CN114890881B - Method for simply synthesizing allyl dicarbonyl compound - Google Patents
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Abstract
The invention discloses a simple synthesis method of allyl dicarbonyl compound, which comprises the steps of adding 0.5mmol of dicarbonyl compound and 0.75mmol of olefin into 3-4 mL of DMSO in a reaction vessel to prepare a solvent, then respectively adding 5%, 10% and 200% of catalyst cobalt (III), agOTf (silver triflate) and additive TFA (trifluoroacetic acid) into the solvent, reacting for 12-24 h under the oil bath condition of 80-100 ℃, cooling to room temperature, adding water, extracting three times by using ethyl acetate, merging organic layers, concentrating under reduced pressure, and purifying the product by column chromatography to obtain the allyl dicarbonyl compound. The method is not only suitable for a large number of functional groups, but also has the advantages of simple operation, high yield, single product, convenient separation and purification, safety, low cost and little pollution.
Description
Technical Field
The invention relates to synthesis of organic matters, in particular to a simple method for synthesizing an allyl dicarbonyl compound, which is a method for synthesizing the allyl dicarbonyl compound by using cobalt (III)/silver triflate to catalyze diketones, olefin and DMSO.
Background
Allyl dicarbonyl compounds are very important organic synthesis reagents and intermediates. Allylation is an important method for constructing carbon-carbon, carbon-heteroatom bonds, and has been a popular field of chemical research. In recent years, stable nucleophiles (C, N, O) have evolved over the field of metal catalyzed allylation reaction research. The traditional allylation reaction of the carbon nucleophile is mainly obtained by coupling an active alkyl metal reagent and an allyl electrophile. However, the metal alkyl reagents are typically prepared by reacting an alkyl halide with an equivalent of an active metal (Mg, zn, li, al, zr, etc.), and require storage and use under anhydrous, oxygen-free, and low temperature conditions. In addition, the strong basicity and nucleophilic nature of the alkyl metal reagent often results in poor chemoselectivity and functional group compatibility of the reaction. Later development of alkyl boron reagent solves the problems of chemoselectivity, functional group compatibility and the like, but the limitation of the reaction is very prominent, and the reaction is mainly characterized in the following three aspects: (1) The substrates to be reacted often require additional steps to be pre-functionalized, such as preparing electrophiles with easy leaving groups; (2) In the reaction process, an equivalent or excessive amount of alkali is required to act with a nucleophile; (3) the range of substrates required for the reaction is relatively narrow. At present, the most common allylation reaction of Tsuji-Trost is brought to extensive attention and intensive research of scientific researchers, and research of catalysts such as metal Ru, rh, pd, ni, ir, fe, cu and the like is achieved with a great deal of effort, and in the catalytic process, the commonly used allylation reagent is an allylation compound containing a leaving group. The more reactive leaving groups are more susceptible to oxidative addition reactions with the low-valence metal catalyst and thus the more susceptible the reaction. Common allyl alcohol, allyl halohydrocarbon, allyl ester, allylamine and the like pre-modify leaving groups before reaction, so that the application range of catalytic reaction is limited to a certain extent, and the synthesis efficiency is also deeply influenced. With the deep research of a catalytic system, the research of substituting common allyl reagents has been advanced to a certain extent. Firstly, taking a carbon nucleophile as an example, in 2008, shi Zhangjie subject composition work realizes allylation reaction of metal Pd (II) catalyzed intermolecular propenyl benzene as an allylation reagent, the novel allylation reaction of Pd (II) catalyzed intermolecular allylation sp 3C-H bond and methylene sp 3C-H bond not only widens the application of the traditional Tsuji-Trost allylation reaction, but also provides possibility for researching chiral stereoselectivity, unfortunately, other unsaturated hydrocarbons (diene, 1, 3-conjugated diene, 1-phenyl-1-propyne and 3-phenyl-1-propyne) are removed from a substrate of the reaction as the allylation reagent, and research on allylation products generated by the reaction of the novel Pd (II) with common nucleophile under the action of transition metal catalysts of nickel, rhodium, palladium and the like is also advanced by the inventor. The reaction of palladium-catalyzed allenes with nucleophiles was reported by the laboratories in the university of bloom Luo San, respectively; the Breit group studied rhodium catalyzed allenes and 3-substituted-1-propynes; the Dong subject group successfully realizes the allylation reaction of the rhodium catalyzed 1-phenyl-1-propyne; the university of south opening Zhou Jilin problem utilizes Ni (0)/DTBM-SegPhos to catalyze 1, 3-conjugated dienes and simple ketones to produce gamma, delta-unsaturated ketones in high yields and regioselectivity. These catalytic reactions all pass through a terminal metal pi-allyl complex and then under the action of a nucleophile, a non-terminal olefin with an allyl stereocenter or with an allyl stereocenter is obtained. Therefore, the novel and simple metal catalytic allylation reaction is researched, carbon-carbon and carbon heteroatom bonds are effectively constructed, and the method still has important theoretical significance and practical value.
With the development of economy, environmental problems are becoming more serious, and most of the main environmental problems in the world today are directly related to chemical reactions, chemical production processes and their products, so green chemistry is naturally an important component of green technology. In the field of organic synthesis, atomic economy has attracted widespread interest to researchers, in which Dimethylsulfoxide (DMSO), not only is a cheap, low-toxic, high-dissolving-capacity general-purpose solvent, but also is capable of providing O, S, me, SMe, SO 2 Me，CH 2 SMe，CHO，CN，CH 2 Has important research and application value in organic synthesis.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a simple method for synthesizing allyl dicarbonyl compound, which is not only applicable to a large number of functional groups, but also has the advantages of simple operation, high yield, single product, convenient separation and purification, safety, low cost and little pollution.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for the simple synthesis of an allyl dicarbonyl compound comprising the steps of:
adding 0.5mmol of dicarbonyl compound and 0.75mmol of olefin into 3-4 mL of DMSO to prepare a solvent, then respectively adding 5%, 10% and 200% of catalyst cobalt (III) of the molar weight of dicarbonyl compound and AgOTf (silver triflate) and additive TFA (trifluoroacetic acid) into the solvent, reacting for 12-24 h under the oil bath condition of 80-100 ℃, cooling to room temperature, adding water, extracting for three times by using ethyl acetate, merging organic layers, concentrating under reduced pressure, and purifying the product by column chromatography to obtain the allyl dicarbonyl compound; the chemical structural general formula is as follows:
wherein R is 1 Is alkyl, alkoxy, phenyl or substituted phenyl, R 2 Is alkyl, alkoxy, phenyl or substituted phenyl, R 3 Is H, alkyl, phenyl or substituted phenyl, R 4 Is H, alkyl, phenyl or substituted phenyl;
the reaction general formula of the synthesis method is shown as follows:
the dicarbonyl compound I is dibenzoylmethane derivative or diethyl malonate derivative.
The olefin II is styrene, p-methylstyrene, p-ethylstyrene, p-tert-butylstyrene, m-methylstyrene, 3, 4-dimethylstyrene, 3, 5-dimethylstyrene, 2-naphthylethylene, indene or 1, 1-diphenylethylene and derivatives thereof.
The column chromatography conditions are as follows: the 300-400 mesh silica gel column, and the eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1:10-1:50.
The invention adopts the method for simply synthesizing the allyl dicarbonyl compound, which is designed by the technical proposal, develops a method for synthesizing the allyl dicarbonyl compound by using cobalt (III)/silver triflate to catalyze diketone, alkene and DMSO, and has the following beneficial effects:
1. the invention has less acid consumption and reduces environmental pollution;
2. the invention has simple reaction substrate and wide sources, is suitable for various functional group substituted olefins (including ortho-position large steric hindrance functional group substituted olefins), and has small influence on the reaction due to the steric effect;
3. the method has the advantages of cheap reaction substrate, high yield, good selectivity, easy separation and purification, less pollution and simple steps, can omit the steps of protecting and deprotecting functional groups for synthesis, and is widely applicable to ligands, drug intermediates and photoelectric materials of organic chemical reactions;
4. compared with the prior art, the method is not only suitable for a large number of functional groups, but also simple in operation, single in product and convenient for separation and purification.
Drawings
FIG. 1 shows 2-cinnamoyl-1, 3-diphenylpropane-1, 3-dione (3 a) of example 1 of the invention 1 H NMR characterization map;
FIG. 2 shows 2-cinnamoyl-1, 3-diphenylpropane-1, 3-dione (3 a) of example 1 of the invention 13 C NMR characterization map.
Detailed Description
The invention discloses a method for simply synthesizing an allyl dicarbonyl compound, which comprises the following steps:
adding 0.5mmol of dicarbonyl compound and 0.75mmol of olefin into 3-4 mL of DMSO to prepare a solvent in a reaction vessel, then adding 5%, 10% and 200% of catalyst cobalt (III) of the molar weight of dicarbonyl compound and AgOTf (silver triflate) and additive TFA (trifluoroacetic acid) into the solvent respectively, reacting for 12-24 h under the oil bath condition of 80-100 ℃, cooling to room temperature, adding water, extracting three times by using ethyl acetate, combining organic layers, concentrating under reduced pressure, and purifying the product by column chromatography to obtain the allyl dicarbonyl compound. The chemical structural general formula is as follows:
wherein R is 1 Alkyl, alkoxy, phenyl or substituted phenyl, such as: F. cl, br, methyl, ethyl or tert-butyl; r is R 2 Alkyl, alkoxy, phenyl or substituted phenyl, such as: F. cl, br, methyl, ethyl or tert-butyl, R 3 H, alkyl, phenyl or substituted phenyl, such as: F. cl, br, methyl, R 4 H, alkyl, phenyl or substituted phenyl, such as: F. cl, br, methyl;
the reaction general formula of the synthesis method is shown as follows:
example 1
A method for synthesizing 2-cinnamoyl-1, 3-diphenylpropane-1, 3-dione (3 a), which comprises the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane, 0.75mmol (1.5 equivalent, 78.0 mg) of styrene (0.75 mmol,1.5 equivalent, 78.0 mg) of TFA (1.0 mol,2.0 equivalent), agOTf (13.0 mg,10 mol%), 4mL of solvent DMSO, were sequentially added into a 25mL reaction vessel, reacted in an oil bath at 100 ℃ for 24 hours, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, a 300-400 mesh silica gel column was used as an eluent, the volume ratio of the two was 1:10, 129.2mg of pale yellow liquid product was obtained, the yield was 76%, and the purity was 99%. 1 H NMR(400 MHz,CDCl 3 )δppm:7.97(d,J＝7.6Hz,4H),7.54-7.57(t,2H),7.42 -7.46(t,4H),7.24-7.25(m,4H),7.17-7.19(m,1H),6.46(d,J＝ 15.6Hz,1H),6.21-6.29(m,1H),5.35-5.39(t,1H),3.00-3.04(t, 2H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.6,136.9,135.9,133.5,132.4, 128.9,128.5,128.4,127.3,126.7,126.1,57.0,32.9；HRMS(ESI-TOF)m/zcalcd for C 24 H 21 O 2 [M+H] + 341.1536,found 341.1533.
Wherein the chemical structural general formula of the 2-cinnamoyl-1, 3-diphenylpropane-1, 3-diketone (3 a) is as follows:
example 2
A method for synthesizing 1, 3-diphenyl-2- (3- (p-tolyl) allyl) propane-1, 3-dione (3 b), comprising the following steps:
to a 25mL reaction vessel was successively charged 0.5mmol (112.0 mg) of dibenzoylmethane, p-methylstyrene (0.75 mmol,1.5 eq, 88.5 mg), TFA (1.0 mo)l,2.0 eq.) AgOTf (13.0 mg,10 mol%), solvent DMSO 3mL, in an oil bath at 100deg.C for 24h, cooling to room temperature, adding 20mL of water, extracting three times with 10mL of ethyl acetate, combining the organic layers, concentrating under reduced pressure, purifying the product by column chromatography, 300-400 mesh silica gel column, eluting with mixture of ethyl acetate and petroleum ether at a volume ratio of 1:10 to obtain 147.0mg of pale yellow liquid product with a yield of 83% and a purity of 99%. 1 H NMR (400MHz,CDCl 3 )δppm:7.97(d,J＝7.6Hz,4H),7.54-7.57(t,2H), 7.42-7.46(t,4H),7.15(d,J＝8.0Hz,2H),7.05(d,J＝8.0Hz,2H), 6.43(d,J＝16.0Hz,1H),6.15-6.21(m,1H),5.34-5.38(t,1H),2.99 -3.02(t,2H),2.29(s,3H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.5,137.1, 135.9,134.1,133.5,132.3,129.1,128.9,128.6,126.0,125.6,57.1,32.9, 21.1；HRMS(ESI-TOF)m/z calcd for C 25 H 23 O 2 [M+H] + 355.1693,found 355.1692.
Wherein, the chemical structural general formula of the 1, 3-diphenyl-2- (3- (p-tolyl) allyl) propane-1, 3-diketone (3 b) is as follows:
example 3
A method for synthesizing 2- (3- (4-ethylphenyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 c), comprising the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane, p-ethylstyrene (0.75 mmol,1.5 eq, 99.0 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 3mL, were sequentially added to a 25mL reaction vessel, reacted in an oil bath at 80℃for 24h, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, a 300-400 mesh silica gel column was a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10, 154.6mg of pale yellow liquid product was obtained in 84% yield and 99% purity. 1 H NMR(400 MHz,CDCl 3 )δppm:7.97(d,J＝7.6Hz,4H),7.54-7.57(t,2H),7.42 -7.46(t,4H),7.18(d,J＝8.0Hz,2H),7.08(d,J＝7.6Hz,2H),6.44 (d,J＝16.0Hz,1H),6.16-6.24(m,1H),5.35-5.38(t,1H),2.99- 3.03(t,2H),2.56-2.62(q,2H),1.17-1.12(t,3H)； 13 C NMR(100MHz, CDCl 3 )δppm:195.5,143.5,135.9,134.4,133.5,132.3,128.9,128.5, 127.9,126.1,125.7,57.1,32.9,28.5,15.5；HRMS(ESI-TOF)m/z calcd for C 26 H 25 O 2 [M+H] + 369.1849,found 369.1847.
Wherein the chemical structural formula of the 2- (3- (4-ethylphenyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 c) is as follows:
example 4
A method for synthesizing 2- (3- (4- (tert-butyl) phenyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 d), comprising the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane, p-tert-butylstyrene (0.75 mmol,1.5 eq, 120.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 3mL, were sequentially added to a 25mL reaction vessel, reacted in an oil bath at 90℃for 18h, cooled to room temperature, 20mL of water was added, extracted three times with 10mL of ethyl acetate, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, a 300-400 mesh silica gel column, the eluent was a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10, to give 156.4mg of a pale yellow liquid product in a yield of 79% and a purity of 99%. 1 H NMR(400 MHz,CDCl 3 )δppm:7.97(d,J＝8.0Hz,4H),7.55-7.59(t,2H),7.42 -7.48(t,4H),7.26-7.30(t,2H),7.21(d,J＝8.4Hz,2H),6.46(d, J＝16.0Hz,1H),6.17-6.25(m,1H),5.33-5.37(t,1H),3.00-3.03 (t,2H),1.29(s,9H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.5,150.4,135.9, 133.6,132.2,128.9,128.6,127.6,125.9,125.8,125.4,57.3,34.5,33.0, 31.2；HRMS(ESI-TOF)m/z calcd for C 28 H 29 O 2 [M+H] + 397.2162,found 397.2165.
Wherein the chemical structural general formula of the 2- (3- (4- (tert-butyl) phenyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 d) is as follows:
example 5
A method for synthesizing 2- (3- (4-ethylphenyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 e), comprising the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane, m-methylstyrene (0.75 mmol,1.5 eq, 88.5 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, were added sequentially to a 25mL reaction vessel, reacted in an oil bath at 100℃for 24h, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, a 300-400 mesh silica gel column, the eluent was a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10, and a pale yellow liquid product 145.1mg was obtained in 82% yield and 99% purity. 1 H NMR (400MHz,CDCl 3 )δppm:7.98(d,J＝7.6Hz,4H),7.54-7.58(t,2H), 7.43-7.47(t,4H),7.12-7.16(t,1H),7.05-7.08(m,2H),7.00(d, J＝7.2Hz,1H),6.43(d,J＝16.0Hz,1H),6.20-6.27(m,1H),5.34-5.38(t,1H),2.99-3.03(t,2H),2.29(s,3H)； 13 C NMR(100MHz,CDCl 3 ) δppm:195.5,138.0,136.9,135.9,133.5,132.5,128.9,128.6,128.3, 128.1,126.8,126.5,123.3,57.1,32.9,21.3；HRMS(ESI-TOF)m/z calcd for C 25 H 23 O 2 [M+H] + 355.1693,found 355.1694.
Wherein the chemical structural general formula of the 2- (3- (4-ethylphenyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 e) is as follows:
example 6
A method for synthesizing 2- (3, 4-xylyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 f), comprising the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane and 0.75m of 3, 4-dimethylstyrene (0.75 m) were successively introduced into a 25mL reaction vesselmol,1.5 eq, 99.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, reacting in an oil bath at 80 ℃ for 12h, cooling to room temperature, adding 20mL of water, extracting three times with 10mL of ethyl acetate, combining the organic layers, concentrating under reduced pressure, purifying the product by column chromatography, 300-400 mesh silica gel column, eluting with a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10, to obtain 158.2mg of pale yellow liquid product with 86% yield and 99% purity. 1 H NMR(400MHz,CDCl 3 )δppm:7.99(d,J＝7.6Hz,4H),7.55-7.58(t, 2H),7.43-7.47(t,4H),7.04(s,1H),6.96(d,J＝7.6Hz,1H),6.91(d,J＝7.6Hz,1H),6.61(d,J＝15.6Hz,1H),6.05-6.12(m,1H),5.36 -5.40(t,1H),3.03-3.06(t,2H),2.24(s,3H),2.18(s,3H)； 13 C NMR (100MHz,CDCl 3 )δppm:195.6,136.0,135.8,135.3,133.5,132.0,130.5, 130.0,128.9,128.6,128.0,127.6,126.2,57.1,33.3,20.9,19.2；HRMS (ESI-TOF)m/z calcd for C 26 H 25 O 2 [M+H] + 369.1846,found 369.1849.
Wherein the chemical structural formula of the 2- (3, 4-xylyl) allyl) -1, 3-diphenylpropane-1, 3-diketone (3 f) is as follows:
example 7
A method for synthesizing 2- (3, 5-xylyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 g), comprising the steps of:
0.5mmol (112.0 mg) of dibenzoylmethane, 0.75mmol (1.5 eq, 99.1 mg) of 3, 5-dimethyl styrene (0.75 mmol,1.5 eq, 99.1 mg) of TFA (1.0 mol,2.0 eq) of AgOTf (13.0 mg,10 mol%), 4mL of solvent DMSO, were sequentially added to a 25mL reaction vessel, reacted in an oil bath at 80 ℃ for 12h, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, and the product was purified by column chromatography with 300-400 mesh silica gel column as eluent, a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to obtain 161.9mg of pale yellow liquid product with 88% yield and 99% purity. 11 H NMR(400MHz,CDCl 3 )δppm:7.98(d,J＝7.6Hz,4H),7.56-7.59(t, 2H),7.44-7.48(t,4H),6.88(s,2H),6.84(s,1H),6.41(d,J＝16.0Hz,1H),6.20-6.26(m,1H),5.33-5.36(t,1H),2.99-3.02(t,2H), 2.56(s,6H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.6,137.9,136.9,135.9, 133.6,132.5,129.0,128.9,128.6,126.4,124.0,57.2,32.9,21.2；HRMS (ESI-TOF)m/z calcd for C 26 H 25 O 2 [M+H] + 369.1846,found 369.1842.
Wherein the chemical structural formula of the 2- (3, 5-xylyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 g) is as follows:
example 8
A method for synthesizing 2- (3- (naphthalene-2-yl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 h), comprising the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane, 0.75mmol,1.5 eq, 115.6mg of 2-vinylnaphthalene, TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), 4mL of solvent DMSO, were sequentially added to a 25mL reaction vessel, reacted in an oil bath at 900 ℃ for 16h, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, a 300-400 mesh silica gel column was used as an eluent, the volume ratio of ethyl acetate and petroleum ether was 1:10, 165.8mg of a pale yellow liquid product was obtained in 85% yield and 99% purity. 1 H NMR(400 MHz,CDCl 3 )δppm:8.00(d,J＝7.6Hz,4H),7.71-7.77(m,4H),7.62 (s,1H),7.56-7.59(t,2H),7.42-7.48(m,6H),6.63(d,J＝15.6Hz,1H),6.34-6.41(m,1H),5.39-5.42(t,1H),3.06-3.10(t,2H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.6,135.9,134.4,133.6,133.5,132.8, 132.6,128.9,128.6,128.1,127.9,127.6,127.2,126.2,125.9,125.7, 123.5,57.1,33.1；HRMS(ESI-TOF)m/z calcd for C 28 H 23 O 2 [M+H] + 391.1693, found 391.1695.
Wherein the chemical structural formula of the 2- (3- (naphthalene-2-yl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 h) is as follows:
example 9
A method for synthesizing 2- (3, 3-diphenylallyl) -1, 3-diphenylpropane-1, 3-dione (3 i), comprising the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane, 1-diphenylethylene (0.75 mmol,1.5 eq, 135.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, were sequentially added to a 25mL reaction vessel, reacted in an oil bath at 80℃for 10h, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, a 300-400 mesh silica gel column was used as an eluent, and the volume ratio of ethyl acetate and petroleum ether was 1:10, to obtain 185.1mg of a pale yellow liquid product with a yield of 89% and a purity of 99%. 1 H NMR(400 MHz,CDCl 3 )δppm:7.79(d,J＝7.6Hz,4H),7.50-7.54(t,2H),7.34 -7.39(m,7H),7.10-7.23(m,7H),6.26-6.30(t,1H),5.21-5.26 (m,1H),2.91-2.95(t,2H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.6,143.9, 141.7,139.5,135.8,133.4,129.7,128.8,128.5,128.46,128.0,127.2,127.0,125.5,57.1,29.2；HRMS(ESI-TOF)m/z calcd for C 30 H 25 O 2 [M+H] + 417.1849,found 417.1853.
Wherein the chemical structural formula of the 2- (3, 3-diphenylallyl) -1, 3-diphenylpropane-1, 3-dione (3 i) is as follows:
example 10
A method for synthesizing 2- (3, 3-di-p-tolylallyl) -1, 3-diphenylpropane-1, 3-dione (3 j), comprising the following steps:
to a 25mL reaction vessel was successively added 0.5mmol (112.0 mg) of dibenzoylmethane, 4' - (ethylene-1, 1-diyl) bis (toluene) (0.75 mmol,1.5 eq, 156.1 mg), TFA (1.0 mol,2.0 eq)) AgOTf (13.0 mg,10 mol%), solvent DMSO 4mL, in 80 ℃ oil bath reaction for 10h, cooling to room temperature, adding water 20mL, extracting with ethyl acetate 10mL three times, combining organic layers, concentrating under reduced pressure, purifying the product by column chromatography, 300-400 mesh silica gel column, eluting with ethyl acetate and petroleum ether mixture at volume ratio of 1:10, to obtain pale yellow liquid product 206.5mg, yield 93%, purity 99%. 1 H NMR(400MHz,CDCl 3 )δppm:7.79(d,J＝7.6Hz,4H),7.49-7.53(t, 2H),7.33-7.37(m,4H),7.17(d,J＝7.6Hz,2H),7.00-7.04(m,6H), 6.20-6.23(t,1H),5.21-5.25(t,1H),2.91-2.95(t,2H),2.39(s, 3H),2.27(s,3H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.7,143.7,139.1, 136.8,136.7,135.8,133.4,129.6,129.1,128.70,128.66,128.5,126.9,124.4,57.1,29.2,21.2,21.0；HRMS(ESI-TOF)m/z calcd for C 32 H 29 O 2 [M+ H] + 445.2162,found 445.2164.
Wherein the chemical structural formula of the 2- (3, 3-di-p-tolylallyl) -1, 3-diphenylpropane-1, 3-dione (3 j) is as follows:
example 11
A method for synthesizing 3- (3, 3-di (4-fluorophenyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 k), comprising the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane, 4' - (ethylene-1, 1-diyl) difluorobenzene (0.75 mmol,1.5 eq, 162.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, were sequentially added to a 25mL reaction vessel, reacted in an 80℃oil bath for 15h, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, 300-400 mesh silica gel column, eluent was a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10, to give 189.8mg of pale yellow liquid product with a yield of 84%, purity of 99%. 1 H NMR(400MHz,CDCl 3 )δppm:7.82(d,J＝8.0Hz,4H),7.53-7.57(t, 2H),7.38-7.42(m,4H),7.03-7.05(m,6H),6.87-6.91(t,2H),6.15 -6.19(t,1H),5.19-5.22(t,1H),2.90-2.93(t,2H)； 13 C NMR(100 MHz,CDCl 3 )δppm:195.6,163.3(d,J＝19.6Hz),160.9(d,J＝19.6Hz), 141.9,137.9(d,J＝3.4Hz),135.7,135.1(d,J＝3.4Hz),133.6,131.3 (d,J＝7.9Hz),128.9,128.6(d,J＝7.9Hz),128.5,125.7,115.5(d,J＝19.6Hz),114.9(d,J＝21.2Hz),114.9(d,J＝21.3Hz),57.1,29.2； 19 F NMR(376MHz,CDCl 3 )δppm:-114.7(m,1F),-115.1(m,1F)；HRMS (ESI-TOF)m/z calcd for C 30 H 23 O 2 F 2 [M+H] + 453.1661,found 453.1667.
Wherein the chemical structural formula of the 3- (3, 3-di (4-fluorophenyl) allyl) -1, 3-diphenylpropane-1, 3-dione (3 k) is as follows:
example 12
A method for synthesizing 2- (2- (10, 11-dihydro-5 h-dibenzo [ a, d ] [7] rotaene-5-methylene) ethyl) -1, 3-diphenylpropane-1, 3-dione (3 l), comprising the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane, 5-methylene-10, 11-dihydro-5H-dibenzo [ a, d ] was successively introduced into a 25mL reaction vessel][7]The rotaene (0.75 mmol,1.5 eq., 154.6 mg), TFA (1.0 mol,2.0 eq.), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, reacted in an oil bath at 100℃for 24h, cooled to room temperature, added 20mL of water, extracted three times with 10mL of ethyl acetate, combined with the organic layers, concentrated under reduced pressure, the product purified by column chromatography, 300-400 mesh silica gel column, eluent a mixture of ethyl acetate and petroleum ether, volume ratio of the two 1:10, gives 163.5mg of pale yellow liquid product with yield 74%, purity 99%. 1 H NMR(400MHz,CDCl 3 )δppm:7.86(d, J＝7.2Hz,2H),7.62(d,J＝7.2Hz,2H),7.49-7.52(t,2H),7.30- 7.39(m,4H),7.24(d,J＝4.4Hz,2H),7.19(d,J＝6.4Hz,1H),7.07 -7.14(m,4H),6.97(d,J＝6.8Hz,1H),6.03-6.06(t,1H),5.16-5.20(t,1H),3.17-3.27(m,2H),2.86-2.99(m,3H),2.69(d,J＝12.8 Hz,1H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.7,195.2,145.0,140.4,139.8, 139.4,136.8,133.4,130.1,128.79,128.78,128.55,128.52,128.46, 128.39,128.0,127.9,127.7,127.2,126.2,126.0,56.9,33.7,31.8,28.8； HRMS(ESI-TOF)m/z calcd for C 32 H 27 O 2 [M+H] + 443.2006,found 443.2002.
Wherein the chemical structural formula of the 2- (2- (10, 11-dihydro-5 h-dibenzo [ a, d ] [7] rotaene-5-methylene) ethyl) -1, 3-diphenylpropane-1, 3-dione (3 l) is as follows:
example 13
A method for synthesizing 2- (1H-indenyl-2-methyl) -1, 3-diphenylpropane-1, 3-dione (3 m), comprising the following steps:
0.5mmol (112.0 mg) of dibenzoylmethane, indene (0.75 mmol,1.5 equivalent, 87.1 mg) of TFA (1.0 mol,2.0 equivalent), agOTf (13.0 mg,10 mol%) of solvent DMSO 3mL, were sequentially added into a 25mL reaction vessel, reacted in an oil bath at 100 ℃ for 24 hours, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, a 300-400 mesh silica gel column was used as an eluent, and the volume ratio of ethyl acetate and petroleum ether was 1:10, thus obtaining 153.1mg of pale yellow liquid product with a yield of 87% and a purity of 99%. 1 H NMR(400MHz,CDCl 3 ) δppm:7.98(d,J＝8.0Hz,4H),7.52-7.56(t,2H),7.41-7.44(t, 4H),7.32(d,J＝7.2Hz,1H),7.15-7.22(m,2H),7.06-7.10(t,1H), 6.55(s,1H),5.55-5.59(t,1H),3.32(d,J＝7.2Hz,4H)； 13 C NMR(100 MHz,CDCl 3 )δppm:195.2,146.6,144.7,142.9,135.6,133.6,128.9,128.5, 128.2,126.2,124.1,123.3,120.2,56.9,41.5,30.3；HRMS(ESI-TOF)m/zcalcd for C 25 H 21 O 2 [M+H] + 353.1536,found 353.1531.
Wherein the chemical structural general formula of the 2- (1H-indenyl-2-methyl) -1, 3-diphenyl propane-1, 3-diketone (3 m) is as follows:
example 14
A method for synthesizing 2-cinnamyl-1-phenyl-3- (o-tolyl) propane-1, 3-dione (3 n), which comprises the following steps:
to a 25mL reaction vessel was successively added 0.5mmol (119.0 mg) of 1-phenyl-3- (o-tolyl) propane-1, 3-dione, styrene (0.75 mmol,1.5 eq, 78.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, reacted 24h in a 100℃oil bath, cooled to room temperature, added 20mL of water, extracted three times with 10mL of ethyl acetate, combined organic layers, concentrated under reduced pressure, the product purified by column chromatography, 300-400 mesh silica gel column, eluent a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to give 138.1mg of pale yellow liquid product with a yield of 78% and a purity of 99%. 1 H NMR(400MHz,CDCl 3 )δppm:7.91(d,J＝7.2Hz,2H),7.67(d, J＝7.6Hz,1H),7.49-7.53(t,1H),7.37-7.41(t,2H),7.31-7.34 (t,1H),7.16-7.24(m,7H),6.44(d,J＝15.6Hz,1H),6.20-6.28(m,1H),5.32-5.35(t,1H),2.94-3.05(m,2H),2.40(s,3H)； 13 C NMR(100 MHz,CDCl 3 )δppm:198.7,195.6,139.1,137.1,136.9,136.1,133.4,132.4, 132.1,131.6,128.7,128.42,128.37,127.9,127.2,126.6,126.0,125.7, 59.2,32.9,21.0；HRMS(ESI-TOF)m/z calcd for C 25 H 23 O 2 [M+H] + 355.1693, found 355.1692.
Wherein the chemical structural general formula of the 2-cinnamyl-1-phenyl-3- (o-tolyl) propane-1, 3-dione (3 n) is as follows:
example 15
A method for synthesizing 2-cinnamoyl-1-phenyl-3- (m-tolyl) propane-1, 3-dione (3 o), comprising the following steps:
to a 25mL reaction vessel was successively added 0.5mmol (119.0 mg) of 1-phenyl-3- (m-tolyl) propane-1, 3-dione, styrene (0.75 mmol,1.5 eq., 78.1 mg), TFA (1.0 mol,2.0 eq.), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, oil bath at 100 ℃The reaction is carried out for 24 hours, cooled to room temperature, 20mL of water is added, 10mL of ethyl acetate is used for extraction three times, the organic layers are combined, the reduced pressure concentration is carried out, the product is purified by column chromatography, a 300-400 mesh silica gel column is adopted, the eluent is a mixture of ethyl acetate and petroleum ether, the volume ratio of the two is 1:10, 134.5mg of pale yellow liquid product is obtained, the yield is 76%, and the purity is 99%. 1 H NMR(400MHz,CDCl 3 )δppm:7.96(d,J＝8.0Hz,2H),7.75 -7.80(m,2H),7.53-7.57(t,1H),7.41-7.45(t,2H),7.32-7.38 (m,2H),7.24-7.25(m,4H),7.17-7.19(m,1H),6.46(d,J＝15.6Hz,1H),6.21-6.28(m,1H),5.34-5.38(t,1H),2.99-3.03(t,2H),2.35 (s,3H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.7,195.5,138.8,136.9,135.93,135.87,134.4,133.5,132.4,129.1,128.8,128.7,128.5,128.4,127.3, 126.8,126.1,125.7,57.0,32.9,21.3；HRMS(ESI-TOF)m/z calcd for C 25 H 23 O 2 [M+H] + 355.1693,found 355.1695.
Wherein the chemical structural formula of the 2-cinnamoyl-1-phenyl-3- (m-tolyl) propane-1, 3-dione (3 o) is as follows:
example 16
A method for synthesizing 2-cinnamyl-1-phenyl-3- (p-tolyl) propane-1, 3-dione (3 p), comprising the following steps:
to a 25mL reaction vessel was successively added 0.5mmol (119.0 mg) of 1-phenyl-3- (p-tolyl) propane-1, 3-dione, styrene (0.75 mmol,1.5 eq, 78.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, reacted in an oil bath at 100℃for 24h, cooled to room temperature, added 20mL of water, extracted three times with 10mL of ethyl acetate, combined with the organic layers, concentrated under reduced pressure, the product purified by column chromatography, 300-400 mesh silica gel column with eluent as a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to give 143.4mg of pale yellow liquid product with a yield of 81% and a purity of 99%. 1 H NMR(400MHz,CDCl 3 )δppm:7.96(d,J＝7.6Hz,2H),7.88 (d,J＝8.4Hz,2H),7.52-7.55(t,1H),7.40-7.44(t,2H),7.16- 7.25(m,7H),6.45(d,J＝16.0Hz,1H),6.21-6.28(m,1H),5.32-5.36(t,1H),2.95-3.07(m,2H),2.37(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ ppm:195.5,195.1,144.5,136.9,135.9,133.4,133.3,132.3,129.6,128.8,128.7,128.5,128.4,127.2,126.8,126.1,56.9,32.9,21.6；HRMS(ESI-TOF) m/z calcd for C 25 H 23 O 2 [M+H] + 355.1693,found 355.1691.
Wherein the chemical structural general formula of the 2-cinnamyl-1-phenyl-3- (p-tolyl) propane-1, 3-dione (3 p) is as follows:
example 17
A method for synthesizing 2-cinnamoyl-1- (4-fluorophenyl) -3-phenylpropane-1, 3-dione (3 q), comprising the following steps:
to a 25mL reaction vessel was successively added 0.5mmol (121.0 mg) of 1- (4-fluorophenyl) -3-phenylpropane-1, 3-dione, styrene (0.75 mmol,1.5 eq, 78.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, reacted 24h in a 100℃oil bath, cooled to room temperature, added 20mL of water, extracted three times with 10mL of ethyl acetate, combined organic layers, concentrated under reduced pressure, and the product purified by column chromatography with 300-400 mesh silica gel column as eluent in a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to give 128.9mg of pale yellow liquid product with a yield of 72% and a purity of 99%. 1 H NMR(400MHz,CDCl 3 )δppm:7.96-8.01(m,4H),7.57-7.60 (t,1H),7.45-7.48(t,2H),7.25-7.29(t,4H),7.18-7.22(m,1H),7.09-7.13(t,2H),6.46(d,J＝16.0Hz,1H),6.19-6.21(m,1H),5.28 -5.32(t,1H),3.00-3.03(m,2H)； 13 C NMR(100MHz,CDCl 3 )δppm:195.4, 193.9,167.2,164.6,136.9,135.8,133.6(d,J＝13.8Hz),132.6,131.2(d,J＝9.4Hz),128.9(d,J＝6.2Hz),128.6,128.5,127.4,126.5,126.1, 116.1(d,J＝21.9Hz),57.3,32.9； 19 F NMR(376MHz,CDCl 3 )δppm:-103.9 (m,1F)；HRMS(ESI-TOF)m/z calcd for C 24 H 20 O 2 F[M+H] + 359.1442,found 359.1445.
Wherein the chemical structural general formula of the 2-cinnamoyl-1- (4-fluorophenyl) -3-phenylpropane-1, 3-dione (3 q) is as follows:
example 18
A method for synthesizing 2-cinnamoyl-1, 3-di-p-tolylpropane-1, 3-dione (3 r), comprising the following steps:
to a 25mL reaction vessel was successively added 0.5mmol (126.0 mg) of 1, 3-di-p-tolylpropane-1, 3-dione, styrene (0.75 mmol,1.5 eq, 78.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, reacted in an oil bath at 100℃for 24h, cooled to room temperature, added with 20mL of water, extracted three times with 10mL of ethyl acetate, combined with an organic layer, concentrated under reduced pressure, the product purified by column chromatography, 300-400 mesh silica gel column with eluent as a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to give 154.6mg of pale yellow liquid product with a yield of 84% and a purity of 99%. 1 H NMR(400MHz,CDCl 3 )δppm:7.87(d,J＝7.6Hz,4H),7.17- 7.25(m,9H),6.45(d,J＝16.0Hz,1H),6.21-6.29(m,1H),5.29-5.33(t,1H),2.98-3.02(t,2H),2.37(s,6H)； 13 C NMR(100MHz,CDCl 3 )δ ppm:195.2,144.4,137.0,133.4,132.2,129.5,128.7,128.4,127.2,127.0,126.1,56.9,33.0,21.6；HRMS(ESI-TOF)m/z calcd for C 26 H 25 O 2 [M+H] + 369.1849,found 369.1853.
Wherein the chemical structural general formula of the 2-cinnamoyl-1, 3-di-p-tolylpropane-1, 3-dione (3 r) is as follows:
example 19
A method for synthesizing 2-cinnamoyl-1-phenylbutane-1, 3-dione (3 s), comprising the following steps:
to a 25mL reaction vessel was successively charged 0.5mmol (81.0 mg) of 1-phenylbutane-1, 3-dione, styrene (0.75 mmol,1.5 equivalents,78.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, in a 100 ℃ oil bath reaction for 24h, cooling to room temperature, adding 20mL of water, extracting three times with 10mL of ethyl acetate, combining organic layers, concentrating under reduced pressure, purifying the product by column chromatography, 300-400 mesh silica gel column, eluting with a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10, to obtain 84.8mg of pale yellow liquid product with a yield of 61% and a purity of 99%. 1 H NMR (400MHz,CDCl 3 )δppm:8.01(d,J＝7.6Hz,2H),7.59-7.63(t,1H), 7.48-7.51(t,2H),7.20-7.28(m,5H),6.46(d,J＝15.6Hz,1H),6.10 -6.17(m,1H),4.60-4.64(t,1H),2.84-2.96(m,2H),2.18(s,3H)； 13 C NMR(100MHz,CDCl 3 )δppm:203.5,195.7,136.8,136.2,133.8,132.6, 128.9,128.7,128.5,127.4,126.1,125.8,63.1,32.4,28.3；HRMS(ESI-TOF)m/z calcd for C 19 H 19 O 2 [M+H] + 279.1380,found 279.1384.
Wherein the chemical structural general formula of the 2-cinnamoyl-1-phenylbutane-1, 3-diketone (3 s) is as follows:
example 20
A synthetic method of 2-cinnamyl-4, 4-dimethyl-1-phenylpentane-1, 3-dione (3 t), comprising the following steps:
to a 25mL reaction vessel was successively added 0.5mmol (102.0 mg) of 4, 4-dimethyl-1-phenylpentane-1, 3-dione, styrene (0.75 mmol,1.5 eq, 78.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, reacted 24h in a 100℃oil bath, cooled to room temperature, added 20mL of water, extracted three times with 10mL of ethyl acetate, combined organic layers, concentrated under reduced pressure, the product purified by column chromatography, 300-400 mesh silica gel column with eluent of a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10 to give 105.6mg of pale yellow liquid product with a yield of 66% and a purity of 99%. 1 H NMR(400MHz,CDCl 3 )δppm:8.02(d,J＝7.6Hz,2H),7.58- 7.62(t,1H),7.48-7.52(t,2H),7.23-7.26(m,4H),7.17-7.20(m, 1H),6.44(d,J＝16.0Hz,1H),6.08-6.15(m,1H),5.04-5.07(q,1H),2.95-3.02(m,1H),2.64-2.70(m,1H),1.11(s,9H)； 13 C NMR(100MHz, CDCl 3 )δppm:208.9,195.4,136.8,135.6,133.5,132.4,128.8,128.4, 128.3,127.2,126.3,125.9,55.2,44.6,33.7,26.2；HRMS(ESI-TOF)m/zcalcd for C 22 H 25 O 2 [M+H] + 321.1849,found 321.1852.
Wherein the chemical structural general formula of the 2-cinnamyl-4, 4-dimethyl-1-phenylpentane-1, 3-diketone (3 t) is as follows:
example 21
A method for synthesizing ethyl 2-benzoyl-5-phenyl-4-pentenoate (3 u), comprising the steps of:
to a 25mL reaction vessel were successively added 0.5mmol (146.0 mg) of ethyl benzoylacetate, 0.75mmol (0.75 mmol,1.5 eq, 78.1 mg) of styrene, TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), 4mL of solvent DMSO, reacted in an oil bath at 100℃for 24 hours, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, a 300-400 mesh silica gel column was used as an eluent, and the volume ratio of ethyl acetate and petroleum ether was 1:10, to give 78.5mg of a pale yellow liquid product, yield 51%, purity 99%. 1 H NMR(400 MHz,CDCl 3 )δppm:8.02(d,J＝6.8Hz,2H),7.58-7.61(t,1H),7.47 -7.51(t,2H),7.26-7.30(m,4H),7.20-7.22(m,1H),6.49(d,J＝15.6Hz,1H),6.19-6.23(m,1H),4.47(s,1H),4.14-4.16(t,2H), 2.91-2.92(m,2H),1.15-1.19(t,3H)； 13 C NMR(100MHz,CDCl 3 )δppm: 194.5,169.4,137.0,136.1,133.6,132.6,128.8,128.6,128.5,127.3,126.1,126.0,61.5,54.3,32.4,14.0；HRMS(ESI-TOF)m/z calcd for C 20 H 21 O 3 [M+H] + 309.1485,found 309.1488.
Wherein, the chemical structural general formula of the ethyl 2-benzoyl-5-phenyl-4-pentenoate (3 u) is as follows:
example 22
A synthesis method of diethyl 2-cinnamyl malonate (3 v), comprising the following steps:
to a 25mL reaction vessel were successively added diethyl malonate 0.5mmol (80.0 mg), styrene (0.75 mmol,1.5 eq, 78.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, reacted in an oil bath at 100℃for 24h, cooled to room temperature, added water 20mL, extracted three times with ethyl acetate 10mL, combined organic layers, concentrated under reduced pressure, the product purified by column chromatography, 300-400 mesh silica gel column, eluent a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10, to give 73.1mg of pale yellow liquid product with a yield of 53% and a purity of 99%. 1 H NMR(400MHz, CDCl 3 )δppm:7.25 7.33(m,4H),7.19-7.22(t,1H),6.48(d,J＝15.6 Hz,1H),6.12-6.19(m,1H),4.18-4.23(m,4H),3.47-3.51(t,1H), 2.78-2.82(t,2H),1.24-1.27(t,6H)； 13 C NMR(100MHz,CDCl 3 )δppm: 168.8,137.0,132.7,128.4,127.3,126.1,125.5,61.4,52.0,32.2,14.0； HRMS(ESI-TOF)m/z calcd for C 16 H 21 O 4 [M+H] + 277.1440,found 277.1443.
Wherein the chemical structural general formula of the diethyl 2-cinnamyl malonate (3 v) is as follows:
example 23
A synthesis method of 2-cinnamyl diisopropyl malonate (3 w), comprising the following steps:
into a 25mL reaction vessel, 0.5mmol (94.0 mg) of diisopropyl malonate, styrene (0.75 mmol,1.5 eq, 78.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, were sequentially added, reacted in an oil bath at 100 ℃ for 24h, cooled to room temperature, added with 20mL of water, extracted three times with 10mL of ethyl acetate, combined with an organic layer, concentrated under reduced pressure, and the product was purified by column chromatography on a 300-400 mesh silica gel column with an eluent of ethyl acetate andthe petroleum ether mixture, the volume ratio of which is 1:10, gives 48.6mg of pale yellow liquid product with a yield of 32% and a purity of 99%. 1 H NMR(400MHz, CDCl 3 )δppm:7.27-7.33(m,4H),7.19-7.22(t,1H),6.47(d,J＝16.0 Hz,1H),6.13-6.20(m,1H),5.02-5.11(t,2H),3.41-3.45(t,1H), 2.76-2.80(t,2H),1.24(d,J＝6.4Hz,12H)； 13 C NMR(100MHz,CDCl 3 ) δppm:168.4,137.0,132.6,128.4,127.3,126.1,125.7,68.9,52.2,32.1, 21.63,21.58；HRMS(ESI-TOF)m/z calcd for C 18 H 25 O 4 [M+H] + 305.1747,found 305.1743.
Wherein, the chemical structural general formula of the 2-cinnamyl diisopropyl malonate (3 w) is as follows:
example 24
A method for synthesizing 2-cinnamoyl-2-phenyl-1H-indene-1, 3 (2H) -diketone (3 x), which comprises the following steps:
to a 25mL reaction vessel was successively added 0.5mmol (111.0 mg) of diphenyl-1, 3-indanone, styrene (0.75 mmol,1.5 eq, 78.1 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, reacted in an oil bath at 100℃for 24h, cooled to room temperature, 20mL of water was added, 10mL of ethyl acetate was used for extraction three times, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography, 300-400 mesh silica gel column with eluent of a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10, to give 108.2mg of a pale yellow liquid product in a yield of 64% and a purity of 99%. 1 H NMR (400MHz,CDCl 3 )δppm:7.96-7.99(m,2H),7.77-7.79(m,2H),7.46 (d,J＝7.2Hz,2H),7.29-7.33(t,2H),7.23-7.26(m,1H),7.11- 7.19(m,5H),6.46(d,J＝16.0Hz,1H),5.91-5.98(m,1H),3.18(d, J＝7.6Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δppm:142.0,136.8,136.6,135.9, 134.8,128.8,128.3,127.8,127.3,126.8,126.2,123.5,123.2,62.6,39.3； HRMS(ESI-TOF)m/z calcd for C 24 H 19 O 2 [M+H] + 339.1385,found 339.1386.
Wherein, the chemical structural general formula of the 2-cinnamoyl-2-phenyl-1H-indene-1, 3 (2H) -diketone (3 x) is as follows:
example 25
A synthesis method of 2-allyl dimethyl malonate (3 y), comprising the following steps:
dimethyl malonate 0.5mmol (61.0 mg), allylthiomethyl ether (0.75 mmol,1.5 eq, 66.0 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, were sequentially added to a 25mL reaction vessel, reacted in an oil bath at 100℃for 24h, cooled to room temperature, 20mL of water was added, extracted three times with 10mL of ethyl acetate, the organic layers were combined, concentrated under reduced pressure, the product was purified by column chromatography on a 300-400 mesh silica gel column with eluent as a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:10, to give a pale yellow liquid product 67.1mg, yield 78%, purity 99%. 1 H NMR (400MHz,CDCl 3 )δppm:5.72-5.82(m,1H),5.06-5.15(m,2H),3.74 (s,6H),3.45-3.49(t,1H),2.64-2.67(t,2H)； 13 C NMR(100MHz,CDCl 3 ) δppm:169.3,133.9,117.6,52.5,51.4,32.8；HRMS(ESI-TOF)m/z calcd for C 10 H 13 O 4 [M+H] + 173.0814,found 173.0816.
Wherein, the chemical structural general formula of the 2-allyl dimethyl malonate (3 y) is as follows:
example 26
A synthesis method of diethyl 2-allylmalonate (3 z) comprises the following steps:
diethyl malonate 0.5mmol (80.0 mg), allylthiomethyl ether (0.75 mmol,1.5 eq, 66.0 mg), TFA (1.0 mol,2.0 eq), agOTf (13.0 mg,10 mol%), solvent DMSO 4mL, were sequentially added to a 25mL reaction vessel, reacted in an oil bath at 100℃for 24h, cooled to room temperature, 20mL of water was added, extracted three times with 10mL of ethyl acetate, and combinedThe organic layer is concentrated under reduced pressure, the product is purified by column chromatography, a 300-400 mesh silica gel column is adopted, the eluent is a mixture of ethyl acetate and petroleum ether, the volume ratio of the ethyl acetate to the petroleum ether is 1:10, and the light yellow liquid product is 69.0mg, the yield is 69%, and the purity is 99%. 1 H NMR (400MHz,CDCl 3 )δppm:5.73-5.84(m,1H),5.05-5.15(m,2H),4.16 -4.24(m,4H),3.04-3.44(t,1H),2.63-2.66(t,2H),1.25-1.29 (t,6H)； 13 C NMR(100MHz,CDCl 3 )δppm:168.9,134.1,117.4,61.3,51.6, 32.8,14.0；HRMS(ESI-TOF)m/z calcd for C 10 H 17 O 4 [M+H] + 201.1127,found 201.1128.
Wherein the chemical structural general formula of the 2-allyl diethyl malonate (3 z) is as follows:
Claims (4)
1. a method for simply synthesizing an allyl dicarbonyl compound, which is characterized by comprising the following steps:
adding 0.5mmol of dicarbonyl compound and 0.75mmol of olefin into 3-4 mL of DMSO in a reaction vessel to prepare a solvent, and adding 5%, 10% and 200% of catalyst of the dicarbonyl compound molar weight into the solvent
Reacting AgOTf and additive TFA for 12-24 h under the oil bath condition of 80-100 ℃, cooling to room temperature, adding water, extracting with ethyl acetate for three times, combining organic layers, concentrating under reduced pressure, purifying the product by column chromatography to obtain the allyl dicarbonyl compound; the chemical structural general formula is as follows:
wherein R is 1 Is alkyl, alkoxy, phenyl or substituted phenyl, R 2 Is alkoxy, phenyl or substituted phenyl, when R 1 When alkyl, R 2 Is phenyl or substituted phenyl, R 3 Is H, alkyl, phenyl or substituted phenyl, R 4 Is phenyl or substituted phenyl; or the olefin is 2-naphthalene ethylene and indene;
the reaction general formula of the synthesis method is shown as follows:
2. a method for the simple synthesis of allyldicarbonyl compounds according to claim 1, characterized in that the dicarbonyl compound i is dibenzoylmethane and a derivative or diethyl malonate derivative.
3. A simple process for the synthesis of allyl dicarbonyl compounds according to claim 1, characterized in that the olefin ii is styrene, p-methylstyrene, p-ethylstyrene, p-tert-butylstyrene, m-methylstyrene, 3, 4-dimethylstyrene, 3, 5-dimethylstyrene or 1, 1-diphenylethylene.
4. A method for the simple synthesis of allyldicarbonyl compounds according to claim 1, characterized in that the column chromatography conditions are: the 300-400 mesh silica gel column, and the eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1:10-1:50.
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