KR20150000576A - New pfos alternatives and preparing method thereof - Google Patents

Abstract

The present invention relates to a novel sulfonic acid derivative substituting for perfluorooctanesulfonic acid (PFOS) and synthesis thereof. The sulfonic acid derivative is denoted by chemical formula (1). In the chemical formula (1), R^f is a formula, X is an independent hydrogen atom or fluorine, n is integer between 0 and 3, and R is a metal atom, ammonium, or alkyl-ammonium. The sulfonic acid derivative has proper and good activities such as a significant biodegradability and surfactant in terms of environment, public health and industry.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel PFOS substitute material,

The present invention relates to fluorinated sulfonic acid derivatives as substitutes for perfluorooctanesulfonic acid (PFOS) and their synthesis, and more particularly to a fluorinated sulfonic acid derivative which reduces the number of fluorine atoms in perfluorooctanesulfonic acid, A novel sulfonic acid derivative exhibiting good activity, and a process for producing the same.

BACKGROUND ART Perfluoroalkyl materials have been detected in all kinds of water, animals and human blood in the world, among which perfluorooctanesulfonic acid (PFOS) has been found to be the most prevalent in humans. PFOS and perfluorooctanoic acid (PFOA) -related materials are used in many applications because they exhibit special properties including heat resistance, chemical resistance and abrasion resistance, and are also used for surface treatment. The fluorinated surfactants are superior to the hydrogenated surfactants because of their low surface micellar concentration (CMC) values and low surface tension. Fluorine-based surfactants are used for commercial stain-proofing agents, fire-extinguishing agents for fire extinguishers, paints, leather, paper coatings, photographic emulsions, aircraft working fluids, pharmaceuticals and electroplating. While the inherent properties of PFOS-related materials are valuable for industrial and consumer applications, the release of these non-degradable compounds into the environment has proven to be a serious issue from a global perspective. Thus, despite the fact that fluorinated surfactants are common in the environment and humans inevitably have to use them, PFOS derivatives have been used for POPs since May 2009 due to persistence, toxicity and bioaccumulation. The Stockholm Convention [Rayne, S .; Forest, K .; Friesen, KJ Journal of Environmental Science and Health, Part A: Toxic / Hazardous Substances and Environmental Engineering, 2008 , 43 , 1391-1401, Rayne, S .; Forest, K .; Friesen, KJ Journal of Environmental Science and Health, Part A : Toxic / Hazardous Substances and Environmental Engineering , 2009 , 44 , 866-879, Peden-Adams, MM; Keil, DE; Romano, T .; Mollenhauer, MAM; Fort, DJ; Guiney, PD; Houde, M .; Kannan, K. Reproductive Toxicology 2009 , 27 , 414-414 ).

Thus, PFOS substitutes with reduced toxic effects remain in the spotlight while still retaining their activity. Recently, a great improvement has been made in the study of biodegradable / non-bioaccumulative PFOS replacement compounds. These amphoteric species are composed of a perfluorinated chain, which is a hydrophilic group, and a hydrophilic group, which is mainly a sulfonic acid group or a carboxylic acid group. Generally, PFOS has been produced by an electrochemical overfire process, a short-chain polymerization of vinylidene fluoride, or a radical copolymerization of vinylidene fluoride and 3,3,3-trifluoropropene.

The hyperpolarised chain can not be degraded under enzymatic or metabolic degradation conditions and therefore remains for a longer period of time. Surfactants can be expected to be highly degradable when they have significant degradation points that can be degraded by enzymatic or chemical modification of the structure of these compounds. Scientific research has shown that the industry is also active in this area, such as 3M, which synthesizes the first surfactant with a C ₄ F ₉ chain at one end [Lehmler, JH Chemosphere 2005 , 58 , 1471-1496].

[Patent Document 1] Korean Registered Patent No. KR0932415 (Merck Patents GmbH), December 9, 2009

With these in mind, the present inventors have designed, synthesized, and characterized PFOS substitution compounds capable of decomposing by reducing the number of fluorine atoms in the surfactant PFOS and introducing conventional hydrocarbons.

It is therefore an object of the present invention to prepare novel sulfonic acid derivatives which can replace the surfactant perfluorooctanesulfonic acid (PFOS).

It is still another object of the present invention to provide a method for producing the novel sulfonic acid derivative.

In order to achieve the above object, the present invention provides a novel sulfonic acid derivative represented by the following formula (1):

Wherein R &_lt; _f >

, X is independently a hydrogen atom or a fluorine atom, n is an integer of 0 to 3, and R is a metal atom, ammonium or alkylammonium.

In one embodiment of the present invention, X in the formula (1) is a fluorine atom.

In one embodiment of the invention, R of Formula (1) is _{Li, Na, K, NH 4} , (C 2 H 5) 4 N and _{(CH 3) 2 (C 10} H 21) the group consisting of ₂ N . ≪ / RTI >

In one embodiment of the present invention, the sulfonic acid derivative is 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonic acid (n = 3), 5,5,6, Sulfonic acid (n = 1) and derivatives of 5,5,5-trifluoropentane-1-sulfonic acid (n = 0).

In order to achieve the above object, the present invention provides a process for preparing a sulfonic acid derivative of the above formula (1), which comprises the following steps:

(a) conjugating an alkyl halide to phenylvinylsulfonate to obtain phenylsulfonate; And

(b) hydrolyzing the phenylsulfonate to obtain a sulfonic acid metal salt.

In one embodiment of the present invention, the sulfonic acid metal salt further reacts with an ammonium salt to obtain an ammonium sulfonate.

In one embodiment of the present invention, the addition reaction of step (a) is carried out in the presence of zinc and copper (I) iodide in the ionic liquid.

In one embodiment of the invention, in step (a), the alkyl halide is partially perfluorinated, preferably partially perfluorinated alkyl iodide, and the ionic liquid is 1-butyl-3-methyl- Imidazolium chloride ([BMIM] Cl) or 1-ethyl-3-methylimidazolium acetate ([EMIM] OAc).

In an embodiment of the present invention, step (b) is characterized in that the phenylsulfonate is hydrolyzed in aqueous solution of metal hydroxide in ethanol.

In one embodiment of the present invention, the metal hydroxide is potassium hydroxide, lithium hydroxide or sodium hydroxide.

In one embodiment of the present invention, the ammonium salt is tetraethylammonium chloride, didecyldimethylammonium bromide or ammonium hydroxide.

The sulfonic acid derivative of the above formula (1) exists in the form of a metal salt of sulfonic acid or an ammonium salt, and forms a cation and an anion when dissociated in water.

The novel sulfonic acid derivatives according to the present invention have remarkable biodegradability. Therefore, unlike conventional fluorinated surfactants, persistence, toxicity and bioaccumulation are reduced. In addition, the novel sulfonic acid derivatives of the present invention exhibit excellent surface activity due to their low surface tension. Therefore, it can be effectively used for commercial stain-proofing agents, fire-extinguishing agents for paints, paints, leather, paper coatings, photographic emulsions, aircraft working fluids, pharmaceuticals and electroplating [Buck, RC; Murphy, PM; Pabon, M. Hdb. Env. Chem. 2012 , 17, 1-24].

1 is a structural formula of a conventional PFOS and a PFOS substitute compound according to an embodiment of the present invention.
2 is a graph showing changes in the surface tension of the potassium sulfonates ( 3a, 3b and 3c ) synthesized in Example 1-3 among the aqueous medium at 25 ° C.

Hereinafter, the present invention will be described in more detail with reference to the drawings.

One aspect of the present invention relates to a novel sulfonic acid derivative represented by the following formula (1): < EMI ID =

(One)

Wherein R &_lt; _f >

, X is independently a hydrogen atom or a fluorine atom, n is an integer of 0 to 3, and R is a metal atom, ammonium or alkylammonium.

Regarding the biodegradability and toxicity of persistent organic pollutants, the sulfonic acid derivatives of the present invention are amphoteric species reducing the number of fluorine atoms in perfluorooctanesulfonic acid (PFOS), a well-known surfactant, It is a compound that can replace PFOS which is suitable and exhibits good activity.

In a preferred embodiment, X in formula (1) is a fluorine atom. The sulfonic acid derivative of the present invention is a partially perfluorinated compound as opposed to a fluorinated PFOS as a whole.

In one preferred embodiment, R of Formula (1) is _{Li, Na, K, NH 4} , (C 2 H 5) 4 N and _{(CH 3) 2 (C 10} H 21) , selected from the group consisting of ₂ N Characterized by one or more. That is, the sulfonic acid derivative of the present invention exists in the form of a metal sulfonate or an ammonium salt, and forms a cation and an anion when dissolved in water.

The sulfonic acid derivative of the present invention is a compound in which the number of fluorine atoms is smaller than that of PFOS and ordinary hydrocarbons are introduced.

In a preferred embodiment, the sulfonic acid derivative is 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonic acid (n = 3), 5,5,6,6, (N = 1) and derivatives of 5,5,5-trifluoropentane-1-sulfonic acid (n = 0).

Examples of preferable sulfonic acid derivatives are shown in (1), (2), (3) and (4), respectively. Specifically, the structural formula (2) shown in FIG. 1 represents a 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonic acid derivative, the structural formula (3) 6,6,6-pentafluorohexane-1-sulfonic acid, and the structural formula (4) represents a derivative of 5,5,5-trifluoropentane-1-sulfonic acid.

Another aspect of the present invention relates to a method for preparing a sulfonic acid derivative of formula (1), which comprises the steps of:

(a) conjugating an alkyl halide to phenylvinylsulfonate to obtain phenylsulfonate;

(b) hydrolyzing the phenylsulfonate to obtain a sulfonic acid metal salt.

In one embodiment, the sulfonic acid metal salt may further react with an ammonium salt to obtain ammonium sulfonate.

Hereinafter, the production method of the present invention will be described in more detail with respect to each reaction step in each step.

In step (a), an alkyl halide is conjugated to phenylvinylsulfonate to obtain phenylsulfonate.

In a preferred embodiment, the addition reaction of step (a) is carried out in the presence of zinc and copper iodide (I) in the ionic liquid.

Step (a) can be represented by the following Reaction Scheme 1.

Reaction 1: Conjugation addition of alkyl halides in ionic liquids and formamides

Wherein R _f is as defined in formula (1).

In the above formula, a is a case where R _f is CF ₃ CF ₂ CF ₂ CF ₂ , b is a case where R _f is CF ₃ CF ₂ CF ₂ , and c means a case where R _f is CF ₃ .

In a preferred embodiment, said alkyl halide of step (a) is partially perfluorinated, in particular partially fluorinated alkyl iodide, said ionic liquid being selected from the group consisting of formamide, 1-butyl- ([BMIM] Cl) or 1-ethyl-3-methylimidazolium acetate ([EMIM] OAc).

This conjugation addition reaction has been successful in protonic as well as quantum ionic liquids as reported [Zhao, MM; Qu, C .; Lynch, JE; J. Org. Chem. 2005 , 70 , 6944-6947]. However, consequently, in the conjugation addition reaction together with the mixture of solvents as shown in Table 1, a low yield ranging from 36 to 43% was obtained.

In various solvents, the conjugation addition reaction of Scheme 1 Solvent number menstruum Temperature time yield(%) One Formamide 0 ℃ - room temperature 5-8 hours 71 2 [BMIM] Cl

0 ℃ - room temperature 5 hours 43 3 [BMIM] Cl / H ₂ O (3: 1) 0 ℃ - room temperature 5 hours 40 4 [EMIM] OAc

0 ℃ - room temperature 5 hours 36 5 [BMIM] Cl / formamide (3: 1) 0 ℃ - room temperature 5 hours 41 6 [EHEIM] Br

0 ℃ - room temperature 5 hours 37

Similar results were observed when this reaction was carried out in other ionic liquids [EMIM] OAc and 1-ethyl-3-hydroxyethylimidazolium bromide ([EHEIM] Br). Formamide has been found to be an optimized solvent for this reaction. However, in the present invention, since the ionic liquid has a low yield but no harmful by-products including an ionic liquid which can be recovered, the most environmentally friendly reaction conditions are possible.

Specifically, the experimental procedure for the conjugation addition reaction involves forming a Zn-Cu pair in [BMIM] Cl by adding CuI very slowly to the Zn powder immersed in the ionic liquid at room temperature (also at 0 ° C) do. After 15 minutes, phenyl vinyl sulphonate and alkyl halide are slowly added to the reaction mixture in sequence for 5 minutes. After 4-6 hours at room temperature, the reaction is repeated by adding the ether to the reaction mixture and pouring it down five times to obtain the product. The remaining ionic liquid is dissolved in chloroform and filtered to remove the Zn-Cu pair, remove the volatile substances and reuse.

In step (b), the phenylsulfonate is hydrolyzed to obtain a sulfonic acid metal salt.

In a preferred embodiment, in step (b) the phenylsulfonate is hydrolyzed in aqueous solution of metal hydroxide in ethanol.

Step (b) can be represented by Reaction Scheme 2.

Scheme 2: Hydrolysis of phenylsulfonate

Wherein R _f is as defined in formula (1), and R is a metal atom.

In the above formula, a is a case where R _f is CF ₃ CF ₂ CF ₂ CF ₂ , b is a case where R _f is CF ₃ CF ₂ CF ₂ , and c means a case where R _f is CF ₃ .

The metal hydroxide is preferably potassium hydroxide, lithium hydroxide or sodium hydroxide.

Specifically, the phenylsulfonate is hydrolyzed with KOH aqueous solution in ethanol at 90 占 폚 for 6 hours to obtain potassium sulfonate. The sulfonic acid lithium salt and the sodium salt are synthesized by hydrolyzing the corresponding phenyl sulfonate with LiOH and NaOH, respectively. Removal of the phenol from the hydrolysis reaction mixture is nearly successful, but 5-10% of aromatic impurities may remain in the salt after washing with ether and ethyl acetate. In this case, the reaction mixture is continuously acid / base treated to remove phenol completely.

The sulfonic acid metal salt reacts further with the ammonium salt to obtain the ammonium sulfonate. As a result of the reaction, the metal ion is replaced with an ammonium ion.

In a preferred embodiment, the ammonium salt is tetraethylammonium chloride, didecyldimethylammonium bromide or ammonium hydroxide.

In one example, the sulfonic acid metal salt is synthesized by simply heating in acetonitrile with tetraethylammonium chloride under nitrogen reflux condition for 12 hours (Scheme 3). The inorganic salt is separated by filtration and the filtrate is concentrated to give tetraethylammonium sulfonate in quantitative yield.

Scheme 3: Synthesis of tetraethylammonium sulfonate

Wherein R _f is as defined in formula (1), and R is a metal atom.

In the above formula, a is a case where R _f is CF ₃ CF ₂ CF ₂ CF ₂ , b is a case where R _f is CF ₃ CF ₂ CF ₂ , and c means a case where R _f is CF ₃ .

As another example, the dodecyldimethylammonium sulfonate may be obtained by heating the sulfonic acid metal salt with dicyclohexylmethylammonium bromide in acetonitrile at 80 占 폚 for 12 hours (Scheme 4). The salt may also be prepared by adding a sulfonic acid metal salt and the same equivalent amount of didecyldimethylammonium bromide in water at room temperature for 24 hours.

Scheme 4: Synthesis of didecyldimethylammonium sulfonate

Wherein R _f is as defined in formula (1), and R is a metal atom.

In the above formula, a is a case where R _f is CF ₃ CF ₂ CF ₂ CF ₂ , b is a case where R _f is CF ₃ CF ₂ CF ₂ , and c means a case where R _f is CF ₃ .

As another example, an ammonium salt may be prepared by neutralizing a sulfonic acid metal salt and then basifying it with NH ₄ OH in water as shown in Reaction Scheme 5 below.

Scheme 5: Synthesis of ammonium sulfonate

Wherein R _f is as defined in formula (1), and R is a metal atom.

In the above formula, a is a case where R _f is CF ₃ CF ₂ CF ₂ CF ₂ , b is a case where R _f is CF ₃ CF ₂ CF ₂ , and c means a case where R _f is CF ₃ .

The present invention will be described in more detail with reference to the following examples. However, these embodiments are illustrative of the present invention and are not intended to limit the scope of the present invention.

In this example, a partially fluorinated new type of sulfonic acid and derivatives thereof were synthesized and characterized.

Materials and Methods:

Partially perfluorinated alkyl halides were supplied by Tokyo Chemical Industries, Inc. (Japan). NMR spectra were recorded on a BRUKER AVANCE 400 (BRUKER, Germany) spectrometer, IR spectra were recorded on a FT-IR-6300 (JASCO, Japan) spectrometer and MS spectra were recorded on a Thermo LCQ fleet MS spectrometer .

(1) Synthesis of phenyl 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonate (hereinafter referred to as 2a)

Method 1: In a clean, dry round bottom flask, a mixture of zinc powder (4.34 g, 66.8 mmol) and copper (I) iodide (2.54 g, 13.3 mmol) in formamide (33 mL) Lt; / RTI > To this mixture, 5,5,6,6,7,7,8,8,8-nonafluorohexyl iodide 1a (4.91 mL, 26.7 mmol) was added followed by phenyl vinylsulfonate (10.0 g, 26.7 mmol) were added and aged only at 0 ° C for several hours. Then, the mixture was warmed to room temperature and stirred until completion of the reaction. Diluted with ethyl acetate (90 mL), filtered off and washed with 1N HCl (60 mL). Hexane (90 mL) was added thereto and the organic layer was separated, dried over Na ₂ SO ₄ , concentrated and purified by silica gel column chromatography using EA: hexane (1: 9) to give 8a (16.7 g, yield 71.3% .

Method 2: A mixture of zinc powder (0.434 g, 6.68 mmol) and copper iodide (I) (0.254 g, 1.33 mmol) in a [BMIM] [Cl] C < / RTI > for 15 minutes. To this mixture was added alkyl halide 1a (0.491 mL, 2.67 mmol) followed by addition of phenylvinylsulfonate (1.0 g, 2.67 mmol) and aging at 0 < 0 > C for several hours, Lt; / RTI > To this was added diethyl ether (3 x 10 mL) followed by stirring. The ether layer was collected, concentrated, and purified by silica gel column chromatography using EA / hexane (1: 9) to give 2a (1.0 g, yield 43%).

The spectrum peaks of synthesized 2a are as follows.

IR (neat)? / Cm ^-1 : 3459, 2967, 1605, 1505, 1379, 1238, 1196, 1149, 1133, 1023, 882, 724, 573;

^{1 H NMR (400 MHz, CDCl} 3) δ 7.45-7.39 (m, 2H), 7.35-7.31 (m, 1H), 7.28-7.21 (m, 2H), 3.31-3.27 (m, 2H), 2.21-2.05 (m, 4 H), 1.87 - 1.79 (m, 2 H);

_{^{19 F NMR (CDCl 3, 376}} MHz) δ -81.98 (3F, tt, J1 = 11.2 Hz, J2 = 3.7 Hz), -115.37 (2F, quintet, J = 15.0 Hz), -125.33 ~ -125.36 (2F, m), -126.89 to -126.96 (2F, m);

¹³ C NMR (100 MHz, CDCl ₃ ) ? 149.10, 130.08, 127.38, 121.97, 50.07, 30.39 (t), 23.24, 19.29 (t);

MS (EI) m / z : 455 (M + Na) < ^{+ &}

(2) Synthesis of potassium 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonate (hereinafter referred to as 3a)

Method 1: KOH (0.4 g in 4 mL of H ₂ O) was added to compound 2a (1.0 g, 2.31 mmol) dissolved in ethanol (4 mL) and THF (4 mL) and the mixture was heated to 80 ° C for 5 hours. Next, the reaction mixture was concentrated to obtain a product. The pure salt 3a was obtained in a yield of 50% (0.46 g) by washing with cooling water.

Method 2: KOH (4.0 g in H ₂ O) was added to compound 2a (10.0 g, 23.1 mmol) dissolved in ethanol (40 mL) and H ₂ O (5 mL) While warming up. Next, the reaction mixture was concentrated and the resulting product was dissolved in water (40 mL) and acidified with 1 N HCI. The phenol was then extracted with ether and the aqueous layer was slightly basicized with KOH. All water was removed in vacuo and the resulting product was recrystallized from methanol to give pure salt 3a in 96% yield (8.8 g).

The spectrum peaks of synthesized 3a are as follows.

IR (neat)? / Cm ^-1 : 3414, 2961, 2880, 1585, 1404, 1362, 1225, 1205, 1132, 1052, 1021, 883, 719, 611

^{1 H NMR (400 MHz, CDCl} 3) δ 2.86-2.82 (m, 2H), 2.27-2.13 (m, 2H), 1.91-1.84 (m, 2H), 1.79-1.71 (m, 2H);

_{^{19 F NMR (CD 3 OD,}} 376 MHz) δ -81.14 (3F, tt, J1 = 11.2 Hz, J2 = 3.7 Hz), -115.00 (2F, quintet, J = 15.0 Hz), -124.94 ~ -124.96 (2F , m), -126.65 ~ -126.72 (2F, m);

MS (EI) m / z : 433 (M + K) < ⁺ & gt ^;

(3) Synthesis of lithium 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonate (hereinafter referred to as 4a)

To the compound 2a (1.0 g, 2.31 mmol) dissolved in ethanol (4 mL) and H ₂ O (5 mL) was added LiOH.H ₂ O (0.145 g in 1 mL H ₂ O) Lt; / RTI > The reaction mixture was then concentrated to give the product. Ether (5 mL x 2) was added to the product solids obtained above, followed by removal of phenol (> 95%). The compound thus obtained was recrystallized from methanol to obtain pure salt 4a as a white glossy powder in a yield of 93% (0.82 g).

The spectral peaks of synthesized 4a are as follows.

IR (neat)? / Cm ^-1 : 3582, 3453, 3307, 2905, 1588, 1268, 1246, 1215, 1170, 1128, 1069, 768, 719, 636

^{1 H NMR (400 MHz, CDCl} 3) δ 2.85-2.82 (m, 2H), 2.28-2.12 (m, 2H), 1.91-1.84 (m, 2H), 1.80-1.71 (m, 2H);

_{^{19 F NMR (CD 3 OD,}} 376 MHz) δ -82.10 ~ -82.17 (3F, m), -114.96 ~ -115.08 (2F, m), -124.95 ~ -124.97 (2F, m), -126.66 ~ -126.73 (2F, m);

MS (EI) m / z : 369 (M + Li) < ^{+ &}

(4) Synthesis of sodium 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonate (hereinafter referred to as 5a)

To the compound 2a (10.0 g, 23.1 mmol) dissolved in ethanol (40 mL) and H ₂ O (5 mL) was added NaOH (1.85 g in 5 mL H ₂ O) and the mixture was heated to 80 ° C. for 5-6 hours . Next, the crude solid obtained by concentrating the reaction mixture was dissolved in water (40 mL) and acidified with 1 N HCl. The resulting compound was extracted with ether to separate the phenol, and the aqueous layer was slightly basicized with NaOH. All water was removed in vacuo and the resulting product was recrystallized from methanol to give pure salt 5a in 96% (8.8 g) yield.

The spectrum peaks of synthesized 5a are as follows.

IR (neat)? / Cm ^-1 : 3540, 3479, 2956, 2884, 1629, 1477, 1229, 1220, 1179, 1134, 1050, 900, 723, 611

^{1 H NMR (400 MHz, MD} 3 OD) δ 2.87-2.82 (m, 2H), 2.28-2.12 (m, 2H), 1.91-1.82 (m, 2H), 1.80-1.71 (m, 2H);

_{^{19 F NMR (CD 3 OD,}} 376MHz) δ -81.15 (3F, tt, J1 = 11.2 Hz, J2 = 3.7 Hz), -115.03 (2F, quintet, J = 15.0Hz), -124.95 ~ -125.99 (2F, m), -126.64 to -126.70 (2F, m);

MS (EI) m / z : 401 (M + Na) < ^{+ &}

(5) Synthesis of tetraethylammonium 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonate (hereinafter referred to as 6a)

To a 50 mL round bottom flask equipped with a reflux condenser was added potassium 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonate 3a (0.500 g, 1.26 mmol) and tetraethylammonium chloride (0.209 g, 1.26 mmol). The stirrer was turned on and the reactor was heated to 80 < 0 > C. After 5 hours, the heating and stirring were stopped, the KCl was separated by filtration through a funnel and concentrated to obtain a liquid compound, tetraethylammonium sulfonate 6a , in a yield of 96% (0.590 g).

The spectral peaks of synthesized 6a are as follows.

IR (KBr)? / Cm ^-1 : 3450, 2917, 2847, 1461, 1216, 1129, 1043, 748

^{1 H NMR (400 MHz, CDCl} 3) δ 3.40 (q, J = 7.3 Hz, 8H), 2.86-2.82 (m, 2H), 2.16-2.01 (m, 2H), 1.97-1.89 (m, 2H), 1.78-1.69 (m, 2H), 1.37 (tt, J = 7.3, 1.7 Hz, 12H);

_{^{19 F NMR (CDCl 3, 376}} MHz) δ -82.00 ~ -82.06 (3F, m), -115.33 ~ -115.43 (2F, m), -125.43 ~ -125.46 (2F, m), -126.94 ~ -127.05 ( 2F, m);

MS (EI) m / z : 615 (M + NEt ₄ ) ^< ^{+ &}

(6) N - Dešil - N , N -Dimethyldecane-1-aminium 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonate (hereinafter referred to as 7a)

Method 1: To a 50 mL round bottom flask equipped with a reflux condenser is added 10 mL of potassium 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonate 3a ( 0.500 g, 1.26 mmol) and N -decyl- N , N -dimethyldecane-1-aminium bromide (0.510 g, 1.26 mmol). The stirrer was turned on and the reactor was heated to 80 < 0 > C. After 5 hours, the heating and stirring were stopped, and the KCl was separated by filtration through a funnel and concentrated to obtain dimethyldecyl ammonium sulfonate 7a in a yield of 92% (0.789 g).

Method 2: 500 mL 2 obtain the potassium salt of 3a (50 g, 126.9 mmol) in a round bottom flask (RBF) was dissolved in deionized water of 300 mL, deionized water of 100 mL here N - decyl - N, N - Dimethyl decane-1-aminium bromide (51 g, 126.9 mmol) was added. The reaction mixture was left to stir at room temperature for 17 hours. A brown liquid was deposited on the bottom of the RBF and separated using a separatory funnel. Water (100 mL) was added thereto and extracted with ether (2 x 100 mL). The ether layer was collected, dried over Na ₂ SO ₄ , concentrated and the resulting salt was vacuum-dried at 35 ° C to obtain dimethyldicecylammonium sulfonate 7a in a yield of 97% (83.5 g).

The spectral peaks of synthesized 7a are as follows.

IR (KBr)? / Cm ^-1 : 3450, 2923, 2847, 1471, 1227, 1135, 1043, 885, 748, 602

^{1 H NMR (400 MHz, CDCl} 3) δ 3.39-3.32 (m, 4H), 3.25 (s, 6H), 2.86-2.81 (m, 2H), 2.14-1.99 (m, 2H), 1.96-1.88 (m , 2H), 1.77-1.69 (m, 2H), 1.69-1.65 (m, 4H), 0.87 (t, J = 6.8 Hz, 6), 1.34-1.25 (m, 28H);

_{^{19 F NMR (CDCl 3, 376}} MHz) δ -82.01 ~ -82.08 (3F, m), -115.40 ~ -115.48 (2F, m), -125.42 ~ -125.44 (2F, m), -126.97 ~ -127.04 ( 2F, m);

MS (EI) m / z: 1008 (M + Me 2 (C 10 H 21) 2 N) +

(7) Synthesis of 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonic acid, ammonia salt (hereinafter referred to as 8a)

To a 50 mL round bottom flask was added potassium 5,5,6,6,7,7,8,8,8-nonafluorooctane-l-sulfonate 3a (0.200 g, 0.50 mmol) dissolved in water (2 mL) Was neutralized with 1N HCl and then basified by addition of aqueous NH ₄ OH and heated for 2 h. All water was then removed under reduced pressure to give ammonium sulfonate 8a in 80% (0.110 g) yield.

The spectrum peak value of synthesized 8a is as follows.

IR (neat)? / Cm ^-1 : 3146, 3041, 1411, 1225, 1202, 1132, 1052, 880, 719, 615

¹ H NMR (400 MHz, D ₂ O) ? 2.80-2.75 (m, 2H), 2.12-1.98 (m, 2H), 1.70-1.61 (m, 2H), 1.58-1.49 (m, 2H);

_{^{19 F NMR (CD 3 OD,}} 376 MHz) δ -81.48 (3F, tt, J1 = 11.2 Hz, J2 = 3.7 Hz), -115.34 ~ -115.36 (2F, m), -125.43 ~ -125.45 (2F, m ), -126.85 to -126.92 (2F, m);

MS (EI) m / z : 412 (M + K) < ^{+ &}

(1) Synthesis of phenyl 5,5,6,6,6-pentafluorohexane-1-sulfonate (hereinafter referred to as 2b)

Compound 2b was obtained in 54% yield in the same manner as in Method 1 or 2 of Example 1- (1), except that 5,5,6,6,6-pentafluorobutyl iodide 1b was used instead of compound 1a. . ≪ / RTI >

The spectral peaks of synthesized 2b are as follows.

IR (neat)? / Cm ^-1 : 3447, 3065, 2957, 2879, 1590, 1486, 1366, 1359, 1231, 1195, 1182, 1075, 1016, 799

^{1 H NMR (400 MHz, CDCl} 3) δ 7.44-7.39 (m, 2H), 7.34-7.29 (m, 1H), 7.28-7.25 (m, 2H), 3.30-3.26 (m, 2H), 2.16-2.03 (m, 4 H), 1.83 - 1.77 (m, 2 H);

¹⁹ F NMR (CDCl ₃ , 376 MHz) ? -86.36 to -86.41 (3F, m), -119.04 (2F, t, J = 18.8 Hz);

¹³ C NMR (100 MHz, CDCl ₃ ) ? 149.12, 129.97, 127.24, 121.86, 50.03 (t), 30.14, 23.10, 19.26 (t);

MS (EI) m / z : 355 (M + Na) < ^{+ &}

(2) Synthesis of potassium 5,5,6,6,6-pentafluorohexane-1-sulfonate (hereinafter referred to as 3b)

Compound 3b was obtained in a yield of 91% in the same manner as in the method 2 of Example 1- (2), except that 2b was used instead of the compound 2a .

The spectral peaks of synthesized 3b are as follows.

IR (neat)? / Cm ^-1 : 3432, 2950, 2887, 1658, 1578, 1393, 1261, 1236, 1198, 1158, 1020, 800, 618

^{1 H NMR (400 MHz, CDCl} 3) δ 7.45-7.39 (m, 2H), 7.35-7.31 (m, 1H), 7.28-7.21 (m, 2H), 3.29 (t, J = 7.5, 2H), 2.21 -2.05 (m, 4H), 1.87 - 1.79 (m, 2H);

¹⁹ F NMR (CD ₃ OD, 376 MHz) ? -86.47 to -86.51 (3F, m), -118.84 (2F, t, J = 18.8 Hz);

MS (EI) m / z : 627 (2M + K) < ^{+ &}

(3) Synthesis of lithium 5,5,6,6,6-pentafluorohexane-1-sulfonate (hereinafter referred to as 4b)

Compound 4b was obtained in 90% yield in the same manner as in Example 1- (3), except that 2b was used instead of Compound 2a .

The spectral peaks of synthesized 4b are as follows.

IR (neat)? / Cm ^-1 : 3453, 2944, 2877, 1578, 1442, 1344, 1305, 1232, 1208, 1187, 1069, 1012, 799

^{1 H NMR (400 MHz, CDCl} 3) δ 7.45-7.39 (m, 2H), 7.35-7.31 (m, 1H), 7.28-7.21 (m, 2H), 3.29 (t, J = 7.5, 2H), 2.21 -2.05 (m, 4H), 1.87 - 1.79 (m, 2H);

¹⁹ F NMR (CD ₃ OD, 376 MHz) ? -86.45? -86.49 (3F, m), -118.81 (2F, t, J = 18.8 Hz);

MS (EI) m / z : 269 (M + Li) < ^{+ &}

(4) Synthesis of sodium 5,5,6,6,6-pentafluorohexane-1-sulfonate (hereinafter referred to as 5b)

The procedure of Example 1- (4) was repeated except that 2b was used instead of Compound 2a. In the same manner, compound 5b was obtained in a yield of 86%.

The spectral peaks of synthesized 5b are as follows.

IR (neat)? / Cm ^-1 : 3544, 3481, 2950, 1628, 1578, 1348, 1235, 1202, 1185, 1052, 1026, 987, 799

^{1 H NMR (400 MHz, CDCl} 3) δ 7.45-7.39 (m, 2H), 7.35-7.31 (m, 1H), 7.28-7.21 (m, 2H), 3.29 (t, J = 7.5, 2H), 2.21 -2.05 (m, 4H), 1.87 - 1.79 (m, 2H);

¹⁹ F NMR (CD ₃ OD, 376 MHz) ? -86.47 to -86.52 (3F, m), -118.82 (2F, t, J = 18.8 Hz);

MS (EI) m / z : 317 (M + K) < ^{+ &}

(5) Synthesis of tetraethylammonium 5,5,6,6,6-pentafluorohexane-1-sulfonate (hereinafter referred to as 6b)

The procedure of Example 1- (5) was repeated except that 3b was used instead of the compound 3a. In the same manner, Compound 6b was obtained in a yield of 98%.

The spectral peaks of synthesized 6b are as follows.

IR (KBr)? / Cm ^-1 : 3455, 2972, 2880, 1738, 1184, 1037, 744, 422

^{1 H NMR (400 MHz, CDCl} 3) δ 3.37 (q, J = 7.3 Hz, 8H), 2.83-2.79 (m, 2H), 2.11-1.97 (m, 2H), 1.94-1.86 (m, 2H), 1.75-1.67 (m, 2H), 1.36 (tt, J = 7.3, 1.7 Hz, 12H);

¹⁹ F NMR (CDCl ₃ , 376 MHz) ? -86.40 to -86.44 (3F, m), -119.01 (2F, t, J = 18.8 Hz);

MS (EI) m / z: 515 (M + NEt 4) +

(6)  N - Dešil - N , N -Dimethyldecane-1-aminium 5,5,6,6,6-pentafluorohexane-1-sulfonate (hereinafter referred to as 7b)

The procedure of Example 1- (6) was repeated except that 3b was used instead of the compound 3a. In the same manner, compound 7b was obtained in a yield of 90%.

The spectral peaks of synthesized 7b are as follows.

IR (KBr)? / Cm ^-1 : 2923, 2858, 1254, 754, 412

^{1 H NMR (400 MHz, CDCl} 3) δ 3.39-3.32 (m, 4H), 3.25 (s, 6H), 2.86-2.81 (m, 2H), 2.14-1.99 (m, 2H), 1.96-1.88 (m , 2H), 1.77-1.69 (m, 2H), 1.69-1.65 (m, 4H), 0.87 (t, J = 6.8 Hz, 6), 1.34-1.25 (m, 28H);

¹⁹ F NMR (CDCl ₃ , 376 MHz) ? -85.44 to -86.47 (3F, m), -118.07 (2F, t, J = 18.8 Hz;

MS (EI) m / z: 907 (M + Me 2 (C 10 H 21) 2 N) +

(7) Synthesis of 5,5,6,6,6-pentafluorohexane-1-sulfonic acid, ammonia salt (hereinafter referred to as 8b)

The procedure of Example 1- (7) was repeated except that 3b was used instead of the compound 3a. In the same manner, compound 8b was obtained in a yield of 90%.

The spectral peak values of synthesized 8b are as follows.

IR (neat)? / Cm ^-1 : 3180, 1396, 1257, 1232, 1201, 1162, 1135, 1082, 1051, 600

¹ H NMR (400 MHz, D ₂ O) ? 2.81-2.77 (m, 2H), 2.14-2.01 (m, 2H), 1.71-1.62 (m, 2H), 1.59-1.50 (m, 2H);

¹⁹ F NMR (CD ₃ OD, 376 MHz) ? -86.45? -86.49 (3F, m), -118.22 (2F, t, J = 18.8 Hz);

MS (EI) m / z : 312 (M + K) < ⁺ & gt ^;

(1) Synthesis of phenyl 5,5,5-trifluoropentane-1-sulfonate (hereinafter referred to as 2c)

Compound 2c was obtained in a yield of 49% in the same manner as in Method 1 or 2 of Example 1- (1) except that 5,5,5-trifluoropropyliodide 1c was used instead of Compound 1a . Respectively.

The spectrum peaks of synthesized 2c are as follows.

IR (KBr)? / Cm ^-1 : 3450, 2977, 2362, 1591, 1488, 1373, 1260, 1140, 1015, 863, 754, 689

^{1 H NMR (400 MHz, CDCl} 3) δ 7.37-7.32 (m, 2H), 7.27-7.23 (m, 1H), 7.21-7.18 (m, 2H), 3.21-3.17 (m, 2H), 2.14-2.04 (m, 2H), 2.03 - 1.95 (m, 2H), 1.74 - 1.66 (m, 2H);

_{^{19 F NMR (CDCl 3, 376}} MHz) δ -67.21 (3F, t, J = 11.28 Hz);

¹³ C NMR (100 MHz, CDCl ₃ ) ? 149.12, 129.99, 127.26, 121.88, 50.02, 33.13 (q), 22.73, 20.68 (q);

MS (EI) m / z : 305 (M + Na) < ^{+ &}

The reaction of the alkyl halides 1b with 1c was carried out in an ionic liquid and formamide, showing no significant difference in yield when providing 2b and 2c , respectively.

The reaction mechanism of this reaction is expected to follow the radical-type addition reaction, in which the ionic liquid prefers the conjugation addition reaction instead of the homogeneous coupling reaction and also serves as the proton source in the presence of the Zn-Cu pair .

(2) Synthesis of potassium 5,5,5-trifluoropentane-1-sulfonate (hereinafter referred to as 3c)

Compound 3c was obtained in a yield of 93% in the same manner as in the method 2 of Example 1- (2), except that 2c was used instead of the compound 2a .

The spectral peaks of synthesized 3c are as follows.

IR (neat)? / Cm ^-1 : 3446, 2954, 2882, 1578, 1348, 1194, 1086, 1058, 799, 614

^{1 H NMR (400 MHz, CDCl} 3) δ 7.45-7.39 (m, 2H), 7.35-7.31 (m, 1H), 7.28-7.21 (m, 2H), 3.29 (t, J = 7.5, 2H), 2.21 -2.05 (m, 4H), 1.87 - 1.79 (m, 2H);

_{^{19 F NMR (CD 3 OD,}} 376 MHz) δ -67.52 (3F, t, J = 11.28 Hz);

MS (EI) m / z : 283 (M + K) < ^{+ &}

(3) Synthesis of lithium 5,5,5-trifluoropentane-1-sulfonate (hereinafter referred to as 4c)

The procedure of Example 1- (3) was repeated except that 2c was used instead of Compound 2a. In the same manner, compound 4c was obtained in a yield of 85%.

The spectral peaks of synthesized 4c are as follows.

IR (neat)? / Cm ^-1 : 3446, 2954, 2881, 1594, 1576, 1447, 1309, 1215, 1203, 1179, 1149, 1072, 656

^{1 H NMR (400 MHz, CDCl} 3) δ 7.45-7.39 (m, 2H), 7.35-7.31 (m, 1H), 7.28-7.21 (m, 2H), 3.29 (t, J = 7.5, 2H), 2.21 -2.05 (m, 4H), 1.87 - 1.79 (m, 2H);

_{^{19 F NMR (CD 3 OD,}} 376 MHz) δ -67.43 (3F, t, J = 11.28 Hz);

MS (EI) m / z : 219 (M + Li) < ^{+ &}

(4) Synthesis of sodium 5,5,5-trifluoropentane-1-sulfonate (hereinafter referred to as 5c)

The procedure of Example 1- (4) was repeated except that 2c was used instead of Compound 2a. In the same manner, compound 5c was obtained in a yield of 80%.

The spectrum peaks of synthesized 5c are as follows.

IR (neat)? / Cm ^-1 : 3477, 2981, 2884, 1588, 1445, 1316, 1259, 1235, 1210, 1137, 1053, 1022, 802, 652

^{1 H NMR (400 MHz, CDCl} 3) δ 7.45-7.39 (m, 2H), 7.35-7.31 (m, 1H), 7.28-7.21 (m, 2H), 3.29 (t, J = 7.5, 2H), 2.21 -2.05 (m, 4H), 1.87 - 1.79 (m, 2H);

_{^{19 F NMR (CD 3 OD,}} 376 MHz) δ -67.66 (3F, t, J = 11.28 Hz);

MS (EI) m / z : 251 (M + Na) < ^{+ &}

(5) Synthesis of tetraethylammonium 5,5,5-trifluoropentane-1-sulfonate (hereinafter referred to as 6c)

An in Example 1-Compound 6c to the same manner as in the method (5), except for using the compound 3a instead of 3c was obtained in 95% yield.

The spectrum peaks of synthesized 6c are as follows.

IR (KBr)? / Cm ^-1 : 3455, 2956, 1738, 1477, 1395, 1281, 1194, 1093, 748, 602

^{1 H NMR (400 MHz, CDCl} 3) δ 3.46-3.39 (q, J = 7.3 Hz, 8H), 2.82-2.78 (m, 2H), 2.10-1.97 (m, 2H), 1.94-1.86 (m, 2H ), 1.75-1.69 (m, 2H), 1.38-1.35 (m, 12H);

_{^{19 F NMR (CDCl 3, 376}} MHz) δ -67.70 (3F, t, J = 11.28 Hz);

MS (EI) m / z: 465 (M + NEt 4) +

(6) N - Dešil - N , N -Dimethyldecane-1-aminium 5,5,5-trifluoropentane-1-sulfonate (hereinafter referred to as 7c)

(3) was prepared in the same manner as in Example 1- (6), except that 3c was used instead of the compound 3a . , The compound 7c was obtained in a yield of 91%.

The spectral peak values of synthesized 7c are as follows.

IR (KBr)? / Cm ^-1 : 3445, 2928, 2847, 2341, 1471, 1281, 1260, 1199, 754

^{1 H NMR (400 MHz, CDCl} 3) δ 3.39-3.32 (m, 4H), 3.25 (s, 6H), 2.86-2.81 (m, 2H), 2.14-1.99 (m, 2H), 1.96-1.88 (m , 2H), 1.77-1.69 (m, 2H), 1.69-1.65 (m, 4H), 0.87 (t, J = 6.8 Hz, 6), 1.34-1.25 (m, 28H);

_{^{19 F NMR (CDCl 3, 376}} MHz) δ -67.32 (3F, t, J = 11.28 Hz);

MS (EI) m / z: 857 (M + Me 2 (C 10 H 21) 2 N) +

(7) Synthesis of 5,5,5-trifluoropentane-1-sulfonic acid, ammonia salt (8c)

Compound 8c was obtained in a yield of 87% in the same manner as in Example 1- (7) except that 3c was used instead of the compound 3a .

The peak values of synthesized 8c are as follows.

IR (neat)? / Cm ^-1 : 3188, 1470, 1415, 1352, 1236, 1188, 1079, 1048, 796, 604

¹ H NMR (400 MHz, D ₂ O) ? 2.82-2.76 (m, 2H), 2.16-2.00 (m, 2H), 1.73-1.61 (m, 2H), 1.60-1.52 (m, 2H);

_{^{19 F NMR (CD 3 OD,}} 376 MHz) δ -66.98 (3F, t, J = 11.28 Hz);

MS (EI) m / z : 262 (M + K) < ^{+ &}

[Experimental Example] Surface tension measurement

The surface tension of aqueous solutions of potassium sulfonate ( 3a , 3b and 3c ) at different concentrations was measured to evaluate the surfactant activity of the sulfonic acid derivatives prepared in Examples 1 to 3.

The surface tension of the potassium salt aqueous solution was measured approximately by the equation given in Equation 1 below.

m ₁ /? ₁ = m ₂ /? ₂ (1)

Where m ₁ and γ ₁ are the weight of the water droplet and the surface tension at 25 ° C., respectively, and m ₂ and γ ₂ are the surface tension at the same temperature as the weight of the surfactant aqueous solution, respectively.

FIG. 2 is a graph showing changes in the surface tension of potassium sulfonates ( 3a, 3b and 3c ) in an aqueous medium at 25 ° C. The surface tension of all potassium sulfonates decreased with increasing concentration as expected. When from Figure 2, compared to other acid potassium 3a can be observed that the surface tension is low, the surfactant can be seen the excellent and also the longer the chain, as expected, the surface tension is reduced.

Claims (11)

A sulfonic acid derivative represented by the following formula (1):

(One)
Wherein R &_lt; _f >

, X is independently a hydrogen atom or a fluorine atom, n is an integer of 0 to 3, and R is a metal atom, ammonium or alkylammonium.

The sulfonic acid derivative according to claim 1, wherein X in the above formula (1) is a fluorine atom.

According to claim 1 wherein, R of Formula (1) is selected from Li, Na, K, NH _4, (C ₂ H _{5), 4} N and (CH _{3), 2} (C ₁₀ H ₂₁₎ the group consisting of ₂ N A sulfonic acid derivative.

The method according to claim 1, wherein the sulfonic acid derivative is selected from the group consisting of 5,5,6,6,7,7,8,8,8-nonafluorooctane-1-sulfonic acid (n = 3), 5,5,6,6, Sulfonic acid (n = 1) and derivatives of 5,5,5-trifluoropentane-1-sulfonic acid (n = 0).

A process for preparing a sulfonic acid derivative of formula (1) according to claim 1, comprising the steps of:
(a) conjugating an alkyl halide to phenylvinylsulfonate to obtain phenylsulfonate; And
(b) hydrolyzing the phenylsulfonate to obtain a sulfonic acid metal salt.

6. The method according to claim 5, wherein the sulfonic acid metal salt further reacts with an ammonium salt to obtain ammonium sulfonate.

6. The process according to claim 5, wherein the addition reaction of step (a) is carried out in the presence of zinc and copper (I) iodide in the ionic liquid.

6. The method of claim 5, wherein in step (a) the alkyl halide is partially perfluorinated alkyl iodide and the ionic liquid is 1-butyl-3-methyl-imidazolium chloride ([ -Ethyl-3-methylimidazolium acetate ([EMIM] OAc).

6. A process according to claim 5, characterized in that in step (b) the phenylsulfonate is hydrolyzed in aqueous solution of a metal hydroxide in ethanol.

The process according to claim 9, wherein the metal hydroxide is potassium hydroxide, lithium hydroxide or sodium hydroxide.

7. The process according to claim 6, wherein the ammonium salt is tetraethylammonium chloride, didecyldimethylammonium bromide or ammonium hydroxide.

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