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Preparation method of beta-aminoethylphosphonyl derivatives

A technology of aminoethylphosphonyl derivatives and ethylene derivatives, which is applied in the field of organic synthesis, can solve the problems of difficulty in obtaining raw materials, rare reaction raw materials, harsh reaction conditions, etc., and achieves reduction of waste generation, reaction operation and post-processing The effect of simple processing and easy availability of raw materials

Active Publication Date: 2015-11-04
翁后科
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Problems solved by technology

[0005]2. Starting from β-carbonyl phosphonate, react with hydrazine, reduce and hydrolyze to obtain β-aminoethylphosphonyl derivatives; this method requires β- - Carbonyl phosphonate is the starting material, the raw material is difficult to obtain, the reaction steps are many, and the yield is low
[0006]3. Starting from β-carbonyl phosphonate, obtain β-aminoethylphosphonyl derivatives through ammoniation, reduction and hydrolysis; this method requires β- Carbonyl phosphonate is the starting material, the raw material is difficult to obtain, need to use expensive sodium cyanoborohydride as reducing agent, and the yield is low
[0007] 4. Reaction of brominated heteroaryl hydrocarbon with β-aminoethylphosphonate under basic conditions, and then hydrolyzed under acidic conditions to obtain β-aminoethylphosphine acyl derivatives; this method needs to use β-aminoethyl phosphonate as the starting material, the raw materials are difficult to obtain, and the yield is low
[0008] In summary, although some β-aminoethylphosphono derivatives can be prepared in the prior art, there are harsh reaction conditions, rare reaction raw materials, and reaction costs. Therefore, it is very important to develop a method for the preparation of β-aminoethylphosphonyl derivatives with mild reaction conditions, a wide range of applications, few reaction steps, high yield, low cost, and meeting the requirements of green chemistry.

Method used

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  • Preparation method of beta-aminoethylphosphonyl derivatives
  • Preparation method of beta-aminoethylphosphonyl derivatives
  • Preparation method of beta-aminoethylphosphonyl derivatives

Examples

Experimental program
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Effect test

Embodiment 1

[0051] Example 1: Synthesis of 2-amino-2-phenylethylphosphonic acid

[0052] Add methanol (6 mL), styrene (0.104 g, 1 mmol), ammonia (0.12 g, 4.0 mmol), dimethyl phosphinate (0.22 g, 2 mmol), silver nitrate (0.340 g, 2 mmol), copper bromide (0.045 g, 0.2 mmol), the mixture was stirred and reacted at 40 °C, and the reaction was tracked by TLC until the end. After the reaction, half of the reaction solution was taken out, and the crude product obtained after concentration was separated by column chromatography (petroleum ether / acetone / dichloromethane=20 / 1 / 1) to obtain the target product 2-amino-2-phenylethane phosphonate (yield 81%); 1 H NMR (400 MHz, CDCl 3 ): δ 8.50 (s, 2H),7.18-7.42 (m, 5H ), 4.11-4.31 (m, 1H ) , 3.63 (d, J = 10.8 Hz, 6H), 1.60-1.80 (m, 2H ) .

[0053] Add 7.5 mL of 20% hydrochloric acid to the remaining half of the reaction solution in the reaction bottle, heat the mixture to reflux, and follow the reaction by TLC until the end; add an appropriate ...

Embodiment 2

[0054] Example two: Synthesis of 2-amino-2-(4-chlorophenyl)ethylphosphonic acid

[0055] Add ethanol (6 mL), 4-chlorostyrene (0.139 g, 1 mmol), ammonia water (0.12 g, 4.0 mmol), dimethyl phosphinate (0.22 g, 1 mmol), silver nitrate ( 0.340 g, 2 mmol), copper bromide (0.045 g, 0.2 mmol), the mixture was stirred and reacted at 30°C, and the reaction was tracked by TLC until the end. After the reaction, half of the reaction solution was taken out, and the crude product obtained after concentration was separated by column chromatography (petroleum ether / acetone / dichloromethane=20 / 1 / 1) to obtain the target product 2-amino-2-(4- Chlorophenyl) ethylphosphonate (84% yield). Its analysis data is as follows: 1 H NMR (400 MHz, CDCl 3 ): δ 8.50 (s, 2H), 7.57–7.43 (m, 4H), 4.11-4.31 (m, 1H ) , 3.64 (d, J = 10.8 Hz, 6H), 1.61-1.80 (m, 2H ) .

[0056] Add 7.5 mL of 20% hydrochloric acid to the remaining half of the reaction solution in the reaction bottle, heat the mixture to reflux...

Embodiment 3

[0057] Embodiment three: the synthesis of 2-aminoethylphosphonic acid

[0058] Acetonitrile (6 mL), acrylic acid (0.072 g, 1 mmol), ammonia water (0.24 g, 8.0 mmol), diethyl phosphinate (0.276 g, 2 mmol), silver nitrate (0.340 g, 2 mmol) were added to the reactor. mmol), copper bromide (0.045 g, 0.2 mmol), the mixture was stirred and reacted at 50 °C, and the reaction was tracked by TLC until the end. After the reaction, half of the reaction solution was taken out, and the crude product obtained after concentration was separated by column chromatography (petroleum ether / acetone / methylene chloride=20 / 1 / 1) to obtain the target product 2-aminoethylphosphonate ( Yield 78%). Its analysis data is as follows: 1 H NMR (300 MHz, D 2 O): δ 4.30-4.50 (m, 1H ) , 4.10?3.95 (m, 4H), 1.72-1.93 (m, 2H), 1.27 (t, J = 7.1 Hz, 6H) .

[0059] Add 7.5 mL of 20% hydrochloric acid to the remaining half of the reaction solution in the reaction flask, heat the mixture to reflux, and track the ...

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Abstract

The invention discloses a preparation method of beta-aminoethylphosphonyl derivatives. The method comprises the following steps: adding an ethylene derivative, an ammonia derivative, an organic phosphine compound, silver nitrate, a catalytic amount of copper bromide, and a solvent into a reactor, reacting at 30-50DEG C to prepare a beta-aminoethylphosphonyl derivative, adding hydrochloric acid, and further reacting to obtain more beta-aminoethylphosphonyl derivatives. The ethylene derivative is used as an initiator, so raw materials are easy to obtain and have many kinds; and the products obtained by using the method are various, can be directly used, and can also be used in other further reactions. The method has the advantages of mild reaction conditions, simple reaction operation and post-treatment process, concise production technology, high yield, and suitableness for large scale production.

Description

technical field [0001] The invention relates to a nitrogen-containing organic phosphine compound, in particular to a preparation method of a β-aminoethylphosphonyl derivative, and belongs to the field of organic compound synthesis. Background technique [0002] The structure of β-aminoethylphosphonyl derivatives is similar to that of β-amino acids, and has a wide range of physiological activities, such as antibacterial, stimulating nerves, affecting cell growth and metabolism, analgesic, regulating blood pressure, regulating plant growth, etc., so it can Used as medicine, pesticide, antagonist, anthocyanin synthesis inhibitor, fructose bisphosphatase inhibitor (see Maier, L. Phosphorus Sulfur 1983, 14, 295; Abbenante, Giovanni; Australian J. Chem., 1997, 50 , 523-527; L. Maier, P. J. Diel, Phosphorus, Sulfur Silicon., 1995, 107, 245-255; L. Maier, P. J. Diel, Phosphorus, Sulfur Silicon., 1996, 109-110, 341-344; Erion , M. D.; Dang, Q.; Reddy, M. R.; Kasibhatla, S. R.; Huang...

Claims

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Application Information

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IPC IPC(8): C07F9/38C07F9/6561
CPCC07F9/3808C07F9/3882C07F9/4056C07F9/5333C07F9/65616
Inventor 邹建平刘奎张沛之
Owner 翁后科
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