JPH0214346B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to a high yield, useful and simple process for preparing hydroxyalkyl perfluoroalkanesulfonamides. Water and oil repellents and surfactants having perfluoroalkyl groups have superior properties compared to other silicon-based and wax-based agents, and their uses have been expanded in recent years. The hydroxyalkyl perfluoroalkanesulfonamides of the present invention are essential and useful compounds as intermediates in the production process of fluorine-based water and oil repellents and surfactants. However, conventional methods for producing hydroxyalkyl perfluoroalkanesulfonamides have had many problems in terms of productivity, reaction operability, product quality, yield, and the like. For example, a method for producing a corresponding alcohol by reacting an alkali metal salt of perfluoroalkanesulfonamide with a halogenated alcohol (Japanese Patent Publication No. 1988-8838) is a process for producing an alkali metal salt of perfluoroalkanesulfonamide. Since it consists of a two-step reaction in which this is reacted with a halogenated alcohol, the reaction operation is complicated and requires a long reaction time, and at the same time, the yield is low and the product remains colored. Ta. Furthermore, a method for obtaining hydroxyalkyl perfluoroalcarsulfonamides by contacting perfluoroalkanesulfonamide with a cyclic carbonate or sulfite is described in JP-A-46-7264; Since there is a risk of bumping from the reaction tube accompanied by foaming, the amount charged has to be reduced, resulting in a low pot yield and low productivity. Furthermore, a method of reacting perfluoroalkanesulfonamide with an alkylene oxide in the presence of a basic organic compound or inorganic metal compound or a basic ion exchange resin catalyst includes:
There were problems such as the need to use alkylene oxide with low volatility and a low flash point, and the production of by-products from polymerization of alkylene oxide. Also known reactions for producing hydroxyalkyl perfluoroalkylsulfonamides, namely the reaction of perfluoroalkylsulfonyl fluoride with, for example, N-alkylethanolamine, involve competitive reactions of both the imino and hydroxyl groups with the sulfonyl halide, It cannot be carried out because it causes many side reactions. Furthermore, in JP-A-48-100439, Example 8
as C ₈ F ₁₇ SO ₂ NH ₂ 25 parts by weight (hereinafter referred to as parts),
Heat 150 parts of water, 1.4 parts of sodium hydroxide, 18.6 parts of ethylene chlorohydrin and 15 parts of dioxane.
Keep it at 80℃ and add 30 parts of water and sodium hydroxide in it.
Add dropwise a solution containing 5.4 parts of C ₈ F ₁₇ SO ₂ N―
A method for obtaining (CH ₂ —CH ₂ —OH) ₂ is described. The disadvantage of this method is that it requires 6 times the amount of water as a solvent by weight, as well as 3.4 times as much sodium hydroxide and 4.6 times as much ethylene chlorohydrin in terms of molar ratio as _compared to C ₈ F _{17 SO} 2 NH 2. Therefore, the reaction time is long, the yield is poor, and the productivity is low. In addition, foaming during the reaction is intense and there is always a danger of bumping.
Furthermore, in the compound represented by the general formula [], R
When perfluorosulfonamide with a large number of carbon atoms is used, it has the disadvantage that the reaction hardly progresses. The present inventors conducted intensive research in view of the above-mentioned drawbacks, and as a result, high-quality hydroxyalkyl perfluoroalkanesulfonamides were obtained, which are easy to operate, require a short reaction time, and have good yields. We have discovered a highly productive manufacturing method and completed the present invention. That is, the present invention provides (a) a basic compound, preferably an organic compound or an inorganic metal compound, and (b) a perfluoroalkylsulfonamide, preferably represented by the general formula [] (However, Rf represents a linear or branched perfluoroalkyl group having 3 to 18 carbon atoms, and R represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.) A compound [], and (c) Halogenated alcohol, preferably represented by the general formula ( ) (However, R ₁ to _{R 4} are hydrogen atoms or carbon atoms from 1 to
represents an alkyl group of 8 or X, where X represents a halogen atom. ) A hydroxyl compound characterized in that (d) water is preferably used in an amount of 20% by weight or less based on the total amount of (a), (b), (c), and (d) when reacting the compound []. Method for producing alkyl perfluoroalkanesulfonamides, and surfactants, water and oil repellents, working fluids, antifungal agents, and pharmaceutical ingredients containing hydroxyalkylperfluoroalkanesulfonamides obtained by such production methods. It provides: In the present invention, inorganic metal compounds that are basic during the reaction include inorganic metal compounds such as alkali metal oxides, hydroxides, carbonates, or phosphates, or alkaline earth metal oxides or hydroxides. Compounds and organic compounds exhibiting basicity include tertiary amines such as triethylamine, secondary metal amides, metal alcoholates, metal carboxylates, and alkali metal salts of the sulfonamides used, among others. Sodium hydroxide or potassium hydroxide is preferred. (b) The perfluoroalkylsulfonamide is preferably one defined by the general formula [], for example, C ₄ F ₉ SO ₂ NH ₂ , C ₄ F ₉ SO ₂ NH—CH ₃ ,
C ₅ F ₁₃ SO ₂ NH ₂ , C ₆ F ₁₃ SO ₂ NH―CH ₃ ,
C ₆ F ₁₃ SO ₂ NH―C ₃ H ₇ , C ₈ F ₁₇ SO ₂ NH ₂ ,
Examples include C ₈ F ₁₇ SO ₂ NH―CH ₃ and C ₈ F ₁₇ SO ₂ NH―C ₃ H ₇ . (c) The halogenated alcohol is preferably one defined by the general formula [], but for example,
ClCH ₂ CH ₂ OH, BrCH ₂ CH ₂ ―OH, ClCH ₂ ―
CH(OH) _―CH3 , _CH3 ―CHCl― _CH2 ―OH,
BrCH ₂ ―CH(OH)―CH ₃ , CH ₃ ―CHBr―
Examples include CH ₂ -OH. When R in the general formula [] is an alkyl group, the following general formula (However, R _f and R in the formula, and R ₁ , R ₂ ,
It is assumed that R ₃ and R ₄ are each as described above. ) is obtained, and on the other hand,
When R in the general formula [] is a hydrogen atom, the monoalcohol represented by the general formula [] or the general formula (However, R _f and R ₁ , R ₂ , R ₃ and R ₄ in the formula
are as described above, R ₅ , R ₆ ,
R ₇ and R ₈ represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms. ) is obtained. The amount of the basic organic or inorganic metal compound and the amount of the halogenated alcohol are preferably 0.5 to 2.0 times the gram equivalent of the perfluoroalkylsulfonamide, and if the amount is more or less than that, the reaction rate will be reduced. Or the yield will decrease. The reaction temperature may be room temperature, but preferably 60°C to 90°C. The amount of water as a reaction aid is 20% by weight of the total raw materials, (a) basic compound, (b) perfluoroalkylsulfonamide, (c) halogenated alcohol, and (d) water. % or less, but in a system without water, the reaction is extremely slow, and in the presence of a large amount of water, productivity decreases, such as a decrease in kettle yield and a slow reaction rate.
~15% by weight is preferred. One of the roles of water as a reaction aid is to provide a suitable field for the reaction by making the system creamy. That is, it is considered that perfluoroalkylsulfonamide having surface activity in the presence of a small amount of water forms micelles or a field similar to them, highly concentrating reactive species and promoting the reaction. The method for producing hydroxyalkyl perfluoroalkanesulfonamides of the present invention using this small amount of water as a reaction aid has dramatically higher productivity, higher quality products, and simpler reaction operations than conventional production methods. , and provide high yields. The hydroxyalkyl perfluoroalkanesulfonamides obtained according to the present invention can be used as water and oil repellents by increasing the molecular weight, and as surfactants, pharmaceuticals, agricultural chemicals, intermediates for dyes, and mold-proofing agents by adding a hydrophilic group or lipophilic group. used as agents, working fluids, and lubricating oil additives. Next, the present invention will be specifically explained with reference to Examples, where "part" indicates weight. Example 1 In a four-neck flask equipped with a stir bar, internal thermometer, and condenser, 104.2 parts of N-methyl perfluorooctane sulfonamide, sodium hydroxide
When 8.9 parts of ethylene chlorohydrin, 18.0 parts of ethylene chlorohydrin, and 15.0 parts of ion-exchanged water (equivalent to 10.3% by weight) were stirred at 80°C for 1 hour, 109.4 parts of the following formula of displayability were obtained: C ₈ F ₁₇ SO ₂ N (CH ₃ ) A hydroxyalkyl perfluoroalkanesulfonamide corresponding to CH ₂ CH ₂ OH was obtained. The composition of the product was confirmed by gas chromatography. Example 2 In a four-necked flask equipped with a stir bar, internal thermometer, and condenser, N-methyl perfluorooctane sulfonamide, sodium hydroxide, ethylene chlorohydrin, and ion-exchanged water were each added.
When the reaction was carried out at the proportions corresponding to experiment numbers 1 to 6 shown in column 1A of the table below and under the conditions shown in column B, the following formula C ₈ F ₁₇ SO ₂ N ( Hydroxyperfluorooctane sulfonamide corresponding to CH ₃ )CH ₂ CH ₂ OH was obtained. The composition of the product was confirmed by gas chromatography.

[Table] Example 3 In the same manner as in Example 1, 50 parts of perfluorooctane sulfonamide, 17.9 parts of ethylene chlorohydrin, 8.8 parts of sodium hydroxide, and 5.0 parts of ion-exchanged water were stirred at 80°C for 1 hour. place, 57
A hydroxyalkyl perfluoroalkanesulfonamide corresponding to the following formula C ₈ F ₁₇ SO ₂ N(CH ₂ CH ₂ OH) ₂ was obtained. The composition of the product was confirmed by gas chromatography. Comparative Example 1 Synthesis was carried out according to the reaction example of Example 8 of JP-A-48-100439, except that perfluorooctane sulfonamide was changed to N-methyl perfluorooctane sulfonamide, and all other conditions were met. . That is, in a four-necked flask equipped with a stirrer, an internal thermometer, and a condenser, 25 parts of N-methyl perfluorooctane sulfonamide, 150 parts of water, 1.4 parts of sodium hydroxide, and ethylene chlorohydrin were added.
18.6 parts of dioxane and 15 parts of dioxane were heated and kept at 80°C, and a solution of 5.4 parts of sodium hydroxide dissolved in 30 parts of water was added dropwise thereto. Finish the dripping in 2 hours,
Despite heating and stirring for an additional 6 hours, only 48% of the desired reaction product was obtained.

Claims (1)

[Claims] 1. A hydroxyl compound characterized by reacting (a) a basic compound, (b) a perfluoroalkylsulfonamide, and (c) a halogenated alcohol in the presence of (d) water. A method for producing alkyl perfluoroalkanesulfonamides. 2 (a) the basic compound is a basic organic compound or a basic inorganic metal compound, (b) the perfluoroalkylsulfonamide is a compound represented by the general formula [], (However, Rf represents a linear or branched perfluoroalkyl group having 3 to 18 carbon atoms, and R represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.) (c) Halogenated alcohol has the general formula It is a compound represented by [ ]. (However, R ₁ to _{R 4} are hydrogen atoms or carbon atoms 1 to 8
represents an alkyl group or X, where X represents a halogen atom. ) The method according to claim 1, characterized in that: 3 (d) Water is (a) a basic organic compound or inorganic metal compound, (b) a perfluoroalkylsulfonamide represented by the general formula [], (c) a halogenated alcohol represented by the general formula [] and
(d) Claim 1 or 2 characterized in that water is used in an amount of 20% by weight or less in the total amount of water.
The method described in section.