A kind of preparation method of α-cyanoamine

A technology of cyanoamine and cyanoacetic acid, which is applied in the preparation of organic compounds, carboxylic acid nitrile preparation, chemical instruments and methods, etc., can solve the problems affecting the safety of the experiment, the low utilization rate of atoms, environmental pollution and other problems, and achieve the goal of reaction Good activity, beneficial to purification, simple post-treatment effect

Active Publication Date: 2018-03-09
SUZHOU UNIV
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Problems solved by technology

[0003] Murahashi et al. reported that in RuCl 3 , O 2 , NaCN system to synthesize α-cyanoamine, which uses highly toxic NaCN, 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 Catalytic synthesis of α-cyanoamine using TMSCN as a cyanogen source, the use of transition metals is very polluting to the environment, and the reaction atom utilization is not high (see: Han, W.; Ofial, A. R. Chem. Commun. 2009, 5024); Stephenson C. 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 metal catalysts such as Ru and Ir were used (See: Freeman, D. B.; Frust, L.; Condie, A. G.; Stephenson, C. R. J. Org. Lett. 2012, 14, 94)

Method used

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  • A kind of preparation method of α-cyanoamine
  • A kind of preparation method of α-cyanoamine
  • A kind of preparation method of α-cyanoamine

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027]

[0028] The reaction vial was filled with TBAI (0.3 mmol, 111 mg), compound 1a (2 mmol, 214 mg), compound 2 (4 mmol, 341 mg), NaOAc (4 mmol, 164 mg), TBHP (0.6 mL), Water (4.0 mL), Tetrahydrofuran (4.0 mL). Then the system was heated at 80 °C in air for about 12 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40 mL × 3), adsorbed on silica gel, and the product 3a was obtained by simple column chromatography, The yield was 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 H NMR (400 MHz, CDCl 3 ) δ 7.32 – 7.28 (m, 2H), 6.93 – 6.84 (m, 3H), 4.12 (s, 2H), 2.97 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 147.7, 129.4, 120.1,115.5, 114.8, 42.1, 39.1; MS (ESI-quadrupole): Anal. Calcd. For C 9 h 10 N 2 +H + :147, Found: 147 (M+H + ); IR (neat, cm -1 ): υ 2960, 2891, 2237, 1599, 1500.

Embodiment 2

[0031]

[0032] The reaction vial was filled with TBAI (0.3 mmol, 111 mg), compound 1a (2 mmol, 214 mg), compound 2 (4 mmol, 341 mg), NaOAc (4 mmol, 164 mg), TBHP (0.6 mL), Water (4.0 mL), Tetrahydrofuran (4.0 mL). Then the system was heated at 90°C in air for about 12 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40 mL × 3), adsorbed on silica gel, and the product 3a was obtained by simple column chromatography, 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 H NMR (400 MHz, CDCl 3 ) δ 7.32 – 7.28 (m, 2H), 6.93 – 6.84 (m, 3H), 4.12 (s, 2H), 2.97 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 147.7, 129.4, 120.1,115.5, 114.8, 42.1, 39.1; MS (ESI-quadrupole): Anal. Calcd. For C 9 h 10 N 2 +H + :147, Found: 147 (M+H + ); IR (neat, cm -1 ): υ 2960, 2891, 2237, 1599, 1500.

Embodiment 3

[0035]

[0036]The reaction vial was filled with TBAI (0.3 mmol, 111 mg), compound 1a (2 mmol, 214 mg), compound 2 (4 mmol, 341 mg), NaOAc (4 mmol, 164 mg), TBHP (0.6 mL), Water (4.0 mL), Tetrahydrofuran (4.0 mL). Then the system was heated at 100 °C in air for about 12 hours, quenched with saturated sodium sulfite solution, extracted with ethyl acetate (40 mL × 3), adsorbed on silica gel, and the product 3a was obtained by simple column chromatography, The yield was 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 H NMR (400 MHz, CDCl 3 ) δ 7.32 – 7.28 (m, 2H), 6.93 – 6.84 (m, 3H), 4.12 (s, 2H), 2.97 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 147.7, 129.4, 120.1,115.5, 114.8, 42.1, 39.1; MS (ESI-quadrupole): Anal. Calcd. For C 9 h 10 N 2 +H + :147, Found: 147 (M+H + ); IR (neat, cm -1 ): υ 2960, 2891, 2237, 1599, 1500.

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Abstract

The invention discloses a method for preparing α-cyanoamine. In the presence of an oxidizing agent, an amine compound and cyanoacetic acid are used as reactants, iodide is used as a catalyst, and sodium acetate is used as a base. The nuclear substitution reaction prepares the product α-cyanoamine. The method of the invention has high catalyst reactivity, mild reaction conditions, wide application range of substrates, convenient post-treatment, high yield of target product, simple preparation process, green and environmental protection, and wide sources of raw materials used.

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 antineoplastic drug extracted in recent years containing an α-cyanoamine structure. 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 tha...

Claims

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Application Information

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