadrupole): Anal.Calcd.ForC 9 h 10 N 2 +H + :147,Found:147(M+H + );IR(neat,cm -1 ):υ2960, 2891, 2237, 1599, 1500.

Embodiment 2

[0031]

[0032] The reaction bottle was loaded with TBAI (0.3mmol, 111mg) sequentially, and the compound 1a (2mmol, 214mg), compound 2 (4mmol, 341mg), NaOAc (4mmol, 164mg), TBHP (0.6mL), water (4.0mL), tetrahydrofuran (4.0mL). Then the system was heated at 90°C in the air for about 12 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40mL×3), adsorbed on silica gel, and the product was obtained by simple column chromatography 3a , the yield is 80%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0033] 1 HNMR (400MHz, CDCl 3 )δ7.32–7.28(m,2H),6.93–6.84(m,3H),4.12(s,2H),2.97(s,3H); 13 CNMR (100MHz, CDCl 3 )δ147.7, 129.4, 120.1, 115.5, 114.8, 42.1, 39.1; MS (ESI-quadrupole): Anal.Calcd.ForC 9 h 10 N 2 +H + :147,Found:147(M+H + );IR(neat,cm -1 ):υ2960, 2891, 2237, 1599, 1500.

Embodiment 3

[0035]

[0036] The reaction bottle was loaded with TBAI (0.3mmol, 111mg) sequentially, and the compound 1a (2mmol, 214mg), compound 2(4mmol, 341mg), NaOAc (4mmol, 164mg), TBHP (0.6mL), water (4.0mL), tetrahydrofuran (4.0mL). Then the system was heated in the air at 100°C for about 12 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40mL×3), adsorbed on silica gel, and the product was obtained by simple column chromatography 3a , the yield is 77%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0037] 1 HNMR (400MHz, CDCl 3 )δ7.32–7.28(m,2H),6.93–6.84(m,3H),4.12(s,2H),2.97(s,3H); 13 CNMR (100MHz, CDCl 3 )δ147.7, 129.4, 120.1, 115.5, 114.8, 42.1, 39.1; MS (ESI-quadrupole): Anal.Calcd.ForC 9 h 10 N 2 +H + :147,Found:147(M+H + );IR(neat,cm -1 ):υ2960, 2891, 2237, 1599, 1500.

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Abstract

The invention discloses a preparation method for alpha-cyanoamine. According to the method, the product alpha-cyanoamine is prepared through nucleophilic substitution in a mixed solvent in the presence of an oxidizing agent with an amine compound and cyanoacetic acid as reactants, iodide as a catalyst and sodium acetate as alkali. The catalyst used in the method has high reactivity; reaction conditions are mild; the application scope of a substrate is wide; post-treatment is convenient; the yield of the target product is high; preparation process is simple, green and environment-friendly; and used raw materials are widely available.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis and relates to a method for preparing α-cyanoamine. Background technique [0002] The oxidative cyanation of amines has attracted widespread attention in recent years, because α-cyanoamine is one of the most common structural units, and has a wide range of applications in biology, medicine, pesticides, food, and chemical industries. For example, the compound Saframycin A is an anti-tumor drug containing α-cyanoamine structure extracted in recent years. In addition, it is also a very useful synthetic intermediate, which can be used to prepare a variety of biologically active compounds, such as alkaloids, amino acids, and 1,2-diamine compounds. At present, highly toxic MCN is used as the cyanide source in the preparation of α-cyanoamine, and transition metals which are expensive and pollute the environment are used as catalysts. For example: [0003] Murahashi et al. reported that in Ru...

Claims

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Application Information

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IPC IPC(8): C07C253/30C07C255/24C07D215/06C07D295/15C07D213/74
Inventor 万小兵王宏祥张杰邵莺
Owner SUZHOU UNIV