CN1315854C - Methyl-phospho-acid pentaerythritol ester with hydroxy and its preparation - Google Patents
Methyl-phospho-acid pentaerythritol ester with hydroxy and its preparation Download PDFInfo
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- CN1315854C CN1315854C CNB2005100234486A CN200510023448A CN1315854C CN 1315854 C CN1315854 C CN 1315854C CN B2005100234486 A CNB2005100234486 A CN B2005100234486A CN 200510023448 A CN200510023448 A CN 200510023448A CN 1315854 C CN1315854 C CN 1315854C
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- pentaerythritol ester
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Abstract
The present invention relates to methyl phosphonic acid pentaerythritol ester with hydroxy and shown as the following chemical formula, and a preparation method thereof. The chemical name of methyl phosphonic acid pentaerythritol ester with hydroxy is 5, 5-dihydroxy methyl-2-oxygen-1, 3, 2-dioxy dioxy phospha cyclohexane. In the method, pentaerythritol, organic solvents and dialkyl methyl phosphonate are mixed, stirred and heated with catalysts; reaction temperature and time are controlled; coarse products of 5, 5-dihydroxy methyl-2-oxygen-1, 3, 2-dioxy dioxy phospha cyclohexane are obtained; the coarse products are separated by a column chromatography method and are recrystallized for obtaining white needle-shaped methyl phosphonic acid pentaerythritol ester. The methyl phosphonate ester has two methylol, and the methyl phosphonate ester can be used as organic synthesis intermediate bodies and fire retarding agents.
Description
Technical field:
The present invention relates to a kind of organic phosphorus compound and preparation method thereof, particularly a kind of can be as hydroxyl methyl-phosphorous acid pentaerythritol ester of fire retardant and organic synthesis intermediate and preparation method thereof.
Background technology:
Organic phosphine compound can be used as the organic synthesis raw material, prepares compound new, that have property.At present, a series of phosphonic acid esters such as common organic phosphine compound such as methyl-phosphorous acid dialkyl be important synthesis intermediates very, but they itself are not with reactive group, and the reaction conditions that requires during as reactant is higher, and this brings some inconvenience to building-up reactions.(Liu Guantong, Dong Shuzhi execute all the year round and wait, synthetic technology and application as people such as Liu Guantong, 1997,12 (4), 21) use dimethyl methyl phosphonate as the reactant intermediate, the fire retardant that the preparation fiber is used, product is two kinds of mixture of products, is not easy to obtain than pure products.Present existing organic phospho acid dialkyl, also not having bibliographical information is the hydroxyl phosphonate compound of parent with the phosphonic acid ester.
Summary of the invention:
The objective of the invention is synthetic a kind of hydroxyl methyl-phosphorous acid pentaerythritol ester.The stable performance at normal temperatures of this phosphonic acid ester contains two carbon hydroxyls, can be used as reaction intermediate and be applied in the organic synthesis in solution; Simultaneously because phosphorus element-containing also can be used as fire retardant.
A kind of hydroxyl methyl-phosphorous acid pentaerythritol ester of the present invention, its chemical name is 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinanes, its structural formula is as follows:
Of the present invention 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, the concrete preparation method of 2 dioxaphosphorinanes is as follows:
(a) 1mol tetramethylolmethane and 0～1000ml organic solvent are joined in the three-necked bottle, stir, add 1.0～1.5mol dialkyl methyl phosphonate and 0.001～0.1mol catalyzer then, reacted 2～40 hours controlled temperature to 100～240 ℃, and distillation removes and desolvates and unreacted reactant, obtain 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinane crude products;
(b) with 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinane crude products separate with column chromatography, wherein sorbent material is a silica gel, makes leacheate with organic solvent, and recrystallization obtains white needle-like crystals again, promptly 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinanes.
The chemical structural formula of the methyl-phosphorous acid dialkyl that the present invention uses is as follows:
R
1, R
2Be selected from CH respectively
3Or C
2H
5, dimethyl methyl phosphonate is wherein arranged, methyl-phosphorous acid methyl ethyl ester, methyl-phosphorous acid diethyl ester.
The organic solvent that the present invention uses has N, N ' dimethyl formamide, N, N ' N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), sherwood oil, ethyl acetate, acetone, ethanol or tetrahydrofuran (THF).
The catalyzer that the present invention uses has sodium methylate or tertiary butyl potassium.
The present invention prepares 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, and the entire reaction equation of 2 dioxaphosphorinanes can be expressed as:
Of the present invention 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, the characteristics of 2 dioxaphosphorinanes are to contain phosphoric, tetramethylolmethane skeleton and hydroxyl in the molecular structure simultaneously, these characteristics are given this compounds property and purposes has: molecule has the acid source (phosphoric) and the carbon source (tetramethylolmethane skeleton) of expansion type flame retardant simultaneously, can use as the fire retardant that contains expansion type flame retardant two key elements simultaneously; Compare with the dialkyl alkylphosphonate before the reaction, it is white crystal at normal temperatures, preserves easily and adds in the material; 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3 also contains 2 hydroxyls in 2 dioxaphosphorinanes, and hydroxyl can be used as active group and participates in other organic syntheses.Such as, with phosphorus oxychloride and its reaction, can synthesize another and can be used for fire-retardant organic phosphine compound.
Description of drawings:
Fig. 1 is among the embodiment 15,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, the infrared spectra of 2 dioxaphosphorinanes;
Fig. 2 is among the embodiment 15,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, the mass spectrum of 2 dioxaphosphorinanes;
Fig. 3 is among the embodiment 15,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, the proton nmr spectra of 2 dioxaphosphorinanes (deuterated dimethyl sulfoxide);
Fig. 4 is among the embodiment 15,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, the proton nmr spectra of 2 dioxaphosphorinanes (adding a small amount of heavy water exchange reactive hydrogen in the deuterated dimethyl sulfoxide);
Embodiment:
The present invention will be described in more details technical scheme of the present invention by the following specific embodiments, but the present invention is not limited to embodiment proposed below.
Embodiment 1:
(a) with 1mol tetramethylolmethane and 400mlN, the N dimethyl formamide joins in the three-necked bottle, stirs, and adds the 1.1mol dimethyl methyl phosphonate then, the 0.005mol sodium methylate, and controlled temperature to 153 ℃ refluxes, and reacts 10 hours.Distillation removes and desolvates and unreacted reactant, obtains 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinane crude products;
(b) with 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 two dioxaphosphorinane crude products separate with column chromatography, the above silica gel of 300 orders is made sorbent material, use ethyl acetate: ethanol: the mixed solvent of water=4: 1: 0.5 is made leacheate, and the drip washing separating mixture is monitored sepn process with thin layer chromatography, with the component re-crystallizing in ethyl acetate that leaches out, up to obtaining the white needles solid, this solid is the methyl-phosphorous acid pentaerythritol ester, and its chemical name is 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinanes, fusing point are 117～119 ℃.Fig. 1 is 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, the infrared spectrogram of 2 dioxaphosphorinanes: FTIR (KBr, cm
-1): 3437～3400 (C-OH); 2980～2875 (CH
2-,-CH
3); 1324,1240 (P=O); 1046,839 (P-O-C).Fig. 2 is 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, and the mass spectrum of 2 dioxaphosphorinanes, mass-to-charge ratio is 197 to be molecular ion peaks (molecular weight of methyl-phosphorous acid pentaerythritol ester is 196) of M+1.Fig. 3 is 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, and the proton nmr spectra of 2 dioxaphosphorinanes (deuterated dimethyl sulfoxide), the ownership at its each peak is as shown in the figure; Fig. 4 is 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3, and the proton nmr spectra of 2 dioxaphosphorinanes (adding heavy water exchange reactive hydrogen in the deuterated dimethyl sulfoxide), the ownership at its peak is as shown.
Embodiment 2:
(a) with the 1mol tetramethylolmethane, 1.2mol dimethyl methyl phosphonate and 0.002mol sodium methylate directly add in the three-necked bottle, stir, and controlled temperature to 200 ℃ refluxes, and reacts after 2 hours, obtains crude product;
(b) crude product is separated with column chromatography, the above silica gel of 300 orders is made sorbent material, make leacheate with ethyl acetate, the drip washing separating mixture is monitored sepn process with thin layer chromatography, then with the component re-crystallizing in ethyl acetate that leaches out, obtain the white needles solid, this solid is 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinanes.
Claims (4)
1. the preparation method of a hydroxyl methyl-phosphorous acid pentaerythritol ester is characterized in that the preparation method is as follows:
(a) 1mol tetramethylolmethane and 0～1000ml organic solvent are joined in the three-necked bottle, stir, add 1.0～1.5mol methyl-phosphorous acid dialkyl then, 0.001～0.1mol catalyzer, controlled temperature to 100～240 ℃, reacted 2～40 hours, distillation removes and desolvates and unreacted reactant, obtains 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinane crude products;
(b) with 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinane crude products separate with column chromatography, used sorbent material is a silica gel, and organic solvent is a leacheate, and recrystallization obtains white needle-like crystals again, promptly 5,5-dihydroxymethyl-2-methyl-2-oxygen-1,3,2 dioxaphosphorinanes.
2. the preparation method of a kind of hydroxyl methyl-phosphorous acid pentaerythritol ester according to claim 1 is characterized in that the chemical structural formula of methyl-phosphorous acid dialkyl is as follows:
R
1, R
2Be selected from CH respectively
3Or C
2H
5
3. the preparation method of a kind of hydroxyl methyl-phosphorous acid pentaerythritol ester according to claim 1 is characterized in that organic solvent is N, N ' dimethyl formamide, N, N ' N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), sherwood oil, ethyl acetate, acetone, ethanol or tetrahydrofuran (THF).
4. the preparation method of a kind of hydroxyl methyl-phosphorous acid pentaerythritol ester according to claim 1 is characterized in that catalyzer is sodium methylate or tertiary butyl potassium.
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| CNB2005100234486A CN1315854C (en) | 2005-01-20 | 2005-01-20 | Methyl-phospho-acid pentaerythritol ester with hydroxy and its preparation |
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| CN1315854C true CN1315854C (en) | 2007-05-16 |
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| CN101775135B (en) * | 2009-10-20 | 2012-09-05 | 苏州科技学院 | Carboxyethyl phenyl phosphinic acid piperazine polymer and preparation method thereof |
| CN105218859B (en) * | 2015-10-26 | 2018-06-19 | 苏州科技大学 | Reactive flame retardant organic phosphonate compounds and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU166034A1 (en) * | Б. И. Голованенко, И. Г. Ахметов , О. А. Шарипов | METHOD OF OBTAINING PHTHALIC ANHYDRIDE | ||
| US3984502A (en) * | 1974-04-12 | 1976-10-05 | Stauffer Chemical Company | Method of preparing vinyl phosphonate ester of pentaerythritol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU166034A1 (en) * | Б. И. Голованенко, И. Г. Ахметов , О. А. Шарипов | METHOD OF OBTAINING PHTHALIC ANHYDRIDE | ||
| US3984502A (en) * | 1974-04-12 | 1976-10-05 | Stauffer Chemical Company | Method of preparing vinyl phosphonate ester of pentaerythritol |
Non-Patent Citations (4)
| Title |
|---|
| 1，3，2-二氧磷杂环己烷衍生物的合成 周少林等，华中师范大学学报(自然科学版)，第38卷第2期 2004 * |
| 1，3，2-二氧磷杂环己烷衍生物的合成 周少林等，华中师范大学学报(自然科学版)，第38卷第2期 2004;聚磷酸酯阻燃剂研究进展 汪朝阳等，塑料，第32卷第3期 2003;磷***涤纶纤维用阻燃剂YHD的研制及应用 刘贯通等，合成技术及应用，第12卷第4期 1997 * |
| 磷***涤纶纤维用阻燃剂YHD的研制及应用 刘贯通等，合成技术及应用，第12卷第4期 1997 * |
| 聚磷酸酯阻燃剂研究进展 汪朝阳等，塑料，第32卷第3期 2003 * |
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