EP2035363A1

EP2035363A1 - Fluorosurfacants

Info

Publication number: EP2035363A1
Application number: EP07764995A
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: US20090264525A1; WO2008003444A1; DE102006031149A1; US8067625B2; JP2009541400A

Abstract

The invention relates to fatty acid esters of polyols or sulphonated fatty acid esters or sulphonated fatty acid amides having at least one 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)rO-, CF3-(CH2)rS-, 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), C(O)-N1 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 producing said compounds and to the use of said surface-active compounds.

Description

fluorosurfactants

The present invention relates to fatty acid esters of polyols or sulfonated fatty acid esters or sulfonated fatty acid amides having 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

means, where

Rf is CF ₃ - (CH ₂ Jr, CF ₃ - (CH ₂ ) _r O-, CF ₃ - (CH ₂ ) _r -S-, CF ₃ CF ₂ -S-, SF ₅ - ₅ (CH ₂ ) _r or [CF ₃ - (CH ₂ Jr] ₂ N-, [CF ₃ - (CH ₂ ) JN H- 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 0, 1, 2, 3, 4 or 5, preparation process for these compounds and uses of these surface-active compounds.

Fluorosurfactants have a superior ability to reduce surface energy, for example, in the hydrophobization of

Surfaces, such as textile impregnation, the hydrophobization of glass, or the so-called deicing of aircraft wings, is used.

In general, however, fluorosurfactants contain perfluoroalkyl substituents that inQ allow the environment through 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., JL Butenhoff, GW Olsen, JC ^O'Connor, AM Seacat, RG Perkins, LB Bieget, 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. In this connection, compounds which leave behind no persistent organofluorine degradation products are particularly advantageous.

From the company Omnova polymers are sold whose side chains have terminal CF ₃ - or C ^ Fs groups. In the International patent application WO 03/010128 are perfluoroalkyl-substituted amines described acids, amino acids and thioether, a C ₃ - having perfluoroalkyl group - _20th

JP-A-2001/133984 discloses surface-active compounds containing perfluoroalkoxy chains which are suitable for use in antireflective

Coatings are suitable. 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 pentafluorosulfurane group or at least one terminal trifluoromethoxy group and have a polar end group, are surface-active and are excellently suitable as surfactants.

Fatty acid esters of polyols and sulfonated fatty acid esters that have no F atoms are known as surfactants. These fatty acid esters of polyols are used, for example, as emulsifiers for food and in cosmetics.

This class of fatty acid esters of polyols or sulfonated fatty acid esters or sulfonated fatty acid amides 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 fatty acid esters of polyols according to the invention or sulfonated fatty acid esters or sulfonated fatty acid amides having at least one Y group, 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

in which

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, 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 0, 1, 2, 3, 4 or 5, surface active and excellently suitable as surfactants.

A first subject of the invention are therefore fatty acid esters of polyols or sulfonated fatty acid esters or sulfonated fatty acid amides having at least one group Y, wherein Y is CF ₃ - (CH ₂ ) _a -O-, SF ₅ -, CF ₃ - (CH ₂ J _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

^ _c means, 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 Jr or [CF ₃ - (CH ₂ Jr] 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 ₁ O-SO ₂ or SO ₂ -O,

2Q 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.

In this case, the compounds according to the invention preferably contain no further fluorinated groups in addition to the stated fluorinated groups Y.

The fatty acid ester derived from fatty acids according to the invention from that _OQ can be saturated or unsaturated, and 4 to 25 carbon atoms, preferably 8 to 22 carbon atoms, particularly preferably 12 to 20 carbon atoms. The Fatty acids may also carry, for example, OH groups in the side chain.

Examples of fatty acids include lauric acid (C ₁₁ H ₂₃ COOH), myristic acid (C ₃ H ₂₇ COOH), palmitic acid (C ₅ H _3I COOH), stearic acid (C ₇ H ₃₅ COOH),

Oleic acid (Ci ₇ H ₃₃ COOH), linoleic acid (C ₁₇ H ₃₁ COOH), ricinoleic acid (Ci ₇ H ₃₂ (OH) COOH) ₁ linolenic acid

(CH ₃ CH ₂ CH = CHCH ₂ CH = CH ₂ CH = CH (CH ₂ ) ₇ COOH), arachic acid (Ci ₉ H ₃₉ COOH) or erucic acid (C ₂₁ H ₄₃ COOH).

In a variant of the invention, straight-chain fatty acids are preferred, i. preferably with 8, 10, 12, 14, 16, 18, 20 or 22 C atoms, particularly preferably with 12, 14, 16, 18 or 20 C atoms. However, it is also possible to use synthetic fatty acids with an odd number of carbon atoms.

In the fatty acid esters of the invention, the group Y is preferably terminal to the ester function. For fatty acids having free OH groups in the side chain, these may also be replaced by Y, in particular by the group Y selected from the subgroup CF ₃ - (CH ₂ ) _a -O-, where a is an integer selected from the range from 0 to 5 or

means, where

Rf is CF ₃ - (CH ₂ Jr, 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 ) J ₂ N-, [CF ₃ - (CH ₂ ) JNH- or (CF ₃ ) ₂ N- (CH ₂ ) _r -,

B is 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 C atoms, b is O or 1 and c is 0 or 1, q is 0 or 1, wherein at least one of b and q is 1, and r is 0 , 1, 2, 3, 4 or 5.

In a variant of the invention, the fatty acid is esterified with polyols, wherein in the fatty acid ester of the polyol radical of a radical -0-CH ₂ - (CHOH) _n -CH ₂ - OH with n = 1, 2, 3, 4 or 5, a monosaccharide radical , a disaccharide radical or an oligosaccharide radical.

Examples of the polyols to be esterified HO-CH ₂ - (CHOH) _n -CH ₂ -OH with n = 1, 2, 3, 4 or 5 are glycerol (or synonymously glycerol), D-threitol, L-threitol, erythrol , D-arabinitol, L-arabinitol, adonitol, xylitol, D-sorbitol, D-glucitol, D-mannitol, dulcitol, galactitol or even the tetravalent branched alcohol pentaerythritol.

From the group of these polyols are preferably used glycerol, erythrol, pentaerythritol, xylitol, sorbitol or mannitol, more preferably glycerol or sorbitol.

Examples of monosaccharides to be esterified are ribose, arabinose xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribulose, xylulose, psicose, fructose, sorbose or tagatose. In this list both isomers, i. each contain the D or L forms.

From the group of monosaccharides, glucose, galactose or fructose are preferably used.

Examples of disaccharides to be esterified are sucrose (also called sucrose), lactose, trehalose, maltose, cellobiose, gentiobiose or melibiose. This list includes both the α and β forms. From the group of disaccharides are preferably sucrose or lactose, particularly preferably sucrose used.

Examples of polysaccharides to be esterified include trisaccharides such as raffinose, pseudo oligosaccharides such as acarbose, but also amylose, amylopectin, xanthan, inulin, chitin, pectins or cellulose.

In the case of the fatty acid esters of polyols according to the invention, the esterification can in each case be completely equal to the number of hydroxyl groups in the

Polyol residue adapted, or the esterification may be incomplete, i. there are both esterified and free hydroxyl groups in the polyol residue.

Depending on the application, as disclosed below, defined compounds, i. Fatty acid esters are used with only one variant of the esterification of the polyol, or mixtures of these fatty acid esters with different variants of the esterification of the polyol. The fatty acid esters of the polyols according to the invention with at least one fatty acid radical containing the group Y, as defined above, are preferably used. The composition of the mixtures can be controlled by the choice of reagents and reaction conditions.

In a further preferred embodiment, fatty acid esters of polyols are particularly preferred in which the polyol residue is derived from glycerol, sorbitol or sucrose.

In the group Y, a is preferably 0, 1 or 2, particularly preferably 0 or 2, very particularly preferably 0 and r is preferably 0 to 3, in particular 0 to 1.

In a variant of the present invention, it is preferred if in the group Y q is 0 and at least one c and / or b is in each case 1 - -

stand. In particular, it is preferred that all c and b are 1, i. the aromatics are substituted in the o- and / or p-position with fluorine groups, in particular in o, p, o-position.

In a further variant of the invention it is preferred if all q and b are each 0 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-position with fluorine groups, in particular in o, o-position.

In a further variant of the invention, it is preferred that all c and q are each 0 and b is 1, i. the aromatics are substituted in the p position with fluorine groups.

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, where r is preferably 0. , CF ₃ S-, CF ₃ CF ₂ -S-, SF ₅ - or - (CF ₃₎ ₂ N- particularly preferred are the groups Rf = CF ₃ correspond to the invention.

The group Y, as defined above, which determines the modification of the fatty acid, in a preferred variant of the invention consists of CF ₃ -O-, CF ₃ -CF ₂ -S-, CF ₃ -S-, (CFs) ₂ N- or

in which

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 Jr 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, 0-C (O) ₁ NC (O), C (O) -N, QC (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. ,

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

In a particularly preferred embodiment of the present 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-, (CF ₃ ) ₂ -N- and (CF ₃ -CH ₂ -CH ₂ ) ₂ -N-, especially for CF ₃ -, CF ₃ -O-, CF ₃ -S- and (CFg) ₂ -N-.

A further preferred variant of the invention comprises the groups Rf equal to 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), CF ₃ -CH ₂ -CH ₂ -S- Ar-OC (O), (CFa) ₂ -N-Ar-OC (O) and (CF ₃ -CH ₂ -CH ₂ ) ₂ -N-Ar-OC (O), in particular equal to 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 represents 0 and at least one c and / or b each represents 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 0 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.

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.

Another preferred embodiment is fatty acid esters of sorbitol, which can be represented by the formula IA

in which

R 1 to R 6 represent a fatty acid radical containing the group Y as defined above or H, where the radicals R 1 to R 6 may not all be equal to H. - -

Another preferred embodiment is fatty acid esters of sucrose, which can be represented by the formula IB

in which

R 1 to R 8 is a fatty acid radical containing the group Y as defined above or H, wherein the radicals R 1 to R 8 may not all be equal to H.

The preparation of the fatty acid esters of polyols according to the invention can be carried out according to methods known to the person skilled in the art from literature. The esterification reaction conditions are well known in the art, and selecting the appropriate reaction conditions is standard in the art. Preferably, the esterification with the free acid takes place, for example, with acid catalysis, but it can also be carried out enzymatically. Another variant is the reaction of fatty acid chlorides under mild conditions in the presence of pyridine.

Fatty acid esters of carbohydrates, i. the mono-, di- or polysaccharides are prepared alkali-catalyzed, for example, via the fatty acid methyl esters, wherein the resulting methanol is distilled off, wherein the

Temperature should remain below 100 ^c C in this reaction. Literature in this regard is Ullmann's Encyclopaedia of Industrial Chemistry Release 2006, 7th Edition, there Contribution "Surfactants", Author: Kurt Kosswig, DOI: 10.1002 / 14356007.a25_747.

The invention therefore further provides a process for the preparation of the fatty acid esters of polyols according to the invention, characterized - -

in that a fatty acid containing the group Y ₁ as defined above or a derivative of this fatty acid is esterified with a polyol.

Derivatives of this fatty acid are, as previously described, fatty acid chlorides or lower esters of the fatty acids, for example the methyl esters.

Examples of the synthesis of the modified saturated fatty acids are shown in the following scheme. The synthesis of the modified unsaturated fatty acids is accordingly analog.

1. For the group Y = OCF ₃ and for saturated fatty acids CH ₃ - (CH ₂ ) _s -i- COOH, whose alkylene units are represented in the schemes by (CH ₂ ) _S , where s can be 4 to 25: variant A:

1. NaK THF DBH,

2. CS ₂ 70% HF pyridine

Z [OWJH ³ ^ '. Z (CH ₂ J ₁ OCSSMB ^ ² ^ Z (CH ₂ J ₁ CCF ₃

AB _C

Z = HaI, OPg (Pg = protecting group)

The aliphatic OCF ₃ group can be obtained, for example, from a precursor A = Z (CH ₂ ) _s -OH via the fluorodeulfuration of xanthogenates (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, p. 67 ff., P. 144 f.). The corresponding disclosure of the method mentioned in the cited references thus expressly also belongs to the disclosure of the present application.

The derivatization to the acid is then carried out from the deprotected alcohol by oxidation. - -

Alternatively, the modified fatty acid can be prepared according to variant B:

2-bromoethanol is converted to the fluoroformate and then the

Carbonyl group transformed with SF ₄ to OCF ₃ -Ether. Literature: 5 1. Aldrich, PE; Sheppard, William AJ Org. Chem. 1964, 29, 11-15

2. Sheppard, William A. et al. J.Org:Chem. 1964, 29, 1-11

3. Yagupol ^' skii, LM; Alekseenko, AN; N ^' Chenenko, A.Y. Ukrainskii Khimicheskii Zhurnal 1978, 44, 1057-1059 Q The fatty acid is now obtained by: 1. Williamson ether synthesis, 2. the subsequent hydrogenolytic debenzylation, and 3. the subsequent oxidation with stoichiometric amounts of sodium periodate and catalytic Amounts of ruthenium chloride. 5

⁰ 2. For the group Y = CF ₃ - (CH ₂₎ _a -O- with a = 1 to 5 and for saturated fatty acids, the alkylene units are shown in Schemes by (CH ₂₎ _S, where s may be the same 4 to 25 can:

The introduction of the CF ₃ - (CH ₂ ) _a -O group is achieved by reaction of CF ₃ - (CH ₂ ) _a -OH with a = 1, 2, 3, 4 or 5 with a primary hydroxy ester via Mitsunobu reaction ( Mitsunobu, O. Synthesis, 1981, 1) to the corresponding fatty acid esters.

O I D_ / IIΛAΛLD> ,, r PπPhiß3 Q

HO- (CH ₂ ) A ₀ / FF ₃₃ CC - ((CCHH ₂₂ )) _aa --OOHH ^ F ₃ C- (CH ₂ ) _a -O- (CH ₂ ) _s - ( _. W ^{-TH ■} - FO - N NNaaaOuuHiiϊϊ

DIAD = diisopropyl azodicarboxylate

Alternatively, the modified fatty acid can also be prepared by double etherification of the alcohol CF ₃ - (CH ₂ ) _a -OH with a = 1 to 5 to a corresponding brominated alkene and subsequent ozonolysis with oxidative work-up. F ₃ C- (CH ₂ ) _a -OH + Br- (CH ₂ ) _S -CH = CH- (CH ₂ ) _S -Br

T ^HF

F ₃ C- (CH ₂ ) _a -O- (CH ₂ ) _s -CH = CH- (CH ₂ ) _s -O- (CH ₂ ) _a -CF ₃

O ₃ / H ₂ O ₂

2xF ₃ C- (CH ₂ ) _a -O- (CH ₂ ) _s -COOH - -

3. For the group Y = SF ₅ and for saturated fatty acids whose alkylene units in the schemes are represented by (CHb) ₅ , where s can be 4 to 25:

The aliphatic SF ₅ 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 a SF ₅ function also (P. Kirsch, M. Bremer, M. Heckmeier, K. Tarumi, Angew Chem. 1999, 111, 2174-2178; Angew. Chem. Int. Ed. Engl. 1999, 38, 1989-1992). The corresponding disclosure of the method mentioned in the cited references is thus expressly also to

Disclosure of the present application. Examples are given in the following scheme:

or altyllithium ^ derivatization for Z = OPg (eg OBn):

Z (

WZ - -

HOOC (CH ₂ ) _S. ₃ CH = CHSF ₅ CrO ₃ , H ₂ SO ₄ ^

Y or Z

Oxidation HOOC (CH ₂ ) ^ ₁ SF ₅

AF

An alternative synthesis of the SF ₅ -modifιzierten fatty acid is the addition of SF ₅ CI to a terminal double bond of a fatty acid ester, such as a methyl ester, the elimination of HCl and subsequent ester cleavage.

4. For the group Y = CF ₃ -S or CF ₃ -CF ₂ -S and for saturated fatty acids whose alkylene units are represented in the Schemes by (CH ₂ ) _S , where s can be 4 to 25:

Acids or acid derivatives with a terminal thiol group are commercially available (by whom?) Or can be prepared by methods known in the art, for example, as described in insert please citation. The conversion into the desired CF ₃ -S or CF ₃ -CF ₂ -S group takes place, for example, according to the following scheme and according to Anselmi, E. et al. J. Fluorine Chem. 2000, 105, 1, 41-44 or, where appropriate, preparable by:

(trifluoromethyl) dibenzoselenophenium triflate (Umemoto's reagent): T. Umemoto et al. J. Am. Chem. Soc. 1993, 115, 2156-2164.

Or via: N.V. Ignatiev, Ukr. Khim. Zh. 2001, No. 10, pp. 98-102.

Pf - f * ρ f * PX ⁼ Cl, Br, I

^{3 2 5} R = Me or Et

RfX NaSO ₂ CH ₂ OH

HS- (CH ₂ ) _S -CO ₂ R - RfS- (CH ₂ J ₅ -CO ₂ R

UU

1. LiOH 2. HVH ₂ O

* RfS- (CH ₂ ) _s -COOH - -

5. For the group Y = (CF ₃ ) ₂ N- and for saturated fatty acids whose alkylene units are represented in the Schemes by (CH ₂ ) S, where s can be 4 to 25:

The introduction of the aliphatic (CF ₃ ) ₂ N- to the fatty acids succeeds first by reacting corresponding tetramethylammonium salts with halides, which have a corresponding number of C atoms for the desired fatty acid and a terminal double bond according to the scheme given. The respective tetramethylammonium salts can be obtained analogously to the description of EP 1081129. The corresponding disclosure to the mentioned method in the cited references thus expressly also belongs to the disclosure content of the present application.

Me ₄ NW

X = a, Br, I Rf = -N (CF ₃ ). The terminal double bond may be known to those skilled in the art

Methods are converted into the carboxy function. Examples are given in the following scheme, wherein Rf in the following scheme can be N (CF ₃ ) ₂ but also SCF ₃ or SC ₂ F ₅ :

- -

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 by means of the Gabriel synthesis (Organikum: Basic Organic Chemistry , 16th edition, 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.

A subsequent oxidation by, for example, C1O ₃ / H ₂ SO ₄ results in the modified acid.

6. For the group Y = CF ₃ - (CH ₂ ) _a -S- with a = 1 to 5 and for saturated fatty acids whose alkylene units in the schemes are represented by (CH ₂ ) _S , where s is 4 to 25 can:

The introduction of the CF ₃ - (CH ₂₎ _a -S- group is, for example, by reaction of CF ₃ - (CH 2) _a -OH with a = 1, 2, 3, 4 or 5 to the corresponding Fettsäureestern with a fatty acid ester, the terminally having a thiol group, via Mitsunobu reaction (Mitsunobu, O. Synthesis, 1981, 1) wherein the alcohols of the formula CF ₃ - (CH ₂ ) _a -OH are commercially available or readily available from commercially available substances.

Analogously to Example 5a-c, CF ₃ S or CF ₃ CF ₂ S or CF ₃ (CH) _a end groups can also be introduced instead of (CF ₃ ) ₂ N end groups. In the case of the sulfur-containing compounds, instead of Pd

Catalysts Pt or Ru catalysts used.

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

The end group CF ₃ NH- in compounds CF ₃ NH-R can by means of literature methods by reacting corresponding

Compounds CI ₂ C = NR are introduced with an excess of HF

(Corresponding syntheses are described, for example, in Petrow et al., Zh. Obshch. Khim. 29 (1959) 2169-2172.) Alternatively, also tifluoromethyl isocyanate with an alcohol to a compound CF ₃ - NHC (= O) -OR (according to Knunyants et al., Mendeleev, formerly J. 22 (1977) 15- 105 or Motornyi et al., Zh. Obshch. Khim. 29 (1959) 2157-2122). The corresponding starting materials are each after

Literature known methods available and the residues R of the products can be chemically modified by established methods.

8. For the group Y =

c being

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 ₁ NC (O) -N, O-SO ₂ or SO ₂ -O, _Q 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, wherein at least one of b and q is 1, and r is 0, 1, 2, 3, 4 or 5 and saturated fatty acids, wherein the alkylene units in Schemes 5 are represented by (CH ₂ ) _S s can be 4 to 25, then:

Introduction of this aromatic group into fatty acids succeeds according to the given scheme. In part, the respective Rf-substituted aromatics are commercially available. Otherwise, methods of synthesisQ 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 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 V-) , [CF ₃ - (CH ₂ V] 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 If Rf is used in the following schemes, unless otherwise stated, the definition given here applies.

The attachment of a spacer to aryl-Rf or further linkages via various functionalities are shown in Schemes I to VIII:

I. Etherification by Mitsunobu Reaction:

c = 0 and / or 1 n = 4 - 25

II. Linkage by thioether or sulfone unit

n = 4 - 25 - -

I. Amine formation

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 = 4 - 25

IV. Esterification or amide formation

c = 0 and / or 1 n = 4 - 25

- 2 -

V. Linkage via sulfonic acid esters and amides

R ¹ = H or alkyl with 1 to 4 C atoms q = 0 and / or 1 b = = 0 and / or 1 c = = 0 and / or 1 n = 4 - 25

The Arylsulfonsäurechlorid is obtained by reaction with CISO ₃ H from the corresponding aromatic.

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 n = 4 - 25 VI. Link via keto function

W = O, NH, NR ¹

HaI = Cl ₁ Br, I q = 0 and / or 1 b = 0 and / or 1 c = 0 and / or 1 n = 4 - 25

VII. Linkage via isocyanates or isothiocyanates

n = 4 - 25

VIII. Connection via Heck reaction

A = -CO ₂ R with R = Me, Et

HaI = Cl, Br, I q = 0 and / or 1 b = 0 and / or 1 c = 0 and / or 1 n = 4 - 25

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 (O or at least 1) b: para-position (O 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 ₁ is -CH ₂ CO ₂ H,

CH = CH ₂ , -CH = CHCO ₂ H, -C≡CCH ₂ OH.

Derivatization for aromatic systems with fluorinated CF ₃ groups:

Derivatization for aromatic systems with 3 fluorinated CF3 groups:

DCC: dicyclohexylcarbodiimide

TPAP: Tetra-π-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 '= -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 ₁ -NH ₂ , -NO ₂ , -N = C = O, -CHO, -CO ₂ H ₁ -CN ₁ -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:

or

For F ₃ CO:

Commercially available reagents or readily available substances are: G "= -OH, -I, -Br, -Cl, -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.

Concrete example

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 stands for an integer selected from the range from 0 to 5, can be carried out with the aid of the Gabriel synthesis (Organikum: Organic-Chemisches Grundpraktikum , 16th ed., VEB Deutscher Verlag der Wissenschaften, Berlin, 1986), followed by the release of the primary amine by reaction with hydrazine - -

respectively. 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 (CFa) 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 ₁ -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 SF4 / HF : - -

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:

Pur CP ₃ NH- applies:

The end group CP ₃ NH- in compounds CF ₃ NH-R can be introduced by methods known from the literature by reacting corresponding compounds CI ₂ C = NR with an excess of HR - -

(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 Motomyi et al., Zh. Obshch. Khim. 29 (1959) 2157-2122). The corresponding starting materials are in each case obtainable according to 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 SOCl ₂ and the radicals R of the products can be chemically modified by means of established methods.

The following schemes show chain extensions that are feasible regardless of Rf:

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

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 the reactions mentioned any difficulties (Organikum: Organic Chemical Basic Practical, 16th ed., VEB Deutscher Verlag der Wissenschaften, Berlin, 1986).

The invention further provides sulfonated fatty acid esters having at least one Y group, Y being 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 Jr, 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 ) 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 ₁

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. In the group Y, a is preferably 0, 1 or 2, particularly preferably 0 or 2, very particularly preferably 0 and r is preferably 0 to 3, in particular 0 to 1.

In a variant of the present invention it is preferred if in the

Group Y q stands for 0 and at least one c and / or b each stand for 1. In particular, it is preferred that all c and b are 1, i. the aromatics are substituted in the o- and / or p-position with fluorine groups, in particular in o, p, o-position.

In a preferred embodiment, the sulfonated radical may be replaced by the

partial formula

-O- (CH ₂ ) _o -SO ₃ M are described, where o = 1, 2, 3, 4, 5 or 6, preferably 2 or 4 and M = metal cation.

In the aforementioned partial formula, M represents a metal cation, in particular selected from an alkali metal cation, an alkaline earth metal cation or an ammonium ion. The lithium, sodium or potassium cation or NH ₄ ⁺ is preferably used for M. The group Y, as defined above, consists in a preferred variant of the invention from the subgroup CF ₃ -O-, SF ₅ -, CF ₃ -S-, CF ₃ CF ₂ S-, (CFa) ₂ N- or

where Rf 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 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,

Rf is preferably CF ₃ - (CH ₂ ) _r , CF ₃ - (CH ₂ XO-, 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, wherein r is preferably O.

In a particularly preferred embodiment of the present 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-.

A further preferred variant of the invention comprises the groups Rf equal to CF ₃ -, CF ₃ -S-, CF ₃ CF ₂ -S-, SF ₅ - or (CF ₃ ) ₂ N-. Particularly preferred groups B are O, S ₁ CH ₂ O ₁ 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) ₁ CF ₃ -S-Ar-OC (O), CF ₃ CF ₂ -S-Ar-OC (O), SF ₅ -Ar-OC (O), CF ₃ -CH ₂ -CH ₂ -S- Ar-OC (O), (CF ₃ ) ₂ -N-Ar-OC (O) and (CF ₃ -CH ₂ -CH ₂ ) ₂ -N-Ar-OC (O), in particular equal to 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.

The particularly preferred compounds of the sulfonated fatty acid esters include the following compounds:

The sulfonated fatty acid esters having at least one group Y, preferably terminally attached to the ester function, can be obtained by reacting a fatty acid having at least one group Y as described above for the fatty acid esters of polyols (items 1 to 7 and the accompanying schemes) with a sodium salt of a hydroxysulfonic acid 1 to 6 C atoms are reacted.

The hydroxysulfonic acids are commercially available or accessible by known synthesis.

The invention further provides sulfonated fatty acid amides having at least one Y group, Y being 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

R f = CF ₃ - (CH ₂ ) r, CF ₃ - (CH ₂ ) _r -O-, CF ₃ - (CH ₂ JrS-, CF ₃ CF ₂ -S-, SF ₅ - (CH ₂ ) _r - or [CF ₃ - (CH ₂ ) r] ₂ N-, [CF ₃ - (CH ₂ V] 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.

In a preferred embodiment, the sulfonated radical can be described by the partial formula -O- (CH ₂ ) o -SO ₃ M, where o = 1, 2, 3, 4, 5 or 6, preferably 2 or 4 and

M = metal cation.

In the aforementioned partial formula, M represents a metal cation, in particular selected from an alkali metal cation, an alkaline earth metal cation or an ammonium ion. The lithium, sodium or potassium cation or NH ₄ ⁺ is preferably used for M.

The group Y as defined above is a preferred one

Invention variant of the subgroup CF ₃ -O-, SF ₅ -, CF ₃ -S-, CF ₃ CF ₂ S-, (CF ₃ ) ₂ N- or in which

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, 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.

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-, (CF ₃ ) 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) ₁ CF ₃ -S-Ar-OC (O), CF ₃ CF ₂ -S-Ar-OC (O), SF ₅ -Ar-OC (O), 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).

Further preferred combinations are disclosed in the claims. The particularly preferred compounds of the sulfonated fatty acid amides include the following compounds:

The sulfonated fatty acid amides having at least one group Y, preferably terminally attached to the amide function, may be obtained by reacting a fatty acid having at least one group Y as described above for the fatty acid esters of polyols (items 1 to 7 and the accompanying Schemes) with a sodium salt of an aminosulfonic acid 1 to 6 C atoms are reacted.

The aminosulfonic acids are commercially available or accessible by known synthesis.

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.

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, inks, lacquers, photographic coatings (for photographic plates, films and papers), special coatings for semiconductor photolithography (photoresists, top anti-reflective coatings, bottom anti-reflective coatings) or other surface coating compositions, the compounds of the invention or the invention The compounds to be used are advantageously used with one or more of the following functions: anti-fogging agents, dispersants, emulsion stabilizers, defoamers, deaerators, antistatic agents, flameproofing agents, gloss enhancers, lubricants, pigment or filler compatibility improvers, scratch resistance improvers, substrate adhesion promoters, surface adhesion promoters , Anti-skinning agent, water repellent, oil repellent, UV stabilizer, wetting agent, leveling agent, viscosity reducer, migration inhibitor, drying accelerator. In printing inks, the compounds according to the invention or the compounds to be used according to the invention can likewise be used advantageously and have one or more of the following functions: defoamer, deaerator, agent for Friction control, wetting agents, leveling agents, pigment compatibility improvers, printing resolution enhancers, drying accelerators.

The use of the compounds according to the invention or 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 formulations for the addition of appropriate 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 of the invention or compounds to be used according to the invention as a foam stabilizer and / or to support film formation, especially in aqueous film-forming 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 In particular, antistatic effect is in the treatment of textiles, in particular clothing, carpets and rugs, upholstery in furniture and automobiles, non-woven textile materials, leather goods, papers and cartons, wood and wood-based materials, mineral substrates such as stone, cement, concrete, gypsum .

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 advantageously having one or more of the following functions: wetting agent, flow control agent, water repellent, oil repellent, stain and soil protection agent, Lubricant, defoamer, deaerator, drying accelerator can be used. 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, flow control agents, water repellents, oil repellents, stain and soil protectants, lubricants, defoamers, deaerators or drying accelerators is therefore another object of the invention.

Also as additives in polymeric materials (plastics) compounds of the invention or compounds according to the invention can advantageously with one or more of the following functions: lubricants, internal friction reducer, UV stabilizer, water repellents, Oleophobiermittel, protectants against stains and contaminants, coupling agents for 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. Next, the invention as

Surfactants useful compounds are advantageously used in cosmetic products, such as foam baths and hair shampoos or as emulsifiers in creams and lotions. As additives in hair and personal care products (e.g., hair conditioners and hair conditioners) having one or more of the following functions: wetting agents, foaming agents, lubricants, antistatic agents, skin fats enhancers, the compounds of the invention or the compounds to be used in accordance with the invention may also be used to advantage.

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 according to the invention or compounds to be used according to the invention having one or more of the following functions: hydrophobizing agent, oleophobizing agent, protective agent

Dirt, weathering improvers, UV stabilizer, anti-silicone bleed.

Another field of application for the compounds useful as surfactants in the present invention is flotation, i. the spreading 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 a carrier suitable for the particular intended use and optionally further specific active substances and / or, if appropriate, auxiliaries.

Preferred agents are colored and

Paint preparations, fire-extinguishing compositions, lubricants, detergents and cleaners, de-icers 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, The hydrophobic finish of textiles, especially weatherproof clothing, is used to make it either water-repellent or impermeable to water.The hydrophobing agent is applied to the fibers of the textiles and arranges them in such a way that the hydrophobic parts of the molecule are perpendicular to the surface of the fiber, thus reducing the tendency of the water 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 dyed and

Paint 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.

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 characteristics, properties and advantages of the compounds of the examples in question are also applicable to other substances and compounds not mentioned in detail but covered by the scope of protection, unless otherwise stated elsewhere. Incidentally, the invention is throughout range and not limited to the examples given here.

- 5 -

Examples

List of abbreviations used:

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

DCM: dichloromethane

DMAP: 4- (dimethylamino) pyridine

Me: methyl

MTB: methyl tert-butyl ether RT room temperature (20 ^° C.)

THF: tetrahydrofuran

PE: Petroleum ether

DCC N.N'-dicyclohexylcarbodiimide

RT room temperature TPAP tetra-n-propylammonium perruthenate

VE fully desalted

TLC thin layer chromatography

DIAD diisopropyl azodicarboxylate

example 1

1. Synthesis of (E) -10-pentafluorosulfanyl-dec-9-ene-carboxylic acid

In 250 ml of DCM (dichloromethane), 15 g of decenol are dissolved and cooled to -4O 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 ^ B solution are added. When Gaseinieitung the approach is cloudy. The activation is repeated until the mixture no longer warms up when the gas is introduced. The mixture is stirred for two hours at the same temperature. The reaction mixture is added by addition to ice / NaHCO ₃ . Solution (saturated) hydrolyzed and then adjusted with NaOH pH10. The separated aqueous phase is washed twice more with MTB ether (MTB ether = methyl tert-butyl ether). The collected organic phases are extracted once with NaCl solution, dried over sodium sulfate, filtered and concentrated by rotary evaporation. After chromatography, the product is obtained in pure form.

elimination:

9 g of the starting material (28.2 mmol) are dissolved in 120 ml of ethanol in a 250 ml one-necked flask with reflux condenser and then KOH powder (4.75 g, 85 mmol, 3 eq) is added. The reaction mixture is stirred overnight, then concentrated and water and MTB ether added. After separation of the phases, the aqueous phase is extracted 3 times with MTB ether, the collected organic phases with sat. NaCl solution, dried over Na ₂ SO ₄ , filtered off and distilled off from the solvent. There are obtained 8.3 g of yellowish liquid. The Rf value is slightly higher (more apolar substance) than the educt.

Oxidation:

O ^xidalion .

Literature: Tetrahedron Vol. 44, no. 9, pp.2636 1988 11.3 mmol of the alcohol are dissolved in a solvent mixture of carbon tetrachloride (40 ml), acetonitrile (40 ml) and water (50 ml), then the sodium metaperiodate (5.44 g, 25.4 mmol, 2.25 eq) and the ruthenium ( III) chloride (234 mg, 1.13 mmol, 0.1 eq) was added and the reaction mixture stirred for 3 hours at 22 ° C - 26 ° C (RT). Thereafter, 50 ml of dichloromethane are added to the reaction mixture, the phases separated and the aqueous phase is extracted twice with 50 ml dichloromethane. The combined dichloromethane solutions are dried with sodium sulfate, filtered and the solvent is distilled off. The product is obtained as an oily residue.

2. Esterification with sorbitol

30 g of (E) -10-pentafluorosulfanyl-dec-9-ene-carboxylic acid in 100 g of toluene are introduced and 24 g of SOCl _{2 are} added. The reaction mixture is heated to 70 ⁰ C and distilled off the excess of SOCb and solvent. The resulting acid chloride is used without further purification in the subsequent acylation.

sorbitol R1 ... R6 = H or

18 g of sorbitol are suspended in 150 g of THF (tetrahydrofuran), followed by addition of 32 g of the acid chloride (1 equivalent) and 10 g of triethylamine. After completion of the reaction, the product mixture is isolated by conventional laboratory methods and purified.

The degree of acylation can be increased by using more acid chloride (2-20 equivalents). A monoacylation takes place preferentially for R1 or R6; a diacylation preferably takes place for R1 and R6.

Example 2

R1 ... R8 = H or

34 g of sucrose are suspended in 100 g of THF and then 31 g of (E) -10-pentafluorosulfanyl-dec-θ-ene-carboxylic acid chloride, prepared according to Example 1, and 10 g of triethylamine (10 g) are added. After completion of the reaction, the product mixture is isolated by conventional laboratory methods and purified. The degree of acylation can be increased by using more acid chloride (2-20 equivalents).

A monoacylation takes place preferentially for R1 or R5 or R8; Diacylation preferably takes place for R1 / R5 or R1 / R8 or R5 / R6.

Example 3

1. Synthesis of 7- (3,3,3-trifluoropropoxy) -heptanoic acid methyl esters

3,3,3-trifluoropropanol (10 ml, 110 mmol), 7-hydroxyheptanoic acid methyl ester (133 mmol, 1.2 eq), triphenylphosphine (35 g, 133 mmol, 1.2 eq) in 37 ml of THF are placed in a round-bottomed flask and sonicated for a few minutes brought to mix the substances. During the Upon exposure to ultrasound, DIAD (26.5 ml, 133 mmol, 1.2 eq) is added dropwise very slowly (temperature rises) and the reaction mixture is left under ultrasound for 15 min. A DC sample is taken and then left in the ultrasonic bath for a further 2 hours. The solvent is removed on a rotary evaporator. Subsequently, 90 ml of cold MTB ether are added, whereby triphenylphosphine oxide precipitates. The solid is sucked off and the solution stored over the weekend in the refrigerator, so that the rest still falls. The residual solid is filtered off with suction and the residue is washed with MTB. The product solution is concentrated by rotary evaporation and purified by column chromatography.

2. Synthesis of 7- (3,3,3-trifluoropropoxy) heptanoic acid

In a round-bottomed flask, 7- (3,3,3-trifluoropropoxy) - heptanoic acid methyl ester (50 mmol) are dissolved in 500 ml of THF and treated at RT with lithium hydroxide (65mmol, 1.3eq) in portions. The mixture is stirred for 1 h at RT and then 100 ml of water and 200 ml of MTB ether are added. The mixture is acidified to pH 1 with aqueous HCl, the phases are separated and the aqueous phase is extracted several times with MTB. The combined organic phases are dried over sodium sulfate and concentrated by rotary evaporation. The resulting carboxylic acid is used directly in the next step.

3. Esterification with sorbitol

R1 ... R6 = H or

Analogously to Example 1, initially 24 g of 7- (3,3,3-trifluoropropoxy) heptanoic acid are initially charged in 100 g of toluene and reacted with 24 g of SOCl ₂ and the resulting acid chloride is esterified with 18 g of sorbitol in THF and in the presence of triethylamine.

Example 4

R1 ... R8 = H or

Analogously to Example 2, 34 g of sucrose in 100 g of THF are reacted with 30 g of (7- (3,3,3-trifluoro-propoxy) -heptanoic acid chloride, prepared according to Example 3, and 10 g of triethylamine (10 g) Reaction, the product mixture is isolated and purified by standard laboratory methods and the degree of acylation can be increased by using more acid chloride (2-20 equivalents). Example 5

1. Synthesis of the acid

F> Jx ^F

O.

OH

a: Preparation of the ammonium salt:

(CH ₃ ) ₄ N ⁺ F- + CF ₃ SO ₂ N (CF ₃ ) ₂ - (CH ₃ ) ₄ N ⁺ N (CF ₃ ) ₂ -O

A solution of 0.017 g (0.18 mmol) (CH ₃ ) ₄ N ⁺ F ^' in 0.5 ml of dry

Dichloromethane is treated with 0.052 g (0.18 mmol) of CF ₃ SO ₂ N (CF ₃ ) ₂ at -40 ⁰ C added. The reaction solution is warmed to room temperature, diluted with the same amount of dry acetonitrile. ₅ after distillative removal of the solvent in a dry argon atmosphere 0.037 g of a colorless, highly hygroscopic material are obtained in a yield of 90.2%.

19F NMR (CCI ₃ F): -40.8 s; Melting point: 120-125 ⁰ C 0 b: Preparation of the allyl compounds:

X = Br

A mixture of 0.837 g (2.12 mmol) of (CH ₃ ) ₄ ⁺ N (CF ₃ ) ₂ ^' and 0.196 g (1.62 mmol) of allyl bromide is heated at reflux under argon atmosphere for several hours. After complete conversion, the product is distilled off. c: chain extension

To a solution of the olefinic methyl ester (28.1 mmol) in 70 ml

Dichloromethane is added to the allylamine derivative (4.2 g, 21.8 mmol) followed by the Grubbs II metathesis catalyst (0.9 g, 1 mmol). The mixture is refluxed for 17 hrs.

Thereafter, the mixture is evaporated and purified on a column. To completely separate the catalyst is chromatographed again with. The coupled product is thus obtained.

d. Hydrogenation of the double bond

The methyl ester (27 mmol) is taken up in 250 ml of THF and treated with 5% palladium on activated carbon (10 mol%). After creating the

Hydrogen atmosphere (increased pressure), the reaction mixture is stirred for 3 h and worked up after completion of the reaction. For this purpose, the catalyst is filtered off under a protective gas atmosphere and the solution is evaporated on a rotary evaporator. The product can be used directly in the next stage.

e: Preparation of the acid

10 mmol of the methyl ester are dissolved in 100 ml of THF and, at RT, mixed in portions with solid lithium hydroxide (13 mmol, 1.3 eq). The mixture is stirred for 1 h at RT and then 40 ml of water and 100 ml of MTB ether are added. The mixture is acidified to pH 1 with aqueous HCl, the phases are separated and the aqueous phase is extracted several times with MTB. The combined organic phases are dried over sodium sulfate and concentrated by rotary evaporation. The resulting carboxylic acid is used directly in the next step.

2. Esterification

S orbital

Analogously to Example 1, initially 0.1 mol of the carboxylic acid in 100 g of toluene are introduced and reacted with 24 g of SOC ^ and the resulting acid chloride esterified with 18 g of sorbitol in THF and in the presence of triethylamine.

Example 6

R1 ... R8 = H or

Analogously to Example 2, 34 g of sucrose in 100 g of THF are reacted with 0.1 mol of acid chloride prepared according to Example 5 and 10 g of triethylamine (10 g). After completion of the reaction, the product mixture is isolated by conventional laboratory methods and purified. The degree of acylation can be increased by using more acid chloride (2-20 equivalents).

Example 7

Sodium hydride (92g, 2.3mol, 1.36eq) was suspended in 1200 ml of THF and cooled to 0 ⁰ C. To this suspension, heptane-1, 7-diol (224g, 1.7 mol) dissolved in 400 ml of THF is added dropwise (attention: ^ -Developung). The reaction mixture is warmed to room temperature and stirred for 3 hrs. Then benzyl bromide (251.3 ml, 2.11 mol, 1.25 eq) and tetrabutylammonium iodide (32 g, dδδmmol, 0.05 eq) are added and the mixture is stirred overnight (9 h). For workup, the reaction mixture is quenched with 1200 ml of ice water, the organic phase is separated off, the aqueous phase is extracted twice with MTB ether and the combined organic extracts are washed with saturated NaCl solution. After drying the organ. phase and rotary evaporation, the crude product is obtained, which is purified on silica gel.

200 ml of THF and 10.15 g of NaH (253 mmol, 1.2 eq) are placed in a nitrogen-lavated 11 four-neck glass apparatus and cooled to -25 ° C. with stirring. in

7-Benzyloxyheptan-1-ol (211 mmol, 1 eq) is mixed with 100 ml THF and added dropwise within 30 min (rinsed with 50 ml THF), while the internal temperature is maintained at 0-5 ⁰ C. Thereafter, the reaction mixture is heated to RT within 30 min.

It is stirred for 120 min at RT and then cooled to -25 ° C. ¹⁵ The carbon disulfide (32.1 g, 421.6 mmol, 2 eq) is added dropwise within 10 min. The reaction mixture is warmed to 0 ⁰ C. It is stirred at 0 ⁰ C for 2.5 h. The color of the reaction mixture changes from light brown to brown.

For the addition of the methyl iodide is cooled again to -2O ⁰ C and

Subsequently, MeI (35.9 g, 253 mmol, 1.2 eq) is added dropwise within 5 min (strong evolution of heat: countercooled at -78 ° C). The

Reaction mixture is warmed slowly to RT and 24 hrs at this

Stirred temperature.

For workup is then with about 10% NH ₄ Cl solution (200 ml) of the

Approach quenched.

The phases are separated. The water phase is washed twice with 100 ml

MTB ether washed. The organic phases are combined and then washed 1 time with about 10% 100 ml of saturated NaCl solution, separated and dried with Na ₂ SO ₄ , filtered and on

Rotary evaporator concentrated to residue. - -

To a suspension of DBH (211 g, 738 mmol, 3.1 eq) in 1000 ml DCM is added at -78 ° C successively (HF) g / Py (200ml, 7.14mol, 30eq) and then methylxanthogenate (238mmol) in 400ml DCM.

The reaction mixture is 1 h at

Stirred at -78 ° C and slowly warmed overnight with stirring (temperature in the morning 2 ° C). The RG is heated to 19 ⁰ C and then about 1 hour at this

Temperature stirred.

It is then cooled again to hydrolyze.

In a 4L four-necked flask, 640 ml NaHSO ₃ solution and 600 ml

Submitted 47% KOH and cooled to ⁰ ° C. Then the reaction mixture is sucked by means of vacuum in the four-necked flask.

The whole thing is done in portions. The maximum temperature should be

20 ⁰ C be.

The dark red reaction solution becomes a yellowish suspension. As much 47% KOH in 400 ml deionised water are added to this suspension until a pH of 7 is reached. The suspension is getting thinner and thinner.

The phases are separated and the aqueous extracted with MTB ether 2 times.

The collected organic phases are washed once with a

Washed brine, dried over sodium sulfate and then concentrated.

The crude product is stirred with activated charcoal and purified by column chromatography in petroleum ether.

The benzyl ether (150 mmol) is taken up in ethanol (1000 ml) and provided with 5% palladium (0.1 eq) on activated charcoal. After applying a hydrogen atmosphere (elevated pressure), the reaction progress is monitored by TLC every hour. To complete the reaction, spent catalyst is filtered off and re-added fresh catalyst. After completion of the reaction, the palladium catalyst is filtered off and the reaction mixture is concentrated. The crude product is used directly in the next step.

According to Example 1, 22.6 mmol of the alcohol in one

Solvent mixture of carbon tetrachloride (80 ml), acetonitrile (80 ml) and water (100 ml), then the sodium metaperiodate (10.88 g,

50.8 mmol, 2.25 eq) and the ruthenium (III) chloride (468 mg, 2.26 mmol, 0.1 eq) were added and the reaction mixture was stirred at 22 ° C.-26 ° C. (RT) for 3 hours. Thereafter, 100 ml of dichloromethane are added to the reaction mixture, the phases are separated and the aqueous phase is back-extracted twice with 100 ml of dichloromethane. The combined dichloromethane solutions are dried with sodium sulfate, filtered and the solvent is distilled off. The carboxylic acid is obtained as an oily residue.

Analogously to Example 1, initially 21 g of 7-trifluoromethoxyheptanoic acid are initially charged in 100 g of toluene and reacted with 24 g of SOCl ₂ and the resulting acid chloride is esterified with 18 g of sorbitol in THF and in the presence of triethylamine.

Example 8

Analogously to Example 2, 34 g of sucrose in 100 g of THF are reacted with 0.1 mol of the acid chloride prepared according to Example 7 and 10 g of triethylamine (10 g). After completion of the reaction, the product mixture is isolated by conventional laboratory methods and purified. The degree of acylation can be increased by using more acid chloride (2-20 equivalents).

Example A:

(X: Cl)

31 g of (E, IO-pentafluorosulfanyl-dec-O-ene-carboxylic acid chloride prepared according to Example 1 are dissolved in 100 g of THF, with 2-hydroxy-ethanesulfonic acid Na salt (15 g) and triethylamine (10 g ) was added and stirred for 6 hours at 3O C ^0th

For product isolation is added to ice / methyl tert-butyl ether, the water phase is extracted with this solvency and all org. Phases evaporated. Ethanol is added and then 1.2 equivalents of sodium hydroxide. It is briefly heated and after cooling, the resulting crystals are isolated and dried.

Example B:

(X: Cl)

(E) -1 O-Pentafluorosulfanyl-dec-O-ene-carboxylic acid chloride, prepared according to Example 1, is dissolved in THF (100 g), with 2-methylamino-ethanesulfonic acid Na salt (16 g) and triethylamine ( 10 g) and stirred. For product isolation is added to ice / methyl tert-butyl ether, the water phase is extracted with this solvency and all org. Phases evaporated. Ethanol is added and then 1.2 equiv. Sodium hydroxide. - -

It is briefly heated and after cooling, the resulting crystals are isolated and dried.

Example C:

(X: Cl)

Analogously to Example A, 26 g of 7- (3,3,3-trifluoropropoxy) heptanoic acid chloride in THF are reacted with 2-hydroxyethanesulfonic acid Na salt (15 g) and triethylamine (10 g). The resulting crystals are isolated and dried.

Analogously to Example B, 26 g of 7- (3,3,3-trifluoropropoxy) heptanoic acid chloride in THF are reacted with 2-methylaminoethanesulfonic acid Na salt (16 g) and triethylamine (10 g). The resulting crystals are isolated and dried.

Example D: - -

(X: Cl)

Analogously to Example A, 23 g of 7- (trifluoromethoxy) -heptanoic acid chloride _> prepared according to Example 7 in THF are reacted with 2-hydroxy-ethanesulfonic acid sodium salt (15 g) and triethylamine (10 g). The resulting crystals are isolated and dried.

Analogously to Example B, 23 g of 7- (trifluoromethoxy) heptanoyl chloride in THF are reacted with 2-methylaminoethanesulfonic acid Na salt (16 g) and triethylamine (10 g). The resulting crystals are isolated and dried.

Example E:

Analogously to Example A, 34 g of acid chloride, prepared according to Example 5 in THF with 2-hydroxy-ethanesulfonic acid Na salt (15 g) and triethylamine (10 g) were reacted. The resulting crystals are isolated and dried.

34 g of acid chloride prepared according to Example 5 are reacted in THF with 2-methylaminoethanesulfonic acid Na salt (16 g) and triethylamine (10 g) in analogy to Example B. The resulting crystals are isolated and dried.

_{1 5} Example 9: 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

2Q European Union, Part II - Test Methods, Annex V - Methods for

Determination of Physicochemical Properties, Toxicity and Ecotoxicity, Part B, Biochemical Degradability - Zahn-Wellens Test (C9.), January 1997, pages 353-357. Batch volume: 1, 5 1 p _c activated sludge concentration: 1 gTS / l

Origin of the sludge: WWTP of Merck KGaA;

Darmstadt (not adapted)

Amount used of the test substances: approx. 100 to 200 mg / l as DOC ventilation: with purified air

2Q 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 also in the OECD Guideline for the testing of chemicals, section 3, degradation and accumulation, method 302 B, page 1-8, adopted: 17.07.92, whose contents are expressly to the disclosure content belongs to 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 10: Determination of the surface tension

Device: Tensiometer from Krüss (model K12)

Temperature of the measuring solutions: 20 ^° C

Measurement module used: Ring Concentration of the measurement solutions: approx. 0.5 to 3.0 g / l in deionized

water

Further details on the method can be found in the publication European 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 are taken from their content in this regard expressly to the disclosure content of belongs to the present application.

Claims

- Patent claims

1. fatty acid esters of polyols or sulfonated fatty acid esters or sulfonated fatty acid amides having at least one group Y, wherein Y is CF ₃ - (CH ₂ ) _a -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 ) _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 - ₁₅ ( CH ₂ ) _r - 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) ₁ S, CH ₂ -O,

0-C (O) ₁ NC (O), C (O) -N, 0-C (O) N, NC (O) -N, 0-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, 2Q 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.

2. Compounds according to claim 1, characterized in that the fatty acid radical may be saturated or unsaturated with 4 to 25 C atoms,

Preferably 25 with 8 to 22 carbon atoms.

3. Compounds according to claim 1 or 2, characterized in that the group Y is terminal to the ester function.

2Q 4. Compounds according to one or more of claims 1 to 3, characterized in that the polyol radical of a radical -0-CH ₂ - (CHOH) _n -CH ₂ -OH with n = 1, 2, 3,

4 or 5, a monosaccharide radical, - -

a disaccharide radical or an oligosaccharide radical.

5. Compounds according to one or more of claims 1 to 4, characterized in that the fatty acid radical with the group Y occurs at least once.

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

8. Compounds according to one or more of claims 1 to 7, characterized in that the group Y CF ₃ - (CH ₂ ) aS- 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, 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.

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.

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 ) P-, CF ₃ - (CH ₂ XO-, 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 ) JNH- or (CF ₃ ) ₂ N- (CH ₂ ) _r , B is a single bond, O ₁ NH, NR , CH _2, C (O) -O, C (O), S, CH ₂ -O, ₀ OC (O) NC (O), C (O) N, OC (O) N, NC ( O) -N, O-SO ₂ or SO ₂ -O, 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 a residue of b and q is 1, and r is O, 1, 2, 3, 4 or 5. 5

Process for the preparation of compounds according to one or more of Claims 1 to 12, characterized in that a fatty acid having a group Y as defined in one or more of Claims 1 to 12 or a derivative of this fatty acid is esterified with a polyol.

14. Compounds according to one or more of claims 1 to 3, characterized in that the sulfonated radical is described by -O- (CH ₂ ) _o -SO ₃ M 5, where o = 1, 2, 3, 4, 5 or 6, preferably 2 or 4 and M = metal cation.

Compounds according to claim 14, characterized in that the metal cation is an alkali metal cation, an alkaline earth metal cation or a

Ammonium ion is.

16. Compounds according to claim 14 or 15, characterized in that the group Y CF ₃ - (CH ₂ ) _a -O- with a = 0, 1, 2, 3, 4 or 5, preferably a = 0, 1 or 2 means.

17. Compounds according to one or more of claims 14 to 16, characterized in that the group Y SF ₅ means.

18. Compounds according to one or more of claims 14 to 17, 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.

19. Compounds according to one or more of claims 14 to 18, characterized in that the group Y CF ₃ -CF ₂ -S- means.

20. Compounds according to one or more of claims 14 to 19, 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.

21. Compounds according to one or more of claims 14 to 20, 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.

22. Compounds according to one or more of claims 14 to 21, characterized in that the group Y

means, where

Rf is CF ₃ - (CH ₂ Jr, 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 ) J ₂ N-, [CF ₃ - (CH ₂ ) JNH- or (CF ₃ ) ₂ N- (CH ₂ ) _r -, B represents a single bond, O ₁ NH, NR, 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 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 0, 1, 2, 3, 4 or 5.

Process for the preparation of compounds according to one or more of Claims 14 to 22, characterized in that a fatty acid having a group Y as defined in one or more of Claims 1 to 3 or 14-22 is reacted with a sodium salt of a hydroxysulfonic acid 1 to 6 carbon atoms is esterified.

24. Composition containing at least one compound according to one or more of claims 1 to 12 or 14 to 22.

25. A composition according to claim 24, characterized in that a suitable carrier for the respective purpose and optionally further specific active ingredients are included.

26. Composition according to claim 24 or 26, characterized in that it is the agent to dye and lacquer preparations, fire-extinguishing agents, lubricants, detergents and cleaners, deicers or water repellents for textile finishing or glass treatment.

27. A process for preparing a composition according to one or more of claims 24 to 26, characterized in that at least one compound is mixed according to one or more of claims 1 to 12 or 14 to 22 with a suitable carrier and optionally with other specific active ingredients. - -

28. Use of compounds according to one or more of claims 1 to 12 or 14 to 22 as surfactants.

29. Use of compounds according to one or more of claims 1 to 12 or 14 to 22 as a water repellent or

Oleophobiermittel, in particular in the surface modification of textiles, paper, glass, porous building materials or adsorbents is used.

30. Use of compounds according to one or more of claims 1 to 12 or 14 to 22 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 cartonboard, 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.

31. Use of compounds according to one or more of claims 1 to 12 or 14 to 22 as additives in surface coating preparations, 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.

32. Use of compounds according to one or more of claims 1 to 12 or 14 to 22 as a foam stabilizer and / or to aid the film formation, in particular in fire-extinguishing foams. - -

33. Use of compounds according to one or more of claims 1 to 12 or 14 to 22 as an interface mediator or emulsifier, in particular for the production of fluoropolymers.

34. Use of compounds according to one or more of claims 1 to 12 or 14 to 22 as antimicrobial agent, in particular as a reagent for the antimicrobial surface modification.