Beta-phosphoryl nitrate ester compounds and preparation method thereof

A technology of diphenylphosphoethyl nitrate and compound, which is applied in the field of β-phosphorylated nitrate compound and its preparation, can solve the problems of poor substrate compatibility, poor atom economy, and limited application, and achieve substrate Good compatibility, high conversion rate, and various effects

Active Publication Date: 2018-05-01
YANTAI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The traditional method for preparing nitrate compounds mainly contains following two kinds: (1) strong acid nitration method of alcohol, this method usually uses concentrated nitric acid as nitration reagent, because its strong oxidizing property makes it poor to substrate compatibility, and Post-treatment is serious to environmental pollution (Fleming, W.J.; Rowe, E.J.; Meyers, D.B.Journal of the American Pharmaceutical Association (1912-1977), 1958, 47, 368); For silver nitrate, the large amount of generation and waste of by-product silver halide after the reaction finishes leads to poor atom economy of this type of reaction, which limits its application in large-scale production (Kuchurov, I.V.; Fomenkov, I.V.; Zlotin, S.G.; Tartakovsky, V.A. Mendeleev Commun., 2012, 22, 67)

Method used

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  • Beta-phosphoryl nitrate ester compounds and preparation method thereof
  • Beta-phosphoryl nitrate ester compounds and preparation method thereof
  • Beta-phosphoryl nitrate ester compounds and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Using styrene and diphenylphosphine oxide as raw materials, the reaction formula and experimental steps are as follows:

[0043]

[0044] Add diphenylphosphine oxide (40.4mg, 0.2mmol) and ammonium cerium nitrate (219mg, 0.4mmol) into a Schlenk tube equipped with magnetic stirring, and use double row tubes to replace nitrogen repeatedly, so that the whole system is under nitrogen atmosphere , and then added styrene (52mg, 0.5mmol) and 2mL 1,4-dioxane to the system, the reaction was carried out at 40°C, and the reaction was tracked by TLC until the end of the reaction. After the reaction was finished, the reaction solution was concentrated, and the mixed solution of petroleum ether and ethyl acetate with a volume ratio of 3:1 was used as an eluent, and the product 2-diphenylphosphine-1-phenylethyl nitrate was obtained by column chromatography. The rate is 88%.

[0045] 1 H NMR (400MHz, CDCl 3 ): δ7.74-7.79(m, 2H), 7.42-7.60(m, 6H), 7.29-7.37(m, 4H), 7.23-7.27(m, 3H)...

Embodiment 2

[0047] With 4-fluorostyrene and diphenylphosphine oxide as raw materials, the reaction formula and experimental steps are as follows:

[0048]

[0049] Add diphenylphosphine oxide (40.4mg, 0.2mmol) and ammonium cerium nitrate (219mg, 0.4mmol) into a Schlenk tube equipped with magnetic stirring, and use double row tubes to replace nitrogen repeatedly, so that the whole system is under nitrogen atmosphere , and then added 4-fluorostyrene (61mg, 0.5mmol) and 2mL 1,4-dioxane to the system, the reaction was carried out at 40°C, and the reaction was followed by TLC until the end of the reaction. After the reaction, the reaction solution was concentrated, and the mixture of petroleum ether and ethyl acetate with a volume ratio of 3:1 was used as the eluent, and the product 1-(4-fluorophenyl)-2-diphenylphosphine was separated by column chromatography Ethyl nitrate, 84% yield.

[0050] 1 H NMR (400MHz, CDCl 3 ): δ7.72-7.77(m, 2H), 7.43-7.58(m, 6H), 7.27-7.37(m, 4H), 6.86-6.92(m, ...

Embodiment 3

[0052] With 4-chlorostyrene and diphenyl phosphorus oxide as raw materials, the reaction formula and experimental steps are as follows:

[0053]

[0054] Add diphenylphosphine oxide (40.4mg, 0.2mmol) and ammonium cerium nitrate (219mg, 0.4mmol) into a Schlenk tube equipped with magnetic stirring, and use double row tubes to replace nitrogen repeatedly, so that the whole system is under nitrogen atmosphere , and then added 4-chlorostyrene (27.6mg, 0.5mmol) and 2mL 1,4-dioxane to the system, the reaction was carried out at 40°C, and the reaction was tracked by TLC until the end of the reaction. After the reaction, the reaction solution was concentrated, and the mixture of petroleum ether and ethyl acetate with a volume ratio of 3:1 was used as the eluent, and the product 1-(4-chlorophenyl)-2-diphenylphosphine was separated by column chromatography Ethyl nitrate, 78% yield.

[0055] 1 H NMR (400MHz, CDCl 3 ): δ7.72-7.77(m, 2H), 7.44-7.58(m, 6H), 7.32-7.37(m, 2H), 7.22-7.25(...

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Abstract

The invention relates to beta-phosphoryl nitrate ester compounds and a preparation method thereof. Novel compounds, namely the beta-phosphoryl nitrate ester compounds as shown in a general formula (I)are synthesized, and the prepared beta-phosphoryl nitrate ester compounds will have a dual property both of nitrate esters and organic phosphines. The invention also discloses the preparation methodof the beta-phosphoryl nitrate ester compounds, and the preparation method is that olefin compounds, phosphorus reagents and an oxidant are dissolved in a solvent, and are allowed to react at 30-60DEGC under a nitrogen atmosphere, so as to prepare and obtain the beta-phosphoryl nitrate ester compounds in one-step with a one-pot method. According to the beta-phosphoryl nitrate ester compounds andthe preparation method thereof, the starting raw material is olefins which are cheap, readily available, low in cost, and have many types for selection; step economy and atom economy are high; the obtained products have various types and generally have high yields; and meanwhile, the preparation method has mild reaction conditions, is safe for operation, is easy to control, has simple post-treatment, and is suitable for large-scale production.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a β-phosphorylated nitrate compound and a preparation method thereof. Background technique [0002] Nitrate esters are an important class of organic compounds, which are widely used in military fields, material science, petrochemicals, dyes, sugar production and many other fields. Especially in the field of medicine, nitrates have excellent curative effects in the treatment of angina pectoris and other related diseases. Not only that, because NO plays a vital role in maintaining the normal physiological functions of the nervous, cardiovascular and immune systems in the human body. As an efficient NO donor, nitrate has been introduced into the synthesis of various drugs and bioactive molecules. [0003] The traditional method for preparing nitrate compounds mainly contains following two kinds: (1) strong acid nitration method of alcohol, this method usually uses conce...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/40C07F9/53
CPCC07F9/4056C07F9/5333
Inventor 杨斌王雪侯淑敏丁仕钰赵晓楠
Owner YANTAI UNIV
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