CN101362779B

CN101362779B - Synthesis method of octaphenyltetrasiloxanyl cyclic ether

Info

Publication number: CN101362779B
Application number: CN2008101965317A
Authority: CN
Inventors: 罗梅
Original assignee: Hefei University of Technology
Current assignee: Hefei University of Technology
Priority date: 2008-09-10
Filing date: 2008-09-10
Publication date: 2011-03-16
Anticipated expiration: 2028-09-10
Also published as: CN101362779A

Abstract

The invention relates to a synthesizing method for octaphenyl tetra-silica-oxo-cyclic ether. Diphenyl dichlorosilane and alpha-phenethylamine are taken as raw materials. The method is characterized in that: the diphenyl dichlorosilane is stirred and added to the alpha-phenethylamine in a dropwise manner for refluxing reaction for 48 hours and is added with 30 percent to 50 percent of NaOH solution; an organic phase is extracted by using dichloromethane; rotation and precipitation are carried out to extraction liquid, thus obtaining a crude product; after the crude product is placed stilly for one night, the crude product separates out white crystals which are target products. The raw materials of the synthesizing method are easy to obtain, technique is simple and operation is convenient, thus laying a foundation for conveniently preparing octaphenyl tetra-silica-oxo-cyclic ether with low cost.

Description

A kind of synthetic method of octaphenyltetrasiloxcyclic cyclic ether

One, technical field

The present invention relates to a kind of preparation method of compound, particularly the preparation method of cyclic organic ether, specifically a kind of synthetic method of octaphenyltetrasiloxcyclic cyclic ether.

Two, background technology

The compound octaphenyltetrasiloxcyclic cyclic ether is the monomer of synthetic polysiloxane, and polysiloxane is important Industrial products, has multiple important purposes.For example, silicone oil, silicon lacquer, silicone resin, silicon rubber can be used as quality lubricant, fabric waterproofing agent, high-grade insulating materials etc., and as far back as 1945, J.Am.Chem.Soc. reported the structure [1-2] of ring-type silicon ether compound.Subsequently, the many reports [3-4] that occurred this material synthetic method again.But the synthetic method of this material is normally used Ph ₂Si (0H) ₂With aminated compounds such as diethylamine, or monoethanolamine etc. at high temperature burns, and still, just obtain this material through the treating processes of a series of complexity.

1.Burkhard，C.A.；Decker，B.F.；Harker，D.J.Am.Chem.Soc.，1945，67，2174-2175.

2.Hede，J.F.；Frevel，L.K.；Nutting，H.S.；Petrie，P.S.；Purcell，M.A.J.Am.Chem.Soc.，1947，69，488-492.

3.Yang，M.H.；Chou，C.；Lin，C.H.Journal?of?Chinese?Chemical?Society，1995，42(6)，923-8

4.Takiguchi，T.J.Org.Chem.，1959，24，989-90.

Three, summary of the invention

The alleged octaphenyltetrasiloxcyclic cyclic ether of the present invention is the compound shown in the following chemical formula:

The present invention aim to provide a kind of synthetic method with the preparation above-claimed cpd, the institute will with regard to the solution technical problem be to select raw material and synthesis condition.

This synthetic method is a raw material with diphenyl dichlorosilane and α-Ben Yian, synthetic in toluene solvant, it is characterized in that and to be added drop-wise in the α-Ben Yian toluene solution under the diphenyl dichlorosilane stirring, at this moment a large amount of amorphous hydrochloride white precipitates appears, added the back back flow reaction 48 hours, back flow reaction finishes the back and add 30～50% (weight percents in reaction solution, aqueous sodium hydroxide solution down together), the white precipitate dissolving separates and removes water, organic phase dichloromethane extraction, obtain extraction liquid, the rotation precipitation obtains crude product, with the crude product standing over night, separates out white crystal automatically in crude product, through nucleus magnetic resonance, infrared, mass spectrum and X-diffraction characterize, and confirm that this white crystal is the target product octaphenyltetrasiloxcyclic cyclic ether.

To this synthetic method, applicant's original meaning is the preparation silicon-nitrogen compound, but has obtained silicon oxide compound inadvertently, and so-called " accidentally " is meant the storing of crude product.Originally think that reagent or instrument are wrong, but there is no careless omission, so carry out compound experiment, unanimity, and process stabilization as a result, favorable reproducibility repeatedly through carefully examining.In repeating compound experiment, once the crude product that obtains behind the extraction liquid precipitation was in time measured sign, the non-target product of crude product needs can separate out target product through standing over night.

Does oxygen go out wherefrom? the applicant has carried out deep thinking.General knowledge is told us, and it is difficult that α-Ben Yian and diphenyl dichlorosilane dehydrochlorination generate silazine link, because sterically hindered big.Whether under this synthesis condition, make the unstable more and very easily suction of unsettled silazine link originally, in the storing process, absorbed airborne water and generated silicon oxide compound.But following synthetic method also can obtain target product.

The applicant adds triethylamine in the toluene solvant with α-Ben Yian, drip diphenyl dichlorosilane then, the hydrochloride white precipitate is arranged in the dropping process, dropwised the back back flow reaction 48 hours, cooling, filtering separation, remove triethylamine hydrochloride, filtrate concentrates the back and goes up the silica gel column chromatography separation, presses the volume ratio of 1:5 with methylene dichloride and sherwood oil and mixes eluent drip washing, collects leacheate, obtain white crystal behind the rotation precipitation, characterizing this white crystal after measured is target product.

Perhaps filtering separation not adds water and makes the triethylamine hydrochloride dissolving, separates and removes water, organic phase dichloromethane extraction, obtain extraction liquid, extraction liquid rotation precipitation obtains crude product, and standing over night obtains target product again, or crude product silica gel column chromatography column chromatography for separation, operate the samely, obtain target product.

This synthetic method raw material is easy to get, and technology is simple, and is easy to operate, opened convenience for cheapness prepares octaphenyltetrasiloxcyclic cyclic ether.

Four, description of drawings

Fig. 1. compound ¹HNMR figure

Fig. 2. compound ¹³CNMR figure

Fig. 3. the IR figure of compound

Fig. 4. the X-diffractogram of compound

Five, embodiment

1, under the anhydrous and oxygen-free condition, in two-mouth bottle, add α-Ben Yian 6.1mL (47.6mmol), toluene 30mL, stir and in dropping funnel, slowly add diphenyl dichlorosilane 5mL (23.8mmol) down, there are a large amount of white precipitates to occur in the solution, after the back flow reaction 48 hours, add the 10mL50% aqueous sodium hydroxide solution, separate and remove water, organic phase dichloromethane extraction, extraction liquid anhydrous sodium sulfate drying, rotation removes and desolvates, get thick product 5g, after static the spending the night, have a large amount of white crystals to separate out. ¹HNMR(500MHz，CDCl ₃)7.19(t，J＝0Hz，4H，Ar-H)，7.35(t，J＝2.5Hz，2H，Ar-H)，7.48～7.49(d，J＝6.5Hz，4H，Ar-H). ¹³C?NMR(125MHz，CDCl ₃)127.70(x4)，130.11(x4)，134.46(x4).IR(KBr)：3440，3070，3049，3024，1591，1487，1429，1187，1119，1103，1028，997，741，717，698，528，510，493；HRMS(EI)：m/z(％)：calcd?for?C ₄₈H ₄₀Si ₄O ₄：792.2004；found：792.1998.Elemental?analysis：found：C：72.37％，H：5.10％；Calculate：C：72.77％，H：5.08％。

2, under the anhydrous and oxygen-free condition, in two-mouth bottle, add α-Ben Yian 6.1mL (47.6mmol), triethylamine 20ml, toluene 30mL, stir and in dropping funnel, slowly add diphenyl dichlorosilane 5mL (23.8mmol) and toluene 20mL down, there are a large amount of white precipitates to occur in the solution, after the back flow reaction 48 hours, cooling, filtering separation, filtrate concentrate back upper prop chromatography column separates, and presses the drip washing of 1:5 volume ratio blended eluent with methylene dichloride and sherwood oil, collect leacheate, obtain the white crystal target product behind the rotation precipitation.Measure and characterize with example 1.

3, under the anhydrous and oxygen-free condition, in two-mouth bottle, add α-Ben Yian 6.1mL (47.6mmol), triethylamine 20mL, toluene 30mL, stir slow diphenyl dichlorosilane 5mL (23.8mmol) of adding and toluene 20mL in dropping funnel down,, there are a large amount of white precipitates to occur in the solution, after the back flow reaction 48 hours, add 30mL water, separate and remove water, organic phase dichloromethane extraction, the extraction liquid anhydrous sodium sulfate drying, rotation removes and desolvates, and gets thick product 5g, and perhaps standing over night obtains target product, or on the crude product behind the silica gel column chromatography (sherwood oil/methylene dichloride 5/1 is an eluent), white crystal 0.8g.Target product is white crystal.Measure and characterize with example 1.

Claims

1. the synthetic method of an octaphenyltetrasiloxcyclic cyclic ether, with diphenyl dichlorosilane and α-Ben Yian is raw material, synthetic in toluene solvant, it is characterized in that: be added drop-wise in the α-Ben Yian toluene solution under diphenyl dichlorosilane is stirred, added the back back flow reaction 48 hours, add 30～50% NaOH solution to reaction solution, use the dichloromethane extraction organic phase, extraction liquid rotation precipitation obtains crude product, the crude product standing over night, and the white crystal of separating out in crude product promptly is an octaphenyltetrasiloxcyclic cyclic ether.

2. the synthetic method of an octaphenyltetrasiloxcyclic cyclic ether, with diphenyl dichlorosilane and α-Ben Yian is raw material, synthetic in toluene solvant, it is characterized in that: be added drop-wise in α-Ben Yian and the triethylamine toluene solution under diphenyl dichlorosilane is stirred, added the back back flow reaction 48 hours, cooling, separate and remove precipitation, filtrate concentrates after silica gel column chromatography separates, mix eluent drip washing with sherwood oil and methylene dichloride by 5: 1 volume ratio, collect leacheate, obtaining white crystal behind the rotation precipitation promptly is octaphenyltetrasiloxcyclic cyclic ether.

3. synthetic method according to claim 2, it is characterized in that: 48 hours steps afterwards of back flow reaction replace with: add water and make resolution of precipitate in reaction solution, use the dichloromethane extraction organic phase, extraction liquid rotation precipitation obtains crude product, crude product standing over night, the white crystal of separating out in crude product promptly are octaphenyltetrasiloxcyclic cyclic ethers.

4. synthetic method according to claim 3, it is characterized in that: the step that extraction liquid rotation precipitation obtains after the crude product replaces with: crude product separates through silica gel column chromatography, mix eluent drip washing with sherwood oil and methylene dichloride by 5: 1 volume ratio, collect leacheate, obtaining white crystal behind the rotation precipitation promptly is octaphenyltetrasiloxcyclic cyclic ether.