CN110256491A - One kind class ligand of phosphorus oxygen containing triaryl and preparation method thereof - Google Patents
One kind class ligand of phosphorus oxygen containing triaryl and preparation method thereof Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 53
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 6
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000007445 Chromatographic isolation Methods 0.000 claims description 3
- 238000011097 chromatography purification Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 238000003809 water extraction Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000007704 transition Effects 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000010499 C–H functionalization reaction Methods 0.000 abstract description 2
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 2
- 238000010523 cascade reaction Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 4
- BPVHWNVBBDHIQU-UHFFFAOYSA-N 2-bromoethynylbenzene Chemical group BrC#CC1=CC=CC=C1 BPVHWNVBBDHIQU-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- AZQCFLDDJHERFZ-UHFFFAOYSA-N Br.C#Cc1ccccc1 Chemical compound Br.C#Cc1ccccc1 AZQCFLDDJHERFZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- -1 that is Chemical class 0.000 description 1
- 238000005406 washing Methods 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)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of class ligands of phosphorus oxygen containing triaryl and preparation method thereof.The class ligand of phosphorus oxygen containing triaryl is constructed by tandem reaction with different multiple alkynes substrates, it is tediously long that the reaction overcomes route in previous reaction, substrate and reaction condition require harsh, the disadvantages of replacing functional group's extension limited, not only substrate synthesis is simple, reagent is relatively cheap for the reaction, and there is high atom economy, be concisely and efficiently to obtain target molecule, provide a kind of completely new approach to application of the class ligand of phosphorus oxygen containing triaryl in transition metal-catalyzed carbon-hydrogen bond activation field.
Description
Technical field
The invention belongs to organic compound synthesis technical fields, and in particular to one kind class ligand of phosphorus oxygen containing triaryl and its system
Preparation Method.
Background technique
Transition metal-catalyzed carbon-hydrogen link activation and function dough are due to its wide application range of substrates and atom economy
The advantages that property and receive more and more attention.In these catalytic conversion reactions, the structure by changing ligand influences metal
The activity and selectivity of catalyst is one of means the most strong.Ligand can change the electrical property of metal and influence catalysis
Activity, while ligand also can change the stereoeffect of metallic perimeter and influence the stereoselectivity reacted.Wherein, phosphorus ligand by
(Scheme 1) is received more and more attention in its important function in transition metal-catalyzed reaction.
Recent years, the carbon-hydrogen link functional group of phosphorus oxygen guiding are melted into order to which everybody falls over each other the hot spot of report.According to reacting
The difference of transition state in journey can be divided into following a few classes: hexatomic ring palladium transition state, five-membered ring rhodium transition state, five-membered ring iridium transition
(Scheme 2) such as state, five-membered ring ruthenium transition state, five-membered ring palladium transition state, five-membered ring cobalt transition states.
Organic phosphorus oxygen ligand has important role in transition metal-catalyzed reaction.Therefore, it finds simple and direct efficient
Method synthesizes the target that various organic phosphorus oxygen ligands are just pursued at many chemists.Although in the past several years
In the type of phosphorus oxygen class ligand that has been achieved for very big progress in this respect, but synthesize at present be not very much, so
It is still essential for developing more new and effective phosphorus oxygen ligand.
Summary of the invention
The purpose of the present invention is to provide a kind of class ligands of phosphorus oxygen containing triaryl, and with polycyclic presence, structure is more complicated,
Have broad application prospects.
The present invention also provides a kind of preparation method of the class of phosphorus oxygen containing triaryl ligand, easy, green, atom economy
Property.
The technical scheme adopted by the invention is as follows:
A kind of class ligand of phosphorus oxygen containing triaryl, the general structure of the class of phosphorus oxygen containing the triaryl ligand are as follows:
Wherein, R1For straight chained alkyl, branched alkyl, saturated hydrocarbons, unsaturated hydro carbons or arene group；
R2For halogen, straight chained alkyl, branched alkyl, ester group, alkoxy and its corresponding derivative；R2It can be at phenyl ring
Any position.
Further, the R1Preferably four carbon straight chained alkyl below, branched alkyl, saturated hydrocarbons, unsaturated hydrocarbons
Class or arene group；R2Preferably halogen, four carbon straight chained alkyl below, branched alkyl, ester group, alkoxy and its
Corresponding derivative；R2It can be at any position of phenyl ring.
Further, the R1Preferably ethyl；R2Preferably hydrogen.
The present invention also provides a kind of preparation method of the class of phosphorus oxygen containing triaryl ligand, the preparation method includes following step
It is rapid:
(1) precursor compound is synthesized, the structural formula of the precursor compound is
Wherein, R1For straight chained alkyl, branched alkyl, saturated hydrocarbons, unsaturated hydro carbons or arene group；
R2For halogen, straight chained alkyl, branched alkyl, ester group, alkoxy and its corresponding derivative；R2It can be at phenyl ring
Any position；
(2) precursor compound reacts in dry toluene with diphenylphosphine, isolates and purifies after reaction, and institute can be obtained
State the class ligand of phosphorus oxygen containing triaryl.
In step (1), the R1Preferably ethyl；R2Preferably hydrogen.
In step (1), the preparation method of the precursor compound the following steps are included:
(1-1) is anti-in ice-water bath by malonate and propargyl bromide in anhydrous acetonitrile solvent using sodium hydride as catalyst
It answers 5~8 hours, obtains compound a after isolating and purifying；
The general formula of the malonate are as follows:
(1-2) is urging the substituent of compound a and phenyl bromoacetylene that step (1) obtains under the conditions of anhydrous and oxygen-free
Under the action of agent and organic base, is reacted 10~14 hours for 0~5 DEG C in anhydrous acetonitrile solvent, after isolating and purifying, obtain precursor
Compound, that is, compound b；
The chemical structural formula of the substituent of the phenyl bromoacetylene are as follows:
In the step (1-1), the ratio between amount of substance between malonate, propargyl bromide and sodium hydride be 1:2.2~
3.2:4~5, concentration of the malonate in anhydrous acetonitrile are 0.8~1.5mol/L.
In the step (1-2), catalyst is Pd (PPh3)2Cl2With the mixture of CuI, organic base is triethylamine.Pd
(PPh3)2Cl2The ratio between amount of substance between CuI is 3:1.
In the step (1-2), substance between compound a, the substituent of phenyl bromoacetylene, catalyst and organic base
The ratio between amount is 1:2.2~3.2:0.03~0.05:4~5, and concentration of the compound a in anhydrous acetonitrile is 0.5~0.8mol/L.
The isolation and purification method that the step (1-2) is taken are as follows: by crude product ethyl acetate and water extraction and separation, concentration
Afterwards, be the ethyl acetate of 1:40~60 with volume ratio: petroleum ether is that eluant, eluent carries out column chromatographic isolation and purification.
In step (2), the condition of the reaction be 95-110 DEG C reaction 8-10 hours.
In step (2), the ratio between amount of substance of the precursor compound and diphenylphosphine is 1:1.0-1.2.
In step (2), concentration of the precursor compound in dry toluene is 0.3-1.0mol/L, preferably
0.5mol/L。
In step (2), the method isolated and purified are as follows: by crude product ethyl acetate and water extraction and separation, after concentration,
Be the ethyl acetate of 1:20~40 with volume ratio: petroleum ether is that eluant, eluent carries out column chromatographic isolation and purification.
Compared with prior art, the present invention provides a series of new class ligands of phosphorus oxygen containing triaryl.With different multiple
Alkynes substrate constructs the class ligand of phosphorus oxygen containing triaryl by tandem reaction, and it is tediously long which overcomes route in previous reaction, bottom
The disadvantages of object and reaction condition require harshness, replace functional group's extension limited, not only substrate synthesizes simple, reagent ratio for the reaction
It is relatively inexpensive, and there is high atom economy, be concisely and efficiently to obtain target molecule, to the class of phosphorus oxygen containing triaryl ligand in transition
Application in the carbon-hydrogen bond activation field of metal catalytic provides a kind of completely new approach.
The synthesis mechanism of triaryl phosphorus oxygen class ligand is as depicted in figure 8 in the present invention: precursor compound is reacted via HDDA first
Obtain benzyne intermediate A；Then, with the compound diphenylphosphine with strong nucleophilicity nucleophilic addition occurs for benzyne intermediate A again
Reaction, obtains intermediate B；Finally, intermediate B is oxidized to obtain triaryl phosphorus oxygen class ligand rapidly.
Relative to the common class ligand of phosphorus oxygen containing triaryl, the class of phosphorus oxygen containing triaryl ligand prepared by the present invention has polycyclic deposit
The more complicated multiplicity of structure will also show more wide purposes prospect in Synthetic Organic Chemistry.Also, this hair
The preparation method of bright offer is easy, efficient, and the reaction time is short, high-efficient.
Detailed description of the invention
Fig. 1 is the general structure of the class of phosphorus oxygen containing triaryl ligand；
Fig. 2 is the synthetic route chart of the class of phosphorus oxygen containing triaryl ligand；
Fig. 3 is the synthetic route chart of the class ligand of phosphorus oxygen containing triaryl c-1 prepared by embodiment 1；
Fig. 4 is the nuclear magnetic resonance spectroscopy of the class ligand of phosphorus oxygen containing triaryl c-1 prepared by embodiment 1；
Fig. 5 is the carbon-13 nmr spectra of the class ligand of phosphorus oxygen containing triaryl c-1 prepared by embodiment 1；
The nuclear magnetic resonance phosphorus spectrum that Fig. 6 is the class ligand of phosphorus oxygen containing triaryl c-1 prepared by embodiment 1；
Fig. 7 is the XRD single crystal diffraction figure of the class ligand of phosphorus oxygen containing triaryl c-1 prepared by embodiment 1；
Fig. 8 is the synthesis mechanism figure of the class ligand of phosphorus oxygen containing triaryl in embodiment 1.
Specific embodiment
Embodiment 1
A kind of class ligand of phosphorus oxygen containing triaryl, the class ligand structure formula of phosphorus oxygen containing triaryl are as follows:
A kind of preparation method of the class of phosphorus oxygen containing triaryl ligand, the preparation method the following steps are included:
(1) using 830mmol sodium hydride as catalyst, 200mmol diethyl malonate and 440mmol propargyl bromide are added
The ice-water bath into 210mL anhydrous acetonitrile is stirred to react 8 hours, and product adds water washing, is extracted with ethyl acetate, and decompression is spin-dried for, and obtains
To white solid product, i.e. compound a -1；
(2) 80mmol compound a -1 and 200mmol phenylacetylene bromide are blended in Pd (PPh3)2Cl2The anhydrous nothing of/CuI
In oxygen catalyst system (2.56mmol/0.85mmol), molar ratio Pd (PPh3)2Cl2: CuI=3:1, with 336mmol triethylamine work
Alkali, using 150mL anhydrous acetonitrile as solvent, 0 DEG C is stirred to react 12 hours, and product is washed with water, and is extracted with ethyl acetate, decompression rotation
Dry, the ethyl acetate for being 1:40 with volume ratio: petroleum ether column chromatography for separation obtains white solid product, i.e. compound b-1.
(3) under conditions of 110 DEG C, 1.0mmol compound b-1 prepared by step (2) and 1.1mmol diphenylphosphine exist
2mL dry toluene solvent reaction 10 hours obtains compound c-1, the i.e. crude product of the class of phosphorus oxygen containing triaryl ligand；By containing for preparation
The crude product with water of triaryl phosphorus oxygen class ligand washs, and ethyl acetate extraction, decompression is spin-dried for, with volume ratio ethyl acetate: petroleum
Ether=1:20 column chromatography for separation, obtains white solid product, the i.e. class of phosphorus oxygen containing triaryl ligand c-1, and column chromatography yield is about
85%.
Product structure passes through1H NMR、13C NMR、31P NMR is measured, as a result as follows:
1H NMR(500MHz,CDCl3)δ7.34-7.27(m,8H),7.25-7.17(m,8H),7.11-7.07(m,4H),
6.80 (s, 1H), 4.24 (q, J=8.5Hz, 4H), 3.81 (s, 2H), 3.57 (s, 2H), 1.28 (t, J=7.0Hz, 6H)；
13C NMR (125MHz, CDCl3)δ171.5,148.6.(d,JC-P=25Hz), 143.1,139.7,139.6,
139.0,137.2,137.1,135.9,135.8,133.9,133.7,131.2,130.3,130.2,128.5,128.3,
128.2,128.1,127.9,127.1,127.0,123.0,120.0,119.9,96.8,86.7,61.7,59.2,40.7,
13.9；
31P NMR (202MHz, CDCl3)δ-12.88(s)。
The above-mentioned detailed description carried out referring to embodiment to a kind of class of phosphorus oxygen containing triaryl ligand and preparation method thereof, is to say
Bright property without being restrictive, several embodiments can be enumerated according to limited range, therefore of the invention total not departing from
Change and modification under body design, should belong within protection scope of the present invention.
Claims (9)
1. a kind of class ligand of phosphorus oxygen containing triaryl, which is characterized in that the general structure of the class of phosphorus oxygen containing the triaryl ligand is as follows:
Wherein, R1For straight chained alkyl, branched alkyl, saturated hydrocarbons, unsaturated hydro carbons or arene group；
R2For halogen, straight chained alkyl, branched alkyl, ester group, alkoxy and its corresponding derivative；R2It can be at appointing for phenyl ring
Meaning position.
2. the class of phosphorus oxygen containing triaryl ligand according to claim 1, which is characterized in that the R1It is below straight for four carbon
Alkyl group, branched alkyl, saturated hydrocarbons, unsaturated hydro carbons or arene group；R2For halogen, four carbon straight chain alkane below
Base, branched alkyl, ester group, alkoxy and its corresponding derivative；R2It can be at any position of phenyl ring.
3. the class of phosphorus oxygen containing triaryl ligand according to claim 1, which is characterized in that the R1For ethyl；R2For hydrogen.
4. a kind of preparation method of the class of phosphorus oxygen containing triaryl ligand as described in claim 1, which is characterized in that the preparation side
Method the following steps are included:
(1) precursor compound is synthesized, the structural formula of the precursor compound is
Wherein, R1For straight chained alkyl, branched alkyl, saturated hydrocarbons, unsaturated hydro carbons or arene group；
R2For halogen, straight chained alkyl, branched alkyl, ester group, alkoxy and its corresponding derivative；R2It can be at appointing for phenyl ring
Meaning position；
(2) precursor compound reacts in dry toluene with diphenylphosphine, isolates and purifies after reaction, and described contain can be obtained
Triaryl phosphorus oxygen class ligand.
5. the preparation method of the class of phosphorus oxygen containing triaryl ligand according to claim 4, which is characterized in that in step (1), institute
State R1For ethyl；R2For hydrogen.
6. the preparation method of the class of phosphorus oxygen containing triaryl ligand according to claim 4, which is characterized in that in step (2), institute
State reaction condition be 95-110 DEG C reaction 8-10 hours.
7. the preparation method of the class of phosphorus oxygen containing triaryl ligand according to claim 4, which is characterized in that in step (2), institute
Stating the ratio between amount of substance of precursor compound and diphenylphosphine is 1:1.0-1.2.
8. the preparation method of the class of phosphorus oxygen containing triaryl ligand according to claim 4, which is characterized in that in step (2), institute
Stating concentration of the precursor compound in dry toluene is 0.3-1.0mol/L.
9. the preparation method of the class of phosphorus oxygen containing triaryl ligand according to claim 4, which is characterized in that in step (2), institute
State the method isolated and purified are as follows: be 1:20~40 with volume ratio after concentration by crude product ethyl acetate and water extraction and separation
Ethyl acetate: petroleum ether is that eluant, eluent carries out column chromatographic isolation and purification.
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| US20150210725A1 (en) * | 2012-08-06 | 2015-07-30 | Council Of Scientific & Industrial Research | Process for preparation of aryl phosphorous compounds |
| CN105949152A (en) * | 2016-07-08 | 2016-09-21 | 安徽师范大学 | Benzofuran derivative and preparation method thereof |
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| CN106946704A (en) * | 2017-03-15 | 2017-07-14 | 安徽师范大学 | A kind of polysubstituted condensed aromatics analog derivative and preparation method thereof |
| CN106966937A (en) * | 2017-04-06 | 2017-07-21 | 盐城工学院 | Diaryl selenide analog derivative and preparation method thereof |
| CN107043342A (en) * | 2017-04-06 | 2017-08-15 | 盐城工学院 | Arylalkyl thioethers analog derivative and preparation method thereof |
| CN107641080A (en) * | 2017-09-29 | 2018-01-30 | 安徽师范大学 | A kind of dihydronaphthalene ketones derivant containing spirane structure and preparation method thereof |
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| CN105949152A (en) * | 2016-07-08 | 2016-09-21 | 安徽师范大学 | Benzofuran derivative and preparation method thereof |
| CN106905205A (en) * | 2017-02-27 | 2017-06-30 | 安徽师范大学 | An a kind of step constructs C O and C Bifunctionalized products of S keys and preparation method thereof |
| CN106946704A (en) * | 2017-03-15 | 2017-07-14 | 安徽师范大学 | A kind of polysubstituted condensed aromatics analog derivative and preparation method thereof |
| CN106966937A (en) * | 2017-04-06 | 2017-07-21 | 盐城工学院 | Diaryl selenide analog derivative and preparation method thereof |
| CN107043342A (en) * | 2017-04-06 | 2017-08-15 | 盐城工学院 | Arylalkyl thioethers analog derivative and preparation method thereof |
| CN107641080A (en) * | 2017-09-29 | 2018-01-30 | 安徽师范大学 | A kind of dihydronaphthalene ketones derivant containing spirane structure and preparation method thereof |
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