CN114622226B - Method for electrocatalytic synthesis of alkyl borate - Google Patents

Method for electrocatalytic synthesis of alkyl borate Download PDF

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CN114622226B
CN114622226B CN202011463932.1A CN202011463932A CN114622226B CN 114622226 B CN114622226 B CN 114622226B CN 202011463932 A CN202011463932 A CN 202011463932A CN 114622226 B CN114622226 B CN 114622226B
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CN114622226A (en
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卿光焱
张亚会
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Dalian Institute of Chemical Physics of CAS
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B3/00—Electrolytic production of organic compounds
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    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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Abstract

The invention relates to a method for preparing an alkyl borate compound based on electrocatalysis, and belongs to the field of compound preparation. The method takes aryl alkene compound and pinacol borane as raw materials, and under the action of rated current, the raw materials react in the presence of electrolyte and N, N-diisopropylethylamine to selectively obtain two alkyl boric acid esters shown in structural formulas I and II respectively. The invention takes low-cost and easily available electricity as energy for the first time, and provides a new scheme for preparing alkyl borate by using acetonitrile solvent under the assistance of N, N-diisopropylethylamine by utilizing the characteristics that acetonitrile solvent can be electrolyzed with high efficiency and hydrogen protons are released.

Description

Method for electrocatalytic synthesis of alkyl borate
Technical Field
The invention belongs to the field of compound preparation, and particularly relates to a method for electrocatalytic synthesis of alkyl borate.
Background
Alkyl borate is an indispensable important intermediate, and has been widely applied to the fields of organic synthesis, drug development, high polymer materials and the like due to low toxicity and stability. At present, there are many methods for efficiently converting C-B bonds into various functional groups, such as C-C bonds, C-N bonds, C-O bonds, C-F bonds, and particularly for efficiently utilizing the C (sp 3 ) Organoboron species and aryl or haloalkyl groups to build new c—c bonds. In view of the irreplaceable role that alkyl borates play in various fields, it is important to develop a more efficient, simple, economical and green preparation process.
At present, a representative preparation method of alkyl borate is transition metal catalyzed alkene hydroboration, namely, addition of B-H bond in pi system of unsaturated double bond. Since Wilkinson's catalyst (Ph) 3 P) 3 After the successful development of RhCl, various noble metal (ruthenium, rhodium, iridium) and non-noble metal catalysts (iron, cobalt, nickel) have also been developed successively. While these transition metal catalysts exhibit high chemo-, regio-and stereoselectivity in some cases, such reactions often require relatively harsh reaction conditions and expensive, difficult-to-synthesize organic ligands, and even in some reactions require the synthesis of metal complexes of a single configuration. In particular, in the large scale preparation of alkyl borates, the preparation, storage, removal or recovery of metal catalysts is facing significant challenges.
Disclosure of Invention
The invention aims to provide a method for synthesizing alkyl borate by using electricity as an energy source, which is a simple, efficient, economic and green preparation method for synthesizing alkyl borate with rich functional groups by using aryl alkene compound as a raw material and pinacol borane as a boration reagent in the presence of electrolyte and additives. By utilizing the property that a solvent can be electrolyzed efficiently and release hydrogen protons under the action of N, N-diisopropylethylamine, a novel method for synthesizing alkyl borate efficiently by utilizing aryl alkene compounds and pinacol borane is provided.
The invention solves the technical problems by adopting the following technical scheme:
an electrocatalytic synthesis method of alkyl borate, which takes aryl alkene compound as raw material and pinacol borane as boration reagent in the presence of electrolyte and additive, and electrocatalytic synthesis method of alkyl borate compound
The alkyl borate compound has the following structural formula:
wherein R is 1 Ar, R taken from C10 or less 2 An alkyl group of H, C or less or an aryl group of 10 or less;
R 3 alkyl groups taken from H or C8 or less;
the Ar is a compound with a general formula IV or V,
wherein R is 4 An alkyl group of H, C or less, an alkoxy group of 5 or less, a halogen group, a trifluoromethyl group, a cyano group, an amino group of 10 or less, an aryl group, an ester group, an aryloxy group, an alkylthio group, or an arylthio group; n is taken from an integer between 0 and 5.
The invention provides a method conforming to the green chemistry principle, which is to select proper electrode and set rated current in a solvent containing electrolyte, take a compound with a general formula III and pinacol borane as substrates, synthesize the compounds with the general formulas I and II under the auxiliary action of additives according to the following reaction formula,
a method for electrocatalytic synthesis of alkyl borate, comprising an electrode, rated current, electrolyte, solvent, reaction temperature, reaction time, aryl alkene compound, pinacol borane and additive;
the catalytic system is required to be carried out in an anhydrous and anaerobic environment;
in the technical route, the electrode comprises a combined electrode of 1 or 2 of nickel sheets, copper sheets, iron sheets, gold sheets, zinc sheets, platinum sheets, carbon rods and carbon cloth.
In the above technical route, the rated current is set to a value of 1mA to 100mA, and more preferably 8mA to 25mA.
In the above technical route, the electrolyte comprises the selection and the dosage of the electrolyte. The electrolyte comprises 1 of tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, lithium perchlorate, tetrabutylammonium iodide and acetic acid; the electrolyte is used in an amount of 0.1 to 5 times, more preferably 0.1 to 1.0 times the amount of the aryl alkene compound substance.
In the above technical route, the solvent comprises 1 or 2 of tetrahydrofuran, acetonitrile, acetone, dichloromethane, chloroform, pyridine, N-dimethylformamide, dimethyl sulfoxide, 1, 4-epoxyhexaane, methanol, ethanol, diethyl ether, N-hexane, tert-butanol, isopropanol, toluene and methyl tert-butyl ether. Wherein the volume ratio of the composition of 2 solvents is 1:9 to 9:1, preferably 7:3 to 9:1.
In the technical route, the reaction temperature comprises 0 ℃ to solvent reflux temperature, and the temperature is 0 ℃ to 85 ℃.
In the above technical route, the reaction time includes 0 to 12 hours.
In the above technical scheme, the aryl alkene compound has a compound of formula II.
In the compound with the general formula II, R 1 Ar is selected from C10 or less, ar is selected from compounds of formula III or IV, R 4 An alkyl group of H, C or less, an alkoxy group of 5 or less, a halogen group, a trifluoromethyl group, a cyano group, an amino group of 10 or less, an aryl group, an ester group, an aryloxy group, an alkylthio group, or an arylthio group; n is taken from an integer between 0 and 5.
R 2 From an alkyl group of H, C or less and an aryl group of 10 or less,
R 3 alkyl groups from H, C or less.
In the above technical route, the amount of the pinacolborane is 1 to 20 times the amount of the aryl alkene compound substance in terms of the amount of the substance.
In the above technical route, the additive comprises additive selection and dosage. The additive is 1 of triethylamine, pyridine and N, N-diisopropylethylamine; the additive is used in an amount of 0.1 to 1.1 times the amount of the aryl alkene compound material based on the amount of the material.
The term "alkyl" as used herein includes both straight chain alkyl and branched alkyl groups, and similar descriptions apply to other groups used in this description.
The term "halogen" as used herein includes fluorine, chlorine, bromine, iodine.
The specific structures of the substituents of the respective raw material compounds in the above reaction formulas are listed in table 1.
TABLE 1 specific Structure of substituent of each raw material Compound in the above reaction formula
The invention has the advantages that:
the invention uses sustainable electricity as energy, does not need an additional oxidant or reducer, and can realize the hydroboration reaction of olefin with high selectivity by taking pinacol borane as a substrate through the characteristic that acetonitrile is electrolyzed under the action of DIIEA to release hydrogen protons (examples 1-20). Meanwhile, the products after diborane addition (examples 21 to 27) can be selectively synthesized by adjusting the amount of pinacolborane. In addition, gram-scale amplification experiments of various substrates are completed, and finally, target products are obtained in high yields, so that the method has reference significance in scientific research and industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The protection scope of the present invention is not limited thereto, and any person skilled in the art who is familiar with the technology disclosed in the present invention shall cover the protection scope of the present invention by making equivalents or alternatives to the technical scheme and the inventive concept of the present invention.
Example 1 2-Phenylethyl-1-boronic acid pinacol ester (Compound 1)
To an argon-shielded three-necked flask equipped with two platinum sheets, 114. Mu.L (1.0 mmol) of styrene, 160. Mu.L (1.1 mmol) of HBpin, 132. Mu.L (0.8 mmol) of DIEA were successively added at room temperature, n Bu 4 NBF 4 65.8 mg (0.2 mmol), anhydrous CH 3 CN 8mL and anhydrous THF 2mL. The reaction mixture was then reacted at 15mA for 3 hours. The solvent is removed by a rotary evaporator after the post-treatment, the target compound is obtained by column chromatography, the filling material is silica gel, and the eluent is petroleum ether: ethyl acetate (100:1-20:1), separationThe yield thereof was found to be 70%.
Example 2 2- (4-fluorophenyl) ethyl-1-boronic acid pinacol ester (Compound 2)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 4-fluorostyrene in an equimolar amount, to obtain a target compound in a yield of 69%.
Example 3 2- (3-fluorophenyl) ethyl-1-boronic acid pinacol ester (Compound 3)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 3-fluorostyrene in an equimolar amount, to obtain a target compound isolation yield of 61%.
Example 4 2- (2-fluorophenyl) ethyl-1-boronic acid pinacol ester (Compound 4)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 2-fluorostyrene in an equimolar amount, to obtain a target compound isolation yield of 66%.
Example 5 2- (4-tert-butylphenyl) ethyl-1-boronic acid pinacol ester (Compound 5)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 4-t-butylstyrene in an equimolar amount, to obtain a yield of the objective compound isolated by 74%.
Example 6 2- (4-methoxyphenyl) ethyl-1-boronic acid pinacol ester (Compound 6)
The same procedures as in example 1 were repeated except for changing styrene in example 1 to 4-methoxystyrene in an equimolar amount, whereby the isolated yield of the target compound was 69%.
Example 7 2- (4-methylphenyl) ethyl-1-boronic acid pinacol ester (Compound 7)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 4-methylstyrene in an equimolar amount to obtain 77% of the isolated yield of the target compound.
Example 8 2-pinacol borate-1-phenyl-n-propane (Compound 8)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to an equimolar amount of beta-methylstyrene to obtain 71% of the isolated yield of the target compound.
Example 9 2 pinacol borate-1-phenylisobutane (Compound 9)
The same procedures as in example 1 were repeated except for changing styrene in example 1 to 2-methyl-1-phenylpropene in equimolar amounts to obtain a target compound isolation yield of 57%.
Example 10 2- (2, 5-dimethylphenyl) ethyl-1-boronic acid pinacol ester (Compound 10)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 2, 5-dimethylstyrene in an equimolar amount, to obtain a target compound isolation yield of 70%.
Example 11 2- (2, 4, 6-trimethylphenyl) ethyl-1-boronic acid pinacol ester (Compound 11)
The procedure of example 1 was repeated except that styrene in example 1 was changed to 2,4, 6-trimethylstyrene in an equimolar amount, to obtain a target compound isolation yield of 67%.
Example 12 2- (4-ethoxyphenyl) ethyl-1-boronic acid pinacol ester (Compound 12)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to an equimolar amount of 4-ethoxystyrene to obtain a target compound isolation yield of 61%.
Example 13 2- (4-Biphenyl) ethyl-1-boronic acid pinacol ester (Compound 13)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 4-biphenylethylene in an equimolar amount, to obtain a target compound isolation yield of 57%.
EXAMPLE 14 pinacol ester of 1-boronic acid-2-phenylphenylethane (Compound 14)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to trans-1, 2-stilbene in an equimolar amount, to obtain a target compound isolation yield of 65%.
Example 15 2-indanyl boronic acid pinacol ester (Compound 15)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to indene in an equimolar amount, to obtain a target compound in a separation yield of 65%.
EXAMPLE 16 pinacol 2- (1, 2,3, 4-tetrahydronaphthyl) borate (Compound 16)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 1, 2-dihydronaphthalene in an equimolar amount, to obtain a target compound isolation yield of 64%.
Example 17 2- (1, 2-Dihydroacenaphthene) -1-boronic acid pinacol ester (Compound 17)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to acenaphthylene in an equimolar amount, to obtain an isolated yield of the objective compound of 84%.
Example 18 2- (2-naphthyl) ethyl-1-boronic acid pinacol ester (Compound 18)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 2-vinylnaphthalene in an equimolar amount to obtain a target compound isolation yield of 43%.
Example 19 2- (1-naphthyl) ethyl-1-boronic acid pinacol ester (Compound 19)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 1-vinylnaphthalene in an equimolar amount, to obtain a target compound isolation yield of 42%.
Example 20 2-methyl-2- (2-naphthyl) ethyl-1-boronic acid pinacol ester (Compound 14)
The same procedures as in example 1 were repeated except that styrene in example 1 was changed to 2-isopropenylnaphthalene in an equimolar amount, whereby the isolated yield of the target compound was 40%.
Example 21 2- (2-naphthyl) ethyl-1, 2-diboronic acid pinacol ester (Compound 21)
To an argon-shielded three-necked flask equipped with two platinum sheets were successively charged 154mg (1.0 mmol) of 2-vinylnaphthalene, 640. Mu.L (4.4 mmol) of HBpin, 132. Mu.L (0.8 mmol) of DIEA, at room temperature, n Bu 4 NBF 4 65.8 mg (0.2 mmol), anhydrous CH 3 CN 8mL and anhydrous THF 2mL. The reaction mixture was then reacted at 20mA for 4 hours. Post-treatment is removed by rotary evaporatorRemoving solvent, obtaining target compound by column chromatography, wherein the filler is silica gel, and the eluent is petroleum ether: ethyl acetate (100:1-20:1), isolated in 71% yield.
Example 22 2- (1-naphthyl) ethyl-1, 2-diboronic acid pinacol ester (Compound 22)
The isolation yield of the target compound was 84% by the same manner as in example 21, except that 2-vinylnaphthalene in example 21 was changed to 1-vinylnaphthalene in an equimolar amount.
Example 23 2-methyl-2- (2-naphthyl) ethyl-1, 2-diboronic acid pinacol ester (Compound 23)
The separation yield of the target compound was 88% by the same procedure as in example 21, except that 2-vinylnaphthalene in example 21 was changed to 2-isopropenylnaphthalene in an equimolar amount.
EXAMPLE 24 1, 2-Diboronic acid pinacol ester-2-phenylphenylethane (Compound 24)
To an argon-shielded three-necked flask equipped with two platinum sheets were successively charged 114. Mu.L (1.0 mmol), 1280. Mu.L (8.8 mmol) of HBpin, 132. Mu.L (0.8 mmol) of DIEA, and, n Bu 4 NBF 4 65.8 mg (0.2 mmol), anhydrous CH 3 CN 8mL and anhydrous THF 2mL. The reaction mixture was then reacted at 20mA for 4 hours. The solvent is removed by a rotary evaporator after the post-treatment, the target compound is obtained by column chromatography, the filling material is silica gel, and the eluent is petroleum ether: ethyl acetate (100:1-20:1), isolated in 41% yield.
EXAMPLE 25 pinacol ester of 1, 2-Diboronate-2- (4-fluorophenyl) phenylethane (Compound 25)
The same procedures as in example 24 were repeated except for changing styrene in example 24 to 4-fluorostyrene in an equimolar amount, whereby a target compound isolation yield of 43% was obtained.
EXAMPLE 26 pinacol ester of 1, 2-Diboronate-2- (4-methoxyphenyl) phenylethane (Compound 26)
The same procedures as in example 24 were repeated except for changing styrene in example 24 to 4-methoxystyrene in an equimolar amount, to obtain 38% of the isolated yield of the target compound.
EXAMPLE 27 pinacol ester of 1, 2-Diboronate-2- (4-methylphenyl) phenylethane (Compound 27)
The isolation yield of the objective compound was 20% by the same manner as in example 24, except that styrene in example 24 was changed to an equimolar amount of 4-methylstyrene.
The specific structure, physical properties and nuclear magnetic data of the compounds prepared in examples 1 to 27 above are shown in Table 2 below.
TABLE 2 specific Structure, physical Properties and Nuclear magnetic data of the Compounds prepared in examples 1-27
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Claims (6)

1. A method for electrocatalytic synthesis of alkyl borate is characterized in that: in the presence of electrolyte and additive, using aryl alkene compound as raw material, using pinacol borane as boration reagent, and selectively electrocatalytic synthesizing alkyl borate compound by adjusting the amount of pinacol borane; the synthetic route is as follows:
wherein R is 1 A compound of the general formula IV or V,
R 2 an alkyl group of H, C or less or an aryl group of 10 or less;
R 3 alkyl groups taken from H or C8 or less;
wherein R is 4 An alkyl group of H, C or less, an alkoxy group of 5 or less, a halogen group, a trifluoromethyl group, a cyano group, an amino group of 10 or less, an aryl group, an ester group, an aryloxy group, an alkylthio group, or an arylthio group; n is an integer from 0 to 5;
the catalytic system is required to be carried out in an anhydrous and anaerobic environment; the electrocatalytic electrode is a platinum sheet; the solvent is tetrahydrofuran and acetonitrile; the additive is N, N-diisopropylethylamine.
2. The method for electrocatalytic synthesis of alkylborate as claimed in claim 1, wherein the rated current is set to a magnitude of 1mA to 100mA.
3. The method for electrocatalytic synthesis of alkyl borate according to claim 1, wherein the electrolyte in the electrocatalytic reaction is 1 of tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, lithium perchlorate, tetrabutylammonium iodide and acetic acid; the electrolyte is used in an amount of 0.1 to 5 times the amount of the olefin compound substance.
4. The method for electrocatalytic synthesis of alkyl borates according to claim 1, wherein the reaction temperature is 0-85 ℃; the reaction time is 3-12h.
5. The method for electrocatalytic synthesis of alkylborate as claimed in claim 1, wherein the amount of pinacol borane added is 1-20 times the amount of aryl alkene compound based on the amount of the substance.
6. The method for electrocatalytic synthesis of alkylborate as claimed in claim 1, wherein the additive is used in an amount of 0.1 to 1.1 times the amount of aryl alkene compound based on the amount of the substance.
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