Method of preparing 3-amino-2-thiocyano-alpha, beta-unsaturated compound

A technology for thiocyano group and compound, which is applied in the field of visible light-driven synthesis of 3-amino-2-thiocyano-α,β-unsaturated compounds, can solve the problems of low yield, by-products, toxicity, etc. The effect of high utilization rate, lower industrial cost and abundant sources

Active Publication Date: 2019-01-18
LANZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In addition, it has been disclosed that the synthesis of amine thiocyanate compounds has been realized by using electrocatalysis, but the synthesis method still has great defects, such as pre-functionalization of starting materials, complex thiocyanate reagents, low yield, and the formation of toxic by-product of
Under the current development trend of green chemistry, this kind of reaction obviously cannot meet the demand

Method used

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  • Method of preparing 3-amino-2-thiocyano-alpha, beta-unsaturated compound
  • Method of preparing 3-amino-2-thiocyano-alpha, beta-unsaturated compound
  • Method of preparing 3-amino-2-thiocyano-alpha, beta-unsaturated compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: Synthesis of 3-amino-2-thiocyanobutenoic acid ethyl ester

[0026]

[0027] At room temperature, ethyl acetoacetate (65.1mg, 0.5mmol), ammonium thiocyanate (114, 2mg, 1.5mmol), fluorescein (3.3mg, 2mol%) were added to a 10mL reaction tube, and then the solvent acetonitrile was added 2mL, under the irradiation of 3.0W blue LED, react in the air for 6 hours, and detect by TLC. After the reaction was completed, the reaction mixture was concentrated in vacuo, and the remaining crude product was separated by column chromatography to obtain 88.4 mg of ethyl 3-amino-2-thiocyanobutenoate as a white solid, with a yield of 95%.

[0028] Ethyl(E)-3-amino-2-thiocyanatobut-2-enoate White solid, (95% yield) 1 HNMR (400MHz, CDCl 3 )δ9.25(s, 1H), 5.73(s, 1H), 4.22(q, J=7.1Hz, 2H), 2.38(s, 3H), 1.34(t, J=7.1Hz, 3H); 13 C NMR (100MHz, CDCl 3 )δ168.4, 168.3, 113.5, 75.6, 60.7, 23.2, 14.3; MS (ESI, m / z): Calculated for [C 7 h 10 N 2 o 2 S](M+H) + 187.0, found 187.0. ...

Embodiment 2

[0029] Example 2: Synthesis of 3-amino-2-thiocyanobutenoic acid methyl ester

[0030]

[0031] At room temperature, methyl acetoacetate (58 mg, 0.5 mmol), ammonium thiocyanate (114, 2 mg, 1.5 mmol), and fluorescein (3.3 mg, 2 mol%) were added to a 10 mL reaction tube, and then 2 mL of solvent acetonitrile was added , reacted in the air for 6 hours under the irradiation of 3.0W blue LED, and detected by TLC. After the reaction was completed, the reaction mixture was concentrated in vacuo, and the remaining crude product was separated by column chromatography to obtain 79.1 mg of 3-amino-2-thiocyanobutenoic acid methyl ester as a white solid, with a yield of 92%.

[0032] Methyl(E)-3-amino-2-thiocyanatobut-2-enoate White solid, (92% yield); 1 H NMR (400MHz, CDCl 3 )δ9.24(s,1H),5.82(s,1H),3.77(s,3H),2.38(s,3H); 13 C NMR (100MHz, CDCl 3 )δ168.7, 168.6, 113.4, 75.5, 51.9, 23.2; MS (ESI, m / z): Calculated for [C 6 h 8 N 2 o 2 S](M+H) + 173.0, found 173.0.

Embodiment 3

[0033] Example 3: Synthesis of 3-amino-2-thiocyanobutenoic acid isopropyl ester

[0034]

[0035] At room temperature, isopropyl acetoacetate (72.1mg, 0.5mmol), ammonium thiocyanate (114,2mg, 1.5mmol), fluorescein (3.3mg, 2mol%) was added to a 10mL reaction tube, and then the solvent was added 2mL of acetonitrile was reacted in air for 6 hours under the irradiation of 3.0W blue LED, and detected by TLC. After the reaction was completed, the reaction mixture was concentrated in vacuo, and the remaining crude product was separated by column chromatography to obtain 90 mg of isopropyl 3-amino-2-thiocyanobutenoate as a white solid, with a yield of 90%.

[0036] Isopropyl(E)-3-amino-2-thiocyanatobut-2-enoate White solid, (90% yield); 1 H NMR (CDCl 3 ,400MHz)δ9.23(s,1H),5.85(s,1H),5.06-4.96(m,1H),2.35(s,3H),1.30(s,3H),1.29(s,3H); 13 C NMR (CDCl 3,100MHz) δ168.2,167.9,113.7,75.8,68.1,23.2,21.9; HRMS(ESI):m / z calculated for C 8 h 12 N 2 o 2 S[M+H] + 201.0692, found 201.069...

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Abstract

The invention discloses a method of preparing a 3-amino-2-thiocyano-alpha, beta-unsaturated compound. The preparation method comprises the following steps of adding activated ketone, ammonium thiocyanate and dye fluorescein in acetonitrile as a solvent, performing driven reaction for 6-12h with visible light at the temperature of 25 DEG C, performing spin drying on reaction liquid to obtain a concentrate, and performing silica gel column chromatography on the concentrate to obtain a target compound. The method has the advantages of no use of additional oxidizing agent, low preparation cost, no toxic and side products emission and accords with the requirement for green chemical engineering development.

Description

technical field [0001] The invention relates to a method for synthesizing amine-thiocyano compounds, in particular to a method for synthesizing 3-amino-2-thiocyano-α,β-unsaturated compounds driven by visible light. Background technique [0002] Multi-substituted alkenes have extremely important application value in organic synthesis. The introduction of new functional groups on alkenes has been the tireless pursuit of chemists for nearly a hundred years, and various synthetic methods are changing with each passing day. 3-Amino-2-thiocyano-α, β-unsaturated compound is an important synthetic intermediate, including amine group, thiocyano group, ester group (carbonyl, phospholipid, cyano, thioester), etc. Multifunctional alkenes. Especially the thiocyano group can be converted into different functional groups such as SCF 3 ,SCF 2 H, phosphorothioate, tetrazole, sulfide, asymmetric disulfide and other sulfur compounds. Asymmetric chemistry, a hot research direction in today'...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C331/14C07D333/24C07F9/40C07J1/00C07J9/00C07B45/00
CPCC07B45/00C07C331/14C07C2601/08C07C2603/74C07D333/24C07F9/4015C07J1/0011C07J9/00
Inventor 刘强袁盼锋
Owner LANZHOU UNIVERSITY
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