JPH0789892A - Production of fluorocarbonyl compound - Google Patents

Abstract

PURPOSE:To easily obtain the subject compound important as a raw material for medicines, agrochemicals, functional materials etc. CONSTITUTION:The objective fluorocarbonyl compound of formula Y-CF2-CR2- CR2-C(=O)-R' Of R'-C(=O)-CR2-CR2-(CF2)n-CR2-CR2-C(=O)-R' (R' is alkenyl, alkynyl, aralkyl or aromatic group; R'' is alkyl; Y is H, halogen or polyfluoroalkyl; X is halogen; R is H, alkyl, alkenyl, alkynyl or aromatic group; n is an integer of 1-20) can be obtained by reaction between (A) an organotin compound of formula R'SnR''3 and (B) a halide of formula Y-CF2-CR2-CR2-X or X-CR2-CR2-(CF2)n-CR2-CR2-X in the presence of carbon monoxide using a transition metal catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a functional material such as a liquid crystal material, a medicinal and agrochemical product such as an insecticide and an acaricide, and a method for producing a fluorine-containing carbonyl compound useful as a synthetic intermediate thereof. .

[0002]

2. Description of the Related Art Conventionally, as a method for synthesizing a fluorine-containing carbonyl compound which can be synthesized according to the present invention, (1) a fluorine-containing alkyl Grignard reagent prepared from a fluorine-containing halide and metallic magnesium is added to an acid halide or ester. How to make it work [eg P. Moreau e
t. al., J. Fluorine Chem., 1987, 34, 421.],
(2) A method of oxidizing a fluorine-containing alcohol obtained by reacting a ketone with a fluorine-containing alkyl Grignard reagent prepared from a fluorine-containing halide and metallic magnesium with an appropriate oxidizing agent [eg, A. Matsubara
et. al., Eur. Pat. Appl. EP 414,391.], (3) A method of reducing the radical addition reaction product of a fluorine-containing iodide with an α, β-unsaturated ketone by zinc [eg, W. Bloech.
l, Ger. Offen. 2,140,261.], (4) A method of carrying out a Friedel-Crafts reaction of a fluorine-containing alkyl acid halide with an aromatic compound using a Lewis acid [eg Nodaira,
JP-A-3-220140.], (5) A method of reacting a fluorine-containing alkylaryl iodonium compound with allyl alcohol [eg, Umemoto et al., JP-A-57-118530.], (6) using a fluoride ion, A method of reacting a fluoroalkylaryl iodonium compound with an enol ether of a ketone [eg, T. Umemoto et al., Bull. Chem. So
c. Jpn., 1991, 64, 1542.], (7) A method of reacting an α, β-unsaturated ketone with perfluoroalkyl iodide and triethylborane [eg, K. Oshima and T. Utim.
oto, Bull. Chem. Soc. Jpn., 1991, 64, 403.],
(8) A method of radically reducing an α-chlorotrifluoroethylidene derivative obtained by reacting an enol ether of a ketone with CF ₃ CCl ₃ -CuCl [eg, AJ
Laurent et al., Tetrahedron Lett., 1992, 33 (52), 8
091.] is known. However, the methods (1) and (2) have drawbacks in that a Grignard reagent that is unstable and inconvenient to handle must be used, and that the yield of the fluorinated alkyl Grignard reagent is poor. Further, the method (2) has a drawback that it requires two steps. The method (3) has the drawback of using a dangerous radical initiator and requiring two steps. The method (4) has a drawback that a Lewis acid, which requires careful handling, is used and that the compounds that can be synthesized are limited. The methods (5) and (6) have a drawback that the yield is low and the fluorine-containing alkylaryl iodonium compound must be synthesized using dangerous trifluoroacetic acid and concentrated sulfuric acid which require careful handling. The method (7) has the disadvantage that dangerous triethylborane must be used. The method (8) requires two steps and has a drawback that a dangerous radical reducing agent must be used.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a simple method for producing a fluorine-containing carbonyl compound which can overcome the above-mentioned many drawbacks of the prior art.

[0004]

The present invention provides a compound represented by the general formula R'SnR " ₃ (I) in the presence of a transition metal catalyst, wherein R'is an alkenyl group, an alkynyl group, an aralkyl group, or an aromatic group. And R ″ represents an alkyl group which may be different from each other, and an organic tin compound represented by the general formula Y—CF ₂ —CR ₂ —CR ₂ —X (II) Represents a hydrogen atom, a halogen atom, or a polyfluoroalkyl group, X represents a halogen atom, and each R
May be different from each other and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aromatic group. Further, two Rs may be integrated to form a ring together with the carbon atom to which they are bonded. A halide represented by), consists in the presence of carbon monoxide reaction formula _{Y-CF 2 -CR 2 -CR 2} -C (= O) -R '(III) ( in the formula, Y , R, and R ′ are the same as those described above), and in the presence of a transition metal catalyst, a compound represented by the general formula R′SnR ″ ₃ (I) (wherein R ′ is , An alkenyl group, an alkynyl group, an aralkyl group, or an aromatic group, and R ″ represents an alkyl group which may be different from each other.), And the general formula X-CR ₂ —CR ₂ - (CF ₂₎ in _{n -CR 2 -CR 2 -X (IV} ) ( wherein, X represents a halogen atom, each R may be different from each other, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group , Or an aromatic group, and when two R's are united, May form a ring together with the combined carbon atoms, n is an integer of 1 to 20) in the presence of carbon monoxide in the general formula R ′. _{-C (= O) -CR 2 -CR} 2 - (CF 2) n -CR 2 -CR 2 -C (= O) -R '(V) ( wherein, R, R', and n are as above The same shall apply) to a method for producing a fluorinated carbonyl compound.

The alkyl group in the present invention means a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent which does not participate in the reaction. The alkenyl group in the present invention means a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent which does not participate in the reaction, and the position of the unsaturated bond is not particularly limited. .
The alkynyl group in the present invention means a linear or branched alkynyl group having 2 to 20 carbon atoms which may have a substituent that does not participate in the reaction, and the position of the unsaturated bond is not particularly limited. . The aralkyl group in the present invention means an aralkyl group which may have a substituent which does not participate in the reaction. The aromatic group in the present invention means an aromatic group which may have a substituent not involved in the reaction, a phenyl group, a naphthyl group, a pyrrolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, Imidazolyl group, pyrazolyl group, isothiazolyl group, isoxazolyl group, indolizinyl group, purinyl group, furyl group,
A thienyl group etc. can be illustrated. The substituent not involved in the reaction in the above, a fluorine atom, a chlorine atom, a hydroxyl group, a protected hydroxyl group, an amino group, a protected amino group, an alkoxy group, an aryloxy group, an alkyl group, an alkenyl group, an alkynyl group, and An aromatic group etc. can be illustrated.

The above-mentioned general formula (II) used in the present invention
The halides represented by the formulas (IV) and (IV) are commercially available in part and are also commercially available, but they are known from polyfluorinated alkyl halides and olefins [eg, T. Fuchikami and I. Ojima]. , Tetrahedron Lett.,
1984, 25, 303.].

The halogen atom represented by X is preferably a bromine atom or an iodine atom.

The organotin compound represented by the general formula (I) used in the present invention is industrially available, and
Known methods [eg, D. Seyferth et al., J. Organome
tal. Chem., 1964, 1, 437.].

The organotin compound represented by the general formula (I) is in the range of 0.7 to 5.0 equivalents with respect to the halide represented by the general formula (II), and 1.5 to 1 with respect to the halide represented by (IV)
Within the range of 0.0 equivalent, they can be preferably used.

The method of the present invention is carried out in the presence of a transition metal catalyst, and usable catalysts include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum metals, metal salts, A metal complex compound, an organometallic complex having carbon monoxide as a ligand, an organometallic complex having a halogen atom as a ligand, an organometallic complex having a tertiary phosphine as a ligand, olefins or acetylenes, etc. It is possible to use an organometallic complex serving as a ligand, and those obtained by carrying these former Group VIII transition metal compounds on a carrier such as silica gel or alumina. Suitable catalysts include iron carbonyl, cobalt carbonyl, nickel carbonyl, ruthenium carbonyl,
Rhodium carbonyl, osmium carbonyl, iridium carbonyl, iron chloride, cobalt chloride, cobalt iodide, nickel chloride, nickel bromide, nickel iodide, ruthenium chloride, ruthenium iodide, rhodium chloride, rhodium iodide, palladium chloride, palladium bromide , Palladium iodide, osmium chloride, iridium chloride, platinum chloride, platinum bromide, platinum iodide, cobalt acetylacetonate, cobalt oxalate, nickel acetylacetonate, ruthenium acetylacetonate, bis (rhodium acetate), rhodium acetylacetate Nato, palladium acetate, palladium acetylacetonate, platinum acetylacetonate, cyclohexadiene iron tricarbonyl, dichlorobis (triphenylphosphine) nickel, bis
(Cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, dichloro [1,2-bis (diphenylphosphino) ethane] nickel, dichloro [1,3-bis
(Diphenylphosphino) propane] nickel, bis (triphenylphosphine) nickel dicarbonyl, dichlorotris (triphenylphosphine) ruthenium, dichloro
(1,5-Cyclooctadiene) ruthenium, dichlorodicarbonylbis (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, chlorocarbonylbis (triphenylphosphine) rhodium, acetylacetonatobis (ethylene) rhodium, bis [Chloro (1,5-cyclooctadiene) rhodium], bis (chlorodicarbonylrhodium), dichlorobis (triphenylphosphine) palladium, dichloro [1,2-bis (diphenylphosphino) ethane] palladium, dichloro [1, 3-bis (diphenylphosphino) propane] palladium, dichloro [1,4
-Bis (diphenylphosphino) butane] palladium, dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium, dichlorobis (diphenylmethylphosphine)
Palladium, dichlorobis (trimethylphosphine) palladium, dichlorobis (triethylphosphine) palladium, dichloro (cyclooctadiene) palladium, tetrakis (triphenylphosphine) palladium, dichloro
[2,2'-bis (diphenylphosphino) -1,1'-binaphthyl]
Palladium, dichlorobis (triphenylarsine) palladium, trans-benzyl (chloro) bis (triphenylphosphine) palladium, diacetate bis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) iridium, chlorocarbonylbis (triphenylphosphine) Iridium, chlorotricarbonyliridium, dicarbonylacetylacetonatoiridium, dichlorobis (triethylphosphine) platinum, dichlorobis (triphenylphosphine) platinum, dichloro (1,5-
Examples thereof include cyclooctadiene) platinum and tetrakis (triphenylphosphine) platinum.

The transition metal catalyst is used in the range of 0.005 to 0.5 equivalents relative to the halide represented by the general formula (II), and the halide represented by the general formula (IV). On the other hand, it can be suitably used in the range of 0.01 to 1.0 equivalent. Further, in the present invention, the reaction may be carried out by further adding a suitable coordinating compound. Coordinating compounds that can be used include triphenylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis
(Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, diphenylmethylphosphine, trimethylphosphine, triethylphosphine, trioctylphosphine, 2,2 ′ -Bis (diphenylphosphino) -1,1'-
Tertiary phosphines such as binaphthyl, 1-diphenylphosphino-2-diphenylarsinoethane, tertiary phosphites such as triphenylphosphite, trioctylphosphite, triphenylarsine, trimethylarsine,
Examples thereof include tertiary arsines such as triethylarsine, cyclopentadiene such as cyclopentadiene and pentamethylcyclopentadiene, olefins such as butadiene, norbornadiene, cyclohexadiene, cyclooctadiene and cyclooctatetraene. When the coordinating compound is added, the amount of the coordinating compound used is preferably in the range of up to 20.0 equivalents with respect to the above transition metal catalyst.

In carrying out the present invention, the product may undergo isomerization of unsaturated bonds under the present reaction conditions.

The method of the present invention is carried out in the presence of carbon monoxide, but the reaction can also be carried out in a mixed gas of carbon monoxide and a gas such as argon, nitrogen or helium which does not participate in the reaction. The reaction proceeds at a carbon monoxide pressure of 1 atm to 150 atm, but it is preferably carried out at 10 atm to 80 atm in terms of reaction efficiency, economy, safety and the like.

Although the reaction can be carried out without solvent,
A solvent that does not participate in the reaction can be preferably used. Examples of the solvent that can be used include aromatic hydrocarbon solvents such as benzene, toluene and xylene, hydrocarbon solvents such as hexane, heptane, octane and decalin, halogen solvents such as chloroform, ketone solvents such as acetone and methyl ethyl ketone. Solvents, protic polar solvents such as tert-butanol, aprotic polar solvents such as acetonitrile, propionitrile, butyronitrile, benzonitrile, nitromethane and the like can be mentioned.

The reaction proceeds at room temperature to 200 ° C, but it is preferable to carry out at about 50 ° C to 160 ° C in view of reaction efficiency, economy, safety and the like.

[0016]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1

[Chemical 1]

A stainless steel pressure-resistant reaction vessel containing a magnetic stirrer was charged with 2- (perfluoro-n-octyl) ethyl iodide.
(287 mg, 0.50 mmol), dichlorobis (triphenylphosphine) palladium (35 mg, 0.05 mmol), (phenylethynyl) tributyltin (195 μl, 0.55 mmol), and dry benzene (1.5 ml) were added. The mixture was stirred under carbon monoxide pressure (50 atm) at 120 ° C. for 16 hours. n-tridecane
(20 μl, 82.4 μmol) was added as an internal standard and quantified by gas chromatography.
n-octyl) -1-phenyl-3-oxo-1-pentyne yield 48
It turns out that it is generated by%. An excess amount of potassium fluoride was added to the reaction mixed solution, and the mixture was stirred at room temperature for 24 hours. The precipitate was filtered off and the solvent was evaporated under reduced pressure, followed by thin layer chromatography (silica gel; n-hexane / methylene chloride = 3 /
1) by 5- (perfluoro-n-octyl) -1-phenyl-3-
Oxo-1-pentyne was isolated. ¹ H-NMR (CDCl ₃ , TMS, ppm) δ 2.40-2.70 (2H, m), 3.00
-3.10 (2H, m), 7.30-7.55 (3H, m), 7.55-7.65 (2H, m). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ , ppm) δ -126.6 (2F, bs), -12
4.0 (2F, bs), -123.2 (2F, bs), -122.3 (6F, bs), -114.
7 (2F, bs), -81.2 (3F, t, J = 10Hz) .MS (m / z) 576 (M ⁺ , 1.40), 575 (M ⁺ -1, 5.17), 557 (M ⁺ -1)
9, 1.86), 556 (M ⁺ -20, 9.44), 129 (M ⁺ -C ₈ F ₁₇ -CH ₂ -CH ₂ ,
100.00).

Example 2

[Chemical 2]

In a pressure resistant reaction vessel made of stainless steel containing a magnetic stirrer, 2- (perfluoro-n-octyl) ethyl iodide was added.
(287 mg, 0.50 mmol), tetrakis (triphenylphosphine) palladium (58 mg, 0.05 mmol), (phenylethynyl) tributyltin (522 μl, 1.50 mmol), and dry benzene (1.5 ml) were added. The above mixture is pressurized with carbon monoxide.
The mixture was stirred at (50 atm) and 120 ° C. for 16 hours. n-tridecane (20
(μl, 82.4 μmol) was added as an internal standard, and the result of quantification by gas chromatography showed that 5- (perfluoro-n-octyl) -1-phenyl-3-oxo-1-pentyne was produced in a yield of 31%. It has been found.

Example 3

[Chemical 3]

A stainless steel pressure-resistant reaction vessel containing a magnetic stirrer was charged with 2- (perfluoro-n-octyl) ethyl iodide.
(287 mg, 0.50 mmol), dichlorobis (triphenylphosphine) palladium (35 mg, 0.05 mmol), allyltributyltin (170 μl, 0.55 mmol), and dry benzene (1.5 mg).
ml) was added. The above mixture is pressurized with carbon monoxide (50 atm)
The mixture was stirred at 120 ° C for 16 hours. n-Tridecane (20 μl, 82.4
(mol) was added as an internal standard, and the result of quantification by gas chromatography was 14% of 2- (perfluoro-n-octyl) ethyl iodide, and (E) -6- (perfluoro-n-octyl) -4. -Oxo-2-hexene and 6-
(Perfluoro-n-octyl) -4-oxo-1-hexene
Yields 39% (conversion yield: 46%) and 16% (conversion yield:
19%). An excess amount of potassium fluoride was added to the reaction mixed solution, and the mixture was stirred at room temperature for 24 hours.
The precipitate was filtered off and the solvent was distilled off under reduced pressure, followed by thin layer chromatography (silica gel; n-hexane / methylene chloride =
3/1) to (E) -6- (perfluoro-n-octyl) -4-oxo
A mixture of -2-hexene and 6- (perfluoro-n-octyl) -4-oxo-1-hexene was obtained. (E) -6- (Perfluoro-n-octyl) -4-oxo-2-hexene ¹ H-NMR (CDCl ₃ , TMS, ppm) δ 1.94 (3H, dd, J = 1.7 and
6.9Hz), 2.30-2.60 (2H, m), 2.80-2.93 (2H, m), 6.17 (1
H, qd, J _q = 1.7Hz, J _d = 15.8Hz), 6.94 (1H, qd, J _q = 6.9H
z, J _d = 15.8Hz). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ , ppm) δ -126.6 (2F, bs), -12
3.4 (2F, bs), -123.2 (2F, bs), -122.4 (6F, bs), -114.
7 (2F, bs), -81.3 (3F, t, J = 9.5Hz) .MS (m / z) 516 (M ⁺ , trace), 497 (M ⁺ -19, 1.28), 69 (M ⁺ -C
₈ F ₁₇ -CH ₂ -CH ₂ , 100.00). 6- (perfluoro-n-octyl) -4-oxo- ¹ -hexene ¹ H-NMR (CDCl ₃ , TMS, ppm) δ 2.25-2.60 (2H, m ), 2.70
-2.85 (2H, m), 3.24 (2H, J = 7.0Hz), 5.18 (1H, dd, J = 13.
1 and 1.4Hz), 5.25 (1H, dd, J = 6.1 and 1.4Hz), 5.93
(1H, ddt, J _d = 13.1 and 6.1Hz, J _t = 7.0 Hz). Similarly, under pressure of carbon monoxide (50 atm), 2- (perfluoro-n-octyl) ethyl iodide (287 mg, 0.50). mmol)
Allyltributyltin (170 μl, 0.55 mmol) was allowed to act at 120 ° C. for 64 hours on a benzene solution containing and and dichlorobis (triphenylphosphine) palladium (35 mg, 0.05 mmol). As a result of quantification by gas chromatography (internal standard: n-tridecane), (E) -6- (perfluoro-n
-Octyl) -4-oxo-2-hexene was found to be produced at a yield of 61%, and the formation of 6- (perfluoro-n-octyl) -4-oxo-1-hexene was not detected. It was An excess amount of potassium fluoride was added to the reaction mixed solution, and the mixture was stirred at room temperature for 24 hours. The precipitate was filtered off, the solvent was evaporated under reduced pressure, and then (E) -6- (perfluoro) was analyzed by thin layer chromatography (silica gel; n-hexane / methylene chloride = 3/1).
-n-octyl) -4-oxo-2-hexene was isolated.

Example 4

[Chemical 4]

A stainless steel pressure-resistant reaction vessel containing a magnetic stirrer was charged with 2- (perfluoro-n-octyl) ethyl iodide.
(287 mg, 0.50 mmol), tetrakis (triphenylphosphine) palladium (58 mg, 0.05 mmol), allyltributyltin (170 μl, 0.55 mmol), and dry benzene (1.5 m
l) was added. The above mixture is pressurized under carbon monoxide (50 atm).
The mixture was stirred at 120 ° C for 16 hours. n-Tridecane (20 μl, 82.4
μmol) was added as an internal standard, and the result of quantification by gas chromatography was (E) -6- (perfluoro-n-octyl) -4-oxo-2-hexene and 6- (perfluoro-n-octyl) -4-. It was found that oxo-1-hexene was produced in yields of 50% and 7%, respectively.

Example 5

[Chemical 5]

In a pressure resistant reaction vessel made of stainless steel containing a magnetic stirrer, 2- (perfluoro-n-octyl) ethyl iodide was added.
(287 mg, 0.50 mmol), dichlorobis (triphenylphosphine) palladium (35 mg, 0.05 mmol), a mixture of (phenylethenyl) tributyltin ((E) -form and (Z) -form,
(E)-/ (Z)-= 2.3 / 1.0, purity> 95% (GC), 600 μl, 1.50
mmol) and dry benzene (1.5 ml) were added. The mixture was stirred under carbon monoxide pressure (50 atm) at 120 ° C. for 16 hours. n-Tridecane (20 μl, 82.4 μmol) was added as an internal standard, and the result of quantification by gas chromatography was
It was found that (E) -5- (perfluoro-n-octyl) -1-phenyl-3-oxo-1-pentene was produced in a yield of 79%. An excess amount of potassium fluoride was added to the reaction mixed solution, and the mixture was stirred at room temperature for 24 hours. The precipitate was filtered off and the solvent was distilled off under reduced pressure, followed by thin layer chromatography (silica gel; n-hexane / methylene chloride = 3/1) to (E) -5- (perfluoro
-n-octyl) -1-phenyl-3-oxo-1-pentene was isolated. ¹ H-NMR (CDCl ₃ , TMS, ppm) δ 2.40-2.70 (2H, m), 2.93
-3.08 (2H, m), 6.78 (1H, d, J = 16.2Hz), 7.30-7.45 (3H,
m), 7.50-7.65 (2H, m), 7.62 (1H, d, J = 16.2Hz). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ , ppm) δ -126.6 (2F, bs), -12
3.9 (2F, bs), -123.2 (2F, bs), -122.3 (6F, bs), -114.
6 (2F, bs), -81.2 (3F, t, J = 10Hz). MS (m / z) 579 (M ⁺ +1, 2.01), 578 (M ⁺ , 9.40), 577 (M ⁺ -1,
4.00), 559 (M ⁺ -19, 3.07), 209 (M ⁺ -C ₇ F ₁₅ , 1.17), 131
(M ⁺ -C ₈ F ₁₇ -CH ₂ -CH ₂ , 100.00).

Example 6

[Chemical 6]

In a pressure resistant reaction vessel made of stainless steel containing a magnetic stirrer, 2- (perfluoro-n-octyl) ethyl iodide was added.
(287 mg, 0.50 mmol), tetrakis (triphenylphosphine) palladium (58 mg, 0.05 mmol), (phenylethenyl) tributyltin ((E) -form and (Z) -form mixture, (E)-
/ (Z)-= 2.3 / 1.0, purity> 95% (GC), 600 μl, 1.50 mmo
l) and dry benzene (1.5 ml) were added. The mixture was stirred under carbon monoxide pressure (50 atm) at 120 ° C. for 16 hours.
n-Tridecane (20 μl, 82.4 μmol) was added as an internal standard, and the result of quantification by gas chromatography was (E)-
5- (perfluoro-n-octyl) -1-phenyl-3-oxo-1-
It was found that pentene was produced in a yield of 65%.

Example 7

[Chemical 7]

In a pressure resistant reaction vessel made of stainless steel containing a magnetic stirrer, 2- (perfluoro-n-octyl) ethyl iodide was added.
(287 mg, 0.50 mmol), dichlorobis (triphenylphosphine) palladium (35 mg, 0.05 mmol), tributylphenyltin (180 μl, 0.55 mmol), and dry benzene.
(1.5 ml) was added. The above mixture was pressurized with carbon monoxide (50
The mixture was stirred at 120 ° C. for 16 hours. n-tridecane (20 μl,
(82.4 μmol) was added as an internal standard, and the result of quantification by gas chromatography revealed that 3- (perfluoro-n-octyl) -1-oxo-1-phenylpropane was produced in a yield of 89%. An excess amount of potassium fluoride was added to the reaction mixed solution, and the mixture was stirred at room temperature for 24 hours. The precipitate was filtered off, the solvent was distilled off under reduced pressure, and then thin layer chromatography was performed.
3- (silica gel; n-hexane / methylene chloride = 3/1)
(Perfluoro-n-octyl) -1-oxo-1-phenylpropane was isolated. ¹ H-NMR (CDCl ₃ , TMS, ppm) δ 2.45-2.77 (2H, m), 3.25
-3.40 (2H, m), 7.40-7.70 (3H, m), 7.85-8.05 (2H, m). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ , ppm) δ -126.6 (2F, bs), -12
3.9 (2F, bs), -123.2 (2F, bs), -122.3 (6F, bs), -114.
6 (2F, bs), -81.2 (3F, t, J = 10Hz). MS (m / z) 552 (M ⁺ , trace), 533 (M ⁺ -19, 1.57), 532 (M ⁺ -
20, 8.47), 105 (M ⁺ -C ₈ F _{1 7} -CH ₂ -CH ₂ , 100.00).

Example 8

[Chemical 8]

In a pressure resistant reaction vessel made of stainless steel containing a magnetic stirrer, 2- (perfluoro-n-octyl) ethyl iodide was added.
(287 mg, 0.50 mmol), tetrakis (triphenylphosphine) palladium (58 mg, 0.05 mmol), tributylphenyltin (180 μl, 0.55 mmol), and dry benzene (1.5 mg).
ml) was added. The above mixture is pressurized with carbon monoxide (50 atm)
The mixture was stirred at 120 ° C for 16 hours. n-Tridecane (20 μl, 82.4
μmol) was added as an internal standard, and the result of quantification by gas chromatography was 3- (perfluoro-n-octyl)-
It was found that 1-oxo-1-phenylpropane was produced in a yield of 93%.

Example 9

[Chemical 9]

A stainless steel pressure-resistant reaction vessel containing a magnetic stirrer was charged with 2- (perfluoro-n-octyl) ethyl bromide.
(264 mg, 0.50 mmol), dichlorobis (triphenylphosphine) palladium (35 mg, 0.05 mmol), tributylphenyltin (180 μl, 0.55 mmol), and dry benzene.
(1.5 ml) was added. The above mixture was pressurized with carbon monoxide (50
The mixture was stirred at 160 ° C. for 16 hours. n-tridecane (20 μl,
(82.4 μmol) was added as an internal standard, and the result of quantification by gas chromatography was 41% 2- (perfluoro-n-
It was found that octyl) ethyl bromide was recovered, and 3- (perfluoro-n-octyl) -1-oxo-1-phenylpropane was produced in a yield of 23% (conversion yield: 39%). .

Example 10

[Chemical 10]

A stainless steel pressure-resistant reaction vessel containing a magnetic stirrer was charged with 2- (perfluoro-n-octyl) ethyl bromide.
(264 mg, 0.50 mmol), tetrakis (triphenylphosphine) palladium (58 mg, 0.05 mmol), tributylphenyltin (480 μl, 1.50 mmol), and dry benzene (1.5 mg).
ml) was added. The above mixture is pressurized with carbon monoxide (50 atm)
The mixture was stirred at 120 ° C for 64 hours. n-Tridecane (20 μl, 82.4
μmol) was added as an internal standard, and the result of quantification by gas chromatography was that 64% of 2- (perfluoro-n-octyl) ethyl bromide was recovered and 3- (perfluoro-n-octyl) -1-oxo- 1-phenylpropane yield
It was found that 29% (conversion yield: 82%) was produced.

Example 11

[Chemical 11]

In a pressure resistant reaction vessel made of stainless steel containing a magnetic stirrer, 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,1
0-diiododecane (305 mg, 0.50 mmol), dichlorobis
(Triphenylphosphine) palladium (70 mg, 0.10 mmo
l), tributylphenyltin (360 μl, 1.10 mmol), and dry benzene (1.5 ml) were added. The mixture was stirred under carbon monoxide pressure (50 atm) at 120 ° C. for 16 hours. An excess amount of potassium fluoride was added to the reaction mixed solution, and the mixture was stirred at room temperature for 24 hours. After the precipitate was filtered off and the solvent was distilled off under reduced pressure,
Thin-layer chromatography (silica gel; n-hexane / methylene chloride = 3/1) 4,4,5,5,6,6,7,7,8,8,9,9-dodecafluoro-1,12- Dioxo-1,12-diphenyldodecane was isolated in 15% yield. ¹ H-NMR (CDCl ₃ , TMS, ppm) δ 2.45-2.77 (4H, m), 3.26
-3.38 (4H, m), 7.45-7.66 (6H, m), 7.95-8.03 (4H, m). ¹⁹ F-NMR (CDCl ₃ , CFCl ₃ , ppm) δ -124.0 (4F, bs), -12
2.3 (4F, bs), -114.6 (4F, bs). MS (m / z) 566 (M ⁺ , trace), 547 (M ⁺ -19, trace), 489 (M ⁺
-77, trace), 461 (M ⁺ -105, trace), 105 (C ₆ H ₅ CO, 100.0
0).

Claims (2)

[Claims] 1. In the presence of a transition metal catalyst, a compound represented by the general formula R′SnR ″ ₃ (wherein R ′ represents an alkenyl group, an alkynyl group, an aralkyl group, or an aromatic group, and R ″ s are different from each other. represents an organic tin compound represented by the representative.) the alkyl group in the general formula _{Y-CF 2 -CR 2 -CR 2} -X ( wherein, Y is a hydrogen atom, a halogen atom, or a polyfluoroalkyl group, X represents a halogen atom, and each R
May be different from each other and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aromatic group. Further, two Rs may be integrated to form a ring together with the carbon atom to which they are bonded. A halide represented by), consists in the presence of carbon monoxide reaction formula _{Y-CF 2 -CR 2 -CR 2} -C (= O) -R '( wherein, Y, R, And R ′ are the same as the above.). 2. In the presence of a transition metal catalyst, a compound represented by the general formula R′SnR ″ ₃ (wherein R ′ represents an alkenyl group, an alkynyl group, an aralkyl group, or an aromatic group, and R ″ s are different from each other. an organic tin compound represented by) represents an alkyl group, the general formula _{X-CR 2 -CR 2 -.} (CF 2) in _n -CR ₂ -CR ₂ -X (wherein, X represents a halogen atom, Each R may be different from each other and represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aromatic group, and two R together form a ring together with the carbon atom to which they are bonded. And n is an integer of 1 to 20) in the presence of carbon monoxide in the general formula R'-C (= O) -CR. _{2 -CR 2 - (CF 2)} n -CR 2 -C
_{R 2 -C (= O) -R} '( wherein, R, R', and n are as defined above.) Process for producing a fluorinated carbonyl compound represented by the.