CN116925139A - Purification method of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus - Google Patents
Purification method of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus Download PDFInfo
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- CN116925139A CN116925139A CN202210337078.7A CN202210337078A CN116925139A CN 116925139 A CN116925139 A CN 116925139A CN 202210337078 A CN202210337078 A CN 202210337078A CN 116925139 A CN116925139 A CN 116925139A
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- trimethylbenzoyl
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- degrees celsius
- butyrate
- formate
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- DKKXSNXGIOPYGQ-UHFFFAOYSA-N diphenylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 DKKXSNXGIOPYGQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000000746 purification Methods 0.000 title abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000005859 coupling reaction Methods 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- CFNJLPHOBMVMNS-UHFFFAOYSA-N pentyl butyrate Chemical compound CCCCCOC(=O)CCC CFNJLPHOBMVMNS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229940072049 amyl acetate Drugs 0.000 claims description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 claims description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- KEEXOYPZMIJIEP-UHFFFAOYSA-N diphenoxyphosphoryl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 KEEXOYPZMIJIEP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000000016 photochemical curing Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract 2
- 238000002360 preparation method Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- UKRQMDIFLKHCRO-UHFFFAOYSA-N 2,4,6-trimethylbenzoyl chloride Chemical compound CC1=CC(C)=C(C(Cl)=O)C(C)=C1 UKRQMDIFLKHCRO-UHFFFAOYSA-N 0.000 description 6
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 6
- -1 lithium aluminum hydride Chemical compound 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CMRWTDCXKPPUEG-UHFFFAOYSA-N (2,3,4-trimethylphenyl) formate Chemical compound CC1=CC=C(OC=O)C(C)=C1C CMRWTDCXKPPUEG-UHFFFAOYSA-N 0.000 description 1
- LESMLVDJJCWZAJ-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)-1,3,5-trimethylbenzene Chemical group CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 LESMLVDJJCWZAJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- USZLCYNVCCDPLQ-UHFFFAOYSA-N hydron;n-methoxymethanamine;chloride Chemical compound Cl.CNOC USZLCYNVCCDPLQ-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FVOMJWZIGNBHOA-UHFFFAOYSA-M sodium;diphenyl phosphate Chemical compound [Na+].C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 FVOMJWZIGNBHOA-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to the technical field of separation and purification of new material chemicals with a photocuring function, and provides a purification method of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus. The technology aims at the preparation technology for synthesizing 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, and belongs to the purification category of intermediates. The high-purity 2,4, 6-trimethylbenzoyl diphenyl phosphate is directly obtained by utilizing the coupling reaction participated by metal, the intermediate is separated out in the reaction liquid, the reaction liquid is directly filtered, and the reaction liquid is leached by a solvent, so that the white solid with the purity of more than 99 percent is obtained. The invention has the characteristics of simple operation and environmental protection, and has higher industrial application value.
Description
[ field of technology ]
The invention relates to the technical field of separation and purification of new material chemicals with a photocuring function, in particular to a purification method of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus.
[ background Art ]
2,4, 6-trimethylbenzoyl-diphenylphosphorus, the English name is diphenylphosphoryl- (2, 4, 6-trimethylphenyl) methane, and the molecular formula is C 22 H 21 OP is white solid at normal temperature, and has the following chemical structural formula:
2,4, 6-trimethylbenzoyl-diphenyl phosphorus is an important chemical raw material and is also an intermediate for synthesizing TPO (2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide).
The synthesis of 2,4, 6-trimethylbenzoyl-diphenylphosphorus is currently carried out in a number of ways, the main synthesis being that patent CN105541913 discloses the use of triphenylphosphine and metallic sodium to react with phosphorus trichloride to form sodium diphenylphosphate which is then condensed with 2,4, 6-trimethylbenzoyl chloride to prepare the intermediate. Triphenylphosphine has high self-cost, and the use of phosphorus trichloride also causes the problems of waste acid recovery and treatment. Patent US4447520 discloses that diphenyl phosphorus chloride is reduced to a phosphine intermediate by lithium aluminum hydride and then reacted with sodium tert-butoxide and acyl chloride to prepare the intermediate, but the method has a plurality of steps, and materials with harsh operating conditions such as lithium aluminum hydride and the like are used, so that the risk is extremely high. Patent CN110343134 reports that phenylphosphorus metal compound and CO2 directly construct phenylphosphoryl diformate, then N, O-dimethylhydroxylamine hydrochloride is used to activate the carboxyl group of phenylphosphoryl diformate in situ to prepare Weinreb amide, then trimethylphenyl format reagent or organolithium reagent is used to attack and add to construct the intermediate, but rather harsh format reagent is used in the reaction process, and the equipment and reaction conditions are relatively strict.
In conclusion, the 2,4, 6-trimethylbenzoyl-diphenyl phosphine can be separated through a process with mild conditions and simple operation, and the method has important significance for realizing industrialization of the intermediate.
[ invention ]
Aiming at the defects, the invention aims to solve the technical problems that the high-purity 2,4, 6-trimethylbenzoyl diphenyl phosphate is directly obtained by utilizing the coupling reaction participated by metal, the intermediate is separated out in the reaction liquid, is directly filtered, and is leached by a solvent to obtain white solid with the purity of more than 99 percent. The invention has the characteristics of simple operation and environmental protection, and has higher industrial application value.
The technical problem to be solved by the invention is realized by the following technical scheme, and the specific reaction steps are as follows:
(1) Primary solvent crystallization: coupling reaction to obtain 2,4,6-trimethyl benzoyl diphenyl phosphorus
The mixed solution was allowed to stand to obtain a preliminary solvent crystal.
(2) And (3) optimizing temperature crystallization: by controlling the temperature, the crystallization is promoted, and the mixture is filtered and used as the liquid phase.
(3) Washing a crude product: pulping, washing, filtering and drying are carried out through a solvent and a controlled dosage, and the high-purity 2,4, 6-trimethylbenzoyl-diphenyl phosphorus crystal is further refined.
The organic solvent used in the invention can be selected from substituted or unsubstituted aromatic hydrocarbon containing 1-24 carbons, straight-chain or branched-chain aliphatic hydrocarbon, amide, alcohol, ether, ester, carbonic ester, ketone, nitrile, carboxylic acid, water, amine, ionic liquid, supercritical carbon dioxide or a mixed solvent composed of any two or more types of solvents; preferred solvents are methyl formate, ethyl formate, propyl formate, butyl formate, pentyl formate, butyl acetate, ethyl acetate, methyl acetate, amyl acetate, methyl propionate, ethyl propionate, propyl propionate, pentyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, amyl butyrate, methyl valerate,N, N-a solvent of the type dimethylformamide, which is chosen,N, N-dimethylacetamide, formylmorpholine,N, N-a solvent of the type of diethylformamide,N-methyl pyrrolidone, or a mixed solvent of any two or more of the above solvents.
The crystallization temperature is 10-30 DEG C o The volume consumption of the solvent between C is 2-8 times of that of the separated crystals, and the drying condition is 40-60 o Drying under C for 2-5h.
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
1. by selecting the reaction solvent effect, the crystal is easy to be separated out in the reaction system, and the crystallization yield is high.
2. Less solvent can be used for leaching, and the consumption of the solvent is reduced.
3. The crystallization condition is mild, the process is simple, the requirement on equipment is low, and industrialization is easy to realize.
We will further describe in the examples.
[ detailed description ] of the invention
The gist of the present invention is further described below with reference to specific examples:
embodiment one:
26.5 g of 100-mesh silver gray zinc powder and 600 ml of ethyl acetate are sequentially added into a 1-liter flask at room temperature under the protection of nitrogen, cooled to below 5 ℃, then 60.0 g of diphenyl phosphorus chloride and 74.5 g of 2,4,6-trimethyl benzoyl chloride are sequentially added dropwise, and after the dropwise addition is finished, the mixture is continuously and fully stirred for 5 hours. Then adding 45 g of hydrogen peroxide into the reaction system in turn for oxidation, recovering to room temperature, adding 100 g of sodium bicarbonate aqueous solution for shaking and washing, separating an organic phase for desolventizing, adding ethanol for cooling crystallization, filtering and drying to obtain 80.1 g of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide yellow-green pure product with the yield of 85%.
Embodiment two:
26.5 g of 1000-mesh silver gray zinc powder and 600 ml of ethyl acetate are sequentially added into a 1-liter flask at room temperature under the protection of nitrogen, cooled to below 5 ℃, then 60.0 g of diphenyl phosphorus chloride and 74.5 g of 2,4,6-trimethyl benzoyl chloride are sequentially added dropwise, and after the dropwise addition is finished, the mixture is continuously and fully stirred for 5 hours. Then adding 45 g of hydrogen peroxide into the reaction system in turn for oxidation, recovering to room temperature, adding 100 g of sodium bicarbonate aqueous solution for shaking and washing, separating an organic phase for desolventizing, adding ethanol for cooling crystallization, filtering and drying to obtain 81 g of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide yellow-green pure product with the yield of 90%.
Embodiment III:
26.5 g of 500-mesh silver gray zinc powder and 600 ml of ethyl acetate are sequentially added into a 1-liter flask at room temperature under the protection of nitrogen, cooled to below 5 ℃, then 60.0 g of diphenyl phosphorus chloride and 74.5 g of 2,4,6-trimethyl benzoyl chloride are sequentially added dropwise, and after the dropwise addition is finished, the mixture is continuously and fully stirred for 5 hours. Then adding 45 g of hydrogen peroxide into the reaction system in turn for oxidation, recovering to room temperature, adding 100 g of sodium bicarbonate aqueous solution for shaking and washing, separating an organic phase for desolventizing, adding ethanol for cooling crystallization, filtering and drying to obtain 88.3 g of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide yellow-green pure product with the yield of 93%.
Embodiment four:
26.5 g of 100-mesh dark gray zinc powder and 600 ml of ethyl acetate are sequentially added into a 1-liter flask at room temperature under the protection of nitrogen, cooled to below 5 ℃, then 60.0 g of diphenyl phosphorus chloride and 74.5 g of 2,4,6-trimethyl benzoyl chloride are sequentially added dropwise, and after the dropwise addition is finished, the mixture is continuously and fully stirred for 5 hours. Then adding 45 g of hydrogen peroxide into the reaction system in turn for oxidation, recovering to room temperature, adding 100 g of sodium bicarbonate aqueous solution for shaking and washing, separating an organic phase for desolventizing, adding ethanol for cooling crystallization, filtering and drying to obtain 74.1 g of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide yellow-green pure product with the yield of 78%.
Fifth embodiment:
26.5 g of zinc powder with dark gray color of 500 meshes and 600 ml of ethyl acetate are sequentially added into a 1 liter flask at room temperature under the protection of nitrogen, the temperature is reduced to below 5 ℃, 60.0 g of diphenyl phosphorus chloride and 74.5 g of 2,4,6-trimethyl benzoyl chloride are sequentially added dropwise, and after the dropwise addition is finished, the stirring is continued for 5 hours. Then adding 45 g of hydrogen peroxide into the reaction system in turn for oxidation, recovering to room temperature, adding 100 g of sodium bicarbonate aqueous solution for shaking and washing, separating an organic phase for desolventizing, adding ethanol for cooling crystallization, filtering and drying to obtain 81.7 g of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide yellow-green pure product with the yield of 86 percent.
It should be emphasized that the above examples are merely illustrative and not limiting, and that any adjustments or variations in reaction conditions or parameters, etc. that may be commonly employed by practitioners based on the disclosure of this application, should not depart from the gist of the present invention, and that the scope of this patent shall be subject to the relevant claim recitations.
Claims (5)
1. A method for purifying 2,4, 6-trimethylbenzoyl-diphenyl phosphorus, characterized by comprising the steps of:
(1) Primary solvent crystallization: the 2,4, 6-trimethylbenzoyl-diphenyl phosphorus mixed solution obtained by the coupling reaction is stood to realize a preliminary solvent crystal;
(2) And (3) optimizing temperature crystallization: by controlling the temperature, the crystallization is promoted, the solution is filtered, and the liquid phase is mixed solution;
(3) Washing a crude product: pulping, washing, filtering and drying are carried out through a solvent and a controlled dosage, and the high-purity 2,4, 6-trimethylbenzoyl-diphenyl phosphorus crystal is further refined.
2. The method for purifying 2,4, 6-trimethylbenzoyl-diphenylphosphorus according to claim 1, wherein said organic solvent is selected from the group consisting of substituted or unsubstituted aromatic hydrocarbons having 1 to 24 carbons, straight-chain or branched aliphatic hydrocarbons, amides, alcohols, ethers, esters, carbonates, ketones, nitriles, carboxylic acids, water, amines, ionic liquids, supercritical carbon dioxide, and mixtures of any two or more of the foregoing types of solvents; preferred solvents are methyl formate, ethyl formate, propyl formate, butyl formate, pentyl formate, butyl acetate, ethyl acetate, methyl acetate, amyl acetate, methyl propionate, ethyl propionate, propyl propionate, pentyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, amyl butyrate, methyl valerate, N, N-dimethylformamide, N, N-dimethylacetamide, formylmorpholine, N, N-diethylformamide, N-methylpyrrolidone, or a mixture of any two or more of the above solvents.
3. The process for purifying 2,4, 6-trimethylbenzoyl-diphenylphosphorus according to claim 1, wherein the temperature is selected from the range of-20 degrees celsius to 200 degrees celsius, preferably from 0 degrees celsius to 100 degrees celsius, more preferably from 10 degrees celsius to 30 degrees celsius.
4. The method for purifying 2,4, 6-trimethylbenzoyl-diphenylphosphorus according to claim 1, wherein the solvent is used in an amount of 2 to 8 times the volume of the isolated crystals.
5. The method for purifying 2,4, 6-trimethylbenzoyl-diphenylphosphorus as defined in claim 1, wherein said drying conditions are 40 to 60 o Drying under C for 2-5h.
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