CN1275974C - Catalystic preparation of nitrine diphenyl posphate - Google Patents
Catalystic preparation of nitrine diphenyl posphate Download PDFInfo
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Abstract
本发明公开了一种叠氮磷酸二苯酯的制备方法，其主要步骤是以氯代磷酸二苯酯和叠氮钠为原料，以季铵盐、叔胺无机盐、强碱性叔胺或冠醚化合物为相转移催化剂，在15～30℃反应10～15小时后制得叠氮磷酸二苯酯。该方法具有制备反应所需时间短，操作简单，反应条件温和及所得产品纯度高等优点，避免了现有技术中需高真空度的减压蒸馏等一些复杂操作，是一种易于大规模工业化生产叠氮磷酸二苯酯的制备方法。The invention discloses a preparation method of diphenylphosphoric azide. The main steps are to use diphenyl chlorophosphate and sodium azide as raw materials, and use quaternary ammonium salt, tertiary amine inorganic salt, strong basic tertiary amine or The crown ether compound is a phase transfer catalyst, and diphenyl phosphoric acid azide is prepared after reacting at 15-30°C for 10-15 hours. The method has the advantages of short time required for the preparation reaction, simple operation, mild reaction conditions and high purity of the obtained product, and avoids some complex operations such as vacuum distillation requiring high vacuum degree in the prior art, and is a method that is easy for large-scale industrial production. The preparation method of diphenylphosphoryl azide.
Description
技术领域technical field
本发明涉及一种叠氮磷酸二苯酯的制备方法，特别涉及一种采用相转移催化剂催化制备叠氮磷酸二苯酯的方法。The invention relates to a preparation method of diphenyl phosphoric azide, in particular to a method for preparing diphenyl phosphoric azide as catalyzed by a phase transfer catalyst.
技术背景technical background
叠氮磷酸二苯酯(简称DPPA)是一种在有机合成上被广泛的使用的有机磷试剂，其化学结构式如下：Diphenylphosphoryl azide (DPPA for short) is a widely used organophosphorus reagent in organic synthesis, and its chemical structural formula is as follows:
现有的叠氮磷酸二苯酯的制备方法主要分为二种，一种是溶剂法，即以氯代磷酸二苯酯为原料，以无水丙酮为溶剂，与叠氮钠反应制得了叠氮磷酸二苯酯(JP805459)；另一种为无溶剂法，即在常温下，氯代磷酸二苯酯和叠氮钠在无溶剂情况下反应制得目标化合物(《化学试剂》1992，14(6)377)。The existing preparation method of diphenylphosphoric azide is mainly divided into two kinds, one is the solvent method, that is, diphenyl chlorophosphoric acid is used as raw material, and anhydrous acetone is used as solvent to react with sodium azide to obtain azide Nitrophosphoric acid diphenyl ester (JP805459); The other is a solvent-free method, that is, at normal temperature, chlorophosphoric acid diphenyl ester and sodium azide react under solvent-free conditions to obtain the target compound ("Chemical Reagent" 1992, 14 (6) 377).
上述两种方法都存在着制备反应时间长、操作复杂、反应物和目标产物难以分离及目标产物的产率和纯度都不高等缺陷。The above two methods all have defects such as long preparation reaction time, complex operation, difficult separation of reactant and target product, and low yield and purity of target product.
发明内容Contents of the invention
本发明的目的在于，提供一种制备叠氮磷酸二苯酯的新制备方法，以克服上述现有技术中存在的缺陷。The purpose of the present invention is to provide a new preparation method for preparing diphenylphosphoryl azide, so as to overcome the defects in the above-mentioned prior art.
发明构思：Invention idea:
在本发明的合成方法中，考虑到氯代磷酸二苯酯和叠氮钠的反应，是液一固之间的反应，固相并不溶于液相，反应中必须使两相充分接触，采用相转移催化剂有助于反应的进行。In the synthetic method of the present invention, considering that the reaction of diphenyl chlorophosphate and sodium azide is a reaction between liquid and solid, the solid phase is not soluble in the liquid phase, and the two phases must be fully contacted in the reaction. Phase transfer catalysts facilitate the reaction.
技术方案：Technical solutions:
本发明所述的叠氮磷酸二苯酯的制备方法的主要步骤是以氯代磷酸二苯酯和叠氮钠为原料，以季铵盐、叔胺无机盐或强碱性叔胺为相转移催化剂，在15～30℃反应10～15小时后制得叠氮磷酸二苯酯。The main steps of the preparation method of diphenylphosphoryl azide in the present invention are to use diphenyl chlorophosphate and sodium azide as raw materials, and use quaternary ammonium salts, inorganic salts of tertiary amines or strongly basic tertiary amines as phase transfer Catalyst, after reacting for 10-15 hours at 15-30°C, diphenyl phosphoric acid azide can be prepared.
其中：氯代磷酸二苯酯、叠氮钠与相转移催化剂的摩尔比为1∶1～5∶0.001～0.1；Wherein: the molar ratio of diphenyl chlorophosphate, sodium azide and phase transfer catalyst is 1:1～5:0.001～0.1;
所说的季铵盐，叔胺无机盐和强碱性叔胺分别具有如下分子式：Said quaternary ammonium salt, tertiary amine inorganic salt and strongly basic tertiary amine have following molecular formula respectively:
R1R2R3NR4X，R1R2R3NHX，[CH3(OCH2CH2)n]3N；R 1 R 2 R 3 NR 4 X, R 1 R 2 R 3 NHX, [CH 3 (OCH 2 CH 2 )n] 3 N;
式中：R1、R2和R3分别为C1-18的烷基、苯基和苄基中的一种，R4为C1-4的烷基、苄基或苯基，X＝Cl、Br或I，n＝1～3。In the formula: R 1 , R 2 and R 3 are respectively one of C 1-18 alkyl, phenyl and benzyl, R 4 is C 1-4 alkyl, benzyl or phenyl, X= Cl, Br or I, n=1-3.
本发明的反应方程式如下：Reaction equation of the present invention is as follows:
由上述技术方案可知，在本发明所述的制备方法中无需溶剂，只需加入一种相转移催化剂，在15～30℃搅拌反应，停止反应后滤去不溶物，即可得到叠氮磷酸二苯酯。该方法具有制备反应所需时间短，操作简单，反应条件温和及所得产品纯度高(可达99.3％)等优点，避免了现有技术中需高真空度的减压蒸馏等一些复杂操作，是一种易于大规模工业化制备叠氮磷酸二苯酯的制备方法。It can be seen from the above technical scheme that no solvent is needed in the preparation method of the present invention, only a phase transfer catalyst is added, the reaction is stirred at 15-30°C, the insoluble matter is filtered off after the reaction is stopped, and phosphoric acid diazide can be obtained. phenyl esters. The method has the advantages of short time required for the preparation reaction, simple operation, mild reaction conditions and high purity of the obtained product (up to 99.3%), and avoids some complex operations such as high-vacuum vacuum distillation in the prior art. A preparation method for large-scale industrial preparation of diphenylphosphoryl azide is easy.
具体实施方式Detailed ways
下面通过实施例对本发明作进一步的说明，其目的仅为更好理解本发明的内容，因此，所举之例并不限制本发明的保护范围：Below by embodiment the present invention will be further described, and its purpose is only to better understand content of the present invention, therefore, example does not limit protection scope of the present invention:
实施例1Example 1
氯代磷酸二苯酯47.9g(0.178mol)，叠氮钠20.7g(0.32mol)，四丁基溴化铵2.5g加入100ml的三口烧瓶中室温剧烈搅拌反应10小时，混合物逐渐乳浊，变粘，再逐渐变稀薄，颜色由无色变为浅灰色，过滤即可得到略带浅黄色或无色的微粘液体42.5g，产率86.2％，HPLC含量99.3％。Add 47.9g (0.178mol) of diphenyl chlorophosphate, 20.7g (0.32mol) of sodium azide, and 2.5g of tetrabutylammonium bromide into a 100ml three-necked flask and stir vigorously at room temperature for 10 hours. Viscous, then gradually become thinner, the color changes from colorless to light gray, and can be filtered to obtain 42.5g of slightly light yellow or colorless slightly viscous liquid, the yield is 86.2%, and the HPLC content is 99.3%.
分析数据：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)。Analysis data: IR(cm -1 ) 3060(w, CH), 2170(s, -N3), 1590(m), 1490(s, C=C), 1270(m, P=O), 960(s , PO-Aryl).
实施例2Example 2
在100ml的三口烧瓶中加入氯代磷酸二苯酯48.1g(0.18mol)，叠氮钠27.6g(0.42mol)，TEBA 3.0g，室温下强烈搅拌反应15h，过滤得略带浅黄色液体41.8g，HPLC含量97.7％，产率85.2％。Add 48.1g (0.18mol) of diphenyl chlorophosphate, 27.6g (0.42mol) of sodium azide, and 3.0g of TEBA into a 100ml three-necked flask, stir vigorously at room temperature for 15 hours, and filter to obtain 41.8g of slightly light yellow liquid , HPLC content 97.7%, yield 85.2%.
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| CN 03128979 CN1275974C (en) | 2003-05-30 | 2003-05-30 | Catalystic preparation of nitrine diphenyl posphate |
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