FLUORINE-CONTAINING AMINOSULFONATE

Abstract: A fluorine-containing aminosulfonate of the general formula R f -Q₁-N(R₁)-Q₂-N(R₂)-Q₃-SO₃M wherein R f represents a perfluorinated aliphatic group having 3 to 16 carbon atoms; Q₁ represents (CH₂) n in which h represents an integer of 1 to 6, ( CH₂CH₂Z) i in which Z represents -O- or -S-, and i represents an integer of 1 to 4, or a combination of these; Q₂ and Q₃ are identical or different and each represents (CH₂) i in which j represents an integer of 1 to 6, in which R₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or M represents a hydrogen atom, an alkali metal atom, an alkaline earth methal atom, or -N(H) m (R₄) n in which R₄ represents an alkyl group having 1 to 3 carbon atoms, and m and n represent 0 or an integer of 1 to 4 provided that m + n = 4; R₁ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; and R₂ represents a hydrogen atom, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, -Q₃SO₃M in which Q₃ and M are as defined, or (CH₂) k COOM in which M is as defined and k represents an integer of 1 to 4.

Description: FLUORINE-CONTAINING AMINOSULFONATE This invention relates to a novel fluorinecontaining aminosulfonic acid-type amphoteric compound characterized by containing a perfluorinated aliphatic group and an aminosulfonate group in the molecule. Amphoteric surface-active agents have recently attracted attention as general-purpose surfactants because they have superior compatibility with other kinds of surfactants having different ionic properties. Amphoteric surface-active agents containing a perfluoroalkyl group as a fluorinated aliphatic group have better surface-activating properties such as the ability to reduce surface tension and foamability than amphoteric surface-active agents containing an alkyl group. Attempts have therefore been made to apply these amphoteric surfactants to various uses in spite of their higher costs than the alkyl-containing amphoteric surfactants. Known fluorine-containing amphoteric surfactants contain nitrogen atoms quaternized with a methyl, ethyl or hydroxyethyl group, and are classified as betaine-type amphoteric surfactants. Frequently, these known betaine-type amphoteric surfactants cannot fully exhibit sufficient performance at a pH near their isoelectric point in regard to surface activating properties such as the ability to reduce surface tension, foamability, solubility in water and resistance to hard water. It is an object of this invention to provide an amphoteric surface-active agent free from these defects. As an amphoteric surface-active agent meeting the above object, the present invention provides a fluorine-containing aminosulfonate of the general formula Rf'Q1 N(Rl)-Q2-N(R2)-Q3-So3M [I) wherein R represents a perfluorinated aliphatic group having 3 to 16 carbon atoms; Q represents -+CH2t-h in which h represents an integer of 1 to 6, -iCH2CH2Z t in which Z represents -0- or -S-, and i represents an integer EMI2.1 or a combination of these (examples of preferred combinations are CH2)hSO2, EMI2.2 EMI2.3 and Q3 are identical or different and each represents sCH2bj in which j represents an integer EMI2.4 in which R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or EMI2.5 M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or -N(H)m(R4)n in which R4 represents an alkyl group having 1 to 3 carbon atoms, and m and n represent 0 or an integer of 1 to 4 provided that m + n = 4; R1 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; and R2 represents a hydrogen atom, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, -Q3SO3M in which Q3 and M are as defined, or SCH2AkCOGM in which M is as defined and k represents an integer of 1 to 4. In formula tIl, typical examples of Rf are linear, branched and/or cyclic (e.g. cyclohexyl) perfluoroalkyl and perfluoroalkenyl groups. Rf may also represent a group having an oxygen atom in the main chain, such as (CF3)2CFOCF2CF2- . Specific examples of the fluorine-containing aminosulfonate of general formula (I) are listed below. C8F17S02NH(CH2)3N(CH3)(CH2)3S03Na, C8F17SO2NH(CH2)3N(CH2CH2OH)(CH2)3SO3Na, C6F13S02N(CH3)(CH2)3N(C2H5)CH2CH(OH)CH2S03K, CF15C0NH(CH2)2N(CH3)(CH2)3S03Na, EMI2.6 C3F7OCF(CF3)CF2OCF(CF3)CF2CONH(CH2)3N(CH3)- (CH2)3S03Na, CF3CF2CF2[OCF(CF3)CF2)4OCF(CF3)CF2CONH- (CH2)3N(CH3)(CH2)2SO3K, EMI3.1 The fluorine-containing aminosulfonate of general formula [I) can be produced in a high yield by, for example, reacting a perfluoroalkylcarboxylic acid, a perfluoroalkylsulfonic acid or an acid halide or EMI3.2 in which X is a halogen atom, which is reactive and readily available, with a diamine of the formula HR1NQ2NR2H, and condensing the resulting fluorinecontaining amino compound RfQl NR1 -o 2NR2H with a compound of the formula Y03 SO 3M in which Y is OH or a halogen other than fluorine, preferably in the presence of an alkali. The intermediate fluorine-containing amino compound RfQl-NRl-02NR2H can also be produced by using another known method. For example, a fluorine-containing hydroxyamino compound of the formula RfB1-NR1-CH2CH(OH)CH2- NR2H is produced by converting an acid amide of the formula R O 1NR1H into its Na salt by using NaOCH3 or NaH, and reacting it with epichlorohydrin to form a fluorinecontaining epoxide of the formula EMI3.3 and then reacting it with an amine of the formula H2NHR2. Table 1 summarizes the foamabilities and surface tensions of aqueous solutions of some of the fluorinecontaining aminosulfonates of the invention. Table I EMI4.1 <tb> <SEP> 0.1% <SEP> aqueous <SEP> solution <tb> Fluorine-containing <SEP> aminosulfonate <tb> <SEP> Formability <SEP> (*1) <SEP> Surface <SEP> (*2) <tb> <SEP> tension <tb> <SEP> (Solution <SEP> (Solution <SEP> (dyne/cm) <tb> <SEP> in <SEP> distilled <SEP> in <SEP> sea <tb> <SEP> water) <SEP> water) <tb> C6F13SO2NH(CH2)3N(CH3)(CH2)3SO3Na <SEP> 192 <SEP> 220 <SEP> 16.4 <tb> C6F13SO2NH(CH2)3NH(CH2)3SO3Na <SEP> 217 <SEP> 216 <SEP> 15.9 <tb> C6F13SO2NH(CH2)3N(CH3)(CH2)2SO3Na <SEP> 188 <SEP> 192 <SEP> 15.8 <tb> C6F13SO2NH(CH2)3NH(CH2)2SO3Na <SEP> 210 <SEP> 195 <SEP> 15.8 <tb> C6F13S0NH(CH2)3N(CH3)- <SEP> 230 <SEP> 230 <SEP> 16.5 <tb> CH2CHCH2SO3Na <SEP> <tb> <SEP> OH <SEP> <tb> C6F13SO2NH(CH2)3NHCH2CHCH2SO3Na <SEP> 206 <SEP> 222 <SEP> 15.4 <tb> <SEP> OH <SEP> <tb> C6Fl3So2N(C3H7)(CH2)3N(cH3)- <SEP> 218 <SEP> 220 <SEP> 16.9 <tb> CH2CHCH2SO3Na <SEP> <tb> OH <SEP> <tb> C6F13SO2N(C3H7)- <SEP> 200 <SEP> 215 <SEP> 18.0 <tb> (CH2)3NHCH2,CHCH2SO3Na <SEP> <tb> <SEP> OH <SEP> <tb> C7F15CONH(CH2)3N(CH3)(CH2)3SO3Na <SEP> 220 <SEP> 220 <SEP> 16.0 <tb> parison <SEP> C6F13SO2NH(CH2)3#N(CH3)2- <SEP> <SEP> 110 <SEP> 70 <SEP> 21.6 <tb> <SEP> CH2COO# <tb> <SEP> 2 <tb> (*1) Ross-Miles method (250C) Height of foams immediately after agitation by liquid dropping. (*2) Wilhelmy method (25 C) (Solution in distilled water) A known betaine-type amphoteric surface-active agent, such as C8F17SO2NH(CH2)30N(CH3)2CH2COO in aqueous solution, undergoes phase separation at a pH of less than 8.0, and its surface-activating properties are markedly deteriorated. Hence, the pH must always be maintained at neutrality or a higher value in use, and this constitutes a drawback against its actual use. In contrast, it has been found that the compounds in accordance with this invention dissolve completely in water even under strong acidity represented by a pH of 2 for example, and their surface-activating properties are not deteriorated in any pH region, i.e. in any of acidity, neutrality and basicity. The stability of the compounds of this invention against changes in pH is very useful in practical applications. It has further been found that the compounds of this invention have very good calcium ion stability. Ca 2+ Examination of Ca stability by the improved Hardt method (B. G. Wilkes et al., Ind. Eng. Chem., Vol. 29, p. 1234, 1937) shows that the compounds of this invention form a complete solution in water having a hardness of at least 5,000 ppm (calculated as CaCO3) even at a pH of 8.0. In contrast, a known betaine compound, such as C6F13SO2NH(CH2)3+N(CH3)2CH2COO , begins to undergo phase separation when the water has a hardness of 1,300 ppm. It is difficult to elucidate theoretically such excellent surface-activating properties of the compounds of this invention. It is presumed however that these properties are ascribable to the hydrophobic effect based on the perfluoroalkyl group and the hydrophilic effect based on the aminosulfonate group. By utilizing the excellent surface-activating proper ties of the fluorine-containing aminosulfonate compounds of the invention, such as foamability, the ability to reduce surface tension, resistance to hard water, and dissolving stability against pH changes, they are useful in application to foam fire extinguishing agents, water film-forming fire extinguishing agents for oil fire, foaming agents, detergents, wetting agents, etc. They are also suitably applicable to levelling agents, paint additives, antifouling agents, oil repelling agents, plastics additives, antistatic agents, mold releasing agents, etc. releasing agents, etc. The following Examples illustrate the present invention more specifically. Example 1 EMI6.1 264g (3.0 moles) of N-methyl-1,3-diaminopropane and 400g of sufficiently dehydrated isopropyl ether were weighed into a 2-liter three-necked round-bottomed flask equipped with a cooling condenser and a stirrer in an atmosphere of nitrogen. With sufficient stirring, 422g (1.05 moles) of perfluorohexylsulfonyl fluoride was added dropwise at room temperature. The mixture was stirred at 50 C for 3 hours, and then the isopropyl ether was removed under reduced pressure. The yellow solid residue was dissolved in 500 ml of ethanol, and with stirring, gradually poured into 8 liters of distilled water. The resulting crystals were aged. The supernatant liwuid was removed by decantation, and decantation was performed three more times using 5 liters of distilled water each time. The crystals were collected by filtration, washed with distilled water, and dried at 700C under reduced pressure. The product had a sufficient purity for use in the subsequent reaction. The amount of the product yieldedlwas 446g. Elemental analysis: C H N Found (%): 25.5 2.4 5.9 Calculated (%): 25.5 2.3 6.0 IR spectrum: 1370 cm 1 (-S02N NMR spectrum (CD3OD solvent: TMS standard): 1.80 ppm (m, 2H), 2.65 ppm (s, 3H), 3.05 ppm (t, 2H), 3.26 ppm (t, 2H). EMI7.1 46g (0.098 mole) of N-(3-methylaminopropyl) perfluorohexyl sulfonamide and 250g of isopropyl alcohol were weighed into a l-liter four-necked round-bottomed flask equipped with a cooling condenser and a stirrer, and heated to form a solution. With vigorous stirring at 800C, 100 ml of an aqueous solution of 25.3g (0.12 mole) of sodium 2-bromoethanesulfonate and 100 ml of an aqueous solution of 4.sag (0.12 mole) of sodium hydroxide were simultaneously added dropwise to the solution. After the addition, the mixture was reacted under reflux at 80 to 90 0C for 10 hours. The isopropyl alcohol and water were distilled off under reduced pressure. The solid residue was dried at 500C under reduced pressure, and recrystallized from ethanol to give 60g of the captioned compound. Elemental analysis: C H N Found (%): 24.3 2.4 4.6 Calculated (%): 24.0 2.3 4.7 IR spectrum: 1370 cm 1 (-SO N( vas), 1080 cm1 2 (-S03Na NMR spectrum (D20 solvent: DSS standard): 1.80 ppm (m, 2H), 2.60 ppm (S, 3H), 3.10 ppm (m, 4H), 3.18 ppm (m, 4H). Example 2 Synthesis of EMI7.2 30g (0.064 mole) of N-(3-methylaminopropyl)perfluorohexyl sulfonamide and 180g of isopropyl alcohol were weighed into a 500 ml four-necked round-bottomed flask equipped with a cooling condenser and a stirrer, and heated to form a solution. With stirring at 80 C, 50 ml of an aqueous solution of 13.9 g (0.077 mole) of sodium 3-chloropropanesulfonate and 50 ml of an aqueous solution of 3.lg (0.077 mole) of sodium hydroxide were simultaneously added dropwise to the solution. After the addition, the mixture was reacted under reflux at 80 to 90 C for 10 hours. The isopropyl alcohol and water were distilled off under reduced pressure. The oily residue was dried with hot air at 500 C, and recrystallized from ethanol to give 28g of the captioned compouned. Elemental analysis: C H N Found (%): 25.3 2.8 4.6 Calculated (%): 25.4 2.6 4.6 IR spectrum: 1370 cm 1 (-SO vas), 1085 cm 1 (-SO2 no vs). 1085 cm-1 (-SO3Na vs). NMR spectrum (D2O solvent: DSS standard): 1.80 ppm (m, 2H), 2.10 ppm (m, 2H), 2.60 ppm (s, 3H), 2.98 ppm (m, 4H), 3.08 ppm (m, 4H). Example 3 EMI8.1 18g (0.032 mole) of N-(3-methylaminopropyl)- perfluorohexyl sulfonamide and 100g of isopropyl alcohol were weighed into a 500 ml four-necked flask equipped with a cooling condenser and a stirrer, and heated to form a solution. With stirring at 80 C, 50 ml of an aqueous solution of 7.4g (0.038 mole) of sodium 2-hydroxy3-chloropropanesulfonate and 50 ml of an aqueous solution of 1.5g (0.038 mole) of sodium hydroxide were simultaneously added dropwise to the solution. After the addition, the mixture was reacted under reflux at 80 to 90 0C for 10 hours. The isopropyl alcohol and water were distilled off under reduced pressure. The yellow solid residue was dried at 600C under reduced pressure, and recrystallized from a mixture of ethanol and ethyl acetate to give 15g of the captioned compound. Elemental analysis: C H N Found (%) 25.0 2.2 4.0 Calculated (%) 25.2 2.2 3.9 IR spectrum: 1372 cm 1 (-S02Nz 1080 cm (-SO3Na vs). NMR spectrum (D20 solvent: DSS standard): 1.82 ppm (m, 2H), 2.60 ppm (s, 3H), 2.95 ppm (m, 4H), 3.04 ppm (m, 4H), 4.34 ppm (m, 1H). Example 4 Synthesis of C6F13SO2NCH2CH2CH2NCH2CH2S03Na: - H H (1) Synthesis of C6F13SO2NCH2CH2CH2NH :- H 2 lllg (1.5 moles) of 1,3-diaminopropane and 3CÈ of fully dehydrated isopropyl ether were weighed in an atmosphere of nitrogen into a 2-liter three-necked round-bottomed flask equipped with a cooling condenser and stirrer. With sufficient stirring, 237g (0.59 mole) of perfluorohexyl sulfonyl fluoride was added dropwise at room temperature from a dropping funnel. The mixture was stirred at 50 C for 3 hours, and then the isopropyl ether was removed under reduced pressure. The oily residue was dissolved in 200 ml of ethanol, and gradually poured into 5 liters of distilled water with stirring. The resulting crystals were aged. The supernatant liquid was removed by decantation, and 1 liter of 0.5N aqueous sodium hydroxide solution was added to wash the crystals. Decantation was performed for three more times using 5 liters of distilled water each time. The crystals were collected by filtration, washed with distilled water and dried at 60 C under reduced pressure. There was obtained 268g of N-(3-aminopropyl)perfluorohexyl sulfonamide having a sufficient purity for use in the subsequent reaction. Elemental analysis: C H N Found (%): 23.8 1.9 6.0 Calculated (%): 23.7 2.0 6.1 IR spectrum: 1370 cm (-S02Nz vats). NMR spectrum (CD30D solvent; TMS standard): 1.76 ppm (m, 2H), 2.85 ppm (t, 2H), 3.20 ppm (t, 2H). (2) Synthesis of C6F13SO2NCH2CH2CH2NCH2CH2SO3Na: - H H 15g (0.033 mole) of N-(3-aminopropyl)perfluorohexyl sulfonamide and 100g of isopropyl alcohol were weighed into a 500 ml four-necked round-bottomed flask equipped with a cooling condenser and a stirrer, and heated to form a solution. With vigorous stirring at 800C, 30 ml of an aqueous solution of 8.4g (0.04 mole) of sodium 2-bromoethanesulfonate was added dropwise to the solution while maintaining the pH of the solution at 8-9 with a 2N aqueous solution of sodium hydroxide using a pH stat. (As shown in Examples 1, 2 and 3, an aqueous solution containing an equimolar amount of sodium hydroxide may be added dropwise at the same time as the aqueous solution of sodium 2-bromoethanesulfonate.) After the addition, the mixture was refluxed at 80 to 90 C for 10 hours. The isopropyl alcohol and water were distilled off under reduced pressure. The solid residue was dried at 50 0C under reduced pressure, and recrystallized from a mixture of ethanol and ethyl acetate to give 13g of the captioned compound. Elemental analysis C H N Found (%): 22.8 2.1 4.6 Calculated (%): 22.5 2.0 4.8 IR spectrum: 1370 cm (-SO N ';as), 1070 cm-1 (-SO3Na vs). NMR spectrum (D2O solvent: DSS standard): 1.77 ppm (m, 2H), 3.06 ppm (m, 4H) 3.12 ppm (m, 4H). Example 5 Synthesis of C - H H 15g (0.033 mole) of N-(3-aminopropyl)- perfluorohexyl sulfonamide and lOOg of isopropyl alcohol were weighed into a 500 ml four-necked round-bottomed flask equipped with a cooling condenser and a stirrer, and heated to form a solution. With stirring at 80 C, 30 ml of an aqueous solution of 7.2g (0.04 mole) of sodium 3chloropropanesulfonate and 30 ml of an aqueous solution of 1.5g of sodium hydroxide were simultaneously added dropwise to the solution. After the addition, the mixture was reacted under reflux at 80 to 900C for 9 hours. The isopropyl alcohol and water were distilled off under reduced pressure. The yellow solid residue was dried at 60 C under reduced pressure, and recrystallized from a mixture of ethanol and ethyl acetate to give 13.8g of the captioned compound. Elemental analysis: C H N Found (%): 23.8 2.2 4.9 Calculated (%) 24.0 2.3 4.7 IR spectrum: 1370 cm-1 (-SO2N# vas), 1070 cm-1 (-SO3Na vs). NMR spectrum (D20 solvent: DSS standard): 1.90 ppm (m, 2H), 2.05 ppm (m, 2H), 2.99 ppm (m, 4H), 3.11 ppm (m, 4H). Example 6 Synthesis of EMI11.1 15g (0.033 mole) of N-(3-aminopropyl)perfluorohexyl sulfonamide was dissolved under heat in 100g of isopropyl alcohol in a 500 ml four-necked roundbottomed flask equipped with a cooling condenser and a stirrer. With stirring at 80 C, 30 ml of an aqueous solution of 7.8g (0.04 mole) of sodium 2-hydroxy-3chloropropanesulfonate and 30 ml of an aqueous solution of 1.6g (0.04 mole) of sodium hydroxide were simultaneously added dropwise to the solution. The mixture was reacted under reflux at 80 to 90 0C for 10 hours. Then, the isopropyl alcohol and water were distilled off under reduced pressure. The orange-colored solid residue was dried at 600C under reduced pressure, and recrystallized from a mixture of ethanol and ethyl acetate to give 14.lg of the captioned compound. Elemental analysis: C H N Found (%): 23.4 2.2 4.7 Calculated (%) 23.4 2.3 4.5 IR spectrum: 1370 cm 1 (S02Nz N 1070 cm-1 (-SO3Na vs). NMR spectrum (D2O solvent: DSS standard): 1.88 ppm (m, 2H), 2.82 ppm (m, 4H), 3.12 ppm (m, 4H), 4.23 ppm (m, 1H). Example 7 Synthesis of EMI12.1 10g (0.017 mole) of sodium N-methyl-N-(N' perfluoroheXylsulfonyl-y-aminopropyl)-2-aminoethanesulfonate and 80g of fully dehydrated dimethyl sulfoxide were weighed in an atmosphere of nitrogen into a 200 ml three-necked round-bottomed flask equipped with a cooling condenser and a stirrer, and heated to form a solution. At 80 C, 4.0g (0.02 mole) of a 28% methanol solution of sodium methylate was added dropwise, and the mixture was heated to 1100C to distill off methanol. Then, 3.8g (0.02 mole) of n-propyl iodide was added dropwise. The reaction was carried out at 1100C for 6 hours, and the dimethyl sulfoxide was removed under reduced pressure. The yellow solid residue was dried at 70 C under reduced pressure, and recrystallized from ethanol to give 10.5g of the captioned compound. As the following results of NMR spectroscopy show, the tertiary nitrogen atom was not quaternized with n-propyl iodide in the above process. Elemental analysis: C H N Found (%): 28.3 3.2 4.2 Calculated (%) 28.0 3.1 4.4 IR spectrum: 2950 - 2860 cm 1 (-CH2-, -CH3 vas, ups), 1370 cm (-S02N, 1070 cm 1 (-SO3Na vs). NMR spectrum (D20 solvent: DSS standard): 0.87 ppm (t, 3H), 1.63 ppm (m, 2H), 1.80 ppm (m, 2H), 2.60 ppm (s, 3H), 3.10 ppm (m, 4H), 3.20 ppm (m, 6H). Example 8 Synthesis of EMI13.1 In a 500 ml four-necked round-bottomed flask equipped with a cooling condenser and a stirrer, 14.2g (0.021 mole) of N-(3-methylaminopropyl)-p-perfluorononenyloxybenzene sulfonamide was dissolved under heat in 100g of isopropyl alcohol. With stirring at 800C, 30 ml of an aqueous solution of 5.3g (0.025 mole) of sodium 2-bromoethanesulfonate and 30 ml of 1.0g (0.025 mole) of sodium hydroxide were simultaneously added dropwise to the solution. The mixture was reacted under reflux at 80 to 90 C for 10 hours, and then the isopropyl alcohol and water were distilled off under reduced pressure. The solid residue was dried at 600 C under reduced pressure, and recrystallized from a mixture of ethanol and ethyl acetate to give 16.0g of the captioned compound. Elemental analysis: C H N Found (%): 29.7 2.2 3.5 Calculated (%): 29.9 2.1 3.3 IR spectrum: 1370 cm 1 (-S02Nz 1070 cm-1 (-SO3Na vs), EMI14.1 IR spectrum (D20 solvent: DSS standard): 1.80 ppm (m, 2H), 2.65 ppm (s, 3H), 3.05 ppm (t, 2H), 3.26 ppm (t, 2H). Example 9 Synthesis of EMI14.2 In a 500 ml four-necked flask equipped with a cooling condenser and a stirrer, 12g (0.02 mole) of td- (3-methylaminopropyl)-2-perfluorooctylethanesulfonamide was dissolved under heat in 100g of isopropyl alcohol. With stirring at 80 C, 30 ml of an aqueous solution of 5.lg (0.024 mole) of sodium 2-bromoethanesulfonate and 30 ml of an aqueous solution of 0.96g (0.024 mole) of sodium hydroxide were simultaneously added dropwise to the solution. The mixture was reacted under reflux at 80 to 90 0C for 9 hours. Then, the isopropyl alcohol and water were distilled off under reduced pressure. The solid residue was dried at 60 C under reduced pressure, and recrystallized from a mixture of ethanol and ethyl acetate to give 12.7g of the captioned compound. Elemental analysis: C H N Found (%): 26.6 2.7 3.8 Calculated (%): 26.4 2.5 3.8 IR spectrum: 1370 cm 1 (-SO vas), ), 1070 cm-1 (-SO3Na vs). NMR spectrum (D20 solvent: DSS standard): 1.85 ppm (m, 4H), 2.60 ppm (s, 3H), 3.05 ppm (m, 6H), 3.18 ppm (m, 4H). Example 10 Synthesis of EMI14.3 In a 500 ml four-necked round-bottomed flask equipped with a cooling condenser and a stirrer, 14.5g (0.03 mole) of N-(3-methylaminopropyl)perfluoroheptanamide was dissolved under heat in 100g of isopropyl alcohol. With stirring at 800C, 40 ml of an aqueous solution of 7.6g (0.036 mole) of sodium 2-bromoethanesulfonate and 40 ml of an aqueous solution of 1.4g (0.036 mole) of sodium hydroxide were simultaneously added dropwise to the solution. The mixture was reacted under reflux at 80 to 90 C for 9 hours, and then the isopropyl alcohol and water were distilled off under reduced pressure. The solid residue was dried at 600C under reduced pressure, and recrystallized from a mixture of ethanol and ethyl acetate to give 16.3g of the captioned compound. Elemental analysis: C H N Found (%): 27.3 2.1 4.6 Calculated (%) 27.4 2.3 4.6 IR spectrum: 1650 cm (-CONs = amide I absorption band) 1070 cm 1 (-SO3Na vs). NMR spectrum (D2O solvent: DSS standard): 1.82 ppm (m, 2H), 2.60 ppm (s, 3H), 3.10 ppm (m, 4H), 3.19 ppm (m, 4H). Example 11 Synthesis of EMI15.1 (1) Synthesis of C6F13S0 2NCH2CH2CH 2NCH2CO0Na:- H H 15g (0.033 mole) of N-(3-aminopropyl)perfluorohexyl sulfonamide and 100g of isopropyl alcohol were weighed into a 500 ml four-necked round-bottomed flask equipped with a cooling condenser and stirrer, and heated to form a solution. With stirring at 80 C, 30 ml of an aqueous solution of 4.6g (0.04 mole) of sodium monochloroacetate and 30 ml of an aqueous solution of 1.5g (0.04 mole) of sodium hydroxide were simultaneously added dropwise to the solution. The mixture was reacted under reflux at 80 to 900C for 9 hours, and then the isopropyl alcohol and water were distilled off under reduced pressure. The yellow solid residue was dried at 60 0C under reduced pressure and recrystallized from ethanol to give 15.5g of the captioned compound. Elemental analysis: C H N Found (%): 24.6 1.8 5.2 Calculated (%) 24.6 1.9 5.2 IR spectrum: 1590 cm-1 (-COO #), -l 1370 cm 1 (-S02Nz vas). NMR spectrum (D20 solvent: DSS standard): 1.81 ppm (m, 2H), 3.00 ppm (t, 2H), 3.30 ppm (t, 2H), 4.18 ppm (s, 2E4.). (2) Synthesis of EMI16.1 In a 500 ml four-necked round-bottomed flask equipped with a cooling condenser and a stirrer, 15g (0.028 mole) of sodium N-(N'-perfluorohexylsulfonyl-y- aminopropyl)glycine was dissolved under heat in 100g of isopropyl alcohol. With stirring at 80 C, 40 ml of an aqueous solution of 7.lg (0.034 mole) of sodium 2bromoethanesulfonate and 40 ml of an aqueous solution of 1.4g (0.034 mole) of sodium hydroxide were simultaneously added dropwise to the solution. The mixture was reacted under reflux at 80 0C for 13 hours, and then the isopropyl alcohol and water were removed under reduced pressure. The yellow solid residue was dried at 60 0C under reduced pressure, and recrystallized from ethanol to give 9.7g of the captioned compound. Elemental analysis: C H N Found (%): 26.3 2.3 4.9 Calculated (%): 26.6 2.2 4.8 IR spectrum: 1590 cm1 (-COO0), 1370 cm (-S02Ns vas), 1070 cm-1 (-SO3Na vs). NMR spectrum (D2O solvent: DSS standard): 1.80 ppm (m, 2H), 3.06 ppm (m, 4H), 3.20 ppm (m, 4H), 4.10 ppm (s, 2H). Example 12 Synthesis of EMI17.1 15g (0.033 mole) of N-(3-aminopropyl)perfluorohexyl sulfonamide and 100g of isopropyl alcohol were weighed into a 500 ml four-necked round-bottomed flask equipped with a cooling condenser and a stirrer, and heated to form a solution. At 80 C, 20 ml of an aqueous solution of 8.4g (0.04 mole) of sodium 2bromoethanesulfonate was added gradually to the solution, and the mixture was stirred for 15 minutes. Then, 20 ml of an aqueous solution of 1.5g (0.04 mole) of sodium hydroxide was added, and the mixture was stirred for 30 minutes. The same operation as above was performed using the same amounts of the aqueous sodium 2-bromoethanesulfonate solution and the aqueous sodium hydroxide solution, and the mixture was reacted under reflux for 12 hours. The isopropyl alcohol and water were distilled off under reduced pressure. The yellow solid residue was dried at 60 0C under reduced pressure, and recrystallized three times from ethanol to give 8.3g of the coptic ed compound. Elemental analysis: C H N Found (%): 22.1 2.0 3.7 Calculated (%): 21.8 2.1 3.9 IR spectrum: 1370 cm (-SO vas), 1070 cm-1 (-SO3Na vs). NMR spectrum (D2O solvent: DSS standard): 1.81 ppm (m, 2H), 3.08 ppm (m, 6H), 3.17 ppm (m, 6H).

Claims: CLAIMS 1. A fluorine-containing aminosulfonate characterised by the general formula RfQ1N( Q1 -Q2-N(R2) -Q3-SO3M wherein Rf represents a perfluorinated aliphatic group of 3 to 16 carbon atoms; Q1 represents sCH2ph in which h represents an integer of 1 to 6, sCH2CH2zAi in which Z represents -0- or -S- and i represents an integer of 1 to EMI18.1 or a combination of these; Q2 and Q3 are identical or different and each represents -(-CH2-)-j in which j represents an integer of 1 to 6, EMI18.2 in which R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or EMI18.3 M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or -N(H)m(R4)n in which R4 represents an alkyl group having 1 to 3 carbon atoms, and m and n represent 0 or an integer of 1 to 4 provided that m + n = 4; R1 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; and R2 represents a hydrogen atom, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms1 -QeS03M in which Q3 and M are as defined, or XCH2+kCOOM in which M is as defined and k represents an integer of 1 to 4. 2. A fluorine-containing aminosulfonate according to claim 1 wherein Q1 is -(-CH2-)-hSO2-, -(-CH2CH2Z-)-jSO2-, EMI18.4 3. Use of a fluorine-containing aminosulfonate as claimed in claim 1 or 2 as an amphoteric surface-active agent.

Inventors: HASHIMOTO, YUTAKA, ITO, TADASHI, KAMEI, MASAYUKI, UMABA, TOSHIHIKO
Applicants: DAINIPPON INK AND CHEMICALS, INC., KAWAMURA INSTITUTE OF CHEMICAL RESEARCH
Application year: 1981
Main classification: C07C143
IPC codes: B01F17