CN108912171A - The synthetic method of 4- dimethylamino benzoyl diphenyl phosphine oxide or 4- di-n-hexyl amino benzoyl diphenyl phosphine oxide - Google Patents
The synthetic method of 4- dimethylamino benzoyl diphenyl phosphine oxide or 4- di-n-hexyl amino benzoyl diphenyl phosphine oxide Download PDFInfo
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- CN108912171A CN108912171A CN201810639220.7A CN201810639220A CN108912171A CN 108912171 A CN108912171 A CN 108912171A CN 201810639220 A CN201810639220 A CN 201810639220A CN 108912171 A CN108912171 A CN 108912171A
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- Prior art keywords
- reaction
- phosphine oxide
- mmol
- diphenyl phosphine
- compound
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- ATYJNUPYAOFIAK-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-diphenylphosphorylmethanone Chemical compound CN(C)c1ccc(cc1)C(=O)P(=O)(c1ccccc1)c1ccccc1 ATYJNUPYAOFIAK-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 180
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 144
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 108
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 80
- 239000000047 product Substances 0.000 claims description 77
- 230000015572 biosynthetic process Effects 0.000 claims description 51
- 238000003786 synthesis reaction Methods 0.000 claims description 51
- 238000000926 separation method Methods 0.000 claims description 39
- 238000004440 column chromatography Methods 0.000 claims description 38
- 238000004458 analytical method Methods 0.000 claims description 34
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 33
- 235000019394 potassium persulphate Nutrition 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- WQBCAASPALGAKX-UHFFFAOYSA-N Benzenemethanol, 4-(dimethylamino)- Chemical compound CN(C)C1=CC=C(CO)C=C1 WQBCAASPALGAKX-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- QTQUJRIHTSIVOF-UHFFFAOYSA-N amino(phenyl)methanol Chemical compound NC(O)C1=CC=CC=C1 QTQUJRIHTSIVOF-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 35
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 abstract description 21
- -1 Aryl carbinol derivatives Chemical class 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000002390 adhesive tape Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229910052703 rhodium Inorganic materials 0.000 abstract description 2
- 239000010948 rhodium Substances 0.000 abstract description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000004809 thin layer chromatography Methods 0.000 description 35
- 238000005160 1H NMR spectroscopy Methods 0.000 description 33
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 9
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 description 8
- 235000019445 benzyl alcohol Nutrition 0.000 description 8
- 229960004217 benzyl alcohol Drugs 0.000 description 8
- PTMBWNZJOQBTBK-UHFFFAOYSA-N pyridin-4-ylmethanol Chemical compound OCC1=CC=NC=C1 PTMBWNZJOQBTBK-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 5
- MBYQPPXEXWRMQC-UHFFFAOYSA-N (2-chlorophenyl)methanol Chemical compound OCC1=CC=CC=C1Cl MBYQPPXEXWRMQC-UHFFFAOYSA-N 0.000 description 4
- ZSRDNPVYGSFUMD-UHFFFAOYSA-N (3-chlorophenyl)methanol Chemical compound OCC1=CC=CC(Cl)=C1 ZSRDNPVYGSFUMD-UHFFFAOYSA-N 0.000 description 4
- GEZMEIHVFSWOCA-UHFFFAOYSA-N (4-fluorophenyl)methanol Chemical compound OCC1=CC=C(F)C=C1 GEZMEIHVFSWOCA-UHFFFAOYSA-N 0.000 description 4
- VEDDBHYQWFOITD-UHFFFAOYSA-N para-bromobenzyl alcohol Chemical compound OCC1=CC=C(Br)C=C1 VEDDBHYQWFOITD-UHFFFAOYSA-N 0.000 description 4
- KORIJXKQGMTQTO-UHFFFAOYSA-N 1h-pyrrol-2-ylmethanol Chemical compound OCC1=CC=CN1 KORIJXKQGMTQTO-UHFFFAOYSA-N 0.000 description 3
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical class OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 description 3
- HZGCZRCZOMANHK-UHFFFAOYSA-N pyrimidin-2-ylmethanol Chemical compound OCC1=NC=CC=N1 HZGCZRCZOMANHK-UHFFFAOYSA-N 0.000 description 3
- HREHOXSRYOZKNT-UHFFFAOYSA-N quinolin-2-ylmethanol Chemical compound C1=CC=CC2=NC(CO)=CC=C21 HREHOXSRYOZKNT-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LODDFDHPSIYCTK-UHFFFAOYSA-N (2,4,6-trimethylphenyl)methanol Chemical class CC1=CC(C)=C(CO)C(C)=C1 LODDFDHPSIYCTK-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- KTLIMPGQZDZPSB-UHFFFAOYSA-M diethylphosphinate Chemical compound CCP([O-])(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-M 0.000 description 2
- GOJNABIZVJCYFL-UHFFFAOYSA-M dimethylphosphinate Chemical compound CP(C)([O-])=O GOJNABIZVJCYFL-UHFFFAOYSA-M 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZPHGMBGIFODUMF-UHFFFAOYSA-N thiophen-2-ylmethanol Chemical compound OCC1=CC=CS1 ZPHGMBGIFODUMF-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PBLNHHSDYFYZNC-UHFFFAOYSA-N (1-naphthyl)methanol Chemical compound C1=CC=C2C(CO)=CC=CC2=C1 PBLNHHSDYFYZNC-UHFFFAOYSA-N 0.000 description 1
- WYLYBQSHRJMURN-UHFFFAOYSA-N (2-methoxyphenyl)methanol Chemical compound COC1=CC=CC=C1CO WYLYBQSHRJMURN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- 125000001999 4-Methoxybenzoyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C(*)=O 0.000 description 1
- WDDZWGBIZWBYGS-UHFFFAOYSA-N CO.[N+](=O)([O-])C1=CC=C(C(=O)C2=CC=CC=C2)C=C1 Chemical compound CO.[N+](=O)([O-])C1=CC=C(C(=O)C2=CC=CC=C2)C=C1 WDDZWGBIZWBYGS-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- FTFHSGKASINZBY-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanol Chemical compound NCC1=CC=CC=C1CO FTFHSGKASINZBY-UHFFFAOYSA-N 0.000 description 1
- KCTYUINIEPILPS-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanol Chemical compound NCC1=CC=CC(CO)=C1 KCTYUINIEPILPS-UHFFFAOYSA-N 0.000 description 1
- WMOUKOAUAFESMR-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanol Chemical compound NCC1=CC=C(CO)C=C1 WMOUKOAUAFESMR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VEIHOXBXWMAUNZ-UHFFFAOYSA-N bis(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)C1=CC=C(C)C(C)=C1C VEIHOXBXWMAUNZ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 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 description 1
- KJXMHAKLXQDNFB-UHFFFAOYSA-N diphenylphosphoryl-(4-methylphenyl)methanone Chemical compound C1=CC(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 KJXMHAKLXQDNFB-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- VBWFYEFYHJRJER-UHFFFAOYSA-N methyl 4-(hydroxymethyl)benzoate Chemical compound COC(=O)C1=CC=C(CO)C=C1 VBWFYEFYHJRJER-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical class COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- XYORSKKUGAGNPC-UHFFFAOYSA-N phosphonocarbonylphosphonic acid Chemical class OP(O)(=O)C(=O)P(O)(O)=O XYORSKKUGAGNPC-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5333—Arylalkane phosphine oxides or thioxides
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/60—Quinoline or hydrogenated quinoline ring systems
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses the synthetic methods of a kind of 4- dimethylamino benzoyl diphenyl phosphine oxide or 4- di-n-hexyl amino benzoyl diphenyl phosphine oxide.The present invention uses（It is miscellaneous）Aryl carbinol derivatives are starting material, and raw material is easy to get, and there are many type；The product types multiplicity obtained using the method for the present invention, it is widely used, it is coordinated as ligand and rhodium for catalyzing and synthesizing all kinds of aldehyde；Phosphono replaces（It is miscellaneous）Aryl methanol is converted into phosphono base class compound in which can be convenient, such compound is as photoinitiator, in the production that can be widely used for high molecular material, coating, adhesive and adhesive tape etc..In addition, method disclosed by the invention, reaction carries out in air, reaction condition is mild, target product high income, the small, operation of pollution and last handling process are simple, is suitable for industrialized production.
Description
The present invention be a kind of entitled phosphono replace carbinol derivatives and the preparation method and application thereof, application No. is
201610813032.2, the applying date is the divisional application of the patent application on the 9th of September in 2016, belongs to derivative preparation part.
Technical field
The invention belongs to the preparation technical fields of organic compound, and in particular to a kind of 4- dimethylamino benzoyl hexichol
The synthetic method of phosphine oxide or 4- di-n-hexyl amino benzoyl diphenyl phosphine oxide.
Background technique
In in the past few decades, people replace the relevant report of carbinol derivatives few phosphono；Phosphono replaces
Methanol（1）And its derivative can be used as ligand, in the hydroformylation reaction of rhodium catalysis.Hydroformylation reaction is industrial
The essential industry method of aldehyde is synthesized from common raw material of industry alkene, carbon monoxide and hydrogen.Aldehyde can further add
Work is alcohol, acid and its derivative, and the latter is made extensively as plasticizer, fabric additive, surfactant, solvent and fragrance etc.
For in industrial production and daily life（Referring to:Clark H J, Wang R, Alper H.The Journal of Organic Chemistry, 2002, 67, 6224）.
Meanwhile phosphono replaces（It is miscellaneous）It is derivative that aryl carbinol derivatives can easily be converted into phosphono aryl ketone
Object can be used as a photoinitiator, be widely used in the production of coating, adhesive, adhesive tape and high molecular material etc..1997
Year, the prior art reports diphenyl phosphine oxide base trimethylphenyl ketone as photoinitiator, can be used for causing free radical polymerization,
One of most widely used photoinitiator in polymerization reaction is become.So far, a variety of diphenyl phosphine oxide base aryl ketones are as light
Initiator is used in the synthesis of various high molecular materials.
Existing phosphono replaces the synthesis of carbinol derivatives to be all to react to obtain by aldehyde and phosphorus reagent, needs to use aldehyde,
Aldehyde has the taste stimulated very much, will cause biggish injury to operator and environment；Aldehyde is oxidized easily simultaneously, increases storage
Difficulty and cost.Therefore find that a kind of raw material sources are simple, meet Green Chemistry and require, reaction condition is mild, it is easy to operate,
The good preparation method of universality replaces carbinol derivatives necessary effectively to synthesize phosphono.
Summary of the invention
The object of the present invention is to provide a kind of methods for preparing phosphono and replacing carbinol derivatives, with raw material sources letter
Singly, the advantages that reaction condition is mild, reaction process is environmentally protective, post-processing is simple, yield is high.
To achieve the above object of the invention, the technical solution adopted by the present invention is that：It is a kind of to prepare phosphono substitution methanol derivative
The method of object, includes the following steps：Carbinol derivatives, phosphorus reagent, potassium peroxydisulfate are dissolved in solvent, it is anti-at room temperature ~ 100 DEG C
It answers, obtains phosphono and replace carbinol derivatives；
The carbinol derivatives are as shown in following general formula of the chemical structure：
Wherein Ar is selected from one of following general formula：：
Wherein R is selected from：One of alkyl, aryl, alkoxy, halogen, nitro, ester group, pyridyl group；X is selected from：O, in S, N
It is a kind of；
The phosphorus reagent is as shown in following general formula of the chemical structure：
Wherein R1Selected from one of following group：
The phosphono replaces carbinol derivatives as shown in following general formula of the chemical structure：
The solvent is selected from：Methanol, ethyl alcohol, acetonitrile, acetone, ethyl acetate, water, 1,2- dichloroethanes, toluene, N, N- dimethyl
One of formamide.
In above-mentioned technical proposal, the carbinol derivatives are selected from:Benzylalcohol, 2- chlorobenzyl alcohol, 3- chlorobenzyl alcohol, 4- chlorobenzyl alcohol, 4-
Bromobenzyl alcohol, 4- fluoro benzyl alcohol, 2- xylyl alcohol, 3- xylyl alcohol, 4- xylyl alcohol, 2- methoxyl group benzylalcohol, 4- methoxyl group benzylalcohol, 4-
Methyl hydroxy-benzoate, 4- nitrobenzyl alcohol, 2- pyridinemethanol, 4- pyridinemethanol, 1- naphthalene methanol, 2- hydroxymethylfurans, 2- hydroxyl
One of methylthiophene, 2- hydroxymethylpyrrol, 2- hydroxymethylpyrimidine, 2- hydroxymethyl quinoline；The phosphorus reagent is selected from:Diformazan
Base phosphite ester, diethyl phosphite, diphenyl phosphine oxide, two（4- methoxyphenyl）Phosphine oxide, two（4- cyano-phenyl）In phosphine oxide
One kind.
In above-mentioned technical proposal, thin-layer chromatography is utilized（TLC）Tracking reaction is until be fully completed.
In above-mentioned technical proposal, in molar ratio,（It is miscellaneous）Aryl carbinol derivatives: phosphorus reagent: potassium peroxydisulfate is（1~3）:（1~
3）:（1~3）.
In above-mentioned technical proposal, column chromatography for separation purification processes are carried out to product after reaction.
The present invention further discloses the phosphonos for the preparation method preparation for replacing carbinol derivatives according to above-mentioned phosphono
Replace carbinol derivatives, aldehyde derivatives can be prepared by hydrolysis, therefore the present invention further discloses the substitutions of above-mentioned phosphono
Carbinol derivatives are preparing the application in phosphono aldehyde derivatives；Phosphono of the invention simultaneously replaces carbinol derivatives that can turn
Phosphono ketone derivatives are turned to, therefore the present invention further discloses above-mentioned phosphonos, and carbinol derivatives to be replaced to prepare phosphono
Application in base aldehyde derivatives.
The invention also discloses above-mentioned phosphonos, and carbinol derivatives to be replaced to prepare plasticizer, photoinitiator, surface-active
Application in agent.Product structure multiplicity of the invention, can directly use, it is particularly possible to further react and obtain as intermediate
Downstream compound has expanded the application of organic compound significantly.
The reaction process of above-mentioned technical proposal is represented by：
Due to the application of the above technical scheme, the present invention has following advantages compared with prior art:
1, the present invention is starting material using 01 derivatives, and product phosphono is prepared in the presence of phosphorus reagent, potassium peroxydisulfate for the first time
Base replaces carbinol derivatives；Have the advantages that raw material is easy to get, toxicity is low, low in cost, product structure type is more.
2, the phosphono disclosed by the invention for preparing replaces the method for carbinol derivatives using 01 derivatives as starting material, and alcohol is derivative
Object is small on operator and environment influence, and convenient for storage；Solve that prior art material toxicity is big, be not easy to store lacks
It falls into.
3, the phosphono disclosed by the invention for preparing replaces in the method for carbinol derivatives, and reaction carries out in air, reacts
Mild condition, the reaction time is short, and the high income of target product, operation and last handling process are simple, product structure multiplicity, can
Directly to use, it is particularly possible to further be reacted as intermediate and obtain downstream compound, expand organic compound significantly
Using being suitable for industrialized production.
Specific embodiment
The present invention will be further described below with reference to examples：
Embodiment one：The synthesis of diphenyl phosphine oxide base benzyl alcohol
Using benzylalcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
Benzylalcohol is added in reaction flask（0.054 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5 mmol）, over cure
Sour potassium（0.270 g, 1.0 mmol）And methanol（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 76%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ 7.97 - 7.72 (m, 4H),
7.64 – 7.37 (m, 6H), 7.34 – 7.09 (m, 5H), 6.55 (d, J = 17.1 Hz, 1H), 5.64 (s,
1H).The product can be used for the formylation reaction of alkene as ligand in the industrial production.
Embodiment two：The synthesis of diphenyl phosphine oxide base (2- chlorphenyl) methanol
Using 2- chlorobenzyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- chlorobenzyl alcohol is added in reaction flask（0.143 g, 1.0 mmol）, diphenyl phosphine oxide（0.101 g, 0.5 mmol）,
Potassium peroxydisulfate（0.270 g, 1.0 mmol）And ethyl alcohol（2 mL）, 30 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 73%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.81 (dd, J = 11.2,
7.7 Hz, 2H), 7.74 (dd, J = 11.5, 7.7 Hz, 2H), 7.64 – 7.44 (m, 6H), 7.35 –
7.14 (m, 4H), 6.70 (dd, J = 18.3, 5.8 Hz, 1H), 5.96 (t, J = 6.1 Hz, 1H).
Embodiment three：The synthesis of diphenyl phosphine oxide base (3- chlorphenyl) methanol
Using 3- chlorobenzyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
3- chlorobenzyl alcohol is added in reaction flask（0.214 g, 1.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5 mmol）,
Potassium peroxydisulfate（0.270 g, 1.0 mmol）And water（2 mL）, 40 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 75%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.91 – 7.75 (m, 4H),
7.64 – 7.44 (m, 6H), 7.36 – 7.12 (m, 4H), 6.65 (dt, J = 24.7, 12.3 Hz, 1H),
5.70 (t, J = 6.7 Hz, 1H).
Example IV：The synthesis of diphenyl phosphine oxide base (4- chlorphenyl) methanol
Using 4- chlorobenzyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- chlorobenzyl alcohol is added in reaction flask（0.071 g, 0.5 mmol）, diphenyl phosphine oxide（0.202 g, 1.0 mmol）,
Potassium peroxydisulfate（0.270 g, 1.0 mmol）And ethyl acetate（2 mL）, 50 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 80%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.86 – 7.77 (m, 4H),
7.58 – 7.44 (m, 6H), 7.33 – 7.19 (m, 4H), 6.61 (dd, J = 17.4, 5.8 Hz, 1H),
5.68 (t, J = 6.5 Hz, 1H).
Embodiment five：The synthesis of diphenyl phosphine oxide base (2- aminomethyl phenyl) methanol
Using 2- xylyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- xylyl alcohol is added in reaction flask（0.061 g, 0.5 mmol）, diphenyl phosphine oxide（0.303 g, 1.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And acetone（2 mL）, 50 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 83%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.91 – 7.75 (m, 4H),
7.62 – 7.53 (m, 2H), 7.52 – 7.46 (m, 4H), 7.14 – 7.03 (m, 3H), 7.01 – 6.89
(m, 1H), 6.43 (dd, J = 20.2, 5.2 Hz, 1H), 5.78 (dd, J = 7.9, 5.3 Hz, 1H),
2.29 (s, 3H).
Embodiment six：The synthesis of diphenyl phosphine oxide base (4- aminomethyl phenyl) methanol
Using 4- xylyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- xylyl alcohol is added in reaction flask（0.061 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.135 g, 0.5 mmol）And acetonitrile（2 mL）, 60 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 71%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.89 – 7.70 (m, 4H),
7.61 – 7.38 (m, 6H), 7.14 (d, J = 7.0 Hz, 2H), 7.00 (d, J = 7.6 Hz, 2H), 6.44
(dd, J = 17.7, 5.7 Hz, 1H), 5.58 (t, J = 6.0 Hz, 1H), 2.22 (s, 3H).
Embodiment seven：The synthesis of diphenyl phosphine oxide base (3- aminomethyl phenyl) methanol
Using 3- xylyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
3- xylyl alcohol is added in reaction flask（0.061 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.405 g, 1.5 mmol）With 1,2- dichloroethanes（2 mL）, 70 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 82%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.90 -7.70 (m, 4H),
7.60 – 7.39 (m, 6H), 7.13 – 6.90 (m, 4H), 6.44 (dd, J = 17.8, 5.6 Hz, 1H),
5.56 (t, J = 6.2 Hz, 1H), 2.17 (s, 3H).
Embodiment eight：The synthesis of diphenyl phosphine oxide base (4- methoxyphenyl) methanol
Using 4- methoxyl group benzylalcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- methoxyl group benzylalcohol is added in reaction flask（0.069 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And toluene（2 mL）, 80 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 83%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.82 (dd, J = 18.1,
9.8 Hz, 4H), 7.59 – 7.41 (m, 6H), 7.18 (d, J = 7.7 Hz, 2H), 6.77 (d, J = 8.2
Hz, 2H), 6.42 (dd, J = 17.7, 5.6 Hz, 1H), 5.58 (t, J = 5.5 Hz, 1H), 3.70 (s,
3H).
Embodiment nine：The synthesis of diphenyl phosphine oxide base (2- methoxyphenyl) methanol
Using 2- methoxyl group benzylalcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- methoxyl group benzylalcohol is added in reaction flask（0.069 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, 90 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 79%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.86 – 7.70 (m, 2H),
7.67 – 7.46 (m, 6H), 7.44 – 7.36 (m, 2H), 7.28 (d, J = 7.6 Hz, 1H), 7.18 (t,J = 7.8 Hz, 1H), 6.84 (t, J = 7.4 Hz, 1H), 6.79 (d, J = 8.3 Hz, 1H), 6.28
(dd, J = 16.1, 6.3 Hz, 1H), 5.96 (dd, J = 6.1, 4.2 Hz, 1H), 3.47 (s, 3H).
Embodiment ten：The synthesis of diphenyl phosphine oxide base (4- nitrobenzophenone) methanol
Using 4- nitrobenzyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- nitrobenzyl alcohol is added in reaction flask（0.076 g, 0.5 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, 100 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 71%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ8.08 (d, J = 8.6 Hz,
2H), 7.85 (dd, J = 10.8, 7.1 Hz, 2H), 7.78 (dd, J = 10.5, 7.2 Hz, 2H), 7.61 –
7.44 (m, 8H), 6.85 (dd, J = 17.0, 5.8 Hz, 1H), 5.88 (dd, J = 9.4, 5.9 Hz,
1H).
Embodiment 11：The synthesis of diphenyl phosphine oxide base (4- bromophenyl) methanol
Using 4- bromobenzyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- bromobenzyl alcohol is added in reaction flask（0.093 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And ethyl alcohol（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 86%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.81 (dd, J = 17.5,
7.1 Hz, 4H), 7.60 – 7.44 (m, 6H), 7.40 (d, J = 8.2 Hz, 2H), 7.19 (d, J = 7.0
Hz, 2H), 6.61 (dd, J = 17.4, 5.8 Hz, 1H), 5.66 (t, J = 6.6 Hz, 1H).
Embodiment 12：The synthesis of diphenyl phosphine oxide base (4- fluorophenyl) methanol
Using 4- fluoro benzyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- fluoro benzyl alcohol is added in reaction flask（0.063 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And ethyl alcohol（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 77%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.83 (dd, J = 9.5,
8.3 Hz, 2H), 7.77 (dd, J = 9.6, 8.3 Hz, 2H), 7.64 – 7.43 (m, 6H), 7.25 (t, J
= 6.7 Hz, 2H), 7.05 (dd, J = 16.6, 8.7 Hz, 2H), 6.58 (dd, J = 17.7, 5.9 Hz,
1H), 5.83 (t, J = 6.0 Hz, 1H).
Embodiment 13：The synthesis of diphenyl phosphine oxide base (4- methoxycarbonyl-phenyl) methanol
Using 4- methyl hydroxy-benzoate, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- methyl hydroxy-benzoate is added in reaction flask（0.083 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g,
0.75 mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the petroleum ether obtained after reaction:Ethyl acetate=4:1) target product, is obtained
（Yield 74%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.87 – 7.73 (m, 6H),
7.60 – 7.33 (m, 8H), 6.68 (dd, J = 17.3, 5.7 Hz, 1H), 5.75 (dd, J = 7.7, 6.3
Hz, 1H), 3.81 (s, 3H).
Embodiment 14：The synthesis of diphenyl phosphine oxide base (pyridine -2- base) methanol
Using 2- pyridinemethanol, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- pyridinemethanol is added in reaction flask（0.544 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 71%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ8.35 (d, J = 4.3 Hz,
1H), 7.84 – 7.74 (m, 4H), 7.70 (td, J = 7.7, 1.4 Hz, 1H), 7.59 – 7.43 (m,
6H), 7.36 (d, J = 7.8 Hz, 1H), 7.25 – 7.18 (m, 1H), 6.45 (dd, J = 13.8, 6.1
Hz, 1H), 5.72 (t, J = 5.8 Hz, 1H).
Embodiment 15：The synthesis of diphenyl phosphine oxide base (pyridin-4-yl) methanol
Using 4- pyridinemethanol, diphenyl phosphine oxide as raw material, reaction step is as follows：
4- pyridinemethanol is added in reaction flask（0.544 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 71%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ8.46 – 8.30 (m, 2H),
7.89 – 7.73 (m, 4H), 7.62 – 7.43 (m, 6H), 7.28 – 7.16 (m, 2H), 6.77 (dd, J =
16.6, 5.7 Hz, 1H), 5.75 (dd, J = 9.1, 5.9 Hz, 1H).
Embodiment 16：The synthesis of diphenyl phosphine oxide base (naphthalene -2- base) methanol
Using β-naphthalene methanol, diphenyl phosphine oxide as raw material, reaction step is as follows：
β-naphthalene methanol is added in reaction flask（0.079 g, 0.5 mmol）, diphenyl phosphine oxide（0.152 g, 0.75
mmol）, potassium peroxydisulfate（0.270 g, 1.0 mmol）And N,N-dimethylformamide（2 mL）, 30 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 85%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ8.32 (d, J = 8.0 Hz,
1H), 7.93 – 7.82 (m, 4H), 7.78 (d, J = 8.0 Hz, 1H), 7.59 (t, J = 7.0 Hz, 1H),
7.54 – 7.37 (m, 8H), 7.32 (t, J = 7.7 Hz, 1H), 6.61 (dd, J = 19.0, 5.4 Hz,
1H), 6.49 – 6.40 (m, 1H).
Embodiment 17：The synthesis of diphenyl phosphine oxide base (furans -2- base) methanol
Using 2- hydroxymethylfurans, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethylfurans are added in reaction flask（0.078 g, 0.8 mmol）, diphenyl phosphine oxide（0.242 g, 1.2
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetonitrile（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 79%）.The analysis data of product are as follows： 1H NMR (400 MHz, CDCl3): δ 7.80 ( dd, J = 7.8
Hz, 4 H ), 7.55 (t, J = 7.6 Hz, 6 H), 7.23 (dd, J = 3.2 Hz, 1 H), 6.28 (dd, J
= 3.6 Hz, 1H), 6.21 (dd, J = 3.6 Hz, 1 H), 5.50 (d, J = 5.6 Hz, 1 H), 4.98
(s, 1 H).
Embodiment 18：The synthesis of diphenyl phosphine oxide base (thiophene -2- base) methanol
Using 2- hydroxymethyl thiophene, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethyl thiophene is added in reaction flask（0.090 g, 0.8 mmol）, diphenyl phosphine oxide（0.101 g, 0.5
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetonitrile（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 75%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ 7.94 – 7.75 (m,
4H), 7.62 – 7.42 (m, 6H), 7.36 (d, J = 4.3 Hz, 1H), 6.98 – 6.87 (m, 2H), 6.84
(dd, J = 16.3, 6.0 Hz, 1H), 5.90 (t, J = 6.1 Hz, 1H).
Embodiment 19：The synthesis of diphenyl phosphine oxide base (pyrroles -2- base) methanol
Using 2- hydroxymethylpyrrol, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethylpyrrol is added in reaction flask（0.078 g, 0.8 mmol）, diphenyl phosphine oxide（0.242 g, 1.2
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetonitrile（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 71%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ11.85 (s, 1H), 7.87 –
7.69 (m, 4H), 7.62 – 7.42 (m, 6H), 6.64 (d, J = 4.3 Hz, 1H), 6.11 (t, J = 6.1
Hz, 1H), 5.88 (d, J = 4.3 Hz, 1H), 5.84 (dd, J = 16.3, 6.0 Hz, 1H), 5.12 (t,J = 6.1 Hz, 1H).
Embodiment 20：The synthesis of diphenyl phosphine oxide base (pyrimidine -2-base) methanol
Using 2- hydroxymethylpyrimidine, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethylpyrimidine is added in reaction flask（0.088 g, 0.8 mmol）, diphenyl phosphine oxide（0.242 g, 1.2
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetone（2 mL）, 40 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 81%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ8.70 (d, J = 4.3 Hz,
2H), 7.84 – 7.74 (m, 4H), 7.59 – 7.43 (m, 6H), 7.39 (t, J = 6.1 Hz, 1H), 6.45
(dd, J = 13.8, 6.1 Hz, 1H), 5.72 (t, J = 5.8 Hz, 1H).
Embodiment 21：The synthesis of diphenyl phosphine oxide base (quinoline -2- base) methanol
Using 2- hydroxymethyl quinoline, diphenyl phosphine oxide as raw material, reaction step is as follows：
2- hydroxymethyl quinoline is added in reaction flask（0.127 g, 0.8 mmol）, diphenyl phosphine oxide（0.242 g, 1.2
mmol）, potassium peroxydisulfate（0.432 g, 1.6 mmol）And acetone（2 mL）, 40 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 76%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ8.16 (d, J = 8.0 Hz,
1H), 8.04 (d, J = 8.0 Hz, 1H), 7.86 – 7.63 (m, 6H), 7.58 – 7.43 (m, 7H), 7.30
(d, J = 8.0 Hz, 1H), 6.61 (dd, J = 19.0, 5.4 Hz, 1H), 6.49 (t, J = 5.8 Hz,
1H).
Embodiment 22：The synthesis of dimethoxyphosphinvl benzyl alcohol
Using benzylalcohol, dimethyl phosphinate as raw material, reaction step is as follows：
Benzylalcohol is added in reaction flask（0.086 g, 0.8 mmol）, dimethyl phosphinate（0.132g, 1.2 mmol）,
Potassium peroxydisulfate（0.648 g, 2.4 mmol）And acetone（2 mL）, 40 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 75%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.27-7.47 (m, 5H), 5.12
(s, 1H), 5.05 (d, J = 12 Hz, 1H), 3.64-3.72 (m, 6H).
Embodiment 23：The synthesis of diethoxy phosphinyl benzyl alcohol
Using benzylalcohol, diethyl phosphinate as raw material, reaction step is as follows：
Benzylalcohol is added in reaction flask（0.086 g, 0.8 mmol）, diethyl phosphinate（0.168,1.2 mmol）, mistake
Potassium sulfate（0.648 g, 2.4 mmol）And acetone（2 mL）, 40 DEG C of reactions；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 81%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.38-7.41 (m, 2H),
7.22-7.25 (m, 3H), 5.12 (s, 1H), 4.92 (d, J = 10 Hz, 1H), 3.90-3.98 (m, 4H),
1.08-1.19 (m, 6H).
Embodiment 24：Two（4- methoxyphenyl）Phosphinyl（4- chlorphenyl）The synthesis of methanol
With 4- chlorobenzyl alcohol, two（4- methoxyphenyl）For phosphine oxide as raw material, reaction step is as follows：
4- chlorobenzyl alcohol is added in reaction flask（0.114 g, 0.8 mmol）, two（4- methoxyphenyl）Phosphine oxide（0.314 g,
1.2 mmol）, potassium peroxydisulfate（0.648 g, 2.4 mmol）And acetone（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 87%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.77 (dd, J = 9.5,
8.3 Hz, 4H), 7.38 (d, J = 8.3 Hz, 2H), 7.22 (d, J = 8.3 Hz, 2H), 7.16 (dd, J
= 9.6, 8.3 Hz, 4H), 6.58 (dd, J = 17.7, 5.9 Hz, 1H), 5.83 (t, J = 6.0 Hz,
1H).
Embodiment 25：Two（4- cyano-phenyl）Phosphinyl（4- chlorphenyl）The synthesis of methanol
With 4- chlorobenzyl alcohol, two（4- cyano-phenyl）For phosphine oxide as raw material, reaction step is as follows：
4- chlorobenzyl alcohol is added in reaction flask（0.114 g, 0.8 mmol）, two（4- cyano-phenyl）Phosphine oxide（0.302 g,
1.2 mmol）, potassium peroxydisulfate（0.648 g, 2.4 mmol）And acetone（2 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
（Yield 84%）.The analysis data of product are as follows： 1H NMR (400 MHz, DMSO-d 6): δ7.83 (dd, J = 9.5,
8.3 Hz, 4H), 7.77 (dd, J = 9.6, 8.3 Hz, 4H), 7.38 (d, J = 6.7 Hz, 2H), 7.22
(d, J = 6.7 Hz, 2H), 6.58 (dd, J = 17.7, 5.9 Hz, 1H), 5.83 (t, J = 6.0 Hz,
1H).
Embodiment 26：The synthesis of 4- dimethylamino benzoyl diphenyl phosphine oxide
Using 4- dimethylaminobenzyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
The synthesis step of compound 26-2：
4- dimethylaminobenzyl alcohol is added in reaction flask（0.151 g, 1.0 mmol）, diphenyl phosphine oxide（0.304 g, 1.5
mmol）, potassium peroxydisulfate（0.540 g, 2.0 mmol）And acetone（5 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
26-2（Yield 82%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.30−7.82 (m, 10H),
7.03 (dd, J = 1.5, 2.0 Hz, 2H), 6.52 (d, J = 8.5 Hz, 1H), 5.36 (d, J = 4 Hz,
1H), 4.13 (s, 1H), 2.90 (s, 1H), 2.51 (s, 6H).
The synthesis step of compound 26-3：
Compound 26-2 is added in reaction flask（0.176 g, 0.5 mmol）, manganese dioxide (0.870 g, 10 mmol)
With methylene chloride (10 mL), mixture is stirred to react at room temperature；
TLC tracking reaction is until be fully completed；
The crude product obtained after reaction is through obtaining target product 26-3 with re crystallization from toluene（Yield 94%）.Point of product
It is as follows to analyse data：1H NMR (400 MHz, CDCl3): δ8.51 (d, J = 9.0 Hz, 2H), 7.89−7.85 (m,
4H), 7.50−7.42 (m, 6H), 6.63 (d, J=9.0 Hz, 2H), 2.53 (s, 6H) compound 26-3 can
Photoinitiator for synthesis of polymer material.
Embodiment 27：The synthesis of 4- di-n-hexyl amino benzoyl diphenyl phosphine oxide
Using 4- di-n-hexyl aminobenzyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
The synthesis step of compound 27-2：
4- di-n-hexyl aminobenzyl alcohol is added in reaction flask（0.291 g, 1.0 mmol）, diphenyl phosphine oxide（0.304 g,
1.5 mmol）, potassium peroxydisulfate（0.540 g, 2.0 mmol）And acetone（5 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
27-2（Yield 84%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.80−7.35 (m, 10H),
6.99 (d, J = 7.5 Hz, 2H), 6.45 (d, J = 9.0 Hz, 2H), 5.34 (s, 1H), 3.22 (t, J
= 15.5 Hz, 4H), 1.54−1.50 (m, 8H), 1.33−1.27 (m, 8H), 0.88 (t, J = 13.5 Hz,
6H).
The synthesis step of compound 27-3：
Compound 27-2 is added in reaction flask（0.246 g, 0.5 mmol）, manganese dioxide (0.870 g, 10 mmol)
With methylene chloride (10 mL), mixture is stirred to react at room temperature；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the n-hexane obtained after reaction:Ethyl acetate=5:1) target product, is obtained
27-3（Yield 96%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ8.47 (d, J = 9.0
Hz, 2H), 7.93−7.85 (m, 4H), 7.54−7.43(m, 6H), 6.59 (d, J = 9.0 Hz, 2H), 3.31
(t, J = 15.5 Hz, 4H), 1.61−1.56 (m, 8H), 1.31−1.24 (m, 8H), 0.88 (t, J = 13.5
Hz, 6H) compound 27-3 can be used for the photoinitiator of synthesis of polymer material.
Embodiment 28：The synthesis of 4- methyl benzoyl diphenyl phosphine oxide
Using 4- xylyl alcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
Embodiment six is shown in the synthesis of compound 28-1.
The synthesis step of compound 28-2：
Compound 28-1 is added in reaction flask（0.161 g, 0.5 mmol）, manganese dioxide (0.870 g, 10 mmol)
With methylene chloride (10 mL), mixture is stirred to react at room temperature；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the n-hexane obtained after reaction:Ethyl acetate=5:1) target product, is obtained
28-2（Yield 97%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.90 – 7.70 (m,
4H), 7.63 – 7.30 (m, 6H), 7.12 (d, J = 7.0 Hz, 2H), 7.01 (d, J = 7.6 Hz, 2H),
2.26 (s, 3H) compound 28-2 can be used for the photoinitiator of synthesis of polymer material.
Embodiment 29：The synthesis of 4- methoxybenzoyl base diphenyl phosphine oxide
Using 4- methoxyl group benzylalcohol, diphenyl phosphine oxide as raw material, reaction step is as follows：
Embodiment eight is shown in the synthesis of compound 29-1.
The synthesis step of compound 29-2：
Compound 29-1 is added in reaction flask（0.169 g, 0.5 mmol）, manganese dioxide (0.870 g, 10 mmol)
With methylene chloride (10 mL), mixture is stirred to react at room temperature；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the n-hexane obtained after reaction:Ethyl acetate=5:1) target product, is obtained
29-2（Yield 95%）.The analysis data of product are as follows：1H NMR (400 MHz, DMSO-d 6): δ7.85 (dd, J =
18.1, 9.8 Hz, 4H), 7.61 – 7.41 (m, 6H), 7.21 (d, J = 7.7 Hz, 2H), 6.79 (d, J
=8.2 Hz, 2H), 3.74 (s, 3H) compound 29-2 can be used for the photoinitiator of synthesis of polymer material.
Embodiment 30：The synthesis of 2,4,6- trimethyl benzoyl diphenyl phosphine oxide
With 2,4,6- trimethyl benzylalcohols, diphenyl phosphine oxide as raw material, reaction step is as follows：
The synthesis step of compound 30-2：
2,4,6- trimethyl benzylalcohol is added in reaction flask（0.150 g, 1.0 mmol）, diphenyl phosphine oxide（0.304 g,
1.5 mmol）, potassium peroxydisulfate（0.540 g, 2.0 mmol）And acetone（5 mL）, room temperature reaction；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the methylene chloride obtained after reaction:Methanol=40:1) target product, is obtained
30-2（Yield 79%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.40−7.90 (m, 10H),
6.90−7.10 (m, 2H), 5.49 (d, J=4.0 Hz, 1H), 4.41 (s, 1H), 2.31 (s, 6H), 2.17
(s, 3H).
The synthesis step of compound 30-3：
Compound 30-2 is added in reaction flask（0.175 g, 0.5 mmol）, manganese dioxide (0.870 g, 10 mmol)
With methylene chloride (10 mL), mixture is stirred to react at room temperature；
TLC tracking reaction is until be fully completed；
Crude by column chromatography separation (the n-hexane obtained after reaction:Ethyl acetate=5:1) target product, is obtained
29-2（Yield 98%）.The analysis data of product are as follows：1H NMR (400 MHz, CDCl3): δ7.40−7.90 (m, 10H),
7.11 7.30 (m, 2H), 2.52 (s, 6H), 2.29 (s, 3H) compound 30-3 can be used for synthesis of polymer material
Photoinitiator.
Claims (6)
- The synthetic method of 1.4- dimethylamino benzoyl diphenyl phosphine oxide, includes the following steps：（1）4- dimethylaminobenzyl alcohol, diphenyl phosphine oxide, potassium peroxydisulfate and acetone, room temperature reaction are added in reaction flask；TLC with Track reaction is until be fully completed；The crude by column chromatography separation obtained after reaction, obtains target product 26-2；（2）Compound 26-2, manganese dioxide and methylene chloride, mixture are added in reaction flask to be stirred to react at room temperature；TLC with Track reaction is until be fully completed；The crude product obtained after reaction is through obtaining target product 26-3 with re crystallization from toluene.
- 2. the synthetic method of 4- dimethylamino benzoyl diphenyl phosphine oxide according to claim 1, which is characterized in that 4- diformazan Aminobenzyl alcohol, diphenyl phosphine oxide, potassium peroxydisulfate dosage be respectively 1.0 mmol, 1.5 mmol, 2.0 mmol；Compound 26- 2, the dosage of manganese dioxide is respectively 0.5 mmol, 10 mmol.
- 3. the synthetic method of 4- dimethylamino benzoyl diphenyl phosphine oxide according to claim 1, which is characterized in that column chromatography Separation carries out in the presence of methylene chloride is with methanol.
- The synthetic method of 4.4- di-n-hexyl amino benzoyl diphenyl phosphine oxide, includes the following steps：The synthesis step of compound 27-2：（1）4- di-n-hexyl aminobenzyl alcohol, diphenyl phosphine oxide, potassium peroxydisulfate and acetone, room temperature reaction are added in reaction flask；（2）TLC tracking reaction is until be fully completed；（3）The crude by column chromatography separation obtained after reaction, obtains target product 27-2；The synthesis step of compound 27-3：（1）Compound 27-2, manganese dioxide and methylene chloride, mixture are added in reaction flask to be stirred to react at room temperature；（2）TLC tracking reaction is until be fully completed；（3）The crude by column chromatography separation obtained after reaction, obtains target product 27-3.
- 5. the synthetic method of 4- di-n-hexyl amino benzoyl diphenyl phosphine oxide according to claim 4, which is characterized in that 4- Di-n-hexyl aminobenzyl alcohol, diphenyl phosphine oxide, potassium peroxydisulfate dosage be respectively 1.0 mmol, 1.5 mmol, 2.0 mmol；Change Close object 27-2, the dosage of manganese dioxide is respectively 0.5 mmol, 10 mmol.
- 6. the synthetic method of 4- di-n-hexyl amino benzoyl diphenyl phosphine oxide according to claim 4, which is characterized in that change In the synthesis for closing object 27-2, column chromatography for separation carries out in the presence of methylene chloride is with methanol；In the synthesis of compound 27-3, column layer Analysis separation carries out in the presence of n-hexane is with ethyl acetate.
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