CN111393269A - Method for synthesizing 1, 3-dicarbonyl compound based on one-pot method of terminal alkyne and acyl halide - Google Patents

Method for synthesizing 1, 3-dicarbonyl compound based on one-pot method of terminal alkyne and acyl halide Download PDF

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CN111393269A
CN111393269A CN202010213233.5A CN202010213233A CN111393269A CN 111393269 A CN111393269 A CN 111393269A CN 202010213233 A CN202010213233 A CN 202010213233A CN 111393269 A CN111393269 A CN 111393269A
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acyl halide
terminal alkyne
dicarbonyl compound
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夏远志
陈建辉
华振国
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Wenzhou University
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Abstract

The invention belongs to the technical field of catalytic synthesis, and discloses a method for synthesizing a 1, 3-dicarbonyl compound by a one-pot method, wherein a simple palladium salt and a copper salt are used as catalysts, and under the action of trifluoromethanesulfonic acid, terminal alkyne and acyl halide react for 0.5 min-12 h at the temperature of 0-80 ℃ to prepare the 1, 3-dicarbonyl compound; the mol ratio of the terminal alkyne, acyl halide, palladium salt, copper salt and trifluoromethanesulfonic acid is 1: (1-2): (0.00001-0.10): (0.00001-0.10): (0.00004-0.40); the catalyst used in the method is common commercial palladium salt and copper salt, and the reagents used in the reaction are commercial reagents, in addition, the raw materials are cheap and easy to obtain, the tolerance of functional groups is good, the reaction conditions are mild, the operation is simple and convenient, and the atom economy is high.

Description

Method for synthesizing 1, 3-dicarbonyl compound based on one-pot method of terminal alkyne and acyl halide
Technical Field
The invention belongs to the technical field of organic catalytic synthesis, and particularly relates to a method for synthesizing a 1, 3-dicarbonyl compound based on a one-pot method of terminal alkyne and acyl halide.
Background
In recent years, 1, 3-dicarbonyl compounds have attracted attention as important synthetic intermediates in organic chemistry. A large body of literature shows that these intermediates can be further reacted to form various heterocyclic compounds, such as: isoxazoles, pyrazoles, benzimidazoles, pyrroles and the like (reaction formula a). The compounds have the characteristics of high efficiency, low toxicity and the like in the aspects of medicines and pesticides, and have wide application, such as: oxolic Acid, a quinolinone fungicide; fripronil, an insecticide, these compounds are hot spots for the development of new pesticides and medicines (chemical formula b).
Figure BDA0002423525490000011
At present, a method for synthesizing a 1, 3-dicarbonyl compound by different methods and different raw materials has been reported more, but each method has disadvantages, such as:
the Villar project group in 2002 reported a method for synthesizing 1, 3-dicarbonyl compounds by using a microwave reactor, and the reaction formula is as follows:
Figure BDA0002423525490000021
however, this method has the following disadvantages: the raw material of the silicon ether is unstable and easy to hydrolyze; the raw material acyl nitrile is difficult to obtain; the reaction time is long; moreover, the reaction regulation is strict and needs to be carried out in a microwave reactor.
In 2006, Dudley subjects prepared β -dicarbonyl acetylene bond-linked products using a claisen condensation reaction, which has the following reaction formula:
Figure BDA0002423525490000022
but the preparation of raw material ketene of the method is difficult; lithium salts are expensive and dangerous.
The Ryu and Ando subject groups respectively report the method for synthesizing the 1, 3-dicarbonyl compound by using [ Ru ] and [ Rh ] as catalysts, and the reaction formula is as follows:
Figure BDA0002423525490000023
however, this method also requires a ketene starting material, which is difficult to prepare and [ Ru ] and [ Rh ] are expensive.
The Beaudry task group in 2011 reported the reaction of β -hydroxyketone oxidized to β -dione, which has the following formula:
Figure BDA0002423525490000024
however, the raw materials in the method are special and not universal; the use of IBX oxidizer produces by-products, which are poor in atomic economy; the reaction needs to be carried out under the reflux condition, the operation is inconvenient, and the safety is poor.
The 2012 Skrydstrp group reported that a palladium-catalyzed carbonylation α -arylation reaction synthesized 1, 3-dicarbonyl compounds.
Figure BDA0002423525490000031
However, CO in this process is a highly toxic gas; and the reaction requires the addition of a ligand.
The You topic group in 2017 reported a transition metal-free catalyzed decarbonylation coupling reaction. The method comprises the following two steps of firstly, taking potassium carbonate as a base, adding a solvent, reacting for 2 hours at room temperature, then continuously adding KOH into the reaction within 0.5 hour, continuously stirring for 1.5 hours, and reacting by using a mixed solvent of NMP/MeOH/hydroxyyacetone, wherein the reaction formula is as follows:
Figure BDA0002423525490000032
however, the raw materials in the method are special, and the preparation is difficult; moreover, a mixed solvent is required, and the reaction conditions are strict.
The Xia topic group in 2019 reported the regioselective synthesis of 1, 3-diketones from gold (I) catalyzed alkynones. The reaction is carried out for 12 hours at room temperature by using two catalysts of gold/silver, MeOH as a solvent and equivalent amount of water to generate 1, 3-diketone, and the reaction formula is as follows:
Figure BDA0002423525490000033
however, the raw materials in the method are special and need to be prepared in advance; and the catalysts used therein are expensive.
In summary, the problems of the prior art are as follows: 1. various raw materials which are difficult to obtain need to be prepared; 2. the use of toxic gases in the reaction; 3. various expensive inorganic salts are used, and some are dangerous medicines.
The difficulty in solving the technical problems is as follows: how to use simple raw materials and react under mild conditions to generate the 1, 3-dicarbonyl compound.
Figure BDA0002423525490000041
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing a 1, 3-dicarbonyl compound based on a one-pot method of terminal alkyne and acyl halide, which uses simple raw materials and reacts under mild conditions to generate the 1, 3-dicarbonyl compound.
In order to achieve the above object, the present invention provides a method for synthesizing a 1, 3-dicarbonyl compound based on a one-pot method of terminal alkyne and acyl halide, which is characterized by comprising the following steps: firstly, taking terminal alkyne and acyl halide as raw materials, reacting for 0.5 min-12 h at 0-80 ℃ in an organic solvent by taking palladium salt and copper salt as a common catalyst in an alkaline environment, filtering without separating an alkynone intermediate product after the reaction is finished, removing insoluble substances, removing the solvent from filtrate, secondly, directly adding trifluoromethanesulfonic acid and an alcohol solvent, continuing to react for 2h to prepare a final product 1, 3-dicarbonyl compound,
wherein the mol ratio of the terminal alkyne, acyl halide, palladium salt, copper salt and acid is 1: (1-2): (0.00001-0.10): (0.00001-0.10): (0.00004-0.40);
the structural formula of the terminal alkyne is
Figure BDA0002423525490000042
R1Optionally selected from substituted aryl, C1-C16Alkyl of (C)1-C16Cycloalkyl of, C1-C16One of alkyl alcohols; the acyl halide has the structural formula
Figure BDA0002423525490000043
R2Optionally selected from substituted aryl, C1-C16Alkyl of (C)1-C16One of the cycloalkyl groups of (a) or (b),
x is selected from one of F, Cl, Br and I.
Further, the palladium salt adopts PdCl2(PPh3) And the copper salt adopts CuI.
Further, the mol ratio of the terminal alkyne, the acyl halide, the palladium salt, the copper salt and the acid is 1: (1.1-1.5): (0.001-0.10): (0.001-0.10): (0.004-0.40).
Further, the mol ratio of the terminal alkyne, the acyl halide, the palladium salt, the copper salt and the acid is 1: 1.1: 0.001: 0.002: 0.4.
further, in the first step, the reaction temperature is 0 ℃ to 60 ℃.
Further, in the first step, the reaction time is 10 minutes to 6 hours.
Further, in the first step, a base is added to form a basic environment, and the base is selected from any one of triethylamine, potassium carbonate, cesium carbonate and pyridine.
Further, the organic solvent used in the first step is any one of super-dry tetrahydrofuran, super-dry cyclohexane, tetrahydrofuran, dichloromethane and dichloroethane.
Further, the alcohol solvent used in the second step is any one of methanol, ethanol, isopropanol and tert-butanol.
Another object of the present invention is to provide a 1, 3-dicarbonyl compound synthesized by the method for synthesizing the 1, 3-dicarbonyl compound based on the one-pot method of terminal alkyne and acyl halide,
the structural formula of the 1, 3-dicarbonyl compound is shown in the specification
Figure BDA0002423525490000051
R1Optionally selected from substituted aryl, C1-C16Alkyl of (C)1-C16Cycloalkyl of, C1-C16One of alkyl alcohols;
R2optionally selected from substituted aryl, C1-C16Alkyl of (C)1-C16One of cycloalkyl groups of (a).
In summary, the advantages and positive effects of the invention are: the method is environment-friendly and efficient, raw materials are simple and easy to obtain, the dosage of the catalyst is small, the reaction time is short under the room temperature condition, the application range of the substrate is wide, the conversion of the alkynone to the 1, 3-dicarbonyl compound can be realized by using the trifluoromethanesulfonic acid, and importantly, the operation of separation and purification of the alkynone is omitted in the reaction.
Compared with the traditional method, the method of the invention provides an efficient method for synthesizing the 1, 3-dicarbonyl compound in a one-pot method. The method has the advantages of simple reaction process and post-treatment operation, simple and easily obtained reaction substrate and mild reaction condition. In view of the important role of the 1, 3-dicarbonyl compound in the aspects of medicine and materials, the 1, 3-dicarbonyl compound is a particularly important synthetic intermediate, and the method has very high application prospect and value.
Compared with the prior art, the method of the invention is a one-pot method initiated by acid to generate the 1, 3-dicarbonyl compound. The reaction substrates are simple and easy to obtain, the catalyst used in the method is common palladium salt and copper salt, the reagents used in the reaction are all commercial reagents, in addition, the raw materials are cheap and easy to obtain, the tolerance of the functional groups is good, the reaction conditions are mild, the operation is simple and convenient, and the atom economy is high.
Drawings
FIG. 1 is a reaction scheme of synthesizing 1, 3-dicarbonyl compound based on one-pot method of terminal alkyne and acyl halide provided by the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a method for synthesizing a 1, 3-dicarbonyl compound based on a one-pot method of terminal alkyne and acyl halide, and the invention is described in detail with reference to the attached drawing.
As shown in fig. 1, the method for synthesizing a 1, 3-dicarbonyl compound based on a one-pot method of terminal alkyne and acyl halide provided by the embodiment of the invention comprises the following steps:
s101: with PdCl2(PPh3) the/CuI is a catalyst;
s102: in the presence of trifluoromethanesulfonic acid, methanol is used as a solvent, and the 1, 3-dicarbonyl compound is prepared by reacting at the temperature of 0-80 ℃ for 0.5 min-12 h.
Specifically, terminal alkyne and acyl halide are used as raw materials, and PdCl is used in the first step2(PPh3) As catalyst, CuI as cocatalyst, triethylamine (Et)3N) as base, in ultra-dry Tetrahydrofuran (THF) solvent, reacting for 10 min; through the operations of suction filtration and spin drying, under the condition of not separating an alkynone intermediate, trifluoromethanesulfonic acid (HOTf) and methanol (MeOH) are added, and the reaction is continued for 2h, so that the efficient synthesis of a series of 1, 3-dicarbonyl compounds can be realized. The chemical reaction formula is as follows:
Figure BDA0002423525490000061
the structural formula of the terminal alkyne is
Figure BDA0002423525490000062
The acyl halide has the structural formula
Figure BDA0002423525490000063
Wherein R is1Optionally selected from substituted aryl, C1-C16Alkyl of (C)1-C16Cycloalkyl of, C1-C16One of alkyl alcohols;
R2optionally selected from substituted aryl, C1-C16Alkyl of (C)1-C16One of cycloalkyl groups of (a);
x is selected from one of F, Cl, Br and I.
The mol ratio of the terminal alkyne, acyl halide, palladium salt, copper salt and acid is 1: (1-2): (0.00001-0.10): (0.00001-0.10): (0.00004-0.40), further preferably 1: (1.1-1.5): (0.001-0.10): (0.001-0.10): (0.004 to 0.40), particularly recommending that the mol ratio of the terminal alkyne, acyl halide, palladium salt, copper salt and acid is 1: 1.1: 0.001: 0.002: 0.4.
the reaction temperature is preferably from 0 ℃ to 80 ℃, more preferably from 0 ℃ to 60 ℃, particularly preferably 25 ℃.
The reaction time is preferably from 0.5 minutes to 12 hours, more preferably from 10 minutes to 6 hours, in particular 2 hours.
The alkyl groups mentioned in the present invention are each preferably a group having 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. The cycloalkyl groups mentioned in the invention are all recommended to be groups with 3-16 carbon atoms, further recommended to be groups with 3-10 carbon atoms, and particularly recommended to be groups with 3-6 carbon atoms. The aryl groups mentioned in the invention all refer to phenyl, naphthyl and heteroaryl containing N, O and S.
The method can separate the product by recrystallization, thin-layer chromatography, column chromatography or reduced pressure distillation.
The technical solution of the present invention is further described by the following specific examples.
Example 1: one-pot synthesis of 1, 3-dicarbonyl compound by terminal alkyne and acyl halide
Figure BDA0002423525490000071
The method comprises the following operation steps: PdCl was added to a dry reaction tube at 25 deg.C2(PPh3)2(0.4mg,0.1 mol%), CuI (0.2mg,0.2 mol%), evacuating the tube and introducing nitrogen as a shielding gas, and Et is added under nitrogen shielding3N (33.3 mu L, 1.2equiv), alkyne (0.2mmol), acyl chloride (0.22mmol), and then adding super-dry THF (1m L) to react for 10min at room temperature, adding HOTf (26.5 mu L, 1.5equiv.) and MeOH (1m L) by suction filtration and spin drying operations without isolating the alkyne ketone intermediate, continuing the reaction for 2h, and then carrying out column chromatography to obtain the product.
Product 1: 1,3-diphenylpropane-1,3-dione
Figure BDA0002423525490000081
(enol form)Yellow solid；mp 63-66℃；1H NMR(400MHz,CDCl3)16.89(s, 1H),7.99(d,J＝8.4Hz,4H),7.58-7.54(m,2H),7.51-7.47(m,4H),6.87(s,1H)；13C NMR(100MHz,CDCl3)185.7,135.5,132.4,128.7,127.1,93.1.
And (3) a product 2: 1- (4-chlorophenylyl) -3-phenylpropane-1,3-dione
Figure BDA0002423525490000082
(enol form)Yellow solid；mp 87-89℃；1H NMR(400MHz,CDCl3)16.83(s, 1H),7.97-7.92(m,J＝8.0Hz,4H),7.60-7.54(m,1H),7.50-7.46(m,4H),6.82(s,1H)；13C NMR(100MHz,CDCl3)185.8,184.6,138.7,135.3,134.0,132.6,129.0,128.7, 128.5,127.2,93.0.
And (3) a product: 1- (3-chlorophenylyl) -3-phenylpropane-1,3-dione
Figure BDA0002423525490000083
(enol form)Yellow solid；mp 66-67℃；1H NMR(400MHz,CDCl3)16.76(s, 1H),7.99(d,J＝7.2Hz,2H),7.95(s,1H),7.86(d,J＝8.0Hz,1H),7.55-7.51(m,1H), 7.50-7.44(m,3H),7.43-7.36(m,1H),6.81(s,1H)；13C NMR(100MHz,CDCl3) 186.1,184.1,137.3,135.2,134.9,132.7,132.3,130.0,128.7,127.2,125.2,93.3 .
And (3) a product 4: 1- (2-chlorophenylyl) -3-phenylpropane-1,3-dione
Figure BDA0002423525490000091
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)16.36(s,1H),7.96(d,J＝7.2Hz,2H),7.68(d,J＝7.2Hz,1H),7.58-7.53(m,1H),7.48-7.45(m,3H),7.44-7.33 (m,2H),6.74(s,1H)；13C NMR(100MHz,CDCl3)186.9,184.5,136.2,134.8,132.7, 131.7,130.7,130.1,128.7,127.2,127.0,98.3.
And (3) a product 5: 1- (4-fluorophenyl) -3-phenylpropane-1,3-dione
Figure BDA0002423525490000092
(enol form)Yellow solid；mp 71-73℃；1H NMR(400MHz,CDCl3)16.85(s, 1H),8.09-7.93(m,4H),7.56-7.54(m,1H),7.51-7.47(m,2H),7.18-7.14(m,2H),6.80 (s,1H)；13C NMR(100MHz,CDCl3)185.1,165.4(d,J＝253.0),135.2,132.5,131.5, 129.6(d,J＝9.0Hz),129.6,128.7,127.1,115.8(d,J＝22.0Hz),92.8.
And (3) a product 6: 1,3-di (thiophen-2-yl) propane-1,3-dione
Figure BDA0002423525490000093
(enol form)Yellow solid；mp 90-92℃；1H NMR(400MHz,CDCl3)16.19(s,1H),7.77(d,J＝3.6Hz,2H),7.61(d,J＝4.8Hz,2H),7.18-7.14(m,3H),6.54(s,1H)；13C NMR(100MHz,CDCl3)178.7,132.0,130.0,128.3,92.6,52.3.
And (3) a product 7: 1-phenyl-3- (4-propylphenyl) propane-1,3-dione
Figure BDA0002423525490000101
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)16.92(s,1H),7.98(d,J＝7.2Hz,2H),7.91(d,J＝8.4Hz,2H),7.56-7.52(m,1H),7.50-7.46(m,2H),7.29(d,J ＝8.0Hz,2H),6.84(s,1H),2.65(t,J＝7.2Hz,2H),1.72-1.63(m,2H),0.96(t,J＝7.2 Hz,3H)；13C NMR(100MHz,CDCl3)186.1,185.2,148.0,135.6,133.0,132.3, 128.8,128.6,127.2,127.1,92.8,38.0,24.3,13.8.
And (3) a product 8: 1, 3-di-p-tolyprophane-1, 3-dione
Figure BDA0002423525490000102
(enol form)Yellow solid；mp 120-123℃；1H NMR(400MHz,CDCl3)16.97(s,1H),7.88(d,J＝7.6Hz,4H),7.28(d,J＝7.6Hz,4H),6.80(s,1H),2.42(s,6H)；13C NMR(100MHz,CDCl3)185.4,143.1,132.8,129.3,127.1,92.4,21.6.
And (3) a product: 1-phenyl-3- (p-tolyl) propane-1,3-dione
Figure BDA0002423525490000103
(enol form)Yellow solid；mp 83-85℃；1H NMR(400MHz,CDCl3)16.92(s, 1H),7.98(d,J＝8.0Hz,2H),7.89(d,J＝6.8Hz,2H),7.56-7.52(m,1H),7.50-7.46(m, 2H),7.28(d,J＝7.6Hz,2H),6.83(s,1H),2.42(s,3H)；13C NMR(100MHz,CDCl3) 186.0,185.1,143.3,135.6,132.8,132.3,129.4,128.6,127.2,127.1,92.8,21.6.
And (3) a product: 1-phenyl-3- (m-tolyl) propane-1,3-dione
Figure BDA0002423525490000104
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)16.89(s,1H),7.99(d,J＝7.2Hz,2H),7.81-7.73(m,2H),7.56-7.52(m,1H),7.50-7.46(m,2H),7.41-7.31(m, 2H),6.84(s,1H),2.43(s,3H)；13C NMR(100MHz,CDCl3)186.0,185.6,138.4, 135.5,135.4,133.2,132.4,128.6,128.5,127.7,127.1,124.3,93.1,21.4.
And (3) a product 11: 1-phenyl-3- (o-tolyl) propane-1,3-dione
Figure BDA0002423525490000111
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)16.64(s,1H),7.94(d,J＝7.2Hz,2H),7.57-7.52(m,2H),7.48-7.45(m,2H),7.38-7.35(m,1H),7.30-7.14(m, 2H),6.53(s,1H),2.55(s,3H)；13C NMR(100MHz,CDCl3)190.4,184.9,137.0, 136.6,135.2,132.4,131.4,130.7,128.6,128.3,127.1,125.8,97.2,20.7.
Product 12: 1-phenyl-3- (thiophen-2-yl) propane-1,3-dione
Figure BDA0002423525490000112
(enol form)Yellow solid；mp 74-76℃；1H NMR(400MHz,CDCl3)16.31(s, 1H),7.95(d,J＝8.0Hz,2H),7.81(d,J＝4.0Hz,1H),7.64(d,J＝3.2Hz,1H), 7.56-7.53(m,1H),7.50-7.46(m,2H),7.18-7.16(m,1H),6.69(s,1H)；13C NMR(100 MHz,CDCl3)183.0,180.7,142.2,134.4,132.6,132.3,130.4,128.7,128.3,126.8, 93.1
Product 13: 1- (1-hydroxycyclohexyl) -4,4-dimethylpentane-1,3-dione
Figure BDA0002423525490000113
(enol form)Colorless oil；1H NMR(400MHz,CDCl3)7.86(d,J＝6.8Hz, 2H),7.58-7.54(m,1H),7.51-7.48(m,2H),5.98(s,1H),1.83-1.72(m,10H)；13C NMR(100MHz,CDCl3)206.9,183.4,132.5,129.3,128.8,127.1,99.2,90.8,31.8, 24.5,21.9.
Product 14: 1-phenylheptane-1,3-dione
Figure BDA0002423525490000121
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)16.20(s,1H),7.88(d,J＝7.2Hz,2H),7.53-7.50(m,1H),7.46-7.43(m,2H),6.17(s,1H),2.43(t,J＝7.6Hz 2H),1.71-1.63(m,2H),1.48-1.34(m,2H),0.95(t,J＝7.2Hz,3H)；13C NMR(100MHz, CDCl3)197.0,183.5,135.0,132.2,128.6,126.9,96.0,38.9,27.9,22.4,13.8.
Product 15: 4,4-dimethyl-1-phenylpentane-1,3-dione
Figure BDA0002423525490000122
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)16.49(s,1H),7.89(d,J＝7.2Hz,2H),7.53-7.50(m,1H),7.47-7.43(m,2H),6.30(s,1H),1.25(s,9H)；13C NMR(100MHz,CDCl3)202.9,184.5,135.5,132.1,128.5,126.9,92.1,39.8,27.4.
Product 16: 5-hydroxy-1-phenyl pentane-1,3-dione
Figure BDA0002423525490000123
(enol form)Yellow solid；mp 65-67℃；1H NMR(400MHz,CDCl3)7.74(d,J＝7.2Hz,2H),7.51-7.47(m,1H),7.46-7.40(m,3H),6.03(s,1H),4.67(t,J＝6.8Hz, 2H),2.66(t,J＝6.8Hz,2H)；13C NMR(100MHz,CDCl3)192.7,170.5,132.6,131.7, 128.6,126.5,102.4,68.2,36.0.
Product 17: 4-hydroxy-4-methyl-1-phenyl-pentane-1, 3-dione
Figure BDA0002423525490000131
(enol form)Yellow solid；mp 64-65℃；1H NMR(400MHz,CDCl3)7.84(d,J＝7.2Hz,2H),7.58-7.54(m,1H),7.51-7.47(m,2H),5.97(s,1H),1.50(s,9H)；13C NMR(100MHz,CDCl3)207.0,183.4,132.6,129.1,128.8,127.1,98.5,89.0,23.1.
Product 18: 1-cyclopropy-3-phenylpropane-1, 3-dione
Figure BDA0002423525490000132
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)16.25(s,1H),7.87(d,J＝7.2Hz,2H),7.52-7.48(m,1H),7.46-7.42(m,2H),6.29(s,1H),1.96-1.50(m,1H), 1.50-1.05(m,2H),1.05-0.82(m,2H)；13C NMR(100MHz,CDCl3)200.4,178.4, 134.3,133.7,131.9,128.6,126.7,96.1,19.4,10.7.
Product 19: 4-methyl-1-phenyl pentane-1,3-dione
Figure BDA0002423525490000133
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)16.24(s,1H),7.89(d,J＝8.0Hz,2H),7.54-7.50(m,1H),7.48-7.44(m,2H),6.20(s,1H),2.66-2.59(m,1H), 1.23(m,6H)；13C NMR(100MHz,CDCl3)201.2,183.8,135.1,132.2,128.6,126.9, 94.2,37.5,19.4.
And (3) a product 20: 1- (4-bromophenyl) -4,4-dimethylpentane-1,3-dione
Figure BDA0002423525490000141
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)16.45(s,1H),7.75(d,J＝8.8Hz,2H),7.58(d,J＝8.8Hz,2H),6.26(s,1H),1.25(s,9H)；13C NMR(100MHz, CDCl3)203.1,183.4,134.4,131.8,128.5,126.9,92.0,39.9,27.3.
Product 21: 1- (4-methoxyphenyl) -4,4-dimethylpentane-1,3-dione
Figure BDA0002423525490000142
(enol form)Colorless oil；1H NMR(400MHz,CDCl3)16.60(s,1H), 7.79-7.75(m,2H),6.86-6.84(m,2H),6.16(s,1H),3.78(s,3H),1.16(s,9H)；13C NMR(100MHz,CDCl3)200.7,185.3,162.9 129.0,128.1,113.8,91.1 55.4,39.3, 27.4.
Product 22: 2,2,6,6-tetramethylheptane-3,5-dione
Figure BDA0002423525490000143
(enol form)Colorless oil；1H NMR(400MHz,CDCl3)16.17(s,1H),5.73(s, 1H),1.18(s,18H)；13C NMR(100MHz,CDCl3)201.5,90.7,39.4,27.4.
Product 23: 1-cyclohexenyl-4, 4-dimethylpentane-1,3-dione
Figure BDA0002423525490000144
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)15.98(s,1H),5.60(s,1H),2.20(m,1H),1.92-1.74(m,4H),1.45-1.36(m,2H),1.34-1.19(m,4H),1.17(s,9H)；13C NMR(100MHz,CDCl3)201.1,198.6,93.3,47.0,39.2,29.6,27.3,25.8.
Product 24: 2,2-dimethylnonane-3,5-dione
Figure BDA0002423525490000151
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)15.86(s,1H),5.60(s,1H),2.31(t,J＝7.6Hz,3H),1.66-1.52(m,2H),1.42-1.32(m,2H),1.16(s,9H),0.93(t,J ＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)200.3,195.7,95.0,38.6,27.9,27.3,26.0, 22.4,13.8.
Product 25: 1-hydroxy-6,6-dimethylheptane-3,5-dione
Figure BDA0002423525490000152
(enol form)Yellow oil；1H NMR(400MHz,CDCl3)5.43(s,1H),4.45(t,J＝7.2Hz,2H),2.51(t,J＝7.2Hz,2H),1.15(s,9H)；13C NMR(100MHz,CDCl3)193.3, 184.6,101.2,68.1,36.5,35.6,27.4.
Product 26: 2-hydroxy-2,6,6-trimethylheptane-3,5-dione
Figure BDA0002423525490000153
(enol form)Yellow crystal；1H NMR(400MHz,CDCl3)5.33(s,1H),1.36(s, 6H),1.24(s,9H)；13C NMR(100MHz,CDCl3)208.0,198.9,97.9,88.3,34.5,27.3, 22.8.
Product 27: 1- (1-hydroxycyclohexyl) -4,4-dimethylpentane-1,3-dione
Figure BDA0002423525490000161
(enol form)Colorless crystal；1H NMR(400 MHz,CDCl3)5.34(s,1H),1.89–1.47(m,10H),1.26(s,9H)；13C NMR(100 MHz,CDCl3)208.1,199.1,98.6,34.6, 31.6,27.5,26.0,24.5,21.8。

Claims (10)

1. A method for synthesizing a 1, 3-dicarbonyl compound based on a one-pot method of terminal alkyne and acyl halide is characterized by comprising the following steps: firstly, taking terminal alkyne and acyl halide as raw materials, reacting for 0.5 min-12 h at 0-80 ℃ in an organic solvent by taking palladium salt and copper salt as a common catalyst in an alkaline environment at the temperature of 0-80 ℃, not separating an alkyne ketone intermediate product after the reaction is finished, filtering to remove insoluble substances, removing the solvent from filtrate, and directly adding trifluoromethanesulfonic acid and an alcohol solvent in a second step to continue the reaction for 2h to prepare a final product 1, 3-dicarbonyl compound, wherein the molar ratio of the terminal alkyne, the acyl halide, the palladium salt, the copper salt and the acid is 1: (1-2): (0.00001-0.10): (0.00001-0.10): (0.00004-0.40); the structural formula of the terminal alkyne is
Figure FDA0002423525480000011
R1 is one selected from substituted aryl, C1-C16 alkyl, C1-C16 cycloalkyl and C1-C16 alkyl alcohol; the acyl halide has the structural formula
Figure FDA0002423525480000012
R2 is selected from substituted aryl, C1-C16 alkyl, C1-C16 cycloalkyl, X is selected from F, Cl, Br, I.
2. The method for synthesizing a 1, 3-dicarbonyl compound based on a terminal alkyne and acyl halide as claimed in claim 1, wherein the palladium salt is PdCl2(PPh3) And the copper salt adopts CuI.
3. The method for synthesizing a 1, 3-dicarbonyl compound based on a terminal alkyne and acyl halide in a one-pot method according to claim 1, wherein the molar ratio of the terminal alkyne, the acyl halide, the palladium salt, the copper salt and the acid is 1: (1.1-1.5): (0.001-0.10): (0.001-0.10): (0.004-0.40).
4. The method for synthesizing a 1, 3-dicarbonyl compound based on a terminal alkyne and acyl halide in a one-pot method according to claim 3, wherein the molar ratio of the terminal alkyne, the acyl halide, the palladium salt, the copper salt and the acid is 1: 1.1: 0.001: 0.002: 0.4.
5. the method for synthesizing a 1, 3-dicarbonyl compound based on a terminal alkyne and acyl halide in a one-pot method according to claim 1, wherein the reaction temperature in the first step is 0 ℃ to 60 ℃.
6. The method for synthesizing a 1, 3-dicarbonyl compound based on a one-pot method of terminal alkyne and acyl halide as claimed in claim 1, wherein the reaction time in the first step is 10 minutes to 6 hours.
7. The method for synthesizing the 1, 3-dicarbonyl compound based on terminal alkyne and acyl halide in one pot as claimed in claim 1, wherein in the first step, a base is added to form a basic environment, and the base is selected from any one of triethylamine, potassium carbonate, cesium carbonate and pyridine.
8. The method for synthesizing the 1, 3-dicarbonyl compound based on terminal alkyne and acyl halide as claimed in claim 1, wherein the organic solvent used in the first step is any one of super-dry tetrahydrofuran, super-dry cyclohexane, tetrahydrofuran, dichloromethane and dichloroethane.
9. The method for synthesizing a 1, 3-dicarbonyl compound based on terminal alkyne and acyl halide as claimed in claim 1, wherein the alcoholic solvent used in the second step is any one of methanol, ethanol, isopropanol and tert-butanol.
10. A 1, 3-dicarbonyl compound synthesized by the one-pot method for synthesizing a 1, 3-dicarbonyl compound based on a terminal alkyne and an acyl halide as claimed in any one of claims 1 to 9, wherein:
the structural formula of the 1, 3-dicarbonyl compound is shown in the specification
Figure FDA0002423525480000021
R1Optionally selected from substituted aryl, C1-C16Alkyl of (C)1-C16Cycloalkyl of, C1-C16One of alkyl alcohols;
R2optionally selected from substituted aryl, C1-C16Alkyl of (C)1-C16One of cycloalkyl groups of (a).
CN202010213233.5A 2020-03-24 2020-03-24 Method for synthesizing 1, 3-dicarbonyl compound based on one-pot method of terminal alkyne and acyl halide Pending CN111393269A (en)

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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JINQIANG KUANG等: "Facile Access to 1,3-Diketones by Gold(I)-Catalyzed Regioselective Hydration of Ynones", 《ORG. BIOMOL. CHEM.》 *
LIANG CHEN等: "A Remarkably Efficient Coupling of Acid Chlorides with Alkynes in Water", 《ORGANIC LETTERS》 *
RUSSELL J. COX等: "Room temperature palladium catalysed coupling of acyl chlorides with terminal alkynes", 《CHEM. COMMUN.》 *

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