JP5194332B2 - Method for producing fluorine-containing alkylethyl halide - Google Patents

Description

  The present invention relates to a method for producing a fluorine-containing alkylethyl halide.

General formula (V):
^{_{R f 1 -CH 2 CH 2 OCOCR}} = CH 2 (V)
(Wherein R _f ¹ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms, and R represents H Or represents CH ₃ )
The fluorine-containing ester represented by is a compound useful as a raw material for water and oil repellents and the production method thereof is represented by the general formula (IIIa):
R _f ¹ —CH ₂ CH ₂ I (IIIa)
(Wherein R _f ¹ is the same as above)
A fluorine-containing alkyl iodide represented by the general formula (IV):
CH ₂ = CRCOOM (IV)
(Wherein M represents an alkali metal and R is the same as above)
There is known a method of reacting with a carboxylate represented by the formula (for example, see Patent Document 1).

However, in this production method, the general formula (I):
^{_{R f 1 -CH = CH 2 (}} I)
(Wherein R _f ¹ is the same as above)
There is a problem that a large amount of fluorine-containing alkene represented by

The fluorine-containing alkene (I) produced as a by-product is represented by the general formula (A):
R _f ¹ CH ₂ CH ₂ SiR ′ _n X _3-n (A)
(Wherein, n is 0, 1 or 2, R ′ represents an alkyl group or an aryl group, and R _f ¹ is the same as described above). For example, refer to Patent Document 2), the demand amount is not sufficient only for this use, and it is desired to effectively use surplus fluorine-containing alkene.

  For example, if fluorine-containing alkene (I) can be converted to fluorine-containing alkyl iodide (IIIa), it can be recycled as a raw material for the above-mentioned fluorine-containing ester (V), and production efficiency can be improved. Is done.

  As a method for converting the fluorinated alkene (I) into the fluorinated alkyl iodide (IIIa), for example, a method of adding hydrogen iodide to the fluorinated alkene (I) is conceivable. However, in this method, since it is necessary to once produce hydrogen iodide and to isolate and purify it, the production process becomes complicated. In addition, hydrogen iodide is highly toxic and corrosive, and is difficult to handle because it has the property of being easily decomposed in the presence of oxygen and light.

Moreover, as a method of adding hydrogen halides such as hydrogen chloride and hydrogen bromide to a fluorine-containing olefin, a method using AlBr ₃ as a catalyst (see, for example, Non-Patent Document 1), and a method using CaSO ₄ / C as a catalyst. (For example, refer nonpatent literature 2) etc. are reported, However, Since each method needs to isolate | separate a solid catalyst, manufacturing efficiency is inferior.
Japanese Examined Patent Publication No. 39-18112 Japanese Patent Laid-Open No. 50-126621 Journal of the American Chemical Society (J. Am. Chem. Soc.), 72, 3369 (1950) Journal of the American Chemical Society (J. Am. Chem. Soc.), 75, 5618 (1953)

  An object of the present invention is to efficiently produce a fluorine-containing alkylethyl halide using a fluorine-containing alkene as a starting material. Another object is to efficiently produce a fluorinated ester using a fluorinated alkylethyl halide obtained by this method.

As a result of intensive studies to achieve the above-mentioned object, the present inventor made hydrogen halide gas once by reacting a fluorine-containing alkene with a combination of reagents capable of generating hydrogen halide in the reaction system. The inventors have found that fluorine-containing alkylethyl halides can be produced in one step without producing and isolating and pursuing the present invention.
That is, the present invention relates to the following technique.
1. Formula (I):
^{_{R f 1 -CH = CH 2 (}} I)
(Wherein R _f ¹ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms)
A fluorine-containing alkene represented by the general formula (II):
X ₂ (II)
(Wherein X represents Cl, Br or I)
Wherein the halogen molecule represented by formula (II) is reacted with an alkyl-substituted aromatic compound in the presence or absence of a catalyst, the general formula (III):
^{_{R f 1 -CH 2 CH 2 -X}} (III)
(Wherein R _f ¹ and X are as defined above)
A process for producing a fluorine-containing alkylethyl halide represented by the formula:
2. Formula (I):
^{_{R f 1 -CH = CH 2 (}} I)
(Wherein R _f ¹ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms)
A fluorine-containing alkene represented by the formula: -CF ₂ X group (wherein X represents Cl, Br, or I) in the molecule; and n is an alkyl-substituted compound. Reacting with an aromatic compound in the presence or absence of a catalyst, general formula (III):
^{_{R f 1 -CH 2 CH 2 -X}} (III)
(Wherein R _f ¹ and X are as defined above)
A process for producing a fluorine-containing alkylethyl halide represented by the formula:
3. Item 3. The method according to Item 1 or 2, wherein the alkyl group of the alkyl-substituted aromatic compound is a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms, and has a number that can be substituted from 1 as a substituent.
4). The alkyl group of the alkyl-substituted aromatic compound is at least one selected from the group consisting of methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group; Item 3. The method according to Item 1 or 2, wherein the number of substitutable groups from 1 is substituted.
5. Item 5. The method according to any one of Items 1 to 4, wherein the aromatic moiety of the alkyl-substituted aromatic compound has at least one selected from the group consisting of benzene, naphthalene, anthracene, and phenanthrene.
6). A compound having n —CF ₂ X groups (X represents Cl, Br, or I) in the molecule (wherein n represents an integer of 1 or more) is represented by the general formula (IIa)
^{_{R f 2 - (CF 2 X}} ) n (IIa)
(In the formula, R _f ² represents a linear or branched perfluoroalkyl group having 1 to 50 carbon atoms or a linear or branched polyfluoroalkyl group having 1 to 50 carbon atoms, and X represents Cl Or, Br or I is indicated, and n is an integer of 1 or more)
Item 3. The method according to Item 2.
7). Item 7. The method according to any one of Items 1 to 6, wherein the catalyst is at least one selected from the group consisting of activated carbon, metal sulfate, metal, Lewis acid, and aromatic compound.
8). The metal sulfate is at least one selected from the group consisting of potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate and aluminum sulfate, and the metal is copper, platinum, zinc, palladium, tin, titanium, zirconium, gallium. At least one selected from the group consisting of cobalt, nickel and iron, and Lewis acid is boron halide, antimony halide, tin halide, titanium halide, zinc halide, aluminum halide, gallium halide At least one selected from the group consisting of arsenic halide, iron halide, mercury halide and zirconium halide, and the aromatic compound is benzene, naphthalene, phenanthrene, anthracene, pyrene, naphthacene, benzanthracene and benzpyrene Kara The method according to claim 7 which is at least one selected from the group.
9. After obtaining the fluorine-containing alkylethyl halide represented by the general formula (III) by the method according to any one of Items 1 to 8, this is represented by the general formula (IV):
CH ₂ = CRCOOM (IV)
(In the formula, M represents an alkali metal, and R represents H or CH ₃ )
It is reacted with a carboxylate represented by the general formula (V):
R _f ¹ —CH ₂ CH ₂ —OCOCR═CH ₂ (V)
(Wherein R _f ¹ and R are the same as above)
The manufacturing method of fluorine-containing ester represented by these.
10. General formula (III):
^{_{R f 1 -CH 2 CH 2 -X}} (III)
(Wherein R _f ¹ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms, and X represents Cl, Br Or I)
A fluorine-containing alkylethyl halide represented by the general formula (IV):
CH ₂ = CRCOOM (IV)
(In the formula, M represents an alkali metal, and R represents H or CH ₃ )
Is reacted with a carboxylate represented by the general formula (V):
R _f ¹ —CH ₂ CH ₂ —OCOCR═CH ₂ (V)
(Wherein R _f ¹ and R are the same as above)
In the method for producing a fluorine-containing ester represented by general formula (I):
^{_{R f 1 -CH = CH 2 (}} I)
(Wherein R _f ¹ is the same as above)
In the production process of the fluorine-containing ester of the general formula (V), the fluorine-containing alkene represented by the formula A method for producing a fluorinated ester represented by the general formula (V), which is recycled as a raw material.

The present invention is described in detail below.
The method of the present invention is represented by the general formula (I):
^{_{R f 1 -CH = CH 2 (}} I)
(Wherein R _f ¹ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms)
A fluorine-containing alkene represented by the general formula (II):
X ₂ (II)
(Wherein X represents Cl, Br or I)
Wherein the halogen molecule represented by formula (II) is reacted with an alkyl-substituted aromatic compound in the presence or absence of a catalyst, the general formula (III):
^{_{R f 1 -CH 2 CH 2 -X}} (III)
(Wherein R _f ¹ and X are as defined above)
Is a method for producing a fluorine-containing alkylethyl halide represented by the formula:
Compound (I) is a known compound, and examples of the perfluoroalkyl represented by Rf ¹ include linear or branched perfluoroalkyl having 1 to 20 carbon atoms, such as CF ₃ , C ₂ F ₅ , (n- or iso-) C ₃ F ₇ , (n- or iso-, sec- or tert-) C ₄ F ₉ , CF ₃ (CF ₂ ) _m (m is an integer of 4 to 19) , (CF ₃ ) ₂ CF (CF ₂ ) _k (k is an integer of _{2 to} 17), and the like.

Examples of the polyfluoroalkyl include linear or branched polyfluoroalkyl having 1 to 20 carbon atoms, such as CHF ₂ (CF ₂ ) _p (p is an integer of 1 to 5), CH ₂ F ( CF ₂ ) _q (q is an integer of 1 to 5) and the like.
General formula (II):
X ₂ (II)
(Wherein X represents Cl, Br or I)
In the halogen molecule represented by X, X is preferably Br or I, more preferably I.

  The alkyl-substituted aromatic compound is preferably a benzene or naphthalene derivative, more preferably a benzene derivative. Moreover, the alkyl-substituted aromatic compound can be used alone or in combination of two or more. The amount of the alkyl-substituted aromatic compound used is preferably about 1 to 100 mol, more preferably about 1 to 10 mol, per 1 mol of the fluorinated alkene (I).

In the reaction of the present invention, the reaction with the fluorinated alkene (I), X ₂ (X represents Cl, Br or I) (II) and the alkyl-substituted aromatic compound is carried out in the presence or absence of a catalyst. Can be done. Specifically, when X ₂ and an alkyl-substituted aromatic compound are used as a reagent capable of generating hydrogen halide in the reaction system, the reaction can be performed in the presence or absence of a catalyst. .

  As the catalyst, activated carbon, metal sulfate, metal, Lewis acid, aromatic compound and the like can be used. These catalysts can be used singly or in combination of two or more.

  There is no limitation in particular as activated carbon, The well-known well-known activated carbon can be used.

  Specific examples of the metal sulfate include potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate, aluminum sulfate and the like, and these can be used alone or in combination of two or more.

  Examples of the metal include copper, platinum, zinc, palladium, tin, titanium, zirconium, gallium, cobalt, nickel, iron, and the like, and these can be used alone or in combination of two or more.

  Lewis acids include boron halide, antimony halide, tin halide, titanium halide, zinc halide, aluminum halide, gallium halide, arsenic halide, iron halide, mercury halide, zirconium halide, etc. Can be used. In these compounds, examples of the halogen include chlorine, bromine and iodine. These Lewis acids can be used alone or in combination of two or more.

As the aromatic compound, benzene, naphthalene, phenanthrene, anthracene, pyrene, naphthacene, benzanthracene, benzpyrene and the like can be used, and these can be used singly or in combination.
About the usage-amount of a catalyst, when using activated carbon, a metal sulfate, or an aromatic compound, it is preferable to set it as about 0.1-10 mol with respect to 1 mol of fluorine-containing alkenes (I). In addition, when a Lewis acid salt is used as a catalyst, it is preferable that about 0.1 to 1 mol is required per 1 mol of the fluorine-containing alkene.

  In the reaction of the fluorine-containing alkene (I), the halogen molecule (II) and the alkyl-substituted aromatic compound, the reaction temperature is preferably about 50 to 400 ° C, more preferably about 100 to 300 ° C. The reaction time is usually about 1 to 100 hours.

  The reaction can be carried out using 0.01 to 10 mol of halogen molecule (II) and 0.01 to 100 mol of alkyl-substituted aromatic compound per 1 mol of fluorine-containing alkene (I).

The reaction is preferably carried out after substituting the inside of the reaction system with an inert gas (N ₂ , Ar, CO _2, etc.) and reducing the pressure to about 0 to 5 × 10 ⁴ Pa.

  The specific reaction method is not particularly limited. For example, a raw material and a catalyst as necessary are charged into a pressure vessel such as an autoclave, the vessel is replaced with an inert gas such as nitrogen, and then the pressure is reduced. The temperature may be raised to the reaction temperature and stirred for a predetermined time at the same temperature.

  The fluorine-containing alkylethyl halide (III) obtained by the production method of the present invention can be purified by a known method such as extraction, distillation, recrystallization, column chromatography.

  The reaction between compound (III) and compound (IV) is carried out at 100 to 300 ° C. for 1 to 50 hours using 0.1 to 100 mol of compound (IV) per 1 mol of compound (III). The fluorine-containing ester of the general formula (V) can be produced.

  In the reaction of obtaining the compound (V) by reacting the compound (III) and the compound (IV), the fluorine-containing alkene represented by the general formula (I) as a by-product is separated and purified by, for example, distillation, and the general formula (III) ) And can be recycled.

  The reaction for obtaining the compound (V) may be carried out in accordance with known reaction conditions described in JP-B-39-18112 and the like, for example, fluorine-containing alkyl in an alcohol solvent (for example, t-butanol) under normal pressure. Halide (III) and carboxylate (IV) are mixed and usually heated and stirred at about 100 to 300 ° C for about 1 to 50 hours. By purifying the reaction mixture thus obtained, the fluorinated ester (V) can be obtained.

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

Fluorine-containing alkene (C ₈ F ₁₇ CH = CH ₂ ) 40.5 g (91 mmol), iodine (I ₂ ) 11.5 g (91 mmol), ethylbenzene (C ₈ H ₁₀ ) 46.3 g (436 mmol) ), Purged with nitrogen and evacuated, and then heated to 170 ° C. with stirring at 400 rpm to carry out a 4 hr reaction.

  After the reaction, the obtained liquid was analyzed by gas chromatography (GC).

GC conditions Carrier gas: Helium, 50 ml / min
Inlet: 250 ℃
Detector: 250 ℃, TCD 100mA
Column: 3m SE-30
Column heating conditions: 50 ° C, 5 min → 10 ° C / min, rising temperature → 250 ° C, 5 min
It was found that C ₈ F ₁₇ CH ₂ CH ₂ I was obtained at a conversion of 10.6% and a selectivity of 99.7%.

Fluorine-containing alkene (C ₈ F ₁₇ CH = CH ₂ ) 40.5 g (91 mmol), iodine (I ₂ ) 11.5 g (91 mmol), ethylbenzene (C ₈ H ₁₀ ) 46.3 g (436 mmol) ), Purged with nitrogen and evacuated, and then heated to 200 ° C. with stirring at 400 rpm for 4 hr reaction.
After the reaction, the obtained liquid was analyzed by gas chromatography (GC).

As a result, it was found that C ₈ F ₁₇ CH ₂ CH ₂ I was obtained at a conversion of 19.1% and a selectivity of 97.4%.

Fluorine-containing alkene (C ₈ F ₁₇ CH = CH ₂ ) 40.5 g (91 mmol), iodine (I ₂ ) 11.5 g (91 mmol), n-propylbenzene (C ₉ H ₁₂ ) 52.6 g in a 200 ml Hastelloy autoclave (438 mmol) was added, and after purging with nitrogen and evacuating, the temperature was raised to 170 ° C. while stirring at 400 rpm to carry out a 4 hr reaction.
After the reaction, the obtained liquid was analyzed by gas chromatography (GC).

As a result, it was found that C ₈ F ₁₇ CH ₂ CH ₂ I was obtained at a conversion rate of 11.8% and a selectivity of 94.5%.

Fluorine-containing alkene (C ₈ F ₁₇ CH = CH ₂ ) 40.5 g (91 mmol), iodine (I ₂ ) 11.5 g (91 mmol), n-butylbenzene (C ₁₀ H ₁₄ ) 58.6 g in a 200 ml Hastelloy autoclave (436 mmol) was added, and after purging with nitrogen and evacuating, the temperature was raised to 170 ° C. while stirring at 400 rpm to carry out a 4 hr reaction.
After the reaction, the obtained liquid was analyzed by gas chromatography (GC).

As a result, it was found that C ₈ F ₁₇ CH ₂ CH ₂ I was obtained at a conversion of 7.5% and a selectivity of 96.4%.

  According to the production method of the present invention, the fluorine-containing alkylethyl halide (III) can be produced in one step without using hydrogen iodide gas which is difficult to handle.

  It is also possible to proceed the reaction without using a solid catalyst. In this case, it is not necessary to separate the solid catalyst by a method such as filtration, and the fluorinated alkylethyl halide (III) can be produced efficiently.

  The fluorinated alkene (I) can be efficiently converted to the fluorinated alkylethyl halide (III), and the fluorinated alkene, which has a low utility value, can be reused to lead to a fluorinated ester. As a result, the production efficiency of the fluorine-containing ester is improved, and as a result, the resources can be effectively used.

Claims (5)

Formula (I):
^{_{R f 1 -CH = CH 2 (}} I)
(Wherein R _f ¹ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms)
A fluorine-containing alkene represented by the general formula (II):
X ₂ (II)
(Wherein X represents Cl, Br or I)
General formula (III) characterized by reacting a halogen molecule represented by the formula (1) with an alkyl-substituted aromatic compound in the presence or absence of a catalyst:
^{_{R f 1 -CH 2 CH 2 -X}} (III)
(Wherein R _f ¹ and X are as defined above)
A process for producing a fluorine-containing alkylethyl halide represented by the formula :
The alkyl group of the alkyl-substituted aromatic compound has at least one selected from the group consisting of ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group from 1 There are as many substituents as possible,
The aromatic moiety of the alkyl-substituted aromatic compound is selected from the group consisting of benzene, naphthalene, anthracene and phenanthrene;
A method for producing a fluorine-containing alkylethyl halide . The method according to claim 1 , wherein the catalyst is at least one selected from the group consisting of activated carbon, metal sulfate, metal, Lewis acid, and aromatic compound. The metal sulfate is at least one selected from the group consisting of potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate and aluminum sulfate, and the metal is copper, platinum, zinc, palladium, tin, titanium, zirconium, gallium. At least one selected from the group consisting of cobalt, nickel and iron, and Lewis acid is boron halide, antimony halide, tin halide, titanium halide, zinc halide, aluminum halide, gallium halide At least one selected from the group consisting of arsenic halide, iron halide, mercury halide and zirconium halide, and the aromatic compound is benzene, naphthalene, phenanthrene, anthracene, pyrene, naphthacene, benzanthracene and benzpyrene Kara The method of claim 2 is at least one selected from the group. After obtaining the fluorine-containing alkylethyl halide represented by the general formula (III) by the method according to any one of claims 1 to 3 , this is represented by the general formula (IV):
CH ₂ = CRCOOM (IV)
(In the formula, M represents an alkali metal, and R represents H or CH ₃ )
General formula (V) characterized by reacting with a carboxylate represented by the formula:
^{_{R f 1 -CH 2 CH 2 -OCOCR}} = CH 2 (V)
(Wherein R _f ¹ and R are the same as above)
The manufacturing method of fluorine-containing ester represented by these. General formula (III):
^{_{R f 1 -CH 2 CH 2 -X}} (III)
(Wherein R _f ¹ represents a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or a linear or branched polyfluoroalkyl group having 1 to 20 carbon atoms, and X represents Cl, Br Or I)
A fluorine-containing alkylethyl halide represented by the general formula (IV):
CH ₂ = CRCOOM (IV)
(In the formula, M represents an alkali metal, and R represents H or CH ₃ )
Is reacted with a carboxylate represented by the general formula (V):
^{_{R f 1 -CH 2 CH 2 -OCOCR}} = CH 2 (V)
(Wherein R _f ¹ and R are the same as above)
In the method for producing a fluorine-containing ester represented by the general formula (I):
^{_{R f 1 -CH = CH 2 (}} I)
(Wherein R _f ¹ is the same as above)
In the production process of the fluorine-containing ester of the general formula (V), the fluorine-containing alkene represented by the formula is converted into the fluorine-containing alkylethyl halide of the general formula (III) by the method of any one of claims 1 to 3 . A method for producing a fluorinated ester represented by the general formula (V), which is recycled as a raw material.