CN111909194A - Method for catalyzing ketone cyanogen silicification reaction by deprotonated phenyl bridging beta-ketimine lithium complex - Google Patents
Method for catalyzing ketone cyanogen silicification reaction by deprotonated phenyl bridging beta-ketimine lithium complex Download PDFInfo
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- CN111909194A CN111909194A CN202010839957.0A CN202010839957A CN111909194A CN 111909194 A CN111909194 A CN 111909194A CN 202010839957 A CN202010839957 A CN 202010839957A CN 111909194 A CN111909194 A CN 111909194A
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- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/11—Lithium
Abstract
The invention discloses a method for catalyzing ketone cyanogen silicification reaction by a deprotonated phenyl bridging beta-ketimine lithium complex, which comprises the following steps of taking the deprotonated phenyl bridging beta-ketimine lithium complex as a catalyst, taking ketone and silane as raw materials, reacting for 15 minutes at room temperature, and completing cyanogen silicification reaction, wherein each beta-ketimine unit in the complex is a double negative ion, and the double negative ion beta-ketimine group is a group with high activity, and the complex is applied to the cyanogen silicification reaction of the ketone, wherein the reaction temperature is room temperature, and the reaction time is short, so that the high-efficiency reduction of the ketone and TMSCN can be realized.
Description
Technical Field
The invention relates to a lithium complex and application thereof in the field of organic synthesis, in particular to a deprotonated beta-ketimine lithium complex, a preparation method thereof and application thereof in cyanide silicification of ketone.
Background
The beta-ketimine is used as an important non-cyclopentadienyl ligand, and has the characteristics of easy synthesis, convenient regulation and control of charge and space effect through the change of alpha-position and beta-position substituent groups, capability of being coordinated with metal in various coordination modes to form a metal complex with structural diversity and the like. However, the use of beta-ketimine anionic ligands has been less investigated than the study of beta-diimine anionic ligands in organometallic chemistry. The existing reports focus on the complex taking single negative ion beta-ketimine as a framework. There have been no reports to date on complexes of dianionic-ketimine ligands.
In the prior art, n-butyllithium, ketone and silane are mixed and then subjected to a cyanosilicification reaction, so that the method has a good catalytic effect on ketone, the substrate is wide in trial range, but n-butyllithium uses a high catalyst dosage, and the time for catalyzing the cyanosilicification reaction of ketone is long. In the prior art, firstly, a Mg-Al hydrotalcite laminate is prepared; polyacid intercalation hydrotalcite catalytic material prepared by intercalating polyacid into a hydrotalcite laminate by a stripping recombination method not only avoids the problem of impurity equality easily occurring in the traditional polyacid intercalation hydrotalcite process, but also has higher catalytic activity on the addition reaction of aliphatic aldehyde, aromatic aldehyde and ketone, but the preparation process is complex. In the prior art, a metal organic framework Ni-MOF-1 is synthesized by an organic ligand L, then, crystals of the Ni-MOF-1 are heated for 4-6 hours at 100 ℃ to prepare Ni-MOF-2, and finally, the Ni-MOF-2 is immersed in an iodine gas phase atmosphere for 24 hours to obtain a novel iodine-loaded catalyst Ni-MOF-3, wherein the catalyst can effectively catalyze a benzaldehyde siliconizing reaction without a solvent reaction, so that the harm of a toxic solvent to the environment is reduced; but the catalyst preparation is complicated.
Disclosure of Invention
The invention aims to provide the application of a deprotonated phenyl bridged beta-ketimine lithium complex in the cyanide silicification reaction, which is a novel ketone cyanide silicification reaction method and has a good substrate application range.
In order to achieve the purpose, the invention adopts the technical scheme that:
the method for catalyzing the ketone cyanogen silicification reaction by the deprotonated phenyl bridging beta-ketimine lithium complex comprises the following steps of taking the deprotonated phenyl bridging beta-ketimine lithium complex as a catalyst and taking ketone and silane as raw materials to complete the cyanogen silicification reaction.
The application of the deprotonated phenyl bridged beta-ketimine lithium complex in ketone cyanation reaction, wherein ketone and silane are used as reaction substrates in the cyanation reaction.
In the invention, the chemical structural formula of the deprotonated phenyl bridged beta-ketimine lithium complex is as follows:
in the invention, the preparation method of the deprotonated phenyl bridged beta-ketimine lithium complex comprises the following steps of mixing a small molecular organic lithium solution and a ligand solution under the protection of argon gas, and then reacting to obtain a catalyst deprotonated phenyl bridged beta-ketimine lithium complex; the ligand has the following chemical structural formula:
in the technical scheme, the temperature of the cyanide silicification reaction is room temperature, the time is 10-18 min, preferably 15min, and then the reaction is terminated by contacting with air.
In the above technical scheme, the silane is trimethylsilyl cyanide (TMSCN); the ketone is acetophenone, p-methylacetophenone, o-fluoroacetophenone, benzophenone and 3-acetylpyridine.
In the technical scheme, the dosage of the catalyst deprotonated phenyl bridged beta-ketimine lithium complex is 0.05 percent of the molar weight of ketone; the silane to ketone molar ratio was 1.1: 1.
The cyanosilicification reaction of the invention is carried out under the condition of no solvent.
In the present invention, the cyanation reaction is carried out under an inert atmosphere, and the inert atmosphere is preferably nitrogen.
The reaction of the cyanosilicidation reaction of the present invention is schematically as follows:
due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention relates to a beta-ketimine ligand L bridged by ortho-phenylphH2When the compound reacts with four times equivalent of n-butyllithium hexane solution in THF, deprotonated o-phenyl bridged beta-ketimine lithium complex can be conveniently obtained, wherein each beta-ketimine unit is a double negative ion, and the double negative ion beta-ketimine group is a group with high activity, and can react with small molecules containing active hydrogen and unsaturated bond organic small molecules. Meanwhile, the complex can also be used as a precursor for further synthesizing the double-negative ion beta-ketimine rare earth metal complex. When the complex is applied to the cyanide silicification reaction of ketone, the efficient reduction of the ketone and TMSCN can be realized when 0.05 mol% of deprotonated phenyl bridged beta-ketiminate lithium complex is used as a catalyst, the reaction temperature is room temperature, and the reaction time is 15 min.
Drawings
FIG. 1 is a nuclear magnetic map of a product of example one;
FIG. 2 is a nuclear magnetic map of the four products of example.
Detailed Description
The raw materials involved in the invention are all commercial products, and under the preparation method of the invention, the specific operation steps and the test method are all conventional methods in the field; the synthesis of the beta-ketimine ligand is carried out in the air; the synthesis of the deprotonated phenyl bridged beta-ketimine lithium complex is carried out under the protection of argon; the cyanosilicidation reaction product may be used as such or subjected to conventional purification.
Calculating the nuclear magnetic yield:
nuclear magnetic yield = product characteristic peak area/raw material ketone characteristic peak area.
The first embodiment is as follows: [ L ]ph’Li4(THF)4]2Catalytic reduction reaction of acetophenone and TMSCN
Adding catalyst 0.6 mg (0.0005 mmol, 0.05%) into the reaction flask after dehydration and deoxidation treatment under nitrogen atmosphere, sequentially adding acetophenone (116.6 μ L, 1.0 mmol) and TMSCN (137.6 μ L, 1.1 mmol) with pipette after reaction at room temperature for 15min, dropping one drop with dropper into nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.49-7.46 (m, 2H, ArH), 7.33-7.24 (m, 3H, ArH), 1.77 (s, 3H, CMe), 0.11 (s, 9H, Si(CH 3)3) The spectrum is shown in figure 1.
Example two: [ L ]ph’Li4(THF)4]2Catalyzing reduction reaction of p-methylacetophenone and TMSCN
Adding 0.6 mg (0.0005 mmol) of catalyst into a reaction flask subjected to dehydration and deoxidation treatment under nitrogen atmosphere, sequentially adding p-methylacetophenone (133.5 μ L, 1.0 mmol) and TMSCN (137.6 μ L, 1.1 mmol) with a pipette, reacting at room temperature for 15min, sucking one drop with a dropper into a nuclear magnetic tube, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.46 (d, 3 J H-H = 8.3 Hz, 2H, ArH), 7.22 (d, 3 J H-H = 8.0 Hz, 2H, ArH), 2.38 (s, 3H, Ar-CH 3), 1.86 (s, 3H, CMe), 0.19 (s, 9H, Si(CH 3)3)。
example three: [ L ]ph’Li4(THF)4]2Catalytic reduction reaction of o-fluoro acetophenone and TMSCN
0.6 mg (0.0005 mmo) of a catalyst was added to the dehydrated and deoxidized reaction flask in a nitrogen atmosphereL), adding o-fluoro acetophenone (124.1 μ L, 1.0 mmol) and TMSCN (137.6 μ L, 1.1 mmol) in sequence by using a pipette, reacting at room temperature for 15min, sucking one drop by using a dropper, placing in a nuclear magnetic tube, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 7.54-7.50 (m, 1H, ArH), 7.30-7.25 (m, 1H, ArH), 7.13-7.09 (m, 1H, ArH), 7.04-6.99 (m, 1H, ArH), 1.87 (s, 3H, CMe), 0.19 (s, 9H, Si(CH 3)3)。
example four: [ L ]ph’Li4(THF)4]2Catalytic reduction reaction of benzophenone and TMSCN
Adding 0.6 mg (0.0005 mmol) of catalyst and benzophenone (182.2 mg, 1.0 mmol) into a reaction flask subjected to dehydration and deoxidation treatment under nitrogen atmosphere, adding TMSCN (137.6 μ L, 1.1 mmol) by using a pipette, reacting at room temperature for 30 min, dropping one drop by using a dropper into a nuclear magnetic tube, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%.1H NMR (400 MHz, CDCl3) 7.44-7.41 (m, 4H, ArH), 7.27-7.21 (m, 6H, ArH), 0.06 (s, 9H, Si(CH 3)3) The spectrum is shown in FIG. 2.
Example five: [ L ]ph’Li4(THF)4]2Catalytic reduction reaction of 3-acetylpyridine and TMSCN
Adding 0.6 mg (0.0005 mmol) of catalyst into a reaction flask subjected to dehydration and deoxidation treatment under nitrogen atmosphere, sequentially adding 3-acetylpyridine (109.9 μ L, 1.0 mmol) and TMSCN (137.6 μ L, 1.1 mmol) with a pipette, reacting at room temperature for 15min, sucking one drop with a dropper into a nuclear magnetic tube, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 97%. Nuclear magnetic data of the product:1H NMR (400 MHz, CDCl3) 8.77 (d, 3 J H-H = 1.9 Hz, 1H, ArH), 8.56 (d, 3 J H-H = 4.8, 1.5 Hz, 1H, ArH), 7.87-7.75 (m, 1H, ArH), 7.29 (d, 3 J H-H = 8.4, 5.2 Hz, 1H, ArH), 1.83 (s, 3H, CMe), 0.16 (s, 9H, Si(CH 3)3)。
synthesis example
Ortho-phenyl bridged beta-ketimine ligands (L)phH2) Synthesis of (2)
Adding 150 mL of absolute ethyl alcohol, 10.8 g of m-phenylenediamine (100 mmol) and 20.5 mL of acetylacetone (200 mmol) into a three-necked bottle, heating and refluxing the mixture for 24 hours by using a catalytic amount of p-toluenesulfonic acid to obtain a mixture of a reddish brown liquid and a light yellow solid, performing suction filtration, and recrystallizing the solid by using the absolute ethyl alcohol to obtain 24.5 g of light yellow needle-shaped crystals, wherein the yield is 90 percent and is ligand LphH2。1H NMR (400 MHz, CDCl3)：12.47 (2H, s, NH)，7.32-7.27 (1H, m, ArH), 6.94-6.91 (2H, m, ArH), 6.86 (1H, s, ArH), 5.21 (2H, s, CH=C(CH3)N)，2.10 (6H, s, CH 3)，2.01 (6H, s, CH 3)。13C NMR (101 MHz, CDCl3): 196.54 (COCH3), 159.62 (C=CH), 139.63 (ArC), 129.71 (ArC), 121.45 (ArC), 120.43 (ArC), 98.20 (=CH), 29.25 (CH3), 19.94 (CH3)。HRMS (ESI-MS) calcd. for C16H20N2O2 [M+H]+: 273.1558, found: 273.1633。
Deprotonated phenyl bridged beta-ketiminate lithium complexes [ Lph’Li4(THF)4]2Synthesis of (2)
A solution of n-butyllithium (19.40 mmol, 2.5M) in hexane was added to L under ice-bath conditionsphH2(4.85 mmol) of tetrahydrofuran solutionIn the solution, the solution is gradually changed into light orange red turbid solution from light yellow clear solution, and after the solution is added for 1 minute, the reaction is carried out for 12 hours at room temperature; after the reaction, the reaction solution was heated to 100 deg.CoC, changing the supernatant into orange red clear liquid, concentrating the clear liquid until turbidity appears, centrifuging, continuously concentrating the supernatant until a large amount of broken crystals are generated, heating to dissolve, naturally cooling to room temperature, sealing the bottle, standing at room temperature for 50 minutes to precipitate a large amount of light yellow crystals [ L ]ph’Li4(THF)4]2 {Lph’ = C6H4[NC(CH3)=CHCO=CH2]2Dry it by routine separation to give 2.22 g of product in 78% yield. Melting point: 194.6-196.7oC。1H NMR (400 MHz, d8-THF)： 7.29 (s, 1H, ArH), 6.95 (t, J = 7.7 Hz, 3H, ArH), 6.31 (d, J = 2.0 Hz, 2H, =CH 2), 6.29 (d, J = 2.0 Hz, 2H, =CH 2), 5.18 (t, J = 1.9 Hz, 2H, CH=C(CH3)N), 1.66 (s, 6H, CH 3). IR (KBr, cm-1): 3677, 3189, 2972, 1567, 1501, 1470, 1413, 1379, 1358, 1311, 1277, 1239, 1194, 1153, 1065, 1021, 968, 926, 886, 744, 697, 643。
Complex [ Lph’Li4(THF)4]2：
From complexes [ Lph’Li4(THF)4]2The single crystal structure and the crystallographic parameters of (A) show that the complex is a beta-ketimine lithium complex with a symmetrical structure, and THF (tetrahydrofuran) is respectively complexed on different Li atoms. There is no coordinating solvent around the Li (1) atom, two THF molecules are complexed around the Li (2) atom, and one THF molecule is complexed around the Li (3) atom and the Li (4) atom, respectively. It belongs to the triclinic system, P1 space group.
Crystal structure parameter of complex 1
The invention utilizes the deprotonated phenyl bridging beta-ketiminate lithium complex to catalyze the cyanation reaction of ketone and TMSCN, thereby developing a high-efficiency method for catalyzing the cyanation reaction, which has simple structure and easy synthesis, can catalyze the cyanation reaction of ketone and TMSCN with high activity at room temperature, the dosage of the catalyst is only 0.05 percent of the molar weight of ketone, the reaction yield can reach more than 99 percent, and compared with the existing catalytic system, the dosage of the catalyst is reduced, the temperature is mild, and the yield is very high.
Claims (9)
1. The method for catalyzing the ketone cyanogen silicification reaction by the deprotonated phenyl bridging beta-ketimine lithium complex comprises the following steps of taking the deprotonated phenyl bridging beta-ketimine lithium complex as a catalyst and taking ketone and silane as raw materials to complete the cyanogen silicification reaction; the chemical structural formula of the deprotonated phenyl bridged beta-ketimine lithium complex is as follows:
2. the method of claim 1 wherein the deprotonated lithium phenyl bridged beta-ketiminate complex catalyzes the reaction of cyanosilicidation of a ketone at a silane to ketone molar ratio of 1.1: 1.
3. The method of claim 1, wherein the ketone is acetophenone, p-methylacetophenone, o-fluoroacetophenone, benzophenone, or 3-acetylpyridine.
4. The method of claim 1, wherein the silane is trimethylsilyl cyanide.
5. The method of claim 1 wherein the cyanation reaction is carried out under an inert atmosphere.
6. Use of the deprotonated phenyl bridged beta-ketiminate lithium complex of claim 1 in a ketocyansilicidation reaction.
7. The use of a deprotonated phenyl bridged beta-ketiminate lithium complex according to claim 6 in a ketone cyanation reaction, characterized in that the temperature of the cyanation reaction is room temperature.
8. The use of a deprotonated phenyl-bridged lithium β -ketiminate complex according to claim 6 in a ketocyanation reaction, characterized in that the catalyst is used in an amount of 0.05% by mole based on the ketone.
9. The application of the deprotonated phenyl bridged beta-ketimine lithium complex in ketone cyanation silicification reaction according to claim 6, characterized in that the cyanation silicification reaction time is 10-18 min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021253846A1 (en) * | 2020-06-16 | 2021-12-23 | 苏州大学 | DEPROTONATED β-KETIMINE LITHIUM COMPOUND AND PREPARATION METHOD THEREFOR |
| WO2021253868A1 (en) * | 2020-06-16 | 2021-12-23 | 苏州大学 | Method for hydroboration of carbonate |
| WO2022040891A1 (en) * | 2020-08-24 | 2022-03-03 | 苏州大学 | USE OF DEPROTONATED PHENYL-BRIDGED β-KETIMINE LITHIUM COORDINATION COMPLEX IN CYANOSILICATE REACTION |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021253846A1 (en) * | 2020-06-16 | 2021-12-23 | 苏州大学 | DEPROTONATED β-KETIMINE LITHIUM COMPOUND AND PREPARATION METHOD THEREFOR |
| WO2021253868A1 (en) * | 2020-06-16 | 2021-12-23 | 苏州大学 | Method for hydroboration of carbonate |
| WO2022040891A1 (en) * | 2020-08-24 | 2022-03-03 | 苏州大学 | USE OF DEPROTONATED PHENYL-BRIDGED β-KETIMINE LITHIUM COORDINATION COMPLEX IN CYANOSILICATE REACTION |
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