FLUORINE-CONTAINING COMPOUNDS

Abstract: A fluorine-containing compound of the formula: wherein R f is a C₃-C₂₁ fluorinated hydrocarbon group or a C₃-C₂₁ fluorinated oxyhydrocarbon group; X¹ is a C₁-C₁₁ hydrocarbon group; X², X³ and X⁴ are each a C₂-C₆ hydrocarbon group; Y¹ is a group of the formula: Y₂ is a group of the formula: W¹ is a group of the formula: W² is a C₁-C₁₀ hydrocarbon group optionally having -OH or -COOH or a amide group in the backbone; Z¹ is halogen or a group of the formula: Z² is a group of the formula: Z³ is a group of the formula; -COOM, -SO₃M, -OSO₃M, -O (OM)₂ or R¹ is hydrogen or a C₁-C₅ hydrocarbon group; R² is hydrogen or a C₂-C₄ acyl group; R³ is hydrogen or a group of the formula: -(X¹O) q H or -R⁷Z³; R⁴ is a group of the formula: -(X¹O) q H or -R⁷Z³; R⁵ and R⁶ are each a C₁-C₂₀ hydrocarbon group or a group of the formula; -(X¹O) q H, -X¹ k COOM, -R f or -Y¹X¹ k R f ; R⁷ is a C₁-C₂₀ hydrocarbon group or a group of the formula: -(CH₂CH₂OCH₂CH₂) r -; R⁸, R⁹ and R¹⁰ are each a C₁-C₂₀ hydrocarbon group or a group of the formula: -(X¹O) q H, -R f or -Y¹X¹ k R f ; R¹¹ is C₂-C₆ alkylene group optionally having one or two oxygen or sulfur atoms; R¹² is hydrogen, a C₁-C₂₀ hydrocarbon group or a C₂-C₂₀ acyl group; R¹³ is hydrogen or a C₁-C₂₀ hydrocarbon group; M is hydrogen, an alkali metal, an alkaline earth metal or a NH₄ group; k is zero or one; m is an integer of 1 to 50; n is an integer of 1 to 5; q is an integer of 1 to 20; and r is an integer of 1 to 5.

Description: FLUORINE-CONTAINING COMPOUNDS FIELD OF THE INVENTION The present invention relates to fluorine-containing compounds. More particularly, it relates to fluorinecontaining compounds which are soluble in organic solvents and greatly reduce their surface tension. BACKGROUND OF THE INVENTION Hitherto, fluorine-containing compounds, for example, of the following formulas are known: EMI1.1 wherein Rf is the same as defined below (cf. U.S. Pat. No. 4,165,338) Although these fluorine-containing compounds are useful as leveling agents for various waxes, additives for foam extinguishing agents, surface-modifying agents of resins, etc., they have some drawbacks such that their solubility in solvents is poor and even if they are dissolved in the solvents, they are poor in lowering the surface tension thereof and that they have poor compatibility with a plasticizer contained in the resin. Also, a fluorine-containing quarternary ammonium compound of the following formula is known: EMI2.1 Although this quarternary ammonium compound is soluble in water, its solubility in an organic solvent other than lower alcohols is poor. Further, a fluorine-containing betaine compound of the following formula is known: EMI2.2 Although this betaine compound is soluble in water, its solubility in organic solvents is poor. SUMMARY OF THE INVENTION One object of the invention is to provide a novel fluorine-containing compound which has excellent solubility in an organic solvent. Another object of the invention is to provide a fluorine-containing compound which greatly decreases surface tension of an organic solvent in which the compound is dissolved. DETAILED DESCRIPTION OF THE INVENTION The novel fluorine-containing compound of the invention has a following general formula: EMI3.1 wherein Rf is a C3-C2l fluorinated hydrocarbon group or a C3-C2l fluorinated oxyhydrocarbon group; X1 is a C1-C11 hydrocarbon group; X2, X3 and X4 are each a C2-C6 hydrocarbon. group; yl is a group of the formula: EMI3.2 y2 is a group of the formula: EMI3.3 wl is a group of the formula: EMI3.4 W2 is a C1-C10 hydrocarbon group optionally having -OH or -COOH or a amide group in the backbone; Z is halogen or a group of the formula: EMI3.5 Z is a group of the formula: EMI4.1 Z is a group of the formula: : EMI4.2 R is hydrogen or a C1-C5 hydrocarbon group; R2 is hydrogen or a C2-C4 acyl group; R3 is hydrogen or a group of the formula: -(X1O) qH or -R7Z3; R4 is a group of the formula : -(X1O)qH or -R7Z3 ; R5 and R6 are each a C1-C20 hydrocarbon group or a group of the formula: -(X1o)@H, X1kCOOM, -Rf or Y1x1kRf; R7 is a C1-C20 hydrocarbon group or a group of the formula : - (CH2CH2OCH2CH2)@- ; R8, R9 and R10 are each a Cl-C20 hydrocarbon group or a group of the formula: -(X1O)qH,, -Pf or - Y1X1 R11 is C2-C6 alkylene group optionally having one or two oxygen or sulfur atoms ; R12 is hydrogen, a C1-C20 hydrocarbon group or a C2-C20 acy1 group ; R13 is hydrogen or a C1 C20 hydrocarbon group; M is hydrogen, an alkali metal, an alkaline earth metal of a NH4 group; k is zero or one; m is an integer of 1 to 50; n is an integer of 1 to 5; q is an integer of 1 to 20; and r is an integer of 1 to 5. Rf group in the formula (I) usually has 3 to 21, preferably 5 to 15 carbon atoms. Preferably, Rf is a C5-C15 fluorinated aliphatic group, C5-C15 fluorinated oxyhydrocarbon groups and a C5-C15 perfluorinated saturated aliphatic group. Specific examples of Rf group are groups of the formula: CtF2t+l-, r H-(CtF2t)-, r CtF(2tl) and EMI5.1 wherein t is an integer of 3 to 21 and u is an integer of 0 to 5. The hydrocarbon group may be an aliphatic, alicyclic, aromatic or aralkyl and/or straight or branched group which optionally substituted with one or more suitable substituents such as -OH, -COOH, etc. When the hydrocarbon group is a monovalent group, it is preferably an alkyl group. When it is a divalent group, it is preferably an alkenyl group. Halogen is usually iodine, bromine or chlorine. m is preferably an integer of 5 to 30. xl, x2 x3 and X4 are each preferably a C2-C4 aliphatic group, more preferably, -CH2CH2-, -CH(CH3)CH2- and -(CH2)4 zl is preferably halogen or a group of the formula: -OR or -oSo3Rl3. R12 is preferably hydrogen or a C1-C6 aliphatic group, more preferably hydrogen or a C1-C6 satureted alkyl group. R13 is preferably hydrogen or a C1-C6 aliphatic group, more preferably a C1-C6 satureted alkyl group. R1 and R2 are each preferably hydrogen. Each of R5 to R10 which is the hydrocarbon group is preferably an aliphatic, aryl or aralkyl group. More preferably, R5 and R6 are each a group of the formula: -(X1O)@H, -X1kCOMM, -Rf or -Y1X1kRf. Specific examples of the compound (I) wherein y2 is EMI6.1 are as follows: EMI6.2 H CH3 CH3 CH3 CH2CH2OH # # # # # C2F18CH2CH2N-CHCH2O(CHCH2O)2CHCH2N OH CH2CH2OH # # # C7F15C-N(CH2)3O((CH2)4O)27(CH2)3N CH2CH2OH OH (CH2CH2O)10H H(CF2CF2)4C-N(CH2)3O((CH2)4O)8(CH2)3N 2CH2O)10H OH H CH2CH2OH # C9F19CH2CHCH2N(CH2)3O((CH2)4O)8(CH2)3N CH2CH2OH OCOCH3 CH2CH2OH # # C15F31CH2CHCH2N(CH2)3O((CH2)4O)8(CH2)N I CH2CH2OH H OH CH2CH2OH # # # C8F17CH2CH2SON(CH2)3O((CH2)4O)27(CH2)3N # CH2CH2OH OH H (CH2CH2O)10H # # # C9F19CH2CHCH2N(CH2)3O((CH2)4O)8(CH2)3N (CH2CH2O)10H OH H H # # # C9F19CH2CHCH2N(CH2)3O((CH2)4O)8(CH2)3NCH2COONa OH H H # # # C9F19CH2CHCH2N(CH2)3O((CH2)4O)8(CH2)3NCH2CH2COONa OH H # # # C7F15C-N(CH2)3O(CH2CH2O)20(CH2)3NCH2COONa EMI8.1 Specific examples of the compound (I) wherein y2 is -W1-Z1 are as follows: EMI8.2 EMI9.1 EMI10.1 EMI11.1 Specific examples of the compound (I) wherein Y2 EMI12.1 EMI13.1 EMI14.1 EMI15.1 The fluorine-containing compound (I) of the invention can be prepared as follows: (A) In the first step, a compound of the formula : AHR1X2O(X3O)mX4NH2 (a1) wherein Rl, X2, X3, X4 and m are the same as defined above is reacted with a compound of the formula: : EMI16.1 wherein Rf, X1 and k are the same as defined above, RfCOA (a3) wherein Rf is the same as defined above and A is an alkoxy group, RfXkCOB (a4) wherein Rf, X1 and k are the same as defined above and B is halogen, RfX1kSO2B1 (a5) wherein Rf, Xl, B and k are the same as defined above, or RfX1k(ch2)nB (a6) wherein Rf, Xl, B, k and n are the same as defined above, in equimolar amounts to obtain a compound of the formula: PFX1kY1NR1X2O(X3O)mX4NH2 (a7) wherein Rf, X1 to X4, R1, k and m are the same as defined above and Y1 is a group of the formula: EMI16.2 wherein n is the same as defined above. (B-l) In the second step, for the preparation of the compound (I) wherein y2 is EMI17.1 the compound (a7) obtained in the step (A) is reacted with a compound of the formula: B-R (bl) wherein B is the same as defined above and R is a group of the formula: -(X1kO)q-H or - R7-Z3 wherein Xl, R7, Z3, k and q are the same as defined above in a molar ratio of 1:1 to 1:2. (B-2) For the preparation of the compound (I) wherein Y2 is -W1-Z1, the compound (a7) is reacted with a compound of the formula: B-R' (b2) wherein B is the same as defined above and R' is a C1-C20 hydrocarbon group, or a group of the formula: -(X1kO)q-H or -Rf wherein Rf, X1, k and q are the same as defined above, EMI17.2 wherein Rf, X1 and k are the same as defined above, or B-R11-B (b3) wherein R11 and B ae the same as defined above to obtain a compound (I) wherein Y2 is the group of the formula: EMI18.1 wherein R31 R4 and R11 are the same as defined above. (C-1) The compound (I) obtained in the step (B-2) is then reacted with the compound (b2) or a compound of the formula: R2-Q-R10 (cl) wherein R2 and R10 are the same as defined above and Q is -S03-, 504 or -CO3- to obtain the compound (I) wherein y2 is -W1-Z1. (B-3) Further, for the preparation of the compound (I) wherein Y2 is EMI18.2 the compound -(a?) is reacted with the compound of the formula EMI18.3 wherein Rf, X and k are the same as defined above, or a compound of the formula: B-R" (b4) wherein B is the same as defined above and R" is a C1-C20 hydrocarbon group, a group of the formula: (X1kO)a-H, -X1COOM or Rf wherein Rf, Xl, k and q are the same as defined above to obtain the compound (I) wherein 2 is EMI19.1 (C-2) Subsequently, the compound (I) obtained in the step (B-3) is reacted with a compound of the formula: : B-W2-Z2H (c2) wherein B, W2 and Z2 are the same as defined above, or CH2=CHX1kCOOH (c3) wherein X1 and k is the same as defined above to obtain the compound (I) wherein Y2 is EMI19.2 Reaction conditions in each steps are as follows: In the step (A), the reactions of the compound (al) with the compound (a2), (a3) or (a6) are preferably carried out in a solvent selected from the group consisting of alcohols, ethers, hydrocarbons, halogenated hydrocarbons, aromatic compounds, etc. The reaction temperature is from 20 to 1500C, preferably from 40 to l000C. The reaction time is from 3 to 10 hours, preferably from 5 to 8 hours. The reaction of the compound (al) with the compounds (a4) or (a5) is carried out in a solvent selected from the group consisting of ethers, hydrocarbons, halogenated hydrocarbons, aromatic compounds, etc. The reaction temperature is from -10 to 1000C, preferably from 0 to 500C. The reaction time is from 1 to 5 hours, preferably from 2 to 3 hours. The compound obtained in the step (A) is used in the reaction in the step (B-l), (B-2) or (B-3) without isolation or purification. Thus, the compound (bl), (b2), (b3), (b4) or (a2) is added to the reaction mixture resulted in the step (A) in an equimolar or twice equimolar amount. The reaction temperature in this step is from 20 to l500C, preferably from 40 to 1000C. The reaction time is from 3 to 10 hours, preferably from 5 to 8 hours. The -CH(OH)- group born in the compound (a7Y obtained in the step (A) may be converted to the -CHtOR2)- group by reacting the compound (a7) with a corresponding acid halide or anhydride at a room temperature. The compound obtained in the step (B-2) and (B-3) is also used in the step (C-l) and (C-2) without isolation or purification, rjpectively. The reaction temperature in this step is fm 20 to l500C, preferably from 40 to l000C. The reaction time is from 3 to 10 hours, preferably from 5 to 8 hours When the compounds to be reacted in the steps (B) and (C) are the same, the reactions in the both steps can be simultineously carried out. T compound (I) of the invention has far better solubility ii solvents, particularly in water or organic solvents, and the solution of the compound (I) has better surface tension-lowering property than the above described conventional fluorine-containing compounds. Therefore, the compound (I) of the invention is preferably used as an leveling agent for various waxes and coatings, an additive for a fire extinguisher (eg. an aqueous foam fire extinguisher, a synthetic surfactant fire extinguisher, a protein fire extinguisher and a powder fire extinguisher), a penetrating agent for a fiber, metal or photograph processing agent, an antistatic agent for a resin, a non-tackifier, a stainproofing agent, an anti-clouding and anti-fogging agent for polyvinyl film, a mold release agent, an emulsifier for an emulsion polymerization, etc. The present invention will be hereinafter explained further in detail by following Examples. Example 1 Preparation of EMI22.1 (a) To a four-necked 100 ml flask equipped with thermometer, a condenser and a stirrer, EMI22.2 (5.26 g, 0.01 mole), H2N(CH2)3O((CH2)4O)8(CH2)3NH2 (7.08 g, 0.01 mole) and isopropanol (15 g) were charged and reacted at 700C for 6 hours. Gas chromatography analysis of the reaction mixture revealed that the epoxide raw material was consumed. (b) To the reaction mixture obtained in the step (a), ClCH2COOH (0.95 g, 0.01 mole) and NaOH (0.80 g, 0.02 mole) were added and reacted at 700C for 7 hours. Thereafter, isopropanol was distilled off, and the residue was washed with a mixture of acetonitrile and trichlorotrifluoroethane in a weight ratio of 50:50 to obtain a solid compound (12.22 g). Yield 93 %. The compound was analyzed by NMR and IR spectrum and identified as the title compound. The results of the analyses are shown below. 19F-NMR (External standard: CF3COOH) EMI23.1 <tb> Chemical <SEP> shift <SEP> 6 <SEP> (ppm) <SEP> Signal <SEP> strength <tb> <SEP> -5.7 <SEP> 6F <tb> <SEP> 34.6 <SEP> 2F <tb> <SEP> 37.1 <SEP> 2F <tb> <SEP> 42.8 <SEP> 2F <tb> <SEP> 43.7 <SEP> 4F <tb> <SEP> 45.6 <SEP> 2F <tb> <SEP> 108.2 <SEP> 1F <tb> lH-NMR EMI24.1 <tb> Chemical <SEP> shift <SEP> Assignment <SEP> Signal <SEP> strength <tb> 6 <SEP> (ppm) <tb> <SEP> 1.50-1.80 <SEP> -OCH2CH2CH2CH2O- <SEP> 32H <tb> <SEP> -NHCH2CH2CH2O- <SEP> 4H <tb> <SEP> 2.27 <SEP> OH <SEP> 2H <tb> <SEP> -CF <SEP> 2CH2CH <tb> <SEP> 2.58-2.90 <SEP> OH <SEP> 2H <tb> <SEP> -CHCH2N= <tb> <SEP> =NCH2 <SEP> CH2 <SEP> - <SEP> 4H <tb> <SEP> 3.30-3.61 <SEP> -OCH2CH2CH2CH2O- <SEP> 32H <tb> <SEP> =NCH2CH2CH2O <SEP> 4H <tb> <SEP> -NCH2 <SEP> COONa <SEP> 2H <tb> <SEP> 4.18 <SEP> OH <SEP> 1H <tb> <SEP> -CH <tb> <SEP> 4.45-4.72 <SEP> =N-H <SEP> 2H <tb> <SEP> 4.83 <SEP> C-OH <SEP> 1H <tb> -1 IR spectrum: 1,610 cm 1 (C=O). Example 2 Preparation of EMI24.2 To the reaction mixture obtained in the same manner as in Example 1 (a), ClCH2CH2OH (1.61 g, 0.02 mole) and NaOH (0.80 g, 0.02 mole) were added and reacted at 70 C for 7 hours. Thereafter, isopropanol was distilled off, and the residue was washed with the same solvent mixture as used in Example 1 to obtain the title compound (12.03 g). Yield 91 %. 9F-NMR (External standard: CF3COOH) EMI25.1 <tb> Chemical <SEP> shift <SEP> 6 <SEP> (ppm) <SEP> Signal <SEP> strength <tb> <SEP> -5.6 <SEP> 6F <tb> <SEP> 34.6 <SEP> 2F <tb> <SEP> 37.2 <SEP> 2F <tb> <SEP> 42.8 <SEP> 2F <tb> <SEP> 43.7 <SEP> 4F <tb> <SEP> 45.6 <SEP> 2F <tb> <SEP> 108.1 <SEP> 1F <SEP> <tb> 1H-NMR EMI26.1 <tb> <SEP> Chemical <SEP> shift <SEP> Assignment <SEP> Signal <SEP> strength <tb> <SEP> 6 <SEP> (ppm) <tb> <SEP> 1.50-1.80 <SEP> -OCH2CH2CH2CH2O- <SEP> 32H <tb> <SEP> -NHCH <SEP> 2CH2CH2O- <SEP> 4H <tb> <SEP> 2.28 <SEP> OH <SEP> 2H <tb> <SEP> -CF <SEP> 2CH2CH <tb> <SEP> 2.58-2.92 <SEP> OH <SEP> 2H <tb> <SEP> -CHCH2N= <tb> <SEP> =NCH2CH2 <SEP> - <SEP> 4H <tb> <SEP> CH2CH2OH <SEP> I <SEP> 4H <tb> <SEP> CH2CH2OH <tb> <SEP> 3.29-3.60 <SEP> -OCH2CH2CH2CH2O- <SEP> 32H <tb> <SEP> =NCH2CH2CH2O <tb> <SEP> L <SEP> L <SEP> -L <tb> <SEP> CH2CH2OH <SEP> ! <SEP> ! <tb> <SEP> CH,CH,OH <SEP> i <SEP> 4H <tb> &verbar; <SEP> 4.10 <SEP> 2 <SEP> 2 <SEP> - <SEP> 2H <SEP> ! <tb> <SEP> t:H,CH,oH <tb> <SEP> -CH- <SEP> . <SEP> . <SEP> &verbar; <tb> <SEP> 4.65 <SEP> =NH <SEP> 1H <tb> <SEP> 4.83 <SEP> C-OH <SEP> 1H <tb> Example 3 Preparation of EMI26.2 (a) To the same flask as used in Example 1, C7F15COOC2H5 (4.42 g, 0.01 mole), H2N(CH2)3O((CH2)4O)8 (CH2)3NH2 (7.08 g, 0.01 mole) and isopropanol (15 g) were charged and reacted at 700C for 6 hours. Gas chromatography analysis of the reaction mixture revealed that the epoxide raw material was consumed. (b) To the reaction mixture obtained in the step (a), ClCH2CH2OH (1.61 g, 0.02 mole) and NaOH (0.80 g, 0.02 mole) were added and reacted in the same manner as in Example 2 (b) to obtain the title compound (10.7 g). Yield 90 %. Elemental analysis: C H F N O Calc'd: 50.51 7.32 23.99 2.02 16.16 Found: 50.47 7.30 24.05 2.00 16.18 -1 IR spectrum: 1,720 cm (-CO-NH-). Example 4 Preparation of EMI27.1 (a) To the same flask as used in Example 1, C8F17CH2CH2SO2Cl (5.47 g, 0.01 mole), H2N(CH23O((CH2) 40)27 (CH2)3NH2 (20.8 g, 0.01 mole) and trichlorotrifluoroethane (20 g) were charged and reacted at OOC for 30 minutes and then at a room temperature for 2 hours. (b) To the reaction mixture obtained in the step (a), ClCH2CH2OH (1.61 g, 0.02 mole) and NaOH (0.80 g, 0.02 mole) were added and reacted in the same manner as in Example 2 (b) to obtain the title compound (24.6 g). Yield 92 %. Elemental analysis: C H F N O S Calc'd: 57.44 9.09 12.08 1.05 19.15 1.20 Found: 57.40 9.08 12.09 1.04 19.21 1.18 IR spectrum: 1,170 cm 1 (-CH2SO2N=). Example 5 Preparation of EMI28.1 (a) To the same flask as used in Example 1, C8F17CH2CH2I (5.74 g, 0.01 mole), H2N(CH2)3O((CH2)4O)13 (Ch2)3NH2 (10.7 g, 0.01 mole) and isopropanol (15 g) were charged and reacted at 700C for 6 hours. Gas chromatography analysis revealed that the iodide compound was consumed. (b) To the reaction mixture obtained in the step (a), ClCH2CH2SO3Na (1.67 g, 0.01 mole) and NaOH (0.40 g, 0.01 mole) were added and reacted in the same manner as in Example 2 (b) to obtain the title compound (14.6 g). Yield 89 %. Elemental analysis: C H F N O S Na Calc'd: 51.09 7.66 19.65 1.70 16.55 1.95 1.40 Found: 51.05 7.68 19.68 1.70 16.54 1.94 1.41 Example 6 Preparation of EMI29.1 To the reaction mixture obtained in the same manner as in Example 1 (a), ClCH2COOH (1.9 g, 0.02 mole) and NaOH (1.6 g, 0.04 mole) were added and reacted in the same manner as in Example 1 (b) to obtain the title compound (12.5 g). Yield 90 %. Elemental analysis: C H F N O Na Calc'd: 46.48 6.24 25.90 2.01 16.07 3.30 Found: 46.45 6.27 25.92 2.00 16.01 3.35 Test Examples and Comparative Examples Solubility of the following compounds of the invention and comparative compounds in some organic solvents, and their surface tension of a 0.1 % by weight solution in toluene were measured at 250C. The surface tension was measured by the Wilhelmy method. Compounds of the invention EMI29.2 EMI30.1 Comparative compounds EMI30.2 (Fluorine-containing surfactant manufactured by 3M) Table 1 EMI31.1 <tb> <SEP> Compound <SEP> Methanol <SEP> Toluene <SEP> Hexane <tb> <SEP> 1 <SEP> wt <SEP> % <SEP> 0.1 <SEP> wt% <SEP> 1 <SEP> wt <SEP> % <SEP> 0.1 <SEP> wt <SEP> % <tb> <SEP> i <SEP> 0 <SEP> 0 <SEP> 0 <SEP> # <SEP> 0 <SEP> <tb> <SEP> ii <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> <tb> iii <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> iv <SEP> O <SEP> 0 <SEP> A <SEP> x <tb> <SEP> V <SEP> <SEP> ! <SEP> 0 <SEP> # <SEP> X <SEP> <tb> <SEP> vi <SEP> O <SEP> 0 <SEP> X <SEP> X <tb> <SEP> vii <SEP> 0 <SEP> 0 <SEP> O <SEP> A <tb> viii <SEP> 0 <SEP> O <SEP> 0 <SEP> A <tb> <SEP> ix <SEP> O <SEP> A <SEP> X <SEP> X <SEP> <tb> <SEP> x <SEP> X <SEP> X <SEP> X <SEP> X <tb> <SEP> xi <SEP> 0 <SEP> 0 <SEP> # <SEP> <SEP> X <tb> Note:o, # and X denote "Soluble", "Slightly opaque or dispersed" and "Insoluble", respectively. Table 2 EMI32.1 <tb> Compound <SEP> Surface <SEP> tension <SEP> <tb> <SEP> (dyn/cm) <tb> (Toluene) <SEP> (28.5) <tb> <SEP> 20.2 <tb> <SEP> ii <SEP> 21.4 <tb> <SEP> iii <SEP> 20.5 <tb> <SEP> iv <SEP> 21.5 <tb> <SEP> v <SEP> 20.8 <tb> <SEP> vi <SEP> 19.8 <tb> <SEP> vii <SEP> 19.9 <tb> <SEP> viii <SEP> 22.0 <tb> <SEP> ix <SEP> 25.2 <tb> <SEP> xi <SEP> 25.0 <tb> <SEP> xii <SEP> 26.5 <tb> Note: 1) Surface tension of 0.1 wt % ; solution in toluene. Compound (x) was not dissolved in toluene. Example 7 Preparation of EMI32.2 To the reaction mixture prepared in the same manner as in Example 1 (a), CH3I (4.97 g, 0.035 mole) was added and reacted at 700C for 7 hours. Thereafter, unreacted CH3I and isopropanol were distilled off, and the residue was washed with ether to obtain the title compound (12.63 g). Yield 90 %. Elemental analysis: C H N O I F Calc'd: 45.30 6.55 1.99 11.40 9.05 25.71 Found: 45.28 6.55 2.02 11.41 9.01 25.73 Bromophenol Blue test To 10 ml of a 1 wt % aqueous solution of the thus prepared compound, there added a few drops of a mixture of 0.2 N aqueous solution of sodium acetate (75 ml), 0.2 N aqueous solution of acetic acid (925 ml) and 96 % ethanol containing 0.1 % by weight of Bromophenol Blue (20 ml). The aqueous solution turned blue, which indicated the presence of an cationic surfactant. Example 8 Preparation of EMI33.1 (a) To the same flask as used in Example 1 (b), C7F15C0OC2H5 (4.42 g, 0.01 mole), H2N(CH2)3O((CH2)40)8- (CH2) 3NH2 (7.08 g, 0.01 mole) and isopropanol (15 g) were charged and reacted. Gas chromatography analysis revealed that the ester was consumed. (b) and (c) To the reaction mixture prepared in the step (a), CH3I (4.97 g, 0.035 mole) was added and reacted at 800C for 7 hours. Thereafter, unreacted CH3 I and isopropanol were distilled off, and the residue was washed eith ether to obtain the title compound (11.46 g). Xield 90 %. 19F-NMR (External standard : CF3COOH) EMI34.1 <tb> Chemical <SEP> shift <SEP> 6 <SEP> (ppm) <SEP> Signal <SEP> strength <tb> <SEP> 3.4 <SEP> 3F <tb> <SEP> 41.6 <SEP> 2F <tb> <SEP> 44.0 <SEP> 4F <tb> <SEP> 44.8- <SEP> 4F <tb> <SEP> 48.3 <SEP> 2F <tb> -1 IR spectrum: 1,720 cm (-CO-NH-). The result or the Bromophenol Blue test was identical to that of Example 7. Example 9 Preparation of EMI34.2 (a) To the same flask as used in Example ; (a), C7F15CH2CH2SOCl (4.97 g, 0.01 mole), H2N(CH2) 30((CH2)4O)8- (CH2)3NH2 (7.08 g, 0.01 mole) and trichlorotrifluoroethane (20 g) were charged and reacted at 0 C for 30 minutes and then at a room temperature for 2 hours. (b) and (c) To the reaction mixture prepared in the step (a), CH3I (4.97 g, 0.035 mole) and isopropanol (15 g) were added and reacted at 800C for 7 hours. Thereafter, unreacted CH3I, isopropanol and trichlorotrifluoroethane were distilled off, and the residue was washed with ether to obtain the title compound (12.31 g). Yield 92 %. Elemental analysis: C H N O S I F Calc'd: 44.84 6.73 2.09 13.15 2.39 9.49 21.30 Found: 44.82 6.73 2.06 13.18 2.43 9.47 21.31 The result of the Bromophenol Blue test was identical to that of Example 7. Example 10 Preparation of EMI35.1 (a) To the same flask as used in Example 1 (a), C8F17CH2CH2I (5.74 g, 0.01 mole), H2N(CH2)3O((CH2)4O)8- (CH2)3NH2 (7.08 g, 0.01 mole) and isopropanol (15 g) were charged and reacted at 700C for 6 hours. Gas chromatography analysis revealed that the iodide compound was consumed. (c) To the reaction mixture prepared in the step (a), C2H5Br (2.18 g, 0.02 mole) was added and reacted at 700C for 5 hours. Gas chromatography analysis revealed that C H Br was consumed. (c) To the reaction mixture prepared in the step (a), EMI35.2 (1.27 g, 0.01 mole) was added and reacted at 700C for 5 hours. Gas chromatography analysis revealed that EMI35.3 was consumed. Thereafter, isopropanol was distilled off, and the residue was washed with ether to obtain the title compound (12.03 g). Yield 90 %. Elemental analysis: C H N O C1 F Calc'd: 52.97 7.33 2.10 10.77 2.66 24.17 Found: 53.01 7.35 2.10 10.77 2.62 24.15 The result of the Bromophenol Blue test was identical to that of Example 7. Example 11 Preparation of EMI36.1 (a) The same procedure as in Example 1 (a) was repeated. (b) To the reaction mixture prepared in the step (a), ClCH2CH2OH (1.61 g, 0.02 mole) was added and reacted at 70 C for 6 hours. Gas chromatography analysis revealed that ClCH2CH2OH was consumed. (c) To the reaction mixture prepared in the step (b), S04(CH3)2 (1.39 g, 0.011 mole) was added and reacted at 600C for 2 hours. Thereafter, isopropanol was distilled off, and the residue was washed with ether to obtain the title compound (13.03 g). Yield 90 %. Elemental analysis: C H N O S F Calc'd: 46.41 6.84 1.93 17.68 2.21 24.93 Found: 46.39 6.80 1.97 17.76 2.18 24.90 The result of the Bromophenol Blue test was identical to that of Example 7. Test Examples and Comparative Examples Solubility of the following compounds of the invention and comparative compounds in some organic solvents, and their surface tension of a 0.1 % by weight solution in toluene were measured at 25 C. The surface tension was measured by the Wilhelmy method. Compounds of the invention EMI37.1 EMI38.1 Comparative compounds EMI38.2 Table 3 EMI39.1 <tb> <SEP> Compound <SEP> ethyl <SEP> Ethyl <SEP> Dimethyl <SEP> Toluene <tb> <SEP> ethyl <SEP> acetate <SEP> formamide <tb> <SEP> ketone <tb> Q <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> ii <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> <tb> <SEP> iii <SEP> 0 <SEP> # <SEP> 0 <SEP> 0 <tb> <SEP> iv <SEP> 0 <SEP> 0 <SEP> 0 <SEP> X <tb> <SEP> v <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> vi <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> vii <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> viii <SEP> X <SEP> X <SEP> X <SEP> <SEP> X <SEP> <tb> <SEP> ix <SEP> x <SEP> x <SEP> O <SEP> X <SEP> <tb> <SEP> x <SEP> O <SEP> X <SEP> X <SEP> X <tb> <SEP> xi <SEP> X <SEP> X <SEP> X <SEP> X <tb> <SEP> xii <SEP> 0 <SEP> 0 <SEP> O <SEP> X <SEP> <tb> Note: O, A and X denote "Soluble", "Slightly opaque or dispersed" and "Insoluble", respectively. Table 4 EMI40.1 <tb> Compound <SEP> Surface <SEP> tension1) <tb> <SEP> (dyn/cm) <tb> (Toluene) <SEP> (28.5) <tb> <SEP> 18.5 <tb> <SEP> ii <SEP> 22.8 <tb> <SEP> iii <SEP> 18.2 <tb> <SEP> iv <SEP> 16.4 <tb> <SEP> v <SEP> 19.0 <tb> <SEP> vi <SEP> 19.2 <tb> <SEP> vii <SEP> 18.9 <tb> <SEP> xi <SEP> 25.2 <tb> <SEP> xii <SEP> 25.0 <tb> <SEP> xiii <SEP> 26.7 <tb> Note: 1) Surfacc tension of 0.1 wt % solution in toluene. Compounds (viii) to (x) were not dissolved in toluene. Example 12 Preparation of EMI40.2 (a) To the same flask as used in Example 1, 7F15 COOC2H5 (4.42 g, 0.01 mole), H2N(CH2)3O((CH2)4O)13 (CH2)3NH2 (10.68 g, 0.01 mole) and isopropanol (15 g) were charged and reacted to 70 C for 7 hours. Gas chromatography analysis of the reaction mixture revealed that the ester was consumed. (b) To the reaction mixture prepared in the step (a), CH3I (12.84 g, 0.02 mole) was added and reacted at 700C for 5 hours. (c) To the reaction mixture prepared in the step (b), CH2=CHCOOH (0.86 g, 0-.012 mole) was added and reacted at 700C for 7 hours. Thereafter, isopropanol was distilled off, and the residue was washed with a mixture of acetonitrile and trichlorotrifluoroethane in a weight ratio of 1:1 to obtain the title compound (14.08 g). Yield 90 %. Elemental analysis: C H N O F Calc'd: 54.48 8.12 1.79 17.39 18.22 Found: 54.35 8.15 1.80 17.50 18.20 IR spectrum: 1,600 (-CH2COO ) and 1,720 cm (-CO-NH-). Example 13 Preparation of EMI41.1 (a) To the same flask as used in Example 1 (a), EMI41.2 (CH2)3NH2 (7.08 g, 0.01 mole) and isopropanol (1S g) were charged and reacted to 700C for 6 hours. Gas chromatography analysis of the reaction mixture revealed that the epoxide was consumed. (b) and (c) To the reaction mixture prepared in the step (a), ClCH2COOH (2.84 g, 0.03 mole) was added and reacted at 700C for 7 hours. Thereafter, isopropanol was distilled off, and the residue was washed with the same solvent mixture as used in Example 12 to obtain the title compound (13.37 g). Yield 95 t. Elemental analysis: C H N O F Calc'd: 47.73 6.46 1.99 18.18 25.64 Found : 47.70 6.32 2.01 18.30 25.67 IR spectrum : 1,600 (-CH2COO-) and 1,755 cm-1 (-CH2COOH). Example 14 Preparation of EMI42.1 (a) To the same flask as used in Example 1 (a), C8F17SO2Cl (5.19 g, 0.01 mole), H2N(CH2)30((CH2)4O)27(CH2)3- NH2 (20.76 g, 0.01 mole) and trichlorotrifluoroethane (20 g) were charged and reacted at OOC for 30 minutes and then at a room temperature for 2 hours. (b) To the reaction mixture prepared in the step (a), CH3I (2.84 g, 0.02 mole) and isopropanol (15 g) were added and reacted at 700C for 6 hours. (c) To the reaction mixture prepared in the step (b), EMI43.1 (1.53 g, 0.01 mole) was added and reacted at 700C for 6 hours. Thereafter, isopropanol and trichlorotrifluoroethane were distilled off, and the residue was washed with the same solvent mixture as used in Example 12 to obtain the title compound (24.05 g). Yield 89 %. Elemental analysis: C H N O S F Calc'd: 56.85 8.85 1.04 20.13 1.18 11.95 Found: 56.71 8.95 1.03 20.11 1.22 11.98 -1 IR spectrum: 1,600 (-COO ) and 1,755 cm (-COOH). Example 15 Preparation of EMI43.2 (a) To the same flask as used in Example 1 (a), C8F17CH2CH2I (5.74 g, 0.01 mole), EMI43.3 (2.48 g, 0.01 mole) and isopropanol (15 g) were charged and reacted at 700C for 6 hours. Gas chromatography analysis of the reaction mixture revealed that the iodide compound was consumed. (b) To the reaction mixture prepared in the step (a), CH3I (2.84 g, 0.02 mole) was added and reacted at 700C for 5 hours. Gas chromatography analysis of the reaction mixture revealed that CH3 I was consumed. (c) To the reaction mixture prepared in the step (b), BrCH2CH2SO3H (1.89 g, 0.01 mole) was added and reacted at 700C for 5 hours. Thereafter, isopropanol was distilled off, and the residue was washed with the same solvent mixture as used in Example 12 to obtain the title compound (7.47 g) . Yield 90 %. Elemental analysis: C H N O S F Calc'd: 37.59 4.70 3.37 11.57 3.86 38.92 Found: 37.61 4.59 3.35 11.70 3.86 38.90 Test Examples and Comparative Examples Solubility of the following compounds of the invention and comparative compounds in some organic solvents, and their surface tension of a 0.1 8 by weight solution in toluene were measured at 250C. The surface tension was measured by the Wilhelmy method. Compounds of the invention EMI44.1 EMI45.1 Comparative fluorine-containing betaine compounds EMI45.2 Comparative fluorine-containing surfactant EMI46.1 FC-430 (xiii) Table 5 EMI46.2 <tb> <SEP> Compound <SEP> Acetone <SEP> Ethyl <SEP> Toluene <tb> <SEP> acetate <tb> <SEP> i <SEP> 0 <SEP> # <SEP> <SEP> # <tb> <SEP> ii <SEP> 0 <SEP> # <SEP> <SEP> # <tb> <SEP> iii <SEP> 0 <SEP> 0 <SEP> 0 <tb> iv <SEP> O <SEP> # <SEP> <SEP> 0 <SEP> 0 <tb> V <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> vi <SEP> 0 <tb> vii <SEP> 0 <SEP> 0 <SEP> O <tb> <SEP> viii <SEP> X <SEP> X <SEP> <SEP> X <SEP> <tb> <SEP> ix <SEP> X <SEP> X <SEP> X <tb> <SEP> x <SEP> X <SEP> X <SEP> X <tb> Note: 0, # and X denote "Soluble", "Slightly opaque or dispersed" and "Insoluble", respectively. Table 4 EMI47.1 <tb> Compound <SEP> Surface <SEP> tension1) <tb> <SEP> (dyn/cm) <tb> (Toluene) <SEP> (28.5) <tb> <SEP> i <SEP> 16.3 <tb> <SEP> ii <SEP> 17.6 <tb> <SEP> iii <SEP> 19.8 <SEP> <tb> <SEP> iv <SEP> 23.3 <tb> <SEP> 18.7 <tb> <SEP> vi <SEP> 17.1 <tb> <SEP> vii <SEP> 23.4 <tb> <SEP> xi <SEP> 25.2 <tb> <SEP> xii <SEP> 25.0 <tb> <SEP> xiii <SEP> 26.7 <tb> Note: Surface tension of 0.1 wt % solution in toluene. Compounds (viii) to (x) are not dissolved in toluene.

Claims: CLAIMS : 1. A fluorine-containing compound of the formula: EMI48.1 wherein Rf is a C3 -C21 fluorinated hydrocarbon group or a C3-C21 fluorinated oxyhydrocarbon group; X1 is a C1-C11 hydrocarbon group; X2, X3 and X4 are each a C2-C6 hydrocarbon group ; yl is a group of the formula: EMI48.2 y2 is a group of the formula: EMI48.3 W1 is a group of the formula: EMI48.4 W2 is a C1-Cl0 hydrocarbon group optionally having -OH or -COOH or a amide group in the backbone; Z1 is halogen or a group of the formula: EMI49.1 22 is a group of the formula: EMI49.2 Z3 is a group of the formula: EMI49.3 R1 is hydrogen or a C1-C5 hydrocarbon group; R2 is hydrogen or a C2-C4 acyl group ; R3 is hydrogen or a group of the formula : -(XÚO)qH or -R7Z3; R4 is a group of the formula: -(X10) H or -R7Z3; q R5 and R6 are each a C1-C20 hydrocarbon group or a group of the formula: -(X1O)qH, -X1kCOOM, -Rf or -Y1X1kRf ; R7 is a C1-C20 hydrocarbon group or a group of the formula : -(CH2CH2OCH2CH2)@- ; R8, R9 and R10 are each a C1-C20 hydrocarbon group or a group of the formula: -(X1O)-H, -Rf or -Y1X2kRf ; R11 is C2-C6 alkylene group optionally having one or two oxygen or sulfur atoms; R12 is hydrogen, a C1-C20 hydrocarbon group or a C2-C20 acyl group; R13 is hydrogen or a C1-C20 hydrocarbon group; M is hydrogen, an alkali metal, an alkaline earth metal or a NH4 group; k is zero or one; m is an integer of 1 to 50; n is an integer of i to 5; q is an integer of 1 to 20; and r is an integer of 1 to 5. 2. A fluorine-containing compound according to claim 1, wherein Y2 is a group of the formula: EMI50.1 wherein R3 and R4 are the same as defined above. 3. A fluorine-containing compound according to claim 1, wherein Y2 is a group of the formula: -W1-Z1 wherein 1 and Glare the same as defined above. 4. A fluorine-containing compound according to claim 1, wherein Y2 is a group of the formula: EMI51.1 wherein W Z2 R5 and R6 are the same as defined above. 5. A fluorine-containing compound according to claim 1, wherein Rf is selected from the group consisting of C5-C15 fluorinated aliphatic groups and C5-C15 fluorinated oxyhydrocarbon groups. 6. h fluorine-containing compound according to claim 1, wherein Rf is a C5-C15 perfluorinated saturated aliphatic group. 7. A fluorine-containing compound according to claim 1, wherein Rf is a group of the formula: CtF2t+l-, H-(CtF2t)- CtF(2tl) or EMI51.2 wherein t is an integer of 3 to 21 and u is an integer of 0 to 5. 8. A fluorine-containing compound according to claim 1, wherein X1 is a C1-C4 aliphatic group. 9. A fluorine-containing compound according to claim 8, wherein X1 is selected from the group consisting -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2- and -(CH2)4-. 10. A fluorine-containing compound according to claim 1, wherein X2 is a C2-C4 aliphatic group. 11. A fluorine-containing compound according to claim 10, wherein X2 is selected from the group consisting of -CH2CH2-, -CH(CH3)CH2- and -(CH2)4-. 12. A fluorine-containing compound according to claim 1, wherein X3 is a C2-C4 aliphatic group. 13. A fluorine-containing compound according to claim 12, wherein X3 is selected from the group consisting of -CH2CH2-, -CH(CH3)CH2- and -(CH2)4-. 14. A fluorine-containing compound according to claim 1, wherein X4 is a C Cq aliphatic group. 15. A fluorine-containing compound according to claim 14, wherein X4 is selected from the group consisting of -CH2CH2-, -CH(CH3)CH2- and -(CH2)4-. 16. A fluorine-containing compound according to claim 1, wherein Z is selected from the group of halogen and groups of the formulas: -OR12 and -OSO3R 3. 17. A fluorine-containing compound according to claim 1, wherein hologen is selected from the group of iodine, bromine and chlorine. 18. A fluorine-containing compound according to claim 1, wherein R12 is hydrogen or a C1-C6 aliphatic group. 19. A fluorine-containing compound according to claim 18, wherein R12 is hydrogen or a C1-C6 saturated alkyl group. 20. A fluorine-containing compound according to claim 1, wherein R13 is hydrogen or a C1-C6 aliphatic group. 21. A fluorine-containing compound according to claim 20, wherein R13 is a C1-C6 saturated alkyl group. 22. A fluorine-containing compound according to claim 20, wherein R1 and R2 are hydrogens. 23. A fluorine-containing compound according to claim 1, wherein each of R5 to R10 which is the hydrocarbon group is an aliphatic, aryl or aralkyl group. 24. A fluorine-containing compound according to claim 1, wherein R5 and R6 are each a group of the formula: -(X1O)qH, -XlkCOOM, Rf or -Y1XlkRf.

Inventors: HISAMOTO, IWAO, YAMANA, MASAYUKI
Applicants: DAIKIN INDUSTRIES, LIMITED
Application year: 1984
Main classification: C07C103
IPC codes: B01F17, B01D19