CN109503641B - Method for preparing borate ester based on anilino lithium compound - Google Patents
Method for preparing borate ester based on anilino lithium compound Download PDFInfo
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- CN109503641B CN109503641B CN201811555578.8A CN201811555578A CN109503641B CN 109503641 B CN109503641 B CN 109503641B CN 201811555578 A CN201811555578 A CN 201811555578A CN 109503641 B CN109503641 B CN 109503641B
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Abstract
The invention discloses a method for preparing borate ester based on an anilino lithium compound. And stirring and mixing the catalyst, the borane and the aromatic carboxylic acid uniformly in sequence, reacting for 35-45 minutes, exposing the mixture to air to terminate the reaction, and decompressing the reaction liquid to remove the solvent to obtain the borate with different substituents. The anilino lithium compound disclosed by the invention can catalyze the hydroboration reaction of carboxylic acid and borane with high activity at room temperature, the dosage of the catalyst is only 0.8mol% of the molar weight of the carboxylic acid, compared with the existing catalytic system, the anilino lithium compound which is a commercial reagent is utilized, the reaction condition is mild, and the yield of borate ester of different substituent groups under the limited condition can reach 99%.
Description
Technical Field
The invention relates to application of a commercial reagent anilino lithium compound, in particular to a method for preparing boric acid ester based on the anilino lithium compound.
Background
The organoborates may be regarded as orthoboric acid B (OH)3Wherein hydrogen is substituted by an organic group, and a metaborate (ROBO)3. Boric acid esters are widely used in various fields due to their stability and low toxicity, and are a main raw material for synthesizing boron-containing compounds. The borate compound can be used as an antirust agent, an antiseptic, a polymer additive, an antiwear additive, automobile brake fluid, a gasoline additive and a flame retardant in a cleaning agent, and can also be used as a lubricating oil additive and the like.
The existing hydroboration methods all have obvious disadvantages: LiAlH4And NaBH4The system has great risk of safety, Smi2-H2O-Et3The N system needs a lot of excessive reagents, the transition metal complex system needs to be carried out at high temperature and high pressure, and on one hand, a catalyst which is difficult to synthesize is utilized, so that the cost is high; on the other hand, 60 is required for the catalytic reactionoC reaction temperature and 24 hours reaction time. The aromatic carboxylic acid is generally a solid and the reaction of the aromatic carboxylic acid with the pinacol borane is a heterogeneous reaction.
Disclosure of Invention
The invention aims to provide a method for preparing boric acid ester by aromatic carboxylic acid hydroboration reaction, namely, an anilino lithium compound is used as a high-efficiency catalyst to catalyze carboxylic acid and borane to perform hydroboration reaction.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the method for preparing the borate ester based on the anilino lithium compound comprises the following steps of mixing borane and aromatic carboxylic acid under an inert gas atmosphere, adding a catalyst anilino lithium compound, and carrying out a hydroboration reaction to obtain the borate ester.
The application of anilino lithium compound in catalyzing the hydroboration reaction of aromatic carboxylic acid and borane.
In the invention, the anilino lithium compound is a commercial anilino lithium reagent and comprises anilino lithium, p-methylanilino lithium, o-methylanilino lithium, 2-methoxyanilino lithium, 4-methoxyanilino lithium, 2, 6-dimethylanilino lithium and 2, 6-diisopropylanilino lithium.
In the technical scheme, the borane is pinacol borane; the aromatic carboxylic acid is benzoic acid, 4-bromobenzoic acid, 4-fluorobenzoic acid, 1-naphthoic acid, 2-methoxybenzoic acid, o-carboxyphenylacetic acid, 3-indoleacetic acid, 2-phenylbutyric acid, 2-methyl-5-bromo-benzoic acid, 4-tert-butylbenzoic acid, 2-bromobenzoic acid, 4-iodobenzoic acid, 3-phenylpropionic acid, diphenylacetic acid and the like.
In the technical scheme, the molar ratio of the aromatic carboxylic acid to the borane is 1: 3-1: 7.
In the technical scheme, the temperature of the hydroboration reaction is room temperature, and the time is 70-80 minutes.
In the technical scheme, the dosage of the anilino lithium is 0.7-0.9% of the molar weight of the aromatic carboxylic acid.
The hydroboration reaction disclosed by the invention comprises the following specific steps:
under the inert gas atmosphere, mixing borane and aromatic carboxylic acid, adding a catalyst anilino lithium compound, and then carrying out hydroboration reaction; after the reaction is finished, contacting air to stop the reaction, and decompressing the reaction liquid to remove the solvent to obtain the different substituted boric acid esters. An inert gas atmosphere can be achieved in a glove box, which is a conventional technique.
In the invention, all raw materials are subjected to anhydrous and anaerobic treatment.
The above technical solution can be expressed as follows:
due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention discovers for the first time that the commercialized anilino lithium compound can efficiently catalyze the hydroboration reaction of aromatic carboxylic acid and borane, and is highly in line with the atom economic synthesis.
2. The lithium anilino-complex disclosed by the invention has the advantages of high catalytic activity (0.8% of the mole number of the catalyst), mild reaction conditions (room temperature), short reaction time, high reaction yield, simple and controllable reaction and simple post-treatment, and aromatic carboxylic acid and borane are subjected to hydroboration reaction under the catalysis of the lithium anilino-complex.
The anilino lithium compound disclosed by the invention has a wide application range on a substrate in catalyzing hydroboration of aromatic carboxylic acid, is suitable for carboxylic acids with different substituent positions and different electronic effects, and provides more choices for industrial synthesis of boric acid ester; and the reaction process is simple and controllable, the yield is high, the product is easy to post-treat, and the method is suitable for industrial production.
Detailed Description
The invention is further described below with reference to the following examples:
example I lithium anilino catalyzes the hydroboration reaction of benzoic acid with pinacol borane
Benzoic acid (61.1 mg, 0.5 mmol) was added to a reaction flask after dehydration and deoxidation treatment under an inert gas atmosphere, pinacolborane (218. mu.L, 1.5 mmol) was added by a pipette, and finally 40. mu.L of anilino lithium in tetrahydrofuran (0.1M) (0.8mol% amount, the same applies hereinafter) was added thereto, reaction was carried out at room temperature for 75 minutes, and the reaction solution was brought into contact with airTerminating the reaction with gas, removing the solvent under reduced pressure to obtain the product boric acid ester, taking sym-trimethoxybenzene (84.15 mg, 0.5 mmol) as an internal standard and using CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield is 99%; if the anilino lithium is replaced by a triaryloxy rare earth catalyst Nd (OAr)3(THF)2No product is obtained. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) ： 7.20– 7.30 (m, 5H, ArH)，4.91 (s, 2H, CH2), 1.24 (s, 36H, CH3)。
the using amount of pinacol borane is 285 mu L, and when the using amount of pinacol borane is 2 mmol, the product yield is 99%; the dosage of pinacolborane is 361.2 mu L, and the product yield is 99 percent when the dosage is 2.5 mmol.
The reaction was carried out at room temperature for 80 minutes at a yield of 99%.
Comparative example: 2, 4-di (2, 6-diisopropylanilino) -2-pentenyl lithium catalyzed hydroboration reaction of benzoic acid and pinacol borane
Adding benzoic acid (60.5 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (238 mu L, 1.65 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution (0.1M) of 2, 4-bis (2, 6-diisopropylanilino) -2-pentenyl lithium (0.8mol% using amount), reacting at room temperature for 75 minutes, contacting the reaction liquid with air to terminate the reaction, removing the solvent under reduced pressure to obtain a product boric acid ester, taking trimethoxybenzene (83.32 mg, 0.5 mmol) as an internal standard, and using CDCl3Dissolving, stirring for 10 min, sampling, and performing nuclear magnetic assay. Is calculated by1The H yield was 14%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) ： 7.20– 7.30 (m, 5H, ArH)，4.91 (s, 2H, CH2), 1.24 (s, 36H, CH3)。
the chemical structural formula of the 2, 4-di (2, 6-diisopropylanilino) -2-pentenyl lithium is as follows:
EXAMPLE II lithium anilino catalysis of the hydroboration reaction of 4-fluorobenzoic acid with pinacol borane
Adding 4-fluorobenzoic acid (70.8 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (290 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol% of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, removing the solvent under reduced pressure to obtain a product boric acid ester, taking trimethoxy benzene (84.99 mg, 0.5 mmol) as an internal standard, and using CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 91%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.20– 7.30 (m, 5H, ArH)，4.91 (s, 2H, CH2), 1.24 (s, 36H, CH3)。
EXAMPLE III lithium o-methylbenzamido catalyzed hydroboration of 4-bromobenzoic acid with pinacol borane
Adding 4-bromobenzoic acid (100 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (289 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of o-methylanilino lithium (0.8mol percent of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the product boric acid ester uses sym-trimethoxybenzene (83.67 mg, 0.5 mmol) as an internal standard and CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 93%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.39 (br s, 2H, ArCH), 7.16 (t, 2H, ArCH), 4.80 (s, 2H, OCH2), 1.19 (s, 36H, CH3)。
EXAMPLE IV lithium anilino catalyzed hydroboration of 2-methoxybenzoic acid with pinacol borane
Adding 2-methoxybenzoic acid (76.2 mg, 0.5 mmol) into a reaction flask subjected to dehydration and deoxidation treatment under inert gas atmosphere, adding pinacolborane (290 μ L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol% of the amount), reacting for 75 minutes at room temperature, contacting the reaction solution with air to terminate the reaction, and removing the dissolved solution under reduced pressureReagent to obtain the product boric acid ester, internal standard sym-trimethoxybenzene (84.23 mg, 0.5 mmol) and CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product 1H NMR (400 MHz, CDCl)3)： 7.40 (d, 1H, ArCH), 7.21 (t, 1H, ArCH), 6.94 (t, 1H, ArCH), 6.82 (d, 1H, ArCH), 4.96 (s,2H,OCH2), 1.25 (s,36H,CH3)。
EXAMPLE V lithium anilino catalyzed hydroboration of 1-naphthoic acid with pinacol borane
Adding 1-naphthoic acid (85.4 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (289 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol% of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the internal standard of sym-trimethoxybenzene (83.42 mg, 0.5 mmol) is used as an internal standard, and CDCl is used3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 93%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 8.01 (d, 1H, ArCH), 7.78-7.80 (m, 2H, ArCH), 7.73(d, 1H, ArCH), 7.36-7.46 (m, 3H, ArCH), 5.35 (s, 2H, OCH2 ), 1.21 (s, 36H, CH3)。
EXAMPLE sixthly, lithium 2-methoxyanilino catalyzes the hydroboration reaction of 4-tert-butylbenzoic acid with pinacol borane
Adding 4-tert-butylbenzoic acid (88.9 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (290 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of 2-methoxyanilino lithium (0.8mol% in amount), reacting for 80 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the product boric acid ester uses sym-trimethoxybenzene (83.89 mg, 0.5 mmol) as an internal standard and CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.25 ( d, 2H, ArCH), 7.16 (d, 2H, ArCH) , 4.79 (s, 2H, OCH2 ), 1.20 (s, 9H, CH3, tBu), 1.15 (s, 36H, CH3)。
EXAMPLE seventhly, lithium anilino catalyzed hydroboration of 2-bromobenzoic acid with pinacol borane
Adding 2-bromobenzoic acid (100.6 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (290 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol percent of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the internal standard of sym-trimethoxybenzene (84.17 mg, 0.5 mmol) is CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.39 (d, 2H, ArCH), 7.17-7.20 (m, 1H, ArCH), 7.01 (t, 1H, ArCH), 4.88 (s, 2H, OCH2), 1.17 (s, 36H, CH3)。
EXAMPLE octakis 4-methoxyanilino lithium catalyzed hydroboration of 4-iodobenzoic acid with pinacol borane
Adding 4-iodobenzoic acid (124.0 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (290 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of 4-methoxyanilino lithium (0.8mol percent of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the boric acid ester uses symtrimethoxybenzene (84.09 mg, 0.5 mmol) as an internal standard and CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.55 (d, 2H, ArCH), 7.01 (d, 2H, ArCH), 4.76 (s, 2H, OCH2), 1.16 (s, 36H, CH3)。
EXAMPLE nine lithium anilino catalyzes the hydroboration reaction of 3-phenylpropionic acid with pinacol borane
In the inert gas atmosphere, the reaction bottle is dehydrated and deoxidizedAdding 3-phenylpropionic acid (74.9 mg, 0.5 mmol), adding pinacolborane (289 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol percent of the dosage), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product of boric acid ester, wherein the internal standard of sym-trimethoxybenzene (83.89 mg, 0.5 mmol) is used, and CDCl is used3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.16 (t, 2H, ,ArCH), 7.03- 7.08 (m, 3H, ArCH), 3.78 (t, 2H, CH2, OCH2), 2.60 (t, 2H, CH2), 1.74-1.81 (m, 2H, CH2), 1.15 (s, 36H, CH3)。
EXAMPLE ten lithium anilino catalyzed hydroboration of Diphenylacetic acid with pinacol borane
Under inert gas atmosphere, adding diphenylacetic acid (105.8 mg, 0.5 mmol) into a reaction bottle after dehydration and deoxidation treatment, adding pinacolborane (289 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol percent of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester which uses sym-trimethoxybenzene (83.84 mg, 0.5 mmol) as an internal standard and CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.12-7.31 (m, 10H, ArCH), 4.40 (d, 2H, CH2, OCH2), 4.23 (t, 1H, CH), 1.22 (s,24H, CH3, pinBOBpin), 1.11 (s, 12H, CH3, OBpin)。
EXAMPLE eleventh lithium anilino catalyzed hydroboration of 2-methyl-5-bromo-benzoic acid with pinacol borane
Adding 2-methyl-5-bromo-benzoic acid (107.1 mg, 0.5 mmol) into a reaction flask subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (289. mu.L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol% of the amount), reacting at room temperature for 75 minutes, and connecting the reaction solution to a reaction vesselThe reaction was terminated by air-exposure and the solvent was removed under reduced pressure to give the product boronic ester, internal standard sym-trimethoxybenzene (83.77 mg, 0.5 mmol) and CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 6.91 (d, 1H, ArCH), 7.20 (d, 1H, ArCH), 7.48 (s, 1H, ArCH), 4.78 (s, 2H, OCH2), 2.13 (s, 3H, CH3), 1.18 (s, 36H, CH3)。
EXAMPLE twelve lithium anilino catalysts for hydroboration of 2-phenylbutyric acid with pinacol borane
Adding 2-phenylbutyric acid (82.2 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (290 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol% of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the internal standard is sym-trimethoxybenzene (84.20 mg, 0.5 mmol), and CDCl is used3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.14-7.18 (m, 2H, ArCH), 7.07-7.10 (m, 3H, ArCH), 3.82-3.92 (m, 2H, CH2, OCH2), 2.56-2.65 (m, 1H, CH), 1.70-1.80 (m, 1H, CH2), 1.45-1.54 (m, 1H, CH2), 1.15 (s, 36H, CH3, OBpin & pinBOBpin), 0.73 (t, 3H, CH3)。
EXAMPLE thirteen lithium anilino catalysis of the hydroboration reaction of 3-indoleacetic acid with pinacol borane
Adding 3-indoleacetic acid (88.0 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (363 mu L, 2.5 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol% dosage), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the internal standard of sym-trimethoxybenzene (84.49 mg, 0.5 mmol) is CDCl3The mixture is dissolved and then is added with water,stirring for 10 min, sampling and preparing nuclear magnetism. Is calculated by1The H yield was 96%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.81 (d, 1H, ArCH), 7.44(d, 1H, ArCH), 7.01-7.13 (m, 3H, ArCH), 4.05 (t, 2H, OCH2), 2.89 (t, 2H, CH2), 1.28 (s, 12H, CH3, N-Bpin ) 1.13 (s, 24H, CH3, pinBOBpin), 1.05 (s, 12H, CH3, OBpin)。
example fourteen lithium anilino catalysis of the hydroboration reaction of o-carboxyphenylacetic acid with pinacol borane
Adding o-carboxyphenylacetic acid (90.0 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (508 mu L, 3.5 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of anilino lithium (0.8mol% dosage), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the internal standard is sym-trimethoxybenzene (84.02 mg, 0.5 mmol), and CDCl is used as the internal standard3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.32 (br s, 1H, ArCH), 7.10 (br s, 3H, ArCH), 4.89 (s, 2H, CH2)，3.95 (t, 2H, CH2), 2.85 (t, 2H, CH2), 1.16 (s, 72H, CH3, OBpin & pinBOBpin)。
example fifteen lithium p-methylanilino catalysis of the hydroboration reaction of benzoic acid with pinacol borane
Adding benzoic acid (61.1 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (218 mu L, 1.5 mmol) by using a liquid transfer gun, finally adding 40 microliter of a tetrahydrofuran solution (0.1M) (0.8mol% using amount) of p-methylanilino lithium, reacting for 70 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the boric acid ester uses sym-trimethoxybenzene (84.15 mg, 0.5 mmol) as an internal standard and CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) ： 7.23– 7.33(m, 5H, ArH)，4.93 (s, 2H, CH2), 1.27 (s, 36H, CH3)。
EXAMPLE sixteen lithium 2, 6-dimethylanilino catalysis of the hydroboration reaction of 3-indoleacetic acid with pinacol borane
Adding 3-indoleacetic acid (88.0 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (363 mu L, 2.5 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of 2, 6-dimethylanilinium (0.8mol percent of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the boric acid ester uses sym-trimethoxybenzene (84.49 mg, 0.5 mmol) as an internal standard and CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 96%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.86 (d, 1H, ArCH), 7.49 (d, 1H, ArCH), 7.06-7.18 (m, 3H, ArCH), 4.10 (t, 2H, OCH2), 2.94 (t, 2H, CH2), 1.33 (s, 12H, CH3, N-Bpin ) 1.18 (s, 24H, CH3, pinBOBpin), 1.10 (s, 12H, CH3, OBpin)。
EXAMPLE seventeen-2, 6-diisopropylanilinium lithium catalyses the hydroboration reaction of 2-phenylbutyric acid with pinacol borane
Adding 2-phenylbutyric acid (82.2 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (290 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of 2, 6-diisopropylanilino lithium (0.8mol% of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the boric acid ester uses symtrimethoxybenzene (84.20 mg, 0.5 mmol) as an internal standard and CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.20-7.24 (m, 2H, ArCH), 7.13-7.15 (m, 3H, ArCH), 3.88-3.98 (m, 2H, CH2, OCH2), 2.62-2.71 (m, 1H, CH), 1.75-1.84 (m, 1H, CH2), 1.51-1.60 (m, 1H, CH2), 1.21 (s, 36H, CH3, OBpin & pinBOBpin), 0.79 (t, 3H, CH3)。
EXAMPLE eighteen lithium p-methylanilino catalysis of the hydroboration reaction of 2-methyl-5-bromo-benzoic acid with pinacol borane
Adding 2-methyl-5-bromo-benzoic acid (107.1 mg, 0.5 mmol) into a reaction flask subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (289 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of p-methylanilino lithium (0.8mol% of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, removing the solvent under reduced pressure to obtain a product boric acid ester, taking trimethoxy benzene (83.77 mg, 0.5 mmol) as an internal standard, and using CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 6.92 (d, 1H, ArCH), 7.21 (d, 1H, ArCH), 7.49 (s, 1H, ArCH), 4.79 (s, 2H, OCH2), 2.14 (s, 3H, CH3), 1.19 (s, 36H, CH3)。
example nineteen O-methylanilino lithium catalysis of the hydroboration reaction of o-carboxyphenylacetic acid and pinacol borane
Adding o-carboxyphenylacetic acid (90.0 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment in an inert gas atmosphere, adding pinacolborane (508 mu L, 3.5 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of o-methylanilino lithium (0.8mol percent of the amount), reacting for 80 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, removing the solvent under reduced pressure to obtain a product boric acid ester, taking sym-trimethoxybenzene (84.02 mg, 0.5 mmol) as an internal standard, and using CDCl3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 7.36 (br s, 1H, ArCH), 7.14 (br s, 3H, ArCH), 4.93 (s, 2H, CH2)，3.99 (t, 2H, CH2), 2.89 (t, 2H, CH2), 1.20 (s, 72H, CH3, OBpin & pinBOBpin)。
EXAMPLE twenty-2, 6-dimethylanilinium catalyzed hydroboration of 1-naphthoic acid with pinacol borane
Adding 1-naphthoic acid (85.4 mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (289 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of 2, 6-dimethylanilinium (0.7mol percent of the amount), reacting for 75 minutes at room temperature, contacting the reaction liquid with air to terminate the reaction, and removing the solvent under reduced pressure to obtain a product boric acid ester, wherein the boric acid ester uses sym-trimethoxybenzene (83.42 mg, 0.5 mmol) as an internal standard and CDCl as an internal standard3Dissolving, stirring for 10 min, sampling, and preparing nuclear magnetism. Is calculated by1The H yield was 93%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 8.05 (d, 1H, ArCH), 7.83-7.85 (m, 2H, ArCH), 7.78 (d, 1H, ArCH), 7.38-7.48 (m, 3H, ArCH), 5.37 (s, 2H, OCH2 ), 1.26 (s, 36H, CH3)。
differences in nucleophilic addition reaction activities of carboxylic acids and aldehydes and ketones: (1) the active hydrogen of the carboxylic acid is easy to leave, so that two O groups of the carboxylic acid are equivalent in practice, and the steric hindrance of the carboxyl group is larger in the view of the spatial structure, and the existence of the carboxyl hydrogen bond ensures that the electron cloud density of the whole carbonyl group is larger, and the nucleophilic reagent is difficult to attack the active center; (2) the nucleophilic reagent firstly attacks carbonyl carbon, which is related to the electron cloud density on carbon, and the attack with small density is firstly carried out, for example, aldehyde ketone has smaller electron cloud density than ester and amide, so that the activity is high, the reaction can be carried out preferentially, and the space effect is large and difficult to react; (3) when a transition state is formed, a leaving group is needed, and the leaving group of the aldehyde ketone is alkyl and hydrogen, and the alkyl and the hydrogen are not easy to leave, so that the aldehyde ketone only undergoes addition and does not undergo elimination, and the aldehyde ketone is different from carboxylic acid and derivatives thereof. On one hand, the existing method needs to utilize a catalyst which is difficult to synthesize, so that the cost is high; on the other hand, 60 is required for the catalytic reactionoC reaction temperature and 24 hours reaction time. The lithium anilino-complex disclosed by the invention has the advantages of high catalytic activity (0.8% of the mole number of the catalyst), mild reaction conditions (room temperature), short reaction time, high reaction yield, simple and controllable reaction and simple post-treatment, and aromatic carboxylic acid and borane are subjected to hydroboration reaction under the catalysis of the lithium anilino-complex.
Claims (2)
1. The method for preparing the borate based on the anilino lithium compound comprises the following steps of mixing borane and aromatic carboxylic acid in an inert gas atmosphere, adding a catalyst anilino lithium compound, and carrying out a hydroboration reaction to obtain the borate; the borane is pinacol borane; the aromatic carboxylic acid is one of benzoic acid, 4-bromobenzoic acid, 4-fluorobenzoic acid, 2-methoxybenzoic acid, 2-methyl-5-bromo-benzoic acid, 4-tert-butylbenzoic acid, 2-bromobenzoic acid and 4-iodobenzoic acid; the anilino lithium compound is selected from anilino lithium, p-methylanilino lithium, o-methylanilino lithium, 2-methoxyanilino lithium or 4-methoxyanilino lithium; the aromatic carboxylic acid and the borane are used in a molar ratio of 1: 3-1: 7; the dosage of the anilino lithium compound is 0.7 to 0.9 percent of the molar weight of the aromatic carboxylic acid; the temperature of the hydroboration reaction is room temperature, and the time is 70-80 minutes.
2. The method for preparing the borate ester based on the anilino lithium compound, according to claim 1, is characterized in that after the hydroboration reaction is finished, the reaction is stopped by contacting with air, and the solvent is removed from the reaction liquid under reduced pressure to obtain the different substituted borate esters.
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