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Synthetic method of cyclic enamine-3-formic acid ester compound

A technology of ester compounds and synthesis methods, which is applied in the field of synthesis of cyclic enamine-3-carboxylate compounds, can solve the problems of harsh reaction conditions, difficult to obtain raw materials, and low atom economy, and achieve easy operation and low Environmental burden, high effect of atom economy

Active Publication Date: 2017-06-13
HENAN NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although these methods can effectively synthesize cyclic enamine-3-carboxylates, there are still some problems that need to be solved urgently, such as: the atom economy of the reaction is low, the reaction conditions are harsh, and the raw materials are not easy to obtain. These deficiencies Also makes the practicability of the above method be greatly limited

Method used

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  • Synthetic method of cyclic enamine-3-formic acid ester compound
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  • Synthetic method of cyclic enamine-3-formic acid ester compound

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Experimental program
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Embodiment 1

[0015]

[0016] Add 1a (0.5 mmol, 88 mg) and acetonitrile (CH 3 CN, 5 mL), then 2a (5 mmol, 292 µL), palladium chloride (PdCl 2 , 0.05 mmol, 9 mg), copper acetate (Cu(OAc) 2 , 0.1 mmol, 18mg) and potassium iodide (KI, 0.5 mmol, 83 mg). at CO / O 2 (1 atm) atmosphere, stirred the reaction at 80°C for 12 hours, then added 10 mL of saturated sodium chloride solution to quench the reaction, extracted with ethyl acetate (10 mL × 3), combined the organic phases, and dried over anhydrous sodium sulfate . It was filtered, spin-dried, and separated on a silica gel column (petroleum ether / ethyl acetate = 20:1) to obtain product 3a (92 mg, 75%) as a yellow liquid. The characterization data of this compound are as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 1.28 (t, J = 7.2Hz, 3H), 1.79-1.82 (m, 2H), 2.31 (t, J = 6.4 Hz, 2H), 3.00 (t, J = 6.0 Hz,2H), 4.16 (q, J = 7.2 Hz, 2H), 4.30 (s, 2H), 7.23 (d, J = 6.8 Hz, 2H), 7.31-7.36 (m, 3H), 7.56 (s, 1H). 13 C NMR (100 MHz, CDCl 3 )...

Embodiment 2

[0018] According to the method described in Example 1, 1a (0.5 mmol, 88 mg) and acetonitrile (5 mL) were added to a 25 mL reaction vial, and then 2a (5 mmol, 292 µL), palladium acetate (0.05 mmol, 11 mg ) and copper acetate (0.5 mmol, 91mg). In a CO (1 atm) atmosphere, stir the reaction at 80°C for 12 hours, then add 10 mL of saturated sodium chloride solution to quench the reaction, extract with ethyl acetate (10 mL × 3), combine the organic phases, and wash with anhydrous sulfuric acid Sodium dry. After filtration, spin-drying, and separation on a silica gel column (petroleum ether / ethyl acetate = 20:1), the product 3a (59 mg, 48%) was obtained as a yellow liquid.

Embodiment 3

[0020] According to the method described in Example 1, 1a (0.5 mmol, 88 mg) and acetonitrile (5 mL) were added to a 25 mL reaction flask, and then 2a (5 mmol, 292 µL), tris(dibenzylideneacetone) Dipalladium (0.05 mmol, 46 mg) and copper acetate (0.5 mmol, 91 mg). In a CO (1 atm) atmosphere, stir the reaction at 80°C for 12 hours, then add 10 mL of saturated sodium chloride solution to quench the reaction, extract with ethyl acetate (10 mL × 3), combine the organic phases, and wash with anhydrous sulfuric acid Sodium dry. After filtration, spin-drying, and separation on a silica gel column (petroleum ether / ethyl acetate = 20:1), the yellow liquid product 3a (43 mg, 35%) was obtained.

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Abstract

The invention discloses a synthetic method of a cyclic enamine-3-formic acid ester compound and belongs to the field of organic synthesis technology. The main point of the technical scheme is as shown in the specification. In comparison with the prior art, the invention has the following advantages: (1) by the adoption of one-pot cascade reaction, tedious intermediate separation purification process is avoided, waste emission is decreased, and environmental burden is reduced; (2) raw materials are easily available; (3) the reaction is carried out at the temperature of minus 100 DEG C, condition is mild, and operation is simple; (4) the application range of a substrate is wide; and (5) atom economy of the reaction is high.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a method for synthesizing cyclic enamine-3-carboxylate compounds. Background technique [0002] Cyclic enamine-3-carboxylates not only have remarkable biological activity, but also have been widely used as intermediates in the synthesis of many fine chemicals. Based on its importance, research on new synthetic methods of this type of compound has always attracted the attention of chemists. At present, such compounds are mainly obtained through the following ways: 1) N -Condensation reaction of benzyl-γ-chloropropylamine with conjugated alkynoate; 2) Triphenylphosphine catalyzed the [3+3] cyclization reaction of aziridine and allenoate; 3) Primary amine compounds , β-dicarbonyl compounds, α, β-unsaturated aldehydes and alcohols in one-pot four-component reaction, etc. Although these methods can effectively synthesize cyclic enamine-3-carboxylates, there are still some...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D211/78C07D223/06
CPCC07D211/78C07D223/06
Inventor 范学森王芳何艳张新迎
Owner HENAN NORMAL UNIV
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