Composition, fluorinating reagent, and method for producing fluorinated organic compound

Abstract

An object of the present invention is to provide a method for producing a fluorinated organic compound with a high yield without using carbon tetrachloride in view of the fact that the production of a fluorinated organic compound with a sufficient yield was impossible for a hitherto-known method that uses a fluorinating agent that contains IF.sub.5-pyridine-HF alone. Another object of the present invention is to provide a fluorinating reagent that is capable of achieving this object. The present invention provides a composition comprising (1) IF.sub.5 and (2) an aprotic solvent (with the proviso that carbon tetrachloride is excluded), wherein the aprotic solvent is contained in an amount within a range of 50 mass ppm to 20 mass %.

Claims

1. A solid composition comprising: (1) IF.sub.5-pyridine-HF and (2) at least one aprotic solvent selected from the group consisting of (cyclo)alkanes, aromatic solvents, and fluorine-containing organic solvents, wherein the aprotic solvent is contained in the solid composition in an amount within a range of 50 mass ppm to 20 mass %.

2. The solid composition according to claim 1, wherein the aprotic solvent is at least one member selected from the group consisting of C.sub.1-10(cyclo)alkanes, and C.sub.1-7 fluorine-containing organic solvents.

3. The solid composition according to claim 1, wherein the aprotic solvent is a C.sub.1-10(cyclo)alkane.

4. The solid composition according to claim 1, wherein the aprotic solvent is cyclohexane.

5. The solid composition according to claim 1, which is a fluorinating reagent.

6. A method for producing a fluorinated organic compound, the method comprising Step A of fluorinating an organic compound by bringing the organic compound into contact with the solid composition of claim 1.

7. The solid composition according to claim 2, which is a fluorinating reagent.

8. The solid composition according to claim 3, which is a fluorinating reagent.

9. The solid composition according to claim 4, which is a fluorinating reagent.

10. A method for producing a fluorinated organic compound, the method comprising Step A of fluorinating an organic compound by bringing the organic compound into contact with the solid composition of claim 2.

11. A method for producing a fluorinated organic compound, the method comprising Step A of fluorinating an organic compound by bringing the organic compound into contact with the solid composition of claim 3.

12. A method for producing a fluorinated organic compound, the method comprising Step A of fluorinating an organic compound by bringing the organic compound into contact with the solid composition of claim 4.

13. A method for producing a fluorinated organic compound, the method comprising Step A of fluorinating an organic compound by bringing the organic compound into contact with the solid composition of claim 5.

14. A method for producing a fluorinated organic compound, the method comprising Step A of fluorinating an organic compound by bringing the organic compound into contact with the solid composition of claim 7.

15. A method for producing a fluorinated organic compound, the method comprising Step A of fluorinating an organic compound by bringing the organic compound into contact with the solid composition of claim 8.

16. A method for producing a fluorinated organic compound, the method comprising Step A of fluorinating an organic compound by bringing the organic compound into contact with the solid composition of claim 9.

Description

EXAMPLES

(1) The present invention is described below in further detail. However, the present invention is not limited to these Examples.

(2) In the Examples, the unit “ppm” refers to mass ppm, unless otherwise specified.

(3) The following is the meaning of the symbol used in the Examples. pen: Pentyl

(4) In each Example, the amount of cyclohexane residue was measured according to the following measurement method.

(5) Measurement Method

(6) i) Accurately weigh about 50 to 150 mg of a sample composition; ii) Add 4 ml of 0.1N KOH aqueous solution; iii) Add 2 ml of toluene; iv) Stir the mixture for 5 minutes, and allow the resulting mixture to stand for 10 minutes; v) Subject the cyclohexane residue in the toluene layer to GC measurement; and vi) Calculate the amount of cyclohexane residue, based on the calibration curve value. The average value obtained with n=3 is considered the amount of cyclohexane residue. The “amount of cyclohexane residue” as used herein means the amount of cyclohexane contained in the sample composition, i.e., (mass of cyclohexane)/(mass of the sample composition).

Production Example 1

(7) IF.sub.5 (45 g, 0.20 mol) was placed in a container, to which 200 ml of cyclohexane was added at 0° C., followed by further addition of pyridine-HF (pyridine 50 mol %, HF 50 mol %) (20 g, 0.20 mol each). The resulting mixture was stirred for 30 minutes at 0° C., and then left to stand at room temperature for 1 hour to thus obtain a solid containing IF.sub.5-pyridine-HF and cyclohexane.

(8) The obtained solid was dried under reduced pressure while varying the conditions for drying under pressure. In this manner, solid compositions containing IF.sub.5-pyridine-HF and cyclohexane were obtained with various cyclohexane amounts. Hereinafter, these solid compositions are referred to as IF.sub.5-pyridine-HF, and its cyclohexane content is referred to as the amount of cyclohexane residue.

Example 1

Fluorination Reaction Test

(9) ##STR00009##

(10) IF.sub.5-pyridine-HF (1.1 mmol) (the amount of cyclohexane residue: 202 mass ppm) and dichloromethane (2.0 mL) were placed in a reactor with a lid, to which substrate 1 (1.0 mmol) was added, and the mixture was allowed to react at 0° C. for 3 hours.

(11) After purification, an internal standard (hexafluorobenzene) was added to the residue, and the product was quantified by .sup.19F-NMR. The results indicate that difluoro body 2 was produced with a yield of 60%.

Comparative Example 1

Fluorination Reaction Test

(12) IF.sub.5-pyridine-HF (1.1 mmol) (the amount of cyclohexane residue: 43 mass ppm) and dichloromethane (2.0 mL) were placed in a reactor with a lid, to which substrate 1 (1.0 mmol) was added at room temperature, and the mixture was allowed to react at 0° C. for 3 hours. After purification, an internal standard (hexafluorobenzene) was added to the residue, and the product was quantified by .sup.19F-NMR. As a result, difluoro body 2 was not detected, and the yield was 0%, indicating that difluoro body 2 was not produced.

Test Example 1

Fluorination Reaction Test

(13) Table 1 shows the results of the fluorination reaction test performed with respect to the samples of each product produced as in Example 1 and Comparative Example 1, using IF.sub.5-pyridine-HF with various amounts of cyclohexane residue (Examples 1 to 4 and Comparative Examples 1 and 2). As is clear from the results, the use of the composition of the present invention allows the fluorination reaction to proceed to thus yield the target product.

(14) TABLE-US-00001 TABLE 1 No. 1 2 3 4 5 6 (Ex. 2) (Ex. 1) (Ex. 3) (Ex. 4) (Comp. Ex. 1) (Comp. Ex. 2) Amount of 19 mass % 202 ppm 99 ppm 87 ppm 43 ppm 33 ppm cyclohexane residue Fluorination + + + + n.d. n.d. reaction +: The fluorinated reaction product (difluoro body 2) was detected. n.d.: The fluorinated reaction product (difluoro body 2) was not detected.