CN109369716A - A kind of aryl oxidized phosphine compound and its synthetic method and application - Google Patents
A kind of aryl oxidized phosphine compound and its synthetic method and application Download PDFInfo
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- CN109369716A CN109369716A CN201811074886.9A CN201811074886A CN109369716A CN 109369716 A CN109369716 A CN 109369716A CN 201811074886 A CN201811074886 A CN 201811074886A CN 109369716 A CN109369716 A CN 109369716A
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- phosphine compound
- synthetic method
- oxidized phosphine
- aryl
- aryl oxidized
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- -1 phosphine compound Chemical class 0.000 title claims abstract description 59
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 28
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000004458 analytical method Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000011017 operating method Methods 0.000 claims abstract description 3
- 238000000746 purification Methods 0.000 claims abstract description 3
- 238000010898 silica gel chromatography Methods 0.000 claims abstract 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical group [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 17
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 9
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 8
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Chemical group 0.000 claims description 6
- 239000001257 hydrogen Chemical group 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000006254 arylation reaction Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 abstract description 2
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 38
- JOJZEZRGUFALOK-UHFFFAOYSA-N O=[PH2]C(C=CC=C1)=C1OC1=CC=CC=C1 Chemical compound O=[PH2]C(C=CC=C1)=C1OC1=CC=CC=C1 JOJZEZRGUFALOK-UHFFFAOYSA-N 0.000 description 19
- 239000002585 base Substances 0.000 description 16
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- 230000005311 nuclear magnetism Effects 0.000 description 12
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- RATXVKFWHCDGBF-UHFFFAOYSA-N 1-diphenylphosphoryl-2-phenoxybenzene Chemical compound O=P(c1ccccc1)(c1ccccc1)c1ccccc1Oc1ccccc1 RATXVKFWHCDGBF-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 4
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 3
- NJONDUGZLPLGNT-UHFFFAOYSA-N (3,6-dimethyl-2-trimethylsilylphenyl) trifluoromethanesulfonate Chemical compound CC1=CC=C(C)C([Si](C)(C)C)=C1OS(=O)(=O)C(F)(F)F NJONDUGZLPLGNT-UHFFFAOYSA-N 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YLWUHANSWDDWCX-UHFFFAOYSA-N 1-bis(4-fluorophenyl)phosphoryl-2-phenoxybenzene Chemical compound FC1=CC=C(C=C1)P(C1=C(C=CC=C1)OC1=CC=CC=C1)(C1=CC=C(C=C1)F)=O YLWUHANSWDDWCX-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- PQTLSVRQJMZPSJ-UHFFFAOYSA-N bis(4-chlorophenyl)phosphinic acid Chemical class C=1C=C(Cl)C=CC=1P(=O)(O)C1=CC=C(Cl)C=C1 PQTLSVRQJMZPSJ-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KXFSUVJPEQYUGN-UHFFFAOYSA-N trimethyl(phenyl)silane Chemical compound C[Si](C)(C)C1=CC=CC=C1 KXFSUVJPEQYUGN-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 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
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention belongs to technical field of organic synthesis, a kind of aryl oxidized phosphine compound and its synthetic method and application are disclosed.The compound has the structure as shown in formula (I).The present invention is synthesized according to following operating procedure: in the presence of the solvent by aryne precursor and diaryl hypophosphorous acid, alkali and Fluorine source is added, it is stirred at 60~80 DEG C, aryl oxidized phosphine compound is made through extraction, drying, filtering, silica gel column chromatography analysis purification and vacuum distillation processing.Rapidly and efficiently a step constructs carbon-phosphorus to this method in a mild condition, carbon-oxygen bond, reaction is related to aryl hypophosphorous acid for the oxygen arylation of the addition of aryne and excessive aryne, the method of the invention is simple and efficient, and it is suitable for that substrate spectrum is extensive, a green method is provided for being synthetically prepared for aromatic yl phosphine compound.
Description
Technical field
The invention belongs to technical field of organic synthesis, in particular to a kind of aryl oxidized phosphine compound and its synthetic method and
Using.
Background technique
Aromatic yl phosphine compound is widely used in transition metal-catalyzed and organic synthesis field, develops effective synthesis side
Method is of great significance (Tang, W.；Zhang, X.Chem.Rev.2003,103,3029.), such as with palladium chtalyst aryl bromination
Object and dialkyl phosphine synthesis of organo-phosphines compound (Bull.Chem.Soc.Jpn.1982,55,909.), the Bu Hewaer of big steric hindrance
Moral ligand plays a crucial role (Acc.Chem.Res.2008,41,1461.), transition metal in palladium chtalyst coupling field
The phosphorus arylation for being catalyzed organic phosphine groups increasingly payes attention to (Curr.Org.Synth.2014,11,429.) by everybody.Based on
The report of upper pertinent literature, method used require transition metal, and reagent is very sensitive for water, and substrate needs pre- function
Change, it is therefore desirable to a kind of method for developing efficient synthesizing aryl phosphine oxide.
Summary of the invention
In place of solving shortcoming and defect in the prior art, the primary purpose of the present invention is that providing a kind of aryl oxide
Change phosphine compound.
Another object of the present invention is to provide a kind of synthetic methods of above-mentioned aryl oxidized phosphine compound.This method is only
It need to be stirred to react at a certain temperature under the action of weak base, make aryl hypophosphorous acid compound for aryne addition, then mistake
The oxygen arylation of the aryne of amount, can obtain aryl oxidized phosphine compound.It is not required to addition metallic catalyst, high temperature is not needed, does not have
There is by-product generation, there is high conversion, convenient and environmentally friendly feature.
A further object of the present invention is to provide a kind of applications of above-mentioned aryl oxidized phosphine compound.
The object of the invention is achieved through the following technical solutions:
A kind of aryl oxidized phosphine compound, the compound have the structure as shown in formula (I):
Wherein, R is methyl, methoxyl group or hydrogen；
Ar is to have methyl, methoxyl group, chlorine or fluorine-substituted phenyl on phenyl, naphthalene or phenyl ring.
A kind of synthetic method of above-mentioned aryl oxidized phosphine compound, according to following operating procedure: by aryne precursor and
Diaryl hypophosphorous acid in the presence of the solvent, is added alkali and Fluorine source, stirs at 60~80 DEG C, through extraction, drying, filtering, silicon
Aryl oxidized phosphine compound is made in plastic column chromatography analysis purification and vacuum distillation processing.
The aryne precursor has the structure as shown in following formula (II):
Wherein, R1For alkyl or hydrogen；
The diaryl hypophosphorous acid compound has the structure as shown in following formula (III):
Wherein, R2For hydrogen, phenyl, methoxyl group, chlorine or fluorine.
The aryne precursor, diaryl hypophosphorous acid, alkali, Fluorine source reaction molar ratio be 3:1:3:(2~6).
The aryne precursor, diaryl hypophosphorous acid, alkali, Fluorine source reaction molar ratio be 3:1:3:6.
The solvent is acetonitrile or tetrahydrofuran；The time of the stirring is 6~9h；Solvent used in the extraction is
Ethyl acetate；Reagent used by the drying be anhydrous sodium sulfate, dry temperature be 25 DEG C, the dry time be 10~
15min。
The temperature of the vacuum distillation is 35~45 DEG C, and the pressure of the vacuum distillation is -0.085~-0.095MPa.
The alkali is cesium carbonate；The Fluorine source is cesium fluoride.
Application of the above-mentioned aryl oxidized phosphine compound in transition metal-catalyzed and organic synthesis field.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) for the present invention using cesium carbonate as alkali, cesium fluoride makes adjacent halogen trimethylsilylbenzene base trifluoro sulphonic acid ester as Fluorine source
It sloughs protecting group and forms aryne and aryl hypophosphorous acid compound addition, the alkalinity of the alkali is weak, is easily obtained and saves, and effect is bright
It is aobvious.
(2) present invention using weak base make aryl hypophosphorous acid slough proton and then and aryne nucleophilic addition method synthesizing aryl
Phosphine oxide-type compound, raw material is simple, and it is wide that reaction can fit substrate spectrum, and synthesis is simple, and reaction condition is mild, and yield is high, by-product
Object is few, solves and needs the metal that overuses in the prior art, and reaction substrate is for water sensitive, and at high cost, product is difficult to separate
The problems such as, new high efficiency method is provided for the preparation of aryl oxidized phosphine compound.
Detailed description of the invention
Fig. 1 is final product in embodiment 11H NMR spectra.
Fig. 2 is final product in embodiment 113C NMR spectra.
Fig. 3 is final product in embodiment 21H NMR spectra.
Fig. 4 is final product in embodiment 213C NMR spectra.
Fig. 5 is final product in embodiment 31H NMR spectra.
Fig. 6 is final product in embodiment 313C NMR spectra.
Fig. 7 is final product in embodiment 41H NMR spectra.
Fig. 8 is final product in embodiment 413C NMR spectra.
Fig. 9 is final product in embodiment 51H NMR spectra.
Figure 10 is final product in embodiment 513C NMR spectra.
Figure 11 is final product in embodiment 61H NMR spectra.
Figure 12 is final product in embodiment 613C NMR spectra.
Specific implementation method
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment is served only for pair
The present invention is further described, but should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made according to the content of aforementioned present invention.
Unless stated otherwise, the present invention uses reagent, method and apparatus for the art conventional reagent, method and are set
It is standby.
Embodiment 1 synthesizes 2- Phenoxyphenyl diphenyl phosphine oxide
Weigh the o- trimethylsilyl phenyl trifluoromethanesulfonate methanesulfonates of 0.6mmol, 0.2mmol diphenyl hypophosphorous acid, 0.6mmol carbon
Sour caesium, 1.2mmol cesium fluoride are added in 15mL pressure resistance reaction tube, and magnetic stir bar and 2mL acetonitrile is added, is stirred to react at 80 DEG C
8h, as shown in formula (1).Solvent is boiled off with Rotary Evaporators after reaction, then is extracted with 10mL ethyl acetate, anhydrous slufuric acid is used
Sodium is dried 15 minutes and is filtered at 25 DEG C, and vacuum distillation removing is finally carried out at -0.09MPa, 40 DEG C with Rotary Evaporators
Product 2- Phenoxyphenyl diphenyl phosphine oxide, yield 85% can be obtained in organic solvent.
The nuclear-magnetism characterization map of 2- Phenoxyphenyl diphenyl phosphine oxide is as depicted in figs. 1 and 2.Wherein, Fig. 1 is 2- benzene oxygen
Base phenyl diphenyl phosphine oxide1H NMR spectra, Fig. 2 are 2- Phenoxyphenyl diphenyl phosphine oxide13C NMR spectra.2- benzene
Phenyl diphenyl phosphine oxide is characterized by nuclear-magnetism and is confirmed with existing chromatogram characteristic structure.The characterize data of the compound
It is as follows:1H NMR(400MHz,CDCl3)δ8.11–8.05(m,3H),7.81–7.76(m,4H),7.49–7.36(m,7H),
7.24-7.17 (m, 3H), 7.05 (t, J=8.0Hz, 1H), 6.73 (q, J=8.0,5.2Hz, 1H), 6.60 (d, J=8.0Hz,
2H).13C NMR(100MHz,CDCl3) δ 159.0 (d, J=3.0Hz), 154.8,135.2 (d, J=7.0Hz), 134.1 (d, J
=2.0Hz), 132.9 (d, J=107Hz), 132.1 (d, J=10.0Hz), 131.7 (d, J=4.0Hz), 129.8,128.3
(d, J=13.0Hz), 124.5,122.9 (d, J=11.0Hz), 122.4 (d, J=104Hz), 119.9,116.6 (d, J=
6.0Hz).31P NMR(162MHz,CDCl3)δ26.5.
Embodiment 2 synthesizes bis- (3- methoxyphenyls) (2- Phenoxyphenyl) phosphine oxide
Weigh the o- trimethylsilyl phenyl trifluoromethanesulfonate methanesulfonates of 0.6mmol, bis- (4- methoxyphenyl) hypophosphorous acid of 0.2mmol,
0.6mmol cesium carbonate, 1.2mmol cesium fluoride are added in 15mL pressure resistance reaction tube, addition magnetic stir bar and 2mL acetonitrile, and 60 DEG C
Under be stirred to react 8h, as shown in formula (2).Solvent is boiled off with Rotary Evaporators after reaction, then is extracted with 10mL ethyl acetate,
It is dried 15 minutes and is filtered at 25 DEG C with anhydrous sodium sulfate, finally subtracted at -0.09MPa, 40 DEG C with Rotary Evaporators
Organic solvent is distilled off in pressure, and product 2- Phenoxyphenyl diphenyl phosphine oxide, yield 90% can be obtained.
The nuclear-magnetism characterization map of bis- (3- methoxyphenyls) (2- Phenoxyphenyl) phosphine oxide is as shown in Figure 3 and Figure 4.Its
In, Fig. 3 is bis- (3- methoxyphenyls) (2- Phenoxyphenyl) phosphine oxide1H NMR spectra, Fig. 4 are bis- (3- methoxybenzenes
Base) (2- Phenoxyphenyl) phosphine oxide13C NMR spectra.Bis- (3- methoxyphenyls) (2- Phenoxyphenyl) phosphine oxide passes through
Nuclear-magnetism characterization is confirmed with existing chromatogram characteristic structure.The characterize data of the compound is as follows:
1H NMR(400MHz,CDCl3)δ8.0–7.95(m,1H),7.46–7.42(m,1H),7.36–7.26(m,6H),
7.22-7.16 (m, 3H), 7.04 (t, J=8.0Hz, 1H), 7.00-6.97 (m, 2H), 6.77 (dd, J=8.0,4.0Hz, 1H),
6.63 (d, J=8.0Hz, 2H), 3.73 (s, 6H)13C NMR(100MHz,CDCl3) δ 159.4 (d, J=16.0Hz), 159.0
(d, J=3.0Hz), 155.0,135.1 (d, J=7.0Hz), 134.1 (d, J=107Hz), 134.0 (d, J=1.9Hz),
129.7,129.5 (d, J=14.8Hz), 124.4,124.3 (d, J=4.1Hz), 123.1 (d, J=11.1Hz), 122.6 (d, J
=102Hz), 119.7,118.0 (d, J=2.7Hz), 117.1 (d, J=6.4Hz), 116.8 (d, J=11.5Hz), 55.4.31P
NMR(162MHz,CDCl3)δ26.9.
Embodiment 3 synthesizes bis- (4- chlorphenyls) (2- Phenoxyphenyl) phosphine oxide
Weigh the o- trimethylsilyl phenyl trifluoromethanesulfonate methanesulfonates of 0.6mmol, bis- (4- chlorphenyl) phosphinic acids of 0.2mmol,
0.6mmol cesium carbonate, 1.2mmol cesium fluoride are added in 15mL pressure resistance reaction tube, and magnetic stir bar and 2mL tetrahydrofuran is added,
It is stirred to react 9h at 80 DEG C, as shown in formula (3).Solvent is boiled off with Rotary Evaporators after reaction, then with 10mL ethyl acetate
Extraction dry 15 minutes and is filtered at 25 DEG C with anhydrous sodium sulfate, finally with Rotary Evaporators at -0.09MPa, 40 DEG C into
Row vacuum distillation removes organic solvent, and product 2- Phenoxyphenyl diphenyl phosphine oxide, yield 88% can be obtained.
The nuclear-magnetism characterization map of bis- (4- chlorphenyls) (2- Phenoxyphenyl) phosphine oxide is as shown in Figure 5 and Figure 6.Wherein, Fig. 5
For bis- (4- chlorphenyls) (2- Phenoxyphenyl) phosphine oxide1H NMR spectra, Fig. 6 are bis- (4- chlorphenyl) (2- phenoxy group benzene
Base) phosphine oxide13C NMR spectra.(4- chlorphenyl) (2- Phenoxyphenyl) phosphine oxide is special by nuclear-magnetism characterization and existing spectrogram
Sign structure is confirmed.The characterize data of the compound is as follows:
1H NMR(400MHz,CDCl3) δ 8.09 (dd, J=12.0,8.0Hz, 1H), 7.69 (dd, J=12.0,8.0Hz,
4H), 7.48 (t, J=8.0Hz, 1H), 7.37 (d, J=8.0Hz, 4H), 7.25-7.21 (m, 3H), 7.10 (t, J=8.0Hz,
1H), 6.75 (dd, J=8.0,4.0Hz, 1H), 6.60 (d, J=8.0Hz, 2H)13C NMR(101MHz,CDCl3)δ158.7
(d, J=4.0Hz), 154.6,138.5 (d, J=3.0Hz), 135.2 (d, J=7.0Hz), 134.6 (d, J=2.0Hz),
133.5 (d, J=11.0Hz), 131.2 (d, J=109.0Hz), 129.9,128.7 (d, J=13.0Hz), 124.77,123.3
(d, J=11.0Hz), 121.5 (d, J=103Hz), 119.7,116.8 (d, J=6.0Hz)31P NMR(162MHz,CDCl3)δ
25.0.
Embodiment 4 synthesizes bis- (4- fluorophenyls) (2- Phenoxyphenyl) phosphine oxide
Weigh the o- trimethylsilyl phenyl trifluoromethanesulfonate methanesulfonates of 0.6mmol, bis- (4- fluorophenyl) hypophosphorous acid of 0.2mmol,
0.6mmol cesium carbonate, 1.2mmol cesium fluoride are added in 15mL pressure resistance reaction tube, addition magnetic stir bar and 2mL acetonitrile, and 70 DEG C
Under be stirred to react 8h, as shown in formula (4).Solvent is boiled off with Rotary Evaporators after reaction, then is extracted with 10mL ethyl acetate,
It is dried 15 minutes and is filtered at 25 DEG C with anhydrous sodium sulfate, finally subtracted at -0.09MPa, 40 DEG C with Rotary Evaporators
Organic solvent is distilled off in pressure, and product bis- (4- fluorophenyls) (2- Phenoxyphenyl) phosphine oxide, yield 86% can be obtained.
The nuclear-magnetism characterization map of bis- (4- fluorophenyls) (2- Phenoxyphenyl) phosphine oxide is as shown in Figure 7 and Figure 8.Wherein, Fig. 7
For bis- (4- fluorophenyls) (2- Phenoxyphenyl) phosphine oxide1H NMR spectra, Fig. 8 are bis- (4- fluorophenyl) (2- phenoxy group benzene
Base) phosphine oxide13C NMR spectra.Bis- (4- fluorophenyl) (2- Phenoxyphenyl) phosphine oxides pass through nuclear-magnetism characterization and existing spectrogram
Feature structure is confirmed.The characterize data of the compound is as follows:
1H NMR(400MHz,CDCl3) δ 8.14-8.09 (m, 1H), 7.80-7.73 (m, 4H), 7.47 (t, J=7.7Hz,
1H), 7.28-7.16 (m, 3H), 7.10-7.05 (m, 5H), 6.75 (dd, J=8.1,5.4Hz, 1H), 6.60 (d, J=7.8Hz,
2H).13C NMR(100MHz,CDCl3)δ165.1(dd,JC-F=254, JC-P=4.0Hz), 158.7 (d, JC-P=3.5Hz),
154.7,135.2(d,JC-P=6.2Hz), 134.6 (dd, JC-F=13.5Hz, JC-P=10.2Hz), 134.5 (d, J=
2.9Hz),129.9,128.8(dd,JC-P=111.2Hz, JC-F=3.4Hz), 124.7,123.2 (d, JC-P=11.1Hz),
121.9(d,JC-P=104Hz), 119.7,116.8 (d, JC-P=6.4Hz), 115.7 (dd, JC-P=21.4Hz, JC-F=
13.8Hz).31P NMR(162MHz,CDCl3)δ24.7.19F NMR(376MHz,CDCl3)δ-107.0.
Embodiment 5 synthesizes (2- (2,5- dimethyl phenoxy) -3,6- 3,5-dimethylphenyl) diphenyl phosphine oxide
Weigh 0.6mmol 3,6- dimethyl -2- (trimethyl silyl) phenyl trifluoromethanesulfonate methanesulfonates, 0.2mmol hexichol
Base hypo acid, 0.6mmol cesium carbonate, 1.2mmol cesium fluoride are added in 15mL pressure resistance reaction tube, and magnetic stir bar and 2mL second is added
Nitrile is stirred to react 9h at 70 DEG C, as shown in formula (5).Solvent is boiled off with Rotary Evaporators after reaction, then with 10mL acetic acid second
Ester extraction is dried 15 minutes and is filtered at 25 DEG C with anhydrous sodium sulfate, finally with Rotary Evaporators at -0.09MPa, 40 DEG C
It carries out vacuum distillation and removes organic solvent, it is bis- (2- (2,5- dimethyl phenoxy) -3,6- 3,5-dimethylphenyl) that product can be obtained
Diphenyl phosphine oxide, yield 92%.
The nuclear-magnetism of (2- (2,5- dimethyl phenoxy) -3,6- 3,5-dimethylphenyl) diphenyl phosphine oxide characterizes map such as Fig. 9
With shown in Figure 10.Wherein, Fig. 9 is bis- (4- fluorophenyls) (2- Phenoxyphenyl) phosphine oxide1H NMR spectra, Figure 10 are bis- (4-
Fluorophenyl) (2- Phenoxyphenyl) phosphine oxide13C NMR spectra.(2- (2,5- dimethyl phenoxy) -3,6- 3,5-dimethylphenyl)
Diphenyl phosphine oxide is characterized by nuclear-magnetism and is confirmed with existing chromatogram characteristic structure.The characterize data of the compound is as follows:
1H NMR(400MHz,CDCl3) δ 7.75 (dd, J=12.1,7.5Hz, 2H), 7.56-7.36 (m, 5H), 7.25 (d,
J=6.9Hz, 1H), 7.06 (dd, J=13.0,5.4Hz, 2H), 6.98 (d, J=5.2Hz, 2H), 6.69 (d, J=7.5Hz,
1H), 6.47 (d, J=7.4Hz, 1H), 5.64 (s, 1H), 2.70 (s, 3H), 1.99 (s, 3H), 1.74 (d, J=8.0Hz, 6H)
.13C NMR(101MHz,CDCl3) δ 155.03 (d, J=4.2Hz), 154.70,144.45 (d, J=6.2Hz), 135.95,
131.83 (d, J=10.1Hz), 131.56 (d, J=2.7Hz), 131.33 (d, J=10.4Hz), 130.45 (d, J=
2.7Hz), 130.20,129.08 (d, J=11.2Hz), 128.45 (d, J=4.2Hz), 128.37 (d, J=12.3Hz),
127.46 (d, J=12.6Hz), 122.64,122.19,114.92,22.47 (d, J=3.5Hz), 20.94,17.13 (d, J=
1.0Hz),15.6.31P NMR(162MHz,CDCl3)δ30.2.
Embodiment 6 synthesizes two (naphthalene -1- base) (2- Phenoxyphenyl) phosphine oxides
Weigh 0.6mmol 3,6- dimethyl -2- (trimethyl silyl) phenyl trifluoromethanesulfonate methanesulfonates, 0.2mmol hexichol
Base phosphinic acids, 0.6mmol cesium carbonate, 1.2mmol cesium fluoride are added in 15mL pressure resistance reaction tube, and magnetic stir bar and 2mL is added
Acetonitrile is stirred to react 8h at 80 DEG C, as shown in formula (6).Solvent is boiled off with Rotary Evaporators after reaction, then with 10mL acetic acid
Ethyl ester extraction dry 15 minutes and is filtered at 25 DEG C with anhydrous sodium sulfate, finally with Rotary Evaporators in -0.09MPa, 40 DEG C
Under carry out vacuum distillation remove organic solvent, product two (naphthalene -1- base) (2- Phenoxyphenyl) phosphine oxide can be obtained, yield is
81%.
The nuclear-magnetism characterization map of two (naphthalene -1- base) (2- Phenoxyphenyl) phosphine oxides is as is illustrated by figs. 11 and 12.Wherein, scheme
11 be two (naphthalene -1- base) (2- Phenoxyphenyl) phosphine oxides1H NMR spectra, Figure 12 are two (naphthalene -1- base) (2- phenoxy group benzene
Base) phosphine oxide13C NMR spectra.Two (naphthalene -1- base) (2- Phenoxyphenyl) phosphine oxides are special by nuclear-magnetism characterization and existing spectrogram
Sign structure is confirmed.The characterize data of the compound is as follows:
1H NMR(400MHz,CDCl3) δ 8.81 (d, J=8.2Hz, 2H), 8.46-8.40 (m, 1H), 7.85 (d, J=
7.7Hz, 4H), 7.61-7.42 (m, 7H), 7.36 (t, J=7.4Hz, 1H), 7.33-7.15 (m, 2H), 6.91-6.82 (m,
3H), 6.74 (dd, J=8.1,5.1Hz, 1H), 6.07 (d, J=7.6Hz, 2H)13C NMR(100MHz,CDCl3)δ158.6
(d, J=3.0Hz), 155.2,135.7 (d, J=6.5Hz), 134.09 (dd, J=7.2,2.1Hz), 133.9 (d, J=
3.2Hz), 133.7 (d, J=12.7Hz), 133.28 (d, J=104Hz) .132.8 (d, J=1.6Hz), 129.2,128.9 (d,
), J=0.8Hz 127.3,126.3,124.5 (d, J=15.0Hz), 123.8 (d, J=11.1Hz), 123.7 (d, J=
102Hz), 123.5,118.6,117.9 (d, J=6.5Hz)31P NMR(162MHz,CDCl3)δ32.8.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. a kind of aryl oxidized phosphine compound, it is characterised in that: the compound has the structure as shown in formula (I):
Wherein, R is methyl, methoxyl group or hydrogen；
Ar is to have methyl, methoxyl group, chlorine or fluorine-substituted phenyl on phenyl, naphthalene or phenyl ring.
2. a kind of synthetic method of aryl oxidized phosphine compound according to claim 1, it is characterised in that according to following
Operating procedure: in the presence of the solvent by aryne precursor and diaryl hypophosphorous acid, alkali and Fluorine source is added, is stirred at 60~80 DEG C
It mixes, aryl oxidized phosphine compound is made through extraction, drying, filtering, silica gel column chromatography analysis purification and vacuum distillation processing.
3. a kind of synthetic method of aryl oxidized phosphine compound according to claim 2, it is characterised in that: the aryne
Precursor has the structure as shown in following formula (II):
Wherein, R1For alkyl or hydrogen；
The diaryl hypophosphorous acid compound has the structure as shown in following formula (III):
Wherein, R2For hydrogen, phenyl, methoxyl group, chlorine or fluorine.
4. a kind of synthetic method of aryl oxidized phosphine compound according to claim 2, it is characterised in that: the aryne
Precursor, diaryl hypophosphorous acid, alkali, Fluorine source reaction molar ratio be 3:1:3:(2~6).
5. a kind of synthetic method of aryl oxidized phosphine compound according to claim 2, it is characterised in that: the aryne
Precursor, diaryl hypophosphorous acid, alkali, Fluorine source reaction molar ratio be 3:1:3:6.
6. a kind of synthetic method of aryl oxidized phosphine compound according to claim 2, it is characterised in that: the solvent
For acetonitrile or tetrahydrofuran；The time of the stirring is 6~9h；Solvent used in the extraction is ethyl acetate；It is described dry
Reagent used by dry is anhydrous sodium sulfate, and dry temperature is 25 DEG C, and the dry time is 10~15min.
7. a kind of synthetic method of aryl oxidized phosphine compound according to claim 2, it is characterised in that: the decompression
The temperature of distillation is 35~45 DEG C, and the pressure of the vacuum distillation is -0.085~-0.095MPa.
8. a kind of synthetic method of aryl oxidized phosphine compound according to claim 2, it is characterised in that: the alkali is
Cesium carbonate；The Fluorine source is cesium fluoride.
9. aryl oxidized phosphine compound according to claim 1 answering in transition metal-catalyzed and organic synthesis field
With.
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