DE2243371A1 - PERFLUORALKYL SULPHONES - Google Patents

Description

Bayer Aktiengesellschaft

Central Department Patents, Trademarks and Licenses ''

• ß / Tj _e 509 Leverkusen, Bayerwerk

Sep 1, 1972

Perfluoroalkyl sulfoae

The invention "relates to perfluoralky! Sulfones of the formula

R _f - SO ₂ - CH ₂ - CH - X (I),

in the

R _{f represents} a C ₁ -C ₁₂ perfluoroalkyl radical and R represents hydrogen or a methyl group and

X denotes a cyano, carbonamides or preferably a -COOM- or -COOR ₁ group, in which M represents hydrogen or an alkali, alkaline earth metal

or ammonium! on and
R _{1 represents} a C ₁ -C ₂ -alkyl radical or a C ₂ -Cc ~ alkenyl radical, preferably a C ₂ -C 6 -alkenyl radical,

furthermore a process for the hexification of the perfluoroalkyl sulfones the j? ormel I.

Pur R _f are C ₁ -C, ₂ ~ Perf luoralky Ir este z. B «der OSy» _s 11C ₅ F ₇ -, nC ₆ F ₁₅ -, nC _1o F ₂₁ - _f ieo-C _1o P ₂₁ - _f nC ₁₂ P ₂₅ - and inabe-

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especially the nC ^ iy-, nC ^ γ- and iso-CgF., called γ-remainder.

Sodium and in particular come as alkali ions Potassium ion; as alkaline earth ions especially the magnesium and calcium ions and as ammonium ions the ammonium ion and the Alkylammonium ions, such as the mono-, di- and triethanolamine anion or the cyclohexylammonium ion.

For the preparation of the ferfluoroalkyl sulfones of the formula I. are perfluoroalkanesulfinic acids of the formula

R _f - SO ₂ H (II),

in which R ~ has the meaning given under formula I, with unsaturated compounds of the formula

CH ₂ = C - X (III), R

in which R and X have the meaning given under formula I, at temperatures of 1o to 12o C, preferably 2o to 7o ° C, optionally in inert under the reaction conditions organic diluents such as halogenated hydrocarbons, z. B. chloroform, carbon tetrachloride, 1,2-dichloroethane, or ketones, e.g. B. acetone or methyl ethyl ketone, and optionally reacted in the presence of polymerization inhibitors such as hydroquinone, phenothiazine, copper salts or copper powder.

The proportions of the reactants are in this way chosen that to 1 mole of perfluoroalkanesulfinic acid of the formula II 1 to 1.5 mol of unsaturated compound of the formula III are omitted.

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! '243371

The perfluoroalkyl sulfones of the formula I in which X is for -COOM and M is an alkali, alkaline-earth or ammonium ion means, are expediently by neutralizing the corresponding free carboxylic acids produced "

The compounds of the formula I, in which X stands for a -GQQR ₁ group, can be very advantageously also by subsequent esterification of the perfluoroalkylsulfones of the formula I, in which X stands for a -COOH group, with alcohols of the formula

R ₁ - OH (IV),

in which R _{1 has} the meaning given under formula I, produce.

The preparation of the perfluoroalkanesulfinic acids of the formula II can in a known manner, for. B »after the one in German German Offenlegungsschrift 2,148,597.

_{Acrylic and methacrylic acid and their nitriles 9} amides and esters, such as the methyl, ethyl, Butyl ™ and 2-ethylhexyl esters, may be mentioned as representatives of the unsaturated compounds of the formula III.

The perfluoroalkyl sulfones of the formula I are valuable Intermediate products for the production of new compounds with per « fluoroalkyl groups. Compounds of the formula I which contain a carboxyl group have surface-active substances in the form of S © 1 ^ © Properties; they can be, for example, as

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Wetting agents and surfactants in emulsions, dispersions, cleaning and fire extinguishing agents and as emulsifying agents find use in polymerizations.

Compounds of formula I which have an alkoxycarbonyl group containing an unsaturated alkyl group can be converted into homo- or copolymers with which textiles can be made water and oil repellent.

The parts given in the following examples are parts by weight, unless stated otherwise.

example 1

15.5 parts of acrylic acid and 0.5 parts of hydroquinone are dissolved in 50 parts of acetone. 51 parts Perfluorbutansulfinsäure are added dropwise to this solution at 5o to 60 ⁰ C. After 3> minutes of stirring at the same temperature, the solvent is distilled off in vacuo. There remain 53 parts of residue, which solidify on cooling to a brownish crystal mass which is recrystallized from toluene.

FP (after recrystallization from toluene): 142 to 145 ° C

C ₄ F ₉ -SO ₂ -CH ₂ -CH ₂ -COOH

C ₇ H ₅ F ₉ O ₄ S (MG 356)

calc.: C 23.6 £ H 1.42 $ F 48, o1 f> S 9.00 jC found. : C 23.6 H ^ 1.5 $> F 47.3 Ji-S 8.8 $

The IR spectrum corresponds to the structure given.

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Example 2

The mixture of 48 parts of perfluorooctanesulfinic acid, 11 parts Acrylic acid, 0.5 parts of copper powder and 6o parts of acetone is stirred at 50 to 60 ° C. for 2 hours. After distilling off of the solvent, 56 parts of dark brown crystals are obtained, which were recrystallized from benzene / acetone.

FP (after recrystallization from benzene-acetone): 18o to

183 C

G ₈ F ₁₇ -SO ₂ -GH ₂ -CH ₂ -COOH G ₁₁ H ₅ F ₁₇ O ₄ S (MW 556)

ber .: C. 23, 75 ψ O, 9 F. 58 o7 * S. 5 , 77 found : C. -24, ο io 1, 1 F. 57, 4th 1o S. 5 , 4 • H '< H

The IR spectrum agrees with the structure indicated.

To produce the sodium salt, 25 parts of the 2- (Perfluorooctylsulfonyl) propionic acid in 200 parts of acetone and 150 parts of methanol dissolved in the heat and treated with a solution of 1.7 parts of sodium hydroxide in 2 parts of water. To the sodium salt which has crystallized out is filtered off with suction after cooling.

Example 3

17 parts of acrylamide are dissolved in 50 parts of acetone. After adding 0.5 part of copper powder, 51 parts of perfluorobutanesulfinic acid are added dropwise to the solution at 40 to 50 ° C. After the reaction has ended, the reaction mixture is ^{cooled to 0} ° C. and the crystalline precipitate which has separated out is filtered off with suction. 56 parts of a colorless crystalline compound are obtained.

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FP (after recrystallization from benzene / acetone): 150-153 ⁰ C.

C ₄ F ₉ -SO ₂ -CH ₂ -CH ₂ -CONH ₂ C ₇ H ₆ F ₉ NO ₃ S (355)

calc .: C 23 £ 7% H 1.70% F 48.14% N 3.94% S 9P3% found : C 24 £ 0% H 10% F 47.70% N 4.01% S Q80%

The IR spectrum agrees with the structure indicated.

Example 4

36 parts of the 2- (perfluorobutylsulfonyl) propionic acid described in Example 1 are dissolved in 2oo parts of methanol with the addition of 3 parts of concentrated sulfuric acid and refluxed for 6 hours. After cooling, the reaction mixture is poured into water and the precipitated crystalline compound sucked off. 35 parts of crystalline substance are obtained.

FP (after recrystallization from toluene): 45 to 48 ^° C

C ₈ H ₇ F ₉ O ₄ S (MG 37o)

calc .: C 25.95% H 1.91% F 46.19% S 8.66% found: C 26, oo% H 2.1% F 45.5% S 8.3%

The IR spectrum agrees with the specified structure a.

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Example 5 r

52 parts of the 2- (perfluorobutylsulfonyl) propionic acid described in Example 1 are dissolved with 17 parts of allyl alcohol and 1 part of p-toluenesulfonic acid in 150 parts of benzene. The reaction mixture is heated to reflux temperature. The water formed during the reaction (4 parts) is removed by azeotropic distillation. When the esterification is complete, the reaction solution is washed with 25 parts of water and then freed from the solvent. 49 parts of a crystalline substance remain, which are recrystallized from toluene. FP (after recrystallization from toluene): 49 to 51 ⁰ G

C ₄ F ₉ -SO ₂ -CH ₂ -CH ₂ -COOCH ₂ -CH = Ch ₂

C ₁₀ H ₉ F ₉ O ₄ S (MG 396)

ber .: C 3o, 33 $ H 2.29 # Ϊ ¹ 43.15 $ S 8, o9 # "found.: C 3o, 4 # H 2.4 # ■ F 43.7 $ S 8.00 Jf

The IR spectrum agrees with the structure indicated.

In an analogous manner, esterification with n-Doöecylal » alcohol or n-octadecyl alcohol of the dodecyl ester

C ₄ F ₉ -SO ₂ -CH ₂ -CH ₂ -COO-C ₁₂ H ₂₅

or the n-octadecyl ester

C ₄ F ₉ -SO ₂ -CH ₂ -CH ₂ -GOO-C ₁₈ H ₃₇

obtain.

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Example 6 °

18 parts Perfluorbutansulfinsäure, 0.5 parts of hydroquinone and 7.7 parts of methacrylic acid are dissolved in 20 parts of acetone and 2 hours at 40 - 50 ⁰ C stirred. After the solvent has been distilled off, 23 parts of residue remain, which are recrystallized from toluene. FP: 110-113 ⁰ C

C ₄ P ₉ -SO ₂ -CH ₂ -CH-COOH CH,

C ₈ H ₇ P ₉ O ₄ S (370)

Calc .: C 25.98 ft H 1.91 $> P 46.15 # S 8.67 found: C 25.60? t H 1.70 f> P 45.70 # S 8.20

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Claims (8)

Patent claims Perfluoroalky! Sulfones of the formula R _f - SO ₂ - CH ₂ - QH - X in the R _f for a G ₁ -C ₁₂ perfluoroalkyl radical and R for hydrogen or a methyl group stand and X denotes a cyano, carbonamide, -COOM or -COOR ₁ group, in which M represents hydrogen or an alkali, alkaline earth or ammonium ion and R _{1 stands} for a C ₁ -C _2ii , -alkyl radical or a C ₂ -Cc-alkenyl radical. 2.) Perfluoroalky! Sulfones according to claim 1, in which X is for a -COOM group is available. 3.) Perfluoroalkylsulfones according to claim 1, in which X is a -COOR ₁ -GrUpPe in which R _{1 is} a C ₂ -Cj ₅ -alkenyl radical. 4.) Perfluoroalkylsulfones according to claim 3, in which R _{1 is} a vinyl or ally! Group. Le A 14 624 - 9 - 40981 1/1 19 5.) Process for the preparation of perfluoroalkyl sulfones of the formula - SO ₂ - CH ₂ - CH - X in the R _f stands for a Cj-C ^ perfluoroalkyl radical and R stands for hydrogen or a methyl group and X denotes a cyano, carbonamide, -COOM or -COOR ₁ group in which M for hydrogen or an alkali, alkaline earth or ammonium ion and R _{1 stands} for a C ₁ -C ₂ ^ alkyl radical or Cg-Cc-alkenyl radical, characterized in that perfluoroalkanesulfinic acids Formula 4 R _f - SO ₂ H, in R. has the meaning given above with unsaturated compounds of the formula CH ₂ = C-X
R. in which R and X have the meaning given above, at temperatures from 10 to 12o ° C., optionally in inert organic diluents and in the presence of polymerization inhibitors. Le A 14 624 -10- 40981 1/1 1 9 p 6.) Method according to claim 5? characterized, that the reaction can be carried out at temperatures from 2o "to 7o C. undertakes. 7.) Method according to claim 5 and 6, characterized in that that one perfluoroalkanesulfinic acids and unsaturated compounds in a molar ratio of 1: 1 to 1.5. 8.) Process according to claim 5 for the preparation of perfluoroalkyl _{sulfones in which R 1 is} a G ₁ -Cg ^ -alkyl radical or C ₂ -Ct - alkenyl radical, characterized in that perfluoroalkylsulfones of the formula R _f - SO ₂ - CH ₂ -CH- COOH with alcohols of the formula R ₁ - OH esterified in the usual way, Ie A 14 624 - 11 - 409811 / 119S