CN107556343A - DOPO and its intermediate preparation method - Google Patents
DOPO and its intermediate preparation method Download PDFInfo
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- CN107556343A CN107556343A CN201710984288.4A CN201710984288A CN107556343A CN 107556343 A CN107556343 A CN 107556343A CN 201710984288 A CN201710984288 A CN 201710984288A CN 107556343 A CN107556343 A CN 107556343A
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- UBEUAZASIHVFOB-UHFFFAOYSA-N ClP1Oc(cccc2)c2-c2c1cccc2 Chemical compound ClP1Oc(cccc2)c2-c2c1cccc2 UBEUAZASIHVFOB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to DOPO and its intermediate preparation method, belong to chemical field.The technical problems to be solved by the invention are to provide DOPO intermediates CDOP preparation method, and this method comprises the following steps：The mixture of o-phenyl phenol, zinc chloride and phosphorus trichloride is warming up to 60~140 DEG C, after esterification, 160~220 DEG C of reactions is continuously heating to, produces.Phosphorus trichloride can disposably be added when feeding intake using preparation method of the present invention, and reaction terminate after without removing excessive POCl3 and byproduct of reaction by being evaporated under reduced pressure, enormously simplify production operation, there is significant advantage compared to existing process.
Description
Technical field
The present invention relates to DOPO and its intermediate preparation method, belong to chemical field.
Background technology
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviation DOPO, molecular formula C12H9PO2, No. CAS：
35948-25-5, molecular weight 216.2,117~121 DEG C of fusing point, it is white plates or pulverulent solids.DOPO and its derivative close
Into fire retardant have the characteristics that efficiently, Halogen, few cigarette, low toxicity, do not migrate, fire resistance it is lasting, be the nothing developed in recent years
Halogen environment friendly flame retardant new varieties.At present, its synthesis has caused extensive concern with application.
DOPO synthetic route is as follows：
Mainly include the following steps that：1st, o-phenyl phenol OPP and phosphorus trichloride are in the presence of catalyst (such as zinc chloride)
The friedel-crafts acylation reaction of esterification and intramolecular occurs for one kettle way, generates CDOP；2nd, CDOP ring opening hydrolysis, HPPA is generated；
3rd, HPPA intramolecular dehydrations esterification cyclization, obtains DOPO.
In existing synthesis technique, the processing of phosphorus trichloride is always a great problem.First, CDOP process is being prepared
In, if phosphorus trichloride is excessively too many, side reaction is easily caused, the not only purifying to intermediate product causes difficulty, can also influence to react
Yield and finished product purity；Therefore, the side of phosphorus trichloride is added portionwise in existing preparation method generally use during the course of the reaction
Formula, and mostly by be added dropwise, operation it is excessively cumbersome (referring to：CN102219806A).Secondly, also needed after the completion of friedel-craft reaction
The phosphorus trichloride and some other accessory substance for being not engaged in reaction is removed by distillation, the hydrolysis work of next step could be entered
Sequence, the generation of side reaction is otherwise also resulted in, which in turns increases the complexity of preparation technology.
The content of the invention
It is an object of the invention to provide DOPO intermediates CDOP synthesis technique, to solve on present in prior art
State defect.Another object of the present invention is to provide DOPO preparation method.
The invention provides the preparation method of compound shown in formula I, comprise the following steps：
The mixture of o-phenyl phenol, zinc chloride and phosphorus trichloride is warming up to 60~140 DEG C, after esterification, continued
160~220 DEG C of reactions are warming up to, produce compound shown in formula I.
Further, the mol ratio of phosphorus trichloride and o-phenyl phenol is (1: 1.25)~(2: 1).It is excellent
The mol ratio of selection of land, phosphorus trichloride and o-phenyl phenol is (1.2: 1)~(2: 1).
It is further preferred that the mol ratio of phosphorus trichloride and o-phenyl phenol is 1.4: 1.
Further, the mol ratio of zinc chloride and o-phenyl phenol is (0.00125: 1)~(0.125: 1).If chlorination
Zinc dosage is less than above range, yield can be caused to reduce；Dosage is excessive, more difficult to post-processing, and improves and be produced into
This.
Preferably, the mol ratio of zinc chloride and o-phenyl phenol is 0.0125: 1.
Further, the mixture of o-phenyl phenol, zinc chloride and phosphorus trichloride is warming up to 80 DEG C, after esterification,
It is continuously heating to 180~220 DEG C of reactions.
Further, reaction time of esterification is 1~4h.If reaction time of esterification is less than 1h, reaction carries out incomplete.
Preferably, reaction time of esterification 2h.
The invention provides the preparation method of compound shown in formula II, comprise the following steps：
A, compound shown in formula I is prepared according to methods described, reaction solution is standby；
B, benzene series solvent and adsorbent are added into reaction solution obtained by step a, is filtered after stirring, filtrate is standby；
C, water is added into filtrate obtained by step b, temperature rising reflux is complete to hydrolyzing, and is cooled to less than 5 DEG C, separates out solid,
Filtering, it is standby to collect filter cake；
D, filter cake obtained by taking step c, is dehydrated under conditions of below vacuum 100mbar, 140~210 DEG C of temperature, produces
Compound shown in formula II.
Wherein, the adsorbent excludes the adsorbent of meta-alkalescence, can be selected from neutral or slant acidity adsorbent, such as
Carbon, activated carbon, diatomite or silica gel.
Preferably, the adsorbent is diatomite；When using diatomite as adsorbent, diatomite dosage is adjacent phenyl
The 5%w/w of phenol.
Preferably, step c is cooled to -20~0 DEG C.
It is further preferred that step c is cooled to 0 DEG C.
Preferably, for step d control vacuums in below 5mbar, temperature is 180~210 DEG C.
It is further preferred that it is 5mbar that step d, which controls vacuum, temperature is 190 DEG C.
Further, the mass ratio of benzene series solvent and o-phenyl phenol is (2: 1)~(1: 1).
Preferably, the mass ratio of benzene series solvent and o-phenyl phenol is 1.5: 1.
Further, the mass ratio of water and o-phenyl phenol is (1: 2)~(4: 1).
Preferably, the mass ratio of water and o-phenyl phenol is 1: 2.
Further, the benzene series solvent is one or more kinds of in toluene, mesitylene, pseudocumene or chlorobenzene
Mixed solvent.Wherein, experiment results proved, toluene effect are preferable.
The invention provides DOPO intermediates CDOP preparation method, can disposably be added when feeding intake using this method
Phosphorus trichloride, and reaction terminate after without removing excessive POCl3 and byproduct of reaction by being evaporated under reduced pressure, it is significantly simple
Production operation is changed.Present invention also offers DOPO complete preparation technology, can be prepared with more than 90% high yield
Obtain DOPO, and be the product that can obtain high purity 99.7% by the direct crystallization of final step dehydration liquid, be not required into
One step purification process, there is significant advantage compared to existing preparation technology.
Embodiment
The raw material that is used in the specific embodiment of the invention, equipment are known product, are obtained by buying commercially available prod.
One side, DOPO intermediates CDOP provided by the invention synthetic route are as follows：
The mixture of o-phenyl phenol, zinc chloride and phosphorus trichloride is warming up to 60~140 DEG C, after esterification, continued
160~220 DEG C of reactions are warming up to, are produced.
Inventor, by continuously attempting to find, first allows o-phenyl phenol and phosphorus trichloride 60~140 in actual production
It is esterified as fully as possible under conditions of DEG C, then is warming up to 160~220 DEG C and friedel-craft reaction occurs, can be largely
Upper reduction side reaction caused by phosphorus trichloride excess.Therefore, phosphorus trichloride can be disposably added when reaction feeds intake, is simplified
Operation, and follow-up purifying also becomes easy, finished product DOPO can be prepared more conveniently.
Second aspect, the invention provides DOPO preparation method, is first prepared intermediate using the above method
CDOP, DOPO is then synthesized according to following route：
Inventor has found, due to less using byproduct of reaction caused by the inventive method synthesis CDOP, therefore prepares
The CDOP filtered hydrolyzing process that can be directly entered next step of reaction solution, it is not necessary to carry out the distillation procedure of complexity.Wherein,
Diatomite drainage is added, the phosphorous salts in reaction solution can be removed well, filter effect is greatly improved, so that water
Solid HPPA is easily separated out after solution；If on the contrary, being added without diatomite drainage during filtering, what is obtained after hydrolysis is Chinese red muddiness
Liquid, it is not easy to separate out solid, even if the content for separating out solid wherein impurity is also higher.
Embodiment 1 prepares DOPO using the inventive method
1st, by 100g o-phenyl phenols (1eq, 0.588mol), 1g anhydrous zinc chlorides (0.0125eq, 0.0073mol) and
80.7g phosphorus trichlorides (1eq, 0.588mol) are added in 500mL four-hole boiling flasks, after being warming up to 100 DEG C of reaction 2h, are continuously heating to
160 DEG C of reaction 2h, HPLC detection reactions are complete, and reaction solution is directly used in react in next step.
2nd, 150g toluene and 5g diatomite are added in step reaction solution upwards, 0.5h is stirred at room temperature, filters to obtain colorless and clear liquid.
50g purified waters are added in filtrate, temperature rising reflux 4h, TLC detection reaction is complete.0 DEG C is cooled to, it is solid that strong stirring separates out white
Body, filtering, filter cake washes twice with 50g purified waters, filter cake be detected as HPPA-DOPO mixtures (detected through HPLC, wherein
DOPO content is reacted in next step 12%), to be directly used in.
3rd, upper step crude product is gone in reaction flask, heating makes its thawing, under the conditions of vacuum 50mbar, is warming up to 160
DEG C, stirring dehydration 6h, HPLC monitoring reaction end, it is cooled to room temperature crystallization and obtains target compound 57.1g (0.264mol).
Above three-step reaction total recovery 45%, through vapor detection, the purity ＞ 98% of products therefrom.
Embodiment 2 prepares DOPO using the inventive method
1st, by 100g o-phenyl phenols (1eq, 0.588mol), 1g anhydrous zinc chlorides (0.0125eq, 0.0073mol) and
112.98g phosphorus trichlorides (1.4eq) are added in 500mL four-hole boiling flasks, after being warming up to 80 DEG C of reaction 2h, are continuously heating to 180 DEG C
2h is reacted, HPLC detection reactions are complete, and reaction solution is directly used in react in next step.
2nd, 150g toluene and 5g diatomite are added in step reaction solution upwards, 0.5h is stirred at room temperature, filters to obtain colorless and clear liquid.
50g purified waters are added in filtrate, temperature rising reflux 4h, TLC detection reaction is complete.0 DEG C is cooled to, it is solid that strong stirring separates out white
Body, filtering, filter cake are washed twice with 50g purified waters, collect filter cake, are directly used in and are reacted in next step.
3rd, upper step crude product is gone in reaction flask, heating makes its thawing, under the conditions of vacuum 5mbar, is warming up to 180
DEG C, stirring dehydration 6h, HPLC monitoring reaction end, it is cooled to room temperature crystallization and obtains target compound.
Above three-step reaction total recovery 90%, through vapor detection, the purity of products therefrom is 98.7%.
Beneficial effects of the present invention are proved below by way of test example.
The PCl of test example 13Influence of/OPP the mol ratios to DOPO yields
Using PCl as shown in the table3/ OPP mol ratios prepare DOPO, and remaining process conditions is the same as embodiment 1：
The PCl of table 13Influence of/OPP the mol ratios to DOPO yields
| PCl3/ OPP mol ratios | DOPO yields |
| 1.00∶1.25 | 37.8% |
| 1.00∶1.00 | 44.9% |
| 1.20∶1.00 | 64.6% |
| 1.40∶1.00 | 76.3% |
| 1.50∶1.00 | 77.3% |
| 1.80∶1.00 | 77.5% |
| 2.00∶1.00 | 78.1% |
From the foregoing, it will be observed that the mol ratio of phosphorus trichloride and o-phenyl phenol is (1：1.25)~(2：1) equal energy in the range of
DOPO is prepared；Both mol ratio yields in the range of (1.2: 1)~(2: 1) are higher, can reach more than 64.6%, are
Preferable scope；Comprehensive yield saw that both optimum proportionings were 1.4: 1 with feeding intake into originally.
Influence of the esterification reaction temperature of test example 2 to DOPO yields
DOPO, PCl are prepared under the conditions of esterification reaction temperature as shown in the table3/ OPP mol ratio is 1.4: 1,
Friedel-crafts acylation reaction controls temperature, and in 160 DEG C, remaining process conditions is the same as embodiment 1：
Influence of the esterification reaction temperature of table 2 to DOPO yields
| Esterification reaction temperature | DOPO yields |
| 40℃ | 50.7% |
| 60℃ | 65.7% |
| 80℃ | 79.1% |
| 100℃ | 75.3% |
| 120℃ | 74.6% |
| 140℃ | 73.9% |
From the foregoing, it will be observed that DOPO can be prepared with higher yield when esterification reaction temperature is controlled in 60~140 DEG C；Its
In, yield highest when esterification reaction temperature is 80 DEG C.
Influence of the friedel-crafts acylation reaction temperature of test example 3 to DOPO yields
DOPO, PCl are prepared under friedel-crafts acylation reaction temperature conditionss as shown in the table3/ OPP mol ratio is
1.4: 1, esterification controls temperature, and in 80 DEG C, remaining process conditions is the same as embodiment 1：
Influence of the friedel-crafts acylation reaction temperature of table 3 to DOPO yields
From the foregoing, it will be observed that friedel-crafts acylation reaction temperature control can be prepared into when 160~220 DEG C with higher yield
To DOPO；Comprehensive yield saw that friedel-crafts acylation reaction temperature was 180 DEG C optimal with being produced into originally.
Influence of the recrystallization temperature to DOPO yields after test example 4 hydrolyzes
Control PCl3/ OPP mol ratio is 1.4: 1, and esterification reaction temperature is 80 DEG C, friedel-crafts acylation reaction temperature
For 180 DEG C, solid is separated out at temperature as shown in the table respectively after hydrolysis, remaining process conditions is the same as embodiment 1：
Influence of the recrystallization temperature to DOPO yields after table 4 hydrolyzes
If from the foregoing, it will be observed that being cooled to 25 DEG C after hydrolysis, reaction solution is in semi-solid, and more sticky, product crystallization is incomplete, and
And impurity is easily wrapped up, cause the reduction of DOPO yields；If being cooled to less than 0 DEG C, solid can be smoothly separated out, DOPO yields are reachable
To more than 90.0%；Comprehensive yield saw that recrystallization temperature was 0 DEG C optimal with being produced into originally.
Influence of the dehydration vacuum of test example 5 to DOPO purity
Control PCl3/ OPP mol ratio is 1.4: 1, and esterification reaction temperature is 80 DEG C, friedel-crafts acylation reaction temperature
For 180 DEG C, recrystallization temperature is 0 DEG C after hydrolysis, is dehydrated under conditions of vacuum as shown in the table and 200 DEG C, remaining technique
Condition is the same as embodiment 1：
Influence of the dehydration vacuum of table 5 to DOPO purity
From the foregoing, it will be observed that being dehydrated under conditions of 0.1~100mbar of vacuum, the direct crystallization of reaction solution can obtain purity
Reach more than 95.3% DOPO；In below 5mbar, purity can further improve to 99.7% vacuum, be preferable scope；
Condensation products purity saw that vacuum was that 5mbar is optimal with being produced into originally.
Influence of the dehydration temperature of test example 6 to DOPO purity
Control PCl3/ OPP mol ratio is 1.4: 1, and esterification reaction temperature is 80 DEG C, friedel-crafts acylation reaction temperature
For 180 DEG C, recrystallization temperature is 0 DEG C after hydrolysis, is dehydrated under vacuum 5mbar and temperature conditionss as shown in the table, remaining work
Skill condition is the same as embodiment 1：
Influence of the dehydration temperature of table 6 to DOPO purity
| Reaction temperature | (HPLC)HPPA∶DOPO |
| 140℃ | 7.8∶92.2 |
| 160℃ | 3.5∶93.9 |
| 180℃ | 1.3∶98.7 |
| 190℃ | 0.3∶99.7 |
| 210℃ | 0.27∶99.73 |
From the foregoing, it will be observed that being dehydrated under 140~210 DEG C of temperature conditionss, the direct crystallization of reaction solution can obtain purity and reach
More than 92.2% DOPO；Under conditions of 180~210 DEG C, purity can further improve to more than 98.7% temperature, be preferred
Scope；Condensation products purity saw that temperature was 190 DEG C optimal with being produced into originally.
Claims (9)
1. the preparation method of compound shown in formula I, it is characterized in that：Comprise the following steps：
The mixture of o-phenyl phenol, zinc chloride and phosphorus trichloride is warming up to 60~140 DEG C, after esterification, continues to heat up
To 160~220 DEG C of reactions, compound shown in formula I is produced.
2. preparation method as claimed in claim 1, it is characterized in that：The mol ratio of phosphorus trichloride and o-phenyl phenol is (1：
1.25)~(2：1)；Preferably (1.2：1)~(2：1)；More preferably 1.4：1.
3. preparation method as claimed in claim 1, it is characterized in that：The mol ratio of zinc chloride and o-phenyl phenol is
(0.00125：1)~(0.125：1)；Preferably 0.0125：1.
4. preparation method as claimed in claim 1, it is characterized in that：By the mixing of o-phenyl phenol, zinc chloride and phosphorus trichloride
Thing is warming up to 80 DEG C, after esterification, is continuously heating to 180~220 DEG C of reactions.
5. the preparation method as described in claim 1 or 4, it is characterized in that：Reaction time of esterification is 1~4h；Preferably 2h.
6. the preparation method of compound shown in formula II, it is characterized in that：Comprise the following steps：
A, compound shown in formula I is prepared according to Claims 1 to 5 any one methods described, reaction solution is standby；
B, benzene series solvent and adsorbent are added into reaction solution obtained by step a, is filtered after stirring, filtrate is standby；Preferably, it is described
Adsorbent is diatomite；
C, water is added into step b gained filtrates, temperature rising reflux is complete to hydrolyzing, and is cooled to less than 5 DEG C, separates out solid, filters,
It is standby to collect filter cake；Preferably, it is cooled to -20~0 DEG C；It is further preferred that it is cooled to 0 DEG C；
D, filter cake obtained by taking step c, is dehydrated under conditions of below vacuum 100mbar, 140~210 DEG C of temperature, produces formula II
Shown compound；Preferably, vacuum is below 5mbar, and temperature is 180~210 DEG C；It is further preferred that vacuum is
5mbar, temperature are 190 DEG C.
7. preparation method as claimed in claim 6, it is characterized in that：The mass ratio of benzene series solvent and o-phenyl phenol is (2：1)
~(1：1)；Preferably 1.5：1.
8. preparation method as claimed in claim 6, it is characterized in that：The mass ratio of water and o-phenyl phenol is (1：2)~(4：
1)；Preferably 1：2.
9. preparation method as claimed in claims 6 or 7, it is characterized in that：The benzene series solvent is toluene, mesitylene, inclined three
One or more kinds of mixed solvent in toluene or chlorobenzene；It is preferred that toluene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111041591A (en) * | 2019-12-27 | 2020-04-21 | 刘大刚 | Modified polyester for labor protection fabric |
| CN115838384A (en) * | 2022-11-18 | 2023-03-24 | 浙江万盛股份有限公司 | Efficient and safe preparation method of 6-chloro- (6-hydrogen) -diphenyl [ C, E ] [1,2] -phosphaphenanthrene |
| CN115974926A (en) * | 2022-12-23 | 2023-04-18 | 沧州临港丰亚化工有限公司 | Refining method of low-metal-ion low-chroma DOPO flame retardant |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111041591A (en) * | 2019-12-27 | 2020-04-21 | 刘大刚 | Modified polyester for labor protection fabric |
| CN115838384A (en) * | 2022-11-18 | 2023-03-24 | 浙江万盛股份有限公司 | Efficient and safe preparation method of 6-chloro- (6-hydrogen) -diphenyl [ C, E ] [1,2] -phosphaphenanthrene |
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| CN115974926A (en) * | 2022-12-23 | 2023-04-18 | 沧州临港丰亚化工有限公司 | Refining method of low-metal-ion low-chroma DOPO flame retardant |
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