RU2005718C1 - FLUORINE-CONTAINING β-KETOSULFONIC ACIDS OR SALTS THEREOF AS SURFACTANTS FOR PROCESSES IN AQUEOUS MEDIA, AND METHOD FOR THEIR PREPARATION - Google Patents

Abstract

FIELD: surface-active agent for processes in aqueous media. SUBSTANCE: provided is fluorine-containing b-ketosulfonic acid derivatives of the following formula R_FCOCH₂SO₂OZ, wherein R_F is group C_nF_2n+1, n is 5-8; or C₆H₁₁ or CF₃O(CF₂CF₂O)_mCF₂, where m is 1-3; or C₃H₇O(CF(CF₃)CF₂O)_xCF(CF₃), wherein X is 0-2, Z is H, or their salts of ammonium, alkaline or alkaline earth metal, primary, secondary or ternary amines. Reagent 1: fluoralkylketone of the formula -R_FCOCH. Reaction conditions: in equimolar ratio and at temperatures of 20-50 C. EFFECT: increased efficiency.

Description

CF₂O)

- при х = 0,1,2;
Z = H или соль аммония, щелочного или щелочно-земельного металла или первичного, вторичного или третичного амина.The invention relates to the production of fluorine-containing sulfonic acids, namely, new fluorine-containing β-ketosulfonic acids and their salts of general formula I
R _F COCH ₂ SO ₂ OZ, (I) where R _F takes the values C _n F _{2n + 1} with n = 5-8; c - C ₆ H ₁₁ , CF ₃ O (CF ₂ CF ₂ O) _m CF ₂ - at m = 1-3;
C ₃ F ₇ O (

CF ₂ O)

- at x = 0,1,2;
Z = H or a salt of ammonium, an alkali or alkaline earth metal, or a primary, secondary or tertiary amine.

 Fluorine-containing β-ketosulfonic acids and their salts can be used as general-purpose surfactants (surfactants), i.e., in all areas associated with an increase in mass transfer processes and an increase in the efficiency of processes associated with surface phenomena (increased oil recovery in oil-bearing formations, fire extinguishing agents, emulsification and demulsification, imparting hydro- and oleophobic properties, electrolytic processes, components of biologically and physiologically active formulations, etc.).

 Structural analogues of fluorine-containing β-ketosulfonic acids, for example benzoylmethanesulfonic acid, are known. These compounds are prepared by reacting the corresponding ketone with a complex of sulfuric anhydride with dioxane or pyridine.

 These compounds are not surfactants.

 The known method for producing sulfonic acids does not allow to obtain the target products in a free state, because after processing the ketone with a complex of sulfuric anhydride with dioxane, and most often pyridine, a sulfonic acid salt is obtained. To separate sulfonic acid in an individual state, it must be purified, usually recrystallized.

 There is no information on the possibility of using free sulfuric anhydride to obtain β-ketosulfonic acids from aliphatic methyl-containing ketones.

CF

o___→
Известная перфторпропан-2-он-сульфокислота не является поверхностно-активным веществом.Also known is perfluoropropan-2-one-sulfonic acid, which is obtained by the interaction of pentafluoropropenol with sulfuric anhydride, followed by isomerization of a sulfuric acid ester into β-ketasulfonic acid (2) according to the scheme:
C

CF

o ___ →
Known perfluoropropan-2-one-sulfonic acid is not a surfactant.

 However, the preparation of β-ketosulfonic acids by this method is limited by the practical inaccessibility of polyfluorinated unsaturated alcohols.

 Fluorine-containing surfactants are known (3), for example, the “chromin” preparation (potassium perfluoro-4-ethylcyclohexyl sulfonate) and the “chromoxane” preparation (potassium perfluoro-4-methyl-3,6-dioxa octanesulfonate). Chromin at a concentration of 0.3% in a chromium plating electrolyte reduces surface tension from 72 mN / m to 30 mN / m, and a chromoxane preparation at a concentration of 0.1% to 14.6 mN / m.

 "Chromoxane" is a fairly effective surfactant, but the method of obtaining it is multi-stage, fire and explosive.

 The objective of the invention is to expand the range of highly effective surfactants by attracting a new class of compounds, as well as the development of a new and simple method for their preparation.

F₂O)

при x = 0,1,2; с серным ангидридом при 20-50^оС в эквимолярном соотношении и целевые сульфокислоты выделяют в свободном виде или нейтрализуют с получением соответствующих солей.The problem is solved by the proposed fluorine-containing β-ketosulfonic acids and their salts of the general formula (I), as well as by the method for their preparation, consisting in the interaction of methyl polyfluoroalkyl ketones of the general formula (II)
R _F COCH ₃ (II) where RF takes the values C _n F _{2n + 1} , c-C ₆ F ₁₁ , at n = 5-8; CF ₃ O (CF ₂ CF ₂ O) _m CF ₂ - at m = 1,2,3; C ₃ F ₇ O (

F ₂ O)

when x = 0,1,2; with sulfuric anhydride at 20-50 ^{° C} in an equimolar ratio and target sulfonic acid is isolated in free form or neutralized to give the corresponding salts.

R

C

В заявляемом способе вместо ненасыщенных спиртов - фенолов - используют кетоны, что исключает необходимость промежуточной стадии изомеризации. Принципиально способ получения заявляемых β-кетосульфокислот заключается во взаимодействии метилополифторалкилкетов общей формулы II в эквимолярном соотношении со свободным серным ангидридом при температуре 20-50^оС. Верхний предел температурного интервала проведения процесса определяется необходимостью более полного завершения реакции.The reaction is carried out according to the following scheme:

R

C

In the inventive method, instead of unsaturated alcohols - phenols - ketones are used, which eliminates the need for an intermediate stage of isomerization. In principle the inventive method for producing β-ketosulfokislot comprises reacting metilopoliftoralkilketov general Formula II in equimolar ratio with the free sulfur trioxide at a temperature of 20-50 ^C. The upper limit of the temperature range of the process is determined by the need for more complete reaction.

The starting methyl polyfluoroalkyl ketones are prepared by decomposing (polyfluoroacyl) malonate of the general formula R _F COCH (COOEt) ₂ , where R _F has the above meanings, or its triethylammonium salt of concentrated sulfuric acid with a volume ratio of malonate or its salt to sulfuric acid equal to 1: 1 with a gradual increase temperatures from 100 to 180 ^about C.

CF₂O)

при x = 0,1,2 являются новыми неописанными в литературе соединениями. Способ их получения описан в примерах 1-6.Ketones of the general formula II at R _F = CF ₃ O (CF ₂ CF ₂ O) _m CF ₂ - at m = 1,2,3 and
C ₃ F ₇ O (

CF ₂ O)

at x = 0,1,2 are new compounds not described in the literature. The method for their preparation is described in examples 1-6.

To obtain salts of fluorine-containing β-ketosulfonic acids, a neutralization reaction was used with the corresponding alkalis or tertiary amines under ordinary conditions, for example, NH ₃ , NaOH, KOH, N (C ₂ H ₅ ) ₃ , etc.

EXAMPLE Example 1. Upon heating, the mixture of equal volumes of concentrated sulfuric acid and 43.8 g (0.1 mmol) of perfluoro-3,6-dioksageptanoildietilmalonata while gradually raising the temperature from 100 to 180 ^C. 22.4 g of ( 76%) methylperfluoro-2,5-dioxahexylketone CF ₃ OCF ₂ CF ₂ OCF ₂ COCH ₃ with so on. 115 ^about S.

 Found,%: C 24.68; H 1.33; F 56.12.

C ₆ H ₃ F ₉ O.

 Calculated,%: C 24.51; H 1.02; F 58.15.

Nuclear Magnetic Resonance Spectrum H, δ, ppm: 2.11 C (CH ₃ ).

PRI me R 2. Analogously to example 1 of 55.4 g (0.1 mol) of perfluoro-3,6,9-trioxadecanoyl diethyl malonate receive 33.2 g (81%) of methylperfluoro-2,5,8-trioxanonyl ketone CF ₃ O (CF ₂ CF ₂ O) ₂ OCF ₂ COCH ₃ s bp 95-96 ^about With 100 mm RT. Art.

 Found,%: C 23.35; H 0.52; F 59.68.

C ₈ H ₃ O ₄ F ₁₃ .

 Calculated,%: C 23.43; H 0.74; F 60.23.

Nuclear Magnetic Resonance Spectrum H, δ, ppm: 2.06 C (CH ₃ ).

PRI me R 3. Analogously to example 1 of 33.5 g (0.05 mol) of perfluoro-3,6,9,12-tetraoxatridecanoyldiethyl malonate receive 20.6 g (78%) of methylperfluoro-2,5,8, 11-tetraoxadodecyl ketone CF ₃ O (CF ₂ CF ₂ O) ₃ OCF ₂ COCH ₃ bp 70-71 ^about With 10 mm RT. Art.

 Found,%: C 22.95; H 0.62; F 60.25.

C ₁₀ H ₃ O ₅ F ₁₇
Calculated,%: C 22.83; H 0.57; F 61.39.

H NMR spectrum, δ, ppm: 2.08 C (CH ₃ ).

PRI me R 4. Analogously to example 1 of 47.22 g (0.1 mol) of perfluoro-3-oxa-2-methylhexanoyl malonic acid diethyl ether, 27.9 g (85%) of methylperfluoro-2-oxa-1 are obtained -methylpentylketone C ₃ F ₇ OCF (CF ₃ ) COCH ₃ with so kip. 94-95 ^about S.

 Found,%: C 26.00; H 1.01; F 62.49.

C ₇ H ₃ F ₁₁ O ₂
Calculated,%: C 25.63; H 0.92; F 63.70.

Nuclear Magnetic Resonance Spectrum H, δ, ppm: 2.12 g (I = 6 Hz, CH ₃ ).

PRI me R 5. Analogously to example 1 of 63.8 g (0.1 mol) of diethyl ether perfluoro-3,6-dioxa-2,5-dimethylnonanoylmalonic acid receive 39.1 (79%) methylperfluoro-2, 5-dioxa-1,4-dimethioctylketone C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COCH ₃ with so on. 151-2 ^about C.

 Found,%: C 24.68; H 1.06; F 64.42.

 Calculated,%: C 24.31; H 0.61; F 65.37.

Spectrum, NMR′H, δ, ppm 2.15 d (I = 6 Hz, CH ₃ ).

PRI me R 6. Analogously to example 1 of 40.2 g (0.05 mol) of diethyl ether perfluoro-3,6,9-trioxo-2,5,8-trimethyldodecanoyl-yl malonic acid receive 29.9 g ( 90.5%) methyl-2,5,8-trioxa-1,4,7-trimethylundecanyl ketone C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF3) COCH ₃ with so on . 87-8 ^about With at 15 mm RT. Art. Found,%: C 24.00; H 0.53; F 66.02
C ₁₃ H ₃ F ₂₃ O ₄
Calculated,%: C 23.65; H 0.46; F 66.19.

Nuclear Magnetic Resonance Spectrum H, δ, ppm: 2.09 d (I = 6 Hz, CH ₃ ).

PRI me R 7. Obtaining 1,1-dihydroperfluorooctanone-2-sulfonic acid. To 36.2 g (0.1 mol) metilperftorgeksilketona at 40-50 ^{° C} was added dropwise 8.0 g (0.1 mol) of sulfur trioxide. After completion of the reaction, the mixture crystallized. Subsequent sublimation of the reaction mass in vacuum 2 mm RT. Art. at 50-60 ^{° C} is obtained 32.2 g (73%) of the title compound of m. pl. 102 ^about S.

Found,%: C 21.93; H 0.75; S 7.10; F 53.22
C ₈ H ₃ F ₁₃ O ₄ S.

 Calculated,%: C 321.73; H 0.68; S 7.25; F 55.86.

H NMR spectrum, 50% in CH ₃ CN, δ, ppm: 4.52 s (CH ₂ ): 12.00 s (OH).

PRI me R 8. Obtaining 1,1-dihydroperfluorodecanone-2-sulfonic acid. To 46.2 g (0.1 mmol) metilperftoroktilketona at 40-50 ^{° C} was added dropwise 8.0 g (0.1 mol) of sulfur trioxide. After completion of the reaction, the mixture crystallized. Subsequent sublimation of the reaction mass in vacuum 2 mm RT. Art. at 80-90 ^{° C} is obtained 44.4 g (82%) of the title compound of m. pl. 116-117 ^about S.

 Found,%: C 21.93; H 0.63; S 5.47.

C ₁₀ H ₃ F ₁₇ O ₄ S
Calculated,%: C 22.15; H 0.56; S 5.91.

¹ H NMR Spectrum (50% in CH ₃ CN), δ. ppm; 4.80 s (CH ₂ ; 14.0 s (OH).

PRI me R 9. Obtaining 1,1-dihydroperfluorocyclohexylethanone-2-sulfonic acid. To 32.4 (0.1 mol) metilperftortsiklogeksilketona at 30-40 ^{° C} was added dropwise 8.0 g (0.1 mol) of sulfur trioxide. After completion of the reaction, the mixture crystallized. Subsequent sublimation in vacuum of 2 mm RT. Art. at 50-60 ^{° C} is obtained 30.3 g (75%) of the title compound of m. pl. 96 ^about S.

 Found,%: C 32.71; H 0.82; S 8.03; F 50.42.

C ₈ H ₃ F ₁₁ O ₄ S.

 Calculated,%: C 23.77; H 0.75; S 7.93; F 51.71.

¹ H NMR spectrum (50% in CH ₃ CN), δ, ppm: 4.46 d (CH ₂ ,] = 4 Hz): 12.80 s (OH).

PRI me R 10. Obtaining 1,1-dihydroperfluoro-4,7-dioxahexanone-2-sulfonic acid. To 29.4 g (0.1 mol) of 2,5-metilperftor dioksageksilketona at 20-30 ^{° C} was added dropwise 8.0 g (0.1 mol) of sulfur trioxide. Subsequent distillation of the reaction mixture in vacuo yields 27.3 g (73%) of the target compound with mp. 145 ^about With 1 mm RT. Art. , n _D ²³ 1.3570; d ₄ ²³ 1.842.

 Found,%: C 19.01; H 1.02; F 44.35.

C ₆ H ₃ F ₉ O ₆ S.

 Calculated,%: C 19.26; H 0.81; F, 45.70.

¹ H NMR spectrum, ppm: 4.57 s (CH ₂ ); 13.50 s (OH).

PRI me R 11. Obtaining 1,1-dihydroperfluoro-4,7,10-trioxaundecanone-2-sulfonic acid. To 41.0 g (0.1 mol) metilperftor-2,5,8-trioksanonilketona at 20-30 ^{° C} was added dropwise 0.01 g, 8.0 mol sulfur trioxide. Subsequent sublimation of the reaction mixture in vacuo give 35.8 g (73%) of the target compound with so on. 168-173 ^about With at 1 mm RT. Art.

Found,%: C 19.02; H 0.83; F 48.33;
C ₈ H ₃ F ₁₃ O ₇ S.

 Calculated,%: C 19.59; H 0.61; F, 50.41.

¹ H NMR spectrum, δ, ppm: 4.50 s (CH ₂ ); 12.90 s (OH).

EXAMPLE Example 12. 26.3 g (0.05 mol) of the ketone prepared as described in Example 3, at 20-30 ^{° C} was added dropwise 4.0 g (0.05 mol) of sulfur trioxide. Subsequent distillation of the mixture in vacuo gives 27.9 g (92%) of 1,1-di-H-perfluoro-4,7,10,13-tetraoxatetradecanone-2-sulfonic acid with so on. 195-8 ^about With 1 mm RT. Art.

 Found,%: C 20.02; H 0.75; F 52.10.

C ₁₀ H ₃ F ₁₇ O ₈ S.

Calculated,%: C 19.82; H 0.50; F 53.29
¹ H NMR spectrum, δ, ppm: 4.50 s (CH ₂ ); 12.90 s (OH).

PRI me R 13. Obtaining 1,1-dihydroperfluoro-4-oxa-3-methylhectanone-2-sulfonic acid. To 32.8 g (0.1 mol) metilperftor-2-oxa-4-metilpentilketona at 30-40 ^{° C} was added dropwise 8.0 g (0.1 mol) of sulfur trioxide. Subsequent distillation of the reaction mixture in vacuo give 33.5 g (82%) of the target compound with so on. 165-170 ^about With 1 mm RT. Art. n _D ^23, 1.3509; d ₄ ²³ 1.848.

 Found,%: C 20.12; H 0.92; F 49.60; S 7.33.

C ₇ H ₃ F ₁₁ O ₅ S.

 Calculated,%: C 20.59; H 0.74; F 51.20; S 7.86.

¹ H NMR spectrum, δ, ppm: 4.70 M (CH ₂ ); 11.55 s (OH).

PRI me R 14. Obtaining 1,1-dihydroperfluoro-4,7-dioxa-3,6-dimethyldecanone-2-sulfonic acid. To 49.4 g (0.1 mol) metilperftor-2,5-dioxa-1,4-dimetiloksilketona added dropwise at 40-50 ^C. 8.0 g (0.1 mol) of sulfur trioxide. Subsequent distillation of the reaction mass in vacuo get 48.8 g (85%) of the target compound with so bales. 170-175 ^about With 1 mm RT. Art. d ₄ ²⁰ 1.855.

 Found,%: C 21.11; H 0.63; F 53.60.

C ₁₀ H ₃ F ₁₇ O ₆ S.

 Calculated,%: C 20.92; H 0.53; F 53.25.

¹ H NMR spectrum, δ, ppm: 4.50 br. s (CH ₂ ); 11.40 s (OH).

PRI me R 15. To 33.0 g (0.05 mol) of the ketone obtained as described in example 6 at 20-30 ^about With add dropwise 4.0 g (0.05 mol) of sulfuric anhydride. Subsequent distillation of the mixture in vacuo gives 31.8 g (86%) of 1,1-di-H-perfluoro-4,7,10-trioxa-3,6,9-trimethyltridecanone-2-sulfonic acid with so on.

 Found,%: C 21.63; H 0.58; F 58.60.

C ₁₃ H ₃ F ₂₃ O ₇ S
Calculated,%: C 21.10; H 0.41; F 59.04.

¹ H NMR spectrum, δ, ppm: 4.50 br. s (CH ₂ ); 11.40 s (OH).

 Example 16. To a solution of 5.74 g (0.01 mol) of the sulfonic acid described in Example 14 in 0.5 ml of methanol was added 0.54 g (0.01 mol) of ammonium chloride. After evaporation of the solvent in vacuo, the residue is reprecipitated from 20 ml of toluene, 5.82 g (98.5%) of the ammonium salt of sulfonic acid are obtained in the form of a colorless transparent paste.

 Found,%: C 20.19; H 0.98; N, 2.03.

C ₁₀ H ₆ NO ₆ F ₁₇ S.

 Calculated,%: C 20.32; H 1.02; N, 2.37.

PRI me R 17. To a solution of 5.74 g (0.01 mol) of the sulfonic acid described in example 14 in 20 ml of ethanol is added a solution of 0.40 g (0.01 mol) of sodium hydroxide in 5 ml of ethanol. After evaporation of the solvent in vacuo and heating ^to 50 ° C is obtained 5.96 g (≈100%) of the sodium salt of sulfonic acid as a white paste.

 Found,%: C 20.66; H 0.45.

C ₁₀ H ₂ O ₆ F ₁₇ SNa
Calculated,%: 20.15; H 0.34.

 PRI me R 18. Similarly to the preparation of the sodium salt described in example 17, from 5.74 g (0.01 mol) of sulfonic acid and 0.56 g (0.01 mol) of potassium hydroxide, 6.10 g (99 , 6%) potassium salt of sulfonic acid in the form of a white paste.

 Found,%: C 20.03; H 0.53.

C ₁₀ H ₂ F ₁₇ O ₆ SK.

 Calculated,%: C 19.62; H 0.53.

 Example 19. To a solution of 5.74 g (0.01 mol) of the sulfonic acid described in Example 14 in 20 ml of methylene chloride, 1.01 g (0.01 mol) of triethylamine was added. After distilling off the solvent in vacuo, 6.76 g (≈100%) of the triethylammonium salt of the sulfonic acid are obtained in the form of a clear, light yellow, very viscous liquid.

 Found,%: C 29.11; H 2.33; N, 2.16.

C ₁₆ H ₁₈ NF ₁₇ O ₆ S.

 Calculated,%: C 29.46; H 2.67; N, 2.07.

 The inventive compounds according to examples N 7-19 were tested for the possibility of using them as surfactants. It was found that all investigated compounds have the ability in a concentration of 0.1 wt. % reduce the surface tension of water to 14-15 mN / m. Among them, 1,1-dihydroperfluoro-4,7-dioxa-3,6-dimethyldecanon-2-sulfonic acid, which at a concentration of already 0.05 wt. % reduces the surface tension of water to 13.4 mN / m.

 It was found that all of the above surfactants are characterized by high efficiency in relation to solutions of chromium electrolytes. So when, under standard conditions, the sulfonation of chromic acid described in Example 14 is introduced into the electrolyte, the desired effect is achieved when the concentration is 20 times lower than the known, most effective surfactant - “chromoxane”, that is, the surfactant consumption decreases from 100 mg / l to 5 mg / l.

 Thus, the proposed technical solution allows to obtain a new class of fluorine-containing surfactants with a particularly low value of surface tension, which will dramatically increase the efficiency of using surfactants in known processes and, in addition, may open up new possibilities for application.

 The proposed method is characterized by the simplicity of the process, one-stage, high yield of target products, the rejection of complexing agents of sulfuric anhydride (dioxane, pyridine). (56) Gilbert, E. B. Sulfonation of Organic Compounds. M.: Chemistry, 1969, p. 46.

 Becker R.A. et al. ZhORKh, vol. II, no. 8. 1975, p. 1601-1607.

 Maksimov B.N. et al. Handbook. Organofluorine industrial products. Chemistry. 1990. p. 394, 396.

Claims (2)

1. Fluorine-containing β-ketosulfonic acids of the general formula
R _F COCH ₂ SO ₂ OZ,
where R _F is the group C _n F _{2n + 1} with n = 5 - 8;
or c = C ₆ H ₁₁ ,
or CF ₃ O (CF ₂ CF ₂ O) _m CF ₂ at m = 1 - 3,
or

at x = 0 - 2; Z - H
or their salts of ammonium, alkaline, alkaline earth metal, primary, secondary or tertiary amine, as surface-active substances for processes occurring in aqueous media. 2. A method of obtaining a fluorine-containing β-ketosulfonic acid of the General formula
R _F COCH ₂ SO ₂ OZ,
where R _F is a group C _n F _{2n + 1} at n = 5 - 8, or c = C ₆ H ₁₁ , or CF ₃ O (CF ₂ CF ₂ O) _m CF ₂ at m = 1 - 3;
or

at x = 0 - 2;
Z - H
or their salts of ammonium, an alkaline, alkaline earth metal, primary, secondary or tertiary amine, characterized in that methyl polyfluoroalkyl ketone of the general formula
R _F COCH ₃ ,
where R _F has the indicated meanings,
subjected to interaction with sulfuric anhydride in an equimolar ratio at a temperature of 20 - 50 ^o With the subsequent isolation of the target product in free form or in the form of salt.