CN110790649A - Method for synthesizing polysubstituted α unsaturated ketone - Google Patents
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
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- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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Abstract
The invention relates in particular to a synthesisA process for polysubstituted α unsaturated ketone includes such steps as mixing Ni (cod)2Nitrogen heterocyclic carbene ligands, Cs2CO3β, adding gamma unsaturated ketone into nonpolar aprotic organic solvent, mixing to obtain a mixture, adding the mixture obtained in the step one into a dried container for reaction at 120-180 ℃ for 10-40 hours, cooling to room temperature after the reaction to obtain a crude product, and purifying in the step three, wherein the method adopts cheap Ni (cod)2As a catalyst, carbon-carbon bonds are activated by transition metals, and the isomerization of double bonds provides power for the reaction, the synthetic method is simple, the substrate is stable and cheap, the reaction is less limited by the substrate, and the substrate has wide applicability.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for synthesizing polysubstituted α unsaturated ketone.
Background
The traditional method for synthesizing the compound is greatly limited by substrates, and requires that two ketones participating in the reaction are the same compound or one ketone does not have a hydrogen atom at α, so that the compound cannot participate in the reaction as an electrophilic reagent.
In addition, foreign literature reports new methods for synthesizing these compounds.A new method for synthesizing these compounds by ring opening of cyclopropane is reported, for example, in (J.Am. chem. Soc.1981,103,2404-2405), but this method requires the use of an unstable three-membered ring as a substrate for the reaction, and the synthesis of the three-membered ring itself has a great difficulty.A three-component reaction involving a allene is reported, for example, in (J.Am. chem. Soc.2003,125,12576-12583), but this reaction also uses a highly active allene as a substrate, and for this reason, it is necessary to invent a new method for synthesizing α unsaturated ketones.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for synthesizing polysubstituted α unsaturated ketoneThe method of (1), which uses inexpensive Ni (cod)2As a catalyst, carbon-carbon bonds are activated by transition metals, and the isomerization of double bonds provides power for the reaction, the synthetic method is simple, the substrate is stable and cheap, the reaction is less limited by the substrate, and the substrate has wide applicability.
The technical problem to be solved by the invention is realized by the following technical scheme:
a method of synthesizing a polysubstituted α unsaturated ketone, comprising the steps of:
the method comprises the following steps: mixing Ni (cod)2Nitrogen heterocyclic carbene ligands, Cs2CO3β, adding gamma unsaturated ketone into nonpolar aprotic organic solvent, and mixing to obtain mixture;
step two: and (3) adding the mixture obtained in the step one into a dried container for reaction at the temperature of 120-180 ℃ for 10-40 hours, and cooling to room temperature after the reaction is finished to obtain a crude product.
Preferably, the method for synthesizing the polysubstituted α unsaturated ketone further comprises a third step of filtering the crude product obtained in the second step, concentrating the filtrate in vacuum to obtain filter residue, and purifying the filter residue by using a silica gel column chromatography to obtain α unsaturated ketone.
Preferably, the nitrogen heterocyclic carbene ligand is 1, 3-bis (2,4, 6-trimethylphenyl) imidazolium chloride, 1, 3-bis- (2, 6-diisopropylphenyl) imidazolium chloride, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride or 1, 3-dicyclohexylimidazole chloride.
Preferably, the nonpolar aprotic organic solvent is dioxane, toluene, or xylene.
Preferably, the above-mentioned Ni (cod)2And the nitrogen heterocyclic carbene ligand is prepared from the following raw materials in a molar ratio of 1: 2.
preferably, the above-mentioned Ni (cod)2The content of (a) is 5-15 mol%, the content of the azacyclo-carbene ligand is 10-30 mol%, and the content of Cs is2CO3The content of (B) is 20 to 35 mol%.
Preferably, the above-mentioned Ni (cod)2The content of (a) is 10 mol%, and the content of the nitrogen heterocyclic carbene ligand20 mol% of the total amount of the above-mentioned Cs2CO3The content of (B) is 30 mol%.
Preferably, the reaction temperature is 150 ℃ and the reaction time is 24 hours.
Preferably, the reaction formula of the method for synthesizing the polysubstituted α unsaturated ketone is shown as the formula (A):
wherein R is: phenyl, 2-methylphenyl, 3-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-cyanophenyl, 4-ethylphenyl, 4-methoxyphenyl, phenol, 4-isopropylphenyl, 4-tert-butylphenyl, 4-phenylphenyl, 2-naphthyl, 2-furyl, 2-thienyl, a phenyl five-membered cyclic group, 2- (2-propenyl) phenyl or phenethyl.
Preferably, the reaction formula of the method for synthesizing the polysubstituted α unsaturated ketone is shown as the formula (B):
wherein R is1、R2、R3Respectively selected from any one of ethyl, phenyl, methyl, n-hexyl, phenethyl, five-membered (benzo) ring to eight-membered ring, androsteronyl, heptyl or nonyl.
Compared with the prior art, the invention has the beneficial effects that:
1. the reaction system is simple, only a catalyst and a ligand need to be added in the reaction, and the adopted α -site acyl-substituted olefin compound substrate is obtained, so that the substrate is stable and easy to obtain, and the preparation cost is low;
2. the reaction system is clean, the conversion rate is high, the catalyst in the system is only required to be filtered, and the product is easy to separate;
3. the process of the present invention is widely applicable, most common functional groups are applicable to the process, substrates are widely applicable, and cyclic α unsaturated ketones and acyclic α unsaturated ketones can be prepared according to the process.
Drawings
FIG. 1 is a drawing of the product of example 11H NMR spectrum.
FIG. 2 is a photograph of the product of example 113C NMR spectrum.
FIG. 3 is an X-RAY spectrum of the product of example 1.
FIG. 4 is β of example 1, a process for preparing gamma-unsaturated ketones1H NMR spectrum.
FIG. 5 is β of example 1, a process for preparing gamma-unsaturated ketones13C NMR spectrum.
FIG. 6 is the HRMS spectrum of β, a gamma unsaturated ketone, from example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
The invention provides a method for synthesizing α unsaturated ketone, which comprises the following steps:
the method comprises the following steps: 5 to 15 mol% of Ni (cod)210-30 mol% of nitrogen heterocyclic carbene ligand and 20-35 mol% of Cs2CO3β, adding gamma unsaturated ketone into nonpolar aprotic organic solvent, and mixing to obtain mixture;
step two: adding the mixture obtained in the step one into a dried container for reaction, wherein the reaction temperature is 120-180 ℃, the reaction time is 10-40 hours, and cooling to room temperature after the reaction is finished to obtain a crude product;
and step three, filtering the crude product in the step two, concentrating the filtrate in vacuum to obtain filter residue, and purifying the filter residue by using a silica gel column chromatography method to obtain α unsaturated ketone.
Wherein the nitrogen heterocyclic carbene ligand can be 1, 3-bis (2,4, 6-trimethylphenyl) imidazolium chloride, 1, 3-bis- (2, 6-diisopropylphenyl) imidazolium chloride, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride or 1, 3-dicyclohexyl imidazolium chloride, and the nitrogen heterocyclic carbene ligand can adjust the electronic effect and the stereoscopic effect of a catalyst Ni center. Ni (cod)2And the nitrogen heterocyclic carbene ligand is prepared from the following raw materials in a molar ratio of 1: 2, 1 mol of Ni(cod)2Coordinated to 2 moles of azacyclo-carbene ligand. In view of the solubility of the substrate and the catalyst, the nonpolar aprotic organic solvent is selected for the method, and dioxane, toluene or xylene is selected for the nonpolar aprotic organic solvent in the embodiment.
The method of the invention can synthesize α unsaturated ketone of non-cyclic product and α unsaturated ketone of cyclic product by the same mechanism according to different reaction substrate structures.
(1) The reaction formula for the synthesis of the α unsaturated ketone for the acyclic product is as follows:
wherein R is: phenyl, 2-methylphenyl, 3-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-cyanophenyl, 4-ethylphenyl, 4-methoxyphenyl, phenol, 4-isopropylphenyl, 4-tert-butylphenyl, 4-phenylphenyl, 2-naphthyl, 2-furyl, 2-thienyl, a phenyl five-membered cyclic group, 2- (2-propenyl) phenyl or phenethyl.
The structural formula of the product is as follows:
(2) the reaction formula for the synthesis of the α unsaturated ketone for the acyclic product is as follows:
wherein R is1、R2、R3Respectively selected from any one of ethyl, phenyl, methyl, n-hexyl, phenethyl, five-membered (benzo) ring to eight-membered ring, androsteronyl, heptyl or nonyl.
The structural formula of the product is as follows:
example 1:
adding 0.02mmol of Ni (cod)20.04mmol of 1, 3-bis- (2, 6-diisopropylphenyl) imidazolium chloride (SIPr. HCl), 0.06mmol of Cs2CO3And 0.2mmol of β gamma unsaturated ketone is added into 2mL of dioxane to be mixed, the mixture is added into a sealed and dried test tube in a glove box to react, oil bath heating is adopted, the temperature is controlled to be 150 ℃, the reaction is carried out for 24 hours under the stirring condition, a crude mixture is prepared, the crude mixture is naturally cooled to the room temperature and is filtered through a silica gel pad, filter residue is obtained after the filtrate is vacuum-concentrated, silica gel column chromatography is used for purifying by using ethyl acetate and petroleum ether, α unsaturated ketone is obtained, and the yield is 76%.
The product is detected by NMR, HRMS and x-Ray1The H NMR spectrum is shown in FIG. 1, and the product is13The C NMR spectrum is shown in FIG. 2, and the X-RAY spectrum of the product is shown in FIG. 3.
With reference to figure 1 of the drawings,1H NMR(600MHz,CDCl3):δ7.80–7.79(m,2H),7.39–7.36(m,1H),7.30–7.27(m,2H),6.13–6.08(dd,J＝10.8Hz,J＝18.0Hz,1H),5.17–5.12(m,
2H),1.31(s,6H)；13C NMR(125MHz,CDCl3):δ204.6,143.7,136.9,131.6,129.2,127.8,113.9,50.0,25.9.HRMS(ESI)m/z calculated for C12H14ONa[M+Na]+
197.0937,found 197.0923。
in this example, β, the synthesis method of γ unsaturated ketone is:
step 1: in THF/H2To O (30.0ml/30.0ml) were added aldehyde (10.0mmol) and bromide 2(12.0mmol), and zinc powder (12.0mmol) was added in portions at 0 ℃. The reaction mixture was stirred at room temperature for 12 h, then filtered and extracted with EtOAc (3X 50 mL). The combined organic phases were washed with brine, Na2SO4And (5) drying. In the presence of a solventFiltering and evaporating under reduced pressure, and purifying the crude product by silica gel column chromatography to obtain the alcohol.
Step 2: ethanol (10.0mmol) was dissolved in DCM (50.0mL), PCC (25.0mmol) was added at rt, stirred for 3h and the consumption of ethanol was determined by TLC analysis. The reaction mixture was filtered through EtOAc (3X 50mL) and extracted. The combined organic phases were washed with brine, Na2SO4Drying, filtering the solvent under reduced pressure, evaporating, purifying the crude product by silica gel column chromatography to obtain β, gamma unsaturated ketone, detecting the product by NMR and HRMS, and obtaining the product1The H NMR spectrum is shown in FIG. 4, of the product13The C NMR spectrum is shown in FIG. 5, and the HRMS spectrum of the product is shown in FIG. 6.
The method for synthesizing the polysubstituted α unsaturated ketone adopts cheap Ni (cod)2The catalyst is used as a catalyst, the most advanced carbon-carbon bond activation method is adopted at present, α unsaturated ketone is quickly and efficiently obtained from simple compounds of benzaldehyde and allyl bromide through three-step reaction, the synthesis method is simple, the substrate is stable and cheap, and the substrate limitation is less.
Example 2:
0.02mmol of Ni (cod)2, 0.04mmol of 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride (IPr), 0.06mmol of Cs2CO3And 0.2mmol of β, gamma unsaturated ketone is added into 2mL of dioxane to be mixed, the mixture is added into a sealed and dried test tube in a glove box to react, oil bath heating is adopted, the temperature is controlled at 150 ℃, the reaction is carried out for 24 hours under the stirring condition, a crude mixture is prepared, the crude mixture is naturally cooled to the room temperature and is filtered through a silica gel pad, filter residue is obtained after the filtrate is vacuum-concentrated, silica gel column chromatography is used for purifying by using ethyl acetate and petroleum ether, α unsaturated ketone is obtained, and the yield is 66%.
Example 3:
adding 0.02mmol of Ni (cod)20.04mmol of 1, 3-bis (2,4, 6-trimethylphenyl) imidazolium chloride (IMEs), 0.06mmol of Cs2CO3And 0.2mmol of β, gamma-unsaturated ketone to 2mL of dioxane, mixing, adding into a sealed and dried test tube in a glove boxAnd (2) heating the mixture by adopting an oil bath, controlling the temperature to be 150 ℃, reacting for 24 hours under the stirring condition to obtain a crude mixture, naturally cooling the crude mixture to room temperature, filtering the crude mixture by using a silica gel pad, concentrating the filtrate in vacuum to obtain filter residue, and purifying the filter residue by using ethyl acetate and petroleum ether by using a silica gel column chromatography to obtain α unsaturated ketone, wherein the yield is 31%.
Example 4:
adding 0.02mmol of Ni (cod)20.04mmol of 1, 3-dicyclohexylimidazole chloride (ICy) and 0.06mmol of Cs2CO3And 0.2mmol of β gamma unsaturated ketone and 2mL of dioxane are added, mixed, added into a sealed and dried test tube in a glove box after mixing, and then reacted, oil bath heating is adopted, the temperature is controlled at 150 ℃, the reaction is carried out for 24 hours under the stirring condition, so as to obtain a crude mixture, the crude mixture is naturally cooled to the room temperature, then filtered through a silica gel pad, the filtrate is subjected to vacuum concentration to obtain filter residue, and silica gel column chromatography is used for purifying by using ethyl acetate and petroleum ether, so as to obtain α unsaturated ketone, wherein the yield is 46%.
Example 5:
adding 0.02mmol of Ni (cod)20.04mmol of 1, 3-bis- (2, 6-diisopropylphenyl) imidazolium chloride (SIPr. HCl), 0.06mmol of Cs2CO3Adding 0.2mmol of β gamma unsaturated ketone and 2mL of toluene, mixing, adding the mixture into a sealed and dried test tube in a glove box for reaction, heating by adopting an oil bath, controlling the temperature at 150 ℃, reacting for 24 hours under the stirring condition to obtain a crude mixture, naturally cooling the crude mixture to room temperature, filtering by using a silica gel pad, concentrating the filtrate in vacuum to obtain filter residue, and purifying by using ethyl acetate and petroleum ether by using a silica gel column chromatography to obtain α unsaturated ketone, wherein the yield is 58%.
Example 6:
adding 0.02mmol of Ni (cod)20.04mmol of 1, 3-bis- (2, 6-diisopropylphenyl) imidazolium chloride (SIPr. HCl), 0.06mmol of Cs2CO3And 0.2mmol of β, gamma-unsaturated ketone into 2mL of xylene, mixing, adding into a glove box, sealing and dryingAnd (2) reacting in the dried test tube, heating by adopting an oil bath, controlling the temperature to be 150 ℃, reacting for 24 hours under the stirring condition to obtain a crude mixture, naturally cooling the crude mixture to room temperature, filtering by using a silica gel pad, concentrating the filtrate in vacuum to obtain filter residue, and purifying by using ethyl acetate and petroleum ether by using a silica gel column chromatography to obtain α unsaturated ketone, wherein the yield is 35%.
Example 7:
adding 0.02mmol of Ni (cod)20.04mmol of 1, 3-bis- (2, 6-diisopropylphenyl) imidazolium chloride (SIPr. HCl), 0.06mmol of Cs2CO3Adding 0.2mmol of β gamma unsaturated ketone and 2mL of toluene, mixing, adding the mixture into a sealed and dried test tube in a glove box for reaction, heating by adopting an oil bath, controlling the temperature at 120 ℃, reacting for 24 hours under the stirring condition to obtain a crude mixture, naturally cooling the crude mixture to room temperature, filtering by using a silica gel pad, concentrating the filtrate in vacuum to obtain filter residue, and purifying by using ethyl acetate and petroleum ether by using a silica gel column chromatography to obtain α unsaturated ketone, wherein the yield is 40%.
Example 8:
adding 0.01mmol of Ni (cod)20.02mmol of 1, 3-bis- (2, 6-diisopropylphenyl) imidazolium chloride (SIPr. HCl), 0.04mmol of Cs2CO3Adding 0.2mmol of β gamma unsaturated ketone and 2mL of toluene, mixing, adding the mixture into a sealed and dried test tube in a glove box for reaction, heating by adopting an oil bath, controlling the temperature at 180 ℃, reacting for 10 hours under the stirring condition to obtain a crude mixture, naturally cooling the crude mixture to room temperature, filtering by using a silica gel pad, concentrating the filtrate in vacuum to obtain filter residue, and purifying by using ethyl acetate and petroleum ether by using a silica gel column chromatography to obtain α unsaturated ketone, wherein the yield is 50%.
Example 9:
adding 0.03mmol of Ni (cod)20.06mmol of 1, 3-bis- (2, 6-diisopropylphenyl) imidazolium chloride (SIPr. HCl), 0.07mmol of Cs2CO3And 0.2mmol of β, gamma-unsaturated ketone was added to 2mL of toluene and mixedMixing, adding the mixture into a sealed and dried test tube in a glove box for reaction, heating the mixture by adopting an oil bath, controlling the temperature at 150 ℃, reacting for 40 hours under the condition of stirring to obtain a crude mixture, naturally cooling the crude mixture to the room temperature, filtering the crude mixture by using a silica gel pad, concentrating the filtrate in vacuum to obtain filter residue, and purifying the filter residue by using ethyl acetate and petroleum ether by using a silica gel column chromatography to obtain α unsaturated ketone, wherein the yield is 62%.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A method for synthesizing polysubstituted α unsaturated ketone is characterized by comprising the following steps:
the method comprises the following steps: mixing Ni (cod)2Nitrogen heterocyclic carbene ligands, Cs2CO3β, adding gamma unsaturated ketone into nonpolar aprotic organic solvent, and mixing to obtain mixture;
step two: and (3) adding the mixture obtained in the step one into a dried container for reaction at the temperature of 120-180 ℃ for 10-40 hours, and cooling to room temperature after the reaction is finished to obtain a crude product.
2. The method for synthesizing polysubstituted α unsaturated ketone according to claim 1, further comprising the steps of, filtering the crude product obtained in step two, vacuum concentrating the filtrate to obtain a residue, and purifying the residue by silica gel column chromatography to obtain α unsaturated ketone.
3. The method for synthesizing polysubstituted α unsaturated ketones according to claim 1, wherein said azacyclo-carbene ligand is 1, 3-bis (2,4, 6-trimethylphenyl) imidazolium chloride, 1, 3-bis- (2, 6-diisopropylphenyl) imidazolium chloride, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride or 1, 3-dicyclohexylimidazolium chloride.
4. The method of synthesizing a polysubstituted α unsaturated ketone according to claim 1, wherein said non-polar aprotic organic solvent is dioxane, toluene or xylene.
5. The method for synthesizing polysubstituted α unsaturated ketone according to claim 1, wherein said Ni (cod)2And the nitrogen heterocyclic carbene ligand is prepared from the following raw materials in a molar ratio of 1: 2.
6. the method for synthesizing polysubstituted α unsaturated ketone according to claim 1, wherein said Ni (cod)2The content of (a) is 5-15 mol%, the content of the azacyclo-carbene ligand is 10-30 mol%, and the content of Cs is2CO3The content of (B) is 20 to 35 mol%.
7. The method of synthesizing polysubstituted α unsaturated ketones according to claim 6, wherein said Ni (cod)2The content of (A) is 10 mol%, the content of the azacyclo-carbene ligand is 20 mol%, and the content of Cs is2CO3The content of (B) is 30 mol%.
8. The method of claim 7, wherein the reaction temperature is 150 ℃ and the reaction time is 24 hours.
9. The method for synthesizing polysubstituted α unsaturated ketones according to any one of claims 1-8, wherein the reaction formula is represented by formula (A):
wherein R is: phenyl, 2-methylphenyl, 3-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-cyanophenyl, 4-ethylphenyl, 4-methoxyphenyl, phenol, 4-isopropylphenyl, 4-tert-butylphenyl, 4-phenylphenyl, 2-naphthyl, 2-furyl, 2-thienyl, a phenyl five-membered cyclic group, 2- (2-propenyl) phenyl or phenethyl.
10. The method for synthesizing polysubstituted α unsaturated ketones according to any one of claims 1-8, wherein the reaction formula is represented by formula (B):
wherein R is1、R2、R3Respectively selected from any one of ethyl, phenyl, methyl, n-hexyl, phenethyl, five-membered (benzo) ring to eight-membered ring, androsteronyl, heptyl or nonyl.
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| CN114380679A (en) * | 2020-10-19 | 2022-04-22 | 中国科学院大连化学物理研究所 | Palladium catalytic oxidation coupling method |
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| CN1343191A (en) * | 1999-03-12 | 2002-04-03 | 巴斯福股份公司 | Method of producing cyclic, bata-unsaturated ketones |
| CN108929215A (en) * | 2018-08-03 | 2018-12-04 | 浙江工业大学 | A kind of synthetic method of the halogenated alpha, beta unsaturated ketone class compound of cis- α |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380679A (en) * | 2020-10-19 | 2022-04-22 | 中国科学院大连化学物理研究所 | Palladium catalytic oxidation coupling method |
| CN114380679B (en) * | 2020-10-19 | 2022-12-20 | 中国科学院大连化学物理研究所 | Palladium catalytic oxidation coupling method |
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