CN102766167A - Synthetic method of 6(4-hydroxyl ethyoxyl) cyclotriphophazene - Google Patents
Synthetic method of 6(4-hydroxyl ethyoxyl) cyclotriphophazene Download PDFInfo
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Abstract
The invention discloses a synthetic method of 6(4-hydroxyl ethyoxyl) cyclotriphophazene. The method includes the following steps: (1) enabling methyl cellosolve and sodium hydride to react to obtain methyl sodium ethoxide, adding a tetrahydrofuran solution of hexachlorocyclotriphosphazene, reacting for 30min-45min at the temperature of 20 DEG C-35 DEG C, filtering, removing solvent by steaming, extracting, washing and conducting reduced pressure distillation to obtain 6(4-methoxyl ethyoxyl) cyclotriphophazene; (2) enabling the 6(4-methoxyl ethyoxyl) cyclotriphophazene and iodotrimethylsilane to react for 30h-40h at the temperature of 25 DEG C-35 DEG C under the condition of stirring, adding a methanol solution of sodium hydroxide, reacting for 6h-8h at the temperature of 15-30 DEG C under the condition of stirring, filtering, and conducting reduced pressure removing of the solvent by steaming to obtain the 6(4-hydroxyl ethyoxyl) cyclotriphophazene. The synthetic method of the 6(4-hydroxyl ethyoxyl) cyclotriphophazene is high in reacting yield and is mainly used for synthesis of the 6(4-hydroxyl ethyoxyl) cyclotriphophazene.
Description
Technical field
The present invention relates to a kind of compound method of six (4-hydroxyl-oxethyls) ring, three phosphonitriles, belong to the field of chemical synthesis.
Background technology
Encircle three phosphonitrile structures good thermotolerance and superior flame retardant resistance can be provided, receive much concern at fire-resistant, fire retardant material and speciality polymer investigation of materials field.Six (4-hydroxyl-oxethyls) ring, three phosphonitriles are a kind of special aliphatics ring three phosphazene derivatives; Because of containing six activity hydroxies in its structure, can be used as heat-resisting, the properties-correcting agent of flame retardant polyurethane material and the poly-hydroxy initiator for preparing six arm star polymkeric substance usually.
Six (4-hydroxyl-oxethyls) ring, three phosphonitriles can obtain with hexachlorocyclotriphosphazene and sodium alkoxide substitution reaction." Poly (organophosphazene) s and related compounds:synthesis such as Jaeger R.D. for example; Properties and applications " Prog.Polym.Sci.; 1998,23 (2): 179-276 discloses a kind of compound method of six (4-hydroxyl-oxethyls) ring, three phosphonitriles, and this method is raw material with the hexachlorocyclotriphosphazene; Directly carry out nucleophilic substitution reaction with glycol monomethyl sodium and obtain target compound, reaction yield is 43.5%.But the yield of this method is lower, traces it to its cause, and possibly be because the hydroxyl in the glycol monomethyl sodium molecule has the certain reaction activity, easily five yuan of annulations or bimolecular phosphonitrile ring linked reaction takes place on same phosphorus atom and produces a large amount of by products.Its reaction process is as follows:
Summary of the invention
Technical problem to be solved by this invention is to overcome disadvantages of background technology and defective, and the compound method of higher six (4-hydroxyl-oxethyls) ring, three phosphonitriles of a kind of reaction yield is provided.
Synthetic route of the present invention is as follows:
In order to solve the problems of the technologies described above, six (4-hydroxyl-oxethyls) of the present invention encircle the compound method of three phosphonitriles, and its structural formula is a raw material with the hexachlorocyclotriphosphazene shown in (I), and its structural formula is as follows shown in (II): comprise the steps:
1) sodium hydride and THF are joined in the reaction flask, under 20 ℃～30 ℃ stirrings of temperature, drip the tetrahydrofuran solution that is dissolved with methyl cellosolve, drip off the back and react 30min～45min down for 20 ℃～35 ℃ in temperature; Being cooled to temperature is 0 ℃～10 ℃, drips the tetrahydrofuran solution that is dissolved with hexachlorocyclotriphosphazene again, and dripping off the back is 30 ℃～60 ℃ reaction 24h～30h in temperature; After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Add methylene dichloride then, distilled water wash aforesaid liquid to water is told organic phase to neutral; Remove the methylene dichloride step of removing in this organic phase under reduced pressure; Get six (4-methoxy ethoxy) ring, three phosphonitriles, wherein the mol ratio of methyl cellosolve and hexachlorocyclotriphosphazene is 7.2: 1～8.0: 1, and the mol ratio of sodium hydride and methyl cellosolve is 1.2: 1～1.5: 1.
2) six (4-methoxy ethoxy) ring, three phosphonitriles, copper powder and the chloroform that step 1) are obtained add in the reaction flask; In temperature is that the chloroformic solution that will be dissolved with Iodotrimethylsilane under 0 ℃～5 ℃ stirrings adds in the reaction flask, add the chloroformic solution that is dissolved with Iodotrimethylsilane after, at 25 ℃～35 ℃ reactions of temperature 30h～40h; After reaction is accomplished; Filtering reacting liquid removes the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid; Under 15 ℃～30 ℃ stirrings of temperature; The methanol solution that in light yellow viscous liquid, adds the sodium hydroxide of 600ml0.4moL/L～0.8moL/L, reaction 6h～8h is through filtering reaction solution; Underpressure distillation removes the methyl alcohol in the gained filtrating; Obtain six (4-hydroxyl-oxethyls) ring, three phosphonitriles, wherein the mol ratio of Iodotrimethylsilane and six (4-methoxy ethoxy) ring three phosphonitriles is 1.5: 1～2.0: 1, and the mol ratio of copper powder and Iodotrimethylsilane is 0.05: 1～0.1: 1.
Optimal technical scheme of the present invention; Comprise the steps: 1) 300ml THF and 149.28g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 157.78g methyl cellosolve in the downhill reaction bottle; After dripping off, at 30 ℃ of reactions of temperature 30min.Being cooled to temperature then is 5 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 50 ℃ of reactions of temperature 30h.After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid; Add the 150ml methylene dichloride to this liquid then, be neutral, tell organic phase with distilled water wash aforesaid liquid to water; Remove the methylene dichloride in this organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, three phosphonitriles;
2) 100g six (4-methoxy ethoxy) ring three phosphonitriles and the 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 63.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 30h for 25 ℃ in temperature after being added dropwise to complete.After reaction was accomplished, filtering reacting liquid removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid; Under 20 ℃ of stirrings of temperature; The methanol solution that in light yellow viscous liquid, adds the sodium hydroxide of 600m10.6mol/L, reaction 6h is then through filtering reaction solution; Remove the methyl alcohol in the gained filtrating under reduced pressure, obtain six (4-hydroxyl-oxethyls) ring, three phosphonitriles of white solid.
Advantage of the present invention:
The compound method reaction yield of six (4-hydroxyl-oxethyls) ring, three phosphonitriles of the present invention is higher, and its total recovery reaches as high as 97.82%, and the method six in the documents (4-hydroxyl-oxethyl) ring three phosphonitrile reaction yields are 43.5%; The compound method aftertreatment of six (4-hydroxyl-oxethyls) ring, three phosphonitriles of the present invention in addition is simple; Only need remove solvent under reduced pressure and just can obtain six (4-hydroxyl-oxethyls) rings, three phosphonitriles, and the method aftertreatment in the documents need be carried out column chromatography and separates and just can obtain six (4-hydroxyl-oxethyls) ring, three phosphonitriles.
Embodiment:
Further invention is elaborated below in conjunction with embodiment.
The ir spectra instrument is the Nexus 870 type FTIR Spectrometer FTIRs of U.S. Nicolet company;
Nuclear magnetic resonance apparatus is Switzerland Bruker AV 500 type magnetic nuclear resonance analyzers.
The ultimate analysis instrument is a Vario ELIII type elemental analyser;
Synthesizing of hexachlorocyclotriphosphazene
In the 10L there-necked flask, add 1000g phosphorus pentachloride, 258g ammonium chloride and 7.5L sym.-tetrachloroethane, be to add pyridine under 20 ℃～25 ℃ stirrings in temperature, heat temperature raising is to refluxing stopped reaction when back flow reaction to reaction system does not have the generation of HCl gas.Filter brown filtrating through cooling off, crossing, distilled water wash filtrating 3～4 times is told organic layer; And spend the night with anhydrous magnesium sulfate drying, filter, remove under reduced pressure the solvent 1,1 in the filtrating; 2, the 2-tetrachloroethane obtains faint yellow thick product; With sherwood oil recrystallization twice, obtain the hexachlorocyclotriphosphazene 1213.37g of white rhomboidan shape, productive rate 65.8%.
Below be the embodiment that the contriver provides, need to prove that these embodiment are more excellent examples, be mainly used in and understand the present invention, but the invention is not restricted to these embodiment.
Embodiment 1
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
With 300ml THF and 149.28g sodium hydride (50%?) join in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 157.78g methyl cellosolve in the downhill reaction bottle; After dripping off, at 30 ℃ of reactions of temperature 30min.Being cooled to temperature then is 5 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 50 ℃ of reactions of temperature 30h.Filtering reacting liquid, and remove the THF in the gained filtrating under reduced pressure, obtain faint yellow muddy viscous liquid; Add the 150ml methylene dichloride to this liquid then, be neutral, tell organic phase with distilled water wash aforesaid liquid to water; Remove the methylene dichloride in this organic phase under reduced pressure; Get six (4-methoxy ethoxy) ring, the three phosphonitrile 167.93g of yellow thickness transparent liquid shape,, yield is 99.59%.
Structure is identified:
Molecular formula: C
18H
42N
3O
12P
3
Theoretical value: C 36.93, H 7.23, and N 7.18
Measured value: C 36.95, H 7.20, and N 7.16
IR(KBr，cm
-1)：2920(-CH
3)，2850(-CH
2)；1197，1172(P＝N)；1031(P-O-C)；893(P-N)。
1H?NMR(Acetone-d
6，δppm)：3.32(-C
H 3)；3.56～3.73(-C
H 2)。
13C?NMR(Acetone-d
6，δppm)：59.5(-
CH
3)；55.2，73.1(-
CH
2)。
31P?NMR(Acetone-d
6，δppm)：10.09。
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; In 0 ℃～5 ℃ stirrings of temperature downhill reaction bottle, drip the chloroformic solution 100ml that is dissolved with the 63.03g Iodotrimethylsilane; After being added dropwise to complete, at 25 ℃ of reactions of temperature 30h.After reaction was accomplished, filtering reacting liquid removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that in this light yellow viscous liquid, adds the sodium hydroxide of 600ml 0.6mol/L then; At 20 ℃ of stirring reaction 6h of temperature; Then through filtering reaction solution; Remove the methyl alcohol in the gained filtrating under reduced pressure, obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 86.17g of white solid, productive rate is 98.22%.
Structure is identified:
Molecular formula: C
12H
30N
3O
12P
3
Theoretical value: C 28.75, H 6.03, and N 8.38
Measured value: C 28.71, H 6.05, and N 8.36
IR(KBr，cm
-1)：3301(-OH)，2872(-CH
2)；1192(P＝N)；1098(P-O-C)；840(P-N)。
1H?NMR(Acetone-d
6，δppm)：3.65(-O
H)；3.46～3.72(-C
H 2)。
13C?NMR(Acetone-d
6，δppm)：57.7，62.6(-
CH
2)。
31P?NMR(Acetone-d
6，δppm)：7.29。
Above-mentioned appraising datum confirms material that compound method of the present invention obtains six (4-hydroxyl-oxethyls) ring, three phosphonitriles really.
Embodiment 2
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
300ml THF and 129.60g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 164.35g methyl cellosolve in the downhill reaction bottle; After dripping off, at 30 ℃ of reactions of temperature 45min.Being cooled to temperature then is 5 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 50 ℃ of reactions of temperature 30h.After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid, add the 150ml methylene dichloride to this liquid then, be neutral with distilled water wash aforesaid liquid to water; Tell organic phase; Remove the methylene dichloride in the organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, the three phosphonitrile 166.57g of yellow thickness transparent liquid shape, yield is 98.79%.
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 52.52g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 30h for 25 ℃ in temperature after being added dropwise to complete.After reaction was accomplished, filtering reacting liquid removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that adds the sodium hydroxide of 600ml 0.6mol/L then; At 15 ℃ of stirring reaction 6h of temperature,, remove the methyl alcohol in the gained filtrating under reduced pressure then through filtering reaction solution; Obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 85.96g of white solid, productive rate is 97.98%.
Embodiment 3
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
300ml THF and 129.60g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 164.35g methyl cellosolve in the downhill reaction bottle; After dripping off, at 35 ℃ of reactions of temperature 40min.Being cooled to temperature then is 0 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 60 ℃ of reactions of temperature 24h.After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid, add the 150ml methylene dichloride to this liquid then, be neutral with distilled water wash aforesaid liquid to water; Tell organic phase; Remove the methylene dichloride in this organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, the three phosphonitrile 165.96g of yellow thickness transparent liquid shape, yield is 98.42%.
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 70.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 30h for 30 ℃ in temperature after being added dropwise to complete.After-filtration is accomplished in reaction, removes the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that adds the sodium hydroxide of 600ml 0.6mol/L then; At 20 ℃ of stirring reaction 6h of temperature,, remove the methyl alcohol in the gained filtrating under reduced pressure then through filtering reaction solution; Obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 86.02g of white solid, productive rate is 98.05%.
Embodiment 4
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
300ml THF and 119.46g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 175.31g methyl cellosolve in the downhill reaction bottle; After dripping off, at 35 ℃ of reactions of temperature 40min.Being cooled to temperature then is 5 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 50 ℃ of reactions of temperature 24h.After reaction was accomplished, filtering reacting liquid removed the THF in this filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid, add the 150ml methylene dichloride to this liquid then, be neutral with distilled water wash aforesaid liquid to water; Tell organic phase; Remove the methylene dichloride that changes in the organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, the three phosphonitrile 167.09g of yellow thickness transparent liquid shape, yield is 99.10%.
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 1.60g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 63.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 30h for 25 ℃ in temperature after being added dropwise to complete.After reaction was accomplished, filtering reacting liquid removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that adds the sodium hydroxide of 600ml 0.6mol/L then; At 20 ℃ of stirring reaction 6h of temperature,, remove the methyl alcohol in the gained filtrating under reduced pressure then through filtering reaction solution; Obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 85.93g of white solid, productive rate is 97.95%.
Embodiment 5
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
300ml THF and 129.60g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 175.31g methyl cellosolve in the downhill reaction bottle; After dripping off, at 35 ℃ of reactions of temperature 40min.Being cooled to temperature then is 10 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 60 ℃ of reactions of temperature 30h.After reaction was accomplished, filtering reacting liquid removed the THF in this filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid, add the 150ml methylene dichloride to this liquid then, be washed with distilled water to water and be neutral; Tell organic phase; Remove the methylene dichloride in this organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, the three phosphonitrile 166.96g of yellow thickness transparent liquid shape, yield is 99.02%.
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 2.05g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 63.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 30h for 25 ℃ in temperature after being added dropwise to complete.After reaction was accomplished, filtering reacting liquid removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that adds the sodium hydroxide of 600ml 0.6mol/L then; At 20 ℃ of stirring reaction 6h of temperature,, remove the methyl alcohol in the gained filtrating under reduced pressure then through filtering reaction solution; Obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 85.24g of white solid, productive rate is 97.16%.
Embodiment 6
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
300ml THF and 119.46g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 157.78g methyl cellosolve in the downhill reaction bottle; After dripping off, at 20 ℃ of reactions of temperature 30min.Being cooled to temperature then is 10 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 30 ℃ of reactions of temperature 30h.After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid, add the 150ml methylene dichloride to this liquid then, be neutral with distilled water wash aforesaid liquid to water; Tell organic phase; Remove the methylene dichloride in this organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, the three phosphonitrile 166.25g of yellow thickness transparent liquid shape, yield is 98.6%.
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 63.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 35h for 30 ℃ in temperature after being added dropwise to complete.After reaction was accomplished, filtering reacting liquid removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that adds the sodium hydroxide of 600ml 0.6mol/L then; At 25 ℃ of stirring reaction 6h of temperature,, remove the methyl alcohol in the gained filtrating under reduced pressure then through filtering reaction solution; Obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 86.00g of white solid, productive rate is 98.03%.
Embodiment 7
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
300ml THF and 129.60g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 164.35g methyl cellosolve in the downhill reaction bottle; After dripping off, at 35 ℃ of reactions of temperature 45min.Being cooled to temperature then is 5 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 45 ℃ of reactions of temperature 30h.After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid, add the 150ml methylene dichloride to this liquid then, be neutral with distilled water wash aforesaid liquid to water; Tell organic phase; Remove the methylene dichloride in this organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, the three phosphonitrile 167.11g of yellow thickness transparent liquid shape, yield is 99.11%.
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 63.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 40h for 35 ℃ in temperature after being added dropwise to complete.After reaction was accomplished, the filtering reacting liquid reaction solution removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that adds the sodium hydroxide of 600ml 0.6mol/L then; At 30 ℃ of stirring reaction 6h of temperature,, remove the methyl alcohol in the gained filtrating under reduced pressure then through filtering reaction solution; Obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 85.98g of white solid, productive rate is 98.00%.
Embodiment 8
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
300ml THF and 129.60g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 164.35g methyl cellosolve in the downhill reaction bottle; After dripping off, at 35 ℃ of reactions of temperature 45min.Being cooled to temperature then is 0 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 50 ℃ of reactions of temperature 24h.After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid, add the 150ml methylene dichloride to this liquid then, be washed with distilled water to water and be neutral; Tell organic phase; Remove the methylene dichloride in this organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, the three phosphonitrile 167.03g of yellow thickness transparent liquid shape, yield is 99.06%.
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 63.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 40h for 35 ℃ in temperature after being added dropwise to complete.After reaction was accomplished, filtering reacting liquid removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that adds the sodium hydroxide of 600ml 0.6mol/L then; At 30 ℃ of stirring reaction 6h of temperature,, remove the methyl alcohol in the gained filtrating under reduced pressure then through filtering reaction solution; Obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 86.11g of white solid, productive rate is 98.15%.
Embodiment 9
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
300ml THF and 149.28g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 157.78g methyl cellosolve in the downhill reaction bottle; After dripping off, at 30 ℃ of reactions of temperature 30min.Being cooled to temperature then is 5 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 50 ℃ of reactions of temperature 30h.After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid, add the 150ml methylene dichloride to this liquid then, be washed with distilled water to water and be neutral; Tell organic phase; Remove the methylene dichloride in this organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, the three phosphonitrile 167.11g of yellow thickness transparent liquid shape, yield is 99.10%.
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 63.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 40h for 35 ℃ in temperature after being added dropwise to complete.After reaction was accomplished, filtering reacting liquid removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that adds the sodium hydroxide of 600ml 0.8mol/L then; At 30 ℃ of stirring reaction 6h of temperature,, remove the methyl alcohol in the gained filtrating under reduced pressure then through filtering reaction solution; Obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 86.05g of white solid, productive rate is 98.09%.
Embodiment 10
Synthesizing of (1) six (4-methoxy ethoxy) ring three phosphonitriles
300ml THF and 119.46g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 175.31g methyl cellosolve in the downhill reaction bottle; After dripping off, at 35 ℃ of reactions of temperature 40min.Being cooled to temperature then is 5 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 50 ℃ of reactions of temperature 24h.After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid, add the 150ml methylene dichloride to this liquid then, be washed with distilled water to water and be neutral; Tell organic phase; Remove the methylene dichloride in this organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, the three phosphonitrile 167.35g of yellow thickness transparent liquid shape, yield is 99.25%.
Synthesizing of (2) six (4-hydroxyl-oxethyls) ring three phosphonitriles
100g six (4-methoxy ethoxy) ring three phosphonitriles and 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 63.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 30h for 30 ℃ in temperature after being added dropwise to complete.The after-filtration reaction solution is accomplished in reaction, removes the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid.The methanol solution that adds the sodium hydroxide of 600ml 0.8mol/L then; At 30 ℃ of stirring reaction 8h of temperature,, remove the methyl alcohol in the gained filtrating under reduced pressure then through filtering reaction solution; Obtain six (4-hydroxyl-oxethyls) ring, the three phosphonitrile 85.94g of white solid, productive rate is 97.96%.
Claims (2)
1. the compound method of one kind six (4-hydroxyl-oxethyl) ring, three phosphonitriles, its structure is a raw material with the hexachlorocyclotriphosphazene shown in (I), its structure comprises the steps: shown in (II)
1) sodium hydride and THF are joined in the reaction flask, under 20 ℃～30 ℃ stirrings of temperature, drip the tetrahydrofuran solution that is dissolved with methyl cellosolve, drip off the back and react 30min～45min down for 20 ℃～35 ℃ in temperature; Being cooled to temperature is 0 ℃～10 ℃, drips the tetrahydrofuran solution that is dissolved with hexachlorocyclotriphosphazene again, and dripping off the back is 30 ℃～60 ℃ reaction 24h～30h in temperature; After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Add methylene dichloride then, distilled water wash aforesaid liquid to water is told organic phase to neutral; Remove the methylene dichloride that removes in this organic phase under reduced pressure; Get six (4-methoxy ethoxy) ring, three phosphonitriles, wherein the mol ratio of methyl cellosolve and hexachlorocyclotriphosphazene is 7.2: 1～8.0: 1, and the mol ratio of sodium hydride and methyl cellosolve is 1.2: 1～1.5: 1;
2) six (4-methoxy ethoxy) ring, three phosphonitriles, copper powder and the chloroform that step 1) are obtained add in the reaction flask; In temperature is that the chloroformic solution that will be dissolved with Iodotrimethylsilane under 0 ℃～5 ℃ stirrings adds in the reaction flask, add the chloroformic solution that is dissolved with Iodotrimethylsilane after, at 25 ℃～35 ℃ reactions of temperature 30h～40h; After reaction is accomplished; Filtering reacting liquid removes the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid; Under 15 ℃～30 ℃ stirrings of temperature; The methanol solution that in light yellow viscous liquid, adds the sodium hydroxide of 600ml0.4moL/L～0.8moL/L, reaction 6h～8h is through filtering reaction solution; Underpressure distillation removes the methyl alcohol in the gained filtrating; Obtain six (4-hydroxyl-oxethyls) ring, three phosphonitriles, wherein the mol ratio of Iodotrimethylsilane and six (4-methoxy ethoxy) ring three phosphonitriles is 1.5: 1～2.0: 1, and the mol ratio of copper powder and Iodotrimethylsilane is 0.05: 1～0.1: 1.
2. the compound method of six (4-hydroxyl-oxethyls) ring, three phosphonitriles according to claim 1 comprises the steps:
1) 300ml THF and 149.28g sodium hydride (50%) are joined in three mouthfuls of reaction flasks of 1L; Stir 20 ℃～30 ℃ of temperature then and drip the tetrahydrofuran solution 50ml that is dissolved with the 157.78g methyl cellosolve in the downhill reaction bottle; After dripping off, at 30 ℃ of reactions of temperature 30min.Being cooled to temperature then is 5 ℃, in reaction flask, drips the tetrahydrofuran solution 100ml that is dissolved with the 100g hexachlorocyclotriphosphazene again, drips off the back at 50 ℃ of reactions of temperature 30h.After reaction was accomplished, filtering reacting liquid removed the THF in the gained filtrating under reduced pressure; Obtain faint yellow muddy viscous liquid; Add the 150ml methylene dichloride to this liquid then, be neutral, tell organic phase with distilled water wash aforesaid liquid to water; Remove the methylene dichloride in this organic phase under reduced pressure, get six (4-methoxy ethoxy) ring, three phosphonitriles;
2) 100g six (4-methoxy ethoxy) ring three phosphonitriles and the 0.84g copper powder that 400ml chloroform, step (1) are obtained join in the 1L reaction flask; Stir the chloroformic solution 100ml that dropping is dissolved with the 63.03g Iodotrimethylsilane in the downhill reaction bottle at 0 ℃～5 ℃, react 30h for 25 ℃ in temperature after being added dropwise to complete.After reaction was accomplished, filtering reacting liquid removed the chloroform in the gained filtrating under reduced pressure, gets light yellow viscous liquid; Under 20 ℃ of stirrings of temperature; The methanol solution that in light yellow viscous liquid, adds the sodium hydroxide of 600ml0.6mol/L, reaction 6h is then through filtering reaction solution; Remove the methyl alcohol in the gained filtrating under reduced pressure, obtain six (4-hydroxyl-oxethyls) ring, three phosphonitriles of white solid.
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