CN108558923A - Application of the anilino- lithium in catalysis ketone and borine hydroboration - Google Patents
Application of the anilino- lithium in catalysis ketone and borine hydroboration Download PDFInfo
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- CN108558923A CN108558923A CN201810336699.7A CN201810336699A CN108558923A CN 108558923 A CN108558923 A CN 108558923A CN 201810336699 A CN201810336699 A CN 201810336699A CN 108558923 A CN108558923 A CN 108558923A
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- China
- Prior art keywords
- ketone
- borine
- hydroboration
- lithium
- anilino
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- 150000002576 ketones Chemical class 0.000 title claims abstract description 31
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 29
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 28
- IFOBAKIQHNOSRE-UHFFFAOYSA-N lithium;phenylazanide Chemical compound [Li+].[NH-]C1=CC=CC=C1 IFOBAKIQHNOSRE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical group OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims abstract description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 boric acid ester compound Chemical class 0.000 claims abstract description 7
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 claims description 10
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical group CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 10
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical group CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0252—Nitrogen containing compounds with a metal-nitrogen link, e.g. metal amides, metal guanidides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The application of anilino- lithium of the present invention, and in particular to anilino- lithium is in catalysis ketone and the efficient application in borine hydroboration；Under anhydrous and oxygen-free environment, in atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, catalyst aniline base lithium is then added, is uniformly mixed, adds ketone, hydroboration occurs, is exposed in air and terminates reaction, obtain borate；The ketone is aliphatic ketone.Catalyst disclosed by the invention has preferable universality for the aliphatic ketone of different structure, and the boric acid ester compound to obtain different substituents structure provides more selections.
Description
Technical field
The application of anilino- lithium of the present invention, and in particular to anilino- lithium is in catalysis ketone and borine hydroboration
Efficient application.
Technical background
For the hydroboration of equivalent catalysis of carbonyl class compound, obtained borate ester product is hydrolyzed,
It is the very effective method of synthol in contemporary Synthetic Organic Chemistry.The product boric acid ester compound of hydroboration, no
But it can be used as polymeric additive, gasoline additive, fire retardant, bactericidal agent use, it is also possible to make special surfactant, moisten
Oil additive and motor vehicle brake fluid etc., application range is very extensive.Therefore, for the hydroboration research of unsaturated bond,
All have great importance for modern industry and Synthetic Organic Chemistry, is widely paid close attention to so as to cause researcher.
Various catalyst have been used for the hydroboration of ketone, especially in recent years, about this kind of reaction
It reports many.Since under no catalysts conditions, the hydroboration of carbonyls is difficult to occur.So for this one kind
The research emphasis of reaction exactly develops efficient catalyst system and catalyzing.But the catalyst system and catalyzing reported at present, catalyst are all opposite
Costliness or reaction condition are more harsh.
Although belonging to carbonyls, ketone and aldehyde have different reaction properties, this is common sense, and the prior art exists simultaneously
Using keto-aldehyde as raw material, but only there is a situation where a kind of raw materials to react；Electron donating group can weaken the electropositive of carbonyl carbon, to cut
The nucleophilic addition activity of weak carbonyl, aromatic aldehyde is since conjugation reduces carbonyl activity, to different the position of substitution, different electronic effects
Aromatic compound and fatty compound have and larger react difference.So developing efficient catalytic ketone under new temperate condition
Hydroboration catalyst system and catalyzing it is particularly urgent.
Invention content
The goal of the invention of the present invention is to provide the application of anilino- lithium, i.e., using anilino- lithium be effective catalyst be catalyzed ketone and
The application of hydroboration occurs for borine；The anilino- lithium chemical formula is：PhNHLi, chemical structural formula are as follows：
To achieve the above object of the invention, the technical solution adopted by the present invention is：Anilino- lithium is anti-in catalysis ketone and borine hydroboration
Application in answering；The ketone is aliphatic ketone.
The invention also discloses the methods of anilino- lithium catalysis ketone and borine generation hydroboration, include the following steps：
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter anilino- lithium, be uniformly mixed, add ketone, hydroboration occurs.
The present invention further discloses a kind of preparation method of borate, includes the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter catalyst aniline base lithium, be uniformly mixed, add ketone, hydroboration occurs, is exposed in air and terminates reaction, obtain boron
Acid esters；The ketone is aliphatic ketone.
In above-mentioned technical proposal, the aliphatic ketone is selected from methyl isopropyl ketone, 4- heptanone；The borine is selected from pinacol
Borine；The dosage of the catalyst is the 0.2-0.3% of ketone mole, and the molar ratio of ketone and borine is 1: 1.1, hydroboration
Temperature be room temperature, the reaction time be 30-40 minutes.
Above-mentioned technical proposal can indicate as follows：
R1, R2Come from raw ketone.
Due to the application of the above technical scheme, the present invention has the following advantages compared with prior art：
1. present invention firstly discovers that anilino- lithium, which extremely can efficiently be catalyzed methyl isopropyl ketone, 4- heptanone and borine, occurs boron
Hydrogenation provides new scheme to prepare borate with borine generation hydroboration using carbonyls.
2. high (the catalyst use of catalytic activity that hydroboration occurs with borine for anilino- lithium catalysis ketone disclosed by the invention
Amount is only 0.2-0.3 %), reaction condition is mild (room temperature), and the reaction time is short (30 ~ 40 min), and reaction yield is high, reaction letter
Single controllable, post-processing is simple, and reaction uses solvent-free system, reduces the pollution to environment.
3. catalyst disclosed by the invention has preferable universality for the aliphatic ketone of different structure, taken to obtain difference
More selections are provided for the boric acid ester compound of based structures.
Specific implementation mode
The present invention is described further with reference to embodiment：
Embodiment one：Anilino- lithium is catalyzed methyl isopropyl ketone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran solution that 40ul anilino- lithiums are added of argon gas protection
(0.05M) (0.2 mol% dosages) is then added 0.1596 mL borines with syringe, is uniformly mixed, then be added with syringe
0.1072 mL methyl isopropyl ketones, mixture are stirred at room temperature, and after reacting 30 min, nuclear-magnetism yield is 99%, is subtracted later
Pressure removes a small amount of tetrahydrofuran and excessive borine to get to corresponding pinacol borate.1H NMR (400 MHz,
CDCl3) δ 3.94 (p, J = 6.2 Hz, 1H, OCH), 1.66 (dq, J = 13.5, 6.8 Hz, 1H,
CH3CH), 1.25 (s, 12H, CH3), 1.14 (d, J = 6.3 Hz, 3H, CH3), 0.91-0.85 (m, 6H,
CHCH3). 13C NMR (101 MHz, CDCl3) δ 82.34 (OC), 75.40 (OCH), 34.25 (OCHCH),
24.50 (d, J = 7.4 Hz, CH3), 19.30 (CH3), 18.10 (CH3), 17.74 (CH3)。
Embodiment two：Anilino- lithium is catalyzed 4- heptanone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran solution that 60ul anilino- lithiums are added of argon gas protection
(0.05M) (0.3 mol% dosages) is then added 0.1596 mL borines with syringe, is uniformly mixed, then be added with syringe
0.1398 mL4- heptanone, mixture are stirred at room temperature, and after reacting 40 min, nuclear-magnetism yield is 99%, are removed under reduced pressure later few
The tetrahydrofuran of amount and excessive borine are to get to corresponding pinacol borate.1H NMR (400 MHz, CDCl3) δ
4.03 (td, J = 8.0, 3.9 Hz, 1H, CH), 1.51 – 1.31 (m, 8H, CH2), 1.24 (s, 12H,
CH3), 0.90 (t, J = 7.1 Hz, 6H, CH3). 13C NMR (101 MHz, CDCl3) δ 81.82 (OC),
73.55 (OCH), 38.18 (CH2), 23.97 (CH3), 18.10 (CH3), 13.48 (CH3)。
Anilino- lithium is replaced with to the amido lithium compound of formula I, it is virtually impossible to obtain product, yield is less than 8%.
Present invention firstly discovers that anilino- lithium can be catalyzed the hydroboration of ketone with high catalytic activity, and have
Very wide substrate usage range.Cheap catalyst and lower catalyst amount, mild catalytic condition are work
Industry application provides possibility.
Claims (10)
1. anilino- lithium is in catalysis ketone and the application in borine hydroboration；The ketone is aliphatic ketone.
2. application according to claim 1, which is characterized in that the hydroboration includes the following steps：
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter anilino- lithium, be uniformly mixed, add ketone, hydroboration occurs.
3. application according to claim 1, which is characterized in that the aliphatic ketone is selected from methyl isopropyl ketone, 4- heptanone；
The borine is selected from pinacol borine.
4. application according to claim 1, which is characterized in that the dosage of the anilino- lithium is the 0.2- of ketone mole
0.3%, the molar ratio of ketone and borine is 1: 1.1.
5. application according to claim 1, which is characterized in that the temperature of hydroboration is room temperature, and the time is 30-40 points
Clock.
6. a kind of preparation method of borate, includes the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter catalyst aniline base lithium, be uniformly mixed, add ketone, hydroboration occurs, is exposed in air and terminates reaction, obtain boron
Acid esters；The ketone is aliphatic ketone.
7. the preparation method of borate according to claim 6, which is characterized in that the aliphatic ketone is selected from isopropyl methyl first
Ketone, 4- heptanone.
8. the preparation method of borate according to claim 6, which is characterized in that the borine is selected from pinacol borine.
9. the preparation method of borate according to claim 6, which is characterized in that the dosage of the catalyst is ketone mole
0.2-0.3%, the molar ratio of ketone and borine is 1: 1.1.
10. the preparation method of borate according to claim 6, which is characterized in that the temperature of hydroboration is room temperature, when
Between be 30-40 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810336699.7A CN108558923A (en) | 2018-04-16 | 2018-04-16 | Application of the anilino- lithium in catalysis ketone and borine hydroboration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810336699.7A CN108558923A (en) | 2018-04-16 | 2018-04-16 | Application of the anilino- lithium in catalysis ketone and borine hydroboration |
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| Publication Number | Publication Date |
|---|---|
| CN108558923A true CN108558923A (en) | 2018-09-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810336699.7A Withdrawn CN108558923A (en) | 2018-04-16 | 2018-04-16 | Application of the anilino- lithium in catalysis ketone and borine hydroboration |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503318A (en) * | 2018-12-24 | 2019-03-22 | 苏州大学 | A method of alcoholic compound is prepared by the non-catalytic reaction of aliphatic carboxylic acid |
| WO2019200521A1 (en) * | 2018-04-17 | 2019-10-24 | 南通纺织丝绸产业技术研究院 | Application of anilino lithium in catalyzing hydroboration of carbonyl compound and borane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749372A (en) * | 2016-12-07 | 2017-05-31 | 厦门大学 | A kind of preparation method of organic boronic ester compounds |
| CN107501309A (en) * | 2017-09-01 | 2017-12-22 | 南京林业大学 | A kind of condensate Schiff base rare-earth ytterbium iodide and its preparation method and application |
-
2018
- 2018-04-16 CN CN201810336699.7A patent/CN108558923A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749372A (en) * | 2016-12-07 | 2017-05-31 | 厦门大学 | A kind of preparation method of organic boronic ester compounds |
| CN107501309A (en) * | 2017-09-01 | 2017-12-22 | 南京林业大学 | A kind of condensate Schiff base rare-earth ytterbium iodide and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| DEBABRATA MUKHERJEE: "Alkali Metal hydridotriphenylborates [(L)M][HBPh3](M=Li,Na,K):Chemoselective Catalysts for Carbonyl and CO2 Hydroboration", 《J.A.C.S》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019200521A1 (en) * | 2018-04-17 | 2019-10-24 | 南通纺织丝绸产业技术研究院 | Application of anilino lithium in catalyzing hydroboration of carbonyl compound and borane |
| CN109503318A (en) * | 2018-12-24 | 2019-03-22 | 苏州大学 | A method of alcoholic compound is prepared by the non-catalytic reaction of aliphatic carboxylic acid |
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