Phosphine nitrogen compound and metal complex, preparation method thereof, composition and application thereof, and carbonylation reaction method

Abstract

The invention relates to the technical field of carbonylation, and discloses a phosphine nitrogen compound and a metal complex as well as a preparation method, a composition and application thereof and a carbonylation reaction method. Wherein the phosphine-nitrogen compound has a chemical structure as shown in a formula (II), and the metal complex prepared from the phosphine-nitrogen compound has the characteristics of high catalytic activity, good thermal stability, difficulty in inactivation and high product selectivity in catalytic carbonylation reaction. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of carbonylation, in particular to a phosphine nitrogen compound and a metal complex, a preparation method and a composition thereof, and an application and carbonylation reaction method thereof. Background Art

[0002] The carbonylation reaction, which utilizes transition metal catalysts to convert olefins, methanol, and carbon monoxide into ester compounds, has important industrial applications because it can convert olefins commonly found in the petroleum industry into esters and achieve carbon chain extension. The carbonylation reaction produces linear and branched carbonylation products, as well as other reactions such as the isomerization of olefin substrates to produce corresponding isomerized olefins. Therefore, improving the selectivity of carbonylation reactions and obtaining high yields of target products have long been important challenges, and the most important approach to addressing this issue is the development of new, efficient carbonylation catalysts.

[0003] The catalyst for olefin carbonylation reaction is generally based on Rh catalyst. In the early stage, Rh catalyzed linear carbonylation reaction used monodentate phosphine ligand. Due to the weak coordination effect of monodentate phosphine ligand, in order to obtain high selectivity, a large excess of monodentate phosphine ligand needs to be added in the reaction. However, a large excess of ligand is not conducive to subsequent separation operation, and it is also uneconomical and environmentally unfriendly. At the same time, there are also catalysts using copper / nickel catalytic systems. Nickel / ketone catalytic system catalysts are low in cost and have mature processes, but the ethylene activation selectivity for carbonylation reaction is low, the carbonyl insertion rate is slow, the reaction system is high temperature and high pressure, it is incompatible with alcohols, and the ligand regulation is not obvious. In contrast, palladium catalysts have high ethylene activation selectivity, fast carbonyl insertion rate, mild reaction conditions, and compatibility with alcohols, but palladium catalysts are expensive and easily deactivated. Therefore, there is an urgent need for a phosphine nitrogen compound and a metal complex and their preparation method and composition and application in carbonylation reaction to overcome the above problems. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problems of easy deactivation, low product selectivity and yield in the prior art, and to provide a phosphine nitrogen compound and a metal complex, a preparation method thereof, and a method for their application and carbonylation reaction.

[0005] In order to achieve the above object, the first aspect of the present invention provides a phosphine nitrogen compound, characterized in that the compound has a chemical structure shown in formula (II):

[0006]

[0007] Wherein, n and n' are each independently selected from positive integers in the range of 1 to 3;

[0008] R1 and R1' are each independently selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, and R1 and R1' are the same or different;

[0009] R2 and R2' are each independently selected from substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, and R2 and R2' are the same or different;

[0010] R3 and R4 are selected from H, C1-C8 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, and R3 and R4 are the same or different.

[0011] A second aspect of the present invention provides a metal complex, characterized in that the complex has a chemical structure shown in formula (I):

[0012]

[0013] wherein X and X' are each independently selected from halogen, C1-C8 alkyl or aryl;

[0014] The definitions of n, R1, R2, R3 and R4 are the same as those described in the first aspect of the present invention.

[0015] A third aspect of the present invention provides a method for preparing a metal complex, the method comprising: reacting a compound represented by formula II with a metal compound in the presence of a protective gas and a solvent A to obtain the metal complex;

[0016]

[0017] Wherein, the definitions of n, R1, R2, R3 and R4 are the same as those described in the first aspect of the present invention.

[0018] The fourth aspect of the present invention provides a composition, which includes a metal complex and an auxiliary agent, wherein the metal complex is the complex described in the second aspect of the present invention.

[0019] The fifth aspect of the present invention provides use of the composition described in the fourth aspect of the present invention in catalyzing olefin carbonylation.

[0020] A sixth aspect of the present invention provides a method for carbonylation reaction, the method comprising:

[0021] In the presence of protective gas, catalyst and solvent B, a compound having a double bond undergoes carbonylation reaction with carbon monoxide and alcohol to obtain an ester compound;

[0022] Wherein, the catalyst is the composition described in the fourth aspect of the present invention.

[0023] Through the above technical solution, the technical solution of the present invention has the following beneficial effects:

[0024] Compared with monodentate phosphine catalysts, the metal complexes described in this invention enable more flexible and convenient control of the ligand's electronic and steric effects by varying the substituents on phosphorus and nitrogen. This allows for more diverse adjustment of the substituents, enabling the optimal catalyst ligand to be tailored to the specific olefin feedstock. Furthermore, these metal complexes exhibit high catalytic activity, excellent thermal stability, and resistance to deactivation, making them suitable for carbonylation reactions of various olefins, with high product selectivity and yield. DETAILED DESCRIPTION

[0025] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0026] In this invention, the terms involved are interpreted as follows:

[0027] Halogen refers to fluorine, chlorine, bromine and iodine.

[0028] Alkyl refers to an alkyl group in the form of a straight chain or branched chain, excluding cycloalkyl. The C1-C8 alkyl refers to an alkyl group having 1-8 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc.

[0029] Cycloalkyl refers to an alkyl group containing a cyclic chain, and the C3-C8 cycloalkyl refers to a cycloalkyl group having 3-8 carbon atoms, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0030] As mentioned above, the first aspect of the present invention provides a phosphine nitrogen compound, characterized in that the compound has a chemical structure shown in formula (II):

[0031]

[0032] Wherein, n and n' are each independently selected from positive integers in the range of 1 to 3;

[0033] R1 and R1' are each independently selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, and R1 and R1' are the same or different;

[0034] R2 and R2' are each independently selected from substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, and R2 and R2' are the same or different;

[0035] R3 and R4 are selected from H, C1-C8 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, and R3 and R4 are the same or different.

[0036] In some embodiments of the present invention, preferably, R1 and R1' are each independently selected from C1-C8 alkyl, C1-C8 haloalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, substituted or unsubstituted phenyl;

[0037] and / or, R2 and R2' are each independently selected from C3-C8 cycloalkyl, substituted or unsubstituted phenyl;

[0038] and / or, R3 is selected from H, C1-C4 alkyl, C3-C8 cycloalkyl, substituted or unsubstituted phenyl;

[0039] and / or, R4 is selected from H, C1-C4 alkyl, C3-C8 cycloalkyl, substituted or unsubstituted phenyl;

[0040] Wherein, the substituted substituent is selected from halogen and C1-C6 alkyl.

[0041] Further preferably, R1 and R1' are each independently selected from C1-C4 alkyl, C4-C7 cycloalkyl or phenyl;

[0042] and / or, R2 and R2' are each independently selected from C4-C7 cycloalkyl or phenyl;

[0043] and / or, R3 is selected from H, C1-C4 alkyl, substituted or unsubstituted phenyl;

[0044] and / or, R4 is selected from H, C1-C4 alkyl, substituted or unsubstituted phenyl;

[0045] Wherein, the substituted substituent is selected from C2-C4 alkyl.

[0046] In some embodiments of the present invention, preferably, the compound has the chemical structure shown in L1-L18:

[0047]

[0048]

[0049] The preparation method of the compound of the present invention can be: using a biaryl compound (as shown in Formula III) as a starting material, first synthesizing a double Grignard reagent (as shown in Formula IV), and then reacting the double Grignard reagent with a phosphine compound and an amine compound to prepare the compound (as shown in Formula II).

[0050]

[0051] In some embodiments of the present invention, preferably, a biaryl compound (as shown in Formula III) is reacted with N-bromosuccinimide NBS and azobisisobutyronitrile AIBN to generate a brominated biaryl compound, which is then reacted with magnesium powder and elemental iodine to generate a bis-Grignard reagent (as shown in Formula IV).

[0052] In some embodiments of the present invention, preferably, the reaction of the biphenyl compound (as shown in Formula III) with N-bromosuccinimide NBS and azobisisobutyronitrile AIBN is carried out in a solvent selected from dichloromethane, N,N-dimethylacetamide, toluene or tetrahydrofuran, and the reaction is carried out under reflux; the reaction of the brominated biphenyl compound with magnesium powder and elemental iodine is carried out in a solvent selected from tetrahydrofuran, N,N-dimethylacetamide, toluene or dichloromethane, and the reaction is carried out under reflux.

[0053] In some embodiments of the present invention, preferably, N,N,N',N'-tetramethylethylenediamine is added when the double Grignard reagent (as shown in Formula IV) reacts with the phosphine compound and the amine compound.

[0054] The reaction of the double Grignard reagent (as shown in formula IV) with the phosphine compound and the amine compound

[0055] The reaction is carried out in a solvent selected from toluene, N,N-dimethylacetamide, dichloromethane or tetrahydrofuran, and the reaction is carried out under reflux.

[0056] A second aspect of the present invention provides a metal complex, characterized in that the complex has a chemical structure shown in formula (I):

[0057]

[0058] wherein X and X' are each independently selected from halogen, C1-C8 alkyl or aryl;

[0059] The definitions of n, R1, R2, R3 and R4 are the same as those described in the first aspect of the present invention.

[0060] In some embodiments of the present invention, preferably, X and X' are each independently halogen.

[0061] In some embodiments of the present invention, preferably, the complex has the chemical structure shown by C1-C18:

[0062]

[0063]

[0064] A third aspect of the present invention provides a method for preparing a metal complex, the method comprising: reacting a compound represented by formula II with a metal compound in the presence of a protective gas and a solvent A to obtain the metal complex;

[0065]

[0066] Wherein, the definitions of n, R1, R2, R3 and R4 are the same as those described in the first aspect of the present invention.

[0067] In some embodiments of the present invention, preferably, after the reaction is completed, post-treatment is performed, which comprises: filtering the reaction solution obtained after the reaction, removing the solvent A from the filtrate obtained by filtration under reduced pressure, adding a mixed solvent of dichloromethane / n-hexane (2 mL / 20 mL) to wash the solid 2-3 times, and drying the remaining solid after filtration under vacuum to obtain the metal complex.

[0068] In some embodiments of the present invention, preferably, the metal compound is selected from Pd halides, preferably palladium chloride and / or palladium bromide.

[0069] In some embodiments of the present invention, preferably, the protective gas is selected from nitrogen and / or argon.

[0070] In some embodiments of the present invention, preferably, the solvent A is selected from at least one of dichloromethane, tetrahydrofuran and toluene.

[0071] In some embodiments of the present invention, preferably, the molar ratio of the compound represented by Formula II to the metal compound is 1-5:1, more preferably 1-2.5:1.

[0072] In some embodiments of the present invention, preferably, the reaction temperature is 0-100°C.

[0073] In some embodiments of the present invention, preferably, the reaction time is 3-20 hours.

[0074] The fourth aspect of the present invention provides a composition, which includes a metal complex and an auxiliary agent, wherein the metal complex is the complex described in the second aspect of the present invention.

[0075] In some embodiments of the present invention, preferably, the auxiliary agent is selected from sulfonic acid compounds, preferably methylbenzenesulfonic acid compounds and / or ethylbenzenesulfonic acid compounds, more preferably at least one of o-methylbenzenesulfonic acid, m-methylbenzenesulfonic acid, p-methylbenzenesulfonic acid, o-ethylbenzenesulfonic acid, m-ethylbenzenesulfonic acid and p-ethylbenzenesulfonic acid.

[0076] In some embodiments of the present invention, the molar ratio of the metal complex to the additive is preferably 1:2-200, more preferably 1:2-100, and even more preferably 1:2-10. This molar ratio range can improve the overall activity of the catalyst, thereby increasing yield and product selectivity.

[0077] The fifth aspect of the present invention provides use of the composition described in the fourth aspect of the present invention in catalyzing olefin carbonylation.

[0078] A sixth aspect of the present invention provides a method for carbonylation reaction, the method comprising:

[0079] In the presence of protective gas, catalyst and solvent B, a compound having a double bond undergoes carbonylation reaction with carbon monoxide and alcohol to obtain an ester compound.

[0080] Wherein, the catalyst is the composition described in the fourth aspect of the present invention.

[0081] In some embodiments of the present invention, preferably, the protective gas is selected from nitrogen and / or argon.

[0082] In some embodiments of the present invention, preferably, the solvent B is selected from at least one of n-hexane, toluene, ethyl acetate and ethyl propionate.

[0083] In some embodiments of the present invention, preferably, the compound having a double bond is selected from ethylene, propylene, 1-butene or 2-butene, preferably ethylene or propylene.

[0084] In some embodiments of the present invention, preferably, the alcohol is selected from methanol, ethanol or n-propanol, preferably methanol.

[0085] In some embodiments of the present invention, preferably, the molar ratio of the compound having a double bond to carbon monoxide is 1:1-1:10, preferably 1:1-1:2.

[0086] In some embodiments of the present invention, preferably, the molar ratio of the compound having a double bond to the metal complex in the composition is 2000:1-200000:1, preferably 10000:1-120000:1.

[0087] In some embodiments of the present invention, preferably, the molar ratio of the alcohol to the metal complex in the composition is 1000:1-100000:1, preferably 5000:1-60000:1.

[0088] In some embodiments of the present invention, preferably, the carbonylation reaction temperature is 0-150° C.; the pressure is 0.1-10 MPa; and the time is 5-600 min.

[0089] In order to demonstrate the good stability and non-deactivation effect of the catalyst of the present invention, in the carbonylation reaction, the catalyst can be a catalyst that is recycled 3-10 times; the recycling method is to remove the liquid from the reaction liquid after the carbonylation reaction by rotary evaporation and then put it into a new carbonylation reaction.

[0090] The present invention will be described in detail below by way of examples. 1 The H NMR spectrum was measured using a nuclear magnetic spectrometer, and elemental analysis data were obtained using a German Elementarvario MicroCube instrument. Methanol was a commercial product from Sinopharm Chemical Reagent Co., Ltd. with an AR purity, ethylene was a commercial product from Sigma-Aldrich (Shanghai) Trading Co., Ltd. with a purity of 99.5%, and carbon monoxide was a commercial product from Sigma-Aldrich (Shanghai) Trading Co., Ltd. with a purity of 99%. All solvents and reactants (e.g., toluene, n-hexane, and ethyl acetate) were purified using an anhydrous and oxygen-free environment.

[0091] Preparation Example: Synthesis of compounds represented by phosphine nitrogen compounds L1-L18

[0092] 5g of 2,2-dimethylbiphenyl (a biphenyl compound, 27mmol) was placed in 50mL of dichloromethane (DCM), followed by the addition of 10g (56mmol) of N-bromosuccinimide (NBS) and 250mg (1.5mmol) of azobisisobutyronitrile (AIBN). The mixture was refluxed under nitrogen for 16h. After completion of the reaction, the system was cooled to room temperature and filtered. The filter cake was rinsed twice with DCM, and the filtrate was collected. The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was rotary evaporated to dryness. After recrystallization from n-hexane, a large amount of white solid precipitated. The resulting white solid was collected by suction filtration and dried to obtain 7.5g of the product, 2,2-bromomethylbiphenyl, with a yield of 82%.

[0093] Under argon, 7.5 g (22 mmol) of 2,2-bromomethylbiphenyl, 100 mL of ultra-dry tetrahydrofuran, 1.15 g of magnesium powder, and 0.012 g of iodine were added to a 250 mL three-necked flask. The mixture was refluxed under argon for 4 h. After cooling to room temperature, 4.3 g of tetramethylethylenediamine was added, followed by a 50 mL toluene solution of 4.9 g of diphenylphosphine chloride and 4.5 g of diphenylchloramine. The system was heated to 65°C under argon throughout the reaction. TLC was performed until the reaction was complete, after which the reaction was quenched. The reaction mixture was separated and the organic phase was collected, dried, and concentrated by rotary evaporation. The organic phase was then purified by silica gel column chromatography (ethyl acetate / petroleum ether = 1 / 30-1 / 10, with the silica gel soaked overnight in pure triethylamine and flushed with petroleum ether until neutral) to yield 4.31 g of L1 as a pale yellow solid in 37% yield.

[0094] 1 H NMR(500MHz,Chloroform-d)δ7.53(dt,J=6.0,3.6Hz,2H),7.42-7.21(m,19H),7.21-7.16(m,1H),7.16-7.10(m,4 H),7.05(tt,J=7.4,2.1Hz,2H),4.94(d,J=1.1Hz,2H),3.46(dd,J=12.4,1.0Hz,1H),3.36(dd,J=12.4,1.0Hz,1H).

[0095] Different biphenyl compounds, chlorophosphine compounds and chloramine compounds were used to replace the corresponding compounds in the preparation examples, thereby preparing the compounds shown as phosphine nitrogen compounds L2 to L18, respectively. Their structural characterization data (H-NMR spectra) are shown in Table 1.

[0096] Table 1

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] Example 1

[0103] In the presence of nitrogen (protective gas) and 20mL of dichloromethane (solvent A), 1.05mmol of the compound shown in L1 (one of the compounds shown in Formula II) was reacted with 1mmol of PdCl2 (metal compound). The molar ratio of the compound shown in L1 to PdCl2 was 1.05:1, the reaction temperature was 40°C, and the reaction time was 12h. After the reaction, the reaction solution was filtered and the solvent was removed under reduced pressure. A mixed solvent of dichloromethane / n-hexane (2mL / 20mL) was added to wash the filtered solid 2-3 times, and the remaining solid was dried under vacuum. The product was obtained as a yellow solid, i.e., the compound shown in the metal complex C1, with a yield of 85%. Elemental analysis results Anal.Calcd.For C 24 H 32 Br2N2Ni: C, 50.84; H, 5.69; N, 4.94; Found: C, 50.74; H, 5.39; N, 4.84. (Compounds L2-L18 are used to replace the compound L1, respectively. Alternatively, PdBr2 is used to replace PdCl2. The metal complexes C2-C18 can be prepared according to the above-described technical scheme. The structural characterization data are shown in Table 2.)

[0104] In the presence of nitrogen (protective gas), a catalyst (25 mg (0.03 mmol) of the compound represented by C1 and 25 mg (0.14 mmol) of p-toluenesulfonic acid, with a molar ratio of 1:4.5) and 15 mL of toluene (solvent B), a mixed gas of ethylene, a compound having a double bond, and carbon monoxide (molar ratio of 1:1) and 45 g of methanol (1.4 mol, alcohol) were subjected to a carbonylation reaction. The molar ratio of the ethylene, a compound having a double bond, to the compound represented by C1 was 50,000:1, and the molar ratio of the alcohol to the compound represented by C1 was 47,000:1. The carbonylation reaction was carried out at a temperature of 50°C, a pressure of 2 MPa and a reaction time of 180 min to obtain methyl propionate (ester compound) with a yield of 80% and a product selectivity of 98.3%.

[0105] Example 2

[0106] The method of Example 1 was followed, except that the carbonylation reaction temperature was 70° C., the pressure was 3 MPa, and the reaction time was 180 min. Methyl propionate (ester compound) was obtained with a yield of 88% and a product selectivity of 98.6%.

[0107] Example 3

[0108] The method of Example 1 was followed, except that the carbonylation reaction temperature was 120° C., the pressure was 3 MPa, and the reaction time was 180 min. Methyl propionate (ester compound) was obtained with a yield of 83% and a product selectivity of 96.8%.

[0109] Example 4

[0110] The method of Example 1 was followed, except that the carbonylation reaction temperature was 80° C., the pressure was 7 MPa, and the reaction time was 180 min. Methyl propionate (ester compound) was obtained with a yield of 89% and a product selectivity of 97.5%.

[0111] Example 5

[0112] The method of Example 3 was followed, except that the carbonylation reaction time was 420 min, to obtain methyl propionate (ester compound) with a yield of 95.8% and a product selectivity of 98.3%.

[0113] Example 6

[0114] The method of Example 3 was followed, except that the compound represented by C3 was used instead of the compound represented by C1. The carbonylation reaction lasted 480 min to obtain methyl propionate (ester compound) with a yield of 95.4% and a product selectivity of 98.0%.

[0115] Example 7

[0116] The method of Example 3 was followed, except that the compound represented by C8 was used instead of the compound represented by C1. The carbonylation reaction lasted 480 min to obtain methyl propionate (ester compound) with a yield of 94.7% and a product selectivity of 98.5%.

[0117] Example 8

[0118] The method of Example 3 was followed, except that the compound represented by C10 was used instead of the compound represented by C1. The carbonylation reaction lasted 420 minutes to obtain methyl propionate (ester compound) with a yield of 95.3% and a product selectivity of 98.2%.

[0119] Example 9

[0120] The method of Example 1 was followed, except that the compound shown in C2 was used instead of the compound shown in C1, to obtain methyl propionate (ester compound) with a yield of 62% and a selectivity of 97.5%.

[0121] Example 10

[0122] The method of Example 1 was followed, except that the compound represented by C4 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 78% and a selectivity of 98.1%.

[0123] Example 11

[0124] The method of Example 1 was followed, except that the compound represented by C5 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 73% and a selectivity of 98.4%.

[0125] Example 12

[0126] The method of Example 1 was followed, except that the compound represented by C7 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 82% and a selectivity of 96.8%.

[0127] Example 13

[0128] The method of Example 1 was followed, except that the compound represented by C13 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 76% and a selectivity of 97.7%.

[0129] Example 14

[0130] The method of Example 1 was followed, except that the compound represented by C17 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 83% and a selectivity of 98.3%.

[0131] Example 15

[0132] The method of Example 2 was followed, except that the compound represented by C6 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 85% and a selectivity of 98.2%.

[0133] Example 16

[0134] The method of Example 2 was followed, except that the compound represented by C9 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 81% and a selectivity of 97.5%.

[0135] Example 17

[0136] The method of Example 2 was followed, except that the compound represented by C12 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 88% and a selectivity of 97.5%.

[0137] Example 18

[0138] The method of Example 2 was followed, except that the compound represented by C14 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 70% and a selectivity of 98.0%.

[0139] Example 19

[0140] The method of Example 2 was followed, except that the compound represented by C15 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 86% and a selectivity of 98.7%.

[0141] Example 20

[0142] The method of Example 2 was followed, except that the compound represented by C16 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 78% and a selectivity of 98.2%.

[0143] Example 21

[0144] The method of Example 4 was followed, except that the compound represented by C10 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 85% and a selectivity of 96.6%.

[0145] Example 22

[0146] The method of Example 4 was followed, except that the compound represented by C11 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 88% and a selectivity of 95.6%.

[0147] Example 23

[0148] The method of Example 4 was followed, except that the compound represented by C18 was used instead of the compound represented by C1, to obtain methyl propionate (ester compound) with a yield of 83% and a selectivity of 97.2%.

[0149] Example 24

[0150] The method of Example 4 was followed, except that propylene was used instead of ethylene, to obtain methyl butyrate (ester compound) with a yield of 83% and a product selectivity of 98.1%.

[0151] Example 25

[0152] The method of Example 2 was followed, except that 1-butene was used instead of ethylene to obtain methyl valerate (ester compound) with a yield of 77% and a product selectivity of 97.5%.

[0153] Example 26

[0154] According to the method of Example 5, except that the catalyst was recycled three times, methyl propionate (ester compound) was obtained with a yield of 95.6% and a product selectivity of 98.2%.

[0155] Example 27

[0156] According to the method of Example 5, except that the catalyst was recycled 6 times, methyl propionate (ester compound) was obtained with a yield of 95.5% and a product selectivity of 98.3%.

[0157] Example 28

[0158] According to the method of Example 5, except that the catalyst was recycled 8 times, methyl propionate (ester compound) was obtained with a yield of 95.1% and a product selectivity of 98.1%.

[0159] Comparative Example 1

[0160] The method of Example 2 was followed, except that the compound Substituting the compound shown in C1, methyl propionate (ester compound) was obtained with a yield of 73% and a product selectivity of 83%.

[0161] Comparative Example 2

[0162] The method of Example 2 was followed, except that the compound Substituting the compound shown in C1, methyl propionate (ester compound) was obtained with a yield of 78% and a product selectivity of 86%.

[0163] Table 2

[0164]

[0165]

[0166]

[0167]

[0168]

[0169] By comparing the data of Examples 1-25 with Comparative Examples 1 and 2, it can be seen that the examples using the technical solution of the present invention have significantly better effects in terms of reaction selectivity and yield of olefin carbonylation reaction.

[0170] It can be seen from Examples 26-28 that by adopting the technical solution of the present invention, a high reaction selectivity and yield of olefin carbonylation reaction can still be achieved by selecting a catalyst that has been applied 3-8 times, which reflects the beneficial effect of the catalyst of the present invention that it is not easy to deactivate and has strong stability.

[0171] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A phosphine nitrogen compound, characterized in that: The compound has a chemical structure shown in formula (II): Wherein, n and n' are each independently selected from positive integers in the range of 1 to 3; R1 and R1' are each independently selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, and R1 and R1' are the same or different; R2 and R2' are each independently selected from substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, and R2 and R2' are the same or different; R3 and R4 are selected from H, C1-C8 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted aryl, and R3 and R4 are the same or different.

2. The compound according to claim 1, wherein R1 and R1' are each independently selected from C1-C8 alkyl, C1-C8 haloalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, substituted or unsubstituted phenyl; and / or, R2 and R2' are each independently selected from C3-C8 cycloalkyl, substituted or unsubstituted phenyl; and / or, R3 is selected from H, C1-C4 alkyl, C3-C8 cycloalkyl, substituted or unsubstituted phenyl; and / or, R4 is selected from H, C1-C4 alkyl, C3-C8 cycloalkyl, substituted or unsubstituted phenyl; Wherein, the substituted substituent is selected from halogen and C1-C6 alkyl.

3. The compound according to claim 1 or 2, wherein R1 and R1' are each independently selected from C1-C4 alkyl, C4-C7 cycloalkyl or phenyl; and / or, R2 and R2' are each independently selected from C4-C7 cycloalkyl or phenyl; and / or, R3 is selected from H, C1-C4 alkyl, substituted or unsubstituted phenyl; and / or, R4 is selected from H, C1-C4 alkyl, substituted or unsubstituted phenyl; Wherein, the substituted substituent is selected from C2-C4 alkyl.

4. The compound according to any one of claims 1 to 3, wherein The compounds have the chemical structures shown in L1-L18:

5. A metal complex, characterized in that The complex has a chemical structure shown in formula (I): Wherein, X and X' are each independently selected from halogen, C1-C8 alkyl or aryl; The definitions of n, R1, R2, R3 and R4 are the same as those in any one of claims 1 to 3.

6. The complex according to claim 5, wherein X and X' are each independently halogen.

7. The complex according to claim 5 or 6, wherein The complex has the chemical structure shown by C1-C18:

8. A method for preparing a metal complex, the method comprising: In the presence of a protective gas and a solvent A, reacting the compound represented by formula II with a metal compound to obtain the metal complex; Wherein, the definitions of n, R1, R2, R3 and R4 correspond to and are the same as those in any one of claims 1 to 3.

9. The method according to claim 8, wherein: The metal compound is selected from Pd halides, preferably palladium chloride and / or palladium bromide; Preferably, the protective gas is selected from nitrogen and / or argon; Preferably, the solvent A is selected from at least one of dichloromethane, tetrahydrofuran and toluene; Preferably, the molar ratio of the compound represented by formula II to the metal compound is 1-5:1, more preferably 1-2.5:1; Preferably, the reaction temperature is 0-100°C; and the reaction time is 3-20h.

10. A composition, wherein It comprises a metal complex and an auxiliary agent, wherein the metal complex is the complex described in any one of claims 5-7.

11. The composition according to claim 10, wherein The auxiliary agent is selected from sulfonic acid compounds, preferably methylbenzenesulfonic acid compounds and / or ethylbenzenesulfonic acid compounds, more preferably at least one of o-methylbenzenesulfonic acid, m-methylbenzenesulfonic acid, p-methylbenzenesulfonic acid, o-ethylbenzenesulfonic acid, m-ethylbenzenesulfonic acid and p-ethylbenzenesulfonic acid.

12. The composition according to claim 10 or 11, wherein The molar ratio of the metal complex to the auxiliary agent is 1:2-200, more preferably 1:2-100, and more preferably 1:2-10.

13. Use of the composition according to any one of claims 10 to 12 in catalyzing olefin carbonylation.

14. A method for carbonylation reaction, the method comprising: In the presence of protective gas, catalyst and solvent B, a compound having a double bond undergoes carbonylation reaction with carbon monoxide and alcohol to obtain an ester compound; Wherein, the catalyst is the composition described in any one of claims 11-13.

15. The method according to claim 14, wherein: The protective gas is selected from nitrogen and / or argon; The solvent B is selected from at least one of n-hexane, toluene, ethyl acetate and ethyl propionate; The compound having a double bond is selected from ethylene, propylene, 1-butene or 2-butene, preferably ethylene or propylene; The alcohol is selected from methanol, ethanol or n-propanol, preferably methanol.

16. The method according to claim 14 or 15, wherein: The molar ratio of the compound having a double bond to carbon monoxide is 1:1-1:10, preferably 1:1-1:2; The molar ratio of the compound having a double bond to the metal complex in the composition is 2000:1-200000:1, preferably 10000:1-120000:1; The molar ratio of the alcohol to the metal complex in the composition is 1000:1-100000:1, preferably 5000:1-60000:1; The carbonylation reaction is carried out at a temperature of 0-150°C, a pressure of 0.1-10 MPa and a time of 5-600 min.

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