CN1709897A - Synthesis of compound 9,10-dihydro-9-oxy-10-phospha phenanthrene and purification process thereof - Google Patents
Synthesis of compound 9,10-dihydro-9-oxy-10-phospha phenanthrene and purification process thereof Download PDFInfo
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Abstract
This invention involves synthetic and purification craft of 9-10-dihydrodithiin -9-oxa-10-pho-phenalenes-10-oxide. This method is divided into four parts:1. Phosphorus trichloride react with OPP, regard lewis acid as the catalyst, become intermediate of 6-chlorine-( sexahydrogen)-dibenzene[C,E][ 1,2]- pho-phenalenes;2. Through hydrolysis excessivly of CDOP, synthesis HPPA (2-hydroxybiphenyl-2- hypophosphorous acid);3. Washing hydrolysate with alcohol material;4. Distillation by pressure reduction to synthesis DOPO.All synthetic raw materials are: arene or alcohol material, such as aliphatic hydrocarbon, o-phenylphenol, phosphorus trichloride, methyl alcohol, ethanol or isobatyalcohol isobutyl alcohol, and distilled water, etc. This invention has reduced difficulty of craft condition, raised efficiency, solved question of removing zinc ion and chlorine ion.
Description
Affiliated technical field
The present invention relates to a kind of compound 9, the 10-dihydro-9-oxy is assorted-the synthetic and purifying process of 10-phospho hetero phenanthrene-10-oxide compound.9, the 10-dihydro-9-oxy is assorted-English name 9 of 10-phospho hetero phenanthrene-10-oxide compound, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, it uses its english abbreviation DOPO in the commodity domain name, and the name in the CA naming system is called 6-oxo-(6h)-dibenz-(c, e) (1,2)-oxaphosphorines is called for short ODOPs, or 6H-dibenz-[c, e] [1,2]-oxa-phosphorin-6-one.
Reagent when itself can be used as antiseptic-germicide, oxidation inhibitor, anti-fading agent, fire retardant, synthon etc.Particularly in flame retardant area, DOPO is widely used as Halogen of new generation, environmental protection, green novel flame-retardant modified monomer.Belong to the field of chemical synthesis.
Background technology
At present, carried out extensive studies to the synthetic of DOPO and in the application in each field both at home and abroad, remove outside the purposes of above-mentioned introduction, DOPO has also carried out corresponding research abroad being applied in of field such as features superpolymer, Resins, epoxy, luminescent materials, particularly Japan and Taiwan have been carried out extensive studies for this modified monomer in the application aspect above-mentioned.
9,10-dihydro-9-oxy-10-phosphinylidyne assorted luxuriant and rich with fragrance (DOPO)
External relevant patent
[1]SaitoToranosuke，Kobe?Hyogo.Neue?organophosphor-verbindungen?und?verfahren?zu?derenherstellung[P].DE：2034887，1972-1-20.
[2]Saito，Toranosuke，Kitani.Organophosphoms?compounds?and?process?for?the?productionthereof[P].US：4086206，1978-4-25.
[3]Buysch，Hans-josef，Glock..Process?for?preparing6-oxo-(6H)-dibenz-[c，e][1，2]-oxaphosphorins(ODOPs)[P].US：5650530，1997-7-22.
[4]Buysch?Hans-josef，Glock.Preparation?of?6-chloro-[6H]-dibenzo-[c，e][1，2]-phosphorinenes[P].DE：19505353，1996-3-21.
[5]Buysch?Hans-josef，Glock.Preparation?of?6-oxo-[6H]-dibenzo-[c，e][1，2]-phosphorinenes[P].DE：19505352，1996-3-21.
[6]Buysch?Hans-josef.，Glock.Process?for?the?preparation?of6-oxo-(6H)-dibenz-(c，e)(1，2)-oxaphosphorines[p].EP：739896，1996-10-30.
[7]Hans-josef?Buysh，Volker?Glock.Process?for?preparing6-oxo-(6H)-dibenz-[c，e][1，2]-oxaphosphorins[P].US：5717127，1998-2-10.
[8]Regnat，Dieter，Kleiner.Oxaphosphorins?and?a?process?for?their?preparation[P].US：5739372，1998-4-14.
[9]Kleiner?Hans-Jerg.Preparation?of?6-chloro-[6H]-dibenzo-[c，e][1，2]-phosphorin-6-one[P].EP：632050，1995-1-4.
[10]Kleiner?Hans-jerg.Process?for?preparing?6-chloro-(6H)-dibenz?[C，-E][1，2]-oxaphosphorin[P].US：5391798，1995-2-21.
[11]Kleiner?Hans-jerg.Method?for?preparing6H-dibenzo[c，e][1，2]oxaphosphorin-6-one.US：5481071，1996-1-2.
[12]Rathfelder?Paul，Rieckert?Horst，Dietrich?Jorg.Process?for?the?preparation?of?a?dop-containingmixture[P].US：5821376，1998-10-13.
[13]Chun?Shan?Wang，Jeng?Yueh?Shieh.Synthesis?and?properties?of?epoxy?resins?containing2-(6-oxid-6H-dibenz[c，e][1，2]oxaphosphorin-6-yl)1，4-benzenediol[J].Polymer，1998，39：5819-5826
[14]Chun?Shan?Wang，Jeng?Yueh?Shieh.Synthesis?and?properties?of?epoxy?resins?containing2-(6-oxid-6H-dibenz[c，e][1，2]oxaphosphorin-6-yl)1，4-benzenediol[J].Polymer，1998，39：5819-5826
[15] Jiang Jianzhong, Cai Chun. BACN intermediate DOPO is synthetic to summarize [J] with application. Jiangsu chemical industry .2004,32 (1): 12.
[16] Jiang Jianzhong, Cai Chun. the synthetic and process modification of BACN intermediate DOPO-HPPA. chemistry and biotechnology [J] .2003,116-117.
From the external at present patent of application, main applicant is from Japan and German, and wherein the method for application protection is summarized as follows:
Above-mentioned patent document for the synthetic employing without exception of DOPO same composition principle, but in concrete operations, slightly Difference is arranged, such as the feed way difference, the adjustment of charging sequence, the difference in reaction temperature, reaction time, the addition of catalyst Difference, the difference of reactant purity productive rate.
Composition principle is as follows:
See figure one
The synthetic reaction by phosphorus trichloride and OPP of DOPO as catalyzer, removes bimolecular hydrogenchloride with lewis acid, generate midbody product 6-chloro-(6 hydrogen)-hexichol [C, E] [1,2]-phospho hetero phenanthrene (CDOP), then, by hydrolysis to CDOP, synthetic DOPO.
2.6-chloro-(6 hydrogen)-hexichol [C, E] [1,2]-phospho hetero phenanthrene (CDOP) is synthetic
In the building-up process of CDOP, catalyzer all uses lewis acid as catalyzer, and all patents are all chosen zinc chloride as the most representative material catalysis annulation.
The hydroxyl hydrogen that drips phosphorus trichloride and OPP at first again 80 ℃ carry out dehydrochlorination reaction, add catalyzer ZnCl2 at 142-146 ℃ then and carry out ring-closure reaction, and in 13 hours, being warming up to 210 ℃ of reactions gradually to there being the hydrogenchloride generation, reaction finishes, synthetic CDOP.Underpressure distillation again obtains CDOP.US：5650530
The hydroxyl hydrogen that drips phosphorus trichloride and OPP reacts at 80 ℃, and adds catalyzer ZnCl2 simultaneously and react, and is warming up to 200 ℃ gradually.
At first add phosphorus trichloride, be warming up to boiling point, the OPP that drip to melt, and dropwising when being warming up to 140 ℃, add catalyzer, and be warming up to 200 ℃ gradually.
The OPP thawing is warming up to 180 ℃, adds zinc chloride, in 5 hours, drip phosphorus trichloride, keep reaction 4 hours, steam and remove excessive phosphorus trichloride, underpressure distillation acquisition CDOP under high vacuum as catalyzer.US：5391798
The CDOP hydrolysis prepares DOPO
The mode that the CDOP hydrolysis prepares DOPO differs greatly, and the route in reaction process is slightly adjusted.The alkaline hydrolysis acidifying evaporation that the Wang Chunshan people such as [14] who is German Patent [1-5] and Taiwan as following method 5 adopts; Method 1,2 is modal method for hydrolysis, and following synthetic method described in patent [5-13] article [14-16] etc.
The direct hydrolysis method is got the equimolar deionized water of CDOP, is hydrolyzed hydrolysis time 3-10 hour between 80-130 ℃.
The aqueous solvent solution adds compound fragrant hydrocarbon and is hydrolyzed under the situation that organic solvent exists in CDOP, the hydrolysis post crystallization is separated out.
Alcohols auxiliary water solution is got the equimolar deionized water of CDOP, and adds an amount of alcohol compound, and promotion water contacts with CDOP's, quickens hydrolysis.
The ice solution adds CDOP in the ice cube, and reaction generates HPPA, obtains DOPO in dehydration.
The alkali lye hydrolysis method at first is hydrolyzed into salt with CDOP in alkali lye, carry out acidifying with sulfuric acid again, generates HPPA, dewaters to generate DOPO under the vacuum of 90KPa.
The shortcoming of existing patented technology:
Existing patented technology is purified to synthetic CDOP and has all been adopted the distillation under vacuum under the high vacuum, this method needs higher appointed condition, stopping property to conversion unit requires high, vacuum tightness to vacuum pump requires high, industrialization to this product exists than big difficulty for domestic chemical enterprise, domestic have article to adopt the filter paper filtering method CDOP that purifies in the laboratory, but do not pay close attention for wherein too high zine ion and chloride ion content; The CDOP generated time (10-20 hour) and the hydrolysis time of foreign patent are grown (6-10 hour) simultaneously, production efficiency is low, the synthesis temperature height of CDOP (180-220 ℃), generate inflammable substance in process of production, through experimental verification, synthesis temperature is higher than 180 ℃, can produce the material of spontaneous combustion in the reactor, this is for extensively a large amount of chemical plant with an organic solvent in the production process, and is abnormally dangerous.
The content of innovation and creation
For simplifying and reduce the processing condition difficulty, raise the efficiency, by research, avoided enterprise in the DOPO synthesis technique comparatively to be difficult to the part that realizes, as have to use high vacuum, make enterprise produce in the unnecessary high-vacuum pump of acquiring, solved simultaneously because zine ion that technique change produces and chlorion are removed problem.
The synthetic DOPO of present method is divided into four parts and carries out the first step: by the reaction of phosphorus trichloride and OPP, as catalyzer, remove bimolecular hydrogenchloride with lewis acid, generate midbody product 6-chloro-(6 hydrogen)-hexichol [C, E] [1,2]-phospho hetero phenanthrene (CDOP); Second step: by excessive hydrolysis, remove the hydrogenchloride of a part, synthetic HPPA (2-Hydroxybiphenyl-2-Hypophosporous Acid, 50) to CDOP; The 3rd step: by adopting alcohols material hydrolysate is washed, remove impurity; The 4th step: by the underpressure distillation under the certain temperature, remove HPPA moisture, synthetic DOPO.See the building-up reactions formula of accompanying drawing 1DOPO.All synthesis materials are: alcohols material such as aromatic hydrocarbon (as toluene, chlorobenzene, dimethylbenzene, dichlorobenzene) or fat hydrocarbon material (sherwood oil), orthoxenol (OPP), phosphorus trichloride, methyl alcohol, ethanol or isopropylcarbinol and distilled water etc.
Synthesis route is specially:
The first step: by the reaction of phosphorus trichloride and OPP, as catalyzer, remove bimolecular hydrogenchloride, generate midbody product 6-chloro-(6 hydrogen)-hexichol [C, E] [1,2]-phospho hetero phenanthrene (CDOP) with lewis acid.The synthetic middle OPP of the first step and the synthetic molar ratio of phosphorus trichloride are 1: 1.25-1: 1.35, addition manner adopts and drip phosphorus trichloride among the OPP in container in temperature 168-180 ℃ scope, added Zinc Chloride Anhydrous before dripping in OPP, addition is the 0.6-2% of OPP quality.The dropping process of phosphorus trichloride needs 7-10 hour altogether, in preceding 2-3 hour, drip phosphorus trichloride 50%, next dripped 45% in 2.5-4.5 hour, at remaining 2.5-3.5 hour, 5% phosphorus trichloride of remainder is added reactor, make phosphorus trichloride maintenance backflow in the reactor.After 9 hours, at 120-140 ℃, under the vacuum 60-95kpa condition, remove excessive phosphorus trichloride under reduced pressure, be cooled to 80-115 ℃, add aromatic hydrocarbon (as toluene, chlorobenzene, dimethylbenzene, dichlorobenzene) or fat hydrocarbon material (sherwood oil), the add-on of aromatic hydrocarbon is the 0.4-1.2 of OPP quality, uses filter cloth to filter then.Specifically see accompanying drawing 2.
This step is the deciding step in intermediate CDOP synthetic of synthetic DOPO, by adopting changing conditions that Gauss's program quantizes the energy in the B switching process of A in the building-up process that energy calculates CDOP as can be known: the G of substance A is-1799.7258042KJ/mol, the G of substance B is-1338.797577KJ/mol, the G value of hydrogenchloride is-95.299KJ/mol, from A to the B process is the process that an energy increases, dG is that 365.497354KJ/mol is the process that an energy raises, this means the reverse spontaneous reaction of reaction, forward reaction need be in hot conditions, and reaction needed is constantly got rid of byproduct hydrogen chloride, reaches the purpose that promotes that reaction forward is carried out.In the processing condition of synthetic CDOP, the optimum temps that document provides is at 200-220 ℃.Temperature too high on the reagent not only can not produce promoter action to reaction, also can increase the speed of side reaction on the contrary, reduces the product yield of reaction; Certainly temperature is low excessively, then can cause reacting slow, perhaps can not react.So select a suitable temperature to be very important.
Synthesized after the CDOP, product in the presence of solvent, has been filtered, avoided using high vacuum to carry out rectifying, helped domestic small business, adopted this cover technology to produce.
Second step: by excessive hydrolysis, remove the hydrogenchloride of a part, synthetic HPPA to CDOP.
The filtrate of the first step is warming up to 40-100 ℃, slowly drips and the equimolar water of OPP, at the uniform velocity dripped in 20 minutes, reaction is violent, follows a large amount of hydrogen chloride gas to emerge.Continue to add the water of the OPP molar weight more than a times, liquid is heated up, temperature 70-105 ℃, and kept 1-4 hour.Reaction finishes, and mainly obtains the mixture of HPPA (2-Hydroxybiphenyl-2-Hypophosporous Acid, 50) and a small amount of DOPO.
Hydrolytic process is the reaction of taking off a part hydrogenchloride that CDOP and water carry out, and be reflected at when temperature of charge is higher than 85 ℃ to be very easy to carry out, and reaction is very violent, has a large amount of hydrogen chloride gas to produce.Mode that foreign literature usually adopts long-time (5-10) hour accurately to drip reaction that is hydrolyzed, though this method, in water saving, this method the best, it is long that to be reflected at industrial be inappropriate.In addition, the terminal point of this method control is difficult because can contain a spot of phosphorus trichloride in the reactant, its can and water vigorous reaction, make on the equimolar addition that is reflected at water of CDOP and water restive.Based on the problems referred to above that this method exists, for shortening the reaction times, raise the efficiency, adopt excessive water (adopting 1.2-4 times of theoretical value of OPP molar mass) to react, make organochlorine reaction rapidly at short notice.
The 3rd step: by adopting alcohols material hydrolysate is washed, remove impurity.The 0.3-1.2 alcohols materials such as methyl alcohol, ethanol or isopropylcarbinol doubly that in hydrolysate, add the OPP quality.Stirred 10-60 minute at 60-100 ℃, cooling, crystallization leaches crystal.
The 4th step: by the underpressure distillation under the certain temperature, remove HPPA moisture, synthetic DOPO.Crystal is transferred in the encloses container, begin to carry out underpressure distillation, along with cut distillates, strengthen vacuum gradually, carry out dehydration reaction, keep fluid temperature more than 80 ℃, liquid can be along with the continuous minimizing of moisture, and temperature raises gradually, when temperature rises between 110-135 ℃, keep this temperature 15 minutes-8 hours, and keep vacuum tightness 〉=90KPa.Slowly remove vacuum, be discharged to crystallizer tank, crystallization and freezing gets white block product, productive rate 92%.Through ultimate analysis: C66.77%, H4.36%, P14.42, O14.45%.Purity: 98.6% (HPLC).Fusing point mp:117-119 ℃.Zinc ion content 8ppm.
The product that obtains after the hydrolysis is the mixture of DOPO and HPPA, the HPPA in the product is carried out processed after, this material is transformed into DOPO.
Innovation part of the present invention is:
1. in the first step CDOP building-up process, adopt 169-180 ℃ synthesis temperature 8-10 hour.
2. on the purifying technique of CDOP, avoid using the high vacuum underpressure distillation, adopt filter cloth to filter.
3. on the technology of CDOP hydrolysis, adopt the 1.2-2.5 water doubly of direct OPP molar mass to carry out excessive hydrolysis, (1-4 hour) hydrolysis is in the short period of time finished, and product all generates HPPA.
4. adopt 0.3-1.2 times of alcoholic solvent of OPP quality that reaction product is washed, remove excessive zine ion, make zinc ion content be lower than 10ppm.Simultaneously in aromatic hydrocarbons alcohols mixing solutions to the further crystallization of reaction product, and crystallization filtered.
5. HPPA is being carried out in the dehydration reaction process, adopting 110-125 ℃, carrying out the decompression dehydration reaction, in 15 minutes-8 hours, dewatering and finish.
Description of drawings
The building-up reactions formula of accompanying drawing 1:DOPO
Accompanying drawing 2: be the building-up reactions formula of 6-chloro-(6 hydrogen)-hexichol [C, E] [1,2]-phospho hetero phenanthrene (CDOP)
Embodiment
Embodiment 1 adds OPP170g and 1.0g Zinc Chloride Anhydrous in the 500ML four-hole boiling flask, stirs and is warming up to 170-175 ℃, drips phosphorus trichloride 170g at 6 hours, keeps 8 hours.Underpressure distillation, vacuum tightness 90kpa between 120-140 ℃, steams and removes excessive phosphorus trichloride, is cooled to 110 ℃, adds 50ML toluene, by the cloth formula funnel filtration of liner middling speed quantitative paper.Filtrate is warming up to 85 ℃, slowly drips 20ML water, at the uniform velocity dripped in 20 minutes, reaction is violent, follows a large amount of hydrogen chloride gas to emerge.Continue to add 60ml ethanol, 20ml water, and liquid has been warming up to a large amount of backflows generations, temperature 98-100 ℃.Kept 3 hours.Cooling, crystallization.Crystal is leached.Crystal is transferred in the flask, begin to carry out underpressure distillation, along with cut distillates, strengthen vacuum gradually, carry out dehydration reaction, keep fluid temperature more than 90 ℃, liquid can be along with the continuous minimizing of moisture, and temperature raises gradually, when temperature rises between 120-125 ℃, keep this temperature 60 minutes, and keep vacuum tightness 〉=90KPa.Slowly remove vacuum, be discharged to crystallizer tank (Fig.1), stirred crystallization is solidified, and gets white block product, productive rate 98%.Through ultimate analysis: C66.77%, H4.36%, P14.42, O14.45%.Purity: 98.6% (HPLC).Fusing point mp:117-119 ℃.Zinc ion content 8ppm.
Embodiment 2 adds OPP170g and 1.0g Zinc Chloride Anhydrous in the 500ML four-hole boiling flask, stirs and is warming up to 170-175 ℃, drips phosphorus trichloride 170g at 6 hours, keeps 8 hours.Underpressure distillation, vacuum tightness 90kpa between 120-140 ℃, steams and removes excessive phosphorus trichloride, is cooled to 120 ℃, adds the cloth formula funnel filtration of 100ML chlorobenzene by liner middling speed quantitative paper.Filtrate is warming up to 85 ℃, slowly drips 20ML water, at the uniform velocity dripped in 20 minutes, reaction is violent, follows a large amount of hydrogen chloride gas to emerge.Continue to add 60ml methyl alcohol, 20ml water, and liquid has been warming up to a large amount of backflows generations, temperature 98-100 ℃.Kept 3 hours.Cooling, crystallization.Crystal is leached.Crystal is transferred in the flask, begin to carry out underpressure distillation, along with cut distillates, strengthen vacuum gradually, carry out dehydration reaction, keep fluid temperature more than 90 ℃, liquid can be along with the continuous minimizing of moisture, and temperature raises gradually, when temperature rises between 115-120 ℃, keep this temperature 60 minutes, and keep vacuum tightness 〉=90KPa.Slowly remove vacuum, add in the 500ml toluene, stir, dissolving is cooled to 20-22 ℃, crystallizes into Powderedly, and filtering product is put into the enamel pallet, oven dry, the white powder product, productive rate 95%.Purity: 99.2% (HPLC).Fusing point mp:117-119 ℃.Zinc ion content 10ppm.
Embodiment 3 adds OPP170g and 1.0g Zinc Chloride Anhydrous in the 500ML four-hole boiling flask, stirs and is warming up to 170-175 ℃, drips phosphorus trichloride 170g at 6 hours, keeps 10 hours.Underpressure distillation, vacuum tightness 90kpa between 120-140 ℃, steams and removes excessive phosphorus trichloride, is cooled to 120 ℃, by the cloth formula funnel filtration of liner middling speed quantitative paper.Filtrate is warming up to 85 ℃, slowly drips 20ML water, at the uniform velocity dripped in 20 minutes, reaction is violent, follows a large amount of hydrogen chloride gas to emerge.Continue to add 50ML toluene and 60ml ethanol, 60ml water, and liquid has been warming up to a large amount of backflows generations, temperature 98-100 ℃.Kept 1 hour.Cooling, crystallization.Crystal is leached.Crystal is transferred in the flask, begin to carry out underpressure distillation, along with cut distillates, strengthen vacuum gradually, carry out dehydration reaction, keep fluid temperature more than 90 ℃, liquid can be along with the continuous minimizing of moisture, and temperature raises gradually, when temperature rises between 125 ℃, keep this temperature 60 minutes, and keep vacuum tightness 〉=90KPa.Slowly remove vacuum, be discharged to the enamel pallet, left standstill 5 hours, crystallization and freezing gets white block product, productive rate 99.3%.Purity: 98.6% (HPLC).Fusing point mp:117-119 ℃.Zinc ion content 8ppm.
Embodiment 4 adds OPP170g and 1.0g Zinc Chloride Anhydrous in the 500ML four-hole boiling flask, stirs and is warming up to 168-170 ℃, drips phosphorus trichloride 172g at 6 hours, keeps 10 hours.Underpressure distillation, vacuum tightness 90kpa between 120-140 ℃, steams and removes excessive phosphorus trichloride, is cooled to 120 ℃, adds the cloth formula funnel filtration of 200ML chlorobenzene by liner middling speed quantitative paper.Filtrate is warming up to 85 ℃, slowly drips 20ML water, at the uniform velocity dripped in 20 minutes, reaction is violent, follows a large amount of hydrogen chloride gas to emerge.Continue to add 60ml ethanol, 60ml water, and liquid has been warming up to a large amount of backflows generations, temperature 98-100 ℃.Kept 1 hour.Cooling, crystallization.Crystal is leached.Crystal is transferred in the flask, begin to carry out underpressure distillation, along with cut distillates, strengthen vacuum gradually, carry out dehydration reaction, keep fluid temperature more than 90 ℃, liquid can be along with the continuous minimizing of moisture, and temperature raises gradually, when temperature rises between 125 ℃, keep this temperature 60 minutes, and keep vacuum tightness 〉=90KPa.Slowly remove vacuum, be discharged to the enamel pallet, left standstill 5 hours, crystallization and freezing gets white block product, productive rate 95%.Purity: 98.4% (HPLC).Fusing point mp:117-119 ℃.Zinc ion content 10ppm.
Embodiment 5 adds OPP170g and 1.0g Zinc Chloride Anhydrous in the 500ML four-hole boiling flask, stirs and is warming up to 175-180 ℃, drips phosphorus trichloride 170g at 6 hours, keeps 7 hours.Underpressure distillation, vacuum tightness 90kpa between 120-140 ℃, steams and removes excessive phosphorus trichloride, is cooled to 120 ℃, by the cloth formula funnel filtration of liner middling speed quantitative paper.Filtrate is warming up to 85 ℃, slowly drips 20ML water, at the uniform velocity dripped in 20 minutes, reaction is violent, follows a large amount of hydrogen chloride gas to emerge.Continue to add 50ML toluene and 60ml ethanol, 60ml water, and liquid has been warming up to a large amount of backflows generations, temperature 98-100 ℃.Kept 1 hour.Cooling, crystallization.Crystal is leached.Crystal is transferred in the flask, begin to carry out underpressure distillation, along with cut distillates, strengthen vacuum gradually, carry out dehydration reaction, keep fluid temperature more than 90 ℃, liquid can be along with the continuous minimizing of moisture, and temperature raises gradually, when temperature rises between 125 ℃, keep this temperature 60 minutes, and keep vacuum tightness 〉=90KPa.Slowly remove vacuum, be discharged to the enamel pallet, left standstill 5 hours, crystallization and freezing gets white block product, productive rate 97%.Purity: 98.1% (HPLC).Fusing point mp:117-119 ℃.Zinc ion content 10ppm.
Embodiment 6 adds OPP170g and 1.0g Zinc Chloride Anhydrous in the 500ML four-hole boiling flask, stirs and is warming up to 175-180 ℃, drips phosphorus trichloride 170g at 6 hours, keeps 9 hours.Underpressure distillation, vacuum tightness 90kpa between 120-140 ℃, steams and removes excessive phosphorus trichloride, is cooled to 120 ℃, adds the cloth formula funnel filtration of 100ML toluene by liner middling speed quantitative paper.Filtrate is warming up to 85 ℃, slowly drips 20ML water, at the uniform velocity dripped in 20 minutes, reaction is violent, follows a large amount of hydrogen chloride gas to emerge.Continue to add 100ml ethanol, 60ml water, and liquid has been warming up to a large amount of backflows generations, temperature 98-103 ℃.Kept 1 hour.Cooling, crystallization.Crystal is leached.Crystal is transferred in the flask, begin to carry out underpressure distillation, along with cut distillates, strengthen vacuum gradually, carry out dehydration reaction, keep fluid temperature more than 90 ℃, liquid can be along with the continuous minimizing of moisture, and temperature raises gradually, when temperature rises to 125 ℃, keep this temperature 60 minutes, and keep vacuum tightness 〉=90KPa.Slowly remove vacuum, be discharged to the enamel pallet, left standstill 5 hours, crystallization and freezing gets white block product, productive rate 96%.Purity: 99% (HPLC).Fusing point mp:117-119 ℃.Zinc ion content 5ppm.
Claims (6)
1. the present invention relates to a kind of compound 9, the 10-dihydro-9-oxy is assorted-the synthetic and purifying process of 10-phospho hetero phenanthrene-10-oxide compound, it uses its english abbreviation DOPO in the commodity domain name, it is characterized in that: all synthesis materials comprise alcohols materials such as aromatic hydrocarbon (as toluene, chlorobenzene, dimethylbenzene, dichlorobenzene) or fat hydrocarbon material (sherwood oil), orthoxenol (OPP), phosphorus trichloride, methyl alcohol, ethanol or isopropylcarbinol and distilled water etc.Synthetic route divides four parts to carry out the first step: by the reaction of phosphorus trichloride and OPP, as catalyzer, remove bimolecular hydrogenchloride with lewis acid, generate midbody product 6-chloro-(6 hydrogen)-hexichol [C, E] [1,2]-phospho hetero phenanthrene (CDOP); Second step: by excessive hydrolysis, remove the hydrogenchloride of a part, synthetic HPPA (2-Hydroxybiphenyl-2-Hypophosporous Acid, 50) to CDOP; The 3rd step: by adopting alcohols material hydrolysate is washed, remove impurity; The 4th step: by the underpressure distillation under the certain temperature, remove HPPA moisture, synthetic DOPO.See the building-up reactions formula of accompanying drawing 1DOPO.
2. as claim 1 described a kind of compound 9, the 10-dihydro-9-oxy is assorted-the synthetic and purifying process of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that in the first step CDOP building-up process, adopting 169-180 ℃ synthesis temperature 8-10 hour.
3. as claim 1 described a kind of compound 9, the 10-dihydro-9-oxy is assorted-the synthetic and purifying process of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that in the first step CDOP building-up process, on the purifying technique of CDOP, avoid using the high vacuum underpressure distillation, adopt filter cloth to filter.
4. as claim 1 described a kind of compound 9, the 10-dihydro-9-oxy is assorted-the synthetic and purifying process of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that second step is on the technology of CDOP hydrolysis, adopt the 1.2-2.5 water doubly of direct OPP molar mass to carry out excessive hydrolysis, can finish hydrolysis in 1-4 hour, product all generates HPPA.
5. as claim 1 described a kind of compound 9, the 10-dihydro-9-oxy is assorted-the synthetic and purifying process of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that the 3rd step alcohols water washing, when removing impurity, adopt 0.3-1.2 times of alcoholic solvent of OPP quality that reaction product is washed, remove excessive zine ion, make zinc ion content be lower than 10ppm.Simultaneously in aromatic hydrocarbons alcohols mixing solutions to the further crystallization of reaction product, and crystallization filtered.
6. as claim 1 described a kind of compound 9, the 10-dihydro-9-oxy is assorted-the synthetic and purifying process of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that the 4th step underpressure distillation, remove HPPA moisture, in the process of synthetic DOPO, HPPA is being carried out in the dehydration reaction process, adopting 110-125 ℃, carry out the decompression dehydration reaction, in 15 minutes-8 hours, dewater and finish.
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| CN101089005B (en) * | 2006-06-16 | 2011-06-15 | 沈阳博美达化学有限公司 | Prepn process of cyclic phosphonate compound |
| CN102219806A (en) * | 2011-05-07 | 2011-10-19 | 普塞呋（清远）磷化学有限公司 | Preparation method of high purity cyclic phosphonate 9,10-dihydro-9-oxa-10-phosphaphenanathrene-10-oxide |
| CN102229624A (en) * | 2011-05-15 | 2011-11-02 | 西北化工研究院 | Synthesis and purification process for DOPO |
| CN102759593A (en) * | 2012-07-20 | 2012-10-31 | 青岛普仁仪器有限公司 | Chromatograph detection method for inorganic anions and cations in DOPO |
| CN103193445A (en) * | 2013-05-03 | 2013-07-10 | 张敬敏 | Cement mortar for preparing waterproof and fireproof thermal insulation material |
| CN103703070A (en) * | 2011-07-28 | 2014-04-02 | 丸菱油化工业株式会社 | Flame retarder comprising condensed phosphonic acid ester and flame-retardant resin composition |
| CN105949242A (en) * | 2016-05-18 | 2016-09-21 | 衡阳师范学院 | Method for synthesizing 9, 10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide |
| CN107556343A (en) * | 2017-10-20 | 2018-01-09 | 利尔化学股份有限公司 | DOPO and its intermediate preparation method |
| CN111072515A (en) * | 2019-12-25 | 2020-04-28 | 山东普洛得邦医药有限公司 | Method for continuously synthesizing thiaminoximic acid intermediate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101089005B (en) * | 2006-06-16 | 2011-06-15 | 沈阳博美达化学有限公司 | Prepn process of cyclic phosphonate compound |
| CN102219806A (en) * | 2011-05-07 | 2011-10-19 | 普塞呋（清远）磷化学有限公司 | Preparation method of high purity cyclic phosphonate 9,10-dihydro-9-oxa-10-phosphaphenanathrene-10-oxide |
| CN102219806B (en) * | 2011-05-07 | 2014-09-17 | 清远市普塞呋磷化学有限公司 | Preparation method of high purity cyclic phosphonate 9,10-dihydro-9-oxa-10-phosphaphenanathrene-10-oxide |
| CN102229624A (en) * | 2011-05-15 | 2011-11-02 | 西北化工研究院 | Synthesis and purification process for DOPO |
| CN102229624B (en) * | 2011-05-15 | 2013-08-14 | 西北化工研究院 | Synthesis and purification process for DOPO |
| CN103703070B (en) * | 2011-07-28 | 2016-01-06 | 丸菱油化工业株式会社 | Fire retardant containing condensed type phosphonic acid ester and flame retardant resin composition |
| CN103703070A (en) * | 2011-07-28 | 2014-04-02 | 丸菱油化工业株式会社 | Flame retarder comprising condensed phosphonic acid ester and flame-retardant resin composition |
| CN102759593A (en) * | 2012-07-20 | 2012-10-31 | 青岛普仁仪器有限公司 | Chromatograph detection method for inorganic anions and cations in DOPO |
| CN102759593B (en) * | 2012-07-20 | 2014-12-17 | 青岛普仁仪器有限公司 | Chromatograph detection method for inorganic anions and cations in DOPO |
| CN103193445A (en) * | 2013-05-03 | 2013-07-10 | 张敬敏 | Cement mortar for preparing waterproof and fireproof thermal insulation material |
| CN103193445B (en) * | 2013-05-03 | 2015-08-19 | 温州市兴海市政建设有限公司 | A kind of sand-cement slurry for the preparation of waterproof, fire-retardant heat-insulation material |
| CN105949242A (en) * | 2016-05-18 | 2016-09-21 | 衡阳师范学院 | Method for synthesizing 9, 10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide |
| CN105949242B (en) * | 2016-05-18 | 2018-10-30 | 衡阳师范学院 | A kind of synthetic method of 9,10- dihydro-9-oxies -10- phospho hetero phenanthrene -10- oxides |
| CN107556343A (en) * | 2017-10-20 | 2018-01-09 | 利尔化学股份有限公司 | DOPO and its intermediate preparation method |
| CN111072515A (en) * | 2019-12-25 | 2020-04-28 | 山东普洛得邦医药有限公司 | Method for continuously synthesizing thiaminoximic acid intermediate |
| CN111072515B (en) * | 2019-12-25 | 2023-02-28 | 普洛药业股份有限公司 | Method for continuously synthesizing thiaminoximic acid intermediate |
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