CN115403459B - Preparation method of 1, 4-dicarbonyl compound - Google Patents

Preparation method of 1, 4-dicarbonyl compound Download PDF

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CN115403459B
CN115403459B CN202110593153.1A CN202110593153A CN115403459B CN 115403459 B CN115403459 B CN 115403459B CN 202110593153 A CN202110593153 A CN 202110593153A CN 115403459 B CN115403459 B CN 115403459B
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ppy
fac
dtbbpy
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CN115403459A (en
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祝诗发
杨波
王永东
黄志鹏
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Xinyuan Guangzhou Pharmaceutical Research Co ltd
GENIFARM (GUANGZHOU) TECHNOLOGY Inc
South China University of Technology SCUT
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Xinyuan Guangzhou Pharmaceutical Research Co ltd
GENIFARM (GUANGZHOU) TECHNOLOGY Inc
South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

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Abstract

The invention discloses a preparation method of a 1, 4-dicarbonyl compound, which comprises the following steps: taking a compound shown in a formula (I) and acetylene as raw materials, reacting under the action of a solvent, a metal iridium bipyridine catalyst and alkali, and preparing the compound shown in a formula (II) through illumination;wherein R in formula (I) 1 Is thatOne of them; the R is 2 The substituent on the benzene ring can be one or more, and is independently selected from hydrogen atom, halogen atom, C1-C6 alkyl, C1-C6 ether group, C1-C6 ester group, phenoxy or trifluoromethyl; the preparation method has the advantages of simple raw material source, wide substrate range and simple operation, and can meet the requirements of research, development and production in the fields of organic, chemical industry, medicine and the like.

Description

Preparation method of 1, 4-dicarbonyl compound
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of a 1, 4-dicarbonyl compound.
Background
1, 4-dicarbonyl compounds are a very important structural unit, widely exist in natural products and drug molecules with physiological drug activity, are also very important organic synthesis intermediates, and can be used for synthesizing various cyclic compounds such as cyclopentenone, furan, pyrrole, thiophene and the like.
In the prior art, there are various methods for synthesizing 1, 4-dicarbonyl compounds or similar compounds, and previous researches report that the synthesis of the compounds is mainly performed through a Stetter reaction or a metal catalysis reaction.
Because of a plurality of limiting factors such as complex sources of raw materials, complex catalytic systems, low atomic economic effects, unfriendly environment and the like, the application range of the reaction is limited strongly, for example, chinese patent (CN 106966877A) discloses a 1, 4-dicarbonyl compound and a preparation method thereof, and the preparation method does not use a metal catalyst, but has complex sources of raw materials, and the application is limited due to overhigh reaction temperature.
Therefore, it is necessary to provide a process for producing a 1, 4-dicarbonyl compound having a simple raw material source and a low reaction temperature.
Disclosure of Invention
The invention provides a preparation method of a 1, 4-dicarbonyl compound, which is simple to operate and wide in substrate range, and aims to overcome the defects of complex sources of raw materials and overhigh reaction temperature.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a 1, 4-dicarbonyl compound comprises the following steps:
taking a compound shown in a formula (I) and acetylene as raw materials, reacting under the action of a solvent, a metal iridium bipyridine catalyst and alkali, and preparing the compound shown in a formula (II) through illumination;
wherein R in formula (I) 1 Is thatOne of them;
the R is 2 The substituent on the benzene ring may be one or more substituents independently selected from hydrogen atom, halogen atom, C1-C6 alkyl group, C1-C6 ether group, C1-C6 ester group, phenoxy group or trifluoromethyl group.
The preparation method disclosed by the invention has the advantages of simple raw material source, wide substrate range, simplicity in operation, capability of carrying out reaction without pressurization, and capability of meeting the requirements of research, development and production in the fields of organic, chemical industry, medicine and the like.
Substituent definition and general terminology
The term "halogen" as used herein refers to fluorine, chlorine, bromine, iodine.
The term "alkyl" as used herein, means a saturated straight, branched or cyclic monovalent hydrocarbon radical containing from 1 to 6 carbon atoms.
The term "ether group" as used herein refers to a group in which one of the carbon atoms in the alkyl group described herein is replaced with an oxygen atom.
The term "ester group" as used herein refers to-C (=o) O-. The ester groups may be linked to the substituents described herein to form the corresponding ester substituents.
A series of 1, 4-dicarbonyl compounds can be prepared by the above preparation method, and are partially listed as follows:
preferably, the metallic iridium bipyridine-based catalyst includes, but is not limited to [ Ir (ppy) 2 (dtbbpy)]PF 6 、 Ir[dF(CF 3 )ppy] 2 bpyPF 6 、Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 、Ir[dF(CF 3 )ppy] 2 (phen)PF 6 、 Ir[dFCF 3 ppy] 2 (bpy)PF 6 、Ir[dFppy] 2 (bpy)PF 6 、Ir[dFppy] 2 (dtbbpy)PF 6 、 Ir[p-Fppy] 2 (bpy)PF 6 、Ir[p-Fppy] 2 (dtbpy)PF 6 、Ir[4- t- Bu-Phenyl-4- t- Bu-Py] 2 (dtbpy)PF 6 、 Ir[dF(Me)ppy] 2 (dtbbpy)PF 6 、Ir(ppy) 2 (dtbbpy)PF 6 、Ir[dF(F)ppy] 2 (dCF 3 )PF 6 、 [Ir(ppy) 2 (bpy)]PF 6 、Ir[p-F(Me)ppy] 2 (dtbbpy)PF 6 、Ir[d( t- Bu)(CF 3 )ppy] 2 (dtbbpy)Cl、 Ir[d( t- Bu)(CF 3 )ppy] 2 (dtbbpy)PF 6 、Fac-Ir(ppy) 3 、Fac-Ir(dFppy) 3 、 Fac-Ir[d-F(p-t-Bu)ppy] 3 、Fac-Ir(p-CF 3 ppy) 3 、Fac-Ir(p-Fppy) 3 、Fac-Ir(p- t- Bu-ppy) 3 、 Fac-Ir(d-Fppy) 3 、Fac-Ir(3- t- Bu-ppy) 3 、Fac-Ir[(3- t- Bu-phenyl)-4- t- Bu-py)] 3 。
More preferably, the metal iridium bipyridine-based catalyst is more preferably Ir [ dF (CF) 3 )ppy] 2 bpyPF 6 、 Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 、Ir[dF(CF 3 )ppy] 2 (phen)PF 6 、Ir[dFCF 3 ppy] 2 (bpy)PF 6 、 Ir[p-Fppy] 2 (bpy)PF 6 、Ir[d( t- Bu)(CF 3 )ppy] 2 (dtbbpy)PF 6 。
Preferably, the light of illumination is monochromatic light or mixed light with the wavelength range of 200-800 nm.
More preferably, the light is blue or white light.
Preferably, the base is selected from potassium carbonate, cesium carbonate, potassium fluoride, potassium phosphate, potassium bicarbonate, sodium bicarbonate, dipotassium phosphate, pyridine, 2, 6-lutidine, triethylamine or tetramethylguanidine.
More preferably, the base is selected from potassium fluoride or dipotassium hydrogen phosphate.
Preferably, the molar ratio of the compound shown in the formula (I), the metal iridium dipyridine catalyst and the alkali is 1: (0.005-0.1): (0.1-3).
More preferably, the molar ratio of the compound shown in the formula (I), the metal iridium bipyridine catalyst and the alkali is 1: (0.01-0.05): (1-1.5).
Preferably, the solvent is one or more of dichloromethane, dichloroethane, acetone, acetonitrile, methanol, ethanol, tetrahydrofuran, 1, 4-dioxane or water.
Preferably, the solvent is added in an amount such that the concentration of the raw materials in the system is 0.01M to 0.1M.
Preferably, the solvent is a mixture of water with dichloromethane, dichloroethane, acetone, acetonitrile, methanol, ethanol, tetrahydrofuran or 1, 4-dioxane.
More preferably, the water content in the solvent is 5 to 60 equivalents of the compound represented by formula (I).
More preferably, the solvent is more preferably a mixture of acetonitrile and water, a mixture of dichloromethane and water, a mixture of tetrahydrofuran and water.
Acetylene may be provided by an acetylene pressure vessel or generated in situ from calcium carbide.
Preferably, acetylene in the reaction is provided by a pressure vessel, which refers to a vessel for collection, storage, such as a balloon, bladder, gas sampling bag, gas tank, steel cylinder.
Preferably, the acetylene pressure ranges from 1 to 10atm.
More preferably, the acetylene pressure ranges from 1 to 5atm.
More preferably, the acetylene pressure ranges from 1 to 3atm.
Preferably, the reaction temperature is 10 to 60 ℃. More preferably, the reaction temperature is more preferably 20 to 40 ℃.
Preferably, the reaction time is from 6 to 48 hours. More preferably, the reaction time is more preferably 12 to 24 hours.
The compounds of the formula (I) according to the invention can be obtained directly by purchase or by reference to known literature methods. For example: acetophenone compounds are prepared by oxidation of tin oxide (Kuldeep, w.; yang, c.; west, p.r.; doming, k.c.; chemmburkar, s.; reddy, r.r.e. synth Commun.2008,38,4434).
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a 1, 4-dicarbonyl compound, which can effectively synthesize the 1, 4-dicarbonyl compound by photocatalysis and using simple and easily available raw materials such as acetylene and the like. The method has wide substrate range, simple operation and lower reaction temperature, and can meet the requirements of research, development and production in the fields of organic, chemical industry, medicine and the like.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art and can be purchased directly or synthesized by known literature methods.
Example 1
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-diphenylbutane-1, 4-dione (II-1), having the following structural formula:
into a 25mL flask under nitrogen atmosphereThe phenylacetaldehyde acid (0.3 mmol) and the catalyst Ir (ppy) are added in sequence 2 [dF(CF 3 )ppy] 2 (phen)PF 6 (0.003mmol)、K 2 HPO 4 (0.36 mmol,1.2 eq.) H 2 O (6.0 mmol,20 eq.) and DCM (12 mL). The mixture was degassed under acetylene gas for three freeze-pump-thaw cycles and then inserted into an acetylene balloon. The reaction mixture was kept at room temperature during 24h of irradiation with a 12w blue light emitting diode at a distance of 5cm by fan cooling. After the reaction was completed, the reaction mixture was diluted with EtOAc and filtered. The filtrate was concentrated in vacuo, and then purified by column chromatography to give 1, 4-diphenylbutane-1, 4-dione (28.4 mg,0.12mmol,79% yield).
1 H NMR(500MHz,CDCl 3 )δ8.07-8.01(m,4H),7.61-7.55(m,2H),7.51-7.45(m, 4H),3.47(s,4H)； 13 C NMR(126MHz,CDCl 3 )δ198.6,136.8,133.1,128.6,128.1, 32.6.
Examples 2 to 9
This example provides a series of 1, 4-dicarbonyl compounds prepared by the same method and starting materials as in example 1, using different catalysts to prepare 1, 4-diphenylbutane-1, 4-dione (II-1), with the specific results shown in Table 1:
table 1 examples 2 to 9
Examples 10 to 18
This example provides a series of 1, 4-dicarbonyl compounds prepared by the same method and starting materials as in example 1, using different solvents to prepare 1, 4-diphenylbutane-1, 4-dione (II-1), with the specific results shown in Table 2:
table 2 examples 10 to 18
Examples Solvent(s) Yield%
10 DCM/H 2 O＝3/2(0.1M) 16
11 THF/H 2 O＝3/2(0.1M) 13
12 acetonitrile/H 2 O＝3/2(0.1M) 15
13 EA/H 2 O＝3/2(0.1M) 8
14 DCM(5eq H 2 O)(0.05M) 38
15 DCM(5eq H 2 O)(0.025M) 51
16 DCM(5eq H 2 O)(0.017M) 44
17 THF 10
18 Dichloroethane (dichloroethane) 10
Examples 19 to 27
This example provides a series of processes for the preparation of 1, 4-dicarbonyl compounds, the processes and materials being the same as in example 1, with varying partial conditions to prepare 1, 4-diphenylbutane-1, 4-dione (II-1), the specific results being shown in Table 3:
TABLE 3 EXAMPLES 19 to 27
Examples 28 to 31
This example provides a series of processes for the preparation of 1, 4-dicarbonyl compounds, the processes and materials being the same as in example 1, with varying partial conditions to prepare 1, 4-diphenylbutane-1, 4-dione (II-1), the specific results being shown in Table 4:
table 4 examples 28 to 31
Examples Water addition amount Yield%
28 5eq 51
29 10eq 48
1 20eq 79
30 40eq 49
31 60eq 49
Examples 32 to 40
This example provides a series of processes for the preparation of 1, 4-dicarbonyl compounds, the processes and materials being the same as in example 1, with varying partial conditions to prepare 1, 4-diphenylbutane-1, 4-dione (II-1), the specific results being shown in Table 5:
table 5 examples 32 to 40
Examples Light source Acetylene pressure Time/h Yield%
32 Blue light 1atm 12 51
33 Blue light 1atm 36 75
34 Blue light 3atm 12 63
35 Blue light 5atm 12 45
36 Blue light 10atm 12 42
37 Ultraviolet light 1atm 24 35
38 Green light 1atm 24 47
39 Yellow light 1atm 24 43
40 White light 1atm 24 37
Example 41
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-diortholylbutane-1, 4-dione (II-2), having the following structural formula:
the same procedures as in example 1 were repeated except for using o-tolylacetaldehyde (82.2 mg,0.5 mmol) instead of phenylglyoxylic acid in example 1 to give 1, 4-dion-tolyltutane-1, 4-dione (26.5 mg, 0.099mmol,40% yield). 1 H NMR(500MHz,CDCl 3 )δ7.80-7.77(m,2H),7.40-7.35 (m,2H),7.28(t,J＝10.0Hz,2H),7.25(d,J＝5.0Hz,2H),3.33(s,4H),2.50(s,6H)； 13 C NMR(126MHz,CDCl 3 )δ202.64,138.0,137.9,131.9,131.2,128.5,125.7,35.6, 21.2.
Example 42
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-di-m-tolyltutane-1, 4-dione (II-3), having the following structural formula:
the procedure of example 1 was repeated except for using m-methyl phenylglyoxylic acid (78.3 mg,0.47 mmol) instead of phenylglyoxylic acid in example 1 to give 1, 4-dimethylbenzene-butane-1, 4-dione (37.2 mg, 0.14mmol,59% yield).
1 H NMR(500MHz,CDCl 3 )δ7.87-7.81(m,4H),7.43-7.33(m,4H),3.44(s,4H), 2.42(s,6H)； 13 C NMR(126MHz,CDCl 3 )δ198.9,138.3,136.8,133.8,128.6,128.4, 125.3,32.7,21.3.
Example 43
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-di-p-tolyltutane-1, 4-dione (II-4), having the following structural formula:
the same procedures used in example 1 were repeated except for using p-tolualdehyde acid instead of phenylglyoxylic acid in example 1 to give 1, 4-di-p-tolyltutane-1, 4-dione (24.8 mg,0.186mmol,62% yield).
1 H NMR(500MHz,CDCl 3 )δ7.94(d,J＝5.0Hz,4H),7.27(d,J＝10.0Hz,4H), 3.42(s,4H),2.42(s,6H)； 13 C NMR(126MHz,CDCl 3 )δ198.4,143.8,134.4,129.2, 128.2,32.5,21.6.
Example 44
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4-ethylphenyl) butane-1, 4-dione (II-5), having the following structural formula:
the same procedures used in example 1 were repeated except for using p-ethyl phenylacetaldehyde acid instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (4-ethylphenyl) butane-1, 4-dione (26.3 mg,0.089mmol,59% yield).
1 H NMR(500MHz,CDCl 3 )δ7.96(d,J＝5.0Hz,4H),7.29(d,J＝10.0Hz,4H), 3.43(s,4H),2.71(q,J＝5.0Hz,4H),1.26(t,J＝5.0Hz,6H)； 13 C NMR(126MHz, CDCl 3 )δ198.4,150.0,134.6,128.3,128.0,32.5,28.9,15.2.
Example 45
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4-propylphenyl) butane-1, 4-dione (II-6), having the following structural formula:
the same procedures used in example 1 were repeated except for using p-propylphenylacetaldehyde in place of phenylglyoxylic acid in example 1 to give 1, 4-bis (4-propylphenyl) butane-1, 4-dione (26.0 mg,0.084mmol,57% yield).
1 H NMR(500MHz,CDCl 3 )δ7.96(d,J＝5.0Hz,4H),7.27(d,J＝10.0Hz,4H), 3.43(s,4H),2.65(t,J＝7.5Hz,4H),1.73-1.62(m,4H),0.95(t,J＝7.5Hz,2H)； 13 C NMR(126MHz,CDCl 3 )δ198.4,148.5,134.6,128.6,128.2,38.0,32.5,24.2,13.7.
Example 46
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4-butylphenyl) butane-1, 4-dione (II-7), having the following structural formula:
the procedure of example 1 was repeated except for using o-tolylacetaldehyde (98.8 mg,0.48 mmol) instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (4-butylphenyl) butane-1, 4-dione (57.7 mg,0.165mmol,69% yield).
1 H NMR(500MHz,CDCl 3 )δ7.95(d,J＝7.5Hz,4H),7.27(d,J＝7.5Hz,4H),3.43 (s,4H),2.67(t,J＝10.0Hz,4H),1.68-1.57(m,4H),1.41-1.31(m,4H),0.93(t,J＝ 7.5Hz,6H)； 13 C NMR(126MHz,CDCl 3 )δ198.4,148.8,134.5,128.6,128.2,35.7, 33.2,32.5,22.3,13.9.
Example 47
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4-isobutylphenyl) butane-1, 4-dione (II-8), having the structural formula:
the same procedures used in example 1 were repeated except for using 4-isobutylphenylacetaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (4-isobutylphenyl) butane-1, 4-dione (33.0 mg,0.094mmol,57% yield).
1 H NMR(500MHz,CDCl 3 )δ7.95(d,J＝10.0Hz,4H),7.24(d,J＝10.0Hz,4H), 3.43(s,4H),2.54(d,J＝5.0Hz,4H),1.97-1.84(m,2H),0.91(d,J＝5.0Hz,6H)； 13 C NMR(126MHz,CDCl 3 )δ198.4,147.5,134.6,129.3,128.1,45.4,32.5,30.1,22.3； HRMS(ESI-TOF)Calcd for C 24 H 31 O 2 [M+H] + :351.2324；found 351.2318.
Example 48
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4-isopropylphenyl) butane-1, 4-dione (II-9), having the following structural formula:
the same procedures used in example 1 were repeated except for using 4-isopropylglyoxylic acid instead of the phenylglyoxylic acid used in example 1 to give 1, 4-bis (4-isopropylphenyl) butane-1, 4-dione (21.8 mg,0.068mmol,45% yield).
1 H NMR(500MHz,CDCl 3 )δ7.97(d,J＝5.0Hz,4H),7.32(d,J＝5.0Hz,4H),3.43 (s,4H),3.02-2.92(m,2H),1.27(d,J＝5.0Hz,12H)； 13 C NMR(126MHz,CDCl 3 )δ 198.4,154.6,134.7,128.4,126.6,34.2,32.5,23.6.
Example 49
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4- (tert-butyl) phenyl) butane-1, 4-dione (II-10), having the following structural formula:
the procedure of example 1 was repeated except for using 4-tert-butylphenylacetaldehyde (105.1 mg,0.51 mmol) instead of phenylglyoxylic acid in example 1 and for adding the same materials, to give 1, 4-bis (4- (tert-butyl) phenyl) butane-1, 4-dione (42.4 mg,0.121mmol,47% yield).
1 H NMR(500MHz,CDCl 3 )δ7.98(d,J＝10.0Hz,4H),7.49(d,J＝10.0Hz,4H), 3.43(s,4H),1.35(s,18H)； 13 C NMR(126MHz,CDCl 3 )δ198.4,156.8,134.3,128.1, 125.5,35.1,32.6,31.1.
Example 50
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4-cyclohexylphenyl) butane-1, 4-dione (II-11), having the structural formula:
the same procedures used in example 1 were repeated except for using 4-cyclohexylphenylacetaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (4-cyclohexylphenyl) butane-1, 4-dione (32.5 mg,0.081mmol,54% yield).
1 H NMR(500MHz,CDCl 3 )δ7.96(d,J＝5.0Hz,4H),7.30(d,J＝5.0Hz,4H),3.43 (s,4H),2.62-2.53(m,2H),1.93-1.82(m,9H),1.81-1.71(m,2H),1.49-1.35(m,9H)； 13 C NMR(126MHz,CDCl 3 )δ198.5,153.7,134.7,128.3,127.0,44.7,34.1,32.5, 26.7,26.0；HRMS(ESI-TOF)Calcd for C 28 H 35 O 2 [M+H] + :403.2637；found 403.2639.
Example 51
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4-phenoxyphenyl) butane-1, 4-dione (II-12), having the following structural formula:
the same procedures used in example 1 were repeated except for using 4-phenoxyphenylacetaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (4-phenoxyphenyl) butane-1, 4-dione (40.4 mg,0.096mmol,39% yield).
1 H NMR(500MHz,CDCl 3 )δ8.02(d,J＝10.0Hz,4H),7.40(t,J＝7.5Hz,4H),7.20 (t,J＝7.5Hz,2H),7.08(d,J＝5.0Hz,4H),7.02(d,J＝5.0Hz,4H),3.41(s,4H)； 13 C NMR(126MHz,CDCl 3 )δ197.3,162.0,155.5,131.5,130.4,130.0,124.6,120.1, 117.4,32.4；HRMS(ESI-TOF)Calcd for C 28 H 23 O 4 [M+H] + :423.1596；found 423.1598.
Example 52
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (3, 5-dimethylphenyl) butane-1, 4-dione (II-13), having the following structural formula:
the same procedures used in example 1 were repeated except for using 3, 5-dimethylbenzene glyoxylic acid instead of the phenylglyoxylic acid used in example 1 to give 1, 4-bis (3, 5-dimethylphenyl) butane-1, 4-dione (27.3 mg,0.093mmol,61% yield).
1 H NMR(500MHz,CDCl 3 )δ7.65(s,4H),7.21(s,2H),3.42(s,4H),2.38(s,12H)； 13 C NMR(126MHz,CDCl 3 )δ199.20,138.2,136.9,134.7,125.9,32.8,21.2.
Example 53
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (2-fluorophenyl) butane-1, 4-dione (II-14) having the following structural formula:
the same procedures used in example 1 were repeated except for using 2-fluorobenzaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (2-fluorophenyl) butane-1, 4-dione (18.9 mg,0.069mmol,46% yield).
1 H NMR(500MHz,CDCl 3 )δ7.90(td,J＝5.0,10.0Hz,2H),7.56-7.49(m,2H), 7.26-7.21(m,2H),7.19-7.12(m,2H),3.47-3.41(m,4H)； 113 C NMR(126MHz, CDCl 3 )δ196.7(d,J＝4.0Hz),162.1(d,J＝255.1Hz),134.5(d,J＝9.0Hz),130.7 (d,J＝2.6Hz),125.5(d,J＝13.1Hz),124.4(d,J＝3.3Hz),116.6(d,J＝23.8Hz),37.42(dd,J＝8.2,2.0Hz)； 19 F NMR(471MHz,CDCl 3 )δ-109.0；
Example 54
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4-fluorophenyl) butane-1, 4-dione (II-15) having the following structural formula:
the procedure of example 1 was repeated except for using 4-fluorobenzaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (4-fluorophenyl) butane-1, 4-dione (24.2 mg,0.088mmol,59% yield).
1 H NMR(500MHz,CDCl 3 )δ8.10-8.03(m,4H),7.19-7.11(m,4H),3.43(s,4H)； 19 F NMR(471MHz,CDCl 3 )δ-105.11； 13 C NMR(126MHz,CDCl 3 )δ197.0,165.8 (d,J＝255.8Hz),133.2(d,J＝2.5Hz),130.7(d,J＝8.8Hz),115.7(d,J＝22.7Hz), 32.4.
Example 55
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4 bromophenyl) butane-1, 4-dione (II-16), having the structural formula:
the same procedures used in example 1 were repeated except for using 4-bromophenylacetaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (4-bromophenyl) butane-1, 4-dione (24.0 mg,0.061mmol,38% yield).
1 H NMR(500MHz,CDCl 3 )δ7.62(d,J＝10.0Hz,2H),7.57(dd,J＝10.0,5.0Hz, 2H),7.41-7.37(m,2H),7.33-7.28(m,2H),3.38(s,4H)； 13 C NMR(126MHz,CDCl 3 ) δ202.2,141.3,133.7,131.6,128.8,127.5,118.6,36.9.
Example 56
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (2-bromophenyl) butane-1, 4-dione (II-17), having the structural formula:
the procedure of example 1 was repeated except for using 2-bromophenylacetaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (2-bromophenyl) butane-1, 4-dione (24.0 mg,0.061mmol,40% yield).
1 H NMR(500MHz,CDCl 3 )δ7.89(d,J＝10.0Hz,4H),7.63(d,J＝10.0Hz,4H), 3.41(s,4H)； 13 C NMR(126MHz,CDCl 3 )δ197.5,135.5,132.0,129.6,128.4,32.5.
Example 57
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (2-trifluoromethylphenyl) butane-1, 4-dione (II-18), having the structural formula:
the same procedures used in example 1 were repeated except for using 2-trifluoromethylphenylacetaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (2-trifluoromethylphenyl) butane-1, 4-dione (25.9 mg,0.069mmol,45% yield).
1 H NMR(500MHz,CDCl 3 )δ7.75-7.69(m,4H),7.68-7.63(m,2H),7.61-7.55(m, 2H),3.30(s,4H)； 19 F NMR(471MHz,CDCl 3 )δ-58.2； 13 C NMR(126MHz,CDCl 3 ) δ202.6,140.0,131.9,130.2,127.5,127.0(dd,J＝49.0,32.8Hz),126.6(q,J＝5.0 Hz),122.5(t,J＝274.5Hz),37.0；HRMS(ESI-TOF)Calcd for C 18 H 12 F 6 O 2 Na [M+Na] + :397.0639；found 397.0637.
Example 58
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (5, 6,7, 8-tetrahydronaphthalen-2-yl) butane-1, 4-dione (II-19), having the following structural formula:
the procedure of example 1 was repeated except for using 5,6,7, 8-tetrahydronaphthaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (5, 6,7, 8-tetrahydronaphthalen-2-yl) butane-1, 4-dione (27.0 mg,0.078mmol,52% yield).
1 H NMR(500MHz,CDCl 3 )δ7.77-7.72(m,4H),7.17-7.12(m,2H),3.40(s,4H), 2.88-2.76(m,8H),1.88-1.74(m,8H)； 13 C NMR(126MHz,CDCl 3 )δ198.8,143.1, 137.4,134.3,129.3,129.0,125.1,32.6,29.6,29.3,23.0,22.82；HRMS(ESI-TOF)Calcd for C 24 H 27 O 2 [M+H] + :347.2011；found 347.2013.
Example 59
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (2, 3-dihydro-1H-inden-5-yl) butane-1, 4-dione (II-20), having the following structural formula:
the procedure of example 1 was repeated except for using 2- (2, 3-dihydro-1H-inden-5-yl) -2-oxoacetic acid instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (2, 3-dihydro-1H-inden-5-yl) butane-1, 4-dione (18.8mg,0.059 mmol,41% yield).
1 H NMR(500MHz,CDCl 3 )δ7.89(s,2H),7.86-7.82(m,2H),7.30(d,J＝10.0Hz, 2H),3.43(s,4H),2.96(t,J＝7.5Hz,8H),2.16-2.08(m,4H)； 13 C NMR(126MHz, CDCl 3 )δ198.8,150.2,144.7,135.3,126.6,124.3,124.1,33.0,32.8,32.6,25.4； HRMS(ESI-TOF)Calcd for C 22 H 22 O 2 Na[M+Na] + :341.1517；found 341.1511.
Example 60
This example provides a process for the preparation of 1, 4-dicarbonyl compounds, 1, 4-bis (4- (3-methoxypropyl) phenyl) butane-1, 4-dione (II-21), having the following structural formula:
the procedure of example 1 was repeated except for using 4- (3-methoxypropyl) phenylacetaldehyde instead of phenylglyoxylic acid in example 1 to give 1, 4-bis (4- (3-methoxypropyl) phenyl) butane-1, 4-dione (30.0 mg,0.078mmol, 53% yield).
1 H NMR(500MHz,CDCl 3 )δ7.96(d,J＝10.0Hz,4H),7.29(d,J＝10.0Hz,4H), 3.43(s,4H),3.38(t,J＝5.0Hz,4H),3.34(s,6H),2.76(t,J＝7.5Hz,4H),1.95-1.86(m,4H)； 13 C NMR(126MHz,CDCl 3 )δ198.3,147.8,134.8,128.6,128.3,71.6,58.5, 32.5,32.3,30.9；HRMS(ESI-TOF)Calcd for C 24 H 30 O 4 Na[M+Na] + :405.2042；found 405.2042.
Example 61
This example provides a method for preparing 1, 4-dicarbonyl compound, which prepares bis ((1R, 2S, 5R) -2-isopropyl-5-methylcyclohexyl) 3,3' - (succinylbis (4, 1-phenylene)) dipropionate (II-22) with the following structural formula:
(1) 3- (4-Acetylbenzene)Base) propionic acid (695.6 mg,3.6 mmol), L-menthol (466.8 mg,3.0 mmol), DMAP (46.4 mg,0.38 mmol) and DCM (10 mL) were added sequentially to a dry 50mL flask under nitrogen at 0deg.C. DCC (759.8 mg,3.68 mmol) was then added, stirred at this temperature for 10min, and stirred at room temperature overnight. The reaction mixture was filtered, concentrated in vacuo, and then purified by column chromatography to give the desired compound (1 r,2s,5 r) -2-isopropyl-5-methylcyclohexyl 3- (4-acetylphenyl) propionate (793.0 mg,2.40mmol, 80%). 1 H NMR(500MHz,CDCl 3 ) δ7.87(d,J＝8.5Hz,2H),7.29(d,J＝8.0Hz,2H),4.66(td,J＝11.0,4.5Hz,1H),3.00(t,J＝7.5Hz,2H),2.63(t,J＝7.5Hz,2H),2.56(s,3H),1.96-1.86(m,1H), 1.72-1.59(m,3H),1.50-1.39(m,1H),1.36-1.25(m,1H),1.07-0.96(m,1H), 0.90-0.84(m,4H),0.82(d,J＝7.0Hz,3H),0.68(d,J＝7.0Hz,3H)； 13 C NMR(126 MHz,CDCl 3 )δ197.6,171.9,146.2,135.3,128.51,128.48,74.3,46.9,40.8,35.5, 34.1,31.3,30.9,26.5,26.1,23.3,21.9,20.7,16.2.HRMS(ESI-TOF)Calcd for C 21 H 30 O 3 Na[M+Na] + :353.2093；Found 353.2097.
(2) The compound (1R, 2S, 5R) -2-isopropyl-5-methylcyclohexyl 3- (4-acetylphenyl) propionate (1 mmol,1.0 eq), selenium dioxide (1.5 eq) and dry pyridine, 10 ml) were added in this order, heated to 110℃and reacted for 1 hour, cooled to 90℃and incubated for 4 hours. After reaction interpretation, the mixture was filtered, washed with ethyl acetate, acidified with 1N hydrochloric acid (10 ml), the organic phase was separated and the aqueous phase extracted with ethyl acetate (3X 50 ml). The organic phases were combined and 1N sodium hydroxide (50 ml) was added and the aqueous phase was discarded. The organic phase was washed with water (25 ml) and adjusted to a pH of about 1.5 with 1N hydrochloric acid. The organic phases were combined, dried, concentrated, and purified by column chromatography to give 4- (3- (((1R, 2S, 5R) -2-isopropyl-5-methylcyclohexyl) oxy) -3-oxopropyl) phenylglyoxylic acid. 1 H NMR(500MHz,CDCl 3 )δ8.24-8.03(m,3H), 7.35-7.27(m,2H),4.67(td,J＝11.0,4.5Hz,1H),3.00(t,J＝7.0Hz,2H),2.63(t,J＝7.0Hz,2H),1.96-1.87(m,1H),1.75-1.58(m,3H),1.52-1.41(m,1H),1.38-1.28(m, 2H),1.07-0.90(m,2H),0.88(d,J＝6.5Hz,3H),0.83(d,J＝6.5Hz,3H),0.68(d,J＝ 7.0Hz,3H)； 13 C NMR(126MHz,CDCl 3 )δ185.1,172.4,163.4,148.9,131.2,130.2, 128.9,74.8,46.9,40.8,35.3,34.1,31.3,31.1,26.1,23.3,21.9,20.7,16.2:HRMS(ESI-TOF)Calcd for C 21 H 29 O 5 [M+H] + :361.2015；Found 361.2014.
(3) The procedure of example 1 was repeated except for using 4- (3- (((1R, 2S, 5R) -2-isopropyl-5-methylcyclohexyl) oxy) -3-oxopropyl) phenylacetic acid instead of phenylglyoxylic acid in example 1 to give bis ((1R, 2S, 5R) -2-isopropyl-5-methylcyclohexyl) 3,3' - (succinylbis (4, 1-phenylene)) dipropionate (45.0 mg,0.068mmol,46% yield).
1 H NMR(500MHz,CDCl 3 )δ7.96(d,J＝7.5Hz,4H),7.31(d,J＝7.5Hz,4H), 4.68(td,J＝10.0,5.0Hz,2H),3.42(s,4H),3.01(t,J＝7.5Hz,4H),2.64(t,J＝7.5Hz,4H),1.98-1.89(m,2H),1.77-1.60(m,8H),1.52-1.40(m,2H),1.38-1.24(m,2H), 1.10-0.97(m,2H),0.89(d,J＝10.0Hz,6H),0.84(d,J＝5.0Hz,6H),0.70(d,J＝ 10.0Hz,2H)； 13 C NMR(126MHz,CDCl 3 )δ198.2,172.0,146.3,135.1,128.5,128.3, 74.4,47.0,40.9,35.6,34.2,32.5,31.3,31.0,26.2,23.4,21.9,20.7,16.3；HRMS(ESI-TOF)Calcd for C 44 H 55 O 6 [M+H] + :679.3999；found 679.4001.
Example 62
This example provides a process for the preparation of a 1, 4-dicarbonyl compound, which produces (1 r,3r,5r,7 r) -adamantan-2-yl 4- (4- (4- (3- ((1 r,3r,5r,7 r) -adamantan-2-yl) oxy) -3-oxopropyl) phenyl) -4-oxobutanoyl) butanoate (II-23) having the following structural formula:
(1) Reference example 61 step (1), adamantan alcohol (468.7 mg,3.08 mmol) was used in place of L-menthol to prepare (1 r,3r,5r,7 r) -adamantan-2-yl 3- (4-acetylphenyl) propionate (882.1 mg,2.96mmol,83%).
(2) Reference example 61 step (2) 4- (3- (((1 r,3r,5r,7 r) -adamantan-2-yl) oxy) -3-oxopropyl) phenylglyoxylic acid was prepared.
1 H NMR(500MHz,CDCl 3 )δ8.16(d,J＝8.5Hz,2H),7.83(s,1H),7.38(d,J＝ 8.0Hz,2H),4.96-4.91(m,1H),3.07(t,J＝7.5Hz,2H),2.73(t,J＝7.5Hz,2H),1.99-1.67(m,12H),1.52(d,J＝12.0Hz,2H)； 13 C NMR(126MHz,CDCl 3 )δ184.9, 172.2,163.3,149.0,131.2,130.2,128.9,77.7,37.2,36.2,35.4,31.8,31.6,31.2,27.1, 26.8；HRMS(ESI-TOF)Calcd for C 22 H 27 O 5 [M+H] + :371.1858；Found 371.1853.
(3) The same procedures used in example 1 were repeated except for using 4- (3- (((1 r,3r,5r,7 r) -adamantan-2-yl) oxy) -3-oxopropyl) phenylacetic acid instead of the phenylglyoxylic acid used in example 1 to give (1 r,3r,5r,7 r) -adamantan-2-yl 4- (4- (4- (3- ((1 r,3r,5r,7 r) -adamantan-2-yl) oxy) -3-oxopropyl) phenyl) -4-oxobutanoyl) butanoic acid ester (69.6 mg,0.105mmol,42% yield).
1 H NMR(500MHz,CDCl 3 )δ7.96(d,J＝10.0Hz,4H),7.32(d,J＝10.0Hz,4H), 4.96-4.90(m,2H),3.42(s,4H),3.04(t,J＝7.5Hz,4H),2.69(t,J＝7.5Hz,4H), 1.98-1.88(m,9H),1.87-1.78(m,9H),1.78-1.75(m,2H),1.75-1.68(m,4H),1.56-1.49(m,4H)； 13 C NMR(126MHz,CDCl 3 )δ198.2,171.8,146.3,135.0,128.4, 128.3,37.3,36.2,35.6,32.5,31.8,31.7,31.0,27.1,26.9；HRMS(ESI-TOF)Calcd for C 42 H 59 O 6 [M+H] + :659.4312；found 659.4312.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (8)

1. The preparation method of the 1, 4-dicarbonyl compound is characterized by comprising the following steps:
taking a compound shown in a formula (I) and acetylene as raw materials, reacting under the action of a solvent, a metal iridium bipyridine catalyst and alkali, and preparing the compound shown in a formula (II) through illumination;
wherein R in formula (I) 1 Is thatOne of them;
the R is 2 The substituent on the benzene ring can be one or more, and is independently selected from hydrogen atom, halogen atom, C1-C6 alkyl, C1-C6 ether group, C1-C6 ester group, phenoxy or trifluoromethyl;
the iridium bipyridine catalyst is [ Ir (ppy) 2 (dtbbpy)]PF 6 、Ir[dF(CF 3 )ppy] 2 bpyPF 6 、Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 、Ir[dF(CF 3 )ppy] 2 (phen)PF 6 、Ir[dFCF 3 ppy] 2 (bpy)PF 6 、Ir[dFppy] 2 (bpy)PF 6 、Ir[dFppy] 2 (dtbbpy)PF 6 、Ir[p-Fppy] 2 (bpy)PF 6 、Ir[p-Fppy] 2 (dtbpy)PF 6 、Ir[4-t-Bu-Phenyl-4-t-Bu-Py] 2 (dtbpy)PF 6 、Ir[dF(Me)ppy] 2 (dtbbpy)PF 6 、Ir(ppy) 2 (dtbbpy)PF 6 、Ir[dF(F)ppy] 2 (dCF 3 )PF 6 、[Ir(ppy) 2 (bpy)]PF 6 、Ir[p-F(Me)ppy] 2 (dtbbpy)PF 6 、Ir[d(t-Bu)(CF 3 )ppy] 2 (dtbbpy)Cl、Ir[d(t-Bu)(CF 3 )ppy] 2 (dtbbpy)PF 6 、Fac-Ir(ppy) 3 、Fac-Ir(dFppy) 3 、Fac-Ir[d-F(p-t-Bu)ppy] 3 、Fac-Ir(p-CF 3 ppy) 3 、Fac-Ir(p-Fppy) 3 、Fac-Ir(p-t-Bu-ppy) 3 、Fac-Ir(d-Fppy) 3 、Fac-Ir(3-t-Bu-ppy) 3 Or Fac-Ir [ (3-t-Bu-phenyl) -4-t-Bu-py)] 3 ；
The light of illumination is monochromatic light or mixed light with the wavelength range of 200-800 nm.
2. The method according to claim 1, wherein the base is one of potassium carbonate, cesium carbonate, potassium fluoride, potassium phosphate, potassium bicarbonate, sodium bicarbonate, dipotassium hydrogen phosphate, pyridine, 2, 6-lutidine, triethylamine, and tetramethylguanidine.
3. The method according to claim 2, wherein the base is selected from potassium fluoride or dipotassium hydrogen phosphate.
4. The preparation method according to claim 1, wherein the molar ratio of the compound represented by the formula (I), the iridium metal bipyridine-based catalyst and the base is 1: (0.005-0.1): (0.1-3).
5. The method of claim 1, wherein the solvent is one or more of dichloromethane, dichloroethane, acetone, acetonitrile, methanol, ethanol, tetrahydrofuran, 1, 4-dioxane, or water.
6. The process according to claim 5, wherein the solvent is a mixture of water with dichloromethane, dichloroethane, acetone, acetonitrile, methanol, ethanol, tetrahydrofuran or 1, 4-dioxane.
7. The method of claim 1, wherein acetylene in the reaction is provided by a pressure vessel.
8. The method according to claim 1, wherein the pressure of acetylene is in the range of 1 to 10atm.
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