Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
  • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms

Definitions

• the present invention relates to a mixture of
• polyfluoroalkylsulfonamido alkyl amines including at least one
• the invention also relates to polyfluoroalkylsulfonamido alkyl halide intermediate used to make the aforementioned mixture.
• Polyfluoroalkylsulfonamido alkyl amines are useful starting materials for various products including: fluorinated surfactants, including cationic, non-ionic, anionic, and amphoteric surfactants, and fluorinated repellents, including poly-(meth)acrylamides, ureas, imides.
• fluorinated surfactants including cationic, non-ionic, anionic, and amphoteric surfactants
• fluorinated repellents including poly-(meth)acrylamides, ureas, imides.
• Specific applications for the products made from polyfluoroalkylsulfonamido alkyl amines include: electronics applications, nanotechnology, pharmaceutical and pesticide intermediates, catalysts, and firefighting foaming agents.
• US Patent 4,486,391 provides a synthetic route requiring a diamine reagent that, by definition, has two reactive amine sites per molecule, both of which can be converted to sulfonamido groups thereby forming a bis-sulfonamide by-product, which is also described in the GB patent 1 ,378,984.
• Conventional methods fail to disclose a synthetic route to a polyfluoroalkylsulfonannido alkyl amine that avoids the production of a bis-sulfonamide by-product, an undesirable impurity that typically worsens surfactancy, foaming properties, or other performance characteristics of desired products made from the
• the bis-sulfonamide by-product shares very similar physical properties with the desired polyfluoroalkylsulfonannido alkyl amine thus making its isolation and purification difficult and costly.
• the bis-sulfonamide by-product constitutes a substantial loss of costly fluorinated starting material instead of the efficient incorporation of fluorine to make the desired
• the present invention provides a method of making a
• polyfluoroalkylsulfonannido alkyl amine which avoids the use of a diamine reagent and the concomitant production of a bis-sulfonamide by-product.
• the present invention also avoids or drastically reduces the production of non-useful fluorine containing by-products. Contrary to conventional methods which use a diaminoalkane and
• the present invention subjects a polyfluoroalkylsulfonamido alkyl halide to amino-de-halogenation with an amine thereby producing a polyfluoroalkylsulfonamido alkyl amine.
• the amino-de-halogenation also produces a
• di(polyfluoroalkylsulfonamido alkyl) amine itself a useful product which can provide an advantage in lowering the surface tension and other performance characteristics of surfactants, made from the
• the present invention provides a method for making a mixture of polyfluoroalkylsulfonamido alkyl amines comprising at least one polyfluoroalkylsulfonamido alkyl amine and at least one di(polyfluoroalkylsulfonamido alkyl) amine.
• polyfluoroalkylsulfonamido alkyl amines can be made by amino-de- halogenation wherein a polyfluoroalkylsulfonamido alkyl halide is reacted with ammonia or an amine, the polyfluoroalkylsulfonamido alkyl halide represented by
• R f is chosen from a C 2 -C 12 polyfluoroalkyl optionally interrupted by one to four groups chosen from:— O— ,— S— ,— S(O)— , and— S(O) 2 — ; n is chosen from an integer from 0 to 6; R 1 , R 5 , R 6 are independently chosen from hydrogen, Ci to C6 hydroxyalkyl, Ci to C6 halogen
• C m H 2 m is linear or branched alkyl, and m is chosen from an integer from 1 to 10; and X is a halogen selected from CI, Br, I, and mixtures thereof.
• Preferred polyfluoroalkylsulfonannido alkyi halides of Formula 1 are those wherein;
• Rf is chosen from CF 3 (CF 2 )5 or CF 3 (CF 2 )3;
• R 1 , R 5 , R 6 are independently chosen from hydrogen, methyl, or ethyl, Ci to C3 halogen substituted alkyi, Ci to C3 hydroxyalkyi, and most preferably hydrogen; n is chosen from 0 or 2; m is 2; and
• X is chlorine
• ammonia or amine used during amino-de-halogenation of the polyfluoroalkylsulfonannido alkyi halide of Formula 1 to form the mixture of polyfluoroalkylsulfonannido alkyi amines is represented by:
• each R 4 is independently selected from hydrogen or a Ci to 3 alkyi, or a Ci to C 6 hydroxyalkyi, preferably each R 4 is hydrogen thereby representing ammonia.
• the polyfluoroalkylsulfonannido alkyi halides of Formula 1 can be made by reacting a polyfluoroalkylsulfonic compound with a monoamino alkyi halide, or salt thereof under suitable conditions to make a
• polyfluoroalkylsulfonannido alkyi halide wherein: i) the polyfluoroalkylsulfonic compound is represented by
• Rf— (CH 2 )n— S(O) 2 — Y (Formula 3) wherein R f and n are defined as above and Y is chosen from aryloxy, substituted aryloxy, or a halide such as F, CI, or Br; and ii) the monoamino alkyi halide or salt thereof is represented by HN(R 1 )— C(R 5 )(R 6 )— C m H 2m — X (Formula 4A) or
• polyfluoroalkylsulfonamido alkyl halides of Formula 1 can be made by reacting a polyfluoroalkylsulfonamido alkyl alcohol with a halogenating agent under suitable conditions to make a polyfluoroalkylsulfonamido alkyl halide wherein the
• polyfluoroalkylsulfonamido alkyl alcohol is represented by
• R f (CH 2 )n— S(O) 2 — N(R 1 )— C(R 5 )(R 6 )— C m H 2m — OH (Formula 5) wherein R f , n, R 1 , R 5 , R 6 , and m are defined as above.
• the polyfluoroalkylsulfonamido alkyl alcohols of Formula 5 can be made by reacting a polyfluoroalkylsulfonic compound of Formula 3 with an amino alkyl alcohol under suitable conditions to make a
• polyfluoroalkylsulfonamido alkyl alcohols wherein: i) the amino alkyl alcohol is represented by
• polyfluoroalkylsulfonamido alkyl amines comprises i) at least one polyfluoroalkylsulfonamido alkyl amine represented by
• Q is a monovalent anion preferebly chosen from halogen
• each R f is the same in i) and ii) and chosen from a C 2 -Ci 2 polyfluoroalkyl optionally interrupted by one to four groups chosen from:— O— ,— S— , — S(O)— , and— S(O) 2 — ; each n in i) and ii) is the same and chosen from an integer from 0 to 6; each m in i) and ii) is the same and chosen from an integer from 0 to 10; each R 1 , R 5 , R 6 is independently chosen from hydrogen, Ci to Ce hydroxyalkyl, Ci to Ce halogen substituted alkyl, or a Ci to Ce linear or branched alkyl; provided that each R 1 in i) and ii) are the same, each R 5 in i) and ii) are the same, and each R 6 in
• Reaction 1 Formation of the mixture of polyfluoroalkylsulfonamido alkyl amines of Formulae 7 and 8
• Reaction 3 Formation of polyfluoroalkylsulfonamido alkyl halide of Formula 1 by halo-de-hydroxylation of alcohols of Formula 5
• polyfluoroalkylsulfonamido alkyi halide of Formula 1 undergoes amino-de- halogenation with ammonia, producing polyfluoroalkylsulfonamido alkyi amine of Formula 7, which upon further amino-de-halogenation reaction with alkyi halide of Formula 1 produces di(polyfluoroalkylsulfonamido alkyi) amine of Formula 8. Therefore, polyfluoroalkylsulfonamido alkyi amines of Formulae 7 and 8 are both present in the product mixture.
• reaction conditions for subjecting a polyfluoroalkylsulfonamido alkyi halide (Formula 1 ) to amino-de-halogenation thereby producing a mixture of polyfluoroalkylsulfonamido alkyi amines includes charging a reaction vessel with a polyfluoroalkylsulfonamido alkyi halide, and optionally an iodide salt catalyst, and solvent, which is then sealed, evacuated, and then charged with concentrated ammonia solution in water or methanol, preferably anhydrous ammonia, and heated to a reaction temperature of about 100 to 130 °C, more preferably between 1 10 and 120 °C in a pressurized reactor.
• the pressure of the reactor is primarily determined by the partial pressure of ammonia at the reaction temperature and is about 70 to 600 psi.
• a 10 to 200 fold molar excess of ammonia to polyfluoroalkylsulfonamido alkyi halide may be used; preferably a 25 to 150 molar excess, and more preferably a 30 to 100 molar excess.
• the reaction temperature is maintained for about 4 to 12 hours.
• the contents of the reactor are then cooled to about 20 to 25 °C, and excess of ammonia is vented out.
• the unused ammonia can be scrubbed or condensed to recycle into the next reaction batch.
• a strong base e.g., NaOH, KOH
• a strong base e.g., NaOH, KOH
• a strong base e.g., NaOH, KOH
• preferably in powdered form to convert the ammonium salts to a corresponding amines, and, optionally, activated carbon, to reduce the color of the mixture or final product
• the solvent can then be evaporated from the filtrate with vacuum to obtain a solid product comprising typically 70 to 98 wt. % of a mixture of polyfluoroalkylsulfonamido alkyl amines (Formulae 7 and 8).
• Suitable solvents for conducting the amino-de-halogenation of Reaction 1 include polar solvents such as ethers, e.g., 1 ,2- dimethoxyethane, or alkyl alcohols.
• polar solvents such as ethers, e.g., 1 ,2- dimethoxyethane, or alkyl alcohols.
• Alkyl alcohols e.g., methanol, ethanol, 2-propanol, and 1 -butanol
• Alkyl alcohols are preferred for their ability to dissolve the product of Reaction 1 and the reactants thereof.
• Suitable amino-de-halogenation catalysts for use in Reaction 1 include iodide salts such as Nal, Kl, Bu 4 NI. These iodide salts are used preferably at 0.1 to 1 .5 molar equivalents based on the starting compound of Formula 1 , and more preferably at 0.1 to 0.3 molar equivalents. When polyfluoroalkylsulfonamido alkyl iodides are used for the Reaction 1 , the use of additional iodide salts is not necessary.
• alkyl amines represented by Formula 2
• alkyl amines may be used instead of ammonia.
• examples of such amines include methylamine, ethylamine, butylamine, hexylamine, 2- aminoethanol, 2-(methylamino)-1 -ethanol.
• an example of the reaction conditions for forming a polyfluoroalkylsulfonamido alkyl halide of Formula 1 includes dissolving a monoamino alkyl halide or salt thereof (Formulae 4A or 4B) in a vessel (preferably under inert anhydrous conditions, e.g., with nitrogen purge) containing an appropriate aprotic solvent and additional base.
• a vessel preferably under inert anhydrous conditions, e.g., with nitrogen purge
• the vessel is equipped with mechanical stirrer and a condenser.
• the contents of the vessel are heated to a temperature of about 10-20 °C; after which, a polyfluoroalkylsulfonic compound (Formula 3) is added to the vessel over a period of about 15 to 120 minutes while maintaining the temperature between about 10 to 50 °C, more preferably between 20 and 40 °C.
• the temperature can be controlled by means of the addition rate and external cooling.
• a reaction temperature is maintained at about 25 to 65 ° C depending upon what additional base is used. After about 98 to 100 wt.
• a strong acid e.g., HCI or H 3 PO 4
• a strong acid may be added to adjust the pH to about 2 to 7 (preferably 4 to 5) causing the conversion of unreacted monoamino alkyl halide to a corresponding ammonium alkyl halide salts of Formula 4B, and conversion of additional base to its corresponding salts of these strong acids, which are removed by filtration.
• the filtrate can be further dried in vacuum to remove solvent and obtain solid product.
• Product or its solution in appropriate solvent can be optionally washed with water to remove traces of salts.
• tertiary amines e.g., triethylamine, diisopropyl ethyl amine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl ethylene diamine, a hindered tertiary amine such as
• reaction temperature can vary. When a tertiary amine base is used, the typical reaction temperature is about 10 to 40 °C. When the potassium carbonate is used, a higher reaction temperature, about 50 to 65 °C, is preferred to increase the rate of the reaction.
• the molar ratio of the monoamino alkyl halide with respect to the polyfluoroalkylsulfonic compound is preferably between 2.5:1 and 2:1 , and more preferably between 2.2:1 and 2:1 .
• the excess beyond the first molar equivalent of the monoamino alkyl halide of Formula 4A is intended as a base to neutralize the generated HY acid, where Y is defined above.
• the molar ratio of monoamino alkyl halide or salt thereof to the polyfluoroalkylsulfonic compound can be reduced below 2:1 down to about 1 :1 , and more preferably between 1 .4:1 and 1 :1 .
• Examples of suitable monoamino alkyl halides (Formula 4A) for use in the amination of Reaction 2 include 2-chloro-1 -ethaneamine, 2-bromo- 1 -ethanamine, 3-chloro-1 -propanamine, 3-bromo-1 -propanamine, 3- chloro-N-methyl-1 -propanamine, 3-bromo-N-methyl-1 -propanamine, 3- chloro-N-(3-chloropropyl)-1 -propanamine, 2-chloro-N-(2-chloroethyl)-1 - ethanamine, 4-chloro-1 -butanamine, 4-bromo-1 -butanamine, 4-chloro-2- butanamine, 4-chloro-N-methyl-1 -butanamine, 4-bromo-N-methyl-1 -butanamine, 5-chloro-1 -pentanamine, 5-chloro-N-methyl-1 -pentanamine, 5-bromo-1 -pent
• Examples of suitable monoamino alkyl halide salts (Formula 4B) for use in the amination of Reaction 2 include 2-chloro-1 - ethaneaminehydrochloride, 3-chloro-1 -propanamine hydrochloride, N-(2- chloroethyl)-2-amino-1 -chloroethane hydrochloride.
• Monoamino alkyl halide salts are more readily commercially available and are thus preferred over their monoamino alkyl halide counterparts.
• Suitable solvents for conducting the Reaction 2 are commercially available and include methylene chloride, butyronitrile, 1 ,2- dimethoxyethane, 1 ,2-diethoxyethane, diethyl ether, tetrahydrofuran, ethyl acetate, toluene, and mixtures thereof.
• an example of the reaction conditions for forming a polyfluoroalkylsulfonamido alkyl halide (Formula 1 ) by halo-de- hydroxylation of a polyfluoroalkylsulfonamido alkyl alcohol of (Formula 5) includes: charging a stirred vessel with polyfluoroalkylsulfonamido alkyl alcohol dissolved in an aprotic solvent; the addition of a halogenation agent; reacting the contents of the vessel at a temperatures determined by the reactivity of the halogenating agent, typically between about 40 to 130 ° C, for about 30 to 240 minutes; and removing solvent and excess halogenation agent by distillation, and, optionally, hydrolysis, and further aqueous washing, to obtain crude product.
• the crude product can be further purified by recrystallization, e.g., from hydrocarbon solvent such as hexane or heptane.
• halogenation agents for use in Reaction 3 include various chlorinating or brominating agents, such as: acid halides, e.g., thionyl chloride, thionyl bromide, oxalyl chloride, or hydrogen chloride; as well as other reagents that enable the exchange of -OH for -CI, such as PPh 3 /CI 3 CCONH 2 .
• the halogenation agent is thionyl chloride used in an amount suitable to achieve substantially complete conversion of the polyfluoroalkylsulfonamido alkyl alcohol while avoiding significant excess of thionyl chloride.
• Suitable molar equivalents of thionyl chloride to polyfluoroalkylsulfonamido alkyl alcohol include about 1 to 5 molar equivalents, with about 1 .5 molar equivalents being preferable.
• Typical reaction with thionyl chloride involves controlling its addition and maintaining the reaction temperature at about 20 to 60 °C. Higher reaction temperatures for thionyl chloride are possible, but have been found to generate a greater proportion of undesirable and dark-colored byproducts.
• Suitable aprotic solvents for use in the halogenation of Reaction 3 include methylene chloride, butyronitrile, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane, diethyl ether, tetrahydrofuran, ethyl acetate, toluene, and mixtures thereof.
• an example of the reaction conditions for forming a polyfluoroalkylsulfonamido alkyl alcohol of Formula 5 includes dissolving a amino alkyl alcohol (Formula 6) preferably 2 to 2.3
• a vessel preferably under inert anhydrous conditions, e.g., with nitrogen purge
• the vessel is equipped with mechanical stirrer and a condenser.
• the contents of the vessel are maintained at a temperature of about 10-20 0 C; after which, a
• polyfluoroalkylsulfonic compound (Formula 3) is added to the vessel over a period of about 15 to 120 minutes while maintaining the temperature between about 10-50 °C, more preferably between 20 and 40 °C.
• the temperature can be controlled by means of the addition rate and external cooling.
• the reaction is maintained at a temperature of about 25 to 55 ° C. After about 99 to 100 wt.
• a strong acid e.g., HCI or H 3 PO 4
• HCI or H 3 PO 4 is added to adjust the pH to about 2 to 7 (preferably 4 to 5) causing the neutralization of unreacted aminoalkylalcohol of Formula 6, to form additional amount of ammonium halide salts of aminoalkylalcohol byproducts which have lower solubility in the reaction solvent and are removed by filtration.
• the filtrate solution can be further dried in vacuum to remove solvent and obtain solid product.
• Product or its solution in appropriate solvent can be optionally washed with water to remove traces of salts.
• aprotic solvents such as methylene chloride, butyronitrile, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane, diethyl ether, tetrahydrofuran, ethyl acetate, toluene, as well as tertiary alcohols (e.g., t-butanol and t-amyl alcohol), and mixtures thereof.
• the molar ratio of the amino alkyl alcohol to the polyfluoroalkylsulfonic compound is preferably at least 2:1 , more preferably between 2.5:1 and 2.0:1 , and still more preferably between 2.2:1 and 2:1 .
• the excess beyond the first molar equivalent of the polyfluoroalkylsulfonamido alkyl alcohol is intended as a base to neutralize generated acid represented in Reaction 4 as HM. If an additional base is used, then the molar ratio of amino alkyl alcohol (Formula 6) to the polyfluoroalkylsulfonic compound (Formula 3) can be reduced below 2:1 down to about 1 :1 .
• Suitable amino alkyl alcohols for use in Reaction 4 are commercially available and include 2- (methylamino)ethanol, 3-amino-1 -propanol, ethanolamine, diethanolamine, 3-(3-hydroxypropyl-amino)-propan-1 -ol, 4-amino butan-1 - ol, 1 -amino-2-propanol, 2-amino-1 -propanol, 3-(methylamino)-1 -propanol, 3-amino-2-nnethyl-1 -Propanol, 4-amino-1 -butanol, 3-amino-1 -butanol, 2- amino-3-nnethyl-1 -butanol, 4-amino-2-nnethyl-1 -butanol, 4-(methylannino)- 1 -butanol, 5-amino-1 -pentanol, 5-(ethylamino)-1 -pentano
• Examples 1 -7 show how embodiments of Reaction 1 were conducted.
• the shaker tube was sealed, evacuated, and charged with NH 3 (gas, anhydrous, 13.6g, 0.8 mol) and heated at 120 °C for 4 hours at 355 psi.
• the reaction mixture was cooled and the excess of NH 3 was vented.
• the product mixture was treated with solid NaOH powder and additional 2-propanol at 60 °C and filtered.
• the solvent from the filtrate was evaporated in vacuum to obtain yellow solid containing CF 3 (CF 2 )5C 2 H 4 SO 2 NH(CH 2 ) 3 NH 2 (56 wt.%), CF 3 (CF2)5C 2 H 4 SO 2 NH2 (16 wt.%), and
• CF 3 (CF2)5(CH2)2SO2NH(CH 2 )3CI (3.8g, 0.008 mol), amino ethanol (1 .3g, 0.021 mol), 1 -butanol (14g), and Nal (0.3g, 0.002 mol) were placed in the 50ml_ flask with magnetic stirring.
• the reaction mixture was heated at 100 °C for 18 hours.
• the GC analysis indicated complete conversion of CF 3 (CF2)5(CH2)2S0 2 NH(CH2)3CI.
• the reaction mixture was cooled to 50 °C, and the excess of base was neutralized with 0.57g of 35% HCI and washed with water (12g).
• the butanol solution was dried on rotary evaporator to obtain 3.8g of product (87% purity by GC, 83% yield).
• CF 3 (CF2)5(CH2)2SO2NH(CH 2 )3CI (2.9g, 0.006 mol), 2-(N- methylamino)ethanol (1 .4g, 0.019 mol), 1 -butanol (1 1 g), and Nal (0.22g, 0.001 mol) were placed in the 50ml_ flask with magnetic stirring. The reaction mixture was heated at 100 °C for 10 hours. The GC analysis indicated complete conversion of CF 3 (CF2)5(CH2)2SO 2 NH(CH2)3CI. The reaction mixture was washed with water at 50 °C (2x 9g). The butanol solution was dried to obtain 2.67 g of product (93% purity by GC, 80% yield).
• Examples 8-10 show how embodiments of Reaction 2 were conducted wherein a polyfluoroalkylsulfonamido alkyl halide
• Example 8 used Et 3 N (triethylamine) as an added base.
• Example 9 used K2CO3 as an added base.
• Example 10 used DBU
• Examples 1 1 -15 show how embodiments of Reaction 3 were conducted.
• CF 3 (CF 2 ) 5 CH 2 CH 2 SO 2 NH(CH 2 ) 3 OH (7g, 0.014 mol), and 1 ,2- dimethoxyethane (10g) were charged to the 400mL HASTELLOY-C shaker tube.
• the shaker tube was sealed, evacuated, and charged with Hydrogen Chloride (gas, anhydrous, 7.5g, 0.2 mol) and heated at 140 °C for 3 hours.
• the GC analysis of the product mixture indicated 92% conversion of CF 3 (CF 2 ) 5 CH 2 CH 2 SO 2 NH(CH 2 ) 3 OH to
• Example 16 shows how an embodiment of Reaction 4 was conducted.
• 3-aminopropan-1 -ol (68.2g, 0.91 mol) and 1 ,2-dimethoxyethane (276g) were placed in 1 Liter round bottom flask equipped with mechanical stirring under nitrogen.
• Solution of CF 3 (CF2)5(CH2)2SO 2 CI (200.1 g, 0.45 mol.), in 1 ,2-dimethoxyethane (121g) was added dropwise during 2.5 hours at 20-40 °C while stirring at 350 rpm.
• reaction mixture was stirred at 55 °C for 2h after the addition is completed, and monitored by GC to ensure the complete conversion of CF3(CF 2 )5(CH2)2SO 2 CI.

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