CN111892489B - Method for difluoroalkylation of deaminated fatty amine - Google Patents

Method for difluoroalkylation of deaminated fatty amine Download PDF

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CN111892489B
CN111892489B CN202010843682.8A CN202010843682A CN111892489B CN 111892489 B CN111892489 B CN 111892489B CN 202010843682 A CN202010843682 A CN 202010843682A CN 111892489 B CN111892489 B CN 111892489B
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贺春阳
黄洋
赵亮
黄启平
贾佳
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Zunyi Medical University
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Abstract

The application discloses a method for difluoroalkylation of fatty amine after deamination in the field of organic synthesis, and particularly relates to a method for difluoroalkylation of fatty amine after deamination, which is characterized in that simple and easily-obtained fatty amine in a formula A is used as a raw material and reacts with a pyranyl tetrafluoroborate in a formula B under the condition of heating or room temperature to obtain an alkylpyridinium salt in a formula C; then selecting commercially available [ Ir (dtbbpy) (ppy) 2 ]PF 6 As a catalyst, the difluoroenolsilyl ether D is a difluoroalkylation reagent, and a plurality of difluoroalkyl substituted alkanes and cycloalkanes and derivatives thereof can be obtained with high yield. The method is simple and convenient to operate, simple and mild in reaction conditions, has excellent functional group compatibility, and is suitable for large-scale production and synthesis. The catalytic synthesis method can obtain the fluorine-containing amino acid with potential application value, and the obtained product can easily obtain various compounds containing difluoroalkyl, which have novel structures and are significant in the fields of medicines, pesticides and materials through further conversion.

Description

Method for difluoroalkylation after deamination of aliphatic amine
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for difluoroalkylation after deamination of fatty amine
Background
Difluoroalkyl groups are a very important class of fluorine-containing groups, present in many biologically active compounds and functional materials, which are thought to be bioisosteres of oxygen atoms and carbonyl groups and which are capable of modulating the pKa of the ortho-functional groups.
Over the last decade scientists have developed a number of methods for introducing difluoroalkyl groups into organic molecules, but these methods have focused on the difluoroalkylation of aromatics, heteroarenes, alkynes and alkenes, and few documents have been reported for the direct introduction of this group on the alkyl chain. At present, activated alcohol can be used as a reaction substrate for directly introducing difluoroalkyl on an aliphatic chain, but the dehydrofluorination reaction of aliphatic amine is not reported in documents. Based on the above, the invention provides a method for difluoroalkylation of fatty amine after deamination, which provides a feasible method for the difluoroalkylation of fatty amine widely existing in nature, and obtains some novel compounds by the method.
Disclosure of Invention
The method for carrying out difluoroalkylation after deaminizing the fatty amine is simple and efficient, and fills the gap of synthesizing the compounds at present.
The invention aims to provide a method for difluoroalkylation of fatty amine after deamination, which comprises the following steps of reacting fatty amine shown in a formula A with pyranyl tetrafluoroborate shown in a formula B under the condition of heating or room temperature to obtain alkyl pyridinium shown in a formula C; then under the condition of illumination, using photocatalyst and using difluoroenolsilyl ether with formula D as difluoroalkylation reagent to obtain various difluoroalkyl substituted alkanes and cycloalkanes with formula E and derivatives thereof, wherein the reaction formula is as follows:
Figure BDA0002642320860000011
in the above formulae, R 1 Is H, C 1-15 Alkyl, ester, halogen substituted C 1-15 Alkyl or tert-butoxycarbonyl protected amino substituted C 1-15 An alkyl group;
R 2 is phenyl, pyridyl, C 1-15 Alkyl, methylthio substituted C 1-15 Alkyl, tert-butoxycarbonyl protected amino substituted C 1-15 Alkyl, halogen substituted C 1-15 Alkyl, phenyl substituted C 1-15 Alkyl, ester substituted C 1-15 Alkyl radical, C 1-15 Alkyl, halogen, ester, cyano, tert-butoxy or trifluoromethyl substituted aryl.
Preferably, the molar ratio of the formula A to the formula B is 1 to 3:1 to 3; the molar ratio of the formula C to the photocatalyst to the formula D is 1-3: 0.01 to 0.1:1 to 3.
Preferably, the molar amount of the photocatalyst is 0.1 to 10 percent of the molar amount of the formula A. More preferably 2%.
Preferably, the reaction is carried out at 20 ℃ to 90 ℃.
Preferably, the photocatalyst is selected from: (4, 4 '-di-tert-butyl-2, 2' -bipyridine) bis [ (2-pyridyl) phenyl group]Iridium (III) hexafluorophosphate [ Ir (dtbbpy) (ppy) 2 ]PF 6 ) Terpyridyl ruthenium chloride hexahydrate (Ru for short) (bpy) 3 Cl 2 ) Tris (2-phenylpyridine) iridium (Ir (ppy) for short) 3 ) Or (2, 2' -bipyridine) bis (2-phenylpyridine) iridium (III) hexafluorophosphate (abbreviated as [ Ir (ppy) 2 (bpy)]PF 6 )。
The photocatalyst is most preferably (4, 4 '-di-tert-butyl-2, 2' -bipyridine) bis [ (2-pyridyl) phenyl group]Iridium (III) hexafluorophosphate ([ Ir (dtbbpy) (ppy) for short) 2 ]PF 6 )。
Preferably, the solvent is selected from: one or more of N-methylpyrrolidone (NMP for short), tetrahydrofuran (THF for short), N-dimethylformamide (DMF for short), N-dimethylacetamide (DMA for short) or ethylene glycol dimethyl ether (DME for short).
Most preferably, the solvent is a mixture of N, N-dimethylacetamide and ethylene glycol dimethyl ether in a molar ratio of 1.
It is another object of the present invention to provide difluoroalkyl-containing compounds prepared by the above process, which are of great significance in the fields of medicine, pesticide and materials, the compound of formula E being
Figure BDA0002642320860000021
In the above formula, R 1 Is H, C 1-15 Alkyl, ester, halogen substituted C 1-15 Alkyl or tert-butoxycarbonyl protected amino substituted C 1-15 An alkyl group;
R 2 is phenyl, pyridyl, C 1-15 Alkyl, methylthio substituted C 1-15 Alkyl, tert-butoxycarbonyl protected amino substituted C 1-15 Alkyl, halogen substituted C 1-15 Alkyl, phenyl substituted C 1-15 Alkyl, ester substituted C 1-15 Alkyl radical, by C 1-15 Alkyl, halogen, ester, cyano, tert-butoxy or trifluoromethyl-substituted aryl.
Further, the compound of formula E includes the following structure:
Figure BDA0002642320860000031
the invention relates to a method for difluoroalkylation after deamination of fatty amine, which is characterized in that simple and easily-obtained fatty amine of formula A is used as a raw material and reacts with pyranyl tetrafluoroborate of formula B under the condition of heating or room temperature to obtain alkyl pyridinium of formula C; then selecting commercially available [ Ir (dtbbpy) (ppy) 2 ]PF 6 The difluoroenolsilyl ether is used as catalyst and difluoroalkylating reagent to obtain various kinds of difluoroalkyl substituted organic matter. The raw materials selected by the method are from industrial raw materials, so that the method has excellent economy; meanwhile, the catalytic system is simple in reaction system and has excellent functional group compatibility.
The invention has the beneficial effects that: (1) The raw materials selected by the method are from industrial raw materials, and the method is mild in reaction conditions, economic, green and environment-friendly. (2) The reaction system is simple and homogeneous, and is suitable for large-scale production; (3) The reaction has excellent functional group compatibility and reaction diversity (4) partial products synthesized by the method have very important application in biology and material science.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. For reasons of space, they will not be described in detail.
The terms: as used herein, the term "C 1-15 Alkyl "means a straight or branched chain alkyl group having 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or the like.
The term "halogen" refers to fluorine, chlorine, bromine or iodine.
Detailed Description
The following is further detailed by way of specific embodiments:
the invention provides a method for deamination and difluoroalkylation of fatty amine, which preferably comprises the following steps: taking simple and easily-obtained fatty amine shown in the formula A as a raw material, and reacting the fatty amine with pyranyl tetrafluoroborate shown in the formula B under the condition of heating (90 ℃) or room temperature to obtain alkyl pyridinium shown in the formula C; then reacting the alkylpyridinium salt of formula C with the compound of formula D in a solvent at a temperature (e.g., 30 ℃ to 60 ℃, preferably 50 ℃) to form the compound of formula E;
Figure BDA0002642320860000041
in the formulae, R 1 、R 2 The definition is as described above.
More preferably, said compound of formula a is a compound selected from the group consisting of:
Figure BDA0002642320860000051
the formula a, formula B, formula D of the present invention can be prepared by methods commercially available or well known to those skilled in the art to which the present invention pertains, however, the specific conditions of the method, such as reactants, solvents, amounts of compounds used, reaction temperature, time required for the reaction, etc., are not limited to the following explanation.
As the catalyst, a photocatalyst known to those skilled in the art, (4, 4' -di-t-butyl-2, 2' -bipyridine) bis [ (2-pyridyl) phenyl ] iridium (III) hexafluorophosphate, ruthenium terpyridine chloride hexahydrate, tris (2-phenylpyridine) iridium or (2, 2' -bipyridine) bis (2-phenylpyridine) iridium (III) hexafluorophosphate can be used.
In the reaction system, the molar percentage of the used photocatalyst is 0.1 to 10 percent of the molar amount of the compound shown in the formula A, and the preferred molar percentage is 2 percent.
The compound of formula E prepared according to the present invention can be further modified as desired to prepare various functional compounds.
The product prepared by the preparation method can be separated and purified by various methods, and the methods comprise the following steps: thin layer chromatography, column chromatography, etc. The above purification methods are all conventional methods in the art, and for example, when thin layer chromatography and column chromatography are used, the developing solvent used may be a single solvent, or a mixed solvent such as petroleum ether or a mixed solvent of ethyl acetate and petroleum ether may be used.
The features mentioned above with reference to the invention, or the features mentioned with reference to the embodiments, can be combined arbitrarily. All the features disclosed in this specification may be combined in any combination, and each feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
The invention is further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Purification was carried out by a method of post-treatment which is conventional in the art in the following examples.
Examples 1 to 18
Figure BDA0002642320860000061
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of anhydrous ethanol and 297.5mg (3 mmol,1.2 equivalent) of Compound A-1 were injected, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-1.
To a 25mL reaction tube, 47.7mg (0.1mmol, 1 equivalent) of compound C-1,1.8mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon for three times, the corresponding solvent in the following table was added, 54.1mg (0.2mmol, 2 equivalents) of the compound D was injected, and after heating and stirring at 50 ℃ for 24 hours under blue light irradiation, the compound E-1, fluorine spectral yield is given in the table below. 1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝8.0Hz,2H),7.62(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),2.30–2.18(m,1H),1.84–1.80(m,4H),1.70–1.66(m,1H),1.34–1.16(m,5H). 19 F NMR(376MHz,CDCl 3 ) Delta-108.56 (d, J =14.7hz, 2f) compound E-1 is a novel compound.
Figure BDA0002642320860000062
Figure BDA0002642320860000071
Examples 19 to 21
Figure BDA0002642320860000072
To a 25mL reaction tube, 47.7mg (0.1mmol, 1 equivalent) of Compound C-1, the corresponding catalyst [ PC ] in the table below, was added](2.0 mol%), after replacement with argon three times, 0.25mL of N, N-Dimethylacetamide (DMA) and 0.75mL of ethylene glycol dimethyl ether (DME) were added, and 54.1mg (0.2mmol, 2 equivalents) of compound D was injected, and after heating and stirring at 50 ℃ for 24 hours under blue light irradiation, compound E-1 was obtained with the fluorine spectral yield shown in the following table. 1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝8.0Hz,2H),7.62(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),2.30–2.18(m,1H),1.84–1.80(m,4H),1.70–1.66(m,1H),1.34–1.16(m,5H). 19 F NMR(376MHz,CDCl 3 ) Delta-108.56 (d, J =14.7hz, 2f) compound E-1 is a novel compound.
Figure BDA0002642320860000073
Example 22
Figure BDA0002642320860000074
To a 25mL reaction tube, 47.7mg (0.1mmol, 1 equivalent) of compound C-1,1.8mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon for three times, 0.25mL of N, N-Dimethylacetamide (DMA) and 0.75mL of ethylene glycol dimethyl ether (DME) were added, 54.1mg (0.2 mmol,2 equivalents) of compound D was injected, and after heating and stirring at 35 ℃ for 24 hours under blue light irradiation, compound E-1 was obtained with a fluorine spectrum yield of 75%. 1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝8.0Hz,2H),7.62(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),2.30–2.18(m,1H),1.84–1.80(m,4H),1.70–1.66(m,1H),1.34–1.16(m,5H). 19 F NMR(376MHz,CDCl 3 ) Delta-108.56 (d, J =14.7hz, 2f) compound E-1 is a novel compound.
Example 23
Figure BDA0002642320860000081
To a 25mL reaction tube, 47.7mg (0.1mmol, 1 equivalent) of Compound C-1 was added, after three times of replacement with argon, 0.25mL of N, N-Dimethylacetamide (DMA) and 0.75mL of ethylene glycol dimethyl ether (DME) were added, and 54.1mg (0.2 mmol,2 equivalents) of Compound D was injected, and after stirring at 50 ℃ for 24 hours under irradiation with blue light, the formation of Compound E-1 was not monitored.
Example 24
Figure BDA0002642320860000082
To a 25mL reaction tube, 47.7mg (0.1mmol, 1 equivalent) of compound C-1,1.8mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon three times, 0.25mL of N, N-Dimethylacetamide (DMA) and 0.75mL of ethylene glycol dimethyl ether (DME) were added, and 54.1mg (0.2 mmol,2 equivalents) of compound D was injected, and after stirring at 50 ℃ for 24 hours in the dark, the formation of compound E-1 was not detected.
Example 25
Figure BDA0002642320860000083
To a 25mL reaction tube, 95.5mg (0.2mmol, 1 equivalent) of Compound C-1,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under irradiation with blue light to obtain Compound E-1 with a yield of 92%. 1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝8.0Hz,2H),7.62(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),2.30–2.18(m,1H),1.84–1.80(m,4H),1.70–1.66(m,1H),1.34–1.16(m,5H). 19 F NMR(376MHz,CDCl 3 ) Delta-108.56 (d, J =14.7hz, 2f) compound E-1 is a novel compound.
Example 26
Figure BDA0002642320860000091
Into a 25mL reaction tube, 990.5mg (2.5 mmol,1 equivalent) of Compound B was added, 2.5mL of absolute ethanol and 255.4mg (3 mmol,1.2 equivalents) of Compound A-2 were injected, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-2.
To a 25mL reaction tube, 92.7mg (0.2mmol, 1 equivalent) of Compound C-2,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under irradiation with blue light to obtain Compound E-2 with a yield of 55%. 1 H NMR(400MHz,CDCl 3 )δ8.11(d,J＝7.6Hz,2H),7.62(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),2.88–2.71(m,1H),1.86–1.79(m,2H),1.73–1.64(m,4H),1.61–1.58(m.2H). 19 F NMR(376MHz,CDCl 3 ) δ -106.17 (d, J =16.9hz, 2f) compound E-2 is a novel compound.
Example 27
Figure BDA0002642320860000092
To a 25mL reaction tube, 990.5mg (2.5mmol, 1 equivalent) of Compound B was added, 5mL of methylene chloride was injected, 333.0mg (2.5mmol, 1 equivalent) of Compound A-3 and 253.0mg (2.5mmol, 1 equivalent) of triethylamine were added, and after stirring at room temperature for 30 minutes, 300.2mg (5mmol, 2 equivalent) of acetic acid was added, and the stirring was continued for 6 hours, whereby Compound C-3 was obtained.
To a 25mL reaction tube, 102.3mg (0.2mmol, 1 equivalent) of Compound C-3,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4mmol, 2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation, to obtain Compound E-3 with a yield of 63%. 1 H NMR(400MHz,CDCl 3 )δ8.17(d,J＝7.6Hz,2H),7.66(t,J＝7.4Hz,1H),7.53(t,J＝7.8Hz,2H),7.24–7.17(m,4H),3.52–3.37(m,1H),3.20–3.18(m,4H). 19 F NMR(376MHz,CDCl 3 ) Delta-105.5 (d, J =15.8hz, 2f) compound E-3 is a novel compound.
Example 28
Figure BDA0002642320860000101
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 339.6mg (3 mmol,1.2 equivalents) of Compound A-4 were injected, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-4.
To a 25mL reaction tube, 98.3mg (0.2mmol, 1 equivalent) of Compound C-4,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-4 with a yield of 86%. 1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝8.0Hz,2H),7.62(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),2.49–2.35(m,1H),1.88–1.82(m,2H),1.77–1.74(m,2H),1.59–1.41(m,8H). 19 F NMR(376MHz,CDCl 3 ) Delta-104.18 (d, J =16.5hz, 2f) compound E-4 is a novel compound.
Example 29
Figure BDA0002642320860000102
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 550.0mg (3 mmol,1.2 equivalent) of Compound A-5 were injected, and the mixture was heated and stirred at 90 ℃ for 5 hours to obtain Compound C-5.
To a 25mL reaction tube, 112.3mg (0.2mmol, 1 equivalent) of Compound C-5,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-5 with a yield of 78%. 1 H NMR(400MHz,CDCl 3 )δ8.07(d,J＝8.0Hz,2H),7.62(t,J＝7.6Hz,1H),7.49(t,J＝7.8Hz,2H),2.52–2.43(m,1H),1.57–1.43(m,9H),1.38–1.29(s,13H). 19 F NMR(376MHz,CDCl 3 ) Delta-105.37 (d, J =16.5hz, 2f) compound E-5 is a novel compound.
Example 30
Figure BDA0002642320860000111
Into a 25mL reaction tube, 990.5mg (2.5 mmol,1 equivalent) of Compound B was added, 2.5mL of absolute ethanol and 381.7mg (3 mmol,1.2 equivalents) of Compound A-6 were injected, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-6.
To a 25mL reaction tube, 101.1mg (0.2mmol, 1 equivalent) of Compound C-6,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4mmol, 2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation, whereby Compound E-6 was obtained at a yield of 80%. 1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝7.6Hz,2H),7.62(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),2.59–2.45(m,1H),1.80–1.71(m,4H),1.61–1.45(m,10H). 19 F NMR(376MHz,CDCl 3 ) Delta-114.3 (d, J =16.5hz, 2f) compound E-6 is a novel compound.
Example 31
Figure BDA0002642320860000112
To a 25mL reaction tube, 514.8mg (3 mmol,1.2 equiv.) of Compound A-7 was added, 2.5mL of anhydrous ethanol and 303.6mg (3 mmol,1.2 equiv.) of triethylamine were injected, and the mixture was stirred at room temperature for 30 minutes, then 990.5mg (2.5 mmol,1 equiv.) of Compound B was added, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-7.
To a 25mL reaction tube, 102.7mg (0.2mmol, 1 equivalent) of Compound C-7,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-7 with a yield of 69%. 1 H NMR(400MHz,CDCl 3 )δ8.09(d,J＝8.0Hz,2H),7.65(t,J＝7.2Hz,1H),7.51(t,J＝7.6Hz,2H),2.45–2.33(m,1H),2.21–2.18(m,2H),1.97–1.95(m,2H),1.83–1.63(m,4H). 19 F NMR(376MHz,CDCl 3 ) δ -92.24 (d, J =236.9hz, 1f), -102.44-103.24 (m, 1F), -107.04 (d, J =14.3hz, 2f), compound E-7 is a novel compound.
Example 32
Figure BDA0002642320860000121
Into a 25mL reaction tube, 990.5mg (2.5mmol, 1 equivalent) of Compound B and 642.9mg (3mmol, 1.2 equivalent) of Compound A-8 were added, and 2.5mL of absolute ethanol was injected, followed by heating and stirring at 90 ℃ for 5 hours to obtain Compound C-8.
Into a 25mL reaction tube, 118.5mg (0.2mmol, 1 equivalent) of Compound C-8,3.7mg (2 mol)％)[Ir(dtbbpy)(ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-8 with a yield of 50%. For the texture: 1 H NMR(400MHz,CDCl 3 )δ8.07(d,J＝6.8Hz,4H),7.64–7.61(m,2H),7.51–7.47(m,4H),4.73–4.40(m,2H),3.85–3.40(m,2H),2.33–2.19(m,2H),2.10–2.07(m,2H),1.91–1.85(m,4H),1.72–1.70(m,2H),1.58–1.38(m,6H),1.44(s,9H),1.43(s,9H),1.15–1.06(m,2H).For the mixture: 19 F NMR(376MHz,CDCl 3 ) δ -107.76 (t, J =13.5hz, 2f), -107.52 (t, J =14.3hz, 2f) compound E-8 is a novel compound.
Example 33
Figure BDA0002642320860000122
Into a 25mL reaction tube were added 990.5mg (2.5mmol, 1 equivalent) of Compound B and 600.8mg (3mmol, 1.2 equivalent) of Compound A-9, and 2.5mL of absolute ethanol was injected, followed by heating and stirring at 90 ℃ for 5 hours to obtain Compound C-9.
To a 25mL reaction tube, 115.7mg (0.2mmol, 1 equivalent) of Compound C-9,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-9 with a yield of 81%. 1 H NMR(400MHz,CDCl 3 )δ8.08(d,J＝7.6Hz,2H),7.64(t,J＝7.4Hz,1H),7.50(t,J＝7.8Hz,2H),4.22–4.19(m,2H),2.72–2.66(m,2H),2.47–2.41(m,1H),1.80–1.77(m,2H),1.56–1.48(m,2H),1.45(s,9H). 19 F NMR(376MHz,CDCl 3 ) Delta-107.86 (t, J =12.6hz, 2f) compound E-9 is a novel compound.
Example 34
Figure BDA0002642320860000131
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 558.8mg (3 mmol,1.2 equivalents) of Compound A-10 were injected, and the mixture was heated and stirred at 90 ℃ for 5 hours to obtain Compound C-10.
To a 25mL reaction tube, 112.9mg (0.2mmol, 1 equivalent) of Compound C-10,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under irradiation with blue light to obtain Compound E-10 with a yield of 45%. 1 H NMR(400MHz,CDCl 3 )δ8.12(d,J＝7.6Hz,2H),7.65(t,J＝7.4Hz,1H),7.51(t,J＝7.8Hz,2H),3.71–3.66(m,2H),3.56(br,1H),3.42–3.32(m,2H),3.21–3.09(m,1H),2.17–2.00(m,1H),1.46(s,9H). 19 F NMR(376MHz,CDCl 3 ) Delta-105.61-105.86 (m, 2F). Compound E-10 is a novel compound.
Example 35
Figure BDA0002642320860000132
Into a 25mL reaction tube, 990.5mg (2.5 mmol,1 equivalent) of Compound B was added, 2.5mL of anhydrous ethanol and 303.4mg (3 mmol,1.2 equivalents) of Compound A-11 were injected, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-11.
To a 25mL reaction tube, 95.9mg (0.2mmol, 1 equivalent) of Compound C-11,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-11 with a yield of 60%. 1 H NMR(400MHz,CDCl 3 )δ8.09(d,J＝8.0Hz,2H),7.65(t,J＝7.4Hz,1H),7.51(t,J＝7.6Hz,2H),4.04–4.03(m,2H),3.44–3.38(m,2H),2.62–2.51(m,1H),1.74–1.69(m,4H). 19 F NMR(376MHz,CDCl 3 )δ-108.68(dJ =14.3hz, 2f) compound E-11 is a novel compound.
Example 36
Figure BDA0002642320860000141
Into a 25mL reaction tube, 990.5mg (2.5 mmol,1 equivalent) of Compound B was added, 2.5mL of absolute ethanol and 447.7mg (3 mmol,1.2 equivalents) of Compound A-12 were injected, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-12.
To a 25mL reaction tube, 105.5mg (0.2mmol, 1 equivalent) of Compound C-12,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-12 with a yield of 66%. 1 H NMR(400MHz,CDCl 3 )δ8.02(d,J＝7.6Hz,2H),7.59(t,J＝7.4Hz,1H),7.44(t,J＝7.8Hz,2H),7.23(d,J＝6.8Hz,2H),7.18–7.12(m,3H),2.82–2.75(m,1H),2.60–2.53(m,1H),2.50–2.34(m,1H),2.04–1.95(m,1H),1.66–1.56(m,1H),1.11(d,J＝6.8Hz,3H). 19 F NMR(376MHz,CDCl 3 ) Delta-107.7 to 107.8 (m, 2F). Compound E-12 is a novel compound.
Example 37
Figure BDA0002642320860000142
To a 25mL reaction tube, 990.5mg (2.5mmol, 1 equivalent) of Compound B was added, 5mL of methylene chloride, 574.3mg (2.5mmol, 1 equivalent) of Compound A-13, and 506.0mg (5mmol, 2 equivalent) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 300.2mg (5mmol, 2 equivalent) of acetic acid was added, and the stirring was continued for 6 hours, whereby Compound C-13 was obtained.
To a 25mL reaction tube, 114.3mg (0.2mmol, 1 equivalent) of Compound C-13,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DMA) were addedDME), 108.2mg (0.4 mmol,2 equivalents) of compound D was injected, and after heating and stirring at 50 ℃ for 36 hours under blue light irradiation, compound E-13 was obtained with a yield of 94%. 1 H NMR(400MHz,CDCl 3 )δ8.07(d,J＝7.6Hz,2H),7.64(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),7.33–7.29(m,2H),7.23–7.21(m,3H),3.72(s,3H),3.51–3.40(m,1H),2.88–2.80(m,1H),2.75–2.67(m,1H),2.33–2.15(m,2H). 19 F NMR(376MHz,CDCl 3 ) Delta-101.09 (dd, J =293.8,11.8hz, 1f), -105.00 (dd, J =294.0,17.7hz, 1f) compound E-13 is a novel compound.
Example 38
Figure BDA0002642320860000151
To a 25mL reaction tube, 647.0mg (3 mmol,1.2 equiv.) of Compound A-14 was added, 2.5mL of anhydrous ethanol and 303.6mg (3 mmol,1.2 equiv.) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 990.5mg (2.5 mmol,1 equiv.) of Compound B was added, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-14.
Into a 25mL reaction tube, 111.5mg (0.2mmol, 1 equivalent) of compound C-14,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain compound E-14 with a yield of 81%. 1 H NMR(400MHz,CDCl 3 )δ8.10(d,J＝8.0Hz,2H),7.65(t,J＝7.4Hz,1H),7.51(t,J＝7.8Hz,2H),7.32–7.28(m,2H),7.26–7.23(m,3H),3.77–3.66(m,1H),3.57(s,3H),3.19(d,J＝7.6Hz,2H). 19 F NMR(376MHz,CDCl 3 ) δ -101.94 (dd, J =295.5,13.2hz, 1f), -103.74 (dd, J =295.5,15.0hz, 1f), compound E-14 is a novel compound.
Example 39
Figure BDA0002642320860000152
To a 25mL reaction tube, 750.4mg (3 mmol,1.2 equiv.) of Compound A-15 was added, 2.5mL of anhydrous ethanol and 303.6mg (3 mmol,1.2 equiv.) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 990.5mg (2.5 mmol,1 equiv.) of Compound B was added, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-15.
To a 25mL reaction tube, 118.4mg (0.2mmol, 1 equivalent) of Compound C-15,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-15 with a yield of 80%. 1 H NMR(400MHz,CDCl 3 )δ8.05(d,J＝8.0Hz,2H),7.61(t,J＝7.4Hz,1H),7.46(t,J＝7.8Hz,2H),7.22(d,J＝8.0Hz,2H),7.13(d,J＝8.0Hz,2H),3.70–3.61(m,1H),3.54(s,3H),3.11(d,J＝7.6Hz,2H). 19 F NMR(376MHz,CDCl 3 ) Delta-101.80 (dd, J =296.1,13.7hz, 1f), -103.59 (dd, J =296.3,15.0hz, 1f), compound E-15 is a novel compound.
Example 40
Figure BDA0002642320860000161
To a 25mL reaction tube, 701.0mg (3 mmol,1.2 equiv.) of Compound A-16 was added, 2.5mL of anhydrous ethanol and 303.6mg (3 mmol,1.2 equiv.) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 990.5mg (2.5 mmol,1 equiv.) of Compound B was added, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-16.
To a 25mL reaction tube, 115.1mg (0.2mmol, 1 equivalent) of Compound C-16,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-16 with a yield of 85%. 1 H NMR(400MHz,CDCl 3 )δ8.10(d,J＝8.0Hz,2H),7.66(t,J＝7.4Hz,1H),7.51(t,J＝7.6Hz,2H),7.22–7.18(m,2H),6.98(d,J＝8.6Hz,2H),3.74–3.63(m,1H),3.58(s,3H),3.16(d,J＝7.2Hz,2H). 19 F NMR(376MHz,CDCl 3 ) Delta-101.91 (dd, J =296.1,13.7hz, 1f), -103.57 (dd, J =296.1,15.2hz, 1f), -115.97-116.05 (m, 1F) compound E-16 is a novel compound.
EXAMPLE 41
Figure BDA0002642320860000162
To a 25mL reaction tube, 990.5mg (2.5mmol, 1 equivalent) of Compound B was added, 5mL of dichloromethane, 719.5mg (2.5mmol, 1 equivalent) of Compound A-17, and 506.0mg (5mmol, 2 equivalent) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 300.2mg (5mmol, 2 equivalent) of acetic acid was added, and stirring was continued for 6 hours to obtain Compound C-17.
To a 25mL reaction tube, 125.9mg (0.2mmol, 1 equivalent) of Compound C-17,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain compound E-17 with a yield of 64%. 1 H NMR(400MHz,CDCl 3 )δ8.10(d,J＝8.0Hz,2H),7.65(t,J＝7.4Hz,1H),7.50(t,J＝7.8Hz,2H),7.11(d,J＝8.0Hz,2H),6.92(d,J＝8.0Hz,2H),3.73–3.62(m,1H),3.54(s,3H),3.15–3.13(m,2H),1.32(s,9H). 19 F NMR(376MHz,CDCl 3 ) δ -102.00 (dd, J =295.5,13.5hz, 1f), -103.73 (dd, J =295.5,15.4hz, 1f) compound E-17 is a novel compound.
Example 42
Figure BDA0002642320860000171
634.9mg (3mmol, 1.2 equivalents) of Compound A-18 was added to a 25mL reaction tube, 2.5mL of anhydrous ethanol and 303.6mg (3mmol, 1.2 equivalents) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 990.5mg (2.5mmol, 1 equivalent) of Compound B was added and stirred at 90 ℃ for 5 hours to obtain Compound C-18.
To a 25mL reaction tube, 110.7mg (0.2mmol, 1 equivalent)Compound C-18,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-18 with a yield of 87%. 1 H NMR(400MHz,CDCl 3 )δ8.07(d,J＝7.6Hz,2H),7.64(t,J＝7.4Hz,1H),7.51(t,J＝7.6Hz,2H),3.70(s,3H),3.69(s,3H),3.56–3.46(m,1H),2.60–2.43(m,2H),2.27–2.17(m,2H). 19 F NMR(376MHz,CDCl 3 ) δ -100.75 (dd, J =295.5,10.5hz, 1f), -106.28 (dd, J =295.3,19.0hz, 1f), compound E-18 is a novel compound.
Example 43
Figure BDA0002642320860000172
Into a 25mL reaction tube, 592.8mg (3 mmol,1.2 equivalents) of Compound A-19 was added, 2.5mL of anhydrous ethanol and 303.6mg (3 mmol,1.2 equivalents) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 990.5mg (2.5 mmol,1 equivalent) of Compound B was added, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-19.
To a 25mL reaction tube, 107.9mg (0.2mmol, 1 equivalent) of compound C-19,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-19 with a yield of 71%. 1 H NMR(400MHz,CDCl 3 )δ8.05(d,J＝8.0Hz,2H),7.64(t,J＝7.4Hz,1H),7.50(t,J＝7.8Hz,2H),4.12–4.01(m,1H),3.73(s,3H),3.67(s,3H),3.07–3.01(m,1H),2.86–2.81(m,1H). 19 F NMR(376MHz,CDCl 3 ) δ -99.76 (dd, J =288.4,10.5hz, 1f), -105.59 (dd, J =288.0,18.4hz, 1f) compound E-19 is a novel compound.
Example 44
Figure BDA0002642320860000181
Into a 25mL reaction tube, 890.4mg (3mmol, 1.2 equivalents) of Compound A-20 was added, 2.5mL of anhydrous ethanol and 303.6mg (3mmol, 1.2 equivalents) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 990.5mg (2.5mmol, 1 equivalent) of Compound B was added, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-20.
To a 25mL reaction tube, 127.7mg (0.2mmol, 1 equivalent) of Compound C-20,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-20 with a yield of 69%. 1 H NMR(400MHz,CDCl 3 ) δ 8.06 (d, J =7.2hz, 2h), 7.62 (t, J =7.4hz, 1h), 7.48 (t, J =7.8hz, 2h), 4.57 (br, 1H), 3.69 (s, 3H), 3.43-3.32 (m, 1H), 3.11 (m, 2H), 1.96-1.79 (m, 2H), 1.53-1.45 (m, 4H), 1.42 (s, 9H). Compound E-20 is a novel compound.
Example 45
Figure BDA0002642320860000182
To a 25mL reaction tube, 599.1mg (3mmol, 1.2 equivalents) of Compound A-21, 2.5mL of anhydrous ethanol and 303.6mg (3mmol, 1.2 equivalents) of triethylamine were added, and after stirring at room temperature for 30 minutes, 990.5mg (2.5mmol, 1 equivalent) of Compound B was added, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-21.
To a 25mL reaction tube, 108.3mg (0.2mmol, 1 equivalent) of Compound C-21,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain compound E-21 with a yield of 67%. 1 H NMR(400MHz,CDCl 3 )δ8.07(d,J＝8.4Hz,2H),7.64(t,J＝7.4Hz,1H),7.50(t,J＝7.8Hz,2H),3.70(s,3H),3.69–3.64(m,1H),2.72–2.66(m,1H),2.61–2.54(m,1H),2.28–2.13(m,2H),2.10(s,3H). 19 F NMR(376MHz,CDCl 3 ) Delta-100.57 (dd, J =293.3,11.7hz, 1f), -105.04 (dd, J =293.3,18.0hz, 1f), compound E-21 is a novel compound.
Example 46
Figure BDA0002642320860000191
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 321.5mg (3 mmol,1.2 equivalents) of Compound A-22 were injected, and the mixture was heated and stirred at 90 ℃ for 5 hours to obtain Compound C-22.
To a 25mL reaction tube, 97.1mg (0.2mmol, 1 equivalent) of Compound C-22,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4mmol, 2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation, to obtain Compound E-22 in a yield of 77%. 1 H NMR(400MHz,CDCl 3 )δ8.05(d,J＝7.6Hz,2H),7.62(t,J＝7.4Hz,1H),7.47(t,J＝7.8Hz,2H),7.33(s,5H),3.54(t,J＝17.8Hz,2H). 19 F NMR(376MHz,CDCl 3 )δ-98.75(t,J＝17.9Hz,2F).
Example 47
Figure BDA0002642320860000192
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 375.4mg (3 mmol,1.2 equivalents) of Compound A-23 were injected, and the mixture was heated and stirred at 90 ℃ for 5 hours to obtain Compound C-23.
To a 25mL reaction tube, 100.7mg (0.2mmol, 1 equivalent) of Compound C-23,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected, and after heating and stirring were carried out at 50 ℃ for 36 hours under blue light irradiation, compound E-23 was obtained,the yield was 55%. 1 H NMR(400MHz,CDCl 3 )δ8.04(d,J＝8.0Hz,2H),7.62(t,J＝7.4Hz,1H),7.48(t,J＝7.8Hz,2H),7.29–7.26(m,2H),7.01(t,J＝8.6Hz,2H),3.49(t,J＝17.6Hz,2H). 19 F NMR(367MHz,CDCl 3 ) Delta-98.86 (t, J =17.5hz, 2f), -114.98-115.08 (m, 1F), compound E-23 is a novel compound.
Example 48
Figure BDA0002642320860000201
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 424.8mg (3 mmol,1.2 equivalents) of Compound A-24 were injected, and the mixture was heated and stirred at 90 ℃ for 5 hours to obtain Compound C-24.
To a 25mL reaction tube, 104.0mg (0.2mmol, 1 equivalent) of Compound C-24,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4mmol, 2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation, to obtain Compound E-24 in 54% yield. 1 H NMR(400MHz,CDCl 3 )δ8.02(d,J＝7.6Hz,2H),7.60(t,J＝7.4Hz,1H),7.45(t,J＝7.8Hz,2H),7.28–7.21(m,4H),3.46(t,J＝17.6Hz,2H). 19 F NMR(367MHz,CDCl 3 ) Delta-98.61 (t, J =17.7hz, 2f) compound E-24 is a novel compound.
Example 49
Figure BDA0002642320860000202
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 558.2mg (3 mmol,1.2 equivalent) of Compound A-25 were injected, and the mixture was heated and stirred at 90 ℃ for 5 hours to obtain Compound C-25.
To a 25mL reaction tube, 112.8mg (0.2mmol, 1 equivalent) of Compound C-25,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 Replacement with argon three timesThen, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, 108.2mg (0.4 mmol,2 equivalents) of compound D was injected, and after heating and stirring at 50 ℃ for 36 hours under blue light irradiation, compound E-25 was obtained with a yield of 60%. 1 H NMR(400MHz,CDCl 3 )δ8.05(d,J＝7.6Hz,2H),7.63(t,J＝7.0Hz,1H),7.50–7.44(m,4H),7.19(d,J＝7.6Hz,2H),3.47(t,J＝17.6Hz,2H). 19 F NMR(367MHz,CDCl 3 ) Delta-98.56 (t, J =17.7hz, 2f) compound E-25 is a novel compound.
Example 50
Figure BDA0002642320860000211
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 558.2mg (3 mmol,1.2 equivalents) of Compound A-26 were injected, and the mixture was heated and stirred at 90 ℃ for 5 hours to obtain Compound C-26.
To a 25mL reaction tube, 112.8mg (0.2mmol, 1 equivalent) of Compound C-26,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation, to obtain Compound E-26 with a yield of 71%. 1 H NMR(400MHz,CDCl 3 )δ8.12(d,J＝7.6Hz,2H),7.61(t,J＝8.0Hz,2H),7.49(t,J＝7.8Hz,2H),7.42(d,J＝7.6Hz,1H),7.3(t,J＝7.4Hz,1H),7.19–7.15(m,1H),3.77(t,J＝18.2Hz,2H). 19 F NMR(376MHz,CDCl 3 ) δ -98.87 (t, J =18.0hz, 2f), compound E-26 is a novel compound.
Example 51
Figure BDA0002642320860000212
Into a 25mL reaction tube, 990.5mg (2.5 mmol,1 equivalent) of Compound B was added, 2.5mL of absolute ethanol and 396.5mg (3 mmol,1.2 equivalent) of Compound A-27 were injected, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-27.
To a 25mL reaction tube, 102.1mg (0.2mmol, 1 equivalent) of Compound C-27,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After replacement with argon three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain compound E-27 with a yield of 61%. 1 H NMR(400MHz,CDCl 3 )δ8.06(d,J＝7.6Hz,2H),7.66–7.62(m,3H),7.51–7.45(m,4H),3.58(t,J＝17.4Hz,2H). 19 F NMR(367MHz,CDCl 3 )δ-98.01(t,J＝17.5Hz,2F).
Example 52
Figure BDA0002642320860000221
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 525.5mg (3 mmol,1.2 equivalent) of Compound A-28 were injected, and the mixture was heated and stirred at 90 ℃ for 5 hours to obtain Compound C-28.
To a 25mL reaction tube, 110.7mg (0.2mmol, 1 equivalent) of Compound C-28,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-28 with a yield of 75%. 1 H NMR(400MHz,CDCl 3 )δ8.07(d,J＝7.6Hz,2H),7.64(t,J＝7.2Hz,1H),7.60–7.44(m,6H),3.58(t,J＝17.6Hz,2H). 19 F NMR(376MHz,CDCl 3 )δ-69.95(s,3F),-105.78(t,J＝17.5Hz,2F).
Example 53
Figure BDA0002642320860000222
990.5mg (2.5 mmol,1 equivalent) of Compound B was added to a 25mL reaction tube, 2.5mL of absolute ethanol and 525.5mg (3 mmol,1.2 equivalents) of Compound A-29 were injected, and the mixture was heated and stirred at 90 ℃ for 5 hours to obtain Compound C-29.
To a 25mL reaction tube, 110.7mg (0.2mmol, 1 equivalent) of Compound C-29,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain compound E-29 with a yield of 61%. 1 H NMR(400MHz,CDCl 3 )δ8.12(d,J＝7.6Hz,2H),7.71(d,J＝8.0Hz,1H),7.64(t,J＝7.4Hz,1H),7.57–7.54(m,2H),7.51–7.48(m,2H),7.43(t,J＝7.2Hz,1H),3.77(t,J＝18.2Hz,2H). 19 F NMR(376MHz,CDCl 3 ) Delta-58.66 (t, J =6.2hz, 3f), -98.34-98.49 (m, 2F), compound E-29 is a novel compound.
Example 54
Figure BDA0002642320860000231
To a 25mL reaction tube, 605.0mg (3 mmol,1.2 equivalents) of Compound A-30 was added, 2.5mL of anhydrous ethanol and 303.6mg (3 mmol,1.2 equivalents) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 990.5mg (2.5 mmol,1 equivalent) of Compound B was added, and the mixture was stirred at 90 ℃ for 5 hours to obtain Compound C-30.
To a 25mL reaction tube, 108.7mg (0.2mmol, 1 equivalent) of Compound C-30,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation, whereby Compound E-30 was obtained at a yield of 76%. 1 H NMR(400MHz,CDCl 3 )δ8.05(d,J＝7.6Hz,2H),7.99(d,J＝8.0Hz,2H),7.62(t,J＝7.4Hz,1H),7.47(t,J＝7.8Hz,2H),7.40(d,J＝8.0Hz,2H),3.91(s,3H),3.57(t,J＝17.8Hz,2H).
Example 55
Figure BDA0002642320860000232
Into a 25mL reaction tube, 990.5mg (2.5mmol, 1 equivalent) of Compound B was added, 5mL of methylene chloride, 303.0mg (2.5mmol, 1 equivalent) of Compound A-31, and 253.0mg (2.5mmol, 1 equivalent) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 300.2mg (5mmol, 2 equivalent) of acetic acid was added, and stirring was continued for 6 hours to obtain Compound C-31.
To a 25mL reaction tube, 99.9mg (0.2mmol, 1 equivalent) of Compound C-31,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain compound E-31 with a yield of 41%. 1 H NMR(400MHz,CDCl 3 )δ8.04(d,J＝7.6Hz,2H),7.62(d,J＝7.6Hz,1H),7.47(t,J＝7.6Hz,2H),7.21–7.12(m,4H),3.48(t,J＝18.0Hz,2H),2.34(s,3H). 19 F NMR(376MHz,CDCl 3 )δ-98.85(t,J＝17.9Hz,2F).
Example 56
Figure BDA0002642320860000241
Into a 25mL reaction tube, 990.5mg (2.5mmol, 1 equivalent) of Compound B was added, 5mL of methylene chloride, 303.0mg (2.5mmol, 1 equivalent) of Compound A-32, and 253.0mg (2.5mmol, 1 equivalent) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 300.2mg (5mmol, 2 equivalent) of acetic acid was added, and stirring was continued for 6 hours to obtain Compound C-32.
To a 25mL reaction tube, 99.9mg (0.2mmol, 1 equivalent) of Compound C-32,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-32 with a yield of 56%. 1 H NMR(400MHz,CDCl 3 )δ8.06(d,J＝7.6Hz,2H),7.63(d,J＝7.6Hz,1H),7.48(t,J＝7.8Hz,2H),7.27(d,J＝7.6Hz,1H),7.22–7.15(m,3H),3.57(t,J＝18.4Hz,2H),2.38(s,3H). 19 F NMR(376MHz,CDCl 3 )δ-98.67(t,J＝18.0Hz,2F).
Example 57
Figure BDA0002642320860000242
Into a 25mL reaction tube, 990.5mg (2.5 mmol,1 equivalent) of Compound B was added, 5mL of methylene chloride, 270.4mg (2.5 mmol,1 equivalent) of Compound A-33, and 253.0mg (2.5 mmol,1 equivalent) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 300.2mg (5 mmol,2 equivalents) of acetic acid was added, and stirring was continued for 6 hours to obtain Compound C-33.
To a 25mL reaction tube, 97.3mg (0.2mmol, 1 equivalent) of compound C-33,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 After the replacement with argon for three times, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, and 108.2mg (0.4 mmol,2 equivalents) of Compound D was injected and heated and stirred at 50 ℃ for 36 hours under blue light irradiation to obtain Compound E-33 with a yield of 65%. 1 H NMR(400MHz,CDCl 3 )δ8.58–8.54(m,2H),8.07(d,J＝7.6Hz,2H),7.70(d,J＝7.6Hz,1H),7.64(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),7.28–7.26(m,1H),3.53(t,J＝17.6Hz,2H). 19 F NMR(376MHz,CDCl 3 ) δ -98.34 (t, J =16.9hz, 2f) compound E-33 is a novel compound.
Example 58
Figure BDA0002642320860000251
Into a 25mL reaction tube, 990.5mg (2.5 mmol,1 equivalent) of Compound B was added, 5mL of methylene chloride, 305.4mg (2.5 mmol,1 equivalent) of Compound A-34, and 253.0mg (2.5 mmol,1 equivalent) of triethylamine were injected, and after stirring at room temperature for 30 minutes, 300.2mg (5 mmol,2 equivalents) of acetic acid was added, and stirring was continued for 6 hours to obtain Compound C-34.
To a 25mL reaction tube, 100.1mg (0.2mmol, 1 equivalent) of compound C-34,3.7mg (2 mol%) [ Ir (dtbbpy) (ppy) 2 ]PF 6 Argon gasAfter the three-time substitution, 0.5mL of N, N-Dimethylacetamide (DMA) and 1.5mL of ethylene glycol dimethyl ether (DME) were added, 108.2mg (0.4 mmol,2 equivalents) of compound D was injected, and after heating and stirring at 50 ℃ for 36 hours under blue light irradiation, compound E-34 was obtained with a yield of 44%. 1 H NMR(400MHz,CDCl 3 )δ8.53–8.51(m,2H),7.99(d,J＝8.0Hz,2H),7.71(d,J＝8.0Hz,1H),7.62(t,J＝7.6Hz,1H),7.46(t,J＝7.8Hz,2H),7.29–7.26(m,1H),3.87–3.74(m,1H),1.51(d,J＝7.2Hz,3H). 19 F NMR(376MHz,CDCl 3 ) δ -104.06 (dd, J =282.9,15.6hz, 1f), -105.64 (dd, J =282.8,15.8hz, 1f) compound E-34 is a novel compound.
Example 59
Figure BDA0002642320860000252
Into a 25mL reaction tube were added 64.5mg (0.2mmol, 1 eq) of Compound E-5 and 89.8mg (0.8mmol, 4 eq) of potassium tert-butoxide, and 2mL of tert-butanol was injected, followed by stirring at 100 ℃ for 6 hours to give Compound F-5 in 65% yield. 1 H NMR(400MHz,CDCl 3 )δ5.64(td,J＝57.0,4.4Hz,1H),1.95–1.87(m,1H),1.43–1.31(m,22H). 19 F NMR(376MHz,CDCl 3 ) Delta-121.83 (dd, J =57.0,15.2hz, 2f) compound F-5 is a novel compound.
Example 60
Figure BDA0002642320860000253
67.9mg (0.2mmol, 1 equivalent) of Compound E-9 and 89.8mg (0.8mmol, 4 equivalents) of potassium tert-butoxide were added to a 25mL reaction tube, and 2mL of tert-butanol was injected and stirred at 100 ℃ for 6 hours to obtain Compound F-9 in 81% yield. 1 H NMR(400MHz,CDCl 3 )δ5.57(td,J＝56.7,4.5Hz,1H),4.17(br,2H),2.68(t,J＝11.8Hz,2H),1.97–1.84(m,1H),1.74–1.70(m,2H),1.45(s,9H),1.38–1.29(m,2H). 19 F NMR(376MHz,CDCl 3 )δ-119.13–-119.39(m,2F).
Example 61
Figure BDA0002642320860000261
To a 25mL reaction tube, 65.1mg (0.2mmol, 1 equivalent) of Compound E-10 and 89.8mg (0.8mmol, 4 equivalents) of potassium tert-butoxide were added, and 2mL of tert-butanol was injected and stirred at 100 ℃ for 6 hours to give Compound F-10 in 71% yield. 1 H NMR(400MHz,CDCl 3 )δ5.72(td,J＝56.4,5.2Hz,1H),3.53–3.44(m,2H),3.37–3.29(m,2H),2.68–2.56(m,1H),2.06–1.98(m,1H),1.93–1.84(m,1H),1.44(s,9H). 19 F NMR(376MHz,CDCl 3 )δ-119.24–-121.30(m,2F).
Example 62
Figure BDA0002642320860000262
To a 25mL reaction tube, 57.7mg (0.2mmol, 1 equivalent) of Compound E-12 and 89.8mg (0.8mmol, 4 equivalents) of potassium tert-butoxide were added, and 2mL of tert-butanol was injected and stirred at 100 ℃ for 6 hours to obtain Compound F-12 with a yield of 63%. 1 H NMR(400MHz,CDCl 3 )δ7.31(t,J＝7.4Hz,2H),7.21(t,J＝7.8Hz,3H),5.65(td,J＝56.9,3.5Hz,1H),2.80–2.73(m,1H),2.67–2.59(m,1H),1.96–1.86(m,2H),1.61–1.52(m,1H),1.07(d,J＝6.8Hz,3H). 19 F NMR(376MHz,CDCl 3 ) δ -122.6 (ddd, J =276.7,56.8,13.5hz, 1f), -124.17 (ddd, J =276.7,57.0,16.4hz, 1f) — compound F-12 is a novel compound.
Example 63
Figure BDA0002642320860000263
67.9mg (0.2mmol, 1 equivalent) of the compound E-9 was charged into a 25mL reaction tube, 3 argon gas was substituted three times, 2.0mL ethylene glycol dimethyl ether (DME) was added, the mixture was cooled to-78 deg.C, 645mg (4 mmol,20 equivalents) of diethylaminosulfur trifluoride was added dropwise, the mixture was stirred at room temperature for ten minutes, then slowly heated to 80 deg.C, and the mixture was stirred for 12 hours to obtain the compound G-9 with a yield of 55%. 1 H NMR(400MHz,CDCl 3 )δ7.56–7.44(m,5H),4.20(br,2H),2.70–2.65(m,2H),2.34–2.21(m,1H),1.94–1.91(m,2H),1.57–1.52(m,2H),1.46(s,9H). 19 F NMR(376MHz,CDCl 3 ) Delta-109.41-109.42 (m, 1F), -117.74-117.77 (m, 1F) compound G-9 is a novel compound.
Example 64
Figure BDA0002642320860000271
57.7mg (0.2 mmol,1 equivalent) of the compound E-12 was charged into a 25mL reaction tube, and after three times of replacement with argon, 2.0mL of ethylene glycol dimethyl ether (DME) was added, and cooled to-78 deg.C, 645mg (4 mmol,20 equivalents) of diethylaminosulfur trifluoride was added dropwise, and after stirring at room temperature for ten minutes, it was slowly heated to 80 deg.C, and then it was stirred under heating for 12 hours to obtain the compound G-12 with a yield of 56%. 1 H NMR(400MHz,CDCl 3 )δ7.56–7.43(m,5H),7.31(t,J＝7.4Hz,2H),7.24–7.19(m,3H),2.85–2.77(m,1H),2.63–2.55(m,1H),2.33–2.21(m,1H),2.19–2.11(m,1H),1.73–1.63(m,1H),1.23(d,J＝7.2Hz,3H). 19 F NMR(376MHz,CDCl 3 ) Delta-108.05-109.99 (m, 2F), -114.93-117.57 (m, 2F) compound G-12 is a novel compound.
Example 65
Figure BDA0002642320860000272
To a 25mL reaction tube, 64.5mg (0.2mmol, 1 eq) of compound E-5 was added, after three times replacement with argon, 2.0mL of anhydrous Tetrahydrofuran (THF) was added, cooled to 0 deg.C, 1mL of vinylmagnesium bromide (1.0 mmol/mL in THF) was injected, and stirring was continued for 10 hours to give compound H-5 in 82% yield. 1 H NMR(400MHz,CDCl 3 )δ7.59(d,J＝7.6Hz,2H),7.38–7.29(m,3H),6.70–6.62(m,1H),5.45–5.33(m,2H),2.43(br,1H),2.09–1.97(m,1H),1.72–1.65(m,1H),1.43–1.19(m,19H),1.13–0.99(m,2H). 19 F NMR(376MHz,CDCl 3 ) Delta-105.91-106.63 (m 1F), -112.28-113.02 (m, 1F), compound H-5 is a novel compound.
Example 66
Figure BDA0002642320860000273
67.9mg (0.2 mmol,1 eq) of compound E-9 was added to a 25mL reaction tube, replaced with argon three times, then 2.0mL anhydrous Tetrahydrofuran (THF) was added, cooled to 0 deg.C, 1mL vinyl magnesium bromide (1.0 mmol/mL in THF) was injected, and stirring was continued for 10 hours to give compound H-9 in 60% yield. 1 H NMR(400MHz,CDCl 3 )δ7.58–7.56(m,2H),7.39–7.31(m,3H),6.64–6.57(m,1H),5.44–5.33(m,2H),4.06–3.98(m,2H),2.56(br,1H),2.44(t,J＝12.8,2H),2.00–1.85(m,2H),1.45–1.32(m,3H),1.42(s,9H). 19 F NMR(376MHz,CDCl 3 ) Delta-110.01-110.72 (m, 1F), -116.26-116.97 (m, 1F) compound H-9 is a novel compound.
Example 67
Figure BDA0002642320860000281
To a 25mL reaction tube, 64.5mg (0.2mmol, 1 equivalent) of Compound E-5 and 22.7mg (0.6 mmol,3 equivalents) of sodium borohydride were added, 2mL of absolute ethanol was injected, and after stirring at room temperature for 0.5 hour, compound I-5 was obtained in 88% yield. 1 H NMR(400MHz,CDCl 3 )δ7.45–7.43(m,2H),7.40–7.37(m,3H),4.96–4.90(m,1H),2.34(br,1H),2.08–1.99(m,1H),1.65–1.58(m,1H),1.54–1.31(m,21H). 19 F NMR(376MHz,CDCl 3 ) Delta-113.00-113.75 (m 1F), -114.04-114.77 (m, 1F), compound I-5 is a novel compound.
Example 68
Figure BDA0002642320860000282
67.9mg (0.2mmol, 1 equivalent) of the compound E-9 and 22.7mg (0.6 mmol,3 equivalents) of sodium borohydride were added to a 25mL reaction tube, and 2mL of absolute ethanol was injected and stirred at room temperature for 0.5 hour to obtain a reaction solutionCompound I-9, at a yield of 94%. 1 H NMR(400MHz,CDCl 3 )δ7.42–7.40(m,2H),7.36–7.34(m,3H),4.85(t,J＝12.2,1H),4.11–4.09(m,2H),3.07(br,1H),2.61–2.55(m,2H),2.09–2.00(m,1H),1.84(d,J＝13.2,1H),1.70(d,J＝13.2,1H),1.51–1.43(m,2H),1.41(s,9H). 19 F NMR(376MHz,CDCl 3 ) Delta-117.13 (s, 2F). Compound I-9 is a novel compound.
Example 69
Figure BDA0002642320860000283
To a 25mL reaction tube, 57.7mg (0.2mmol, 1 equivalent) of Compound E-12 and 22.7mg (0.6 mmol,3 equivalents) of sodium borohydride were added, and 2mL of absolute ethanol was injected and stirred at room temperature for 0.5 hour to obtain Compound I-12 with a yield of 97%. Forthe texture: 1 H NMR(400MHz,CDCl 3 )δ7.44–7.35(m,10H),7.31–7.26(m,4H),7.22–7.14(m,6H),4.97–4.91(m,2H),2.80–2.73(m,2H),2.56–2.49(m,2H),2.33(br,2H),2.11–1.96(m,4H),1.67–1.54(m,2H),1.17(d,J＝7.2Hz,3H),1.10(d,J＝6.8Hz,3H).For the mixture: 19 F NMR(376MHz,CDCl 3 ) δ -115.64 (dt, J =250.4,14.1hz, 1f), -117.57 (dt, J =250.0,13.7hz, 1f), -116.49 (dt, J =250.4,14.1hz, 1f), -117.08-117.82 (m, 1F). Compound I-12 is a novel compound.
Example 1 to example 69 the synthesized compound E-1, compound E-2, compound E-3, compound E-4, compound E-5, compound E-6, compound E-7, compound E-8, compound E-9, compound E-10, compound E-11, compound E-12, compound E-13, compound E-14, compound E-15, compound E-16, and compound E-17, compound E-18, compound E-19, compound E-20, compound E-21, compound E-23, compound E-24, compound E-25, compound E-26, compound E-29, compound E-33, compound E-34, compound F-5, compound F-12, compound G-9, compound G-12, compound H-5, compound H-9, compound I-5, compound I-9, compound I-12 are novel compounds, and have potential applications in pesticides, materials, and molecular imaging.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. For reasons of space, they will not be described in detail.

Claims (6)

1. A method for difluoroalkylation of an aliphatic amine after deamination, comprising the steps of: taking fatty amine in a formula A as a raw material, and reacting the fatty amine with a pyropyran tetrafluoroborate in a formula B under the condition of heating or room temperature to obtain alkyl pyridinium in a formula C; then under the condition of illumination, in a solvent and by using a photocatalyst, difluoroenolsilyl ether with a formula D is used as a difluoroalkylation reagent, and a plurality of difluoroalkyl substituted alkanes and cycloalkanes with a formula E and derivatives thereof are obtained, wherein the reaction formula is as follows:
Figure 86834DEST_PATH_IMAGE001
，
in the above formulae, R 1 Is H, C 1-15 Alkyl, ester, halogen substituted C 1-15 Alkyl or tert-butoxycarbonyl protected amino substituted C 1-15 An alkyl group;
R 2 is phenyl, pyridyl, C 1-15 Alkyl, methylthio substituted C 1-15 Alkyl, tert-butoxycarbonyl protected amino substituted C 1-15 Alkyl, halogen substituted C 1-15 Alkyl, phenyl substituted C 1-15 Alkyl, ester substituted C 1-15 Alkyl radical, C 1-15 Alkyl, halogen, ester, cyano, tert-butoxy or trifluoromethyl-substituted aryl;
wherein the photocatalyst is selected from: (4, 4' -di-tert-butyl-2, 2' -bipyridine) bis [ (2-pyridyl) phenyl ] iridium (III) hexafluorophosphate, ruthenium terpyridine chloride hexahydrate, tris (2-phenylpyridine) iridium, or (2, 2' -bipyridine) bis (2-phenylpyridine) iridium (III) hexafluorophosphate;
the solvent is selected from: one or more of N-methylpyrrolidone, dichloromethane, N-dimethylformamide, N-dimethylacetamide or ethylene glycol dimethyl ether.
2. The method of claim 1, wherein: the molar ratio of the formula A to the formula B is 1-3: 1 to 3; the molar ratio of the formula C to the photocatalyst to the formula D is 1-3: 0.01 to 0.1:1 to 3.
3. The method of claim 1, wherein: the molar weight of the photocatalyst is 0.1-10% of the molar weight of the formula A.
4. The method of claim 1, wherein: the reaction is carried out at 20-90 ℃.
5. The method of claim 4, wherein: the photocatalyst is selected from (4, 4 '-di-tert-butyl-2, 2' -bipyridine) bis [ (2-pyridyl) phenyl ] iridium (III) hexafluorophosphate.
6. The method of claim 5, wherein: the solvent is a mixture of N, N-dimethylacetamide and ethylene glycol dimethyl ether according to a molar ratio of 1.
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