CN102875598B - (二苯膦氧基)(均三甲苯基)甲酮和(苯膦氧基)双(均三甲苯基甲酮)的制备方法 - Google Patents
(二苯膦氧基)(均三甲苯基)甲酮和(苯膦氧基)双(均三甲苯基甲酮)的制备方法 Download PDFInfo
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- ketone
- mesitylene base
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- benzene
- phosphine
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 title claims abstract description 44
- 150000002576 ketones Chemical class 0.000 title claims abstract description 35
- -1 diphenyl phosphinyl Chemical group 0.000 title claims abstract description 31
- 150000002118 epoxides Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002585 base Substances 0.000 claims description 35
- 239000002994 raw material Substances 0.000 claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000011065 in-situ storage Methods 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- KJYSFXXGQXIPIG-UHFFFAOYSA-N 1,3,5-trimethyl-2-(trichloromethyl)benzene Chemical compound CC1=CC(C)=C(C(Cl)(Cl)Cl)C(C)=C1 KJYSFXXGQXIPIG-UHFFFAOYSA-N 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- JUMDHCZEQHHUGI-UHFFFAOYSA-N ClP.[O] Chemical compound ClP.[O] JUMDHCZEQHHUGI-UHFFFAOYSA-N 0.000 claims description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical class Cl* 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229960002163 hydrogen peroxide Drugs 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 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 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- BTCBJVLJLQFVSC-UHFFFAOYSA-N C(C1=CC=CC=C1)=O.C1(=CC(=CC(=C1)C)C)C Chemical compound C(C1=CC=CC=C1)=O.C1(=CC(=CC(=C1)C)C)C BTCBJVLJLQFVSC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical class C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CDQUDPXGOQEYKG-UHFFFAOYSA-N Cc1cc(C)c(C(P(c2ccccc2)(c2ccccc2)=O)(Cl)Cl)c(C)c1 Chemical compound Cc1cc(C)c(C(P(c2ccccc2)(c2ccccc2)=O)(Cl)Cl)c(C)c1 CDQUDPXGOQEYKG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 1
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical compound P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000736199 Paeonia Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- CBXOEWNRYOSZTE-UHFFFAOYSA-N [Na].P Chemical compound [Na].P CBXOEWNRYOSZTE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N c(cc1)ccc1Pc1ccccc1 Chemical compound c(cc1)ccc1Pc1ccccc1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical class ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- PXRDVIVDFIVDHI-UHFFFAOYSA-N diphenylphosphane;hydrochloride Chemical class [Cl-].C=1C=CC=CC=1[PH2+]C1=CC=CC=C1 PXRDVIVDFIVDHI-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 229910052700 potassium Chemical group 0.000 description 1
- 239000011591 potassium Chemical group 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
本发明涉及光辐射自由基聚合新材料技术领域，特别涉及商用光起始剂化合物(二苯膦氧基)(均三甲苯基)甲酮和(苯膦氧基)双(均三甲苯基甲酮)的新的合成工艺技术。本发明以1，3，5‑三甲基‑2‑(三氯甲基)‑苯为关键原料，分别和相应的有机膦前体经由缩合反应制备得到目标化合物。本申请披露的工艺以其化学反应技术的新颖性，成本经济竞争力以及环境友好性与已知工艺路线相比均具有显著的优势。
Description
【技术领域】
本发明涉及光辐射自由基聚合新材料技术领域，特别涉及商用光起始剂化合物(二苯膦氧基)(均三甲苯基)甲酮和(苯膦氧基)双(均三甲苯基甲酮)的新的合成工艺技术。
【背景技术】
在紫外光辐射固化领域，单和双膦酰型芳香酮化合物是具有重要工业应用价值的含烯不饱和体系自由基光聚合起始引发剂，已经成功商业化的代表性结构分别是如下所示的(二苯膦氧基)(均三甲苯基)甲酮[该化合物相应的英文名称为(diphenylphosphoryl)(mesityl)methanone]和(苯膦氧基)双(均三甲苯基甲酮)[该化合物相应的英文名称为(phenylphosphoryl)bis(mesitylmethanone)]。
关于上述化合物及其结构衍生物的制备方法，文献已有较多披露，典型的例如专利CN101830931和PCT2006056541。这些技术路线可以经由其关键起始原料清晰地加以区分为两类。
其一是以均三甲苯基苯甲酸或其相应的酰氯为关键起始原料，经由均三甲苯基苯甲酰氯和二苯基烷氧基膦的Arbuzov反应制备(二苯膦氧基)(均三甲苯基)甲酮。这个工艺在酰氯制备过程中释放大量盐酸酸气和二氧化硫，在后一步反应中释放大量污染大气且对臭氧层有显著破坏作用的氯代烷烃，例如氯甲烷或氯乙烷，因而环保压力巨大。二苯基烷氧基膦通常由二苯基氯化膦和相应的脂肪醇在碱作用下缩合制备，近年来为了消除高挥发性氯甲烷或氯乙烷的 排放压力，有使用长链脂肪醇例如丁醇的改进，由此生成的氯丁烷是液体从而可以较方便地实施回收，然而由于长链造成空间位阻较大，反应很难彻底，从而直接造成(二苯膦氧基)(均三甲苯基)甲酮产物纯度难以经济地保证和提高。在制备(苯膦氧基)双(均三甲苯基甲酮)的工艺中，均三甲苯基苯甲酰氯也是关键起始原料，同样存在大量盐酸酸气和难以碱液吸收的二氧化硫气体排放的环保问题。
其二是以均三甲苯基苯甲醛为关键起始原料，经由均三甲苯基苯甲醛和二苯基氧化膦Ph2P(O)H的羰基加成反应至得相应的膦氧醇中间体，然后用氧化剂氧化该中间体得到(二苯膦氧基)(均三甲苯基)甲酮目标产物。鉴于该膦氧醇结构的特殊性和空间位阻，目前被发现有效的氧化剂局限于重金属类，包括含Mo，W或V的金属盐，例如双乙酰丙酮氧化钒，鉬酸酐，鉬酸盐，磷鉬酸盐，钨酸酐，钨酸盐，或含有这些金属的杂多酸或杂多酸盐的一种或多种。因此重金属污染造成的环保风险仍然相当显著。
上述两种路线中的关键起始原料不管是均三甲苯基苯甲酸或其相应酰氯，还是均三甲苯基苯甲醛，均由均三甲苯在压力条件下制备得到。因此探索新的相比上述原料更经济的关键原料和工艺来制备(二苯膦氧基)(均三甲苯基)甲酮或(苯膦氧基)双(均三甲苯基甲酮)，同时避免排放臭氧破坏性氯代烃或重金属化合物，具有重要的经济和社会价值。
【发明内容】
本项申请现已首次发现(二苯膦氧基)(均三甲苯基)甲酮和(苯膦氧基)双(均三甲苯基甲酮)化合物可以以1，3，5-三甲基-2-三氯甲基-苯及相应的有机膦前体为关键原材料制备。
具体地，对化合物(二苯膦氧基)(均三甲苯基)甲酮的制备可用下述反应通式描述。该工艺的本质特征在于使用1，3，5-三甲基-2-三氯甲基-苯和通式为Ph2PM的试剂(其中M是H，Li，Na，或K)为关键限定性原材料，经由二者缩合制得相应的氯代膦中间体，再用氧化剂氧化该氯代膦后水解的方式制备(二苯膦氧基)(均三甲苯基)甲酮。合适的氧化剂包括过氧化氢，空气，氧气，叔丁醇过氧化氢，过氧乙酸等。Ph2PM试剂可以方便地由二苯基氯化膦和水(当M是氢时)或二苯基氯化膦和碱金属(当M是锂，钠，或钾)原位反应制备。当M是氢时，缩合需要适当的碱促进剂，合适的碱促进剂可以是有机胺(例如三乙胺，吡啶等)或无机碱(例如氢氧化钠，碳酸钠，碳酸钾，氢 氧化钾等)。该工艺路线权利要求的核心特征是以1，3，5-三甲基-2-三氯甲基-苯和通式为Ph2PM的有机膦前体为实质限定性反应原料，而无论这两种原料是以单独制备的纯化合物还是自相应原料原位制备的未经分离纯化的中间体形式参与所示反应。
关键原材料1，3，5-三甲基-2-三氯甲基-苯可以经由均三甲苯和四氯化碳在三氯化铝催化下的傅-克烷基化反应制备；而关键原材料Ph2PM可以参照文献步骤制备，例如：E.A.Mintz，et.al.J.Org.Chem.1988，53，4417；J.S.Filippo Jr，et.al.J.Org.Chem.1979，44，2705；I.P.Smoliakova，et.al.Organometallics，2009，68，2546等。
具体地，对化合物(二苯膦氧基)(均三甲苯基)甲酮的另一条制备路线可用下述反应通式描述。该工艺的本质特征在于使用1，3，5-三甲基-2-三氯甲基-苯和通式为Ph2P(O)M(其中M是H，Li，Na，或K)为关键限定性原材料，经由二者缩合制得相应的氯代膦氧中间体，该氯代膦氧原位水解即可制得(二苯膦氧基)(均三甲苯基)甲酮。当M是氢时，缩合需要适当的碱促进剂，合适的碱促进剂可以是有机胺(例如三乙胺，吡啶等)或无机碱(例如氢氧化钠，碳酸钠，碳酸钾，氢氧化钾等)。该工艺路线权利要求的核心特征是以1，3，5-三甲基-2-三氯甲基-苯和通式为Ph2P(O)M的有机膦前体为实质限定性反应原料，而无论这两种原料是以单独制备的纯化合物还是自相应原料原位制备的未经分离纯化的中间体形式参与所示反应。关键原材料1，3，5-三甲基-2-三氯甲基-苯可以经由均三甲苯和四氯化碳在三氯化铝催化下的傅-克烷基化反应制备；而关键原材料Ph2P(O)M可以参照文献步骤制备，例如专利WO8904315。
具体地，对化合物(苯膦氧基)双(均三甲苯基甲酮)的制备可用下述反应通式描述。该工艺的本质特征在于使用1，3，5-三甲基-2-三氯甲基-苯和通式为PhPM2(其中M是H，Li，Na，或K)的试剂为关键限定性原材料，经由二者缩合制得相应的双氯代膦中间体，再用氧化剂氧化该双氯代膦后水解的方式制备(苯膦氧基)双(均三甲苯基甲酮)。合适的氧化剂包括过氧化氢，空气，氧气，叔丁醇过氧化氢，过氧乙酸等。当M是氢时，缩合可以适当的使用碱促进剂，合适的碱促进剂可以是有机胺(例如三乙胺，吡啶等)或无机碱(例如氢氧化钠，碳酸钠，碳酸钾，氢氧化钾等)。该工艺路线权利要求的核心特征是以1，3，5-三甲基-2-三氯甲基-苯和通式为PhPM2的有机膦前体为实质限定性反应原料，而无论这两种原料是以单独制备的纯化合物还是自相应原料原位制备的未经分离纯化的中间体形式参与所示反应。
关键原材料1，3，5-三甲基-2-三氯甲基-苯可以经由均三甲苯和四氯化碳在三氯化铝催化下的傅-克烷基化反应制备；而关键原材料PhPM2可以参照文献步骤制备，例如专利CN1823077和WO2006/056541。
与已知文献方法相比，该工艺无论从原材料成本，反应操作简单性，还是反应条件的温和程度，以及环境友好性等方面考量均具有显著的优势和经济竞争力。
【具体实施方式】
下面结合具体实施例进一步说明本工艺流程。
目标化合物(二苯膦氧基)(均三甲苯基)甲酮的制备(路线一)：
1，3，5-三甲基-2-三氯甲基-苯的合成：室温下在一个反应瓶中混合1.82升四氯化碳和2.5千克无水AlCl3，有效机械搅拌下于一小时内滴加1.5千克均三甲苯(即1，3，5-三甲基苯)，反应体系立即呈现深红色并释放出盐酸气体(注意吸收酸气)，加毕在45摄氏度继续搅拌2小时，反应液徐徐倾倒入等体积1N冰盐酸里，分离有机相，用等体积二氯甲烷萃取2次，合并有机相，无水硫酸钠干燥，过滤，浓缩，油状残液减压蒸馏得到无色1，3，5-三甲基-2-三氯甲基-苯液体，收率约95％。
核磁共振数据：1H-NMR(CDCl3，500MHz)：6.88(s，2H)，2.74(s，6H)，2.25ppm(s，3H)；13C-NMR(CDCl3，125MHz)：139.1，138.1，136.7，132.5，98.3，25.6，20.5ppm。
在氮气保护下将31.6克金属锂和2升新鲜蒸馏的四氢呋喃混合，升温并维持反应温度在35摄氏度，缓缓滴加416克二苯基氯化膦，滴毕搅拌过夜，核磁共振分析反应已经完全。将448克1，3，5-三甲基-2-三氯甲基-苯用0.5升四氢呋喃稀释后缓缓加入，反应在室温下继续搅拌至TLC检测反应结束，滤除部分生成的固体不溶物后，溶液减压回收溶剂。残余物和3升甲苯混合，机械搅拌下加入30％过氧化氢溶液，检测反应进程直至氧化完全。反应液和等体积的碳酸氢钠饱和溶液混合，机械搅拌2小时，分离有机相后干燥，旋蒸回收甲苯溶剂后得(二苯膦氧基)(均三甲苯基)甲酮粗品可重结晶精制，产率84％。
目标化合物(二苯膦氧基)(均三甲苯基)甲酮的制备(路线二)：
将125克二苯基氧膦溶解在2升无水四氢呋喃里，冰水浴冷却后向其缓慢滴加一当量的丁基锂，溶液由无色变为红棕色，滴毕搅拌半小时，将150克的1，3，5-三甲基-2-三氯甲基-苯的1升四氢呋喃溶液缓慢加入，溶液红棕色缓慢褪去，反应继续搅拌半小时，TLC检测反应结束，加入2升碳酸氢钠饱和溶液，用5升乙酸乙酯萃取，有机相干燥，旋蒸除去溶剂后得到(二苯膦氧基)(均三甲苯基)甲酮产品，产率87％。
目标化合物(苯膦氧基)双(均三甲苯基甲酮)的制备(路线三)：
参照文献CN1823077步骤，经由23克金属钠和44.9克苯基二氯化膦在1升甲苯中制得苯基二钠化膦后，向其缓缓加入120克经100毫升甲苯稀释的1，3，5-三甲基-2-三氯甲基-苯液体，加毕搅拌反应直至TLC检测反应终止。向反应混合体系分小批加入90克的30％过氧化氢溶液，检测反应进程直至氧化完全。反应液和等体积的碳酸氢钠饱和溶液混合，机械搅拌2小时，分离有机相后干燥，旋蒸回收甲苯溶剂后得到的淡黄色粗品用适量石油醚洗涤即为目标产物(苯膦氧基)双(均三甲苯基甲酮)，产率78％。
Claims (3)
1.结构式如下的商用芳香酮化合物(二苯膦氧基)(均三甲苯基)甲酮的制备方法，该工艺的本质特征在于使用1，3，5-三甲基-2-三氯甲基-苯和通式为Ph2PM的试剂为关键限定性原材料，其中M是Li，Na，或K，经由二者缩合制得相应的氯代膦中间体，再用氧化剂氧化该氯代膦后水解的方式制备(二苯膦氧基)(均三甲苯基)甲酮；氧化剂包括过氧化氢，叔丁醇过氧化氢，过氧乙酸；Ph2PM试剂由二苯基氯化膦和碱金属原位反应制备；该工艺路线权利要求的核心特征是以1，3，5-三甲基-2-三氯甲基-苯和通式为Ph2PM的有机膦前体为实质限定性反应原料，而无论这两种原料是以单独制备的纯化合物还是自相应原料原位制备的未经分离纯化的中间体形式参与所示反应
2.结构式如下的商用芳香酮化合物(二苯膦氧基)(均三甲苯基)甲酮的制备方法，该工艺的本质特征在于使用1，3，5-三甲基-2-三氯甲基-苯和通式为Ph2P(O)M为关键限定性原材料，其中M是Li，Na，或K，经由二者缩合制得相应的氯代膦氧中间体，该氯代膦氧原位水解即可制得(二苯膦氧基)(均三甲苯基)甲酮；该工艺路线权利要求的核心特征是以1，3，5-三甲基-2-三氯甲基-苯和通式为Ph2P(O)M的有机膦前体为实质限定性反应原料，而无论这两种原料是以单独制备的纯化合物还是自相应原料原位制备的未经分离纯化的中间体形式参与所示反应
3.结构式如下的商用芳香酮化合物(苯膦氧基)双(均三甲苯基甲酮)的制备方法，该工艺的本质特征在于使用1，3，5-三甲基-2-三氯甲基-苯和通式为PhPM2的试剂为关键限定性原材料，其中M是Li，Na，或K，经由二者缩合制得相应的双氯代膦中间体，再用氧化剂氧化该双氯代膦后水解的方式制备(苯膦氧基)双(均三甲苯基甲酮)；氧化剂包括过氧化氢，叔丁醇过氧化氢，过氧乙酸；该工艺路线权利要求的核心特征是以1，3，5-三甲基-2-三氯甲基-苯和通式为PhPM2的有机膦前体为实质限定性反应原料，而无论这两种原料是以单独制备的纯化合物还是自相应原料原位制备的未经分离纯化的中间体形式参与所示反应
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