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Preparation method for synthesizing beta-carbonyl phosphonate derivatives via olefin

A technology of carbonyl phosphonates and derivatives, which is applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., can solve the problems of complicated steps, difficult to save the price of reagents, and complicated reaction system. , to achieve the effect of being beneficial to industrial production, the catalyst is cheap and easy to obtain, and the experimental operation is simple

Inactive Publication Date: 2017-01-04
HENAN ACADEMY OF SCI CHEM RES INST CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, these synthetic methods have disadvantages such as complex steps, use of noble metal catalysts, harsh reaction conditions, poor substrate applicability, complex reaction system, many by-products, low yield, unfriendly to the environment, and the reagents used are difficult to preserve and expensive.

Method used

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  • Preparation method for synthesizing beta-carbonyl phosphonate derivatives via olefin
  • Preparation method for synthesizing beta-carbonyl phosphonate derivatives via olefin
  • Preparation method for synthesizing beta-carbonyl phosphonate derivatives via olefin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1 2

[0016] Example 1 Diethyl-(2-oxo-2-phenyl)phosphonate

[0017] Styrene (0.104g, 1mmol) or phenylacrylic acid (0.148g, 1mmol), H-diethyl phosphite (0.276g, 2mmol), CuSO 4 ·5H 2 O (0.026g, 0.1mmol), 10mL of acetonitrile in a 25mL three-necked flask, heated to 60°C in an oil bath, continued the reaction at this temperature for 2h, and checked the reaction progress with a TLC plate. Extract with methane (15x 3mL), combine the organic phases, wash with Na 2 SO 4 After drying, the solvent was distilled off under reduced pressure and separated by column chromatography (petroleum ether / ethyl acetate, V / V=1:1) to obtain the target compound as a yellow oil with a yield of 91%.

[0018]

[0019] 1 H NMR (CDCl 3 ,400MHz,)δ:7.90(d,2H,J=7.6Hz),7.46(t,1H,J=7.2Hz),7.35(t,2H,J=7.6Hz),4.05-3.98(m,4H) ,3.56(d,2H,J=22.8Hz),1.15(t,6H,J=7.2Hz); 13 C NMR (CDCl 3 ,100MHz); δ:191.8(d,J P-C =6.5Hz), 136.4(J P-C =1.9Hz), 133.6, 128.9, 128.5, 62.6 (d, J P-C =6.4Hz), 38.9(d, J P-C 129.3Hz),...

Embodiment 2 2

[0020] Example 2 Diisopropyl-(2-oxo-2-phenyl)phosphonate

[0021]Styrene (0.104g, 1mmol) or phenylacrylic acid (0.148g, 1mmol), H-diisopropyl phosphite (0.332g, 2mmol), CuSO 4 ·5H 2 O (0.026g, 0.1mmol), 10mL of acetonitrile in a 25mL three-necked flask, heated to 50°C in an oil bath, continued the reaction at this temperature for 4h, and checked the reaction progress with a TLC plate. Extract with methane (15x 3mL), combine the organic phases, wash with Na 2 SO 4 After drying, the solvent was distilled off under reduced pressure and separated by column chromatography (petroleum ether / ethyl acetate, V / V=1:1) to obtain the target compound as a yellow oil with a yield of 87%.

[0022]

[0023] 1 H NMR (CDCl 3 ,400MHz,)δ:8.04(d,2H,J=7.2Hz),7.59(t,1H,J=7.6Hz),7.49(t,2H,J=8.0Hz),4.80-4.69(m,2H) ,3.61(d,2H,J=22.8),1.29(dd,12H,J=3.2Hz,6.8Hz); 13 C NMR (CDCl 3 ,100MHz); δ:192.1(d,J P-C =6.6Hz), 136.7, 133.5, 129.1, 128.5, 71.5 (d, J P-C =6.6Hz), 39.7(d, J P-C =129.5Hz), 2...

Embodiment 3 2

[0024] Example 3 Dibenzyl-(2-oxo-2-phenyl)phosphonate

[0025] Styrene (0.104g, 1mmol) or phenylacrylic acid (0.148g, 1mmol), H-dibenzyl phosphite (0.524g, 2mmol), CuSO 4 ·5H 2 O (0.026g, 0.1mmol), 10mL of ethanol in a 25mL three-necked flask, heated to 60°C in an oil bath, and continued to react at this temperature for 2h, using a TLC plate to detect the reaction progress, after the reaction was completed, dichloromethane Extract with methane (15x 3mL), combine the organic phases, wash with Na 2 SO 4 After drying, the solvent was distilled off under reduced pressure and separated by column chromatography (petroleum ether / ethyl acetate, V / V=1:1) to obtain the target compound as a yellow oil with a yield of 91%.

[0026]

[0027] 1 H NMR (CDCl 3 ,400MHz,)δ:7.95(d,2H,J=7.6Hz),7.54(t,1H,J=7.2Hz),7.40(t,2H,J=7.6Hz),7.34-7.28(10H),5.09 -4.98(m,4H),3.68(d,2H,J=22.4); 13 C NMR (CDCl 3 ,100MHz); δ:191.7(d,J P-C =6.5Hz), 136.44(d,J P-C =2.4Hz), 135.9(d, J P-C =5.2Hz), 133...

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Abstract

The invention discloses a method for synthesizing beta-carbonyl phosphonate derivatives via olefin and belongs to the field of organic chemistry. In the method, olefin (or olefin acid) and H-phosphite are used as raw materials, CuSO4.5H2O is used as a catalyst, and beta-carbonyl phosphonate derivatives are synthesized by heating reaction. The method is cheap and readily available in raw materials, simple in operation, mild in reaction condition and high in synthetic yield, and is suitable for industrialized production. The derivatives are often used as intermediates for synthesizing alpha, beta-unsaturated carbonyl compounds, and the derivatives also have wide bioactivity and significant metal compounding capability and play an irreplaceable role in medicinal chemistry, biological chemistry and inorganic chemistry.

Description

technical field [0001] The present invention relates to a CuSO 4 ·5H 2 The invention discloses a method for synthesizing β-carbonyl phosphonate derivatives through alkenes under O catalysis, which belongs to the field of organic chemistry. Background technique [0002] β-carbonyl phosphonate occupies a very important position in organophosphorus chemistry, has a wide range of biological activities and significant metal complexing ability, and plays an irreplaceable role in organic synthesis, medicinal chemistry, biochemistry, and inorganic chemistry. In the field of organic synthesis, it is often used as a reaction intermediate for the synthesis of α, β-unsaturated carbonyl compounds. For example, the famous Horner-Wadsworth-Emmons reaction is to use β-carbonyl phosphonate and aldehyde (or ketone) to synthesize α, β-unsaturated carbonyl compound under the action of base; in medicinal chemistry, it is used as a chiral precursor substance It is widely used in the synthesis ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/40C07F9/53C07F9/655
CPCC07F9/4006C07F9/4059C07F9/5333C07F9/65515
Inventor 李旭陈茜刘海涛王建莉郝旭东郭利兵王金良周晓楠李玉宁
Owner HENAN ACADEMY OF SCI CHEM RES INST CO LTD