JP2583470B2 - Fluorine-containing organic compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing organic compound having an acryloxyl group or a methacryloxyl group, a vinyl group and a trifluoromethyl group in one molecule.

[0002]

2. Description of the Related Art Conventionally, allyl acrylate or allyl methacrylate having an acryloxyl group or a methacryloxyl group and a vinyl group in one molecule has been known.
They are widely used industrially because they form a polymer by polymerizing alone or copolymerize with a compound having a carbon-carbon double bond in the molecule to form a polymer. . Also, since it has an acryl group and a methacryl group in the molecule, it is used as a cross-linking agent for acrylic resin, and further, by adding various silanes,
Used as a silane coupling agent. However, a fluorine-containing organic compound having an acryloxyl group or a methacryloxyl group, a vinyl group and a trifluoromethyl group in one molecule has not yet been known.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel fluorine-containing organic compound having an acryloxyl group or a methacryloxyl group, a vinyl group and a trifluoromethyl group in one molecule. .

[0004]

According to the present invention, there is provided a compound represented by formula (1):

Embedded image (Wherein, R is a hydrogen atom or a methyl group, and n is an integer of 0 or 1). Further, the present invention provides a compound represented by formula (2):

Embedded image Wherein n is an integer of 0 or 1; and reacting the fluorinated unsaturated alcohol represented by the formula (1) with acrylic acid or methacrylic acid in the presence of a dehydrating agent. A method for producing a fluorine-containing organic compound represented by the formula: Further, the present invention is characterized in that the compound represented by the formula (2) is reacted with an organic lithium to form a lithium alkoxide, and then the lithium alkoxide is reacted with acryl or methacryl chloride. A method for producing a fluorine-containing organic compound represented by the formula (1) is provided. The fluorine-containing organic compound of the present invention has an acryloxyl group or a methacryloxyl group at one end, has a vinyl group at the other end, and further has a trifluoromethyl group -CF
_{It has three} groups.

The fluorine-containing organic compound of the present invention has the above formula
In the presence of a dehydrating agent, a fluorine-containing unsaturated alcohol represented by (2) and acrylic acid or methacrylic acid, usually at −30 ° C.
It can be produced by reacting at -30 ° C, preferably -5 ° C to 10 ° C, usually for about 0 to 120 minutes, preferably for about 0 to 30 minutes.

The fluorinated unsaturated alcohol represented by the above formula (2) is a conventionally known compound, and has the formula (3):

Embedded image 1,1,1-trifluoro-2-trifluoromethyl-3-buten-2-ol represented by or a formula (4):

Embedded image 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol. These can be manufactured by an ordinary method. For example, it can be produced by a so-called Grignard reaction.The alcohol represented by the formula (3) is produced by reacting vinylmagnesium bromide and hexafluoroacetone in a solvent such as anhydrous ether and then hydrolyzing. can do. Further, the alcohol represented by the formula (4) can be produced by reacting allyl magnesium bromide with hexafluoroacetone in a solvent such as anhydrous ether and then hydrolyzing. Further, the alcohol represented by the formula (4) is produced by reacting propylene and hexafluoroacetone at a pressure of 40 to 50 kg / cm ² at a temperature of 100 to 150 ° C. for about 5 to 18 hours. You can also.

[0007] Examples of the dehydrating agent include concentrated sulfuric acid, fuming sulfuric acid, and diphosphorus pentoxide. Among them, fuming sulfuric acid is preferred. When using oleum, concentration of sulfur trioxide SO ₃ fuming sulfuric acid is preferably 5 to 60 wt%, further preferably 20 to 40 wt%.

The fluorinated organic compound of the present invention comprises a fluorinated unsaturated alcohol represented by the above formula (3) or (4) and an organic lithium in an ether organic solvent.
78-20 ° C, preferably -20-0 ° C, usually 0-120
Minutes, preferably from 0 to 30 minutes, to give a lithium alkoxide.Then, the lithium alkoxide and acryl or methacryl chloride are usually reacted for -20 minutes.
It can be produced by reacting at ~ 80 ° C, preferably 0-70 ° C for about 1-5 hours.

The above-mentioned organic lithium includes, for example, methyllithium, n-butyllithium, i-butyllithium, s-butyllithium, t-butyllithium, phenyllithium and the like. Preferred among them are
Methyl lithium and n-butyl lithium.

Examples of the ether organic solvent include diethyl ether, di-n-propyl ether and di-n-propyl.
Butyl ether, tetrahydrofuran and the like.
Of these, preferred are diethyl ether and tetrahydrofuran.

[0011]

EXAMPLE 1 In a 200 ml three-necked flask, 49.0 g (0.1%) of 1,1,1-trifluoro-2-trifluoromethyl-3-buten-2-ol was added.
25 mol) and 22.1 g (0.25 mol) of methacrylic acid, and a condenser was attached to the upper part of the flask. While the flask was placed in an ice bath and the temperature in the flask was kept at 3 to 10 ° C., fuming sulfuric acid (SO ₃ : 30% by weight, 0.19 mol) was added dropwise little by little under reflux and stirring with a magnetic stirrer. Chloroform and water were added to the above reaction mixture and solvent extraction was performed, and a chloroform phase was recovered. Anhydrous sodium sulfate was added to the chloroform phase, dried, and distilled under reduced pressure to obtain 11.4 g of a product at 57 to 58 ° C./23 torr (16.6% yield). For this compound, ¹
H-NMR, infrared absorption spectrum, elemental analysis and MS
Was measured. The results are shown below. From this result, the compound obtained has the formula:

Embedded image It is recognized that it is a compound represented by these.

¹ H-NMR; solvent CCl ₄ , internal standard T
MS 1.9ppm (s, 3H, -C H 3) 5.7ppm (m, 4H, C H 2 = C H -,

Embedded image ) 6.1ppm (s, 1H,

Embedded image )

Infrared absorption spectrum; liquid film method FIG. ^{MS 262 (M +), 177} , 157, 137, 69 (· CF 3)

Example 2 In a 1000 ml three-necked flask, 50.0 g of 1,1,1-trifluoro-2-trifluoromethyl-3-buten-2-ol (20.0 g) was added.
5.8 mmol) and 350 ml of tetrahydrofuran.
A condenser was attached to the top of the flask. The flask was placed in an ice bath and the temperature in the flask was kept at 2 to 15 ° C., while refluxing and stirring with a magnetic stirrer, n-
121.1 g of a butyllithium / n-hexane solution (n-butyllithium: 15% by weight) (n-butyllithium: 2
8.3 mmol) was added dropwise. After completion of the dropwise addition, the ice bath was removed, and tetrahydrofuran 250
A solution of 29.6 g (28.3 mmol) of methacrylic chloride dissolved in ml was added dropwise. After dropping, further 1.3 hours, 60-64 ° C
And heated to reflux. After washing the above reaction mixture with water, the organic solvent phase was recovered. Anhydrous sodium sulfate was added to the organic solvent phase, dried and distilled under reduced pressure to obtain 38.8 g of a product at 58 ° C./23 torr (yield: 57.4%). This compound was subjected to ¹ H-NMR, infrared absorption spectrum, elemental analysis, and MS measurement in the same manner as in Example 1. As a result, it was confirmed that the compound was the same as that in Example 1.

Example 3 In a 5000 ml three-necked flask, 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol was added to 294.1.
g (1.41 mol) and 1500 ml of tetrahydrofuran,
A condenser was attached to the top of the flask. The flask was placed in an ice bath and the temperature in the flask was kept at 3 to 13 ° C., and the mixture was refluxed and stirred with a magnetic stirrer.
682.0 g of a butyllithium / n-hexane solution (n-butyllithium: 15% by weight) (n-butyllithium: 1.60%)
Mol) was added dropwise. After completion of the dropwise addition, while stirring at 5 to 15 ° C, methacrylic chloride 166.2 was added to tetrahydrofuran 1500 ml.
g (1.59 mol) was added dropwise. After completion of the dropwise addition, the ice bath was removed, and the mixture was heated at 40 to 58 ° C. for another 40 minutes. After washing the above reaction mixture with water, the organic solvent phase was recovered. Anhydrous sodium sulfate was added to the organic solvent phase and dried, followed by distillation under reduced pressure to obtain 267.8 at 61 ° C / 27 torr.
g (1.11 mol) of the product was obtained (69% yield). This compound was subjected to ¹ H-NMR, infrared absorption spectrum, elemental analysis, and MS measurement. The results are shown below. From this result, the compound obtained has the formula:

Embedded image It is recognized that it is a compound represented by these.

¹ H-NMR; solvent CCl ₄ , internal standard T
MS 1.9ppm (d, 3H, -C H 3) 3.2ppm (d, 2H, -C H 2 -) 5.2ppm (m, 3H, -C H = C H 2) 5.6ppm (m, 1H,

Embedded image ) 6.1ppm (d, 1H,

Embedded image )

Infrared absorption spectrum; liquid film method FIG. MS 276 (M ⁺ ), 231, 211, 190, 171, 145, 121, 101, 8
6, 69 (· CF ₃₎

[0018]

The fluorinated organic compound of the present invention has a trifluoromethyl group --CF ₃ in the molecule, and further has a highly reactive acryloxyl or methacryloxyl group at one end. And the other end has a vinyl group having high reactivity as described above. Therefore, by reacting with various compounds,
It is expected that a trifluoromethyl group can be introduced into these compounds, and that such compounds can be improved in water repellency, moisture resistance, compatibility with other fluorine materials, and the like. The fluorine-containing organic compound of the present invention is expected to be useful, for example, as an intermediate material for producing carbon functional silane and the like.

[Brief description of the drawings]

FIG. 1 is a graph showing an infrared absorption spectrum of a fluorine-containing organic compound synthesized in Example 1.

FIG. 2 is a graph showing an infrared absorption spectrum of a fluorinated organic compound synthesized in Example 3.

 ──────────────────────────────────────────────────の Continued on the front page (72) Hiromasa Yamaguchi 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Kenichi Fukuda Matsui, Usui-gun, Gunma Prefecture Tamachi Daito Hitomi 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (72) Inventor Kazutoshi Munezawa 1-10-10 Matsuida-cho Matsuida-cho Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone electronic material technology research Inside

Claims (3)

(57) [Claims] (1) Formula (1): (Wherein, R is a hydrogen atom or a methyl group, and n is an integer of 0 or 1). (2) Formula (2): (Wherein n is an integer of 0 or 1), and the fluorinated unsaturated alcohol is reacted with acrylic acid or methacrylic acid in the presence of a dehydrating agent. The method for producing a fluorine-containing organic compound according to the above. 3. The method according to claim 1, wherein the compound represented by the formula (2) is reacted with an organic lithium to form a lithium alkoxide, and then the lithium alkoxide is reacted with acryl chloride or methacryl chloride. 2. The method for producing a fluorine-containing organic compound according to item 1.