Fluorine-containing diaryliodonium salt and application thereof

Abstract

The invention relates to fluorine-containing diaryliodonium salt as well as a preparation method and an application thereof. The fluorine-containing diaryliodonium salt has a structure represented as a formula I and is taken as an arylation reagent. The fluorine-containing diaryliodonium salt has the advantages that the preparation is easy, when the fluorine-containing diaryliodonium salt is applied to an arylation reaction, the arylation reaction condition is relatively mild, the selectivity of an arylation product is good and the like; in the formula I shown in the specification, R1 represents an aromatic ring group or a heteroaromatic ring group or represents a substituted aromatic ring group or a substituted heteroaromatic ring group, and Y represents a univalent organic or inorganic acid radical anion.

Description

technical field

[0001] The invention relates to a fluorine-containing diaryliodonium salt and its preparation method and application, in particular to a pentafluorophenyl-containing diaryliodonium salt and its preparation method and application. Background technique

[0002] Diaryliodonium salts are recognized as good arylation reagents and are widely used in organic (especially pharmaceutical) synthesis (Eleanor A. Merritt, Berit Olofsson. Diaryliodonium Salts: A Journey from Obscurity to Fame, Angew. Chem. Int. Ed. 2009, 48, 9052–9070.).

[0003] However, the disadvantages of existing diaryliodonium salts (especially fluorine-containing diaryliodonium salts) are: ① difficult to prepare, ② when used in arylation reaction, the conditions of arylation reaction are relatively harsh and aryl The selectivity of the product is poor.

[0004] In view of this, it is a technical problem to be solved in the present invention to provide a diaryliodonium salt that is easy to prepare,...

Examples

Embodiment 1

[0030] (1) Synthesis of pentafluoroiodobenzene trifluoroacetic acid (compound shown in formula III):

[0031]

[0032] Pentafluoroiodobenzene (1.47g, 5mmol, 1 equiv.), 5ml~10ml of chloroform and trifluoroacetic acid (15ml, 400equiv.) were placed in the reactor, stirred for 10-30min, the temperature was lowered to 0°C, and added in batches over a period of Potassium bisulfate compound salt (Oxone) (4.61g, 7.5mmol, 1.5equiv.), after adding, warm up to room temperature, stir at room temperature for 1-10h, filter, wash the filter cake with dichloromethane (3×20ml ), the combined filtrates were evaporated to remove the solvent and dried to obtain 2.39 g of light yellow solid (compound shown in formula III), Mp: 95.5-96.5 ° C, yield 92%.

[0033] 19 F NMR (300MHz, DMSO-d 6 ): δ-73.9(s), -123.6(s), -144.8(s), -157.3(s).

[0034] 13 C NMR (125.6MHz, DMSO-d 6 ):δ159.7(q,J CF =37Hz), 148.2(m), 146.3(m), 138.2(m), 136.2(m), 115.6(q, J CF =289Hz).

[0035] (2) Synthesis of pent...

Embodiment 2

[0047] According to the teaching of Example 1, except using different acids (such as: trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, HCl, H 2 SO 4 or tetrafluoroboric acid, etc.) to replace embodiment 1 step (2) p-toluenesulfonic acid monohydrate, or / and different substituted or unsubstituted aromatic ring hydrocarbons or aromatic heterocyclic hydrocarbons (such as: methoxybenzene, bromobenzene, Replace 1,3,5- Except for trimethylbenzene, other steps and conditions are similar to those in Example 1. Compounds shown in Table 1 can be prepared.

[0048] Table 1

[0049]

[0050] Continued Table 1

[0051]

[0052] Example of arylation reaction

Embodiment 3

[0054] The reaction of pentafluorophenyl diaryliodonium salt (compound Ⅰ-1) with benzoic acid:

[0055]

[0056] Compound Ⅰ-1 (0.584g, 1mmol), benzoic acid (0.122g, 1mmol), silver acetate (0.167g, 1mmol) and tetrahydrofuran (5ml) were placed in the reactor and kept at 40°C for 2-4 hours , the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether / ethyl acetate=10 / 1) to obtain 0.216 g of mesityl benzoate with a yield of 90%.

[0057] 1 H NMR (400MHz, CDCl 3 )δ: 8.27–8.25(m,2H), 7.68–7.64(m,1H), 7.56–7.52(m,2H), 6.93(s,2H), 2.31(s,3H), 2.17(s,6H) ;

[0058] 13 C NMR (100MHz, CDCl 3 )δ: 164.7, 146.3, 135.5, 133.7, 130.3, 130.0, 129.6, 129.4, 128.8, 21.0, 16.5.

technical field

[0001] The invention relates to a fluorine-containing diaryliodonium salt and its preparation method and application, in particular to a pentafluorophenyl-containing diaryliodonium salt and its preparation method and application. Background technique

[0002] Diaryliodonium salts are recognized as good arylation reagents and are widely used in organic (especially pharmaceutical) synthesis (Eleanor A. Merritt, Berit Olofsson. Diaryliodonium Salts: A Journey from Obscurity to Fame, Angew. Chem. Int. Ed. 2009, 48, 9052–9070.).

[0003] However, the disadvantages of existing diaryliodonium salts (especially fluorine-containing diaryliodonium salts) are: ① difficult to prepare, ② when used in arylation reaction, the conditions of arylation reaction are relatively harsh and aryl The selectivity of the product is poor.

[0004] In view of this, it is a technical problem to be solved in the present invention to provide a diaryliodonium salt that is easy to prepare,...

Examples

Embodiment 1

[0030] (1) Synthesis of pentafluoroiodobenzene trifluoroacetic acid (compound shown in formula III):

[0031]

[0032] Pentafluoroiodobenzene (1.47g, 5mmol, 1 equiv.), 5ml~10ml of chloroform and trifluoroacetic acid (15ml, 400equiv.) were placed in the reactor, stirred for 10-30min, the temperature was lowered to 0°C, and added in batches over a period of Potassium bisulfate compound salt (Oxone) (4.61g, 7.5mmol, 1.5equiv.), after adding, warm up to room temperature, stir at room temperature for 1-10h, filter, wash the filter cake with dichloromethane (3×20ml ), the combined filtrates were evaporated to remove the solvent and dried to obtain 2.39 g of light yellow solid (compound shown in formula III), Mp: 95.5-96.5 ° C, yield 92%.

[0033] 19 F NMR (300MHz, DMSO-d 6 ): δ-73.9(s), -123.6(s), -144.8(s), -157.3(s).

[0034] 13 C NMR (125.6MHz, DMSO-d 6 ):δ159.7(q,J CF =37Hz), 148.2(m), 146.3(m), 138.2(m), 136.2(m), 115.6(q, J CF =289Hz).

[0035] (2) Synthesis of pent...

Embodiment 2

[0047] According to the teaching of Example 1, except using different acids (such as: trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, HCl, H 2 SO 4 or tetrafluoroboric acid, etc.) to replace embodiment 1 step (2) p-toluenesulfonic acid monohydrate, or / and different substituted or unsubstituted aromatic ring hydrocarbons or aromatic heterocyclic hydrocarbons (such as: methoxybenzene, bromobenzene, Replace 1,3,5- Except for trimethylbenzene, other steps and conditions are similar to those in Example 1. Compounds shown in Table 1 can be prepared.

[0048] Table 1

[0049]

[0050] Continued Table 1

[0051]

[0052] Example of arylation reaction

Embodiment 3

[0054] The reaction of pentafluorophenyl diaryliodonium salt (compound Ⅰ-1) with benzoic acid:

[0055]

[0056] Compound Ⅰ-1 (0.584g, 1mmol), benzoic acid (0.122g, 1mmol), silver acetate (0.167g, 1mmol) and tetrahydrofuran (5ml) were placed in the reactor and kept at 40°C for 2-4 hours , the solvent was distilled off, and the residue was separated by column chromatography (petroleum ether / ethyl acetate=10 / 1) to obtain 0.216 g of mesityl benzoate with a yield of 90%.

[0057] 1 H NMR (400MHz, CDCl 3 )δ: 8.27–8.25(m,2H), 7.68–7.64(m,1H), 7.56–7.52(m,2H), 6.93(s,2H), 2.31(s,3H), 2.17(s,6H) ;

[0058] 13 C NMR (100MHz, CDCl 3 )δ: 164.7, 146.3, 135.5, 133.7, 130.3, 130.0, 129.6, 129.4, 128.8, 21.0, 16.5.

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