CN117756950A - Bio-based carbonylation reagent and application thereof - Google Patents

Bio-based carbonylation reagent and application thereof Download PDF

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CN117756950A
CN117756950A CN202311472978.3A CN202311472978A CN117756950A CN 117756950 A CN117756950 A CN 117756950A CN 202311472978 A CN202311472978 A CN 202311472978A CN 117756950 A CN117756950 A CN 117756950A
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田兵
李淑君
阎睿
王游
陈志俊
刘守新
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Northeast Forestry University
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Northeast Forestry University
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Abstract

The application provides a bio-based carbonylation reagent, a preparation method and application thereof. The bio-based carbonylation reagents provided herein include methyl esterified cellulose. The carbonylation reagent provided by the invention has the advantages of convenient preparation, low cost, stable property, mild carbon monoxide release condition and capability of being applied to various carbonylation reactions.

Description

Bio-based carbonylation reagent and application thereof
Technical Field
The invention relates to a bio-based carbonylation reagent and application thereof.
Background
Carbonyl structures are not only widely found in pharmaceuticals, agrochemicals and functional materials, but also as precursor structures for a variety of conversion activities in synthetic chemistry, and carbonylation reactions are the most powerful method of constructing carbonyl structures. Incorporating one in the moleculeCarbon oxide is the most direct and effective method of constructing complex carbonyl-containing compounds (Wu, x. -f., neumann, h., beller, M.Chem.Soc.Rev.2011,40,4986;Franke,R, selent, d.,chem. Rev.2012,112, 5675.). Although carbon monoxide has been widely used in the field of organic synthesis by coupling and series carbonylation reactions using the gas, the high toxicity and high flammability of carbon monoxide gas has led to extremely high requirements on the proficiency of storage and use equipment, operation, and the general need for high pressure resistant tanks and carbon monoxide detectors, which are detrimental to its safe and convenient use in academic research, especially in laboratories. In order to overcome the hazards and inconveniences associated with the use of carbon monoxide gas, a number of carbon monoxide substitutes such as formic acid and its derivatives, aldehydes, carboxylic acids, acid chlorides, carbon dioxide, chloroform, metal carbonyls, etc. have been developed as a series of carbonylation reagents that release carbon monoxide by reaction (Cao, j., zheng, z. -j., xu, z., xu, l. -W.Coord.Chem.Rev.2017,336,43;Morimoto,T, kakichi, K.Angew.Chem.Int.Ed.2004,43,5580;Grushin,V.V, alper, h.organometallics 1993,12,3846; konishi, h., manabae, k.synlett 2014,25,1971), and are widely used in carbonylation reactions.
Classical liquid carbonylation reagents, such as formic acid, formamide, aldehydes and acid chlorides, are generally highly toxic, volatile and air sensitive and often require additional activators such as metal catalysts and acetic anhydride to release carbon monoxide gas during use. The solid carbonylation reagent has the advantages of more stability, more convenient operation, less toxicity and the like. In recent years, research studies on Wu, yudin, skrydstrup and Manabe have developed organic molecule-based carbonylation reagents with more stable performance and more convenient carbonylation operations, such as benzene-1, 3, 5-tricarboxylic acid triester (Jiang, l. -b., qi, x., wu, x. -f.tetrahedron lett.2016,57,3368), 6-methyl-4, 8-dioxo-1, 3,6, 2-dioxaborane-2-carboxylic acid (tie, c. -h.et al angelw.chem.int.ed.2021, 60,4342), 9-methyl-9H-fluorene-9-carbonyl chloride (Hermange, p.et.j.am.chem.soc.2011, 133, 6061), and 3-oxo-benzisothiazole-2 (3H) -formaldehyde 1, 1-dioxide (Ueda, t., koni, h., angele, k.62.chem.62.d.62.62). However, these solid carbonylation reagent synthesis precursors, as reported so far, are derived from fossil raw materials, are expensive, require complex synthesis steps, require additional activating reagents or high temperatures to release carbon monoxide, and are poorly compatible, resulting in very limited types of carbonylation reactions involved. Therefore, there is a strong need in the art for a solid carbonylation reagent that is convenient to prepare, inexpensive, stable in properties, mild in carbon monoxide release conditions, and applicable to a wide variety of carbonylation reactions.
Disclosure of Invention
The invention provides a novel carbonylation reagent and a preparation method and application thereof, in order to overcome the defects of complex preparation, high cost, limited carbonylation reaction types and poor functional group compatibility of the solid carbonylation reagent in the prior art. The carbonylation reagent provided by the invention is a solid carbonylation reagent which is convenient to prepare, low in cost, stable in property, mild in carbon monoxide release condition and applicable to various carbonylation reactions.
In a first aspect, the present invention provides a bio-based carbonylation reagent comprising methyl esterified cellulose.
According to some embodiments of the invention, the methyl esterified cellulose has structural units represented by formula 1:
in formula 1, R 1 、R 2 And R is 3 Is hydrogen orAnd at least R 1 、R 2 And R is 3 At least one of which is->
According to some embodiments of the invention, the methyl esterified cellulose has a degree of substitution of 0.1 to 3, preferably 0.5 to 2, further preferably 1 to 1.5, most preferably 1.2 to 1.4.
In a second aspect, the present invention provides a process for the preparation of a carbonylation reagent comprising the steps of:
(1) Reacting a cellulosic feedstock in a formic acid solution to produce a reaction mixture comprising methyl esterified cellulose;
(2) Subjecting the reaction mixture to solid-liquid separation;
(3) Concentrating and drying the liquid separated in the step (2).
According to some embodiments of the invention, the formic acid solution is 10-100% (e.g., 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70, 75, 80, 85, 90, 95, 100%) formic acid by mass fraction of formic acid.
According to some embodiments of the invention, the mass to volume ratio of the formic acid solution to the cellulosic feedstock is from 1mL/g to 100mL/g, e.g., 1mL/g, 10mL/g, 15mL/g, 20mL/g, 30mL/g, 40mL/g, 50mL/g, 60mL/g, 70mL/g, 80mL/g, 100mL/g.
According to some embodiments of the invention, in step (1), the temperature of the reaction is between 10 and 120 ℃.
According to some embodiments of the invention, in step (1), the reaction time is from 1 minute to 24 hours; for example 1 hour, 2 hours, 4 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours or 22 hours.
According to some embodiments of the invention, the reaction comprises a first stage and a second stage, the first stage being carried out at 80-120 ℃, preferably 90-110 ℃, more preferably e.g. 95 ℃ for 4-8 hours, preferably 5-6.5 hours, e.g. 6 hours; the second stage is carried out at 20-40 c, preferably 20-30 c, e.g. 25 c, for 8-14 hours, preferably 10-13 hours, e.g. 12 hours.
According to some embodiments of the invention, the first stage is carried out at 90-110 ℃ for 4-8 hours, preferably 5-6.5 hours; the second stage is carried out at 20-30deg.C for 8-14 hr.
According to some embodiments of the invention, the first stage is carried out at 95 ℃ for 6 hours; the second stage is carried out at 20-30deg.C for 8-14 hr.
According to some embodiments of the invention, the degree of substitution of the methyl esterified cellulose obtained in step (1) is from 0.1 to 3, preferably from 0.5 to 2. In some preferred embodiments, the degree of substitution of the methyl esterified cellulose obtained in step (1) is from 0.8 to 2, preferably from 1 to 1.5, most preferably from 1.2 to 1.4. In a preferred embodiment, the methyl esterified cellulose has a degree of substitution of 1.3 to 1.4.
In a third aspect, the present invention provides the use of a carbonylation reagent as described in the first aspect or as prepared by a method as described in the second aspect in a carbonylation reaction. In some embodiments, in the carbonylation reaction, a carbonyl group is introducedSpecifically, the compound can be ester->Amide group->
In a fourth aspect, the present invention provides a carbonylation reaction process comprising:
reacting reactant a, reactant B, and the carbonylation reagent of the first aspect or the carbonylation reagent prepared by the method of the second aspect, to form a carbonyl-containing compound, wherein reactant a is selected from an organic compound having a halogen group, preferably an aryl halide or heteroaryl halide; the reactant B is selected from hydroxyl, NH 2 Organic compounds of terminal alkynyl, boric acid and/or boric acid ester groups.
According to some embodiments of the invention, the organic compound having a halogen group is represented by formula I:
ring a represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms;
in the formula I, R 1 Represents one or more substituents selected from hydrogen, deuterium, cyano, amino, nitro, C1-C5 alkylamino, halogen, C1-C5 alkyl, C1-C5 alkoxy, phenyl, benzoyl, methoxycarbonyl, ethoxycarbonyl.
In some embodiments, ring A is a benzene ring, 4-methyl benzene ring, 4-tert-butyl benzene ring, 4-methoxy benzene ring, 3-methoxy benzene ring, 2-methoxy benzene ring/4-phenyl benzene ring, 4-benzoyl benzene ring, 4-cyano benzene ring, 4-methyl ester benzene ring, 4-trifluoromethyl benzene ring, 4-n-butyl oxygen benzene ring, 2-trifluoromethyl benzene ring, 3, 5-dimethyl benzene ring, 3, 5-dimethoxy benzene ring, 3,4, 5-trimethyl benzene ring, 2-naphthalene ring, 1, 2-methylenedioxy benzene ring, 2, 3-dihydrobenzo [ b ] [1,4] dioxin, 2-methylbenzoxazole, benzofuran ring, furan ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, fluorene, indole ring, quinoline ring, quinoxaline ring, carbamate benzene ring, ethylamine benzene ring or halogenated benzene ring.
In some embodiments, the halogen-containing organic compound is selected from one or more of the following compounds:
preferably bromine or iodine.
In some embodiments, the reactant B is selected from compounds of the following structural formula:
wherein n is 0, 1, 2, 3 or 4; r is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro, cyano, halogen, hydroxy, amino; x and Y are each independently halogen or amino, halogen preferably bromine or iodine.
Examples of the reactant B include, but are not limited to:
according to some embodiments of the invention, the reactant B is selected from hydroxyl-containing organic compounds, NH-containing or NH-containing 2 An organic compound containing an alkynyl group, and an organic compound containing a boric acid group or a boric acid ester group.
In some embodiments, the hydroxyl-containing organic compound is an alcohol compound.
In some embodiments, the alcohol compound is selected from C1-C10 alkyl alcohols, the C1-C10 alkyl optionally substituted with a substituent selected from cyano, nitro, halogen, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C6-C10 aryl, amino, C1-C5 alkoxy, C1-C5 alkyl substituted amino.
In some embodiments, the alcohol compound is selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, isobutanol, sec-butanol, n-pentanol, 2-methylbutanol, 3-methylbutanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, cyclopropanol, cyclobutylalcohol, cyclopentanol, cyclohexanol, ethylene glycol, benzyl alcohol, phenethyl alcohol, phenylpropanol, Or 1-cyclohexenyl methanol, etc.
In some embodiments, the NH or NH-containing 2 The organic compound of (2) is selected from the group consisting of C3-C10 alkylamine, C6-C20 arylamine, C3-C20 heteroarylamine, said C3-C10 alkyl optionally substituted with a substituent selected from the group consisting of cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C10 aryl, C3-C10 heteroaryl, amino, C1-C5 alkoxy, C1-C5 alkyl substituted amino, said C6-C20 aryl and C3-C20 heteroaryl optionally substituted with C1-C5 alkyl, C1-C5 alkoxy, halogen, cyano, nitro and amino.
In some embodiments, the NH or NH-containing 2 Is selected from one or more of the following compounds:
in some embodiments, the terminal alkynyl-containing organic compound is selected from R 2 D, wherein R is 2 Representation ofD is selected from the group consisting of C3-C10 alkyl, C6-C20 aryl, and C3-C20 heteroaryl, said C3-C10 alkyl, C6-C20 aryl, and C3-C20 heteroaryl being optionally substituted with a substituent selected from the group consisting of cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C14 aryl, amino, C1-C5 alkoxy, C6-C10 aryl, C3-C10 heteroaryl, C1-C5 alkyl-substituted amino;
in some embodiments, the terminal alkynyl-containing organic compound is selected from one or more of the following compounds:
In some embodiments, the organic compound containing a boric acid group or a borate group is selected from R 3 E, wherein R is 3 Is thatR 4 And R is 5 Each independently is C1-C6 alkyl or linked together to form a 5-6 membered ring; e is selected from the group consisting of C3-C10 alkyl, C6-C20 aryl and C3-C20 heteroaryl, said C3-C10 alkyl, C6-C20 aryl and C3-C20 heteroaryl being optionally substituted with a substituent selected from the group consisting of cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C14 aryl, amino, C1-C5 alkoxy, C6-C10 aryl, C3-C10 heteroaryl, C1-C5 alkyl-substituted amino.
In some embodiments, the boric acid-based compound is selected from
In some embodiments, the reaction is carried out in a solvent, which may be one or more of an alkane solvent, a substituted aryl solvent, a nitrile solvent, a halogenated hydrocarbon solvent, an ether solvent, a ketone solvent, an ester solvent, and an amide solvent. The alkane solvent may be n-hexane. The substituted aromatic solvent may be one or more of chlorobenzene, toluene and trifluoromethylbenzene. The nitrile solvent may be acetonitrile. The halogenated hydrocarbon solvent can be dichloromethane and chloroform. The ether solvent can be tetrahydrofuran, diethyl ether, methyl tertiary butyl ether, ethyl tertiary butyl ether, anisole, ethylene glycol dimethyl ether and 1, 4-dioxane. The ketone solvent may be acetone. The ester solvent can be ethyl acetate and ethylene glycol diacetate. The amide solvent can be N, N-Dimethylformamide (DMF). The amount of the solvent to be used is not particularly limited as long as the reaction is not affected. The solvent may be subjected to anhydrous treatment (the operation and method of anhydrous treatment are conventional in the art).
In some embodiments, the carbonylation reaction is carried out in an aprotic polar solvent, preferably selected from acetonitrile, methanol, ethanol, isopropanol, tetrahydrofuran, dioxane, DMF or DMSO. Preferably, the solvent is DMF.
In some embodiments, the carbonylation reaction is performed in the presence of a palladium catalyst and the presence or absence of a phosphorus ligand,
in some embodiments, the palladium catalyst may be one or more of palladium acetate, palladium trifluoroacetate, palladium quaternary valerate, palladium dichlorodiacetonitrile, bis (benzonitrile) palladium chloride, palladium bromide, palladium iodide, palladium tetra acetonitrile tetrafluoroborate, palladium hexafluoroacetylacetonate, palladium di (acetylacetonate), palladium tetra acetonitrile triflate, palladium pivalate, and (1 e,4 e) -bis (dibenzylideneacetone) palladium, and may be one or more of bis (dibenzylideneacetone) dipalladium and tris (dibenzylideneacetone) dipalladium;
in some embodiments, the phosphorus ligand is selected from the group consisting of 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene, 1' -bis (diphenylphosphino) ferrocene, tri-o-tolylphosphine, tricyclohexylphosphine tetrafluoroborate, tri-t-butylphosphine tetrafluoroborate, di-t-butylmethylphosphine tetrafluoroborate, triphenylphosphine, 2-di-t-butylphosphino-2 ',4',6' -triisopropylbiphenyl, 2-dicyclohexylphosphorus-2 ' -methylbiphenyl, tris (2-furyl) phosphine, 2- (dicyclohexylphosphino) biphenyl, N-butylbis (1-adamantyl) phosphine, 2- (di-t-butylphosphine) -2' - (N, N-dimethylamino) biphenyl, 2- (di-t-butylphosphine) biphenyl, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1-biphenyl, 3 2-dicyclohexylphosphine-2 ',6' -diisopropyloxybiphenyl, 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl, rac-2- (di-t-butylphosphine) -1, 3 ' -bis (di-tert-butylphosphine) 2' - (N, N-dimethylamino) biphenyl, 2- (di-t-butylphosphine) -2' - (N, N-dimethylamino) biphenyl, 2' -dicyclohexylphosphine-2 ',6' -dicyclohexylphosphine-1, 1-diphenyl phosphine, 2-di-tert-butylphosphine-2 ' -methylbiphenyl, 2-dicyclohexylphosphino-2 ' - (N, N-dimethylamine) biphenyl, 1' -bis (di-tert-butylphosphino) ferrocene, bis (2-diphenylphosphinophenyl) ether, 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene, 1' -bis (diisopropylphosphino) ferrocene, 1, 2-bis (diphenylphosphino) benzene, 1,2,3,4, 5-pentaphenyl-1 ' - (di-tert-butylphosphino) ferrocene, or bis (diphenylphosphinomethane;
In some embodiments, the reaction is carried out in the presence of a base, preferably the base is selected from Na 3 PO 4 、K 3 PO 4 、LiOH、Na 2 CO 3 、K 2 CO 3 、t-BuOK、t-BuONa、t-BuOLi、NEt 3 1, 8-diazabicyclo [5.4.0]Undec-7-ene, diisopropylamine, or a combination thereof.
In some embodiments, the molar ratio of the palladium catalyst to the ligand in the carbonylation process may be in a conventional molar ratio in the art, preferably from 2.0:1 to 1.0:3, for example 1:1.5.
In some embodiments, the concentration of the halide in the carbonylation process may be conventional in the art, preferably from 0.01 to 5.00mol/L, and may preferably be from 0.01 to 0.20mol/L.
In some embodiments, the molar ratio of the alcohol compound to the halide compound in the carbonylation reaction process may be 1.0:1 to 100:1, and may preferably be 2.5:1 to 3.0:1.
In some embodiments, the carbonylation process wherein the base, such as a base, is selected from the group consisting of: na3PO 4 、K 3 PO 4 、LiOH、Na 2 CO 3 、K 2 CO 3 T-BuOK, t-Buona, t-Buoli, NEt3, 1, 8-diazabicyclo [5.4.0]Undec-7-ene, diisopropylamine, or a combination thereof.
In some embodiments, the carbonylation process has a molar ratio of base to halide of 1 to 10:1.
In some embodiments, the carbonylation reaction process, the reaction temperature can be 0 to 120 ℃, such as 0 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 85 ℃, 90 ℃, 100 ℃, 110 ℃, or 120 ℃. In some embodiments, the temperature of the reaction is from 20 ℃ to 50 ℃. In some embodiments, the temperature of the reaction is from 20 ℃ to 50 ℃. In some embodiments, the temperature of the reaction is from 20 ℃ to 50 ℃. In some embodiments, the temperature of the reaction is from 60 ℃ to 90 ℃. In some embodiments, the temperature of the reaction is from 80 ℃ to 120 ℃.
In some embodiments, the carbonylation reaction process may also be carried out under a protective gas. The shielding gas can be nitrogen and/or argon. The progress of the reaction may be monitored using detection methods conventional in the art (e.g., TLC, HPLC, HNMR), preferably with the halide disappearing or no longer reacting as an endpoint of the reaction. The reaction time may be 1 to 168 hours.
The invention has the positive progress effects that: the solid carbonylation reagent is cellulose formate, is derived from biological materials, and has the advantages of high yield, simple preparation, easy separation, good stability, low price, wide substrate universality, good functional group compatibility and mild reaction condition and simple operation when being applied to carbonylation reaction.
Drawings
FIG. 1 is a cellulose formate prepared in example 1 13 C NMR spectrum.
FIG. 2 is an FT-IR spectrum of a cellulose formate prepared in example 1.
FIG. 3 is a thermogram of the cellulose formate prepared in example 1.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below.
EXAMPLE 1 preparation of cellulose formate
In a 500mL round bottom reaction flask, 10g of cellulose and 300mL of formic acid were added in one portion under nitrogen or argon. The reaction was stirred at 95℃for 6 hours, followed by turning off the heating and stirring at room temperature for 12 hours. After the reaction is finished, filtering to remove solid residues, distilling filtrate by rotary distillation under reduced pressure to obtain a solid product, and recycling formic acid obtained by distillation. 400mL of deionized water was added to the solid product, stirred for 10 minutes, and the solid was collected after filtration. The solid was dried in an oven at 100 ℃ for 12 hours to give the desired product, cellulose formate 1. The target product 13 The C NMR spectrum is shown in FIG. 1, the FT-IR spectrum is shown in FIG. 2, and the thermogravimetric analysis spectrum is shown in FIG. 3.
Warp yarn 13 C NMR spectrum confirmed that the substitution degree of cellulose formate 1 prepared in this example was 1.27.
Example 2
Substantially the same as in example 1, except that the temperature was changed to 95℃to 50 ℃. Warp yarn 13 C NMR confirmed that the degree of substitution of cellulose formate 2 prepared in this example was 0.8.
Example 3
Substantially the same as in example 1, except that the temperature was changed to 95℃to 120 ℃. Warp yarn 13 C NMR confirmed that the degree of substitution of cellulose formate 3 prepared in this example was 1.34.
EXAMPLE 4 application of the cellulose formate prepared in examples 1-3 as carbonylation reagent to carbonylation reactions
The reaction route is as follows:
general operation step 1: pd (OAc) was reacted in a 10mL reaction tube under nitrogen blanket 2 (0.09 mmol,3 mol%), xantphos (0.012 mmol,4 mol%), t-BuOK (1.2 mmol,4 equiv.), carbonylation reagent (105 mg,1.77 equiv.), aryl halide (0.3 mmol,1 equiv.), alcohol compound (6 mmol,20 equiv.) and anhydrous DMF (3 mL). The reaction was then stirred at 100℃for 36 hours. After completion of the reaction, the mixture was diluted with 10mL of ethyl acetate and washed with water (10 mL. Times.3). The organic phase was dried over anhydrous MgSO 4 Drying, filtering, concentrating the filtrate, and separating by flash column chromatography (petroleum ether/ethyl acetate) to obtain the target product.
The reaction starting materials and products and yields are shown in table 1.
TABLE 1
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EXAMPLE 5 application of cellulose formate as carbonylation reagent to carbonylation reaction
The reaction route is as follows:
general operation step 2: pd (OAc) was reacted in a 10mL reaction tube under nitrogen blanket 2 (0.012 mmol,6 mol%), phosphorus ligand dppf (0.02 mmol,10 mol%), t-BuOK (1.2 mmol,4 equiv.), cellulose formate 1 (105 mg,1.77 equiv.), aryl iodide or aryl bromide (0.3 mmol,1 equiv.), amine compounds (0.4 mmol,2 equiv.) and anhydrous DMF (2 mL) as prepared in example 1. The reaction was then stirred at 80℃for 96 hours. After completion of the reaction, the mixture was diluted with 10mL of ethyl acetate and washed with water (10 mL. Times.3). The organic phase was dried over anhydrous MgSO 4 Drying, filtering, concentrating the filtrate, and separating by flash column chromatography (petroleum ether/ethyl acetate) to obtain the target product.
TABLE 2
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EXAMPLE 6 application of cellulose formate solid carbonylation reagent to carbonylation reaction
General operation step 3: pd (OAc) was reacted in a 10mL reaction tube under nitrogen blanket 2 (0.006mmol, 3 mol%) phosphorus ligand Ph 3 P (0.012 mmol,6 mol%), t-BuOK (0.6 mmol,3 equiv.), solid carbonylation reagent of cellulose formate 1 (70 mg,1.77 equiv.), aryl iodide or aryl bromide (0.3 mmol,1 equiv.), alkyne (0.4 mmol,2 equiv.) and anhydrous DMF (2 mL) prepared in example 1. The reaction was then stirred at room temperature (20-30 ℃ C.) for 24 hours. After completion of the reaction, the mixture was diluted with 10mL of ethyl acetate and washed with water (10 mL. Times.3). The organic phase was dried over anhydrous MgSO 4 Drying, filtering, concentrating the filtrate, and separating by flash column chromatography (petroleum ether/ethyl acetate) to obtain the target product.
TABLE 3 Table 3
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EXAMPLE 7 application of cellulose formate as carbonylation reagent to carbonylation reaction
The reaction route is as follows:
general operation step 4: pd (OAc) was reacted in a 10mL reaction tube under nitrogen blanket 2 (0.006mmol, 3 mol%) phosphorus ligand Ph 3 P (0.012 mmol,6 mol%), t-BuOK (0.6 mmol,3 equiv.), carbonylation reagent (70 mg,1.77 equiv.), aryl iodide or aryl bromide (0.3 mmol,1 equiv.), arylboronic acid (0.22 mmol,1.1 equiv.) and anhydrous DMF (2 mL). The reaction was then stirred at 80℃for 24 hours. After completion of the reaction, the mixture was diluted with 10mL of ethyl acetate and washed with water (10 mL. Times.3). The organic phase was dried over anhydrous MgSO 4 Drying, filtering, concentrating the filtrate, and separating by flash column chromatography (petroleum ether/ethyl acetate) to obtain the target product.
TABLE 4 Table 4
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Partial compound purification and profile data:
the reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. ( X=br, 49.35mg,99% yield; x=i, 49.35mg,99% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.90(d,J＝9Hz,2H),6.91(d,J＝9Hz,2H),3.88(s,3H),3.85(s,3H). 13 C NMR(125MHz,CDCl 3 )δ166.82,163.24,131.53,122.49,113.52,55.36,51.83.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. ( X=br, 40.38mg,81% yield; x=i, 37.89mg,76% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.63(d,J＝9.5Hz,1H),7.56(d,J＝1.5Hz,1H),7.33(t,J＝10Hz,1H),7.09(dd,J＝3.5,10.5Hz,1H),3.90(s,3H),3.84(s,3H). 13 C NMR(125MHz,CDCl 3 )δ166.90,159.45,131.34,129.31,121.89,119.43,113.84,55.33,52.11.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. ( X=br, 40.38mg,81% yield; x=i, 42.87mg,86% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.80(dd,J＝1.5,8Hz,1H),7.48-7.45(m,1H),6.99-6.96(m,2H),3.90(s,3H),3.89(s,3H). 13 C NMR(125MHz,CDCl 3 )δ166.70,159.07,133.50,131.64,120.10,199.96,111.96,55.95,52.00.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (29.29 mg,65% yield). 1 H NMR(500MHz,CDCl 3 )δ7.93(d,J＝10Hz,2H),7.23(d,J＝9.5Hz,2H),3.90(s,3H),2.40(s,3H). 13 C NMR(125MHz,CDCl 3 )δ167.15,143.52,129.54,129.03,127.33,51.93,21.62.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. ( X=br, 50.18mg,87% yield; x=i, 43.26mg,75% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.97(d,J＝10.5Hz,2H),7.45(d,J＝10.5Hz,2H),3.90(s,3H),1.34(s,9H). 13 C NMR(125MHz,CDCl 3 )δ167.05,156.43,129.36,127.28,125.25,51.86,34.98,31.03.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (29.4 mg,72% yield). 1 H NMR(500MHz,CDCl 3 )δ8.05-8.03(m,2H),7.57-7.53(m,1H),7.45-7.41(m,2H),3.91(s,3H). 13 C NMR(125MHz,CDCl 3 )δ167.04,132.85,130.03,129.48,128.28,52.04.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. ( X=br, 58.58mg,92% yield; x=i, 63.04mg,99% yield ). 1 H NMR(500MHz,CDCl 3 )δ8.12-8.10(m,2H),7.68-7.66(m,2H),7.64-7.62(m,2H),7.49-7.46(m,2H),7.40(t,J＝7.5Hz,1H),3.95(s,3H). 13 C NMR(125MHz,CDCl 3 )δ167.00,145.61,139.98,130.08,128.90,128.86,128.12,127.26,127.03,52.12.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. (36.76 mg,51% yield). 1 H NMR(500MHz,CDCl 3 )δ8.15(d,J＝8Hz,2H),7.84(d,J＝8Hz,2H),7.80(d,J＝8Hz,2H),7.62(t,J＝7.5Hz,1H),7.50(t,J＝7.5Hz,2H),3.97(s,3H). 13 C NMR(125MHz,CDCl 3 )δ196.03,166.30,141.29,136.91,133.19,132.93,130.09,129.76,129.48,128.44,52.46./>
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. (26.59 mg,55% yield). 1 H NMR(500MHz,CDCl 3 )δ8.15-8.13(m,2H),7.76-7.74(m,2H),3.96(s,3H). 13 C NMR(125MHz,CDCl 3 )δ165.42,133.90,132.21,130.08,117.95,116.38,52.72.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. ( X=br, 30.54mg,62% yield; x=i, 42.86mg,87% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.66(s,2H),7.19(s,1H),3.90(s,3H),2.36(s,6H). 13 C NMR(125MHz,CDCl 3 )δ167.46,138.00,134.55,129.99,127.27,51.99,21.14.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. ( X=br, 42.97mg,73% yield; x=i, 54.15mg,92% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.18(d,J＝2.5Hz,2H),6.64(t,J＝2.5Hz,1H),3.91(s,3H),3.82(s,6H). 13 C NMR(125MHz,CDCl 3 )δ166.84,160.60,131.97,107.07,105.75,55.54,52.23.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. ( X=br, 50.84mg,91% yield; x=i, 55.30mg,99% yield ). 1 H NMR(500MHz,CDCl 3 )δ8.62(s,1H),8.07(dd,J＝1,8.5Hz,1H),7.96(d,J＝8Hz,1H),7.89(d,J＝8.5Hz,2H),7.59(t,J＝7Hz,1H),7.55(t,J＝7Hz,1H),3.99(s,3H). 13 C NMR(125MHz,CDCl 3 )δ167.26,135.49,132.47,131.05,129.34,128.22,128.12,127.74,127.37,126.62,125.21,52.22.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. ( X=br, 45.94mg,85% yield; x=i, 53.51mg,99% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.63(dd,J＝2,10Hz,1H),7.44(s,1H),6.81(d,J＝10Hz,1H),6.01(s,2H),3.86(s,3H). 13 C NMR(125MHz,CDCl 3 )δ166.37,151.48,147.61,125.23,124.04,109.40,107.86,101.71,51.98./>
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. ( X=br, 48.44mg,84% yield; x=i, 44.41mg,77% yield ). 1 H NMR(500MHz,CDCl 3 )δ8.35(d,J＝1Hz,1H),8.03(dd,J＝1.5,8.5Hz,1H),7.69(d,J＝2Hz,1H),7.53(d,J＝9Hz,1H),6.84(dd,J＝0.5,2Hz,1H),3.94(s,3H). 13 C NMR(125MHz,CDCl 3 )δ167.27,157.45,146.21,127.41,126.01,125.15,123.74,111.26,107.11,52.11.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. (55.36 mg,96% yield). 1 H NMR(500MHz,CDCl 3 )δ8.54(s,1H),8.00(d,J＝8.5Hz,1H),7.92(d,J＝8.5Hz,1H),7.52(d,J＝5.5Hz,1H),7.42(d,J＝5.5Hz,1H),3.96(s,3H). 13 C NMR(125MHz,CDCl 3 )δ167.38,144.11,139.31,127.65,126.41,125.53,124.62,124.41,122.34,52.16.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. (55.06 mg,97% yield). 1 H NMR(500MHz,CDCl 3 )δ8.40(d,J＝1Hz,1H),7.93(dd,J＝4,8.5Hz,1H),7.33(d,J＝9Hz,1H),7.11(d,J＝3.5Hz,1H),6.59(dd,J＝1,3.5Hz,1H),3.93(s,3H),3.82(s,3H). 13 C NMR(125MHz,CDCl 3 )δ168.26,139.08,130.19,127.93,123.91,122.90,121.32,108.81,102.62,51.81,33.02.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. (37.07 mg,66% yield). 1 H NMR(500 MHz,CDCl 3 )δ9.01(s,1H),8.60(s,1H),8.30(d,J＝8.5 Hz,1H),8.27(d,J＝8.5 Hz,1H),8.15(d,J＝8.5 Hz,1H),7.48(dd,J＝4,7.5 Hz,1H),4.00(s,3H). 13 CNMR(125 MHz,CDCl 3 )δ166.59,152.52,150.07,137.33,131.00,129.81,128.94,128.10,127.40,121.84,52.44.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. (33.31 mg,59% yield). 1 H NMR(500 MHz,CDCl 3 )δ9.56(s,1H),8.32-8.30(m,1H),8.21-8.20(m,1H),7.93-7.86(m,2H),4.13(s,3H). 13 C NMR(125 MHz,CDCl 3 )δ164.66,145.07,143.78,142.33,141.44,132.40,131.08,130.59,129.38,53.42./>
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate)=15:1) to give the product as a white solid. (38.43 mg,67% yield). 1 H NMR(500 MHz,CDCl 3 )δ8.16(d,J＝1 Hz,1H),8.04(dd,J＝1.5,9.5 Hz,1H),7.67(d,J＝8.5 Hz,1H),3.95(s,3H),2.68(s,3H). 13 C NMR(125 MHz,CDCl 3 )δ166.72,166.69,150.63,145.48,126.66,125.97,119.02,111.90,52.34,14.75.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. (71.23 mg,98% yield). 1 H NMR(500 MHz,CDCl 3 )δ8.83(d,J＝1 Hz,1H),8.24-8.22(m,1H),8.11(dd,J＝1.5,8.5 Hz,1H),7.89(d,J＝8.5 Hz,1H),7.87-7.85(m,1H),7.52-7.48(m,2H),4.00(s,3H). 13 C NMR(125 MHz,CDCl 3 )δ167.18,144.32,139.61,135.51,135.10,127.29,127.23,126.43,124.83,123.11,122.83,122.56,121.90,52.22.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (34.32 mg,51% yield). 1 H NMR(500 MHz,CDCl 3 )δ7.80(dd,J＝1,3.5 Hz,1H),7.54(dd,J＝1,5 Hz,1H),7.10(dd,J＝3.5,5 Hz,1H),4.11(d,J＝6.5 Hz,2H),1.82-1.78(m,2H),1.78-1.74(m,2H),1.72-1.67(m,1H),1.32-1.14(m,4H),1.08-1.01(m,2H). 13 C NMR(125 MHz,CDCl 3 )δ162.36,134.11,133.19,132.12,127.68,70.16,37.22,29.66,26.35,25.67.IR(ATR)ν(cm -1 )＝2919,2851,1709,1529,1449,1417,1355,1258,1091,1077,1035,1023,891,751,714.HRMS:m/z(ESI-TOF)calculated[M+H] + :225.0944,measured:225.0945.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give an oily liquidThe product is obtained. (44.36 mg,71% yield). 1 H NMR(500 MHz,CDCl 3 )δ7.58(d,J＝1,Hz,1H),7.17(dd,J＝0.5,3.5 Hz,1H),6.50(dd,J＝1.5,3.5 Hz,1H),4.11(d,J＝6.5 Hz,2H),1.80(d,J＝12 Hz,2H),1.77-1.74(m,2H),1.70-1.67(m,1H),1.32-1.14(m,4H),1.07-0.99(m,2H). 13 C NMR(125 MHz,CDCl 3 )δ158.91,146.16,144.88,117.63,111.74,70.00,37.16,29.62,26.33,25.63.IR(ATR)ν(cm -1 )＝2919,2851,1719,1445,1088,1080,1032,1023,983,952,890,842,738.HRMS:m/z(ESI-TOF)calculated[M+H] + :209.1172,measured:209.1185./>
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (48.65 mg,90% yield). 1 H NMR(500MHz,CDCl 3 )δ7.99(dd,J＝2.5,8.5Hz,2H),6.90(dd,J＝2.5,8.5Hz,2H),4.33(q,J＝9Hz,2H),3.83(s,3H),1.36(t,J＝9Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ166.30,163.13,131.43,122.79,113.42,60.54,55.29,14.29.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (61.23 mg,98% yield). 1 H NMR(500MHz,CDCl 3 )δ7.99(dd,J＝2.5,9Hz,2H),6.93-6.89(m,2H),4.28(t,J＝8.5Hz,2H),3.85(s,3H),1.77-1.70(m,2H),1.51-1.42(m,2H),0.97(t,J＝9Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ166.41,163.15,131.47,122.87,113.47,64.48,55.34,30.76,19.24,13.74.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give an oily liquid product. (64.81 mg,87% yield). 1 H NMR(500MHz,CDCl 3 )δ8.01-7.99(m,2H),6.93-6.90(m,2H),4.10(d,J＝6.5Hz,2H),3.86(s,3H),1.82(d,J＝13Hz,2H),1.79-1.76(m,1H),1.75-1.74(m,1H),1.71-1.67(m,1H),1.33-1.15(m,4H),1.10-1.02(m,2H). 13 C NMR(125MHz,CDCl 3 )δ166.44,163.21,131.52,122.99,113.53,69.77,55.40,37.30,29.77,26.39,25.72.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (39.29 mg,60% yield). 1 H NMR(500MHz,CDCl 3 )δ8.06-8.04(m,2H),7.57-7.54(m,1H),7.46-7.43(m,2H),4.14(d,J＝6Hz,2H),1.85-1.81(m,2H),1.80-1.77(m,1H),1.77-1.75(m,1H),1.72-1.68(m,1H),1.33-1.16(m,4H),1.10-1.03(m,2H). 13 C NMR(125MHz,CDCl 3 )δ166.68,132.78,130.53,129.52,128.31,70.06,37.26,29.75,26.37,25.70.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (53.78 mg,74% yield). 1 H NMR(500MHz,CDCl 3 )δ8.06-8.03(m,2H),7.46-7.44(m,2H),7.42-7.34(m,3H),6.93-6.91(m,2H),5.35(s,2H),3.86(s,3H). 13 C NMR(125MHz,CDCl 3 )δ166.15,163.36,136.22,131.67,128.52,128.11,128.07,122.44,113.56,66.35,55.39.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. (30.29 mg,52% yield). 1 H NMR(500MHz,CDCl 3 )δ8.09(s,4H),3.94(s,6H). 13 C NMR(125MHz,CDCl 3 )δ166.25,133.83,129.51,52.43.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (87.14 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ7.96(d,J＝9Hz,2H),6.88(d,J＝9Hz,2H),4.39(t,J＝6Hz,2H),4.00(t,J＝6.5Hz,2H),2.89(t,J＝6Hz,2H),2.68(q,J＝7Hz,4H),1.80-1.74(m,2H),1.52-1.45(m,2H),1.09(t,J＝7Hz,6H),0.97(t,J＝7.5Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ166.30,162.96,131.55,122.23,114.01,67.83,62.56,50.79,47.64,31.09,19.14,13.78,11.66.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=9:1) to give the product as a white solid. ( X=i, 29.44mg,84% yield; x=br, 28.04mg,80% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.52-7.50(m,2H),7.42-7.37(m,3H),3.65(t,J＝7Hz,2H),3.42(t,J＝6.5Hz,2H),1.99-1.94(m,2H),1.90-1.84(s,2H). 13 C NMR(125MHz,CDCl 3 )δ169.74,137.23,129.74,128.22,127.07,49.59,46.15,26.38,24.46.
The reaction was carried out according to general procedure 1, and column chromatography (petroleum ether: ethyl acetate=9:1) gave the product as an oily liquid. ( X=i, 35.10mg,99% yield; x=br, 30.13mg,85% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.76(d,J＝8Hz,2H),7.46(t,J＝7.5Hz,1H),7.39(t,J＝7.5Hz,2H),6.36(s,1H),3.43(q,J＝6.5Hz,2H),1.61-1.55(m,2H),1.43-1.35(m,2H),0.93(t,J＝7.5Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ167.51,134.79,131.20,128.43，126.79，39.74，31.66，20.10，13.73.
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=9:1) to give the product as a white solid. (31.71 mg,78% yield). 1 H NMR(500MHz,CDCl 3 )δ7.75(d,J＝8Hz,2H),7.48(t,J＝7Hz,1H),7.42(t,J＝7.5Hz,2H),5.99(s,1H),4.01-3.94(m,1H),2.04-2.01(m,2H),1.77-1.73(m,2H),1.66-1.64(m,1H),1.47-1.38(m,2H),1.27-1.16(m,3H). 13 C NMR(125MHz,CDCl 3 )δ166.59,135.08,131.20,128.48,126.79,48.63,33.22,25.55,24.89./>
The reaction was carried out according to general procedure 1, column chromatography (petroleum ether: ethyl acetate=9:1) to give the product as a white solid. (27.54 mg,72% yield). 1 H NMR(500MHz,CDCl 3 )δ7.42-7.40(m,5H),3.78-3.44(m,8H). 13 C NMR(125MHz,CDCl 3 )δ170.40,135.28,129.85,128.53,127.05,66.87.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a yellow solid. (24.06 mg,61% yield). 1 H NMR(500MHz,CDCl 3 )δ7.89-7.86(m,3H),7.65(d,J＝7.5Hz,2H),7.55(t,J＝7Hz,1H),7.48(t,J＝8Hz,2H),7.37(t,J＝7.5Hz,2H),7.16(t,J＝7.5Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ165.74,137.89,134.97,131.82,129.08,128.77,127.00,124.55,120.18.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. ( X=i, 41.83mg,99% yield; x=br, 30.80mg,80% yield ). 1 H NMR(500MHz,CDCl 3 )δ7.80–7.78(m,2H),7.50(t,J＝7.5Hz,1H),7.44-7.41(m,2H),7.35(d,J＝4.5Hz,4H),7.33-7.28(m,1H),6.51(s,1H),4.64(d,J＝5.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ167.33,138.14,134.33,131.52,128.76,128.56,127.89,127.59,126.93,44.10.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (44.61 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ7.69(d,J＝7.5Hz,2H),7.48(t,J＝7.5Hz,1H),7.40(t,J＝7.5Hz,2H),7.33(d,J＝7.5Hz,2H),7.24(d,J＝8Hz,3H),6.21(s,1H),3.72(q,J＝6.5Hz,2H),2.94(t,J＝7Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ167.46,138.87,134.59,131.39,128.80,128.70,128.53,126.78,126.58,41.11,35.67.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (38.06 mg,72% yield). 1 H NMR(500MHz,CDCl 3 )δ7.80(d,J＝7.5Hz,2H),7.45(t,J＝7.5Hz,1H),7.39-7.36(m,3H),5.29-5.28(m,1H),3.53(q,J＝5Hz,2H),3.38-3.37(m,2H),1.40(s,9H). 13 CNMR(125MHz,CDCl 3 )δ167.92,157.43,134.06,131.35,128.39,126.98,79.78,41.82,39.91,28.27./>
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (43.42 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ7.42-7.38(m,5H),4.58(d,J＝11Hz,1H),3.65(s,1H),3.53(s,2H),2.80(s,1H),2.54(s,1H),1.25(s,3H),1.09(s,3H). 13 C NMR(125MHz,CDCl 3 )δ170.10,135.55,129.79,128.54,127.07,71.94,53.24,47.49,18.57.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (59.23 mg,93% yield). 1 H NMR(500MHz,CDCl 3 )δ7.74(d,J＝7.5Hz,2H),7.49(t,J＝7Hz,1H),7.42(t,J＝7.5Hz,2H),6.11(d,J＝6.5Hz,1H),4.59(s,1H),4.09(d,J＝3Hz,1H),3.66(s,1H),1.85-1.79(m,4H),1.63-1.62(m,4H),1.44(s,9H). 13 C NMR(125MHz,CDCl 3 )δ166.76,156.69,134.81,131.39,128.55,126.77,46.34,28.78,28.39,28.18.IR(ATR)ν(cm -1 )＝3274,2923,1678,1637,1527,1365,1328,1270,1247,1165,1095,1025,978,875,687.HRMS:m/z(ESI-TOF)calculated[M+Na] + :341.1836,measured:341.1823.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a brown solid. (52.93 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ7.74(d,J＝7.5Hz,2H),7.44(d,J＝7.5Hz,2H),7.35(d,J＝4.5Hz,4H),7.31–7.28(m,1H),6.42(s,1H),4.65(s,2H),1.33(s,9H). 13 C NMR(125MHz,CDCl 3 )δ167.27,155.06,138.28,131.43,128.75,127.89,127.55,126.80,125.53,44.07,34.90,31.14.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a pale yellow solid. (43.71 mg,97% yield). 1 H NMR(500MHz,CDCl 3 )δ7.69(d,J＝8Hz,2H),7.35(d,J＝4.5Hz,4H),7.32-7.28(m,1H),7.23(d,J＝8Hz,2H),6.41(s,1H),4.64(d,J＝5.5Hz,2H),2.39(s,3H). 13 C NMR(125MHz,CDCl 3 )δ167.27,141.96,138.26,131.48,129.22,128.75,127.90,127.57,126.92,44.06,21.42.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (47.78 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ7.60(d,J＝8.5Hz,2H),7.36-7.33(m,4H),7.32-7.27(m,1H),6.91(d,J＝9Hz,2H),6.38(s,1H),4.32(d,J＝5.5Hz,2H),3.84(s,3H). 13 C NMR(125MHz,CDCl 3 )δ166.90,162.19,138.36,128.74,127.90,127.54,126.61,113.74,55.39,44.05.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (46.55 mg,81% yield). 1 H NMR(500MHz,CDCl 3 )δ7.87(d,J＝8Hz,2H),7.66(d,J＝8.5Hz,2H),7.61(d,J＝7.5Hz,2H),7.46(t,J＝7Hz,2H),7.40-7.36(m,5H),7.33-7.30(m,1H),6.45(s,1H),4.68(d,J＝5.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ167.02,144.38,139.95,138.14,132.96,128.90,128.81,128.00,127.95,127.66,127.47,127.26,127.19,44.18.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (24.10 mg,51% yield). 1 H NMR(500MHz,CDCl 3 )δ7.88(d,J＝8Hz,2H),7.72(d,J＝8Hz,2H),7.38-7.32(m,5H),6.48(s,1H),4.65(d,J＝5.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ165.50,138.25,137.48,132.46,128.92,127.99,127.92,127.68,117.93,115.18,44.41.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) gave the product as a yellow oil. (45.47 mg,95% yield). 1 H NMR(500MHz,CDCl 3 )δ7.40(s,2H),7.36(d,J＝4.5Hz,4H),7.32-7.28(m,1H),7.13(s,1H),6.44(s,1H),4.63(d,J＝4Hz,2H),2.34(s,6H). 13 C NMR(125MHz,CDCl 3 )δ167.72,138.25,134.32,133.10,128.73,127.91,127.54,124.71,44.07,21.20.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) gave the product as a pale yellow oily liquid. (51.55 mg,95% yield). 1 H NMR(500MHz,CDCl 3 )δ7.37-7.34(m,4H),7.32-7.29(m,1H),6.91(d,J＝1.5Hz,2H),6.57(s,1H),6.46(s,1H),4.62(d,J＝5Hz,2H),3.80(s,6H). 13 CNMR(125MHz,CDCl 3 )δ167.19,160.86,138.05,136.58,128.75,127.87,127.60,104.89,103.57,55.56,44.15./>
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (37.27 mg,73% yield). 1 H NMR(500MHz,CDCl 3 )δ7.35-7.26(m,7H),6.79(d,J＝8Hz,1H),6.48(s,1H),6.00(s,2H),4.58(d,J＝5.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ166.64,150.30,147.91,138.20,128.70,128.50,127.82,127.52,121.53,107.92,107.63,101.63,44.09.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (27.18 mg,52% yield). 1 H NMR(500MHz,CDCl 3 )δ8.31(s,1H),7.88-7.85(m,4H),7.57-7.51(m,2H),7.40-7.35(m,4H),7.32-7.30(m,1H),6.72(s,1H),4.69(d,J＝5.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ167.41,138.18,134.70,132.55,131.51,128.87,128.67,128.44,127.93,127.70,127.62,127.59,127.43,126.71,123.56,44.21.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) gave the product as an oily liquid. (33.97 mg,65% yield). 1 H NMR(500MHz,CDCl 3 )δ8.35(d,J＝8.5Hz,1H),7.91(d,J＝8Hz,1H),7.87(d,J＝8Hz,1H),7.62(d,J＝7Hz,1H),7.58-7.51(m,2H),7.45(d,J＝7.5Hz,1H),7.43-7.36(m,4H),7.31(t,J＝7Hz,1H),6.31(s,1H),4.73(d,J＝5.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ169.36,138.04,134.26,133.67,130.70,130.14,128.83,128.30,127.88,127.66,127.16,136.44,125.38,124.89,124.66,44.12.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) gave the product as an oily liquid. ( X=i, 44.23mg,88% yield; x=br, 43.22mg,86% yield ). 1 H NMR(500MHz,CDCl 3 )δ8.09(s,1H),7.75(dd,J＝1.5,8.5Hz,1H),7.68(d,J＝2Hz,1H),7.52(d,J＝8.5Hz,1H),7.39-7.35(m,4H),7.32-7.29(m,1H),6.81(d,J＝2Hz,1H),6.48(s,1H),4.67(d,J＝5.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ167.53,156.56,146.28,138.24,129.51,128.78,127.93,127.61,127.55,123.37,120.67,111.42,106.96,44.25.IR(ATR)ν(cm -1 )＝3264,3110,1632,1540,1450,1413,1322,1263,1174,1119,1103,1025,995,904,881,836,775,745,727,696,662.HRMS:m/z(ESI-TOF)calculated[M+H] + :252.1019,measured:252.1011./>
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) gave the product as an oily liquid. (33.90 mg,78% yield). 1 H NMR(500MHz,CDCl 3 )δ7.88(d,J＝1.5Hz,1H),7.40(d,J＝5Hz,1H),7.35-7.28(m,6H),6.52(s,1H),4.58(d,J＝6Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ162.96,138.14,137.23,128.70,128.35,127.83,127.53,126.46,126.02,43.74.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (33.90 mg,78% yield). 1 H NMR(500MHz,CDCl 3 )δ6.93(d,J＝1.5Hz,1H),6.89-6.84(m,2H),4.26(s,4H),3.52(s,4H),1.66-1.57(m,6H). 13 C NMR(125MHz,CDCl 3 )δ169.76,144.60,143.23,129.55,120.41,117.09,116.43,64.40,64.26,26.00,24.60.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a pale yellow solid. (54.96 mg,85% yield). 1 H NMR(500MHz,CDCl 3 )δ7.74(d,J＝7.5Hz,1H),7.64-7.62(m,2H),7.60-7.59(m,1H),7.44(s,1H),7.32(s,1H),7.26-7.22(m,1H),7.03(d,J＝8Hz,1H),6.71(d,J＝8Hz,1H),4.62-4.55(m,1H),1.35(d,J＝6Hz,6H). 13 C NMR(125MHz,CDCl 3 )δ165.56,158.56,138.59,135.81,132.20,130.19,129.81,128.61,127.23(d,J＝31.9Hz),126.50(q,J＝4.8Hz),123.57(d,J＝272.1Hz),112.55,112.08,107.86,70.02,22.00.IR(ATR)ν(cm -1 )＝3249,2982,1655,1599,1543,1492,1415,1314,1259,1159,1126,1108,1054,1032,997,980,901,852,775,764,736,678,645,604.HRMS:m/z(ESI-TOF)calculated[M+H] + :324.1206,measured:324.1189.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a brown solid. (31.96 mg,51% yield). 1 H NMR(500MHz,CDCl 3 )δ7.21(d,J＝7.5Hz,1H),7.12(br,1H),7.01(s,1H),6.78(s,2H),4.11(s,2H),3.89(s,3H),3.86(s,6H),3.13(t,J＝8.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ168.55,153.33,142.48,139.69,132.41,132.13,127.20,124.93,123.89,116.90,104.47,60.94,56.24,50.09,28.31.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (54.48 mg,76% yield). 1 H NMR(500MHz,CDCl 3 )δ7.46(s,1H),7.28(d,J＝8Hz,3H),6.90(d,J＝8.5Hz,2H),6.84(d,J＝8.5Hz,1H),6.37(s,1H),4.56(d,J＝5.5Hz,2H),4.09(t,J＝5.5Hz,2H),3.92(d,J＝7.5Hz,6H),2.78(t,J＝5.5Hz,2H),2.38(s,6H). 13 C NMR(125MHz,CDCl 3 )δ166.78,158.19,151.68,148.94,130.57,129.25,127.02,119.20,114.75,110.61,110.15,65.76,58.13,56.00,55.97,45.72,43.59.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) afforded the product as a white solid. (26.36 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ7.92(s,1H),7.87(d,J＝7.5Hz,1H),7.57(t,J＝7.5Hz,1H),7.49-7.47(m,2H),4.48(s,2H). 13 C NMR(125MHz,CDCl 3 )δ172.15,143.65,132.15,131.68,127.96,123.65,123.15,45.73.
The reaction was carried out according to general procedure 2, and column chromatography (petroleum ether: ethyl acetate=9:1) gave the product as an oily liquid. (21.78 mg,74% yield). 1 H NMR(500MHz,CDCl 3 )δ8.06(d,J＝7.5Hz,1H),7.46-7.43(m,1H),7.35(t,J＝7.5Hz,1H),7.21(d,J＝7.5Hz,1H),7.06-6.75(m,1H),3.59-3.56(m,2H),3.01-2.98(m,2H). 13 CNMR(125MHz,CDCl 3 )δ166.42,138.83,132.10,128.89,127.92,127.21,127.03,40.16,28.29.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (40.84 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ8.24-8.22(m,2H),7.71-7.69(m,2H),7.66-7.62(m,1H),7.53(t,J＝8Hz,2H),7.50-7.47(m,1H),7.45-7.42(m,2H). 13 C NMR(125MHz,CDCl 3 )δ178.03,136.87,134.12,133.07,130.79,139.57,128.68,128.62,120.12,93.10,86.87.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (41.41 mg,94% yield). 1 H NMR(500MHz,CDCl 3 )δ8.25-8.23(m,2H),7.66-7.61(m,2H),7.52(t,J＝8Hz,2H),7.39-7.35(m,1H),7.28(d,J＝7.5Hz,1H),7.25-7.22(m,1H),2.59(s,3H). 13 CNMR(125MHz,CDCl 3 )δ178.00,142.13,136.98,134.00,133.62,130.77,139.84,129.49,128.59,125.90,119.94,92.13,90.71,20.85.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (35.68 mg,81% yield). 1 H NMR(500MHz,CDCl 3 )δ8.24-8.23(m,2H),7.63(t,J＝7.5Hz,1H),7.54-7.50(m,4H),7.33-7.29(m,2H),2.39(s,3H). 13 C NMR(125MHz,CDCl 3 )δ178.01,138.48,136.87,134.03,133.51,131.72,130.19,139.52,128.57,128.54,119.86,93.47,86.62,21.15.
The reaction was carried out according to general procedure 3, column chromatography (petroleum ether: ethyl acetate=15:1) to give yellowThe product was a coloured liquid. (39.25 mg,98% yield). 1 H NMR(500MHz,CDCl 3 )δ8.24-8.22(m,2H),7.64-7.58(m,3H),7.52(t,J＝7.5Hz,2H),7.23(d,J＝8Hz,2H),2.41(s,3H). 13 C NMR(125MHz,CDCl 3 )δ178.06,141.54,136.93,133.99,133.10,129.52,129.46,128.56,116.97,93.81,86.75,21.75.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (41.58 mg,88% yield). 1 H NMR(500MHz,CDCl 3 )δ8.23-8.21(m,2H),7.67-7.61(m,3H),7.53-7.50(m,2H),6.95-6.92(m,2H),3.86(s,3H). 13 C NMR(125MHz,CDCl 3 )δ178.04,161.72,137.03,135.14,133.89,129.48,128.55,114.41,111.89,94.30,86.86,55.43.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (23.34 mg,55% yield). 1 H NMR(500MHz,CDCl 3 )δ8.23-8.21(m,2H),7.62-7.59(m,1H),7.53-7.49(m,4H),6.67(d,J＝8.5Hz,2H),4.09(s,2H). 13 C NMR(125MHz,CDCl 3 )δ178.07,149.18,137.23,135.34,133.67,129.42,128.48,114.57,108.58,96.17,87.05.IR(ATR)ν(cm -1 )＝3354,3218,2919,2167,1592,1512,1314,1291,1213,1166,1030,1006,826,696.HRMS:m/z(ESI-TOF)calculated[M+H] + :222.0913,measured:222.0903./>
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (39.98 mg,67% yield). 1 H NMR(500MHz,CDCl 3 )δ8.22(d,J＝7Hz,2H),7.67-7.62(m,3H),7.52(t,J＝7.5Hz,2H),7.41(d,J＝7.5Hz,2H),7.21(t,J＝7Hz,1H),7.09-7.07(m,2H),7.01(d,J＝9Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ177.99,160.14,155.43,136.92,135.13,134.01,130.06,129.51,128.58,124.60,120.07,117.98,113.95,93.43,86.90.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (45.56 mg,61% yield). 1 H NMR(500MHz,CDCl 3 )δ8.23-8.21(m,2H),7.61(t,J＝7.5Hz,1H),7.53-7.49(m,4H),7.33(t,J＝7.5Hz,4H),7.17-7.12(m,6H),7.00(d,J＝8.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ177.97,150.32,146.41,137.16,134.55,133.78,129.62,129.44,128.52,125.82,124.59,120.53,111.23,95.21,87.39.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (42.23 mg,77% yield). 1 H NMR(500MHz,CDCl 3 )δ8.23-8.21(m,2H),7.80(d,J＝8Hz,2H),7.70-7.65(m,3H),7.54(t,J＝8Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ177.66,136.55,134.46,133.16,132.24(q,J＝32.5Hz),139.63,128.74,125.63(q,J＝3.9Hz),123.95,123.54(q,J＝270.9Hz),90.45,88.07.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (50.75 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ8.43(d,J＝8.5Hz,1H),8.33-8.32(m,2H),8.00-7.96(m,2H),7.92(d,J＝8Hz,1H),7.69-7.66(m,2H),7.61-7.51(m,4H). 13 C NMR(125MHz,CDCl 3 )δ178.01,137.04,134.13,133.63,133.19,133.08,131.49,129.61,128.70,128.58,127.57,126.96,125.82,125.20,117.71,91.60,91.42.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (33.32 mg,65% yield). 1 H NMR(500MHz,CDCl 3 )δ8.29-8.26(m,3H),7.89-7.86(m,3H),7.69-7.64(m,2H),7.60-7.54(m,4H). 13 C NMR(125MHz,CDCl 3 )δ178.00,136.93,134.35,134.12,133.92,132.67,129.60,128.64,128.50,128.40,128.20,128.02,127.91,127.05,117.28,93.62,87.15.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (50.24 mg,82% yield). 1 H NMR(500MHz,CDCl 3 )δ8.74-8.71(m,1H),8.69(d,J＝8.5Hz,1H),8.53-8.50(m,1H),6.36-8.34(m,2H),8.30(s,1H),7.93(d,J＝8.5Hz,1H),7.77-7.74(m,3H),7.70-7.64(m,2H),7.59(t,J＝7.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ177.96,137.05,135.62,134.17,131.28,130.68,130.64,130.06,129.64,129.14,128.84,128.73,127.61,127.59,127.28,126.63,122.97,122.76,116.65,91.62,91.15.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (20.72 mg,50% yield). 1 H NMR(500MHz,CDCl 3 )δ8.92(s,1H),8.70(d,J＝3.5Hz,1H),8.22(d,J＝7.5Hz,2H),8.00-7.98(m,1H),7.66(t,J＝7.5Hz,1H),7.54(t,J＝7.5Hz,2H),7.41-7.38(m,1H). 13 C NMR(125MHz,CDCl 3 )δ177.55,153.15,150.65,140.00,136.49,134.48,129.62,128.76,123.28,89.42,88.83.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (39.91 mg,94% yield). 1 H NMR(500MHz,CDCl 3 )δ8.22-8.20(m,2H),7.86-7.85(m,1H),7.65-7.62(m,1H),7.52(t,J＝7.5Hz,2H),7.39-7.38(m,4H),7.33(dd,J＝1,5Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ178.01,136.82,134.08,133.90,130.28,129.52,128.60,126.25,119.38,88.48,87.14.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as a yellow liquid. (23.55 mg,56% yield). 1 H NMR(500MHz,CDCl 3 )δ8.14(d,J＝8Hz,2H),7.59(t,J＝7Hz,1H),7.48(t,J＝7.5Hz,2H),6.58(s,1H),2.28-2.20(m,4H),1.73-1.62(m,4H). 13 C NMR(125MHz,CDCl 3 )δ178.19,142.65,137.01,133.78,129,42,128.46,119.11,95.73,85.17,28.35,26.15,21.92,21.07.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily colourless liquid. (32.45 mg,81% yield). 1 H NMR(500MHz,CDCl 3 )δ8.14-8.13(m,2H),7.59(t,J＝7Hz,1H),7.47(t,J＝8Hz,2H),2.50(t,J＝7Hz,2H),1.69-1.63(m,2H),1.54-1.47(m,2H),0.96(t,J＝7Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ178.24,136.88,133.83,139.51,128.45,96.83,29.80,22.05,18.88,13.50.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily yellow liquid. 1 H NMR(500MHz,CDCl 3 )δ8.15-8.13(m,2H),7.61-7.58(m,1H),7.47(t,J＝7.5Hz,2H),2.49(t,J＝7Hz,2H),1.70-1.64(m,2H),1.50-1.44(m,2H),1.35-1.27(m,10H),0.88(t,J＝6.5Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ178.21,136.89,133.81,129.50,128.43,98.89,79.64,31.81,29.38,29.21,29.01,28.93,27.77,22.62,19.18,14.07.IR(ATR)ν(cm -1 )＝2923,2851,2233,2195,1643,1594,1578,1448,1311,1259,1173,906,699.HRMS:m/z(ESI-TOF)calculated[M+H] + :257.1900,measured:257.1886.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily yellow liquid. (33.15 mg,87% yield). 1 H NMR(500MHz,CDCl 3 )δ8.14-8.12(m,2H),7.58(t,J＝7Hz,1H),7.47(t,J＝8.5Hz,2H),2.71-2.66(m,1H),1.94-1.91(m,2H),1.79-1.69(m,2H),1.65-1.53(m,3H),1.41-1.39(m,3H). 13 C NMR(125MHz,CDCl 3 )δ178.30,136.95,133.76,129.46,128.41,100.33,79.47,31.63,29.31,25.58,24.65.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (36.39 mg,77% yield). 1 H NMR(500MHz,CDCl 3 )δ8.21-8.18(m,2H),7.68-7.66(m,2H),7.49-7.46(m,1H),7.43-7.40(m,2H),6.99(dd,J＝2,7Hz,2H),3.90(s,3H). 13 C NMR(125MHz,CDCl 3 )δ176.65,164.45,132.92,131.95,130.55,130.27,128.62,120.32,113.85,92.27,86.89,55.57.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (49.55 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ7.89(dd,J＝1.5,8Hz,1H),7.67-7.65(m,2H),7.61(d,J＝1.5Hz,1H),7.49-7.46(m,1H),7.42-7.40(m,2H),6.91(d,J＝8Hz,1H),6.07(s,2H). 13 C NMR(125MHz,CDCl 3 )δ176.10,152.85,148.20,132.92,132.06,130.62,128.61,127.20,120.16,108.29,107.99,102.09,92.32,86.74.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a brown solid. (50.23 mg,98% yield). 1 H NMR(500MHz,CDCl 3 )δ8.80(s,1H),8.23-8.21(m,1H),8.04(d,J＝8Hz,1H),7.94-7.90(m,2H),7.76-7.74(m,2H),7.66-7.63(m,1H),7.60-7.57(m,1H),7.53-7.50(m,1H),7.47-7.44(m,2H). 13 C NMR(125MHz,CDCl 3 )δ177.93,136.16,134.43,133.05,132.64,132.41,130.76,129.88,129.01,128.70,128.54,127.91,126.94,123.97,120.22,93.03,87.06.
The reaction was carried out according to general procedure 3, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a yellow oil. (48.26 mg,98% yield). 1 H NMR(500MHz,CDCl 3 )δ8.54(d,J＝1.5Hz,1H),8.22(dd,J＝1.5,8.5Hz,1H),7.73-7.71(m,3H),7.60(d,J＝9Hz,1H),7.51-7.48(m,1H),7.45-7.32(m,2H),6.91d,J＝1.5Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ177.60,158.18,146.67,132.99,132.59,130.68,128.67,127.66,126.06,124.29,120.24,111.63,107.38,92.68,87.03.IR(ATR)ν(cm -1 )＝3118,3065,2191,1630,1603,1581,1487,1438,1327,1285,1260,1145,1122,1102,1028,1007,995,745,685.HRMS:m/z(ESI-TOF)calculated[M+H] + :247.0754,measured:247.0746.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (56.52 mg,96% yield). 1 H NMR(500MHz,CDCl 3 )δ8.38(s,1H),8.30(d,J＝8Hz,1H),7.89(t,J＝8Hz,2H),7.73(d,J＝7Hz,2H),7.61(d,J＝7Hz,1H),7.52-7.49(m,1H),7.46-7.39(m,4H),4.00(s,2H). 13 C NMR(125MHz,CDCl 3 )δ177.81,147.60,144.79,143.32,140.33,135.54,133.01,130.66,129.36,128.67,128.33,127.14,126.00,125.30,121.11,120.32,119.74,92.70,87.24,36.86.
The reaction was carried out according to general procedure 3, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a yellow oil. (50.37 mg,96% yield). 1 H NMR(500MHz,CDCl 3 )δ8.70(d,J＝1Hz,1H),8.18-8.16(m,1H),7.97(d,J＝8.5Hz,1H),7.73-7.71(m,2H),7.55(d,J＝5.5Hz,1H),7.51-7.48(m,2H),7.45-7.42(m,2H). 13 C NMR(125MHz,CDCl 3 )δ177.83,145.37,139.32,133.65,133.00,130.71,128.65,128.11,126.07,124.69,124.07,122.60,120.17,92.80,87.02.IR(ATR)ν(cm -1 )＝3065,2195,1627,1590,1544,1490,1441,1422,1327,1280,1217,1151,1086,1048,994,900,823,785,755,732,682.HRMS:m/z(ESI-TOF)calculated[M+H] + :263.0525,measured:263.0523.
The reaction was carried out according to general procedure 3, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a yellow oil. (60.60 mg,97% yield). 1 H NMR(500MHz,CDCl 3 )δ8.99(d,J＝1.5Hz,1H),8.31(dd,J＝1.5,8.5Hz,1H),8.28-8.26(m,1H),7.96(d,J＝8.5Hz,1H),7.89-7.87(m,1H),7.76-7.74(m,2H),7.55-7.51(m,3H),7.48-7.45(m,2H). 13 C NMR(125MHz,CDCl 3 )δ177.55,145.87,139.72,135.72,135.06,133.66,133.08,130.82,128.74,127.59,127.38,125.06,122.96,122.93,122.80,121.98,120.21,93.17,87.08.IR(ATR)ν(cm -1 )＝3062,2923,2202,1647,1601,1584,1547,1489,1444,1317,1268,1227,1193,1174,1063,1009,991,889,841,781,753,725,681.HRMS:m/z(ESI-TOF)calculated M + :313.0682,measured:313.0676./>The reaction was carried out according to general procedure 3, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a yellow oil. (34.39 mg,81% yield). 1 H NMR(500MHz,CDCl 3 )δ8.36(dd,J＝1,3Hz,1H),7.69-7.65(m,3H),7.50-7.47(m,1H),7.43-7.40(m,2H),7.36(dd,J＝2.5,5Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ171.40,142.96,135.43,132.98,130.74,128.67,126.80,126.79,120.20,91.30,87.28.
The reaction was carried out according to general procedure 3, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a yellow oil. (42.03 mg,99% yield). 1 H NMR(500MHz,CDCl 3 )δ8.02-8.01(m,1H),7.74-7.73(m,1H),7.67-7.66(m,2H),7.49(d,J＝7.5Hz,1H),7.42(t,J＝7.5Hz,2H),7.19(t,J＝4Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ169.77,144.93,135.22,135.05,133.02,130.83,128.68,128.32,119.93,91.70,86.46.
The reaction was carried out according to general procedure 3, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a yellow oil. (65.63 mg,95% yield). 1 H NMR(500MHz,CDCl 3 )δ8.52(s,1H),8.42-8.41(m,1H),8.13(d,J＝8Hz,1H),7.68(d,J＝7Hz,2H),7.48(t,J＝7Hz,1H),7.44-7.36(m,4H),1.74(s,9H). 13 C NMR(125MHz,CDCl 3 )δ172.29,148.92,135.76,135.68,132.90,130.52,128.65,126.72,125.84,124.62,122.48,121.96,120.27,115.10,89.23,87.27,85.70,28.05.IR(ATR)ν(cm -1 )＝2978,2931,2187,1740,1623,1540,1485,1448,1368,1307,1278,1231,1134,1103,1048,949,850,833,758,748,688.HRMS:m/z(ESI-TOF)calculated M + :346.1438,measured:346.1425.
The reaction was carried out according to general procedure 3, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (50.38 mg,96% yield). 1 H NMR(500MHz,CDCl 3 )δ8.81(d,J＝8.5Hz,1H),8.73(s,1H),7.88(d,J＝8Hz,1H),7.70-7.68(m,2H),7.55-7.42(m,5H). 13 C NMR(125MHz,CDCl 3 )δ171.81,142.09,140.25,136.28,135.74,132.89,130.64,128.68,126.14,125.86,125.48,122.39,120.13,90.49,87.33.IR(ATR)ν(cm -1 )＝3079,2218,2185,1618,1487,1458,1416,1368,1268,1154,1142,1117,1051,935,859,818,781,767,755,734,705,687.HRMS:m/z(ESI-TOF)calculated[M+H] + :263.0525,measured:263.0526.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (30.61 mg,84% yield). 1 H NMR(500MHz,CDCl 3 )δ7.83-7.80(m,4H),7.61-7.57(m,2H),7.51-7.47(m,4H). 13 C NMR(125MHz,CDCl 3 )δ196.76,137.49,132.40,130.03,128.23.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (34.38 mg,81% yield; 30.56mg,72% yield). 1 H NMR(500MHz,CDCl 3 )δ7.85-7.82(m,2H),7.77-7.74(m,2H),7.59-7.55(m,1H),7.49-7.46(m,2H),6.98-6.95(m,2H). 13 C NMR(125MHz,CDCl 3 )δ195.58,163.16,138.20,132.55,131.88,130.07,129.71,128.16,113.50,55.47.
The reaction was carried out according to general procedure 4, column chromatography (petroleum ether: ethyl acetate=15:1) to give a white solidThe product is obtained. (42.88 mg,83% yield; 32.55mg,53% yield). 1 H NMR(500MHz,CDCl 3 )δ7.91(d,J＝8.5Hz,2H),7.86-7.84(m,2H),7.71(d,J＝8.5Hz,2H),7.67-7.65(m,2H),7.61(t,J＝7.5Hz,1H),7.53-7.48(m,4H),7.43-7.40(m,1H). 13 C NMR(125MHz,CDCl 3 )δ196.34,145.21,139.95,137.73,136.20,132.36,130.71,129.98,128.95,128.29,128.16,127.28,126.95./>
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (20.72 mg,50% yield). 1 H NMR(500MHz,CDCl 3 )δ7.87(d,J＝10Hz,2H),7.80-7.76(m,4H),7.66-7.62(m,1H),7.53-7.49(m,2H). 13 C NMR(125MHz,CDCl 3 )δ194.99,141.09,136.18,133.27,132.10,130.17,129.99,128.56,117.96,115.53.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (25.52 mg,51% yield; 29.52mg,59% yield). 1 H NMR(500MHz,CDCl 3 )δ7.90(d,J＝8Hz,2H),7.81(d,J＝7.5Hz,2H),7.76(d,J＝8Hz,2H),7.63(t,J＝7.5Hz,1H),7.51(t,J＝8Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ195.55,140.70,136.71,133.71(d,J＝32.6Hz),133.09,130.13,130.10,128.52,125.34(q,J＝3.6Hz),123.64(q,J＝273Hz).
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (24.62 mg,53% yield). 1 H NMR(500MHz,CDCl 3 )δ8.11(d,J＝8.5Hz,1H),8.01(d,J＝8Hz,1H),7.94-7.92(m,1H),7.88-7.87(m,2H),7.62-7.58(m,2H),7.56-7.49(m,3H),7.47(t,J＝8Hz,2H). 13 CNMR(125MHz,CDCl 3 )δ198.01,138.28,136.32,133.69,133.21,131.24,130.93,130.39,128.42,128.38,127.75,127.23,126.43,125.67,124.31.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (26.94 mg,58% yield). 1 H NMR(500MHz,CDCl 3 )δ8.27(s,1H),7.95(s,2H),7.92(dd,J＝2.5,8Hz,2H),7.88-7.86(m,2H),7.64-7.61(m,2H),7.58-7.51(m,3H). 13 C NMR(125MHz,CDCl 3 )δ196.76,137.87,135.24,134.79,132.37,132.22,131.86,130.08,129.40,128.32,128.31,128.28,127.80,126.78,125.76.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (42.08 mg,93% yield; 37.56mg,93% yield). 1 H NMR(500MHz,CDCl 3 )δ7.75-7.73(m,2H),7.56(t,J＝7Hz,1H),7.47(t,J＝7.5Hz,2H),7.38-7.37(m,2H),6.86(d,J＝8Hz,1H),6.06(s,2H). 13 C NMR(125MHz,CDCl 3 )δ195.11,151.48,147.90,138.09,131.96,131.86,129.67,128.17,126.83,109.88,107.66,101.82.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (44.99 mg,70% yield; 40.49mg,63% yield). 1 H NMR(500MHz,CDCl 3 )δ8.37-8.35(m,1H),8.16(d,J＝8Hz,1H),8.08(s,1H),7.89-7.87(m,2H),7.60(t,J＝7.5Hz,1H),7.52(t,J＝7.5Hz,2H),7.44-7.38(m,2H),1.70(s,9H). 13 C NMR(125MHz,CDCl 3 )δ191.37,149.21,139.55,135.51,133.94,132.02,128.92,128.47,128.32,125.65,124.35,122.59,119.39,114.99,85.44,28.06.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (18.82 mg,50% yield; 24.47mg,65% yield). 1 H NMR(500MHz,CDCl 3 )δ7.94-7.93(m,1H),7.86-7.84(m,2H),7.61-7.57(m,2H),7.49(t,J＝8Hz,2H),7.39-7.38(m,1H). 13 CNMR(125MHz,CDCl 3 )δ189.98,141.26,138.59,133.90,132.28,129.34,128.58,128.35,126.18.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (30.50 mg,64% yield; 25.26mg,53% yield). 1 H NMR(500MHz,CDCl 3 )δ8.58(d,J＝8Hz,1H),8.01(s,1H),7.92(d,J＝8Hz,1H),7.88-7.87(m,2H),7.61(t,J＝7.5Hz,1H),7.54-7.50(m,3H),7.48-7.45(m,1H). 13 C NMR(125MHz,CDCl 3 )δ190.85,140.00,139.25,138.24,137.40,134.77,132.31,129.47,128.41,125.65,125.55,125.15,122.31.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a brown solid. (23.43 mg,50% yield;). 1 H NMR(500MHz,CDCl 3 )δ8.95-8.94(m,2H),8.59(s,1H),8.27-8.23(m,2H),7.89(d,J＝7.5Hz,2H),7.65(t,J＝7.5Hz,1H),7.53(t,J＝8Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ195.56,146.57,146.01,144.70,142.15,138.59,136.92,133.01,132.51,130.16,130.07,129.97,128.55.
The reaction was carried out according to general procedure 4, column chromatography (petroleum ether: ethyl acetate=15:1) to give the product as a white solid. (44.42 mg,94% yield;). 1 H NMR(500MHz,CDCl 3 )δ8.07(d,J＝1Hz,1H),7.82(dd,J＝1.5,8.5Hz,1H),7.74-7.71(m,3H),7.57(d,J＝8.5Hz,1H),7.29(d,J＝8Hz,2H),6.84(t,J＝1Hz,1H),2.45(s,3H). 13 C NMR(125MHz,CDCl 3 )δ196.30,157.06,146.30,142.88,135.45,133.13,130.23,128.90,127.17,126.69,124.27,111.13,107.19,21.61.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (46.71 mg,81% yield; 54.79mg,95% yield). 1 HNMR(500MHz,CDCl 3 )δ8.62(s,1H),8.20-8.19(m,1H),7.96-7.86(m,5H),7.64(t,J＝7.5Hz,1H),7.55-7.48(m,4H). 13 C NMR(125MHz,CDCl 3 )δ196.47,144.08,139.72,137.98,135.45,135.17,133.97,132.37,130.06,128.36,128.15,127.41,124.88,123.64,122.94,122.54,121.98.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an off-white solid. (41.94 mg,88% yield; 34.79mg,73% yield). 1 H NMR(500MHz,CDCl 3 )δ8.26(s,1H),7.98(t,J＝8.5Hz,1H),7.85-7.83(m,3H),7.61(t,J＝7.5Hz,1H),7.54-7.49(m,3H),7.42(d,J＝5.5Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ196.70,143.77,139.03,138.00,133.91,132.23,129.99,128.25,127.82,126.24,125.29,124.50,122.40.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (52.98 mg,98% yield). 1 H NMR(500MHz,CDCl 3 )δ8.03(s,1H),7.88-7.83(m,5H),7.61(t,J＝7.5Hz,2H),7.51(t,J＝7.5Hz,2H),7.45-7.37(m,2H),3.97(s,2H). 13 C NMR(125MHz,CDCl 3 )δ196.74,145.95,144.40,143.06,140.52,138.18,135.85,132.13,129.94,129.63,128.23,127.96,127.05,126.79,125.24,120.82,119.38,36.89.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (28.26 mg,72% yield). 1 H NMR(500MHz,CDCl 3 )δ7.79(d,J＝9.5Hz,2H),7.73(d,J＝10Hz,2H),7.60-7.56(m,1H),7.48(t,J＝9.5Hz,2H),7.28(d,J＝9.5Hz,2H),2.44(s,3H). 13 C NMR(125MHz,CDCl 3 )δ196.50,143.22,137.85,134.77,132.13,130.27,129.89,128.92,128.16,21.63./>
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (43.12 mg,89% yield). 1 H NMR(500MHz,CDCl 3 )δ7.80-7.78(m,4H),6.98-6.95(m,4H),3.89(s,6H). 13 C NMR(125MHz,CDCl 3 )δ194.47,162.80,132.22,130.72,113.42,55.45.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (38.04 mg,95% yield). 1 H NMR(500MHz,CDCl 3 )δ7.86-7.84(m,2H),7.78-7.76(m,2H),7.60(t,J＝7.5Hz,1H),7.49(t,J＝8Hz,2H),7.16(t,J＝8.5Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ195.26,165.38(d,J＝252.6Hz),137.49,133.78(d,J＝2.9Hz),132.69,132.54(d,J＝20.3Hz),129.86,128.34,115.44(d,J＝21.6Hz).
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (35.14 mg,82% yield). 1 H NMR(500MHz,CDCl 3 )δ7.79-7.77(m,2H),7.59(t,J＝7.5Hz,1H),7.50-7.47(m,4H),7.29(t,J＝8Hz,1H),2.37(d,J＝1.5Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ195.21,160.90(d,J＝245Hz),137.36,137.04(d,J＝6.4Hz),132.47,131.28(d,J＝4.6Hz),130.14(d,J＝17.4Hz),129.87,128.31,125.77(d,J＝3.1Hz),116.47(d,J＝23.3Hz),14.81(d,J＝3.5Hz).
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (41.27 mg,92% yield). 1 H NMR(500MHz,CDCl 3 )δ7.80(d,J＝7.5Hz,2H),7.57(t,J＝7.5Hz,1H),7.45(t,J＝8Hz,2H),7.10(s,1H),7.06(s,1H),2.29(s,3H),2.28(s,3H),2.23(s,3H). 13 C NMR(125MHz,CDCl 3 )δ198.72,139.25,138.23,135.94,134.46,133.27,132.77,132.39,130.18,130.07,128.32,19.69,19.57,19.17.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a white solid. (40.00 mg,90% yield). 1 H NMR(500MHz,CDCl 3 )δ8.09(d,J＝1.5Hz,1H),7.85-7.80(m,3H),7.71(d,J＝2Hz,1H),7.61-7.57(m,2H),7.49(t,J＝7.5Hz,2H),6.85(d,J＝1.5Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ196.51,157.15,146.37,138.17,132.76,132.10,129.94,128.19,127.21,126.75,124.46,111.30,107.19./>
The reaction was carried out according to general procedure 4, column chromatography (petroleum ether: ethyl acetate=15:1) to give an oily formA liquid product. (23.33 mg,50% yield). 1 H NMR(500MHz,CDCl 3 )δ9.04(s,1H),8.27-8.16(m,4H),7.87(d,J＝7.5Hz,2H),7.64(t,J＝7.5Hz,1H),7.55-7.49(m,3H). 13 C NMR(125MHz,CDCl 3 )δ196.04,152.47,149.70,137.42,137.39,135.48,132.70,131.37,130.10,129.85,129.54,128.56,127.29,121.99.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (30.30 mg,88% yield). 1 H NMR(500MHz,CDCl 3 )δ7.97-7.96(m,2H),7.71(d,J＝1Hz,1H),7.61-7.58(m,1H),7.50(d,J＝7.5Hz,2H),7.24-7.23(m,1H),6.60(dd,J＝1.5,8.5Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ182.55,152.25,147.08,137.23,132.55,129.25,128.39,120.55,112.18.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) gave the product as an oily liquid. (27.89 mg,81% yield). 1 H NMR(500MHz,CDCl 3 )δ7.92(s,1H),7.86-7.85(m,2H),7.61-7.57(m,1H),7.51-7.48(m,3H),6.91(d,J＝1Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ189.42,148.55,143.94,138.79,132.46,128.80,128.53,126.49,110.19.
The reaction was carried out according to general procedure 4, and column chromatography (petroleum ether: ethyl acetate=15:1) afforded the product as a yellow solid. (37.78 mg,85% yield). 1 H NMR(500MHz,CDCl 3 )δ8.26-8.25(m,1H),8.09(s,1H),7.91-7.89(m,2H),7.62(t,J＝7.5Hz,1H),7.58-7.51(m,3H),7.44-7.40(m,2H). 13 C NMR(125MHz,CDCl 3 )δ190.21,155.56,152.19,139.24,132.45,128.77,128.64,125.81,125.18,124.52,122.88,121.22,111.48./>

Claims (10)

1. A bio-based carbonylation reagent comprising methyl esterified cellulose.
2. The carbonylation reagent according to claim 1, wherein the methyl esterified cellulose has a structural unit represented by formula 1:
in formula 1, R 1 、R 2 And R is 3 Is hydrogen orAnd at least R 1 、R 2 And R is 3 At least one of which is->
3. The carbonylation reagent according to claim 1, wherein the methyl esterified cellulose has a degree of substitution of 0.1 to 3, preferably 0.5 to 2, further preferably 1 to 1.5, most preferably 1.2 to 1.4.
4. A process for preparing a carbonylation reagent comprising the steps of:
(1) Reacting a cellulosic feedstock in a formic acid solution to produce a reaction mixture comprising methyl esterified cellulose;
(2) Subjecting the reaction mixture to solid-liquid separation;
(3) Concentrating and drying the liquid separated in the step (2).
5. The method according to claim 4, wherein,
the formic acid solution is 10-100% formic acid aqueous solution by mass fraction; and/or the number of the groups of groups,
the mass volume ratio of the formic acid solution to the cellulose raw material is 1 mL/g-100 mL/g; and/or the number of the groups of groups,
The temperature of the reaction is 10-120 ℃, and the reaction time is 1 minute-24 hours;
preferably, the reaction comprises a first stage and a second stage, the first stage being carried out at 80-120 ℃, preferably 90-110 ℃, more preferably e.g. 95 ℃, for 4-8 hours, preferably 5-6.5 hours, e.g. 6 hours; the second stage is carried out at 20-40 c, preferably 20-30 c, e.g. 25 c, for 8-14 hours, preferably 10-13 hours, e.g. 12 hours.
6. A carbonylation reaction process comprising:
reacting reactant A, reactant B and the carbonylation reagent of any one of claims 1-3 to produce a carbonyl-containing compound,
the reactant a is selected from organic compounds having a halogen group, preferably an aryl halide or a heteroaryl halide;
the reactant B is selected from hydroxyl, NH 2 Organic compounds of terminal alkynyl, boric acid and/or boric acid ester groups.
7. The method of claim 6, wherein the step of providing the first layer comprises,
the organic compound with the halogen group is shown as a formula I:
ring a represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms;
in the formula I, R 1 Represents one or more substituents selected from hydrogen, deuterium, cyano, amino, nitro, C1-C5 alkylamino, halogen, C1-C5 alkyl, C1-C5 alkoxy, phenyl, benzoyl, methoxycarbonyl, ethoxycarbonyl;
Preferably, ring A is a benzene ring, 4-methylbenzene ring, 4-t-butylbenzene ring, 4-methoxybenzene ring, 3-methoxybenzene ring, 2-methoxybenzene ring/4-phenylbenzene ring, 4-benzoyl benzene ring, 4-cyanobenzene ring, 4-carbomethoxy benzene ring, 4-trifluoromethyl benzene ring, 4-n-butyloxy benzene ring, 2-trifluoromethyl benzene ring, 3, 5-dimethylbenzene ring, 3, 5-dimethoxy benzene ring, 3,4, 5-trimethylbenzene ring, 2-naphthalene ring, 1, 2-methylenedioxybenzene ring, 2, 3-dihydrobenzo [ b ] [1,4] dioxin, 2-methylbenzoxazole, benzofuran ring, furan ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, fluorene, indole ring, quinoline ring, quinoxaline ring, carbamate benzene ring, ethylamine benzene ring or halogenated;
preferably, the organic compound containing a halogen group is selected from one or more of the following compounds:
x represents chlorine, bromine or iodine, preferably bromine or iodine;
preferably, the reactant B is selected from compounds of the following structural formula:
wherein n is 0, 1,2, 3 or 4; r is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro, cyano, halogen, hydroxy, amino; wherein n is 0, 1,2, 3 or 4; r is selected from C1-C5 alkyl, C1-C5 alkoxy, nitro, cyano, halogen, hydroxy, amino; x and Y are each independently halogen or amino, halogen preferably bromine or iodine;
The reactant B is, for example:
8. the method according to claim 6 or 7, wherein,
the reactant B is selected from organic compound containing hydroxyl, NH or NH 2 An organic compound containing an alkynyl group, and an organic compound containing a boric acid group or a boric acid ester group;
(1) The hydroxyl-containing organic compound is preferably an alcohol compound, further preferably the alcohol compound is selected from the group consisting of C1-C10 alkyl alcohols, the C1-C10 alkyl groups optionally substituted with substituents selected from the group consisting of cyano, nitro, halogen, C3-C10 cycloalkyl, C3-C10 cycloalkenyl, C6-C10 aryl, amino, C1-C5 alkoxy, C1-C5 alkyl substituted amino;
specifically, the alcohol compound is selected from methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, isobutanol, sec-butanol, n-pentanol, 2-methyl butanol, 3-methyl butanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, cyclopropyl alcohol, cyclobutyl alcohol, cyclopentyl alcohol, cyclohexanol, ethylene glycol, benzyl alcohol, phenethyl alcohol, phenylpropanol,1-cyclohexenyl methanol;
(2) Said NH or NH containing 2 The organic compound of (2) is selected from the group consisting of C3-C10 alkylamine, C6-C20 arylamine, C3-C20 heteroarylamine, said C3-C10 alkyl optionally substituted with a substituent selected from the group consisting of cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C10 aryl, C3-C10 heteroaryl, amino, C1-C5 alkoxy, C1-C5 alkyl substituted amino, said C6-C20 aryl and C3-C20 heteroaryl optionally substituted with C1-C5 alkyl, C1-C5 alkoxy, halogen, cyano, nitro and amino;
In particular, the NH or NH-containing 2 The organic compound of (2) is selected from the following compounds:
(3) The organic compound containing terminal alkynyl is selected from R 2 D，Wherein R is 2 Representation ofD is selected from the group consisting of C3-C10 alkyl, C6-C20 aryl and C3-C20 heteroaryl, said C3-C10 alkyl, C6-C20 aryl and C3-C20 heteroaryl being optionally substituted with a member selected from the group consisting of cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C14 aryl, amino, C1-C5 alkoxy, C6-C10 aryl, C3-C10 heteroaryl,
A substituent of a C1-C5 alkyl-substituted amino group;
specifically, the organic compound containing terminal alkynyl is selected from the following compounds:
(4) The organic compound containing boric acid group or boric acid ester group is selected from R 3 E, wherein R is 3 Is thatR 4 And R is 5 Each independently is C1-C6 alkyl or taken together to form a 5-6 membered ring, E is selected from C3-C10 alkyl, C6-C20 aryl and C3-C20 heteroaryl, said C3-C10 alkyl, C6-C20 aryl and C3-C20 heteroaryl being optionally substituted with a substituent selected from cyano, nitro, halogen, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C6-C14 aryl, amino, C1-C5 alkoxy, C6-C10 aryl, C3-C10 heteroaryl, C1-C5 alkyl-substituted amino;
specifically, the boric acid compound is selected from
9. The process according to claim 6 or 7, characterized in that the reaction is carried out in an aprotic polar solvent, preferably selected from acetonitrile, methanol, ethanol, isopropanol, tetrahydrofuran, dioxane, DMF, DMSO; and/or
The temperature of the reaction is 20-120 ℃;
the reaction is carried out in the presence or absence of a palladium catalyst and a phosphorus ligand;
specifically, the palladium catalyst can be one or more of palladium acetate, palladium trifluoroacetate, palladium quaternary valerate, palladium dichlorodiacetonitrile, bis (benzonitrile) palladium chloride, palladium bromide, palladium iodide, palladium tetrafluoroborate, palladium hexafluoroacetylacetonate, palladium bis (acetylacetonate), palladium tetrafluoroacetonitrile triflate, palladium pivalate and (1E, 4E) -bis (dibenzylideneacetone) palladium, and can be one or more of bis (dibenzylideneacetone) dipalladium and tris (dibenzylideneacetone) dipalladium; and/or
Specifically, the phosphorus ligand is selected from 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene, 1 '-bis (diphenylphosphino) ferrocene, tri-o-tolylphosphine, tricyclohexylphosphine tetrafluoroborate, tri-t-butylphosphine tetrafluoroborate, di-t-butylmethylphosphine tetrafluoroborate, triphenylphosphine, 2-di-t-butylphosphino-2', 4',6' -triisopropylbiphenyl, 2-dicyclohexylphosphine-2 '-methylbiphenyl, tris (2-furyl) phosphine, 2- (dicyclohexylphosphino) biphenyl, N-butylbis (1-adamantyl) phosphine, 2- (di-t-butylphosphine) -2' - (N, N-dimethylamino) biphenyl, 2- (di-t-butylphosphine) biphenyl, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1-biphenyl, 3 2-dicyclohexylphosphine-2 ',6' -diisopropylphosphino-biphenyl, 2-dicyclohexylphosphine-2 ',4',6 '-triisopropylbiphenyl, rac-2- (di-t-butylphosphine) -1, 3' -bis (diphenylphosphine) -2'- (N, N-dimethylamino) biphenyl, 2- (di-t-butylphosphine) -1, 3' -diisopropylphosphine, 2, 3-bis (diphenylphosphine), 2-di-tert-butylphosphine-2 ' -methylbiphenyl, 2-dicyclohexylphosphino-2 ' - (N, N-dimethylamine) biphenyl, 1' -bis (di-tert-butylphosphino) ferrocene, bis (2-diphenylphosphinophenyl) ether, 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene, 1' -bis (diisopropylphosphino) ferrocene, 1, 2-bis (diphenylphosphino) benzene, 1,2,3,4, 5-pentaphenyl-1 ' - (di-tert-butylphosphino) ferrocene, or bis (diphenylphosphinomethane;
Preferably, the reaction is carried out in the presence of a base, preferably selected from Na 3 PO 4 、K 3 PO 4 、LiOH、Na 2 CO 3 、K 2 CO 3 、t-BuOK、t-BuONa、t-BuOLi、NEt 3 1, 8-diazabicyclo [5.4.0]Undec-7-ene, diisopropylamine, or a combination thereof.
10. The method according to claim 6 or 7, wherein,
in the carbonylation reaction, the structural formula of the reactant A, B and the carbonyl-containing compound is shown in any one of the following reactions 1 to 124:
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CN202311472978.3A 2023-11-07 2023-11-07 Bio-based carbonylation reagent and application thereof Pending CN117756950A (en)

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