CN114213462A - O-phenylenedioxy bis-neopentyl glycol phosphate and its synthesis method - Google Patents
O-phenylenedioxy bis-neopentyl glycol phosphate and its synthesis method Download PDFInfo
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- neopentyl glycol
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- -1 bis-neopentyl glycol phosphate Chemical compound 0.000 title claims abstract description 65
- 238000001308 synthesis method Methods 0.000 title description 8
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 20
- VTDOZTKLYMTWQU-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol phosphoryl trichloride Chemical compound OCC(C)(CO)C.P(=O)(Cl)(Cl)Cl VTDOZTKLYMTWQU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 94
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 abstract description 2
- HEORQRHVQJVWEH-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) dihydrogen phosphate Chemical compound OCC(C)(C)COP(O)(O)=O HEORQRHVQJVWEH-UHFFFAOYSA-N 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YBHILYKTIRIUTE-UHFFFAOYSA-N berberine Chemical compound C1=C2CC[N+]3=CC4=C(OC)C(OC)=CC=C4C=C3C2=CC2=C1OCO2 YBHILYKTIRIUTE-UHFFFAOYSA-N 0.000 description 1
- 229940093265 berberine Drugs 0.000 description 1
- QISXPYZVZJBNDM-UHFFFAOYSA-N berberine Natural products COc1ccc2C=C3N(Cc2c1OC)C=Cc4cc5OCOc5cc34 QISXPYZVZJBNDM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229940039009 isoproterenol Drugs 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
Abstract
A method for synthesizing o-phenylenedioxy bis-neopentyl glycol phosphate ester comprises the steps of taking catechol as a skeleton, introducing a phosphorus-containing annular structure of neopentyl glycol, mixing neopentyl glycol phosphoryl chloride, catechol, a catalyst and an organic solvent, then dripping an acid-binding agent at a low temperature, heating for reaction for a period of time, purifying, and removing the solvent to obtain the target product o-phenylenedioxy bis-neopentyl glycol phosphate ester. The o-phenylenedioxy neopentyl glycol diphosphate synthesized by the method has the characteristics of high specific symmetry, good heat resistance and the like, and has good rigid structure and high thermal stability; the two five-membered rings have stable structures and are not easy to hydrolyze.
Description
Technical Field
The invention relates to the technical field of aryl phosphate flame retardance, in particular to a method for synthesizing o-phenylenedioxy neopentyl glycol phosphate, and also relates to the o-phenylenedioxy neopentyl glycol phosphate synthesized by the method for synthesizing the o-phenylenedioxy neopentyl glycol phosphate.
Background
In recent years, with the rapid development of polymer materials, the polymer materials are widely applied in various fields of national economy, but the occurrence frequency of fire is increased, and the serious threat is brought to the life and property safety of people, so that the materials are widely concerned in flame retardant treatment, people begin to carry out systematic research on organic phosphorus flame retardants under the drive of non-halogenation, and the phosphorus flame retardants become hot spots for research and development of national flame retardant research units.
The phosphate flame retardant has the advantages of low smoke, no toxicity, no halogen, good compatibility with materials, lasting flame retardant effect, water resistance, heat resistance, migration resistance and the like, so the phosphate flame retardant accords with the development direction of the flame retardant and has good development prospect.
Catechol is a phenol substance containing two hydroxyl groups, is used for manufacturing rubber hardeners and electroplating additives, and is an important chemical intermediate; can be used for producing berberine and isoproterenol as pharmaceutical intermediate; the synthesis of the bactericide and the pesticide also needs catechol as a raw material, which accounts for a large proportion in the aspects of the use of antioxidants and light stabilizers, and the synthesis of the bactericide and the pesticide as the synthesis raw material of the flame retardant has fewer varieties of synthesized products.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the o-phenylenedioxy bis-neopentyl glycol phosphate which takes pyrocatechol as a framework, introduces a phosphorus-containing annular structure of neopentyl glycol, has the characteristics of high symmetry, good heat resistance and the like, and has good rigid structure and high thermal stability; the two five-membered rings have stable structures and are not easy to hydrolyze.
The invention also provides a synthesis method of the o-phenylenedioxy neopentyl glycol phosphate.
The technical problem to be solved by the present invention is achieved by the following technical means. The invention relates to a method for synthesizing o-phenylenedioxy neopentyl glycol diphosphate, which comprises the steps of mixing neopentyl glycol phosphoryl chloride, catechol, a catalyst and an organic solvent, then dripping an acid-binding agent at a low temperature, heating for reaction for a period of time, and then purifying and removing the solvent to obtain a target product o-phenylenedioxy neopentyl glycol diphosphate, wherein the reaction route of the synthetic method is as follows:
the technical problem to be solved by the invention can be further realized by the following technical scheme that for the above method for synthesizing the o-phenylenedioxy neopentyl glycol diphosphate, the molar ratio of the catechol to the neopentyl glycol phosphoryl chloride is 1: 2-5.
The technical problem to be solved by the invention can be further realized by the following technical scheme that for the synthetic method of the o-dioxy neopentyl glycol phosphate, the adding amount of the organic solvent is 10-20 times of the mass of catechol.
The technical problem to be solved by the invention can be further realized by the following technical scheme that for the synthetic method of the o-dioxy neopentyl glycol phosphate, the dosage of the catalyst is 0.1-5% of the molar mass of catechol.
The technical problem to be solved by the present invention can be further solved by the following technical scheme, wherein for the above-mentioned synthetic method of the o-phenylenedioxy neopentyl glycol diphosphate, the catalyst is selected from one or more of aluminum chloride, magnesium chloride and 4-dimethylaminopyridine.
The technical problem to be solved by the present invention can be further solved by the following technical scheme, wherein for the above-mentioned synthetic method of o-phenylenedioxy neopentyl glycol diphosphate, the organic solvent is selected from one or more of acetonitrile, chloroform, 1, 2-dichloroethane, acetone and dichloromethane.
The technical problem to be solved by the present invention can be further solved by the following technical scheme, wherein for the above-mentioned method for synthesizing the o-phenylenedioxy neopentyl glycol diphosphate, the acid-binding agent is selected from one or more of triethylamine, pyridine and ethylenediamine.
The technical problem to be solved by the invention can be further realized by the following technical scheme that for the method for synthesizing the o-phenylenedioxy neopentyl glycol diphosphate, the acid-binding agent is dropwise added at the temperature of 0-10 ℃, the temperature of the temperature-rising reaction is 20-60 ℃, and the time of the temperature-rising reaction is 3-10 hours.
The technical problem to be solved by the present invention can be further solved by the following technical scheme, wherein the purification treatment is filtration treatment, and then the obtained liquid is subjected to solvent removal and is placed into a vacuum drying oven for drying.
The technical problem to be solved by the invention can be further realized by the following technical scheme that for the synthesis method of the o-phenylenedioxy neopentyl glycol diphosphate, the o-phenylenedioxy neopentyl glycol diphosphate is the o-phenylenedioxy neopentyl glycol diphosphate synthesized by the o-phenylenedioxy neopentyl glycol diphosphate synthesis method, catechol is used as a framework, a neopentyl glycol phosphorus-containing annular structure is introduced, and the o-phenylenedioxy neopentyl glycol phosphorus-containing annular structure has the characteristics of high symmetry and good heat resistance, can be used as a novel single-component phosphorus flame retardant, and is good in rigid structure and high in thermal stability due to the benzene-containing annular structure, and two five-membered rings are stable in structure and are not easy to hydrolyze.
Compared with the prior art, the o-phenylenedioxy neopentyl glycol diphosphate obtained by the synthesis method provided by the invention contains symmetrical aromatic rings and 2 rigid rings in the structure, so that the o-phenylenedioxy neopentyl glycol diphosphate has high phosphorus content and good thermal stability, and can be used for flame-retardant polypropylene, epoxy resin, polyurethane and other systems.
Drawings
FIG. 1 is a hydrogen spectrum of a target product of the present application;
FIG. 2 is a phosphorus spectrum of a target product of the present application;
FIG. 3 is a phosphorus spectrum of a target product of the present application;
FIG. 4 is an infrared spectrum of a target product of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to FIGS. 1 to 4, example 1, a method for synthesizing bis-neopentyl glycol phosphate ester phthalate dioxy comprises the steps of firstly, preparing 11g (0.1 mol) of catechol, 36.8g (0.2 mol) of neopentyl glycol phosphoryl chloride and 0.665g of AlCl3The mixture was dissolved in 300g of methylene chloride,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to drip 30g (0.3 mol) of triethylamine, finishing dripping within half an hour, transferring into an oil pan, reacting for 4.5h at the temperature of 35 ℃,
finally, triethylamine hydrochloride is removed by filtration, a dichloromethane layer is washed by 200ml of water, and dichloromethane is removed by rotary evaporation, so that light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) is obtained, wherein the yield is 83.1%.
Example 2. A method for synthesizing bis-neopentyl glycol phosphate ester phthalate dioxy, first 11g (0.1 mol) of catechol, 55.2g (0.3 mol) of neopentyl glycol phosphoryl chloride and 0.665g of AlCl3 were dissolved in 300g of dichloromethane,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to dropwise add 30g (0.3 mol) of triethylamine, finishing dropping for half an hour, transferring into an oil pan, reacting for 4.5 hours at 35 ℃,
and finally, filtering to remove triethylamine hydrochloride, washing a dichloromethane layer by 200ml of water, and removing dichloromethane by rotary evaporation to obtain light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) ester, wherein the yield is 86.3%.
Example 3A method for synthesizing bis-neopentyl glycol phosphate ester phthalate dioxy comprises dissolving 11g (0.1 mol) of catechol, 73.6g (0.4 mol) of neopentyl glycol phosphoryl chloride and 0.665g of AlCl3 in 300g of dichloromethane,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to dropwise add 30g (0.3 mol) of triethylamine, finishing dropping for half an hour, transferring into an oil pan, reacting for 4.5 hours at 35 ℃,
finally, triethylamine hydrochloride is removed by filtration, a dichloromethane layer is washed by 200ml of water, and dichloromethane is removed by rotary evaporation, so that light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) is obtained, wherein the yield is 89.8%.
Example 4A method for the synthesis of o-phenylenedioxy bis-neopentyl glycol phosphate by dissolving 11g (0.1 mol) of catechol, 73.6g (0.4 mol) of neopentyl glycol phosphoryl chloride and 0.48 g of MgCl2 in 300g of dichloromethane,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to dropwise add 30g (0.3 mol) of triethylamine, finishing dropping for half an hour, transferring into an oil pan, reacting for 4.5 hours at 35 ℃,
and finally, filtering to remove triethylamine hydrochloride, washing a dichloromethane layer by 200ml of water, and removing dichloromethane by rotary evaporation to obtain light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) ester, wherein the yield is 83.2%.
Example 5A method for the synthesis of o-phenylenedioxy bis-neopentyl glycol phosphate by dissolving 11g (0.1 mol) of catechol, 73.6g (0.4 mol) of neopentyl glycol phosphoryl chloride and 0.61g of DMAP in 300g of dichloromethane,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to dropwise add 30g (0.3 mol) of triethylamine, finishing dropping for half an hour, transferring into an oil pan, reacting for 4.5 hours at 35 ℃,
and finally, filtering to remove triethylamine hydrochloride, washing a dichloromethane layer by 200ml of water, and removing dichloromethane by rotary evaporation to obtain light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) with the yield of 94.8%.
Example 6A method for the synthesis of o-phenylenedioxy bis-neopentyl glycol phosphate by dissolving 11g (0.1 mol) of catechol, 73.6g (0.4 mol) of neopentyl glycol phosphoryl chloride and 0.61g of DMAP in 300g of dichloromethane,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to dropwise add 30g (0.3 mol) of triethylamine, finishing dropping for half an hour, transferring into an oil pan, reacting for 4.5 hours at 45 ℃,
finally, triethylamine hydrochloride was removed by filtration, and the dichloromethane layer was washed with 200ml of water. Methylene dichloride is removed by rotary evaporation, and light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) is obtained, wherein the yield is 96.8 percent.
Example 7 an o-phenylenedioxy neopentyl glycol phosphate which was synthesized using the synthesis method of o-phenylenedioxy neopentyl glycol phosphate of example 6.
Example 8A method for the synthesis of o-phenylenedioxy bis-neopentyl glycol phosphate by dissolving 11g (0.1 mol) of catechol, 73.6g (0.4 mol) of neopentyl glycol phosphoryl chloride and 0.61g of DMAP in 300g of dichloromethane,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to dropwise add 30g (0.3 mol) of triethylamine, finishing dropping for half an hour, transferring into an oil pan, reacting for 4.5 hours at 55 ℃,
finally, triethylamine hydrochloride was removed by filtration, and the dichloromethane layer was washed with 200ml of water. Methylene dichloride is removed by rotary evaporation, and light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) is obtained, wherein the yield is 95.8 percent.
Example 9 an o-phenylenedioxy neopentyl glycol phosphate synthesized using the synthesis method of o-phenylenedioxy neopentyl glycol phosphate of example 8.
Example 10A method for the synthesis of o-phenylenedioxy bis-neopentyl glycol phosphate by dissolving 11g (0.1 mol) of catechol, 73.6g (0.4 mol) of neopentyl glycol phosphoryl chloride and 0.61g of DMAP in 300g of dichloromethane,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to dropwise add 30g (0.3 mol) of triethylamine, finishing dropping for half an hour, transferring into an oil pan, reacting for 3 hours at 45 ℃,
and finally, filtering to remove triethylamine hydrochloride, washing a dichloromethane layer by 200ml of water, and removing dichloromethane by rotary evaporation to obtain light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) ester, wherein the yield is 90.1%.
Example 11, a method for synthesizing o-phenylenedioxy bis-neopentyl glycol phosphate, first 11g (0.1 mol) of catechol, 73.6g (0.4 mol) of neopentyl glycol phosphoryl chloride and 0.61g of DMAP were dissolved in 300g of dichloromethane,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to dropwise add 30g (0.3 mol) of triethylamine, finishing dropping for half an hour, transferring into an oil pan, reacting for 6 hours at 45 ℃,
and finally, filtering to remove triethylamine hydrochloride, washing a dichloromethane layer by 200ml of water, and removing dichloromethane by rotary evaporation to obtain light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) ester, wherein the yield is 95.3%.
Example 12A method for the synthesis of o-phenylenedioxy bis-neopentyl glycol phosphate by dissolving 11g (0.1 mol) of catechol, 73.6g (0.4 mol) of neopentyl glycol phosphoryl chloride and 0.61g of DMAP in 300g of dichloromethane,
then transferring into a low-temperature cold bath, after the temperature is reduced to about 0 ℃, beginning to dropwise add 30g (0.3 mol) of triethylamine, finishing dropping for half an hour, transferring into an oil pan, reacting for 8 hours at 45 ℃,
and finally, filtering to remove triethylamine hydrochloride, washing a dichloromethane layer by 200ml of water, and removing dichloromethane by rotary evaporation to obtain light yellow powder solid o-phenylenedioxy bis (neopentyl glycol phosphate) ester with the yield of 95%.
Claims (10)
1. A method for synthesizing o-phenylenedioxy neopentyl glycol phosphate is characterized by comprising the following steps: mixing neopentyl glycol phosphoryl chloride, catechol, a catalyst and an organic solvent, then dripping an acid-binding agent at a low temperature, heating for reaction for a period of time, and then purifying and removing the solvent to obtain the target product of o-phenylenedioxy bis-neopentyl glycol phosphate.
2. The method for synthesizing o-phenylenedioxy neopentyl glycol phosphate as claimed in claim 1, wherein: the molar ratio of catechol to neopentyl glycol phosphoryl chloride is 1: 2-5.
3. The method for synthesizing o-phenylenedioxy neopentyl glycol phosphate as claimed in claim 1 or 2, wherein: the adding amount of the organic solvent is 10-20 times of the mass of the catechol.
4. The method for synthesizing o-phenylenedioxy neopentyl glycol phosphate as claimed in claim 1 or 2, wherein: the dosage of the catalyst is 0.1-5% of the molar mass of the catechol.
5. The method for synthesizing o-phenylenedioxy neopentyl glycol phosphate as claimed in claim 1, wherein: the catalyst is selected from one or more of aluminum chloride, magnesium chloride and 4-dimethylamino pyridine.
6. The method for synthesizing o-phenylenedioxy neopentyl glycol phosphate as claimed in claim 1, wherein: the organic solvent is selected from one or more of acetonitrile, chloroform, 1, 2-dichloroethane, acetone and dichloromethane.
7. The method for synthesizing o-phenylenedioxy neopentyl glycol phosphate as claimed in claim 1, wherein: the acid-binding agent is selected from one or more of triethylamine, pyridine and ethylenediamine.
8. The method for synthesizing o-phenylenedioxy neopentyl glycol phosphate as claimed in claim 1, wherein: the dripping temperature of the acid-binding agent is 0-10 ℃, the temperature of the heating reaction is 20-60 ℃, and the time of the heating reaction is 3-10 h.
9. An o-phenylenedioxy bis-neopentyl glycol phosphate as claimed in claim 1, characterized in that: the purification treatment is filtration treatment, then the solvent is removed from the obtained liquid, and the liquid is placed in a vacuum drying oven for drying.
10. An o-phenylenedioxy bis-neopentyl glycol phosphate ester, characterized in that: the o-phenylenedioxy neopentyl glycol phosphate is an o-phenylenedioxy neopentyl glycol phosphate synthesized by the method for synthesizing an o-phenylenedioxy neopentyl glycol phosphate according to any of claims 1 to 9.
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