Preparation method of 2, 7-octadienyl compound

Abstract

The invention provides a preparation method of a 2, 7-octadienyl compound, and relates to the technical field of homogeneous catalysis and organic synthesis.The preparation method comprises the step that conjugated diene with at least two conjugated double bonds and a nucleophilic reagent are subjected to telomerization reaction under the action of a catalyst and a reaction accelerant to obtain the 2, 7-octadienyl compound. According to the preparation method, a small amount of reaction accelerant is added, the reaction accelerant has a good synergistic effect with the catalyst, the stability of a reaction intermediate can be remarkably improved, the use amount of an organic phosphine ligand is reduced, the cost of the catalyst is reduced, rapid circulation of active components, namely zero-valent palladium and divalent palladium in the catalyst can be accelerated, and the yield of the catalyst is increased. The catalytic efficiency is improved, side reactions are reduced, and the reaction selectivity is effectively improved.

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 can be used as important precursors for solvents, plasticizers, fine chemicals, and intermediates for active compounds. For example, the chain C8-alcohols and C8 olefins synthesized from 1,3-butadiene are precursors for 1-octanol and 1-octene, which are then used in flavors and fragrances such as hexyl cinnamaldehyde and plasticizers such as DONP. 1-Octene is a high-value comonomer for the synthesis of polyolefin elastomers.

[0003] Telomerization reactions have been extensively described in the literature, but known telomerization methods have problems with high catalyst costs and / or by-products. Currently, the only telomerization reaction that has been industrially applied is the butadiene telomerization process used by Kuraray to synthesize 1-octanol.

[0004] The publication number is CN1096286A, and the patent name is "Method for preparing chain diene alcohol compounds". It discloses a method for using palladium compounds and phosphine ligands for homogeneous catalysis to carry out polymerization reaction. In the presence of carbon dioxide, palladium compounds and phosphine ligands are used as catalysts to react conjugated dienes with water. The reaction is carried out under the condition that free phosphine compounds are present in the reaction solution. This requires that the amount of phosphine ligand used is much larger than the amount of palladium catalyst used, which is costly, and 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 the requirements of industrialization.

[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 a mixed C4 hydrocarbon component as a raw material and methanol for a polymerization reaction to synthesize 2,7-octadiene-1-ol. However, this process has many reaction by-products, the ligand synthesis is 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 conversion rate of the reaction is only 74.4~81.6%, the recovery rate of palladium is only 67~91%, and the recovery rate of phosphine 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 a reaction. After the reaction is completed, the catalyst is filtered out and directly reacted again. No deactivation phenomenon is observed after 50 consecutive applications. 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, affecting 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; Wherein, 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 formula of compound (IIa), compound (IIb) and compound (IIc) is as follows: ; In the formula, R 1 , R 2 , R 3 , R 4 It is any one of hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl.

[0010] In one embodiment, 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: ; In the formula, R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28is 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; 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 above, 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 - It represents any one of the halogen ions.

[0011] In one embodiment, the benzoquinone compound (Va) and the anthraquinone compound (Vb) include but are not limited to compounds with the following structural formulas: ; ; In one embodiment, the nucleophilic reagent includes any one of water, methanol, acetic acid and propionic acid; 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.

[0012] In one embodiment, the catalyst comprises an organic phosphine ligand and a palladium compound, wherein the organic phosphine ligand is a triaryl phosphine compound, and the general formula (IV) of the triaryl phosphine compound is as follows: ; In the formula, 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 , COR a ,OCOR a , halogen, nitro, trifluoromethyl or cyano; M + is an alkali metal ion or a cation N + F 1 F 2 F 3 F4 Any one of Z - is any one of the halogen ions; 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; 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; 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.

[0013] In one embodiment, the structural formula of the triarylphosphine compound includes but is not limited to the compound described in the following structure: ; ; .

[0014] In one embodiment, the palladium compound is a complex or salt compound in oxidation state (0), or the palladium compound is a complex or salt compound in oxidation state (II); 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; Preferably, the palladium compound with oxidation state (II) includes at least one or more of palladium acetate, palladium chloride, palladium sulfate, palladium nitrate, palladium iodide, palladium pivalate, palladium trifluoroacetate, trimethyl palladium 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 di-μ-dichlorobis(triphenylphosphine)dipalladium.

[0015] 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.

[0016] 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).

[0017] In one embodiment, the molar ratio of the reaction accelerator to the palladium atom 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 atom in the catalyst to the conjugated diene is (0.000001-0.1):1; 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; 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.

[0018] In one embodiment, a water-soluble solvent is further added during the polyolation reaction, and the water-soluble solvent includes at least one or more of acetone, acetonitrile, heptanone, tetrahydrofuran, 1,4-dioxane, cyclopentane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and / or, the mass ratio of the water-soluble solvent of the polyolation reaction to the conjugated diene is (0.5~2):1.

[0019] In one embodiment, a base is further added during the polymerization reaction, and the base of the polymerization reaction includes one or more of trialkylamines, alicyclic tertiary amines, and pyridines; preferably, the base of the polymerization 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 of the polymerization reaction includes at least one or more of trimethylamine, triethylamine and tripropylamine; And / or, the molar ratio of the base in the polyolation reaction to the conjugated diene is (0.01-100):1, preferably, the molar ratio of the base in the polyolation reaction to the conjugated diene is (0.1-10):1; more preferably, the molar ratio of the base in the polyolation reaction to the conjugated diene is (0.5-2):1.

[0020] In one embodiment, the reaction temperature of the telomerization reaction is 40~160°C, the reaction pressure of the telomerization reaction is 0.1~10MPa, and the reaction time of the telomerization reaction is 3~20h; preferably, the reaction temperature of the telomerization reaction is 50~100°C, the reaction pressure of the telomerization reaction is 0.5~5MPa, and the reaction time of the telomerization reaction is 3~10h.

[0021] 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 polyreaction 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, and the reaction promoter not only has a good synergistic effect with the catalyst, can significantly improve the stability of the reaction intermediate, reduce the amount of organic phosphine ligand, and reduce the cost of the catalyst, but also can accelerate the rapid circulation of the active components zero-valent palladium and divalent palladium in the catalyst, improve the catalytic efficiency, reduce the occurrence of side reactions, and effectively improve the reaction selectivity. DETAILED DESCRIPTION

[0022] 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 may be combined with other embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians of this field without making creative work are within the scope of protection of this application.

[0023] Unless otherwise specified, all reagents used in this application are commercially available.

[0024] In the present application, the palladium concentration and phosphine concentration contained in the raffinate phase obtained by the extraction operation were quantitatively analyzed by an inductively coupled plasma mass spectrometer (Agilent). The raw materials and product 2,7-octadienyl compounds contained in the reaction liquid of the telomerization reaction were analyzed and quantified by gas chromatography under the following measurement conditions. On this basis, the conversion rate of the reactants, the selectivity and yield of the products were calculated.

[0025] The gas chromatography analysis conditions are as follows: chromatographic column: Agilent DB-Wax (specifications: 30m×0.32mm×0.25mm); inlet temperature: 300°C; split ratio: 30:1; column flow: 1.5mL / min; column temperature: 100°C for 0.5min; heating program: 15°C / min to 300°C, maintained for 8min; detector temperature: 300°C, hydrogen flow: 35mL / min, air flow: 350mL / min.

[0026] Example 1 Under 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, and then 3.01 g of triphenylphosphine tris-sulfonic acid sodium salt (5.72 mmol) was added to the glass flask. The mixture was stirred at room temperature for 20 min to prepare a catalyst solution.

[0027] 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 were added to a 1 L autoclave, the autoclave was fully replaced with carbon dioxide, and the temperature was raised to 30° C. while stirring at 500 rpm. Subsequently, 108 g of butadiene (2 mol) was added, and the autoclave was pressurized to 1.2 MPa with carbon dioxide, and the reaction was carried out at 70° C. for 6 hours. After the reaction was completed, the temperature was cooled to room temperature to obtain a reaction liquid mixture, which included a series of mixtures of raw materials, products, catalysts, solvents, etc. The reaction mixture included 1,3,7-cyclooctatriene (OCT), 4-vinyl-1-cyclohexene (VCH), 2,7-octadiene-1-ol (NODA) and 1,7-octadiene-3-ol (IODA).

[0028] The reaction mixture was extracted with 100 mL of n-hexane for 3 times, and the product was separated into an extract phase and a raffinate phase containing the raw material and the 2,7-octadienyl compound. The extract phase was analyzed by gas chromatography, and the conversion rate of the raw material, the selectivity and the yield of the product were calculated on this basis; 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.

[0029] Formula 1; Formula 2; According to calculation, 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.

[0030] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are quantitatively analyzed by an inductively coupled plasma mass spectrometer (Agilent), respectively. The recovery rate of palladium atoms is calculated by formula 3, and the recovery rate of the organic phosphine ligand is calculated by formula 4, where the units of each quantity are mol.

[0031] Formula 3; Formula 4; The recovery rates of palladium atoms and organophosphine ligands were calculated to be 99.2% and 98.3%, respectively.

[0032] Example 2 The implementation method of Example 2 is the same as that of Example 1, except that: 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).

[0033] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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.

[0034] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are respectively obtained by quantitative analysis by an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 1. After calculation, the recovery rate of palladium atoms is 99.1%, and the recovery rate of the organic phosphine ligand is 97.1%.

[0035] Example 3 The implementation method of Example 3 is the same as that of Example 1, except that: 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).

[0036] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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.

[0037] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are respectively obtained by quantitative analysis by an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 2. After calculation, the recovery rate of palladium atoms is 98.3%, and the recovery rate of the organic phosphine ligand is 97.7%.

[0038] Example 4 Under nitrogen atmosphere, 20 g of a sulfolane solution containing 0.231 g of palladium acetate (1.03 mmol of palladium atom) was added to a 100 mL glass flask, and then 1.07 g of triphenylphosphine (3.96 mmol) was added to the glass flask. The mixture was stirred at room temperature for 20 min to prepare a catalyst solution.

[0039] In a 1L autoclave, 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 were added, the autoclave was fully replaced with nitrogen, stirred at 500rpm and heated to 30°C, then 160g (2.96mol) of butadiene was added, and the autoclave was pressurized to 0.5MPa with nitrogen, and reacted at 70°C for 8h. After the reaction was completed, the temperature was cooled to room temperature to obtain a reaction liquid mixture, which included a series of mixtures of raw materials, products, catalysts, solvents, etc. The reaction mixture included 1,3,7-cyclooctatriene (OCT), 4-vinyl-1-cyclohexene (VCH), 2,7-octadiene-1-ol acetate (NODAc) and 1,7-octadiene-3-ol acetate (IODAc).

[0040] The reaction mixture was extracted with 100 mL of n-hexane for 3 times, and the product was separated into an extract phase and a raffinate phase containing the raw material and the 2,7-octadienyl compound. 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 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. 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.

[0041] The amount of palladium atoms and the 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 quantitatively analyzed by an inductively coupled plasma mass spectrometer (Agilent), respectively, the recovery rate of palladium atoms was calculated by formula 3 in Example 1, and the recovery rate of the organic phosphine ligand was calculated by formula 4 in Example 1. According to calculation, the recovery rate of palladium atoms was 99.4%, and the recovery rate of the organic phosphine ligand was 99.2%.

[0042] Example 5 The implementation method of Example 5 is the same as that of Example 4, except that: The organic phosphine ligand is triphenylphosphine, and the amount of triphenylphosphine used is 0.408 g (1.56 mmol).

[0043] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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.

[0044] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are quantitatively analyzed by an inductively coupled plasma mass spectrometer (Agilent), respectively. The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 1. After calculation, the recovery rate of palladium atoms is 99.1%, and the recovery rate of the organic phosphine ligand is 98.7%.

[0045] Example 6 The implementation method of Example 6 is the same as that of Example 4, except that: The reaction accelerator is p-benzoquinone, and the amount of p-benzoquinone used is 0.542 g (5.01 mmol).

[0046] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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.

[0047] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are quantitatively analyzed by an inductively coupled plasma mass spectrometer (Agilent), respectively. The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 1. After calculation, the recovery rates of palladium atoms are 98.9%, and the recovery rates of the organic phosphine ligands are 98.9%.

[0048] Example 7 The implementation method of Example 7 is the same as that of Example 4, except that: The reaction accelerator is p-benzoquinone, and the amount of p-benzoquinone used is 0.223 g (2.06 mmol).

[0049] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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.

[0050] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are respectively obtained by quantitative analysis by an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 1. After calculation, the recovery rate of palladium atoms is 98.5%, and the recovery rate of the organic phosphine ligand is 98.4%.

[0051] Example 8 The implementation method of Example 8 is the same as that of Example 4, except that: The reaction promoter is 9,10-anthraquinone, and the amount of 9,10-anthraquinone used is 0.423 g (2.03 mmol).

[0052] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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 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.

[0053] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are quantitatively analyzed by an inductively coupled plasma mass spectrometer (Agilent), respectively. The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 1. After calculation, the recovery rate of palladium atoms is 97.8%, and the recovery rate of the organic phosphine ligand is 97.7%.

[0054] Example 9 The implementation method of Example 9 is the same as that of Example 4, except that: The reaction promoter is 2-ethyl-9,10-anthraquinone, and the amount of 2-ethyl-9,10-anthraquinone used is 0.483 g (2.04 mmol).

[0055] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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.

[0056] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are respectively obtained by quantitative analysis by an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 1. After calculation, the recovery rate of palladium atoms is 98.3%, and the recovery rate of the organic phosphine ligand is 97.7%.

[0057] Example 10 The implementation method of Example 10 is the same as that of Example 4, except that: The reaction promoter was 2-tert-butyl-9,10-anthraquinone (0.529 g, 2.00 mmol).

[0058] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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 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.

[0059] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are quantitatively analyzed by an inductively coupled plasma mass spectrometer (Agilent), respectively. The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 1. After calculation, the recovery rate of palladium atoms is 97.1%, and the recovery rate of the organic phosphine ligand is 97.1%.

[0060] Embodiment 11 The implementation method of Example 11 is the same as that of Example 5, except that: After each reaction is completed, 100 mL of n-hexane is used to extract the reaction mixture, and the raffinate phase is recovered and recycled to the next reaction. The results of 50 applications are shown in Table 1. It can be seen from Table 1 that a reaction promoter 2,5-di-tert-butyl-p-benzoquinone is 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, avoid the loss of active components 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 can still be maintained at a high level. After 50 consecutive applications, the conversion rate of the raw material butadiene is still greater than 94%, and the selectivity of NODAc is only reduced by 1.4%.

[0061] Table 1: Recovery and recycling of the raffinate phase after the reaction of Example 11 is completed Number of reactions Butadiene conversion rate (%) NODAc selectivity (%) Palladium atomic 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 Comparative Example 1 The implementation method of Comparative Example 1 is the same as that of Example 1, except that: No reaction accelerator 2,5-di-tert-butyl-p-benzoquinone was added.

[0062] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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.

[0063] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are respectively obtained by quantitative analysis by an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 1. After calculation, the recovery rate of palladium atoms is 85.6%, and the recovery rate of the organic phosphine ligand is 84.4%.

[0064] Comparative Example 2 The implementation method of Comparative Example 2 is the same as that of Example 4, except that: No reaction accelerator 2,5-di-tert-butyl-p-benzoquinone was added.

[0065] 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 for 3 times. The extract phase was analyzed by gas chromatography, 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 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.

[0066] The amount of palladium atoms and the phosphine content contained in the raffinate phase are calculated by the palladium concentration, the phosphine concentration and the weight of the recovered extract phase, wherein the palladium concentration and the phosphine concentration are respectively obtained by quantitative analysis by an inductively coupled plasma mass spectrometer (Agilent). The recovery rate of palladium atoms is calculated by formula 3 of Example 1, and the recovery rate of the organic phosphine ligand is calculated by formula 4 of Example 1. After calculation, the recovery rate of palladium atoms is 90.6%, and the recovery rate of the organic phosphine ligand is 88.9%.

[0067] Comparative Example 3 The implementation method of Comparative Example 3 is the same as that of Example 4, except that: 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 for 3 times. The raffinate phase was recovered and recycled for the next reaction. The results are shown in Table 2.

[0068] It can be seen from Table 2 that no reaction promoter was added during the polymerization reaction. After 10 cycles, the conversion rate of raw material butadiene was reduced to 36.8%, which was 41.3% lower than the conversion rate 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.

[0069] Table 2 Results of recycling the raffinate phase after the reaction of Comparative Example 3

[0070] Table 3 Comparison of results of the embodiments and comparative examples

[0071] Table 3 is a comparison table of the results of the embodiments and the comparative examples. It can be seen from Table 3 that the reaction promoter is added in the embodiments 1-10, and the reaction promoter is not added in the comparative example 1-2. Compared with the comparative example 1, the conversion rate of butadiene with the reaction promoter added in the reaction process of the embodiments 1-3 is greater than 95%, while the conversion rate of butadiene without the reaction promoter is 66.3% and 78.1%. The conversion rate of butadiene with the reaction promoter added is much greater than the conversion rate of butadiene without the reaction promoter. This is because adding a small amount of reaction promoter to the catalyst system can greatly reduce the loss of the active components of the catalyst. In the usual homogeneous palladium catalytic system, a considerable amount of zero-valent palladium will be aggregated and formed due to the inability to participate in the redox cycle. The catalytically inactive palladium black is precipitated from the homogeneous system, and the reaction promoter can oxidize it into a soluble divalent palladium salt, thereby re-participating in the catalytic system. At the same time, when the reaction promoter 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, which greatly reduces the cost of using the catalyst. When the amount of ligand is reduced, the palladium metal center of the reaction intermediate is more inclined to complex with the double bond of the olefin, which is conducive to the formation of normal products. Correspondingly, the selectivity of the reaction can also be further improved.

[0072] The present application, under the synergistic catalysis of palladium catalyst, organic phosphine ligand and reaction accelerator, cooperates with organic tertiary amine to achieve a raw material conversion rate of more than 95%, the selectivity of the target product is more than 90%, and the normal / isomer ratio is (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.

[0073] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions, etc. made within the spirit and principles of the present application shall be included in the protection scope 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 agent 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 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: ； In the formula, R 1 , R 2 , R 3 , R 4 It is any one of hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl.

2. The preparation method according to claim 1, characterized in that: 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: ； In the formula, 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 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; 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 above, 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 - It represents any one of the halogen ions.

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

4. 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.

5. The preparation method according to claim 1, characterized in that: The catalyst comprises an organic phosphine ligand and a palladium compound, wherein the organic phosphine ligand is a triaryl phosphine compound, and the general formula (IV) of the triaryl phosphine compound is as follows: ； In the formula, 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 , COR a ,OCOR a , halogen, nitro, trifluoromethyl or cyano; M + is an alkali metal ion or a cation N + F 1 F 2 F 3 F 4 Any one of Z - is any one of the halogen ions; 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.

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

7. The preparation method according to claim 5, characterized in that: The molar ratio of palladium atoms to phosphine atoms in the catalyst is 1:(0.5-10).

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

9. The preparation method according to claim 5, 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.

10. The preparation method according to claim 1, characterized in that: A water-soluble solvent is also added during the polyolation reaction, and the water-soluble solvent includes at least one or more of acetone, acetonitrile, heptanone, tetrahydrofuran, 1,4-dioxane, cyclopentane, 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.

11. The preparation method according to claim 1, characterized in that: A base is also added during the telomerization reaction, and the base for the telomerization reaction includes one or more of trialkylamines, alicyclic tertiary amines, and pyridines; And / or, the molar ratio of the base in the polymerization reaction to the conjugated diene is (0.01-100):

1.

12. The preparation method according to claim 1, characterized in that: 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.

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