EP2035131A2

EP2035131A2 - Fluorosurfactants

Info

Publication number: EP2035131A2
Application number: EP07764997A
Authority: EP
Inventors: Wolfgang Hierse; Nikolai Ignatyev (Mykola); Martin Seidel; Elvira Montenegro; Peer Kirsch; Andreas Bathe
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2006-07-04
Filing date: 2007-07-02
Publication date: 2009-03-18
Also published as: WO2008003446A2; DE102006032391A1; WO2008003446A3; US20100152081A1; JP2009541402A

Abstract

The invention relates to compounds comprising an aryl sulfonate group, a spacer and a Y group, wherein Y represents CF3- (CH2)a-O-, SF5-, CF3-(CH2)a-S-, CF3CF2S-, [CF3-(CH2)a]2N- or [CF3- (CH2)a]NH-, a represents a whole number selected from the range of 0 to 5 or (formula I), Rf represents CF3-(CH2)r-, CF3-(CH2)r-O-, CF3-(CH2)r-S-, CF3CF2-S-, SF5- (CH2)r- or [CF3-(CH2)r]2N-, [CF3-(CH2)r]NH- or (CF3)2N-(CH2)r-, B represents a simple bond, O, NH, NR, CH2, C(O)-O, C(O), S, CH2-O, O-C(O), N-C(O)1 C(O)-N, O-C(O)-N, N-C(O)-N, O-SO2 or SO2-O, R represents alkyl having 1 to 4 C-atoms, b represents 0 or 1 and c represents 0 or 1, q represents 0 or 1, at least one radical from b and q represents 1, and r represents 0, 1, 2, 3, 4 or 5. The invention also relates to a method for the production of said compounds and to the uses of said surface-active compounds.

Description

fluorosurfactants

The present invention relates to compounds having an arylsulfonate group, a spacer and a group Y, wherein Y is CF ₃ - (CH ₂ Ja-O-, SF ₅ -, CF ₃ - (CH ₂ ) aS-, CF ₃ CF ₂ S -, [CF ₃ - (CH ₂ ) _a ] ₂ N- or [CF ₃ - (CH ₂ Ja] NH-, where a is an integer selected from the range of 0 to 5 or

stands, where

Rf is CF ₃ - (CH ₂ Jr, CF ₃ - (CH ₂ JrO-, CF ₃ - (CH ₂ J _n -S-, CF ₃ CF ₂ -S-, SF ₅ - 5 (CH ₂ Jr or [ CF ₃ - (CH ₂ Jr) ₂ N-, [CF ₃ - (CH ₂ Jr] NH- or (CF ₃ J ₂ N- (CH ₂ Jr,

B is a single bond, O, NH, NR, CH ₂ , C (O) -O, C (O), S, CH ₂ -O,

OC (O), NC (O), C (O) -N, O-C (O) -N, NC (O) -N, O-SO ₂ or SO ₂ -O

R is alkyl of 1 to 4 carbon atoms, b is O or 1 and c is O or 1, Q q is O or 1, wherein at least one of b and q is 1, and r is O, 1, 2, 3, 4 or 5, preparation process for these compounds and

Uses of these surface-active compounds.

Fluorosurfactants have a superior ability to lower the surface energy used, for example, in the hydrophobization of surfaces such as textile impregnation, hydrophobization of glass, or the so-called deicing of aircraft wings.

In general, however, fluorosurfactants contain perfluoroalkyl substituents that in the environment due to biological and other oxidation processes

Perfluoralkancarbonsäuren and sulfonic acids are degraded. These are considered persistent and are z. T. suspected damage to health causing (GL Kennedy, Jr ₁ JL Butenhoff, GW Olsen, JC ^O'Connor, AM Seacat, RG Perkins, LB Biegel, SR Murphy, DG Farrar, Critical Reviews in Toxicology 2004, 34, 351-384). Longer-chain perfluoroalkanecarboxylic acids and sulfonic acids also accumulate in the food chain.

There is therefore a need for surface-active substances with a property profile comparable to the conventional fluorosurfactants, which are preferably oxidatively or reductively degradable. Particularly advantageous are compounds which leave no persistent fluorine-organic degradation products in their oxidative or reductive degradation.

A known perfluorinated arylsulfonate is the sodium salt of 4- (heptadecafluorooctyl) -benzenesulfonic acid (CAN 118: 126988).

From the company Omnova polymers are sold whose side chains have terminal CF ₃ - or CaFs groups. International Patent Application WO 03/010128 describes perfluoroalkyl-substituted amines, acids, amino acids and thioether acids which have a C _3-2 o-perfluoroalkyl group.

JP-A-2001/133984 discloses surface-active compounds containing perfluoroalkoxy chains, which are suitable for use in antireflection coatings. JP-A-09/111286 discloses the use of perfluoropolyether surfactants in emulsions.

However, these known fluorosurfactants ultimately lead to the formation of persistent perfluoroalkanesulfonic acids and carboxylic acids during degradation. Even substitutes with a terminal CF ₃ group that are better tolerated in terms of ecology can be degraded to persistent trifluoroacetic acid. In the earlier German patent application DE 102005000858, compounds which carry at least one terminal pentafluorosulfuranyl group or at least one terminal trifluoromethoxy group and have a polar end group are surface-active and are described in an outstanding manner as surfactants.

Linear aryl sulfonates without fluorination, such as sodium nonyl benzene sulfonate, are among the most widely used surfactants because they are biodegradable. They have good chemical and thermal stability and can be used in spray-dried formulations. Due to their cost-effective production, the linear arylsulfonates are used as detergents in the household, as detergents and in industrial products.

This class of arylsulfonates with OCF ₃ or SF ₅ groups as modification were not described in DE 102005000858.

There is still a need for further, preferably degradable, substitutes for perfluorinated surfactants.

It has now been found that the compounds according to the invention which contain at least one Y group selected from the group CF ₃ - (CH ₂ ) _a -O-, SF ₅ -, CF ₃ - (CH ₂ ) _a -S-, CF ₃ CF ₂ S-, [CF ₃ - (CH ₂ ) _a ] 2 N- or [CF ₃ - (CH ₂ ) _a ] NH-, where a is an integer selected from the range of 0 to 5 or

in which - A -

Rf is CF ₃ - (CH ₂ Jr, CF ₃ - (CH ₂ ) r 0 -, CF ₃ - (CH ₂ JrS-, CF ₃ CF ₂ -S-, SF ₅ - (CH ₂ Jr or [CF ₃ - (CH ₂ Jr] ₂ N-, [CF ₃ - (CH ₂ Jr] NH- or (CF ₃ J ₂ N- (CH ₂ Jr, B is a single bond, O, NH, NR, CH ₂ , C ( O) -O, C (O), S, CH ₂ -O, OC (O) ₁ NC (O), C (O) -N, 0-C (O) N, NC (O) -N, 0-SO ₂ or SO ₂ -OR is alkyl having 1 to 4 C atoms, b is O or 1 and c is O or 1, q is O or 1, where at least one of b and q is 1, and r is 0, 1, 2, 3, 4 or 5, which are preferably terminal, are surface active and are outstandingly useful as surfactants.

A first subject of the invention are therefore compounds having an arylsulfonate group, a spacer and at least one group Y, where Y is CF ₃ - (CH ₂ ) _a -O-, SF ₅ -, CF ₃ - (CH ₂ ) _a -S- , CF ₃ CF ₂ S-, [CF ₃ - (CH ₂ ) a] ₂ N- or [CF ₃ - (CH ₂ ) _a ] NH-, where a is an integer selected from the range of 0 to 5 or

stands, where

Rf is CF ₃ - (CH ₂ ) r, CF ₃ - (CH ₂ K ⁾ -, CF ₃ - (CH ₂ ) _r S-, CF ₃ CF ₂ -S-, SF ₅ -

(CH ₂ ) _r or [CF ₃ - (CH ₂ ) J ₂ N-, [CF ₃ - (CH ₂ ) _r ] NH- or (CF ₃ ) ₂ N- (CH ₂ ) _r , B is a single bond , O, NH, NR, CH ₂ , C (O) -O, C (O), S, CH ₂ -O,

OC (O), NC (O), C (O) -N, O-C (O) -N, NC (O) -N, O-SO ₂ or SO ₂ -O

R is alkyl of 1 to 4 carbon atoms, b is O or 1 and c is O or 1, q is O or 1, wherein at least one of b and q is 1, and r is O. , 1, 2, 3, 4 or 5. The compounds according to the invention preferably contain no further fluorinated groups in addition to the stated fluorinated end groups.

Preferably, the group Y in the surface-active compounds is bound to a saturated or unsaturated, branched or unbranched hydrocarbon unit, the spacer, wherein the hydrocarbon unit in the chain or in a branch may optionally be provided with one or more heteroatoms. The hydrocarbon units may be aliphatic or aromatic units.

In a variant of the invention, the group Y occurs several times in the surface-active compound and the surface-active compound is preferably an oligomer or polymer.

In another likewise preferred variant of the invention, the group Y in the surface-active compound occurs only once, twice or three times, compounds in which the group occurs only once being particularly preferred.

The compounds according to the invention are preferably low molecular weight compounds of the formulas IA to IB

correspond, wherein Y is CF ₃ - (CH ₂₎ AO- _(SF ₅ -, CF 3 (CH ₂₎ AS, CF ₃ CF ₂ S-, [CF ₃ - (CH ₂₎ _a] ₂ N- or [CF ₃ - (CH ₂ ) _a ] NH-, where a is an integer selected from the range of 0 to 5 or

, where 1 ₀ Rf is CF 3 (CH ₂₎ r CF ₃ - (CH ₂₎ R-O-, CF ₃ - (CH ₂₎ _r -S-, CF ₃ CF ₂ -S-, SF ₅ -

(CH ₂ ) _r - or [CF ₃ - (CH ₂ ) _r ] ₂ N-, [CF ₃ - (CH ₂ ) _r ] NH- or (CF ₃ ) ₂ N- (CH ₂ ) _r ,

B is a single bond, O, NH, NR, CH ₂ , C (O) -O, C (O), S, CH ₂ -O,

OC (O), NC (O), C (O) -N, O-C (O) -N, NC (O) -N, O-SO ₂ or SO ₂ -O

R is alkyl having 1 to 4 C atoms, - _{j 5} b is O or 1 and c is O or 1, q is O or 1, wherein at least one of b and q is 1, and r stands for O, 1, 2, 3, 4 or 5,

Spacer is a saturated or unsaturated, branched or unbranched

Hydrocarbon moiety, wherein the hydrocarbon moiety in 2Q of the chain or in a branch may optionally be provided with one or more heteroatoms,

M is a metal cation and m is 1, 2 or 3. According to the invention, compounds of the formulas IA and / or IB are particularly preferred.

in the form IA or IB, M represents a metal cation, in particular selected from an alkali metal cation, an alkaline earth metal cation or Q an ammonium ion. The lithium, sodium or potassium cation or NH ₄ ⁺ is preferably used for M. In the formulas IA or IB, m indicates the number of sulfonyl radicals present, m being preferably 1 or 2, very particularly preferably 1.

For m = 1, the position of the sulfonyl radical for the formula IA in the ortho, meta or para position is possible. The para position is preferred.

For m = 1, the position of the sulfonyl radical is the formula IB

Carbon atom C-4, C-5 or C-6 is preferred, more preferably at C-5 or C-6, which is illustrated by the following sub-formulas:

Spacer-Y

or

Y-spacer

The position of the spacer carrying the group Y is preferably C-1 or C-2, more preferably C-1.

Heteroatoms in the hydrocarbon moiety of the spacer can be, for example, O, S or NH, preferably O or S, very particularly preferably O.

In a further preferred embodiment of the compounds according to the invention, the spacer can formally by

- (CHz) _n -,

- (CH ₂ ) -CH (HalMCH ₂ ) (n-ir, - (CHz) _n -O-, - (CH ₂₎ n O- (CH ₂₎ _p - or CH 2 CH = CH (CH 2) (n) -,

- (CH 2) ni-Ar- (CH 2) ₍ ni) -

- (CH ₂ ) niC≡C- (CH ₂ ) n-

- (CH ₂ ) nQ- (CH ₂ ) n-, where

Ar stands for aryl,

Q is O, S or N, n and n 'are an integer from the range 1 to 30,

Hal is Cl, Br or I and p is an integer from the range 1 to 4.

n and / or n 'preferably stands for an integer from the range from 4 to 24, and particularly preferably for an integer from the range from 6 to 18. In one variant of the invention, it is again preferred for n to be an even number.

HaI in a variant of the invention is preferably Cl or Br, very particularly preferably Br.

In a variant of the invention, p is preferably 2 or 3, very particularly preferably 3.

The spacers

- (CH ₂ ) -CH (Hal) - (CH ₂ ) _(n-1) -, are preferred in a variant of the invention for Y = SF ₅ .

The spacers - (CH ₂ ) _n -, - (CH ₂ ) _n -O-, - (CH ₂ ) _n -O- (CH ₂ ) p- or -CH 2 CH = CH- (CH 2) (ni) -, in a variant of the invention are preferred for Y is CF ₃ - (CH ₂ ) aO-, CF ₃ - (CH ₂ ) _a -S-, CF ₃ CF ₂ S-, [CF ₃ - (CH ₂₎ _a] ₂ N- or [CF ₃ - (CH ₂₎ _a] NH-, where a is an integer selected from the range of 0 to 5 or

- _Q stands, where

Rf is CF ₃ - (CH ₂ ) r, CF ₃ - (CH ₂ ) rO-, CF ₃ - (CH ₂ JrS-, CF ₃ CF ₂ -S-, SF ₅ - (CH ₂ ) _Γ or [CF ₃ - (CH ₂ ) _r ] ₂ N-, [CF ₃ - (CH ₂ ) JNH- or (CF ₃ ) ₂ N- (CH ₂ ) _r -, B is a single bond, O, NH, NR, CH ₂ , C (O) -O, C (O), S, CH ₂ -O, OC (O), NC (O), C (O) -N, O-C (O) -N, NC (O ) -N, O-SO ₂ or SO ₂ -O

<lg R is alkyl having 1 to 4 C atoms, b is O or 1 and c is O or 1, q is O or 1, where at least one of b and q is 1, and r is for 0, 1, 2, 3, 4 or 5.

2Q In group Y, a is preferably 0, 1 or 2, more preferably O or 2, most preferably O.

Among the fluorine groups as aryl substituents, which are also referred to below as Rf for short, those are preferred in which r is 0, 1 or 2, 5 where r is preferably O. , CF ₃ S-, CF ₃ CF ₂ -S-, SF ₅ - or - (CF ₃ Y ₂ N- particularly preferred are the groups Rf = CF ₃ correspond to the invention.

The group Y, as defined above, in a preferred variant of the invention consists of CF ₃ -O-, CF ₃ -S-, CF ₃ CF ₂ -S-, (CF ₃ J ₂ N-, CF ₃ NH- or stands, where

Rf is CF ₃ - (CH ₂ ) r, CF ₃ - (CH ₂ ) rO-, CF ₃ - (CH ₂ ) rS-, CF ₃ CF ₂ -S-, SF ₅ - (CH ₂ ) _r - or [CF ₃ - (CH ₂ ) J ₂ N-, [CF ₃ - (CH ₂ ) JNH- or (CF ₃ ) ₂ N- (CH ₂ ) r, B represents a single bond, O, NH, NR, CH ₂ , C (O) -O, C (O), S, CH ₂ -O, OC (O), NC (O), C (O) -N, O-C (O) -N, NC (O ) -N, O-SO ₂ or SO ₂ -OR is alkyl having 1 to 4 carbon atoms, b is O or 1 and c is O or 1, q is O or 1, wherein at least one radical b and q are 1, and r is O.

Rf is preferably CF ₃ - (CH ₂ ) _r> CF ₃ - (CH ₂ ) _r O-, CF ₃ - (CH ₂ ) _r -S or [CF ₃ -

(CH ₂ ) J ₂ N-. A preferred variant of the invention comprises fluorine groups, also referred to below as Rf for short, in which r stands for 0, 1, 2 or 3, in particular for O, 1 or 2, where r is preferably O.

In a particularly preferred embodiment of the present invention

Invention Rf is CF ₃ -, CF ₃ -O-, CF ₃ -CH ₂ -CH ₂ -O-, CF ₃ -S-, CF ₃ CF ₂ -S-, SF ₅ -, CF ₃ -CH ₂ - CH ₂ -S-, (CFs) ₂ -N- and (CF ₃ -CH ₂ -CH ₂ ) ₂ -N-, especially for CF ₃ -, CF ₃ -O-, CF ₃ -S- and (CF ₃ ) ₂ -N-.

Another preferred variant of the invention comprises the groups Rf the same

CF ₃ , CF ₃ -S, CF ₃ CF ₂ -S, SF ₅ - or (CF ₃ ) ₂ N-.

Particularly preferred groups B are O, S, CH ₂ O, CH ₂ , C (O) and OC (O). In particular, B is O and OC (O) are preferred. A particularly preferred variant of the invention comprises the groups Y being CF ₃ -Ar-O, CF ₃ -O-Ar-O, CF ₃ -CH ₂ -CH ₂ -O-Ar-O, CF ₃ -S-Ar-O, CF ₃ CF ₂ -S-Ar-O, SF ₅ -Ar-O, CF ₃ -CH ₂ -CH ₂ -S-Ar-O, (CF ₃ ) ₂ -N-Ar-O, (CF ₃ -CH ₂ -CH ₂ ) ₂ -N-Ar-O, CF ₃ -Ar-OC (O), CF ₃ -O-Ar-OC (O), CF ₃ -CH ₂ -CH ₂ -O-Ar-OC ( O), CF ₃ -S-Ar-OC (O), CF ₃ CF ₂ -S-Ar-OC (O), SF ₅ -Ar-OC (O) ₁ CF ₃ -CH ₂ -CH ₂ -S- working

OC (O), (CF ₃ ) ₂ -N-Ar-OC (O) and (CF ₃ -CH ₂ -CH ₂ ) ₂ -N-Ar-OC (O), especially CF ₃ -Ar-O, CF ₃ -O-Ar-O, CF ₃ -S-Ar-O, (CF ₃ ) ₂ -N-Ar-O, CF ₃ -Ar-OC (O), CF ₃ -O-Ar-OC (O) , CF ₃ -S-Ar-OC (O) and (CF ₃ ) ₂ -N-Ar-OC (O).

A particularly preferred variant of the invention comprises Y equal to CF ₃ -Ar-O and CF ₃ -Ar-OC (O).

In a variant of the present invention, it is preferred that q is O and at least one c and / or b are each 1. In particular, it is preferred that all c and b are 1, i. the aromatics are substituted in the o, p, o position by fluorine groups.

In a further variant of the invention it is preferred if all q and b are each O and at least one c is 1. In particular, it is preferred that both c are 1, i. the aromatics are substituted in the o, o position with fluorine groups.

In a further variant of the invention it is preferred that all c and q are each O and b is 1, i. the aromatics are substituted in the p position with fluorine groups.

Particular preference is given to using compounds which have a combination of the variabein in their preferred or particularly preferred ranges.

Further preferred combinations are disclosed in the claims. Advantages of the compounds according to the invention or the compositions or compositions according to the invention can be in particular:

a surface activity which may be the same or superior to conventional hydrocarbon surfactants in terms of efficiency and / or effectiveness; and / or

- biological and / or abiotic degradability of the substances without formation of persistent, perfluorinated degradation products and / or

good processability in formulations and / or

- storage stability.

Particularly preferred compounds include the following compounds:

The compounds which can be used according to the invention as surfactants are particularly suitable for use as water repellents or oleophobicizing agents. Applications include the surface modification of textiles, paper, glass, porous building materials or adsorbents. In paints, paints, varnishes, photographic coatings (for photographic plates, films and papers), special coatings for the semiconductor

Photolithography (photoresists, top anti-reflective coatings, bottom anti-reflective coatings) or other surface coating compositions, the compounds of the invention or the compounds to be used according to the invention can be advantageously used with one or more of the following functions: anti-fogging agent, dispersant, emulsion stabilizer, defoamer, deaerator, antistatic agent , Flame retardants, gloss enhancers, lubricants, improvers of pigment or filler compatibility, scratch resistance improvers, substrate adhesion promoters, surface tack reducers, skin inhibitors, water repellents, oleophobic agents, UV stabilizers, wetting agents, leveling agents, viscosity reducers, migration inhibitors, drying accelerators. In printing inks, the compounds according to the invention or the compounds to be used according to the invention can also be used advantageously and have one or more of the following functions: defoamer, deaerator, friction control agent, wetting agent, leveling agent, pigment compatibility improver, printing resolution improver, drying accelerator.

The use of the compounds according to the invention or of the compounds to be used according to the invention as additives in surface coating formulations, such as printing inks, paints, paints, coatings, photographic coatings, special coatings for semiconductor photolithography, such as photoresists, top anti-reflective coatings, bottom anti-reflective coatings, or Additive preparations for Additization of corresponding preparations is therefore a further subject of the present invention.

Another use according to the invention of compounds according to the invention or the compounds to be used according to the invention is the use as an interface mediator or emulsifier. In particular, for the preparation of fluoropolymers by means of emulsion polymerization, these properties can be advantageously exploited.

Compounds according to the invention or compounds to be used according to the invention can be used as foam stabilizers, in particular in preparations known as "fire-extinguishing foams." The use of compounds according to the invention or compounds to be used according to the invention as a foam stabilizer and / or to support film formation, in particular in aqueous film-forming compositions Fire-extinguishing foams, both synthetic and protein-based and also for alcohol-resistant formulations (AFFF and AFFF-AR, FP, FFFP and FFFP-AR fire-extinguishing foams) is therefore a further subject of the invention.

It is also possible to use antistatic agents according to the invention or compounds to be used according to the invention. The antistatic effect is particularly useful in the treatment of textiles, in particular clothing, carpets and rugs, upholstery in furniture and automobiles, non-woven textile materials, leather goods, paper and cardboard, wood and wood-based materials, mineral substrates such as stone, cement, concrete, Plaster, ceramics (glazed and unglazed bricks, stoneware, porcelain) and glasses, and for plastics and metallic substrates of importance. The corresponding use is an object of the present application. For metallic substrates, the use of compounds according to the invention in anticorrosives is additionally an object of the present invention.

Their use as mold release agents in plastics processing is another object of the present invention.

In general, compounds of the invention or compounds to be used according to the invention are useful as protectants against stains and stains, stain releases, anti-fogging agents, lubricants, and as abrasion resistance and mechanical durability improvers.

As additives in detergents and stain removers for textiles (in particular clothing, carpets and carpets, upholstery coverings in furniture and automobiles) and hard surfaces (in particular kitchen surfaces, sanitary facilities, tiles, glass) and in polishing agents and waxes (in particular for furniture, floors and automobiles) Compounds according to the invention or compounds to be used according to the invention are advantageously used with one or more of the following functions: wetting agent, leveling agent, hydrophobizing agent, oleophobizing agent, stain and soil protection agent, lubricant, defoamer, deaerator, drying accelerator. In the case of detergents and stain removers, the use as detergent or soil emulsifying and dispersing agent is additionally an advantageous embodiment of the present invention. The use of compounds according to the invention or compounds to be used according to the invention in cleaning agents and stain removers or as wetting agents, leveling agents, water repellents, oil repellents, stain and soil protection agents,

Lubricant, defoamer, deaerator or drying accelerator is therefore a further subject of the invention. Also as additives in polymeric materials (plastics), the compounds according to the invention or compounds to be used according to the invention may advantageously have one or more of the following functions: lubricant, internal friction reducer, UV stabilizer,

Hydrophobic, Oleophobiermittel, stain and soil protection agents, fillers, flame retardants, migration inhibitor (especially against migration of plasticizers), anti-fogging agents are used.

When used as additives in liquid media for cleaning, etching, reactive modification and / or substance deposition on metal surfaces (especially electroplating and anodization) or semiconductor surfaces (especially for semiconductor photolithography) compounds of the invention or used according to the invention compounds act as a developer , Stripper, Edge Bead Remover, Etching and cleaning agents, as wetting agents and / or enhancers of the quality of deposited films. In the case of galvanic processes (in particular of chrome electroplating), the function as a haze inhibitor with or without foaming action is additionally an object of the present invention.

In addition, the compounds which can be used according to the invention as surfactants are suitable for washing and cleaning applications, in particular of textiles. Cleaning and polishing hard surfaces is also a possible field of application for the compounds which can be used according to the invention as surfactants. Furthermore, the compounds which can be used according to the invention as surfactants can advantageously be used in cosmetic products, such as, for example, foam baths and hair shampoos, or as emulsifiers in creams and lotions. As additives in hair and personal care products (eg hair conditioners and hair conditioners), having one or more of the following functions: Wetting agents, foaming agents, lubricants, antistatic agents, increase in resistance to skin fats, the compounds of the invention or the compounds used according to the invention can also be used advantageously.

As additives in herbicides, pesticides and fungicides, compounds according to the invention or compounds to be used according to the invention have one or more of the following functions: substrate wetting agent, adjuvant, foam inhibitor, dispersant, emulsion stabilizer.

As additives in adhesives, with one or more of the following functions: wetting agents, penetrating agents, substrate adhesion promoters, defoamers, compounds according to the invention or compounds to be used according to the invention can likewise be used to advantage.

Also as additives in lubricants and hydraulic fluids, with one or more of the following functions: wetting agent, corrosion inhibitor, compounds of the invention or used according to the invention compounds can serve. In the case of lubricants, the use as a dispersant (in particular for fluoropolymer particles) is additionally an essential aspect.

When used as additives in putties and fillers, compounds of the invention or compounds to be used according to the invention may have one or more of the following functions: water repellents, oil repellents, soil protection agents, weatherability improvers, UV stabilizers, silicone bleed-off agents.

Another field of application for the compounds which can be used according to the invention as surfactants is flotation, ie the application and Separation of ores and minerals from dusty rocks. For this purpose, they are used as additives in preparations for mineral processing, in particular flotation and leaching solutions, with one or more of the following functions: wetting agent, foaming agent, foam inhibitor. Also related is the use as additives in petroleum source stimulation means, with one or more of the following functions: wetting agent, foaming agent, emulsifier.

In addition, they can be used as additives in deicers or anti-icing agents.

In addition, preferred compounds of the invention which can be used as surfactants can also be used as emulsifiers or dispersing agents in foods. Further fields of application lie in the metal treatment, as leather auxiliary, the building chemistry and in the plant protection.

Furthermore, surfactants of the invention are also useful as antimicrobial agents, especially as reagents for antimicrobial surface modification.

All uses of compounds according to the invention to be used according to the invention are the subject of the present invention. The particular use of surfactants for the stated purposes is known to the person skilled in the art, so that the use of the compounds to be used according to the invention causes no problems.

In this case, the compounds according to the invention for the application are usually introduced into appropriately designed preparations. Corresponding agents containing at least one compound according to the invention are likewise provided by the present invention. Such agents preferably contain one for the respective one Intended use suitable carrier and optionally other specific active ingredients and / or optionally adjuvants.

In preferred compositions, these are color and lacquer preparations, fire-extinguishing agents, lubricants, detergents and

Detergents, deicers or water repellents for textile finishing or glass treatment. In a preferred variant of the invention, the agents are water repellents for finishing textiles and carpets.

For the hydrophobic finishing of textiles, water repellents based on polysiloxanes, fluorohydrocarbons or mixtures of aluminum or zirconium salts with paraffins are generally used (cf. "Handbook of Textile Auxiliaries", A. Chwala, V. Anger, Verlag Chemie, New York 1977,

Chapter 3.24 "Phobizing agents", page 735 ff). The hydrophobic finishing of textiles, especially weatherproof clothing, serves to render it either water-repellent or water-impermeable. The hydrophobizing agent is applied to the fibers of the textiles and arranges there so that the hydrophobic parts of the molecule perpendicular to

Fiber surface stand. In this way, the tendency of the water to spread over the whole area, greatly reduced. The water takes on the spherical shape due to the cohesive forces and rolls off the textile surface.

Further fields of application for agents according to the invention are dyestuff and lacquer preparations, fire-extinguishing agents (powders and foams), lubricants, detergents and de-icers.

The preparation of the agent can be carried out according to known methods; for example, by mixing the inventive Compounds having a carrier suitable for the respective intended use and, if appropriate, further specific active substances and optionally excipients. The preparation of the compounds to be used according to the invention can be carried out by methods known to the skilled person from the literature.

The preparation of the compounds according to the invention can be carried out according to methods known to the skilled person from the literature. Examples are described below.

The invention therefore further provides a process for the preparation of the compounds according to the invention, characterized in that a compound of the formula II Y spacer Z II where Y and -Spacer- can have one of the meanings given above, and

Z is OH, Br, Cl or vinyl, are reacted with the corresponding aromatic, selected from the group benzene or naphthalene, and then carried out a sulfonation and salt formation.

The connection of the compounds of the formula II, as defined above, preferably takes place via a Friedel-Crafts alkylation. The reaction conditions and reaction routes for Friedel-Crafts alkylations are the

Known in the art and described in detail in the standard literature.

The reaction of the compounds of formula II with the aromatic takes place in the presence of the Lewis acid aluminum trichloride. In this case, both by Y modified alcohols, as well as chlorides or bromides, or

Compounds of formula II are used with a terminal double bond. The synthesis of these compounds will be described below. The sulfonation according to Friedel-Crafts alkylation is likewise a standard procedure and can be carried out, for example, by reaction with sulfur trioxide. The subsequent salt formation in alkali hydroxide / water leads to the corresponding salts. 5

Alternatively to a Friedel-Crafts alkylation, a Grignard reaction is also possible. This reaction is known to the art as a standard reaction.

10 The synthesis of the compounds of the formula II Y spacer Z II where the spacer is denoted by - (CHz) _n -,

- (CH ₂ ) -CH (HalHCH ₂ ) (n-ir, - (CH ₂ ) π-O-,

- (CHz) _n -O- (CH ₂ ) _P - or -CH ₂ CH = CH- (CH ₂ ) (ni) -, 2 ⁰ - (CH ₂ ) _{n -i} -Ar- (CH ₂ ) _{n , _ir - (CH ₂ ) _n-1 -C = C- (CH ₂ ) _n - - (CHz) _n -Q- (CHz) _n - wherein Ar is aryl,

OK

Q is O, S or N, n and n ^{1 are} an integer from the range 1 to 30,

HaI Cl _{1 is} Br or I and p is an integer from the range 1 to 4 and

Y is CF ₃ - (CH ₂ ) _a -O-, SF ₅ -, CF ₃ - (CH ₂ ) _a -S-, CF ₃ CF ₂ S-, [CF ₃ - (CH ₂ ) _a ] ₂ N- or

30

[CF ₃ - (CH ₂ ) _a ] NH-, where a is an integer selected from the group

Range from 0 to 5 or stands, where

Rf is CF ₃ - (CH ₂ ) r-, CF ₃ - (CH ₂ ) rO-, CF ₃ - (CH ₂ VS-, CF ₃ CF ₂ -S-, SF ₅ -

(CH ₂ ) _r - or [CF ₃ - (CH ₂ ) J ₂ N-, [CF ₃ - (CH ₂ ) _r ] NH- or (CF ₃ ) ₂ N- (CH ₂ ) _r ,

B is a single bond, O, NH, NR ₁ CH ₂ , C (O) -O, C (O), S, CH ₂ -O, OC (O), NC (O), C (O) -N , 0-C (O) -N, NC (O) -N, O-SO ₂ or SO ₂ -O

R is alkyl having 1 to 4 carbon atoms, b is O or 1 and c is O or 1, q is O or 1, where at least one of b and q is 1, and r is 0 , 1, 2, 3, 4 or 5 and Z = OH, Cl, Br or vinyl, will now be described in detail for each group Y.

The groups Y can generally be introduced according to the following schemes:

or

In addition, chain extensions via ester or amide formation are possible / feasible

Further functionalization to the arylsulfonate (surfactant end product):

Attachment of the aromatic: Sulfonate introduction:

Term group),

, Hal

In addition to these methods for attaching the arylsulfonate, the linker functionalities listed below (linkage of aromatic Y with linkers) are also applicable.

The CF ₃ -O group can be introduced according to the following schemes: , Hal

.... (for Rf = -CF ₃ )

Me ₄ N ⁺ OCF ₃ - Me ₄ N ⁺ OCF ₃ -

Grubbs Metathesis

Hal = Cl, Br, I

Rf = - (CH ₂ J ₃ CF ₃ ; -CF ₃

or

For Y = CF ₃ -O the following applies:

The aliphatic OCF ₃ group can be obtained, for example, from alcohols via the fluorodeulfuration of xanthates (K. Kanie, Y. Tanaka, K. Suzuki, M. Kuroboshi, T. Hiyama, Bull. Chem. Soc. Jpn., 2000, 73, 471-484, P. Kirsch, Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications, Wiley-VCH, Weinheim, 2004, pp. 67 ff., Pp. 144 f.). The corresponding disclosure to the mentioned method in the cited references thus expressly also belongs to the disclosure content of the present application. The introduction of the Arylsulfonatgruppe is possible by methods known in the art.

Option A: Z (CH ₂ ) _n OH

AZ = HaI, OPg (

Variant B:

Z (CH ₂ ) _n OH

A Z = HaI, OPg (Pg = protecting group)

Derivatization for Z = OP, e.g. OBn:

BnO (CH ₂ X ₁ OCF ₃

C

D, E or G

From the compound D or E, the vinyl compound G can be obtained by elimination

For Y = CF ₃ - (CH ₂ ) _a -O- with a = 2, the following applies:

The introduction of the CF ₃ - (CH ₂ ) ₂ -O group is possible by reacting CF ₃ - (CHa) ₂ -OH with a compound Z- (CH ₂ ) _n -Br, where CF ₃ - (CH ₂ ) ₂ -OH is commercially available and Z represents a protected OH group and subsequent deprotection of the hydroxy group.

Derivatization for Z = OPg (eg OBn):

H ₂ , Pd / C

F ₃ C- (CH ₂ ) ₂ -O- (CH ₂ ) _n -OPg THF

F ₃ C- (CH ₂ ) ₂ -O- (CH ₂ ) _n -OH

PBr ₃ CH ₂ Cl ₂

F ₃ C- (CH ₂ ) ₂ -O- (CH ₂ ) _n -OH F ₃ C- (CH ₂ ) ₂ -O- (CH ₂ ) _n -Br

1. MeSO 2 Cl / toluene

2. NEt3 1. NaO-t-Bu

3. K-O-t-Bu 2. THF

F ₃ C- (CH ₂ ) ₂ -O- (CH ₂ ) _n . ₂ -CH = CH ₂

In an analogous manner, the CF ₃ (CH ₂ ) _a S group can also be prepared via Mitsunobu

Reaction or nucleophilic substitution can be introduced. According to the

Graphs provide analogous transformations the corresponding ones

Compounds (e.g., having alcohol, halide, or olefin functionality on the

Terminus).

The SF ₅ group can be introduced according to the following schemes:

For alcohols, halides:

LiEt ₃ BH

Bu ₃ SnH or

Pg = H, acetyl, pivaloyl, radical starter

Benzyl, tetrahydropyranyl Hal = Cl, Br, I -OPg n = 0 to 30 i)

deprotection

2) PPh ₃ , CCI ₄ or

PPh ₃ Br ₂ or PPh I. ₃ , I ₂

1) 99 *.

deprotection

2) PPh ₃ , CCI ₄ or PPPPhh ₃₃ ,, BBrr _{; 2} or PPh ₃ , I ₂ ^' For esters, carboxylic acids, acid chlorides:

For nitriles, amines, aldehydes, ketones: stepwise or direct oxidation:

SF,

(COCI) ₂ n Cl or

SF. Cl

For olefins, alkynes:

KOtBu

I) Br ₂ or

Ph3P = 2) KOH _SF

SF, ⁵ ^ lr _n - _H

The aliphatic SFs group may, for. B. at terminal double bonds via the radical addition of SF ₅ CI or SF ₅ Br are inserted. Optionally, then, for example, a dehydrohalogenation or a hydrogenation can be carried out. The first two of these reaction steps are described in the literature (R. Winter, PG Nixon, GL Gard, DH Radford, NR Holcomb, DW Grainger, J. Fluorine Chem. 2001, 107, 23-30), catalytic hydrogenations in the presence of SF ₅ function as well (P. Kirsch, M. Brenner, M. Heckmeier, K. Tarumi, Angew Chem, 1999, 111, 2174-2178, Angew Chem Chem Int., Engl., 1999, 38, 1989-1992 ). The corresponding disclosure to the mentioned method in the cited references thus expressly also belongs to the disclosure content of the present application. The introduction of the hydrophilic, reactive or polymerizable component is via the corresponding ω-SF ₅ alcohol by methods known in the art possible. Examples are given in the following scheme:

Derivatization for Z = OPg (e.g., OBn):

The CF ₃ - (CH ₂ ) _a -S or C ₂ F ₅ -S groups may be introduced according to the following schemes:

or or or

or

The end groups CF ₃ (CF ₂ ) _y S- with y = O or 1 may also preferably be prepared by reacting the corresponding Rf bromide with a thiolate as described in NV Ignatiev et al., Zh. Organich. Khim. 1985, 21 (3), p. 653, are introduced into suitable molecules or intermediates. The direct reaction of the thiol with Rf-Br or Rf-I can, as in NV Ignatiev, Ukr. Khim. Zh. 2001, No. 10, pp. 98-102. According to NV Kondartenko et al. Ukr. Khim. Zh. 1975, 41 (6), p. 516ff. For example, the introduction of CF ₃ S groups can also be carried out by means of AgSFC ₃ or according to WA Sheppard, J. Org. Chem. 1964, 29 (4), 895ff by means of CF ₃ SCI. The corresponding disclosure to the mentioned method in the cited references thus expressly also belongs to the disclosure content of the present application.

For Y = CF ₃ - (CH ₂ ) _a -S- with a = 2:

The introduction of the CF ₃ - (CH ₂ ) ₂ -S group is achieved by the reaction of

CF ₃ - (CH ₂ ) ₂ -I with a compound Z- (CH ₂ ) _n -SH, where Z- (CH ₂ ) _n -SH is readily accessible from the corresponding halide and Z is a protected OH group and subsequently Deprotection of

Hydroxy group.

Derivatization for Z = OPg (eg OTHP):

The (CF ₃ ) ₂ N group can be introduced according to the following schemes:

or

Gabriel Synthesis: J. March in March's Advanced Organic Chemistry, 5th ed.

John Wiley and Sons, Ine, New York, 2001, p. 500, 513, 864. or

or

or or

The terminal double bond can be used immediately in the Friedel-Crafts alkylation. A modification to the corresponding alcohols or bromides is shown in the following scheme:

The introduction of the amine building block [CF ₃ - (CH ₂ ) _a ] ₂ N-, where a is an integer selected from the range of 1 to 5, can be carried out using the Gabriel synthesis (Organikum: Organic-Chemical praktikum, 16th ed., VEB Deutscher Verlag der Wissenschaften, Berlin, 1986), followed by the release of the primary amine by reaction with hydrazine. Subsequent alkylation of this amine with CF ₃ (CH ₂ ) Hal gives, after debenzylation, the tertiary amino alcohol as a key building block.

For Y = CF ₃ NH-, the following applies:

The end group CF ₃ NH- in compounds CF ₃ NH-R can be introduced by methods known from the literature by reacting corresponding compounds CbC = NR with an excess of HF (Corresponding syntheses are described, for example, in Petrow et al., Zh. Obshch. Khim. 1959) 2169-2172.) Alternatively, tifluoromethyl isocyanate can also be combined with an alcohol to form a compound CF ₃ -NHC (OO) -OR (according to Knunyants et al., Mendeleev, ex., J. 22 (1977) 15-105 and Motornyi et al., Zh. Obshch. Khim. 29 (1959) 2157-2122). The corresponding starting materials are in each case obtainable by methods known from the literature and the radicals R of the products can be chemically modified by means of established methods.

The group Y with

Y =

in which

_R f = CF ₃ - (CH ₂ ) T, CF ₃ - (CH ₂ ) _r O-, CF ₃ - (CH ₂ ) _r -S-, CF ₃ CF ₂ -S-, SF ₅ - (CH ₂ ) T .

[CF ₃ - (CH ₂ ) _r ] ₂ N-, [CF ₃ - (CH ₂ ) _r ] NH- or (CF ₃ ) ₂ N- (CH ₂ ) _r , B is a single bond, O, NH, NR, CH ₂ , C (O) -O, C (O) ₁ S, CH ₂ -O,

OC (O), NC (O), C (O) -N, OC (O) -N, NC (O) -N, O-SO ₂ or SO ₂ -O

R is alkyl of 1 to 4 carbon atoms, b is O or 1 and c is O or 1, q is O or 1, wherein at least one of b and q is 1, and r is O. ₁ 1, 2, 3, 4 or 5 can be introduced according to the following schemes:

or

A = Hal, OPg (Pg = protecting group), -C = C, -CO ₂ R, -C (O) NR ₁ R ₂ q = 0 and / or 1 b = Q and / or 1 c = 0 and / or 1

or

R ¹ = H or alkyl having 1 to 4 C atoms q = 0 and / or 1 b = 0 and / or 1 c = 0 and / or 1 or

A = Hal, OPg (Pg = protecting group), -C = C, -CO ₂ R, -C (O) NR ¹ R ²

W = O ₁ NH ₁ NO

R '= H or alkyl having 1 to 4 C atoms q = 0 and / or 1 b = 0 and / or 1 c = 0 and / or 1 n = 1 to 30

or

A = Hal, OPg (Pg = protective), -C = C, -CO ₂ R, -C (O) NR ¹ R ²

W = O ₁ NH ₁ NO

or

A = Hal, OPg (Pg = protecting group), -C = C ₁ -CO ₂ R, -C (O) NR ¹ R ²

W = O ₁ NH ₁ NR q = 0 and / or 1 b = 0 and / or 1 c = 0 and / or 1 n = 1 to 30

A = HaI ₁ OPg (Pg = protection group), -C = C, -CO ₂ R, -C (O) NR ¹ R ²

W = O ₁ NH, NR

L = O ₁ S q = 0 and / or 1 b = 0 and / or 1 c = 0 and / or 1 n = 1 to 30

or

A = Hal, OPg (Pg = protecting group), -C = C, -CO ₂ R, -C (O) NR ¹ R ²

W = O, NH ₁ NO

R '= H or alkyl having 1 to 4 C atoms q = O and / or 1 b = O and / or 1 c = 0 and / or 1 n = 1 to 30

A = Hal, OPg (Pg = protecting group), -C = C, -CO ₂ R, -C (O) NR ¹ R ²

W = O ₁ NH ₁ NO

Hal = Cl, Br, I q = O and / or 1 b = O and / or 1 c = 0 and / or 1 n = 1 to 30

or

A = Hal, OPg (Pg = protecting group), -CO ₂ R, -C (O) NR ¹ R ²

Hal = Cl, Br, I

The introduction of this aromatic group, for example, a diol or an alkene succeeds according to the scheme given. In part, the respective Rf-substituted aromatics are commercially available. Otherwise, synthetic methods are also indicated. The corresponding disclosure to the mentioned method in the cited references thus expressly also belongs to the disclosure content of the present application.

The group R f is CF ₃ - (CH ₂ ) r, CF ₃ - (CH ₂ ) rO-, CF ₃ - (CH ₂ ) r S-, CF ₃ CF ₂ -S-, SF ₅ - (CH ₂ ) _r - , [CF ₃ - (CH ₂ ) _r ] ₂ N-, [CF ₃ - (CH ₂ ) _r ] NH- or (CF ₃ ) ₂ N- (CH ₂ ) r-, with indices as described above, can be obtained by means of substitution reactions on aromatics be introduced. If Rf is used in the following schemes, unless otherwise stated, the definition given here applies.

The introduction of the Rf-substituted aryl units can be carried out by reacting the corresponding phenols in a Mitsunobu reaction to form an ether bridge (O. Mitsunobu Synthesis 1981, 1). The attachment of the aryl group via an NH or NR bond also takes place under Mitsunobu conditions according to the following scheme:

Y = OPg or CH = CH ₂ q = 0 or 1 b = 0 or 1

The aryl units with the mentioned Rf substituents can be synthesized by the following reactions:

For CF ₃ substitution: The CF ₃ groups can be obtained by reacting aromatic carboxylic acids with HF and SF ₄ under elevated pressure and elevated temperature, as indicated in the following scheme

1. BuLi number of substituents:

2. (Me ₃ O) ₃ B c: ortho position (O or at least 1)

3. H ₂ O ₂ q: meta position (0 or at least 1) b: para position (0 or at least 1)

DBH = 1,3-dibromo-5,5-dimethylhydantoin Commercially available are compounds of the formula

wherein G = CO ₂ H, CH ₂ NH _2, -CH ₂ OH, -CHO, -COCl, - CH ₂ Br, -CH ₂ CO ₂ H ₁ CH = CH _2, -CH = CHCO ₂ H, - C≡CCH ₂ OH.

Derivatization for aromatic systems with 3 fluorinated CF ₃ groups:

DCC: dicyclohexylcarbodiimide

TPAP: tetra-n-propylammonium perruthenate

THP: tetrahydropyranyl

For SF ₅ - applies:

The modification of commercially available P-nitro-pentafluorosulfurane compounds can be carried out as described in P. Kirsch et al. Angewandte Chemie 1999, 111, 2174-2178 described.

Commercially available reagents are:

G ¹ = -OH, -Br, -NH ₂ , -NO ₂ , -CHO, -CO ₂ H

The m, m-bispentafluorosulfuranyl compounds are as described in W.A. Sheppard J. Am. Chem. Soc. 1962, 84, 3064-3072 or US 3073861 or US 3135736, accessible:

CuBr HBr

The corresponding disclosure of the mentioned methods in the cited references thus expressly also belongs to the disclosure content of the present application. For F ₃ CS- or F ₅ C ₂ S- the following applies:

Commercially available reagents are:

G "= -OH, -Br, -Cl, -NH ₂ , -NO ₂ , -N = C = O, -CHO, -CO ₂ H, -CN, -CH ₂ OH,

CH ₂ Br

Aromatic trifluoromethylthioethers and pentafluoroethylthioethers are obtainable by substitution of iodoaromatics or etherification of thiophenols, as indicated in the following scheme:

For F ₃ CO:

Commercially available reagents or readily available substances are: G "= -OH, -I, -Br ₁ -Cl ₁ -NH ₂ , -SH, -B (OH) ₂ , -CHO, -CO ₂ H, -CO ₂ Me , -CONH ₂ , -CN, -CH ₂ OH, -CH ₂ Br, -CH ₂ CN.

Trifluoromethoxyaromaten can be obtained by reacting phenols with carbon tetrachloride and hydrogen fluoride.

R = subst./unsubst. Aryl, alkyl

R ¹ = -OH

R "= -OCF ₃

X = Cl, Br c = 0 and / or 1 q = 0 and / or 1 b = 0 and / or 1

10

25

30

CuBr HBr

The starting material nitroresorcinol can be prepared according to the following literature: ref. 1 spark; Krucker; BSCFAS; Soc. Soc. Chim. fr .; 1953; 744, 746. Ref. 1 Grosheintz; Fischer; JACSAT; J. Am. Chem. Soc. 70; 1948; 1476, 1478.

For [CF ₃ - (CH ₂ ) _a ] 2N-, the following applies:

The introduction of the amine building block [CF 3 - (CH ₂ ) _a ] ₂ N-, where a is an integer selected from the range from 0 to 5, can be carried out with the aid of the Gabriel synthesis (Organikum: Organic Chemistry Basic Practical, 16th ed., VEB Deutscher Verlag der Wissenschaften, Berlin, 1986), followed by the release of the primary amine by reaction with hydrazine. Subsequent alkylation of this amine with CF ₃ (CH ₂ ) _r Hal gives, after debenzylation, the tertiary amino alcohol as a key building block.

Pd (PPh ₃ ),

LiAlH ₄ CO, MeOH

For (CF ₃ ) ₂ N-:

Commercially available reagents or readily available substances are: G "= -OH, -I, -Br, -Cl, -NH ₂ , -NHAc, -CHO, -CO ₂ H, -CO ₂ Me, -CONH ₂ , -CN , -CH ₂ OH, -CH ₂ Br, -CH ₂ CN.

(CF ₃ ) ₂ N-substituents can be synthesized according to FSFawcett; J. Am. Chem. Soc. 84 (No.22) (1962) 4275-4285 starting from isocyanates by reaction with fluorophosgene and subsequent fluorination with SF ₄ / HF or starting from isothiocyanates by reaction with mercury difluoride and subsequent reaction with fluorophosgene, and subsequent fluorination with SF ₄ ZHF :

An alternative route for the preparation of bis-trifluoromethyl-anilines starts from aromatic aldehydes and is described in detail in R.E.Banks, J. Chem. Soc. Perkin Trans. 1 (1973) 80-82:

For CF ₃ NH- applies:

The end group CF ₃ NH- in compounds CF ₃ NH-R can be introduced by methods known from the literature by reacting corresponding compounds CbC = NR with an excess of HF (Corresponding syntheses are described, for example, in Petrow et al., Zh. Obshch. Khim. 29 (1959) 2169-2173 and E. Kuhle, Angew. Chem. 89 (No.11) (1977), 797-804). Alternatively, tifluoromethyl isocyanate can also be combined with an alcohol to form a compound CF ₃ - NHC (= O) -OR (according to Knunyants et al., Mendeleev Chem., J. 22 (1977) 15-

105 and Motornyi et al., Zh. Obshch. Khim. 29 (1959) 2157-2122). The corresponding starting materials are in each case obtainable by methods known from the literature, or compounds of the type CI ₂ C =NR can be obtained by reacting compounds R-NH-CHO with chlorine and SOCb, and the radicals R of the products can be chemically modified by means of established methods.

The corresponding disclosure relating to the methods mentioned in the cited references hereby expressly also belongs to the disclosure content of the present application.

The choice of suitable solvents and reaction conditions prepares the expert in doing any difficulties (Organikum: Organic Chemical Basic Practical, 16th ed., VEB Deutscher Verlag der Wissenschaften, Berlin, 1986).

In addition to the preferred compounds mentioned in the description, their use, compositions and methods, further preferred combinations of the subject matters of the invention are disclosed in the claims.

The disclosures in the cited references are hereby also expressly incorporated into the disclosure of the present application.

The following examples further illustrate the present invention without limiting the scope of protection. In particular, the features, properties and advantages described in the examples are the applicable to other substances and compounds not covered in detail but covered by the scope of protection, unless otherwise stated elsewhere. Incidentally, the invention is embodied in the entire claimed area and is not limited to the examples mentioned here.

Examples

List of abbreviations used:

5 Bn: benzyl

DBH: 1,3-dibromo-5,5-dimethylhydanthoin

DCM: dichloromethane

DMAP: 4- (dimethylamino) pyridine

Me: methyl

10 MTB: methyl tert-butyl ether

RT room temperature (20 ^° C.)

THF: tetrahydrofuran

PE: Petroleum ether

DCC N.N'-dicyclohexylcarbodiimide

15 RT room temperature

TPAP tetra-n-propylammonium perruthenate

VE fully desalted

9-BBN 9-borabicyclo [3.3.1] nonane

20

example 1

1. Synthesis of the alcohol

In 250 ml of DCM, 15 g of decenol are dissolved and cooled to -40 ⁰ C. 27 g

SF ₅ CI - previously condensed by cold trap - are introduced as gas into the apparatus. For activation, 2 ml of 1-M-Et ₃ B solution are added. The activation is repeated until the mixture no longer warms up when the gas is introduced. The mixture is kept for two hours at the same

OU

Stirred temperature. The reaction mixture is hydrolyzed by addition to ice / NaHCO ₃ solution (saturated), then with NaOH pH10 set. The separated aqueous phase is washed twice with MTB ether. The collected organic phases are extracted once with NaCl solution, dried over sodium sulfate, filtered and the solvent distilled off.

9 g of the starting material are dissolved in 120 ml of ethanol in a 250 ml one-necked flask with reflux condenser and then KOH powder is added. The reaction mixture is stirred overnight. The reaction mixture is concentrated and water and MTB are added, the phases are separated, the aqueous extracted 3 times with MTB, the collected organ. Phases with sat. NaCl, dried over Na ₂ SO 4, filtered off and the solvent distilled off.

2. Friedel-Crafts alkylation:

The alcohol (28 g) is dissolved in 200 g of chlorobenzene, mixed with 13 g of naphthalene and then 13 g of AICI _{3 was} added. After warming to 100 ⁰ C for 12 h, the reaction mixture is added to ice and the organic phase separated. The org. Phase is evaporated and the alkylnaphthalene recrystallized.

3. Conversion to the sulfonate

The alkyl naphthalene (39 g) is sulfonylated at a temperature below 4O ⁰ C without solvent with sulfur trioxide (8 g) and isolated. The isolated product is added to a mixture of NaOH (6 g) and water (30 g). The sulphonate is obtained.

Example 2 Synthesis of Bromide:

1. bromination

The alcohol (8.3 g, 29.4 mmol) is initially charged in dry DCM (0.2 molar solution) and treated with triphenylphosphine (11.6 g, 44 mmol, 1.4 eq) and then in portions with tetrabromomethane (CBr ^ 16.6 g, 50 mmol,

1.5eq). The reaction is stirred for 4 h and then washed with sat.

Quenched NaHCO ₃ solution, extracted with MTB and dried over sodium sulfate.

The resulting crude product is acidified with heptane.

The result is: 9g colorless oil

2. Friedel-Crafts alkylation:

The bromide (34 g) is dissolved in 200 g of chlorobenzene, treated with 13 g of naphthalene and then added 13 g of AICb. After warming to 100 ⁰ C for 12 h, the reaction mixture is added to ice and the organic phase separated. The org. Phase is evaporated and the alkylnaphthalene recrystallized.

3. Conversion to the sulfonate The alkylnaphthalene (39 g) is sulfonylated at a temperature below 40 ° C without solvent with sulfur trioxide (8 g) and isolated. The isolated product is added to a mixture of NaOH (6 g) and water (30 g). The sulphonate is obtained.

4. Analogous surfactant with benzene

1 (E) -10-Bromo-1-pentafluorosulfanyl-dec-1-ene (35 g) is converted to the alkylbenzene in C ₆ H ₆ (200 g) under AICl ₃ catalysis (26 g).

2 In the second step, (E) -10- (pentafluoro) sulfanyl-dec-9-enyl) -benzene (34 g) is sulfonylated with sulfur trioxide (16 g). The salt formation takes place with NaOH water (4g / 20 g)

Example 3 Step 1:

Synthesis of pentafluorothio-bromo-dec-1-ene

The Thiodekan-en-ol - precursor of Thiodekan-en-ylbromids - by

Addition of SF ₅ Cl to 10-bromo-dec-1-ene and subsequent elimination of HCI obtained (see Example 2).

Olefin variant 1

1) Tetrahydrofuran (75 g) is treated with KOt-Bu (0.12 mol), then pentafluorothio-bromo-dec-1-ene (0.1 mol) is added and stirred at 50 ⁰ C for 12 hrs. The reaction mixture is poured on ice. To gain the Building block (E) -1-pentafluorosulfanyl-deca-1, 9-diene is isolated and purified by laboratory methods.

Olefin variant 2

The alcohol (0.1 mol) in THF (75 g) at 10-20 ⁰ C with MeSO ₂ Cl (0.11 mol) and 0.15 mol NaHCO ₃ transferred to the intermediate methanesulfonic acid ester (reaction time: 3 hours 1 ). The reaction mixture is treated with Na-Ot-Bu (0.15 g) and stirred at 25 ° C for 6 hrs. The reaction mixture is poured on ice. To obtain (E) -i-pentafluorosulfanyl-deca-1, 9-diene is isolated and purified by laboratory methods.

1 (E) -1-Pentafluorosulfanyl-deca-1,9-diene (26 g) is initially charged in benzene (120 g) and reacted under AlCb catalysis (16 g) to give corresponding alkylbenzene. For isolation is quenched with ice, the organic phase separated, filtered and evaporated.

2 The alkylbenzene (34 g) is sulfonylated with sulfur trioxide (17 g). For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. It will Ethanol, then NaOH (4 g), briefly heated, after cooling, the resulting crystals were isolated and dried.

Example 4

1) To give 2- (3) -chloronaphthalene (16 g) in toluene (100 g) alcohol (28 g), prepared according to Example 1, base Na-O-t-Bu (0.2 g) and catalyst Pd-

Given DBA (5 g). After heating (6 hours, 100 ⁰ C) and cooling, the

Alkyl-oxy-naphthalene isolated by standard laboratory methods.

2) To 2- (3) -hydroxy-naphthalene (15 g) in toluene (100 g) are added bromo compound (35 g) prepared according to Example 2 and base Na ₂ CO ₃ (11 g). After heating (3 hours, 80 ⁰ C) and cooling the alkyloxy naphthalene is isolated by conventional laboratory methods.

3) The alkyloxy-naphthalene (41 g) is added without solvent (with sulfur trioxide 12 g) sulfonylated (Temp. At 4O ⁰ C) / then after isolation, salt formation (with a mixture of NaOH 6 g) and water (30 g).

Example 5

1) The hexenol (28 g) prepared according to Example 1, (with bromochloroethane 14 g) in 200 ml THF (from triethylamine additional 10 g) at 4O ⁰ C etherified. The product is isolated using laboratory methods.

2) The chloroethyl ether (35 g) and naphthalene (13 g) are then converted to alkylnaphthalene under AlCb catalysis (26 g). The product is also isolated using laboratory methods.

3) The alkylnaphthalene (44 g) is sulfonylated with sulfur trioxide (17 g) and added to ice / methyl tert-butyl ether for salt formation, the water phase is extracted with this solvent and all organic phases are evaporated. Ethanol is added first, then NaOH (4 g), heated briefly and after cooling, the resulting crystals are isolated and dried.

Example 6

1) The alcohol (28 g) prepared according to Example 1, with the Homoallylchlorid (0.1 mol) and Na ₂ CO ₃ 11 g) in THF (100 g) stirred (at 5O ⁰ C for 4 hours, then treated with isolated laboratory methods of homoallyl ether.

2) The homoallyl ether (0.1 mol) is dissolved in chlorobenzene (100 g), treated with naphthalene (13 g) and AICI3 (26 g) and stirred for 6 hours at 80 ⁰ C, then isolated by conventional laboratory methods, the alkylnaphthalene.

3) The alkylnaphthalene (45 g) is converted into the alkylnaphth sulfonic acid with sulfur trioxide (12 g). For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried.

Example 7

1. Analogously to Example 3, 28 g of alcohol prepared according to Example 1 are reacted with 18 g of 2- (3) -chloro-methylnaphthalene in the presence of 0.2 g of Na-O-t-Bu and 5 g of Pd-DBA.

2. The alkyl-oxy-methyl-naphthalene (42 g) is sulfonated with SO ₃ (12 g) and added to ice / methyl tert-butyl ether for salt formation. The water phase is extracted with this solvency and all org. Phases evaporated. Ethanol is added, then NaOH (4 g), heated briefly and after cooling, the resulting crystals are isolated and dried.

Example 8

H2, Pd / C

1 etherification / variant 1. To 3,3,3-trifluoro-propan-1-ol (11 g) (50 g) in THF the bromohexane (27 g) and Na2CO3 (14 g) and 6 hours at 50 ⁰ C stirred. After isolation with standard laboratory methods, the ether is obtained. 2 Etherification / Variant 2. To 3,3,3-trifluoropropanol (11 g) in THF (50 g) are added the hexanol (21 g) and triphenylphosphine (60 g) and brought to ultrasonic bath for sufficient mixing for 10 minutes. Diisopropyl azodicarboxylate (DIAD, 50 g) turns in 15 minutes

5 was added dropwise and the reaction mixture stirred vigorously for a total of 3 hours.

The solvent is evaporated. Subsequently, cold n-hexane (90 ml) is added, whereby triphenylphosphine oxide precipitates. The solid is filtered off, the solution is evaporated, taken up in dichloromethane (100 g) and filtered through a layer of SiO ₂ . The eluate is evaporated, the

10 residue consists of the product.

3. Debenzylation. [6- (3,3,3-trifluoro-propoxy) -hexyloxymethyl] -benzene (5 g) is taken up in ethanol (30 g) and added at 30 ° C. with addition of catalyst Pd / C (5%) (0, 5 g) and hydrogen (normal pressure) hydrogenated. The

15 reaction solution is filtered and evaporated. In this case, the product is obtained 6- (3,3,3-trifluoro-propoxy) -hexane-1-ol.

4. Friedel-Crafts alkylation

1. Alkylnaphthalene. The alcohol (20 g) is dissolved in chlorobenzene (100 g), added with naphthalene (13 g), then with AICI ₃ (26 g). After heating to 100

O U

⁰ C for 12 h is placed on ice and the organic phase separated. It is filtered, evaporated and the alkylnaphthalene recrystallized. 2. Alkylnaphthalenesulfonic acid

The alkylnaphthalene (31 g) is sulfonylated without solvent with sulfur trioxide (12 g) (temp. Below 40 ⁰ C). For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried.

Example 9

1. The pentane alcohol is obtained analogously to Example 6 by Wiliamson's ether synthesis.

2. Alkoxynaphthalene. To 2- (3) -chloro-naphthalene (16 g) add the pentanol (0.1 mol), Na-Ot-Bu (0.2 g) and Cat Pd-DBA (5 g) for 4 hrs 80 ⁰ C heated and isolated after cooling with laboratory-standard methods, the alkyl-oxy-naphthalene

3. Alkoxynaphthalene sulfonic acid. The alkyl-oxy-naphthalene (33 g) is sulfonylated with SO ₃ (12 g). For salt formation, the reaction mixture is added to ice / methyl tert-butyl ether, the water phase is extracted with this solvent and all org. Phases evaporated. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried.

Example 10

1) The alcohol (20 g), obtainable according to Example 6, is washed with 1-chlorobut-3-ene (0.1 mol) and Na ₂ CO ₃ (11 g) in THF (100 g) at 50 ^° C. for 4 Std stirred, then isolated by conventional laboratory methods of homoallyl ether.

2) The homoallyl ether (0.1 mol) is dissolved in chlorobenzene (100 g), treated with naphthalene (13 g) and AICI ₃ (26 g) and stirred for 6 hours at 80 ⁰ C, then isolated by conventional laboratory methods, the alkylnaphthalene.

3) The alkylnaphthalene (0.1 mol) is converted to the alkylnaphthalene sulfonic acid with sulfur trioxide (12 g). For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried.

Example 11

Xanthate variant

1) xanthogenate. To 200 ml of dimethylformamide (DMF) are added sodium hydride (0.12 mol; 60% paraffin suspension) was added, cooled to 0 ⁰ C, then the Benzyloxypentanol (0.1 mol; dissolved in 30 mL DMF) added. It is stirred for 60-90 min. Then carbon disulphide (0.2 mol) is added dropwise at -5 - 0 ⁰ C and stirred for 2 hrs. Finally, methyl iodide (0.12 mol) is metered in and stirred for 10 to 14 hours at 20 ⁰ C. For product recovery is isolated and purified by laboratory methods.

2) CF3-ether. To a suspension of 1, 3-dibromo-5,5-dimethylhydantoin (0.29 mol) in DCM (500 ml) at -78 ⁰ C initially (HF) ₉ / Py (160 ml; 65%) and then Methylxanthogenat (100 mmol, in 80 ml DCM). The reaction mixture is stirred for 1 hr at -78 ° C and then heated to 0 ⁰ C within 2 h and stirred at this temperature for 2 hrs. After complete reaction, the product is isolated and purified by laboratory methods for product recovery.

3) trifluoromethoxypentanol. The trifluoromethoxypentane benzyl ether (0.1 mol) is taken up in ethanol (60 g) and hydrogenated at 30 ⁰ C with the addition of catalyst Pd / C (5%) (0.5 g) and hydrogen (normal pressure). The reaction solution is filtered and evaporated, in which case the product is obtained.

4) Dissolve the alcohol (17 g) in chlorobenzene (100 g), add naphthalene (13 g), then AICI3 (26 g). After heating to 100 ⁰ C for 12 h is placed on ice and the organic phase separated. It is filtered, evaporated and the alkylnaphthalene recrystallized. 5) The alkylnaphthalene (28 g) is sulfonylated without solvent with sulfur trioxide (12 g) (temp. Below 40 ^° C.) / isolation. For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried.

Example 12

1) To 1- (2) -chloro-naphthalene (16 g) are added the alcohol prepared according to Example 11, (17 g), base Na-Ot-Bu (0.2 g) and cat Pd-DBA (5 g ), heated to 70 ⁰ C for 6 h, then cooled. After product isolation by laboratory methods, the alkyl-oxy-naphthalene is obtained.

2) The alkyloxy-naphthalene (30 g) is sulfonylated with SO ₃ (10 g). For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried

Example 13

The alcohol 1 (17 g), prepared according to Example 11, with bromochloroethane (14 g) in 200 ml of THF under triethylamine addition (10 g) etherified at 40 ⁰ C. The product is isolated using laboratory methods.

2 Subsequently, the chloroethyl ether (23 g) and naphthalene (13 g) at 60 ⁰ C in 3 hours under AICI (26 g) was reacted for ₃ catalysis alkylnaphthalene. The product is also isolated using laboratory methods.

3 Alkylnaphthalenesulfonic acid

The alkylnaphthalene (34 g) is sulfonylated with sulfur trioxide (17 g) and added to ice / methyl tert-butyl ether for salt formation, the water phase is extracted with this solvent, and all the organic phases are evaporated. Ethanol is added first, then NaOH (4 g), heated briefly and after cooling, the resulting crystals are isolated and dried.

Example 14

1) To 3,3,3-trifluoro-propan-i-ol (11 g) is added 1-chloro-pent-4-ene (0.1 mol) and Na ₂ CO ₃ (11 g) in THF (100 g), stirred under reflux for 4 h, then isolated by conventional laboratory methods of allyl ether.

2) 5- (3,3,3-trifluoro-propoxy) -pent-1-ene (18 g) is initially charged in benzene (100 g), then 6O ⁰ C under AICI3 catalysis (26 g) for 6 h heated and converted to the corresponding alkylbenzene. Product isolation is carried out according to laboratory methods.

3) The alkylbenzene (25 g) is sulfonylated with sulfur trioxide (12 g). For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried.

Example 15 ^D ^ - \

According to Example 11, the intermediate 5-trifluoromethoxy-pent-1-ene is first obtained from pent-4-en-1-ol by xanthate method.

1) The 5-trifluoromethoxy-pent-1-ene (15 g) is initially charged in benzene (120 g) and reacted under AlCb catalysis (16 g) to the corresponding alkylbenzene. For isolation is quenched with ice, the organic phase separated, filtered and evaporated.

2) The alkylbenzene (22 g) is sulfonylated with sulfur trioxide (17 g). For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried.

Example 16 3- (Bis-trifluoromethyl-amino) -propan-1-ol:

To a stirred solution of 9-BBN (240 ml) in THF (200 ml) is added dropwise the bistrifluoroallylamine (23.2 g, 120 mmol) at RT.

After 24 hours the reaction mixture is cooled to 0 ⁰ C and then 3M NaOH (44ml, heat) and 30% strength H ₂ O ₂ -

Solution ((4OmI) (countercooled with dry ice / acetone bath)

Mixture is heated for 1 h to 50 ⁰ C (the colorless solid goes back into

Solution) and then cooled to RT.

For working up, saturated NaCl solution is added, the phases are separated, the organic phase is extracted by shaking again with Na ₂ SO ₃ solution and then dried over sodium sulfate, the

Desiccant filtered off. The solvent is stripped off and the residue (product) is distilled.

Example 17

1-bromo-3- (Bis-trifluoromethyl-amino) -propane:

The alcohol (110 mmol) is initially charged in dry DCM (0.2 molar solution) and admixed with triphenylphosphine (154 mmol, 1.4 eq) and then in portions with tetrabromomethane (CBr ₄ : 165 mmol, 1.5 eq). The reaction is stirred for 4 h and then washed with sat. Quenched NaHCO ₃ solution, extracted with MTB and dried over sodium sulfate. The resulting crude product is isolated by distillation.

1) Dissolve 1-bromo-3- (bis-trifluoromethyl-amino) -propane (18.2 g) in 100 g of chlorobenzene, add naphthalene (13 g), then AICI ₃ (13 g). After heating to 100 ° C for 12 h is placed on ice and the organic phase separated. The org. Phase is evaporated and the alkylnaphthalene recrystallized

2) The alkylnaphthalene (32 g) is sulfonylated without solvent with sulfur trioxide (12 g) (temp. Below 40 ⁰ C). For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried

Example 18

1) To 1- (2-) chloronaphthalene (16 g) is added 3- (bis-trifluoromethyl-amino) -propan-1-ol (21 g), prepared according to Example 16, and base Na-Ot-Bu (0, 2 g) and the catalyst Pd-DBA (5 g). After heating (6 h, 100 ⁰ C) and cooling, the alkyloxy-naphthalene is isolated by conventional laboratory methods.

2) The alkyloxynaphthalene (30 g) is converted to the alkylnaphth sulfonic acid with sulfur trioxide (12 g). For salt formation on ice / methyl tert-butyl ether, extract the water phase with this solvency and all org. Evaporate phases. Ethanol is added, then NaOH (4 g), briefly heated, after cooling, the resulting crystals are isolated and dried.

Example 19 4- (12-trifluoromethoxy-dodecyl) -benzenesulfonic acid sodium salt

(12-trifluoromethoxy-dodecyl) -benzene

To a solution of 3.33 g of i-bromo-12-trifluoromethoxy-dodecane in 10 ml of benzene is added at 0 ⁰ C under nitrogen and with stirring 0.5 g AICb and stirred for 48 h at 20-25 ⁰ C (analog Gilman, Meals, J. Org. Chem., 1943, 126). For product isolation, the reaction mixture is added to ice, the organic phase separated, filtered and the solvency at 50 ⁰ C in vacuo. It falls to a colorless, waxy solid.

4- (12-trifluoromethoxy-dodecyl) -benzenesulfonic acid sodium salt

A solution of 5.8 g (12-trifluoromethoxy-dodecyl) benzene in 26 ml of 1, 2-dichloroethane is added with stirring at 0 ⁰ C under nitrogen with 2.67 g of chlorosulfonic acid and for 3 hours at 15-20 ⁰ C. touched. For product isolation, the reaction mixture is added to ice, the organic phase separated, filtered and the solvency at 40 ⁰ C in vacuo. The residue is treated with 18 ml of 1 M NaOH, stirred, then the water is carefully removed from the aqueous phase in vacuo. It attracts a pale yellow, amorphous solid.

H NMR (DMSO; 300 MHz): 1, 24-1, 28 (10H, m), 1, 30 (2H, m), 1, 52 (2H, m), 1, 58 (2H, m), 1, 68-1, 70 (4H, m) _I 2.63 (2H, t), 3.94 (2H, t), 7.17 (2H, m), 7.53 (2H, m) MS: 392 (M ⁺ - Na ⁺ ) Example 20 4- (12-trifluoromethylsulfanyl-dodecyl) -benzenesulfonic acid sodium salt

(12-Trifluoromethylsulfanyl-dodecyl) -benzene

Analogous to the recovery of (12-trifluoromethoxy-dodecyl) benzene is dodecane -Bromo-12-trifluoromethylsulfanyl-dosed to a solution of 3.49 g of 1 in 10 ml of benzene under stirring at 0 ⁰ C under nitrogen, 0.5 g AICI ₃ and for 48 hours at 20-25 ⁰ C. (analog Gilman; Meals; J. Org Chem, 1943.. 126). For product isolation, the reaction mixture is added to ice, the organic phase separated, filtered and the solvency at 50 ° C in vacuo. It comes to an almost colorless solid.

4- (12-Trifluoromethylsulfanyl-dodecyl) -benzenesulfonic acid sodium salt

To a solution of 5.6 g (12-trifluoromethylsulfanyl-dodecyl) benzene in 24 ml of 1, 2-dichloroethane is added under stirring at ^{0 0} C under nitrogen 2.43 g of chlorosulfonic acid and for 3 hours at 15-20 ⁰ C. touched. For product isolation, the reaction mixture is added to ice, the organic phase separated, filtered and the solvency at 40 ⁰ C in vacuo. The residue is mixed with 16 ml of 1 M NaOH, stirred, then the water is carefully removed from the aqueous phase in vacuo. An amorphous solid is produced.

H-NMR (DMSO; 300 MHz): 1 _l 22-1, 27 (8H _l m), _1> 31-1 _l 34 (4H, m) _l _I 1 52 (2H, m), 1, 58 (2H , m), 1, 64-1, 68 (4H _I m), 2.63 (2H, t), 2.84 (2H, t), 7.17 (2H, m) ₎ 7.53 (2H, m)

MS: 409 (M ⁺ - Na ⁺ )

Example 21

4- [10- (Bis-trifluoromethyl-amino) decyl] benzene sulfonic acid sodium salt

(IO-phenyl-decyl) -bis-trifluoromethyl-amine

Analogously to the recovery of (12-trifluoromethoxy-dodecyl) benzene is added to a solution of 3.72 g (IO-bromo-decyl) -bis-trifluoromethyl-amine in 10 ml of benzene with stirring at 0 ⁰ C under nitrogen 0.5 g AICI ₃ and stirred for 48 h at 20-25 ⁰ C (analogous Gilman, Meals, J. Org. Chem., 1943, 126). For product isolation, the reaction mixture is added to ice, the organic phase separated, filtered and the solvency at 50 ⁰ C in vacuo. An amorphous solid is produced.

4- [10- (Bis-trifluoromethyl-amino) decyl] benzene sulfonic acid sodium salt

To a solution of 7.00 g (IO-phenyl-decyl) -bis-trifluoromethyl-amine in 29 ml of 1, 2-dichloroethane is added with stirring at ^{0 0} C under nitrogen 2.89 g of chlorosulfonic acid and for 3 hours at 15 -20 ⁰ C stirred. For product isolation, the reaction mixture is added to ice, the organic phase separated, filtered and the solubility at 40 ⁰ C in Vacuum removed. The residue is treated with 19 ml of 1 M NaOH, stirred, then the water is carefully removed from the aqueous phase in vacuo. It turns to a yellowish, amorphous solid.

H-NMR (DMSO; 300 MHz): 1, 23-

1, 28 (8H, m), 1, 52 (2H, m), 1, 58 (2H, m), 1, 68 (2H, m), 1, 73 (2H, m) _> _2I 63 (2H _,)) t 3.18 (2H, t), 7.17 (2H, m), 7 _I 53 (2H, m) MS: 409 (m ⁺ - Na ⁺⁾

Example 22

^ - (bis-trifluoromethyl-amino-1-dodecanecarboxylic acid) -sulfophenylester sodium salt

12- (Bis-trifluoromethyl-amino) -dodecancarbonsäure

To a solution of 4.72 g of 12- (bis-trifluoromethyl-amino) -dodecan-1-ol in 56 ml of acetone is added under stirring and under nitrogen at 0 ⁰ C Jones reagent (obtained by adding 1.68 ml of conc H ₂ SO ₄ at 0 ^° C. to a solution of 2.56 g CrO ₃ in 11 ml water) and stirred for 1 h at 20 ^° C. For product isolation, the reaction mixture is filtered and the solvency at 30 ⁰ C removed in vacuo from the resulting eluate. The crude product is chromatographed over silica gel in a mixture of cyclohexane / ethyl acetate (8: 2). An amorphous solid is produced.

To a solution of 3.51 g of 12- (bis-trifluoromethyl-amino) - dodecanecarboxylic acid in 25 ml of toluene 12 g of SOCl _{2 is} metered with stirring at 0 ⁰ C under nitrogen and stirred for 0.75 hours at 60-70 ⁰ C. , then remove the excess SOCl ₂ and about 50% of the toluene by distillation. Then 10 ml of THF, 2.45 g of 4-hydroxyphenylsulfonic acid sodium salt and 4 ml of triethylamine is added to the remaining in toluene acid chloride at 0-10 ⁰ C successively and stirred for 4 hours at 25 ⁰ C. For product isolation, the reaction mixture is filtered and the solvents removed at 30-40 ⁰ C in vacuo from the resulting eluate. There is a partially crystalline solid.

H-NMR (DMSO; 300 MHz): 1, 23-1, 31 (14H, m), 1, 55 (2H, m), 1 _I 73 (2H, m), 2.50 (2H ₁ ITi), 3.18 (2H, t), 4.11 (2H, t) _I 7.25 (2H, m) _I 8.07 (2H ₎ m) MS: 489 (M ⁺ - Na ⁺ )

Example 23 4- [12- (bis-trifluoromethyl-amino) -dodecyloxy] -benzenesulfonic acid

sodium salt

To a solution of 8.80 g (12-bromo-dodecyl) -bis-trifluoromethyl-amine in 44 ml of DMF with stirring at 20 ⁰ C under nitrogen 4.84 g of 4-hydroxyphenylsulfon-acid sodium salt and 0, 97 g of NaOH (powdered) and stirred for 24 h at 55-65 ⁰ C. For product isolation, the reaction mixture is filtered and the solvency at 40-60 ⁰ C removed in vacuo from the resulting eluate. The resulting crude product is mixed with 55 ml of ethanol, heated to 40 ⁰ C and the suspension cooled to ^{0 0} C. After separation of the solid phase, a pale brown solid is obtained, which is dried at 30 ⁰ C in vacuo.

H-NMR (DMSO; 300 MHz): 1, 23-1, 28 (14H, m), 1, 52 (2H, m) ₎ 1, 73-1, 80 (4H, m), 3.18 (2H , t), 3 _l 98 (2H, t), 6.98 (2H _l m), 7 _I 85 (2H, m) MS: 475 (m ⁺ - Na ⁺⁾

Example 24 Determination of Biochemical Degradability

The biochemical degradability of the compounds is determined according to the Zahn-Wellens test in accordance with the European Commission publication: Classification, packaging and labeling of dangerous substances in the European Union, Part II - Test methods, Annex V - Methods for the determination of physico-chemical properties, Toxicity and Ecotoxicity, Part B, Biochemical Degradability - Zahn-Wellens Test (C9.), January 1997, pages 353-357. Batch volume: 1, 5 1

Activated sludge concentration: 1 gTS / l

Origin of the sludge: WWTP of Merck KGaA;

Darmstadt (not adapted) Use of the test substances: approx. 100 to 200 mg / l as DOC ventilation: with purified air

Processing of samples: filtration (medium-hard filter)

Determination of the DOC: According to the difference method with a device from Dimatec

Further details on the method can be found in the above-mentioned publication or in the OECD Guideline for the testing of Chemicals, section 3, degradation and accumulation, method 302 B, page 1-8, adopted: 17.07.92, the content of which relates expressly to the disclosure content of the present application.

In addition, in addition to the degradation of the compound itself in the test, the degradation of the fluorine-containing groups is observed via a fluoride determination:

Method: Ion chromatography

Device: Dionex 120 Detector Type: Conductivity detector

Column: AS9HC

Eluent: sodium carbonate solution, 9 mmol / l

Flow rate: 1 ml / min

Literature: EN ISO 10304-2

Example 25: Determination of Surface Tension:

Device: Tensiometer from Krüss (model K12) Temperature of the measuring solutions: 20 ^° C.

Used measuring module: ring

Concentration of the measuring solutions: approx. 0.5 to 3.0 g / l in deionized

water

Further details on the method can be found in the European publication

Commission: Classification, Packaging and Labeling of Dangerous Substances in the European Union, Part II - Test Methods, Annex V - Methods for the determination of physico-chemical properties, toxicity and ecotoxicity, Part A, Surface tension (A.5), January 1997, Page 51 -57 and also the OECD Guideline for the testing of Chemicals, section 1, physical-chemical properties, method 115, page 1-7, adopted: 27.07.95, the contents of which belong expressly to the disclosure content of the present application.

Claims

claims

1. Compounds having an arylsulfonate group, a spacer and at least one group Y, wherein Y is CF ₃ - (CH ₂ ) _a -O-, SF ₅ -, CF ₃ - (CH ₂ ) _a - S-, CF ₃ CF ₂ S-, [CF ₃ - (CH ₂ ) _a ] ₂ N- or [CF ₃ - (CH ₂ ) _a ] NH-, where a is an integer selected from the range of 0 to 5 or

stands, where

Rf is CF ₃ - (CH ₂ ) _r -, CF ₃ - (CH ₂ ) _r -O-, CF ₃ - (CH ₂ ) _r -S-, CF ₃ CF ₂ -S-, SF ₅ -

(CH ₂ ) _r or [CF ₃ - (CH ₂ ) _r ] ₂ N-, [CF ₃ - (CH ₂ ) _r ] NH- or (CF ₃ ) ₂ N- (CH ₂ ) _r -, 5 B for a single bond, O, NH, NR, CH ₂ , C (O) -O, C (O) ₁ S, CH ₂ -O,

OC (O), NC (O), C (O) -N, OC (O) -N, NC (O) -N, O-SO ₂ or SO ₂ -O

R is alkyl of 1 to 4 C atoms, b is O or 1 and c is O or 1, q is O or 1, where at least one of b and q is 1, and r is O , 1, 2, 3, 4 or 5.

2. Compounds according to claim 1, characterized in that the spacer contains no fluorine atoms. ₅

3. Compounds according to claim 1 or 2, characterized in that the spacer is a saturated or unsaturated, branched or unbranched hydrocarbon moiety, wherein the hydrocarbon moiety in the chain or in a branch may optionally be provided with one or more heteroatoms. 0

4. Compounds according to one or more of claims 1 to 3, characterized in that they are of the formula IA or IB

where Y is as defined in claim 1,

A spacer as defined in one or more of claims 1 to 3, M is a metal cation and m is 1, 2 or 3.

5. Compounds according to one or more of claims 1 to 4, characterized in that the spacer has one of the following meanings

- (CH ₂ ) _n -,

- (CH ₂ ) -CH (Hal) - (CH ₂ ) (n-ir, -CH = CH- (CH ₂ ) (ni) -,

- (CH ₂ ) _n -O-,

-CH ₂ CH = CH- (CH ₂ ) ( _H-1 ) -,

- (CH ₂ ) _nr Ar- (CH ₂ ) _(n - _-ir - (CH ₂ ) niC≡C- (CH ₂ ) n- or

- (CH ₂ ) nQ- (CH ₂ ) _n -, where n and n 'independently of one another are an integer from the range 1 to 30, Hal is Cl, Br or I and p is an integer from the range 1 to 4,

Ar stands for aryl, Q stands for O, S or N.

6. Compounds according to one or more of claims 1 to 5, characterized in that the group Y CF ₃ - (CH ₂ ) aO- with a = 0, 1, 2,

5 3, 4 or 5, preferably a = 0, 1 or 2, means.

7. Compounds according to one or more of claims 1 to 6, characterized in that the group Y SF ₅ means.

10 8. Compounds according to one or more of claims 1 to 7, characterized in that the group Y CF ₃ - (CH ₂ ) _a -S- with a = 0, 1, 2, 3, 4 or 5, preferably a = 0, 1 or 2, means.

9. Compounds according to one or more of claims 1 to 8, 15 characterized in that the group Y CF ₃ -CF ₂ -S- means.

10. Compounds according to one or more of claims 1 to 9, characterized in that the group Y [CF ₃ - (CH ₂ ) _a ] ₂ N- with a = 0, 1, 2, 3, 4 or 5, preferably a = 0, 1 or 2, means.

20

11. Compounds according to one or more of claims 1 to 10, characterized in that the group Y [CF ₃ - (CH ₂ ) _a ] NH- with a = 0, 1, 2, 3, 4 or 5, preferably a = 0, 1 or 2, means.

25 12. Compounds according to one or more of claims 1 to 11, characterized in that the group Y

means, where Rf is CF ₃ - (CH ₂ ) r-, CF ₃ - (CH ₂ VO-, CF ₃ - (CH ₂ ) r S-, CF ₃ CF ₂ -S-, SF ₅ - (CH ₂ Jr or [CF ₃ - (CH ₂ ) J ₂ N-, [CF ₃ - (CH ₂ ) JNH- or (CF ₃ ) ₂ N- (CH ₂ ) _r , B is a single bond, O, NH, NR, CH ₂ , C (O) -O, C (O), S, CH ₂ -O, OC (O), NC (O), C (O) -N, O-C (O) -N, NC (O) - N, O-SO ₂ or SO ₂ -OR is alkyl having 1 to 4 C atoms, b is O or 1 and c is O or 1, q is O or 1, at least one radical of b and q is 1 and r is O, 1, 2, 3, 4 or 5.

13. A process for the preparation of the compounds according to the invention, characterized in that a compound of the formula II Y spacer Z II wherein Y and -Spacer- have one or more of claims 1 to 12 meanings and Z is OH, Br, Cl or Vinyl, is reacted with the corresponding aromatic, selected from the group benzene or naphthalene, and then carried out a sulfonation and salt formation.

14. Composition comprising at least one compound according to one or more of claims 1 to 12.

15. Composition according to claim 14, characterized in that a suitable carrier for the respective purpose and optionally further specific active ingredients are included.

16. Composition according to claim 14 or 15, characterized in that it is in the means to dye and lacquer preparations, fire-extinguishing agents,

Lubricants, detergents and cleaners, deicers or

Water repellent for textile finishing or glass treatment is.

17. A process for preparing a composition according to one or more of claims 14 to 16, characterized in that at least one compound is mixed according to one or more of claims 1 to 12 with a suitable carrier and optionally with other specific active ingredients.

18. Use of compounds according to one or more of claims 1 to 12 as surfactants.

19. Use of compounds according to one or more of claims 1 to 12 as hydrophobizing or Oleophobiermittel, in particular in the surface modification of textiles, paper, glass, porous building materials or adsorbents is used.

20. Use of compounds according to one or more of claims 1 to 12 as an antistatic agent, in particular in the treatment of textiles, such as clothing, carpets and carpets, upholstery in furniture and automobiles, non-woven textile materials, leather goods, papers and carton, wood and wood-based materials, mineral substrates such as stone, cement, concrete, gypsum, ceramics, such as glazed and unglazed bricks, stoneware, porcelain, and glasses, as well as for plastics and metallic substrates.

21. Use of compounds according to one or more of claims 1 to 12 as additives in preparations for

Surface coating, such as printing inks, paints, paints, varnishes, photographic coatings, special coatings for semiconductor photolithography, such as photoresists, top antireflective coatings, bottom antireflective coatings, or in additive formulations for the addition of appropriate preparations.

22. Use of compounds according to one or more of claims 1 to 12 as a foam stabilizer and / or to support film formation, in particular in fire-extinguishing foams.

23. Use of compounds according to one or more of

Claims 1 to 12 as an interface mediator or emulsifier, in particular for the production of fluoropolymers.

24. Use of compounds according to one or more of claims 1 to 12 as an antimicrobial agent, in particular as a reagent for the antimicrobial surface modification.