JP6211897B2 - Method for producing 3- (perfluoroalkyl) propanal - Google Patents

Description

  The present invention relates to a method for producing 3- (perfluoroalkyl) propanal.

  As a method for producing 3- (perfluoroalkyl) propanal, a method in which (perfluoroalkyl) ethylene is reacted with carbon monoxide and hydrogen in the presence of a metal catalyst, so-called hydroformylation is known. Non-Patent Document 1 discloses 3,3,4,4,4-4-in a 1: 1 gas mixture of carbon monoxide and hydrogen at 110 to 130 atm in the presence of a catalyst composed of a cobalt, platinum, ruthenium or rhodium compound. Pentafluoro-1-butene, 3,3,4,4,5,5,5-heptafluoro-1-pentene, 3,3,4,4,5,5,6,6,7,7,8, A method for hydroformylating 8,9,9,10,10,10-heptadecafluoro-1-decene is disclosed. Non-Patent Documents 2 and 3 include 3,3,3-trifluoropropene in a 1: 1 mixed gas of carbon monoxide and hydrogen at 20 to 100 atm in the presence of a catalyst composed of a rhodium compound and diphosphine. A method for hydroformylating 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene is disclosed.

  In the hydroformylation of (perfluoroalkyl) ethylene, 2-methyl-2- (perfluoroalkyl) ethanal (hereinafter referred to as a branched aldehyde) together with the desired 3- (perfluoroalkyl) propanal (hereinafter referred to as a linear aldehyde). By-product). In order to simplify the separation step after hydroformylation, the by-product of branched aldehydes is suppressed as much as possible, and the ratio of linear aldehydes produced ((linear aldehyde yield) / (linear aldehyde yield + branch). The yield of aldehyde (hereinafter referred to as selectivity) is preferably high. In hydroformylation of 3,3,3-trifluoropropene in the presence of octacarbonyl dicobalt as described in Non-Patent Document 1, the selectivity of 4,4,4-trifluorobutanal, which is a linear aldehyde, is 93 %. Further, in the presence of platinum, ruthenium or rhodium compound, it is 3% -71%. Further, 3,3,4,4,4-pentafluoro-1-butene, 3,3,4,4,5,5,5-heptafluoro-1-pentene, 3,3 in the presence of tetrarhodium dodecacarbonyl 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decene, the selectivity is 5.3. -27.2%. In the hydroformylation of 3,3,3-trifluoropropene in the presence of the rhodium compound described in Non-Patent Documents 2 and 3, the selectivity is 4-12%. In the hydroformylation of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene, the selectivity is 9%.

  1,1 ′-(9,9-Dimethyl-9H-xanthene-4,5-diyl) bis (1,1-diphenylphosphine) and its derivatives have a very high selectivity when used in combination with a rhodium compound. It is disclosed that it becomes a catalyst for hydroformylation (for example, Non-Patent Documents 4 and 5). In addition, 6,6 ′-[(3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-biphenyl-2,2′-diyl) bis (oxy)] bis (dibenzo [ d, f] [1,3,2] dioxaphosphepine) is disclosed to be a catalyst for hydroformylation having a very high selectivity when used in combination with a rhodium compound (for example, non-patent) Reference 6). Hydroformylation using these catalyst systems is also carried out in a 1: 1 mixture gas of carbon monoxide and hydrogen at a high pressure of 10-33 atm. Moreover, there is no example which hydroformylated (perfluoroalkyl) ethylene using these catalyst systems.

Journal of the American Chemical Society, 109, 7714, 1987. Journal of the American Chemical Society, 119, 4413, 1997. Journal of the American Chemical Society, 125, 8555, 2003. Organometallics, 14, 3081, 1995. Journal of the American Chemical Society, 125, 10311, 2003. Angelwandte Chemie, International Edition, 52, 1586, 2013.

An object of the present invention is to provide a method for producing a linear aldehyde with high selectivity under low pressure conditions by hydroformylation of (perfluoroalkyl) ethylene.

As a result of intensive studies in view of the above-mentioned problems, the present inventors have used a rhodium compound and diphosphine, and thereby, by hydroformylation of (perfluoroalkyl) ethylene, a high selectivity to a linear aldehyde at a low pressure of 1 atm or less. As a result, the present invention was completed. That is, the present invention
(I) Rhodium compound and general formula (1-1)

(In the formula, R ¹ represents a hydrogen atom, a halogen atom or an alkoxy group having 1 to 3 carbon atoms. X represents a dimethylmethylene group or an imino group.) Or the general formula (1-2)

(In the formula, R ² represents an alkyl group having 1 to 3 carbon atoms. R ³ represents an alkyl group having 1 to 4 carbon atoms.) In the presence of diphosphine represented by the general formula (2)

(Wherein Rf represents a perfluoroalkyl group having 1 to 16 carbon atoms.) (Perfluoroalkyl) ethylene represented by the general formula (3), characterized by reacting carbon monoxide and hydrogen. )

(Wherein Rf represents the same content as described above) 3- (perfluoroalkyl) propanal production method represented by:
(Ii) The method for producing 3- (perfluoroalkyl) propanal according to claim (i), wherein Rf is a trifluoromethyl group;
(Iii) The partial pressures of carbon monoxide and hydrogen are each independently 0.1 to 0.9 atm, and the sum of the partial pressures of carbon monoxide, hydrogen and (perfluoroalkyl) ethylene (2) is 1 atm The method for producing 3- (perfluoroalkyl) propanal according to (i) or (ii):
(Iv) The method for producing 3- (perfluoroalkyl) propanal according to any one of (i) to (iii), wherein the partial pressure ratio of carbon monoxide to hydrogen is 1: 1 to 9: 1;
(V) The method for producing 3- (perfluoroalkyl) propanal according to any one of (i) to (iv), wherein the reaction temperature is 70 to 120 ° C;
(Vi) The rhodium compound is hexarhodium (0) hexadecacarbonyl, hydroxo (1,5-cyclooctadiene) rhodium (I) dimer, methoxo (1,5-cyclooctadiene) rhodium (I) dimer, (acetyl) Any one of (i) to (v) which is at least one selected from acetonato) dicarbonylrhodium (I), hydridocarbonylbis (triphenylphosphine) rhodium (I) and tris (acetylacetonato) rhodium (III) A process for producing 3- (perfluoroalkyl) propanal according to claim 1;
(Vii) The method for producing 3- (perfluoroalkyl) propanal according to any one of (i) to (iv), wherein X is a dimethylmethylene group, and R ¹ is a hydrogen atom, a fluorine atom or a methoxy group. ;
(Viii) The method for producing 3- (perfluoroalkyl) propanal according to any one of (i) to (iv), wherein X is a dimethylmethylene group, and R ¹ is a hydrogen atom;
(Ix) The method for producing 3- (perfluoroalkyl) propanal according to any one of (i) to (iv), wherein X is an imino group, and R ¹ is a hydrogen atom;
(X) The method for producing 3- (perfluoroalkyl) propanal according to any one of (i) to (iv), wherein R ² is a methyl group and R ³ is a tert-butyl group;
It is about.
The present invention is described in detail below.
Specific examples of the halogen atom represented by R ¹ of diphosphine (1-1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom is preferable in terms of good yield and selectivity.

The alkoxy group having 1 to 3 carbon atoms represented by R ¹ of diphosphine (1-1) may be linear or branched. Specifically, a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group may be used. It can be illustrated. A methoxy group is preferable in terms of good yield and selectivity.
Diphosphine (1-1 X is a dimethylmethylene group or an imino group.
The alkyl group having 1 to 3 carbon atoms represented by R ² of diphosphine (1-2) may be linear or branched, and specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. it can. A methyl group is preferable in terms of good yield and selectivity.
The alkyl group having 1 to 4 carbon atoms represented by R ³ of diphosphine (1-2) may be linear or branched, and specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl Group, isobutyl group, sec-butyl group, and tert-butyl group. A tert-butyl group is preferable in terms of good yield and selectivity.

  (Perfluoroalkyl) The perfluoroalkyl group represented by Rf of ethylene (2) may be linear, branched or cyclic, and specifically includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, Perfluoroisopropyl group, perfluorobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, perfluoropentyl group, perfluoroisopentyl group, perfluorohexyl group, perfluoroisohexyl group, perfluorocyclohexyl group, perfluoroheptyl group, perfluorooctyl Group, perfluorocyclooctyl group, perfluorononyl group, perfluorodecanyl group, perfluoroundecanyl group, perfluorododecanyl group, perfluorotridecanyl group, perfluoro Toradekaniru group, a perfluoroalkyl pentadecanoyl group, perfluoro hexadecanyl group and the like can be exemplified. From the viewpoint of being useful as a fluorine-containing building block for synthesizing drugs and functional materials, a straight chain is preferable, and a trifluoromethyl group is particularly preferable.

  Specific examples of rhodium compounds that can be used in the present invention include zero-valent rhodium compounds such as hexarhodium (0) hexadecacarbonyl and tetrarhodium (0) dodecacarbonyl, and chlorobis (2,2′-bipyridyl) rhodium. (I), (acetylacetonato) (1,5-cyclooctadiene) rhodium (I), chlorobis (triphenylphosphine) rhodium (I) dimer, hydroxo (1,5-cyclooctadiene) rhodium (I) dimer Chloro (1,5-cyclooctadiene) rhodium (I) dimer, methoxo (1,5-cyclooctadiene) rhodium (I) dimer, chloro (norbornadiene) rhodium (I) dimer, (acetylacetonato) dicarbonyl Rhodium (I), chlorotris (triphenylphosphine) Ivalent rhodium compounds such as rhodium (I), hydridocarbonylbis (triphenylphosphine) rhodium (I), rhodium (III) chloride, rhodium (III) acetate, rhodium (III) nitrate, chloropentakis (trichlorostanato) Illustrative are trivalent rhodium compounds such as rhodium (III), chloro (tetraphenylporphyrinato) rhodium (III), hexaammine rhodium (III) salt, tris (acetylacetonato) rhodium (III). Hexalhodium (0) hexadecacarbonyl, hydroxo (1,5-cyclooctadiene) rhodium (I) dimer, chloro (1,5-cyclooctadiene) rhodium (I) dimer in terms of good yield and selectivity , Methoxo (1,5-cyclooctadiene) rhodium (I) dimer, (acetylacetonato) dicarbonylrhodium (I), hydridocarbonylbis (triphenylphosphine) rhodium (I), tris (acetylacetonato) rhodium ( III) is preferred.

  Among these rhodium compounds, chlorobis (2,2′-bipyridyl) rhodium (I), chlorobis (triphenylphosphine) rhodium (I) dimer, chloro (1,5-cyclooctadiene) rhodium (I) dimer Chloro (norbornadiene) rhodium (I) dimer, (chlorotris (triphenylphosphine) rhodium (I), rhodium (III) chloride, chloropentakis (trichlorostanato) rhodium (III), chloro (tetraphenylporphyrinato) rhodium When a rhodium compound having a chloro ligand such as (III) is used, it is preferable to add an organic base from the viewpoint of good yield and selectivity, and examples of the organic base that can be used include pyridine, 4- Aminopyridine, 4- (dimethylamino) pyridine, imida And aromatic amines such as N-methylimidazole, and aliphatic amines such as triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, etc. 4- (dimethylamino) in terms of good yield and selectivity Pyridine, N-methylimidazole, tributylamine and ethyldiisopropylamine are preferred.

Although there is no restriction | limiting in particular in the usage-amount of an organic base, The quantity suitably chosen from 1-500 times mole with respect to the rhodium atom in a rhodium compound can be used.
Specifically, diphosphine (1-1) is 1,1 ′-(9,9-dimethyl-9H-xanthene-4,5-diyl) bis (1,1-diphenylphosphine), 1,1′-. (9,9-Dimethyl-9H-xanthene-4,5-diyl) bis [1,1-di (4-methoxyphenyl) phosphine], 1,1 ′-(9,9-dimethyl-9H-xanthene-4 , 5-Diyl) bis [1,1-di (4-fluorophenyl) phosphine] and 4,6-bis (diphenylphosphino) -10H-phenoxazine are preferable in terms of yield and selectivity. Further, diphosphine (1-2) is specifically 6,6 ′-[(3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-biphenyl-2,2). '-Diyl) bis (oxy)] bis (dibenzo [d, f] [1,3,2] dioxaphosphine) is preferred in terms of good yield and selectivity. These diphosphines (1-1, 1-2) may be commercially available or Organometallics, 14, 1995, p. 3081.
Or US 2002/0049355. It can be synthesized by the method described in 1.

  Although there is no restriction | limiting in particular in the usage-amount of a rhodium compound, 0.001 mol%-5 mol% of rhodium atoms in a rhodium compound are preferable at a point with a good yield and selectivity with respect to (perfluoroalkyl) ethylene (2). 0.01 mol% to 2 mol% is more preferable.

  Although there is no restriction | limiting in particular in the molar ratio of the rhodium atom and diphosphine (1-1, 1-2) in a rhodium compound, 1: 0.1-1: 25 are preferable, and 1: 0.5-1: 15 are further preferable.

  In this production method, the partial pressures of carbon monoxide and hydrogen are each independently 0.1 to 0.9 atm, and the sum of the partial pressures of carbon monoxide, hydrogen and (perfluoroalkyl) ethylene (2) is It is preferable to carry out at 1 atmosphere or less from the viewpoint of good yield and selectivity, and 1 atmosphere is more preferable.

The molar ratio of carbon monoxide to hydrogen is preferably 1: 1 to 9: 1 and more preferably 1: 1 to 7.5: 2.5 in terms of good yield and selectivity.
Carbon monoxide and hydrogen are preferably 3 times mol or more with respect to (perfluoroalkyl) ethylene (2) in terms of yield and selectivity.

  The production method of the present invention may be carried out in an organic solvent and may be any organic solvent that does not cause harm to the reaction. Organic solvents that can be used include aromatic hydrocarbons such as toluene, o-xylene, m-xylene and p-xylene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane and cyclooctane, N, N-dimethylformamide, N, N-diethylformamide, amides such as N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide, nitriles such as acetonitrile and propionitrile, tetrahydrofuran, diethyl ether, cyclopentyl methyl ether, 1 , 4-dioxane, methyl-tert-butyl ether, ethers such as 1,2-dimethoxyethane, acetone, ethyl methyl ketone, ketones such as methyl (tert-butyl) ketone, and lacta such as N-methylpyrrolidone , Dichloromethane can be exemplified by halogenated hydrocarbons such as chloroform, also a mixture of two or more of the above organic solvents no problem. From the viewpoint of good yield and selectivity, toluene, hexane, N, N-dimethylformamide, N, N-dimethylacetamide, acetone, dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone and a mixed solvent thereof are preferable.

  When (perfluoroalkyl) ethylene (2) is a gas at room temperature, it may be supplied as a gas, but it is preferably dissolved in a solvent and used in terms of good yield and selectivity. At that time, it is preferable from the viewpoint of convenience to use the solvent for the above reaction. The concentration at that time depends on the solubility of (perfluoroalkyl) ethylene (2), but is preferably 0.05 to 5 mol / L, more preferably 0.1 to 1 mol / L in terms of good yield and selectivity. preferable.

  The production method of the present invention can be carried out at a temperature appropriately selected from a temperature of 20 ° C to 200 ° C. 70 to 120 degreeC is preferable at a point with a good yield and selectivity.

  Although there is no restriction | limiting in particular in reaction time, A target object can be obtained with a sufficient yield and selectivity by performing for 0.5 hour or more.

  As a method for separating the product from the reaction solution, general-purpose methods such as distillation, column chromatography, preparative chromatography, and recrystallization can be used.

  INDUSTRIAL APPLICABILITY The present invention is effective as a method for producing 3- (perfluoroalkyl) propanal, which is an important compound as a fluorine-containing building block for synthesizing pharmaceuticals and functional materials, under high pressure conditions.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to these.
In the examples and comparative examples, the following abbreviations and chemical formulas are used.
TFP: 3,3,3-trifluoropropene, TFB: 4,4,4-trifluorobutanal, TFMP: 3,3,3-trifluoro-2-methylpropanal, DMF: N, N-dimethylformamide , THF: tetrahydrofuran, Xantphos: 1,1 ′-(9,9-dimethyl-9H-xanthene-4,5-diyl) bis (1,1-diphenylphosphine), [Rh (OH) (cod)] ₂ : hydroxo (1,5-cyclooctadiene) rhodium (I) dimer, CO: carbon monoxide, _{H 2:} hydrogen.

The product was quantified by ¹⁹ F-NMR using benzotrifluoride as an internal standard. Create a calibration curve using five standard samples with the same product concentration as the reaction solution and a linear aldehyde selectivity of 91%, 95%, 97%, 99%, and 99.5%. It was confirmed that the molar ratio of the chain aldehyde to the branched aldehyde was the same as the area ratio of the ¹⁹ F-NMR peak. Further, it was confirmed that the standard samples having selectivity of 97% and 99% agreed with the selectivity calculated using GC.

Example-1

[Rh (OH) (cod)] ₂ 4.6 mg (0.01 mmol), Xantphos 34.7 mg (0.06 mmol) and DMF 5 mL were added to the reaction vessel, and the partial pressure of 0.5 atm CO (0.6 L) and min. The mixture was heated and stirred at 80 ° C. for 1 hour in a mixed gas of H ₂ (0.6 L) at a pressure of 0.5 atm. To this solution, 5 mL of TMF 0.5 mol / L DMF solution (TFP content 2.5 mmol) was added and reacted at 80 ° C. for 15 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that 1.99 mmol of TFB (yield 80%) and 0.025 mmol of TFMP (yield 1.0%) were produced. The selectivity was 99%.
TFB
¹ H-NMR (deuterated chloroform): δ 2.46 (2H, m), 2.77 (2H, t, J = 7.5 Hz), 9.81 (1H, brs).
¹⁹ F-NMR (deuterated chloroform): δ-66.7.
TFMP
¹ H-NMR (deuterated chloroform): δ1.33 (3H, d, J = 7.2 Hz), 3.10 (1H, m), 9.77 (1H, m).
¹⁹ F-NMR (deuterated chloroform): δ-68.5.

Example-2
The same operation as in Example 1 was performed except that the reaction was performed at 90 ° C., and it was confirmed that 1.85 mmol (yield 74%) of TFB and 0.010 mmol (yield 0.4%) of TFMP were produced. . The selectivity was 99%.

Example-3
The same operation as in Example 1 was performed except that the reaction was performed at 100 ° C., and it was confirmed that 1.55 mmol (yield 62%) of TFB was generated. Production of TFMP was not observed.

Example-4
The same operation as in Example 1 was performed except that the amount of Xantphos was changed to 17.4 mg (0.03 mmol), and TFB 1.84 mmol (yield 74%) and TFMP 0.061 mmol (yield 2.5%) were obtained. It was confirmed that it was generated. The selectivity was 97%.

Example-5
The same operation as in Example 1 was performed except that the amount of Xantphos was changed to 52.1 mg (0.09 mmol), and TFB 1.95 mmol (yield 78%) and TFMP 0.029 mmol (yield 1.1%) were obtained. It was confirmed that it was generated. The selectivity was 99%.

Example-6
The same operation as in Example 1 was performed except that DMF was replaced with toluene, and it was confirmed that 1.61 mmol of TFB (yield: 64%) and 0.033 mmol of TFMP (yield: 1.3%) were produced. The selectivity was 98%.

Example-7
The same operation as in Example 1 was performed except that DMF was changed to acetonitrile, and it was confirmed that 1.60 mmol of TFB (64% yield) and 0.029 mmol of TFMP (1.2% yield) were produced. The selectivity was 98%.

Example-8
The same operation as in Example 1 was performed except that DMF was replaced with N, N-dimethylacetamide, and TFB 1.88 mmol (yield 75%) and TFMP 0.051 mmol (yield 2.0%) were produced. It was confirmed. The selectivity was 97%.

Example-9
Except that DMF was replaced with N-methylpyrrolidone, the same operation as in Example-1 was performed, and TFB 1.92 mmol (77% yield) and TFMP 0.009 mmol (0.4% yield) were produced. confirmed. The selectivity was 99.5%.

Example-10
DMF was replaced with dimethyl sulfoxide, and except that 10 mL of TFP 0.2 mol / L dimethyl sulfoxide solution (TFP content 2.0 mmol) was added, the same operation as in Example-1 was performed, and TFB 1.56 mmol (yield 78%) And TFMP 0.034 mmol (yield 1.7%) was confirmed to be produced. The selectivity was 98%.

Example-11
Xantphos was replaced with 41.9 mg (0.06 mmol) of 1,1 ′-(9,9-dimethyl-9H-xanthene-4,5-diyl) bis [1,1-di (4-methoxyphenyl) phosphine]. Except for the above, the same operation as in Example 1 was performed, and it was confirmed that 1.94 mmol (yield 77%) of TFB and 0.012 mmol (0.5% of yield) of TFMP were generated. The selectivity was 99%.

Example-12
Xantphos was replaced with 37.9 mg (0.06 mmol) of 1,1 ′-(9,9-dimethyl-9H-xanthene-4,5-diyl) bis [1,1-di (4-fluorophenyl) phosphine]. Except for the above, the same operation as in Example 1 was carried out, and it was confirmed that 1.90 mmol (76% yield) of TFB and 0.058 mmol (2.3% yield) of TFMP were produced. The selectivity was 97%.

Example-13
The same operation as in Example 1 was carried out except that Xantphos was changed to 3,6-bis (diphenylphosphino) -10H-phenoxazine 33.1 mg (0.06 mmol), and TFB 1.67 mmol (yield 67%) And TFMP 0.063 mmol (yield 2.5%) was confirmed to be produced. The selectivity was 96%.

Example-14
Xantphos is converted to 6,6 ′-[(3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-biphenyl-2,2′-diyl) bis (oxy)] bis (dibenzo [ d, f] [1,3,2] dioxaphosphepine) Except for changing to 47.2 mg (0.06 mmol), the same operation as in Example-1 was performed, and TFB 1.53 mmol (yield 61%) And TFMP 0.061 mmol (yield 2.5%) was confirmed to be produced. The selectivity was 96%.

Example-15
Except that [Rh (OH) (cod)] ₂ was changed to 4.8 mg (0.01 mmol) of methoxo (1,5-cyclooctadiene) rhodium (I) dimer, the same operation as in Example-1 was performed. It was confirmed that 1.90 mmol of TFB (yield 76%) and 0.038 mmol of TFMP (yield 1.5%) were produced. The selectivity was 98%.

Example-16
Except that [Rh (OH) (cod)] ₂ was changed to 4.8 mg (0.02 mmol) of (acetylacetonato) dicarbonylrhodium (I), the same operation as in Example-1 was performed, and 1.95 mmol of TFB ( (Yield 78%) and TFMP 0.012 mmol (yield 0.5%) were confirmed to be produced. The selectivity was 99%.

Example-17
Except that [Rh (OH) (cod)] ₂ was changed to 13.1 mg (0.02 mmol) of hydridocarbonylbis (triphenylphosphine) rhodium (I), the same operation as in Example-1 was carried out to obtain 1.86 mmol of TFB. (Yield 74%) and TFMP 0.015 mmol (yield 0.6%) were confirmed to be produced. The selectivity was 99%.

Example-18
Except that [Rh (OH) (cod)] ₂ was changed to 3.6 mg (0.0033 mmol) of hexarhodium (0) hexadecacarbonyl, the same operation as in Example-1 was carried out to obtain 1.96 mmol of TFB (yield 78 %) And 0.012 mmol (0.5% yield) of TFMP were confirmed to be produced. The selectivity was 99%.

Example-19
Except that [Rh (OH) (cod)] ₂ was replaced with 8.0 mg (0.02 mmol) of tris (acetylacetonato) rhodium (III), the same operation as in Example-1 was carried out to obtain 1.90 mmol (concentration of TFB). And a TFMP of 0.012 mmol (yield 0.5%) was confirmed. The selectivity was 99%.

Example-20
The same operation as in Example 1 was performed except that the mixed gas was changed to a mixed gas of CO (1.08 L) having a partial pressure of 0.6 atm and H ₂ (0.72 L) having a partial pressure of 0.4 atm. , TFB 2.00 mmol (yield 80%) and TFMP 0.028 mmol (yield 1.1%) were confirmed to be produced. The selectivity was 99%.

Example-21
The same operation as in Example 1 was performed except that the mixed gas was changed to a mixed gas of CO (1.26 L) having a partial pressure of 0.7 atm and H ₂ (0.54 L) having a partial pressure of 0.3 atm. , TFB 2.17 mmol (yield 87%) and TFMP 0.032 mmol (yield 1.3%) were confirmed to be produced. The selectivity was 99%.

Example-22
The same operation as in Example 1 was performed except that the mixed gas was changed to a mixed gas of CO (1.35 L) having a partial pressure of 0.75 atm and H ₂ (0.45 L) having a partial pressure of 0.25 atm. It was confirmed that 2.24 mmol (yield 89%) of TFB and 0.031 mmol (yield 1.2%) of TFMP were produced. The selectivity was 99%.

Example-23
The same operation as in Example 1 was performed except that the mixed gas was changed to a mixed gas of CO (1.44 L) having a partial pressure of 0.8 atm and H ₂ (0.36 L) having a partial pressure of 0.2 atm, It was confirmed that 1.96 mmol (yield 78%) of TFB and 0.030 mmol (yield 1.2%) of TFMP were produced. The selectivity was 98%.

Example-24
[Rh (OH) (cod)] ₂ 1.1 mg (0.0025 mmol), Xantphos 17.4 mg (0.03 mmol) and DMF 5 mL were added to the reaction vessel, and partial pressure 0.75 atm CO (1.35 L) and partial pressure were added. The mixture was heated and stirred at 80 ° C. for 1 hour in a mixed gas of 0.25 atm H ₂ (0.45 L). To this solution, 5 mL of TMF 0.5 mol / L DMF solution (TFP content 2.5 mmol) was added and reacted at 80 ° C. for 18 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that TFB 2.06 mmol (yield 82%) and TFMP 0.078 mmol (yield 3.1%) were produced. The selectivity was 96%.

Example-25
The same operation as in Example-24 was performed except that the reaction was performed at 90 ° C., and it was confirmed that TFB2.17 mmol (yield 87%) and TFMP 0.021 mmol (yield 0.8%) were produced. . The selectivity was 99%.

Example-26
[Rh (OH) (cod)] ₂ 0.46 mg (0.001 mmol), Xantphos 10.4 mg (0.018 mmol), and DMF 5 mL were added to the reaction vessel, and the partial pressure of 0.5 atm CO (0.6 L) and min. The mixture was heated and stirred at 80 ° C. for 1 hour in a mixed gas of H ₂ (0.6 L) at a pressure of 0.5 atm. To this solution was added 5 mL of TFP 0.5 mol / L DMF solution (TFP content 2.5 mmol), and the reaction atmosphere was CO (1.35 L) with a partial pressure of 0.75 atm and H _{2 with a} partial pressure of 0.25 atm. The reaction mixture was changed to a mixed gas of (0.45 L) and reacted at 90 ° C. for 18 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that 1.54 mmol (61% yield) of TFB and 0.015 mmol (0.6% yield) of TFMP were produced. The selectivity was 99%.

Example-27
The same operation as in Example -26 was carried out except that the amount of Xantphos was changed to 13.9 mg (0.024 mmol) to produce 1.79 mmol (72% yield) and 0.011 mmol (0.4% yield) TFMP. I confirmed that The selectivity was 99%.

Example-28
Except that the amount of Xantphos was 13.9 mg (0.024 mmol) and the reaction was performed at 100 ° C., all the same operations as in Example-26 were carried out, and TFB 1.66 mmol (yield 66%) was produced. confirmed. Production of TFMP was not observed.

Example-29
The same operation as in Example-26 was carried out except that the amount of Xantphos was 13.9 mg (0.024 mmol) and the reaction was performed for 27 hours, and TFB 1.87 mmol (75% yield) and TFMP 0.010 mmol (yield 0 4%) was confirmed to be produced. The selectivity was 99%.

Example-30
The amount of Xantphos was changed to 13.9 mg (0.024 mmol), and the reaction atmosphere was changed to a mixed gas of CO (1.26 L) with a partial pressure of 0.7 atm and H ₂ (0.54 L) with a partial pressure of 0.3 atm. The same operation as in Example-26 was carried out except that the reaction was carried out for 27 hours, and it was confirmed that 1.92 mmol (yield 77%) of TFB and 0.015 mmol (yield 0.6%) of TFMP were produced. . The selectivity was 99%.

Example-31
The amount of Xantphos was changed to 13.9 mg (0.024 mmol), and the reaction atmosphere was changed to a mixed gas of CO (1.17 L) having a partial pressure of 0.65 atm and H ₂ (0.63 L) having a partial pressure of 0.35 atm. The same operation as in Example 26 was carried out except that the reaction was performed for 27 hours, and it was confirmed that 2.05 mmol (82% yield) of TFB and 0.042 mmol (1.7% yield) of TFMP were produced. . The selectivity was 98%.

Example-32
[Rh (OH) (cod)] ₂ 1.1 mg (0.0025 mmol), Xantphos 8.7 mg (0.015 mmol) and DMF 5 mL were added to the reaction vessel, and the partial pressure of 0.5 atm CO (0.6 L) and min. The mixture was heated and stirred at 80 ° C. for 1 hour in a mixed gas of H ₂ (0.6 L) at a pressure of 0.5 atm. To this solution, 5 mL of TMF 0.5 mol / L DMF solution (TFP content 2.5 mmol) was added and reacted at 80 ° C. for 15 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that TFB 1.94 mmol (yield 77%) and TFMP 0.065 mmol (yield 2.6%) were produced. The selectivity was 97%.

Example-33
[RhCl (cod)] ₂ (4.9 mg, 0.01 mmol), Xantphos (34.7 mg, 0.06 mmol) and DMF (5 mL) were added to the reaction vessel, and partial pressure of 0.75 atm CO (1.35 L) and partial pressure of 0. The mixture was heated and stirred at 80 ° C. for 1 hour in a mixed gas of 25 atm H ₂ (0.45 L). To this solution, 5 mL of TMF 0.5 mol / L DMF solution (TFP content 2.5 mmol) was added and reacted at 80 ° C. for 15 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that 1.97 mmol (79% yield) of TFB and 0.10 mmol (4.0% yield) of TFMP were produced. The selectivity was 95%.

Example-34
To the reaction vessel, 4.8 mg (0.01 mmol) of methoxo (1,5-cyclooctadiene) rhodium (I) dimer, 23.1 mg (0.04 mmol) of Xantphos and 4 mL of toluene were added, and CO ( 0.6 L) and a mixed gas of H ₂ (0.6 L) having a partial pressure of 0.5 atm, and heated and stirred at 80 ° C. for 1 hour. To this solution, 1 mL of THF and 5 mL of a 0.5 mol / L toluene solution of TFP (TFP content 2.5 mmol) were added, and the reaction was performed at 80 ° C. for 15 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that 1.12 mmol (yield 45%) of TFB and 0.046 mmol (yield 1.8%) of TFMP were produced. The selectivity was 96%.

Example-35
Except that 1 mL of hexane was used instead of THF, the same operation as in Example-34 was performed, and it was confirmed that 1.19 mmol (48% yield) and 0.055 mmol (2.2% yield) TFMP were produced. confirmed. The selectivity was 96%.

Example-36
Except that 1 mL of acetone was used instead of THF, the same operation as in Example-34 was performed, and 1.61 mmol (64% yield) of TFB and 0.020 mmol (0.8% yield) of TFMP were produced. confirmed. The selectivity was 99%.

Example-37
Except that 1 mL of DMF was used instead of THF, the same operation as in Example-34 was performed to confirm that 1.70 mmol (68% yield) and 0.031 mmol (TF1.2%) TFMP were produced. did. The selectivity was 98%.

Example-38
[Rh (OH) (cod)] ₂ 4.6 mg (0.01 mmol), Xantphos 34.7 mg (0.06 mmol) and DMF 5 mL were added to the reaction vessel, and the partial pressure of 0.5 atm CO (0.6 L) and min. The mixture was heated and stirred at 80 ° C. for 1 hour in a mixed gas of H ₂ (0.6 L) at a pressure of 0.5 atm. To this solution, 5 mL of TFP 0.5 mol / L DMF solution (TFP content 2.5 mmol) was added and reacted at 80 ° C. for 2 hours. Furthermore, 5 mL (0.5 mol / L, TFP content 2.5 mmol) of DMF solution of TFP was added, and the reaction was performed at 80 ° C. for 2 hours. This operation was repeated three more times (total TFP input 12.5 mmol), and ¹⁹ F-NMR produced 9.84 mmol (79% yield) and 0.11 mmol (0.9% yield) TFMP. I confirmed. The selectivity was 99%.

Example-39
[Rh (OH) (cod)] ₂ 4.6 mg (0.01 mmol), Xantphos 34.7 mg (0.06 mmol) and DMF 10 mL were added to the reaction vessel, and the partial pressure 0.5 atm CO (0.6 L) and min. The mixture was heated at 80 ° C. for 1 hour in a mixed gas of H ₂ (0.6 L) at a pressure of 0.5 atm. TFP (48 mL, TFP amount 2.0 mmol) was added thereto using a gas tight syringe, and the reaction was performed at 80 ° C. for 15 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that TFB 0.99 mmol (yield 50%) and TFMP 0.028 mmol (yield 1.4%) were produced. The selectivity was 97%.

Example-40
[Rh (OH) (cod)] ₂ 4.6 mg (0.01 mmol), Xantphos 34.7 mg (0.06 mmol) and 10 mL of toluene were added to the reaction vessel, and the partial pressure of 0.5 atm CO (0.6 L) and The mixture was heated at 80 ° C. for 1 hour in a mixed gas of H ₂ (0.6 L) having a partial pressure of 0.5 atm. TFP (48 mL, TFP amount 2.0 mmol) was added thereto using a gas tight syringe, and the reaction was performed at 80 ° C. for 15 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that TFB 0.86 mmol (yield 43%) and TFMP 0.029 mmol (yield 1.5%) were produced. The selectivity was 97%.

Example-41
[RhCl (cod)] ₂ 4.9 mg (0.01 mmol), Xantphos 34.7 mg (0.06 mmol), DMAP 3.7 mg (0.03 mmol) and DMF 5 mL were added to the reaction vessel, and CO (partial pressure 0.75 atm) CO ( 1.35 L) and a mixed gas of H ₂ (0.45 L) having a partial pressure of 0.25 atm, and heated and stirred at 80 ° C. for 1 hour. To this solution, 5 mL of TMF 0.5 mol / L DMF solution (TFP content 2.5 mmol) was added and reacted at 80 ° C. for 15 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that 1.97 mmol (yield 87%) and TFMP 0.10 mmol (yield 0.4%) were produced. The selectivity was 99.6%.

Example-42
The same operation as in Example 1 was carried out except that the amount of DMAP was 12.2 mg (0.1 mmol), and it was confirmed that 2.29 mmol (92% yield) of TFB was generated. TFMP was not generated.

Example-43
[RhCl (cod)] ₂ was changed to 1.2 mg (0.0025 mmol) and Xantphos was changed to 17.4 mg (0.03 mmol) and DMAP 0.9 mg (0.0075 mmol). It was confirmed that 0.04 mmol (yield 82%) and TFMP 0.019 mmol (yield 0.8%) were produced. The selectivity was 99%.

Example-44
The same operation as in Example 1 was carried out except that 0.8 mg (0.01 mmol) of N-methylimidazole was used instead of DMAP, and 2.04 mmol (82% yield) of TFB and 0.013 mmol (TF5) of TFMP. %) Was confirmed to be generated. The selectivity was 99%.

Example-45
The same operation as in Example 1 was performed except that 1.9 mg (0.01 mmol) of tributylamine was used instead of DMAP, and TFB2.11 mmol (yield 85%) and TFMP 0.010 mmol (yield 0.4%) were obtained. Was confirmed to be generated. The selectivity was 99.5%.

Example-46
To the reaction vessel were added rhodium (III) trihydrate 5.3 mg (0.02 mmol), Xantphos 34.7 mg (0.06 mmol), DMAP 12.2 mg (0.1 mmol) and DMF 5 mL, with a partial pressure of 0.5 atm. In a mixed gas of CO (0.6 L) and H ₂ (0.6 L) having a partial pressure of 0.5 atm, the mixture was heated and stirred at 80 ° C. for 1 hour. To this solution, 5 mL of TMF 0.5 mol / L DMF solution (TFP content 2.5 mmol) was added and reacted at 80 ° C. for 15 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that 1.61 mmol (64% yield) of TFB was produced. Production of TFMP was not observed.

Example-47

[Rh (OH) (cod)] ₂ 4.6 mg (0.01 mmol), Xantphos 34.7 mg (0.06 mmol) and DMF 10 mL were added to the reaction vessel, and the partial pressure 0.5 atm CO (0.6 L) and min. The mixture was heated and stirred at 80 ° C. for 1 hour in a mixed gas of H ₂ (0.6 L) at a pressure of 0.5 atm. To this solution, 615 mg (2.5 mmol) of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene was added and reacted at 80 ° C. for 15 hours. After the reaction, it was confirmed by ¹⁹ F-NMR that 4,4,5,5,6,6,7,7,7-nonafluoroheptanal 2.28 mmol (yield 91%) was produced. Formation of 3,3,4,4,5,5,6,6,6-nonafluoro-2-methylhexanal was not observed.
4,4,5,5,6,6,7,7,7-nonafluoroheptanal
¹ H-NMR (deuterated chloroform): δ 2.47 (2H, m), 2.83 (2H, t, J = 7.5 Hz), 9.84 (1H, brs).
¹⁹ F-NMR (deuterated chloroform): δ-81.2 (3F, m), -114.6 (2F, m), -124.5 (2F, m), -126.1 (2F, m).

Example-48

3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene instead of 615 mg (2.5 mmol), 3,3,4,4,5,5,6,6,7, Except that 1.12 g (2.5 mmol) of 7,8,8,9,9,10,10,10-heptadecafluoro-1-decene was used, the same operation as in Example-42 was carried out. 5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecoundecenal 2.33 mmol (yield 93%) It was confirmed. Formation of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2-methyldecenal was not observed.
4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecooundesenal
¹ H-NMR (deuterated chloroform): δ 2.47 (2H, m), 2.83 (2H, t, J = 7.4 Hz), 9.84 (1H, brs).
¹⁹ F-NMR (deuterated chloroform): δ-80.7 (3F, t, J = 10.0 Hz), -114.7 (2F, m), -121.7 (2F, m), -121.9 (4F, m), -122.7 (2F, m), -123.5 (2F, m), -126.1 (2F, m).

Claims (10)

Rhodium compound and general formula (1-1)

(In the formula, R ¹ represents a hydrogen atom, a halogen atom or an alkoxy group having 1 to 3 carbon atoms. X represents a dimethylmethylene group or an imino group.) Or the general formula (1-2)

(In the formula, R ² represents an alkyl group having 1 to 3 carbon atoms. R ³ represents an alkyl group having 1 to 4 carbon atoms.) In the presence of diphosphine represented by the general formula (2)

(Wherein Rf represents a perfluoroalkyl group having 1 to 16 carbon atoms.) (Perfluoroalkyl) ethylene represented by the general formula (3), characterized by reacting carbon monoxide and hydrogen. )

(Wherein Rf represents the same content as described above). A method for producing 3- (perfluoroalkyl) propanal represented by: The method for producing 3- (perfluoroalkyl) propanal according to claim 1, wherein Rf is a trifluoromethyl group. The partial pressures of carbon monoxide and hydrogen are each independently 0.1 to 0.9 atm, and the sum of the partial pressures of carbon monoxide, hydrogen and (perfluoroalkyl) ethylene (2) is 1 atm or less. A process for producing 3- (perfluoroalkyl) propanal according to claim 1 or 2.   The method for producing 3- (perfluoroalkyl) propanal according to any one of claims 1 to 3, wherein a partial pressure ratio of carbon monoxide to hydrogen is 1: 1 to 9: 1. The method for producing 3- (perfluoroalkyl) propanal according to any one of claims 1 to 4, wherein the reaction temperature is 70 to 120 ° C. Rhodium compounds are hexarhodium (0) hexadecacarbonyl, hydroxo (1,5-cyclooctadiene) rhodium (I) dimer, methoxo (1,5-cyclooctadiene) rhodium (I) dimer, (acetylacetonato) 6. One or more selected from dicarbonylrhodium (I), hydridocarbonylbis (triphenylphosphine) rhodium (I), and tris (acetylacetonato) rhodium (III). 6. A method for producing (perfluoroalkyl) propanal. The method for producing 3- (perfluoroalkyl) propanal according to any one of claims 1 to 6, wherein X is a dimethylmethylene group, and R ¹ is a hydrogen atom, a fluorine atom or a methoxy group. The method for producing 3- (perfluoroalkyl) propanal according to any one of claims 1 to 6, wherein X is a dimethylmethylene group and R ¹ is a hydrogen atom. The method for producing 3- (perfluoroalkyl) propanal according to any one of claims 1 to 6, wherein X is an imino group and R ¹ is a hydrogen atom. The method for producing 3- (perfluoroalkyl) propanal according to any one of claims 1 to 6, wherein R ² is a methyl group and R ³ is a tert-butyl group.