MXPA06008626A - Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers - Google Patents

Abstract

Production processes and systems are provided that include reacting halogenated compounds, dehalogenating compounds, reacting alcohol’s, reacting olefins and a saturated compounds, reacting reactants having at least two -CF3 groups with reactants having cyclic groups. RF--compositions such as RF-intermediates, RF-surfactants, RF-monomers, RF--monomer units, RF-metal complexes, RF-phosphate esters, RF-glycols, RF--urethanes, and/or RF-foam stabilizers. The RF portion can include at least two -CF3 groups, at least three -CF3 groups, and/or at least two -CF3 groups and at least two -CH2- groups. Detergents, emulsifiers, paints, adhesives, inks, wetting agents, foamers, and defoamers including the RF-surfactant composition are provided. Acrylics, resins, and polymers are provided that include a RF-monomer unit. Compositions are provided that include a substrate having a RF-composition thereover. Aqueous Film Forming Foam ("AFFF") formulations are provided that can include RF-surfactants and/or RF-foam stabilizers are provided.

Description

FR, GB, GR, HU, LE, ÍS, 1T, LT. LU, MC, NL, PL, PT, RO, PubUshed: SE, SI, SK, TR), OAPI (BF, BJ, CE CG, Cl, CM, GA, GN. - with intemalional search report GQ, GW, ML MR, NE, SN, TD, TG). Declarations under Rule 4.17: (88) Date of publication of the internatíonal searcb report: - as applicable, it is eniitleme t the applyfor and be granled to 30 March 2006 patenl (Rule 4.17 (ii)) for all designations - as the applicanl's entilleme and to claim the priority of the For two-leler codes and olher abbrevialions, refer the "Guidearlier application (Rule 4.17 (iii)) for all designations ance Notes on Codes and Abbrevialions" appearing to lite begin- - of inventorship (Rule 4.J7 (iv)) for US only no regular issue of the PCT Gazepe.

PROCEDURES OF PRODUCTION AND SYSTEMS, COMPOSITIONS, SURFACTANT AGENTS, MONOMERIC UNITS, COMPLEXES METALLIC, PHOSPHATE ESTERS, GLYCOLS. FOAMS THAT FORM AQUEOUS FILMS, AND FOAM STABILIZERS PRIORITY CLAIM This application claims priority to the Patent Application Provisional US Serial No. 60 / 540,612, entitled Fluor Functional Groups, Fluorine Compositions, Processes for Manufacturing Fluorine Compositions, and Material Treatments, filed on January 30, 2004, the entirety of which is incorporated by reference in the present invention.

FIELD OF THE TECHNIQUE The present invention relates to the field of halogenated compositions, processes for the preparation of halogenated compositions, and, more specifically, fluorinated compositions, processes for the preparation of fluorinated compositions and methods for the treatment of substrates with fluorinated compositions.

BACKGROUND OF THE INVENTION Compositions such as surfactants and polymers, for example, have incorporated fluorine to affect the performance of the composition when the composition is used as a treatment for the materials and when the composition is used to improve the performance of the materials. For example, surfactants that incorporate fluorinated functional groups can be used as fire extinguishers either alone or in formulations such as foaming aqueous films (AFFF). Traditional surfactant fluoroagents, such as perfluoro-octyl sulfonate derivatives (PFOS), have perfluorinated linear portions. Polymers that incorporate fluorine have been used to treat materials. Exemplary fluorinated treatments include compositions such as Scotchguard®.

BRIEF DESCRIPTION OF THE INVENTION Production methods and systems are provided which include: a reactor having at least one interior side wall including glass; reacting a halogenated compound with a compound comprising allyl in the presence of water to form a halogenated intermediate; dehalogenating a portion of a heterohalogenated alcohol to form a homohalogenated alcohol, with the heterohalogenated alcohol including at least two groups -CF3 and at least one halogen other than fluorine; reacting an alcohol to form an acrylate, with the alcohol including at least two -CF3 groups and a cyclic group; reacting an olefin with a saturated compound to form a saturated product, with the olefin including at least two groups -CF3, the saturated compound including at least two other groups -CF3, and the saturated product including both the -CF3 groups of the olefin and the -CF3 groups of the saturated compound; and / or reacting a first reagent that includes at least two -CF3 groups with a second reagent that includes a cyclic group to form a compound that includes the two -CF3 groups and the cyclic group. RF compositions such as RF-intermediates, RF-surfactants, RF-monomers, RF-monomer units, RF-metal complexes, RF-phosphate esters, RF-glycols, RF-urethanes, and / or foam-RF stabilizers. - The RF portion can include at least two groups -CF3, at least three groups -CF3, and / or at least two groups -CF3 and at least two groups -CH2-. The surfactant-R compositions such as RF-QS are provided, with the RF portion having a greater affinity for a first part of a system having at least two parts compared to the Qs portion, and Qs having a higher portion. affinity for a second part of the system compared to the RF portion. Detergents, emulsifiers, paints, adhesives, inks, wetting agents, foaming adhesives, and defoamer including the surfactant-RF composition are provided. Methods for production are provided including the provision of a first compound, with the first compound including the minus two groups -CF3 and two hydrogens, and a portion of the first compound representing the RF portion of a surfactant-RF and the addition of a portion Qs to the RF portion to form the surfactant-Rp. Methods for altering a surface tension of a part of a system having at least two parts including the addition of an RF-surfactant are provided. Acrylics, resins, and polymers are provided which include a monomeric-RF unit, with the RF portion including, for example, a pendant group of the monomeric unit. The compositions are provided which include a substrate having an RF-composition. Production methods are provided which may include the provision of an RF-monomer and the combination of the monomer-Rp with another monomer to form an oligomer. Exemplary oligomers may include monomeric-RF units. RF-metal complexes that can include a metal and a ligand are provided, with the ligand including RF-OMC- The QMC portion being coordinated with the complex metal, for example. Phosphate-Rp esters that can include RF-QPE >are provided; with the QPE portion including the phosphorous portion of the ester.

The glycols-RF are provided which may include Rp-Q, with Qh including a hydroxyl portion of the glycol. Also supplied are urethanes-RF such as RF-QU, with the portion Qu being the remnant of the urethane. Foamable aqueous film ("AFFF") formulations are provided which may include RF-surfactants and / or foam-RF stabilizers.

BRIEF DESCRIPTION OF THE DRAWINGS The modalities are described below with reference to the following annexed drawings. Figure 1 is a general view of exemplary Rp-compositions. Figure 2 is an exemplary system for preparing compositions according to one embodiment. Figure 3 is an exemplary system for preparing compositions according to one embodiment. Figure 4 is an exemplary system for preparing compositions according to one embodiment. Figure 5 is an exemplary system for preparing compositions according to one embodiment.

Figure 6 is an exemplary system for the preparation of compositions according to one embodiment. Figure 7 is an exemplary system for preparing compositions according to one embodiment. Figure 8 is an exemplary system for preparing compositions according to one embodiment. Figures 9 to 16 show different surface tensions of various solutions DETAILED DESCRIPTION OF THE INVENTION Exemplary RF-compositions and production systems are described with reference to Figures 1-8. With reference to Figure 1, an overview of the exemplary RF-compositions is shown. The RF-compositions include, but are not limited to, RF-surfactants, RF-monomers, Rp-monomer units, RF-metal complexes, Rp-phosphate esters, RF-glycols, RF-urethanes, and foam stabilizers. RF In exemplary embodiments, poly-anhydrides, acrylics, urethanes, metal complexes, poly-ennes, and / or phosphate esters may also include Rp portions. The RF-compositions include compositions having an RF portion and / or RF portions. The RF portion may be Rp-groups, such as pendant groups and / or portions of compositions. The RF portion can include at least two CF-3 groups and the CF-3 groups can be terminal. The RF portion can also include both groups -CF3 and additional groups containing fluorine, such as -CF2- groups. In exemplary embodiments, the RF portion may include a ratio of the-CF2- groups to the -CF3 groups that is less than or equal to two, such as the (CF3) 2CF- groups. The RF portion may also include hydrogen. For example, the R portion may include two -CF3 hydrogen groups, such as the groups (CF3) 2CH-. The RF portion can also include two groups -CF3 and one group -CH2-, in other embodiments. The RF portion can include at least three groups -CF3, such as two groups (CF3) 2CF-. In exemplary embodiments, the RF portion can include cyclic groups such as aromatic groups. The RF portion may include at least two groups -CF3 and at least four carbons with, for example, one of the four carbons including a -CH2- group. In exemplary implementations, the RF-compositions can demonstrate desirable surface energies, affect the surface tension of the solutions to which they are exposed, and / or affect the environmental resistance of materials to which they are applied and / or incorporated. Exemplary compositions include, but are not limited to, substrates having Rp compositions thereon and / or liquids having RF-compositions. The RF portions can be incorporated into compositions such as acrylate polymers, monomers and polymers, glycols, surfactant fluoro-agents, and / or AFFF formulations. These compositions can be used as dispersion agents or to treat substrates such as textile fabrics, textile yarn, leather, paper, plastic, linen for sheets, wood, clay for ceramics, as well as, articles of clothing, tapestries, paper bags, cardboard boxes, porous earthenware, construction materials such as brick, stone, wood, concrete, ceramics, tiles, glass, stucco, plaster, stone wall, chipboard board, gray cardboard, carpets, upholstery, furniture upholstery, automotive elements, awning fabrics, and waterproof clothing. The Rp-compositions can be prepared from the RF-intermediates. The RF portions can be incorporated into the RF-compositions and / or they can be raw materials for the RF-intermediary-RF compositions. Exemplary RF-intermediates include a previously described RF portion, as well as at least one functional portion that allows incorporation of the RF portion within the compositions to form Rp-compositions. The functional portions may include halogens (e.g., iodine), mercaptan, thiocyanate, sulfonyl chloride, acid, acid halides, hydroxyl, cyano, acetate, allyl, epoxide, acrylic ester, ether, sulfate, thiol, phosphate, and / or amines, for example. Without incorporation and / or reaction, the RF-intermediates can include RF-compositions, such as Rp-monomers and / or metal-RF complex ligands, for example. The RF-intermediaries may include RF-Qg with RF representing the RF portion and Qg representing, for example, the functional portion, and / or, as another example, an element of the periodic table of the elements. In exemplary embodiments, Qg is not a proton, methyl, and / or methylene group. Exemplary RF-intermediaries include, but are not limited to, those in Table 1 below.

RF-intermediaries can also include Qfl (R CH) nRF Rpíf CH CF3 CF, and / or one or both of RF (RrCH) nQ9 RF (CH2-CH) nQg CF3 and CF3 with Ri including at least one carbon atom, such as - CH2-, for example. In exemplary modalities, n may be at least 1 and in Other modalities can be a! minus 2 and the RF-broker may include one or more of RF (CH2 H RC? (CH2-CH-CH-CH2) H and / or CF "3, The intermediary-RF (4-Exo-2- (trifluoromethyl) -1,1,1,2-tetrafluorobutane) can be obtain, for example, in Matrix Scientific, P. O. Box 25067, Columbia, SC 92994-5067.

The RF-intermediate (1,1,1-trifluoro-2-trifluoromethyl-2,4-pentadiene) can be prepared in an exemplary manner in accordance with J. Org. Chem., Vol. 35, No. 6, 1970, pp. 2096-2099, incorporated herein by reference. 1, 1, 1-trifluoro-2-trifluoromethyl-2,4-pentadiene can also be prepared according to the following example. 1,1,1-Trifluoro-2-trifluoromethyl-2,4-pentadiene can be prepared according to scheme (1) below, With reference to the aforementioned scheme (1), pentane (300 mL) can be placed in a 500 ml flask with three necks and cooled below -30 ° C. Pentane can be added hexafluoroacetone (59 grams, 0.36 moles), propylene (16.2 grams, 0.38 moles), and anhydrous aluminum trichloride (0.77 g, 0.006 moles) to form a mixture. This mixture can be stirred and the temperature raised to room temperature for a period of 3 hours. An aqueous solution of 15% HCl (w / w) (20 mL) can be added to the mixture, and the mixture can be washed 3 times with H20. The aqueous layer, after washing, can be decanted, and the organic layer (pentane and propylene) can be dried with MgSO4. The remaining pentane and propylene can be vaporized instantaneously at 60 ° C to produce 54.4 grams (70% of the percentage area by gas chromatography) of the 1, 1-bis (trifluoromethyl) -3-penten-1-ol isomeric. Unpurified 1, 1-bis (trifluoromethyl) -3-penten-1-ol (54 grams) can be placed in a 250 ml flask with three necks and 125 mL of concentrated H2SO4 is added to form a mixture which is mixed. can stir and heat slowly to 95 ° C (separating the compounds having lower boiling points from the mixture between 34 ° C and 55 ° C). The 1, 1, 1-trifluoro-2-trifluoromethyl-2,4-pentadiene (15.6 grams, 45.5% yield) produced can be separated from the mixture as a gas between 70 ° C and 74 ° C. Exemplary intermediates-Rp can be prepared from the 2-iodoheptafluoropropane reagent. In an exemplary embodiment, halogenated compounds such as 2-iodoheptafluoropropane can be prepared with reference to Figure 2. With reference to Figure 2, a system 20 is illustrated which includes a reactor 22 coupled to a vessel for the alkyl reagent 24, a container for the halogenating agent 26, and a container for the halogenated compound 28. In accordance with exemplary embodiments, the system 20 can be used to halogenate an alkyl reagent with a halogenating agent within the reactor 22 to form a halogenated compound. The alkyl reagent within the alkyl reagent container 24 may include an olefin such as a fluoro-olefin, for example hexafluoropropene. The halogenating agent within the container for the halogenating agent 26 can include a mixture of a salt and a diatomic halogen, such as KF and 12, KF and Br2, and salts such as ammonium salts, for example. In an exemplary embodiment, reactor 22 can be coated with glass and / or hastelloy®, such as hastelloy® C. In accordance with another embodiment, conduits 29 can be configured to provide the contents of containers 24 and 26 to reactor 22 and / or providing the contents of the reactor 22 to the container 28. The conduits 29 can be coated with glass and / or hastelloy®, such as hastelloy® C. The conduits 29 and the reactor 22 both can be reverted with glass and / or hastelloy ®, ta! like hastelloy® C, for example. In an exemplary embodiment, the halogenating agent can be supplied to the reactor 22 with a reactive medium, such as a polar, aprotic solvent including, for example, acetonitrile and / or dimethyl formamide (DMF). The reactive medium can be added through another conduit (not shown) or, simultaneously with the halogenating agent, through the container 26. Together, the halogenating agent and the reactive medium can form a mixture within the reactor 22 which is you can add the alkyl reagent to form another mixture that includes the agent, the medium, and the reagent. The alkyl reagent can be reacted within this mixture to form the halogenated compound. In an exemplary embodiment, the reactive medium can be found in the liquid phase when the alkyl reactant is reacted within the mixture. The mixture can also be stirred when the alkyl reactant is reacted, for example, and the mixture can also be heated. In an exemplary embodiment, the hexafluoropropene can be supplied to the reactor 22 having KF, 12, and acetonitrile and a portion of the contents of the reactor 22 were heated to at least about 90 ° C, and / or from about 90 ° C to about 135 ° C, to form 2-iodoheptafluoropropane. The hexafluoropropene can also be supplied to the reactor 22 having KF, 12, and acetonitrile with a pressure inside the reactor 22 being from about 446 kPa to 929 kPa to form 2-iodoheptafluoropropane. The halogenated compound can also be removed from reactor 22 a! vessel 28 via conduit 29. In an exemplary embodiment, conduit 29, between vessel 28 and reactor 22, may include a capacitor (not shown). A portion of the halogenated compound formed within the reactor 22 can be converted to a gas, the gas can be transferred to the condenser, the condenser can return the gas to a liquid, and the liquid can be removed from the condenser and transferred to the vessel 28 In exemplary embodiments, conduit 29, between reactor 22 and 28, which is configured to include the condenser, can be referred to as an apparatus for distillation. Halogenated compounds such as the above-described 2-iodoptafluoropropane can be removed from the reactor 22 by heating at least a portion of the 2-iodoheptafluoropropane to at least about 40 ° C. The exemplary halogenated compounds described above can be used to prepare RF-intermediates such as (1,1,1,2-tetrafluoro-2- (trifluoromethyl) -4-iodobutane). For example, and by way of example only, 105.14 grams of 2-iodoheptafluoropropane and 10 grams of ethylene can be added to an 800 mL Parr reactor. The reactor can be heated to about 180 ° C for about 6 hours. The reactor can then be cooled and a portion of the contents removed to produce approximately 105.99 grams of the intermediate-RF 1,1,1-tetrafluoro-2- (trifluoromethyl) -4-iodobutane being approximately 86% pure (as described above). determined by gas chromatography). The 1,1,1,2-tetrafluoro-2- (trifluoromethyl) -4-iodobutane can also be distilled at 56 ° C / 96 Torr. 1, 1, 1, 2-tetrafluoro-2- (trifluoromethyl) -4-iodobutane can also be obtained from Matrix Scientific (catalog number 1104). Halogenated compounds can also be used to prepare RF-intermediates such as the heterohalogenated intermediate 7,8,8,8-tetrafluoro-7- (trifluoromethyl) -5-iodooct-1-ene. The RF-intermediate can be prepared and subsequently dehalogenated to form another RF-intermediate according to the scheme (2) below. With reference to the aforementioned scheme (2), 2- iodoheptafluoropropane (231.3 grams, 0.782 moles), 1,5-hexadiene (126.6 g, 0.767 moles), and 2,2'-azobisisobutyronitrile (AIBN) (13.6 g, 0.083 moles) can be loaded together into a 750 mL clean and dry stainless steel autoclave equipped with a safety disc, thermocouple, heating bands, electronic temperature controller, inner tube with needle valve, gas valve with valve of needle, manometer, and agitator. The apparatus can then be sealed and heated slowly to approximately 60 ° C when an exotherm can be observed and slowly the temperature can be raised to approximately 80 ° C. The contents of the apparatus can be maintained at 80 ° C for approximately 72 hours producing approximately 337 g of unpurified material. The contents can be vacuum distilled (53 ° C / 5.0 Torr) to yield approximately 125 g 99.6% percent area purity (by gas chromatography) of the intermediate-Rp 7,8,8,8-tetrafluoro-7- ( trifluoromethyl) -5-iodooct-1-ene (m / z 377.7 (M +), 251 (M + -l)), IR spectrum: olefinic extension CH in (w) 3082 cm'1, extension C = C in (w) 1643 cm "1, and characteristic bands at 729, 1149, 1224, and 1293 cm" 1, 1 H NMR, 19 F NMR, 13 C NMR, high resolution MS can be used to determine 7,8,8,8-tetrafluoro- 7- (trifluoromethyl) -5-iodooct-1-ene also. With reference again to the above-mentioned scheme (2), 7,8,8,8-tetrafluoro-7- (trifluoromethyl) -5-iodooct-1-ene (36.1 grams, 0.095 mol) can be added to a flask of 100 mL round bottom with three necks equipped with a reflux condenser, an outer cover for heating, thermocoupler, electronic heat controller, and stirrer and heated to 75 ° C. Tributyltin hydride (34.6 grams, 0.119 moles) can be added dropwise through an addition funnel over a period of 3 hours to form a mixture. An exotherm can be observed during the addition. The mixture can be distilled under vacuum (25 ° C / 5.0 Torr) to produce 15.6 grams of the intermediate-RF 7,8,8,8-tetrafluoro-7- (trifluoromethyl) -oct-l-ene as a clear liquid having approximately 99.8% percent area purity (by gas chromatography), and 5.5 g of 7,8,8, 8-tetrafluoro-7- (trifluoromethyl) oct-1-ene with a lower purity (m / z 252 (M + ), 183 (M + -CF 3), 69 (M + -C 8 HnF 4), 55 (M + -C 5 H 4 F 7)); IR: olefinic extension CH at (w) 3087 cm "1, C = C extension at (w) 1644 cm" 1, and characteristic bands at 720, 1135, 1223, and 1315 cm "1; 1 H NMR (CDCI3, 300 MHz ) d 1.40-1.50 (m, 2H), 1.54-1.65 (m, 2H), 1.95-2.14 (m, 2H), 4.95-5.06 (m, 2H), 5.72-5.85 (ddt, J = 17.1, 10.2, 6.7, 1 H), 19 F NMR (CDCl 3, CFCl 3, 282 MHz) d -76.57 (d, J = 7.9, 7F), -183.2 (m, 1F)). Referring to Figure 3, the system is illustrated. which includes a reactor 32 configured to receive a halogenated compound, such as the 2-iodoheptafluoropropane described above, from a container for the halogenated compound 33. The halogenated compound may also include at least two CF3- groups, at least one group ( CF3) 2CF-, and / or at least two CF3- groups and a halogen other than fluorine, for example, Reactor 32 can also be configured to receive a compound comprising allyl from a container of the compound comprising allyl. , and water from the water container 35. The co The compound comprising allyl may include an ester such as allyl acetate, for example. The compound comprising allyl can also include an alcohol such as allyl alcohol, as another example. Reactor 32 can be configured to react the halogenated compound with the compound comprising allyl in the presence of water to form an RF-intermediate and provide an RF-intermediate to the container of! intermediary 36. The halogenated compound, compound comprising allyl and water can be combined in reactor 32 to form a mixture. A salt, such as Na2S205, can be added to the water to form an aqueous solution before forming the mixture, for example. The salt can be as much as 30% (w / w) of the solution. In an exemplary embodiment, wherein the halogenated compound includes 2-iodoheptafluoropropane; the compound comprising allyl includes allyl acetate; and the aqueous solution includes Na2S2? 5, the RF intermediate can include 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate. The reaction of 2-iodoheptafluoropropane with allyl acetate in the presence of the solution can include heating at least a portion of the mixture within the reactor 32 to at least about 80 ° C, from about 65 ° C to about 100 ° C. C, and / or from about 80 ° C to about 90 ° C.

In another exemplary embodiment, wherein the halogen compound includes 2-iodoheptafluoropropane; the compound comprising allyl includes allyl alcohol; and the solution includes Na 2 S 2, 5, the Rp-intermediary may include 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol. The reaction of 2-iodoheptafluoropropane with the allyl alcohol in the presence of the solution can include heating at least a portion of the mixture within the reactor 32 to at least about 80 ° C, from about 65 ° C to about 100 ° C. , and / or from about 80 ° C to about 90 ° C. An initiator may also be provided to reactor 32 to facilitate the reaction of the halogenated compound with the compound comprising allyl. An exemplary initiator can include AIBN. The reactor 32 may contain from about 0.01% (w / w) to about 10% (w / w), and / or from about 0.1% (w / w) to 5% (w / w), of the initiator. In accordance with an exemplary embodiment, the RF-intermediate can be provided to the intermediary container 36 after training within the reactor 32. By providing the RF-intermediary, procedures for the separation of the RF-intermediary can be included from the remaining contents of the reactor, these contents include reagents and / or by-products. Exemplary methods for providing the RF-intermediate to the container 36 may include liquid / liquid separation and / or distillation. The above-formed intermediate-Rp can also be reacted to form additional intermediates including additional RF-intermediates. For example, a portion of the intermediate can be unsaturated to form an RF-intermediate that includes a halogenated olefin. In an exemplary embodiment, the unsaturation of the intermediate can include exposure of the intermediate to a reducing agent. The reducing agent may include Zn and / or a mixture of Zn and diethylene glycol for example. The intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate can be unsaturated to form the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) - pent-1-ene, in accordance with one modality. The intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate can be combined with a mixture of Zn and diethylene glycol, for example, to form another mixture and the other mixture can be heating at least about 120 ° C to form the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene. As another example, the intermediate-Rp 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can be reacted to form the intermediate-RF 4,5,5,5-tetrafluoro -4- (trifluoromethyl) -pent-1-ene in the presence of a reducing reagent such as a mixture of Zn and diethylene glycol. According to another embodiment, the reducing agent may include POCI3 pyridine, and / or a mixture of POCI3 and pyridine. For example, the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can be reacted to form the intermediate-RF 4,5,5,5-tetrafluoro- 4- (trifluoromethyl) -pent-l-ene in the presence of a mixture of POCI3 and pyridine.

This reaction can be carried out while maintaining the temperature of the mixture between about 0 ° C to about 5 ° C, for example.

The intermediary-RF (4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene) is also can prepare in an exemplary aspect in accordance with Synthesis and Characterization of a New Class of Perfiuorinated Alkanes: Tetrabis (perfluoroalkyl) alkane G. Gambaretío et al., Journal of Fluor Chemistry, 5892 (2003) pages 1-7 and United States Patent 3,843,735 a Knell et. al., both incorporated in the present invention as reference. He 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene can also be prepared from according to the scheme (3) below, for example. 1. 1.1.?.3.?.3.h ??ra?l 'oro -í-j'o_oí > rop3r? D 3C «3W of 4.5.5, 5-l« rar joro-4- ijri fluoro m € ft¡l > 2-? fí'per? tl 4. 5.5.5-tetrafluoro (-4- (trifluoromethyropyrrine-ene seeuto < ie 4.5.5, 5-tetra? U nj-4-? Rill?; Oio 5tH - -i 'pehi3 With reference to the scheme (3) mentioned above, AIBN (9.2 g, 0.06 moles), 1,1,1,2,3,3-heptafluoro-2-iodopropane (1651 g, 5.6 moles), and 293 g of aqueous Na2S205 at 30 ° C. % (w / w) can be placed inside a 2 L pressure reactor to form a mixture.The reactor can be sealed and heated to 80 ° C under autogenous pressure.Allyl acetate (587 g, 5.9 moles) It can be added slowly to this mixture and the mixture can be stirred for an additional 4 hours.After stirring, an organic layer can be observed, stirring, washing twice with H20, and drying with MgSO4 to yield 2212 g of 94% ( percentage area by gas chromatography) of the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate Diethylene glycol (2944 g) and zinc powder (1330 g) can be placed inside a 5 L flask with 5 necks equipped with a simple distillation stop to form a mixture. This mixture can be stirred and heated to 120 ° C and 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate (4149 g) can be added slowly. As the 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentyl acetate is added, the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1- eno (2075 grams) can be subjected to flash vaporization and collected in an ice trap of 1 L. The contents of the ice trap can be distilled to produce 4,5,5,5-tetrafluoro-4- (trifluoromethyl) - pent-1-ene > 99.5% (of the percentage area by gas chromatography) (e.g. 54 ° C). The intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene can also be prepared according to scheme (4) below. 1 1 i • With reference to the aforementioned scheme (4), approximately 10.3 grams of 2-iodoheptafluoropropane can be added to a glass tube under pressure. The tube can be sealed with a septum, heated to approximately 75 ° C, and 1.9 mL of 30% aqueous Na2S205 (w / w) can be added to the tube via a syringe through a septum to form a mixture within the septum. tube. The mixture can be heated to approximately 80 ° C, and 0.07 grams of AIBN can be dissolved in allyl alcohol to form a solution. This solution can be added slowly to the tube through the septum to form another mixture. This other mixture can be stirred and maintained at a temperature of about 80 ° C for 3 hours. The mixture can then be cooled and 11.2 grams of 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can be removed as an organic layer after separation. The intermediate or RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can have as much as 93% (of the percentage area by gas chromatography). Approximately 11 g of the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can be added to a glass tube under pressure and approximately 13 grams of acetic acid can be added water at 30% (w / w) to the other tube to form a mixture. The mixture can be heated to approximately 80 ° C, and 4 grams of powdered zinc can be slowly added through a solid addition system. The mixture can be left stirring for an additional 2 hours before being cooled and 2 mL of 1.5 N HCl are added to separate the phases of the mixture. The organic layer can be decanted to produce 3 grams of the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pentan-1-ene which can be 75.14% (of the percentage area by chromatography Of gas). As another example, approximately 254 grams of diethylene glycol and 127.5 grams of Zn powder can be added into a 1000 mL round bottom flask with three necks equipped with a dean-stark apparatus, thermometer, and inner tube to form a mixture . The mixture can be heated to 120 ° C while stirring and approximately 213.81 grams of the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1 -ol can be slowly pumped underneath of the surface inside the mixture. Approximately 111.4 grams of the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pentan-1-ene was collected which may be 88% (of the percentage area by gas chromatography). The intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene can be prepared according to scheme (5) below. 1. 1.I With reference to the aforementioned scheme (5), the intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can be prepared as previously described and converted in accordance with the scheme (6) below.

POS, 4.5.i.5-t '? T / 9t! Uorc < -4- (trifJuc.r «ct? E? L). 5-1 fluon strip > - + 0n1? rüjr? 6:? i; f.trrrt- (-..- no 2-&'Joperc? a? -l-ol With reference to the aforementioned scheme (6), 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol (11.42 g, 0.032 mol) and pyridine (84.17 g, 1.06 mol) are can be added to a 250 mL round bottom flask with two necks equipped with a thermocoupler, magnetic bar for stirring, an outer cover for heating, and a 50 mL addition funnel at compensating pressure containing phosphorous oxychloride (2.23 g, 0.015 moles) to form a mixture. The mixture can be cooled between 0 ° C-5 ° C, and POCI 3 can be added dropwise over a period of 25 minutes. A color change of the reaction mixture can be observed from yellow to dark red and an exotherm. The mixture can be allowed to warm to room temperature and then kept overnight. The portions of the mixture can be removed, washed in H20, and dried over MgSO4, then analyzed by gas chromatography and / or gas chromatography / mass spectrometry. Gas chromatography, gas chromatography / mass spectrometry and 1 H NMR can be used to determine 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene.

The intermediate-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene can be used to prepare other RF-intermediates as well. For example, and by way of example only, 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene can be halogenated to form RF-intermediates that include at least two CF3 groups and a halogen other than fluorine, such as the intermediate-RF 5-bromo-1,1,1,1-tetrafluoro-2- (trifluoromethyl) -pentane according to scheme (7) below.

-J.3.iJ-? Etratluoto-4. (KníluoB> fnít¡l * ps. | Eno í-Wop «-1.l .t.2- trafluwo-2-? JftMut« .rtréi? LT? Í : f < jr.?) With reference to the aforementioned scheme (7), approximately 45 g (0.214 moles) of 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene can be loaded into a 50 mL auto syringe and it was vaporized in a hot spiral before being placed inside a quartz tube via a Claisen adapter, which ends inside a 250 mL round bottom flask with two necks equipped with a HBr treatment tower containing a KOH solution to 10% (w / w). The quartz tube can be equipped with an internal thermocoupler and a reflux condenser with dry ice and acetone, and surrounded by a carousel of ultra violet light (254 nm). Simultaneously with the addition of 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene, anhydrous HBr can be introduced into the quartz tube from a regulated tank through the same adapter Claisen. The rates of entry for HBr and 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pent-1-ene can be set at 39.3 g / hour and 13.4 g / hour, respectively. Approximately 53.94 g (0.19 moles) of the product can be collected and washed with NaHCO 3 then washed with H 2 O and dried over molecular sieves. The product samples can be removed for gas chromatography / mass spectrometry analysis (m / z 290.8 (M +), 209.0 (M + -HBr), 189.1 (M + -101.9)). As another example, the RF-intermediate 7,8,8,8-tetrafluoro-7- (trifluoromethyl) -oct-l-ene, prepared as described above, for example, can be used to prepare another intermediate-Rp including the RF-intermediates such as 8-bromo-1,1,1,1-tetrafluoro-2- (trifluoromethyl) -octane according to scheme (8) below. /. & $ .s-teuai iorß- • * -ítp? luC? on? Tiilocv 1 - «no S- br mo- 1.l.J,? - te1r3i? u r - '* tf Htuorometj jo tai? e' With reference to the scheme (8) mentioned above, inside a 250 mL tube under pressure, equipped with a 9-inch (22.8 cm) Hg Pen-Ray® lamp, pressure gauge, agitator, and inner tube, 67.06 grams (0.266 moles) of the RF-intermediate can be added 7,8,8,8-tetrafluoro-7- (trifluoromethyl) -oct-1-ene. The tube can be sealed, the anhydrous gaseous HBr can be bubbled into the system, and the pressure is maintained at about 184 kPa. The tube can be irradiated for 3 hours, and the mixture inside the tube can be washed with NaHCO3, then twice with water and dried over molecular sieves to produce approximately 68.89 grams (0.21 moles) of the intermediate-RF 8-bromo-1 , 1, 1, 2-tetrafluoro-2- (trifluoromethyl) -octane. Intermediates-Rp having the alcohol functionality can be used as raw materials to produce additional RF-intermediates. For example, and by way of example only, a portion of the RF intermediate 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol, described above, may be dehalohydrogenated. For example, Rp-intermediates such as the heterohalogenated compound 4,5,5,5-tetrafluoro-4- (urea) -2-iodo-entan-1-ol including at least two CF3- groups and a halogen other than fluoride, can be dehalohydrogenated to form a homohalogenated alcohol. Dehydrohydrogenation can include exposure of the intermediate to tributyltin hydride, for example. In accordance with an exemplary embodiment, the -Rp intermediate may include 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol and the alcohol may include for example, in accordance with the scheme (9) below. OR) 4. S.5.J.tí1ra < luon > .4-0pflu < lop, fla > 2.¡ < ) dopínt3r, -l.ol K'C 4.í.5.? l, tí_flu0ro.4. (lplIu «o« .IS.ent-n.). l According to the aforementioned scheme (9), a 500 mL round bottom flask with two necks can be equipped with a thermocoupler, stirrer, and an outer cover for heating.

Approximately 212.1 g (0.599 moles) 4,5,5,5-tetrafluoro-4 (trifluoromethyl) -2-iodopentan-1-ol (212.1 g, 0.599 moles) can be added to the flask and heated to approximately 60 ° C to 70 ° C. ° C. From a 100 mL addition funnel at compensated pressure, approximately 196.4 g (0.675 moles) of the tributyltin hydride can be added dropwise over a period of 4 hours followed by 2 hours of continuous heating and stirring. The intermediate-RF 4,5,5,5-tetrafluoro-4 (trifluoromethyl) -pentan-1-ol can be obtained by vacuum distillation and verified by gas chromatography / mass spectrometry (m / z 228 ( M +), 211 (M + -OH), 159 (M + -CF3)). Even another RF-intermediate, for example, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) -Pentanol, can be prepared according to the procedures described in scheme (10) a below and is detailed in the US Patent 3,467,247, incorporated herein by reference. 0) 2.3.4.5.5.5-l »s > ath? -? ro-2_3-bi; pert'luoropíop-l-íno U.2.3.4,4Ahspl3fluo ™ -3- tfrífj'jororrietífp p? sn- J? í? rifluwo? r? ¿srt > u? -l-ér? t > In accordance with an exemplary embodiment of the disclosure, an RF intermediate having the alcohol functionality such as 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pentan-1-ol and / or 2,3,4 , 5,5,5-hexafluoro-2,4-bis (trifluoromethyl) -pentan-1-ol described above can be reacted with a halogenated olefin to form another RF-intermediate such as an allyl ether compound. As described above, the RF-intermediate can include at least two CF3- groups; at least one group (CF3) 2CF-; and / or at least three CF3- groups. Exemplary halogenated olefins include olefins that include a halogen other than fluorine such as bromine, for example. 3-bromoprop-1-ene can be used as a halogenated olefin. The halogenated olefin can be exposed to the alcohol in the presence of a basic solution, such as an aqueous solution of KOH. In an exemplary embodiment, a mixture of the alcohol, the halogenated olefin, and a reactive medium including a phase transfer catalyst, such as tetrabutylammonium acid sulfate can be prepared, and the basic solution can be added to this mixture while maintaining the mix below at least 10 ° C. Intermediates-RF including the compound allyl ether they can be prepared by reacting the RF-intermediate 1, 1, 1, 3,3, 3-hexafluoropropan-2-ol with 3-bromoprop-1-ene according to the aforementioned and scheme (11) below.

J-0.1. ' .3.3.3 - ?? e3 ri? Oro? R f'3r? -2-tl > '??' rc-; < - l-snc » With reference to the aforementioned scheme (11), a 500 mL flask with three necks can be equipped with a thermometer, stirrer, and a condenser. Approximately 40.86 g of NaOH can be dissolved in 120 g of deionized H20 to form a mixture. Approximately 170.1 grams of hexafluoroisopropan-2-ol may be added to the mixture. After about 15 minutes, 100.5 grams of 3-bromoprop-1-ene can be added to the mixture at room temperature. The mixture can be stirred for approximately 2 days. The mixture can then be separated into phases to produce approximately 178.6 g of the crude product (being approximately 92.4% pure percentage area (by gas chromatography) with 3.2% percent area of allyl bromide The unpurified product can be distilled to yield 99.94% (percentage area by gas chromatography) of 3- (1 , 1, 1, 3,3,3-hexafluoropropan-2-yloxy) prop-1-ene having a boiling point of 83.5 ° C. As another example, the halogenated intermediates including the allyl ether compound can be prepared by reacting the RF-intermediate 1, 2,3,4,4,4-heptafluoro-2,4-bis- (trifluoromethyl) pentane-1-ol with 3-bromoprop-1-ene in accordance with scheme (9) and scheme (12) below.

With reference to the aforementioned scheme (12), 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) -pentan-1- can be added inside a 1 L flask with three necks. ol (551 g, 1.66 mol), aiyl bromide (221.2 g, 1.83 mol) and tetrabutylammonium acid sulfate (5 mol%) to form a mixture. The mixture can be cooled to approximately 10 ° C, and 50% (w / w) KOH (400 grams) can be added over a period of 2 hours. Then the mixture can be allowed to stir at 10 ° C for about 72 hours. After 72 hours, an additional 100 mL of 33% KOH (w / w) can be added, and the mixture can be stirred for an additional 12 hours. The reaction can be monitored by the removal and analysis of the portions, using gas chromatography, and after the non detection of 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentan- 1-ol, the mixture can be washed once with H20, twice with 10% HCl (w / w), and once again with H20. The combined organic layers can be dried with MgSO4 to yield approximately 516 grams of material containing 20.04 grams of 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) -pentyl allyl ether having a 28.21% (of the percentage area by gas chromatography).

According to another embodiment of the disclosure, the RF-intermediate including the homohalogenated alcohol, such as 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pentan-1-ol mentioned above, can be reacted for form an acrylate. The homohalogenated alcohol can be exposed to an acryloyl compound, for example, to form the acrylate. In an exemplary embodiment, the homohalogenated alcohol may include 1, 1, 1, 3,3,3-hexafluoropropan-2-ol and the acryloyl compound may include acryloyl chloride. The 1, 1, 1, 3,3,3-hexafluoropropan-2-ol can be reacted with the acryloyl chloride in the presence of a basic solution while maintaining the temperature of the solution at about 0 ° C to form the intermediate-RF acrylate of 1, 1, 1, 3,3,3-hexafluoropropan-2-yl, for example, according to scheme (13) below. l .l. 1.3. With reference to the aforementioned scheme (13), a 1000 mL flask with three necks can be equipped with a thermometer, stirrer, and a dropping funnel with an inner tube. Approximately 130.6 grams of acryloyl chloride, 168.8 grams 1, 1, 1, 3,3, 3-hexafluoropropan-2-ol, and 1 gram of 2,6-di-tert-butyl-4- can be added into the flask. methylphenol to form a mixture. Approximately 30% (w / w) fumed sulfuric acid can be added later to the mixture through the inner tube while maintaining the mixture at 60 ° C-75 ° C. After the addition, the mixture can be maintained at 60 ° C-70 ° C for about 4 hours. The one stage vacuum distillation of the mixture can yield about 183 grams of the product without purifying 1,1,1,3,3-hexafluoropropan-2-yl acrylate being about 95.7% (of the percentage area by chromatography Of gas). Unpurified 1, 1, 1, 3,3,3-hexafluoropropan-2-yl can be further distilled to increase purity to 99.7% (percent area by gas chromatography). By way of another example, the halogenated intermediate including the homohalogenated alcohol, such as 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol mentioned above, can be reacted to form an acrylate. The 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol can be exposed to acryloyl chloride according to scheme (14) below to form (14) cte Í C C C ac ac ac ac ac ac ac ac ac ac ac ac ac ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 ,5 With reference to the aforementioned scheme (14), 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol (2.59 g, 0.011 mol) and triethylamine (1.3 g, 0.013 mol) can be added to a 15 mL round bottom flask with three necks equipped with a reflux condenser with chilled water, thermocoupler, stirrer, and addition funnel, to form a mixture. The mixture can be maintained at about 0 ° C using a bath with ice water. The acryloyl chloride (1.38 grams, 0.015 moles) can be added to the mixture through a dropping funnel dropwise for about 15 minutes. After approximately a 1 hour maintenance period, 10 mL of H20 can be added to the flask, two phases can be observed, and the organic phase separated. The organic phase can be analyzed and a peak observed and confirmed to have an m / z of 283 by gas chromatography / mass spectrometry. By way of another example, an RF intermediate can be prepared by reacting an alcohol having at least two CF3- groups and a cyclic group such as 3,5-bis (trifluoromethyl) -benzyl alcohol to form an acrylate. The alcohol can be reacted with an acryloyl compound such as acryloyl chloride to form the acrylate. In an exemplary embodiment, the acrylate may include For example, and by way of example only, 200 mL of CH2Cl2 and 25 grams of 3,5-bis (trifluoromethyl) -benzyl alcohol can be placed in a 500 mL flask to form a mixture. While stirring the mixture, approximately 13.8 grams of triethylamine may be added to the mixture.

The mixture can then be cooled in an ice bath and 10.5 mL of acryloyl chloride can be slowly added to the mixture. The mixture can be further stirred for about one hour and then stopped with an aqueous solution of HCl. The mixture can be allowed to stand so that the phases are separated and the organic layer can be washed with a saturated solution of KCl and can be dried over MgSO4. The organic solvent can be removed by evaporation and the remaining 25.16 grams of the solid they can be > 98% (of the percentage area by gas chromatography). RF-intermediaries having a cyclic group can also be prepared. In accordance with an exemplary embodiment, a reagent including at least two CF3- groups such as a heterohalogenated intermediate can be reacted with another reagent including a cyclic group, such as phenol, to form an RF intermediate that includes at least two CF3- groups and a cyclic group. The reagent may include an alcohol such as the 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol previously prepared. For example, and by way of example only, the RF-intermediary can be prepared in accordance with scheme (15) below. 4. With reference to the aforementioned scheme (15), approximately 3.9 grams (0.04 moles) of phenol and 5.5 grams (0.05 moles) of triethylamine can be placed inside a 25 ml round bottom flask with two necks, clean and dry equipped with an agitator, thermocoupler, an outer cover for heating, and a 50 mL addition funnel at compensating pressure containing 4.7 grams (0.042 moles) of 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan -1-ol to form a mixture. The mixture can be gradually heated to 68 ° C and then 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol can be added dropwise over 30 minutes. The performance of It can be 42%. (m / z 320.1 (M +), 94 (M + -226)). By way of another example, an RF intermediate can be prepared which is heterohalogenated and contains a cyclic group according to scheme (16) below. 4.5.5 With reference to the aforementioned scheme (16), approximately 13.7 grams (0.079 moles) of 4-bromophenol and 9.0 grams (0.089 moles) of triethylamine can be added to a 50 mL round bottom flask with two necks equipped with a thermocoupler, stirrer, an outer cover for heating, and a 50 mL addition funnel at compensating pressure. The contents of the round bottom flask can be gradually heated to 93 ° C followed by the dropwise addition of 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -2-iodopentan-1-ol (23.1g, 0.065 moles) using the addition funnel for 15 minutes. Subsequently the contents can be refluxed for 1 hour, then samples are taken and analyzed by gas chromatography. The yield by determination by gas chromatography can be 43% for 2- (4-bromophenoxy) -4,5,5,5-tetrafluoro-4- (trifluoromethyl) pentan-1-ol. According to another embodiment of the description, the bicyclic halogenated intermediates can be prepared according to the schemes (17A and B) below.

With reference to the aforementioned scheme (17A), a 500 mL flask with three necks equipped with an agitator, an inlet for the addition of raw material, and a packed column terminated with a head for reflux distillation, thermocoupler, and a funnel for collection can be loaded with 60.40 g of KOH (0.917 mol), 5.86 g of methyltributylammonium chloride (aliquot 175, -5% by weight) in 150 mL of deionized water to form a solution. The resulting solution can be heated to 97 ° C and 110 g (0.281 moles) of 1 can be added, 1, 1, 2,5,5,5-heptafluoro-2- (trifluoromethyl) -4-iodopentane dropwise and subsurface via a syringe pump over the course of a 2 hour period. During this addition the resulting product can be collected in the upper collection flask and the reaction can continue heating until the highest temperature aicanza 94 ° C. Ei material collected can be dried over magnesium sulfate to yield 74.18 g of unpurified reaction product which by GC analysis consisted of primary product and feedstock. The unpurified reaction material was distilled to yield 42.6 g of (E) -1,1,1,5,5,5-heptafluoro-4- (trifluoromethyl) pent-2-ene (57.5% isolated yield) . (1 H-NMR (CDCl 3): d 6.45 (d, J = 12 Hz, 1 H), 6.45 (dhep, 1 H), 3 C-NMR (CDCl 3): 90.5 (dhep, J = 27, 202 Hz, CFCH), 120 (qd, 27, 287 Hz, CF3CF), 121.6 (q, J = 220 Hz, CHCF3), 124.4 (m, CHCF), 128.2 (qd, J = 21, 36 Hz, CHCF3) .19F-NMR (CDCI3) w / CCI3F): d -66.4 (d, JH-F = 3 HzCF3CH), -76.9 (d, JF-F = 8 Hz, CF3CF), -186.9 (m, CF3CF).

With reference to the aforementioned scheme (17B), 5.26 grams (0.08 moles) of cyclopentadiene and 14.67 grams (0.06 moles) of (E, Z) -1, 1, 1, 4,5,5,5-heptafluoro-4- (trifluoromethyl) -pent-2-ene can be added to form a mixture in a stainless steel autoclave that can be equipped with a 6.9x103 kPa safety disc, stirrer, external thermocoupler, valve, and pressure gauge. The mixture can be maintained at approximately 140 ° C to 250 ° C under autogenous pressure for approximately 4 to 72 hours. The yield of 5- (trifluoromethyl) -6- (perfluoropropan-2-yl) -bicyclo [2.2.1] hept-2-ene can be greater than 12 (of the percentage area by gas chromatography). The reaction mixture can also be analyzed by gas chromatography / mass spectroscopy, (m / z 330 (M +), 261 (M + -CF3), 161 (M + - (CF3) 2CF)). With reference to Figure 4, there is shown a system 40 for the preparation of RF-intermediates including reagents such as a taxogen 42, a telogen 44, and an initiator 46 being provided to a reactor 48 to form a product such as a telomere 49. In exemplary embodiments, the system 40 can carry out a telomerization process. According to one embodiment, taxogen 42 can be exposed to telogen 44 to form telomer 49. According to another embodiment, taxogen 42 can be exposed to telogen 44 in the presence of initiator 46. Reactor 48 can also be configured to that provides heat to the reagents during exposure. The taxogen 42 can include at least one compound comprising a CF3- group. The compound comprising CF3- can have a C-2 group having at least one pendant group CF3-. In exemplary embodiments, taxogen 42 may include an olefin, such as trifluoropropene. Taxogen 42 may also include 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pen-1-tin and / or 6,7,7,7-tetrafluoro-6- (trifluoromethyl) -hept-1 - eno, for example. The telogen 44 may include halogens such as fluorine and / or chlorine.

The telogen 44 may include at least four fluorine atoms and may be represented as R -Q and / or Rci-Q. The Rp may be as described above and may include at least four fluorine atoms, and the Q group may include one or more atoms of the periodic table of the elements. The group Q can be H or I with the RF group being (CF3) 2CF- and / or -C6F13, for example. Rp-Q can be 2-iodo-fluoropropane, for example. The group Reí, can include at least one group -CCI3. Exemplary telogens may include the above-described halogenated compounds, such as (CF3) 2CFI, C3F13I, and / or trichloromethane. In exemplary embodiments, taxogen 42 may include trifluoropropene and telogen 44 may include (CF3) 2CF1, with a molar ratio of taxogen 42 to telogen 44 being from about 0.2: 1 to about 10: 1, from about 1: 1 to about 5: 1, and / or from about 2: 1 to about 4: 1. Taxogen 42 may include 4,5,5,5-tetrafluoro-4- (trifluoromethyl) -pen-1-teno and / or 6,7,7,7-tetrafluoro-6- (trifluoromethyl) hept-1-ene, and telogen 44 may include (CF3) 2CFI, for example. The reactor 48 may be any reactor on a laboratory scale or on an industrial scale and, in certain embodiments, the reactor 48 may be configured to control the temperature of the reagents. In accordance with the exemplary embodiments reactor 48 can be used to provide a temperature during the exposure of the reagents of approximately 90 ° C at approximately 180 ° C, from 60 ° C to approximately 220 ° C and / or from 130 ° C to approximately 150 ° C and, in accordance with other modalities, the reactor 48 may be configured to maintain the temperature of the reagents at approximately 90 ° C.

The telomere 49, produced after the exposure of the taxogen 42 to telogen 44, can include RF (Rt) nQ and / or Rc? (Rt) nH. The RT group can include at least one C-2 group having a pendant group which includes at least one group -CF3, such as -CH2-CH-CF3. exemplary telomeres 49 may include Qg (RrCH) nRF Qg (R, -CH) RF CF3 CF3 and / or one or both of Qa (RrCH) nRF Qg (CH2-CH) nRF CF CF3 y. with RF including at least one carbon atom, such as -CH2-, for example. In exemplary modalities, n can be at least 1 and in others modalities n can be at least 2 and the product can include one or more of CF RF (CH2-CH-CH2-CH) Q, R | :. { CHrCH ^ H3.CH9) Qg Ra (CHa-CH-CH2-CH) H CF3 CF3 (CF3 f CF3 CF3, CF Rc, (CH CH-CH-CH) Z or F3 Z being H, Br, and / or Cl, for example.

In an exemplary embodiment, the taxogen trifiuoropropene can be exposed to the telogen (CF3) 2CFI to form the telomer (CF3) 2CF (CH2-CH) nl CF3 f and, as another example, the irmuoropropene can be exposed to the telogen C6F13I to form the telomer CeF13 (CH2-CH) t, l • CF3. In accordance with another modality, the taxogen trifluoropropene is also can expose the telogen CCI3H to form the telomere CCla (CH2-CH) pH ¿F3. Products that have n of at least 2 can be formed when an excess of taxogen is used in comparison with telogen. For example, at less a mole ratio of 2: 1 of the taxogen with respect to the telogen is you can use to obtain products that have n being at least 2. By example, and by way of example only, at least two moles groups of the taxogen trifluoropropene may be exposed to at least one mole of the telogen (CF3) 2CFI to form one or both of the telomeres (CF3) 2CF (CH2-CH-CH2-CH) I CF3 CF3 In additional embodiments, the initiator 46 can be provided to the reactor 48 during the exposure of the reactants. Initiator 46 may include thermal, photochemical (UV), radical, and / or metal complexes, for example, including a peroxide, such as di-tert-butyl peroxide. Initiator 66 may also include catalysts, such as Cu. Initiator 46 and taxogen 42 can be supplied to reactor 48 at a molar ratio of the initiator 46 with respect to taxogen 42 of between about 0.001 a about 0.05 and / or between about 0.01 a approximately 0.03, for example. The initiator 46 and the taxogen 42 can be supplied to the reactor 48 at a molar ratio of the initiator 46 with respect to the taxogen 42 from about 0.001 to about 0.05 and / or from between about 0.01 to about 0.03, for example In accordance with exemplary modalities, they can be used various initiators 46 and telogens 44 to telomerize taxogen 42 as referred to in Table 2 below. Telomerizations using photochemical initiators and / or metal complexes 46 can be carried out under batch conditions using the Carius 48 tube reactors. Telomerizations using thermal initiators, peroxide and / or initiators in metal complex 46 can be carried out in Hastelloy® Reactors of 160 mL and / or 500 mL 48. Telogen 44 (pure and / or as a peroxide solution) can be supplied as a gas at a temperature of about 60 ° C to about 180 ° C and a molar ratio initial Ro of telogen 44 rrjo / taxogen 42 [Tx] 0 may vary from 0.25 to 3.0 and the reaction time from 2 to 22 hours. The product mixture can be analyzed by gas chromatography and / or the product can be distilled in different fractions and analyzed by 1 H and 19 F NMR and / or 13 C NMR. The products Mono-adduct (n = 1) and di-adduct (n = 2) can be recognized as shown in table 2 below.

TABLE 2 Telomerization of Trifluoropropene Taxogen Ln a) the telogen can be C6F? 3l in processes Nos. 1 -9 and (CF3) 2CFI in processes No 10-13 b) Ro = [T] o / [Tx] 0; Co = [ln] 0 / [Tx] or c) heavy TFP telomeres (n> 2) can make the remainder of the product d) The primers can be Perk. 16s (t-butyl cyclohexyl dicarbonate); AlBN; Trig. 101 (2,5-bis- (t-butyl peroxy) -2,5-dimethylhexane); and DTBP.

For example, and by way of example only, the taxogen trifluoropropene can be combined with telogen 2-iodofluoropropane for form telomere 1, 1, 1, 2,5,5,5-heptafluoro-2- (trifluoromethyl) -4-iodopentane in accordance with the scheme (18) below. 1 .1, 1, 2,3,3,3- eptafluoro ^ .1 .1,5,5,5, S-eplaíl? Oro-2- -2-iodoprope.no (Irifluorometi-iodopenlsno As another example, Ielogen 1, 1,1, 2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-iodohexane can be combined with the taxogen trifluoropropene to form the telomer 1, 1,1,2,2,3,3,4,4,5,5,6,6,9,9,9-hexadecafluoro-8-iodoononane according to the scheme (19) to continuation. - 1, 1, 1, 2,2,3,3,4,4,5,6,6,6- 1, 1 .1, 2, 2, 3, 3, 4, .5,5, 6,6, 9, 9, S-lrdecarluoro-6-iodo e > : 5r? liexaüecailuoro-S-iodorioriano As another example, a taxogen including at least two groups CF3- such as the intermediates-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pen-1-teno and / or 6,7,7,7-tetrafluoro-6- (trifluoromethyl) -hept-1 -one can be combined with a telogen including a saturated compound that has at least two CF3- groups to form a telomer including a saturated compound according to scheme (20) below. 4, 5, 5, 5-1 e? Ra fluoro-4-1, 1, 1, 2,3,3,3-he? Tafluof or 1, 1, 1, 2.S, 7,7,7- oc (atluoro-2,6-bie (triflijrn or? rretil '? erit-1 -ene -2?? odoprc? pano (tt iflu rt m lilj- - -iodohej? an With reference to the aforementioned scheme (20), 3- perfluoroisopropyl-1-propene (20 grams, 0.095 moles) and 2-iodoheptafluoropropene (28.18 grams, 0.095 moles) can be provided to a Pressurized glass tube to form a mixture. This mixture can be add AlBN (0.51 grams), and the mixture can be heated to and maintained at 85 ° C for 24 hours. During heating, additional AlBN can be added (0.11 grams after 3 hours and another 0.1 grams after 21 hours). Then the mixture can be washed twice with H20 and the analysis via Gas chromatography can produce 56% purity of percentage area. 7. 8, 8, B-te! RarlUOrc? -7- (t.'¡f l-oromeia) 1, 1, rodopíopano oci-1-erso 1, 1, 1 .2,3,10,10,10-OClalij «O-2,9-fs (lpffc? Oromelrlj-4-? Dodecano With reference to the scheme (21) mentioned above, to a 250 mL stainless steel autoclave sealed and evacuated equipped with inner tube and a valve, manometer, safety disc, valve vent, stirrer, and a thermocoupler, 30.4 grams (0.121) were added moles) of 6,7,7,7-tetrafluoro-6- (trifluoromethyl) -hept-1-ene, 41.32 grams (0.140 moles) of heptafluoro-2-iodopropane, and 0.209 grams (0. 0013 moles) of 2, 2'-azobisisobutrilonitrilo to form a mixture. The mixture can then be slowly heated to 90 ° C and maintained for 24 hours. After the maintenance period, the samples can be removed and analyzed by gas chromatography and gas chromatography / mass spectrometry. (GC-HP-5 column (RT: 15.9 min), GC / MS (m / z 421 (M + -1), 211 (M + -C6H5F7I), 127 (l +)). In accordance with additional modalities, intermediaries- RF, including telomeres, can be further modified to form additional RF-intermediates For example, and by way of example only, the RF-intermediate 1, 1, 1, 2,5,5,5-heptafluoro-2- (trifiuoromethyl) ) -4-iodopentane can be modified according to scheme (22) below to produce additional intermediates as shown below. 1 (trifluoromethylH-iodopenlarium 6,7,7,7-telrafluoto-4.8-bis (tr? L? Joromethyl) -2-dioxide? Eptide With reference to the scheme (22) mentioned above, a 500 mL flask With three necks can be equipped with a stirrer, thermocoupler, reflux condenser, and septum.Approximately 483 grams (1.23 moles) of 1, 1, 1, 2,5,5,5-heptafluoro-2- (trifluoromethyl) -4 -iodopentane can be added to the flask.Approximately 12.4 grams (0.08 moles) of AlBN can be added to a syringe pump containing approximately 123 grams (1.23 moles) of allyl acetate to form a mixture.The syringe pump can be connected to the flask via a feeding tube made of Teflon through the septum., 1, 1, 2,5,5,5-heptafluoro-2- (trifluoromethyl) -4-iodopentane can be maintained from about 80 ° C to 90 ° C. The mixture of allyl acetate and AlBN in the syringe pump can be loaded (entered) into a flask at a rate of 15 mL per hour. The mixture can be sampled and analyzed by gas chromatography to find the 6,7,7,7-tetrafluoro-4,6-bis (trifluoromethyl) -2-iodoheptyl acetate having about 78.3% percent area purity. et? l) With reference to the aforementioned scheme (23), a 250 mL flask with three necks can be equipped with a thermocoupler, stirrer, 50 mL addition funnel under compensating pressure and an apparatus for short path distillation. Approximately 150 grams of diethylene glycol and 26.01 grams (0.4 moles) of zinc can be added to the flask to form a mixture. The mixture can be maintained at about 50 ° C to 65 ° C and a vacuum of about 5.3 kPa to 8.7 kPa can be maintained. Approximately 33 grams (0.067 moles) of 6,7,7,7-tetrafluoro-4,6-bis (trifluoromethyl) -2-iodoheptyl acetate can be placed into the 50 mL addition funnel and added dropwise for approximately 1 hour. Approximately, according to the addition of 6,7,7,7-tetrafluoro-4,6-bis (trifluoromethyl) -2-iodoheptyl acetate, 6,7,7,7-tetrafluoro-4,6-bis (trifluoromethyl) ) hept-1-ene can be distilled reactive and collected in a 50 mL collecting flask. A total of about 39.7 grams of the unpurified intermediate-RF 6,7,7,7-tetrafluoro-4,6-bis (trifluoromethyl) -hept-1-ene can be collected having 53% purity of percentage area by gas. With reference to Figure 5, it is shown that a system 50 can be used for the production of telomeres that include the ester functionality. The system 50 may include a reactor 56 that is configured to receive reagents such as an ester 54 and a telomer 52, as well as, in other embodiments, an initiator 59. The telomer 52 may be fluorinated and may be represented by the general formula Q1 (Rt) nQ2. The groups Q-i and Q2 may include one or more atoms of the periodic table of the elements including Q and / or Qg and in accordance with the exemplary embodiments, the groups Qi and Q2 need not be different or need to be identical. The group Qi, in exemplary embodiments, can include at least one group -CF3, and in other modalities at least two groups -CF3. The Q-i group can also include a -CF (CF3) 2 group in one modality and a -C6F13 group in other modalities. The group Q2 may include halogens in certain embodiments and in other embodiments may include hydrogen. The telomer 52 may include Rp-intermediates including the telomer 49 described above, such as (CF3) 2CF (CH2-CH) nl C6F13 (CH2-CH) nl CCI3 (CH2-CH) nH CF3 CF3 and or CF3, for example. The ester 54 may include a compound comprising allyl such as allyl acetate.

In accordance with an additional embodiment, the primer 59 is can be used inside reactor 46 during exposure of ester 54 to telomer 52. Initiator 29 may include compounds such as azobisisobutyronitrile (AlBN), peroxides such as: dibenzoyl peroxide, ter-amylperoxypivalate, tert-butyl peroxypivalate, DTBP (di-tert-butyl peroxide), and / or you can also use a metal complex such as copper chloride, ferric chloride, palladium and / or ruinium complexes.

Ester 54 can be exposed to telomer 52 to form a telomer comprising ester 58. The telomer comprising ester 58 can include the composition Q? (Rt) nRE, with the group RE including at least one ester group and / or Qg, such as an acetate group. In exemplary modalities, the telomere 52 can include the formula RF (RT)? Q2, with the RF group including the minus one fluorine atom such as a -CF3 group and / or as described previously. RF (RT)? Q2 can be exposed to ester 54 to form a telomer comprising ester 58 such as RF (RT) RE, for example. From conforming to one modality, the telomer (CF3) 2CF (CH2-CH) nl CF3 can be exposed to the allyl ester acetate to form the telomer that it comprises ester (CF3) 2CF (CH2-CH) nCH2CHCH2? CCH3 CF3 iO In exemplary embodiments, reagents within reactor 56 can be heated to at least 82 ° C for about 10 hours during the exposure of reagents. Reagents can also be exposed in the presence of AlBN at the same temperature for the same amount of time, for example. In some embodiments, the process of the system 50 can be exothermic and the initiator can prevent reaching a temperature that can decompose and / or rearrange the products. For example, when the temperature of the reactor contents is higher than 90 ° C and a dibenzoyl peroxide initiator is used, the reaction temperature of the ester and the telomer can be raised to about 160 ° C-180 ° C, and at At high temperature the obtained ester can carry out a thermal rearrange towards RFCH2CH (OAC) CH2I, for example. AlBN can be used as the initiator and can be added step by step to avoid such rearrangement and provide a product yield of more than 80-82% (by gas chromatography) or 75% (by distillation). With reference to Figure 6, the system 60 includes a reactor 62 configured to receive reagents such as a telomer 64 and a reducing agent 66 and form a telomer comprising allyl 68. The telomer 64 can include RF-intermediates such as telomer that comprises ester 58 described above. For example, telomere 64 can include a QI (RT)? RE >; such as (CF3) 2CF (eH2-CH) nCH2CHCH2OCCH3 CF3 1 O The reducing agent 66 may include one or more reagents, such as a mixture of activated zinc and methanol. Other agents can be used reducers. The reactor 62 can be configured to expose the agent 66 to telomere 64 at about 65 ° C and subject these materials to reflux for approximately 3 hours, plus or minus 2 hours. For example, and by way of example only, the telomere 64, such as (CF3) 2CF (CH2-CH) nCH2CHCH2OCCH3 CF-, i O it can be added to reactor 62 which contains a 2-fold excess of activated Zn powder in MeOH solution. The reactor 62 can be configured to agitate and / or even to vigorously stir the solution during and / or after the addition of the 64 telomere. According to some embodiments, after the addition of the 64 telomere, the reaction of the 64 telomere with the agent 66 can be exothermic and telomere 64 can be added drop by drop under reflux of MeOH to control the exotherms, if desired. The conversion of telomere 64 can be quantitative with the overall telomere production comprising allyl 68 is about 75% after distillation, for example.

In exemplary embodiments, the telomer comprising allyl can include Q1 (RT) nRA, with group RA including Qg as described previously and / or at least one allyl group. The telomere comprising allyl 68 can include RF (RT)? RA > and as such, it includes at least one fluorine atom. For example and by way of example only, the agent zinc and methanol can be exposed to the telomer (CF3) 2CF (CH2-CH) pCH2CHCH2OCCH3 CF3 I O to form the telomere comprising allyl (CF3) 2CF (CH? -CH) pCH2CH = CH2"CF3 The telomere comprising allyl 68 can be used as a monomer in the formation of polymers, for example.

In exemplary embodiments, systems 40, 50, and 60 may be sequentially aligned to produce a telomer comprising allyl 68 from taxogen 42 and telogen 44, when referring to Figures 4, 5, and 6 in the sequence. In this alignment, the telomer 49 produced in the system 40 can be used as the telomer 52 in the system 50, and the telomer 58 produced in the system 50 can be used as the telomer 64 As such, the telomere comprising allyl 68 may include a fluoromonomer that includes a telomer of trifiuoropropene. Telomeres 49, 52, 64, and 68 may include (CH2-CH) n CF3 j with n being at least 1.

For example, and by way of example only, with reference to Table 3 below, telomeres, esters, and monomers having the aforementioned characteristics can be produced.

TABLE 3 Characteristics of telomere, ester, and monomer * GC analysis: column OV1 (3% silicone fat in chromosorb G); 2m length, 1/8"(0.3 cm) in diameter, slope of 50-200 ° C. In accordance with another embodiment of the description, the intermediary-RF including the telomeres described above can be modified in accordance with the scheme (24) below. . ,. ,. , _ alilmagnefío 1.! .1. ¿? ¿J? Ftatk? RQ-2- 6.7. Weíraftuoi c-4 6-. > íluoro > nct? l > 4-rtdopefitar, or (trilluoromeWl epl.I -ene In accordance with the scheme (24) mentioned above, a 150 mL round bottom flask with three necks can be equipped with a reflux condenser, stirrer, thermocoupler, an outer cover for heating, and an addition funnel of 150 mL at compensated pressure that can contain 70 mL of allylmagnesium bromide in a 1.0 M solution of diethyl ether Approximately 27.64 grams (0.07 moles) of 1, 1, 1, 2.5, 5,5-Heptafluoro-2- (trifluoromethyl) -4-iodopentane can be added to the flask The allymagnesium bromide solution can be added slowly to the flask where an exotherm can be observed along with a change in the color of orange to Colorless Allylmagnesium bromide can be added over a period of 2.5 hours then the reaction mixture can be kept at room temperature overnight., the reaction mixture can be washed in water to remove any unreacted allylmagnesium bromide, an organic layer can be observed, decanted, and dried over MgSO4. Samples of the dried organic layer can be analyzed by gas chromatography / mass spectroscopy, (m / z 306 (M +), 237 (M + -CF3)). In accordance with another embodiment of the disclosure, the RF-intermediates including the telomeres described above can be modified to form additional RF-intermediates. For example, and by way of example only, the intermediate-RF 1, 1, 1, 2,6,7,7,7-octafluoro-2,6-bis (trifiuoromethyl) -4-iodoheptane can be modified to form the intermediate -RF 6,7,7,7-tetrafluoro-4- (2,3,3,3-eiefluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) -hept-1-ene in accordance with scheme (25) below. 6.7 .7-letrrsf luoro- * - (2,3,3.3-letr'sti? Oro-2- (lr¡ftjoíoiii-1i) pro? L) -6-Ctr? FiJ? F? Cnil) i? ept-ueno With reference to the aforementioned scheme 25, a dry flask can be charged with (488 grams) and anhydrous ether (306 mL) to form a mixture. The mixture can be cooled to 0 ° C with one year of ice / water and 1 M allylmagnesium bromide in ether (976 mL) can be slowly added to the mixture for 3 hours and the mixture is allowed to warm to room temperature throughout the night. Then saturated ammonium chloride (500 mL) can be added dropwise to the mixture at a rate to maintain the temperature of the mixture at < 5 ° C, and deionized water (250 mL) can be added to aid in the dissolution of the salts and form a biphasic mixture from which the organic layer can be separated and dried over magnesium sulfate, filtered and distilled at 5 ° C. Torr and 41 ° C-43 ° C to produce a clear liquid (361 g, 84.2%). The residual ether can be removed by boiling to produce 359.6 grams as can be identified by NMR. As another example, 120 grams (0.24 mole) of (1, 1, 2, 6, 7, 7, 7) can be added into a dry 500-mL round bottom flask equipped with an addition funnel. Octafluoro-2,6-bis (trifluoromethyl) -4-iodoheptane) to 150 mL of anhydrous THF to form a mixture. Under an atmosphere of N2, the mixture can be cooled to 0 ° C while stirring vigorously. To the mixture can be added 120 mL of a 2M solution of allylmagnesium bromide in THF at a rate to maintain a temperature of the mixture of less than about 5 ° C. After the addition of the allylmagnesium bromide solution, the flask can be allowed to slowly warm to room temperature. A white powder suspension can be formed during the reaction and can be removed by suction filtration to form a concentrate by filtration. The concentrate by filtration can be washed with 100 mL of THF, and the filtrate is collected and added to 3 to 5 mL of water to destroy any remnants of allylmagnesium bromide. The THF can be distilled and the remaining solution can be washed with water. The organic layer (90.7 grams) can be dried with MgSO4 and distilled at 40 ° C-41 ° C / 5 Torr to isolate approximately 63 grams of the RF intermediate at 63.5% (percentage area by gas chromatography) 6.7, 7,7-tetrafluoro-4- (2,3,3,3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) hept-1-ene. As further described in the above-mentioned scheme (25), 6,7,7,7-tetrafluoro-4- (2,3,3,3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) hept-1-ene can be modified to produce another intermediate-Rp. With reference to the aforementioned scheme, inside a 100 mL pressure tube equipped with a 9-inch (22.8 cm) Hg Pen-Ray® lamp, pressure gauge, agitator, and inner tube, 60 grams (0.14 moles) may be added. of 6,7,7,7-tetrafluoro-4- (2,3,3,3-tetrafluoro-2- (trifluoromethyl) propyl) -6- (trifluoromethyl) hept-1-ene. The tube can be sealed and anhydrous gaseous HBr can be bubbled into the system to maintain a pressure of 101.37 kPa at 308.27 kPa. The tube can be irradiated with the Pen-Ray lamp until the pressure does not continue to decrease. The mixture can then be washed once with water and once with 10% aqueous sodium bicarbonate. The organic layer can be assayed as high as 92.7% (percentage area by gas chromatography) and can be dried with MgSO and distill at 73 ° C-74 ° C / 3.1 Torr. 2. 9-bisf! R? Fluor? R? Ei? L} -4-ioctodecsno With reference to the aforementioned scheme (26), to a 250 mL round bottom flask with three necks equipped with thermocoupler, stirrer, and reflux condenser can be added 71.05 grams (0.13 moles) of the intermediate-RF 1, 1, 1, 2,8,9,9,9-octafluoro-2,8-bis (trifluoromethyl) -4-iodooctane, then cooling to 0 ° C in an ice bath. Approximately 121.37 grams (0.14 moles) of 1.0 M allylmagnesium bromide in diethyl ether can be added dropwise with a 150 mL addition funnel at compensated pressure over a period of 3 hours. After the addition, the solution can be gradually heated to room temperature and maintained for 48 hours. The mixture can then be quenched with deionized water and the organic layer decanted and dried over MgSO4. The unpurified RF intermediate-8,9,9,9-tetrafluoro-4- (2,3,3,3-tetrafluoro-2- (trifluoromethyl) propyl) -8- (trifluoromethyl) -non-1-ene can be assay by mass spectrometry (m / z 462 (M +), 420.1 (M + -42), 279.1 (M + -183)). According to a further embodiment, the RF-intermediates, including the telomeres described above, such as 1, 1, 1, 2,2,3,3,4,4,5,5,6,6,9,9, 9-hexadecafluoro-8-iodononane, can be modified according to scheme (27) below. ltkle añusro-8 -. (it¡ttuQiop- & lil! '10 -a oundec & no S, 6, 7, 7, 3, 8.9,9,10,10,11, 1 1, 1 i-lideHuoro-4-ritliiorometi und c.l -ero One embodiment of the disclosure provides surfactant-RF compositions that include the RF portions described above. Exemplary surfactant-Rp compositions can be referred to as Rp-Qs- In a system having at least two parts, Rp may have a higher affinity for a first part of the system compared to Qs, and Qs may have a higher affinity for a second part of the system compared to RF. The system may include liquid / liquid systems, liquid / gas systems, liquid / solid systems, and / or gas / solid systems. Liquid / liquid systems, for example, can include systems having at least one part that includes water and another liquid part that is hydrophobic in relation to the part that includes water. Liquid / liquid systems can also include systems that can also include systems in which water is not a part of the system, such as hydrocarbon liquid systems. In exemplary embodiments, RF may be relatively hydrophobic to Qs and / or Qs may be relatively hydrophilic to RF. RF can be hydrophobic and Qs can be hydrophilic, for example. The hydrophobic portion can be referred to as the tail of the surfactant-RF, and the hydrophilic portion can be referred to as the head of the surfactant-Rp. The surfactant-Rp agents may include those surfactants having a hydrophobic tail or portion containing fluorine. The tail of the surfactant-RF or hydrophobic portion can be referred to as an RF portion, and the head of the surfactant-RF or hydrophilic portion can be referred to as a portion Qs. Exemplary surfactant-Rp include those in Table 4 below.

TABLE 4 Surfactants-RF Surfactants-RF can also include NMR: 1H (D6-DMSO, 300 MHz) d 1.8 (m, 2H), 2.6 (m, 2H), 3.0 (m, 2H), 3.1 (bs, 6H), 3.6 (m, 2H), 3.9 (m, 4H), 7.9 (bs, 1 H); 13C (D6-DMSO, 75 MHz) d 22.6, 22.9, 23.1, 43.1, 50.0, 60.8, 64.4, 88-93 (ds), 114.5-126.5 (qd); and 19F (CFCI3, D6-DMSO, 282 MHz) d -76.4 (d, 6.95 Hz, 6F), -183.4 (m, 1 F) In accordance with a modality of the., description, procedures are provided for the production of the surfactant-RF. Exemplary methods for the production of the surfactant-Rp include the provision of an RF-intermediate such as the RF-intermediates described above having at least two -CF3 groups. Exemplary RF-intermediates can include RF-Q9 with Qg being designed for the subsequent binding to the Qs portion of the RF-surfactants, for example. The exemplary methods for the preparation of surfactants can be found in Germán Offen. 1, 924, 264 and Patent of E.U.A. 3,721, 706 both incorporated in the present invention as references. Exemplary methods for the preparation of surfactant-RF agents are described below. With reference to Figure 7, it is shown that a system 70 can be configured to carry out a process that includes reacting an RF-intermediate to form an RF-surfactant, with the RF-intermediate including at least one fluorine atom. , for example. System 70 may include reactors 71 and 75. Reactor 71 may be configured to expose an RF-intermediate 72 to a reactive radical 73. In exemplary embodiments, RF-intermediate 72 may include an RF portion, such as those described above. . Reagent 73 may include HSCH2C02H, for example. The RF-intermediate 72 can be exposed to a reagent 73 in the presence of a radical initiator, such as AlBN to produce an RF intermediate 74 such as RF-C3H6-S-CH2CO2H, for example. In exemplary embodiments, the reactor 75 can be configured to combine the RF-intermediate 74 and the reagent 76 to produce an RF-77 surfactant. The reagent 76 can include HO (CH2CH2?) N-CH3 and the surfactant-RF 77 can include RF-C3H6 ~ S-CH2C (0) (CH2CH2) nCH3, with n being at least 1, for example. As another example, reagent 73 may include initiator and / or ethylene radicals (CH2 = CH2). After exposure of the RF-intermediate 72 to the reagent 73 within the reactor 71, the RF-intermediate 74, such as RF-CH2CH2I + N (CH3) 3, can be produced, for example. The reactor 72 can be configured to expose the intermediate-Rp 74 to the reagent 76 to form the surfactant-RF 67. The reagent 76 can include pyridine, for example. The surfactant-RF 77 may include Rp-surfactants such as RF-QS, with Qs including a quaternary ammonium ion such as -CH2CH2N + (CH3) 3r, for example. According to another embodiment, the RF-intermediates can be converted to thiocyanate-Rp intermediates such as RF-SCN, by reacting heterohalogen-Rp intermediates such as iodine-RF intermediates, for example, with potassium thiocyanate. The reaction can be carried out in absolute ethanol using acetic acid as a catalyst. A 30% molar excess of KSCN can be used compared to the intermediate-Rp. The ethanol, acetic acid, intermediate-RF, and KSCN can be loaded into a reaction vessel, heated to reflux, and kept so until the reaction is complete. The progress of the reaction can be monitored by analyzing the reaction mixture for the RF-intermediate by gas chromatography. After the end of the reaction, the Kl formed can be filtered from the reaction mixture, the ethanol can be removed by evaporation, and the intermediate thiocyanate-RF can be washed twice with hot water (70 ° C). Reagent 73 may include a mixture of KSCN, ethanol and acetic acid described above. The Rp-intermediary can be exposed to the mixture at a temperature of about 83 ° C and / or reflux temperature to produce an intermediate 74 such as RF-SCN. The intermediary-Rp 74 can then be exposed to! reagent 76 to form intermediate 77. RF-intermediate 74, such as RF-SCN can be wet-chlorinated to produce the sulfonyl chloride of the RF-intermediate as shown below in the exemplary reaction sequence (28). 2RF-SCN + 8H20 + 9CI2_! 2RF-S02CI + 2C02 + N2 + 16HCI (28) The Rp-SCN, water, and acetic acid as a solvent can be charged to a reactor 75. Chlorine can be added to the vessel for reaction in 30 minute increments while the The temperature of the mixture inside the reactor 75 is maintained at 20 ° C to 30 ° C. At the end of each addition of chlorine for 30 minutes, 0.314 grams of water can be added to reactor 75. For each gram of chlorine added, 4.5 moles per mole of Rp-SCN can be added. When this amount has been added, the mixture within the reactor 75 can be sampled and analyzed for RF-SCN by gas chromatography. When the reaction is complete, the mixture within the reactor 75 can be diluted to 65% (w / w) of RF-S02CI with chloroform, heated to about 40 ° C and washed twice with its volume of water at 40 ° C. C. After washing, the wash mixture can be dried by azeotropic water distillation using a Dean Stark trap. The Karl Fischer titration can be used to determine the amount of water. The water content can be less than 0.1%. As described above, reagent 76 may include a mixture of Cl 2, H 20 and acetic acid. The intermediate-Rp 74 can be exposed to the mixture at a temperature of about 30 ° C to 40 ° C to produce the RF-intermediate 67, such as RF-S02CI. With reference to Figure 8, in a further embodiment, a system 80 configured to produce RF-surfactants is shown from the R-intermediates, for example, those produced in the system 70, such as the RF-intermediate 77. System 80 may include reagents 81 and 82. Reactor 81 may be configured to expose an RF-intermediate 83, such as the RF-intermediate 77 described above., to reagent 84. RF-intermediate 83 may have the general formula RF-S02CI described above, for example. In an exemplary embodiment, exposure of the intermediate-Rp 83 to the reagent 84 esterifies the intermediate 83 to form the intermediate-Rp 85, which may include a sulfonamidoamine. Dimethylaminopropylamine (H2N (CH2) 3N (CH3) 2, DMAPA) can be used to esterify intermediate 83 as shown as exemplary reaction scheme (29) and described below. RF-S02CI + H2N (CH2) 3N (CH3) 2- F-S02NH (CH2) 3N (CH3) 2 + HCl (29) The esterification can be carried out in a refluxing chloroform solution. In solvent and the reagents can be so dry that they have at least less than 0.1% by weight of water. The DMAPA can be dissolved in 1.5 times its volume in chloroform in the reactor 81 which can be immersed in a bath for cooling. A molar equivalent of DMAPA of Rp-S02Cl at 65% (w / w) in chloroform solution can be added to the reactor 81 while maintaining the temperature of the contents of the reactor 81 at less than 50 ° C. When the addition is complete, the temperature of the contents can be raised to reflux and maintained at reflux for 5 hours. The contents of the reactor 81 can then be cooled to 60 ° C and washed 3 times with equal volumes of water at 60 ° C. The remaining chloroform can be removed under vacuum, and the pure product can be washed twice with water at 90 ° C. The pure washed product can be sampled and analyzed for free DMAPA using a wet chemistry method that is specific for primary amines. In accordance with an exemplary embodiment, reagent 84 may include a mixture of DMAPA and CHCl3. The intermediate 83 can be exposed to the mixture at a temperature between about 30 ° C-65 ° C to produce the RF-intermediate 85, such as for example. As another example, reagent 84 may include a mixture of 2-aminoacetic acid and CHCI3 and intermediate 83 may be exposed to the mixture at a temperature between about 30 ° C-65 ° C to produce RF-intermediate 85, such as The reagent 84 can also include a mixture of 2- (methylamino) acetic acid and CHCI3 and the intermediate 83 can be exposed to the mixture at a temperature between about 30 ° C-65 ° C to produce the intermediate 85, such as Intermediate 85 can then be betainized, for example, with an acetate reagent such as sodium monochloroacetate within reactor 82 to produce surfactant-RF 87, such as the amphoteric surfactant-RF RF-S? 2NH (CH2) 3N + (CH3) 2 (CH2C? 2Na) as shown as exemplary reaction sequence (30) and described below. RFS? 2NH (CH2) 3N (CH3) 2 + CICH2COO a? RFS? 2NH (CH2) 3N + (CH3) 2 (CH2CO2Na) (30) The sulfonamide can be dissolved in sufficient absolute ethanol to produce a 40% (w / w) solution. An equimolar amount of sodium monochloroacetate can be added to the reactor 82 containing the 40% (w / w) solution to form a mixture. The mixture can then be refluxed for 8 hours and then sampled and titrated to "free OH" If the OH "is greater than 1.5 x 10" 3 equivalents, the mixture is refluxed for an additional hour and re-analyzed This sequence can be repeated until the free OH is less than 1.5 x 10"3 equivalents If there is no decline in OH" in two successive samples, additional sodium monochloroacetate can be added, the amount being calculated as the amount needed to lower the OH "to a value below 1.5 x 10" 3 equivalents. The NaCl by-product can be filtered and enough water added to produce a solution that can be poured at room temperature. The reactor 82 can be configured to expose the intermediate 85, such as to reagent 86 to form the surfactant-RF 87. In accordance with an exemplary embodiment, reagent 86 may include a mixture of and ethanol. The intermediate 83 can be exposed to the mixture while the mixture is refluxed to produce the surfactant-RF 87, such as for example. As another example, reagent 86 may include a mixture of 50% H202 / H20 (w / w) and intermediate 83, such as for example, it can be exposed to the mixture at a temperature of about 35 ° C to produce the surfactant-RF 87, such as Reagent 86 also include 1- (chloromethyl) benzene, and the intermediate 85, as is exposed to 1- (chloromethyl) benzene to produce the surfactant-RF 87, such as In accordance with another example, reagent 86 may include 1- (bromomethyl) benzene, and intermediate 85, such as can be exposed to 1- (bromomethyl) benzene to produce surfactant-RF 87, such as As another example, reagent 86 may include bromomethane and intermediate 85, such as can be exposed to bromomethane to produce the surfactant-RF 87, such as Reagent 86 may also include cioromethane and intermediate 85, such as can be exposed to chloromethane to produce the surfactant-Rp 87, such as According to another embodiment, reagent 86 may also include a basic solution such as NaOH and intermediate 85, such as may be exposed to the solution to produce the surfactant-RF 87, such as The systems 70 and 80 can be combined in sequence and the surfactants-RF are produced in accordance with schemes (31) - (45) below. Where LC / MS can be used to identify the compounds, LC / MS parameter table 5 can be used, below.

TABLE 5 Parameters of LC-MS 3,4,4,4-tet''8ft ~ 'to-3- (trftluc > tomet¡0 butane-I -e? rum? lC' chloride In accordance with the scheme (31) mentioned above, a mixture of 1,1,1,2-tetrafluoro-4-iodo-2-trifluoromethyl-butane (100 grams) and potassium thiocyanate (39 grams) can be dissolved in 55 mL of ethanol and 1 mL of acetic acid and It is heated to reflux, where it can be left to reflux for a couple of days. The mixture can be cooled to room temperature and concentrated to dryness under vacuum. The deionized water (100 mL) can be added to the dry solids and the resulting oil can be decanted and identified as being 1, 1, 1, 2-tetrafluoro-4-thiocyanato-2-trifluoromethyl-butane (69.9 grams, 88.4 %) by NMR analysis. A mixture of 1, 1, 1, 2-tetrafluoro-4-thiocyanato-2-trifluoromethyl-butane (25.5 grams) in 25 mL of acetic acid containing 2 mL of water can be chlorinated in gas at 40 ° C. a couple of days with intermittent heating of the mixture to form a heterogeneous mixture. The mixture can be cooled to room temperature and diluted with chloroform (50 mL). The organic portion can be washed twice with water, dried over sodium sulfate, filtered, and concentrated under vacuum. The resulting yellow oil may contain large amounts of residual acetic acid by NMR analysis. The yellow oil can be dissolved in chloroform and washed twice with water (25 mL / each time), dried over sodium sulfate, filtered, and concentrated under vacuum and identified as being 4,4,4,3-tetrafluoro chloride. -4-trifluoromethyl-butanesulfonyl (23.8 grams, 80%) by NMR analysis. The 4,4,4,3-tetrafluoro-4-trifluoromethyl-butanesulfonyl chloride (23.8 grams) can be dissolved in 50 mL of ether and added dropwise to a solution of dimethylaminopropylamine (8.2 g) and 11.2 mL of triethylamine ( TEA) at room temperature for 20 minutes to form a mixture. The mixture can be partitioned between ethyl acetate (100 mL) and water (150 mL). The organic layer can be separated and washed with saturated bicarbonate solution (50 mL) and brine (50 mL), dried over sodium sulfate, filtered, and concentrated under vacuum to a yellow semi-solid. The NMR and LC / MS analysis may indicate that the yellow semi-solid may be a mixture of the mono- and bis-sulfonate material. The semi-solid can be triturated in hexanes, and the filtered solid was identified as 3,4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonic acid (3-dimethylamino-propyl) -amide. 9.9 grams) by NMR analysis. The 3,4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonic acid (3-dimethylamino-propyl) -amide (10 grams) can be dissolved in 50 mL of ethanol containing 3.2 grams of chloroacetate. sodium to form a mixture and it can be refluxed overnight. The mixture can be filtered, concentrated under vacuum, and distilled twice using chloroform to produce by NMR analysis. The product can be placed in the Kugelrohr at 60 ° C and 0.1 Torr to produce a solid similar to a light yellow foam (10 grams, 84%).

According to the aforementioned scheme (32), 3,4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonic acid (3-dimethylamino-propyl) -amide (9 grams) can be dissolved in 20%. mL of ethanol and 3.5 mL of water and treated with 5.9 mL of 50% hydrogen peroxide (w / w). The resulting mixture can be heated at 35 ° C overnight and the reaction was determined to be complete by LC / MS analysis. Norit, a decolorizing carbon (4 grams) can be added to the mixture, stirred for 30 minutes, and filtered through celite. Additional charcoal (4 grams) can be added, the mixture heated to 50 ° C, the heated mixture filtered through celite again, the resulting filtered concentrate washed with ethanol, and the combined filtrates concentrated in vacuo to leave white solids. The white solid can be identified to be by NMR and LC / MS analysis. The white solid can be dried in the Kugeirohr at 45 ° C and 0.1 Torr to produce 8.7 grams (92%) of the product by NMR analysis.

According to the aforementioned scheme (33), 5.0 grams of 3,4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonic acid (3-dimethylamino-propyl) amide can be dissolved in 15 mL of t -butyl methyl ether in a 100 mL round bottom flask, with three necks equipped with a stir bar, reflux condenser and a thermocoupler. 1.75 grams of benzyl chloride can be added to the flask to form a mixture and the mixture heated to reflux (56 C) and stirred. A white precipitate can form when the temperature reaches 56 ° C. The mixture can be cooled to room temperature after 3 hours. The solids can be collected by filtration, washed with chloroform and air dried to produce 2.83 grams of as identified by NMR.

In accordance with the scheme (34) mentioned above, . 0 grams of 3,4,4,4-tetrafluoro-3-trifluoromethylbutane-1-sulfonic acid (3-dimethylamino-propyl) amide can be dissolved in 15.0 mL of t-butyl methyl ether in a 100 mL bottom flask round, with three necks equipped with a bar for agitation, reflux condenser and a thermocoupler. The benzyl bromide (2.36 grams) can be added to the flask to form a mixture and the mixture is heated to reflux (56 ° C) and stirred for 2 hours. A white precipitate may form when the temperature of the mixture reaches 56 ° C. The mixture may become too thick to stir after 2 hours. The mixture can be cooled to room temperature and the solids are collected by filtration and dried in a vacuum oven at 45 ° C overnight to yield 6.24 grams (99.6%) as can be identified by NMR.

In accordance with the scheme (35) mentioned above, . 0 grams of 3,4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonic acid (3-dimethylamino-propyl) amide can be dissolved in 13.8 mL of a 2.0 M solution of bromomethane in diethyl ether in a tube for 25 x 250 mm culture with a Teflon coating to form a mixture. The mixture can be heated at 45 ° C for 4 hours to form a thick precipitate. The mixture can be cooled to room temperature and the solids are collected by filtration and dried under vacuum to yield a white solid which can be identified as 7.46 grams (59.9%) by LC / MS.

According to the aforementioned scheme (36), 5.0 grams of 3,4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonic acid (3-dimethylamino-propyl) amide can be dissolved in 13.8 mL of a 1.0 M solution of chloromethane in t-butyl methyl ether in a 100 mL round bottom flask, with three necks equipped with a stir bar, reflux condenser and a thermocoupler to form a mixture. The mixture can be heated to reflux (56 ° C) and stirred for 4 hours to form a thicker precipitate that can be filtered to yield 0.56 grams of which can be identified by NMR. Surfactants-Rp can also be prepared according to scheme 37 below. (lp 2-Sm'moc? cfo acid) According to the scheme (38) mentioned above, 9.68 grams of glycine benzyl ester hydrochloride can be partitioned between 100 mL of methylene chloride and 200 mL of a 1: 1 solution of carbonate of aqueous sodium at 15% (w / w) and brine The layers can be separated and the lower organic layer is washed with 200 mL of a 1: 1 solution of 15% aqueous sodium carbonate (w / w) and brine The layers can be separated again, and the organic layer is dried over sodium sulfate, filtered and concentrated under vacuum to yield 5.42 grams (68.3%) of a light yellow oil identified as benzyl glycinate by NMR. A solution of 5,421 grams of the benzyl glycinate shown above, in 15.0 mL of methylene chloride in a 100 mL round bottom flask, with three necks equipped with a stir bar, addition funnel with a nitrogen inlet and a thermocoupler , it can be cooled 0 ° C-5 ° C in a bath with ice. Another solution of 4.75 grams of 3,4,4,4-tetrafluoro-3-trifluoromethylbutane-1-sulfonyl chloride, previously demonstrated, may be added in 15.0 mL of methylene chloride, dropwise under nitrogen, at such a rate that the reaction temperature is maintained < 5 ° C, (15 minutes, Tmax = 3.5 ° C) to form a mixture. The mixture can be stirred for 1 hour at < 5 ° C. The mixture can be filtered and the solids washed three times with 25 mL of methylene chloride. The solids can be identified by NMR as 3,4,4,4-tetrafluoro-3-trifluoromethyl-1-butane-sulfonylamino) -acetic acid benzyl ester. The benzyl ester of 3,4,4,4-tetrafluoro-3-trifluoromethyl-1-butane sulfonylamino) -acetic acid (1.0 gram) can be dissolved in 10 mL of ethanol in a Parr bottle of 250 mL. Palladium on charcoal (10% (w / w), 50% (w / w) water type Degussa E101, 0.2 grams) can be added to the bottle to form a mixture. The bottle can be placed on a Parr shaker at 418 kPa and stirred overnight. The mixture can be sprayed with nitrogen and filtered through a thin pad of Celite. The Celite can be rinsed three times with 20 mL of ethanol, and 1.18 mL of a 2N aqueous sodium hydroxide solution is added to the combined filtrate and stirred. The filtrate can be concentrated under vacuum and dried to yield 0.803 grams (95.7%) of a desired white solid product which can be identified as by NMR.

CH ^ CI? According to the aforementioned scheme (39), sarcosine ethyl ester hydrochloride (7.68 grams) can be partitioned between 100 mL of methylene chloride and 200 mL of a 1: 1 solution of 15% aqueous sodium carbonate. (p / p) and brine. The layers can be separated and the lower organic layer is washed with 200 mL of a 1: 1 solution of 15% aqueous sodium carbonate (w / w) and brine. The organic layer can be dried over sodium sulfate, filtered and concentrated under vacuum to yield 5.45 grams (93.0%) of a colorless oil which can be identified as sarcosine ethyl ester by NMR. A solution of 5.45 grams of the sarcosine ethyl ester in 20.0 mL of methylene chloride in a 100 mL round bottom flask, with three necks equipped with a stir bar, addition funnel with a nitrogen inlet, and a thermocoupler, It can be cooled to 0 ° C-5 ° C in a bath with ice. A solution of 6.91 grams of 3,4,4,4-tetrafluoro-3-trifluoromethyl chloride! butane-1-sulfonyl, described above, in 20.0 mL of methylene chloride can be added, dropwise under nitrogen, at such a rate that the reaction temperature is maintained < 5 ° C, (45 minutes, max - 2.1 ° C) to form a mixture. The mixture can be stirred for 3 hours. < 5 ° C, (Tmax = 3.7 ° C) and washed twice with 20 mL of an aqueous solution of 5% HCl (w / w) and once with brine. The organic layer can be recovered, dried over sodium sulfate, filtered, and concentrated under vacuum to yield 7.78 grams of a light yellow oil that can be placed in a Kugeirohr and heated to 50 ° C, 0.01 Torr to remove the impurities with low boiling point and was identified as [methyl- (3,4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonyl) -amino] -acetic acid ethyl ester (>; 96%) by NMR. A solution of 6.8 grams of [Methyl- (3,4,4,4-tetrafluoro-3-trifluoromethyl-butane-1-sulfonyl) -amino] -acetic acid ethyl ester in 25.0 mL of ethanol in a 100 mL flask. of round bottom, with a single neck can be treated with an equivalent of 2N sodium hydroxide (9.0 mL) to form a mixture. The mixture can be stirred at room temperature overnight, concentrated under vacuum, and placed in a Kugeirohr at 50 ° C, 0.01 Torr for 30 minutes to yield 6.21 grams (93.0%) (> 9?%) By NMR 4- (3-b? O, 1, 2.6,7,, 7-or talluoro bíí (trí! Hjoromet¡0heptar? O -2,6-l: 'faith (trífluoro? El l? ) -4- clone »o (3-lioc-jnatopro? -V? Eplano (tri? Luor In accordance with the scheme (40) mentioned above, a solution of (876 grams), prepared according to the scheme (24) mentioned above, and potassium thiocyanate (255 grams) can be dissolved in ethanol (880 mL) and acetic acid (35 mL) and heated to reflux and then subjected to at reflux for about 2.5 hours to form a heterogeneous mixture which can be cooled to room temperature and concentrated under vacuum to a yellow semi-solid. The semi-solid can be partitioned between methylene chloride (1 L) and deionized water (1 L), the aqueous phase can be extracted with methylene chloride (500 mL) and the combined organic layers are dried over magnesium sulfate, filter, and concentrate under vacuum to a yellow oil. The yellow oil can be placed briefly in the Kugeirohr at room temperature and 0.1 Torr to produce 828.3 grams (99.3%) of 97% by NMR. (828.3 grams) can be dissolved in acetic acid (828 mL) to form a mixture. The mixture can be treated with 33 mL of deionized water and sprayed with chlorine and heated at 40 ° C overnight with additional water treatments. The temperature of the mixture can be increased to 50 ° C and you can continue heating with a chlorine spray for additional days to achieve approximately 80% consumption. The mixture can be cooled to room temperature and stopped using methylene chloride (2 L) and deionized water (2 L). The organic layer can be washed three times with deionized water (1 L each time). The organic layer can then be dried over magnesium sulfate overnight. The dried organic layer can be filtered and concentrated under vacuum to a colorless oil (862.4 grams), and the oil can be dissolved in acetic acid (850 mL) to form a mixture. This mixture can be heated to 50 ° C with a chlorine spray, and deionized water (33 mL) can be added once the reaction reaches 50 ° C. The mixture can be allowed to cool to room temperature and stopped using methylene chloride (2 L) and deionized water (1 L). The organic layer can be washed three times with deionized water (1 L each time) and then dried over magnesium sulfate overnight. The dried organic layer can be filtered and concentrated under vacuum to a colorless oil (859.6 grams, 95.4%). NMR analysis and gas chromatography can indicate (97%, percentage area) Dimethylaminopropuamine oo mL; and chloroform (4 L) can be combined to form a mixture and cooled to 0 ° C using an oil / acetone bath and (839 grams) can be dissolved in chloroform (4 L) and added dropwise to the mixture for four hours to keep the mixture at temperature < 0 ° C. The reaction can be completed one hour after the dropwise addition to form a yellow solution. The yellow homogeneous reaction solution can be washed with saturated bicarbonate (8 L), deionized water (8 L), and brine (8 L) and the organic layer is dried over magnesium sulfate, filtered, and concentrated at vacuum until obtaining a white solid. The white solid can be dried for one hour under vacuum at 35 ° C to produce 899.7 (95.2%, percent area) of by NMR. (600 grams) can be dissolved in ethanol (820 mL) and water (130 mL) with 50% hydrogen peroxide (w / w) (241 mL) to form a mixture and heated to 35 ° C. An exotherm can be observed with a tmax = 49.3 ° C. The reaction can be complete one hour after heating the mixture as determined by NMR analysis, however, by LC / MS analysis a trace amount of raw material can be observed. The mixture can be heated again at 35 ° C for two hours to complete the reaction. The decolorizing carbon (135 grams) and ethanol (820 mL) can be added to the mixture portion by portion and the mixture heated to 50 ° C. An exotherm was observed. The mixture can be allowed to stir at room temperature overnight. The reaction can be evaluated for peroxide using starch test strips Kl, and if it is positive, the mixture can be heated to 50 ° C for 1.5 hours or until it is negative. Then the mixture can be filtered through celite and the celite pad is washed using 1 L of ethanol. The filtrate can be concentrated to a white solid and the white solid placed in the Kugeirohr for 30 minutes at 0.1 Torr and 50 ° C. Then the white solid can be dried under vacuum at 50 ° C for four hours to yield 593.8 grams (96.6%) of 6,7,7,7-tetrafluoro-4- (2,3,3,3-tetrafluoro-2- trifluoromethyl-propyl) -6-trifluoromethyl-heptane-1-sulfonyl amine by NMR and / or LC / MS. 6,7,7,7-Tetrafluoro-4- (2,3,3,3-tetrafluoro-2-trifluoromethyl-propyl) -6-trifluoromethyl-heptane-1-sulfonyl amine (319 grams), ethanol (1290 mL ), and sodium chloroacetate (63.5 grams) can be combined to form a mixture and the mixture is brought to reflux for 48 hours. After 48 hours, the NMR analysis may indicate that the raw material is not present, however, the LC / MS analysis may indicate the ions of the product. The mixture can be filtered and the filtered concentrate washed with ethanol (1 L). The filtrate can be concentrated under vacuum to an orange foam and the orange foam is placed in the Kugeirohr at 0.1 Torr and 50 ° C for one hour. The orange foam-like solid can be dried overnight under vacuum at 50CC to produce 344.4 grams (98.2%) of as demonstrated by NMR.

According to the aforementioned scheme (41), 6,7,7,7-Tetrafluoro-4- (2,3,3,3-tetrafluoro-2-trifluoromethyl-propyl (3-dimethylamino-propyl) -amide). ) -6-trifluoromethyl-heptane-1-sulfonic acid (6.2 grams) can be dissolved in 25 mL of ethanol containing 1.23 grams of sodium chloroacetate to form a solution. The solution can be heated to reflux and allowed to reflux overnight. After refluxing for about 2 days, the solution can be stopped, filtered, and the solvent removed from the filtrate overnight in a vacuum oven (50 ° C, 1 Torr). The remaining solids can be identified as by NMR.

With reference to the aforementioned scheme (42), a solution of 6,7,7,7-tetrafluoro-4- (2,3,3,3-tetrafluoro-2-trifluoromethyl-propyl) -6-trifluoromethyl heptane- chloride 1-Sulphonyl (25 grams), described above, in 125 mL of dichloromethane can be added dropwise to a cooled solution (0 ° C-5 ° C) of ethanolamine (17.6 grams) in dichloromethane (125 mL) to form a mixture. The mixture can be stirred, allowed to warm to room temperature, and diluted with dichloromethane (250 mL). The diluted mixture can be washed with deionized water (250 mL), 5% HCl (w / w) (250 mL), and saturated bicarbonate solution (250 mL). The organic layer can be separated, dried over sodium sulfate, filtered, and concentrated under vacuum to yield 6,7,7,7-tetrafluoro-4- (2-hydroxy-ethyl) -amide. , 3,3,3-tetrafluoro-2-trifluoromethyl-propyl) -6-trifluoromethyl-1-heptane-1-sulfonic acid (5.0 grams) with residual dichloromean and eianolamine by NMR analysis. A solution of the 6,7,7,7-tetrafluoro-4- (2,3,3,3-tetrafluoro-2-trifluoromethyl-propyl) -6-trifluoromethyl-heptane (2-hydroxy-ethyl) -amide. -1-sulphonic (5.0 grams) and 2-chloro- [1,2,2] dioxaphospholane-2-oxide (0.87 mL) can be dissolved in anhydrous ether (30 mL) and cooled to 0 ° C using an ice bath /Water. Triethylamine (0.55 mL) can be added dropwise to the solution to form a white precipitate. The solution can be allowed to warm to room temperature, filter, and concentrate under vacuum. The reaction can start to decompose after 6 hours. The bulk solution can be filtered and concentrated under vacuum to obtain a yellow oil (3.3 grams) that can be identified as by NMR and / or LC / MS analysis.

F-C- --- KSCN - "^ F.r E10M (? 3)? COH" SCN F 83 ° ü r- "> t-3C- j F According to the scheme (43) mentioned above, 5-bromo-1,1,1,2-tetrafluoro-2-trifluoromethyl-pentane (25 grams) can be dissolved in 25 mL of ethanol and 0.2 mL of acetic acid, and 10.9 grams of potassium thiocyanate can be added to form a mixture. The mixture can be heated to reflux and cooled to room temperature after about 1 to 2.5 hours, and concentrated under vacuum. The concentrate can be partitioned between methylene chloride (100 mL) and water (50 mL). The aqueous phase can be extracted with methylene chloride (50 mL), the combined organic layers are dried over magnesium sulfate, filtered, and concentrated under vacuum to yield a yellow oil which can be identified as 1.1. , 1,2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane (21.7 grams, 93.9%) by NMR analysis. The 1,1,1,2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane can be dissolved in 10 mL of acetic acid and 0.4 mL of water, heated to 40 ° C and sprayed with chlorine. Three additional treatments with water (.4 mL) can be added every 2 hours with a slight exotherm temperature observed after each addition. The mixture can be sprayed and additional treatments with water are added for a couple of days to result in a heterogeneous mixture. The heterogeneous mixture can be partitioned between methylene chloride (100 mL) and water (25 mL), the organic layer is dried over magnesium sulfate, filter, and concentrate under vacuum. NMR analysis may indicate 7.1 grams (74.1%) of 4,5,5,5-tetrafluoro-4-trifluoromethyl-pentanesulfonyl chloride. The 4,5,5,5-tetrafluoro-4-trifluoromethyl-pentanesulfonyl chloride (7.1 grams) can be dissolved in 40 mL of chloroform and added to a solution of 8.6 mL of 3-dimethylaminopropylamine in 40 mL of chloroform. at 0 ° C-5 ° C drop by drop for 45 minutes to form a mixture. The mixture can be washed successively with saturated bicarbonate solution (80 mL), water (80 mL), and brine (80 mL). The organic layer can be separated, dried over magnesium sulfate, filtered, and concentrated under vacuum to yield 8 grams (93%) of 4,5,5,5-tetrafluoro-4-dimethylaminopropyl-amide. -trifluoromethyl-pentane-1-sulfonic acid by NMR and LC / MS analysis. 4,5,5,5-tetrafluoro-4-trifluoromethyl-pentane-1-sulfonic acid (3-dimethylamino-propyl) -amide (8 grams) can be dissolved in 25 mL of ethanol containing 3 mL of water and 5.1 mL of 50% hydrogen peroxide (w / w) and the resulting solution was heated at 35 ° C for 30 minutes. Then the reaction can be allowed to cool to room temperature overnight.

Norit, a decolorizing carbon (10 grams) and ethanol (20 mL) can be added and the mixture heated to 50 ° C for 3 hours. The mixture can be filtered through celite, the filtered concentrate is washed with 90% (w / w) ethanol / 10% (w / w) water (60 mL), and the filtrate is concentrated under vacuum, distilled with methanol, and Kugeirohr to produce 7.1 grams (89.9%) of by NMR and LCMS analysis.

According to the aforementioned scheme (44), 4,5,5,5-tetrafluoro-4-trifluoromethyl-pentane-1-sulfonic acid (3-dimethylamino-propyl) -amide (6.0 grams) can be dissolved in 25 g. mL of ethanol containing 1.9 grams of sodium chloroacetate. The resulting solution can be heated to reflux and refluxed for two consecutive nights. After refluxing for approximately 45 hours, the reaction can be stopped, filtered, the salts rinsed and discarded and the filtrate removed from the solvent and identified as (3.6 grams) by NMR. b'lUH F -.C I- ~~ "" "" "" "" '(nal) FjC "); -b -ro'mo-1i .1, 1.2-iÉlrsHuoro-2- (f? llrjoro? neW ) or af »o 1 -1 '1.2-telralli? -2. (lr? llu ro? ftet¡i) -8-l¡oc? arvalo octano According to the aforementioned scheme (45), 8-Bromo-1,1,1,2-tetrafluoro-2-trifluoromethyl-octane (20 grams) can be dissolved in 30 mL of ethanol containing 7.6 grams of potassium thiocyanate . The acetic acid (0.2 mL) can be added to form a mixture and the mixture heated to reflux for 4 hours. The mixture can be left to cool to room temperature overnight, concentrated under vacuum, and partitioned between methylene chloride (200 mL) and water (100 mL). The organic layer can be dried over magnesium sulfate, filtered, and concentrated under vacuum to yield 18.2 grams (97%) of 1,1,1,2-tetrafluoro-8-thiocyanato-2-trifluoromethyl-octane by NMR analysis. 1, 1, 1, 2-tetrafluoro-8-thiocyanato-2-trifluoromethyl-octane (18.2 grams) can be dissolved in 25 mL of acetic acid to form a mixture and the mixture heated to 40 ° C with chlorine spray . Initially, 0.8 mL of water can be added to the mixture. Three additional water treatments (0.8 mL / each) can be added to the mixture every 2 hours and heated with continuous chlorine spray overnight and added with 0.8 mL of additional water, the mixture can be cooled and partitioned between methylene chloride (200 mL) and water (100 mL). The aqueous layer can be extracted with methylene chloride (100 mL). The organic layers can be combined, washed three times with water (100 mL / each), dried over magnesium sulfate, filtered, and concentrated to yield 19.5 grams (94.5%) of 7,8,8,8-tetrafluoro-7. -trifluoromethyl-sulfonyl octanechloride by NMR analysis. 7,8,8,8-Tetrafluoro-7-trifluoromethyl-octansulfonyl chloride (19.5 grams) can be dissolved in 100 mL of chloroform and added to 20.9 mL of dimethylaminopropylamine in 100 mL of chloroform at 0 ° C-5 ° C for 1 hour to form a mixture. When the addition is complete, the mixture can be allowed to warm to room temperature and can be stirred at room temperature for one hour. The mixture can be washed twice with saturated bicarbonate solution (100 mL / each), deionized water (200 mL), and brine (200 mL). The organic layer can be dried over magnesium sulfate, filtered, and concentrated under vacuum to yield a yellow oil which can be identified as 7,8,8,8-tetrafluoro-7- (3-dimethylamino-propyl) -amide. trifluoromethyl-octane-1-sulfonic acid (24.09 grams, 95.97%) by NMR. The 7,8,8,8-tetrafluoro-7-trifluoromethyl-octane-1-sulfonic acid (3-dimethylamino-propyl) -amide (7 grams) can be dissolved in 25 mL of ethanol containing 2.3 mL of water and 4.0 mL of 50% (w / w) hydrogen peroxide and the resulting solution can be heated to 35 ° C overnight. It is possible to add decolorizing charcoal (8 grams) and ethanol (15 mL) to the solution and the solution was heated at 50 ° C for three hours. The solution can then be cooled to room temperature, filtered through celite, the filtered concentrate is washed with 90% (w / w) ethanol / deionized water (50 mL), and the filtrate is concentrated under vacuum until a similar solid is obtained to the wax. The solid can be distilled twice with ethanol to produce a yellow oil that can be placed in a Kugeirohr for two hours at 40 ° C and 0.1 Torr to produce a white solid (5.9 grams, 79.9%) of by NMR analysis.

According to the aforementioned scheme (46), 7,8,8,8-tetrafluoro-7-trifluoromethyl-octane-1-sulfonic acid (3-dimethylamino-propyl) -amide (6.0 grams) can be dissolved in 25 g. mL of ethanol containing 1.6 grams of sodium chloroacetate. The resulting solution can be heated to reflux and refluxed and stirred for 40 hours. The solution can be stopped, filtered, the solvent can be removed, and the resulting solid placed in a drying oven (50 ° C, 1 Torr) overnight. The remaining solids can be identified as by NMR. 2-. { 3-bromopropoxy) -1, 1, 1, 3, 3, 3-hexafluoropropane 2- (3-thiocyanatopropoxy) -1, 1, 3, 3, 3- exafluoropropane 3- (1,1,1,3,3,3-hexafluoropropan-2-yloxy) propane-1-sulfonyl chloride (47) According to the scheme (47) mentioned above, 2- (3-Bromo-propoxy) -1, 1, 1, 3,3,3-hexafluoro-propane (19 grams) and potassium thiocyanate (8.3 grams) can be dissolve in 30 mL of ethanol containing 0. 2 mL of acetic acid and heated to reflux. After 2.5 hours at reflux, the reaction mixture can be cooled to room temperature and concentrated in vacuo to a semi-solid. The semi-solid can be partitioned between ether (100 mL) and deionized water (100 mL). The organic layer can be dried over sodium sulfate, filtered, and concentrated under vacuum to yield a yellow oil (16.88 grams, 90.3%). The yellow oil can be identified as 1, 1, 1, 3,3,3-hexafluoro-2- (3-thiocyanato-propoxy) -propane by NMR. The 1,1,1,3,3-hexafluoro-2- (3-thiocyanato-propoxy) -propane (16.9 grams) can be dissolved in 30 mL of acetic acid and 0.8 mL of water to form a mixture. The mixture can be heated to 40 ° C and sprayed with chlorine. The mixture can then be treated three times with deionized water (0.8 mL) every two hours, and the mixture is heated to 40 ° C under a spray of chlorine for approximately 48 hours. The mixture can be allowed to cool to room temperature, it can be partitioned between methylene chloride (100 mL) and deionized water (100 mL), the organic layer is separated and washed three times with deionized water (100 mL / each), dried over magnesium sulfate, filtered, and concentrated in vacuo to a colorless oil of 3- (2,2,2-trifluoro-1-trifluoromethyl-ethoxy) -propane-1-sulfonyl chloride (18.4 grams, 99.3 g. %) by NMR. The 3- (2,2,2-trifluoro-1-trifluoromethyl-ethoxy) -propane-1-sulfonyl chloride (18.4 grams) can be dissolved in 100 mL of chloroform and added to 22.5 mL of dimethylaminopropylamine in 100 mL of chloroform at 0 ° C-5 ° C for 1 hour to form a mixture. When the addition is complete the mixture can be allowed to warm to room temperature and is stirred at room temperature for 1 hour. The mixture can be washed with saturated bicarbonate solution (200 mL), deionized water (200 mL), and brine (200 mL). The organic layer can be dried over magnesium sulfate, filtered, and concentrated under vacuum to yield a yellow oil which can be placed in the Kugeirohr for 15 minutes at room temperature and 0.1 Torr to produce (3-dimethylamino-propyl) -amide of the 3- (2,2,2-Trifluoro-1-trifluoromethyl-ethoxy) -propane-1-sulfonic acid (20.88g (92.8%)) by NMR. 3- (2,2,2-Trifluoro-1-trifluoromethyl-ethoxy) -propane-1-sulfonic acid (3-dimethylamino-propyl) -amide (7 grams) can be dissolved in 25 mL of ethanol containing 2.6 mL of water and 4.4 mL of 50% hydrogen peroxide (w / w) to form a mixture and the mixture was heated at 35 ° C overnight. It is possible to add decolorizing carbon (8 grams) and ethanol (15 mL) to the mixture, the mixture was heated at 50 ° C for 3 hours, filtered through celite, the filtered concentrate was washed with 90% (w / w) ) of ethanol / water (50 mL) and the filtrate can be concentrated under vacuum to produce a white semi-solid. The solid can be refluxed twice in ethanol before being placed in the Kugeirohr for 1 hour at 40 ° C and 0.1 Torr to produce (6.66 grams (90.0%)) by NMR.

According to the aforementioned scheme (48), 3- (2,2,2-trifluoro-1-trifluoromethyl-ethoxy) -propane-1-sulfonic acid (3-dimethylamino-propyl) -amide (6.0 grams) It can be dissolved in 25 mL of ethanol containing 1.9 grams of sodium chloroacetate. The resulting solution can be refluxed and stirred for 40 hours, the reaction stopped, and filtered. The solvent can be removed and the resulting solid placed in a drying oven (50 ° C, 1 Torr) overnight to produce by NMR.

H According to the aforementioned scheme (49), a solution of 3,5-bis (trifluoromethyl) benzyl bromide (25 g) and 11.9 grams of potassium thiocyanate can be dissolved in 40 mL of ethanol and 0.2 mL of acetic acid and it is heated to reflux, refluxed for 3 hours, cooled to room temperature, and concentrated under vacuum to yield a white solid. The solid can be partitioned between ether (150 mL) and deionized water (150 mL). The organic layer can be dried over sodium sulfate, filtered, and concentrated under vacuum to yield 1,1,1-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane (23.1 grams, 98.8%) by NMR analysis. The 1,1,1,2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane (23.1 grams) can be dissolved in 33 mL of acetic acid and heated to 40 ° C with chlorine spray overnight to produce a precipitate of white color. The heterogeneous mixture can be allowed to cool to room temperature, partition between deionized water (150 mL) and methylene chloride (150 mL). The organic layer can be washed three times with deionized water (100 mL), dried over magnesium sulfate, filtered, and concentrated under vacuum to yield a white solid that can be placed in the Kugeirohr at 0.1 Torr and 40 ° C per 30 minutes. NMR analysis may indicate 3,5-bis-trifluoromethyl phenyl) -methanesulfonyl chloride (18.52 grams, 70.1%). 3,5-Bis-trifluoromethyl-phenyl-methanesulfonyl chloride (18.5 grams) can be dissolved in 100 mL of chloroform and cooled to 0 ° C-5 ° C, then 20 mL of 3-dimethylaminopropylamine can be added in 100 mL of chloroform drop by drop for 1 hour. The mixture can be allowed to warm to room temperature and is stirred at room temperature for 3 hours. The reaction can then be washed with saturated bicarbonate solution (200 mL), deionized water (200 mL), and brine (200 mL). The organic layer can be separated, dried over magnesium sulfate and concentrated under vacuum to yield a yellow solid (20.0 grams). The NMR analysis may indicate that the yellow oil is a 1: 1 mixture of mono- and bis-sulfonyl-amine products.

With reference to the aforementioned scheme (50), the raw material of mono and bisulfonyl amine (10 grams) can be dissolved in 30 mL of ethanol, deionized water (3.7 mL) and 50% hydrogen peroxide (w / w) (4.7 mL). The heterogeneous mixture can be allowed to stir at room temperature for 2 days and decolorizing carbon (7 grams) and ethanol (15 mL) are added to the mixture. The mixture can be stirred for 2 days at room temperature, monitored for peroxide, the reaction in bulk is filtered through celite, the filtered concentrate is washed with 90% ethanol (w / w), water (50 mL), and the filtrate is concentrated under vacuum to yield a yellow solid (7.07 grams). The yellow solid can be identified as a 1: 1 mixture of mono / bis products by NMR and / or LC / MS analysis.

With reference to the aforementioned scheme (51), a solution of 3,5-bis (trifluoromethyl) benzyl bromide (25 grams) and 11.9 grams of potassium thiocyanate can be suspended in 40 mL of ethanol and 0.2 mL of acetic acid and it is heated to reflux, refluxed for 3 hours, allowed to cool to room temperature, and then concentrated under vacuum to produce a white solid. The white solid can be partitioned between ether (100mL) and deionized water (100mL). The organic layer can be separated, dried over sodium sulfate, filtered, and concentrated under vacuum to yield 1,1,1,2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane (22.58 grams, 96.6%), which can be identified by NMR. The 1,1,1,2-tetrafluoro-5-thiocyanato-2-trifluoromethyl-pentane (22.5 grams) can be dissolved in 32 mL of acetic acid and heated at 50 ° C with chlorine spray overnight. The reaction mixture can be allowed to cool to room temperature, partition between methylene chloride (100 mL) and deionized water (100 mL), the organic layer is repeatedly washed with deionized water (100 mL / each), dried over magnesium sulfate, filtered, and concentrated under vacuum to yield a white solid. of 3,5-bis-trifluoromethyl phenyl) -methanesulfonyl chloride (22.94 grams, 89.1%) which can be determined by NMR. The 3,5-bis-trifluoromethyl phenyl) -methanesulfonyl chloride (5 grams) can be dissolved in 25 mL of chloroform and added to a cooled (0 ° C-5 ° C) solution of 4.4 mL of 3-dimethylaminopropylamine in 25 mL of chloroform dropwise for 1 hour, then allow to warm to room temperature after the addition is complete. The homogeneous solution can be washed with saturated bicarbonate solution (50 mL), deionized water (50 mL), and brine (50 mL). The organic layer can be separated, dried over magnesium sulfate, filtered, and concentrated under vacuum to yield a yellow solid (5.26 grams, 87.7%), which can be determined by NMR analysis as being 90% C-. (3,5-bis-trifluoromethyl-phenyl) -N- (3-dimethylamino-propyl) -methanesulfonamide with the impurity being the addition compound bis.

With reference to the aforementioned scheme (52), C- (3,5-Bis-trif-uoromethyl-phenyl) -N- (3-d-methylamino-propyl) -methanesulfonamide (6 grams) can be dissolved in 20 mL of ethanol, deionized water (2.2 mL) and 50% hydrogen peroxide (w / w) (3.6 mL), and the heterogeneous mixture is allowed to stir at room temperature overnight. Subsequently the sample can be cooled, decolorizing carbon (5 grams) and ethanol are added (15 mL), heated at 50 ° C for 2 hours, monitored for peroxide, cooled at room temperature, and filtered through celite. The concentrate by filtration can be washed with 90% (weight / weight) of ethanol, 10% (w / w) of water (50 mL), and the filtrate is concentrated under vacuum to yield C- (3,5-bis-trifluoromethyl-phenyl) -N- (3-dimethylamino-propyl) -methanesulfonamide by NMR analysis.

EtOH With reference to the scheme (53) mentioned above, the O (3,5-bis-trifluoromethyl-phenyl) -N- (3-dimethylamino-propyl) -methanesulfonamide (2 grams) can be dissolved in ethanol (20 mL), and sodium chloroacetate (0.59) grams) and refluxed overnight, the reaction is left cool to room temperature, filter, and the filtrate is concentrated under vacuum until obtaining a white solid. The white solid can be placed in the Kugeirohr at 0.1 Torr and 50 ° C for 1 hour to produce 2.1 grams (91.3%) by NMR analysis.

THF With reference to the scheme (t> 4) mentioned above, a solution of polyethylene glycol (PEG) (12.01 grams) in THF (70 mL) can be added.

Cool (0 ° C) in a nitrogen atmosphere and add lithium bis (trimethylsilyl) amide (33.0 mL) to form a mixture. The mixture can be let stir for 15 minutes at 0 ° C. The intermediary-RF it can be placed in THF (70 mL) and added dropwise to the mixture. The mixture can be allowed to stir at 0 ° C for 30 minutes, then allowed to warm to room temperature and stirred for one hour. Subsequently, the mixture It can be heated to 40 ° C and left to stir overnight to form a clear tan solution, which can have a small amount of Suspended solid matter, which can be acidified with HCl (5% (w / w), 135 mL) until obtaining a pH = 3. The solids can be dissolved in the solution at pH = 9 and the mixture turns to a yellow color Clear. The solution biphasic can be separated, the aqueous layer is left aside, the organic layer is Dry over Na2SO, filter, and remove the solvent. The yellow oil resulting can be placed in the Kugeirohr (40 ° C, 0.1 Torr, 15 minutes) to Remove the residual solvent. A 1H NMR analysis of the heterogeneous oil Yellow (8.1 grams) can be identified as a mixture of raw material and PEG, unwanted product, as LC / MS analysis may suggest. The yellow oil can be distilled in the Kugeirohr and it is determined that the remnants are the desired product (1.8 grams) by NMR and / or LC / MS. tilene With reference to the aforementioned scheme (55), The RF-intermediary it can be combined with thiourea (0.68 grams) in ethanol (25 mL) and heated to reflux overnight. After 22 hours of reflux, the reaction system can be dismantled, the ethanol is removed, and the remaining oil is placed in the Kugeirohr (0.01 mmHg, 20 min, 60 ° C) which can produce 7.8, 8,8-tetrafluoro-7-trifluoromethy1-octane-1-thiol (3.4 grams) which can be determined by NMR and / or LC / MS analysis. The 7,8,8,8-tetrafluoro-7-trifluoromethyl-octane-1-thiol can be placed in a flask and cooled to 0 ° C and NaH (0.08 grams) added to form a mixture. The mixture can be cooled to -78 ° C, subjected to a nitrogen jet, condensed in ethylene oxide (1.6 grams), and allowed to warm to room temperature, then placed in an oil bath at 65 ° C All night long. Ethyl acetate (20 mL) and HCl (1 N, 10 mL) can be added to the mixture, the layers are separated, the aqueous layer is extracted with ethyl acetate (20 mL, 5 times). All organic layers can be combined, dried over Na 2 SO 4, filtered, the solvent removed and the resulting brown oil (2.2 grams) characterized by LC / MS analysis.

With reference to the aforementioned scheme (56), a solution of the RF-intermediary Potassium thiocyanate (8.7 grams), ethanol (40 mL), and acetic acid (0.2 mL) can be combined and brought to reflux, refluxed for 3 hours, and the heterogeneous mixture allowed to cool to room temperature and concentrated under vacuum to produce a white / yellow semi-solid. The semi-solid can be partitioned between ether (100 mL) and deionized water (100 mL). The organic layer can be separated, dried over sodium sulfate, filtered, and concentrated under vacuum to yield an orange oil (21.19 grams, 97.2%) which can be identified as 1,1, 1,2-tetrafluoro-7- thiocyanato-2,4-bistrifluoromethyl-heptane (> 95% pure) by NMR analysis and gas chromatography. The 1,1,1,2-tetrafluoro-7-thiocyanato-2,4-bistrifluoromethyl-heptane can be dissolved in 30 mL of acetic acid and heated at 40 ° C with chlorine spray overnight. The temperature of the mixture can be increased to 50 ° C for 6 hours and allowed to cool to room temperature. The mixture can be partitioned between methylene chloride (100 mL) and deionized water (100 mL), the organic layer can be separated, washed repeatedly with deionized water (100 mL / each), dried over magnesium sulfate, filtered, and Concentrate under vacuum until a colorless oil is obtained. The oil can be placed in the Kugeirohr at 0.1 Torr and 40 ° C for 30 minutes to produce a yellow oil (13.4 grams, 57.3%) that can be identified by NMR analysis and gas chromatography to be indicated as > 94% 6,7,7,7-tetrafluoro-4,6-bis-trifluoromethyl-heptanesulfonyl chloride. Dimethylaminopropyl amine (11.6 mL) can be dissolved in chloroform (75 mL) and cooled to 0 ° C. The 6,7,7,7-tetrafluoro-4,6-bis-trifluoromethyl-heptanesulfonyl chloride (13.4 grams) can be dissolved in chloroform (75 mL) and added dropwise to the cooled solution to form a mixture. Once the addition is complete, the mixture can be allowed to warm to room temperature, and can be washed with saturated bicarbonate solution (150 mL), deionized water (150 mL), and brine (150 mL). The organic layer can be separated, dried over magnesium sulfate, filtered, and concentrated under vacuum to yield an orange oil (14.94 grams, 96.0%). The orange oil can be found to be 6,7,7,7-tetrafluoro-4,6-bis-trifluoromethyl-heptane-1-sulfonic acid (3-dimethylamino-propyl) -amide by NMR analysis.

With reference to the scheme (57) mentioned above, the 6,7,7,7-Tetrafluoro-4,6-bis-trifluoromethyl-heptane-1-sulfonic acid (3-dimethylamino-propyl) -amide (7.5 grams) can be dissolved in 25 mL ethanol, deionized water (30 mL) and 50% hydrogen peroxide (w / w) (3.7 mL). The homogeneous mixture can be allowed to stir at room temperature overnight. Fading carbon (5 g) and ethanol (15 mL) can be added to the mixture and the mixture heated to 50 ° C for 2.5 hours while monitoring for peroxide. The reaction mixture can then be cooled to room temperature and filtered through celite. The concentrate by filtration can be washed with 90% (w / w) ethanol, 10% (w / w) water (50 mL), the filtrate is concentrated under vacuum and the resulting oil is identified as by NMR.

With reference to the aforementioned scheme (58), 6,7,7,7-tetrafluoro-4,6-bis-trifluoromethyl-1-sulfonic acid (3-dimethylamino-propyl) -amide (7.5 grams) ) can be dissolved in ethanol (40 mL), and sodium chloroacetate (1.85 grams) to form a mixture. The mixture can be refluxed overnight. The heterogeneous mixture can be cooled to room temperature and filtered, the filtrate is concentrated under vacuum to produce an orange oil. The orange oil can be dried in the Kugeirohr at 0.1 Torr and 50 ° C for one hour to produce a solid amber color (7.85 grams, 93.1%). The solid amber color can be identified as by NMR analysis. According to another embodiment, a mercapto-RF intermediate can also be produced by reacting an iodine-RF intermediate with thiourea to make the isothiuronium salt and treating the isothiuronium salt with sodium hydroxide to produce the mercapto-RF intermediate more sodium iodide, as described in the US Patent 3,544,663 incorporated herein by reference. In an exemplary aspect of the disclosure, the mercapto-RF intermediate can be attached to a Qs portion such as a 2-acrylamido-2-methyl-1-propanesulfonic acid group available from Lubrizol as AMPS. 2403, as generally described in the U.S. Patent. 4,000,188 embodied in the present invention as a reference. The aminoxides of the surfactants-RF can be produced in accordance with the processes that include those generally described in the patent of E.U.A. 4,983,769, incorporated herein by reference. Accordingly, sulfoamidoamines can be combined with ethanol and water and 70% (w / w) of hydrogen peroxide and heated to at least 35 ° C for 24 hours. The activated carbon can then be added and the mixture refluxed for about 2 hours. The reaction mixture can be filtered and the filtrate evaporated to dry to provide the amine oxide of the surfactant-RF- According to another embodiment of the description, the processes that can be used to alter the surface tension of a part are provided. of a system that has at least two parts. The system may include liquid / solid systems, liquid / gas systems, gas / solid systems, and / or liquid / liquid systems. In an exemplary embodiment, the liquid / liquid systems may have a part that includes water and another part that includes a liquid that is relatively hydrophobic when compared to water. In accordance with the other example, the liquid / liquid system may contain a part that is relatively hydrophobic when compared to water and / or relatively hydrophobic when compared to another part of the system. The surfactants-RF can be used to alter the surface tension of a part of the system, for example, by the addition of the surfactant-RF to the system. The surfactants-RF can be used as relatively pure solutions or as mixtures with other components. For example, and by way of example only, the RF surfactants can be added to a system and the surface tension of the system is determined by the Wilhelmy plate method and / or using the Kruss tensiometer method. The surface tensions of the solutions of - «- can be determined in accordance with the concentrations shown in Figure 9. As another example, the surface tensions of at pH 7"and 5" at various concentrations and the data are indicated in figure 10. As another example, the surface tensions of at various concentrations and the data are indicated in Figure 11. As another example, the surface tensions of At pH 6.8 XX and pH 4.0 XX and the data are indicated in figure 12. As another example, the surface tensions of at various concentrations and the data are indicated in figure 13. As another example, the surface tensions of at various concentrations and the data are indicated in figure 14. As another example, the surface tensions of at various concentrations and the data are indicated in figure 15. As another example, the surface tensions of at pH 6.2-6.8 and pH 5.0 and the data are indicated in Figure 16. The surface tensions and corresponding concentrations of the surfactants-RF are shown in Table 6 below.

TABLE 6 Surface tensions of the surfactant-RF The above-described surfactants-RF can be incorporated into detergents, emulsifiers, paints, adhesives, inks, wetting agents, foaming adhesives, and / or defoamers, for example. The surfactants-RF can be incorporated into the AFFF formulations and these formulations can be used foams to fight the fire, to prevent, and / or extinguish combustion. An exemplary use of AFFFs that include a surfactant-RF agent includes the addition of AFFF to high pressure spray forming systems, spray forming systems can be used to prevent and / or extinguish combustion. The AFFF formulations can be provided to a substrate, for example. The substrate may include liquid and / or solid compositions. The AFFF formulations can also be dispersed in an atmosphere including gaseous atmospheres, such as air to prevent and / or extinguish combustion. The formulations may include other components such as water soluble solvents. These solvents can facilitate the solubilization of surfactants-RF and other surfactants. These solvents can also act as foam stabilizers and / or agents for freeze protection. Exemplary solvents include ethylene glycol, diethylene glycol, glycerol, Cellusolve® ethyl, Carbitol® butyl, Dowanol DPM®, Dowanol TPM®, Dowanol PTB®, propylene glycol, and / or hexylene glycol. Components additional to the formulation, such as polymeric stabilizers and thickeners, can be incorporated into the formulation to improve the foam stability property of a foam produced from the aeration of the aqueous solution of the formulation. Exemplary polymeric stabilizers and thickeners include partially hydrolyzed proteins, starches, polyvinyl resins such as polyvinyl alcohol, polyacrylamides, carboxyvinyl polymers, and / or poly (oxyethylene) glycol. Polysaccharide resins, such as xanthan gum, can be included in the formulation as a foam stabilizer in formulations for use in the prevention or extinction of the combustion of polar solvents, such as combustion by alcohol, ketone, and / or ether, for example. The formulation may also include a pH regulator for regulating the pH of the formulation, for example, tris (2-hydroxyethyl) amine or sodium acetate, and a corrosion inhibitor such as toluoltriazole or sodium nitrite may be included. . Water-soluble electrolytes such as magnesium sulfate can be included and the film's extension characteristics of the formulation can be improved.

For example and by way of example only, the following formulations can be prepared using surfactants-RF. The formulations mentioned in the following tables can be prepared and applied to the substrates indicated.

TABLE 7 Exemplary AFFF Formulations # 1 A premixed solution at 3% (w / w) of the formulation # 1 in water from the aforementioned table 7 can be used to produce a film in the heptane substrate.

TABLE 8 Exemplary formulation of AFFF # 2 A premixed solution at 3% (w / w) of formulation # 2 in water from the aforementioned table 8 can be used to form a film on the heptane substrate.

TABLE 9 Exemplary AFFF formulation mixture A third formulation including 3% (w / w) of the formulation of the mixture of Table 9 above and 0.15% (w / w) of they can form film on heptane and cyclohexane substrates. A fourth formulation that includes 3% (w / w) of the formulation mixture of Table 9 above and 0.15% (w / w) of It can form film on the substrates of heptane and cyclohexane.

TABLE 10 Formulations AFFF 5 and 6 copies The formulations 5 and 6 of the aforementioned Table 10 can be used at 3% (w / w) concentrations to generate foam and film on the heptane substrate. The R-surfactants may also be useful in formulations including other surfactants such as alkyl sulfate, alkyl ether sulphates, alphaolefin sulphonates, alkyl sulfobetaines, alkyl polyglycerides, alkylamidopropyl betaines, alkylimidazolindicarboxylates, sodium salt of 2-alkylthiopropionamido-2-methylpropanesulfonic acid, alkyliminodipropinates, alkyl sulfonates, ethoxylated alkylphenols, dialkylsulfosuccinates, and / or alkyltrimethyl ammonium chloride. A variation of AFFF, AiRAFFF, an acronym for alcohol-resistant aqueous film-forming foam (s), can be used to extinguish fires caused by hydrocarbons in much the same way that the AFFF foams and can also be used to extinguish the fires involving water-soluble solvents such as acetone and isopropanol which are not extinguished by conventional AFFF foams. The ARAFFF formulations may contain the same ingredients as conventional AFFF formulations plus a polysaccharide such as xanthan gum and, in some formulations, a polymeric foam stabilizer. Polymeric foam stabilizers are provided by DuPont® and Dynax®, Inc. An exemplary DuPont product, Forafac® 1268, is a water-soluble acrylic polymer. An exemplary Dynax product, DX5011®, is an ethylene-imine polymer. Xanthan gum is provided by several suppliers, including Kelco CP (Keizan) and Rhodia North America (Rhol).

The polysaccharide may only be suitable for making alcohol-resistant ARAFFF formulations, but the amount required produces a foam concentrate which can be quite viscous. The use of a polymeric foam stabilizer can allow a reduction in the amount of polysaccharide required for the production of a useful alcohol resistance. Due to the possibility of microbial attack on the polysaccharide solutions, the ARAFFF concentrates may contain an effective amount of a bokid such as Kathon CG ICP, made by Rohm & Haas. Many other biocides such as Acticida, Nipacida and Dowicil can also be effective. Some ARAFFF formulations can be designed to be provided at different percentages depending on whether the substrate to be extinguished is a hydrocarbon or an alcohol type substrate, for example. The alcohol type subtracter can include any fuel having a hydroxyl group. Exemplary ARAFFF formulations (3% (w / w) x 3% (w / w)) using RF surfactants are described in tables 11-14 as follows. In all the cases described in tables 11-14, water is the balance of the formulation.

TABLE 11 Exemplary ARAFFF TABLE 12 ARAFFF exemplary TABLE 13 Exemplary ARAFFF TABLE 14 Exemplary ARAFFF Foam stabilizers can be prepared, such as RF-stabilizers that include the RF groups described above, for example. The RF-stabilizers may include RF-QFS-QFS compositions may include portions that have a greater hydrophilic character than RF. Exemplary foam-RF stabilizers include, but are not limited to, those in Table 15 below.

TABLE 15 Exemplary foam stabilizers-RF For example and as an example only, it can be a portion Q s- The RF-stabilizers can be prepared according to the scheme (59) below. 2- . { trillion melil) p ntano FJ meti) 2- (4,5.5.5-tetra0uoro-4- (tr * t * luo rt? E1ir) pentliio) ace1atD CF, O McOíM.-i '"" -X ^ 3 ~ - ^ JL .-S.

With reference to the aforementioned scheme (59), potassium carbonate (2.37 grams), metioglycolate (1.82 grams) and dimethylformamide (DMF) (20 mL) can be added and the mixture heated to 50 ° C for 3 hours. The mixture can be left stirring overnight at room temperature to form a yellow slurry which can be added to water (50 mL) and ethyl acetate (50 mL), the combined organic layers are dried over Na2SO4, they are filtered, and the solvent is removed. In a nitrogen atmosphere, thioester (4.0 grams) and polyethylenimine (PEI, pm = 1200) (5.3 grams) can be placed in isopropanol (5 mL) and stirred until they dissolve to form a mixture. Sodium methoxide (0.15 grams) and sodium borohydride (0.04 grams) can be added to the mixture and the mixture is heated at 115 ° C for 15 hours, then stirred at room temperature for 2 days. The removal of the remaining isopropanal can be difficult. A solution of sodium chloroacetate (10.52 grams) in water (25mL) can be added dropwise to the mixture and the temperature is kept below 55 ° C and then the mixture is heated at 70 ° C for two hours. NaOH (1.23 grams of a 50% (w / w) solution of NaOH and water) can be added to raise the pH of the mixture to at least 7.5 from the initial pH of about 6. Then the mixture can be left in continuous stirring at 70 ° C for 2 additional hours, then the heat is removed, and the resulting (4.4 grams, 82% yield.) Is characterized (1 H NMR analysis). He produced can be compared to other foam stabilizers in accordance with tables 16-19 below.

TABLE 16 Test of foam stabilizer on hot acetone (52 ° C-53 ° C) 150 mm dish -100 grams of mixed solution for foam First hole in the film 11 minutes 08 seconds after the formulation and 50% foam collapse 11 minutes 35 seconds after the formation.

TABLE 17 Test of foam stabilizer on hot acetone (52 ° C-53 ° C) Plate of 150 mm -100 grams of mixed solution for foam First hole 8 minutes 4 seconds after training and 50% collapse 10 minutes 30 seconds after training.

TABLE 18 Test of foam stabilizer on hot acetone (52 ° C-53 ° C) Plate of 150 mm -100 grams of mixed solution for foam First hole 12 minutes 20 seconds after training and 50% collapse 12 minutes 45 seconds after training.

TABLE 19 Test of foam stabilizer on hot acetone (52 ° C-53 ° C) Plate of 150 mm -100 grams of mixed solution for foam First hole 7 minutes 40 seconds after the formation. Also provided are the RF-metal complexes such as RF-QMC incorporating the RF portions. The RF portions can be incorporated as acid halides or carboxylic acids, for example, with the acid halide including, but not limited to, acid fluorides, for example. The RF-metal complexes can include RF-intermediates and, as such, Qg can be interchangeable with QMG-QMC can include the portion of a ligand of a metal complex which is coordinated with the metal forming the complex, for example. Exemplary metal-RF complexes include, but are not limited to, those in Table 20 below.

TABLE 20 RF-metal complexes An exemplary method for the preparation of metal-Rp complexes includes reacting the Rp-intermediary having halogen functionality, so that Qg is 1, described above, with fuming sulfuric acid to produce an intermediate -RF that has an acid fluoride functionality, for example. The metal-RF complexes can be prepared with reference to scheme (60) below.

An acid-RF fluoride intermediate can be reacted with an amino acid such as glycine to produce an amine ester. The amine ester can be reacted with chromic chloride in an alcohol such as methanol or isopropanol to produce an exemplary metal-RF complex such as a chromium-Rp complex. Exemplary acid-RF intermediates for use in the preparation of the metal-Rp complexes may include ethylenecarboxylic acid-RF intermediates and / or mixtures of the ethylenecarboxylic acid-RF intermediates and the carboxylic acid-RF intermediates. The exemplary preparations can be carried out in accordance with the Patents of E.U.A. 3,351, 643, 3,574,518, 3,907,576, 6,525,127, and 6,294,107, incorporated herein by reference. The metal-Rp complexes may include a ligand having an RF portion and a Q C portion associated with the complex metal. In exemplary embodiments, the Q c portion may have a higher affinity for the complex metal than for the RF portion. The metal-RF complexes can be used for the treatment of substrates such as paper, leather, textiles, yarn, fabrics, glass, ceramic products, and / or metals. In some cases the treatment of the substrates with the complexes makes the substrates less permeable to water and / or oil.

An embodiment of the present invention is also provided for the incorporation of the RF portions within the phosphate esters which, in exemplary embodiments, can be used for the treatment of substrates and / or to be used as dispersion agents during the preparation of the polymers. RF-exemplary phosphate esters include RF-QPE, with the portion of the QPE being toward the phosphate portion of the RF composition. Phosphate-Rp esters, include, but are not limited to, those in Table 21 below.

TABLE 21 Phosphate-Phosphate esters Esters of phosphate-RF can be prepared with reference to schemes (61) and (62) below. p2o = (61) or POCI3 Rp-OH »* - (RFO) 3., PO. { OM), M "With reference to the scheme (61) mentioned above, a RF intermediary that have a hydroxyl functionality (Qg = OH) can be obtained by the reaction of the iodine-RF intermediates (Qg = l) with a Strong base such as KOH. Intermediate iodine-RF can be reacted with P205 or POCI3 in the presence of a metal (M) to produce phosphate ester- Exemplary RF or pyrophosphate-Rp in accordance with the Patents of E.U.A. 2,559,749 and 2,597,702, incorporated herein by reference, which generally describe the conversion of hydroxyl compounds to phosphate esters using P205 or POCI3 to produce esters partial These reactions can also be carried out in the presence of pyridine as an HCl receptor. The monoalkyl phosphates can also be prepared by treatment with phosphorous pentoxide P205 with an excess of moles of the hydroxyl-Rp intermediate followed by resulting hydrolysis of the pyrophosphate-Rp. Subsequently the product can be isolated or precipitate as the ammonia salt by adding ammonia to the reaction mixture. Alternatively, a solution of salts of mono- and Mixed di-esters can be prepared by neutralization of a mixture of the acids with aqueous ammonia and amine or alkali metal hydroxide.

The dialkyl phosphates-RF can also be prepared by a molar excess reaction of the RF-intermediate with phosphorous pentoxide (not shown). However, instead of hydrolysis, the pyrophosphate-RF intermediates can be heated at low pressure. Alternatively, the phosphate-RF esters can be prepared and separated by treating the hydroxyl-Rp intermediate with phosphorous pentoxide, neutralizing the resulting mixed acid phosphate with aqueous ammonia, and amine such as the tetraalkylammonium base or the alkali metal hydroxide produces a solution which may include amine or metal salts of the esters (not shown). The salts of the esters can be dissolved in toluene and can be purged with ammonia to precipitate a mixture of the salts of the corresponding esters. Toluene and the unreacted hydroxyl-RF intermediate and by-products, such as the corresponding trialkyl phosphate-R, can be removed by filtration producing compositions having the general formula RpAOPORp, as described in the patent of E.U.A. 4,145,382, incorporated herein by reference. As used in this general formula, the RF is the RF portion, A is a methylene group or another similar spacer group from the phosphate ester and may be present in amounts as high as 3 and as small as nothing, and RF is a salt corresponding to the phosphate including alkali metal acid ammonium or substituted ammonium such as ethanol amine. The RF-phosphates can be used as dispersion agents in the preparation of polymers or they can be diluted and used to treat the substrate materials in aqueous baths, for example, by ordinary means such as filling, submersion, impregnation, spraying, etc. . These compositions can be incorporated or used to treat such materials as textile fabrics, textile yarn, leather, paper, plastic, linen for sheets, wood, clay for ceramics, as well as, prepared articles prepared from them such as articles of clothing, tapestries, paper bags, cardboard boxes, porous earthenware, etc. The Patent of E.U.A. 3,112,241 describes methods for the treatment of materials using phosphate esters and is incorporated herein by reference.

With reference again to the aforementioned scheme (62), the epoxide-RF intermediate and / or the diol-RF intermediate can be prepared as generally described in the patent of E.U.A. 3,919,361 which is incorporated herein by reference. The epoxide-Rp and diol-RF intermediates can be reacted with phosphoric acid to obtain an ester of phosphoric acid-RF. The ester of phosphoric acid-R can be dissolved in a solution and applied to a substrate such as paper to increase the resistance to environmental materials such as oil and water. The phosphoric acid ester-Rp can also exist as a salt such as alkyl amines including ethanol amines as described in the patent of E.U.A. 4,145,382, incorporated herein by reference. The phosphoric acid ester-Rp can be used to treat substrates such as products made with wood pulp, including paper products such as packaging products including products for food packaging. One embodiment includes the RF portions incorporated within the glycols, such as R-glycols, including RF-QI ,, with Qh representing the ether portion of the glycol after conjugation or, as a hydroxyl functionality before conjugation as the ether. Exemplary RF glycols include, but are not limited to, those in Table 22 below.

TABLE 22 Exemplary RF-glycols Rp-glycols can be incorporated into polymers such as urethanes including polyurethane elastomers, films and coatings, for example. The glycols-RF can also be converted to phosphoric acids or phosphate esters of these glycols. With reference to scheme (63) below, the RF portions can be incorporated into the glycols.

Methods for the preparation of glycols are described in the U.S. Patent. 4,898,981, U.S. Patent. 4,491, 261, U.S. Patent. 5,091, 550, and U.S. Patent. 5,132,445, all of which are incorporated in the present invention as references. For example, and by way of example only, an RF intermediate (Qg = SH) can be reacted with a diol sulphide or 2,6 diox-aspiro (3,3) heptane to produce exemplary R-glycols (Qh = H2CH2CSH2CH2 .. .) Therefore the glycol-RF can be used directly or indirectly to prepare an RF condensation product such as polyesters, polyureas, polycarbonates, and polyurethanes. This glycol functionality can also be incorporated into the block polymers using glycols-RF. The Patent of E.U.A. 5,491, 261 describes various other glycols that can benefit from the RF portion of the present invention and is incorporated herein by reference. The Rp-glycols can also be converted to phosphoric acid functionality or phosphate esters (not shown). The Patent of E.U.A. 5,091, 550, 5,132,445, 4,898,981, and 5,491, all disclose the methods of preparation of diols and the conversion of the diols to phosphate esters and are incorporated herein by reference. In an exemplary implementation, the diols can be converted to phosphoric acid or phosphate esters by reacting the diols in the presence of phosphoric acid. These compositions can be incorporated into the compounds which can act as oil and grease proof compounds for paper, as well as soil release agents for textile fibers.

In accordance with another embodiment of the present invention oligomers, polymers, copolymers, acrylics, and / or resins, for example, which include an R-monomer unit, such as RF-Q U-The monomer unit portion, can be prepared, QMu, can be a particular unit within a complex of units and the monomeric unit does not need to be repeated within the complex. In an exemplary embodiment, the monomer unit may be a particular unit within the complex or it may be one of many identical units linked together, such as a homopolymer, for example. The complex may also include block polymers and / or polyurethane resins. The RF of the unit may include a hanging group of the monomer unit. The monomeric unit may be associated with a complex, perhaps it may even be bound to the complex, for example, and QMU may include the portion of the monomeric unit that is associated with the complex. The complex can be coated on a substrate or can be chemically bound to the substrate. For example, a preparation of R-intermediates can be provided to the substrate and groups such as hydroxyl groups common to cotton-like substrates can provide sites that allow the Rp-intermediate to chemically bind to the substrate when it is part of, or it is associated with a complex. In an exemplary embodiment, QMU may represent the acrylate functionality of an acrylic and RF may be a pendant group from chains and / or base structure of the acrylics. Exemplary monomeric-RF units include but are not limited to those in Table 23 below.

TABLE 23 Exemplary Monomeric Units-Rp In exemplary embodiments oligomers containing a monomeric-RF unit can be prepared from Rp-monomers. The RF-monomers may include above-mentioned RF-intermediates, but may conclude functionality that allows their conjugation with another monomer, but not necessarily the same Rp-monomer. Exemplary RF monomers include, but are not limited to, those in Table 24 below.

TABLE 24 Exemplary RF monomer With reference to scheme (64) below, multiple reaction sequences or the preparation of RF-monomers having the RF group are shown. (64) The Patents of E.U.A. 3,491, 169, 3,282,905, 3,497,575, 3,544,663, 6,566,470, 4,147,851, 4,366,299 and 5,439,998 all relating to the use and preparation of acrylic emulsion polymers that can benefit from the RF groups and, are incorporated herein by reference. IO-RF intermediates, iodo-Rp intermediates, hydroxyl-R intermediates, and / or acetate-RF intermediates can be converted to RF-monomers in accordance with the aforementioned scheme (63), and these Rp-monomers can be used for prepare a composition containing a monomeric unit-Rp. For example, and by way of example only, the RF portion can be incorporated into an RF-monomer as described in the U.S. Patent. 6,566,470 represented as RF-W-X-C (= 0) -C (R1) = CH2, with the RF portion as described above. W can be an alkylene with 1 to 15 carbons, hydroxyalkylene with 3 to 15 carbons, - (CnH2n) (OCmH2m) q-, -S02NR2- (CnH2n) -, or -CONR2- (CnH2n) -, with n which is 1 at 12, m is 2 to 4, q is 1 to 10, and Ri is an alkyl group with 1 to 4 carbon atoms, for example, X can be O, S and / or N (R2), where R2 is as Ri. For example, the monomer-RF 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pentyl acrylate can be prepared from the intermediate-Rp 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pent- 1-ene in two steps showing a continuation as the reaction schemes (65) and (66) respectively.

With reference to the aforementioned scheme (65), a 1 M solution of 4,4,5,5-tetramethyl-1, 3,2-dioxaboroiano in tetrahydrofuran (66.1 grams, 0.075 moles), chlorotris (triphenylphosphine) rhodium (0.37 grams) ), and tetrahydrofuran (158.8 grams) can be placed in a 500 mL round bottom funnel with three necks to form a mixture. 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pent-l-ene (18,243, 0.087 mol) can be added to the mixture at room temperature for a period of 15 minutes, allowed to mix for 72 hours, and is monitored by gas chromatography until such time as 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pent-1-ene has been substantially consumed (see Table 25 below for monitoring the reaction).

TABLE 25 Monitoring of the borate ester formation reaction by gas chromatography; All samples were analyzed in the commune DB WAX Column Note: peak at 3.07 minutes = 4,5,5,5-tetrafluoro-4- (trifluoromethyl) pent-l-ene, peak at 9.3 minutes = 4,4,5,5-tetramethyl-1, 3,2-dioxaborlane , peak at 16.8 minutes = 2- (4,5,5,5-tetrafluoro-4- (trifluoromethyl) pentyl) -4,4,5,5-tetramethyl-1,2,2-dioxaborolane To an aqueous solution of hydroxide 3M sodium (7.8 grams) can be added to the mixture via an addition funnel for a period of 15 minutes after which the mixture can be cooled to 0 ° C using an ice bath. Hydrogen peroxide (23.6 grams, 35% (w / w) aqueous solution) can be added dropwise over a period of 15 minutes to the mixture and then the mixture can be washed in H20 (three times). The organic layer can be removed and transferred into a 100 mL round bottom flask with three necks and distilled to produce an 85% pure percentage area (by gas chromatography 4,5,5,5-Tetrafluoro-4- ( trifluoromethyl) pentan-l-ol. 3 r? L3to .5.5.5-t * lr3fl? Ioro-4-0riflu rome "il) pe 51o 4,5,5,5-Tetrafluoro-4- (trifluoromethyl) pentan-1-ol (2.59 grams, 0. 011 moles) and triethylamine (1.3 grams, 0.013 moles) can be added to a 15 mL RBF with three necks to form a mixture. The mixture can be cooled to 0 ° C using a bath with ice water and the acryloyl chloride (1.38 grams, 0.015 moles) can be added to the mixture drop by drop using an addition funnel to the RBF for a period of 15 minutes . After a maintenance period of 1 hour, 10 mL of H20 can be added and two phases can be observed. The water can be decanted from the mixture, the organic phase is dried over MgSO, and analyzed by gas chromatography / mass spectrometry to confirm a new peak having a mass of 283. An exemplary RP-QM such as can be provided in solution and conjugate and / or argue with another or another compound to form a complex, such as an oligomer, which may include with QMU representing a remnant of the complex. For example and by way of example only, the RF-monomer solutions can be supplied to a substrate and leave a complex, for example, via evaporation of the solvent from the solution to form a complex including a monomeric-RF unit. Providing these solutions to a substrate such as glass, nylon, and / or cotton and allowing the RF-monomer to become part of a complex, such as coating the substrate. The surface energy of the complex can be determined using the standard method of Fowkes using diiodomethane and water as liquid probes, and Zisman's method of analyzing surface energy using octane, decane, tetradecane, and hexadecane as liquid probes. The contact angle of the droplets of the Zisman probe fluids, as well as the Fowkes probes can be determined, using a Kruss drop shape analysis system. The surface energy data of the complexes that include monomeric RF-QP units are mentioned in the following tables 26-35.

TABLE 26 Surface energy properties of complexes applied to fabric d TABLE 27 Surface energy properties of complexes applied to clean glass TABLE 28 Surface energy properties of impregnated complexes in clean glass TABLE 29 Surface energy properties of complexes in nylon fabric TABLE 30 Surface energy properties of complexes in cotton fabric TABLE 31 Properties of surface energy of complexes in cotton cloth (a mixture of 1, 2,3,4-butantetracarboxílico acid can be prepared at 87.5% (w / w), 6.5% (w / w), and hypophosphite). sodium at 6.0% (w / w), apply to cotton and bake for 2 minutes at 180 ° C).

TABLE 32 Properties of surface energy of complexes on nylon TABLE 33 Properties of surface energy of complexes on nylon 03 TABLE 34 Properties of surface energy of complexes on glass TABLE 35 Properties of surface energy of complexes on glass 03 O The Rp monomers can be incorporated with other monomers and subsequently incorporated into the construction of paper materials or used to treat paper materials. The RF-monomers can also be used to prepare polymer solutions. The polymer solutions can be diluted to a percentage of an aqueous or non-aqueous solution and subsequently applied to substrates to be treated, such as paper plates. The RF-monomers can also be incorporated into copolymers with comonomers such as the dialkyl amino acrylate or the methacrylate or acrylamide or methacrylamide monomer and its quaternary ammonium amine salt or amine oxide form, as described in the patent. from the USA 4,147,851, incorporated by reference in the present invention. The general formula for the R-monomers can be RFq02CC (R) = CH2, with R being H or CH3, q being an alkylene of 1 to 15 carbon atoms, hydroxyalkylene of 3 to 15 carbon atoms, or CnH2n (0CqH2q) m-, -S02NR1 (CnH2n) -, or -CONR ^ Cn ^) -, n is 1 to 15, q is 2 to 4, and m is 1 to 15. The monomers used to form copolymers with acrylates and the RF-monomers include those having amine functionality. These copolymers can be diluted in a solution and applied or incorporated directly into or onto the substrates to be treated, such as paper. The RF-monomers can also be used to form acrylate polymers or other acrylate monomers consisting of those described in the U.S. Patent. 4,366,299, incorporated herein by reference. As described, RF-monomers can be incorporated into or applied to paper products. The Rp, acrylate and / or acrylic monomers, for example, can be applied to finish carpets or incorporated into the fiber for finishing the carpet before the carpet is laid. The Rp-monomers can be applied to the carpet by a normal textile finishing process known as filler, in which the carpet is passed through a bath containing the RF-monomer and, for example, latex, water, and / or other additives such as non-re-wettable surfaces. Subsequently the carpet can be passed through clamping rollers to control the rate of addition before it dries in a tender frame. The RF-monomers can also be incorporated into the fiber by reacting the fiber with the RF-intermediates having isocyanate, isocyanate-RF functionality, for example. The RF-portions can also be incorporated into materials used to treat materials with calcific and / or siliceous particles. For example, the RF-monomers can be incorporated into a copolymer wherein the copolymer can either be part of a formulation for treating these materials or is used for the treatment of these materials as described in the U.S. Patent. 6,383,569, incorporated herein by reference. The RF-monomer can have the general formula RF-QAC (0) -C (R) = CH2 wherein RF is described above, R is H or CH3, A is O, S, or N (R, where Ri is H or an alkyl of 1 to 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, - (CnH2n) (OCqH2q) m-, -S02-NR? (CnH2n) -, or -CONR ^ CnH ^) -, where R, is H or an alkyl of 1 to 4 carbon atoms, n is 1 to 15, q is 2 to 4, and m is 1 to 15 The RF-compositions and mixtures containing the Rp portion can be used for the treatment of substrates including hard surfaces such as building materials such as brick, stone, wood, concrete, ceramics, tiles, glass, stucco, plaster, wall stones, agglomerate board, gray cardboard. These compositions and mixtures may be used alone or in combination with penetration aids such as nonionic surfactants. These compositions can be applied to the surface of calcitic and / or siliceous architectural construction material by known methods, for example, by wetting, impregnation, dipping, brushing, rolling, or spraying. The compositions can be applied to the surface to be protected by spraying. The right equipment for spraying is commercially available. The sprinkling with a sprinkler with compressed air is an exemplary method of application to the particular substrate. The Patents of E.U.A. 6,197,382 and 5,674,961 also describe methods for the application and use of polymer solutions and are incorporated herein by reference.

In an exemplary process for the production of solutions having Rp components, an Rp intermediate having a methyl-epoxide functionality can be condensed with an alkenoic monocarboxylic acid to prepare an unsaturated Rp-ester (not shown). Exemplary methods for the production of these types of unsaturated esters are described in U.S. Pat. 5,798,415, incorporated herein by reference. Additional esters can be prepared in accordance with the Patent of E.U.A. 4,478,975, incorporated herein by reference. The components of these solutions can also include dimethyl amino ethyl methacrylate, and these components can be applied in organic and inorganic solvents, as described in the patent of E.U.A. 6,120,892 incorporated in the present invention as reference. The Rp-monomers can also be combined with other monomers to produce copolymers or in solutions with amido and sulfur monomers as described by the U.S. Patent. 5,629,372 incorporated herein by reference. Intermediates-RF having an amine functionality can also be reacted with tetrachlorophthalic anhydride using the U.S. Patent. 4,043,923 as an exemplary reaction scheme (not shown). The Patent of E.U.A. 4,043,923 is incorporated herein by reference. The reaction product can be mixed with a carpet cleaning solution to provide dirt repellency.

With reference to scheme (67) below, urethanes can be prepared, including the RF-portions from the intermediates-Rp.

An intermediate-Rp (RF-OH) can be combined with the polymers of hexamethylene diisocyanate (DESMODUR N-100) following the general reaction sequence described in the patent of E.U.A. 5,827,919, incorporated herein by reference, to produce a urethane. Another method for the preparation of urethanes includes reacting an RF-intermediate (RF-SCN) with epichlorohydrin to produce an "RF-intermediate" with twin tails which can be reacted with diisocyanate and / or a urethane prepolymer as is described in the US Patent 4,113,748, incorporated in the present invention as reference (not shown). The urethanes having the RF group can then be incorporated as an additive to the compositions such as latex paint. The Patent of E.U.A. 5,827,919 describes methods for the use of these urethanes and is incorporated herein by reference. RF-urethanes and polyurethanes can be used to treat substrates such as carpet, upholstery, furniture upholstery, automotive elements, awning fabrics, and waterproof clothing. Exemplary RF urethanes such as RF-QU, may include, but are not limited to, those listed in Table 36 below. TABLE 36 Exemplary Uretans-RF The RF portion can also be complexed as an acid with amine and quaternary ammonium polymers as described in the U.S. Patent. 6,486,245, incorporated herein by reference (not shown).

Claims (35)

NOVELTY OF THE INVENTION CLAIMS

1. - A surfactant composition comprising RF-Qs, wherein: RF has a greater affinity for a first part of a system having at least two parts compared to Qs; Qs have a greater affinity for a second part of the system compared to RF; and RF comprises at least two groups -CF3 and at least two hydrogens. 2. The surfactant composition according to claim 1, further characterized in that RF is hydrophobic in relation to

Qs-

3. The composition of surfactant according to claim 1, further characterized in that Qs is hydrophilic in relation to RF.

4. The surfactant composition according to claim 1, further characterized in that RF is hydrophobic and Qs is hydrophilic.

5. The surfactant composition according to claim 1, further characterized in that R comprises at least one -CH2- group.

6. - The surfactant composition according to claim 1, further characterized in that RF comprises at least one cyclic group.

7. The composition of surfactant according to claim 6, further characterized in that the cyclic group comprises a group.

8. The surfactant composition according to claim 1, further characterized in that RF comprises at least one group (CF3) 2CF-.

9. The surfactant composition according to claim 1, further characterized in that RF comprises at least three -CF3 groups.

10. The surfactant composition according to claim 1, further characterized in that RF comprises at least two groups (CF3) 2CF-.

11. The surfactant composition according to claim 1, further characterized in that RF comprises at least four carbons and one of the four carbons comprises a -CH2- group.

12. The surfactant composition according to claim 1, further characterized in that RF-QS is

13. - The surfactant composition according to claim 1, further characterized in that RF-QS is

14. - The surfactant composition according to claim 1, further characterized in that RF-QS is

15. - The surfactant composition according to claim 1, further characterized in that RF-QS is

16. - The surfactant composition according to claim 1, further characterized in that RF-QS is

17. - The surfactant composition according to claim 1, further characterized in that RF-QS is

18. The surfactant composition according to claim 1, further characterized in that RF-QS is

19. - The surfactant composition according to claim 1, further characterized in that Rp-Qs is

20. - The surfactant composition according to claim 1, further characterized in that RF-QS is

21. - The surfactant composition according to claim 1, further characterized in that RF-QS is

22. - The surfactant composition according to claim 1, further characterized in that RF-QS is

23. - The surfactant composition according to claim 1, further characterized in that Rp-Qs is

24. - The surfactant composition according to claim 1, further characterized in that RF-QS is

25. - The surfactant composition according to claim 1, further characterized in that RF-QS is

26. - The surfactant composition according to claim 1, further characterized in that RF-QS is

27. - The surfactant composition according to claim 1, further characterized in that

28. - The surfactant composition according to claim 1, further characterized in that

29. - The surfactant composition according to claim 1, further characterized in that RF-QS is

30. - The surfactant composition according to claim 1, further characterized in that RF-QS is

31. - The surfactant composition according to claim 1, further characterized in that RF-QS is

32. - The surfactant composition according to claim 1, further characterized in that RF-QS is

33. - The surfactant composition according to claim 1, further characterized in that RF-QS is

34. - The surfactant composition according to claim 1, further characterized in that RF-QS is X represents a halogen. 35.- The surfactant composition according to claim 1, further characterized in that it is comprised of a solution comprising one or more of a detergent, emulsifier, paint, adhesive, dye, wetting agent, foaming glue, and / or a defoamer