CN117402063A - Full-carbon tetra-substituted olefin and preparation method thereof - Google Patents

Full-carbon tetra-substituted olefin and preparation method thereof Download PDF

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CN117402063A
CN117402063A CN202311350292.7A CN202311350292A CN117402063A CN 117402063 A CN117402063 A CN 117402063A CN 202311350292 A CN202311350292 A CN 202311350292A CN 117402063 A CN117402063 A CN 117402063A
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substituted olefin
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刘乐
贺重隆
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Xian Jiaotong University
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
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    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/51—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to an acyclic carbon atom of a carbon skeleton containing six-membered aromatic rings
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    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • 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
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
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    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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Abstract

A full-carbon tetra-substituted olefin and a preparation method thereof are provided, wherein the reaction process is as follows:

Description

Full-carbon tetra-substituted olefin and preparation method thereof
Technical Field
The invention belongs to the technical field of chemical synthesis, and mainly relates to an all-carbon tetra-substituted olefin and a preparation method thereof.
Background
The four substituent groups of the full-carbon tetra-substituted olefin are all in a carbide structure, widely exist in bioactive compounds and drug molecules, are key skeletons forming a plurality of drug active molecules, and contain full-carbon tetra-substituted olefin fragments in the structures of anticancer drugs such as tamoxifen, idoxifene, etaxifene, etaxiline, and selective estrogen receptor degradation agent GDC-0810. In addition, due to the unique structural characteristics and physical and chemical properties, the full-carbon tetra-substituted olefin is widely applied to the fields of molecular devices, liquid crystal materials, organic synthesis and the like as a high-activity synthesis intermediate. Therefore, the construction of all-carbon tetra-substituted olefin frameworks has been a research hotspot in the field of organic synthetic chemistry, attracting a great deal of attention from a large number of researchers.
At present, the existing methods for preparing the relevant frameworks mainly comprise the following steps: 1) Wittig reaction, horner-Wadsworth-Emmons (HWE) reaction (chem. Rev.1989,89,863), julia alkenylation reaction (Comp. Org. Syn 1991,1,729), peterson reaction (In Organic Reactions; wiley,1990; vol.38; p 1.) and McMurry reactions et al (Modern Carbonyl Olefination, takeda, t., ed.; wiley-VCH Weinheim, germany, 2004). Related methods generally have poor stereoselectivity; 2) Tetra-substituted olefins are produced by the elimination reaction of tertiary alcohol derivatives. However, synthesis of alcohol precursors in this approach is often challenging and several elimination pathways are difficult to control stereoselectivity (org.process res.dev.2001,5,479). 3) Prepared by internal alkyne carbo-metalation (Pergamon Press: oxford,1995; vol.12, p 387), but this approach lacks regional control and functional group tolerance. And the reaction needs to use a metal catalyst, is difficult to recycle and is easy to cause environmental problems such as metal pollution. In addition, trisubstituted activated olefins (J.Am. Chem. Soc.2017,139, 10777-10783) can be used to prepare highly stereoselective full-carbon tetrasubstituted olefins by the Suzuki-Miyaura coupling method. The method needs to synthesize the activated trisubstituted olefin first, and meanwhile, needs to use noble metal palladium as a reaction catalyst, so that the cost is high, and the problem of environmental pollution can be caused.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide full-carbon tetra-substituted olefin and a preparation method thereof, wherein difunctional reagent formula I and alkyne formula II are used as raw materials under the action of a metal-free catalyst, and the reaction is carried out under the action of visible light irradiation under the action of a photocatalyst and alkali, so that a compound shown in a formula III is obtained after the reaction is finished; the method uses the organic photosensitizer as the catalyst, has the advantages of simple and easily obtained raw materials, mild reaction conditions, simple operation, wide substrate universality, easy mass production and low cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an all-carbon tetra-substituted olefin having the structure shown in formula III:
wherein: x represents a heteroatom including oxygen, nitrogen, carbon, sulfur or other heteroatoms;
R 1 functional groups include methyl, methoxy, t-butyl, electron donating substituents, halogen, trifluoromethyl, cyano, ester, carbonyl, ether, or aryl heterocycles;
R 2 functional groups include methyl, methoxy, t-butyl, electron donating substituents, halogen, trifluoromethyl, cyano, ester, carbonyl, ether, or aryl heterocycles;
R 3 functional groups include methyl, ethyl, propyl, alkyl substituents, benzene rings, substituted benzene rings, or aryl heterocycles;
R 4 the functional group comprises methyl, ethyl, propyl and other alkyl substituents, benzene rings, substituted benzene rings or other aryl heterocycles.
A preparation method of full-carbon tetra-substituted olefin, the reaction formula is as follows:
wherein: x represents a heteroatom including oxygen, nitrogen, carbon, sulfur or other heteroatoms;
y is any one of the following: sulfone, sulfoxide, carbonyl or ester groups;
R 1 functional groups include methyl, methoxy, t-butyl, electron donating substituents, halogen, trifluoromethyl, cyano, ester, carbonyl, etherOr an aryl heterocycle;
R 2 functional groups include methyl, methoxy, t-butyl, electron donating substituents, halogen, trifluoromethyl, cyano, ester, carbonyl, ether, or aryl heterocycles;
R 3 functional groups include methyl, ethyl, propyl, alkyl substituents, benzene rings, substituted benzene rings, or aryl heterocycles;
R 4 the functional group comprises methyl, ethyl, propyl and other alkyl substituents, benzene rings, substituted benzene rings or other aryl heterocycles.
A process for the preparation of an all-carbon tetra-substituted olefin comprising the steps of:
1) Sequentially adding difunctional reagents of formula I Amol, alkyne formula II B mol, photocatalyst C mol%, alkali D mol and reaction solvent into a reaction tube filled with magnetons under the atmosphere of nitrogen, and carrying out illumination reaction after sealing the reaction system, wherein the ratio of A to B to C is that D=1: (1-3.5): (0.1% -10%): (0.5-3.5);
2) The reaction is monitored by a TLC plate until the reaction is complete, after cooling to room temperature, the reaction is quenched by saturated sodium chloride aqueous solution, extracted by ethyl acetate, the organic phase is distilled under reduced pressure, the solvent is distilled off, and the crude product is separated by column chromatography to obtain the full-carbon tetra-substituted olefin.
The photocatalyst is selected from one of the following: eosin Y, fluorescein, rhodamine B, 4-CzTPN, TPT, ru (bpy) 3 Cl 2 6H 2 O、Ir(ppy) 3 NDI, acridine perchlorate.
The base is selected from one of the following: sodium hydroxide, potassium tert-butoxide, sodium carbonate, sodium acetate, disodium hydrogen phosphate, potassium phosphate trihydrate, cesium carbonate, lithium carbonate, sodium hydride.
The reaction solvent is selected from one of the following: ethyl acetate, tetrahydrofuran, dichloromethane, dichloroethane, nitromethane, acetonitrile, benzene, toluene, chlorobenzene, benzotrifluoride, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide; the reaction solvent is calculated by the dosage of the formula I according to the reaction concentration, and the reaction concentration is 0.1-0.5M.
When the crude product is separated by column chromatography, 200-300 mesh silica gel is adopted, and ethyl acetate is adopted for the crude product: petroleum ether=4:1 eluent to give the target all-carbon tetra-substituted olefin.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a novel full-carbon tetra-substituted olefin structure skeleton and a preparation method thereof, wherein the structure comprises a tetra-substituted olefin structure, the substituent group types are various, the post-derivatization modification is easy to carry out, and the support can be provided for the activity test of related medicaments.
2. The invention adopts the raw materials of the difunctional reagent formula I and the alkyne formula II to react under the action of the photocatalyst, and synthesizes the tetra-substituted olefin compound in one step by a butt joint migration strategy, thereby overcoming the difficulties and disadvantages of high cost, poor functional group tolerance, poor substituent selectivity and environmental pollution commonly existing in the existing synthesis method.
3. The invention has simple and mild reaction condition, can realize high-efficiency and high-selectivity conversion by only adding the photosensitizer and the inorganic base, has good economy of the whole reaction atoms and no byproduct generation, and the highest yield of the product can reach 90 percent.
In conclusion, the method has obvious advantages, including mild conditions, safe and simple operation, convenient post-treatment, green and environment-friendly performance, high yield, cheap and easily obtained raw materials, wide application range of substrates, good tolerance of functional groups and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the product IIIa of an all-carbon tetra-substituted olefin.
Fig. 2 is a nuclear magnetic carbon spectrum of the all-carbon tetra-substituted olefin product IIIa.
Fig. 3 is a nuclear magnetic hydrogen spectrum of the all-carbon tetra-substituted olefin product IIIb.
Fig. 4 is a nuclear magnetic carbon spectrum of the all-carbon tetra-substituted olefin product IIIb.
Fig. 5 is a nuclear magnetic hydrogen spectrum of the all-carbon tetra-substituted olefin product IIIc.
Fig. 6 is a nuclear magnetic carbon spectrum of the all-carbon tetra-substituted olefin product IIIc.
Fig. 7 is a nuclear magnetic hydrogen spectrum of the all-carbon tetra-substituted olefin product IIId.
Fig. 8 is a nuclear magnetic carbon spectrum of the all-carbon tetra-substituted olefin product IIId.
Fig. 9 is a nuclear magnetic hydrogen spectrum of the all-carbon tetra-substituted olefin product IIIe.
Fig. 10 is a nuclear magnetic carbon spectrum of the all-carbon tetra-substituted olefin product IIIe.
The present invention will be described in detail with reference to the accompanying drawings.
Example 1
The implementation reaction formula of the invention is shown as follows:
the product prepared in this example has the structure:
the preparation method of the embodiment comprises the following steps: to a 100mL reaction tube containing a magneton under nitrogen atmosphere, ethyl 2- (phenylsulfonyl) acetate (2.3 g,10 mmol), but-1-yn-1-ylbenzone (2.6 g,20 mmol), TPT (200 mg,5 mol), cesium carbonate (6.5 g,20 mmol) and acetone (50 mL) were sequentially added; after the reaction tube was sealed, the reaction tube was transferred to a light source (420-470 nm) and stirred, the progress of the reaction was checked by TLC plate, and after the reaction was completed, the reaction was quenched with saturated aqueous sodium chloride solution, extracted with ethyl acetate and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to give a crude reaction product, which was separated by column chromatography to give tetra-substituted olefin as colorless liquid IIIa (2.6 g, 89%), r.r.>20:1; with reference to figures 1 and 2 of the drawings, 1 H NMR(400MHz,CDCl 3 )δ7.32–7.26(m,4H),7.24–7.19(m,6H),4.19–4.13(m,2H),3.19(s,2H),2.25–2.19(m,2H),1.28(t,J＝7.2Hz,3H),1.06(t,J＝7.5Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ172.2,142.7,142.6,141.4,133.4,129.3,129.2,128.2,128.1,126.7,126.6,60.6,37.7,26.3,14.3,13.2.HRMS(ESI,m/z):calcd.for C 20 H 22 O 2 Na + [M+Na] + 317.1512,found 317.1512。
example 2
The product prepared in this exampleThe structure is as follows:
the preparation method of the embodiment comprises the following steps: to a 100mL reaction tube containing a magneton under nitrogen atmosphere, ethyl 2- (phenylsulfonyl) acetate (2.3 g,10 mmol), prop-1-yn-1-ylbenzene (2.3 g,20 mmol), TPT (200 mg,5 mol%), cesium carbonate (6.5 g,20 mmol) and acetone (50 mL) were sequentially added; sealing the reaction tube, transferring to a light source (420-470 nm), stirring, reacting for 24h, and detecting the reaction progress by a TLC plate; after the reaction was completed, the reaction was quenched with saturated aqueous sodium chloride solution, extracted with ethyl acetate and dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure to give a crude reaction product, which was separated by column chromatography to give tetra-substituted olefin as colorless liquid IIIb (2.4 g, 85%), r.r.>20:1; with reference to figures 3 and 4 of the drawings, 1 H NMR(400MHz,CDCl 3 )δ7.32–7.30(m,4H),7.24–7.19(m,6H),4.21–4.16(m,2H),3.16(s,2H),1.87(s,3H),1.29(t,J＝7.2Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ172.1,142.6,142.5,141.2,129.7,129.5,128.2,128.1,127.7,126.8,126.6,60.6,41.3,20.5,14.4.HRMS(ESI,m/z):calcd.for C 19 H 20 O 2 H + [M+H] + 281.1536,found 281.1541。
example 3
The product prepared in this example has the structure:
the preparation method of the embodiment comprises the following steps: to a 100mL reaction tube containing a magneton under nitrogen atmosphere, ethyl 2- (phenylsulfonyl) acetate (2.3 g,10 mmol), (3-methoxprop-1-yn-1-yl) benzene (2.3 g,20 mmol), TPT (200 mg,5 mol%), cesium carbonate (6.5 g,20 mmol) and acetone (50 mL) were sequentially added; sealing the reaction tube, transferring to a light source (420-470 nm), stirring, reacting for 24h, and detecting the reaction progress by a TLC plate; after the reaction was completed, the reaction was quenched with saturated aqueous sodium chloride solution, extracted with ethyl acetate and dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure to give a crude reaction product, which was separated by column chromatography to give tetra-substituted olefin as colorless liquid IIIc (2.8 g, 90%), r.r.>20, a step of; reference toFig. 5, 6,1; 1 H NMR(400MHz,CDCl 3 )δ7.32–7.25(m,5H),7.24–7.18(m,5H),4.18–4.03(m,2H),4.02(s,2H),3.29(s,3H),3.25(s,2H),1.27(t,J＝7.1Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ172.1,144.7,141.9,141.4,129.4,129.2,129.1,128.3,128.1,127.2(overlapped),72.5,60.6,58.3,36.8,14.3.HRMS(ESI,m/z):calcd.for C 20 H 22 O 3 H + [M+H] + 311.1642,found 311.1657。
example 4
The product prepared in this example has the structure:
the preparation method of the embodiment comprises the following steps: to a 100mL reaction tube containing a magneton under nitrogen atmosphere, ethyl 2- (phenylsulfonyl) acetate (2.3 g,10 mmol), tert-butyl methyl (3-phenylprop-2-yn-1-yl) oxy) silane (4.9 g,20 mmol), TPT (200 mg,5 mol%), cesium carbonate (6.5 g,20 mmol) and acetone (50 mL) were added in this order; sealing the reaction tube, transferring to a light source (420-470 nm), stirring, reacting for 24h, and detecting the reaction progress by a TLC plate; after the reaction was completed, the reaction was quenched with saturated aqueous sodium chloride solution, extracted with ethyl acetate and dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure to give a crude reaction product, which was separated by column chromatography to give tetra-substituted olefin as colorless liquid IIId (2.5 g, 62%), r.r.>20:1; with reference to figures 7 and 8 of the drawings, 1 H NMR(400MHz,CDCl 3 )δ7.31–7.19(m,10H),4.27(s,2H),4.18–4.12(m,2H),3.28(s,2H),1.27(t,J＝7.2Hz,3H),0.89(s,9H),0.01(s,6H). 13 C NMR(101MHz,CDCl 3 )δ172.2,142.7,142.1,141.5,131.5,129.6,129.4,128.3,128.1,127.2,127.1,63.2,60.1,36.3,26.0,18.4,14.3,5.3.HRMS(ESI,m/z):calcd.for C 25 H 34 O 3 SiNa + [M+Na] + 433.2169,found 433.2177。
example 5
The product prepared in this example has the structure:
the preparation method of the embodiment comprises the following steps: to a 100mL reaction tube containing a magneton under nitrogen atmosphere, ethyl 2- (phenylsulfonyl) acetate (2.3 g,10 mmol), ethyl 3-phenylpropionate (3.5 g,20 mmol), TPT (200 mg,5 mol%), cesium carbonate (6.5 g,20 mmol) and acetone (50 mL) were sequentially added; sealing the reaction tube, transferring to a light source (420-470 nm), stirring, reacting for 24h, and detecting the reaction progress by a TLC plate; after the reaction was completed, the reaction was quenched with saturated aqueous sodium chloride solution, extracted with ethyl acetate and dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure to give a crude reaction product, which was separated by column chromatography to give tetra-substituted olefin as colorless liquid IIIe (1.9 g, 55%) and r.r.>20:1; the method comprises the steps of carrying out a first treatment on the surface of the With reference to figures 9 and 10 of the drawings, 1 H NMR(400MHz,CDCl 3 )δ7.36–7.30(m,3H),7.29–7.26(m,3H),7.17–7.12(m,4H),4.20–4.15(m,2H),3.98–3.92(m,2H),3.46(s,2H),1.26(t,J＝7.2Hz,3H),0.87(t,J＝7.1Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ171.2,169.5,151.4,142.1,140.6,129.1,128.7,128.3,128.2,127.8,127.7,125.2,60.8,60.6,38.2,14.1,13.4.HRMS(ESI,m/z):calcd.for C 21 H 22 O 4 Na + [M+Na] + 361.1410,found 361.1423。
with reference to the preparation method, the following is a specific summary of examples of the oxidizing agent, the metal catalyst, the temperature and the solvent:
TABLE 1 summary of examples of the invention for the difunctional reagent (formula I), the photocatalyst, the base and the solvent
Similar experimental results can be obtained by replacing the solvent DMF in example 16 with other solvents such as tetrahydrofuran, dichloroethane, nitromethane, benzene, chlorobenzene, benzotrifluoride, N-dimethylacetamide, etc., and the target product can be obtained in a yield of more than 75%.
TABLE 2 summary of the examples of the reaction raw materials
As can be seen from the examples, the present invention allows the reaction to be carried out on a 10mmol scale, compared to the prior art, with up to 90% yield of the desired product. By utilizing simple condensation reaction, natural products or drug molecules can be introduced into the molecules, so that the conversion efficiency of related reactions is improved, the synthetic steps of all-carbon tetra-substituted olefins are reduced, and the atomic economy of the conversion efficiency is higher. The method has the advantages of simple and easily obtained raw materials, mild reaction conditions, simple operation, wide substrate universality, easy mass production and low cost.

Claims (7)

1. An all-carbon tetra-substituted olefin, characterized by: the structure is shown as a formula III:
wherein: x represents a heteroatom including oxygen, nitrogen, carbon, sulfur or other heteroatoms;
R 1 functional groups include methyl, methoxy, t-butyl, electron donating substituents, halogen, trifluoromethyl, cyano, ester, carbonyl, ether, or aryl heterocycles;
R 2 the functional groups include methyl, methoxy, tert-butyl, electron donating substituents, halogen, triFluoromethyl, cyano, ester, carbonyl, ether or aryl heterocycle;
R 3 functional groups include methyl, ethyl, propyl, alkyl substituents, benzene rings, substituted benzene rings, or aryl heterocycles;
R 4 the functional group comprises methyl, ethyl, propyl and other alkyl substituents, benzene rings, substituted benzene rings or other aryl heterocycles.
2. A method for preparing full-carbon tetra-substituted olefin, which is characterized by comprising the following reaction formula:
wherein: x represents a heteroatom including oxygen, nitrogen, carbon, sulfur or other heteroatoms;
y is any one of the following: sulfone group, sulfoxide group, carbonyl group, ester group;
R 1 functional groups include methyl, methoxy, t-butyl, electron donating substituents, halogen, trifluoromethyl, cyano, ester, carbonyl, ether, or aryl heterocycles;
R 2 functional groups include methyl, methoxy, t-butyl, electron donating substituents, halogen, trifluoromethyl, cyano, ester, carbonyl, ether, or aryl heterocycles;
R 3 functional groups include methyl, ethyl, propyl, alkyl substituents, benzene rings, substituted benzene rings, or aryl heterocycles;
R 4 the functional group comprises methyl, ethyl, propyl and other alkyl substituents, benzene rings, substituted benzene rings or other aryl heterocycles.
3. The method for preparing the full-carbon tetra-substituted olefin according to claim 2, comprising the following steps:
1) Sequentially adding difunctional reagents of formula I Amol, alkyne formula II B mol, photocatalyst C mol%, alkali D mol and reaction solvent into a reaction tube filled with magnetons under the atmosphere of nitrogen, and carrying out illumination reaction after sealing the reaction system, wherein the ratio of A to B to C is that D=1: (1-3.5): (0.1% -10%): (0.5-3.5);
2) The reaction is monitored by a TLC plate until the reaction is complete, after cooling to room temperature, the reaction is quenched by saturated sodium chloride aqueous solution, extracted by ethyl acetate, the organic phase is distilled under reduced pressure, the solvent is distilled off, and the crude product is separated by column chromatography to obtain the full-carbon tetra-substituted olefin.
4. A process for the preparation of an all-carbon tetra-substituted olefin according to claim 3, wherein the photocatalyst is selected from one of the following: eosin Y, fluorescein, rhodamine B, 4-CzTPN, TPT, ru (bpy) 3 Cl 2 6H 2 O、Ir(ppy) 3 NDI, acridine perchlorate.
5. A process for the preparation of an all-carbon tetra-substituted olefin according to claim 3, wherein the base is selected from one of the following: sodium hydroxide, potassium tert-butoxide, sodium carbonate, sodium acetate, disodium hydrogen phosphate, potassium phosphate trihydrate, cesium carbonate, lithium carbonate, sodium hydride.
6. A process for the preparation of an all-carbon tetra-substituted olefin according to claim 3, wherein the reaction solvent is selected from one of the following: ethyl acetate, tetrahydrofuran, dichloromethane, dichloroethane, nitromethane, acetonitrile, benzene, toluene, chlorobenzene, benzotrifluoride, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide; the reaction solvent is calculated by the dosage of the formula I according to the reaction concentration, and the reaction concentration is 0.1-0.5M.
7. The method for preparing full-carbon tetra-substituted olefin according to claim 2, wherein when the crude product is separated by column chromatography, 200-300 mesh silica gel is adopted, and ethyl acetate is used for the crude product: petroleum ether=4:1 eluent to give the target all-carbon tetra-substituted olefin.
CN202311350292.7A 2023-10-18 2023-10-18 Full-carbon tetra-substituted olefin and preparation method thereof Pending CN117402063A (en)

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