CN113801161A - Imidazole ligand derivative, preparation thereof and application thereof in butadiene telomerization reaction - Google Patents

Imidazole ligand derivative, preparation thereof and application thereof in butadiene telomerization reaction Download PDF

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CN113801161A
CN113801161A CN202010544639.1A CN202010544639A CN113801161A CN 113801161 A CN113801161 A CN 113801161A CN 202010544639 A CN202010544639 A CN 202010544639A CN 113801161 A CN113801161 A CN 113801161A
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octadiene
butadiene
palladium
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董开武
姚其义
沈超仁
张鸿儒
许正帅
纪晓雷
史张霖
唐霖
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East China Normal University
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Abstract

The invention discloses an imidazole ligand derivative shown in formula (I) and formula (II) and application thereof as an additive in the telomerization of 1,3-butadiene to generate 1-substituted-2, 7-octadiene or 3-substituted-1, 7-octadiene; wherein, under the action of a catalyst and the additive, 1,3-butadiene reacts with primary aliphatic alcohol compounds or primary alcohol sodium salt to obtain 1-substituted-2, 7-octadiene or 3-substituted-1, 7-octadiene. The additive can obviously improve the TON of the substrate molecule converted by unit active site and the chemical selectivity and the regioselectivity in the preparation process of the telomerization product 1-substituted-2, 7-octadiene or 3-substituted-1, 7-octadiene, wherein the TON of the substrate molecule converted by unit active site is as high as 380000. The invention also discloses a preparation method of the imidazole ligand derivative shown in the formula (I) and the imidazole ligand derivative shown in the formula (II). The invention has practical application value and wide application prospect.

Description

Imidazole ligand derivative, preparation thereof and application thereof in butadiene telomerization reaction
Technical Field
The invention belongs to the technical field of organic compounds and synthesis, and relates to an imidazole ligand derivative, a preparation method thereof and application thereof in butadiene telomerization.
Background
Butadiene is an important organic chemical raw material, and is mainly used for producing polybutadiene rubber, styrene-butadiene rubber, nitrile rubber, styrene-butadiene latex, styrene thermoplastic elastomer (SBC), acrylonitrile-butadiene-styrene copolymer (ABS resin), and the like, and also used for producing adiponitrile, hexamethylenediamine, nylon 66, 1, 4-butanediol, ethylidene norbornene (a third monomer of ethylene-propylene rubber), tetrahydrofuran, and the like. 1,3-butadiene (1,3-butadiene) is not only a common monomer in the field of high polymer materials, but also an important raw material in the field of fine chemical engineering for synthesizing olefin products with high added values. At present, the production method of butadiene mainly comprises an extraction method of ethylene cracking by-products C4 and a deoxidation method of C4 alkane or alkene.
Because octane has significant commercial value in the gasoline fuel industry, improved processes for producing its suitable starting material (1-octene) have long been sought. Included in the process for producing 1-octene is a synthesis step of short-chain polymerized butadiene, wherein the process for synthesizing short-chain polymerized butadiene is described in U.S. (U.S.) patent document No.8,558,030, which includes a process for contacting butadiene and an organic hydroxy compound represented by the formula ROH, where R is a substituted or unsubstituted C1 to C20 hydrocarbon group and the organic hydroxy compound is not glycerol, in a reaction fluid in the presence of a palladium catalyst and a phosphine ligand represented by the formula PAr3, where each Ar is independently a substituted or unsubstituted aryl group having a hydrogen atom in at least one ortho position and at least two Ar groups are ortho-hydrocarboxyl substituted aryl groups. Disadvantages of this process include the need to prepare a catalyst precursor and the reaction including an induction period. Accordingly, it is desirable by those skilled in the art to reduce or eliminate this induction period to the maximum possible extent.
Jacksell et al describe the use of additives in telomerization reactions in the "Industrially useful Catalyst systems for Palladium-Catalyzed telomerization of 1,3-Butadiene with Alcohols (An Industrial visible Catalyst System for Palladium-Catalyzed catalysts of 1,3-Butadiene with Alcohols)", the European journal of chemistry (chem. Eur. J.) 2004,10, 3891-3900. The method has low reaction efficiency, and the substrate molecule number TON converted by unit active site, chemical selectivity and regioselectivity are all to be improved.
Disclosure of Invention
The invention aims to provide two imidazole ligand derivatives shown in formulas (I) and (II), preparation thereof and application thereof as an additive in telomerization of 1,3-butadiene, wherein the additive is used as a ligand of a catalyst to synthesize a target product in one step in the telomerization of 1,3-butadiene to generate 1-substituted-2, 7-octadiene or 3-substituted-1, 7-octadiene, the number of substrate molecules TON converted by unit active sites can be effectively increased, the chemical selectivity and the regioselectivity are improved, and the reaction conversion rate and the yield of a linear target product 1 are high.
The invention provides imidazole ligand derivatives shown in formula (I) and formula (II), which have the following structures:
Figure BDA0002540275770000021
wherein the content of the first and second substances,
R1、R2is alkyl, pyridyl,Alkyl-substituted phenyl; wherein R is1、R2May be the same or different;
R3is phenyl or alkyl substituted by alkyl;
preferably, the first and second electrodes are formed of a metal,
R1、R2is C1-C6 alkyl, pyridyl, C1-C6 alkyl substituted phenyl;
R3is C1-C6 alkyl substituted phenyl, C1-C6 alkyl;
it is further preferred that the first and second liquid crystal compositions,
R1＝R2is tert-butyltBu, or R1Pyridyl Py, R2Is tert-butyltBu；
R34-OMe (methoxy) substituted phenyl, or R31,3, 5-mesityl substituted phenyl.
The invention also provides application of the imidazole ligand derivatives shown in the formulas (I) and (II) as additives in butadiene telomerization reaction; specifically, the imidazole ligand derivatives shown in the formulas (I) and (II) are applied to 1,3-butadiene as an additive to generate 1-substituted-2, 7-octadiene or 3-substituted-1, 7-octadiene.
Wherein, the application specifically comprises the following steps: under the action of a catalyst and an additive, 1,3-butadiene and a primary aliphatic alcohol compound ROH or a corresponding salt thereof perform telomerization to generate 1-substituted-2, 7-octadiene shown in a formula 1 or 3-substituted-1, 7-octadiene shown in a formula 2, and the structural formula is as follows: CH2 ═ CH-CH2-CH2-CH2-CH ═ CH-CH2-OR CH2 ═ CH-CH2-CH2-CH2-CH (OR) -CH ═ CH 2-the reaction process is shown in formula (III):
Figure BDA0002540275770000022
wherein the content of the first and second substances,
r represents a group of a primary aliphatic alcohol, in particular R is a C1 to C20 hydrocarbon group;
wherein the primary aliphatic alcohol compound is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, etc.; preferably methanol, ethanol, propanol.
The corresponding salt of the primary aliphatic alcohol compound comprises one or more of sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide and the like; preferably sodium methoxide, sodium ethoxide, sodium propoxide.
Wherein the reaction catalyst is a palladium catalyst, and comprises one or more of palladium acetylacetonate, palladium formate, palladium acetate, palladium propionate, palladium caprylate, palladium carbonate and the like; preferably palladium acetylacetonate, palladium formate, palladium acetate.
Wherein the molar ratio of the 1,3-butadiene to the primary aliphatic alcohol compound or primary alcohol sodium salt is 2: 1.
wherein the reaction temperature is 60-100 ℃; preferably, it is 60 ℃.
Wherein the reaction time is 5-16 hours; preferably, it is 8 hours.
In the application of the invention, through one-step reaction, the number of substrate molecules TON converted per active site can reach as high as 380000, the chemoselectivity of the compounds 1 and 2 is more than 98%, and the regioselectivity is more than 98%.
The invention also provides a preparation method of the imidazole ligand derivative shown in the formula (I), which comprises the following specific steps:
under the nitrogen atmosphere, 4-amino [2,2] cycloform, paraformaldehyde and NH4Cl are added into a reaction tube filled with magnetons, and 1,4 dioxane and water are added. Glyoxal and 2 drops of phosphoric acid were added. Heating and refluxing for 18 hours, cooling to room temperature, adding a sodium hydroxide (3.0M) quenching system, and performing column chromatography purification to obtain light brown powder 4-imidazo [2,2] ring-like dye; under the atmosphere of nitrogen, adding 4-imidazole [2,2] cyclohexane, tetrahydrofuran and tetramethylethylenediamine into a reaction tube filled with magnetons, stirring for dissolving, cooling to-78 ℃, dropwise adding n-butyllithium into the system, reacting for 1h, dropwise adding phosphine chloride, reacting for 18 h at room temperature, adding a water quenching system, and purifying by column chromatography to obtain the corresponding imidazole ligand.
The invention also provides a preparation method of the imidazole derivative shown in the formula (II), which comprises the following specific steps:
palladium acetate and tri-tert-butylphosphine were added to a 100ml sealed tube under a nitrogen atmosphere, toluene was added, and the mixture was stirred at room temperature for 5 min. Then 1, 2-dibromobenzene, 2,4, 6-trimethylaniline, and sodium tert-butoxide were added, and the system was heated to 110 ℃ for 14 hours. After the reaction is finished, cooling to room temperature, filtering, washing with cold n-hexane and cold water to obtain green powder solid, weighing the solid in a 100ml Schlenk bottle, stirring with triethyl orthoformate at 140 ℃ for 1 hour, cooling to room temperature, adding trimethylchlorosilane to obtain white solid, filtering, washing with n-hexane to obtain a product, and obtaining the corresponding imidazole ligand.
The invention has the beneficial effects that: the invention discloses an imidazole ligand derivative shown in formula (I) and formula (II) and application thereof as an additive in the telomerization of 1,3-butadiene to generate 1-substituted-2, 7-octadiene, wherein the imidazole ligand derivative can be used for efficiently synthesizing a target product 1-substituted-2, 7-octadiene through one-step reaction, so that the substrate molecule number TON converted by unit active site is obviously improved, the chemical selectivity and the regioselectivity are improved, and the imidazole ligand derivative has practical application value and wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1: synthesis of IA
Figure BDA0002540275770000041
Under a nitrogen atmosphere, a reaction tube equipped with magnetons was charged with 4-amino [2,2] cycloform (1.12g,5.03mmol,1.0eq.), paraformaldehyde (388mg,12.81 mmol), and NH4Cl (672mg,12.58mmol), and 1,4 dioxane (20mL) and water (20mL) were added. Glyoxal (1.80mL, 12.58mmol) and 2 drops of phosphoric acid were added. Reflux was carried out for 18 hours under heating, cooled to room temperature, and then 30mL of sodium hydroxide (3.0M) was added to quench the system, extracted with ether, the organic phases were combined, concentrated to remove the solvent to give a brown powder, which was purified by column chromatography (ethyl acetate: petroleum ether ═ 1: 1) to give 4-imidazo [2,2] cyclohexane (0.87g, 63%) as a pale brown powder.
Under a nitrogen atmosphere, 4-imidazo [2,2] cycloform (0.81g,2.96mmol), THF (15mL) and TMEDA (0.47mL,3.10mmol) were added to a reaction tube containing magnetons, the mixture was dissolved with stirring, the temperature was lowered to-78 ℃, n-butyllithium (2.5m1.45ml,2.97mmol) was added dropwise to the system, after 1 hour of reaction, di-tert-butylphosphonium chloride (0.54g,3.00mmol) dissolved in 1.5mL was added dropwise, the reaction was allowed to return to room temperature for 18 hours, 30mL of water was added to quench the system, and then extraction was performed with diethyl ether, the organic phases were combined, and the column chromatography solvent was concentrated to obtain a white powder, which was purified (ethyl acetate: petroleum ether ═ 1: 1) to obtain a white solid (0.6g, 48%).
Example 2: synthesis of IB
Figure BDA0002540275770000042
Under a nitrogen atmosphere, a reaction tube equipped with magnetons was charged with 4-amino [2,2] cycloform (1.12g,5.03mmol,1.0eq.), paraformaldehyde (388mg,12.81 mmol), and NH4Cl (672mg,12.58mmol), and 1,4 dioxane (20mL) and water (20mL) were added. Glyoxal (1.80mL, 12.58mmol) and 2 drops of phosphoric acid were added. Reflux was carried out for 18 hours under heating, cooled to room temperature, and then 30mL of sodium hydroxide (3.0M) was added to quench the system, extracted with ether, the organic phases were combined, concentrated to remove the solvent to give a brown powder, which was purified by column chromatography (ethyl acetate: petroleum ether ═ 1: 1) to give 4-imidazo [2,2] cyclohexane (0.87g, 63%) as a pale brown powder.
Under nitrogen atmosphere, 4-imidazo [2,2] cycloform (0.81g,2.96mmol), THF (15mL) and TMEDA (0.47mL,3.10mmol) were added to a reaction tube containing magnetons, stirred to dissolve, the temperature was lowered to-78 ℃, n-butyllithium (2.5m1.45ml,2.97mmol) was added dropwise to the system, after 1 hour of reaction, tert-butylpyridinyl phosphine chloride (0.64g,3.00mmol) dissolved in 1.5mL was added dropwise, the reaction was allowed to return to room temperature for 18 hours, 30mL of water was added to quench the system, followed by extraction with ether, the organic phases were combined, and the solvent was concentrated to remove the white powder, and column chromatography purification (ethyl acetate: petroleum ether ═ 1: 1) was carried out to obtain a white solid (0.83g, 64%).
Example 3: synthesis of IC
Figure BDA0002540275770000051
Palladium acetate (0.264g,1.18mmol) and tri-tert-butylphosphine (0.71g,3.52mmol) were added to a 100ml sealed tube under a nitrogen atmosphere, toluene (60ml) was added, and the mixture was stirred at room temperature for 5 min. Then, 1, 2-dibromobenzene (6.9g,29.4mmol),2,4, 6-trimethylaniline (7.9g,58.6mmol), and sodium tert-butoxide (8.46g,87.9mmol) were added, and the system was heated to 110 ℃ for 14 hours. After completion of the reaction, it was cooled to room temperature, filtered, and washed with cold n-hexane and cold water to obtain a green powdery solid, and the solid (500mg,1.45mmol) and triethyl orthoformate (30mL) were weighed in a 100mL Schlenk bottle and stirred at 140 ℃ for 1 hour, after cooling to room temperature, trimethylchlorosilane (10mL) was added to obtain a white solid, and filtered and washed with n-hexane to obtain a product as a white powdery solid (412.1mg, 80%).
Example 4: synthesis of ID
Figure BDA0002540275770000052
Palladium acetate (0.264g,1.18mmol) and tri-tert-butylphosphine (0.71g,3.52mmol) were added to a 100ml sealed tube under a nitrogen atmosphere, toluene (60ml) was added, and the mixture was stirred at room temperature for 5 min. Then 1, 2-dibromobenzene (6.9g,29.4mmol),2,4, 6-trimethylaniline (7.9g,58.6mmol), and sodium tert-butoxide (8.46g,87.9mmol) were added, the stopper was screwed and the system was heated to 110 ℃ for 14 hours. After the reaction is finished, cooling to room temperature, filtering, and washing by using cold n-hexane and cold water to obtain a green powder solid.
The above solid (500mg,1.56mmol) and triethyl orthoformate (30mL) were weighed into a 100mL Schlenk bottle and stirred at 140 ℃ for 1 hour, after cooling to room temperature, trimethylchlorosilane (10mL) was added to give a white solid, which was filtered and washed with n-hexane to give a white powdery solid (464.7mg, 90%).
Example 5: IA. IB, IC and ID are applied to butadiene telomerization reaction catalyst
Figure BDA0002540275770000061
To a clean dry 100ml high pressure reactor was added sodium methoxide (40mg,0.74mmol), and the inside of the reactor was evacuated three times to replace the available air with nitrogen gas for 5 minutes each, and Pd was weighed in a 100ml Schlenk bottle2(dba)3(6.4mg,0.0070mmol), sodium methoxide (10mg,0.19mmol) and 4 different imidazole additives IA, IB, IC, ID and triphenylphosphine PPh3(0.028mmol) were added separately and stirred for about 10 min. The above solution was added to the kettle under a stream of nitrogen. The kettle was weighed and the value recorded. And (3) installing an air charging pipeline of 1,3-butadiene on the high-pressure kettle, and charging and ventilating the air in the pipeline for three times. The reaction kettle is placed in ethyl acetate frozen by liquid nitrogen, an inflation valve is opened, 1,3-butadiene is filled into the kettle, a pipeline is closed, the reaction kettle is wiped clean, and the weight of the 1,3-butadiene filled into the reaction kettle is accurately weighed (7.0g,0.13 mol). And putting the reaction kettle into an aluminum block which is preheated to 60 ℃ in advance, and reacting for 16 hours. After the reaction is finished, after the reaction kettle is cooled to room temperature, discharging the residual 1,3-butadiene, and weighing again. About 5ml of isooctane (3.8g,0.033mol) was added to the kettle and stirred with tetrahydrofuran, and the conversion, TON, was calculated by GC analysis and the results are given in table 1 below:
TABLE 1
Sequence of Additive agent Regioselectivity (1/2) Chemical selectivity% TON
1 IA 98:2 98 320000
2 IB 98:2 99 275000
3 IC 99:1 99 385000
4 ID 97:1 98 305000
5 PPh3 58：42 90 93000
As can be seen from the data in Table 1, by adding the additive of the present invention, the number of substrate molecules TON converted per active site can be as high as 380000, the chemical selectivity of compounds 1 and 2 is greater than 98%, and the regioselectivity is greater than 98% in the telomerization of 1,3-butadiene to 1-substituted-2, 7-octadiene, while the number of substrate molecules TON converted per active site is very low when triphenylphosphine is added as the additive. Therefore, the additive prepared by the embodiment of the invention can efficiently synthesize the target product 1-substituted-2, 7-octadiene, so that the substrate molecule number TON converted by unit active site is obviously improved, the chemical selectivity and the regioselectivity are improved, and the additive has practical application value and wide application prospect.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.

Claims (9)

1. The imidazole ligand derivative is characterized by having a structure shown in formulas (I) and (II):
Figure FDA0002540275760000011
wherein the content of the first and second substances,
R1、R2is alkyl, pyridyl, alkyl substituted phenyl;
R3is phenyl and alkyl substituted by alkyl.
2. The imidazole ligand derivative of claim 1, wherein R is1、R2Is C1-C6 alkyl, pyridyl, C1-C6 alkyl substituted phenyl; r3Is phenyl substituted by C1-C6 alkyl, C1-C6 alkyl.
3. The imidazole ligand derivative of claim 2, wherein R is1、R2Is tert-butyl, or R1Is pyridyl, R2Is tert-butyl; r3Is 4-methoxy-substituted phenyl, or R3Is phenyl substituted by 1,3, 5-trimethyl.
4. Use of imidazole ligand derivatives according to any one of claims 1 to 3 as additives in the telomerization of 1,3-butadiene to 1-substituted-2, 7-octadiene or 3-substituted-1, 7-octadiene.
5. The use according to claim 4, wherein the step of telomerizing 1,3-butadiene is specifically: in the presence of a catalyst and an additive, 1,3-butadiene and a primary aliphatic alcohol compound ROH or a corresponding salt thereof are subjected to telomerization to generate 1-substituted-2, 7-octadiene shown in a formula 1 or 3-substituted-1, 7-octadiene shown in a formula 2, and the reaction process is shown in a formula (III):
Figure FDA0002540275760000012
wherein R is C1-C20 hydrocarbyl.
6. Use according to claim 5, wherein the catalyst is a palladium catalyst comprising one or more of palladium acetylacetonate, palladium formate, palladium acetate, palladium propionate, palladium octanoate, palladium carbonate.
7. The use according to claim 5, wherein the temperature of the reaction is between 60 ℃ and 100 ℃.
8. The use according to claim 5, wherein the reaction time is 5 to 16 hours.
9. The use according to claim 5, wherein the molar ratio of 1,3-butadiene, primary aliphatic alcohol compound or primary alcohol sodium salt is 2: 1.
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