CN108383873B - 1- (8- aryl naphthalene) Phosphine ligands and preparation method thereof and phosphine gold complex and application - Google Patents

1- (8- aryl naphthalene) Phosphine ligands and preparation method thereof and phosphine gold complex and application Download PDF

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CN108383873B
CN108383873B CN201810162981.8A CN201810162981A CN108383873B CN 108383873 B CN108383873 B CN 108383873B CN 201810162981 A CN201810162981 A CN 201810162981A CN 108383873 B CN108383873 B CN 108383873B
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aryl
naphthalene
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heteroaryl
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CN108383873A (en
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支志明
余广鳌
陈建
袁佳
罗雪
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Huazhong Normal University
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Abstract

The present invention relates to organic synthesis fields, disclose 1- (8- aryl naphthalene) Phosphine ligands and preparation method thereof and phosphine gold complex and application, the ligand is indicated by following formula (1), wherein, 2 R " are each independently selected from phenyl or cyclohexyl, and M is selected from substituted or unsubstituted heteroaryl or substituted or unsubstituted aryl；The hetero atom of the heteroaryl is nitrogen-atoms, and the substituent group of the heteroaryl is selected from least one of methyl, methoxyl group, trifluoromethyl ,-Cl and-Br；The substituted aryl is indicated by following formula (2), 1- (8- aryl naphthalene) Phosphine ligands can be directly prepared in the present invention, method is easy, and overcome the defect of 1- (8- aryl naphthalene) Phosphine ligands preparation method substrate narrow application range in the prior art, new 1- (8- aryl naphthalene) Phosphine ligands, and method high income provided by the invention has been prepared.

Description

1- (8- aryl naphthalene) Phosphine ligands and preparation method thereof and phosphine gold complex and application
Technical field
The present invention relates to organic synthesis fields, and in particular to a kind of 1- (8- aryl naphthalene) Phosphine ligands and preparation method thereof, A kind of phosphine gold complex and application.
Background technique
1- (8- aryl naphthalene) Phosphine ligands have unique chemical structure, keep it anti-in electroluminescent material and organic transformation There is great potential using value in answering.
Currently, the method for synthesis 1- (the 8- aryl naphthalene) phosphine registered in document is to synthesize the bromo- 8- arylnaphthalene of 1- first Then compound reacts under conditions of stringent anhydrous and oxygen-free and low temperature with n-BuLi, then prepare 1- with chlorination phosphine reaction (8- aryl naphthalene) phosphine (Journal of the American Chemical Society, 2016,138,587-593； Chemistry-A European Journal,2002,8,4633-4648.).This method is not only complicated for operation, condition is harsh, Yield is low, and substrate narrow application range.
It would therefore be highly desirable to develop a kind of synthetic method easy to operate, efficient, applied widely.
Summary of the invention
The purpose of the invention is to overcome 1- of the existing technology (8- aryl naphthalene) Phosphine ligands preparation process it is complicated, Condition is harsh, yield is low, and the defect of substrate narrow application range, provides a kind of 1- (8- aryl naphthalene) Phosphine ligands and preparation side Method and a kind of phosphine gold complex and application of the phosphine gold complex in 4- phenyl -3- crotonylene -one hydration reaction.
The first aspect of the present invention provides a kind of 1- (8- aryl naphthalene) Phosphine ligands, which is indicated by following formula (1),
Wherein, 2 R " are each independently selected from phenyl or cyclohexyl, and M, which is selected from, to be replaced Or unsubstituted heteroaryl or substituted or unsubstituted aryl；The hetero atom of the heteroaryl is nitrogen-atoms, the heteroaryl Substituent group be selected from least one of methyl, methoxyl group, trifluoromethyl ,-Cl and-Br；The substituted aryl is by following formula (2) It indicates,
Wherein, R is selected from-CH3、-OCH3、-CF3Or-Cl.
Second aspect of the present invention provides a kind of preparation method of 1- (8- aryl naphthalene) Phosphine ligands, this method comprises:
Under an inert atmosphere, willM-X1, alkaline matter and c h bond activated catalyst contact, wherein 2 A R " is each independently selected from phenyl or cyclohexyl；X1For halogen, M be selected from substituted or unsubstituted heteroaryl or substitution or Unsubstituted aryl；The hetero atom of the heteroaryl is nitrogen-atoms, and the substituent group of the heteroaryl is selected from methyl, methoxyl group, three At least one of methyl fluoride ,-Cl and-Br；The substituted aryl by following formula (2) indicate,
Wherein, R is selected from-CH3、-OCH3、-CF3Or-Cl.
Third aspect present invention provides 1- made from above-mentioned preparation method (8- aryl naphthalene) ligand.
Fourth aspect present invention provides a kind of phosphine gold complex, which includes 1- provided by the invention (8- aryl Naphthalene) Phosphine ligands, the complex is with structure shown in formula (3):
Wherein, 2 R " are each independently selected from phenyl or cyclohexyl, and X is selected from bromine or chlorine, and M is selected from substituted or unsubstituted Heteroaryl or substituted or unsubstituted aryl；The hetero atom of the heteroaryl is nitrogen-atoms, and the substituent group of the heteroaryl selects From at least one of methyl, methoxyl group, trifluoromethyl ,-Cl and-Br；The substituted aryl by following formula (2) indicate,
Wherein, R is selected from-CH3、-OCH3、-CF3Or-Cl.
Fifth aspect present invention provides above-mentioned phosphine gold complex answering in 4- phenyl -3- crotonylene -one hydration reaction With.
The present inventor is by further investigation discovery, 1- (8- aryl naphthalene) Phosphine ligands provided by the present invention and gold The complex of composition, can be very good be applied to 4- phenyl -3- crotonylene -one hydration reaction in, with the prior art provide its He compares complex, catalytic activity with higher, and the TON value for being catalyzed reaction is higher.
The present invention has found in the course of the research, under an inert atmosphere, incites somebody to actionM-X1, alkaline matter and c h bond 1- (8- aryl naphthalene) Phosphine ligands can be directly prepared in activated catalyst contact, and method is easy, and overcomes the prior art The defect of middle 1- (8- aryl naphthalene) Phosphine ligands preparation method substrate narrow application range, has been prepared new 1- (8- arylnaphthalene Base) Phosphine ligands, and method high income provided by the invention.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, such asStructure on substituent R can any site on ring replaced, and be It is monosubstituted.
In the case of the present invention is without specified otherwise, Ph represents phenyl, and Me represents methyl, and Cy represents cyclohexyl.
First aspect present invention provides a kind of 1- (8- aryl naphthalene) Phosphine ligands, which is indicated by following formula (1),
Wherein, 2 R " are each independently selected from phenyl or cyclohexyl, and M is selected from substituted or unsubstituted heteroaryl or takes Generation or unsubstituted aryl；The hetero atom of the heteroaryl is nitrogen-atoms, and the substituent group of the heteroaryl is selected from methyl, methoxy At least one of base, trifluoromethyl ,-Cl and-Br；The substituted aryl by following formula (2) indicate,
Wherein, R is selected from-CH3、-OCH3、-CF3Or-Cl.
In accordance with the present invention it is preferred that 2 R " are identical.
In the present invention, the M can be the heteroaryl with substituent group, or unsubstituted heteroaryl, it is described miscellaneous The hetero atom of aryl is nitrogen-atoms, and the M can also be the aryl with substituent group, or unsubstituted aryl.
In the heteroaryl can containing one or more nitrogen-atoms, for example, a nitrogen-atoms can be contained, Nitrogen-atoms there are two can containing.The heteroaryl can containing one or more ring, for example, a ring can be contained, Ring there are two can also containing.
A preferred embodiment of the invention, the substituted or unsubstituted heteroaryl are selected fromR1Methyl, methoxyl group or trifluoromethyl are each independently selected from R'. It is further preferred that R1For methoxyl group；R' is selected from methyl or trifluoromethyl.
A preferred embodiment of the invention, unsubstituted aryl be selected from phenyl,
A preferred embodiment of the invention, the ligand are expressed from the next, wherein and Ph represents phenyl,
Wherein, R be selected from H, 3- methoxyl group, 4- methyl, (Ph represents benzene by 4-Cl, 4-COPh Base), 4-CF3, 4-9H- carbazole, 2 R " are each independently selected from phenyl or cyclohexyl；
R' is selected from methyl or trifluoromethyl；
Second aspect of the present invention provides a kind of preparation method of 1- (8- aryl naphthalene) Phosphine ligands, this method comprises:
Under an inert atmosphere, willM-X1, alkaline matter and c h bond activated catalyst contact, wherein 2 A R " is each independently selected from phenyl or cyclohexyl；X1For halogen, M be selected from substituted or unsubstituted heteroaryl or substitution or Unsubstituted aryl；The hetero atom of the heteroaryl is nitrogen-atoms, and the substituent group of the heteroaryl is selected from methyl, methoxyl group, three At least one of methyl fluoride ,-Cl and-Br；The substituted aryl by following formula (2) indicate,
Wherein, R is selected from-CH3、-OCH3、-CF3Or-Cl.
The preparation of above-mentioned ligand can be completed using a step for method provided by the invention.It overcomes and needs elder generation in the prior art The bromo- 8- aryl naphthalene compound of 1- is synthesized, is then reacted under conditions of stringent anhydrous and oxygen-free and low temperature with n-BuLi, then with Chlorination phosphine reaction prepares the relatively complicated defect of 1- (8- aryl naphthalene) phosphine, and method 1- (8- arylnaphthalene provided by the invention Base) Phosphine ligands yield it is higher.
The method provided according to the present invention, the selection of M is as described above, details are not described herein.
The method provided according to the present invention, it is preferable that the X1Selected from bromine or chlorine, further preferably bromine.
A kind of specific embodiment according to the present invention, the contact are being carried out in solvent.The solvent can be selected from first Benzene, Isosorbide-5-Nitrae-at least one of dioxane and the tert-butyl alcohol, preferably toluene.By every moleMeter, the solvent Total amount can for 2000-8000 milliliter, be preferably 4000-6000 milliliters.
The method provided according to the present invention, the inert atmosphere can be provided by nitrogen and/or argon gas.The inert atmosphere A suitable reaction environment is provided for reaction.
A preferred embodiment of the invention, the alkaline matter are selected from tert-butyl alcohol lithium, sodium tert-butoxide and tertiary fourth At least one of potassium alcoholate.Above-mentioned alkaline matter may be used alone, used in two or more.The alkaline matter is optimal It is selected as tert-butyl alcohol lithium.
The method provided according to the present invention, it is preferable that relative to 1 moleThe use of the alkaline matter Measure 1-5mol, preferably 2-4mol.
In the present invention, the c h bond activated catalyst can be the various catalyst that can be used in c h bond activation, excellent Selection of land, the c h bond activated catalyst are selected from [Rh (cod) Cl]2、[Cp*RhCl2]2、[Ir(cod)Cl]2、Ru(cod)Cl2With Acid chloride (Pd (OAc)2At least one of), further preferably [Rh (cod) Cl]2And/or acid chloride, most preferably [Rh (cod)Cl]2。
In the present invention, [Rh (cod) Cl]2Indicate (1,5- cyclo-octadiene) chlorine rhodium (I) dimer；[Cp*RhCl2]2It indicates Dichloro pentamethylcyclopentadiene base closes rhodium (III) dimer；[Ir(cod)Cl]2Indicate (1,5- cyclo-octadiene) iridium chloride (I) two Aggressiveness；Ru(cod)Cl2Indicate (1,5- cyclo-octadiene) ruthenic chloride.
In the present invention, it is preferred to relative to 100 molesThe use of the c h bond activated catalyst Amount is 0.5-3mol, preferably 2-3mol.
In the present invention, it is preferred toWith M-X1Molar ratio be 1:(0.8-1.2), for having for raw material Effect utilizes, further preferably,With M-X1Molar ratio be 1:1.
In the present invention, it is preferred to it is 70-160 DEG C that the condition of the contact, which includes: temperature, time 14-24h.Into one Preferably, temperature is 110-150 DEG C to step, reaction time 18-24h.
In the present invention, willM-X1, alkaline matter, c h bond activated catalyst and solvent mixing after stir. The present invention coupleM-X1, alkaline matter, c h bond activated catalyst and solvent addition sequence be not particularly limited, As long as being all added before stirring starts.
Above-mentioned temperature can be obtained by various conventional heating modes, such as oil bath heating.
In the present invention, the contact can under nitrogen or argon in commonly used equipment (such as pressure pipe) into Row.
In the present invention, the method can also include isolating 1- (8- aryl naphthalene) phosphine from reaction products therefrom to match Body.The process of the separation can be implemented according to the method for purification of this field routine, such as can be column chromatography, the way of distillation, extraction It follows the example of, preferably column chromatography, more preferably silica gel column chromatography.Eluent can be molten for petroleum ether and methylene chloride mixing Agent.
The present invention also provides the 1- as made from above-mentioned preparation method (8- aryl naphthalene) ligands.
Method of the present invention is particularly suitable for preparing following 1- (8- aryl naphthalene) Phosphine ligands: 1- (8- phenylnaphthalene Base) diphenylphosphine, 1- (8- p-methylphenyl naphthalene) diphenylphosphine, 1- (12345 naphthalene of 8- m-methoxyphenyl) diphenyl Phosphine, 1- (8- rubigan naphthalene) diphenylphosphine, 1- (8- p-trifluoromethyl phenyl naphthalene) diphenylphosphine, (8- is to phenyl acyl by 1- Base phenyl napthyl) diphenylphosphine, 1- (8- (9- phenanthryl) naphthalene) diphenylphosphine, 1- (8- (9- anthryl) naphthalene) diphenylphosphine, 1- (8- (3- (6- picolyl)) naphthalene) diphenylphosphine, 1- (8- (3- (6- trifluoromethyl pyridine base)) naphthalene) diphenylphosphine, 1- (8- isoquinolyl naphthalene) diphenylphosphine, 1- (8- (2- pyrazinyl) naphthalene) diphenylphosphine, 1- (8- (4- (2- methoxypyridine Base)) naphthalene) diphenylphosphine, 1- (8- p-trifluoromethyl phenyl naphthalene) dicyclohexylphosphontetrafluoroborate.
Third aspect present invention provides a kind of phosphine gold complex, which includes 1- provided by the invention (8- arylnaphthalene Base) Phosphine ligands, the complex is with structure shown in formula (3):
Wherein, X is selected from bromine or chlorine (preferably chlorine)；M's and R " is selected from as described above, details are not described herein.
The present invention is not particularly limited the preparation method of the phosphine gold complex, as long as being prepared shown in formula (3) Phosphine gold complex.The preparation method of a kind of specific embodiment according to the present invention, the phosphine gold complex can wrap It includes: in the presence of inert atmosphere and solvent, 1- (8- aryl naphthalene) Phosphine ligands (being indicated by formula (1)) are (excellent with Au (I) complex It is selected as Au (THT) Cl) contact.The inert atmosphere can be provided by nitrogen and/or argon gas (preferably nitrogen), and the solvent can Think methylene chloride.The molar ratio of 1- (8- aryl naphthalene) Phosphine ligands and Au (THT) Cl can be 1:(0.8-1.2), preferably 1:1.The present invention is wider to the range of choice of the dosage of the solvent, for example, based on every mole of 1- (8- aryl naphthalene) Phosphine ligands, The total amount of the solvent can be 2000-8000 milliliters, preferably 5000-7000 milliliters.The condition of the contact can for Under room temperature (15-30 DEG C), time of contact 1-4h.It is preferred that the contact carries out under agitation, the rate of the stirring can Think 800-1200r/min.The contact can carry out in commonly used equipment (such as two neck bottles) under nitrogen or argon.
The preparation method of phosphine gold complex according to the present invention, this method further include separating from reaction products therefrom Phosphine gold complex out.The process of the separation can be implemented according to the method for purification of this field routine, for example, can be using recrystallization Method, the solvent that uses of recrystallizing can be methylene chloride and methanol (volume ratio of the two can be 1:3).
It was found by the inventors of the present invention that the phosphine gold that 1- (8- aryl naphthalene) Phosphine ligands provided by the invention and gold are formed cooperates Object is especially suitable for 4- phenyl -3- crotonylene -one hydration reaction.Compared with other complexs that the prior art provides, the present invention The phosphine gold complex catalytic activity with higher of offer, and the TON value for being catalyzed reaction is higher.Therefore, fourth aspect present invention Application of the above-mentioned phosphine gold complex in 4- phenyl -3- crotonylene -one hydration reaction is provided.Specifically, can by phosphine gold match It closes object and silver hexafluoroantimonate is coordinated, the catalyst of the hydration reaction as 4- phenyl -3- crotonylene -one.
A kind of hydration method of 4- phenyl -3- crotonylene -one, includes: by the cyclopentyl-methyl of phosphine gold complex by method Cyclopentyl-methyl ethereal solution (25 DEG C) of room temperature stirrings in cyclopentyl-methyl ether of ethereal solution, silver hexafluoroantimonate, are then added 4- Phenyl -3- crotonylene -one, ethyl alcohol, trifluoromethanesulfonic acid, react under nitrogen protection, wherein the phosphine gold complex is the present invention The above-mentioned phosphine gold complex provided.
The present invention will be described in detail by way of examples below.
In the present invention,It is prepared according to document (J.Org.Chem.2003,68,4590-4593)；[Rh (cod)Cl]2Catalyst, tert-butyl alcohol lithium, M-X1(it specifically includes: ), Au (THT) Cl and 4- phenyl -3- crotonylene - Ketone is commercially available from lark prestige Science and Technology Ltd..
The present invention surveys the structure of ligands and complexes made from embodiment using NMR spectra and high resolution mass spectrum Examination, wherein NMR spectra is measured with Varian-Mercury 400MHz type NMR spectrometer with superconducting magnet, wherein deuterated reagent is deuterium For chloroform (CDCl3), hydrogen spectrum and carbon spectrum are using tetramethylsilane as internal standard, and phosphorus is composed on the basis of 85% phosphoric acid, and fluorine is composed with 47% 3 On the basis of boron fluoride diethyl ether solution.High resolution mass spectrum is measured by Varian 7.0T FTMS high-resolution mass spectrometer.
In the case where not making the statement of any characteristic, agents useful for same and solvent of the present invention all pass through standard method (with reference to " examination Agent Purifica-tion Handbook ") it uses after purification.Column chromatographs 200-300 mesh silica gel used and is purchased from Wuhan Xin Shenshi Chemical Industry Science Co., Ltd.
In following embodiment, the yield of 1- (8- aryl naphthalene) Phosphine ligands is calculated according to the following formula (I).
Public formula (I):
The yield (%) of 1- (8- aryl naphthalene) Phosphine ligands=[the actual production ÷ 1- of 1- (8- aryl naphthalene) Phosphine ligands The theoretical yield of (8- aryl naphthalene) Phosphine ligands] × 100%.
Embodiment 1
The present embodiment is used to illustrate the preparation of 1- (8- phenyl napthyl) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), bromobenzene (1mmol), [Rh (cod) Cl]2(0.025mmol), tert-butyl alcohol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 DEG C under nitrogen protection, and react 24 at such a temperature Hour.After being cooled to room temperature, produced through silica gel column chromatography (volume ratio of petroleum ether and methylene chloride is 1:20) isolated target ObjectYield is 82%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 7.91-7.88 (m, 2H, Ar), 7.48 (t, J=7.5Hz, 1H, Ar), 7.36- 7.29 (m, 2H, Ar), 7.22-7.15 (m, 8H, Ar), 7.09-7.04 (m, 4H, Ar), 6.94 (t, J=7.2Hz, 4H, Ar)13C NMR(101MHz,CDCl3):δ143.5(d,JC-P=5.1Hz, Ar), 141.3 (d, JC-P=3.6Hz, Ar), 139.4 (d, JC-P =16.7Hz, Ar), 137.2 (s, Ar), 135.5 (s, Ar), 135.2 (d, JC-P=10.1Hz, Ar), 134.9 (d, JC-P= 4.3Hz,Ar),133.7(d,JC-P=20.7Hz, Ar), 130.8 (d, JC-P=7.0Hz, Ar), 130.7 (s, Ar), 130.3 (s, Ar),128.9(d,JC-P=1.5Hz, Ar), 128.0 (d, JC-P=2.7Hz, Ar), 128.0 (s, Ar), 127.5 (s, Ar), 126.9(s,Ar),125.2(s,Ar),124.7(s,Ar).31P NMR(162MHz,CDCl3):δ-8.2(s).HRMS(ESI): m/z:[M+H]+calculated for C28H22P:389.1454,found 389.1444。
Embodiment 2
The present embodiment is used to illustrate the preparation of 1- (8- p-methylphenyl naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), to methyl bromobenzene (1mmol), [Rh (cod) Cl]2(0.025mmol), uncle Butanol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 120 DEG C under nitrogen protection, and at such a temperature Reaction 24 hours.It is isolated through silica gel column chromatography (volume ratio of petroleum ether and methylene chloride is 1:20) after being cooled to room temperature Target productYield is 84%.Nuclear magnetic resonance spectroscopy is carried out to the product, as a result as follows:
1H NMR(400MHz,CDCl3): δ 7.87 (t, J=7.4Hz, 2H, Ar), 7.46 (t, J=7.6Hz, 1H, Ar), 7.31 (dd, J=15.4,7.3Hz, 2H, Ar), 7.22-7.15 (m, 7H, Ar), 6.96-6.92 (m, 6H, Ar), 6.84 (d, J= 7.7Hz,2H,Ar),2.33(s,3H,CH3).13C NMR(101MHz,CDCl3):δ141.4(d,JC-P=3.7Hz, Ar), 140.4(d,JC-P=5.1Hz, Ar), 139.6 (s, Ar), 139.4 (s, Ar), 137.3 (s, Ar), 136.5 (s, Ar), 135.4 (d,JC-P=8.7Hz, Ar), 135.2 (s, Ar), 134.8 (d, JC-P=4.5Hz, Ar), 133.6 (d, JC-P=20.7Hz, Ar), 130.7(s,Ar),130.7(s,Ar),130.6(s,Ar),130.2(s,Ar),128.6(d,JC-P=1.5Hz, Ar), 128.2 (s,Ar),127.9(s,Ar),127.9(s,Ar),125.1(s,Ar),124.7(s,Ar),21.3(s,CH3).31P NMR: (162MHz,CDCl3):δ-8.7(s).HRMS(ESI):m/z:[M+H]+calculated for C29H24P:403.1630, found 403.1637。
Embodiment 3
The present embodiment is used to illustrate the preparation of 1- (8- m-methoxyphenyl naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), meta-methoxy bromobenzene (1mmol), [Rh (cod) Cl]2(0.025mmol)、 Tert-butyl alcohol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 DEG C under nitrogen protection, and in the temperature Lower reaction 24 hours.After being cooled to room temperature, separated through silica gel column chromatography (petroleum ether is 1:20 with the volume ratio of methylene chloride) To target productYield is 81%.Nuclear magnetic resonance spectroscopy is carried out to the product, as a result as follows:
1H NMR(400MHz,CDCl3): δ 7.90 (dd, J=7.9,3.2Hz, 2H, Ar), 7.50-7.46 (m, 1H, Ar), 7.35 (t, J=7.6Hz, 2H, Ar), 7.23-7.14 (m, 7H, Ar), 7.09 (t, J=7.9Hz, 1H, Ar), 6.98 (t, J= 6.8Hz, 2H, Ar), 6.92 (t, J=6.7Hz, 2H, Ar), 6.84-6.79 (m, 2H, Ar), 6.46 (s, 1H, Ar), 3.43 (s, 3H,OCH3).13C NMR(101MHz,CDCl3):δ158.7(s,Ar),144.8(d,JC-P=5.2Hz, Ar), 141.1 (d, JC-P =3.4Hz, Ar), 140.2 (d, JC-P=18.3Hz, Ar), 139.1 (d, JC-P=16.9Hz, Ar), 137.5 (s, Ar), 135.4 (s,Ar),135.1(s,Ar),134.9(s,Ar),134.8(d,JC-P=4.5Hz, Ar), 133.5 (d, JC-P=20.7Hz, Ar),130.3(s,Ar),128.8(d,JC-P=28.8Hz, Ar), 128.1 (s, Ar), 128.1 (s, Ar), 128.0 (d, JC-P= 2.8Hz,Ar),128.0(s,Ar),127.8(s,Ar),125.2(s,Ar),124.7(s,Ar),123.6(d,JC-P=7.7Hz, Ar),115.5(d,JC-P=6.9Hz, Ar), 54.7 (s, OCH3).31P NMR(162MHz,CDCl3):δ-8.8(s).HRMS (ESI):m/z:[M+H]+calculated for C29H24OP:419.1559,found 419.1559。
Embodiment 4
The present embodiment is used to illustrate the preparation of 1- (8- rubigan naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), para chlorobromobenzene (1mmol), [Rh (cod) Cl]2(0.025mmol), tertiary fourth Lithium alkoxide (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 DEG C under nitrogen protection, and anti-at such a temperature It answers 24 hours.After being cooled to room temperature, through silica gel column chromatography (volume ratio of petroleum ether and methylene chloride is 1:20) isolated mesh Mark productYield is 69%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 7.89 (d, J=8.0Hz, 2H, Ar), 7.47 (t, J=7.5Hz, 1H, Ar), 7.34 (t, J=7.6Hz, 1H, Ar), 7.23-7.18 (m, 8H, Ar), 7.01-6.94 (m, 8H, Ar)13C NMR(101MHz, CDCl3):δ141.7(d,JC-P=4.8Hz, Ar), 140.0 (d, JC-P=3.5Hz, Ar), 138.9 (d, JC-P=15.8Hz, Ar),137.2(s,Ar),135.1(s,Ar),134.9(s,Ar),134.8(d,JC-P=3.9Hz, Ar), 134.7 (s, Ar), 133.7(d,JC-P=20.7Hz, Ar), 133.0 (s, Ar), 132.1 (d, JC-P=6.9Hz, Ar), 130.6 (s, Ar), 130.3 (s,Ar),129.2(s,Ar),128.2(s,Ar),128.1(s,Ar),128.0(s,Ar),127.4(s,Ar),125.4(s, Ar),124.7(s,Ar).31P NMR(162MHz,CDCl3):δ-8.4(s).HRMS(ESI):m/z:[M+H]+calculated for C28H21ClP:423.1064,found 423.1070。
Embodiment 5
The present embodiment is used to illustrate the preparation of 1- (8- p-trifluoromethyl phenyl naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), to methyl bromobenzene trifluoride (1mmol), [Rh (cod) Cl]2 (0.025mmol), tert-butyl alcohol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 under nitrogen protection DEG C, and react 24 hours at such a temperature.After being cooled to room temperature, through the silica gel column chromatography (volume ratio of petroleum ether and methylene chloride For the isolated target product of 1:20)Yield is 70%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 7.92 (dd, J=7.6,4.2Hz, 2H, Ar), 7.50 (t, J=7.6Hz, 1H, ), Ar 7.37 (t, J=7.6Hz, 1H, Ar), 7.29-7.24 (m, 4H, Ar), 7.21-7.14 (m, 8H, Ar), 6.93 (dd, J= 11.2,4.2Hz,4H,Ar).13C NMR(101MHz,CDCl3):δ147.0(s,Ar),139.9(d,JC-P=4.0Hz, Ar), 138.7(d,JC-P=15.1Hz, Ar), 137.8 (s, Ar), 135.0 (s, Ar), 134.9 (s, Ar), 134.9 (s, Ar), 134.8 (s,Ar),134.7(s,Ar),134.5(s,Ar),133.6(d,JC-P=20.5Hz, Ar), 131.0 (d, JC-P=6.9Hz, Ar),130.5(d,JC-P=8.8Hz, Ar), 129.6 (s, Ar), 128.9 (q, JC-F=96.0Hz, CF3),128.3(s,Ar), 128.2(s,Ar),128.1(s,Ar),125.8(s,Ar),125.5(s,Ar),124.7(s,Ar),124.2(d,JC-P= 3.3Hz,Ar),123.1(s,Ar).31P NMR(162MHz,CDCl3):δ-8.9(s).19F NMR(376MHz,CDCl3):δ- 62.3(s).HRMS(ESI):m/z:[M+H]+calculated for C29H21F3P:457.1328,found 457.1327。
Embodiment 6
The present embodiment is used to illustrate the preparation of 1- (8- is to phenylacyl phenyl napthyl) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), to phenylacyl bromobenzene (1mmol), [Rh (cod) Cl]2 (0.025mmol), tert-butyl alcohol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 under nitrogen protection DEG C, and react 24 hours at such a temperature.After being cooled to room temperature, through the silica gel column chromatography (volume ratio of petroleum ether and methylene chloride For the isolated target product of 1:20)Yield is 65%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 7.93 (d, J=7.9Hz, 2H, Ar), 7.83 (d, J=7.4Hz, 2H, Ar), 7.59 (t, J=7.3Hz, 1H, Ar), 7.53-7.47 (m, 5H, Ar), 7.38 (t, J=7.5Hz, 1H, Ar), 7.32 (d, J= 6.8Hz, 1H, Ar), 7.23-7.19 (m, 9H, Ar), 6.99 (t, J=7.0Hz, 4H, Ar)13C NMR(101MHz,CDCl3):δ 196.5(s,CO),148.0(d,JC-P=4.7Hz, Ar), 140.2 (d, JC-P=4.2Hz, Ar), 139.0 (s, Ar), 138.9 (s,Ar),137.9(s,Ar),137.6(s,Ar),135.8(s,Ar),135.0(d,JC-P=7.1Hz, Ar), 134.8 (d, JC-P =4.7Hz, Ar), 134.7 (s, Ar), 133.6 (d, JC-P=20.5Hz, Ar), 132.1 (s, Ar), 130.6 (d, JC-P= 7.2Hz,Ar),130.5(d,JC-P=5.6Hz, Ar), 130.0 (s, Ar), 129.5 (d, JC-P=1.6Hz, Ar), 129.4 (s, Ar),128.2(d,JC-P=1.2Hz, Ar), 128.1 (s, Ar), 128.1 (s, Ar), 125.5 (s, Ar), 124.7 (s, Ar)31P NMR(162MHz,CDCl3):δ-8.7(s).[M+H]+calculated for C35H26OP:493.1726,found 493.1730。
Embodiment 7
The present embodiment is used to illustrate the preparation of 1- (8- (9- phenanthryl) naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), 9- bromine phenanthrene (1mmol), [Rh (cod) Cl]2(0.025mmol), the tert-butyl alcohol Lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 DEG C under nitrogen protection, and react at such a temperature 24 hours.After being cooled to room temperature, through silica gel column chromatography (volume ratio of petroleum ether and methylene chloride is 1:20) isolated target ProductYield is 90%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 8.71 (dd, J=14.4,8.4Hz, 2H, Ar), 7.99 (t, J=8.8Hz, 2H, ), Ar 7.62-7.55 (m, 3H, Ar), 7.46-7.36 (m, 5H, Ar), 7.18 (dd, J=20.3,7.4Hz, 2H, Ar), 7.08- 7.00 (m, 7H, Ar), 6.59 (t, J=6.7Hz, 2H, Ar), 6.52 (t, J=7.2Hz, 2H, Ar)13C NMR(101MHz, CDCl3):δ140.0(d,JC-P=20.6Hz, Ar), 139.4 (d, JC-P=4.6Hz, Ar), 139.0 (d, JC-P=4.4Hz, Ar),137.8(d,JC-P=14.3Hz, Ar), 137.0 (s), 136.0 (d, JC-P=21.4Hz, Ar), 135.4 (s, Ar), 135.1(s,Ar),134.9(d,JC-P=4.7Hz, Ar), 134.6 (d, JC-P=9.9Hz, Ar), 133.5 (d, JC-P=9.2Hz, Ar),133.3(d,JC-P=8.4Hz, Ar), 131.7 (s, Ar), 131.2 (s, Ar), 130.6 (s, Ar), 130.5 (s, Ar), 130.2(s,Ar),129.4(d,JC-P=1.9Hz, Ar), 129.1 (d, JC-P=6.3Hz, Ar), 128.9 (s, Ar), 128.1 (s,Ar),128.0(s,Ar),127.8(d,JC-P=7.0Hz, Ar), 127.6 (s, Ar), 127.5 (d, JC-P=1.9Hz, Ar), 126.4(s,Ar),126.3(d,JC-P=7.1Hz, Ar), 126.0 (s, Ar), 125.5 (s, Ar), 125.1 (s, Ar), 122.7 (s,Ar),122.4(s,Ar).31P NMR(162MHz,CDCl3):δ-7.9(s).HRMS(ESI):m/z:[M+H]+ calculated for C36H26P:489.1767,found 489.1784。
Embodiment 8
The present embodiment is used to illustrate the preparation of 1- (8- (9- anthryl) naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), 9- bromine anthracene (1mmol), [Rh (cod) Cl]2(0.025mmol), the tert-butyl alcohol Lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 DEG C under nitrogen protection, and react at such a temperature 24 hours.After being cooled to room temperature, through silica gel column chromatography (volume ratio of petroleum ether and methylene chloride is 1:20) isolated target ProductYield is 52%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 8.56 (s, 1H, Ar), 8.07 (dd, J=13.6,8.1Hz, 2H, Ar), 7.97 (d, J=8.5Hz, 2H, Ar), 7.64 (t, J=7.5Hz, 1H, Ar), 7.47 (d, J=7.1Hz, 1H, Ar), 7.40 (t, J= 7.6Hz, 1H, Ar), 7.29-7.26 (m, 3H, Ar), 7.12 (d, J=8.8Hz, 2H, Ar), 7.03 (t, J=7.4Hz, 2H, ), Ar 6.92 (dd, J=13.0,6.6Hz, 6H, Ar), 6.30 (t, J=7.2Hz, 4H, Ar)13C NMR(101MHz,CDCl3): δ138.6(d,JC-P=19.3Hz, Ar), 137.6 (d, JC-P=3.9Hz, Ar), 137.3 (s, Ar), 137.0 (d, JC-P= 4.5Hz,Ar),136.5(s,Ar),136.3(s,Ar),135.2(s,Ar),135.0(s,Ar),134.9(s,Ar),134.9 (s,Ar),133.0(s,Ar),132.8(s,Ar),132.2(d,JC-P=9.2Hz, Ar), 132.0 (s, Ar), 131.6 (s, Ar),130.9(s,Ar),129.6(s,Ar),128.0(s,Ar),127.7(d,JC-P=6.3Hz, Ar), 127.5 (s, Ar), 127.0(s,Ar),126.9(s,Ar),125.3(d,JC-P=23.7Hz, Ar), 124.7 (d, JC-P=16.2Hz, Ar)31P NMR(162MHz,CDCl3):δ-10.1(s).HRMS(ESI):m/z:[M+H]+calculated for C36H26P: 489.1767,found 489.1757。
Embodiment 9
The present embodiment is used to illustrate the preparation of 1- (8- (3- (6- trifluoromethyl pyridine base)) naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), the bromo- 6- trifluoromethyl pyridine (1mmol) of 3-, [Rh (cod) Cl]2 (0.025mmol), tert-butyl alcohol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 under nitrogen protection DEG C, and react 24 hours at such a temperature.After being cooled to room temperature, through the silica gel column chromatography (volume ratio of petroleum ether and methylene chloride For the isolated target product of 1:20)Yield is 47%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 8.47 (s, 1H, Ar), 7.99-7.93 (m, 2H, Ar), 7.52 (t, J= 7.7Hz, 1H, Ar), 7.38 (t, J=7.7Hz, 2H, Ar), 7.30 (s, 1H, Ar), 7.25 (dd, J=5.2,2.8Hz, 2H, ), Ar 7.22-7.19 (m, 5H, Ar), 7.17-7.14 (m, 1H, Ar), 6.91 (t, J=7.7Hz, 4H, Ar)13C NMR (101MHz,CDCl3):δ151.3(d,JC-P=7.1Hz, Ar), 146.1 (d, JC-P=34.4Hz, Ar), 141.8 (d, JC-P= 4.6Hz,Ar),138.5(d,JC-P=7.6Hz, Ar), 134.2 (q, JC-F=39.4Hz, CF3),136.9(s,Ar),136.1 (d,JC-P=3.2Hz, Ar), 134.9 (d, JC-P=4.2Hz, Ar), 134.4 (s, Ar), 134.2 (d, JC-P=8.4Hz, Ar), 134.1(s,Ar),134.0(d,JC-P=3.5Hz, Ar), 133.8 (d, JC-P=3.9Hz, Ar), 131.1 (s.Ar), 130.6 (s,Ar),130.5(s,Ar),128.7(d,JC-P=17.8Hz, Ar), 128.4 (d, JC-P=6.9Hz, Ar), 128.3 (d, JC-P =6.8Hz, Ar), 125.8 (s, Ar), 124.76 (s, Ar), 123.2 (s, Ar), 120.5 (d, JC-P=14.2Hz, Ar), 118.7(s,Ar).31P NMR(162MHz,CDCl3):δ-6.7(s).19F NMR(376MHz,CDCl3):δ-67.6(s).HRMS (ESI):m/z:[M+H]+calculated for C28H20F3NP:458.1280,found 458.1279。
Embodiment 10
The present embodiment is used to illustrate the preparation of 1- (8- (3- (6- picolyl)) naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), the bromo- 6- picoline (1mmol) of 3-, [Rh (cod) Cl]2 (0.025mmol), tert-butyl alcohol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 under nitrogen protection DEG C, and react 24 hours at such a temperature.After being cooled to room temperature, through the silica gel column chromatography (volume ratio of petroleum ether and methylene chloride For the isolated target product of 1:20)Yield is 40%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 8.18 (s, 1H, Ar), 7.91 (t, J=7.6Hz, 2H, Ar), 7.49 (t, J= 7.6Hz, 1H, Ar), 7.35 (t, J=7.6Hz, 1H, Ar), 7.25 (dd, J=7.1,4.5Hz, 4H, Ar), 7.20-7.16 (m, 4H, Ar), 7.13-7.12 (m, 1H, Ar), 6.95-6.90 (m, 4H, Ar), 6.85 (d, J=7.9Hz, 1H, Ar), 2.57 (s, 3H,CH3).13C NMR(101MHz,CDCl3):δ156.4(s,Ar),150.5(d,JC-P=6.7Hz, Ar), 138.4 (d, JC-P =15.1Hz, Ar), 138.1 (t, JC-P=6.1Hz, Ar), 137.6 (d, JC-P=2.9Hz, Ar), 136.4 (s, Ar), 135.8 (d,JC-P=5.3Hz, Ar), 135.1 (s, Ar), 134.9 (s, Ar), 134.7 (s, Ar), 134.5 (s, Ar), 133.9 (d, JC-P =21.2Hz, Ar), 131.2 (s, Ar), 130.3 (s, Ar), 129.6 (s, Ar), 128.6 (s, Ar), 128.2 (d, JC-P= 3.9Hz,Ar),128.2(d,JC-P=3.9Hz, Ar), 128.2 (s, Ar), 128.0 (d, JC-P=6.7Hz, Ar) .125.4 (s, Ar),124.8(s,Ar),121.5(s,Ar),24.2(s,CH3).31P NMR(162MHz,CDCl3):δ-6.8(s).HRMS (ESI):m/z:[M+H]+calculated for C28H23NP:404.1563,found 404.1572。
Embodiment 11
The present embodiment is used to illustrate the preparation of 1- (8- isoquinolyl naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), 8- chlorine isoquinolin (1mmol), [Rh (cod) Cl]2(0.025mmol), uncle Butanol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 150 DEG C under nitrogen protection, and at such a temperature Reaction 24 hours.It is isolated through silica gel column chromatography (volume ratio of petroleum ether and methylene chloride is 1:20) after being cooled to room temperature Target productYield is 65%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 8.23 (d, J=5.7Hz, 1H, Ar), 8.02 (d, J=8.0Hz, 1H, Ar), 7.98 (d, J=8.1Hz, 1H, Ar), 7.79 (d, J=8.2Hz, 1H, Ar), 7.63 (d, J=5.7Hz, 1H, Ar), 7.58 (t, J =7.5Hz, 1H, Ar), 7.53-7.50 (m, 2H, Ar), 7.43-7.38 (m, 2H, Ar), 7.24-7.14 (m, 5H, Ar), 7.08 (t, J=7.2Hz, 1H, Ar), 6.98 (t, J=7.4Hz, 2H, Ar), 6.91 (t, J=7.3Hz, 2H, Ar), 6.51 (t, J= 7.3Hz,2H,Ar).13C NMR(101MHz,CDCl3):δ162.5(s,Ar),142.0(s,Ar),138.7(d,JC-P= 16.3Hz,Ar),138.2(d,JC-P=15.3Hz, Ar), 137.8 (s, Ar), 137.6 (d, JC-P=5.1Hz, Ar), 136.3 (s,Ar),136.0(d,JC-P=24.8Hz, Ar), 134.9 (d, JC-P=5.9Hz, Ar), 134.2 (d, JC-P=26.2Hz, Ar),133.4(s,Ar),133.1(d,JC-P=8.4Hz, Ar), 132.9 (s, Ar), 130.6 (d, JC-P=33.3Hz, Ar), 130.1(s,Ar),129.7(s,Ar),129.6(s,Ar),128.0(s,Ar),127.9(d,JC-P=3.9Hz, Ar), 127.8 (s,Ar),127.6(d,JC-P=25.3Hz, Ar), 126.5 (d, JC-P=7.8Hz, Ar), 125.6 (s, Ar), 124.8 (s, Ar),120.2(s,Ar).31P NMR(162MHz,CDCl3):δ-9.4(s).HRMS(ESI):m/z:[M+H]+calculated for C31H23NP:440.1563,found 440.1562。
Embodiment 12
The present embodiment is used to illustrate the preparation of 1- (8- (2- pyrazinyl) naphthalene) diphenylphosphine.
By 1- naphthalene diphenylphosphine (1mmol), 2- chloropyrazine (1mmol), [Rh (cod) Cl]2(0.025mmol), tertiary fourth Lithium alkoxide (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 150 DEG C under nitrogen protection, and anti-at such a temperature It answers 24 hours.After being cooled to room temperature, through silica gel column chromatography (volume ratio of petroleum ether and methylene chloride is 1:20) isolated mesh Mark productYield is 36%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 8.48 (d, J=19.8Hz, 2H, Ar), 8.27 (s, 1H, Ar), 7.97 (dd, J =21.8,8.1Hz, 2H, Ar), 7.56 (t, J=7.5Hz, 1H, Ar), 7.49-7.36 (m, 2H, Ar), 7.29-7.17 (m, 7H, ), Ar 6.98 (t, J=7.3Hz, 4H, Ar)13C NMR(101MHz,CDCl3):δ157.4(s,Ar),146.1(d,JC-P= 8.5Hz,Ar),143.4(s,Ar),142.2(s,Ar),137.8(d,JC-P=13.8Hz, Ar), 137.6 (s, Ar), 136.4 (d,JC-P=4.3Hz, Ar), 135.0 (s, Ar), 134.9 (d, JC-P=5.5Hz, Ar), 134.8 (s, Ar), 134.2 (s, Ar), 133.9(s,Ar),133.5(d,JC-P=20.2Hz), 130.7 (s, Ar), 130.7 (s, Ar), 130.6 (s, Ar), 128.4 (s, Ar),128.3(d,JC-P=6.6Hz, Ar), 125.8 (s, Ar), 124.8 (s, Ar)31P NMR(162MHz,CDCl3):δ-7.9 (s).HRMS(ESI):m/z:[M+H]+calculated for C26H20N2P:391.1359,found 391.1359。
Embodiment 13
The present embodiment is used to illustrate the preparation of 1- (8- p-trifluoromethyl phenyl naphthalene) dicyclohexylphosphontetrafluoroborate.
By 1- naphthalene dicyclohexylphosphontetrafluoroborate (1mmol), to methyl bromobenzene trifluoride (1mmol), [Rh (cod) Cl]2 (0.025mmol), tert-butyl alcohol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 under nitrogen protection DEG C, and react 24 hours at such a temperature.After being cooled to room temperature, through the silica gel column chromatography (volume ratio of petroleum ether and methylene chloride For the isolated target product of 1:20)Yield is 80%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 7.88 (dd, J=12.2,8.0Hz, 2H, Ar), 7.73 (d, J=7.2Hz, 1H, ), Ar 7.61 (d, J=7.9Hz, 2H, Ar), 7.51-7.45 (m, 2H, Ar), 7.33 (dd, J=12.2,7.5Hz, 3H, Ar), 1.61 (dd, J=27.6,12.5Hz, 8H, Cy), 1.35-1.26 (m, 3H, Cy), 1.16-0.98 (m, 7H, Cy), 0.75-0.72 (m,4H,Cy).13C NMR(101MHz,CDCl3):δ149.7(d,JC-P=5.0Hz, Ar), 140.2 (d, JC-P=5.0Hz, Ar),137.1(d,JC-P=21.4Hz, Ar), 135.3 (s, Ar), 135.0 (s, Ar), 135.0 (s, Ar), 134.9 (s, Ar), 134.1(d,JC-P=2.7Hz, Ar), 130.4 (d, JC-P=8.1Hz, Ar), 130.2 (s, Ar), 129.8 (s, Ar), 129.3 (s,Ar),128.7(q,JC-F=64.6Hz, CF3),124.9(d,JC-P=3.6Hz, Ar), 124.71 (s, Ar), 124.3 (s, Ar),123.4(s,Ar),36.2(s,Cy),36.0(s,Cy),30.4(s,Cy),30.2(s,Cy),29.4(s,Cy),29.3 (s,Cy),27.3(s,Cy),27.2(s,Cy),27.1(s,Cy),27.0(s,Cy),26.4(s,Cy).31P NMR(162MHz, CDCl3):δ-10.0(s).19F NMR(376MHz,CDCl3):δ-62.0(s).HRMS(ESI):m/z:[M+H]+calculated for C29H33F3P:469.2266,found 469.2263。
Embodiment 14
The present embodiment is used to illustrate the preparation of 1- (8- (4- (9- carbazyl) naphthalene)) dicyclohexylphosphontetrafluoroborate.
By 1- naphthalene dicyclohexylphosphontetrafluoroborate (1mmol), 9- (4- bromophenyl) carbazole (1mmol), [Rh (cod) Cl]2 (0.025mmol), tert-butyl alcohol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 110 under nitrogen protection DEG C, and react 24 hours at such a temperature.After being cooled to room temperature, through the silica gel column chromatography (volume ratio of petroleum ether and methylene chloride For the isolated target product of 1:20)Yield is 50%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3): δ 8.18 (d, J=7.7Hz, 2H, Ar), 7.91 (dd, J=12.3,7.9Hz, 2H, ), Ar 7.79 (d, J=6.6Hz, 1H, Ar), 7.62 (d, J=7.5Hz, 2H, Ar), 7.54-7.48 (m, 5H, Ar), 7.45 (t, J =6.7Hz, 4H, Ar), 7.31 (t, J=7.4Hz, 2H, Ar), 1.75-1.56 (m, 10H, Cy), 1.50 (d, J=13.8Hz, 2H,Cy),1.16–1.02(m,6H,Cy),0.90–0.81(m,4H,Cy).13C NMR(101MHz,CDCl3):δ145.2(d, JC-P=6.1Hz, Ar), 141.3 (s, Ar), 140.7 (d, JC-P=4.2Hz, Ar), 137.4 (s, Ar), 137.2 (s, Ar), 136.0(s,Ar),135.4(s,Ar),135.1(s,Ar),135.1(s,Ar),135.0(s,Ar),133.7(s,Ar),131.8 (d,JC-P=8.3Hz, Ar), 130.1 (s, Ar), 129.8 (s, Ar), 129.0 (s, Ar), 127.0 (s, Ar), 125.7 (s, Ar),124.5(d,JC-P=18.8Hz, Ar), 123.2 (s, Ar), 120.2 (s, Ar), 119.7 (s, Ar), 110.2 (s, Ar), 36.2(d,JC-P=20.9Hz, Cy), 30.5 (d, JC-P=20.1Hz, Cy), 29.4 (d, JC-P=10.0Hz, Cy), 27.2 (d, JC-P=7.6Hz, Cy), 27.1 (s, Cy), 26.5 (s, Cy)31P NMR(162MHz,CDCl3):δ-9.0(s).HRMS(ESI): m/z:[M+H]+calculated for C40H41NP:566.2971,found 566.2973。
Embodiment 15
By 1- naphthalene diphenylphosphine (1mmol),[Rh(cod)Cl]2(0.025mmol)、 Tert-butyl alcohol lithium (3mmol) and toluene (5mL) mix in pressure pipe, are heated to 150 DEG C under nitrogen protection, and in the temperature Lower reaction 24 hours.After being cooled to room temperature, separated through silica gel column chromatography (petroleum ether is 1:20 with the volume ratio of methylene chloride) To target productYield is 84%.The product is analyzed, as a result as follows:
1H NMR(400MHz,CDCl3) δ 7.93-7.90 (m, 3H, Ar), 7.49 (t, J=7.5Hz, 1H, Ar), 7.38 (t, J=7.6Hz, 1H, Ar), 7.29 (s, 3H, Ar), 7.20 (dd, J=17.1,8.0Hz, 5H, Ar), 7.02 (t, J=7.1Hz, 2H, Ar), 6.95 (t, J=6.9Hz, 2H, Ar), 6.77 (d, J=5.0Hz, 1H, Ar), 6.35 (s, 1H, Ar), 3.80 (s, 3H, OCH3).13C NMR(101MHz,CDCl3):δ163.4(s,Ar),154.2(d,JC-P=5.1Hz, Ar), 145.6 (s, Ar), 139.2(d,JC-P=16.0Hz, Ar), 138.6 (d, JC-P=4.4Hz, Ar), 138.2 (s, Ar), 138.0 (d, JC-P= 12.5Hz,Ar),134.8(d,JC-P=5.2Hz, Ar), 134.6 (d, JC-P=5.8Hz, Ar), 134.4 (s, Ar), 133.5 (d, JC-P=11.3Hz, Ar), 133.3 (d, JC-P=11.4Hz, Ar), 130.5 (s, Ar), 129.8 (d, JC-P=9.1Hz, Ar), 128.2(d,JC-P=3.4Hz, Ar), 128.2 (d, JC-P=3.0Hz, Ar), 128.1 (s, Ar), 125.5 (s, Ar), 124.7 (s,Ar),119.7(d,JC-P=7.4Hz, Ar), 112.7 (d, JC-P=7.1Hz, Ar), 53.2 (s, OCH3).31P NMR (162MHz,CDCl3):δ-9.8(s).HRMS(ESI):m/z:[M+Na]+calculated for C28H22NOPNa: 442.1331,found 442.1327。
Embodiment 16
According to the method for embodiment 1, unlike, by [Rh (cod) Cl]2Replace with the acid chloride of equimolar amounts, yield It is 21%.
Embodiment 17
According to the method for embodiment 1, unlike, tert-butyl alcohol lithium is replaced with to the sodium tert-butoxide of equimolar amounts, yield is 77%.
Embodiment 18
According to the method for embodiment 1, unlike, tert-butyl alcohol lithium is replaced with to the potassium tert-butoxide of equimolar amounts, by toluene Replace with isometric Isosorbide-5-Nitrae-dioxane, yield 29%.
Following embodiment is used to illustrate the preparation of phosphine gold complex.
The yield (%) of phosphine gold complex=[theoretical yield of the actual production ÷ phosphine gold complex of phosphine gold complex] × 100%.
Embodiment 19
(0.3mmol), Au (THT) Cl (0.3mmol) and methylene chloride made from embodiment 3 are added in two neck bottles (2mL) is stirred 2 hours for (25 DEG C) of room temperature under nitrogen protection, is tied again through methylene chloride and methanol (volume ratio of the two is 1:3) Crystalline substance obtains target product, has structure shown in formula (3), and M is2 R " are phenyl, X Cl, target production The yield of object phosphine gold complex is 94%.Nuclear magnetic resonance spectroscopy is carried out to the product, as a result as follows:
1H NMR(400MHz,CDCl3): δ 8.03 (d, J=7.7Hz, 1H, Ar), 7.91 (d, J=8.0Hz, 1H, Ar), 7.58 (t, J=7.5Hz, 1H, Ar), 7.48 (d, J=7.0Hz, 1H, Ar), 7.45-7.37 (m, 5H, Ar), 7.35-7.28 (m, 5H, Ar), 7.21 (dd, J=13.0,8.0Hz, 2H, Ar), 6.76 (t, J=7.7Hz, 1H, Ar), 6.65 (d, J=7.8Hz, 3H,Ar),3.74(s,3H,OCH3).13C NMR(101MHz,CDCl3):δ159.1(s,Ar),143.0(s,Ar),140.2(d, JC-P=4.5Hz, Ar), 139.1 (d, JC-P=7.4Hz, Ar), 135.2 (d, JC-P=8.2Hz, Ar), 133.9 (d, JC-P= 14.4Hz,Ar),133.5(d,JC-P=10.5Hz, Ar), 133.3 (d, JC-P=14.1Hz, Ar), 132.4 (d, JC-P= 11.4Hz,Ar),132.2(s,Ar),131.6(d,JC-P=19.9Hz, Ar), 131.3 (s, Ar), 131.0 (s, Ar), 129.7 (s,Ar),128.9(s,Ar),128.8(d,JC-P=6.7Hz, Ar), 128.7 (d, JC-P=6.6Hz, Ar), 126.1 (s, Ar), 125.8(s,Ar),125.3(s,Ar),124.4(d,JC-P=11.4Hz, Ar), 124.1 (s, Ar), 115.3 (s, Ar), 113.7 (s,Ar),55.0(s,OCH3).31P NMR(162MHz,CDCl3):δ33.5(s).Anal.Calcd for C29H23AuClOP: C,53.51；H,3.56.Found:C,53.54；H,3.57.
Embodiment 20
In two neck bottles be added embodiment 5 made from 1- (8- p-trifluoromethyl phenyl naphthalene) diphenylphosphine (0.3mmol), Au (THT) Cl (0.3mmol) and methylene chloride (2mL) stir 2 hours for (25 DEG C) of room temperature, under nitrogen protection through methylene chloride It is recrystallized to give target product with methanol (volume ratio of the two is 1:3), there is structure shown in formula (3), M is2 R " is phenyl, and X Cl, the yield of target product phosphine gold complex is 72%.Nuclear magnetic resonance spectroscopy is carried out to the product, as a result It is as follows:
1H NMR(400MHz,CDCl3): δ 8.06 (d, J=8.0Hz, 1H, Ar), 7.96 (d, J=8.1Hz, 1H, Ar), 7.61 (t, J=7.6Hz, 1H, Ar), 7.50-7.46 (m, 3H, Ar), 7.44-7.38 (m, 2H, Ar), 7.37-7.29 (m, 10H, ), Ar 7.04 (d, J=7.9Hz, 2H, Ar)13C NMR(101MHz,CDCl3):δ145.2(s,Ar),139.6(d,JC-P= 6.1Hz,Ar),138.8(d,JC-P=5.4Hz, Ar), 135.4 (s, Ar), 135.3 (s, Ar), 133.7 (s, Ar), 133.6 (s, Ar),133.5(s,Ar),133.0(s,Ar),131.6(s,Ar),130.2(q,JC-F=182.8Hz, CF3),129.1(s, Ar),129.0(s,Ar),126.3(s,Ar),125.3(s,Ar),124.8(s,Ar),124.7(s,Ar),124.6(d,JC-P= 3.5Hz,Ar),122.6(s,Ar).31P NMR(162MHz,CDCl3):δ32.2(s).19F NMR(376MHz,CDCl3):δ- 62.5(s).Anal.Calcd for C29H20AuClF3P:C,50.56；H,2.93.Found:C,50.58；H,2.91.
Embodiment 21
1- (8- (4- (9- carbazyl) naphthalene)) dicyclohexylphosphontetrafluoroborate made from embodiment 14 is added in two neck bottles (0.3mmol), Au (THT) Cl (0.3mmol) and methylene chloride (2mL) stir 2 hours for (25 DEG C) of room temperature under nitrogen protection, It is recrystallized to give target product through methylene chloride and methanol (volume ratio of the two is 1:3), there is structure shown in formula (3), M is2 R " are cyclohexyl, and X Cl, the yield of target product phosphine gold complex is 63%.The product is carried out Nuclear magnetic resonance spectroscopy, as a result as follows:
1H NMR(400MHz,CDCl3): δ 8.15 (d, J=7.7Hz, 2H, Ar), 8.01 (d, J=7.9Hz, 1H, Ar), 7.86 (dd, J=19.9,7.8Hz, 4H, Ar), 7.68 (d, J=7.9Hz, 3H, Ar), 7.64-7.54 (m, 4H, Ar), 7.44 (t, J=7.6Hz, 2H, Ar), 7.31 (t, J=7.4Hz, 2H, Ar), 2.26 (d, J=10.5Hz, 2H, Cy), 2.10 (d, J= 10.6Hz, 2H, Cy), 1.80 (d, J=11.0Hz, 2H, Cy), 1.52 (d, J=10.7Hz, 4H, Cy), 1.41 (d, J= 12.6Hz,2H,Cy),1.29–1.13(m,6H,Cy),1.12–0.93(m,4H,Cy).13C NMR(101MHz,CDCl3):δ 142.9(s,Ar),140.4(s,Ar),139.1(d,JC-P=5.5Hz, Ar), 137.3 (s, Ar), 135.9 (s, Ar), 135.5 (d,JC-P=7.7Hz, Ar), 134.9 (d, JC-P=9.7Hz, Ar), 132.7 (s, Ar), 132.2 (s, Ar), 128.9 (s, Ar), 127.0(s,Ar),126.3(s,Ar),126.1(s,Ar),125.0(s,Ar),124.6(s,Ar),124.5(s,Ar),123.4 (s,Ar),120.2(s,Ar),120.0(s,Ar),109.8(s,Ar),37.6(d,JC-P=31.7Hz, Cy), 31.7 (s, Cy), 30.0(s,Cy),26.6(d,JC-P=13.0Hz, Cy), 26.4 (d, JC-P=14.4Hz, Cy), 25.4 (s, Cy)31P NMR (162MHz,CDCl3):δ46.2(s).Anal.Calcd for C40H40AuClNP:C,60.19；H,5.05；N, 1.75.Found:C,60.13；H,5.04；N,1.76.
Embodiment 22
It is added made from embodiment 15 in two neck bottlesAu(THT)Cl (0.3mmol) and methylene chloride (2mL) stirs 2 hours for (25 DEG C) of room temperature, under nitrogen protection through methylene chloride and methanol (two The volume ratio of person is 1:3) it is recrystallized to give target product, there is structure shown in formula (3), M is2 R " are equal For phenyl, X Cl, the yield of target product phosphine gold complex is 59%.Nuclear magnetic resonance spectroscopy is carried out to the product, as a result such as Under:
1H NMR(400MHz,CDCl3): δ 8.05 (dd, J=7.4,2.1Hz, 1H, Ar), 7.98-7.95 (m, 1H, Ar), 7.91 (d, J=5.2Hz, 1H, Ar), 7.62-7.58 (m, 1H, Ar), 7.50-7.48 (m, 3H, Ar), 7.45-7.35 (m, 6H, ), Ar 7.32-7.27 (m, 2H, Ar), 7.19-7.14 (m, 2H, Ar), 7.08 (dd, J=5.2,1.3Hz, 1H, Ar), 6.17 (s, 1H,Ar),3.68(s,3H,OCH3).13C NMR(101MHz,CDCl3):δ163.2(s,Ar),151.9(s,Ar),147.1(s, Ar),139.6(d,JC-P=6.6Hz, Ar), 137.7 (d, JC-P=5.2Hz, Ar), 135.3 (d, JC-P=8.5Hz, Ar), 133.7(s,Ar),133.6(s,Ar),133.5(d,JC-P=3.0Hz, Ar), 133.4 (s, Ar), 133.3 (t, JC-P= 5.8Hz,Ar),133.1(s,Ar),132.4(s,Ar),132.1(s,Ar),131.5(d,JC-P=2.4Hz, Ar), 131.2 (d, JC-P=2.4Hz, Ar), 130.1 (s, Ar), 129.5 (s, Ar), 129.2 (s, Ar), 129.0 (s, Ar), 129.0 (s, Ar), 128.8(s,Ar),126.3(s,Ar),125.4(s,Ar),124.8(d,JC-P=11.1Hz, Ar), 119.3 (s, Ar), 113.0 (s,Ar),53.2(s,OCH3).31P NMR(162MHz,CDCl3):δ32.8(s).Anal.Calcd for C28H22AuClNOP: C,51.59；H,3.40；N,2.15.Found:C,51.53；H,3.41；N,2.17.
Test example 1
This test example is for illustrating phosphine gold complex provided by the invention in 4- phenyl -3- crotonylene -one hydration reaction Application advantage.Specifically test method includes:
In equipped with the stirring sealable reaction flask of magneton, 50 μ L phosphine gold complex (respectively embodiment 19-22 systems are added Phosphine gold complex) cyclopentyl-methyl ethereal solution (dosage of the phosphine gold complex based on 4- phenyl -3- crotonylene -one be 0.02mol%) (silver hexafluoroantimonate is based on 4- phenyl -3- crotonylene -one with the cyclopentyl-methyl ethereal solution of 10 μ L silver hexafluoroantimonates Dosage be 0.03mol%), then in 1 milliliter of cyclopentyl-methyl ether (25 DEG C) of room temperature stir 30 minutes, then to reaction flask Middle addition 4- phenyl -3- crotonylene -one (1mmol), ethyl alcohol (0.5mmol), trifluoromethanesulfonic acid 0.9mol% (20 μ L, 0.45M) It is reacted 36 hours in lower 110 DEG C of nitrogen protection.It is cooled to room temperature after reaction, calculates the conversion of 4- phenyl -3- crotonylene -one Rate and TON value, the results are shown in Table 1.
The conversion ratio of 4- phenyl -3- crotonylene -one passes through1HNMR measures 4- phenyl -3- butine-in raw material and product respectively The characteristic peak of 2- ketone measures.
=[(amount of the 4- phenyl -3- crotonylene -one of addition)-(4- phenyl -3- crotonylene -one in reaction product Amount)] ÷ be added 4- phenyl -3- crotonylene -one amount × 100%.
The substance of the amount of the substance of the 4- phenyl -3- crotonylene ketone converted in TON value=reaction/participation reaction catalyst Amount.
Comparative example 1
It is added in two neck bottles purchased from lark prestigeAu(THT)Cl(0.3mmol) With methylene chloride (2mL), stir 2 hours for (25 DEG C) of room temperature under nitrogen protection, through methylene chloride and the methanol (volume ratio of the two Target product, yield 83% are recrystallized to give for 1:3).Nuclear magnetic resonance spectroscopy is carried out to the product, as a result as follows:1H NMR (400MHz,CDCl3): δ 7.72 (t, J=8.7Hz, 1H, Ar), 7.57-7.44 (m, 5H, Ar), 7.31 (d, J=4.6Hz, 1H, ), Ar 7.17 (d, J=7.1Hz, 2H, Ar), 2.04 (dd, J=11.7,9.4Hz, 2H, Cy), 1.95 (d, J=11.5Hz, 2H, Cy),1.82–1.75(m,4H,Cy),1.66(s,4H,Cy),1.50–1.40(m,2H,Cy),1.30–1.15(m,8H,Cy).13C NMR(101MHz,CDCl3):δ148.8(d,JC-P=10.8Hz, Ar), 141.3 (d, JC-P=5.1Hz, Ar), 134.2 (d, JC-P =8.2Hz, Ar), 132.4 (d, JC-P=7.5Hz, Ar), 130.7 (s, Ar), 129.2 (s, Ar), 128.4 (d, JC-P= 29.8Hz),127.4(d,JC-P=8.9Hz, Ar), 125.0 (s, Ar), 124.5 (s, Ar) 36.6 (s, Cy), 36.3 (s, Cy), 31.1(d,JC-P=3.9Hz, Cy), 29.3 (s, Cy), 26.4 (dd, JC-P=13.5,8.3Hz, Cy), 25.5 (s, Cy)31P NMR(162MHz,CDCl3):δ43.7(s)。
Comparative example 2
It is added in two neck bottles purchased from lark prestige(0.3mmol, tBu indicate tert-butyl), Au (THT) Cl (0.3mmol) and methylene chloride (2mL) stir 2 hours for (25 DEG C) of room temperature, under nitrogen protection through methylene chloride Target product, yield 62% are recrystallized to give with methanol (volume ratio of the two is 1:3).Nuclear magnetic resonance point is carried out to the product Analysis, as a result as follows:
1H NMR(400MHz,CDCl3): δ 7.85 (t, J=7.9Hz, 1H, Ar), 7.53 (t, J=7.5Hz, 2H, Ar), 7.46 (d, J=7.5Hz, 1H, Ar), 7.35 (s, 1H, Ar), 7.14 (d, J=8.2Hz, 1H, Ar), 7.08 (t, J=7.3Hz, 1H, Ar), 6.97 (d, J=7.0Hz, 1H, Ar), 2.47 (s, 6H, NCH3), 1.53 (d, J=15.5Hz, 9H, tBu), 1.25 (d, J=15.3Hz, 9H, tBu)13C NMR(101MHz,CDCl3):δ151.0(s,Ar),149.0(d,JC-P=13.2Hz, Ar),136.2(d,JC-P=6.0Hz, Ar), 134.3 (d, JC-P=7.9Hz, Ar), 133.7 (s, Ar), 131.0 (d, JC-P= 47.9Hz,Ar),129.2(s,Ar),127.1(s,Ar),126.6(s,Ar),126.2(d,JC-P=6.9Hz, Ar), 122.2 (s,Ar),121.0(s,Ar),43.8(s,NCH3),37.9(d,JC-P=26.2Hz, tBu), 37.4 (d, JC-P=25.9Hz, tBu),31.5(d,JC-P=6.7Hz, tBu), 30.1 (d, JC-P=6.5Hz, tBu)31P NMR(162MHz,CDCl3):δ61.3 (s)。
Comparative experimental example 1-2
According to the method for test example 1, the difference is that, phosphine gold complex is replaced with to 1 He of comparative example of equimolar amounts respectively Phosphine gold complex made from comparative example 2.
The results are shown in Table 1 for the conversion ratio and TON of 4- phenyl -3- crotonylene -one.
Table 1
It can be seen that the preparation method operation letter of Phosphine ligands provided by the invention by the result of above embodiments, table 1 Single, yield is high, and substrate use scope is wide, and phosphine gold complex can efficiently be catalyzed the water of 4- phenyl -3- crotonylene -one Change reaction, such ligand is compared with the ligand of commercialization with higher catalytic activity and higher TON value.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (15)

1. a kind of 1- (8- aryl naphthalene) Phosphine ligands, which is characterized in that the ligand by following formula (1) indicate,
Wherein, 2 R " are each independently selected from phenyl or cyclohexyl, M be selected from substituted or unsubstituted heteroaryl or substitution or Unsubstituted aryl；The hetero atom of the heteroaryl is nitrogen-atoms, and the substituent group of the heteroaryl is selected from methyl, methoxyl group, three At least one of methyl fluoride ,-Cl and-Br；The substituted aryl by following formula (2) indicate,
Wherein, R is selected from-CH3、-OCH3、-CF3Or-Cl；
The substituted or unsubstituted heteroaryl is selected fromR1Respectively with R' Independently selected from methyl, methoxyl group or trifluoromethyl；
Unsubstituted aryl be phenyl,
Wherein, the ligand does not include
2. a kind of preparation method of 1- (8- aryl naphthalene) Phosphine ligands, this method comprises:
Under an inert atmosphere, willM-X1, alkaline matter and the contact of c h bond activated catalyst, wherein 2 R " are each From independently selected from phenyl or cyclohexyl；X1For halogen, M is selected from substituted or unsubstituted heteroaryl or substituted or unsubstituted Aryl；The hetero atom of the heteroaryl is nitrogen-atoms, and the substituent group of the heteroaryl is selected from methyl, methoxyl group, fluoroform At least one of base ,-Cl and-Br；The substituted aryl by following formula (2) indicate,
Wherein, R is selected from-CH3、-OCH3、-CF3Or-Cl；
The substituted or unsubstituted heteroaryl is selected fromR1Respectively with R' Independently selected from methyl, methoxyl group or trifluoromethyl；
Unsubstituted aryl be selected from phenyl,
The c h bond activated catalyst is selected from [Rh (cod) Cl]2、[Cp*RhCl2]2、[Ir(cod)Cl]2、Ru(cod)Cl2And second At least one of sour palladium；
Wherein, the ligand that the preparation method is prepared do not include
3. preparation method according to claim 2, wherein the condition of the contact includes: that temperature is 70-160 DEG C, the time For 12-24h.
4. preparation method according to claim 2, wherein the X1Selected from bromine or chlorine.
5. preparation method according to claim 2, wherein the c h bond activated catalyst is [Rh (cod) Cl]2。
6. preparation method according to claim 2 or 5, wherein relative to 100 molesThe c h bond The dosage of activated catalyst is 0.5-3mol.
7. preparation method according to claim 2 or 5, wherein relative to 100 molesThe C-H The dosage of bond activation catalyst is 2-3mol.
8. preparation method according to claim 2, wherein the alkaline matter is selected from tert-butyl alcohol lithium, sodium tert-butoxide and uncle At least one of butanol potassium.
9. preparation method according to claim 2, wherein the alkaline matter is tert-butyl alcohol lithium.
10. the preparation method according to any one of claim 2,8 and 9, wherein relative to 1 moleThe dosage of the alkaline matter is 1-5mol.
11. the preparation method according to any one of claim 2,8 and 9, wherein relative to 1 moleThe dosage of the alkaline matter is 2-4mol.
12. preparation method according to claim 2, whereinWith M-X1Molar ratio be 1:(0.8-1.2).
13. preparation method according to claim 2 or 3, wherein the condition of the contact includes: that temperature is 110-150 DEG C, time 18-24h.
14. a kind of phosphine gold complex, the ligand of the complex is 1- described in claim 1 (8- aryl naphthalene) Phosphine ligands, institute Complex is stated with structure shown in formula (3):
Wherein, 2 R " are each independently selected from phenyl or cyclohexyl, and X is selected from bromine or chlorine, and M is selected from substituted or unsubstituted heteroaryl Base or substituted or unsubstituted aryl；The hetero atom of the heteroaryl is nitrogen-atoms, and the substituent group of the heteroaryl is selected from first At least one of base, methoxyl group, trifluoromethyl ,-Cl and-Br；The substituted aryl by following formula (2) indicate,
Wherein, R is selected from-CH3、-OCH3、-CF3Or-Cl；
The substituted or unsubstituted heteroaryl is selected fromR1Respectively with R' Independently selected from methyl, methoxyl group or trifluoromethyl；
Unsubstituted aryl be phenyl,
Wherein, the ligand does not include
15. application of the phosphine gold complex described in claim 14 in 4- phenyl -3- crotonylene -one hydration reaction.
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