CN109369695B - Method for preparing boric acid ester based on aliphatic carboxylic acid hydroboration reaction - Google Patents
Method for preparing boric acid ester based on aliphatic carboxylic acid hydroboration reaction Download PDFInfo
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- CN109369695B CN109369695B CN201811520091.6A CN201811520091A CN109369695B CN 109369695 B CN109369695 B CN 109369695B CN 201811520091 A CN201811520091 A CN 201811520091A CN 109369695 B CN109369695 B CN 109369695B
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- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 30
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 title claims abstract description 23
- -1 boric acid ester Chemical class 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000004327 boric acid Substances 0.000 title claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 58
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910000085 borane Inorganic materials 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical group CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 11
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 description 3
- QVXCVTFQUXXVNO-UHFFFAOYSA-N C(C)(C)C1=C(NC(C[Li])=CC(C)NC2=C(C=CC=C2C(C)C)C(C)C)C(=CC=C1)C(C)C Chemical compound C(C)(C)C1=C(NC(C[Li])=CC(C)NC2=C(C=CC=C2C(C)C)C(C)C)C(=CC=C1)C(C)C QVXCVTFQUXXVNO-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 3
- 229940030010 trimethoxybenzene Drugs 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000004429 atom Chemical group 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to application of n-butyl lithium, in particular to a method for preparing borate ester based on an aliphatic carboxylic acid hydroboration reaction. And stirring and mixing the catalyst, the borane and the carboxylic acid uniformly in sequence, reacting for 10-20 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 substituent groups. The n-butyllithium 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 0.2 mol% of the molar weight of the carboxylic acid, compared with the existing catalytic system, the commercial reagent n-butyllithium is utilized, the reaction condition is mild, and the yield of borate ester of different substituents can reach 99% under the limited condition.
Description
Technical Field
The invention relates to application of a commercial reagent n-butyllithium, in particular to a method for preparing borate ester based on an aliphatic carboxylic acid hydroboration reaction.
Background
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. 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. 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.
Disclosure of Invention
The invention aims to provide a method for preparing boric acid ester by hydroboration reaction of aliphatic carboxylic acid, namely, n-butyl lithium is used as a high-efficiency catalyst to catalyze the hydroboration reaction of carboxylic acid and borane, the aliphatic carboxylic acid is generally liquid, and the reaction of the aliphatic carboxylic acid and pinacol borane is homogeneous 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 based on the hydroboration reaction of the aliphatic carboxylic acid comprises the following steps of mixing borane and the aliphatic carboxylic acid under the inert gas atmosphere, adding a catalyst n-butyllithium, and then carrying out the hydroboration reaction to obtain the borate.
Application of n-butyl lithium in catalyzing hydroboration reaction of aliphatic carboxylic acid and borane.
In the present invention, the n-butyllithium is a commercial n-butyllithium reagent.
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 temperature of the hydroboration reaction is room temperature, and the time is 10-20 minutes.
In the technical scheme, the using amount of the n-butyl lithium is 0.1-0.3% of the molar amount of the aliphatic carboxylic acid.
The hydroboration reaction disclosed by the invention comprises the following specific steps:
under the inert gas atmosphere, mixing borane and aliphatic carboxylic acid, adding a catalyst n-butyllithium, and then carrying out a 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:
the existing hydroboration methods all have obvious defects of L iAlH4And 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. 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 commercial n-butyllithium can efficiently catalyze the hydroboration reaction of aliphatic carboxylic acid and borane, and the method is highly suitable for atom economic synthesis.
2. The n-butyllithium disclosed by the invention has the advantages of high catalytic activity (0.2 mol% of catalyst), mild reaction conditions (room temperature), short reaction time (10-20 minutes), high reaction yield, simple and controllable reaction and simple post-treatment, and is used for catalyzing the hydroboration reaction of the aliphatic carboxylic acid and the borane.
3. The application range of the substrate for hydroboration of aliphatic carboxylic acid catalyzed by n-butyl lithium disclosed by the invention is wide, the substrate is suitable for carboxylic acids with different substituent positions and different electronic effects, and more choices are provided 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 hydroboration of acetic acid with pinacol borane catalyzed by n-butyllithium
Adding acetic acid (28.6 mu L, 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 10 mu L n-butyllithium tetrahydrofuran solution (0.1M) (0.2 mol% using amount, the same below), reacting at room temperature for 15 minutes, contacting the reaction liquid with air, removing the solvent to obtain a product boric acid ester, and performing pyromellitic dianhydride reaction to obtain the boric acid esterMethoxybenzene (84.08 mg,0.5 mmol) as internal standard with 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)：3.88 (q, 2H, CH2), 1.25 (s, 36H, CH3), 1.21 (br s, 3H, CH3)。
95% yield when pinacolborane (218. mu. L, 1.5 mmol) and 99% yield when pinacolborane (363. mu. L, 2.5 mmol) and reaction time of 20 minutes and 99% yield when n-butyllithium is replaced by a triaryloxy rare earth catalyst Nd (OAr)3(THF)2No product is obtained.
EXAMPLE II n-butyllithium catalyzed hydroboration of pentanoic acid with pinacol borane
Adding valeric acid (54.38 mu L, 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 n-butyl lithium (0.2 mol percent of the amount), reacting for 15 minutes at room temperature, contacting the reaction liquid with air, removing the solvent to obtain a product boric acid ester, taking sym-trimethoxybenzene (84.12 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 92%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 3.81 (t, 2H,OCH2), 1.52-1.56 (m, 2H,CH2), 1.30-1.52 (m, 4H, CH2), 1.28（s, 36H, CH)，0.86(t, 3H, CH3)。
EXAMPLE III catalysis of the hydroboration reaction of hexanoic acid with pinacol borane by n-butyllithium
Adding caproic acid (62.52 mu L, 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 n-butyl lithium (0.2 mol percent of the amount), reacting for 15 minutes at room temperature, contacting the reaction liquid with air, removing the solvent to obtain a product boric acid ester, taking sym-trimethoxybenzene (84.01 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 90%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3)： 3.76 (t, 2H,OCH2), 1.46-1.52 (m, 2H,CH2), 1.24-1.35 (m, 6H, CH2), 1.19（s, 48H, CH3)，0.82(t, 3H, CH3)。
EXAMPLE IV N-butyllithium catalyzed hydroboration of heptanoic acid with pinacol borane
Adding heptanoic acid (70.90 mu L, 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 n-butyl lithium (0.2 mol percent of the amount), reacting for 15 minutes at room temperature, contacting the reaction liquid with air, removing the solvent to obtain a product boric acid ester, taking trimethoxybenzene (84.05 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 90%. Nuclear magnetic data of the product 1H NMR (400 MHz, CDCl)3)： 3.71 (t, 2H,OCH2), 1.41-1.47 (m, 2H,CH2), 1.19-1.30 (m, 8H, CH2), 1.24（s, 48H, CH3)，0.77(t, 3H, CH3)。
EXAMPLE V catalysis of trimethylacetic acid with pinacol borane hydroboration by n-butyllithium
Adding trimethyl acetic acid (50.7mg, 0.5 mmol) into a reaction bottle subjected to dehydration and deoxidation treatment under an inert gas atmosphere, adding pinacolborane (288 mu L, 2 mmol) by using a liquid transfer gun, finally adding a tetrahydrofuran solution of n-butyl lithium (0.2 mol% dosage), reacting for 15 minutes at room temperature, contacting the reaction liquid with air, removing the solvent to obtain a product boric acid ester, taking trimethoxybenzene (84.08 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) 3.43 (s, 2H,OCH2), 1.17 (s, 36H, CH3, OBpin&pinBOBpin), 0.82 (s, 9H, CH3)。
EXAMPLE sixthly, n-butyllithium catalyzed hydroboration of adipic acid with pinacol borane
Adding adipic acid (72.9 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 n-butyl lithium (0.2 mol% of the amount), reacting for 15 minutes at room temperature, contacting the reaction liquid with air, removing the solvent to obtain a product boric acid ester, taking sym-trimethoxybenzene (83.90 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)： 3.77 (t, 4H,OCH2), 1.48-1.50 (m, 4H, CH2), 1.28-1.30 (m, 4H, CH2), 1.17 (s, 72H, CH3,OBpin&pinBOBpin)。
comparative example: 2, 4-di (2, 6-diisopropylanilino) -2-pentenyl lithium catalyzed hydroboration reaction of acetic acid and pinacol borane
Adding acetic acid (28.6 mu L, 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 (0.1M) (0.2 mol% using amount) of 2, 4-bis (2, 6-diisopropylanilino) -2-pentenyl lithium, reacting for 15 minutes at room temperature, contacting the reaction liquid with air, removing the solvent 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 18%. Nuclear magnetic data of the product:1HNMR (400 MHz, CDCl3) ： 3.87 (q, 2H, CH2), 1.24 (s, 36H, CH3), 1.20 (br s, 3H,CH3)。
the chemical structural formula of the 2, 4-di (2, 6-diisopropylanilino) -2-pentenyl lithium is as follows:
Claims (2)
1. the method for preparing the boric acid ester based on the hydroboration reaction of the aliphatic carboxylic acid comprises the following steps of mixing borane and the aliphatic carboxylic acid under the inert gas atmosphere, adding a catalyst n-butyllithium, and then carrying out the hydroboration reaction to obtain the boric acid ester; the aliphatic carboxylic acid is one of acetic acid, caproic acid, valeric acid and heptanoic acid; the borane is pinacol borane; the dosage of the n-butyl lithium is 0.1 to 0.3 percent of the molar weight of the aliphatic carboxylic acid; the temperature of the hydroboration reaction is room temperature; the hydroboration reaction time is 10-20 minutes; the molar ratio of the aliphatic carboxylic acid to the borane is 1: 3-1: 7.
2. The method for preparing the boric acid ester based on the hydroboration reaction of the aliphatic carboxylic acid as claimed in claim 1, wherein the reaction is terminated by contacting with air after the hydroboration reaction is finished, and the solvent is removed from the reaction solution under reduced pressure to obtain the boric acid ester.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010427456.1A CN111471066A (en) | 2018-12-12 | 2018-12-12 | Application of n-butyl lithium in catalyzing hydroboration reaction of aliphatic carboxylic acid and borane |
| CN201811520091.6A CN109369695B (en) | 2018-12-12 | 2018-12-12 | Method for preparing boric acid ester based on aliphatic carboxylic acid hydroboration reaction |
| PCT/CN2019/077386 WO2020118922A1 (en) | 2018-12-12 | 2019-03-07 | Method for preparing boric acid ester based on lithium compound |
| US17/413,521 US20220024950A1 (en) | 2018-12-12 | 2019-03-07 | Method for preparing boric acid ester based on lithium compound |
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| CN108654692A (en) * | 2018-04-16 | 2018-10-16 | 苏州大学 | Application of the n-BuLi in catalysis ketone and borine hydroboration |
| CN108948059B (en) * | 2018-08-14 | 2020-08-18 | 南京林业大学 | Carboxylic acid deoxygenation hydroboration reaction method |
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