CN109438492B - Method for preparing boric acid ester by non-catalytic hydroboration reaction of aliphatic carboxylic acid - Google Patents
Method for preparing boric acid ester by non-catalytic hydroboration reaction of aliphatic carboxylic acid Download PDFInfo
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- -1 boric acid ester Chemical class 0.000 title claims abstract description 26
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 title claims abstract description 25
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 24
- 239000004327 boric acid Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000085 borane Inorganic materials 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 12
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001361 adipic acid Substances 0.000 claims abstract description 6
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 6
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims abstract description 6
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940005605 valeric acid Drugs 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 9
- 230000018044 dehydration Effects 0.000 abstract description 8
- 238000006297 dehydration reaction Methods 0.000 abstract description 8
- 238000003756 stirring Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000001728 carbonyl compounds Chemical class 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 229960002645 boric acid Drugs 0.000 description 9
- 235000010338 boric acid Nutrition 0.000 description 9
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a method for preparing boric acid ester by non-catalytic hydroboration reaction of aliphatic carboxylic acid. In an inert gas atmosphere, stirring and uniformly mixing pinacolborane and carboxylic acid in a reaction bottle subjected to dehydration and deoxidation treatment, and reacting for 8-10 hours to obtain boric acid ester; the carboxylic acid is acetic acid, caproic acid, valeric acid, heptanoic acid, trimethyl acetic acid, adipic acid and the like. The method has the advantages that the aliphatic carboxylic acid is efficiently subjected to the hydroboration reaction with the borane for the first time under the condition of no catalyst, and a new scheme is provided for the preparation of the boric acid ester by the hydroboration reaction of the carbonyl compound and the borane.
Description
Technical Field
The invention relates to the field of application of green chemistry, in particular to a hydroboration reaction of fatty acid without solvent and catalyst.
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.
Since the pioneering research on borane by Stock et al in 1912, the electron-deficient characteristics and the nature of chemical bonds of borane have attracted attention, and the research on borane has become an important research field in the chemical science. 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) nucleophiles attack carbonyl carbons first, which is related to the electron cloud density on the carbon, with less dense first attacks, such as aldehydes and ketones being less dense than esters and amides, soThe activity is high, the reaction can be carried out preferentially, and the space effect is large and is not easy 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.
Disclosure of Invention
The invention aims to provide a method which accords with the principle of green chemistry, and in the absence of a solvent and a catalyst, pinacol borane is reduced by using hydroboration of carboxylic acid to generate boric acid ester, and then alcohol is generated. The method is green and environment-friendly, and has a good substrate application range.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing boric acid ester through a hydroboration reaction of aliphatic carboxylic acid comprises the following steps of carrying out the hydroboration reaction on the aliphatic carboxylic acid and borane in the absence of a solvent and a catalyst to prepare the boric acid ester.
The application of aliphatic carboxylic acid and borane as raw materials in the preparation of boric acid ester is characterized in that the application is carried out in the absence of solvent, catalyst and inert gas atmosphere.
In the technical scheme, the borane is pinacol borane; the aliphatic carboxylic acid is acetic acid, caproic acid, valeric acid, heptanoic acid, trimethyl acetic acid, adipic acid and the like.
In the technical scheme, the molar ratio of the aliphatic carboxylic acid to the borane is 1: 3-1: 7.
In the technical scheme, the hydroboration reaction temperature is room temperature, and the time is 8-10 hours.
In the technical scheme, the method for preparing the boric acid ester by the hydroboration reaction of the aliphatic carboxylic acid comprises the following specific steps:
under the inert gas atmosphere, stirring and mixing borane and aliphatic carboxylic acid uniformly; reacting for 8-10 hours; and after the reaction is finished, contacting air to stop the reaction to obtain the boric acid ester.
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:
the invention can carry out hydroboration reaction of aliphatic carboxylic acid and pinacol borane for the first time without solvent and catalyst, thereby developing an efficient and green method for preparing alkyl borate. The aromatic carboxylic acid is generally solid, the aliphatic carboxylic acid is generally liquid, the reaction of the aromatic carboxylic acid with the pinacol borane is a heterogeneous reaction, and the reaction of the aliphatic carboxylic acid with the pinacol borane is a homogeneous reaction.
1. The invention can carry out the hydroboration reaction of the aliphatic carboxylic acid and the borane with high activity at room temperature, the reaction lasts for 8-10 hours, the conversion rate can reach more than 90 percent, and compared with the existing catalytic system, the invention can reach high conversion rate without using solvent and catalyst.
2. The solvent-free catalyst-free carboxylic acid hydroboration disclosed by the invention has wide application range on substrates, is suitable for different aliphatic carboxylic acids, and provides more choices for industrial synthesis of borate; 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 Generation of boronic acid esters of pinacol borane and acetic acid in a 4:1 molar ratio
Adding acetic acid (28.6 mu L and 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under the atmosphere of inert gas N2, adding pinacolborane (290 mu L and 2 mmol) by using a liquid transfer gun, reacting for 10 hours at room temperature, removing the reaction from a glove box, and stopping the reaction to obtain a product boric acid ester; sym-trimethoxybenzene (84.08 mg,0.5 mmol) was used as an internal standard, dissolved in CDCl3, stirred for 10 min, sampled and nuclear magnetic prepared. The calculated 1H yield was 99%; the product was not obtained by replacing acetic acid with equimolar acetaldehyde. Nuclear magnetic data of product 1H NMR (400 MHz, CDCl 3): δ 3.89(q, 2H, CH2), 1.26(s, 36H, CH3), 1.22 (br s, 3H, CH 3).
EXAMPLE II 4:1 molar ratio of pinacolborane and pentanoic acid to boronic ester
Under the atmosphere of inert gas N2, pentanoic acid (54.38 muL, 0.5 mmol) is added into a reaction flask after dehydration and deoxidation treatment, pinacolborane (290 muL, 2 mmol) is added by a liquid transfer gun, the reaction is carried out for 10 hours at room temperature, the reaction is removed from a glove box, sym-trimethoxybenzene (84.12 mg,0.5 mmol) is used as an internal standard, and is dissolved by CDCl3, stirred for 10 minutes, sampled and matched with nuclear magnetism. The calculated 1H yield was 92%. Nuclear magnetic data of product 1H NMR (400 MHz, CDCl 3): δ 3.82 (t,2H, OCH2), 1.53-1.57 (m, 2H, CH2), 1.31-1.53 (m, 4H, CH2), 1.29 (s, 36H, CH), 0.87 (t, 3H, CH 3).
EXAMPLE III Synthesis of Borate esters with pinacolborane and hexanoic acid in a 4:1 molar ratio
Adding caproic acid (62.52 mu L and 0.5 mmol) into a reaction flask subjected to dehydration and deoxidation treatment under the atmosphere of inert gas N2, adding pinacolborane (290 mu L and 2 mmol) by using a liquid transfer gun, reacting at room temperature for 10 hours, removing the reaction from a glove box, dissolving with CDCl3 by using sym-trimethoxybenzene (84.01 mg and 0.5 mmol) as an internal standard, stirring for 10 minutes, sampling, and performing nuclear magnetic resonance. The calculated 1H yield was 90%. Nuclear magnetic data of product 1H NMR (400 MHz, CDCl 3): δ 3.77 (t,2H, OCH2), 1.47-1.53 (m, 2H, CH2), 1.25-1.36 (m, 6H, CH2), 1.20 (s, 48H, CH3), 0.83 (t, 3H, CH 3).
EXAMPLE four Synthesis of boronic acid esters with pinacolborane and heptanoic acid in a 4:1 molar ratio
Adding heptanoic acid (70.90 muL, 0.5 mmol) into a reaction flask subjected to dehydration and deoxidation treatment under the atmosphere of inert gas N2, adding pinacolborane (290 muL, 2 mmol) by using a liquid transfer gun, reacting at room temperature for 10 hours, removing the reaction from a glove box, dissolving with CDCl3 by using sym-trimethoxybenzene (84.05 mg,0.5 mmol) as an internal standard, stirring for 10 minutes, sampling, and preparing nuclear magnetism. The calculated 1H yield was 90%. Nuclear magnetic data of product 1H NMR (400 MHz, CDCl 3): δ 3.72 (t,2H, OCH2), 1.42-1.48 (m, 2H, CH2), 1.20-1.31 (m, 8H, CH2), 1.15 (s, 48H, CH3), 0.78 (t, 3H, CH 3).
EXAMPLE penta pinacolborane and acetic acid 3:1 molar ratio to generate boronic acid esters
Acetic acid (28.6. mu.L, 0.5 mmol) was added to the dehydrated and deoxygenated reaction flask under an inert gas N2 atmosphere, pinacolborane (218. mu.L, 1.5 mmol) was added by a pipette, the reaction was reacted at room temperature for 10 hours, the reaction was removed from the glove box, sym-trimethoxybenzene (84.08 mg,0.5 mmol) was used as an internal standard, dissolved in CDCl3, stirred for 10 minutes, sampled, and nuclear magnetic purified. The calculated 1H yield was 95%. Nuclear magnetic data of product 1H NMR (400 MHz, CDCl 3): δ 3.89(q, 2H, CH2), 1.26(s, 36H, CH3), 1.22 (br s, 3H, CH 3).
EXAMPLE sixthly pinacol borane and acetic acid 5:1 molar ratio to yield boronic acid esters
Adding acetic acid (28.6 mu L and 0.5 mmol) into a reaction flask subjected to dehydration and deoxidation treatment under the atmosphere of an inert gas N2, adding pinacol borane (363 mu L and 2.5 mmol) by using a liquid transfer gun, reacting at room temperature for 10 hours, removing the reaction from a glove box, dissolving with CDCl3 by using sym-trimethoxybenzene (84.08 mg and 0.5 mmol) as an internal standard, stirring for 10 minutes, sampling, and performing nuclear magnetic resonance. The calculated 1H yield was 99%; 0.5mL of anhydrous 1, 4-dioxane was added to the reaction system, and the product yield was 16%. Nuclear magnetic data of product 1H NMR (400 MHz, CDCl 3): δ 3.89(q, 2H, CH2), 1.26(s, 36H, CH3), 1.22 (br s, 3H, CH 3).
EXAMPLE heptageneration of boronic acid esters with pinacol borane and trimethylacetic acid in a 4:1 molar ratio
Adding trimethylacetic acid (50.7mg, 0.5 mmol) into a reaction flask subjected to dehydration and deoxidation treatment under the atmosphere of inert gas N2, adding pinacolborane (289 mu L, 2 mmol) by using a liquid transfer gun, reacting at room temperature for 10 hours, removing the reaction from a glove box, dissolving with CDCl3 by using sym-trimethoxybenzene (84.08 mg,0.5 mmol) as an internal standard, stirring for 10 minutes, sampling, and preparing nuclear magnetism. The calculated 1H yield was 99%. Nuclear magnetic data of product 1H NMR (400 MHz, CDCl 3): δ 3.44(s,2H, OCH2), 1.18 (s, 36H, CH3, OBpin & pinBOBpin), 0.83 (s, 9H, CH 3).
EXAMPLE octa pinacol borane and adipic acid 7:1 molar ratio to yield boronic ester
Adding adipic acid (72.9 mg,0.5 mmol) into a reaction flask subjected to dehydration and deoxidation treatment under an inert gas N2 atmosphere, adding pinacolborane (508 μ L, 3.5 mmol) by using a liquid transfer gun, reacting at room temperature for 10 hours, removing the reaction from a glove box, dissolving with CDCl3 by using sym-trimethoxybenzene (83.90 mg,0.5 mmol) as an internal standard, stirring for 10 minutes, sampling, and performing nuclear magnetic resonance. The calculated 1H yield was 99%. Nuclear magnetic data of product 1H NMR (400 MHz, CDCl 3): delta.3.78 (t, 4H, OCH2), 1.49-1.51 (m, 4H, CH2), 1.29-1.31 (m, 4H, CH2), 1.18 (s, 72H, CH3, OBpin & pinBOBpin).
The reaction of the embodiment of the invention is carried out in a glove box; the invention is a hydroboration reaction of carboxylic acid without solvent and catalyst, which accords with the principle of green chemistry.
Claims (4)
1. A method for preparing boric acid ester by hydroboration reaction of aliphatic carboxylic acid is characterized by comprising the following steps of, in the absence of solvent and catalyst, carrying out hydroboration reaction on the aliphatic carboxylic acid and borane to prepare the boric acid ester; the borane is pinacol borane; the aliphatic carboxylic acid is acetic acid, caproic acid, valeric acid, heptanoic acid, trimethyl acetic acid or adipic acid; the temperature of the hydroboration reaction is room temperature; the hydroboration reaction time is 8-10 hours; the molar ratio of the aliphatic carboxylic acid to the borane is 1: 3-1: 7.
2. The method for producing boronic acid esters from hydroboration of aliphatic carboxylic acids according to claim 1, wherein the hydroboration reaction is carried out under an inert gas atmosphere; and after the hydroboration reaction is finished, contacting air to stop the reaction, and obtaining the boric acid ester.
3. The method for preparing boronic acid ester from aliphatic carboxylic acid through hydroboration reaction according to claim 1, wherein the reaction is terminated by contacting with air after the hydroboration reaction is completed, thereby obtaining boronic acid ester.
4. The application of aliphatic carboxylic acid and borane as raw materials in the preparation of boric acid ester is characterized in that the application is carried out in the absence of solvent, catalyst and inert gas atmosphere; the borane is pinacol borane; the aliphatic carboxylic acid is acetic acid, caproic acid, valeric acid, heptanoic acid, trimethyl acetic acid or adipic acid; the temperature for preparing the boric acid ester is room temperature, and the time is 8-10 hours; the molar ratio of the aliphatic carboxylic acid to the borane is 1: 3-1: 7.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811490360.9A CN109438492B (en) | 2018-12-06 | 2018-12-06 | Method for preparing boric acid ester by non-catalytic hydroboration reaction of aliphatic carboxylic acid |
| PCT/CN2019/077387 WO2020113835A1 (en) | 2018-12-06 | 2019-03-07 | Method for preparing boric acid ester using uncatalyzed hydroboration of carboxylic acid |
| US17/311,314 US20220017543A1 (en) | 2018-12-06 | 2019-03-07 | Method for preparing boric acid ester using uncatalyzed hydroboration of carboxylic acid |
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| CN201811490360.9A CN109438492B (en) | 2018-12-06 | 2018-12-06 | Method for preparing boric acid ester by non-catalytic hydroboration reaction of aliphatic carboxylic acid |
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