CN1275974C - Catalystic preparation of nitrine diphenyl posphate - Google Patents

Catalystic preparation of nitrine diphenyl posphate Download PDF

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Publication number
CN1275974C
CN1275974C CN 03128979 CN03128979A CN1275974C CN 1275974 C CN1275974 C CN 1275974C CN 03128979 CN03128979 CN 03128979 CN 03128979 A CN03128979 A CN 03128979A CN 1275974 C CN1275974 C CN 1275974C
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preparation
diphenyl phosphate
azide
diphenylphosphoryl azide
tertiary amine
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CN 03128979
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CN1552719A (en
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吴范宏
辛水波
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Guilin Guikai Biological Science & Technology Co., Ltd.
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East China University of Science and Technology
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Abstract

The present invention discloses a preparation method of diphenylphosphoryl azide, which comprises the following main steps of using chloro diphenyl phosphate and sodium azide as raw materials and quaternary ammonium salt, trialkylamine inorganic salt and strong alkalinity trialkylamine or crown ether compounds as phase transfer catalysts and carrying out the reaction at the temperature of 15 to 30 DEG C for 10 to 15 hours, and thus, obtaining the diphenylphosphoryl azide. The preparation method of diphenylphosphoryl azide has the advantages of short preparation reaction time, simple operation, mild reaction condition and high obtained product purity, avoids microvac reduced pressure distillation and other complicated operations of the prior art and is suitable for diphenylphosphoryl azide large-scale industral production.

Description

Catalysis method prepares diphenyl phosphate azide
Technical field
The present invention relates to a kind of preparation method of diphenyl phosphate azide, particularly a kind of method that adopts phase-transfer catalyst catalytic preparation diphenyl phosphate azide.
Technical background
Diphenyl phosphate azide (being called for short DPPA) is a kind of organophosphorus reagent that is used widely in organic synthesis, and its chemical structural formula is as follows:
Figure C0312897900031
The preparation method of existing diphenyl phosphate azide mainly is divided into two kinds, and a kind of is solvent method, is raw material with the chlorinated diphenyl phosphate promptly, is solvent with the anhydrous propanone, has made diphenyl phosphate azide (JP805459) with the sodium azide reaction; Another kind is a solventless method, and at normal temperatures promptly, chlorinated diphenyl phosphate and sodium azide react under solvent-free situation and make target compound (" chemical reagent " 1992,14 (6) 377).
Above-mentioned two kinds of methods exist all that preparation feedback time length, complicated operation, reactant and target product are difficult to separate and the productive rate and the not high defective of purity of target product.
Summary of the invention
The objective of the invention is to, a kind of new preparation process for preparing diphenyl phosphate azide is provided, to overcome the defective that exists in the above-mentioned prior art.
Inventive concept:
In synthetic method of the present invention, consider the reaction of chlorinated diphenyl phosphate and sodium azide, be the reaction between liquid one is consolidated, solid phase also is insoluble to liquid phase, and two-phase is fully contacted, and adopts phase-transfer catalyst to help the carrying out that reacts.
Technical scheme:
The preparation method's of diphenyl phosphate azide of the present invention key step is to be raw material with chlorinated diphenyl phosphate and sodium azide, with quaternary ammonium salt, tertiary amine inorganic salt or strong alkaline tertiary amine is phase-transfer catalyst, makes diphenyl phosphate azide 15～30 ℃ of reactions after 10～15 hours.
Wherein: the mol ratio of chlorinated diphenyl phosphate, sodium azide and phase-transfer catalyst is 1: 1～5: 0.001～0.1;
Said quaternary ammonium salt, tertiary amine inorganic salt and strong alkaline tertiary amine have following molecular formula respectively:
R 1R 2R 3NR 4X，R 1R 2R 3NHX，[CH 3(OCH 2CH 2)n] 3N；
In the formula: R 1, R 2And R 3Be respectively C 1-18Alkyl, phenyl and benzyl in a kind of, R 4Be C 1-4Alkyl, benzyl or phenyl, X=Cl, Br or I, n=1～3.
Reaction equation of the present invention is as follows:
Figure C0312897900041
As shown from the above technical solution, need not solvent in preparation method of the present invention, only need to add a kind of phase-transfer catalyst, at 15～30 ℃ of stirring reactions, elimination insolubles behind the stopped reaction can obtain diphenyl phosphate azide.It is short that this method has the preparation feedback required time, simple to operate, reaction conditions gentleness and products obtained therefrom purity height advantages such as (can reach 99.3%), needing in the prior art having avoided some complex operations such as underpressure distillation of condition of high vacuum degree, is a kind of preparation method that heavy industrialization prepares diphenyl phosphate azide that is easy to.
Embodiment
The present invention is further illustrated below by embodiment, and its purpose only is the better content of the present invention of understanding, and therefore, the cited case does not limit protection scope of the present invention:
Embodiment 1
Chlorinated diphenyl phosphate 47.9g (0.178mol), sodium azide 20.7g (0.32mol), the reaction of room temperature vigorous stirring is 10 hours in the there-necked flask of Tetrabutyl amonium bromide 2.5g adding 100ml, mixture is milkiness gradually, becomes sticky, and weakens gradually again, color is by the colourless light gray that becomes, filtration can obtain slightly light yellow or colourless little slime body 42.5g, productive rate 86.2%, HPLC content 99.3%.
Analytical data: IR (cm -1) 3060 (w, C-H), 2170 (s ,-N3), 1590 (m), 1490 (s, C=C), 1270 (m, P=O), 960 (s, P-O-Aryl).
Embodiment 2
In the there-necked flask of 100ml, add chlorinated diphenyl phosphate 48.1g (0.18mol), sodium azide 27.6g (0.42mol), TEBA 3.0g, violent stirring reaction 15h under the room temperature, filter light yellow liquid 41.8g slightly, HPLC content 97.7%, productive rate 85.2%.

Claims (2)

1, a kind of preparation method of diphenyl phosphate azide, it is characterized in that, described preparation method's key step is to be raw material with chlorinated diphenyl phosphate and sodium azide, with quaternary ammonium salt, tertiary amine inorganic salt or strong alkaline tertiary amine is phase-transfer catalyst, makes diphenyl phosphate azide 15～30 ℃ of reactions after 10～15 hours;
Wherein: the mol ratio of chlorinated diphenyl phosphate, sodium azide and phase-transfer catalyst is 1: 1～5: 0.001～0.1;
Said quaternary ammonium salt, tertiary amine inorganic salt and strong alkaline tertiary amine have following molecular formula respectively:
R 1R 2R 3NR 4X，R 1R 2R 3NHX，[CH 3(OCH 2CH 2)n] 3N；
In the formula: R 1, R 2And R 3Be respectively C 1-18Alkyl, phenyl and benzyl in a kind of, R 4Be C 1-4Alkyl, benzyl or phenyl, X=Cl, Br or I, n=1～3.
2, preparation method as claimed in claim 1 is characterized in that, wherein said phase-transfer catalyst is a Tetrabutyl amonium bromide.
CN 03128979 2003-05-30 2003-05-30 Catalystic preparation of nitrine diphenyl posphate Expired - Fee Related CN1275974C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153257B (en) * 2014-06-12 2019-03-05 正大天晴药业集团股份有限公司 The preparation method of Suo Feibuwei
CN113980356B (en) * 2021-11-24 2023-07-14 浙江工业大学 Oxygen-containing azide group functionalized modified graphene oxide nanomaterial

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