CN111116666A - Preparation and application of triphenylphosphine allyl palladium halide compound and derivative thereof - Google Patents

Preparation and application of triphenylphosphine allyl palladium halide compound and derivative thereof Download PDF

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CN111116666A
CN111116666A CN201911285379.4A CN201911285379A CN111116666A CN 111116666 A CN111116666 A CN 111116666A CN 201911285379 A CN201911285379 A CN 201911285379A CN 111116666 A CN111116666 A CN 111116666A
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palladium
allyl
compound
triphenylphosphine
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CN111116666B (en
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黄德光
李影华
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Fujian Institute of Research on the Structure of Matter of CAS
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    • C—CHEMISTRY; METALLURGY
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/006—Palladium compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium

Abstract

The application discloses a synthesis method of a triphenylphosphine allyl palladium halide compound and derivatives thereof, which comprises the step of reacting a mixture containing palladium salt, a halogenated allyl compound and a trisubstituted phosphine compound in one step to obtain the triphenylphosphine allyl palladium halide compound and the derivatives thereof. The method has the advantages of low cost, high efficiency, easy operation and high safety. The prepared triphenylphosphine allyl palladium halide compound and derivatives thereof can be widely used as catalysts for catalytic cross-coupling or homocoupling reactions of various organic substrates to prepare various organic reaction intermediates.

Description

Preparation and application of triphenylphosphine allyl palladium halide compound and derivative thereof
Technical Field
The application relates to a preparation method of a triphenylphosphine allyl palladium halide compound and a derivative thereof, belonging to the field of catalyst synthesis.
Background
The palladium complex has rich reactivity in the aspect of metal organic chemistry, and has the advantages of high efficiency, small dosage, high selectivity and the like when used as a catalyst. The pi-allyl palladium complex is a very important chemical reaction intermediate, is easy to react with different nucleophiles to derive abundant chemical changes, and plays an important role in palladium-catalyzed organic reaction. In addition, the phosphine ligand has a special push-pull electronic effect, so that the valence change of central atom palladium can be more flexible, and the application of the palladium complex in the field of catalysis is facilitated.
Existing triphenylphosphine allyl palladium chloride [ Pd (PPh)3)(η3-C3H5)Cl]The synthesis method comprises preparing allyl palladium chloride dimer [ Pd (η) by palladium chloride under reduction condition under the protection of inert gas (such as nitrogen and argon)3-C3H5)Cl]2(W.T.Dent et al, J.chem.Soc.,1964, 1585-. Meanwhile, triphenylphosphine Palladium chloride Compound [ Pd (PPh) substituted with allyl derivative3)(R-C3H4)Cl]The synthesis of (II) has also been reported, and the method used is mainly to synthesize palladium dimer, and then react with allyl derivative to obtain the target product (T. Ohta et al, Organometallics,1985,4, 2080-2085; J. W. Faller et al, Inorg. chem.1985,24, 4483-4490; P.G. Anil kumar et al, Organometallics,2005,24, 1306-1314; M.H. Katcher et al, Organometallics,2014,33, 2121-2133; T.Iwai et al, Organometallics,2016,35, 3959-3969).
In contrast, literature is concerned with the synthesis of triphenylphosphine allyl palladium bromide [ Pd (PPh)3)(η3-C3H5)Br]And triphenylphosphine allyl palladium iodide [ Pd (PPh)3)(η3-C3H5)I]There are few reports and related literature on the synthesis of their derivatives, and the methods are often performed by using palladium salts such as palladium chloride as a raw material, preparing a palladium bromide dimer compound, and then reacting the dimer with a phosphine ligand or an alkene ligand to obtain a phosphine ligand allyl palladium bromide derivative (a.m.johns et al, j.am.chem.soc.,2006,128, 1828-1839; t.murahashi et al, j.am.chem.soc.,2009,131, 9888-9889; b.mart i n-Ruiz et al, Organometallics,2018,37, 1655-1670). Up to now, no one-step synthesis of triphenylphosphine allyl palladium halide [ Pd (PPh)3)(η3-C3H5)X](X ═ Cl, Br, I).
In general, the synthesis method of the phosphine ligand allyl palladium halide compound reported in the literature has the disadvantages of complicated process, high material cost, troublesome operation and poor method universality, so the synthesis method for obtaining the phosphine ligand allyl palladium halide compound and the derivatives thereof by one step with lower cost and simple and convenient method has important significance for the application and popularization of the complex.
Disclosure of Invention
According to one aspect of the application, a synthesis method of triphenylphosphine allyl palladium halide and derivatives thereof is provided, the method synthesizes triphenylphosphine allyl palladium halide and derivatives thereof through one-step reaction, and the method has the advantages of low cost, high efficiency, easy operation and high safety.
A synthesis method of triphenylphosphine allyl palladium halide compounds and derivatives thereof is characterized in that a mixture containing palladium salt, halogenated allyl compounds and trisubstituted phosphine compounds is subjected to one-step reaction to obtain triphenylphosphine allyl palladium halide compounds and derivatives thereof.
Alternatively, the molar ratio of the palladium salt, the halogenated allyl compound and the tri-substituted phosphine compound is in the range of:
1：1-20：1-10；
preferably, the molar ratio of the palladium salt, the halogenated allyl compound and the tri-substituted phosphine compound is in the following range:
1：2-10：1-5。
alternatively, the molar ratio of the palladium salt, the halogenated allyl compound and the tri-substituted phosphine compound is in the range of:
1：4：2。
optionally, the mixture containing the palladium salt, the halogenated allyl compound and the trisubstituted phosphine compound also comprises an activator;
the activating agent comprises at least one of organic base and inorganic base.
Optionally, the inorganic base is selected from at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, cesium bicarbonate.
The organic base is at least one of potassium tert-butoxide, sodium tert-butoxide, potassium ethoxide, sodium ethoxide and sodium methoxide.
Optionally, the activator and palladium salt are in a molar ratio of 1 to 5: 1.
Alternatively, the activator and palladium salt are in a molar ratio of 2: 1.
Alternatively, the activator and palladium salt are in a molar ratio of 2.5: 1.
Optionally, the palladium salt is selected from at least one of palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium tetrafluoroborate, and palladium trifluoromethanesulfonate.
Optionally, the halogenated allyl compound is selected from compounds with the chemical formula of formula I
Figure BDA0002317828290000031
Wherein, X is selected from one of Cl-, Br-and I-.
Alternatively, the trisubstituted phosphine compound is selected from compounds having the formula II-1 or II-2
Figure BDA0002317828290000032
Figure BDA0002317828290000041
Wherein R is1、R2、R3、R4、R5、R6Each independently selected from H-, Ph-, CH3O-, alkyl and halogen elements;
alternatively, the alkyl group is selected from CH3-、CH3CH2-、CH3CH2CH2-、(CH3)2CH-、CH3CH2CH2CH2-、(CH3)2CHCH2-、(CH3)3C-is one of the group; the halogen element is selected from one of F-, Cl-, Br-and I-;
alternatively, R1、R2、R3Are the same hydrogen substituent groups; r4、R5、R6The same hydrogen substituents.
Optionally, the mixture containing the palladium salt, the halogenated allyl compound and the trisubstituted phosphine compound also comprises a solvent;
the solvent is at least one selected from 1, 2-dichloroethane, tetrahydrofuran, dichloromethane, chloroform and 1, 4-dioxane.
Alternatively, the molar ratio of the solvent to the palladium salt is 40-400: 1.
Alternatively, the solvent and palladium salt are in a molar ratio of 80: 1.
Optionally, the reaction atmosphere is air or an inert gas atmosphere.
Optionally, the inert gas is selected from at least one of nitrogen, argon, helium.
Optionally, the reaction temperature is 60-100 ℃, and the reaction time is 16-32 h.
Optionally, the reaction temperature is 70-90 ℃, and the reaction time is 20-28 h.
Optionally, the reaction temperature is 60-80 ℃, and the reaction time is 16-24 h.
Further alternatively, the reaction temperature is 80 ℃ and the reaction time is 24 h.
Optionally, the crude product after the reaction is separated and purified to obtain the triphenylphosphine allyl palladium halide compound and derivatives thereof.
Optionally, the separation and purification mode is washing, recrystallization or column chromatography.
Alternatively, the wash is an ether/acetone wash.
Alternatively, the recrystallization is crude product stirred in petroleum ether/acetone, filtered to give solid product, and recrystallized with dichloromethane/diethyl ether.
Alternatively, the recrystallization is the crude product stirred in petroleum ether/acetone (20:1v/v) for 10 minutes, filtered to give a solid product, which is recrystallized from dichloromethane/diethyl ether.
As a specific implementation mode, the method comprises the following steps:
a) mixing a palladium salt, a halogenated allyl compound, a tri-substituted phosphine compound and an inorganic base in a solvent for reaction;
b) heating to 60-100 deg.C in air or nitrogen atmosphere, stirring for 16-32h, filtering, draining solvent, washing the residual crude product with diethyl ether/acetone, or purifying with column to obtain triphenylphosphine allyl palladium halide compound and its derivatives.
As a preferred embodiment, the method comprises the following steps:
mixing palladium acetate, allyl bromide, triphenylphosphine and potassium tert-butoxide in a 1, 2-dichloroethane solution, heating to 80 ℃ in a nitrogen environment, stirring for 24h, diluting the reaction solution with dichloromethane, filtering, draining the solvent, and washing the crude product with diethyl ether/acetone to obtain the triphenylphosphine allyl palladium bromide compound.
As another aspect of the present application, there is provided a use of the triphenylphosphine allyl palladium halide compound prepared by the above method and its derivatives as a catalyst in a coupling reaction;
optionally, the coupling reaction comprises a cross-coupling reaction, a homocoupling reaction.
Optionally, the triphenylphosphine allyl palladium halide compound and the derivative thereof are used as catalysts in the reaction of synthesizing carbazole by taking aniline and 1-bromo-2-chlorobenzene as raw materials.
Optionally, the triphenylphosphine allyl palladium halide compound and the derivative thereof are used as a catalyst in the reaction of synthesizing (E) -1, 3-diphenyl-1-butene by using styrene as a raw material.
The reaction process according to the method of the present application is exemplified as follows, wherein,
Figure BDA0002317828290000051
the raw material is triphenylphosphine, and the target product is triphenylphosphine allyl palladium bromide.
Figure BDA0002317828290000061
II, taking p-methyl triphenylphosphine as a raw material, and taking p-methyl triphenylphosphine allyl palladium bromide as a target product.
Figure BDA0002317828290000062
III, taking p-fluoro triphenylphosphine as a raw material, and taking p-fluoro triphenylphosphine allyl palladium bromide as a target product.
Figure BDA0002317828290000063
IV, the raw material is tricyclohexylphosphine, and the target product is tricyclohexylphosphine allyl palladium bromide.
Figure BDA0002317828290000064
V, taking allyl chloride as a raw material, and taking trimethylphosphine allyl palladium chloride as a target product.
Figure BDA0002317828290000065
VI, the raw material is allyl iodide, and the target product is trimethyl phosphine allyl palladium iodide.
Figure BDA0002317828290000071
VII, cross coupling reaction with triphenylphosphine allyl palladium bromide as a catalyst.
Figure BDA0002317828290000072
VIII, homogeneous coupling reaction with triphenylphosphine allyl palladium bromide as a catalyst.
Compared with the prior art, the method can synthesize the phosphine ligand allyl halide compound by a one-step method from the most basic divalent palladium raw material, and has the characteristics of higher yield, fewer steps and safer raw material. The palladium compound is stable, insensitive to oxygen and heat, has three different types of coordination groups of strong coordination phosphine atoms, conjugated allyl and halogen atoms, is easy to match with different types of organic substrates to play a role, and can be widely applied to catalytic cross-coupling or homocoupling reaction of various types of organic substrates as a catalyst to prepare various organic reaction intermediates. In addition, the coupling reaction carried out by taking the divalent palladium complex provided by the invention as a catalyst can improve the reaction condition and simplify the steps of separation and purification, and the obtained product has higher yield.
The beneficial effects that this application can produce include:
1) according to the synthesis method of triphenylphosphine allyl palladium halide and derivatives thereof, triphenylphosphine, allyl bromide and palladium acetate are used for synthesizing a target product in one step in nitrogen, the synthesis step is simple, the reaction condition is mild, the raw materials are low in price and low in production cost, and the raw materials are safe and environment-friendly, are wide in applicability and have good economic benefits.
2) The synthesis method of triphenylphosphine allyl palladium halide and derivatives thereof provided by the application has a simple operation flow, and has higher yield and the yield of target products can reach 85% while improving the efficiency due to few steps.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of sample 1 in example 1 of the present application;
FIG. 2 is a nuclear magnetic resonance (hydrogen) chart (solvent CDCl) of sample 1 in example 1 of the present application3)；
FIG. 3 is a nuclear magnetic resonance (carbon spectrum) of sample 1 in example 1 of the present application (solvent CDCl)3)；
FIG. 4 is a schematic diagram of the crystal structure of sample 2 in example 2 of the present application;
FIG. 5 is a nuclear magnetic resonance (hydrogen) chart (solvent CDCl) of sample 2 in example 2 of the present application3)；
FIG. 6 is a nuclear magnetic resonance image (carbon spectrum) of sample 2 in example 2 of the present application (solvent CDCl)3)；
FIG. 7 is a schematic diagram showing the crystal structure of sample 3 in example 3 of the present application;
FIG. 8 is a nuclear magnetic resonance (hydrogen) chart of sample 3 in example 3 of the present application (solvent CDCl)3)；
FIG. 9 is a nuclear magnetic resonance image (carbon spectrum) of sample 3 in example 3 of the present application (solvent CDCl)3)；
FIG. 10 is a nuclear magnetic resonance (hydrogen) chart (solvent CDCl) of sample 4 in example 4 of the present application3)；
FIG. 11 is a nuclear magnetic resonance image (carbon spectrum) of sample 4 in example 4 of the present application (solvent CDCl)3)；
FIG. 12 is a nuclear magnetic resonance (hydrogen) chart (solvent CDCl) of sample 5 in example 5 of the present application3)；
FIG. 13 is a nuclear magnetic resonance image (carbon spectrum) of sample 5 in example 5 of the present application (solvent CDCl)3)；
FIG. 14 is a nuclear magnetic resonance (hydrogen) chart (solvent CDCl) of sample 6 in example 6 of the present application3)；
FIG. 15 is a nuclear magnetic resonance image (carbon spectrum) of sample 6 in example 6 of the present application (solvent CDCl)3)；
FIG. 16 is a nuclear magnetic resonance (hydrogen) chart (solvent CDCl) of sample 7 in example 12 of the present application3)；
FIG. 17 shows a sample obtained in example 12 of the present applicationNuclear magnetic resonance image (carbon spectrum) of product 7 (solvent CDCl)3)；
FIG. 18 is a nuclear magnetic resonance (hydrogen) chart (solvent CDCl) of sample 8 in example 13 of the present application3)；
FIG. 19 is a nuclear magnetic resonance image (carbon spectrum) of sample 8 in example 13 of the present application (solvent CDCl)3)。
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and reagents in the examples of the present application were purchased commercially; wherein palladium acetate, allyl bromide, triphenylphosphine, tricyclohexylphosphine, potassium tert-butoxide are available from Saen chemical technology (Shanghai) Co., Ltd., 1, 2-dichloroethane is available from the national pharmaceutical group, tris (p-methylphenyl) phosphine and tris (p-fluorophenyl) phosphine are available from Inokay; the solvent 1, 2-dichloroethane is subjected to a distillation purification operation before use.
The analysis method in the examples of the present application is as follows:
the crystal structure of the compound was determined using a Supernova single crystal diffractometer (100K) from Agilent.
NMR analysis Using an Avance type III NMR spectrometer from Bruker (R) ((R))1H NMR 400MHz，13C NMR 101MHz)。
Yields in the examples of the present application were calculated as follows:
Figure BDA0002317828290000091
wherein the raw material is palladium salt.
Example 1 preparation of triphenylphosphine allyl palladium bromide and derivatives thereof
The first step is as follows: 36mg of palladium acetate, 84mg of triphenylphosphine, 77mg of allyl bromide, 45mg of potassium tert-butoxide and 1mL of 1, 2-dichloroethane were added to a 50 mL reaction tube, and the mixture was heated to 80 ℃ under a nitrogen atmosphere and reacted for 24 hours.
The second step is that: after completion of the reaction, the reaction mixture was cooled to room temperature, diluted with methylene chloride (20mL), filtered, and dried under reduced pressure.
The third step: the crude product was stirred in petroleum ether/acetone (20:1v/v) for 10 minutes and filtered to give the product (product I) as a yellow solid in the form of a color with a yield of 85%. Recrystallizing the yellow solid with dichloromethane/diethyl ether to obtain the compound with the structural formula of [ Pd (PPh)3)(η3-C3H5)Br]The yellow crystalline product of (1) is noted as sample 1.
And performing single crystal diffraction analysis and nuclear magnetic resonance spectrogram analysis and characterization on the product, and respectively referring to the results of fig. 1, fig. 2 and fig. 3. FIG. 1 is a schematic diagram of the crystal structure of sample 1, from which it can be seen that the valence state of Pd metal is divalent, the coordination configuration with phosphine atom, bromide anion and allyl anion is planar quadrilateral, and the coordination bond length is as follows:
Figure BDA0002317828290000101
Figure BDA0002317828290000102
FIG. 2 is a nuclear magnetic resonance (hydrogen) chart of sample 1 (solvent CDCl)3) (ii) a FIG. 3 is a nuclear magnetic resonance image (carbon spectrum) of sample 1 (solvent CDCl)3) (ii) a As can be seen from FIGS. 2 and 3, the hydrogen spectra of the allylic anion show five independent signals with similar integrated areas, centered in the region of 2.93-5.55ppm, while the signals of hydrogen on triphenylphosphine are divided into two groups, falling in the range of 7.34-7.63 ppm; in addition, the carbon spectrum of the allyl anion shows three small signals with displacements of 64.39, 78.82 and 117.71ppm, while the carbon on the benzene ring of triphenylphosphine shows four groups of signals with two large and two small signals distributed in the region of 128.67-134.19 ppm.
Nuclear magnetic data for sample 1:
1H NMR(400MHz,CDCl3)：δ7.63–7.53(m,6H),7.47–7.34(m,9H),5.55(ddd,J＝20.1,13.2,7.2Hz,1H),4.78(t,J＝6.5Hz,1H),3.68(dd,J＝13.5,10.0Hz,1H),3.32(d,J＝6.4Hz,1H),2.93(d,J＝12.3Hz,1H).
13C NMR(101MHz,CDCl3)：δ134.19(d,J＝12.7Hz),132.57(d,J＝41.9Hz),130.60(d,J＝2.2Hz),128.67(d,J＝10.3Hz),117.71(d,J＝5.1Hz),78.82(d,J＝30.7Hz),64.39(s).
EXAMPLE 2 preparation of tris (p-methylphenyl) phosphinylallyldalladium bromide and its derivatives
The first step is as follows: 36mg of palladium acetate, 97mg of tris (p-methylphenyl) phosphine, 77mg of allyl bromide, 45mg of potassium tert-butoxide and 1mL of 1, 2-dichloroethane were charged into a reaction tube, and the mixture was heated to 80 ℃ under a nitrogen atmosphere and reacted for 24 hours.
The rest of the procedure was the same as in example 1. A bivalent palladium yellow solid (product II) was obtained in 80% yield. The yellow solid was recrystallized from methylene chloride/diethyl ether to give { Pd [ P (P-Me-Ph) ]3](η3-C3H5) Br } as sample 2.
And performing single crystal diffraction analysis and nuclear magnetic resonance spectrogram analysis and characterization on the product, and respectively referring to the results of fig. 4, fig. 5 and fig. 6. FIG. 4 is a schematic diagram of the crystal structure of sample 2, from which it can be seen that the valence of Pd metal is divalent, the coordination configuration with phosphine atom, bromide anion and allyl anion is planar quadrilateral, and the coordination bond length is as follows:
Figure BDA0002317828290000111
Figure BDA0002317828290000112
FIG. 5 is a nuclear magnetic resonance (hydrogen) chart of sample 2 (solvent CDCl)3) (ii) a FIG. 6 is a nuclear magnetic resonance image (carbon spectrum) of sample 2 (solvent CDCl)3) (ii) a From FIGS. 5 and 6, it can be seen that the hydrogen spectrum of the allyl anion shows five independent signals with similar integrated areas, which are concentrated in the region of 2.89-5.64ppm, the signals of the three methyl hydrogen spectra on benzene are the same and show a high peak at the 2.37ppm position, while the signals of hydrogen on triphenylphosphine are divided into two groups and fall in the range of 7.16-7.50 ppm; in addition, the carbon spectrum of the allyl anion shows three small signals with shifts of 63.87 ppm and 78.52,117.51ppm, while the carbon on the benzene ring of triphenylphosphine shows four groups of signals with two large and two small signals distributed in the 129.34-140.66ppm region, and the carbon spectrum signal shift of methyl is 21.53 ppm.
Nuclear magnetic data for sample 2:
1H NMR(400MHz,CDCl3)：δ7.50–7.40(m,6H),7.23–7.16(m,6H),5.64–5.43(m,1H),4.82–4.65(m,1H),3.74–3.55(m,1H),3.30(s,1H),2.89(d,J＝10.2Hz,1H),2.37(s,9H).
13C NMR(101MHz,CDCl3)：δ140.66(d,J＝6.6Hz),134.06(d,J＝51.0Hz),129.75(s),129.34(d,J＝42.1Hz),117.51(d,J＝16.2Hz),78.52(d,J＝116.2Hz),63.87(s),21.53(s).
EXAMPLE 3 preparation of tris (p-fluorophenyl) phosphinylillylpalladium bromide and its derivatives
The first step is as follows: 36mg of palladium acetate, 101mg of tris (p-fluorophenyl) phosphine, 77mg of allyl bromide, 45mg of potassium tert-butoxide and 1mL of 1, 2-dichloroethane were charged into the reaction tube, and the mixture was heated to 80 ℃ under a nitrogen atmosphere and reacted for 24 hours.
The rest of the procedure was the same as in example 1. A divalent palladium yellow solid (product III) was obtained in 85% yield. The yellow solid was recrystallized from methylene chloride/diethyl ether to give { Pd [ P (P-F-Ph) ]3](η3-C3H5) Br } as sample 3.
And performing single crystal diffraction analysis and nuclear magnetic resonance spectrogram analysis and characterization on the product, and respectively referring to the results of fig. 7, fig. 8 and fig. 9. FIG. 7 is a schematic diagram of the crystal structure of sample 3, from which it can be seen that the valence state of Pd metal is divalent, the coordination configuration with phosphine atom, bromide anion and allyl anion is planar quadrilateral, and the coordination bond length is as follows:
Figure BDA0002317828290000113
Figure BDA0002317828290000121
FIG. 8 is a nuclear magnetic resonance (hydrogen) chart of sample 3 (solvent CDCl)3) (ii) a FIG. 9 is a nuclear magnetic resonance image (carbon spectrum) of sample 3 (solvent CDCl)3) (ii) a From FIGS. 8 and 9, it can be seen that the hydrogen spectra of the allylic anion show five independent signals with similar integrated areas, centered in the 2.95-5.69ppm region, while the signals of hydrogen on triphenylphosphine are divided into two groups, falling in the 7.02-7.61ppm range; in addition, the carbon spectrum of the allyl anion shows three small signals,the shift is 64.54 ppm and 79.38,116.24ppm respectively, and the carbon on the benzene ring of triphenylphosphine shows four groups of signals, two large and two small, which are distributed in the 128.04-164.31ppm region.
Nuclear magnetic data for sample 3:
1H NMR(400MHz,CDCl3)：δ7.61–7.49(m,6H),7.20–7.02(m,6H),5.69–5.45(m,1H),4.81(s,1H),3.62(d,J＝59.2Hz,1H),3.33(s,1H),2.95(s,1H).
13C NMR(101MHz,CDCl3)：δ164.31(dd,J＝253.0,2.3Hz),136.20(dd,J＝14.6,8.4Hz),128.04(dd,J＝43.7,3.5Hz),118.08(d,J＝5.1Hz),116.24(dd,J＝21.3,11.5Hz),79.38(d,J＝8.0Hz),64.54(s).
EXAMPLE 4 preparation of Tricyclohexylphosphine allylpalladium bromide and derivatives thereof
The first step is as follows: 36mg of palladium acetate, 90mg of tricyclohexylphosphine, 77mg of allyl bromide, 45mg of potassium tert-butoxide, 1mL of 1, 2-dichloroethane were added to the reaction tube, and the mixture was heated to 80 ℃ under a nitrogen atmosphere and reacted for 24 hours.
The rest of the procedure was the same as in example 1. The divalent palladium compound (product IV) was obtained as a yellow viscous liquid at room temperature, and was identified as sample 4, with a yield of 78%.
And (3) performing analysis and characterization of a nuclear magnetic resonance spectrogram on the yellow viscous liquid, and respectively referring to the results of fig. 10 and fig. 11. FIG. 10 is a nuclear magnetic resonance (hydrogen) chart of sample 4 (solvent CDCl)3) (ii) a FIG. 11 is a nuclear magnetic resonance image (carbon spectrum) of sample 4 (solvent CDCl)3) (ii) a From FIGS. 10 and 11, it can be seen that the hydrogen spectra of the allylic anion show five independent signals with similar integrated areas, centered in the region of 2.67-5.36ppm, while the signals of the hydrogen on tricyclohexylphosphine are mixed in one piece, falling in the range of 1.21-2.20ppm, with the lowest field signal (2.20ppm) being the nuclear magnetic signal of a single hydrogen atom on the carbon atom attached to the phosphine atom on the tricyclohexylphosphine; in addition, the carbon spectrum of the allyl anion shows three small signals with shifts of 54.36 and 79.43,115.89ppm, respectively, while the carbon on the tricyclohexylphosphine ring shows four sets of signals, one large and three small, distributed in the region of 26.46-34.71 ppm.
Nuclear magnetic data for sample 4:
1H NMR(400MHz,CDCl3)：δ5.36(ddd,J＝18.8,13.9,7.7Hz,1H),4.65(t,J＝7.0Hz,1H),3.61(d,J＝5.6Hz,1H),3.50(dd,J＝13.8,9.0Hz,1H),2.67(t,J＝15.3Hz,1H),2.20(td,J＝12.3,10.2Hz,3H),2.01–1.21(m,30H).
13C NMR(101MHz,CDCl3)：δ115.89(d,J＝4.8Hz),79.43(d,J＝29.1Hz),54.36(s),34.71(d,J＝19.1Hz),30.31(s),27.63(d,J＝10.8Hz),26.46(s).
example 5 preparation of triphenylphosphine allyl palladium chloride and derivatives thereof
The first step is as follows: 36mg of palladium acetate, 84mg of triphenylphosphine, 49mg of allyl chloride, 45mg of potassium tert-butoxide and 1mL of 1, 2-dichloroethane were added to a 50 mL reaction tube, and the mixture was heated to 80 ℃ under a nitrogen atmosphere and reacted for 24 hours.
The second step is that: after completion of the reaction, the reaction mixture was cooled to room temperature, diluted with methylene chloride (20mL), filtered, and dried under reduced pressure.
The third step: the crude product was stirred in petroleum ether/acetone (20:1V/V) for 10 minutes and filtered to give the product (product V) as a yellow solid in the form of a color with a yield of 85%. Recrystallizing the yellow solid with dichloromethane/diethyl ether to obtain the compound with the structural formula of [ Pd (PPh)3)(η3-C3H5)Cl]Is recorded as sample 5.
And performing single crystal diffraction analysis and nuclear magnetic resonance spectrogram analysis and characterization on the product, and respectively referring to the results of fig. 12 and fig. 13. FIG. 12 is a nuclear magnetic resonance (hydrogen) chart of sample 5 (solvent CDCl)3) (ii) a FIG. 13 is a nuclear magnetic resonance image (carbon spectrum) of sample 5 (solvent CDCl)3) (ii) a From FIGS. 10 and 11, it can be seen that the hydrogen spectra of the allylic anion show five independent signals with similar integrated areas, centered in the 2.85-5.72ppm region, while the signals for hydrogen on triphenylphosphine are divided into two groups, falling in the 7.36-7.65ppm range; in addition, the carbon spectrum of the allyl anion shows three small signals with the displacement of 61.20 ppm and 80.07,118.18ppm respectively, while the carbon on the benzene ring of triphenylphosphine shows four groups of signals with two large and two small signals distributed in the region of 128.68 ppm to 134.07 ppm.
Nuclear magnetic data of sample 5:
1H NMR(400MHz,CDCl3)：δ7.65–7.56(m,6H),7.49–7.36(m,9H),5.72–5.51(m,1H),4.78(t,J＝6.7Hz,1H),3.88–3.68(m,1H),3.13(s,1H),2.85(d,J＝8.9Hz,1H).
13C NMR(101MHz,CDCl3)：δ134.07(d,J＝12.7Hz),132.37(d,J＝41.8Hz),130.57(d,J＝2.3Hz),128.68(d,J＝10.3Hz),118.18(d,J＝5.0Hz),80.07(d,J＝30.6Hz),61.20(s).
example 6 preparation of triphenylphosphine allyl palladium iodide and derivatives thereof
The first step is as follows: 36mg of palladium acetate, 84mg of triphenylphosphine, 108mg of allyl iodide, 45mg of potassium tert-butoxide and 1mL of 1, 2-dichloroethane were added to a 50 mL reaction tube, and the mixture was heated to 80 ℃ under a nitrogen atmosphere and reacted for 24 hours.
The second step is that: after completion of the reaction, the reaction mixture was cooled to room temperature, diluted with methylene chloride (20mL), filtered, and dried under reduced pressure.
The third step: the crude product was stirred in petroleum ether/acetone (20:1v/v) for 10 minutes and filtered to give the product (product VI) as a yellow solid in the form of a color with a yield of 82%. Recrystallizing the yellow solid with dichloromethane/diethyl ether to obtain the compound with the structural formula of [ Pd (PPh)3)(η3-C3H5)I]Is recorded as sample 6.
And performing single crystal diffraction analysis and nuclear magnetic resonance spectrogram analysis and characterization on the product, and respectively referring to fig. 14 and fig. 15. FIG. 14 is a nuclear magnetic resonance (hydrogen) chart of sample 6 (solvent CDCl)3) (ii) a FIG. 15 is a nuclear magnetic resonance image (carbon spectrum) of sample 6 (solvent CDCl)3) (ii) a From FIGS. 14 and 15, it can be seen that the hydrogen spectra of the allylic anion show five independent signals with similar integrated areas, centered in the 3.08-5.52ppm region, while the signals for hydrogen on triphenylphosphine are divided into two groups, falling in the 7.34-7.64ppm range; in addition, the carbon spectrum of the allyl anion shows three small signals with displacements of 70.29 and 74.47,116.59ppm, while the carbon on the benzene ring of triphenylphosphine shows four groups of signals with two large and two small values distributed in the 128.60-134.33ppm region.
Nuclear magnetic data for sample 6:
1H NMR(400MHz,CDCl3)：δ7.64–7.52(m,6H),7.48–7.34(m,9H),5.52–5.34(m,1H),4.85(s,1H),3.70(s,1H),3.46(s,1H),3.08(s,1H).
13C NMR(101MHz,CDCl3)：δ134.33(d,J＝12.6Hz),132.92(d,J＝42.1Hz),130.58(d,J＝2.2Hz),128.60(d,J＝10.3Hz),116.59(d,J＝7.1Hz),74.47(d,J＝1.6Hz),70.29(s).
example 7 preparation of triphenylphosphine allyl palladium chloride and derivatives thereof
The first step is as follows: to a 50 mL reaction tube were added 28mg of palladium chloride, 84mg of triphenylphosphine, 49mg of allyl chloride, 45mg of potassium tert-butoxide, 1mL of 1, 2-dichloroethane, and the mixture was heated to 80 ℃ under nitrogen atmosphere and reacted for 24 hours.
The second step is that: after completion of the reaction, the reaction mixture was cooled to room temperature, diluted with methylene chloride (20mL), filtered, and dried under reduced pressure.
The third step: the crude product was stirred in petroleum ether/acetone (20:1v/v) for 10 minutes and filtered to give the product (product I) as a yellow solid in the form of a color with a yield of 35%. Recrystallizing the yellow solid with dichloromethane/diethyl ether to obtain the compound with the structural formula of [ Pd (PPh)3)(η3-C3H5)Cl]The yellow crystalline product of (a), is designated sample 5.
The single crystal diffraction analysis and the characterization of nuclear magnetic resonance spectrogram are carried out on the product, and the results are respectively shown in figure 12 and figure 13 (the spectrogram data and the analysis are shown in example 5).
EXAMPLE 8 preparation of triphenylphosphine allyl palladium bromide and its derivatives
The first step is as follows: 36mg of palladium acetate, 84mg of triphenylphosphine, 77mg of allyl bromide, 22mg of potassium hydroxide and 1mL of 1, 2-dichloroethane were added to a 50 mL reaction tube, and the mixture was heated to 80 ℃ under a nitrogen atmosphere and reacted for 24 hours.
The second step is that: after completion of the reaction, the reaction mixture was cooled to room temperature, diluted with methylene chloride (20mL), filtered, and dried under reduced pressure.
The third step: the crude product was stirred in petroleum ether/acetone (20:1v/v) for 10 minutes and filtered to give the product (product I) as a yellow solid in the form of a color with a yield of 71%. Methylene chloride/diethyl ether for yellow solidRecrystallizing to obtain the compound with the structural formula of [ Pd (PPh)3)(η3-C3H5)Br]The yellow crystalline product of (1) is noted as sample 1.
The single crystal diffraction analysis and the characterization of nuclear magnetic resonance spectrogram are carried out on the product, and the results are respectively shown in figure 1, figure 2 and figure 3 (the spectrogram data and the analysis are shown in example 1).
Example 9 preparation of triphenylphosphine allyl palladium bromide and derivatives thereof
The first step is as follows: 36mg of palladium acetate, 84mg of triphenylphosphine, 77mg of allyl bromide, 45mg of potassium tert-butoxide and 1mL of THF were added to a 50 mL reaction tube, and the mixture was heated to 80 ℃ under a nitrogen atmosphere and reacted for 24 hours.
The second step is that: after completion of the reaction, the reaction mixture was cooled to room temperature, diluted with methylene chloride (20mL), filtered, and dried under reduced pressure.
The third step: the crude product was stirred in petroleum ether/acetone (20:1v/v) for 10 minutes and filtered to give the product (product I) as a yellow solid in the form of a color with a yield of 74%. Recrystallizing the yellow solid with dichloromethane/diethyl ether to obtain the compound with the structural formula of [ Pd (PPh)3)(η3-C3H5)Br]The yellow crystalline product of (1) is noted as sample 1.
The single crystal diffraction analysis and the characterization of nuclear magnetic resonance spectrogram are carried out on the product, and the results are respectively shown in figure 1, figure 2 and figure 3 (the spectrogram data and the analysis are shown in example 1).
Example 10 preparation of triphenylphosphine allyl palladium bromide and derivatives thereof
The first step is as follows: 36mg of palladium acetate, 84mg of triphenylphosphine, 77mg of allyl bromide, 45mg of potassium tert-butoxide and 1mL of 1, 2-dichloroethane were added to a 50 mL reaction tube, and the mixture was heated to 80 ℃ under an air atmosphere and reacted for 24 hours.
The second step is that: after completion of the reaction, the reaction mixture was cooled to room temperature, diluted with methylene chloride (20mL), filtered, and dried under reduced pressure.
The third step: the crude product was stirred in petroleum ether/acetone (20:1v/v) for 10 minutes and filtered to give the product (product I) as a yellow solid in the form of a color with a yield of 45%. Recrystallizing the yellow solid with dichloromethane/diethyl ether to obtain the final productHas the formula of [ Pd (PPh)3)(η3-C3H5)Br]The yellow crystalline product of (1) is noted as sample 1.
The single crystal diffraction analysis and the characterization of nuclear magnetic resonance spectrogram are carried out on the product, and the results are respectively shown in figure 1, figure 2 and figure 3 (the spectrogram data and the analysis are shown in example 1).
Example 11 preparation of triphenylphosphine allyl palladium bromide and derivatives thereof
The first step is as follows: 36mg of palladium acetate, 84mg of triphenylphosphine, 77mg of allyl bromide, 45mg of potassium tert-butoxide and 1mL of 1, 2-dichloroethane were added to a 50 mL reaction tube, and the mixture was heated to 60 ℃ under a nitrogen atmosphere and reacted for 16 hours.
The second step is that: after completion of the reaction, the reaction mixture was cooled to room temperature, diluted with methylene chloride (20mL), filtered, and dried under reduced pressure.
The third step: the crude product was stirred in petroleum ether/acetone (20:1v/v) for 10 minutes and filtered to give the product (product I) as a yellow solid in the form of a color with a yield of 50%. Recrystallizing the yellow solid with dichloromethane/diethyl ether to obtain the compound with the structural formula of [ Pd (PPh)3)(η3-C3H5)Br]The yellow crystalline product of (1) is noted as sample 1.
The single crystal diffraction analysis and the characterization of nuclear magnetic resonance spectrogram are carried out on the product, and the results are respectively shown in figure 1, figure 2 and figure 3 (the spectrogram data and the analysis are shown in example 1).
For purposes of this specification, the operating conditions for examples 1-11 are uniformly set forth in the following table.
TABLE 1 preparation of triphenylphosphine allylpalladium halides and derivatives thereof
Figure BDA0002317828290000171
Figure BDA0002317828290000181
Example 12 Cross-coupling reaction with Trimethylphosphineallyl Palladium Bromide as catalyst
Adding 1mL of toluene under the protection of nitrogen37mg of aniline, 113mg of 1-bromo-2-chlorobenzene, 135mg of potassium tert-butoxide, 10mg of [ Pd (PPh) prepared in example 13)(η3-C3H5)Br]And reacted at 120 ℃ for 24 hours. After the reaction was completed, carbazole was obtained by column separation, and the yield thereof was 77%, and it was designated as sample 7.
The carbazole was subjected to nuclear magnetic resonance spectroscopy analysis and characterization, and the results are shown in fig. 16 and 17. FIG. 16 is a nuclear magnetic resonance image (hydrogen spectrum) of sample 7 (solvent CDCl)3) (ii) a FIG. 17 is a nuclear magnetic resonance image (carbon spectrum) of sample 7 (solvent CDCl)3) (ii) a From FIGS. 16 and 17, it can be seen that the broad peak at 8.00-8.07ppm on the hydrogen spectrum is the hydrogen signal on nitrogen, and the other three groups of signals are the hydrogen peaks on benzene ring; on the carbon spectrum, six independent signals respectively correspond to carbon on a benzene ring.
Nuclear magnetic data for sample 7:
1H NMR(400MHz,CDCl3)：δ8.09(d,J＝8.0Hz,2H),8.07–8.00(m,1H),7.46–7.39(m,4H),7.25(ddd,J＝8.0,5.2,3.0Hz,2H).
13C NMR(101MHz,CDCl3)：δ139.61(s),125.97(s),123.48(s),120.47(s),119.58(s),110.71(s).
example 13 Homophilic coupling reaction with trimethylphosphine allylpalladium bromide as catalyst
To 1mL of 1, 4-dioxane in air were added 47mg of styrene, 6mg of trifluoromethanesulfonic acid, and 10mg of [ Pd (PPh) prepared in example 13)(η3-C3H5)Br]And reacted at 100 ℃ for 24 hours. After the reaction was completed, the obtained (E) -1, 3-diphenyl-1-butene was subjected to column separation in a yield of 85% and was designated as sample 8.
The nuclear magnetic resonance spectrogram analysis and characterization of (E) -1, 3-diphenyl-1-butene are carried out, and the results are shown in figure 18 and figure 19. FIG. 18 is a nuclear magnetic resonance image (hydrogen spectrum) of sample 8 (solvent CDCl)3) (ii) a FIG. 19 is a nuclear magnetic resonance image (carbon spectrum) of sample 8 (solvent CDCl)3) (ii) a As can be seen from FIGS. 18 and 19, in the hydrogen spectrum, 1.45ppm of the signal is derived from hydrogen on the methyl group, multiple peaks of 3.57-3.67ppm are assigned to hydrogen on the carbon attached to the methyl group, signals of 6.32-6.44ppm are assigned to two hydrogens on the double bond of the alkane chain, and the hydrogen on the benzene ring falls within the range of 7.14-7.35 ppm; on the carbon spectrum, is located at 21The signals at 36ppm and 42.71ppm are assigned to the methyl carbon and the carbon attached to the methyl group, and the signals from the remaining double bonds and the carbon on the phenyl ring fall within the range of 126.29-145.77 ppm.
Nuclear magnetic data of sample 8:
1H NMR(400MHz,CDCl3)：δ7.35–7.29(m,3H),7.29–7.21(m,5H),7.21–7.14(m,2H),6.44–6.32(m,2H),3.67–3.57(m,1H),1.45(d,J＝7.0Hz,3H).
13C NMR(101MHz,CDCl3)：δ145.77(s),137.71(s),135.38(s),128.63(s),127.45(s),127.18(s),126.36(s),126.29(s),42.71(s),21.36(s).
although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A synthesis method of triphenylphosphine allyl palladium halide compounds and derivatives thereof is characterized in that a mixture containing palladium salt, halogenated allyl compounds and trisubstituted phosphine compounds is subjected to one-step reaction to obtain triphenylphosphine allyl palladium halide compounds and derivatives thereof.
2. The method of claim 1, wherein the palladium salt, the haloallylic compound, and the trisubstituted phosphine compound are used in a molar ratio range of:
1：1-20：1-10；
preferably, the molar ratio of the palladium salt, the halogenated allyl compound and the tri-substituted phosphine compound is in the following range:
1：2-10：1-5；
preferably, the molar ratio of the palladium salt, the halogenated allyl compound and the tri-substituted phosphine compound is in the following range:
1：4：2。
3. the method of claim 1, wherein the mixture comprising the palladium salt, the haloallylic compound, and the trisubstituted phosphine compound further comprises an activator;
the activating agent comprises at least one of organic base and inorganic base;
the inorganic base is at least one of potassium hydroxide, sodium hydroxide, cesium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate and cesium bicarbonate;
the organic base is at least one of potassium tert-butoxide, sodium tert-butoxide, potassium ethoxide, sodium ethoxide and sodium methoxide;
preferably, the molar ratio of the activator to the palladium salt is 1-5: 1;
preferably, the molar ratio of the activator to the palladium salt is 2: 1.
4. The method according to claim 1, wherein the palladium salt is at least one selected from the group consisting of palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium tetrafluoroborate, palladium trifluoromethanesulfonate.
5. The method of claim 1, wherein the haloalkenyl compound is selected from the group consisting of compounds having the formula I
Figure FDA0002317828280000021
Wherein, X is selected from one of Cl-, Br-and I-.
6. The method of claim 1, wherein the trisubstituted phosphine compound is selected from the group consisting of compounds having the formula II-1 or II-2
Figure FDA0002317828280000022
Wherein R is1、R2、R3、R4、R5、R6Each independently selected from H-, Ph-, CH3O-, alkyl and halogen elements;
preferably, the alkyl group is selected from CH3-、CH3CH2-、CH3CH2CH2-、(CH3)2CH-、CH3CH2CH2CH2-、(CH3)2CHCH2-、(CH3)3C-is one of the group; the halogen element is selected from one of F-, Cl-, Br-and I-;
preferably, R1、R2、R3Are the same hydrogen substituent groups; r4、R5、R6The same hydrogen substituents.
7. The method of claim 1, wherein the mixture comprising the palladium salt, the haloallylic compound, and the trisubstituted phosphine compound further comprises a solvent;
the solvent is at least one selected from 1, 2-dichloroethane, tetrahydrofuran, dichloromethane, trichloromethane and 1, 4-dioxane;
preferably, the molar ratio of the solvent to the palladium salt is 40-400: 1;
preferably, the molar ratio of the solvent to the palladium salt is 80: 1.
8. The method of claim 1, wherein the reaction atmosphere is air or an inert gas atmosphere;
preferably, the inert gas is selected from at least one of nitrogen, argon, helium.
9. The method according to claim 1, wherein the reaction temperature is 60-100 ℃ and the reaction time is 16-32 h;
preferably, the reaction temperature is 70-90 ℃, and the reaction time is 20-28 h;
further preferably, the reaction temperature is 80 ℃ and the reaction time is 24 h.
10. Use of triphenylphosphine allyl palladium halide compounds prepared by the process of any of claims 1 to 9 and derivatives thereof as catalysts in coupling reactions;
preferably, the coupling reaction comprises a cross-coupling reaction, a homocoupling reaction.
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