A preparation method of 2,7-octadienyl compound

Abstract

The present application provides a method for preparing a 2,7-octadienyl compound, relating to the field of homogeneous catalysis and organic synthesis technology. In the present application, a conjugated diene having at least two conjugated double bonds is subjected to a telomerization reaction with a nucleophilic reagent under the action of a catalyst and a reaction promoter to obtain a 2,7-octadienyl compound. A small amount of reaction promoter is added to the preparation method. The reaction promoter not only has a good synergistic effect with the catalyst, but also can significantly improve the stability of the reaction intermediate, reduce the amount of organophosphine ligand, reduce the catalyst cost, and can also accelerate the rapid circulation of the active components zero-valent palladium and divalent palladium in the catalyst, improve catalytic efficiency, reduce the occurrence of side reactions, and effectively improve reaction selectivity.

Description

Technical Field

[0001] The present application relates to the technical field of homogeneous catalysis and organic synthesis, and specifically to a method for preparing a 2,7-octadienyl compound. Background Art

[0002] Octadienyl compounds serve as important precursors for solvents, plasticizers, fine chemicals, and reactive compound intermediates. For example, the linear C8-alcohols and C8-olefins synthesized from 1,3-butadiene are precursors to 1-octanol and 1-octene, which are then used in flavors and fragrances like hexylcinnamaldehyde and plasticizers like DONP. 1-Octene is a valuable comonomer used in the synthesis of polyolefin elastomers.

[0003] Telomerization reactions have been extensively described in the literature, but existing methods often suffer from high catalyst costs and / or byproducts. Currently, the only commercially viable telomerization process used is the butadiene telomerization process developed by Kuraray for the synthesis of 1-octanol.

[0004] Publication number CN1096286A, patent name "Method for Preparing Alkadienol Compounds", discloses a method for homogeneously catalyzing a telomerization reaction using a palladium compound and a phosphine ligand. In the presence of carbon dioxide, the palladium compound and the phosphine ligand are used as catalysts to react a conjugated diene with water. The reaction is carried out under the condition that a free phosphine compound is present in the reaction solution. This requires that the amount of phosphine ligand used is much greater than the amount of palladium catalyst used, resulting in high costs. In addition, the yield of the target product is only 50-80%, and the selectivity of the normal product is less than 90%, which is difficult to meet industrial requirements.

[0005] The publication number is CN101010275B, and the patent name is "Method for the Polymerization of Non-cyclic Olefins". It discloses a technical solution using a palladium-carbene complex as a catalyst for a polymerization reaction. This solution can use mixed C4 hydrocarbon components as raw materials and methanol for a polymerization reaction to synthesize 2,7-octadien-1-ol. However, this process has many reaction by-products, the ligand synthesis is relatively difficult, and the catalytic system has no recovery or recycling capabilities.

[0006] The publication number is CN105050993A, and the patent name is "Method for producing 2,7-octadiene-1-ol". It discloses a technical solution using a palladium catalyst and a water-soluble triarylphosphine as a ligand. After the reaction is completed, oil and water are separated and the catalyst is reused. However, the reaction conversion rate is only 74.4~81.6%, the palladium recovery rate is only 67~91%, and the phosphine recovery rate is 62~92%. The catalyst recovery rate is low and the cost is high.

[0007] The publication number is CN107089899A, and the patent name is "A method for preparing n-octanol using a supported bimetallic catalyst." It discloses a one-pot method using a supported catalyst to achieve the reaction. After the reaction is completed, the catalyst is filtered out and directly reacted again. No deactivation is observed after 50 consecutive uses. When the catalyst is used 50 times, the reaction yield only decreases by 1.52 percentage points. The one-pot method for preparing n-octanol has a short reaction route, but its reaction time is as long as 8 to 20 hours, and the yield of n-octanol is 87.6 to 95.6%. Summary of the Invention

[0008] In view of this, the present application provides a method for preparing 2,7-octadienyl compounds, which solves the technical problem in the prior art that in a homogeneous palladium catalytic system, a considerable amount of zero-valent palladium is unable to participate in the redox cycle and aggregates to form catalytically inactive palladium black, which precipitates from the homogeneous system and affects the selectivity of the reaction.

[0009] The present application provides a method for preparing a 2,7-octadienyl compound, wherein a conjugated diene having at least two conjugated double bonds and a nucleophilic reagent are subjected to a telomerization reaction under the action of a catalyst and a reaction accelerator to obtain the 2,7-octadienyl compound;

[0010] The reaction accelerator is a quinone compound; the nucleophilic reagent includes at least one of compound (IIa), compound (IIb), or compound (IIc), and the general formulas of compound (IIa), compound (IIb), and compound (IIc) are as follows:

[0011] ;

[0012] Where R 1 , R 2 , R 3 , R 4 is any one of hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl.

[0013] In one embodiment, the quinone compound is at least one of a benzoquinone compound (Va) or an anthraquinone compound (Vb); the general formulas of the benzoquinone compound (Va) and the anthraquinone compound (Vb) are as follows:

[0014] ;

[0015] Where R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R25 、R 26 、R 27 and R 28 is hydrogen, alkyl, alkoxy, aryl, COOR b 、COO - U + 、SO3R b 、SO3 - U + ,NE 4 E 5 、Alkylene NE 4 E 5 ,NE 4 E 5 E 6 X - 、Alkylene NE 4 E 5 E 6 X - , OR b SR b 、COR b , OCOR b , halogen, nitro, trifluoromethyl or cyano;

[0016] Among them, the R b 、E 4 、E 5 and E 6 is any one of hydrogen, alkyl, cycloalkyl or aryl, and / or, said R b 、E 4 、E 5 and E 6 are the same or different groups; U + Indicates that it includes alkali metal ions or cations N + F 5 F 6 F 7 F 8 Any one of the F 5 、F 6 、F 7 and F 8 is any one of hydrogen, alkyl, cycloalkyl or aryl, and / or, the F 5 、F 6 、F 7 and F 8 are the same or different groups; X - represents any of the halogen ions.

[0017] In one embodiment, the benzoquinone compound (Va) and the anthraquinone compound (Vb) include but are not limited to compounds of the following structural formulas:

[0018] ;

[0019] ;

[0020] In one embodiment, the nucleophile comprises any one of water, methanol, acetic acid and propionic acid;

[0021] Preferably, the conjugated diene comprises at least one of 1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-octadiene and 1,3,7-octatriene; preferably, the conjugated diene comprises one or both of 1,3-butadiene or isoprene.

[0022] In one embodiment, the catalyst comprises an organic phosphine ligand and a palladium compound, wherein the organic phosphine ligand is a triarylphosphine compound, and the general formula (IV) of the triarylphosphine compound is as follows:

[0023] ;

[0024] Where R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 and R 16 is hydrogen, alkyl, alkoxy, aryl, COOR a 、COO - M + 、SO3R a 、SO3 - M + ,NE 1 E 2 、Alkylene NE 1 E 2 ,NE 1 E 2 E 3 Z - 、Alkylene NE 1 E 2 E 3 Z - , OR a SR a 、CORa , OCOR a , halogen, nitro, trifluoromethyl or cyano; M + Including alkali metal ions or cations N + F 1 F 2 F 3 F 4 Any one of Z - is any one of the halogen ions;

[0025] Among them, the R 5 、R 6 、R 7 and R 8 At least two of the substituents are hydrogen, R 9 、R 10 、R 11 and R 12 At least two of the substituents are hydrogen, R 13 、R 14 、R 15 and R 16 At least two of the substituents are hydrogen;

[0026] Preferably, the R a 、E 1 、E 2 and E 3 is any one of hydrogen, alkyl, cycloalkyl or aryl, and / or, R a 、E 1 、E 2 and E 3 are the same or different groups;

[0027] Preferably, the F 1 、F 2 、F 3 and F 4 is any one of hydrogen, alkyl, cycloalkyl or aryl; and / or, the F 1 、F 2 、F 3 and F 4 are the same or different groups.

[0028] In one embodiment, the structural formula of the triarylphosphine compound includes but is not limited to the compound described in the following structure:

[0029] ;

[0030] ;

[0031] .

[0032] In one embodiment, the palladium compound is a complex or salt compound in an oxidation state of (0), or the palladium compound is a complex or salt compound in an oxidation state of (II);

[0033] Preferably, the palladium compound having an oxidation state of (0) includes at least one or more of bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, tris(triphenylphosphine)palladium, tetrakis(dimethylphenylphosphine)palladium, di(tri-tert-butylphosphine)palladium, bis(1,2-bis(diphenylphosphine)ethane)palladium, and (1,5-cyclooctadiene)(maleic anhydride)palladium;

[0034] Preferably, the palladium compound having an oxidation state of (II) includes at least one or more of palladium acetate, palladium chloride, palladium sulfate, palladium nitrate, palladium iodide, palladium pivalate, palladium trifluoroacetate, trimethylpalladium acetate, bis(acetylacetonate)palladium, (1,5-cyclooctadiene)palladium dichloride, bis(triphenylphosphine)palladium dichloride, bis(triethylphosphine)palladium dichloride, bis(tricyclohexylphosphine)palladium dichloride, (1,2-bis(diphenylphosphine)ethane)palladium dichloride, (1,3-bis(diphenylphosphine)propane)palladium dichloride, (1,1'-bis(diphenylphosphine)ferrocene)palladium dichloride, bis(triphenylphosphine)palladium acetate, bis(tri-n-butylphosphine)palladium acetate, and bis-μ-dichlorobis(triphenylphosphine)dipalladium.

[0035] Preferably, the palladium compound is at least one or more of bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, palladium acetate, palladium nitrate or di(acetylacetonate)palladium.

[0036] In one embodiment, the molar ratio of palladium atoms to phosphine atoms in the catalyst is 1:(0.5-10); preferably, the molar ratio of palladium atoms to phosphine atoms in the catalyst is 1:(1-5).

[0037] In one embodiment, the molar ratio of the reaction accelerator to the palladium atoms in the catalyst is (0.1-100):1, and / or the molar ratio of the nucleophile to the conjugated diene is (0.5-2):1, and / or the molar ratio of the palladium atoms in the catalyst to the conjugated diene is (0.000001-0.1):1;

[0038] Preferably, the molar ratio of the reaction accelerator to the palladium atoms in the catalyst is (1-20):1; more preferably, the molar ratio of the reaction accelerator to the palladium atoms in the catalyst is (1-10):1;

[0039] Preferably, the molar ratio of palladium atoms in the catalyst to the conjugated diene is (0.000001-0.01):1; more preferably, the molar ratio of palladium atoms in the catalyst to the conjugated diene is (0.00001-0.001):1.

[0040] In one embodiment, a water-soluble solvent is further added during the telomerization reaction, and the water-soluble solvent includes at least one or more of acetone, acetonitrile, heptanone, tetrahydrofuran, 1,4-dioxane, sulfolane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and / or, the mass ratio of the water-soluble solvent in the telomerization reaction to the conjugated diene is (0.5-2):1.

[0041] In one embodiment, a base is further added during the telomerization reaction, and the base for the telomerization reaction includes one or more of trialkylamines, alicyclic tertiary amines, and pyridines; preferably, the base for the telomerization reaction includes at least one or more of trimethylamine, triethylamine, tripropylamine, N,N-diisopropylethylamine, tetramethylethylenediamine, N-methylcyclohexylamine, 1,8-diazabicycloundec-7-ene, pyridine, and N,N-dimethylaminopyridine; more preferably, the base for the telomerization reaction includes at least one or more of trimethylamine, triethylamine, and tripropylamine;

[0042] And / or, the molar ratio of the base in the telomerization reaction to the conjugated diene is (0.01-100):1, preferably, the molar ratio of the base in the telomerization reaction to the conjugated diene is (0.1-10):1; more preferably, the molar ratio of the base in the telomerization reaction to the conjugated diene is (0.5-2):1.

[0043] In one embodiment, the reaction temperature of the telomerization reaction is 40-160° C., the reaction pressure of the telomerization reaction is 0.1-10 MPa, and the reaction time of the telomerization reaction is 3-20 h; preferably, the reaction temperature of the telomerization reaction is 50-100° C., the reaction pressure of the telomerization reaction is 0.5-5 MPa, and the reaction time of the telomerization reaction is 3-10 h.

[0044] The present application provides a method for preparing a 2,7-octadienyl compound, wherein a conjugated diene having at least two conjugated double bonds is subjected to a telomerization reaction with a nucleophilic reagent in the presence of a catalyst and a reaction promoter to obtain the 2,7-octadienyl compound. A small amount of reaction promoter is added to the preparation method. The reaction promoter not only has a good synergistic effect with the catalyst, significantly improving the stability of the reaction intermediate, reducing the amount of organophosphine ligand used, and lowering the catalyst cost, but also accelerates the rapid circulation of the active components zero-valent palladium and divalent palladium in the catalyst, improving catalytic efficiency, reducing the occurrence of side reactions, and effectively improving reaction selectivity. DETAILED DESCRIPTION

[0045] Mentioning "embodiment" in this article means that the specific features, structures or characteristics described in conjunction with the embodiment may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It will be understood by those skilled in the art that the embodiments described herein can be combined with other embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0046] Unless otherwise specified, all reagents used in this application are commercially available.

[0047] In this application, the palladium and phosphine concentrations in the raffinate phase obtained from the extraction process were quantitatively analyzed using an inductively coupled plasma mass spectrometer (Agilent). The starting materials and the product 2,7-octadienyl compound in the telomerization reaction solution were analyzed and quantified using gas chromatography under the following measurement conditions. Based on this analysis, the conversion of the reactants, the selectivity of the products, and the yield were calculated.

[0048] The gas chromatography analysis conditions are as follows: chromatographic column: Agilent DB-Wax (specifications: 30 m × 0.32 mm × 0.25 mm); inlet temperature: 300 °C; split ratio: 30:1; column flow rate: 1.5 mL / min; column temperature: 100 °C for 0.5 min; heating program: 15 °C / min to 300 °C, hold for 8 min; detector temperature: 300 °C, hydrogen flow rate: 35 mL / min, air flow rate: 350 mL / min.

[0049] Example 1

[0050] Under a nitrogen atmosphere, 20 g of a sulfolane solution containing 0.260 g of palladium acetate (1.16 mmol of palladium atoms) was added to a 100 mL glass flask. Subsequently, 3.01 g of sodium triphenylphosphine tris-metasulfonic acid salt (5.72 mmol) was added to the glass flask, and the mixture was stirred at room temperature for 20 minutes to prepare a catalyst solution.

[0051] To a 1 L autoclave were added 60 g of desalted water (3.33 mol), 60 g of sulfolane, 100 g of triethylamine (0.988 mol), 0.511 g of 2,5-di-tert-butyl-p-benzoquinone (2.32 mmol), and the prepared catalyst solution. The autoclave was fully replaced with carbon dioxide, and the mixture was stirred at 500 rpm and heated to 30°C. Subsequently, 108 g of butadiene (2 mol) was added, and the autoclave was pressurized to 1.2 MPa with carbon dioxide. The reaction was carried out at 70°C for 6 h. After the reaction was completed, the mixture was cooled to room temperature to obtain a reaction mixture. The reaction mixture included a mixture of raw materials, products, catalysts, solvents, etc. The reaction mixture included 1,3,7-cyclooctatriene (OCT), 4-vinyl-1-cyclohexene (VCH), 2,7-octadien-1-ol (NODA), and 1,7-octadien-3-ol (IODA).

[0052] The reaction mixture was extracted three times with 100 mL of n-hexane, and the product was separated into an extract phase containing the raw material and the 2,7-octadienyl compound and a raffinate phase. The extract phase was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated based on this analysis. The conversion rate of the raw material butadiene in the extract phase was calculated according to Formula 1, and the selectivity of each product was calculated according to Formula 2, where the unit of each quantity is mol.

[0053] Formula 1;

[0054] Formula 2;

[0055] Calculation shows that the conversion rate of raw material butadiene is 97.4%, the OCT selectivity is 0.3%, the VCH selectivity is 4.7%, the NODA selectivity is 90.5%, the IODA selectivity is 4.5%, and the normal / isomer ratio is 20.1:1.

[0056] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated from the palladium concentration, the phosphine concentration, and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were quantitatively analyzed by inductively coupled plasma mass spectrometry (Agilent), respectively. The recovery rate of palladium atoms was calculated by Formula 3, and the recovery rate of the organophosphine ligand was calculated by Formula 4, where the units of each quantity are mol.

[0057] Formula 3;

[0058] Formula 4;

[0059] Calculation showed that the recovery rate of palladium atoms was 99.2%, and the recovery rate of organophosphine ligands was 98.3%.

[0060] Example 2

[0061] The implementation of Example 2 is the same as that of Example 1, except that:

[0062] The organic phosphine ligand is triphenylphosphine tris-metasulfonic acid sodium salt, and the amount of triphenylphosphine tris-metasulfonic acid sodium salt used is 1.26 g (2.07 mmol).

[0063] After the reaction was completed, the temperature was cooled to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane, extracted three times, and the extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract phase was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. After calculation, the conversion rate of the raw material butadiene was 95.1%, the selectivity of OCT was 0.4%, the selectivity of VCH was 3.2%, the selectivity of NODA was 92.5%, the selectivity of IODA was 3.9%, and the normal / isomer ratio was 23.7:1.

[0064] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration, and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by formula 4 in Example 1. The calculation showed that the recovery rate of palladium atoms was 99.1%, and the recovery rate of the organophosphine ligand was 97.1%.

[0065] Example 3

[0066] The implementation of Example 3 is the same as that of Example 1, except that:

[0067] The reaction accelerator is 2,5-di-tert-butyl-p-benzoquinone, and the amount of 2,5-di-tert-butyl-p-benzene used is 0.261 g (1.18 mmol).

[0068] After the reaction was completed, the temperature was lowered to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane three times. The extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract phase was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 2. After calculation, the conversion rate of the raw material butadiene was 96.2%, the selectivity of OCT was 0.3%, the selectivity of VCH was 3.1%, the selectivity of NODA was 90.6%, the selectivity of IODA was 6.0%, and the normal / isomer ratio was 15.6:1.

[0069] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration, and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by Formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by Formula 4 in Example 2. The calculation showed that the recovery rate of palladium atoms was 98.3%, and the recovery rate of the organophosphine ligand was 97.7%.

[0070] Example 4

[0071] Under a nitrogen atmosphere, 20 g of a sulfolane solution containing 0.231 g of palladium acetate (1.03 mmol of palladium atoms) was added to a 100 mL glass flask. Subsequently, 1.07 g of triphenylphosphine (3.96 mmol) was added to the glass flask, and the mixture was stirred at room temperature for 20 minutes to prepare a catalyst solution.

[0072] To a 1L autoclave were added 90g (1.50mol) of acetic acid, 80g of sulfolane, 90g (0.889mol) of triethylamine, 0.235g (1.07mmol) of 2,5-di-tert-butyl-p-benzoquinone, and the prepared catalyst solution. The autoclave was fully purged with nitrogen, stirred at 500rpm, and heated to 30°C. Subsequently, 160g (2.96mol) of butadiene was added, and the autoclave was pressurized to 0.5MPa with nitrogen. The reaction was continued at 70°C for 8h. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a reaction mixture containing a mixture of raw materials, products, catalyst, and solvent. The reaction mixture included 1,3,7-cyclooctatriene (OCT), 4-vinyl-1-cyclohexene (VCH), 2,7-octadien-1-ol acetate (NODAc), and 1,7-octadien-3-ol acetate (IODAc).

[0073] The reaction mixture was extracted three times with 100 mL of n-hexane, and the product was separated into an extract phase containing the raw material and the 2,7-octadienyl compound and a raffinate phase. The extract phase was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated based on this. The conversion rate of the raw material butadiene in the extract phase was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. According to calculations, the conversion rate of the raw material butadiene was 98.8%, the selectivity of OCT was 0.7%, the selectivity of VCH was 4.1%, the selectivity of NODAc was 90.9%, the selectivity of IODAc was 4.3%, and the normal / isomer ratio was 21.1:1.

[0074] The palladium atomic weight and phosphine content in the raffinate phase were calculated based on the palladium concentration, phosphine concentration, and the weight of the recovered extract phase. The palladium concentration and phosphine concentration were quantitatively analyzed using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated using Formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated using Formula 4 in Example 1. The calculated recovery rates of palladium atoms were 99.4%, and the recovery rates of the organophosphine ligand were 99.2%.

[0075] Example 5

[0076] The implementation of Example 5 is the same as that of Example 4, except that:

[0077] The organic phosphine ligand is triphenylphosphine, and the amount of triphenylphosphine used is 0.408 g (1.56 mmol).

[0078] After the reaction was completed, the temperature was lowered to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane three times. The extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract phase was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. After calculation, the conversion rate of the raw material butadiene was 98.1%, the selectivity of OCT was 0.5%, the selectivity of VCH was 4.3%, the selectivity of NODAc was 91.7%, the selectivity of IODAc was 3.5%, and the normal / isomer ratio was 26.2:1.

[0079] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration, and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by formula 4 in Example 1. The calculation showed that the recovery rate of palladium atoms was 99.1%, and the recovery rate of the organophosphine ligand was 98.7%.

[0080] Example 6

[0081] The implementation of Example 6 is the same as that of Example 4, except that:

[0082] The reaction accelerator is p-benzoquinone, and the amount of p-benzoquinone used is 0.542 g (5.01 mmol).

[0083] After the reaction was completed, the temperature was lowered to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane three times. The extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract phase was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. After calculation, the conversion rate of the raw material butadiene was 98.0%, the selectivity of OCT was 0.9%, the selectivity of VCH was 3.6%, the selectivity of NODAc was 92.0%, the selectivity of IODAc was 3.5%, and the normal / isomer ratio was 26.3:1.

[0084] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration, and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by formula 4 in Example 1. The calculation showed that the recovery rates of palladium atoms were 98.9%, and the recovery rate of the organophosphine ligand was 98.9%.

[0085] Example 7

[0086] The implementation of Example 7 is the same as that of Example 4, except that:

[0087] The reaction accelerator is p-benzoquinone, and the amount of p-benzoquinone used is 0.223 g (2.06 mmol).

[0088] After the reaction was completed, the temperature was lowered to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane, extracted 3 times, and the extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract phase was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. After calculation, the conversion rate of butadiene in the extract phase was 97.5%, the selectivity of OCT was 0.9%, the selectivity of VCH was 3.8%, the selectivity of NODAc was 92.0%, the selectivity of IODAc was 3.5%, and the normal / isomer ratio was 26.3:1.

[0089] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration, and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by formula 4 in Example 1. The calculation showed that the recovery rate of palladium atoms was 98.5%, and the recovery rate of the organophosphine ligand was 98.4%.

[0090] Example 8

[0091] The implementation of Example 8 is the same as that of Example 4, except that:

[0092] The reaction promoter is 9,10-anthraquinone, and the amount of 9,10-anthraquinone used is 0.423 g (2.03 mmol).

[0093] After the reaction was completed, the temperature was lowered to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane for 3 times. The extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. After calculation, the conversion rate of the raw material butadiene was 97.7%, the selectivity of OCT was 0.8%, the selectivity of VCH was 5.2%, the selectivity of NODAc was 88.4%, the selectivity of IODAc was 5.6%, and the normal / isomer ratio was 15.8:1.

[0094] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration, and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by formula 4 in Example 1. The calculation showed that the recovery rate of palladium atoms was 97.8%, and the recovery rate of the organophosphine ligand was 97.7%.

[0095] Example 9

[0096] The implementation of Example 9 is the same as that of Example 4, except that:

[0097] The reaction accelerator is 2-ethyl-9,10-anthraquinone, and the amount of 2-ethyl-9,10-anthraquinone used is 0.483 g (2.04 mmol).

[0098] After the reaction was completed, the temperature was lowered to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane for 3 times. The extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract phase was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. After calculation, the conversion rate of the raw material butadiene was 98.2%, the selectivity of OCT was 0.6%, the selectivity of VCH was 3.8%, the selectivity of NODAc was 90.2%, the selectivity of IODAc was 5.4%, and the normal / isomer ratio was 16.7:1.

[0099] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration, and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by formula 4 in Example 1. The calculation showed that the recovery rate of palladium atoms was 98.3%, and the recovery rate of the organophosphine ligand was 97.7%.

[0100] Example 10

[0101] The implementation of Example 10 is the same as that of Example 4, except that:

[0102] The reaction promoter was 2-tert-butyl-9,10-anthraquinone (0.529 g, 2.00 mmol).

[0103] After the reaction was completed, the temperature was lowered to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane for 3 times. The extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. After calculation, the conversion rate of the raw material butadiene was 97.6%, the selectivity of OCT was 0.8%, the selectivity of VCH was 5.3%, the selectivity of NODAc was 88.6%, the selectivity of IODAc was 5.3%, and the normal / isomer ratio was 16.7:1.

[0104] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis by an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by Formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by Formula 4 in Example 1. According to the calculation, the recovery rate of palladium atoms was 97.1%, and the recovery rate of the organophosphine ligand was 97.1%.

[0105] Example 11

[0106] The implementation of Example 11 is the same as that of Example 5, except that:

[0107] After each reaction was completed, the reaction mixture was extracted with 100 mL of n-hexane, and the raffinate was recovered and recycled to the next reaction. The results of 50 applications are shown in Table 1. As can be seen from Table 1, the reaction promoter 2,5-di-tert-butyl-p-benzoquinone was added to the reaction system. Under the synergistic effect of the reaction promoter and the catalyst, the reaction promoter can accelerate the conversion of active components in the catalyst in different valence states, prevent the active components from being lost from the homogeneous system, and enable the catalyst to maintain a high catalytic activity for a long time. After 50 applications, the recovery rate of the phosphine ligand reached 98.7%, thereby reducing the amount of the phosphine ligand. After 30 consecutive applications, the reaction conversion rate and selectivity were still high. After 50 consecutive applications, the conversion rate of the raw material butadiene was still greater than 94%, and the selectivity of NODAc was only reduced by 1.4%.

[0108] Table 1 Recovery and recycling of the raffinate phase after the reaction in Example 11

[0109] Number of reactions Butadiene conversion rate (%) NODAc selectivity (%) Palladium atom recovery rate (%) Recovery rate of phosphine ligand (%) 1 98.9 90.9 99.4 99.2 5 98.7 90.5 99.3 99.1 10 98.3 91.0 99.1 99.2 20 97.6 90.6 99.3 99.0 30 96.0 90.2 98.8 98.6 50 94.3 89.6 98.9 98.7

[0110] Comparative Example 1

[0111] The implementation method of Comparative Example 1 is the same as that of Example 1, except that:

[0112] No reaction accelerator 2,5-di-tert-butyl-p-benzoquinone was added.

[0113] After the reaction was completed, the temperature was lowered to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane three times. The extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract phase was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. After calculation, the conversion rate of the raw material butadiene was 66.3%, the selectivity of OCT was 2.3%, the selectivity of VCH was 8.9%, the selectivity of NODA was 79.3%, the selectivity of IODA was 9.5%, and the normal / isomer ratio was 8.3:1.

[0114] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration, and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by formula 4 in Example 1. The calculation showed that the recovery rate of palladium atoms was 85.6%, and the recovery rate of the organophosphine ligand was 84.4%.

[0115] Comparative Example 2

[0116] The implementation method of Comparative Example 2 is the same as that of Example 4, except that:

[0117] No reaction accelerator 2,5-di-tert-butyl-p-benzoquinone was added.

[0118] After the reaction was completed, the temperature was lowered to room temperature to obtain a reaction mixture, and the reaction mixture was extracted with 100 mL of n-hexane for 3 times. The extract was subjected to gas chromatography analysis, and the conversion rate of the raw material, the selectivity of the product, and the yield were calculated on this basis; the conversion rate of the raw material butadiene in the extract was calculated according to Formula 1 in Example 1, and the selectivity of each product was calculated according to Formula 2 in Example 1. After calculation, the conversion rate of the raw material butadiene was 78.1%, the selectivity of OCT was 0.8%, the selectivity of VCH was 8.4%, the selectivity of NODAc was 81.9%, the selectivity of IODAc was 8.9%, and the normal / isomer ratio was 9.2:1.

[0119] The palladium atomic weight and phosphine content contained in the raffinate phase were calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration were respectively obtained by quantitative analysis using an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms was calculated by formula 3 in Example 1, and the recovery rate of the organophosphine ligand was calculated by formula 4 in Example 1. The calculation showed that the recovery rate of palladium atoms was 90.6%, and the recovery rate of the organophosphine ligand was 88.9%.

[0120] Comparative Example 3

[0121] The implementation method of Comparative Example 3 is the same as that of Example 4, except that:

[0122] No reaction promoter 2,5-di-tert-butyl-p-benzoquinone was added. After the reaction was completed, the temperature was cooled to room temperature to obtain a reaction mixture. The reaction mixture was extracted with 100 mL of n-hexane three times. The extract phase was recovered and recycled for the next reaction. The results are shown in Table 2.

[0123] As shown in Table 2, when no reaction promoter was added during the polymerization process, the conversion of the raw material butadiene decreased to 36.8% after 10 cycles. The conversion of the raw material butadiene was 41.3% lower than that after one cycle, and the selectivity of the product NODAc was also reduced by 18.6%. Therefore, when no reaction promoter was added, the catalyst recovery rate was low.

[0124] Table 2 Results of recycling the raffinate phase after the reaction of Comparative Example 3

[0125]

[0126] Table 3 Comparison of results of Examples and Comparative Examples

[0127]

[0128] Table 3 is a comparison table of the results of the examples and the comparative examples. As can be seen from Table 3, a reaction accelerator was added to all of Examples 1-10, while no reaction accelerator was added to Comparative Examples 1-2. Compared with Comparative Example 1, the conversion rate of butadiene with the addition of a reaction accelerator during the reaction was greater than 95%, while the conversion rate of butadiene without the addition of a reaction accelerator was 66.3% and 78.1%. The conversion rate of butadiene with the addition of a reaction accelerator was much greater than the conversion rate of butadiene without the addition of a reaction accelerator. This is because adding a small amount of reaction accelerator to the catalyst system can greatly reduce the loss of active components of the catalyst. In a conventional homogeneous palladium catalytic system, a considerable amount of zero-valent palladium can be aggregated and formed into catalytically inactive palladium black due to its inability to participate in the redox cycle, which precipitates from the homogeneous system. The reaction accelerator can oxidize it into a soluble divalent palladium salt, thereby re-participating in the catalytic system. At the same time, when a reaction accelerator is added, the stability of the reaction intermediate can be improved. While maintaining the same catalytic efficiency, the amount of the organic phosphine ligand is greatly reduced, greatly reducing the cost of the catalyst. When the amount of ligand is reduced, the palladium metal center of the reaction intermediate is more likely to complex with the double bond of the olefin, favoring the formation of the normal product. Correspondingly, the selectivity of the reaction can be further improved.

[0129] The present application, under the synergistic catalysis of a palladium catalyst, an organic phosphine ligand and a reaction promoter, in combination with an organic tertiary amine, can achieve a raw material conversion rate of more than 95%, a selectivity of the target product of more than 90%, and a normal / isomer ratio of (13.5~26.2:1). In addition, the preparation method has strong universality and can be used to prepare a variety of compounds with different substituents, including alcohols, esters, ethers, amines, etc.

[0130] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A method for preparing a 2,7-octadienyl compound, characterized in that: A conjugated diene having at least two conjugated double bonds is subjected to a telomerization reaction with a nucleophilic reagent in the presence of a catalyst and a reaction accelerator to obtain a 2,7-octadienyl compound; Wherein, the reaction accelerator is a quinone compound; the quinone compound is at least one of a benzoquinone compound (Va) or an anthraquinone compound (Vb); the general formula of the benzoquinone compound (Va) and the anthraquinone compound (Vb) is as follows: Where R 17 、R 18 、R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 、R 27 and R 28 Hydrogen, alkyl, alkoxy, aryl, SO3 - U + , halogen, nitro or cyano; wherein, U + represents an alkali metal ion; The catalyst comprises an organic phosphine ligand and a palladium compound, wherein the organic phosphine ligand is a triarylphosphine compound; The nucleophilic reagent includes at least one of compound (IIa), compound (IIb), or compound (IIc), and the general formula of compound (IIa), compound (IIb), and compound (IIc) is as follows: Where R 1 , R 2 , R 3 , R 4 is any one of hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl; A base is further added in the telomerization reaction, and the base in the telomerization reaction includes one or more of trialkylamine, alicyclic tertiary amine, and pyridine.

2. The preparation method according to claim 1, characterized in that The nucleophilic reagent includes any one of water, methanol, acetic acid and propionic acid.

3. The preparation method according to claim 1, characterized in that The conjugated diene comprises at least one of 1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-octadiene and 1,3,7-octatriene.

4. The preparation method according to claim 1, characterized in that The general formula (IV) of the triarylphosphine compound is as follows: Where R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 and R 16 Hydrogen, alkyl, alkoxy, SO3 - M + ,NE 1 E 2 , halogen, trifluoromethyl or cyano; wherein, M + Alkali metal ions or cations N + F 1 F 2 F 3 F 4 Any one of; wherein, the E 1 and E 2 is any one of hydrogen, alkyl, cycloalkyl or aryl, E 1 and E 2 are the same or different groups; the F 1 、F 2 、F 3 and F 4 is any one of hydrogen, alkyl, cycloalkyl or aryl, and the F 1 、F 2 、F 3 and F 4 are the same or different groups; Among them, the R 5 、R 6 、R 7 and R 8 At least two of the substituents are hydrogen, R 9 、R 10 、R 11 and R 12 At least two of the substituents are hydrogen, R 13 、R 14 、R 15 and R 16 At least two of the substituents are hydrogen.

5. The preparation method according to claim 1, characterized in that The palladium compound is a complex or salt compound in an oxidation state of (0), or the palladium compound is a complex or salt compound in an oxidation state of (II).

6. The preparation method according to claim 4, characterized in that The molar ratio of palladium atoms to phosphine atoms in the catalyst is 1:(0.5-10).

7. The preparation method according to claim 4, characterized in that The molar ratio of palladium atoms to phosphine atoms in the catalyst is 1:(1-5).

8. The preparation method according to claim 4, characterized in that The molar ratio of the reaction accelerator to the palladium atoms in the catalyst is (0.1-100):1, and / or the molar ratio of the nucleophile to the conjugated diene is (0.5-2):1, and / or the molar ratio of the palladium atoms in the catalyst to the conjugated diene is (0.000001-0.1):

1.

9. The preparation method according to claim 1, characterized in that A water-soluble solvent is further added to the polyolation reaction, and the water-soluble solvent includes at least one or more of acetone, acetonitrile, heptanone, tetrahydrofuran, 1,4-dioxane, sulfolane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and / or, the mass ratio of the water-soluble solvent in the polyolation reaction to the conjugated diene is (0.5-2):

1.

10. The preparation method according to claim 1, characterized in that The molar ratio of the base in the telomerization reaction to the conjugated diene is (0.01-100):

1.

11. The preparation method according to claim 1, characterized in that The reaction temperature of the telomerization reaction is 40 to 160° C., the reaction pressure of the telomerization reaction is 0.1 to 10 MPa, and the reaction time of the telomerization reaction is 3 to 20 hours.

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