JP4306981B2 - Cleaning agent or electrolyte solvent containing a compound having an alkoxy group - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The compound having an alkoxy group of the present invention can be used as an electrolyte solvent and a cleaning agent, and is useful as an intermediate for a raw material of a fluorine-containing resin, a pharmaceutical, an agrochemical, a surfactant and the like.
[0002]
[Prior art]
Fluorocarbons represented by CFC-113 have a great impact on the environment such as stratospheric ozone depletion and global warming, and their production and use are currently prohibited or restricted. Hydrofluorocarbons and hydrofluoroethers have been proposed as alternatives for the purpose of protecting the stratospheric ozone layer, but there are concerns about the impact on global warming.
[0003]
In addition, as a result of searching a database provided by ACS (American Chemical Society, Chemical Abstracts Service) as a compound having a similar structure to that of the present invention, the following similar compound (number indicates a CAS registration number) was found. No compounds and uses corresponding to the invention were found.
[0004]
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[0005]
[Problems to be solved by the invention]
To provide useful compounds with minimal environmental impact such as global warming and stratospheric ozone depletion.
[0006]
[Concrete means for solving the problem]
As a result of intensive studies, the present inventors have found that a target compound can be synthesized by alkoxylating fluorine-containing cyclopentenes with a predetermined amount of alkoxide or the like, and have completed the present invention.
[0007]
That is, this invention is a cleaning agent containing the compound represented by either of the following structure A-structure E.
[0008]
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[0009]
A characteristic of the alkoxy group-substituted compound obtained in the present invention is that it has a double bond in the molecule. Generally volatile fluorine compound is stable, so long atmospheric lifetimes, a significant impact on the environment such as global warming. However, in general, a compound having a multiple bond in the molecule is easily attacked by OH radicals, and thus has an advantage of a high decomposition rate in the atmosphere and less influence on global warming.
[0010]
The alkoxy group-substituted compound of the present invention can be used as an intermediate for pharmaceuticals, agricultural chemicals and the like, and can be subjected to known reactions for double bonds such as addition reaction, ozonolysis reaction, oxidation reaction and the like. For example, chlorine is added under light irradiation or in the presence of a catalyst such as iron, or fluorine diluted with an inert gas such as helium, argon, or nitrogen is added, or a hydrogen halide such as hydrogen chloride, fluoride is added. Hydrogen or the like can also be added. In addition, hydrogen such as palladium, platinum, ruthenium, and rhodium can be hydrogenated in a gas phase or a liquid phase using a catalyst.
[0011]
Further, by polymerizing the alkoxy group-substituted compound of the present invention, it can be a raw material for highly functional resins. Although the polymerization composition depends on the desires of those skilled in the art, it is recommended to polymerize with other monomers rather than polymerize alone, because a more functional resin can be produced.
[0012]
The alkoxy group-substituted compound of the present invention can be used in various applications alone or by blending an organic compound desired by those skilled in the art . This alkoxy group-substituted compound can synthesize a compound having an almost arbitrary boiling point of 106 ° C. or higher. That is, when a low-boiling compound is desired, it is preferable to use a compound in which only one methoxy group is substituted. When a high-boiling compound is desired, a plurality of alkoxy groups are introduced or an alkoxy having a long chain length is used. The purpose is achieved by substituting groups. Currently, existing hydrocarbon solvents are used as electrolyte solvents for lithium batteries and the like, but in the case of explosion due to overcharge, there is concern about the flammability of the solvent. However, since the compound of the present invention is halogen-substituted, it has an advantage of low combustibility.
[0013]
Further, it can be used as a cleaning agent alone or by blending alcohols such as methanol, ethanol, isopropanol and the like as desired. In particular, since the alkoxy group-substituted compound of the present invention has a π bond and an oxygen atom having a high electron density, the cleaning property is excellent as compared with conventional cleaning agents. Further, since it has a large number of fluorine atoms, it has a small surface tension and is suitable for precision cleaning .
[0014]
Important starting materials for these alkoxy group-substituted compounds include fluorine-containing cyclopentene and alkoxide. Instead of the alkoxide, alcohol and a base such as sodium hydroxide or potassium hydroxide can be used. It goes without saying that hydrocarbon alcohols are basic industrial raw materials, and fluorine-containing alcohols are widely marketed as starting materials for fluorine-containing compounds and functional alcohols. As the fluorine-containing cyclopentenes, octafluorocyclopentene is commercially available as a highly functional etching agent. 1,2-dichlorohexafluorocyclopentene can be obtained by fluorinating octachlorocyclopentene with hydrogen fluoride in the presence of a catalyst. 1-Chloroheptafluorocyclopentene and octafluorocyclopentene can be obtained by partially or entirely fluorinating 1,2-dichlorohexafluorocyclopentene with potassium fluoride in an aprotic organic solvent.
[0015]
A method for synthesizing the alkoxy group-substituted compound obtained in the present invention can be a method desired by those skilled in the art, but a simple method, that is, a reaction between an alkoxide and a fluorinated cyclopentene will be described.
[0016]
First, as a method of synthesizing an alkoxide, a method of reacting an alcohol with an alkali metal such as Li, Na, K, LiH, NaH, or KH or an alkali metal hydride can be given. These alkali metals and alkali metal hydrides have very high reactivity, and attention is required for operation when mass-producing them industrially. In that case, a method of obtaining an alkoxide by mixing and reacting an alcohol and a basic substance such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) is recommended. Although this reaction can be performed using an aqueous solution of a basic substance, since it is a competitive reaction between an alkoxy anion and a hydroxy anion, it is preferable to use as little water as possible.
[0017]
The reaction between the alkoxide and the fluorine-containing cyclopentene can be carried out without a solvent, but the use of a solvent is recommended in order to achieve the object in a high yield. The solvent is preferably an alcohol corresponding to the alkoxide. For example, the solvent in the case of CF ₃ CH ₂ ONa is CF ₃ CH ₂ OH, and the solvent in the case of (CF ₃ ) ₂ CHOK is (CF ₃ ) ₂ CHOH. The amount of the solvent used depends on the solubility of the alkoxide, but a range of 0.5 to 30 mol per 1 mol of the alkoxide is recommended. In addition to the alcohol, an inert solvent in the reaction such as hydrocarbons and ethers can be used together.
[0018]
As the reaction method, all the raw materials can be charged at one time and heated and stirred. However, the following method is recommended for synthesis with good yield. That is, first, a method in which an alkoxide solution is prepared by mixing an aqueous KOH solution and alcohol and then mixed with fluorine-containing cyclopentene is recommended. A method in which the solvent and the fluorinated cyclopentene are first charged and the alkoxide is added sequentially, or a method in which the solvent and the alkoxide are first charged and the fluorinated cyclopentene is sequentially added can be carried out.
[0019]
The reaction temperature depends on the reactivity of the substrate, but 0 ° C to 200 ° C is recommended. In addition, the reaction pressure depends on the vapor pressure of the raw material fluorine-containing cyclopentene, solvent, alcohol and the like. However, the pressure is not limited to this when a reflux tower is installed.
[0020]
Any container can be used as long as the acid and base have corrosion resistance. Since no significant corrosion is observed even when a container made of heat resistant glass or stainless steel is used, a container coated with these materials or fluororesins such as Teflon (R) or those materials is recommended. When octafluorocyclopentene is used as a raw material, a pressure-resistant container is recommended because the boiling point of this compound is 28 ° C.
[0021]
As a result of intensive studies by the present inventors, it has been found that the number of alkoxy groups introduced depends on the ratio of alkoxide to fluorine-containing cyclopentene. That is, when one alkoxy group is introduced into the molecule, the molar ratio between the alkoxide and the fluorine-containing cyclopentene is about 1, and when the two alkoxides are introduced, the molar ratio is about 2. . Similarly, when three or more are introduced, the corresponding molar ratio is appropriate.
[0022]
Moreover, deeper present inventors have made intensive studies, as a result, with respect to an alkoxy group substituted compounds of the present invention obtained by once alkoxylated fluorinated cyclopentene, by yet a different type of alkoxide, it is also possible to alkoxylated is there. By using this technique, an alkoxy group-substituted compound having a different kind of alkoxy group can be produced. By introducing different types of alkoxy groups, it is possible to control the SP value and the KB value, which are indices of solubility. That is, it is possible to design an optical storage medium dye such as CD-R, an electrolyte solvent such as a Li battery, a substrate for organic synthesis, a dirt of an object to be cleaned, and the like in accordance with the solute.
[0023]
【Example】
The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0024]
[Example 1]
A 250 cc glass round bottom flask equipped with a condenser was charged with 50 wt% NaOH aqueous solution (24 g) and 2,2,2-trifluoroethanol CF ₃ CH ₂ OH (90 g) and stirred. After cooling to 5 ° C. in an ice bath, 1,2-dichlorohexafluorocyclopentene (24.5 g) was added dropwise. After completion of the dropwise addition, the temperature was gradually raised in an oil bath to reflux the solvent. When refluxing was continued for 2 hours, a white salt precipitated. This solution was cooled in an ice bath, and it was confirmed that the liquid temperature reached 10 ° C., washed with 300 g of ice water and separated, and the organic layer (lower layer) was washed again with 300 g of water and separated. The lower layer organic matter was dried over anhydrous magnesium sulfate and analyzed by gas chromatography (FID). As a result, the area ratio of the compound of structure A was 97%. The result of analyzing this compound by NMR after precision distillation is shown. As a result of analysis by GC-MS, no fragment inconsistent with this structure was observed.
[0025]
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[0026]
¹ H-NMR 4.6 (q, 2H, —CH ₂ —), 4.2 (q, 4H, —CH ₂ —, —CH ₂ —).
^{19 F-NMR -75.0 (t,} 6F, CF 3 -, CF 3 -), -75.7 (t, 3F, CF 3 -), - 115.5 (m, 2F, -CF 2 -) , 127.0 (m, 2F, -CF 2 -).
[0027]
[Example 2]
NaOH (40 g) and 40 g of water were mixed to prepare 80 g of 50% NaOH aqueous solution. After cooling this solution to room temperature, it was charged into a SUS autoclave (1000 cc) together with CF ₃ CH ₂ OH (500 g) and stirred for 30 minutes. Then, it cooled until the internal temperature became 5 degreeC with the ice bath, and 212 g of octafluorocyclopentene was prepared. While stirring at a rate of 300 revolutions per minute, the temperature was gradually raised to 100 ° C. After 2 hours, the reaction solution was washed twice with ice water, and the organic layer was analyzed by gas chromatography. As a result, the area of the compound of structure B was 95%. The results of analysis by NMR after precision distillation are shown below. As a result of analysis by GC-MS, no fragment inconsistent with this structure was observed.
[0028]
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[0029]
¹ H-NMR 4.6 (qd, 2H, —CH ₂ —).
¹⁹ F-NMR -75.5 (t, 3F, CF _3- ), -116.3 (m, 4F, -CF _2- , -CF _2- ), -130.2 (bs, 2F, -CF ₂ ), -157.7 (bs, 1F, = CF-).
[0030]
[Example 3]
NaOH (40 g) and 40 g of water were mixed to prepare 80 g of 50% NaOH aqueous solution. The solution was cooled to room temperature, charged with 1, 1, 1, _{3, 3, 3-} hexafluoroisopropanol (CF ₃ ) ₂ CHOH (840 g) into an SUS autoclave (1000 cc) and stirred for 30 minutes. Then, it cooled until the internal temperature became 5 degreeC with the ice bath, and 212 g of octafluorocyclopentene was prepared. The temperature was gradually raised to 150 ° C. while stirring at a rate of 300 revolutions per minute. After 2 hours, the reaction solution was washed twice with ice water, and the organic layer was analyzed by gas chromatography. As a result, the area of the compound of structure C was 56%. The results of analysis by NMR after precision distillation are shown below. As a result of analysis by GC-MS, no fragment inconsistent with this structure was observed.
[0031]
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[0032]
¹ H-NMR 5.1 (m, 1H, —CH <).
¹⁹ F-NMR -74.5 (m, 6F, CF _3- , CF _3- ), -116.0 (m, 2F, -CF _2- ), -117.1 (m, 2F, -CF _2- ), -130.3 (m, 2F, -CF 2 -), -151.6 (m, 1F, = CF-).
[0033]
[Example 4]
NaOH (80 g) and 80 g of water were mixed to prepare 160 g of a 50% NaOH aqueous solution. After cooling this solution to room temperature, it was charged into a SUS autoclave (1000 cc) together with (CF ₃ ) ₂ CHOH (840 g) and stirred for 30 minutes. Then, it cooled until the internal temperature became 5 degreeC with the ice bath, and 212 g of octafluorocyclopentene was prepared. While stirring at a rate of 300 revolutions per minute, the temperature was gradually raised to 100 ° C. After 2 hours, the reaction solution was washed twice with ice water, and the organic layer was analyzed by gas chromatography. As a result, the area of the compound of structure D was 58%. The results of analysis by NMR after precision distillation are shown below. As a result of analysis by GC-MS, no fragment inconsistent with this structure was observed.
[0034]
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[0035]
¹ H-NMR 5.1 (m, 2H, —CH <, —CH <).
^{19 F-NMR -74.6 (bd,} 6F, CF 3 -, CF 3 -), -116.0 (bd, 2F, -CF 2 -), -117.2 (bd, 2F, -CF 2 - ), -130.4 (bs, 2F, -CF 2 -).
[0036]
[Example 5]
NaOH (20 g) and 20 g of water were mixed to prepare 40 g of a 50% NaOH aqueous solution. After cooling this solution to room temperature, it was charged into a SUS autoclave (1000 cc) together with CF ₃ CH ₂ OH (250 g) and stirred for 30 minutes. Then, it cooled in the ice bath until internal temperature became 5 degreeC, and the compound (112g) of the structure F was prepared. While stirring at a rate of 300 revolutions per minute, the temperature was gradually raised to 100 ° C. After 2 hours, the reaction solution was washed twice with ice water, and the organic layer was analyzed by gas chromatography. As a result, the area of the compound of structure E was 85%. The results of analysis by NMR after precision distillation are shown below. As a result of analysis by GC-MS, no fragment inconsistent with this structure was observed.
[0037]
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[0038]
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[0039]
¹ H-NMR 4.5 (q, 2H, —CH ₂ —), 4.0 (bs, 3H, CH ₃ —).
¹⁹ F-NMR -75.3 (t, 3F, CF _3- ), -111.9 (Bt, 2F, -CF _2- ), -112.7 (m, 2F, -CF _2- ), 129. _{8 (m, 2F, -CF 2} -).
[0040]
[ Reference Example 1 ]
Dye (copper II) 1, 2, 3, 4, 8, 9, 10, 11, 15, 16, 17, 18, 22, 23, 24, 25-hexa to 100 g of the compound of structure F described in Example 5 Decafluoro-29H, 31H phthalocyanine) 0.1 g was added, and the mixture was heated and stirred at 50 ° C. As a result of standing at room temperature for 24 hours, it was a clear solution and no precipitate was observed.
[0041]
[ Reference Example 2 ]
As a result of adding 0.1 g of a dye (nickel (II) phthalocyanine) to 100 g of the compound of structure G and conducting the same experiment as in Example 6, the solution was clear and no precipitation was observed.
[0042]
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[0043]
[ Reference Example 3 ]
1.129 g of solder flux was applied to a glass plate and heated at 120 ° C. for 10 minutes. This glass plate was put into a solution obtained by adding 50 g of isopropanol to 500 g of the compound of structure F, and washed with an ultrasonic cleaner for 5 minutes. Further, this glass plate was put in a solution of the new structure F alone, and finish ultrasonic cleaning was performed for 1 minute. As a result of measuring the weight of the glass plate after drying, no increase in mass of the glass plate was observed. This represents that the flux has been substantially removed.
[0044]
[Example 6 ]
A spectacle lens having water droplets attached thereto by washing with pure water was placed in a solution obtained by adding 50 g of methanol to 500 g of the compound of structure E. After ultrasonic cleaning for 2 minutes, steam cleaning was performed for 30 seconds, and hot air drying was performed at 120 ° C. As a result of visual inspection, no spots were observed.
[0045]
[Example 7 ]
A nut with attached mechanical oil was put into a solution obtained by adding 10 g of ethanol to 100 g of the compound of structure C, subjected to ultrasonic cleaning for 5 minutes, and dried in warm air at 120 ° C. for 10 minutes. As a result of visual inspection, the surface was clean.
[0046]
[Example 8 and Reference Example 4-5 ]
The solubility of LiAl (HFIP) ₄ which is an electrolyte for Li battery was measured. The results are shown in Table 1 . However, HFIP represents (CF ₃ ) ₂ CHOH.
[0047]
[Table 1]
[0048]
【The invention's effect】
The present invention can provide a novel and useful alkoxy group-substituted compound. In addition, a novel compound can be produced efficiently on an industrial scale using fluorine-containing cyclopentene and alcohol as raw materials.

Claims (2)

A cleaning agent comprising a compound represented by any one of the following structures A to E.
The solvent of the electrolyte for Li batteries containing the compound represented by either of the following structure A-structure H.